Effects of Ga concentration on structural and electrical properties of screen printed-CIGS absorber layers on polyethylene terephthalate

Copper indium gallium diselenide (CIGS) films were deposited as an absorber layer on polyethylene terephthalate (PET) substrates by a screen printing technique using CIGS ink with a Ga content ranging from 0.3 to 0.6. The melting point of PET substrate is 254.9 °C; the average transmission in the visible (400 nm–800 nm) for PET substrates is greater than 85%. Effects of Ga content of the CIGS absorber layer on structural and electrical properties of the CIGS films were studied. The lattice parameters, a and c for all CIGS films were decreased with increasing Ga content. At room temperature, Hall mobility and charge-carrier concentration of the CIGS films varies from 97.2 to 2.69 cm² V⁻¹ s⁻¹ and 9.98×10¹⁶ to 3.23×10¹⁸ cm⁻³, respectively.     

Surface engineering in Cu(In,Ga)Se2 solar cells

Surface modifications of three‐stage co‐evaporated Cu(In,Ga)Se₂ (CIGS) thin films are investigated by finishing the evaporation with gallium‐free (CuInSe₂, CIS) stages of various lengths. Secondary‐ion mass spectrometry shows substantial interdiffusion of indium and gallium, smearing out the Ga/(Ga + In) profile so that the addition of a CIS layer merely lowers the gallium content at the surface. For the thinnest top layer, equivalent to 20 nm of pure CIS, X‐ray photoelectron spectroscopy does not detect any compositional difference compared with the reference device. The modifications are evaluated electrically both by temperature‐dependent characterisation of actual solar‐cell devices and by modelling, using the latest version of scaps‐1d (Electronics and Information Systems, Ghent University, Belgium). The best solar‐cell device from this series is obtained for the 20 nm top layer, with an efficiency of 16.6% after antireflective coating. However, we observe a trend of decreasing open‐circuit voltage for increasingly thick top layers, and we do not find direct evidence that the lowering of the gallium concentration at the CIGS surface should generally be expected to improve the device performance. A simulated device with reduced bulk and interface defect levels achieves nearly 20% efficiency, but the trends concerning the CIS top layer remain the same. Copyright © 2011 John Wiley & Sons, Ltd.     

Gallium gradients in Cu(In,Ga)Se2 thin‐film solar cells

The gallium gradient in Cu(In,Ga)Se₂ (CIGS) layers, which forms during the two industrially relevant deposition routes, the sequential and co‐evaporation processes, plays a key role in the device performance of CIGS thin‐film modules. In this contribution, we present a comprehensive study on the formation, nature, and consequences of gallium gradients in CIGS solar cells. The formation of gallium gradients is analyzed in real time during a rapid selenization process by in situ X‐ray measurements. In addition, the gallium grading of a CIGS layer grown with an in‐line co‐evaporation process is analyzed by means of depth profiling with mass spectrometry. This gallium gradient of a real solar cell served as input data for device simulations. Depth‐dependent occurrence of lateral inhomogeneities on the µm scale in CIGS deposited by the co‐evaporation process was investigated by highly spatially resolved luminescence measurements on etched CIGS samples, which revealed a dependence of the optical bandgap, the quasi‐Fermi level splitting, transition levels, and the vertical gallium gradient. Transmission electron microscopy analyses of CIGS cross‐sections point to a difference in gallium content in the near surface region of neighboring grains. Migration barriers for a copper‐vacancy‐mediated indium and gallium diffusion in CuInSe₂ and CuGaSe₂ were calculated using density functional theory. The migration barrier for the In_Cu antisite in CuGaSe₂ is significantly lower compared with the Ga_Cu antisite in CuInSe₂, which is in accordance with the experimentally observed Ga gradients in CIGS layers grown by co‐evaporation and selenization processes. Copyright © 2014 John Wiley & Sons, Ltd.     

Effects of combined additional indium deposition and potassium fluoride post‐deposition treatments on Cu(In,Ga)Se2 thin film solar cells

The effect of additional indium on copper indium gallium selenide (CIGS) thin films and solar cells was investigated with respect to potassium fluoride post‐deposition treatment (KF‐PDT) using current‐voltage, external quantum efficiency, scanning electron microscopy, X‐ray photoelectron spectroscopy, time‐resolved photoluminescence and capacitance‐voltage measurements. The cell performance, particularly open‐circuit voltage (V _oc) improved drastically by the combined treatments of additional indium deposition after CIGS growth and subsequent KF‐PDT. A Cu deficient layer at the CIGS surface increased after both treatments rather than only KF‐PDT. Photoluminescence intensity, lifetime and net carrier concentration of KF‐untreated CIGS solar cells did not change significantly by only additional indium deposition. However, they improved because of the combined treatments. Copyright © 2017 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.     

Preparation of CuInxGa1−xSe2 solar cells by electron beam evaporation of powdered evaporants

Cu(In,Ga)Se₂ (CIGS) thin films were deposited by electron beam evaporation of ball-milled powders containing various amounts of gallium. The effects of the gallium concentration in the Cu(In,Ga)Se₂ on the structure, surface morphology and optical properties of the films were investigated using X-ray diffraction, energy-dispersive X-ray analysis, atomic force microscopy and optical spectroscopy. All of the films, which were deposited at 450 °C, were polycrystalline and exhibited a chalcopyrite structure with a (112) preferred orientation. The optical constants of the films were calculated. The grain size, the roughness and the band gap increased with increasing amounts of gallium in the films. A glass/TCO/CdS/CIGS/Au solar cell with 12.87% efficiency was prepared directly from the powdered material.     

Structural and electrical properties of co-evaporated In,Garich CIGS thin films

The CIGS thin trims are prepared by co-evaporation of elemental In, Ga and Se on the substrates of Mo-coated glasses at 400℃ followed by co-evaporation of elemental Cu and Se at 550℃. We study the structural and electrical properties using XRD, XRF and Hall effect measurements. In general, Cu（In,Ga）sSes phase exists when Cu/（In＋Ga） ratio is from 0.17 to 0.27, Cu（In,Ga）3Se5 phase exists for Cu/（In＋Ga） ratio between 0.27 and 0.41, Cu2（in,Ga）4Se7 and Cu（In,Ga）2Se3.5 phases exist for Cu/0n＋Ga） ratio between 0.41 and 0.61, and OVC（or ODC） and CuIn0.7Ga0.3Se2 phases exist when Cu/（In＋Ga） ratio is from 0.61 to 0.88. With the increase of Cu/（In＋Ga） ratio, the carrier concentrations of the films gradually increase, but the electrical resistivity gradually decreases.     

Growth of Cu(In,Ga)Se2 thin films by a novel single‐stage route based on pulsed electron deposition

We report a novel route for growing Cu(In,Ga)Se₂ (CIGS) thin films, based upon the Pulsed Electron Deposition (PED) technique. Unlike other well‐known deposition techniques, PED process allows the stoichiometric deposition of CIGS layers in a single stage, without requiring any further treatments for Cu/(In + Ga) ratio adjustment nor selenization. The structural properties of polycrystalline CIGS films strongly depend on the growth temperature, whereas post‐deposition annealing enhances the grain size and the <112> out‐of‐plane preferred orientation of the chalcopyrite structure, without affecting the film composition. Preliminary measurements of the performances of solar cells based on these films confirm the great potentiality of PED‐grown CIGS as absorber layers. Copyright © 2011 John Wiley & Sons, Ltd.     

Reactive Sputtering Process for CuIn1‐xGaxSe2 Thin Film Solar Cells

CuIn_1‐xGa_xSe₂ (CIGS) thin films are grown on Mo/soda lime glass using a reactive sputtering process in which a Se cracker is used to deliver reactive Se molecules. The Cu and (In_0.7Ga_0.3)₂Se₃ targets are simultaneously sputtered under the delivery of reactive Se. The effects of Se flux on film composition are investigated. The Cu/(In+Ga) composition ratio increases as the Se flux increases at a plasma power of less than 30 W for the Cu target. The (112) crystal orientation becomes dominant, and crystal grain size is larger with Se flux. The power conversion efficiency of a solar cell fabricated using an 800‐nm CIGS film is 8.5%.     

铜含量变化对Cu(In,Ga)Se2薄膜微结构的影响

报道了不同的铜含量(Cu/(Ga+In)=0.748~0.982)对Cu(In,Ga)Se2 (CIGS)薄膜微结构的影响.文章中的CIGS薄膜采用磁控溅射金属预置层后硒化的方法制备, 其X射线衍射谱(XRD)中一系列黄铜矿结构CIGS(CH-CIGS)相的衍射峰确认了CH-CIGS相的存在.对CIGS薄膜拉曼光谱的分析表明, 随着铜含量的上升, CIGS薄膜经历了CH-CIGS和有序缺陷化合物(OVC)混合相、CH-CIGS单相、CH-CIGS和CuxSe混合相三种状态.进一步的分析显示, CIGS薄膜拉曼峰的半高宽随铜含量变化, 并在Cu/(Ga+In)=0.9附近时达到最小值, 这说明此时CIGS薄膜具有更好的结晶度和更少的无序性.此外还得到了CIGS薄膜拉曼峰半高宽与铜含量的经验关系公式.这些研究表明拉曼光谱能比XRD更加灵敏地探测CIGS薄膜的微结构, 可望作为一种无损和快速测量方法, 用于对CIGS薄膜晶相和铜含量的初步估计.     

A stacked chalcopyrite thin‐film tandem solar cell with 1.2 V open‐circuit voltage

CuGaSe₂ (CGS) thin films were prepared on tin‐doped indium oxide (ITO) coated soda‐lime glass substrates by thermal co‐evaporation to fabricate transparent solar cells. The films consisted of columnar grains with a diameter of approximately 1 μm. Some deterioration of the transparency of the ITO was observed after deposition of the CGS film. The CGS solar cells were electrically connected in series with Cu(In,Ga)Se₂ (CIGS) solar cells and mechanically stacked on the CIGS cells to construct tandem cells. The tandem solar cell with the CGS cell as the top cell showed an efficiency of 7.4% and an open‐circuit voltage of 1.18 V (AM 1.5, total area). Copyright © 2003 John Wiley & Sons, Ltd.     

Growth of Zn doped Cu(In, Ga)Se2 thin films by RF sputtering for solar cell applications

Cu(In, Ga)Se₂ (CIGS) surface was modified with Zn doping using a magnetron sputtering method. CuInGa:Zn precursor films targeting a CuIn_0.7Ga_0.3Se₂ stoichiometry with increasing Zn content from 0 to 0.8 at% were prepared onto Mo-coated glass substrates via co-sputtering of Cu–Ga alloy, In and Zn targets. The CuInGa:Zn precursors were then selenized with solid Se pellets. The structures and morphologies of grown Zn doped CIGS films were found to depend on the Zn content. At zinc doping level ranging between 0.2 and 0.6 at%, the Zn doping improved the crystallinity and surface morphology of CIGS films. Compared with the performance of the non-doped CIGS cell, the fabricated CIGS solar cell displayed a relative efficiency enhancement of 9–22% and the maximum enhancement was obtained at a Zn content of 0.4 at%.     

Bandgap optimization of submicron‐thick Cu(In,Ga)Se2 solar cells

Reducing Cu(In,Ga)Se₂ (CIGS) absorber thickness into submicron regime provides an opportunity for reducing CIGS solar cell manufacturing time and cost. However, CIGS with submicron‐thick absorber would suffer strong absorption loss in the long‐wavelength region. In this paper, we report a new fabrication route for CIGS solar cells on soda‐lime glass substrates with different Ga content (0.3 < [Ga]/([Ga] + [In]) < 0.6), all with absorber thicknesses around 0.9 µm. Efficiency of 17.52% has been achieved for cells with high Ga content of [Ga]/([Ga] + [In]) = 41%, which is currently the best reported efficiency for submicron‐thick CIGS solar cells. Unlike the normal‐thickness absorber (2–3 µm) that has an optimal [Ga]/([Ga] + [In]) of ~32%, the increased value of optimal [Ga]/([Ga] + [In]) in submicron‐thick absorber greatly enhances the open‐circuit voltage, by nearly 15% compared with that of samples with Ga content optimized at normal absorber thickness. This large gain in V_OC well compensates the absorption loss in the long‐wavelength region and contributes to the enhancement of final solar cell efficiency. Copyright © 2014 John Wiley & Sons, Ltd.     

Cu(In,Ga)Se<Subscript>2</Subscript> Thin Film Preparation from a Cu(In,Ga) Metallic Alloy and Se Nanoparticles by an Intense Pulsed Light Technique

The main contribution of this paper is the development of a novel process for the formation of copper indium gallium diselenide (CIGS) films. CIGS films with a thickness of 4 μm and grain size from 0.3 μm to 1 μm were prepared from a Cu(In_0.7Ga_0.3) (CIG) metallic alloy and Se nanoparticles by the intense pulsed light (IPL) technique. The melting of the CIG and Se nanoparticles and nucleation of CIGS occurred in a very short reaction time of 2 ms. It is believed that the Se diffuses into the CIG lattice to form the CIGS chalcopyrite crystal structure. The tetragonal chalcopyrite crystal structure was confirmed by x-ray powder diffraction (XRD), while the microstructure and composition were determined by field-emission scanning electron microscopy (FESEM), energy-dispersive x-ray spectroscopy (EDAX), and x-ray fluorescence (XRF) spectroscopy.     

Controllable Formation of Ordered Vacancy Compound for High Efficiency Solution Processed Cu(In,Ga)Se2 Solar Cells

Solution processing of Cu(In,Ga)Se₂ (CIGS) absorber makes it cost-competitive in the photovoltaic market. It is reported that copper-poor ordered vacancy compound (OVC) is crucial for high performance CIGS solar cells. However, in solution process method, controllable formation of OVC is unavailable and limited research has been carried out. In this work, the controllable formation of the OVC phase on the CIGS surface is successful by controlling the selenization temperature and intentional variation of Cu/(In+Ga) stoichiometry in precursors for top layers and bulk layers deposition. The effects of OVC contents on the device performance are investigated. The CIGS thin film with OVC phase exhibits a lower valence band position. Meanwhile, the CIGS devices with optimized OVC content show decreased interface defects density and better carrier collection ability. The above advantages translate into a champion PCE of 16.39% for CIGS device with OVC phase, which is the champion performance among non-hydrazine solution-processed CIGS solar cells. The results demonstrate that the controllable formation of OVC phase approach should make a significant contribution to the efficiency promoting of solution processed CIGS solar cells.     

玻璃衬底上RF磁控溅射CIGS薄膜的研究

采用射频磁控溅射的工艺,在玻璃衬底上制备得到了铜铟镓硒(CIGS)薄膜。讨论了衬底温度、溅射气压、退火与否对CIGS薄膜与衬底结合力、显微形貌、晶化程度及电阻率的影响。通过能谱(EDS)测试证明了溅射的CIGS薄膜Ga组分比符合高效吸收层的要求,通过X射线衍射(XRD)与扫描电子显微镜(SEM)测试,证明了衬底加热溅射、溅射后450℃空气退火可以有效提高CIGS薄膜与衬底的结合并提高晶化程度。通过四探针法电阻率测试证明了低气压条件下溅射、溅射后退火可以有效降低CIGS的电阻率,通过透射光谱分析证明了CIGS薄膜对可见光有高吸收效率,适合作为太阳电池的高效吸收层。     

Effect of the chemical composition of Cu–In–Ga–Se layers on the photoconductivity and conversion efficiency of CdS/CIGSe solar cells

The effect of the [Ga]/[In+Ga] ratio of gallium and indium on the microwave photoconductivity of Cu–In–Ga–Se (CIGSe) films and on the efficiency of solar cells fabricated in accordance with the same technology is investigated. According to the observations of a field-emission scanning electron microscopy (FESEM), the grain size decreases with increasing Ga content. With increasing gallium content in the samples, the photogenerated-electron lifetime and the activation energy of the microwave photoconductivity also decrease. The changes in the activation energy of the through conduction in darkness are less than 20%. Analysis of the obtained data shows that the known effect of the gallium gradient on the efficiency should be associated with modification of the internal structure of grains instead of with their boundaries.     

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.     

Texture and morphology variations in (In,Ga)2Se3 and Cu(In,Ga)Se2 thin films grown with various Se source conditions

Texture and morphology variations in co‐evaporated (In,Ga)₂Se₃ and Cu(In,Ga)Se₂ (CIGS) films grown with various Se source conditions during growth were studied. The Se species of simply evaporated, large molecular Se (E‐Se, low‐sticking coefficient), and RF‐plasma cracked atomic Se (R‐Se, high sticking coefficient) were used in the present work. (In,Ga)₂Se₃ precursor films, which were prepared during the first stage of CIGS film growth by the three‐stage process, showed systematic variations in texture and Na distribution profile with varying evaporative Se (E‐Se) flux. The properties of CIGS films and solar cells also showed systematic variations, and the open‐circuit voltage (V_oc) and fill factor were found to be especially sensitive to the E‐Se flux. R‐Se grown (In,Ga)₂Se₃ precursor films featured granular morphology with strong (105) and (301) peaks in the diffraction pattern, and the texture was very similar to an E‐Se grown film fabricated with a Se to group III metal (In + Ga) flux ratio (P_{[Se]/[In + Ga]}) of about 6, although the nominal P_{[Se]/[In + Ga]} used for an R‐Se source was very small and less than 0.5. The R‐Se grown CIGS films displayed, however, highly dense surfaces and larger grain sizes than E‐Se grown CIGS films. The controllability of film morphology and the Na diffusion profile in (In,Ga)₂Se₃ and CIGS films with various Se source conditions are discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Variations in the characteristics of CdxZn1-xS films deposited with little Cd-containing solutions

In order to prepare Cd_xZn_1-xS films with lower cadmium content and better performance as a buffer layer for copper indium gallium selenide(CIGS) solar cells, the performance of Cd_xZn_1-xS films deposited in a mixture of solutions containing extremely low cadmium sources was systematically investigated by chemical bath deposition(CBD) with the synergy of chemical experiments and numerical simulations. The experimental results show that the films have the...