Direct Free Carrier Photogeneration in Single Layer and Stacked Organic Photovoltaic Devices.

High performance organic photovoltaic devices typically rely on type-II P/N junctions for assisting exciton dissociation. Heremans and co-workers recently reported a high efficiency device with a third organic layer which is spatially separated from the active P/N junction; but still contributes to the carrier generation by passing its energy to the P/N junction via a long-range exciton energy transfer mechanism. In this study the authors show that there is an additional mechanism contributing to the high efficiency. Some bipolar materials (e.g., subnaphthalocyanine chloride (SubNc) and subphthalocyanine chloride (SubPc)) are observed to generate free carriers much more effectively than typical organic semiconductors upon photoexcitation. Single-layer devices with SubNc or SubPc sandwiched between two electrodes can give power conversion efficiencies 30 times higher than those of reported single-layer devices. In addition, internal quantum efficiencies (IQEs) of bilayer devices with opposite stacking sequences (i.e., SubNc/SubPc vs SubPc/SubNc) are found to be the sum of IQEs of single layer devices. These results confirm that SubNc and SubPc can directly generate free carriers upon photoexcitation without assistance from a P/N junction. These allow them to be stacked onto each other with reversible sequence or simply stacking onto another P/N junction and contribute to the photocarrier generation.

Ionic Charge Transfer Complex Induced Visible Light Harvesting and Photocharge Generation in Perovskite.

Organometal trihalide perovskite has recently emerged as a new class of promising material for high efficiency solar cells applications. While excess ions in perovskites are recently getting a great deal of attention, there is so far no clear understanding on both their formation and relating ions interaction to the photocharge generation in perovskite. Herein, we showed that tremendous ions indeed form during the initial stage of perovskite formation when the organic methylammonium halide (MAXa, Xa=Br and I) meets the inorganic PbXb2 (Xb=Cl, Br, I). The strong charge exchanges between the Pb2+ cations and Xa- anions result in formation of ionic charge transfer complexes (iCTC). MAXa parties induce empty valence electronic states within the forbidden bandgap of PbXb2. The strong surface dipole provide sufficient driving force for sub-bandgap electron transition with energy identical to the optical bandgap of forming perovskites. Evidences from XPS/UPS and photoluminescence studies showed that the light absorption, exciton dissociation, and photocharge generation of the perovskites are closely related to the strong ionic charge transfer interactions between Pb2+ and Xa- ions in the perovskite lattices. Our results shed light on mechanisms of light harvesting and subsequent free carrier generation in perovskites.