Atomic structures of twin boundaries in CoO

Abstract

The twinning plane of crystals with a face-centered-cubic (FCC) structure is usually the (111) plane, as found in FCC metals and oxides with FCC sublattices of oxygen, like rock-salt-type NiO and spinel-type Fe₃O₄. Surprisingly, we found in this work that the twinning plane of rock-salt-type CoO is the (112) plane, although Co is adjacent to Ni in the periodic table. The atomic and electronic structures of the CoO(112) twin boundary with in-plane shift vector 1/2[111] have been studied combining aberration-corrected scanning transmission electron microscopy (STEM), electron-energy-loss spectroscopy (EELS), and density functional theory (DFT) calculations. It was found that the atoms at the twin boundary have nominal oxidation states, and the twin boundary remains insulating and antiferromagnetically coupled. Importantly, through the electronic structures and the crystal orbital Hamilton population (COHP) analyses, the (112) twin boundary is found to be more stable than the (111) twin boundary.