Electrical conductivity and viscosity of cryolite electrolytes for solar grade silicon(Si-SoG) electrowinning

Electrical conductivity of molten binary and ternary mixtures based on the system NaF-AlF3-SiO2 was investigated by means of a tube–cell （made of pyrolytic boron nitride） with stationary electrodes. Viscosity of the binary system Na3AlF6-SiO2 was measured by computerized torsion pendulum method. It was found that conductivity and viscosity varied linearly with temperature in all investigated mixtures. Obtained content dependence of electrical conductivity （isotherms） was divided into two parts. First, one represented the content region up to 10%（mole fraction） of SiO2;second, the region was with a higher content of SiO2 （from 10%up to 40%）. While the conductivity considerably decreased with content of SiO2 in the second part; it surprisingly rose in the low content range. A small addition of SiO2 to the molten cryolite （up to 10%） could slightly increase viscosity, but had no influence on the slope of this dependence since it is responsible for a glassy-networks formation in the melt. Further addition of SiO2 to the molten cryolite had a huge effect on the viscosity.

Removal of SiC particles from solar grade silicon melts by imposition of high frequency magnetic field

Non-metallic particles and metallic impurities present in the feedstock affect the electrical and mechanical properties of high quality silicon which is used in critical applications such as photovoltaic solar cells and electronic devices. SiC particles strongly deteriorate the mechanical properties of photovoltaic cells and cause shunting problem. Therefore, these particles should be removed from silicon before solar cells are fabricated from this material. Separation of non-metallic particles from liquid metals by imposing an electromagnetic field was identified as an enhanced technology to produce ultra pure metals. Application of this method for removal of SiC particles from metallurgical grade silicon （MG-Si） was presented. Numerical methods based on a combination of classical models for inclusion removal and computational fluid dynamics （CFD） were developed to calculate the particle concentration and separation efficiency from the melt. In order to check efficiency of the method, several experiments were done using an induction furnace. The experimental results show that this method can be effectively applied to purifying silicon melts from the non-metallic inclusions. The results are in a good agreement with the predictions made by the model.

Vacuum distillation refining of metallurgical grade silicon(Ⅰ)——Thermodynamics on removal of phosphorus from metallurgical grade silicon

The removal of impurity phosphorus from metallurgical grade silicon is one of the major problems on purification of metallurgical grade silicon for solar grade silicon preparation. The thermodynamics on vacuum refining process of the metallurgical grade silicon was studied via separation coefficient of impurity phosphorus in the metallurgical grade silicon and vapor-liquid equilibrium composition diagram of Si-P binary alloy at different temperatures. The behaviors of impurity phosphorus in the vacuum distillation process were examined. The results show that the vacuum distillation should be taken to obtain silicon with less than 10-7 P,and the impurity phosphorus is volatilized easily by vacuum distillation in thermodynamics. Phosphorus is distilled from the molten silicon and concentrated in vapor phase.

Removal of iron and aluminum impurities from metallurgical grade-silicon with hydrometallurgical route

A new method for production of solar grade silicon(SoG-Si) at low cost from metallurgical grade silicon(MG-Si) via vacuum metallurgical technique was proposed,which is a promising process to feedstock solar energy silicon material independence of traditional Siemens method. In this procedure,pre-treatment of MG-Si using hydrometallurgical routes to remove the metallic impurities such as iron and aluminum to reduce the production cost is an important process. The influences of acid agents,acid concentration,reaction time and temperature and particle size of raw material ground on the removal efficiency of iron and aluminum impurities were investigated,respectively. The results show that the optimum operation conditions for leaching in acid C are:acid concentration 6 mol/L,temperature 60 ℃,time 4 d,diameter for raw material 50 μm. The removal efficiencies of impurities iron and aluminum are up to 85% and 75%,respectively.

Vacuum distillation refining of metallurgical grade silicon(Ⅱ)——Kinetics on removal of phosphorus from metallurgical grade silicon

The kinetics on vacuum refining process of metallurgical grade silicon was studied using maximum evaporation rate,critical pressure and mean free path of phosphorus in the metallurgical grade silicon at different temperatures. The behaviors of impurity phosphorus in the vacuum distillation process were examined in detail. The results show that the fractional vacuum distillation should be taken to obtain silicon with high purity. Impurity phosphorus volatilize with the maximum evaporation rate of 1.150×105- 1.585×106 g/(cm2·min) in the temperature range of 1 073-2 173 K and the pressure below 2.1 Pa. Because the value of ωmax,P is at least 108 times of ωmax,Si,Si hardly evaporates and remains in the residual,which indicates that phosphorus can be removed from metallurgical grade silicon(MG-Si) completely.

Boron removal from metallurgical silicon using CaO-SiO_2-CaF_2 slags

The removal of boron from metallurgical silicon in slag system of CaO-SiO2-10%CaF2 was investigated. The partition coefficient of boron （LB） between slag and silicon phase was studied under different conditions of slag basicity （CaO/SiO2 ratio）, temperature, mass ratio of slag to silicon and gas blowing. The results show that LB has a maximum value of 4.61 when the CaO/SiO2 mass ratio is around 2 at l 873 K. The logarithm of LB is linear to the reciprocal of temperatures in the range of 1 773-1 973 K. LB increases with the increase of mass ratio of slag to silicon, but it does not increase markedly when the ratio excesses 3. Gas blowing can sionificantlv increase the removal of boron, and LR increases with the increase of water vapor content.

Low-temperature purification process of metallurgical silicon

The removal of B and P consumes most of heat energy in Si metallurgical purification process for solar-grade Si. Metal-liquating purification of metallurgical grade silicon （MG-Si）, also called Si-recrystallization from metal liquid, was a potential energy-saving method for the removal of B and P efficiently, since Si could be melted at lower temperature by alloying with metal. The selection criteria of metal-liquating system was elaborated, and Al, Sn and In were selected out as the optimum metallic mediums. For Sn-Si system, the segregation coefficient of B decreased to 0.038 at 1 500 K, which was much less than 0.8 at the melting point of Si. The mass fraction of B was diminished from 15×10^-6 to 0.1×10^-6 as MG-Si was purified by twice, while that of most metallic elements could be decreased to 0.1×10^-6 by purifying just once. During the metal-liquating process, the formation of compounds between impurity elements and Si was also an important route of impurity removal. Finally, one low-temperature metallurgical process based on metal-liquating method was proposed.

极性相反杂质在硅锭中的抵偿效应研究

采用Scheil方程和四探针法、霍尔效应技术、紫外-可见光吸收光谱以及XRD技术分别模拟和测试太阳能硅锭的杂质分布、电阻率、载流子浓度、带隙以及晶体结构,结果表明:若硅料中施主杂质原子浓度小于受主杂质的0.39倍,铸造的p型硅锭不会出现极性反转。由于极性相反杂质间的抵偿效应,在硅锭极性反转处形成p-n结区,少子寿命和体电阻率均达到最大值,且硅锭的晶体结构未发生改变,带隙比特征硅锭的带隙降低25.89%,对此段硅锭切片,可省略后续硅片的“磷扩散”过程。利用掺杂剂抵偿技术可制备高效率和低成本的晶硅太阳电池。

冶金硅造渣精炼制备太阳级硅研究进展

清洁可再生能源是解决未来能源短缺的重要途经,晶体硅光伏电池因其清洁、无污染的特点被广泛应用。太阳级硅(SOG-Si)要求硅的纯度达到99.9999%,如何研发高纯硅的低成本高效制备工艺是目前产学研界共同研究的热点和难点。由于造渣精炼法具有成本低,能耗低,设备简易,易于工业化生产等特点,被认为是冶金法制备太阳级硅的重要方法之一。本文系统回顾了近年来造渣精炼法提纯冶金硅的研究进展,对比分析二元渣系、多元渣系、合金−渣体系的除杂效果及机制,为研究人员研究造渣精炼法SOG-Si提供理论指导。

太阳能级多晶硅生产技术发展现状及展望

全面介绍了太阳能级多晶硅的生产技术现状及有代表性的新工艺、新技术的研究动态。太阳能级多晶硅生产技术主要包括西门子法、硅烷法和冶金法。冶金法因工艺简单、投资少、能耗低获得广泛的关注，但目前其产品达不到太阳能级硅的质量要求。展望未来，西门子法仍将是生产高纯度多晶硅的主流技术。

冶金法制备太阳能级多晶硅新工艺原理及研究进展

随着光伏市场需求不断增加,能满足光伏电池技术经济指标要求的硅材料出现严重短缺,冶金法制备太阳能级多晶硅新工艺技术由于其能耗低、成本低,越来越受到国内外的广泛重视,成为研究开发的热点。综述了近年来国内外有关冶金法提纯冶金级硅至太阳能级硅的各种工艺路线的原理及成果,并进行了比较分析,展望了其应用前景。

冶金级硅氧化精炼提纯制备太阳能级硅研究进展

综述了目前冶金级硅氧化精炼制备太阳能级硅的研究进展,详细介绍了熔渣精炼、吹气氧化精炼和热等离子体精炼的方法和装置以及杂质的去除效果。研究发现:上述氧化精炼方法对硅中杂质元素Al、Ca、Cu、B、P等具有很好的去除效果;熔渣和吹气氧化精炼对Fe不明显,须借助于定向凝固方法才能彻底的去除;吹气氧化精炼和等离子体精炼对硅中B的去除效果十分明显,可使其降低至0.1ppmw以下,这为当前冶金法提纯制备太阳能级硅在技术和工艺上提供了很好的思路;通过氧化精炼,硅中杂质元素完全可以达到太阳能级硅的要求。本文提出,吹气氧化精炼(或等离子体精炼)与定向凝固精炼联合使用并形成规模化和连续化精炼装置是加快我国太阳能级硅产业化进程最切实可行的办法和措施。

冶金法制备太阳能级多晶硅研究现状及发展趋势

冶金法是我国走出硅原料依赖,发展低成本、环境友好的太阳能级多晶硅制备技术的必经之路,冶金法自诞生以来在世界范围内经历了三次研究高潮,第三次正是在以我国科研和产业工作者为主导和推动下发展的,并形成了大量有益的科学结论和实践经验。本文从冶金法的界定开始,详细分析了冶金法提纯的理论基础,饱和蒸汽压机理、偏析机理和氧化性差异机理,介绍了以上机理所衍生出的技术方法及进展,并对冶金法的发展前景进行了展望。

太阳能级硅制备新工艺研究进展

本文总结了当前国内外多晶硅的几种生产工艺,以及目前国内外多晶硅生产的最新研究和发展趋势。指出了目前多晶硅发展过程中所存在的问题,并结合自己的工作提出了今后多晶硅发展的新思路。

冶金法制备太阳能硅过程的湿法提纯研究

湿法提纯作为冶金法路线制备太阳能级硅的前处理工序,可以去除大部分金属杂质,提高最终产品收率。考察了硅粉粒径、浸出剂浓度、温度、时间、搅拌等因素的影响,采用ICP、SEM等对产品进行了表征。当工艺条件为:硅粉平均粒径44μm、w(HCl)=5%、温度80℃、时间6h,处理后产品中杂质w(Fe)=2.4×10-5,去除率为99.2%,杂质w(Al)=6.4×10-5,去除率为80%。描述了酸浸过程在前后不同阶段分别为受反应速度和内扩散控制历程。为太阳能级硅制备工业化开发,大幅度降低成本提供了参考。

冶金法制备太阳能硅过程的湿法除硼研究

湿法提纯作为冶金法路线制备太阳能级硅前处理工序,可去除大部分铁铝等碱金属及硼杂质,提高最终产品收率。实验考察了湿法除硼过程主要工艺因素:浸出剂浓度、温度、时间、搅拌等对产品纯度的影响,采用SEM对产品进行表征。当工艺条件为c(HNO3)=6.5 mol/L,c(H2SO4)=6 mol/L,温度120℃、时间4 h,处理后产品中杂质质量分数为3.574×10-6,湿法过程单元的去除率为44.58%。实验结果为高等级太阳能级硅制备工业化开发大幅度降低成本提供了技术基础。

太阳能电池硅转换材料现状及发展趋势

目前太阳能电池工业转换材料绝大多数都采用硅,而硅材料主要来自于半导体工业的废料。作为硅集成电路和器件用的多晶硅原料的生产普遍采用西门子法。随着光伏产业的迅速发展,来自半导体级硅的废料预计不会明显增加。因此,将不能满足太阳能电池用硅的需求,硅原料已经成为光伏产业发展的最主要的瓶颈之一。为了满足太阳能电池工业健康发展,研究开发一个不依赖于半导体硅生产的低成本太阳能级硅供应体系是非常必要的。

冶金法制备太阳能级硅的原理及研究进展

随着光伏市场需求不断增加,满足光伏电池技术经济指标要求的硅材料出现严重短缺,低成本提纯冶金硅至太阳能级硅工艺技术越来越受到广泛重视,成为研究开发热点。本文分析了全球光伏产业的发展现状和趋势,对目前获得太阳能级多晶硅的化学路径和冶金路径进行了对比分析;重点介绍了冶金法制备太阳能级硅的工艺原理,以及目前常用的提纯技术;同时,简单介绍低成本生产太阳能级多晶硅的新工艺,并指出了冶金法可能是今后提纯多晶硅的主要研究方向。

精炼法提纯冶金硅至太阳能级硅的研究进展

随着光伏市场需求不断增加,满足光伏电池技术经济指标要求的硅材料出现严重短缺,低成本提纯冶金硅至太阳能级硅工艺技术越来越受到广泛重视,成为研究开发热点。综述了近年来国外有关基于定向凝固原理开发的精炼法提纯冶金硅至太阳能级硅的技术成果,并进行了比较分析,展望了应用前景。

提纯工业硅除铝的实验研究

为了去除工业硅中的杂质制备太阳能级硅,根据工业硅凝固过程中铝在固相和液相中溶解度的差异,采用定向凝固法去除工业硅中的杂质铝。实验结果表明,铝的去除效率可达98%,说明利用定向凝固法去除工业硅中的铝是可行的。但由于在结晶过程中晶界上会富集部分铝元素,因而定向凝固法并不能除去这一部分杂质。结合金相实验中样品腐蚀前后晶界上的变化,可以知道利用酸浸可以除去晶界上的杂质铝。还研究了先酸浸后定向凝固法相结合除铝,实验结果表明铝的含量可以降到1.6×10-5,铝的去除率达98.6%。