Hydrogen‐Driven Phase Differentiation in BN Nucleation on Diamond

Abstract

Boron nitride has attracted scientific interest in recent years due to its potential use in electronics, both as hexagonal (hBN) and cubic (cBN) phases. While both are successfully realized through chemical vapor deposition, the heteroepitaxial growth of cBN on another iconic semiconductor, diamond is plagued with mixed‐phase formation. Employing first‐principles computations and a nanoreactor approach, the BN phase preferences are explored on diamond (001) controlled—as it is discovered—by the hydrogen gas concentration. In a limited‐hydrogen environment, the initial BN‐island expands along the diamond surface, forming a 3D metastable cubic phase that grows in the direction normal to the basal plane through kinetically‐limited nucleation, thus overcoming the thermodynamic preference toward the hBN phase. Comparatively, the amorphous phase is favored in the absence of hydrogen, while the hexagonal phase dominates at its high levels, elucidating numerous experimental observations. A obtained kinetic phase diagram connects the phase with hydrogen chemical potential to facilitate targeted phase selection. The results suggest that gas‐mediated nucleation kinetics provide feasible control for the precise synthesis. It also offers valuable guidance for the controllable synthesis of desired BN phases and advances research toward potential BN electronics.