CuInS2/In2S3 thin film solar cell using spray pyrolysis technique having 9.5% efficiency

Copper indium sulfide (CuInS₂)/In₂S₃ solar cells were fabricated using spray pyrolysis method and high short circuit current density and moderate open circuit voltage were obtained by adjusting the condition of deposition and thickness of both the layers. Consequently, a relatively high efficiency of 9.5% (active area) was obtained without any anti-reflection coating. The cell structure was ITO/CuInS₂/In₂S₃/Ag. We avoided the usual cyanide etching and CdS buffer layer, both toxic, for the fabrication of the cell.     

Photoelectrochemical behavior of In2S3 formed on sintered In2O3 pellets

Microcrystals of In₂S₃ were formed on sintered In₂O₃ pellets by sulfurizing in H₂S atmosphere. The flat band potential of compound In₂S₃|In₂O₃ electrodes was evaluated as −1.0 V vs Ag|AgCl in 1 M KOH, 1 M Na₂S, 10⁻² M S. Significantly enhanced photocurrent was observed on compound In₂S₃|In₂O₃ electrodes with a lower degree of sulfurization to that of compound In₂S₃|In₂O₃ electrodes with higher degree of sulfurization. Photocurrent generation of compound In₂S₃|In₂O₃ electrodes was explained from the viewpoint of semiconductor sensitization.     

Improved CIGS thin-film solar cells by surface sulfurization using In2S3 and sulfur vapor

Surface sulfurization of Cu(In,Ga)Se₂ (CIGS) thin films was carried out using two alternative techniques that do not utilize toxic H₂S gas; a sequential evaporation of In₂S₃ after CIGS deposition and the annealing of CIGS thin films in sulfur vapor. A Cu(In,Ga) (S,Se)₂ thin layer was grown on the surface of the CIGS thin film after sulfurization using In₂S₃, whereas this layer was not observed for CIGS thin films after sulfurization using sulfur vapor, although a trace quantity of S was confirmed by AES analysis. In spite of the difference in the surface modification techniques, the cell performance and process yield of the ZnO:Al/CdS/CIGS/Mo/glass thin-film solar cells were remarkably improved by using both surface sulfurization techniques.     

Optical characterization of In2S3 solar cell buffer layers grown by chemical bath and physical vapor deposition

In this paper, we study the optical properties of indium sulfide thin films to establish the best conditions to obtain a good solar cell buffer layer. The In₂S₃ buffer layers have been prepared by chemical bath deposition (CBD) and thermal evaporation (PVD). Optical behavior differences have been found between CBD and PVD In₂S₃ thin films that have been explained as due to structural, morphological and compositional differences observed in the films prepared by both methods. The resultant refractive index difference has to be attributed to the lower density of the CBD films, which can be related to the presence of oxygen. Its higher refractive index makes PVD film better suited to reduce overall reflectance in a typical CIGS solar cell.     

p-Type CuSbS2 thin films by thermal diffusion of copper into Sb2S3

We report the preparation of copper antimony sulfide (CuSbS₂) thin films by heating Sb₂S₃/Cu multilayer in vacuum. Sb₂S₃ thin film was prepared from a chemical bath containing SbCl₃ and Na₂S₂O₃ salts at room temperature (27 °C) on well cleaned glass substrates. A copper thin film was deposited on Sb₂S₃ film by thermal evaporation and Sb₂S₃/Cu layers were subjected to annealing at different conditions. Structure, morphology, optical and electrical properties of the thin films formed by varying Cu layer thickness and heating conditions were analyzed using different characterization techniques. XRD analysis showed that the thin films formed at 300 and 380 °C consist of CuSbS₂ with chalcostibite structure. These thin films showed p-type conductivity and the conductivity value increased with increase in copper content. The optical band gap of CuSbS₂ was evaluated as nearly 1.5 eV.     

Preparation of In2O3:F thin films grown by spray pyrolysis technique

Transparent conducting fluorine doped indium oxide (In₂O₃:F) thin films have been deposited on Corning 7059 glass substrates by the spray pyrolysis technique. The structural, electrical, and optical properties of these films were investigated as a function of substrate temperature. The X-ray diffraction pattern of the films deposited at lower substrate temperature (T_s=300 °C) showed no peaks of In₂O₃:F. In the useful range for deposition (i.e. 425–600 °C), the orientation of the films was predominantly [400]. For the 4500 Å thick In₂O₃:F deposited with an F content of 10-wt%, the minimum sheet resistance was 120 Ω and average transmission in the visible wavelength rang (400–700 nm) was 88%.     

Semiconductor-sensitized solar cells based on nanocrystalline In2S3/In2O3 thin film electrodes

A possibility of semiconductor-sensitized thin film solar cells have been proposed. Nanocrystalline In₂S₃-modified In₂O₃ electrodes were prepared with sulfidation of In₂O₃ thin film electrodes under H₂S atmosphere. The band gap (E_g) of In₂S₃ estimated from the onset of the absorption spectrum was approximately 2.0 eV. The photovoltaic properties of a photoelectrochemical solar cell based on In₂S₃/In₂O₃ thin film electrodes and I⁻/I₃⁻ redox electrolytes were investigated. This photoelectrochemical cell could convert visible light of 400–700 nm to electron. A highly efficient incident photon-to-electron conversion efficiency (IPCE) of 33% was obtained at 410 nm. The solar energy conversion efficiency, η, under AM 1.5 (100 mW cm⁻²) was 0.31% with a short-circuit photocurrent density (J_sc) of 3.10 mA cm⁻², a open-circuit photovoltage (V_oc) of 0.26 V, and a fill factor ( ff ) of 0.38.     

Study of electron-beam evaporated Sn-doped In2O3 films

Electron beam evaporated Sn-doped In₂O₃ films have been prepared from the starting material with composition of (1 − x) In₂O₃ − -x SnO₂, where x = 0.0, 0.010, 0.025, 0.050, 0.090, and 0.120. X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, and X-ray diffraction analysis were carried out on the films. Luminous transmittance and electrical resistivity of the films, show weak dependence on x. The composition of the film ([Sn]/[In] atomic ratio) was found to differ from that of the starting material. In fact, the atomic ratio was higher in the film than in the starting material by a factor which increases with x (ranging from 1.0 to 2.6). There is a relatively broad resistivity minimum in the layer atomic ratio range Sn/In = 0.06 − -0.09. These results compare well with those reported in the literature for Sn-doped In₂O₃ films, prepared by pyrolitic (spray) method.     

Fabrication of CuInSe2 films and solar cells by the sequential evaporation of In2Se3 and Cu2Se binary compounds

Cu₂Se/In_xSe(x≈1) double layers were prepared by sequentially evaporating In₂Se₃ and Cu₂Se binary compounds at room temperature on glass or Mo-coated glass substrates and CuInSe₂ films were formed by annealing them in a Se atmosphere at 550°C in the same vacuum chamber. The In_xSe thickness was fixed at 1 μm and the Cu₂Se thickness was varied from 0.2 to 0.5 μm. The CuInSe₂ films were single phase and the compositions were Cu-rich when the Cu₂Se thickness was above 0.35 μm. And then, a thin CuIn₃Se₅ layer was formed on the top of the CuInSe₂ film by co-evaporating In₂Se₃ and Se at 550°C. When the thickness of CuIn₃Se₅ layer was about 150 nm, the CuInSe₂ cell showed the active area efficiency of 5.4% with V_oc=286 mV, J_sc=36 mA/cm² and FF=0.52. As the CuIn₃Se₅ thickness increased further, the efficiency decreased.     

Electro deposited In2S3 buffer layers for CuInS2 solar cells

We report the electro deposition of In₂S₃ buffer layers for CuInS₂ solar cells. All materials and deposition conditions were selected taking into account environmental, economic and technological aspects of a potential transfer to large volume industrial production. Different bath compositions and electro deposition parameters were studied. The obtained films exhibited complete substrate coverage, confirmed by SEM and XPS. In/S ratio close to 2/3 was obtained. XPS measurements detected the presence of indium hydroxide, transforming into oxide upon anneal at 200 °C. Maximum photoelectric conversion efficiency of 7.1% was obtained, limited mainly by a low fill factor (51%). Further process optimization is expected to lead to efficiencies comparable to CdS buffers. So far, open-circuit voltages as high as 660 mV were demonstrated.     

Carbon-doped Sb2S3 thin films: Structural, optical and electrical properties

We report the modification of electrical properties of chemical-bath-deposited antimony sulphide (Sb₂S₃) thin films by thermal diffusion of carbon. Sb₂S₃ thin films were obtained from a chemical bath containing SbCl₃ and Na₂S₂O₃ salts at room temperature (27 °C) on glass substrates. A carbon thin film was deposited on Sb₂S₃ film by arc vacuum evaporation and the Sb₂S₃-C layer was subjected to heating at 300 °C in nitrogen atmosphere or in low vacuum for 30 min. The value of resistivity of Sb₂S₃ thin films was substantially reduced from 10⁸ Ω cm for undoped condition to 10² Ω cm for doped thin films. The doped films, Sb₂S₃:C, retained the orthogonal stibnite structure and the optical band gap energy in comparison with that of undoped Sb₂S₃ thin films. By varying the carbon content (wt%) the electrical resistivity of Sb₂S₃ can be controlled in order to make it suitable for various opto-electronic applications.     

Photocurrent enhancement of wide bandgap Bi2O3 by Bi2S3 over layers

Sintered Bi₂O₃ pellets exhibited insulating properties at room temperature. Partial reduction of sintered Bi₂O₃ pellets increased the conductivity. Reduced Bi₂O₃ pellets exhibited n-type semiconductor properties. Microcrystals of Bi₂S₃ were formed on sintered Bi₂O₃ pellets by sulfurizing them in H₂S atmosphere. The direct band-gap and indirect band-gap of Bi₂S₃ were evaluated as 1.2 and 0.4 eV, respectively. A high incident photon to current conversion efficiency in the near IR region was observed on Bi₂S₃|Bi₂O₃ electrodes. Photocurrent generation of Bi₂S₃|Bi₂O₃ electrodes was explained from the viewpoint of semiconductor sensitization. The flat band potential of Bi₂S₃ was evaluated as −1.1 V vs. Ag|AgCl in aqueous polysulfide redox electrolyte (1 M OH⁻, 1 M S²⁻, 10⁻² M S).     

Electrochemical performance of In2O3 thin film electrode in lithium cell

Indium oxide (In₂O₃) coating on Pt, as an electrode of thin film lithium battery was carried out by using cathodic electrochemical synthesis in In₂(SO₄)₃ aqueous solution and subsequently annealing at 400 °C. The coated specimens were characterized by X-ray photoelectron spectroscopy (XPS) for chemical bonding, X-ray diffraction (XRD) for crystal structure, scanning electron microscopy (SEM) for surface morphology, cyclic voltammetry (CV) for electrochemical properties, and charging/discharging test for capacity variations. The In₂O₃ coating film composed of nano-sized particles about 40 nm revealing porous structure was used as the anode of a lithium battery. During discharging, six lithium ions were firstly reacted with In₂O₃ to form Li₂O and In, and finally the Li_4.33In phase was formed between 0.7 and 0.2 V, revealing the finer particles size about 15 nm. The reverse reaction was a removal of Li⁺ from Li_4.33In phase at different oxidative potentials, and the rates of which were controlled by the thermodynamics state initially and diffusion rate finally. Therefore, the total capacity was increased with decreasing current density. However, the cell delivering a stable and reversible capacity of 195 mAh g⁻¹ between 1.2 and 0.2 V at 50 μA cm⁻² may provide a choice of negative electrode applied in thin film lithium batteries.     

Improved performance of Cu(InGa)Se2 thin-film solar cells using evaporated Cd-free buffer layers

Polycrystalline Cu(InGa)Se₂ (CIGS) thin-film solar cells using evaporated In_xSe_y and ZnIn_xSe_y buffer layers are prepared. The purpose of this work is to replace the chemical bath deposited CdS buffer layer with a continuously evaporated buffer layer. In this study, a major effort is made to improve the performance of CIGS thin-film solar cells with these buffer layers. The relationship between the cell performance and the substrate temperature for these buffer layers is demonstrated. Even at the high substrate temperature of about 550°C for the buffer layer, efficiencies of more than 11% were obtained. Furthermore, the I−V characteristics of the cells using these buffer layers are compared with cells using CdS buffer layers fabricated by chemical bath deposition method. We have achieved relatively high efficiencies of over 15% using both the ZnIn_xSe_y and the CdS buffer layers.     

The spray-ILGAR (ion layer gas reaction) method for the deposition of thin semiconductor layers: Process and applications for thin film solar cells

The spray Ion Layer Gas Reaction (ILGAR) process starts with ultrasonic nebulisation of the precursor solution, e.g. InCl₃/ethanol for our successful buffer material In₂S₃. In an aerosol assisted chemical vapour deposition (AACVD) type reaction an In(O,OH,Cl) film is deposited on a heated substrate and is subsequently converted to In₂S₃ by H₂S gas. The cycle of these steps is repeated until the required layer thickness is obtained. The robust and reproducible process allows a wide control of composition and morphology.Results of this “spray-ILGAR” method with respect to process, material properties and its application depositing the buffer layer in chalcopyrite solar cells are reviewed. New aspects such as the investigation of the complex chemical mechanism by mass spectrometry, the process acceleration by the addition of H₂S gas to the aerosol, the controlled deposition of ZnS nano-dot films and finally the latest achievements in process up-scaling are also included.Solar cells based on industrial Cu(In,Ga)(S,Se)₂ absorbers (Avancis GmbH) with a Spray-ILGAR In₂S₃ buffer reached 14.7% efficiency (certified) and 15.3% with a ZnS/In₂S₃ bi-layer buffer comparable to reference cells using standard CdS buffer layers deposited by chemical bath deposition (CBD).The quasi-dry, vacuum-free ILGAR method for In₂S₃ buffer layers is well suited for industrial in-line production and is capable of not only replacing the standard buffer material (the toxic CdS) but also the often slow CBD process. A tape coater for 10 cm wide steel tape was constructed. It was shown that In₂S₃ layers could be produced with an indium yield better than 30% and a linear production speed of 1m/min. A roll-to-roll pilot production line for electrochemically deposited Cu(In,Ga)Se₂ with ILGAR buffer is running in industry (CIS-Solartechnik, Hamburg). A 30x30 cm² prototype of an ILGAR in-line coater developed by Singulus and Helmholtz Zentrum Berlin is currently being optimised. First 30×30 cm² encapsulated modules achieved efficiencies up to 13.0% (CdS buffered reference 13.3%).     

Fabrication of wide-gap Cu(In1−xGax)Se2 thin film solar cells: a study on the correlation of cell performance with highly resistive i-ZnO layer thickness

The correlation of the cell performance of wide-gap Cu(In_1−xGa_x)Se₂ (CIGS) solar cells with the thickness of highly resistive i-ZnO layers, which are commonly introduced between the buffer layer and the transparent conductive oxide (TCO) layer in CIGS solar cell devices, was studied. It was found that cell parameters, in particular, the fill factor (F.F.) varied with the thickness of the i-ZnO layers and the variation of the F.F. was directly related to cell efficiency. A 16%-efficiency was achieved without use of an anti-reflection coating from wide-gap (E_g1.3 eV) CIGS solar cells by adjusting the deposition conditions of the i-ZnO layers.     

Al2O3-coated nanoporous TiO2 electrode for solid-state dye-sensitized solar cell

This paper reports the preparation of a core-shell nanoporous electrode consisting of an inner TiO₂ porous matrix and a thin overlayer of Al₂O₃, and its application for solid-state dye-sensitized solar cell using p-CuI as hole conductor. Al₂O₃ overlayer was coated onto TiO₂ porous film by the surface sol–gel process. The role of Al₂O₃ layer thickness on the cell performance was investigated. The solar cells fabricated from Al₂O₃-coated electrodes showed superior performance to the bare TiO₂ electrode. Under illumination of AM 1.5 simulated sunlight (89 mW/cm²), a ca. 0.19 nm Al₂O₃ overlayer increased the photo-to-electric conversion efficiency from 1.94% to 2.59%.     

Improved performance of dye-sensitized solar cells with TiO2/alumina core-shell formation using atomic layer deposition

Alumina (Al₂O₃) shell formation on TiO₂ core nanoparticles by atomic layer deposition (ALD) is studied to suppress the recombination of charge carriers generated in a dye-sensitized solar cell (DSSC). It is relatively easy to control the shell thickness using the ALD method by controlling the number of cycles. An optimum thickness can be identified, which allows tunneling of the forward current while suppressing recombination. High-resolution TEM measurements show that a uniform Al₂O₃ shell is formed around the TiO₂ core particles and elemental mapping of the porous TiO₂ layer reveals that the Al₂O₃ distribution is uniform throughout the layer. The amount of dye absorption is increased with increase in the shell thickness but electrochemical impedance spectroscopic (EIS) measurement shows a drastic increase in the resistance. With an optimum Al₂O₃ thickness of 2 nm deposited by ALD, a 35% improvement in the cell efficiency (from 6.2 to 8.4%) is achieved.     

Preparation of CuInS2 films with sufficient sulfur content and excellent morphology by one-step electrodeposition

One-step electrodeposition using sodium thiosulfate (Na₂S₂O₃) as a sulfur source has been studied for the preparation of Cu---In---S thin films. A deposited film is found to have a sufficiently high sulfur content compared with films deposited using thiourea as a sulfur source. The film deposited using Na₂S₂O₃ is also found to have an excellent morphology compared with electrodeposited Cu---In precursors. Predominant factors to govern film composition, In/Cu and S/(Cu + In) ratios, are also investigated in this study. An HC1 content added in order to decompose S₂O₃²⁻ ions in the solution is found to be one of the important factors to control composition of deposited films. A sulfur cocentration in the solution influences not only S/(Cu + In) ratio but also In/Cu ratio in the film. Reproducibility of film composition is deteriorated as the solution temperature increases.     

Experimental investigation of Cu(In1−x,Gax)Se2/Zn(O1−z,Sz) solar cell performance

In this study we investigate the performance of Cu(In_1−x,Ga_x)Se₂/Zn(O_1−z,S_z) solar cells by changing the gallium content of the absorber layer in steps from CuInSe₂ to CuGaSe₂ and at each step vary the sulfur content of the Zn(O,S) buffer layer. By incorporating more or less sulfur into the Zn(O,S) buffer layer it is possible to change its morphology and band gap energy. Surprisingly, the best solar cells with Zn(O,S) buffer layers in this study are found for close to or the same Zn(O,S) buffer layer composition for all absorber Ga compositions. In comparison to their CdS references the best solar cells with Zn(O,S) buffer layers have slightly lower open circuit voltage, V_oc, lower fill factor, FF, and higher short circuit current density, J_sc, which result in comparable or slightly lower conversion efficiencies. The exception to this trend is the CuGaSe₂ solar cells, where the best devices with Zn(O,S) have substantially lowered efficiency compared with the CdS reference, because of lower V_oc, FF and J_sc. X-ray photon spectroscopy and X-ray diffraction measurements show that the best Zn(O,S) buffer layers have similar properties independent of the Ga content. In addition, energy dispersive spectroscopy scans in a transmission electron microscope show evidence of lateral variations in the Zn(O,S) buffer layer composition at the absorber/buffer layer interface. Finally, a hypothesis based on the results of the buffer layer analysis is suggested in order to explain the solar cell parameters.