Hexagonal Boron Nitride Crystal Growth in the Li₃BN₂-BN System

Hexagonal boron nitride (hBN) presents valuable intrinsic properties and attracts considerable attention for the development of novel two-dimensional (2D) materials-based technologies. Even though huge efforts have been made to improve the bottom-up synthesis of integrated and high quality hBN, the devices presenting the best performances are still made using hBN exfoliated from bulk crystals. In this context, we explore the Polymer-Derived Ceramics (PDC) route coupled to a high temperature process that produces millimetric and high quality hBN crystals. By investigating the (micro)structure of several samples, we demonstrate that the crystal growth occurs by segregation from a Li3BN2-BN solution upon cooling and from hBN seeds. In particular, we show that crystallization can occur at a temperature as low as 1400{}C. Overall, these results show that hBN crystal growth in the Li3BN2-BN system is compatible with conventional flux methods that may be the most promising platform for continuous seeded hBN crystal growth.