Pulsed laser deposition of (MoO3)1 − x(V2O5)x thin films: Preparation, characterization and gasochromic studies

In this study we demonstrate a new composite oxide thin films of (MoO₃)_1 − x(V₂O₅)_x, x = 0, 0.01, 0.03, and 0.05, fabricated by pulsed laser deposition (PLD). The performance of platinum (Pt) catalyst activated hydrogen gas sensor with modified (MoO₃)_1 − x(V₂O₅)_x thin films were investigated. The thickness of the (MoO₃)_1 − x(V₂O₅)_x thin film is about 600-650 nm and its surface has a uniform morphology. Our results show that the gasochromic sensors prepared by (MoO₃)_0.99(V₂O₅)_0.01 thin film exhibited excellent hydrogen sensibility. The response and recovery time are in the range of 9-15 min for coloration and bleaching at room temperature under H₂ atmosphere. The results also show that (MoO₃)_1 − x(V₂O₅)_x/Pt (x = 0.01, 0.03, 0.05) thin films perform better gasochromic capability than the pristine MoO₃/Pt sample.     

Optical properties and aging of gasochromic WO3

The limits of WO₃ as an optical gas sensor were derived by establishing the change in optical constants induced by 2% H₂ in Ar. Using Langmuir's adsorption equation, it was found that at low H₂ concentrations a high sensitivity is predicted, but the coloration could saturate at 57.9% of the material's maximum ion adsorption. The air poisoning problem observed in these devices was shown to be remedied by coating with a permeable polydimethylsiloxane layer, thus eliminating common atmospheric gases as the possible poisoning agents.     

The effect of heat treatment on physical properties of nanograined (WO3)1-x-(Fe2O3)x thin films

Thin films of (WO₃)_1-x-(Fe₂O₃)_x composition were deposited by thermal evaporation on glass substrates and then all samples were annealed at 200-500 °C in air. Optical properties such as transmittance, reflectance, optical bangap energy, and the optical constants of the “as deposited” and the annealed films were studied using ultraviolet-visible spectrophotometry. It was shown that the annealing process changes the film optical properties which were related to Fe₂O₃ concentration. Moreover, using X-ray photoelectron spectroscopy, we have indicated that WO₃ is stoichiometric, while iron oxide was in both FeO and Fe₂O₃ compositions so that the FeO composition converted to Fe₂O₃ after the annealing process. Using atomic force microscopy, it was observed that surface of the “as deposited” films were smooth with a nanometric grain size. The film surface remained unchanged after annealing up to 300 °C. Surface roughness and the grain size of the films with x = 0, 0.05, and 0.75 highly increased at higher annealing temperatures (400 and 500 °C), but were nearly unchanged for medium x-values (0.3 and 0.4).     

Silver loaded WO3 − x/TiO2 composite multifunctional thin films

Multifunctional WO_3 − x-TiO₂ composite thin films have been prepared by sol-gel synthesis and shown to be good visible light photocatalysts whilst retaining a desirable underlying blue colouration. The WO_3 − x-TiO₂ composite thin films were further enhanced using silver nanoparticles synthesised in-situ on the surface from the photo-degradation of silver nitrate solution. Thin films were characterised using X-ray diffraction, Raman, Scanning electron microscopy and UV-visible spectroscopy and shown to photo degrade stearic acid, using white light λ = 420-800 nm.     

Synthesis and structural characterization of (Bi2O3)1?x (Y2O3)x and (Bi2O3)1?x (Gd2O3)x solid solutions

Solid solution series, (Bi₂O₃)_1−x (Y₂O₃)_x and (Bi₂O₃)_1−x (Gd₂O₃)_x, forx = 0.10, 0.20, 0.30 and 0.40 were synthesized by standard ceramic technique. The structural phase characterization was carried out using X-ray powder diffraction technique. It was found that the solid solution containing 20–40 mole% of Y₂O₃ had face-centred cubic structure. All samples of the solid solution series, (Bi₂O₃)_1−x (Gd₂O₃)_x, had rhombohedral single phase in the concentration range 0.10 ≤x ≤ 0.40. Lattice parameters offcc phase of Y₂O₃ doped samples were calculated from the X-ray diffraction data. The lattice constant ‘a’ gradually decreases with increasing content of dopant concentration (x) for the Y₂O₃ doped system and obeys Vegard’s rule. The unit cell parameters for the (Bi₂O₃)_1−x (Gd₂O₃)_x doped samples showing rhombohedral phase were obtained on hexagonal setting.     

On-line monitoring of CO2 quality using doped WO3 thin film sensors

Thin films of either pure or doped tungsten oxide were grown by radiofrequency (rf) sputtering onto silicon micromachined substrates. Up to 7 different dopant materials (noble metals or metal oxides) were deposited by rf sputtering or by evaporation onto the tungsten oxide films. The responsiveness of the resulting micromachined sensors towards sulfur dioxide and hydrogen sulfide was studied. Other pollutants in CO₂ such as ethylene and methane were also tested. It was found that Au-doped tungsten oxide sensors were highly sensitive to H₂S, poorly sensitive to SO₂ and almost insensitive to hydrocarbons. On the other hand, Pt-doped tungsten oxide was highly sensitive to SO₂, poorly responsive to H₂S and nearly insensitive to hydrocarbons. By applying a principal component analysis (PCA), we show that it would be possible to selectively detect traces of H₂S and SO₂ in a CO₂ stream using doped WO₃ microsensors. These sensors could be used in a low-cost analyzer of beverage-grade CO₂.     

A comparison between V2O5 and WO3 thin films as sensitive elements for NO detection

Vanadium oxide (V₂O₅) and tungsten oxide (WO₃) thin films were investigated with the aim to obtain information about their physical and gas sensing properties. The analysis in the presence of different NO concentrations have shown that both materials are able to detect nitrogen oxide, but their responses exhibit different characteristics. In particular, tungsten oxide was found to be more suitable to be used in the field of application for detecting low concentrations. In addition, a mechanism of detection has been considered.     

Analogy for the maximum obtainable colouration between electrochromic, gasochromic, and electrocolouration in DC-sputtered thin WO3−y films

Tungsten oxide films with varied substoichiometry were deposited by reactive DC-sputtering from a W target at different oxygen partial pressures. The inherent maximum achievable electrochemical colouration and electrocolouration were found to be dependent on the oxygen content and consequently on the film substoichiometry. These results were related to those obtained in a previous study by colouration with hydrogen spillover from a catalyst (gasochromic colouration) of films fabricated in the same way. A clear analogy among the colouration by the three different techniques appeared.     

Waveguiding properties of pulsed-laser deposition Ca4GdO(BO3)3 thin films

Waveguiding properties of stoichiometric Ca₄GdO(BO₃)₃ (GdCOB) thin films deposited on quartz substrates by the pulsed-laser deposition (PLD) technique are reported. The optical properties and the anisotropy of the obtained thin films are investigated using the prism-coupling technique. Refractive indices (n_x=1.666, n_y=1.673 and n_z=1.680 at 632.8 nm) were, respectively, determined from the transverse electric (TE) and the transverse magnetic (TM) mode excitations. These values are found to be 3% lower than those of the bulk material, which is likely due to the structural and morphological features of the deposited GdCOB films.     

Reverse resistance switching in polycrystalline Nb2O5 films

The reverse resistance switching is observed in polycrystalline Nb₂O₅ film, which is one of promising candidates for nonvolatile resistance random access memory (ReRAM) devices. This reverse switching is compared with the usual behavior, in which the switching voltage V_LH from low resistance (LR) to high resistance (HR) states is lower than V_HL from HR to LR states. Based on these experiments, we propose a phenomenological mechanism for the resistance switching, which assumes the coexistence of LR and HR phases and the percolation transition.     

Stability and effect of annealing on the optical properties of plasma-deposited Ta2O5 and Nb2O5 films

Tantalum and niobium oxide optical thin films were prepared at room temperature by plasma-enhanced chemical vapor deposition using tantalum and niobium pentaethoxide (M(OC₂H₅)₅) precursors. We studied the evolution of their optical and microstructural properties as a result of annealing over a broad temperature range from room temperature up to 900 °C. The as-deposited films were amorphous; their refractive index, n, and extinction coefficient, k, at 550 nm were n = 2.13 and k < 10^− 4 for Ta₂O₅, and n = 2.24 and k < 10^− 4 for Nb₂O₅. The films contained a small amount of residual carbon (∼ 2-6 at.%) bonded mostly to oxygen. During annealing, the onset of crystallization was observed at approximately T_C1 = 650 °C for Ta₂O₅ and at T_C1 = 450 °C for Nb₂O₅. Upon annealing close to T₁ (300 °C for Nb₂O₅ and 400 °C for Ta₂O₅), n at 550 nm decreased by less than 1%. This was correlated with the decrease of carbon content, as suggested by Fourier transform infrared spectroscopy, elastic recoil detection and static secondary ion mass spectroscopy (SIMS) results. During annealing, we observed phase transition from the δ- (hexagonal) phase to the L- (orthorhombic) phase between 800 °C and 900 °C for Ta₂O₅, and between 600 °C and 700 °C for Nb₂O₅. The structural changes were also marked by silicon diffusion from the substrate into the oxide layer at annealing temperatures above 500 °C for Ta₂O₅ and above 400 °C for Nb₂O₅. As a consequence of oxygen, silicon and metal interdiffusion, the interface between the Si substrate and the metal oxide (Ta₂O₅ or Nb₂O₅) is characterized by its broadening, well documented by spectroscopic ellipsometry and SIMS data.     

An investigation on electrochromic properties of (WO3)1−x-(Fe2O3)x thin films

In this research, the effect of Fe₂O₃ content on the electrochromic properties of WO₃ in thermally evaporated (WO₃)_1−x-(Fe₂O₃)_x thin films (0 ≤ x ≤ 0.4) has been studied. The atomic composition of the deposited metal oxides was determined by X-ray photoelectron spectroscopy analysis. The surface morphology of the thin films has been examined by atomic force microscopy. The surface roughness of all the films was measured about 1.3 nm with an average lateral grain size of 30 nm showing a smooth and nanostructured surface. The electrochromic properties of (WO₃)_1−x-(Fe₂O₃)_x thin films deposited on ITO/glass substrate were studied in a LiClO₄ + PC electrolyte by using ultraviolet-visible spectrophotometry. It was shown that increasing the Fe₂O₃ content leads to reduction of the optical density (ΔOD) of the colored films and also leads to increasing the optimum coloring voltage from 4 to 6 V in which ΔOD shows its maximum values, in our experimental conditions. Furthermore, by using this procedure, it is possible to make an electrochromical filter which behaves similar to the colored WO₃ film in the visible region, while it can be nearly transparent for near-infrared wavelengths, in contrast of the pure colored WO₃ film.     

Thin films of In2O3 by atomic layer deposition using In(acac)3

Thin films of indium oxide have been deposited using the atomic layer deposition (ALD) technique using In(acac)₃ (acac = acetylacetonate, pentane-2,4-dione) and either H₂O or O₃ as precursors. Successful growth using In(acac)₃ is contradictory to what has been reported previously in the literature [J.W. Elam, A.B.F. Martinson, M.J. Pellin, J.T. Hupp, Chem. Mater. 18 (2006) 3571.]. Investigation of the dependence of temperature on the deposition shows windows where the growth rates are relatively unaffected by temperature in the ranges 165–200 °C for In(acac)₃ and H₂O, 165–225 °C for In(acac)₃ and O₃. The growth rates obtained are of the order 20 pm/cycle for In(acac)₃ and H₂O, 12 pm/cycle for In(acac)₃.     

Surface phase transitions upon reduction of epitaxial WO3(1 0 0) thin films

The surface structure and morphology of WO₃(1 0 0) thin films were studied using scanning tunneling microscopy (STM) and low-energy electron diffraction. The films experienced a net-reducing environment when annealed in oxygen at 800 K leading to surface phase transitions from p(2×2) to p(4×2), and from p(4×2) to a mix p(4×2) and p(3×2). Increasing the annealing temperature to 830 K in ultra-high-vacuum (UHV) led to a fully p(3×2) reconstructed surface. Continued UHV annealing above 800 K caused (1×1) islands to appear on the p(3×2) surface and the film color to darken. Eventually, prolonged UHV annealing led to a (1×1)-terminated surface with straight steps oriented in [0 0 1] or [0 1 0] directions due to crystallographic shear planes. The randomly spaced steps on the (1×1) surface indicated variations in the local stoichiometry in the film. An added row model proposed for the p(4×2) structure is also shown to be consistent with the p(3×2) structure. The formation of the p(4×2) structure from the p(2×2) structure was attributed to W⁵⁺ migration into the bulk to form the troughs between the added rows. Reduction of the p(4×2) structure caused the troughs to narrow rather than deepen, suggesting that W⁵⁺ or added row surface diffusion competes with migration of reduced W ions into the bulk when the p(3×2) structure forms. The STM images also show evidence that the (1×1) structure forms through coalescence of the added rows.     

Influence of spray pyrolysis deposition parameters on the optoelectronic properties of WO3 thin films

The electrochromic (EC) properties of tungsten oxide (WO₃), such as coloration efficiency, cyclic durability and reversibility strongly depend on the structural and morphological properties, which are influenced by the deposition method and parameters.This paper presents the steps for optimizing the deposition parameters (substrate temperature, air flow pressure and precursor solution molarity) for improving the optical and electrical properties of WO₃ thin films for EC applications. WO₃ thin films were deposited by spray pyrolysis using tungsten hexachloride (WCl₆) dissolved in ethanol as precursor solution. The EC properties of optimized films were tested in two different electrolytes (H₂SO₄ 1 M and acetic acid/sodium acetate buffer with pH = 4) and changes in structure, composition and morphology of the films after coloration/bleaching cycles were discussed.The deposition temperature, carrier gas pressure and solution molarity were optimized at 250 °C, 120 kPa and 0.14 M respectively. Under these condition a dense, uniform film, with homogenous distribution of particles, good adhesion to the substrate, low roughness (9.02 nm), high transparency (> 70% in the 500-1100 nm range) and conductivity was obtained. Transmission modulation is higher for the sample cycled in H₂SO₄ 1 M (64% at 630 nm) compared to that cycled in the buffer (21% at 630 nm), whereas opposite results were obtained for coloration efficiencies 28 cm² C^− 1 (at 630 nm) and 35 cm² C^− 1 (at 630 nm), respectively. Changes in surface chemistry and morphology of the optimized sample were observed after cycling in H₂SO₄.     

Pulsed laser deposition of Bi2Te3 thin films

A feasibility study of thin stoichiometric Bi₂Te₃ films by pulsed laser deposition (PLD) was performed, the difficulty arising from the differences of vapour pressure between Te and Bi. The films were elaborated using a pulsed Nd:YAG laser under various experimental conditions and were characterized by electron microsprobe, scanning electron microscopy, X-ray diffraction and secondary ion mass spectroscopy analyses. Congruent transfer of stoichiometry occurs from the target to the substrate on several cm² and a good crystallinity can be achieved, even on glass substrates at room temperature, by combining convenient target to substrate facing and distance, respectively. Depletion in Te observed in some films may result from a laser beam-plume interaction that was put forward during elaboration of films on large scale substrates.     

Face-centered cubic (Al1 − xCrx)2O3

We report the discovery of a face-centered cubic (Al_1−xCr_x)₂O₃ solid solution [0.60 < x < 0.70] in films grown onto Si substrates using reactive radio frequency magnetron sputtering from Al and Cr targets at 400 °C. The proposed structure is NaCl-like with 33% vacancies on the metal sites. The unit cell parameter is 4.04 Å as determined by X-ray diffraction. The films have a <100> preferred crystallographic orientation and exhibit hardness values up to 26 GPa and an elastic modulus of 220-235 GPa.     

Investigations of thin film structures of WO3 and WO3 with Pd for hydrogen detection in a surface acoustic wave sensor system

A single thin film sensor structure of WO₃ (∼ 50 nm) and bilayer sensor structure of WO₃ (∼ 50 nm) with a very thin film of palladium (Pd ∼ 18 nm) on the top, have been studied for hydrogen gas-sensing application at ∼ 30 °C and ∼ 50 °C. The structures were obtained by vacuum deposition (first the WO₃ and than the Pd film) onto a LiNbO₃ Y-cut Z-propagating substrate making use of the surface acoustic wave method and additionally (in this same technological processes) onto a glass substrate with a planar microelectrode array for simultaneously monitoring of the planar resistance of the structure. In the case of a bilayer structure a very good correlation has been observed between these two methods — frequency changes in SAW method correlate very well with decreases of the bilayer structure resistance. These frequency changes are on the level of 2.4 kHz to 4% of hydrogen concentration in dry air, whereas in the case of a single WO₃ structure almost no frequency shift is observed.     

Hydrothermal deposition and photochromic performances of three kinds of hierarchical structure arrays of WO3 thin films

Three kinds of tungsten oxide (WO₃) thin films have been fabricated by a simple hydrothermal deposition method. Scanning electron microscopy images of the products revealed that the capping agents did impact the microstructure of WO₃ films. Films prepared without capping agents were ordered nanorod arrays, while the ones obtained with ethanol and oxalic acid revealed peeled-orange-like and cauliflower-like hierarchical structure arrays, respectively. Both of the two hierarchical structures were composed of much thinner nanorods compared with the one obtained without capping agents. All the WO₃ films exhibited good photochromic properties and the two with inducers performed even better, which could be due to the changes in the microstructure that increased the amount of photogenerated electron-hole pairs and the proton diffusion rates.     

Electron beam irradiation-induced reduction of Sn on epitaxial rutile SnxTi1−xO2 alloy thin films

Epitaxially-grown Sn_xTi_1 − xO₂ alloy thin films with different compositions were fabricated by successive deposition of SnO₂ on ultra-smooth Nb-doped TiO₂ (rutile) (110) substrates. The surface Sn atoms of the Sn_xTi_1 − xO₂, which took a tetravalent state just after the deposition under the present condition, were reduced into a metallic state by electron beam irradiation, but not for a pure SnO₂ film. The reduction process approximately obeys zero-order kinetics; the reaction rate constant linearly increases with an increase of the surface composition of Ti. Based on these results, the reduction mechanism is discussed.