Nano particulate SnO2 based resistive films as a hydrogen and acetone vapour sensor

SnCl₂ (solution) was spin coated on soda lime glass and Al₂O₃ substrate to obtain nano-particulate tin oxide film, directly by sintering at 550 °C for 40 minutes (min). The surface morphology and crystal structure of the tin oxide films were analyzed using atomic force microscopy (AFM) and X-ray diffraction (XRD). The size of SnO₂ nanostructure was determined from UV-vis and found to be ?3 nm. These films were tested for sensing H₂ concentration of 0.1-1000 ppm at optimized operating temperature of 265 °C. The results showed that sensitivity (R_air/R_gas per ppm) goes on increasing with decreasing concentration of test gas, giving concentration dependent changes. Special studies carried out at low concentration levels (0.1-1 and 1-10 ppm) of H₂, give high sensitivity (200 × 10⁻³/ppm) for lowest concentration (0.1-1 ppm) of H₂. The selectivity for H₂ against relative humidity (RH), CO₂, CO and LPG gases is also good. The sensor, at operating temperature of 200 °C, is showing nearly zero response to 300 ppm of H₂, and offering response to acetone vapour of 11 ppm. Selectivity for acetone against RH% and CO₂ was also studied. These sensors can be used as H₂ sensor at an operating temperature of 265 °C, and as an acetone sensor at the operating temperature of 200 °C.     

Structural and properties of nanocrystalline WO3/TiO2-based humidity sensors elements prepared by high energy activation

Nanocrystalline WO₃/TiO₂-based powders have been prepared by the high energy activation method with WO₃ concentration ranging from 1 to 10 mol%. The samples were thermal treated in a microwave oven at 600 °C for 20 min and their structural and micro-structural characteristics were evaluated by X-ray diffraction, Raman spectroscopy, EXAFS measurements at the Ti K-edge, and transmission electron microscopy. Nitrogen adsorption isotherms and H₂ Temperature Programmed Reduction were also carried out for physical characterization. The crystallite and particle mean sizes ranged from 30 to 40 nm and from 100 to 190 nm, respectively. Good sensor response was obtained for samples with at least 5 mol% WO₃ activated for at least 80 min. Ceramics heat-treated in microwave oven for 20 min have shown similar sensor response as those prepared in conventional oven for 120 min, which is highly cost effective. These results indicate that WO₃/TiO₂ ceramics can be used as a humidity sensor element.     

Microstructure control of TiO2 nanotubular films for improved VOC sensing

Porous gas sensing films composed of TiO₂ nanotubes were fabricated for the detection of volatile organic compounds (VOCs), such as alcohol and toluene. In order to control the microstructure of TiO₂ nanotubular films, ball-milling treatments were used to shorten the length of TiO₂ nanotubes and to improve the particle packing density of the films without destroying their tubular morphology and crystal structure. The ball-milling treatment successfully modified the porosity of the gas sensing films by inducing more intimate contacts between nanotubes, as confirmed by scanning electron microscopy (SEM) and mercury porosimetry. The sensor using nanotubes after the ball-milling treatment for 3 h exhibited an improved sensor response and selectivity to toluene (50 ppm) at the operating temperature of 500 °C. However, an extensive ball-milling treatment did not enhance the original sensor response, probably owing to a decrease in the porosity of the film. The results obtained indicated the importance of the microstructure control of sensing layers in terms of particle packing density and porosity for detecting large sized organic gas molecules.     

Effect of La2CuO4 electrode area on potentiometric NOx sensor response and its implications on sensing mechanism

The intent of this work is to look at the effects of varying the La₂CuO₄ electrode area and the asymmetry between the sensing and counter electrode in a solid state potentiometric sensor with respect to NO_x sensitivity. NO₂ sensitivity was observed at 500-600 °C with a maximum sensitivity of ∼22 mV/decade [NO₂] observed at 500 °C for the sensor with a La₂CuO₄ electrode area of ∼30 mm². The relationship between NO₂ sensitivity and area is nearly parabolic at 500 °C, decreases linearly with increasing electrode area at 600 °C, and was a mixture of parabolic and linear behavior 550 °C. NO sensitivity varied non-linearly with electrode area with a minima (maximum sensitivity) of ∼−22 mV/decade [NO] at 450 °C for the sensor with a La₂CuO₄ electrode area of 16 mm². The behavior at 400 °C was similar to that of 450 °C, but with smaller sensitivities due to a saturation effect. At 500 °C, NO sensitivity decreases linearly with area.We also used electrochemical impedance spectroscopy (EIS) to investigate the electrochemical processes that are affected when the sensing electrode area is changed. Changes in impedance with exposure to NO_x were attributed to either changes in La₂CuO₄ conductivity due to gas adsorption (high frequency impedance) or electrocatalysis occurring at the electrode/electrolyte interface (total electrode impedance). NO₂ caused a decrease in high frequency impedance while NO caused an increase. In contrast, NO₂ and NO both caused a decrease in the total electrode impedance. The effect of area on both the potentiometric and impedance responses show relationships that can be explained through the mechanistic contributions included in differential electrode equilibria.     

Ag nanoparticles modified TiO2 spherical heterostructures with enhanced gas-sensing performance

Monodispersed TiO₂ spherical colloids with diameters of about 250 nm were prepared by a sol-gel method. Heterostructural Ag-TiO₂ spheres were manipulated by surface engineering, in which the Ag nanoparticles with an average size of 10 nm were uniformly distributed on the surface of the TiO₂ nanospheres by in situ reduction and growth. The gas-sensing properties of the TiO₂ nanospheres and heterostructural Ag-TiO₂ nanospheres to ethanol and acetone were measured at 350 °C. The results indicated that Ag nanoparticles greatly enhanced the response, stability and response characteristic of TiO₂ nanospheres to the tested gases. Response times of Ag-TiO₂ sensor to 30 ppm acetone and 50 ppm ethanol were <5 s.     

Temperature dependent H2S and Cl2 sensing selectivity of Cr2O3 thin films

The conductometric gas sensing characteristics of Cr₂O₃ thin films - prepared by electron-beam deposition of Cr films on quartz substrate followed by oxygen annealing - have been investigated for a host of gases (CH₄, CO, NO₂, Cl₂, NH₃ and H₂S) as a function of operating temperature (between 30 and 300 °C) and gas concentration (1-30 ppm). We demonstrate that these films are highly selective to H₂S at an operating temperature of 100 °C, while at 220 °C the films become selective to Cl₂. This result has been explained on the basis of depletion of chemisorbed oxygen from the surface of films due to temperature and/or interaction with Cl₂/H₂S, which is supported experimentally by carrying out the work function measurements using Kelvin probe method. The temperature dependent selectivity of Cr₂O₃ thin films provides a flexibility to use same film for the sensing of Cl₂ as well as H₂S.     

Gas sensing properties of p-type hollow NiO hemispheres prepared by polymeric colloidal templating method

This work presents a simple and versatile route to produce macroporous p-type metal oxide thin films. Two-dimensional arrays of p-type NiO films with a hollow hemisphere structure were fabricated by colloidal templating and RF-sputtering followed by a subsequent heat treatment. The diameter and shell thickness of the NiO hemisphere were 800 nm and 20 nm, respectively. X-ray diffraction and high-resolution transmission electron microscopy analysis indicate that the pure NiO phase with grain size of 10 nm was obtained at calcination temperatures that exceeded 450 °C. Close-packed arrays of hollow NiO hemispheres were found to exhibit p-type gas sensing properties against (CO, H₂, C₃H₈, CH₄, NO₂, and C₂H₅OH), leading to significantly enhanced responses to C₂H₅OH (R_gas/R_air = 5.0 at 200 ppm).     

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.     

NO2 gas sensing properties of amorphous InGaZnO4 submicron-tubes prepared by polymeric fiber templating route

One-dimensional (1D) amorphous InGaZnO₄ (a-IGZO) submicron-tubes were synthesized in a method involving an electrospun polymeric fiber template and the direct RF-sputter-coating of a-IGZO films combined with subsequent calcination at 450 °C. The a-IGZO hollow fibers with a diameter of 300 nm and a shell thickness of 20–30 nm showed an amorphous structure, as confirmed by XRD and HR-TEM analyses. Gas sensors using semiconducting a-IGZO tube networks exhibited n-type gas sensing characteristics and a 3.7-fold higher gas response (R_gas/R_air = 109.5 at 2 ppm NO₂) compared to (R_gas/R_air = 29.4) planar a-IGZO thin films at an operating temperature of 300 °C. The enhanced gas response of a-IGZO tubes is attributed to the greater space charge modulation depth associated with the thin shell structures and the porous networks which are readily accessible by gas.     

A route to high sensitivity and rapid response Nb2O5-based gas sensors: TiO2 doping, surface embossing, and voltage optimization

We report a novel route for the fabrication of highly sensitive and rapidly responding Nb₂O₅-based thin film gas sensors. TiO₂ doping of Nb₂O₅ films is carried out by co-sputtering without the formation of secondary phases and the surface area of TiO₂-doped Nb₂O₅ films is increased via the use of colloidal templates composed of sacrificial polystyrene beads. The gas sensitivity of Nb₂O₅ films is enhanced through both the TiO₂ doping and the surface embossing. An additional enhancement on the gas sensitivity is obtained by the optimization of the bias voltage applied between interdigitated electrodes beneath Nb₂O₅-based film. More excitingly, such a voltage optimization leads to a substantial decrease in response time. Upon exposure to 50 ppm CO at 350 °C, a gas sensor based on TiO₂-doped Nb₂O₅ film with embossed surface morphology exhibits a very high sensitivity of 475% change in resistance and a rapid response time of 8 s under 3 V, whereas a sensor based on plain Nb₂O₅ film shows a 70% resistance change and a response time of 65 s under 1 V. Thermal stability tests of our Nb₂O₅-based sensor reveal excellent reliability which is of particular importance for application as resistive sensors for a variety gases.     

Microstructural and electrical properties of 0.65Pb(Mg1/3Nb2/3)O3-0.35PbTiO3 (PMN-PT) epitaxial films grown on Si substrates

Epitaxially grown PMN-PT thin films using the PMN-PT single crystal targets were prepared at 550 °C on appropriate buffer layers of LSCO/CeO₂/YSZ deposited on a Si substrate using pulsed laser deposition. The micro-structural and the electrical properties of the films were investigated as a function of the film thickness. The PMN-PT films with the thickness from 200 to 600 nm exhibited an epitaxial nature with a pure perovskite structure. On the other hand, the films above 700 nm included a pyrochlore phase embedded in the perovskite structure although they exhibited an epitaxial nature. A pyrochlore phase included in the films above 700 nm thickness decreased the dielectric constant and the ferroelectric properties of the PMN-PT films.     

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.     

Electrical and CO gas sensing properties of nanostructured La1−xCexCoO3 perovskite prepared by activated reactive synthesis

A series of nanostructred La_1−xCe_xCoO₃ perovskite-type (x ranging from 0 to 0.2), with a crystallite size of around 10 nm and a specific surface area of up to 55 m²/g were prepared using the activated reactive grinding method. XRD results showed that Ce segregates as CeO₂ when the addition level exceeds 10 at%. CO was chosen as a typical reducing gas and its interaction with surface oxygen was investigated. TPD-O₂ was used to investigate the effect of Ce-doping on total surface oxygen. The experimental results confirmed a positive effect of Ce-doping of up to 10 at% on total surface oxygen (α-O₂). TPD-CO and XPS analyses were performed to find the total carbon adsorption (i.e. related to the adsorption of CO) on the surface of the synthesized samples. Both methods confirmed that more carbon adsorbs on the surface of doped formulations compared to the pure LaCoO₃. Ce-doping increases the surface oxygen, thereby facilitating the adsorption and oxidation processes. CO gas sensing properties of thick La_1−xCe_xCoO₃ films were performed. La_0.9Ce_0.1CoO₃ showed the highest conductivity and the lowest activation energy. The optimum CO sensing temperature for doped formulation was found to be 100 °C compared to 130 °C for pure perovskite. Ce-doped samples showed a maximum response ratio of 240% with respect to 100 ppm CO in air compared to 60% obtained with pure LaCoO₃.     

Influence of doping BiYO3 and Nb2O5 on PTCR characteristics of BaTiO3 thermistor ceramics

Nb₂O₅-doped (1 − x)Ba_0.96Ca_0.04TiO₃-xBiYO₃ (where x = 0.01, 0.02, 0.03 and 0.04) lead-free PTC thermistor ceramics were prepared by a conventional solid state reaction method. X-ray diffraction, scanning electron microscope, Agilent E4980A and resistivity-temperature measurement instrument, were used to characteristic the lattice distortion, microstructure, temperature dependence of permittivity and resitivity-temperature dependence. It was revealed that the tetragonality c/a of the perovskite lattice, the microstructure and the Curie temperature changed with the BiYO₃ content. In order to decrease the room temperature resistivity, the effect of Nb₂O₅ on the room temperature resistivity was also studied, and its optimal doping content was finally chosen as 0.2 mol%. The 0.97Ba_0.96Ca_0.04TiO₃-0.03BiYO₃-0.002Nb₂O₅ thermistor ceramic exhibited a low ρ_RT of 3.98 × 10³ Ω cm, a typical PTCR effect of ρ_max/ρ_min > 10³ and a T_c of 153 °C.     

An interferometric biosensor composed of a prism-chamber assembly and a composite waveguide with a Ta2O5 nanometric layer

A highly sensitive integrated polarimetric interferometer biosensor with improved long-time stability and simple operation was prepared by using a novel prism-chamber assembly and an inexpensive waveguide made by sputtering a tapered nanometric layer of Ta₂O₅ on a single-mode glass waveguide. By comparing the measured refractive-index (RI) sensitivities with those simulated based on a four-layer homogeneous waveguide, both the equivalent thicknesses (T_eq) for the tapered Ta₂O₅ layers and a severe dependence of RI sensitivity on T_eq were obtained. Addition of 1 g of water in 100 g of a Chinese liquor (alcohol concentration = 46% (v/v)) was easily detected by the sensor. Monitoring of anti-human IgG adsorption with a waveguide of T_eq = 31.99 nm indicates that the antibody coverage required for inducing a phase-different change of Δ? = π is less than 0.012 monolayer. The same waveguide presents a quasi-linear dependence of Δ? on water temperature with the slope of d(Δ?)/dT = −28.50°/°C to which the contribution by the thermo-optical effect of the waveguide is 4.24°/°C, equivalent to a liquid RI change of Δn_c = 1.41 × 10⁻⁵. The interferometer exhibits the promising potential for chemical and biological analyses because of its outstanding characteristics.     

Enhanced C2H5OH sensing characteristics of nano-porous In2O3 hollow spheres prepared by sucrose-mediated hydrothermal reaction

In₂O₃ hollow spheres with shell thicknesses of ∼150 nm and ∼300 nm were prepared by the one-pot synthesis of indium-precursor-coated carbon spheres via hydrothermal reaction and subsequent removal of core carbon by heat treatment. The gas response (R_a/R_g, R_a: resistance in air, R_g: resistance in gas) of the thin hollow spheres to 100 ppm C₂H₅OH was 137.2 at 400 °C, which was 1.86 and 3.84 times higher than that of the thick hollow spheres and of the nanopowders prepared by precipitation, respectively. The gas sensing characteristics are discussed in relation to the shell configuration of the hollow spheres. The enhanced gas response of the hollow spheres was attributed to the effective diffusion of analyte gas toward the entire sensor surface via very thin and nano-porous shells.     

Hydrothermal synthesis of hollow ZnSnO3 microspheres and sensing properties toward butane

Hollow ZnSnO₃ microspheres were successfully prepared by hydrothermal method at 160 °C for 12 h. The prepared material was characterized by field emission scanning electron microscope (FESEM), transmission electron microscope (TEM) and X-ray diffraction measurements (XRD). The average diameter of the hollow ZnSnO₃ microspheres was in the range of 400-600 nm. Compared with solid ZnSnO₃ microspheres structure, the hollow ZnSnO₃ microspheres showed better response (S) to butane. To 500 ppm butane, the sensor response (S) of the hollow ZnSnO₃ microspheres was 5.79 at the optimum operating temperature of 380 °C, and the response and recovery time were 0.3 s and 0.65 s, respectively. The sensitivities of sensors based on this material were linear with the concentration of butane in the range of 100-1000 ppm.     

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.     

Selectivity of flame-spray-made Nb/ZnO thick films towards NO2 gas

Unloaded ZnO and Nb/ZnO nanoparticles containing 0.25, 0.5 and 1 mol.% Nb were produced in a single step by flame-spray pyrolysis (FSP) technique. The nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The BET surface area (SSA_BET) of the nanoparticles was measured by nitrogen adsorption. FSP yielded small Nb particles attached to the surface of the supporting ZnO nanoparticles, indicating a high SSA_BET. The morphology and accurate size of the primary particles were further investigated by TEM. Nb/ZnO nanoparticles paste composed of ethyl cellulose and terpineol as binder and solvent respectively was coated on Al₂O₃ substrate interdigitated with gold electrodes to form thick films by spin coating technique. After the sensing tests, the morphology and the cross-section of sensing film were analyzed by SEM and EDS analyses. The influence on a low dynamic range of Nb concentration on NO₂ response (0.1-4 ppm) of thick film sensor elements was studied at the operating temperatures ranging from 250 to 350 °C in the presence of dry air. The optimum Nb concentration was found be 0.5 mol.% and 0.5 mol.% Nb exhibited an optimum NO₂ response of ∼1640 and a short response time (27 s) for NO₂ concentration of 4 ppm at 300 °C.     

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.