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標題: 陽極氧化法製備奈米結構二氧化鈦薄膜於染料敏化太陽能電池之應用研究
Synthesis of nano-structured TiO2 films by anodic oxidation and application of the films in dye sensitized solar cells
作者: 陳冠名
Chen, Kuan-Ming
關鍵字: Anodic oxidation
titanium dioxide
dye-sensitized solar cells
出版社: 材料工程學系所
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摘要: 本研究主要是利用本實驗室既有之專利製程,將於鍍鈦玻璃基材 (Ti/glass) 上所成長之奈米網狀及顆粒狀結構TiO2薄膜應用於染料敏化太陽能電池之薄膜電極,並將不同奈米結構TiO2薄膜對光電轉換效率之影響進行探討。具有奈米網狀及顆粒狀結構之TiO2薄膜分別是在1 M KOH鹼性及1 M H2SO4酸性電解液下,以陽極氧化法之掃描電壓模式進行成長。此外,亦使用鍍鈦矽晶片 (Ti/Si) 為對照組進行比較。 鹼性電解液製備之TiO2薄膜以場發射掃描式電子顯微鏡 (FE-SEM) 觀察之表面形貌為奈米網狀結構。陽極氧化製程中電解液濃度能控制奈米網環大小,而隨著電解液濃度的增加,奈米網環亦會有變大之趨勢。應用於染料敏化太陽能電池之結果顯示,奈米網環大小約在40 nm時可量測到0.0057 %之最佳光電轉換效率,而奈米網環過大或太小都不利於光電轉換效率之提升。 酸性電解液H2SO4製備之TiO2薄膜表面形貌則為奈米顆粒狀結構。改變陽極氧化製程中之掃描電壓速率可控制奈米顆粒狀結構中之顆粒大小,且隨著掃瞄速率的增加,生成之奈米顆粒有變小之趨勢。當TiO2顆粒大小約45 nm時,所組裝之染料敏化太陽能電池可量測到0.125 %之最佳光電轉換效率,而隨著顆粒大小增加光電轉換效率也會增加。另外,不論是奈米網狀或顆粒狀結構,TiO2薄膜之光電轉換效率皆會隨著製程中之掃描截止電壓的增加而下降。以紫外光可見光光譜儀 (UV-Vis) 量測吸收光譜後可得知顆粒狀結構TiO2薄膜之吸收強度比網狀結構TiO2薄膜強,顯示染料對奈米顆粒狀結構TiO2薄膜之敏化效果較好。 以陽極氧化法於Ti/Si上所製備之奈米網狀或顆粒狀結構TiO2薄膜比Ti/glass所製備可獲得較高之光電轉換效率。而由FE-SEM分析得知奈米網狀結構TiO2薄膜厚度約80±10 nm;奈米顆粒狀結構TiO2薄膜厚度則為90±5 nm,而將兩種結構之TiO2薄膜所量測到之最佳光電轉換率和TiO2厚度相除所得之比值分別為0.063 (網狀)及2.2 (顆粒狀)。文獻中之比值最大為8.1,其次為1.3,顯示具有奈米顆粒狀結構之TiO2薄膜於染料敏化太陽能電池的應用上具有較佳之潛力。
The objective of this research is to apply nano-network and nanoparticle structured titanium dioxides (TiO2) films synthesized on Ti-coated glass (Ti/glass) on dye-sensitized solar cells. Influences of on the efficiency of light-to-electricity conversion the different nano-structured films were investigated. Synthesis of nano-network and nanoparticle-structured TiO2 were prepared by using anodic oxidation method with linear voltammetry mode in 1 M KOH alkaline and 1 M H2SO4 acid electrolyte, respectively, which is our lab''s patented process. Ti-coated silicon (Ti/Si) was also utilized as substrates for comparison. Surface morphology of the TiO2 films synthesized in KOH electrolyte was examined by field-emission scanning electron microscopy (FE-SEM), exhibiting a nano-network structure. Results revealed that the ring size of nano-network could be controlled by changing the concentration of electrolytes during anodic oxidation. Moreover, the ring size of the nano-network increased with increasing the electrolyte concentration. As the ring size of nano-network TiO2 films used in dye-sensitized solar cells was about 40 nm, the efficiency of light-to-electricity conversion could reach a highest value of 0.0057 %. Larger or smaller ring size of the nano-network would degrade the device performance. Obtained TiO2 films in H2SO4 electrolyte possessed a dense, nanoparticle surface morphology. The potential scanning rate could affect the nanoparticle sizes significantly. Furthermore, the nanoparticle sizes decreased with increasing the scanning rate. The efficiency of light-to-electricity conversion of the dye-sensitized solar cells could achieve a highest value of 0.125 % when the nanoparticle sizes of TiO2 films was about 45 nm. The light-to-electricity conversion efficiency also increased as the nanoparticle sizes increased. Furthermore, the light-to-electricity conversion efficiency decreased with increasing scanning cut-off voltages irrespective the structure of the TiO2 films. The UV-Vis spectra reveal that the absorption peaks of nanoparticle TiO2 films are stronger than that with nano-network structure. This result implied that the nanoparticle TiO2 films could be performed than nano-network films. Nano-network or nanoparticle structured TiO2 prepared on Ti/Si could result in better light-to-electricity conversion efficiency, compared to those synthesized on Ti/glass. The thickness of nano-network TiO2 obtained by FE-SEM micrographs was 8010 nm, and was 905 nm for nanoparticle TiO2. The best values of the ratio of efficiency and thickness for nano-network and nanoparticle structured TiO2 films were 0.063 and 2.2, respectively. In the literature, the highest efficiency/thickness was 8.1 and the second one was 1.3. Our results show that TiO2 films with nanoparticle structure would performed much better than most of the results in the literature concerning efficiency/thickness ratios in dye-sensitized solar cells application.
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