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Title: 光敏二氧化鈦奈米管陣列製作及研究
Synthesis and Investigation on Photo-sensitized Titanium Oxide Nanotube Arrays
Authors: Wei-jie Tzeng
曾韋傑
Contributors: NTOU:Department of Marine Engineering
國立臺灣海洋大學:輪機工程系
Keywords: 染料敏化太陽電池;陽極氧化法;CBD;SILAR;光敏特性;CuInS2;Cu2S
dye-sensitized solar cell;anodization;CBD;SILAR;photosensitive;CuInS2;Cu2S
Date: 2008
Issue Date: 2011-06-30T08:34:08Z
Abstract: 本研究是藉由定電壓陽極氧化法製作垂直有序的TiO2奈米管陣列,以無機半導體光敏材料取代染料敏化太陽電池之染料製作成光敏電極。TiO2奈米管具高表面積和高幾何方向性,經450℃/30分鐘熱處理,得到Anatase相之多晶奈米管陣列。典型陽極氧化條件0.3wt% NH4F, 3vol% H2O, 60V-3h所得之TiO2奈米管陣列具18m管長、126nm內管徑、12nm管壁厚。 使用四氯化鈦以濕式化學水浴法(CBD)披鍍修飾TiO2奈米管陣列,減少其表面缺陷;再以CBD法浸泡氯化鋁形成氧化鋁阻隔層,皆個別經450℃/30分鐘熱處理以固著披鍍層。以此固著披鍍層進一步用連續離子層吸附反應(SILAR)沉積In2S3,再以CBD法和SILAR沉積CuInS2光敏層;完成TiO2 nanotube/TiO2/Al2O3/In2S3/CuIn2S3之光敏結構。另外以CBD法和SILAR 沉積Cu2S光敏層;完成TiO2 nanotube/TiO2/Al2O3/Cu2S之光敏結構。 利用365nm之UV光照射TiO2奈米管陣列結構分解亞甲基藍溶液之光觸媒效果,以0.3wt% NH4F, 3vol% H2O, 60V-3h條件可得70%分解率;經四氯化鈦披鍍修飾後可達85%分解率。以二極電化學槽照射UV光及可見光,測量光敏電極的光電流。經0.1M四氯化鈦披鍍修飾24h後之TiO2奈米管陣列之UV光電流提昇30%。僅做四氯化鈦披鍍修飾之TiO2奈米管陣列無法以可見光照射產生光電流。0.01M之CuInS2與Cu2S沉積溶液以SILAR沉積光敏層之結構在可見光照射下,可得到比CBD沉積者較大的光電流。其中TiO2 nanotube/TiO2/Al2O3/In2S3/CuIn2S3光敏結構所產生之光電流為TiO2 nanotube/TiO2/Al2O3/Cu2S光敏結構之3倍。
The vertically ordered TiO2 nanotube arrays were prepared by potentiostatic anodization. The inorganic photosensitive films were coated on inner surface of TiO2 nanotubes to form photoelectrode instead of 3D TiO2 nanoparticles network immersed in liquid dyes of dye sensitized solar cell. Such TiO2 nanotubes with anatase poly-grains possess high specific area and high geometric orientation after 450℃/30min post annealing. Typical anodization conditions of 0.3wt% NH4F, 3vol% H2O, 60V-3h could achieve TiO2 nanotube arrays with 18m tube length, 126nm inner tube diameter and 12nm tube-wall thickness. In order to modify the defects of nanotubes and to form the barrier layer, the TiCl4(aq) and AlCl3(aq) were sequentially used to coat the inner surface of TiO2 nanotubes by chemical bath deposition (CBD) method. These two layers transformed into TiO2 and Al2O3, respectively, after 450℃/30min post annealing. Such annealed layers were further deposited with In2S3 buffer layer (by successive ionic layer adsorption reaction, SILAR), then with CuInS2 photosensitive layer (by CBD or SILAR) to complete a photosensitive structure of TiO2 nanotube/TiO2/Al2O3/In2S3 /CuIn2S3. Another photosensitive layer of Cu2S was also deposited by CBD or SILAR method to form photosensitive structure of TiO2 nanotube /TiO2/Al2O3/Cu2S. The decomposition rate of methylene blue solution by TiO2 nanotube arrays under the irradiation of UV light with 365nm wavelength was measured to show the photocatalytic activity. Decomposition rate of 70% was obtained with anodization conditions of 0.3wt% NH4F, 3vol% H2O, 60V-3h. Up to 85% could be achieved by TiO2 nanotube arrays after TiCl4(aq) modification. Various prepared photoelectrodes assembled in two-electrode electrochemical bath were irradiated by UV or visible light to evaluate the photocurrent. Refer to anodized TiO2 nanotube arrays, the photocurrent increased 30% for 0.1M TiCl4(aq) modified TiO2 nanotube arrays under UV light irradiation. However, such TiCl4(aq) modified TiO2 nanotube arrays could not generate photocurrent under visible light irradiation. On the other hand, the photocurrent of 0.01M CuInS2 or Cu2S solution deposited photosensitive layer by SILAR was higher than that by CBD under visible light irradiation. The photocurrent generated by TiO2 nanotube/TiO2/Al2O3/In2S3/CuIn2S3 photoelectrode showed about 3 times of TiO2 nanotube/TiO2/Al2O3/Cu2S photoelectrode.
URI: http://ethesys.lib.ntou.edu.tw/cdrfb3/record/#G0M95660023
http://ntour.ntou.edu.tw/ir/handle/987654321/16200
Appears in Collections:[輪機工程學系] 博碩士論文

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