Fullerene–phosphorene–nanoflake nanostructures: Modulation of their interaction mechanisms and electronic properties through the size of carbon fullerenes

Abstract

In this work, we employed density functional theory modeling to obtain the structure, binding mechanism, and electronic/optical properties of carbon-based interfaces formed by phosphorene nanoflakes and carbon fullerenes (C24 to C70). Fullerenes form stable covalent and non-covalent complexes with phosphorene depending on their molecular size. A continuum solvation model indicates that complexes are stable in solution, independent of the solvent polarity. Two classes of covalent complexes arise by cycloaddition-like reactions (nanobuds): the first class, where short-range effects (charge-transfer and polarization) determine the stability; the second one, where short-range effects decay to avoid steric repulsion, and long-range forces (electrostatics and dispersion) favors the stability. High-size fullerenes (C50–C70) only form non-covalent complexes as experimentally obtained due to strong repulsion at shorter intermolecular distances and lack of dissociation barriers. Fullerenes also act as mild p-dopants for phosphorene, increasing its polar character and ability to acquire induced dipole moments. Moreover, small energy-bandgap (low-size) fullerenes increase the phosphorene metallic character. Fullerenes also act as active sites for orbital-controlled interactions and maximize the phosphorene light absorbance at the UV–Vis region. An outlook of these nanostructures provides practical nanotechnological applications in storage, batteries, sensing, bandgap engineering, and optoelectronics.