Ordering of Interstitial Iron Atoms and Local Structural Distortion Induced by Iron Polycomplex in Fe1+yTe1-xSex as Seen via Transmission Electron Microscopy

Abstract: Employing aberration-corrected scanning transmission electron microscopy (STEM), we meticulously investigated the intrinsic chemical heterogeneity of Fe1+yTe, Fe1+yTe0.8Se0.2, and Fe1+yTe0.5Se0.5. Comprehensive analysis reveals the presence of interstitial iron atoms (Feint) across all samples, pre-dominantly occupying the 2c site of the P4/nmm space group. Moreover, a superstructure phase characterized by a wave vector q = 2/5a + 1/2c, originating from the ordering of Feint, is distinctly observable in the parent compound Fe1+yTe. In this scenario, the Feint atoms interact with adjacent Fe atoms, forming iron polycomplex and leading to an evident distortion of the FeTe4 tetrahedral. Experimental results further demonstrate effective suppression of Feint concentration and ordering through appropriate Se substitution; notably, Fe1+yTe0.5Se0.5 manifests the lowest concentration of Feint atoms. Our findings additionally indicate that Se substitution is random, and nanoscale phase separation induced by Te/Se chemical heterogeneity is commonly observed within Fe1+yTe1-xSex crystals.