Characterization of CuInS2 thin films prepared by electrodeposition and sulfurization with photoluminescence spectroscopy

Potentiostatic electrodeposition and sulfurization techniques were used to prepare polycrystalline CuInS₂ thin films. X-ray diffraction and photoresponse measurements in a photoelectrochemical cell (PEC) revealed that photoactive polycrystalline CuInS₂ films can be deposited on Ti substrate. Photoluminescence (PL) spectroscopy was used to investigate the prepared thin films and optically characterize them. PL spectra revealed the defect structure of the samples with an acceptor energy level at 109 meV above the valance band and a donor energy level at 71 meV below the conduction band. The CuInS₂ thin films prepared in this investigation are observed to be In-rich material with n-type electrical conductivity.     

Chemical-bath ZnO buffer layer for CuInS2 thin-film solar cells

ZnO buffer layers were grown by a chemical-bath deposition (CBD) in order to improve the interface quality in p-CuInS₂ based solar cells, to improve the light transmission in the blue wavelength region, but also as an alternative to eliminate the toxic cadmium. The process consists of immersion of different substrates (glass, CIS) in a dilute solution of tetraamminezinc II, [Zn(NH₂)₄]²⁺, complex at 60–95°C. During the growth process, a homogeneous growth mechanism which proceeds by the sedimentation of a mixture of ZnO and Zn(OH)₂ clusters formed in solution, competes with the heterogeneous growth mechanism. The mechanism consists of specific adsorption of a complex Zn(II) followed by a chemical reaction. The last process of growth results in thin, hard, adherent and specularly reflecting films. The characterization of the deposited CBD-ZnO layers was performed by X-ray diffraction (XRD), optical transmittance, scanning electron microscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The as-deposited films on glass show hexagonal zincite structure with two preferred orientations (1 0 0) and (1 0 1). High optical transmittance up to 80% in the near-infrared and part of the visible region was observed. The low growth rate of the films on CIS suggests an atomic layer-by-layer growth process.The device parameters and performance are compared to heterojunction with a standard CdS buffer layer.     

Solar cells with Cu(In1−xGax)S2 thin films prepared by sulfurization

By rapid thermal processing of Cu/In/GaS precursors, good-quality CuIn_1–xGa_xS₂ films are synthesized. By suppressing the formation of In-rich hillocks, we could obtain homogeneous CuIn_1–xGa_xS₂ surfaces. A conversion efficiency of 12% has been achieved using a relatively low (1.2) Cu/In ratio.     

The influence of sodium on the properties of CuInS2 thin films and solar cells

The controlled incorporation of sodium into the absorber layer of CuInS₂ solar cells improved cell performance remarkably. Without toxic KCN treatment, conversion efficiencies of over 6% were achieved by sulfurization of sodium-containing precursors. We also investigated the characteristics of the sodium-incorporated CuInS₂ films by intentional addition and diffusion from a soda-lime glass. The ternary compound semiconductor of NaInS₂ was found to form mainly on the surface of each of the CuInS₂ films.     

Deposition of CuInS2 films by electrostatic field assisted ultrasonic spray pyrolysis

We studied CuInS₂ (CIS) film growth using high electrostatic field assisted ultrasonic spray (HEFAUS) deposition. CIS films were fabricated with various precursors and substrate temperatures. All the as-sprayed CIS films were observed to be grown with mixed ordering mode, where chalcopyrite (CH) and CuAu (CA) orderings coexisted. It was found that application of additional sulfurization to sprayed CIS films induced re-crystallization of films accompanied by enhancement of CH ordering. After the post-sulfurization, the most improved film showed nearly the same CH-fraction as that for a CIS film which was made by sulfurization of sputtered Cu-In alloy film. These results indicate that our modified spray deposition could be used for fabrication of CIS photoabsorbing layer instead of high-cost vacuum-based process. All fabricated films were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscope and energy dispersive X-ray analysis measurements.     

Electrodeposited CuInS2-based thin-film solar cells

CuInS₂ thin films were prepared by sulfurization of electrodeposited Cu–In precursors. Morphological improvement enabled us to fabricate the solar cells using electrodeposited Cu–In precursors. The photovoltaic property of a conversion efficiency of 1.3% was obtained.     

Influence of Na on the properties of Cu-rich prepared CuInS2 thin films and the performance of corresponding CuInS2/CdS/ZnO solar cells

Using different glass substrate types the Na content in sequentially and Cu-rich prepared CuInS₂ films and corresponding CuInS₂/CdS/ZnO thin-film solar cells is varied. The purpose was to investigate the influence of different Na concentrations on absorbers and devices. While the morphology of the absorbers seems not to be affected by this variation, corresponding PL spectra differ significantly. The properties of the solar cells, however, show no dependence on the Na concentration. This implies that even though the defect chemistry of CuInS₂, sequentially prepared under Cu excess, is changed by the presence of Na this influence has no impact on properties of corresponding solar cells.     

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.     

Influence of In2S3 film properties on the behavior of CuInS2/In2S3/ZnO type solar cells

Solar cells of CuInS₂/In₂S₃/ZnO type are studied as a function of the In₂S₃ buffer deposition conditions. In₂S₃ is deposited from an aqueous solution containing thioacetamide (TA), as sulfur precursor and In³⁺. In parallel, variable amounts of In₂O₃ are deposited that have an important influence on the buffer layer behavior. Starting from deposition conditions determined in a preliminary study, a set of parameters is chosen to be most determining for the buffer layer behavior, namely the solution temperature, the concentration of thioacetamide [TA], and the buffer thickness. The solar cell results are discussed in relation with these parameters. Higher efficiency is attained with buffer deposited at high temperature (70 °C) and [TA] (0.3 M). These conditions are characterized by short induction time, high deposition rate and low In₂O₃ content in the buffer. On the other hand, the film deposited at lower temperature has higher In₂O₃ content, and gives solar cell efficiency sharply decreasing with buffer thickness. This buffer type may attain higher conversion efficiencies if deposited on full covering very thin film.     

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.     

Preparation and properties of CuInS2 thin film prepared from electroplated precursor

Thin CuInS₂ films were prepared by sulfurization of Cu/In bi-layers. First, the precursor layer was electroplated onto the treated surface of Mo-coated glass. Observation of the cross-section prepared by focused ion beam (FIB) etching revealed that the void-free film was initially formed on the top surface of the precursor layer and continued to grow until the advancing front of the film reached the Mo layer. The nucleation of voids near the bottom of the CuInS₂ film followed. To determine whether the condition of the Cu/In alloy influences the CuInS₂ quality we investigated the Cu/In alloy state using FIB. We found that the annealed precursor of low Cu/In ratio (1.2) has several voids in the mid position in the layer compared with Cu-rich precursor (1.6). The cross-sectional view of the Cu-rich absorber layer is uniform compared with the low copper absorber layer. Thin film solar cells were fabricated using the CuInS₂ film (Cu/In ratio: 1.2) as an optical absorber layer. It was found that the optimization of a sulfurization period is important in order to improve the cell efficiency. We have not yet obtained good results with high Cu-rich absorber because of a blister problem. This blister was found before sulfurization. So, we are going to solve this blister problem before sulfurization.     

Sprayed CuInS2 films grown under Cu-rich conditions as absorbers for solar cells

CuInS₂ films were prepared by the spray pyrolysis method using either copper-rich solutions or the recrystallization of low-crystallinity film in the presence of an intentionally deposited Cu_xS layer. KCN-etched films were characterized by XRD, SEM and EDX. The Cu/In molar ratio of 1.5–4.0 in the solution resulted in well-crystallized CuInS₂ films with the mean crystallite size of 120 nm. SEM study showed nonuniform surface with irregularly placed large grain domains in the flat film. The two-step process resulted in a uniform film with the crystallite size of 50 nm. Films exhibited an In-rich composition. Solar cells based on a recrystallized absorber showed an improved quantum efficiency spectrum.     

CuInS2/In2S3 thin film solar cell using spray pyrolysis technique having 9.5% efficiency

Copper indium sulfide (CuInS₂)/In₂S₃ solar cells were fabricated using spray pyrolysis method and high short circuit current density and moderate open circuit voltage were obtained by adjusting the condition of deposition and thickness of both the layers. Consequently, a relatively high efficiency of 9.5% (active area) was obtained without any anti-reflection coating. The cell structure was ITO/CuInS₂/In₂S₃/Ag. We avoided the usual cyanide etching and CdS buffer layer, both toxic, for the fabrication of the cell.     

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.     

Preparation and characterization of CuInS2 thin films solar cells with large grain

The CuInS₂ films with a maximum thickness of about 9 μm and a maximum atomic Cu/In ratio (as-deposited precursor) of 3.0 were prepared, and, to prevent peeling from substrate, were heat treated during Cu/In evaporation and/or intercalated with very thin Pt or Pd (between Mo and CuInS₂ layers). Thus, we could prepare the films with very large grain. It is also worth noting that the large grain films were easily optimized by chemical etching of the films using a thick film and Cu-rich composition. Therefore, the absorber for high-efficiency solar cells can be prepared by varying over a wide range of composition and thickness of precursor. The characterization of CuInS₂ absorbers with various film thickness and compositions were investigated and related with the performance of the photovoltaic device.     

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.     

Control of valence states by a codoping method in CuInS2

We deviate the valence and conduction band energies of stoichiometric CuInS₂ crystals based on ab initio electronic band structure calculations using the augmented spherical wave (ASW) method and discuss that at low doping levels, the Madelung energy is a good intrinsic parameter for stabilization of p- or n-type doped CuInS₂ crystals. We find that P and Sb atoms are eminently suitable dopants substituted for S atoms for p-type doped CuInS₂ crystals with lower resistivity from both the character of electronic states around E_F and the Madelung energy. A closer study of the nature of chemical bonds of CuInS₂ crystals using first-principles band structure calculation method reveals that In with polyvalence codoping for p-type CuInS₂ doped with P results in a decrease of the Madelung energy compared with CuInS₂: P, to be an effective method for stabilizing of its ionic charge distributions.     

Preparation of CuInS2 films with sufficient sulfur content and excellent morphology by one-step electrodeposition

One-step electrodeposition using sodium thiosulfate (Na₂S₂O₃) as a sulfur source has been studied for the preparation of Cu---In---S thin films. A deposited film is found to have a sufficiently high sulfur content compared with films deposited using thiourea as a sulfur source. The film deposited using Na₂S₂O₃ is also found to have an excellent morphology compared with electrodeposited Cu---In precursors. Predominant factors to govern film composition, In/Cu and S/(Cu + In) ratios, are also investigated in this study. An HC1 content added in order to decompose S₂O₃²⁻ ions in the solution is found to be one of the important factors to control composition of deposited films. A sulfur cocentration in the solution influences not only S/(Cu + In) ratio but also In/Cu ratio in the film. Reproducibility of film composition is deteriorated as the solution temperature increases.     

Investigation of capacitance transients in CuInS2 due to ionic migration

Transport of mobile ions in n-TiO₂/n-CuInS₂/p-CuInS₂ thin-film devices is studied with the transient ion-drift (TID) method. In contrast to the normal TID method, a mobile ion profile is created in the CuInS₂ layer, which can be described by the Gouy-Chapman theory. Activation energies for diffusion of 0.5 and 1.0 eV are found. We postulate that these activation energies are related to the associated defect, ( In_Cu)^x, which introduces a deep electronic state inside the bandgap of CuInS₂. This defect can accept or release an electron and drift out of the depletion region. This will lower the concentration of recombination centers in the depletion region, which explains the self-healing property of CuInS₂.     

Study of the Mo/CuInS2/ZnS system by TEM

This work presents results from a study carried out on the Mo/CuInS₂/ZnS stacked layers, using high-resolution transmission electron microscopy (HRTEM). This system will be used later for the fabrication of solar cells with Mo/CuInS₂/ZnS/TCO structure, where the layers conforming it will perform as an electrical contact, absorber layer and buffer layer, respectively. The layers of the Mo/CuInS₂/ZnS system were deposited sequentially on soda lime glass substrates. The Mo film was deposited by DC magnetron sputtering, the CuInS₂ (CIS) layer was grown by co-evaporation of precursors in a two-stage process and the ZnS was deposited by co-evaporation and by CBD (chemical bath deposition) using a solution containing zinc acetate, sodium citrate, ammonia and thiourea.The performed study provided significant information regarding crystalline structure, grain boundaries and defects visualization of each one of the layers as well as of the Mo/CuInS₂ and CuInS₂/ZnS interfaces.