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$_7$

TL;DR

This study compares the effects of Cr$^{3+}$ and Ni$^{2+}$ doping on the magnetic and dielectric properties of CaBaCo$_4$O$_7$, revealing that Ni doping significantly enhances electric polarization and magnetoelectric coupling, unlike Cr doping.

Contribution

It provides a comparative analysis of how different dopant valencies influence multiferroic properties, highlighting the dramatic effects of Ni doping on polarization and magnetoelectric coupling.

Findings

Ni doping increases electric polarization up to 650 μC/m$^2$

Ni doping induces strong magnetoelectric coupling (~12% polarization change in 15 T)

Cr doping has minimal impact on properties

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.