Surface instability and chemical reactivity of ZrSiS and ZrSiSe nodal-line semimetals

Among topological semimetals, in nodal-line semimetals (NLSM) conduction and valence bands cross each other. In particular, in NLSM, topological constraints protect band crossings and, moreover, band touching forms nodal lines or rings. Recently, topological nodal lines have been observed in bulk ZrSiX compounds (X = S, Se, Te). In ZrSiX, a tetragonal structure is formed by the stacking of X-ZrSi-Zr-X slabs covalently bonded between each other, whose strength decreases by replacing S with Se or Te ions. This class of materials exhibits large and non-saturating magnetoresistance and ultrahigh mobility of charge carriers.
The control over surface phenomena, including oxidation, degradation, and surface reconstruction is a crucial step in order to evaluate the feasibility of the exploitation in technology of ZrSiX.
By means of X-ray photoelectron spectroscopy (XPS) carried out at the APE-HE beamline, high-resolution electron energy loss (HREELS) and density functional theory, an international team of researchers from Italy, China, Russia, Taiwan, and USA (coordinated by University of L’Aquila) has studied the evolution of ZrSiS and ZrSiSe surfaces in oxygen and ambient atmosphere.
The chemical activity of ZrSiX compounds is mainly determined by the interactions of Si layer with ZrX sublayer. Any adsorption provides distortion of the Si layer (flat in bulk). In the case of ZrSiS, the ZrS sublayer is almost the same as in bulk and therefore adsorption is unfavorable because it provides distortions of Si layer. In the case of ZrSiSe, the ZrSe sublayer is already strongly distorted (structure different from bulk), and, therefore, further distortion of Si layer by adsorption is favorable (see figure).

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Image: Atomic structure of different steps of the process of the oxidation of ZrSiSe from (a-d) Zr-sites and (e-h) Si-sites. Red, light blue, black and yellow balls represent O, Zr, Se, and Si atoms, respectively. On panels (a) and (e) physical adsorption of single oxygen molecule is depicted. Panels (b) and (f) represent the situation of uniform coverage of the surfaces by molecular oxygen. In panels (c) and (g), decomposition of single oxygen molecule on the surfaces is represented. Panels (d) and (h) show total oxidation of the surfaces.