Hydrogen gas-sensing with bilayer structures of WO3 and Pd in SAW and electric systems

A bi-layer sensor structure of WO₃ (~ 100 nm) with a very thin film of palladium (Pd~ 18 nm) on the top, has been studied for hydrogen gas-sensing application at ~ 80 °C and ~ 120 °C and low hydrogen concentrations (0.025-1%). The structures were obtained by vacuum deposition (first the WO₃ and then 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 simultaneous monitoring of planar resistance of the structure. A very good correlation has been observed between these two methods — frequency changes in SAW method correlate very well with decreases in the bi-layer structure resistance. The SAW method is faster at the lower interaction temperature such as 80 °C, whereas at an elevated temperature of 120 °C, the electrical planar method is also fast and has a lower limit of detection.     

Response kinetics of a fiber-optic gas sensor using Pt/WO3 thin film to hydrogen

Response kinetics of a fiber-optic hydrogen gas sensor in air- and inert-atmosphere were characterized. The sensor is mainly based on the evanescent field interaction in hydrogen sensitive cladding which is used Platinum-supported tungsten trioxide (Pt/WO₃). When the sensor was exposed to 1 vol.% H₂/air and H₂/N₂ gas, the changes in optical power propagating through the fiber were about 30% and 50%, respectively. The detection limit was about 0.1 vol.% in air-atmosphere. The humidity dependence of the response kinetics was also evaluated. While the response speed in N₂-atmosphere was accelerated, the speed in air-atmosphere was suppressed by the humidity.     

Hydrogen activity tuning of Pt-doped WO3 photonic crystal

A photonic crystal responsive to H₂ has been fabricated by replicating polystyrene colloidal crystal template with WO₃ sol-gel, followed with subsequent Pt sputter-deposition. Under H₂ stimulation, the reflection peak of the photonic crystal rapidly shifted to short wavelength and its intensity declined accordingly. The reflection peak returned to its original location after exposure to oxygen atmosphere. The Pt-WO₃ photonic crystal also exhibited excellent, tunable optical performance with high sensitivity to hydrogen in the range of 100% to 0.1%.     

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.     

Pulsed laser deposition of La0.67Ca0.33MnO3 thin films on LiNbO3 and surface acoustic wave studies

Surface Acoustic Waves on piezoelectric substrates can be used to investigate the dynamic conductivity of thin films in a non-contact and very sensitive way, especially at low conductivities. Here, we report on such surface acoustic wave studies to characterize thin manganite film like La_0.67Ca_0.33MnO₃, exhibiting a Jan Teller effect with a strong electron phonon interaction and a metal insulator transition at high temperatures.

We report on the deposition of La_0.67Ca_0.33MnO₃ on piezoelectric substrates (LiNbO₃ in different crystal cuts, employing a pulsed laser deposition technique. The structural quality of the thin films are examined by X-Ray Diffraction, Scanning Electron Microscope and Energy Dispersive X-ray spectroscopy. For the electrical characterization, we employ the surface acoustic wave technique, accompanied by conventional direct current resistance measurements for comparison.     

Morphological and structural characterization of WO3 and Cr-WO3 thin films synthesized by sol-gel process

WO₃ thin films were prepared by spin-coating methanol solutions of a tungsten chloromethoxide, and easily modified with Cr by the addition of Cr 2-ethylhexanoate. The films were heat-treated up to 700 °C, and characterized by X-ray diffraction, Scanning Electron Microscopy, Transmission Electron Microscopy and Electron Energy Loss spectroscopy. The film morphology was rough and porous, not depending on Cr presence, while their structure was constituted by packed spheroidal or elongated dense structures, giving rise to the peculiar film surface morphology. Cr was distributed in the film structure without phase separations, up to as high as 5% Cr atomic concentration.     

Novel electrochromic devices based on complementary nanocrystalline TiO2 and WO3 thin films

Electrochromic devices were elaborated based on two complementary electrodes made of a nanocrystalline metal oxide thin film deposited on conducting glass. The first electrode holds a 5 μm thick nanocrystalline TiO₂ film derivatized by a monolayer of a phosphonated triarylamine which can be rapidly oxidized by electron transfer to the conducting support followed by charge percolation inside the monolayer. The oxidation in accompanied by a blue coloration due to the absorption band at 730 nm of the stable triarylamminum radical cation. The second electrode bears a 0.2 μm thick nanocrystalline WO₃ film which turns from colorless to blue by reduction and lithium ion insertion. The former electrode reaches an absorbance of at least 3 between 700 and 730 nm after full oxidation (16 mC/cm²) at 1.0 V vs. NHE while for the second, complete reduction at −1.3 V (74 mC/cm²) leads to A=2.4 at 774 nm. An electrochromic device comprising both electrodes separated by an electrolytic solution of 0.1 Li⁺ in 4,7-dioxaoctanitrile reaches an absorbance of 2.2 at 700 nm, 4 s after a voltage step to 1.5 V. The system was shown to sustain at least 14400 coloration-discoloration cycles without degradation.     

Pulsed laser deposition of (WO3)1 − x(Nb2O5)x thin films: Characterization and gasochromic studies

A series of (WO₃)_{1 − x}(Nb₂O₅)_x (x = 0, 0.05, 0.1 and 0.15) mixed oxide films were fabricated by pulsed laser deposition (PLD) at 27 Pa oxygen partial pressure on ITO glass substrates. The thickness of the (WO₃)_{1 − x}(Nb₂O₅)_x thin films is about 350 ± 30 nm and their surface has a uniform morphology. A layer of platinum (Pt) was then sputtered onto the surface of the film. The hydrogen gas sensing performance of Pt catalyst activated (WO₃)_{1 − x}(Nb₂O₅)_x thin films were investigated. The cycling of the coloration was obtained from UV–vis spectra. Gasochromic coloration of (WO₃)_{1 − x}(Nb₂O₅)_x thin films were investigated at room temperature in H₂–N₂ mixtures containing 1–100 mol% of H₂. The results show that the shortest response time of (WO₃)_{1 − x}(Nb₂O₅)_x/Pt hydrogen sensor is within 30 s and the highest transmittance change (ΔT) varies from 20% to 30%.     

Fabrication of defect-free Pd/α-Al2O3 composite membranes for hydrogen separation

Hydrogen production and separation are two important chemical processes. The development of membrane technology has opened up a new possibility for in situ separation of hydrogen from a reaction mixture at elevated temperature in an energy effective way. The availability of a membrane with adequate hydrogen permselectivity and good thermal and mechanical stability is the key for the successful application of membrane technology in hydrogen production and separation. In this paper, a thin-film, defect-free Pd/α-Al₂O₃ composite membrane was fabricated by the electroless plating technique combined with osmosis. The hydrogen permeation performance of the fabricated Pd/α-Al₂O₃ composite membrane was investigated using pure hydrogen at various temperatures from 320–577°C. The hydrogen separation performance was studied using a hydrogen/nitrogen mixture at 467°C. The influence of sweep gas was also investigated.     

Study of photoactivity of tungsten trioxide (WO3) for water splitting

The paper presents the properties of WO₃ films considering the possibility to build a photoelectrochemical cell (PECC) for hydrogen production. The photocurrent response of the PECC containing WO₃/TCO as photoanode and Pt as cathode was analysed. The morphology, crystalline structure and electrical aspects were investigated. Tungsten trioxide (WO₃) thin film with porous morphology and high crystallinity was obtained using the spray pyrolysis deposition technique.     

MIS gas sensors based on porous silicon with Pd and WO3/Pd electrodes

Pd and WO₃/Pd gate metal-oxide-semiconductor (MIS) gas sensitive structures based on porous silicon layers are studied by the high frequency C(V) method. The chemical compositions of composite WO₃/Pd electrodes are characterized by secondary-ion mass spectrometry (SIMS). The atomic force microscopy (AFM) was used for morphologic studies of WO₃/Pd films. As shown in the experiments, WO₃/Pd structures are more sensitive and selective to the adsorption of hydrogen sulphide compared to Pd gate. The analyses of kinetic characteristics allow us to determine the response and characteristic times for these structures. The response time of MIS-structures with thin composite WO₃/Pd electrodes (the thickness of Pd is about 50 nm with WO₃ clusters on its surface) is slower compared to the structures with Pd electrodes. Slower sensor responses of WO₃-based gas sensors may be associated with different mechanism of gas sensitivity of given structures. The enhanced sensitivity and selectivity to H₂S action of WO₃/Pd MIS-structures can also be explained by the chemical reaction that occurs at the catalytic active surface of gate electrodes. The possible mechanisms of enhanced sensitivity and selectivity to H₂S adsorption of MIS gas sensors with WO₃/Pd composite gate electrodes compared to pure Pd have been analyzed.     

Changes in atomic and electronic structures of amorphous WO3 films due to electrochemical ion insertion

The structural changes in amorphous WO₃ films were investigated both on the atomic and electronic levels, and the experimental findings were interpreted using molecular orbital calculations. Electrochemical fast intercalation resulted in the splitting of a peak in the valence band region of the X-ray photoelectron spectrum. This splitting could be attributed to the formation of non-bridging oxygen. Decomposition of WO₆ units into WO₄ units could also be inferred from the data. This decomposition was, however, not responsible for the split of the photoelectron peak. From the population analyses it was found that the average bond strength decreased due to the intercalation, while select WO bonds increased in strength. It was expected that these changes in the chemical bonding character lead to localization of electrons and distortion of WO₆ units, which was consistent with the theoretical interpretations of electrochromism, the intervalence charge transfer model and the small polaron absorption theory.     

新型SnO2/WO3双层薄膜NO2敏感性能研究

采用射频磁控反应溅射锡(Sn)靶和钨(W)靶的方法制备了SnO2/WO3双层薄膜材料,通过XRD和XPS实验研究了双层薄膜的物相结构和组份,结果表明,SnO2/WO3双层薄膜经过热处理后形成了SnWO4化合物.在此基础之上,制作了相应的NO2气体敏感薄膜传感器,研究了双层薄膜传感器的制备工艺参数及工作条件对传感器性能的影响,研究了传感器的敏感特性,包括灵敏度、选择性、响应恢复等特性.结果表明,传感器对NO2气体有较好的敏感性,对其他干扰气体不敏感.     

Influence of effective surface area on gas sensing properties of WO3 sputtered thin films

WO₃ thin films having different effective surface areas were deposited under various discharge gas pressures at room temperature by using reactive magnetron sputtering. The microstructure of WO₃ thin films was investigated by X-ray diffraction, scanning electron microscopy, and by the measurement of physical adsorption isotherms. The effective surface area and pore volume of WO₃ thin films increase with increasing discharge gas pressure from 0.4 to 12 Pa. Gas sensors based on WO₃ thin films show reversible response to NO₂ gas and H₂ gas at an operating temperature of 50-300 °C. The peak sensitivity is found at 200 °C for NO₂ gas and the peak sensitivity appears at 300 °C for H₂ gas. For both kinds of detected gases, the sensor sensitivity increases linearly with an increase of effective surface area of WO₃ thin films. The results demonstrate the importance of achieving high effective surface area on improving the gas sensing performance.     

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).     

Synthesis and characterization of WO3 nanostructures prepared by an aged-hydrothermal method

Nanostructures of tungsten trioxide (WO₃) have been successfully synthesized by using an aged route at low temperature (60 °C) followed by a hydrothermal method at 200 °C for 48 h under well controlled conditions. The material was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Energy Dispersive Spectroscopy (EDS), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Specific Surface Area (S_BET) were measured by using the BET method. The lengths of the WO₃ nanostructures obtained are between 30 and 200 nm and their diameters are from 20 to 70 nm. The growth direction of the tungsten oxide nanostructures was determined along [010] axis with an inter-planar distance of 0.38 nm.     

CO2 and H2 detection with a CHx/porous silicon-based sensor

There has been great interest in the last years in gas sensors based on porous silicon (PS). Recently, a gas sensing device based on a hydrocarbon CH_x/porous silicon structure has been fabricated. The porous samples were coated with hydrocarbon groups deposited in a methane argon plasma. We have experimentally demonstrated that the structure can be used for detecting a low concentration of ethylene, ethane and propane gases [Gabouze N, Belhousse S, Cheraga H. Phy State Solidi (C), in press].In this paper, the CH_x/PS/Si structure has been used as a sensing material to detect CO₂ and H₂ gases. The sensitivity of the devices, response time and impedance response to different gas exposures (CO₂, H₂) have been investigated.The results show that current-voltage and impedance-voltage characteristics are modified by the gas reactivity on the PS/CH_x surface and the sensor shows a rapid and reversible response to low concentrations of the gases studied at room temperature.     

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.     

Surface acoustic wave characterization of a thin, rough polymer film

Laser generated surface acoustic waves (SAW) in a heterodyne diffraction scheme is a powerful technique for elastic characterization of thin films and it is frequently used on samples of high optical quality. We show that the method can also be effectively used in difficult conditions, on rough samples. Measurements are presented on a 3 µm thick film of polymer, spin-coated on steel, and on the same sample after addition of an aluminum coating. The experimental data are interpreted using a model assuming a stack of perfect layers. The analyses show good consistency within the SAW results for both configurations, and consistency with nano-indentation results, cross-validating both approaches.     

Real-time investigation on photocatalytic oxidation of gaseous methanol with nanocrystalline WO3-TiO2 composite films

Here we report on our investigation on photocatalytic oxidation (PCO) of gaseous methanol with WO₃-TiO₂ composite films. WO₃ and WO₃-TiO₂ composite thin films were prepared by drop casting method. PCO of gaseous methanol and hydrogen generation process on platinum loaded WO₃-TiO₂ composite thin films in high vacuum were investigated using a home-made reactor with a six-channel quadrupole mass spectrometer at real-time scale under UVA (300-400 nm) light illumination.In the case of Pt loaded WO₃ thin films, PCO of gaseous methanol proceeds through intermediates viz. formaldehyde, CO and finally to CO₂ and H₂. PCO of gaseous methanol occurs via direct hole transfer over Pt loaded WO₃ thin films. On the other hand, PCO of gaseous methanol over Pt loaded WO₃-TiO₂ composite thin films proceeds with competitive direct and indirect hole transfer reactions. Our real-time analysis of gas phase photocatalysis realized the identification of direct and indirect hole transfer processes and the reaction intermediates thereof.