The Impact of Aggregation on the p-Doping Kinetics of Poly(3-hexylthiophene).
The Impact of Aggregation on the p-Doping Kinetics of Poly(3-hexylthiophene).
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聚集对聚（3-己基噻吩）p 掺杂动力学的影响。
DOI：
10.1039/c7tc00189d
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发表时间：
2017
期刊：
影响因子：
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通讯作者：
Guo,Song
中科院分区：
文献类型：
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作者：
McFarland,FrederickM;Bonnette,Lindsey;Acres,ElishaA;Guo,Song
用光学吸收光谱和停流技术研究了区域规则聚(3-己基噻吩基)(P3HT)在溶液中与2，3，5，6-tetrafluoro-7，7，8，8-tetracyanoquinodimethane(F4-TCNQ)对p掺杂动力学的形态效应。研究了两种形态：增溶的(S-P3HT)和纳米晶须(NW-P3HT)。对于F4-TCNQ的整数电荷转移产物，P3HT增溶溶液和聚集溶液都显示出相似的特征近红外吸收带。对P掺杂S-P3HT和F4-TCNQ的动力学分析表明，掺杂反应遵循S-P3HT的一级反应机理。P3HT聚集体溶液的掺杂动力学表现出两种不同的反应机理。慢速机理的反应速率常数与增溶P3HT溶液的反应速率常数相似，这可能是聚集体溶液中存在的S-P3HT组分所致。最快的一个被分配给NW-P3HT组分，可能是因为聚集的P3HT纳米结构中更有效的电荷离域。此外，P掺杂反应的动力学趋势与P3HT的反应性呈高斯分布的考虑更好地拟合，与源于分子量和形态变化的聚合物体系的复杂性相匹配。这项研究强调了考虑不同形态的共轭聚合物在其电荷转移反应动力学中的重要性。所获得的知识对于化学掺杂在有机电子器件制造中的应用具有重要的基础和实际意义。
The morphological effects of regioregular poly(3-hexylthiophene) (P3HT) on its p-doping kinetics with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) in solution are studied using optical absorption spectroscopy and the stopped-flow technique. Two morphological forms, solubilized (s-P3HT) and nanowhiskers (nw-P3HT), are investigated. Both P3HT solubilized and aggregated solutions show similar characteristic near-IR absorption bands for integer charge transfer products with F4-TCNQ. Kinetic analysis on p-doping of s-P3HT with F4-TCNQ indicates that the doping reaction proceeds with a single reaction mechanism that is of first order in s-P3HT. The doping kinetics of P3HT aggregate solution shows two distinctive reaction mechanisms. The slow mechanism has a reaction rate constant similar to that of solubilized P3HT solution, so it likely results from s-P3HT components that are present in the aggregate solution. The fast one is assigned to the nw-P3HT component, probably due to more efficient charge delocalization in the aggregated P3HT nanostructures. Additionally, the kinetic trends of the p-doping reactions are better fitted with the consideration of a Gaussian-like distribution of reactivities from P3HT, matching the complexity of polymeric systems originating from molecular weight and morphology variations. This study highlights the importance of considering different morphological forms of conjugated polymers in their charge-transfer reaction kinetics. The knowledge gained here should be fundamentally and practically important for future chemical doping applications in organic electronic device fabrications.