Multichannel Raman gas analyzer: the data acquisition and control system. Measurement improvement with blue laser light

In this paper, the data acquisition and control system of a multichannel Raman effect-based gas analysis device is presented, together with the improvements achieved in measurement of gas concentration sensitivities as a result of the operation of the system with a new blue laser-light source. The multichannel Raman gas sensor (MRGS) is based on the linear Raman scattering effect and uses photo multiplier tubes (PMTs) in the photon-counting mode of operation. An embedded microcontroller-based data acquisition and control (MDAC) system collects, digitizes, processes, and stores in real time the data from six photon-counting modules and the accompanying sensors, along with an overall system control through appropriate actuators. Recent advances in the development of solid-state laser sources have enabled the use of a new, state-of-the-art, blue laser for the excitation of the Raman effect. Using this blue laser source, improvements in the sensitivities in measurements of concentration for all tested gases (SO/sub 2/, CO/sub 2/, CO, NO/sub 2/, C/sub 6/H/sub 6/, and N/sub 2/) have been substantiated, compared with the green laser source previously used and reported in a related article.     

Dedicated temperature sensing with c-axis oriented single-crystal ruby (Cr/sup 3+/:Al/sub 2/O/sub 3/) fibers: temperature and strain dependences of R-line fluorescence

Single-crystal fibers of ruby (Cr/sup 3+/:Al/sub 2/O/sub 3/) with approximately 0.1 wt.% Cr/sup 3+/ have been produced by the laser heated pedestal growth (LHPG) technique. The fluorescence emissions of the R/sub 1/ and R/sub 2/ lines were studied as functions of temperature and strain. Fluorescence decay lifetime measurements indicate that these fibers may be suitable for thermometric applications up to 973 K while strain measurements show only a very weak dependence. Similarly, characterization of the R-line shifts also show a weak strain sensitivity and an appreciably larger change with temperature. One fiber sample has been tested to destruction to demonstrate this weak strain dependence. Single-crystal ruby fibers are, thus, found to be potential candidates for dedicated temperature sensing from room temperature to /spl sim/923 K.     

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.     

Nonconducting polymers on Prussian Blue modified electrodes: improvement of selectivity and stability of the advanced H/sub 2/O/sub 2/ transducer

An approach to improve the analytical performance of a Prussian Blue (PB)-based hydrogen peroxide transducer is described. In support of this objective, both the stabilizing and anti-interferent properties of nonconducting films were used. Electropolymerization on the top surface of PB modified electrodes is possible due to the high oxidizing ability of Berlin Green, and the growth of nonconductive polymers may be independently monitored by investigating the redox activity of the inorganic polycrystal. The best performance characteristics, which are advantageous over existing H/sub 2/O/sub 2/ sensors, were obtained for PB electrodes covered with electropolymerized o-phenylenediamine (1,2-diaminobenzene). The reported transducer remained at the 100% response state for more than 20 h under continuous flow of 0.1-mM hydrogen peroxide (flow rate 1 mlmin/sup -1/), which improves the stability level among the selective H/sub 2/O/sub 2/ sensors by one order of magnitude. The selectivity factor of the PB-poly (1,2-diaminobenzene) based transducer relative to ascorbate is nominally 600. PB-poly(1,2-diaminobenzene) modified electrode allows the detection hydrogen peroxide in the flow-injection mode down to 10/sup -7/ M with sensitivity of 0.3 AM/sup -1/cm/sup -2/, which is two times lower compared to the uncovered PB-based transducer.     

Improvement in sensitivity and selectivity of InP-based gas sensors: pseudo-Schottky diodes with palladium metallizations

The possibility of using single resistive n-type InP semiconductor gas sensors to perform accurate measurements of ozone or nitrogen dioxide concentration in air comes up against their low sensitivity and the inability to discriminate between the influence of each gas on the sensors without any exterior apparatus. To improve these two fundamental aspects of gas sensors, the sensitive n-InP layers have been included in more complex devices, called pseudo-Schottky diodes. Made by successive evaporation of metallic thin layers on p-InP substrates, their Schottky metallization schemes (Pd/Ge/Pd) satisfy a double objective: the creation of the necessary n-InP gas sensitive layer by activation of Ge dopants and the ozone catalytic conversion by palladium layers. Comparisons between the sensing performances of the two gas sensors (resistive and Schottky diode-type ones) show that sensitivity of the laters is largely higher than that of single resistive gas sensors. On the other hand, a good selectivity toward ozone is achieved with Pd/Ge/Pd/p-InP gas sensors, resulting from different reaction kinetics between O/sub 3/ or NO/sub 2/ and the sensitive layer. These differences can be attributed to the palladium metallization catalytic activity.     

Calibration of Curie temperatures for LiTaO/sub 3/ single crystals by the LFB ultrasonic material characterization system

The line-focus-beam ultrasonic material characterization (LFB-UMC) system is applied to a standardized comparison and evaluation of the Curie temperatures, T/sub C/, exclusively used in evaluating the chemical compositions of commercial LiTaO/sub 3/ crystals by measuring the velocities of Rayleigh-type leaky surface acoustic waves (LSAWs), V/sub LSAW/. We measured V/sub LSAW/ and T/sub C/ (standardized) under the same T/sub C/ measurement conditions for 36/spl deg/Y X-LiTaO/sub 3/ single-crystal wafers produced by four manufacturers and related the results to the T/sub C/ (individual) measured by the individual manufacturers. The relationships between V/sub LSAW/ and T/sub C/ (individual) varied from one company to another, and a single straight line of the proportional relationship between V/sub LSAW/ and T/sub C/ (standardized) was obtained for all wafers regardless of the manufacturer. These experimental results clarify that the problem associated with T/sub C/ measurements lies in the measurement conditions and the absolute accuracy of the measurement instruments. Measurements of the center frequencies of SH-type surface acoustic wave (SAW) filter devices are compared with V/sub LSAW/ measurements. A method of calibrating T/sub C/ using this ultrasonic system is proposed to establish standardized specifications of SAW-device crystal wafers.     

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.     

Use of different sensing materials and deposition techniques for thin-film sensors to increase sensitivity and selectivity

The performances of metal oxide semiconducting materials used as gas-sensing detectors depend strongly on their structural and morphological properties. The average grain size has been proved to play a prominent role and better sensor performances were found in polycrystalline films where the grain size is few tens of nm or smaller. On the other hand, thermal treatments during thin-film deposition and/or sample postprocessing could lead to a grain coalescence, thus decreasing the conductivity of the sensing film. Avoiding such a phenomenon, still keeping optimized processing conditions, will increase the sensor performances, maintaining the resistivity at acceptable values. In this work, new gas-sensing materials and new thin-film deposition procedures have been investigated. Aiming to preserve the sensitivity, to enhance selectivity and to reduce the drift, thin films of WO/sub 3/ and CrTiO/sub 3/ deposited by pulsed-laser ablation (PLA) and of SnO/sub 2/ deposited by rheotaxial growth and thermal oxidation techniques were comparatively characterized. Three issues were mainly addressed: the variation of the conductivity as a function of RH, the sensitivity toward benzene, CO, acetone, and NO/sub 2/, and the selectivity.     

CO/sub 2/ laser pulse monitoring instrument based on PVDF pyroelectric array

This paper proposes to extend the use of low-cost, pyroelectric, polyvinylidene fluoride four-quadrant arrays, originally devoted to monitoring the beam point stability of CO/sub 2/ laser beams, to the temporal profiling of the same laser pulse providing an instrument that is not commercially available. The advantage of using a single sensor for both types of measurements can be fully exploited if the pyroelectric sensor bandwidth is made almost flat in the typical frequency range (10 Hz-20 kHz) of the signal spectrum generated by a modulated CO/sub 2/ laser. In this paper, we present the design of an active analog compensation filter aimed to improve the reconstruction accuracy of the laser pulses and its circuit implementation with a quad operational amplifier for an easy integration of the compensation filter on the same board hosting the sensor. Experimental results obtained with modulated CO/sub 2/ laser beams, at pulse repetition rates from 10 to 1000 Hz and variable duty cycle, proved accurate in the laser pulse reconstruction with sensitivity of commercial semiconductor HgCdZnTe sensors.     

Intrinsic sensitivity of Cd/sub 1-x/Zn/sub x/Te semiconductors for digital radiographic imaging

The intrinsic sensitivity of cadmium zinc telluride (Cd/sub 1-x/Zn/sub x/Te) semiconductor detectors has been experimentally measured, within the X-ray diagnostic energy range. The results of this study indicate that the intrinsic efficiency of Cd/sub 1-x/Zn/sub x/Te can be increased by optimizing geometrical and physical detection parameters such as X-ray irradiation geometry, detector thickness, and applied electric field. These results indicate that Cd/sub 1-x/Zn/sub x/Te is a suitable candidate for digital imaging applications.     

Preparation, morphology, and gas-sensing behavior of Cr/sub 2-x/Ti/sub x/O/sub 3+z/ thin films on standard silicon wafers

The effect of humidity on chromium titanium oxide (Cr/sub 2-x/Ti/sub x/O/sub 3+z/, CTO), on both baseline resistance and sensitivity, is small compared to SnO/sub 2/. This has been the key to development of thick-film sensors based on CTO, for detection of carbon monoxide and ammonia in synthetic air. Thin-film structures on silicon substrates offer the possibility to use fabricating, bonding and housing equipment and, hence, a low cost gas sensor production is possible. CTO thin-film sensors on silicon substrates use conventional photolithography, sputtering and evaporation techniques. A Ta/Pt resistance layer (25/200-nm thick) for heating the device to its operating temperature and interdigital electrodes are evaporated and structured on a silicon substrate which is covered by a 1-/spl mu/m SiO/sub 2/ insulating layer. The polycrystalline p-type CTO is deposited onto the electrodes by oxidizing reactive sputtering or evaporation of Cr/Ti-sandwich structures. The resulting sensors were characterized by means of energy dispersive X-ray analysis, secondary electron microscopy, and X-ray diffraction pattern. Also, gas responses toward NO/sub 2/, NH/sub 3/, CO and CH/sub 4/, and different humidity, were investigated.     

Limiting sensitivity of a differential absorption spectrometer with direct detection in the 2/spl nu//sub 3/ and /spl nu//sub 2/+2/spl nu//sub 3/ vibration bands [methane detection applications]

A differential absorption spectrometer, for methane detection, using tunable laser diodes in the 1.33-/spl mu/m and 1.66-/spl mu/m bands, has been studied. The spectral scanning is carried out by current modulation of the laser diode. We analyzed the performance with a multimode Fabry-Perot laser diode in the /spl nu//sub 2/+2/spl nu//sub 3/ band of methane and a monomode laser diode in the 2/spl nu//sub 3/ band. The theoretical results are validated by several experiments. To determine the sensitivity limit of the sensor, we have examined the influence of the noise sources. A sensitivity of 10 ppm/spl middot/m was obtained in the 2/spl nu//sub 3/ band. The main limiting factors are the relative intensity noise of the laser, optical interferences, and quantization noise. We also analyzed the influence of the temperature on the laser diode emission spectra and the methane absorption spectra.     

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.     

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.     

The /spl plusmn/45/spl deg/ correlation interferometer as a means to measure phase noise of parametric origin

A radiofrequency interferometric detector is combined with the correlation-and-averaging technique in a new scheme for the measurement of the phase noise of a component. The method relies upon the assumption that the phase noise of the component being tested (DUT) exceeds the amplitude noise, which is consistent with the general experience in the field of wireless engineering. The new scheme is based on the amplification of the DUT noise sidebands and on the simultaneous measurement of the amplified noise by means of two mixers driven in quadrature, /spl plusmn/ 45/spl deg/ off the carrier phase. The /spl plusmn/45/spl deg/ detection has two relevant properties, namely 1) the sensitivity is neither limited by the thermal energy k/sub B/T/sub 0/, nor by temperature uniformity, and 2) the noise of the measurement amplifier is rejected, despite a single amplifier being shared by the two channels of the correlator. The article provides the theoretical background and experimental results. The sensitivity of the first 100-MHz prototype, given in terms of the S/sub /spl phi//(f) floor, is some 12 dB below k/sub B/T/P/sub 0/, where P/sub 0/ is the carrier power. Using a dual carrier suppression scheme, the residual flicker is as low as -168 dBrad/sup 2//Hz at f=1 Hz off the carrier.     

Simultaneous electrochemical detection of nitric oxide and carbon monoxide generated from mouse kidney organ tissues

A planar-type amperometric dual microsensor for simultaneous detection of nitric oxide and carbon monoxide is presented. The sensor consists of a dual platinum microdisk-based working electrode (WE) and a Ag/AgCl counter/reference electrode covered with an expanded poly(tetrafluoroethylene) (Tetra-tex) gas-permeable membrane. The dual WE possesses two different platinized platinum disks (WE1 and WE2, 250 and 25 microm in diameter, respectively). The larger WE1 is further modified with electrochemical deposition of tin. Use of two sensing disks different in their size as well as in their surface modification produces apparently different sensitivity ratios of NO to CO at WE1 and at WE2 (approximately 2 and approximately 10, respectively) that are induced by favorable CO oxidation on the surface of tin versus platinum. Anodic currents independently measured at WE1 and at WE2 are successfully converted to the concentrations of NO and CO in the co-presence of these gases using the differentiated sensitivities at each electrode. The sensor is evaluated in terms of its analytical performance: respectable linear dynamic range (sub nM to microM); low detection limit (approximately 1 nM for NO and <5 nM for CO); selectivity (over nitrite up to approximately 1 mM); and sensitivity (sufficient for analyzing physiological levels of NO and CO). Using the NO/CO dual microsensor, real-time, simultaneous, direct, and quantitative measurements of NO and CO generated from living biological tissue (mouse, c57, kidney) surfaces, for the first time, are reported.     

An enhanced fiber-optic temperature sensor system for powertransformer monitoring

The paper deals with a sensor for temperature measurements in fluids. The sensor is based on a fiber-optic sensing element and on microcontroller-based signal processing hardware. The physical principle behind its operation is briefly reviewed, and its application to power transformer hot-spot temperature measurement is reported. Laboratory experimental results are given for both sensor characterization and measurements carried out on a 25-kVA oil-cooled power transformer     

Generation-recombination noise in pseudomorphic Modulation-doped Al/sub 0.2/Ga/sub 0.8/As/In/sub 0.1/Ga/sub 0.9/As/GaAs micro-Hall devices

The noise spectrum in micro-Hall devices based on pseudomorphic Al/sub 0.2/Ga/sub 0.8/As/In/sub 0.1/Ga/sub 0.9/As/GaAs modulation-doped heterostructures was measured between 4 Hz and 65 kHz, allowing components due to thermal, 1/f, and generation-recombination to be characterized. Applying deep level noise spectroscopy (DLNS) in the temperature range of 77-300 K to analyze the generation-recombination part of the spectrum, two electron traps contributing to noise density were identified. An emission activation energy of 474 meV was measured for the dominant trap, corresponding to the well-known DX center originating from the AlGaAs barrier. The other deep level, with an emission activation energy of 242 meV, is probably related to defects in the InGaAs layer. The structures under investigation resulted in high-performance micro-Hall devices: a supply-current-related sensitivity up to 725 V/spl middot/A/sup -1//spl middot/T/sup -1/ at 77 K independent of bias current, a signal-to-noise sensitivity of 155 dB/spl middot/T/sup -1/ and a detection limit of 340 pT/spl middot/mm/spl middot/Hz/sup -1/2/ at 77 K were measured.     

A Microcontroller-Based Architecture to Reduce Gravimeter Output for the Effect of Meteorological Parameters

Continuously running gravimeters are usually adopted to overcome the drawbacks of discrete measurements that are used to monitor gravity changes in volcanic areas (i.e., inaccessibility during wintertime). Exogenous environmental parameters, however, usually affect the performance of these devices, and suitable analytical methodologies are adopted to compensate for these effects. This paper aims to demonstrate the features of the nonlinear compensation strategy that was introduced by the author in the previous works when a real-time reduction of the gravimeter output for the effect of meteorological parameters has to be performed. Moreover, a microcontroller-based electronics that implements such real-time compensation strategy is presented.     

A novel NO/sub 2/ gas sensor based on Bis[phthalocyaninato] samarium complex/silicon hybrid charge-flow transistor

A new kind of sandwich-like bis[2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato] samarium complex Sm[Pc/sup */]/sub 2/(Pc/sup */=Pc(OC/sub 8/H/sub 17/)/sub 8/) is used as film-forming material. Pure Sm[Pc/sup */]/sub 2/ and mixture of Sm[Pc/sup */]/sub 2/ and octadecanol(OA) deposited from both pure water and 10/sup -4/M Cd/sup 2+/ subphases are investigated. It is found that a mixture of 1:3 Sm[Pc/sup */]/sub 2/:OA forms an excellent material for the fabrication of the gas-sensing Langmuir-Blodgett (LB) film by studying the film-forming characteristics. A new gas sensor has been fabricated by incorporating the multilayer LB film into the gate electrode of a metal-oxide-semiconductor field effect transistor, forming an array of charge-flow transistor. On the application of a gate voltage (V/sub GS/), greater than the threshold voltage (V/sub TH/), a delay was observed in the response of the drain current. This is due to the time taken for the resistive gas-sensing film to charge up to V/sub GS/. This delay characteristic was found to depend on the concentration of NO/sub 2/. Results are presented showing that the device can detect reversibly the concentration of NO/sub 2/ gas down to 5 ppm at room temperature.