Optical and photoelectrical properties of β-In2S3 thin films prepared by two-stage process

β-In₂S₃ films were grown on glass as well as on quartz substrates by rapid heating of metallic indium films in H₂S atmosphere. The effect of sulfurization temperature and time on the growth, structural, electrical and photoelectrical properties of β-In₂S₃ films has been investigated. Highly oriented single-phase β-In₂S₃ films were grown by the sulfurization technique. The morphology and composition of films have been characterized. The optical band gap of β-In₂S₃ is found to vary from 1.9 to 2.5 eV when the sulfurization temperature is varied from 300 to 600 °C or by increasing the sulfurization time. The electrical properties of the thin films have also been studied; they have n-type electrical conductivity. The photoelectrical properties of the β-In₂S₃ films are also found to depend on the sulfurizing temperature. A high photoresponse is obtained for films prepared at a sulfurizing temperature of 600 °C. β-In₂S₃ can be used as an alternative to toxic CdS as a window layer in photovoltaic technology.     

Growth and properties of single-phase γ-In2Se3 thin films on (1 1 1) Si substrate by AP-MOCVD using H2Se precursor

A set of In₂Se₃ films was grown on (1 1 1) Si substrate with AlN buffer by metalorganic chemical vapor deposition (MOCVD) using H₂Se as the metalogramic precursors for Se. The In₂Se₃ films on (1 1 1) Si substrate were pinhole-free with homogeneous and lamellar structures. It was found that by properly controlling the substrate temperatures, single-phase γ-In₂Se₃ films with fairly good optical properties can be well fabricated. Photoluminescence spectra of single-phase γ-In₂Se₃ show exciton emissions at 2.140 eV at 10 K. The band gap of single-phase γ-In₂Se₃ at room temperature is estimated at 1.943 eV.     

Different phases of indium selenide prepared by annealing In/Se bilayer at various temperatures: Characterization studies

Thin films of indium selenide were prepared by annealing Indium/Selenium stack layers at different temperatures ranging from 100 to 400 °C. Structural and optical characterizations were done using X-ray diffraction and optical absorption studies, respectively. Compositional analysis was done by employing Rutherford backscattering spectroscopy and X-ray photoelectron spectroscopy confirmed the compound formation. Photosensitivity and sheet resistance of these samples were also determined at room temperature. It was found that multi-phased films were formed at lower annealing temperatures and single phase films at higher annealing temperatures. A structural re-orientation as well as a phase transformation from β-In₂Se₃ to γ-In₂Se₃ was observed on annealing at 400 °C.     

Pyrite (FeS2) thin films prepared by spray method using FeSO4 and (NH4)2Sx

A simple spray method for the preparation of pyrite (FeS₂) thin films has been studied using FeSO₄ and (NH₄)₂S_x as precursors for Fe and S, respectively. Aqueous solutions of these precursors are sprayed alternately onto a substrate heated up to 120°C. Although Fe–S compounds including pyrite are formed on the substrate by the spraying, sulfurization of deposited films is needed to convert other phases such as FeS or marcasite into pyrite. A single-phase pyrite film is obtained after the sulfurization in a H₂S atmosphere at around 500°C for 30 min. All pyrite films prepared show p-type conduction. They have a carrier concentration (p) in the range 10¹⁶–10²⁰ cm⁻³ and a Hall mobility (μ_H) in the range 200–1 cm²/V s. The best electrical properties (p=7×10¹⁶ cm⁻³, μ_H=210 cm²/V s) for a pyrite film prepared here show the excellence of this method. The use of a lower concentration FeSO₄ solution is found to enhance grain growth of pyrite crystals and also to improve electrical properties of pyrite films.     

Sub-micrometer thick CuInSe2 films for solar cells using sequential elemental evaporation

CuInSe₂ thin films were prepared using sequential vacuum evaporation of In, Se and Cu at moderately low substrate temperatures, avoiding any treatment using toxic H₂Se gas. The samples were annealed at 400 °C at a pressure of 10⁻⁵ mbar to form CuInSe₂. Structural, optical, electrical, compositional and morphological characterizations were carried out on these films. We could obtain highly stoichiometric film, using this simple method, without opting for co-evaporation or high substrate temperature for deposition.     

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).     

Structural and electrical properties of CuGaS2 thin films by electron beam evaporation

Single phase CuGaS₂ thin film with a highest diffraction peak of (1 1 2) at a diffraction angle (2θ) of 28.8° was made at a substrate temperature of 70°C, an annealing temperature of 350°C and an annealing time of 60 min. Second highest (2 0 4) peak was shown at diffraction angle of (2θ) 49.1°. Lattice constant of a and c of that CuGaS₂ thin film was 5.37 and 10.54 Å, respectively. The greatest grain size of the thin film was about 1 μm. The (1 1 2) peak of single phase of CuGaS₂ thin film at an annealing temperature of 350°C with excess S supply appeared at a little higher about 10% than that of no excess S supply. The resistivity, mobility and hole density at room temperature of p-type CuGaS₂ thin film was 1.4 Ω cm, 15 cm²/V s and 2.9×10¹⁷ cm⁻³, respectively. It was known that carrier concentration had considerable effect than mobility on a variety of resistivity of the fabricated CuGaS₂ thin film, and the polycrystalline CuGaS₂ thin films were made at these conditions were all p-type.     

Floating zone growth of β-Ga2O3: a new window material for optoelectronic device applications

β-Ga₂O₃ is a transparent oxide and intrinsically an insulator. Doping allows the variation of the conductivity for both p- and n-type over a wide range. There are a number of potential applications in optoelectronics such as insulating or conductive window material, or as a substrate. Consequently, the influence of doping on the electrical and optical properties is an issue of crucial importance for pushing this material forward to applications. We report on the successful growth of undoped, Ge- and Ti-doped β-Ga₂O₃ single crystals by the floating zone technique. Both electrical and optical properties were characterized.     

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.     

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%.     

New trends to grow the n-CdZn (S1−xSex)2/p-CuIn(S1−xSex)2 heterojunction thin films for solar cell applications

The n-CdZn(S_1−xSe_x) and p-CuIn(S_1−xSe_x)₂ thin films have been grown by the solution growth technique (SGT) on glass substrates. Also the heterojunction (p–n) based on n-CdZn (S_1−xSe_x)₂ and p-CuIn (S_1−xSe_x)₂ thin films fabricated by same technique. The n-CdZn(S_1−xSe_x)₂ thin film has been used as a window material which reduced the lattice mismatch problem at the junction with CuIn (S_1−xSe_x)₂ thin film as an absorber layer for stable solar cell preparation. Elemental analysis of the n-CdZn (S_1−xSe_x)₂ and p-CuIn(S_1−xSe_x)₂ thin films was confirmed by energy-dispersive analysis of X-ray (EDAX). The structural and optical properties were changed with respect to composition ‘x’ values. The best results of these parameters were obtained at x=0.5 composition. The uniform morphology of each film as well as the continuous smooth thickness deposition onto the glass substrates was confirmed by SEM study. The optical band gaps were determined from transmittance spectra in the range of 350–1000 nm. These values are 1.22 and 2.39 eV for CuIn(S_0.5Se_0.5)₂ and CdZn(S_0.5Se_0.5)₂ thin films, respectively. J–V characteristic was measured for the n-CdZn(S_1−xSe_x)₂/p-CuIn(S_1−xSe_x)₂ heterojunction thin films under light illumination. The device parameters V_oc=474.4 mV, J_sc=13.21 mA/cm², FF=47.8% and η=3.5% under an illumination of 85 mW/cm² on a cell active area of 1 cm² have been calculated for solar cell fabrication. The J–V characteristic of the device under dark condition was also studied and the ideality factor was calculated which is equal to 1.9 for n-CdZn(S_0.5Se_0.5)₂/p-CuIn(S_0.5Se_0.5)₂ heterojunction thin films.     

Photoelectrochemical properties of spray deposited n-ZnIn2Se4 thin films

Zinc indium selenide (ZnIn₂Se₄) thin films have been prepared by spraying a mixture of an equimolar aqueous solution of zinc sulphate (ZnSO₄), indium trichloride (InCl₃), and selenourea (CH₄N₂Se), onto preheated fluorine-doped tin oxide (FTO)-coated glass substrates at optimized conditions of substrate temperature and a solution concentration. The photoelectrochemical (PEC) cell configuration of n-ZnIn₂Se₄/1 M (NaOH+Na₂S+S)/C has been used for studying the current voltage (I–V), spectral response, and capacitance voltage (C–V) characteristics of the films. The PEC study shows that the ZnIn₂Se₄ thin films exhibited n-type conductivity. The junction quality factor in dark (n_d) and light (n_l), series and shunt resistance (R_s and R_sh), fill factor (FF) and efficiency (η) for the cell have been estimated. The measured (FF) and η of the cell are, respectively, found to be 0.435% and 1.47%.     

A hybrid model for estimating global solar radiation

In view of the site-dependence of Ångström correlation, this study developed a hybrid model to estimate global radiation H. Unlike Ångström correlation H=(α+βS/S₀)H₀, this model suggested that H=(a+b S/S₀)H_b+(c+d S/S₀)H_d, H_b and H_d are effective beam radiation and effective diffuse radiation, which imply latitude, elevation and seasonal effect on radiation. H_b and H_d are calculated by an arithmetic model derived from spectral model. The hybrid model was designed for estimating monthly mean daily global radiation with hourly-recorded bright sunshine time, and its applicability was verified at observatories in Japan.     

Three-stage growth of Cu–In–Se polycrystalline thin films by chemical spray pyrolysis

Structural, optical and electrical properties of polycrystalline Cu–In–Se films, such as CuInSe₂ and ordered vacancy compounds (OVC), prepared by three-stage process of sequential chemical spray pyrolysis (CSP) of In–Se (first stage), Cu–Se (second stage) and In–Se (third stage) solutions have been studied in terms of substrate temperature at the second stage (T_S2). The films grown at T_S2420 °C exhibited larger grains in comparison with the Cu–In–Se films grown by the usual CSP method. Optical gap energy was approximately 1.06 eV for 360 °CT_S2420 °C, but increased dramatically from 1.06 to 1.35 eV when the T_S2 rose from 420 to 500 °C. Conductivity type was p-type for T_S2<420 °C, but n-type for T_S2>420 °C.     

Real-time investigations on the formation of CuInSe2 thin film solar cell absorbers from electrodeposited precursors

In this article, we present results of a detailed real-time X-ray diffraction (XRD) study on the formation of CuInSe₂ from electroplated precursors. The solid-state reactions observed during the selenisation of three different types of precursors are presented. The first type of precursors (I) consists of the nanocrystalline phases Cu_2−xSe and InSe at room temperature, which react to CuInSe₂ starting at 470 K. The second type of precursor (II) shows an inhibited CuInSe₂ formation out of the initial phases Cu_2−xSe and γ-In₂Se₃ starting at 400 K. The third precursor type (III) shows completely different selenisation behaviour. Starting from the intermetallic compound Cu₁₁In₉ and amorphous selenium, the formation of the binary selenides In₄Se₃ and CuSe is observed after the melting point of selenium at 494 K. After selenium transfer reactions, the compound semiconductor CuInSe₂ is formed out of Cu_2−xSe and InSe. This type (III) reaction path is well known for the selenisation of SEL precursors (stacked elemental layers of sputtered copper and indium and thermally evaporated selenium).     

Visible light-induced hydrogen over CuFeO2 via S2O3 oxidation

The properties of CuFeO₂ have been studied according to the catalytic hydrogen production upon visible light. CuFeO₂ with a low band gap E_g, a good chemical stability and a suitable flat band potential appears as a suitable candidate. The potential of photoelectrons allows favorably a thermodynamically H₂-evolution from alkaline thiosulfate S₂O₃²⁻ solution. There is a major difference between pure and loaded oxide with some metal catalysts. Our best results have been obtained with unloaded CuFeO₂ at 50 °C and pH 13.60. Thiosulfate S₂O₃²⁻ ions can be oxidized to sulfite SO₃²⁻ and subsequently to sulfate SO₄²⁻ and the electronic exchange occurs via mediation of surface states. The quite high H₂-formation at the beginning shows a tendency towards saturation, it competes with SO₃²⁻ produced by parallel oxidation of S₂O₃²⁻.     

The thermochromic properties of La1−xSrxMnO3 compounds

La_1−xSr_xMnO₃ (LSMO) compounds (0.175x0.30) were prepared by conventional solid-state reaction method. Temperature dependence of the total hemispherical emittance (ε_H) of the compounds from 173 to 373 K was measured on a calorimetric emissometer (CE) which was constructed based on the steady-state calorimetric method. The compounds show thermochromic properties and ε_H's have low value at low temperature and have high value at high temperature, because the compounds are dominated by metallic phase and insulator phase, respectively. We use the phase separation model to interpret the temperature dependence of ε_H.     

Some physical investigations on AgInS2 sprayed thin films

AgInS₂ thin films have been prepared on glass substrates by the spray pyrolysis process using an aqueous solution which contains silver acetate (AgCH₃CO₂), thiourea (SC(NH₂)₂) and indium chloride (InCl₃) as precursors. The depositions were carried out in the range of the substrate temperature from 260 to 420 °C. The value of the concentration ratio in the spray solution of indium and silver elements x=[Ag⁺]/[In³⁺] was varied from 1 to 1.5 with [In³⁺]=10⁻² M and [S²⁻]/[In³⁺] was taken constant, equal to 4. The structural study shows that AgInS₂ thin film, prepared at 420 °C using optimal concentration ratio x=1.3 crystallizes in the chalcopyrite phase with a strong (1 1 2) X-ray diffraction line. Moreover, microprobe analysis (EPMA) shows that a nearly stoichiometric composition is obtained for these experimental conditions. Indeed, the atomic percentage of elements were. 24.5, 25.0, 49.5 for Ag, In and S, respectively. On the other hand from transmission and reflectance spectra, the obtained band gap energy is 1.83 eV for such film.     

Promising window layer of thin film Si solar cell with p–i–n structure prepared by using SiH2Cl2

The fabrication process for a-Si:H solar cells with p–i–n structure contains a problem of damage to the SnO₂ substrate particularly at higher process temperatures. We have reported that the suppression of darkening and wide optical gap (E_opt) are obtained by using SiH₂Cl₂ instead of SiH₄ as a source gas (Mater. Res. Soc. Symp. Proc. 609 (2000), in press). In this paper, p-type a-Si:H:(Cl) was investigated. Comparable E_opt and dark conductivity (σ_dark) to those of conventional a-SiC:H were obtained. Solar cells using this a-Si:H:(Cl) show higher current density (J_sc) and higher collection efficiency in all wavelength regions as compared to a p-layer not using chlorine processes. The newly developed p-layer has been applied to solar cells with p–i–n structure fabricated at higher substrate temperatures (T_s). Although the a-Si:H material deposited at higher substrate temperatures has been reported as being more stable against light soaking (21st IEEE PVSC Proceeding, Florida, USA, 1990, p. 1656), the high temperature processing is difficult to apply to the a-Si:H p–i–n structure because of the significant darkening of SnO₂ at higher T_s. With an a-Si:H:(Cl) buffer layer, a-Si:H solar cells can be fabricated at higher T_s (300°C) with reasonable cell performance. The best stabilized efficiency was 7.5% obtained at a T_s of 250°C.     

Present status and future prospects of CIGSS thin film solar cells

Efficiencies of CuIn_1−xGa_xSe_2−yS_y (CIGSS) modules are comparable to those of lower end crystalline-Si modules. CIGSS layers are prepared by reactive co-evaporation, selenization/sulfurization of metallic or compound precursors, reactive co-sputtering and non-vacuum techniques. CuIn_1−xGa_xS₂ (CIGS2) layers are prepared by sulfurization of Cu-rich metallic precursors and etching of excess Cu_2−xS. Usually heterojunction partner CdS and transparent-conducting bilayer ZnO/ZnO:Al layers are deposited by chemical bath deposition (CBD) or RF magnetron sputtering. CIGSS solar cell efficiencies have been improved by optimizing Cu, Ga and S proportions and providing a minute amount of Na. This paper reviews preparation and efficiency improvement techniques for CIGSS solar cells.