Effects of morphologies of (Cd+Te) powders on the properties of sintered CdS/CdTe solar cells

Polycrystalline CdS/CdTe solar cells have been prepared by coating and sintering a CdS slurry and a (Cd+Te) slurry. CdS layers were first formed on borosilicate glass substrates at 600°C in nitrogen and then CdTe layers were formed on the sintered CdS layers at 625°C in nitrogen. The (Cd+Te) slurry contained (Cd+Te) powders mixed in a ball mill for 12–220 h instead of more expensive CdTe powders. The shape of cadmium particles changed from spherical to plate-like and the diameter of the plate-shaped particles became smaller as the ball-milling time increased. In addition, a compound CdTe started to form during a long milling time. The sintered CdTe layers were more compact as the diameter of plate-shaped cadmium particles decreased. However, cracks developed in the sintered CdTe layer when the diameter was small ( 2 m). The efficiency of sintered CdS/CdTe solar cells increased with decreasing particle diameter and then decreased with further decrease in particle diameter. The highest efficiency of 12.1% was achieved using a mixture of (Cd+Te) powders which had plate-shaped cadmium particles with a diameter of 5 m. The results suggest that high-efficiency sintered CdS/CdTe solar cells can be fabricated by using CdTe slurry from the mixture of (Cd+Te) powders with an inexpensive ball-milling process.     

Effects of junction formation conditions on the photovoltaic properties of sintered CdS/CdTe solar cells

Microstructures and properties of sintered CdS films on glass substrates and sintered CdTe films on polycrystal CdS substrates have been investigated. The CdS films, which contained 9 wt % CdCl₂ as a sintering aid and were sintered at 650° C for 1 h in nitrogen, are transparent and have an average grain size of 15m and an electrical resistivity of 0.5cm. The CdTe films, which were coated on the sintered CdS substrate and were sintered above 610° C for 1 h in nitrogen, have a dense structure with an average grain size larger than 5m. All polycrystal CdS/CdTe solar cells were fabricated by this successive coating and sintering method. The sintering temperature of CdTe films on the sintered CdS films was varied from 585 to 700° C. Compositional interfaces and p-n juctions are formed during sintering. The highest solar efficiency (7.18%) was found in a solar cell made by sintering the composite layer of glass-CdS-CdTe at 625° C for 1 h. A fabrication temperature below 610° C resulted in poor solar cell efficiencies due to the porous structure of the CdTe films and above 650° C also resulted in poor efficiencies due to the formation of a CdS_1-x Te_x layer at the interface and a large p-n junction depth.     

Preparation of CdTe films by electrodeposition

Single-phase CdTe thin films have been prepared by depositing sequentially a layer of tellurium and a layer of cadmium on a molybdenum substrate followed by a short thermal treatment. Deposition of tellurium films was done in an aqueous solution containing TeO₂ at a current density of ≈ 1 mA/cm². An aqueous solution containing cadmium sulfate was used for cadmium deposition with a current density of ≈1 mA/cm². Solution temperature was ≈ 95°C for tellurium film deposition and was 50°C for cadmium deposition. It was found that after a heat treatment at ≈ 370°C for 10 min the deposited Te/Cd layers were converted to CdTe thin films with a cubic structure. Compositional uniformity of the films was also investigated by electron probe microanalysis.     

Comparative study of CdS/CdTe cells fabricated with and without evaporated Te-layer

Thin film CdS/CdTe solar cells were fabricated by Close space Sublimation (CSS) at the Moldova State University using a Te layer at the back contact deposited by thermal evaporation. The influence of the Te layer thickness and a cadmium chloride solution treatment of the CdTe layer before and after Te layer deposition are studied. A proper comparison of the two CdS/CdTe solar cells shows that the cell with the Te layer has a higher current because of the higher blue photosensitivity, but has a lower open circuit voltage in relation to the absorber band gap.     

Conductive polymer PEDOT:PSS back contact for CdTe solar cell

Two types of superstrate glass/ITO/CdS/CdTe PV structures were prepared by high vacuum evaporation technique with (i) activation of CdS layer and CdS/CdTe bi-layer structure step-by-step and (ii) activation of CdS/CdTe bi-layer structure. The activation was performed by annealing the structures with CdCl₂ in air at 400 °C for 15 min. Main conditions for CdS and CdTe thin films deposition and following treatment were selected from the literature data with the purpose to prepare and compare complete CdTe solar cells with standard p + Cu_xTe back contact and conductive polymer poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonic acid (PEDOT:PSS) back contact. Obtained layers and structures were characterized using the XRD, SEM and I-V methods. Both the methods of activation treatment give comparable results from the point of view PV properties of complete solar cells. It was found that highly conductive PEDOT:PSS intermediate layer can significantly improve the back contact characteristics of CdTe. However these hybrid structures need to be further optimized to compete successfully with conventional inorganic back contacts in complete CdTe solar cells.     

Improvement of composition of CdTe thin films during heat treatment in the presence of CdCl<Subscript>2</Subscript>

CdCl₂ treatment is a crucial step in development of CdS/CdTe solar cells. Although this processing step has been used over a period of three decades, full understanding is not yet achieved. This paper reports the experimental evidence for improvement of composition of CdTe layers during CdCl₂ treatment. This investigation makes use of four selected analytical techniques; Photo-electro-chemical (PEC) cell, X-ray diffraction (XRD), Raman spectroscopy and Scanning electron microscopy (SEM). CdTe layers used were electroplated using three Cd precursors; CdSO₄, Cd(NO₃)₂ and CdCl₂. Results show the improvement of stoichiometry of CdTe layers during CdCl₂ treatment through chemical reaction between Cd from CdCl₂ and elemental Te that usually precipitate during CdTe growth, due to its natural behaviour. XRD and SEM results show that the low-temperature (~85 °C) electroplated CdTe layers consist of ~(20–60) nm size crystallites, but after CdCl₂ treatment, the layers show drastic recrystallisation with grains becoming a few microns in size. These CdCl₂ treated layers are then comparable to high temperature grown CdTe layers by the size of grains.     

Physical properties of Bi doped CdTe thin films grown by CSVT and their influence on the CdS/CdTe solar cells PV-properties

The physical properties of Bi doped CdTe films, grown on glass substrates by the Closed Space Transport Vapour (CSVT) method, from different Bi doped CdTe powders are presented. The CdTe:Bi films were characterized using Photoluminescence, Hall effect, X-Ray diffraction, SEM and Photoconductivity measurements. Moreover, CdS/CdTe:Bi solar cells were made and their characteristics like short circuit current density (J_sc), open circuit voltage (V_OC), fill factor (FF) and efficiency (η) were determined. These devices were fabricated from Bi doped CdTe layers deposited on CdS with the same growth conditions than those used for the single CdTe:Bi layers. A correlation between the CdS/CdTe:Bi solar cell characteristics and the physical properties of the Bi doped CdTe thin films are presented and discussed.     

Dynamics of melting and crystallization processes in CdTe under laser irradiation

Numerical modeling results indicate that cadmium vaporization caused by nanosecond pulses of a ruby laser has a significant effect on the dynamics of phase transitions in the near-surface region of CdTe and leads to surface cooling of the material, resulting in a nonmonotonic temperature profile, with a maximum at a depth of about 20 nm. At incident energy densities above the threshold for CdTe melting, the molten zone forming below the surface layer extends both toward the surface and into the bulk of the semiconductor. Cd vaporization and the diffusion of Cd and Te in the melt give rise to tellurium enrichment in the near-surface region. Taking into account the dependences of the crystallization temperature and the latent heat of the phase transition on the Cd and Te concentrations in the melt, we achieved reasonable agreement with experimental data on the effect of incident energy density on the time during which a molten layer is present in CdTe.     

CdS annealing treatments in various atmospheres and effects on performances of CdTe/CdS solar cells

In this work, a systematic research on CdS annealing treatments under various atmospheres had been done to understand their effects on CdS/CdTe solar cells. CdS films were prepared by a standard CBD method and annealed under various atmospheres, including Ar, Ar+H₂, O₂, Ar+S and Ar+CdCl₂. Morphological, structural, optical and chemical properties were investigated using Atom force microscope (AFM), X-ray diffraction (XRD), UV–VIS spectroscopy and X-ray photoelectron spectroscopy (XPS). Annealing treatments enhanced modifications of morphology, structure and electrical properties of CdS films. AFM showed different surface morphologies and roughnesses of CdS films annealed under various atmospheres. XRD indicated the transition of CdS films from metastable cubic structure to stable hexagonal structure after annealing treatment, especially annealed in Ar+CdCl₂. From XPS analysis, Fermi levels of CdS films shifted closer to conduction band after annealing under O₂ and Ar+CdCl₂, while the levels shifted away from conduction band under Ar+H₂ and Ar+S. The relationships between those modifications by annealing treatments and effects on the performance of solar cells were discussed. Solar cell based on CdS annealed with Ar+CdCl₂ had the best performance due to the high n-doping of CdS layer introduced by annealing process.     

Effect of interdiffusion and impurities on thin film CdTe/CdS photovoltaic junctions

We have used low temperature photoluminescence (PL) to study thin film CdTe/CdS solar cell structures. The devices were produced by close space sublimation (CSS) and have undergone a post-growth treatment, a vital step in increasing device efficiency. The treatment consisted of evaporating a thin layer of CdCl₂ onto the back CdTe surface and heat treating in air at 400 °C for between 10 and 120 min. This produced a range of device efficiencies from 2% to 9%. The efficiency improvements are the result of a complex interaction between the CdCl₂, impurities and sulfur interdiffusion. The structures were prepared for PL by a chemical bevel etching technique which allows the luminescence emission to be studied as a function of depth throughout the sample. The main features in the PL spectra have been identified as being due to the Cl-A center and the Te-dislocation-related Y luminescence band. Using PL we have quantified the S diffusion into the CdTe which has a maximum of 20% at the interface in the most efficient samples. We have also obtained the profiles of recombination and non-radiative recombination centers in the device. We observe correlations between impurity centers and device efficiency which can help explain the effects of the CdCl₂ treatment on the optoelectronic properties of the CdTe/CdS junction.     

Analysis of electrodeposited CdTe thin films grown using cadmium chloride precursor for applications in solar cells

Deposition of cadmium telluride (CdTe) from cadmium chloride (CdCl₂) and tellurium oxide has been achieved by electroplating technique using two-electrode configuration. Cyclic voltammetry shows that near-stoichiometric CdTe is achievable between 1330 and 1400 mV deposition voltage range. The layers grown were characterised using X-ray diffraction (XRD), UV–Visible spectrophotometry, scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), photoelectrochemical (PEC) cell and DC conductivity measurements. The XRD shows that the electrodeposited CdTe layer is polycrystalline in nature. The UV–Visible spectrophotometry shows that the bandgap of both as-deposited and heat-treated CdTe films are in the range of (1.44–1.46) eV. The SEM shows grain growth after CdCl₂ treatment, while, the EDX shows the effect of growth voltage on the atomic composition of CdTe layers. The PEC results show that both p- and n-type CdTe can be electrodeposited and the DC conductivity reveals that the high resistivity is at the inversion growth voltage (V_i) for the as-deposited and CdCl₂ treated layers.     

Effects of copper doping on the electronic properties of CdS films sintered with CdCl2

Chlorine- and copper-doped polycrystalline CdS films were prepared by coating a slurry which consisted of CdS, CdCl₂, CuCl₂ and propylene glycol on a glass substrate and sintering in a nitrogen atmosphere, to investigate the effects of copper doping on the window properties of all-polycrystalline CdS/CdTe heterojunction solar cells. The variations of carrier concentration as a function of the amount of copper doping in CdS films which were doped with the order of 10¹⁸ cm^–3 chlorine have been explained in terms of electronic compensation of the copper impurity. The variations of optical transmission spectra as a function of copper doping have been correlated with the variations of photoconductivity spectra. Even 10 p.p.m. copper in the sintered CdS films degrades the window properties of the CdS films significantly. The degradation is caused by reduced optical transmission rather than by an increase in electrical resistivity.     

In situ deposition of cadmium chloride films using MOCVD for CdTe solar cells

This paper reports on the first deposition of cadmium chloride (CdCl₂) films by metal organic chemical vapour deposition (MOCVD). As the p-n junction can be deposited by MOCVD, the in situ CdCl₂ treatment of the device allows for containment of the whole process. MOCVD allows a high level of control over material properties and excellent repeatability. Deposition of CdCl₂, on glass and silicon, at different II:VII precursor ratios and substrate temperatures are reported. The precursors used are dimethylcadmium and tertiarybutylchloride or n-hexylchloride, respectively for the cadmium and chlorine species. Results are presented on the surface morphology and layer structure. CdCl₂ was in its hydrate form once exposed to ambient air. Preliminary results on the effects of in situ CdCl₂ treatment on MOCVD CdS/CdTe:As devices are reported and compared with untreated devices, using current-voltage characterisation. The CdCl₂ treatment successfully resulted in MOCVD devices having open-circuit voltage higher than 600 mV and fill factor above 50%.     

Effect of CdCl2 annealing treatment on thin CdS films prepared by chemical bath deposition

In order to study the CdS recrystallization mechanism, a comparative study was carried out on thin films prepared by chemical bath deposition. The CdS films were annealed in air with or without a CdCl₂ coating layer. In-situ Raman spectra obtained during the annealing showed that both the air- and the CdCl₂-annealing did not cause rearrangement of the neighboring atoms in the CdS clusters below ~ 300 °C. CdS thin film was partially oxidated to CdO and CdSO₄ on the cluster surface when annealed in air. The oxides and the sulfur stoichiometric deficiency prevented the clusters to coalesce at higher temperatures. Coating thin CdS film with a thin CdCl₂ layer protected it from oxidation during annealing in air and promoted formation of Cl_S and V_Cd point defects in CdS. The anti-oxidation was attributed to the incorporation of a significant amount of Cl into CdS to form the Cl_S, which prevented the oxygen in-diffusion and chemical bonding during the annealing. The anti-oxidation at the CdS nano-crystalline surface and the point defects formed in the CdS promoted coalescence of the neighboring clusters without the need of long-range redistribution of the atoms. Large CdS grains with good crystalline quality formed through recrystallization during the CdCl₂ heat treatment, which provided the solid basis for the subsequent CdTe growth and high efficient CdS/CdTe solar cell fabrication.     

Transmission electron microscopy study of dislocations and interfaces in CdTe solar cells

We report on our transmission electron microscopy study of dislocations and interfaces in CdTe solar cells. The atomic structure of dislocations formed inside CdTe grains have been determined by atomic-resolution transmission electron microscopy. We discuss the electronic properties of the dislocations and explore the effects of oxygen on the interdiffusion at CdS/CdTe interface. We find that the presence of oxygen in either CdS or CdTe suppresses the interdiffusion at the CdS/CdTe interface. We have further investigated interdiffusion at the CdS/Zn₂SnO₄ interface. We find that Zn diffuses into CdS from Zn₂SnO₄ and Cd diffuses into Zn₂SnO₄ from CdS. The possible effects of the interdiffusion are discussed. Finally, we have examined the distribution of intentionally introduced Cu at the CdTe/CdS junction, and we find that Cu is distributed uniformly in the CdS layer.     

Studies of key technologies for large area CdTe thin film solar cells

The structure and main manufacturing technologies of CdTe film solar cells of large area are reviewed. Among the technologies, some have been developed for application in a pilot manufacturing line. The high resistant SnO₂ (HRT) thin films have been fabricated by PECVD. The effects of annealing on the structure and properties have been studied. A surface etching process of CdTe in low temperature and lower concentration of nitric acid has been developed. The Cd_1 − xZn_xTe ternary compound films have been studied. In order to improve the back contact layer, Cd_0.4Zn_0.6Te layer with 1.8 eV band gap as a substitute for ZnTe layer is introduced in CdTe cells. The effects of the technologies on performance of CdTe cells and feasibility of application in the modules are discussed.     

Dependence of photovoltaic performance of solvothermally prepared CdS/CdTe solar cells on morphology and thickness of window and absorber layers

In the present work a new strategy for straightforward fabrication of CdS/CdTe solar cells, containing CdS nanowires and nanoparticles as a window layer and CdTe nanoparticles and microparticles as an absorber layer, are reported. CdS and CdTe nanostructures were synthesized by solvothermal method. X-ray diffraction analysis revealed that highly pure and crystallized CdS nanowires and nanoparticles with hexagonal structure and CdTe nanoparticles with cubic structure were obtained. Atomic force microscope and field emission scanning electron microscope images showed that CdS nanowires with length of several μm and average diameter of 35 nm, CdS nanoparticles with average particle size of 32 nm and CdTe nanoparticles with average particle size of 43 nm, were uniformly coated on the substrate by the homemade formulated pastes. Based on ultraviolet–visible absorption spectra, the band gap energies of CdS nanowires, CdS nanoparticles and CdTe nanoparticles were calculated 2.80, 2.65 and 1.64 eV, respectively. It was found that, the photovoltaic performance of the solar cells depends on thickness of CdTe and CdS films, reaching a maximum at a specific value of 6 μm and 225 nm, respectively. For such cell made of CdS nanowires and CdTe nanoparticles the V_OC, J_SC, fill factor and power conversion efficiency were calculated 0.62 V, 6.82 mA/cm², 59.7 and 2.53 %, respectively. Moreover, photovoltaic characteristics of the solar cells were dependent on CdTe and CdS morphologies. CdS/CdTe solar cell made of CdTe and CdS nanoparticles had the highest cell efficiency (i.e., 2.73 %) amongst all fabricated solar cells. The presented strategy would open up new concept for fabrication of low-cost CdS/CdTe solar cells due to employment of a simple chemical route rather than the vapor phase methods.     

Effects of high-temperature annealing on ultra-thin CdTe solar cells

High-temperature annealing (HTA), a process step prior to vapor cadmium chloride (VCC) treatment, has been found to be useful for improving the crystallinity of CdTe films and the efficiency of ultra-thin CdTe solar cells. Scanning electron microscopy, optical absorption, photoluminescence measurements and analyses on photoluminescence results using spectral deconvolution reveal that the additional HTA step produces substantial grain growth and reduces grain boundary defects. It also reduces excessive sulfur diffusion across the junction that can occur during the VCC treatment. The HTA step helps to produce pinhole-free CdTe films and reduce electrical shorts in ultra-thin CdTe solar cells. An efficiency of about 11.6% has been demonstrated for ultra-thin CdS/CdTe solar cells processed with HTA step.     

Effects of CdCl2 treatment and annealing on CdS/SnO2/glass heterostructures for solar cells

Effects of CdCl₂ post-growth treatments and annealing under different conditions on the surface and interface properties of CdS/SnO₂/glass heterostructure were studied. CdS thin films were grown on SnO₂-coated glass substrates for CdS/CdTe heterojunction solar cells by the solution growth technique. It was found that CdCl₂ post-growth treatments and annealing enhanced the CdS-related XRD peaks, narrowed the CdS characteristic Raman bands, removed or depressed the disorder related Raman features, and improved the CdS film crystalline quality significantly, which are advantageous to the application in solar cells as a window layer material.     

CdTe thin film solar cells: Interrelation of nucleation, structure, and performance

The performance of CdTe solar cells as prototype of thin film solar cells strongly depends on film morphology. The needs for high solar cell performance using thin film materials will be addressed covering nucleation and growth control of thin film materials. In order to understand the basic growth mechanisms and their impact on cell performance, we have systematically investigated the growth of CdTe thin films by Close Spaced Sublimation (CSS) using the integrated ultra-high vacuum system DAISY-SOL. CdTe thin films were deposited on TCO/CdS substrates (transparent conductive oxide) held at 270 °C to 560 °C. The properties of the films were determined before and after CdCl₂ treatment using X-ray diffraction and electron microscopy. In addition, solar cells were prepared to find correlations between material properties and cell efficiency. At low sample temperature the films tend to form compact layers with preferred (111) orientation which is lost at elevated temperatures above 450 °C. For CdS layers without (0001) texture there is in addition a low temperature regime (350 °C) with (111) texture loss. After activation treatment the (111) texture is lost for all deposited layers leading to strong recrystallisation of the grains. But the texture still depends on the previous growth history. The loss of (111) texture is evidently needed for higher performance. A clear correlation between cell efficiency and the texture of the CdTe film is observed.