Unveiling the magnetic behavior of C${}_3$N${}_4$ 2D material by defect creation, defect passivation, and transition metal adsorption

Abstract

Using the density functional tight binding method (DFTB) and the GFN1-xTB (Geometries, Frequencies, and Noncovalent interactions Tight Binding) Hamiltonian, we have investigated the structural, electronic and magnetic properties of vacancy defects, hydrogen and oxygen passivated defects, and Fe adsorption in two-dimensional (2D) graphitic carbon nitride (gt-C${}_3$N${}_4$) 2D material. The ring shape is the most preferred vacancy evolution path, with significant stability of the semicircle fourfold C-N-C-N vacancy. We found that bare gt-C${}_3$N${}_4$ which is non-magnetic becomes magnetic by 2-, and 5-defects creation, hydrogen/oxygen passivation of the defects, and upon Fe adsorption. Interestingly, Fe atoms interact with the gt-C${}_3$N${}_4$ sheet and result in a ground ferromagnetic (FM) state. In addition, we investigate the effects of passivating the vacancies by hydrogen in gt-C${}_3$N${}_4$ on its structural, electrical, and magnetic properties. We found that substituting the 1, 2, and 3 vacancies with hydrogen and passivating the 6-defect with oxygen turns on magnetism in the system. Due to structural distortion, the passivated defects do not have a well-ordered magnetic orientation. However, passivating the remaining defected structures maintains the nonmagnetic state. It is also shown that passivation leads to a semiconductor with a band gap value higher than that of the bare material. We also calculate the electronic and magnetic properties of transition metal (TM) atoms, including V, Cr, Mn, Fe, Co, Ni-adsorbed gt-C${}_3$N${}_4$ monolayer. All TM atoms show slight lattice distortion, and the adsorbed system almost maintains the original structure type. Moreover, a FM alignment was observed with a total magnetic moments of 2.89 ${\mu }_B$, 2 ${\mu }_B$, and 1 ${\mu }_B$ for V, Fe, and Co atoms, respectively. The Cr, Mn, and Ni atoms induce no magnetism to the non magnetic gt-C${}_3$N${}_4$ system.

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