SiO2薄膜制备的现行方法综述

在导电基体上制作薄膜传感器的过程中,需要在基体与薄膜电极之间沉积一层绝缘膜.二氧化硅薄膜具有良好的绝缘性能,并且稳定性好,膜层牢同,长期使用温度可达1000℃以上,应用十分广泛.通常制备SiO2薄膜的现行方法主要有磁控溅射、离子束溅射、化学气相沉积、热氧化法、凝胶-溶胶法等.本文系统阐述了各种方法的基本原理、特点及适用场合,并对这些方法做了比较.     

Zinc oxide thin films: Characterization and potential applications

Zinc oxide (ZnO) has attracted recent interest for a range of applications, including use as a transparent conductive oxide (TCO) and in gas sensor devices. This paper compares ZnO films grown using two methods designed for the production of thin films, namely sol-gel and aerosol assisted chemical vapour deposition (AACVD) for potential use in sensor and TCO applications. Materials produced by the sol-gel route were observed to be amorphous when annealed at 350 °C, but were crystalline when annealed at higher temperatures and had a relatively open grain structure when compared to the AACVD films. Electrical characterization showed that materials were highly resistive, but that their properties varied considerably when the measurements were performed in vacuum or in air. This behaviour was rapidly reversible and reproducible for room temperature measurement.In contrast materials grown by aerosol-assisted CVD were non-porous, polycrystalline and conductive. Measured electrical properties did not vary with changing measurement atmosphere. These differences are discussed in terms of the structural characterisation of the films and some comments are made regarding the suitability of both approaches for the growth of ZnO thin film sensor materials.     

Innovative aspects in thin film technologies for nanostructured materials in gas sensor devices

This work reports on the use of two innovative techniques in the field of gas sensors for preparing nano-structured materials: sol-gel and supersonic cluster beam deposition. By means of sol-gel, nano-structured In₂O₃ thin films have been prepared and deposited under different deposition parameters on silicon wafer. In this way the results have shown a good compatibility of the method with silicon technology, then potentially suitable to be used in the fabrication of integrated devices. The second technique has been applied for the preparation of nano-structured TiO₂ thin films showing its capability to be used in the fabrication of gas sensor devices, mainly when a good control of the grain dimension is required.     

High-basicity determination in mixed water-alcohol solutions by a dual optical sensor approach

The activity of NaOH is known to be significantly affected by the presence of an alcohol in aqueous solutions. A novel linear relationship between (deltaA/deltaC(alcohol)) and C(base) was found in the highly alkaline, mixed H2O-ROH solutions (R = Me, Et, i-Pr). The use of this linear relationship led to a dual-transducer approach to decompose the optical signals of optical base sensors and to give base and alcohol concentrations in concentrated NaOH-H2O-ROH solutions ([OH-] = 0.05-3.6 M). The scope of the new dual-sensor approach was evaluated, and errors in C(base) and C(alcohol) were analyzed. The optical base sensors consist of sol-gel SiO2-ZrO2-organic polymer composites doped with high-pKa indicators. The pKa(s) of the indicators encapsulated in the composite films were determined and found to be affected by the composition of the sol-gel composites. Optical sensors and their uses in multicomponent systems are of intense current interest.( 1-7) In the multicomponent systems, the activity of the analyte and sensor response are often affected by change in ionic strength. For optical sensors that are based on indicator equilibria involving the analyte as their transducing mechanism, such effect is particularly significant. The concentrations of both the analyte and other chemicals affect ionic strength, and the sensor response to concentration of the analyte is thus often indistinguishable from those of other chemicals. An accurate measurement of each component in these multicomponent systems is actively studied. Several approaches have been developed to correct ionic strength in optical sensing for the pH region and solutions of low-to-medium ionic strength. (1-9) We recently reported a dual-transducer approach to measure acid concentrations (2-9 M HCl) in salt-containing, concentrated strong acids such as MClx-HCl (M = Li, Ca, Al) solutions. (10) This approach was shown to reduce the error in C(acid) from, for example,     

Thickness dependency of sol-gel derived ZnO thin films on gas sensing behaviors

ZnO thin films were fabricated by a sol-gel method using Zn(CH₃COO)₂·2H₂O as starting material in order to prepare an acetone gas sensor. A homogeneous and stable solution was prepared by dissolving the zinc acetate in a solution of ethanol and monoethanolamine. The sol-gel solution is coated on alumina substrates with various thicknesses by spin coating technique and heat treated to grow crystalline ZnO thin films. The effect of thickness on physical and electrical properties of as deposited ZnO thin films has been studied. The as deposited ZnO thin films were characterized by X-ray diffraction spectroscopy, field emission scanning electron microscopy and atomic force microscopy. The root mean square surface roughness factors increase with thickness of the films and found 3.9, 6.6, 9.0, and 11.28 nm for 80-, 220-, 450- and 620-nm-thin films respectively. The activation energies of the films are calculated from the resistance temperature characteristics. The sensitivities of the ZnO films towards the acetone gas were determined at an operating temperature of 200 °C. The sensitivity towards acetone vapor is strongly depending on surface morphology of the ZnO thin films.     

Thin film chemical sensors based on p-CuO/n-ZnO heterocontacts

Previous work on bulk ceramic heterocontacts (n-ZnO/p-CuO) has indicated significant sensitivity to the presence of specific adsorbed chemical species. Here, these results are extended to thin film heterostructures fabricated via chemical solution methods. It is expected that thin film sensor architectures will possess significant advantages over their bulk counterparts. In this study, the desired properties of porosity and crystallinity have been optimized with respect to pyrolysis temperature for each ZnO and CuO sol-gel process. The results of microscopy and X-ray diffraction (XRD) indicated that an optimal balance of these two properties is achieved at a pyrolysis temperature of 250 °C. The CuO films were seen to possess a level of porosity significantly higher than that seen in the ZnO films, making them an ideal candidate for the top layer in a planar thin film heterostructure. Results of current-voltage measurements conducted in 4000 ppm hydrogen have confirmed that the inherent porosity of the CuO films led to an enhanced sensor response in CuO on ZnO heterostructures. Lastly, the fabrication and structural characterization of a mixed solution type heterostructure has been detailed. Atomic force microscopy and XRD data indicated the presence of ZnO pillars dispersed among a matrix of CuO.     

Tailoring of sol-gel films for optical sensing of oxygen in gas and aqueous phase

Sol-gel-based optical sensors for both gas-phase and dissolved oxygen have been developed. Both sensors operate on the principle of fluorescence quenching of a ruthenium complex which has been entrapped in a porous sol-gel silica film. A comprehensive investigation was carried out in order to establish optimal film-processing parameters for the two sensing environments. Both tetraethoxysilane and organically modified sol-gel precursors such as methyltriethoxysilane and ethyltriethoxysilane were used. Film hydrophobicity increases as a function of modified precursor content, and this was correlated with enhanced dissolved oxygen (DO) sensor performance. Extending the aliphatic group of the modified precursor further improved DO sensitivity. The influence of water/precursor molar ratio, R, on the sol-gel film microstructure was investigated. R value tailoring of the microstructure and film surface hydrophobicity tailoring were correlated with oxygen diffusion behavior in the films via the Stern-Volmer constants for both gas phase and DO sensing. Excellent performance characteristics were measured for both gas-phase and DO oxygen sensors. The long-term quenching stability of DO sensing films was established over a period of 6 months.     

Optical sensors for the determination of concentrated hydroxide

An optical sensor system has been developed for the determination of concentrated strong bases ([OH-] = 1-10 M). The base sensors consist of SiO2/ZrO2-organic polymer composites and doped high-pKa indicators. Films were obtained by spin-casting these composite materials on glass substrates and were used as sensor elements for the spectrometric determination of hydroxide. The hydrophilic nature of the mixed oxide SiO2/ZrO2 and its chemical stability in concentrated alkali made it attractive as support in the composites. The organic polymers in the composites either provided better mechanical stability and dye immobilization or enhanced OH- diffusion and sensor response. The composite sensors showed a relative standard deviation of less than 2%. The response time of a SiO2/ZrO2-Nafion composite (sensor 2) was short (5 s), and a small hysteresis was observed during reproducibility measurements with 1-4 M NaOH solutions. The sensors were found to be stable in 4 M NaOH during a 30-day durability test, showing a standard deviation of 3.0-4.7%. The diffusion kinetics and hysteresis performance of the sensors were also evaluated.     

Sol-gel-based, planar waveguide sensor for water vapor

A water vapor sensor based on a combination of sol-gel processing and planar optical waveguide technologies has been developed. The indicator erythrosin B was entrapped in a thin sol-gel film (thickness ～100 nm) prepared from methyltriethoxysilane, dimethyldiethoxysilane, and tetraethoxysilane. This dye exhibits an increase in absorbance in the presence of liquid or gaseous water. The sol-gel layer containing the dye was deposited onto a sol-gel-derived, single-mode planar waveguide. Outcoupled light intensity measurements (at 514.5 nm) over a range of water vapor concentrations (in a nitrogen gas stream) yielded a response over a wide range of relative humidity (<1-～70%) at room temperature. Response and reversal times were less than 1 min, which may make this sensor attractive for real-time monitoring applications.     

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.     

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.     

Design of low cost gas sensor based on SrTiO3 and BaTiO3 films

We have prepared SrTiO3/BaTiO3 multilayer film on alumina substrates by a sol-gel technique and investigated their response for sensing ethanol vapor. The surface morphology of the films were characterized by atomic force microscope (AFM) showing that the grain size of the films increase up to 40 nm as the annealing temperature increased to 1000 degrees C. The ethanol sensors based on SrTiO3/BaTiO3 thin films were fabricated by applying interdigitated gold electrodes by sputtering technique. The ethanol sensing characteristics of SrTiO3/BaTiO3 thin films were quantified by the change in resistance of the sensors when they were exposed to ethanol. The optimum operating tempearature of these sensors was found to be 350 degrees C. In addition, the film annealed at 1000 degrees C exhibited p-type gas sensing behavior with the best sensitivity of 30-100 for low ethanol concentration in the range of 100-1000 ppm.     

Optical sensors and the salt effect: a dual-transducer approach to acidity determination in a salt-containing concentrated strong acid

A dual-transducer approach has been developed to decompose the optical signals of acid sensors in salt-containing concentrated acid solutions and to give acid and salt concentrations in concentrated LiCl-HCl, CaCl2-HCl, and AICl3-HCl solutions, respectively. The optical acid sensors in this approach are films of porous sol-gel SiO2 or SiO2-Nafion composite doped with low-pKa indicators. A novel linear relationship (dA/dCsalt)cCacid = beta x (dA0/dCacid)Csalt = 0 (A = absorbance of the sensor in a salt-containing HCl solution; A0 = absorbance of the sensor in a salt-free acid solution) was found, and the current approach is based on a set of nonlinear equations derived from this relationship.     

半导体陶瓷型薄膜气敏传感器的研究进展

半导体陶瓷型薄膜气敏传感器,具有灵敏度高、与气体反应快、制备成本较低等优点,已经成为近年传感器研究和开发的重点．是未来气敏传感器的发展方向之一。本文介绍了陶瓷型半导体薄膜气敏传感器常见的器件结构、薄膜材料的主要制备方法．部分主要的半导体金属氧化物薄膜气敏材料．以及近期相关的研究进展,并扼要分析了今后的发展方向。     

Enhancing sensitivity and selectivity of long-period grating sensors using structure-switching aptamers bound to gold-doped macroporous silica coatings

High surface area, sol-gel derived macroporous silica films doped with gold nanoparticles (AuNP) are used as a platform for high-density affinity-based immobilization of functional structure-switching DNA aptamer molecules onto Michelson interferometer long-period grating (LPG) fiber sensors, allowing for label-free detection of small molecular weight analytes such as adenosine triphosphate (ATP). The high surface area afforded by the sol-gel derived material allowed high loading of DNA aptamers, while the inclusion of gold nanoparticles within the silica film provided a high refractive index (RI) overlay, which is required to enhance the sensitivity of the LPG sensor according to our numerical simulations. By using a structure-switching aptamer construct that could release an oligonucleotide upon binding of ATP, the effective change in RI was both enhanced and inverted (i.e., binding of ATP caused a net reduction in molecular weight and refractive index), resulting in a system that prevented signals originating from nonspecific binding. This is the first report on the coupling of aptamers to LPG fiber sensors and the first use of high RI AuNP/silica films as supports to immobilize biomolecules onto the LPG sensor surface. The dual functionality of such films to both improve binding density and LPG sensor cladding refractive index results in a substantial enhancement in the sensitivity of such sensors for small molecule detection.     

Xerogel optical sensor films for quantitative detection of nitroxyl

Xerogel sensing films were synthesized via sol-gel chemistry were used to fabricate optical nitroxyl (HNO) sensors [corrected] Selective detection of HNO in solution was achieved by monitoring the rates of manganese(III) meso-tetrakis(4-sulfonatophenyl) porphyrinate (MnIIITPPS) reductive nitrosylation in the anaerobic interior of aminoalkoxysilane-derived xerogel films. Nitroxyl permeability in sensor films deposited in round-bottom 96-well plates was enhanced via incorporation of trimethoxysilyl-terminated poly(amidoamine-organosilicon) dendrimers in the xerogel network. The selectivity of MnIIITPPS for HNO, the overall sensitivity, and the working dynamic range of the resulting sensors were characterized. The HNO-sensing microtiter plates were used to quantify pH-dependent HNO generation by the recently described HNO-donor sodium 1-(isopropylamino)diazene-1-ium-1,2-diolate (IPA/NO), and compare HNO production efficiency between IPA/NO and Angeli's salt, a traditional HNO-donor.     

WO3 thin film prepared by PECVD technique and its gas sensing properties to NO2

Tungsten oxide films have been successfully fabricated from tungsten oxychloride (WOCl₄) precursor by using plasma enhanced vapor deposition (PECVD) technique. The films were deposited onto silicon substrates and ceramic tubes maintained at 100°C under a constant operating pressure of He-O₂ gas mixtures. The compositions and the structures of the thin films have been investigated by means of anaysis methods, such as XRD, XPS, UV and IR. The as-deposited WO₃ thin films were amorphous state and became crystalline after annealing above 400°C. The surface analysis of the films indicates that stoichiometry O/W is 2.77 : 1. The gas sensing measurements of the WO₃ thin film sensors indicate that these sensors have a high sensitivity, excellent selectivity and quick response behavior to NO₂.     

Optical-fiber sensor using tailored porous sol-gel fiber core

A new concept in optical-fiber chemical sensors, the active fiber core optical sensor (AFCOS), is presented. In this sensor, the fiber core acts as a transducer. The sensitivity of an AFCOS sensor is compared with that of an active coating [evanescent wave (EW)] based optical-fiber sensor. Requirements for a fiber core to act as a chemical sensor are discussed. Novel techniques for making a porous sol-gel silica fiber, doping chemical reagents into the fiber, and constructing a chemical sensor using the porous fiber as a transducer have been developed. The microstructure of the fabricated sol-gel silica fiber and the effect of the fiber's microstructure on the capability of the porous sol-gel silica fiber for guiding light are discussed. A humidity sensor employing a CoCl/sub 2/-doped porous sol-gel fiber as a transducer has been constructed as an example. The test results for the humidity sensor verified a theoretical analysis indicating that an optical-fiber chemical sensor using an active fiber core as a transducer has a much higher sensitivity than that of an EW-based sensor.     

Comparisons between NO/sub 2/- and O/sub 3/-sensing properties of phthalocyanines and n-InP thin films in controlled and noncontrolled atmospheres

This paper describes two different semiconductor gas sensors devoted to the detection of oxidizing pollutants in the atmosphere. The first sensor consists of thin films of phthalocyanines as sensing layers (CuPc, ZnF/sub 16/Pc, and LuPc/sub 2/) evaporated onto alumina substrate fitted with interdigitated electrodes. The second sensor is realized with a mineral monocrystalline semiconductor: n-doped epitaxial layer grown on a semi-insulating substrate of indium phosphide. Each sensor has been submitted to low-controlled concentrations of ozone and nitrogen dioxide, and their detection characteristics, such as response time, stability, and sensitivity, are described. Comparison of these two sensors shows their complementary sensing characteristics, and NO/sub 2/ and O/sub 3/ act in the same way. Measurements under noncontrolled atmosphere (urban air) have been realized and have demonstrated the potentialities of these structures to be used as oxidizing pollutant detectors. Proposed methods to improve the detection of oxidizing species in urban air are discussed.