無機氣體壓電晶體感測器研製與應用
摘 要
壓電晶體感測器是一種質量感測器，利用質量變化造成頻率改變，再藉由此頻率變化值了來了解被偵測物的特性。本實驗是利用鋅離子/大環胺醚( Zn2+/Cryptand22 ) 、鈦離子/大環胺醚( Ti4+/
Cryptand22 )做為石英壓電晶體膜感測器之塗佈物質，分別對一氧化碳( CO )及二氧化氮( NO2 )進行感測。在此實驗系統中，是利用自製微電腦介面來讀取振盪頻率及其變化，其中包含了數位計數的ALTERA 及8255卡，並以軟體控制介面讀取數據及繪圖。
在本研究曾利用各種金屬離子/大環胺醚錯合物(如Ti4+/
Cryptand22、Zn2+/Cryptand22、Al3+/Cryptand22、Ru3+/Cryptand22等)做為石英晶體塗佈物，用以偵測 CO 及 NO2 ，結果發現，其中以 Zn2+/Cryptand22 為塗佈物之石英壓電晶體感測器中，對 CO為物理性吸附具有可逆性，其吸附、脫附速率分別為0.571、0.404
(Hz/sec)，且具有不錯的偵測下限( 0.26ppm )及再現性( RSD =
2.15%,n=10 )，其中 NO2 不會造成干擾，所以可以使用以 Zn2+/
Cryptand22 為塗佈物之石英壓電晶體感測器，可成功地分辨 CO及NO2。而在 Ti4+/Cryptand22為塗佈物之石英壓電晶體感測器中，對 NO2 的也為物理性吸附具有可逆性，其吸附、脫附速率分別為0.535、0.386(Hz/sec)，有不錯的偵測下限( 0.16ppm )及再現性( RSD
=2.09%,n=10 )，但 CO 會有干擾產生。
水氣與溫度皆對上述之 CO 及 NO2 石英壓電晶體感測器產生干擾，其中使用五氧化二磷( P2O5 )為乾燥劑的效果最好，可將水氣完全去除且允許90%的待測氣體通過。而在溫度干擾的部分，由於本研究中的吸附現象皆屬於物理性吸附，所以感測器的訊號隨著溫度上升而有下降的趨勢。此外，在本研究中亦將石英壓電感測器與氣相層析儀之熱導偵測器( TCD )做比較，結果發現，當待測氣體通過層析管柱後，不僅可以將有機干擾物分離，也可以由石英壓電感測器可得到較好的感測結果，而 TCD 則只能感測到有機干擾物，對無機氣體CO 及 NO2 則不靈敏。
本研究中亦對感測器之使用壽命做探討，結果發現，使用一個月後，感測器之訊號大約下降40%，仍具有相當程度的靈敏度，只需對訊號稍做修正即可繼續使用，具有實用價值。
前述實驗中 CO 、 NO2 個別偵測或混合偵測後，各30組數據經倒傳遞類神經網路( BPN )分析，不管是網路學習或網路測試皆可100%將CO 、 NO2分辨出來，誤判率為0，此結果表示 BPN 可成功地將其定性化。此外，應用多元迴歸分析( MRA )也可成功地將CO 及 NO2 的濃度定量化，個別偵測後CO 及 NO2 的濃度誤差分別為-7.5 ~10%、-5.0~1.3%，而混合偵測後CO 及 NO2 的濃度誤差分別為-17.5 ~5.8%、-3.3~20.0%。此結果表示，本實驗已成功地發展出 CO、NO2 無機氣體石英壓電晶體感測器，輔助以倒傳遞類神經網路及多元迴歸分析，可將 CO及NO2 定性定量化。

Preparation and Application of Piezoelectric Crystal Inorganic Gas Sensors
Abstract
Zinc(Ⅱ)/Cryptand22 and Titanium(Ⅳ)/Cryptand22-coated piezoelectric crystal detection system with a home-made computer interface for data acquisition and processing was prepared and applied for CO and NO2. The home-made computer interface includes the digital counting system Altera and Intell-8255 data processing system. Software was written to control the interface and data acquisition.
In this study, many kinds of metal-ion/Cryptand22 complex(e.g. Ti4+/Cryptand22、Zn2+/Cryptand22、Al3+/Cryptand22、Ru3+/Cryptand22 etc.) were used to detect CO and NO2. A Zn2+/Cryptand22-coated piezoelectric crystal detection system is a reversible type. It is a physical adsorption, and its adsorption、desorption rate is 0.571、0.404 Hz/sec. The detection system also showed the good detection limit of 0.26 ppm and good reproducibility with RSD of 2.15%( n=10 ) for CO, but was insensitive to NO2. The sensor can successfully distinguish between CO and NO2. Furthermore, a Ti4+/Cryptand22-coated piezoelectric crystal detection system is also a reversible type. It is a physical adsorption, and its adsorption、desorption rate is 0.535、0.386 Hz/sec. The detection system showed the good detection limit of 0.16 ppm and good reproducibility with RSD of 2.09%( n=10 ) for NO2, but the sensor was interfered by CO.
The interference effect of water vapor and temperature on the piezoelectric detection system was not negligible. P2O5 was the best dry filter because it reacted completely with water vapor and it permitted that a 90% of tested gases reached the sensor. Besides, the frequency response apparently decreased with the increased temperature, indicating that the adsorption decreased with increase in temperature which is a characteristic of physical adsorption. The piezoelectric crystal detector system was successively connected on-line with a gas chromatograph( GC ) and compared with the thermal conductivity detector( TCD ). The organic interference compounds e.g. acid, amine are separated with the Porapak GC column and, subsequently, detected with the piezoelectric crystal detector and TCD. The piezoelectric crystal detector system seems to show the better response and selection.
The detector lifetime was also discussed in this study. The frequency response decayed 40% after it was used for a month. It only do a easy calibration. The detection system is economical.
The frequency signals from the two channel crystal analyzed sensor array were processed by back- propagation artificial neural network( BPN ) and multiple regression analysis( MRA ). The qualitative and quantitative analyses of CO and NO2 in their mixtures has been successfully realized by using the sensor array、BPN and MRA. In the qualitative analysis, the error of network learning and training was zero. In the quantitative analysis, the error of CO and NO2 concentration was -7.5~10% and -5.0~1.3% for each other. In their mixtures, the error of CO and NO2 concentration was -17.5~5.8%、-3.3~20.0% for each other.

參考資料
1.C. J. Perderson, Cyclic polyethers and their complexs with metal salts, J. Am. Chem. Soc., 89 (1967) 7017-7036.
2.B. Dietrich, J. M. Lehn, T. P. Sauvage, Les cryptates, Tetrahedron Letters, 34 (1969) 2889-2892.
3.施正雄, 化學感測器整合計畫研究規劃與成果報導, 科學發展月刊, 27(10) (1999) 1184-1197.
4.行政院環境保護署, 空氣品質歷年趨勢分析—空氣污染物濃度趨勢圖
5.行政院環境保護署, 交通工具空氣污染排放標準, 中華民國八十八年二月二十四日行政院環境保護署(八八)環署空字第0009384號
6.行政院環境保護署, 空氣品質標準, 中華民國八十八年七月二十一日行政院環境保護署(八八)環署空字第0046665號
7.蔡嬪嬪, 曾明漢, 氣體感測器之簡介、應用及市場, 材料與社會, 68(8) (1992) 50-77.
8.葉陶淵, 化學感測器中氣體感測器的新動向, 科儀新知, 20(4) (1999) 72-76.
9.Ulrich Hoefer, Gerd Kuhner, Werner Schweizer, Gerd Sulz, Klaus Steiner, CO and CO2 thin-film SnO2 gas sensors on Si substrates, Sensors and Actuators B, 22 (1994) 115-119.
10.Klaus Steiner, Ulrich Hofer, Gerd Kuhner, Gerd Sulz, Elmar Wagner, Ca- and Pt-catalysed thin-film SnO2 gas sensors for CO and CO2, Sensors and Actuators B, 24-25 (1995) 529-531.
11.Keiichi Ohta, Hisayoshi Terai, Ikuhiko Kimura, Katsuyuki Tanaka, Simultaneous determination of hydrogen, methane, and carbon monoxide in water by gas chromatography with a semiconductor detector, Anal. Chem., 71 (1999) 2697-2699.
12.N. Barsan, J. R. Stetter, M. Findlay, Jr., W. Gopel, High-performance gas sensing of CO: comparative tests for semiconducting (SnO2-Based) and for amperometic gas sensors, Anal. Chem., 71 (1999) 2512-2517.
13.C. Cantalini, H. T. Sun, M. Faccio, M. Pelino, S. Santucci, L. Lozzi, M. Passacantando, NO2 sensitivity of WO3 thin film obtained by high vacuum thermal evaporation, Sensors and Actuators B, 31 (1996) 81-87.
14.P. Nelli, L. E. Depero, M. Ferroni, S. Groppelli, V. Guidi, F. Ronconi, L. Sangaletti, G. Sberveglieri, Sub-ppm NO2 sensors based on nanosized thin films of titanium-tungsten oxides, Sensors and Actuators B, 31 (1996) 89-92.
15.J. Santos, P. Serrini, B. O’Berirn, L. Manes, A thin film SnO2 gas sensor selective to ultra-low NO2 concentrations in air, Sensors and Actuators B, 43 (1997) 154-160.
16.M. C. Horrillo, P. Serrini, J. Santos, L. Manes, Influence of the deposition conditions of SnO2 thin films by reactive sputtering on the sensitivity to urban pollutants, Sensors and Actuators B, 45 (1997) 193-198.
17.Tomas Eklov, Ingemar Lundstrom, Distributed sensor system for quantification of individual components in a multiple gas mixture, Anal. Chem., 71 (1999) 3544-3550.
18.N. Miura, M. Ono, K. Shimanoe, N. Yamazoe, A compact amperometric NO2 sensor based on Na+ conductive solid electrolyte, Journal of Applied Electrochemistry, 28 (1998) 863-865.
19.Masaki Ono, kengo Shimanoe, Norio Miura, Noboru Yamazoe,Solid-state amperometric sensor based on a sodium ion conductor for detection of total NOx in an atmospheric environment, Electrochemical and Solid-State Letters, 2(7) (1999) 349-351.
20.R. Mukundan, Eric L.Broshs, David R. Brown, fernando H.Garzon, Ceria-electrolyte-based mixed potential sensors for the detection of hydrocarbons and carbon monoxide, Electrochemical and Solid-State Letters, 2(8) (1999) 412-414.
21.彭成鑑, 壓電材料, 科儀新知, 16 (1995) 18-29.
22.Daniel A. Buttry, Michael D. Ward, Measurement of interfacial processes at electrode surfaces with the electrochemical quartz crystal microbalance, Chem. Rev., 92 (1992) 1355-1379.
23.Stephen J.Martin,Gregory C. Frye, Antonio J. Ricco, Stephen D. Senturia,Effect of surface roughness on the response of thickness-shear mode resonators in liquids, Anal. Chem., 65 (1993) 2910-2922.
24.Levenson L. L., “Cimento”, Suppl.2, Ser. I, 5 (1967) 321.
25.紀培錦, “新電子科技雜誌”, 17 (1989) 196.
26.湯進德, “微電腦界面技術”, 金華, 1984.
27.G. Z. Sauerbrey, Z. Phys., 155 (1959) 206.
28.Lu C., Czanderna A. W.,"Applications of Piezoelectric Quartz Crystal Microbalance ", Elsevier Science, New York (1984).
29. King W. H., Piezoelectric sorption detector, Anal. Chem., 36 (1964) 1735-1739.
30.Mat H. Ho, George G. Guilbault, Eugene P. Scheide, Detection of carbon monoxide in ambient air with a piezoelectric crystal, Anal. Chem., 54 (1982) 1998-2002.
31.M. Teresa S. R. Gomes, P. Sergio T. Nogueira, A. C. Duarte, Joao A. B. P. Olivera, Development of a methodology for the determination of carbon monoxide using a quartz crystal microbalance, Analyst, 124 (1999) 1449-1453.
32.Ping Chang, Jeng-Shong Shih, Preparation and application of cryptand-coated piezoelectric crystal gas-chromatographic detector, Analytica Chimica Acta, 360 (1998) 61-68.
33.Yun-Ching Chao, Jeng-Shong Shih, Adsorption study of organic molecules on fullerene with piezoelectric crystal detection system, Analytica Chimica Acta, 374 (1998) 39-46.
34.Ping Chang, Jeng-Shong Shih, Application of piezoelectric Ru(Ⅲ)/cryptand-coated quartz xrystal gas chromatographic detector for olefins, Analytica Chimica Acta, 380 (1999) 55-62.
35.Jeng-Shong Shih, Piezoelectric crystal membrane chemical sensors based on fullerene and macrocyclic polyethers, J. Chin. Chem. Soc., 47 (2000) 21-32.
36.Ping Chang, Jeng-Shong Shih, Multi-channel piezoelectric quartz sensor for organic vapours, Analytica Chimica Acta, 403 (2000) 39-48.
37.Michael Thompson, Arlin L. Kipling, Wendy C. Duncan-Hewitt, Ljubinka V. Rajakovic, Biljana A. Cavic-Vlasak, Thickness-shear-mode acoustic wave sensors in the liquid phase a review, Analyst, 116 (1991) 881-890.
38.Xiaoge Qu, Lili Bao, Xiaoli Su, Wanzhi Wei, A new method based on gelation of tachypleus amebocyte lysate for detection of Escherichia coliform using a series piezoelectric quartz crystal sensor, Analytica Chimica Acta, 374 (1998) 47-52.
39.Kyusik Yun, Eiry Kobatake, Tetsuya Haruyama, Marja-Leena Laukkanen, Kari Keinanen, Masuo Aizawa, Use of a quartz crystal microbalance to monitor immunoliposome-antigen interaction, Anal. Chem., 70 (1998) 260-264.
40.Weifeng Li, Xiaoli Su, Hong Zhang, Lihua Nie, Shuozhuo Yao, Determination of benzydamine hydrochloride in serum and urine by using a benzydamine ion-selective piezoelectric sensor, Analystical Sciences, 14 (1998) 955-960.
41.葉怡成, “應用類神經網路”, 儒林, 1997.
42.葉怡成, “類神經網路模式應用與實作”, 儒林, 1998.
43.Gyorgy Barko, Jozef Hlavay, Application of an artificial neural network (ANN) and piezoelectric chemical sensor array for identification of volatile organic compounds, Talanta, 44 (1997) 2237-2245.
44.Jon M. Sutter, Peter C. Jurs, Neural network classification and quantification of organic vapors based on fluorescence data from a fiber-optic sensor array, Anal. Chem., 69 (1997) 856-862.
45.B. Yang, M. C. Carotta, G. Faglia, M. Ferroni, V. Guidi, G. Martinelli, G. Sberveglieri, Quantification of H2S and NO2 using gas sensor arrays and an artificial neural network, Sensors and Actuators B, 43 (1997) 235-238.
46.Hyung-Ki Hong, Hyun Woo Shin, Hyeon Soo Park, Dong Hyun Yun, Chul Han Kwon, Kyuchung Lee, Sung-Tae Kim, Toyosaka Moriizumi, Gas identification using micro gas sensor array and neural-network pattern recognition, Sensors and Actuators B, 33 (1996) 68-71.
47.T. Nakamoto, A. Fukuda, T. Moriizumi, Perfume and flavour identification by odour-sensing system using quartz-resonator sensor array and neutral-network pattern recognition, Sensors and Actuators B, 10 (1993) 85-90.
48.Hidehito Nanto, Shiro Tsubakino, Mitsuo Ikeda, Fumitaka Endo, Identification of aromas from wine using quartz-resonator gas sensors in conjuction with neural-network analysis, Sensors and Actuators B, 24-25 (1995) 794-796.
49.張平, 有機氣石英壓電晶體感測器的研製與應用, 國立台灣師範大學化學研究所博士論文, 63.
50.凌永健, 陳秋雲, 黃依萍, 化學分析的偵測極限(上), 科儀新知, 16(1) (1994) 70-83.
51.高文弘, 周孟儒譯著, “界面化學”, 黎明書局, 1983 , 26-31.