Wafer-scale AA-stacked hexagonal boron nitride grown on a GaN substrate.

The stacking sequence of two-dimensional hexagonal boron nitride (hBN) is a critical factor that determines its polytypes and its distinct physical properties. Although most hBN layers adopt the thermodynamically stable AA' stacking sequence, achieving alternative stacking configurations has remained a long-standing challenge. Here we demonstrate the scalable synthesis of hBN featuring unprecedented AA stacking, where atomic monolayers align along the c axis without any translation or rotation. This previously considered thermodynamically unfavourable hBN polytype is achieved through epitaxial growth on a two-inch single-crystalline gallium nitride wafer, using a metal-organic chemical vapour deposition technique. Comprehensive structural and optical characterizations, complemented by theoretical modelling, evidence the formation of AA-stacked multilayer hBN and reveal that hBN nucleation on the vicinal gallium nitride surface drives the unidirectional alignment of layers. Here electron doping plays a central role in stabilizing the AA stacking configuration. Our findings provide further insights into the scalable synthesis of engineered hBN polytypes, characterized by unique properties such as large optical nonlinearity.