VOCs气敏传感器的制备及性能研究
|
摘要
随着工业的发展，工业生产和日常生活中使用的化学原料和在生产过程中产生的气体种类和数量越来越多。这些气体中，有毒气体不仅污染环境，而且严重威胁着人类的健康和安全，尤其是芳香族化合物中的芳香烃即苯类化合物(苯、甲苯、二甲苯)和醛类气体对人体健康的损害十分严重。因此对这几类VOCs进行有效便捷的监测，引起了人们极大的关注。
本论文采用固相合成的方法制备了在TiO_2中分别混合不同原子百分比的Al_2O_3、SnO_2、In_2O_3和Cr_2O_3的敏感材料，并采用传统的陶瓷型气敏传感器的制备工艺制备了气敏元件。对上述气敏材料及传感器对苯、甲醛等气体的气敏特性进行了测试。研究了材料的化学组分对气敏特性的影响，加热功率对材料气敏特性的影响及气敏传感器的响应—恢复时间。结果表明：在TiO_2中，分别混合SnO_2、In_2O_3或Cr_2O_3的传感器对苯都有响应，其中以混合SnO_2的传感器对苯的灵敏度最好；混合In_2O_3或Cr_2O_3的传感器对丙酮气体有较好响应；混合SnO_2或Cr_2O_3的传感器元件对甲醛气体都表现出较好的响应，且其中以混合Cr_2O_3的元件更为灵敏。
另外，我们还分别采用固相合成和溶胶—凝胶工艺制备了不同TiO_2／Cr_2O_3配比的一系列TiO_2／Cr_2O_3敏感材料，比较研究了不同材料制备工艺对气敏材料的气敏特性的影响。气敏特性研究结果表明：用固相合成法制备的Cr含量为48.50at％的TiO_2／Cr_2O_3敏感元件对苯和甲醛都有最好的灵敏性和选择性，可有效检测21.5ppm苯和26.1ppm甲醛气体。其最佳工作(加热)电压都为5.5V。对苯和甲醛的平均响应时间分别是20s和2min，恢复时间较长，还需改进。
In recent years, the demand of sensors for safety control and environmental monitoring has been expanded enormously. Especially, more and more people pay much attention on the detection of volatile organic compounds (VOCs) such as formaldehyde, pyridine, trichloroethylene, benzene, toluene, ethylene, etc.. The volatile organic compounds (VOCs) are much harmful to living things. For example, the aromatic hydrocarbons such as benzene, has been found to be responsible for the leucocythemia and lung cancer. And they are frequently encountered in every day life. For example, they exis in unleaded gasoline, paint, etc. So, it is necessary to develop a cheap and portable technique to detect or measure these kinds of substances, in the air.
In this thesis, the VOCs gas sensing materials are prepared by solid state reaction method and sol-gel method respectively using TiO_2, Al_2O_3, SnO_2,In_2O_3 and Cr_2O_3 powders as raw materials. The ceramics gas sensors are made from above sensing materials prepared by means of traditional ceramics gas sensor processing. And the gas properties of these sensors are measured. The optimal composition of the sensing materials and the optimal sensor processing are obstained.
The results demonstrated that the ceramic sensors made from TiO_2 mixed SnO_2, In_2O_3 or Cr_2O_3 powders respectively are all sensitive to benzene, and the sensors made from TiO_2 mixed with SnO_2 powders have the best sensitivity to benzene. The ceramic sensors made from TiO_2 mixed with In_2O_3, or Cr_2O_3 powders respectively show good response to acetone. The ceramic sensors made from TiO_2 mixed SnO_2 or Cr_2O_3 sensors show good sensitivity to formaldehyde and the Cr_2O_3 -mixed sensors
本论文采用固相合成的方法制备了在TiO_2中分别混合不同原子百分比的Al_2O_3、SnO_2、In_2O_3和Cr_2O_3的敏感材料，并采用传统的陶瓷型气敏传感器的制备工艺制备了气敏元件。对上述气敏材料及传感器对苯、甲醛等气体的气敏特性进行了测试。研究了材料的化学组分对气敏特性的影响，加热功率对材料气敏特性的影响及气敏传感器的响应—恢复时间。结果表明：在TiO_2中，分别混合SnO_2、In_2O_3或Cr_2O_3的传感器对苯都有响应，其中以混合SnO_2的传感器对苯的灵敏度最好；混合In_2O_3或Cr_2O_3的传感器对丙酮气体有较好响应；混合SnO_2或Cr_2O_3的传感器元件对甲醛气体都表现出较好的响应，且其中以混合Cr_2O_3的元件更为灵敏。
另外，我们还分别采用固相合成和溶胶—凝胶工艺制备了不同TiO_2／Cr_2O_3配比的一系列TiO_2／Cr_2O_3敏感材料，比较研究了不同材料制备工艺对气敏材料的气敏特性的影响。气敏特性研究结果表明：用固相合成法制备的Cr含量为48.50at％的TiO_2／Cr_2O_3敏感元件对苯和甲醛都有最好的灵敏性和选择性，可有效检测21.5ppm苯和26.1ppm甲醛气体。其最佳工作(加热)电压都为5.5V。对苯和甲醛的平均响应时间分别是20s和2min，恢复时间较长，还需改进。
In recent years, the demand of sensors for safety control and environmental monitoring has been expanded enormously. Especially, more and more people pay much attention on the detection of volatile organic compounds (VOCs) such as formaldehyde, pyridine, trichloroethylene, benzene, toluene, ethylene, etc.. The volatile organic compounds (VOCs) are much harmful to living things. For example, the aromatic hydrocarbons such as benzene, has been found to be responsible for the leucocythemia and lung cancer. And they are frequently encountered in every day life. For example, they exis in unleaded gasoline, paint, etc. So, it is necessary to develop a cheap and portable technique to detect or measure these kinds of substances, in the air.
In this thesis, the VOCs gas sensing materials are prepared by solid state reaction method and sol-gel method respectively using TiO_2, Al_2O_3, SnO_2,In_2O_3 and Cr_2O_3 powders as raw materials. The ceramics gas sensors are made from above sensing materials prepared by means of traditional ceramics gas sensor processing. And the gas properties of these sensors are measured. The optimal composition of the sensing materials and the optimal sensor processing are obstained.
The results demonstrated that the ceramic sensors made from TiO_2 mixed SnO_2, In_2O_3 or Cr_2O_3 powders respectively are all sensitive to benzene, and the sensors made from TiO_2 mixed with SnO_2 powders have the best sensitivity to benzene. The ceramic sensors made from TiO_2 mixed with In_2O_3, or Cr_2O_3 powders respectively show good response to acetone. The ceramic sensors made from TiO_2 mixed SnO_2 or Cr_2O_3 sensors show good sensitivity to formaldehyde and the Cr_2O_3 -mixed sensors
引文
[1] MolhaveT.J..Volatile organic compounds, indoor air quanlity and health[J]. Indoor Air, 1991, 1(1): 357-370.
[2] Lance W.. Indoor air monitoring program and preliminary results of the U. S. EPA [R]. 1982.
[3] 沈学优，罗晓璐，朱利中．空气中挥发性有机化合物的研究进展[J]．浙江大学学报(理学版)，2001，Vol．28，No．5：547—556．
[4] 朱利中，松下秀鹤．空气中多环芳烃的研究现状[J]．环境科学进展，1997，5(5)：18-29．
[5] 谭培功，于彦彬，蒋海威等．大气中醛酮类羰基化合物的研究进展[J]．环境科学进展，1999，7(4)：19-23．
[6] The air quality strategy for England, Scotland, Wales and Northern Ireland, A Consultation Document, Department of the Environment, Transport and the Regions, London, 1999, Chapter 4, Section 12(updated 19 January 2000).
[7] Pellizzari D., Carpenter H., Bunch E.. Collection and analysis of trace organic vapor-pollutanta in ambient atmosphere[J]. En-viron. Sci. Technol., 975, 9(6): 556～560.
[8] Filatova G. N.. Gas chromatographic determination of ultra-trace amounts of halogen containing hydrocarbons in the atmosphere [J]. En-viron. Sci. Technol., 1983, 264(1): 129～131.
[9] 张林，戴树桂，宋春丽等．室内空气中芳香烃的测定与污染源模拟[J]．环境科学，1998，9(5)：63～65．
[10] Bertoni G., Canepari S., Rotatori M., et al. Evaluation tests and applications of a double-layer tube-type passive sampler[J]. Chromatogr., 1990, 522: 285～294.
[11] Whalen M., Ruth K. B.. Detection of aromatic hydrocarbons in the atmosphere at ppt levels[J]. Atmos. Environ., 1994, 28(3): 567～570.
[12] 包志成，张 尊，赵倩雪．空气中C_4～C_(12)烃类分析[J]．中国环境科学，1986，6(3)：74～76．
[13] 戴天有，魏复盛，彭清涛等．空气和废气中10种醛酮污染物的高效液相色谱测定[J]．环境科学研究，1996，9(6)：29～33．
[14] KrUger U.. Field studies of the indoor air quality by photo a-coustic spectroscopy[J]. Environ. Intern., 1995, 21(6): 791～801.
[15] Fan Q., Purnendu K. D.. Continuous automated determination of atmospheric formaldehyde at the parts pertrillion level[J]. Anal. Chem., 1994, 66(4): 551～556.
[16] Cisper M. E., Christopher G. G., Lisa E. T., et al. On-line detection of volatile organic compounds in air at part-per-trillion levels by membrane introduction mass spectrometry[J]. Anal. Chem., 1995, 67(8): 1413～1417.
[17] Mohammed M., Peter H.. A rapidly-responding sensor for benzene, methanol and ethanol vapours based on films of titanium dioxide dispersed in a polymer operating at room temperature [J]. Sensors and Actuators, B75 (2001): 197-202.
[18] Lee D. S., Jung J. K., Lim J. W.. Recognition of volatile organic compounds using SnO_2 sensor array and pattern recognition analysis[J]. Sensors and Actuators B77 (2001): 228-236.
[19] 季振国，孙兰侠，何振杰等．可鉴别室内有害气体的铟锡氧化物薄膜气敏特性研究[J]．传感技术学报，2004，6(2)：277-279．
[20] 王智民，张新，张艳熹等．旁热TiO_2／MoO_3复合厚膜邻二甲苯气敏陶瓷元件的制备及特性表征[J]．黑龙江大学自然科学学报，2003，Vol．20 No．2：89—92．
[21] 裴素华，孙海波，张华等．γ-Fe_2O_3响应苯类气体敏感材料特性研究[J]．功能材料与器件学报，2004，Vol．10 No．1：41—44．
[22] Zhu B. L., Xie C. S., Wang W. Y., et al. Improvement in gas sensitivity of ZnO thick film to volatile organic compounds (VOCs) by adding TiO_2[J]. Materials Letters, 2004, 58: 624-629.
[23] Srivastava A. K.. Detection of volatile organic compounds (VOCs) using SnO_2 gas-sensor array and artificial neural network[J]. Sensors and Actuators B96 (2003): 24-37.
[24] Ivanov P., Hubalek J., Malysz K., et al. A route toward more selective and less humidity sensitive screen-printed SnO_2 and WO_3 gas sensitive layers[J]. Sensors and Actuators B100 (2004): 221-227.
[25] Kanda K., Maekawa T.. Development of a WO_3 thick-film-based sensor for the detection of VOC[J]. Sensors and Actuators B108 (2005): 97-101.
[26] Tadashi T., Naganori D.. CeO_2(WO_3)-based thin film gas sensor for VOC detection The 10th International Meeting on Chemical Sensors 3A06: 290-291.
[27] 王林，张覃轶，祝柏林等．激光烧结纳米ZnO气敏传感器制备及其气敏特性研究[J]．传感技术学报，2003，12(4)：491-493．
[28] 刘延辉，曾大文，王辉虎等．热氧化纳米Zn制备ZnO厚膜及其气敏特性的研究[J]．传感技术学报，2005，3(1)：43-46．
[29] Kim J. S., Cho J. H., Han Y. A., et al. Characteristics of polyaniline sensor coated with poly(vinylidenefluoride) layer for volatile organic compounds The 10th International Meeting on Chemical Sensors 3P016: 676-677.
[30] Leray I., Vernie'res M. C., Claude B. C.. Porphyrins as probe molecules in the detection of gaseous pollutants: detection of benzene using cationic porphyrins in polymer films[J]. Sensors and Actuators B54 (1999): 243-251.
[31] 李茂琼，顾应龙，吴兴惠等．无需掺入贵金属的多元氧化物气敏材料[J]．传感技术学报，2002(3)：248—250．
[32] Munenobu T., Satoshi O., Yoshiteru I., et al. Air quality prediction by using semiconducting gas sensor with newly fabricated SmFeO_3 film[J]. Sensors and Actuators B97(2004): 190-197.
[33] Ichiro M., Kouta H., Norimitsu M., et al. Preparation of intercalative organic/MoO_3 anohybrids and their VOC gas sensing properties The 10th International Meeting on Chemical Sensors 2E12: 276-277.
[34] James A. D., Kristin D., Terry A. R.. NiO thin-film formaldehyde gas sensor[J]. Sensors and Actuators B80(2001): 106-115.
[35] 吴娜，王兢，杜海英等．甲醛气敏元件的研制[J]．传感器技术，2005，Vol．24，No．10：83—85．
[36] Taurino A. M. Capone S., Siciliano P., et al. Nanostructured TiO_2 thin films prepared by supersonic beams and their application in a sensor array for the discrimination of VOC[J]. Sensors and Actuators B92 (2003): 292-302.
[37] Getino J., Horrillo M. C., Gutierrez J., et al. Analysis of VOCs with a tin oxide sensor array[J]. Sensors and Actuators B43(1997): 200-205.
[38] 司士辉，朱德荣．TiO_2纳微孔膜增敏的压电石英晶体传感器[J]．中南工业大学学报，2002，Vol．33，No．5：477-479．
[39] Fung Y. S., Si S. H., Zhu D. R., et al. Nanoporous TiO_2 film as coating for piezoelectric crystal sensor in the detection of organic vapors in air The 10th International Meeting on Chemical Sensors 3P029: 698-699.
[40] Vancura C., Li Y., Hagleitner C., et al. Detection of volatile organic compounds using a new integrated single-chip CMOS cantilever gas sensor with magnetic actuation The 10th International Meeting on Chemical Sensors 2B12: 190-191.
[41] Maute M.,Raible S.,Prins F.E.,et al.Detection of volatile organic compounds VOCs with polymer-coated cantilevers[J].Sensors and Actuators B58 (1999) :505—511.
[42] Sasahara T.,Kido A.,Ishihara H.,et al.Highly sensitive detection of volatile organic compounds by an adsorption/combustion-type sensor based on mesoporous silica The 10th International Meeting on Chemical Sensors 1B 14:60-61.
[43] Shafiqul Islam A.K.M.,Ismail Z.,Shakaff c, A. D.,et al.Transient parameters of a coated quartz crystal microbalance sensor for the detection of volatile organic compounds (VOCs)[J].Sensors and Actuators B109 (2005) :238-243.
[44] Maric,Lorgen J.W.,Herrmann U.,et al.A new method to reduce the desorption time of a QCM sensor,using a halogen spot for heating[J].Sensors and Actuators B101 (2004):265-267.
[45] Masanobu M.,Toshiyuki U..Molecular imprinting strategy for solvent molecules and its application for QCM-based VOC vapor sensing[J].Sensors and Actuators Bl 13 (2006): 94-99.
[46] Fang M.,Vetelino K.,Rothery M.,et al.Detection of organic chemicals by SAW sensor array[J].Sensors and Actuators B56 (1999): 155-157.
[47] Penza M.,Gassano G..Application of principal component analysis and artificial neural networks to recognize the individual VOCs of methanol/2-propanol in a binary mixture by SAW multi-sensor array[J].Sensors and Actuators B89 (2003) :269-284.
[48] Quercia L.,Loffredo F.,Alfano B.,et al.Fabrication and characterization of carbon nanoparticles for polymer based vapor sensors[J].Sensors and Actuators B100 (2004) :22-28.
[49] Guy N. T.,Anthony G.E..On pattern recognition dependency of desorption heat, activation energy, and temperature of polymer-based VOC sensors for the electronic NOSE [J].Sensors and Actuators B110 (2005) :81-88.
[50] Buhlmann K.,Schlatt B.,Cammann K.,et al.Plasticised polymeric electrolytes: new extremely versatile receptor materials for gas sensors (VOC monitoring) and electronic noses (odour identification:discrimination)[J].Sensors and Actuators B49 (1998) :156-165.
[51] Jayaraman V.,Gnanasekar K.I.,Prabhu E,et al.Preparation and characterisation of Cr_(2-x)Ti_xO_(3+x) and its sensor properties[J].Sensors and Actuators B55 (1999): 175-179.
[52] Shaw G.A.,Pratt K.F.E.,Parkin I.P.,et al.Gas sensing properties of thin film (≤3μm)Cr_(2-x)Ti_xO_3(CTO) prepared by atmospheric pressure chemical vapour deposition (APCVD), compared with that prepared by thick film screen-printing[J]. Sensors and Actuators B104 (2005): 151-162.
[53] 娄向东，沈荷生，沈渝生等．ZnO系半导体陶瓷气敏传感器的进展[J]．传感器技术，1991，6(3)：1-5．
[54] Merson A., Dittrich Th., Zidon Y., et al. Charge transfer from TiO_2 into adsorbed benzene diazonium compounds[J]. Applied Physics Letters 2004, Vol. 85, No. 6: 1075-1076.
[55] 潘海波，陈耐生，林德娟等．TiO_2基氧化物半导体氧敏传感器的研究开发进展[J]．功能材料与器件学报，2001，Vol．7，No．1：101—106．
[56] Kumazawa N., Islam M. R., Takeuchi M.. Photoresponse of a titanium dioxide chemical sensor, Journal of Electroanalytical Chemistry 472(1999): 137-141.
[57] 尚静，杜尧国，徐自力．TiO_2纳米粒子气—固复相光催化VOCs作用的研究进展[J]．环境污染治理技术与设备，2000，Vol．1，No．3：67—76．
[58] 尹荔松，沈辉．二氧化钛光催化研究进展及应用[J]．材料导报，2001，Vol．14，No．12：23—25．
[59] 张前程，张风宝，张国亮．苯在TiO_2上的气相光催化氧化反应历程[J]．催化学报，2004，Vol．25，NO．1：39—43．
[60] 胡安正，唐超群．纳米TiO_2光催化材料及其应用于环境保护的研究进展[J]．功能材料，2001．32(6)：586—590．
[61] 于向阳，梁文，杜永娟等．二氧化钛光催化材料的应用进展[J]．材料导报，2000，Vol．14，No．2：8—40．
[62] 孟宪权，王君，何磊等．TiO_2薄膜的制备及结构研究[J]．半导体学报，1999，Vol．20．No．5：395—399．
[63] 徐甲强，朱冬梅，王国庆等．添加剂对氧化钛气敏材料敏感特性的影响[J]．郑州轻工业学院学报，1996，Vol．11，NO．2：83—87．
[64] Ruiz A. M., Sakai G., Cornet A., et al. Cr-doped TiO_2 gas sensor for exhaust NO_2 monitoring[J]. Sensors and Actuators B93 (2003): 509-518.
[2] Lance W.. Indoor air monitoring program and preliminary results of the U. S. EPA [R]. 1982.
[3] 沈学优，罗晓璐，朱利中．空气中挥发性有机化合物的研究进展[J]．浙江大学学报(理学版)，2001，Vol．28，No．5：547—556．
[4] 朱利中，松下秀鹤．空气中多环芳烃的研究现状[J]．环境科学进展，1997，5(5)：18-29．
[5] 谭培功，于彦彬，蒋海威等．大气中醛酮类羰基化合物的研究进展[J]．环境科学进展，1999，7(4)：19-23．
[6] The air quality strategy for England, Scotland, Wales and Northern Ireland, A Consultation Document, Department of the Environment, Transport and the Regions, London, 1999, Chapter 4, Section 12(updated 19 January 2000).
[7] Pellizzari D., Carpenter H., Bunch E.. Collection and analysis of trace organic vapor-pollutanta in ambient atmosphere[J]. En-viron. Sci. Technol., 975, 9(6): 556～560.
[8] Filatova G. N.. Gas chromatographic determination of ultra-trace amounts of halogen containing hydrocarbons in the atmosphere [J]. En-viron. Sci. Technol., 1983, 264(1): 129～131.
[9] 张林，戴树桂，宋春丽等．室内空气中芳香烃的测定与污染源模拟[J]．环境科学，1998，9(5)：63～65．
[10] Bertoni G., Canepari S., Rotatori M., et al. Evaluation tests and applications of a double-layer tube-type passive sampler[J]. Chromatogr., 1990, 522: 285～294.
[11] Whalen M., Ruth K. B.. Detection of aromatic hydrocarbons in the atmosphere at ppt levels[J]. Atmos. Environ., 1994, 28(3): 567～570.
[12] 包志成，张 尊，赵倩雪．空气中C_4～C_(12)烃类分析[J]．中国环境科学，1986，6(3)：74～76．
[13] 戴天有，魏复盛，彭清涛等．空气和废气中10种醛酮污染物的高效液相色谱测定[J]．环境科学研究，1996，9(6)：29～33．
[14] KrUger U.. Field studies of the indoor air quality by photo a-coustic spectroscopy[J]. Environ. Intern., 1995, 21(6): 791～801.
[15] Fan Q., Purnendu K. D.. Continuous automated determination of atmospheric formaldehyde at the parts pertrillion level[J]. Anal. Chem., 1994, 66(4): 551～556.
[16] Cisper M. E., Christopher G. G., Lisa E. T., et al. On-line detection of volatile organic compounds in air at part-per-trillion levels by membrane introduction mass spectrometry[J]. Anal. Chem., 1995, 67(8): 1413～1417.
[17] Mohammed M., Peter H.. A rapidly-responding sensor for benzene, methanol and ethanol vapours based on films of titanium dioxide dispersed in a polymer operating at room temperature [J]. Sensors and Actuators, B75 (2001): 197-202.
[18] Lee D. S., Jung J. K., Lim J. W.. Recognition of volatile organic compounds using SnO_2 sensor array and pattern recognition analysis[J]. Sensors and Actuators B77 (2001): 228-236.
[19] 季振国，孙兰侠，何振杰等．可鉴别室内有害气体的铟锡氧化物薄膜气敏特性研究[J]．传感技术学报，2004，6(2)：277-279．
[20] 王智民，张新，张艳熹等．旁热TiO_2／MoO_3复合厚膜邻二甲苯气敏陶瓷元件的制备及特性表征[J]．黑龙江大学自然科学学报，2003，Vol．20 No．2：89—92．
[21] 裴素华，孙海波，张华等．γ-Fe_2O_3响应苯类气体敏感材料特性研究[J]．功能材料与器件学报，2004，Vol．10 No．1：41—44．
[22] Zhu B. L., Xie C. S., Wang W. Y., et al. Improvement in gas sensitivity of ZnO thick film to volatile organic compounds (VOCs) by adding TiO_2[J]. Materials Letters, 2004, 58: 624-629.
[23] Srivastava A. K.. Detection of volatile organic compounds (VOCs) using SnO_2 gas-sensor array and artificial neural network[J]. Sensors and Actuators B96 (2003): 24-37.
[24] Ivanov P., Hubalek J., Malysz K., et al. A route toward more selective and less humidity sensitive screen-printed SnO_2 and WO_3 gas sensitive layers[J]. Sensors and Actuators B100 (2004): 221-227.
[25] Kanda K., Maekawa T.. Development of a WO_3 thick-film-based sensor for the detection of VOC[J]. Sensors and Actuators B108 (2005): 97-101.
[26] Tadashi T., Naganori D.. CeO_2(WO_3)-based thin film gas sensor for VOC detection The 10th International Meeting on Chemical Sensors 3A06: 290-291.
[27] 王林，张覃轶，祝柏林等．激光烧结纳米ZnO气敏传感器制备及其气敏特性研究[J]．传感技术学报，2003，12(4)：491-493．
[28] 刘延辉，曾大文，王辉虎等．热氧化纳米Zn制备ZnO厚膜及其气敏特性的研究[J]．传感技术学报，2005，3(1)：43-46．
[29] Kim J. S., Cho J. H., Han Y. A., et al. Characteristics of polyaniline sensor coated with poly(vinylidenefluoride) layer for volatile organic compounds The 10th International Meeting on Chemical Sensors 3P016: 676-677.
[30] Leray I., Vernie'res M. C., Claude B. C.. Porphyrins as probe molecules in the detection of gaseous pollutants: detection of benzene using cationic porphyrins in polymer films[J]. Sensors and Actuators B54 (1999): 243-251.
[31] 李茂琼，顾应龙，吴兴惠等．无需掺入贵金属的多元氧化物气敏材料[J]．传感技术学报，2002(3)：248—250．
[32] Munenobu T., Satoshi O., Yoshiteru I., et al. Air quality prediction by using semiconducting gas sensor with newly fabricated SmFeO_3 film[J]. Sensors and Actuators B97(2004): 190-197.
[33] Ichiro M., Kouta H., Norimitsu M., et al. Preparation of intercalative organic/MoO_3 anohybrids and their VOC gas sensing properties The 10th International Meeting on Chemical Sensors 2E12: 276-277.
[34] James A. D., Kristin D., Terry A. R.. NiO thin-film formaldehyde gas sensor[J]. Sensors and Actuators B80(2001): 106-115.
[35] 吴娜，王兢，杜海英等．甲醛气敏元件的研制[J]．传感器技术，2005，Vol．24，No．10：83—85．
[36] Taurino A. M. Capone S., Siciliano P., et al. Nanostructured TiO_2 thin films prepared by supersonic beams and their application in a sensor array for the discrimination of VOC[J]. Sensors and Actuators B92 (2003): 292-302.
[37] Getino J., Horrillo M. C., Gutierrez J., et al. Analysis of VOCs with a tin oxide sensor array[J]. Sensors and Actuators B43(1997): 200-205.
[38] 司士辉，朱德荣．TiO_2纳微孔膜增敏的压电石英晶体传感器[J]．中南工业大学学报，2002，Vol．33，No．5：477-479．
[39] Fung Y. S., Si S. H., Zhu D. R., et al. Nanoporous TiO_2 film as coating for piezoelectric crystal sensor in the detection of organic vapors in air The 10th International Meeting on Chemical Sensors 3P029: 698-699.
[40] Vancura C., Li Y., Hagleitner C., et al. Detection of volatile organic compounds using a new integrated single-chip CMOS cantilever gas sensor with magnetic actuation The 10th International Meeting on Chemical Sensors 2B12: 190-191.
[41] Maute M.,Raible S.,Prins F.E.,et al.Detection of volatile organic compounds VOCs with polymer-coated cantilevers[J].Sensors and Actuators B58 (1999) :505—511.
[42] Sasahara T.,Kido A.,Ishihara H.,et al.Highly sensitive detection of volatile organic compounds by an adsorption/combustion-type sensor based on mesoporous silica The 10th International Meeting on Chemical Sensors 1B 14:60-61.
[43] Shafiqul Islam A.K.M.,Ismail Z.,Shakaff c, A. D.,et al.Transient parameters of a coated quartz crystal microbalance sensor for the detection of volatile organic compounds (VOCs)[J].Sensors and Actuators B109 (2005) :238-243.
[44] Maric,Lorgen J.W.,Herrmann U.,et al.A new method to reduce the desorption time of a QCM sensor,using a halogen spot for heating[J].Sensors and Actuators B101 (2004):265-267.
[45] Masanobu M.,Toshiyuki U..Molecular imprinting strategy for solvent molecules and its application for QCM-based VOC vapor sensing[J].Sensors and Actuators Bl 13 (2006): 94-99.
[46] Fang M.,Vetelino K.,Rothery M.,et al.Detection of organic chemicals by SAW sensor array[J].Sensors and Actuators B56 (1999): 155-157.
[47] Penza M.,Gassano G..Application of principal component analysis and artificial neural networks to recognize the individual VOCs of methanol/2-propanol in a binary mixture by SAW multi-sensor array[J].Sensors and Actuators B89 (2003) :269-284.
[48] Quercia L.,Loffredo F.,Alfano B.,et al.Fabrication and characterization of carbon nanoparticles for polymer based vapor sensors[J].Sensors and Actuators B100 (2004) :22-28.
[49] Guy N. T.,Anthony G.E..On pattern recognition dependency of desorption heat, activation energy, and temperature of polymer-based VOC sensors for the electronic NOSE [J].Sensors and Actuators B110 (2005) :81-88.
[50] Buhlmann K.,Schlatt B.,Cammann K.,et al.Plasticised polymeric electrolytes: new extremely versatile receptor materials for gas sensors (VOC monitoring) and electronic noses (odour identification:discrimination)[J].Sensors and Actuators B49 (1998) :156-165.
[51] Jayaraman V.,Gnanasekar K.I.,Prabhu E,et al.Preparation and characterisation of Cr_(2-x)Ti_xO_(3+x) and its sensor properties[J].Sensors and Actuators B55 (1999): 175-179.
[52] Shaw G.A.,Pratt K.F.E.,Parkin I.P.,et al.Gas sensing properties of thin film (≤3μm)Cr_(2-x)Ti_xO_3(CTO) prepared by atmospheric pressure chemical vapour deposition (APCVD), compared with that prepared by thick film screen-printing[J]. Sensors and Actuators B104 (2005): 151-162.
[53] 娄向东，沈荷生，沈渝生等．ZnO系半导体陶瓷气敏传感器的进展[J]．传感器技术，1991，6(3)：1-5．
[54] Merson A., Dittrich Th., Zidon Y., et al. Charge transfer from TiO_2 into adsorbed benzene diazonium compounds[J]. Applied Physics Letters 2004, Vol. 85, No. 6: 1075-1076.
[55] 潘海波，陈耐生，林德娟等．TiO_2基氧化物半导体氧敏传感器的研究开发进展[J]．功能材料与器件学报，2001，Vol．7，No．1：101—106．
[56] Kumazawa N., Islam M. R., Takeuchi M.. Photoresponse of a titanium dioxide chemical sensor, Journal of Electroanalytical Chemistry 472(1999): 137-141.
[57] 尚静，杜尧国，徐自力．TiO_2纳米粒子气—固复相光催化VOCs作用的研究进展[J]．环境污染治理技术与设备，2000，Vol．1，No．3：67—76．
[58] 尹荔松，沈辉．二氧化钛光催化研究进展及应用[J]．材料导报，2001，Vol．14，No．12：23—25．
[59] 张前程，张风宝，张国亮．苯在TiO_2上的气相光催化氧化反应历程[J]．催化学报，2004，Vol．25，NO．1：39—43．
[60] 胡安正，唐超群．纳米TiO_2光催化材料及其应用于环境保护的研究进展[J]．功能材料，2001．32(6)：586—590．
[61] 于向阳，梁文，杜永娟等．二氧化钛光催化材料的应用进展[J]．材料导报，2000，Vol．14，No．2：8—40．
[62] 孟宪权，王君，何磊等．TiO_2薄膜的制备及结构研究[J]．半导体学报，1999，Vol．20．No．5：395—399．
[63] 徐甲强，朱冬梅，王国庆等．添加剂对氧化钛气敏材料敏感特性的影响[J]．郑州轻工业学院学报，1996，Vol．11，NO．2：83—87．
[64] Ruiz A. M., Sakai G., Cornet A., et al. Cr-doped TiO_2 gas sensor for exhaust NO_2 monitoring[J]. Sensors and Actuators B93 (2003): 509-518.