Abstract
Photocurrent generation in organic photovoltaics (OPVs) relies on the dissociation of excitons into free electrons and holes at donor/acceptor heterointerfaces. The low dielectric constant of organic semiconductors leads to strong Coulomb interactions between electron–hole pairs that should in principle oppose the generation of free charges. The exact mechanism by which electrons and holes overcome this Coulomb trapping is still unsolved, but increasing evidence points to the critical role of hot charge-transfer (CT) excitons in assisting this process. Here we provide a real-time view of hot CT exciton formation and relaxation using femtosecond nonlinear optical spectroscopies and non-adiabatic mixed quantum mechanics/molecular mechanics simulations in the phthalocyanine–fullerene model OPV system. For initial excitation on phthalocyanine, hot CT excitons are formed in 10−13 s, followed by relaxation to lower energies and shorter electron–hole distances on a 10−12 s timescale. This hot CT exciton cooling process and collapse of charge separation sets the fundamental time limit for competitive charge separation channels that lead to efficient photocurrent generation.
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Acknowledgements
The results reported here were based on work supported as part of the Understanding Charge Separation and Transfer at Interfaces in Energy Materials (EFRC:CST), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001091. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the US Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000. Computational resources were provided by TACC and NERSC.
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X-Y.Z. supervised the experiments. P.J.R. supervised QM/MM simulations; A.E.J. and L.G.K. carried out the TR-SHG experiments; J.R.T. and W-L.C. carried out the TR-2PPE experiments; A.P.W. carried out the QM/MM simulations; R.G. assisted in sample preparation; K.J.W. helped with experimental set-up; N.S. and K.L. carried out time-dependent density functional theory calculations. X-Y.Z., A.E.J. and A.P.W. wrote the manuscript.
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Jailaubekov, A., Willard, A., Tritsch, J. et al. Hot charge-transfer excitons set the time limit for charge separation at donor/acceptor interfaces in organic photovoltaics. Nature Mater 12, 66–73 (2013). https://doi.org/10.1038/nmat3500
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DOI: https://doi.org/10.1038/nmat3500
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