臺灣博碩士論文加值系統

目前在太陽電池的領域中，一種新興元件-染料敏化太陽電池被發展出來之後，正面臨一個商品化的關鍵瓶頸，也就是製作具理想結構奈米多孔二氧化鈦電極材之困難性。二氧化鈦結構掌控著染料敏化太陽電池之轉換效率，如能以低製造成本的表面工程發展出理想的奈米多孔結構電極材，將會使染料敏化太陽電池獲得大幅的效能提昇並加速普及化。微弧氧化處理技術係於陽極金屬施加電壓使金屬表面發生電崩潰、融化、氣化、化學反應、擴散、凝固和相變化等物理化學過程，所形成的氧化膜具微米尺度之大量孔洞以及良好的附著性。藉由化學鹼處理及熱處理之後製程，進一步控制表面形態及結晶結構可使表面奈米化及提升結晶性。故本研究利用微弧處理於鈦金屬生長銳鈦礦相二氧化鈦多孔微米結構，結合化學鹼處理及熱處理後製程使表面進一步形成具有高比表面積的奈米多孔結晶結構以利於染料的吸收，成為理想的染料敏化太陽電池異質接面，期望提昇光電轉換效率。
本研究利用微弧氧化處理，在直流模式下改變放電電壓(300 V-500 V)及放電時間(10 min-90 min)；在脈衝模式下改變脈衝頻率(100 Hz-4000 Hz)、放電時間(10 min-90 min)及脈衝占空比(1/9-8/2)，於鈦金屬生長銳鈦礦相二氧化鈦薄膜並將微弧處理後的試片加以封裝成ITO glass/Pt/electrolyte (I2+LiI)/dye/TiO2/Ti反向架構之太陽電池元件，探討二氧化鈦奈米多孔結構之製程參數的變動對元件特性之影響。再從最高光電轉換效率所對應的微弧試片進行鹼處理使試片氧化層進一步獲得奈米形貌，探討鹼溶液溫度(20 oC-40 oC)、濃度(0.5 M-2.5 M NaOH)及浸泡時間(12 h-24 h)的影響。之後再於大氣中不同溫度(300 oC-500 oC)下進行熱處理，探討晶體結構的變化並藉以說明其光電轉換效率之變動。
研究結果顯示；以微弧氧化處理可製備出具有銳鈦礦相為主以及少量金紅石相結構之多孔微米尺度二氧化鈦薄膜。在直流電源模式中，當放電電壓提高和放電時間延長時，氧化膜之厚度隨之增大，但過大的放電電壓及放電時間會造成金紅石相含量提高、銳鈦礦相含量比例降低以及大孔洞的生成，故元件光電轉換效率隨微弧放電電壓先升後降，此一趨勢與提供染料吸附的氧化層總比表面積有關，最高可獲得0.061%的光電轉換效率。在脈衝電源模式中，當放電頻率增加時，氧化膜的銳鈦礦相含量提高，但厚度隨之下降，光電轉換效率先升後降，此仍是受染料吸收含量變化所致。脈衝占空比增加雖能增加膜厚，卻會使孔洞尺寸變大，導致光電轉換效率先升後降，最高可獲得0.078%的光電轉換效率。將微弧處理所得氧化膜進行鹼處理後，表面形態從微米尺度發展成奈米尺度，較高的鹼液溫度可獲得有相當深度的奈米片狀叢集形貌，但會伴隨裂痕的發生，導致電子-電洞再結合與電阻增加。經40 oC鹼處理12 h所獲得的奈米片狀叢集形貌，其光電轉換效率可達0.329%。藉由300 oC以上的後熱處理可促進二氧化鈦結晶性提昇，400 oC熱處理可得最高光電轉換效率2.194%。

Since the invention of the dye-sensitized solar cell (DSSC), it has reached a critical obstruction in commercialization due to the difficulty in manufacturing nano-featured TiO2 electrode with an ideal structure, which is also a key to higher efficiency of DSSC device. A simple and low cost surface engineering technique growing a nano-featured TiO2 electrode as the ideal electron emitter shall expand the promotion of commercial DSSC. Micro-arc oxidation (MAO) is developed recently which is based on the anodic oxidation, but running at a potential above the breakdown voltage of surface oxide layer on metal anodes. As the process through dielectric breakdown, melting, gasification, chemical reactions, diffusion, solidification and phase transformation, leaves an oxide layer on metal surface. This can produce a highly porous TiO2 coating onto titanium with pores in micrometer scale and still remain a good adherence with substrate. Besides, surface morphology and microstructure could be changed by means of different ways such as alkali treatment for developing nano-featured surface and heat treatment for crystallinity of oxide layer.
In this study, the porous anatase TiO2 layer was grown on the titanium plate by MAO. In the direct current (DC) mode, the discharge voltage was set from 300 V to 500 V with various oxidation times from 10 min to 90 min. In pulse mode, the unipolar voltage pulse waveform frequency from 100 Hz to 4000 Hz, duty cycle from 1/9 to 8/2 and oxidation time setting were 10 min to 90 min. Then the inversed-type ITO glass/Pt/electrolyte (I2+LiI)/dye/TiO2/Ti devices were assembled using above MAO specimens, respectively. The influence of the processing parameters on the associated microstructural change of MAO specimens assembled DSSC photovoltaic efficiency was investigated. Base on the DSSC with highest photovoltaic efficiency, the corresponding oxide specimen was treated in various alkali solutions with a concentration 0.5 M to 2.5 M NaOH solution, set temperature 20 oC to 40 oC and soaking time of 12 h to 24 h for further formation of nano-featured TiO2. Finally, a post-heat treatment at different temperatures was carried out for enhancing the crystallinity of oxides for better photovoltaic efficiency.
Experimental results show that a micrometer-scale porous crystalline TiO2 layer can be fabricated by MAO, which composed of predominantly anatase phase and minor rutile phase. In DC power mode, by increasing the discharge voltage and oxidation time, the thickness of oxide layer increases. However, the over discharge voltage and oxidation time leads to the decrease of anatase phase and larger pore size in oxide layer. It reduces the specific surface area of oxide layer for the dye adsorption. Therefore, the photovoltaic efficiency of assembled DSSC also increases to maximun of 0.061% then decrease with discharge voltage or oxidation time. In unipolar pulse power mode, the thickness of TiO2 layer decreases, but the fraction of rutile increases by increasing the pulse frequency, which makes the assembled devices present different photocurrent-voltage curves. The thickness of oxide layer increases with the duty cycle, but result in larger pore size in TiO2 layer. Thus, the photovoltaic efficiency of DSSC increased first to the maximum of 0.078% then decreased. After alkali treatment, the oxide surface exhibits numerous pores. Higher solution temperature could obtain a considerable depth of nano-flaky morphology. However, the formation of cracks in the oxide layer reduced the photovoltaic efficiency. Alkali treatment in 1.25 M NaOH solution for 12 h at 40 oC, the assemble device present a photovoltaic efficiency of 0.329%. Post-annealing at a temperature over 300 oC significantly enhances the formation of anatase phase in oxide. The ultimate photovoltaic efficiency 2.194% appears on the DSSC based on the TiO2 layer annealed at 400 oC.

中文摘要.................................................Ⅰ
英文摘要.................................................Ⅱ
總目錄...................................................Ⅴ
圖目錄...................................................Ⅶ
表目錄...................................................ΧI
符號說明................................................ΧII
第一章 前言.............................................1
第二章 文獻回顧.........................................3
2-1 太陽電池簡介..........................................3
2-1-1 太陽光譜............................................3
2-1-2 太陽電池的光伏效應..................................4
2-1-3 太陽電池的種類......................................6
2-2 染料敏化太陽電池......................................9
2-2-1 染料敏化太陽電池的基本結構及原理....................9
2-2-2 染料敏化太陽電池的電流電壓輸出特性.................20
2-2-3 染料敏化太陽電池的等效電路.........................22
2-2-4 染料敏化太陽電池的發展現況.........................23
2-3 二氧化鈦電極的發展及重要性...........................25
2-3-1 微弧氧化處理生長二氧化鈦薄膜.......................34
2-3-2 化學處理生長奈米多孔性二氧化鈦薄膜.................46
2-4 結合微弧氧化與鹼處理之研究動機.......................49
第三章 實驗方法與流程..................................50
3-1 試片準備及前處理.....................................51
3-2 微弧氧化處理製備多孔性二氧化鈦薄膜...................51
3-2-1 直流電源模式.......................................54
3-2-2 單極脈衝電源模式...................................54
3-3 化學鹼處理...........................................55
3-4 退火熱處理...........................................56
3-5 微觀形態觀察.........................................56
3-6 晶體結構分析.........................................57
3-7 太陽電池元件製作及光電轉換效率測試...................57
第四章 結果與討論......................................60
4-1 直流模式下生長二氧化鈦薄膜...........................60
4-1-1 放電電壓對二氧化鈦薄膜的微觀組織及光電轉換效率之影響.......................................................60
4-1-2 放電時間對二氧化鈦薄膜的微觀組織及光電轉換效率之影響.......................................................67
4-2 脈衝模式下生長二氧化鈦薄膜...........................73
4-2-1 頻率對二氧化鈦薄膜的微觀組織及光電轉換效率之影響...73
4-2-2 占空比對二氧化鈦薄膜的微觀組織及光電轉換效率之影響.80
4-2-3 放電時間對二氧化鈦薄膜的微觀組織及光電轉換效率之影響.......................................................87
4-3 二氧化鈦薄膜後鹼處理的微觀組織及光電轉換效率.........94
4-4 二氧化鈦薄膜後鹼處理及後熱處理的微觀組織及光電轉換效率......................................................101
第五章 結論...........................................104
參考文獻................................................106
誌謝....................................................116

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