Exciton Transport in Organic Semiconductors

Abstract

Photovoltaic cells based on organic semiconductors are attractive for their use as a renewable energy source owing to their abundant feedstock and compatibility with low-cost coating techniques on flexible substrates. In contrast to photovoltaic cells based traditional inorganic semiconductors, photon absorption in an organic semiconductor results in the formation of a coulombically bound electron-hole pair, or exciton. The transport of excitons, consequently, is of critical importance as excitons mediate the interaction between charge and light in organic photovoltaic cells (OPVs). In this dissertation, a strong connection between the fundamental photophysical parameters that control nanoscopic exciton energy transfer and the mesoscopic exciton transport is established. With this connection in place, strategies for enhancing the typically short length scale for exciton diffusion (LD) can be developed. Dilution of the organic semiconductor boron subphthalocyanine chloride (SubPc) is found to increase the LD for SubPc by 50%. In turn, OPVs based on dilute layers of SubPc exhibit a 30% enhancement in power conversion efficiency. The enhancement in power conversion efficiency is realized via enhancements in LD, optimized optical spacing, and directed exciton transport at an exciton permeable interface. The role of spin, energetic disorder, and thermal activation on LD are also addressed. Organic semiconductors that exhibit thermally activated delayed fluorescence and efficient intersystem and reverse intersystem crossing highlight the balance between singlet and triplet exciton energy transfer and diffusion. Temperature dependent measurements for LD provide insight into the inhomogeneously broadened exciton density of states and the thermal nature of exciton energy transfer. Additional topics include energy-cascade OPV architectures and broadband, spectrally tunable photodetectors based on organic semiconductors.