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.     

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.     

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.     

A technique for monitoring SO2 in combustion exhausts: Use of a non-Nernstian sensing element in combination with an upstream catalytic filter

Detection of sulfur dioxide (SO₂) at high temperature (600–750 °C) in the presence of some interferents found in combustion exhausts (NO₂, NO, CO₂, CO, and hydrocarbon (C₃H₆)) is described. The detection scheme involves use of a catalytic filter in front of a non-Nernstian (mixed-potential) sensing element. The catalytic filter was a Ni:Cr powder bed operating at 850 °C, and the sensing elements were pairs of platinum (Pt) and oxide (Ba-promoted copper chromite ((Ba,Cu)_xCr_yO_z) or Sr-modified lanthanum ferrite (LSF)) electrodes on yttria-stabilized zirconia. The Ni:Cr powder bed was capable of reducing the sensing element response to NO₂, NO, CO, and C₃H₆, but the presence of NO₂ or NO (“NO_x”, at 100 ppm by volume) still interfered with the SO₂ response of the Pt–(Ba,Cu)_xCr_yO_z sensing element at 600 °C, causing approximately a 7 mV (20%) reduction in the response to 120 ppm SO₂ and a response equivalent to about 20 ppm SO₂ in the absence of SO₂. The Pt–LSF sensing element, operated at 750 °C, did not suffer from this NO_x interference but at the cost of a reduced SO₂ response magnitude (120 ppm SO₂ yielded 10 mV, in contrast to 30 mV for the Pt-(Ba,Cu)_xCr_yO_z sensing element). The powder bed and Pt–LSF sensing element were operated continuously over approximately 350 h, and the response to SO₂ drifted downward by about 7%, with most of this change occurring during the initial 100 h of operation.     

Au-doped WO3-based sensor for NO2 detection at low operating temperature

Pure and Au-doped WO₃ powders for NO₂ gas detection were prepared by a colloidal chemical method, and characterized via X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The NO₂ sensing properties of the sensors based on pure and Au-doped WO₃ powders were investigated by HW-30A gas sensing measurement. The results showed that the gas sensing properties of the doped WO₃ sensors were superior to those of the undoped one. Especially, the 1.0 wt% Au-doped WO₃ sensor possessed larger response, better selectivity, faster response/recovery and better longer term stability to NO₂ than the others at relatively low operating temperature (150 °C).     

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.     

Necked ZnO nanoparticle-based NO2 sensors with high and fast response

The NO₂ gas sensing characteristics of semiconductor type gas sensors with channels composed of necked ZnO nanoparticles (NPs) were investigated in this study. The heat treatment of the NPs at 400 °C led to their necking and coarsening. The response of the necked-NP-based sensors was as high as 100 when exposed to 0.2 ppm of NO₂ at 200 °C. As the concentration of NO₂ increased to 5 ppm, their response was enhanced to approximately 400. During the repeated injection of NO₂ gas with a concentration of 0.4 ppm, the sensors exhibited stable response characteristics. Furthermore, the 90% response and recovery times of the gas sensor were as fast as 13 and 10 s, respectively. These observations indicate that the non-agglomerated necking of the NPs induced by the heat treatment significantly enhances the gas sensing characteristics of the NP-based gas sensors.     

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.     

Ab initio calculations of NO2 and SO2 chemisorption onto non-polar ZnO surfaces

The authors present an ab initio study of NO₂ and SO₂ chemisorption onto non-polar ZnO and ZnO surfaces with the aim of providing theoretical hints for further developments in gas sensors. From first principles calculations (DFT-GGA approximation), the most relevant surface reduction scenarios are analyzed and, subsequently, considered in the chemisorption study. First, calculations indicate that NO₂ adsorbs avidly onto Zn surface atoms. This is compatible with the oxidizing character of NO₂. Second, results also explain the sensor poisoning by SO₂ adsorption (since this molecule competes with NO₂ for the same adsorption sites) and indicate that poisoning can only be reverted at typical operation temperatures (T ≤ 700 °C) in the case of stoichiometric ZnO surfaces.     

Pulsed laser deposited Y-doped BaZrO3 thin films for high temperature humidity sensors

Pulsed laser deposited (PLD) Y-doped BaZrO₃ thin films (BaZr_1-xY_xO_3-y/2, x = 0.2, y > 0), were investigated as to their viability for reliable humidity microsensors with long-term stability at high operating temperatures (T > 500 °C) as required for in situ point of source emissions control as used in power plant combustion processes. Defect chemistry based models and initial experimental results in recent humidity sensor literature [1] and [2]. indicate that bulk Y-doped BaZrO₃ could be suitable for use in highly selective, high temperature compatible humidity sensors. In order to accomplish faster response and leverage low cost batch microfabrication technologies we have developed thin film deposition processes, characterized layer properties, fabricated and tested high temperature humidity micro sensors using these thin films. Previously published results on sputtering Y-doped BaZrO₃ thin films have confirmed the principle validity of our approach [3]. However, the difficulty in controlling the stoichiometry of the films and their electrical properties as well as mud flat cracking of the films occurring either at films thicker than 400 nm or at annealing temperature above 800 °C have rendered sputtering a difficult process for the fabrication of reproducible and reliable thin film high temperature humidity microsensors, leading to the evaluation of PLD as alternative deposition method for these films.X-ray Photoelectron Spectroscopy (XPS) data was collected from as deposited samples at the sample surface as well as after 4 min of Ar⁺ etching. PLD samples were close to the desired stoichiometry. X-ray diffraction (XRD) spectra from all as deposited BaZrO₃:Y films show that the material is polycrystalline when deposited at substrate temperatures of 800 °C. AFM results revealed that PLD samples have a particle size between 32 nm and 72 nm and root mean square (RMS) roughness between 0.2 nm and 1.2 nm. The film conductivity increases as a function of temperature (from 200 °C to 650 °C) and upon exposure to a humid atmosphere, supporting our hypothesis of a proton conduction based conduction and sensing mechanism. Humidity measurements are presented for 200–500 nm thick films from 500 °C to 650 °C at vapor pressures of between 0.05 and 0.5 atm, with 0.03–2% error in repeatability and 1.2–15.7% error in hysteresis during cycling for over 2 h. Sensitivities of up to 7.5 atm⁻¹ for 200 nm thick PLD samples at 0.058 atm partial pressure of water were measured.     

Polypyrrole functionalized with FePcTSA for NO2 sensor application

The nitrogen dioxide (NO₂) sensing capability of polypyrrole (PPy) was enhanced dramatically after functionalized with iron(III)phthalocyanine-4,4′,4″,4-tetrasulfonic acid monosodium salt (FePcTSA). The incorporated phthalocyanine was confirmed by different characterization techniques such as UV–vis spectroscopy, FTIR, GFAAS, EDAX, etc. The resistance of the functionalized PPy decreased spontaneously during exposure to NO₂ gas at room temperature. This material exhibited excellent stability, reversibility, and reproducibility. The lowest response time (t₅₀) thus obtained is 47 s with a highest response factor (ΔR/R₀ × 100) of 50.25.     

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.     

Controlled synthesis and gas-sensing properties of hollow sea urchin-like α-Fe2O3 nanostructures and α-Fe2O3 nanocubes

Hollow sea urchin-like α-Fe₂O₃ nanostructures were successfully synthesized by a hydrothermal approach using FeCl₃ and Na₂SO₄ as raw materials, and subsequent annealing in air at 600 °C for 2 h. The hollow sea urchin-like α-Fe₂O₃ nanostructures with the diameters of 2–4.5 μm consist of well-aligned α-Fe₂O₃ nanorods with an average length of about 1 μm growing radially from the centers of the nanostructures, have a hollow interior with a diameter of about 2 μm. α-Fe₂O₃ nanocubes with a diameter of 700–900 nm were directly obtained by a hydrothermal reaction of FeCl₃ at 140 °C for 12 h. The response S_r (S_r = R_a/R_g) of the hollow sea urchin-like α-Fe₂O₃ nanostructures reached 2.4, 7.5, 5.9, 14.0 and 7.5 to 56 ppm ammonia, 32 ppm formaldehyde, 18 ppm triethylamine, 34 ppm acetone, and 42 ppm ethanol, respectively, which was excess twice that of the α-Fe₂O₃ nanocubes and the nanoparticle aggregations. Our results demonstrated that the hollow sea urchin-like α-Fe₂O₃ nanostructures were very promising for gas sensors for the detection of flammable and/or toxic gases with good-sensing characteristics.     

Characterization of electrospun ZnO–SnO2 nanofibers for ethanol sensor

ZnO–SnO₂ nanofibers have been developed through in situ electrospinning technique and calcination. Poly(vinyl pyrrolidone) (PVP) is selected as fiber template. The composition of products can be controlled concisely by adjusting the compositions in their precursors. Under the optimized experimental conditions, the prepared product shows the desirable sensing characteristics towards ethanol gas at 300 °C, such as high response, excellent linearity in the range of 1–300 ppm, quick response time (5 s) and recovery time (6 s), good reproducibility, stability and selectivity.     

Influence of Cs doping in spray deposited SnO2 thin films for LPG sensors

Detection of low concentrations of petroleum gas was achieved using transparent conducting SnO₂ thin films doped with 0–4 wt.% caesium (Cs), deposited by spray pyrolysis technique. The electrical resistance change of the films was evaluated in the presence of LPG upon doping with different concentrations of Cs at different working temperatures in the range 250–400 °C. The investigations showed that the tin oxide thin film doped with 2% Cs with a mean grain size of 18 nm at a deposition temperature of 325 °C showed the maximum sensor response (93.4%). At a deposition temperature of 285 °C, the film doped with 3% Cs with a mean grain size of 20 nm showed a high response of 90.0% consistently. The structural properties of Cs-doped SnO₂ were studied by means of X-ray diffraction (XRD); the preferential orientation of the thin films was found to be along the (3 0 1) directions. The crystallite sizes of the films determined from XRD are found to vary between 15 and 60 nm. The electrical investigations revealed that Cs-doped SnO₂ thin film conductivity in a petroleum gas ambience and subsequently the sensor response depended on the dopant concentration and the deposition temperature of the film. The sensors showed a rapid response at an operating temperature of 345 °C. The long-term stability of the sensors is also reported.     

Development of SAW-based multi-gas sensor for simultaneous detection of CO2 and NO2

A 440 MHz wireless and passive surface acoustic wave (SAW)-based multi-gas sensor integrated with a temperature sensor was developed on a 41° YX LiNbO₃ piezoelectric substrate for the simultaneous detection of CO₂, NO₂, and temperature. The developed sensor was composed of a SAW reflective delay lines structured by an interdigital transducer (IDT), ten reflectors, a CO₂ sensitive film (Teflon AF 2400), and a NO₂ sensitive film (indium tin oxide). Teflon AF 2400 was used for the CO₂ sensitive film because it provides a high CO₂ solubility, with good permeability and selectivity. For the NO₂ sensitive film, indium tin oxide (ITO) was used. Coupling of mode (COM) modeling was conducted to determine the optimal device parameters prior to fabrication. Using the parameters determined by the simulation results, the device was fabricated and then wirelessly measured using a network analyzer. The measured reflective coefficient S₁₁ in the time domain showed high signal/noise (S/N) ratio, small signal attenuation, and few spurious peaks. The time positions of the reflection peaks were well matched with the predicted values from the simulation. High sensitivity and selectivity were observed at each target gas testing. The obtained sensitivity was 2.12°/ppm for CO₂ and 51.5°/ppm for NO₂, respectively. With the integrated temperature sensor, temperature compensation was also performed during gas sensitivity evaluation process.     

H2 sensing characteristics of highly textured Pd-doped SnO2 thin films

The effects of the crystallographic orientation on the H₂ gas sensing properties were investigated in highly oriented polycrystalline Pd-doped SnO₂ films, which were obtained using rf magnetron sputtering of a Pd (0.5 wt%)-SnO₂ target on various substrates (a-, m-, r-, and c-cut sapphire and quartz). All the films had a similar thickness (110 nm), root-mean-square (rms) roughness (1.3 nm), surface area, and chemical status (O, Sn, and Pd). However, the orientation of the films was strongly affected by the orientation of the substrates. The (1 0 1), (0 0 2), and (1 0 1) oriented films were grown on (a-cut), (m-cut), and (r-cut) Al₂O₃ substrates, respectively, and rather randomly oriented films were deposited on (0 0 0 1) (c-cut) Al₂O₃ and quartz substrates. In addition, the oriented Pd-doped SnO₂ films were highly textured and had in-plane orientation relationships with the substrates similar to the epitaxial films. The (1 0 1) Pd-doped SnO₂ films on and Al₂O₃ showed a considerably higher H₂ sensitivity, and their gas response decreased with increasing sensing temperature (400–550 °C). The films deposited on and (0 0 0 1) Al₂O₃ showed the maximum sensitivity at 500 °C. The comparison of the H₂ gas response between undoped and Pd-doped SnO₂ films revealed that the Pd-doping shifted the optimum sensing temperature to a lower value instead of improving the gas sensitivity.     

pH sensor based on the crown heteropolyanion K28Li5H7P8W48O184·92H2O immobilized using a layer by layer assembly process

A new sensitive pH sensor based on immobilization of the crown heteropolyanion K₂₈Li₅H₇P₈W₄₈O₁₈₄·92H₂O (P₈W₄₈) on a electrode surface through a layer by layer assembly process is described. The immobilization is based on the electrostatic adsorption of the complex in layers of charged polyelectrolyte poly(allylamine hydrochloride) (PAH). The deposited P₈W₄₈/LBL film was investigated by cyclic voltammetry, potentiometry and electrochemical impedance spectroscopy. Compared to the electrochemical behavior of dissolved P₈W₄₈, a slight shift in the redox peak towards negative potentials is observed, which have been attributed to a slight decrease in the acidity of the interior of the P₈W₄₈/LBL film compared to the testing buffer solution. The relationship between the peak currents of the deposited P₈W₄₈/LBL film and the number of layers is shown to be linear, which demonstrates that equal amounts of P₈W₄₈ are adsorbed in each deposition layer. The P₈W₄₈/LBL modified electrode showed high sensitivities toward pH. Therefore, such electrodes were tested as pH sensors using the titration method. The resulting pH sensor has a detection range of pH 1–13, a sensitivity of 69 ± 2 mV/pH, high repeatability (<3 mV), fast response time (<7 s), low sensitivity toward change in ionic strength and nature of the supporting electrolyte, low internal resistance and a working life time of at least 3 months. Moreover, the sensor is easy to manufacture and can be easily miniaturized for measurements in micro- and nano-systems.     

Glucose-mediated hydrothermal synthesis and gas sensing characteristics of WO3 hollow microspheres

Tungsten-coated carbon microspheres were prepared by one-pot hydrothermal reaction of an aqueous solution containing glucose and sodium tungstate. The spheres were converted into WO₃ hollow microspheres by the decomposition of their core carbon. The [glucose]/[sodium tungstate] ratio of the stock solution determined not only the morphology of the precursors but also the phase of the powders after calcination. The WO₃ hollow microspheres showed a higher gas response and more selective detection of 0.5–2.5 ppm NO₂ than WO₃ solid and nano-porous microspheres did. The enhanced NO₂ sensing characteristics are explained in relation to the surface area, pore volume, and hollow morphology.     

Acoustic wave-based NO2 sensor: Ink-jet printed active layer

Microsphere-templated BaCO₃ films with well-defined area were deposited onto quartz crystal microbalances by thermal ink-jet printing, and the devices were characterized with respect to their microstructures and NO₂ sensing characteristics. Highly porous three-dimensional BaCO₃ frameworks with promising sensor characteristics were obtained. The printed thin films exhibited reversible frequency shifts following exposure to NO₂ and subsequent recovery under CO/CO₂ at 400 °C. The feasibility of controlled deposition of complex functional films in controlled patterns is discussed in the context of the direct-write features of ink-jet printing.