Impact of the Lattice Constant on the Polymorphism of Organic/Inorganic Interfaces

TL;DR

This study investigates how the lattice constant of metal surfaces influences the polymorphism of organic/metal interfaces, revealing that changes in lattice spacing can induce phase transitions in adsorbate arrangements.

Contribution

It demonstrates the impact of lattice constant variations on the energetic landscape and polymorphism of organic/metal interfaces, highlighting a lattice-constant-driven phase transition mechanism.

Findings

Lattice constant affects adsorbate-substrate interaction strength.

Increasing lattice constant can favor tightly packed polymorphs.

Phase transition occurs from repulsive to attractive adsorbate interactions.

Abstract

The polymorphism of organic/metal interfaces influences many of their properties. As a result, a host of contemporary research focuses on analyzing the factors which are pertinent for modifying polymorphism. In this work, we elucidate how the lattice constant of the underlying lattice affects the energetic landscape of adsorbate monolayers for the model system of tetracyanoquinodimethane (TCNQ) on coinage metal surfaces with varying lattice constants. In particular, we focus on how the adsorbateadsorbate and the adsorbate-substrate interaction are affected when increasing the lattice constant and changing the surface chemistry. Based on these investigations, we show that the adsorbate-substrate interaction for some adsorption geometries can change significantly with the lattice constant. In addition, due to a transition from repulsive to attractive adsorbate-adsorbate interactions, polymorphs with tight packing become more favorable, if the lattice constant is increased, resulting in a lattice-constant-based phase transition.