Family behavior and Dirac bands in armchair nanoribbons with 4–8 defect lines

Abstract

Abstract Bottom-up synthesis from molecular precursors is a powerful route for the creation of novel synthetic carbon-based low-dimensional materials, such as planar carbon lattices. The wealth of conceivable precursor molecules introduces a significant number of degrees-of-freedom for the design of materials with defined physical properties. In this context, a priori knowledge of the electronic, vibrational and optical properties provided by modern ab initio simulation methods can act as a valuable guide for the design of novel synthetic carbon-based building blocks. Using density functional theory, we performed simulations of the electronic properties of armchair-edged graphene nanoribbons (AGNR) with a bisecting 4–8 ring defect line. We show that the electronic structures of the defective nanoribbons of increasing width can be classified into three distinct families of semiconductors, similar to the case of pristine AGNR. In contrast to the latter, we find that every third nanoribbon is a zero-gap semiconductor with Dirac-type crossing of linear bands at the Fermi energy. By employing tight-binding models including interactions up to third-nearest neighbors, we show that the family behavior, the formation of direct and indirect band gaps and of linear band crossings in the defective nanoribbons is rooted in the electronic properties of the individual nanoribbon halves on either side of the defect lines, and can be effectively through introduction of additional ‘interhalf’ coupling terms.