本研究藉由印刷電極結合軟性基板的製程，成功開發低成本、低功耗的電阻式氣體感測器。在指叉電極上塗佈一層高分子與導電材(碳黑)複合薄膜，藉由量測其吸脫附氣體的電阻變化值，來得知其量測氣體的能力。透過七個感測器陣列，可在數個感測區塗佈不同的高分子，每種高分子會對氣體有不同的響應，分析其電阻變化值，即可達到辨識或分類氣體的目標。因應環境中對人體的有害的揮發性氣體及易燃性的爆炸性氣體，氣體感測器可即時監控並避免危害，因此其對於物聯網的整合或智慧穿戴式裝置的應用，乃不可或缺的一環。
感測器電極圖形共設計出八種不同線寬線距組合，並與工研院合作，將電極印刷在玻璃及軟性基板PET上，運用已開發的感測材料PNVP塗佈在試片上，進行對乙醇與甲烷的測試，找出反應及靈敏度最大的線寬/線距組合為20μm/20μm，其對乙醇感測極限約為40ppm，對甲烷的感測極限則為32ppm，且乙醇與甲烷的反應變化相反。此外也比較了PNVP、P4VP、PS等三種不同感測材料對乙醇及甲烷的反應大小，以及彎曲感測器對量測的影響，並做穩定性、重覆性、對濕度影響等感測器能力分析，達成建立穿戴式感測平台及其應用的目標。

　　In this research, we combine the printed electrodes and flexible substrate to develop a low-cost resistive gas sensor with low energy-consumption. After coating a thin layer of polymer and carbon black mixture, the ability of measuring gas can be derived by analyzing the resistance change due to the adsorption of the gas molecules by the polymer. The sensor array containing seven sensors can be coated with different polymer so that every polymer will response to gas differently. The goal of identifying or classifying gases can be reached by analyzing the resistance change.The integrated gas sensor not only can monitor those harmful volatile organic compounds and explosive gases real-time and also being part of the Internet of Things acting as the application of smart wearable devices.

Eight different combination of electrode’s width and gap are designed. ITRI helps to do the printing fabrication on the glass and PET substrates. One of the developed sensing materials PNVP is coated on the chips and tested by ethanol and methane. The most sensitive design of electrode’s width/gap is 20μm/20μm.The LOD towards ethanol is 40ppm and 32ppm for methane. The resistance change of the two gases is opposite. Besides PNVP, sensors coated with other polymers such as P4VP and PS are measure by different concentration of gases and derive the sensitivity of each. Since the substrate is flexible, bending influence to sensor is also considered.The stability test, reproducibility test are performed as well. Through these experiments, the gas sensor has great potential to achieve the purpose of establishing a wearable sensing platform.

摘要 i
Abstract ii
圖目錄 v
表目錄 viii
1. 緒論 1
1.1研究動機 1
1.2研究目標 2
2. 文獻回顧 5
2.1人類嗅覺簡介 5
2.2人工嗅覺電子鼻系統 7
2.3感測器定義 9
2.4感測器應用介紹 10
2.5氣體感測器種類介紹 14
2.5.1金氧半導體氣體感測器(Metal oxide semiconductor gas sensor) 14
2.5.2電化學氣體感測器(Electrochemical gas sensor) 15
2.5.3 紅外線氣體感測器(Infrared gas sensor) 16
2.5.4光離子化偵測器(Photoionization Detector, PID) 17
2.5.5石英晶體微量天平(Quartz Crystal Microbalance，QCM) 18
2.5.6懸臂樑氣體感測器(Cantilever beam gas sensor) 19
2.5.7表面聲波氣體感測器(Surface Acoustic Wave Sensor, SAW) 20
2.5.8導電高分子感測器( Conducting Polymer Sensor，CPs ) 20
2.5.9各種電子鼻之比較 21
2.6印刷電極與軟性基板感測器之相關文獻 23
3. 導電高分子氣體感測器原理 28
3.1感測器機制與電子鼻系統 28
3.2高分子黏彈性模型 30
3.2.1黏彈體(Viscoelasticity)介紹 30
3.2.2麥斯威爾模型(Maxwell model)與卡爾文模型(Kelvin model) 32
3.3高分子/基板系統 34
3.3.1高分子於水平方向體積變化模型 35
3.3.2高分子於垂直方向體積變化模型 37
3.3.3電阻式感測器電性模型 37
3.3.4感測器彎曲對感測的影響 38
3.4感測器電極設計 39
3.5氣體感測器指標 41
4. 感測器元件與系統設計 43
4.1電極設計 43
4.2電極印刷製程 45
4.3感測薄膜塗佈 48
4.3.1高分子配製與塗佈方式 48
4.3.2高分子吸附形式 49
4.3.3高分子選擇 51
4.4量測系統與環境 53
4.4.1實驗所用之儀器 53
4.4.2腔體設計與流場分析 61
4.4.3整體量測系統與環境 63
4.5量測方法與步驟 64
4.5.1 Arduino與MQ-3濃度校正 64
4.5.2 應變量測系統 66
4.5.3 氣體量測步驟 69
5. 實驗方法與結果討論 70
5.1穩定性測試 70
5.2吸脫附時間 71
5.3電極選擇 72
5.3.1各電極線寬/線距組合塗佈PNVP對乙醇的反應 72
5.3.2各電極線寬/線距組合塗佈PNVP對甲烷的反應 80
5.4 水氣對感測器之影響 84
5.5 不同高分子感測材料對乙醇/甲烷量測結果 85
5.6 感測器彎曲程度對乙醇感測的影響 87
6. 結論與未來展望 88
7. 參考文獻 90

[1] E. Kress-Rogers and R. ALSTOM, "Instrumentation for food quality assurance," Instrumentation and sensors for the food industry, vol. 2, 2001.
[2] S. Deshmukh, R. Bandyopadhyay, N. Bhattacharyya, R. Pandey, and A. Jana, "Application of electronic nose for industrial odors and gaseous emissions measurement and monitoring–an overview," Talanta, vol. 144, pp. 329-340, 2015.
[3] J. Poprawski, P. Boilot, and F. Tetelin, "Counterfeiting and quantification using an electronic nose in the perfumed cleaner industry," Sensors and Actuators B: Chemical, vol. 116, no. 1, pp. 156-160, 2006.
[4] J. Gardner, M. Craven, C. Dow, and E. Hines, "The prediction of bacteria type and culture growth phase by an electronic nose with a multi-layer perceptron network," Measurement Science and Technology, vol. 9, no. 1, p. 120, 1998.
[5] J. Gardner, E. Hines, F. Molinier, P. Bartlett, and T. Mottram, "Prediction of health of dairy cattle from breath samples using neural network with parametric model of dynamic response of array of semiconducting gas sensors," IEE Proceedings-Science, Measurement and Technology, vol. 146, no. 2, pp. 102-106, 1999.
[6] J. W. Gardner, H. W. Shin, and E. L. Hines, "An electronic nose system to diagnose illness," Sensors and Actuators B: Chemical, vol. 70, no. 1, pp. 19-24, 2000.
[7] H. Guohua, W. Yuling, Y. Dandan, D. Wenwen, Z. Linshan, and W. Lvye, "Study of peach freshness predictive method based on electronic nose," Food Control, vol. 28, no. 1, pp. 25-32, 2012.
[8] M. O’Connell, G. Valdora, G. Peltzer, and R. M. Negri, "A practical approach for fish freshness determinations using a portable electronic nose," Sensors and Actuators B: chemical, vol. 80, no. 2, pp. 149-154, 2001.
[9] S. Trirongjitmoah, Z. Juengmunkong, K. Srikulnath, and P. Somboon, "Classification of garlic cultivars using an electronic nose," Computers and Electronics in Agriculture, vol. 113, pp. 148-153, 2015.
[10] Z. Haddi, A. Amari, H. Alami, N. El Bari, E. Llobet, and B. Bouchikhi, "A portable electronic nose system for the identification of cannabis-based drugs," Sensors and Actuators B: Chemical, vol. 155, no. 2, pp. 456-463, 2011.
[11] T. Alizadeh and S. Zeynali, "Electronic nose based on the polymer coated SAW sensors array for the warfare agent simulants classification," Sensors and Actuators B: Chemical, vol. 129, no. 1, pp. 412-423, 2008.
[12] X. Zhou, J. Cheng, N. Zhao, and S. Chen, "A flexure-based high-throughput roll-to-roll printing system," in Proc. of the Annual Meeting of the ASPE Saint Paul, MN, USA, 2013, pp. 353-357.
[13] X. Zhou, H. Xu, N. Zhao, and S. Chen, "A flexure-based roll-to-roll machine for fabricating flexible photonic devices," in Proceedings of the annual meeting of the ASPE, 2014.
[14] W.-Y. Chung, Y.-D. Lee, and S.-J. Jung, "A wireless sensor network compatible wearable u-healthcare monitoring system using integrated ECG, accelerometer and SpO 2," in 2008 30th Annual International Conference of the IEEE Engineering in Medicine and Biology Society, 2008, pp. 1529-1532: IEEE.
[15] G. Miller, "Axel, Buck share award for deciphering how the nose knows," Science, vol. 306, no. 5694, p. 207, 2004.
[16] G. M. Shepherd, "Smell images and the flavour system in the human brain," Nature, vol. 444, no. 7117, pp. 316-321, 2006.
[17] "Individual sensitivity to odorants: genetic causes and molecular mechanisms," 2013.
[18] J. W. Gardner and P. N. Bartlett, "A brief history of electronic noses," Sensors and Actuators B: Chemical, vol. 18, no. 1, pp. 210-211, 1994/03/01 1994.
[19] J. W. Gardner, P. Bartlett, G. Dodd, and H. Shurmer, "Pattern recognition in the Warwick electronic nose," in 8th Int. Congress of the European Chemoreception Research Organisation, 1988.
[20] J. W. Gardner and P. N. Bartlett, Sensors and sensory systems for an electronic nose. Springer, 1992.
[21] K.-T. Tang, S.-W. Chiu, C.-H. Pan, H.-Y. Hsieh, Y.-S. Liang, and S.-C. Liu, "Development of a portable electronic nose system for the detection and classification of fruity odors," Sensors, vol. 10, no. 10, pp. 9179-9193, 2010.
[22] K. Arshak, E. Moore, G. Lyons, J. Harris, and S. Clifford, "A review of gas sensors employed in electronic nose applications," Sensor review, vol. 24, no. 2, pp. 181-198, 2004.
[23] J. R. Stetter, W. R. Penrose, and S. Yao, "Sensors, chemical sensors, electrochemical sensors, and ECS," Journal of The Electrochemical Society, vol. 150, no. 2, pp. S11-S16, 2003.
[24] N. Yamazoe, "Toward innovations of gas sensor technology," Sensors and Actuators B: Chemical, vol. 108, no. 1, pp. 2-14, 2005.
[25] S. Dragonieri et al., "An electronic nose in the discrimination of patients with non-small cell lung cancer and COPD," Lung Cancer, vol. 64, no. 2, pp. 166-170, 5// 2009.
[26] S. Dragonieri et al., "An electronic nose in the discrimination of patients with asthma and controls," Journal of Allergy and Clinical Immunology, vol. 120, no. 4, pp. 856-862, 10// 2007.
[27] S. Salehi, E. Nikan, A. A. Khodadadi, and Y. Mortazavi, "Highly sensitive carbon nanotubes–SnO 2 nanocomposite sensor for acetone detection in diabetes mellitus breath," Sensors and Actuators B: Chemical, vol. 205, pp. 261-267, 2014.
[28] S. De Prins et al., "Airway oxidative stress and inflammation markers in exhaled breath from children are linked with exposure to black carbon," Environment international, vol. 73, pp. 440-446, 2014.
[29] T. Seiyama and S. Kagawa, "Study on a Detector for Gaseous Components Using Semiconductive Thin Films," Analytical Chemistry, vol. 38, no. 8, pp. 1069-1073, 1966.
[30] N. Yamazoe, G. Sakai, and K. Shimanoe, "Oxide Semiconductor Gas Sensors," Catalysis Surveys from Asia, vol. 7, no. 1, pp. 63-75, 2003// 2003.
[31] S. Choopun, E. Wongrat, and N. Hongsith, Metal-oxide nanowires for gas sensors. INTECH Open Access Publisher, 2012.
[32] M. J. Tierney and H. O. L. Kim, "Electrochemical gas sensor with extremely fast response times," Analytical Chemistry, vol. 65, no. 23, pp. 3435-3440, 1993.
[33] L. Zhang, W.-b. YIN, L. Dong, L.-f. LI, H.-p. DOU, and S.-t. JIA, "Experimental of an infrared gas sensor based on infrared absorption spectrum theory in laboratory [J]," Journal of China Coal Society, vol. 4, p. 015, 2006.
[34] J. Wegener, A. Janshoff, and C. Steinem, "The quartz crystal microbalance as a novel means to study cell-substrate interactions in situ," Cell biochemistry and biophysics, vol. 34, no. 1, pp. 121-151, 2001.
[35] M. Von Schickfus, R. Stanzel, T. Kammereck, D. Weiskat, W. Dittrich, and H. Fuchs, "Improving the SAW gas sensor: device, electronics and sensor layer," Sensors and Actuators B: Chemical, vol. 19, no. 1-3, pp. 443-447, 1994.
[36] J. M. Slater, J. Paynter, and E. Watt, "Multi-layer conducting polymer gas sensor arrays for olfactory sensing," Analyst, vol. 118, no. 4, pp. 379-384, 1993.
[37] T. Syrový et al., "Gravure-printed ammonia sensor based on organic polyaniline colloids," Sensors and Actuators B: Chemical, vol. 225, pp. 510-516, 2016.
[38] T. Kinkeldei, C. Zysset, N. Münzenrieder, and G. Tröster, "An electronic nose on flexible substrates integrated into a smart textile," Sensors and Actuators B: Chemical, vol. 174, pp. 81-86, 2012.
[39] Y. S. Kim, "Microheater-integrated single gas sensor array chip fabricated on flexible polyimide substrate," Sensors and Actuators B: Chemical, vol. 114, no. 1, pp. 410-417, 2006.
[40] M. Ryan, M. Homer, M. Buehler, K. Manatt, F. Zee, and J. Graf, "Monitoring the air quality in a closed chamber using an electronic nose," SAE Technical Paper0148-7191, 1997.
[41] K. Domansky, V. Zapf, J. Grate, A. Ricco, W. Yelton, and J. Janata, "Integrated chemiresistor and work function microsensor array with carbon black/polymer composite materials," Sandia National Labs., Albuquerque, NM (United States)1998.
[42] A. Alexander, "Characterization of polymer based gas sensors with
a continuous system model," Mechanical Engineering Department, Lehigh University, 2006.
[43] M. C. Lonergan, E. J. Severin, B. J. Doleman, S. A. Beaber, R. H. Grubbs, and N. S. Lewis, "Array-based vapor sensing using chemically sensitive, carbon black− polymer resistors," Chemistry of Materials, vol. 8, no. 9, pp. 2298-2312, 1996.
[44] T. Kinkeldei, C. Zysset, N. Münzenrieder, and G. Tröster, "The influence of bending on the performance of flexible carbon black/polymer composite gas sensors," Journal of Polymer Science Part B: Polymer Physics, vol. 51, no. 5, pp. 329-336, 2013.
[45] W. H. Grover, "Interdigitated Array Electrode Sensors:Their Dsign, Efficiency, and Applications," Chemistry, University of Tennessee, Knoxville, 1999.