Raman and Infrared Signatures of Layered Boron Nitride Polytypes: A First-Principles Study

We present a study based on first-principles calculations of the vibrational and spectroscopic properties of four types of layered boron nitride (BN) polymorphs: e-BN (AA), h-BN (AA′), r-BN (ABC), and b-BN (AB). By using density functional perturbation theory with van der Waals corrections, we calculate phonon frequencies and Raman/infrared (IR) activities at the Γ point and extract specific spectral fingerprints for each stack. In e-BN, we observe a sharp, isolated high-frequency E′ mode at 1420.9cm−1 that is active in both Raman and IR. For h-BN, the characteristic Raman E2g line occurs at 1415.5cm−1. The out-of-plane IR-active A2u branch shows a mid-frequency TO/LO pair at 673.5/806.6cm−1, which closely matches experimental results. Rhombohedral r-BN has a strong, coincident Raman/IR high-frequency feature (E) at 1418.5cm−1, along with a large IR LO partner at 1647.3cm−1, consistent with observed Raman and IR signatures. Bernal b-BN displays the most complicated pattern. It combines a robust mid-frequency A2″ pair (TO/LO at 697.9/803.5cm−1) with multiple high-frequency E′ modes (TO near 1416.9 and 1428.1cm−1, each with LO counterparts). These stack-dependent Raman and IR fingerprints match existing experimental data for h-BN and r-BN and provide clear predictions for e-BN and b-BN. The results offer a consistent framework for identifying and interpreting vibrational spectra in layered sp2 boron nitride and related materials.