臺灣博碩士論文加值系統

摘要
本研究我們探討用不同的二氧化鈦電極結構應用在染料敏化太陽能電池上的研究，主要之研究項目有(1)利用溶膠-凝膠法(sol-gel)製作二氧化鈦奈米粒子，並塗佈在ITO導電玻璃上來製作二氧化鈦薄膜電極:(2)利用濺鍍法(sputtering)的方式在ITO導電玻璃上成長二氧化鈦薄膜電極:(3)利用黃光製程的方式將TiO2薄膜做出柱狀結構，並探討在不同的結構下對染料對太陽能電池的影響。
由XRD分析發現，我們製作出來的二氧化鈦奈米粒子在500℃鍛燒下具有最強的銳鈦礦結晶相位(2θ=25.6。(101))，而在TiO2薄膜方面在退火溫度為600℃時，其銳鈦礦結晶相(2θ=25.6。(101))為最強，此晶相有利於染料電子的轉移。
而在接觸角的分析方面，TiO2薄膜在未照光和照紫外光後，接觸角有明顯的變小，而且照光時間越長，其薄膜與DI water 的接觸角越小，故得到光對TiO2激發反應的應證。由光穿透率分析發現，薄膜對於光的穿透影響不大，整體的穿透效果還是不錯的。染料是選用自然的紫質衍生物TCPP，其有如植物中葉綠素的原理一樣，能夠幫助TiO2的光激發波段提昇至可見區，而由吸收光譜圖來看，吸附染料後的TiO2會有較強的吸收能力。
量測的結果發現，利用黃光製程製作出的柱狀TiO2電極其效率優於用溶膠-凝膠法的方式製備的TiO2電極，以及用濺鍍的方式製備的TiO2電極，且在我們染料中加入一種共同吸附劑DCA(deoxycholic acid)的物質，DCA的加入避免染料分子的聚集和減少覆蓋在TiO2表面回電子的轉移，因此有助於太陽電池效率的提升。

Abstract
In the research , Applications of different TiO2 electrode structure on Dye-Sensitized Solar Cell , was investigated. The main items include (1) we synthesized TiO2 nano-particles by sol-gel method and TiO2 films electrode by spin-coating. (2) we fabrication the TiO2 film electrode by RF Sputtering. (3) we fabrication the Rod TiO2 electrode by photo lithography. we analysis the TiO2 nano-particles and TiO2 films by XRD、Contact Angle and Transmittance. we also discussed the different TiO2 electrode structure of solar cell and sensitizers.
The experimental results of titanium dioxide show that the metastable anatase phase have the strongest 2θ=25.6 (101) diffraction peaks at the sintering 500℃. The calcinated TiO2 thin film was identified to possess hydrophilic property while DI water reduces its contact angle on the thin film under the UVlight exposure .The TiO2 thin film photo Excite can be improve. The reason is that the TCPP own the function of “COOH”which can change the energy of the surface of electrode. According to the analysis of UV-Vis Spectroscopy, the TiO2 which was adsorbed by sensitizer can be improve the increase the absorbability.
The efficiency result to find the Rod TiO2 electrode better than the TiO2 nano-particles by sol-gel method and the TiO2 film electrode by RF Sputtering . We add the material of a kind of coadsorbent DCA (deoxycholic acid ) in our dye(TCPP solution). The efficiency can be increase of on the DSSC devices.

目 錄
中文摘要.............................................................i
英文摘要............................................................ii
誌謝...............................................................iii
目錄................................................................iv
圖目錄..............................................................vi
表目錄............................................................viii
第一章 序論.........................................................1
1-1 前言.............................................................1
1-2 染料敏化太陽能電池.................................................4
1-3 研究背景與目的....................................................5
第二章 理論原理與文獻回顧..............................................6
2-1 染料敏化太陽能電池的組成結構...................................6
2-2 染料敏化太陽能電池的工作原理及特性..............................8
2-3 光敏化劑-染料.................................................12
2-4 電解質.....................................................15
2-5 太陽能電池電流-電壓輸出特性...................................16
2-6 染料敏化太陽能電池目前的發展動向..............................18
2-7 二氧化鈦簡介................................................24
第三章 實驗步驟與設備................................................33
3-1 實驗儀器與實驗藥品...........................................33
3-2 染料敏化太陽能電池的製備.....................................35
3-2-1 二氧化鈦薄膜電極的製備..................................36
3-2-2 白金背電極的製備.......................................41
3-2-3 染料與電解質的製備.....................................41
3-2-4 元件的封裝與電解質的注入................................41
3-3多功能X光薄膜繞射儀分析.......................................42
3-4場發射式掃瞄式電子顯微鏡分析...................................42
3-5紫外/可見光光譜儀分析.........................................42
3-6 TiO2薄膜對光吸收後接觸角量測.................................43
3-7 太陽能電池元件量測...........................................43
第四章 結果與討論....................................................44
4-1 薄膜電極的分析..............................................44
4-1-1 二氧化鈦薄膜電極XRD分析.................................44
4-1-2 二氧化鈦薄膜與水之接觸角分析.............................48
4-2光對薄膜穿透率之分析..........................................51
4-3紫外光-可見光吸收光譜分析.....................................52
4-4曝光-顯影後之SEM分析.........................................54
4-5染料敏化太陽能電池元件效率之分析...............................57
第五章 結論.........................................................62
未來研究方向.........................................................63
參考文獻............................................................64

圖 目 錄
圖1-1 各種化石能源存量.................................................1
圖1-2 矽晶片太陽能電池工作原理..........................................2
圖2-1 染料敏化太陽能電池的結構示意圖....................................7
圖2-2 染料敏化太陽能電池的發電示意圖....................................8
圖2-3 為商業化製程窗戶型太陽電池的示意圖(a)剖面圖 (b)結構圖..............11
圖2-4 三種Ru- polypyridine complex..................................13
圖2-5 TCPP之分子結構圖..............................................13
圖2-6 為植物之光合作用示意圖..........................................14
圖2-7 DYSC三明治結構示意圖...........................................15
圖2-8 染料敏化太陽能電池之電壓、電流特徵圖..............................17
圖2-9 DSSCs發展時程.................................................18
圖2-10各式DSSCs整體效率的演進.........................................21
圖2-11常見TiO2的兩種結晶型態..........................................24
圖2-12 Rutile及Anatase之晶格結構.....................................25
圖2-13 二氧化鈦之分子鍵結方式：（a）Rutile；（b）Anatase................26
圖2-14 TiO2光催化反應機制簡圖.........................................28
圖2-15 幾種半導體之band position。紅色區塊為CB，綠色區塊為VB，VB與CB之間即為bandgap............................................................29
圖2-16 電子-電洞對之激發產生光催化效應機制與時間之關係圖..................30
圖3-1 染料敏化太陽能電池的製作流程.....................................35
圖3-2 塗佈TiO2 film流程圖............................................37
圖3-3 塗佈完成之TiO2電極.............................................37
圖4-1 TiO2粉末在不同溫度緞燒下之XRD繞射圖..............................45
圖4-2 TiO2 薄膜在不同溫度退火下之XRD繞射圖.............................46
圖4-3 親疏水性與接觸角關係圖..........................................49
圖4-4 表面作用力示意圖................................................49
圖4-5 TiO2薄膜在不同退火溫度下其接觸角的變化............................50
圖4-6 ITO導電玻璃在鍍膜前後之穿透率的比較...............................51
圖4-7 染料分子TCPP的吸收光譜圖........................................53
圖4-8 TCPP solution及其吸附在TiO2表面之吸收光譜........................53
圖4-9曝光顯影後之SEM正視圖............................................55
圖4-10曝光顯影後之SEM側視圖...........................................55
圖4-11濕蝕刻之後的SEM正視圖...........................................56
圖4-12濕蝕刻之後的SEM側視圖...........................................56
圖4-13為組裝完成之DSSC元件............................................57
圖4-10不同TiO2電極結構添加染料分子(TCPP)後之I-V特性圖...................59
圖4-11 TCPP添加DCA後之I-V特性圖......................................59
圖4-12 Newport Oriel lnstriments太陽能光源模擬器......................61

表 目 錄
表2-1 p/n cells 與 DSSCs 光電發生機制的比較............................9
表2-2 TiO2 Anatase相與Rutile相性質比較表..............................26
表4-1 TiO2 anatase和rutile相位的XRD特性峰值...........................47
表4-2 接觸角數值.....................................................50
表4-3 不同TiO2電極結構添加染料分子(TCPP)後的量測數據....................60
表4-4 TCPP添加DCA後的量測數據.........................................60

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