Two-dimensional fullerene-based monolayer materials assembled by C80 and Sc3N@C80

Abstract

Construction of two-dimensional (2D) materials using fullerenes as building blocks has attracted particular attention, primarily due to their ability to integrate desired functionalities into devices. However, realization of stable 2D phases of polymerized fullerenes remains a big challenge. Here, we propose two stable 2D monolayer phases with covalently bridged C₈₀ cages, namely α-C₈₀-2D and β-C₈₀-2D, which are semiconductors with strong absorption in the long wave range and appreciable carrier mobility, respectively. The high stability originates from the bond energy released by the [2+2] cycloaddition polymerization of C₈₀ is greater than the deformation energy of a cage. Starting from α-C₈₀-2D, endohedral incorporation of the Sc₃N molecule into each C₈₀ cage leads to 2D semiconductors of α-Sc₃N@C₈₀-2D and α′-Sc₃N@C₈₀-2D, which possess exceptional stability and diverse physical properties, including unique electronic band structures, strong optical absorption in the visible (VIS) to near-infrared (NIR) regime, and anisotropic optical characteristics. Remarkably, a temperature-induced order–disorder transition in the α-Sc₃N@C₈₀-2D phase has been observed at elevated temperatures above 600 K. These findings expand the family of 2D carbon materials and provide useful clue for the potential applications of fullerene-assembled monolayer networks.