On the Nature of Interlayer Bonds in Two-dimensional Materials

TL;DR

This study systematically classifies interlayer bonds in 2D materials using first-principles calculations, distinguishing three main types and proposing a practical protocol for identifying the dominant bonding mechanism.

Contribution

It introduces a computationally inexpensive protocol to recognize the main type of interlayer bonds in 2D materials based on charge density and structural analysis.

Findings

Identified three main types of interlayer bonds: van der Waals, electrostatic, and dative bonds.

Proposed a protocol for distinguishing bond types using interlayer distance, binding energy, and charge redistribution.

Demonstrated the approach's applicability to predict material properties like charge density waves and stability.

Abstract

The role of interlayer bonds in the two-dimensional (2D) materials "beyond graphene" and so-called van der Waals heterostructures is vital, and understanding the nature of these bonds in terms of strength and type is essential due to a wide range of their prospective technological applications. However, this issue has not yet been properly addressed in the previous investigations devoted to 2D materials. In our work, by using first-principles calculations we perform a systematic study of the interlayer bonds and charge redistribution of several representative 2D materials that are traditionally referred as van der Waals systems. Our results demonstrate that one can distinguish three main types of inter-layer couplings in the considered 2D structures: one atom thick membranes bonded by London dispersion forces (graphene, hBN), systems with leading electrostatic interaction between layers (diselenides, InSe and bilayer silica) and materials with so-called dative or coordination chemical bonds between layers (ditelurides). We also propose a protocol for recognising the leading type of interlayer bonds in a system that includes comparison of interlayer distances, binding energies and redistribution of the charge densities in interlayer space. Such an approach is computationally cheap and can be used to further prediction of chemical and physical properties such as charge density waves (CDW), work function and chemical stability at ambient conditions.