苯系物碳纳米管气敏传感器的研制
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摘要
碳纳米管由于具有比表面积高、孔隙结构丰富和表面能高等特点,受到了研究人员的广泛关注。采用碳纳米管作为气敏材料的气体传感器具有高灵敏度、低响应时间和良好的稳定性等优点,具有广阔的应用前景。
本文主要针对碳纳米管气敏传感器对苯系物的响应特性开展研究。由于碳纳米管薄膜具有孔状结构,苯系物气体分子能够在其中发生分子吸附以及毛细凝聚。由于苯系物气体分子的吸附,碳纳米管吸附气体后电容值随气体浓度的改变而改变,据此可以通过传感器电容的改变来测试气体浓度的改变。基于上述工作原理,选择丝网印刷工艺制备了掺杂低温玻璃粉的碳纳米管薄膜苯系物传感器。根据气体测试的要求,设计满足气密性好、浓度可控、可观察等要求的碳纳米管苯系物传感器测试装置。
利用蒸镀和光刻的工艺制作出Al电极,通过丝网印刷方式制作出碳纳米管薄膜,进而制作出叉指电容式碳纳米管苯系物气敏传感器。对碳纳米管进行化学修饰,对化学修饰后的碳纳米管传感器的性能进行测试。实验结果表明,经过化学修饰可提高传感器对低浓度被测物的灵敏度和稳定性。通过测试碳纳米管苯系物传感器对不同测试频率的响应,综合考虑灵敏度和稳定性等方面因素,选定测试系统的测试频率为1kHz。以苯、甲苯、二甲苯为被测对象,对碳纳米管苯系物传感器的响应与恢复时间、重复特性、灵敏度、温度特性等性能进行测试。结果表明碳纳米管苯系物传感器具有响应速度快、重复性好等优点,而且在相同温度条件下,对二甲苯的灵敏度最高。
Because of the special characteristics of large surface-volume ratio, abundant hole structure and high surface activity, carbon nanotubes (CNTs) has drawn much more attention by many researchers. They can be used as gas sensing material, so gas adsorption process with high sensitivity, fast response time and advantages of long-term stability. Thus, they exhibit broad application prospects.
This article focuses on carbon nanotube gas sensor response characteristics of benzene gas. As the carbon nanotube film has a pore-like structure, benzene gas molecules can congregate due to molecular adsorption and capillary condensation. As the benzene gas molecules adsorbed, the dielectric constant of carbon nanotubes changes with the gas concentration. Thus, capacitance change of the sensor could test the gas concentration changes. Based on the above concept, we choose the screen printing to prepare carbon nanotube benzene sensor adulterated with low temperature glass power, films doped benzene sensor. With the requirements of the gas test, we design a benzene sensor test device which meets air tightness, concentration control, well observation and other requirements of the carbon nanotubes.
Inter-digital capacitive benzene Multi-walled carbon nanotubes (MWNTs) sensor, whose electrode is made by evaporation and photolithography technology and the films are made by screen printing technology is introduced in this paper. By testing benzene carbon nanotube sensor in different frequencies and considering the sensitivity and stability factors, we selected the test system at a frequency of 1kHz. Characteristics of sensor’s sensitivity response time, recovery time repeatability, temperature performance are evaluated with benzene, toluene, xylene. Test results show that the benzene carbon nanotube sensor performs well. At the same temperature conditions, it is most sensitive to xylene. Finally, chemical modification of carbon nanotubes to improve sensor performance was tested for its effectiveness. The results showed that chemical modification can improve the sensor sensitivity and stability of the low concentration measured object.
本文主要针对碳纳米管气敏传感器对苯系物的响应特性开展研究。由于碳纳米管薄膜具有孔状结构,苯系物气体分子能够在其中发生分子吸附以及毛细凝聚。由于苯系物气体分子的吸附,碳纳米管吸附气体后电容值随气体浓度的改变而改变,据此可以通过传感器电容的改变来测试气体浓度的改变。基于上述工作原理,选择丝网印刷工艺制备了掺杂低温玻璃粉的碳纳米管薄膜苯系物传感器。根据气体测试的要求,设计满足气密性好、浓度可控、可观察等要求的碳纳米管苯系物传感器测试装置。
利用蒸镀和光刻的工艺制作出Al电极,通过丝网印刷方式制作出碳纳米管薄膜,进而制作出叉指电容式碳纳米管苯系物气敏传感器。对碳纳米管进行化学修饰,对化学修饰后的碳纳米管传感器的性能进行测试。实验结果表明,经过化学修饰可提高传感器对低浓度被测物的灵敏度和稳定性。通过测试碳纳米管苯系物传感器对不同测试频率的响应,综合考虑灵敏度和稳定性等方面因素,选定测试系统的测试频率为1kHz。以苯、甲苯、二甲苯为被测对象,对碳纳米管苯系物传感器的响应与恢复时间、重复特性、灵敏度、温度特性等性能进行测试。结果表明碳纳米管苯系物传感器具有响应速度快、重复性好等优点,而且在相同温度条件下,对二甲苯的灵敏度最高。
Because of the special characteristics of large surface-volume ratio, abundant hole structure and high surface activity, carbon nanotubes (CNTs) has drawn much more attention by many researchers. They can be used as gas sensing material, so gas adsorption process with high sensitivity, fast response time and advantages of long-term stability. Thus, they exhibit broad application prospects.
This article focuses on carbon nanotube gas sensor response characteristics of benzene gas. As the carbon nanotube film has a pore-like structure, benzene gas molecules can congregate due to molecular adsorption and capillary condensation. As the benzene gas molecules adsorbed, the dielectric constant of carbon nanotubes changes with the gas concentration. Thus, capacitance change of the sensor could test the gas concentration changes. Based on the above concept, we choose the screen printing to prepare carbon nanotube benzene sensor adulterated with low temperature glass power, films doped benzene sensor. With the requirements of the gas test, we design a benzene sensor test device which meets air tightness, concentration control, well observation and other requirements of the carbon nanotubes.
Inter-digital capacitive benzene Multi-walled carbon nanotubes (MWNTs) sensor, whose electrode is made by evaporation and photolithography technology and the films are made by screen printing technology is introduced in this paper. By testing benzene carbon nanotube sensor in different frequencies and considering the sensitivity and stability factors, we selected the test system at a frequency of 1kHz. Characteristics of sensor’s sensitivity response time, recovery time repeatability, temperature performance are evaluated with benzene, toluene, xylene. Test results show that the benzene carbon nanotube sensor performs well. At the same temperature conditions, it is most sensitive to xylene. Finally, chemical modification of carbon nanotubes to improve sensor performance was tested for its effectiveness. The results showed that chemical modification can improve the sensor sensitivity and stability of the low concentration measured object.
引文
1 J.Gutiérrez, J.Getino, M.C.Horrillo, etc. Electrical characterization of a thin film tin oxide sensor array for VOCs detection. Thin Solid Films. 1998, 317(1-2): 429~431
2 J.Hubálek, K.Malysz, J.Prá?ek, etc. Pt-loaded Al 2 O3 catalytic filters for screen-printed WO3 sensors highly selective to benzene. Sensors and Actuators B. 2004, 101(3): 277~283
3 C.W.Lin,Y.L.Lui,R.Thangamuthu. Investigation of the relationship between surface thermodynamics of the chemically synthesized Polypyrrole films and their gas-sensing responses to BTEX compounds. Sensors and Actuators B. 2003, 94(1): 36~45
4 M.C.Gallazzi, L.Tassoni, C.Bertarelli, etc. Poly (alkoxy- bithiophenes) sensor for organic vapours. Sensors and Actuators B. 2003, 88(2): 178~189
5 Lee D.S, Jung J.K, Lim J.W. Recognition of volatile organic compounds using SnO2 sensor array and Patten recognition analysis. Sensors and Aeotators B. 2001, 77(1-2): 228~236
6 Mohammed Mabrook, Peter Hawkins. A rapidly-responding sensor for benzene, methanol and ethanol vapours based on films of titanium dioxide dispersed in a polymer operating at room temperature. Sensors and Actuators B. 2001, 75(3): 197~202
7王欢. VOCs气敏传感器的制备及性能研究.四川大学硕士学位论文.12~13
8 Huang Wei, Wang Yao, Luo Guohua, et al. 99.9% purity multi-walled carbon nanotubes by vacuum high-temperature annealing. Carbon. 2003, 41(13): 2585~2590
9张登松,代凯,方建慧,等.碳纳米管改性处理的研究.化工矿物与加工. 2004, 33(3): 14~17
10 Young Soo Park, Young Chul Choi, Keun Soo Kim, et al. High yield purification of multiwalled carbon nanotubes by selective oxidation during thermal annealing. Carbon. 2001, 39(5): 655~661
11 A.Modi, N.Koratkar, E.Lass, B. Wei, et a1. Miniaturized Gas IonizationSensors Using Carbon Nanotubes. Nature. 2003, 424(6945): l7l~l74
12 Valentini L, Cantalini C, Lozzi, et al. Reversible oxidation effeets on carbon nanotubes thin films for gas sensing applications. Materials Science and Engineering C. 2003, 23(4): 523~529
13 Cantalini C, Valentini L, Armentanol, et al. Sensitivity to NO2 and cross-sensitivity analysis to NH3, ethanol and humidity of carbon nanotubes thin film prepared by PECVD. Sensors and Aetuators B. 2003, 95(1): 195~202
14 Cantalini C, Valentini L, Lozzi L, et al. NO2 gas sensitivity of carbon nanotubes obtained by plasma enhanced chemical vapor deposition. Sensors and Actuators B. 2003, 93(1-3): 333~337
15 Valentini L, Lozzi L, Cantalini C, et al. Effects of oxygen annealing on gas sensing properties of carbon nanotubes thin films. The Solid Films. 2003, 436(1): 95~100
16 Cantalini C, Valentini L, Armentano I, etal. Carbon nanotubes as new materials for gas sensing applications. Journal of European Ceramic Society. 2004, 24(6): 1405~1408
17 Valentini L, Cantalini C, Armentano I, etal. Highly sensitive and selective sensors based on carbon nanotubes thin films for molecular detection. Diamond and Related Materials. 2004, 13(4-8):1301~1305
18 Youngmin Park, Ki-Young Dong, Jinwoo Lee,etc. Development of an ozone gas sensor using single-walled carbon nanotubes. Sensors and Actuators B. 2009, 140(2):407~411
19 I. Sayago, Terrado E, Aleixandre M, et al. Novel selective sensors based on carbon nanotube films for hydrogen detection. Sensors and Aetuators B. 2006, 122(1): 75~80
20 Nguyen Van Hieu, Luong Thi Bich Thuy, Nguyen Duc Chien. Highly sensitive thin film NH3 gas sensor operating at room temperature based on SnO 2/MWCNTs composite. Sensors and Aetuators B. 2008, 129(2): 888~895
21 Yang L, Huicai W, Mujie Y. n-Type gas sensing characteristics of chemically modified multi-walled carbon nanotubes and PMMA composite. Sensors and Aetuators B. 2006, 121(2): 496~500
22 Yousi C, Yang L, Huicai W, et al. Gas sensitivity of a Composite ofmulti-walled carbon nanotubes and Polypyrrole Prepared by Vapor Phase Polymerization. Carbon. 2006, 45(2): 357~363
23 Bee-Yu W, Ming-Chih H, Pi-Guey S, et al. A novel SnO2 gas sensor doped With carbon nanotubes operating at room temperature. Sensors and Aetuators B. 2004, 101(1-2): 81~89
24 M. Consalesa, A. Crescitellia, M. Penzab, P. Aversab, P. Delli Veneric, M. Giordanod, A. Cusanoa. SWCNT nano-composite optical sensors for VOC and gas trace detection. Sensors and Actuators B. 2009, 138(1): 351~361
25季振国,孙兰侠,何振杰,等.可鉴别室内有害气体的锢锡氧化物薄膜气敏特性研究.传感技术学报,2004,6(2): 277~279
26王智民,张新,张艳熹,等.旁热TiO 2 /MoO3复合厚膜邻二甲苯气敏陶瓷元件的制备及特性表征.黑龙江大学自然科学学报. 2003,20(2): 89~92
27裴素华,孙海波,张华,等.γ- Fe 2 O3响应苯类气体敏感材料特性研究.功能材料与器件学报,2004,10(1) :41~44.
28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.传感技术学报,2003,12(4) :491~493
29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.传感技术学报,2005,3(1) :43~46
30司士辉,朱德荣,陈昕.TiO2纳微孔膜增敏的压电石英晶体传感器.中南工业大学学报. 2002,33(5) :477~479
31黄载福,解玉华,卢贤曜,等.冠醚涂层压电石英晶体传感器对甲苯、二甲苯的检测研究.环境科学.15(1) :6~9
32 Liang Y. X., Chen Y J, Wang T H. Low-resistance gas sensors fabricated from multiwalled carbon nanotubes coated with a thin tin oxide layer. Applied Physics Letters, 2004, 85 (4): 666~668
33 Yan-Li L, Hai-Feng Y, Yu Y, etc. Gas sensing properties of tin dioxide coated onto multi- walled carbon nanotubes. Thin solid Films, 2006, 497(1-2): 355~360
34陈金霞,郭淼,陈文菊,等.基于多壁纳米碳管的传感器对甲苯的气敏性研究.传感技术学报. 2005, 18(1) :39~42
35方向生,郭淼,陈文菊,等.碳纳米管及其修饰物对挥发性有机物气敏性的研究.传感技术学报. 2006, 19(5) :2130~2134
36靳军.多壁碳纳米管的功能化和光化学、电化学传感器的研究兰州大学博士论文. 2008:30~35
37仇巍.碳纳米管应变传感器测量理论与显微拉曼应变测量技术.天津大学博士论文. 2008:42~47
38吴莉莉.纳米碳管气敏传感器及随机共振检测系统的研究.浙江大学博士论文. 2008:12~13
39颜丙勇.碳纳米管电离式气体传感器的基础研究.上海交通大学博士论文. 2006:22~23
40李昱.纳米碳管的制备、表面修饰及其初步用于葡萄糖生物传感器的研究.浙江大学博士论文. 2006: 32~33
41惠国华.基于随机共振和定向多壁纳米碳管气敏传感器阵列的SF6气体检测系统的研究.浙江大学博士论文. 2008: 12~14
42渠凤丽.新型纳米线阵列及碳纳米管复合体系的电化学生物传感器研究.湖南大学博士论文. 2008: 21~24
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44陈金华.基于碳纳米管的化学与生物传感.第十四次全国电化学会议.扬州. 2007:84~85
45毛莉.碳纳米材料的可控制备、表征及应用研究.大连理工大学. 2007:9~15
46丛松颖,碳纳米管在气湿敏传感器中的应用研究。大连理工大学硕士论文. 2007:5~9
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48陈晓峰.碳纳米管复合膜修饰电极对有机污染物的检测研究.华中科技大学硕士论文. 2008:10~12
49王淑敏.化学修饰电极的研制及其在分析化学中的应用研究.河南大学硕士论文. 2008:22~25
2 J.Hubálek, K.Malysz, J.Prá?ek, etc. Pt-loaded Al 2 O3 catalytic filters for screen-printed WO3 sensors highly selective to benzene. Sensors and Actuators B. 2004, 101(3): 277~283
3 C.W.Lin,Y.L.Lui,R.Thangamuthu. Investigation of the relationship between surface thermodynamics of the chemically synthesized Polypyrrole films and their gas-sensing responses to BTEX compounds. Sensors and Actuators B. 2003, 94(1): 36~45
4 M.C.Gallazzi, L.Tassoni, C.Bertarelli, etc. Poly (alkoxy- bithiophenes) sensor for organic vapours. Sensors and Actuators B. 2003, 88(2): 178~189
5 Lee D.S, Jung J.K, Lim J.W. Recognition of volatile organic compounds using SnO2 sensor array and Patten recognition analysis. Sensors and Aeotators B. 2001, 77(1-2): 228~236
6 Mohammed Mabrook, Peter Hawkins. A rapidly-responding sensor for benzene, methanol and ethanol vapours based on films of titanium dioxide dispersed in a polymer operating at room temperature. Sensors and Actuators B. 2001, 75(3): 197~202
7王欢. VOCs气敏传感器的制备及性能研究.四川大学硕士学位论文.12~13
8 Huang Wei, Wang Yao, Luo Guohua, et al. 99.9% purity multi-walled carbon nanotubes by vacuum high-temperature annealing. Carbon. 2003, 41(13): 2585~2590
9张登松,代凯,方建慧,等.碳纳米管改性处理的研究.化工矿物与加工. 2004, 33(3): 14~17
10 Young Soo Park, Young Chul Choi, Keun Soo Kim, et al. High yield purification of multiwalled carbon nanotubes by selective oxidation during thermal annealing. Carbon. 2001, 39(5): 655~661
11 A.Modi, N.Koratkar, E.Lass, B. Wei, et a1. Miniaturized Gas IonizationSensors Using Carbon Nanotubes. Nature. 2003, 424(6945): l7l~l74
12 Valentini L, Cantalini C, Lozzi, et al. Reversible oxidation effeets on carbon nanotubes thin films for gas sensing applications. Materials Science and Engineering C. 2003, 23(4): 523~529
13 Cantalini C, Valentini L, Armentanol, et al. Sensitivity to NO2 and cross-sensitivity analysis to NH3, ethanol and humidity of carbon nanotubes thin film prepared by PECVD. Sensors and Aetuators B. 2003, 95(1): 195~202
14 Cantalini C, Valentini L, Lozzi L, et al. NO2 gas sensitivity of carbon nanotubes obtained by plasma enhanced chemical vapor deposition. Sensors and Actuators B. 2003, 93(1-3): 333~337
15 Valentini L, Lozzi L, Cantalini C, et al. Effects of oxygen annealing on gas sensing properties of carbon nanotubes thin films. The Solid Films. 2003, 436(1): 95~100
16 Cantalini C, Valentini L, Armentano I, etal. Carbon nanotubes as new materials for gas sensing applications. Journal of European Ceramic Society. 2004, 24(6): 1405~1408
17 Valentini L, Cantalini C, Armentano I, etal. Highly sensitive and selective sensors based on carbon nanotubes thin films for molecular detection. Diamond and Related Materials. 2004, 13(4-8):1301~1305
18 Youngmin Park, Ki-Young Dong, Jinwoo Lee,etc. Development of an ozone gas sensor using single-walled carbon nanotubes. Sensors and Actuators B. 2009, 140(2):407~411
19 I. Sayago, Terrado E, Aleixandre M, et al. Novel selective sensors based on carbon nanotube films for hydrogen detection. Sensors and Aetuators B. 2006, 122(1): 75~80
20 Nguyen Van Hieu, Luong Thi Bich Thuy, Nguyen Duc Chien. Highly sensitive thin film NH3 gas sensor operating at room temperature based on SnO 2/MWCNTs composite. Sensors and Aetuators B. 2008, 129(2): 888~895
21 Yang L, Huicai W, Mujie Y. n-Type gas sensing characteristics of chemically modified multi-walled carbon nanotubes and PMMA composite. Sensors and Aetuators B. 2006, 121(2): 496~500
22 Yousi C, Yang L, Huicai W, et al. Gas sensitivity of a Composite ofmulti-walled carbon nanotubes and Polypyrrole Prepared by Vapor Phase Polymerization. Carbon. 2006, 45(2): 357~363
23 Bee-Yu W, Ming-Chih H, Pi-Guey S, et al. A novel SnO2 gas sensor doped With carbon nanotubes operating at room temperature. Sensors and Aetuators B. 2004, 101(1-2): 81~89
24 M. Consalesa, A. Crescitellia, M. Penzab, P. Aversab, P. Delli Veneric, M. Giordanod, A. Cusanoa. SWCNT nano-composite optical sensors for VOC and gas trace detection. Sensors and Actuators B. 2009, 138(1): 351~361
25季振国,孙兰侠,何振杰,等.可鉴别室内有害气体的锢锡氧化物薄膜气敏特性研究.传感技术学报,2004,6(2): 277~279
26王智民,张新,张艳熹,等.旁热TiO 2 /MoO3复合厚膜邻二甲苯气敏陶瓷元件的制备及特性表征.黑龙江大学自然科学学报. 2003,20(2): 89~92
27裴素华,孙海波,张华,等.γ- Fe 2 O3响应苯类气体敏感材料特性研究.功能材料与器件学报,2004,10(1) :41~44.
28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.传感技术学报,2003,12(4) :491~493
29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.传感技术学报,2005,3(1) :43~46
30司士辉,朱德荣,陈昕.TiO2纳微孔膜增敏的压电石英晶体传感器.中南工业大学学报. 2002,33(5) :477~479
31黄载福,解玉华,卢贤曜,等.冠醚涂层压电石英晶体传感器对甲苯、二甲苯的检测研究.环境科学.15(1) :6~9
32 Liang Y. X., Chen Y J, Wang T H. Low-resistance gas sensors fabricated from multiwalled carbon nanotubes coated with a thin tin oxide layer. Applied Physics Letters, 2004, 85 (4): 666~668
33 Yan-Li L, Hai-Feng Y, Yu Y, etc. Gas sensing properties of tin dioxide coated onto multi- walled carbon nanotubes. Thin solid Films, 2006, 497(1-2): 355~360
34陈金霞,郭淼,陈文菊,等.基于多壁纳米碳管的传感器对甲苯的气敏性研究.传感技术学报. 2005, 18(1) :39~42
35方向生,郭淼,陈文菊,等.碳纳米管及其修饰物对挥发性有机物气敏性的研究.传感技术学报. 2006, 19(5) :2130~2134
36靳军.多壁碳纳米管的功能化和光化学、电化学传感器的研究兰州大学博士论文. 2008:30~35
37仇巍.碳纳米管应变传感器测量理论与显微拉曼应变测量技术.天津大学博士论文. 2008:42~47
38吴莉莉.纳米碳管气敏传感器及随机共振检测系统的研究.浙江大学博士论文. 2008:12~13
39颜丙勇.碳纳米管电离式气体传感器的基础研究.上海交通大学博士论文. 2006:22~23
40李昱.纳米碳管的制备、表面修饰及其初步用于葡萄糖生物传感器的研究.浙江大学博士论文. 2006: 32~33
41惠国华.基于随机共振和定向多壁纳米碳管气敏传感器阵列的SF6气体检测系统的研究.浙江大学博士论文. 2008: 12~14
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