Nguyen Thanh-Danh, Nguyen Van-Hai, Song Jongwoo, An Jongdeok, Truong Ngoc-Thuan, Dang Chi-Hien, Im Chan
Department of Chemistry, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul 05029, Korea.
Institute of Chemical Technology, Vietnam Academy of Science and Technology, 1A TL29 Street, Thanh Loc Ward, District 5, Ho Chi Minh City 70000, Vietnam.
Polymers (Basel). 2021 Oct 7;13(19):3440. doi: 10.3390/polym13193440.
A series of poly-3-alkylthiophenes (P3ATs) with butyl (P3BT), hexyl (P3HT), and octyl (P3OT) side-chains and well-defined molecular weights (MWs) were synthesized using Grignard metathesis polymerization. The MWs of P3HTs and P3OTs obtained via gel permeation chromatography agreed well with the calculated MWs ranging from approximately 10 to 70 kDa. Differential scanning calorimetry results showed that the crystalline melting temperature increased with increasing MWs and decreasing alkyl side-chain length, whereas the crystallinity of the P3ATs increased with the growth of MWs. An MW-dependent red shift was observed in the UV-Vis and photoluminiscence spectra of the P3ATs in solution, which might be a strong evidence for the extended effective conjugation occurring in polymers with longer chain lengths. The photoluminescence quantum yields of pristine films in all polymers were lower than those of the diluted solutions, whereas they were higher than those of the phenyl-C-butyric acid methyl ester-blended films. The UV-Vis spectra of the films showed fine structures with pronounced red shifts, and the interchain interaction-induced features were weakly dependent on the MW but significantly dependent on the alkyl side-chain length. The photovoltaic device performances of the P3BT and P3HT samples significantly improved upon blending with a fullerene derivative and subsequent annealing, whereas those of P3OTs mostly degraded, particularly after annealing. The optimal power conversion efficiencies of P3BT, P3HT, and P3OT were 2.4%, 3.6%, and 1.5%, respectively, after annealing with MWs of ~11, ~39, and ~38 kDa, respectively.
采用格氏易位聚合法合成了一系列带有丁基（P3BT）、己基（P3HT）和辛基（P3OT）侧链且分子量明确的聚3-烷基噻吩（P3AT）。通过凝胶渗透色谱法测得的P3HT和P3OT的分子量与计算得到的分子量吻合良好，范围约为10至70 kDa。差示扫描量热法结果表明，结晶熔点随分子量增加和烷基侧链长度减小而升高，而P3AT的结晶度随分子量增长而增加。在溶液中P3AT的紫外可见光谱和光致发光光谱中观察到了分子量依赖性红移，这可能是长链聚合物中发生有效共轭扩展的有力证据。所有聚合物中原始薄膜的光致发光量子产率均低于稀释溶液的光致发光量子产率，但其高于苯基-C-丁酸甲酯共混薄膜的光致发光量子产率。薄膜的紫外可见光谱显示出具有明显红移的精细结构，链间相互作用诱导的特征对分子量的依赖性较弱，但对烷基侧链长度的依赖性显著。与富勒烯衍生物共混并随后退火后，P3BT和P3HT样品的光伏器件性能显著提高，而P3OT的光伏器件性能大多下降，尤其是退火后。分别用分子量约为11 kDa、39 kDa和38 kDa的P3BT、P3HT和P3OT退火后，其最佳功率转换效率分别为2.4%、3.6%和1.5%。
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