Deuteration as a Means to Tune Crystallinity of Conducting Polymers

Jakowski, Jacek; Huang, Jingsong; Garashchuk, Sophya; Luo, Yingdong; Hong, Kunlun; Keum, Jong; Sumpter, Bobby G.

doi:10.1021/acs.jpclett.7b01803

Deuteration as a Means to Tune Crystallinity of Conducting Polymers

Journal Article · Fri Aug 25 00:00:00 EDT 2017 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b01803· OSTI ID:1394393

^[1]; ^[1]; Garashchuk, Sophya ^[2]; Luo, Yingdong ^[1]; ^[1]; Keum, Jong ^[1]; ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of South Carolina, Columbia, SC (United States)

The effects of deuterium isotope substitution on conjugated polymer chain stacking of poly(3-hexylthiophene) is studied in this paper experimentally by X-ray diffraction (XRD) in combination with gel permeation chromatography and theoretically using density functional theory and quantum molecular dynamics. For four P3HT materials with different levels of deuteration (pristine, main-chain deuterated, side-chain deuterated, and fully deuterated), the XRD measurements show that main-chain thiophene deuteration significantly reduces crystallinity, regardless of the side-chain deuteration. The reduction of crystallinity due to the main-chain deuteration is a quantum nuclear effect resulting from a static zero-point vibrational energy combined with a dynamic correlation of the dipole fluctuations. The quantum molecular dynamics simulations confirm the interchain correlation of the proton–proton and deuteron–deuteron motions but not of the proton–deuteron motion. Thus and finally, isotopic purity is an important factor affecting stability and properties of conjugated polymer crystals, which should be considered in the design of electronic and spintronic devices.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Science Foundation (NSF) (United States); ORNL Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1394393

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 18 Vol. 8; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε‐Caprolactone) Li, Lengwan; Chang, Dongsook; Arras, Matthias M. L. Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 12 https://doi.org/10.1002/polb.24831	journal	April 2019
Theoretical assessment of the nuclear quantum effects on polymer crystallinity via perturbation theory and dynamics Jakowski, Jacek; Huang, Jingsong; Sumpter, Bobby G. International Journal of Quantum Chemistry, Vol. 118, Issue 20 https://doi.org/10.1002/qua.25712	journal	September 2018

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