本研究利用靜電逐層(ELbL)組裝技術製備一透明且為可見光激發自潔表面。薄膜為商用鐵離子掺雜的二氧化鈦，MPT-428，搭配二氧化矽奈米粒子，利用靜電逐層組裝製備而成。另一方面，利用旋轉塗佈法將商用氮掺雜的二氧化鈦，BA-PW 25，製備成可見光激發二氧化鈦自潔表面。所有薄膜最後皆在空氣下經過四種不同溫度的鍛燒，藉此研究熱處理溫度在薄膜特性與自潔效能上的影響。
實驗結果顯示利用靜電逐層組裝所製備而成之透明且自潔的表面具有線性成長、高穿透度、低折射率與均勻表面形態的特性。雙層數目最高且鍛燒溫度最低的薄膜展現了最佳的光催化活性與表面潤濕永續性，其中光催化活性及表面潤濕永續性是分別藉由可見光燈源照射下亞甲基藍的降解及水滴接觸角隨暗處存放天數變化的實驗結果判定。但是利用旋轉塗佈法所製備的可見光激發二氧化鈦自潔表面形態較不均勻，鍛燒溫度對光催化活性與表面潤濕永續性的影響也不顯著。但自潔表面的接觸角在經過暗處存放20天後依然可以維持在10度以下。

Transparent and self-cleaning surfaces in this work are defined as surfaces with visible-light-active, antireflective, and self-cleaning properties. They were prepared by electrostatic layer-by-layer (ELbL) assembly technique using MPT-428 particles, which are commercial Fe-doped TiO2 photocatalyst, and SiO2 nanoparticles. On the other hand, self-cleaning surfaces in this work were prepared by spin coating method using BA-PW 25 particles, which are commercial nitrogen-doped TiO2 photocatalyst. All the thin films were calcinated with four different calcination temperatures under air to study the effect of calcination temperature on the characteristics of the thin films.
The experimental results revealed that the transparent and self-cleaning surfaces fabricated by ELbL assembly have linear growth behavior, high transmittance, low refractive index and uniform surface morphology. The photocatalytic activity and surface wetting sustainability of all the thin films were evaluated by monitoring the absorbance of methylene blue adsorbed thin film during visible light illumination and by measuring the change of water contact angle with dark storage time, respectively. The best photocatalytic activity and surface wetting sustainability of the transparent and self-cleaning surfaces can be realized by the highest number of bilayer and the lowest calcination temperature. On the other hand, the self-cleaning surfaces indicated visible-light-active photocatalysis but nonuniform surface morphology. Experimental results also revealed that the calcination temperature had insignificant effect on the photocatalytic activity and surface wetting sustainability of self-cleaning surfaces. However, the self-cleaning surfaces can maintain water contact angle less than 10o even after storing in the dark place for 20 days.

Ariga, K., Hill, J.P., Ji, Q., “Layer-by-layer assembly as a versatile bottom-up nanofabrication technique for exploratory research and realistic application,” Phys. Chem. Chem. Phys., 9, 2319-2340 (2007)
Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K., Taga, Y., “Visible-light photocatalysis in nitrogen-doped titanium oxides,” Science, 293, 269-271 (2001)
Chen, D., “Anti-reflection (AR) coatings made by sol-gel processes: A review,” Solar Energy Materials & Solar Cells, 68, 313-336 (2001)
Choi, W., Termin, A., Hoffmann, M.R., “The role of metal ion dopants in quantum-sized TiO2: correlation between photoreactivity and charge carrier recombination dynamics,” J. Phys. Chem., 98, 13669-13679 (1994)
Decher, G., “Fuzzy nanoassemblies : toward layered polymeric multicomposites,” Science, 277, 1232-1237 (1997)
Diebold, U., “The surface science of titanium dioxide,” Surface Science Reports, 48, 53-229 (2003)
Fujishima, A. and Zhang, X., “Titanium dioxide photocatalysis: present situation and future approaches,” C. R. Chimie 9, 750-760 (2006)
Fujishima, A., Rao, T.N., Tryk, D.A., “Titanium dioxide photocatalysis,” J. Photochemistry and Photobiology C: Photochemistry Reviews, 1, 1-21 (2000)
Gao, S.A., Xian, A.P., Cao, L.H., Xie, R.C., Shang, J.K., “Influence of calcining temperature on photoresponse of TiO2 film under nitrogen and oxygen in room,” Sensors and Actuators B, 134, 718-726 (2008)
Guan, K., “Relationship between photocatalytic activity, hydrophilicity and self-cleaning effect of TiO2/SiO2 films,” Surface and Coatings Technology, 191, 155-160 (2005)

Guan, K., Lu, B., Yin, Y., “Enhanced effect and mechanism of SiO2 addition in super-hydrophilic property of TiO2 films,” Surface and Coatings Technology, 173, 219-223 (2003)
Habibi, M.H, Talebian, N., Choi, J.H, “The effect of annealing on photocatalytic properties on nanostructured titanium dioxide thin films,” Dyes and Pigments, 73, 103-110 (2007)
Hasan, M.M, Haseeb, A.S.M.A., Saidur, R., Masjuki, H.H., “Effects of annealing treatment on optical properties of anatase TiO2 thin films,” Proceedings of World Academy of Science, Engineering and Technology, 30, 1307-6884 (2008)
Hashimoto, K., Irie, H., Fujishima, A., “TiO2 Photocatalysis: A historical overview and future prospects,” Japanese J. Applied Phys., 44, 8269-8285 (2005)
Hou, Y.Q., Zhuang, D.M., Zhang, G., Zhao, M., Wu, M.S., “Influence of annealing temperature on the properties of titanium oxide thin film,” Applied Surface Science, 218, 97-105 (2003)
Hwang, K.S., Jeong, J.H, Jeon, Y.S., Jeon, K.O., Kim, B.H., “Preparation of titanium oxide layer on silica glass substrate with titanium naphthenate precursor,” J. Sol-Gel Science and Technology, 35, 237-243 (2005)
Ihara, T., Miyoshi, M., Iriyama, Y., Matsumoto, O., Sugihara, S., “Visible-light-active titanium oxide photocatalyst realized by an oxygen-deficient structure and by nitrogen doping,” Applied Catalysis B: Environmental, 42, 403-409 (2003)
Irie,H., Watanabe,Y., Hashimoto, K., “Nitrogen-concentration dependence on photocatalytic activity of TiO2-xNx powders,” J. Phys. Chem. B, 107, 5483-5486 (2003)
Langlet, M., Permpoon, S., Riassetto, D., Berthome, G., Pernot, E., Joud, J.C., “Photocatalytic activity and photo-induced superhydrophilicity of sol-gel derived TiO2 films,” J. Photochemistry and Photobiology A: Chemistry, 181, 203-214 (2006)
Lee, D., Omolade, D., Cohen, R.E., Rubner, M.F., “pH-dependent structure and properties of TiO2/SiO2 nanoparticle multilayer thin films,” Chem. Mater., 19, 1427-1433 (2007)
Lee, D., Rubner, M.F., Cohen, R.E., “All-nanoparticle thin-film coatings,” Nano Lett., 6, 2305-2312 (2006)
Lee, F.K., Andeatta, G., Benattar, J.J., “Role of water adsorption in photoinduced superhydrophilicity on TiO2 films,“ Applied Phys. Lett., 90, 181928 (2007)
Lee, H.J., Hahn, S.H., Kim, E.J., You, Y.Z., “Influence of calcination temperature structural and optical properties of TiO2-SiO2 thin films prepared by sol-gel dip coating,” J. Materials Science, 39, 3683-3688 (2004)
Lee, S.K., Mills, A., “Novel photochemistry of leuco-methylene blue,” Chem. Commun., 2366-2367 (2003)
Liu, J.W., Zheng, Z.X ., Zuo, K.H., Wu, Y.C., “Preparation and characterization of Fe3+-doped nanometer TiO2 photocatalyst,” J. Wuhan University of Technology – Mater. Sci. Ed., 21, 57-60 (2006)
Mills, A., Wang, J., “Photobleaching of methylene blue sensitized by TiO2: an ambiguous system?,” J. Photochemistry and Photobiology A: Chemistry, 127, 123-134 (1999)
Mitzi, D.B., “Thin-film deposition of organic-inorganic hybrid materials,” Chem. Mater., 13, 3283-3298 (2001)
Miyauchi, M., Ikezawa, A., Tobimatsu, H., Irie H., Hashimoto, K., “Zeta potential and photocatalytic activity of nitrogen doped TiO2 thin films,” Phys. Chem. Chem. Phys., 6, 865-870 (2004)
Nakamura, I., Negishi, N., Kutsuna, S., Ihara, T., Sugihara, S., Takeuchi, K., “Role of oxygen vacancy in the plasma-treated TiO2 photocatalyst with visible light activity for NO removal,” J. Molecular Catalysis A: Chemical, 161, 205-212 (2000)
Nakamura, I., Sugihara, S., Takeuchi, K., “Mechanism for NO photooxidation over the oxygen-deficient TiO2 powder under visible light irradiation,” Chem. Lett, 1276-1277 (2000)
Parkin, I.P. and Palgrave, R.G., “Self-cleaning coatings,” J. Mater. Chem., 15, 1689-1695 (2005)
Permpoon, S., Hourmard, M., Riassetto, D., Rapenee, L., Berthome, G., Baroux, B., Joud, J.C., Langlet, M., “Natural and persistent superhydrophilicity of SiO2/TiO2 and TiO2/SiO2 bi-layer films,” Thin Solid Films, 516, 957-966, (2008)
Sano, T., Puzenat, E., Guillard, C., Geantet, C., Matsuzawa, S., “Degradation of C2H2 with modified-TiO2 photocatalystsunder visible light irradiation,” J. Molecular Catalysis A: Chemical, 284, 127-133 (2008)
Stathatos, E., Lianos, P., Tsakiroglou, C., “Metachromatic effects and photodegradation of basic blue on nanocrystalline titania films,” Langmuir, 20, 9103-9107 (2004)
Sun, R.D., Nakajima, A., Fujishima, A., Watanabe, T., Hashimoto, K., “Photoinduced surface wettability conversion of ZnO and TiO2 thin films,” J. Phys. Chem. B, 105, 1984-1990 (2001)
Surovtseva, N.I., Eremenko,A.M., Smirnova, N.P., Pokrovskii, V.A., Fesenko, T.V., Starukh, G.N., “The effect of nanosized titania-silica film composition on the photostability of adsorbed methylene blue dye,” Theoritical and Experimental Chemisty, 43, No 4, 235-239 (2007)
Tanaka, Y. and Suganuma, M., “Effects of heat treatment on photocatalytic property of sol-gel derived polycrystalline TiO2,” J. Sol-Gel Science and Technology, 22, 83-89 (2001)
Tryba, B., “Increase of the photocatalytic activity of TiO2 by carbon and iron modifications,“ Int. J. Photoenergy (2008)
Tseng, Y.H., Kuo, C. H., Huang, C.H., Li, Y.Y., Chou, P.C., Cheng, C.L., Wong, M.S., “Visible-light-responsive nano-TiO2 with mixed crystal lattice and its photocatalytic activity,” Nanotechnology, 17, 2490–2497 (2006)
University of Colorado, http://ruby.colorado.edu/~smyth/min/tio2.html (1997)
Wang, J., Zhu, W., Zhang, Y., Liu, S., “An efficient two-step technique for nitrogen-doped titanium dioxide synthesizing: visible-light-induced photodecomposition of methylene blue,” J. Phys. Chem. C, 111, 1010-1014 (2007)
Wang, Z., Gong, W., Hong, X., Cai, W., Jiang, J., Zhou, B., “Preparation, characterization and visible light photocatalytic activity of nitrogen-doped TiO2,” J. Wuhan University of Technology – Mater. Sci. Ed., 21, 71-77 (2006)
WebElements, http://www.webelements.com/compounds/titanium/titanium_dioxide.html (2009)
Wu, Z., Dong, F., Zhao, W., Guo, S., “Visible light induced electron transfer process over nitrogen doped TiO2 nanocrystals prepared by oxidation of titanium nitride,” J. Hazardous Materials, 157, 57-63 (2008)
Yamada, K., Yamane, H., Matsushima, S., Nakamura, H., Ohira, K., Kouya, M., Kumada, K., “Effect of thermal treatment on photocatalytic activity of N-doped TiO2 particles under visible light,” Thin Solid Films, 516, 7428-7487 (2008)
Yan, X., Ohno, T., Nishijima, K., Abe,. R., Ohtani, B., “Is methylene blue an appropriate substrate for a photocatalytic activity test? A study with visible-light responsive titania,” Chem. Phys. Lett., 429, 606-610 (2006)
Yoldas, B.E., “Investigations of porous oxides as an antireflective coating for glass surfaces,” Applied Optics 19, 9, 1425-1429 (1980)
Yu, J., Yu, K.C., Hoa, W., Jianga, Z., “Effects of calcination temperature on the photocatalytic activity and photo-induced super-hydrophilicity of mesoporous TiO2 thin films,” New J. Chem., 26, 607-613 (2002)
Zhang, H., Liu, H., Mu, C., Qiu, C., Wu, D., “Antibacterial properties of nanometer Fe3+-TiO2 thin films,” Proceedings of the 1st IEEE International Conference on Nano/Micro Engineered and Molecular Systems, 955-958 (2006)
Zhang, X.T., Fujishima, A., Jin, M., Emeline, A.V., Murakami, T., “Double-layered TiO2-SiO2 nanostructured films with self-cleaning and antireflective properties,” J. Phys. Chem. B, 110, 25142-25148 (2006)
Zhang, X.T., Sato, O., Taguchi, M., Einaga, Y., Murakami, T., Fujishima, A., “Self-cleaning particle coating with antireflection properties,” Chem. Mater., 17, 696-700 (2005)
Zhou, L., Tan, X., Zhao, L., Sun, M., “Photocatalytic oxidation of NOx over visible-light-responsive nitrogen-doped TiO2,” Korean J. Chem. Eng., 24 (6), 1017-1021 (2007)
Zhou, M., Yu, J., Cheng, B., “Effect of Fe-doping on the photocatalytic activity of mesoporous TiO2 powders prepared by an ultrasonic method,” J. Hazardous Materials B, 137, 1838-1847 (2006)
吳伊旎 ,『透明可見光催化二氧化鈦自潔表面的製備與鑑定』，成功大學化工系碩士論文 (2008)
林書玄,『具抗反射性質的超親水自潔表面之設計與製備』，成功大學化工系碩士論文 (2008)