Connecting Molecular Conformation to Aggregation in P3HT Using Near Edge X-ray Absorption Fine Structure Spectroscopy

Urquhart, Stephen G.; Martinson, Mercedes; Eger, Shaylin; Murcia, Victor; Ade, Harald; Collins, Brian A.

doi:10.1021/acs.jpcc.7b07143

Title: Connecting Molecular Conformation to Aggregation in P3HT Using Near Edge X-ray Absorption Fine Structure Spectroscopy

Journal Article · Mon Sep 11 00:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b07143· OSTI ID:1539213

Urquhart, Stephen G. ^[1]; Martinson, Mercedes ^[1]; Eger, Shaylin ^[1]; Murcia, Victor ^[2]; Ade, Harald ^[3]; Collins, Brian A. ^[2]

University of Saskatchewan, Saskatoon, SK (Canada)
Washington State University, Pullman, WA (United States)
North Carolina State University, Raleigh, NC (United States)

Carbon 1s near edge X-ray absorption fine structure (NEXAFS) and UV–vis spectroscopy are used to examine differences between highly aggregated and poorly aggregated forms of the polymer poly(3-hexylthiophene) (P3HT), based on as-cast and annealed regiorandom and regioregular P₃HT samples. UV–vis spectra show characteristic signatures of unaggregated P₃HT in regiorandom P₃HT, and of H-aggregation in regioregular P₃HT samples. Distinct spectroscopic differences, including energy shifts, are observed in the NEXAFS spectra of aggregated P₃HT relative to the unaggregated forms. These differences are reproduced with transition-potential density functional theory (TP-DFT) calculations which explore aggregation and molecular conformation. Differences in the NEXAFS spectra of P₃HT are assigned to thiophene backbone twisting in the unaggregated forms of P₃HT, and to various degrees of chain planarization in aggregated forms of P₃HT that also correlate to the exciton bandwidth. Here these results open up the prospect of characterizing conformation and related difficult to assess structural details through NEXAFS spectroscopy and correlative theory and electronic structure analysis.

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Research Organization:: North Carolina State University, Raleigh, NC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); Nature Sciences and Engineering Research Council (NSERC)

Grant/Contract Number:: FG02-98ER45737; AC02-05CH11231

OSTI ID:: 1539213

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 39; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 19 works

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