Gd3+ rattling triggered by a weak M-I transition at 140-160 K in the Ce1-xGdxFe4$P12 x ~ 0.001 skutterudite compounds: an ESR study

In this work we report electron spin resonance (ESR) measurements in the semiconducting Ce1-xGdxFe4P12 (x ~ 0.001) filled skutterudite compounds. Investigation of the temperature (T) dependence of the ESR spectra and relaxation process suggests, that in the T-interval of 140-160 K, the onset of a weak metal-insulator (M-I) transition takes place due to the increasing density of thermally activated carriers across the semiconducting gap of ~ 1500 K. In addition, the observed low-T fine and hyperfine structures start to collapse at ~ 140 K and is completely absent for > 160 K. We claim that the increasing carrier density is able to trigger the rattling of the Gd3+ ions which in turn is responsible, via a motional narrowing mechanism, for the collapse of the ESR spectra.

Direct determination of the crystal field parameters of Dy, Er and Yb impurities in the skutterudite compound CeFe$_{4}$P$_{12}$ by Electron Spin Resonance

Despite extensive research on the skutterudites for the last decade, their electric crystalline field ground state is still a matter of controversy. We show that Electron Spin Resonance (ESR) measurements can determine the full set of crystal field parameters (CFPs) for the Th cubic symmetry (Im3) of the Ce$_{1-x}$R$_{x}$Fe$_{4}$P$_{12}$ (R = Dy, Er, Yb, $xlesssim 0.003$) skutterudite compounds. From the analysis of the ESR data the three CFPs, B4c, B6c and B6t were determined for each of these rare-earths at the Ce$^{3+}$ site. The field and temperature dependence of the measured magnetization for the doped crystals are in excellent agreement with the one predicted by the CFPs Bnm derived from ESR.