Structural and magnetic transformations in the system YBaCo4O7+X (x = 0, 0.1, 0.2)

Abstract

The modification of magnetic and elastic properties of YBaCo4O7+x (x = 0, 0.1) cobaltite series at a small controlled deviation x = 0, 0.1, 0.2 from stoichiometry has been investigated. The non-stoichiometric cobaltites with x > 0.1 are found to be separated into two structural phases with different values of x under certain synthesis and heat-treatment conditions of the YBaCo4O7+x system (x = 0, 0.1, 0.2). A non-trivial magnetic behavior is observed in stoichiometric YBaCo4O7. Magnetic moment ΔM = MFC–MZFC induced by an external magnetic field (an analog of thermo-residual magnetization) exhibits anomalies at magnetic phase transition temperatures TN1 and TN2 that coincide with Young’s modulus anomalies. Conversely, in the magnetic susceptibility curves taken in the FC and ZFC modes, phase transitions are not discerned. When x deviates from stoichiometry, the ratio between two magnetic ions Co3+/Co2+ changes, the induced moment ΔM increases, and a residual ferromagnetic moment of ∼ 10-2μB appears in the magnetization curves at low temperatures. At a slight deviation from the oxygen stoichiometry in the samples, the structural distortion disappears, and the anomalies in the elastic characteristics near the TN region rapidly diffuse and vanish. It has been found that when YBaCo4O7+x cobaltites deviate from stoichiometry, the evolution of their magnetic properties is similar to that observed at the transition from Y-based to Ca-based cobaltite. Two scenarios of the cobalt subsystem magnetic behavior with an increasing fraction of cobalt Co3+ ions have been discussed.