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

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

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.     

Selective NH3 gas sensor based on Langmuir-Blodgett polypyrrole film

Polypyrrole thin films have been deposited onto a glass substrate by the Langmuir-Blodgett technique to fabricate a selective ammonia (NH₃) gas sensor. The d.c. electrical resistance of the sensing elements is found to exhibit a specific increase upon exposure to different gases such as NH₃, CO, CH₄, H₂ in N₂ and pure O₂. The polypyrrole thin-film detector shows a considerable increase of resistance when exposed to NH₃ in N₂, and negligible response when exposed to comparable concentrations of interfering gases such as CO, CH₄, H₂ in N₂ and pure O₂. The calibration curve for NH₃ in N₂ at room temperature is measured in the concentration range from 0.01 to 1%. The relative change of the electrical resistance is about 10% for the lower detectable limit of 100 ppm of NH₃ in N₂. The sensitivity of the Langmuir-Blodgett polypyrrole towards ammonia is considerably higher than that of the electrochemical polypyrrole. The fast rise time and the high sensitivity of the detector are reported as a function of number of the polypyrrole layers. Long-term aging tests of the selective NH₃ gas sensor are performed.     

Compact electrochemical bifunctional NOx/O2 sensor with metal/metal oxide internal reference electrode for high temperature applications

Simultaneous measurement of total NO_x and O₂ using two electrochemical methods are demonstrated using metal/metal oxide internal oxygen reference electrode-based sensors at high temperatures. The Pd/PdO-containing reference chamber was sealed within a stabilized zirconia superstructure by a high pressure/temperature plastic deformation bonding method exploiting grain boundary sliding between the ceramic components. Amperometric and potentiometric NO_x sensing devices were assembled on the outside of the sensor. Pt-loaded zeolite Y was used to obtain total NO_x capability. Both the amperometric and potentiometric type sensors showed total NO_x response, with the potentiometric device showing better NO_x/O₂ signal stability and lower NO_x–O₂ cross-interference. Since these sensors do not require plumbing for reference air, there is more flexibility in the placement of such sensors in a combustion stream.     

A MEMS Singlet Oxygen Generator—Part II: Experimental Exploration of the Performance Space

This paper reports the quantitative experimental exploration of the performance space of a microfabricated singlet oxygen generator (muSOG). SOGs are multiphase reactors that mix H₂O₂, KOH, and Cl₂ to produce singlet delta oxygen, or O₂ (a). A scaled-down SOG is being developed as the pump source for a microfabricated chemical oxygen-iodine laser system because scaling down a SOG yields improved performance compared to the macroscaled versions. The performance of the muSOG was characterized using O₂ (a) yield, chlorine utilization, power in the flow, molar flow rate per unit of reactor volume, and steady-state operation as metrics. The performance of the muSOG is measured through a series of optical diagnostics and mass spectrometry. The test rig, which enables the monitoring of temperatures, pressures, and the molar flow rate of O₂ (a), is described in detail. Infrared spectra and mass spectrometry confirm the steady-state operation of the device. Experimental results reveal O₂ (a) concentrations in excess of 10¹⁷ cm^-3, O₂ (a) yield at the chip outlet approaching 80%, and molar flow rates of 02(a) per unit of reactor volume exceeding 600 times 10^-4 mol/L/s.     

Characterization of ozone sensors based on WO3 reactively sputtered films: influence of O2 concentration in the sputtering gas, and working temperature

We report on electrical responses of tungsten oxide thin film ozone sensors based on a tungsten trioxide (WO₃)/tin oxide (SiO₂)/Si structure with interdigitated Pt electrodes. The influence of O₂ concentration in the sputtering gas and working temperature of the sensor are investigated. Sensitivity to ozone increases with O₂ content in the sputtering gas. It reaches its highest value for sensors fabricated with 50% O₂. For these sensors, the best ozone sensitivity and shortest response and recovery times are obtained at a working temperature of 523 K. Ozone sensitivity is compared to other ozone sensors.     

Titania NOx sensors for exhaust monitoring

Oxide semiconductors have been examined to develop NO_x sensors for exhaust monitoring. Titania doped with trivalent elements, such as Al³⁺, Sc³⁺, Ga³⁺ or In³⁺, has a good sensitivity and selectivity to NO between 450 and 550 °C, and shows rapid response. A sensor probe for monitoring exhaust NO_x has been fabricated. Many kinds of interference gases, such as C₃H₆, CO and SO₂, have been found to have only a slight influence on the sensor response to NO. The influence of O₂ and H₂O is also negligible, except for the cases of 0% H₂O and fuel-rich conditions. In accordance with these results, the sensor probe operates satisfactority in the exhaust gas of various combustion conditions without interference from the various kinds of gas species in the exhaust gases.     

Integrated optical pH sensor using replicated chirped grating coupler sensor chips

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

Fast response of undoped and Li-doped titania thick-films at low temperature

The fast response of undoped and Li-doped TiO₂ operating at low temperature to hydrogen and oxygen is investigated. The TiO₂ sensors are fabricated using thick-film technique. The prepared materials exhibit the presence of only rutile phase of TiO₂ but enlarged crystal lattice parameters were confirmed by X-ray diffraction (XRD). Scanning electron microscopy (SEM) shows that the grain size of the material has not obviously changed with different Li-doping (2–4 mol%), but the undoped is much smaller. Kroger–Vink model indicates that Li mainly substitutes for the lattice point of Ti. Because the material resistance decreases as the oxygen pressure increases, Li-doped samples can be regarded as a p-type semiconductor compared with pure TiO₂. The operating temperature of the Li-doped TiO₂ samples is found to be lower than that of pure TiO₂ in H₂ and O₂ environment. At less than 3 mol% Li content, the response time of the Li-doped TiO₂ gas sensors is much shorter than that of pure TiO_2, at the same temperature under both H₂ and O₂ environment. Moreover, the sample of 3 mol% Li-doping exhibits the best response characteristics. The response mechanism is suggested to arise from the conduction holes ionized by Li and the surface potential barrier change in different gas environments.     

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.     

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.     

Light-addressable suspended-gate gas sensor

A light-addressable potentiometric sensing (LAPS) system has been applied to construct an oxygen sensor using a suspended-gate electrode. The sensor principally consists of an MIS structure, i.e., suspended gate/air gap/LaF₃/SiO₂/Si. The use of the suspended gate makes it possible to realize a contactless sensing system, which provides a flexible structure to integrate multiple sensing elements on a single-chip semiconductor surface. The sensor shows a stable response at room temperature to oxygen partial-pressure changes in the range 0.25-1.0 atm. The fabrication conditions of the LaF₂ film are also discussed.     

A silicon integrated opto-electro-mechanical displacement sensor

This paper describes a compact and low cost micro-opto-electro-mechanical displacement sensor. Our purpose is the fabrication of a long range, nanometer resolved encoder using a standard CMOS technology, in order to integrate the optical metrology system (photodiodes, analog and digital circuits) on a single chip. We introduce the interferometric linear encoder principle using diffraction gratings; then we present results of optical and electrical characterization of an optoASIC including photodiodes and associated electronic integrated on a standard 0.6 μm CMOS process. This CMOS circuitry is then included inside of a prototype of linear displacement encoder using the principle of diffraction gratings in reflection. Finally, we present the fabrication of micrometer and sub-micrometer diffraction gratings etched in silicon material, in order to obtain a higher encoder integration.     

A MEMS Singlet Oxygen Generator—Part I: Device Fabrication and Proof of Concept Demonstration

This paper reports the design, fabrication, and proof of concept demonstration of a singlet oxygen generator (SOG) that operates on the microscale. The micro-SOG (muSOG) chip is implemented in a three-wafer stack using deep reactive ion etching (DRIE) and wafer bonding as key technologies. The device creates singlet delta oxygen (O₂(a)) in an array of packed-bed reaction channels fed by inlet manifolds with pressure drop channels that ballast the flow. An integrated capillary array separates the liquid and gas by-products, and a microscale heat exchanger removes excess heat of reaction. The fabrication process and package are designed to minimize collisional losses and wall deactivation of O₂(a). The design, fabrication, and package of the device are documented. Proof of concept demonstration of the device is given by optical emission measurements of the spontaneous decay of the O₂ (a) molecule into its triplet state and by the observation of the emission from dimol pairs of O₂ (a) molecules.     

Hydrogen sensor based on antimonium pentoxide-phosphoric acid solid electrolyte

A solid composite electrolyte with high proton conductivity based on antimonium pentoxide with additives of phosphoric acid has been obtained. A potentiometric solid-state gas sensor using this electrolyte has been developed for detecting small amounts of hydrogen (10–2000 ppm) in gas mixtures at ambient temperature. The sensor consists of the reference electrode: Ag or Ag/(Ag + Ag₂SO₄), the solid composite electrolyte and H₂-sensitive electrode: Pt or Pd. The electromotive force (e.m.f.) of the sensor varies logarithmically with H₂ concentration for hydrogen partial pressures in the range 100–2000 ppm and depends on the oxygen partial pressure. The slope of e.m.f.-log(pH₂) dependence is 170 and 200 mV for Pt and Pd, respectively, which exceeds the Nernst value, presumably due to the formation of a mixed potential. The sensor can operate at a wide range (20–95%) of a relative humidity.     

The comparative XPS and PYS studies of SnO2 thin films prepared by L-CVD technique and exposed to oxygen and hydrogen

The electronic properties of the space charge layer of the tin dioxide thin films, prepared by the laser-induced chemical vapour deposition (L-CVD), have been studied using X-ray photoelectron spectroscopy (XPS) and photoemission yield spectroscopy (PYS). Based on the analysis of Sn3d_5/2 XPS peak, the influence of exposition to molecular oxygen O₂ and hydrogen H₂ on the stoichiometry of the L-CVD deposited SnO₂ thin films, as well as the interface Fermi level position in the band gap, have been determined and compared to the variation of the work function determined from the threshold of the ex situ recorded photoemission yield spectra. The observed changes of the interface Fermi level position and the work function upon adsorption/desorption of O₂ and H₂ were attributed to decrease/increase of the concentration of oxygen vacancies in the near surface region.     

Fabrication of miniature Clark oxygen sensor integrated with microstructure

A miniature Clark-type oxygen sensor has been integrated with a microstructure using a novel fabrication technique. The oxygen chip consists of a glass substrate with a three-electrode configuration, which is separated and connected by a groove, and a poly(dimethylsiloxane) (PDMS) container with an immobilized PDMS oxygen-permeable membrane. The assembly of the different substrates only uses the O₂ plasma bonding technique, and the fabrication temperatures do not exceed 95 °C. Characteristics of the miniature sensor include the fastest response time of 6.8 s, good linearity with a correlation coefficient of 0.995, and a long lifetime of at least 60 h. The present miniature Clark oxygen sensor can be readily integrated with a microfluidic system to form a μ-TAS.     

Plasma planarization for sensor applications

Filling trenches in silicon using phosphosilicate glass (PSG) provides many possibilities for novel device structures for sensors and actuators. This paper describes a plasma planarization technique that provides fully planarized PSG filled silicon trenches for sensor applications. The technique consists of planarizing the substrate using two photoresist layers and plasma etching-back. The lower resist layer is the AZ5214 image reversal resist, which is patterned and then thermally cured. The upper resist layer is a global HPR204 coating. The plasma etching-back is carried out using CHF₃/C₂F ₆ gas mixture with an O₂ addition. It is shown that by using the image reversal photoresist approach, fully planarized surface coating can be obtained without resorting to an additional mask. By adding 25 sccm (14%) O₂ into the 137 sccm CHF₃+18 sccm C₂F₆ gas mixture, the etch rates for the photoresist and PSG can be matched. Process optimization for the two layer resist coating and plasma etching is discussed     

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

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