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  • 學位論文

紫質雙體應用於染料敏化太陽能電池

Porphyrin Dimers for Dye-sensitized Solar Cells

指導教授 : 林敬堯
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摘要


在本篇論文中,利用 Sonogashira cross-coupling 方法合成了一系列紫質雙體 (porphyrin dimers) 光敏劑並應用於染料敏化太陽能電池的研究上◦ 六個新穎紫質雙體 (LDD1~LDD6) 分別修飾上 4-ethynyl-N,N-dimethylaniline 的推電子基團,並以碳-碳參鍵連接在兩個紫質單體的 meso-meso 位置做為 π-bridge (乙炔基),且依照中心是否配位上金屬設計成對稱 (Zn-Zn) 及不對稱 ( Zn-fb ) 兩種雙體類型,此外,為了能進一步利用近紅外光區的太陽光,兩紫質環除了以 ethynyl group 直接連接,更分別修飾上 anthracene 及 tetracene 基團,希望能夠藉由 π 共軛系統的擴張來延伸吸光的範圍◦ 由電化學結果得知,修飾 anthracene 及 tetracene 能夠使染料的還原電位往正電位方向移動, Zn-fb dimers 之氧化及還原電位相對 Zn-Zn dimers 亦有往正方向移動的趨勢◦由紫外光-可見光光譜圖及螢光放射光譜圖得知,相似結構的比較下,不對稱紫質雙體相較對稱雙體皆有吸收峰較紅移的趨勢;電子能階方面,染料激發態能階 (S*) 位置都高於 TiO2 導帶,使得電子應有足夠的驅動力注入 TiO2,而基態能階 (So/S+) 低於碘液能階,表示電解液能夠有效的再生染料,同時意味著這系列的紫質雙體適合應用於 n-type 的染敏太陽能電池中◦ LDD1~LDD6 的單一元件總轉換效率趨式為: LDD1 (8.6%) > LDD3 (5.98%) > LDD2 (5.22%) > LDD5 (2.26%) > LDD4 (2.16%) > LDD6 (0.78%); 其中 LDD1 與實驗室於 2011 年發表的 LD14 染料共敏化效率可高達 10.4% ◦

並列摘要


In this thesis, a series of ethynyl-linked, push-pull porphyrin dimers were synthesized and studied for dye-sensitized solar cells by Sonogashira cross-coupling method. These porphyrin dimers (denoted as LDD1~LDD6) bear a 4-ethynyl-N,N-dimethylaniline substituent as the electron-donating group, ethynyl goups as the π-bridges, and 4-ethynyl-benzoic acid as the anchoring group. Two versions of dimers were prepared : Zn-Zn and zinc-free-base (Zn-fb) dimers. In order to increase light-harvesting capability in the near-IR region, we also introduced anthracene and tetracene groups into the dimers. Electrochemical data show that the reduction potentials of the anthracene- and tetracene- modified porphyrin dimers are positive-shifted from those of the dimers without acenes, demonstrating the effect of extended π-conjugation. Both of the UV-Visible absorption spectra and fluorescence emission spectra show strong bathochromic shifts of the Zn-fb porphyrin dimers. The PCE values of LDD1~LDD6 DSSC show a trend of LDD1 (8.6%) > LDD3 (5.98%) > LDD2 (5.22%) > LDD5 (2.26%) > LDD4 (2.16%) > LDD6 (0.78%). Significantly, co-sensitizing LDD1 with LD14 gives rise to η = 10.4% of the DSSC. For the solid-state dye-sensitized solar cells, these dyes showed efficiencies in the range of 0.63%~1.63%.

參考文獻


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[4] Fraunhofer Institute for Solar Energy Systems ISE; Soitec; CEA-Leti; the Helmholtz Center Berlin.
[5] Loferski, J. J. J. Appl. Phys. 1956, 27, 777-784.

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