近年來，研究有機共軛聚合物應用領域蓬勃發展，歸因於其分子結構具有導電特性，在發展太陽能領域具有龐大發展潛力，其中光催化產氫、光伏打電池便是目前熱門研究題目。此兩者的共通點皆是應用聚合物的分子設計去調控內部的能階差以形成予體-受體機制。然而，影響裝置功能的關鍵並不僅限於化學上的分子設計，更與其在溶液以及固態的單體與聚集結構特徵相關，故研究其結構特徵並進行調控極為重要。本研究利用小角度-廣角度X光散射技術(Small- and Wide-Angle X-ray Scattering, SAXS-WAXS or SWAXS)針對此類材料分別探討其於溶液狀態下的聚集結構特徵與其催化產氫或薄膜態太陽光電能表現的關聯性。第一部分探討側鏈橋接(side chain briged)的PCz2S聚合物於水溶液下的聚集網路對於產氫速率(HER)的影響，透過SWAXS數據的模型擬合，可以發現在水溶液中擁有最鬆散聚集網絡結構的PCz2S-PEG共軛聚合物，對應至最佳產氫速率。由此推測，寡乙二醇側鏈長度可助於調控聚集網絡內部大小，以導引水分子進入進行照催化光電子與氫離子的產生與電子交換形成氫氣。原位(in operando)照光產氫的SWAXS結果顯示，PCz2S-PEG與鉑離子照光共催化產氫的過程可能是以氫氣生成後再聚集形成約1.4 nm 大小的氫團簇，其初期產氫的動態可以成核量產方式描述。第二部分則探討雙成分系統有機太陽能電池於有機溶液中的結構特徵對光電轉換效率(PCE)之影響，使用模型擬合混摻系統，可得知在與幾個不同的非富勒烯受體(NFAs)的小分子混摻的系統中，PM6共軛聚合物所呈現出的鏈僵直度皆不相同，在氯苯溶液中展現出最僵直鏈的PM6:CB16二元系統，透露出與小分子CB16有較佳的交互作用，其對應的元件薄膜也有最好的光電轉換效率。在PM6:SB16混摻系統，則可以觀測到在進行旋轉塗佈成膜前的氯苯溶液中，SB16即已形成層狀排列的結構。這代表其混摻前SB16間即形成自我層狀排列。此種較大尺度的相分離現象大量減少到其與PM6的予體-受體的交互作用(電子交換)，造成低光電轉換效率的現象。本研究結果清楚顯示出調控溶液狀態下的聚集結構特徵對於提升有機共軛聚合物的工作表現有相當重要的影響。

In recent years, there has been significant development in the field of organic conjugated polymers due to their advanced molecular structures for improved electrical properties. Among the feature applications, photocatalytic hydrogen production and photovoltaic devices have particularly gained attention. These applications rely on molecular design of the conjugate polymers for appropriate energy levels that can form efficient donor-acceptor(D-A) pairs. However, factors influencing the photovoltaic device performance go beyond the molecular architecture design; tuning aggregation or network structures in solution and device thin films is also critically relevant. Understanding the solution aggregation structures of these materials is of help in controlling the structures formed in the corresponding device films. In this study, we have utilized small/wide- angle X-ray scattering (SWAXS) to investigate the correlations between the morphology in solution and the optoelectronic performance for two types of conjugate polymers. In the first system, we study the influence of network aggregation in aqueous solution of several side-chain bridged conjugate polymers, which can perform hydrogen evolution reaction (HER) under light illumination. The SWAXS data analysis reveals that PCz2S-PEG exhibits a mass fractal structure of relatively loose aggregate networks in water-based solution, among the three side-chain bridged conjugate polymers synthesized, and performs a best hydrogen evolution rate. The higher performance is attributed to the lengthened oligoethylene glycol side chains of PCz2S-PEG that can provide more internal space for water molecules to permeate inside the polymer fractal aggregates. Consequently, proton-electron pair production followed by electron transfer for hydrogen production can be better promoted. Furthermore, in-situ SAXS observation of PCz2S-PEG in solution under light illumination reveals a nucleation formation of 1.4 nm nanoclusters that are attributed to hydrogen clusters. In the second system, we investigate the solution structures of a conjugate polymer PM6 and its mixtures with several Y6-inspired small conjugate molecules in organic solutions; the solution structures are correlated to the photovoltaic performance (PCE) of the solar-cell films spin-coated from the binary solutions. SAXS model fitting of the blend system shows that the conjugated polymer PM6 exhibits different chain rigidity and network structures in chlorobenzene solutions containing the respective small molecules. Among them, PM6:CB16 complex exhibits the most rigid worm-like chains; which is associated with the highest photovoltaic conversion efficiency achieved with the spin-coated device film. In contrast, the PM6:SB16 mixture in chlorobenzene exhibits a lamellar structure, which resembles that for the SB16 solution alone and that in the thin films spin-coated from the mixture. The result suggests that SB16 phase-segregates strongly from PM6 in the solution and self-assembles into lamellar nanodomains. Consequently, the large-scale phase segregation and aggregation lead to a lowest device performance, due to less interfaces between PM6 and SB16 for charge separation and transfer. Understanding the solution structures of the organic conjugate polymers and their complexes with the small-molecule acceptors is of help in future optimization of the molecular design and device processing for improving further organic photovoltaic and photocatalytic performances.

摘要......1
ABSTRACT......3
目錄......5
圖目錄......7
表目錄......10
第1章 緒論......11
1.1共軛聚合物......11
1.2 有機共軛聚合物於溶液狀態下型態觀察......13
1.3 有機半導體機制......20
1.4 光催化產氫之有機共軛聚合物......22
1.5 有機太陽能電池......28
1.6 研究動機......30
第2章 研究方法......32
2.1 小角散射原理......32
2.2 小角散射模型擬合......33
2.3 幕次散射定律(power-law scattering)與質量碎形(mass fractal)......35
2.4 蠕蟲鏈(worm-like)......38
第3章 實驗設置......40
3.1 小角-廣角X光散射實驗設置......40
3.2 原位(in-operando)小角及廣角散射測量......45
3.3 相關性質測量1: 光催化產氫系統......46
3.4 相關性質測量2: 有機太陽能電池......49
第4章 結果與討論一: 側鏈橋接共軛聚合物於水溶液結構特徵探討......56
4.1 側鏈橋接共軛高分子於水溶液下結構特徵分析......57
4.2 受可見光激發原位(In-situ)小角X光散射分析......63
第5章 結果與討論之二: 太陽能有機電池(OSCS)二元系統於溶液狀態結構特徵探討......66
5.1 PM6聚合物結構特徵擬合 ......68
5.2 於氯苯下混摻系統結構特徵分析......71
第6章 結論......82
參考文獻......84
附錄......89

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