Highly sensitive and fast responding CO sensor using SnO2 nanosheets

A highly sensitive and fast responding CO sensor was fabricated from a sheet-like SnO₂. The SnO sheets were prepared by a room temperature reaction between SnCl₂, hydrazine and NaOH, and they were subsequently oxidized into SnO₂ sheets at high temperature (600 °C). The morphology and size of the SnO₂ sheets could be controlled during the formation of SnO, which influence the sensor response (R_a/R_g) and response time to a great extent. The sensor response of SnO nanosheets to 10 ppm CO was enhanced up to 2.34, and the 90% sensor response time could be reduced to 6 s, which are significantly higher and shorter than those of SnO₂ powders (1.57 and 88 s), respectively. The realization of both a high sensitivity and rapid response were explained in terms of rapid gas diffusion onto the entire sensing surface due to the less-agglomerated and very thin structure of SnO₂ nanosheets and the catalytic effect of Pt.     

Selective detection of ethanol vapor and hydrogen using Cd-doped SnO2-based sensors

The effect of CdO doping on microstructure, conductance and gas-sensing properties of SnO₂-based sensors has been presented in this study. Precursor powders with Cd/Sn molar ratios ranging from 0 to 0.5 were prepared by chemical coprecipitation. X-ray diffraction (XRD) analysis indicates that the solid-state reaction in the CdO–SnO₂ system occurs and -CdSnO₃ with pervoskite structure is formed between 600 and 650°C. CdO doping suppresses SnO₂ crystallite growth effectively which has been confirmed by means of XRD, transmission electron microscopy (TEM) and BET method. The 10 mol% Cd-doped SnO₂-based sensor shows an excellent ethanol-sensing performance, such as high sensitivity (275 for 100 ppm C₂H₅OH), rapid response rate (12 s for 90% response time) and high selectivity over CO, H₂ and i-C₄H₁₀. On the other hand, this sensor has good H₂-sensing properties in the absence of ethanol vapor. The sensor operates at 300°C, the sensitivity to 1000 ppm H₂ is up to 98, but only 16 and 7 for 1000 ppm CO and i-C₄H₁₀, respectively.     

Highly sensitive gas sensors based on hollow SnO2 spheres prepared by carbon sphere template method

Hollow SnO₂ spheres were prepared in dimethylfomamide (DMF) by controlled hydrolysis of SnCl₂ using newly made carbon microspheres as templates. The phase composition and morphology of the material particles were characterized by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The gas sensing properties of sensors based on the hollow SnO₂ spheres were investigated. It was found that the sensor exhibited good performances, characterized by high response, good selectivity and very short response time to dilute (C₂H₅)₃N operating at 150 °C, especially, the response to 1 ppb (C₂H₅)₃N attained 7.1 at 150 °C. It was noteworthy that the response to 0.1 ppm C₂H₅OH of the sensor was 2.7 at 250 °C.     

Influence of Pd doping on morphology and LPG response of SnO2

In the present study nanocrystalline pristine and Pd-doped SnO₂ (Pd:SnO₂) with various mol% Pd have been synthesized by a modified Pechini citrate route. Transmission electron microscopy and X-ray powder diffraction studies were used to characterize the morphology, crystallinity, and structure of the SnO₂ and Pd:SnO₂. The response of the pristine SnO₂ and Pd:SnO₂ was studied towards different reducing gases. The 1.5 mol% Pd doping showed an enhanced response of 75 and 95% towards LPG at as low as 50 and 100 °C, respectively, which were quite large high value as compared with pristine SnO₂ (38 and 35% at 50 and 100 °C, respectively). Structural characterization revealed that Pd doping reduced the crystallite size of SnO₂ and helps in the formation of distinct spherical nanospheres at a calcinations temperature of 500 °C. Thus the increase in LPG response can be correlated with the spherical morphology, a decrease in the crystallite size (11 nm) due to doping with Pd as compared with the pristine SnO₂ (26 nm) and main role of Pd as a catalyst.     

Cerium oxide/SnO2-based semiconductor gas sensors with improved sensitivity to CO

SnO₂-based semiconductor gas sensors have been successfully fabricated and tested for detecting carbon monoxide and methane. The sensitivity and selectivity of the sensors are tailored by incorporation of different additives such as platinum and cerium oxide. While platinum enhances the sensor response to CH₄, ceria suppresses its sensitivity in favor of carbon monoxide. The effect of operating temperature on the performance of sensors is reported. Addition of 10% cerium oxide in the SnO₂ sample leads to an insignificant response to methane even at an elevated temperature of 450°C, while its response to CO remains intact.     

Characterization and gas sensitivity study of polyaniline/SnO2 hybrid material prepared by hydrothermal route

A polyaniline (PAni)/SnO₂ hybrid material was prepared by a hydrothermal method and characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The XRD pattern suggested that PAni did not modify the crystal structure of SnO₂, but SnO₂ affected the crystallization of PAni to some extent. The gas sensitivity of the PAni/SnO₂ hybrid was also studied to ethanol and acetone at operation temperatures of 30, 60 and 90 °C. It was found that the PAni/SnO₂ hybrid material had gas sensitivity only when operated at 60 and 90 °C, and it showed a linear relationship between the responses and the concentrations of ethanol and acetone at 90 °C. The sensing mechanism was also discussed.     

Humidity sensing and electrical properties of a composite material of nano-sized SiO2 and poly(2-acrylamido-2-methylpropane sulfonate)

A composite material of nano-sized SiO₂ and poly(2-acrylamido-2-methylpropane sulfonate) (poly(AMPS)) was used to make a humidity sensor. The infrared (IR) spectra and microstructure of the material were analyzed, and the humidity sensing and electrical properties of the sensor were measured. The sensor well responded to humidity with a relative good linearity, though it depended on the applied frequency. The temperature influence between 15 and 35 °C was −0.71 and −0.15% RH/°C at 30 and 90% RH, respectively. The sensor showed a negligible hysteresis and fast response time upon humidification and desiccation. The stability of the sensor in a highly humid and alcoholic environment increased with increasing the SiO₂ content. The activation energy for conduction reduced with water adsorption. The different impedance plots observed at low and high relative humidity suggested different sensing mechanisms of the SiO₂/poly(AMPS) composite material.     

CuO/SnO2 thin film heterostructures as chemical sensors to H2S

CuO/SnO₂ heterostructures as well as SnO₂(CuO) polycrystalline films have been studied for H₂S sensing. Gas sensing properties of these materials have been compared in conditions: 25–300 ppm H₂S in N₂ at 100–250°C. A shorter response time of the heterostructures as compared to that of the SnO₂(CuO) films has been found. It is suggested that the improvement of dynamic sensor properties of SnO₂/CuO heterostructures is caused by the localization of electrical barrier between CuO and SnO₂ layers.     

Tin oxide microsensor for LPG monitoring

A silicon-based SnO₂ gas sensor has been fabricated for monitoring liquified petroleum gas (LPG), commonly used as town gas. The gas sensor is made by silicon IC technology together with SnO_f2 thin-film processing. The whole chip with a size of 9 mm x 9 mm consists of nine sensors (three by three array). each sensor is supported by a thin membrane of SiO₂/Si₃N₄/SiO₂ layers that provides a low thermal mass and prevents heat conduction through the surrounding substrate material. Tin oxide thin film is prepared by thermal evaporation of metallic tin granules and subsequent thermal oxidation of the metallic film at 600 °C. To form the SnO₂(Pt) thin film, a layer of Pt with a thickness of several tens of angstroms is sputtered onto the tin oxide film and heat treated at 500 °C in air for several hours in order to stabilize its electrical response. The fabricated SnO₂(Pt) microsensors exhibit about 85 and 92% sensitivities to 5000 ppm C₃H₈ and 5000 ppm C₄H₁₀ (the main components of LPG) at 250 °C, respectively, and show a rapid response time of less than 5 s.     

Calorimetric hydrocarbon sensor for automotive exhaust applications

We have developed a calorimetric sensor utilizing a thermoelectric device supported on a planar alumina substrate. By using a highly selective carbon monoxide (CO) oxidation catalyst and a non-selective platinum (Pt) catalyst, the device can be built to detect either CO or hydrocarbons with high selectivity. The CO oxidation catalyst comprises lead-modified platinum and exhibits excellent selectivity over the 200–400 °C temperature range. The thermoelectric device consists of two thick film junctions made of niobium pentoxide (Nb₂O₅)-doped titanium dioxide (TiO₂) and a lithiated nickel (Ni), which are supported on a planar alumina substrate. The thermocouple detects the difference in temperature due to different catalytic reactions over the two junctions and shows a high output signal because of the high Seebeck coefficient of Nb₂O₅-doped TiO₂ (−400 μV/°C). In gas bench tests, the sensor has a linear output of 0–2.75 mV over 0–1000 ppm of propylene and a response time of 2.5 s (at 90% of amplitude) at a gas temperature of 350 °C. An engine dynamometer evaluation shows that the response of the sensor parallels the change in CO and hydrocarbon constituent concentrations when the engine air-to-fuel ratio is varied.     

Effect of surface modification on NO2 sensing properties of SnO2 varistor-type sensors

NO₂ sensing properties of SnO₂-based varistor-type sensors have been investigated in the temperature range of 400-650°C and in the NO₂ concentration range of 15–30 ppm. Pure SnO₂ exhibited a weak nonlinear I–V characteristic in air, but clear nonlinearity in NO₂ at 450°C. The breakdown voltage of SnO₂ shifted to a high electric field upon exposure to NO₂ and the magnitude of the shift was well correlated with NO₂ concentration. Thus, SnO₂ exhibited some sensitivity to NO₂ as a varistor-type sensor. When SnO₂ particles coated with a SiO₂ thin film were used as a raw material for fabricating a varistor, the breakdown voltage in air was approximately the double that of pure SnO₂ and the sensitivity to 15 ppm NO₂ was enhanced slightly. However, the sensitivity to 30 ppm NO₂ decreased. The Cr₂O₃-loading on SnO₂ also led to an increase in the breakdown voltage in air, but the Cr₂O₃ addition was not effective for promoting the NO₂ sensitivity under the present experimental conditions.     

Potentiometric CO2 gas sensor with lithium phosphorous oxynitride electrolyte

Potentiometric cell, Au/LiCoO₂ 5 m/o Co₃O₄/Li_2.88PO_3.73N_0.14/Li₂CO₃/Au, has been fabricated and investigated for monitoring CO₂ gas. A LiCoO₂–Co₃O₄ mixture was used as the solid-state reference electrode instead of a reference gas. The idea is to keep the lithium activity constant on the reference side using thermodynamic equilibrium at a given temperature. The thermodynamic stability of the reference electrode was studied from the phase stability diagram of Li–Co–C–O system. The Gibb’s free energy of formation of LiCoO₂ was estimated at 500°C from the measured value of the cell emf. The sensors showed good reversibility and fast response toward changing CO₂ concentrations from 200 to 3000 ppm. The emf values were found to follow a logarithmic Nernstian behavior in the 400–500°C temperature range. CH₄ gas did not show any interference effect. Humidity and CO gas decreased the emf values of the sensor slightly. NO and NO₂ gases affect this sensor significantly at low temperatures. However, increased operating temperature seems to reduce the interference.     

Microstructure, electrical and ethanol-sensing properties of perovskite-type SmFe0.7Co0.3O3

Ultrafine SmFe_0.7Co_0.3O₃ powder, prepared by a sol–gel method, shows a single-phase orthogonal perovskite structure. The influence of annealing temperature upon its crystal cell volume, microstructure, electrical and ethanol-sensing properties was investigated in detail. When the annealing temperature increases from 600 to 950 °C, the unit cell volume of the SmFe_0.7Co_0.3O₃ sample reduces, and its average grain size increases. When the annealing temperature increases from 600 to 850 °C, the optimal working temperature and response to ethanol of the SmFe_0.7Co_0.3O₃ sensor increase, and the response–recovery time shortens. But when the annealing temperature further increases from 850 to 950 °C, there are decreases of the optimal working temperature and sensor response, and the response–recovery time is prolonged. The results indicate that, as for sensor response, its optimal annealing temperature is about 850 °C, and the sensor based on SmFe_0.7Co_0.3O₃ annealed at 850 °C shows the highest response S = 80.8 to 300 ppm ethanol gas, and it has the best response–recovery and selectivity characteristics. When the ethanol concentration is as low as 500 ppm, the curve of its optimal response versus concentration is nearly linear. Meanwhile, the influence mechanisms of annealing temperature upon the conductance, the optimal working temperature and sensor response for SmFe_0.7Co_0.3O₃ were studied.     

Microstructure evolution and gas sensitivities of Pd-doped SnO2-based sensor prepared by three different catalyst-addition processes

We have investigated three ways of impregnating PdO on an SnO₂ gas sensor to achieve a simple and reliable sensor-fabrication process. These impregnating processes are: (1) coprecipitation of SnO₂ and Pd compounds in the solution; (2) addition of PdCl₂ to SnO₂ gel, followed by precipitation; and (3) infiltration of PdCl₂ into calcined SnO₂ powder. Processes (1) and (2) introduce Pd into SnO₂ particles before particle growth is completed. The phase and microstructures of particles have been analysed by X-ray diffraction, scanning and transmission electron microscopes, and an energy-dispering X-ray spectroscope. The presence of Pd in the process of SnO₂ precipitation restrains the growth of SnO₂ particles and enhances a uniform distribution of fine PdO powder on the SnO₂ grains. SnO₂ gas sensors have been fabricated and tested for response to CH₄, C₂H₆ and CO. Processes (1) and (2) show many possibilities of improving SnO₂ gas-sensor sensitivity with a simplified fabrication process.     

Nanoparticle engineering for gas sensor optimisation: improved sol–gel fabricated nanocrystalline SnO2 thick film gas sensor for NO2 detection by calcination, catalytic metal introduction and grinding treatments

The control of the technological steps such as calcination temperature and introduction of catalytic additives are accepted to be key points in the obtaining of improved sol–gel fabricated SnO₂ thick film gas sensors with different sensitivity to NO₂ and CO. In this work, after proving that the undoped material calcined at 1000°C is optimum for NO₂ detection, grinding is added as third technological step for further modification of particle surface characteristics, allowing to reduce cross-sensitivity to CO. The influence of grinding on the base resistance and on the sensor signals to NO₂ and CO is discussed in detail as a function of the structural differences of the sensing material.     

High sensitivity ethanol gas sensor integrated with a solid-state heater and thermal isolation improvement structure for legal drink-drive limit detecting

The paper reports the successful fabrication of ethanol gas sensors with tin-dioxide (SnO₂) thin films integrated with a solid-state heater, which is realized with technologies of micro-electro-mechanical systems (MEMS), and are compatible with VLSI processes. The main sensing part with dimensions of 450×400 μm² in this developed device is composed of a sensing SnO₂ film, which is fabricated by electron-gun evaporation with proper annealing in ambient oxygen gas to yield fine particles and good structure. An integrated solid-state heater with a 4.5 μm-thick cantilever bridge (1000×500 μm²) structure is made of silicon carbide (SiC) material by MEMS technologies. The sensitivity for 1000 ppm ethanol gas reaches as high as 90 with 10 s and 2 min for the response and recovery time, respectively, at an operating temperature of 300°C. Those experimental results also exhibit a much superior performance to that of a popular commercial ethanol gas sensor TGS-822. Therefore, the developed sensor with high performance is a good candidate for some specific application in automobile to detect drink-drive limit and allows an array integration available with various films for controlling each element at separate resistance.     

Material properties and the influence of metallic catalysts at the surface of highly dense SnO2 films

We present an approach to optimize the specific response to gases by using specially prepared nanosized platinum on highly dense sputtered polycrystalline SnO₂. Structural and morphological analyses of the SnO₂ and platinum thin films were performed. Gas measurements were carried out with single chip thin-film SnO₂ sensor arrays on silicon substrates. Pt nanoclusters covering the sensitive layer significantly affect the O₃, CO and NO₂ sensitivities and the corresponding dynamic response.     

Impedancemetric gas sensor based on Pt and WO3 co-loaded TiO2 and ZrO2 as total NOx sensing materials

Pt-loaded metal oxides [WO₃/ZrO₂, MO_x/TiO₂ (MO_x = WO₃, MoO₃, V₂O₅), WO₃ and TiO₂] equipped with interdigital Au electrodes have been tested as a NO_x (NO and NO₂) gas sensor at 500 °C. The impedance value at 4 Hz was used as a sensing signal. Among the samples tested, Pt-WO₃/TiO₂ showed the highest sensor response magnitude to NO. The sensor was found to respond consistently and rapidly to change in concentration of NO and NO₂ in the oxygen rich and moist gas mixture at 500 °C. The 90% response and 90% recovery times were as short as less than 5–10 s. The impedance at 4 Hz of the present device was found to vary almost linearly with the logarithm of NO_x (NO or NO₂) concentration from 10 to 570 ppm. Pt-WO₃/TiO₂ showed responses to NO and NO₂ of the same algebraic sign and nearly the same magnitude, while Pt/WO₃ and WO₃/TiO₂ showed higher response to NO than NO₂. The impedance at 4 Hz in the presence of NO for Pt-WO₃/TiO₂ was almost equal at any O₂ concentration examined (1–99%), while in the case of Pt/WO₃ and WO₃/TiO₂ the impedance increased with the oxygen concentration. The features of Pt-WO₃/TiO₂ are favorable as a NO_x sensor that can monitor and control the NO_x concentration in automotive exhaust. The effect of WO₃ loading of Pt-WO₃/ZrO₂-based sensor is studied to discuss the role of surface W-OH sites on the NO_x sensing.     

Micromachined sol–gel carbon nanotube/SnO2 nanocomposite hydrogen sensor

A novel micromachined single wall carbon nanotube (SWCNT) reinforced nanocrystalline tin dioxide gas sensor has been developed. The presence of SWCNT in SnO₂ matrix was realized by a spin-on sol–gel process. The SWCNT/SnO₂ sensor's sensitivity for hydrogen detection has greatly increased by a factor of three, in comparison to that of pure SnO₂ sensor. The novel sensor also lowers the working temperature, response time and recovery time. The greatly improved performances are mainly attributed to the effective gas accessing nano passes through SWCNT plus the smaller distance between adjacent gas accessing boundaries formed by the distribution of tiny SWCNTs. Therefore, both the spatial requirement (D ≤ 2L, D is the distance between adjacent gas accessing boundaries and L is the space charge layer thickness) and surficial requirement (adequate gas activation area) are met and the maximum inherent sensitivity of SnO₂ is achieved.     

Selective NH3 gas sensor based on Langmuir-Blodgett polypyrrole film

Polypyrrole thin films have been deposited onto a glass substrate by the Langmuir-Blodgett technique to fabricate a selective ammonia (NH₃) gas sensor. The d.c. electrical resistance of the sensing elements is found to exhibit a specific increase upon exposure to different gases such as NH₃, CO, CH₄, H₂ in N₂ and pure O₂. The polypyrrole thin-film detector shows a considerable increase of resistance when exposed to NH₃ in N₂, and negligible response when exposed to comparable concentrations of interfering gases such as CO, CH₄, H₂ in N₂ and pure O₂. The calibration curve for NH₃ in N₂ at room temperature is measured in the concentration range from 0.01 to 1%. The relative change of the electrical resistance is about 10% for the lower detectable limit of 100 ppm of NH₃ in N₂. The sensitivity of the Langmuir-Blodgett polypyrrole towards ammonia is considerably higher than that of the electrochemical polypyrrole. The fast rise time and the high sensitivity of the detector are reported as a function of number of the polypyrrole layers. Long-term aging tests of the selective NH₃ gas sensor are performed.