聚吡咯/二氧化钛复合薄膜的制备及气敏性研究

运用静电力自组装和原位化学氧化聚合相结合的方法制备了聚吡咯/纳米二氧化钛(PPy/TiO₂)复合薄膜, 并进行了紫外－可见光谱分析和原子力显微镜分析. 采用平面叉指电极制备了PPy/TiO₂复合薄膜气体传感器, 研究了其在常温下对有毒气体NH₃和CO的敏感性. 最后测试了该传感器的温度湿度特性. 结果表明, 该传感器对NH₃具有较高的灵敏度, 对CO几乎没有响应. 同时讨论了复合薄膜沉积时间对气敏特性的影响, 实验表明当沉积时间为20min时, 该传感器的NH₃敏感特性最好.     

Device optimization of CO2 gas sensor using planar technology

A planar type Li+ ion based potentiometric CO2 micro gas sensor of size 2 x 3 mm has been fabricated on alumina substrate by combining thin and thick film technology. The heater, electrodes and electrolyte were deposited by thin film deposition technique and the sensing and reference electrodes were printed by silk screen printing technology. The optimal thickness and sintering temperature of electrolyte are 1.2 microm and 775 degrees C. The sensor with Li2CO3 and 20 mol% BaCO3 not only exhibits a good Nernstian behavior but also consistent results over a long time at 450 degrees C in dry as well as 70% RH humidity condition between 160-5000 ppm CO2 concentrations. The spreading effect of the sensing and reference materials was controlled by the addition of Al2O3:B2O3 (1:2 mol%) glass.     

Microsensor based on low temperature cofired ceramics and gas-sensitive thin film

A novel design of gas sensor using low temperature cofired ceramics (LTCC) and thin film technologies is presented. The LTCC structure is composed essentially of two ceramic layers with interlayer thick film Pt heater, interdigitated electrodes on top, contact pads and metallic connections realised by vias. The thin films of both SnO₂ and In₂O₃, intentionally doped and activated, were deposited on top of the structure. With some modifications of the lamination process and heat treatment parameters, the authors obtained the upper ceramic layer with the roughness not exceeding 250 nm, what was suitable for thin film technology. The films deposited onto such LTCC structure revealed the sensing properties very similar to the reference films deposited onto glass. The gas-sensitive films were tested with changing concentrations of reducing and oxidising gases in air. The necessary sensor working temperature was obtained and stabilised using a custom-built digital controller. The low heat capacity of the sensor structure enabled also a sinusoidal temperature control. The satisfactory results obtained by the authors indicate that the connection of LTCC and thin film technologies can lead to the fabrication of good quality gas sensors.     

Indium oxide thin film based ammonia gas and ethanol vapour sensor

A sensor for ammonia gas and ethanol vapour has been fabricated using indium oxide thin film as sensing layer and indium tin oxide thin film encapsulated in poly(methyl methacrylate) (PMMA) as a miniature heater. For the fabrication of miniature heater indium tin oxide thin film was grown on special high temperature corning glass substrate by flash evaporation method. Gold was deposited on the film using thermal evaporation technique under high vacuum. The film was then annealed at 700 K for an hour. The thermocouple attached on sensing surface measures the appropriate operating temperature. The thin film gas sensor for ammonia was operated at different concentrations in the temperature range 323–493 K. At 473 K the sensitivity of the sensor was found to be saturate. The detrimental effect of humidity on ammonia sensing is removed by intermittent periodic heating of the sensor at the two temperatures 323K and 448 K, respectively. The indium oxide ethanol vapour sensor operated at fixed concentration of 400 ppm in the temperature range 293–393 K. Above 373 K, the sensor conductance was found to be saturate. With various thicknesses from 150–300 nm of indium oxide sensor there was no variation in the sensitivity measurements of ethanol vapour. The block diagram of circuits for detecting the ammonia gas and ethanol vapour has been included in this paper.     

Pulsed laser deposited ZnO films and their humidity sensing behavior

The present paper describes an opto-electronic humidity sensor based on thin film of zinc oxide prepared by pulsed laser deposition method. Being optical in nature it gives electromagnetic disturbance-free monitoring. The sensing element is a right-angled isosceles prism with its base coated with ZnO thin film. Films have been characterized by XRD, SEM, and optical transmission. Film grown with substrate at room temperature is amorphous whereas that grown at elevated temperature is single crystalline with grain size 38.52 nm. Film deposited at room temperature is sensitive to humidity over a wide range i.e. 5–90RH% while that deposited at elevated temperature is found to be insensitive to humidity. The sensor shows better sensitivity for higher range of humidity. The response and recovery time of the sensor element have also been evaluated. This sensor configuration can be used for on-line applications and in-situ monitoring.     

The effect of carbon nanotube dispersion on CO gas sensing characteristics of polyaniline gas sensor

Polyaniline is one of the most promising conducting polymers for gas sensing applications due to its relatively high stability and n or p type doping capability. However, the conventionally doped polyaniline still exhibits relatively high resistivity, which causes difficulty in gas sensing measurement. In this work, the effect of carbon nanotube (CNT) dispersion on CO gas sensing characteristics of polyaniline gas sensor is studied. The carbon nanotube was synthesized by Chemical Vapor Deposition (CVD) using acetylene and argon gases at 600 degrees C. The Maleic acid doped Emeradine based polyaniline was synthesized by chemical polymerization of aniline. CNT was then added and dispersed in the solution by ultrasonication and deposited on to interdigitated AI electrode by solvent casting. The sensors were tested for CO sensing at room temperature with CO concentrations in the range of 100-1000 ppm. It was found that the gas sensing characteristics of polyaniline based gas sensor were considerably improved with the inclusion of CNT in polyaniline. The sensitivity was increased and response/recovery times were reduced by more than the factor of 2. The results, therefore, suggest that the inclusion of CNT in MA-doped polyaniline is a promising method for achieving a conductive polymer gas sensor with good sensitivity, fast response, low-concentration detection and room-operating-temperature capability.     

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.     

Sensitivity to Combustible Gas for ZnO Thin Films

A fine polycrystalline ZnO thin film with 0.3～0.6 μm grain size was obtained by sol-gel process and a consequential heat treatment at 500℃. The process of preparing ZnO thin film was analysed. The sensitivity and conductivity of ZnO thin films as combustible gas (CO, CH4,H2) sensor as well as the influence of catalyst and pH value of the precursor on its sensitivity were studied in detail. The structure characteristics of ZnO thin film by different process were irlvestigated by X-ray diffraction, thermal analysis and photoelectron spectrometer. The atomic ratio of Zn to O on the surface of ZnO thin film was found to be 1.14:1 measured from XPS result. The conductivity of the thin film increases greatly when doped with Al3+ ion but decreases while doped with Na+ ion     

Influence of effective surface area on gas sensing properties of WO3 sputtered thin films

WO₃ thin films having different effective surface areas were deposited under various discharge gas pressures at room temperature by using reactive magnetron sputtering. The microstructure of WO₃ thin films was investigated by X-ray diffraction, scanning electron microscopy, and by the measurement of physical adsorption isotherms. The effective surface area and pore volume of WO₃ thin films increase with increasing discharge gas pressure from 0.4 to 12 Pa. Gas sensors based on WO₃ thin films show reversible response to NO₂ gas and H₂ gas at an operating temperature of 50-300 °C. The peak sensitivity is found at 200 °C for NO₂ gas and the peak sensitivity appears at 300 °C for H₂ gas. For both kinds of detected gases, the sensor sensitivity increases linearly with an increase of effective surface area of WO₃ thin films. The results demonstrate the importance of achieving high effective surface area on improving the gas sensing performance.     

介孔硅基WO3纳米颗粒薄膜室温气敏元件特性

采用双槽电化学腐蚀法在p＋单晶硅片表面制备介孔硅层（meso-PSlayer）,然后用对向靶磁控反应溅射法在介孔硅表面沉积WO3纳米颗粒薄膜,在干燥空气中于400℃下保温4h进行退火热处理,制备出介孔硅基WO3纳米颗粒薄膜（WO3-PS）室温气敏元件.利用扫描电子显微镜（SEM）分析介孔硅层及WO3-PS的表面形貌,通过X射线衍射（XRD）研究WO3的结晶状态,测试WO3-PS气敏元件在室温下对NO2、NH3的气敏性能,并探讨了WO3-PS气敏元件的工作机理.实验结果表明,在介孔硅表面沉积WO3纳米颗粒薄膜可使介孔硅的气敏性能显著提高,其中在室温下对10×10^-6NO2的灵敏度由5提高至56,大大提高了介孔硅的灵敏度,并降低了其响应/恢复时间,提高了对NO2的选择性.     

NH3 sensing characteristics of nano-WO3 thin films deposited on porous silicon

The NH3 sensing characteristics of nano-tungsten trioxide (WO3) thin films deposited on porous silicon (PS) were investigated in the present study. Porous silicon layer was first prepared by electrochemical etching in an HF-based solution on a p(+)-type silicon substrate. Then, WO3 nano-films were deposited on the porous silicon layer by DC magnetron sputtering. Pt electrodes were deposited on the top surface of the WO3 films to obtain the WO3/PS gas sensor. The WO3 films deposited on PS were characterized by SEM, XRD and XPS. The NH3 sensing characteristics for WO3/PS gas sensor were tested at room temperature and 50 degrees C. The results showed that the NH3 sensing characteristics of WO3/PS were superior to WO3/Al2O3 at room temperature. The sensing mechanism of the nano-WO3 thin films based on PS was also discussed.     

Room temperature hydrogen gas sensitivity of nanocrystalline pure tin oxide

Nanocrystalline (6-8 nm) tin oxide (SnO2) thin film (100-150 nm) sensor is synthesized via sol-gel dip-coating process. The thin film is characterized using focused ion-beam microscopy (FIB) and high-resolution transmission electron microscopy (HRTEM) techniques to determine the film thickness and the nanocrystallite size. The utilization of nanocrystalline pure-SnO2 thin film to sense a typical reducing gas such as hydrogen, at room temperature, is demonstrated in this investigation. The grain growth behavior of nanocrystalline pure-SnO2 is analyzed, which shows very low activation energy (9 kJ/mol) for the grain growth within the nanocrystallite size range of 3-20 nm. This low activation energy value is correlated, via excess oxygen-ion vacancy concentration, with the room temperature hydrogen gas sensitivity of the nanocrystalline pure-SnO2 thin film sensor.     

Room temperature CO and H2 sensing with carbon nanoparticles

We report on a shell-shaped carbon nanoparticle (SCNP)-based gas sensor that reversibly detects reducing gas molecules such as CO and H(2) at room temperature both in air and inert atmosphere. Crystalline SCNPs were synthesized by laser-assisted reactions in pure acetylene gas flow, chemically treated to obtain well-dispersed SCNPs and then patterned on a substrate by the ion-induced focusing method. Our chemically functionalized SCNP-based gas sensor works for low concentrations of CO and H(2) at room temperature even without Pd or Pt catalysts commonly used for splitting H(2) molecules into reactive H atoms, while metal oxide gas sensors and bare carbon-nanotube-based gas sensors for sensing CO and H(2) molecules can operate only at elevated temperatures. A pristine SCNP-based gas sensor was also examined to prove the role of functional groups formed on the surface of functionalized SCNPs. A pristine SCNP gas sensor showed no response to reducing gases at room temperature but a significant response at elevated temperature, indicating a different sensing mechanism from a chemically functionalized SCNP sensor.     

二氧化锡薄膜的电阻气敏和光透射率气敏性能

以无机盐为原料,采用新颖的溶胶－凝胶工艺制备了具有优良电阻－气敏性能的纳米晶二氧化锡薄膜,其在最佳工作温度２００℃对６００ｐｐｍＣＯ的灵敏度可达５００,响应时间和恢复时间分别为１３ｓ和２０ｓ,进一步研究了薄膜的光透射率－气敏性能,发现当通ＣＯ时,透射率下降,最佳工作温度与电阻－气敏性能一致,当提高薄膜的退火温度时,电阻－气敏和光透射率－气敏的灵敏度均下降,分析了产生这些现象的原因。     

Pulsed laser deposited ZnO film on side-polished fiber as a gas sensing element

A simple sensor element consisting of a side-polished single-mode fiber and a planar metal oxide waveguide is described. The thin ZnO planar waveguide was produced on the polished fiber surface by pulsed laser deposition at optimized processing parameters. A measurement scheme for in situ control of the film thickness during the deposition process was developed and used. X-ray diffraction measurements and scanning electron microscopy were used to characterize the structure and the surface morphology of the planar waveguide, respectively. The numerical evaluation of the sensor sensitivity predicts the possibility to detect refractive index changes of less than 10(-4). Furthermore, preliminary gas sensor tests were performed by using a mixture of 1.5% butane diluted in N(2) and pure butane. A shift of the spectral position of the resonance points was observed from 3 to 5 s after gas exposure, which corresponds to refractive index changes of 3 x 10(-5) and 1.2 x 10(-3) for 1.5% butane and for pure butane, respectively.     

Chemical diagnosis of DLC by ESR spectral analysis

Diamond-like carbon (DLC) films were deposited utilizing plasma enhanced chemical vapor deposition (PECVD) with four precursor gases such as methane, ethylene, acetylene and benzene in gas phase. Electron spin resonance (ESR) spectra showed that dangling-bond sites (DBSs) observed in all films were characterized by an isotropic broad single line. The DLC film with unsaturated precursor gases had the higher film growth rate and the higher DBS accumulative rate. Although the DBS in DLC films were quite stable at room temperature under anaerobic conditions, the DBS decayed rapidly to level off toward a limiting value when exposed to air. The stability and reactivity of the DBS in DLC film were assumed to depend on chemical structure of organic gas used as precursor. The detailed-ESR study on DBS of the DLC films could be one of the powerful tools for diagnosing the micro-structural properties and the quality of films.     

金属涂层SPR的单端面LPFG折射率传感器(英文)

提出了一种新型的单端面反射的镀有金属膜的长周期光纤光栅传感器.这种基于表面等离子体谐振的具有三层结构的传感器分为两个部分,光栅部分用连续CO2激光脉冲制作,金属膜是由真空镀膜制成.在光栅上镀上各种不同厚度的薄金属膜来激发表面等离子体波,用这种光纤光栅传感器来测量液体的折射率,并研究它的反射谐振谱的特性.在标准气压下,镀有80 nm银膜的光栅从水(ns=1.33)到酒精(ns=1.36)中光栅谐振波长改变了1.14nm,其敏感度达到折射率变化～5×10-4谐振波长改变20 pm.研究发现不同厚度的不同金属膜显示了不同的敏感度.通过比较光栅在空气,水,酒精,甘油,以及在它们的混合物溶液中的谐振波长,得到这种反射式的长周期光纤光栅传感器的敏感特性.为制作一种高性能的用来测量折射率的光纤光栅传感器提供了一个有益的参考.     

Optical properties and sensing applications of lithium iron phosphate thin films

A composite optical waveguide sensor, consisting of lithium iron phosphate (LiFePO₄, LFP) as the sensing material, was constructed and utilized for the detection of volatile organic compound gases. Nano-LFP powder was prepared via the hydrothermal method and was subsequently utilized in a dip-coating procedure for the fabrication of LFP thin films. The effect of heat treating temperature on the refractive index of the thin films was studied. A glass optical waveguide gas sensor was fabricated by coating an LFP thin film on the surface of single-mode tin-diffused glass optical waveguide. The sensor was found to exhibit a linear response to xylene in the range of 50-1000 ppm, with response times of less than 5 s.     

Chemical gas sensor application of open-pore mesoporous thin films based on integrated optical polarimetric interferometry

Chemical gas sensors that employ integrated optical polarimetric interferometry were fabricated by the sol-gel synthesis of transparent mesoporous thin films of TiO2-P2O5 nanocomposite on tapered layers of TiO2 sputtered on tin-diffused glass waveguides. Atomic force microscopy images of the mesoporous thin film clearly show the open pore mouths on the film surface that favor rapid diffusion and adsorption of gas-phase analytes within the entire film. Adsorption of gas and vapor induces changes (Deltan) in the refractive index of the mesoporous thin film that lead to shifts in the phase difference between the fundamental transverse electric and magnetic modes simultaneously excited in the glass waveguide via single-beam incidence. Upon exposure to NH3 gas at concentrations as low as 100 ppb in dry air at room temperature, the sensor exhibits a reversible change in the phase difference with the response and recovery times of less than 60 and 90 s, respectively. It is unexpected that the sensor is unresponsive to either NO2 or C6H6 vapor, leading to a somewhat selective sensitivity to NH3. Determination of Deltan was carried out with a combination of the experimental results and the theoretical calculations. The sensor design represents a novel, effective, and easily accessible approach to mesoporous thin-film-based integrated optical chemical sensors.     

CO<Subscript>2</Subscript> gas sensitivity of sputtered zinc oxide thin films

For the first time, sputtered zinc oxide (ZnO) thin films have been used as a CO₂ gas sensor. Zinc oxide thin films have been synthesized using reactive d.c. sputtering method for gas sensor applications, in the deposition temperature range from 130–153°C at a chamber pressure of 8·5 mbar for 18 h. Argon and oxygen gases were used as sputtering and reactive gases, respectively. ZnO phase could be crystallized using a pure metal target of zinc. The structure of the films determined by means of X-ray diffraction method indicates that the zinc oxide single phase can be fabricated in this substrate temperature range. The sensitivity of the film synthesized at substrate temperature of 130°C is 2·17 in the presence of CO₂ gas at a measuring temperature of 100°C.