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.     

Preparation and study of structural and optical properties of CSVT deposited CuInSe2 thin films

A simple close-spaced vapour transport (CSVT) system has been designed and fabricated. Copper indium diselenide (CuInSe₂) thin films of wide range of thickness (4000–60000 Å) have been prepared using the fabricated CSVT system at source temperatures 713, 758 and 843 K. A detailed study on the deposition temperature has been made and the temperature profile along with the reaction kinetics is reported. The composition of the chemical constituents of the films has been determined by energy dispersive X-ray analysis. The structural characterization of the as-deposited CuInSe₂ films of various thicknesses has been carried out by X-ray diffraction method. The diffractogram revealed that the CuInSe₂ films are polycrystalline in nature with chalcopyrite structure. The structural parameters such as lattice constants, axial ratio, tetragonal distortion, crystallite size, dislocation density and strain have been evaluated and the results are discussed. The surface morphology of the as-deposited CuInSe₂ thin films has been studied using scanning electron microscope. The transmittance characteristics of the CuInSe₂ films have been studied using double beam spectrophotometer in the wavelength range 4000–15000 Å and the optical constants n and k are evaluated. The absorption coefficient has been found to be very high and is of the order of 10⁵–10⁶ m⁻¹. CuInSe₂ films are found to have a direct allowed transition and the optical band gap is found to be in the range 0.85–1.05 eV.     

Structural, optical and electrical properties of indium tin oxide thin films prepared by spray pyrolysis

Spray pyrolysis process has been used to deposit highly transparent and conducting films of tin-doped indium oxide onto glass substrates. The electrical, structural and optical properties have been investigated as a function of various deposition parameters namely dopant concentrations, temperature and nature of substrate. The morphology of the surface as a function of the substrate temperature has been studied using atomic force microscopy. XRD has shown that deposited films are polycrystalline without second phases and have a preferred orientation (4 0 0). Indium tin oxide layers with low resistivity values around 4×10⁻⁵ Ω cm and transmission coefficients in the visible and near-infrared range of about 85–90% have been easily obtained.     

Preparation and photoelectrochemical study of BiVO4 thin films deposited by ultrasonic spray pyrolysis

Thin films of BiVO₄ with monoclinic structure were deposited onto indium-doped tin oxide (ITO)-coated glass substrates by ultrasonic spray pyrolysis. The effects of tungsten doping and hydrogen reducing were investigated. The films were characterized with XRD, Raman spectra, SEM, UV–Vis transmittance spectra. Furthermore, the films were investigated by electrochemical and photoelectrochemical measurements with regard to splitting water for solar energy conversion. The films possessed a scheelite-monoclinic structure with good absorption to visible light. The optical band gaps were evaluated to be about 2.65 eV. The flat band potentials were estimated to be about −0.61 V vs. saturated calomel electrode (SCE) in 0.5 M Na₂SO₄ solution from Mott–Schottky plots. For non-doping samples, the incident photon to current conversion efficiency (IPCE) was relative low because of low density and activity of carriers. When treated with hydrogen reducing, the carrier density increased due to more oxygen vacancies, resulting in the increase of IPCE. In addition, substituting 1% vanadium with equal mole tungsten can increase IPCE remarkably, which achieved about 10% at 0.3 V vs. SCE potential under 400–450 nm wavelength photo irradiation.     

Preparation of Cu(In,Ga)Se2 thin films from Cu–Se/In–Ga–Se precursors for high-efficiency solar cells

Improved preparation process of a device quality Cu(In,Ga)Se₂ (CIGS) thin film was proposed for production of CIGS solar cells. In–Ga–Se layer were deposited on Mo-coated soda-lime glass, and then the layer was exposed to Cu and Se fluxes to form Cu–Se/In–Ga–Se precursor film at substrate temperature of over 200°C. The precursor film was annealed in Se flux at substrate temperature of over 500°C to obtain high-quality CIGS film. The solar cell with a MgF₂/ITO/ZnO/CdS/CIGS/Mo/glass structure showed an efficiency of 17.5% (V_oc=0.634 V, J_sc=36.4 mA/cm², FF=0.756).     

Study of the sub-bandgap absorption and the optical transitions in CuInSe2 polycrystalline thin films

Optical transitions near the fundamental band edge are studied for CuInSe₂ films having various Cu/In ratios by analysing the variations of the absorption coefficient with incident photon energy. The results indicate different transitions depending upon the Cu/In ratio. There are sub-bandgap absorption for near stoichiometric and Cu-rich films. The results are compared to some literature data.     

Electrochromic characteristics of fibrous reticulated WO3 thin films prepared by pulsed spray pyrolysis technique

The electrochromic (EC) behavior of fibrous reticulated WO₃ films prepared from ammonium tungstate precursor by pulsed spray pyrolysis method was investigated. All the films were prepared using identical technological parameters and a thorough investigation of the electrochromic properties of the films deposited at 300 °C is reported. The structural properties were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochromic and optical properties were measured using cyclic voltammetry and ultraviolet (UV)-visible spectrophotometry. The films are amorphous and have a fibrous reticulate-like morphology having micron-size circular rings. The films show high transparency in the visible range and the optical band gap energy is about 3.1 eV. Electrical measurements show that the resistivity monotonically decreases as temperature increases, which indicates thermal hopping transport. The activation energy for hopping transport is of the order 4×10⁻⁴ eV. The electrochromic coloration efficiency (CE) is found to be 34 cm²/C at 630 nm.     

TiO2 thin films - Influence of annealing temperature on structural, optical and photocatalytic properties

Nanostructured TiO₂ thin films were deposited on glass substrates by sol-gel dip coating technique. The structural, morphological and optical characterizations of the as deposited and annealed films were carried out using X-ray diffraction (XRD), Raman spectroscopy, atomic force microscopy (AFM), and UV-vis transmittance spectroscopy. As-deposited films were amorphous, and the XRD studies showed that the formation of anatase phase was initiated at annealing temperature close to 400 °C. The grain size of the film annealed at 600 °C was about 20 nm. The lattice parameters for the films annealed at 600 °C were a = 3.7862 ? and c = 9.5172 ?, which is close to the reported values of anatase phase. Band gap of the as deposited film was estimated as 3.42 eV and was found to decrease with the annealing temperature. At 550 nm the refractive index of the films annealed at 600 °C was 2.11, which is low compared to a pore free anatase TiO₂. The room temperature electrical resistivity in the dark was of the order of 4.45 × 10⁶ ohm-cm. Photocatalytic activity of the TiO₂ films were studied by monitoring the degradation of aqueous methylene blue under UV light irradiation and was observed that films annealed above 400 °C had good photocatalytic activity which is explained as due to the structural and morphological properties of the films.     

CuInSe2 thin film preparation through a new selenisation process using chemical bath deposited selenium

Copper indium selenide thin films were prepared through a novel and an eco-friendly selenisation process. In this method, selenium film required for selenisation was prepared using chemical bath deposition technique, at room temperature. Thus, totally avoided usage of highly toxic H₂Se or selenium vapour. Here, the process involved annealing the Stacked layer, Se/In/Cu in which Cu and In were deposited using vacuum evaporation technique. Investigations on the solid-state reaction between the layers were done by analysing structural and optical properties of films formed at different annealing temperatures. Optimum annealing condition for the formation of copper indium selenide thin film was found to be 673 K for 1 h in high vacuum. Compositional dependence of the growth process was also studied using various Cu/In ratios. Optical band gap was decreased with increase in Cu/In ratio. Carrier concentration and hence conductivity were found to be increased with increase in Cu/In ratio. The films obtained were p-type and highly Cu-rich films were degenerate.     

Studies on electrochromic properties of nickel oxide thin films prepared by spray pyrolysis technique

Electrochromic nickel oxide thin films were prepared by using a simple and inexpensive spray pyrolysis technique (SPT) onto fluorine-doped tin oxide (FTO) coated glass substrates from nickel chloride solution. Transparent NiO-thin films were obtained at a substrate temperature 350°C. The films were cubic NiO with preferred orientation in the (1 1 1) direction. Infrared spectroscopy results show presence of free hydroxyl ion and water in nickel oxide thin films. The electrochromic properties of the thin films were studied in an aqueous alkaline electrolyte (0.1 M KOH) using cyclic voltammetry (CV), chronoamperometry (CA) and spectrophotometry. The films exhibit anodic electrochromism, changing colour from transparent to black. The colouration efficiency at 630 nm was calculated to be 37 cm²/C.     

Structural,optical, and H2 gas sensing analyses of Cr doped CuO thin films grown by ultrasonic spray pyrolysis

Here, a specific metal oxide (CuO) and its impurity (Cr) added composites were grown onto glass substrates as nanostructured thin films by executing ultrasonic spray pyrolysis method. The effects of the varied Cr dopant concentration on the morphological, structural, optical and H₂ gas sensor properties of the synthesized CuO thin films were determined by conducting scanning electron microscopy, X-ray Diffraction, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, ultraviolet–visible spectroscopy, and gas detection analyses. The X-Ray Diffraction analysis revealed the presence of CuO crystals with predominant (111) plane and it changed to (002) orientation for the doped samples, where crystallite sizes varied between 32 and 46 nm. The structural studies disclosed that the crystalline structure modified due to the added impurities. The scanning electron microscopy observations unveiled polyhedron-like shape formations of the synthesized nanostructures which also showed clear indications of changed morphology due to the impacts of different Cr doping percentages. Besides, the presence of copper, oxygen, and chromium was confirmed by EDX elemental analysis as well as X-ray photoelectron spectroscopy. The optical examination concluded that absorbance values followed a random trend with respect to the increased impurity contents while bandgap decreased with the increase of doping concentration. And, it was also noted that the luminescent emission peaks decreased in the photoluminescence spectroscopy as a result of introduced impurity levels. Finally, H₂ responsivity was detected for the grown films and found out that the impurity doping notably increased the sensitivity of the gas sensor based on the prepared CuO nanostructures.     

Defects generation by hydrogen passivation of polycrystalline silicon thin films

Hydrogen passivation technique is essential for improving the properties of polycrystalline silicon thin films. Elastic Recoil Detection Analysis (ERDA) indicated depth profiles of hydrogen concentration in poly-Si after hydrogen passivation. We have observed that plasma hydrogenation with duration up to 30 min effectively passivated the defects and improved photoluminescence intensity. Over 60 min of hydrogenation, PL intensity started to decrease. Raman scattering spectroscopy and X-ray rocking curve indicated that hydrogen created new defects and/or disorder with an increase in the hydrogen passivation time. Over 60 min, hydrogen started to form Si–H₂ bonding and hydrogen molecules (H₂), which lead to degradation of PL intensity. These peak positions were largely influenced by the grain size.These formations must be formed in quasi-stable sites, which are located at close to grain boundaries. Thus hydrogenation treatment may lead to defect passivation and new defects and/or disorder creation.     

Complexing agent effect on the stoichiometric ratio of the electrochemically prepared CuInSe2 thin films

The electrodeposition of CuInSe₂ is investigated to improve the stoichiometric properties of CuInSe₂ layers on indium tin oxide (ITO)-coated glass substrates and to develop one-step electrodeposition method for solar cell applications. XPS was utilized for the characterization of the surface properties of CuInSe₂ layers. The influence of the complexing agent, e.g. benzotriazole, bulk concentration of Cu and Se and deposition potentials on the stoichiometric properties, are discussed.     

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%.     

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%.     

Electrical characterization of Al, Ag and In contacts on CuInS2 thin films deposited by spray pyrolysis

The specific contact resistivity (ρ_C) for aluminum (Al), silver (Ag) and indium (In) metallic contacts on CuInS₂ thin films was determined from I-V measurements, with the purpose of having the most appropriate ohmic contact for TCO/CdS/CuInS₂ solar cells; ρ_C was measured using the transmission line method (TLM) for the metallic contacts evaporated on CuInS₂ thin films deposited by spray pyrolysis with ratios x=[Cu]/[In]=1.0, 1.1, 1.3 and 1.5 in the spray solution. The results show that In contacts have the lowest ρ_C values for CuInS₂ samples grown with x=1.5. The minimum ρ_C was 0.26 Ω cm² for the In contacts. This value, although not very low, will allow the fabrication of CuInS₂ solar cells with a small series resistance.     

Transformation of amorphous iron oxide thin films predeposited by spray pyrolysis into a single FeSe2-phase by selenisation

The present paper investigates a simple and non-toxic method to transform amorphous iron oxide pre-deposited by spray pyrolysis of FeCl₃·6H₂O (0.03 M)-based aqueous solution onto glass substrates heated at 350 °C into FeSe₂ thin films. The amorphous iron oxide films were heat treated under a selenium atmosphere (10⁻⁴ Pa) at different temperatures for 6 h. X-ray diffraction (XRD) was used to investigate the structure of the obtained films. Single FeSe₂-phase films having good crystallinity were obtained at a selenisation temperature of 550 °C. Optical analyses of the FeSe₂ films obtained at 550 °C enabled us to deduce a large absorption coefficient (, ). Surface scanning electron microscopy (SEM) observations show inhomogeneous films. Electrical conductivity of the as-prepared films was measured at high and low temperatures.     

Electrical and optical characterisation of CuInS2 crystals and polycrystalline coevaporated thin films

Single crystals CuInS₂ were grown by iodine vapour transport method, whereas polycrystalline thin films were obtained by coevaporation technique from three sources. The temperature dependence of the hole mobility in valence band is analysed by taking into account contributions from several scattering mechanisms of the charge carriers. To account for the temperature dependant conductivity of polycrystalline CuInS₂ thin films, grainboundary conduction process was suggested. In the low temperature region, we interpret the data in terms of the Mott law and the analysis is very consistent with the variable range hopping. However, thermionic emission is predominant at high temperatures. Photoluminescence measurements have been performed on CuInS₂ crystals and the analysis has revealed that the emission is mainly due to free-to-bound and donor–acceptor pair transitions. The band gap of that compound is derived from the excitonic emission line at 1.53 eV.     

Thin films of Cu(In,Ga)Se2 and ordered vacancy compound prepared by thermal crystallization and their photovoltaic applications

Thin films of Cu–In–Ga–Se alloy system with various composition were prepared by thermal crystallization from In/CuInGaSe/In precursor. Electron probe microanalysis and X-ray diffraction study revealed that these samples were assigned to chalcopyrite Cu(In,Ga)Se₂ or ordered vacancy compound Cu(In,Ga)₂Se_3.5. Solar cell with ZnO:Al/i–ZnO/CdS/Cu(In,Ga)Se₂/Mo/soda-lime glass substrate structure was fabricated by using thermal crystallization technique, and demonstrated a 9.58% efficiency without AR-coating.     

Structural and optical properties of CuInTe2 films prepared by thermal vacuum evaporation from a single source

The CuInTe₂ thin films were prepared by thermal vacuum evaporation from a single source. The effects of heat treatment on both structural an optical properties of CuInTe₂ films were studied. X-ray diffraction studies reveal that the films prepared by the present method showed formation of single phase CuInTe₂ at heating treatment temperature higher than 300°C. The calculated lattice constants for CuInTe₂ films annealed at 300°C were found to be and . The value of the grain size obtained in these films was of the order of 50 nm. The value of optical energy gap (0.97 eV) and the dispersive refractive index n(λ) for CuInTe₂ film annealed at 300°C were evaluated by optical absorption measurement.