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 properties of CdS/CdTe thin film solar cell produced by periodic pulse electrodeposition technique

CdS/CdTe solar cells have been prepared by periodic pulse electrodepositionmethod. 10.8% efficient cell was made with open circuit voltage (V_oc)≈753mV, short-circuit current (J_sc)≈23.6 mA/cm² and fill factor (FF)≈0.61. Current-voltage-temperature measurments showed the variation of ideality factor (A) from 1.88 at 344 K to 4.49 at 202 K whereas voltage factor (α) was almost constant above 276 K. The junction transport is possibly dominated by a tunneling mechanism. Capacitance measurements gave the value of diffusion potential as 1.2 eV, ionized charged density as 5.9 × 10¹⁵ cm⁻³ and number of interface states (N_IS) as 2.8 × 10¹¹ cm⁻² eV⁻¹ at zero volt bias. Measurements of open circuit voltage (V_oc) with temperature gave the value of barrier height as 1.42 eV.     

Characterisation of CdCl2 treated electrodeposited CdS/CdTe thin film solar cell

An over 10% efficient electrodeposited CdS/CdTe solar cell has been prepared after CdCl₂ treatment. The open circuit voltage, V_oc, short-circuit current, J_sc and fill factor, FF were 758 mV, 21 mA cm⁻² and 0.65 respectively. The diode factor calculated from current-voltage-temperature measurements changed from 1.54 at 324 K to 2.64 at 146 K. The voltage factor, α ranged from 22.83 at 324 K to 29.46 at 146 K. Data from current-voltage-temperature measurements agrees with the model of Miller and Olsen and indicates that the current transport was a combination of tunneling and interface recombination. Capacitance-voltage-temperature measurements showed that capacitance decreased with increasing frequency and increased with temperature. Capacitance was insensitive to temperature indicating an intrinsic or low-doped depletion layer. The density of interface states was found to be 6.4 × 10¹⁰ cm⁻² eV⁻¹ at 293 K. The carrier concentration of CdTe calculated from Mott-Schottky plot was 1.5 × 10¹⁶ cm⁻³.     

Optical and electrochromic properties of oxygen sputtered tungsten oxide (WO3) thin films

Thin films of tungsten oxide (WO₃) were deposited onto glass, ITO coated glass and silicon substrates by pulsed DC magnetron sputtering (in active arc suppression mode) of tungsten metal with pure oxygen as sputter gas. The films were deposited at various oxygen pressures in the range 1.5×10⁻²−5.2×10⁻² mbar. The influence of oxygen sputters gas pressure on the structural, optical and electrochromic properties of the WO₃ thin films has been investigated. All the films grown at various oxygen pressures were found to be amorphous and near stoichiometric. A high refractive index of 2.1 (at λ=550 nm) was obtained for the film deposited at a sputtering pressure of 5.2×10⁻² mbar and it decreases at lower oxygen sputter pressure. The maximum optical band gap of 3.14 eV was obtained for the film deposited at 3.1×10⁻² mbar, and it decreases with increasing sputter pressure. The decrease in band gap and increase in refractive index for the films deposited at 5.2×10⁻² mbar is attributed to the densification of films due to ‘negative ion effects’ in sputter deposition of highly oxygenated targets. The electrochromic studies were performed by protonic intercalation/de-intercalation in the films using 0.5 M HCl dissolved in distilled water as electrolyte. The films deposited at high oxygen pressure are found to exhibit better electrochromic properties with high optical modulation (75%), high coloration efficiency (CE) (141.0 cm²/C) and less switching time at λ=550 nm; the enhanced electrochromism in these films is attributed to their low film density, smaller particle size and larger thickness. However, the faster color/bleach dynamics is these films is ascribed to the large insertion/removal of protons, as evident from the contact potential measurements (CPD) using Kelvin probe. The work function of the films deposited at 1.5 and 5.2×10⁻² mbar are 4.41 and 4.30 eV, respectively.     

Dye sensitization of antimony-doped CdS photoelectrochemical solar cell

Sb-doped CdS single crystal was used as a photoanode to fabricate a photoelectrochemical solar (PECS) cell. The three organic dyes; eosin, thymol blue and rhodamin 6G were used as sensitizers in (PECS) cell. In the absence of the dye, the results showed that with Sb-doped CdS single crystal electrode, a higher power conversion efficiency 9.27% has been achieved compared to 5.7–7.4% for pure crystal. Application of the dye in PECS cell increases the efficiency to about 13%. The efficiency reaches its maximum value when the dye concentration is (2.5×10⁻⁵)M, sufficient to cover the surface of the semiconductor electrode with a continuous monolayer of the dye. Exceeding this value resulted in a gradual decrease of the efficiency from its maximum value. Mott–Schottky plots gave a doping density of 3.14×10¹⁷ cm⁻³ and a space charge width of 4.95×10⁻⁶ cm for the sample used. A flat-band potential equal to −0.84 V, independent of both frequency and pH, was also predicted. Cyclic voltammetry (c.v.) measurements showed an anodic current peak at 0.4 V vs. SCE. The disappearance of this peak after excess addition of the reducing agent Na₂S, indicates that this peak is due to the PEC corrosion of the semiconductor electrode.     

Diffusion and influence of Cu on properties of CdTe thin films and CdTe/CdS cells

The effective diffusion coefficients of Cu for thermal and photodiffusion in the CdTe films have been estimated from resistivity versus duration of thermal or photoannealing curves. In the temperature range 60–200°C the effective coefficient of thermal diffusion (D_t) and photodiffusion (D_ph) are described as D_t=7.3×10⁻⁷exp(−0.33/kT) and D_ph=4.7×10⁻⁸exp(−0.20/kT).It is found that the diffusion doping of CdTe thin films by Cu at 400°C results in a sharp decrease of resistivity up to 7 orders of magnitude of p-type material, depending on thickness of Cu film. The comparative study of performance of CdTe(Cu)/CdS and CdTe/CdS cells has been studied. It is shown that the diffusion doping of CdTe film by Cu increases efficiency of CdTe(Cu)/CdS cells from 0.9% to 6.8%. The degradation of photovoltaic parameters of CdTe(Cu)/CdS cell, during testing under forward and reverse bias at room temperature, proceeds at a larger rate than those of CdTe/CdS cell without Cu. The degradation of performance of CdTe(Cu)/CdS cells is tentatively assigned to electrodiffusion of Cu in CdTe, resulting in redistribution of concentration of Cu-related centers in CdTe film and heterojunction region.     

Photovoltaic activity in a ZnTe/PEO–chitosan blend electrolyte junction

A ZnTe/polymer junction has been fabricated and the photovoltaic properties studied. The polymer is a blend of 50 wt% chitosan and 50 wt% polyethylene oxide (PEO). The polymer blend was complexed with ammonium iodide (NH₄I) and some iodine crystals were added to the polymer–NH₄I solution to provide the I⁻/I³⁻ redox couple. The ionic conductivity of the polymer electrolyte is 4.32×10⁻⁶ S cm⁻¹ at room temperature. ZnTe was electrodeposited on ITO conducting glass. The polymer film was sandwiched between the ZnTe semiconductor and an ITO glass to form a ZnTe/polymer electrolyte/ITO photovoltaic cell. The open circuit voltage (V_oc) of the fabricated cells ranges between 300 and 400 mV and the short circuit current between 2 and 5 μA.     

Highly conducting transparent nanocrystalline Cd1−xSnxS thin film synthesized by RF magnetron sputtering and studies on its optical, electrical and field emission properties

Transparent conducting Cd_1−xSn_xS thin films have been synthesized by radio frequency magnetron sputtering technique on glass and Si substrates for various tin concentrations in the films. X-ray diffraction studies showed broadening of peaks due to smaller crystal size of the Cd_1−xSn_xS films, and SEM micrographs showed fine particles with average size of 100 nm. Sn concentration in the films was varied from 0% to 12.6% as determined from energy-dispersive X-ray analysis. The room-temperature electrical conductivity was found to vary from 8.086 to 939.7 S cm⁻¹ and corresponding activation energy varied from 0.226 to 0.076 eV. The optimum Sn concentration for obtaining maximum conductivity was found to be 9.3%. The corresponding electrical conductivity was found to be 939.7 S cm⁻¹, and the mobility 49.7 cm² V⁻¹ s⁻¹. Hall measurement showed very high carrier concentrations in the films lying in the range of 8.0218×10¹⁸–1.7225×10²⁰ cm⁻³. The conducting Cd_1−xSn_xS thin films also showed good field emission properties with a turn on field 4.74–7.86 V μm⁻¹ with variation of electrode distance 60–100 μm. UV–Vis–NIR spectrophotometric studies of the films showed not needed the optical band gap energy increased from 2.62 to 2.80 eV with increase of Sn concentration in the range 0–12.6%. The optical band gap was Burstein–Moss shifted, and the corresponding carrier concentration obtained from the shift also well matched with that obtained from Hall measurement.     

Solar cells using iodine-doped polythiophene–porphyrin polymer films

Wet-type organic solar cells containing 5,10,15,20-3-tetrathienylporphyrin (TThP) and polythiophene (PTh) films were fabricated. The TThP/PTh film was prepared on indium-tin-oxide (ITO) glass using an electrochemical polymerization method in an n-Bu₄NPF₆/CH₂Cl₂ solution. It was found that a small amount of iodine doping of the film improved the incident photon-to-electron conversion efficiency (IPCE) of a solar cell consisting of a TThP/PTh film and an aqueous electrolyte. A HOMO level measurement suggested that a modified HOMO level of the low iodine-doped TThP/PTh film allowed a fast electron transfer from PTh to a porphyrin moiety. To obtain further improvement, a sandwich-type solar cell using a 5% (w/w) aqueous solution of acetonitrile containing 0.05 M iodine and 0.5 M lithium iodide as an electrolyte was then fabricated. The solar cell absorbed light in the 300–800 nm wavelength range, converting this to a cathodic photocurrent with a maximum IPCE of 32% at 430 nm under irradiation of 5.0×10¹⁴ photon cm⁻² s⁻¹. This value is about 10 times higher than that of the solar cells using an aqueous electrolyte. The total energy conversion efficiency (η) of the solar cell under simulated sunlight reached 0.12% for 2.59 mW cm⁻² at AM1.5 and 0.05% for 100 mW cm⁻² at air mass 1.5.     

Effect of proton irradiation on electrical properties of CuInSe2 thin films

High-energy proton irradiation (380 keV and 1 MeV) on the electrical properties of CuInSe₂ (CIS) thin films has been investigated. The samples were epitaxially grown on GaAs (0 0 1) substrates by Radio Frequency sputtering. As the proton fluence exceeded 1×10¹³ cm⁻², the carrier concentration and mobility of the CIS thin films were decreased. The carrier removal rate with proton fluence was estimated to be about 1000 cm⁻¹. The electrical properties of CIS thin films before and after irradiation were studied between 80 and 300 K. From the temperature dependence of the carrier concentration in CIS thin films, we found N_D=9.5×10¹⁶ cm⁻³, N_A=3.7×10¹⁶ cm⁻³ and E_D=21 meV from the fitting to the experimental data on the basis of the charge balance equation. After irradiation, a defect level was created, and N_T=1×10¹⁷ cm⁻³ for a fluence of 3×10¹³ cm⁻², N_T=5.7×10¹⁷ cm⁻³ for a fluence of 1×10¹⁴ cm⁻² and E_T=95 meV were also obtained from the same fitting. The new defect, which acted as an electron trap, was due to proton irradiation, and the defect density was increased with proton fluence.     

Effect of 8 MeV electron irradiation on electrical properties of CuInSe2 thin films

Radiation damages due to 8 MeV electron irradiation in electrical properties of CuInSe₂ thin films have been investigated. The n-type CuInSe₂ films in which the carrier concentration was about 3×10¹⁶ cm⁻³, were epitaxially grown on a GaAs(0 0 1) substrate by RF diode sputtering. No significant change in the electrical properties was observed under the electron fluence <3×10¹⁶ e cm⁻². As the electron fluence exceeded 10¹⁷ e cm⁻², both the carrier concentration and Hall mobility slightly decreased. The carrier removal rate was estimated to be about 0.8 cm⁻¹, which is slightly lower than that of III–V compound materials.     

Dye-sensitized solar cells: Scale up and current–voltage characterization

Large size, dye-sensitized solar cells (DSSC) have been prepared on silver grid embedded, transparent conductive oxide (TCO) glass substrate by screen printing method. Under one sun condition (AM 1.5, P_in 100 mW cm⁻²), achieved active area energy conversion efficiency of 5 cm×5 cm device approaches that of small-size DSSC prepared at similar condition. To improve the accuracy of efficiency measurement, current–voltage characterizations were carried out with shadow mask and different light reflective backgrounds. It was found that transparent and stripe-like non-active area, arising due to current collector and overcoat layer, of large size DSSC does not strongly influence the energy conversion efficiency.     

Electronic and photovoltaic properties of Al/p-Si/copper phthalocyanine photodiode junction barrier

Al/p-Si/copper phthalocyanine photovoltaic device has been fabricated and characterised by current–voltage and capacitance–voltage measurements. Electrical properties of the device were determined by current–voltage characterizations under dark and illumination conditions. The density distribution of the interface states of the photodiode was found to vary from 8.88×10¹² eV⁻¹ cm⁻² in E_ss-0.54 eV to 4.51×10¹² eV⁻¹ cm⁻² in E_ss-0.61 eV. The device shows a photovoltaic behaviour with a maximum open circuit voltage Voc of 0.16 V and short-circuits current I_sc of 0.45 μA under 3500 lux light intensity.     

Photovoltaic cells based on cadmium sulphide–phthalocyanine heterojunction

Hybrid photovoltaic (PV) cells based on cadmium sulphide (CdS) single crystal and phthalocyanine (Pc) films have been developed and their PV performance was measured. Five different Pcs have been selected as candidates for the PV cell, PcCu, PcMn, PcZn, PcMg, and PcVO. It was found that all the chosen Pcs are capable of forming a hybrid heterojunction with the CdS surface, and that illumination results in charge separation at the interface. However, the performance of the In/CdS/Pc/Au device was dependent on the Pc used. PV cells with PcMg and PcZn showed the best results. An unoptimized cell with the PcZn film showed an open-circuit voltage V_oc=0.595 V, a short-circuit current density J_sc=1.88 μA/cm², a fill factor FF=0.265, and a power conversion efficiency PCE=3.0×10⁻⁴% under the AM1.5 conditions.     

Synthesis and characterization of aluminum-doped CdO thin films by sol–gel process

Aluminum-doped cadmium oxide (CdO:Al) thin films are deposited on glass substrates by the sol–gel dip-coating method, taking cadmium acetate dihydrate as the precursor material. Aluminum nitrate has been taken as a source of Al-dopant. XRD pattern reveals the good crystallinity of CdO thin films. SEM micrograph showed the presence of faceted crystallites. Optical study shows 40–85% transparency with a bandgap value lying in the range 2.76–2.52 eV, depending upon the Al content in the films. Optimum percentage of Al was 5.22 for a maximum room temperature conductivity of 2.81×10³ (Ω cm)⁻¹. Hall measurement confirmed that the material is of n-type, with mobility and carrier concentrations lying in the range 413–14.7 cm²/V s, and 3.4×10¹⁹–8.11×10²⁰ cm⁻³, when percentage of Al varies in the range 1.32–7.24.     

Preparation of sulfonated poly(ether ether ketone)s containing amino groups/epoxy resin composite membranes and their in situ crosslinking for application in fuel cells

A series of amino-containing sulfonated poly(aryl ether ketone)/4,4′-diglycidyl(biphenyl) epoxy resin (DGBP) composite membranes for proton exchange membranes fuel cells (PEMFCs) are prepared by solution blending and casting. The reaction kinetics and the effects of introduction of DGBP content on the properties of the composite membranes are thoroughly investigated. The crosslinked composite membranes after treatment at either 120 °C or 200 °C have improved oxidative and dimensional stability than those without crosslinking. Despite the fact that crosslinked membranes generally have lower proton conductivity in comparison with the original ones, the proton conductivities of the membranes treated at 120 °C are above 2.22 × 10⁻² S cm⁻¹ at room temperature and 9.42 × 10⁻² S cm⁻¹ at 100 °C. Even for the samples treated at 200 °C, their proton conductivities are still higher than 1.26 × 10⁻² S cm⁻¹ at room temperature and higher than 8.67 × 10⁻² S cm⁻¹ at 100 °C, which are well satisfied with elementary requirement of fuel cells. In addition, all the evaluated membranes have low methanol permeability. For example, the methanol permeability of AP6FSPEEK/DGBP1 cured at 200 °C is 0.33 × 10⁻⁶ cm² s⁻¹, which is an order magnitude lower than Nafion 117. Therefore, these novel crosslinked composite membranes could be potential usage in fuel cells.     

Depletion layer characteristics of Al/microcrystalline chlorophyll a/Ag sandwich cells

The capacitance measurements of Al/microcrystalline chlorophyll a/Ag sandwich cells have been carried out at various frequencies in the dark and under illumination. The voltage-dependent capacitance, C, and the linear Schottky plots obtained at only low frequencies, 0.1 Hz, and under illumination suggest that the depletion layer mainly consists of trapped charges that are not able to follow the variations in applied voltage at high frequencies 100 Hz. From the linear Schottky plots, the depletion parameters, e.g., built-in potential, width at zero bias, and space charge density have been determined in the dark and under illumination (11 μW cm⁻²), which are, respectively, 620 mV, 300 Å and 2 × 10²³ m⁻³, and 700 mV, 205 Å and 4.78 × 10²³ m⁻³. The ageing of the cells in ambient air has been found to have dramatic effect on the capacitance characteristics of the cells. The diffusion of oxygen and presence of water vapour are most probably responsible for an inhomogeneous space charge developing within the depletion layer and the decrease of space charge density with time, respectively.     

Growth and characterization of lead sulfide films deposited on glass substrates

Lead sulfide (PbS) films have been deposited by chemical deposition on a glass substrate. Microstructure characterization was carried out by X-ray diffraction and scanning electron microscopy in order to determine the average crystallite size (15 nm) and study the surface morphologies of the as-deposited and heat-treated films. The PbS films obtained had p-type conductivity and low resisitivity (5 Ω cm). The carrier density, Hall mobility and mean free path of carriers in PbS films were in the range 2.5×10¹⁷ cm⁻³, 5 cm²/V s and 0.642 μm, respectively.     

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.     

Electrochemical deposition of Zn3P2 thin film semiconductors on tin oxide substrates

Zn₃P₂ semiconductor thin films were prepared by electrodeposition technique form aqueous solutions. The deposition mechanism was investigated by cyclic voltammetry technique. Crystal structure, morphology and composition of as deposited and annealed Zn₃P₂ thin films grown on SnO₂/glass substrates were determined by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray analysis. X-ray diffraction data indicated the formation of Zn₃P₂ as the predominant phase for both as-deposited and annealed films. The compositions of the deposited films were controlled by the bath temperature, deposition potential and Zn/P ratio in the solution.The dark current–voltage measurements of SnO₂/Zn₃P₂/C devices indicated a rectifying behavior and a reverse saturation current density of 1.7×10⁻⁷ A/cm², which is in good accordance with that obtained from films prepared using vacuum technique. Also, the capacitance–voltage measurements showed that the number of interface states and the built in potential are in the order of 5×10⁻⁹ cm⁻³ and 0.85 V, respectively. These preliminary results for Zn₃P₂ thin films reveal that, this semiconductor material can be used for solar cell applications.