Ce2Pd21Si6 vs. Ce3Pd20Si6: Effect of Ce/Pd substitution on the physical properties

In this study, polycrystalline intermetallic compounds Ce3-xPd20+xSi6 (x = 0; 0.5; 1) as well as La-based analogues La3-xPd20+xSi6 (x = 0; 1) are synthesized. At the same time, R2Pd21Si6 (R=Ce, La) are new rare earth compounds presented here. An analysis of the crystal structure shows that the increase in x leads to partial (x = 0.5) or complete (x = 1) replacement of Ce/La ions by Pd in one of the two Wyckoff positions, namely, in position 4a. Ab initio DFT calculations demonstrate good agreement between the determined lattice parameters and those found experimentally for both Ce3-xPd20+xSi6 (x = 0; 0.5; 1) and La3-xPd20+xSi6 (x = 0; 1). A comparative analysis of resistivity and specific heat of Ce3-xPd20+xSi6 with x = 0; 0.5; 1 makes it possible to associate the Ce ions in the 8c position with Kondo behaviour in all three compositions, which manifests itself in an increase in resistivity with cooling, as well as in a broad peak of the magnetic contribution of specific heat. The Kondo temperature T-K approximate to 25 K obtained from the analysis of the temperature dependences of the heat capacity turns out to be the same for all Ce compounds. The appearance of cerium ions in the position 4a in compositions with x = 0 and x = 0.5 leads to an additional contribution to the specific heat, the value of which increases with decreasing temperature, as well as, to the formation of a coherent Kondo-lattice state with a maximum of the resistivity at T-coh approximate to 15 K, followed by the subsequent onset of negative magnetoresistance regime below T-inv approximate to 7 K. Apparently, this behaviour is associated with the appearance of spin and orbital correlations proceeding the quadrupole and antiferromagnetic transitions occurring at lower temperatures. Magnetization measurements show more localized character of magnetic moments of Ce ions at T = 2 K in Ce3Pd20Si6 as compared to the Ce2Pd21Si6.