Manufacture and characterization of sol–gel V1−x−yWxSiyO2 films for uncooled thermal detectors

V_1−x−yW_xSi_yO₂ films for uncooled thermal detectors were coated on sodium-free glass slides with sol–gel process, followed by the calcination under a reducing atmosphere (Ar/H₂ 5%). The V_1−x−yW_xSi_yO₂ films as prepared inherit various phase transition temperatures ranging from 20 to 70 °C depending on the dopant concentrations and the fabrication conditions. Compared to the hysteresis loop of plain VO₂ films, a rather steep loop was obtained with the addition of tungsten components, while a relaxed hysteresis loop with the tight bandwidth was contributed by Si dopants. Furthermore, the films with switching temperature close to room temperature were fabricated to one-element bolometers to characterize their figures of merit. Results showed that the V_0.905W_0.02Si_0.075O₂ film presented a satisfactory responsivity of 2600 V/W and detectivity of 9 × 10⁶ cm  Hz^1/2/W with chopper frequencies ranging from 30 to 60 Hz at room temperature. It was proposed that with appropriate amount of silicon and tungsten dopants mixed in the VO₂, the film would characterize both a relaxed hysteresis loop and a fair TCR value, which effectively reduced the magnitude of noise equivalent power without compromising its performance in detectivity and responsivity.     

Trace detection of nitroaromatic compounds with layer-by-layer assembled {SBA/PSS}n/PDDA modified electrode

The {SBA/PSS}_n/PDDA films modified electrode was prepared by layer-by-layer (LBL) assembly with mesoporous SiO₂ (SBA), poly(sodium 4-styrene-sulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDDA) in this paper. SBA is a large pore-size mesoporous material with highly ordered hexagonally arranged mesochannels and high thermal stability etc. The electrochemical characteristics of the {SBA/PSS}_n/PDDA films have been studied by electrochemical impedance spectroscopy in 0.1 M KCl solution containing 5.0 mM Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ at the formal potential of 0.230 V. The ultratrace nitroaromatic compounds (NACs) such as TNT, TNB, DNT and DNB were determined by differential pulse voltammetry (DPV) measurement. The sensitivities for NACs determination with {SBA/PSS}_n/PDDA modified electrode were dependent on the number of layers, pH and ionic strength of electrolyte, based on which a set of optimized conditions for film fabrication was inferred. The current responses were linear with NACs ranging from 10⁻⁹ to 10⁻⁷ mol/l. The results showed that the {SBA/PSS}_n/PDDA modified electrode established a new way for fast, simple and sensitive analysis of NACs.     

Sn1-xFexOy: a new material with high carbon monoxide sensitivity

The preparation method and the sensing properties (sensitivity and selectivity to interfering gases) towards carbon monoxide of the new ternary compound Sn_1-xFe_xO_y deposited in the form of thin films, are presented in this paper. The metal of the VIIIB group is introduced with concentrations in the range 0<x<25 at %. Thin films are sputtered using the RGTO (rhotaxial growth and thermal oxidation) technique. This technique consists of metal deposition onto a substrate maintained at a temperature higher than the metal melting point and metal oxidation by means of an annealing cycle in pure oxygen. Particular emphasis is given to the relations between some preparation parameters of the material, namely the atomic percentage ofiron or the annealing cycle, and to the sensor sensitivity towards CO and other interfering gases like C₂H₅OH, H₂ and NO_x diluted in dry air. A sensitivity S=(G_gas-G_air)/G_air=3.5 towards 10 ppm of CO has been measured: the kinetic characteristics of the sensors are also presented, together with the working mechanism.     

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.     

3-D silicon vector sensor based on a novel parallel-field Hall microdevice

A single-chip 3-D silicon vector sensor for magnetic-field measurement is presented. This triaxial device functionally integrates in a common transducer region two novel five-contacts parallel-field Hall elements for in-plane components B_x and B_y and four cross-coupled orthogonal triple Hall elements for the B_z component, perpendicular to the chip surface. The effective sensor volume is 150 μm×150 μm×100 μm. The main advantage of this 3-D vector magnetometer is the strongly reduced (with about 45%) channel cross-sensitivities. This is achieved by amperometric output mode of operation using an original read-out circuitry, keeping equal voltage conditions on the top of the chip with and without magnetic field. The sensitivities per channel reaches S_A(B_x)=S_A(B_y)=356 μA/T and S_A(B_z)=260 μA/T at a supply current 10 mA, the measured equivalent offsets of the three channel outputs are 25/35 mT and the low frequency noise is mainly a 1/f. The lowest detected magnetic induction of the three output channels is about 15/20 μT in the range 1≤f≤ 10² Hz and the frequency response of the 3-D device together with the read-out electronics is at least 30 kHz.     

NOx sensing properties of In2O3 nanoparticles prepared by metal organic chemical vapor deposition

In₂O₃ nanoparticles were deposited by low-temperature metal organic chemical vapor deposition. The response of 10-nm thick In₂O₃ particle containing layers to NO_x and O₂ gases is investigated. The lowest detectable NO_x concentration is 200 ppb and the sensor performance is strongly dependent on the gas partial pressure as well as on the operating temperature. The sensor response towards 200 ppm of NO_x is found to be above 10⁴. Furthermore, the cross-sensitivity against O₂ is very low, demonstrating that the In₂O₃ nanoparticles are very suitable for the selective NO_x detection.     

Gas-sensing property and mechanism of CaxLa1−xFeO3 ceramics

LaFEO₃ and Ca_xLa_1−xFeO₃ ceramic powders have been prepared by the coprecipitation method from La(NO₃)₃, Fe(NO₃)₃ and Ca(NO₃)₂ aqueous solutions. The orthorhombic perovskite phases of LaFeO₃ and Ca_xLa_1−xFeO₃ are characterized by X-ray diffraction patterns. The sensors fabricated with those powders have high sensitivity to alcohol. Partial substitution of La³⁺ in LaFeO₃ with Ca²⁺ can enhance the sensitivity of the materials to reducing gases. The resistance of an LaFeO₃ sensor in air, vacuum and alcohol-containing air has been measured. Complex impedance spectroscopy has been used to try and analyse the gas-sensing mechanism. According to the experimental results, it can be deduced that the surface adsorptive and lattice oxygen govern the sensing properties of LaFeO₃ and Ca_xLa_1−xFeO₃ ceramics.     

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.     

Characterizations of VO2-based uncooled microbolometer linear array

Vanadium dioxide (VO₂) thin films are materials for uncooled microbolometer due to their high temperature coefficient of resistance (TCR) at room temperature. This paper describes the design and fabrication of eight-element uncooled microbolometer linear array using the films and micromachining technology. The characteristics of the array is investigated in the spectral region of 8–12 μm. The fabricated detectors exhibit responsivity of over 10 kV/W, detectivity of approximate 1.94×10⁸ cm Hz^1/2/W, and thermal time constant of 11 ms, at 300 K and at a frequency of 30 Hz. Furthermore, the uncorrected response uniformity of the linear array bolometers is less than 20%.     

Silicon condenser microphones with corrugated silicon oxide/nitride electret membranes

Corrugated electret membranes are used in a micromachined silicon microphone. The membranes consist of a permanently corona-charged double layer of silicon dioxide and silicon nitride, known to have excellent charge-storing properties. This electret can replace the external bias needed for condenser microphones. The well-known LOCOS technique—also combined with dry etching—is used for the first time to fabricate membranes with corrugation depths of several microns. The membrane thickness amounts to 600 nm.

The interferometrically measured center deflection is up to 40 nm/Pa for diaphragms with four corrugations of up to 3.3 μm depth and a size of A_M=1 mm². This high mechanical sensitivity limits the dynamic range to sound pressures below 50 Pa. The obtained mechanical sensitivities are in excellent agreement with the theory.

The most compliant corrugated diaphragms result in a microphone sensitivity of 2.9 mV/Pa, an equivalent noise level of 39 dB(A) and a total harmonic distortion below 1.7% at 28 Pa (123 dB SPL). The corrugation depth in the sensors has been only 1.3 μm. All sensors cover the whole audio and low ultrasonic range. The temperature coefficient is between 0.05 and 0.1 dB/K.     

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.     

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.     

Comparative study of spin coated and sputtered PMMA as an etch mask material for silicon micromachining

SiO₂ and Si₃N₄, are usually used to mask the selected portions during etching of silicon in anisotropic etchants like KOH but polymers are expected to be very good alternative to SiO₂ and Si₃N₄ as masking materials for MEMS applications. An adherent spin coated PMMA layer is reported to work as a mask material. It is a low temperature process, cheaper and films can be easily deposited and removed. One of the problems in its use is its adhesion to the substrate. Our previous experience in the field made us feel that sputtered PMMA will act as better mask because of its better adhesion to silicon. In the present article, a comparative study of spin coated PMMA with sputtered PMMA as an etch mask for silicon micromachining is reported. Structural and adhesive characteristics of the films are determined and compared with those available in the literature. These films deposited on silicon wafer were exposed to anisotropic etchant, KOH, to estimate the masking behavior. The maximum masking time of 32 min in 20 wt.% KOH at 80 °C was obtained for spin coated PMMA samples, which were prebaked at 90 °C. Masking time of sputter deposited PMMA films was found to be 300 min under similar conditions such as 20 wt.% KOH at 80 °C. This masking time is sufficient for fabrication of various MEMS structures, thus indicating candidature of sputtered PMMA as masking material. Various properties of the films are discussed and compared with the ones obtained through literature.     

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-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.     

Properties of Noncentral Dirichlet Distributions

Let X₁,…, X_r+1 be independent random variables, X_iGa (a_i, θ, δ_i), i = 1,…, r + 1. Define and V_i = X_i/X_r+1, i = 1,…, r. Then, (U₁,…, U_r) and (V₁,…, V_r) follow noncentral Dirichlet Type 1 and Type 2 distributions, respectively. In this article several properties of these distributions and their connections with the uniform, the noncentral multivariate-F and the noncentral multivariate-t distributions are discussed.     

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.     

Electric and ferroelectric properties of PZT/SBT multilayer films prepared by photochemical metal-organic deposition

The electric and ferroelectric properties of lead zirconate titanate and strontium bismuth tantalate multilayer films prepared using photosensitive starting precursors were characterized. The electric and ferroelectric properties were investigated by characterization of the effect of stacking order of four ferroelectric layers of PZT or SBT in the multilayer films of 4-PZT, PZT/2-SBT/PZT, SBT/2-PZT/SBT, and 4-SBT. The P_r value of the 4-SBT multilayer film was relatively small (6 μC/cm²) and a two times higher value (12 μC/cm²) was obtained with the SBT/2-PZT/SBT multilayer film. The films with SBT layers at the top and bottom showed improved leakage current and fatigue resistance compared to the films with PZT layers at the top and bottom. It was revealed that the defect dipole was reduced at the SBT/Pt interface due to a self-regulation layer such as (Bi₂O₂)²⁺ in the SBT film. Also, the bottom layer on the Pt substrate showed a significant influence on the growth orientation of the entire ferroelectric films.     

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.     

Metallic thin-film thermocouple for thermoelectric microgenerators

A new metallic thin-film thermocouple orientated towards thermoelectric microgenerators has been developed. It consists of a 3 μm thick NiCr/SiO₂/Sb multilayer structure sputter deposited onto a thermally oxidized silicon substrate. A relative Seebeck coefficient of _ab = 76 μV K⁻¹ and an optimal figure of merit of z_ab = 0.08 × 10⁻³ K⁻¹ have been measured for this material combination. Both parameters are very close to the theoretical values.