Nanostructured pyramidal black silicon with ultra-low reflectance and high passivation

In this study, nanostructured pyramidal black silicon is prepared by metal assisted chemical etching method, in which the silver nitrate (AgNO₃) is used as the metal catalyst. Effects of the concentration of AgNO₃ on passivation and optical properties of the black silicon are investigated. The experimental results show that at the AgNO₃ concentration of 0.03 M, the nanostructure length is about 300 nm, and the reflectance of the black silicon with a stack of silicon nitride (SiN_x) and aluminum oxide (Al₂O₃) is 0.8%, which is comparable to that of the conventional black silicon with micrometer-long nanowires. In addition, an acceptably low surface recombination rate of 42 cm/s can be obtained. Plasma chemical vapor deposited SiN_x is deposited well on the top of nanostructures of black silicon, but shows poor coverage at the bottom region. Spatial atomic layer deposited Al₂O₃ can conformally cover the nanostructures with high passivation quality. Simulation result indicates an improvement of 5.5% of conversion efficiency for the nanostructured pyramidal black silicon solar cell compared to industrial silicon solar cell. The short nanostructured pyramidal surface with low reflectance and high passivation is expected to be helpful for black silicon technology applied to photovoltaic applications.     

A Novel Silicon Etching Method Using Vapor of Tetramethylammonium Hydroxide Solution

Silicon bulk etching is an important part of micro-electro-mechanical system (MEMS) technology. In this work, a novel etching method is proposed based on the vapor from tetramethylammonium hydroxide (TMAH) solution heated up to boiling point. The monocrystalline silicon wafer is positioned over the solution surface and can be anisotropically etched by the produced vapor. This etching method does not rely on the expensive vacuum equipment used in dry etching. Meanwhile, it presents several advantages like low roughness, high etching rate and high uniformity compared with the conventional wet etching methods. The etching rate and roughness can reach 2.13 μm/min and 1.02 nm, respectively. Furthermore, the diaphragm structure and Al-based pattern on the non-etched side of wafer can maintain intact without any damage during the back-cavity fabrication. Finally, an etching mechanism has been proposed to illustrate the observed experimental phenomenon. It is suggested that there is a water thin film on the etched surface during the solution evaporation. It is in this water layer that the ionization and etching reaction of TMAH proceed, facilitating the desorption of hydrogen bubble and the enhancement of molecular exchange rate. This new etching method is of great significance in the low-cost and high-quality micro-electro-mechanical system industrial fabrication.     

Effect of current density on morphological,structural and optical properties of porous silicon

The morphology of porous silicon (PS) layers produced by electrochemical etching of n-type (100) silicon (Si) at different low current densities was studied using SEM, image J analysis and WSxM software. From FTIR spectroscopy analysis, the Si dangling bonds of the as-prepared PS layer have large amount of Hydrogen to form weak Si–H bonds. From Raman analysis, a full width half maximum (FWHM) of the Raman peak was gradually increased with increased current density, shifted towards lower energies due to reduce of crystallite size, the crystallite size in the PS varied from 63 nm to 20 nm depending on the current density. The optical response of the PS layer has been performed by the absorbance and Photoluminescence was studied experimentally in the visible range. The optical absorption and photo luminescence in PS is due to excitonic recombination between the defect states as well as on the surface of nanocrystals, and this was attributed to the presence of silicon hydride species which are confirmed by FTIR spectra. The red shift was observed in absorbance and Photoluminescence due to decrease in the size of Si crystallites and growth of Si=O bonds. The contact angle varied from 76° to 120.1°. From the wettability studies, the surface nature of the PS was converted from hydrophilic to hydrophobic when the current density increased.     

优化金属辅助法腐蚀液组分制备多孔硅

金属辅助化学腐蚀法可以在无外加电路的条件下,在40%HF/30%H2O2/乙醇的混合溶液中完成多孔硅的制备,该方法简单快速。本文研究了金属辅助法腐蚀液体系各组分(HF、H2O2、乙醇)含量对多孔硅表面的SiHx成分和多孔层结构的影响,根据Si-H和Si-O的红外吸收峰强度的变化曲线优化了腐蚀液体系中各组分含量。在腐蚀液各组分体积比为V40%HF∶V30%H2O2∶V乙醇=2∶2∶1和腐蚀时间为4 min的条件下制备了形貌均匀、化学活性(SiHx成分)和多孔结构稳定性较好的多孔硅,并对金属辅助法与阳极蚀刻法制得的两种多孔硅进行比较,结果显示金属辅助法制备的多孔硅的化学活性和稳定性在后续的生物技术应用中具有明显的优越性。     

湿化学法制备硅纳米线阵列及其光电化学产氢性能分析

为了探究不同方法条件下制备的硅纳米线阵列电极产氢性能异同,文中分别采用了两步金属辅助催化无电刻蚀法、一步金属辅助催化无电刻蚀法以及阳极氧化法来制备硅纳米线阵列用作为光电分解水电池光阴极材料。通过FESEM、XRD和UVVis-IR DRS等手段对实验样品的形貌、晶型、减反性表征,发现相比于其他2种方法所得硅纳米线样品,两步金属辅助催化无电刻蚀法制备的硅纳米线结构晶型保持更好,表面缺陷更少。光电化学测试表明两步金属辅助催化无电刻蚀法制备的硅纳米线光电化学性能表现最优,其光电流密度值是一步法的4倍,阳极氧化法的40倍;转移电荷电阻仅是一步法制备的硅纳米线阵列阻值的1/3,阳极氧化法制备的1/1 000。     

湿化学法制备硅纳米线阵列及其光电化学产氢性能分析

为了探究不同方法条件下制备的硅纳米线阵列电极产氢性能异同,文中分别采用了两步金属辅助催化无电刻蚀法、一步金属辅助催化无电刻蚀法以及阳极氧化法来制备硅纳米线阵列用作为光电分解水电池光阴极材料.通过FESEM、XRD和UV-Vis-IRDRS等手段对实验样品的形貌、晶型、减反性表征,发现相比于其他2种方法所得硅纳米线样品,两步金属辅助催化无电刻蚀法制备的硅纳米线结构晶型保持更好,表面缺陷更少.光电化学测试表明两步金属辅助催化无电刻蚀法制备的硅纳米线光电化学性能表现最优,其光电流密度值是一步法的4倍,阳极氧化法的40倍;转移电荷电阻仅是一步法制备的硅纳米线阵列阻值的1/3,阳极氧化法制备的1/1000.     

Chemical etching of zinc oxide for thin-film silicon solar cells

Chemical etching is widely applied to texture the surface of sputter-deposited zinc oxide for light scattering in thin-film silicon solar cells. Based on experimental findings from the literature and our own results we propose a model that explains the etching behavior of ZnO depending on the structural material properties and etching agent. All grain boundaries are prone to be etched to a certain threshold, that is defined by the deposition conditions and etching solution. Additionally, several approaches to modify the etching behavior through special preparation and etching steps are provided.     

金属辅助化学刻蚀法制备硅纳米线及应用

金属辅助化学刻蚀是近些年发展起来的一种各向异性湿法刻蚀,利用该方法可以制备出高长径比的半导体一维纳米结构。 本文综述了金属辅助化学刻蚀法可控制备硅纳米线的最新进展,简要概述了刻蚀的基本过程与机制,重点阐述了基于不同模板的金属辅助化学刻蚀可控制备高度有序、高长径比的硅纳米线阵列的具体流程与工艺,并介绍了其在锂离子电池、太阳能电池、气体传感检测和仿生超疏水等方面的潜在应用,探讨了目前存在的问题及其今后的研究发展方向。     

Enhancement and stabilization of the photoluminescence from porous silicon prepared by Ag‐assisted electrochemical etching

In this paper, we present the results of studies on the photoluminescence (PL) of porous silicon (PSi) samples obtained by etching with the assistance of silver metal in different ways. If the Si sample, after being coated with a layer of silver nanoparticles, is electrochemically etched, its PL intensity becomes hundreds of times stronger than the PL intensity when it is chemically etched in the similar conditions. The difference in the PL intensities is explained partly by the anodic oxidation of silicon which occurs during the electrochemical etching process. The most obvious evidence that silicon had been oxidized anodically in the electrochemical etching process is the disappearance of the PSi layer and the appearance of the silicon oxide layer with mosaic structure when the anodization current density is large enough. The anodic oxidation has the effect of PSi surface passivation. Because of that, the PL of obtained PSi becomes stronger and more stable with time. Copyright © 2012 John Wiley & Sons, Ltd.     

Thin film processing using S-layer proteins: biotemplated assembly of colloidal gold etch masks for fabrication of silicon nanopillar arrays

We explored the bionanofabrication of silicon nanopillar structures using ordered gold nanoparticle arrays generated from microbial surface layer (S-layer) protein templates. The S-layer template used for these thin film processing experiments was isolated from the Gram-positive bacterium Deinococcus radiodurans. In this preliminary work, S-layers preimmobilized onto chemically modified silicon substrates were initially used to template the fabrication of a nanolithographic hard mask pattern comprised of a hexagonally ordered array of 5-nm gold nanoparticles (lattice constant = 18 nm). Significantly, the use of the biotemplated gold nanoparticle mask patterns in an inductively coupled plasma (ICP) etching process successfully yielded silicon nanopillar structures. However, it was found that the resultant nanopillars (8–13 nm wide at the tip, 15–20 nm wide at half-height, 20–30 nm wide at the base, and 60–90 nm tall) appeared to lack any significant degree of translational ordering. The results suggest that further studies are needed in order to elucidate the optimal plasma processing parameters that will lead to the generation of long-range ordered arrays of silicon-based nanostructures using S-layer protein templates.     

Regular arrays of triangular‐microstructure formed on silicon (111) surface via ultrafast laser irradiation in KOH solution

The regular micrometer‐scale triangular arrays were formed using ultrafast femtosecond laser irradiation on (111) surface of silicon wafer immersed in KOH solution (0.1 g/ml). At low laser fluence, the resulting surface is covered by triangular pits microstructures, whereas at high laser fluence, the structures are transformed to multilayer‐triangular stacks‐microstructures. The number of triangular stacks layer increased as the laser fluence increased. The formation of triangle microstructure arrays depends on both silicon surface crystallographic orientation and the concentration of KOH solution. Either for lower KOH solution concentration (0.02 g/ml) or other silicon crystallographic orientation, triangle arrays cannot be obtained. We attribute the formation of triangular microstructure arrays to the laser‐assisted chemical etching process. Copyright © 2013 John Wiley & Sons, Ltd.     

Application of ZnO nanoparticles to enhance photoluminescence in porous silicon and its possible utilization for improving the short wavelength quantum efficiency of silicon solar cell

We have formed photoluminescent porous silicon (PS) layers and over which a ZnO layer (hereafter called ZnOPS layers) is deposited. We studied the photoluminescent properties of individual layers as well as the composite layer under excitation with 405 nm wavelength. Using the data of PL a theoretical analysis of a solar cell having such a composite layer of a given photoluminescent conversion efficiency η_PL on the front surface has been done. The condition of a photoluminescent composite layer (ZnOPS) useful for enhancing the spectral response of n⁺-p-p⁺ structured silicon solar cell has been identified.     

Titrimetric determination of silicon dissolved in concentrated HF-HNO3-etching solutions

The wet chemical etching of silicon by concentrated HF-HNO₃ mixtures in solar and semiconductor wafer fabrication requires the strict control of the etching conditions. Surface morphology and etch rates are mainly affected by the amount of dissolved silicon, that is continuously enriched in the etching solution with each etching run. A fast and robust method for the titrimetric determination of the total dissolved silicon content out of the concentrated etching solution is presented. This method is based on the difference between the two equivalence points of the total amount of acid and the hydrolysis of the hexafluorosilicic anion. This approach allows a silicon determination directly from the etching process in spite of the presence of dissolved nitric oxides in the etching solution. The influences of different acid mixing ratios and of the etching solution density depending on the silicon content is considered and discussed in detail.     

Metal-particle-induced, highly localized site-specific etching of Si and formation of single-crystalline Si nanowires in aqueous fluoride solution

A straightforward metal-particle-induced, highly localized site-specific corrosion-like mechanism was proposed for the formation of aligned silicon-nanowire arrays on silicon in aqueous HF/AgNO3 solution on the basis of convincing experimental results. The etching process features weak dependence on the doping of the silicon wafers and, thus, provides an efficient method to prepare silicon nanowires with desirable doping characteristics. The novel electrochemical properties between silicon and active noble metals should be useful for preparing novel silicon nanostructures and also new optoelectronic devices.     

碱性水溶液中甲醛在硅电极表面的电化学行为及其对硅化学刻蚀的影响

研究了KOH水溶液中氧化剂甲醛在p-Si和n-Si(100)单晶半导体电极表面的电化学行为及其对硅化学刻蚀表面形貌的影响．实验结果表明,甲醛不仅影响p-和n-型半导体电极在碱性溶液中的阳极氧化峰电流,而且在负电位区能在Si(100)电极上发生还原．在光照条件下,p-Si(100)电极上也观测到了HCHO的电化学还原及光电流倍增效应．甲醛在硅电极表面的电化学还原反应分两步进行,反应终产物为甲醇．此外,HCHO能有效抑制碱性溶液中Si表面“金字塔”型表面粗糙颗粒的形成。     

Nano Silicon from Nano Silica Using Natural Resource (Rha) for Solar Cell Fabrication

Abstract

High purity (～99%) nano silica with an average particle size of ～100 nm was extracted at pH 3 at 650°C from a natural resource, rice husk, using alkaline extraction followed by acid precipitation method. Using nano silica as a precursor, silicon (Si) nanoparticles have been synthesized by high-temperature magnesiothermic reduction method. The prepared sample was characterized by X-ray diffraction, particle size analyzer, Fourier transform infrared spectroscopy, transmission electron microscopy, X-ray fluorescence analyzer, and UV–Vis spectroscopy. The comprehensive characterization studies indicate the pure phase formation of Si and the variation of particle size from 70 nm to 100 nm for samples synthesized at different sintering temperatures. Moreover, the silicon nanoparticles produced at 850°C have pure phase formation, high purity, and good absorption peaks. The efficiency calculated through IV characteristics is found to be increasing in silicon and ruthenium combination (2.67%), which is better than that achieved from the conventional solar cells. The produced silicon nanoparticles could be applied as an anode material for solar cell fabrication.     

Extremely superhydrophobic surfaces with micro- and nanostructures fabricated by copper catalytic etching

We demonstrate a simple method for the fabrication of rough silicon surfaces with micro- and nanostructures, which exhibited superhydrophobic behaviors. Hierarchically rough silicon surfaces were prepared by copper (Cu)-assisted chemical etching process where Cu nanoparticles having particle size of 10-30 nm were deposited on silicon surface, depending on the period of time of electroless Cu plating. Surface roughness was controlled by both the size of Cu nanoparticles and etching conditions. As-synthesized rough silicon surfaces showed water contact angles ranging from 93° to 149°. Moreover, the hierarchically rough silicon surfaces were chemically modified by spin-coating of a thin layer of Teflon precursor with low surface energy. And thus it exhibited nonsticky and enhanced hydrophobic properties with extremely high contact angle of nearly 180°.     

激光刻蚀模板中电沉积特殊结构CIGS薄膜

本文利用激光刻蚀模板,在水溶液中电沉积制备金属铜薄膜,讨论了温度、电流、硫酸铜浓度对薄膜形貌的影响. 采用SEM对制备的铜薄膜进行表征,结果表明在沉积温度为30 ℃,沉积电流为4 A·dm^-2(表观工作电流密度),硫酸铜浓度在20 ~ 50 g·L^-1的水溶液中电沉积可以得到中空馒头状和开口碗状结构的铜薄膜. 利用激光刻蚀模板,在离子液体1-丁基-3-甲基咪唑三氟甲磺酸盐([BMI][TfO]) - 30 Vol%丙醇混合电解质中电沉积CIGS薄膜,研究了沉积电势、沉积时间对薄膜形貌的影响. SEM观察发现,在沉积电势为-1.8 V,沉积时间为1.5 h条件下电沉积可以得到近似柱状的簇状花束样的CIGS薄膜, 电沉积铜后再进一步电沉积CIGS,得到了均匀有序的鼓包柱状结构的Cu/CIGS复合薄膜. 用恒电势方波法对制备的薄膜真实表面积进行测试,计算结果表明,与无模板电沉积制备的CIGS薄膜相比,激光刻蚀模板法制备的Cu/CIGS复合薄膜的表面积提高了约8倍.     

Silicon nanowire radial p-n junction solar cells

We have demonstrated a low-temperature wafer-scale etching and thin film deposition method for fabricating silicon n-p core-shell nanowire solar cells. Our devices showed efficiencies up to nearly 0.5%, limited primarily by interfacial recombination and high series resistance. Surface passivation and contact optimization will be critical to improve device performance in the future.     

Determination of phosphorus death profiles in semiconductor silicon by chemical etching and filament vaporization inductively-coupled plasma atomic emission spectrometry

Silicon slices are dissolved by anodizin and removal of the silica film by hydrofluoric acid. The phosphorus in the etching solution is determined by the filament vaporization technique and the depth of silicon is measured by determining the silicon content in the etching solution by conventional inductively-coupled plasma atomic emission spectrometry. A lower limit of 10¹⁸ phosphorus atoms cm^?3 can be determined by sectioning intervals of 30–50 nm.