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Application of Fluorescence Resonance Energy Transfer in Dye-Sensitized Solar Cells
|關鍵字:||螢光團;energy relay dye;光捕獲;太陽能電池;螢光共振能量轉移;fluorophore;energy relay dye;light harvesting;solar cell;fluorescence resonance energy transfer||引用:|| Wikipedia. (accessed January 4, 2017). Energy crisis [Online]. Available: https://en.wikipedia.org/wiki/Energy_crisis  Wikipedia. (accessed January 4, 2017). 核子動力 [Online]. Available: https://zh.wikipedia.org/wiki/%E6%A0%B8%E5%8B%95%E5%8A%9B  Wikipedia. (accessed January 4, 2017). Nuclear power [Online]. Available: https://en.wikipedia.org/wiki/Nuclear_power  N. R. E. Laboratory. (accessed January 6, 2017). Photovoltaic Research NREL [Online]. Available: http://www.nrel.gov/pv/  B. O''Regan and M. Grätzel, 'A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films,' Nature, Vol. 353, pp. 737-740 (1991).  A. Yella, H.-W. Lee, H. N. Tsao, C. Yi, A. K. Chandiran, M. K. Nazeeruddin, E. W.-G. Diau, C.-Y. Yeh, S. M. Zakeeruddin, and M. 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本論文探討1,8-naphthalimide derivative有機螢光團引發之螢光共振能量轉移(fluorescence resonance energy transfer, FRET)效應於染料敏化太陽能電池(dye-sensitized solar cell, DSSC)之應用，研究內容主要依有機螢光團有無羧基概分為二。研究主題一採用無羧基之有機螢光團(簡稱N-Bu)摻雜於網印之中孔二氧化鈦光電極中，摻雜方法為將二氧化鈦光電極進行兩步驟依序浸泡於螢光染料N-Bu及敏化染料N719溶液中。在照光的情況下，N-Bu螢光團會吸收紫外光成為激發態，由於N-Bu螢光團之放射光譜與敏化染料N719之吸收光譜緊密重疊，當N-Bu與N719分子相距於Förster radius內，激發態之N-Bu會經由FRET方式將能量傳遞予N719，驅使N719產生更多電子，提升DSSC於紫外光區間之光捕獲強度，同時提升紫外光區間之光電轉化效率(incident photon to current conversion efficiencies, IPCE)。當使用10-4 M之N-Bu溶液摻雜螢光團，DSSC之能量轉換效率(power conversion efficiencies, PCE)可由7.63 %提升至8.13 %，改善幅度約為6.6 %。
主題二使用含有羧基之有機螢光團(1,8-naphthalimide derivative with carboxylic group, 簡稱N-COOH)，透過羧基與二氧化鈦的附著力，使摻雜之N-COOH能與N719共同吸附在二氧化鈦表面，藉此增強FRET效應，摻雜方法可簡化為光電極浸泡於敏化染料N719與螢光團N-COOH混合液中之一步驟共吸附方式。N-COOH光學性質相似於研究主題一之N-Bu，因此N-COOH亦會吸收紫外光並經由FRET方式將能量傳遞予N719。研究結果發現在N-COOH與N719共吸附過程中，N-COOH不會影響N719於二氧化鈦薄膜中之吸附量，且吸附N-COOH可減少二氧化鈦直接與電解液之接觸面積，減少電子逆反應發生。採用最佳混合比例之溶液(N719:N-COOH = 5:1)進行共吸附，DSSC於1 sun (AM1.5G)下其能量轉換效率改善幅度達10.8 % (從9.16 %提升至10.15 %)，優於主題一的改善幅度。而在600 lux之T5燈具(600 lux之三波長)下其能量轉換效率改善幅度達21 % (PCE從16.46 %提升至19.92 %)，Pmax可由31.77 μW/cm2提升至38.44 μW/cm2。
This dissertation investigates the application of the fluorescence resonance energy transfer (FRET) effect induced by an organic fluorophores (1,8-naphthalimide derivative) in dye-sensitized solar cell (DSSC). There are two parts of research in this dissertation based on two organic fluorophores with and without a carboxylic group. In Part I, an organic fluorophore without a carboxylic group, named as N-Bu, is doped into a mesoporous TiO2 photoanode by a two-step dipping procedure sequentially in the N-Bu and N719 solutions. The N-Bu fluorophore can be excited via absorbing ultraviolet light and then transfers the absorbed energy to the N719 sensitizing dye by means of the FRET effect when the N-Bu and N719 molecules are within the Förster radius. The high spectral overlap between the emission spectrum of fluorophore and the absorption spectrum of sensitizing dye is also advantageous for the FRET effect. Therefore, the FRET effect promotes the light harvesting of DSSC in the ultraviolet spectrum range and the incident photon to current conversion efficiencies (IPCE). An improved power conversion efficiency (PCE) of 8.13% is obtained for the fluorophore-doped (10-4 M) DSSC as compared with that without the doping of fluorophore (7.63%).
In Part II, a 1,8-naphthalimide derivative with a carboxylic group, N-COOH, is doped into a mesoporous TiO2 film together with N719 by a co-adsorption method which is performed by dipping the mesoporous TiO2 photoanodes into the mixed solutions of N719 and N-Bu. The photobehavior of N-COOH is similar to the N-Bu fluorophore which is used in the Part I. Hence, the N-COOH fluorophore can also absorb the ultraviolet light and transit the absorbed energy to N719 by means of FRET. Because the N-COOH fluorophore can adsorb on the TiO2 surface with its carboxylic group as N719 does, an in-situ FRET system can be built up to induce more efficient energy transfer from the FRET donor (N-COOH) to the FRET acceptor (N719). The co-adsorption of N-COOH with N719 does not influence the dye-loading amount of N719 in the mesoporous TiO2 film, and it can further inhibit charge recombination owing to reduced contact area between TiO2 and electrolyte. The results show that the DSSCs with doping of the N-COOH fluorophore are efficient for 1 sun (AM1.5G) and indoor lighting conditions. Upon using optimal mixed solution (N719:N-COOH = 5:1), the PCE of DSSC under 1 sun illumination increases by 10.8 % (from 9.16 to 10.15 %), and that for T5 fluorescent lamps of 600 lux increases by 21 % (PCE from 16.46 to 19.92 % and Pmax from 31.77 to 38.44 μW/cm2), as compared with that adsorbing N719 only.
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