See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/256854965

HF/HNO 3 etching of the saw damage

Article  in  Energy Procedia · December 2013

DOI: 10.1016/j.egypro.2013.07.271

CITATIONS

25READS

1,335

5 authors, including:

Some of the authors of this publication are also working on these related projects:

Texturization of silicon wafer View project

Mechanism of Silicon Etching by HF/HNO3 mixtures View project

Jörg Acker

Brandenburg University of Technology Cottbus - Senftenberg

113 PUBLICATIONS   1,710 CITATIONS   

SEE PROFILE

Tim Koschwitz

Brandenburg University of Technology Cottbus - Senftenberg

14 PUBLICATIONS   184 CITATIONS   

SEE PROFILE

Robert Heinemann

Brandenburg University of Technology Cottbus - Senftenberg

6 PUBLICATIONS   47 CITATIONS   

SEE PROFILE

All content following this page was uploaded by Jörg Acker on 28 May 2014.

The user has requested enhancement of the downloaded file.

Energy Procedia 38 ( 2013 ) 223 – 233

1876-6102 © 2013 The Authors. Published by Elsevier Ltd.Selection and/or peer-review under responsibility of the scientifi c committee of the SiliconPV 2013 conferencedoi: 10.1016/j.egypro.2013.07.271

ScienceDirect

SiliconPV: March 25-27, 2013, Hamelin, Germany

HF/HNO3 etching of the saw damage

Jörg Acker*, Tim Koschwitz, Birgit Meinel, Robert Heinemann, Christian Blocks

Hochschule Lausitz (FH), Fakultät für Naturwissenschaften, Großenhainer Straße 57, D-01968 Senftenberg, Germany

Abstract

Wet chemical etching of multicrystalline Si wafer in mixtures of hydrofluoric (HF) and nitric acid (HNO3) combines the removal of the saw damaged silicon lattice on top of the wafer with the creation of a certain surface morphology (texture) on the surface of the underlying bulk silicon. However, it is yet unclear how the kinetics of silicon etching, the constitution of the saw damage, and the resulting surface morphology are related to each other. As a first step to answer this question the etching of the saw damage was studied at three different levels: (i) The development of the surface morphology was studied with increasing etch depth. Regions of key morphological features were identified and parameters describing the morphological development were derived from the surface topography. (ii) The etch rate was studied as parameter that is very sensitive to changes regarding the bonding state of the etched silicon atoms. (iii) The surface chemistry of HF/HNO3 etched Si wafer was monitored by diffuse reflectance Fourier-transform infrared spectroscopy (DRIFT) in order to identify processes that are related to changes in the surface termination of silicon. By the combination of these three approaches a detailed picture from the etching of the saw damage, the development of the texture, and the interaction between structure and etch rate can be drawn. © 2013 The Authors. Published by Elsevier Ltd. Selection and/or peer-review under responsibility of the scientific committee of the SiliconPV 2013 conference Keywords: etching; texturization; morphology; saw damage; hydrogen termination

1. Introduction

The very intensively studies of the past years led to new and exciting kinetic, stoichiometric, and mechanistic information about the wet-chemical etching of monocrystalline silicon in hydrofluoric (HF) and nitric acid (HNO3) mixtures [1-7].

The major practical application of HF/HNO3 silicon etching is found in photovoltaics where it is the

* Corresponding author. Tel.: +49-3573-85-839; fax: +49-3573-85-809. E-mail address: joerg.acker@hs-lausitz.de.

Available online at www.sciencedirect.com

© 2013 The Authors. Published by Elsevier Ltd.Selection and/or peer-review under responsibility of the scientifi c committee of the SiliconPV 2013 conference

224 Jörg Acker et al. / Energy Procedia 38 ( 2013 ) 223 – 233

method of choice to remove the saw damage from multi crystalline as cut wafer. Furthermore, the etching generates a low reflective surface morphology, the texture, on the bulk silicon material consisting of shallow valleys (similar to partly hemispherical structures) in the micrometer range. This texture has the function to reflect the incident light to other spots within the wafer surface in order to increase the harvest of light and therefore the efficiency of the solar cell.

The etching of saw damaged silicon is full of challenges. The manufacture of solar wafer by multi-wire sawing of silicon bricks generates a mechanically damaged surface layer of very heterogeneous constitution. The topmost layer consists of amorphous silicon [8,9] followed by a very defect-rich region of fractures, cracks, and rifts caused by the fracture of the silicon lattice during the slicing process [10-12]. The defect density decreases by depth until the bulk silicon is reached. However, there are still isolated, very deep median cracks that can reach several micrometers into the bulk silicon [10-12]. Even the chemical behavior of the saw damaged silicon is unique. Recent results showed that etching the saw damage consumes more nitric acid than for monocrystalline bulk silicon [13], that horizontal etching leads to different morphologies between the upper and lower wafer side [14], and that the development of the morphology is different between slurry sawn and diamond wire sawn wafer [15].

To meet the both challenges of silicon etching in photovoltaics, namely removing the saw damage and proper shaping the bulk silicon material, requires the understanding of the ongoing processes. The present paper describes three different approaches to the etching of the saw damage as they are (i) the development of the surface morphology, (ii) the kinetics of etching, and (iii) the surface chemistry of HF/HNO3 etched Si wafers. The results show the manifold aspects and how they interact with each other and give a deeper inside about the importance of the saw damage for the formation of the surface texture.

Nomenclature

mas cut mass of the unetched as cut wafer

metched mass of the etched wafer

etch time

waferA wafer area

Si density of Si

r etch rate

d single side etch depth

2. Experimental

Etch solutions were prepared by weighing of aliquots from analytical grade hydrofluoric acid (40% (w/w)), nitric acid (65% (w/w) both from Merck, Darmstadt Germany), hexafluosilicic acid (35% (w/w)

were performed by horizontal immersion of 15 mm x 15 mm wafer pieces into 50mL etch solution thermostatted to a constant temperature by a refrigerated bath K12+CC2 (Huber Kältemaschinenbau GmbH Offenburg) and immersed in 3% (w/w) NaOH solution to remove the porous silicon layer. The following wafer material was studied: i) slurry sawn multicrystalline p-type silicon wafer of 180-200 μm thickness (neighboring wafer within one

Jörg Acker et al. / Energy Procedia 38 ( 2013 ) 223 – 233 225

brick), and ii) slurry sawn Si(100) single crystalline p-type silicon wafer of 180-200 μm. The etch rate, r, is calculated from eq. 1.

as cut etched

etch Si wafer etch

m mdrt A t

(1)

Eq. 1 can be rearranged to obtain the single side etch depth, d, which is used for the discussion

throughout this paper. The morphology of the etched surface was characterized by confocal microscopic

the etched wafer was determined by diffuse reflectance Fourier-transform Infrared spectroscopy (DRIFT) using an FT-IR spectrometer Nicolet iZ10 equipped with a liquid N2 cooled MCT detector and a Tech Collector II DRIFT unit all from ThermoFischer Scientific. Slurry sawn Si(100) wafer were hydrogen-terminated by etching in a mixture of 25 % (w/w) HNO3 and 20 % (w/w) HF in order to avoid the formation of amorphous silicon. To slow the etch rate a temperature of -5 °C was chosen.

3. Results and discussion

3.1. The development of the morphology

The micrograph of a 4° angle polished as cut slurry sawn mc-Si wafer in Fig. 1 visualizes the structure of a typical saw damage originated by slurry sawing. Starting the discussion from the top the surface of the wafer shows the typical fractured and cracked structure. This fractured zone of cracks and rifts persist within a depth of about 1.2 μm. Approximately at this depth the first appearance of a widely undamaged bulk silicon is observed. However, the zone below this depth exhibits still a considerable damage of deep median cracks and craters originated by deep lateral crack from which silicon material had been chipped away. The last zone starting at a depth of 2.8 μm consists exclusively of median cracks which reach very deep into the bulk material.

50 μm

2.8 μm ~1.2 μm

saw damage 50 μm

2.8 μm ~1.2 μm

saw damage

Fig. 1. Structure of the saw damage of a slurry sawn mc-Si wafer. The microscopic image was obtained from a 4° angle polished wafer. The beginning transition between saw damage and bulk silicon is found at a depth of about 1.2 μm.

226 Jörg Acker et al. / Energy Procedia 38 ( 2013 ) 223 – 233

8.20 μm6.58 μm5.15 μm3.24 μm

2.67 μm2.19 μm1.72 μm1.53 μm

0.38 μm 0.95 μm 1.14 μm 1.34 μm

8.20 μm6.58 μm5.15 μm3.24 μm

2.67 μm2.19 μm1.72 μm1.53 μm

0.38 μm 0.95 μm 1.14 μm 1.34 μm

Fig. 2. Micrographs from the upper side of horizontally etched slurry sawn mc-Si wafer as function of the single side etch depth (etch mixture: 30% (w/w) HNO3, 5% (w/w) HF, 10% (w/w) H2SiF6; temperature 10 °C; magnification 2100fold).

Fig. 2 shows a typical series of micrographs from the stepwise etching of the slurry sawn mc-Si wafer shown in Fig. 1. Already after a short time of etching the number of rifts (visibly as dark lines) seems to increase. It had already been shown that hidden details of the saw damage are revealed if the topmost silicon layer and silicon debris is removed by etching [14]. There is the very surprising observation that a substructure of tiny shallow pits, similar to the worm-like morphology of a textured surface, are already formed at etch depth between 0.95 μm and 1.14 μm. It is assumed that these worm-like pits are only formed on tiny islands of bulk silicon within the zone of the heavily damaged surface. As consequence, this depth range marks the beginning of the transition from the heavily damaged zone into mainly undamaged bulk material.

Ongoing etching leads to a broadening of the dark rifts and to a growth of the worm-like pits. At a depth between 1.72 μm and 2.19 μm all features of the heavily damaged surface, i.e. nests of tightly spaced fractures and trenches, are removed. However, the typical shell like fracture areas are still visibly and are apparently not yet attacked by the etchant. Any features of the saw damaged zone are etched away at a depth of 3.24 μm and the bottoms of very deep median cracks turned mainly into the bottoms of deep worm like valleys. Further etching to 5.15 μm increases the size of the worm-like structures in length and width on the expense of smaller ones. Finally, at depth around 6 μm and more the valleys grow wider and rounder. The same development is found for slurry sawn monocrystalline Si(100) wafer.

The development of the morphology of an etched wafer surface by means of quantitative parameters in

Jörg Acker et al. / Energy Procedia 38 ( 2013 ) 223 – 233 227

Fig. 3 is much more instructive than the visual inspection of micrographs. As relevant morphology parameters the count of valleys, the average valley area, and the area of the folded surface were identified. Remarkably, the curves in Fig. 3 are very similar regardless whether single or multi crystalline slurry sawn as cut wafer is etched and regardless whether the upper or lower side is considered.

0 1 2 3 4 5 6 7 8 9

2024283236

sur

face

are

a

etched depth (single wafer side) / μm

120016002000240028003200

ave

rage

valle

y ar

ea

mono Si(100) up side mono Si(100) down side multi Si up side multi Si down side

200

400

600

800

c)

b)

a)co

unt o

f val

leys

Fig. 3. Surface morphology parameters of horizontally etched slurry sawn mc-Si wafer vs. the single side etch depth (etch mixture: 30% (w/w) HNO3, 5% (w/w) HF, 10% (w/w) H2SiF6; temperature 10 °C; size of the analyzed surface area: 65 μm 90 μm).

The count of valleys increases up to an etch depth ob about 2.2 μm. Cracks and fractures are uncovered by etching and new etch pits are formed within the saw damage zone. The maximum count of valleys reached at the depth 2.2 μm coincidences with the point at which all features of the heavily damaged surface are removed. It appears that the period in which new etch pits can be formed is now finished. The count of valleys starts to decrease by etching the existing valleys in width and depth and leads to a growth of large valleys on the expense of the smaller ones. As more bulk silicon is removed as wider the valleys are etched yielding to fewer, but larger and round-shaped valleys (Fig. 3 at 8.20 μm).

The development of the average valley area (Fig. 3b) and the surface area (Fig. 3c) supports this interpretation. Within the first 2.2 μm the average valley size is initially low and decreases further; at the same time the total area increases. These accounts for the formation of new etch pits and for a preferential etching into the depth. According to Fig. 2 the surface morphology at 2.2 μm is characterized by many small worm-like valleys, shell like fracture areas, and a considerable number of deep median cracks are shaped by etching into large and wide trenches. Starting from here, these features are now transferred into the known uniform worm-like valleys of several micrometers in length. This decreases the number of valleys, increases their average size and flattens the surface so that the folded surface area decreases. At the same time the reflectivity of the surface increases (not shown here).

It has to be concluded that the etching of the as cut wafer proceeds in different stages. As long as the damages surface zone exists etching proceeds preferentially into the depth at cracks and fractures initially exposed or uncovered by etching of the top-most layer, or at other newly formed spots. As soon as the bulk phase is reached worm-like etch pits created in the bulk material. Then, the etching turns into a uniform enlargement of these worm-like structures.

228 Jörg Acker et al. / Energy Procedia 38 ( 2013 ) 223 – 233

3.2. Etch rates within the saw damage

Fig. 4a shows the typical dependence of the etch rate of as cut slurry sawn wafer from the etch time. The shape of the curves is very similar; the obvious difference are the diverging etch rates for long etch times. These differences display the variation of the etch rate with the composition of the etchant. The closer look reveals three different regions in which the etch rate shows a significant dependence that should be discussed as follows.

0 50 100 150 200 250 3000

100

200

300

400

500

etch depth / μm

b)a)

etch

rate

/ nm

per

sec

ond

etch time / s

Si(100) (30/5/10) mc-Si (30/5/10) mc-Si (36/4/13) mc-Si (32/4/13) mc-Si (28/4/13) mc-Si (24/4/13)

0 1 2 3 4 50

50

100

150

200

250

300

Fig. 4. Etch rate as function of the etch time for different slurry sawn as cut Si wafer (a) (etch temperature: 10 °C). The etch rate in the shoulder region is magnified and plotted vs. the etch depth (b). The numbers in round brackets indicate the composition of the

etchant. 30/5/10 corresponds to a mixture consisting of 30% (w/w) of HNO3, 5% (w/w) HF, and 10% (w/w) H2SiF6.

Region I covers the topmost approx. 0.3 μm of a single side wafer and is denoted a surface etch rate. This corresponds to the first few seconds of etching in which the initial etch rates is dramatically high with a maximum exceeding values up to 500 nm·s-1 depending on the composition of the etch mixture. The etching of this region lasts approx. from 10 s to 12 s. Within this period the etch rate drops dramatically indicating that this topmost layer is in fact very thin and the underlying saw damage region has its own etch rate. So far, this topmost region has no correspondence to the morphology discussed in the previous paragraph. The kinetic measurements give no hint why the silicon in the topmost region has a higher reactivity than bulk silicon. However, the existence of amorphous silicon on the wafer surface as shown by Bidiville et al. [8] was excluded by Raman measurements.

Region III starts at an etch depth of around 2 μm and can be described as bulk etch rate which depends on the given etchant composition and given temperature. This region is in accordance with the morphological features discussed above: The heavily damaged zone is mainly removed (except the deep median and lateral cracks) and the worm-like valleys start to growth in width (see Fig. 2). This is related with a very slightly decreasing of the bulk etch rate with increasing etch depth. It is known from chemical kinetics that the rate of an interface reaction depends on the interface area. This basic principle is fulfilled in a good agreement as shown by a plot of the etch rate vs. the surface area in Fig. 5. This relationship starts to be valid for etch depths of approx. 2 μm and deeper. The micrographs in Fig. 2 show that between 2 μm and 5 μm very deep median cracks are present. These isolated trenches have apparently no impact on the etch rate, i.e. their walls and bottoms seem to behave like bulk silicon at this stage.

Jörg Acker et al. / Energy Procedia 38 ( 2013 ) 223 – 233 229

16 20 24 28 32

30

40

50

60

surface area / a.u.

mono Si(100) up side mono Si(100) down side multi Si up side multi Si down side

etch

rate

/ nm

/s

2050 2100 2150 2200

Kub

elka

-Mun

k (n

orm

aliz

ed) /

a.u

.

wavenumber / cm-1

2138 cm-1

SiH3

2090 cm-1SiH

2114 cm-1

SiH2etch depth:

0.10 μm 0.19 μm 0.29 μm 0.48 μm 2.09 μm 4.56 μm

Fig. 5. Plot of the etch rate vs. the surface are for multicrystalline slurry sawn Si wafer. The linear relationship starts to be valid for a minimum etch depth of approx. 2 μm (etch mixture: 30% (w/w) HNO3, 5% (w/w) HF, 10% (w/w)

H2SiF6, temperature 10 °C).

Fig. 6. Intensity normalized DRIFT spectra of a successively etched slurry sawn Si(100) wafer (etch mixture: 25 % (w/w)

HNO3 and 20 % (w/w) HF, etch temperature: -5 °C).

Finally, the range between approx. 0.3 μm and approx. 2 μm in depth is denoted as region II. Their main feature is the shown shoulder in the etch rate which is more or less pronounced and more or less expanded to increasing etch depth depending on the composition of the etchant. This region corresponds mainly to the removal of the heavily damaged zone on one hand side as well as the beginning etching of bulk silicon islands within this damaged layer. Therefore, this region is characterized by a transition between saw damage etch rate and bulk etch rate.

3.3. Surface chemistry

In order to clarify the initially very high etch rates the surface species at etched slurry sawn as cut Si(100) wafer were monitored by DRIFT measurements as function of the etch depth (Fig. 6). The spectra in Fig. 6 are normalized by intensity because the intensity of diffuse scattered IR light decreases as flatter i.e. as higher reflective the silicon surface becomes by the etching. The loss of total intensity obeys the Kubelka-Munk equation. The peaks at 2090 cm-1, 2114 cm-1, and 2138 cm-1 are attributed to the monohydride (SiH), dihydride (SiH2), and trihydride (SiH3), respectively [16, 17]. A comprehensive survey about IR peak assignment of silicon surface species is found in [18-20].

The DRIFT spectra show that the Si surface is covered with hydrogen, mainly with SiH2 groups. Other species, such as partially fluorinated, were not detected. SiH2 is expected as the major species on the Si(100) surface since the ideal and bare Si(100) surface has two dangling bonds per Si atom, and hydrogen termination of those dangling bonds yields the dihydride Si. [17]. Monohydride species are only found in the very early stage of etching. The presence of SiH beside a vast majority of SiH2 on Si(100) surfaces is characteristic of a rough, hydrogen-terminated Si(100) surface with steps and kinks [21]. Niwano et al. studied the immersion of Si(100) in diluted HF solution and explained the loss of the SiH peak intensity by time by a slow etching of defect sites such as steps and kinks [22]. However, it is not clear whether this explanation is also valid for the loss of the SiH and SiH3 peak intensities in the present

230 Jörg Acker et al. / Energy Procedia 38 ( 2013 ) 223 – 233

study (Fig. 6). Nevertheless, the contributions of SiH and SiH3 signal to the total peak intensity is negligible so these surface species are not likely to impact the initial etch rate so dramatically as shown in Fig. 4. In consequence, the high etch rate found for the as cut wafer surface can not be explained by an initial termination with a specific, highly reactive SiHx species.

2050 2100 2150 2200 2250 2300

b)a)

2090 cm-12138 cm-1

SiH2

SiH

SiH3

HNO3 immersion time: 0 s (as etched) 20 s 60 s 100 s 200 s

2114 cm-1

2090 cm-1

2138 cm-1

Kub

elka

-Mun

k

wave number cm-1

2050 2100 2150 2200 2250 2300

2114 cm-1

Fig. 7. DRIFT spectra of the oxidation of a hydrogen terminated Si(100) wafer by immersion in 30% (w/w) HNO3 for several times. The hydrogen termination was obtained by etching a slurry sawn as cut Si(100) wafer by a 25 % (w/w) HNO3 and 20 % (w/w) HF

etch mixture at -5 °C to a depth of a) 4.56 μm and b) 0.10 μm.

The key to explain the initial high etch rate of the silicon atom located close to the as cut surface is found in a high oxidation rate of the SiHx species. For this purpose the etched wafer were immersed in 30% (w/w) HNO3 and the DRIFT spectra immediately measured after rinsing the wafer with deionized and degassed water. Oxidation of hydrogen terminated surfaces by water, in water dissolved air, air or humidified air leads primary to the insertion of oxygen atoms in the Si-Si backbond of the silicon-hydrogen surface species resulting to configurations in which, besides hydrogen atoms, two, or three oxygen atoms can be bound to the surface Si atom [17, 23-25]. This insertion leads to a shift of the SiHx bands to higher wave numbers resulting into a convolution of the DRIFT signal due to the variety of SiHx species and of (O)y-SiHx species (with x+y=3) in the range between 2050-2300 cm-1. [19, 20]

Fig. 7a shows the DRIFT spectra of a slurry sawn as cut Si(100) wafer surface that was etched by HNO3/HF to a depth of 4.56 μm and then subsequently oxidized by HNO3. The oxidation leads to an only decrease of the total peak area and to a only slight shift of the total peak towards higher wave numbers. However, due to the convolution single oxidized species can not be identified. The shown behavior is exemplarily for all wafer samples etched to a depth of 1.52 μm and more. This picture changes for wafer etched to depth of 0.76 μm or less. Fig. 7b) shows this exemplarily for a Si(100) wafer etched to a depth of 0.10 μm. Already after a 20 s immersion in HNO3 the wafer surface starts to oxidize as indicated by a loss of peak intensity in the SiH and SiH2 region and an immediately grown intensity at wave numbers above 2150 cm-1. An assignment of individual species is difficult, however, in these region the signals of mono and dihydride species with one or two oxygen atoms inserted per Si atom (e.g. H2Si(O)2 · · · SiH2, H2Si(O)2 · · · Si(O)H2, H2Si(O)2 · · · Si(O)2H2) and species bridged by oxygen atoms (e.g. H Si(O)2 O SiH, H Si(O)2 O Si(O) H, H Si(O)2 O Si(O)2 H) are located.

A simplified kinetic treatment of the oxidation is possible under the following assumption: The loss of SiHx peak area is exclusively due to the oxidation of the Si backbonds of SiH2 surface groups. The IR

Jörg Acker et al. / Energy Procedia 38 ( 2013 ) 223 – 233 231

signals of back bond oxidized SiH2 species are found at wavenumbers of 2150 cm-1 and higher so that only SiHx groups and no oxidized species contribute to the signal in the range between 2050 cm-1 and 2150 cm-1. By plotting the relative loss of the SiHx peak area in the range from 2050 cm-1 to the 2150 cm-1 (normalized to the peak area measured before HNO3 oxidation, i.e. immerdiately after HF/HNO3 etching) versus the etch time an exponential decay is obtained that can be fitted by a first order rate law. The resulting rate constants in Table 1 show clearly that the hydrogen terminated silicon surface is as slower oxidized as more of the saw damage is removed by etching.

Table 1. First-order rate constant for the oxidation of a hydrogen terminated slurry sawn Si(100) wafer vs. the etch depth.

Single side etch depth / μm 0.10 0.29 0.76 1.52 2.43 4.56

First-order rate constant / s-1 0.038 0.029 0.024 0.021 0.020 0.015

It has to be concluded that the upmost hydrogenates surface of the heavily damaged surface region up

to a depth of approx. 1.5 μm is much faster oxidized than the hydrogen termination on the bulk silicon. It is assumed that the silicon lattice in the heavily damaged region suffers from an enormous distortion of its lattice as well as from defects. This leads to a higher reactivity of the silicon surface causing the enormous high initial etch rate, the preferential etching of the saw damage into the depth, the creation of many new etch pits, and an increased count of valleys. The reactivity of the Si atoms decreases with the etch depth until the bulk silicon with its comparable less reactive hydrogen termination is present. This corresponds to the bulk etch rate.

4. Conclusion

The combination of confocal microscopy images, morphological parameters, kinetic measurements, and the study of the surface chemistry of the etching of slurry sawn Si wafer in HF/HNO3 mixtures gives a detailed insight into the structure of the saw damage. Based on the presented results, the following model is suggested:

The top of the saw damage is formed by a very strongly fractured surface possessing the typical saw teeth like morphology with a thickness of about 0.3 μm. Due to the abrasion and deformation processes during sawing a considerable number of cracks and fractures remain hidden until this top layer is etched away. Their etching proceeds with a very high etch rate because the saw damage weakens the Si lattice making the atoms more reactive and less stable against oxidation. The region between 0.3 and 2 μm in depth can be characterized as heavily saw damaged zone. Their top region between approx. 0.3 and 1.6 μm is dominated by the heavy lattice defects like in the surface layer. The Si-Si backbonds of SiHx species are easily oxidized, however, not as fast as in the top layer. However, this layer is etched with a still considerably high etch rate. At a depth of about 1 μm the first islands of bulk silicon appear within the saw damage, however, without any impact on the chemical properties of this defect controlled layer. In the region of 1.6 to 2 μm the heavily damaged zone becomes dominated by bulk silicon. The bulk number of silicon islands between the damaged zones increases strongly at a depth of about 1.7 μm. At the same time the etch rate in this zone decreases more and more. The oxidation behavior of silicon is now similar to that of bulk silicon. At a depth of about 2 μm any feature of the heavily damaged zone, like the nests of tight fractures are almost entirely removed. The surface is dominated by wide trenches and bulk silicon islands with tiny worm-like etch pits. At a depth of 2.8 μm the deepest lateral cracks and the deepest shell like fracture patterns are etched away. The deepest median cracks are found down to 3.3 μm. Once they are etched away the surface is covered with the worm-like moulds which are typical for a textured surface. Further etching leads to an increase of the mould size and at a depth of 5 μm and

232 Jörg Acker et al. / Energy Procedia 38 ( 2013 ) 223 – 233

more the moulds get wider, rounder, and flatter indication the chemical polishing of the wafer surface.

References

[1] Steinert M, Acker J, Henssge A, Wetzig K. Experimental studies on the mechanism of wet chemical etching of silicon in HF/HNO3 mixtures. J. Electrochem. Soc. 2005;152: C843-C850.

[2] Steinert M, Acker J, Krause M, Oswald S, Wetzig K. Reactive species generated during wet chemical etching of silicon in HF / HNO3 mixtures. J. Phys. Chem. B 2006;110:11377-11382.

[3] Weinreich W, Acker J, Gräber I. The effect of H2SiF6 on the surface morphology of textured multi-crystalline silicon. Semicond. Sci. Technol. 2006;21:1278-1286.

[4] Steinert M, Acker J, Oswald S, Wetzig K. Study on the mechanism of silicon etching in HNO3-rich HF/HNO3 mixtures. J. Phys. Chem. C 2007;111:2133-2140.

[5] Steinert M, Acker J, Wetzig K. New aspects on the reduction of nitric acid during wet chemical etching of silicon in concentrated HF/HNO3-mixtures. J. Phys. Chem. C 2008;112:14139-14144.

[6] Hoffmann V, Steinert M, Acker J. Analysis of gaseous reaction products of wet chemical silicon etching by conventional direct current glow discharge optical emission spectrometry (DC-GD-OES). J. Anal. At. Spectrom. 2011;26:1990-1996.

[7] Acker J, Rietig A, Steinert M, Hoffmann V. Mass and electron balance for the oxidation of silicon during the wet chemical etching in HF/HNO3 mixtures. J. Phys. Chem. C 2012;116:20380 20388.

[8] Bidiville A, Wasmer K, Kraft R, Ballif C. Diamond wire-sawn silicon wafer from the lab to the cell production. Proceedings of the 26th European Photovoltaic Solar Energy Conference and Exhibition; 2009, 1400-1405.

[9] Domnich V, Gogotsi Y. Phase transformation in silicon under contact loading. Rev. Adv. Mater. Sci. 2002;3:1-36. [10] Möller HJ. Basic mechanisms and models of multi-wire sawing. Advanced Engineering Materials 2004;7:501-513. [11] Möller HJ, Funke C, Rinio M, Scholz S. Multicrystalline silicon for solar cells. Thin Solid Films 2005;487:179 187. [12] Möller HJ. Wafering of silicon crystals. phys. stat. sol. (a) 2006;203:659 669. [13] Acker J, Steinert M, Hoffmann V, Schramm N, Suckow M. Mass and electron balance of silicon etching using HF/HNO3

mixtures - The formation of hydrogen and nitrous gases. Proceedings of the 26th European Photovoltaic Solar Energy Conference and Exhibition; 2011, 1662-1665.

[14] Meinel B, Heinemann R, Koschwitz T, Acker J. Etch kinetics and morphological investigation on the horizontal etching process. Proceedings of the 26th European Photovoltaic Solar Energy Conference and Exhibition; 2011, 1671-1673.

[15] Meinel B, Koschwitz T, Acker J. Textural development of SiC and diamond wire sawed sc-silicon wafer. Energy Procedia 2012;27:330-336.

[16] Niwano M, Miura T, Tajima R, Miyamoto N. Infrared study of chemistry of Si surfaces in etching solution. Appl. Surf. Sci. 1996;100/101:607-611.

[17] Miura T, Niwano M, Shoji D, Miyamoto N. Kinetics of oxidation on hydrogen-terminated Si(100) and (111) surfaces stored in air. J. Appl. Phys. 1996;79:4373-4380.

[18] Ehrley W, Butz R, Mantl S. External infrared reflection absorption spectroscopy of methanol on an epitaxially grown Si(100)2 × 1 surface. Surf. Sci. 1991;248:193-200.

[19] Rao GR, Wang ZH, Watanabe H, Aoyagi M, Urisu T. A comparative infrared study of H2O reactivity on Si(100)-(2 1), (2 1)-H, (1 1)-H and (3 1)-H surfaces. Surf. Sci. 2004;570: 178-188.

[20] Wang ZH, Urisu T, Watanabe H, Ooi K, Rao GR, Nanbu S, Maki J, Aoyagi M. Assignment of surface IR absorption spectra observed in the oxidation reactions: 2H + HO/Si(100) and HO + H/Si(100). Surf. Sci. 2005;575: 330-342.

[21] Dumas P, Chabal YJ, Jacob P. Morphology of hydrogen-terminated Si(111) and Si(100) surfaces upon etching in HF and buffered-HF solutions. Surf. Sci. 1992;269/270:867-878.

[22] Niwano M, Miura T, Kimura Y, Tajima R, Miyamoto N. Real-time, in situ infrared study of etching of Si(100) and (111) surfaces in dilute hydrofluoric acid solution. J. Appl. Phys. 1996;79:3708-3713.

Jörg Acker et al. / Energy Procedia 38 ( 2013 ) 223 – 233 233

[23] Cerofolini GF, Mascolo D, Vlad MO. A model for oxidation kinetics in air at room temperature of hydrogen-terminated (100) Si. J. Appl. Phys. 2006;100:054308.

[24] Niwano M, Kageyama J, Kinashi K, Sawahata J, Miyamoto N. Oxidation of hydrogen-terminated Si surfaces studied by infrared spectroscopy. Surf. Sci. 1994;301:L245-L249.

[25] Niwano M, Kageyama J, Kinashi K, Miyamoto N. Infrared spectroscopy study of initial stages of oxidation of hydrogen-terminated Si surfaces stored in air. J. Appl. Phys. 1994:76;2157-2163.

View publication statsView publication stats