What can the activation energy tell about the energetics at grain boundaries in polycrystalline organic films?

TL;DR

This study investigates how grain boundaries affect charge transport in organic thin films by comparing experimental activation energy measurements with kinetic Monte Carlo simulations, revealing limitations in using activation energy as a microscopic probe.

Contribution

The paper provides a systematic comparison of experimental and simulation data to understand the influence of grain boundaries on activation energies in organic semiconductor films.

Findings

Activation energy increases with the number of grain boundaries.

Energy barriers and valleys at grain boundaries affect activation energies.

Activation energy measurements serve as a general quality indicator, not a microscopic probe.

Abstract

Charge-carrier transport at the semiconductor-gate dielectric interface in organic field-effect transistors is critically dependent on the degree of disorder in the typically semi-crystalline semiconductor layer. Charge trapping can occur at the interface as well as in the current-carrying semiconductor layer itself. A detailed and systematic understanding of the role of grain boundaries between crystallites and how to avoid their potentially detrimental effects is still an important focus of research in the organic electronics community. A typical macroscopic measurement technique to extract information about the energetics of the grain boundaries is an activation energy measurement. Here, we compare detailed experiments on the energetic properties of monolayer thin films implemented in organic field-effect transistors, having controlled numbers of grain boundaries within the channel region to kinetic Monte-Carlo simulations of charge-carrier transport to elucidate the influence of grain boundaries on the extracted activation energies. Two important findings are: 1) whereas the energy at the grain boundary does not change with the number of grain boundaries in a thin film, both the measured and simulated activation energy increases with the number of grain boundaries. 2) In simulations where both energy barriers and valleys are present at the grain boundaries there is no systematic relation between the number of grain boundaries and extracted activation energies. We conclude, that a macroscopic measurement of the activation energy can serve as general quality indicator of the thin film, but does not allow microscopic conclusions about the energy landscape of the thin film.