Electrical and optical properties of Cu2ZnSnS4 thin films prepared by rf magnetron sputtering process

Cu₂ZnSnS₄ thin films were deposited on corning 7059 glass substrates without substrates heating by rf magnetron sputtering. The Cu/(Zn+Sn) ratio of the thin film sputtered at 75 W was close to the stoichiometry of Cu₂ZnSnS₄. However, the S/(Cu+Zn+Sn) ratio was less than the stoichiometry. The as-deposited films were amorphous and annealed in the atmosphere of Ar+S₂ (g). The annealed (1 1 2), (2 0 0), (2 2 0), (3 1 2) planes were conformed to all the reflection of a kesterite structure. A preferred (1 1 2) orientation was observed with the increase of the annealing temperature. The optical absorption coefficient of the thin film was about 1.0×10⁴ cm⁻¹. The optical band energy was derived to be 1.51 eV. The optical absorption coefficient of the sputtered Cu₂ZnSnS₄ thin films was less than that of CuInS₂ thin film, however, the band gap energy was more appropriate for photovoltaic materials.     

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.     

Electrical characterization of Al, Ag and In contacts on CuInS2 thin films deposited by spray pyrolysis

The specific contact resistivity (ρ_C) for aluminum (Al), silver (Ag) and indium (In) metallic contacts on CuInS₂ thin films was determined from I-V measurements, with the purpose of having the most appropriate ohmic contact for TCO/CdS/CuInS₂ solar cells; ρ_C was measured using the transmission line method (TLM) for the metallic contacts evaporated on CuInS₂ thin films deposited by spray pyrolysis with ratios x=[Cu]/[In]=1.0, 1.1, 1.3 and 1.5 in the spray solution. The results show that In contacts have the lowest ρ_C values for CuInS₂ samples grown with x=1.5. The minimum ρ_C was 0.26 Ω cm² for the In contacts. This value, although not very low, will allow the fabrication of CuInS₂ solar cells with a small series resistance.     

Physical properties and photoresponse of Cu-Ag-In-S semiconductor electrodes created using chemical bath deposition

Cu-Ag-In-S solid solution semiconductor films were grown on indium-tin oxide-coated glass substrates using chemical bath deposition. New procedures for the growth of Cu-Ag-In-S semiconductor films are presented. The optical, electrical, and photoelectrochemical performances of the ternary CuInS₂, AgIn₅S₈, and their solid solutions are investigated. The X-ray diffraction patterns of samples reveal a change in the crystal phase of the samples from the tetragonal CuInS₂ to the cubic AgIn₅S₈ phase with an increase in the [Ag/(Cu+Ag)] molar ratio in precursor solutions. The thicknesses and band gaps of the samples, determined from the surface profile measurements and transmittance spectra, are in the ranges of 841-2107 nm and 1.42-1.75 eV, respectively. The highest photoresponse was observed in the sample with [Ag/(Ag+Cu)]=0.4 (sample (d)) under illumination with a white light intensity of 100 mW/cm². The results show that Cu-Ag-In-S film electrodes have potential in solar to hydrogen applications.     

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.     

Mechanistic investigation on tuning the conductivity type of cuprous oxide (Cu2O) thin films via deposition potential

The conductivity type of cuprous oxide (Cu₂O) thin films is tuned by controlling the deposition potential of an electrochemical process in an acid cupric acetate solution containing sodium dodecyl sulfate. The morphology and chemical composition of the deposited Cu₂O films are studied by SEM, XRD and XPS. The change of the conductivity type of Cu₂O films is further studied through zero-bias photocurrent and Mott-Schottky measurements. The results indicate that the Cu₂O films behave as n-type semiconductors when the overpotentials are low (potentials higher than ?0.05 V) and p-type semiconductors when the overpotentials are high (potentials lower than ?0.10 V). The transformation of conductivity from n-type to p-type comes from the competition reactions between forming Cu₂O and forming metallic Cu from Cu²⁺. When the potential is lower than ?0.10 V, most of Cu²⁺ are consumed by the growth of metallic Cu at the film/solution interface, so that the Cu²⁺ provided to grow Cu₂O film are insufficient and copper vacancies form in the film, leading to the p-type conductivity.     

Highly efficient TiO2 nanotube photocatalyst for simultaneous hydrogen production and copper removal from water

1-D mesoporous TiO₂ nanotube (TNT) with large BET surface area was successfully synthesized by a hydrothermal-calcination process, and employed for simultaneous photocatalytic H₂ production and Cu²⁺ removal from water. Cu²⁺, across a wide concentration range of 8-800 ppm, was removed rapidly from water under irradiation. The removed Cu²⁺ then combined with TNT to produce efficient Cu incorporated TNT (Cu-TNT) photocatalyst for H₂ production. Average H₂ generation rate recorded across a 4 h reaction was between 15.7 and 40.2 mmol h⁻¹ g⁻¹_catalyst, depending on initial Cu²⁺/Ti ratio in solution, which was optimized at 10 atom%. In addition, reduction process of Cu²⁺ was also a critical factor in governing H₂ evolution. In comparison with P25, its large surface area and 1-D tubular structure endowed TNT with higher photocatalytic activity in both Cu²⁺ removal and H₂ production.     

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.     

Sulfurization of Cu–In electrodeposited precursors for CuInS2-based solar cells

Cu–In electrodeposited layers were annealed using rapid thermal processing (RTP) in a reactive atmosphere containing sulfur vapors. The CuInS₂ formation mechanism during sulfurization of electrodeposited precursors proceeds mainly through direct sulfurization of the metallic Cu–In alloy, forming spinel CuIn₅S₈ and chalcopyrite CuInS₂ ternary phases. During the heating step, the Cu–In metallic alloy gets richer in copper as the temperature increases and transforms from CuIn₂ to Cu₁₁In₉, then Cu₁₆In₉ and finally to Cu₇In₃. The use of rapidly cooled samples stopped after different durations of the process along with ex-situ XRD analysis enabled us to differentiate the Cu₁₆In₉ and Cu₇In₃ phases. Finally, the efficiency of the solar cells made with the two-step electrodeposition and RTP low-cost process reaches 11% (active area 0.421 cm²), which is close to the results obtained for cells made with PVD 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%.     

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).     

Influence of H2S concentration on the properties of Cu2ZnSnS4 thin films and solar cells prepared by sol-gel sulfurization

Cu₂ZnSnS₄ (CZTS) thin films prepared by a non-vacuum process based on the sulfurization of precursor coatings, consisting of a sol-gel solution of Cu, Zn, and Sn, under H₂S+N₂ atmosphere were investigated. The structure, microstructure, and electronic properties of the CZTS thin films as well as solar cell parameters were studied in dependence on the H₂S concentration. The sulfurization process was carried out at 500 °C for 1 h in an H₂S+N₂ mixed-gas atmosphere with H₂S concentrations of 3%, 5%, 10%, and 20%. As the H₂S concentration decreased from 20% to 5%, the S content of the CZTS thin films decreased. However, when the H₂S concentration was decreased below 3%, the S content of the films began to increase. A CZTS thin film prepared with an H₂S concentration of 3% had grains in the order of 1 μm in size, which were larger than those of films prepared at other H₂S concentrations. Furthermore, the most efficient solar cell, with a conversion efficiency of 2.23%, was obtained from a sample sulfurized at an H₂S concentration of 3%.     

Ex-situ and in-situ analyses on reaction mechanism of CuInSe2 (CIS) formed by selenization of sputter deposited CuIn precursor with Se vapor

Formation mechanism of CIS thin films by selenization of sputter deposited CuIn precursor with Se vapor was investigated by ex-situ and in-situ phase analysis tools. Precursor films were composed of In, CuIn and Cu₂In compounds, and their relative fractions were systematically changed with Cu/In ratios. Those films were found to have a double layered structure with nearly pure In particles (top layer) placed on the flat Cu-rich bottom layer, and the morphologies were also significantly affected by Cu/In ratio. At the initial stage of selenization, the outer In-rich layer reacted with Se vapor to form In-Se binary, which is the first selenide phase appeared, and inner Cu-rich phases acted as a Cu source to supply Cu to outer In-Se phase to form ordered vacancy compounds (OVC). As these reactions continues, in conjunction with Se incorporation into inner Cu-rich region, the films gradually changes from OVC to α-CIS, reflecting that the formation route of CIS is closely related to the elemental and phase distribution in precursor films. Selenized CIS films were further processed to fabricate CIS thin film solar cells, resulting in the best cell efficiency of 10.44%.     

Stoichiometry controlled conversion efficiency in nanostructured heterojunction solar cell of CdS/CuInSXSe2−X grown by chemical ion exchange method at room temperature

Here in the present paper, we report on growth of stoichiometric and nonstoichiometric nanostructured heterojunction solar cell of CdS/CuInS_XSe_2-X varying X from 0 to 2 in the interval of 0.5 using cost effective, simple, chemical ion exchange method at room temperature on ITO glass substrate. The as-grown varying composition solar cells annealed at 200 °C in air and characterized for structural, compositional, optical and illumination studies. The X-ray diffraction pattern obtained from CdS/CuInS_XSe_2-X solar cell confirms the formation of CuInSe₂, CuInS_0.5Se_1.5, CuInS₁Se₁, CuInS_1.5Se_0.5 and CuInS₂ phases having tetragonal structure with varying crystallite size from 19, 19.37, 28, 33 and 20 nm respectively. The energy dispersive X-ray analysis (EDAX) confirms the expected elemental composition in the heterojunction solar cell. Optical absorbance analysis confirms composition controlled electronic transitions in the thin films while energy band gap observed to be red shifted with increase the value of X. The solar energy conversion efficiency achieved upon illuminating to 100 mW/cm² observed to be 0.27%, 0.06%, 0.17%, 0.02% and 0.23% for CuInSe₂, CuInS_0.5Se_1.5, CuInS₁Se₁, CuInS_1.5Se_0.5 and CuInS₂ respectively, which correspond for stoichiometric dependent electron-hole pair generation and separation phenomenon.     

One step hydrothermal synthesis of novel Cu2S-MoO3 nanocomposite for lithium ion battery and photocatalytic applications

Novel Cu₂S-MoO₃ nanocomposite (NC) has been synthesized successfully by single step hydrothermal method. The crystal structure, morphology and optical properties of Cu₂S-MoO₃ NC were individualised by XRD, FTIR, SEM, TEM, UV–Visible spectroscopy. As synthesized Cu₂S-MoO₃ NC was used as anode material for lithium ion battery (LIB) and manifested first discharge capacity 1516 mAhg^?1 at C/4 current rate. Cu₂S-MoO₃ NC is also implemented for photocatalytic hydrogen generation. In addition to above applications, it is materialized for degradation of organic dye (methylene blue) and chromium reduction [Cr(VI) to Cr(III)] with peerless activity.     

CdO/Cu2O solar cells by chemical deposition

CdO and Cu₂O thin films have been grown on glass substrates by chemical deposition method. Optical transmittances of the CdO and Cu₂O thin films have been measured as 60–70% and 3–8%, respectively in 400–900 nm range at room temperature. Bandgaps of the CdO and Cu₂O thin films were calculated as 2.3 and 2.1 eV respectively from the optical transmission curves. The X-ray diffraction spectra showed that films are polycrystalline. Their resistivity, as measured by Van der Pauw method yielded 10⁻²–10⁻³ Ω cm for CdO and approximately 10³ Ω cm for Cu₂O. CdO/Cu₂O solar cells were made by using CdO and Cu₂O thin films. Open circuit voltages and short circuit currents of these solar cells were measured by silver paste contacts and were found to be between 1–8 mV and 1–4 μA.     

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.     

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.     

Electrochemical deposition of thin ZnTe films as a contact for CdTe solar cells

ZnTe films doped with Cu were deposited by an electrochemical method for the first time directly onto CdTe/CdS/ITO/glass substrates to form a low resistance contact to CdTe. The depositions were carried out in an aqueous solution of ZnCl₂, TeO₂ and CuCl₂ or CuSO₄ in which the substrate was externally short circuited to a Zn counter electrode to complete an electrochemical cell. Single phase films 50 nm to 300 nm thick were obtained for specific pH and TeO₂ concentrations and bath temperature. Complexing the Cu²⁺ with triethanolamine (TEA) allowed reproducible deposition of p-type ZnTe:Cu films. ZnTe/Cu/CdTe/CdS solar cells fabricated using this method have achieved AM1.5 efficiencies of 8.7%.     

Effect of impurities in TiO2 thin films on trichloroethylene conversion

In this study, we investigate the physical properties and photocatalytic activities of TiO₂ thin films doped with low valence (Fe³⁺, Co²⁺, and Ni²⁺) and high valence (Mo⁵⁺, Nb⁵⁺, and W⁶⁺) cations. Clear difference in results from various analytical tools between groups was identified. The presence of different oxidation states and a higher degree of crystallinity in the high valence cation doped-TiO₂ thin films seemed beneficial in terms of the transfer and separation of photo-generated electrons and holes in the TiO₂ medium and on the surface, resulting in higher photocatalytic conversion of trichloroetylene.