Influence of surface Pd doping on gas sensing characteristics of SnO2 thin films deposited by spray pirolysis

In this article the analysis of steady state and transient gas sensing characteristics of undoped and Pd surface doped SnO₂ films, deposited by spray pyrolysis, is described. The influence of parameters such as air humidity (2-50% RH), operation temperature (25-500 °C) and Pd surface concentration (0-1% ML Pd) on gas response to CO and H₂ (0.1-0.5%), response time, shape of sensitivity S(T) curves and activation energy of τ(1/kT) dependencies are discussed. A mechanism based on a chemisorption model is proposed to explain how Pd influences the gas sensing characteristics of SnO₂ films.     

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.     

The gas sensitivity of nano TiO2-SnO2 film doped with Cd(II) ion

The nanocomposite oxide (0.2TiO₂-0.8SnO₂) doped with Cd²⁺ powder have been prepared and characterized by XRD and their gas-sensing sensitivity were characterized using gas sensing measurement. Experimental results show that, bicomponent nano anatase TiO₂ and rutile SnO₂ particulate thick film doped with Cd²⁺ behaves with good sensitivity to formaldehyde gas of 200 ppm in the air, and the optimum sensing temperature was reduced from 360 °C to 320 °C compared with the undoped Cd²⁺ thick film. The gas sensing thick films doped with Cd²⁺ also show good selectivity to formaldehyde among benzene, toluene, xylene and ammonia as disturbed gas and could be effectively used as an indoor formaldehyde sensor.     

Solid-state reaction synthesized Pd-doped tin oxide thick film sensor for detection of H2, CO, LPG and CH4

This paper deals with the synthesis of tin oxide (SnO₂) nano-powders by a solid-state reaction technique. The synthesized powders have been characterized by simultaneous thermo gravimetric and differential thermal analysis (TG–DTA) and X-ray diffraction (XRD) techniques. Suitable calcination temperature is established by XRD and TG–DTA analysis. Thick film sensors have been developed from as-prepared undoped and palladium (Pd) doped (0.5 and 1 wt%) SnO₂ powders using screen printing technology for the detection of various pollutant gases such as, hydrogen (H₂), carbon monoxide (CO), liquefied petroleum gas (LPG) and methane (CH₄). The surface of the thick film sensor has been characterized by field emission scanning electron microscopy (FESEM). The sensing characteristics of thick films have been studied from the aspect of crystallite size of sensing material and microstructure of the thick film surface. It is found that SnO₂ doped with 1 % Pd exhibits the maximum sensitivity (79 %) towards CO gas along with fast response/recovery time (80 s, 197 s) and almost insensitive for H₂, LPG and CH₄.     

Interaction of reducing gases with tin oxide films prepared by reactive evaporation techniques

SnO_2−x films were prepared by reactive thermal and e-beam evaporation of Sn on alumina substrates and by post deposition thermal treatment. X-ray diffraction measurements found that films are tin dioxide (SnO₂) phase with small amounts of SnO phase. The surface conductivity of films was measured in air and in presence of H₂S, H₂ and C₂H₅OH vapors at four sensor operating temperatures of 433-493 K. The resistance of SnO_2−x films decreases on exposure to H₂S but shows no change with hydrogen and ethanol. H₂S response decreases with rise in sensor temperature while both response and recovery times improve. H₂S signal enhances with increase in resistivity of SnO_2−x coatings. Our experiments conclude that increase in film conductance is due to chemical reaction between H₂S and SnO_2−x surface and there is little or no role of interaction of gas molecules with surface adsorbed charged oxygen species.     

Gas sensing characteristics of MEMS gas sensor arrays in binary mixed-gas system

MOS gas sensor arrays based on MEMS gas sensor platforms were developed for the detection of carbon monoxide (CO), nitrogen oxides (NO_x) and ammonia (NH₃), and their gas sensing characteristics in binary mixed-gas system were investigated. Three gas sensing materials with nano-sized particles for these target gases, Pd–SnO₂ for CO, In₂O₃ for NO_x and Ru–WO₃ for NH₃ were synthesized using a sol–gel method. All the sensors showed good properties for their target gases at the optimum points for micro-heater operation. From the experimental data in MEMS gas sensor arrays in a binary mixed system, the gas sensing behavior and sensor response in mixed gas systems were scrutinized. The gas sensing behaviors to the mixed gas systems suggested that specific adsorption and selective activation of adsorption sites might occur in gas mixtures and offer the priority for the adsorption of specific gas. Thorough analysis of the sensing performance of the sensor arrays will make it possible to discriminate the components in gas mixtures as well as their concentrations.     

Selective detection of hydrogen sulfide using copper oxide-doped tin oxide based thick film sensor array

In this work, copper oxide-doped (1, 3 and 5 wt%) tin oxide powders have been synthesised by sol–gel method and thick film sensor array has been developed by screen printing technique for the detection of H₂S gas. Powder X-ray diffraction pattern shows that the tin oxide (SnO₂) doped with 3 wt% copper oxide (CuO) has smaller crystallite size in comparison to 0, 1 and 5 wt% CuO-doped SnO₂. Furthermore, field emission scanning electron microscopy manifests the formation of porous film consisting of loosely interconnected small crystallites. The effect of various amounts of CuO dopant has been studied on the sensing properties of sensor array with respect to hydrogen sulfide (H₂S) gas. It is found that the SnO₂ doped with 3 wt% CuO is extremely sensitive (82%) to H₂S gas at 150 °C, while it is almost insensitive to many other gases, i.e., hydrogen (H₂), carbon monoxide (CO), sulphur dioxide (SO₂) and liquefied petroleum gas (LPG). Moreover, at low concentration of gas, it shows fast recovery as compared to response time. Such high performance of 3 wt% CuO-doped SnO₂ thick film sensor is probably due to the diminishing of the p–n junction and the smallest crystallite size (11 nm) along with porous structure.     

Investigation of ethanol gas sensing properties of Dy-doped SnO<Subscript>2</Subscript> nanostructures

In this paper we report doping induced enhanced sensor response of SnO₂ based sensor towards ethanol at a working temperature of 200 °C. Undoped and dysprosium-doped (Dy-doped) SnO₂ nanoparticles were characterized by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). XRD and Raman results verified tetragonal rutile structure of the prepared samples. It has been observed that crystallite size reduced with increase in dopant concentration. In addition, the particle size has been calculated from Raman spectroscopy using phonon confinement model and the values match very well with results obtained from TEM and X-ray diffraction investigations. Dy-doped SnO₂ sensors exhibited significantly enhanced response towards ethanol as compared to undoped sensor. The optimum operating temperature of doped sensor reduced to 200 °C as compared to 320 °C for that of undoped sensor. Moreover, sensor fabricated from Dy-doped SnO₂ nanostructures was highly selective toward ethanol which signifies its potential use for commercial applications. The gas sensing mechanism of SnO₂ and possible origin of enhanced sensor response has been discussed.     

Gas sensors based on doped-CNT/SnO2 composites for NO2 detection at room temperature

For the first time nitrogen or boron doped carbon nanotubes were added into a SnO₂ matrix to develop a new hybrid CNTs/SnO₂ gas sensors. The hybrid sensor is utilised to detect low ppb concentrations of NO₂ in air, by measuring resistance changes of thin CNTs/SnO₂ films. The tests are performed at room temperature. For comparison, pure SnO₂ and N or B-substituted CNT sensors are also examined. Comparative gas sensing results reveal that the CNTs/SnO₂ hybrid sensors exhibit much higher response towards NO₂, at least by a factor of 10, and good baseline recovery properties at room temperature than the blank SnO₂ and the N or B-substituted CNT sensors. This finding shows that doping SnO₂ with low quantity of CNTs doped with heteroatoms can dramatically improve sensitivity.     

Effect of variation of sintering temperature on the gas sensing characteristics of SnO2:Cu (Cu=9 wt.%) system

The effect of variation of sintering temperature (600–800 °C/4 h) on the gas sensing characteristics of a SnO₂:Cu (Cu=9 wt.%) system (a high-performance temperature-selective composition) in the form of pellets is investigated systematically for the CO, H₂ and LPG gases at a concentration level of 1000 ppm. The XRD, SEM and half-bridge techniques were employed to establish the structural, morphological and gas sensing characteristics of the materials, respectively. A very high value of sensitivity factor (SF) equal to 1400 is obtained for CO gas at an optimal operating temperature of 160 °C for the pellets sintered at 750 °C. The selectivity values of CO gas against H₂ and LPG (S_CO/S_H2∼14 and S_CO/S_LPG∼280) at an optimum temperature of 160 °C are also improved considerably. This material (SnO₂:Cu, Cu=9 wt.% sintered at 750 °C with an optimal temperature of 160 °C) may prove to have tremendous potential for CO gas sensing applications.     

Characterization of nanosized TiO2 based H2S gas sensor

The present investigation deals with the fabrication of H₂S gas sensor based on semiconducting oxide,TiO₂. Among the various metal oxide additives tested, Al₂O₃ is outstanding in promoting the sensing properties of nanosized TiO₂ based H₂S gas sensor. XRD pattern of TiO₂ /Al₂O₃ shows complete phase formation with anatase structure and grain growth 45 nm. The TiO₂ sensor loaded with 5 wt% Al₂O₃ and 0.5 wt% Pd shows increase in sensitivity to H₂S. The cross sensitivity of 0.5 wt% Pd:5 wt% Al₂O₃ doped TiO₂ also checked for CO, LPG and H₂ gases. The highest sensitivity for low concentration of H₂S was observed using TiO₂ based mixed Al₂O₃ and Pd. The H₂S sensor shows high sensitivity and undesirable cross sensitivity effect using TiO₂/Al₂O₃/Pd as sensing materials.     

Gas sensing selectivity of oxygen-regulated SnO2 films with different microstructure and texture

The selectivity of gas sensing materials is increasingly important for their applications. The oxygen-regulated SnO₂ films with (110) and (101) preferred orientation were obtained through magnetron sputtering, followed by annealing treatment. Their micro-structure, surface morphology and gas response were investigated by advanced structural characterization and property measurement. The results showed that the as-prepared (110)-oriented SnO₂ film was oxygen-rich and had more adsorption sites while the as-prepared (101)-oriented SnO₂ film was oxygen-poor and more sensitive to de-oxidation. H₂ gas sensitivity, response speed, selectivity between H₂ and CO of the (110)-orientated SnO₂ film was superior to that of the (101)-orientated SnO₂ film. After treated at high temperature and high vacuum, the reduction of gas-sensing properties of the annealed (110) SnO₂ film was much more than that of the annealed (101) SnO₂ film. The lattice oxygen was responsible for the difference in gas-sensing response between (110) and (101)-oriented SnO₂ films under oxygen regulation. This work indicated the gas-sensing selectivity of the different crystal planes in SnO₂ film, providing a significant reference for design and extension of the related materials.     

Nature of V ions in SnO2: EPR and photoluminescence studies

SnO₂ and 5 at.% V doped SnO₂ samples were prepared by citrate-gel method. From Raman study on vanadium doped SnO₂, the existence of phase separated V₂O₅ clusters has been established. EPR study on the V doped sample clearly revealed the existence of V⁴⁺ ions, which are incorporated in SnO₂ lattice and the existence of conduction electrons with g = 1.993. For vanadium doped SnO₂ sample, there is a decrease in luminescence at 400 nm and an increase in activation energy of electrical conduction compared to undoped SnO₂, and this has been attributed to the decrease in oxygen vacancies brought about by the incorporation of V⁵⁺ in the SnO₂ lattice.     

Fast response detection of H2S by CuO-doped SnO2 films prepared by electrodeposition and oxidization at low temperature

Fast response detection of H₂S by CuO-doped SnO₂ films prepared was prepared by a simple two-step process: electrodeposition from aqueous solutions of SnCl₂ and CuCl₂, and oxidization at 600 °C. The phase constitution and morphology of the CuO-doped SnO₂ films were characterized by X-ray diffraction and scanning electron microscopy. In all cases, a polycrystalline porous film of SnO₂ was the product, with the CuO deposited on the individual SnO₂ particles. Two types of CuO-doped SnO₂ films with different microstructures were obtained via control of oxidation time: nanosized CuO dotted island doped SnO₂ and ultra-uniform, porous, and thin CuO film coated SnO₂. The sensor response of the CuO doped SnO₂ films to H₂S gas at 50–300 ppm was investigated within the temperature range of 25–125 °C. Both of the CuO-doped SnO₂ films show fast response and recovery properties. The response time of the ultra-uniform, porous, and thin CuO coated SnO₂ to H₂S gas at 50 ppm was 34 s at 100 °C, and its corresponding recovery time was about 1/3 of the response time.     

Study on simultaneous detection of CO and H<Subscript>2</Subscript> with (Pd,Fe)-modified SnO<Subscript>2</Subscript> and Pt-loaded SnO<Subscript>2</Subscript> sensors

The (Pd, Fe)-modified SnO₂ (S1) and Pt-loaded SnO₂ (S2) are synthesized via a sol–gel method. As S1 has better selectivity to CO against H₂ while S2 to H₂ against CO at 400 °C. Thus S1 and S2 can be used to detect the concentration of CO and H₂, respectively. However, neither S1 nor S2 can detect the concentration of CO and H₂ when they coexist. In this paper, S1 and S2 sensors are used simultaneously for mixed gas of CO and H₂ detection, and the respective concentration of CO and H₂ is calculated. The calculation process is explained as follows: the response of S1 (R₁) and S2 (R₂) to a fixed concentration of mixed gas of CO and H₂ is obtained in experiment, respectively. So we can calculate the concentration of CO and H₂ by using simultaneous equations with the independent variable R₁ and R₂. Contrast real values with calculated values of CO and H₂ concentration, the error margin are all less than 5%, which indicates that this method may be a promising candidate for enhancing the selectivity of semiconductor-based gas sensor to two or more gases.     

Sensitivity and selectivity of (Au,Pt, Pd)-loaded and (In,Fe)-doped SnO2 sensors for H2 and CO detection

(Au, Pt, Pd)-loaded and (In, Fe)-doped SnO₂ are synthesized by a sol–gel method. The composition, morphology and electrochemical property of the materials were characterized by XRD, SEM and electrochemical workstation, respectively. The results show that Au, Pd loading and In, Fe doping prefer to enhance the selectivity to CO against H₂, while Pt loading can enhance the selectivity to H₂ against CO. Furthermore, 1 mol% Pt-loaded SnO₂ sensor has preferable selectivity to H₂ against CO when Pt loading amount is changed. The response time of the Pt-loaded SnO₂ sensor to 5,000 ppm H₂ is 5 s at 400 °C, which is much shorter than that of pure SnO₂ sensor. Meanwhile the effect of operating temperature and Pt loading on n value (the slope of logarithm of response versus logarithm of gas concentration) is studied. The Pt-loaded SnO₂ sensor can detect H₂ down to 1 ppm. These results show that the Pt-loaded SnO₂ sensor is a good candidate for practical H₂ sensors.     

Determination of oxygen activities in highly diluted gas mixtures using a solid-state electrolyte cell

The applicability ofan oxygen sensor using stabilized zirconia as the solid-state electrolyte and catalytic Pt electrodes to measure oxygen activities in highly diluted gas mixtures was investigated. Various helium atmospheres containing low concentrations (in the µbar range) ofgaseous H₂,H₂O, CO, CO₂ and CH₄ impurities were used. For all gas mixtures considered an oxygen activity could be measured corresponding to the partial equilibrium ofH₂ and H₂O. The gas components CO and CO₂ did not affect the EMF ofthe cell, due to the low rates of their reactions at the Pt electrode relative to the H₂/H₂O equilibrium. Only CH₄ was seen to influence the measured oxygen partial pressure, P(O₂). It was found that the oxidation of CH₄ at Pt obeys a first-order rate law. Due to the extremely low kinetics of this reaction, only a slight reduction of p(O₂) from the H₂/H₂O equilibrium value of the bulk gas occurred.     

Ethanol gas sensing properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-doped ZnO thick film resistors

The characterization and ethanol gas sensing properties of pure and doped ZnO thick films were investigated. Thick films of pure zinc oxide were prepared by the screen printing technique. Pure zinc oxide was almost insensitive to ethanol. Thick films of Al₂O₃ (1 wt%) doped ZnO were observed to be highly sensitive to ethanol vapours at 300°C. Aluminium oxide grains dispersed around ZnO grains would result into the barrier height among the grains. Upon exposure of ethanol vapours, the barrier height would decrease greatly leading to drastic increase in conductance. It is reported that the surface misfits, calcination temperature and operating temperature can affect the microstructure and gas sensing performance of the sensor. The efforts are, therefore, made to create surface misfits by doping Al₂O₃ into zinc oxide and to study the sensing performance. The quick response and fast recovery are the main features of this sensor. The effects of microstructure and additive concentration on the gas response, selectivity, response time and recovery time of the sensor in the presence of ethanol vapours were studied and discussed.     

Mg/Ca decorated on carbon-doped boron nitride sheet: Application for gas adsorption

Through first-principles calculations, we investigate the adsorption of alkaline-earth(AE) metal (Mg/Ca) on carbon doped hexagonal boron nitride (h-BN) sheet, as well as its potential application as a sensor for gas molecules H₂, H₂O, CO, CO₂, O₂, and NO. With carbon substitution of nitrogen, Mg and Ca were energetically favorable to doped on the BN sheet with binding energies of 1.464 and 2.047 eV, respectively, due to the strong binding between AE atoms and substrate. With the Mg/Ca dopant, the binding interaction between gas molecules and the moderated BN sheet becomes stronger. For all the studied gases, the overall process of adsorption was found to be exothermic, moreover, NO, H₂O, and O₂ are chemisorbed while CO, H₂, and CO₂ are physisorbed. After adsorption, the electronic structures of systems are also affected judging from the electronic density of the state calculation.     

Gas sensing properties of lead doped tin oxide thick films

The present investigation deals with the fabrication of liquid petroleum gas (LPG) sensor materials based on semiconducting oxide SnO₂. The gas sensor materials have been prepared by conventional solid-state route. The effect of Pb incorporation, operating temperature, morphology, and sensitivity is discussed using the results of X-ray diffraction (XRD), along with sensing performance. Out of various sensor compositions, Pb doped SnO₂ sintered at 1000 °C for 2 h has shown high sensitivity towards LPG at an operating temperature of 150 °C. Different characterization techniques have been employed, such as surface area analyzer, X-ray diffraction (XRD), to study the formation of SnO₂, surface area and crystallite size, respectively. The results suggested the possibility of utilizing the sensor element for the detection of LPG.