晶体硅太阳电池表面纳米线阵列减反射特性研究

为增强晶体硅太阳电池的光利用率, 提高光电转换效率, 研究了硅纳米线阵列的光学散射性质. 运用严格耦合波理论对硅纳米线阵列在310—1127 nm波段的反射率进行了模拟计算, 用田口方法对硅纳米线阵列的表面传输效率进行了优化. 结果表明, 当硅纳米线阵列的周期为50 nm, 占空比为0.6, 高度约1000 nm时减反射效果最佳; 该结构在上述波段的平均反射率约为2%, 且在较大入射角度范围保持不变. 采用金属催化化学腐蚀法, 于室温、室压条件下在单晶硅表面制备周期为60 nm,占空比为0.53, 高度为500 nm的硅纳米线阵列结构, 其反射率的实验测试结果与计算模拟值相符, 在上述波段的平均反射率为4%—5%, 相对于单晶硅35%左右的反射率, 减反射效果明显. 这种减反射微结构能够在降低太阳电池成本的同时有效减小单晶硅表面的光反射损失, 提高光电转换效率.     

Novel and low reflective silicon surface fabricated by Ni-assisted electroless etching and coated with atomic layer deposited Al2O3 film

In this paper, nickel nanoparticles (Ni NPs) were deposited on planar silicon and pyramidal silicon wafers by the magnetron sputtering method, and then these Ni NP-covered samples were etched in a hydrofluoric acid, hydrogen peroxide, and deionized water mixed solution at room temperature to fabricate a low reflective silicon surface. An alumina (Al₂O₃) film was then deposited on the surface of the as-etched pyramidal sample by atomic layer deposition to further reduce the reflectance. The morphologies and compositions of these samples were studied by using a field emission scanning electron microscope attached to an energy-dispersive X-ray spectrometer. The surface reflectance measurements were carried out with a UV-Vis-NIR spectrophotometer in a wavelength range of 200–1100 nm. The SEM images show that the as-etched planar and pyramidal silicon samples were covered with many rhombic nanostructures and that some nanostructures on the planar silicon surface were ready to exhibit a flower-like burst. The reflectances of the as-etched planar and pyramidal silicon samples were 5.22 % and 3.21 % in the wavelength range of 400–800 nm, respectively. After being coated with a 75-nm-thick Al₂O₃ film, the etched pyramidal silicon sample showed an even lower reflectance of 2.37 % from 400 nm to 800 nm.     

等离子体浸没离子注入制备黑硅抗反射层及其光学特性研究

表面织构是一种有效降低表面反射率、提高硅基太阳能电池效率的方法. 采用等离子体浸没离子注入的方法制备了黑硅抗反射层.分别通过原子力显微镜和紫外-可见-近红外分光光度计对黑硅样品表面形貌和反射率进行分析, 结果发现黑硅样品表面布满了高度为0—550 nm的山峰状结构, 结构层中硅体积分数和折射率随抗反射层厚度增加而连续降低. 在300—1000 nm波段范围内,黑硅样品的加权平均反射率低至6.0%. 通过传递矩阵方法对黑硅样品反射谱进行模拟,得到的反射谱与实测反射谱非常符合.     

Thermal annealing dependence of some optical properties of plasma-modified porous silicon

The photoluminescence and reflectance of porous silicon (PS) with and without hydrocarbon (CH_x) deposition fabricated by plasma enhanced chemical vapour deposition (PECVD) technique have been investigated. The PS samples were then, annealed at temperatures between 200 and 800 °C. The influence of thermal annealing on optical properties of the hydrocarbon layer/porous silicon/silicon structure (CH_x/PS/Si) was studied by means of photoluminescence (PL) measurements, reflectivity and ellipsometry spectroscopy. The composition of the PS surface was monitored by transmission Fourier transform infrared (FTIR) spectroscopy. Photoluminescence and reflectance measurements were carried out before and after annealing on the carbonized samples for wavelengths between 250 and 1200 nm. A reduction of the reflectance in the ultraviolet region of the spectrum was observed for the hydrocarbon deposited polished silicon samples but an opposite behaviour was found in the case of the CH_x/PS ones. From the comparison of the photoluminescence and reflectance spectra, it was found that most of the contribution of the PL in the porous silicon came from its upper interface. The PL and reflectance spectra were found to be opposite to one another. Increasing the annealing temperature reduced the PL intensity and an increase in the ultraviolet reflectance was observed. These observations, consistent with a surface dominated emission process, suggest that the surface state of the PS is the principal determinant of the PL spectrum and the PL efficiency.     

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.     

多晶硅表面陷阱坑形貌对表面光反射率的影响

利用光学傅里叶变换研究多晶硅绒面微结构形貌与反射率之间的关系。理论分析表明:多晶硅绒面反射率与表面微结构形貌、单位面积上陷阱坑数量有关。如绒面由V字型槽或坑构成,则绒面反射率比较高;如多晶硅表面上密集布满U字形坑或槽、内表面绒面化,这种结构构成的绒面反射率低。实验上用不同比例的酸液刻蚀多晶体表面,用扫描电镜(SEM)观察多晶硅表面SEM图,测量了其表面反射率,分析表面结构形貌与反射率的关系。实验结果与理论分析相吻合。     

Frequency selective IR-filter produced by using EB-lithography

This paper reports on the fabrication of Jerusalem cross diplexer by direct write electron beam (EB) lithography followed by reactive ion etching (RIE) on a phosphorus doped polished silicon wafer substrate. Such structures can be used as frequency selective components in visible, microwave and near infra-red wavelength region. Replication of the patterns is accomplished by micron or sub-micron order mould fabricated from the silicon (Si) master. Fourier transform infra-red reflectance (FT-IR) measurements were performed to characterize the structured patterns. The spectral reflectance from these patterns clearly show a reflection dip due to surface plasmon excitation in the near infra-red wavelength at about 1.42 and 2.5 μm, respectively. Potential applications such as antireflection surface (ARS) can be realized.     

Study of the relationship between particle sizes of polymer powders and their radiative properties

The reflectance of a surface considered as smooth relative to the wavelength mainly consists of a specular component while for a rough surface, the reflectance is composed of both specular and diffuse (or volume) components, their relative importance depending on the nature of the reflecting material. The present samples consist of polypropylene powders and the influence of particle size on total and diffuse reflectance is discussed over two wavelength ranges: 0.25–2.5 and 2.5–15.5 μm. The results of this study indicate firstly, that in the first wavelength range, the areas of the absorbance peaks increase while they decrease for the other wavelength range with particle size and secondly, that the reflectance values calculated for the wavelength range 0.25–2.5 μm, with respect to a blackbody at 5800 K, vary with particle size.     

Effect of Density and Surface Roughness on Optical Properties of Silicon Carbide Optical Components

The effect of density and surface roughness on the optical properties of silicon carbide optical components is investigated. The density is the major factor of the total reflectance while the surface roughness is the major factor of the diffuse reflectance. The specular reflectance of silicon carbide optical components can be improved by increasing the density and decreasing the surface roughness, in the form of reducing bulk absorption and surface-related scattering, respectively. The contribution of the surface roughness to the specular reflectance is much greater than that of the density. When the rms surface roughness decreases to 2.228nm, the specular reflectance decreases to less than 0. 7% accordingly.     

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.     

The effect of silicon substrate on thickness of SiO2 thin film analysed by spectral reflectometry and interferometry

Techniques of spectral reflectometry and interferometry are used for measuring small changes in thickness of SiO₂ thin film grown by thermal oxidation on different silicon substrates. A slightly dispersive Michelson interferometer with one of its mirrors replaced by a thin-film structure is used to measure the reflectance and interferometric phase of the thin-film structure at the same time. The experimental data are used to determine precisely the thickness of the SiO₂ thin film on silicon wafers of two crystallographic orientations and different dopant concentrations. We confirmed very good agreement between the experimental data and theory and revealed that the thin-film thickness, which varies with the type of silicon substrate, depends linearly on the wavelength at which minimum in the spectral reflectance occurs. Similar behaviour was revealed for the interferometric phase.     

微纳混合结构黑硅的制备及其关键工艺技术讨论

黑硅是一种能大幅提高器件光电转换效率的新型电子材料,微纳混合结构黑硅是一种比普通黑硅材料更高效的新型黑硅材料,如何制备出大面积、形貌特征好、表面洁净度高的黑硅材料是制备高效的黑硅太阳能电池的前提。首先,利用湿法腐蚀方法,通过设计合适的反应固体装置和良好的工艺控制手段,在金字塔硅表面制备了大面积的微纳混合结构黑硅;然后,对其制备的关键工艺技术进行了研究讨论。实验结果表明,该方法制备的微纳混合结构黑硅具有形貌特征好、表面洁净度高和低表面反射率等特征。有效去除表面银沉积物后,该黑硅在300~1 100 nm范围内的加权平均反射率低至4.06%。该制备工艺方法适用于大面积高效微纳混合结构黑硅的规模制备,在高效黑硅太阳能电池领域具有重要的应用价值。     

光管理在晶体硅电池中的应用

光管理是提高晶体硅太阳能电池光吸收和短路电流（Jsc）进而提高转换效率的重要因素之一。本文回顾了最常见的光管理方式,包括表面抗反射、散射以及陷光等。为了降低晶体硅电池的表面反射损失,开发了多种表面抗反射结构。例如,仿生蛾眼结构利用渐变折射率实现了宽光谱低反射率,其表面反射率可达1％以下。随着晶体硅电池衬底减薄,光管理要求更加严格,除了在更宽波长范围内达到超低反射率外,还需要在更高的入射角范围内实现低反射率。此外,利用前表面散射以及背表面陷光结构提高红外光的吸收光程对于晶体硅电池特别是薄衬底晶体硅电池的有效光吸收具有重要意义。     

Long-time stabilization of porous silicon photoluminescence by surface modification

We present results on the photoluminescence (PL) properties of porous silicon (PS) as a function of time. Stabilization of PL from PS has been achieved by replacing silicon-hydrogen bonds terminating the surface with more stable silicon-carbon bonds. The composition of the PS surface was monitored by transmission Fourier transform infrared (FTIR) spectroscopy at intervals of 1 month in ageing time up to 1 year. The position of the maximum PL peak wavelength oscillates between a blue-shift and a red-shift in the 615-660 nm range with time.     

Modeling of optical spectroscopy for the crystalline silicon

The paper is aimed at modeling optical spectra of silicon. Optical spectra of silicon are described with the Logistic function. A satisfactory agreement between the measured and the modeled optical spectra are obtained. The minimum magnitude of the correlation coefficient between experiment and theoretical results is 0.994, and the maximum average relative error is 4.21%. Meanwhile, it is found that the band gap of semiconductor may be determined by fitting absorption coefficient as a function of wavelength. Lastly, the mathematical relationships between the parameters, which are used to link the reflectance of silicon and wavelength, and radiation fluency, are obtained. Consequently, the change of reflectance for silicon can be predicted by both wavelength and dose radiation fluency only one function. All results in this paper are of interest from both optics and materials point of view.     

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.     

Optical Transmittance and Band Gap of Ferroelectric BaTi2O5 Bulk Glass

Optical transmittance and reflectance on ferroelectric BaTi₂O₅ glasses prepared recently by a containerless synthesis technique are measured at room temperature in the wavelength range 190-800nm. The fundamental absorption edge located around 340nm demonstrates the colourless and transparent character of the glass. The optical band gap of 3.32eV has been estimated. The tail of the optical absorption near the fundamental absorption edge is found to follow the Urbach rule. Our analysis of the experimental spectra supports an indirect allowed interband transition between the valence band formed by O-2p orbitals and the conduction band formed by Ti-3d orbitals.     

Measurement of Refractive Index for High Reflectance Materials with Terahertz Time Domain Reflection Spectroscopy

A method to measure the refractive index for high reflectance materials in the terahertz range with terahertz time domain reflection spectroscopy is proposed. In this method, the THz waveforms reflected by a silicon wafer and high reflectance sample are measured respectively. The refractive index of the silicon wafer, measured with the THz time domain transmission spectroscopy, is used as a reference in the THz time domain reflective spectroscopy. Therefore, the complex refractive index of the sample can be obtained by resorting to the known reflective index of the silicon and the Fresnel law. To improve the accuracy of the phase shift, the Kramers-Kronig transform is adopted. This method is also verified by the index of the silicon in THz reflection spectroscopy. The bulk metal plates have been taken as the sample, and the experimentally obtained metallic refractive indexes are compared with the simple Drude model.     

New method to measure whole-wavelength transmittance of TCO substrates for thin-film silicon solar cells

High transmittance of transparent conductive oxide (TCO) substrates is one of the most important factors for achieving high efficiency in thin-film silicon solar cells. Immersion (IM) method with CH₂I₂ liquid is widely used for the evaluation of optical properties (transmittance, reflectance and absorption) for TCO substrates with textured surface in order to reduce the scattering at the TCO surface. However, in order to measure transmittance accurately, three problems have been found. (1) CH₂I₂ liquid itself absorbs the light in short wavelength region. (2) The transmittance around the absorption edge of CH₂I₂ liquids is very sensitive to its amount. (3) Scattering cannot be suppressed when the scattering surfaces are more than 2 surfaces (for example, TCO on reactive ion etching (RIE) processed glass). To overcome these problems, we proposed a new setup to measure optical properties of TCO substrates by holding the samples inside the integral sphere. As the results, we have confirmed that their absorption in all wavelength could be measured accurately and the transmittance measured by the new method was well consistent with the external quantum efficiency (EQE) of the fabricated cell while the transmittance measured with conventional IM method showed differently. Therefore, this new method could be a useful tool to evaluate TCO substrates for thin-film silicon solar cells.     

On the morphology of stain-etched porous silicon films

Morphology of stain-etched porous silicon films was investigated by a non-destructive technique, based on reflectance spectrometry: dielectric function profiles were computed by spectral reflectance via a finite difference model, and porosity was deduced by the effective medium approximation. Theoretical calculations were supported by high-resolution electron microscopy observations. The relations among oxidising species concentration in the etching solution, porosity profile and surface reflectance of the films were investigated.