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Title: Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics

Abstract

Recent experimental studies revealed that charge carriers harvested by bulk heterojunction organic photovoltaics can be collected on ultrafast time scales. To investigate ultrafast exciton mobility, we construct simple, nonatomistic models of a common polymeric electron donor material. We first explore the relationship between the magnitude of energetic noise in the model Hamiltonian and the spatial extent of resulting eigenstates. We then employ a quantum master equation approach to simulate migration of chromophore-localized initial excited states. Excitons initially localized on a single chromophore at the center of the model delocalize down polymer chains and across pi-stacked chromophores through a coherent, wavelike mechanism during the first few tens of femtoseconds. We explore the dependence of this coherent delocalization on coupling strength and on the magnitude of energetic noise. At longer times we observe continued migration toward a uniform population distribution that proceeds through an incoherent, diffusive mechanism. A series of simulations modeling exciton harvesting in domains of varying size demonstrates that smaller domains enhance ultrafast exciton harvesting yield. Finally, our nonatomistic model falls short of quantitative accuracy but demonstrates that excitons are mobile within electron donor domains on ultrafast time scales and that coherent exciton transport can enhance ultrafast exciton harvesting.

Authors:
 [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. DePaul Univ., Chicago, IL (United States)
  2. The Univ. of Chicago, Chicago, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
DePaul University; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Materials Sciences and Engineering Division
OSTI Identifier:
1352534
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 10; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Bednarz, Mateusz, Lapin, Joel, McGillicuddy, Ryan, Pelzer, Kenley M., Engel, Gregory S., and Griffin, Graham B.. Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.6b11332.
Bednarz, Mateusz, Lapin, Joel, McGillicuddy, Ryan, Pelzer, Kenley M., Engel, Gregory S., & Griffin, Graham B.. Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics. United States. doi:10.1021/acs.jpcc.6b11332.
Bednarz, Mateusz, Lapin, Joel, McGillicuddy, Ryan, Pelzer, Kenley M., Engel, Gregory S., and Griffin, Graham B.. Tue . "Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics". United States. doi:10.1021/acs.jpcc.6b11332. https://www.osti.gov/servlets/purl/1352534.
@article{osti_1352534,
title = {Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics},
author = {Bednarz, Mateusz and Lapin, Joel and McGillicuddy, Ryan and Pelzer, Kenley M. and Engel, Gregory S. and Griffin, Graham B.},
abstractNote = {Recent experimental studies revealed that charge carriers harvested by bulk heterojunction organic photovoltaics can be collected on ultrafast time scales. To investigate ultrafast exciton mobility, we construct simple, nonatomistic models of a common polymeric electron donor material. We first explore the relationship between the magnitude of energetic noise in the model Hamiltonian and the spatial extent of resulting eigenstates. We then employ a quantum master equation approach to simulate migration of chromophore-localized initial excited states. Excitons initially localized on a single chromophore at the center of the model delocalize down polymer chains and across pi-stacked chromophores through a coherent, wavelike mechanism during the first few tens of femtoseconds. We explore the dependence of this coherent delocalization on coupling strength and on the magnitude of energetic noise. At longer times we observe continued migration toward a uniform population distribution that proceeds through an incoherent, diffusive mechanism. A series of simulations modeling exciton harvesting in domains of varying size demonstrates that smaller domains enhance ultrafast exciton harvesting yield. Finally, our nonatomistic model falls short of quantitative accuracy but demonstrates that excitons are mobile within electron donor domains on ultrafast time scales and that coherent exciton transport can enhance ultrafast exciton harvesting.},
doi = {10.1021/acs.jpcc.6b11332},
journal = {Journal of Physical Chemistry. C},
number = 10,
volume = 121,
place = {United States},
year = {Tue Feb 21 00:00:00 EST 2017},
month = {Tue Feb 21 00:00:00 EST 2017}
}

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