Engineering of flat bands and Dirac bands in two-dimensional covalent organic frameworks (COFs): relationships among molecular orbital symmetry, lattice symmetry, and electronic-structure characteristics

Abstract

Two-dimensional covalent organic frameworks (2D-COFs), also referred to as 2D polymer networks, display unusual electronic-structure characteristics, which can significantly enrich and broaden the fields of electronics and spintronics. In this Focus article, our objective is to lay the groundwork for the conceptual description of the fundamental relationships among the COF electronic structures, the symmetries of their 2D lattices, and the frontier molecular orbitals (MOs) of their core and linker components. We focus on monolayers of hexagonal COFs and use tight-binding model analyses to highlight the critical role of the frontier-MO symmetry, in addition to lattice symmetry, in determining the nature of the electronic bands near the Fermi level. We rationalize the intriguing feature that, when the core unit has degenerate highest occupied MOs [or lowest unoccupied MOs], the COF highest valence band [or lowest conduction band] is flat but degenerate with a dispersive band at a high-symmetry point of the Brillouin zone; the consequences of having such band characteristics are briefly described. Multi-layer and bulk 2D COFs are found to maintain the salient features of the monolayer electronic structures albeit with a reduced bandgap due to the interlayer coupling. This Focus article is thus meant to provide an effective framework for the engineering of flat and Dirac bands in 2D polymer networks.