Micro-electronic gas sensor devices were developed for the detection of carbon monoxide (CO), nitrogen oxides (NOx), ammonia (NH3), and formaldehyde (HCHO), as well as binary mixed-gas systems. Four gas sensing materials for different target gases, Pd-SnO2 for CO, In2O3 for NOx, Ru-WO3 for NH3, and SnO2-ZnO for HCHO, were synthesized using a sol-gel method, and sensor devices were then fabricated using a micro sensor platform. The gas sensing behavior and sensor response to the gas mixture were examined for six mixed gas systems using the experimental data in MEMS gas sensor arrays in sole gases and their mixtures. The gas sensing behavior with the mixed gas system suggests that specific adsorption and selective activation of the adsorption sites might occur in gas mixtures, and allow selectivity for the adsorption of a particular gas. The careful pattern recognition of sensing data obtained by the sensor array made it possible to distinguish a gas species from a gas mixture and to measure its concentration.

The gas sensor is essential to monitoring dangerous gases in our environment. Metal oxide (MO) gas sensors are primarily utilized for flammable, toxic and organic gases and O3 because of their high sensitivity, high response and high stability. Tungsten oxides (WO3) have versatile applications, particularly for gas sensor applications because of the wide bandgap and stability of WO3. Nanosize WO3 are synthesized using the hydrothermal method. Asprepared WO3 nanopowders are in the form of nanorods and nanorulers. The crystal structure is hexagonal tungsten bronze (MxWO3, x =< 0.33), characterized as a tunnel structure that accommodates alkali ions and the phase stabilizer. A gas detection test reveals that WO3 can detect acetone, butanol, ethanol, and gasoline. This is the first study to report this capability of WO3.

In2O3 doped WO3 powders were prepared by a polymer solution route and their NO2 gas sensing properties were analyzed. The synthesized powders showed nano-sized particles with specific surface areas of 6.01~21.5 m2/g and the particle size and shape changed according to the content of In2O3. The gas sensors fabricated with the synthesized powders were tested at operating temperatures of 400~500 oC and 100~500 ppm concentrations of NO2 atmosphere. The particle size and In2O3 content affected on the initial sensor resistance in an air atmosphere. The highest sensitivity (8.57 at 500 oC), which was 1.77 higher than the sensor consisting of the pure WO3 sample, was measured in the 0.5 mol% In2O3 doping sample. In addition, the response time and recovery time were improved by the addition of In2O3.

Tin dioxide nanoparticles are prepared using a newly developed synthesis method of plasma-assisted electrolysis. A high voltage is applied to the tin metal plate to apply a high pressure and temperature to the synthesized oxide layer on the metal surface, producing nanoparticles in a low concentration of sulfuric acid. The particle size, morphology, and size distribution is controlled by the concentration of electrolytes and frequency of the power supply. The as-prepared powder of tin dioxide nanoparticles is used to fabricate a gas sensor to investigate the potential application. The particle-based gas sensor exhibits a short response and recovery time. There is sensitivity to the reduction gas for the gas flowing at rates of 50, 250, and 500 ppm of H2S gas.

Polyacrylonitrile/pitch nanofibers were prepared by electrospinning as a precursor for a gas sensor material. Pitch nanofibers were properly fabricated by incorporating polyacrylonitrile as an electrospinning supplement component. Polyacrylonitrile/pitch nanofibers were activated with steam at various temperatures followed by subsequent carbonization to make carbon nanofibers with a highly conductive graphitic structure. Steam activation was effective in facilitating gas adsorption onto the carbon nanofibers due to the increased surface area. The carbon nanofibers activated at 800°C had a larger surface area and a lower micro pore fraction resulting in a higher variation in electrical resistance for improved CO gas sensing properties.

Activated carbon fiber (ACF) surfaces are modified using an electron beam under different aqueous solutions to improve the NO gas sensitivity of a gas sensor based on ACFs. The oxygen functional group on the ACF surface is changed, resulting in an increase of the number of non-carbonyl (-C-O-C-) groups from 32.5% for pristine ACFs to 39.53% and 41.75% for ACFs treated with hydrogen peroxide and potassium hydroxide solutions, respectively. We discover that the NO gas sensitivity of the gas sensor fabricated using the modified ACFs as an electrode material is increased, although the specific surface area of the ACFs is decreased because of the recovery of their crystal structure. This is attributed to the static electric interaction between NO gas and the non-carbonyl groups introduced onto the ACF surfaces.

We present the rectifying and nitrogen monoxide (NO) gas sensing properties of an oxide semiconductor heterostructure composed of n-type zinc oxide (ZnO) and p-type copper oxide thin layers. A CuO thin layer was first formed on an indium-tin-oxide-coated glass substrate by sol-gel spin coating method using copper acetate monohydrate and diethanolamine as precursors; then, to form a p-n oxide heterostructure, a ZnO thin layer was spin-coated on the CuO layer using copper zinc dihydrate and diethanolamine. The crystalline structures and microstructures of the heterojunction materials were examined using X-ray diffraction and scanning electron microscopy. The observed current-voltage characteristics of the p-n oxide heterostructure showed a non-linear diode-like rectifying behavior at various temperatures ranging from room temperature to 200 oC. When the spin-coated ZnO/CuO heterojunction was exposed to the acceptor gas NO in dry air, a significant increase in the forward diode current of the p-n junction was observed. It was found that the NO gas response of the ZnO/CuO heterostructure exhibited a maximum value at an operating temperature as low as 100 oC and increased gradually with increasing of the NO gas concentration up to 30 ppm. The experimental results indicate that the spin-coated ZnO/CuO heterojunction structure has significant potential applications for gas sensors and other oxide electronics.

Impedancemetric NOx (NO and NO2) gas sensors were designed with a stacked-layer structure and fabricated using LaCrxCo1-xO3 (x = 0, 0.2, 0.5, 0.8 and 1) as the receptor material and Li1.3Al0.3Ti1.7(PO4)3 plates as the solid-electrolyte transducer material. The LaCrxCo1-xO3 layers were prepared with a polymeric precursor method that used ethylene glycol as the solvent, acetyl acetone as the chelating agent, and polyvinylpyrrolidone as the polymer additive. The effects of the Co concentration on the structural, morphological, and NOx sensing properties of the LaCrxCo1-xO3 powders were investigated with powder Xray diffraction, field emission scanning electron microscopy, and its response to 20~250 ppm of NOx at 400 oC (for 1 kHz and 0.5 V), respectively. When the as-prepared precursors were calcined at 700 oC, only a single phase was detected, which corresponded to a perovskite-type structure. The XRD results showed that as the Co concentration of the LaCrxCo1-xO3 powders increased, the crystal structure was transformed from an orthorhombic phase to a rhombohedral phase. Moreover, the LaCrxCo1-xO3 powders with 0 ≤ x < 0.8 had a rhombohedral symmetry. The size of the particles in the LaCrxCo1-xO3 powders increased from 0.1 to 0.5 μm as the Co concentration increased. The sensing performance of the stack-structured LaCrxCo1-xO3/Li1.3Al0.3Ti1.7(PO4)3 sensors was found to divide the impedance component between the resistance and capacitance. The response of these sensors to NO gas was more sensitive than that to NO2 gas. Compared to other impedancemetric sensors, the LaCr0.8Co0.2O3/Li1.3Al0.3Ti1.7(PO4)3 sensor exhibited good reversibility and reliable sensingresponse properties for NOx gases.

We present the detection characteristics of nitrogen monoxide(NO) gas using p-type copper oxide(CuO) thin film gas sensors. The CuO thin films were fabricated on glass substrates by a sol-gel spin coating method using copper acetate hydrate and diethanolamine as precursors. Structural characterizations revealed that we prepared the pure CuO thin films having a monoclinic crystalline structure without any obvious formation of secondary phase. It was found from the NO gas sensin measurements that the p-type CuO thin film gas sensors exhibited a maximum sensitivity to NO gas in dry air at an operating temperature as low as 100 oC. Additionally, these CuO thin film gas sensors were found to show reversible and reliable electrical response to NO gas in a range of operating temperatures from 60 oC to 200 oC. It is supposed from these results that the ptype oxide semiconductor CuO thin film could have significant potential for use in future gas sensors and other oxide electronics applications using oxide p-n heterojunction structures.

We developed a high-performance methane gas sensor based on a SnO2 hollow hemisphere array structure of nano-thickness. The sensor structures were fabricated by sputter deposition of Sn metal over an array of polystyrene spheres distributed on a planar substrate, followed by an oxidation process to oxidize the Sn to SnO2 while removing the polystyrene template cores. The surface morphology and structural properties were examined by scanning electron microscopy. An optimization of the structure for methane sensing was also carried out. The effects of oxidation temperature, film thickness, gold doping, and morphology were examined. An impressive response of ~220% was observed for a 200 ppm concentration of CH4 gas at an operating temperature of 400˚C for a sample fabricated by 30 sec sputtering of Sn, and oxidation at 800˚C for 2 hr in air. This high response was enabled by the open structure of the hemisphere array thin films.

We report the effect of the fabric of the surface microstructure on the CO gas sensing properties of SnO2 thin films deposited on self-assembled Au nanodots (SnO2/Au) that were formed on SiO2/Si substrates. We characterized structural and morphological properties, comparing them to those of SnO2 thin films deposited directly onto SiO2/Si substrates. We observed a significant enhancement of CO gas sensing properties in the SnO2/Au gas sensors, specifically exhibiting a high maximum response at 200˚C and quite a low detection limit of 1 ppm level in dry air. In particular, the response of the SnO2/Au gas sensor was found to reach the maximum value of 32.5 at 200˚C, which is roughly 27 times higher than the response (~1.2) of the SnO2 gas sensor obtained at the same operating temperature of 200˚C. Furthermore, the SnO2/Au gas sensors displayed very fast response and recovery behaviors. The observed enhancement in the CO gas sensing properties of the SnO2/Au sensors is mainly ascribed to the formation of a nanostructured morphology in the active SnO2 layer having a high specific surface-reaction area by the insertion of a nanodot form of Au nucleation layer.

We report the nitrogen monoxide (NO) gas sensing properties of p-type CuO-nanorod-based gas sensors. We synthesized the p-type CuO nanorods with breadth of about 30 nm and length of about 330 nm by a hydrothermal method using an as-deposited CuO seed layer prepared on a Si/SiO2 substrate by the sputtering method. We fabricated polycrystalline CuO nanorod arrays at 80˚C under the hydrothermal condition of 1:1 morality ratio between copper nitrate trihydrate [Cu(NO2)2·3H2O] and hexamethylenetetramine (C6H12N4). Structural characterizations revealed that we prepared the pure CuO nanorod array of a monoclinic crystalline structure without any obvious formation of secondary phase. It was found from the gas sensing measurements that the p-type CuO nanorod gas sensors exhibited a maximum sensitivity to NO gas in dry air at an operating temperature as low as 200˚C. We also found that these CuO nanorod gas sensors showed reversible and reliable electrical response to NO gas at a range of operating temperatures. These results would indicate some potential applications of the p-type semiconductor CuO nanorods as promising sensing materials for gas sensors, including various types of p-n junction gas sensors.

We present an easy method of preparing two-dimensional (2D) periodic hollow tin oxide (SnO2) hemisphere array gas sensors using polystyrene (PS) spheres as a template. The structures were fabricated by the sputter deposition of thin tin (Sn) metal over an array of PS spheres on a planar substrate followed by calcination at an elevated temperature to oxidize Sn to SnO2 while removing the PS template cores. The SnO2 hemisphere array structures were examined by scanning electron microscopy and X-ray diffraction. The structures were calcined at various temperatures and their sensing properties were examined with varying operation temperatures and concentrations of nitric oxide (NO) gas. Their gas-sensing properties were investigated by measuring the electrical resistances in air and the target gases. The measurements were conducted at different NO concentrations and substrate temperatures. A minimum detection limit of 30 ppb, showing a sensitivity of S = 1.6, was observed for NO gas at an operation temperature of 150˚C for a sample having an Sn metal layer thickness corresponding to 30 sec sputtering time and calcined at 600˚C for 2 hr in air. We proved that high porosity in a hollow SnO2 hemisphere structure allows easy diffusion of the target gas molecules. The results confirm that a 2D hollow SnO2 hemisphere array structure of micronmeter sizes can be a good structural morphology for high sensitivity gas sensors.

We investigated the detection properties of nitrogen monoxide (NO) gas using transparent p-type CuAlO2 thin film gas sensors. The CuAlO2 film was fabricated on an indium tin oxide (ITO)/glass substrate by pulsed laser deposition (PLD), and then the transparent p-type CuAlO2 active layer was formed by annealing. Structural and optical characterizations revealed that the transparent p-type CuAlO2 layer with a thickness of around 200 nm had a non-crystalline structure, showing a quite flat surface and a high transparency above 65 % in the range of visible light. From the NO gas sensing measurements, it was found that the transparent p-type CuAlO2 thin film gas sensors exhibited the maximum sensitivity to NO gas in dry air at an operating temperature of 180˚C. We also found that these CuAlO2 thin film gas sensors showed reversible and reliable electrical resistance-response to NO gas in the operating temperature range. These results indicate that the transparent p-type semiconductor CuAlO2 thin films are very promising for application as sensing materials for gas sensors, in particular, various types of transparent p-n junction gas sensors. Also, these transparent p-type semiconductor CuAlO2 thin films could be combined with an n-type oxide semiconductor to fabricate p-n heterojunction oxide semiconductor gas sensors.

Co and Ni as catalysts in SnO2 sensors to improve the sensitivity for CH4 gas and CH3CH2CH3 gas were coated by a solution reduction method. SnO2 thick films were prepared by a screen-printing method onto Al2O3 substrates with an electrode. The sensing characteristics were investigated by measuring the electrical resistance of each sensor in a chamber. The structural properties of SnO2 with a rutile structure investigated by XRD showed a (110) dominant SnO2 peak. The particle size of the SnO2:Ni powders with Ni at 6 wt% was about 0.1 μm. The SnO2 particles were found to contain many pores according to a SEM analysis. The sensitivity of SnO2-based sensors was measured for 5 ppm of CH4 gas and CH3CH2CH3 gas at room temperature by comparing the resistance in air to that in the target gases. The results showed that the best sensitivity of SnO2:Ni and SnO2:Co sensors for CH4 gas and CH3CH2CH3 gas at room temperature was observed in SnO2:Ni sensors coated with 6 wt% Ni. The SnO2:Ni gas sensors showed good selectivity to CH4 gas. The response time and recovery time of the SnO2:Ni gas sensors for the CH4 and CH3CH2CH3 gases were 20 seconds and 9 seconds, respectively.

Polypyrrole (PPy)/multi-walled carbon nanotubes (MWCNTs) composites were prepared by in situ polymerization of pyrrole on the surface of MWCNTs templates to improve the ammonia gas sensing properties. PPy morphologies, formed on the surface of MWCNTs, were investigated by field emission scanning electron microscopy. The thermal stabilities of the PPy/MWCNTs composites were improved as the content of MWCNTs increased due to the higher thermal stability of the MWCNTs. PPy/MWCNTs composites showed synergistic effects in improving the ammonia gas sensing properties, attributed to the combination of efficient electron transfer between PPy/MWCNTs composites and ammonia gas, and the reproducible electrical resistance variation on PPy during the gas sensing process.

We report on the NO gas sensing properties of Al-doped zinc oxide-carbon nanotube (ZnO-CNT) wire-like layered composites fabricated by coaxially coating Al-doped ZnO thin films on randomly oriented single-walled carbon nanotubes. We were able to wrap thin ZnO layers around the CNTs using the pulsed laser deposition method, forming wire-like nanostructures of ZnO-CNT. Microstructural observations revealed an ultrathin wire-like structure with a diameter of several tens of nm. Gas sensors based on ZnO-CNT wire-like layered composites were found to exhibit a novel sensing capability that originated from the genuine characteristics of the composites. Specifically, it was observed by measured gas sensing characteristics that the gas sensors based on ZnO-CNT layered composites showed a very high sensitivity of above 1,500% for NO gas in dry air at an optimal operating temperature of 200˚C; the sensors also showed a low NO gas detection limit at a sub-ppm level in dry air. The enhanced gas sensing properties of the ZnO-CNT wire-like layered composites are ascribed to a catalytic effect of Al elements on the surface reaction and an increase in the effective surface reaction area of the active ZnO layer due to the coating of CNT templates with a higher surface-to-volume ratio structure. These results suggest that ZnO-CNT composites made of ultrathin Al-doped ZnO layers uniformly coated around carbon nanotubes can be promising materials for use in practical high-performance NO gas sensors.

Nano-sized SnO2 thick films were prepared by a screen-printing method onto Al2O3 substrates. The sensing characteristics were investigated by measuring the electrical resistance of each sensor in a test box as a function of the detection gas. The nano-sized SnO2 thick film sensors were treated in a N2 atmosphere. The structural properties of the nano SnO2with a rutile structure according to XRD showed a (110) dominant SnO2 peak. The particle size of SnO2:Ni nano powders at Ni 8 wt% was about 45 nm, and the SnO2 particles were found to contain many pores according to the SEM analysis. The sensitivity of the nano SnO2-based sensors was measured for 5 ppm CH4 gas and CH3CH2CH3 gas at room temperature by comparing the resistance in air with that in the target gases. The results showed that the best sensitivity of SnO2:Ni and SnO2:Co sensors for CH4 gas and CH3CH2CH3 gas at room temperature was observed in SnO2:Ni sensors doped with 8 wt% Ni. The response time of the SnO2:Ni gas sensors was 10 seconds and recovery time was 15 seconds for the CH4 and CH3CH2CH3 gases.

[ LaMeO3 ](Me = Cr, Co) powders were prepared using the polymeric precursor method. The effects of the chelating agent and the polymeric additive on the synthesis of the LaMeO3 perovskite were studied. The samples were synthesized using ethylene glycol (EG) as the solvent, acetyl acetone (AcAc) as the chelating agent, and polyvinylpyrrolidone (PVP) as the polymer additive. The thermal decomposition behavior of the precursor powder was characterized using a thermal analysis (TG-DTA). The crystallization and particle sizes of the LaMeO3 powders were investigated via powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and particle size analyzer, respectively. The as-prepared precursor primarily has LaMeO3 at the optimum condition, i.e. for a molar ratio of both metal-source (a : a) : EG (80a : 80a) : AcAc (8a) inclusive of 1 wt% PVP. When the as-prepared precursor was calcined at 700˚C, only a single phase was observed to correspond with the orthorhombic structure of LaCrO3 and the rhombohedral structure of LaCoO3. A solid-electrolyte impedance-metric sensor device composed of Li1.5Al0.5Ti1.5(PO4)3 as a transducer and LaMeO3 as a receptor has been systematically investigated for the detection of NOx in the range of 20 to 250 ppm at 400˚C. The sensor responses were able to divide the component between resistance and capacitance. The impedance-metric sensor for the NO showed higher sensitivity compared with NO2. The responses of the impedance-metric sensor device showed dependence on each value of the NOx concentration.