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.     

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.     

Characterization of protective coatings for planar automotive gas sensors

Alumina support material suitable for use as a planar automotive gas sensor support was coated in thin films of yttria-stabilised zirconia (YSZ) and titania. The morphology, composition, thickness and homogeneity of the coating was measured. The coating was applied to the ‘green’ form of a tape cast alumina substrate which was subsequently fired at 1500 °C to produce the final form of the coated alumina. The YSZ coating gave a continuous 5 μm thick coating with no evidence of mixed oxide formation between the YSZ and the alumina substrate. XRD indicated a face centred cubic Y doped ZrO₂ or primitive tetragonal Zr_0.9Y_0.1O_1.95 phase. The titania coatings were much thinner (<1 μm) with signs of trace amounts of aluminium titanium oxide (Al₂TiO₅) as well as rutile titania in XRD. Spot analysis using X-ray photoelectron spectroscopy showed a fairly regular titania coverage. Atomic force microscopy analysis showed a particle size of 1–3 μm for the YSZ coating and 0.5 μm for titania.     

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.     

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.     

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.     

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.     

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.     

Sol–gel derived polycrystalline Cr1.8Ti0.2O3 thick films for alcohols sensing application

The powder sample of Cr_1.8Ti_0.2O₃ (CTO) was obtained by a sol–gel method. The thick films were developed on identical ceramic tubes of 4 mm length comprising of two Au-electrodes and printing an eight-layer film prepared by mixing CTO with glass powder and -terpinol as an organic vehicle. X-ray powder diffraction (XRD) patterns showed the formation of a single phase. The scanning electron microscope (SEM) images of the ceramic sensor treated at 850 °C revealed that the grain size was larger than 400 nm for the individual isolated grains on the surface, and the agglomerated dense spheroidal platelets had the size of 1–4 μm in diameter. The AC impedance measurement in ambient air showed that the resistance decreased nearly by two orders of magnitude with an increase in temperature in the range of 400–600 °C for both the powder sample and the thick film, and the activation energy E_a derived from the measurement was found to be 0.35 and 0.36 eV for the powder and the film, respectively. The films were exposed to various concentrations of alcohols (0.4–1.2 ppm of methanol and 1.0–5.0 ppm of ethanol), followed by determination of sensor response, sensitivity and reversibility and reproducibility. The origin of the gas response was attributed to the surface reaction of R-OH (R = methyl and ethyl group) with O⁻_(ads) to form adsorbed R-CHO, which was desorbed as a gas at 400 °C after the sensor departing from the gas.     

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.     

Fabrication and characterization of low temperature sintering PMN–PZN–PZT step-down multilayer piezoelectric transformer

For the fabrication as step-down multilayer piezoelectric transformer, piezoelectric properties of Pb(Mg_1/3Nb_2/3)O₃–Pb(Zn_1/3Nb_2/3)O₃–Pb(Zr_0.52Ti_0.48)O₃ (PMN–PZN–PZT) ceramics were optimized by ZnO–Li₂CO₃ (ZL) and Pb₃O₄ content. Effects of the additions on the structure, bulk density and electrical properties of ceramics were investigated. The results revealed that the proper additions of ZL with Pb₃O₄ content could modify the electrical properties of the PMN–PZN–PZT ceramics. The composition sintered at 995 °C with 0. 01 wt.% ZL and 0.10 wt.% Pb₃O₄ content showed higher values, which were listed as follows: d₃₃ = 256 pC/N, K_p = 0.60, Q_m = 1910, _r = 1032, tan δ = 0.0070 and r = 2.09 Ω. In addition, the step-down piezoelectric transformers with optimized PMN–PZN–PZT composites were fabricated and the characteristics as the output power and resistance loads were measured. Meanwhile, the step-down piezoelectric transformers sintered at 995 °C showed the favorable characteristics with a higher gain G of 0.204 and a lower temperature rise of 6 °C when the output power was 5 W, and the driving frequency were approximately constant (≈126 kHz) when the output power was from 5 to 13 W. Moreover, the maximum efficiency (90.2%) was obtained at load resistance of 10 Ω.     

High aspect ratio In2O3 nanowires: Synthesis, mechanism and NO2 gas-sensing properties

Flexural In₂O₃ nanowires with high aspect ratios were synthesized via a hydrothermal–annealing route. The as-synthesized In₂O₃ nanowires had diameters of 30–50 nm and length up to several microns. Various reaction parameters, such as the kind of reagents, the time of hydrothermal treatment, annealing time and annealing temperature, were investigated by a series of control experiments. The as-synthesized In₂O₃ nanowires showed excellent gas-sensing properties to NO₂ in terms of sensor response and selectivity.     

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.     

A fibre-optic oxygen sensor based on contact charge-transfer absorption

A fibre-optic oxygen (O₂) sensor monitoring at a wavelength of 400 nm has been successfully developed for the determination of gaseous O₂. Its working principle is based on the contact charge-transfer absorption of N,N-dimethyl-p-toluidine and O₂. The response to changes in O₂ concentrations is reversible and in good agreement with the Beer-Lambert law. The response and recovery times are 12 and 26 min, respectively. The sensor can detect a wide range of O₂ concentrations, ranging from 4.3 to 100% O₂. The precision is 1.45% (n=5) in a gas mixture of 95% O₂ in N₂ and the limit of detection is 4.3% O₂ (3σ_b). The sensor is stable with a 0.53% change in sensitivity per hour. There is a 0.25% °C⁻¹ decrease of the sensitivity of the sensor to O₂ in the range 20–34°C. Water vapour and nitrogen dioxide interfere slightly, whereas hydrogen sulphide and hydrogen chloride have moderate interference on the sensor. However, chlorine and sulphur dioxide seriously interfere with the sensor.     

Room temperature hydrogen response kinetics of nano–micro-integrated doped tin oxide sensor

The nano–micro-integrated sensor has been fabricated by sol–gel depositing the nanocrystalline indium oxide (In₂O₃)-doped tin oxide (SnO₂) thin film on microelectromechanical systems (MEMS) device having interdigitated electrode configurations with two different electrode spacing (10 μm and 20 μm) and two different number of fingers (8 and 20). The present nano–micro-integrated sensor exhibits high H₂ sensitivity range (S = 3–10⁵) for the H₂ concentration within the range of 100–15,000 ppm at room temperature. It has been demonstrated that, the room temperature response kinetics of the present nano–micro-integrated sensor is a function of finger spacing, H₂ concentration and air-pressure, but independent of number of fingers. Such dependence has been explained on the basis of Le Chatelier's principle applied to the associated H₂ sensing mechanism and the role of above parameters in shifting the dynamic equilibrium of the involved surface reactions under the described test conditions. A new definition of the response time has been proposed, which is not only suitable for the theoretical analysis but also for the practical applications, where a gas-leak detection alarm is required to be triggered.     

Integrated optical pH sensor using replicated chirped grating coupler sensor chips

Integrated optical sensor chips suitable for high-resolution pH measurements are presented. The pH-sensitive swelling of a polymer membrane is detected by refractometry using a compact multi-channel sensor module. The signal transduction is achieved by means of chirped grating couplers which allow simple yet high functionality sensor modules to be built. The experiments have been performed with high sensitivity replicated polycarbonate TiO₂ waveguide sensor chips coated with an ultrathin photopatterned hydrogel membrane having functional groups which reversibly change from the neutral state to a charged state upon acidification. A resolution δpH <±1.1×10⁻⁴ in terms of the pH (at pH 7.5) has been obtained in a dual-channel module with size 10×10×10 cm³.     

ZnFe2O4 tubes: Synthesis and application to gas sensors with high sensitivity and low-energy consumption

ZnFe₂O₄ tubes with mesoscale dimensions were synthesized by pyrolysis of polyvinyl alcohol (PVA)-mediated xerogel using porous alumina as a template. The product formation was analyzed by X-ray powder diffraction (XRD), Fourier transformation infrared spectroscopy (FT-IR), thermogravimetry and differential thermal analysis (TG–DTA), scanning electronic microscopy (SEM), transmission electron microscopy (TEM) and high-resolution TEM (HRTEM). This synthetic method yielded open-ended ZnFe₂O₄ tubes with a typical length of several micrometers, an outer diameter of about 200 nm, and an average thin wall of 20 nm composed of small nanocrystals. Application of the ZnFe₂O₄ tubes as gas sensor materials displayed low-energy consumption and high sensitivity to organics such as ethanol and acetone, due to the unique interconnected channel structure and small crystal size of the tubes, showing their potential application in sensor areas.     

Searching for optimal sensitivity of single-mode D-type optical fiber sensor in the phase measurement

To improve the sensitivity of a single-mode D-type optical fiber sensor, we selected a D-type optical fiber sensor with 4 mm long and 4 μm core thickness made of a single-mode fiber, a Au-coating on the sensor with a thickness range of 15–32 nm, a light wavelength of 632.8 nm, and an incident angle of 86.5–89.5° for different refractive index (1.33–1.40) sensing. These simulations are based on the surface plasmon resonance (SPR) theory using the phase method which shows that the sensitivity is proportional to the refractive index, Au film thickness and lower incident angle on the sensing interface. The sensitivity is higher than 4000 (degree/RIU), and the resolution is better than 2.5 × 10⁻⁶(RIU) as the minimum phase variation is 0.01°. This device is used to detect the refractive index or gas or liquid concentration in real-time. The proposed sensor is small, simple, inexpensive, and provides an in vivo test.     

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.     

High-resolution high-voltage sensor based on SAW

A surface acoustic wave (SAW)-based high-voltage sensor is described. The sensor consists of a SAW oscillator fabricated on a 10 mm × 10 mm 128° rotated Y-cut, X-propagating LiNbO₃ substrate. The voltage is applied to electrodes on the substrate, and the resulting electric field changes the propagation time of the SAW. The propagation time is directly related to the output frequency of the SAW oscillator. The high-voltage sensor offers a small-sized high-voltage measurement device with several attractive features: a high resolution (better than 0.2 V up to 2.4 kV, better than 0.4 V for higher voltages), a large range (−10 to +10 kV), a high input impedance (> 10¹³ ω) and a low input capacitance (< 10 pF). The sensitivity amounts to 16 Hz V⁻¹.