Characterization of CdTe films with in situ CdCl2 treatment grown by a simple vapor phase deposition technique

A unique vapor phase deposition (VPD) technique was designed and built to achieve in situ CdCl₂ treatment of CdTe film. The substrate temperature was 400 °C, and the temperature of CdTe mixture with CdCl₂ source was 500 °C. The structural and morphological properties of CdTe have been studied as a function of wt.% CdCl₂ concentration by using X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). XRD measurements show that the presence of CdCl₂ vapor induces (1 1 1)-oriented growth in the CdTe film. SEM measurements have shown enhance growth of grains, in the presence of CdCl₂. From AFM the roughness of the films showed a heavy dependence on CdCl₂ concentration. In the presence of 4% CdCl₂ concentration, the CdTe films roughness has a root mean square (rms) value of about 275 Å. This value is about 831 Å for the non-treated CdTe films.     

Investigation of the effect of CdCl2 processing on vacuum deposited CdS/CdTe thin film solar cells by DLTS

Thin film CdS/CdTe solar cells have been prepared by conventional vacuum deposition technique. Deep level transient spectroscopy (DLTS), temperature and frequency dependent capacitance-voltage (C-V) measurements were utilised to investigate the performance limiting defect states in the CdTe layer subjected to the post deposition treatments such as CdCl₂-dipping and/or annealing in air. Five hole traps, all of which have been previously reported in the literature, were identified in as-grown CdTe at 0.19, 0.20, 0.22, 0.30 and 0.40 eV above the valence band. A single hole trap level has been evidenced at 0.45 eV after both post deposition heat and CdCl₂ treatments.     

Correlation of stability to varied CdCl2 treatment and related defects in CdS/CdTe PV devices as measured by thermal admittance spectroscopy

A correlation between the CdCl₂ treatment and the change in conversion efficiency with light and heat stress indoors (stability) has been shown previously by our group for CdS/CdTe:Cu PV devices. In the present work CdTe devices were fabricated with various CdCl₂ treatments and with and without a Cu containing back contact. The electrical characteristics of the defects acting as traps in these devices were studied using thermal admittance spectroscopy (TAS). The activation energy E_t−E_V, the apparent capture cross section and the densities of state functions (using Walter's method) of the traps in the devices were estimated.     

Thermally evaporated CdS/CdTe thin film solar cells: Optimization of CdCl2 evaporation treatment on absorber layer

CdCl₂ treatment is crucial in the fabrication of highly efficient CdS/CdTe thin-film solar cells. This study reports a comprehensive analysis of thermal evaporated CdS/CdTe thin-film solar cells when the CdTe absorber layer is CdCl₂ annealed at temperatures from 340 to 440 °C. Samples were characterized for structural, optical, morphological and electrical properties. The films annealed at 400 °C showed better crystallinity with a cubic zinc blende structure having large grains. Higher refractive index, optical conductivity, and absorption coefficient were recorded for the CdTe films annealed at 400 °C with CdCl₂. Optimum photoactive properties for CdS/CdTe thin-film solar cells were also obtained when samples were annealed at 400 °C for 20 min with CdCl₂, and the best device exhibited V_OC of 668.4 mV, J_SC of 13.6 mA cm⁻², FF of 53.9% and an efficiency of 4.9%.     

Injection electroluminescence from CdTe p-n junctions prepared by LPE

CdTep-n junction diodes were prepared by LPE using CdCl₂ as a solvent. Excess cadmium was added to the CdCl₂-CdTe solution. Capacitance-voltage characteristics show that the diode structure is ofp-i-n type. Injection electroluminescence spectra reveal that radiative transitions occur mainly in thep-type region; relevant recombination centers are discussed in connection with those in a previous paper on the photoluminescence of CdTe:P crystals. Temperature dependences of the electroluminescence spectra were explained taking into account a change in sites where electrons radiatively recombine.     

CdTe epilayers for uses in optical waveguides

CdTe epilayers have been grown by vapor phase epitaxy (VPE) on glass, MgO, sapphire, LiNbO₃ and mica substrates. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) studies show the good structural quality of the epilayers. In these epilayers, a few optical modes were excited with a 1.33-μm laser. The measured propagation losses were in the range between 5 dB/cm and less than 0.5 dB/cm. From dark-mode m-lines, the epilayer thickness was found to be in the 1–3 μm range, in good accord with that obtained by SEM measurements. The refractive index obtained from the fitting is also in good accord with that of bulk CdTe. Received: 7 October 1999 / Accepted: 13 March 2000 / Published online: 5 July 2000     

Growth and characterization of oriented cadmium sulphide nanocrystals under Langmuir-Blodgett monolayer of arachidic acid

Cadmium sulphide nanocrystals were grown at room temperature (20 °C) under arachidic acid monolayers floating over an aqueous solution of CdCl₂ inside an enclosed Langmuir-Blodgett set-up, through slow infusion of H₂S gas. X-ray diffraction spectra suggest an oriented growth of the crystallites. The particle sizes were found to increase with duration of exposure to the H₂S gas. Atomic force microscopy indicated that the particles were nearly circular pellets with uniform morphology throughout. In Raman spectra, the FWHM of the LO phonon was found to be large (≈20 cm^-1) for all the films grown with different exposure times in H₂S gas, and was found to reduce to 8 cm^-1 after annealing a typical sample at 500 °C for 45 min. Received: 30 September 1998 / Accepted: 29 March 1999 / Published online: 11 August 1999     

Improvement of metal–ferroelectric–silicon structures without buffer layers between Si and ferroelectric films

Si-based metal–ferroelectric–semiconductor (MFS) structures without buffer layers between Si and ferroelectric films have been developed by depositing SrBi₂Ta₂O₉ (SBT) directly on n-type (100)-oriented Si. Some effective processes are adopted to improve the electrical properties of these MFS structures. Contrary to the conventional MFS structures with top electrodes directly on ferroelectrics, our MFS structures have been developed with thin dense SiO₂ films deposited between ferroelectric films and top electrodes. Due to the SiO₂ films, the leakage current densities of MFS structures are reduced to 2×10^-8 A/cm² under the bias of 5 V. The C-V electrical properties of the MFS structures are greatly improved after annealing at 400 °C in N₂ ambient for 1 h. The C-V memory windows are increased to 3 V, which probably results from the decrease of the interface trap density at the Si/SBT interface. Received: 7 September 1999 / Accepted: 24 November 1999 / Published online: 2 August 2000     

Analysis of Bulk and Interface Phenomena in CdTe/CdS Thin-Film Solar Cells

CdTe layers have been grown on CdS layers to produce thin-film photovoltaic devices. Because of the large lattice mismatch of roughly 10%, CdTe and CdS can only be joined at the expense of a high density of misfit dislocations. Additionally, after deposition the CdTe layer contains submicrometer sized, [111] oriented, columnar grains with a high density of stacking faults and microtwins resulting in a poor electrical performance of the p-n junction. The performance of these cells can be improved by depositing a CdCl₂ layer on the CdTe absorber layer and subsequent annealing of the stack in air. This treatment induces interdiffusion of S and Te across the interface, which results in a better lattice match. During this anneal, CdTe is subject to grain growth, recovery and recrystallization. In samples annealed for different durations after different amounts of CdCl₂ were applied, grain growth is completed during the first minutes of annealing. Subsequent diffusion of Cl is detected along the CdTe grain boundaries. The presence of Cl enhances the recrystallization of the CdTe layer, starting from the CdTe surface, while recovery of the CdTe layer, mostly by the reduction of microtwins, takes place at the interface. The simultaneous occurrence of recrystallization and recovery leads to a preferred alignment of grain boundaries in CdTe parallel to the interface. Electron beam induced current measurements show the detrimental effect of these grain boundaries on the charge carrier collection efficiency of the cell. Based on these results, a modified growth procedure is proposed.     

Defect reduction and surface passivation of SiO2/Si by heat treatment with high-pressure H2O vapor

Heat treatment with high-pressure H₂O vapor was applied to improve interface properties of SiO₂/Si and passivate the silicon surface. Heat treatment at 180–420 °C with high-pressure H₂O vapor changed SiO_x films, 150 nm thick formed at room temperature by thermal evaporation in vacuum, into SiO₂ films with a Si-O-Si bonding network similar to that of thermally grown SiO₂ films. Heat treatment at 130 °C with 2.8×10⁵ Pa H₂O for 3 h reduced the recombination velocity for the electron minority carriers from 405 cm/s (as-fabricated 150-nm-thick SiO_x/Si) to 5 cm/s. Field-effect passivation was demonstrated by an additional deposition of defective SiO_x films on the SiO₂ films formed by heat treatment at 340 °C with high-pressure H₂O vapor. The SiO_x deposition reduced the recombination velocity from 100 cm/s to 48 cm/s. Received: 1 March 1999 / Accepted: 28 March 1999 / Published online: 24 June 1999     

Wet chemical etched CdTe thin film solar cells

Wet chemical etching process on as-deposited CdTe surface using nitric-phosphoric (NP) acid improved the efficiency of CdS/CdTe solar cells from 10.1% to 13.8%. Nitric-phosphoric (NP) acid solution etched native oxide (TeO₂) layer and resolved excess cadmium on CdTe surface. After the heat treatment process activated the CdCl₂, CdO layer which was believed to be a diffusion barrier of chlorine did not grow on the etched CdTe surface and new (V_Cd^2?–2Cl_Te¹⁺)⁰ complexes was located at E_V + 0.045 eV. New (V_Cd^2?–2Cl_Te¹⁺)⁰ complexes acted as a shallow acceptors and induced to improve V_oc and J_sc. The surface of CdTe thin film has been studied using Scanning Electron Microscope (SEM), X-ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and low temperature Photoluminescence (PL).     

Interface photoluminescence of the SnO2:F/CdS:In/CdTe thin film solar cells prepared partially by the spray pyrolysis technique

CdS/CdTe solar cells were built by depositing a 200 nm layer of SnO₂:F on glass substrates by the spray pyrolysis (SP) technique, a 500 nm CdS:In layer by the same technique and a 1–1.5 μm CdTe layer by vacuum evaporation. The cells were CdCl₂ heat-treated in nitrogen atmosphere for 30 min at 350 °C. The photoluminescence (PL) spectra were measured at the CdS/CdTe interface for two cells with different values of the CdTe layer's thickness at the temperature T=60 K. A deconvolution peak fit was performed from which it is found that the peaks are characteristic of the solid solution CdS_xTe_1?x. The parabolic relation that relates the bandgap energy with the composition was used to estimate x, where x is [S]/([Te]+[S]) and [Te], [S] are the concentrations of Te and S atoms, respectively. The results show that the interface is smooth and the change of the bandgap occurs gradually. The solar cell of the thicker CdTe layer showed more interdiffusion at the CdS/CdTe interface and better photovoltaic characteristics.     

Degradation sources of CdTe thin film PV: CdCl2 residue and shunting pinholes

The present work considers two observable phenomena through the experimental fabrication and electrical characterization of the rf-sputtered CdS/CdTe thin film solar cells that extremely reduce the overall conversion efficiency of the device: CdCl₂ residue on the surface of the semiconductor and shunting pinholes. The former happens through nonuniform treatment of the As-deposited solar cells before annealing at high temperature and the latter occurs by shunting pinholes when the cell surface is shunted by defects, wire-like pathways or scratches on the metallic back contact caused from the external contacts. Such physical problems may be quite common in the experimental activities and reduce the performance down to 4–5 % which leads to dismantle the device despite its precise fabrication. We present our electrical characterization on the samples that received wet CdCl₂ surface treatment (uniform or nonuniform) and are damaged by the pinholes.     

Molecular beam epitaxy of GaN on a substrate of MoS2 layered compound

The feasibility of MoS₂ layered compound as a substrate for GaN growth was investigated. GaN films were successfully grown on MoS₂ by plasma-enhanced molecular beam epitaxy and the crystal quality of GaN on MoS₂ was compared with that on Al₂O₃. For GaN grown on MoS₂ substrate, it was found that the surface flatness observed by atomic force microscopy, stress in the film measured by Raman spectroscopy, optical properties measured by photoluminescence spectroscopy, and threading dislocation density observed by transmission electron microscopy show superior properties compared with that grown on Al₂O₃. These results suggest the layered compound such as MoS₂, which has no dangling bonds on the surface and has lattice mismatching of 0.9% to GaN, has high potential for a substrate of GaN growth. Received: 1 March 1999 / Accepted: 8 March 1999 / Published online: 26 May 1999     

Fabrication and electrical properties of sol-gel-derived Ba0.8Sr0.2TiO3 ferroelectric films from a 0.05-M spin-on solution

Barium strontium titanate (Ba_0.8Sr_0.2TiO₃) films with good ferroelectricity have been obtained by a developed sol-gel processing, using a 0.05-M spin-on solution. X-ray diffraction and Raman spectroscopy investigations showed that the Ba_0.8Sr_0.2TiO₃ film exhibited a tetragonal structure at room temperature. Field-emission scanning electron microscopy measurements revealed that large columnar grains with the size of 100 to 200 nm in the film were formed from the highly dilute spin-on solution with layer-by-layer homoepitaxy. Electrical measurements for the prepared Ba_0.8Sr_0.2TiO₃ film showed a remnant polarization of 3.5 μC/cm², a coercive field of 53 kV/cm, two distinctive phase transitions, lower dissipation factor, and good insulating properties. These results indicate the sol-gel-derived Ba_0.8Sr_0.2TiO₃ film from a 0.05-M solution is suitable for uncooled infrared detector applications. Received: 19 August 1999 / Accepted: 11 October 1999 / Published online: 1 March 2000     

Investigation of CdS and CdTe thin films and influence of CdCl2 on CdTe/CdS structure

CdTe/CdS heterojunction solar cell structure has been fabricated using simple, easy and low-cost methods. To fabricate this structure, CdS and CdTe thin films are deposited onto FTO-coated conducting glass substrates by chemical bath deposition (CBD) and electrodeposition method, respectively. The optimized growth conditions are chosen for both CdS and CdTe films by investigating the optical, structural and morphological properties of both the as-deposited and annealed films. Optical measurement showed that CdS films have higher transmittance and lower absorbance, and CdTe films have lower transmittance and higher absorbance in the near infrared region. The band gap of CdS films is estimated to lie in the range 2.29–2.41 eV and that of CdTe films is in the range 1.53–1.55 eV. X-ray diffraction (XRD) study reveals that CdS and CdTe films are polycrystalline with preferential orientation of (1 1 1) plane. Scanning electron microscopy (SEM) study reveals that both films are smooth, void-free and uniformly distributed over the surface of the substrate. Fabricated CdTe/CdS structure showed the anticipated rectifying behaviour, and the rectifying behaviour is observed to improve due to CdCl₂ treatment.     

Dependence of the interband transition and the activation energy on the ZnTe spacer thickness in CdTe/ZnTe double quantum dots

Photoluminescence (PL) measurements were carried out to investigate the interband transition and the activation energy in CdTe/ZnTe double quantum dots (QDs). While the excitonic peaks corresponding to the interband transition from the ground electronic subband to the ground heavy-hole (E₁-HH₁) in the CdTe/ZnTe double QDs shifted to higher energy with decreasing ZnTe spacer thickness from 30 to 10 nm due to transformation from CdTe QDs to Cd_xZn_1−xTe QDs, the peaks of the (E₁-HH₁) transitions shifted to lower energy with decreasing spacer thickness from 10 to 3 nm due to the tunneling effects of the electrons between CdTe double QDs. The decrease in the activation energy with decreasing ZnTe spacer thickness might originate from an increase in the number of defects in the ZnTe spacer. The present results can help improve the understanding of the interband transition and the activation energy in CdTe/ZnTe double QDs.     

Electronic properties of Cu(In,Ga)Se2 heterojunction solar cells–recent achievements, current understanding, and future challenges

The recent achievements of high-efficiency Cu(In,Ga)Se₂ heterojunction solar cells are reviewed with a special focus on the understanding of the electronic transport properties of the devices. We discuss the basic limitations of the device performance, the present understanding of electronic device analysis, as well as the role of intrinsic defects and of the interfaces for the performance of the solar cells. Received: 12 March 1999 / Accepted: 28 March 1999 / Published online: 24 June 1999     

Preparation and characterization of ZnS/CdS bi-layer for CdTe solar cell application

In this work, bilayer ZnS/CdS film was prepared as an improved window layer of CdTe solar cell. TEM was used to observe the cross section of the bilayer structure. The total thickness of ZnS/CdS film was about 60 nm, which could allow more photons to pass through it and contribute to the photocurrent. Optical properties of the bilayers were investigated using UV–vis spectroscopy. Compared with poor transmission of standard CdS film in the short wavelength range of 350–550 nm, the transmission of ZnS/CdS was improved and reached above 50%. The ZnS/CdS was annealed with CdCl₂. X-ray photoelectron spectroscopy (XPS) was used to investigate its chemical properties. A possible diffusion between CdS and ZnS was observed after annealing. The efficiency of standard CdS/CdTe solar cell was 9.53%. The device based on ZnS/CdS window layer had a poor 6% efficiency. With annealing treatment on ZnS/CdS layer, the performance was improved and reached 10.3%. In addition, the homogeneity of solar cell performance was improved using ZnS/CdS window layer. A thin ZnS layer was quite effective to reduce the possible shunt paths and short parts of window layer and consequently contributed to fabrication of a homogeneous CdTe solar cell.     

X-ray diffraction and ab initio determinations of the structure of Rb4CdCl6

The structure of Rb₄CdCl₆ has been examined both at the experimental and at the ab initio levels. Experimentally, new X-ray diffraction measurements have been performed on a single crystal grown at room temperature from aqueous solution. The compound is confirmed to crystallize with a rhombohedral unit cell (space group ) but with a distorsion from cubic symmetry noticeably smaller than in a previous study [Kristallografiya, 37 (1992) 815]. From the ab initio point of view, three distinct sets of first-principles density functional theory calculations (Perdew-Wang generalized-gradient-approximation (PWGGA), Perdew, Burke and Ernzerhof parametrization and Becke-Lyp exchange-correlation functions) have been carried out. These ab initio results corresponding to the ideal crystal (i.e. infinite, periodic in a definite phase and defect-free) are in correct agreement with our own experimental findings, especially for the distorsion. Nevertheless, due to the relative flatness of the ideal crystal potential energy surface with respect to distorsion around the minimum, it is quite plausible the two presently available X-ray diffraction analyses, made on two different real (imperfect) samples, are both correct even though they come out onto significantly different mean distorsion parameters. The shape, orientation and relative sizes of the thermal vibration ellipsoids are discussed in relation with relevant aspects of the calculated potential energy surface. The PWGGA wavefunction is used to plot valence electronic charge density maps. The comparison of the charge distribution in Rb₄CdCl₆ with that in Rb₂CdCl₄ is discussed in terms of compound structures.