APPLIED PHYSICS LETTERS 88, 203107 2006

Black nonreecting silicon surfaces for solar cells

Svetoslav Koynov,a Martin S. Brandt, and Martin Stutzmann
Walter Schottky Institut, Technische Universitt Mnchen, 85748 Garching, Germany

Received 28 December 2005; accepted 2 April 2006; published online 16 May 2006 We present a wet chemical process for nanoscale texturing of Si surfaces, which results in an almost complete suppression of the reectivity in a broad spectral range, leading to black Si surfaces. The process affects only the topmost 200 300 nm of the material and is independent of the surface orientation and doping. Thus, it can be applied to various structural forms of bulk silicon single, poly-, or multicrystalline as well as to thin Si lms amorphous or microcrystalline . The optical properties of various black Si samples are presented and discussed in correlation with the surface morphology. 2006 American Institute of Physics. DOI: 10.1063/1.2204573 Silicon with various structural morphologies is widely used for solar cells and other optoelectronic devices. However, at Si surfaces have a high natural reectivity with a strong spectral dependence. The minimization of reection losses is of crucial importance, in particular, for high efciency solar cells, and hence, a variety of approaches has been developed to this end, in many cases specic to a particular surface morphology. A common solution is antireection coatings ARC based on interference. For example, quarter wavelength transparent layers of SiOx, TiOx, ZnO, ITO, or Si3N4 are regularly used as ARCs on Si.1 Alternatively, ARCs from oxidized nanoporous silicon can be formed by electrochemical etching.2 Such coatings are resonant structures and perform well only in a limited spectral range and for specic angles of incidence. Their typical net effect in the entire usable spectral range of Si is an average reduction of the surface reection to about 8%15%. Efcient suppression of reection in a broad spectral range has been achieved by deep surface texturing.3 Rough surfaces with spikes and pits having typical sizes of several micrometers exhibit a reduced reectivity due to the multiple reection and absorption. The best antireection textures, prepared by anisotropic etching of Si in KOH / C2H5OH mixtures, consist of densely packed pyramids and appear black, but are limited to single crystalline Si with 100 surface orientation. Also, the large penetration of the etched pyramids into the Si wafer complicates solar cell design. In addition, the reectivity of these surfaces increases rapidly with the angle of light incidence. An appealing approach to minimize reectivity utilizes a ne surface texture, comprising features on the nanometer scale. Stephens and Cody have proposed a model assuming that a textured surface with features smaller than the wavelength of light is an effective medium with gradually varying optical constants.4 The model predicts that the reectivity of such a boundary layer is vanishing for wavelengths below a cutoff threshold which depends on the complex refractive index of the bulk material as well as on the density prole and depth of the textured layer. Accordingly, the reectivity cutoff for textured silicon surfaces with a linearly increasing density should appear at a wavelength four to six times larger
a

than the depth of the textured layeri.e., a ne texture of only 200 300 nm in depth should be enough to suppress the reectivity of a Si surface in the whole usable spectral range of photon energies above the band gap. These predictions have been conrmed experimentally via the preparation of randomly textured Si surfaces with nanoscale features by sputtering etching.5 Similar techniques based on reactive ion etching RIE have been developed recently, employing selective etching through discontinuous SiO2 micromasks6 or utilizing the catalytic action of various metals during the ion etch process.7 However, the ion damage associated with RIE, difculties with obtaining an uniform texturing on larger areas above 100 cm2 , and the complexity of the plasma processes involved are of concern regarding a large scale solar cell production. Here, we present a method for nanoscale texturing of silicon surfaces, which utilizes simple wet chemical etching, facilitated by the presence of small metal clusters. Three kinds of silicon samples were used to demonstrate the universality of the method with respect to surface structure and doping: single crystalline Si n type , bulk multicrystalline Si p type , and thin lms of amorphous hydrogenated Si a-Si: H, intrinsic . Using optical transmission and reection measurements, we demonstrate that the optical losses due to surface reection can be reduced to below 5% throughout the entire usable spectrum, from 350 to 1000 nm wavelength for crystalline Si. The samples are rst cleaned in acetone and isopropyl alcohol, followed by a HF dip to remove the natural oxide from the surface. The texturing process, referred to as black etch in the following, is performed in three steps. i A tiny amount of metal is deposited in the form of nanoclusters onto the at Si surface. The composition and structure of this initial coating determine the texture and optical properties obtained. A typical treatment starts from Au layers with a nominal thickness of 1 2 nm, deposited by thermal evaporation at a pressure of 105 106 mbar. Such layers are discontinuous, comprising clustered grains of several nanometer sizes with about 20%40% of exposed Si surface between them. For other nominal layer thicknesses, no pronounced suppression of reectivity has been achieved. A detailed survey of the engineering of the initial metal coating using different metals, deposition techniques, and postdeposition treatments with

Author to whom correspondence should be addressed; electronic mail: koynov@wsi.tum.de

0003-6951/2006/88 20 /203107/3/$23.00 88, 203107-1 2006 American Institute of Physics Downloaded 15 Jul 2008 to 129.187.254.46. Redistribution subject to AIP license or copyright; see http://apl.aip.org/apl/copyright.jsp

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FIG. 2. a Atomic force micrograph of a textured crystalline Si surface. b Depth histogram of a . c Variation of the Si fraction with depth from the surface. FIG. 1. Total reection spectra a and total transmission spectra b of black etched crystalline Si surfaces. Three different samples are compared: wafer 1, where both sides are polished; wafer 2, where the illuminated side has been treated; wafer 3, where both sides are treated. Egap denotes the indirect band gap of crystalline Si.

ii

iii

respect to the optical effects obtained will be published separately. A wet chemical etching of the Si substrate is performed as the second step of the texturing process. The etching is carried out at room temperature in an aqueous solution of hydrouoric acid and hydrogen peroxide with volume ratio HF 50% : H2O2 30% : H2O = 1 : 5 : 10. This solution etches clean Si surfaces very slowly etch rate below 1 nm/ min , preserving the surface polish and not changing the reectivity. An exception is heavily doped p-type Si, on which the formation of a thin porous silicon layer was observed. In contrast, dramatic modications of the optical properties occur if the Si substrates are partially covered by Au clusters according to i . The duration of this etching step can be conveniently controlled visually, as an initially polished Si surface turns completely black within 50 90 s only. Finally, the remaining Au is removed from the textured Si surface by room temperature etching in aqueous solution of iodine and potassium iodide 25 g I and 100 g KI per 1 l H2O .

Figure 1 summarizes the major optical effects of the black etch treatment applied to a 100 oriented, n-type, single crystalline Si sample with initially double-side polished surfaces. The same effects have been observed for samples with different crystallographic orientation and doping. All optical spectra were measured for nearly normal light incidence 3 offset covering the spectral regions above and below the Si band gap with a standard UV-VIS spectrometer Perkin Elmer Lambda 900 and an integrating Ulbrich sphere. In the region of Si absorption, the reection spectrum of the untreated sample Fig. 1 a , curve 1 shows the typical high reectivity of the front polished surface. The high reectivity below the fundamental absorption gap Egap of Si is

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due to the contribution of both polished surfaces. The corresponding transmission Fig. 1 b , curve 1 in this region is limited exclusively by the total reectivity of the sample. After performing a black etch treatment only on the front surface for 90 s, the total reectivity in the usable spectral region above Egap has decreased down to a few percent Fig. 1 a , curve 2 . In the region of Si transparency, the decreased reection of the treated surface is accompanied by a corresponding increase of the transmission. A subsequent black etch of the rear surface both sides treated, curves 3 results in the suppression of reectivity also in the region of Si transparency, and in a corresponding increase of the transmission through the entire sample to levels exceeding 90%. In the region below Egap, the sum of reection and transmission for each sample equals 100% within an experimental error of 2% . This clearly demonstrates that there is no additional absorption at the modied surfacesi.e., the treated surfaces are genuinely antireecting. Moreover, the optical effect of the treatment is bidirectional, it equally affects photons crossing the surface from air into Si and vice versa. The origin of the optical effects produced by the black etch can be understood from the morphology of the etched Si surface shown in Fig. 2. The atomic force micrograph AFM, Fig. 2 a shows densely packed random hillocks of lateral sizes within the range of 50 100 nm. The histogram in Fig. 2 b shows the depth distribution of the surface and reveals that the texture penetrates about 250 nm into the Si bulk. The same distribution is observed in AFM images taken from other spots of the sample on areas up to 12 12 m2, indicating that the texture is uniform. The lateral sizes of the texture features are smaller than the wavelength of the incident light within the Si material in the whole range of strong absorption and, so, the effective medium approximation can be applied. The fractional area occupied by Si as a function of the depth across the textured layer, calculated from the histogram, is shown in Fig. 2 c . It reveals a very smooth increase of density i.e., of refractive index up to a depth, 1 which is about 4 of the wavelength corresponding to Egap, as required by the model of Stephens and Cody.4 The fact that in the presence of Au clusters a texture with a depth of up to 250 nm forms in Si by the etching within 90 s, while the etch rate of clean Si in the same etching solution is lower than 1 nm/ min, clearly shows the catalytic action of the Au clusters. A suitable reaction scheme, where

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Appl. Phys. Lett. 88, 203107 2006

FIG. 3. a Photograph of black etched Si samples of different crystal structures and dopings. c-Si n denotes a bulk single crystalline silicon sample with 100 orientation, n-type doping, and 2.5 cm resistivity; cast-Si p a bulk multicrystalline silicon, p-doped sample also with 2.5 cm resistivity; and a-Si: H i a nominally undoped thin lm of amorphous hydrogenated a-Si: H on a glass substrate, with a thickness of 500 nm. For comparison with the initial surfaces, the upper part of each sample is left untreated. b Total hemispherical reection spectra of the treated areas of the samples from a . The data for a-Si: H are shown as measured and after removal of the interference fringes.

FIG. 4. Internal absorption spectra of the black etched crystalline Si a and thin lm a-Si: H b in comparison with the corresponding absorption of the untreated samples.

metal clusters act as nanocathodes and the exposed Si spots between them as nanoanodes, can be found, e.g., in the work of Li and Bohn.8 However, the pronounced optical effects described here have not been observed in that work, although a very similar etching process was investigated. This discrepancy might be related to the slightly thicker metal coatings 3 8 nm or to the more concentrated etching solution HF : H2O2 : C2H5OH = 1 : 1 : 1 used by Li and Bohn. We have also observed formation of textures with larger features, resulting in much weaker optical effects, when using metal coatings thicker than 3 nm. This indicates that the structure of the initial metal coating is of crucial importance for the nal Si surface topology. Figure 3 illustrates the ability of the black etch treatment to produce the desired optical antireection properties on different silicon surfaces. Three silicon samples with different morphologies crystalline, multicrystalline, and amorphous and doping n type, p type, and intrinsic are shown. Initially, all three samples had polished or smooth surfaces. The major part of each sample surface bottom parts in Fig. 3 a has been modied, while the rest remained untreated for direct comparison. The treated areas of all samples appear similarly black, even under non-normal incidence. Small differences in the reectivity of the crystallites in the cast-Si sample are visible after treatment, indicating a slight variation in the textures obtained. In distinct contrast, all untreated areas have a high reectivity, as seen by the mirror images of the labels above them. The spectra in Fig. 3 b quantify the similar, uniformly suppressed reectivity of as little as 2%5% in the high absorption ranges of all three samples. The benecial optical effects of the modied surfaces can be seen in Figs. 4 a bulk Si and 4 b a-Si: H thin lm . The net internal absorption A is calculated from the

corresponding reection R and transmission T, according to R + T + A = 1. The amount of absorbed light is signicantly increased after the surface treatment. The increase at wavelengths below the absorption edge obviously originates from the suppressed reection. The spectrum of the treated a-Si: H lm also shows an apparent shift of the absorption edge towards longer wavelengths. This can be attributed to the enhancement of absorption in this region due to efcient light trapping. A detailed study of this phenomenon will be published separately. The simple and fast black etch treatment, demonstrated in this work, can be applied to the surfaces of bulk and thin lm silicon of various structural forms and doping. It results in a nearly complete suppression of surface reectivity in the entire region of high optical absorption of Si, with a concomitant enhancement of the light coupling into the absorbing Si bulk. Moreover, an efcient light trapping in the region of weak optical absorption of thin Si lms can be obtained. These effects represent signicant improvements of the optical performance for bulk single- or multicrystalline Si, as well as for thin lms of a-Si: H and c-Si: H. The observed optical effects are explained by the formation of a nanoscale texture on the Si surface, representing an effective medium with a smooth transition of the refractive index from that of air to that of Si. The texture, created by the black etch, affects only the topmost 200 300 nm of the Si material and is laterally uniform on large areas. This opens opportunities for the design of efcient solar cells and other optoelectronic devices.
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A. Atzek, J. J. Capart, R. L. Carabb, K. H. Heffels, and G. Seibert, Proceedings of the International Colloquium ECOSEC, Toulouse, 1970 Gordon and Breach, New York, 1971 , p. 349. 2 A. Prasad, S. Balakrishnan, S. K. Jain, and G. C. Jain, J. Electrochem. Soc. 129, 596 1982 . 3 M. A. Green, Silicon Solar Cells: Advanced Principles and Practice Bridge, Sydney, 1995 . 4 R. B. Stephens and G. D. Cody, Thin Solid Films 45, 19 1977 . 5 J. I. Gittleman, E. K. Sichel, H. W. Lehmann, and R. Widmer, Appl. Phys. Lett. 35, 742 1979 . 6 D. S. Ruby, W. K. Schubert, J. M. Gee, and S. H. Zaidi, U.S. Patent No. 6,091,021 2000 . 7 D. S. Ruby and S. H. Zaidi, U.S. Patent No. 6,329,296 2001 . 8 X. Li and P. W. Bohn, Appl. Phys. Lett. 77, 2572 2000 . Downloaded 15 Jul 2008 to 129.187.254.46. Redistribution subject to AIP license or copyright; see http://apl.aip.org/apl/copyright.jsp