染料敏化太陽能電池(Dye-Sensitized Solar Cell, DSC)因成本低、製作簡易、多色彩等優點，深具商業化應用之潛力。DSC中製作光電極所用之TiO2顆粒的粒徑大小對於元件之光電轉換效率具有極大影響，小粒徑之TiO2顆粒擁有較大的表面積，染料吸附量較大，而大粒徑之TiO2顆粒的光散射能力較強，且燒結後的膜具有較大孔洞利於電解液的流動。本篇論文使用不同粒徑大小的T5 (20 nm)、T1 (25 nm)、C1 (40 nm)與SC (400nm)所配成的TiO2漿料交錯塗佈在導電玻璃(FTO)上，並以Ethanol進行TiO2膜的平整化，減少TiO2層與層間的空隙，最後所得的含四層TiO2膜之光電極(FTO/T5/C1/T5/SC)，搭配釕金屬錯合物染料DUY2並以25 μm Surlyn spacer 進行元件組裝後，有良好的光伏表現，光電轉換效率最高可達10.02%。此外，將最佳TiO2膜結構之光電極應用於DUY1~DUY4染料，其中DUY2染料所敏化之元件有最高光電轉換效率，原因在於DUY2染料吸附於TiO2膜時有最大的吸收度，且DUY2染料結構中兩個-CF3取代基的位置利於電解液中的I- 靠近染料金屬中心使染料還原再生，因此有較短的染料還原再生時間，使得在四個染料中，DUY2染料所敏化之元件有最高的短路電流密度值，為18.40 mA/cm2。;Great attention has been devoted to the new generation dye-sensitized solar cell (DSC) due to its several advantages such as colorful, easy fabrication and low cost. The particle size of TiO2 of the photoelectrode plays an important role in the photovoltaic conversion efficiency of DSC. Smaller sized particle has larger surface area but lacks light-scattering ability. By contrast, larger particle has stronger light scattering ability, the resulting film has good porosity in favour of electrolyte diffusing although it has smaller surface area. How to arrange the large and small sized particles in the photoelectrode is an important task for achieving high cell performance. This study focuses on the preparation of photoelectrode with multiple TiO2 layers made from different particle sizes (T5: 20 nm, T1: 25 nm, C1: 40 nm, SC: 400 nm). Each TiO2 layer was further leveled with ethanol vapor before calcining. It was found that the architecture of photoelectrode composed of four TiO2 layer (FTO glass/T5/C1/T5/SC) achieves highest efficiency of 10.2% when applied to DUY2 sensitizer. Furthermore, for the optimal photoelectrode DUY2 sensitizer has the highest Jsc (18.40 mA/cm2) and efficiency amongst the ruthenium sensitizers DUY1 ~ 4 studied here, due to its high absorption, high dye-loading and less structure hindrance for restricting the RuIII-I- interaction.