Study of x/spl alpha/-Fe/sub 2/O/sub 3/-(1-x)ZrO/sub 2/ solid solution for low-temperature resistive oxygen gas sensors

A noble type of oxygen-sensitive and electrical-conductive material, ZrO/sub 2/-based with /spl alpha/-Fe/sub 2/O/sub 3/ thick-film gas sensor, was investigated for low operating temperature. Amorphous-like solid solutions of x/spl alpha/-Fe/sub 2/O/sub 3/-(1-x)ZrO/sub 2/ powders were derived using the high-energy ball milling technique, and their physical and microstructural properties were characterized from DTA, XRD, TEM, and XPS. The oxygen gas-sensing properties of the screen-printed thick-film gas sensors fabricated from such mechanically-alloyed materials were characterized systematically. Very good sensing properties were obtained with a relative resistance value of 82 in 20% oxygen, and at a low operating temperature of 320/spl deg/C. AC impedance spectra and thermally stimulated current were characterized to investigate the conduction properties of the solid solution, 0.2/spl alpha/-Fe/sub 2/O/sub 3/-0.8ZrO/sub 2/, in air and nitrogen (carrier gas), respectively. It was found that the Arrhenius plots of /spl sigma/T versus 1000/T have two distinct gradients corresponding to two activation energies in the high and low temperature regions. The transition temperature occurs at about 320/spl deg/C that corresponds to an optimal operating temperature of the gas sensor. It is believed that the high oxygen vacancy concentration present in the solid solution, 0.2/spl alpha/-Fe/sub 2/O/sub 3/-0.8ZrO/sub 2/, and the dissociation of the associated oxygen vacancy defect complexes at 320/spl deg/C are the critical factors for the high relative resistance to oxygen gas at low operating temperature.     

Ultrahigh-sensitive tin-oxide microsensors for H/sub 2/S detection

Ultrahigh-sensitivity SnO/sub 2/-CuO sensors were fabricated on Si(100) substrates for detection of low concentrations of hydrogen sulfide. The sensing material was spin coated over platinum electrodes with a thickness of 300 nm applying a sol-gel process. The SnO/sub 2/-based sensors doped with copper oxide were prepared by adding various amounts of Cu(NO/sub 3/)/sub 2/.3H/sub 2/O to a sol suspension. Conductivity measurements of the sensors annealed at different temperatures have been carried out in dry air and in the presence of 100 ppb to 10-ppm H/sub 2/S. The nanocrystalline SnO/sub 2/-CuO thin films showed excellent sensing characteristics upon exposure to low concentrations of H/sub 2/S below 1 ppm. The 5% CuO-doped sensor having an average grain size of 20 nm exhibits a high sensitivity of 2.15/spl times/10/sup 6/ (R/sub a//R/sub g/) for 10-ppm H/sub 2/S at a temperature of 85/spl deg/C. By raising the operating temperature to 170/spl deg/C, a high sensitivity of /spl sim/10/sup 5/ is measured and response and recovery times drop to less than 2 min and 15 s, respectively. Selectivity of the sensing material was studied toward various concentrations of CO, CH/sub 4/, H/sub 2/, and ethanol. SEM, XRD, and TEM analyses were used to investigate surface morphology and crystallinity of SnO/sub 2/ films.     

The comparative effect of two different annealing temperatures and times on the sensitivity and long-term stability of WO/sub 3/ thin films for detecting NO/sub 2/

We have deposited 150-nm-thick WO/sub 3/ films on Si/sub 3/N/sub 4//Si substrates provided with platinum interdigital electrodes and annealed in static air at 300/spl deg/C and 500/spl deg/C temperatures for 24 h and 200 h. The morphology, crystalline phase, and chemical composition of the films have been characterized using AFM, grazing incidence XRD and high resolution XPS techniques. The sensor resistance response curve has been obtained in the 0.2 -4 ppm NO/sub 2/ gas concentration range in humid air (50% relative humidity), varying the operating temperature between 25 and 250/spl deg/C. By plotting both sensor resistance and gas concentration logarithmically, the response is linear over the investigated dynamic range. Sensor sensitivities, here defined as the ratio of sensor resistance in gas to that in air (i.e., S=R/sub Gas//R/sub Air/), have been compared at a given NO/sub 2/ gas concentration (0.2 ppm). The long-term stability properties have been evaluated by recording film sensitivity for 1 yr under standardized test conditions. Increasing the annealing temperature from 300 to 500/spl deg/C causes the sensitivities to decrease. The 300/24h film is shown to be the most sensitive at S=233, but with poor long-term stability properties. The 300/200h film with S=32 is stable over the examined period. The 500/24 and the 500/200 films are shown to be less sensitive with S=16 and S=14, respectively. The longer the annealing time and the higher the temperature, the poorer the sensitivity, but with positive effects upon the long-term stability of the electrical response. The influence of the annealing conditions on sensitivity and long-term stability has been correlated with the concentration of surface defects, like reduced WO/sub 3/ phase (i.e., W/sup 4+/), which resulted in a strong effect on the sensors' response.     

Enhanced catalytic activity of ultrathin CuO islands on SnO/sub 2/ films for fast response H/sub 2/S gas sensors

H/sub 2/S gas-sensing properties of a novel SnO/sub 2/-CuO structure consisting of ultrathin (/spl sim/10 nm) CuO dotted islands (600 /spl mu/m diameter) on 120-nm thick, sputtered SnO/sub 2/ film are compared with a pure SnO/sub 2/ and a SnO/sub 2/-CuO bilayer sensor. The SnO/sub 2/-CuO-dotted sensor exhibited a high sensitivity of 7.3/spl times/10/sup 3/ at a low operating temperature of 150/spl deg/C. A fast response time of 14 s for 20 ppm of H/sub 2/S gas and a recovery time of 118 s under flowing air have been measured. The electronic interaction due to modulation of the space charge regions between the distributed p-type CuO islands on the n-type SnO/sub 2/ thin-film surface and the presence of adsorbed oxygen on the SnO/sub 2/ support have been analyzed. Dissociated hydrogen available from the CuO-H/sub 2/S interaction spills over and its chemical interaction with the adsorbed oxygen on the SnO/sub 2/ surface is found to play a dominant role in the observed fast response characteristics.     

Preparation of ferroelectric Ba(Ti/sub 0.85/Sn/sub 0.15/)O/sub 3/ thin films by metal-organic decomposition

Ferroelectric Ba(Ti/sub 0.85/Sn/sub 0.15/)O/sub 3/ (BTS/sub 15/) thin film is newly prepared on the Pt/Ti/SiO/sub 2//Si substrate by metal-organic decomposition. The firing condition is determined by thermogravimetric and differential thermal analysis. The BTS/sub 15/ thin film with a flat surface and uniform thickness is obtained by spin coating in N/sub 2/ atmosphere that avoids moisture. The BTS/sub 15/ film has a perovskite phase and a preferential [110] texture. It is also found that the crystalline structure is cubic at 24/spl deg/C with a lattice constant of 4.01 /spl Aring/, and a grain size of about 30 nm was estimated by Scherrer equation and SEM image. From P-E hysteresis loop at 20/spl deg/C, the polarization at E=0 and the electric field at P=0 are found to be 1.07 /spl mu/C/cm/sup 2/ and 24.0 kV/cm, respectively. It is observed that the dielectric constant decreases monotonously from about 830 to 630 with increasing temperature ranging from 20/spl deg/C to 50/spl deg/C. Finally, it is found that the BTS/sub 15/ thin film shows a sufficient ferroelectricity and is an attractive material for functional ferroelectric devices, such as thermal-type infrared sensors.     

Magnetic and structural properties of Co ion-implanted GaN

A GaN epilayer was grown on Al/sub 2/O/sub 3/ substrate by metal-organic chemical vapor deposition, and Co/sup -/ ions with a dose of 3/spl times/10/sup 16/ cm/sup -2/ were implanted into GaN at 350/spl deg/C. The implanted samples were postannealed at 700/spl deg/C-900/spl deg/C to recrystallize the samples and to remove implantation damage. We have investigated the magnetic and structural properties of Co ion-implanted GaN by using X-ray diffraction (XRD), superconducting quantum interference device (SQUID) magnetometer, and X-ray photoelectron spectroscopy (XPS). XRD results did not show any peaks associated with the second phase formation, and only the diffraction from the GaN layer and substrate structure were observed. The temperature dependence of magnetization taken in zero-field-cooling and field-cooling conditions showed the features of superparamagnetic system in films annealed at 700/spl deg/C-900/spl deg/C. The magnetization curves at 5 K for samples annealed at 700/spl deg/C-900/spl deg/C exhibits ferromagnetic hysteresis loops, and the highest residual magnetization (M/sub R/) and coercivity (H/sub c/) of M/sub R/=1.5/spl times/10/sup -4/ emu/g and H/sub c/=107 Oe were found in the 800/spl deg/C annealed sample. XPS measurement showed the metallic Co 2p core levels and the metallic valence band spectra for as-implanted and 700/spl deg/C-900/spl deg/C annealed samples. From these, it could be explained that the magnetic property of our films originated from Co and CoGa magnetic clusters.     

A Pt/Ga/sub 2/O/sub 3/-ZnO/SiC Schottky diode-based hydrocarbon gas sensor

In this paper, a novel metal-reactive insulator-silicon carbide device with a catalytic layer for hydrocarbon gas-sensing is presented. This structure, employed as a Schottky diode, utilizes sol-gel prepared Ga/sub 2/O/sub 3/-ZnO layer as the reactive insulator. The sensor has been exposed to propene gas, which lowers the barrier height of the diode. The responses were stable and repeatable at operating temperatures between 300 and 600/spl deg/C. The response to propene in different ambients was examined. The effect of diode bias has been investigated by analyzing the sensors response to various propene concentrations when held at constant currents of 2 and 8 mA.     

Nanosized Metal-Oxide Semiconducting SrTi1 ±xO3 − δ Oxygen Gas Sensors for Low-Temperature Application

The X-ray diffraction and transmission electron microscope results show that nanosized-SrTi_1plusmnxO_3-delta material series (27 nm) with perovskite structure can be synthesized using the high-energy ball milling technique. The thick-film screen-printed nanosized-SrTi_1plusmnxO_3-delta-based sensor series with annealing temperature of 400 degC are found to have good oxygen-sensing property at near human-body temperature for the first time for such a low temperature. The effect of the deviating stoichiometry of the nanosized-SrTi_1plusmnxO_3-delta -based sensors on their sensing properties was also investigated. The optimal relative resistance (R_nitrogen/R_20%oxygen ) value of 6.35 was obtained by a nanosized-SrTiO_3-delta -based sensor at 40 degC operating temperature. Their near human-body operating temperature is much lower than that of the conventional low-temperature semiconducting oxygen gas sensors (300degC-500degC) and SrTiO₃ oxygen sensors (>700degC). This can extend the application of the semiconducting oxygen gas sensors from the conventional high and medium temperature to the lower operating temperature areas such as the medical, environmental, and domestic fields, etc     

AlGaN/GaN-based diodes and gateless HEMTs for gas and chemical sensing

The characteristics of Pt/GaN Schottky diodes and Sc/sub 2/O/sub 3//AlGaN/GaN metal-oxide semiconductor (MOS) diodes as hydrogen and ethylene gas sensors and of gateless AlGaN/GaN high-electron mobility transistors (HEMTs) as polar liquid sensors are reported. At 25/spl deg/C, a change in forward current of /spl sim/6 mA at a bias of 2 V was obtained in the MOS diodes in response to a change in ambient from pure N/sub 2/ to 10% H/sub 2// 90% N/sub 2/. This is approximately double the change in forward current obtained in Pt/GaN Schottky diodes measured under the same conditions. The mechanism appears to be formation of a dipole layer at the oxide/GaN interface that screens some of the piezo-induced channel charge. The MOS-diode response time is limited by the mass transport of gas into the test chamber and not by the diffusion of atomic hydrogen through the metal/oxide stack, even at 25/spl deg/C. Gateless AlGaN/GaN HEMT structures exhibit large changes in source-drain current upon exposing the gate region to various polar liquids, including block co-polymer solutions. The polar nature of some of these polymer chains lead to a change of surface charges in gate region on the HEMT, producing a change in surface potential at the semiconductor/liquid interface. The nitride sensors appear to be promising for a wide range of chemicals, combustion gases and liquids.     

Low-temperature catalyst adding for tin-oxide nanostructure gas sensors

Thick-film gas sensors are successfully fabricated using the nanostructure tin-oxide powder. In order to suppress the coarsening of the nanostructure tin-oxide particles during the adding process, the low-temperature catalyst adding (LTCA) method is proposed in this paper. LTCA is an adding method of noble Pd catalyst onto the nanostructure tin-oxide particles under the lower temperature below 300/spl deg/C by excluding chloride. It turned out that the adding without particle coarsening is successfully carried out by means of LTCA. Applying LTCA to the fabrication of the thick film using nanostructure tin-oxide powder having a size smaller than 5 nm leads to an excellent performance with respect to the methane gas sensing. After aging at 400/spl deg/C, a good sensitivity (R/sub 3500//R/sub 1000/) of 0.66 is obtained for the sensor doped with 5 wt% of Pd catalyst. Also, the sensitivity of the sensor is so stable that the deviation of the electrical resistance is within 3% after 400 h of aging.     

Iridium oxide as low temperature NO/sub 2/-sensitive material for work function-based gas sensors

This paper presents the results on work function-based NO/sub 2/-sensing properties of iridium-oxide thin films at 130/spl deg/C. Films of 20-nm and 100-nm thickness were deposited on silicon substrates using dc sputtering followed by annealing in oxygen ambient. Sensitivity of these films to different concentrations of NO/sub 2/, H/sub 2/, CO, Cl/sub 2/, and NH/sub 3/ in synthetic air was measured using a Kelvin probe. It was observed that work function of 20-nm-thick iridium-oxide film changed by /spl sim/100 mV on exposure to 5-ppm NO/sub 2/ (German safety limit). Cross sensitivity to other gases (except NH/sub 3/) and interference of humidity was found to be negligibly small. The film was incorporated as a gate electrode in a hybrid suspended gate field effect transistor (HSGFET) structure to examine its suitability in FET-type sensors. The films were characterized using Rutherford backscattering spectroscopy, X-ray diffraction analysis, and scanning electron microscopy to determine their composition, phase, and surface morphology. The results suggest that iridium-oxide film is a promising material for the realization of a FET-based NO/sub 2/ sensor.     

Recent developments in high curie temperature perovskite single crystals

The temperature behavior of various relaxor-PT piezoelectric single crystals was investigated. Owing to a strongly-curved morphotropic phase boundary, the usage temperature of these perovskite single crystals is limited by T/sub R-T/- the rhombohedral to tetragonal phase transformation temperature - which occurs at the significantly lower temperatures than the Curie temperature T/sub c/. Attempts to modify the temperature usage range of Pb(Zn/sub 1/3/Nb/sub 2/3/)O/sub 3/-PbTiO/sub 3/ (PZNT) and Pb(Mg/sub 1/3/Nb/sub 2/3/)O/sub 3/-PbTiO/sub 3/ (PMNT) rhombohedral crystals (T/sub c/ /spl sim/ 150-170/spl deg/C, T/sub R-T/ /spl sim/ 60-120/spl deg/C) using minor dopant modifications were limited, with little success. Of significant potential are crystals near the morphotropic phase boundary in the Pb(Yb/sub 1/2/Nb/sub 1/2/)O/sub 3/-PbTiO/sub 3/ (PYNT) system, with a T/sub c/ > 330/spl deg/C, even though T/sub R-T/ was found to be only half the value at /spl sim/160/spl deg/C. Single crystals in the novel BiScO/sub 3/-PbTiO/sub 3/ system offer significantly higher T/sub c/s > 400/spl deg/C, while exhibiting electromechanical coupling coefficients k/sub 33/ > 90% being nearly constant till the T/sub R-T/ temperature around 350/spl deg/C, which greatly increases the temperature range for transducer applications.     

Gas-sensing properties of sprayed films of (CdO)/sub x/(ZnO)/sub 1-x/ mixed oxide

A novel NO/sub 2/ sensor based on (CdO)/sub x/(ZnO)/sub 1-x/ mixed-oxide thin films deposited by the spray pyrolysis technique is developed. The sensor response to 3-ppm NO/sub 2/ is studied in the range 50/spl deg/C-350/spl deg/C for three different film compositions. The device is also tested for other harmful gases, such as CO (300 ppm) and CH/sub 4/ (3000 ppm). The sensor response to these reducing gases is different at different temperatures varying from the response typical for the p-type semiconductor to that typical for the n-type semiconductor. Satisfactory response to NO/sub 2/ and dynamic behavior at 230/spl deg/C, as well as low resistivity, are observed for the mixed-oxide film with 30% Cd. The response to interfering gas is poor at working temperature (230/spl deg/C). On the basis of this study, a possible sensing mechanism is proposed.     

Surface and in depth chemistry of polycrystalline WO/sub 3/ thin films studied by X-ray and soft X-ray photoemission spectroscopies

The chemical composition of surface and underneath layers of WO/sub 3/ thin films, deposited by thermal evaporation and annealed in air at different temperatures, has been studied by means of soft X-ray and X-ray photoemission spectroscopies. Both the W 4f and valence band spectra have been analyzed. The analysis has been performed on samples as inserted and after an annealing process in an ultra high vacuum. The results have shown that the surface always presents a nonstoichiometric WO/sub 3/ compound, whose spectral components do not depend on the sample preparation. Instead, the study of the underneath layers has shown that the WO/sub 3/ films annealed in air at 500/spl deg/C are highly stoichiometric and stable, while the samples heated in air at 300/spl deg/C are much more sensitive to the vacuum thermal treatment showing the presence of reduced WO/sub x/ phases, whose intensity and chemical states change after the in vacuum annealing procedure.     

High-sensitivity sensor of low relative humidity based on overlay on side-polished fibers

A low relative humidity (RH) sensor based on overlay on side-polished fiber is presented. The evanescent field from a single-mode optical fiber is coupled to a TiO/sub 2/ waveguide overlay. The transmission response exhibits sharp resonances whose central wavelengths are linearly shifted with RH. This behavior is due to the porous columnar nanostructure of the TiO/sub 2/ film. The water is adsorbed in the pores of the nanostructure changing the refractive index of the layer and causing a shift of the wavelength resonances. The response of the sensor is determined by the shape and size of the pores. The optical fiber evanescent field sensor developed has a linear response and high sensitivity (0.5 nm/% RH) for low RH (RH/spl sim/0%-15%) at 26.1/spl deg/C/spl plusmn/0.6/spl deg/C. The lack of hysteresis in the adsorption-desorption cycle has been checked. The development of a sensor with tailored response is envisaged using properly techniques to control the porosity of the material.     

Design of low cost gas sensor based on SrTiO3 and BaTiO3 films

We have prepared SrTiO3/BaTiO3 multilayer film on alumina substrates by a sol-gel technique and investigated their response for sensing ethanol vapor. The surface morphology of the films were characterized by atomic force microscope (AFM) showing that the grain size of the films increase up to 40 nm as the annealing temperature increased to 1000 degrees C. The ethanol sensors based on SrTiO3/BaTiO3 thin films were fabricated by applying interdigitated gold electrodes by sputtering technique. The ethanol sensing characteristics of SrTiO3/BaTiO3 thin films were quantified by the change in resistance of the sensors when they were exposed to ethanol. The optimum operating tempearature of these sensors was found to be 350 degrees C. In addition, the film annealed at 1000 degrees C exhibited p-type gas sensing behavior with the best sensitivity of 30-100 for low ethanol concentration in the range of 100-1000 ppm.     

Gas-sensing properties of catalytically modified WO/sub 3/ with copper and vanadium for NH/sub 3/ detection

Ammonia gas detection by pure and catalytically modified WO/sub 3/-based gas sensors was analyzed. Sensor response of pure tungsten oxide to NH/sub 3/ was unsatisfactory, probably due to the unselective oxidation of ammonia into NO/sub x/. Copper and vanadium were introduced in different concentrations and the resulting material was annealed at different temperatures in order to improve the sensing properties for NH/sub 3/ detection. The introduction of Cu and V as catalytic additives improved the sensor response to NH/sub 3/. Possible reaction mechanisms of NH/sub 3/ over these materials are discussed. Sensor responses to other gases like NO/sub 2/ or CO and interference of humidity on ammonia detection were also analyzed so as to choose the best sensing element.     

Fabrication and testing of bulk micromachined silicon carbide piezoresistive pressure sensors for high temperature applications

This paper explores the development of high-temperature pressure sensors based on polycrystalline and single-crystalline 3C-SiC piezoresistors and fabricated by bulk micromachining the underlying 100-mm diameter (100) silicon substrate. In one embodiment, phosphorus-doped APCVD polycrystalline 3C-SiC (poly-SiC) was used for the piezoresistors and sensor diaphragm, with LPCVD silicon nitride employed to electrically isolate the piezoresistor from the diaphragm. These piezoresistors fabricated from poly-SiC films deposited at different temperatures and doping levels were characterized, showing -2.1 as the best gauge factor and exhibited a sensitivities up to 20.9-mV/V*psi at room temperature. In a second embodiment, epitaxially-grown unintentionally nitrogen-doped single-crystalline 3C-SiC piezoresistors were fabricated on silicon diaphragms, with thermally grown silicon dioxide employed for the piezoresistor electrical isolation from the diaphragm. The associated 3C-SiC/SiO/sub 2//Si substrate was fabricated by bonding a (100) silicon wafer carrying the 3C-SiC onto a silicon wafer with thermal oxide covering its surface. The 3C-SiC handle wafer was then etched away in KOH. The diaphragm was fabricated by time etching the silicon substrate. The sensors were tested at temperatures up to 400/spl deg/C and exhibited a sensitivity of 177.6-mV/V*psi at room temperature and 63.1-mV/V*psi at 400/spl deg/C. The estimated longitudinal gauge factor of 3C-SiC piezoresistors along the [100] direction was estimated at about -18 at room temperature and -7 at 400/spl deg/C.     

Working mechanism of an ethanol filter for selective high-temperature methane gas sensors

Semiconducting metal-oxide gas sensors are generally nonselective, which limits their use as natural gas detectors in domestic environments when ethanol is present in high background concentrations. Using a thin-film Ga/sub 2/O/sub 3/ sensor with a thick-film catalyst filter of Ga/sub 2/O/sub 3/ and an operating temperature of 800/spl deg/C, the cross-sensitivity to ethanol is strongly reduced and the sensor response to methane is enhanced. Detection of natural gas is made reliable and the rate of false alarms is reduced. Oxidation of ethanol and methane over gallium oxide is studied using GC product analysis. These measurements of catalytic activity help to clarify the reactions involved in the filtering mechanism. Elimination of the ethanol cross-sensitivity is attributed to the thermal combustion of ethanol as it passes over the hot filter. The sensor response to methane is enhanced as methane is activated by the active catalytic Ga/sub 2/O/sub 3/ thick-film.     

Temperature stable Hall effect sensors

Magnetic field sensors are needed for high-accuracy position, angle, force, strain, torque, and current flow measurements. Molecular beam epitaxy was used to grow tellurium-doped indium-gallium antimonide thin films. Hall effect sensors made from these films have been studied for their magnetic sensitivity and thermal stability. For a range of alloy composition near In/sub 0.8/Ga/sub 0.2/Sb and n-type doping levels near 2/spl times/10/sup 17/ cm/sup -3/, high magnetic sensitivity from -40/spl deg/C to +200/spl deg/C was found with a resolution of better than /spl plusmn/0.5% over the entire temperature range.