Quenching of low-energy optical absorption in bilayer C$_3$N polytypes

TL;DR

This study uses first-principles calculations to explore how stacking variations in bilayer C₃N affect its electronic and optical properties, revealing a unique quenching of low-energy optical absorption due to excitonic effects.

Contribution

It provides the first detailed theoretical analysis of excitonic optical properties in bilayer C₃N with different stacking arrangements, highlighting a novel quenching phenomenon.

Findings

Strong optical absorption near monolayer energies

Negligible oscillator strength for low-lying excitons in bilayers

Quenching linked to small interband dipole matrix elements

Abstract

In this work we provide a first principles description of the electronic and optical properties of bilayers C$_3$N, with different stacking motifs AB, AB$'$ and AA$'$. Starting from quasi-particle electronic band-structures, we solve the Bethe Salpeter Equation (BSE) to access the excitonic properties of these bilayers. For all stacking sequences, we see strong optical absorption at energies lower than but close to that of the monolayer. Most relevant, we predict a strong quenching of the low-energy optical absorption, with negligible oscillator strength of low-lying bound excitons. This is a unique phenomenology that does not arise in the monolayer case, nor in other common homo-bilayers. We explain these findings in terms of the small interband dipole matrix elements associated to the valence-conduction transitions involved in these excitons, and discuss them in view of the different stacking motifs.