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Spontaneous Exciton Dissociation at Organic Semiconductor Interfaces Facilitated by the Orientation of the Delocalized Electron–Hole Wavefunction
Author(s) -
Kafle Tika R.,
Kattel Bhupal,
Wanigasekara Shanika,
Wang Ti,
Chan WaiLun
Publication year - 2020
Publication title -
advanced energy materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.08
H-Index - 220
eISSN - 1614-6840
pISSN - 1614-6832
DOI - 10.1002/aenm.201904013
Subject(s) - exciton , delocalized electron , biexciton , materials science , wave function , electron , organic solar cell , semiconductor , chemical physics , dissociation (chemistry) , organic semiconductor , atomic physics , condensed matter physics , molecular physics , physics , optoelectronics , chemistry , quantum mechanics , composite material , polymer
In organic semiconductors, optical excitation does not necessarily produce free carriers. Very often, electron and hole are bound together to form an exciton. Releasing free carriers from the exciton is essential for the functioning of photovoltaics and optoelectronic devices, but it is a bottleneck process because of the high exciton binding energy. Inefficient exciton dissociation can limit the efficiency of organic photovoltaics. Here, nanoscale features that can allow the free carrier generation to occur spontaneously despite being an energy uphill process are determined. Specifically, by comparing the dissociation dynamics of the charge transfer (CT) exciton at two donor–acceptor interfaces, it is found that the relative orientation of the electron and hole wavefunction within a CT exciton plays an important role in determining whether the CT exciton will decompose into the higher energy free electron–hole pair or relax to the lower energy tightly‐bound CT exciton. The concept of the entropic driving force is combined with the structural anisotropy of typical organic crystals to devise a framework that can describe how the orientation of the delocalized electronic wavefunction can be manipulated to favor the energy‐uphill spontaneous dissociation of CT excitons over the energy‐downhill CT exciton cooling.