Structural and properties of nanocrystalline WO3/TiO2-based humidity sensors elements prepared by high energy activation

Nanocrystalline WO₃/TiO₂-based powders have been prepared by the high energy activation method with WO₃ concentration ranging from 1 to 10 mol%. The samples were thermal treated in a microwave oven at 600 °C for 20 min and their structural and micro-structural characteristics were evaluated by X-ray diffraction, Raman spectroscopy, EXAFS measurements at the Ti K-edge, and transmission electron microscopy. Nitrogen adsorption isotherms and H₂ Temperature Programmed Reduction were also carried out for physical characterization. The crystallite and particle mean sizes ranged from 30 to 40 nm and from 100 to 190 nm, respectively. Good sensor response was obtained for samples with at least 5 mol% WO₃ activated for at least 80 min. Ceramics heat-treated in microwave oven for 20 min have shown similar sensor response as those prepared in conventional oven for 120 min, which is highly cost effective. These results indicate that WO₃/TiO₂ ceramics can be used as a humidity sensor element.     

Influence of Cs doping in spray deposited SnO2 thin films for LPG sensors

Detection of low concentrations of petroleum gas was achieved using transparent conducting SnO₂ thin films doped with 0–4 wt.% caesium (Cs), deposited by spray pyrolysis technique. The electrical resistance change of the films was evaluated in the presence of LPG upon doping with different concentrations of Cs at different working temperatures in the range 250–400 °C. The investigations showed that the tin oxide thin film doped with 2% Cs with a mean grain size of 18 nm at a deposition temperature of 325 °C showed the maximum sensor response (93.4%). At a deposition temperature of 285 °C, the film doped with 3% Cs with a mean grain size of 20 nm showed a high response of 90.0% consistently. The structural properties of Cs-doped SnO₂ were studied by means of X-ray diffraction (XRD); the preferential orientation of the thin films was found to be along the (3 0 1) directions. The crystallite sizes of the films determined from XRD are found to vary between 15 and 60 nm. The electrical investigations revealed that Cs-doped SnO₂ thin film conductivity in a petroleum gas ambience and subsequently the sensor response depended on the dopant concentration and the deposition temperature of the film. The sensors showed a rapid response at an operating temperature of 345 °C. The long-term stability of the sensors is also reported.     

Plasma enhanced-CVD of undoped and fluorine-doped Co3O4 nanosystems for novel gas sensors

Co₃O₄-based nanosystems were prepared on polycrystalline Al₂O₃ by plasma enhanced-chemical vapor deposition (PE-CVD), at temperatures ranging between 200 and 400 °C. The use of two different precursors, Co(dpm)₂ (dpm = 2,2,6,6-tetramethyl-3,5-heptanedionate) and Co(hfa)₂·TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′-tetramethylethylenediamine) enabled the synthesis of undoped and fluorine-doped Co₃O₄ specimens, respectively. A thorough characterization of their properties was performed by glancing incidence X-ray diffraction (GIXRD), atomic force microscopy (AFM), field emission-scanning electron microscopy (FE-SEM), secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS). For the first time, the gas sensing properties of such PE-CVD nanosystems were investigated in the detection of ethanol and acetone. The results show an appreciable response improvement upon doping and functional performances directly dependent on the fluorine content in the Co₃O₄ system.     

Room-temperature CO2 sensing using metal-insulator-semiconductor capacitors comprising atomic-layer-deposited La2O3 thin films

Room temperature detection of CO₂ using metal-insulator-silicon (MIS) devices is reported. These devices comprise atomic layer deposited La₂O₃ thin films as the gas-sensitive dielectric layer and Pt, Pt/Ta and Al as the electrodes. Physical mechanisms that lead to the detection of CO₂ at room temperature are discussed.     

Characterization and humidity sensing properties of Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3 powder synthesized by metal-organic decomposition

Bi_0.5Na_0.5TiO₃-Bi_0.5K_0.5TiO₃ (BNT-BKT) powder is synthesized by a metal-organic decomposition method and characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). A humidity sensor, which is consisted of five pairs of Ag-Pd interdigitated electrodes and an Al₂O₃ ceramic substrate, is fabricated by spin-coating the BNT-BKT powder on the substrate. Good humidity sensing properties such as high response value, short response and recovery times, and small hysteresis are observed in the sensing measurement. The impedance changes more than four orders of magnitude within the whole humidity range from 11% to 95% relative humidity (RH) at 100 Hz. The response time and recovery time are about 20 and 60 s, respectively. The maximum hysteresis is around 4% RH. The results indicate that BNT-BKT powder is of potential applications for fabricating high performance humidity sensors.     

Electrical response of Sm2O3-doped SnO2 to C2H2 and effect of humidity interference

Pure and Sm₂O₃-doped SnO₂ are prepared through a sol–gel method and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The sensor based on 6 wt% Sm₂O₃-doped SnO₂ displays superior response at an operating temperature of 180 °C, and the response magnitude to 1000 ppm C₂H₂ can reach 63.8, which is 16.8 times larger than that of pure SnO₂. This sensor also shows high sensitivity under various humidity conditions. These results make our product be a good candidate in fabricating C₂H₂ sensors.     

Comparative study on TeO2 and TeO3 thin film for γ-ray sensor application

Tellurium trioxide (TeO₃) and tellurium dioxide (TeO₂) thin film has been deposited by rf sputtering. The influence of γ-radiation doses (in the range 10–50 Gy) on the optical and electrical properties of as-deposited films were studied. Optical band gap values were found to decrease with increasing radiation dose whereas electrical conductivity was increased by about five orders in magnitude. Monotonic decrease in the values of dielectric constant for the deposited TeO₃ films with increase in radiation dose was observed. The γ-ray response behavior of TeO₃ and TeO₂ thin films are compared, and TeO₃ thin film is found to be more suitable in amorphous form for γ-ray detection.     

Sprayed CdIn2O4 thin films for liquefied petroleum gas (LPG) detection

Nanocrystalline cadmium indium oxide (CdIn₂O₄) thin films of different thicknesses were deposited by chemical spray pyrolysis technique and utilized as a liquefied petroleum gas (LPG) sensors. These CdIn₂O₄ films were characterized for their structural and morphological properties by means of X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. The dependence of the LPG response on the operating temperature, LPG concentration and CdIn₂O₄ film thickness were investigated. The results showed that the phase structure and the LPG sensing properties changes with the different thicknesses. The maximum LPG response of 46% at the operation temperature of 673 K was achieved for the CdIn₂O₄ film of thickness of 695 nm. The CdIn₂O₄ thin films exhibited good response and rapid response/recovery characteristics to LPG.     

Au-doped WO3-based sensor for NO2 detection at low operating temperature

Pure and Au-doped WO₃ powders for NO₂ gas detection were prepared by a colloidal chemical method, and characterized via X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The NO₂ sensing properties of the sensors based on pure and Au-doped WO₃ powders were investigated by HW-30A gas sensing measurement. The results showed that the gas sensing properties of the doped WO₃ sensors were superior to those of the undoped one. Especially, the 1.0 wt% Au-doped WO₃ sensor possessed larger response, better selectivity, faster response/recovery and better longer term stability to NO₂ than the others at relatively low operating temperature (150 °C).     

Fabrication at wafer level of miniaturized gas sensors based on SnO2 nanorods deposited by PECVD and gas sensing characteristics

SnO₂ nanorods were successfully deposited on 3″ Si/SiO₂ wafers by inductively coupled plasma-enhanced chemical vapour deposition (PECVD) and a wafer-level patterning of nanorods layer for miniaturized solid state gas sensor fabrication were performed. Uniform needle-shaped SnO₂ nanorods in situ grown were obtained under catalyst- and high temperature treatment-free growth condition. These nanorods have an average diameter between 5 and 15 nm and a length of 160-300 nm. The SnO₂-nanorods based gas sensors were tested towards NH₃ and CH₃OH and gas sensing tests show remarkable response, showing promising and repeatable results compared with the SnO₂ thin films gas sensors.     

Structural, optical and electrical properties of CdO/Cd(OH)2 thin films grown by the SILAR method

Successive Ionic Layer Adsorption and Reaction (SILAR) was used to form Cd(OH)₂ thin films from aqueous cadmium–ammonia complex on glass substrates at room temperature and the thermal annealing effect on thin films was studied. The as-deposited films were annealed at 200, 300 and 400 °C for 1 h in an oxygen atmosphere for conversion from Cd(OH)₂ to CdO and change in the structural, optical and electrical properties of the films and the effect of the light on the electrical properties of the films were investigated. The structural and surface morphological properties of the films were studied using X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that Cd(OH)₂ phase is converted into the cubic CdO films by annealing. The band gap energy values of films decreased from 3.59 to 2.13 eV through increasing annealing temperature. It was found that the current increased with increasing light intensity and CdO films were more conductive than the as-deposited films.     

Temperature dependent H2S and Cl2 sensing selectivity of Cr2O3 thin films

The conductometric gas sensing characteristics of Cr₂O₃ thin films - prepared by electron-beam deposition of Cr films on quartz substrate followed by oxygen annealing - have been investigated for a host of gases (CH₄, CO, NO₂, Cl₂, NH₃ and H₂S) as a function of operating temperature (between 30 and 300 °C) and gas concentration (1-30 ppm). We demonstrate that these films are highly selective to H₂S at an operating temperature of 100 °C, while at 220 °C the films become selective to Cl₂. This result has been explained on the basis of depletion of chemisorbed oxygen from the surface of films due to temperature and/or interaction with Cl₂/H₂S, which is supported experimentally by carrying out the work function measurements using Kelvin probe method. The temperature dependent selectivity of Cr₂O₃ thin films provides a flexibility to use same film for the sensing of Cl₂ as well as H₂S.     

Tetrakis(alkylthio)-substituted lutetium bisphthalocyanines for sensing NO2 and O3

In this study, the nitrogen dioxide (NO₂) and ozone (O₃) sensing properties of a series bis[tetrakis(alkylthio) phthalocyaninato] lutetium(III) complexes [(C_nH_2n+1S)₄Pc]₂Lu(III) (n = 6, 10, 16) are investigated as a function of concentration in the temperature range between 25 °C and 150 °C. The concentration ranges were 1–10 ppm for NO₂, and 50 ppb–1 ppm for O₃. The response time and the sensor response to NO₂ are measured for approximately 1 min and 100% ppm⁻¹, respectively, for compound 1 at room temperature. At room temperature, all compounds are in the solid phase. The response time decreases to a few seconds with increasing operation temperature to 150 °C. At this temperature, all compounds are in the liquid crystal phase. The fastest response to oxidizing gases is observed at the liquid crystal phase of the Pcs. It has also been observed that the response time and the sensor response depend on the alkyl chain lengths of the Pcs. The doping effect of oxygen has been determined under high purity nitrogen N₂ flow, after exposure to dry air, at a different period of time and after annealing. It has been found that the conductivities of [(C_nH_2n+1S)₄Pc]₂Lu(III) thin films increased after exposure to dry air and the conduction mechanism also changed from ohmic behavior to space-charge-limited conduction.     

Preparation and characterization of unimorph actuators based on piezoelectric Pb(Zr0.52Ti0.48)O3 materials

This paper describes the preparation and characterization of unimorph actuators for deformable mirrors, based on Pb(Zr_0.52Ti_0.48)O₃ (PZT52) thin film. As comparison, two different designs, where the PZT layer in the unimorph actuators was driven by either interdigitated electrodes (IDT-mode) or parallel plate electrodes (d₃₁-mode), were investigated. The actuators utilize a unimorph membrane (diaphragm) structure consisting of an active PZT piezoelectric layer and a passive SiO₂/Si composite layer. To fabricate the diaphragm structures, n-type (1 0 0) silicon-on-insulator (SOI) wafers with 1 μm thermal SiO₂ were used as substrates (for d₃₁-mode actuators, the upper Si part of SOI need to be heavily doped and used as bottom electrodes simultaneously). Sol-gel derived PZT piezoelectric layers with PbTiO₃ (PT) bufferlayer in total of 0.86 μm were then fabricated on them, and 0.15 μm Al reflective layers were deposited and patterned into top electrode geometries, subsequently. The diaphragms were released using orientation-dependent wet etching (ODE) with 5-10 μm residual silicon layers. The complete unimorph actuators comprise 4 × 4 discrete units (4 mm² in size) with patterned PZT films for parallel plate configuration or 3 × 3 individual pixels (2 mm in IDT diameter) with continuous PZT films in graphic region for IDT configuration. The measurement results indicated that both of the two configurations can generate considerable deflections at low voltage. The measured maximum central deflections at 15 V were approximately 2.5 μm and 2.8 μm, respectively. The intrinsic strain conditions shaping the deflection profiles for the diaphragm actuators were also analyzed. In this paper, the behaviors of clamped parallel plate configuration without a diaphragm were also evaluated.     

Sensing of 2-chloroethyl ethyl sulfide (2-CEES) – a CWA simulant – using pure and platinum doped nanostructured CdSnO3 thin films prepared from ultrasonic spray pyrolysis technique

Nanostructured perovskite CdSnO₃ and Pt-CdSnO₃ thin films were prepared using ultrasonic spray pyrolysis technique. The nozzle (driven by ultrasonic frequency of 120 kHz) fixed on microprocessor controlled motorized arm could move in X–Y direction and spray onto heated (300 °C) glass substrate to give the films of repeatable thickness and microstructure. Structural and microstructural properties of the films were studied using X-ray diffraction and transmission electron microscopy (TEM), respectively. The sensing performance of the films was tested for CWA simulants, such as, CEES (2-chloroethyl ethyl sulfide C₄H₉ClS), DMMP (dimethyl methyl phosphonate C₃H₉O₃P) and CEPS (2-chloroethyl phenyl sulfide C₈H₉ClS). Both CdSnO₃ and Pt-CdSnO₃ showed higher response, better selectivity and faster speed of response to CEES as compared to their responses of DMMP and CEPS. CEES response of Pt-CdSnO₃ is larger than the response of CdSnO₃. The results are discussed and interpreted.     

Fe2O3 modified thick films of nanostructured SnO2 powder consisting of hollow microspheres synthesized from pyrolysis of ultrasonically atomized aerosol for LPG sensing

Nanostructured hollow spheres of SnO₂ with fine nanoparticles were synthesized by ultrasonic atomization. Thick film gas sensors were fabricated by screen printing technique. Different surface modified films (Fe₂O₃ modified SnO₂) were obtained by dipping them into an aqueous solution (0.01 M) of ferric chloride for different intervals of time followed by firing at 500 °C. The structural and microstructural studies of the samples were carried out using XRD, SEM, and TEM. The sensing performance of pure and modified films was studied by exposing various gases at different operating temperatures. One of the modified sample exhibited high response (1990) to 1000 ppm of LPG at 350 °C. Optimum amount of Fe₂O₃ dispersed evenly on the surface_, adsorption and spillover of LPG on Fe₂O₃ misfits and high capacity of adsorption of oxygen on nanostructured hollow spheres may be the reasons of high response.     

Flexible H2 sensor fabricated by layer-by-layer self-assembly of thin films of polypyrrole and modified in situ with Pt nanoparticles

A novel flexible H₂ gas sensor was fabricated by the layer-by-layer (LBL) self-assembly of a polypyrrole (PPy) thin film on a polyester (PET) substrate. A Pt-based complex was self-assembled in situ on the as-prepared PPy thin film, which was reduced to form a Pt-PPy thin film. Microstructural observations revealed that Pt nanoparticles formed on the surface of the PPy film. The sensitivity of the PPy thin film was improved by the Pt nanoparticles, providing catalytically active sites for H₂ gas molecules. The interfering gas NH₃ affected the limit of detection (LOD) of a targeted H₂ gas in a real-world binary gas mixture. A plausible H₂ gas sensing mechanism involves catalytic effects of Pt particles and the formation of charge carriers in the PPy thin film. The flexible H₂ gas sensor exhibited a strong sensitivity that was greater than that of sensors that were made of Pd-MWCNTs at room temperature.     

C-doped WO3 microtubes assembled by nanoparticles with ultrahigh sensitivity to toluene at low operating temperature

Novel C-doped WO₃ microtubes (MTs) were successfully synthesized by a facile infiltration and calcination process using the cotton fibers as templates. The prepared MTs were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), N₂ adsorption and desorption measurements and ultraviolet-visible spectroscopy. XPS spectra show the carbon was doped into the lattice of the WO₃ phase, resulting in a decrease of the band gap of the C-doped WO₃ MTs from 2.45 eV to 2.12 eV. Moreover, the WO₃ MTs were assembled by nanoparticles in size of ca. 40 nm and had larger specific surface area (21.3 m²/g) due to existence of meso/macro-pores inside them. At low operating temperature of 90 °C, the gas sensor based on the C-doped WO₃ MTs had a detected limit of 50 ppb to the toluene gas (response of 2.0). The enhancement of toluene sensing performance of C-doped WO₃ MTs was attributed to a larger surface area and higher porosity, which arises from its unique MTs. Furthermore, the band gap reduction and a new intragap band formation for C-doped WO₃ MTs were proposed as the reason for the decrease in optimal operating temperature.     

Microstructure control of TiO2 nanotubular films for improved VOC sensing

Porous gas sensing films composed of TiO₂ nanotubes were fabricated for the detection of volatile organic compounds (VOCs), such as alcohol and toluene. In order to control the microstructure of TiO₂ nanotubular films, ball-milling treatments were used to shorten the length of TiO₂ nanotubes and to improve the particle packing density of the films without destroying their tubular morphology and crystal structure. The ball-milling treatment successfully modified the porosity of the gas sensing films by inducing more intimate contacts between nanotubes, as confirmed by scanning electron microscopy (SEM) and mercury porosimetry. The sensor using nanotubes after the ball-milling treatment for 3 h exhibited an improved sensor response and selectivity to toluene (50 ppm) at the operating temperature of 500 °C. However, an extensive ball-milling treatment did not enhance the original sensor response, probably owing to a decrease in the porosity of the film. The results obtained indicated the importance of the microstructure control of sensing layers in terms of particle packing density and porosity for detecting large sized organic gas molecules.