Nanoscale phase separation in the oxide layer at GeTe (111) surfaces.

As a semiconductor ferroelectric, GeTe has become a focus of renewed attention due to the recent discovery of giant Rashba splitting. It already has a wide range of applications, from thermoelectricity to data storage. Its stability in ambient air, as well as the structure and properties of an oxide layer, define the processing media for device production and operation. Here, we studied a reaction between the GeTe (111) surface and molecular oxygen for crystals having solely inversion domains. We evaluated the reaction kinetics both ex situ and in situ using NAP XPS. The structure of the oxide layer is extensively discussed, where, according to HAADF-STEM and STEM-EDX, nanoscale phase separation of GeO2 and Te is observed, which is unusual for semiconductors. We believe that such behaviour is closely related to the ferroelectric properties and the domain structure of GeTe.

Observation of hidden atomic order at the interface between Fe and topological insulator Bi2Te3.

To realize spintronic devices based on topological insulators (TIs), well-defined interfaces between magnetic metals and TIs are required. Here, we characterize atomically precisely the interface between the 3d transition metal Fe and the TI Bi2Te3 at different stages of its formation. Using photoelectron diffraction and holography, we show that after deposition of up to 3 monolayers Fe on Bi2Te3 at room temperature, the Fe atoms are ordered at the interface despite the surface disorder revealed by our scanning-tunneling microscopy images. We find that Fe occupies two different sites: a hollow adatom deeply relaxed into the Bi2Te3 quintuple layers and an interstitial atom between the third (Te) and fourth (Bi) atomic layers. For both sites, our core-level photoemission spectra and density-functional theory calculations demonstrate simultaneous chemical bonding of Fe to both Te and Bi atoms. We further show that upon deposition of Fe up to a thickness of 20 nm, the Fe atoms penetrate deeper into the bulk forming a 2-5 nm interface layer containing FeTe. In addition, excessive Bi is pushed down into the bulk of Bi2Te3 leading to the formation of septuple layers of Bi3Te4 within a distance of ∼25 nm from the interface. Controlling the magnetic properties of the complex interface structures revealed by our work will be of critical importance when optimizing the efficiency of spin injection in TI-based devices.

Experimental and Computational Insight into the Chemical Bonding and Electronic Structure of Clathrate Compounds in the Sn-In-As-I System.

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.

Oxygen reduction by lithiated graphene and graphene-based materials.

Oxygen reduction reaction (ORR) plays a key role in lithium-air batteries (LABs) that attract great attention thanks to their high theoretical specific energy several times exceeding that of lithium-ion batteries. Because of their high surface area, high electric conductivity, and low specific weight, various carbons are often materials of choice for applications as the LAB cathode. Unfortunately, the possibility of practical application of such batteries is still under question as the sustainable operation of LABs with carbon cathodes is not demonstrated yet and the cyclability is quite poor, which is usually associated with oxygen reduced species side reactions. However, the mechanisms of carbon reactivity toward these species are still unclear. Here, we report a direct in situ X-ray photoelectron spectroscopy study of oxygen reduction by lithiated graphene and graphene-based materials. Although lithium peroxide (Li2O2) and lithium oxide (Li2O) reactions with carbon are thermodynamically favorable, neither of them was found to react even at elevated temperatures. As lithium superoxide is not stable at room temperature, potassium superoxide (KO2) prepared in situ was used instead to test the reactivity of graphene with superoxide species. In contrast to Li2O2 and Li2O, KO2 was demonstrated to be strongly reactive.

The chemistry of imperfections in N-graphene.

Many propositions have been already put forth for the practical use of N-graphene in various devices, such as batteries, sensors, ultracapacitors, and next generation electronics. However, the chemistry of nitrogen imperfections in this material still remains an enigma. Here we demonstrate a method to handle N-impurities in graphene, which allows efficient conversion of pyridinic N to graphitic N and therefore precise tuning of the charge carrier concentration. By applying photoemission spectroscopy and density functional calculations, we show that the electron doping effect of graphitic N is strongly suppressed by pyridinic N. As the latter is converted into the graphitic configuration, the efficiency of doping rises up to half of electron charge per N atom.

Negligible surface reactivity of topological insulators Bi2Se3 and Bi2Te3 towards oxygen and water.

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.