Effect of Packing on Formation of Deep Carrier Traps in Amorphous Conjugated Polymers

We theoretically investigate the role of conformational disorder and intermolecular interactions on the localization properties of electronic states, leading to the formation of carrier traps in amorphous aggregates of conjugated polymers. Samples of amorphous conformations of poly(p-phenylene vinylene) (PPV), poly2-methoxy-5-(2-ethyl-hexyloxy)PPV (MEH-PPV), and [poly-(9,9'-dioctyluorene)] (PFO) oligomers are simulated by classical molecular dynamics, while their electronic structure is calculated using first-principles density functional theory. Localization and delocalization properties of molecular orbitals are studied based on the participation ratio analysis, an approach commonly used in inorganic semiconductors. Our simulations confirm that the alkyl side chains insignificantly affect the conformational disorder in amorphous polymers while having a dramatic effect on the intermolecular disorder and packing. The nature of the disorder and its impact on charge-carrier localization in amorphous polymers with alkyl side chains differ drastically from those of disordered polymers without side chains, such as PPVs. Thus, long-range intermolecular interactions and sparse packing are responsible for the formation of multiple, deep, highly localized trap states in amorphous MEH-PPVs and PFOs, while close packing in combination with conformational disorder leads to the trap states distributed mostly near the bandgap edges in PPV aggregates.