Modifications in the frustrated magnetism, oxidation state of Co and magnetoelectric coupling effects induced by a partial replacement of Ca by Gd in the spin chain compound Ca3Co2O6

Abstract: We have systematically investigated the influence of gradual replacement of Ca by Gd on the magnetic and complex dielectric properties of the well-known geometrically frustrated spin-chain system, Ca3Co2O6 (T_N= 24 K with additional magnetic transitions below 12K), by studying the series, Ca3-xGdxCo2O6 (x less than 0.7), down to 1.8K. Heat capacity measurements establish that the reduction of T_N with Gd substitution is much less as compared to that by Y substitution. The magnetic moment data reveal that there are changes in the oxidation state of Co as well, unlike for Y-substitution, beyond x= 0.2. Thus, despite being isovalent, both these substitutions interestingly differ in changing these magnetic properties in these oxides. We propose that the valence electrons of Y and those of R ions play different roles on deciding these magnetic characteristics of these mixed oxides. It is observed that a small amount (x= 0.3) of Gd substitution for Ca is enough to suppress glassy ac magnetic susceptibility behavior for the peak around 12 K. An additional low-temperature magnetic anomaly close to 5 K gets more prominent with increasing Gd concentration as revealed by heat-capacity data. Trends in temperature dependence of complex dielectric behavior were also tracked with varying composition and a frequency dependence is observed, not only for the transition in the region around 10 K (for some compositions), but also for the 5 K transition which is well-resolved for a higher concentration of Gd. Thus, Gd-substituted Ca3Co2O6 series is shown to reveal interesting magnetic and dielectric behavior of this family of oxides.