本研究的目標為製作出偵測香菸氣體的表面聲波( surface acoustic wave，SAW )氣體感測器，為了達到快速且低濃度的香菸偵測，將會對感測器靈敏度、穩定度、水氣影響等進行探討。靈敏度提升的方面，利用經過硝酸改質HMC而形成的非高分子式材料：氧化空心中孔洞碳球( oxidized hollow meso-porous carbon nano-sphere，O-HMC )取代SAW常用的高分子感測材料，獲得比聚丙烯酸( polyacrylic acid )更大的變化量；感測二手菸指示物( 3-ethenylpyridine )時，靈敏度從37.8 Hz/ppm提高到51.2 Hz/ppm。穩定度提升方面，本研究設計出體積為800μL的微型腔體，能在低流率( 20mL/min )的條件下加快反應時間之外亦可阻絕許多外界環境的干擾，同時也發現當實驗組與對照組的表面狀態越接近可以得到較高的穩定度，以未改質的HMC作為背景值，雜訊可下降至約5Hz，有助於提高S/N ratio。
香菸量測的部分，濾除粒徑超過1μm以上的香菸樣本後，即可大幅去除焦油與微粒黏附在晶片上的問題，並可重複的感測而且反應非常靈敏；同時和氨氣、甲烷、一氧化碳、二氧化碳這四種干擾氣體相比也有著5倍以上的選擇性。此外亦進行水氣的偵測，藉此去除濕度的影響，並利用得到的趨勢線對香菸產生的頻率變化量做校正。而除了偵測二手菸之外，本研究還對不同衣料纖維(羊毛、棉花、聚酯)上的三手菸進行感測，最終得知羊毛會吸附最大量的三手菸且殘留時間會最長。

Statistical data says that people exposed to secondhand smoke (SHS) have a higher risk of getting lung cancer and coronary heart disease. The research goal is making a cigarette sensor by surface acoustic wave (SAW) to prevent from tobacco hazards. In order to detect low concentration of cigarette marker, sensitivity and stability are two important issues. The SAW sensor is coated with oxidized hollow meso-porous carbon nano-sphere (O-HMC) to replace generally used polymer as new type sensing material, which is more sensitive than poly-acrylic acid due to the much more carboxyl group bonded by HNO3 treated, increasing the sensitivity of 3-EP from 37.8 to 51.2 Hz/ppm and also preventing the drawbacks of polymer based sensing material, such as lack of thermal stability and swelling effect. An 800μL micro-chamber is designed for enhancing stability by blocking environmental interferences, and the HMC coated chip is used as control due to the higher similarity of surface state between experiment and reference would increase stability, finally the noise can down to 5 Hz. The small volume of chamber and the large surface area of sensing material, caused by porous structure is leading to rapid detection at the low flow rate of 20 mL/min.
The SAW sensor successfully detects cigarette smoke with high sensitivity and good repeatability by filtering above 1μm particles and tar to solve the adhesion problem; as compared to four interfered gas, ammonia, methane, carbon monoxide and carbon dioxide, the SAW sensor has 5 times more selective to cigarette smoke. This SAW sensor also detects water vapor to remove the influence of humidity and uses the resulting trend line to calibrate the frequency shift by detecting cigarette. In addition to detect SHS, this research takes the same SAW detector to sense the thirdhand smoke (THS) on different clothing fabrics, such as wool, cotton and polyester, finally knows that wool will absorb the maximum amount of THS and get the longest residual time.

摘要 i
Abstract ii
致謝 vi
圖目錄 xi
表目錄 xv
第一章 緒論 1
1.1研究動機 1
1.2研究目標 8
第二章 文獻回顧 10
2.1 即時性香菸氣體感測器 10
2.2 GC用於香菸氣體分析 14
2.3氣體感測器種類 17
2.3.1半導體氣體感測器 17
2.3.2催化燃燒式氣體感測器 18
2.3.3電化學氣體感測器 18
2.3.4紅外線氣體感測器 20
2.3.5光離子化偵測器 20
2.3.6石英晶體微量天平 21
2.3.7表面聲波氣體感測器 21
2.3.8其他氣體感測器 22
2.3.9各種氣體感測器之比較 23
第三章 表面聲波感測器原理 25
3.1表面聲波簡介 25
3.2壓電效應 28
3.3壓電材料種類及材料參數 32
3.3.1尤拉角( Euler-angle )及切面 33
3.3.2機電耦合係數( electromechanical coupling coefficient, K2 ) 34
3.3.3溫度延遲係數( temperature coefficient of delay，TCD ) 35
3.3.4壓電基材的插入損失( insertion loss，IL ) 36
3.4指叉式電極轉換器 39
3.5表面聲波元件感測機制 45
3.6頻率飄移效應 46
3.7質量負載效應 48
第四章 表面聲波感測元件與系統設計 50
4.1表面聲波晶片製備 50
4.1.1表面聲波晶片設計 50
4.1.2黃光製程 52
4.2感測薄膜 57
4.2.1高分子塗佈方式 57
4.2.2高分子吸附形式 58
4.2.3高分子選擇 60
4.2.4摻雜碳載體之複合感測高分子薄膜 61
4.3電路設計 63
4.4量測系統與環境 66
4.4.1實驗所用之儀器 66
4.4.2微型腔體設計 70
4.4.3感測器量測系統與環境 72
4.4.4水氣量測系統 73
4.4.5三手菸量測系統 74
第五章 實驗結果 76
5.1感測材料之特性分析 76
5.1.1高分子式 76
5.1.2非高分子式 78
5.2感測材料造成之頻率飄移量 82
5.3穩定性測試 85
5.3.1溫度穩定性測試 85
5.3.2電壓穩定性測試 88
5.3.3表面狀態穩定性測試 89
5.4氣體樣品採集與鑑定 93
5.5水氣對感測器之影響 98
5.6三乙烯基吡啶(3-EP)氣體量測結果 103
5.6.1感測材料：PAA-HMC 103
5.6.2感測材料：O-HMC 107
5.6.3綜合比較 109
5.7尼古丁(Nicotine)氣體量測結果 114
5.8香菸量測 116
5.8.1濾除20μm之焦油與微粒 117
5.8.2濾除1μm之焦油與微粒 117
5.8.3濾除0.22μm之焦油與微粒 119
5.8.4綜合比較 120
5.9干擾氣體之選擇性 122
5.10氣體感測器指標 126
第六章 實驗結果-三手菸偵測 128
6.1重量法 128
6.2表面聲波感測法 130
第七章 結論 133
第八章 參考文獻 135

[1] R. Windom, "The health consequences of involuntary smoking. A report of the Surgeon General," U. S. DEPARTMENT HEALTH AND HUMAN SERVICE. 1986.
[2] S. K. Pandey and K.-H. Kim, "A review of environmental tobacco smoke and its determination in air," TrAC Trends in Analytical Chemistry, vol. 29, pp. 804-819, 2010.
[3] B. J. Apelberg, L. M. Hepp, E. Avila-Tang, L. Gundel, S. K. Hammond, M. F. Hovell, et al., "Environmental monitoring of secondhand smoke exposure," Tob Control, vol. 22, pp. 147-55, May 2013.
[4] M. Sleiman, H. Destaillats, J. D. Smith, C.-L. Liu, M. Ahmed, K. R. Wilson, et al., "Secondary organic aerosol formation from ozone-initiated reactions with nicotine and secondhand tobacco smoke," Atmospheric Environment, vol. 44, pp. 4191-4198, 2010.
[5] J. P. Winickoff, J. Friebely, S. E. Tanski, C. Sherrod, G. E. Matt, M. F. Hovell, et al., "Beliefs about the health effects of "thirdhand" smoke and home smoking bans," Pediatrics, vol. 123, pp. e74-9, Jan 2009.
[6] S. Vainiotalo, R. Vaaranrinta, J. Tornaeus, N. Aremo, T. Hase, and K. Peltonen, "Passive monitoring method for 3-ethenylpyridine: a marker for environmental tobacco smoke," Environmental science & technology, vol. 35, pp. 1818-1822, 2001.
[7] L. Kuusimäki, K. Peltonen, and S. Vainiotalo, "Assessment of environmental tobacco smoke exposure of Finnish restaurant workers, using 3‐ethenylpyridine as marker," Indoor Air, vol. 17, pp. 394-403, 2007.
[8] B. Koszowski, M. L. Goniewicz, J. Czogala, A. Zymelka, and A. Sobczak, "Simultaneous determination of nicotine and 3-vinylpyridine in single cigarette tobacco smoke and in indoor air using direct extraction to solid phase," International Journal of Environmental and Analytical Chemistry, vol. 89, pp. 105-117, 2009.
[9] D. Chowdhury, "Ni-Coated Polyaniline Nanowire As Chemical Sensing Material for Cigarette Smoke," The Journal of Physical Chemistry C, vol. 115, pp. 13554-13559, 2011.
[10] Y. Liu, S. Antwi-Boampong, J. J. BelBruno, M. A. Crane, and S. E. Tanski, "Detection of secondhand cigarette smoke via nicotine using conductive polymer films," Nicotine Tob Res, vol. 15, pp. 1511-8, Sep 2013.
[11] P. Ködderitzsch, R. Bischoff, P. Veitenhansl, W. Lorenz, and G. Bischoff, "Sensor array based measurement technique for fast-responding cigarette smoke analysis," Sensors and Actuators B: Chemical, vol. 107, pp. 479-489, 2005.
[12] C.-Y. Jiang, S.-H. Sun, Q.-D. Zhang, J.-H. Liu, J.-X. Zhang, Y.-L. Zong, et al., "Fast determination of 3-ethenylpyridine as a marker of environmental tobacco smoke at trace level using direct atmospheric pressure chemical ionization tandem mass spectrometry," Atmospheric Environment, vol. 67, pp. 1-7, 2013.
[13] I. Saito and H. Seto, "Measurement of Nicotine in Indoor Air Collected by Alkaline-coated Solid Phase Cartridge Followed by GC-MS Analysis," Journal of Health Science, vol. 53, pp. 53-59, 2007.
[14] H. Aikata, H. Takaishi, Y. Kawakami, S. Takahashi, M. Kitamoto, T. Nakanishi, et al., "Telomere Reduction in Human Liver Tissues with Age and Chronic Inflammation," Experimental Cell Research, vol. 256, pp. 578-582, 5/1/ 2000.
[15] P. H. Ku, C. Y. Hsiao, M. J. Chen, T. H. Lin, Y. T. Li, S. C. Liu, et al., "Polymer/Ordered Mesoporous Carbon Nanocomposite Platelets as Superior Sensing Materials for Gas Detection with Surface Acoustic Wave Devices," presented at the Langmuir, 2012.
[16] M. Thompson, Surface-Launched Acoustic Wave Sensors, 1997.
[17] C.-Y. Shen and S.-Y. Liou, "Surface acoustic wave gas monitor for ppm ammonia detection," Sensors and Actuators B: Chemical, vol. 131, pp. 673-679, 5/14/ 2008.
[18] G. Bidan, "Electroconducting conjugated polymers: New sensitive matrices to build up chemical or electrochemical sensors. A review," Sensors and Actuators B: Chemical, vol. 6, pp. 45-56, 1// 1992.
[19] L. Zhang, F. Meng, Y. Chen, J. Liu, Y. Sun, T. Luo, et al., "A novel ammonia sensor based on high density, small diameter polypyrrole nanowire arrays," Sensors and Actuators B: Chemical, vol. 142, pp. 204-209, 2009.
[20] P. Pacher, A. Lex, S. Eder, G. Trimmel, C. Slugovc, E. J. List, et al., "A novel concept for humidity compensated sub-ppm ammonia detection," Sensors and Actuators B: Chemical, vol. 145, pp. 181-184, 2010.
[21] H. T. Nagle, R. Gutierrez-Osuna, and S. S. Schiffman, "The how and why of electronic noses," Spectrum, IEEE, vol. 35, pp. 22-31, 1998.
[22] L. Rayleigh, "On waves propagated along the plane surface of an elastic solid," Proc. London Math. Soc., vol. 17, p. 4, 1885.
[23] 楊啟榮, 李清鋒, 施建富, "表面聲波生化感測器原理與應用技術," 2004.
[24] B. Drafts, "Acoustic wave technology sensors," Microwave Theory and Techniques, IEEE Transactions on, vol. 49, pp. 795-802, 2001.
[25] R. M. White, "Direct piezoelectric coupling to surface elastic waves," Appl. Phys. Lett., vol. 7, pp. 314-316, 1965.
[26] A. H. Fahmy and E. L. Adler, "Propagation of acoustic surface waves in multilayers: A matrix description," Applied Physics Letters, vol. 22, pp. 495-497, 1973.
[27] A. Slobodnik Jr, T. Szabo, and K. Laker, "Miniature surface-acoustic-wave filters," Proceedings of the IEEE, vol. 67, pp. 129-146, 1979.
[28] H. Wohltjen and R. Dessy, "Surface acoustic wave probe for chemical analysis. I. Introduction and instrument description," Analytical Chemistry, vol. 51, pp. 1458-1464, 1979/08/01 1979.
[29] A. Bryant, D. L. Lee, and J. F. Vetelino, "A Surface Acoustic Wave Gas Detector," in 1981 Ultrasonics Symposium, 1981, pp. 171-174.
[30] J. W. Gardner, V. K. Varadan, and O. O. Awadelkarim, Microsensors, MEMS, and smart devices vol. 1: Wiley Online Library, 2001.
[31] 吳朗, 電子陶瓷: 壓電陶瓷: 全欣, 1994.
[32] C. K. Campbell, Surface acoustic wave devices for mobile and wireless communications: Academic Press, 1998.
[33] H. Tanaka, "Suppression of bulk-wave responses in SAW devices using the difference of power flow angles," Ultrasonics, Ferroelectrics and Frequency Control, IEEE Transactions on, vol. 42, pp. 938-942, 1995.
[34] C. Campbell, Surface acoustic wave devices and their signal processing applications: Elsevier, 2012.
[35] J. W. Gardner, H. W. Shin, E. L. Hines, and C. S. Dow, "An electronic nose system for monitoring the quality of potable water," Sensors and Actuators B: Chemical, vol. 69, pp. 336-341, 2000.
[36] S. Letcher, "Surface acoustic wave devices," Oceanic Engineering, IEEE Journal of, vol. 11, pp. 487-488, 1986.
[37] H. Ken-Ya, "Surface acoustic wave devices in telecommunications modelling and simulation," NY: Springer, 2000.
[38] J. Kirschner, "Surface Acoustic Wave Sensors (SAWS)."
[39] J. W. Grate and R. A. McGill, "Dewetting effects on polymer-coated surface acoustic wave vapor sensors," Analytical Chemistry, vol. 67, pp. 4015-4019, 1995.
[40] W. P. Jakubik, "Surface acoustic wave-based gas sensors," Thin Solid Films, vol. 520, pp. 986-993, 2011.
[41] R. A. McGill, M. H. Abraham, and J. W. Grate, "Choosing polymer coatings for chemical sensors," Chemtech, vol. 24, pp. 27-37, 1994.
[42] G. Socrates, Infrared and Raman characteristic group frequencies: tables and charts: John Wiley & Sons, 2004.
[43] 趙哲新, "以表面聲波陣列式震盪電路為基礎之氣體感測系統," 清華大學工程與系統科學系學位論文, pp. 1-97, 2009.
[44] 江明璋, "設計改良式表面聲波感測器應用於低濃度混合氣體量測," 清華大學動力機械工程學系學位論文, pp. 1-114, 2013.
[45] Y. Li, C. Deng, and M. Yang, "A novel surface acoustic wave-impedance humidity sensor based on the composite of polyaniline and poly(vinyl alcohol) with a capability of detecting low humidity," Sensors and Actuators B: Chemical, vol. 165, pp. 7-12, 2012.
[46] Y. C. Chien, C. P. Chang, and Z. Z. Liu, "Volatile organics off-gassed among tobacco-exposed clothing fabrics," J Hazard Mater, vol. 193, pp. 139-48, 2011.
[47] I. Ueta, Y. Saito, K. Teraoka, T. Miura, and K. Jinno, "Determination of Volatile Organic Compounds for a Systematic Evaluation of Third-Hand Smoking," Analytical Sciences, vol. 26, pp. 569-574, 2010.
[48] R. E. Noble, "Environmental tobacco smoke uptake by clothing fabrics," Science of The Total Environment, vol. 262, pp. 1-3, 10/30/ 2000.
[49] P. A. Bazuła, A.-H. Lu, J.-J. Nitz, and F. Schüth, "Surface and pore structure modification of ordered mesoporous carbons via a chemical oxidation approach," Microporous and Mesoporous Materials, vol. 108, pp. 266-275, 2008.
[50] J. Wu, P. Joza, M. Sharifi, W. S. Rickert, and J. H. Lauterbach, "Quantitative Method for the Analysis of Tobacco-Specific Nitrosamines in Cigarette Tobacco and Mainstream Cigarette Smoke by Use of Isotope Dilution Liquid Chromatography Tandem Mass Spectrometry," Analytical Chemistry, vol. 80, pp. 1341-1345, 2008/02/01 2008.
[51] Y. J. Guo, J. Zhang, C. Zhao, P. A. Hu, X. T. Zu, and Y. Q. Fu, "Graphene/LiNbO3 surface acoustic wave device based relative humidity sensor," Optik - International Journal for Light and Electron Optics, vol. 125, pp. 5800-5802, 2014.
[52] W. W. Nazaroff and N. E. Klepeis, "Environmental Tobacco Smoke Particles," in Indoor Environment, ed: Wiley-VCH Verlag GmbH & Co. KGaA, 2006, pp. 245-274.
[53] T. L. Tan and G. B. Lebron, "Determination of Carbon Dioxide, Carbon Monoxide, and Methane Concentrations in Cigarette Smoke by Fourier Transform Infrared Spectroscopy," Journal of Chemical Education, vol. 89, pp. 383-386, 2012/02/14 2012.