硅基氧化钨薄膜的制备及其性质研究
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摘要
本项研究针对当前对于有毒、易燃、易爆等危险气体的探测越来越紧迫,而当下常用的气敏材料识别能力差,气敏性能低,自我修复能力差,制备工艺复杂等问题,提出利用磁控溅射法结合分子模板技术,通过优化制备工艺,结合化学原位修饰、真空退火、光刻等后处理工艺,在硅衬底上制备出具有空间立体结构、高的比表面积,与衬底黏附力强、结构稳定的具有不同化学剂量比的掺Cu或掺In半导体纳米多孔WO_3薄膜。这类材料具有较强的气敏性质,对多种有害气体如:NO_x、SO_x在较宽(ppm量级)浓度范围内有较强和快速识别能力。
根据气体吸附-脱附理论,由于不同的气体会在WO_3气体传感材料表面产生不同的施主或受主表面态,从而影响气敏材料的能带结构,提出了利用C-V,C-F法,结合通用的I-V法来联合研究有害气体的气敏响应特性,从而标定和识别出不同有害气体ppm浓度范围内的NO_x、SO_x等有害气体。
氧化钨是一种典型的n型半导体金属氧化物气敏材料,它有优异的电致变色、气敏特性,已被开发制备了各种类型器件(电致变色器件,智能灵巧窗等),近来又开始了对其气敏特性的研究。在国外已有WO_3气敏特性方面的报道,国内近年来才开始有相关报道。
本论文着重研究了氧化钨薄膜的光电特性,为进一步的气敏探测器件的研制取得有益的探索。
本文首先简单介绍了氧化钨薄膜的研究历史及背景,本课题的研究意义,样品薄膜的制备方法、测试分析手段,然后叙述了我们在前人研究的基础上进行的一些探索,制备了五个系列的氧化钨薄膜(包括:单层氧化钨薄膜、氧化钨同质多层膜、氧化铟锡薄膜、氧化钨/氧化铟锡/氧化钨复合膜、氧化铟锡/氧化钨/氧化铟锡复合膜),并采用Raman等表征分析手段,测试分析了各系列薄膜。
The detection of the flammable, explosive, toxic or/and other dangerous gas are becoming more and more urgent, while the current commonly used gas-sening material has so many problems, such as bad indentify ability, poor self-repair capacity, complex preparation process, and so on. In view of the above questions, we proposed using magnetron sputtering combined with molecular template technolegy, by optimizing the preparation processs, combining chemical modification in situ, vacuum annealing, lithography, etc, to prepare the tungsten oxide semiconductor nano-porous films with three-dimensional structure, high pecific structural stability with different chemical dosage ration of Cu-doped or In-doped. Such material has a strong gas-sensing properties of a variety of harmful gases, such as: NO_x, SO_x at a wide concentration range.
According to the gas adsorption-desorption theory, because different gases will have different donor or acceptor surface state at the surface of tungsten oxide gas-sensing materials’band structure, we proposed using C-V, C-F and I-V methods to study the gas-sensing properties, thus to identify and demarcate the different ppm concentrations scope of harmful gases.
Tungsten oxide is typical gas-sensing material of semiconductor oxide. Its gas-sensing property is very exceptional.The paper focused on the electrical and optical characteristics of WO_3 thin film to make a beneficial exploration to develop the gas sensor.
This article have reviewed the research history, research significance, preparation method and various analysis and detection methods, and then stated our research on the basis of former research results. We prepared five series WO_3 thin films, and made measurement and analysis through Raman, and so on.
根据气体吸附-脱附理论,由于不同的气体会在WO_3气体传感材料表面产生不同的施主或受主表面态,从而影响气敏材料的能带结构,提出了利用C-V,C-F法,结合通用的I-V法来联合研究有害气体的气敏响应特性,从而标定和识别出不同有害气体ppm浓度范围内的NO_x、SO_x等有害气体。
氧化钨是一种典型的n型半导体金属氧化物气敏材料,它有优异的电致变色、气敏特性,已被开发制备了各种类型器件(电致变色器件,智能灵巧窗等),近来又开始了对其气敏特性的研究。在国外已有WO_3气敏特性方面的报道,国内近年来才开始有相关报道。
本论文着重研究了氧化钨薄膜的光电特性,为进一步的气敏探测器件的研制取得有益的探索。
本文首先简单介绍了氧化钨薄膜的研究历史及背景,本课题的研究意义,样品薄膜的制备方法、测试分析手段,然后叙述了我们在前人研究的基础上进行的一些探索,制备了五个系列的氧化钨薄膜(包括:单层氧化钨薄膜、氧化钨同质多层膜、氧化铟锡薄膜、氧化钨/氧化铟锡/氧化钨复合膜、氧化铟锡/氧化钨/氧化铟锡复合膜),并采用Raman等表征分析手段,测试分析了各系列薄膜。
The detection of the flammable, explosive, toxic or/and other dangerous gas are becoming more and more urgent, while the current commonly used gas-sening material has so many problems, such as bad indentify ability, poor self-repair capacity, complex preparation process, and so on. In view of the above questions, we proposed using magnetron sputtering combined with molecular template technolegy, by optimizing the preparation processs, combining chemical modification in situ, vacuum annealing, lithography, etc, to prepare the tungsten oxide semiconductor nano-porous films with three-dimensional structure, high pecific structural stability with different chemical dosage ration of Cu-doped or In-doped. Such material has a strong gas-sensing properties of a variety of harmful gases, such as: NO_x, SO_x at a wide concentration range.
According to the gas adsorption-desorption theory, because different gases will have different donor or acceptor surface state at the surface of tungsten oxide gas-sensing materials’band structure, we proposed using C-V, C-F and I-V methods to study the gas-sensing properties, thus to identify and demarcate the different ppm concentrations scope of harmful gases.
Tungsten oxide is typical gas-sensing material of semiconductor oxide. Its gas-sensing property is very exceptional.The paper focused on the electrical and optical characteristics of WO_3 thin film to make a beneficial exploration to develop the gas sensor.
This article have reviewed the research history, research significance, preparation method and various analysis and detection methods, and then stated our research on the basis of former research results. We prepared five series WO_3 thin films, and made measurement and analysis through Raman, and so on.
引文
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[3]周维.WO3薄膜的制备工艺与氢敏特性的研究[M]。重庆大学,2007.
[4] Di Gregorio F, Keller V. Activation and isomerization of hydrocarbons over WO3/ZrO2 catalysts I. Prparation,characterization,and X-ray photoelectron spectroscopy studies[J]. Journal of Catalysis,2004,225(1):45-55.
[5] Vedrine J. C. Industrial features[J]. Catalysis Today,2000,56(4):333-334.
[6] Yoshiaki Suda, Hiroharu Kawasaki, Tamiko Ohshima, Yoshihito Yagyuu. Characteristics of tungsten oxide thin films prepared on the flexible substrates using pulsed laser deposition[J]. Thin Solid Films,2008,516:4397-4401.
[7] Qun Zhang, Xifeng Li, Guifeng Li. Dependence of electrical and optical properties on thickness of tungsten-doped indium oxide thin films[J]. Thin Solid Films, 2008,517(2):613-616.
[8] G. Leftheriotis, P. Yianoulis. Development of electrodeposited WO3 films with modified surface morphology and improved electrochromic properties[J]. Solid State Ionics, 2008,179(38): 2192-2197.
[9] O. Lavi, G. L. Frey, A. Siegmann, Y. Ein-Eli. Enhanced tungstate electrochromism via formation of transparent conductive networks[J]. Electrochemistry Communications, 2008,10:1210-1213.
[10] Amit Kumar Chawla, Sonal Singhal,Hari Om Gupta, Ramesh Candra. Effect of sputtering gas on structural and optical properties of nanocrystalline tungsten oxide films[J]. Thin Solid Films, 2008,517(3):1042-1046.
[11]尚福亮,杨海涛,韩海涛.光致变色纳米WO3薄膜研究进展[J]。化工新型材料,2006,34(5):8—10.
[12] Ippolito S. J., Kandasamy S., Kalantar-zadeh K., et al. Hydrogen sensing characteristics of WO3 thin film conductometric sensors activated by Pt and Au catalysts[J]. Sensors and Actuators B, 2005,108:154-158.
[13] Sekinoto S, Nakagawa H,Okazaki S.,et al. A fiber-optic evanescent-wave hydrogen gas sensorusing palladium-supported tungsten oxide[J]. Sensor and Actuators B, 2002,66:142-145.
[14] Opara U, Rasovee K, Orel B. The gaso-chrcmic properties of sol-gel WO3 films with sputtered Pt catalyst[J]. Solar Energy, 2000, 68(6):541-551.
[15] Michel Levy,Thierry Pagnier. Ab initio DFT computation of SnO2 and WO3 slabs and gas-surface interactions[J]. Sensors and Actuators B, 2007,126:204-208.
[16] Deb S. K. The reversible couration-bleaching process in tungsten trioxide under the action of an applied electric. Appl. Opt. Suppl., 1969,3:193-196.
[17]侯长军,范小花,唐一科,霍丹群等.纳米结构Pt/WO3薄膜的制备、表征及氢敏性能[J]。功能材料与器件学报,2008,14(1):218—222.
[18]庄琳,徐雪青,沈辉,卢志坚等.掺钯WO3薄膜的气致变色性能[J]。华南理工大学学报(自然科学版),2002,30(2):45—47.
[19]杨晓红,王新强,马勇,冯庆等.WO3薄膜气敏光学传感特性研究[J]。功能材料,2007,8(38):1254—1256.
[20] T. Siciliano, A. Tepore, G. Micocci, A. Serra, D. Manno, E. Filippo.WO3 gas sensors prepared by thermal oxidization if tungsten[J]. Sensors and Actuators B, 2008,133:321-326.
[21] Emma Rossinyol, Anna Prim,Eva Pellicer,et al. Mesostructured pure and copper-catalyed tungsten oxide for NO2 detection[J]. Sensors and Actuators B,2007, 126:18-23.
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