Electronic structure of black SmS. I. 4d-4f resonance and angle-integrated valence-band photoemission spectroscopy

We study the electronic structure of single-crystal "black" semiconducting SmS using x-ray absorption and resonance photoemission spectroscopy across the 4d-4f threshold and high-resolution temperature-dependent valence-band photoemission spectroscopy. The 4d-4f on-resonance spectra show mixed valency of Sm²⁺ and Sm³⁺ states in semiconducting SmS at low temperature (T = 30 K). The high-resolution spectra show a pseudogap within 20 meV of the Fermi level at low temperatures. This pseudogap is gradually filled up accompanied by a redistribution of spectral weight over a larger energy scale of ∼200 meV on increasing temperature, resulting in an incipient metallic phase at room temperature. The two energy scales can be associated with the coherence temperature T_c and the Kondo temperature T_K, respectively. The changes in the single-particle density of states at and about the Fermi level are compatible with recent theoretical results on "exhaustion physics" in the periodic Anderson model. The present study indicates a Kondo lattice picture for SmS and suggests a relation between the mixed valency and the temperature dependence of the pseudogap for "black" semiconducting SmS.