Conduction mechanisms in SnO2 based polycrystalline thick film gas sensors exposed to CO and H2 in different oxygen backgrounds

The conduction mechanism in polycrystalline SnO₂ thick sensing films was modeled and experimentally investigated by means of simultaneous DC electrical resistance and work function changes measurements under CO and H₂ exposure in different oxygen backgrounds. It was shown that, according to the composition of the ambient atmosphere, the conduction changes from the case in which it is controlled by the surface depletion layers to a situation in which the main contribution comes from free charge transport in the surface accumulation layer. This is significant for the interpretation of work function changes measurements results because the relation between the different measured electrical resistance and surface band bending depends on the conduction model. Furthermore, the CO sensing mechanism dependence on the oxygen amount in the ambient was explained.     

Hydrogen sensing and mechanism of M-doped SnO2 (M = Cr, Cu and Pd) nanocomposite

The microstructure of M-doped SnO₂ (M = Cr³⁺, Cu²⁺ and Pd²⁺) prepared by the sol–gel method and their gas-sensing performance were investigated. In particular, we focus on the effects of metallic ions on the hydrogen sensing behavior of the SnO₂-based sensor. It is found that hydrogen gas response of SnO₂ can be enhanced evidently by adding Pd²⁺, while such effect from Cr³⁺ and Cu²⁺ exhibits somewhat slight. A theoretical study based on first principles calculation shows that SnO₂–Pd (1 1 0) surface enable adsorb more H₂ gas and receive larger electrons from adsorbed H₂ molecule, thereby holding the potential for the improvement of gas response to hydrogen.     

Water pre-adsorption effect on room temperature SnO2 nanobelt ethanol sensitivity in oxygen-deficient conditions

The water adsorption effects on room temperature ethanol sensitivity of a SnO₂ single crystal nanobelt was studied. SnO₂ nanobelt showed better electrical conductivity in air than in vacuum. The current increased linearly with relative humidity in air and with water concentration in vacuum. In the presence of water vapor, the SnO₂ nanobelt electrical response was quite different, depending on the H₂O and C₂H₅OH molecules adsorption sequence. The current response to ethanol gas increased substantially when water was pre-adsorbed. However, no change was found without water pre-adsorbtion. This interesting behavior is ascribed to competition between the H₂O and C₂H₅OH molecules trying to adsorb on oxygen sites at the tin oxide surface. Dissociated water acts as the surface conduction channel resulting in better conductivity, while ethanol is physisorbed without water pre-adsorption. Based on this sensing mechanism, SnO₂ nanobelt can be used as a highly efficient ethanol detector in humid air.     

On the temperature dependence of the resistive and surface ionisation response of SnO2 gas sensing layers

Gas sensing experiments have been performed on SnO₂ thin films using a wide range of different analyte gases. In these experiments, the SnO₂ layers were specifically configured to observe the familiar resistive (RES) gas response alongside with the novel surface ionisation (SI) response. It is shown that the RES and SI responses, in general, occur in dissimilar temperature ranges and that both follow very different selectivity criteria. Microscopically, both kinds of response proceed through analyte-specific sequences of adsorption, surface reaction, charge transfer and desorption steps. A generalisation of the Ahlers model [1], originally developed to account for the bell-shaped temperature variation of the RES response of thin film metal oxide layers, is shown to quantitatively account for the whole range of SI data. Fits to experimental SI response vs. temperature curves allow the total energy input into the surface ionisation process to be determined and insights into the ionisation mechanism to be gained.     

Ultrahigh ethanol response of SnO2 nanorods at low working temperature arising from La2O3 loading

The influences of La₂O₃ loading on the ethanol sensing properties of SnO₂ nanorods were investigated. An obvious enhancement of response was obtained. The response of 5 wt% La₂O₃ loaded SnO₂ nanorods was up to 213 for 100 ppm ethanol at low working temperature of 200 °C, while that of pure SnO₂ nanorods is 45.1. The improvement in response might be attributed to the presence of basic sites, which facilitated the dehydrogenation process. While the working temperature was increased to 300 °C, the sensor response decreased to 16 for 100 ppm ethanol. Additionally, the La₂O₃ loaded SnO₂ nanorods sensors showed good selectivity to ethanol over methane and hydrogen. Our results demonstrated that the La₂O₃ loaded SnO₂ nanorods were promising in fabricating high performance ethanol sensors which could work at low temperature.     

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.     

The influence of catalytic activity on the response of Pt/SnO2 gas sensors to carbon monoxide and hydrogen

The article presents the results of research studies on ceramics SnO₂ sensors with Pt catalysts. The role of catalysis in gas sensing mechanisms was investigated. In order to obtain samples with different catalytic activity but with identical Pt loading, the Pt/SnO₂ catalysts were calcined at different temperatures (400-800 °C). Structural analysis of these samples was performed. Among the sensors manufactured with Pt/SnO₂, the highest sensitivity was shown for the sensor obtained with Pt/SnO₂ sample sintered at 800 °C. The correlation between catalytic activity and sensor sensitivity is given.     

SnO2 thin films modified by the SnO2–Au nanocomposites: Response to reducing gases

The influence of the SnO₂ surface modification by the SnO₂–Au nanocomposites on conductivity response to such reducing gases as CO and H₂ has been analyzed in the present paper. Both initial SnO₂ films, subjected for surface modification, and SnO₂–Au nanocomposites were deposited by Successive Ionic Layer Deposition (SILD) method. The SnO₂–Au nanocomposites with Au/Sn ratio 1 were synthesized using HAuCl₄ and SnCl₂ precursors. The thickness of the Au-SnO₂ nanolayers varied from 0.7–1.0 nm to 10–15 nm. It was established that the increase in the thickness of the SnO₂–Au nanocomposite layer formed on the surface of the SnO₂ films was accompanied by both the improvement of sensor response and the decrease in response and recovery times. An explanation of the observed effects has been proposed.     

Improved crystalline structure and H2S sensing performance of CuO-Au-SnO2 thin film using SiO2 additive concentration

In situ SiO₂-doped SnO₂ thin films were successfully prepared by liquid phase deposition. The influence of SiO₂ additive as an inhibitor on the surface morphology and the grain size for the thin film has been investigated. These results show that the morphology of SnO₂ film changes significantly by increasing the concentration of H₂SiF₆ solution which decreases the grain size of SnO₂. The stoichiometric analysis of Si content in the SnO₂ film prepared from various Si/Sn molar ratios has also been estimated. For the sensing performance of H₂S gas, the SiO₂-doped Cu-Au-SnO₂ sensor presents better sensitivity to H₂S gas compared with Cu-Au-SnO₂ sensor due to the fact that the distribution of SiO₂ particles in grain boundaries of nano-crystallines SnO₂ inhibited the grain growth (<6 nm) and formed a porous film. By increasing the Si/Sn molar ratio, the SiO₂-doped Cu-Au-SnO₂ gas sensors (Si/Sn = 0.5) exhibit a good sensitivity (S = 67), a short response time (t_90% < 3 s) and a good gas concentration characteristic (α = 0.6074). Consequently, the improvement of the nano-crystalline structures and high sensitivity for sensing films can be achieved by introducing SiO₂ additive into the SnO₂ film prepared by LPD method.     

Electrostatic sprayed SnO2 and Cu-doped SnO2 films for H2S detection

This paper presents the ability of electrostatic sprayed tin oxide (SnO₂) and tin oxide doped with copper oxide (1, 2, and 4 at.% Cu) films to detect different pollutant gases, i.e., H₂S, SO₂, and NO₂. The influence of a copper oxide dopant on the SnO₂ morphology is studied using scanning electron microscopy (SEM) technique, which reveals a small decrease in the porosity and particle size when the amount of dopant is increased. The sensing properties of the SnO₂ films are greatly improved by doping, i.e., the Cu-doped SnO₂ films have large response to low concentration (10 ppm) of H₂S at low operating temperature (100 °C). Furthermore, no cross-sensitivity to 1 ppm NO₂ and 20 ppm SO₂ is observed. Among the studied films, the 1 at.% Cu-doped SnO₂ layer is the most sensitive in the detection of all the studied gases.     

Synthesis of novel SnO2/ZnSnO3 core-shell microspheres and their gas sensing properities

Large-scale novel core-shell structural SnO₂/ZnSnO₃ microspheres were successfully synthesized by a simple hydrothermal method with the help of the surfactant poly(vinyl pyrrolidone) PVP. The as-synthesized samples were characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The results indicate that the shell was formed by single crystalline ZnSnO₃ nanorods and the core was formed by aggregated SnO₂ nanoparticles. The effects of PVP and hydrothermal time on the morphology of SnO₂/ZnSnO₃ were investigated. A possible formation mechanism of these hierarchical structures was discussed. Moreover, the sensor performance of the prepared core-shell SnO₂/ZnSnO₃ nanostructures to ethanol was studied. The results indicate that the as-synthesized samples exhibited high response and quick response-recovery to ethanol.     

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.     

Development and application of micromachined Pd/SnO2 gas sensors with zeolite coatings

Zeolite A (LTA)-coated micromachined sensors have been prepared and used in the sensing of individual gases (H₂, CH₄, C₂H₅OH, C₃H₈ and CO, in the 10–1000 ppm range) and gas mixtures. Unlike previous works with conventional sensors, a hydrothermal synthesis was not used to prepare a zeolite film. Instead, a zeolite coating was formed on top of the Pd/SnO₂ surface by microdropping from a zeolite suspension. In spite of this, the response of the sensor with zeolite is significantly different from that of unmodified sensors, and essentially reproduces the performance of zeolite-coated conventional sensors. By avoiding the use of a hydrothermal synthesis the integrity of the sensor is better preserved, and the resulting non-continuous zeolite film has the added advantage of a strong reduction in response times.     

Examination of Au/SnO2 core-shell architecture nanoparticle for low temperature gas sensing applications

Au/SnO₂ core-shell structure nanoparticles (NPs) were synthesized using two methods, microwave and conventional precipitation. In both cases, the size of the Au core was 12-18 nm and the thickness of the SnO₂ shell was 8-12 nm. The particle size of SnO₂ synthesized using the microwave and precipitation method was 3-5 nm and 1-2 nm, respectively. Upon heating to 400-600 °C, both particles maintained their core-shell morphology but the smaller SnO₂ particles prepared using the precipitation method were more sintered. The resistance changes in films of these particles were measured as a function of CO concentration. The Au/SnO₂ particles prepared using the microwave method showed higher sensor response than those prepared using the precipitation method, even providing a significant signal at testing temperatures approaching ambient conditions, thereby affording a new class of material for gas sensing. Both sets of core-shell particles showed higher sensor response than the SnO₂ nanoparticles. The role of the Au core as a catalyst in improving the adsorption and oxidation of CO gas is important for improving the low temperature response. In addition, the maintenance of the size of SnO₂ in the microwave method during sintering contributed to the higher response towards CO sensing.     

Enhanced H2S sensing characteristics of SnO2 nanowires functionalized with CuO

The CuO-functionalized SnO₂ nanowire (NW) sensors were fabricated by depositing a slurry containing SnO₂ NWs on a polydimethylsiloxane (PDMS)-guided substrate and subsequently dropping Cu nitrate aqueous solution. The CuO coating increased the gas responses to 20 ppm H₂S up to 74-fold. The R_a/R_g value of the CuO-doped SnO₂ NWs to 20 ppm H₂S was as high as 809 at 300 °C, while the cross-gas responses to 5 ppm NO₂, 100 ppm CO, 200 ppm C₂H₅OH, and 100 ppm C₃H₈ were negligibly low (1.5–4.0). Moreover, the 90% response times to H₂S were as short as 1–2 s at 300–400 °C. The selective detection of H₂S and enhancement of the gas response were attributed to the uniform distribution of the sensitizer (CuO) on the surface of the less agglomerated network of the SnO₂ NWs.     

Ordered mesoporous Pd/SnO2 synthesized by a nanocasting route for high hydrogen sensing performance

Ordered mesoporous SnO₂ and mesoporous Pd/SnO₂ have been successfully synthesized via nanocasting method using the hexagonal mesoporous SBA-15 as template. Two different procedures, impregnation technique and direct synthesis, were utilized for the doping of Pd in the mesoporous SnO₂. The results of small angle X-ray diffraction (SAXD), nitrogen adsorption–desorption and transmission electron microscopy (TEM) demonstrate that the SnO₂ and Pd/SnO₂ display ordered mesoporous structures and high surface areas. Wide angle X-ray diffraction (WAXD) and X-ray photoelectron spectroscopy (XPS) reveal tetragonal structure of SnO₂ and the existence of Pd element. The sensing properties of mesoporous SnO₂ and mesoporous Pd/SnO₂ for H₂ were detected. The sensor utilizing mesoporous Pd/SnO₂ via direct synthesis method exhibits excellent response and recovery behavior and much higher sensitivity to H₂, compared to those using mesoporous SnO₂ and mesoporous Pd/SnO₂ via impregnation technique. It is believed that its high gas sensing performance is derived from the large surface area, high activity and well dispersion of Pd additive, as well as high porosity, which lead to highly effective surface interaction between the target gas molecules and the surface active sites.     

SnO2-based R134a gas sensor: Sensing materials preparation, gas response and sensing mechanism

Undoped SnO₂ and porous Al₂O₃ powders were obtained through a simple chemical precipitation process. SnO₂-based gas sensing materials and Al₂O₃ catalytic coating loaded with a noble metal were prepared by impregnation. The SnO₂ and Al₂O₃ powders were characterized by TEM, SEM, nitrogen adsorption-desorption experiment, FT-IR and in situ XRD. Gas responses of the SnO₂-based gas sensors were measured in a static state. The experimental results indicated that the response towards R134a of the SnO₂-based gas sensor can be significantly enhanced by loading noble metal and using catalytic coating. The sensor based on a double layer film SnO₂ (Au)/Al₂O₃ (Au) showed satisfactory results including large response, good selectivity, high long-term stability, fast response and recovery, revealing its potential application in the detection of refrigerants and the maintenance of air condition systems. Finally, a gas sensing mechanism for R134a is suggested and proved by bond energy data, FT-IR spectrum and in situ XRD.     

Effect of thickness of platinum catalyst clusters on response of SnO2 thin film sensor for LPG

This paper reports the sensing response characteristics of rf-sputtered SnO₂ thin films (90 nm thick) loaded with platinum catalyst cluster of varying thickness (2-20 nm) for LPG detection. The enhanced response (5 × 10³) was obtained for 200 ppm LPG with the presence of 10 nm thin and uniformly distributed Pt catalyst clusters on the surface of SnO₂ thin film at a relatively low operating temperature (220 °C). The high response for LPG is shown to be primarily due to the enhanced catalytic activity for adsorbed oxygen on the surface of SnO₂ thin film besides the spill over mechanism at elevated temperature.     

Enhancing performance of FSP SnO2-based gas sensors through Sb-doping and Pd-functionalization

Via flame spray pyrolysis (FSP), SnO₂ gas sensing layers have been doped with 0.01-4 wt% Sb as well as 0.01 wt% Pd in combination with 1 wt% Sb. Characterization of these materials through X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface analysis, and transmission electron microscopy (TEM) revealed particle grain sizes and crystallinity unchanged by the presence of Sb and/or Pd. The addition of Sb to SnO₂ resulted in the significant decrease in baseline resistance; up to two orders of magnitude in dry air at 300 °C and three orders of magnitude in humid air at 300 °C, which is significant for FSP-prepared gas sensors with high porosity and low particle coordination number since they typically suffer from high baseline resistance. While the baseline resistance was improved with Sb-doping, the sensor signal (R₀/R_gas) remained constant over all concentrations explored. Moreover, regarding the surface functionalization of SnO₂ with Pd in combination with Sb-doping, the reduction of baseline resistance was preserved without influencing sensor signal.     

Growth kinetics of nanograins in SnO2 fibers and size dependent sensing properties

The present study investigates the growth kinetics of SnO₂ nanograins and determines the activation energy and mechanism of the growth in nanofiber form. The activation energy for the growth of the SnO₂ nanograins was estimated to be ∼28.28 kJ/mol, which is an order of magnitude smaller than that of bulk SnO₂. The estimated m value suggests that the growth mechanism of the nanograins is primarily through lattice diffusion in the pore control scheme. Precise control of the calcination temperature and time is necessary to maximize the efficiency of electrospinning-synthesized SnO₂ nanofibers for sensor applications. Importantly, the sensor fabricated with nanofibers of small nanograins showed much better sensing properties to CO and NO₂ comparing with the sensor fabricated with nanofibers of large nanograins. A mechanism to explain this finding is suggested.