a review of nucleation, growth and low temperature synthesis of...

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A review of nucleation growth and lowtemperature synthesis of diamond thin films

D Das and R N Singh

Diamond thin films have outstanding optical electrical mechanical and thermal properties which

make these attractive for applications in a variety of current and future systems In particular the

wide band gap optical transparency and unusually high thermal conductivity of diamond thin

films make them an ideal semiconductor for applications in current and future electronics

However synthesis of diamond thin films with adequate quality remains a challenging task

Synthesis of diamond at low temperatures is even more challenging because of the difficulties in

the nucleation and growth steps involved in diamond thin film deposition on a variety of

substrates Among the several deposition techniques for synthesising diamond films plasma

enhanced chemical vapour deposition is the most promising technique because of its potential for

low temperature synthesis Consequently the first part of this paper reviews the current state of

the nucleation and growth of diamond during chemical vapour deposition A uniform and high

nucleation density is a prerequisite for getting a good quality diamond film with significant growth

rate Also since the process conditions for nucleation and growth steps are different attempts are

made in this review to identify the important parameters responsible for enhancing the nucleation

and growth rates of diamond film Describing the indispensable need for low temperature growth

of diamond film the second part of the paper reviews the research on the growth of diamond thin

films at low temperatures In spite of the slower kinetics at lower deposition temperatures an

attempt is made to identify the key processing conditions which enhance the low temperature

growth process In addition the mechanisms of diamond nucleation and growth are discussed

based on the observations from in situ characterisation techniques such as Fourier transform

infrared reflection absorption spectroscopy real time spectroscopic ellipsometry and molecular

beam mass spectroscopy

Keywords Low temperature growth CVD Nucleation and growth Diamond film

IntroductionThe diamond film research has attracted renewedinterest in recent years owing to its outstanding opticalelectrical mechanical and thermal properties1 Amongthe various diamond deposition processes developedover the past 15 years the hot filament chemical vapourdeposition (HF-CVD) process and the microwaveplasma CVD (MP-CVD) method have proven to bethe most used diamond deposition processes in achiev-ing a good quality diamond film2 Diamond researchover the years established conditions for well definedgrowth of the films which included high substratetemperature (typically 700uC) and a carbon containingprecursor gas diluted in excess of H2 However the highsubstrate temperature limits the use of diamond films in

many industrially important systems such as electronicssubstrate Consequently a major goal in the diamondresearch has been to lower the substrate temperaturerequired for diamond growth This will permit the use ofa much wider range of substrate materials of industrialimportance such as Al Si SiC GaN GaAs Ni and steelin different mechanical electrical optical and electronicapplications Lowering of substrate temperature duringdiamond synthesis could be an important step fordeposition on low melting materials as well

Nucleation is the first and probably the mostimportant step in achieving a good quality diamondfilm A uniform nucleation throughout the substratesurface along with its density affects the subsequentgrowth stage A slight change in the processingparameter such as gas composition concentration ofthe precursor gases in the mixture temperature pressureand microwave (MW) power can alter the nucleationprocess A good pretreatment of the substrate is aprerequisite for good nucleation A uniform and dense

Department of Chemical and Materials Engineering University ofCincinnati Cincinnati Ohio 452210012 USA

Corresponding author email RajSinghucedu

2007 Institute of Materials Minerals and Mining and ASM InternationalPublished by Maney for the Institute and ASM InternationalDOI 101179174328007X160245 International Materials Reviews 2007 VOL 52 NO 1 29

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nucleation leads to a better growth of the diamond filmJust like nucleation growth of diamond film is verymuch dependent on the deposition parameters The firstpart of this paper deals with the effect of the processingconditions on nucleation and growth of diamond filmTo have a better understanding and control of thedeposition process the underlying mechanism of nuclea-tion and growth has been discussed in view of some ofthe recent research findings in this area The surfacereaction and the gas phase chemistry involved indiamond film formation are explained in the light ofsome in situ characterisation technique such as real timespectroscopic ellipsometry (RTSE) and molecular beammass spectroscopy (MBMS)

The second part of this paper reviews the recentresults on low temperature growth of diamond film Theinterest in low temperature deposition of CVD diamondfilms stems from its excellent mechanical electricalelectronics optical and thermal properties Low coeffi-cient of friction close to that of teflon high hardness(hardest material) insensitivity towards moisture high-est elastic modulus and high thermal conductivity makediamond very attractive for large scale mechanicalapplications3 One of the main applications of diamondfilm in this area is the wear resistant coatings on cuttingtools drills and milling tools4 Numerous reports in theliterature show the advantage of the low temperaturedeposition of diamond film on hard tool materials5ndash14

However low deposition temperatures strongly reducethe growth rate and change the film morphology Evenfor very thin films high roughness is frequently obtainedwhen the film is deposited at low temperatures Lowtemperature diamond deposition is also important inelectronics15ndash18 Growing diamond films at low tem-peratures typically 500uC is important for manyapplications in electronics since substrate materials likeGaAs GaN plastics ZnS and MgF2 are unstable athigh temperatures19 and also to fabricate stress freediamond film on substrate because of the difference incoefficient of thermal expansion between diamond andsubstrates For optical applications the low temperaturedeposition of diamond films is inevitably requiredbecause of the low melting point of the optical materialssuch as glass Diamond deposition on optically trans-parent substrates such as sapphire zirconia and zincsulphide is of immense technological importance formany applications such as infrared windows20ndash22 Singlecrystal diamond possesses the highest thermal conduc-tivity (20ndash25 W cm21 K21) at room temperature of anymaterials This property coupled with a low thermalexpansion coefficient and a large electrical resistancemakes it the best material for heat sink application inelectronic devices23ndash25 But the use of diamond filmsfor thermal applications requires a high crystallinityreduced grain boundary network and very low contam-ination by non-carbon elements Low temperaturedeposition also eliminates the risk of any Si (for Siwafer) or other substrate material diffusion into thedeposited diamond layers

A review on the growth of diamond films at lowtemperatures was written by Muranaka et al in 199426

Limitations of substrate temperature in getting goodquality diamond films were discussed in the review Ingeneral the authors have suggested that low tempera-ture growth promotes the formation of amorphous

component at the cost of crystallinity of the film In spiteof the above difficulties several groups have tried todeposit good quality diamond films at low substratetemperatures using different precursor gases and sub-strates for various mechanical electrical optical elec-tronics and thermal properties in successive years27ndash34

However there are still some obvious problems forlow temperature CVD such as heating of the substratesby the plasma forced cooling of the substrate stage(holder) measurement of the real substrate temperatureand poor nucleation and slow growth rates Theinfluence of deposition parameters on low temperaturegrowth of diamond film has been discussed andparameters that enhance the low temperature growthhave been identified Since the kinetics of diamondgrowth is slow at low deposition temperatures a suitablepretreatment of the substrate which ensures a uniformand high nucleation density is an essential step beforedeposition For further understanding of the low tem-perature growth process the gas phase chemistryinvolved and the mechanism of the film formation atlow temperature are discussed

Nucleation of diamond

Effect of substrateDiamond nucleation is influenced by the choice ofsubstrates Since the lattice parameter and structure ofthe substrate materials with respect to diamond areimportant considerations in deciding a good filmgrowth all substrate materials do not respond equallyin getting a good adhesion of the film Early develop-ment of the CVD diamond films has been performed onsingle crystal diamond substrates3536 Diamond seedshave also been used in realising good diamond films37

The previous works are mostly confined to gettinghomoepitaxy of diamond In 1982 a breakthrough inCVD diamond technology was achieved by Matsumotoet al by growing diamond on to a non-diamond Si (100)substrate36 Hydrogen and hydrocarbon were activatedby passing through a hot filament at 2000uC and thediamond film was deposited onto a non-diamondsubstrate located 10 mm away from the filamentGraphite was etched simultaneously by atomic hydrogenleading to a higher growth rate (1 mm h21) Apartfrom having a very low nucleation density a continuousfilm was not achieved Diamond deposition was alsocarried out on a commercial purity titanium and Tindash6Alndash4V alloy substrates using a hot filament (tantalum)CVD and H2ndash1CH4 gas precursors38

The nucleation and early stages of growth of diamondwas studied on high performance ceramics Si3N4 using agas mixture of H2 and CH4 by an MPCVD process39

The influence of the substrate on the nucleationbehaviour was shown to be related to the change inmicrostructure during etching and to the reaction ofcarbon plasma species with Si3N4 where the incubationstage was mainly affected An optimisation of thenucleation and growth of diamond was performed withSi3N4 using the same gas mixture and MPCVD where anorthogonal design of experiments was used to optimisethe process parameters for achieving high nucleationdensity and growth40 The nucleation density increasedconsiderably with decreasing reactor pressure duringinitial nucleation stage Since the attack of the aggressive

Das and Singh A review of nucleation growth and low temperature synthesis of diamond thin films

30 International Materials Reviews 2007 VOL 52 NO 1

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plasma (mainly H atoms) destroys the nuclei formed onthe substrate surface at higher reactor pressure lowergas pressure favours nucleation at early stage of growthHigh pressure on the other hand favoured the growthrate because of the higher concentration of the reactingspecies in the denser plasma at higher pressure

The quality and adhesion of diamond coatings oncommercial silicon nitride (Si3N4) cutting tools werestudied by low pressure MPCVD at various processingconditions41 The nucleation density decreased withincreasing pressure while it increased with increase inthe CH4 concentration Substrate temperature and CH4

concentration were the most important parameters indeciding overall growth rate as well as the quality of thediamond films It was suggested that the intermediatesilicon carbonitride SiCxNy layers can provide nuclea-tion sites for diamond crystallite growth enhancediamond nucleation density on non-diamond substratesand control morphology orientation and texture ofthe diamond films Several nucleation mechanisms ondifferent intermediate layers were proposed based on anextensive review by Liu and Dandy in the literatureswhich are discussed below42

Nucleation on intermediate layer of diamond like

amorphous carbon

It has been proposed that diamond crystallites grow froman intermediate amorphous a-C layer which serves asnucleation sites43 The bonding structure of the depositedcarbon clusters are changed from sp1 to sp2 These sp2

bonded carbon atoms in turn are converted into arelatively stable network of sp3 bonded carbon Theetching of the unstable phases (sp1 and sp2) by H plasmaor OH rich plasma (for oxygen containing precursors)promotes stabilisation of the sp3 phase The carbon atomstry to rearrange towards 111 planes during crystal-lisation to minimise the energy content which act asnucleation sites for the subsequent growth stage

Nucleation on intermediate layer of metal carbide

Because of the better lattice matching between diamondand b-SiC (22 against 52 between diamond and Si)diamond nucleation is believed to occur on an inter-mediate carbide layer Carbon from the hydrocarbonprecursor gets dissolved in the substrate forming a stablecarbide on top of the substrate When the carbonconcentration in the carbide layer reaches a super-saturation diamond starts to nucleate on top of it Thiseffect is much more prominent on the transition metalsubstrate because of their strong carbide formingtendency On Si3N4 substrate also diamond nucleationoccurs on SiC interlayer The thin native oxide layer(SiO2) on Si3N4 is first converted to SiC duringdeposition in the hydrocarbon atmosphere (carburisingatmosphere) which then acts as a nucleation enhancingintermediate layer

Nucleation on intermediate layer of graphite

Diamond nucleation is also believed to occur from anunderneath graphite layer Graphite has been suggestedto condense initially on the substrate surface whose1100 prism planes are hydrogenated44 Diamondnuclei then grow preferentially on the prism planes ofgraphite which act as interface between graphite and thediamond nuclei

Commercial cemented WC tools of different cobaltconcentrations (3 6 and 12Co) have also been used assubstrate to deposit diamond by low pressure MPCVDto assess the role of cobalt on the quality and adhesionof the diamond coatings13 At lower deposition tem-peratures surface Co appeared to affect the diamondgrowth in the early stages especially with the higher Coconcentrations (6 and 12Co) Cobalt was found tocover the growing diamond nuclei and dissolved some ofthe carbon (owing to its high solubility with Co) therebyextending the incubation period This effect was moreprominent at higher deposition temperature since moreCo was diffused to the surface from the bulk throughthe grain boundaries An improved nucleation densityadhesion and surface properties were observed in coat-ing polycrystalline diamond onto three dimensionalcomplex shaped cemented tungsten carbide (WCndashCo)burs used for dental applications under the applicationof a negative bias voltage to the substrate in a modifiedvertical HFCVD system45

Varying methane (CH4) to hydrogen (H2) ratios of4 to 9 was used to coat stainless steel substrates withdiamond thin film using electron cyclotron resonance(ECR) MPCVD technique46 Below CH4H2 ratio of 4no diamond deposition was detected In the depositedfilms graphite peak at 1600 cm21 disappeared at theCH4H2 ratio of 5 and then at higher ratio itreappeared which was confirmed by Raman spectro-scopy An in situ Fourier transform infrared reflectionabsorption spectroscopy (FTIR-RAS) and optical emis-sion spectroscopy (OES) were employed to study theearly stages of nucleation and growth The outwarddiffusion of substrate atoms to the growing surfacefollowed by supersaturation of carbon forming metalcarbon species was established The appearance ofinfrared absorption peaks at 1340 and 1400 cm21 werespeculated to be indications of CH3 radicals attached tothe substrate as diamond precursors The symmetric andasymmetric stretching vibration of the CndashH bond of sp3

bonded hydrocarbon occurs at 1340 and 1400 cm21 inthe infrared spectroscopy The graphitic carbon phaseon the substrate was believed to originate from thesubstratersquos chemical structure rather than from speciesoccurring in the plasma

Chemical vapour deposition of diamond onto nitridedchromium by an oxyacetylene flame was reported47

Although polycrystalline diamond films were obtainedat very low substrate temperatures (400uC) extremelyweak bonding or no bonding at all between thedeposited layer and the substrate was observed

Heteroepitaxy of single crystal diamond films haverecently been realised on iridium films deposited on theSrTiO3 (001) substrate48 The resulting films showed acube on cube orientation relationship with the substrateand a minimum mosaic spread of 015u High depositiontemperature (920uC) was found to produce low nuclea-tion densities and modified the Ir surface Nucleation at700uC produced highly aligned diamond grains with lowmosaic spread and very low fraction of randomlyoriented grains This proved the better performance ofIr films on SrTiO3 for diamond nucleation as comparedwith pure silicon substrates Exposure of the Ir filmsgrown at 950uC to the biased enhanced nucleation(BEN) process and diamond growth conditions in theCVD reactor at 920uC (nucleation step) and 770uC


International Materials Reviews 2007 VOL 52 NO 1 31

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(growth step) was found to yield a very low diamondnucleation density and strong modification of the Ir filmsurface Since a harsh aggravated environment helps inachieving rough surface owing to ion bombardment ahigh temperature was employed during nucleation Lowtemperature growth environment avoids the holesformation underneath the Ir layer Although the above-mentioned conditions such as high temperature in thenucleation step followed by low temperature growthenvironment modified the Ir surface to a large extentthe diamond nucleation density was very low

A two step diamond (001) film deposition wasachieved on a-plane (1120) a-Al2O3 (sapphire) sub-strate49 First epitaxial (001) iridium films were grownon terraced vicinal a-plane sapphire by ultra highvacuum electron beam evaporation at 950uC Diamondfilm was then grown on the Ir layer by low pressureCVD using methane and hydrogen The initial exposureof the epitaxial Ir to a dc biased plasma led to uniformcoverage of the surface by a dense array of diamondcrystallites before growth A subsequent 60 min growthstep yielded a continuous and highly homogenous (001)diamond film over areas 50 mm2 The films werecharacterised by atomic force microscopy (AFM)scanning electron microscopy (SEM) transmissionelectron microscopy (TEM) and Raman The initial dcbiasing step was helpful in achieving high nucleationdensity Because of its interfacial stability in a hydrogenplasma and high crystalline perfection Al2O3 has beensuggested as a valuable substrate for diamond filmgrowth

Nucleation and growth of diamond films on singlecrystal and polycrystalline tungsten substrates werestudied50 Using a range of bias and reactor conditionsdiamond films were nucleated and grown and werecharacterised by Raman spectroscopy and SEM Highquality and (100) textured films (Raman full width athalf maximum 4 cm21) were deposited on both singleand polycrystalline tungsten substrates The substratespolished with diamond paste resulted in high unbiasednucleation density up to 109 cm22 A 60 increase inthe nucleation density was observed using a 2200 V biason these substrates However for substrates that hadbeen subjected to an additional polishing step with05 mm Al2O3 a much stronger enhancement of four tofive orders of magnitude from an unbiased value of105 cm22 was observed But Raman measurementsrevealed that the diamond films grown on bulk tungstenexhibited considerable thermal stress (11 GPa)which together with a thin carbide layer resulted infilm delaminating on cooling owing to thermal expan-sion mismatch between diamond and tungsten Carefuloptimisation of the reactor parameters (CH4 4 P 5

30 torr power 5 800 W and total gas flow 5 400 sccm)yielded (100) textured growth with a growth rate of022 mm h21

Beryllium metal was employed as a substrate materialfor the MPCVD of diamond films51 As long as a nativeoxide BeO with the hexagonal wurtzite structure wasfound in the temperature range of 700ndash800uC nodeposition was observed The formation of the carbide(Be2C with the cubic antifluorite structure) layer formedabove a critical substrate temperature of y750uCtriggered diamond nucleation Without Be2C thediamond growth rate was low and a significant

amorphous carbon component was observed Just abovethe critical temperature high growth rates wereobserved with high phase purity diamond But thisBe2C layer was found to be detrimental for thickfilms (30 mm) grown above the critical temperatureFormation of diamond on beryllium required theelectrophoresis seeding technique which helped ingetting a significant degree of the epitaxial growth

Since the formation of diamond on carbon materialsoccurs on the edges of the grapheme planes owing to thehigher reactivity than that of the basal planes and ahighly disordered carbon surface gives a better diamondnucleation than a surface consisting of the basal planesseveral carbonndashcarbon composites with tailored surfacefeatures have been used as substrates for diamonddeposition A carbonndashcarbon composite reinforced withvapour grown carbon fibre and another reinforced withpolyacrilonitrile fibres were used as substrates to depositdiamond films using a low pressure CVD with a mixtureof methane hydrogen and oxygen as the precursors52

The activation energy for diamond growth was depen-dent on the nature of the substrate and either a higherdeposition temperature or a higher oxygen concentra-tion produced diamond films with higher crystallinequalities

Diamond deposition was reported on polycrystallineCoSi2 substrates53ndash55 The diamond film grown onCoSi2Si substrate by bias enhanced MPCVD showedhigh nucleation density of 109 cm22 with a positivebiasing which was much higher than with negativebiasing

Because of similar cubic crystal structure excellentlattice matching (just 114 between diamond andcopper) poor solubility of carbon in copper and nocarbide formation between copper and carbon Cu hasbeen used as substrate to study the possibility ofdiamond heteroepitaxy56ndash59 Bias enhanced nucleationof diamond on polycrystalline Cu substrates wasused6061 The results indicated that with higher CH4

concentration the nucleation density was increased andsaturated at 10CH4 but the quality of the diamondwas decreased Bias voltages played an important role inthe nucleation of diamond The nucleation density washighest at 2250 V Thin transparent films of diamondwere grown onto highly polished copper substrate at arate of y1 mm h21 by CVD method using an HFCVDreactor62

Nucleation and growth of diamond film was studiedon c-BN crystal and microstructural characterisationwas performed using high resolution SEM and micro-Raman spectroscopy63 c-BN crystal of 200ndash350 mm wasgrown by a high pressure high temperature process andwas embedded in a Cu substrate to be used as asubstrate material for diamond nucleation The deposi-tion experiment was carried out from 15 min to 5 h Awell shaped cuboctahedral diamond crystallites withdiameter of 100 nm were realised on 111 faces of c-BNwithin 15 min of the experiment As the depositionproceeded diamond crystallites grew in size and formedclusters on c-BN faces After 40 min 05 mm diamondparticle was observed with very high particle density ofthe order of 108 cm22 with a pseudo fivefold symmetryowing to presence of multiple twins in it After longdeposition period some carbon tubes of y100 nm indiameter and 1 mm length were found and attributed to



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the plasma sputtered contamination from Cu substrateAn unusual diamond crystal with a deep pyramidalshaped hole in the centre was observed on the Cusubstrate between the c-BN crystals

Effect of substrate pretreatmentBecause of very low nucleation density only of theorder of 104 cm22 on non-scratched substrates64 surfacemodifications of different kinds like mechanicalabrasionscratching seeding electrical biasing cover-ingcoating ion implantation pulsed laser irradiationand carburisation have been used to realise very highand uniform nucleation density leading to a goodquality diamond film (Table 1 (Ref 42)) For Sisubstrates which is the most extensively studiedsubstrate material for diamond growth a nucleationdensity of 107ndash108 cm22 has been obtained afterscratching with diamond powder Among differentsurface pretreatment techniques biasing is found to bethe most effective in achieving high nucleation densityfollowed by scratching seeding coveringcoating andion implantation Nucleation on activated surfacegenerally occurs on carbon rich particles or defects likescratches grain boundaries particle boundaries dis-locations electron bombardment induced damages andedges of pits or craters as discussed in Ref 42 andreferences therein

Mechanical abrasion

The effect of scratching of the substrate surface withdiamond powder was first observed in 198765 and sincethen it has been extensively studied using differentabrasive materials like oxides silicides nitrides carbidesand borides Scratching with SiC cubic boron nitrideCu or stainless steel ZrB2 TaC and even Fe powder hasbeen proposed in the literature4266ndash69 But scratching bythese materials was not as effective as by the diamondpowder The effectiveness of abrasion on the nucleationfollowed the order silicides SiO2 nitrides ZrO2

carbides borides Al2O3 c-BN diamond70

Scratching or abrasion of the Si substrate surface withdiamond grit enhanced the nucleation density byroughly three orders of magnitude compared with non-scratched Si (up to 107 cm22) The grit size of thediamond powder used for scratching also affected the

nucleation density a 025 mm grit was the most effectivefor scratching by hand and a 40ndash50 mm powder was thebest for scratching by ultrasonic agitation64 The methodused for scratching the substrate surface by diamondalso influenced the nucleation density The nucleationdensity decreased with increasing particle size ofdiamond abrasive paste used for polishing but itincreased with increasing particle size in the ultrasonicscratching treatment71 However the optimum size ofabrasive particle was dependent on the pretreatmentmethods deposition process growth conditions andnature of substrate materials The nucleation densitywas proportional to the scratching time and themorphology of the deposited film depended on thescratching time Large isolated crystal was found forshort scratching times whereas longer scratching pro-duced crystals of smaller size and higher density72

Mechanism of nucleation enhancement by mechanicalabrasion

Mechanical abrasion with diamond powder followed bycleaning the surface with acetone or alcohol damagesthe surface because of the continuous bombardmentof the substrate surface by diamond particles Somediamond debris also might be left on the surface evenafter cleaning Whether the surface defects caused by theabrasion is responsible or the diamond debris left behindis causing the nucleation enhancement is not clearAbrasion with materials other than diamond has alsobeen tried The findings of these experiments anddifferent opinions are discussed below

Nucleation enhancement by scratching was attributedto seeding effects minimisation of the interfacial energyon sharp convex surfaces breaking up of the surfacebonds or presence of the dangling bonds at sharp edgesstrain field effects rapid carbon saturation (fast carbideformation) at sharp edges and removal of surfaceoxides42 A schematic diagram of mechanisms fordiamond nucleation enhancement on scratched surfaceswas presented in Ref 73

One possible mechanism for nucleation enhancementby scratching was the production of non-volatilegraphitic particles through local pyrolysis of absorbedhydrocarbons at the scratched surface of the substrateThese graphitic clusters in turn get hydrogenated in theatomic H environment under the CVD conditions toform the precursor molecules which enhanced nuclea-tion Another view is that during scratching withdiamond c-BN or a-SiC powder the residual powderor fragments left in the scratched groove act as seeds forthe diamond growth Although c-BN and a-SiC are notdiamond their structures are close enough to that ofdiamond Thus diamond grows easily on them It hasbeen observed that fragments of diamond existed in thescratched grooves of Si and diamond growth occurredon them74 The nucleation density was found to belinearly proportional to the diamond seed particledensity and it is approximately one tenth of the seedparticle density75

It was also suggested that scratching with powdercreated a change in the surface morphology andproduced defects such as edges steps and dislocationsThese defected regions were identified as chemicallyactive sites which preferred to adsorb diamond pre-cursors owing to enhanced bonding at high energy

Table 1 Typical surface nucleation densities of diamondon non-diamond substrates after various surfacepretreatments42

Pretreatment methodNucleationdensity cm22

No pretreatment 103ndash105

Scratching 106ndash1010

Ultrasonic scratching 107ndash1011

Seeding 106ndash1010

Biasing 108ndash1011

Coating with Fe film 4846105

Coating with graphite film 106

Coating with graphite fibre 109

Coating with a-C film (first scratched) 361010

Coating with C70 cluster and applying bias 106ndash1010

Coating with Y2O3ndashZrO2 a-BN cSiC layer EnhancementCz ion implantation on Cu EnhancementAsz ion implantation on Si 105ndash106

Pulsed laser irradiation z coating a-CWC c-BN layer

Enhancement

Carburisation Enhancement



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interfaces with a high density of unsaturated bonds andlow coordination numbers76

Chemical treatment

Apart from mechanical abrasion a number of chemicaletching were tried to enhance the nucleation density fordifferent applications of the diamond films Diamondnucleation on the ridges lithographically etched on non-scratched Si was observed by SEM studies69 Enhancednucleation on Si etched by HFHNO3 was alsoobserved76 However attempts to enhance nucleationby creating etch pits on non-scratched Si using acidsHz or other reactive gases were unsuccessful6468

Surface passivation was tried to suppress the deleter-ious effect of Si surface oxides (like SiO2) in order toenhance heteroepitaxial diamond nucleation77 X-rayphotoelectron spectroscopy showed the H Br and Ipassivated Si surfaces to be free from silicon oxides andcarbides A dramatic enhancement of nucleation densityof the order of 1010 cm22 was observed on Br passivatedSi surface The degree of nucleation enhancement wasrelated to the saturation value of electron emissioncurrent from the passivated surfaces which increased inthe order of H I and Br passivation The same orderwas also observed in the adsorbate desorption tempera-ture from the Si surface Greater nucleation enhance-ment was observed when the adsorbate desorptiontemperature was closer to the nucleation temperatureFairly uniform and high nucleation density for the Brpassivated Si substrate is shown in Fig 1

Surface coating

Nucleation enhancement was achieved by covering thesubstrate with thin films of metals (Fe Cu Ti Nb MoNi) C-70 Y2O3ndashZrO2 amorphous-BN SiC hydrocar-bon oil graphite amorphous-C diamond like carbon(DLC) C-60 and even with mechanical oil4278ndash82 Theeffect of these coatings in nucleation enhancement wasranked as C-70 amorphous-C DLC graphitefibre graphite film Fe Cu Ti Ni Mo

Nb The nucleation enhancement was attributed to thephysical and chemical changes to the substrate surface(the coatings enhance carbon saturation on the surfaceand provide high energy sites or nucleation centres) andchanges to the gas chemistry in the immediate vicinity ofthe substrate surface78 In order to avoid delaminationof the diamond film from the tool materials surfacebecause of the thermal expansion mismatch between thetwo and to avoid the detrimental effect of some metalslike Co Fe on the nucleation and growth of diamondseveral interlayer coatings were applied on the toolmaterials8ndash10 The hard coatings of TiN TiC Si3N4SiC SiCxNy (Ti Si)Nx and pulsed arc deposited a-C(laser arc) were also investigated for their suitability asinterlayers for diamond growth7 The nucleation densitywas dependent on the interlayer materials and substratetemperature The nucleation densities were 105ndash108 cm22 for the titanium and silicon containing inter-layers The ultrasonic pretreated amorphous-C layershad nucleation density of y1010 cm22 compared with46107 to 66107 cm22 for the untreated samples Nodependence of the nucleation density on amorphous-Clayer thickness was found The nucleation density fordifferent interlayer and process conditions is sum-marised in Table 2

A high nucleation density was obtained on a carbonfilm coated Si (100) substrate over a wide region in amagneto active MPCVD method using CH4CO2He gasmixtures83 Nucleation densities as high as 109 cm22 wasattained for small CO2 concentrations of 1ndash2 duringthe pretreatment process while no successful enhance-ment was observed for Si substrates pretreated at highCO2 concentrations beyond 37 Diamond nucleationwas dependent on the structure and property of thepredeposited carbon films which influenced the etchingand agglomeration in the subsequent growth process Amodel was proposed for the diamond nucleation basedon a two step process as shown in Fig 2 When thecarbon film consisting of a mixture of microcrystallinegraphite and an amorphous-C phase is deposited(Fig 2a) the initial stage the anisotropic etching creates

1 Nucleation density on Br passivated Si substrate with

following deposition conditions temperature 620uC

nucleation time 30 min CH4H2 51 MW power

1000 W (reprinted with permission from Ref 77 copy-

right 2000 by American Physical Society)

Table 2 Diamond nucleation densities for different interlayers and process conditions7

InterlayerInterlayerthickness mm

Substrate pretreatmentwith diamond powder

Substrate temperatureK

Nucleation densitycm22

TiN 58 Yes 920 108

TiN 46 Yes 1140 26105

S3N4 68 Yes 910 108

S3N4 50 Yes 1080 66106

SiCxNy 78 Yes 960 108


SiC 96 Yes 920 108

SiC 150 Yes 1070 108

a-C 001 No 850 46107

a-C 01 No 860 66107

a-C 001 Yes 860 1010



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graphite islands Since the graphite crystallites are largeenough in size to remain stable in the diamond growthplasma during the subsequent treatment process thehighly disordered and defective carbon regions aroundthe microcrystalline graphite are etched off first by H Oand OH radicals and ions (Fig 2b) This createdgraphite crystallites or carbon granules (such as thosein carbon black or fullerenes) which remain non-volatileor aggregate to form various kinds of carbon clustersSome of these clusters may be converted to precursorsfor diamond nucleation (Fig 2c) and growth ofdiamond particles (Fig 2d)

Ion implantationion bombardment

The ion implantation is generally employed to modify thesurface energy and surface structure of the substrate inorder to enhance the nucleation density Howeverimplantation induced reduction in nucleation is alsoreported in the literature Implantation of Cz (with adose of 1018 ions cm22 65ndash120 keV) on Cu substrate andAsz (with a dose of 1014 ions cm22 100 keV) on Sisubstrate enhanced nucleation42 Siz implantation (with adose of 261017 cm22 25 keV) on a mirror polished Siwafer also enhanced nucleation84 The surface structurewas changed owing to implantation but the Si composi-tion of the surface remained unchanged However Arz

implantation (with a dose of 361015 ions cm22 100 keV)on Si substrate was deleterious in enhancing the nuclea-tion density85 Siz implantation enhanced nucleationbecause it created nanoscale surface defects on the Sisubstrate which served as the active sites for theadsorption of hydrocarbon radicals necessary for initialdiamond nucleation A similar effect was found in thegrowth of diamond on porous silicon whose surface hadnanoscale microstructure86 The lattice damages likestrain amorphous disorder and twinning created by theion implantation were suggested for enhanced nucleationThe strain was the main reason for enhanced diamondnucleation on ion implanted substrates

Biasing

Among the various pretreatment techniques studied inthe literature biasing the substrate has been the mosteffective in enhancing the nucleation density of diamondfilm Since the surface free energies and lattice constantsof SiSiC are different from those of diamond it isdifficult to nucleate diamond on mirror polished Sisubstrate Both the positive and negative biases havebeen fruitful in achieving high nucleation density fordiamond growth4264 An enhanced diamond nucleationdensity of about 109ndash1011 cm22 on a mirror polished Sisubstrate was obtained by applying a negative substratebias voltage8788 Biasing a substrate helps in reducingthe oxide formation on the substrate removing thealready formed oxide layer and overcome the activationenergy required for the stable nuclei formation Negativebias produced roughening of the grown surface owingto continuous bombardment by the cations whereaspositive bias led to a smooth surface The grain size andnon-diamond phase in diamond films were decreasedwith increasing bias current leading to high Youngrsquosmodulus and fracture strength By applying a negativebias to the substrate the nucleation density adhesionand surface properties were improved while trying tocoat complex shaped tools such as dental burs withpolycrystalline diamond films in a modified HFCVDsystem45

The nucleation density also increased with bias time ata bias voltage of ndash300 V The highest nucleation densitywas 0961010 cm22 for a bias time of 30 min Thenucleation density and crystallinity of the diamond filmwas studied recently by applying a negative substratebias as a function of bias time using an ECR plasma89

The mean ion energy onto the substrate was kept at 30and 50 eV by controlling the bias voltage For short biastimes of 10ndash60 min the nucleation density increasedwith time and the highest nucleation density of 107ndash108 cm22 and crystallinity were obtained at 60 min ofbiasing (Fig 3) For long bias times of 60ndash150 min the

a carbon film consisting of microcrystalline graphite and amorphous-C phase b graphite crystallites and carbon granulesare created on silicon oxide rich layer on substrate c diamond precursors are nucleated from carbon clusters d dia-mond particles grows on carbide intermediate layer

2 Schematic model of diamond nucleation and growth processes after nucleation enhancing treatment (reprinted with

permission from Ref 83 copyright 2000 American Institute of Physics)



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nucleation density decreased with time The deteriora-tion of the film crystallinity for longer bias times was dueto a reduction of the effective substrate bias voltagecaused by the delamination of the deposited amorphouscarbon film The incubation period for nucleation wasestimated between 10 and 30 min which were associatedwith the formation of an amorphous hydrogenatedcarbon matrix suitable for nucleation

A negative bias is not found helpful in achievingnucleation enhancement for films grown by HFCVDmethod Positive bias enhanced nucleation has helped inachieving the growth of textured diamond films on Si(111) and carbon face 6HndashSiC (0001) in an MPCVD90

A bias voltage of 100 to 300 V 3CH4 concentrationin bias step and 033CH4 concentration in growthstep were used to synthesise the films Highly orienteddiamond films were observed by SEM and X-raydiffraction (XRD) The interface between diamondand Si substrate was smooth (revealed in cross-sectionalTEM) while it was normally rough between diamondand SiC without the bias More examples of the positivebias in enhancing the nucleation density in dc plasmaenhanced CVD (PECVD) and HFCVD were reported inRef 42

However if the plasma is generated by the biasvoltage an enhancement of nucleation similar to thatobtained for MPCVD can also be achieved for HFCVDStubhan et al91 and Chen et al9293 demonstrated thatin HFCVD system diamond nucleation enhancementcan also be realised when a negative bias is applied to thesubstrate The highest nucleation density can reach 109ndash1010 cm22 on mirror polished Si which is similar to theresults obtained using the MPCVD system

Bias enhanced nucleation mechanism has been widelystudied and different models have been proposed Yugoet al94 and Gerber et al95 have suggested a shallow ionimplantation model in which the sp3 bonded carbonclusters formed by low energy ion implantationfunction as the nucleation precursors The negative biascauses the positively charged ions in the growth chamber

to accelerate towards the substrate surface and bombardit This process helps in removing the surface contam-ination and facilitates cluster formation on the surfaceThese events in turn advance diamond nucleationStoner et al96 on the other hand have suggested thatcritical process should be a change in plasma chemistrySubstrate biasing can increase the concentration ofatomic hydrogen in the plasma or help in the formationof a thin carbide layer on the surface which helps inenhancing the nucleation Jiang et al found the overalltemporal evolution of the nucleation density agreed wellwith a surface kinetic model involving immobile activenucleation sites germs (an intermediate species in theformation of nucleus) and nuclei9798 They also sug-gested that in addition to surface defects (point defectssteps and sp3 bonded carbon clusters) serving as thenucleation sites the enhanced surface diffusion andsticking probability of carbon on Si surface owing to ionbombardment should be the decisive factors Theenhancement of the surface diffusion of carbon specieswas identified by investigation of the distribution of thefirst nearest neighbour distances97 Therefore the role ofion bombardment is crucial to enhancing the diamondnucleation

It has also been suggested that diamond crystallitesformed during the bias enhanced nucleation stage serveas nucleation centres for the subsequent diamondgrowth99 It is concluded that the variation in the sub-strate temperature rather than the changes in the MWinput power or plasma chemistry drive the observedstructural changes and increase in nuclei density Themodel for bias enhanced nucleation suggests that the ionbombardment leads to the formation of predominantlysp3 coordinated carbon clusters which then undergo arecrystallisation to form diamond crystallites Thesediamond crystallites subsequently serve as nucleationcentres for the growth of diamond films

An electron emission enhanced nucleation mechanismhas been proposed to describe the bias enhancednucleation of diamond on a Si substrate using a SiO2

mask (Fig 4)100 The variation of nucleation density onthe partially patterned SiO2Si substrate also reveals thatthe BEN of diamonds in the MPECVD process followsthe proposed mechanism The results suggest that thediamonds cannot be formed on sample which is coveredby the completely insulated (patterned) SiO2 Otherworkers also have claimed that diamond nucleationalways begins in areas covered by bias plasma (orsecondary plasma) during the BEN step in MPECVD

3 Nucleation density on n-Si (100) substrate as function

of time for bias voltages of 230 and 250 V horizontal

broken line represents density after growth step but

without nucleation step reprinted from Ref 89 copy-

right 2004 with permission from Elsevier

4 Schematic diagram of electron emission enhanced dia-

mond nucleation on partially patterned SiO2Si sub-

strate (reprinted with permission from Ref 100

copyright 2001 American Institute of Physics)



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Electron emission has been found to enhance thenucleation of diamonds on the edge of the insulatedsubstrates by initially forming diamond nuclei onneighbouring Si substrates that are not electricallyinsulated The emitted electrons come from the dia-monds on the Si surface of the patterns Reactive gasesare generated and the concentration has been found toincrease with the pattern size since more electronsgenerated more reactive gases over a larger Si areaThis assumption is supported by the fact that thenucleation density can reach 561010 cm22 on the mostexposed Si on the two sides This observation supportsthat the BEN behaviour of diamonds in the MPECVDprocess is generated by electron emission enhancednucleation

In general the nucleation of a particular phasedemands formation of a nucleus exceeding a criticalsize and to become thermodynamically stableAccording to the kinetic theory the nucleation proceedsvia the following steps101

(i) vapour species such as atoms molecules andorradicals arrive on the substrate surface and getadsorbed

(ii) the species then diffuse over the substratesurface and part of the adatoms get desorbedfrom the surface into the vacuum

(iii) the adatoms get combined with each other andform clusters owing to fluctuations of the localspecies concentration

(iv) nuclei then grow by capturing the adatoms orby direct impingement of the atoms fromvapour phase

The critical size of the nuclei is dependent on the totalfree enthalpy of formation which is related to thesurface free energies of the nuclei and the substrate The

above sequence has been pictorially depicted in thereference mentioned above The author has suggestedthat because of an energetic advantage the nuclei areformed on the surface defects like steps dislocations orsurface impurities which are often called active sites fornucleation Roles of factors contributing to biasenhanced nucleation of diamond are described below

Role of ion bombardment

The directional flux of the energetic species on thesubstrate surface is essential to achieve a bias enhancednucleation This has been shown by performing BEN ontopographically structured Si wafers containing grooveswith vertical side walls as shown in Fig 5102 This wascreated either by reactive ion etching or by SiO2 maskedSi substrates The mean free path of ions in the flux isy5 mm at gas pressure y19 torr Consequently theions flying towards the substrate cannot feel the groovesurface structure and hence the parallel faces (with thesubstrate surface) will get bombarded with the highenergy ion flux while the side walls will not Diamondnucleation on the parallel surface of the wafer justifiesthe role of ion bombardment in BEN

Role of kinetics

Since a surface kinetic model103 involving immobileactive sites germs (intermediate species in the formationof nucleus) and nuclei is insufficient in describing thetemporal evolution of overall nucleation density on Siwafers a three step kinetic model was proposed104 Sincein the BEN unscratched Si wafer is used as the substratethe nucleation centres are only formed during the BENstage Therefore an extra step for the generation of thenucleation sites has to be incorporated into the kineticscheme With this extra step the kinetic scheme becomes

RNzmN (1)

where R Nz m and N are densities of the surfacecentres that can be transformed into a nucleation sitethe nucleation sites the unstable clusters and the stablenuclei (nucleation density) respectively The excellentagreement (as is shown in Fig 6) between the theoretical

5 Selective growth of diamond crystals on grooved sili-

con wafer containing both faces perpendicular and

parallel to substrate difference in nucleation densities

on different faces is noticeable reprinted with permis-

sion from Ref 102 copyright 1998 by American

Physical Society

6 Nucleation density (islands per mm2) v deposition

time solid curve is obtained by computer modelling

using three step kinetic models open and full circles

in plots represent data calculated from crystal size dis-

tribution (inset) and obtained by direct particle count-

ing respectively reprinted with permission from

Ref 102 copyright 1998 by American Physical Society



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curve obtained from the computer modelling using thethree step kinetic scheme as proposed by Tomellini andPolini104 and the experimental data calculated fromcrystal size distribution (open circles) (inset) and thoseobtained by direct particle counting (solid circles)justifies the role of kinetics in BEN

Role of surface diffusion

The role of surface diffusion of the growth species inBEN was demonstrated by measuring the first nearestneighbour distance distribution of the nuclei If surfacediffusion of the mobile species (adatoms) towardsimmobile nuclei is involved in the nucleation processthen the presence of nuclei (act as sink to the mobilespecies) should reduce the probability of formation ofnew nuclei in their immediate vicinity The first nearestneighbour distance distribution of the nuclei shouldtherefore deviate from a random distribution102 Thishas really been observed in SEM and AFM investiga-tions The measured distributions were found to shift tolarger distances compared with the random distributionfor a fixed nucleation density of the order of 1010 cm22

for different samples A depletion zone of the nuclei isfound to increase from 12 nm for Vb52150 V to 35 nmfor Vb52250 V The increased depletion as a functionof bias voltage confirms the contribution of surfacediffusion towards BEN

Based on the above observations the nucleationsequence under BEN condition is thought to proceed as

(i) formation of nucleation sites(ii) formation of carbon clusters owing to enhanced

surface diffusion(iii) formation of stable diamond nuclei

Pulsed laser irradiation

Pulsed laser irradiation of a thin layer of a-C or WC orc-BN deposited on various substrates enhanced dia-mond nucleation as well as the adhesion of the film tothe substrate42 It was speculated that the irradiationconverted a part of the a-C on the substrate surface intodiamond

Carburisation

Carburisation of the substrate surface also helps inachieving high nucleation density because of its abilityto cover the substrate surface with a thin coating ofcarbide or to make the surface layer saturated withcarbon both of which help in diamond nucleation42

Most of the pretreatment techniques used to enhancenucleation also lead to damage of the surface byintroducing different kinds of defects on it Moreoverall the surface treatment procedures (like scratchingseeding) can not be applied equally well to substratewith complicated geometry and shape Also someapplications demand very smooth and clean surfaceslike those used in electronics device applications opticalwindows and smooth wear resistant coatings There aresome alternative ways to improve the nucleation withoutdamaging the substrate surface These include changesin process parameters such as substrate temperaturegas pressure precursor composition or the effect ofdifferent additives into the precursor gases for enhancingnucleation as described below

Seeding

Seeding the substrate by diamond particle of differentdimensions (nanometre to micrometre range) has long

been known to enhance the nucleation density Seedingis achieved either by dip coating or by electrophoresisIn dip coating the substrate is immersed in a purifieddiamond suspension of ultrafine particle size In electro-phoresis diamond particle in suspension being nega-tively charged gets deposited at the positive electrode(the substrate to be seeded) under the application of anelectric field between two electrodes dipped in thesuspension

Dip coating used a methyl alcohol based ultra pureand unltrafine (5 nm) diamond suspension in water andachieved a very high nucleation density of the order of1011 cm22 in 10 min on single crystal Si (100) wafer in amagneto active MW plasma process105106 An acetonebased diamond suspension of particle size 3ndash6 nm isused for seeding the single crystal Si wafer by dip coatingprocess to achieve high nucleation density in a lowtemperature CVD diamond growth process107 A veryhigh nucleation density of the same order (1011 cm22)led to diamond growth at 200uC106

Electrophoresis technique is used to seed the substratewith micrometre size diamond particle to achieve (111)oriented diamond film synthesis108 or to coat WCndashCocutting tool by CVD diamond109 Electrophoretic seed-ing in acetone medium produced a more uniformseeding at 500 V with high nucleation density leadingto highest diamond growth in an HFCVD process108

Seeding with smaller grains (025 mm) produced ran-domly oriented non-faceted diamond growth whereasseeding with 5 mm grain size led to (111) orientedgrowth For coating the WCndashCo cutting tool by CVDdiamond film insufficient nucleation density of thescratched substrate led to no film formation when thesubstrate Co was not removed by acid But electro-phoretic seeding of the substrate produced film typedeposit under similar conditions Although the nuclea-tion density was not high it increased with appliedvoltage An increase in voltage from 10 to 1000 V led toan increase in nucleation density from 2061026 to35061026 cm22 after 600 s of the electrophoresisAlthough most of the work on electrophoresis describediamond particle as negatively charged in the suspensionand hence deposited at positive electrode positivelycharged diamond particle in electrophoretic suspensionis also reported110 The origin of the surface positivecharge of the diamond particle was attributed to theadsorption of the Hz ion in the suspension In acetonemedium Hz ions are generated as a result of keto enoltautomerism catalysed by H2O and I2 which getsadsorbed on diamond surface The author has suggestedisopropyl alcohol solvent to provide more stablesuspension when I2ndashH2Ondashacetone is used for electro-phoresis It was observed that for smaller particledimension (05ndash1 mm) low applied voltage (50 V) ispreferable to generate uniform coating and to preventparticle agglomeration110

Beside the electrophoresis and dip coating in nano-diamond suspension another important techniqueincludes imparting a positive surface charge to thesubstrate surface followed by dip coating in a diamondsuspension111 A high and uniform nucleation density isreported on a variety of substrate material such assingle crystal silicon wafer a commercial glass capillarytube (Fisher Scientific) soda lime silicate commercialglass slide (Fisher Scientific) fused quartz commercial



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slide (SPI) Using polyethyleneimine as cationic polymerto impart a surface positive charge to the negativelycharged substrate surface followed by dip coating indiamond suspension of different grain sizes (34 mm)very high and uniform nucleation density was obtainedover a wide area111

All these seeding techniques are important particu-larly when dealing with very large and wide substratearea pretreatment Since seeding of the diamond particleover wider substrate area produce uniform and densenucleation in a shorter time and at lower substratetemperature this technique is particularly suitable forlow temperature growth of CVD diamond film

Effect of temperatureNucleation density Nd generally increased with tem-perature for a fixed set of other deposition parameterssuch as pressure MW power gas composition andparticular gas flow rate An enhancement of nuclea-tion density from (16106 cm22 to 161010 cm22 in anarrow temperature range between 670 and 700uC wasobtained during deposition of a polycrystalline diamondfilm using bias enhanced nucleation while the otherdeposition parameters such as the MW input powerwere kept constant99 The enhancement of nucleationdensity with temperature is shown in Fig 7 Theintensity of the diamond plasmon in the electron energyloss spectroscopy increased with the substrate tempera-ture which was the signature of enhanced diamondcrystallites concentration embedded in the amorphouscarbon matrix It was suggested that diamond crystal-lites formed during the pretreatment served as nuclea-tion centres The variation in the substrate temperaturerather than the changes in the MW input power orplasma chemistry was proposed to drive the observedstructural changes and enhanced nucleation density

The nucleation density increased with increasingfilament temperature reached the maximum at 2100uC

and then decreased thereafter in HFCVD112 Thedecreased nucleation beyond 2100uC was attributed tothe enhanced etching of the nucleation sites A numberof examples of enhanced nucleation with temperatureare found in for different deposition methods and anoptimum temperature has been found to exist y860uCwhere the nucleation density becomes maximum42 Theenhanced nucleation with increasing temperature issuggested to be caused by the change in the adsorptionstate and surface diffusion length of growth species Thereactive species or molecules get adsorbed on thesubstrate surface physically 900uC and chemicallybeyond this temperature This results in an abruptchange in diffusion length at y900uC The stickingprobability of the reactive species on the substratesurface increases as the temperature approaches 860uC

Effect of pressureThe pressure dependence of nucleation density is a resultof competition between b-SiC formation (whichenhances the diamond nucleation density) and theatomic H etching (which decreases the nucleation sites)Recently a high density of diamond nucleation (109ndash1011 cm22) was achieved on mirror polished Sisubstrates using HFCVD under very low pressures(01ndash1 torr) without applying surface scratching or asubstrate bias113 Using this method diamond grainswith a density 1010 cm22 can be achieved which ismore than two orders of magnitude higher than thehighest density (107ndash108 cm22) that can be obtained onscratched substrates under conventional pressure (10ndash50 torr) High nucleation density of diamond is achievedon a 4 in Si (100) wafer in a low pressure (02 torr)process but the quality of the film was not good114

Effect of precursor gasesThe precursor gas also affects the nucleation densityeither by stabilising the diamond nucleus precursor115 orby enhancing the carbon saturation of the substratesurface which triggers nucleation83116 The enhancedmethyl radical (CH3) density produced by the precursorgases is also responsible for enhanced nucleation densityas reported in most of the literatures117

An increase in overall growth rate by 7 16 and 39 atsubstrate temperatures of 850 750 and 650uC respec-tively using chloromethane instead of methane asprecursor in an MWCVD was attributed to the highernucleation density induced by chloromethane precur-sor115 Chloromethane was found to reduce the timerequired for film formation and increased the nucleationdensity significantly particularly at low growth tem-peratures (Table 3) In Table 3 time period for filmforming stages is defined by the end of the temperaturerise programme to the moment of first reflectionintensity minimum The time periods of film forming

7 Nuclei density (after complete deposition cycle) as

function of substrate temperature open symbols ndash

substrate temperature adjusted by external heating

(MW input power 280 W (open square) 320 W (bold

open square)) closed symbols ndash substrate temperature

adjusted by variation of the MW input power reprinted

with permission from Ref 99 copyright 1996

American Institute of Physics

Table 3 Time period for film forming stages andnucleation densities at first reflection intensityminimum for 15 of CH4 and CHCl3 (Ref 115)

TemperatureuC

Time minNucleation density6108 cm22

CHCl3 CH4 CHCl3 CH4

850 392 571 18 92750 308 638 18 31650 307 1006 36 13



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stages were measured by laser reflective interferometryNucleation densities were counted from SEM micro-graph The reason that chloromethane enhances thetotal growth rates was attributed mainly to its ability tostabilise diamond nucleus precursor particularly at lowtemperatures to enhance diamond nucleation

Diamond film with high nucleation density wasobtained using a CH4CO2H2 gas mixture83

Nucleation densities as high as 109 cm22 was obtainedfor small CO2 concentrations of 1ndash2 during thepretreatment process while no successful enhancementwas observed for pretreatment at high CO2 concentra-tions beyond 37 The curved sheet like structure of thepredeposited carbon films and its porous natureinfluenced diamond nucleation The nature of reactingspecies present in the plasma and their emissionintensities with increasing CO

2in the precursor gases

were monitored by in situ OES and quadrupole massspectroscopy These informations were used to supportthe enhanced nucleation for 19CO2 concentration inthe gas mixture The morphology and composition ofthe specimens also supported the observed effect

A high CH3 radical density leading to enhancednucleation was observed from a CH4He gas mixture ina bias enhanced large area diamond nucleation on Si(001) using ECR MPCVD117 With a CH4H2 gasmixture the nucleation density of the order of107 cm22 was obtained using high CH4 concentrationHowever CH4He produced a nucleation density as highas 109 cm22 even at low concentration of CH4 gas with abias voltage of z30 V The main difference between thetwo plasmas was the difference in H concentrationrather than CH3 concentration and plasma density Itwas suggested that the proper balance between thecarbon related radicals and H radical density on thesubstrate surface could make the nucleation densityhigh

Effect of variation in process or additives inprecursor gasesVariation in the synthesis process or addition of anyspecial gases with the precursors affects the nucleationprocess greatly

A rapid increase in nucleation density was obtainedon mirror polished Si substrate by a pulsed NdYAGlaser beam118 The laser beam was used to excite and

decompose the reactive gases and to enhance the etchingof the non-diamond phases An enhanced nucleationdensity from 108 to 1010 cm22 was observed withdecreasing laser power density from 13861010 to1176109 W cm22 and deposition pressure from 760to 3 torr which is one to two orders of magnitude higherthan that obtained on a similarly treated substrate usinghot filament activation with a pulsed laser power densityrange 466104 to 2656105 W cm22 At lower substratetemperature (as low as 650uC) however the pulsed laserbeam could not help in enhancing nucleation Thevariation of nucleation density at the centre of the laserirradiation spot with laser power density is shown inFig 8a for nucleation at the substrate temperature of700uC CH4 concentration of 2 pressure of 30 torrand irradiation time of 40 min The enhanced nucleationand growth of diamond crystallites was attributed to theeffective excitation of reactive gases and etching ofthe non-diamond carbon phases by pulsed laser beamThe highest nucleation density obtained was up to 109ndash1010 cm22 at 1176109 to 1076109 W cm22 laserpower density range and then decreased with furtherincrease in the laser powder density Since high laserpowder density was not beneficial to the adsorption andreconstruction of the nucleating species on the substratesurface high laser power reduced the diamond nuclea-tion The nucleation density also increased with irradia-tion time at a constant laser power density as shown inFig 8b The nucleation density increased steadily from236108 to 326109 cm22 during an irradiation timefrom about 2 s up to 40 min

N2 addition in the precursor gases has sometimes beenfound beneficial for enhancing the nucleation density119

An increase in the nucleation density was obtained insynthesising diamond films by an HFCVD using a CH4N2H2 gas mixture With increasing nitrogen concentra-tion in the gas mixture the nucleation density increasedand the crystal size decreased The increase in nucleationdensity with increasing N2 content is shown in Fig 9The observed result agreed well with those reported byZhou et al where nanocrystalline diamond (NCD) wassynthesised by MPECVD using N2CH4 as the reactantgases without any additional H2120 But an adverseeffect was found in the work of Yang et al whereincreasing NC ratio in the feed gases (CH4ArH2)decreased the nucleation density as shown in Fig 10121

8 Diamond nucleation density as function of a laser power density and b irradiation time nucleation density in ordinate

(of a and b) was expressed in unit of cm22 and laser power density in abscissa (of b) in unit of W cm22 reprinted

from Ref 118 copyright 2001 with permission from Elsevier



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and these authors have suggested a lower covering ratioof the diamond grains on the substrate with increasingNC ratio in the nucleation stage

Diamond is a metastable phase under CVD conditionand its formation needs high activation energy com-pared with more stable phase of graphite So thenucleation of diamond from carbon containing pre-cursors under CVD conditions does not follow theconventional route where the adatoms get agglomeratedto form a critical nucleus of a stable size The processparametric window is narrow for diamond nucleation onnon-diamond substrates On an atomistic scale diamondnucleation can be thought of proceeding via thefollowing steps The atoms or ions from the gas phaseimpinge the deposition surface and get adsorbed on highenergy sites The adatoms may either desorbs or diffuseover the surface In course of time the surfaceconcentrations of the adatoms increase and get com-bined to form clusters These clusters may grow or decaydepending on the statistical fluctuations of the localadatom concentrations97

Beyond a critical size (3ndash5 nm) the probability ofgrowth is more than the decay So the cluster whichqualifies the critical size during concentration fluctua-tions becomes stable The stable cluster eventually groweither from the continued migration of the adatoms orfrom the impingement of ions or atoms from the gasphase For deposition surfaces which already havediamond grains on it provide better nucleation byshortening the incubation period (time to start nuclea-tion) All the pretreatments contribute to one or more ofthe above stages to occur more efficiently therebyenhancing nucleation keeping in view the same mechan-ism Since diamond being known as the material ofhighest surface energy (53 J m22 for (111) surface) amajority of the pretreatment procedures for diamonddeposition on non-diamond surface are mainly aimed atcreating a high energy surfaces by generating defects orsharp edges or by creating unsatisfied bonds on thesurface Mechanical abrasion ion bombardmentionimplantation chemical treatments all provide a defectedsurface with high energy sites on it which accelerates theadsorption of the atoms or ions from the gas phaseSeeding the substrate helps in lowering the incubationperiod for nucleation Pretreatments like coating orcarburisation is targeted for providing carbon rich areas

on the surface which are potential sites for cluster toform and trigger nucleation Substrate materials inmany cases (like transition metals such as Ti Mo NiFe) have been chosen which are either susceptible tocarbide formation or carbide itself such as WC SiCBe2C TiC Lattice match and crystal structure of thesubstrate plays an important role in enhancing nuclea-tion on non-diamond substrate Ir and c-BN forexample have very good lattice match with diamond(diamond 357 A versus c-BN 362 A and Ir 384 A)which helps in achieving heteroepitaxial nucleation onthese substrates Biasing the substrate is aimed ataccelerating the ionic flux towards the deposition surfacethereby enhancing the growth of the stable cluster whosesizes are bigger than the critical size

Besides the pretreatment procedures process para-meters like temperature pressure gas compositions alsohelp in nucleation in view of the general mechanismdiscussed before Temperature helps in adatom diffu-sionmigration on the surface to form a stable clusterPressures and gas composition are critical in promotingthe cluster to achieve the critical size otherwise they willreevaporatedesorbs from the surface rendering nuclea-tion to occur

Growth of diamondThe nucleation is followed by the growth stage Asuccessful nucleation is required in order to have a goodquality diamond film since nucleation affects the growthprocess in terms of growth rate texture roughness andthe overall quality of the film Diamond films are oftenclassified as microcrystalline diamond (MCD) NCDultrananocrystalline diamond (UNCD) and ballas dia-mond based on the morphology (especially grain size)and the hybridisation of the carbon atoms present inthat phase Microcrystalline diamond consists of micronsize grains which range from one to hundreds ofmicrometres and sp3 bonded carbon atom in the crystalstructure Whereas in NCD the grain sizes are normally100 nm The UNCD consists of equiaxed grains ofdimension 3ndash5 nm Both the NCD and UNCD containa significant fraction of sp2 bonded carbon atom along

9 Dependence of nucleation density on N2 additions in

reactant gases N2H2CH4 nucleation density in ordi-

nate was expressed in unit of cm22 deposition experi-

ments were carried out at 35 torr pressure and at

substrate temperature of 650ndash750uC on (100) Si wafer

reprinted from Ref 119 copyright 1999 with permis-

sion from Elsevier10 Effect of NC ratio on nucleation density of diamond

films deposited on molybdenum substrate by dc arc

plasma jet (reprinted from Ref 121 copyright 2004

with permission from Elsevier)



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with sp3 bonded carbon in the diamond structureAmorphous carbon film with NCD normally consists ofsp2 clusters connected by sp3 network Ballas diamondis roughly ball shaped the pieces are very tough andimpact resistant They do not show the cleavagecharacteristics of single crystal diamond

Many investigations have been carried out in order tostudy the effect of nucleation on the growth of diamondfilms Diamond films were grown on silicon substrateswith low (104ndash105 cm22) and high nucleation densities(1010 cm22) From the same growth run a highlyn110m textured 300 mm thick white diamond film with agrowth rate of 24 mm h21 was obtained from highnucleation densities (1010 cm22) and a white diamondfilm of 370 mm in thickness with a higher growth rate of3 mm h21 was obtained from low nucleation densities(56104 to 105 cm22)122 The best quality film obtainedin this experiment was found to have very smoothcrystalline facets free of secondary nucleation and thefull width at half maximum of the diamond Raman peakwas 22 cm21 which was as narrow as that of IIanatural diamond The results suggested that undersuitable growth conditions nucleation density had littleeffect on the film quality and low nucleation densityresulted in higher growth rate than the high nucleationdensity owing to less intense grain growth competitionSince the grains in a polycrystalline film with the highestvertical growth velocity with respect to the substratesurface has the highest probability of survival grainsthat grew normal to the Si surface propagated andsurvived But the growth of the grains that grew offnormal to the substrate surface was terminated

Sometimes the nucleation rate affects the subsequentgrowth of diamond film The nucleation rate had asignificant effect on the heteroepitaxial growth ofdiamond films on silicon surface Highly orientedepitaxial growth of diamond was achieved on mirrorpolished silicon substrate123 Low and high nucleationrates led to some discrete big diamond crystals andpolycrystalline diamond films respectively A highnucleation rate resulted in a simultaneous and rapidgrowth of multi-oriented nuclei facilitating the forma-tion of polycrystalline grains

The relative quality of the diamond film grown at lowpressures (2 torr) using an ECR PECVD system wasfound to be dependent on the initial nucleation densityand amount of the grain boundary fractions present inthe film124

Nucleation density also affected the surface roughnessof the deposited film in the early stages of deposition Anucleation density in the range of 108ndash1011 cm22

(obtained by applying a coating of the diamond powder(diameter 0038 mm) in a fluid on Si substrate) was usedto study the effect of nucleation density on the filmquality surface roughness and growth rate125 Samplespretreated and processed under similar conditions tominimise the effect of different deposition conditions onfilm morphology showed similar surface texture andmorphology Samples with the highest primary nuclea-tion density had the smoothest film surfaces at alldeposition conditions

Besides the quality the morphology of the diamondfilm is related to the nucleation and growth rate It hasbeen found in several studies that high secondarynucleation with low growth rate generally favours the

NCD whereas low secondary nucleation with very highgrowth rate produces MCD The processing parametersalso affect the morphology of the produced film A highbias voltage substrate temperature CH4 concentrationand low total gas pressure enhance the frequency ofsecondary nucleation and hence favour an NCD A highgas pressure and MW power gives MCD The effect ofan additive gas in the precursor sometimes changes themorphology of the film Addition of noble gases such asAr He and Xe to the conventional CH4H2 mixtureproduces NCD films Presence of N2 gas in the precursorfavours NCD film formation Recently an Ar richplasma (CH4Ar) has been very effective in producingUNCD film37

The growth and quality of diamond film is stronglydependent on the processing conditions The substratepretreatment precursor gases any additive gas in theprecursor and process parameters such as temperaturepressure and MW power equally influence the growthrate and the quality of the film A lot of research hasbeen conducted in the past 25 years to study the effectof different processing parameters on the growth ofdiamond film on different substrates126ndash134 Besides theconventional CH4H2 mixture graphiteH2 has also beenused to form the film126 But instead of continuous filmonly blocks of films and particles were obtained Amongthe catalytic effect of various metal particles thosecontaining Co and Ni were found to enhance the growthrate and the growth mechanism in the presence of metalparticle was found similar to that of low pressure CVDSince the growth of the diamond phase occurred asa result of gas phase reaction either from methaneconversion or from hydrogen radicals generated fromhydrogen reacted with graphite on the sample surfacegrowth mechanisms for diamond synthesis methodseither from gas precursor or solid precursor were similarto that of low pressure CVD diamond The RTSE studywas conducted to monitor the effect of different proces-sing conditions during the course of deposition133 Inaddition to the accurate surface temperature measure-ment and close monitoring of the nucleation and earlygrowth stage this study also provided information onbulk layer thickness mass thickness of the sp2 C in thebulk layer and void volume fraction in the bulk layer Anattempt was made to optimise the different processvariable such as reactor pressure substrate temperaturegas flow rate and CH4 concentration upon diamond filmgrowth on Si3N4 and SiC substrates40134 It was shownthat the conditions for initial nucleation and film growthwere different in two cases For SiC substrate nucleationdensity was strongly dependent on the CH4 concentrationand on pressure but growth rate mainly was influenced byCH4 percentage at the deposition temperature range of780ndash885uC For the Si3N4 substrate on the other handnucleation was favoured by low process pressure andCH4 concentrations (12ndash16) while the growth ratewas enhanced mainly by increasing the reactor pres-sure The deposition experiments were carried out at800ndash900uC

Since the conditions for growth related to a specificsubstratendashprecursor combination are different from theother substratendashprecursor combination we briefly dis-cuss the effect of the different process parameters on thegrowth of diamond films for a particular substratendashprecursor combination below



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Effect of temperatureThe homoepitaxial diamond film deposition on (111)face of high pressure and high temperature synthesiseddiamond in a cylindrically coupled MW plasma reactorwith a radio frequency (RF) induction heating systemusing CH4H2 gas mixture showed an increased hydro-gen incorporation and enhanced growth rate withincreasing substrate temperature128 The increasedgrowth rate with temperature (600ndash920uC) is shown inFig 11 The growth rate was found to follow anArrhenius behaviour and was expressed as

G~A expE

RT

(2)

where A E R and T are the pre-exponential factor theactivation energy for growth the universal gas constantand the absolute temperature respectively A similarbehaviour of growth rate with temperature was reportedin the literature129ndash131 However the activation energyfor growth (36iexcl6 kJ mol21) calculated from the leastsquare fitting of the Arrhenius plot is different fromthose reported earlier for growth on (100) and (111)faces The observed difference in activation energy wassuggested to be due to the difference in heating methodemployed for the deposition experiment It might also bedue to uncertainty in measuring the actual surfacetemperature during deposition

The effect of decreasing filament temperature ongrowth of diamond films using HFCVD has beenreported135 Well faceted diamond crystals wereobtained at a low filament temperature in the range1500ndash1700uC using a CH4ndashH2 gas mixture The deposi-tion rate decreased with decreasing filament tempera-ture Although at lower filament temperature (1300uC)the morphology of the grains looked ball like thediamond characteristics was still there as confirmed byXRD and Raman spectroscopy However the growthrate and quality of the film improved to a certain extentby introducing an inert gas

The influence of substrate temperature and CH4

percentage on diamond film quality texture morphol-ogy and growth rate was already reported in theliterature136ndash138 Besides CH4 concentration texturedgrowth of diamond film is a function of the growthtemperature The competitive growth between (100) and(111) planes decides the texture of diamond filmDisplacement of these planes from the nucleation centreis a function of CH4 concentration as well as depositiontemperature For textured growth the lsquoarsquo parameter(which is defined as a5312V100V111 where V100 andV111 represents the displacement rates of the (100) and(111) planes respectively) is dependent on the substratetemperature When a51 cubic crystallites are formedwith (111) texture but when a53 pure octahedrondiamond crystallites are obtained with distinct (100)morphology The variation of lsquoarsquo with CH4 and TS

(substrate temperature) is shown in Fig 12a It showsthat decreasing CH4 concentration and increasingsubstrate temperature gradually favours cubic crystal-lites with (111) morphology than the octahedroncrystallites with (100) texture Therefore the n100mtexture associated with (111) morphology is favoured byhigh CH4 percentage and low substrate temperatures(conditions which provide high hydrocarbon super-saturation) But the n110m texture associated with(100)(111) morphology is favoured by low CH4 percen-tage and high substrate temperature (low supersatura-tion) The combined effect of CH4 and substratetemperature on diamond film characteristics were dis-cussed for two different MW power densities and thecombined effect of CH4 substrate temperature andMW power density is shown in Fig 12b and c17 It isinteresting to note that a (100) texture with an a valueof 25 was obtained either at 17CH4 780uC and15 W cm23 or at 4CH4 875uC and 23 W cm23However n110m texture associated with (111)(100)morphology was obtained at high temperature and lowmethane concentration irrespective of the MW powerdensity

Effect of pressureHigh pressure normally increases the growth rateRecently some reports showed very high growth rateusing high gas pressures139140 High growth rates up to45 mm h21 were obtained at high pressure (188 torr)and low CH4 concentration for diamond deposition byMPCVD process using ellipsoidal reactor H2 deso-rption from the diamond surface under atomic hydrogenflux was found to limit diamond deposition rate Anearly linear increase of the diamond deposition ratewith the total pressure was observed at a CH4

concentration of 05 The deposition rate increasedfrom 07 mm h21 at low pressure (94 torr) to 45 mm h21

at 188 torr The observed variation of the growth ratefrom 07 to 45 mm h21 was correlated to the depositiontemperature from 727 to 1060uC respectively A similartrend of growth rate was obtained at high power highCH4 concentration high temperature and at highpressure up to 150 torr by Chein et al141

Homoepitaxial growth of diamond film with growthrate as high as 50 mm h21 was achieved140 by anMPCVD process with 170 torr pressure 252 kW MWpower and 7CH4 as the precursor A cooled stage wasused for the experiment The variation of the processparameters produced films with lower growth rates

11 Temperature dependence of diamond growth rate

(reprinted with permission from Ref 128 copyright

1999 American Institute of Physics)



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(10ndash20 mm h21) However the surface conductive elec-trical properties of the film with highest growth ratewere inferior to those deposited at lower growth ratesowing to their increased surface roughness Since thesurface roughness affects the carrier transport surfaceconductive properties are greatly deteriorated by theincreased surface roughness of the film The filmdeposited at such high growth rates was found compar-able with those obtained by other methods such as dcarcjet142

Effect of MW powerA high MW power coupled with high gas pressure andtemperature has sometimes been found to affect thegrowth rate and morphology of the deposited film Thetexture of the film is related to the input MW powerduring the deposition Pulsing of the MW helps inachieving the low substrate temperature as well as thegood growth rate

A growth rate of 93 mm h21 was obtained fordiamond films deposited at CH4 concentration of 2ndash4 in H2 an input power of 45 kW and gas pressure of120 torr using a 5 kW MPCVD reactor143 The filmswere found to be either n100m or n111m textured whichwas determined from the peak height ratio of the (111)and (400) reflections in the XRD pattern The depen-dence of film texture on CH4 concentration andsubstrate temperature for the 5 kW CVD reactor washowever significantly different from that of 15 kWCVD reactors Addition of small amount of oxygen (O2CH4 5 006) in the precursor gases increased the growthrate by 50 from that without the oxygen while theaddition of larger amount (O2CH4 5 006 to 05)suppressed the growth rate to 38ndash28 mm h21

An increased deposition rate of polycrystalline dia-mond film was obtained by varying the MW pulserepetition rate and duty cycle144 An increase in growthrate was found with pulsing frequency for the sameaverage power Changing the duty cycle for a fixed totalplasma on time resulted in the same film thickness for allduty cycles which suggested that growth took place onlywhen pulse was on The dependence of growth rate onpulse frequency and film thickness on duty cycle isshown in Fig 13

Effect of precursor gasesThe precursor gas composition also affects the growth ofdiamond film Despite the most commonly used CH4H2

mixture CH4N2 COH2 or COH2O2 or halogenatedprecursor like chloro- and fluoro-carbon have also beenused to enhance the growth rate145ndash152 Sometimesdifferent gas mixtures have been used to deposit highlyoriented diamond film153 Effect of CH4H2 ratios havebeen used to study the effect of CH4 concentration onthe quality of the film46 The presence of a small amountof N2 in the precursor gases proved beneficial to gettingNCD films Presence of O2 in the precursor gases eitheras a pure O2 or in the form of some oxides like CO2

or CO helps in achieving low temperature growthHalogenated precursors are also suitable for the lowtemperature growth of diamond

Varying proportion of diamond and graphite wasobtained in Raman spectroscopy during deposition ofdiamond on stainless steel substrate at low pressure andtemperature with different CH4H2 ratios from 4 to946 The early stage of film growth revealed that theadsorbed amount of sp3 and sp2 C on the substrate wasrelated to the ratio of CH4 to H2 in the precursor gaseswhich was identified from an in situ FTIR employingreflectionndashabsorption geometry (FTIRRAS) and OESThe sample grown with 5CH4 in H2 showed nocontribution from graphitic carbon but it reappeared aty1650 cm21 in Raman spectra for CH4 concentrationgt6 However the presence of a graphitic carbonphase on the substrates was believed to occur owing tofactors related predominantly to the substrate chemical

12 a variations of a-parameter as function of CH4 concen-

tration and substrate temperature Ts at MW power den-

sity of 23 W cm23 and combined effect of CH4

concentration (CH4) and substrate temperature TS on

diamond film characteristics at MW power density of b

15 W cm23 and c 23 W cm23 grey zone indicates

domains where nucleation of non-diamond phases first

occurs on (111) faces and then on both (111) and (100)

faces (as CH4 or Ts increases) reprinted from Ref 17

copyright 2001 with permission from Elsevier



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structure rather than to factors associated with speciesoccurring in the plasma No diamond growth wasobserved for 4CH4 in H2 owing to high etching ofthe film by atomic H in the CH4H2 plasma Forintermediate CH4H2 ratios about 4 to 9 sp3 carbonwas present in the form of diamond

Presence of N2 in CH4N2 mixtures strongly influ-enced the growth rate and morphology of the NCD filmsprepared by MPCVD process145 The bonding howeverwas almost unaffected Raman spectra showed thepresence of sp2 bonded carbon in the matrix althoughaccording to electron energy loss spectroscopy and X-ray photoelectron spectroscopy investigations the sp2

content was very small Infrared spectra showed thehydrogen atom to be bonded primarily to the sp3 CHx

groups

Different types of growth behaviour of diamond filmwere seen on Si Zn Al and glass substrates at substratetemperatures between 650 and 1073 K with 05ndash20C2H5Cl z H2 precursor gas using HFCVD andMPCVD processes149 C2H5Cl helped in reducing thesubstrate temperature for diamond deposition 700 KIncreased halogen content in the feed gas increased thegrowth rate as shown in Fig 14 at the cost of decreasedphase purity This was suggested to be due to a lack of

etching of the carbon phases by halogens (Cl and F)On Si substrate the adhesion of diamond filmsdeposited at low temperature was poor probably owingto the lack of an intermediate SiC layer On Alsubstrates good adhesion was observed even at a verylow substrate temperature of 643 K Deposition ontoglass and Zn substrates was difficult On glass theformation of diamond films was observed only at lowtemperature However the adhesion of these films waspoor The deposit on Zn was mainly consisted of anamorphous graphitic phase with some sporadic dia-mond crystallites

Diamond deposition domain is very much dependenton the feed gas composition which was predictedby Bachmann in 1991 Recent research shows thatthe diamond growth domain is also dependent on theradical species present inside the reactor154155 The newCndashHndashO ternary diagram based on the radical speciesclearly distinguishes three different regions non-diamond carbon growth region diamond growth regionand no growth region The analysis of the computa-tional results explains the contradicting experimentalresults based on the non-typical gases (H2CH4 gasmixture is considered as the typical precursor fordiamond growth) Although the CO containing pre-cursors such as COH2 or COH2O2 have been usedquite extensively to grow diamond at relatively lowdeposition temperatures with high growth rate andadequate quality the simulation results predicted CO asa non-participatory species in the growth process Theeffect of pressure temperature and MW power on thegrowth of diamond phase is also predicted based onthe participating species on the growth processAlthough at lower pressure the diamond depositiondomain widens it is very difficult to distinguish the non-diamond carbon growth region diamond growth regionand no growth region at higher pressure which suggeststhat non-diamond deposition at higher pressure isobvious The simulation results also suggest that forthe processes operating at MW power of 500ndash1500 Wthe participating species decrease with increasing pres-sure The main effect of increase in power and pressureis to affect the bulk gas phase temperature andcomposition With increase in power and pressure theproportion of the radical species increases near the

13 Dependence of a growth rate on MW pulse frequency and b film thickness on duty cycle for total plasma on time of

4 h reprinted with permission from Ref 144 copyright 1999 American Institute of Physics

14 Growth rate for diamond films deposited from

C2H5ClH2 gas mixtures at T51073 K as function of

C2H5Cl content (reprinted from Ref 149 copyright

2001 with permission from Elsevier)



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vicinity of the growth surface thereby widening thediamond deposition domain Temperature also affectsthe participating species composition in the growthprocess For constant feed gas composition the parti-cipating species composition migrates from diamondgrowth domain to the non-diamond carbon growthdomain for temperature beyond 1400 K So the higherdeposition temperature will end up with higher non-diamond fraction in the deposited diamond phase Eventhough the new CndashHndashO ternary diagram based on theradical species inside the reactor chamber nicely explainsmany experimental data points in the Bachmanndiagram the computational results do not apply whenthe bulk gas phase temperature is 1150 K Theassumption that the bulk gas phase temperature is equalto the growth surface temperature of y1150 K restrictsthe analysis of diamond growth behaviour based on theradical species involving Ar rich plasma where the bulkgas phase temperature is much higher than 1150 K

Effect of variation in processing conditions andadditives in precursor gasesSometimes the variation in the processing conditionssuch as local laser assisted heating of the selectedsubstrate area pulse modulation of the ECR plasmaearly CH4 introduction in the reaction chamber andcombination of a RF plasma with HFCVD influencesthe diamond growth156ndash159 The presence of an additivesuch as H2 N2 F2 Ar Xe H2S and PH3 in theprecursor gas also affected the diamond growth160ndash169

The enhanced nucleation and growth of diamond filmwas achieved by introducing CH4 right from thebeginning instead of introducing it after 5 min atsubstrate temperature TS700uC using the RF andHFCVD methods159 The film obtained was verysmooth and the contamination from W filament wasreduced to a large extent by preheating the filament inCH4 and H2 atmosphere and placing it close to theupper electrode Although graphite formation could notbe avoided in the initial phase of the growth it stoppedafter some time

A factor of three increases in growth rate of diamondfilm was obtained by using an ECR MW plasmadischarged in pulse modulation mode compared withthat obtained in a continuous plasma of time averagedpower near the threshold value required to triggerdiamond growth157 The time averaged CH3 radicaldensity measured by infrared laser absorption spectro-scopy was also enhanced by pulse modulation and wasup to 13 times larger than that in the continuousplasma The number of carbon atoms supplied as CH3

radicals (measured by infrared laser absorption spectro-scopy) was found larger than the actual growth rate byalmost two orders of magnitude The enhancement ofgrowth rate and CH3C2H2 radical density with MWpower is shown in Fig 15 The enhancement of CH3 andC2H2 radical density showed a similar trend with MWpower The radical density did not change much up to2 kW but beyond that it increased monotonically withpower up to 5 kW The density of CO2 on the otherhand decreased continuously with increasing MWpower The growth rate did not show any significantchange initially but beyond 25 kW it suddenlyincreased from 005 mm h21 (at 25 kW) to035 mm h21 (at 5 kW)

The effect of N2 addition in the precursor feed gas(CH4H2Ar) was found beneficial to diamond synthesisIn small quantities (100 ppm) it improved the dia-mond quality and favoured growth of 100 textureHowever in higher quantity it led to black diamondfilms owing to the presence of a large amount ofgraphitic or amorphous carbon in the film Nitrogendoped diamond film grown at 30 torr pressure 800uCand at varying (NC) ratio from 006 to 068 using CH4H2Ar mixtures by a 100 KW dc arc plasma jet CVDshowed significantly improved film morphology growthrate crystalline orientation nucleation density andfracture strength for freestanding diamond films121

Although the grain size decreased with small additionof nitrogen (NC5006) and increased further withincreasing nitrogen content from NC5012 to 022resulting in grain size of hundreds on nanometres for anMCD films It was not mentioned whether the nitrogenwas incorporated in the diamond structure or was at thegrain boundary The variation of growth rate withincreasing NC ratio is shown in Fig 16 The growthrate of this diamond film grown by dc arc plasma jetsystem increased rapidly from 12 mm h21 for NC50to 235 mmh21 for NC520 But for larger nitrogenfraction in the gas mixture the growth rate decreased to165 mm h21 for NC568 The deleterious effect of N2

addition in the precursor gas (CH4H2) on the mechan-ical properties was displayed by a continuous decrease inmeasured fracture strength with increasing NC ratioAn enhanced secondary nucleation and the 100 facetdevelopment was observed in nitrogen doped diamondfilms at CH4 concentrations 05ndash3 and N2 concentra-tions from 0 to 3000 ppm in the feed gas with averagedpower density of 15 W cm23162 Along with enhancedgrowth rate and chemical purity of the film surfaceelectrical resistance and surface morphology was alsoaffected The presence of nitrogen in the feed gasaffected the quality of the film R which was defined as

R~Isp3

IflzIsp3zPk

Ik

(3)

15 Growth rate and densities of CH3 C2H2 and CO2 ver-

sus MW power in continuous wave discharge plasma


1996 IOP Publishing Limited)



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where Isp3 was the intensity of the diamond line Ifl theintensity of the fluorescence background and Ik was theintensities of the non-diamond contributions originatingfrom adjacent Raman bands (especially graphite D andG bands) The variation of the quality factor and thesurface resistance at 300uC are shown with varying N2

concentration in Fig 17a and b respectively Theincorporation of N2 in the feed gas affected the diamondfilm quality in different ways for a range of CH4

concentration in the gas mixture An optimal value of032 for R was obtained for the N2 concentrations from1030 to 1430 ppm Thereafter it continuously decreasedto 012 for 2500 ppm N2 in the film For 05CH4 onthe contrary the quality R monotonously decreasedfrom 032 to 023 for N2 content varying from 0 to1430 ppm But for higher CH4 concentration (namely3) the N2 concentration dependence of quality factorwas very weak and the R value remained constant y05At low CH4 concentration nitrogen degrades the filmcrystallinity and structural properties of the film but athigher CH4 level nitrogen improves the (100) textureformation causing secondary nucleation on the (111)faces resulting in MCD films The surface resistancealso increased by six orders of magnitude (from 108 to1014 V) with N2 in the film The resistance graduallyincreased with increasing N2 concentration and reacheda maximum at 1014 V corresponding to N2 concentra-tion of 1430 ppm It decreased thereafter up to2500 ppm N2 This unusual behaviour was explainedon the basis of the compensation of the doping state ofthe diamond Diamond film grown in the absence of N2

behaved as a p-type doping material but in the presenceof N2 it behaved as an n-type doping material When N2

is incorporated in small amount in the film the p-typedoping may become compensated which progressivelyincreased the resistance For further increase in N2

concentration the film resistance reached a maximumfor y1430 ppm N2 a situation where p-type doping wastotally compensated by the n-type doping A furtherincrease in N2 concentration induced the n-type dopingbehaviour and the resistance decreased

These results showed that nitrogen was incorporatedin the diamond structure and contributed to the

electrical conduction of the film The deleterious effectof N2 is also reported in the literature161163 Thesestudies were conducted with conventional H2CH4 gasmixture Although no discussions were made whethernitrogen was incorporated into the diamond structure orwas at the grain boundary region Increasing nitrogencontent changed the faceted morphology to cauliflowerstructure and for nitrogen content 1000 ppm in the gasmixture NCD structure was observed161 The effect ofnitrogen addition in the conventional H2CH4 gasmixture in an HFCVD process resulted in reduced grainsize with increasing nitrogen content and finally endedup with ball like morphology163 Nitrogen was foundto be chemically bonded to diamond structure to amaximum content of 33 at- which was confirmed byX-ray photoelectron spectroscopy studies

An enhanced growth rate of diamond film wasobserved in presence of Ar gas (0ndash85 vol-) in the feedmixture of ethanol and hydrogen gas which wasassociated with an increase in carbon free radicals C2

(up to 40 vol-Ar) or to the increase in the filamenttemperature in an HFCVD process165 The increasedgrowth rate with Ar addition is shown in Fig 18Analysis of SEM showed an increase in the diamondgrain size and increased defects in the deposited filmswhich was also confirmed from room temperaturephotoluminescence spectroscopic studies However well

16 Growth rates of diamond film as function of nitrogen

to carbon ratio (reprinted from Ref 121 copyright


17 Variation of a diamond film quality factor R as func-

tion of N2 concentration for various CH4 concentra-

tions and b surface resistance (measured at 300uC)

as function of N2

concentration for 1CH4 reprinted

from Ref 162 copyright 2002 with permission from

Elsevier



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Ltd faceted diamond films of good quality were obtained

only at lower Ar concentration up to 65 vol- Higherconcentrations (85 vol-Ar) led to diamond likecarbon or other complex carbon structures

Ar addition to the precursor gases was found toincrease the growth rate and decrease the grain size ofpolycrystalline diamond film synthesised by an MPCVDmethod in our laboratory Using ultrasonically activatedSi substrate in a 20ndash40 mm diamond slurry depositiontemperature of 800uC pressure of 95 torr and 900 WMW power polycrystalline diamond film was fabricatedusing 1CH4 4ndash99H2 and 95ndash0Ar The growth rateincreased from 049 mm h21 for no Ar addition to137 mm h21 for 80Ar addition in the CH4H2 mixtureHowever at higher Ar concentration (95Ar) the ratedecreased to 076 mm h21 The biggest grain size(224 mm) was obtained for a gas mixture compositionof 39H2 60Ar and 1CH4 using the abovedeposition parameters166

A positive driving force for diamond growth wasobserved in presence of F2 in the precursor gas164 Thedriving force was taken as the difference in chemicalpotential of carbon in the solid (diamond) and gas phasesA positive driving force indicated a decrease in thechemical potential of carbon in diamond phase or in otherwords only a positive driving force dictated diamondformation from the gas phase The experiment showedthat the driving force for diamond growth was positive ata particular temperature range (980ndash1240 K) and withinthat temperature range the growth of diamond under lowpressures was possible The driving force for graphite wasnegative in the temperature range of 980ndash1240 K Theeffect of F2 addition in the reaction system on the drivingforce for diamond and graphite formation was dividedinto two parts For l (the molar ratio of fluorine to themixture of fluorine and hydrogen F(FzH)) 5 0 to 012the driving force for diamond growth was positivewhereas that for graphite was negative which meant thatonly diamond could be grown in that region (free of anygraphite contamination) But for higher F2 content(l012) diamond quality deteriorated owing to thepresence of graphite in the deposited film

A decreased growth rate at higher temperatureowing to a reduction in the concentration of CHx

species in the plasma (in the presence of H2S gas in theprecursor) was observed in a CVD diamond filmdeposition experiment168 At lower substrate tempera-tures (560ndash690uC) the authors speculated that anincreasing adsorption of atomic sulphur in the growingdiamond surfaces influenced the growth mechanismThe deposited diamond films preserved their excellentquality even for the highest H2S concentrations (nearly1) which was evident from micro-Raman measure-ments The electrical properties were unchanged by the Sincorporation As per the author sufficient S incorpora-tion is required to make the S doped diamond filmelectrically active The S doped diamond film whichshowed n-type conductivity also contained B as thecontamination and the presence of B accelerated the Sincorporation in the film Since these S doped diamondfilms were devoid of any B contamination no change inelectrical properties was observed

Diamond growth conditions are strongly influencedby the presence of phosphine (PH3) in the precursorgases At a methane to hydrogen ratio of 015 andsubstrate temperature of 950uC a smooth (111) orientedhomoepitaxial diamond thin film was obtained in anMPCVD process in the presence of PH3 gas up to1000 ppm169 The (111) surface was found to be the bestsurface for the growth of phosphorous doped diamondThe film showed n-type conductivity over a wide rangeof temperature which was confirmed by Hall effectmeasurement For the best sample (PH3 concentration600 ppm) the Hall mobility was 28 cm2 Vs21 measuredover a temperature range of 400ndash600 K

About 50 increase in growth rate was observed inthe presence of 1Xe in the CH4 and H2 precursorsusing an MPCVD process167 A morphological changefrom the cubic to platelet grain structure was observedwithout degradation of the crystallinity The favourableeffects of Xe addition were attributed to its lowdissociation and excitation energies (828 eV for Xeradicals) which were sufficient for the formation of CH3

but not CH2 radicals The addition of Xe led to a higherdensity plasma and lower temperature The enhancedgrowth rate and good quality of the film was due to thepresence of a large amount of the atomic H and CH3

radical (precursors for diamond formation) and a smallamount of the CH2 in the plasma The increased growthrate with Xe addition is shown in Fig 19

18 Diamond growth rate as function of argon concentra-

tion in gas feed (reprinted from Ref 165 copyright


19 Variation of diamond growth rate with Xe addition at

790ndash830uC (reprinted with permission from Ref 167




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The growth of chemical vapour deposited diamondfilm is influenced by the deposition process conditionssuch as substrate nucleation temperature pressure gascompositions and presence of additive gases in theprecursor gases The quality and the morphology of thedeposited film are dependent on these parametersSmaller grain sizes and smoother surface finish isobtained at high nucleation density for a particulartemperature pressure and MW power Lower nuclea-tion density on the other hand produces diamond filmsof bigger grain sizes and rougher surface texture Gascompositions and the presence of additive gases in theprecursor affect mainly the quality and texture ofthe film Presence of N2 in the precursor gases reducesthe grain sizes leading to NCD film O2 and O2

containing precursors or the presence of small amountof halogen gas in the precursor help in achieving lowtemperature growth of diamond film Small amount ofinert gas additives such as He Ar Xe in the precursorgases reduce the grain size of the diamond film owing toenhanced secondary nucleation in the deposition pro-cess Temperature or pressure affects the growth rate ofdiamond film irrespective of the deposition process suchas MPECVD or HFCVD An increase in substratetemperature and gas pressure increases the growth rateowing to enhanced diffusion of the growth species onthe substrate surface and increased concentration of thegrowth species respectively But the success in achievinghigh growth rate of vapour deposited diamond film inthe recent research results has mostly come throughincreased power density irrespective of the depositionsystem employed Four orders of magnitude increase inlinear growth rate was observed with increasing powerdensity per unit area for major types of the depositionprocesses such as MW hot filament RF oxyacetylenetorch atmospheric plasma jets and ion beam170

Although the rate depends mainly on the type of CVDprocess used the source gas composition and pressurealso affects the growth rate The increased growth ratewith increased power density is associated with thecreation of hydrogen free radical or atomic hydrogen inthe reaction environment The strong endothermicconversion of atomic hydrogen from molecular hydro-gen is strongly favoured by the increased energy input inthe system The generation of hydrocarbon species in thegas phase with increased power density also affectsthe growth rate significantly Since atomic hydrogen andthe hydrocarbon species do contribute to the diamondgrowth mechanism the enhanced growth rate withincreasing power density is expected

Growth mechanisms in plasma environmentSince diamond is a metastable phase compared withgraphite the conversion of diamond Cd from the morestable graphite Cg seems to be a thermodynamicparadox This should be impossible at the subatmo-spheric pressure owing to an overall increase in theGibbs free energy

CgCdDG0298~29 kJ mol1 (4)

A careful look at the CVD diamond process suggestedthat the conversion of diamond from stable graphiteunder the typical CVD conditions did not violate thethermodynamic laws which require a negative change inGibbs free energy for a chemical reaction to occur

spontaneously The diamond formation from graphiteproceeds through the following steps3 molecular H2

dissociation by hot filament plasma or electric gasdischarge

H22H DG02500~75 kJ mol1 (5)

Cgz4HCH4(gasification of graphite)

DG01500~470 kJ mol1 (6)

formation of CHx radicals (x53)

CH4zHCH3zH2 DG01500~42 kJ mol1 (7)


CH2zHCHzH2 DG01500~38 kJ mol1 (9)

CHzHCzH2 DG01500~84 kJ mol1 (10)

The generated carbon atoms are then added to the dia-mond lattice (Cd represents a C atom in diamond lattice)

CzCd2Cd DG01500~480 kJ mol1 (11)

Although it is seen that all the reactions shown aboveare not thermodynamically favourable owing to positivechange in Gibbs free energy addition of all thethermochemical reactions from equations (5) to (11)gives a thermodynamically favoured net reaction for thegraphite to diamond transformation driven by the inputof atomic H

Cgz8HCdz2H2 DG01500~1097 kJ mol1 (12)

Hydrocarbon species (ions or radicals) are generatedduring the interaction of the precursor gases withplasma and hot filament These species are then eitherattracted with applied bias or without applied bias to thesubstrate surface They then tend to migrate towardseach other and get combined to form the diamond filmThe energy required for migration in the neighbouringsite is different for different species Surface migration ofCH2 on diamond (111) surface requires less energy thanthat of CH3171 The chemisorption and desorption ofthese reactive species followed by surface reactionconstitute diamond growth Although a lot of workhas been carried out to study the growth mechanism andample evidences are there to support each and everystep the exact nature of nucleation and growth is still amatter of controversy Though the basic mechanism issame for all the systems little variation is observed fromsystem to system depending on the precursor gasessubstrate used diluent gas used deposition temperatureand gas pressure

Although the above approach was only applied togrowth on (100) facets the key role of CH3 radicals andH atoms in diamond growth was verified by anothermechanism which tried to depict the correct qualitativebehaviour172173

CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



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CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)

where CdH stands for a generic hydrogenated surfacesite and Cd the site with hydrogen removed ie aradical site CdM represents an adsorbate methyl groupCdM with a hydrogen atom removed and Cd an atomof bulk diamond Without considering each step indetails the model considered the following steps inexplaining the diamond growth mechanism

(i) establishment of a steady state surface radicalsite coverage via reactions (13) and (14)

(ii) attachment of reactive hydrocarbon species(unsaturated molecules or radicals) to the surfaceat these sites via reaction (15)

(iii) removal back of the surface adsorbates to the gasphase either by thermal desorption (via reac-tion (16)) or attack by atomic hydrogen (etchingvia reaction (17)) and finally incorporation ofthe adsorbate into the diamond lattice (withabstraction of adsorbate hydrogens by H) viareaction (18)

The role of CH3 radical and atomic H in diamondgrowth is also evident from the observed reduction ofgrowth rate with depleting H and CH3 radical fordiamond synthesis in an HFCVD process using CH4H2N2 and CH4H2NH3 gas mixtures174 With NH3contrary to N2 clear depletion of both H atom and CH3

radical number densities were observed which were alsoconfirmed from a modelling of the gas phase chemistryincluding CHN Calculations for CHN gas mixturesshowed significant N atom production owing tosuccessive lsquoH shiftingrsquo reactions NHxzH u NHx21

zH2 (51 to 3) which accounted for the observed Hdepletion in the system Irreversible reaction of theseatomic N with CH3 radical produced HCN therebyreducing the hydrocarbon species available for diamondgrowth Molecular nitrogen N2 in the prevailing CVDenvironment was found unreactive

For bias enhanced growth of diamond the mechan-ism was said to be a combination of the surface processwhich is typical of CVD diamond growth and sub-plantation process typical for growth by energeticspecies175 Since CVD conditions help in etching outthe graphitic carbon from the surfaces and the biasingconditions used in the experiment was the same as theenergy required for subplantation process the highconcentration of smooth NCD films consisting ofmainly sp3 carbon was thought to form by the proposedmechanism

But the diamond formation looked different in caseof the laser ablation of the graphite target in an oxygenatmosphere The presence of C2 CO or ionised carbonspecies was observed near the substrate surface whichwas identified in the optical emission spectra176 COmolecules were formed by the reaction of the emittedcarbon species with O2 gas It was suggested that theionised carbon species with a high kinetic energy reactwith each other or with ambient oxygen gas to form C2

or CO The formation of diamond crystals wereproposed to be related to the existence and reaction ofthese highly excited molecules near the substrate surface

Current understanding on growth of chemicalvapour deposited diamond filmsThe chemical and physical processes that take placeduring the CVD of diamond films in the MW plasma arecomplex The gases after mixing in the depositionchamber face an activation region (hot filament in caseof HFCVD or MW plasma in case of MPCVD) wherebythey form ions radicals neutral atoms and electronsThese reactive species undergo complex reactions beforethey get adsorbed onto the substrate Surface diffusionof these adsorbed species followed by addition orsubtraction reaction with the neighbouring species (ionsor radicals or neutral atoms) leads to the formation ofstable diamond nuclei After 70 deposition experimentswith different reactors and process gases Bachmannconcluded that diamond film will only grow when thegas composition is close to just above the CO tie line inFig 20 Below the tie line no deposition is found tooccur Above the tie line non-diamond carbon is themajor phase except for a narrow window wherepolycrystalline diamond film grows He also found thatthe diamond growth is independent of the nature of gasphase precursor Since the gas phase chemistry is rapidthe precursor gases essentially brake down to smallerreactive components to form the diamond filmAlthough the presence of many atomic molecular orionic species such as C CH C2 C2H CH3 C2H2 CH3

z

is detected in the plasma CH3 C2 and H have beenidentified as the principal growth species for diamondsynthesis In the H2 rich plasma like in conventional H2CH4 plasma CH3 radical was found to be responsiblediamond growth species But in H2 poor plasma like inArH2CH4 plasma C2 was considered as the primarydiamond growth species But some authors have alsosuggested C2 radical as the responsible growth speciesfor growth of MCD at high rates by high pressure andhigh power density MW plasmas in gas mixtures of CH4

and H2 without the Ar gas177178

20 Simplified form of Bachmann triangle CndashHndashO compo-

sition diagram numbers in axes represent atomic

fractions lsquoacetonersquo in non-diamond carbon region

represents undiluted compound reprinted with per-

mission from Ref 1 copyright 2000 the Royal

Society



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Atomic H plays an important role and considered tobe the most critical component driving the depositionchemistry Therefore a high concentration of atomic His crucial to the diamond growth process Terminationof the surface dangling bonds to prevent the cross-linkage and surface graphitisation is performed by theatomic H Atomic H is also responsible for etching ofgraphitic sp2 carbon In addition it breaks the longchain hydrocarbon into smaller pieces to reduce thechances of sticking those hydrocarbons onto the grow-ing diamond surface Creation of the reactive radicalssuch as CH3 by reacting with the neutral species CH4 isalso performed by atomic H The growing diamondsurface is fully saturated with atomic H which limits thenumber of sites available for hydrocarbon speciesnamely CH3 to get adsorbed and block the surfacediffusion of the adsorbed species The sequence ofdiamond growth is schematically shown in Fig 21Atomic H abstracts a surface H to form molecular H2

and leaves behind a reactive site on the surface (step 1)This reactive site either may get engaged by aneighbouring H to go back to the original stableconfiguration or may react with a CH3 radicaleffectively adding one C atom in the diamond lattice(steps 2 and 3) This process of H subtraction andconsequent CH3 addition may occur on a neighbouringsite to the attached CH3 group (step 4) A further Hreduction from any one of the attached methyl groupleaves behind a radical (steps 5 and 6) which thencombines with the neighbouring CH3 group to form thering structure (step 7) making two C atom incorporatedinto the diamond lattice Therefore diamond growthcan be considered as a stepwise addition of carbon atomto the existing diamond lattice catalysed by atomic HFor oxygen containing precursor OH plays the role of

H and also since OH is more effective in etching thegraphitic carbon from the growing diamond surface thegrowth rate and quality of the film is improved

The growth of UNCD involves C2 dimer radical asthe principal growth species179180 Since the chemisorp-tion of C2 to diamond (110) and (100) surfaces is highlyexothermic and involves lower activation energy dia-mond growth may proceed on these surfaces without theneed of atomic H The growth mechanism involving C2

dimer does not require any hydrogen abstractionreactions from the surface as proposed by Gruenet al181 The proposed mechanism involves the successiveaddition of the C2 molecule onto the surface CndashC dimerbond as follows the growing diamond surface wasconsidered as [(100)2(261)]H reconstructed surfacewhich is shown in Fig 22a where big atoms are C andsmaller atoms are H terminating the surface A reactingC2 molecules hit the surface and insert into the surfaceCndashC dimer bond (Fig 22b) Another C2 molecule getsinserted into the adjacent CndashC bond to form a newsurface carbon dimer (Fig 22c) In the same way C2

molecule forms a new surface dimer on an adjacent row(Fig 22d) In the next step a new C2 molecule getsinserted into the trough between the two new surfacedimer formed (Fig 22e and f) This new surface dimerrow formed by the C2 molecules is perpendicular to theprevious dimer row In this way C2 molecules getincorporated into the surface CndashC dimer bond of thegrowing diamond surface and form the new surfacedimer CndashC and the growth process continues

Low temperature diamond synthesisFrom different investigations diamond nucleation andgrowth have been found to be a surface phenomena andthermally activated process So lowering of the substratetemperature leads to a very slow growth rate whichmakes the process economically unviable Numerousinvestigations have been conducted concerning the

21 Schematic of reaction process occurring at diamond

surface leading to stepwise addition of CH3 species

and diamond growth (reprinted with permission from

Ref 1 copyright 2000 the Royal Society)

a [(100)ndash(261)]H reconstructed diamond surface b C2

molecule inserts into CndashC surface dimer bond c C2

molecule inserts into adjacent CndashC surface dimer bondforming new surface dimer perpendicular to previousdimer row d second C2 molecule forms new surfacedimer in adjacent dimer row e third C2 moleculeinserts into trough between two previously incorpo-rated C2 molecules f third C2 molecule completesinsertion into trough forming dimer row perpendicularto previous surface row

22 C2 diamond growth model (reprinted with permission

from Ref 181 copyright 1995 American Institute of

Physics)



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thermodynamics of the processes involving either a CndashHCndashHndashO precursor systems or a halogen containinggas phase182ndash184

The deposition of diamond or graphite from the gasphase is a problem of kinetics or a kinetic barrier Butthermodynamically the conditions can be predictedunder which diamond or graphite is not stable withrespect to the gas phase The thermodynamic limit ofthe substrate temperature for which diamond can bedeposited at a particular pressure was evaluated in theCndashH and CndashHndashO systems182 The conditions for thelower limit of substrate temperature were different forthe CndashH and CndashHndashO systems In the CndashH system thepressure of the CVD reactor was an importantparameter for the lower limit of the substrate tempera-ture which is shown in Fig 23a For a gas mixture of1CH4ndash99H2 which is shown by the left verticaldashed line in the figure the lower limits were 1400 900

and 600 K under 101 325 Pa (760 torr) 101325 Pa(76 torr) and 101325 Pa (76 mtorr) respectively Atatmospheric pressure (760 torr) diamond was depositedinside the C shape domain at temperatures 1400 KBut 1400 K only the gas phase was stable Withincreasing CH4 concentration to 5 (indicated by theright vertical broken line in the figure) the depositiondomain was extended and the lower limit was 1100 KBut increasing the CH4 concentration degraded thequality of diamond by producing the non-diamondphase It was suggested that reducing reactor pressurewas more effective in achieving low temperaturedeposition than increasing the CH4 concentration inthe CndashH system

In the CndashHndashO system however the thermodynamiclower limit of the substrate temperature was found aslow as room temperature Unlike the CndashH system thecarbon solubility continuously decreased with decreas-ing temperature which is shown in Fig 23b at the fixedratio of OH51 for three different pressures Butaccording to Bachmannrsquos diagram the diamond deposi-tion is possible along the narrow composition bandclose to the ratio of OC51185 Since the data in Fig 23bwere based on OH 51 an overall composition ratio ofCOH51 1 1 was proposed in Fig 23b for diamonddeposition This ratio corresponded to the gas mixtureof 50 C2H2O2 for which the atomic fraction of carbonbecame 033 This carbon fraction is close to thesolubility line at 1200 K for 101 325 Pa at 900 K for101325 Pa and at 700 K for 101325 Pa The carbonsolubility decreased below these temperatures

Thermodynamics of diamond film deposition atlow pressure in the CndashHndashX (X5F Cl) system wasstudied183 according to a non-equilibrium thermody-namic coupling model proposed by Wang186 which isnot discussed in this article The projective and sectionaltemperaturendashgas composition phase diagrams for the CndashHndashF system in the pressure range of 100ndash6670 Pa andfor the CndashHndashCl system between 100ndash5000 Pa are shownin Fig 24a and b respectively The projective phasediagrams were drawn to cover a wide range of pressuresstudied in the literature Each phase diagram consistedof three regions a gas phase region a possible diamondgrowth region and a non-diamond carbon growthregion The possible diamond growth region signified adiamond deposition probability for the constraint ofsubstrate temperature and C(C z H z X) ratio withinthe region The coincidence of the experimental data(solid triangles for diamond growth experimental pointsand solid circle for non-diamond carbon growthexperimental point) with the probable diamond growthregion predicted by the theory (model) showed thevalidity of the proposed model Thermodynamicanalyses also showed a lower temperature range ofdeposition with increasing X in the precursor whichbecame narrower with further increase in X as shown inFig 25 A continuously decreasing trend of substratetemperature is observed with increasing FH ratio at6700 Pa pressure and carbon content of C(C z H z X)5 001

Although low temperature is a hindrance to thegrowth of diamond films with good growth rate severalresearchers have tried to deposit diamond at lowsubstrate temperatures using various experimental con-ditions as discussed below

23 Metastable CVD phase diagram for a CndashH system and

b CndashHndashO system for diamond (continuous lines) and

graphite (broken lines) deposition in left of curves

only gas phase is stable but in right of curves two

phases (gas and diamond) are stable reprinted from

Ref 182 copyright 2000 with permission from

Elsevier



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A thorough review of the low temperature diamondgrowth was conducted by Muranaka et al in 199426

The low temperature studies were divided into twocategories experiments which achieved the low tem-perature deposition without heating the substrate at alland which achieved the low temperature by controllingthe substrate temperature itself by varying the experi-mental conditions The non-substrate heating driven lowtemperature deposition was achieved by varying theprocess itself like sputtering RF plasma and laserexcitation The substrate heating process on the otherhand was achieved by using different precursor gassystems like COndashH2 COndashH2ndashO2 or halogenated hydro-carbons Source gases capable of generating atomic Oand an excess of H was beneficial for low temperaturegrowth since these species were capable of removing theamorphous and non-diamond component from thefilm The lowest substrate temperature suggested wasy400uC for the diamond growth with crystallinity closeto that of natural diamond Growth rates of 001ndash02 mm h21 near 400uC and 0035ndash03 mm h21 at 130uCwere suggested Ar or He addition to source gases werebeneficial for higher growth rate but at the cost oflowered film quality

Halogen containing hydrocarbons such as differentchloromethane (CCl4 CHCl3 CH2Cl2) and fluro-methane (CF4 CHF3) has long been known as diamond

precursors In early days diamond has been grown atmuch higher growth rate and with better quality usingthese halogenated precursors compared with the con-ventional CH4H2 precursor Most of the early experi-ments involving halogenated precursors were carried outat typical diamond growth temperatures of 700ndash900uCIn 1991 polycrystalline diamond film was grown on Si(100) substrate from an 8 CF4H2 mixture without anysurface pretreatment in a low pressure RF plasmaassisted CVD process at 850uC187 Very high nucleationdensity followed by high growth rate was obtainedwithout any pretreatment of the substrate First reportof diamond growth in an MW plasma assisted CVDusing CF4H2 precursor came in 1992188 CF4 (25ndash40)in H2 precursor was used to grow polycrystallinediamond film at 750ndash820uC temperature 40 torr pres-sure and low MW power of 300ndash400 W Although at40CF4 carbon soot was formed the diamond qualitywas good at lower concentration of CF4 The differencein diamond growth rate was studied using CH4 versuschloromethane reactants CCl4 CHCl3 and CH2Cl2 at10 torr pressure 700ndash900uC temperature in an HFCVDprocess in 1993189 Whereas the growth rate decreaseddrastically with decreasing temperature for CH4 pre-cursor the effect was insignificant for the chloromethanereactants In the same year diamond growth at lowertemperatures of 380ndash700uC was reported by the samegroup using the chloromethane precursors in HFCVDprocess190 Although the growth rate of diamond wasonly 005 mm h21 at 380uC using CCl4 it was almostimpossible to grow diamond 600uC using CH4

precursor Better adhesion and higher growth rate ofdiamond film on WCndashCo tool material was obtained at900uC using CF4 as the reactant in an MWCVD processin 1993191 Three times increase in adhesion and fourtimes increase in growth rate was observed using CF4

instead of CH4 reactant A difference in growthbehaviour 850uC was noticed owing to terminationof the active sites on the diamond surface by fluorinecompounds in an MWCVD process performed usingfluorocarbon species CF4 CHF3 as against one usingCH4 in 1994192 The growth rate as well as quality of thefilm improved 850uC owing to rapid removal of non-diamond phase by fluorination reaction Although inmost of the diamond growth experiments enhanced

25 Dependence of substrate temperature range suitable

for diamond deposition on FH ratio at 670 Pa pres-

sure (C(C z H z X) 5 001) reprinted from Ref 183


24 Comparison of temperaturendashgas composition phase

diagram of carbon deposition with reported experi-

mental results from a CndashHndashF systems over pressure

range from 100 to 6670 Pa and b CndashHndashCl systems

over pressure range from 100 to 5000 Pa reprinted


Elsevier



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growth rate is observed using halogenated precursordecreased growth rate at higher chloromethane concen-tration owing to faster etching rate is also reported193

The enhanced growth rate in these diamond growthexperiments in the halogenated precursor environmentattributed mainly to

(i) increased halogenated carbon radical generationin the gas phase owing to the lower CndashX (X 5 ClF) bond energy compared with CndashH bond energy

(ii) faster surface dehydrochlorination or dehydro-fluorination compared with dehydrogenationreaction

Since hydrogen abstraction or dehydrogenation fromthe growing diamond surface has been found to be therate determining step in the diamond growth processenhanced growth rate is observed for the halogenatedhydrocarbon precursors Low temperature diamondgrowth research using halogenated precursors becameintense in the successive years The deposition tempera-tures were obtained typically 550uC Some interestingresults on the low temperature diamond growth experi-ments using halogenated precursors in the recent yearsare discussed below

Recently different halogenated precursors likeC2H5Cl CHF3 and CF4 with an abundance of H2 gaswere used to achieve low temperature diamond growthA substrate temperature of 370uC was reported fordiamond films grown by an HFCVD process usingCHF3 C2H5Cl and H2 gas as the precursor150 The roleof halogen was suggested in creating active surface sitesfor diamond nucleation and growth The role of halogencontaining precursor on the growth rate is shown inFig 26 where growth rate is plotted against substratetemperature for two precursors H2C2H5Cl and H2CH4 A significant (although low) growth rate wasobserved even at 370uC for H2C2H5Cl gas systemwhereas no growth at all was observed for H2CH4 gassystem below 600uC The growth rate suddenlyincreased from zero to 008 mm h21 upon changing thesubstrate temperature from 600 to 650uC and thenincreased monotonically with temperature for H2CH4

system but for H2C2H5Cl a gradual increase of growthrate was observed with temperature in the range of 370

to 850uC To confirm the low deposition temperaturediamond film was also grown onto low melting substratelike Al Zn and glass using 05ndash20 C2H5ClH2 byHFCVD and MPCVD processes in the temperaturerange between 650 and 1073 K149 In another experi-ment a significant decrease in Tsub down to 370uC wasachieved during processing of the diamond films by anHFCVD process using CHF3 and C2H5Cl in theprecursor gas151 However at lower temperature onlygraphitic deposition was observed and the lowestsubstrate temperature for diamond growth was sug-gested to be dependent on the deposition parameters Adecrease in temperature was observed with decreasing Ccontent in the precursor gas in the case of MPCVDprocess or decreasing filament to substrate distance inthe case of HFCVD process

Different oxygen containing precursors have also beenused to deposit diamond film A high growth rate of upto 25 mm h21 at relatively low plasma powers (05 kW)was observed at low substrate temperature range350uCT500uC for fabricating NCD film byMPCVD process using COH2 gas mixtures147 A COrich mixture of CO and H2 was found to exhibit anincrease and sharp maximum in growth rate as thetemperature was reduced The conventional H2 richmixtures of CH4 or CO and H2 exhibited monotonicdecrease in the diamond growth rate with temperaturebetween 800 and 400uC The low temperature growthbehaviour of diamond as function of the COH2 andCH4H2 ratios was studied by an RTSE and the resultsare shown in Fig 27 The growth rate measured byRTSE was expressed in terms of the mass thicknessgiven by dmass 5 fddb z 05ds where fd was the volumefraction of diamond in the bulk layer of thickness dband ds was the thickness of the surface roughness layerThis figure also shows that when CO or CH4 is highlydiluted with H2 the rate decreases with decreasingtemperature with an activation energy of 8 kcal mol2In another experiment using the same precursor system

26 Comparison of growth rates of diamond films depos-

ited using H2CH4 and H2C2H5Cl (reprinted from


Elsevier) 27 Growth rate of MPECVD diamond on diamond film

substrates as function of inverse temperature using

different COH2 and CH4H2 gas mixtures (reprinted


American Institute of Physics)



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a COH2 gas flow ratio of 18 produced a growth ratepeak near 450uC which was 20 times higher than thatobtained with the standard H2 rich mixtures of CH4H2

and COH2 as shown in Fig 28146 The growthparameters in this study were a substrate temperatureof 480uC an MW power of 500 W a pressure of 10 torrand a CO flow rate of 9 sccm The growth rate wasmeasured by RTSE and was expressed in terms of thediamond mass per area

CH3OHH2 CH4H2 and CH4CO2 have also beenemployed to fabricate diamond films at low tempera-tures Adherent diamond thin films was obtained onsapphire substrates using 1CH3OH and 99H2 gasmixture at substrate temperature of 500ndash550uC and lowpressure (1 torr) in an ECR MPCVD process34 Theshifting of the diamond peak by y6 cm21 in Ramanspectroscopy suggested the presence of very largecompressive stresses (32 GPa) in the film Howeverthe film showed excellent transmission characteristicswith 80 optical transmission at wavelengths 2 mm

Using CH4ndashCO2 gas mixture polycrystalline diamondfilm was deposited at 250uC by an MPCVD method22

The low temperature deposited films showed electricalresistivity three orders of magnitude less than thatobtained in case of conventionally deposited diamondfilms The trapped H atom in the film was found todominate the conduction mechanism The films werefound to exhibit a rectifying behaviour using Pt as theupper electrode

Conventional CH4H2 gas mixture was also used toachieve low temperature ((600uC) deposition of dia-mond on single crystal Si substrate by cooling thesubstrate holder with nitrogen gas194 on WCndashCo basedcutting tools15 to improve the adhesion and themechanical properties and on Tindash6Alndash4V alloy30 usingMPCVD method A decrease in the diamond grain sizeand growth rate and an increased surface smoothnesswere observed with decreasing Si substrate temperature

The limits for low temperature growth of diamondfilms depend substantially on the gases employed as wellas on the carbon concentration in the particularsystem195 With decreasing substrate temperature the

non-diamond fraction normally increases in the depos-ited film The addition of oxygen improves the filmquality and also helps in getting low temperaturedeposition The lowest temperature has been realisedin CO rich systems

The intentional addition of small amounts of N2 todifferent CHO gas systems was studied in getting lowtemperature diamond deposition161 The effect of N2 ongrowth was found different for different gas mixtureswith or without oxygen Whereas adding N2 to CHmixtures resulted in a significant change in filmmorphology growth rate defect formation and incor-poration of H2 its effect on growth from CO rich CHOsystems was much less pronounced The film qualityseriously deteriorated with increasing N2 concentrationin the CH gas mixture However the quality did notchange with increasing N2 concentration in the CO richCHO gas mixtures The presence of oxygen in these gasmixtures somehow removed the deleterious effect ofnitrogen in the formation of defects

Low temperature growth through changes inprocessing conditionsLow temperature diamond growth has also beenachieved by alteration of the processing conditions likecoating the substrate with another material pulsemodulation of the MW plasma cyclic modulation ofthe CH4 flow rate and changing the substrate state

Polycrystalline diamond film with very smooth sur-face was obtained at 600uC by controlling thesecondary nucleation and growth process at lowtemperature14 Since 700uC secondary nucleation wasdifficult on diamond (111) surface a thin gold layer wasdeposited on top of the diamond film grown initiallywhich enhanced the renucleation process Application ofgold layer on diamond film helped in getting lowroughness film as well at low temperature

Low temperature (500 uC) deposition of diamondfilms was achieved by placing the substrate away fromthe plasma source otherwise under the normal deposi-tion condition (4CH4 40 torr 1100 W)196 Both theuntreated and pretreated (by 30 mm diamond powder)substrates were used for the experiment Among varioussubstrates studied (untreated Si pretreated Si pre-treated quartz untreated glass and pretreated glass)pretreated quartz and pretreated glass enhanced thediamond formation at low temperature while untreatedglass gave only graphite formation under the samedeposition conditions Diamond films were also depos-ited on pretreated glass at various CH4 concentrationsand produced the largest grain size with 3 of CH4

concentration The growth rate of the film increasedwith increasing CH4 concentration

Using magnetic field discharge activation and by pulsemodulation of the input MW power polycrystallinediamond films were synthesised at backside substratetemperatures down to 300uC in a low pressure CH4ndashH2ndashO2 MW plasma197 Diamond films grown at backsidesubstrate temperatures of 300ndash500uC exhibited charac-teristic 1333 cm21 Raman phonon peaks with linewidths of 57ndash31 cm21 and clearly defined crystallitesin SEM images The non-diamond carbon content of thefilms was low for temperatures down to 350uC asestimated from the broad peak of the Raman spectray1550 cm21 The non-diamond carbon content was

28 Growth rate of MPECVD diamond on diamond film

substrates as function of COH2 gas flow ratio (rep-

rinted with permission from Ref 146 copyright 1997




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estimated by considering the area under the Ramanpeak at y1550 cm21

An oxyacetylene flame was used to deposit polycrys-talline diamond films onto nitrided chromium using verylow substrate temperatures (400uC)47 But at theselow temperatures extremely weak bonding or nobonding at all was observed between the depositedlayer and the substrate To obtain stronger bondingalthough higher substrate temperatures (700ndash1000uC)were used initially but it was lowered down step by stepto 250uC at the later stages of the growth Howeverlowering the substrate temperature below y500uC fromthe initial temperature led to delamination owing togeneration of thermal stresses in the film

Using a combination of diamondndashnanoseeding on thesubstrate and magnetoactive plasma CVD diamondgrowth was obtained at 200uC19 The lowering of thesubstrate temperature was achieved by forced cooling ofthe substrate holder by a circulating fluid containingwater and ethylene glycol A colloidal solution of 3ndash5 nm diamond powder was used for the diamondndashnanoseeding on the Si substrate The deposited filmhowever was inferior to those fabricated at conven-tional temperature owing to the presence of non-diamond carbon phase in the film

A cyclic modulation of CH4 flow rate was used toenhance deposition of diamond film with high nuclea-tion density on pretreated glass substrate at relativelylow temperature of y450uC18 The cyclic modulationwas carried out through the onoff control of the CH4

flow which was started from H2 and CH4 plasma (CH4

flow on) and ended in H2 plasma (CH4 flow off) Longercyclic modulation time interval was suggested beneficialfor growth enhancement owing to the increased amountof the atomic H concentration in the reaction systemSince atomic H concentration gradually increases duringCH4 flow off time and decreases when CH4 flow is on alarger modulation time (like 90 s 90 s) produced largerconcentration of the atomic H than smaller modulationtime (like 30 s 30 s)

The study of the low temperature growth of diamondfilm reveals that since the low temperature growth ofdiamond is limited by slow kinetics a good pretreatmentis necessary in order to achieve an appreciable growthrate at lower deposition temperatures Seeding thesubstrate by nano-diamond particle has been aneffective way to improve the nucleation density byreducing the incubation period Low temperaturediamond growth from conventional H2CH4 precursorends up with very poor quality film with high content ofgraphitic sp2 phase Extremely low growth rate and poorquality of the film at lower temperature is associatedwith the reduced surface diffusion of the growth specieson the substrate surface The faster and efficient etchingof the graphitic phase by hydroxyl radical (OH)compared with that by atomic H helps in achievingbetter quality diamond film with significant growth rateat lower deposition temperatures using oxygen oroxygen containing precursors The lower bond energiesof the CndashX (X5Cl F) bond in the halogen containinghydrocarbons compared with CndashH bond energy in thehydrocarbon itself provides lots of hydrocarbon ions oratoms in the plasma containing halogenated precursorsThe increased growth rate from the halogenatedprecursors at lower deposition temperature is due to

the availability of the excess growth species in the gasphase

Low temperature growth mechanismThe enhanced low temperature growth rate using thehalogenated precursors like CHF3 and CHCl3 comparedwith that using the common CH4 precursor wasexplained by considering both the thermodynamicequilibrium states and reaction kinetics152 Based onthe observation that CHF3H2 helped in reducing thedeposition temperature whereas no deposition wasobtained with CF4H2 precursor suggested that thebond energies alone could not explain the positive effectof the CHF3 towards growth at low temperature But forCHCl3 the low temperature growth could be explainedbased on the bond energy data Since CndashCl bondenergies in CHCl3 are much smaller (331 kJ mol21) thanthe CndashH bond energies in CH4 (426 kJ mol21) and CndashFbond energies in CHF3 (527 kJ mol21) the generationof CH3 radical is much easier and thermodynamicallyfavourable for CHCl3

For CHCl3 both bond energies CndashH (402 kJ mol21)and CndashCl (331 kJ mol21) are lower than for methaneCndashH (427 kJndashmol21) But for CHF3 both bond energiesCndashH (431 kJ mol21) and CndashF (527 kJ mol21) are higherthan for methane Since radical formation also involvesa chemical reaction both the thermodynamic equili-brium and reaction kinetics have been suggested asfactors The formation of HF from any fluorinecontaining molecule in the gas phase is thermodynami-cally favourable The activation energies for the radical(CH3 and CF3) formation from the precursor gases usedare

HzCH4H2zCH3 Ea~20 to 63 kJ mol1 (19)

HzCF4HFzCF3 Ea~83 to 160 kJ mol1 (20)

HzCHF3H2zCF3 Ea~40 kJ mol1 (21)

Since CF4 is a non-polar and very stable compoundformation of CF3 from CF4 requires very high activa-tion energy and was suggested to be the main obstacle todiamond formation from CF4 Because of the similaractivation energies CHF3 or CH4 could not bedistinguished as a better option for a precursor as perthe kinetic data However surface chemistry was founddifferent for the two precursors Considering CH3 as themain diamond growth species the H2 abstraction fromtwo neighbouring CH3 groups on the surface was foundto be an endothermic process

H3CzCH3H2CCH2zH2 DH~68 kJ mol1(22)

This would require higher temperature in order to shiftthe equilibrium in the direction of the products But forthe fluorinated system the process requires the abstrac-tion of HF instead of H2 which is an exothermic processand thermodynamically favourable

HFCFzHCHFHFCCHFzHF DHv0 (23)

Therefore to shift the thermodynamic equilibrium tothe product side low temperature is required (LeChatelierrsquos principle) The above mechanism justifiesthe faster growth rate using CH4H2 at higher tempera-tures and CHF3H2 at lower temperatures



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In another low temperature growth studies usingCHF3 C2H5Cl and Cl2 precursors at 350uC by HFCVDand MPCVD method the role of halogens weresuggested in the surface reaction leading to the forma-tion of active surface sites at which diamond growthspecies could be adsorbed198

But the mechanism involved in the CndashHndashO systemfor the low temperature diamond growth is differentThe lower value of the activation energy for thediamond growth in CndashHndashO system than for the CH4H2 systems suggested a different gas surface chemistryfor CH4CO2 plasmas199200 Using MBMS the domi-nant gas phase species present during growth over awide range of plasma gas mixtures (0ndash80CH4 balanceCO2) was measured and the experimental results weresimulated using CHEMKIN computer package Thecalculated trends for all species agreed well with theexperimental observations Using the experimental andsimulated data the overall gas phase chemistry wasreduced to only four overall reactions as

CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)

The simulated result showed that the gas phaseconcentration of CO within the CO2CH4 plasma was100 times that of atomic H and CO was considered asan alternative species that could terminate the growingdiamond surface The surface chemistry of diamondgrowth involving CO is shown in Fig 29 The Fig 29arepresents a reactive site on the growing diamondsurface with an unpaired electron (indicated by dot) onthe C atom This unpaired electron reacts with a gasphase CO molecule to form an unstable carbonyl radicaladduct as shown in Fig 29b Since CO contains anunpaired electron this CO terminated structure isunstable and prone to desorbs back to stage inFig 29a in subsequent stages This unstable carbonyladduct might react either with a H atom from the gasphase and form an aldehyde as shown in Fig 29c orwith a terminating H atom from the neighbouringsurface site (Fig 29d) In this process a lsquodangling bondrsquocan migrate across the growing diamond surface (eg toa step edge) A CH3 radical in the CH4CO2 plasma react

with dangling bonds on the surface adding a carbon tothe lattice Since in the mixtures the observed concen-tration of CH3 both in experiment and simulationcoincided very precisely with the narrow window foroptimum diamond deposition (50CO250CH4) andthe similar maxima in the concentration of CO or anyother species around this narrow concentration windowwas absent CH3 was considered to be the main speciesresponsible for diamond growth rather than the CO orC2H2

Growth of polycrystalline diamond thin film hasrecently been demonstrated on single crystal Si (100) andSiC (6H) substrates at low surface temperatures of 370ndash530uC from an Ar rich ArH2CH4 plasma using highMW power and gas pressures in an MPECVD system byour group201 The phase pure diamond samples withvery high growth rate (13 mm h21 on SiC) and grainsizes of 2ndash7 mm show very high thermal conductivity of65 W cm21 K at room temperature202 Different lowtemperature diamond deposition reports based ondifferent processes used precursors substrates pretreat-ments process parameters like temperature pressureand power used are summarised in Table 4 The growthrates obtained for different experiments are alsoincluded in the table

ConclusionsThe need for synthesis of diamond film at temperatures500uC is described because of the requirements inmany applications in electronics An understanding ofthe nucleation and growth phenomena during proces-sing of diamond films is essential to achieve a successfullowest temperature growth possible Since at lowtemperatures the kinetics itself is slow a good surfacepretreatment is required for enhanced nucleation

Consequently the first part of the review coverednucleation and growth of the diamond films Theinfluence of processing parameters such as temperaturepressure MW power and pretreatment of the substrateson the nucleation and growth is discussed Differentpretreatment techniques such as scratchingabrasionwith hard powder materials surface passivation withHz Br2 I2 ions surface coating with different carboncontaining materials or metals ion implantation bias-ing pulsed laser irradiation and carburisation have beenfound beneficial for enhancing nucleation density Fortyto fifty micrometres diamond slurry activation is mosteffective nucleation promoting mechanical abrasionprocess Br passivated Si surface produced a dramaticincrease in nucleation density of 1010 cm22 Among thevarious nucleation enhancement approaches the appli-cation of a bias potential to the substrate is quiteeffective in achieving high nucleation density Biasenhanced nucleation produced nucleation density onthe order of 109ndash1011 cm22

In general substrate pretreatments produce defectssuch as scratches grain boundaries particle boundariesdislocations electron bombardment induced damagesedges of pits or craters or coating of a thin layer ofcarbide or amorphous carbon which are identified aspotential sites for nucleation either because of the highenergy interface with a high density of unsaturatedbonds and low coordination number or carbon super-saturation regions on the surface

29 Model for growth of diamond film in gases containing

CO on diamond surface (reprinted with permission


Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

The process conditions for achieving good nucleationand growth are different In general high temperaturefavours both nucleation and growth processes Usingbias enhanced nucleation an increase in temperaturefrom 670 to 700uC led to an increase in nucleationdensity from 106 to 1010 cm22 A low pressure of 01ndash1 torr produced a high nucleation density of 109ndash1011 cm22 on mirror polished Si wafer without theapplication of bias in an HFCVD method Doubling thepressure from 94 to 188 torr increased the growth ratefrom 07 to 45 mm h21 with 05CH4 concentrationThe conditions of nucleation and growth are alsodifferent on different substrates On SiC substratenucleation is favoured by the CH4 concentration andprocess pressure whereas growth is favoured only by theCH4 concentration and is not affected by the tempera-ture and gas flow in the temperature range of 780ndash885uC On Si3N4 substrate nucleation increased withdecreasing pressure but growth increased with increas-ing pressure in the temperature range of 800ndash900uC

CH3 radical is considered as the main speciesresponsible for diamond growth in CH4ndashH2 plasmasHowever recent low temperature studies based on Arbased plasma suggested C2 as the main speciesresponsible for growth

The second part of the paper dealt with the LTDGand influence of the processing parameters Most of thelow temperature diamond growth work in the literaturementioned the substrate backside temperature as thesurface temperature was not measured directly But thereal surface temperature of the growing film is sig-nificantly different from the substrate backside tem-perature In spite of the slower growth rate atlower deposition temperatures factors responsible forimproved growth rate are identified The lowest tem-perature to grow diamond is different for differentprecursors as predicted by the thermodynamic calcula-tions In CndashH system the lowest temperature is pressuredependent It is 1127uC at 760 torr 627uC at 76 torrand 327uC at 76 mtorr based on thermodynamics Butin CndashHndashO system the lower limit is all the way to roomtemperature In the CndashHndashO system the carbon solubi-lity decreased with decreasing temperature

Using a seeding of the Si wafer with 3ndash5 nm diamondgrains a good adherent diamond film is obtained at200uC The halogenated precursor gas (fluorides andchlorides) and oxygen containing precursors also helpedin getting diamond film with good growth rate at lowtemperatures A growth rate of 004 mm h21 is obtainedwith H2C2H5Cl gas mixture at 370uC which increasedgradually from 004 mm h21 at 370uC to almost02 mm h21 at 850uC A growth rate of 25 mm h21 isobtained using COH2 gas mixtures in an MPECVDprocess in the temperature range of 350uCT500uCand at 500 W MW power A 20 times increase in growthrate is observed at 450uC in an experiment using COH2

ratio of 18 pressure of 10 torr power of 500 W and COgas flow rate of 9 sccm

Since nucleation and growth of diamond film areaffected by surface phenomena and these are thermallyactivated processes a thorough and better understand-ing of the surface characterisation is needed to havea superior control of the final diamond film Inaddition in situ techniques for monitoring the growthchemistry and parameters are very useful tools to further

understand and control the diamond synthesis In situRaman FTIR RTSE and MBMS are powerfulmethods to analyse and control the growth process

Acknowledgements

This work is supported by the Office of Naval Research(ONR) through a grant number N 00014-04-1-0229 Theguidance and support of Dr Colin Wood ProgramManager ONR throughout this research is very muchappreciated The partial supports of National ScienceFoundation (NSF) under grant numbers CMS-0210351and DMR-0200839 are acknowledged Any opinionsfindings and conclusions or recommendations expressedin this material are those of the authors and do notnecessarily reflect views of the NSF or the ONR

References1 P W May lsquoDiamond thin films a 21st-century materialrsquo Philos

Trans R Soc Lond A 2000 358A 473ndash4952 C-P Klages lsquoChemical vapor deposition of diamond filmsrsquo in

lsquoHandbook of ceramic hard materialsrsquo Vol 1 (ed R Riedel)391ndash419 2000 Weinheim Chichester Wiley-VCH

3 B Lux and R Haubner lsquoDiamond as a wear-resistant coatingrsquo inlsquoDiamond films and coatingsrsquo (ed R F Davis) 183ndash234 1993Park Ridge NJ Noyes Publications

4 J Karner M Pedrazzini I Reineck M E Sjostrand andE Bergmann lsquoCVD diamond coated cemented carbide cuttingtoolsrsquo Mater Sci Eng A 1996 A209 405 ndash413

5 A Ababou B Carriere G Goetz J Guille B MarcusM Mermoux A Mosser M Romeo and F Le NormandlsquoSurface characterization of microwave-assisted chemically vapordeposited carbon deposits on silicon and transition metalsubstratesrsquo Diamond Relat Mater 1992 1 875ndash881

6 R Haubner A Lindlbauer and B Lux lsquoDiamond deposition onchromium cobalt and nickel substrates by microwave plasmachemical vapor depositionrsquo Diamond Relat Mater 1993 21505ndash1515

7 I Endler A Leonhardt H-J Scheibe and R Born lsquoInterlayersfor diamond deposition on tool materialsrsquo Diamond RelatMater 1996 5 299ndash303

8 H Chen M L Nielsen C J Gold and R O Dillon lsquoDiamondgrowth on ferrous metalsrsquo Mater Sci Monogr 1991 73 137ndash142

9 E R Kupp W R Drawl and K E Spear lsquoInterlayers fordiamond-coated cutting toolsrsquo Surf Coat Technol 1994 6869378ndash383

10 J K Wright R L Willamson and K J Maggs lsquoFinite elementanalysis of the effectiveness of interlayers in reducing thermalresidual stresses in diamond filmsrsquo Mater Sci Eng A 1994A187 87ndash96

11 F Silva A Gicquel A Chiron and J Achard lsquoLow roughnessdiamond films produced at temperatures less than 600uCrsquoDiamond Relat Mater 2000 9 1965ndash1970

12 Y Sakamoto and M Takaya lsquoPreparation of diamond-coatedtools and their cutting performancersquo J Mater Process Technol2002 127 151ndash154

13 K Mallika and R Komanduri lsquoDiamond coatings on cementedtungsten carbide tools by low-pressure microwave CVDrsquo Wear1999 224 245ndash266

14 F H Sun Z M Zhang M Chen and H S Shen lsquoImprovementof adhesive strength and surface roughness of diamond films onco-cemented tungsten carbide toolsrsquo Diamond Relat Mater2003 12 711ndash718

15 S-H Kim lsquoEnhancement of low temperature selective depositionof diamond filmrsquo J Korean Chem Soc 2001 45 286ndash289

16 A Hiraki lsquoElectron-emitter fabricated at low temperature bydiamond-nano-seeding techniquersquo Mater Chem Phys 2001 72196ndash200

17 A Gicquel K Hassouni F Silva and J Achard lsquoCVD diamondfilms from growth to applicationsrsquo Curr Appl Phys 2001 1479ndash496

18 W Zhu G P Kochanski S Lin and L Seibles lsquoDefect-enhancedelectron field emission from chemical vapor deposited diamondrsquoJ Appl Phys 1995 78 2707ndash2711

19 C-F Chen S-H Chen and K-M Lin lsquoElectrical properties ofdiamond films grown at low temperaturersquo Thin Solid Films 1995270 205ndash209



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

20 M D Drory and J W Hutchinson lsquoDiamond coating oftitanium alloysrsquo Science 1994 263 1753ndash1755

21 R Ramesham and T Roppel lsquoSelective growth of polycrystallinediamond thin films on a variety of substrates using selectivedamaging by ultrasonic agitationrsquo J Mater Res 1992 7 1144ndash1151

22 D K Snood W R Drawl and R Messier lsquoThe effect of carbonion implantation on the nucleation of diamond on Tindash6Alndash4Valloyrsquo Surf Coat Technol 1992 51 307ndash312

23 J E Graebner J A Mucha L Seibles and G W KammlottlsquoThe thermal conductivity of chemical-vapor-deposited diamondfilms on siliconrsquo J Appl Phys 1992 71 3143ndash3146

24 J E Graebner S Jin G W Kammlott J A Herb and C FGardinier lsquoUnusually high thermal conductivity in diamondfilmsrsquo Appl Phys Lett 1992 60 1576ndash1578

25 K Plamann D Fournier E Anger and A GicquellsquoPhotothermal examination of the heat diffusion inhomogeneityin diamond films of submicron thicknessrsquo Diamond Relat Mater1994 3 752ndash756

26 Y Muranaka H Yamashita and H Miyadera lsquoWorldwide statusof low temperature growth of diamondrsquo Diamond Relat Mater1994 3 313ndash318

27 S A Catledge and Y K Vohra lsquomechanical properties andquality of diamond films synthesized on Tindash6Alndash4V alloy usingthe microwave plasmas of CH4H2 and COH2 systemsrsquo J ApplPhys 1998 83 198ndash204

28 C-F Chen S-H Chen T-M Hong H-W Ko and S E SheulsquoLow-temperature growth of diamond films by microwave plasmachemical vapor deposition using CH4 zCO2 gas mixturesrsquoDiamond Relat Mater 1994 3 443ndash447

29 C-F Chen S-H Chen T-M Hong and D-P Wang lsquoLow-temperature diamond growth and plasma species analysis usingmethane-carbon dioxide gas mixturesrsquo Scr Metall Mater 199431 775ndash780

30 M D Whitfield B Audic C M Flannery L P Kehoe G MCrean and R B Jackman lsquoAcoustic wave propagation in freestanding CVD diamond influence of film quality and tempera-turersquo Diamond Relat Mater 1999 8 732ndash737

31 R K Singh D R Gilbert and J Laveigne lsquoGrowth of adherentdiamond films on optically transparent sapphire substratesrsquo ApplPhys Lett 1996 69 2181ndash2183

32 H Verhoeven E Boettger A Floter H Reiszlig and R ZachailsquoThermal resistance and electrical insulation of thin low-tempera-ture-deposited diamond filmsrsquo Diamond Relat Mater 1997 6298ndash302

33 H Verhoeven A Floter H Reiszlig R Zachai D Wittorf andW Jager lsquoInfluence of the microstructure on the thermalproperties of thin polycrystalline diamond filmsrsquo Appl PhysLett 1997 71 1329ndash1331

34 H Verhoeven H Reiszlig H-J Fuszliger and R Zachai lsquoThermalresistance of thin diamond films deposited at low temperaturesrsquoAppl Phys Lett 1996 69 1562ndash1564

35 B V Spitsyn L L Bouilov and B V Deryagin lsquoVapor growth ofdiamond on diamond and other surfacesrsquo J Cryst Growth 198152 219ndash226

36 S Matsumoto Y Sato M Kamo J Tanaka and N SetakalsquoChemical vapor deposition of diamond from methanendashhydrogengasrsquo Proc 7th Int Conf on lsquoVacuum metallurgyrsquo Tokyo JapanNovember 1982 Iron and Steel Institute of Japan 386ndash391

37 J C Angus Y Wang and M Sunkara lsquoMetastable growth ofdiamond and diamond-like phasesrsquo Ann Rev Mater Sci 199121 221ndash248

38 X L Peng and T W Clyne lsquoformation and adhesion of hotfilament CVD diamond films on titanium substratesrsquo Thin SolidFilms 1997 293 261ndash269

39 H Buchkremer-Hermanns H Ren G Kohlschein and H WeiblsquoNucleation and early growth of CVD diamond on silicon nitridersquoSurf Coat Technol 1998 98 1038ndash1046

40 H Buchkremer-Hermanns H Ren J Utsch and H WeisslsquoOptimization of MW-PACVD diamond deposition parametersfor high nucleation density and growth rate on Si3N4 substratersquoDiamond Relat Mater 1997 6 411ndash416

41 K Mallika and R Komanduri lsquoLow pressure microwave plasmaassisted chemical vapor deposition (MPCVD) of diamond coat-ings on silicon nitride cutting toolsrsquo Thin Solid Films 2001 396145ndash166

42 H Liu and D D Dandy lsquoStudies on nucleation process indiamond CVD an overview of recent developmentsrsquo DiamondRelat Mater 1995 4 1173ndash1188

43 J Singh lsquoNucleation and growth mechanism of diamond duringhot-filament chemical vapor depositionrsquo J Mater Sci 1994 292761ndash2766

44 W R L Lambrecht C H Lee B V Segall J C Angus Z Liand M Sunkara lsquoDiamond nucleation by hydrogenation of theedges of graphitic precursorsrsquo Nature 1993 364 607ndash610

45 H Sein W Ahmed M Jackson R Polini I Hassan M Amarand C Rego lsquoEnhancing nucleation density and adhesion ofpolycrystalline diamond films deposited by HFCVD using surfacetreatments on Co cemented tungsten carbidersquo Diamond RelatMater 2004 13 610ndash615

46 F Shahedipour B P Conner and H W White lsquoOpticalproperties of plasma species absorbed during diamond depositionon steelrsquo J Appl Phys 2000 88 3039ndash3046

47 J G Buijnsters F M van Bouwelen J J Schermer W J P vanEnckevort and J J ter Meulen lsquoChemical vapor deposition ofdiamond on nitrided chromium using an oxyacetylene flamersquoDiamond Relat Mater 2000 9 341ndash345

48 F Hormann H Roll M Schreck and B Stritzker lsquoEpitaxial Irlayers on SrTiO3 as substrates for diamond nucleation depositionof the films and modification in the CVD environmentrsquo DiamondRelat Mater 2000 9 256ndash261

49 Z Dai C Bednarski-Meinke and B Golding lsquoHeteroepitaxialdiamond film growth the a-plane sapphirendashiridium systemrsquoDiamond Relat Mater 2004 13 552ndash556

50 M D Whitfield J A Savage and R B Jackman lsquoNucleationand growth of diamond films on single crystal and polycrystallinetungsten substratesrsquo Diamond Relat Mater 2000 9 262ndash266

51 S A Catledge and Y K Vohra lsquoInterfacial oxide and carbidephases in the deposition of diamond films on beryllium metalrsquoDiamond Relat Mater 2000 9 1327ndash1330

52 J-M Ting and W Shih lsquoGrowth kinetics of diamond film ondiamond composite materialsrsquo Mater Chem Phys 2001 72185ndash190

53 M R Chen L Chang D F Chang and H G Chen lsquoDiamondgrowth on CoSi2Si by bias-enhanced microwave plasma chemicalvapor deposition methodrsquo Mater Chem Phys 2001 72 172ndash175

54 J C Arnault B Lang and L Normand lsquoHot filament chemicalvapor deposition diamond growth kinetics on an epitaxial cosi2surface monitored by three electron spectroscopiesrsquo J Vac SciA 1998 16A 494ndash501

55 C Z Gu X Jiang L Kapplus and S Mantl lsquoComparisonstudy of nucleation and growth characteristics of chemical-vapor-deposited diamond films on CoSi2(001) and Si(001)rsquo J ApplPhys 2000 87 1743ndash1747

56 T P Ong F Xiong R P H Chang and C W WhitelsquoNucleation and growth of diamond on carbon-implanted singlecrystal copper surfacesrsquo J Mater Res 1992 7 2429ndash2439

57 N Jiang C L Wang J H Won M H Jaen Y Mori A HattaT Ito T Sasaki and A Hiraki lsquoInterface characterization ofchemical-vapor-deposited diamond on Cu and Pt substratesstudied by transmission electron microscopyrsquo Appl Surf Sci1997 117118 587ndash591

58 N Jiang C L Wang J H Won M H Jaen Y Mori A HattaT Ito T Sasaki and A Hiraki lsquoInterfacial analysis of CVDdiamond on copper substratesrsquo Diamond Relat Mater 1997 6743ndash746

59 S Ojika S Yamashita K Kataoka and T Ishikura lsquoLow-pressure diamond nucleation and growth on cu substratersquo Jpn JAppl Phys 1993 32 L200ndashL203

60 K-L Chuang L Chang and C-A Lu lsquoDiamond nucleation onCu by using MPCVD with a biasing pretreatmentrsquo Mater ChemPhys 2001 72 176ndash180

61 N Ali W Ahmed C A Rego and Q H Fan lsquoCombinedsubstrate polishing and biasing during hot-filament chemicalvapor deposition of diamond on copperrsquo J Mater Res 2000 15593ndash595

62 H-K Chung and J C Sung lsquoThe rapid growth of thintransparent films of diamondrsquo Mater Chem Phys 2001 72130ndash132

63 L Nistor V Buschmann V Ralchenko G Dinca I VlasovJ Van Landuyt and H Fuess lsquoMicrostructural characterizationof diamond films deposited on c-BN crystalsrsquo Diamond RelatMater 2000 9 269ndash273

64 S-T Lee Z D Lin and X Jiang lsquoCVD diamond filmsnucleation and growthrsquo Mater Sci Eng 1999 25 123ndash154

65 K Mitsuda Y Kojima T Yoshida and K Akashi lsquoThe growthof diamond in microwave plasma under low pressurersquo J MaterSci 1987 22 1557ndash1562

66 A Sawabe and T Inuzuka lsquoGrowth of diamond thin films byelectron-assisted chemical vapor deposition and their character-izationrsquo Thin Solid Films 1986 137 89ndash99

67 K Suzuki A Swabe H Yasuda and T Inuzuka lsquoGrowth ofdiamond thin films by dc plasma chemical vapor depositionrsquoAppl Phys Lett 1987 50 728ndash729

68 C P Chang D L Flamm D E Ibbotson and J A MuchalsquoDiamond crystal growth by plasma chemical vapor depositionrsquoJ Appl Phys 63 1988 1744ndash1748

69 P A Denning and D A Stevenson lsquoInfluence of substratepreparation upon the nucleation of diamond thin filmsrsquo Proc 2nd



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Int Conf on lsquoNew diamond science and technologyrsquo 403ndash4081991 Pittsburg PA MRS

70 H Maeda S Masuda K Kusakabe and S MorookalsquoNucleation and growth of diamond in a microwave plasma onsubstratersquo J Cryst Growth 1992 121 507ndash515

71 P Ascarelli and S Fontana lsquoDissimilar grit-size dependence ofthe diamond nucleation density on substrate surface pretreat-mentsrsquo Appl Surf Sci 1993 64 307ndash311

72 B Singh Y Arie A W Levine and O R Mesker lsquoEffects offilament and reactor wall materials in low-pressure chemicalvapor deposition synthesis of diamondrsquo Appl Phys Lett 198852 451ndash452

73 B Lux and R Haubner lsquoNucleation and growth of low pressurediamondrsquo in lsquoDiamond and diamond-like films and coatingsrsquo(eds R E Clausing et al) 579ndash609 1991 New York PlenumPress

74 S Iijima Y Aikawa and K Baba lsquoGrowth of diamond particlesin chemical vapor depositionrsquo J Mater Res 1991 6 1491ndash1497

75 M Ihara H Komiyama and T Okubo lsquoCorrelation betweennucleation site density and residual diamond dust density indiamond film depositionrsquo Appl Phys Lett 1994 65 1192ndash1194

76 S Yugo A Izumi T Kanai T Muto and T Kimura lsquoSomeobservations on nucleation sites in diamond growth by plasmaCVDrsquo Proc 2nd Int Conf on lsquoNew diamond science andtechnologyrsquo 385ndash389 1991 Pittsburg PA MRS

77 C H Lee Z D Lin N G Shang L S Liao I Bello N Wangand S T Lee lsquoSurface passivation in diamond nucleationrsquo PhysRev B 2000 62B 17134ndash17137

78 Z Feng K Komvopoulos I G Brown and D C Bogy lsquoEffectof graphitic carbon films on diamond nucleation by microwave-plasma-enhanced chemical-vapor depositionrsquo J Appl Phys1993 74 2841ndash2849

79 A A Morrish and P E Pehesson lsquoEffects of surface pretreat-ments on nucleation and growth of diamond films on a variety ofsubstratesrsquo Appl Phys Lett 1991 59 417ndash419

80 J Singh and M Vellaikal lsquoNucleation of diamond during hotfilament chemical vapor depositionrsquo J Appl Phys 1993 732831ndash2834

81 K V Ravi and C A Koch lsquoNucleation enhancement of diamondsynthesized by combustion flame techniquesrsquo Appl Phys Lett1992 57 348ndash350

82 K V Ravi C A Koch H S Hu and A Joshi lsquoNucleation andmorphology of diamond crystals and films synthesized by thecombustion flame techniquersquo J Mater Res1990 5 2356ndash2366

83 H Jeon C L Wang A Hatta and T Ito lsquoNucleation-enhancingtreatment for diamond growth over a large-area using magne-toactive microwave plasma chemical vapor depositionrsquo J ApplPhys 2000 88 2979ndash2983

84 J Yang X W Su Q J Chen and Z D Lin lsquoSiz implantation apretreatment method for diamond nucleation on a Si waferrsquo ApplPhys Lett 1995 66 3284ndash3286

85 K Kobayashi M Kumagai S Karasawa T Watanabe andF Togashi lsquoEffect of ion implantation and surface structure ofsilicon on diamond film nucleationrsquo J Cryst Growth 1993 128408ndash412

86 Z H Liu B Q Zong and Z D Lin lsquoDiamond growth on poroussilicon by hot-filament chemical vapor depositionrsquo Thin SolidFilms 1995 254 3ndash6

87 S Yugo T Kanai T Kimura and T Muto lsquoGeneration ofdiamond nuclei by electric field in plasma chemical vapordepositionrsquo Appl Phys Lett 1991 58 1036ndash1038

88 B R Stoner G-H M Ma S D Wolter and J T GlasslsquoCharacterization of bias-enhanced nucleation of diamond onsilicon by invacuo surface analysis and transmission electronmicroscopyrsquo Phys Rev B 1992 45B 11067ndash11084

89 Y Kouzuma K Teii S Mizobe K Uchino and K MuraokalsquoTime dependence of nucleation density and crystallinity ofdiamond in low-pressure ion-enhanced depositionrsquo DiamondRelat Mater 2004 13 656ndash660

90 T-F Chang and L Chang lsquoDiamond deposition on Si (111)and carbon face 6HndashSiC (0001) substrates by positivelybiased pretreatmentrsquo Diamond Relat Mater 2002 11 509ndash512

91 F Stubhan M Ferguson H-J Fusser and R J BehmlsquoHeteroepitaxial nucleation of diamond on Si(001) in hot filamentchemical vapor depositionrsquo Appl Phys Lett 1995 66 1900ndash1902

92 Q J Chen and Z D Lin lsquoElectron-emission-enhanced diamondnucleation on si by hot filament chemical vapor depositionrsquo ApplPhys Lett 1996 68 2450ndash2452

93 Q J Chen J Yang and Z D Lin lsquoSynthesis of oriented textureddiamond films on silicon via hot filament chemical vapordepositionrsquo Appl Phys Lett 1995 67 1853ndash1855

94 S Yugo T Kimura and T Kanai lsquoNucleation mechanisms ofdiamond in plasma chemical vapor depositionlsquo Diamond RelatMater 1993 2 328ndash332

95 J Gerber S Sattel K Jung H Ehrhard and J RobertsonlsquoExperimental characterization of bias-enhanced nucleation ofdiamond on Sirsquo Diamond Relat Mater 1995 4 559ndash562

96 B R Stoner G H Ma S D Wolter W Zhou Y-C WangR F Davis and J T Glass lsquoEpitaxial nucleation of diamond onb-SiC via bias-enhanced microwave plasma chemical vapordepositionrsquo Diamond Relat Mater 1993 2 142ndash146

97 X Jiang K Schiffmann and C-P Klages lsquoNucleation and initialgrowth phase of diamond thin films on (100) siliconrsquo Phys RevB 1994 50B 8402ndash8410

98 X Jiang and C-P Klages lsquoRecent developments in heteroepitax-ial nucleation and growth of diamond on siliconrsquo Phys Stat SolA 1996 154A 175ndash183

99 P Reinke P Kania P Oelhafen and R GuggenheimlsquoInvestigation of the nucleation mechanism in bias-enhanceddiamond depositionrsquo Appl Phys Lett 1996 68 22ndash24

100 K G Perng K-S Liu and I-N Lin lsquoEvidence of electron-emission-enhanced nucleation of diamonds in microwave plasma-enhanced chemical vapor depositionrsquo Appl Phys Lett 2001 793257ndash3259

101 X Jiang lsquoTextured and heteroepitaxial CVD diamond filmsrsquo inlsquoThin-film diamond Irsquo Vol 76 lsquoSemiconductors and semimetalsrsquo(eds C E Nebel and J Ristein) 1ndash47 2003 San Diego CAElsevier Academic Press

102 X Jiang W J Zhang and C-P Klages lsquoEffects of ionbombardment on the nucleation and growth of diamond filmsrsquoPhys Rev B 1998 58B 7064ndash7075

103 M Tomellini R Polini and V Sessa lsquoA model kinetics fornucleation at a solid surface with application to diamonddeposition from the gas phasersquo J Appl Phys 1991 70 7573ndash7578

104 R Polini and M Tomelini lsquoAnalysis of size distribution functionsof diamond crystallites formed in the early stages of chemicalvapor depositionrsquo Diamond Relat Mater 1995 4 1311ndash1316

105 H Makita K Nishimura N Jiang A Hatta T Ito andA Hiraki lsquoUltrahigh particle density seeding with nanocrystaldiamond particlesrsquo Thin Solid Films 1996 281ndash282 279ndash281

106 H Makita T Yara N Jiang K Nishimura A Hatta T Ito andA Hiraki lsquoSeeding with purified ultrafine diamond particles fordiamond synthesis by CVDrsquo Proc ADC 1995 (ed A Feldmanet al) 333ndash336 1995 Gaithersburg NIST

107 T Yara H Makita A Hatta T Ito and A Hiraki lsquoLowtemperature fabrication of diamond film with nanocrystalseedingrsquo Jpn J Appl Phys 1995 34 L312ndashL315

108 D-G Lee and R K Singh lsquoSynthesis of (111) oriented diamondthin film by electrophoretic deposition processrsquo Appl Phys Lett1997 70 1542ndash1544

109 T Tsubota S Ida N Okada M Nagata Y Matsumoto andN Yatsushiro lsquoCVD diamond coating on WC-Co cutting toolusing ECR MPCVD apparatus via electrophoretic seedingpretreatmentrsquo Surf Coat Technol 2003 169ndash170 262ndash265

110 I Zhitomirsky lsquoCathodic electrophoretic deposition of diamondparticlesrsquo Mater Lett 1998 37 72ndash78

111 J J Adair and R K Singh lsquoEnhanced chemical vapor depositionof diamond and related materialsrsquo US patent 5485804 1996

112 S Park and J Lee lsquoNucleation behavior of diamond particleson silicon substrates in a hot-filament chemical vapor depositionrsquoJ Mater Sci 28 1993 1799ndash1804

113 S T Lee Y W Lam Z D Lin Y Chen and Q J ChenlsquoPressure effect on diamond nucleation in a hot-filament CVDsystemrsquo Phys Rev B 1997 55B 15937ndash15941

114 W Y Yeh J Hwang T J Wu W J Guan C S Kou andH Chang lsquoDeposition of diamond films at low pressure in aplanar large-area microwave surface wave plasma sourcersquo J VacSci Technol A 2001 19A 2835ndash2839

115 J-J Wu S-H Yeh C-T Su and F C-N HonglsquoCharacterization of diamond deposition from chloromethanereactants by laser reflective interferometryrsquo Appl Phys Lett1996 68 3254ndash3256

116 R S Edelstein I Gouzman M Folman S Rotter andA HoVman lsquoSurface carbon saturation as a means of CVDdiamond nucleation enhancementrsquo Diamond Relat Mater 19998 139ndash145

117 H Jeon A Hatta H Suzuki T Ito T Sasaki C Lee andA Hiraki lsquoLarge area diamond nucleation on Si(001) usingmagnetoactive microwave plasma CVDrsquo Appl Surf Sci 199713114 244ndash248

118 G F Zhang and V Buck lsquoRapid nucleation of diamond films bypulsed laser chemical vapor depositionrsquo Appl Surf Sci 2001180 255ndash260

119 G F Zhang D S Geng and Z J Yang lsquoHigh nitrogen amountsincorporated diamond films deposited by the addition of nitrogen



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

in a hot-filament CVD systemrsquo Surf Coat Technol 1999 122268ndash272

120 D Zhou A R Krauss L C Qin T G McCauley D M GruenT D Corrigan R P H Chang and H Gnaser lsquoSynthesis andelectron field emission of nanocrystalline diamond thin filmsgrown from N2CH4 microwave plasmasrsquo J Appl Phys 1997 824546ndash4550

121 J X Yang H D Zhang CM Li G C Chen F X Lu W ZTang and Y M Tong lsquoEffects of nitrogen addition onmorphology and mechanical property of DC arc plasma jetCVD diamond filmsrsquo Diamond Relat Mater 2004 13 139ndash144

122 C J Tang A J Neves and A J S Fernandes lsquoInfluence ofnucleation density on film quality growth rate and morphology ofthick CVD diamond filmsrsquo Diamond Relat Mater 2003 121488ndash1494

123 K J Liao W L Wang and B Feng lsquoeffect of nucleation rate onheteroepitaxial diamond growth on Si (100) via electron-emission-enhanced nucleation by hot filament chemical vapor depositionrsquoPhys Stat Sol A 1998 167A 117ndash123

124 D R Gilbert R Singh R Clarke and S Murugkar lsquoDynamicgrowth effects during low-pressure deposition of diamond filmsrsquoAppl Phys Lett 1997 70 1974ndash1976

125 G S Yang M Aslam K P Kuo D K Reinhard andJ Asmussen lsquoEffect of ultrahigh nucleation density on diamondgrowth at different growth rates and temperaturesrsquo J Vac SciTechnol B 1995 13B 1030ndash1036

126 M-S Wong C-A Lu H-K Chang T-S Yang J-H Wu andY Liou lsquoDiamond Synthesis via CndashH metal precursors processedin hot filament chemical vapor deposition and microwave plasmachemical vapor depositionrsquo Thin Solid Films 2000 377ndash378 274ndash279

127 W Ahmed C A Rego R Cherry A Afzal N Ali and I UHassan lsquoCVD diamond controlling structure and morphologyrsquoVacuum 2000 56 153ndash158

128 I Sakaguchi M Nishitani-Gamo K P Loh H Haneda andT Ando lsquoHomoepitaxial growth and hydrogen incorporation onthe chemical vapor deposited (111) diamondrsquo J Appl Phys1999 86 1306ndash1310

129 C J Chu M P DrsquoEvelyn R H Hauge and J L MargravelsquoMechanism of diamond growth by chemical vapor depositionon diamond (100) (111) and (110) surfaces carbon-13 studiesrsquoJ Appl Phys 1991 70 1695ndash1705

130 H Maeda K Ohtsubo M Irie N Ohya K Kusakabe andS Morooka lsquoDetermination of diamond [100] and [111] growthrate and formation of highly oriented diamond film by microwaveplasma-assisted chemical vapor depositionrsquo J Mater Res 199510 3115ndash3123

131 K A Snail and C M Marks lsquoIn situ diamond growth ratemeasurement using emission interferometryrsquo Appl Phys Lett1992 60 3135ndash3137

132 Q H Fan E Pereira and J Gracio lsquoDiamond deposition oncopper studies on nucleation growth and adhesion behaviorsrsquoJ Mater Sci 1999 34 1353ndash1365

133 B Y Hong J Lee R W Collins Y L Kuang W DrawlR Messier T T Tsong and Y E Strausser lsquoEffects of processingconditions on the growth of nanocrystalline diamond thin filmsreal time spectroscopic ellipsometry studiesrsquo Diamond RelatMater 1997 6 55ndash80

134 H Buchkremer-Hermanns H Ren and H Weib lsquoOptimizationof diamond nucleation and growth using MW-PACVD methodrsquoDiamond Relat Mater 1996 5 312ndash316

135 G F Zhang and V Buck lsquoLower filament temperature limit ofdiamond growth in a hot-filament CVD systemrsquo Surf CoatTechnol 2002 160 14ndash19

136 F Silva A Gicquel A Tardieu P Cledat and T ChauveaulsquoControl of an MPACVD reactor for polycrystalline textureddiamond films synthesis role of microwave power densityrsquoDiamond Relat Mater 1996 5 338ndash344

137 C Wild R Kohl N Herres W Mueller-Sebert and P KoidllsquoOriented CVD diamond films twin formation structure andmorphologyrsquo Diamond Relat Mater 1994 3 373ndash381

138 K Kobashi K Nishimura Y Kawate and T HoriuchilsquoSynthesis of diamonds by use of microwave plasma chemical-vapor deposition morphology and growth of diamond filmsrsquoPhys Rev 1988 38 4067ndash4084

139 V Mortet A Kromka R Kravets J Rosa V Vorlicek J Zemekand M Vanecek lsquoInvestigation of diamond growth at highpressure by microwave plasma chemical vapor depositionrsquoDiamond Relat Mater 2004 13 604ndash609

140 O A Williams and R B Jackman lsquoHigh Growth rateMWPECVD of single crystal diamondrsquo Diamond Relat Mater2004 13 557ndash560

141 T-H Chein J Wei and Y Tzeng lsquoSynthesis of diamond in highpower-density microwave methanehydrogenoxygen plasmas at

elevated substrate temperaturesrsquo Diamond Relat Mater 1999 81686ndash1696

142 H Guo Z L Sun Q Y He S M Du X B Wu Z N WangX J Liu Y H Cai X G Diao G H Li W Z Tang G FZhong T B Huang J M Liu Z Jiang and F X LulsquoDeposition of large area high quality diamond wafers with highgrowth rate by DC arc plasma jetrsquo Diamond Relat Mater 20009 1673ndash1677

143 Y Andoa T Tachibana and K Kobashi lsquoGrowth of diamondfilms by a 5-kw microwave plasma CVD reactorrsquo Diamond RelatMater 2001 10 312ndash315

144 J Khachan and D Gardner lsquoThe effect of frequency and dutycycle of a pulsed microwave plasma on the chemical vapordeposition of diamondrsquo J Appl Phys 1999 86 6576ndash6579

145 C Popov W Kulisch P N Gibson G Ceccone and M JelineklsquoGrowth and characterization of nanocrystalline diamondamor-phous carbon composite films prepared by MWCVDrsquo DiamondRelat Mater 2004 13 1371ndash1376

146 J Lee R W Collins B Y Hong R Messier and Y E StrausserlsquoAnalysis of the growth processes of plasma-enhanced chemicalvapor deposited diamond Films from COH2 and CH4H2

mixtures using real-time spectroellipsometryrsquo J Vac SciTechnol A 1997 15A 1929ndash1936

147 J Lee R W Collins R Messier and Y E Strausser lsquoLowtemperature plasma process based on CO-Rich COH2 mixturesfor high rate diamond film depositionrsquo Appl Phys Lett 1997 701527ndash1529

148 Y Muranaka H Yamashita and H Miyadera lsquoCharacterizationof diamond films synthesized in the microwave plasmas of COH2

and COO2H2 systems at low temperatures (403ndash1023 K)rsquoJ Appl Phys 1991 69 8145ndash8153

149 I Schmidt and C Benndorf lsquoLow temperature CVD diamonddeposition using halogenated precursors ndash deposition on lowmelting materials Al Zn and glassrsquo Diamond Relat Mater 200110 347ndash351

150 I Schmidt and C Benndorf lsquoUsing fluorine and chlorine inthe diamond CVD processrsquo Diamond Relat Mater 1999 8 231ndash235

151 I Schmidt F Hentschel and C Benndorf lsquoLow temperaturediamond growth using halogenated hydrocarbonsrsquo Solid StateIonics 1997 101ndash103 97ndash101

152 I Schmidt F Hentschel and C Benndorf lsquoLow temperaturediamond growth using fluorinated hydrocarbonsrsquo Diamond RelatMater 1996 5 1318ndash1322

153 I-H Choi P Weisbecker S Barrat and E Bauer-GrosselsquoGrowth of highly oriented diamond films by the MPCVDtechnique using COndashH2 CH4ndashH2 and CH4ndashN2ndashH2 gas mixturesrsquoDiamond Relat Mater 2004 13 574ndash580rsquo

154 S C Eaton and M K Sunkara lsquoConstruction of a new CndashHndashOternary diagram for diamond deposition from the vapor phasersquoDiamond Relat Mater 2000 9 1320ndash1326

155 G Bhimarasetti and M K Sunkara lsquoThe process windowfor diamond deposition from the vapor phase with sulpher in theCndashHndashO feed gas mixturesrsquo Thin Solid Films 2003 440 78ndash86

156 Z TOth A Mechler and P Heszler lsquoLocal laser-assisted chemicalvapor deposition of diamondrsquo Appl Surf Sci 2000 168 5ndash8

157 A Hatta H Suzuki K Kadota H Makita T Ito and A HirakilsquoFabrication of diamond films at low temperature by pulse-modulated magneto-active microwave plasma CVDrsquo PlasmaSour Sci Technol 1996 5 235ndash240

158 A A Shaik M A Khan H A Naseem and W D BrownlsquoEffect of early methane introduction on the properties of nano-seeded MPCVD-diamond filmsrsquo Thin Solid films 1999 355ndash356139ndash145

159 S Liu E Q Xie J W Sun C C Ning and Y F Jiang lsquoA Studyon nano-nucleation and interface of diamond film prepared byhot filament assisted with radio frequency plasmarsquo Mater Lett2003 57 1662ndash1669

160 Y Liu C Liu Y Chen Y Tzeng P Tso and I Lin lsquoEffects ofhydrogen additive on microwave plasma CVD of nanocrystallinediamond in mixtures of argon and methanersquo Diamond RelatMater 2004 13 671ndash678

161 J Stiegler A Bergmaier J Michler S Laufer G Dollinger andE Blank lsquoThe effect of nitrogen on low temperature growth ofdiamond filmsrsquo Thin Solid Films 1999 352 29ndash40

162 F Benedic M Belmahi O Elmazria M B Assouar J-JFundenberger and P Alnot lsquoInvestigations on nitrogen additionin the CH4ndashH2 Gas mixture used for diamond deposition for abetter understanding and the optimisation of the synthesisprocessrsquo Surf Coat Technol 2003 176 37ndash49

163 G F Zhang D S Geng and Z J Yang lsquoHigh nitrogen amountsincorporated diamond films deposited by the addition of nitrogenin a hot-filament CVD systemrsquo Surf Coat Technol 1999 122268ndash272



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

164 Z-J Liu S-J Ding P-F Wang D W Zhang J-Y Zhang J-TWang and K Kohse-Hoinghaus lsquoEffects of fluorine addition ondriving force for CVD diamond growthrsquo Thin Solid Films 2000368 208ndash210

165 V Baranauskas H J Ceragioli A C Peterlevitz M C Tosinand S F Durrant lsquoEffects of argon dilution of an ethanolhydrogen gas feed on the growth of diamond by hot-filamentchemical vapor depositionrsquo Thin Solid Films 2000 377ndash378 303ndash308

166 R Ramamurti V Shanov and R N Singh lsquoSynthesis ofnanocrystalline diamond films by microwave plasma CVDrsquoProc Symp on lsquoInnovative processingsynthesis ceramicsglasses composites VIrsquo St Louise MO AprilndashMay 2002American Ceramics Society 39ndash50

167 T Hosomi T Maki T Kobayashi Y Yoshizako M Taniguchiand M Sugiyo lsquoRole of xenon additive in microwave plasma-assisted (H2zCH4) chemical vapor deposition of diamond thinfilmrsquo J Appl Phys 1998 84 6059ndash6063

168 H Sternschulte M Schreck B Stritzker A Bergmaier andG Dollinger lsquoGrowth and properties of CVD diamond filmsgrown under H2S additionrsquo Diamond Relat Mater 2003 12318ndash323

169 S Koizumi M Kamo Y Sato S Mita A Sawabe A ReznikC Uzan-Saguy and R Kalish lsquoGrowth and characterization ofphosphorous doped n-type diamond thin filmsrsquo Diamond RelatMater 1998 7 540ndash544

170 J C Angus F A Buck M Sunkara T F Groth C C Haymanand R Gat lsquoDiamond growth at low pressuresrsquo Mater Res Bull1989 13 38ndash47

171 K Larsson and J-O Carlsson lsquoSurface migration duringdiamond growth studied by molecular orbital calculationsrsquoPhys Rev B 1999 59B 8315ndash8322

172 D G Goodwin lsquoScaling laws for diamond chemical-vapordeposition I diamond surface chemistryrsquo J Appl Phys 199374 6888ndash6894

173 D Goodwin and J Butler lsquoTheory of diamond chemical vapordepositionrsquo in lsquoHandbook of industrial diamonds and diamondfilmsrsquo Vol 57 (eds M Prelas et al) 527ndash581 1998 New YorkMarcel Dekker

174 Y A Mankelevich N V Suetin J A Smith and M N RAshfold lsquoInvestigations of the gas phase chemistry in a hotfilament CVD reactor operating with CH4N2H2 and CH4NH3H2 gas mixturesrsquo Diamond Relat Mater 2002 11 567ndash572

175 T Sharda M Umeno T Soga and T Jimbo lsquoGrowth ofnanocrystalline diamond films by biased enhanced microwaveplasma chemical vapor deposition a different regime of growthrsquoAppl Phys Lett 2000 77 4304ndash4306

176 M Yoshimoto M Furusawa K Nakajima M Takakura andY Hishitani lsquoDiamond film growth in an oxygen atmospherersquoDiamond Relat Mater 2001 10 295ndash299

177 Y K Liu Y Tzeng C Liu P Tso and I N Lin lsquoGrowth ofmicrocrystalline and nanocrystalline diamond films by microwaveplasmas in a gas mixture of 1 methane5 hydrogen94argonrsquo Diamond Relat Mater 2004 13 1859ndash1864

178 T-H Chein J Wei and Y H Tzeng lsquoSynthesis of diamond inhigh power-density microwave methanehydrogenoxygen plas-mas at elevated substrate temperaturesrsquo Diamond Relat Mater1999 8 1686ndash1696

179 X Xiao J Birrell J E Gerbi O Auciello and J A CarlislelsquoLow temperature growth of ultrananocrystalline diamondrsquoJ Appl Phys 2004 94 2232ndash2239

180 M Sternberg P Zapol and L A Curtiss lsquoCarbon dimmers onthe diamond (100) surface growth and nucleationrsquo Phys Rev B2003 68B 205330-1-205330-9

181 D M Gruen C D Zuiker A R Krauss and X Z Pan lsquoCarbondimer C2 as a growth species for diamond films from methanehydrogenargon microwave plasmasrsquo J Vac Sci Technol A1995 13A 1628ndash1632

182 L Gueroudji and N M Hwang lsquoThermodynamic limits for thesubstrate temperature in the CVD diamond processrsquo DiamondRelat Mater 2000 9 205ndash211

183 Z-J Liu D W Zhang J-Y Zhang Y-Z Wan and J-T WanglsquoPhase diagrams for CVD diamond deposition from halogen-containing gas phasersquo Thin Solid Films 1999 342 42ndash46

184 Z-J Liu D W Zhang Y-ZWan J-Y Zhang and J-T WanglsquoThermodynamics of diamond film deposition at low pressurefrom chlorinated precursorsrsquo Appl Phys A 1999 68A 359ndash362

185 P K Bachmann D Leers and H Lydtin lsquoTowards a generalconcept of diamond chemical vapor depositionrsquo Diamond RelatMater 1991 1 1ndash12

186 J T Wang Y Z Wan Z J Liu H Wang D W Zhang andZ Q Huang lsquoPhase diagrams for activated CVD diamondgrowthrsquo Mater Lett 1998 33 311ndash314

187 R A Rudder G C Hudson J B Posthill R E Thomas andR J Markunas lsquoDirect deposition of polycrystalline diamondfilms on Si (100) without surface pretreatmentrsquo Appl Phys Lett1991 59 791ndash793

188 M Kadono T Inoue A Miyanaga and S Yamazaki lsquoDiamonddeposition from CF4ndashH2 mixed gas by microwave plasmarsquo ApplPhys Lett 1992 61 772ndash773

189 F C-N Hong G-T Liang J-J Wu D Chang and J-C HsiehlsquoDiamond deposition from halogenated methane reactants in ahot-filament chemical vapor deposition reactorrsquo Appl Phys Lett1993 63 3149ndash3151

190 F C-N Hong J-C Hsieh J-J Wu G-T Liang and J-HHwang lsquoLow temperature deposition of diamond using chlor-omethane in a hot-filament chemical vapor deposition reactorrsquoDiamond Relat Mater 1993 2 365ndash372

191 K J Grannen F Xiong and R P H Chang lsquoA comparisonstudy of diamond film grown on tungsten carbide cobalt toolinsert with CH4 and CF4 gas sourcesrsquo Surf Coat Technol 199357 155ndash162

192 H Maeda M Irie T Hino K Kusakabe and S MorookalsquoDiamond growth from a mixture of fluorocarbon and hydrogenin a microwave plasmarsquo Diamond Relat Mater 1994 3 1072ndash1078

193 T Nagano and N Shibata lsquoDiamond synthesis by microwave-plasma chemical vapor deposition using CH3Cl and CH2Cl2 ascarbon sourcersquo Jpn J Appl Phys 1993 32 5067ndash5071

194 R Ramesham T Roppel C Ellis D A Jaworske and W BaughlsquoSelective and low temperature synthesis of polycrystallinediamondrsquo J Mater Res 1991 6 1278ndash1286

195 J Stiegler T Lang M Nygard-Ferguson Y von Kaenel andE Blank lsquoLow temperature limits of diamond film growth bymicrowave plasma-assisted CVDrsquo Diamond Relat Mater 19965 226ndash230

196 S H Kim Y S Park S K Jung D H Kang and J-W LeelsquoEffect of the substrate state on the formation of diamond film ina low temperature microwave-plasma-enhanced chemical vapordeposition systemrsquo J Vac Sci Technol A 1995 13A 1619ndash1623

197 Z Ring T D Mantei S Tlali and H E Jackson lsquoLow-temperature diamond growth in a pulsed microwave plasmarsquoJ Vac Sci Technol A 1995 13A 1617ndash1618

198 I Schmidt and C Benndorf lsquoMechanisms of low temperaturegrowth of diamond using halogenated precursor-gasesrsquo DiamondRelat Mater 1998 7 266ndash271

199 J R Petherbridge P W May S R J Pearce K N Rosser andM N R Ashfold lsquoLow temperature diamond growth using CO2CH4 plasmas molecular beam mass spectrometry and computersimulation investigationsrsquo J Appl Phys 2001 89 1484ndash1492

200 J Petherbridge P W May S R J Pearce K N Rosser andM N R Ashfold lsquoMolecular beam mass spectrometry investiga-tions of low temperature diamond growth using CO2CH4

plasmasrsquo Diamond Relat Mater 2001 10 393ndash398201 D Das V Jayaseelan R Ramamurti R S Kukreja L Guo and

R N Singh lsquoLow surface temperature synthesis and character-ization of diamond thin filmsrsquo Diamond Relat Mater 2006 151336ndash1349

202 D Das R N Singh S Chattopadhyay and K H ChenlsquoThermal conductivity of diamond films deposited at low surfacetemperaturesrsquo J Mater Res 2006 21 379ndash388

203 J H D Rebello V V Subramaniam and T S SudarshanlsquoDiamond growth by laser-driven reactions in a COH2 mixturersquoAppl Phys Lett 1993 62 899ndash901

204 M Ihara H Maeno K Miyamoto and H Komiyama lsquoDiamonddeposition on silicon surfaces heated to temperature as low as 135uCrsquo Appl Phys Lett 1991 59 1473ndash1475

205 G Capote F L Freire L G Jacobsohn and G MariottolsquoAmorphous hydrogenated carbon films deposited by PECVD inmethane atmospheres highly diluted in argon effect of thesubstrate temperaturersquo Diamond Relat Mater 2004 13 1454ndash1458

206 J M Lopez F J Gordillo- Vazquez and J M AlbellalsquoNanocrystalline diamond thin films deposited by 35 kHz Ar-richplasmasrsquo Appl Surf Scie 2002 185 321ndash325

207 J Stiegler J Michler and E Blank lsquoAn investigation of structuraldefects in diamond films grown at low substrate temperaturesrsquoDiamond Relat Mater 1999 8 651ndash656

208 J Stiegler A Bergmaier J Michler Y von Kaenel G Dollingerand E Blank lsquoImpurity and defect incorporation in diamondfilms deposited at low substrate temperaturesrsquo Diamond RelatMater 1998 7 193ndash199



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nucleation leads to a better growth of the diamond filmJust like nucleation growth of diamond film is verymuch dependent on the deposition parameters The firstpart of this paper deals with the effect of the processingconditions on nucleation and growth of diamond filmTo have a better understanding and control of thedeposition process the underlying mechanism of nuclea-tion and growth has been discussed in view of some ofthe recent research findings in this area The surfacereaction and the gas phase chemistry involved indiamond film formation are explained in the light ofsome in situ characterisation technique such as real timespectroscopic ellipsometry (RTSE) and molecular beammass spectroscopy (MBMS)

The second part of this paper reviews the recentresults on low temperature growth of diamond film Theinterest in low temperature deposition of CVD diamondfilms stems from its excellent mechanical electricalelectronics optical and thermal properties Low coeffi-cient of friction close to that of teflon high hardness(hardest material) insensitivity towards moisture high-est elastic modulus and high thermal conductivity makediamond very attractive for large scale mechanicalapplications3 One of the main applications of diamondfilm in this area is the wear resistant coatings on cuttingtools drills and milling tools4 Numerous reports in theliterature show the advantage of the low temperaturedeposition of diamond film on hard tool materials5ndash14

However low deposition temperatures strongly reducethe growth rate and change the film morphology Evenfor very thin films high roughness is frequently obtainedwhen the film is deposited at low temperatures Lowtemperature diamond deposition is also important inelectronics15ndash18 Growing diamond films at low tem-peratures typically 500uC is important for manyapplications in electronics since substrate materials likeGaAs GaN plastics ZnS and MgF2 are unstable athigh temperatures19 and also to fabricate stress freediamond film on substrate because of the difference incoefficient of thermal expansion between diamond andsubstrates For optical applications the low temperaturedeposition of diamond films is inevitably requiredbecause of the low melting point of the optical materialssuch as glass Diamond deposition on optically trans-parent substrates such as sapphire zirconia and zincsulphide is of immense technological importance formany applications such as infrared windows20ndash22 Singlecrystal diamond possesses the highest thermal conduc-tivity (20ndash25 W cm21 K21) at room temperature of anymaterials This property coupled with a low thermalexpansion coefficient and a large electrical resistancemakes it the best material for heat sink application inelectronic devices23ndash25 But the use of diamond filmsfor thermal applications requires a high crystallinityreduced grain boundary network and very low contam-ination by non-carbon elements Low temperaturedeposition also eliminates the risk of any Si (for Siwafer) or other substrate material diffusion into thedeposited diamond layers

A review on the growth of diamond films at lowtemperatures was written by Muranaka et al in 199426

Limitations of substrate temperature in getting goodquality diamond films were discussed in the review Ingeneral the authors have suggested that low tempera-ture growth promotes the formation of amorphous

component at the cost of crystallinity of the film In spiteof the above difficulties several groups have tried todeposit good quality diamond films at low substratetemperatures using different precursor gases and sub-strates for various mechanical electrical optical elec-tronics and thermal properties in successive years27ndash34

However there are still some obvious problems forlow temperature CVD such as heating of the substratesby the plasma forced cooling of the substrate stage(holder) measurement of the real substrate temperatureand poor nucleation and slow growth rates Theinfluence of deposition parameters on low temperaturegrowth of diamond film has been discussed andparameters that enhance the low temperature growthhave been identified Since the kinetics of diamondgrowth is slow at low deposition temperatures a suitablepretreatment of the substrate which ensures a uniformand high nucleation density is an essential step beforedeposition For further understanding of the low tem-perature growth process the gas phase chemistryinvolved and the mechanism of the film formation atlow temperature are discussed

Nucleation of diamond

Effect of substrateDiamond nucleation is influenced by the choice ofsubstrates Since the lattice parameter and structure ofthe substrate materials with respect to diamond areimportant considerations in deciding a good filmgrowth all substrate materials do not respond equallyin getting a good adhesion of the film Early develop-ment of the CVD diamond films has been performed onsingle crystal diamond substrates3536 Diamond seedshave also been used in realising good diamond films37

The previous works are mostly confined to gettinghomoepitaxy of diamond In 1982 a breakthrough inCVD diamond technology was achieved by Matsumotoet al by growing diamond on to a non-diamond Si (100)substrate36 Hydrogen and hydrocarbon were activatedby passing through a hot filament at 2000uC and thediamond film was deposited onto a non-diamondsubstrate located 10 mm away from the filamentGraphite was etched simultaneously by atomic hydrogenleading to a higher growth rate (1 mm h21) Apartfrom having a very low nucleation density a continuousfilm was not achieved Diamond deposition was alsocarried out on a commercial purity titanium and Tindash6Alndash4V alloy substrates using a hot filament (tantalum)CVD and H2ndash1CH4 gas precursors38

The nucleation and early stages of growth of diamondwas studied on high performance ceramics Si3N4 using agas mixture of H2 and CH4 by an MPCVD process39

The influence of the substrate on the nucleationbehaviour was shown to be related to the change inmicrostructure during etching and to the reaction ofcarbon plasma species with Si3N4 where the incubationstage was mainly affected An optimisation of thenucleation and growth of diamond was performed withSi3N4 using the same gas mixture and MPCVD where anorthogonal design of experiments was used to optimisethe process parameters for achieving high nucleationdensity and growth40 The nucleation density increasedconsiderably with decreasing reactor pressure duringinitial nucleation stage Since the attack of the aggressive



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amorphous carbon















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Man

ey P

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hing

(c)

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ions

Ltd















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Man

ey P

ublis

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(c)

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ions

Ltd



Mechanical abrasion
























Enhancement




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Man

ey P

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hing

(c)

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mun

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Ltd


Chemical treatment



Surface coating














TiN 58 Yes 920 108

TiN 46 Yes 1140 26105

S3N4 68 Yes 910 108

S3N4 50 Yes 1080 66106



SiC 96 Yes 920 108

SiC 150 Yes 1070 108

a-C 001 No 850 46107

a-C 01 No 860 66107

a-C 001 Yes 860 1010



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(c)

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Biasing









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ey P

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hing

(c)

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mun

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ions

Ltd





















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d by

Man

ey P

ublis

hing

(c)

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Com

mun

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ions

Ltd











Role of kinetics


RNzmN (1)







Physical Society










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ey P

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(c)

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mun

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ions

Ltd










Carburisation



Seeding









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d by

Man

ey P

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hing

(c)

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Com

mun

icat

ions

Ltd


















TemperatureuC


CHCl3 CH4 CHCl3 CH4

850 392 571 18 92750 308 638 18 31650 307 1006 36 13



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d by

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(c)

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mun

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Pub

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ey P

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(c)

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mun

icat

ions

Ltd



















Pub

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Man

ey P

ublis

hing

(c)

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mun

icat

ions

Ltd













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d by

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ey P

ublis

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(c)

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mun

icat

ions

Ltd


G~A expE

RT

(2)















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d by

Man

ey P

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hing

(c)

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Com

mun

icat

ions

Ltd





















Pub

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Man

ey P

ublis

hing

(c)

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mun

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ions

Ltd




groups












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d by

Man

ey P

ublis

hing

(c)

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Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

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hing

(c)

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Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

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mun

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ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



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CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



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d by

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ey P

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(c)

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mun

icat

ions

Ltd

















Physics)



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ey P

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(c)

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mun

icat

ions

Ltd













Elsevier



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lishe

d by

Man

ey P

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(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

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(c)

IOM

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mun

icat

ions

Ltd





















Pub

lishe

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Man

ey P

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(c)

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mun

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ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



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lishe

d by

Man

ey P

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(c)

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mun

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ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

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Man

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Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





amorphous carbon















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



Mechanical abrasion
























Enhancement




Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


Chemical treatment



Surface coating














TiN 58 Yes 920 108

TiN 46 Yes 1140 26105

S3N4 68 Yes 910 108

S3N4 50 Yes 1080 66106



SiC 96 Yes 920 108

SiC 150 Yes 1070 108

a-C 001 No 850 46107

a-C 01 No 860 66107

a-C 001 Yes 860 1010



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





Biasing









Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd











Role of kinetics


RNzmN (1)







Physical Society










Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd










Carburisation



Seeding









Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


















TemperatureuC


CHCl3 CH4 CHCl3 CH4

850 392 571 18 92750 308 638 18 31650 307 1006 36 13



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


G~A expE

RT

(2)















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

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ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




groups












Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

lishe

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ey P

ublis

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(c)

IOM

Com

mun

icat

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Ltd

CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Physics)



Pub

lishe

d by

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ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



Mechanical abrasion
























Enhancement




Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


Chemical treatment



Surface coating














TiN 58 Yes 920 108

TiN 46 Yes 1140 26105

S3N4 68 Yes 910 108

S3N4 50 Yes 1080 66106



SiC 96 Yes 920 108

SiC 150 Yes 1070 108

a-C 001 No 850 46107

a-C 01 No 860 66107

a-C 001 Yes 860 1010



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Role of kinetics


RNzmN (1)







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Carburisation



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TemperatureuC


CHCl3 CH4 CHCl3 CH4

850 392 571 18 92750 308 638 18 31650 307 1006 36 13



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G~A expE

RT

(2)















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groups












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R~Isp3

IflzIsp3zPk

Ik

(3)







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as function of N2



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H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



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CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








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CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



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Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



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Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

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ey P

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Com

mun

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Acknowledgements
























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lishe

d by

Man

ey P

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hing

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Com

mun

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Ltd





















































Pub

lishe

d by

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ey P

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hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

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hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

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ey P

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(c)

IOM

Com

mun

icat

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Ltd

















































Pub

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Mechanical abrasion
























Enhancement




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Chemical treatment



Surface coating














TiN 58 Yes 920 108

TiN 46 Yes 1140 26105

S3N4 68 Yes 910 108

S3N4 50 Yes 1080 66106



SiC 96 Yes 920 108

SiC 150 Yes 1070 108

a-C 001 No 850 46107

a-C 01 No 860 66107

a-C 001 Yes 860 1010



Pub

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ey P

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mun

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Biasing









Pub

lishe

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Man

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IOM

Com

mun

icat

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Ltd





















Pub

lishe

d by

Man

ey P

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(c)

IOM

Com

mun

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ions

Ltd











Role of kinetics


RNzmN (1)







Physical Society










Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd










Carburisation



Seeding









Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


















TemperatureuC


CHCl3 CH4 CHCl3 CH4

850 392 571 18 92750 308 638 18 31650 307 1006 36 13



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















Pub

lishe

d by

Man

ey P

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(c)

IOM

Com

mun

icat

ions

Ltd













Pub

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(c)

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Com

mun

icat

ions

Ltd


G~A expE

RT

(2)















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

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IOM

Com

mun

icat

ions

Ltd




groups












Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



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lishe

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(c)

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Com

mun

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Pub

lishe

d by

Man

ey P

ublis

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(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

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CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



Pub

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ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Physics)



Pub

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ey P

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hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

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Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















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ey P

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Com

mun

icat

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Ltd





















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Com

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CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

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d by

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ey P

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(c)

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Com

mun

icat

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Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

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Man

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Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

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hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

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ey P

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(c)

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Com

mun

icat

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Ltd


Chemical treatment



Surface coating














TiN 58 Yes 920 108

TiN 46 Yes 1140 26105

S3N4 68 Yes 910 108

S3N4 50 Yes 1080 66106



SiC 96 Yes 920 108

SiC 150 Yes 1070 108

a-C 001 No 850 46107

a-C 01 No 860 66107

a-C 001 Yes 860 1010



Pub

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mun

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Biasing









Pub

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hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

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ey P

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(c)

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Com

mun

icat

ions

Ltd











Role of kinetics


RNzmN (1)







Physical Society










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(c)

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mun

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ions

Ltd










Carburisation



Seeding









Pub

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d by

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ey P

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hing

(c)

IOM

Com

mun

icat

ions

Ltd


















TemperatureuC


CHCl3 CH4 CHCl3 CH4

850 392 571 18 92750 308 638 18 31650 307 1006 36 13



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(c)

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(c)

IOM

Com

mun

icat

ions

Ltd



















Pub

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mun

icat

ions

Ltd













Pub

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mun

icat

ions

Ltd


G~A expE

RT

(2)















Pub

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hing

(c)

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Com

mun

icat

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Ltd





















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groups












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mun

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ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

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(c)

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mun

icat

ions

Ltd

















as function of N2



Elsevier



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Pub

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mun

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ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



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CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



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Ltd

















Physics)



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Elsevier



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Com

mun

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Ltd

















Elsevier



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lishe

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ey P

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hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

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hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

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(c)

IOM

Com

mun

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ions

Ltd





















Pub

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CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





Biasing









Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd











Role of kinetics


RNzmN (1)







Physical Society










Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd










Carburisation



Seeding









Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


















TemperatureuC


CHCl3 CH4 CHCl3 CH4

850 392 571 18 92750 308 638 18 31650 307 1006 36 13



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


G~A expE

RT

(2)















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




groups












Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

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mun

icat

ions

Ltd

CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Physics)



Pub

lishe

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Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd











Role of kinetics


RNzmN (1)







Physical Society










Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd










Carburisation



Seeding









Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


















TemperatureuC


CHCl3 CH4 CHCl3 CH4

850 392 571 18 92750 308 638 18 31650 307 1006 36 13



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


G~A expE

RT

(2)















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




groups












Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

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Com

mun

icat

ions

Ltd








Acknowledgements
























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lishe

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ey P

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hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd











Role of kinetics


RNzmN (1)







Physical Society










Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd










Carburisation



Seeding









Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


















TemperatureuC


CHCl3 CH4 CHCl3 CH4

850 392 571 18 92750 308 638 18 31650 307 1006 36 13



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Pub

lishe

d by

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ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


G~A expE

RT

(2)















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




groups












Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



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lishe

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ey P

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Pub

lishe

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ey P

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(c)

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Com

mun

icat

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Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

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CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



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hing

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Com

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icat

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Ltd

















Physics)



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ey P

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Elsevier



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lishe

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icat

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Ltd




















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lishe

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ey P

ublis

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(c)

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Com

mun

icat

ions

Ltd





















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lishe

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ey P

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Com

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icat

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Ltd





















Pub

lishe

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Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd










Carburisation



Seeding









Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


















TemperatureuC


CHCl3 CH4 CHCl3 CH4

850 392 571 18 92750 308 638 18 31650 307 1006 36 13



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


G~A expE

RT

(2)















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




groups












Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

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H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



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CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












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CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

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d by

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ey P

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(c)

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mun

icat

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Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

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Man

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Com

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icat

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Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

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ey P

ublis

hing

(c)

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Com

mun

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ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

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hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

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(c)

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Com

mun

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TemperatureuC


CHCl3 CH4 CHCl3 CH4

850 392 571 18 92750 308 638 18 31650 307 1006 36 13



Pub

lishe

d by

Man

ey P

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hing

(c)

IOM

Com

mun

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ions

Ltd

















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















Pub

lishe

d by

Man

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ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Pub

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d by

Man

ey P

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hing

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Com

mun

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ions

Ltd


G~A expE

RT

(2)















Pub

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d by

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hing

(c)

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Com

mun

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Ltd





















Pub

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mun

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ions

Ltd




groups












Pub

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d by

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Com

mun

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ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

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ey P

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hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



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Pub

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Com

mun

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H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

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d by

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ey P

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(c)

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CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












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Elsevier



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hing

(c)

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Com

mun

icat

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Ltd




















Pub

lishe

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(c)

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Com

mun

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Ltd





















Pub

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Ltd





















Pub

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mun

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Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


G~A expE

RT

(2)















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




groups












Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


G~A expE

RT

(2)















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




groups












Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


G~A expE

RT

(2)















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




groups












Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



Pub

lishe

d by

Man

ey P

ublis

hing

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IOM

Com

mun

icat

ions

Ltd

















Physics)



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lishe

d by

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ey P

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hing

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Com

mun

icat

ions

Ltd













Elsevier



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lishe

d by

Man

ey P

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hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd


G~A expE

RT

(2)















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




groups












Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




groups












Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




groups












Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









R~Isp3

IflzIsp3zPk

Ik

(3)







Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

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Ltd

CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








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ey P

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Ltd

















Physics)



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hing

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Com

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icat

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Ltd













Elsevier



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lishe

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ey P

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hing

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Com

mun

icat

ions

Ltd

















Elsevier



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lishe

d by

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ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

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Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















as function of N2



Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions



















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd









H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



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H22H DG02500~75 kJ mol1 (5)


DG01500~470 kJ mol1 (6)












CdHzHCdzH2 (13)

CdzHCdH (14)

CdzCH3CdM (15)



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CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












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CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



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Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

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Man

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Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

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hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

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hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

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(c)

IOM

Com

mun

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Ltd

















































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CdMCdzCH3 (16)

CdMzHCdMzH2 (17)

CdMzHCdHzCdzH2 (18)












z








Society



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lishe

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Man

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hing

(c)

IOM

Com

mun

icat

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Ltd

















Physics)



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Com

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Ltd













Elsevier



Pub

lishe

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Ltd

















Elsevier



Pub

lishe

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Man

ey P

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hing

(c)

IOM

Com

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Ltd




















Pub

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(c)

IOM

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CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd













Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















Elsevier



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd




















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



CO2zCH42COz2H2 (24)

CH4C2H2z3H2 (25)

CO2zH2COzH2O (26)

H2OzC2H2CH4zCO (27)










Physics)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Tab

le4

Su

mm

ary

of

LT

DG

stu

die

sre

po

rted

inli

tera

ture

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

ArF

excim

er

laser

(193

nm

)99 3

H

20

7

CO

Sin

gle

cry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

4ndash80

5ndash1mm

dia

p

art

icle

RT

8N

A5ndash10

203

Gro

wth

isob

serv

ed

within

1h

HFC

VD

1

CH

4H

2(t

ota

lg

as

flow

5300

sccm

)S

ing

lecry

sta

lS

i(1

11)

Mechanic

alab

rasio

nw

ith

dia

mond

pow

der

135

50N

A1

(700uC

)0 3

6(2

50uC

)0 2

8(1

35uC

)0

(70uC

)

204

Gro

wth

tem

p

can

be

low

ere

dd

ow

nb

ylo

wering

CH

4conc

RF

PE

CV

D100

CH

4and

98

CH

42

A

rS

iR

F(1

3 5

6M

Hz)

bia

sin

gb

etw

een

250

and

2500

V2

23

27

0 1

NA

2205

a-C

Hfilm

isob

tain

ed

(VT5

50

sccm

)147

35

kH

zR

Fp

lasm

aC

H4A

r(8

0and

95

)S

ing

lecry

sta

lS

i(1

00)

Ultra

sonic

ation

ina

bath

of

aceto

ne

and

eth

anol

zA

rp

lasm

ap

reheate

dfo

r5

min

15

and

200

0 1

and

0 3

NA

0 1

(15)

and

0 2

(200)

206

Surf

ace

roug

hness

0 2

nm

nanod

iam

ond

fraction

isvery

less

hard

ness

15

GP

aM

WC

VD

CH

4H

2and

CH

4C

O2

Si(1

00)

2340ndash740

(IR

pyro

mete

r)608

00

ndash207

Defe

cts

im

purities

are

incre

ased

with

N2

conta

min

ation

and

low

er

TS

MW

CV

DC

H4C

O2

(293

1sccm

)S

i(1

00)

ndash275ndash560

(IR

pyro

mete

r)606

00

ndash208

Very

low

N2

conta

min

ation

levelis

req

uired

for

good

qualit

yfilm

HFC

VD

CH

F3H

2and

CF

4H

2

(VT5

200

sccm

)S

iA

bra

sio

nw

ith

dia

mond

pow

der

350ndash850

(NiC

rN

ith

erm

ocoup

le)

15N

A0 3

5(f

or

1 5

ndash2 0

C

HF

3)

and

0fo

rC

F4

152

Show

sp

oor

ad

hesio

nw

ith

the

sub

str

ate

surf

ace

HFC

VD

MW

CV

DC

HF

3C

2H

5C

lS

i(1

00)

Ab

rasio

nw

ith

dia

mond

pow

der

(0 2

5mm

)350

(NiC

rN

ith

erm

ocoup

le)

154

80

ndash198

Halo

gen

low

ers

the

dep

ositio

nte

mp

era

ture

by

surf

ace

reaction

Cl 2

MW

CV

DC

O2C

H4(0

ndash80

)(V

T5

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

ndash200

Conc

of

CO

inp

lasm

ais

contr

olli

ng

facto

rin

LTD

GM

WC

VD

CH

4C

O2

(11

80

sccm

)S

ing

lecry

sta

lS

i(1

00)

Ab

rasio

nw

ith

1ndash3mm

dia

m

grit

435ndash845

(calib

rate

dK

typ

eth

erm

ocoup

le)

401

000

0 1

(500uC

)199

CH

3is

the

key

gro

wth

sp

ecie

sfo

rC

O2C

H4

pla

sm

aH

FC

VD

H2C

H4

H2C

HF

3

H2C

2H

5C

lS

iM

op

late

sS

cra

tchin

gw

ith

dia

m

pow

der

370

(NiC

rN

ith

erm

ocoup

le)

15N

Andash

151

Decre

ase

inC

conte

nt

inp

recurs

or

shifts

TS

tolo

wer

Tem

p

HFC

VD

and

MW

CV

D0 5

ndash2

C2H

5C

lz

H2

Si

Zn

Aland

gla

ss

Mechanic

alab

rasio

nw

ith

0 2

5mm

dia

m

pow

der

377ndash800

(IR

pyro

mete

rand

NiC

rN

ith

erm

ocoup

le)

15N

Andash

149

Gro

wth

rate

incre

ases

with

incre

asin

ghalo

gen

inp

recurs

or

MW

CV

DC

H4H

2

CH

4C

O2(O

2)

H2

CH

4C

O2

invary

ing

pro

port

ions

Si(1

00)

ndash270ndash540

(IR

pyro

mete

r)608

00

(CH

4H

2)

606

00

(CH

4C

O2)

ndash195

LTD

Gis

influenced

by

O2

and

O2

conta

inin

gsp

ecie

s

HFC

VD

and

H2C

H4C

l 2

Si(1

00)

Mechanic

alab

rasio

nw

ith

370

(Si)

154

80

ndash150

Halo

gen

pro

mote

sLTD

GM

WC

VD

H2C

2H

5C

lG

lass

0 2

5mm

dia

m

pow

der

490

(gla

ss

Al)

H2C

HF

3A

l



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

Pro

cess

Pre

cu

rso

rS

ub

str

ate

Pre

treatm

en

tS

ub

sT

em

pT

SuC

Pp

ow

er

torr

WG

row

thra

te

mm

h2

1R

ef

Rem

ark

s

PE

CV

D17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

17 5

CH

4ndash30C

O2

16 1

CH

4ndash30C

O2

p-S

i(1

00)

Mechanic

alscra

tchin

gw

ith

1ndash2mm

dia

m

pow

der

550ndash250

25ndash6N

Andash

19

Thre

eord

ers

of

mag

nitud

ele

ss

inre

sis

tivity

than

that

of

conventionalfilm

EC

RC

VD

1

CH

3O

Hndash99

H2

Sap

phire

(Al 2

O3)

Ultra

sonic

ation

ina

slu

rry

of

0 2

5mm

dia

mond

z

aceto

ne

500ndash550

1N

A0 2

31

Show

80

op

tical

transm

issio

nat

l

2mm

Low

outp

ut

pow

er

MW

CV

DC

O(7

)

H2

CO

(7

)O

2(2

2

)H

2

Sin

gle

cry

sta

lS

iU

ltra

sonic

ation

ina

slu

rry

of

dia

mond

zm

eth

anol

zcle

anin

gin

org

anic

solv

ent

130ndash750

(Therm

ocoup

le)

ndash0 1

9ndash0 7

3(4

03ndash750)

0 0

35ndash0 2

(411ndash750)

148

CndashH

ndashO

isa

bett

er

syste

mfo

rLTD

G

MW

CV

DC

OH

2(C

O

9sccm

)S

iand

NC

Dfilm

(800uC

)on

seed

ed

Si

Ab

rad

ed

with

0 2

5mm

dia

mond

pow

der

350ndash500

105

00

2 5

146

NC

Dcoating

isto

avoid

pro

pert

ies

variation

147

MW

CV

DC

H4

6sccm

H2

194

sccm

WC

ndash6

CO

Ultra

sonic

ation

inH

NO

3H

2O

5

12

(vol)

5m

inth

en

scra

tchin

gw

ith

dia

mond

pow

der

ina

CH

3O

Hb

ath

400

9 7

53

00

ndash12

Cutt

ing

perf

orm

ance

imp

roved

MP

CV

D200

sccm

H24

sccm

CH

4P

att

ern

ed

gla

ss

H2

pla

sm

acle

anin

gfo

rfe

wm

inute

s450

134

00

ndash15

Cyclic

mod

ula

tion

of

CH

4

and

keep

ing

the

sub

str

ate

3cm

rem

ote

from

pla

sm

aenhanced

LTD

GM

ag

neto

active

MW

CV

DC

H3O

H

15

sccm

H285

sccm

p-S

i(1

00)

Ultra

sonic

ag

itate

d

z30

Vb

ias

200ndash600

0 0

751

300

ndash16

Nanod

iam

ond

phase

found

MP

CV

D4

CH

4H

2n-S

i(1

00)

gla

ss

quart

zU

ntr

eate

dor

ultra

sonic

ation

in30mm

dia

mond

aceto

ne

slu

rry

for

5h

460

(op

ticalp

yro

mete

r)401

100

ndash196

LTD

Gachie

ved

by

puttin

gth

esub

str

ate

3cm

rem

ote

from

pla

sm

aM

WC

VD

H2C

H4

(0 2

5ndash7

)V

T5

200

sccm

Si(1

00)

Coating

of

a20

AA

uP

din

terlayer

by

sp

utt

ering

400ndash700

(bic

hro

matic

op

ticalp

yro

mete

r)37 5

1000

0 0

01ndash0 0

111

Pro

duced

low

roug

hness

film

ow

ing

toenhanced

second

ary

nucle

ation

MW

CV

DC

H4H

2ndashO

2

H25

100

sccm

CH

45

17

sccm

O25

16

sccm

n-S

iA

bra

sio

nw

ith

alc

oholsolu

tion

of

5mm

dia

mond

pow

der

300ndash500

(backsid

eT

S

with

Kty

pe

therm

ocoup

le)

3(

avera

ge

300

peak

3kW

)0 0

8ndash0 2

197

Puls

ing

of

MW

Gro

wth

rate

incre

ased

to20ndash50

tim

es

than

inC

Wm

od

e

T

s

sub

str

ate

tem

pera

ture

V

T

tota

lvolu

me

of

gas

flow

R

F

rad

iofr

eq

uency

IR

infr

are

d

LTD

G

low

tem

pera

ture

dia

mond

gro

wth

N

CD

nanocry

sta

lline

dia

mond

M

W

mic

row

ave

CW

continuous

wave

Tab

le4

(Co

nti

nu

ed

)



Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd








Acknowledgements
























Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd





















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd






















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd



















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































Pub

lishe

d by

Man

ey P

ublis

hing

(c)

IOM

Com

mun

icat

ions

Ltd

















































a review of nucleation, growth and low temperature synthesis of...

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