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     

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).     

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     

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.     

Effects of textured morphology on the short circuit current of single crystalline silicon solar cells: Evaluation of alkaline wet-texture processes

The effect of different surface morphologies obtained by anisotropic etching on the light trapping and short circuit current of single crystalline silicon solar cells was investigated. The anisotropic texturing of a (1 0 0) silicon surface was performed using potassium hydroxide (KOH) solution and/or tetramethylammonium hydroxide (TMAH) solution including isopropyl alcohol (IPA) additive or tertiary butyl alcohol (TBA) additive. Texturing in TMAH solution formed smaller pyramids on the textured surface compared with texturing in KOH solution. Although the textured samples showed similar reflectances (except in the case of the TBA additive), they showed different short circuit currents. Texturing in KOH/TMAH solution led to a 9.6% increase in short circuit current compared with texturing in KOH/IPA solution, a typical etchant in commercial processes. Based on these results, the reflectivity has no simple proportionality relationship to the short circuit current, and the short circuit current of silicon solar cells should be the criterion used in evaluating texturing effects on reducing reflectance and forming a sound junction with high collection efficiency.     

Electrical and optical properties of nanowires based solar cell with radial p-n junction

In our studies the absorption, transmittance and reflectance spectra for periodic nanostructures with different parameters were calculated by the FDTD (Finite-Difference Time-Domain) method. It is shown that the proportion of reflected light in periodic structures is smaller than in case of thin films. The experimental results showed the light reflectance in the spectral range of 400–900 nm lower than 1% and it was significantly lower in comparison with surface texturing by pyramids or porous silicon.Silicon nanowires on p-type Si substrate were formed by the Metal-Assisted Chemical Etching method (MacEtch). At solar cells with radial p-n junction formation the thermal diffusion of phosphorus has been used at 790 °C. Such low temperature ensures the formation of an ultra-shallow p-n junction. Investigation of the photoelectrical properties of solar cells was carried out under light illumination with an intensity of 100 mW/cm². The obtained parameters of NWs' solar cell were I_sc = 22 mA/cm², U_oc = 0.62 V, FF = 0.51 for an overall efficiency η = 7%. The relatively low efficiency of obtained SiNWs solar cells is attributed to the excessive surface recombination at high surface areas of SiNWs and high series resistance.     

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...     

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.     

Wet-chemical passivation of atomically flat and structured silicon substrates for solar cell application

Special sequences of wet-chemical oxidation and etching steps were optimised with respect to the etching behaviour of differently oriented silicon to prepare very smooth silicon interfaces with excellent electronic properties on mono- and poly-crystalline substrates. Surface photovoltage (SPV) and photoluminescence (PL) measurements, atomic force microscopy (AFM) and scanning electron microscopy (SEM) investigations were utilised to develop wet-chemical smoothing procedures for atomically flat and structured surfaces, respectively. Hydrogen-termination as well as passivation by wet-chemical oxides were used to inhibit surface contamination and native oxidation during the technological processing. Compared to conventional pre-treatments, significantly lower micro-roughness and densities of surface states were achieved on mono-crystalline Si(100), on evenly distributed atomic steps, such as on vicinal Si(111), on silicon wafers with randomly distributed upside pyramids, and on poly-crystalline EFG (Edge-defined Film-fed-Growth) silicon substrates.The recombination loss at a-Si:H/c-Si interfaces prepared on c-Si substrates with randomly distributed upside pyramids was markedly reduced by an optimised wet-chemical smoothing procedure, as determined by PL measurements. For amorphous-crystalline hetero-junction solar cells (ZnO/a-Si:H(n)/c-Si(p)/Al) with textured c-Si substrates the smoothening procedure results in a significant increase of short circuit current I_sc, fill factor and efficiency η. The scatter in the cell parameters for measurements on different cells is much narrower, as compared to conventional pre-treatments, indicating more well-defined and reproducible surface conditions prior to a-Si:H emitter deposition and/or a higher stability of the c-Si surface against variations in the a-Si:H deposition conditions.     

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)     

Porous silicon with β-cyclodextrin modified surface for photoluminescence sensing of organic molecules in gas and liquid phase

Porous silicon surface was modified by photochemically activated hydrosilylation reaction with permethyl-6^I-alkenoylamino-6^I-deoxy-β-cyclodextrins terminated with linear alkenoyl spacers of various lengths. As compared to unmodified surface, derivatized surfaces revealed modified photoluminescence response in the presence of controlled amounts of various organic molecules in gas and liquid phase. For the selected set of analytes we observed most significant modification of photoluminescence response for aromatic compounds what corresponds to optimum molecular size for strong host–guest interaction with β-cyclodextrin cavity. Aliphatic compounds quenched photoluminescence from both unmodified and surface modified porous silicon. For low gas phase concentrations of aromatic analytes β-cyclodextrin modified porous silicon revealed photoluminescence enhancement, at higher concentrations common photoluminescence quenching was observed. The size-dependent host–guest interaction between β-cyclodextrin cavity and detected molecule was observed in photoluminescence quenching in the presence of aliphatic molecules in liquid phase. The role of the strength of host–guest interactions between detected analytes and β-cyclodextrin cavity on photoluminescence sensor response is discussed.     

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.     

Staleya guttiformis attachment on poly(tert-butylmethacrylate) polymeric surfaces

The attachment behaviour of Staleya guttiformis DSM 11458^T on poly(tert-butyl methacrylate) (P(tBMA)) polymeric surfaces has been studied. The electrostatic charge of the S. guttiformis cell surface (measured as zeta potential via microelectrophoresis) was −43.18 mV. S. guttiformis cells appeared weakly hydrophilic as the water contact angle measured on lawns of bacterial cells was found to be 55 ± 4.9°. It was found that while attaching on P(tBMA) surfaces, S. guttiformis cells produced extracellular polymeric substances (EPS) as observed from atomic force microscopy (AFM) and scanning electron microscopy (SEM) analysis. The AFM high resolution imaging revealed the nano-topography of the ‘free’ (the EPS that is produced by the bacterial cells, but no longer directly attached to the cells) EPS associated on the cell surface and also found on P(tBMA) surface. The ‘free’ EPS exhibited granular structure with lateral dimensions of 30–50 nm and a vertical nano-roughness of 7–10 nm. Another type of the EPS secreted by S. guttiformis cells appeared as a hydogel substance, presumably polysaccharide that formed a biopolymer network that facilitated bacterial attachment.     

A glass thinning and texturing method for light incoupling in thin‐film polycrystalline silicon solar cells application

For polycrystalline silicon (poly‐Si) thin‐film solar cells on ～3 mm borosilicate glass, glass thinning reduces the glass absorption and light leaking to neighbouring cells; the glass texturing of the sun‐facing side suppresses reflection. In this Letter, a labour‐free wet etching method is developed to texture and thin the glass at the same time in contrast to conventionally separated labour‐intensive glass thinning and texturing processes. For 2 cm² size poly‐Si thin‐film solar cells on glass superstrate, this wet etching successfully thins down the glass from 3 mm to 0.5 mm to check the ultimate benefit of the process and introduces a large micron texture on the sun‐facing glass surface. The process enhances J_sc by 6.3% on average, with the optimal J_sc enhancement of 8%, better than the value of 4.6% found in the literature. This process also reduces the loss in external quantum efficiency (EQE loss), which is due to light leaking to neighbouring cells, dramatically. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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%.     

Influence of Iodine-Containing Solutions on the Condition of a Porous Silicon Surface and Its Photoluminescent Properties

The influence of surface treatment of porous silicon in iodine-containing solutions on its photoluminescent properties has been investigated. The porous silicon samples were prepared by anodizing in HF-based electrolytes and placed in fluoride-hydrogen solutions with the addition of iodine immediately after their formation. The surface condition was controlled by IR Fourier spectroscopy methods in the 400–4000-cm^–1 range. It has been established that the result of the porous silicon treatment in iodine-containing solutions is a decrease in the intensity of Si–H _x -bonds without the appearance of additional vibrations in the range under investigation. At the same time, such a treatment substantially affects the spectrum and intensity of porous silicon photoluminescence and increases its stability in subsequent storage. The possible reasons for the revealed phenomena are discussed.     

Accurate, high-order representation of complex three-dimensional surfaces via Fourier continuation analysis

We present a new method for construction of high-order parametrizations of surfaces: starting from point clouds, the method we propose can be used to produce full surface parametrizations (by sets of local charts, each one representing a large surface patch – which, typically, contains thousands of the points in the original point-cloud) for complex surfaces of scientific and engineering relevance. The proposed approach accurately renders both smooth and non-smooth portions of a surface: it yields super-algebraically convergent Fourier series approximations to a given surface up to and including all points of geometric singularity, such as corners, edges, conical points, etc. In view of their C^∞ smoothness (except at true geometric singularities) and their properties of high-order approximation, the surfaces produced by this method are suitable for use in conjunction with high-order numerical methods for boundary value problems in domains with complex boundaries, including PDE solvers, integral equation solvers, etc. Our approach is based on a very simple concept: use of Fourier analysis to continue smooth portions of a piecewise smooth function into new functions which, defined on larger domains, are both smooth and periodic. The “continuation functions” arising from a function f converge super-algebraically to f in its domain of definition as discretizations are refined. We demonstrate the capabilities of the proposed approach for a number of surfaces of engineering relevance.     

Nonlinear optical investigations of the dynamics of hydrogen interaction with silicon surfaces

Optical second-harmonic generation (SHG) from silicon surfaces may be resonantly enhanced by dangling-bond-derived surface states. The resulting high sensitivity to hydrogen adsorption combined with unique features of SHG as an optical probe has been exploited to study various kinetical and dynamical aspects of the adsorption system H₂/Si. Studies of surface diffusion of H/Si(111)7×7 and recombinative desorption of hydrogen from Si(111)7 × 7 and Si(100)2 × 1 revealed that the covalent nature of hydrogen bonding on silicon surfaces leads to high diffusion barriers and to desorption kinetics that strongly depend on the surface structure. Recently, dissociative adsorption of molecular hydrogen on Si(100)2×1 and Si(111)7×7 could be observed for the first time by heating the surfaces to temperatures between 550 K and 1050 K and monitoring the SH response during exposure to a high flux of H₂ or D₂. The measured initial sticking coefficients for a gas temperature of 300K range from 10^–9 to 10^–5 and strongly increase as a function of surface temperature. These results demonstrate that the lattice degrees of freedom may play a decisive role in the reaction dynamics on semiconductor surfaces.     

Ultrafast-laser-assisted chemical restructuring of silicon and germanium surfaces

This article reports a comparative study on texturing in silicon and germanium surfaces after exposure to femtosecond laser irradiation in the gaseous environments of sulfur hexafluoride (SF₆) and hydrogen chloride (HCl). The surface texturing results from the combined effect of laser-assisted chemical etching and laser ablation. Optimized processing conditions have produced features on the order of nanometers in size. We demonstrate for the first time that regular conical pillars can be formed in Ge and that HCl can be used to form regular conical pillars in Si.     

Development of surface-textured hydrogenated ZnO:Al thin-films for μc-Si solar cells

This study addresses the optimization of rf magnetron-sputtered hydrogenated ZnO:Al (HAZO) films as front contacts in microcrystalline silicon solar cells. The front contact of a solar cell has to be highly conductive and highly transparent to visible and infrared radiation. Furthermore, it has to scatter the incident light efficiently in order for the light to be effectively trapped in the underlying silicon layers. In this research, HAZO films were rf-magnetron-sputtered on glass substrates from a ceramic (98 wt% ZnO, 2 wt% Al₂O₃) target. Various compositions of AZO films on glass substrates were prepared by changing the H₂/(Ar + H₂) ratio of the sputtering gas. The resulting smooth films exhibited high transparencies (T  85% for visible light including all reflection losses) and excellent electrical properties (ρ = 2.7 × 10⁻⁴ Ω · cm). Depending on their structural properties, these films developed different surface textures upon post-deposition etching using diluted hydrochloric acid. The light-scattering properties of these films could be controlled simply by varying the etching time. Moreover, the electrical properties of the films were not affected by the etching process. Therefore, within certain limits, it is possible to optimize the electro-optical and light-scattering properties separately. The microcrystalline silicon (μc-Si:H)-based p–i–n solar cells prepared using these new texture-etched AZO:H substrates showed high quantum efficiencies in the long wavelength range, thereby demonstrating effective light trapping. Using the optimum AZO:H thin-film textured surface, we achieved a p–i–n μc-Si solar cell efficiency of 7.78%.