簡易檢索 / 詳目顯示

研究生: 蔡其成
Chi-Cheng Tsai
論文名稱: 感光型聚偏二氟乙烯壓電薄膜之微影與應用特性探討
Development of photosensitive Poly(vinylidene fluoride) piezoelectric film lithographic characteristics and its application
指導教授: 楊啓榮
Yang, Chii-Rong
學位類別: 碩士
Master
系所名稱: 機電工程學系
Department of Mechatronic Engineering
論文出版年: 2004
畢業學年度: 92
語文別: 中文
論文頁數: 126
中文關鍵詞: 聚偏二氟乙烯感光特性微影製程負型光阻壓電材料
英文關鍵詞: poly(vinylidene fluoride), photolithographic characteristics, photolithography fabrication, negative photoresist, piezoelectric material, PVDF
論文種類: 學術論文
相關次數: 點閱:146下載:17
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報
  • 傳統之陶瓷壓電材料,如鋯鈦酸鉛(PZT)等,必須使用射頻磁控濺鍍法來進行薄膜沈積,或是以溶膠-凝膠法(sol-gel)旋塗後再高溫燒結(650 C-700 C),所產生之製程設備昂貴、薄膜結構製程複雜或高溫燒結會使微元件受到破壞等缺點。然而,在微機電領域製作微小型結構,若材料承受高溫燒結,必會造成材料產生殘留應力過大之現象,使得微小結構遭受破壞、表面破裂等缺點。因此,必須發展新型焦電材料與結合低溫製程,以實現低成本微元件之開發。
    高分子壓電薄膜材料聚偏二氟乙烯(polyvinylidene fluoride, PVDF),以低溫烘烤(< 80 ℃)成貝塔相(β phase)後,再以外加強電場方式將薄膜極化,使其具備焦電與壓電特性。如此一來,薄膜成相不必經過高溫燒結過程,較不易造成殘留應力過大、微結構彎曲變形等問題。壓電材料PVDF本身具有高撓性之優點且屬低溫之製程,使在製作過程中不會產生應力過大現象。
    本研究主要可分為兩大部份:
    1. 利用添加感光藥劑,進行聚偏二氟乙烯溶液的改質,已開發出具備感光特性之溶液,並且以霍式轉換紅外光譜儀與X-ray粉末繞射儀,確定材料的結晶相。
    2. 將可微影之聚偏二氟乙烯壓電材料,配合微機電製程技術,成功地釋放微結構。

    In this study, the focal point is to change intrinsic character of polymer piezoelectric PVDF as photosensitive. After that, PVDF is provided with photolithography properties and still has piezoelectric and pyroelectric functions. The photosensitive PVDF solution has advantages of defining the patterns easily and having low temperature processes. Replacing traditional pyro-materials such as PbTiO3, (Pb, Ca)TiO3, LiTaO3, PZT that deposit piezo-film using RF sputter, sol-gel with high temperature sintering. The disadvantages of these traditional materials are expensive facilities, complex fabrication processes and CMOS circuit damaged by high-temperature sintering.

    The major contents in this proposal include:
    1. To develop the photosensitive PVDF solution and find the optimal fabrication parameters: it can prepare the photosensitivity of PVDF solution by adding appropriate photo-initiator, photo-sensitizer and crosslinker etc. And to confirm the  phase of PVDF using FTIR and X-ray.
    2. Using microelectro mechanical system technologies to release the cantilever beams using photolithographic PVDF solution. The PS-PVDF solution is suit for MEMS field.

    總 目 錄 摘 要 Ⅰ 總目錄 Ⅲ 圖目錄 Ⅵ 表目錄 XI 第一章 緒論 1 1.1 前言 1 1.2 壓電材料分類 4 1.3 壓電材料之特性 7 1.3.1 壓電效應 7 1.3.2 焦電效應 7 1.3.3 鐵電效應 8 1.4 壓電材料之極化過程 11 1.5 研究動機 14 第二章 文獻回顧 15 2.1 改質高分子之應用 15 2.2 壓電材料之特性研究 18 2.2.1 聚偏二氟乙烯 18 2.2.2 聚偏二氟乙烯之結構分析 19 2.3 聚偏二氟乙烯之成形方式 26 2.3.1 旋轉塗佈法 26 2.3.2 鹵素燈加熱蒸發法 27 2.3.3 裁剪黏貼法 27 2.3.4 電極噴霧法 28 2.3.5 同步輻射光刻法 29 第三章 研究設計與實驗方法 37 3.1 研究設計法則 37 3.1.1 實驗步驟設計 37 3.1.2 結構設計 42 3.2 實驗規劃與方法 48 3.3 實驗設備 55 3.4 材料分析儀器 64 3.4.1 霍式轉換紅外光譜儀 64 3.4.2 X-ray粉末繞射儀 65 第四章 實驗結果與討論 66 4.1 感光型聚偏二氟乙烯之特性探討 66 4.1.1 感光型聚偏二氟乙烯溶液之製備 66 4.1.2 黏著層之選用 66 4.1.3 黃光微影參數探討 68 4.2 壓電材料特性分析 82 4.2.1 霍式轉換紅外光譜分析 82 4.2.2 X-ray粉末繞射儀 84 4.3 壓電微懸臂樑之製作 96 4.3.1 溼式蝕刻製作下電極 96 4.3.2 壓電懸臂樑之製作 97 4.4 電性量測結果 116 第五章 結論 118 5.1 結論 118 5.2 未來展望 120 參考文獻 121

    參考文獻
    1.楊啟榮等人, "微機電系統技術與應用", 精密儀器發展中心, 第四章, pp. 142 (2003).
    2.R. G. Kepler and R. A. Anderson, "Ferroelectricity in polyvinylidene fluoride", Journal of Applied Physics, Vol. 49, No. 3, pp. 1232-1235 (1978).
    3.A. P, "Pyroelectrics for smart munitions", Reprinted from Sensors, April (1988).
    4.Z. Ounaies, J. S. Harrison and R. J. Silcox, "Piezoelectric materials for sensor and actuator applications at NASA LaRC", ICASE Research Quarterly, Quarterly Newsletter of the Institute for Computer Applications in Science and Engineering, Vol. 8, No. 2, pp. 12-23 (1999).
    5.R. F. M. Marcal, J. L. Kovaleski and A. A. Suzim, "A poly vinylidene fluoride (PVF2) piezoelectric film based accelerometer", IEEE Instrumentation and Measurement Technology Conference, Vol. 19-21, pp. 908-913 (1997).
    6.N. Fujitsuka, J. Sakata, Y. Miyachi, K. Mizuno, K. Ohtsuka and Y. Taga, "Monolithic pyroelectric infrared image sensor using PVDF thin film", Transducers’97, pp. 1237-1240 (1997).
    7.B. Ploss, P. Lehmann, H. Schopf, T. Lessle, S. Bauer and U. Thiemann, "Integrated pyroelectric detector arrays with the sensor material PVDF", Ferroelectrics, Vol. 109, pp. 223-228 (1990).
    8.S. Bauer, S. B. Gogonea, W. Becker, R. Fettig, B. Ploss and W. Ruppel, "Thin metal films as absorbers for infrared sensors", Sensors and Actuators A, Vol. 37-38, pp. 497-501 (1993).
    9.D. Cathignol and A. Thomas, "PVDF hydrophone with liquid electrodes for shock wave measurements", Ultrasonics Symposium, 1990. Proceedings., IEEE 1990, Vol. 1, pp. 341-344 (1990).
    10.G. W. Taylor, J. R. Burns, S. M. Kammann, W. B. Powers and T. R. Welsh, "The energy harvesting eel: a small subsurface ocean/river power generator", IEEE Journal of Oceanic Engineering, Vol. 26, No. 4, pp. 539-547 (2001).
    11.M. E. Motamedi, "Acoustic sensor technology", Microwave Symposium Digest, 1994., IEEE MTT-S International, Vol. 1, pp. 521-524 (1994).
    12.P. D. Wilcox, P. Cawley and M. J. S. Lowe, "Acoustic fields from PVDF interdigital transducers", IEE Proceedings-Science Measurement and Technology, Vol. 145, No. 5, pp. 250-259 (1998).
    13.M. Lebedev and J. Akedo, "Effect of thickness on the piezoelectric properties of lead zirconate titanate films fabricated by aerosol deposition method", Japanese Journal of Applied Physics, Vol. 41, pp. 6669-6673 (2002).
    14.A. Mahrane and M. D. Rouhani, "P(VDF-TrFE) copolymer sensor for passive IR detection in automotives", Sensors and Actuators A, Vol. 46-47, pp. 399-402 (1995).
    15.Y. Daben, "Composite piezoelectric film made from PVDF polymer and PCM-PZT ferroelectric ceramics", Ferroelectrics, Vol. 101, pp. 291-296 (1990).
    16.D. Sinha, N. Shroff and P. K. Pillai, "Dc conduction mechanism in the composite system of lead zirconate titanate and polyvinylidene fluoride", Ferroelectrics, Vol. 103, pp. 49-56 (1990).
    17.D. Sinha and P. K. C. Pillai, "The conductivity behavior in lead zirconate titanate polyvinylidene fluoride composites", Journal of Applied Physics, Vol. 64, No. 5, pp. 2571-2574 (1988).
    18.P. Ueberschlag, "PVDF piezoelectric polymer", Sensor Review, Vol. 21, No. 2, pp. 118-125 (2001).
    19.M. Okuyama, "Microsensors and microactuators using ferroelectric thin films", IEEE International Symposium on Micromechatronics and Human Science, pp. 29-34 (1998).
    20.T. Evans, S. Sun, J. Ruffner and P. Clem, "Proceedings of ISAF 2000: aerogel isolated pyroelectric IR detector", IEEE Applications of Ferroelectrics, 12th IEEE International Symposium on, Vol. 1, pp. 221-226 (2001).
    21.K. Takashima and T. Oda, "Space and surface charge behavior analysis of plasma pre-processed dielectric thin films", IEEE Industry Applications Conference, pp. 2052-2057 (1997).
    22.T. T. Wang and J. E. West, "Polarization of poly(vinylidene fluoride) by application of breakdown field", Journal of Applied Physics, Vol. 53, No. 10, pp. 6552-6556 (1982).
    23.T. Oda and K. Takashima, "Space charge distribution measuring system using PVDF piezoelectric thin film", IEEE Industry Applications Conference, pp. 1949-1954 (1996).
    24.H. Kueppers, T. Leuerer, U. Schnakenberg, W. Mokwa and M. Hoffmann, "PZT thin films for piezoelectric microactuator applications", Sensors and Actuators A, Vol. 97-98, pp. 680-684 (2002).
    25.Q. Q. Zhang, S. J. Gross, S. Tadigadapa and T. N. Jackson, "Lead zirconate titanate films for d33 mode", Sensors and Actuators A, Vol. 105, pp. 91-97 (2003).
    26.G. M. Sessler, "Piezoelectricity on polyvinylidenefluoride", Journal of the Acoustical Society America, Vol. 70, No. 6, pp. 1596-1608 (1981).
    27.N. Alves, C. X. Cardoso, A. E. Job and J. A. Giacometti, "Effects of thermal treatment on phase transitions and on the mechanical relaxation in poly(vinylidene fluoride)", Electrets, 2002. ISE 11. Proceedings. 11th International Symposium on, pp. 263-266 (2002).
    28.R. Gregorio and E. M. Ueno, "Effect of crystalline phase, orientation and temperature on the dielectric properties of poly(vinylidene fluoride)(PVDF)", Journal of Materials Science, Vol. 34, pp. 4489-4500 (1999).

    29.H. J. Suh, P. Bharathi, D. J. Beebe and J. S. Moore, "Dendritic material as a dry-release sacrificial layer", Journal of Microelectromechanical Systems, Vol. 9, No. 2, pp.198-205 (2000).
    30.J. P. Jayachandran, H. A. Reed, H. Zhen, L. Rhodes, C. L. Henderson, S. A. B. Allen and P. A. Kohl, "Air-channel fabrication for microelectromechanical systems via sacrificial photosensitive polycarbonates", Journal of Microelectromechanical Systems, Vol. 12, No. 2, pp. 147-159 (2003).
    31.H. Kawai, "The piezoelectricity of poly(vinylidene fluoride) ", Japanese Journal of Applied Physics, Vol. 8, pp. 975-976 (1969).
    32.J. G. Bergman, J. H. Mcfee and G. R. Crane, "Pyroelectricity and optical second harmonic generation in polyvinylidene fluoride films", Applied Physics Letters, Vol. 18, No. 5, pp. 203-205 (1971).
    33.江文彥, "神奇的氟聚合物-鐵氟龍和聚偏二氟乙烯", 化工技術, 第七卷, pp. 230-237 (1999).
    34.J. I. Scheinbeim, "Poly(vinylidene fluoride) ", Polymer Data Handbook, Oxford University, pp. 949-955 (1999).
    35.K. Tashiro, H. Tadokoro and M. Kobayashi, "Structure and piezoelectricity of poly(vinylidene fluoride)", Ferroelectrics, Vol. 32, pp. 167-175 (1981).
    36.M. G. Broadhurst, G. T. Davis and J. E. Mckinney, "Piezoelectricity and pyroelectricity in polyvinylidene fluoride-A model", Journal of Applied Physics, Vol. 49, No. 10, pp. 4992-4997 (1978).
    37.A. Salimi and A. A. Yousefi, "FTIR studies of -phase crystal formation in stretched PVDF films", Polymer Testing, Vol. 22, pp. 699-704 (2003).
    38.M. Kobayashi, K. Tashiro and H. Tadokoro, "Molecular vibrations of three crystal forms of Poly(vinylidene fluoride) ", Macromolecules, Vol. 8, No. 2, pp. 158-171 (1975).
    39.K. Tashiro, M. Kobayashi, H. Tadokoro and E. Fukada, "Calculation of elastic and piezoelectric constants of polymer crystals by a point charge model: application to Poly(vinylidene fluoride) form Ⅰ", Macromolecules, Vol. 13, pp. 691-698 (1980).
    40.H. L. V. Chan, A. H. Ramelan, I. L. Guy and D. C. Price, "VF2/VF3 copolymer hydrophone for ultrasonic power measurements", IEEE Proceeding Ultrasonics Symposium, Vol. 1, pp. 617-620 (1989).
    41.C. M. Wang, M. C. Kao and Y. C. Chen, "Preparation and electrical property of -PVDF/PbTiO3 thin films", Applications of Ferroelectrics, 2002. ISAF 2002. Proceedings of the 13th IEEE International Symposium on, Vol. 28, pp. 175-178 (2002).
    42.H. Don, "Putting piezo polymer film to work", Machine Design, Vol. 66, No. 14, pp. 47-51 (1994).
    43.R. Schellin, G. Hess and W. Kuehnel, "Silicon subminiature microphones with organic piezoelectric layers", IEEE Transactions on Electrical Insulation, Vol. 27, No. 4, pp. 867-871 (1992).
    44.S. H. Park, E. C. Lim and K. S. Park, "The dielectric properties of functional PVDF thin films by physical vapor deposition method", IEEE Proceedings of the 5th International Conference on Properties and Applications of Dielectric Materials, Vol. 25-30, pp. 1144-1146 (1997).
    45.Y. Takahashi, M. Iijima and E. Fukada, "Pyroelectricity in poled thin films of aromatic polyurea prepared by vapor deposition polymerization", Japanese Journal of Applied Physics, Vol. 28, No. 12, pp. 2245-2247 (1989).
    46.J. Dargahi and M. Parameswaran, "A micromachined piezoelectric tactile sensor for an endoscopic grasper-theory, fabrication and experiments", Journal of Microelectromechanical Systems, Vol. 9, No. 3, pp. 329-335 (2000).
    47.K. L. Choy and W. Bai, "Preparation of oriented poly(vinylidene fluoride) thin films by a cost-effective electrostatic spray-assisted vapour deposition-based method", Thin Solid Films, Vol. 372, pp. 6-9 (2000).
    48.H. M. Manohara, E. Morikawa, J. Choi and P. T. Sprunger, "Pattern transfer by direct photo etching of poly(vinylidene fluoride) using X rays", Journal of Microelectromechanical System, Vol. 8, No. 4, pp. 417-422 (1999).
    49.E. Morikawa, J. Choi and H. M. Manohara, "Photoemission study of direct photomicromachining in poly(vinylidene fluoride)", Journal of Applied Physics, Vol. 87, No. 8, pp. 4010-4016 (2000).
    50.W. Y. Chiang and H. T. Kuo, "Preparation of trimethylsilyl group containing copolymer for negative-type photoresists that enable stripped by an alkaline solution", European Polymer Journal, Vol. 38, pp. 1761-1768 (2002).
    51.J. Soon and S. I. Hong, "Synthesis of acrylic rosin derivatives and application as negative photoresist", European Polymer Journal, Vol. 38, pp. 387-392 (2002).
    52.S. Osaki and T. Kotaka, "Electrical properties of form Ⅲ Poly(vinylidene fluoride) ", Ferroelectrics, Vol. 32, pp. 1-11 (1981).
    53.R. Gregorio, J. R and M. Cestari, "Effect of crystallization temperature on the crystalline phase content and morphology of Poly(vinylidene fluoride) ", Journal of Polymer Science: Part B: Polymer Physics, Vol. 32, pp. 859-870 (1994).
    54.S. J. Oh, J. Zhang, Y. Cheng, H. Shimoda and O. Zhou, "Liquid-phase fabrication of patterned carbon nanotube field emission cathodes", Applied Physics Letters, Vol. 84, No. 19, pp. 3738-3740 (2004).
    55.賴昀星, "雙層(聚偏二氟乙烯/鈦酸鉛)薄膜型焦電感測器之研究", 國立中山大學電機工程學系研究所, 碩士論文, p. 29 (2001).
    56.G. T. Davis, J. E. Mckinney, M. G. Broadhurst and S. C. Roth, "Electric-field-induced phase changes in poly(vinylidene fluoride) ", Journal of Applied Physics, Vol. 49, No. 10, pp. 4998-5002 (1978).

    QR CODE