Synthesis and characterization of CdO-doped nanocrystalline ZnO:TiO2-based H2S gas sensor

This paper reports the preparation and gas-sensing characteristic of ZnO:TiO₂-based hydrogen sulfide (H₂S) gas sensor with different mol% of CdO by polymerized complex method. The structural and gas-sensing properties of ZnO:TiO₂ materials have been characterized using X-ray diffraction and gas-sensing measurement. The electrical resistance response of the sensor based on the materials was investigated at different operating temperatures and different gas concentrations. The sensor with 10 mol% CdO-doped ZnO:TiO₂ shows excellent electrical resistance response toward H₂S gas. The cross sensitivity was also checked for reducing gases like CH₄, CO and H₂ gas. The selectivity and sensitivity of ZnO:TiO₂-based H₂S gas sensor were improved by the addition of 10 mol% of CdO at an operating temperature of 250 °C.     

Nanoporous TiO2 thin film based conductometric H2 sensor

Nanoporous titanium dioxide (TiO₂) based conductometric sensors have been fabricated and their sensitivity to hydrogen (H₂) gas has been investigated. A filtered cathodic vacuum arc (FCVA) system was used to deposit ultra-smooth Ti thin films on a transducer having patterned inter-digital gold electrodes (IDTs). Nanoporous TiO₂ films were obtained by anodization of the titanium (Ti) thin films using a neutral 0.5% (wt) NH₄F in ethylene glycol solution at 5 V for 1 h. After anodization, the films were annealed at 600 °C for 8 h to convert the remaining Ti into TiO₂. The scanning electron microscopy (SEM) images revealed that the average diameters of the nanopores are in the range of 20 to 25 nm. The sensor was exposed to different concentrations of H₂ in synthetic air at operating temperatures between 100 °C and 300 °C. The sensor responded with a highest sensitivity of 1.24 to 1% of H₂ gas at 225 °C.     

Gas sensor based on ordered mesoporous In2O3

We present the preparation of a semiconductor gas sensor based on ordered mesoporous In₂O₃. The In₂O₃ was synthesized by structure replication procedure from cubic KIT-6 silica. A detailed analysis of the morphology of the mesoporous powders as well as of the prepared sensing layer will be shown. Unique properties arise from the synthesis method of structure replication such as well defined porosity in the mesoporous regime and nanocrystallites with high thermal stability up to 450 °C. These properties are useful for the application in semiconducting gas sensors. Test measurements show sensitivity to methane gas in concentrations relevant for explosion prevention.     

Synthesis of size-tunable ZnO nanorod arrays from NH3·H2O/ZnNO3 solutions

Well-aligned crystalline ZnO nanorod arrays were fabricated via an aqueous solution route with zinc nitrate and ammonia as precursors. Dip-coating was firstly utilized to form a ZnO film on ITO substrate as a seed layer for subsequent growth of ZnO nanorods. The effects of NH₃·H₂O/ZnNO₃ molar ratio, ZnNO₃ concentration, growth temperature and time on nanorod morphology were respectively investigated. It was found that the size of nanorod is mainly determined by the molar ratio and concentration. XRD demonstrates that ZnO nanorods are wurtzite crystal structures preferentially orienting in the direction of the c-axis. SEM confirms that ZnO nanorods grew up perpendicular to the substrate. The diameter and length were tunable in a broad range from 80 nm to 500 nm and 250 nm up to 8 μm, respectively. The aspect ratio changed from 3 to 17 mainly dependent on composition of the aqueous solution.     

Nanocrystalline chemically modified CdIn2O4 thick films for H2S gas sensor

CdIn₂O₄ sensor with high sensitivity and excellent selectivity for H₂S gas was synthesized by using sol-gel technique. Structural, electrical and gas sensing properties of doped and undoped CdIn₂O₄ thick films were studied. XRD revealed the single-phase polycrystalline nature of the synthesized CdIn₂O₄ nanomaterials. Since the resistance change of a sensing material is the measure of its response, selectivity and sensitivity was found to be enhanced by doping different concentrations of cobalt in CdIn₂O₄ thick films. The sensor exhibits high response and selectivity toward H₂S for 10 wt.% Co doped CdIn₂O₄ thick films. The current-voltage characteristics of 10 wt.% Co doped CdIn₂O₄ calcined at 650 °C shows one order increase in current with change in the bias voltage at an operating temperature of 200 °C for 1000 ppm H₂S gas.     

Structural and gas sensing behavior of nanocrystalline BaTiO3 based liquid petroleum gas sensors

In this paper nanosized BaTiO₃ thick films based gas sensor has been fabricated for liquid petroleum gas (LPG). Doping with different concentrations of metal oxides influenced the sensitivity of BaTiO₃ thick films for LPG sensor. We present the characterization of both their structural properties by means of X-ray powder diffraction (XRD) and the electrical characteristics by using gas-sensing properties. X-ray powder diffraction analyses revealed the persistence of cubic phase with grain growth 65 nm. The LPG-sensing properties of BaTiO₃ thick films doped with CuO and CdO are investigated. It was found that 10 wt.% CuO: 10 wt.% CdO doped BaTiO₃ based LPG sensor shows better sensitivity and selectivity at an operating temperature 250 °C which is an important commercial range for LPG alarm development. Incorporation of 0.3 wt.% Pd doped CuO:CdO:BaTiO₃ element shows maximum sensitivity with high cross selectivity to the other gases including CO, H₂ and H₂S at an operating temperature 225 °C for low concentrations of LPG sensor.     

A comparative study on the NO2 gas sensing properties of ZnO thin films, nanowires and nanorods

ZnO thin films were fabricated using the spin coating method, ZnO nanowires by cathodically induced sol-gel deposition by the means of an anodic aluminum oxide (AAO) template, and ZnO nanorods with the hydrothermal technique. For thin film preparation, a clear, homogeneous and stable ZnO solution was prepared by the sol-gel method using zinc acetate (ZnAc) precursor which was then coated on a glass substrate with a spin coater. Vertically aligned ZnO nanowires which were approximately 65 nm in diameter and 10 μm in length were grown in an AAO template by applying a cathodic voltage in aqueous zinc nitrate solution at room temperature. For fabrication of the ZnO nanorods, the sol-gel ZnO solution was coated on glass substrate by spin coating as a seed layer. Then ZnO nanorods were grown in zinc nitrate and hexamthylenetetramine aqueous solution. The ZnO nanorods are approximately 30 nm in diameter and 500 nm in length. The ZnO thin film, ZnO nanowires and nanorods were characterized by X-ray diffraction (XRD) analysis and scanning electron microscope (SEM). The NO₂ gas sensing properties of ZnO thin films, nanowires and nanorods were investigated in a dark chamber at 200 °C in the concentration range of 100 ppb-10 ppm. It was found that the response times of both ZnO thin films and ZnO nanorods were approximately 30 s, and the sensor response was depended on shape and size of ZnO nanostructures and electrode configurations.     

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.     

Effect of ZnO doping on morphology and electrochemical properties of sub-micron RuO2 sensing electrode of DO sensor

Thick-film 20 mol% ZnO-doped RuO₂ sensing electrodes (SEs) were fabricated by screen-printing technique on the platinised alumina substrate of the planar electrochemical dissolved oxygen (DO) sensor. The effect of ZnO doping on morphology, electrochemical properties and sensing characteristics of the sensor was investigated. It was found that ZnO doping has not only improved the SE structure, but has also enhanced selectivity of the DO sensor. Selectivity testing exhibited that the presence of Cl⁻, Li⁺, SO₄²⁻, NO³⁻, Ca²⁺, PO₄³⁻, Mg²⁺, Na⁺ and K⁺ with a concentration range of 10⁻⁷ to 10⁻¹ mol/L in the solution had practically no effect on the sensor's emf. The reason in enhancement of the sensor characteristics could be related to the establishment of the better structured SE as more advanced crystallization is achieved for the doped RuO₂-SE.     

Ammonia gas sensor based on PPy/ZnSnO3 nanocomposites

In this paper, Zinc stannate (ZnSnO₃) nanoparticles were synthesized by a sol-gel method. Then, polypyrrole (PPy)/ZnSnO₃ nanocomposites were prepared by a simple in situ chemical polymerization method. By means of X-ray diffraction, Fourier transform infrared and scanning electron microscopy, the microstructure of PPy/ZnSnO₃ nanocomposites was characterized. The XRD patterns indicate that ZnSnO₃ nanoparticles have a perovskite phase with an orthorhombic structure, and incorporation of PPy did not change the crystalline structure of ZnSnO₃. The PPy was evenly dispersed on the surface of ZnSnO₃ particles, which was endorsed by FTIR spectral analyses. SEM images indicate that the PPy was evenly dispersed on the surface of ZnSnO₃ particles without apparent agglomeration. We found that the nanocomposites exhibited a higher response to NH₃ gas.     

H2S sensing properties of La-doped nanocrystalline In2O3

The nanocrystalline powders of pure and La³⁺-doped In₂O₃ with cubic structure were prepared by a simple hydrothermal decomposition route. The structure and crystal phase of the powders were characterized by X-ray diffraction (XRD) and microstructure by transmission electron microscopy (TEM). All the compositions exhibited a single phase, suggesting a formation of solid solution in the concentration of doping investigated. Gas-sensing properties of the sensor elements were tested by mixing a gas in air at static state, as a function of concentration of dopant, operating temperature and concentrations of the test gases. The pure In₂O₃ exhibited high response towards H₂S gas at an operating temperature 150 °C. Doping of In₂O₃ with La³⁺ increases its response towards H₂S and La³⁺ (5.0 wt.% La₂O₃)-doped In₂O₃ showed the maximum response at 125 °C. The selectivity of the sensor elements for H₂S against different reducing gases was studied. The results on response and recovery time were also discussed.     

Fabrication of TiO2/Au nanorod arrays employing a positive sacrificial ZnO template and their electrochromic property

A novel method to fabricate large scale TiO₂/Au nanorod array using a positive sacrificial ZnO template has been developed. This method includes a two-step process, (1) preparation of ZnO/Au nanorod array by a simple low-temperature hydrothermal process, and (2) preparation of TiO₂/Au nanorod array by electrochemically induced sol-gel process. The TiO₂/Au nanorod array has showed a reversible electrochromism in lithium-ion-containing organic electrolyte. The coloration and bleaching throughout a visible range can be switched on and off within a few seconds.     

Low-temperature hydrothermal synthesis of flower-like ZnO microstructure and nanorod array on nanoporous TiO2 film

A novel ZnO architecture, with flower-like microstructure on the top layer and nanorod arrays on the bottom layer, was hydrothermally synthesized on the Fluorine-doped SnO₂ (FTO) conducting glass pre-coated with nanoporous TiO₂ film. The as-prepared architecture was characterized with Field-emission scanning electron microscopy (FE-SEM) and X-ray diffractometer (XRD). Dye-sensitized solar cell studies showed that the power conversion efficiency (η) was 1.26% for this novel ZnO architecture-covered TiO₂ electrode.     

TiO2 nanorod films grown on Si wafers by a nanodot-assisted hydrothermal growth

We report the controlled hydrothermal growth of rutile TiO₂ nanorods on Si wafers by using an anatase TiO₂ nanodot film as an assisted growth layer. The anatase nanodot film was prepared on the wafer by phase-separation-induced self-assembly and subsequent heat-treatment at 500 °C. The nanodots on the wafer were then subjected to hydrothermal treatment to induce the growth of rutile TiO₂ nanorod films. The size and dispersion density of the resulting TiO₂ nanorods could be varied by adjusting the Ti ion concentration in the growth solution. The TiO₂ nanorods were of the rutile phase and grew in the [001] direction. The growth mechanism reveals that the growth of the rutile nanorods was wholly dependent on the existence of rutile TiO₂ seeds, which could be formed by the dissolution-reprecipitation of the anatase nanodots during hydrothermal treatment or under the high-temperature conditions of the subsequent heat-treatment of the as-prepared nanodots. In controlling the rutile nanorod growth, the anatase nanodots show more efficiency than a dense anatase film. Preliminary evaluations of the rutile nanorod films have demonstrated that the wettability changed from highly hydrophobic to superhydrophilic and that the photocatalytic activity was enhanced with increasing nanorod dispersion density.     

Rutile TiO2 nanorod arrays directly grown on Ti foil substrates towards lithium-ion micro-batteries

Nanosized rutile TiO₂ is one of the most promising candidates for anode material in lithium-ion micro-batteries owing to their smaller dimension in ab-plane resulting in an enhanced performance for area capacity. However, few reports have yet emerged up to date of rutile TiO₂ nanorod arrays growing along c-axis for Li-ion battery electrode application. In this study, single-crystalline rutile TiO₂ nanorod arrays growing directly on Ti foil substrates have been fabricated using a template-free method. These nanorods can significantly improve the electrochemical performance of rutile TiO₂ in Li-ion batteries. The capacity increase is about 10 times in comparison with rutile TiO₂ compact layer.     

Substrate engineering of LaAlO3 for non-polar ZnO growth

We demonstrate that growth of non-polar ZnO in a-plane and m-plane can be achieved through substrate engineering of LaAlO₃ with (001) and (112) surface. X-ray diffraction, reflection high energy electron diffraction and cross-sectional transmission electron microscopy with selected area diffraction reveal that a-plane ZnO on LaAlO₃ (001) consists of two types of domains perpendicular to each other with in-plane orientation relationships of [0001]_ZnO // [11?0]_LAO and [11?00]_ZnO // [11?0]_LAO. Single domain epitaxy of m-plane ZnO on LaAlO₃ (112) can be obtained with in-plane orientation relationships of (101?0)_ZnO//(112)_LAO, [0001]_ZnO // [1?10]_LAO and [12?10]_ZnO // [1?1?1]_LAO.     

In2O3 nanowires for gas sensors: morphology and sensing characterisation

Thin and densely packed In₂O₃ nanowires have been synthesised on alumina substrates via transport and condensation method, starting from nanoparticles of indium or palladium as catalysts for the condensation process. Indium catalyst promoted wires growth according to vapour-solid (VS) mechanism, while palladium catalyst leads to wires formation based on vapour-liquid-solid (VLS) condensation. Electron microscopy and related diffraction analysis demonstrated that the wires are monocrystalline, with atomically sharp termination of the lateral sides, and are free from extended defects. The sensing properties of nanowires bundles have been tested to acetone using the flow through technique in the temperature range between 100 and 500 °C.     

TiO2-SnO2 system for gas sensing—Photodegradation of organic contaminants

Catalytic photodegradation of organic contaminants by means of UV light has been demonstrated for gas sensors based on composites of TiO₂-SnO₂. Thin film resistive-type gas sensors of TiO₂-SnO₂ have been deposited at 350 °C by RF sputtering from a Ti-SnO₂ target with varying surface ratio of SnO₂/Ti. Photodegradation experiments of bromothymol blue by UV light have been performed by means of the optical spectrophotometry over the wavelength range extending from 300 nm to 600 nm. The influence of the UV illumination on the sensor response to 100-20,000 ppm of H₂ has been investigated in situ on motor oil contaminated sensors. It has been found that sequential exposures to UV light lead to a partial recovery of the sensor signal to hydrogen.     

Semiconducting BaTiO3-CuO mixed oxide thin films for CO2 detection

A full study of the BaTiO₃-CuO thin-film technology properties as carbon dioxide sensing material is presented. The coatings are deposited by RF-Sputtering and the CO₂ concentration is monitored by impedance measurements. Theoretical foundations are correlated to the experimental results and the principal fabrication and operation parameters are clarified: working temperature and frequency, thickness influence and the introduction of silver as an additive. The BaTiO₃-CuO layer shows higher sensitivity than the actual low-cost commercial CO₂ sensors in the range of the principal applications.