Coherent and diffusive time scales for exciton dissociation in bulk heterojunction photovoltaic cells

K. Birgitta Whaley*, Aleksey A. Kocherzhenko, Abraham Nitzan

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


We study the dynamics of charge separation in bulk heterojunction organic photovoltaic systems in light of recent experimental observations that this process is characterized by multiple time scales in the range of 10 fs to 100 ps. Coherent evolution of the excitonic state has been suggested to dominate the early stages of the charge separation process and diffusion of localized excitons to be dominant at longer times. Both of these processes obviously depend on the system morphology, in particular on the grain sizes of the donor and acceptor phases. Here we analyze these mechanisms and their characteristic time scales, aiming to verify the consistency of the proposed mechanisms with the experimentally observed time scales of charge separation. We suggest that the coherent mechanism that dominates the early stage of charge separation involves delocalized excitons. These excitons are formed by optical excitation of clusters of strongly interacting donor sites, and the charge separation rate is determined by the probability that such sites lie at the donor-acceptor interface. The (relatively) slow diffusive rate is estimated from the mean first passage time for a diffusing exciton to reach the donor grain surface. Our estimates, based on available exciton diffusion rates and morphology data, are consistent with experimental observations. (Figure Presented).

Original languageEnglish
Pages (from-to)27235-27244
Number of pages10
JournalJournal of Physical Chemistry C
Issue number47
StatePublished - 26 Nov 2014


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