单晶硅表面均匀小尺寸金字塔制备及其特性研究

表面织构是一种通过有效的光俘获增加短路电流从而提高太阳电池效率的主要途径之一.在加入间隙式超声和NaClO添加剂的碱性四甲基氢氧化铵(TMAH)溶液中对单晶硅表面进行织构化处理,研究超声与NaClO在织构过程中对金字塔成核和生长的影响,以及金字塔大小对高温工艺之后的单晶硅少子寿命的影响.研究表明,通过在织构溶液中加入间隙式超声控制气泡停留在硅片表面的时间和脱离硅片表面速度,增强了小尺寸金字塔的均匀分布.织构之后硅片在AM1.5G光谱下的加权平均反射率能够达到12.4%,在高温扩散和氧化之后少子寿命的大小与金字塔大小之间存在近似于指数衰减函数的关系. 关键词： 表面织构化 反射率 少子寿命 单晶硅太阳电池     

Reflectivity of porous-pyramids structured silicon surface

The antireflection of porous-pyramids structured silicon surface has been studied. The porous surface is formed by stain etching in HF/Fe(NO₃)₃ aqueous solution after textured in KOH/IPA solution. Reflectivity measurements show an overall reflectance of 4.2% for porous-pyramids textured silicon surface in the range from 400 to 900 nm. An optimal etching time of 30 min is obtained when both reflectivity and photo-generated carriers lifetime are considered. This technique may be probably used in the texturization process for high-efficiency silicon solar cells.     

A new texturing technique of monocrystalline silicon surface with sodium hypochlorite

This work proposes a new texturing technique of monocrystalline silicon surface for solar cells with sodium hypochlorite. A mixed solution consisting of 5 wt% sodium hypochlorite and 10 vl% ethanol has been found that results in a homogeneous pyramidal structure, and an optimal size of pyramids on the silicon surface. The textured silicon surface exhibits a lower average reflectivity (about 10.8%) in the main range of solar spectrum (400–1000 nm).     

Buried contact solar cell using tri-crystalline CZ silicon wafers

Tri-crystalline silicon wafers have been used for fabrication of buried contact solar cells. Optical properties and microstructures after texturing in KOH solution have been studied and compared with those of multi-crystalline silicon wafers. The textured surface of tri-crystalline wafer has a shape of V-groove with an angle of 109.48°. The efficiency of buried contact solar cell fabricated on tri-crystalline wafer measured to be 14.27% without optimization of cell process for tri-crystalline CZ wafer. Ray tracing computer simulations showed that V-groove composed of (1 1 1) after texturing can decrease reflectance significantly when cells are encapsulated. The reflectance can be reduced to about 4%, averaged over the 400–1100 nm wavelength range. The life time of tri-grain wafer was longer than that of multi-crystalline silicon wafer because it has only three twin boundaries in a wafer.     

Effect of surface morphology on screen printed solar cells

Surface texturing is well known as one of the major paths to improving the efficiency of silicon solar cells by increasing the short circuit current through effective photon trapping. However, the effects of the pyramids created after surface texturing on the other properties remain obscure. In this work, we studied the effect of the surface morphologies on the formation of both the emitter layer and metal electrode using the screen printing method, which is a cost-effective method of fabricating silicon solar cells. Various textured surfaces, such as with large, small, sharp or smooth pyramids, were investigated in comparison with a flat surface. The contact resistance was measured from a TLM patterned cell by I–V measurement under dark conditions and SEM, TEM and UV–vis spectrophotometer were used to evaluate the surfaces.     

新型添加剂对单晶硅表面金字塔形貌的影响

单晶硅表面微结构对晶体硅光电转换性能有非常重要的影响, 晶体硅表面微结构的调节技术一直是半导体、 太阳能电池领域研究的热点之一.利用碱液与单晶硅异向腐蚀特性的刻蚀技术, 在单晶硅表面可以获得布满金字塔的绒面, 但普通碱液刻蚀的绒面, 其金字塔大小、 形貌和分布随机性大, 不利于提高硅太阳电池的转换效率.在普通的碱腐蚀液中加入不同量的特种添加剂, 然后在相同的温度、 时间下刻蚀单晶硅表面, 通过观察样品表面SEM图, 发现在普通碱液中加入适量添加剂后刻蚀的单晶硅表面能形成均匀密集分布金字塔, 金字塔大小在2—4μupm 之间, 棱边圆滑, 表面金字塔覆盖率高; 用积分反射仪测量了样品的反射率曲线, 发现样品平均反射率下降到12.51%.实验结果表明, 在普通碱液中加入特种添加剂, 能控制单晶硅表面金字塔的大小和分布.     

氧化随机织构硅表面对单晶硅太阳电池性能的影响研究

热氧化生长的SiO\-2 薄膜经常在高效单晶硅太阳电池中被用作扩散掩膜,化学镀掩膜,钝化层或者基本的减反射层.在这些高效太阳电池中,经常使用碱性溶液对单晶硅表面进行处理,得到随机分布的正金字塔结构的织绒表面,减少表面的光反射.表面氧化后的正金字塔太阳电池暗反向电流-电压呈现"软击穿"现象,并联电阻明显下降.研究结果表明引起这些现象的原因在于氧化正金字塔表面会导致在体内形成位错型缺陷,这些缺陷能够贯穿整个pn 结,导致太阳电池的并联电阻下降,同时载流子在位错型缺陷在能隙中引入的能级处发生复合,导致空间电荷区 关键词： 热氧化 随机织构 位错 太阳电池     

Black multi‐crystalline silicon solar cells

A simple method for nano‐scale texturing of silicon surfaces based on local metal‐catalyzed wet chemical etching, which results in an almost complete suppression of reflectivity in a broad spectral range, has been successfully applied to produce black multi‐crystalline silicon solar cells. The performance of the cells is compared to that of reference cells without surface nano‐texturing. A considerable increase of the short circuit current (by 36–42% with respect to the reference cells) without deterioration of other performance parameters is observed under natural sun illumination. Means of further optimization of such black solar cells are discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Light trapping for a‐Si:H/µc‐Si:H tandem solar cells using direct pulsed laser interference texturing

We present a‐Si:H/µc‐Si:H tandem solar cells on laser textured ZnO:Al front contact layers. Direct pulsed laser interference patterning (DLIP) was used for writing arrays of one‐dimensional micro gratings of submicron period into ZnO:Al films. The laser texture provides good light trapping which is indicated by an increase in short‐circuit current density of 20% of the bottom cell limited device compared to cells on planar ZnO:Al. The open‐circuit voltage of the cells on laser textured ZnO:Al is almost the same as for cells on planar substrates, indicating excellent growth conditions for amorphous and microcrystalline silicon on the U‐shaped grating grooves. DLIP is a simple, single step and industrially applicable method for large area periodic texturing of ZnO:Al thin films. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Low cost anisotropic etching of monocrystalline Si (1 0 0): Optimization using response surface methodology

Reduced surface reflectance and enhanced light trapping is required by any high efficiency solar cell. Anisotropic etching was done on silicon (1 0 0) by using tetramethyl ammonium hydroxide TMAH, (CH₃)₄NOH, solution at 85 °C. Process variables considered were solution concentration and time proposed by response surface methodology (RSM). An effective surface texture was resulted with reflectance less than 8% without antireflection coating. The antireflection mechanism was also co-related with the etch rate of Si. Optimized values predicted by RSM for time and TMAH concentration were 5 min and 3.50% respectively. The technique and optimization of parameters by using response surface methodology (RSM) could be valuable in the texturization process for high-efficiency Si solar cells.     

表面钝化对多晶硅绒面形貌的影响

多晶硅表面制绒技术是太阳能光伏产业亟待突破的一个关键技术.本文根据多晶硅强酸制绒的基本原理,提出了表面活性剂钝化多晶硅表面以降低硅原子与酸反应速度从而改善多晶硅绒面形貌的方法.实验研究了不同含量的添加剂对酸液刻蚀多晶硅绒面形貌的影响,用扫描电镜观察对应的绒面结构,用积分反射仪测量其绒面的表面反射率.实验结果表明:加入活性剂后酸液能使多晶硅表面陷阱坑分布更加均匀,并且能有效消除产生漏电流的缺陷性深沟槽,样品表面反射率比较低,其表面反射率降低到21.5%.与传统酸液腐蚀的多晶硅绒面结构相比,陷阱坑密度明显增加,这种方法在多晶硅太阳电池的生产中是有价值的.     

单晶硅表面金字塔生长过程的实验研究

在普通碱液中添加一种特殊的添加剂,在不同时间下对单晶硅表面进行刻蚀.用扫描电子显微镜观察样品表面形貌,结果显示：单晶硅片放入加入添加剂2 mL的刻蚀液中,经过10 min刻蚀后晶体表面零星出现大小不一的金字塔,并有大面积的平滑区|刻蚀15 min后金字塔大小趋向一致,平滑区面积缩小|刻蚀20 min硅片表面形成平均尺寸为2～4 μm金字塔绒面结构,并且均匀性好、覆盖率高|刻蚀25 min后,进入过腐蚀阶段,金字塔出现变大的现象.研究表明：与传统碱腐蚀相比,添加剂可以缩短单晶硅刻蚀时间,并获得较为理想的绒面结构,在工业上应用可以降低生产成本和生产时间,提高生产率.     

Rapid optical measurement of surface texturing result of crystalline silicon wafers for high efficiency solar cells application

Surface texturing of crystalline silicon (c-Si wafers) wafers is a frequently used technique in high efficiency solar cells processing to reduce the light reflectance. Measuring the surface texturing result is important in the manufacturing process of high efficiency solar cells because the surface texturing of c-Si wafers is sensitive to the performance of reducing front reflection. Traditional approach for measuring surface roughness of texturing of c-Si wafers is atomic force microscopy. The disadvantage of this approach include long lead-time and slow measurement speed. To solve this problem, an optical inspection system for rapid measuring the surface roughness of texturing of c-Si wafers is proposed in this study. It is found that the incident angle of 60° is a good candidate for measuring surface roughness of texturing of c-Si wafers and y = ?188.62x + 70.987 is a trend equation for predicting the surface roughness of texturing of c-Si wafers. Roughness average (Ra) of texturing of c-Si wafers (y) can be directly determined from the peak power density (x) using the optical inspection system developed. The results were verified by atomic force microscopy. The measurement error of the optical inspection system developed is approximately 0.89%. The saving in inspection time of the surface roughness of texturing of c-Si wafers is up to 87.5%.     

Photonic nanostructures for advanced light trapping in silicon solar cells: the impact of etching on the material electronic quality

Dry plasma etching, commonly used by the Photonics community as the etching technique for the fabrication of photonic nanostructures, could be a source of device performance limitations when used in the frame of silicon photovoltaics. So far, the lack of silicon solar cells with state‐of‐the‐art efficiencies utilizing nanophotonic concepts shows how challenging their integration is, owing to the trade‐off between optical and electrical properties. In this study we show that dry plasma etching results in the degradation of the silicon material quality due to (i) a high density of dangling bonds and (ii) the presence of sub‐surface defects, resulting in high surface recombination velocities and low minority carrier lifetimes. On the contrary, wet chemical anisotropic etching used as an alternative, leads to the formation of inverted nanopyramids that result in low surface recombination velocity and low density of dangling bonds. The proposed inverted nanopyramids could enable high efficiency photonic assisted solar cells by offering the potential to achieve higher short‐circuit current without degrading the open circuit voltage. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

X-ray diffraction analysis of the silicon (111) surface during alkaline etching

We present a surface X-ray diffraction determination of the silicon (111)-liquid interface structure during alkaline etching. Preparation of an atomically smooth surface was realized by an in-situ procedure using an aqueous NH₄F solution devoid of oxygen. Using diluted aqueous potassium hydroxide (KOH) and ammonium fluoride (NH₄F) etchant, we have observed that the crystal surface is hydrogen terminated and is not reconstructed at open circuit potential. In addition, a partial liquid ordering of two water layers on top of the crystal surface was found, indicating a weak interaction with the hydrophobic, hydrogen terminated surface. We have followed in-situ the development of the oxide layer by a birth and spread mechanism during anodic passivation of the silicon surface.     

非晶硅锗电池性能的调控研究

采用射频等离子体增强化学气相沉积技术, 研究了非晶硅锗薄膜太阳电池. 针对非晶硅锗薄膜材料的本身特性, 通过调控硅锗合金中硅锗的比例, 实现了对硅锗薄膜太阳电池中开路电压和短路电流密度的分别控制. 借助于本征层硅锗材料帯隙梯度的设计, 获得了可有效用于多结叠层电池中的非晶硅锗电池. 关键词： 非晶硅锗薄膜太阳电池 短路电流密度 开路电压 带隙梯度     

Wet-chemical treatment and electronic interface properties of silicon solar cell substrates

On textured n-type silicon substrates for solar cell manufacturing, the relation between light trapping behavior, structural imperfections, energetic distribution of interface state densities and interface recombination losses were investigated by applying surface sensitive techniques. The field-modulated surface photovoltage (SPV), in-situ photoluminescence (PL) measurements, total hemispherical UV-NIR-reflectance measurements and electron microscopy (SEM) were employed to yield detailed information on the influence of wet-chemical treatments on preparation induced micro-roughness and electronic properties of polished and textured silicon substrates. It was shown that isotropic as well as anisotropic etching of light trapping structures result in high surface micro-roughness and density of interface states. Removing damaged surface layers in the nm range by wet-chemical treatments, the density of these states and the related interface recombination loss can be reduced. In-situ PL measurements were applied to optimise HF-treatment times aimed at undamaged, oxide-free and hydrogen-terminated substrate surfaces as starting material for subsequent solar cell preparations.      

基于BiFeO_3/ITO复合膜表面钝化的黑硅太阳电池性能研究

采用金属银辅助化学刻蚀法在制绒的硅片表面刻蚀纳米孔形成微纳米双层结构,以期获得高吸收率的太阳能电池用黑硅材料.鉴于微纳米结构会在晶硅表面引入大量的载流子复合中心,利用磁控溅射技术在黑硅太阳电池表面制备了BiFeO_3/ITO复合膜,并对其表面性能和优化效果进行了探索.实验制备的具有微纳米双层结构的黑硅纳米线长约180—320 nm,在300—1000 nm波长范围内入射光反射率均在5%以下.沉积BiFeO_3/ITO复合薄膜后的黑硅太阳能电池反射率略有提高,但仍然具有较强的光吸收性能;采用BiFeO_3/ITO复合膜的黑硅太阳能电池开路电压和短路电流密度分别由最初的0.61 V和28.42 mA/cm~2提升至0.68 V和34.57 mA/cm~2,相应电池的光电转化效率由13.3%上升至16.8%.电池综合性能的改善主要是因为沉积BiFeO_3/ITO复合膜提高了电池光生载流子的有效分离,从而增强了黑硅太阳电池短波区域的光谱响应,表明具有自发极化性能的BiFeO_3薄膜对黑硅太阳能电池的表面性能可起到较好的优化作用.     

Nanocrystalline ZnO film deposited by ultrasonic spray on textured silicon substrate as an anti-reflection coating layer

A ZnO thin film was successfully synthesized on glass, flat surface and textured silicon substrates by chemical spray deposition. The textured silicon substrate was carried out using two solutions (NaOH/IPA and Na₂CO₃). Textured with Na₂CO₃ solution, the sample surface exhibits uniform pyramids with an average height of 5 μm. The properties and morphology of ZnO films were investigated. X-ray diffraction (XRD) spectra revealed a preferred orientation of the ZnO nanocrystalline film along the c-axis where the low value of the tensile strain 0.26% was obtained. SEM images show that all films display a granular, polycrystalline morphology. The morphology of the ZnO layers depends dramatically on the substrate used and follows the contours of the pyramids on the substrate surface. The average reflectance of the textured surface was found to be around 13% and it decreases dramatically to 2.57% after deposition of a ZnO antireflection coating. FT-IR peaks arising from the bonding between Zn–O are clearly represented using a silicon textured surface. A very intense photoluminescence (PL) emission peak is observed for ZnO/textured Si, revealing the good quality of the layer. The PL peak at 380.5 nm (UV emission) and the high-intensity PL peak at 427.5 nm are observed and a high luminescence occurs when using a textured Si substrate.