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).     

Influence of In2S3 film properties on the behavior of CuInS2/In2S3/ZnO type solar cells

Solar cells of CuInS₂/In₂S₃/ZnO type are studied as a function of the In₂S₃ buffer deposition conditions. In₂S₃ is deposited from an aqueous solution containing thioacetamide (TA), as sulfur precursor and In³⁺. In parallel, variable amounts of In₂O₃ are deposited that have an important influence on the buffer layer behavior. Starting from deposition conditions determined in a preliminary study, a set of parameters is chosen to be most determining for the buffer layer behavior, namely the solution temperature, the concentration of thioacetamide [TA], and the buffer thickness. The solar cell results are discussed in relation with these parameters. Higher efficiency is attained with buffer deposited at high temperature (70 °C) and [TA] (0.3 M). These conditions are characterized by short induction time, high deposition rate and low In₂O₃ content in the buffer. On the other hand, the film deposited at lower temperature has higher In₂O₃ content, and gives solar cell efficiency sharply decreasing with buffer thickness. This buffer type may attain higher conversion efficiencies if deposited on full covering very thin film.     

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.     

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.     

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.     

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.     

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.     

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.     

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%.     

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.     

Effect of Ga incorporation in sequentially prepared CuInS2 thin film absorbers

Thin film CuInS₂:Ga solar cell absorber films were prepared by sequential evaporation of Cu–In–Ga precursors and sulfurization in sulfur vapor. The depth distribution of Ga was found to be highly inhomogeneous caused by CuGaS₂ phase segregation at the back contact. Depending on overall Ga content and sulfurization temperature a quaternary CuGa_xIn_1−xS₂ compound formed exhibiting a shift in absorber lattice constant and band gap. Micro Raman measurements showed that crystal quality was also affected by Ga. Open-circuit voltages well above 800 mV were achieved while sustaining high fill factors of 71%.     

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.     

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.     

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⁻.     

In2O3:Sn/TiO2/CdS heterojunction nanowire array photoanode in photoelectrochemical cells

The design of photoanode with highly efficient light harvesting and charge collection properties is important in photoelectrochemical (PEC) cell performance for hydrogen production. Here, we report the hierarchical In₂O₃:Sn/TiO₂/CdS heterojunction nanowire array photoanode (ITO/TiO₂/CdS-nanowire array photoanode) as it provides a short travel distance for charge carrier and long light absorption pathway by scattering effect. In addition, optical properties and device performance of the ITO/TiO₂/CdS-nanowire array photoanode were compared with the TiO₂ nanoparticle/CdS photoanode. The photocatalytic properties for water splitting were measured in the presence of sacrificial agent such as SO₃²⁻ and S²⁻ ions. Under illumination (AM 1.5G, 100 mW/cm²), ITO/TiO₂/CdS-nanowire array photoanode exhibits a photocurrent density of 8.36 mA/cm² at 0 V versus Ag/AgCl, which is four times higher than the TiO₂ nanoparticle/CdS photoanode. The maximum applied bias photon-to-current efficiency for the ITO/TiO₂/CdS-nanowire array and the TiO₂ nanoparticle/CdS photoanode were 3.33% and 2.09%, respectively. The improved light harvesting and the charge collection properties due to the increased light absorption pathway and reduced electron travel distance by ITO nanowire lead to enhancement of PEC performance.     

Bulk p-CuInSe2 photo-electrochemical solar cells

Dense CuInSe₂ of high quality, prepared by the fusion technique in evacuated quartz ampoule from stoichiometric melt, crystallizes in the chalcopyrite structure. Compositional analysis carried out by secondary ion mass spectrometry (SIMS) and energy dispersive spectroscopy (EDS) indicates a uniform distribution of elements through the depth and a composition close to the stoichiometry. The diffuse reflectance spectrum gives a band gap at 0.94 eV. The electrical conductivity follows an Arrhenius-type law with activation energy of 23 meV in conformity with polarons hopping. Above 320 °C, CuInSe₂ undergoes an irreversible oxidation. The thermal variation of the thermopower indicates p-type behavior attributed to copper deficiency and a hole mobility μ_300 K of 0.133 cm² V⁻¹ s⁻¹, thermally activated. In KCl media, the compound exhibits an excellent chemical stability with a corrosion rate of 8 μmol cm⁻² month⁻¹. The photo-electrochemical properties, investigated for the first time on the ingots, confirm the p-type conductivity. From the capacitance measurements, the flat band potential (V_fb=−0.62V_SCE) and the holes density (N_A=4×10¹⁷ cm⁻³) were determined. The valence band, located at 4.43 eV below vacuum, is made up of mainly Se orbital with little admixture of Cu character. The change of the electrolyte causes a variation in the potential V_fb (dV_fb/dpH=−0.058 V pH⁻¹) indicating strong OH⁻ adsorption. The fill factor in S²⁻ media was found to be 0.54; such result was corroborated by semi-logarithmic plots.     

The photoinduced evolution of O2 and H2 from a WO3 aqueous suspension in the presence of Ce/Ce

This is a report on the production of O₂ and H₂ from photocatalytic and photochemical processes in the WO₃–H₂O–Ce⁴⁺_aq–hν system. The photoproduction of O₂ and H₂ was studied over the range of WO₃ concentrations from 2 to 8 g dm⁻³, and conduction band electron scavenger concentrations 1–20 mM Ce_aq⁴⁺. Medium and high concentrations of the electron scavenger gave mainly O₂ as the main product. Dilute solutions of [Ce_aq⁴⁺]< 2 mM initially produced dioxygen, and then hydrogen after an induction period of 3–4 h. Yields of 140–250 μmol O₂  h⁻¹ and 1–7 μmol H₂ h⁻¹ were obtained and were found to depend on the physical properties and content of WO₃, the concentration of the electron scavenger, illumination period and wavelength, and the radiation geometry. The photoactivity of the suspension was correlated to the level of crystallinity of WO₃ powders. The studied system utilizes WO₃ to accomplish the initial light absorption, charge separation, and production of O₂ and H⁺ from the interaction of water molecules with photogenerated WO₃ valence band holes, in the presence of Ce⁴⁺_aq species as a scavenger of conduction band electrons. This is followed by the evolution of H₂ from a homogeneous photochemical reduction of H⁺ and/or H₂O by photoexcited Ce³⁺_aq, formed from the earlier reduction of Ce⁴⁺_aq. The obtained results show that, with an appropriate design, tungsten trioxide is a promising material that can be used as a photoactive component in energy conversion systems or in environmental photocatalysis, using artificial or solar light.     

The obstructed diffusion of the I3 ion in mesoscopic TiO2 membranes

The diffusional permeability of I⁻₃ ion in acetonitrile in free standing TiO₂ membrane with a porosity of 55% was examined. The apparent diffusion coefficient, D_app at 25°C of the ion was found to be 3.4×10⁻⁶ cm^{2 −1}, an order of magnitude smaller than the free diffusion at the same temperature. The temperature dependency of D_app was measured in the range 0–30°C and analysed in terms of the Walden product. The diffusional activation energy was found to be 13.5 kJ/mol. The parameters of interest for the efficiency of mesoscopic wet solar cells are discussed. A back of an envelope calculation shows that although the obstructed diffusion coefficient of the I⁻₃ ion was an order of magnitude smaller than the free diffusion the diffusional flux is still sufficient to meet a current density of 50 mA cm⁻². At incident photon flux of 1 kW m⁻² and at a photopotential of 0.6 V this would correspond to a solar energy efficiency of approximately 30%.     

Stable, easily sintered BaCe0.5Zr0.3Y0.16Zn0.04O3−δ electrolyte-based protonic ceramic membrane fuel cells with Ba0.5Sr0.5Zn0.2Fe0.8O3−δ perovskite cathode

A stable, easily sintered perovskite oxide BaCe_0.5Zr_0.3Y_0.16Zn_0.04O_3−δ (BCZYZn) as an electrolyte for protonic ceramic membrane fuel cells (PCMFCs) with Ba_0.5Sr_0.5Zn_0.2Fe_0.8O_3−δ (BSZF) perovskite cathode was investigated. The BCZYZn perovskite electrolyte synthesized by a modified Pechini method exhibited higher sinterability and reached 97.4% relative density at 1200 °C for 5 h in air, which is about 200 °C lower than that without Zn dopant. By fabricating thin membrane BCZYZn electrolyte (about 30 μm in thickness) on NiO–BCZYZn anode support, PCMFCs were assembled and tested by selecting stable BSZF perovskite cathode. An open-circuit potential of 1.00 V, a maximum power density of 236 mW cm⁻², and a low polarization resistance of the electrodes of 0.17 Ω cm² were achieved at 700 °C. This investigation indicated that proton conducting electrolyte BCZYZn with BSZF perovskite cathode is a promising material system for the next generation solid oxide fuel cells.     

Enhanced performance of solid oxide fuel cells with Ni/CeO2 modified La0.75Sr0.25Cr0.5Mn0.5O3−δ anodes

The optimization of electrodes for solid oxide fuel cells (SOFCs) has been achieved via a wet impregnation method. Pure La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCrM) anodes are modified using Ni(NO₃)₂ and/or Ce(NO₃)₃/(Sm,Ce)(NO₃)_x solution. Several yttria-stabilized zirconia (YSZ) electrolyte-supported fuel cells are tested to clarify the contribution of Ni and/or CeO₂ to the cell performance. For the cell using pure-LSCrM anodes, the maximum power density (P_max) at 850 °C is 198 mW cm⁻² when dry H₂ and air are used as the fuel and oxidant, respectively. When H₂ is changed to CH₄, the value of P_max is 32 mW cm⁻². After 8.9 wt.% Ni and 5.8 wt.% CeO₂ are introduced into the LSCrM anode, the cell exhibits increased values of P_max 432, 681, 948 and 1135 mW cm⁻² at 700, 750, 800 and 850 °C, respectively, with dry H₂ as fuel and air as oxidant. When O₂ at 50 mL min⁻¹ is used as the oxidant, the value of P_max increases to 1450 mW cm⁻² at 850 °C. When dry CH₄ is used as fuel and air as oxidant, the values of P_max reach 95, 197, 421 and 645 mW cm⁻² at 750, 800, 850 and 900 °C, respectively. The introduction of Ni greatly improves the performance of the LSCrM anode but does not cause any carbon deposit.