Synthesis of Crystalline Black Phosphorus Thin Film on Sapphire

Abstract Black phosphorus (BP) has recently attracted significant attention due to its exceptional physical properties. Currently, high‐quality few‐layer and thin‐film BP are produced primarily by mechanical exfoliation, limiting their potential in future applications. Here, the synthesis of highly crystalline thin‐film BP on 5 mm sapphire substrates by conversion from red to black phosphorus at 700 °C and 1.5 GPa is demonstrated. The synthesized ≈50 nm thick BP thin films are polycrystalline with a crystal domain size ranging from 40 to 70 µm long, as indicated by Raman mapping and infrared extinction spectroscopy. At room temperature, field‐effect mobility of the synthesized BP thin film is found to be around 160 cm² V⁻¹ s⁻¹ along armchair direction and reaches up to about 200 cm² V⁻¹ s⁻¹ at around 90 K. Moreover, red phosphorus (RP) covered by exfoliated hexagonal boron nitride (hBN) before conversion shows atomically sharp hBN/BP interface and perfectly layered BP after the conversion. This demonstration represents a critical step toward the future realization of large scale, high‐quality BP devices and circuits.