Hydrogen sensing properties of ZnO nanorods: Effects of annealing,temperature and electrode structure

In this study, the hydrogen (H₂) sensing properties of vertically aligned zinc oxide (ZnO) nanorods were investigated depending on annealing, Pd coating, temperature and electrode structure. ZnO nanorods were fabricated by using hydrothermal method on a glass substrate and an indium tin oxide (ITO) coated glass substrate. In order to determine the effects of annealing on the H₂ sensor performance, the nanorods were heated at 500 °C in dry air. H₂ sensing measurements were done in the temperature range of 25–200 °C. It was found that, the sensor response of Pd coated ZnO nanorods were much higher than the un-coated nanorods due to the catalytic effect of Pd thin film. Moreover, the un-annealed samples showed better sensor response than the annealed samples due to the number of oxygen deficiency. In addition, the lateral electrode structure showed higher sensor response than the sandwich electrode structure.     

TiO2 thin films - Influence of annealing temperature on structural, optical and photocatalytic properties

Nanostructured TiO₂ thin films were deposited on glass substrates by sol-gel dip coating technique. The structural, morphological and optical characterizations of the as deposited and annealed films were carried out using X-ray diffraction (XRD), Raman spectroscopy, atomic force microscopy (AFM), and UV-vis transmittance spectroscopy. As-deposited films were amorphous, and the XRD studies showed that the formation of anatase phase was initiated at annealing temperature close to 400 °C. The grain size of the film annealed at 600 °C was about 20 nm. The lattice parameters for the films annealed at 600 °C were a = 3.7862 ? and c = 9.5172 ?, which is close to the reported values of anatase phase. Band gap of the as deposited film was estimated as 3.42 eV and was found to decrease with the annealing temperature. At 550 nm the refractive index of the films annealed at 600 °C was 2.11, which is low compared to a pore free anatase TiO₂. The room temperature electrical resistivity in the dark was of the order of 4.45 × 10⁶ ohm-cm. Photocatalytic activity of the TiO₂ films were studied by monitoring the degradation of aqueous methylene blue under UV light irradiation and was observed that films annealed above 400 °C had good photocatalytic activity which is explained as due to the structural and morphological properties of the films.     

Cu(In,Ga)Se2 solar cells on stainless steel substrates covered with insulating layers

We have developed the flexible Cu(In,Ga)Se₂ (CIGS) solar cells on the stainless steel substrates with the insulating layer for the fabrication of the integrated module. The CIGS films have strong adhesion to the Mo films with insulating layers. An efficiency of 12.3% was achieved by the flexible CIGS solar cell with a structure of ITO/ZnO/CdS/CIGS/Mo/SiO₂/stainless steel. The insertion of the SiO₂ insulating layer did not have an influence on the formation of the CIGS film and solar cell performances.     

Fabricating CdS/BiVO4 and BiVO4/CdS heterostructured film photoelectrodes for photoelectrochemical applications

The photoelectrochemical (PEC) properties of heterostructured CdS/BiVO₄ and BiVO₄/CdS film electrodes on conducting glass for hydrogen production under visible light were investigated. These two types heterostructured film electrodes were prepared using spin coating method and ultrasonic spray pyrolysis method. The structural analyses of the prepared films were determined by using XRD, SEM, EDX and UV–vis. Photoelectrochemical measurements were carried out in a convenient three electrodes cell with 0.5 M Na₂SO₃ aqueous solution. In order to investigate band gap influence of electrode PEC property, a series ITO/Cd_1−xZn_xS/BiVO₄ and ITO/BiVO₄/Cd_1−xZn_xS (x = 0 ∼ 1) film electrodes were also synthesized. After PEC test, a maximum photocurrent density from ITO/CdS/BiVO₄ film electrode was confirmed. The maximum photocurrent density, 3 times and 113 times as that of single CdS film electrode and single BiVO₄ film electrode, respectively. Incident photon to current conversion (IPCE) of as prepared film electrodes were measured and the value were 65% (ITO/CdS/BiVO₄), 22% (single CdS film) and 10% (ITO/BiVO₄/CdS) at 480 nm with 0.3 V external bias. Comparison with ITO/BiVO₄/CdS electrode and single Cd_1−xZn_xS electrodes, the heterostructured ITO/CdS/BiVO₄ electrode can effectively suppress photogenerated electron-hole recombination and enhance light harvesting. Therefore, the ITO/CdS/BiVO₄ electrode gave the maximum photocurrent density and IPCE value.     

TiO2 and TiO2–SiO2 thin films and powders by one-step soft-solution method: Synthesis and characterizations

Simple soft-solution method has been developed to synthesize films and powders of TiO₂ and mixed TiO₂–SiO₂ at relatively low temperatures. This method is simple and inexpensive. Furthermore, reactor can be designed for large-scale applications as well as to produce large quantities of composite powders in a single step. For the preparation of TiO₂, we used aqueous acidic medium containing TiOSO₄ and H₂O₂, which results in a peroxo-titanium precursor while colloidal SiO₂ has been added to the precursor for the formation of TiO₂–SiO₂. Post annealing at 500 °C is necessary to have anatase structure. Resulting films and powders were characterized by different techniques. TiO₂ (anatase) phase with (1 0 1) preferred orientation has been obtained. Also in TiO₂–SiO₂ mixed films and powders, TiO₂ (anatase) phase was found. Fourier transform infrared spectroscopy (FTIR) results for TiO₂ and mixed TiO₂–SiO₂ films have been presented and discussed. The method developed in this paper allowed obtaining compact and homogeneous TiO₂ films. These compact films are highly photoactive when TiO₂ is used as photo anode in an photoelectrochemical cell. Nanoporous morphology is obtained when SiO₂ colloids are added into the solution.     

Effect of under nitrogen annealing on photo-electrochemical characteristics of films deposited from authentic Cu2SnSe3 sources by thermal vacuum under argon gas condensation

This communication describes how annealing under nitrogen affects photo-electrochemical characteristics of films deposited from authentic Cu₂SnSe₃ sources by vacuum evaporation under argon gas (low flow rate 5 cm³/min) using substrate 300 °C. Annealing lowered the photoresponse of the deposited film, by affecting crystallite structure, morphology, composition and pores in the films. Annealing at temperatures in the range 150–350 °C improved crystallinity of the film but lead to pore formation between adjacent, which lowered photoresponse by increased resistance across the electrode/redox interface. Higher temperature (450 °C) annealing lead to SnO₂ formation, as an additional phase, at the expense of Cu₂SnS₃ decomposition. Porosity and mixed phases with SnO₂ presumably increased film internal resistance and resulted in poor charge transfer across the solid/redox couple interface. By affecting film characteristics, annealing lowered photoresponse for the deposited films.     

Nano-structured Cu2O solar cells fabricated on sparse ZnO nanorods

Nano-structured Cu₂O/ZnO nanorod (NR) heterojunction solar cells fabricated on indium tin oxide (ITO)-coated glass are studied. Substrate film and NR density have a strong influence on the preferred growth of the Cu₂O film. The X-ray diffractometer (XRD) analysis results show that highly (2 0 0)-preferred Cu₂O film was formed when plating on plain ITO substrate. However, a highly (1 1 1)-preferred Cu₂O film was obtained when plating on sparse ZnO NRs. SEM, TEM and XRD studies on sparse NR samples indicate that the Cu₂O nano-crystallites mostly initiate its nucleation on the peripheral surfaces of the ZnO NRs, and are also highly (1 1 1)-oriented. Solar cells with ZnO NRs yielded much higher efficiency than those without. In addition, ZnO NRs plated on a ZnO-coated ITO glass significantly improve the shunt resistance and open-circuit voltage (V_oc) of the devices, with consistently much higher efficiency obtained than when ZnO NRs are directly plated on ITO film. However, longer NRs do not improve the efficiency due to low short-circuit current (J_sc) and slightly higher series resistance. The best conversion efficiency of 0.56% was obtained from a Cu₂O/ZnO NRs heterojunction solar cell fabricated on a 80 nm ZnO-coated ITO glass with V_oc=0.514 V, J_sc=2.64 mA/cm² and 41.5% fill factor.     

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.     

Oxidative photoelectrochemical technology with Ti/TiO2 anodes

Rutile and anatase TiO₂ films have been grown on Ti plates by thermal (500–800°C) and anodic oxidation followed by thermal annealing (400–500°C), respectively. The photoelectrochemical efficiency of these photoanodes, evaluated by current density measurements in the photooxidation of 4-methoxybenzyl alcohol in deaerated CH₃CN, has been determined. The photocurrent efficiency increases with the thickness of the TiO₂ rutile film up to 1 μm (the most efficient thickness). At the wavelengths furnished by the irradiation apparatus similar thicknesses of anatase and rutile films show nearly the same efficiencies. Anodic bias produces similar relative increases of current intensity in both crystalline forms.     

Effect of TiO2 photo-electrode growth condition on dye-sensitised solar cells

Titanium dioxide- (TiO₂) based photo-electrode for dye-sensitised solar cells (DSSCs) use is fabricated with the electro-phoretic deposition (EPD) technique on indium-tin-oxide (ITO). TiO₂ films were synthesised at different EPD biases ranging from 70 to 110 V. We correlate the morphological and optical properties of formed films to the electrical characteristics of fabricated DSSCs. In addition, by neglecting the tunnelling and the tunnelling-assisted thermo-ionic currents with respect to the pure thermo-ionic current at the ITO/TiO₂ interface, we evaluate the high potential barrier, e?_B. Investigation of the electrical properties of the formed DSSCs shows a best result when the TiO₂ film is elaborated at 100 V. Furthermore, by taking into account the high band energy of 0.6 eV at an aluminium-based counter electrode/electrolyte interface, we deduce that aluminium reduces drastically the short-circuit current of the DSSC.     

ZnO/CuInS2 core/shell heterojunction nanoarray for photoelectrochemical water splitting

ZnO/CuInS₂ core/shell nanorods array thin film was synthesized on conducting glass substrates for photoelectrochemical water splitting via a simple hydrothermal and cation exchange reaction, using ZnO nanorods array as reactive template. Uniform CuInS₂ films were obtained on the surface of ZnO nanorods, based on the ion-by-ion growth mechanism. The optical property of core/shell nanoarray was characterized, and enhanced absorption spectrum was observed. Hydrogen generation efficiency of 3.2% at 0.29 V versus saturated calomel electrode was achieved with synthesized ZnO/CuInS₂ core/shell nanoarray electrode due to the improved absorption and appropriate energy gap structure. The synthesized core/shell nanoarray has potential application in photoelectrochemical water splitting.     

TiO2 thin films as protective material for transparent-conducting oxides used in Si thin film solar cells

Nb-doped TiO₂ films have been fabricated by RF magnetron sputtering as protective material for transparent-conducting oxide (TCO) films used in Si thin film solar cells. It is found that TiO₂ has higher resistance against hydrogen radical exposure, utilizing the hot-wire CVD (catalytic CVD) apparatus, compared with SnO₂ and ZnO. Further, the minimum thickness of TiO₂ film as protective material for TCO was experimentally investigated. Electrical conductivity of TiO₂ in the as-deposited film is found to be 10⁻⁶ S/cm due to the Nb doping. Higher conductivity of 10⁻² S/cm is achieved in thermally annealed films. Nitrogen treatments of Nb-doped TiO₂ film have been also performed for improvements of optical and electric properties of the film. The electrical conductivity becomes 4.5×10⁻² S/cm by N₂ annealing of TiO₂ films at 500 °C for 30 min. It is found that the refractive index n of Nb-doped TiO₂ films can be controlled by nitrogen doping (from n=2.2 to 2.5 at λ = 550 nm) using N₂ as a reactive gas. The controllability of n implies a better optical matching at the TCO/p-layer interface in Si thin film solar cells.     

Engineering of hybrid interfaces in organic photovoltaic devices

In this study, we engineer and investigate the interface structure and chemistry at the indium tin oxide (ITO) anode (front-side electrode) as well as at the Mg−Ag cathode (back-side electrode) in metal phthalocyanine (MePc)/C₆₀ organic solar cells (OSCs).For the front-side electrode, Zn-phthalocyaninetetraphosphonic acid (Zn-PTPA) and Sn-phthalocyanine axially substituted with tartaric acid (Sn-PTA) have been used for the surface termination of ITO coated glass substrates. Both terminations yielded OSCs with higher fill factors and open circuit voltages, thus increasing the power conversion efficiency by 33% and 67%, respectively. A possible influence of a chemisorbed Zn-PTPA on the film growth of the adjacent ZnPc absorber in the vicinity of the hybrid interface is discussed using X-ray reflectivity and near edge X-ray absorption fine structure data. Distinct effects of the Zn-PTPA and Sn-PTA terminations on the electronic properties of the ITO surface were found by X-ray photoelectron spectroscopy (XPS) measurements at the valence band edge. We demonstrate the possibility to engineer the hybrid interface without additional buffer.For the back-side electrode we report the formation of buffer-free charge carrier selective Mg−Ag cathodes, which are applied for bulk heterojunction organic absorbers consisting of copper phthalocyanine (CuPc) donor and fullerene C₆₀ acceptor materials. The chemical and structural properties of the CuPc:C₆₀/Mg−Ag interface are investigated by element depth profiling using secondary ion mass spectrometry (SIMS), grazing incidence X-ray diffraction analysis (GI-XRD) and XPS.We demonstrate that an optimum charge carrier selectivity is achieved with Mg:Ag/Ag cathode structures, where the Mg:Ag alloy layer has a composition close to that of Ag₃Mg. In addition, Mg diffusion into CuPc:C₆₀ layer is observed. As a result, an interaction between Mg and Cu²⁺ with a concurrent change in oxidation state of both metals takes place. However, no formation of MgPc is observed.The findings of this work are discussed against the background of the performance and electrical properties of the corresponding MePc/C₆₀-based organic solar cells.     

3D-nano-hetero-structured n/n junction,CuO/Ru–ZnO thin films,for hydrogen generation with enhanced photoelectrochemical performances

Hydrogen, derived from solar-water splitting, is a clean and renewable fuel for which per gram energy storage capacity is even higher than fossil fuels. Towards the development of a viable technology for above conversion, this report describes enhanced performance in photoelectrochemical water splitting using uniquely evolved nano-hetero-structured bilayered thin films, CuO/Ru–ZnO as photoanode. Grown over ITO (In:SnO₂) glass substrates by using low-cost and easily up-scalable wet chemical methods, films were characterized for microstructure, optical behaviour and surface characteristics, using XRD and other spectral measurements viz. FESEM, AFM, TEM, UV–Visible Spectroscopy, EDX and XPS. Against monolayered pristine films of CuO and ZnO, bilayered films yielded a major gain in PEC water splitting photocurrent, on being used as working electrode in PEC cell, in conjunction with platinum counter electrode and saturated calomel reference electrode (electrolyte solution 0.1 M NaOH solution, pH 13, temperature 30 ± 3.6 °C). Films with 1% Ru-incorporation yielded highest photocurrent (2.04 mA/cm²). Enhanced photoactivity of bilayered films was found correlated with increments in light absorption, charge carrier density and film surface area, coupled with reduced electrical resistivity. The study highlights an important role played by Ru added in ZnO overlayer, apparently existing as RuO₂ nanoparticles dispersed in ZnO lattice, in hole-transfer from valence band of CuO underlayer to electrolyte, thereby imparting a significant boost on photocurrent generation.     

Synthesis and characterization of nanocrystalline Zn1−xMxO (M = Ni, Cr) thin films for efficient photoelectrochemical splitting of water under UV irradiation

Nanocrystalline thin films of Zn_1−xM_xO (M = Ni, Cr) were deposited on glass substrate by sol-gel method. To a solution of zinc acetate 2-hydrate in dimethyl formamide, calculated quantities of nickel nitrate or chromium acetate were added. The clear solution, obtained after 2 h of continuous stirring, was coated on conducting glass (ITO plates). After preannealing at 250 °C to remove organic impurities, films were sintered at 400, 500 and 600 °C. XRD analysis reveals dominant evolution of hexagonal ZnO with a possible simultaneous growth of meta-stable cubic ZnO. AFM analysis indicated preferential growth of nanocrystallites along c-axis, while SEM analysis confirmed films having uniform morphology. Optical characterization led to two band gap values; one matching with the band gap of bulk ZnO and the second slightly higher, which suggest quantum confinement effect in nanocrystallites. Ni and Cr incorporation influenced the two band gap energies differently. Photoelectrochemical (PEC) splitting of water was attempted, using prepared thin films as working electrode, in conjunction with Pt counter electrode and saturated calomel reference electrode along with 150 W Xenon Arc light source and aqueous solution of NaOH (0.01 M). Results indicate Ni:ZnO films yielding improved photoresponse compared to Cr:ZnO films. Ni:ZnO (5 % at.) films sintered at 600 °C resulted in significantly enhanced photocurrent due to improved optical absorption and decrease in resistivity.     

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.     

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.     

Comprehensive evaluation of ITO thick films produced under optimum annealing conditions

Indium-tin-oxide (ITO) is a transparent semiconductor that can be formed so that it exhibits a very low resistivity. The applications of this material include solar cells, photodetectors, and transparent contacts for devices such as flat panel displays, and touch sensitive cathode ray tube screens. The authors have investigated the role of both vacuum and reducing atmosphere (N₂ + H₂) annealing on the properties of thick film ITO. Both vacuum annealing and forming gas (N₂ + H₂) annealing result in films with significantly lower resistivity than unannealed films. Samples with sheet resistances of 150 Ω/square have been produced. These values are the lowest reported to date for ITO thick films. Optical characterization including transmission and reflectivity have been conducted, as well as examination of the conductivity as a function of temperature.     

Physically and chemically synthesized TiO2 composite thin films for hydrogen production by photocatalytic water splitting

TiO₂ thin films have been synthesized by radio-frequency magnetron sputtering and sol–gel method to study the hydrogen generation by photocatalytic water splitting under visible light irradiation. Photoelectrochemical cell with chemical bias, involving photo-anode in form of TiO₂ film deposited on conducting indium tin oxide (ITO) film and Pt as cathode, is developed. The effect of conducting ITO layer on photo-voltage is studied by varying the thickness of ITO films. Constant H₂ generation rate is obtained for long period of time by both the TiO₂ films because of the separated evolution of H₂ and O₂ gas, thus eliminating the back-reaction effect. Sputter-deposited film as compared to sol–gel-synthesized film showed better H₂ generation rate, mainly explained in terms of the higher visible light absorption achieved by oxygen vacancies created in the TiO₂ film by the energetic target ions during deposition in pure Ar gas pressure.     

Photovoltage enhancement of dye sensitised solar cells by using ZnO modified TiO2 electrode

Abstract

A ZnO modified TiO₂ (ZnO/TiO₂) film was prepared by immersing TiO₂ electrodes in Zn(Ac)₂ aqueous solution. The open circuit voltage of a dye sensitised solar cell (DSSC) with the ZnO/TiO2 film electrode has a dramatic enhancement, compared to the DSSC with the TiO₂ film electrode. However, the short circuit current density of the DSSC with the ZnO/TiO₂ film electrode is lower than that with TiO₂ electrode. The film electrodes were characterised by SEM, EDX and UV-vis, and the photoelectric performance of DSSCs were measured. The photovoltage enhancement is attributed to the formation of a flat-band potential energy barrier by ZnO at TiO₂/electrolyte interface. The decline of the photocurrent with ZnO/TiO₂ film electrode is due to poor dye absorption on larger particles of ZnO.