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NanoMas Technologies, IncNanoMas Technologies, Inc
Nanoparticle Inks Nanoparticle Inks
for Printed Electronicsfor Printed Electronics
ZhihaoZhihao YangYangPresident & CTOPresident & CTO
NanoMas Technologies, Inc.NanoMas Technologies, [email protected]@nanomastech.com
Technology Revolutions in Electronics Technology Revolutions in Electronics
for the Past 100 Yearsfor the Past 100 Years
•• Vacuum Tube Transistors: 1906 Vacuum Tube Transistors: 1906 by Lee De Forest by Lee De Forest
•• Solid State Transistors: 1947 by Solid State Transistors: 1947 by John Bardeen and Walter John Bardeen and Walter Brattain (Bell Telephone Brattain (Bell Telephone Laboratories)Laboratories)
•• Integrated Circuits: 1958 by Jack Integrated Circuits: 1958 by Jack KilbyKilby (Texas Instruments)(Texas Instruments)
What Next?What Next? The industry has followed the prediction of MooreThe industry has followed the prediction of Moore’’s Law s Law for the last 40 years without major technology revolution.for the last 40 years without major technology revolution.
MooreMoore’’s Laws Law: The number of transistors per unit area is : The number of transistors per unit area is doubling every 1.5 years. doubling every 1.5 years. ----Gordon Moore (founder of Gordon Moore (founder of Intel Corporation).Intel Corporation).
MooreMoore’’s Law is reaching its physical limit in next 5 to 10 s Law is reaching its physical limit in next 5 to 10 years. years.
What will be the next technology revolution in the What will be the next technology revolution in the electronics industry?electronics industry?
Look beyond the Silicon
Pentacene organic circuits on polymeric or cloth substrates
Polymeric substrate AMLCD
a-Si:H active matrix Gamma ray detector on polyimide substrate
a-Si:H strain bridge array
Plastic solar cell
LowLow--Cost ICs on Arbitrary SubstratesCost ICs on Arbitrary Substrates
Large Area & Flexible DisplaysLarge Area & Flexible Displays
World's thinnest flexible active-matrix display (Philips)
Flexible active matrix e-paper SVGA display (Plastic Logic)
World's first 3mm thick flexible digital watch (Citizen)
The plastic TFT-LCD display (Samsung)
LowLow--cost RFIDs and Disposable Electronicscost RFIDs and Disposable Electronics
Current cost: 7Current cost: 7--10 cents per tag10 cents per tag
Target cost: 1Target cost: 1--2 cents per tag2 cents per tag
Tremendous Market Growth Potential for Tremendous Market Growth Potential for
Printed Electronics in Next 20 YearsPrinted Electronics in Next 20 Years
Recent report by Recent report by IDTechExIDTechEx predicts the PE market will reach $300B in 2027predicts the PE market will reach $300B in 2027
$0.0
$2,000.0
$4,000.0
$6,000.0
$8,000.0
$10,000.0
$12,000.0
$14,000.0
2006 2007 2008 2009 2010 2011
Year
$ in Million
(Data from NanoMarkets LLC)
2011 Total PE Reveue $12,385 (in Million)
Printable Display, $3,801
RFID, $2,557 Printable Signage,
$1,250
Printable Backplanes, $1,134
Printable Photovoltaic, $1,042
Other (21% Overall), $2,601
(Data from NanoMarkets LLC)
Highly conductive and high resolution patterns fabricated using Highly conductive and high resolution patterns fabricated using lowlow--cost and cost and rollroll--toto--roll processes (such as inkjet and gravure printing) are one of roll processes (such as inkjet and gravure printing) are one of the most the most critical technology components in making printed electronics andcritical technology components in making printed electronics and displaysdisplays
Market of Applications: Market of Applications: Flat panel display backplanes (TFT electrodes and busFlat panel display backplanes (TFT electrodes and bus--bars) bars) EMI Shielding : plasma display, LCD, etc EMI Shielding : plasma display, LCD, etc RFID tagsRFID tags
Electroluminescent lighting Electroluminescent lighting Printed circuit boards (PCBs) Printed circuit boards (PCBs) Touch screensTouch screens
Printed ConductorsPrinted Conductors
NanoMas Solutions:Make conducting patterns using metal nanoparticle inks!
Technology Comparison for Printed ConductorsTechnology Comparison for Printed Conductors
10 100 10-1
10010-1
10-610-510-410-310-2
10 102 103 104 105 106
Conductive Polymers
Carbon Nanotubes
Sputtered ITO
Resistivity
Conductivity
(Ohm-cm)
(S/cm)
Silver Micro-Powder Pastes
Evaporated Metals
Metal Nanoparticle InksPrintable
Vacuum Processed
SizeSize--Dependent Melting Point of NanoparticlesDependent Melting Point of Nanoparticles
232
b m s
s l
m s s l
T T
T L R
ργ γ
ρ ρ
− = −
Ph. Ph. BuffatBuffat and Jand J--P. P. BorelBorel, , Phys. Phys.
Rev. A,Rev. A, 1313, 1976, 1976, 2287, 2287
Small particle size (in nanometers) Small particle size (in nanometers) significantly reduces the melting significantly reduces the melting temperature of NPs from the bulk temperature of NPs from the bulk melting point, allowing for very low melting point, allowing for very low processing temperatures (based on processing temperatures (based on surface melting) for sintering NPs surface melting) for sintering NPs into conducting films.into conducting films.
Nanoparticle Inks for Printed ElectronicsNanoparticle Inks for Printed Electronics
200 nm
Deposited Ag nanoparticlesConductive Ag film on PET cured from printed nanoparticle inks
•• Nanoparticles can be stabilized in ink solutions by organic Nanoparticles can be stabilized in ink solutions by organic ligandligandshells, which can be removed after printing. shells, which can be removed after printing.
•• Nanoparticles can be further cured or sintered to highly conductNanoparticles can be further cured or sintered to highly conductive ive films at low temperatures.films at low temperatures.
100-150°C70-90°C
150°C
NanoMas Proprietary Technology: Producing High Quality NanoMas Proprietary Technology: Producing High Quality
NanoparticlesNanoparticles with Largewith Large--Scale and LowScale and Low--Cost ProcessesCost Processes
A 50L pilot production A 50L pilot production reactor at NanoMasreactor at NanoMas
NanoMas NanoMas silver silver nanoparticles nanoparticles with 5with 5--6 nm 6 nm in size (SEM)in size (SEM)
NanoMas Ag nanoparticle powders and inksNanoMas Ag nanoparticle powders and inks
NanoMas Proprietary Printable Metal NanoMas Proprietary Printable Metal
Nanoparticle Conductive Inks TechnologyNanoparticle Conductive Inks Technology
•• Unique all solution based nanoparticle synthesis technology Unique all solution based nanoparticle synthesis technology (patent pending), widely compatible with the low cost (patent pending), widely compatible with the low cost production processes in the chemical industryproduction processes in the chemical industry
•• Low cost and fully scalable to large scale mass productionLow cost and fully scalable to large scale mass production–– Scaled up to pilot production with a 50 litter reactorScaled up to pilot production with a 50 litter reactor
•• UltraUltra--small nanoparticle size (2 to 10 nm) with specially small nanoparticle size (2 to 10 nm) with specially designed surface chemistry allows low annealing designed surface chemistry allows low annealing temperature, short process time, and high conductivitytemperature, short process time, and high conductivity
•• Variety of surface chemistry for different solvent dispersion Variety of surface chemistry for different solvent dispersion and applicationsand applications
•• Low resistivity (as low as ~2.3 Low resistivity (as low as ~2.3 µΩµΩ--ccm, 1.5x of pure Ag) m, 1.5x of pure Ag) •• Low process temperature (as low as ~90Low process temperature (as low as ~90°°C) compatible with C) compatible with most plastic substratesmost plastic substrates
•• Also curable by laser or UV light at room temperatureAlso curable by laser or UV light at room temperature
Nano-Au (4 nm) nanoparticle solution in cyclohexane
Nano-Ag (5 nm) nanoparticle solution in cyclohexane
Ag nanoparticles in cyclohexane(λmax ~ 416 nm)
Au nanoparticles in cyclohexane
UV-Vis Absorption Spectra of Au and Ag Nanoparticle Solutions
UVUV--visvis Characterization of NanoMas Characterization of NanoMas
Gold and Silver NanoparticlesGold and Silver Nanoparticles
Nano-Ag
Nano-Au
NanoMas Au Nanoparticles (<5 nm)NanoMas Au Nanoparticles (<5 nm)
TEMDSC
• DSC: exothermic sintering between 180ºC and 210ºC
• TGA: ~10-15% weight loss between 180ºC and 250ºC due to loss of surface capping agent
• Resistivity: ~8 µΩ-cm (annealed at 200°C, 3x of bulk Au)
• DSC: exothermic sintering between 110ºC and 160ºC• TGA: ~10% weight loss between 100ºC and 200ºC due to loss of surface capping agent• Resistivity: 2.4 µΩ-cm (annealed at 150°C, 1.5x of bulk Ag)
ECD Distribution of ZHY-050616 by TEM
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
1 10 100
ECD [nm]
Frequency
Frequency Data Lognormal Fit
Metric ValueMean ECD [nm] 5.72Std Dev ECD [nm] 1.79Count 726GMD ECD [nm] 5.43GSD 1.41Fit GMD [nm] 5.98Fit GSD [nm] 1.24
TEM
NanoMas Ag Nanoparticles NanoMas Ag Nanoparticles
Particle size: 6 ±1 nm
DSC
sintering
Core radius: 23 ± 1 ǺCore radius σ: 5.5 ǺShell thickness: 6 ±1 Ǻsample
θ
detector
Incident neutron
Scattered neutron
Small Angle Neutron Scattering (SANS) Small Angle Neutron Scattering (SANS)
Characterization of NanoMas NanoCharacterization of NanoMas Nano--Ag Ag
SANS spectra confirmed that the Nano-Ag has an Ag core diameter of 4.6 ±1.1 nm and a 0.6 ±0.1 nm thick shell in solvent or a 0.3 nm shell in packed (solid) state.
-2.0 -1.5 -1.0 -0.5
-1.0
-0.5
0.0
0.5
1.0
Intensity (cm
-1)
Log (Q) [A]
SANS Data Core-Shell Model Fitting
Core radius: 23 ± 1 ǺCore radius σ: 5.5 ǺShell thickness: 6 ±1 Ǻ
SANS on NanoSANS on Nano--Ag Solutions Ag Solutions (10 wt% in d(10 wt% in d--Toluene)Toluene)
0.05 0.10 0.15 0.20 0.250
1
2
3
4
5
Intensity (cm
-1)
Q (A)
Qmax= 0.120 Ǻ-1
interparticle distance ~ 5.2 nm
SANS of Packed NanoSANS of Packed Nano--Ag (Solid)Ag (Solid)
Cabot PED (20-30 nm)
Cima NanoTech(80-100 nm)
NovaCentrix(~20 nm broad distribution)
ManoMas (~ 5 nm)
Superior Performance of NanoMas Superior Performance of NanoMas NanoSilverNanoSilver Inks Inks
due to the Ultradue to the Ultra--Small Nanoparticle SizeSmall Nanoparticle Size
25
20
15
10
5
0
Resistivity (µΩ-cm)
250200150100
Annealing Temperature (C)
NanoMas NanoAg (5 nm)
NanoAg (~25 nm)from competitors
Ag bulk resistivity
PET Kapton
Printed Conductive Patterns on Plastic Substrates
13.56 MHz RFID antenna printed on PET and polyimide
Miniature RF coil printed on PET Printed flex circuit on polyimide
Inkjet Printed Inkjet Printed NanoSilverNanoSilver Contacts in Contacts in
Fabricating aFabricating a--Si:HSi:H TFTsTFTs on Glasson Glass
Source
Drain
Ag (~ 30 nm)Cr (~ 5 nm)n+ a-Si:H (~ 50 nm)a-Si:H (~ 200 nm)a-SiNx:H (~ 300 nm)Cr (~ 35 nm)Glass Substrate
Probes
-10 0 10 20 30 40
10-6
10-5
10-4
I DS (A)
VGS (V)
VDS = 40 V L = 110 um L = 140 um
0
100
200
I DS (uA)
~ 1.41~ 1.41~ 1.68~ 1.68VVTT (V)(V)
~ 0.97~ 0.97~ 0.91~ 0.91µµ ((cmcm22/Vs/Vs))
140140110110L (L (µµm)m)
* Data curtsey of Dr. * Data curtsey of Dr. YongtaekYongtaek Hong of Hong of Seoul National University, Korea Seoul National University, Korea
Single crystal silicon gate
Silicon dioxide gate dielectric
Ag AgPQT
Printed Printed NanoSilverNanoSilver Contacts in Contacts in
Fabricating Organic Fabricating Organic TFTsTFTs
•• Organic Semiconductor: poly(3,3 Organic Semiconductor: poly(3,3 --didodecyldidodecyl--quaterthiophenequaterthiophene) or PQT) or PQT--1212•• Source and drain printed with NanoMas Source and drain printed with NanoMas NanoSilverNanoSilver inks and annealed at 145inks and annealed at 145ººCC•• Device channel length of ~43 um and Device channel length of ~43 um and width of ~300 umwidth of ~300 um•• No obvious contact resistance No obvious contact resistance
* Data curtsey of Dr. * Data curtsey of Dr. JurgenJurgen Daniel of PARC Daniel of PARC
Inkjet Printed Inkjet Printed TFTsTFTs with with ZnOZnO and Ag and Ag
Nanoparticle InksNanoparticle Inks
• Print or coat with ZnO nanoparticle ink• Heat step at 200 C to anneal • Print silver nanoparticles for source/drain, and annealed at 150C
Mobilities: 0.1-0.15 cm2/Vs On/Off: ~105
1.0E-101.0E-091.0E-081.0E-071.0E-061.0E-051.0E-04
-30 -10 10 30 50
Vg
Log(Id)
0.0E+00
2.0E-03
4.0E-03
6.0E-03
8.0E-03ZnO TFT with printed Ag contacts
About CostAbout Cost……
•• What Printed Electronics should shoot for are high What Printed Electronics should shoot for are high productivity, large size and volume, high flexibility, and productivity, large size and volume, high flexibility, and ultimately the LOW COST.ultimately the LOW COST.
•• The nanoparticle inks should also be made by LOW COST The nanoparticle inks should also be made by LOW COST processes.processes.
•• NanoMas makes sure all the nanoNanoMas makes sure all the nano--materials it makes can materials it makes can be mass produced with LOW COST processes.be mass produced with LOW COST processes.
LabLab Mass ProductionMass ProductionPilot ProductionPilot Production
Functional Functional NanomaterialsNanomaterials
•• Silver Silver nanoparticlesnanoparticles•• Gold Gold nanoparticlesnanoparticles•• Carbon Carbon nanotubesnanotubes•• Carbon Carbon nanofibersnanofibers•• Decorated carbon Decorated carbon nanotubesnanotubes•• Magnetic Magnetic nanoparticlesnanoparticles•• Novel catalysts for making Novel catalysts for making carbon carbon nanomaterialsnanomaterials
NanoMas Technology and Product RoadmapNanoMas Technology and Product Roadmap
•• NanoMas current products include NanoMas current products include NanoSilverNanoSilver™™ and and NanoGoldNanoGold™™conductive inks. conductive inks.
•• Under development with its proprietary technology, NanoMas will Under development with its proprietary technology, NanoMas will also also provide inorganic nanoparticle and polymer semiconductor inks, aprovide inorganic nanoparticle and polymer semiconductor inks, as well s well as electroluminescent (EL or LED) inks for PE applications. as electroluminescent (EL or LED) inks for PE applications.
•• NanoMas also has the technologies to mass produce high quality cNanoMas also has the technologies to mass produce high quality carbon arbon nanotubesnanotubes and carbon and carbon nanofibersnanofibers..
Printable Electronics & DisplaysPrintable Electronics & Displays
•• Silver nanoparticle inksSilver nanoparticle inks•• Gold nanoparticle inksGold nanoparticle inks•• ELEL nanoparticle inksnanoparticle inks•• Semiconductor nanoparticle inksSemiconductor nanoparticle inks•• Polymer semiconductor inks Polymer semiconductor inks •• Inorganic dielectric inksInorganic dielectric inks•• Polymer dielectric inks Polymer dielectric inks
NanoMas Product Portfolio
Other Other NanomaterialsNanomaterials Developed at Developed at
NanoMas Technologies, Inc.NanoMas Technologies, Inc.
NanoMas Technologies, IncNanoMas Technologies, Inc
NanoMas Technologies, Inc. is an early stage startNanoMas Technologies, Inc. is an early stage start--up company, up company, located in the Innovative Technologies Complex (ITC) on the camplocated in the Innovative Technologies Complex (ITC) on the campus of us of Binghamton University (SUNY) in Binghamton, New York, where is aBinghamton University (SUNY) in Binghamton, New York, where is also lso the home of Center for Advanced Microelectronics Manufacturing the home of Center for Advanced Microelectronics Manufacturing (CAMM), funded by the USDC to lead the development of next (CAMM), funded by the USDC to lead the development of next generation rollgeneration roll--toto--roll (R2R) microelectronics manufacturing.roll (R2R) microelectronics manufacturing.
Innovative Technologies Complex Innovative Technologies Complex Suite 2109 Suite 2109 85 Murray Hill Road 85 Murray Hill Road Vestal, NY 13850Vestal, NY 13850
Phone: 607Phone: 607--821821--42084208Fax: 866Fax: 866--367367--1128 (toll1128 (toll--free)free)Website: Website: www.nanomastech.comwww.nanomastech.com