Advanced etching of silicon based on deep reactive ion etching for silicon high aspect ratio microstructures and three-dimensional micro- and nanostructures

Different processes involving an inductively coupled plasma reactor are presented either for deep reactive ion etching or for isotropic etching of silicon. On one hand, high aspect ratio microstructures with aspect ratio up to 107 were obtained on sub-micron trenches. Application to photonic MEMS is presented. Isotropic etching is also used either alone or in combination with anisotropic etching to realize various 3D shapes.     

Characteristics of large‐scale nanohole arrays for thin‐silicon photovoltaics

Nanostructured crystalline silicon is promising for thin‐silicon photovoltaic devices because of reduced material usage and wafer quality constraint. This paper presents the optical and photovoltaic characteristics of silicon nanohole (SiNH) arrays fabricated using polystyrene nanosphere lithography and reactive‐ion etching (RIE) techniques for large‐area processes. A post‐RIE damage removal etching is subsequently introduced to mitigate the surface recombination issues and also suppress the surface reflection due to modifications in the nanohole sidewall profile, resulting in a 19% increase in the power conversion efficiency. We show that the damage removal etching treatment can effectively recover the carrier lifetime and dark current–voltage characteristics of SiNH solar cells to resemble the planar counterpart without RIE damages. Furthermore, the reflectance spectra exhibit broadband and omnidirectional anti‐reflective properties, where an AM1.5 G spectrum‐weighted reflectance achieves 4.7% for SiNH arrays. Finally, a three‐dimensional optical modeling has also been established to investigate the dimension and wafer thickness dependence of light absorption. We conclude that the SiNH arrays reveal great potential for efficient light harvesting in thin‐silicon photovoltaics with a 95% material reduction compared to a typical cell thickness of 200 µm. Copyright © 2012 John Wiley & Sons, Ltd.     

Studies on non-thermal atmospheric pressure plasma process conditions for groove formation on silicon nitride for silicon solar cells

Fabrications of narrow electrode grooves for front electrodes on single crystalline silicon solar cells were examined using surface discharges, in which the electrode grooves were formed by etching a silicon nitride (SiN) film on substrates. The surface discharge could effectively etch the SiN film within 10 s and that a high etching rate more than 1800 nm/min was obtained. An optimum ratio of Ar gas, which was enough to maintain the formation of innumerable surface streamers, was 2.3 times larger than that of etching gas, and a short-term etching with the high discharge voltage was effective to narrow groove width.     

多晶硅太阳电池背表面刻蚀提升其性能的产线工艺研究

对比研究了产线上多晶硅太阳电池背表面刻蚀对 其光电转换性能的影响。示范性实验结果表明:多晶硅太阳电池背表面刻蚀能够改善其短路 电流, 从而相应的光电转换效 率提升了约 0．1％。依据多晶硅太阳电池背表面刻蚀前后的扫描 电镜(SEM)形貌、背表面漫 反射光谱及完整电池片外量子效率的测试结果,改进的光电转换的原因可能源于背表面刻蚀 “镜面”化有利于太阳光子在背表面内反射和改进印刷Al浆与背表面覆盖接触。背表面刻蚀 与当前晶硅电池产线工艺兼容,能够提升电池片的光电转换效率,是一种可供选择的产线升 级工艺。     

Nanoporous black multi-crystalline silicon solar cells: realization of low reflectance and explanation of high recombination loss

Nanoporous black silicon (nb–Si) structures with/without saw damage removal (SDR) on solar-grade multi-crystalline silicon substrates have been formed by simple Ag-induced chemical etching. The  nb–Si shows a unique morphology of nano-scale holes on micron-scale patterns with low reflectance (<5%). The photovoltaic properties of nb–Si solar cells show that SDR process prior to Ag-induced chemical etching is an effective way to lower recombination and ohmic losses, resulting in significant efficiency enhancement of 26.0%. To further reduce the recombination loss for the nb–Si solar cells with ～10% efficiency, a two-layer emitter model has been introduced to explain the reduced emitter diffusion length that significantly lower spectral response. This suggests that removing residual Ag nanoparticles completely might be the key approach to enhance the spectral response of nb–Si solar cells with very low surface reflectance, thus increasing the final conversion efficiency.     

One-dimensional photonic crystal obtained by vertical anisotropic etching of silicon

The potentialities of vertical anisotropic etching of (110) silicon for the fabrication of one-dimensional photonic crystal with a high refractive index contrast have been studied. It is shown that advances toward the near-IR spectral range are limited by the mechanical strength of thin silicon walls. The device structures obtained consist of 50 trenches, 114 μm deep, with 1.8-μm-thick Si walls (structure period 8 μm). Their reflectance spectra in the wavelength range 2.5–16.5 μm show good agreement with calculation results, although the main photonic band gap at λ≈28±10 μm remained outside the spectral region of measurements. __________ Translated from Fizika i Tekhnika Poluprovodnikov, Vol. 36, No. 8, 2002, pp. 996–1000. Original Russian Text Copyright ? 2002 by Tolmachev, Granitsyna, Vlasova, Volchek, Nashchekin, Remenyuk, Astrova.     

准分子激光电化学刻蚀硅的刻蚀质量研究

为了解决现有硅刻蚀工艺中存在的刻蚀质量等问题,采用激光加工技术和电化学加工技术相结合的工艺对硅进行了刻蚀,研究了该复合工艺的工艺特性。实验中采用248nm-KrF准分子激光作光源聚焦照射浸在KOH溶液中的阳极n-Si上,实现激光诱导电化学刻蚀。在实验的基础上,研究了激光电化学刻蚀Si的刻蚀孔的基本形貌,并对横向刻蚀和背面冲击等质量问题进行了分析。结果表明,该工艺刻蚀的孔表面质量好、垂直度高;解决了碱液中Si各向异性刻蚀的自停止问题,具有加工大深宽比微结构的能力;也具有不需光刻显影就能进行图形加工的优越性。     

Optical and electrical properties of porous silicon layer formed on the textured surface by electrochemical etching

Porous silicon (PS) layers were formed on textured crystalline silicon by electrochemical etching in HF-based electrolyte. Optical and electrical properties of the TMAH textured surfaces with PS formation are studied. Moreover, the influences of the initial structures and the anodizing time on the optical and electrical properties of the surfaces after PS formation are investigated. The results show that the TMAH textured surfaces with PS formation present a dramatic decrease of reflectance. The longer is the anodizing time, the lower is the reflectance. Moreover, an initial surface with bigger pyramids achieved lower reflectance in short wavelength range. A minimum reflectance of 3.86 % at 460 nm is achieved for a short anodizing time of 2 min. Furthermore, the reflectance spectrum of the sample, which was etched in 3 vol.% TMAH for 25 min and then anodized for 20 min, is extremely flat and lies between 3.67% and 6.15% in the wavelength range from 400 to 1040 nm. In addition, for a short anodizing time, a slight increase in the effective carrier lifetime is observed. Our results indicate that PS layers formed on a TMAH textured surface for a short anodization treatment can be used as both broadband antireflection coatings and passivation layers for the application in solar cells.     

Formation of a silicon micropore array of a two-dimension electron multiplier by photo electrochemical etching

A semiconductor PEC etching method is applied to fabricate the n-type silicon deep micropore channel array. In this method, it is important to arrange the direction of the micropore array along the crystal orientation of the Si substrate. Otherwise, serious lateral erosion will happen. The etching process is also relative to the light intensity and HF concentration. 5% HF concentration and 10-15 cm distance between the light source and the silicon wafer are demonstrated to be the best in our experiments. The n-type silicon deep micropore channel array with aperture of 3μm and aspect ratio of 40-60, whose inner walls are smooth, is finally obtained.     

用于高效太阳电池的硅基微纳结构及制备

介绍了用于高效太阳电池的几种硅基微纳结构的最新研究进展,重点介绍了几种硅基微纳结构的制备方法,如阳极腐蚀制备多孔硅、各向异性制绒以及气液固(VLS)生长纳米线等,并对各种方法的特点作了分析比较,指出了各种方法存在的问题。最后对今后研究的方向做了展望,由于太阳电池在性能提高以及产业应用方面的需求,未来用于高效太阳电池的硅基微纳结构仍是研究的热点之一。进一步提升其对太阳电池效率的优化能力将是研究的重要关注点,而其制备技术也将向着低成本、大规模及可控制的方向发展。     

Research and development of deep anisotropic plasma silicon etching process to form MEMS structures

Process characteristics of deep silicon etching as a function of its operational parameters are investigated. A process of deep anisotropic plasma etching process is developed and optimized to form MEMS silicon structures. The results of the work are used in forming MEMS working structures.     

Passivation of photonic nanostructures for crystalline silicon solar cells

We report on the optical and electrical performances of periodic photonic nanostructures, prepared by nanoimprint lithography (NIL) and two different etching routes, plasma, and wet chemical etching. Optically, these periodic nanostructures offer a lower integrated reflectance compared with the industrial state‐of‐the‐art random pyramid texturing. However, electrically, they are known to be more challenging for solar cell integration. We propose the use of wet chemical etching for fabricating inverted nanopyramids as a way to minimize the surface recombination velocities and maintain a conventional cell integration flow. In contrast to the broadly used plasma etching for nanopatterning, the wet chemically etched nanopatterning results in low surface recombination velocities, comparable with the state‐of‐the‐art random pyramid texturing. Applied to 40‐µm thick epitaxially grown crystalline silicon foils bonded to a glass carrier superstrate, the periodic‐inverted nanopyramids show carrier lifetimes comparable with the non‐textured reference foils (τ_eff = 250 µs). We estimate a maximum effective surface recombination velocity of ~8 cm/s at the patterned surface, which is comparable with the state‐of‐the‐art values for crystalline silicon solar cells. Copyright © 2014 John Wiley & Sons, Ltd.     

Reactive sputter etching of silicon with very low mask-material etch rates

Directional etching of deep structures in silicon is often made difficult by a high mask erosion rate. Recent results have given a Si/SiO2etch rate ratio of up to 8 without the undercut problems associated with other selective etches. In this paper a new selectivity mechanism is described which can reproducibly give Si/SiO2etch rate ratios of more than 100 with a nonloading target, and more than about 50 with a loading target. Similar etch ratios are also obtained with masks of MgF2, Al2O3, Al, and Cr. The inherently high Si/SiO2etch rate ratio obtained in Ar/Cl2discharges is here enhanced by causing selective deposition of SiO2onto slowly etched materials. The silicon may be obtained from the target, or, for easier control, from input gases such as SiCl4. The deposition rate is controlled by the oxygen concentration. The results of etching deep grooves in Si are presented. Etch-mask faceting and Si surface decoration appear to limit the attainable etch rate ratios with fine structures; however, 18-µm-deep gratings of 4.5-µm period have been etched in Si.     

One-mask process for silicon accelerometers on Pyrex glass utilising notching effect in inductively coupled plasma DRIE

A one-mask process technology is proposed to fabricate silicon capacitive accelerometers using comb drive structures. A doped silicon wafer is anodically bonded on Pyrex glass substrate. High aspect ratio silicon accelerometer structures are micromachined using deep reactive ion etching (DRIE) and released from the glass substrate by further DRIE due to its notching effect.     

Highly transparent modulated surface textured front electrodes for high‐efficiency multijunction thin‐film silicon solar cells

To further increase the efficiency of multijunction thin‐film silicon (TF‐Si) solar cells, it is crucial for the front electrode to have a good transparency and conduction, to provide efficient light trapping for each subcell, and to ensure a suitable morphology for the growth of high‐quality silicon layers. Here, we present the implementation of highly transparent modulated surface textured (MST) front electrodes as light‐trapping structures in multijunction TF‐Si solar cells. The MST substrates comprise a micro‐textured glass, a thin layer of hydrogenated indium oxide (IOH), and a sub‐micron nano‐textured ZnO layer grown by low‐pressure chemical vapor deposition (LPCVD ZnO). The bilayer IOH/LPCVD ZnO stack guarantees efficient light in‐coupling and light trapping for the top amorphous silicon (a‐Si:H) solar cell while minimizing the parasitic absorption losses. The crater‐shaped micro‐textured glass provides both efficient light trapping in the red and infrared wavelength range and a suitable morphology for the growth of high‐quality nanocrystalline silicon (nc‐Si:H) layers. Thanks to the efficient light trapping for the individual subcells and suitable morphology for the growth of high‐quality silicon layers, multijunction solar cells deposited on MST substrates have a higher efficiency than those on single‐textured state‐of‐the‐art LPCVD ZnO substrates. Efficiencies of 14.8% (initial) and 12.5% (stable) have been achieved for a‐Si:H/nc‐Si:H tandem solar cells with the MST front electrode, surpassing efficiencies obtained on state‐of‐the‐art LPCVD ZnO, thereby highlighting the high potential of MST front electrodes for high‐efficiency multijunction solar cells. Copyright © 2015 John Wiley & Sons, Ltd.     

On the application of thin films of silicon nanoparticles for increasing solar cell efficiency

The effect of thin films of silicon nanoparticles (nc-Si), deposited onto the front surface of single-crystal silicon solar cells, on their conversion efficiency is studied. The thin films are grown using non-luminescent silicon nanoparticles with an average diameter of 12 nm with SiO _x (0 ≤ x ≤ 2) shells and silicon nanoparticles 2 nm in diameter with organic shells of octadecene, which exhibit photoluminescence in the red spectral region. It was found that nc-Si film deposition increases the solar-cell conversion efficiency by 12% with respect to the initial value. An analysis of the current-voltage characteristics and reflectance spectra of solar cells allows the conclusion that the increase in the conversion efficiency is controlled by the passivation of defects on the front surface of the solar cell by nanoparticles and a decrease in the light reflectance of this surface.     

Relation between light trapping and surface topography of plasma textured crystalline silicon wafers

Currently, in the photovoltaic industry, wet chemical etching technologies are used for saw damage removal and surface texturing. Alternative to wet chemical etching is plasma etching. However, as for example, the linear microwave plasma technique, developed by Roth&Rau, has not been implemented in the photovoltaic industry for etching, because of the very low etch rate (<1 µm/min) and the high cost of ownership related to the etching process. In this study, different front surface textured crystalline silicon wafers obtained by means of the linear microwave plasma technique and the expanding thermal plasma technique are investigated in terms of weighted reflection by using reflectometry (250–1200 nm) to study the optical properties of the textures in detail. In addition, atomic force microscopy is used to measure the surface topography to determine statistical roughness parameters, as presented in this paper. Effective light trapping can be obtained by multiple reflections as well as by a graded layer, which leads to a diffuse front surface, or a combination of both. A graded layer can be described as a smooth transition with increasing refractive index from air to silicon with typical thickness of (200 ± 50) nm. We have found that the average plane tilt angle correlates to the measured weighted reflection. Moreover, we can determine from the aspect ratio whether the light trapping is effective by multiple reflections. From the roughness exponent, which is a measure for the micro roughness, we can determine whether the light trapping is effective by a graded layer. Copyright © 2013 John Wiley & Sons, Ltd.     

亚硝酸钠刻蚀液对多晶硅表面陷阱坑形貌的影响

酸刻蚀多晶硅表面技术是当前太阳能研究的热点之一。利用亚硝酸钠比硝酸钠氧化能力弱的特点,在普通酸刻蚀液中用亚硝酸钠取代硝酸配制多晶硅表面刻蚀液,然后在相同的工艺条件下刻蚀多晶硅表面。实验样品的SEM显示:含有NaNO2酸刻蚀液使多晶硅表面能布满蚯蚓状的腐蚀坑,腐蚀坑的深度比传统的酸刻蚀的陷阱坑深,而且密度分布比较均匀,样品平均反射率下降到23.5%,与传统配方酸刻蚀液刻蚀的多晶硅表面相比,平均反射率下降了8%左右。     

Theoretical comparison of conventional and multilayer thin silicon solar cells

Thin solar cells based on low-quality silicon are assessed for a range of possible material parameter values and device structures. Device thickness is freely optimized for maximum efficiency for a range of doping densities and numbers of junctions, le ading to results differing markedly from previous investigations. Modelling of conventional and multilayer structures in this paper indicates little difference in efficiency potential on low-lifetime (<50 ns) crystalline silicon layers. Moderate effici encies (>15%) are possible given adequate light trapping. Conventional structures (single and double junction cells) are superior if excellent light trapping is assumed. Thicker multilayer structures are advantageous in the case of poor light trapping or surface passivation. In an optimized cell in low-quality silicon, increasing the number of junctions allows a high current to be maintained, but at the cost of a reduced voltage and fill factor caused by increased junction recombination. Formidable pra ctical difficulties are likely to be encountered to realize the theoretical performances discussed.     

三维掩膜硅各向异性腐蚀工艺释放微悬空结构

提出了一种新颖的基于三维掩膜的硅各向异性腐蚀工艺,即利用深反应离子刻蚀、湿法腐蚀等常规体硅刻蚀工艺和氧化、化学气相沉积(CVD)等薄膜工艺制作出具有三维结构的氧化硅(SiO2)或氮化硅(Si3N4)薄膜,以该三维薄膜作为掩膜进行各向异性腐蚀,该工艺可以应用于MEMS微悬空结构的制作。利用该工艺成功地在单片n-Si(100)衬底上完成了一种十字梁结构的释放,并对腐蚀的过程和工艺参数进行了研究。