CIGS Thin Films for Cd-Free Solar Cells by One-Step Sputtering Process

Cu(In_1?x Ga _x )Se₂ (CIGS) thin films were deposited by a one-step radio frequency (RF) magnetron sputtering process using a quaternary CIGS target. The influence of substrate temperature on the composition, structure, and optical properties of the CIGS films was investigated. All the CIGS films exhibited the chalcopyrite structure with a preferential orientation along the (112) direction. The CIGS film deposited at 623 K showed significant improvement in film crystallinity and surface morphology compared to films deposited at 523 and 573 K. To simplify the manufacturing procedure of solar cells and avoid the use of the toxic element Cd, the properties of ZnS films prepared by RF sputtering were also investigated. The results revealed that the sputtered ZnS film exhibits good lattice matching with the sputtered CIGS film with significantly lower optical absorption loss. Finally, all-sputtered Cd-free CIGS-based heterojunction solar cells with the structure SLG/Mo/CIGS/ZnS/AZO/Al grids were fabricated without post-selenization. Furthermore, the results demonstrated the feasibility of using a full sputtering process for the fabrication of Cd-free CIGS-based solar cell.     

Cu(In,Ga)Se2太阳电池缓冲层ZnS薄膜性质及应用

在含有ZnSO4,SC(NH2)2,NH4OH的水溶液中采用CBD法沉积ZnS薄膜,XRF和热处理前后的XRD测试表明,ZnS沉积薄膜为立方相结构,薄膜含有非晶态的Zn(OH)2.光学透射谱测试表明,制备的薄膜透过率(λ＞500nm)约为90%,薄膜的禁带宽度约为3.51eV.ZnS薄膜沉积时间对Cu(In,Ga)Se2太阳电池影响显著,当薄膜沉积时间在25～35min时,电池的综合性能最好.对比了不同缓冲层的电池性能,采用CBD-CdS为缓冲层的电池转换效率、填充因子、开路电压稍高于CBD-ZnS为缓冲层的无镉电池,但无镉电池的短路电流密度高于前者,两者转换效率相差2%左右.ZnS可以作为CIGS电池的缓冲层,替代CdS,实现电池的无镉化.     

Cu(In,Ga)Se2太阳电池缓冲层ZnS薄膜性质及应用

在含有ZnSO4,SC(NH2)2,NH4OH的水溶液中采用CBD法沉积ZnS薄膜,XRF和热处理前后的XRD测试表明,ZnS沉积薄膜为立方相结构,薄膜含有非晶态的Zn(OH)2.光学透射谱测试表明,制备的薄膜透过率(λ＞500nm)约为90%,薄膜的禁带宽度约为3.51eV.ZnS薄膜沉积时间对Cu(In,Ga)Se2太阳电池影响显著,当薄膜沉积时间在25～35min时,电池的综合性能最好.对比了不同缓冲层的电池性能,采用CBD-CdS为缓冲层的电池转换效率、填充因子、开路电压稍高于CBD-ZnS为缓冲层的无镉电池,但无镉电池的短路电流密度高于前者,两者转换效率相差2%左右.ZnS可以作为CIGS电池的缓冲层,替代CdS,实现电池的无镉化.     

Improvement of the cell performance in the ZnS/Cu(In,Ga)Se2 solar cells by the sputter deposition of a bilayer ZnO : Al film

ZnS is a candidate to replace CdS as the buffer layer in Cu(In,Ga)Se₂ (CIGS) solar cells for Cd‐free commercial product. However, the resistance of ZnS is too large, and the photoconductivity is too small. Therefore, the thickness of the ZnS should be as thin as possible. However, a CIGS solar cell with a very thin ZnS buffer layer is vulnerable to the sputtering power of the ZnO : Al window layer deposition because of plasma damage. To improve the efficiency of CIGS solar cells with a chemical‐bath‐deposited ZnS buffer layer, the effect of the plasma damage by the sputter deposition of the ZnO : Al window layer should be understood. We have found that the efficiency of a CIGS solar cell consistently decreases with an increase in the sputtering power for the ZnO : Al window layer deposition onto the ZnS buffer layer because of plasma damage. To protect the ZnS/CIGS interface, a bilayer ZnO : Al film was developed. It consists of a 50‐nm‐thick ZnO : Al plasma protection layer deposited at a sputtering power of 50 W and a 100‐nm‐thick ZnO : Al conducting layer deposited at a sputtering power of 200 W. The introduction of a 50‐nm‐thick ZnO : Al layer deposited at 50 W prevented plasma damage by sputtering, resulting in a high open‐circuit voltage, a large fill factor, and shunt resistance. The ZnS/CIGS solar cell with the bilayer ZnO : Al film yielded a cell efficiency of 14.68%. Therefore, the application of bilayer ZnO : Al film to the window layer is suitable for CIGS solar cells with a ZnS buffer layer. Copyright © 2012 John Wiley & Sons, Ltd.     

Theoretical simulation of performances in CIGS thin-film solar cells with cadmium-free buffer layer

Copper indium gallium selenium (CIGS) thin film solar cells have become one of the hottest topics in solar energy due to their high photoelectric transformation efficiency. To real applications, CIGS thin film is covered by the buffer layer and absorption layer. Traditionally, cadmium sulfide (CdS) is inserted into the middle of the window layer (ZnO) and absorption layer (CIGS) as a buffer layer. However, the application of the GIGS/CdS thin film solar cells has been limited because of the environmental pollution resulting from the toxic cadmium atom. Although zinc sulfide (ZnS) has been proposed to be one of the candidates, the performance of such battery cells has not been investigated. Here, in this paper, we systematically study the possibility of using zinc sulfide (ZnS) as a buffer layer. By including the effects of thickness, concentration of a buffer layer, intrinsic layer and the absorbing layer, we find that photoelectric transformation efficiency of ZnO/ZnS(n)/CIGS(i)/CIGS(p) solar cell is about 17.22%, which is qualified as a commercial solar cell. Moreover, we also find that the open-circuit voltage is~0.60 V, the short-circuit current is~36.99 mA/cm² and the filled factor is~77.44%. Therefore, our results suggest that zinc sulfide may be the potential candidate of CdS as a buffer layer.     

无镉的铜铟镓硒太阳电池关键膜层XPS及AFM分析

应用溅射后硒化法和原子层沉积法分别制备了无镉的铜铟镓硒电池关键膜层CIGS光吸收薄膜和ZnO缓冲层,着重对该两膜层进行XPS和AFM表面分析,得到比较理想的制备工艺条件,并结合其它检测方法:SEM、XRD及吸收光谱等,证明采用操作简便、成本低廉的该工艺能制备出无镉的铜铟镓硒电池。通过I-V测试结果,该电池有一定的光电转换效率。     

Interface Analysis of Cu(In,Ga)Se2 and ZnS Formed Using Sulfur Thermal Cracker

We analyzed the interface characteristics of Zn‐based thin‐film buffer layers formed by a sulfur thermal cracker on a Cu(In,Ga)Se₂ (CIGS) light‐absorber layer. The analyzed Zn‐based thin‐film buffer layers are processed by a proposed method comprising two processes — Zn‐sputtering and cracker‐sulfurization. The processed buffer layers are then suitable to be used in the fabrication of highly efficient CIGS solar cells. Among the various Zn‐based film thicknesses, an 8 nm–thick Zn‐based film shows the highest power conversion efficiency for a solar cell. The band alignment of the buffer/CIGS was investigated by measuring the band‐gap energies and valence band levels across the depth direction. The conduction band difference between the near surface and interface in the buffer layer enables an efficient electron transport across the junction. We found the origin of the energy band structure by observing the chemical states. The fabricated buffer/CIGS layers have a structurally and chemically distinct interface with little elemental inter‐diffusion.     

Fabrication and characterization of thin-film Cu (In,Ga) Se2 solar cells on a PET plastic substrate using screen printing

Chalcopyrite copper indium gallium diselenide (CIGS) ink was prepared by dissolving copper, indium, gallium acetylacetonate and Se powder in oleylamine using the hot injection methods. CIGS films were deposited on a PET plastic substrate by a screen-printing technique using CIGS ink with a Ga content ranging from 0.3 to 0.6. X-ray diffraction patterns reveal that the films exhibit a chalcopyrite-type structure. The crystalline grain sizes of the films decrease with increasing Ga content. AFM data shows that the root mean square (RMS) surface roughness of the CIGS film decreases with increasing Ga content. The effects of the Ga content in the CIGS absorber layer on the optical properties of the corresponding thin films and solar cells were studied. The band-gap energies of the CIGS thin films increased with an increasing Ga/(In+Ga) ratio. The short-circuit current (I_SC) of the solar cell decreased linearly with the Ga/(In+Ga) ratio, while the open-circuit voltage (V_OC) increased with this ratio. The solar cell exhibited its highest efficiency of 4.122% at a Ga/(In+Ga) ratio of 0.3.     

ZnS thin films deposition by thermal evaporation for photovoltaic applications

ZnS thin films were deposited on a glass substrate by thermal evaporation from millimetric crystals of ZnS.The structural, compositional and optical properties of the films are studied by X-ray diffraction, SEM microscopy, and UV-VIS spectroscopy.The obtained results show that the films are pin hole free and have a cubic zinc blend structure with (111) preferential orientation.The estimated optical band gap is 3.5 eV and the refractive index in the visible wavelength ranges from 2.5 to 1.8.The good cubic structure obtained for thin layers enabled us to conclude that the prepared ZnS films may have application as buffer layer in replacement of the harmful CdS in CIGS thin film solar cells or as an antireflection coating in silicon-based solar cells.     

Effects of residual copper selenide on CuInGaSe2 solar cells

Large-grain, copper-poor CuInGaSe₂ (CIGS) films are favored in the fabrication of highly efficient solar cells. However, the degradation of cell performance caused by residual copper selenide (Cu_2−xSe) remains a problem. This work studies the formation and behavior of excess Cu_xSe and further compares the cell performance of typical copper-poor with that of copper-rich solar cells. Since excess Cu_2−xSe cannot be exhausted during the growth, it fully surrounds the polycrystalline CIGS grains. Excess Cu_2−xSe in the CIGS film produces serious shunt paths and causes the pn junction to be of poor quality. A short circuit in copper-rich CIGS solar cells is attributable to the conductive Cu_2−xSe. The best way to ensure high-efficiency of the cells is to exhaust Cu_2−xSe during growth. Otherwise, a dense, chemically treated CIGS film is required to prevent the negative effects of excess Cu_2−xSe.     

Zn1?xMgxO用于 CIGS 太阳电池的研究进展

Zn1-xMgxO透过率高、带隙可调,且与CIGS太阳电池在晶格和能带结构上匹配良好,可用作CIGS太阳电池缓冲层、窗口层,因此制备高质量的Zn1-xMgxO薄膜是提高太阳电池性能的关键。文章介绍了Zn1-xMgxO薄膜的结构特性、光学特性及制备方法;从Mg含量、Zn1-xMgxO膜厚及Zn1-xMgxO/CIGS界面处缺陷密度等方面概述了Zn1-xMgxO用于CIGS太阳电池的研究进展,并比较了Zn1-xMgxO与In2S3,ZnS,CdS等其他材料作缓冲层的CIGS太阳电池性能的差别。     

13·7%-Efficient Zn(Se,OH)x/Cu(In,Ga)(SSe)2 thin-film solar cell

Cu(In,Ga)Se₂ (CIGS) and related semiconducting compounds have demonstrated their high potential for high-efficiency thin-film solar cells. The highest efficiency for CIGS-based thin-film solar cells has been achieved with CdS buffer layers prepared by a solution growth method known as chemical bath deposition (CBD). With the aim of developing Cd-free chalcopyrite-based thin-film solar cells, Zn(Se,OH)_x buffer layers were deposited by CBD on polycrystalline Cu(In,Ga)(S,Se)₂ (CIGSS). A total-area conversion efficiency of 13·7% was certified by the Frauenhofer Institute for Solar Energy Systems. The CIGSS absorber was fabricated by Siemens Solar Industries (California). For device optimization, the thickness and good surface coverage were controlled by XPS–UPS photoemission spectroscopy. A Zn(Se,OH)_x thickness below 7 nm has been found to be optimum for achieving a homogeneous and compact buffer film on CIGSS, with open-circuit photovoltage V_oc=535 mV, fill factor FF=70·76% and a high short-circuit photocurrent density J_sc=36·1 mA cm⁻². Copyright © 1998 John Wiley & Sons, Ltd.     

Effects of combined heat and light soaking on device performance of Cu(In,Ga)Se2 solar cells with ZnS(O,OH) buffer layer

The impacts of air annealing, light soaking (LS), and heat–light soaking (HLS) on cell performances were investigated for ZnS(O,OH)/Cu(In,Ga)Se₂ (CIGS) thin‐film solar cells. It was found that the HLS post‐treatment, a combination of LS and air annealing at 130 °C, is the most effective process for improving the cell performances of ZnS(O,OH)/CIGS devices. The best solar cell yielded a total area efficiency of 18.4% after the HLS post‐treatment. X‐ray photoelectron spectroscopy showed that the improved cell performance was attributable to the decreased S/(S + O) atomic ratio, not only in the surface region but also the interface region between the ZnS(O,OH) and CIGS layers, implying the shift to an adequate conduction‐band offset at the ZnS(O,OH)/CIGS interface. Copyright © 2013 John Wiley & Sons, Ltd.     

Beam injection methods for characterizing thin‐film solar cells

II–VI and I–III–VI solar cells are promising for future thin‐film photovoltaics. In this paper, the roles of electron‐beam‐induced current (EBIC) and cathodoluminescence in evaluating the influence of interfaces on those solar cells are reviewed. CdTe and Cu(In,Ga)Se₂ (CIGS) are the absorbers of the cells investigated. For CdTe/CdS solar cells, a detailed study has been conducted of the effects of grain boundaries and the Te/CdTe or ZnTe:Cu/CdTe interfaces for back‐contacting. For CIGS solar cells, we have investigated different buffer layer schemes, showing that these interfaces are critical in the definition of the mechanisms for carrier collection. Copyright © 2002 John Wiley & Sons, Ltd.     

Improved fill factor and open circuit voltage by crystalline selenium at the Cu(In,Ga)Se2/buffer layer interface in thin film solar cells

A surface treatment by evaporated selenium on Cu(In,Ga)Se₂ (CIGS) is shown to improve open circuit voltage, V_oc, and in some cases fill factor, FF, in solar cells with CdS, (Zn,Mg)O or Zn(O,S) buffer layers. V_oc increases with increasing amount of crystalline Se, while FF improves only for small amounts. The improvements are counteracted by a decreasing short circuit current assigned to absorption in hexagonal Se. Improved efficiency is shown for device structures with (Zn,Mg)O and Zn(O,S) buffer layers by atomic layer deposition. Analysis by grazing incidence X‐ray diffraction and photoelectron spectroscopy show partial coverage of the CIGS surface by hexagonal selenium. The effects on device performance from replacing part of the CIGS/buffer interface area by a Se/buffer junction are discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Cu-In-Ga-Se nanoparticle colloids as spray deposition precursors for Cu(In, Ga)Se2 solar cell materials

The use of nanoparticle colloids for spray deposition of Cu(In,Ga)Se₂ (CIGS) precursor films and subsequent fabrication of CIGS solar cells has been investigated. According to this approach, amorphous Cu-In-Ga-Se nanoparticle colloids were first prepared by reacting a mixture of CuI, InI₃, and GaI₃ in pyridine with Na₂Se in methanol at reduced temperature. Purified colloid was sprayed onto heated molybdenum-coated sodalime glass substrates to form Cu-In-Ga-Se precursor films. After thermal processing of the precursor films under a selenium ambient, CIGS solar cells were fabricated. Cu-In-Ga-Se colloids and films were characterized by inductively coupled plasma atomic emission spectroscopy, thermogravimetric analysis, transmission electron microscopy, x-ray diffraction, scanning electron microscopy, and Auger electron spectroscopy. Standard current-voltage characterization was performed on the CIGS solar cell devices with the best film exhibiting a solar conversion efficiency of 4.6%.     

Effect of processing parameter on structural,optical and electrical properties of photovoltaic chalcogenide nanostructured RF magnetron sputtered thin absorbing films

The aim of this work was to develop high quality of CuIn_1−xGa_xSe₂ thin absorbing films with x (Ga/In+Ga)<0.3 by sputtering without selenization process. CuIn_0.8Ga_0.2Se₂ (CIGS) thin absorbing films were deposited on soda lime glass substrate by RF magnetron sputtering using single quaternary chalcogenide (CIGS) target. The effect of substrate temperature, sputtering power & working pressure on structural, morphological, optical and electrical properties of deposited films were studied. CIGS thin films were characterised by X-ray diffraction (XRD), Field emission scanning electron microscope (FE-SEM), Energy dispersive X-ray spectroscopy (EDAX), Atomic force microscopy (AFM), UV–vis–NIR spectroscopy and four probe methods. It was observed that microstructure, surface morphology, elemental composition, transmittance as well as conductivity of thin films were strongly dependent on deposition parameters. The optimum parameters for CIGS thin films were obtained at a power 100 W, pressure 5 mT and substrate temperature 500 °C. XRD revealed that thin film deposited at above said parameters was polycrystalline in nature with larger crystallite size (32 nm) and low dislocation density (0.97×10¹⁵ lines m⁻²). The deposited film also showed preferred orientation along (112) plane. The morphology of the film depicted by FE-SEM was compact and uniform without any micro cracks and pits. The deposited film exhibited good stoichiometry (Ga/In+Ga=0.19 and In/In+Ga=0.8) with desired Cu/In+Ga ratio (0.92), which is essential for high efficiency solar cells. Transmittance of deposited film was found to be very low (1.09%). The absorption coefficient of film was ~10⁵ cm⁻¹ for high energy photon. The band gap of CIGS thin film evaluated from transmission data was found to be 1.13 eV which is optimum for solar cell application. The electrical conductivity (7.87 Ω⁻¹ cm⁻¹) of deposited CIGS thin film at optimum parameters was also high enough for practical purpose.     

A comparative study of Cd‐ and Zn‐compound buffer layers on Cu(In1−x,Gax)(Sy,Se1−y)2 thin film solar cells

This paper reports a comparative study of Cu(In,Ga)(S,Se)₂ (CIGSSe) thin‐film solar cells with CBD‐CdS, CBD‐ZnS(O,OH) and ALD‐Zn(O,S) buffer layers. Each buffer layer was deposited on CIGSSe absorber layers which were prepared by sulfurization after selenization (SAS) process by Solar Frontier K. K. Cell efficiencies of CBD‐CdS/CIGSSe, CBD‐ZnS(O,OH)/CIGSSe and ALD‐Zn(O,S)/CIGSSe solar cells exceeded 18%, for a cell area of 0.5 cm². The solar cells underwent a heat‐light soaking (HLS) post‐treatment at 170 °C under one‐sun illumination in the air; among the three condtions, the ALD‐Zn(O,S)/CIGSSe solar cells showed the highest cell efficiency of 19.78% with the highest open‐circuit voltage of 0.718 V. Admittance spectroscopy measurements showed a shift of the N₁ defect's energy position toward shallower energy positions for ALD‐Zn(O,S)/CIGSSe solar cells after HLS post‐treatment, which is in good agreement with their higher open‐circuit voltage and smaller interface recombination than that of CBD‐ZnS(O,OH)/CIGSSe solar cells. Copyright © 2015 John Wiley & Sons, Ltd.     

Investigation of damage caused by partial shading of CuInxGa(1‐x)Se2 photovoltaic modules with bypass diodes

This study evaluated the impact of partial shading on CuInxGa_(1‐x)Se₂ (CIGS) photovoltaic (PV) modules equipped with bypass diodes. When the CIGS PV modules were partially shaded, they were subjected to partial reverse bias, leading to the formation of hotspots and a possible occurrence of junction damage. In a module with a cadmium sulfide buffer layer, hotspots and wormlike defects were formed. The hotspots were formed as soon as the modules were shaded; the hotspots caused permanent damage (wormlike defects) in the CIGS module. Specifically, the wormlike defects were caused by the window layer, leading to increased recombination and decay of the solar cell properties. However, a CIGS module with a zinc sulfide buffer layer did not exhibit the formation of hotspots or any visual damage. The reverse bias breakdown voltage of the CIGS PV module with the cadmium sulfide buffer layer was higher than that of the CIGS PV module with the zinc sulfide buffer layer. Copyright © 2016 John Wiley & Sons, Ltd.     

Study#$TABon#$TABsputtering#$TABZn(O,S)#$TABbuffer#$TABlayers for eco-friendly Cu(In,Ga)Se2 solar cells

An eco-friendly Zn(O,S) film with a wider band gap is emerging as one of the promising Cd-free replacement material, which can be deposited by radio frequency sputtering. The effect of sputtering pressure on the Zn(O,S) films properties and the devices performance are studied systematically. At high pressure, the ZnS phase is found in the Zn(O,S) films resulting in a higher barrier at Zn(O,S) /CIGS interface which would lead to a low recombination activation energy (Ea). By reducing sputtering pressure, single phase of Zn(O,S) films are conducive to carrier transport as well as pro- mote the films electric properties, ultimately improving the performance of Zn(O,S)/CIGS solar cells. This work has been supported by the National Natural Science Foundation of China (Nos.61774089, 51572132 and 61504067), and the Yang Fan Innovative & Entrepreneurial Research Team Project (No.2014YT02N037). E-mail:wwl@nankai.edu.cn