Room temperature Multiferroicity and Magnetoelectric coupling in Ca/Mn modified BaTiO3

Materials with magnetoelectric coupling (MEC) between ferroic orders at room temperature are emerging field in modern technology and physics. BaTiO3 is a robust ferroelectric in which several doping has led to MEC. In Ca and Mn modified BaTiO3 has been study with a series of Ba(1-x)Ca(x)Ti(1-y)Mn(y)O3 (x=y= 0, 0.03, 0.06, 0.09), in this MEC was only observed in x=0.03. The structural modifications with changing substitution reveal a reduced Ti-O-Ti bond angle for this sample which is the most ferromagnetic in nature. A mixed phase of tetragonal P4mm and hexagonal P63/mmc space groups of BaTiO3 is observed in the substituted samples, with nominal contribution of the hexagonal phase for x=0.03. A valence state study using XPS and XANES reveals the presence of enhanced proportion of Mn3+ ions in the sample which support a pseudo Jahn-Teller distortion, thereby supporting the ferroelectricity for x=0.03. Direct evidences of MEC was obtained from magnetoelectric measurements. A magnetoelectric coupling coefficient, {\alpha}ME ~44 mVcm-1Oe-1 was obtained for dc magnetic field of 600 Oe and a 10Hz ac field of 40 Oe. Such MEC was not observed for higher substitution which emphasizes the sensitivity of the structural properties on substitution.