Cation disorder in stoichiometric MgSnN2 and ambipolar self-doping behavior in off-stoichiometric MgSnN2 (2110.14289v1)

Abstract: Investigations on II-Sn-N2 (II = Mg, Ca) have been started very recently compared to the intense research of the Zn-IV-N2 (IV = Si, Ge, Sn). In this work, we perform a comprehensive study of cation disorder in stoichiometric MgSnN2 and crystal structure characteristic, doping behavior of off-stoichiometric Mg1+xSn1-xN2 (x = -0.8, -0.6, -0.5, -0.4, -0.2, 0.2, 0.4, 0.5, 0.6, 0.8) by using the cluster expansion method and first principles calculations. It is found that cation disorder in stoichiometric MgSnN2 induces a band gap reduction because of a violation of the octet rule. Moreover, the local disorder, namely forming (4,0) or (0,4) tetrahedra, would lead to an appreciable band gap reduction and hinder the enhancement of the optical absorption. An off-stoichiometric Mg/Sn ratio can strongly affect the morphology of Mg1+xSn1-xN2 samples due to the higher ionicity of the Mg-N bonds in comparison with Zn-N bonds. Furthermore, Mg1+xSn1-xN2 compounds show an ambipolar self-doping behavior, i.e., Mg-rich Mg1+xSn1-xN2 show p-type doping while Sn-rich ones exhibit n-type doping owing to the formation of acceptor-type antisite defect MgSn or donor-type antisite defect SnMg, respectively.