Electronic Structure Investigation Of A Charge Density Wave Coupled To A Metal-To-Metal Transition In Ce3co4sn13

We study the electronic structure of the skutterudite Ce3Co4Sn13, which is known to exhibit a charge density wave (CDW) transition, at temperature T-CDW similar to 160 K, coupled to a metal-to-metal transition. We use temperature dependent hard x-ray photoemission spectroscopy (HAXPES) and x-ray absorption spectroscopy (XAS) to investigate the occupied and unoccupied electronic states of Ce3Co4Sn13. The Co 2p and Sn 3p core level spectra show small but finite shifts in binding energy positions across T-CDW while Ce 3d core level spectra do not show any change across the transition. The Ce M-4,M-5-edge XAS spectrum compared with calculations indicate a typical trivalent ionic Ce3+ spectral shape, ruling out Kondo screening in Ce3Co4Sn13. In contrast, the Co L-2,L-3-edge XAS spectrum compared with a calculated spectrum shows evidence for hybridization with neighboring Sn atoms in a trigonal prismatic co-ordination. Temperature dependent XAS across the Co L-2,L-3-edge shows a small shift across T-CDW, consistent with HAXPES results. Detailed XAS measurements as a function of temperature show that the spectral shifts occur with a hysteresis across T-CDW , indicative of a first-order transition. Valence band spectra show a normal Fermi edge above and below T-CDW. The Co 3d states are observed at a binding energy of similar to 2 eV while the Ce 4f states occur as a weak feature within 0.5 eV of the Fermi level. The results suggest an unusual CDW transition coupled to a metal-to-metal transition in Ce3Co4Sn13.