Research on Removal of Impurities from Metallurgical Grade Silicon（MG-Si） by Electron Beam Melting（EBM）

Solar cells are currently fabricated from a variety of silicon-based materials.Now the major silicon material for solar cells is the scrap of electronic grade silicon(EG-Si).But in the current market it is difficult to secure a steady supply of this material.Therefore,alternative production processes are needed to increase the feedstock.In this paper,EBM is used to purify silicon.MG-Si particles after leaching with an initial purity of 99.88%in mass as starting materials were used.The final purity of the...     

废弃多晶硅太阳电池回收高纯硅片工艺研究

论述分析了国内外晶体硅太阳电池回收技术现状,研究了太阳电池的结构及制备工艺,提出了废弃多晶硅太阳电池回收高纯硅片的工艺.依次去除铝背场/铝硅合金层/背银、氮化硅减反膜/正银、磷扩散层及金属杂质,得到高纯硅片.硅原料的回收率高达76.4％,回收的高纯硅片经检验检测,其电阻率、间隙氧浓度、代位碳含量和少子寿命均符合GB/T 29055-2012中规定的性能参数.该回收工艺路线简单,回收率高,成本低,适于产业化推广.废弃太阳电池的回收再利用不仅可以在一定程度上缓解硅原料短缺的问题,还可以减少废弃的太阳电池给环境造成负担.     

多晶黑硅表面微结构对电池效率的影响

采用Ag离子辅助化学刻蚀法制备了多晶黑硅薄片,使用NaOH溶液处理多晶黑硅表面,增大其表面纳米孔直径,使SiNx薄膜能够均匀覆盖整个黑硅表面,提高黑硅的钝化效果,进而提高多晶黑硅电池光电转化效率.通过反射谱仪、扫描电子显微镜(SEM)、太阳电池测试系统等测试和表征不同扩孔时间对多晶黑硅各方面性能的影响.结果表明:未被NaOH扩孔处理的多晶黑硅的反射率最低,为5.03％,多晶黑硅太阳电池的光电转化效率为16.51％.当多晶黑硅被NaOH腐蚀40 s时,反射率为10.01％,电池的效率为18.00％,比普通多晶硅太阳电池的效率高2.19％,比未被扩孔处理的多晶黑硅太阳电池的效率高1.49％.     

多孔硅可见光发射研究

用常规电化学方法制备了发射高效可见光的多孔硅样品。对样品进行了光谱研究。用非化学方法从样品表面得到了粉末状荧光物质(非多孔硅膜研磨产物),光谱测定证实它的光致发光光谱与原多孔硅样品光致发光光谱相同,粉末进一步研磨后仍能发出同样的可见光。多孔硅样品还可以实现阴极射线激发发出同样的高效可见光,但易因电子束的轰击而发光强度较快减弱。用扫描电镜(SEM)对多孔硅样品的形貌、结构、荧光粉末的形状、尺寸、多孔硅样品阴极荧光发射区域进行了系统的研究。实验结果表明多孔硅样品一般可分为三层结构:表面层、多孔层和单晶硅衬底,样品荧光是来源于其表面层的。对样品表层组分的x射线光电子谱(XPS)分析表明,此时的多孔硅表层有大量非硅元素存在,如:C、O、F(没考虑H),硅元素的原子个数比只占30％～50％。用同样的电化学方法在单晶硅未抛光面上和多晶硅未抛光面上制得了均匀发射可见光样品。上述实验结果说明,多孔硅的高效可见光发射是来源于样品制备过程中在其表面层中形成的粉末状荧光物质。     

High‐efficiency solar cells on phosphorus gettered multicrystalline silicon substrates

Measurements of the dislocation density are compared with locally resolved measurements of carrier lifetime for p‐type multicrystalline silicon. A correlation between dislocation density and carrier recombination was found: high carrier lifetimes (>100 µs) were only measured in areas with low dislocation density (<10⁵ cm⁻²), in areas of high dislocation density (>10⁶ cm⁻²) relatively low lifetimes (<20 µs) were observed. In order to remove mobile impurities from the silicon, a phosphorus diffusion gettering process was applied. An increase of the carrier lifetime by about a factor of three was observed in lowly dislocated regions whereas in highly dislocated areas no gettering efficiency was observed. To test the effectiveness of the gettering in a solar cell manufacturing process, five different multicrystalline silicon materials from four manufacturers were phosphorus gettered. Base resistivity varied between 0·5 and 5 Ω cm for the boron‐ and gallium‐doped p‐type wafers which were used in this study. The high‐efficiency solar cell structure, which has led to the highest conversion efficiencies of multicrystalline silicon solar cells to date, was used to fabricate numerous solar cells with aperture areas of 1 and 4 cm². Efficiencies in the 20% range were achieved for all materials with an average value of 18%. Best efficiencies for 1 cm² (20·3%) and 4 cm² (19·8%) cells were achieved on 0·6 and 1·5 Ω cm, respectively. This proves that multicrystalline silicon of very different material specification can yield very high efficiencies if an appropriate cell process is applied. Copyright © 2006 John Wiley & Sons, Ltd.     

Investigation of bulk and solar cell properties of ingots cast from compensated solar grade silicon

In this work, the effect of the concurrent presence of B and P on bulk and solar cell properties of directionally solidified multicrystalline ingots from commercially compensated solar grade silicon (SoG‐Si) feedstock produced by Elkem Solar was investigated. The initial B and P content prior to the directional solidification experiment was 1260 and 762 ppba, respectively. Two reference ingots have been solidified in a silica crucible from 100% electronic grade silicon (EG‐Si) feedstock, with 332 ppba of boron added. All ingots have been cast under similar process parameters. The resistivity measurements by Four Point Probe (FPP) are in good agreement with the net dopant content, i.e., N_A − N_D for p‐type material, measured by Glow Discharge Mass Spectrometer (GDMS). Bulk lifetime measurements show a decrease in the values compared to the EG reference. Lifetime distributions show the highest values of 13 and 19 µs at approximately half ingot height, compared to 30 and 44 µs in the reference ingots. This decrease can be due to the concurrent effect of compensation and of other impurities present in the ingot. However, the content of several transition metals measured by GDMS at half ingot height was not significantly higher than that of the reference ingots. Oxygen content as measured by Fourier Transform Infra‐Red (FTIR) spectroscopy shows no significant difference compared to the references. Solar cells made from the compensated ingots and processed under standard process conditions show efficiency values up to 15.5% and fill factor values up to 78%, comparable to conventional multicrystalline silicon cells. Copyright © 2010 John Wiley & Sons, Ltd.     

超快激光微构造硅的研究与应用

在特定的气体氛围下,用一定能量密度的超短脉冲激光连续照射单晶硅片表面,或者离子注入在硅中引入硫族元素等方法,可在硅表面得到具有奇特光电性质的微米量级尖锥结构,该微锥结构被称为黑硅。这一新材料有奇特的光电性质,如对0.25～17μm波长的光有强烈的吸收,具有良好的场致发射特性等,为硅提供许多新的功能。Mazur教授预言这种新材料相当于60年前的半导体,在探测器、传感器、显示技术及微电子等领域都有重要的潜在应用价值,尤其在高效太阳能电池领域具有其他材料无可比拟的优越性。本文介绍了超快激光微构造硅的形成机理,研究进展、光电特性以及应用前景。     

不同直径张应变锗材料对光谱和晶体质量的影响

绝缘体上张应变锗材料是通过能带工程提高锗材料光电性能得到的一种新型半导体材料,在微电子和光电子领域具有重要的应用前景.采用微电子技术中的图形加工方法以及利用锗浓缩的技术原理,在绝缘体上硅(SOI)材料上制备了绝缘体上张应变锗材料.喇曼与室温光致发光(PL)测试结果表明,不同圆形半径的绝缘体上锗材料张应变均为0.54％.对于绝缘体上张应变锗材料,应变使其发光红移的效果强于量子阱使其发生蓝移的效果,总体将使绝缘体上张应变锗材料的直接带发光峰位红移.同时0.54％张应变锗材料的直接带发光强度随着圆形半径的增大而减弱,这主要是因为圆形半径大的样品其晶体质量较差.该材料可进一步用于制备锗微电子和光电子器件.     

Efficiency-limiting defects in silicon solar cell material

The precipitation rate of intentionally introduced iron during low-temperature heating is studied among a variety of single-crystal and polycrystalline silicon solar cell materials. A correlation exists between the iron precipitation rate and the carrier recombination rate in dislocation-free as-grown material, suggesting that diffusion-length-limiting defects in as-grown material are structural defects which accelerate iron precipitation. Phosphorous diffusion gettering was found to be particularly ineffective at improving diffusion length after intentional iron contamination in materials with high iron precipitation rates. We propose that intragranular structural defects in solar cell silicon greatly enhance transition metal precipitation during cooling from the melt and become highly recombination-active when decorated with these impurities. The defects then greatly impair diffusion length improvement during phosphorus gettering and limit carrier lifetimes in as-grown material.     

Ohmic contacts on high purity P-type silicon

A new method of forming electrical contacts on high purity p-type silicon has been developed. The resultant contacts are ohmic from 18 to 300K. The electrical sparking technique permits localized doping in the contact region of the device while avoiding the over-all high annealing temperatures required by diffusion. Indium solder is used for metallization and attachment of wires to the sparked regions. The process is simple and easily applied to samples for measuring electrical transport properties or to devices, such as silicon solar cells.     

SiC sedimentation and carbon migration in mc-Si by election beam melting with slow cooling pattern

The development of photovoltaic industry demands great amount of multicrystalline silicon. Carbon and SiC in silicon need to be contained in a limited amount since they can cause great adverse affect to solar cells. The behavior of carbon and its precipitation SiC in silicon by electron beam melting (EBM) with a slow cooling pattern was investigated in this study. SiC is found to sedimentate to ingot bottom after EBM. The presence of Si₃N₄ can be heterogeneous nucleation agent for SiC to nucleate continually and both of them precipitate to the ingot bottom. The comprehensive effect of slow solidification condition, temperature gradient and melt convection causes the sedimentation of SiC. It is also found that oxygen plays an important role on the migration of the dissolved carbon. The formation of carbon-oxygen complexes tend to migrate to ingot top since oxygen can transfer from silicon melt to vacuum environment during EBM.     

Improved micromorph solar cells by means of mixed‐phase n‐doped silicon oxide layers

A good light trapping scheme is necessary to improve the performance of amorphous/microcrystalline silicon tandem cells. This is generally achieved by using a highly reflective transparent conducting oxide/metal back contact plus an intermediate reflector between the component cells. In this work, the use of doped silicon oxide as alternative n‐layer in micromorph solar cells is proposed as a means to obtain high current values using a simple Ag back contact and no extra reflector between the component cells n‐doped silicon oxide layers with a wide range of optical and electrical properties have been prepared. The influence of different deposition regimes on the material properties has been studied. The main findings are the following: (i) when carbon dioxide is added to the gas mixture, sufficiently high hydrogen dilution is necessary to widen the transition region from highly conductive microcrystalline‐like films to amorphous material characterized by low electrical conductivity; (ii) lower refractive index values are found with lower deposition pressure. Optimal n‐doped silicon oxide layers have been used in both component cells of micromorph devices, adopting a simple Ag back contact. Higher current values for both cells are obtained in comparison with the values obtained using standard n‐doped microcrystalline silicon, whereas similar values of fill factor and open circuit voltage are measured. The current enhancement is particularly evident for the bottom cell, as revealed by the increased spectral response in the red/infrared region. The results prove the high potential of n‐doped silicon oxide as ideal reflector for thin‐film silicon solar cells. Copyright © 2011 John Wiley & Sons, Ltd.     

High efficiency UMG silicon solar cells: impact of compensation on cell parameters

High efficiency solar cells have been fabricated with wafers from an n‐type Czochralski grown (Cz) ingot using 100% Upgraded Metallurgical‐Grade (UMG) silicon feedstock. The UMG cells fabricated with a passivated emitter and rear totally diffused (PERT) structure have an independently confirmed cell efficiency of 19.8%. This is the highest efficiency reported for a cell based on 100% UMG silicon at the time of publication. The current and power losses are analysed as a function of measured material parameters, including carrier mobility, lifetime and the presence of the boron–oxygen defect. Dopant compensation is shown to reduce both the minority carrier lifetime and mobility, which significantly affects both the current and voltage of the device. Copyright © 2015 John Wiley & Sons, Ltd.     

A New View of Microcrystalline Silicon: The Role of Plasma Processing in Achieving a Dense and Stable Absorber Material for Photovoltaic Applications

To further lower production costs and increase conversion efficiency of thin‐film silicon solar modules, challenges are the deposition of high‐quality microcrystalline silicon (μc‐Si:H) at an increased rate and on textured substrates that guarantee efficient light trapping. A qualitative model that explains how plasma processes act on the properties of μc‐Si:H and on the related solar cell performance is presented, evidencing the growth of two different material phases. The first phase, which gives signature for bulk defect density, can be obtained at high quality over a wide range of plasma process parameters and dominates cell performance on flat substrates. The second phase, which consists of nanoporous 2D regions, typically appears when the material is grown on substrates with inappropriate roughness, and alters or even dominates the electrical performance of the device. The formation of this second material phase is shown to be highly sensitive to deposition conditions and substrate geometry, especially at high deposition rates. This porous material phase is more prone to the incorporation of contaminants present in the plasma during film deposition and is reported to lead to solar cells with instabilities with respect to humidity exposure and post‐deposition oxidation. It is demonstrated how defective zones influence can be mitigated by the choice of suitable plasma processes and silicon sub‐oxide doped layers, for reaching high efficiency stable thin film silicon solar cells.     

大马士革铜阻挡氮化硅薄膜沉积工艺优化研究

在铜大马士革（Damascene）工艺中,为避免由于铜向FSG中扩散所致电迁移的问题,需要在铜表面沉积一层氮化硅作为隔离铜和随后的介电材料的直接接触,通常人们使用HDP—CVD来沉积该氮化硅层。但针对HDP—CVD沉积速率快和工艺设备成本高等问题,文中研究了一种优化了的PECVD氮化硅沉积工艺来取代HDP—CVD氮化硅工艺。优化主要包含硬件改进和工艺参数调整。硬件改进主要通过引入锥形阴极盘面代替传统的直通形阴极盘面,以实现气体分子的更有效电离。在工艺参数上从RF功率、SiH4流量等方面也有所调整。优化后形成的氮化硅薄膜与HDP—CVD氮化硅薄膜性能非常接近,完全符合大马士革工艺的要求。同时氮化硅薄膜的沉积速率也有明显提高,工艺成本随之降低。     

The effect of cathode materials on reactive ion etching of silicon and silicon dioxide in a CF4 plasma

Silicon and silicon dioxide have been Reactive Ion Etched in a CF₄ plasma using a diode sputtering configuration to achieve etching. Pressures ranged from 20 to 100 millitorr and power densities to the RF cathode were between 0.1 and 1.0 W/cm². The effect of cathode material on the quality of etched surfaces and on etch rates has been investigated. It has been observed that the etch rate of silicon decreases as the area of silicon exposed to the plasma is increased and that this silicon loading effect is strongly influenced by the material covering the balance of the cathode. For instance, the silicon loading effect is much more pronounced when silicon dioxide rather than aluminum is used to cover the balance of the cathode. This silicon loading effect was investigated further by varying RF power. It was found that loading a silicon dioxide covered cathode with silicon wafers decreases the dependence of silicon etch rate on power. The silicon dioxide etch rate and its dependence on RF power are the same whether silicon, silicon dioxide or aluminum is used to cover the balance of the cathode. Possible explanations for these experimental results will be discussed.     

VHF-PECVD制备微晶硅材料及电池

采用VHF-PECVD技术制备了不同功率系列的微晶硅薄膜和电池,测试结果表明：制备的适用于微晶硅电池的有源层材料的暗电导和光敏性都在电池要求的参数范围内．低功率或高功率条件下,电池从n和p方向的喇曼测试结果是不同的,在晶化率方面材料和电池也有很大的差别,把相应的材料应用于电池上时,这一点很重要．采用VHFPECVD技术制备的微晶硅电池效率为5%,Voc=0.45V,Jsc=22mA/cm2,FF=50%,Area=0.253cm2．     

多孔硅的应用研究进展

多孔硅是一种新型的纳米半导体光电材料,室温下具有优异的光致发光、电致发光等特性,易与现有硅技术兼容,极有可能实现硅基光电器件等多个领域的应用．扼要论述了多孔硅在绝缘材料、敏感元件及传感器、照明材料及太阳能电池、光电器件以及作为合成其它材料的模板等多个领域内的应用进展情况,并对其发展前景作了展望。     

Interpenetrated Gel Polymer Binder for High‐Performance Silicon Anodes in Lithium‐ion Batteries

Silicon has attracted ever‐increasing attention as a high‐capacity anode material in Li‐ion batteries owing to its extremely high theoretical capacity. However, practical application of silicon anodes is seriously hindered by its fast capacity fading as a result of huge volume changes during the charge/discharge process. Here, an interpenetrated gel polymer binder for high‐performance silicon anodes is created through in‐situ crosslinking of water‐soluble poly(acrylic acid) (PAA) and polyvinyl alcohol (PVA) precursors. This gel polymer binder with deformable polymer network and strong adhesion on silicon particles can effectively accommodate the large volume change of silicon anodes upon lithiation/delithiation, leading to an excellent cycling stability and high Coulombic efficiency even at high current densities. Moreover, high areal capacity of ～4.3 mAh/cm² is achieved based on the silicon anode using the gel PAA–PVA polymer binder with a high mass loading. In view of simplicity in using the water soluble gel polymer binder, it is believed that this novel binder has a great potential to be used for high capacity silicon anodes in next generation Li‐ion batteries, as well as for other electrode materials with large volume change during cycling.     

Large‐area epitaxial silicon solar cells based on industrial screen‐printing processes

Thin‐film epitaxial silicon solar cells are an attractive future alternative for bulk silicon solar cells incorporating many of the process advantages of the latter, but on a potentially cheap substrate. Several challenges have to be tackled before this potential can be successfully exploited on a large scale. This paper describes the points of interest and how IMEC aims to solve them. It presents a new step forward towards our final objective: the development of an industrial cell process based on screen‐printing for > 15% efficient epitaxial silicon solar cells on a low‐cost substrate. Included in the discussion are the substrates onto which the epitaxial deposition is done and how work is progressing in several research institutes and universities on the topic of a high‐throughput epitaxial reactor. The industrial screen‐printing process sequence developed at IMEC for these epitaxial silicon solar cells is presented, with emphasis on plasma texturing and improvement of the quality of the epitaxial layer. Efficiencies between 12 and 13% are presented for large‐area (98 cm²) epitaxial layers on highly doped UMG‐Si, off‐spec and reclaim material. Finally, the need for an internal reflection scheme is explained. A realistically achievable internal reflection at the epi/substrate interface of 70% will result in a calculated increase of 3 mA/cm² in short‐circuit current. An interfacial stack of porous silicon layers (Bragg reflectors) is chosen as a promising candidate and the challenges facing its incorporation between the epitaxial layer and the substrate are presented. Experimental work on this topic is reported and concentrates on the extraction of the internal reflection at the epi/substrate interface from reflectance measurements. Initial results show an internal reflectance between 30 and 60% with a four‐layer porous silicon stack. Resistance measurements for majority carrier flow through these porous silicon stacks are also included and show that no resistance increase is measurable for stacks up to four layers. Copyright © 2005 John Wiley & Sons, Ltd.