NaSnAs: An Exfoliatable Layered van der Waals Zintl Phase.

The discovery of new families of exfoliatable 2D crystals that have diverse sets of electronic, optical, and spin-orbit coupling properties enables the realization of unique physical phenomena in these few-atom-thick building blocks and in proximity to other materials. Herein, using NaSnAs as a model system, we demonstrate that layered Zintl phases having the stoichiometry ATtPn (A = group 1 or 2 element, Tt = group 14 tetrel element, and Pn = group 15 pnictogen element) and feature networks separated by van der Waals gaps can be readily exfoliated with both mechanical and liquid-phase methods. We identified the symmetries of the Raman-active modes of the bulk crystals via polarized Raman spectroscopy. The bulk and mechanically exfoliated NaSnAs samples are resistant toward oxidation, with only the top surface oxidizing in ambient conditions over a couple of days, while the liquid-exfoliated samples oxidize much more quickly in ambient conditions. Employing angle-resolved photoemission spectroscopy, density functional theory, and transport on bulk and exfoliated samples, we show that NaSnAs is a highly conducting 2D semimetal, with resistivities on the order of 10 Ω·m. Due to peculiarities in the band structure, the dominating p-type carriers at low temperature are nearly compensated by the opening of n-type conduction channels as temperature increases. This work further expands the family of exfoliatable 2D materials to layered van der Waals Zintl phases, opening up opportunities in electronics and spintronics.