Effect of electrodeposition and annealing of ZnO on optical and photovoltaic properties of the p-Cu2O/n-ZnO solar cells

Cu₂O/ZnO p–n heterojunction solar cells were fabricated by rf sputtering deposition of n-ZnO layer, followed by electrodeposition of p-Cu₂O layer. The different electrodeposition potentials were applied to deposit Cu₂O on ZnO. The particle size, crystal faces, crystallinity of Cu₂O is important factor which determine the p–n junction interface and consequently their effect on the performance of the heterojunction solar cell. It is observed that at −0.6 V, p-Cu₂O film generates fewer surface states in the interband region due to the termination of [1 1 0] resulting in higher efficiency (0.24%) with maximum particle size (53 nm). The bandgap of Cu₂O at this potential is found to be 2.17 eV. Furthermore, annealing of ZnO film was performed to get rid of deteriorating one and two dimensional defects, which always reduce the performance of solar cell significantly. We found that the solar cell performance efficiency is nearly doubled by increasing the annealing temperature of ZnO thin films due to increasing electrical conductance and electron mobility. Doping studies and fine tuning of the junction morphology will be necessary to further improve the performance of Cu₂O/ZnO heterojunction solar cells.     

Insights into Cu2O thin film absorber via pulsed laser deposition

Cuprous oxide materials are of growing interest for optoelectronic devices and were produced by several chemical and physical methods. Here, we report on the structural, optical, and electrical properties of Cu_xO thin films prepared by the pulsed laser deposition technique. The substrate temperature, as well as the oxygen partial pressure in the deposition chamber, were varied to monitor the copper to oxygen ratio within the deposited films. The growth conditions were carefully optimized to provide the highest conductivity and mobility. Thus, 100 nm thick cuprous oxide films (Cu₂O) deposited at 750 °C exhibited a resistivity of 16 Ω?cm, high mobility of 30 cm²/(V?s), and a bandgap of around 2 eV. The film deposited at the optimized deposition parameters on Nb:STO (001) substrate with Au top electrode showed a photovoltaic response with an open circuit voltage of 0.56 V. These results path the way to efficient solar cells made with Cu₂O films via the pulsed laser deposition technique.     

Performance of Cu2O/ZnO Solar Cell Prepared By Two-Step Electrodeposition

Cu₂O/ZnO solar cells with improved performance were fabricated by an inexpensive two-step process. The process involves potentiostatic deposition of ZnO on NESA glass (tin-oxide-coated glass) followed by galvanostatic deposition of Cu₂O to form Cu₂O/ZnO/NESA solar cells with a short-circuit photocurrent density of 2.08 mA cm⁻²,an open-circuit voltage of 0.19 V, a fill factor of 0.295 and conversion efficiency of 0.117%. The performance of the solar cells thus prepared is discussed in terms of the laminated structure, construction of the heterojunction, and the crystallinity and optical properties of each semiconductor.     

Effect of Al doped ZnO on optical and photovoltaic properties of the p-Cu2O/n-AZO solar cells

Metal oxide thin films have fared so well in the semiconductor industry because of their superior physical, electrical, and optical properties. The applications of these materials in solar cells, biosensors, biomedicine, supercapacitors, photocatalysis, luminous materials, and laser systems are becoming increasingly popular. In this study, the influence of Al concentration on Cu₂O/AZO heterojunction thin films was examined systematically. First, arrays of n-ZnO and AZO rods were produced on an ITO substrate using a hydrothermal technique at 140 °C. Then, using an alkaline cupric lactate solution, a thin films of p-Cu₂O were electrodeposited at 60 °C onto the ZnO arrays. The structure and morphology of the produced materials and the solar cells were studied using X-ray diffraction and scanning electron microscopy. The optical measurements demonstrate a shift in the absorption edge with increasing Al content. Solar cells have been created with a device structure of ITO/ZnO/Cu₂O/Al and ITO/Al-doped ZnO/Cu₂O/Al configurations. The power conversion efficiency (?) of the inorganic solar cell with 6% Al-doped ZnO is ? = 0.282%, which is greater than the ? of the ZnO-based solar cell (? = 0.17%).     

Influence of ZnO buffer layer on AZO film properties by radio frequency magnetron sputtering

Transparent conductive films of Al-doped zinc oxide (AZO) were deposited on glass substrates under various ZnO buffer layer deposition conditions (radio frequency (r.f.) power, sputtering pressure, thickness, and annealing) using r.f. magnetron sputtering at room temperature. This work investigates the influence of ZnO buffer layer on structural, electrical, and optical properties of AZO films. The use of grey-based Taguchi method to determine the ZnO buffer layer deposition processing parameters by considering multiple performance characteristics has been reported. Findings show that the ZnO buffer layer improves the optoelectronic performances of AZO films. The AZO films deposited on the 150-nm thick ZnO buffer layer exhibit a very smooth surface with excellent optical properties. Highly c-axis-orientated AZO/ZnO/glass films were grown. Under the optimized ZnO buffer layer deposition conditions, the AZO films show lowest electrical resistivity of 6.75 × 10⁻⁴ Ω cm, about 85% optical transmittance in the visible region, and the best surface roughness of R_a = 0.933 nm.     

Thermochromic properties of ZnO/VO2/ZnO films on soda lime silicate glass deposited by RF magnetron sputtering

A smart window based on VO₂ is a promising thermochromic (TC) glass that can regulate heat flow through windows by solar modulation near room temperature. TC glasses with high visible-light transmittance and large difference in infrared transmittance between high- and low-temperature VO₂ phases are required to save large amounts of energy in buildings. VO₂-based multilayer films with a buffer layer and/or an anti-reflective (AR) layer are used when the films are deposited by sputtering. In this study, VO₂-based multilayer films were prepared on soda lime glass using ZnO as both the buffer and the AR layers. The structure of the multilayer film was simulated using the optical constants measured from the deposited films. The effect of buffer and AR layers on the TC properties of VO₂-based multilayer films prepared by sputtering was investigated by simulation of the multilayer structure and deposition of the films with the simulated structure. The TC properties were measured and compared with the calculated properties. Improved TC properties (luminous transmittance (T_lum) of ～50%/46% (30 °C/80 °C) and solar modulation ability (ΔT_sol) of ～14%), compared to those without the buffer and AR layer, were obtained from the ZnO/VO₂/ZnO film deposited on glass. The calculated transmittances agree better with the measured ones when the optical constants measured directly from the deposited films are used and the roughnesses of the surface/interface of the multilayer films are considered in the calculation of the optical constants.     

Preparation and optical properties of W-doped VO2/AZO bilayer composite film

In order to improve its visible light transmittance, W-doped VO₂ thin film was prepared with direct current (DC) reactive magnetron sputtering on the surface of Al-doped ZnO (AZO) thin film deposited on quartz glass substrate in advance with radio frequency (RF) magnetron sputtering. The effects of sputtering power for AZO film were investigated on the crystal structures, surface morphologies and optical properties of AZO thin film and W-doped VO₂/AZO bilayer composite film. The results show that the crystallinity of both AZO monolayer film and the bilayer film first increases and then decreases with the increase of sputtering power. As the sputtering power increases, the film thickness increases. The integral visible luminous transmittance (T_lum) of the W-doped VO₂/AZO bilayer film decreases continuously, and the solar modulation efficiency (ΔT_sol) increases first and then decreases. When the sputtering power is 150 W, T_lum and ΔT_sol of W-doped VO₂/AZO bilayer film are 30.14% and 11.95%, 2.77% and 1.71% higher than those of W-doped VO₂ monolayer film, respectively.     

Effect of Cu2O thin film on Cu–Sn alloy coated steel surface in promoting interfacial adhesion with rubber

In the present study, effect of Cu₂O film deposited via successive ionic layer adsorption and corresponding chemical reaction (SILAR method) on Cu–Sn coated steel substrate was explored for the purpose of improving the adhesion of steel with rubber. The effect of the relative alkali concentration in the oxide film deposition bath and the number of immersion cycles on the interfacial adhesion affecting the nature of oxide film deposited, its thickness and surface coverage were investigated. In the current study, Cu–Sn coated steel bead wire with coated surface roughness (R_a) around 2 μm showed an improvement of 33% in adhesion (in terms of pull out force) with an optimum alkali/Cu ion concentration of 25:1 with single dipping cycle attributed to an optimum oxide coating thickness of ~70 nm. Surface morphology study exhibited formation of thicker coating with increase in number of dipping cycles. Satisfactory thermal stability of the Cu₂O film was confirmed as no re-oxidation of the Cu₂O film to CuO was observed in the 200 °C heat treated samples.     

Macroscopically uniform electrodeposited ZnO films on conducting glass by surface tension modification and consequent demonstration of significantly improved p–n heterojunctions

An alternative water–ethanol zinc nitrate solution is demonstrated to completely eliminate macroscopic defects that are normally prevalent in ZnO films electrochemically deposited from aqueous zinc nitrate solutions. The inclusion of 25% ethanol (by volume) reduces the surface tension of the mixture and eliminates bubble formation on the conducting glass surface during deposition. To demonstrate the importance of film uniformity, the ZnO films are employed in ZnO–Cu₂O n–p heterojunctions and an order of magnitude improvement in diode behaviour is observed.     

Transparent and high infrared reflection film having sandwich structure of SiO2/Al:ZnO/SiO2

New transparent and high infrared reflection films having the sandwich structure of SiO₂/Al:ZnO(AZO)/SiO₂ were deposited on the soda-lime silicate glass at room temperature by radio frequency (R.F.) magnetron sputtering. The optical and electrical properties of SiO₂ (110 nm)/AZO (860 nm)/SiO₂ (110 nm) sandwich films were compared with those of single layer AZO (860 nm) films and double layer SiO₂ (110 nm)/AZO (860 nm) films. The results show that these sandwich films exhibit high transmittance of over 85% in the visible light range (380–760 nm), and low reflection rate of below 4.5% in the wavelength range of 350–525 nm, which is not shown in the conventional single layer AZO (860 nm) films and double layer SiO₂ (110 nm)/AZO (860 nm) films. Further these sandwich films display a low sheet resistance of 20 Ω/sq by sheet resistance formula and high infrared reflection rate of above 80% in the wavelength range of 15–25 μm. In addition, the infrared reflection property of these sandwich films is determined mainly by the AZO film. The outer SiO₂ film can diminish the interference coloring and increase transparency; the inner SiO₂ film improves the adhesion of the coating to the glass substrate and prevents Ca²⁺ and Na⁺ in the glass substrate from entering the AZO film.     

Preparation and properties of AZO/PS/AZO tri-layer transparent conductive film with a light-trapping structure

The light-trapping structure is an effective method to increase solar light capture efficiency in the solar cells. In this study, Al-doped ZnO (AZO)/polystyrene (PS)/AZO tri-layer transparent conductive film with light-trapping structure was fabricated by magnetron sputtering and liquid phase methods. The structural, optical and electrical properties of the AZO films could be controlled by different growth conditions. When the sputtering pressure of the under-layer AZO film was 0.2 Pa, the discharge voltage was around 80 V, which was within the optimal process window for obtaining AZO film with high crystallinity. The optimal under-layer AZO film had a large surface roughness and a very low static water contact angle of 75.71°, promoting the relatively uniform distribution of PS spheres. Under this sputtering condition, the prepared AZO/PS/AZO tri-layer film had the highest crystallinity and least point defects. The highest carrier concentration and Hall mobility are 3.0 × 10²¹ cm^-3and 5.39 cm² V^-1 s^-1, respectively. Additionally, a transparent conductive film with the lowest resistivity value (3.88 × 10^-4 Ω cm) and the highest average haze value (26.5%) was obtained by optimizing the process parameters. These properties were comparable to or exceed the reported values of surface-textured SnO₂-based as well as ZnO-based TCOs films, making our films suitable for transparent electrode applications, especially in thin-film solar cells.     

不同衬底上ZnO:Al透明导电薄膜的性能

室温下,采用射频磁控溅射法在玻璃和聚对苯二甲酸乙二醇酯（polyethylene terephthalate,PET）上沉积了掺铝的氧化锌（ZnO：Al,AZO）透明导电薄膜。通过X射线衍射仪分析不同衬底上AZO薄膜的结构,采用四探针测试仪及紫外可见光分光光度计测试薄膜的光电性能。结果表明：沉积在两种衬底上的AZO薄膜都具有六方纤锌矿结构,最佳取向均为[002]方向;玻璃衬底和PET衬底上制备的AZO薄膜的方阻分别为19/sq和45/sq,薄膜透光率均高于90%。实验表明,柔性衬底透明导电氧化物薄膜可以代替硬质衬底透明导电薄膜使电子器件向小型化、轻便化方向发展。     

The Effects of Magnetic Field Size on the Electronic Structure of Al‐Doped ZnO Thin Films Studied by X‐ray Absorption and Emission Spectroscopy

This study examines Al‐doped ZnO (AZO) transparent conductive thin films prepared on glass substrate using the pulsed laser deposition method with an expanding magnetic field perpendicular to the sample surface. O K‐, Zn L₃‐, and Al K‐edge X‐ray absorption near‐edge structure (XANES) and X‐ray emission spectroscopy (XES) were used to investigate the relationship between the effects of magnetic field size and the electronic structure of AZO thin films. Analysis of the XANES spectra showed increasing O 2p states as film resistance decreases, suggesting that the enrichment of the O 2p‐dangling bond along the c‐axis is the main factor affecting the electric performance of AZO thin films. Magnetic field size affects electrons itinerating from Zn atoms to Al sites through O 2p–Zn 3d and O 2p–Al 3sp hybridization and consequently weakens O 2p–Zn 3d hybridization with the downsizing of the crystallite size. XES and XANES spectra of O 2p states at the O K‐edge exhibit that the conduction‐band minimum affects E_g and the valence‐band maximum is nearly unaffected by changes in magnetic field size. Factors affecting the resistance/electric conductivity of AZO thin films are the preferential orientation of (002) along the c‐axis, the thermal/annealing effect accompanied by the changes of magnetic field size, the surface effect, energy bandgap, and the density of unoccupied O 2p‐derived states.     

Microstructure,Surface Morphology and Photoluminescence Properties of Al-Doped ZnO Thin Films Prepared by Plasma Focus Method

Al-doped ZnO (AZO), as one of the most promising transparent conducting oxide (TCO) materials, has now been widely utilized in thin film solar cells. In this research the optimization process of AZO thin films deposited by plasma focus device was carried out by investigation of its physical properties under different deposition conditions for its utilize as a front contact for the Cadmium Telluride (CdTe) based thin film solar cell applications. The effects of number of focus shots and angular position of substrate on the microstructure, surface morphology and photoluminescence properties of the thin films have been systematically studied. X-ray diffraction (XRD) study confirmed the polycrystalline nature of the all deposited AZO thin films. XRD analysis also revealed that crystal structure characteristics of obtained samples strongly depend on deposition conditions (number of shots and angular position). Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses revealed the structure growth and enhancement of surface roughness, with increasing of focus shots or decreasing of angular position. From Photoluminescence (PL) emission spectra, the variations of structural defects and band gap energy for all the AZO thin films prepared under different deposition conditions were also discussed.     

Single step electrosynthesis of Cu2ZnSnS4 (CZTS) thin films for solar cell application

The Cu₂ZnSnS₄ (CZTS) thin films have been electrodeposited onto the Mo coated and ITO glass substrates, in potentiostatic mode at room temperature. The deposition mechanism of the CZTS thin film has been studied using electrochemical techniques like cyclic voltammetery. For the synthesis of these CZTS films, tri-sodium citrate and tartaric acid were used as complexing agents in precursor solution. The structural, morphological, compositional, and optical properties of the CZTS thin films have been studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), EDAX and optical absorption techniques respectively. These properties are found to be strongly dependent on the post-annealing treatment. The polycrystalline CZTS thin films with kieserite crystal structure have been obtained after annealing as-deposited thin films at 550 in Ar atmosphere for 1 h. The electrosynthesized CZTS film exhibits a quite smooth, uniform and dense topography. EDAX study reveals that the deposited thin films are nearly stoichiometric. The direct band gap energy for the CZTS thin films is found to be about 1.50 eV. The photoelectrochemical (PEC) characterization showed that the annealed CZTS thin films are photoactive.     

Influence of argon plasma on the deposition of Al2O3 film onto the PET surfaces by atomic layer deposition

In this paper, polyethyleneterephthalate (PET) films with and without plasma pretreatment were modified by atomic layer deposition (ALD) and plasma-assisted atomic layer deposition (PA-ALD). It demonstrates that the Al₂O₃ films are successfully deposited onto the surface of PET films. The cracks formed on the deposited Al₂O₃ films in the ALD, plasma pretreated ALD, and PA-ALD were attributed to the energetic ion bombardment in plasmas. The surface wettability in terms of water contact angle shows that the deposited Al₂O₃ layer can enhance the wetting property of modified PET surface. Further characterizations of the Al₂O₃ films suggest that the elevated density of hydroxyl -OH group improve the initial growth of ALD deposition. Chemical composition of the Al₂O₃-coated PET film was characterized by X-ray photoelectron spectroscopy, which shows that the content of C 1s reduces with the growing of O 1s in the Al₂O₃-coated PET films, and the introduction of plasma in the ALD process helps the normal growth of Al₂O₃ on PET in PA-ALD.     

Studying the composition and structure of films obtained by thermal oxidation of copper

The composition and structure of copper oxide thin films obtained by thermal oxidation of copper layers with a thickness of 100 nm, deposited onto quartz glass by high-frequency magnetron sputtering, have been studied. The dependences of the film thickness and content of CuO and Cu₂O oxides in it on the temperature–time conditions of thermal treatment are obtained. The studies have shown that depending on the preparation modes, the films can be multiphase and contain different copper oxides, predominantly, CuO and Cu₂O, which possess different bandgaps and p-type conductivity.     

Effects of NIR annealing on the characteristics of al-doped ZnO thin films prepared by RF sputtering

Aluminum-doped zinc oxide (AZO) thin films have been deposited on glass substrates by employing radio frequency (RF) sputtering method for transparent conducting oxide applications. For the RF sputtering process, a ZnO:Al₂O₃ (2 wt.%) target was employed. In this paper, the effects of near infrared ray (NIR) annealing technique on the structural, optical, and electrical properties of the AZO thin films have been researched. Experimental results showed that NIR annealing affected the microstructure, electrical resistance, and optical transmittance of the AZO thin films. X-ray diffraction analysis revealed that all films have a hexagonal wurtzite crystal structure with the preferentially c-axis oriented normal to the substrate surface. Optical transmittance spectra of the AZO thin films exhibited transmittance higher than about 80% within the visible wavelength region, and the optical direct bandgap (E_g) of the AZO films was increased with increasing the NIR energy efficiency.     

Influence of Ca/Al Ratio on Properties of Amorphous/Nanocrystalline Cu–Al–Ca–O Thin Films

This article reports the characterization of thin films sputtered from CuAl_1?xCa_xO targets (x = 0, 0.05, 0.1, 0.15, and 0.2) at room temperature. All films exhibit amorphous/nanocrystalline structures. Their transparency increases slightly with the addition of Ca. Furthermore, the resistivity decreases as the Ca/Al atomic ratio increases. Transmission electron microscopy with energy dispersive spectroscopy mapping indicates that the composition is uniform throughout the films deposited from the highest Ca doping concentration target. Some nanocrystals are present at the top surface of the CuAl_0.8Ca_0.2O thin film as well as the interface region between the CuAl_0.8Ca_0.2O thin film and the glass substrate, whereas the interior of the film is pretty amorphous with some embedded nanocrystals. X‐ray photoelectron spectroscopy shows that the Cu²⁺/Cu⁺ atomic ratio increases with the Ca/Al atomic ratio, indicating the enhancement of p‐type conductivity from the nonisovalent Cu–O alloying.     

A composite poly(3,3-diethyl-3,4-dihydro-2H-thieno-[3,4-b][1,4]-dioxepine) and Pt film as a counter electrode catalyst in dye-sensitized solar cells

A composite poly(3,3-diethyl-3,4-dihydro-2H-thieno-[3,4-b][1,4]-dioxepine) and platinum (PProDOT-Et₂/Pt) film was prepared for using as a counter electrode (CE) catalyst in a dye-sensitized solar cell (DSSC). Four composite films were prepared by electropolymerization of ProDOT-Et₂ on indium tin oxide (ITO) conducting glass, followed by Pt sputtering for 10, 30, 120, and 720 s. The Pt content in the composite film was verified by energy dispersive X-ray spectroscopy (EDX). The composite films possessed three-dimensional (3D) porous structures, as determined by scanning electron microscopy (SEM). The DSSC with the composite film that was subject to 10 s of Pt deposition (PProDOT-Et₂/Pt-10 s) exhibited the highest solar to electricity conversion efficiency (η) of 6.68%, while the cells with the bare polymer film (PProDOT-Et₂) and Pt that was sputtered for 720 s (s-Pt-720 s) demonstrated efficiencies of 4.76% and 6.43%, respectively. The cell photovoltaic parameters were substantiated through dark current, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) analyses. Incident photon-to-current conversion efficiency (IPCE) curves were used to explain the cell photocurrent behaviors.