Polymorphism controls the degree of charge transfer in a molecularly doped semiconducting polymer

被引:108
作者
Jacobs, Ian E. [1 ,4 ]
Cendra, Camila [2 ]
Harrelson, Thomas F. [3 ]
Valdez, Zaira I. Bedolla [3 ]
Faller, Roland [3 ]
Salleo, Alberto [2 ]
Moule, Adam J. [3 ]
机构
[1] Univ Calif Davis, Dept Mat Sci & Engn, Davis, CA 95616 USA
[2] Stanford Univ, Dept Mat Sci & Engn, Stanford, CA 94305 USA
[3] Univ Calif Davis, Dept Chem Engn, Davis, CA 95616 USA
[4] Univ Cambridge, Cavendish Lab, Cambridge, England
基金
美国国家科学基金会;
关键词
IONIC PHASE-TRANSITION; DOPING EFFICIENCY; POLY(3-HEXYLTHIOPHENE); P3HT; FILMS; CONDUCTIVITY; AGGREGATION; SOLUBILITY; TRANSPORT; DOPANTS;
D O I
10.1039/c8mh00223a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
When an organic semiconductor (OSC) is blended with an electron acceptor molecule that can act as a p-type dopant, there should ideally be complete (integer) transfer of charge from the OSC to the dopant. However, some dopant-OSC blends instead form charge transfer complexes (CTCs), characterized by fractional charge transfer (CT) and strong orbital hybridization between the two molecules. Fractional CT doping does not efficiently generate free charge carriers, but it is unclear what conditions lead to incomplete charge transfer. Here we show that by modifying film processing conditions in the semiconductor-dopant couple poly(3-hexylthiophene): 2,3,5,6tetrafluoro- 7,7,8,8,-tetracyanoquinodimethane (P3HT: F4TCNQ), we can selectively obtain nearly pure integer or fractional CT phases. Fractional CT films show electrical conductivities approximately 2 orders of magnitude lower than corresponding integer CT films, and remarkably different optical absorption spectra. Grazing incidence wide-angle X-ray diffraction (GIXD) reveals that fractional CT films display an unusually dense and well-ordered crystal structure. These films show lower paracrystallinity and shorter lamellar and p-stacking distances than undoped films processed under similar conditions. Using plane-wave DFT we obtain a structure with unit cell parameters closely matching those observed by GIXD. This first-ever observation of both fractional and integer CT in a single OSC-dopant system demonstrates the importance of structural effects on OSC doping and opens the door to further studies.
引用
收藏
页码:655 / 660
页数:6
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