Photodegradation and van der Waals Passivation of Violet Phosphorus

Violet phosphorus (VP), a novel two-dimensional (2D) nanomaterial, boasts structural anisotropy, a tunable optical bandgap, and superior thermal stability compared with its allotropes. Its multifunctionality has sparked widespread interest in the community. Yet, the VP's air susceptibility impedes both probing its intrinsic features and device integration, thus making it of urgent significance to unveil the degradation mechanism. Herein, we conduct a comprehensive study of photoactivated degradation effects on VP. A nitrogen annealing method is presented for the effective elimination of surface adsorbates from VP, as evidenced by a giant surface-roughness improvement from 65.639 nm to 7.09 nm, enabling direct observation of the intrinsic morphology changes induced by photodegradation. Laser illumination demonstrates a significant thickness-thinning effect on VP, manifested in the remarkable morphological changes and the 73% quenching of PL intensity within 160 s, implying its great potential for the efficient selected-area etching of VP at high resolution. Furthermore, van der Waals passivation of VP using 2D hexagonal boron nitride (hBN) was achieved. The hBN-passivated channel exhibited improved surface roughness (0.512 nm), reduced photocurrent hysteresis, and lower responsivity (0.11 A/W @ 450 nm; 2 μW), effectively excluding adsorbate-induced electrical and optoelectrical effects while disabling photodegradation. Based on our experimental results, we conclude that three possible factors contribute to the photodegradation of VP: illumination with photon energy higher than the bandgap, adsorbed H₂O, and adsorbed O₂.