Beyond Bloch: A Theoretical Blueprint for Conjugated Polymer Optoelectronics

Abstract

Conjugated polymers are experiencing a surge of renewed interest due to their promising applications in various organic electronic devices. These include organic light-emitting diodes (OLEDs), field-effect transistors (FETs), and organic photovoltaic (OPV) devices, among many others. Their appeal stems from distinct advantages they hold over traditional inorganic semiconductors. Unlike inorganic semiconductors, where electrons are often considered to be in delocalized, free, or quasi-free states (as described by Bloch's theory), electrons in conjugated polymers behave differently. They are strongly coupled within highly localized $σ$ or $π$-orbitals and interact significantly with the ionic cores. This means they are far from the idealized delocalized states presumed by Bloch's theory approaches. Consequently, after nearly a century of applying Bloch's theory to the electronic transport properties of inorganic materials, there is a clear need for a new theoretical framework to explain efficient charge transport in these organic solids. Our presented model addresses this need by incorporating crucial electron-electron interactions. Specifically, it accounts for both intra-site interactions and interactions between the $π$-states located at alternating sites along the polymer chain. This framework provides a many-body charge conduction mechanism and explains the semiconducting properties of the undoped material. A significant outcome of our model is the prediction of two novel flat bands of excited bonding states. Intriguingly, these states obey Bose--Einstein statistics and facilitate charge transport. Furthermore, our model accurately reproduces experimental data, providing an excellent fit for measured UV-Vis absorption and electroluminescent spectra.