Highly sensitive and selective LPG sensor based on α-Fe2O3 nanorods

The α-Fe₂O₃ nanorods were successfully synthesized without any templates by calcining the α-FeOOH precursor in air at 300 °C for 2 h and their LPG sensing characteristics were investigated. The α-FeOOH precursor was prepared through a simple and low cost wet chemical route at low temperature (40 °C) using FeSO₄·7H₂O and CH₃COONa as starting materials. The formation of α-FeOOH precursor and its topotactic transformation to α-Fe₂O₃ upon calcination was confirmed by X-ray diffraction measurement (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) analysis. The α-Fe₂O₃ nanorods exhibited outstanding gas sensing characteristics such as, higher gas response (∼1746-50 ppm LPG at 300 °C), extremely rapid response (∼3-4 s), relatively slow recovery (∼8-9 min), excellent repeatability, good selectivity and lower operating temperature (∼300 °C). Furthermore, the α-Fe₂O₃ nanorods are able to detect up to 5 ppm for LPG with reasonable response (∼15) at the operating temperature of 300 °C and they can be reliably used to monitor the concentration of LPG over the range (5-60 ppm). The experimental results clearly demonstrate the potential of using the α-Fe₂O₃ nanorods as sensing material in the fabrication of LPG sensors. Plausible LP G sensing mechanism of the α-Fe₂O₃ nanorods is also discussed.     

Nanostructured spinel ZnCo2O4 for the detection of LPG

Nanostrucutred spinel ZnCo₂O₄ (∼26-30 nm) was synthesized by calcining the mixed precursor (consisting of cobalt hydroxyl carbonate and zinc hydroxyl carbonate) in air at 600 °C for 5 h. The mixed precursor was prepared through a low cost and simple co-precipitation/digestion method. The transformation of the mixed precursor into nanostructured spinel ZnCo₂O₄ upon calcinations was confirmed by X-ray diffraction (XRD) measurement, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM). To demonstrate the potential applicability of ZnCo₂O₄ spinel in the fabrication of gas sensors, its LPG sensing characteristics were systematically investigated. The ZnCo₂O₄ spinel exhibited outstanding gas sensing characteristics such as, higher gas response (∼72-50 ppm LPG gas at 350 °C), response time (∼85-90 s), recovery time (∼75-80 s), excellent repeatability, good selectivity and relatively lower operating temperature (∼350 °C). The experimental results demonstrated that the nanostructured spinel ZnCo₂O₄ is a very promising material for the fabrication of LPG sensors with good sensing characteristics. Plausible LPG sensing mechanism is also discussed.     

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.     

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.     

Gas sensors based on anodic tungsten oxide

Nanostructured porous tungsten oxide materials were synthesized by the means of electrochemical etching (anodization) of tungsten foils in aqueous NaF electrolyte. Formation of the sub-micrometer size mesoporous particles has been achieved by infiltrating the pores with water. The obtained colloidal anodic tungsten oxide dispersions have been used to fabricate resistive WO₃ gas sensors by drop casting the sub-micrometer size mesoporous particles between Pt electrodes on Si/SiO₂ substrate followed by calcination at 400 °C in air for 2 h. The synthesized WO₃ films show slightly nonlinear current-voltage characteristics with strong thermally activated carrier transport behavior measured at temperatures between −20 °C and 280 °C. Gas response measurements carried out in CO, H₂, NO and O₂ analytes (concentration from 1 to 640 ppm) in air as well as in Ar buffers (O₂ only in Ar) exhibited a rapid change of sensor conductance for each gas and showed pronounced response towards H₂ and NO in Ar and air, respectively. The response of the sensors was dependent on temperature and yielded highest values between 170 °C and 220 °C.     

Carbon dioxide sensing properties of bismuth cobaltite

Bismuth cobaltite with sillenite-type structure was prepared from Co(OH)₂ and Bi(NO₃)₃·6H₂O through solid state reaction at 600 °C. Neutron powder diffraction (NPD) data and X-ray absorption spectroscopy revealed the existence of mixed oxidation states for cobalt in this compound, the chemical formula being Bi₁₂(Bi_0.55Co_0.45)O_19.6. The gas sensing properties of Bi₁₂(Bi_0.55Co_0.45)O_19.6 were characterized by alternating current, at 200, 300 and 400 °C. The optimal response was observed at 400 °C, using a frequency of 100 kHz.     

Synthesis and gas sensing properties of bundle-like α-Fe2O3 nanorods

Bundle-like α-Fe₂O₃ nanostructures were successfully synthesized by a simple calcination of β-FeOOH precursor derived from a hydrothermal method in the presence of poly(vinyl pyrrolidone). The as-prepared products were characterized by X-ray power diffraction, field emission scanning electron microscopy, and transmission electron microscopy. The results indicated that bundle-like nanostructures were composed of well-aligned single crystalline nanorods with the diameters of 20-30 nm and the lengths of 200-300 nm. The gas sensing properties of as-prepared products were investigated. It was found that the sensor based on α-Fe₂O₃ nanostructure exhibited high response, quick response-recovery, and good repeatability to acetone at 250 °C.     

Synthesis and characterisation of nanosized TiO2-ZrO2 binary system prepared by an aqueous sol-gel process: Physical and sensing properties

Nanostructured TiO₂-ZrO₂ thin films and powders were prepared by a straightforward aqueous particulate sol-gel route. Titanium (IV) isopropoxide and zirconium (IV) acetate hydrate were used as precursors, and hydroxypropyl cellulose was used as a polymeric fugitive agent in order to increase the specific surface area. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy revealed that the powder were crystallised at the low temperature of 500 °C, containing anatase-TiO₂ and tetragonal-ZrO₂ phases. Furthermore, it was found that ZrO₂ retarded the anatase-to-rutile transformation up to 900 °C. The activation energies for crystallite growth of TiO₂ and ZrO₂ components in the binary system were calculated 10.16 and 3.12 kJ/mol, respectively. Transmission electron microscope (TEM) image showed that one of the smallest crystallite sizes was obtained for TiO₂-ZrO₂ binary mixed oxide, being 5 nm at 500 °C. Field emission scanning electron microscope (FESEM) analysis revealed that the deposited thin films had nanostructured morphology with the average grain size of 20 nm at 500 °C and 36 nm at 900 °C. Thin films produced under optimised conditions showed excellent microstructural properties for gas sensing applications. They exhibited a remarkable response towards low concentrations of CO and NO₂ gases at low operating temperature of 150 °C, resulted in an increase of thermal stability of sensing films as well as a decrease in the power consumption. Furthermore, calibration curves revealed that TiO₂-ZrO₂ sensor follows the power law, S = A[gas]^B (where S is sensor response, coefficients A and B are constants and [gas] is gas concentration) for the two types of gases, and it has excellent capability for the detection of low gas concentrations.     

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.     

Fabrication of N-type Fe2O3 and P-type LaFeO3 nanobelts by electrospinning and determination of gas-sensing properties

N-type Fe₂O₃ nanobelts and P-type LaFeO₃ nanobelts were prepared by electrospinning. The structure and micro-morphology of the materials were characterized by X-ray diffraction (XRD) and scanning of electron microscopy (SEM). The gas sensing properties of the materials were investigated. The results show that the optimum operating temperature of the gas sensors fabricated from Fe₂O₃ nanobelts is 285 °C, whereas that from LaFeO₃ nanobelts is 170 °C. Under optimum operating temperatures at 500 ppm ethanol, the response of the gas sensors based on these two materials is 4.9 and 8.9, respectively. The response of LaFeO₃-based gas sensors behaves linearly with the ethanol concentration at 10-200 ppm. Sensitivities to different gases were examined, and the results show that LaFeO₃ nanobelts exhibit good selectivity to ethanol, making them promising candidates as practical detectors of ethanol.     

Nanosized titania derived from a novel sol-gel process for ammonia gas sensor applications

Highly redispersible anatase nanoparticles were prepared by a novel sol-gel based hydrothermal process for gas sensing applications. Thin titania films composed of nanoparticles were deposited on Au interdigital electrodes by dip-coating, annealed and tested in a gas test bench at 350 °C. The anatase films showed a very high sensitivity towards ammonia and no cross interference by CO₂, O₂ and C₃H₈. To classify the sensor as an ammonia gas sensor, a comparison with other sensor designs from literature has been performed.     

Suppression of NO and SO2 cross-sensitivity in electrochemical CO2 sensors with filter layers

Interfering effects of NO and SO₂ gases on CO₂ sensing performance of the solid state galvanic cell, Pt, O₂, CO₂, Na₂CO₃–BaCO₃ǀǀNa⁺ǀǀNa₂Ti₆O₁₃–TiO₂, O₂, Pt were investigated at 673 K and 773 K. In the interfering gases concentration ranges of 50–150 ppm NO and 5–15 ppm SO₂, exposure to NO gas guaranteed a recovery of electromotive force (EMF) from the relatively small EMF deviation. However, SO₂ gas remarkably degraded the performance of the sensor arising from the formation of sulfate on the sensing electrode. Na₂CO₃–SnO₂, Na₂CO₃–SnO₂–Cu, and Na₂CO₃–SnO₂–CuO were heat-treated and adopted as filter materials adjacent to the sensing electrode. The EMF response of the CO₂ sensors with filters was compared in terms of filter efficiency. Among them, Na₂CO₃–SnO₂–CuO filter showed the most promising characteristics in suppressing NO and SO₂ gas interference.     

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.     

Solid-state potentiometric SO2 sensor combining NASICON with V2O5-doped TiO2 electrode

A compact tubular sensor based on NASICON (sodium super ionic conductor) and V₂O₅-doped TiO₂ sensing electrode was designed for the detection of SO₂. In order to reduce the size of the sensor, a thick-film of NASICON was formed on the outer surface of a small Al₂O₃ tube; furthermore, a thin layer of V₂O₅-doped TiO₂ with nanometer size was attached on the NASICON as a sensing electrode. This paper investigated the influence of V₂O₅ doping and sintering temperature on the characteristics of the sensor. The sensor attached with 5 wt% V₂O₅-doped TiO₂ sintered at 600 °C exhibited excellent sensing properties to 1–50 ppm SO₂ in air at 200–400 °C. The EMF value of the sensor was almost proportional to the logarithm of SO₂ concentration and the sensitivity (slope) was −78 mV/decade at 300 °C. It was also seen that the sensor showed a good selectivity to SO₂ against NO, NO₂, CH₄, CO, NH₃ and CO₂. Moreover, the sensor had speedy response kinetics to SO₂ too, the 90% response time to 50 ppm SO₂ was 10 s, and the recovery time was 35 s. On the basis of XPS analysis for the SO₂-adsorbed sensing electrode, a sensing mechanism involving the mixed potential at the sensing electrode was proposed.     

Synthesis of ZnO nanorods and its application in NO2 sensors

One-dimensional (1D) ZnO nanorods with pencil-like shape and high aspect ratio were successfully synthesized using a cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process at 90 °C. The surface morphology and structure of nanocrystals were characterized by FE-SEM, XRD and XPS analysis. Experimental results show that the surfactant and base concentration play important roles in the formation and growth orientation of ZnO nanorods. The ZnO nanorods synthesized exhibits high response and selectivity to NO₂, the highest response to 40 ppm NO₂ reached 206 and the selectivity with respect to CO and CH₄ at same concentration reached 10.3 and 30 times, respectively. The effects of synthesis method, surfactant and calcination condition on sensing properties were systematically investigated. The results indicate that the CTAB-assisted low temperature hydrothermal process is a potentially facile method for synthesis of 1D ZnO nanorods and excellent potential candidates as gas sensing materials.     

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.     

Synthesis of nearly monodisperse Co3O4 nanocubes via a microwave-assisted solvothermal process and their gas sensing properties

Nearly monodisperse Co₃O₄ nanocubes have been prepared by a microwave-assisted solvothermal (MS) method at 180 °C for 20 min. The samples are characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD pattern and TEM images of the products illustrated that Co₃O₄ nanocubes had a cubic phase with a lateral size of ∼20 nm. The gas response of the Co₃O₄ nanocubes was studied to several typical organic gases. The Co₃O₄ nanocubes showed good gas sensing performance towards xylene and ethanol vapors with rapid and high responses at a low-operating temperature. The results showed that the Co₃O₄ nanocubes can be used to fabricate high performance gas sensors.     

Novel solid-state manganese oxide-based reference electrode for YSZ-based oxygen sensors

Various Mn-based oxides have been screened to find a suitable all-solid-state gas-insensitive reference-electrode (RE) for yttria-stabilized zirconia (YSZ)-based potentiometric oxygen sensor. The experimental observation of tubular YSZ-based sensors attached with each of the outer Mn-based oxide sensing electrodes (SEs) and the inner Pt-RE revealed that Mn₂O₃-SE was insensitive to all gases including oxygen at operating temperatures below 550 °C. Thus, the planar-like rod-type YSZ-based sensor using Pt-SE, Au-SE and Mn₂O₃-RE was then fabricated and its sensing performances were evaluated at 550 °C. As a result, the planar sensor using a couple of Pt-SE and Mn₂O₃-RE exhibited excellent responses to oxygen in the concentration range of 0.05-21 vol.% obeying Nernst equation and gave negligible responses to other co-existing gases. Close similarity of the results for tubular and planar sensors operated in a wide range of air/fuel (A/F) ratio indicated that the tubular YSZ-based sensor using the inner Pt-RE could be successfully miniaturized to the planar one using Mn₂O₃-RE without sacrificing its performance.     

New gas sensitive MIS structures Pt/Al2O3(M = Pt, Rh)/Si with a granular dielectric layer

New gas sensitive MIS structures Pt/Al₂O₃(M)/p-Si, where M = Pt, Rh, with granular dielectric Al₂O₃ layers doped with noble metals were obtained by an aerosol pyrolysis method. Surface morphology and composition of the structures were studied by TEM, AFM and EPMA. Sensor properties of the MIS structures were studied towards reducing gases (1000 ppm H₂, 300 ppm CO, 1000 ppm CH₄ in air) at 100 and 200 °C. The Pt/Al₂O₃(M = Pt, Rh)/Si structures showed a very high sensor response to reducing gases. A shift of C–V characteristics was up to 2.5 V under CO, 2.2 V under hydrogen and 0.7 V under methane. High values of shift of C–V curves can be related with cooperative influence of a change of surface state density in dielectric layer, reduction of platinum electrode and dipole layer formation.     

CdO activated Sn-doped ZnO for highly sensitive, selective and stable formaldehyde sensor

Sn-, Ni-, Fe- and Al-doped ZnO and pure ZnO are prepared by coprecipitation method, and characterized by scanning electron microscope (SEM), energy diffraction spectra (EDS) and X-ray diffraction (XRD). Their formaldehyde gas sensing properties are evaluated and the results show that 2.2 mol% Sn dopant can increase the response of ZnO by more than 2 folds, while other dopants increase little response or even decrease response. Further, CdO is used to activate ZnO based formaldehyde sensing material. It is demonstrated that 10 mol% CdO activated 2.2 mol% Sn-doped ZnO has the highest formaldehyde gas response, with a linear sensitivity of ∼10/ppm at lowered work temperature of 200 °C than 400 °C of pure ZnO, and high selectivity over toluene, CO and NH₃, as well as good stability tested in 1 month.