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.     

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.     

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.     

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.     

Potentiometric CO2 gas sensor with lithium phosphorous oxynitride electrolyte

Potentiometric cell, Au/LiCoO₂ 5 m/o Co₃O₄/Li_2.88PO_3.73N_0.14/Li₂CO₃/Au, has been fabricated and investigated for monitoring CO₂ gas. A LiCoO₂–Co₃O₄ mixture was used as the solid-state reference electrode instead of a reference gas. The idea is to keep the lithium activity constant on the reference side using thermodynamic equilibrium at a given temperature. The thermodynamic stability of the reference electrode was studied from the phase stability diagram of Li–Co–C–O system. The Gibb’s free energy of formation of LiCoO₂ was estimated at 500°C from the measured value of the cell emf. The sensors showed good reversibility and fast response toward changing CO₂ concentrations from 200 to 3000 ppm. The emf values were found to follow a logarithmic Nernstian behavior in the 400–500°C temperature range. CH₄ gas did not show any interference effect. Humidity and CO gas decreased the emf values of the sensor slightly. NO and NO₂ gases affect this sensor significantly at low temperatures. However, increased operating temperature seems to reduce the interference.     

Hydrolyzed colloid reaction (HCR) technique for phosphor powder preparation

Undoped and Eu³⁺, Ce³⁺ and Tb³⁺-doped YVO₄ YPO₄, LaPO₄ and YV_xP_1−xO₄ were prepared in H₂O by the recently introduced hydrolyzed colloid reaction (HCR) technique working at low temperature (<100°C) and atmospheric pressure. Two intermediate — partially hydrophobic — complex colloidal mixtures with metastable characteristics can transform into the stable orthovanadate–orthophosphate phase due to intensive hydrolysis. In contrast with the other low temperature reacting processes — like the sol-gel technique, which makes an amorphous structure — the HCR method can produce crystalline structures in nanometer size ranges. The reaction, morphology, incorporation of activators and different luminescent characteristics are surveyed in this letter-type paper selected from our previous results.     

EPR and DRS evidence for NO2 sensing in Al-doped ZnO

Zinc oxide (ZnO) is a well-known semiconducting multifunctional material wherein properties right from the morphology to gas sensitivity can be tailor-made by doping or surface modification. Aluminum (Al)-incorporated porous zinc oxide (Al:ZnO) exhibits good response towards NO₂ at low-operating temperature. The NO₂ gas concentration as low as 20 ppm exhibits S = 17% for 5 wt.% Al-incorporated ZnO. The NO₂ response increases with operating temperature and concentration and reaches to its maximum at 300 °C without any interference from other gases such as SO₃, HCl, LPG and alcohol. Physico-chemical characterization likes differential thermogravimetric analysis (TG-DTA) electron paramagnetic resonance (EPR) and diffused reflectance spectroscopy (DRS) have been used to understand the sensing behavior for pure and Al-incorporated ZnO. The TG-DTA depicts formation of ZnO phase at 287 °C. The EPR study reveals distinct variation for O⁻ (g = 2.003) and Zn interstitial (g = 1.98) defect sites in pure and Al:ZnO. The DRS studies elucidate signature of adsorbed NO_x species in aluminium-incorporated zinc oxide indicating its tendency to adsorb these species even at low temperatures. This paper is an attempt to correlate the gas sensing behavior with the physico-chemical studies such as EPR and DRS.     

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.     

PECVD-SiOxNy films for large area self-sustained grids applications

In this work we study the structural properties and mechanical stress of silicon oxynitride (SiO_xN_y) films obtained by plasma enhanced chemical vapor deposition (PECVD) technique at low temperatures (320 °C) and report the feasibility of using this material for the fabrication of large area self-sustained grids. The films were obtained at different deposition conditions, varying the gas flow ratio between the precursor gases (N₂O and SiH₄) and maintaining all the other deposition parameters constant. The films were characterized by ellipsometry, by Fourier transform infrared (FT-IR) spectroscopy and by optically levered laser technique to measure the total mechanical stress. The results demonstrate that for appropriated deposition conditions, it is possible to obtain SiO_xN_y with very low mechanical stress, a necessary condition for the fabrication of mechanically stable thick films (up to 10 μm). Since this material (SiO_xN_y) is very resistant to KOH wet chemical etching it can be utilized to fabricate, by silicon substrate bulk micromachining, very large self-sustained grids and membranes, with areas up to 1 cm² and with thickness in the 2–6 μm range. These results allied with the compatibility of the PECVD SiO_xN_y films deposition with the standard silicon based microelectronic processing technology makes this material promising for micro electro mechanical system (MEMS) fabrication.     

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.     

Plasma-deposited copper phthalocyanine: A single gas-sensing material with multiple responses

Copper phthalocyanine (CuPc) thin films have been deposited by glow discharge-induced sublimation (GDS). This physical technique allows to produce very high porosity films, whose response to gases is much more intense than evaporated films. It has been found that both electrical and optical properties of these films change upon gas exposure due to the gas/film interaction. Electrical response of the films has been tested by exposing the samples to NO_x-containing atmospheres and by measuring the slope of the electrical surface current versus gas concentration. This way NO₂ and NO concentrations down to 0.1 ppm and 10 ppm have been measured, respectively, with response times shorter than 2 min. Optical responses have been tested by measuring the change of light reflectance at a fixed wavelength upon exposure to ethanol-containing atmospheres down to concentrations of few thousands of ppm. Response times of less than 10 s have been obtained.     

Etch rates for micromachining processing

The etch rates for 317 combinations of 16 materials (single-crystal silicon, doped, and undoped polysilicon, several types of silicon dioxide, stoichiometric and silicon-rich silicon nitride, aluminum, tungsten, titanium, Ti/W alloy, and two brands of positive photoresist) used in the fabrication of microelectromechanical systems and integrated circuits in 28 wet, plasma, and plasmaless-gas-phase etches (several HF solutions, H₃PO₄, HNO₃ +H₂O+NH₄F, KOH, Type A aluminum etchant, H ₂O+H₂O₂+HF, H₂O₂, piranha, acetone, HF vapor, XeF₂, and various combinations of SF₆, CF₄, CHF₃, Cl₂, O₂ , N₂, and He in plasmas) were measured and are tabulated. Etch preparation, use, and chemical reactions (from the technical literature) are given. Sample preparation and MEMS applications are described for the materials     

Electrochemical measurement of SO3-SO2 in process gas streams

The two major industrial sources of sulphur dioxide emissions are electrical generation and non-ferrous smelting. While flue-gas scrubbing and acid-plant technology are well established, continuous methods for the determination of SO₂ in these process streams are based on expensive conventional UV or IR spectroscopic instrumentation in which the gases must be conditioned prior to analysis. Additionally, there appears to be no reliable continuous low-maintenance method of analysis for SO₃ in gases. Solid-state sensors for the continuous real-time measurement of concentrations of SO₃ and SO₂ in process gas streams offer the possibility of monitoring the efficiency of flue-gas scrubbing, determining the concentrations of SO₃ in corrosion-susceptible ducting or in acid-plant conversion towers and guarding against excessive releases of SO₃ from acid-plant tail gas. The measurement of SO₂ and SO₃ in gases by solid-state electrochemistry is reviewed. The electrochemical cells are described, and wherever possible, the temperature and concentration ranges of the various solid-state devices reported in the literature are given. We conclude with a summary of the further requirements for a successful inexpensive commercial solid-state sensor for SO₃ and SO₂ measurement in process gas streams.     

基于特征气体SO2F2的SF6气体绝缘设备的过热性故障诊断

利用SF₆分解产物检测来判断GIS故障发展程度已成为一种有效手段,在搭建的实验平台上展开200℃~360℃局部过热模拟实验,研究SF₆热分解特性。当实验温度较高时(320℃~360℃),新增SO₂F₂、H₂S、COS三种产物。在绝缘设备充满大量SF₆子的背景下,分解产生的H₂和COS的含量极少,给气体检测带来了困难。文中提出将SO₂F₂作为设备故障进入严重状态的标志气体,同时用量子化学计算法在B3LYP/6-311G(+d,p)水平下对SO₂F₂生成机理和能量条件进行研究。发现SO₂F₂通过F₂碎片与气室内SO₂反应、F原子与SO₂F结合、SOF 4水解反应这三条途径得到,其中SO₂与F₂反应是SO₂F₂的主要来源。实验现象与理论计算均表明:SO₂F₂的形成机制与高温息息相关,SO₂F₂出现,标志着设备故障处温度较高,SF₆绝缘能力已遭到严重破坏。     

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.     

Room temperature hydrogen response kinetics of nano–micro-integrated doped tin oxide sensor

The nano–micro-integrated sensor has been fabricated by sol–gel depositing the nanocrystalline indium oxide (In₂O₃)-doped tin oxide (SnO₂) thin film on microelectromechanical systems (MEMS) device having interdigitated electrode configurations with two different electrode spacing (10 μm and 20 μm) and two different number of fingers (8 and 20). The present nano–micro-integrated sensor exhibits high H₂ sensitivity range (S = 3–10⁵) for the H₂ concentration within the range of 100–15,000 ppm at room temperature. It has been demonstrated that, the room temperature response kinetics of the present nano–micro-integrated sensor is a function of finger spacing, H₂ concentration and air-pressure, but independent of number of fingers. Such dependence has been explained on the basis of Le Chatelier's principle applied to the associated H₂ sensing mechanism and the role of above parameters in shifting the dynamic equilibrium of the involved surface reactions under the described test conditions. A new definition of the response time has been proposed, which is not only suitable for the theoretical analysis but also for the practical applications, where a gas-leak detection alarm is required to be triggered.     

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.     

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.     

量子化学方法研究阴离子表面活性剂在气液界面上的吸附

用量子化学方法中的密度泛函理论,在B3LYP/6-3IG水平上,对十二烷基硫酸钠（SDS）阴离子表面活性剂与水分子形成的水合物CH₃（CH₂）₁₁OSO₃ˉ（H₂O）_n（n=0～7）进行结构优化和频率计算。从分子水平上研究了CH₃（CH₂）₁₁OSO₃ˉ在气液界面上与水分子的相互作用。计算结果表明:（1）7个水分子与极性头均采用1:1型和2:1型,即极性头中一个氧原子或2个氧原子与水分子以氢键形式构成水合层;（2）CH₃（CH₂）₁₁OSO₃中的氧原子与水分子中的氧原子最短氢键的键长（O-O键长）在0.27～0.31 nm之间,H…O键长在0.19～0.21 nm之间,O-H…O键角在140°～167°之间,均属于中强氢键:（3）水合物R（S-O）平均键长比表面活性剂单体分子分别增长了,说明形成水合物后S-O间的键减弱;（4）结合能D₀从64.04 kJ/mol增加到.428.29 kJ/mol,说明随着水分子数的增加,所获得的7种水合物的稳定性依次增强,表明最终形成的水合层是稳定的:（5）随着水分子数增加疏水基链长收缩,亲水基总电荷增加,C12-O13-S14的键角增大;（6）由于烷烃链带有了弱电荷,使胶束内核带有了部分极性,此种极性介于烷烃油相和水相的极性之间,利于表面活性剂在溶液中的聚集。