Energy offset at the donor (D)/acceptor (A) interface plays an important role in charge separation in organic photovoltaics. Its magnitude determines the charge separation process under illumination. Extensive studies have been carried out for elucidating the charge transfer (CT) process at different D/A junctions. These works lead to two different views: upon photoexcitation, energies would be (1) consumed in molecular polarization and orientation such that those opposite charges would overcome mutual Coulombic attractive potential at the interface and (2) spent on promoting charges to high-lying delocalized energy states (i.e., hot states), which is necessarily important prior to charge separation. Under these two scheme of studies, the electronic structures and the charge behaviors at the D/A interface should be different under photoexcitation, yet there is so far no direct experimental approach for probing the changes in electronics structures (i.e., Fermi level, vacuum level, frontier molecular orbitals, etc.) upon photoexcitation. Herein, a modified photoelectron spectroscopy (PES) system with an additional solar simulator is used to study the charge distributions and electronic interactions for a standard D/A heterojunction (i.e., copper phthalocyanine (CuPc)/ fullerene (C60)) under photoexcitation. CT states formed as a result of photon energy transfer at the CuPc/C60 junction. Subsequent superpositions of charge transfer and electron polarization effects increase the D/A energy level offsets from 0.75 (ground state measured in the dark) to 1.07 eV (high-lying state measured upon illumination). We showed that there is excess energy consumed for a subtle change in the energy level alignment of the CuPc/C60 junction under illumination, suggesting a new insight for the energy loss mechanism during the photocharge generation processes.
Keywords: charge transfer; exciton dissociation; organic semiconductors; photoemission spectroscopy; photovoltaics.