Valence-band structure of the skutterudite compounds CoAs3, CoSb3, and RhSb3 studied by x-ray photoelectron spectroscopy

The valence-band structure of CoAs3, CoSb3, and RhSb3 with a skutterudite-t ype crystal structure has been investigated by x-ray photoelectron spectros copy. The photoemission spectra are compared with recent density-of-states calculations. Our photoemission spectra results and theoretical results are in good agreement for the energy positions in the metal d states and the p nicogen p states, but relatively large differences are found for the positi ons in the pnicogen s states. Based on our photoemission spectra, the elect ronic bonding states and the chemical trends are explained qualitatively in terms of a simple tight-binding model. The double localized and itinerant nature of the metal d states is also discussed in relation to the propertie s of the skutterudites. The metal d-derived density of states feature is cl early observed at about 1.2-, 1.4-, and 2.4-eV binding energies for CoSb3, CoAs3, and RhSb3, respectively. From the point of View of the crystal-held effects, it can be considered that this d-character band originates predomi nantly from the d orbitals with T-2g symmetry, while d orbitals with E-g sy mmetry hybridize strongly with the p orbitals forming the conduction band. Since the t(2g) states are considered to be almost completely filled, corre sponding to the zero spin S = 0 state ((1)A(1), t(2g)(6)), most of skutteru dites exhibit diamagnetic properties. On the other hand, the slight chemica l shifts of the core levels as compared with the pure elements indicate a s mall charge transfer from metal to pnicogen atoms in the skutterudites, lea ding to hybridization between metal d states and pnicogen p states. p-d hyb ridization causes not only a substantial screening of atomic Coulomb intera ctions at metal sites, but also a strong covalent bonding in these material s. Concerning a particular point of the band structure in skutterudites, ou r photoemission spectra near the valence-band edge show clear experimental evidence of a small density of states around the Fermi level due to a singl e band crossing the pseudogap.