Molecular weight dependent structure and charge transport in MAPLE‐deposited poly(3‐hexylthiophene) thin films

In this work, poly(3‐hexylthiophene) (P3HT) films prepared using the matrix‐assisted pulsed laser evaporation (MAPLE) technique are shown to possess morphological structures that are dependent on molecular weight (MW). Specifically, the structures of low MW samples of MAPLE‐deposited film are composed of crystallites/aggregates embedded within highly disordered environments, whereas those of high MW samples are composed of aggregated domains connected by long polymer chains. Additionally, the crystallite size along the side‐chain (100) direction decreases, whereas the conjugation length increases with increasing molecular weight. This is qualitatively similar to the structure of spin‐cast films, though the MAPLE‐deposited films are more disordered. In‐plane carrier mobilities in the MAPLE‐deposited samples increase with MW, consistent with the notion that longer chains bridge adjacent aggregated domains thereby facilitating more effective charge transport. The carrier mobilities in the MAPLE‐deposited simples are consistently lower than those in the solvent‐cast samples for all molecular weights, consistent with the shorter conjugation length in samples prepared by this deposition technique. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 652–662The structure of MAPLE‐deposited P3HT thin films is shown to possess molecular weight (MW) dependence behavior. The MAPLE films deposited from low MW materials consist of crystallite domains embedded within a highly amorphous environment, whereas those deposited from high MW materials are composed of long polymer chains bridging the aggregate domains. The in‐plane mobility is shown to increase with MW, highlighting the importance of domain connectivity in facilitating charge transport in conjugated polymers.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/142537/1/polb24588-sup-0001-suppinfo1.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/142537/2/polb24588_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/142537/3/polb24588.pd