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%.     

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.     

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.     

Metamorphic GayIn1−yP/Ga1−xInxAs tandem solar cells for space and for terrestrial concentrator applications at C > 1000 suns

The use of Ga_1−xIn_xAs instead of GaAs as a bottom solar cell in a Ga_yIn_1−yP/Ga_1−xIn_xAs tandem structure increases the flexibility of choosing the optimum bandgap combination of materials for a multijunction solar cell. Higher theoretical efficiencies are calculated and different cell concepts are suggested for space and terrestrial concentrator applications. Various Ga_yIn_1−yP/Ga_1−xIn_xAs material combinations have been investigated for the first time and efficiencies up to 24·1% (AM0) and 27·0% (AM1·5 direct) have been reached under one-sun conditions. An efficiency of 30·0–31·3% was measured for a Ga_0·35In_0·65P/Ga_0·83In_0·17As tandem concentrator cell with prismatic cover at 300 suns. The top and bottom cell layers of this structure are grown lattice-matched to each other, but a large mismatch is introduced at the interface to the GaAs substrate. This cell structure is well suited for the use in next-generation terrestrial concentrators working at high concentration ratios. For the first time a cell efficiency up to 29–30% has been measured at concentration levels up to 1300 suns. A small prototype concentrator with Fresnel lenses and four tandem solar cells working at C = 120 has been constructed, with an outdoor efficiency of 23%. Copyright © 2001 John Wiley & Sons, Ltd.     

Study on ALD In2S3/Cu(In,Ga)Se2 interface formation

The formation of the interface between In₂S₃ grown by atomic layer deposition (ALD) and co‐evaporated Cu(In,Ga)Se₂ (CIGS) has been studied by X‐ray and UV photoelectron spectroscopy. The valence band offset at 160°C ALD substrate temperature was determined as −1·2±0·2 eV for CIGS deposited on soda‐lime glass substrates and −1·4±0·2 eV when a Na barrier substrate was used. Wavelength dependent complex refractive index of In₂S₃ grown directly on glass was determined from inversion of reflectance and transmittance spectra. From these data, an indirect optical bandgap of 2·08±0·05 eV was deduced, independent of film thickness, of substrate temperature and of Na content. CIGS solar cells with ALD In₂S₃ buffer layers were fabricated. Highest device efficiency of 12·1% was obtained at a substrate temperature of 120°C. Using the bandgap obtained for In₂S₃ on glass and a 1·15±0·05 eV bandgap determined for the bulk of the CIGS absorber, the conduction band offset at the buffer interface was estimated as −0·25±0·2 eV (−0·45±0·2 eV) for Na‐containing (Na‐free) CIGS. Copyright © 2005 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.     

The Zn(S,O,OH)/ZnMgO buffer in thin‐film Cu(In,Ga)(Se,S)2‐based solar cells part II: Magnetron sputtering of the ZnMgO buffer layer for in‐line co‐evaporated Cu(In,Ga)Se2 solar cells

A ZnS/Zn_1‐xMg_xO buffer combination was developed to replace the CdS/i‐ZnO layers in in‐line co‐evaporated Cu(In,Ga)Se₂(CIGS)‐based solar cells. The ZnS was deposited by the chemical bath deposition (CBD) technique and the Zn_1‐xMg_xO layer by RF magnetron sputtering from ceramic targets. The [Mg]/([Mg] + [Zn]) ratio in the target was varied between x = 0·0 and 0·4. The composition, the crystal structure, and the optical properties of the resulting layers were analyzed. Small laboratory cells and 10 × 10 cm² modules were realized with high reproducibility and enhanced stability. The transmission is improved in the wavelength region between 330 and 550 nm for the ZnS/Zn_1‐xMg_xO layers. Therefore, a large gain in the short‐circuit current density up to 12% was obtained, which resulted in higher conversion efficiencies up to 9% relative as compared to cells with the CdS/i‐ZnO buffer system. Peak efficiencies of 18% with small laboratory cells and 15·2% with 10 × 10 cm² mini‐modules were demonstrated. Copyright © 2009 John Wiley & Sons, Ltd.     

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.     

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.     

Cu2ZnSn(S,Se)4薄膜太阳电池研究进展

Cu2ZnSn(S,Se)4(CZTS)材料具有与Cu(In,Ga)Se2(CIGS)材料相似的光学性质和半导体性质,且原料丰富,是CIGS薄膜太阳电池重要的后备材料。有关CZTS薄膜制备工艺的研究和电池器件转换效率提升的研究正成为本领域新的研究开发热点。目前,有实力的薄膜太阳电池研究队伍已经针对CZTS薄膜太阳电池开展了持续的研究,试图通过不同的CZTS吸收层制备方式和优化电池组装工艺过程,进一步提高CZTS薄膜太阳电池的光电转换效率。文章阐述了CZTS材料特性,着重介绍了目前国内外所采用的CZTS薄膜制备方法,详细讨论了各种薄膜沉积技术的优缺点。最后展望了CZTS电池的发展趋势。     

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.     

Thick In x Ga1−x N Films Prepared by Reactive Sputtering with Single Cermet Targets

In _x Ga_1?x N films with x = 0, 0.25, and 0.5 were grown on SiO₂/Si(100) substrates by reactive sputtering at 200°C for 90 min with single cermet targets made by hot pressing a powder mixture of metallic indium and gallium and gallium nitride. After alloying with In, InGaN showed preferential (10 $ \mathop 1\limits^{ - } $ 0) diffraction, smooth surface with roughness less than 1.80 nm, reduced mismatch with the Si substrate, enhanced electron mobility above 7 cm² V^?1 s^?1, and blue and green light-emitting capabilities.     

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.     

KF post deposition treatment in co‐evaporated Cu(In,Ga)Se2 thin film solar cells: Beneficial or detrimental effect induced by the absorber characteristics

Recent breakthroughs in Cu(In,Ga)Se₂ (CIGS) thin film solar cell energy conversion efficiency are related to the application of a potassium fluoride post‐deposition treatment (KF‐PDT) to the completed absorber. Using X‐ray photoelectron spectroscopy and Raman scattering, we compare CIGS layers prior and after the KF‐PDT in the case of a deterioration and an improvement of the solar cells photovoltaic performance. The purpose is to study and model the modification of the surface in both cases and address some of the required characteristics of the absorber, grown on soda lime glass by 3‐stage process, in order to take advantage of the treatment. We show that, in both cases, KF‐PDT induces the formation of GaF₃, which is removed during the subsequent chemical bath deposition of CdS, explaining the Ga depleted absorber surface, already reported in literature. However, the presence or not of an ordered defect compound (ODC), correlated with the third stage duration during the CIGS growth, is shown to be crucial in the modifications of the surface induced by the treatment. When an ODC is present prior the treatment, KF‐PDT leads to the formation of a surface layer of In₂Se₃ containing K, and the photovoltaic performance of completed solar cells are improved. When no ODC is present prior KF‐PDT, no trace of K is found at the absorber surface after the treatment, copper (Cu) segregates into detrimental Cu_xSe phases, high amount of elemental Se is formed, and the photovoltaic performance are lowered. The role of the ODC during the KF‐PDT is finally discussed.     

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.     

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.     

CuIn1−xGaxSe2‐based thin‐film solar cells by the selenization of sequentially evaporated metallic layers

Polycrystalline CuIn_1−xGa_xSe₂ (CIGS) thin films were deposited by the non‐vacuum, near‐atmospheric‐pressure selenization of stacked metallic precursor layers. A study was carried out to investigate the influence of significant factors of the absorber on the solar cells performance. An efficiency enhancement was obtained for Cu/(In+Ga) atomic ratios between 0·93 and 0·95. The slope of the observed energy bandgap grading showed a strong influence on the V_OC and the short circuit current density J_SC. An increase of the Ga content in the active region of the absorber was achieved by the introduction of a thin Ga layer on the Mo back contact. This led to an improvement of efficiency and V_OC. Furthermore, an enhanced carrier collection was detected by quantum efficiency measurements when the absorber layer thickness was slightly decreased. Conversion efficiencies close to 10% have been obtained for these devices. Copyright © 2005 John Wiley & Sons, Ltd.     

Na‐induced efficiency boost for Se‐deficient Cu(In,Ga)Se2 solar cells

Among different process routes for Cu(In,Ga)Se₂ (CIGS) solar cells, sufficient Se supply is commonly required to obtain high‐quality CIGS films. However, supplying extra Se increases the cost and the complexity. In this work, we demonstrate that extra Na incorporation can substantially increase efficiency of Se‐deficient CIGS solar cells, fabricated by sputtering from a quaternary CIGS target without extra Se supply, from 1.5% to 11.0%. The Se‐deficient CIGS device without extra NaF reveals a roll‐over I–V curve at room temperature as well as significantly reduced J_sc and fill factor at low temperatures. The electrical characteristics of Se‐deficient CIGS films are well explained and modeled by the low p‐type doping due to high density of compensating donors and the presence of deep defects possibly originating from the anti‐bonding levels of Se vacancies. The significant improvement after extra Na incorporation is attributable to the Na‐induced passivation of Se vacancies and the increased p‐type doping. Our result suggests that extra Na addition can effectively compensate the Se deficiency in CIGS films, which provides a valuable tuning knob for compositional tolerance of absorbers, especially for the Se‐deficient CIGS films. We believe that our findings can shine light on the development of novel CIGS processes, distinct from previous ones fabricated in Se‐rich atmosphere. Copyright © 2015 John Wiley & Sons, Ltd.     

All‐Solution‐Processed Indium‐Free Transparent Composite Electrodes based on Ag Nanowire and Metal Oxide for Thin‐Film Solar Cells

Fully solution‐processed Al‐doped ZnO/silver nanowire (AgNW)/Al‐doped ZnO/ZnO multi‐stacked composite electrodes are introduced as a transparent, conductive window layer for thin‐film solar cells. Unlike conventional sol–gel synthetic pathways, a newly developed combustion reaction‐based sol–gel chemical approach allows dense and uniform composite electrodes at temperatures as low as 200 °C. The resulting composite layer exhibits high transmittance (93.4% at 550 nm) and low sheet resistance (11.3 Ω sq^‐1), which are far superior to those of other solution‐processed transparent electrodes and are comparable to their sputtered counterparts. Conductive atomic force microscopy reveals that the multi‐stacked metal‐oxide layers embedded with the AgNWs enhance the photocarrier collection efficiency by broadening the lateral conduction range. This as‐developed composite electrode is successfully applied in Cu(In_1‐x,Ga_x)S₂ (CIGS) thin‐film solar cells and exhibits a power conversion efficiency of 11.03%. The fully solution‐processed indium‐free composite films demonstrate not only good performance as transparent electrodes but also the potential for applications in various optoelectronic and photovoltaic devices as a cost‐effective and sustainable alternative electrode.     

Atomic layer deposition of Zn1−xMgxO buffer layers for Cu(In,Ga)Se2 solar cells

Fabrication of Zn_1−xMg_xO films by atomic layer deposition (ALD) has been studied for use as buffer layers in Cu(In,Ga)Se₂ (CIGS)‐based solar cell devices. The Zn_1−xMg_xO films were grown using diethyl zinc, bis‐cyclopentadienyl magnesium and water as precursors in the temperature range from 105 to 180°C. Single‐phase ZnO‐like films were obtained for x < 0·2, followed by a two phase region of ZnO‐ and MgO‐like structures for higher Mg concentrations. Increasing optical band gaps of up to above 3·8 eV were obtained for Zn_1−xMg_xO with increasing x. It was found that the composition of the Zn_1−xMg_xO films varied as an effect of deposition temperature as well as by increasing the relative amount of magnesium precursor pulses during film growth. Completely Cd‐free CIGS‐based solar cells devices with ALD‐Zn_1−xMg_xO buffer layers were fabricated and showed efficiencies of up to 14·1%, which was higher than that of the CdS references. Copyright © 2006 John Wiley & Sons, Ltd.