本文利用矽烷單分子膜及LB膜將親水性玻璃基板表面進行表面改質後，再利用(Physical Vapor Deposited, PVD)物理氣相沈積技術，將四第三丁基銅花青(Copper-Tetra-Tert-Butyl Phthalocyanine, CuTTBPc)加熱沈積至矽烷單分子膜改質玻璃基板、單層LB膜改質玻璃基板和玻璃基板上。由動態接觸角(Dynamic Contact Angle, DCA)的測量來分析花青薄膜的表面潤濕性，並藉由原子力顯微鏡(Atomic Force Microscope, AFM)及X-ray繞射儀(X-ray Diffraction, XRD)來觀察其在固體基板上的型態及結構。探討在不同沈積時間下，基板效應的差異對薄膜成長行為的影響。
由實驗結果發現，在矽烷改質的疏水性玻璃基板上，晶粒數目較高，表面較為平坦，顯示花青分子與矽烷表面親和力較大，於成長初期之成核速率較快，且薄膜傾向於細小多晶的結構，而在較低的厚度便形成連續膜。在玻璃基板上的晶粒數目相形較少、半徑較大，且平均粗糙度大，使得沈積的薄膜分子傾向於縱向成長，而呈現結晶性較高的情況。在單層LB膜改質玻璃基板上，因花青分子並非以均勻單分子膜形式排列，而是以細小的分子團分散於玻璃面上，這些分子團在花青沈積過程中，提供穩定的成核位置，使得薄膜結構亦傾向細小多晶，類似於在矽烷改質玻璃基板面上所得之結果。

Three substrates including hydrophilic glass, silane monolayer, and LB film of CuTTBPc, were used to study the substrate effects on the nucleation and growth behavior of CuTTBPc thin films in the process of physical vapor deposition. The surface morphology and structure of the films were investigated, respectively, by AFM and XRD spectrum.
The results show that the cluster density is small and the morphology is rougher for the films grown on the glass. That is, the nucleation rate is small on the glass and the growth tends to the direction normal to the substrate surface, which leads to a larger grain structure. On the contrary, the cluster density is comparatively higher and the mean roughness is smaller on the substrate of silane monolayer. These phenomena indicate that CuTTBPc molecules have higher adhesive force to the silane surface and a poly-fine-grained structure is resulted.
For the substrate of CuTTBPc LB film, the CuTTBPc molecules aggregate into separated domains of multi-layers. These domains, with higher density, act as stable nucleation sites in the later process of vapor deposition and thus, a poly-fine-grained structure is also resulted.

參考文獻
Angst, D.L., and Simmons, G.W., “Moisture Absorption Characteristics of Organosiloxane Self-Assembled Monolayers,” Langmuir 7, 2236, 1991.
Baker, S., Petty, M.C., Roberts, G.G., and Twigg, M.V., “The Preparation and Properties of Stable Metal-Free Phthalocyanine Langmuir-Blodgett Films”, Thin Solid Films 99, 53, 1983.
Barger, W.R., Snow, A.W., Wohltjen H., and Jarvis, N.L., “Derivatives of Phthalocyanine Prepared for Deposition as Thin Films by the Langmuir-Blodgett Technique,” Thin Solid Films 133, 197, 1985.
Bauer, E. and Poppa, H., “Recent Advances in Epitaxy, ” Thin Solid Films 12, 167, 1972.
Berg, J.C., “Wettability,“ Marcel Dekker, New York, 1993.
Bierbaum, K., Grunze, M., Baski, A.A., Chi, L.F., Schrepp, W., and Fuchs, H., ”Growth of Self-Assembled n-Alkyltrichlorosilane Films on Si(100) Investigated by Atomic Force Microscopy,” Langmuir 11, 2143, 1995.
Brzoska,, J.B., Shahidzadeh, N., and Rondelez, F., “Evidence of a Transition-Temperature for the Optimum Deposition of Grafted Monolayer Coatings,” Nature 360, 719, 1992.
Brynda, E., Koropecky, I., Kalvoda L., and Nespurek, S., “Electrical and Photoelectrical Properties of Copper Tetra-4-t-butyl Phthalocyanine Langmuir-Blodgett Films,” Thin Solid Films 199, 375, 1991.
Burack, J.J., LeGrange, J.D., Markham, J.L., and Rocaward, W., “Spectroscopic Studies of Phthalocyanine Monolayers,” Langmuir 8, 613, 1992.
Chen, L.H., Chen, C.Y., and Lee, Y.L., Surface Sci., 429, 150, 1999.
Cohen, S. R., Naaman, Ron and Sagiv, J., J. Phys. Chem., 90, 3054, 1986
Cook, M.J., Daniel, M.F., Dunn, A.J., Gold, A.A., and Thomson, A.J., “Determination of Molecular Orientation of Copper Phthalocyanine in a Langmuir-Blodgett Film Using E.S.R. Spectroscopy,” J. Chem. Soc. Chem. Comm. 11, 863, 1986.
Cook, M.J., Dunn, A.J., Gold, A.A., Thomson, A.J., and Daniel, M.F., “Association and Orientation of Copper Tetra-t-butyl Phthalocyanine in Multilayer Langmuir-Blodgett Films as Determined by Electron Paramagnetic Resonance Spectroscopy,” J. Chem. Soc. Dalton Trans. 5/6, 1583, 1988.
DePalma, V., and Tillman, N., “Friction and Wear of Self-Assembled Trichlorosilane Monolayer Films on Silicon,” Langmuir 5, 868, 1989.
Emelyanov, Y.L., Kohatko, V.V., and Tomchenko, A.A., “Preparation and Thermostable Properties of Langmuir-Blodgett Films of Copper Tetra-tert-butyl Phthalocyanine Complex,” Synthetic Metals 79, 173, 1996.
Flinn, D.H., Guzonas, D.A., and Yoon, R.-H., “Characterization of Silica Surfaces Hydrophobized by Octadecyltrichlorosilane,” Colloids and Surfaces A: Physicochemical and Engineering Aspects 87, 163, 1994.
Fryer, J.R., Hann R.A., and Eyres, B.L., “Single Organic Monolayer Imaging by Electron Microscopy,” Nature 313, 382, 1985.
Fryer, J.R., McConnell, C.M., Hann, R.A., Eyres B.L., and Gupta, S.K., “The Structure of Some Langmuir-Blodgett Films. Part I. Substituted Phthalocyanines,” Philosophical Magazine B 61, 843, 1990.
Hann, R.A., Gupta, S.K., Fryer, J.R., and Eyres, B.L, “Electrical and Structural Studies on Copper Tetra-tert-butyl Phthalocyanine Langmuir-Blodgett Films,” Thin Solid Films 134, 35, 1985.
Johnstone, J., Peacock, C.A., Roberts, K.J., Hann, R.A., Oldman, R.J., and Gupta, S.K., “Investigating the Orientation of Langmuir Blodgett Films of Copper Tetra-t-butyl Phthalocyanine Using Polarised, Ultra-soft Xanes Spectroscopy,” Molecular Crystals and Liquid Crystals Science and Technology: Section A-Molecular Crystals and Liquid Crystals 278, 157, 1996.
Kalina, D.W., and Crane, S.W., “Langmuir-Blodgett Films of Soluble Copper Octa(dodecoxymethyl) Phthalocyanine,” Thin Solid Films 134, 109, 1985.
Kutzler, F.W., Barger, W.R., Snow, A.W., and Wohltjen, H., “An Investigation of Conductivity in Metal-Substituted Langmuir Blodgett Films,” Thin Solid Films 155, 1, 1987.
Lander, L.M., Siewierski, L.M., Brittain, W.J. and Vogler, E.A., “A Systematic Comparison of Contact Angle Methods,” Langmuir 9, 2237, 1993.
Le Grange, J.D., Markhan, J.L., and KurKjian C.R., “Effects of Surface Hydration on the Deposition of Silane Monolayers on Silica,” Langmuir 9, 1749, 1993.
Leznoff, C. C. and A. B. P. Lever, “Phthalocyanines Properties and Applications,” VCH, 1992
Lloyd, J.P., Pearson, C., and Petty, M.C., ”Surface Plasmon Resonance Studies of Gas Effects in Phthalocyanine Langmuir-Blodgett Films,” Thin Sold Films 160, 431-443, 1988.
McGovern, M.E., Kallury, K.M.R., and Thompson, M., “Role of Solvent on the Silanization of Glass with Octadecyltrichlorosilane,” Langmuir 10, 3607, 1994.
Nabok, A.V., Kazantseva, Z.I., Lavrik, N.V., and Nesterenko, B.A., “Nitrogen Oxide Gas Sensor Based on Tetra-tert-butyl Copper Phthalocyanine Langmuir-Blodgett Films,” Int. J. Electronics 78, 129, 1995.
Nichogi, K., Waragai, K., Taomoto, A., Saito, Y., and Asakawa, S., “Lead Phthalocyanine Langmuir-Blodgett Films,” Thin Solid Films 179, 297, 1989.
Parikh, A.N., Allara, D.L., Azouz, I.B., and Rondelez, F., “An Intrinsic Relationship between Molecular Structure in Self-Assembled n-Alkylsiloxane Monolayers and Deposition Temperature,” J. Phys. Chem. 98, 7577, 1994.
Robert, G.G., Petty, M.C., Baker, S., Fowler, M.T., and Thomas, N.J., “Electronic Devices Incorporation Stable Phthalocyanine Langmuir-Blodgett Films,” Thin Solid Films 132, 113, 1985.
Rye, R.R., “Transition Temperature for n-Alkyltrichlorosilane Monolayer,” Langmuir 13, 2588, 1997.
Sadaoka, Y., T. A. Jones, G. S. Revell, W. Göpel, “Effects of Morphology on NO2 Detection in Air at Room-Temperature with Phthalocyanine Thin Films,” J. Materials Science 25, 5257, 1990.
Sagiv, J., ”Organized Monolayers by Adsorption. 1. Formation and Structure of Oleophobic Mixed Monolayers on Solid Surfaces,” J. Am. Chem. Soc., 102, 92, 1980.
Silberzan, P., Leger, L., Ausserre, D., and Benattar, J.J., “Silanation of Silica Surface. A New Method of Constructing Pure or Mixed Monolayers,” Langmuir 7, 1647, 1991.
Snow, A.W., and Barger, W.R., in Leznoff, C.C., and Lever, A.B.P. (Eds.), Phthalocyanines: Properties and Applications, Chapter 5, VCH, New York, 1989.
Snow, A.W., and Jarvis, N.L., “Molecular Association and Monolayer Formation of Soluble Phthalocyanine Compounds,” J. Am. Chem. Soc. 106, 4706, 1984.
Souto, J., and Saja, J.A., “NOx Gas Detection with Langmuir-Blodgett Monolayers of Tetra-tert-butyl Phthalocyanine Complexes,” Sensors and Actuators B 16, 306, 1993.
Ulman, A., An Introduction to Ultrathin Organic Films, Academic Press, New York, 1991.
Wasserman, S.R., Tao, Y.T., and Whitesides, G.M., “Structure and Reactivity of Alkylsiloxane Monolayers Formed by Reaction of Alkyltrichlorosilane on Silica Substrates,” Langmuir 5, 1074, 1989.
Woodward, J.T., Ulman, A., and Schwartz, D.K., “Self-Assembled Monolayer Growth of Octadecylphosphonic Acid on Mica,” Langmuir 12, 3626, 1996.
林昆模，多層花青LB膜的製備及氣體感測特性之研究，成功大學化學工程學系碩士論文，2001.
古宜訓，沈積促進劑對花青LB膜沈積的影響，成功大學化學工程學系碩士論文，2000.
蔡怡杏，自聚性分子膜成膜動力學之臨界溫度研究，台灣大學化學工程學系碩士論文，1999.
陳永昌，有機金屬LB膜之製備及其特性之探討，成功大學化學工程學系碩士論文，1999.
鄭熤騰、鄭耀宗，”氣體感測器的市場分析與發展概況，” 科儀新知 18, 76, 1997.
方聰賢，固體表面潤濕性與滴式冷凝之研究，成功大學化學工程學系碩士論文，1996.
林麗娟，”X光繞射原理及其應用，” 工業材料86, 100, 1994.