Detection of H2S,SO2, and NO2 using electrostatic sprayed tungsten oxide films

This paper presents the electrostatic spray deposition of tungsten oxide (WO₃) films for the detection of different pollutant gases. The influence of several types of precursors on the structure and morphology of the films was studied by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. This preliminary study allowed to select the proper precursor for the preparation of pure and porous WO₃ films which offer high gas response (R_air/R_gas=1200) to low concentrations of H₂S (10 ppm) at low operating temperature (200 °C). The gas response to NO₂ and SO₂ is low at this temperature suggesting no possible interference with these two gases during the H₂S detection. Furthermore, the films are able to detect very low concentrations of NO₂ (less than 1 ppm) at 150 °C.     

Low temperature TiO2 rutile phase thin film synthesis by chemical spray pyrolysis (CSP) of titanyl acetylacetonate

Rutile phase TiO₂ thin films have been synthesized using chemical spray pyrolysis of titanyl acetylacetonate TiAcAc in ethanol at 500 °C. The first part of the paper focuses on the thermal decomposition behavior of the precursor by simultaneous thermogravimetry and differential thermal analysis (TG/DTA) coupled with differential scanning calorimetry (DSC). The second part of the paper focuses on the evolution of TiO₂ thin films and their structural transformation with substrate temperature. XRD revealed amorphous TiO₂ thin film at low substrate temperatures (<350 °C) and on high substrate temperatures anatase (3.84 g/cm³) or rutile (4.25 g/cm³) crystalline structure was obtained. The lattice constant, grain size, microstrain and the dislocation density of the film were obtained from the peak width. FTIR spectra of both anatase and rutile TiO₂ revealed stretching vibration of the Ti–O bond for tetrahedral and octahedral surroundings of the titanium atom. Scanning electron micrograph showed the compactness of the rutile film.     

Cr2WO6 nanoparticles prepared by hydrothermal assisted method with selective adsorption properties for methylene blue in water

Cr₂WO₆ nanocrystallites were prepared using a facile hydrothermal assisted process. The microstructures and preferential adsorption performance for methylene blue (MB) of the prepared nanoparticles were investigated using a solid state reaction resulted in Cr₂WO₆ crystallites as a baseline. Their structural information were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectrometer, transmission electron microscopy, N₂–sorption BET surface area, thermogravimetric and differential scanning calorimeters. Results show that the Cr₂WO₆ nanocrystallines with ~50 nm in size are achieved by calcination at 650 °C for only 2 h using a hydrothermal product as precursor, while the micrometer sized Cr₂WO₆ crystallites synthesized by the solid state reaction at higher temperature (950 °C) for at least 20 h. For the as-prepared Cr₂WO₆ nanocrystallines, the adsorption performance were tested using methyl orange (MO), Rhodamine B (RhB) and methylene blue (MB). The adsorption ability was found to be in the order of MB>>RhB>MO owing to electrostatic interactions between the adsorbent and the dye. Results of this study provide a kind of promising alternative adsorbent for color removal from industrial wastewaters.     

Effects of ammonia concentration on property of Cd1−xZnxS films by chemical bath deposition

Cd_1−xZn_xS thin films were grown on soda–lime glass substrates by chemical-bath deposition (CBD) at 80 °C with stirring. All the samples were annealed at 200 °C for 60 min in the air. The crystal structure, surface morphology, thickness and optical properties of the films were studied with transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), step height measurement instrument and spectrophotometer respectively. The results revealed that Cd_1−xZn_xS thin films had cubic crystal structure and the intensity of the diffraction peak increased gradually as ammonia concentration rose and the grain size varied from 5.1 to 8.3 nm. All of Cd_1−xZn_xS thin films had a granular surface with some smaller pores and the average granule sizes increased from 92 to 163 nm with an increase in ammonia concentration. The Cd_1−xZn_xS thin films had the highest transmittance with ammonia concentration of 0.5 M L⁻¹, whose thickness was 50 nm and band gap was 2.62 eV.     

Template free titiania photoanodes modified with carbon black or multi-wall carbon nanotubes: Thermal treatment at low and high temperature for the fabrication of quasi-solid state dye sensitized solar cells

A simple procedure was developed to prepare modified titiania (TiO₂) photoanodes for dye sensitized solar cells at low and high temperature in order to improve overall cell efficiency. Modification of TiO₂ films achieved by the incorporation of either carbon black powder (CBP) or multi-wall carbon nanotubes (MWCNTs). A small quantity of titanium alkoxide was added in a dispersion of titiania (TiO₂) powder consisting of nanoparticles at room temperature, which after alkoxide׳s hydrolysis helps to the connection between titiania (TiO₂) particles and to the formation of mechanically stable relatively thick films on conductive glass substrates. The absence of surfactant allowed us to prepare films at relatively low temperature (~100 °C), while the effect of sintering at a higher temperature (500 °C) was also studied. The structural properties of the films were examined with porosimetry method and microscopy analysis. Better electrical results were obtained for the MWCNT (0.1 wt%) modified TiO₂ films, with 3.14% and 4.68% conversion efficiencies under 1 sun illumination after treatment at 100 °C and 500 °C, respectively. The enhancement in photocurrent for MWCNT-TiO₂ films compared to pure TiO₂ films is attributed to the improved interconnectivity between TiO₂ nanoparticles, which further improved the electron transport through the film. For carbon doped CBP-TiO₂ cells, lower efficiencies were observed compared to pure TiO₂.     

Synthesis of GaN nanowires by ammoniation of Ga2O3 films on Nb layer deposited on Si(1 1 1) substrates

Single-crystalline GaN nanowires have been successfully synthesized on Si(1 1 1) substrates by magnetron sputtering through ammoniation of Ga₂O₃/Nb films at 900 °C in a quartz tube. The as-synthesized GaN nanowires are confirmed to be single-crystalline GaN with wurtzite structure by X-ray diffraction (XRD), selected-area electron diffraction (SAED) and field-emission transmission electron microscopy (FETEM); scanning electron microscopy (SEM) shows that the GaN nanowires are smooth, with diameters of about 50 nm and lengths typically up to several microns, which could provide an attractive potential for incorporation in future GaN electronic devices into Si-based large-scale integrated circuits. Finally, the growth mechanism of GaN nanowires is also briefly discussed.     

Photo-electrochemical and interfacial-process analysis of WO3 nanostructures supported on TiO2: An approach to BPA oxidation

The photo-electrooxidation of bisphenol A (BPA) at the interface of nanostructured materials of TiO₂ and WO₃-TiO₂ was studied under neutral conditions. The tested materials were synthesized via the sol-gel method, and characterized by X-ray diffraction (XRD), UV–Vis diffuse reflectance spectroscopy (DRS), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS); as well as electrochemical techniques. X-ray diffraction indicated the formation of pure anatase phase and the presence of monoclinic WO₃. XRD-HRTEM revealed WO₃ nanoparticles of ca. 5 nm in diameter and anatase nanoparticles of 14.8–24 nm. The XPS analysis confirmed the predominance of WO₃ (W⁶⁺) and TiO₂ (Ti⁴⁺) as an heterostructured couple. The semiconductor properties of the synthesized composites were evaluated in 0.1 M KCl using cyclic voltammetry, linear sweep voltammetry, chronoamperometry and electrochemical impedance spectroscopy (EIS). The electrochemical analysis confirmed the formation of the tungsten-oxide bronze sites, and it is proposed that WO₃–(OH)_ads species are responsible of BPA oxidation. The assays using frequency variation demonstrated that both the flat-band potential and the electrical resistance decrease in the presence of WO₃. The evaluation from linear voltammetry during illumination in visible-light region confirmed that the better performance for BPA oxidation was with nanostructured WO₃-TiO₂ obtaining a faster rate of interfacial electron transfer.     

Synthesis of TiO2 thin films with highly efficient surfaces using a sol–gel technique

Three different strong acid catalysts were used in a simple sol–gel synthesis to produce TiO₂ thin films with increased homogeneity and enhanced photocatalytic activity on their mesoporous surfaces. Various techniques were used to characterize the samples, including UV–visible spectrophotometry, X-ray diffraction, micro-Raman spectrometry, photobleaching, scanning electron microscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The band gaps varied from 3.73 to 3.75 eV and the transmittance was >80%. An anatase phase was obtained in all the samples and the crystal size varied from 20 to 45 nm as a function of the annealing temperature. The increase in the efficiency of the surface of the TiO₂ thin films was evaluated by photodegradation of methylene blue in water. The results showed that the acid catalysts used in the synthesis had an important effect on the morphology and photocatalytic activity of the thin films, resulting in more efficient surfaces. Synthesis with hydrofluoric acid produced thin films with a homogenous mesoporous structure and improved the photodegradation of the methylene blue dye to 92% in 2.5 h.     

Effects of silver substrates on the visible light photocatalytic activities of copper-doped titanium dioxide thin films

Novel copper-doped titanium dioxide (Cu-doped TiO₂) thin films on silver (Ag) substrates with different thicknesses were prepared by sol–gel and magnetron sputtering methods. The influences of the Ag substrate thickness on the morphology and performance of the films were investigated by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, UV–visible spectroscopy, and photocatalytic degradation testing with methylene blue aqueous solution under visible light irradiation. The results indicated that Ag substrates with an optimal thickness of 30 nm not only maintained the tiny nanocrystals but also greatly improved dispersion of the nanoparticles on the surface of the nanofilms. Furthermore, during the calcination process, part of the Ag atoms diffused from the substrates into the Cu–TiO₂ films and substituted for the Cu ions to form Ag–TiO₂. A proper Ag substrate thickness (30 nm) greatly improved the photocatalytic properties of TiO₂ with photocatalytic efficiency, reaching approximately 86% in 300 minutes under visible light irradiation. However, an excess of Ag substrate not only led to the Cu ion separating out in the form of CuO but also resulted in the agglomeration of TiO₂ particles on the surface, which were detrimental to photocatalytic activities.     

WO3/TiO2 nanocomposites: Salt–ultrasonic assisted hydrothermal synthesis and enhanced photocatalytic activity

A series of WO₃/TiO₂ composite photocatalysts were fabricated via a facile salt–ultrasonic assisted hydrothermal process. The obtained samples were characterized by X-ray diffraction, scanning eletron microscopy, energy dispersive X-ray spectroscopy and UV–vis diffused reflectance spectroscopy. It was confirmed that anatase TiO₂ and monoclinic WO₃ coexisted in the composites. The photocatalytic activity of as-prepared WO₃/TiO₂ composites for degradation of Rhodamin B (RhB) under visible light irradiation was investigated. The results showed that WO₃/TiO₂ composites have a higher photocatalytic activity than those of pure TiO₂ and pure WO₃. First-principle calculations based on density functional theory were performed to explore the electronic structure and illustrate the photocatalytic mechanism of WO₃/TiO₂. The calculated energy gap was 2.53 eV, which was close to the experimental observation (2.58 eV). Due to the combination of WO₃/TiO₂, the photoinduced electrons and holes transfer between the WO₃ and TiO₂ in opposite directions, thus providing sufficient charge separation, which contributed to the photocatalytic activity enhancement.     

Influence of Ti film thickness and oxidation temperature on TiO2 thin film formation via thermal oxidation of sputtered Ti film

Single-phase rutile TiO₂ films with good crystallinity were obtained by thermal oxidation of sputtered Ti films on Si and quartz substrates. The influence of the Ti film thickness on oxidation was systematically investigated. A temperature of 823 K was sufficient to fully oxidize Ti films of <0.2 μm in thickness, but 923 K was required for complete oxidation of thicker films. The crystal structure, phase, composition, and optical properties of the TiO₂ films were investigated using X-ray diffraction (XRD), Raman spectroscopy, energy-dispersive X-ray analysis (EDAX), and UV-vis-NIR spectroscopy. XRD and Raman analyses showed that the TiO₂ films are rutile phase. The bandgap of the TiO₂ films decreased with increasing thickness. A growth mechanism for TiO₂ thin films due to thermal oxidation of sputtered Ti films is proposed. Oxidation commences from the surface and proceeds inside the bulk and Ti→TiO₂ phase transformation occurs via different intermediate phases. We found that the oxidation temperature rather than the duration is the dominant factor in the growth of TiO₂ thin films.     

Nanotribological properties of ALD-processed bilayer TiO2/ZnO films

TiO₂/ZnO films grown by atomic layer deposition (ALD) demonstrated nanotribological behaviors using scratch testing. TEM profiles obtained an amorphous structure TiO₂ and nanocrystalline structure ZnO, whereas the sample has significant interface between the TiO₂/ZnO films. The experimental results show the relative XRD peak intensities are mainly contributed by a wurtzite oxide ZnO structure and no signal from the amorphous TiO₂.With respect to tribology, increased friction causes plastic deformation between the TiO₂ and ZnO films, in addition to delamination and particle loosening. The plastic deformation caused by adhesion and/or cohesion failure is reflected in the nanoscratch traces. The pile-up events at a loading penetration of 30 nm were measured at 21.8 μN for RT, 22.4 μN for 300 °C, and 36 μN for 400 °C. In comparison to the other conditions, the TiO₂/ZnO films annealed at 400 °C exhibited higher scratch resistance and friction with large debris, indicating the wear volume is reduced with increased annealing temperature and loading.     

Nitrogen dioxide (NO2) sensing performance of p-polypyrrole/n-tungsten oxide hybrid nanocomposites at room temperature

Polypyrrole (PPy)–tungsten oxide (WO₃) hybrid nanocomposite have been successfully synthesized using different weight percentages of tungsten oxide (10–50%) dispersed in polypyrrole matrix by solid state synthesis method. The sensor based on PPy–WO₃ was fabricated on glass substrate using cost effective spin coating method for detection of NO₂ gas in the low concentration range of 5–100 ppm. The gas sensing performance of hybrid material was studied and compared with those of pure PPy and WO₃. It was found that PPy–WO₃ hybrid nanocomposite sensor can complement the drawbacks of pure PPy and WO₃. The structure, morphology and surface composition properties of PPy–WO₃ hybrid nanocomposites were employed by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The presence of WO₃ in PPy matrix and their interaction was confirmed using XRD, FTIR techniques. The porous surface morphology was observed with addition of WO₃ in PPy matrix which is useful morphology for gas sensing applications. TEM image of PPy–WO₃ hybrid nanocomposites shows the average diameter of 80–90 nm. X-ray photoelectron spectroscopy (XPS) was used to characterize the chemical composition of nanocomposites. It was observed that 50% WO₃ loaded PPy sensor operating at room temperature exhibit maximum response of 61% towards 100 ppm of NO₂ gas and able to detect low concentration of 5 ppm NO₂ gas with reasonable response of 8%. The hybrid sensor shows better sensitivity, selectivity, reproducibility and stability compared to pure PPy and WO₃. The proposed sensing mechanism of hybrid nanocomposite in presence of air and NO₂ atmosphere was discussed with the help of energy band diagram. Furthermore, the interaction of NO₂ gas with PPy–WO₃ hybrid nanocomposites sensor was studied by cole–cole plot using impedance spectroscopy.     

Structural phase-dependent resistivity of intrinsic-extrinsic co-doped transparent titanium dioxide films

The authors report a method of enhancing the conductivity of TiO₂ films by controlling their structural phases. Thin films of Nb:TiO₂ (TNO) were prepared on glass and silicon substrates by RF sputtering with varying Nb content at 200 °C. It is shown that fine control over the structural phases of TiO₂ is critical for achieving low resistivity. The resistivity values of the films doped with oxygen vacancies and Nb⁺⁵ decreased from 3.8 × 10⁻¹ to 4.1 × 10⁻³ Ω cm when the weight percent of rutile in anatase-rutile phase mixture decreases from 52.8% to 32%. Furthermore, the lowest resistivity value of 2.37 × 10⁻³ Ω cm was obtained for the doped TiO₂ films having single phase anatase structure. The physical processes responsible for the diverse electrical properties are discussed and are associated with the growth conditions. Our result indicates that highly conductive doped-TiO₂ film can be obtained by controlling the anatase phase formation via the growth temperature. The obtained results can significantly contribute to the development of transparent electrodes by RF sputtering, a suitable technique for coating large area substrates.     

The effects of carrier gas and substrate temperature on ZnO films prepared by ultrasonic spray pyrolysis

ZnO films were deposited on glass substrates in the temperature range of 350–470 °C under an atmosphere of compressed air or nitrogen (N₂) by using ultrasonic spray pyrolysis technique. Structural, electrical and optical properties of the ZnO films were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), electrical two-probe and optical transmittance measurements. The ZnO films deposited in the range of 350–430 °C were polycrystalline with the wurtzite hexagonal structure having preferred orientation depending on the substrate temperature. The ZnO films deposited below 400 °C had a preferred (100) orientation while those deposited above 400 °C mostly had a preferred (002) orientation. The resistivity values of ZnO films depended on the types of carrier gas. The ZnO thin films deposited under N₂ atmosphere in the range of 370–410 °C showed dense surface morphologies and resistivity values of 0.6–1.1 Ω-cm, a few orders of magnitude lower than those deposited under compressed air. Hydrogen substition in ZnO possibly contributed to decreasing resistivity in ZnO thin films deposited under N₂ gas. The Hall measurements showed that the behavior of ZnO films deposited at 410 °C under the N₂ atmosphere was n-type with a carrier density of 8.9–9.2×10¹⁶ cm^-3 and mobility of ～70 cm²/Vs. ZnO thin films showed transmission values at 550 nm wavelength in a range of 70–80%. The values of band gaps extrapolated from the transmission results showed bandgap shrinkage in an order of milli electron volts in ZnO films deposited under N₂ compared to those deposited under compressed air. The calculation showed that the bandgap reduction was possibly a result of carrier–carrier interactions.     

Synthesis and characterization of TiO2-doped Polyaniline nanocomposites by chemical oxidation method

Polyaniline (PANI)/TiO₂ nanocomposite samples with various dopant percentages of TiO₂ were synthesized at room temperature using a chemical oxidative method. The samples were characterized by ultraviolet-visible spectrometer, Fourier transform infrared (FTIR) spectrometer, X-ray diffraction (XRD), scanning electron microscopy (SEM), EDAX and conductivity measurements. Incorporation of TiO₂ nanoparticles caused a slight red shift at 310 nm in the absorption spectra due to the interactions between the conjugated polymer chains and TiO₂ nanoparticles with π–π^? transition. FTIR confirmed the presence of TiO₂ in the molecular structure. In PANI/TiO₂ composites, two additional bands at 1623 cm^?1 and 1105 cm^?1 assigned to Ti–O and Ti–O^–C stretching modes were present. It can be concluded that Ti organic compounds are formed with an alignment structure of TiO₂ particles. XRD patterns revealed that, as the TiO₂ percentage was increased, the amorphous nature disappeared and the composites became more strongly oriented along the (1 1 0) direction, which showed the tetragonal structure of nanocrystalline TiO₂. SEM studies revealed the formation of uniform granular morphology with average grain size of 200 nm for (50%) PANI/TiO₂ nanocomposite samples.     

Nanocrystalline Bi2S3 thin films grown by thio-glycolic acid mediated successive ionic layer adsorption and reaction (SILAR) technique

Bismuth sulfide (Bi₂S₃) nanocrystalline thin films were deposited on glass substrate by a simple and low-cost thioglycolic-assisted successive ionic layer adsorption and reaction method, using bismuth acetate and thioacetamide as cationic and anionic precursors respectively. Influence of cationic concentration on the structural, optical and electrical properties of Bi₂S₃ thin films were investigated. X-ray diffraction pattern revealed that the prepared Bi₂S₃ thin films are polycrystalline with orthorhombic structure. The surface morphology of Bi₂S₃ thin films examined by atomic force microscopy showed cluster like morphology, and having small hillocks of fairly uniform distribution. Optical studies showed a direct band-to-band transition, and the estimated optical band gap decreases from 1.81 eV to 1.25 eV with the increase in cationic concentration from 0.01 M to 0.03 M. Electrical resistivity measurements by four probe technique revealed negative temperature coefficient of resistance, which confirms the semiconducting nature of Bi₂S₃ thin films. The activation energy of Bi₂S₃ thin films was found to decrease from 0.059 eV to 0.022 eV with the increase in cationic concentration from 0.01 M to 0.03 M, which is attributed to improved grain size and reduction in the defect levels.     

Annealing temperature dependent structural and optical properties of electrodeposited CdSe thin films

Cadmium selenide films were synthesized using simple electrodeposition method on indium tin oxide coated glass substrates. The synthesized films were post annealed at 200 °C, 300 °C and 400 °C. X-ray diffraction of the films showed the hexagonal structure with crystallite size <3 nm for as deposited films and 3–25 nm for annealed films. The surface morphology of films using field emission scanning electron microscopy showed granular surface. The high resolution transmission electron microscopy of a crystallite of the film revealed lattice fringes which measured lattice spacing of 3.13 Å corresponding to (002) plane, indicating the lattice contraction effect, due to small size of CdSe nanocrystallite. The calculation of optical band gap using UV–visible absorption spectrum showed strong red-shift with increase in crystallite size, indicating to the charge confinement in CdSe nanocrystallite.     

Structural and optoelectronic properties of nanostructured TiO2 thin films with annealing

About 480 nm thick titanium oxide (TiO₂) thin films have been deposited by electron beam evaporation followed by annealing in air at 300–600 °C with a step of 100 °C for a period of 2 h. Optical, electrical and structural properties are studied as a function of annealing temperature. All the films are crystalline (having tetragonal anatase structure) with small amount of amorphous phase. Crystallinity of the films improves with annealing at elevated temperatures. XRD and FESEM results suggest that the films are composed of nanoparticles of 25–35 nm. Raman analysis and optical measurements suggest quantum confinement effects since Raman peaks of the as-deposited films are blue-shifted as compared to those for bulk TiO₂ Optical band gap energy of the as-deposited TiO₂ film is 3.24 eV, which decreases to about 3.09 eV after annealing at 600 °C. Refractive index of the as-deposited TiO₂ film is 2.26, which increases to about 2.32 after annealing at 600 °C. However the films annealed at 500 °C present peculiar behavior as their band gap increases to the highest value of 3.27 eV whereas refractive index, RMS roughness and dc-resistance illustrate a drop as compared to all other films. Illumination to sunlight decreases the dc-resistance of the as-deposited and annealed films as compared to dark measurements possibly due to charge carrier enhancement by photon absorption.     

Structural,morphological, electrical and optical studies of Cr doped SnO2 thin films deposited by the spray pyrolysis technique

Tin oxide (SnO₂) and chromium (Cr) doped tin oxide (Cr:SnO₂) thin films were deposited on the preheated glass substrates at 673 K by spray pyrolysis. Concentration of Cr was varied in the solution by adding chromium (III) chloride hexahydrate from 0 to 3 at%. The effect of Cr doping on the structural, electrical and optical properties of tin oxide films is reported. X-ray diffraction pattern confirms the tetragonal crystal structure for undoped and Cr doped tin oxide films. Scanning electron microscopic photographs show the modification of surface morphology of tin oxide film due to varying concentration of Cr. X-ray photoelectron spectra of Cr:SnO₂ (3 at%) thin film revealed the presence of carbon, tin, oxygen, and chromium. Carrier concentration and mobility of the SnO₂ films decrease with increasing concentration of Cr and 0.5 at% Cr doped tin oxide film acquires a mobility of 70 cm²/V s. Average optical transmittance in the 550–850 nm range varies from 38% to 47% with varying Cr concentration in the solution.