Remarkable effects of dopant valency $-$ a comparative study of CaBaCo$_{3.96}$Cr$_{0.04}$O$_7$ and CaBaCo$_{3.96}$Ni$_{0.04}$O$_7$

Abstract: Distinctive effects of dopant valency is discussed using an impurity level 1% doping each of Cr$^{3+}$ and Ni$^{2+}$ in CaBaCo$4$O$_7$. Through a comparative study of the magnetic and dielectric properties of multiferroic CaBaCo${3.96}$Cr${0.04}$O$_7$ and CaBaCo${3.96}$Ni${0.04}$O$_7$, we highlight that Cr doping does not significantly alter the properties in spite of differences in magnetic spin and ionic radius compared to Co$^{3+}$ and Co$^{2+}$ while Ni doping induces spectacular changes. Particularly, a manifold increase of electric polarization change up to 650 ${\rm \mu}$C/m$^2$ at 5.6 kV/cm is observed in CaBaCo${3.96}$Ni${0.04}$O$_7$ compared to CaBaCo${3.96}$Cr$_{0.04}$O$_7$ and a stronger magnetoelectric coupling leading to a polarization change of $\sim$ 12% in 15 T magnetic field and below 40 K. Further, magnetodielectric effects hint to competing magnetic phases over the temperature range of magnetic transitions. We discuss the observed disparity in the light of a possible site selective doping of Cr$^{3+}$ and Ni$^{2+}$ in the triangular and kagom\'e layers, respectively, of the parent compound.