Abstract: Large-scale hexagonal boron nitride (h-BN) single crystals are highly desirable not only as the substrate or dielectric for van der Waals heterostructures, but also the promising candidates in optoelectronics, electronics, detectors, as well as recently boomed room-temperature single-photon sources. Here, we report the synthesis of centimeter-scale single-crystal h-BN films with hundreds of micrometer thickness via the metal flux method. The growth control along the out-of-plane and in-plane directions of h-BN crystals is realized by the adjustment of NiCr alloy composition, from which the limited solubility of N atoms can be promoted by high diffusion in molten reactants. This also benefits to forming a distinct interface between the synthesized h-BN crystals and the metal ingot, giving rise to an easy exfoliation of the large area high-quality thick films. Such h-BN crystals have been demonstrated as both self-powered flexible and rigid vacuum-ultraviolet photodetectors, allowing for efficient photodetection in terms of high responsivity, rapid response speed, and high operational temperature. A maximum photoresponsivity of 3.35 mA/W is achieved at a wavelength of 185 nm with an operational temperature spanning to 500 °C (and possibly beyond). The large-area freestanding h-BN single crystal described herein reveals great potential as a high-performance photodetector, and versatile platform for other superb electronic and optoelectronic devices.

Key words: h-BN single crystal, Flexible device, Ultraviolet photodetection, High-temperature device