光纖開創電信傳輸新紀元，隨著光纖及光電零組件品質的精進，現今結合光纖及光電元件製作的光纖感測器，已廣泛應用於環境及汙染監測、國防、實驗室分析、臨床診斷及其他醫學應用；光纖感測器針對每一個特殊的應用，其對靈敏度，準確性，選擇性，感測器壽命及成本都有個別需求。近年來，光纖已被用來量測生物醫學及生物科技領域的各種參數。
本研究以漸逝波光纖感測器的製作技術為基礎，製作出微檢體量光纖酸鹼值感測器。本研究採用1mm直徑，纖衣材料氟化聚合物，纖核材料PMMA，型號CK-40 Eska的多模光纖，保留纖衣於此光纖上製作一個0.2mm圓形孔隙，貫穿纖衣和纖核；同時使用酸鹼值廣域指示劑，配合溶膠－凝膠法製作酸鹼值感測材料，並將此感測材料注入前述貫穿纖衣與纖核的0.2mm小孔，其間形成玻璃的固體束狀感測區，本穿孔式微量酸鹼值感測器所需檢體量為50～150μl，響應時間40秒，感測範圍為pH4至pH10。

Optical fiber created a new era of telecommunications transmission. Associated with sophisticated quality of the optical and optoelectronic components, the fiber optic sensors manufactured by combining optical and optoelectronic components have been widely used in environmental and pollution monitoring, defense, laboratory analysis, clinical diagnosis and other medical applications. Every specific application of the fiber optic sensors has its own individual needs and concerns, such as sensitivity, accuracy, selectivity, lifetime and cost. Recently, fiber optic has been used to measure various parameters of biomedicine and biotechnology.
In this thesis, basing on the production technology of the evanescent wave fiber optic sensors we present a pH sensor with smaller volume of specimen. The specifications of the fiber optic we used are multimode plastic optical fiber, Model CK-40 Eska, 1mm diameter. And the material of fiber cladding is fluorinated polymers, fiber core is PMMA. Retaining the fiber cladding, drilled a 0.2mm round hole that the fiber cladding and the fiber core are penetrating through. We defined this as core-defect. Applying the sol-gel method and pH indicator constructed pH sensing materials. This sensing material is injected into the hole mentioned above and built a bundle sensing area itself. The core-defect pH sensors that we produced require a specimen amount 50 ~ 150μl, its response time is 40 seconds and the sensing range is pH4 to pH10.

論文審定書 (中文) i
論文審定書 (英文) ii
誌謝 iii
中文摘要 iv
Abstract v
目錄 vi
圖目錄 viii
表目錄 x
第一章序論 1
1.1前言 1
1.2研究背景 4
1.3研究動機與目的 5
1.4本文架構 5
第二章原理和實驗流程 6
2.1光纖漸逝波感測器 6
2.1.1漸逝波理論 8
2.1.2漸逝波光纖酸鹼值感測器之文獻回顧 11
2.1.3纖核感測光纖感測器之理論分析 12
2.2酸鹼值指示劑 14
2.2.1廣域酸鹼值指示劑 14
2.2.2酸鹼值指示劑變色原理 14
2.3溶膠－凝膠法 16
2.3.1溶膠－凝膠法原理 16
2.3.2溶膠－凝膠法於不同酸鹼值環境催化 18
2.3.3溶膠－凝膠法加入共摻物降低材料密度 18
2.3.4溶膠－凝膠法加入乾燥控制化學添加劑減少破裂 21
2.3.5溶膠－凝膠法加入表面活性劑減少指示劑滲出 22
2.4實驗流程 24
第三章實驗步驟與量測原理 25
3.1使用溶膠－凝膠法製備酸鹼值感測材料 25
3.1.1使用藥品一覽表 25
3.1.2廣域指示劑之製備 26
3.1.3酸鹼值感測材料之製備 26
3.2光纖酸鹼值感測器之製備 26
3.3酸鹼值感測元件特性量測 27
3.3.1吸收、穿透光譜 27
3.3.2指示劑滲出量測 28
3.3.3光功率量測 28
第四章實驗結果與量測分析 29
4.1酸鹼值感測材料光學特性分析 29
4.1.1多孔隙材料吸收光譜 29
4.1.2酸鹼值指示劑吸收光譜分析 29
4.2酸鹼值感測材料指示劑滲出測試 31
4.3光纖酸鹼值感測器特性量測 32
第五章結論與未來展望 34
參考文獻 36

[1]Paras N. Prasad, Barry R. Masters, "Introduction to Biophotonics," Journal of Biomedical Optics, vol. 10, issue 3, 1 June 2005.

[2]E. Udd, William B. Spillman Jr., "Fiber Optic Sensors: An Introduction for Engineers and Scientists," Second Edition, John Wiley & Sons, Inc., 2011.

[3]S. Caras, J. Janata, "Field Effect Transistor Sensitive to Penicillin," Analytical Chemistry, Vol. 52, pp.1935-1937, 1980.

[4]謝振傑，光纖生物感測器，物理雙月刊(28卷4期)，2006。

[5]甯孝真、彭淑玉、張育欣、黃雅卿、鄧芳蜜、周雅蘋，以尿液自動分析儀URISYS 2400之反射比值定量尿液試紙化學檢查，生物醫學暨檢驗科學雜誌(20卷3-4期)，頁數47-55，2009。

[6] C. Rottman, M. Ottolenghi, R. Zusman, O. Lev, M. Smith, G. Gong, M.L. Kagan, D. Avnir, "Doped sol-gel glasses as pH sensors," Materials Letters, vol. 13, issue 6, pp. 293-298, May 1992.

[7] O. BelhadjMiled, H. Ben Ouada, and J. Livage, "pH sensor based on a detection sol–gel layer onto optical fiber," Materials Science and Engineering: C, vol. 21, issues 1-2, pp. 183-188, 1 September 2002.

[8] S. T. Lee, J. Gin, V. P. N. Nampoori, C. P. G. Vallabhan, N. V. Unnikrishnan, and P. Radhakrishnan "A sensitive fibre optic pH sensor using multiple sol-gel coatings," Journal of Optics A: Pure and Applied Optics, vol. 3, pp. 355-359, 2001.

[9] J. Rayss and G. Sudolski, "Ion adsorption in the porous sol-gel silica layer in the fibre optic pH sensor," Sensors and Actuators B: Chemical, vol. 87, issue 3, pp. 397-405, 20 December 2002.

[10] A. Armin, M. Soltanolkotabi, and P. Feizollah, "On the pH and concentration response of an evanescent field absorption sensor using a coiled-shape plastic optical fiber," Sensors and Actuators, A: Physical, vol. 165, no. 2, pp. 181-184, February 2011.

[11] ZhengfangGe ,Chris W. Brown ,Linfeng Sun ,Sze Cheng Yang, "Fiber-optic pH sensor based on evanescent wave absorption spectroscopy," Anal. Chem., vol. 65, issue 17, pp. 2335-2338, 1993.

[12] S. Dong, M. Luo, G. Peng, W. Cheng, "Broad range pH sensor based on sol-gel entrapped indicators on fibre optic," Sensors and Actuators B: Chemical, vol. 129, issue 1, pp. 94-98, 29 January 2008.

[13] C. Egami, K. Takeda, M. Isai, M. Ogita, "Evanescent-wave spectroscopic fiber optic pH sensor," Optics Communications, vol. 122, issues 4-6, pp. 122-126, 1 January 1996.

[14] K. T. V. Grattan, B. T. Meggitt, "Optical Fiber Sensor Technology Volume 4 Chemical and Environmental Sensing," Kluwer Academic Publishers, 1999.

[15] B.D. Gupta, Navneet K. Sharma, "Fabrication and characterization of U-shaped fiber-optic pH probes,"Sensors and Actuators B: Chemical, vol. 82, issue 1, pp. 89-93, 1 February 2002.

[16] Shinn-Fwu Wang, "U-shaped optical fiber sensor based on multiple total internal reflections in heterodyne interferometry," Optics and Lasers in Engineering, vol. 47, issue 10, pp. 1039-1043, October 2009.

[17] P.K. Choudhurya, Toshihiko Yoshino, "On the pH response of fiber optic evanescent field absorption sensor having a U-shaped probe: An experimental analysis," Optik - International Journal for Light and Electron Optics, vol. 114, issue 1, pp. 13-18, 2003

[18]Tao, S., Winstead, C.B., Jindal, R., Singh, J.P., "Optical-fiber sensor using tailored porous sol-gel fiber core," Sensors Journal, IEEE, vol. 4, issue. 3, pp.322-328, 2004.
[19]A.W. Snyder, J. Love, "Optical Waveguide Theory," Chapman and Hall Ltd, 1983.

[20] Larry L. Hench, Jon K. West, "The sol-gel process," Chem. Rev., vol. 90, issue 1, pp. 33-72, 1990.

[21] A.H. Boonstra, T.N.M. Bernards, J.J.T. Smits, "The effect of formamide on silica sol-gel processes," Journal of Non-Crystalline Solids, vol. 109, issues 2-3, pp. 141-152, June 1989.

[22]歐邑辰，以溶膠凝膠包覆法共固定化融合VHb之D型胺基酸氧化酶及過氧化氫酶之研究，碩士論文，國立臺灣科技大學，2006。

[23]林振國，生醫用漸逝波光纖酸鹼值感應器之研究，碩士論文，國立中山大學，2012。

[24]A.-M Siouffi, "Silica gel-based monoliths prepared by the sol-gel method: facts and figures," Journal of Chromatography A, vol. 1000, issues 1-2, pp. 801-818, 6 June 2003.

[25] J. Homola, Sinclair S. Yeea, G. Gauglitzb, "Surface plasmon resonance sensors: review," Sensors and Actuators B: Chemical, vol. 54, issues 1-2, pp. 3-15, 25 January 1999.

[26] B. D. Gupta and R. K. Verma, "Surface Plasmon Resonance-Based Fiber Optic Sensors: Principle, Probe Designs, and Some Applications," Journal of Sensors, vol. 2009, 2009.

[27] D. K. Cheng, "Field and Wave Electromagnetics," Addison-Wesley Publishing Company, 1989.

[28] Izaak M. Kolthoff ,Miran K. Chantooni , Sadhana. Bhowmik, "Acid-Base Indicator Constants in Acetonitrile," Anal.Chem., vol. 39, issue 3, pp. 315-320, 1967.

[29] Jie Lin, Dong Liu, "An optical pH sensor with a linear response over a broad range," AnalyticaChimicaActa, vol. 408, issues 1-2, pp. 49-55, 9 March 2000.

[30] Claudio Rottman, Gideon Grader, Yoram De Hazan, Sharona Melchior, and David Avnir, "Surfactant-Induced Modification of Dopants Reactivity in Sol-Gel Matrixes," J. Am. Chem. Soc., vol. 121, issue 37, pp. 8533-8543, 1999.

[31]吳惠榮，光纖多工生化感測系統之研發與血糖病變監測，碩士論文，國立成功大學，2002。

[32] Sharad D. Bhagat, A. VenkateswaraRao, "Surface chemical modification of TEOS based silica aerogels synthesized by two step (acid–base) sol-gel process," Applied Surface Science, vol. 252, issue 12, pp. 4289-4297, 15 April 2006.

[33] EnjuWanga, Kwok-Fan Chowa, Vivian Kwana, Tammy China, Crystal Wonga, Andrew Bocarslyb, "Fast and long term optical sensors for pH based on sol-gels," AnalyticaChimicaActa, vol. 495, issues 1-2, pp. 45-50, 24 October 2003.

[34] A. V. Rao, R. R. Kalesh, G. M. Pajonk, "Hydrophobicity and physical properties of TEOS based silica aerogels using phenyltriethoxysilane as a synthesis component," Journal of Materials Science, vol. 38, issue 21, pp. 4407-4413, 2003.

[35] N. Uchida, N. Ishiyama, Z. Kato, K. Uematsu, "Chemical effects of DCCA to the sol-gel reaction process," Journal of Materials Science, vol. 29, issue 19, pp. 5188-5192, 1 October 1994.

[36] K. T. V. Grattan, B. T. Meggitt, "Optical Fiber Sensor Technology Volume 3 Applications and Systems," Kluwer Academic Publishers, 1999.

[37]陳育嘉，二氧化鈦與氧化鉀對摻鉻氧化矽玻璃與玻璃陶瓷之光學特性影響暨雷射誘發結晶之影響，碩士論文，國立中山大學，2012。

[38] Ainhoa Gaston, Ibon Lozano, Fátima Perez, Fernando Auza, and Joaquín Sevilla, "Evanescent Wave Optical-Fiber Sensing (Temperature, Relative Humidity, and pH Sensors)," Sensors Journal, IEEE, vol. 3, issue 6, pp. 806-811, Dec. 2003.

[39] G. L. Klunder, J. Bürck, H.-J. Ache, R. J. Silva, and R. E. Russo, "Temperature Effects on a Fiber-Optic Evanescent Wave Absorption Sensor," Applied Spectroscopy, vol. 48, issue 3, pp. 387-393, 1994.

[40]蔡源展，溫度無感之光纖光柵振動感測器之研究，碩士論文，國立清華大學，2005。

[41]張元哲，光纖式氧氣感測器之溫度補償研究，碩士論文，國立成功大學，2006。