Interfacial charge transfer influences thin-film polymorphism

TL;DR

This study investigates how different substrates influence the polymorphism of organic thin films, revealing substrate-dependent stability of layered structures driven by charge transfer effects.

Contribution

The paper combines first principles calculations and machine learning to analyze substrate effects on thin-film polymorphism, highlighting charge transfer as a key factor.

Findings

Similar first-layer structures on both substrates.

Different second-layer structures favored by each substrate.

Charge transfer explains stability differences.

Abstract

The structure and chemical composition are the key parameters influencing the properties of organic thin films deposited on inorganic substrates. Such films often display structures that substantially differ from the bulk, and the substrate has a relevant influence on their polymorphism. In this work, we illuminate the role of the substrate by studying its influence for para-benzoquinone on two different substrates, Ag(111) and graphene. We employ a combination of first principles calculations and machine learning to identify the energetically most favorable structures on both substrates and study their electronic properties. Our results indicate that for the first layer, similar structures are favorable for both substrates. For the second layer we find two significantly different structures. Interestingly, graphene favors the one with less, while Ag favors the one with more electronic coupling. We explain this switch in stability as an effect of the different charge transfer on the two substrates.