摘要
本研究利用化學水浴法在ITO導電玻璃上鍍製出二氧化鈦薄膜，並改變硼酸濃度、水浴溫度、鍍膜層數、熱處理溫度及熱處理氣氛，用以探討薄膜的晶體結構、表面型態、光學性質及光電化學性質。利用光電化學原理於水溶液中吸收太陽能，並將其解離成氫氣應用於發電系統上。
本實驗在改變硼酸濃度下，發現增加硼酸濃度會產生過多的氫氧根離子(OH-)，過多的氫氧根離子會影響二氧化鈦薄膜的生長，導致二氧化鈦薄膜有脫落的現象發生，使得薄膜成形性質變差，且光電流也會降低。鍍膜層數的增加會使薄膜結晶強度增強，當薄膜內外層結構形成之後，鍍膜層數增加至一定程度，會使得薄膜沉積速率開始下降，表面也會越來越粗糙。在真空下燒結，由於缺少氧氣，會使得薄膜於再結晶下形成二氧化鈦時，無法將薄膜完全轉化成二氧化鈦。另外還改變熱處理溫度與水浴溫度對薄膜的影響；實驗結果顯示，在硼酸濃度0.05M、水浴溫度90℃、鍍膜層數2層、熱處理溫度500℃、熱處理氣氛-空氣下，擁有較好的光暗電流值，在無施加偏壓下，其值為126µA/cm2，相當於0.126mA/cm2。

ABSTRACT
In this study, titanium dioxide thin films are deposited on ITO conductive glass substrates with chemical bath deposition (CBD). By changing concentration of boric acid, temperature of bath, number of depositon layers, temperature of annealing and different atmospheres in annealing, the distructure of crystal, surface morphology, and optical and pholoelectrochemical properties of thin films are investigated. The principle of photoelectrochemical is applied in aqueous solution by absorbing solar energy and to convert water into hydrogen, which can then be used in electric generating systems.
It is found that hydroxide ions would be exceeded if concentration of boric acid increases. It would affect the growth of titanium dioxide thin film and result in corrosion and poor forming property of thin films, and the corresponding photocurrent would be thus reduced. The crystaling strength is increased as the number of deposition layers increases. Since the thin film structure is formed, the deposition rate would be decreased as the number of deposition layers achieves in some extent and the surface would be rougher. If the annealing is operated in the vacuum atmosphere, the thin film is unable to form titanium dioxide completely because of the lack of oxygen. Moreover, the influences of annealing and bath temperature are also discussed. The results showed that photocurrent has a better value at the circumstance as following: 0.05M of boric acid concentration, 90℃ of bath temperature, 2 of the number of deposition layers, 500℃ of annealing temperature and air of annealing atmosphere. The photocurrent is 126µA/cm^2, i.e. 0.126 mA/cm^2, without applying bias voltage.

參考文獻
[1] 聯合國政府間氣候變化專門委員會，http://www.ipcc.ch/。
[2] A.Fujishim , K.Honda , ‘‘Electrochemical photolysis of water at a
semiconductor electrode ‘‘, Nature , Vol. 238 , pp. 37-38,
(1972).
[3] A.Kudo , Y.Miseki , ‘‘Heterogeneous photocatalyst
materials for water splitting ‘‘, Chemical Society Reviews , Vol.
38, pp. 253-278, (2009).
[4] 蔡佳霖, ‘‘以化學浴沉積法製備四元化合物光電極薄膜之研究‘‘,
國立中央大學能源工程研究所碩士論文 (2010) 。
[5] 方俊、王秀峰、程冰、繆凌波，微波輔助化學浴沉積法製備ZnO
薄膜，電子元件與材料，第25卷，第10期，pp.17-19 (2006)。
[6] 賴致遠，以化學浴沉積法合成氧化鋅奈米線及其特性分析，國立
成功大學化學工程研究所碩士論文 (2006) 。
[7] 王應名、張萌、徐鵬、劉洋文、李禾、徐飛，化學浴沉積法製備
ZnS薄膜，南昌大學學報，第30卷，第3期，pp.279-282 (2006) 。
[8] M.R.D. Guire , T.P.Niesen , ‘‘Review：deposition of ceramic thin
films at low temperatures from aqueous solutions‘‘ , Solid State Ionics , Vol. 151 , pp. 61-68, (2002).
[9] T.P.Niesen , M.R.D. Guire , ‘‘Review：Deposition of ceramic thin films at low temperatures from aqueous solutions‘‘ , Journal of Electroceramics , Vol. 6 , pp. 169-207, (2001).
[10] H.Y.Xu , H.Wang , T.N.Jin , H.Yan , ‘‘Rapid fabrication of luminescent Eu：YVO4 films by microwace-assisted chemical
solution deposition‘‘, Institute of Physics Publishing ,
Nanotechnology , Vol. 16 , pp. 65-69, (2005).
[11] H.Y.Xu , S.L.Xu, X.D.Li , H. Wang , ‘‘Chemical bath deposition of hausmannite Mn3O4 thin films ‘‘ , Applied Surface Science , Vol. 252 , pp. 4091-4096, (2006).
[12] P.O’Brien , J.McAleese , ‘‘Developing an understanding of the processes controlling the chemical bath deposition of ZnS and
CdS ‘‘ , Journal of Materials Chemistry , Vol. 8 , pp. 2309–2314, (1998).
[13] Y.Masuda , T.Sugiyama , W.S.Seo , K.Koumoto , ‘‘Deposition Mechanism of Anatase TiO2 on Self-Assembled Monolayers from an Aqueous Solution ‘‘ , Chemistry of Materials , Vol. 15 , pp. 2469-2476, (2003).
[14] A.M.More , T.P.Gujar , J.L.Gunjakar , C.D.Lokhande , O.S. Joo , ‘‘Growth of TiO2 nanorods by chemical bath deposition method ‘‘ , Applied Surface Science , Vol. 255 , pp. 2682–2687, (2008).
[15] B.R.Sankapal , S.D.Sartale , M.C.Lux-Steiner, A.Ennaoui ‘‘Chemical and electrochemical synthesis of nanosized TiO2 anatase for large-area photon conversion ‘‘ , Applied Surface Science , Vol. 9 , pp. 702–707, (2006).
[16] 張振昌, ‘‘化學水浴沉積法成長硫化鎘薄膜之研究‘‘,國立中山大學科學材料研究所碩士論文 (2006)
[17] M.O.Lopez , A.A.Garica , M.L.A.Aguilera , V.M.S.Resendiz , ‘‘Improved efficiency of the chemical bath deposition method during growth of ZnO thin films ‘‘ , Materials Research Bulletin , Vol. 38 , pp. 1241–1248, (2003).
[18] P.O''Brien , T.Saeed , J.Knowled , ‘‘Speciation and the nature of ZnO thin films from chemical bath deposition ‘‘ , Journal of Materials Chemistry , Vol. 6 , pp. 1135-1139, (1996)
[19] T.Saeed , P.O’Brien , ‘‘Deposition and characterisation of ZnO thin films grown by chemical bath deposition ‘‘ , Thin Solid Films , Vol. 271 , pp. 35-38, (1995)
[20] J.Ouerfelli , M.Regragui , M.Morsli , G.Djeteli , K.Jondo , C.Amory , G.Tchangbedji , K.Napo , J.C.Bern`ede , ‘‘Properties of ZnO thin films deposited by chemical bath deposition and post annealed ‘‘ , Journal of PhysicsD:Applied Physics , Vol. 39 , pp. 1954-1959, (2006)
[21] R.S. Mane, C.D. Lokhande , ‘‘Chemical deposition method for metal chalcogenide thin films ‘‘ , Materials Chemistry and Physics , Vol. 65 , pp. 1-31, (2000)
[22] T.Bak, J.Nowotny ,M.Rekas, C.C.Sorrell , ‘‘Photo-electrochemical hydrogen generation from water using solar energy. Materials-related aspects ‘‘ , International Journal of Hydrogen Energy , Vol. 27 , pp. 991 – 1022, (2007)
[23] K.S.Ahn , Y.Y. , S.H.Lee. ,T.Deutsch. ,J.Turner , C.E.Tracy , C.L.Perkins , M. Al-Jassim , ‘‘Photoelectrochemical properties of N-incorporated ZnO films deposited by reactive RF magnetron sputtering ‘‘ , Journal of the Electrochemical Society , Vol. 154 (9) , pp. B956-B959, (2007)
[24] 市川勝著 李漢庭譯, ‘‘圖解氫能源 ‘‘ , 世茂出版有限公司 ,
2009年8月。
[25] S.M.Pawar , B.S.Pawar , J.H.Kim , O.S.Joo , C.D.Lokhande , ‘‘Recent status of chemical bath deposited metal chalcogenide and metal oxide thin films ‘‘ , Current Applied Physics , Vol. 11 , pp. 117-161, (2011)
[26] Y.Masuda , K.Kato, ‘‘Anatase TiO2 films crystallized on SnO2:F substrates in an aqueous solution ‘‘ , Thin Solid Films , Vol. 516 , pp. 2547–2552, (2008)
[27] X.P.Wang, Y.Yu, X.F.Hu, L.Gao, ‘‘Hydrophilicity of TiO2 films prepared by liquid phase deposition ‘‘ , Thin Solid Films , Vol. 371 , pp. 148-152, (2000)
[28] S.Deki, Y.Aoi , O.Hiroi, A.Kajinami, ‘‘Titanium (Ⅳ) oxide thin films prepared from aqueous solutiom ‘‘ , Chemistry , Vol. 25 , pp. 433-434, (1996)
[29] C.D.Lokhande , A.M.More , T.P.Gujar , J.L.Gunjakar , O.S.Joo , ‘‘Growth of TiO2 nanorods by chemical bath deposition method ‘‘ , Applied Surface Science , Vol. 255 , pp. 2682–2687, (2008)
[30] O.S.Joo , C.D.Lokhande, E.H.lee, K.D.Jung, ‘‘Room temperature chemical deposition of amorphous TiO2 thin films from Ti(III) chloride solution ‘‘ , Journal of Materials Science , Vol. 39 , pp. 2915 – 2918, (2004)
[31] A.Ennaoui , B.R.Sankapal , M.Ch.Lux-Steiner , ‘‘Synthesis and characterization of anatase-TiO2 thin films ‘‘ , Applied Surface Science , Vol. 239 , pp. 165–170, (2005)
[32] H.Imai, T.Watanabe, H.Hayashi, ‘‘Low-temperature preparation of dye-sensitized solar cells through crystal growth of anatase titania in aqueous solutions ‘‘ , Solar Energy Materials & Solar Cells , Vol. 90 , pp. 640–648, (2006)
[33] S.Karuppuchamy, M.Iwasaki, H.Minoura, ‘‘Physico-chemical, photoelectrochemical and photocatalytic properties of electrodeposited nanocrystalline titanium dioxide thin films ‘‘ , Vacuum , Vol. 81 , pp. 708–712, (2007)
[34] R.Amal, Y.K.Kho, A.Iwase, W.Y.Teoh, L.Ma¨dler, A.Kudo, ‘‘Photocatalytic H2 evolution over TiO2 nanoparticles. The synergistic effect of anatase and rutile ‘‘ , J. Phys. Chem. C , Vol. 114 , pp. 2821–2829, (2010)
[35] R.Dholam, N.Patel, A.Miotello , ‘‘Efficient H2 production by water-splitting using indiumetin-oxide/V-doped TiO2 multilayer thin film photocatalyst ‘‘ , International Journal of Hydrogen Energy , In Press, Corrected Proof, (2011)
[36] 超音波工學理論實務 賴耿陽編著 復漢出版社有限公司，民國
87年9月
[37] 薄膜與科技應用 羅吉宗編著 全華圖書股份有限公司，2009
年3月
[38] H. Yang, L. Guo, W. Yan, H.Liu, ‘‘A novel composite
photocatalyst for water splitting hydrogen production ‘‘ , Journal of
Power Sources , Vol. 159 , pp. 1305–1309, (2006)
[39] L.LYang ,Q.X.Zhao ,M.Willander , ‘‘Size-controlled growth of well-aligned ZnO nanorod arrays with two-step chemical bath deposition method ‘‘ , Journal of Alloys and Compounds , Vol. 469 , pp. 623–629, (2009)
[40] 徐彥翔, ‘‘以化學水浴法沉積氧化鋅光電極薄膜之研究‘‘,國立中央大學能源工程研究所碩士論文 (2010) 。
[41] ‘‘Optical processs of semiconductors ‘‘,J.I.Pankove, Prentice Hall,New York (1971) 。
[42] 半導體元件物理及製作技術 施敏原著 黃調元譯 國立交通
大學出版社，民國91年9月。