title: Hot charge-transfer excitons set the time limit for charge separation at donor/acceptor interfaces in organic photovoltaics.
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.
authors.affiliation: Energy Frontier Research Center (EFRC: CST), University of Texas, Austin, Texas 78712, USA.
authors.forename: Askat E
authors.initials: AE
authors.lastname: Jailaubekov
authors.forename: Adam P
authors.initials: AP
authors.lastname: Willard
authors.forename: John R
authors.initials: JR
authors.lastname: Tritsch
authors.forename: Wai-Lun
authors.initials: WL
authors.lastname: Chan
authors.forename: Na
authors.initials: N
authors.lastname: Sai
authors.forename: Raluca
authors.initials: R
authors.lastname: Gearba
authors.forename: Loren G
authors.initials: LG
authors.lastname: Kaake
authors.forename: Kenrick J
authors.initials: KJ
authors.lastname: Williams
authors.forename: Kevin
authors.initials: K
authors.lastname: Leung
authors.forename: Peter J
authors.initials: PJ
authors.lastname: Rossky
authors.forename: X-Y
authors.initials: XY
authors.lastname: Zhu