Growth and Raman scattering characterization of Cu2ZnSnS4 thin films

In the present work we report the results of the growth, morphological and structural characterization of Cu₂ZnSnS₄ (CZTS) thin films prepared by sulfurization of DC magnetron sputtered Cu/Zn/Sn precursor layers. The adjustment of the thicknesses and the properties of the precursors were used to control the final composition of the films. Its properties were studied by SEM/EDS, XRD and Raman scattering. The influence of the sulfurization temperature on the morphology, composition and structure of the films has been studied. With the presented method we have been able to prepare CZTS thin films with the kesterite structure.     

Influence of precursor stacking on the absorber growth in Cu(In,Ga)S2 based solar cells prepared by a rapid thermal process

Rapid thermal sulfurization of metallic precursors has proven to be a successful method for the preparation of Cu(In,Ga)S₂ based solar cells. However, during the sulfurization, several problems can be encountered. Due to the difference in reaction rates between ternary sulfides, the process can result in absorbers with a layered CuInS₂/CuGaS₂ structure or slow and incomplete sulfurization that leads to samples where an unreacted Cu-Ga metallic phase remains at the back of the sample. The formation kinetics of single phase Cu(In,Ga)S₂ is a complex process which depends on several parameters. In this work, we focus on the influence of precursor stacking and investigate the growth of Cu(In,Ga)S₂ thin films using scanning electron microscopy and X-ray diffraction. It is observed that precursor alloying occurs prior to sulfurization and that the Cu(In,Ga)S₂ compound is formed by the interdiffusion of the ternary CuInS₂ and CuGaS₂ phases. Correlation between the structural properties of the precursors/absorbers and the obtained solar cells is made.     

Effect of copper-deficiency on multi-stage co-evaporated Cu(In,Ga)S2 absorber layers and solar cells

Solar cell absorber films of Cu(In,Ga)S₂ have been fabricated by multi-stage co-evaporation resulting in compositional ratios [Cu]/([In] + [Ga]) = 0.93-0.99 and [Ga]/([In] + [Ga]) = 0.15. Intentional doping is provided by sodium supplied from NaF precursor layers of different thicknesses. Phases, structure and morphology of the resulting films are investigated by X-ray diffraction (XRD) and scanning electron microscopy. The XRD patterns show CuIn₅S₈ thiospinel formation predominantly at the surface in order to accommodate decreasing Cu content. Correlated with the CuIn₅S₈ formation, a Ga-enrichment of the chalcopyrite phase is seen at the surface. Since no CuS layer is present on the as-deposited films, functioning solar cells with CdS buffer and ZnO window layers were fabricated without KCN etch. The open-circuit voltage of solar cells correlates with the copper content and with the amount of sodium supplied. The highest efficiency cell (open-circuit voltage 738 mV, short-circuit current 19.3 mA/cm², fill factor 65%, efficiency 9.3%) is based on the absorber with the least Cu deficiency, [Cu]/([In] + [Ga]) = 0.99. The activation energy of the diode saturation current density of such a cell is extracted from temperature- and illumination-dependent current-voltage measurements. A value of 1.04 eV, less than the band gap, suggests the heterojunction interface as the dominant recombination zone, just as in cells based on Cu-rich grown Cu(In,Ga)S₂.     

Progress in the development of CuInS2 based mini-modules

A sequential process is used to synthesise CuInS₂ absorber layers for photovoltaic application. In this process CuIn precursor layers sputtered on molybdenum coated float glass are converted to CuInS₂ via sulphurisation in an elemental sulphur vapour ambient. A re-evaluation of process parameters has been performed including fine tuning of numerous minor aspects. Using optimised process conditions has led to improved device performance, especially a narrowed distribution at higher module efficiencies is achieved. At the same time the process yield is improved resulting in fewer devices with poor electrical quality.     

Reactive sputtering of precursors for Cu2ZnSnS4 thin film solar cells

The quaternary semiconductor Cu₂ZnSnS₄ (CZTS) is a possible In-free replacement for Cu(In,Ga)Se₂. Here we present reactive sputtering with the possibility to obtain homogeneous CZTS-precursors with tunable composition and a stoichiometric quantity of sulfur. The precursors can be rapidly annealed to create large grained films to be used in solar cells. The reactive sputtering process is flexible, and morphology, stress and metal and sulfur contents were varied by changing the H₂S/Ar-flow ratio, pressure and substrate temperature. A process curve for the reactive sputtering from CuSn and Zn targets is presented. The Zn-target is shown to switch to compound mode earlier and faster compared to the CuSn-target. The precursors containing a stoichiometric amount of sulfur exhibit columnar grains, have a crystal structure best matching ZnS and give a broad peak, best matching CZTS, in Raman scattering. In comparing process gas flows it is shown that the sulfur content is strongly dependent on the H₂S partial pressure but the total pressures compared in this study have little effect on the precursor properties. Increasing the substrate temperature changes the film composition due to the high vapor pressures of Zn, SnS and S. High substrate temperatures also give slightly denser and increasingly oriented films. The precursors are under compressive stress, which is reduced with higher deposition temperatures.     

The optical and structural properties of polycrystalline Cu(In,Ga)(Se,S)2 absorber thin films

The pentenary compound semiconductor Cu(In,Ga)(Se,S)₂ is one of the most attractive materials for high-efficiency solar cells due to its tunable band gap to match well the solar spectrum. In this study, semiconducting Cu(In,Ga)(Se,S)₂ thin films were prepared by a classical two-step growth process, which involves the selenization and/or sulfurization of In/Cu–Ga precursor. During the precursor formation step metallic In/Cu–Ga alloys were deposited onto the Mo-coated soda-lime glass substrates by DC magnetron sputter process. The respective precursors were subsequently reacted with H₂Se and/or H₂S gasses, at elevated temperatures. By optimizing the selenization parameters, such as the gas concentrations, reaction time, reaction temperature, and the flow of H₂Se and H₂S, high quality, single phase pentenary films were obtained. The gallium and sulfur diffusion behaviors were found to depend strongly on the selenization/sulfurization profile. The surface morphology, phase structure, and composition of the layers were analyzed by scanning electron microscope, atomic force microscopy, X-ray diffraction, and electron diffraction spectroscopy. Photoluminescence measurements were performed to examine the optical properties of the films.     

Thermal stability of sputtered Mo/polyimide films and formation of MoSe2 and MoS2 layers for application in flexible Cu(In,Ga)(Se,S)2 based solar cells

Molybdenum (Mo) films with a thickness of about 800 nm were room temperature sputtered onto flexible polymeric substrates. Upilex® films were chosen as substrates on the basis of their high thermal endurance and reduced coefficient of thermal expansion. Thermal stability of Mo films has been proved by heat treatment of the Mo/Upilex® structures at a temperature comparable to that used in the preparation of the Cu(In,Ga)(Se,S)₂ absorber layer. A combination of high optical reflectance (maximum values of 75-80%), low electrical resistivity (about 30 μΩ cm) and a smooth surface free of cracks for heated films highlights their good thermal stability. The formation of MoSe₂ and MoS₂ layers, after selenization/sulfurization of the Mo/Upilex® structures, has been further investigated in view of their application as back contact layers in flexible CIGS based solar cells.     

Non-toxic selenization using thermal annealing for CuGa/In bi-layer precursors deposited by sputtering

Cu(In_xGa_1?x)Se₂ (CIGS) thin films were produced using a two-step sputtering process consisting of precursor formation and selenization. In the first stage, we prepared Cu_0.75Ga_0.25/In bi-layer precursors by direct current sputtering on Mo/soda-lime glass substrates. In the second stage, the stacked precursors were selenized using non-toxic Se pellets in a graphite box in which the temperature was controlled at 475–680 °C during rapid thermal annealing. We investigated the effect of thermal annealing temperature on Ga distribution and the crystallinity of the Cu(In_xGa_1?x)Se₂ films. Thermal annealing significantly affected the distribution of Ga atoms. At low temperatures, segregation of Ga atoms into the CIGS/Mo interface and an absence of Ga content on the surface were observed. In addition, a phase-separated CuInSe₂/CuGaSe₂ structure and incomplete selenization phases were observed. At high temperatures, CIGS films were formed with the proper distribution of Ga content.     

Influence of GaSe deposition temperature on the structural properties and in-depth compositional features of two-step grown Cu(In,Ga)Se2 thin films

In this study, Cu(In,Ga)Se₂ thin films were prepared by a classical two-stage growth process, which involved the selenization of thermally evaporated InSe/Cu/GaSe precursors. During the precursor-formation step the InSe and Cu were always deposited at 200 °C, while the GaSe layers were deposited at temperatures between 200 °C and 400 °C. The respective precursors were simultaneously selenized under identical conditions in elemental Se vapor. In cases where the GaSe layers were deposited at low temperatures around 200 °C, X-ray fluorescence (XRF) analysis revealed a large variation in element concentration with sample depth after selenization. In correspondence, X-ray diffraction (XRD) studies revealed the presence of separate CuInSe₂ and CuGaSe₂ phases in these specific samples. Optimum structural properties were obtained when the GaSe films were deposited at 300 °C, followed by selenization. In general, these films were uniform and dense and XRD studies revealed single-phase Cu(In,Ga)Se₂ material. Even more importantly, XRF analysis revealed a remarkable improvement in in-depth compositional uniformity when the GaSe films were deposited at or above 300 °C. An increase in GaSe deposition temperature to 400 °C, however, resulted in a deterioration in the structural features of the Cu(In,Ga)Se₂ thin films. In contradiction with other reports, these results indicated that the in-depth composition uniformity and especially the Ga diffusion profile in two-step grown Cu(In,Ga)Se₂ thin films can be controlled. The crucial factor influencing the depth profile of these films is the GaSe deposition temperature during the precursor formation step.     

Properties of Cu(In,Ga)(S,Se)2 thin films prepared by selenization/sulfurization of metallic alloys

Single-phase Cu(In,Ga)(S,Se)₂ (CIGSS) thin films have been prepared using a two-step process consisting of annealing of Cu-In-Ga precursors in S/Se ambient. Full characterizations have been carried out using XRD, SEM, EDS, Raman spectroscopy and optical absorption measurements. The depth profiles of constituent elements Cu, In, Ga, S and Se were almost constant throughout the film. Depending on overall Ga content and recrystallization temperature CIGSS thin films exhibited a shift in band gap from 1.04 to 1.19 eV.     

Growth of Cu2ZnSnS4 thin films using sulfurization of stacked metallic films

We fabricated Cu₂ZnSnS₄ (CZTS) thin films through sulfurization of stacked metallic films. Three types of Cu-Zn-Sn metallic films, i.e., Cu-rich, Cu-correct and Cu-poor precursor films were sputtered onto Mo-coated glass. The sulfurization of stacked Cu-Zn-Sn alloy films was performed at a relatively high temperature, 570 °C, with S-powder evaporation. CZTS films from Cu-rich and Cu-correct precursors showed a Cu_2 − xS phase on the film surface, while CZTS films from Cu-poor precursors didn't show the Cu_2 − xS phase. However, all films didn't exhibit any extra secondary phase and exhibited good crystalline textures even with Cu-ratio differences in metallic precursor films. Fabricated CZTS films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and Raman scattering measurements. SEM cross-section images of CZTS films showed that Cu-poor CZTS films were grown with more smooth film surface compared with other types of CZTS films.     

Preparation of wide gap Cu(In,Ga)S2 films on ZnO coated substrates

We have prepared Cu(In,Ga)S₂ films at growth temperatures from 300 °C to 580 °C with a homogeneous gallium depth distribution (estimated band gap 1.67 eV) onto soda lime glass (SLG) substrates with one of three different kinds of back contact: Mo(1000 nm), ZnO(500 nm), and Mo(30 nm)/ZnO(500 nm), respectively. We have also investigated the depth profiles of Zn and Na (diffused from SLG) in Cu(In,Ga)S₂ films by secondary ion mass spectroscopy (SIMS). The efficiency of solar cells on Mo increases with increasing growth temperature. It is higher on Mo/ZnO than on ZnO, and increases from 350 °C to 450 °C, then decreases above 450 °C. It was observed by SIMS that the amount of Zn in Cu(In,Ga)S₂ on Mo/ZnO is lower than it is on ZnO up to 450 °C, and a large amount of Zn diffuses into absorbers over 450 °C, which contributes to decreasing efficiency. The amount of Na in the back contact increases with growth temperature. The depth distribution of Na in Cu(In,Ga)S₂ films on Mo is almost constant in the order of 10¹⁷-10¹⁸ cm^− 3, on ZnO and Mo/ZnO the Na concentration increases towards the surface and is in the range of 10¹⁵-10¹⁷ cm^− 3.     

Alternative deposition methods of copper and silver indium ternary sulphides with spinel structure

We compared properties of CuIn₅S₈ and AgIn₅S₈ spinel thin films deposited on soda lime glass and sapphire substrates by three methods: a) conventional sulphurisation of a metallic precursor (I), b) alternative evaporation of the binary sulphides with a post-annealing step in sulphur vapour (II), and c) with a post-annealing in decomposition products of bulk spinel in an evacuated ampoule (III). X-ray diffractometry reveals the polycrystalline nature of the films and demonstrates the presence of cubic spinel phases in the films prepared by all the methods. However, the morphology and the electrical transport properties of the spinel films are essentially different. A high Hall mobility of electrons of 10-50 cm²/(V s) was determined in AgIn₅S₈ films prepared from binary sulphides.     

Growth and properties of Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> thin films prepared by multiple metallic layer stacks as a function of sulfurization time

In this paper, we report the two stage growth of Cu₂ZnSnS₄ (CZTS) thin films as a function of sulfurization time. First, magnetron sputtered metallic precursors were deposited sequentially (Zn/Cu/Sn/Cu) over rotating glass substrates held at 230?°C. Later, the sputtered precursors were heat treated at 500?°C in the ambiance of sulfur for various time durations in the range, 10–120 min. The sulfur treated samples were examined using various analytical tools to understand the role of sulfurization time on the CZTS growth and properties. From composition and structural analysis, Zn/Cu/Sn/Cu precursors sulfurized for shorter duration (10 and 20 min) revealed severe deficiency of sulfur that resulted in several metallic, bi-metallic and metal sulfide phases. With the increase of sulfurization time to 30 min, sulfur incorporation was enhanced and reached stoichiometric ratio (~50% S) for CZTS growth, however, samples were poorly crystalline in nature and consisted of prominent Cu_2?xS phase as well. The Zn/Cu/Sn/Cu precursors sulfurized for 60 min exhibited prominent CZTS phase without Cu_2?xS phase. Further, rise in sulfurization time to 120 min enabled drastic improvement in crystallinity of CZTS phase. Raman mapping over 60 µm × 60 µm for these films confirmed the homogeneous phase growth of CZTS. XPS study revealed the oxidation states of Cu¹⁺, Zn²⁺, Sn⁴⁺ and S^2? in CZTS films. The optimized films showed high absorption coefficient of 10⁵ cm^?1 with an optical band gap of 1.51 eV. These films showed leaf like grain morphology with high mobility and low resistivity of 18.2 cm²/V-s and 0.7 Ω-cm, respectively.     

Sulfo-selenization of metallic thin films of Cu, In and Cu-In

To achieve an optimized adaptation of the semiconductor bandgap to the terrestrial solar spectrum, CIS (CuInSe₂, CuInS₂) based chalcopyrite absorber materials are usually substituted in the cation and anion lattice to yield mixed pentanary crystals with general composition Cu(In,Ga)(Se,S)₂. In the past, in-situ XRD (X-ray diffraction) measurements helped to clarify the phase formation sequences and reaction kinetics while crystallising the ternary chalcopyrites CuInSe₂ and CuInS₂ from metallic precursors in the presence of Se or S atmosphere. To better understand the reaction paths towards pentanary mixed chalcopyrites, the experiments are now extended to a study of the combined sulfo-selenization of metallic precursors. The experimental results of the simultaneous sulfo-selenization of Cu, In and Cu-In precursor thin films are presented and their relevance for the crystallisation of a mixed CuIn(S,Se)₂ phase discussed.The affinity of the metals Cu and In is higher to sulfur. A crystallisation of mixed sulfo-selenides of Cu, In and Cu-In due to exchange reactions between S and Se is observed. Within the Cu-Se-S subsystem a wider solid solution range of S and Se is apparent as compared to the In-Se-S system. The reactions during the chalcopyrite crystallisation for chalcogen ratio [S]:[Se] = 1:1 are similar to those of the pure sulfur system at least within the In-Se-S subsystem.     

Ultrasonically sprayed indium sulfide buffer layers for Cu(In,Ga)(S,Se)2 thin-film solar cells

Indium sulfide layers were grown by an ultrasonic spray pyrolysis method for application in Cu(In,Ga)(S,Se)₂ solar cells. X-ray diffraction measurements of layers on soda lime glass showed polycrystalline In₂S₃ with preferential orientation along the [103] direction and X-ray photoelectron spectroscopy revealed presence or absence of oxygen and chlorine impurities depending on the composition of the spray solution. For more quantitative chemical composition measurements In₂S₃ layers were sprayed on silicon substrates and analyzed with Rutherford backscattering spectrometry. The structural and chemical information on the In₂S₃ layer sprayed with different sulfur concentrations in the chemical precursor solution are correlated to the photovoltaic performance of solar cells. Best cell efficiency of 12.4% was achieved with an ultrasonically sprayed In₂S₃ buffer layer on a Cu(In,Ga)(S,Se)₂ absorber.     

Effect of precursor structure on Cu(InGa)Se2 formation by reactive annealing

Precursor structures of Mo/CuGa/In, Mo/In/CuGa, Mo/In/CuGa/In and Mo/CuGaIn were prepared on thin sodium-free glass by the sputtering of CuGa and In targets. In-situ phase evolution of precursors with temperature was investigated by a high-temperature X-ray diffraction system, which verified the existence and transformation of several intermetallics: Cu₂In, Cu₁₁In₉, Cu₃Ga, Cu₇In₃, Cu₉Ga₄ and Cu₁₆In₉ as well as elemental In. MoSe₂ layers produced during selenization were detected by scanning electron microscope and X-ray diffraction, with their thicknesses varying by precursor structure. Adhesion strength of Cu(InGa)Se₂ to each Mo layer was assessed by applying CdS chemical bath deposition process to each sample.     

Instantaneous preparation of CuInSe2 films from elemental In, Cu, Se particles precursor films in a non-vacuum process

CuInSe₂ (CIS) films are successfully prepared by means of non-vacuum, instantaneous, direct synthesis from elemental In, Cu, Se particles precursor films without prior synthesis of CIS nanoparticle precursors and without selenization with H₂Se or Se vapor. Our precursor films were prepared on metal substrates by spraying the solvent with added elemental In, Cu, and Se particles. Precursor films were instantaneously sintered using a spot welding machine. When the electric power was fixed to 0.6 kVA, elemental In, Cu, or Se peaks were not observed and only peaks of CIS are observed by X-ray diffraction (XRD) on the film sintered for 7/8 s. We can observe XRD peaks indicative of the chalcopyrite-type structure, such as (101), (103) and (211) diffraction peaks. We conclude that the synthesized CIS crystals have chalcopyrite-type structure with high crystallinity.     

Preparation and characterization of sol-gel derived copper-strontium-oxide thin films

P-type transparent conductive oxides have potential applications in photovoltaics, transparent electronics, and organic optoelectronics. In this paper, results are presented on the synthesis of Cu₂SrO₂ thin films, a p-type transparent conducting oxide by a sol-gel route. Cu(II)methoxide and Sr-metal dissolved in anhydrous isopropanol were used as precursor for the sol preparation. For potassium (K) doping, K-acetate dissolved in anhydrous isopropanol was used as the precursor. Films were spin-coated onto substrates and partially pyrolysed in air at 225°C. After partial pyrolization, a two stage annealing sequence was used to achieve the final film microstructure and composition. Although combinations of oxygen pressure, annealing time, and annealing temperature were used to obtain phase pure Cu₂SrO₂ thin films, X-ray diffraction consistently showed the presence of Cu₂O as a second phase with Cu₂SrO₂−the desired phase. Microstructural studies showed similar phase separation in the films and confirmed the microcrystalline nature. The best conductivities obtained for the undoped and 1% K-doped films were 2 × 10^− 3 and 1.2 × 10^− 2 S/cm, respectively. Both films showed a broad optical absorption edge in the visible range.     

Effect of stacking type in precursors on composition, morphology and electrical properties of the CIGS films

The copper-indium-gallium (CIG) metallic precursors with different stacking type (A: CuGa/CuIn/CuGa/glass and B: CuInGa/CuIn/CuInGa/glass) were prepared onto glass substrates by magnetron sputtering method. In order to prepare Cu(In_1?xGa_x)Se₂ (CIGS) thin films, the CIG precursors were then selenized with solid Se powder using a three-step reaction temperature profile. The influence of stacking type in precursors on structure, composition, morphology and electrical properties of the CIGS films is investigated by X-ray diffraction, energy dispersive spectrometer, scanning electron microscope and Hall effect measurement. The results reveal that the stacking type of the precursor has a strong influence on composition, morphology and properties of the CIGS thin films. The atomic ratios of Cu/(In+Ga)/Se of the CIGS films A and B are 1.61:1:2.11 and 1.39:1:2.04, respectively. The better quality CIGS thin films can be obtained through selenization of metallic precursor of CuInGa/CuIn/CuInGa/glass. The CIGS films are p-type semiconductor material. The hole concentration, resistivity and hole mobility of the CIGS thin films is 2.51 × 10¹⁷ cm^?3, 3.11 × 10⁴ Ω cm and 19.8 cm² V^?1 s^?1, respectively.