Abstract

In this work, we employed density functional theory modeling to obtain the structure, binding mech-anism, and electronic/optical properties of carbon-based interfaces formed by phosphorene nanoflakes and carbon fullerenes (C-24 to C-70). 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 (C-50-C-70) 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. (C) 2021 Elsevier Ltd. All rights reserved.