Charge Transport in Organic Molecular Semiconductors from First Principles: The Band-Like Hole Mobility in Naphthalene Crystal

TL;DR

This paper presents a first-principles approach to accurately predict charge transport and hole mobility in naphthalene crystals, bridging band theory and traditional hopping models.

Contribution

It introduces a comprehensive ab initio framework combining GW band structures, electron-phonon scattering, and Boltzmann transport to predict charge mobility in organic crystals.

Findings

Calculated hole mobility matches experimental data between 100-300 K.

Inter-molecular phonons regulate mobility, intra-molecular phonons have strong coupling.

Revises the understanding of molecular motions affecting charge transport.

Abstract

Predicting charge transport in organic molecular crystals is notoriously challenging. Carrier mobility calculations in organic semiconductors are dominated by quantum chemistry methods based on charge hopping, which are laborious and only moderately accurate. We compute from first principles the electron-phonon scattering and the phonon-limited hole mobility of naphthalene crystal in the framework of ab initio band theory. Our calculations combine GW electronic bandstructures, ab initio electron-phonon scattering, and the Boltzmann transport equation. The calculated hole mobility is in very good agreement with experiment between 100$-$300 K, and we can predict its temperature dependence with high accuracy. We show that scattering between inter-molecular phonons and holes regulates the mobility, though intra-molecular phonons possess the strongest coupling with holes. We revisit the common belief that only rigid molecular motions affect carrier dynamics in organic molecular crystals. Our work provides a quantitative and rigorous framework to compute charge transport in organic crystals, and is a first step toward reconciling band theory and carrier hopping computational methods.