Origin of the monolayer Raman signature in hexagonal boron nitride: a first-principles analysis

TL;DR

This study uses first-principles calculations to determine that the Raman shift in monolayer hexagonal boron nitride is primarily due to in-plane contraction and thermal expansion effects, clarifying its origin.

Contribution

It demonstrates that the intrinsic Raman shift is caused by in-plane contraction, and thermal effects diminish this signature, resolving debates on the shift's origin.

Findings

In-plane contraction explains the Raman shift from bulk to monolayer.

Thermal expansion reduces the in-plane difference between bulk and monolayer.

Non-local correlation effects are essential for accurate predictions.

Abstract

Monolayers of hexagonal boron nitride (h-BN) can in principle be identified by a Raman signature, consisting of an upshift in the frequency of the E2g vibrational mode with respect to the bulk value, but the origin of this shift (intrinsic or support-induced) is still debated. Herein we use density functional theory calculations to investigate whether there is an intrinsic Raman shift in the h-BN monolayer in comparison with the bulk. There is universal agreement among all tested functionals in predicting the magnitude of the frequency shift upon a variation in the in-plane cell parameter. It is clear that a small in-plane contraction can explain the Raman peak upshift from bulk to monolayer. However, we show that the larger in-plane parameter in the bulk (compared to the monolayer) results from non-local correlation effects, which cannot be accounted for by local functionals or those with empirical dispersion corrections. Using a non-local-correlation functional, we then investigate the effect of finite temperatures on the Raman signature. We demonstrate that bulk h-BN thermally expands in the direction perpendicular to the layers, while the intralayer distances slightly contract, in agreement with observed experimental behavior. Interestingly, the difference in in-plane cell parameter between bulk and monolayer decreases with temperature, and becomes very small at room temperature. We conclude that the different thermal expansion of bulk and monolayer partially "erases" the intrinsic Raman signature, accounting for its small magnitude in recent experiments on suspended samples.