Covalent Heteroepitaxy of Large‐Area Vertical Hexagonal Boron Nitride for High‐Temperature VUV Photodetectors

Hexagonal boron nitride (h‐BN) is a van der Waals (vdW) ultrawide bandgap semiconductor with high band‐edge absorption coefficient and chemical/thermal resistance, demonstrating great potential for vacuum ultraviolet (VUV) and UV‐C detection. Hitherto, most of their prevailing applications have exploited epitaxial films and multilayers either grown on substrates or transferred, which tend to form energy‐favorable noncovalent vdW epitaxy. Here, an alternative heteroepitaxy of 2‐inch h‐BN is reported with desirable thickness and vertically aligned vdW layers covalently bonded to sapphire, enabled by activating the inert substrate surface using ion impingement during deposition and the dislocation‐mediated epitaxial transition. The fabricated photodetectors allow efficient photon absorption and carrier collection using a simple planar device design, showing excellent VUV/UV‐C detection performance with ultrafast response of 270 ns/60 µs (rise/decay) and remarkable operating stability until 500 °C. This covalent heteroepitaxy of wafer‐scale h‐BN opens new avenues for optoelectronics and electronics significant to harsh environment applications.