CdS/CdSe量子點敏化TiO2光電極在光電化學電池產氫以及固態太陽能電池之應用

Applications of CdS/CdSe Quantum Dot-sensitized TiO2 Photoelectrodes for Photoelectrochemical Hydrogen generation and Solid-State Solar Cells

10.6844/NCKU.2011.00777

紀景發

硫化鎘 ； 硒化鎘 ； 量子點 ； 共敏化效應 ； 光電化學製氫 ； 固態電池 ； 電洞傳輸層 ； 偶極距 ； 表面修飾 ； Cadmium sulfide (CdS) ； cadmium selenide (CdSe) ； Quantum dots (QDs) ； Co-sensitization effect ； Photoelectrochemical hydrogen generation ； Solid state solar cell ； Hole transfer materials ； Dipole moment ； Surface treatment

成功大學化學工程學系學位論文

2011年

博士

李玉郎

英文

本研究利用連續離子吸附反應成膜法(Successive ionic layer adsorption reaction, SILAR)將硫化鎘與硒化鎘量子點組裝到二氧化鈦薄膜表面，作為TiO2/CdS/CdSe共敏化光電極，並應用在光電化學系統進行水分解製氫。結果顯示，TiO2/CdS/CdSe光電極具有互補的吸光特性，且硫化鎘與硒化鎘的組裝順序對於共敏化電極之效能有很大的影響。由暗電流與平帶電位量測結果發現TiO2/CdS比TiO2/CdSe有較高的費米能階；而TiO2/CdS/CdSe、TiO2/CdSe/CdS的費米能階位置較TiO2/CdS低，推測CdS與CdSe界面之間可能有能階重排的機制存在。 紫外光光電子譜結果顯示在TiO2/CdS/CdSe電極中，沉積在CdS外層的CdSe，其導帶位置向上移動證實了上述的機制。因此TiO2/CdS/CdSe電極在能階位置上有順向階梯狀的排列，有助於電子電洞對分離，效能相較TiO2/CdS、TiO2/CdSe可提升三倍達到飽和電流密度14.9 mA/cm2 (AM1.5 100 mW/cm2,UV cut-off)。 進一步在此電極上沉積上ZnS保護層，可增加電極穩定性並減少漏電流發生，目前TiO2/CdS/CdSe/ZnS光電極的最佳產氫速率可達到220uL/hr-cm2。 時間解析光激螢光(Time resolved photoluminescence)與開路電壓衰退分析(OCVD)顯示順向能階排列的TiO2/CdS/CdSe光電極導致電子有效地注入到二氧化鈦並維持較低的再結合速率。 另一方面，本研究進一步利用順向能階結構的TiO2/CdS/CdSe共敏化光電極，結合固態電解質(Spiro-OMeTAD)取代液態電解質製作全固態量子點敏化太陽電池。對於2um 膜厚的電極，電池之光電轉換效率為0.61%(AM 1.5, 100mW/cm2)。進一步以雙異戊磷酸(Diisooxy phosphonic acid, DIOPA)，與苯硫醇衍生物(Benzenethiol, BT)進行TiO2/CdS/CdSe光電極表面修飾：可抑制漏電流的發生並藉由BT分子的偶極矩促進電子注入到二氧化鈦導帶，改善元件的光電壓與光電流。同時以此兩種分子對光電極表面修飾(TiO2/QDs-BTOMe-DIOPA)，元件之光電轉換效率可達0.88% (AM 1.5, 100mW/cm2)。

The method of successive ionic layer adsorption reaction (SILAR) was used to assemble cadmium sulfide (CdS) and cadmium selenide (CdSe) onto mesoporous TiO2 films. CdS/CdSe co-sensitized photoelectrodes were prepared and applied for photoelectrochemical hydrogen generation. The results show that the CdS/CdSe co-sensitized photoelectrodes have a complementary effect on the light harvest, and furthermore, the performance of the electrodes is strongly dependent on the order of CdS and CdSe with respected to the TiO2. Dark current and flat-band measurements revealed that TiO2/CdS has a Fermi-level higher than that of TiO2/CdSe while both Fermi-levels of TiO2/CdS/CdSe and TiO2/CdSe/CdS locate between those of TiO2/CdS and TiO2/CdSe, which implies energy level reorganization occurs at the CdS/CdSe interface. The ultraviolet photoelectron spectroscopy (UPS) analysis showed an upward shift of CdSe conduction band edge in the TiO2/CdS/CdSe, sustaining the inference mentioned above. Therefore, TiO2/CdS/CdSe electrode possess a stepwise structure of energy levels, which is advantageous to the electron injection and hole regeneration in the photoelectrode. The saturated photocurrent achieved by the TiO2/CdS/CdSe electrode is 14.9 mA/cm2 (AM1.5 100 mW/cm2, UV cut-off) which is three times the values obtained by the TiO2/CdS and TiO2/CdSe. By using zinc sulfide as a passivation layer to improve the stability and reduce the leakage current, the corresponding hydrogen evolution rate measured for the TiO2/CdS/CdSe/ZnS electrode is 220 µmol/cm2h. Time resolved photoluminescence (PL) and open-circuit photovoltae decay (OCVD) experiments revealed that the photogenerated electrons in the TiO2/CdS/CdSe have higher injection efficiency, but lower recombination rate to the electrolyte, attributable to the stepwise structure of band-edge levels constructed by the effect of the energy level alignment. Furthermore, TiO2/CdS/CdSe co-sensitized electrode was utilized to fabricate all-solid-state quantum dot sensitized solar cells (QD-SSCs) by using an organic hole transport material (Spiro-OMeTAD), instead of liquid electrolytes. An overall conversion efficiency of 0.65 % (AM 1.5, 100 mW/cm2) was obtained for the TiO2/CdS/CdSe electrode of 2 μm in thickness. Moreover, diisooctyl phosphonic acid (DIOPA) and benzenethiol derivatives were used as surface-modifying agents of the TiO2/CdS/CdSe electrode. It was found that the dipole-moment induced by the surface-modified layers can inhibit the charge recombination, facilitate charge injection from QDs to TiO2, and therefore, enhance photovoltage and photocurrent of the QD-SSC. The overall conversion efficiency achieved by the TiO2/QDs-BTOMe-DIOPA electrode is 0.88%.

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