Beyond Hexagonal Boron Nitride: First-Principles Study of Pentaoctite-BN and Pop-BN Monolayers

Abstract

We investigate two novel non-hexagonal boron nitride monolayers, pentaoctite-BN (PO-BN) and pop-BN (PP-BN), using first-principles calculations. Their structural, electronic, mechanical, vibrational, thermal, and optical properties are systematically analyzed to assess their stability and potential applications. Despite being metastable with respect to hexagonal BN, both polymorphs satisfy the criteria for dynamical, mechanical, and thermal stability, indicating that they are viable two-dimensional materials. Both systems are indirect-gap semiconductors whose electronic states near the band edges are dominated by out-of-plane pz orbitals. Their distinct pentagon-octagon ring networks also give rise to different in-plane elastic anisotropies. Many-body optical calculations reveal strong excitonic effects and pronounced polarization-dependent optical absorption, with lattice engineering shifting the optical response from the ultraviolet toward the visible and infrared regions. These findings demonstrate that engineering non-hexagonal lattice architectures provides an effective strategy for tuning the electronic and optical properties of two-dimensional BN, highlighting PO-BN and PP-BN as promising candidates for future optoelectronic and photonic applications.