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IV-VI semiconductor SnSe has been known as the material with record highthermoelectric performance.The multiple close-to-degenerate valence bands inthe electronic band structure has been one of the key factors contributing tothe high power factor and thus figure of merit in the SnSe single crystal. Todate, there have been primarily theoretical calculations of this particularelectronic band structure. In this paper, however, using angle-resolvedphotoemission spectroscopy, we perform a systematic investigation of theelectronic structure of SnSe. We directly observe three predicted hole bandswith small energy differences between their band tops and relatively smallin-plane effective masses, in good agreement with the ab initio calculationsand critical for the enhancement of the Seebeck coefficient while keeping highelectrical conductivity. Our results reveal the complete band structure of SnSeand help to provide a deeper understanding of the electronic origin of theexcellent thermoelectric performances in SnSe.

Photoemission Study of the Electronic Structure of Valence Band Convergent SnSe