氨敏薄膜的制备及特性研究
摘要
气敏材料与传感器已广泛用于电子鼻、电子舌等仿生系统的设计。在食品工业、环保检测、反恐、防恐、毒品检测、人类及动物的一些疾病的早期预测和实时在线监控等方面具有重要的应用价值。研究高灵敏度、快速响应、重现性良好的有机薄膜传感器，同时，通过材料-工艺-器件性能的相关性研究，探讨有机膜的气敏规律性，用于指导新材料及器件的设计和开发，对该领域的深入研究及新器件的推广应用具有重要的意义。本文概述了气体传感器的研究进展，分析了影响气敏性能的主要因素及改进措施。针对这些问题，从敏感材料和制备工艺入手，探讨了如何改善这些性能的有效途径。本文首先探讨了气体敏感材料的选择。目前有机敏感材料、有机-无机复合材料因具有诸多优点而成为研究的热点。本文采用原位化学氧化聚合法制备了PEDT(3，4-聚乙撑二氧噻吩)、PPy(聚吡咯)、PPy-TiO_2三种敏感薄膜。对于PEDT，本文采用化学氧化法的工艺，探讨了工艺对成膜的影响，用扫描电子显微镜(SEM)观察膜的表面形貌，运用红外吸收光谱(IR)分析验证了所生成的PEDT聚合物。采用场效应管制备了PEDT气体传感器，研究了其对氨气的敏感特性，测量了其漏电流随温湿度的变化。结果表明PEDT对氨气有一定的敏感性。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PPy薄膜和PPy-TiO_2复合膜，并进行了紫外-可见光谱分析、红外吸收光谱(IR)分析和原子力显微镜分析比较。采用平面叉指电极分别制备了PPy和PPy-TiO_2气体传感器，研究了他们在常温下对有毒气体NH_3的敏感性，测试了其电阻随温湿度的变化，并做了相关比较。结果表明，掺杂了TiO_2无机物的PPy-TiO_2传感器虽然在灵敏度上略低于纯的PPy传感器，但是在响应-恢复时间上却得到了很大提高，同时在温湿度和稳定性方面也得到了一定改善。本论文的结论对聚合物及其复合材料的气体传感器的进一步研究具有一定的参考价值。
Gas sensitive materials and gas sensors have been widely used in the design of electronic nose and electronic tongue of bionic systems. They have many potential applications in food industry, environmental monitoring, anti-terrorism, the inspection of drugs and toxic gases, and the prognoses of some diseases. It is important to study the sensors consisted of organic films with high sensitivity, rapid response and good reproducibility and research the relationship among the materials, technologies and properties of devices, which is helpful in exploring the rules in these kinds of gas sensors to conduct the design, development and applications of new materials and new devices.
The progress of gas sensors was reviewed in this paper, and the influence factors and approaches to improve gas sensitivity were also analyzed. Aiming at high sensitivity, fast response rate, reproducibility and reversibility at room temperature, we have made some research in sensitive materials and film processing techniques.
First, the selection of sensitive materials was discussed. As the organic sensitive materials and the organic-inorganic composite materials have many advantages, they become the research hot topics. Three sensitive materials such as 3, 4-polyethylenedioxythiophene (PEDT), polypyrrole (PPy), PPy-TiO_2 were prepared via in-situ chemical oxidation polymerization.
PEDT was synthesized using chemical oxidation method. The film was characterized by infrared (IR) spectrophy and scanning electron microscope (SEM). Some factors affecting the properties of PEDT film were studied. Chemical field-effect transistor (ChemFET) gas sensor had been fabricated with the obtained PEDT film. The ammonia (NH_3) gas-sensitive characteristics and the drain current variation caused by the temperature and humidity were investigated. The results show that PEDT film is sensitive to NH_3.
PPy and PPy-TiO_2 thin films were also prepared by in-situ chemical oxidation polymerization and electrostatic self-assembly combined technique. The films were characterized by UV-Vis absorption spectrum, IR and atomic force microscopy. With the assistance of interdigitated electrodes, gas sensors using PPy, PPy-TiO_2 composite thin films were achieved, respectively. The sensitivity of the sensors to toxic gase NH_3 and the resistance changes induced by the temperature and humidity were investigated. The results show that the PPy-TiO_2 film sensor is less sensitive to NH_3 than PPy film sensor, but its response-recovery time becomes shorter, its temperature and humidity properties and its stability have been improved a lot.
The result in this dissertation would be beneficial for the further study of gas sensors composed of polymer films and their composite films.
Gas sensitive materials and gas sensors have been widely used in the design of electronic nose and electronic tongue of bionic systems. They have many potential applications in food industry, environmental monitoring, anti-terrorism, the inspection of drugs and toxic gases, and the prognoses of some diseases. It is important to study the sensors consisted of organic films with high sensitivity, rapid response and good reproducibility and research the relationship among the materials, technologies and properties of devices, which is helpful in exploring the rules in these kinds of gas sensors to conduct the design, development and applications of new materials and new devices.
The progress of gas sensors was reviewed in this paper, and the influence factors and approaches to improve gas sensitivity were also analyzed. Aiming at high sensitivity, fast response rate, reproducibility and reversibility at room temperature, we have made some research in sensitive materials and film processing techniques.
First, the selection of sensitive materials was discussed. As the organic sensitive materials and the organic-inorganic composite materials have many advantages, they become the research hot topics. Three sensitive materials such as 3, 4-polyethylenedioxythiophene (PEDT), polypyrrole (PPy), PPy-TiO_2 were prepared via in-situ chemical oxidation polymerization.
PEDT was synthesized using chemical oxidation method. The film was characterized by infrared (IR) spectrophy and scanning electron microscope (SEM). Some factors affecting the properties of PEDT film were studied. Chemical field-effect transistor (ChemFET) gas sensor had been fabricated with the obtained PEDT film. The ammonia (NH_3) gas-sensitive characteristics and the drain current variation caused by the temperature and humidity were investigated. The results show that PEDT film is sensitive to NH_3.
PPy and PPy-TiO_2 thin films were also prepared by in-situ chemical oxidation polymerization and electrostatic self-assembly combined technique. The films were characterized by UV-Vis absorption spectrum, IR and atomic force microscopy. With the assistance of interdigitated electrodes, gas sensors using PPy, PPy-TiO_2 composite thin films were achieved, respectively. The sensitivity of the sensors to toxic gase NH_3 and the resistance changes induced by the temperature and humidity were investigated. The results show that the PPy-TiO_2 film sensor is less sensitive to NH_3 than PPy film sensor, but its response-recovery time becomes shorter, its temperature and humidity properties and its stability have been improved a lot.
The result in this dissertation would be beneficial for the further study of gas sensors composed of polymer films and their composite films.
引文
[1] 王冲．微型薄膜气体传感器研究：[硕士学位论文]．华中科技大学，2005，1-56
[2] F. Quarantaa, R. Rellaa, et al, Preparation and characterization of nanostructured materials for an artificial olfactory sensing system, Sensors and Actuators, 2002, B 84: 55-59
[3] Manuela O'Connell, Gabriela Valdora, et al, A practical approach for fish freshness determinations using a portable electronic nose, Sensors and Actuators, 2001, B 80: 149-154
[4] Julian W. Gardner, et al, An electronic nose system to diagnose illness, Sensors and Actuators, 2000, B 70: 17-24
[5] Susanne Hulmin, et al, Compression of electronic tongue data based on voltammetry-a comparative study, Sensors and Actuators, 2001, B76: 455-464
[6] Seiyama T, Kato A, Fujishi K, et al. A new detector for gaseous using semiconductor thin film, Anal Chem. 1962, 34: 1502-1505
[7] Mexner H, Lampe U. Metal Oxide sensors. Sensors and Actuators B, 1996, 33: 198-202
[8] Srczurek A., Szecowka P. M., Licmmki B. W.. Application of sensor amy and neural networks for quantification of organic solvents vapors in air, Sensors and Actuators B, 1999, (58): 427-432
[9] 张覃铁．电子鼻传感器阵列系统及应用研究：[博士学位论文]．华中科技大学，2005，1-147
[10] Naksimovich N. P, Yeremina L. E. Sensors and Actuators B, 1993, 13-14: 256-258
[11] 马戎，周王民，陈明．气体传感器的研究及发展方向．航空计测技术综合评述，2004，24(4)：1-4
[12] 王玮．基于气体传感器阵列的混合气体检测系统：[博士学位论文]．西北工业大学，2002，1-128
[13] 刘义祥．气体传感器在气体泄漏事故处理中的应用．消防技术与产品信息，2002，(2)：36-38
[14] WANG Y D, SLTN X D, LI Y F, et al. Perovskite-type NiSnO3 used as the ethanol sensitive material. Solid-State Electron, 2000, 44: 2009-2014.
[15] Yun E S, Park T H,. Biotechnol Bioprocess Eng, 2000, 5(2): 150.
[16] Wenyi Zhang, H. Uchida, T. Katsube, et al. A novel semiconductor NO gas sensor operating at room temperature. Sensors and Actuators B, 1998, 49: 58-62
[17] Satoshi Ozawa, Peter C. Hauser, Kurt Seiler et al. Ammonia gas selective optical sensors based on neutral ionophores. Anal. Chem, 1991, 63, 640-644
[18] M. Penza, E. Milella, V. I. Anisimkin. Monitoring of NH_3 gas by LB polypyrrole-based SAW sensor. Sensors and Actuators B, 1998, 47: 218-224.
[19] Kong J, Franklin N. R, Zhou C. W. et al. Nanotube molecular wires as chemicalsensors. Science, 2000, 287(1): 622-625
[20] 段振新．氨敏场效应晶体管微型化的研究．传感器技术，1991，2：10-12
[21] 皱德恕，王东风，高国．MOS集成氨敏传感器．传感器技术，1997，7：6-8
[22] Xusheng Wang, Norio Miura, Noboru Yamazoe. Study of WO3 based sensing materials for NH3 and NO detection. Sensor and Actutors B, 2000, 66: 74-76.
[23] A. Teeramongkonrasmee, M. Sriyudthsak Methanol and ammonia sensing characteristics of sol-gel derived thin film gas sensor. Sensors and Actuators B, 2000, 66: 256-259.
[24] G. S. Trivikrama Rao, D. Tarakarama Rao. Gas sensitivity of ZnO based thick film sensor to NH3 at room temperature. Sensors and Actuators B, 1999, 55: 166-169
[25] L. H. Huo, X. L. Lia, W. Lia et al. Gas sensitivity of composite Langrnuir-Blodgett films of Fe_2O_3 nanoparticle-copper phthalocyanine. Sensors and Actuators B, 2000, 71: 77-81
[26] A. Galdikas, A. Mironas, V. Strazdiene et al. Room temperature functioning ammonia sensor based on solid-state Cu_xS films. Sensors and Actuators B, 2000, 67: 76-83.
[27] V. Romanovakaya, M. Ivanovskaya, P. Bogdanov. A Study of sensing properties of Pt-and Au-loaded In_2O_3 ceramics. Sensors and Actuators B, 1999, 56: 31-36.
[28] D. Mutschall, K. Holzner, E. Obermeier. Sputtered molybdenum oxide thin films for NH_3 detection. Sensors and Actuators B, 1996, 35-36: 320-324
[29] Afshad Talaie, Conducting polymer based pH detector: a new outlook to pH sensing technology, Polymer, 1997, 38(5): 1145-1150
[30] S. C. K. Misraa, Prafull Mathura, Maneesha Yadava, M. K. Tiwaria, S. C. Garga, P. Tripathib, Preparation and characterization of vacuum deposited semiconducting nanocrystalline polymeric thin film sensors for detection of HCI, Polymer 45 (2004) 8623-8628
[31] V. V. Chabukswar, Sushama Pethkar, Anjali A. Athawale, Acrylic acid doped polyaniline as an ammonia sensor, Sensors and Actuators, 2001, B77: 657663
[32] 肖恺，于贵，刘云圻．有机场效应晶体管研究和应用进展．科学通，2002，47(12)：881-890
[33] Burgmair M., Eisels I. Contribution of the gate insulator surface to work function measurements with a gas sensitive FET. Sensors, 2002. Proceedings of IEEE, 1: 439-442
[34] 王阳元，关旭东，马俊如．集成电路工艺基础．北京：高等教育出版社，1991，1-609
[35] 叶龙，李焰．有机敏感材料NO_2气体传感器．传感器技术，1994，(4)：1-6
[36] 陈湘宁．导电薄膜BAYTRON及其应用．华工新型材料，1999，27(9)：36-37
[37] Liu Niu, Carita Kvarnstrom, K. Froberg, et al. Electrochemically controlled surface morphology and crystallinity in poly(3,4-ethylenedioxythioxythiophene). Synthetic Metals, 2001, 56: 425-429
[38] M Brown, J. S. Kim, R. H. Friend, et al. Effect of poly(3,4-ethylene dioxythiophene) on the built-in field in polymer light-emitting diodes probed by electroabsorption spectroscopy, Synthetic Metals, 2000, 111: 285-287
[39] M. Bouguettaya, N. Vedie, C. Chevrol. New conductive adhesive based on Poly(3,4-ethylene dioxythiophene), Synthetic Metals, 1999, 102: 1428-1431.
[40] K. E Aasmundtveit, E. J. Samuelsen, L. A. A. Pettersson, et all. Structure of thin films of poly(3,4-ethylenedioxythioxythiophene). Synthetic Metals, 1999, 112: 561-564
[41] Andersson M, Holmberg M., Lundstrom l., et al. Development of a ChemFET sensor with molecular films of porphyrins as sensitive layer. Sensors and Actuators B, 2001, 77: 567-571
[42] 陈国华，颜文礼．化学法合成导电聚吡咯的研究现状．华侨大学学报(自然科学版)，1994，15(2)：172-176
[43] De Souza J E G, Dos Santos F L, Barros-Neto B. Polypyrrole thin films gas sensors. Synthetic Metals, 2001, 119: 383-384
[44] Sgritski V S, Reut J, Opik A, et al. Environmental QCM sensors toted with polypyrrole. Synthetic Metals, 1999, 102: 1326-132
[45] Lin-Xia Wang, Xin-Gui Li, Yu-Liang Yang. Praparation, properties and applications of polypyrroles. Reactive&Functional Polymers, 2001, 47(2): 125-139
[46] 尹五生．聚吡咯导电材料合成方法的进展．功能材料，1996，27 C2)：97-102
[47] 徐友龙，季锐，王飞．影响掺杂聚吡咯(PPy)导电性能的因素．电子元件与材料，2000，19(5)：17-19
[48] 万本强，吴婉群．催化电合成聚吡咯的电化学性质研究．西南师范大学学报(自然科学版)，1993，18(1)：52-55
[49] 贝建中，钱人元．在水溶液中电化学反应制备大面积聚吡咯膜．功能高分子学报，1991，4(4)：320-324
[50] Gouri Smithy Akundy, Jude O. Iroh. Polypyrrole coatings on aluminum-synthesis and characterization. Polymer, 2001, 42 (24): 9665-9669
[51] 丁文艳，李丹，汪信，陆路德，杨绪杰．聚电解质自组装膜对聚吡咯原位沉积的影响．功能材料，2002，33(4)：437～439
[52] M. K. Rima, M. Adamib, P. FaRicib, C. Nicolinic. Physical insight in the in-situ self-assembled firms of polypyrrole. Polymer, 2000, 41: 7499-7509
[53] 许均，曾幸荣，李鹏，邓惠萍，苏海霞．聚吡咯／二氧化硅复合材料的制备及导电性的研究．化学与黏合，2005，No．1，Vol．27：1～4
[54] 裘式纶，等，纳米材料研究进展．化学研究及应用，1998，10(4)：331
[55] Danielle C. Schnitzler, Michelle S. Meruvia, No A. Hummelgen, and Aldo J. G zarbin. Preparation and Characterization of Novel Hybrid Materials Formed from (Ti,Sn)O_2 Nanoparticles and Polyaniline. Chem. Mater, 2003, 15: 4658-4665
[56] George Z. Chen, Milo S. P. Shaffer, Dan Coleby, Gemma Dixon, Wuzong Zhou, Derek J. Fray, and Alan H. Windle. Carbon Nanotube and Polypyrrole Composites. Coating and Doping, Adv. Mater. 2000, 12(7): 522-526.
[57] Kay Hyeok An, Seung Yol Jeong, Ha Ryong Hwang, and Young Hee Lee. Enhanced Sensitivity of a Gas Sensor Incorporing Single-Walled Carbon Nanotube-Polypyrrole Nanocomposites. Advanced Materials, 2004, 16(12): 1005-1009
[58] Huseyin Zengin, Wensheng Zhou, Jiangyong Jin, Richard Czerw, Dennis W. Smith, Luis Echegoyen, David L. carroll, Stephen H. Foulger, and John Ballato. Carbon Nanotube Doped Polyaniline. Advanced Materials, 2002, 14(20): 1480-1483
[59] Jiaxing Huang and Richard B. Kaner. A General Chemical Route to Polyaniline Nanofibers. J. AM. CHEM. SOC, 2004, 126, 851-855
[60] M. Matsuguchi, J. Io, G Sugiyama, Y. Sakai, Effects of NH3 gas on the electrical conductivity of polyaniline blend films. Synthetic Metals, 2002, 128: 1519
[61] M. Baibarac, I. Baltog, S. Lefrant, J. Y. Mevellec, and O. Chauvet, Polyaniline and Carbon Nanotube Based Composites Containting Whole Units and Fragments of Nanotubes. Chem. Mater, 2003, 15: 4149-4155
[62] M. K. Rama,, M. Adamib, P. Faracib, C. Nicolinic, Physical insight in the in-situ self-assembled films of polypyrrole, Polymer 41 (2000) 7499-7509
[63] Marie-isabelle Baraton, Lhadi Merhari, Jianzhao Wang and Kenneth E Gonsalves, Investigation of the TiO_2/PPV nanocomposite for gas sensing application. Nanotechnoiogy, 1998, 9: 356～359
[64] 张玉泉，于跃华，丁雪佳，崔国强，刘丽敏，李长江．聚吡咯／纳米氧化钇复合材料的结构与性能研究．现代化工，2004，No．1，Vol．24：37-39
[65] Manoj K. Ram, Ozlem Yavuz, Matt AIdissi, NO_2 gas sensing based on ordered ultrathin films of conducting polymer and its nanocomposite, Synthetic Metals 151 (2005) 77-84
[2] F. Quarantaa, R. Rellaa, et al, Preparation and characterization of nanostructured materials for an artificial olfactory sensing system, Sensors and Actuators, 2002, B 84: 55-59
[3] Manuela O'Connell, Gabriela Valdora, et al, A practical approach for fish freshness determinations using a portable electronic nose, Sensors and Actuators, 2001, B 80: 149-154
[4] Julian W. Gardner, et al, An electronic nose system to diagnose illness, Sensors and Actuators, 2000, B 70: 17-24
[5] Susanne Hulmin, et al, Compression of electronic tongue data based on voltammetry-a comparative study, Sensors and Actuators, 2001, B76: 455-464
[6] Seiyama T, Kato A, Fujishi K, et al. A new detector for gaseous using semiconductor thin film, Anal Chem. 1962, 34: 1502-1505
[7] Mexner H, Lampe U. Metal Oxide sensors. Sensors and Actuators B, 1996, 33: 198-202
[8] Srczurek A., Szecowka P. M., Licmmki B. W.. Application of sensor amy and neural networks for quantification of organic solvents vapors in air, Sensors and Actuators B, 1999, (58): 427-432
[9] 张覃铁．电子鼻传感器阵列系统及应用研究：[博士学位论文]．华中科技大学，2005，1-147
[10] Naksimovich N. P, Yeremina L. E. Sensors and Actuators B, 1993, 13-14: 256-258
[11] 马戎，周王民，陈明．气体传感器的研究及发展方向．航空计测技术综合评述，2004，24(4)：1-4
[12] 王玮．基于气体传感器阵列的混合气体检测系统：[博士学位论文]．西北工业大学，2002，1-128
[13] 刘义祥．气体传感器在气体泄漏事故处理中的应用．消防技术与产品信息，2002，(2)：36-38
[14] WANG Y D, SLTN X D, LI Y F, et al. Perovskite-type NiSnO3 used as the ethanol sensitive material. Solid-State Electron, 2000, 44: 2009-2014.
[15] Yun E S, Park T H,. Biotechnol Bioprocess Eng, 2000, 5(2): 150.
[16] Wenyi Zhang, H. Uchida, T. Katsube, et al. A novel semiconductor NO gas sensor operating at room temperature. Sensors and Actuators B, 1998, 49: 58-62
[17] Satoshi Ozawa, Peter C. Hauser, Kurt Seiler et al. Ammonia gas selective optical sensors based on neutral ionophores. Anal. Chem, 1991, 63, 640-644
[18] M. Penza, E. Milella, V. I. Anisimkin. Monitoring of NH_3 gas by LB polypyrrole-based SAW sensor. Sensors and Actuators B, 1998, 47: 218-224.
[19] Kong J, Franklin N. R, Zhou C. W. et al. Nanotube molecular wires as chemicalsensors. Science, 2000, 287(1): 622-625
[20] 段振新．氨敏场效应晶体管微型化的研究．传感器技术，1991，2：10-12
[21] 皱德恕，王东风，高国．MOS集成氨敏传感器．传感器技术，1997，7：6-8
[22] Xusheng Wang, Norio Miura, Noboru Yamazoe. Study of WO3 based sensing materials for NH3 and NO detection. Sensor and Actutors B, 2000, 66: 74-76.
[23] A. Teeramongkonrasmee, M. Sriyudthsak Methanol and ammonia sensing characteristics of sol-gel derived thin film gas sensor. Sensors and Actuators B, 2000, 66: 256-259.
[24] G. S. Trivikrama Rao, D. Tarakarama Rao. Gas sensitivity of ZnO based thick film sensor to NH3 at room temperature. Sensors and Actuators B, 1999, 55: 166-169
[25] L. H. Huo, X. L. Lia, W. Lia et al. Gas sensitivity of composite Langrnuir-Blodgett films of Fe_2O_3 nanoparticle-copper phthalocyanine. Sensors and Actuators B, 2000, 71: 77-81
[26] A. Galdikas, A. Mironas, V. Strazdiene et al. Room temperature functioning ammonia sensor based on solid-state Cu_xS films. Sensors and Actuators B, 2000, 67: 76-83.
[27] V. Romanovakaya, M. Ivanovskaya, P. Bogdanov. A Study of sensing properties of Pt-and Au-loaded In_2O_3 ceramics. Sensors and Actuators B, 1999, 56: 31-36.
[28] D. Mutschall, K. Holzner, E. Obermeier. Sputtered molybdenum oxide thin films for NH_3 detection. Sensors and Actuators B, 1996, 35-36: 320-324
[29] Afshad Talaie, Conducting polymer based pH detector: a new outlook to pH sensing technology, Polymer, 1997, 38(5): 1145-1150
[30] S. C. K. Misraa, Prafull Mathura, Maneesha Yadava, M. K. Tiwaria, S. C. Garga, P. Tripathib, Preparation and characterization of vacuum deposited semiconducting nanocrystalline polymeric thin film sensors for detection of HCI, Polymer 45 (2004) 8623-8628
[31] V. V. Chabukswar, Sushama Pethkar, Anjali A. Athawale, Acrylic acid doped polyaniline as an ammonia sensor, Sensors and Actuators, 2001, B77: 657663
[32] 肖恺，于贵，刘云圻．有机场效应晶体管研究和应用进展．科学通，2002，47(12)：881-890
[33] Burgmair M., Eisels I. Contribution of the gate insulator surface to work function measurements with a gas sensitive FET. Sensors, 2002. Proceedings of IEEE, 1: 439-442
[34] 王阳元，关旭东，马俊如．集成电路工艺基础．北京：高等教育出版社，1991，1-609
[35] 叶龙，李焰．有机敏感材料NO_2气体传感器．传感器技术，1994，(4)：1-6
[36] 陈湘宁．导电薄膜BAYTRON及其应用．华工新型材料，1999，27(9)：36-37
[37] Liu Niu, Carita Kvarnstrom, K. Froberg, et al. Electrochemically controlled surface morphology and crystallinity in poly(3,4-ethylenedioxythioxythiophene). Synthetic Metals, 2001, 56: 425-429
[38] M Brown, J. S. Kim, R. H. Friend, et al. Effect of poly(3,4-ethylene dioxythiophene) on the built-in field in polymer light-emitting diodes probed by electroabsorption spectroscopy, Synthetic Metals, 2000, 111: 285-287
[39] M. Bouguettaya, N. Vedie, C. Chevrol. New conductive adhesive based on Poly(3,4-ethylene dioxythiophene), Synthetic Metals, 1999, 102: 1428-1431.
[40] K. E Aasmundtveit, E. J. Samuelsen, L. A. A. Pettersson, et all. Structure of thin films of poly(3,4-ethylenedioxythioxythiophene). Synthetic Metals, 1999, 112: 561-564
[41] Andersson M, Holmberg M., Lundstrom l., et al. Development of a ChemFET sensor with molecular films of porphyrins as sensitive layer. Sensors and Actuators B, 2001, 77: 567-571
[42] 陈国华，颜文礼．化学法合成导电聚吡咯的研究现状．华侨大学学报(自然科学版)，1994，15(2)：172-176
[43] De Souza J E G, Dos Santos F L, Barros-Neto B. Polypyrrole thin films gas sensors. Synthetic Metals, 2001, 119: 383-384
[44] Sgritski V S, Reut J, Opik A, et al. Environmental QCM sensors toted with polypyrrole. Synthetic Metals, 1999, 102: 1326-132
[45] Lin-Xia Wang, Xin-Gui Li, Yu-Liang Yang. Praparation, properties and applications of polypyrroles. Reactive&Functional Polymers, 2001, 47(2): 125-139
[46] 尹五生．聚吡咯导电材料合成方法的进展．功能材料，1996，27 C2)：97-102
[47] 徐友龙，季锐，王飞．影响掺杂聚吡咯(PPy)导电性能的因素．电子元件与材料，2000，19(5)：17-19
[48] 万本强，吴婉群．催化电合成聚吡咯的电化学性质研究．西南师范大学学报(自然科学版)，1993，18(1)：52-55
[49] 贝建中，钱人元．在水溶液中电化学反应制备大面积聚吡咯膜．功能高分子学报，1991，4(4)：320-324
[50] Gouri Smithy Akundy, Jude O. Iroh. Polypyrrole coatings on aluminum-synthesis and characterization. Polymer, 2001, 42 (24): 9665-9669
[51] 丁文艳，李丹，汪信，陆路德，杨绪杰．聚电解质自组装膜对聚吡咯原位沉积的影响．功能材料，2002，33(4)：437～439
[52] M. K. Rima, M. Adamib, P. FaRicib, C. Nicolinic. Physical insight in the in-situ self-assembled firms of polypyrrole. Polymer, 2000, 41: 7499-7509
[53] 许均，曾幸荣，李鹏，邓惠萍，苏海霞．聚吡咯／二氧化硅复合材料的制备及导电性的研究．化学与黏合，2005，No．1，Vol．27：1～4
[54] 裘式纶，等，纳米材料研究进展．化学研究及应用，1998，10(4)：331
[55] Danielle C. Schnitzler, Michelle S. Meruvia, No A. Hummelgen, and Aldo J. G zarbin. Preparation and Characterization of Novel Hybrid Materials Formed from (Ti,Sn)O_2 Nanoparticles and Polyaniline. Chem. Mater, 2003, 15: 4658-4665
[56] George Z. Chen, Milo S. P. Shaffer, Dan Coleby, Gemma Dixon, Wuzong Zhou, Derek J. Fray, and Alan H. Windle. Carbon Nanotube and Polypyrrole Composites. Coating and Doping, Adv. Mater. 2000, 12(7): 522-526.
[57] Kay Hyeok An, Seung Yol Jeong, Ha Ryong Hwang, and Young Hee Lee. Enhanced Sensitivity of a Gas Sensor Incorporing Single-Walled Carbon Nanotube-Polypyrrole Nanocomposites. Advanced Materials, 2004, 16(12): 1005-1009
[58] Huseyin Zengin, Wensheng Zhou, Jiangyong Jin, Richard Czerw, Dennis W. Smith, Luis Echegoyen, David L. carroll, Stephen H. Foulger, and John Ballato. Carbon Nanotube Doped Polyaniline. Advanced Materials, 2002, 14(20): 1480-1483
[59] Jiaxing Huang and Richard B. Kaner. A General Chemical Route to Polyaniline Nanofibers. J. AM. CHEM. SOC, 2004, 126, 851-855
[60] M. Matsuguchi, J. Io, G Sugiyama, Y. Sakai, Effects of NH3 gas on the electrical conductivity of polyaniline blend films. Synthetic Metals, 2002, 128: 1519
[61] M. Baibarac, I. Baltog, S. Lefrant, J. Y. Mevellec, and O. Chauvet, Polyaniline and Carbon Nanotube Based Composites Containting Whole Units and Fragments of Nanotubes. Chem. Mater, 2003, 15: 4149-4155
[62] M. K. Rama,, M. Adamib, P. Faracib, C. Nicolinic, Physical insight in the in-situ self-assembled films of polypyrrole, Polymer 41 (2000) 7499-7509
[63] Marie-isabelle Baraton, Lhadi Merhari, Jianzhao Wang and Kenneth E Gonsalves, Investigation of the TiO_2/PPV nanocomposite for gas sensing application. Nanotechnoiogy, 1998, 9: 356～359
[64] 张玉泉，于跃华，丁雪佳，崔国强，刘丽敏，李长江．聚吡咯／纳米氧化钇复合材料的结构与性能研究．现代化工，2004，No．1，Vol．24：37-39
[65] Manoj K. Ram, Ozlem Yavuz, Matt AIdissi, NO_2 gas sensing based on ordered ultrathin films of conducting polymer and its nanocomposite, Synthetic Metals 151 (2005) 77-84
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |