Correlation between oxygen vacancies and sites of Mn ions in YMnO3

In multiferroic hexagonal manganites (RMnO3, R = Y, Sc, Ho-Lu), positions of Mn ions can affect both their in-plane and inter-plane exchange interactions, thus they are of utmost importance for the magneto-elastic coupling of rare-earth compounds. However, the reported in-plane positions of Mn ions by different groups are controversial and there is a lack of convenient method to identify the shift of Mn ions from the center of MnO5 bipyramids. Here, we demonstrate that the transmission electron microscopy is an efficient technique to characterize the positions of Mn ions and the shift of Mn ions can be directly recognized from the selected area electron diffraction (SAED) patterns. Through systematic studies on the SAED patterns acquired from regions with stoichiometric and non-stoichiometric ratio, we conclude that the intensities of (1 (1) over bar0) and (2 (2) over bar0) diffraction spots are very sensitive to the in-plane positions of Mn ions. We ascribe the off-centered shift of Mn ions to the in-plane oxygen vacancies and this is verified by combined electron microscopy and electron diffraction pattern calculations. Our results indicate that SAED can be used to judge both local positions of Mn ions and local oxygen deficiency in RMnO3 systems. (C) 2015 AIP Publishing LLC.