We report electron spin resonance (ESR) measurements in the Gd3+ doped semiconducting filled skutterudite compound Ce1-xGdxFe4P12 (x = 0.001). As the temperature T varies from T = 150 K to T = 165 K, the Gd3+ ESR fine and hyperfine structures coalesc
e into a broad inhomogeneous single resonance. At T = 200 K the line narrows and as T increases further, the resonance becomes homogeneous with a thermal broadening of 1.1(2) Oe/K. These results suggest that the origin of these features may be associated to a subtle interdependence of thermally activated mechanisms that combine: i) an increase with T of the density of activated conduction-carriers across the T-dependent semiconducting pseudogap; ii) the Gd3+ Korringa relaxation process due to an exchange interaction, J_{fd}S.s, between the Gd3+ localized magnetic moments and the thermally activated conduction-carriers and; iii) a relatively weak confining potential of the rare-earth ions inside the oversized (Fe2P3)4 cage, which allows the rare-earths to become rattler Einstein oscillators above T = 148 K. We argue that the rattling of the Gd3+ ions, via a motional narrowing mechanism, also contributes to the coalescence of the ESR fine and hyperfine structure.
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.
