Molecular organization in MAPLE‐deposited conjugated polymer thin films and the implications for carrier transport characteristics

The morphological structure of poly(3‐hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin‐casting methods are investigated. The MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side‐chain stacking, π–π stacking, and conjugated backbone directions. Moreover, the average molecular orientations and relative degrees of crystallinity of MAPLE‐deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin‐casting technique. Despite the seemingly unfavorable molecular orientations and the highly disordered morphologies, the in‐plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin‐cast samples, exhibiting similar transport activation energies (56 vs. 54 meV) to those reported in the literature for high mobility polymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 39–48Molecular order in poly(3‐hexylthiophene) (P3HT) films deposited by the novel vapor‐assisted deposition technique Matrix Assisted Pulsed Laser Evaporation (MAPLE) was investigated. The structure of MAPLE‐deposited films is insensitive to the substrate chemistries and processes random crystallite orientation. The seemingly unfavorable morphology in MAPLE‐deposited samples however does not have detrimental effects on in‐plane transport characteristics, suggesting that field‐effect carrier transport in conjugated polymer devices is resilient to structure.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/135123/1/polb24237.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/135123/2/polb24237_am.pd