Tuning the Electronic and Optical Properties of Impurity-Engineered Two-Dimensional Graphullerene Half-Semiconductors

Abstract

A novel material consisting of a monolayer of C$_{60}$ buckyballs with hexagonal symmetry has recently been observed experimentally, named graphullerene. In this study, we present a comprehensive \textit{ab-initio} theoretical analysis of the electronic and optical properties of both pristine and impurity-engineered monolayer graphullerene using spin-dependent density functional theory (spin-DFT). Our findings reveal that graphullerene is a direct band gap semiconductor with a band gap of approximately 1.5 eV at the $\Gamma$ point, agreeing well with experimental data. Notably, we demonstrate that by adding impurities, in particular substitutional nitrogen, substitutional boron, or adsorbent hydrogen, to graphullerene results in the formation of spin-dependent deep donor and deep acceptor levels, thereby giving rise to a variety of half-semiconductors. All the impurities exhibit a magnetic moment of approximately $\mu_B$ per impurity. This impurity engineering enables the tuning of spin-polarized exciton properties in graphullerene, with spin-dependent band gap energies ranging from 0.43 eV ($\lambda \sim$ 2.9 $\mu$m) to 1.5 eV ($\lambda \sim$ 820 nm), covering the near-infrared (NIR) and short-wavelength infrared (SWIR) regimes. Our results suggest that both pristine and impurity-engineered graphullerene have significant potential for the development of carbon-based 2D semiconductor spintronic and opto-spintronic devices.