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The Effects of Crystallinity on Charge Transport and the Structure of Sequentially Processed F4TCNQ‐Doped Conjugated Polymer Films
Authors:D Tyler Scholes  Patrick Y Yee  Jeffrey R Lindemuth  Hyeyeon Kang  Jonathan Onorato  Raja Ghosh  Christine K Luscombe  Frank C Spano  Sarah H Tolbert  Benjamin J Schwartz
Affiliation:1. Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, USA;2. Lake Shore Cryotronics, Westerville, OH, USA;3. Materials Science and Engineering Department, University of Washington, Seattle, WA, USA;4. Department of Chemistry, Temple University, Philadelphia, PA, USA;5. Department of Materials Science and Engineering, University of California, Los Angeles, Los Angeles, CA, USA;6. California NanoSystems Institute, University of California, Los Angeles, Los Angeles, CA, USA
Abstract:The properties of molecularly doped films of conjugated polymers are explored as the crystallinity of the polymer is systematically varied. Solution sequential processing (SqP) was used to introduce 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ) into poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) while preserving the pristine polymer's degree of crystallinity. X‐ray data suggest that F4TCNQ anions reside primarily in the amorphous regions of the film as well as in the P3HT lamellae between the side chains, but do not π‐stack within the polymer crystallites. Optical spectroscopy shows that the polaron absorption redshifts with increasing polymer crystallinity and increases in cross section. Theoretical modeling suggests that the polaron spectrum is inhomogeneously broadened by the presence of the anions, which reside on average 6–8 Å from the polymer backbone. Electrical measurements show that the conductivity of P3HT films doped by F4TCNQ via SqP can be improved by increasing the polymer crystallinity. AC magnetic field Hall measurements show that the increased conductivity results from improved mobility of the carriers with increasing crystallinity, reaching over 0.1 cm2 V?1 s?1 in the most crystalline P3HT samples. Temperature‐dependent conductivity measurements show that polaron mobility in SqP‐doped P3HT is still dominated by hopping transport, but that more crystalline samples are on the edge of a transition to diffusive transport at room temperature.
Keywords:charge transport  doping  Hall Effect  morphology  semiconducting polymers
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