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.     

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.     

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.     

Influence of Ni and Cr impurities on the electronic properties of Cu(In,Ga)Se2 thin film solar cells

Deposition of Cu(In,Ga)Se₂ (CIGS) thin film solar cells on metallic substrate is an attractive approach for development of low cost solar modules. However, in such devices, special care has to be taken to avoid diffusion of impurities, such as Fe, Ni, and Cr, from the substrate into the active layers. In this work, the influence of Ni and Cr impurities on the electronic properties of CIGS thin film solar cells is investigated in detail. Impurities were introduced into the CIGS layer by diffusion during the CIGS deposition process from a Ni or Cr precursor layer below the Mo electrical back contact. A high temperature and a low temperature CIGS deposition process were applied in order to correlate the changes in the photovoltaic parameters with the amount of impurities diffused into the absorber layer. Solar cells with Ni and Cr impurities show a reduction in the device performance, whereas the effect was most pronounced in Ni containing devices. The presence of deep defect levels in the absorber layer was identified with admittance spectroscopy and can be related to Ni and Cr impurities, which diffused into the CIGS layer according to secondary ion mass spectroscopy depth profiles and inductively coupled plasma mass spectrometry. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Determination of activation barriers for the diffusion of sodium through CIGS thin‐film solar cells

We have determined the activation energies of sodium diffusion from the soda‐lime glass substrate through the Mo back‐contact layer, as well as through copper indium gallium diselenide (CIGS) deposited on the Mo back‐contact layer of CIGS thin‐film solar cells. The activation energies were determined by X‐ray photoelectron spectroscopy (XPS) to measure surface sodium concentrations before and after thermally induced diffusion. The activation energies were found to be similar for the diffusion of Na through the Mo/glass and CIGS/Mo/glass thin films, approximately 8·6 and 9·6 kcal/mol, respectively. Furthermore, the sodium diffusion was found to occur by annealing in an environment of 1·0×10⁻⁵ Torr of air, oxygen, or water vapor, but not in vacuum of less than 1×10⁻⁸ Torr. In addition, the diffusion of Na was found to occur faster in the presence of oxygen than in water under identical annealing conditions. Copyright © 2003 John Wiley & Sons, Ltd.     

Inkjet printed metallizations for Cu(In1−x Ga x )Se2 photovoltaic cells

This study reports the inkjet printing of Ag front contacts on Aluminum doped Zinc Oxide (AZO)/intrinsic Zinc Oxide (i‐ZnO)/CdS/Cu(In_1−xGa_x)Se₂ (CIGS)/Mo thin film photovoltaic cells. The printed Ag contacts are being developed to replace the currently employed evaporated Ni/Al bi‐layer contacts. Inkjet deposition conditions were optimized to reduce line resistivity and reduce contact resistance to the Al:ZnO layer. Ag lines printed at a substrate temperature of 200°C showed a line resistivity of 2.06 µΩ · cm and a contact resistance to Al:ZnO of 8.2 ± 0.2 mΩ · cm² compared to 6.93 ± 0.3 mΩ · cm² for thermally evaporated contacts. These deposition conditions were used to deposit front contacts onto high quality CIGS thin film photovoltaic cells. The heating required to print the Ag contacts caused the performance to degrade compared to similar devices with evaporated Ni/Al contacts that were not heated. Devices with inkjet printed contacts showed 11.4% conversion efficiency compared to 14.8% with evaporated contacts. Strategies to minimize heating, which is detrimental for efficiency, during inkjet printing are proposed. Copyright © 2011 John Wiley & Sons, Ltd.     

Parameterized complex dielectric functions of CuIn1−xGaxSe2: applications in optical characterization of compositional non‐uniformities and depth profiles in materials and solar cells

In‐situ spectroscopic ellipsometry (SE) was employed to extract the complex dielectric functions ε = ε₁ + iε₂ over the spectral range of 0.75–6.5 eV for a set of polycrystalline CuIn_1−xGa_xSe₂ (CIGS) thin films with different alloy compositions x = [Ga]/{[In] + [Ga]}. For highest possible accuracy in ε for each CIGS thin film, specialized SE procedures were adopted including (i) deposition to a thickness of ~600 Å on smooth native oxide covered crystal silicon wafers, which minimizes the surface roughness on the film and thus the required corrections in data analysis, and (ii) measurement in‐situ, which minimizes ambient contamination and oxidation of the film surface. Assuming an analytical form for each of the ε spectra for these CIGS films, oscillator parameters were obtained in best fits, and these parameters were fit in turn to polynomials in x. With the resulting database of polynomial coefficients, the ε spectra for any composition of CIGS can be generated from the single parameter, x. In addition to enabling accurate contactless determination of bulk and surface roughness layer thicknesses of CIGS films by high speed multichannel SE, the database enables characterization of the composition and its profile with depth into these films, and even how the depth profile varies spatially within the plane of the films. In this study, depth profile parameters were found to correlate spatially with solar cell performance parameters. As a result, SE provides the capability of contactless compositional analysis of production‐scale CIGS photovoltaic modules at high speed. Copyright © 2016 John Wiley & Sons, Ltd.     

Impacts of surface sulfurization on Cu(In1−x,Gax)Se2 thin‐film solar cells

In this work, the impacts of surface sulfurization of high‐quality Cu(In_1−x,Ga_x)Se₂ (CIGS) thin films deposited by three‐stage process on the film properties and the cell performance were investigated. The CIGS thin films were sulfurized at 550 °C for 30 min using H₂S gas. The X‐ray photoelectron spectroscopy analysis revealed that sulfur atoms diffused into the CIGS surface layer and that the valence band minimum was lowered by the film sulfurization. The open circuit voltage (V_oc) drastically increased from 0.590 to 0.674 V as a result of the sulfurization process. Temperature‐dependent current–voltage and capacitance–frequency measurements also revealed that interface recombination was drastically decreased by the lowering of the defect's activation energy level at the vicinity of the buffer/CIGS interface after the sulfurization. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Properties of the Mo Back Contact for the Formation of a Thin-Film Photovoltaic Absorber

A Taguchi experimental design was used to find which deposition parameter has the most dominant effect on the electrical resistivity of molybdenum (Mo) films. Based on the most important parameter, the Mo films were further characterized by structural, electrical, and adhesive methods. Then, a copper indium gallium selenide (CIGS) thin film was fabricated by a two-stage process on the obtained Mo layer. The results show that working pressure had a dominant effect on electrical resistivity. The Mo films deposited at 1 mTorr and 2 mTorr exhibited compressive strain and dense polycrystalline microstructure, whereas those deposited at 3 mTorr and 4 mTorr exhibited tensile strain and an elongated grain with open boundaries. A Mo film with open porous structure, tensile strain, and lower resistivity was suitable for the formation of CIGS films. After selenization at 560°C, a single-phase chalcopyrite CIGS film with a layer of MoSe₂ at the Mo/CIGS interface was obtained.     

金属Cr阻挡层对柔性不锈钢衬底Cu(In,Ga)Se2太阳电池性能的影响

研究了Cr扩散阻挡层对柔性不锈钢衬底Cu(InxGa1-x)Se2(CIGS)太阳电池性能的影响.XRD和SEM分析表明,Cr阻挡层能够部分阻挡Fe等杂质从不锈钢衬底热扩散进入CIGS吸收层中,同时可以显著降低CIGS吸收层的粗糙度,提高薄膜结晶质量.从衬底扩散进入吸收层中的Fe元素以FeInSe2的形式存在,并形成FeCu等深能级缺陷,钝化了器件的性能.相同工艺条件下,在玻璃、不锈钢以及不锈钢/Cr阻挡层上所制备电池的(有效面积0.87cm2)转换效率分别为10.7%,7.95%和8.58%,不锈钢衬底电池效率的提高归因于Cr阻挡层的作用.     

Preferred orientation of Cu(In,Ga)Se2 thin film deposited on stainless steel substrate

The influences of process parameters and Fe diffusing into Cu(In,Ga)Se₂ (CIGS) films on the orientation of CIGS absorbers grown on the stainless steel (SS) foils are investigated. The structural properties, morphology, and elemental profiles are characterized using X‐ray diffraction, scanning electron microscopy, and second ion mass spectroscopy, respectively. The orientation of CIGS thin films on the SS substrates strongly depends on the texture of the (In,Ga)₂Se₃ precursor, determined by the substrate temperature at the first stage (Ts1) and the flux ratio of Se to (In + Ga). Among these factors, Ts1 is the prerequisite to achieve [300]‐oriented IGS layer, which will yield [200]‐oriented CIGS thin film in the later process. The results indicate that through the comparison of CIGS thin films on the Mo/SS substrates and on the Mo/ZnO/SS substrates and combined with simply calculation, Fe diffusing into the CIGS layer will hinder the growth of the CIGS grains along [112] orientation. The grazing‐incidence X‐ray diffraction results suggest that the surface of the [220]‐textured CIGS thin film on the SS substrate still has [220] predominance, whereas the surface texture of the [220]‐texture CIGS thin film on the Mo/soda‐lime glass substrate became [112] predominant, which is due to the different compensation ability between Fe and Na elements. Finally, the relations between the device parameters and the degrees of the preferred orientation of CIGS absorbers are investigated. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of Se flux on CuIn1‐xGaxSe2 film in reactive sputtering process

CuIn_1‐xGa_xSe₂ (CIGS) thin films were grown on Mo/soda lime glass using a reactive sputtering process in which a Se cracker was used to deliver reactive Se molecules. The Cu_0·6 Ga_0·4 and Cu_0·4In_0·6 targets were simultaneously sputtered under the delivery of reactive Se. The effects of Se flux on CIGS film deposition were investigated. The CIGS film growth rate decreased, and the surface roughness of a film increased as the Se flux increased. The [112] crystal orientation was dominant, and metallic crystal phases such as Cu₉Ga₄ and Cu₁₆In₉ in a film were disappearing with increasing Se flux. A solar cell fabricated using a 900‐nm CIGS film showed the power conversion efficiency of 8·6%, the highest value found in a sub‐micron thick CIGS solar cell related to a reactive sputtering process with metallic targets. Copyright © 2011 John Wiley & Sons, Ltd.     

新型CIGS阻挡层多横向界面Mo的特性及对器件性能的影响

采用磁控溅射方法,在不锈钢箔上制备多横向界 面Mo(M-Mo,multi-transverse interface Mo)和单横向界面Mo(S-Mo)薄 膜,并利用共蒸发三步法分别在M-Mo和S-Mo薄膜上制备Cu(In,Ga)Se₂(CIGS)薄膜及 器件。通过二次离子质谱仪(SIMS)、X射线衍射仪(XRD)和扫描电子显微镜(SEM)研究了不同 结构的Mo薄膜对CIGS影响。通过I-V测试,表征M-Mo和S -Mo作为背电极的CIGS电池电学性能。XRD结果显示,M-Mo和S-Mo 薄膜均以(110)为择优取向。SEM结果显示,M-Mo薄膜相对 于S-Mo,薄膜晶粒 较小,粗糙度较大。J-V测试结果显示,M-Mo薄膜作为背 电极的电池的开路电压Voc、短路电流J sc和填充因子(FF)均有所提高。     

Accelerated development of CuSbS2 thin film photovoltaic device prototypes

Development of alternative thin film photovoltaic technologies is an important research topic because of the potential of low‐cost, high‐efficiency solar cells to produce terawatt levels of clean power. However, this development of unexplored yet promising absorbers can be hindered by complications that arise during solar cell fabrication. Here, a high‐throughput combinatorial method is applied to accelerate development of photovoltaic devices, in this case, using the novel CuSbS₂ absorber via a newly developed three‐stage self‐regulated growth process to control absorber purity and orientation. Photovoltaic performance of the absorber, using the typical substrate CuIn_xGa_{1 − x}Se₂ (CIGS) device architecture, is explored as a function of absorber quality and thickness using a variety of back contacts. This study yields CuSbS₂ device prototypes with ~1% conversion efficiency, suggesting that the optimal CuSbS₂ device fabrication parameters and contact selection criteria are quite different than for CIGS, despite the similarity of these two absorbers. The CuSbS₂ device efficiency is at present limited by low short‐circuit current because of bulk recombination related to defects, and a small open‐circuit voltage because of a theoretically predicted cliff‐type conduction band offset between CuSbS₂ and CdS. Overall, these results illustrate both the potential and limits of combinatorial methods to accelerate the development of thin film photovoltaic devices using novel absorbers. Copyright © 2016 John Wiley & Sons, Ltd.     

High photo‐conversion efficiency in double‐graded Cu(In,Ga)(S,Se)2 thin film solar cells with two‐step sulfurization post‐treatment

Sulfur is extensively used to increase the bandgap of Cu(In,Ga)(S,Se)₂ (CIGSSe) solar cells and to improve the open circuit voltage (V_OC ) in order to optimize the characteristics of the devices. This study uses a sulfurization process to obtain a double‐graded bandgap profile. Selenization was carried out on Cu(In,Ga) precursors, followed by one sulfurization process or two consecutive sulfurization processes on top of the CIGSe absorber layer surface. The optimum two‐step sulfurization process provides an increase of V_OC of 0.05 V and an improvement of conversion efficiency of 1.17%. The efficiency of the 30 × 30 cm² monolithic module, which has 64 CIGS cells connected in series (aperture area: 878.6 cm²), is 15.85%. The optical and electrical properties of the phase and the work function distribution were investigated using the depth profiles of the absorber layer as a function of the sulfurization conditions. The CIGSSe thin film formed by two‐step sulfurization with a high sulfur concentration exhibits a single work function peak, better crystallinity, and higher conversion efficiency than those of the thin film formed by two‐step sulfurization at low sulfur concentration. In terms of the Raman spectra depth profile, the phase areas for the CIGSSe thin film that underwent the optimized high sulfur concentration two‐step‐sulfurization appeared to have less of Cu_2‐xSe phase than that with low sulfur concentration. Consequently, surface and interface phase analysis is an essential consideration to improve cell efficiency. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.     

Electrical properties of CIGS/Mo junctions as a function of MoSe2 orientation and Na doping

The electrical properties of Cu(In,Ga)Se₂/Mo junctions were characterized with respect of MoSe₂ orientation and Na doping level using an inverse transmission line method, in which the Cu(In,Ga)Se₂ (CIGS)/Mo contact resistance could be measured separately from the CIGS film sheet resistance. The MoSe₂ orientation was controlled by varying the Mo surface density, with the c‐axis parallel and normal orientations favored on Mo surfaces of lower and higher density, respectively. The effect of Na doping was compared by using samples with and without a SiO_x film on sodalime glass. The conversion of the MoSe₂ orientation from c‐axis normal to parallel produced a twofold reduction in CIGS/Mo contact resistance. Measurements of the contact resistances as a function of temperature showed that the difference in CIGS/Mo contact resistance between the samples with different MoSe₂ orientations was due to different barrier heights at the back contact. Comparison between Na‐doped and Na‐reduced samples revealed that the contact resistance for the Na‐reduced system was four times of that of the doped sample, which showed more pronounced Schottky‐junction behavior at lower temperature, indicating that Na doping effectively reduced the barrier height at the back contact. Copyright © 2013 John Wiley & Sons, Ltd.     

Effects of Sb-doping on the grain growth of CIGS thin films fabricated by electrodeposition

Cu(InGa)Se2 (CIGS) solar cells become one of the most important thin film photovoltaic devices thus far. The doping of Sb has improved the grain size of CIGS thin film and therefore led to the enhancement of solar cell efficiency. Various approaches have been used for the Sb doping. Not many reports of electrodeposition of In, Ga and Sb alloy have been reported. In this work, the Sb thin film was coated over Cu film surface prior to the In and Ga deposition in order to form a Cu/Sb/In/Ga metal precursor. After selenization, the Sb doped CIGS film was prepared. The structure and morphology of Sb doped CIGS films were investigated compared with the undoped CIGS reference samples. A modified selenization method was proposed, which improved the grain size. Finally, the conversion efficiency of Sb doped CIGS based solar cells has been improved by 1.02%.     

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.