本研究利用CeO2-ZrO2固態氧化物為參考端來製備薄膜型氧氣感測器。首先以磁控式共濺鍍系統沉積Pt-YSZ薄膜，並利用不同還原條件以形成多孔的Pt-YSZ電極。多孔的電極結構是為了增加其三相介面比例，並滅少其應答時間。以不同Ar與O2比例，進行反應式共濺鍍出的白金氧化先趨物(PtOx-8YSZ)經由真空或大氣氣氛之下還原，熱處理溫度與時間分別為600°C，及1小時，可以於SiO2/Si基材上形成多孔的Pt-YSZ薄膜，發現於CeO2-ZrO2基材會形成以裂隙為主體的薄膜。經以上實驗發現，在CeO2-ZrO2上的Pt-8YSZ薄膜很難形成多孔結構。
以CeO2-ZrO2為基材，8YSZ為電解質，利用指叉電極來製作Pt-8YSZ電極的氧氣感測器，經單氣室量測系統，以流量皆為200sccm的O2/N2氣氛進行感測器效能的量測。在600°C下量測時，其電壓差為2mV，而應答時間為0.5s~1.5s。由實驗結果可知，以CeO2-ZrO2為參考端的薄膜型氧氣感測器是可行的。

In this research, we fabricate thin film oxygen sensors with CeO2-ZrO2 solid-state reference. First, we use magnetron co-sputter to deposit Pt-8YSZ films and use different reduced conditions to form porous Pt-8YSZ electrode. The electrode with porous structure is expected to increase the three-phase area and reduce response time. We used different Ar and O2 ratios to form PtOx-8YSZ film by co-sputter technology and the PtOx-8YSZ film could be reduced to Pt-YSZ film in vacuum or atmosphere at 600°C for 1hrs. Pt-8YSZ film is porous structure on SiO2/Si substrate, but it is hard to form the porous structure on CeO2-ZrO2 substrate.
We use the CeO2-ZrO2 as reference, 8YSZ as electrolyte and Pt-8YSZ as electrode by shadow mask to form a sensor cell, then tested the sensor performance in a single chamber system using 200 sccm flow rate in O2/N2 environment. The emf value is 0.4mV~2mV and the response time is 0.5s~1.5s for this cell measured at 600°C~800°C. This result is not as good as conventional oxygen sensor, but we already prove feasibility of a thin film oxygen sensor with CeO2-ZrO2 solid-state reference.

參考文獻

1. R. J. Furness, “Intelligent Sensor Based Manufacturing: Applications, Needs, and Future Directions”, Porceedings of the Japan/USA Symposium on Flexible Automation 2, 1055(1996).
2. N. T. Nguyen, “Micromachined Flow Sensors-A Review”, Flow Measurement and Instrumentation 8, 7 (1997).
3. M. M. O. Lee, “Merged Technology on MEMS”, Proceedings of the IEEEE Hong Kong Electron Device Meeting 1997, IEEE Piscataway, NJ USA, P.128.
4. 張玉清,宋隆裕,李英正,楊淑卿,陶惟翰, “微型氧氣感測器簡介”, 科儀新知, 第二十卷, 第五期, 第84-89頁, 民國88年4月
5. 黃炳照,”固態電解質電化學氧氣感測器”, CHEMISTRY (THE CHINESE CHEM. SOC., TAIPEI), Vol.59, No. 2, pp. 207~217 (2001).
6. W. C. Maskell, “Inorganic solid state chemically sensitive devices: electrochemical oxygen gas sensors”, J. Phys. E. Sci. Instrum., 20, 1156(1987).
7. T. Takeuchi, “Oxygen sensors”, Sens. Actuators, 14, 109(1998).
8. S. Matsumoto, H. Miura, K. Uchida, Y. Otsuka, “Oxygen sensor and manufacturing method thereof”, US Patent 4,096,048 (1978).
9. T.M. Gur, R.A. Huggins, “Oxygen sensor”, US Patent 5,827,415 (1998).
10. H. Kaneko, T. okamura, H. Taimatsu, “Characterization of zirconia oxygen sensors with a molten internal referece for low-temperature operation”, Sens. Actuators B 93, 205-208 (2003).
11. J. W. Bae, J. Y. Park, S. W. Hwang, G. Y. Yeom, K. D. Kim, Y. A. Cho, J. S. Jeon, and D. Choi, “Characterization of Yttria-Stabilized Zirconia Thin Film Prepared by Radio Frequency Magnetron Sputtering for a Combustion Control Oxygen Sensor”, J. Electrochem. Soc., 147(6) 2380-2384 (2000).
12. N. Rajabbeigi, B. Elyassi, A. Khodadadi, S. S. Mohajerzadeh, M. Sahimi, “A novel miniaturized oxygen sensor with solid-state ceria-zirconia reference”, Sens. Actuators B, 100, 139-142, (2004).
13. B. Elyassi, N. Rajabbeigi, A. Khodadadi, S. S. Mohajerzadeh, M. Sahimi, “An yttria-doped ceria-based oxygen sensor with solid-state reference”, Sens. Actuators B, 100, 178-183 (2004).
14. N. Rajabbeigi, B. Elyassi, A. Khodadadi, S. S. Mohajerzadeh, Y. Mortazavi, M. Sahimi, “Oxygen sensor with solid-state CeO2-ZrO2-TiO2 reference”, Sens Actuators B, 108, 341-345 (2005).
15. N.M. Sammes, Z. Cai, “Ionic conductivity of ceria/yttria stabilized zirconia electrolyte materials”, Solid State Ionics, 100, 39-44 (1997).
16. C.E. Hori, Permana, K.Y. Simon Ng, A. Brenner, K. More, K.M. Rahmoeller, D. Belton, “Thermal stability of oxygen storage properties in a mixed CeO2-ZrO2 system”, Appl. Catal. B: Environ. 16, 105-117 (1998).
17. D. Yuan and F. A. Kroger, “Stabilized Zirconia as an Oxygen Pump”, J. Electrochem. Soc., 116, 5, 594 (1969).
18. Ron Steven “Textbook on Zriconia” Magnesium Elektron;2nd , p38 (1983)
19. N. Bonanos, R. K. Soltwinski, B. C. H. steele, and E. P. Butler “High ionic conductivity in polycrystalline tetragonal Y2O3-ZrO2”, J. Mat. Sci. Lett., 3, p245(1984)
20. E. P. Butler, R. K. Soltwinski, N. Bonanos, J. Drennan and B. H. steele, “Microstructural-Electrical Property Relationship n High-Conductivity Zirconias”, in Advance in Ceramics, Vol. 12, Science and Technology of Zirconia II (N. Claussen, M. Ruhle and A. H. Heuer, eds.),p.572, The American Ceramic Society, Inc., Columbus, Ohio, USA(1983).
21. A. H. Heuer and L. W. Hobbs, Science and Technology of Zirconia, Vol.3, p.216, American Ceramic Society, Columbus, Ohio(1981).
22. E. C. Subbarao and H. S. Maiti, “Solid Electrolytes With Oxygen Ion Conduction”, Solid State Ionics, 11, 317(1984).
23. B. C. H. Steele, J. Drennan, R. K. Slotwinski, N. Bonanps and E. P. Butler, “Factors Influencing The Performance of Zirconia-Based Oxygen Monitors”, in Advances in Ceramics, Vol.3, Science and Technology of Zirconia (A. H. Heuer and L. W. Hobbs, eds.), p.286, The American Ceramic Society, Inc., Columbus, Ohio, U.S.A (1980).
24. K. Kinoshita in Electrochemical Oxygen Technology, (John Wiley & Sons, Inc., New York, U.S.A., 1992) Chapter 7, Industrial Electrochemistry, p.37.
25. 紀廷瑋，“以反應式濺鍍製備安定性氧化鋯(3YSZ)薄膜之研究”，台灣科技大學工程所材料學程碩士論文，民國91年，12月。
26. T. Inoue, N. Seki, K. Eguchi and H. Arai, “Low-temperature operation of solid electrolyte oxygen sensors using perovskite-type electrodes”, J. Electrochem. Soc. 137, 2523(1990).
27. S. P. S. Badwal, F. T. Ciacchi, “Microstructure of Pt Electrodes and its Influence on the Oxygen Transfer Kinetics”, Solid State Ionics, vol.18/19, p.1054 (1986).
28. S. P. S. Badwal, F. T. Ciacchi and J. W. Haylock, “Nernstian Behavior of Zirconia Oxygen Sensors Incorporating Composite Electrodes”, J. Appl. Electrochem. 18, 232(1988).
29. S. Kim, Y. L. Yang, A. J. Jacobson and B. Abeles, “Diffusion and Surface Exchange Coefficients in Mixed Ionic Electronic Conducting Oxides From the Pressure Dependence of Oxygen Permeation”, Solid State Ionics 106, 189(1998).
30. T. H. Etsell and S. N. Flengas, “Overpotential Behavior of Stabilized Zirconia Solid Electrolyte Fuel Cells”, J. Electrochem. Soc. 118, p.1890 (1971).
31. N. L. Robertson and J. N. Michaels, “Oxygen Exchange on Platinum Electrodes in Zirconia Cells: Location of Electrochemical Reaction Sites”, J. Electrochem. Soc. 137, 129(1990).
32. 莊眭賢，”氧化鋯型固態電解質氧氣感測器之研發”, 台灣科技大學, 化學工程研究所, 碩士論文(1990)
33. J. R. McBride, G. W. Graham, C. R. Peters and W. H. Weber, “Growth and Characterization of Reactively Sputtered Thin-Film Platinm Oxides”, J. Appl. Phys. 69, 1596(1991).
34. 許凱超，“以反應式濺鍍及還原反應製備多孔性薄膜電極”，台灣科技大學工程所材料學程碩士論文，民國90年，7月。
35. J. Chapin, U.S. Patent No.438482,1974；S. Schiller, “Use of the ring gap plasmatron for high rate sputtering”, Thin Solid Films, 40, 327(1997).
36. J.R. Hollahan and W.Kern (Eds), Thin Film Process, Academic Press, New York , 1978.
37. W. D. Westwood, “Reactive Sputter Deposition, Handbook of Plasma Processing Technology”, Springer-Verlag Berlin Heidelberg, U.S.A., Chap 9, (1992).
38. 羅吉宗編，「第二章 電漿物理」，薄膜科技與應用，台北，全華科技，民國94年。
39. 柯賢文編，「第五章 濺鍍鍍膜」，表面與薄膜處理技術，台北，全華科技，民國94年。
40. W.D. Kingery, H.K. Bowen and D.R. Uhlmann，Introduction to Ceramics Second Edition , John Wiley & Sons, Inc., New York,(1976)
41. S. Huang, L. Li, O. Van der Biest, J. Vleugels, “Influence of the oxygen partial pressure on the reduction of CeO2 and CeO2-ZrO2 ceramics”, Solid State Sciences, 7, 539-544(2005).