本研究利用電化學方法，輔助製備半導體敏化二氧化鈦光電極，藉由施加於二氧化鈦電極上的偏壓，促進反應半導體之前驅物離子的擴散能力，使其吸附至多孔性二氧化鈦薄膜的孔洞內部，藉此增進後續所沉積半導體於薄膜中的沉積量與縱向分佈均勻度，稱為電化學輔助吸附程序(Electrochemically-assisted adsorption, 以下簡稱EA)。實驗中利用ESCA及SEM來分析，經EA程序所吸附之元素的電子組態及薄膜表面形態，利用紫外光-可見光吸收光譜儀、EDS來分析半導體的沉積量及分布狀態，並以電化學阻抗分析儀分析，量測元件效能與內部電荷傳輸之界面阻力。

由研究結果得知，EA程序能夠增進半導體沉積量，且促進半導體於薄膜深部的批覆程度，進而抑制二氧化鈦/電解液之界面的電荷再結合反應，因此原件效能得以提升。在硒化鎘半導體敏化元件的製備上，以EA程序所製備的硒化镉敏化原件，可達到3.37%的光電轉換效率，此效率值遠高於利用傳統SILAR製程所製備之元件效能(2.75%)。研究中利用SILAR製程來增加EA所製備之光電極上半導體沉積量，將原件效能提升由3.37%至4.2%。本研究最後將此一策略應用在硫化镉/硒化鎘半導體共敏化二氧化鈦光電極的製備，原件最佳光電效能可達5.02%。

關鍵字: 電化學程序、半導體敏化原件、硒化鎘、硫化鎘、SILAR

In this study, electrochemically-assisted adsorption was applied to modify the TiO2 electrode for the improvement of ionic diffusion and surface coverage in the further CdSe deposition by successive ionic layer adsorption and reaction (SILAR).
The ionic diffusion of Cd2+ was promoted by applying an electric field between 2 V and -2 V bias on TiO2 / FTO electrode before SILAR process in the Cd2+/ EtOH solution. From the UV-Vis. absorption analysis, pretreated electrodes showed a better light-harvesting ability, which could be considered as the promotion of deposited sensitizers in porous TiO2 matrices. The pretreated electrode showed the high coverage of deposited CdSe on TiO2 surface was facilitated by well penetrated Cd2+ during the electrochemically-assisted adsorption in the inner side of film. The impedance spectroscopy showed an increase in the charge transfer resistance and electron lifetime indicate an improved surface coverage of CdSe sensitizers and a suppression of charge recombination at the TiO2/electrolyte interface.
The TiO2 films after adsorption of Cd+2 ions were dipped into another solution containing Se precursors to deposit the CdSe sensitizer, the energy conversion efficiency of 3.37% can be obtained for a reaction time of 15 min which is higher than 2.75% obtained by the traditional SILAR process. Electrochemically-assisted adsorption method combined with SILAR process was applied to prepare CdSe-sensitized solar cell and CdS/CdSe co-sensitized solar cell, the energy conversion efficiency about 4.3% and 5.02% could be achieved, respectively.
Keywords: Electrochemical process, Semiconductor-Sensitized Solar Cells, Cadmium Sulfide, Cadmium Selenide, SILAR

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