WO_3薄膜的制备工艺与氢敏特性的研究
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摘要
三氧化钨(WO3)薄膜是一种重要的功能材料,因具有良好的电致变色、气致变色、光致变色、电化学性能而得到广泛的研究和应用。本论文对三氧化钨的氢敏机理做了相应的阐述,由于纯三氧化钨薄膜在常温下对氢气不敏感,本文采用掺杂钯或铂来改善三氧化钨薄膜材料的氢敏性能。
本文采用溶胶-凝胶法与磁控溅射法相结合来制备三氧化钨的掺杂薄膜,此种方法将综合溶胶-凝胶法与直流磁控溅射法的优点,其薄膜疏松多微孔,充分快速响应了铂或钯催化剂离化的氢,具有良好的氢敏性能,是制备氢气传感器薄膜的非常好的方法。
首先用溶胶-凝胶法制备三氧化钨薄膜,详细介绍了掺杂薄膜的制备方法、使用的材料设备及工艺流程,并对薄膜的光学性质、表面形态、结构等进行了深入的研究;然后用磁控溅射法对制备好的薄膜上溅射一层钯或铂的催化剂,介绍了溅射仪的工作原理、工艺流程,优化了制备参数,并对掺杂后的薄膜进行一系列的检测分析。
本文分别用X衍射仪、隧道-原子力显微镜、傅立叶变换红外光谱仪、双光束紫外可见分光光度计等表征了用溶胶凝胶法制备的纯三氧化钨薄膜和经磁控溅射掺杂后的薄膜。X衍射结果表明:掺铂的三氧化钨溶胶凝胶薄膜的晶化温度比三氧化钨溶胶凝胶薄膜的晶化温度有所提高;隧道显微镜测试结果表明:非晶态时,磁控溅射掺铂薄膜样品表面和溶胶凝胶样品表面都有明显的平行线状结构,长程无序,分子趋于四面体结构,只是前者比后者表面较平整;晶态时,磁控掺铂样品在自然生长面上原子呈平面分布,长程有序,溶胶掺铂样品则呈WO6面心结构。用双光束紫外可见分光光度计测透光率表明溶胶凝胶制作的薄膜可见光易通过其原因是薄膜组织疏松,存在孔洞、水分子,而掺铂的样品的透光率较低,这就是磁控溅射的膜组织比较致密,晶粒较完善的原因。傅立叶变换红外光谱仪测试结果表明:掺钯三氧化钨薄膜的特征振动在400～1000nm波段内随退火温度的提高越明显。
本文对WO3薄膜氢敏性的研究为研发新型氢敏材料奠定了一定的基础。
Tungsten trioxide film is one kind of the important functional material. It is studied and applied extensively because of its electrochromic property, gasochromic property, photochromic property, electrochemistry, etc. This article makes the elaboration to the structure of tungsten trioxide molecular and color changed mechanism .Because of it is not sensitive to hydrogen at normal temperature, so tungsten trioxide with doped Pd or Pt as catalyst to improving its hydrogen response was adopted.
The Pt or Pd sputtered tungsten trioxide sol-gel film by DC magnetron sputtering method has better property as loosen holes which have fast hydrogen response ionized by Pt or Pd. The film has excellent hydrogen absorbing property and the method is preferred for the sensor to distinguish hydrogen.materials, instrumentation, technological process were introduced in detail.And the optical property and surface structure of the films was also studied.Secondly, the Pt or Pd as catalyst were sputtered tungsten trioxide sol-gel film by DC magnetron sputtering.And the theory, technological process and the optimized preparation parameters of DC magnetron sputtering were presented in detail.At the same time , the films were tested and the importance factors which affect the properties of the films were analyzed particularly.
The tungsten trioxide films prepared by sol-gel and the films with catalyst sputtered by DC magnetron sputtering were characterized by XRD, STM, FT-IR, UV-VIS and so on. As the result of XRD, the temperature from amorphous to crystal of tungsten trioxide sol-gel films with catalyst is higher than sol-gel films’.As results of STM, both Pt sputtered tungsten trioxide films and Pt sputtered tungsten trioxide sol-gel films there is distinct and out-of-order parallel line structure on the surface of amorphous. Molecules of the sample tend to tetrahedron and the former has more planarer structure. Atoms of the film by DC reactive magnetron with Pt sputtered tend to plane ordinal structure. Molecules of the the film by sol-gel with Pt sputtered tend to be surface center structure as WO6. As results of transmission, the film with Pt catalyst has better hydrogen response than the film with Pd catalyst.As results of FT-IR, the characteristic oscillation of the tungsten oxide sol-gel film with Pd catalyst is more distinct with the higher temperature at the wave band 400~1000nm.
The study of tungsten trioxide provided some foundation for developing the hydrogen sensitive optical fibersensor.
本文采用溶胶-凝胶法与磁控溅射法相结合来制备三氧化钨的掺杂薄膜,此种方法将综合溶胶-凝胶法与直流磁控溅射法的优点,其薄膜疏松多微孔,充分快速响应了铂或钯催化剂离化的氢,具有良好的氢敏性能,是制备氢气传感器薄膜的非常好的方法。
首先用溶胶-凝胶法制备三氧化钨薄膜,详细介绍了掺杂薄膜的制备方法、使用的材料设备及工艺流程,并对薄膜的光学性质、表面形态、结构等进行了深入的研究;然后用磁控溅射法对制备好的薄膜上溅射一层钯或铂的催化剂,介绍了溅射仪的工作原理、工艺流程,优化了制备参数,并对掺杂后的薄膜进行一系列的检测分析。
本文分别用X衍射仪、隧道-原子力显微镜、傅立叶变换红外光谱仪、双光束紫外可见分光光度计等表征了用溶胶凝胶法制备的纯三氧化钨薄膜和经磁控溅射掺杂后的薄膜。X衍射结果表明:掺铂的三氧化钨溶胶凝胶薄膜的晶化温度比三氧化钨溶胶凝胶薄膜的晶化温度有所提高;隧道显微镜测试结果表明:非晶态时,磁控溅射掺铂薄膜样品表面和溶胶凝胶样品表面都有明显的平行线状结构,长程无序,分子趋于四面体结构,只是前者比后者表面较平整;晶态时,磁控掺铂样品在自然生长面上原子呈平面分布,长程有序,溶胶掺铂样品则呈WO6面心结构。用双光束紫外可见分光光度计测透光率表明溶胶凝胶制作的薄膜可见光易通过其原因是薄膜组织疏松,存在孔洞、水分子,而掺铂的样品的透光率较低,这就是磁控溅射的膜组织比较致密,晶粒较完善的原因。傅立叶变换红外光谱仪测试结果表明:掺钯三氧化钨薄膜的特征振动在400～1000nm波段内随退火温度的提高越明显。
本文对WO3薄膜氢敏性的研究为研发新型氢敏材料奠定了一定的基础。
Tungsten trioxide film is one kind of the important functional material. It is studied and applied extensively because of its electrochromic property, gasochromic property, photochromic property, electrochemistry, etc. This article makes the elaboration to the structure of tungsten trioxide molecular and color changed mechanism .Because of it is not sensitive to hydrogen at normal temperature, so tungsten trioxide with doped Pd or Pt as catalyst to improving its hydrogen response was adopted.
The Pt or Pd sputtered tungsten trioxide sol-gel film by DC magnetron sputtering method has better property as loosen holes which have fast hydrogen response ionized by Pt or Pd. The film has excellent hydrogen absorbing property and the method is preferred for the sensor to distinguish hydrogen.materials, instrumentation, technological process were introduced in detail.And the optical property and surface structure of the films was also studied.Secondly, the Pt or Pd as catalyst were sputtered tungsten trioxide sol-gel film by DC magnetron sputtering.And the theory, technological process and the optimized preparation parameters of DC magnetron sputtering were presented in detail.At the same time , the films were tested and the importance factors which affect the properties of the films were analyzed particularly.
The tungsten trioxide films prepared by sol-gel and the films with catalyst sputtered by DC magnetron sputtering were characterized by XRD, STM, FT-IR, UV-VIS and so on. As the result of XRD, the temperature from amorphous to crystal of tungsten trioxide sol-gel films with catalyst is higher than sol-gel films’.As results of STM, both Pt sputtered tungsten trioxide films and Pt sputtered tungsten trioxide sol-gel films there is distinct and out-of-order parallel line structure on the surface of amorphous. Molecules of the sample tend to tetrahedron and the former has more planarer structure. Atoms of the film by DC reactive magnetron with Pt sputtered tend to plane ordinal structure. Molecules of the the film by sol-gel with Pt sputtered tend to be surface center structure as WO6. As results of transmission, the film with Pt catalyst has better hydrogen response than the film with Pd catalyst.As results of FT-IR, the characteristic oscillation of the tungsten oxide sol-gel film with Pd catalyst is more distinct with the higher temperature at the wave band 400~1000nm.
The study of tungsten trioxide provided some foundation for developing the hydrogen sensitive optical fibersensor.
引文
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[2] Esra Ozkan, Se-Hee Lee, C.Edwin Tracy, et al. Comparison of electrochromic amorphous and crystalline tungsten oxide films[J]. Solar Energy Materials&Solar Cells. 2003.79.439-448
[3] Tokuro Nanba, Tadashi Takahashi, Jun Takada, et al. Characterization of amorphous tungsten trioxide thin films prepared by r.f.magnetron sputtering method[J]. Joural of Non-Crystalline Sloids. 1994.178.233-237
[4] 杨秋红,顾莹,郭存济.Sol-gel 法制备 WO3 电致变色薄膜[J].上海大学学报(自然科学版).1997.3(3).313-318
[5] 徐敏华,苏连永,肖忠党等.电沉积三氧化钨薄膜致变色及其光电化学性能[J].电子原件与材料.1998.17(1).17-19
[6] Hiroharu Kawasaki, Tsuyoshi Ueda, Yoshiaki Suada, et al. Properties of metal doped tungsten oxide thin films for NOx gas sensors grown by PLD method combined with sputtering process[J]. Sensors and Actuators.2004.B.100.266-269
[7] 李捍东,曾志国,高健存等.低压反应离子镀氧化钨电致变色薄膜[J].激光与红外.1996.26(4). 271-274
[8] A.I. Gavrilyuk. Photochromism in W03 thin films. Electrochimica Acta, 1999,44:3027～3037.
[9] G. Leftheriotis, S. Papaefthimiou. Effect of the tungsten oxidation states in thethermalcoloration and bleaching of amorphous W03 films. Thin Solid Films,2001,384:298～306.
[10] P. Gerard, A. Deneuville. Color in "tungsten trioxide" thin films. J.Appl.Phys., 1997,4R: 4265~4255.
[11] C. Trimble. Infrared emittance modulation devices using electrochromic crystalline tungsten oxide, polymer conductor, and nickel oxide. Thin Solid Films, 1999,355～356:2634
[12] S. Sawada, G.C. Danielson, Electrical conduction in crystals and ceramics of W03.Phys Rev, 1959, 113:803～805.
[13] M. Penza thin films M.A. Tagliente, L for a NOX gas sensor. Mirenghi, et al. Tungsten trioxide (W03) sputtered Sensors and Actuators B, 1998, 50:9～18.
[14] H.YWang, P. Xu, T.M. Wang. The preparation and prDesign2002, 23:331～336.
[15] Esra Ozkan, Se-Hee Lee, C.Edwin Tracy, et al. Compoperties study ofphotocatalytic nanocrystalline/nanoporous W03 thin films. Materials and arison of electrochromicamorphous and crystalline tungsten oxide films[J]. Solar Energy Materials&Solar Cells, 2003,79:439～448.
[16] Solis J L, Sauk ko S, Kish L, et al. Semiconductor gas sensor based on naniostructured tungsten oxide[J]. Thin Solid Films.2001.391(2).255-260
[17] 陈杰等. WO3 薄膜的电致变色特性的研究. 光学学报. 1996 年 10 月第 16 卷第 10期.1475-1478
[18] DuXM, Almeida R. Effect of thermal on the structure and properties of SiO2-TiO2 gel gilms on silicon substrates[J].Journal of Sol-Gel Science anTechnology.1997(8).377-380
[19] A. Georg , W. Graf, R. Neumann, V. Wittwer,Solid State Ionics 127 (2000) 319
[20] U. OPARA KRASOVEC, B. OREL , A. GEORG and V. WITTWER,Solar Energy Vol. 68, No. 6, pp. 541–551, 2000.
[21] C.N.Xu, N.Miura, Y.Ishida, et al. Selective detection of NH3 over NO in combustion exhausts by using Au and MoO3 doubly promoted WO3 element[J].Sensors and actuators. 2000.B65.163-165
[22] 颜肖慈,余林颇等.纳米氧化锌微乳液法的研制和表征[J].十堰职业技术学院学报,2002,15(2):67-68.
[23] G. A. deWijs, R.A. deGroot, Ekectrochimica Acta.,46(2001) 1989.
[24] Ocana M, Fornes V, Serna C J. The variability of the infrared powder spectrum of a morphous SiO2[J].Journal of Non-Crystalline Solids.1989.107.187-192
[25] Se-Hee Lee, Hyeonsikm Cheong, etc, Ekectrochimica Acta.,44(1999) 3111.
[26] C.G. Granqvist, Handbook of Inorganic Electrochromic Materials, Elsevier, Amsterdam, 1995.
[27] C.G. Granqvist, Handbook of Inorganic Electrochromic Materials, Elsevier, Amsterdam,1997.
[28] A. Georg, W. Graf, D. Schweiger, V. Wittwer, P. Nitz, H.R. Wilson, Solar Energy 62 (1998) 215.
[29] A. Georg, W. Graf, R. Neumann, V. Wittwer, Sol. State Ion. 127 (2000) 319.
[30] C.G. Granqvist, Sol. Energy Mat. Sol. C 60 (2000) 201.
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