Ion Coordination and Chelation in a Glycolated Polymer Semiconductor: Molecular Dynamics and X-ray Fluorescence Study
Paulsen, Bryan D.
Petty, Anthony J.
Schatz, George C
KAUST DepartmentKAUST Solar Center (KSC)
Physical Science and Engineering (PSE) Division
Chemical Science Program
Online Publication Date2020-08-04
Print Publication Date2020-09-08
Embargo End Date2021-08-04
Permanent link to this recordhttp://hdl.handle.net/10754/663432
MetadataShow full item record
AbstractPolythiophenes bearing glycolated side chains have rapidly surged as the highest performing materials for organic electrochemical transistors (OECTs) because of their ability to conjugate volumetric ion penetration with high hole mobility and charge density. Among them, p(g2T-TT) has one of the highest figures of merit. Our work provides an atomistic picture of the p(g2T-TT)-electrolyte interface in the "off"state of an OECT, expected to be dominated by cation-polymer interactions. Using a combination of molecular dynamics simulations and X-ray fluorescence, we show how different anions effectively tune the coordination and chelation of cations by p(g2T-TT). At the same time, softer and hydrophobic anions such as TFSI- and ClO4- are found to preferentially interact with the p(g2T-TT) phase, further enhancing the polymer-cation chelation. We highlight how the stronger hydrophobic nature of TFSI- causes its preferential accumulation at the polymer interface, further enhancing the anion-enabled cation-polymer chelation. Besides opening the way for a full study of electrolyte doping mechanisms in operating devices, our results suggest that tailoring the electrolyte for different applications and materials might be a viable strategy to tune the performance of mixed conducting devices.
CitationMatta, M., Wu, R., Paulsen, B. D., Petty, A. J., Sheelamanthula, R., McCulloch, I., … Rivnay, J. (2020). Ion Coordination and Chelation in a Glycolated Polymer Semiconductor: Molecular Dynamics and X-ray Fluorescence Study. Chemistry of Materials, 32(17), 7301–7308. doi:10.1021/acs.chemmater.0c01984
SponsorsM.M. and G.C.S. were supported by NSF grant CMMI1848613. RW, BDP, and J.R. gratefully acknowledge support from the National Science Foundation grant no. NSF DMR1751308. This work used the Extreme Science and Engineering Discovery Environment (XSEDE) BRIDGES at the Pittsburgh Supercomputing Center (PSC) through allocation CHE190029. This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). Portions of this work were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, The Dow Chemical Company, and DuPont de Nemours, Inc. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357.
PublisherAmerican Chemical Society (ACS)
JournalChemistry of Materials
Except where otherwise noted, this item's license is described as This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.chemmater.0c01984.