Thin film deposition of Cu2O and application for solar cells

Deposition conditions of cuprous oxide (Cu₂O) thin films on glass substrates and nitrogen doping into Cu₂O were studied by using reactive radio-frequency magnetron sputtering method. The effects of defect passivation by crown-ether cyanide treatment, which simply involves immersion in KCN solutions containing 18-crown-6 followed by rinse, were also studied. By the crown-ether cyanide treatment, the luminescence intensity due to the near-band-edge emission of Cu₂O at around 680 nm was enhanced, and the hole density was increased from 10¹⁶ to 10¹⁷ cm⁻³. Finally, polycrystalline p-Cu₂O/n-ZnO heterojunctions were grown for use in solar cells. Two deposition sequences were studied, ZnO deposited on Cu₂O and Cu₂O deposited on ZnO. It was found that the crystallographic orientation and current–voltage characteristics of the heterojunction were significantly influenced by the deposition sequence, both being far superior for the heterojunction with structure Cu₂O on ZnO than for the inverse structure. We successfully obtained a photoresponse for the first time in the deposited thin film of Cu₂O/ZnO.     

Properties of fluorine-doped SnO2 films prepared by the pyrosol deposition method

Fluorine-doped SnO₂ (SnO₂:F) films were prepared in ordinary atmosphere on heated Corning 7059 glass substrates by the pyrosol deposition method with solutions consisting of SnCl₄·5H₂O, NH₄F, CH₃OH, H₂O and HCl. It was found that the substrate temperature and the chemical composition of the solutions largely affect the deposition rate and the properties of the SnO₂:F films. Under the optimized deposition condition, a resistivity as low as ≈4.3 × 10⁻⁴ Ω cm and a specular transmittance of ≈79% could be attained for a ≈0.6 μm thick film. X-ray diffraction measurements showed that these films were polycrystalline with the tetragonal cassiterite structure and grew with a (200) preferred orientation. The surface morphology observed by scanning electron microscopy changed from round-shape to pyramidal-shape above a substrate temperature of 450°C. A similar change in the surface morphology also took place when the CH₃OH/H₂O mol ratio in solution was less than 0.1. X-ray photoelectron spectroscopy indicated that the fluorine concentrations in the films, being significantly diminished, also increase with increasing the fluorine concentrations in the starting solutions.     

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.     

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.     

MgH2 thin films deposited by one-step reactive plasma sputtering

The morphology, crystal structure, hydrogen content, and sorption properties of magnesium hydride thin films prepared by reactive plasma-assisted sputter deposition were investigated. Few micrometers-thick films were deposited on Si and SiO₂/Si substrates, at low pressure (0.4 Pa) and close to room temperature using (Ar + H₂) plasma with H₂ fraction in the range 15–70%. The microstructure and hydrogen content of the films are closely related to the surface temperature and hydrogen partial pressure during the deposition process. Operating in pulsed-plasma mode allows the hydrogenation rate of the MgH₂ thin film to top up to 98%, thereby producing a nearly fully hydrogenated film in a single-step process. The positive effect of the pulsed process is explained by the significant decrease in the whole energy flux incident on the surface and the favourable impact of the transient process for the rearrangement/relaxation of the materials. As for the hydrogen storage properties, desorption experiments and cycling of the films show the destabilizing effect of Mg₂Si formation at the interface between the film and the Si substrate resulting in a drastically increased desorption kinetics compared to less reactive SiO₂ substrate. However, the reaction is regrettably not reversible upon hydrogenation and the hydrogen storage capacity is consequently reduced upon cycling. Nevertheless, the deposition process carried out on inert substrates would offer true potential for reversible storage. Finally, our experimental results, which show the possibility to preferentially grow the metastable medium pressure γ-MgH₂ phase, open possibilities for the synthesis of more complex metastable phases such as magnesium-based ternary compounds.     

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.     

Investigations on ZnxCd1−xO thin films obtained by spray pyrolysis

Zn_xCd_1−xO thin films were prepared on glass substrates by spray pyrolysis technique. The precursor solutions were obtained by varying the concentration of Zn(NO₃)₂·6H₂O and Cd(NO₃)₂·4H₂O in bi-distilled water. The structural properties have been studied using X-ray diffraction spectra. All the structures include the basic compounds, i.e. ZnO and CdO. The orientation and the crystalline phases of the deposited films were specified. With the addition of Zn to the precursor solution, we can observe the preferential orientation of the CdO in the [2 0 0] direction. The electrical measurements were performed using method of four contacts. Thin films transmittances, in the 1.5–4.3 eV range, for different compositions have been measured and the optical gaps have been determined. The variations are explained considering the gaps of the two pure films. The influence of increased Cd concentration in the films on the structural, electrical and optical properties is investigated in this study.     

Field effect surface passivation of SiO2/Si interfaces by heat treatment with high-pressure H2O vapor

We investigated a simple field effect passivation of the silicon surfaces using the high-pressure H₂O vapor heating. Heat treatment with 2.1×10⁶ Pa H₂O vapor at 260°C for 3 h reduced the surface recombination velocity from 405 cm/s (before the heat treatment) to 38 cm/s for the thermally evaporated SiO_x film/Si. Additional deposition of 140 nm-SiO_x films (x<2) with a high density of fixed positive charges on the SiO₂/Si samples further decreased the surface recombination velocity to 22 cm/s. We also demonstrated the field effect passivation for n-type silicon wafer coated with thermally grown SiO₂. Additional deposition of 210 nm SiO_x films on both the front and rear surfaces increased the effective lifetime from 1.4 to 4.6 ms. Combination of thermal evaporation of SiO_x film and the heat treatment with high-pressure H₂O vapor is effective for low-temperature passivation of the silicon surface.     

Growth of Zn1−xMgxO films with single wurtzite structure by MOCVD process and their application to Cu(InGa)(SSe)2 solar cells

The effect of the growth temperature and Mg/(Mg+Zn) molar flow rate ratio of metal organic sources on the crystalline structure of Zn_1−xMg_xO (ZMO) films is investigated in thin films prepared by metal organic chemical vapor deposition (MOCVD) process on fused silica in order to obtain the wide-bandgap ZMO films with single wurtzite structure, which is very important to achieve high-efficiency chalcopyrite solar cells. Based on the measurements and analysis of the fabricated samples, the ZMO films with the controllable bandgap from 3.3 to 3.72 eV can exhibit a single wurtzite phase depending on the growth temperature and Mg content. Furthermore, the resistivity of ZMO films is comparable to that of ZnO film. It is a good indication that ZMO film is superior to CdS or ZnO films as buffer and window layers mainly due to its controllable bandgap energy and safety. As a result, the solar cells with ZMO buffer were fabricated without any surface treatment of Cu(InGa)(SSe)₂ (CIGSSe) absorber or antireflection coating, and the efficiency of 10.24% was obtained.     

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.     

Photoelectrochemical studies of Cu2O Photoelectrode coated with Au and SiO thin films

An attempt has been made to stabilize the photocurrent in a photoelectrochemical cell by depositing thin Au and SiO films onto the Cu₂O photoelectrode. In case of Au deposition, the photocurrent was either quenched or reduced. This may be the cause of insufficient formation of surface states in the electrode-electrolyte interfaces. In a Sio deposited photoelectrode, its effect was to decrease the quantum efficiency of a fresh sample, however, this deposition does not affect the value obtained for the band gap at 2.11 eV for an uncoated sample. It may be interpreted that the observed deterioration is not due strictly to surface effects or chemical reaction at the surface.     

Nanostructured SrTiO3 thin films sensitized by Cu2O for photoelectrochemical hydrogen generation

We prepared nanostructured thin films of pristine SrTiO₃, Cu₂O and SrTiO₃/Cu₂O heterojunction with varying the thickness of Cu₂O. SrTiO₃ and Cu₂O thin films were deposited on ITO (Sn:In₂O₃) glass substrate using sol–gel spin-coating technique and spray pyrolysis method respectively. Samples were characterized using XRD (X-ray diffractometry), SEM (Scanning electron microscopy), and UV–Visible absorption spectroscopy. Nanostructured thin films of pristine SrTiO₃, Cu₂O and SrTiO₃/Cu₂O heterojunction systems were used as photoelectrode in the Photoelectrochemical (PEC) cell for water splitting reaction. Maximum photocurrent density value of 2.44 mA cm⁻² at 0.95 V/SCE were observed for SrTiO₃/Cu₂O heterojunction photoelectrode with 454 nm thickness, which was approximately 34 times higher than pristine SrTiO₃ thin film. Increased photocurrent density observed for the heterojunction can be attributed to the improved conductivity and better separation of the photogenerated charge carriers at the SrTiO₃/Cu₂O interface.     

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).     

ZnO thin films,surface embedded with biologically derived Ag/Au nanoparticles,for efficient photoelectrochemical splitting of water

ZnO thin films, showing nano-ridges at the surface and the top layer embedded with metal (Ag/Au) nanoparticles (MNP), were obtained by sol-gel synthesis, using zinc acetate dihydrate [(CH₃.COO)₂Zn.2H₂O] as precursor. The method involved prior synthesis of Ag and Au nanoparticles via biological reduction of AgNO₃ and HAuCl₄, respectively, using algae Spirulina platensis. The XRD analysis indicated dominant evolution of wurtzite ZnO phase. Low-angle shift in peaks, seen with nanoparticles embedded films, indicated partial diffusion of metals into ZnO lattice. Band gap energy was least affected and lied in the expected range. AFM and SEM analysis revealed the surface topography and morphology, while EDX analysis confirmed the elemental stoichiometry and existence of Ag/Au nanoparticles in samples. Significant gain in photoelectrochemical current using MNP embedded films is largely accountable to the improvement in electrical conductance and the role played by metal nanoparticles in charge-carrier separation, collection and transport.     

Photoluminescence properties of sodium incorporation in CuInSe2 and CuIn3Se5 thin films

CuInSe₂ and CuIn₃Se₅ thin films have been deposited using sodium compounds such as Na₂Se and Na₂S onto Corning 7059 glass substrates by the two-stage co-evaporation method. Enhanced grain growth and preferred (1 1 2) grain orientation as well as a decrease in resistivity with respect to undoped films were observed with sodium incorporation. A clear correlation between the photoluminescence spectra and the resistivity of the films was found by comparing the properties of films with and without Na incorporation. These observations suggest that compensation is reduced due to the suppression of donor-type defects by the presence of Na.     

Optical transmittance and photoconductivity studies on ZnO : Al thin films prepared by the sol–gel technique

Polycrystalline ZnO : Al thin films have been prepared by the (Sol–gel) chemical deposition method. The ZnO : Al thin films are very transparent (90%) in the near UV, VIS and IR regions. The films are oriented along the c-axis ([0 0 2] direction) in the hexagonal structure. It is known that pure ZnO thin films are not chemically stable in corrosive media, but aluminium stabilizes the ZnO system and increases its electrical conductivity. Finally, the ZnO : Al thin films are reasonably stable under storage in air and in reactive atmospheres like O₂, H₂O, H₂ or in weak acids. Dark- and photo-conductivity of the ZnO : Al films are very high (1–100 Ω⁻¹ cm⁻¹), so that they can be used as transparent conductors in solar cells or in electrochromic devices.     

Preparation of CuGaS2 thin films by two-stage MOCVD method

Copper gallium disulfide (CuGaS₂; CGS) films were deposited on glass or ITO glass by two-stage metal-organic chemical vapor deposition (MOCVD) method, using Cu- and Ga/S-containing precursors without toxic H₂S gas. First, pure Cu thin films were prepared on glass substrates by using a single-source precursor, bis(ethylbutyrylacetato)copper(II) or bis(ethylisobutyrylacetato)copper(II). Second, the resulting Cu films were processed using tris(N,N-ethylbutyldithiocarbamato)gallium(III) at 410-470 °C to produce CuGaS₂ films. The optical band gap of the CGS film grown at 440 °C was about 2.53 eV. In addition, it was found that the elemental ratio of Cu and Ga elements of the CGS films can be elaborately adjusted by controlling deposition conditions on demand.     

Growth of highly c-axis oriented Mg:ZnO nanorods on Al2O3 substrate towards high-performance H2 sensing

Highly c-axis oriented Mg:ZnO films were fabricated on Al₂O₃ substrate by radio frequency sputtering for different substrate temperatures. The crystal structure revealed that the Mg dopants are well integrated into ZnO wurtzite lattice. X-ray photoelectron spectroscopy measurements also confirmed the successful incorporation of Mg into ZnO. The substrate temperature exhibit significant influence on the optical absorbance and band gap of Mg:ZnO films. Scanning electron microscope images revealed the formation of Mg:ZnO nanorods with good crystalline quality. The films prepared at 1200 °C show well grown rods of Mg:ZnO due to strengthening of the preferred orientation of ZnO along the c-axis. The Mg:ZnO/Al₂O₃ films prepared at different temperature were tested for its sensing performance towards 200 ppm of H₂ at room temperature. The Mg:ZnO sensor prepared at 1200 °C revealed fast response and recovery time of about 85 s and 70 s, respectively. The response of the sensor was linear to H₂ concentration in the range of 100–500 ppm. It can be summarized that this high performance H₂ sensor has potential for use as a portable room temperature gas sensor.     

Characteristics of Sn/Li2O multilayer composite anode for thin film microbattery

Sputtering growth of a Sn/Li₂O multilayer composite thin film is conducted to produce an anode thin film with less capacity fading than that of a pure SnO₂ film for a thin-film battery. The structural properties of the Sn/Li₂O multilayer are examined. In addition, the electrochemical characteristics of the Sn/Li₂O and pure SnO₂ thin films are compared. X-ray diffraction and transmission electron microscopy measurements reveal a Sn crystalline peak only and a Sn–Li₂O multilayer structure, respectively, in the Sn/Li₂O thin film. A SnO₂ thin film with a polycrystalline phase shows an irreversible side-reaction at 0.8 V versus Li/Li⁺, an initial charge retention of about 29%, and poor cycleability in the cut-off voltage range from 1.2 to 0 V versus Li/Li⁺. By contrast, no irreversible side-reaction is found in the Sn/Li₂O multilayer composite thin film while there is an initial charge retention of 49% and better cycleability (more than twice) than that of pure SnO₂ film after about 150 cycles. These results indicate that the Sn/Li₂O multilayer composite thin film can be used for tin-based, thin-film, microbatteries and provide motivation to pursue fabrication of Sn–Li₂O anode powder for bulk type batteries.     

Multi-electron storage of photoenergy using Cu2O–TiO2 thin film photocatalyst

UV–vis irradiation of thin films of TiO₂ (ITO/TiO₂) and Cu₂O/TiO₂ (ITO/Cu₂O/TiO₂) coated on conducting glasses generate H₂ from H₂O and once the illumination is ceased, the H₂ production was still noticeable under dark for ITO/Cu₂O/TiO₂ at a lesser production rate for up to 2 h. No such dark reactions were observed for ITO/TiO₂ or TiO₂-coated copper metal foil (Cu/TiO₂). It was noticed that the irradiation of ITO/Cu₂O/TiO₂ leads to formation of trapped electrons and this stored energy leads to generate H₂ from H₂O in the dark.