Functionalization of antimonene and bismuthene with Lewis acids

Elemental 2D pnictogens (group 15) are an interesting class of materials with tunable band structures and high carrier mobilities. Heavier pnictogens (Sb and Bi) are stable under ambient conditions compared to lighter members (P and As) and are emerging as interesting candidates for various electronic and optoelectronic applications. The reactivity of these materials is due to the presence of a lone pair which can be effectively utilized to tune material properties via different functionalization strategies. In this work, we have synthesized antimonene and bismuthene nanosheets by liquid exfoliation which are emissive in the visible range and functionalized these nanosheets with group 12 and 13 Lewis acids (ZnCl₂, CdCl₂, BCl₃, GaCl₃, AlCl₃, and InCl₃). Interaction of these Lewis acids with the lone pairs on Sb/Bi leads to the formation of Lewis acid-base adducts with the corresponding changes in the bonding environment along with lattice distortion and rehybridization of the band structure. Interestingly, the changes in band structure upon functionalization were realized as a blue shift in the emission of few-layered Sb and Bi. This is the first report on the functionalization of heavier pnictogens by the formation of Lewis acid-base adducts and opens a path for tuning their properties for integration in electronic and optoelectronic devices.