Time-resolved pH/pO2 mapping with luminescent hybrid sensors

A method for simultaneous and referenced 2D mapping of pH and pO2 is described. The experimental setup combines a fast gateable CCD camera as detector, a LED as excitation light source and a single-layer sensor membrane as optical transducer. The planar optode comprises a lipophilic fluorescein derivative (lifetime approximately 5 ns) and platinum(II) mesotetrakis(pentafluorophenyl)porphyrin (approximately 70 micros in the absence of a quencher) immobilized in a hydrogel matrix. Depending on the fluorescent pH indicator, a pH transition in the physiological range (pH 6-pH 8) or in the near-basic region (pH 7-pH 9) can be achieved. The measuring scheme involves the time-resolved acquisition of images in three windows during a series of square-shaped excitation pulses. A method allowing the calculation of both parameters from these three images is presented. The pH/pO2 hybrid sensor incorporating the pH indicator 2',7'-dihexyl-5(6)-N-octadecyl-carboxamidofluorescein was characterized in detail. The pH and pO2 were determined with a maximum deviation of 0.03 pH unit and 6.5 hPa pO2, respectively, within the range of pH 7.6-pH 8.7 and 0-200 hPa pO2 in test measurements. The ionic strength (IS) cross-sensitivity was found to be relatively small (pH/IS < 3.5 x 10(-4) mM(-1) and pO2/IS <-0.053 hPa mM(-1) at a transition from 0.5 to 0.1 M IS). Whereas a strong temperature effect on the sensor signal was observed (DeltapH/DeltaT = 0.011-0.034 K-1 and DeltapO2/DeltaT = 1.85-7.17 hPa K-1 in the range from 277 to 308 K). Examples of pH/pO2 images obtained in natural marine sediment are presented.     

Temperature profile investigation of SnO/sub 2/ sensors for CO detection enhancement

SnO/sub 2/ sensors are widely used for the detection of air contaminants such as CO. Nevertheless, their application encounters several problems, mainly the effect of interfering gases. The low selectivity is, in fact, a well-known problem of these sensors. Moreover, the high operating temperature of metal oxide sensors implies, in general, high power consumption. We present a study aimed at the selection of an appropriate measurement technique for detection of CO for indoor applications (lower threshold 100 ppm), in the presence of high concentrations of ethanol (up to 1000 ppm), by using only one sensor. Moreover, the paper aims at developing portable CO detectors that are very small, low power, and could be battery operated.     

CO-sensing properties of In/sub 2/O/sub 3/-doped SnO/sub 2/ thick-film sensors: effect of doping concentration and grain size

In/sub 2/O/sub 3/-doped SnO/sub 2/ nanoparticles were prepared using sol-gel technique from 0.1-M solutions of both stannic chloride (SnCl/sub 4/ 5H/sub 2/O) and indium nitrate. The doping concentration was varied from 7.718/spl times/10/sup -5/ to 3.859/spl times/10/sup -4/ moles. The average particle size, as measured from XRD, SEM, and TEM analyses, varies from 34-130 nm as a result of powder calcination at different temperatures ranging from 300/spl deg/C-900/spl deg/C. Thick-film samples with a thickness of /spl sim/15 /spl mu/m, were tested for low concentration (15-1000 ppm) of CO in air ambient. The optimal temperature for CO sensing is found to be 220/spl deg/C-240/spl deg/C. A blue shift in the sensing temperature and increase in sensitivity factor (S/sub f/) is observed with increasing doping concentration of indium oxide. Maximum sensitivity factor of /spl sim/5 is found for the highest doping concentration (3.859/spl times/10/sup -4/ moles) at 1000 ppm of CO concentration. The morphological and elemental studies of the film are carried out using SEM, TEM, XRD, and EDAX techniques. The results are discussed based on elemental analyses and available theories.     

Nanosized Nb-TiO/sub 2/ gas sensors derived from alkoxides hydrolization

Nanocrystalline TiO/sub 2/ modified with Nb has been produced through the sol-gel technique. Nanopowders have been obtained by means of the hydrolysis of pure alkoxides with deionized water and peptization of the resulting hydrolysate with diluted acid nitric at 100/spl deg/C. The addition of Nb stabilizes the anatase phase to higher temperatures. XRD spectra of the undoped and the Nb-doped samples show that the undoped sample has been almost totally converted to rutile at 600/spl deg/C, meanwhile the doped samples present still a low percentage of rutile phase. Nanocrystalline powders stabilized at 600/spl deg/C with grain sizes of about 17 nm have successfully been synthesized by the addition of Nb with a concentration of 2% at., which appears to be an adequate additive concentration to improve the gas sensor performances, such as it is suggested by the catalytic conversion efficiency experiments performed from FTIR measurements. FTIR absorbance spectra show that catalytic conversion of CO occurs at lower temperatures when niobium is introduced. The electrical response of the films to different concentrations of CO and ethanol has been monitored in dry and wet environments in order to test the influence of humidity in the sensor response. The addition of Nb decreases the working temperature and increases the stability of the layers. Also, large enhancement of the response time is obtained even with lower working temperatures. Moreover, humidity effects on the gas sensor response toward CO and ethanol are less important in Nb-doped samples than in the undoped ones.     

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.     

Gamma radiation nose system based on In/sub 2/O/sub 3//SiO thick-film sensors

A prototype gamma radiation monitoring system based on In/sub 2/O/sub 3//SiO thick-film sensors array was designed. Four sensors had an identical pn-heterojunction structure with different material compositions. These sensors were subjected to gamma radiation emitted by /sup 137/Cs source with an activity of 370 kBq. Changes in their current-voltage characteristics were recorded and compared. The performance parameters of the devices, such as sensitivity to /spl gamma/ radiation exposure and working dose region, were found to be highly dependent on the composition of the materials used. To cover a wider range of radiation and improve the overall sensitivity, an approach of using sensor arrays was utilized. A dynamic selection of the multiple sensors of various sensitivities and working dose ranges was implemented by applying a pattern recognition analysis.     

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.     

Improving sensitivity and selectivity of SnO/sub 2/ gas sensors by temperature variation

A microcontroller-based gas-sensing system is presented in this paper. The analysis presented here exploits the differences in the steady-state performance of SnO/sub 2/ gas sensors at different operating temperatures and the potential use of such differences for improving their selectivity and sensitivity. Sets of experimental measurements of sensitivity versus temperature are used for the detailed presentation of the proposed approach. The results indicate that selective identification and rather accurate measurement of a mixture of CH/sub 4/ and CO gases are quite possible. Finally, a microcontroller-based configuration is presented as a working example of a small-size implementation, which may offer measurements of improved sensitivity and selectivity along with high accuracy and reliability.     

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.     

Optical and electrical H/sub 2/- and NO/sub 2/-sensing properties of Au/In/sub x/O/sub y/N/sub z/ films

In this paper, we describe the optical and electrical gas-sensing properties of In/sub x/O/sub y/N/sub z/ films with an ultrathin gold promoter overlayer. We have fabricated In/sub x/O/sub y/N/sub z/ films with a nanocrystalline porous structure by RF-sputtering in Ar/N/sub 2/ followed by an annealing process. Gold particles with 20-30-nm diameter have been formed on top of the In/sub x/O/sub y/N/sub z/ films by dc sputtering and an annealing process. We have investigated the optical H/sub 2/and NO/sub 2/-sensing properties (change of absorbance) and also the electrical sensing effect (change of electrical resistance) for these two gases. A combined optical/electrical sensor for H/sub 2//NO/sub 2/ is proposed.     

O/sub 2/ sensing properties of Zn- and Au-doped Fe/sub 2/O/sub 3/ thin films

Zn- and Au-doped iron oxide thin films have been prepared by liquid phase deposition. These films have been characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Their performance as oxygen gas sensors has been measured. It has been shown that both the Zn and Au dopants increase the oxygen response of the pure iron oxide films. The XRD and SEM results show that Zn changes both the microstructure and the particles size of the sensing layer through the formation of a solid solution with iron oxide. However, the strong increase in sensitivity to oxygen of the Au-doped Fe/sub 2/O/sub 3/ film has been related to the more favorable chemisorption of oxygen on the small gold particles at the interface with the semiconductor oxide. The results show that Au-doped iron oxide sensors are most promising for oxygen gas sensing.     

Phase-transition temperatures and piezoelectric properties of (Bi/sub 1/2/Li/sub 1/2/)TiO/sub 3/-(Bi/sub 1/2/K/sub 1/2/)TiO/sub 3/ lead-free ferroelectric ceramics

The phase-transition temperatures and piezoelectric properties of x(Bi_1/2Na_1/2)TiO_3-y(Bi_1/2Li_1/2)TiO_3-z(Bi_1/2K_1/2)TiO₃ [x + y + z = 1] (abbreviated as BNLKT100y-100z) ceramics were investigated. These ceramics were prepared using a conventional ceramic fabrication process. The phase-transition temperatures such as depolarization temperatures T_d, rhombohedral-tetragonal phase transition temperature T_R-T, and dielectric-maximum temperature T_m were determined using electrical measurements such as dielectric and piezoelectric properties. The X-ray powder diffraction patterns of BNLKT100y-100z show the morphotropic phase boundary (MPB) between rhombohedral and tetragonal at approximately z = 0.20, and the piezoelectric properties show the maximum at the MPB. The electromechanical coupling factor &33, piezoelectric constant d₃₃ and T_d of BNLKT4-20 and BNLKT8-20 were 0.603, 176 pC/N, and 171degC, and 0.590, 190 pC/N, and 115degC, respectively. In addition, the relationship between d₃₃ and T_d of tetragonal side and rhombohedral side for BNLKT4-100z and BNLKT8-100z were presented. Considering both high T_d and high d₃₃, the tetragonal side of BNLKT4-100z is thought to be the superior composition. The d₃₃ and T_d of BNLKT4-28 were 135 pC/N and 218degC, respectively. Moreover, this study revealed that the variation of Td is related to the variation of lattice distortion such as rhombohedrality 90-alpha and tetragonality c/a.     

Comparison of Fe/Al/sub 2/O/sub 3/ and Fe, Co/Al/sub 2/O/sub 3/ catalysts used for production of carbon nanotubes from acetylene by CCVD

Characterization of iron containing alumina supported catalysts was performed by transmission electron microcopy (TEM), Mo/spl uml/ssbauer, and XPS spectroscopy during formation of multiwall carbon nanotubes from acetylene at 1000 K. TEM images showed that carbon fibers (outer diameter is around 20-40 nm) were generated on Fe/Al/sub 2/O/sub 3/ samples while on the bimetallic Fe,Co/Al/sub 2/O/sub 3/ carbon nanotubes with an average diameter of 8-12 nm were formed. XPS spectra revealed that Fe-Co alloy formed during the interaction of Fe,Co/Al/sub 2/O/sub 3/ and acetylene at 1000 K. The formation of the bimetallic alloy was proven by Mo/spl uml/ssbauer spectroscopy as well.     

Hall effect measurements in gas sensors based on nanosized Os-doped sol-gel derived SnO/sub 2/ thin films

The influence of dopants on the electrical properties of gas sensitive layers used in semiconductor gas sensors has to be carefully understood for getting a deeper insight in the relationship between the sensor performance and its chemical composition. In this work, undoped and Os-doped SnO/sub 2/ thin films have been prepared by the sol-gel process with an Os-Sn atomic ratio of 5%. The films have been characterized by resistivity and Hall effect measurements in a temperature range from 100 K to 500 K, both in air and in vacuum. The results have been investigated according to grain boundary scattering mechanism. We found that in air, the ambient oxygen species adsorbed on the film increase the height of the grain boundary barriers and the activation energy for the electrical conductivity increases in the doped film. In vacuum, the results showed that the height of the intergranular barrier is lower than the corresponding value in air. Both in air and in vacuum, the conductivity of the Os-doped sample is higher than the value in the undoped SnO/sub 2/ sample. The same occurs for the Hall mobility and the carrier concentration. The experimental results have been used to explain the better methane sensitivity, at low temperature, of the Os-doped films as compared with the undoped ones.     

Zr/ZrO2 sensors for in situ measurement of pH in high-temperature and -pressure aqueous solutions

The aim of this study is to develop new pH sensors that can be used to test and monitor hydrogen ion activity in hydrothermal conditions. A Zr/ZrO2 oxidation electrode is fabricated for in situ pH measurement of high-temperature aqueous solutions. This sensor responds rapidly and precisely to pH over a wide range of temperature and pressure. The Zr/ZrO2 electrode was made by oxidizing zirconium metal wire with Na2CO3 melt, which produced a thin film of ZrO2 on its surface. Thus, an oxidation-reduction electrode was produced. The Zr/ZrO2 electrode has a good electrochemical stability over a wide range of pH in high-temperature aqueous solutions when used with a Ag/AgCl reference electrode. Measurements of the Zr/ZrO2 sensor potential against a Ag/AgCl reference electrode is shown to vary linearly with pH between temperatures 20 and 200 degrees C. The slope of the potential versus pH at high temperature is slightly below the theoretical value indicated by the Nernst equation; such deviation is attributed to the fact that the sensor is not strictly at equilibrium with the solution to be tested in a short period of time. The Zr/ZrO2 sensor can be calibrated over the conditions that exist in the natural deep-seawater. Our studies showed that the Zr/ZrO2 electrode is a suitable pH sensor for the hydrothermal systems at midocean ridge or other geothermal systems with the high-temperature environment. Yttria-stabilized zirconia sensors have also been used to investigate the pH of hydrothermal fluids in hot springs vents at midocean ridge. These sensors, however, are not sensitive below 200 degrees C. Zr/ZrO2 sensors have wider temperature range and can be severed as good alternative sensors for measuring the pH of hydrothermal fluids.     

Evolution of nanodomains in the uniaxial relaxor Sr/sub 0.61/Ba/sub 0.39/Nb/sub 2/O/sub 6/:Ce

The evolution of the nanodomain pattern of the uniaxial relaxor ferroelectric strontium barium niobate doped with cerium was studied by piezoresponse force microscopy (PFM). The fractal-like nanodomains observed at room temperature decay on heating. At temperatures up to about 15 K above the Curie temperature, T_c = 320 K, areas of correlated polarization are still visible. On cooling from the paraelectric state to below T_c, a slow isothermal growth of nanodomain was found. The mean domain size increases according to a logarithmic law as predicted for the three-dimensional random field Ising model     

Reduced response times using adsorption kinetics and pulsed-mode operation for the detection of oxides of nitrogen with nanocrystalline SnO/sub 2/ sensors

The work presented in this paper investigates the use of pulsed temperature operation of nanocrystalline SnO/sub 2/ sensors for detecting oxides of nitrogen. Pulsed-mode operation was employed to expand the detection range of these sensors while maintaining high sensitivity at low concentrations. In an attempt to reduce the response times of these devices, adsorption kinetics were applied to the response data. Gas concentrations as low as 10 ppb could be rapidly determined without waiting for a steady-state response to be achieved. The sensors also showed a strong response to ppb levels of NO even at low pulsing temperatures.     

Mechanical and electrical characterization of /spl beta/-Ga/sub 2/O/sub 3/ nanostructures for sensing applications

Single crystalline /spl beta/-Ga/sub 2/O/sub 3/ nanowire and nanoribbon materials were synthesized, and electrical and mechanical properties were studied for sensing applications. The structural analysis showed that the Ga/sub 2/O/sub 3/ nanomaterials were stoichiometric and had the same crystal lattice structure as the /spl beta/ phase Ga/sub 2/O/sub 3/ crystal. The mechanical study on individual Ga/sub 2/O/sub 3/ nanowires and nanoribbons showed that they had a bending modulus of around 300 GPa, are flexible (in bending and twisting), and are easy to be cleaved along their crystal lattice. The current-voltage electrical characterization through the thickness of nanoribbon and along the length of nanowire confirmed their semiconducting characteristic. A two-terminal device fabricated with an individual Ga/sub 2/O/sub 3/ nanowire showed good sensing response to ethanol gas at low-operating temperature, which revealed the potential of using such nanostructures for effective sensing applications.     

SnO/sub 2/ RGTO UV activation for CO monitoring

In this paper, we present recent results regarding the activation of sensors with high density power light of energy in the range of the energy gap of the semiconductor. We report the measurements registered for tin-oxide rheotaxial growth and thermal oxidation deposited layers using CO as a target gas. The influence of doping on the activated gas-sensing properties has been investigated. We have found the value of the incident power corresponding to the best gas-sensing performances (response enhancement and kinetics). The comparison between dark and irradiation condition is presented for the different kind of layers tested.