Effect of deposited temperatures of the buffer layer on the band offset of CZTS/In_2S_3 heterostructure and its solar cell performance

The effect of the deposition temperature of the buffer layer In_2S_3 on the band alignment of CZTS/In_2S_3 heterostructures and the solar cell performance have been investigated.The In_2S_3 films are prepared by thermal evaporation method at temperatures of 30,100,150,and 200 ℃,respectively.By using x-ray photoelectron spectroscopy(XPS),the valence band offsets(VBO) are determined to be-0.28 ±0.1,-0.28 ±0.1,-0.34 ±0.1,and-0.42 ±0.1 eV for the CZTS/In_2S_3heterostructures deposited at 30,100,150,and 200 ℃,respectively,and the corresponding conduction band offsets(CBO)are found to be 0.3 ±0.1,0.41 ±0.1,0.22±0.1,and 0.01 ±0.1 eV,respectively.The XPS study also reveals that interdiffusion of In and Cu occurs at the interface of the heterostructures,which is especially serious at 200 ℃ leading to large amount of interface defects or the formation of CuInS_2 phase at the interface.The CZTS solar cell with the buffer layer In_2S_3 deposited at 150 ℃ shows the best performance due to the proper CBO value at the heterostructure interface and the improved crystal quality of In_2S_3 film induced by the appropriate deposition temperature.The device prepared at 100 ℃presents the poorest performance owing to too high a value of CBO.It is demonstrated that the deposition temperature is a crucial parameter to control the quality of the solar cells.     

Buffer-less Cu(In,Ga)Se2 solar cells by band offset control using novel transparent electrode

Cu(In,Ga)Se₂ (CIGS) solar cells without buffer layers have been demonstrated. Currently, CdS, Zn(O,S,OH), ZnS, or InS buffer layers are used in high efficiency CIGS solar cells to suppress interface recombination. One of the important parameters to reduce the recombination is the conduction band offset (CBO) between the buffer and CIGS layers. In this study, we have proposed the use of a novel transparent conductive oxide (TCO) which can control the CBO to reduce interface recombination and eliminate the buffer layers. The device simulation was used to verify the effect of CBO control theoretically. Then, the novel TCO material of ZnO_1?xS_x:Al prepared by co-sputtering of ZnO:Al₂O₃ and ZnS targets was fabricated to verify the CBO effect experimentally. The efficiency of a CIGS solar cell with a ZnO:Al/CIGS/Mo/soda-lime glass structure, i.e. buffer-less structure using a conventional TCO, was significantly low because of severe shunting. In contrast, the use of ZnO_1-xS_x:Al instead of ZnO:Al increased the shunt resistance of the CIGS solar cell, resulting in higher open-circuit voltage and efficiency. The result is the first proof of the concept of the buffer-less CIGS solar cells.     

Band offsets engineering at Cd_xZn_(1-x)S/Cu_2ZnSnS_4 heterointerface

Cd_xZn_(1-x)S/Cu_2ZnSnS_4 (CZTS)-based thin film solar cells usually use Cd S as a buffer layer, but due to its smaller band gap(2.4 e V), Cd S film has been replaced with higher band gap materials. The cadmium zinc sulfide(Cd Zn S) ternary compound has a higher band gap than other compounds, which leads to a decrease in window absorption loss. In this paper, the band offsets at Cd_xZn_(1-x)S/Cu_2ZnSnS_4 (CZTS) heterointerface are calculated by the first-principles, densityfunctional and pseudopotential method. The band offsets at Cd_(1-x)Zn_x S/CZTS heterointerface are tuned by controlling the composition of Zn in Cd_(1-x)Zn_x S alloy, the calculated valence band offsets are small, which is consistent with the commonanion rule. The favorable heterointerface of type-I with a moderate barrier height( 0.3 e V) can be obtained by controlling the composition of Zn in Cd_(1-x)Zn_x S alloy between 0.25 and 0.375.     

Lithium/Silver-Doped Cu_2ZnSnS_4 with Tunable Band Gaps and Phase Structures: a First-Principles Study

Doping is an effective approach for improving the photovoltaic performance of Cu_2 ZnSnS_4(CZTS). The doping by substitution of Cu atoms in CZTS with Li and Ag atoms is investigated using density functional theory. The results show that the band gaps of Li_(2 x)Cu_(2(1-x))ZnSnS_4 and Ag_(2 x)Cu_(2(1-x))ZnSnS4 can be tuned in the ranges of 1.30-3.43 and 1.30-1.63 eV, respectively. The calculation also reveals a phase transition from kesterite to wurtzite-kesterite for Li_(2 x)Cu_(2(1-x))ZnSnS_4 as x is larger than 0.9. The tunable band gaps of Li_(2 x)Cu_(2(1-x))ZnSnS_4 and Ag_(2 x)Cu_(2(1-x)) ZnSnS_4 make them beneficial for achieving band-gap-graded solar cells.     

First-principles study of Cu2ZnSnS4 and the related band offsets for photovoltaic applications

First-principles calculations of the band offsets between Cu(2)ZnSnS(4) (CZTS) and XS (X = Cd, Zn) are performed. While the interface dipole contribution for the band offsets is calculated using the Perdew-Burke-Ernzerhof functional, the Heyd-Scuseria-Ernzerhof hybrid functional is employed to introduce the quasiparticle corrections to the band offsets. The calculated conduction band offset between CZTS and CdS is 0.2 eV, validating CdS for the buffer layer of the CZTS solar cell. The small conduction band offset stems from the band gap narrowing of CdS under the interface strain caused by the lattice misfit with CZTS. A large valence band offset over 0.9 eV between CZTS and ZnS indicates that precipitated ZnS is regarded as an inactive insulator phase in CZTS absorbers.     

Enhancement of output performance of Cu2ZnSnS4 thin film solar cells—A numerical simulation approach and comparison to experiments

The formation of stable, low resistance and nonrectifying contacts to Cu₂ZnSnS₄ (CZTS) thin film photovoltaic material are the major and critical challenges associated with its effect over the output performance of fabricated solar cells. The solution of continuity equation in one dimension for a soda lime glass substrates (SLG) |Mo | CZTS | CdS | ZnO:Al cell structure is considered in the simulation of its current–voltage characteristics that is governed by the back contact material, acceptor concentration as well as thickness of the CZTS layer. Our primary simulation shows a 6.44% efficiency of the CZTS solar cell which is comparable to reported experimental data if these parameters are not optimized. However, by optimizing them a simulated conversion efficiency as high as 13.41% (V_oc=1.002 V, J_sc=19.31 mA/cm², fill factor (FF)=69.35%) could be achievable. The solar cell with a back contact metal work function of 5.5 eV, an absorber layer's thickness of 2.68 μm and an acceptor concentration of 5×10¹⁶ cm⁻³ were optimum. The presented optimization is ideal and subject to experimental verification with a precise control of the process parameters along with reduced surface as well as bulk recombination, secondary phases and thermalization losses.     

连续离子层吸附反应沉积后硫化法制备柔性铜锌锡硫薄膜太阳电池

在柔性钼箔衬底上采用连续离子层吸附反应法(successive ionic layer absorption and reaction)制备ZnS/Cu2SnSx叠层结构的预制层薄膜,预制层薄膜在蒸发硫气氛、550 C温度条件下进行退火得到Cu2ZnSnS4吸收层.分别采用EDS,XRD,Raman,SEM表征吸收层薄膜的成分、物相和表面形貌.结果表明,退火后薄膜结晶质量良好,表面形貌致密.用在普通钠钙玻璃上采用相同工艺制备的CZTS薄膜表征薄膜的光学和电学性能,表明退火后薄膜带隙宽度为1.49 eV,在可见光区光吸收系数大于104cm 1,载流子浓度与电阻率均满足薄膜太阳电池器件对吸收层的要求.用上述柔性衬底上的吸收层制备Mo foil/CZTS/CdS/i-ZnO/ZnO:Al/Ag结构的薄膜太阳电池得到2.42%的效率,是目前报道柔性CZTS太阳电池最高效率.     

n-ZnO:Al/i-ZnO/n-CdS/p-Cu2ZnSnS4太阳能电池光伏特性的分析

具有高光吸收系数的半导体Cu₂ZnSnS₄ (CZTS)薄膜是一种新型太阳能电池材料. 本文对n-ZnO:Al/i-ZnO/n-CdS/p-CZTS结构的CZTS薄膜太阳能电池进行分析, 讨论CZTS薄膜的掺杂浓度、厚度、缺陷态和CdS薄膜的掺杂浓度、 厚度对太阳能电池转换效率的影响以及太阳能电池的温度特性. 分析表明, CZTS薄膜作为太阳能电池的主要光吸收层, CZTS薄膜的掺杂浓度和厚度的取值对太阳能电池的转换效率有显著影响, CZTS薄膜结构缺陷态的存在会导致太阳能电池性能的下降. CdS缓冲层的掺杂浓度、厚度对太阳能电池光伏特性的影响较小. 经结构参数优化得到的n-ZnO:Al/i-ZnO/n-CdS/p-CZTS薄膜太阳能电池的最佳光 伏特性为开路电压1.127 V、短路电流密度27.39 mA/cm²、填充因子87.5%、 转换效率27.02%,转换效率温度系数为-0.14%/K.     

电镀法在氧化铟锡上制备铜锌锡硫薄膜的光谱特征

低成本、环境友好的铜锌锡硫替代含贵金属和有毒金属的铜铟镓硒,是薄膜太阳能电池的最佳选择。电镀法是一种无需真空设备和靶材的低成本方法。一种更简单的制膜方法是在水溶液中共电镀沉积Cu-Zn-Sn（CZT)合金于FTO衬底上。采用氩气保护气氛下在550 ℃硫化电镀法制得的CZT合金前驱体,成功制备了CZTS薄膜。采用三电极体系将CZT合金前驱体电镀在FTO上,其中FTO作为工作电极,铂（Pt）网和Ag/AgCl分别作为对电极和参比电极。电解质由CuSO₄,ZnSO₄,SnSO₄,络合剂-三乙醇胺（TEA）和柠檬酸钠组成。前驱体在氩气保护气氛下550℃硫化得到CZTS薄膜。采用X射线衍射（XRD）、拉曼光谱、扫描电子显微镜（SEM）、紫外可见光光谱仪和光电化学测量（PEC）等方法,表征了CZTS薄膜的结构、形貌、成分和光谱学性质。XRD和拉曼光谱证明了550 ℃硫化后的CZTS薄膜具有锌黄锡矿结构。一个Raman主峰位于342 cm-1,两个Raman次强峰分别位于289和370 cm-1,这些峰位与锌黄锡矿CZTS的峰位相吻合。SEM结果证明优化后CZTS薄膜成分接近CZTS的理想化学计量比,CZTS薄膜中Cu/(Zn+Sn）和 S/(Zn+Sn+Cu)分别为0.52和1.01,这表明CZTS薄膜中S的含量非常合适。PEC结果证实,采用前照射或后照射FTO/CZTS均产生光电流,并且两种照射下产生的光电流方向一致。通过紫外可见光光谱测量并由此计算出的CZTS能隙为1.45 eV。通过上述分析证明制备的CZTS薄膜具有高品质,可用于制备CZTS薄膜太阳能电池。     

四元硫化物Cu2Zn(Ti,Zr, Hf)S4:一类新颖光伏材料

采用第一性原理电子结构方法研究了四价过渡金属Ti, Zr和Hf替代Cu₂ZnSnS₄(CZTS)中Sn原子以及Se替代S原子所得到的四元硫族化合物的电子结构、光学性质和晶体结构的稳定性. 实验上用Se替代CZTS中部分S得到的Cu₂ZnSnS_4-xSe_x(CZTSSe)作为光吸收材料, 可以进一步提高光伏效率. 我们计算表明用Se替代S后, CZTSe的价带顶明显下移, 并接近Cu(In, Ga) Se₂ (CIGS)价带顶位置. 与CZTSe的电子结构特征一样, Cu₂Zn(Ti, Zr, Hf)S₄四元硫化物的价带顶与母体材料CZTS相比也向低能移动, 并接近CIGS价带顶位置. 由于高光伏效率要求窗口材料ZnO、缓冲层材料和光吸收材料的价带顶和带隙满足一定的渐进的变化关系, 因此可以预见用Cu₂Zn(Ti, Zr, Hf)S₄作光吸收材料可以有效地提高甚至接近CIGS的光伏效率. 通过计算弹性常数和声子谱, 以及有限温度下第一性原理分子动力学模拟, 发现Cu₂Zn(Ti, Zr, Hf)S₄的结构稳定性与CZTS相近. 进一步计算Cu₂Zn(Ti, Zr, Hf)S₄与不同缓冲层间和窗口材料与缓冲层间的反射系数, 并讨论了ZnSe, In₂S₃, ZnS作为缓冲层材料和TiO₂作为窗口材料对光伏效率可能的影响.     

Magnetic-Field-Induced Spin Nematicity in FeSe_(1-x)S_x and FeSe_(1-y)Te_y Superconductor Systems

The angular-dependent magnetoresistance(AMR) of the ab plane is measured on the single crystals of ironchalcogenide FeSe_(1-x)S_x(x=0,0.07,0.13 and 1) and FeSe_(1-y)Te_y(y=0.06,0.61 and 1) at various temperatures under fields up to 9 T.A pronounced twofold-anisotropic carrier-scattering effect is identified by AMR,and attributed to a magnetic-field-induced spin nematicity that emerges from the tetragonal normal-state regime below a characteristic temperature Tsn.This magnetically polarized spin nematicity is found to be ubiquitous in the isoelectronic FeSe_(1-x)S_x and FeSe_(1-y)Te_y systems,no matter whether the sample shows an electronic nematic order at T_s(?)T_(sn),or an antiferromagnetic order at T_N T_(sn),or neither order.Importantly,we find that the induced spin nematicity shows a very different response to sulfur substitution from the spontaneous electronic nematicity:The spin-nematic Tsn is not suppressed but even enhanced by the substitution,whereas the electronicnematic Ts is rapidly suppressed,in the FeSe_(1-x)S_x system.Furthermore,we find that the superconductivity is significantly suppressed with the enhancement of the induced spin nematicity in both FeSe_(1-x)S_x and FeSe_(1-y)Te_y samples.     

单靶溅射制备铜锌锡硫薄膜及原位退火研究

采用衬底加热溅射铜锌锡硫(CZTS)四元化合物单靶制备CZTS薄膜,并研究原位退火对制备薄膜的影响.结果表明:在溅射结束后快速升温并保持一段时间,所得到的样品相比于未原位退火的CZTS薄膜结晶质量更好,且表面更平整致密;原位退火后的CZTS薄膜太阳电池性能参数也相应地有所提升,其开路电压(V_(OC))为575 mV,短路电流密度(J_(SC))为8.32 mA/cm~2,光电转换效率达到1.82%.     

Valence band offset of MgO/TiO2 (rutile) heterojunction measured by X-ray photoelectron spectroscopy

The valence band offset (VBO) of MgO/TiO₂ (rutile) heterojunction has been directly measured by X-ray photoelectron spectroscopy. The VBO of the heterojunction is determined to be 1.6 ± 0.3 eV and the conduction band offset (CBO) is deduced to be 3.2 ± 0.3 eV, indicating that the heterojunction exhibits a type-I band alignment. These large values are sufficient for MgO to act as tunneling barriers in TiO₂ based devices. The accurate determination of the valence and conduction band offsets is important for use of MgO as a buffer layer in TiO₂ based field-effect transistors and dye-sensitized solar cells.     

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.     

Preparing Cu₂ZnSnS₄ films using the co-electrodeposition method with ionic liquids

Cu₂ZnSnS4（CZTS） films are successfully prepared by co-electrodeposition in aqueous ionic solution and sulfurized in elemental sulfur vapor ambient at 400 C for 30 min using nitrogen as the protective gas.It is found that the CZTS film synthesized at Cu/（Zn+Sn）=0.71 has a kesterite structure,a bandgap of about 1.51 eV,and an absorption coefficient of the order of 10 4 cm 1.This indicates that the co-electrodeposition method with aqueous ionic solution is a viable process for the growth of CZTS films for application in photovoltaic devices.     

Computational analysis of the effect of the surface defect layer (SDL) properties on Cu(In,Ga)Se2-based solar cell performances

In this article, the performances of Cu(In,Ga)Se₂ (CIGS) solar cells have been modelled and numerically simulated using the one-dimensional simulation program Solar Cell Capacitance Simulator in 1 Dimension (SCAPS-1D), and a detailed analysis of the effect of surface defect layer (SDL) thickness, band gap and carrier mobility with Fermi level pinning is presented. Furthermore, donor-type defect state density in the SDL has been investigated, and their effect on device performances has been presented. Based on the simulation results, optimal properties of the SDL for the CIGS solar cell are proposed. The simulated results show that the optimal thickness of the SDL to optimise the solar cells is in the range of 100–200 nm. The increase in the band gap of the SDL >1.3 eV improves the device performance by enhancing the open-circuit voltage (V_oc), fill factor (FF) and conversion efficiency due to the larger quasi-Fermi energy-level splitting, and optimal band offset between the SDL and the buffer layer (CdS). The simulation results suggest that the SDL defect density as well as carrier mobilities are the critical parameters for the limitation of the performances for the CIGS solar cells. All these results show that the SDL plays an important role in designing high-efficiency and high-performance CIGS-based solar cells.     

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)     

Characterization of CBO and defect states of CZTSe solar cells prepared by using two-step process

We fabricated kesterite Cu₂ZnSnSe₄ (CZTSe) solar cells and studied device characteristics, where CZTSe absorbers were made by using two-step process. First, we deposited precursor CZTSe films with spin-coating or sputtering, and performed sulfurization and subsequent selenization. To complete the device, we applied In₂S₃ as a buffer layer. We obtained power conversion efficiency (PCE) of 4.18% with spin-coated CZTSe absorber and 5.60% with sputtered CZTSe absorber. Both devices showed deep defects in the bulk and strong interface recombinations near the pn junction. In addition, we observed red-kinks in the current density-voltage (J-V) curves for both devices under the filtered light illumination (>660 nm), which is attributed to large conduction band offset (CBO) between the CZTSe absorber and the buffer layer and defect states in the buffer/CZTSe absorber or in the buffer. The red-kink was also observed in CZTSe (PCE of 7.76%) solar cell with CdS buffer. Hence, to enhance the PCE with CZTSe absorber, along with suppression of deep defects which act as recombination center, optimization of CBO between absorber and buffer is also required.     

Preparing Cu2ZnSnS4 films using the co-electro-deposition method with ionic liquids

Cu2ZnSnS4（CZTS） films are successfully prepared by co-electrodeposition in aqueous ionic solution and sulfurized in elemental sulfur vapor ambient at 400 C for 30 min using nitrogen as the protective gas.It is found that the CZTS film synthesized at Cu/（Zn＋Sn）=0.71 has a kesterite structure,a bandgap of about 1.51 eV,and an absorption coefficient of the order of 10 4 cm 1.This indicates that the co-electrodeposition method with aqueous ionic solution is a viable process for the growth of CZTS films for application in photovoltaic devices.     

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.