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

Bednarz, Mateusz; Lapin, Joel; McGillicuddy, Ryan; Pelzer, Kenley M.; Engel, Gregory S.; Griffin, Graham B.

doi:10.1021/acs.jpcc.6b11332

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

Journal Article · 21 February 2017 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.6b11332 · OSTI ID:1352534

Bednarz, Mateusz ^[1]; Lapin, Joel ^[1]; McGillicuddy, Ryan ^[2];

^[3];

^[2];

^[1]

DePaul Univ., Chicago, IL (United States)
The Univ. of Chicago, Chicago, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: DePaul University; USDOE Office of Science (SC), Basic Energy Sciences (BES); Materials Sciences and Engineering Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1352534

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 10; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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