低起始温度的线性升温热处理对直拉硅中氧沉淀的影响

研究了直拉硅片从不同的温度线性升温(Ramping)到750℃,然后在750℃退火64 h过程中的氧沉淀行为. 结果表明,Ramping对硅片中氧沉淀的形成有明显的促进作用,且起始温度越低促进作用越强. 这是因为在Ramping处理中,低温(450—650℃)热处理阶段氧的扩散速率显著增强,促进了氧沉淀核心的形成,且较低的Ramping升温速率有利于氧沉淀核心的稳定和继续长大. 进一步的实验结果还表明,低起始温度的Ramping处理可应用于硅片的内吸杂工艺,能促进氧沉淀的生成提高硅片的内吸杂能力,减少热预 关键词： 直拉硅 氧沉淀 退火     

晶硅太阳电池中Fe-B对与少子寿命、陷阱浓度及内量子效率的相关性

以太阳电池级直拉单晶硅片为材料,利用瞬态微波反射光电导衰减仪研究了硅片分别经过单、双面扩散后Fe-B对与少子寿命τ、陷阱浓度及制备成电池的内量子效率（IQE）的相关性.对于单面扩散后的样品,Fe-B对浓度分布在较大程度上决定了少子寿命分布;对于双面扩散后的样品,Fe-B对浓度显著降低（在135×10¹¹ cm^-3左右）,已不及其他杂质和缺陷对少子寿命的影响.结合瞬态微波衰减信号和陷阱模型,对单、双面吸杂前后硅片的陷阱浓度进行数值计算,发现经过扩散 关键词： 少子寿命 陷阱浓度 内量子效率 Fe-B对     

高纯区熔单晶硅高增益光晶体管的研究

区熔单晶硅与直拉单晶硅以及其他半导体材料相比杂质含量少,少子寿命长,所以以区熔单晶硅为衬底制作的光晶体管在弱的光信号下仍然有高的增益,适宜于弱光探测.报道了以区熔单晶硅为衬底的光晶体管的实验结果.为了保持区熔高纯单晶硅内的少子寿命,背面淀积了一层掺磷多晶硅作为外吸杂层.已经测量得到对于实验中发射极直径为2mm的光晶体管在波长为0.83 μm的入射光照射下,光功率低至0.16 nW时,光晶体管的增益仍然高达4400.     

多晶硅太阳电池激光掺杂选择性发射极

研究了多晶硅片扩散工艺与激光掺杂工艺的匹配性.采用波长532nm的纳秒脉冲激光器对扩散后未去磷硅玻璃的多晶硅片表面进行激光扫描掺杂,激光扫描掺杂后硅片方块电阻降低为扩散后硅片方阻的50%左右,而且随着激光功率的增加,扩散到硅片表面的磷原子浓度增大,硅片方阻下降更明显.测试了激光掺杂后多晶硅太阳能电池的外量子效率,其外量子效率在340~480nm波段范围与常规多晶硅太阳能电池相比提高18%~5%.研究了激光掺杂后多晶硅电池的光电转换特性,分析了较高激光功率掺杂时多晶硅电池的失效特性,结果表明:优化工艺后多晶硅太阳电池平均光电转换效率达到17.11%,比普通工艺多晶硅太阳电池提高0.34%,最高转换效率达到17.47%.激光掺杂选择性发射极工艺流程简单,电池效率提升明显,易于实现产业化.     

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     

低起始温度的线性升温热处理对直拉硅中氧沉淀的影响

研究了直拉硅片从不同的温度线性升温(Ramping)到750℃，然后在750℃退火64 h过程中的氧沉淀行为. 结果表明，Ramping对硅片中氧沉淀的形成有明显的促进作用，且起始温度越低促进作用越强. 这是因为在Ramping处理中，低温(450—650℃)热处理阶段氧的扩散速率显著增强，促进了氧沉淀核心的形成，且较低的Ramping升温速率有利于氧沉淀核心的稳定和继续长大. 进一步的实验结果还表明，低起始温度的Ramping处理可应用于硅片的内吸杂工艺，能促进氧沉淀的生成提高硅片的内吸杂能力，减少热预     

步进扫描时间分辨光谱及其在太阳电池光电导上的应用

建立傅里叶变换步进扫描时间分辨光电导光谱，并研究太阳电池中与转换效率密切相关的少数载流子寿命.实验选取三种典型的硅太阳电池(单晶硅样品1、多晶硅样品2和多晶硅样品3 )，发现其瞬态光电导的上升和衰退曲线可以分别用两个简单的指数函数描述.由于有复合中心的参与，复合过程中少数载流子的寿命比产生过程中的寿命短.为验证实验结果的可靠性，采用了提取样品少数载流子的体寿命和计算其有效扩散长度两种方法.通过与太阳电池暗伏安特性和负载特性研究相结合，进一步分析和讨论了少数载流子寿命与短路电流、开路电压和转换效率的关系.同时探讨了步进扫描时间分辨光谱实验的其他用途. 关键词： 步进扫描 时间分辨 硅太阳电池 瞬态光电导     

硅片及其太阳电池的光衰规律研究

采用氙灯模拟太阳光源,将光强调至1000 W/m2,研究常规太阳能级单晶硅片、多晶硅片和物理提纯硅片的原片、去损减薄片、热氧化钝化片、双面镀氮化硅(SiN x:H)膜钝化片、碘酒钝化片以及太阳电池的光衰规律.利用WT-2000少子寿命测试仪以及太阳电池I-V特性测试仪分别对硅片的少子寿命和太阳电池的I-V特性参数随光照时间的变化进行了测试.结果表明:所有硅片以及太阳电池在光照的最初60 min内衰减很快随后衰减变慢,180 min之后光衰速率变得很小,几乎趋于零.     

银铜双原子MACE法可控制备倒金字塔多晶黑硅的结构与性能

采用一步银铜双原子金属辅助化学腐蚀法,室温下在多晶硅表面制备纳米陷光结构,再利用纳米结构修正溶液在温度为50℃时对硅片进行各向异性重构,可控制备出不同尺寸的倒金字塔陷光结构.用分光光度计测量了多晶硅表面的反射率,用扫描电镜观察了多晶硅表面形貌,用少子寿命测试仪测量了多晶硅钝化后的少子寿命.结果表明:影响倒金字塔结构尺寸的主要影响因素是制备态黑硅纳米结构的深度,当深度越深,最终形成的结构尺寸也越大;纳米结构修正溶液重构时间越长,所形成的倒金字塔结构尺寸越大,反射率也变大;经原子层沉积钝化后的倒金字塔结构中少子寿命随其尺寸的增大而增加;当倒金字塔边长为600nm时综合效果最佳,反射率为9.87%,少子寿命为37.82μs.     

多晶硅中的氧碳行为及其对太阳电池转换效率的影响

认识及控制多晶硅中杂质行为对于实现低成本、高效率多晶硅太阳电池有着重要的意义.利用红外光谱技术研究了定向凝固多晶硅锭中不同部位材料热处理前后的氧浓度、碳浓度变化,结合少子寿命、光电转换效率、内量子效率等电池性能,探索不同含量的氧、碳杂质对电池性能影响的物理机制.提出一种考虑碳影响的氧沉淀生长模型,并模拟了热处理后氧沉淀的尺寸分布和数量.研究发现,碳除了使利用硅锭顶部材料制备得到的电池转换效率降低外,还是决定氧沉淀作用的重要因素.由于碳含量多造成中部材料氧沉淀的尺寸大、数量多,引起缺陷,增加复合,而碳在底部 关键词： 氧 碳 太阳电池 转换效率     

Effects of phosphorus diffusion gettering on minority carrier lifetimes of single-crystalline,multi-crystalline and UMG silicon wafer

Phosphorus diffusion gettering, which can effectively reduce the transition-metal impurities in the bulk of Si wafer and enhance the minority carrier lifetime (MCLT), is a well-known process to improve the performances of solar cells. Especially, the appropriate gettering process is further required for manufacturing solar cells using an upgraded metallurgical-grade silicon (UMG Si) wafer. In this work, an improvement in the MCLT of the UMG Si wafer including the single-crystalline and multi-crystalline Si wafer after phosphorus diffusion gettering was confirmed by using the quasi-steady state photo-conductivity (QSSPC) measurement and the microwave photo-conductance decay (μW-PCD) method. The experimental results were compared with the MCLT variations calculated through the simulation of the Fe distributions in the Si wafers. It was also observed that the efficiency of the UMG Si solar cell increased by 0.53% due to the two-step gettering process.     

Enhancement of optoelectronic properties in multicrystalline silicon via combination of grooving grain boundaries and porous silicon gettering

In multi-crystalline silicon (mc-Si), the detrimental effect of impurities and grain boundaries (GBs) on charge carrier transport has driven the research focus since many years. In view of curing these limitations, we present an innovative method to enhance the optoelectronic performance of mc-Si wafers via a combination between GBs grooving and porous silicon (PS) gettering. A preferential grooving of GBs was achieved using the HF/HNO₃ based solution, the PS layers were formed on both sides of the samples using stain-etching method and the gettering experiment was performed at temperatures ranging from 750 to 900 °C. As a result, it has been shown that the rapid thermal annealing process with chemical grooving gives a positive trend of improvement of the electronic quality and found to be more efficient when used in combination with PS. After removing the PS layer, the minority carrier lifetime increases by a factor of more than 27. In addition, a significant enhancement of majority carrier mobility was obtained, which led to an important decrease of the resistivity.     

Low‐Temperature Saw Damage Gettering to Improve Minority Carrier Lifetime in Multicrystalline Silicon

The minority carrier lifetime in multicrystalline silicon ? a material used in the majority of today's manufactured solar cells ? is limited by defects within the material, including metallic impurities which are relatively mobile at low temperatures (≤700 °C). Addition of an optimised thermal process which can facilitate impurity diffusion to the saw damage at the wafer surfaces can result in permanent removal of the impurities when the saw damage is etched away. We demonstrate that this saw damage gettering is effective at 500 to 700 °C and, when combined with subsequent low‐temperature processing, lifetimes are improved by a factor of more than four relative to the as‐grown state. The simple method has the potential to be a low thermal budget process for the improvement of low‐lifetime “red zone” wafers.

     

Electrical properties of purified solar grade silicon substrates using a combination of porous silicon and SiCl4

This work investigates the photo-thermal treatment of solar grade (SG) silicon to reduce impurities to a low level suitable for high efficiency low-cost solar cells application. It describes experiment carried out by using a tungsten lamps furnace (rapid thermal processing, RTP) to purify solar grade silicon wafers using a combination of porous silicon (PS) and silicon tetrachloride. This process enables to attract the impurities towards the porous layer where they react with SiCl₄ to form metallic chlorides. The gettering effect was studied using the Hall Effect and the Van Der Pauw methods to measure the resistivity, the majority carrier concentration and mobility. We have obtained a significant improvement of the majority carrier mobility after such thermo-chemical treatment. The gettering efficiency is also evaluated by the relative increase of the minority carrier diffusion length L, measured by the light beam induced current (LBIC) technique.     

Improving the material quality of silicon ingots by aluminum gettering during crystal growth

We present a method for the purification of silicon ingots during the crystallization process that reduces significantly the width of the low charge carrier lifetime region at the ingot top. The back‐diffusion of impurities from the ingot top is suppressed by adding a small amount of pure aluminum into the silicon melt right at the end of the solidification. We study the aluminum gettering effect by instrumental neutron activation analysis (INAA) and Fe_i imaging. Furthermore, we present a model for aluminum gettering of Fe in the silicon ingot that is in agreement with literature data for aluminum gettering at lower temperature. The distribution of iron in the ingots with and without aluminum is fairly well predicted by a combination of this model with a model for Fe contamination from the crucible system. A simulation with varying Al content exhibits further potential for an increased yield of silicon wafers with high charge carrier lifetime. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Gettering of metallic impurities in photovoltaic silicon

 This work addresses the issue of structural defect-metallic impurity interactions in photovoltaic silicon and their effect on minority carrier diffusion length values. Aluminium and phosphorus segregation gettering studies were performed on photovoltaic silicon in order to gain insight into these interactions and quantify the effect of gettering on solar cell performance. Integrated circuit grade silicon was also studied for comparative purposes. Additionally, a novel rapid thermal annealing technique, designed to dissolve metallic impurity precipitates, and Deep Level Transient Spectroscopy were utilized to determine the as-grown impurity concentration in both grades of materials. Significant differences in gettering responses between the two grades of silicon are observed. Gettering treatments greatly improve I.C. grade silicon with a specific gettering temperature providing the optimal response. Photovoltaic grade silicon does not respond as well to the gettering treatments and, in some cases, the material degrades at higher gettering temperatures. The degradation is primarily observed in dislocated regions of multicrystalline photovoltaic silicon. Additionally, these dislocated regions were found to possess the highest as-grown metallic impurity concentration of all the materials studied. The dislocation-free photovoltaic silicon has a higher diffusion length relative to dislocated silicon but could not be improved by the gettering methods employed in this study. A model is presented to describe these phenomena where the high concentration of metallic impurities at dislocations produce relatively low minority carrier diffusion lengths as well as the degrading response with higher gettering temperatures while microdefects create an upper limit to the photovoltaic grade material’s diffusion length. Received: 21 June 1996/Accepted: 2 September 1996     

Iron contamination in silicon technology

This article continues the review of fundamental physical properties of iron and its complexes in silicon (Appl. Phys. A 69, 13 (1999)), and is focused on ongoing applied research of iron in silicon technology. The first section of this article presents an analysis of the effect of iron on devices, including integrated circuits, power devices, and solar cells. Then, sources of unintentional iron contamination and reaction paths of iron during device manufacturing are discussed. Experimental techniques to measure trace contamination levels of iron in silicon, such as minority carrier lifetime techniques (SPV, μ-PCD, and ELYMAT), deep-level transient spectroscopy (DLTS), total X-ray fluorescence (TXRF) and vapor-phase decomposition TXRF (VPD-TXRF), atomic absorption spectroscopy (AAS), mass spectrometry and its modifications (SIMS, SNMS, ICP-MS), and neutron activation analysis (NAA) are reviewed in the second section of the article. Prospective analytical tools, such as heavy-ion backscattering spectroscopy (HIBS) and synchrotron-based X-ray microprobe techniques (XPS, XANES, XRF) are briefly discussed. The third section includes a discussion of the present achievements and challenges of the electrochemistry and physics of cleaning of silicon wafers, with an emphasis on removal of iron contamination from the wafers. Finally, the techniques for gettering of iron are presented. Received: 16 November 1999 / Accepted: 7 January 2000 / Published online: 5 April 2000     

Electronic states at dislocations and metal silicide precipitates in?crystalline silicon and their role in?solar cell materials

Predominant dislocation types in solar silicon are dissociated into 30°- and 90°-partials with reconstructed cores. Besides shallow 1D-band localized in their strain field and a quasi-2D band at the stacking fault connecting the two partials, the existence of several intrinsic core defects with deep lying levels has been demonstrated by electron spin resonance. The majority of core defects occur in nonequilibrium situations and, with the exception of a small EPR-signal assigned to a reconstruction defect, vanish after careful annealing above 800°C. There is good evidence now that part of deep levels observed in dislocated silicon is associated with impurities, especially with transition metal impurities. Electron-hole-pair recombination at a dislocation mainly runs via its shallow bands and is strongly increased by impurities bound to its core or in the strain field. The concentration of these impurities can be reduced by gettering processes to such a low level that radiative recombination at dislocations yields a luminescence efficiency of 0.1% at room temperature. A quite coherent picture has emerged for metal impurity precipitation in silicon. Early stages of precipitation in defect-free silicon are characterised by kinetically selected metastable defects forming as a result of large chemical driving forces for precipitation. Such defects are associated with deep level spectra which show the properties of extended multielectron defects. The evolution of the system to energetically more favourable configurations proceeds via ordinary particle coarsening but also via internal ripening, a process reminiscent of the above-mentioned metastable defects. Electronically, the defects evolve into metal-like inclusions which in general seem to act as strong recombination centers for minority carriers. In the presence of dislocations metastable defects quickly transform into equilibrium structures in the course of precipitation or do not form at all. In the presence of several metal impurities silicide precipitates which can be described as solid solutions of the respective metal atoms are observed, which is at least qualitatively in accord with ternary phase diagrams. Like single-metal silicide precipitates, strong minority carrier recombination is also typical for those multi-metal silicide particles.