Calorimetric hydrocarbon sensor for automotive exhaust applications

We have developed a calorimetric sensor utilizing a thermoelectric device supported on a planar alumina substrate. By using a highly selective carbon monoxide (CO) oxidation catalyst and a non-selective platinum (Pt) catalyst, the device can be built to detect either CO or hydrocarbons with high selectivity. The CO oxidation catalyst comprises lead-modified platinum and exhibits excellent selectivity over the 200–400 °C temperature range. The thermoelectric device consists of two thick film junctions made of niobium pentoxide (Nb₂O₅)-doped titanium dioxide (TiO₂) and a lithiated nickel (Ni), which are supported on a planar alumina substrate. The thermocouple detects the difference in temperature due to different catalytic reactions over the two junctions and shows a high output signal because of the high Seebeck coefficient of Nb₂O₅-doped TiO₂ (−400 μV/°C). In gas bench tests, the sensor has a linear output of 0–2.75 mV over 0–1000 ppm of propylene and a response time of 2.5 s (at 90% of amplitude) at a gas temperature of 350 °C. An engine dynamometer evaluation shows that the response of the sensor parallels the change in CO and hydrocarbon constituent concentrations when the engine air-to-fuel ratio is varied.     

Microstructure, electrical and ethanol-sensing properties of perovskite-type SmFe0.7Co0.3O3

Ultrafine SmFe_0.7Co_0.3O₃ powder, prepared by a sol–gel method, shows a single-phase orthogonal perovskite structure. The influence of annealing temperature upon its crystal cell volume, microstructure, electrical and ethanol-sensing properties was investigated in detail. When the annealing temperature increases from 600 to 950 °C, the unit cell volume of the SmFe_0.7Co_0.3O₃ sample reduces, and its average grain size increases. When the annealing temperature increases from 600 to 850 °C, the optimal working temperature and response to ethanol of the SmFe_0.7Co_0.3O₃ sensor increase, and the response–recovery time shortens. But when the annealing temperature further increases from 850 to 950 °C, there are decreases of the optimal working temperature and sensor response, and the response–recovery time is prolonged. The results indicate that, as for sensor response, its optimal annealing temperature is about 850 °C, and the sensor based on SmFe_0.7Co_0.3O₃ annealed at 850 °C shows the highest response S = 80.8 to 300 ppm ethanol gas, and it has the best response–recovery and selectivity characteristics. When the ethanol concentration is as low as 500 ppm, the curve of its optimal response versus concentration is nearly linear. Meanwhile, the influence mechanisms of annealing temperature upon the conductance, the optimal working temperature and sensor response for SmFe_0.7Co_0.3O₃ were studied.     

Characterization of transition metal oxide ceramic material for continuous thermocouple and its use as NTC fire wire sensor

The ceramic powder prepared from the mixture of Mn₃O₄ and La₂O₃ have been characterized for NTC behavior and the same have been used as CT²C (continuous thermocouple) sensor in the form of a thin metal cable to detect over-heating. These materials have mega ohm resistance at room temperature and showed exponential drop in resistance with the rise in temperature over a temperature range of 100–400 °C. It has been observed that as the concentration of La₂O₃ increases from 0 to 10% the NTC behavior drops from (400–260 °C) ±10%. The material was pressed into pellets and sintered at 700 °C for 3 h resulting in good bonding strength. Electrical characterization of the material was done by measuring the resistance over a temperature range of 100–400 °C. The material showed reproducible NTC characteristics over the temperature range 400, 370, 340, 280, and 260 °C with decreasing thermistor constant values (B = 9588, 9210, 8500, 5170, 3330 K⁻¹) and activation energy (ΔE = 826, 794, 733, 445, 287 meV), respectively. The decrease in activation energy of the ceramic powder with increase in La₂O₃ concentration makes it possible to fabricate thermal sensors which can be used in different temperature ranges. The microstructure was studied using SEM and evidence of a sintered body with grain size around 1 μm was observed in the material. XRD analysis indicated the single-phase tetragonal structure of the ceramic material. The process of using this ceramic material for fabrication of 10 ft continuous fire wire sensor has been explained.     

TiO2 thin films from titanium butoxide: Synthesis, Pt addition, structural stability, microelectronic processing and gas-sensing properties

TiO₂ thin films were prepared by spin-coating of a Ti butoxide-derived sol onto oxidized silicon wafers, followed by a heat-treatment at temperatures ranging from 500 to 800 °C. The film thickness after heat-treatment at 500 °C was 50 nm. Pt addition, with a Pt:Ti nominal atomic ratio ranging from 0.01 to 0.1, was achieved by adding solutions of Pt(II) acetylacetonate to the TiO₂ sols. The thin films were investigated by X-ray diffraction, evidencing that Pt promoted the structural transformation of the starting anatase phase of TiO₂ to rutile, with a more enhanced effect with increasing the Pt concentration and/or the heat-treatment temperature. High-resolution transmission electron microscopy evidenced that, when a Pt:Ti atomic ratio of 0.05 and a heat treatment at 500 °C were used, the TiO₂ contained both anatase and rutile phases and interspersed Pt nanocrystals (2–3 nm). This result allowed attributing the structural transformation in TiO₂ to the strain created by the Pt nanocrystals—a conclusion which was further corroborated by the observation that Pd-modified films, prepared under similar conditions, were only composed of anatase TiO₂ and did not contain any Pd nanocrystals. The films heat-treated at 500 °C were able to withstand a full microelectronic processing sequence, including dry etching for gas sensors sensitive area definition, Ti/Pt contact formation, and heater processing on the backside of the sensor substrates. H₂ gas-sensing tests evidenced that the anatase TiO₂ phase was much more sensitive than the rutile one. The presence of Pt further enhanced the gas-sensing properties, lowering the optimum sensor operation temperature to about 330 °C and allowing for the detection of a minimum H₂ concentration of about 1000 ppm.     

Potentiometric CO2 gas sensor with lithium phosphorous oxynitride electrolyte

Potentiometric cell, Au/LiCoO₂ 5 m/o Co₃O₄/Li_2.88PO_3.73N_0.14/Li₂CO₃/Au, has been fabricated and investigated for monitoring CO₂ gas. A LiCoO₂–Co₃O₄ mixture was used as the solid-state reference electrode instead of a reference gas. The idea is to keep the lithium activity constant on the reference side using thermodynamic equilibrium at a given temperature. The thermodynamic stability of the reference electrode was studied from the phase stability diagram of Li–Co–C–O system. The Gibb’s free energy of formation of LiCoO₂ was estimated at 500°C from the measured value of the cell emf. The sensors showed good reversibility and fast response toward changing CO₂ concentrations from 200 to 3000 ppm. The emf values were found to follow a logarithmic Nernstian behavior in the 400–500°C temperature range. CH₄ gas did not show any interference effect. Humidity and CO gas decreased the emf values of the sensor slightly. NO and NO₂ gases affect this sensor significantly at low temperatures. However, increased operating temperature seems to reduce the interference.     

Room temperature synthesis of γ-Fe2O3 by sonochemical route and its response towards butane

Nanocrystalline gamma iron oxide (γ-Fe₂O₃) has been synthesized at room temperature through sonication-assisted precipitation technique. The key in obtaining γ-Fe₂O₃ at room temperature lies in exploiting high-power ultrasound (600 W). The gas-sensing properties to n-butane of pure γ-Fe₂O₃ were investigated by studying the electrical properties of the sensor elements fabricated from the synthesized powder. The maximum response (90%) of the sensor to 1000 ppm n-butane at 300 °C can be explained on the basis of catalytic activity of the nanocrystallites. The response and recovery time of the sensor to 1000 ppm n-butane were less than 12 s and 120 s, respectively.     

Pyroelectric and dielectric properties of sol–gel derived barium–strontium–titanate (Ba0.64Sr0.36TiO3) thin films

The barium–strontium–titanate (BST, Ba_0.64Sr_0.36TiO₃) thin films have been prepared by the sol–gel method on a platinum-coated silicon substrate. The resulting thin films show very good dielectric and pyroelectric properties. The dielectric constant and dissipation factor for Ba_0.64Sr_0.36TiO₃ thin film at a frequency of 200 Hz were 592 and 0.028, respectively. The dependence of the capacitance as a function of the voltage shows a strongly non-linear character, and two peaks characterizing spontaneous polarization switching can be clearly seen in this curve, indicating that the films have a ferroelectric nature. The capacitance changed from 495 to 1108 pF with the applied voltage in the −5 to +5 V range at a frequency of 100 kHz. The peak pyroelectric coefficient at 30 °C is 1080 μC/m² K. The pyroelectric coefficient at room temperature (25 °C) is 1860 μC/m² K, and the figure-of-merit of this film is 37.4 μC/m³ K. The high pyroelectric coefficients and the greater figures-of-merit of Ba_0.64Sr_0.36TiO₃ thin films make it possible to be used for thermal infrared detection and imaging.     

High-performance solid-electrolyte SOx sensor using MgO-stabilized zirconia tube and Li2SO4---CaSO4---SiO2 auxiliary phase

Solid-electrolyte-based electrochemical SO_x sensors fabricated with MgO-stabilized zirconia and Li₂SO₄---CaSO₄---SiO₂ (4:4:2 in molar ratio) exhibit fairly good sensing characteristics for 2–200 ppm SO₂ in air at 600–750 °C, with the e.m.f. responses following the Nernst equation for the two-electron reduction of SO₂. The 90% response and 90% recovery times to 20 ppm SO₂ are 10 s and 7 min at 650 °C, and 10 s and 3 min at 700 °C, respectively. It is further found that the sensor exhibits excellent selectivity to SO_x in the coexistence of CO₂ and NO_x, and good long-term stability. The sensor is simple in structure, easy to prepare, and quite tough chemically and mechanically. These features should ensure practical use for this SO_x sensor.     

CuO/SnO2 thin film heterostructures as chemical sensors to H2S

CuO/SnO₂ heterostructures as well as SnO₂(CuO) polycrystalline films have been studied for H₂S sensing. Gas sensing properties of these materials have been compared in conditions: 25–300 ppm H₂S in N₂ at 100–250°C. A shorter response time of the heterostructures as compared to that of the SnO₂(CuO) films has been found. It is suggested that the improvement of dynamic sensor properties of SnO₂/CuO heterostructures is caused by the localization of electrical barrier between CuO and SnO₂ layers.     

Impedancemetric gas sensor based on Pt and WO3 co-loaded TiO2 and ZrO2 as total NOx sensing materials

Pt-loaded metal oxides [WO₃/ZrO₂, MO_x/TiO₂ (MO_x = WO₃, MoO₃, V₂O₅), WO₃ and TiO₂] equipped with interdigital Au electrodes have been tested as a NO_x (NO and NO₂) gas sensor at 500 °C. The impedance value at 4 Hz was used as a sensing signal. Among the samples tested, Pt-WO₃/TiO₂ showed the highest sensor response magnitude to NO. The sensor was found to respond consistently and rapidly to change in concentration of NO and NO₂ in the oxygen rich and moist gas mixture at 500 °C. The 90% response and 90% recovery times were as short as less than 5–10 s. The impedance at 4 Hz of the present device was found to vary almost linearly with the logarithm of NO_x (NO or NO₂) concentration from 10 to 570 ppm. Pt-WO₃/TiO₂ showed responses to NO and NO₂ of the same algebraic sign and nearly the same magnitude, while Pt/WO₃ and WO₃/TiO₂ showed higher response to NO than NO₂. The impedance at 4 Hz in the presence of NO for Pt-WO₃/TiO₂ was almost equal at any O₂ concentration examined (1–99%), while in the case of Pt/WO₃ and WO₃/TiO₂ the impedance increased with the oxygen concentration. The features of Pt-WO₃/TiO₂ are favorable as a NO_x sensor that can monitor and control the NO_x concentration in automotive exhaust. The effect of WO₃ loading of Pt-WO₃/ZrO₂-based sensor is studied to discuss the role of surface W-OH sites on the NO_x sensing.     

Effect of surface modification on NO2 sensing properties of SnO2 varistor-type sensors

NO₂ sensing properties of SnO₂-based varistor-type sensors have been investigated in the temperature range of 400-650°C and in the NO₂ concentration range of 15–30 ppm. Pure SnO₂ exhibited a weak nonlinear I–V characteristic in air, but clear nonlinearity in NO₂ at 450°C. The breakdown voltage of SnO₂ shifted to a high electric field upon exposure to NO₂ and the magnitude of the shift was well correlated with NO₂ concentration. Thus, SnO₂ exhibited some sensitivity to NO₂ as a varistor-type sensor. When SnO₂ particles coated with a SiO₂ thin film were used as a raw material for fabricating a varistor, the breakdown voltage in air was approximately the double that of pure SnO₂ and the sensitivity to 15 ppm NO₂ was enhanced slightly. However, the sensitivity to 30 ppm NO₂ decreased. The Cr₂O₃-loading on SnO₂ also led to an increase in the breakdown voltage in air, but the Cr₂O₃ addition was not effective for promoting the NO₂ sensitivity under the present experimental conditions.     

H2 sensors using Fe2O3-based thin film

This paper describes the fabrication procedure as well as the sensing properties of new hydrogen sensors using Fe₂O₃-based thin film. The film is deposited by the r.f. sputtering technique; its composition is Fe₂O₃, TiO₂(5 mol%) and MgO(0–12 mol%). The conductance change of the film is examined in various test gases. The sensitivity to hydrogen gas is enhanced by treating the film in vacuum at 550 °C for 4 h and then in air at 700 °C for 2 h. The sputtered film is identified to be polycrystalline -Fe₂O₃ based on X-ray diffraction patterns. However, the surface layer is considered to be changed to Fe₃O₄ after heating in vacuum and then to γ-Fe₂O₃ after heating in air. The film is thus a multilayer one with a thin γ-Fe₂O₃ layer on a -Fe₂O₃ layer. The sensing mechanism is discussed based on measurements of the physical properties of the film, such as the temperature dependence of the sensor conductance, X-ray diffraction pattern, surface morphology, RBS (Rutherford back-scattering) spectrum and optical absorption spectrum.     

Ceria-doped SnO2 sensor highly selective to ethanol in humid air

In our earlier study, we reported that at 300 °C, a 2.0 wt.% CeO₂-doped SnO₂ sensor is highly selective to ethanol in the presence of CO and CH₄ gases [F. Pourfayaz, A. Khodadadi, Y. Mortazavi, S.S. Mohajerzadeh, CeO₂ doped SnO₂ sensor selective to ethanol in presence of CO, LPG and CH₄, Sens. Actuators B 108 (2005) 172–176]. In the present investigation, we report the influence of ambient air humidity on the ethanol selective SnO₂ sensor doped with 2.0 wt.% CeO₂. Maximum response to ethanol occurs at 300 °C which decreases with the relative humidity. The relative humidity was changed from 0 to 80% for different ambient air temperatures of 30, 40 and 50 °C and the response of the sensor was monitored in a 250–450 °C temperature range. As the relative humidity in 50 °C air increased from 0 to 30%, a 15% reduction in the maximum response to ethanol was observed. A further increase in the relative humidity no longer reduced the response significantly. The presence of humidity improved the sensor response to both CO and CH₄ up to 350 °C after which the extent of improvement became smaller and at 450 °C was almost diminished. The sensor is shown to be quite selective to ethanol in the presence of humid air containing CO and CH₄. The selectivity passes a maximum at 300 °C; however it declines at higher operating temperatures.     

Highly sensitive gas sensors based on hollow SnO2 spheres prepared by carbon sphere template method

Hollow SnO₂ spheres were prepared in dimethylfomamide (DMF) by controlled hydrolysis of SnCl₂ using newly made carbon microspheres as templates. The phase composition and morphology of the material particles were characterized by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The gas sensing properties of sensors based on the hollow SnO₂ spheres were investigated. It was found that the sensor exhibited good performances, characterized by high response, good selectivity and very short response time to dilute (C₂H₅)₃N operating at 150 °C, especially, the response to 1 ppb (C₂H₅)₃N attained 7.1 at 150 °C. It was noteworthy that the response to 0.1 ppm C₂H₅OH of the sensor was 2.7 at 250 °C.     

Pulsed laser deposition of Y2O3 : Eu thin film phosphors

Thin films of Y₂O₃ : Eu cathodoluminescent (CL) phosphors were deposited using pulsed laser deposition using deposition temperature between 250°C and 800°C, O₂ pressures between residual vacuum (2×10⁻⁵ Torr) and 6 Torr, and post annealing up to 1200° for 1 h in air. The CL efficiency of the best thin film was about one third that of the starting powder. The brightness and efficiency of the thin films improved as the deposition temperature, O₂ pressure and post annealing temperature were increased, except that O₂ pressures above 600 mTorr did not significantly improve the CL properties. At deposition temperatures >600°C, the surface morphology changed from a smooth film to a nodular deposit for O₂ pressures >200 mTorr, with nodule dimensions ≈100 nm. Simultaneously, the CL properties improved dramatically because of enhanced optical scattering out of the thin film. Optical scattering was discussed in terms of anomalous diffraction. The CL properties also improved dramatically with high temperature post annealing. This effect was interpreted in terms of improved crystallinity and activation of the Eu. The low brightness and efficiency of thin films versus powder was affected by depletion of the Eu in the thin films owing to the deposition process.     

High sensitivity ethanol gas sensor integrated with a solid-state heater and thermal isolation improvement structure for legal drink-drive limit detecting

The paper reports the successful fabrication of ethanol gas sensors with tin-dioxide (SnO₂) thin films integrated with a solid-state heater, which is realized with technologies of micro-electro-mechanical systems (MEMS), and are compatible with VLSI processes. The main sensing part with dimensions of 450×400 μm² in this developed device is composed of a sensing SnO₂ film, which is fabricated by electron-gun evaporation with proper annealing in ambient oxygen gas to yield fine particles and good structure. An integrated solid-state heater with a 4.5 μm-thick cantilever bridge (1000×500 μm²) structure is made of silicon carbide (SiC) material by MEMS technologies. The sensitivity for 1000 ppm ethanol gas reaches as high as 90 with 10 s and 2 min for the response and recovery time, respectively, at an operating temperature of 300°C. Those experimental results also exhibit a much superior performance to that of a popular commercial ethanol gas sensor TGS-822. Therefore, the developed sensor with high performance is a good candidate for some specific application in automobile to detect drink-drive limit and allows an array integration available with various films for controlling each element at separate resistance.     

PECVD-SiOxNy films for large area self-sustained grids applications

In this work we study the structural properties and mechanical stress of silicon oxynitride (SiO_xN_y) films obtained by plasma enhanced chemical vapor deposition (PECVD) technique at low temperatures (320 °C) and report the feasibility of using this material for the fabrication of large area self-sustained grids. The films were obtained at different deposition conditions, varying the gas flow ratio between the precursor gases (N₂O and SiH₄) and maintaining all the other deposition parameters constant. The films were characterized by ellipsometry, by Fourier transform infrared (FT-IR) spectroscopy and by optically levered laser technique to measure the total mechanical stress. The results demonstrate that for appropriated deposition conditions, it is possible to obtain SiO_xN_y with very low mechanical stress, a necessary condition for the fabrication of mechanically stable thick films (up to 10 μm). Since this material (SiO_xN_y) is very resistant to KOH wet chemical etching it can be utilized to fabricate, by silicon substrate bulk micromachining, very large self-sustained grids and membranes, with areas up to 1 cm² and with thickness in the 2–6 μm range. These results allied with the compatibility of the PECVD SiO_xN_y films deposition with the standard silicon based microelectronic processing technology makes this material promising for micro electro mechanical system (MEMS) fabrication.     

Novel ammonia-sensing phenomena in sol–gel derived Ba0.5Sr0.5TiO3 thin films

In this paper, ammonia-sensing behavior of barium strontium titanate (BST) thin films have been reported for the first time. Thin films of BST deposited by sol–gel spin coating technique have been found to show an increase in resistance when exposed to ammonia gas. The sensitivity variation was from 20 to 60%, with lowest detection limit of about 160 ppm. The films were prepared with different pre-sintering temperatures and thickness and effect of these parameters on the ammonia-sensing have been studied. The optimum temperature for operation was found to be close to 270 °C. The ammonia-sensing studies were also performed for other gases like ethanol, NO₂ and CO; but the sensitivity in these cases was negligibly smaller than that in case of ammonia.     

Tin oxide microsensor for LPG monitoring

A silicon-based SnO₂ gas sensor has been fabricated for monitoring liquified petroleum gas (LPG), commonly used as town gas. The gas sensor is made by silicon IC technology together with SnO_f2 thin-film processing. The whole chip with a size of 9 mm x 9 mm consists of nine sensors (three by three array). each sensor is supported by a thin membrane of SiO₂/Si₃N₄/SiO₂ layers that provides a low thermal mass and prevents heat conduction through the surrounding substrate material. Tin oxide thin film is prepared by thermal evaporation of metallic tin granules and subsequent thermal oxidation of the metallic film at 600 °C. To form the SnO₂(Pt) thin film, a layer of Pt with a thickness of several tens of angstroms is sputtered onto the tin oxide film and heat treated at 500 °C in air for several hours in order to stabilize its electrical response. The fabricated SnO₂(Pt) microsensors exhibit about 85 and 92% sensitivities to 5000 ppm C₃H₈ and 5000 ppm C₄H₁₀ (the main components of LPG) at 250 °C, respectively, and show a rapid response time of less than 5 s.     

Nanoparticle engineering for gas sensor optimisation: improved sol–gel fabricated nanocrystalline SnO2 thick film gas sensor for NO2 detection by calcination, catalytic metal introduction and grinding treatments

The control of the technological steps such as calcination temperature and introduction of catalytic additives are accepted to be key points in the obtaining of improved sol–gel fabricated SnO₂ thick film gas sensors with different sensitivity to NO₂ and CO. In this work, after proving that the undoped material calcined at 1000°C is optimum for NO₂ detection, grinding is added as third technological step for further modification of particle surface characteristics, allowing to reduce cross-sensitivity to CO. The influence of grinding on the base resistance and on the sensor signals to NO₂ and CO is discussed in detail as a function of the structural differences of the sensing material.