ABSTRACT
Inorganic clathrate materials are of great fundamental interest and potential practical use for application as thermoelectric materials in freon-free refrigerators, waste-heat converters, direct solar thermal energy converters, and many others. Experimental studies of their electronic structure and bonding have been, however, strongly restricted by (i) the crystal size and (ii) essential difficulties linked with the clean surface preparation. Overcoming these handicaps, we present for the first time a comprehensive picture of the electronic band structure and the chemical bonding for the Sn(24-x-δ)InxAs(22-y)I8 clathrates obtained by means of photoelectron spectroscopy and complementary quantum modeling.
ABSTRACT
The long-term stability of functional properties of topological insulator materials is crucial for the operation of future topological insulator based devices. Water and oxygen have been reported to be the main sources of surface deterioration by chemical reactions. In the present work, we investigate the behavior of the topological surface states on Bi2X3 (X = Se, Te) by valence-band and core level photoemission in a wide range of water and oxygen pressures both in situ (from 10(-8) to 0.1 mbar) and ex situ (at 1 bar). We find that no chemical reactions occur in pure oxygen and in pure water. Water itself does not chemically react with both Bi2Se3 and Bi2Te3 surfaces and only leads to slight p-doping. In dry air, the oxidation of the Bi2Te3 surface occurs on the time scale of months, in the case of Bi2Se3 surface of cleaved crystal, not even on the time scale of years. The presence of water, however, promotes the oxidation in air, and we suggest the underlying reactions supported by density functional calculations. All in all, the surface reactivity is found to be negligible, which allows expanding the acceptable ranges of conditions for preparation, handling and operation of future Bi2X3-based devices.
