Cu(In,Sn)Se2 thin films for absorption of energy from infrared radiation

In this study, we sought to lower the bandgap of thin film solar cells by replacing the Ga used in the absorber layer of Cu(In,Ga)Se₂ with Sn (bandgap of 0.07?eV) to form Cu(In,Sn)Se₂. The proposed scheme was shown to reduce the bandgap of the absorber layer from 1.0?eV to 0.88?eV. Sn films of various thicknesses were deposited using precursors of Sn–In–Cu metal in order to study the effects of Sn/(In?+?Sn) ratio (SIR) on the structure of the material and photoelectrical characteristics of the Cu(In,Sn)Se₂ absorber layer. Experiment results revealed that a higher SIR following selenization increased the grain size and surface roughness of the absorber layer. It increased the quantity of secondary phases of SnSe₂ and Cu₂SnSe₃ and improved the distribution of Cu and In in the absorber layer. A higher SIR was also shown to increase electron mobility while decreasing carrier concentration and conductivity. When SIR≧0.25, the replacement of In³⁺ with Sn⁴⁺in the Cu⁺ vacancies decreased the electron strength of In. We speculate that an increase in SIR caused a relative increase in the quantity of Sn²⁺ compared to Sn⁴⁺, thereby increasing the electron strength of Sn and switching the absorber layer from a p-type to an n-type semiconductor.     

基于锡组分和双轴张应力调控的临界带隙应变Ge_(1-x)Sn_x能带特性与迁移率计算

能带工程通过改变材料的能带结构可以显著提升其电学和光学性质,已广泛应用于半导体材料的改性研究.双轴张应力和Sn组分共同作用下的Ge_(1-x)Sn_x合金,不仅可以解决直接带隙转变所需高Sn组分带来的工艺难题,而且载流子迁移率会显著提升,在单片光电集成领域有很好的应用前景.根据形变势理论,分析了(001)面双轴张应变Ge_(1-x)Sn_x的带隙转变条件,并给出了在带隙转变临界点Sn组分和双轴张应力的关系;采用8κ·p方法,得到了临界带隙双轴张应变Ge_(1-x)Sn_x在布里渊区中心点附近的能带结构,进而计算得到电子与空穴有效质量;基于载流子散射模型,计算了电子与空穴迁移率.计算结果表明:较低Sn组分和双轴张应力的组合即可得到直接带隙Ge_(1-x)Sn_x合金,且直接带隙宽度随着应力的增大而减小;临界带隙双轴张应变Ge_(1-x)Sn_x具有极高的电子迁移率,空穴迁移率在较小应力作用下即可显著提升.考虑工艺实现难度和材料性能两个方面,可以选择4%Sn组分与1.2 GPa双轴张应力或3%Sn组分与1.5 GPa双轴张应力的组合用于高速器件和光电器件的设计.     

Interfaces of high-efficiency kesterite Cu_2ZnSnS(e)_4 thin film solar cells

Cu_2ZnSnS(e)_4(CZTS(e)) solar cells have attracted much attention due to the elemental abundance and the nontoxicity.However,the record efficiency of 12.6% for Cu_2ZnSn(S,Se)_4(CZTSSe)solar cells is much lower than that of Cu(In,Ga)Se_2(CIGS)solar cells.One crucial reason is the recombination at interfaces.In recent years,large amount investigations have been done to analyze the interfacial problems and improve the interfacial properties via a variety of methods.This paper gives a review of progresses on interfaces of CZTS(e)solar cells,including:(i)the band alignment optimization at buffer/CZTS(e)interface,(ii)tailoring the thickness of MoS(e)_2 interfacial layers between CZTS(e)absorber and Mo back contact,(iii)the passivation of rear interface,(iv)the passivation of front interface,and(v)the etching of secondary phases.     

Prediction and optimization of the performance characteristics of CZTS thin film solar cell using band gap grading

The results of the numerical simulation of the performance characteristics of (Cu₂ZnSnS₄) CZTS thin film solar cell due to bandgap grading is presented in this work. The investigation of the performance of this solar cell was carried out using the Analysis of Microelectronics and Photonics software (AMPS-1D). A substrate cell structure FTO/CdS/CZTS/Mo(SLG) was used as the base model. An efficiency of 8.33% was obtained from the simulation with baseline parameters while an intentional grading of the device was carried out on the device both at the front and back interface of the absorber. Front grading was observed to degrade the device performance while significant improvement of the device performance was observed with back grading. An intentional double grading of the device further enhanced the efficiency up to 12.26%.     

Compositional investigation of potassium doped Cu(In,Ga)Se2 solar cells with efficiencies up to 20.8%

We report on the interaction between intentional potassium doping of thin film Cu(In,Ga)Se₂ (CIGS) solar cells, CIGS absorber composition, and device efficiency. Up to now high efficiency CIGS solar cells could not be produced with a gallium/(gallium + indium) ratio higher than 35%. The new doping process step does not only increase solar cell conversion efficiencies up to 20.8%, but also allows a shift in the CIGS absorber composition towards higher gallium content whilst maintaining this high efficiencies level. We find that the saturation of the open circuit voltages for higher gallium content that is normally observed can partially be overcome by the new doping procedure. This observation leads us to the conclusion that even on this high performance level CIGS solar cells still hold a potential for further development beyond the record values reported here. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

空间用倒装三结太阳能电池及其抗辐射性能研究

使用金属有机化学气相沉积技术,在4英寸GaAs衬底上获得了空间用GaInP/GaAs/In_(0.3)Ga_(0.7)As倒装三结太阳能电池.高分辨X射线衍射和阴极射线发光测试结果表明AlInGaAs应力渐变缓冲层的晶格弛豫度约100%,其整面平均穿透位错密度约5.4×10~6/cm~2.与GaInP/InGaAs/Ge常规三结太阳能电池相比,在AM0光谱、25℃测试条件下,面积24 cm~2的倒装三结太阳能电池转换效率达到32%,输出功率提高了5%.采用1 MeV高能电子对倒装三结电池进行粒子辐照测试,电池各项性能参数随不同辐照剂量发生改变,在1×10~(15)/cm~2辐照总剂量下电池转换效率衰降比例达到15%.     

The characteristic of Cu2ZnSnS4 thin film solar cells prepared by sputtering CuSn and CuZn alloy targets

Recent study shows that the main reason for limiting CZTS device performance lies in the low open circuit voltage, and crucial factor that could affect the V_oc is secondary phases like ZnS existing in absorber layer and its interfaces. In this work, the Cu₂ZnSnS₄ thin film solar cells were prepared by sputtering CuSn and CuZn alloy targets. Through tuning the Zn/Sn ratios of the CZTS thin films, the crystal structure, morphology, chemical composition and phase purity of CZTS thin films were characterized by X-Ray Diffraction (XRD), scanning electron microscopy (SEM) equipped with an energy dispersive spectrometer (EDS) and Raman spectroscopy. The statistics data show that the CZTS solar cell with a ratio of Zn/Sn = 1.2 have the best power convention efficiency of 5.07%. After HCl etching process, the CZTS thin film solar cell with the highest efficiency 5.41% was obtained, which demonstrated that CZTS film solar cells with high efficiency could be developed by sputtering CuSn and CuZn alloy targets.     

Regulation of Zn/Sn ratio in kesterite absorbers to boost 10% efficiency of Cu_2ZnSn(S,Se)_4 solar cells

The Zn/Sn ratio in Cu_2ZnSn(S,Se)_4(CZTSSe)films has been regulated to control the composition-related phase,defect,and photoelectric properties for high performance kesterite solar cells.It is found that the increase in the Zn/Sn ratio can slightly narrow the energy band gap to extend the light absorption range and improve the photocurrent.Optimal Zn/Sn ratio of 1.39 in CZTSSe film is obtained with the least secondary phase,the lowest defect density,and the longest charge recombination lifetime.Up to 10.1%photoelectric conversion efficiency has been achieved by this composition regulation.     

Prediction of optoelectronic features and efficiency for CuMX2 (M=Ga,In; X=S,Se) semiconductors using mbj+U approximation

The optoelectronic properties of a selected group of Cu-III-VI₂ chalcopyrites-based materials are deeply investigated by using the modified Becke-Johnson (mBJ) potential, combined with DFT + U approach. The obtained results are further used to calculate these materials’ theoretical efficiency limit for solar cell applications. The bandgap findings indicate a reliable ±0.2 eV agreement. After evaluating the electronic and optical properties, the spectroscopic limited maximum efficiency (SLME) model was used as a metric for the screening. Besides the bandgap value considered in the Shockley–Queisser model, the SLME requires that the absorption spectra, the radiative recombination losses, and the absorber layer thickness must be considered to adequately calculate the efficiency of considered cells. Our findings unveil that some candidates, such as CuInS₂, where an SLME of 30.25% is achieved at a film width of 500 nm can be classified in the category of materials with higher power conversion efficiency.     

Device simulation of quasi-two-dimensional perovskite/silicon tandem solar cells towards 30%-efficiency

Perovskite/silicon (Si) tandem solar cells have been recognized as the next-generation photovoltaic technology with efficiency over 30% and low cost. However, the intrinsic instability of traditional three-dimensional (3D) hybrid perovskite seriously hinders the lifetimes of tandem devices. In this work, the quasi-two-dimensional (2D) (BA)₂(MA)_n-1Pb_nI_3n+1 (n=1, 2, 3, 4, 5) (where MA denotes methylammonium and BA represents butylammonium), with senior stability and wider bandgap, are first used as an absorber of semitransparent top perovskite solar cells (PSCs) to construct a four-terminal (4T) tandem devices with a bottom Si-heterojunction cell. The device model is established by Silvaco Atlas based on experimental parameters. Simulation results show that in the optimized tandem device, the top cell (n=4) obtains a power conversion efficiency (PCE) of 17.39% and the Si bottom cell shows a PCE of 11.44%, thus an overall PCE of 28.83%. Furthermore, by introducing a 90-nm lithium fluoride (LiF) anti-reflection layer to reduce the surface reflection loss, the current density (J_sc) of the top cell is enhanced from 15.56 mA/cm² to 17.09 mA/cm², the corresponding PCE reaches 19.05%, and the tandem PCE increases to 30.58%. Simultaneously, in the cases of n=3, 4, and 5, all the tandem PCEs exceed the limiting theoretical efficiency of Si cells. Therefore, the 4T quasi-2D perovskite/Si devices provide a more cost-effective tandem strategy and long-term stability solutions.     

CZTS‐based materials and interfaces and their effects on the performance of thin film solar cells

Cu₂ZnSnS₄ (CZTS) and its related materials such as Cu₂ZnSnSe₄ (CZTSe) and Cu₂ZnSn(S,Se)₄ (CZTSSe) have attracted considerable attention as an absorber material for thin film solar cells due to the non‐toxicity, elemental abundance, and large production capacity of their constituents. Despite the similarities between CZTS‐based materials and Cu(In,Ga)Se₂(CIGS), the record efficiency of CZTS‐based solar cells remains significantly lower than that of CIGS solar cells. Considering that the difference between the two lies in the choice of the absorber material, the cause of the lower efficiency of CZTS‐based solar cells can be isolated to the issues associated with CZTS‐based materials and their related interfaces. Herein, these issues and the work done to understand and resolve them is reviewed. Unlike existing review papers, every unique region of CZTS‐based solar cells that contributes to its lower efficiency, namely: (1) the bulk of the absorber, (2) the grain boundaries of the absorber, (3) the absorber/buffer layer interface, and (4) the absorber/back contact interface are surveyed. This review also intends to identify the major unresolved issues and the potential improvement approaches of realizing sizable improvements in the solar cells' efficiency, thus providing a guide as to where research efforts should be focused. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

无机钙钛矿太阳能电池Cs2SnI6的电子结构和光学性质的第一性原理研究

近年来,Cs2SnI6作为一种无毒性、稳定性好的新型钙钛矿材料应用于太阳能电池中,其电池的光电转换效率由最初不到1%增长到现在的8.5%,使之成为有可能替代铅基钙钛矿太阳能电池的新型太阳能电池。本文采用基于广义密度泛函和杂化密度泛函的第一性原理方法研究了Cs2SnI6的电子结构、光学特性和钙钛矿太阳能电池的光电性能参数。研究结果表明,导带底和价带顶位于同一高对称点Γ而属于直接跃迁型半导体,且电子态主要来自于I-5p轨道和Sn-5s轨道。在近红外和可见光波长范围内有较高的吸收系数,当Cs2SnI6钙钛矿厚度达到10μm时,吸收率在311~989 nm之间接近100%,不考虑潜在损失的情况下,理论上太阳能电池可获得短路电流为32.86 mA/cm2、开路电压0.91 V、填充因子87.4%、光电转换效率26.1%。为实验上制备高效Cs2SnI6钙钛矿太阳能电池提供了参考。     

A PL and PLE Study of High Cu Content Cu2ZnSnSe4 Films on Mo/Glass and Solar Cells

Physics of the Solid State - Cu2ZnSnSe4 (CZTSe) is amongst leading candidates for the absorber layer in sustainable solar cells. We examine CZTSe thin films with [Cu]/[Zn + Sn] of 0.99 and...     

Graphene/Ag2ZnSnSe4诱导p-n结薄膜太阳电池数值模拟

银锌锡硒(Ag2ZnSnSe4)是一种禁带宽度为1.4 eV的n型半导体材料.本文提出一种由n型Ag2ZnSnSe4与石墨烯(Graphene)组成的Graphene/Ag2ZnSnSe4诱导p-n结薄膜太阳电池,并借助wxAMPS软件对电池的物理机理和性能影响因素进行模拟研究.模拟结果表明,高功函数的石墨烯与n型Ag2ZnSnSe4半导体接触时,Ag2ZnSnSe4吸收层的前端能带向上弯曲,在n型Ag2ZnSnSe4吸收层表面诱导形成p型Ag2ZnSnSe4反型层,p型Ag2ZnSnSe4和n型Ag2ZnSnSe4组成p-n同质结.模拟发现石墨烯和背接触的功函数会影响载流子的分离、输运和收集,严重影响器件性能,石墨烯功函数达到5.5 eV,背接触功函数不高于4.4 eV,都有利于提高器件性能.Ag2ZnSnSe4吸收层的掺杂浓度主要影响器件的短路电流,而Ag2ZnSnSe4吸收层的体内缺陷对器件整体性能产生影响.在石墨烯和背接触功函数分别为5.5和3.8 eV,Ag2ZnSnSe4吸收层的掺杂浓度和缺陷密度分别为1016和1014 cm–3时,Graphene/Ag2ZnSnSe4诱导p-n结薄膜太阳电池能够取得高达23.42%的效率.这些模拟结果为设计新型高效低成本太阳电池提供了思路和物理阐释.     

Extending absorption of near-infrared wavelength range for high efficiency CIGS solar cell via adjusting energy band

The efficient photon harvesting in near infrared wavelength range is still a challenging problem for high performance Cu(In_1-x, Ga_x)Se₂ (CIGS) solar cell. Herein, adjusting the energy band distribution of CIGS solar cell could provide significant academic guidance for devices with superior output electric power. To understand the role of each functional layer, the optimal 3000 nm CIGS absorber layer with 1.3 eV bandgap and 30 nm CdS buffer layer were firstly obtained via simulating the uniform band-gap structures. By introducing CIGS absorber layer with a double grading Ga/(Ga+In) profile, the power conversion efficiency of the double gradient band gap cell is superior to that of uniform band-gap cell through extending absorption of near-infrared wavelength range. Upon optimization, the best power conversion efficiency of CIGS with a double gradient band gap solar cell is improved significantly to 24.90%, among the best values reported in literatures, which is an 8.17% relative increase compared with that of the uniform band-gap cell. Our findings provide a theoretical guide toward the design of high performance solar cells and enrich the understandings of the energy band engineering for developing of novel semiconductor devices.     

直接带隙Ge$lt;sub$gt;1-$lt;em$gt;x$lt;/em$gt;$lt;/sub$gt;Sn$lt;sub$gt;$lt;em$gt;x$lt;/em$gt;$lt;/sub$gt;本征载流子浓度研究

通过合金化改性技术, Ge可由间接带隙半导体转变为直接带隙半导体. 改性后的Ge半导体可同时应用于光子器件和电子器件, 极具发展潜力. 基于直接带隙Ge_1-xSn_x半导体合金8带Kronig-Penny模型, 重点研究了其导带有效状态密度、价带有效状态密度及本征载流子浓度, 旨在为直接带隙改性Ge半导体物理的理解及相关器件的研究设计提供有价值的参考. 研究结果表明: 直接带隙Ge_1-xSn_x合金导带有效状态密度随着Sn组分x的增加而明显减小, 价带有效状态密度几乎不随Sn组分变化. 与体Ge半导体相比, 直接带隙Ge_1-xSn_x合金导带有效状态密度、价带有效状态密度分别低两个和一个数量级; 直接带隙Ge_1-xSn_x合金本征载流子浓度随着Sn组分的增加而增加, 比体Ge半导体高一个数量级以上. 关键词： 1-xSn_x')" href="#">Ge_1-xSn_x 直接带隙 本征载流子浓度     

微晶硅锗薄膜作为近红外光吸收层在硅基薄膜太阳电池中的应用

采用射频等离子体增强化学气相沉积技术,制备了具有一定晶化率不同Ge含量的氢化微晶硅锗(μcSi1-xGex:H)薄膜.通过Ⅹ射线荧光谱、拉曼光谱、X射线衍射谱、傅里叶红外谱、吸收系数谱和电导率的测试,表征了μc-Si_(1-x)Ge_x:H的材料微结构随Ge含量的演变.研究表明:提高Ge含量可以增强μc-Si_(1-x)Ge_x:H薄膜的吸收系数.将其应用到硅基薄膜太阳电池的本征层中可以有效提高电池的短路电流密度(J_(sc)).特别是在电池厚度较薄或陷光不充分的情况下,长波响应的提高会更为显著.应用ZnO衬底后,在Ge含量分别为9%和27%时,μc-Si_(1-x)Ge_x:H太阳电池的转换效率均超过了7%.最后,将μc-Si_(1-x)Ge_x:H太阳电池应用在双结叠层太阳电池的底电池中,发现μc-Si_(0.73)Ge_(0.27):H底电池在厚度为800 nm时即可得到比1700 nm厚微晶硅(μc-Si:H)底电池更高的长波响应.以上结果体现μc-Si_(1-x)Ge_x:H太阳电池作为高效近红外光吸收层,在硅基薄膜太阳电池中应用的前景.     

GaInP/GaInAs/GaInNAs/Ge Four-Junction Solar Cell Grown by Metal Organic Chemical Vapor Deposition with High Efficiency

We directly grow a lattice matched GafnP/GaInAs/GaInNAs/Ge(1.88 eV/1.42eV/1.05eV/0.67eV) four-junction(43) solar cell on a Ge substrate by the metal organic chemical vapor deposition technology.To solve the current limit of the GalnNAs sub cell,we design three kinds of anti-reflection coatings and adjust the base region thickness of the GalnNAs sub cell.Developed by a series of experiments,the external quantum efficiency of the GafnNAs sub cell exceeds 80%.and its current density reaches 11.24 mA/cm~2.Therefore the current limit of the 4 J solar cell is significantly improved.Moreover,we discuss the difference of test results between 4J and GalnP/GalnAs/Ge solar cells under the 1 sun AMO spectrum.     

Improved efficiency in GaAs solar cells by 1D and 2D nanopatterns fabricated by laser interference lithography

We demonstrate an improvement in efficiency of GaAs solar cells using front surface texturing with dielectric 1D and 2D nanopatterns obtained by a low cost laser interference lithography technique. The strong light scattering by the surface dielectric nanopatterns effectively increases the optical path of the incident light in the absorber layers resulting in an efficiency increase up to 23.5% compared to that of the reference solar cell. The observed efficiency improvement in the studied solar cells shows the potential use of low cost photoresist as an antireflection coating material and further application of other robust dielectric materials as texturing layer.     

Fabrication of Cu2ZnSn(SxSe1−x)4 thin film solar cell by single step sulfo-selenization of stacked metallic precursors

We have synthesized an efficient Cu₂ZnSn(S_xSe_1−x)₄ (CZTSSe) absorbers by using single-step rapid thermal sulfo-selenization process of sputtered stack metallic precursor (Zn/Sn/Cu) films. The structural and morphological studies confirm that the suitability of the rapid thermal sulfo-selenization process for the synthesis of a CZTSSe absorber without any secondary phases with large grains. The annealing atmosphere with a mixed-chalcogen source enhances the grain growth of the CZTSSe absorber as compared with pure Cu₂ZnSnS₄ (CZTS) and Cu₂ZnSnSe₄ (CZTSe) absorbers. The CZTSSe thin film solar cell shows the best conversion efficiency of ∼7%.