Direct observation of electronic bandgap and hot carrier dynamics in GeAs semiconductor

Germanium arsenide (GeAs) is a layered semiconductor with remarkably anisotropic thermoelectric and optical properties and a promising candidate for multifunctional devices based on in-plane polarization dependent response. Understanding the underlying mechanism of such devices requires knowledge of GeAs electronic band structure and of the hot carrier dynamics in its conduction band, whose details are still unclear. In this work, we investigate the properties of occupied and photoexcited states of GeAs, by combining scanning tunneling spectroscopy, angle-resolved photoemission spectroscopy (ARPES), and time-resolved ARPES. We find that GeAs is an ∼0.8 eV indirect gap semiconductor, for which the conduction band minimum (CBM) is located at the Γ¯ point while the valence band maximum is out of Γ¯. A Stark broadening of the valence band is observed immediately after photoexcitation, which can be attributed to the effects of the electrical field at the surface induced by inhomogeneous screening. Moreover, the hot electron relaxation time of 1.56 ps is down to the CBM, which is dominated by electron–phonon coupling. Besides their relevance for our understanding of GeAs, these findings present general interest for the design of high performance thermoelectric and optoelectronic devices based on 2D semiconductors.