Direct Cation–Cation Interactions Induced by Mg Dopants for Electron–Gas Behavior in α-Fe₂O₃

Abstract

α-Fe 2 O 3 and its derivatives have been extensively studied for many years, but fascinating structural chemistry and physical behaviors continue to be reported in these systems to date. Here, we show that Mg doping in α-Fe 2 O 3 could induce direct cation−cation interactions, which result in electron−gas behaviors. Rather than a simple replacement of Fe in FeO 6 octahedra, the Mg dopant in α-Fe 2 O 3 is eight-coordinated by six oxygen and two Fe in neighboring FeO 6 octahedra via direct Fe−Mg−Fe interactions. The Mg 2+ dopant takes both Fe 3+ and empty octahedral interstitial sites so that one Mg-doped octahedron is sandwiched by two neighboring FeO 6 octahedra, yielding an arrangement of three neighboring Fe−Mg−Fe polyhedra over the medium-range order. The valence electrons confined in the Fe−Mg bonds exhibit twodimensional electron−gas (2DEG) characteristics, which may provide a new approach to other 2DEG systems, and the couplings with Fe 3d spins and the distortion of local symmetry lead to the spin-glass-like (SGL) magnetism, distinct from the antiferromagnetism of α-Fe 2 O 3 and SGL/superparamagnetic behaviors in related materials due to the ultrasmall particle size. This study illustrates the complexity of the doped structure not only in local symmetries but also in the chemical bonding and electron spins for emerging physical properties even in low-cost oxides.