Donor Halogenation Effects on Electronic Structures and Electron Process Rates of Donor/C Heterojunction Interface: A Theoretical Study on F ZnPc ( n = 0, 4, 8, 16) and Cl SubPc ( n = 0, 6).

Molecular engineering is significantly important for developing electron donor and acceptor materials of active layers in organic photovoltaics (OPVs). The OPVs based on halogenated donors frequently produced high power conversion efficiencies. Here, based upon density functional theory calculations with optimally tuned range separation parameters and solid polarization effects, we studied the effects of donor halogenation on molecular geometries, electronic structures, excitation, and spectroscopic properties for F ZnPc ( n = 0, 4, 8, 16) and Cl SubPc ( n = 0, 6) monomers and the complexes with C as well as the photoinduced direct charge transfer (CT), exciton dissociation (ED), and charge recombination (CR) processes that were described by rate constants calculated using Marcus theory.