Investigation of non-aqueous electrodeposited CdS/Cd1−xZnxTe heterojunction solar cells

Polycrystalline Cd_1−xZn_xTe solar cells with efficiency of 8.3% were grown by cathodic electrodeposition on glass/ITO/CdS substrates using non-aqueous ethylene glycol bath. The deposit is characterised versus the process conditions by XRD and found to possess a preferred (1 1 1) orientation on Sb doping in the electroplating bath. The surface morphology of the deposit is studied using atomic force microscope. The average RMS roughness for the ternary film was higher than that for the binary CdTe. Optical properties of the films were carried out to study the band gap and calculation of molar concentration ‘x’. The effects of Sb doping in CdS/Cd_1−xZn_xTe heterojunctions have been studied. The short circuit current density (c) was found to improve and series resistance (R_s) reduced drastically upon Sb doping. This improvement in J_sc is attributed to an increase in quantum efficiency. The evaluation of solar cell parameters was also carried out using the current–voltage characteristics in dark and illumination. The best results were obtained when 2×10⁻³ M ZnCl₂ along with antimony were present in the deposition bath. Under AM 1.5 conditions the open circuit voltage, short circuit current density, and fill factor of our best cell were V_oc=600 mV, J_sc=26.66 mA/cm², FF=0.42 and efficiency, η=8.3%. The carrier concentration and built-in potential of Cd_1−xZn_xTe calculated from Mott–Schottky plot was 2.72×10¹⁷ cm⁻³ and 1.02 eV.     

Preparation and characterization of semiconducting Zn1−xCdxSe thin films

The electrodeposition of Zn_1−xCd_xSe polycrystalline semiconducting thin films from aqueous acidic bath without any additives onto tin oxide-coated conducting glass and titanium substrates are described. The influence of deposition parameters on the film formation and deposition mechanism based on cyclic voltammetry is discussed. X-ray diffraction studies showed the polycrystalline wurtzite nature for all the films deposited under the proposed conditions. The optical studies revealed the band gap values in the range between 2.82 and 1.72 eV as the film composition changes from ZnSe to CdSe. It has been observed that the concentration of cadmium salt plays an essential role on the alloy formation. The surface morphological studies and composition analysis were carried out and the results are discussed.     

CuIn1−xGaxSe2-based photovoltaic cells from electrodeposited precursor films

We have developed an electrodeposition bath based on a buffer solution so that the stability of the electrodeposition process is enhanced and no metal oxides or hydroxides precipitate out of solution. The buffer-solution-based bath also deposits more gallium in the precursor films. As-deposited precursors are stoichiometric or slightly Cu-rich CuIn_1−xGa_xSe₂. Only a minimal amount of indium was added to the electrodeposited precursor films by physical vapor deposition to obtain a 9.4%-efficient device.     

Metal/CdTe/CdS/Cd1−xZnxS/TCO/glass: A new CdTe thin film solar cell structure

The potential of CdTe/CdS/Cd_1−xZn_xS structure as an alternative to CdTe/CdS structure in photovoltaic application has been demonstrated. The unoptimized solar cell structure grown on transparent conducting oxide coated soda lime glass of 3 mm thickness with no antireflection coating yielded a 10% efficiency. This efficiency is the highest ever recorded in any Cd_1−xZn_xS film containing CdTe solar cells.     

Photoconductivity and defect levels in ZnxCd1−xSe with (x=0.5, 0.55) crystals

Gold surface barriers on Zn_xCd_1−xSe alloys have been investigated for composition with x=(0.5, 0.55). The electrical characteristics were studied as a function of air annealing. The common feature of all the Schottky devices was the reduction of reverse bias leakage current after heating in air. Typical measurements of capacitance as a function of bias voltage can provide information on the charge density and diffusion potential. The barrier height was found to increase after air annealing at 200°C for 2 min. The spectral response of the photocurrent and photocapacitance associated with these device layers enable a donor level at 0.13 eV and acceptor levels at 1.08, 1.3 and 1.45 eV below the bottom of the conduction band to be identified. The results are discussed in terms of the effects of oxygen absorption.     

Properties of brush plated CdxZn1−xTe thin films

Cd_xZn_1−xTe (0  x  0.5) thin films were deposited for the first time by the brush plating technique using cadmium sulphate, zinc sulphate and tellurium dioxide precursors. The deposition current density was maintained at 100 mA cm⁻². X-ray diffraction studies indicated the formation of cubic phase with (1 1 1), (2 2 0), (3 1 1) orientations. From optical absorption measurements the band gaps of the films are found to be direct. AFM studies indicate a surface roughness around 54 Å. Density of the films of different composition has been estimated. Laser Raman studies indicated CdTe like LO and TO phonons.     

Investigations on ZnxCd1−xO thin films obtained by spray pyrolysis

Zn_xCd_1−xO thin films were prepared on glass substrates by spray pyrolysis technique. The precursor solutions were obtained by varying the concentration of Zn(NO₃)₂·6H₂O and Cd(NO₃)₂·4H₂O in bi-distilled water. The structural properties have been studied using X-ray diffraction spectra. All the structures include the basic compounds, i.e. ZnO and CdO. The orientation and the crystalline phases of the deposited films were specified. With the addition of Zn to the precursor solution, we can observe the preferential orientation of the CdO in the [2 0 0] direction. The electrical measurements were performed using method of four contacts. Thin films transmittances, in the 1.5–4.3 eV range, for different compositions have been measured and the optical gaps have been determined. The variations are explained considering the gaps of the two pure films. The influence of increased Cd concentration in the films on the structural, electrical and optical properties is investigated in this study.     

The performance of CuIn1−xGaxSe2-based photovoltaic cells prepared from low-cost precursor films

In this paper we report the 15.4%- and 13.4%-efficient CuIn_1−xGa_xSe₂ (CIGS)-based devices from electrodeposited (ED) and electroless deposited (EL) precursors. The efficiency of the device prepared from electroless precursor film has been improved from 12.4% to 13.4%. The dependence of quantum efficiencies on reverse-bias voltage has been measured for a 15.4%-efficient ED device, 18.8%-efficient physical-vapor-deposited device, and 14.2%-efficient Cd-free device. The purpose of this work is to explore and improve the current collection mechanism.     

Growth and characterization of CuInxGa1−xTe2 used for photovoltaic conversion

Bulk and thin films of CuIn_0.75Ga_0.25Te₂ have been grown using respectively the sealed quartz ampoule and the flash evaporation techniques. X-ray diffraction results showed that the semiconductor has the chalcopyrite structure. The gaps of the materials were determined from optical measurements and found to be 0.99 and 1.14 eV, respectively for bulk and annealed films. Photoluminescence data showed a broad emission localised at 1.05 eV.     

Electrodeposition of CuInxGa1−xSe2 thin films

CuIn_xGa_1−xSe₂ (CIGS) polycrystalline thin films with various Ga to In ratios were grown using a new two-step electrodeposition process. This process involves the electrodeposition of a Cu–Ga precursor film onto a molybdenum substrate, followed by the electrodeposition of a Cu–In–Se thin film. The resulting CuGa/CuInSe bilayer is then annealed at 600°C for 60 min in flowing Argon to form a CIGS thin film. The individual precursor films and subsequent CIGS films were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy and Auger electron spectroscopy. The as-deposited precursor films were found to be crystalline with a crystal structure matching that of CuGa₂. The annealed bi-layers were found to have the same basic chalcopyrite structure of CuInSe₂, but with peak shifts due to the Ga incorporation. Energy dispersive spectroscopy results show that the observed shifts correlate to the composition of the films.     

Structural and optical characterization of hot wall deposited CdSexTe1−x films

CdSe_0.3Te_0.7 alloy was prepared from the individual components and its composition and structural analysis were done. Films were prepared by hot wall deposition technique using 0.15 m length tube under a vacuum of 5×10⁻⁵ Torr on well cleaned glass substrates. The composition, structural, morphological, and optical properties of hot wall deposited films were investigated. The XRD analysis revealed that the films are like amorphous in nature for lower thicknesses but with increasing thickness a more preferred orientation along (1 0 1) direction was observed. The crystallite size (D), dislocation density (δ) and strain () were evaluated. From the EDX composition analysis, the individual concentrations of Se and Te in the films were estimated. An analysis of optical measurements shows that all the films have fairly good transparency above 850 nm. The optical band gap was found to be around 1.55 eV and decreases with increasing thickness. Also comparison of band gap with corresponding values for CdSe and CdTe are made.     

Structural, optical and photoelectrochemical properties of screen-printed and sintered (CdS)x(ZnS)1−x (0<x<1) films

Sulfides of zinc and cadmium have been used effectively in various optolectronic devices and recently as photocatalysts in the production of molecular hydrogen in photoelectrochemical processes. We have prepared sintered CdZnS films by the screen printing method without the presence of the typical flux material. The formation of crystalline ternary compounds is inferred from the X-ray diffraction pattern of these films. Their structural and optical properties are studied by reflection spectra in a wavelength range of 300–600 nm. The films have a direct band gap, which varies from 3.7 eV for zinc sulfide to 2.45 eV for cadmium sulfide. Films with a narrow range of composition were found to be stable in Na₂SO₃ solution under cathodic or anodic polarization in dark and illuminated conditions. This potential interval allowed to determine the flat band potentials from capacity measurements in the dark, which indicated strong contribution of double layer capacitance, surfaces states, and non-uniform doping concentration. Electrochemical impedance measurements where further performed, giving detailed information about the relevance of these factors and the optimum composition of coupled semiconductor films for photocatalytic purposes.     

Novel cobalt-free cathode materials BaCexFe1−xO3−δ for proton-conducting solid oxide fuel cells

A series of cobalt-free and low cost BaCe_xFe_1−xO_3−δ (x = 0.15, 0.50, 0.85) materials are successful synthesized and used as the cathode materials for proton-conducting solid oxide fuel cells (SOFCs). The single cell, consisting of a BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7)-NiO anode substrate, a BZCY7 anode functional layer, a BZCY7 electrolyte membrane and a BaCe_xFe_1−xO_3−δ cathode layer, is assembled and tested from 600 to 700 °C with humidified hydrogen (3% H₂O) as the fuel and the static air as the oxidant. Within all the cathode materials above, the cathode BaCe_0.5Fe_0.5O_3−δ shows the highest cell performance which could obtain an open-circuit potential of 0.99 V and a maximum power density of 395 mW cm⁻² at 700 °C. The results indicate that the Fe-doped barium cerates can be promising cathodes for proton-conducting SOFCs.     

La1−xSrxMyFe1−yO3−δ perovskites as oxygen-carrier materials for chemical-looping reforming

The use of perovskites with the general formula La_1−xSr_xM_yFe_1−yO₃ (M = Ni, Co, Cr, Cu) as oxygen carriers for syngas generation from methane by Chemical Looping Reforming is investigated in the present work. The experimental study concerns the oxidation of a fuel, using the oxygen from a solid oxygen carrier, instead of oxygen from air. Subsequent oxidation of the reduced solid is performed either with gaseous oxygen or with water. In the latter case additional hydrogen is produced, which is very pure and therefore appropriate to be used in fuel cell applications. The performance of the candidate materials is ranked by taking into account the hydrogen and carbon monoxide yields during the fuel oxidation step as well as the amount of oxygen per mole solid (δ) that can be delivered reversibly to the fuel. The effect of the materials composition and of NiO addition is examined. The best performance was obtained with the La_0.7Sr_0.3Cr_0.1Fe_0.9O₃ sample mixed with 5% NiO. The H₂ yield was up to 90%.     

Compositional dependence of electrical conductivity of Ce1−xTbxO2−δ (0x1)

Well dispersed Ce_1−xTb_xO_2−δ nano-powders were synthesized by using the carbonate coprecipitation method in an entire compositional range of 0x1, which allowed the preparation of highly dense pellets by sintering at 1673 K and the systematical study of the electrical conductivity in such a wide compositional range. It was found that the conductivity increased with increasing Tb concentration except that of x=0.80. Secondary phase were observed by using X-ray diffraction in the samples with x0.80, which might have negative impact on the conductivity of the samples.     

CuIn1−xGaxSe2-based photovoltaic cells from electrodeposited and chemical bath deposited precursors

We have fabricated 13.7%- and 7.3%-efficient CuIn_1−xGa_xSe₂ (CIGS)-based devices from electrodeposited and chemical bath deposited precursors. As-deposited precursors are Cu-rich films and polycrystalline (grain size is very small) in nature. Only preliminary data is presented on chemical bath deposited precursors. Additional In, Ga, and Se were added to the precursor films by physical evaporation to adjust the final composition to CuIn_1−xGa_xSe₂. Addition of In and Ga and also selenization at high temperature are very crucial to obtain high efficiency devices. Three devices with Ga/(In+Ga) ratios of 0.16, 0.26, and 0.39 were fabricated from electrodeposited precursors. The device fabricated from the chemical bath deposited precursor had a Ga/(In+Ga) ratio of 0.19. The films/devices have been characterized by inductive-coupled plasma spectrometry, Auger electron spectroscopy, X-ray diffraction, electron-probe microanalysis, current-voltage characteristics, capacitance–voltage, and spectral response. The compositional uniformity of the electrodeposited precursor films both in the vertical and horizontal directions were studied. The electrodeposited device parameters are compared with those of a 17.7% physical vapor deposited device.     

Deep level transient spectroscopy on ZnO/CdS/CuGaxIn1−xSe2 photovoltaic cells

The trap properties of ZnO/CdS/CuInSe₂ and ZnO/CdS/CuGa_0.3Ino_0.7Se₂ PV cells were investigated. It is believed that an argon (Ar) annealing prior to the junction formation could reduce the density of deep traps close to the mid-gap of single-crystal CuInSe₂. While no minority carrier traps were observed in ZnO/CdS/CuInSe₂ PV cells, results on ZnO/CdS/CuGa_0.3Ino_0.7Sen₂ PV cells suggested the co-existence of both the majority and minority carrier traps. Furthermore, there is evidence showing deep traps close to the mid-gap of Ar annealed single-crystal CuGa_0.3In_0.7Se₂.     

Characterization and electrochromic properties of CuxNi1−xO films prepared by sol–gel dip-coating

Cu_xNi_1−xO electrochromic thin films were prepared by sol–gel dip coating and characterized by XRD, UV–vis absorption and electrochromic test. XRD results show that the structure of the Cu_x Ni_1−xO thin films is still in cubic NiO structure. UV–vis absorption spectra show that the absorption edges of the Cu_xNi_1−xO films can be tuned from 335 nm (x = 0) to 550 nm (x = 0.3), and the transmittance of the colored films decrease as the content of Cu increases. Cu_xNi_1−xO films show good electrochromic behavior, both the coloring and bleaching time for a Cu_0.2Ni_0.8O film were less than 1 s, with a variation of transmittance up to 75% at the wavelength of 632.8 nm.     

Electrical and photoluminescence properties of evaporated CuIn1−xGaxTe2 thin films

Polycrystalline thin films of CuIn_1−xGa_xTe₂ have been deposited by flash evaporation on Corning glass 7059 substrates at T_s=200°C. Hall and resistivity measurements have been carried out down to 77 K. These films are p-type and the variation of the resistivity may be linked to defects, disorder of the material or grain boundaries. The PL spectra of these films after annealing in argon atmosphere at T_a=450°C have showed a broad band emission between 0.98 and 1.12 eV in which the main peak appears at 1.05 eV (at 4.2 K).     

Preparation of CuIn1−xGaxSe2 thin films by sputtering and selenization process

CuIn_1−xGa_xSe₂ polycrystalline thin films were prepared by a two-step method. The metal precursors were deposited either sequentially or simultaneously using Cu–Ga (23 at%) alloy and In targets by DC magnetron sputtering. The Cu–In–Ga alloy precursor was deposited on glass or on Mo/glass substrates at either room temperature or 150°C. These metallic precursors were then selenized with Se pellets in a vacuum furnace. The CuIn_1−xGa_xSe₂ films had a smooth surface morphology and a single chalcopyrite phase.