Fabrication of Cu2ZnSnS4 films by sulfurization of Cu/ZnSn/Cu precursor layers in sulfur atmosphere for solar cells

Cu₂ZnSnS₄ (CZTS) absorbers were grown by sulfurization of Cu/ZnSn/Cu precursors in sulfur atmosphere. The reaction mechanism of CZTS formation from the precursor was analyzed using XRD and Raman spectroscopy. The films with a single phase CZTS were formed at 560 and 580 °C by sulfurization for 30 min. The film grown at 560 °C showed bi-layer morphology with grooved large grains on the top and dense small grains near the bottom of the film. On the other hand, the film grown at 580 °C showed large grains with grooves that are extended from surface top to bottom of the film. The solar cell fabricated with the CZTS film grown at 560 °C showed the best conversion efficiency of 4.59% for 0.44 cm² with V_oc=0.545 V, J_sc=15.44 mA/cm², and FF=54.6. We found that further improvement of the microstructure of CZTS films can increase the efficiency of CZTS solar cells.     

Studies on Cu2ZnSnS4 (CZTS) absorber layer using different stacking orders in precursor thin films

Cu₂ZnSnS₄ (CZTS) thin films were deposited by sputtering on glass substrates using stacked precursors. The stacked precursor thin films were prepared from Cu, SnS₂ and ZnS targets at room temperature with different stacking orders of Cu/SnS₂/ZnS/glass (A), ZnS/Cu/SnS₂/glass (B) and SnS₂/ZnS/Cu/glass (C). The stacked precursor thin films were sulfurized using a tubular rapid thermal annealing system in a mixed N₂ (95%)+H₂S (5%) atmosphere at 550 °C for 10 min. The effects of the stacking order in the precursor thin films on the structural, morphological, chemical, electrical and optical properties of the CZTS thin films were investigated. X-ray diffraction, Raman spectroscopy and X-ray photoelectron spectroscopy studies showed that the annealed CZTS thin film using a stacking order A had a single kesterite crystal structure without secondary phases, whereas stacking orders B and C have a kesterite phase with secondary phases, such as Cu_2−xS, SnS₂ and SnS. The annealed CZTS thin film using stacking order A showed a very dense morphology without voids. On the other hand, the annealed CZTS thin films using stacking orders B and C contained the volcano shape voids (B) and Sn-based secondary phases (C) on the surface of the annealed thin films. The direct band gap energies of the CZTS thin films were approximately 1.45 eV (A), 1.35 eV (B) and 1.1 eV (C).     

Pyrite (FeS2) thin films prepared by spray method using FeSO4 and (NH4)2Sx

A simple spray method for the preparation of pyrite (FeS₂) thin films has been studied using FeSO₄ and (NH₄)₂S_x as precursors for Fe and S, respectively. Aqueous solutions of these precursors are sprayed alternately onto a substrate heated up to 120°C. Although Fe–S compounds including pyrite are formed on the substrate by the spraying, sulfurization of deposited films is needed to convert other phases such as FeS or marcasite into pyrite. A single-phase pyrite film is obtained after the sulfurization in a H₂S atmosphere at around 500°C for 30 min. All pyrite films prepared show p-type conduction. They have a carrier concentration (p) in the range 10¹⁶–10²⁰ cm⁻³ and a Hall mobility (μ_H) in the range 200–1 cm²/V s. The best electrical properties (p=7×10¹⁶ cm⁻³, μ_H=210 cm²/V s) for a pyrite film prepared here show the excellence of this method. The use of a lower concentration FeSO₄ solution is found to enhance grain growth of pyrite crystals and also to improve electrical properties of pyrite films.     

Preparation and evaluation of Cu2ZnSnS4 thin films by sulfurization of E---B evaporated precursors

By sulfurization of E---B evaporated precursors, CZTS(Cu₂ZnSnS₄) films could be prepared successfully. This semiconductor does not consist of any rare-metal such as In. The X-ray diffraction pattern of CZTS thin films showed that these films had a stannite structure. This study estimated the optical band gap energy as 1.45 eV. The optical absorption coefficient was in the order of 10⁴cm⁻¹. The resistivity was in the the order of 10⁴ Ω cm and the conduction type was p-type. Fabricated solar cells, Al/ZnO/CdS/CZTS/Mo/Soda Lime Glass, showed an open-circuit voltage up to 400 mV.     

The influence of hydrogen in the incorporation of Zn during the growth of Cu2ZnSnS4 thin films

Cu₂ZnSnS₄ (CZTS) is a p-type semiconductor, candidate to replace Cu(In,Ga)Se₂ as absorber layer in thin film solar cells. The best solar cells based on CZTS present efficiencies up to 6.8%. These results were improved when metallic Zn was replaced by ZnS, which may imply a different chemical path for the formation of CZTS. In this study it is compared with the diffusion of Zn on Cu₂SnS₃ by introducing metallic Zn or ZnS. For this CZTS films were grown by sulphurization of Cu₂SnS₃, some with a Zn layer and others with a ZnS layer. The influence of H₂ during the annealing process is also studied and for this some sulphurizations were done in the presence of a partial atmosphere of H₂.The SEM micrographs of the samples show a columnar growth structure of the films with different degrees of compactness. The compactness is improved in the samples where a ZnS layer was present in the precursor and the sulphurization was done in the presence of H₂. EDS chemical profiling revealed regular zinc distribution for the samples with metallic Zn whilst the ones with ZnS exhibited a Zn-rich surface. X-ray diffraction (XRD) indicated the presence of CZTS and Cu_2−xS phases in all samples. These results were confirmed by Raman scattering.It was concluded that the sulphurization of Cu₂SnS₃ films with the use of ZnS layers under H₂ atmosphere produces better quality CZTS thin films, since it promotes Zn diffusion and avoids Zn losses by evaporation.     

CuInS2 thin-films solar cells fabricated by sulfurization of oxide precursors

CuInS₂ thin-films were prepared by sulfurization of Cu---In---O precursors in H₂S gas. X-ray diffraction patterns showed that In₂O₃ phases did not remain in the CuInS₂ films sulfurized in a H₂S and H₂ atmosphere, whereas In₂O₃ phase remained in the films sulfurized in a H₂S and Ar atmosphere. The performance of CuInS₂ solar cells were studied as a function of the H₂ gas pressure during sulfurization. The open-circuit voltage, short-circuit current and fill factor increased with increasing the H₂ gas pressure. The conversion efficiency of the CuInS₂ solar cells is strongly affected by the reduction of the Cu---In---O precursors.     

Chemical composition dependence of morphological and optical properties of Cu2ZnSnS4 thin films deposited by sol-gel sulfurization and Cu2ZnSnS4 thin film solar cell efficiency

The properties of Cu₂ZnSnS₄ (CZTS) thin films deposited by sol-gel sulfurization were investigated as a function of the chemical composition of the sol-gel solutions used. The chemical composition ratio Cu/(Zn+Sn) of the sol-gel solution was varied from 0.73 to 1.00, while the ratio Zn/Sn was kept constant at 1.15. CZTS films deposited using sol-gel solutions with Cu/(Zn+Sn)<0.80 exhibited large grains. In addition, the band gaps of these Cu-poor CZTS thin films were blue shifted. Solar cells with the structure Al/ZnO:Al/CdS/CZTS/Mo/soda lime glass were fabricated under non-vacuum conditions. The solar cell with the CZTS layer deposited using the sol-gel solution with Cu/(Zn+Sn)=0.80 exhibited the highest conversion efficiency of 2.03%.     

Development of thin film solar cell based on Cu2ZnSnS4 thin films

Cu₂ZnSnS₄ (hereafter CZTS) thin films were successfully formed by vapor-phase sulfurization of precursors on a soda lime glass substrate (hereafter SLG) and a Mo-coated one (hereafter Mo-SLG). From the optical properties, we estimate the band-gap energy of this thin film as 1.45–1.6 eV which is quite close to the optimum value for a solar cell. By using this thin film as an absorber layer, we could fabricate a new type of thin film solar cell, which was composed of Al/ZnO:Al/CdS/CZTS/Mo-SLG. The best conversion efficiency achieved in our study was 2.62% and the highest open-circuit voltage was 735 mV. These device results are the best reported so far for CZTS.     

Optical and photoelectrical properties of β-In2S3 thin films prepared by two-stage process

β-In₂S₃ films were grown on glass as well as on quartz substrates by rapid heating of metallic indium films in H₂S atmosphere. The effect of sulfurization temperature and time on the growth, structural, electrical and photoelectrical properties of β-In₂S₃ films has been investigated. Highly oriented single-phase β-In₂S₃ films were grown by the sulfurization technique. The morphology and composition of films have been characterized. The optical band gap of β-In₂S₃ is found to vary from 1.9 to 2.5 eV when the sulfurization temperature is varied from 300 to 600 °C or by increasing the sulfurization time. The electrical properties of the thin films have also been studied; they have n-type electrical conductivity. The photoelectrical properties of the β-In₂S₃ films are also found to depend on the sulfurizing temperature. A high photoresponse is obtained for films prepared at a sulfurizing temperature of 600 °C. β-In₂S₃ can be used as an alternative to toxic CdS as a window layer in photovoltaic technology.     

Preparation and characterization of spray-deposited Cu2ZnSnS4 thin films

Thin films of Cu₂ZnSnS₄ (CZTS), a potential candidate for absorber layer in thin film heterojunction solar cell, have been successfully deposited by spray pyrolysis technique on soda-lime glass substrates. The effect of substrate temperature on the growth of CZTS films is investigated. X-ray diffraction studies reveal that polycrystalline CZTS films with better crystallinity could be obtained for substrate temperatures in the range 643-683 K. The lattice parameters are found to be a=0.542 and c=1.085 nm. The optical band gap of films deposited at various substrate temperatures is found to lie between 1.40 and 1.45 eV. The average optical absorption coefficient is found to be >10⁴ cm⁻¹.     

Structure, composition and optical properties of Cu2ZnSnS4 thin films deposited by Pulsed Laser Deposition method

Polycrystalline Cu₂ZnSnS₄ (CZTS) thin films have been directly deposited on heating Mo-coated glass substrates by Pulsed Laser Deposition (PLD) method. The results of energy dispersive X-ray spectroscopy (EDX) indicate that these CZTS thin films are Cu-rich and S-poor. The combination of X-ray diffraction (XRD) results and Raman spectroscopy reveals that these thin films exhibit strong preferential orientation of grains along [1 1 2] direction and small Cu_2−xS phase easily exists in CZTS thin films. The lattice parameters and grain sizes have been examined based on XRD patterns and Atom Force Microscopy (AFM). The band gap (E_g) of CZTS thin films, which are determined by reflection spectroscopy varies from 1.53 to 1.98 eV, depending on substrate temperature (T_sub). The optical absorption coefficient of CZTS thin film (T_sub=450 °C) measured by spectroscopic ellipsometry (SE) is above 10⁴ cm⁻¹.     

Comparative study of Cu2ZnSnS4 film growth

We fabricated Cu₂ZnSnS₄ (CZTS) thin films using two different methods, spray pyrolysis and sulfurization of Cu-Zn-Sn metallic films. Spray pyrolysis was carried out under air ambient with modified ultrasonic spray system. Sulfurizations of metallic Cu-Zn-Sn films were done for stacked metallic films, Cu/Sn/Zn/glass, Cu/Sn/Cu/Zn/glass and Sn/Cu/Zn/glass, which were prepared by sputtering method in high vacuum chamber. The sprayed films were not observed to be grown well with good crystallinity, compared with CZTS films made by sulfurization of stacked metallic films. However, it was found that application of additional sulfurization to sprayed CZTS films induced great improvement of crystallinity to the level of the sulfurized metallic films. This implicates that spray pyrolysis with additional sulfurization is a good method for fabrication of CZTS films, especially as a low-cost fabrication technique. All CZTS films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and Raman spectroscopy measurements.     

Improved CIGS thin-film solar cells by surface sulfurization using In2S3 and sulfur vapor

Surface sulfurization of Cu(In,Ga)Se₂ (CIGS) thin films was carried out using two alternative techniques that do not utilize toxic H₂S gas; a sequential evaporation of In₂S₃ after CIGS deposition and the annealing of CIGS thin films in sulfur vapor. A Cu(In,Ga) (S,Se)₂ thin layer was grown on the surface of the CIGS thin film after sulfurization using In₂S₃, whereas this layer was not observed for CIGS thin films after sulfurization using sulfur vapor, although a trace quantity of S was confirmed by AES analysis. In spite of the difference in the surface modification techniques, the cell performance and process yield of the ZnO:Al/CdS/CIGS/Mo/glass thin-film solar cells were remarkably improved by using both surface sulfurization techniques.     

Synthesis and characterization of co-electroplated Cu2ZnSnS4 thin films as potential photovoltaic material

Cu₂ZnSnS₄ thin films have been successfully prepared by a novel synthesis process that involves a single step deposition of Cu₂ZnSnS₄ followed by a post-annealing treatment at 550 °C for 60 min in the atmosphere of N₂+H₂S (5%). The microstructure, morphology, composition and optical property of the film have been investigated in detail. It is found that the Na₂S₂O₃5H₂O concentration in the solution has a significant effect on the Cu₂ZnSnS₄ thin films. X-ray diffraction data indicates that the annealed Cu₂ZnSnS₄ thin films have a kesterite structure with preferred orientation along the (1 1 2) plane. Uniform and compact topographies are observed in some annealed films. From the energy dispersive X-ray spectroscopy analysis, it can be seen that Cu-poor and Zn-rich Cu₂ZnSnS₄ thin films have been obtained. The direct band gap energy of the film is about 1.5 eV.     

Preparation of Cu(In,Ga)(S,Se)2 thin films by sequential evaporation and annealing in sulfur atmosphere

Cu(In,Ga)(S,Se)₂ thin films with high Ga/III ratio (around 0.8) were prepared by sequential evaporation from CuGaSe₂, CuInSe₂, In₂Se₃ and Ga₂Se₃ compounds and then annealing in H₂S gas atmosphere. The annealing temperature was varied from 400 to 500 °C. These samples were characterized by means of XRF, EPMA, XRD and SEM. The S/(S+Se) mole ratio in the thin films increased with increase in the annealing temperature, keeping the Cu, In and Ga contents nearly constant. The open circuit voltage increased and the short circuit current density decreased with increase in the annealing temperature. The best solar cell using Cu(In,Ga)(S,Se)₂ thin film with Ga/(In+Ga)=0.79 and S/(S+Se)=0.11 annealed at 400 °C demonstrated V_oc=535 mV, I_sc=13.3 mA/cm², FF=0.61 and efficiency=4.34% without AR-coating.     

Iron doped nanostructured TiO2 for photoelectrochemical generation of hydrogen

This paper describes the photoelectrochemical studies on nanostructured iron doped titanium dioxide (TiO₂) thin films prepared by sol-gel spin coating method. Thin films were characterized by X-ray diffraction, Raman spectroscopy, spectral absorbance, atomic force microscopy and photoelectrochemical (PEC) measurements. XRD study shows that the films were polycrystalline with the photoactive anatase phase of TiO₂. Doping of Fe in TiO₂ resulted in a shift of absorption edge towards the visible region of solar spectrum. The observed bandgap energy decreased from 3.3 to 2.89 eV on increasing the doping concentration upto 0.2 at.% Fe. 0.2 at.% Fe doped TiO₂ exhibited the highest photocurrent density, ∼0.92 mA/cm² at zero external bias. Flatband potential and donor density determined from the Mott–Schottky plots were found to vary with doping concentration from −0.54 to −0.92 V/SCE and 1.7 × 10¹⁹ to 4.3 × 10¹⁹ cm⁻³, respectively.     

A novel one-step electrodeposition to prepare single-phase CuInS2 thin films for solar cells

Copper indium disulfide (CuInS₂) thin films have been successfully prepared on Ni substrates using a novel one-step potentiostatic electrodeposition combined with a potassium hydrogen phthalate (C₈H₅KO₄) complexing agent, accompanied by annealing at 350 °C. Electrodeposition in the solution of Cu and In salts and sodium thiosulfate (Na₂S₂O₃) containing an adequate concentration of C₈H₅KO₄ (e.g., [C₈H₅KO₄]=23 mM) provides thin films comprised of a CuInS₂ single phase as the bulk composition, without forming Cu_xS secondary phases. In addition to the effect on bulk-phase compositions, the adjustment of [C₈H₅KO₄] causes variation in morphology and atomic composition of the film surface. The surface states of the films change from the Cu-rich rough surface at low [C₈H₅KO₄] (15 mM) to the In-rich smooth surface at high [C₈H₅KO₄] (23 mM). The higher [C₈H₅KO₄] induces the grains constructing the film to interconnect and form a densely packed CuInS₂ film without voids and pinholes. The single-phase and void-free CuInS₂ film shows a band gap of 1.54 eV, satisfying the requirement of the absorber layers in solar cells. The electrical properties tests denote its n-type conductivity with a resistivity of 9.6×10⁻⁵ Ω cm, a carrier concentration of 2.9×10²¹ cm⁻³ and a carrier mobility of 22.2 cm² V⁻¹ s⁻¹.     

Carbon-doped Sb2S3 thin films: Structural, optical and electrical properties

We report the modification of electrical properties of chemical-bath-deposited antimony sulphide (Sb₂S₃) thin films by thermal diffusion of carbon. Sb₂S₃ thin films were obtained from a chemical bath containing SbCl₃ and Na₂S₂O₃ salts at room temperature (27 °C) on glass substrates. A carbon thin film was deposited on Sb₂S₃ film by arc vacuum evaporation and the Sb₂S₃-C layer was subjected to heating at 300 °C in nitrogen atmosphere or in low vacuum for 30 min. The value of resistivity of Sb₂S₃ thin films was substantially reduced from 10⁸ Ω cm for undoped condition to 10² Ω cm for doped thin films. The doped films, Sb₂S₃:C, retained the orthogonal stibnite structure and the optical band gap energy in comparison with that of undoped Sb₂S₃ thin films. By varying the carbon content (wt%) the electrical resistivity of Sb₂S₃ can be controlled in order to make it suitable for various opto-electronic applications.     

Photoelectrochemical performance of sprayed n-CdIn2Se4 photoanodes

Cadmium indium selenide thin films have been synthesized by spraying mixture of equimolar solution concentrations of cadmium chloride, indium trichloride and selenourea in aqueous media onto preheated FTO coated glass substrates at optimized substrate temperature and solution concentration. The photoelectrochemical cell configuration of n-CdIn₂Se₄/(1 M NaOH + 1 M Na₂S + 1 M S)/C has been used for investigate the current-voltage characteristics under dark and white light illumination, photovoltaic output, spectral response, photovoltaic rise and decay characteristics. It reveals the film of CdIn₂Se₄ exhibits n-type conductivity. The junction quality factor in dark (n_d) and light (n_l), series and shunt resistance (R_s and R_sh), fill factor (FF) and efficiency (η) for the cell have been estimated. Gartner’s model was used to calculate minority carrier diffusion length and donor concentration (n_D). The observed efficiency and FF of PEC solar cell is 1.95% and 0.37% respectively. Mott-Schottky plot shows the flat-band potential (V_fb) of CdIn₂Se₄ films is −0.655 V/SCE.     

Photoelectrochemical behavior of In2S3 formed on sintered In2O3 pellets

Microcrystals of In₂S₃ were formed on sintered In₂O₃ pellets by sulfurizing in H₂S atmosphere. The flat band potential of compound In₂S₃|In₂O₃ electrodes was evaluated as −1.0 V vs Ag|AgCl in 1 M KOH, 1 M Na₂S, 10⁻² M S. Significantly enhanced photocurrent was observed on compound In₂S₃|In₂O₃ electrodes with a lower degree of sulfurization to that of compound In₂S₃|In₂O₃ electrodes with higher degree of sulfurization. Photocurrent generation of compound In₂S₃|In₂O₃ electrodes was explained from the viewpoint of semiconductor sensitization.