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.     

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.     

Sputtered Cd1−xZnxTe films for top junctions in tandem solar cells

Cd_1−xZn_xTe alloy films with 1.6 and 1.7 eV band gaps were deposited by RF magnetron sputtering from targets made either of mixed powders or alloys of CdTe and ZnTe (25% and 40%). High-quality polycrystalline films with the (1 1 1) preferred orientation were obtained. The films were characterized using X-ray diffraction (XRD), scanning electron microscopy, resistivity, optical absorption, Raman, and photoluminescence. The EDS, XRD, and optical absorption analysis indicated that the x-value of the as-grown films were typically 0.20 and 0.30 for films sputtered from 25% and 40% ZnTe containing targets, respectively. The as-deposited alloy films exhibit quite low photovoltaic performance when used to make cells with CdS as the hetero-junction partner. Therefore, we have studied various post-deposition treatments with vapors of chlorine-containing materials, CdCl₂ and ZnCl₂, in dry air or H₂/Ar ambient at 390 °C. The best performance of a Cd_1−xZn_xTe cell (, ) was found for treatment with vapors of the mixed CdCl₂+0.5%ZnCl₂ in an H₂/Ar ambient after pre-annealing at 520 °C in pure H₂/Ar.     

Dependence of dark current on zinc concentration in ZnxCd1−xS/ZnTe heterojunctions

Zn_xCd_1−xS/ZnTe heterojunctions were fabricated by radio frequency (RF) sputtering of n-type Zn_xCd_1−xS thin films on phosphorus doped p-type ZnTe sinxgle crystals. Current-voltage and capacitance-voltage characteristics of these heterojunctions were studied. Especially, the influence of Zn concentration x in the Zn_xCd_1−xS layer on the characteristics of the heterojunction was investigated. The complicated dependence of the reverse saturation current J₀ on the Zn concentration in the film material was explained.     

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.     

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.     

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.     

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.     

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.     

Composition, surface topography, structure, Raman, and electrochemical/photoelectrochemical characterisation of CdxHg1−xTe films

Cd-rich Cd_xHg_{1 − x}Te films have been electrodeposited under potentiostatic conditions on conducting glass and Ti substrates from an acidic solution containing the respective ions as Cd²⁺:Hg²⁺:HTeO₂⁺ = 100:1:2. Six films one after another have been prepared from a single electrochemical cell. EDAX analysis of the air annealed films show decreasing Hg content in the deposit as the number of film preparation increases. SEM analysis indicate undulatory surface with Hg-rich clusters at the top surface. XRD analysis indicate the presence of Cd_xHg_{1 − x}Te along with . The Cd_xHg_{1 − x}Te alloy formation have been confirmed from Raman shift measurements which change with composition, x. The as-deposited films are n-type but converts to p-type after air annealing. Spectral response measurements gave band gap values that change with Hg content in the deposit. Band gap values ranging from 1.1 eV to 1.45 eV have been estimated. Photoelectrochemical solar cells using polysulphide electrolyte have been fabricated which gave an open-circuit photovoltage and short-circuit photocurrent, respectively, as 325 mV and 5.5 mA/cm² under 60 mW/cm² intensity of illumination.     

Optical and electrical studies on molybdenum sulphoselenide [Mo(S1−xSex)2] thin films prepared by arrested precipitation technique (APT)

Nanocrystalline stoichiometric [Mo(S_1−xSe_x)₂] thin films were deposited by using arrested precipitation technique (APT) developed in our laboratory. The precursors used for this are namely, molybdenum triethanolamine complex, thioacetamide and sodium selenosulphite; and various preparative conditions are finalised at the initial stages of deposition. Formation of [Mo(S_1−xSe_x)₂] semiconducting thin films are confirmed by studying growth mechanism, optical and electrical properties. X-ray diffraction analysis showed that the composites are nanocrystalline being mixed ternary chalcogenides of the general formula [Mo(S_1−xSe_x)₂]. The optical studies revealed that the films are highly absorptive (α×10⁴ cm⁻¹) with a band-to-band direct type of transitions and the energy gap decreased typically from 1.86 eV for pure MoS₂ down to 1.42 eV for MoSe₂. The thermoelectrical power measurement shows negative polarity for the generated voltage across the two ends of semiconductor thin films. This indicate that the [Mo(S_1−xSe_x)₂] thin film samples show n-type conduction.     

Photovoltaic cells based on pulsed electrochemically deposited SnS and photochemically deposited CdS and Cd1−xZnxS

CdS/SnS and Cd_1−xZn_xS/SnS solar cells were fabricated. SnS films were deposited by the pulsed electrochemical deposition method using an aqueous solution containing SnSO₄ and Na₂S₂O₃. CdS and Cd_1−xZn_xS window layers were deposited by using the photochemical deposition method using an aqueous solution containing CdSO₄, ZnSO₄ and Na₂S₂O₃. Both the techniques were simple, economical and advantageous for fabricating cheap solar cells. The fabricated cells showed rectification characteristics. The photovoltaic properties were measured under AM 1.5 illumination. The cells with the Cd_1−xZn_xS window layer show larger photocurrent than those with the CdS window layer.     

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.     

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.     

Compositional dependence of the optical properties and the H local bonding in a-Si1−xGex: H (x<0.4) thin films

A study on hydrogenated amorphous silicon-germanium alloys is presented. Amorphous thin films are prepared by RF magnetron co-sputtering. The dependence of the optical properties and parameters and the local hydrogen bonding on the composition of a-Si_1−xGe_x: H films (x < 0.4) has been investigated. It is very important to take into account the variation of hydrogen concentration when the influence of Ge content on optical properties and parameters is considered.     

II-VI thin-film polycrystalline multilayer converters for solar photovoltaics

Some new structures of thin-film solar converters (SC) based on heterojunctions (HJ) with intermediate semiconductor layers are suggested. Thin protective layers and a quasi-electric field incorporated into the space charge region (SCR) prevent cross-diffusion of HJ components and increase efficiency of charge carrier separation. They also decrease the diode dark current and provide high stability of the converter parameters. Thin ( 0.1 μM) (CdSe)_x(ZnTe)_1−x or Zn_xCd_1−xSe layers were used as graded band-gap layers. They were places between a photosensitive II-VI-compound (CdTe, CdSe, CdSe_xTe_1−x) base layer and the transparent Cu_1.8S layer. The above structures were prepared by vacuum closed space sublimation. The properties of these compounds were studied by electron microscopy and X-ray photoelectron spectroscopy (XPS) with ion etching. The photoelectron properties of structures such as Cu_1.8S/(CdSe)_x)(ZnTe)_1−x/CdSe are presented in detail. The manufacturing technology for the integrated solar batteries based on CdTe, CdSe, and CdSe_xTe_1−x compounds was developed. The solar cell parameters under low illumination intensities are comparable to those of solar batteries based on c-Si and a-Si. The competitiveness of the polycrystalline thin-film SC is due to ease and low cost of fabrication (as compared with c-Si and a-Si) and also to the extended photosensitivity range (as compared to a-Si).     

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.     

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.     

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.     

Synthesis and characterization of Cd0.7Pb0.3Se thin films for photoelectrochemical solar cell

Optimum composition Cd_0.7Pb_0.3Se thin films have been deposited using the chemical bath containing cadmium sulfate octahydrate, lead nitrate, tartaric acid, potassium hydroxide, ammonia, and sodium selenosulfate onto fluorine-doped tin oxide glass substrate. The various deposition parameters such as composition of reactive bath, pH of the solution, deposition temperature, deposition time, speed of rotation, etc. have been optimized for obtaining good quality film. X-ray diffraction studies revealed the polycrystalline nature of sample with the solid solution of lead (II) ions in CdSe host lattice, having a hexagonal phase structure. Scanning electron micrograph suggested that the grains were non-uniformly distributed over the substrate surface. Film composition was determined by atomic absorption spectroscopy as well as energy dispersive X-ray atomic spectroscopy. Optical absorption data showed the presence of direct transition with energy band gap 1.80 eV for the deposited thin films. The dark specific conductance of Cd_0.7Pb_0.3Se thin films was found to the order of 10⁻⁶ (Ω cm)⁻¹ having n-type semiconducting nature. Photoelectrochemical characterization was carried out using sulfide/polysulfide electrolyte with 1.401% efficiency.