利用模板分子合成的中孔洞材料具孔徑大小一致、規則的孔道排列、高表面積、高熱穩定性等特性，其中中孔洞薄膜因可以塗佈於各種基材上最具應用性，可應用於催化與分離反應、低介電值( low-k dielectrics)薄膜材料、抗反射材料等。薄膜的應用性與薄膜的性質有密切的關係，除了需調整製備過程中的參數外，最後仍需配合各種方法的鑑定才能獲得較完整的資訊。
在各種影響薄膜性質的實驗參數中，模板分子的移除是影響薄膜性質重要的關鍵，本論文即以三塊狀聚合高分子P123為模板分子，製備孔徑較大的中孔洞薄膜，並探討各種模板分子移除法(包括高溫鍛燒法、UV-O3照射移除法、溶劑萃取法及溶劑萃取法的結合)對薄膜結構及孔洞性質的影響。並以低掠角反射式IR、XRR、XRD、氪氣吸附、n&k analyzer等鑑定對各種移除法作完整性的探討。
本論文的第一章為文獻回顧，介紹中孔洞薄膜的製備、薄膜鑑定技術、目前常用的模板分子移除法等; 第二章為實驗部分，對實驗的條件、流程、使用到的儀器等作介紹 ; 第三章為結果與分析，主要分為二氧化矽前驅液老化時間的探討、各種模板分子移除法移除效率及對結構性質的影響、HMDS疏水性改質對孔洞性質的影響、氨氣預處理對孔洞性質的影響; 第四章為結論，將實驗結果作最後的統整。

Inorganic-organic mesostructured materials obtained by a cooperative organization of inorganic species and surfactants have uniform pore size, ordered pore channel, high surface area, and high thermal stability. Thin films of silica-surfactant mesostructured materials have an ideal morphology; therefore, they could find applications in fields such as catalysis, separation, low-k materials and anti-reflective coatings. Different syntheses have been proposed in order to obtain a wide range of mesoporous geometries to match the specificities of the applications. Besides the preparation conditions, it is very important to characterize film properties for their applications.
Film properties of the final mesostructured material are markedly affected by methods of eliminating the organic templates. We use P123 as the templating agents to prepare mesoporous films with larger pores. Emphasis is given on the effect of the template removal by thermal calcination, solvent extraction ,UV-O3 irradiation or solvent extraction combined with UV-O3 irradiation.
In this thesis the evolution of the film structure and pore properties are studied as a function of the template removal processing by coupling with grazing incident reflectance IR, X-ray reflection (XRR), X-ray diffraction (XRD), Kr adsorption, and n&k analyzer.
In Chapter 1, an introduction of mesoporous films, thin film characterization techniques and template removal methods are described. In Chapter 2, the experimental condition and characterization techniques are described. In Chapter 3, the preparation parameters are discussed including﹕aging time, template removal methods, HMDS hydrophobic modifications and NH3 pretreatment effects. In Chapter 4, the final conclusion is described.

[1] J. S. Beck, J. C. Vartuli, W. J. Roth, M. E. Leonowicz,C. T. Kresge,
K. D. Schmitt, J. Am. Chem. Soc. 1992, 114, 10834-10843.
[2] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck,
Nature. 1992, 359, 710-712
[3] J.C. Vartuli, W. J. Roth, J. S. Beck, S. B. McCullen, C. T. Kresge, Molecular Sieves, Vol. 1 (Springer- Verlag, 1998) pp.97-119
[4] Osamu Terasaki, Mesoporous crystals and related nano-structured materials (Elsevier, 2004) pp.69-71
[5] Makoto Ogawa, J. Am. Chem. Soc. 1994, 116, 7941-7942
[6] Lu, Y.; Ganguil, R.; Drewien, C. A.; Anderson, M. T.; Brinker, C. J.; Gong, W.; Guo, Y.; Soyez, Z.; Dunn, B.; Huang, M. H.; Zink, J. I. Nature 1997, 389, 364-368
[7] Sellinger, A.; Weiss, P.M.; Nguyen, A.; Lu, Y.; Assink, R.A.; Gong, W.; Brinker, C.J.; Nature 1998, 394, 256-260
[8] Zhao, D.; Yang, P.; Melosh, N.; Feng, J.; Chmelka, B. F.; Stucky, G. D. Adv. Mater. 1998, 10 (6), 1380-1385
[9] Zhao, D.; Yang, P.; Margolese, D. I.; Feng, J.; Chmelka, B. F.; Stucky, G.D. Chem. Comm. 1998, 2499-2500
[10]Yang, P.; Wirnsberger, G.; Huang, H. C.; Cordero, S.R.; McGehee, M. D.; Scott, B.; Deng, T.; Whitesides, G. M.; Chmelka, B. F.; Buratto, S. K.; Stucky, G. D. Science 2000, 287 (21), 465-467
[11] C.M.Yang, A. T. Cho, F. M. Pan, T. G. Tsai, K. J. Chao, Advanced Materials 2001, 13(14), 1099-1102

[12] T. G. Tsai, A. T. Cho, C. M. Yang, F. M. Pan and K. J. Chao, Journal of The Electrochemical Society, 2002, 149(9), 116-121
[13] C. J. Brinker, Yunfeng Lu, Alan Sellinger and Hongyou Fan,
Adv. Mater. 1999, 11(7), 579-585
[14] Makoto Ogawa , Naoshi Masukawa, Microporous and Mesoporous Materials , 2000, 38, 35-41
[15] S. Che, Z. Liu, T. Ohsuna, K. Sakamoto, O. Terasaki and T. Tatsumi, Nature, 2004, 429, 281-284
[16] D. Zhao, J. Sun, Q. Li, and G. D. Stucky, Chem. Mater. 2000, 12, 275-279
[17] C. Yu, J. Fan, B. Tian, and D.Zhao, Chem. Mater. 2004, 16, 889-898
[18] Corma, A. Chem. Rev. 1997, 97, 2373-2419
[19] J. Y. Chen, F. M. Pan, A. T. Cho, K. J. Chao, T. G. Tsai, B. W. Wu, C. M. Yang, and Li Chang, Journal of The Electrochemical Society 2003, 150 (6), 123-127
[20] A. R. Balkenende, F. K. de Theije, and J. C. Koen Kriege, Adv.Mater. 2003, 15(2), 139-143
[21] M.C. Bautista and A. Morales, Solar Energy Materials & Solar Cells 2003, 80, 217–225
[22] N. Raman, M. Anderson, C. J. Brinker, Chem. Mater. 1996, 8, 1682-1701
[23] H. W. Hillhouse, J. W. van Egmond, M. Tsapatsis, J. C. Hanson, J. Z. Larese, Microporous and Mesoporous Materials, 2001, 44-45, 639-643

[24] T. Yamada, K. Asai , A. Endo, H. S. Zhou, I . Honma, Journal of Materials science letters, 2000, 19, 2167-2169
[25] H. Miyata and K. Kuroda, Chem. Mater. 1999, 11, 1609-1614
[26] K. J. Chao , P. H. Liu, K. Y. Huang, C. R. Chimie 2005, 8, 727–739
[27] Jorg Bolze, Moonhor Ree, and Kookheon Char, Langmuir 2001, 17, 6683-6691
[28] X. Li, T. K. S.Wong, Rusli, D. Yang, Diamond and Related Materials 2003, 12, 963-967
[29] http://www.rigakumsc.com/semi/about_tech.html
[30] 黃國瑩，國立清華大學化學研究所碩士論文，2004年。
[31] Gregg, S. J. and Sing, K. S. W. Adsorption, surface area and porosity (London, Academic press 2nd, 1982) pp.111-133
[32] S. Brunauer, P. H. Emmett, E. Teller, J. Am. Chem. Soc. 1938, 60, 309-319
[33] Hans-Jürgen Butt, Karlheinz Graf, Michael Kappl, Physics and Chemistry of Interfaces (Wiley-VCH, 2003) pp.177-192
[34] E. P. Barrett, Joyner, L. G. and Halenda, P. P., J. Am. Chem. Soc., 1951, 73, 373
[35] Harkins, M. R.; Jura, G. J. Am. Chem. Soc. 1944, 66, 1366-1373.
[36] Halsey, G.D., J. Chem. Phys., 1948, 16, 931-937.
[37] Magee, R.W., Presented Paper, Rubber Div., J. Am. Chem. Soc. Meeting, Pittsburgh, Pa., Oct., 11-14, (1994).
[38] M. Kruk, M. Jaroniec, R. Ryoo and S. H. Joo, Chem. Mater. 2000, 12, 1414-1421

[39] Kenneth Sing, Colloids and Surfaces A: Physicochemical and Engineering Aspects 2001, 187–188, 3–9
[40] C.Y. Chiu , A. S.T. Chiang , K. J. Chao , Microporous and Mesoporous Materials 2006, 91, 244–253
[41] A. R. Forouhi and I. Bloomer, Physical Review B 1986, 34(10), 7018-7026
[42] A. R. Forouhi and I. Bloomer Physical Review B 1988, 38(3), 1865-1874
[43] P. C. A. Alberius, K. L. Frindell, R. C. Hayward, E. J. Kramer,G. D. Stucky and B. F. Chmelka, Chem. Mater. 2002, 14, 3284-3294
[44] Xu-Feng Zhou, Cheng-Zhong Yu *, Jia-Wei Tang, Xiao-Xia Yan, Dong-Yuan Zhao, Microporous and Mesoporous Materials 79 (2005) 283–289
[45] S. Yua, T. K.S. Wonga, X. Hub, T. K. Goha, Thin Solid Films 2004, 462–463, 306– 310
[46] T. Yamada, K. Asai , A. Endo, H. S. Zhou, I . Honma, Journal of Materials Science Letters 2000, 19, 2167 – 2169
[47] F. Cagnol, D. Grosso, Galo J.de A. A. Soler-Illia, E. L. Crepaldi, F. Babonneau, H. Amenitschb and C. Sanchez J. Mater. Chem., 2003, 13, 61–66
[48] Schüth, F., Ciesla, U., Schacht, S., Thieme, M., Huo, Q., Stucky, G. Mater. Res. Bull. 1999, 34, 483-494
[49] J.Blanchard, F. Schüth, P. Trens, M. Hudson, Microporous and Mesoporous Materials 2000, 39, 163-170

[50] F. Kleitz, W. Schmidt, F. Schüth, Microporous and Mesoporous Materials 2001, 44-45, 95-109
[51] D. Zhao, Q. Huo, J. Feng, B. F. Chmelka, and G. D. Stucky, J. Am.
Chem. Soc. 1998, 120, 6024-6036
[52] D.Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B. F.
Chmelka, G. D. Stucky. Science 1998, 279, 548-552
[53] F. Kleitz, W. Schmidt, F. Schüth, Microporous and Mesoporous Materials 2003, 65, 1-29
[54] S. Hitz and R. Prins, Journal of Catalysis 1997, 168, 194-206
[55] Hua Z. L., Shi J. L., Wang L., Zhang W. H., Journal of Non-Crystalline Solids 2001, 292 (1-3), 177-183
[56] D. Grosso, A. R. Balkenende, P. A. Albouy, A. Ayral, H. Amenitsch, and F. Babonneau Chem. Mater. 2001, 13, 1848-1856
[57] Atsushi, H.; Hiroyuki, S., Katsumasa, H., Tetsuya, K.,and Osamu, T. Nanoletters, 2001, 1, 395-399.
[58] John R. Vig, J. Vac. Sci. Technol. 1985, A 3 (3), 1027-1034.
[59] Matthew T. J. Keene, R. Denoyel and Philip L. Llewellyn, Chem. Commun., 1998 , 2203-2204
[60] T. C. Jr., J. D. Ruiz, H. Fan, □C. J. Brinker, B. I. Swanson and A. N. Parikh, Chem. Mater. 2000, 12, 3879-3884
[61] A. M. Dattelbaum, M. L. Amweg, J. D. Ruiz, L. E. Ecke, A. P.
Shreve and A. N. Parikh, J. Phys. Chem. B 2005, 109, 14551-14556
[62] D. A. Doshi, N. K. Huesing, M. Lu, H. Fan, Y. Lu, K. S.Potter,
B. G. Potter Jr., A. J. Hurd, C. J. Brinker, Science 2000, 290, 107-111
[63] S. Kawi and M. W. Lai, Chem. Commun., 1998, 1407-1408

[64] R.V. Grieken, G.Calleja, G. D. Stucky, J. A. Melero, R. A. Garcý´ and J. Iglesias, Langmuir 2003, 19, 3966-3973
[65] L. Huang, C. Poh, S. C. Ng, K. Hidajat and S. Kawi, Langmuir 2005, 21, 1171-1174
[66] Yang,H.; Coombs, N.; Ozin, G. A., J. Mater. Chem., 1998, 8 , 1205-1211
[67] L. L. Hench, Sol-gel silica: properties, processing and technology transfer (Noyes, Westwood, N.J.,1998), pp.24-26
[68] C. J. Brinker and G. W. Scherer, Sol-gel science: The physics and chemistry of sol-gel processing (Academic Press, New York, 1990), pp.358
[69] Y. K. Hwang , K. R. Patil , S. H. Jhung , J-S Chang , Y. J. Ko , S-E Park ,Microporous and Mesoporous Materials 2005, 78, 245-253
[70] A. Jentys *, K. Kleestorfer, H. Vinek, Microporous and Mesoporous Materials 1999, 27, 321–328
[71] Hozumi, A.; Yokogawa, Y.; Kameyama, T.; Hiraku, K.; Sugimura, H.; Takai, O.; Okido, M. , Adv. Mater. 2000 , 12, 985-987
[72] A. Chougnet, C. Heitz, E. Søndergard, P. A. Albouyb and M. Klotz Thin Solid Films 2006, 495, 40 – 44
[73] A. Chougnet, C. Heitz, E. Søndergard, J. M. Berquier, P. A. Albouyb and M. Klotz, J. Mater. Chem., 2005, 15, 3340–3345
[74] Bolze, J.; Ree, M.; Youn, H. S.; Chu, S. H.; Char, K. Langmuir ,2001, 17, 6683-6691
[75] 清華大學化學所邱建洋碩士論文，2004年

[76] C. J. Brinker and G. W. Scherer, Sol-gel science: The physics and chemistry of sol-gel processing (Academic Press, New York, 1990), pp.628-631
[77] A. P. Rao ; G. M. Pajonk ; A. V. Rao, J. Mater. Sci. 2005, 40, 3481-3489
[78] E. F. Vansant, P. VanDer Voort and K. C. Vrancken, Characterization and chemical modification of the silica surface (Elsevier, 1995) pp.62-67
[79] K. Y. Huang, Z. P. He, K. J. Chao, Thin Solid Films 2006, 495, 197-204
[80] X. S. Zhao, G. Q. Lu, J. Phys. Chem. B 1998, 102, 1556
[81] E. F. Vansant, P. VanDer Voort and K. C. Vrancken, Characterization and chemical modification of the silica surface (Elsevier, 1995) pp.83-85
[82] Jason Rim, www.picotrack.com/Process/hmds.htm
[83] Joe Daggett ; Samuel Villareal ; Roger Robbins ; John Goodnight, www.utdallas.edu/research/cleanroom/documents/HMDS-Process.pdf
[84] Rao A.V.; Nilsen E, Einarsrud M.-A. Journal of non-crystalline solids 2001, 296(3), 165-171
[85] W. Hertl and M. L. Hair, J. Phys. Chem. 1971, 75, 2181-2185
[86] Valentyn Antochshuk and Mietek Jaroniec, Chem. Commun., 1999, 2373–2374