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As an important phase-change material, GeTe has many high-pressure phases as well, but its phase transitions under pressure are still lack of clarity. It is challenging to identify high-pressure GeTe crystal structures owing to the phase coexistence in a wide pressure range and the reversibility of phase transitions. Hence, first-principles calculations are required to provide further information in addition to limited experimental characterizations. In this work, a new orthorhombic Cmca GeTe high-pressure phase has been predicted via the CALYPSO method as the most energetically favorable phase in the pressure range between ∼30 and ∼38.5 GPa, which would update the GeTe high-pressure phase transition sequence. The crystal structure of the Cmca phase is composed of alternate stacking puckered layers of Ge six-membered rings and Te four-membered rings along the b direction. The high density of states near the Fermi level and delocalization of electrons from the two-dimensional electron localization function indicate a strong metallic property of the Cmca phase. Electron–phonon coupling calculations indicate that the Cmca phase is superconductive below ∼4.2 K at 35 GPa. The simulated x-ray diffraction pattern of the Cmca phase implies that this phase might coexist with the Pnma-boat phase under high pressure. These results offer further understanding on the high-pressure structural evolution and physical properties in GeTe and other IV–VI semiconductors. [ABSTRACT FROM AUTHOR]

The presence of interstitial electrons in electrides endows them with interesting attributes, such as low work function, high carrier concentration, and unique magnetic properties. Thorough knowledge and understanding of electrides are thus of both scientific and technological significance. Here, we employ first-principles calculations to investigate Mott-insulating Ae5X3 (Ae = Ca, Sr, and Ba; X = As and Sb) electrides with Mn5Si3-type structure, in which half-filled interstitial electrons serve as ions and are spin-polarized. The Mott-insulating property is induced by strong electron correlation between the nearest interstitial electrons, resulting in spin splitting and a separation between occupied and unoccupied states. The half-filled antiferromagnetic configuration and localization of the interstitial electrons are critical for the Mott-insulating properties of these materials. Compared with that in intermetallic electrides, the orbital hybridization between the half-filled interstitial electrons and the surrounding atoms is weak, leading to highly localized magnetic centers and pronounced correlation effects. Therefore, the Mott-insulating electrides Ae5X3 have very large indirect bandgaps (∼0.30 eV). In addition, high pressure is found to strengthen the strong correlation effects and enlarge the bandgap. The present results provide a deeper understanding of the formation mechanism of Mott-insulating electrides and provide guidance for the search for new strongly correlated electrides. [ABSTRACT FROM AUTHOR]

Ultra-high-temperature ceramics are required for many aerospace applications. In this work, HfB2-30 vol.% HfC and HfB2-26 vol.% HfC-43 vol.% MoB high-density composites were prepared by one-step in-situ reactive spark plasma sintering (R-SPS) using Hf, B4C and Mo powders as starting materials. The influences of sintering temperature on the densification mechanism, microstructural evolution, mechanical properties and oxidation resistance of the composites were thoroughly investigated. The results demonstrate that the raw materials undergo a complete chemical reaction to form new binary HfB2-HfC and ternary HfB2-HfC-MoB composite structures at a temperature of 1300°C. The HfB2-HfC and HfB2-HfC-MoB composites prepared at the optimal conditions (pressure = 50 MPa, temperature = 1800°C, holding time = 5 min) had highre densities of 97% and 98%, respectively. The Vickers hardness, Young's modulus and fracture toughness of the HfB2-HfC composite were 18.3 GPa, 525 GPa and 6.34 MPa·m1/2, respectively. However, after molybdenum was added, the Vickers hardness of the ternary HfB2-HfC-MoB composite increased to 19.4 GPa but its fracture toughness decreased slightly to 6.1 MPa·m1/2. Compared with the binary composite, the ternary composite exhibited a low and thermally stable oxidation rate up to a temperature of 1400°C, and the test was conducted in air atmosphere. [ABSTRACT FROM AUTHOR]

Transition metal dichalcogenides (TMDs) are uniquely multifunctional materials with optical, electronic, and catalytic properties. Despite the advantages of low cost, low toxicity, and high abundance, the thermoelectric transport properties of MoSe2 were not extensively investigated. Meanwhile, MoSe2 bulk material with 3R phase was rarely reported compared to 2H phase. In this work, controllable phase transition from 2H to 3 R for MoSe2 bulk polycrystalline material was achieved with various Nb contents by a simple and feasible high-pressure method. The preferred orientation resulted in anisotropy of both electrical and thermal transport. The samples converted from n type for pristine sample to p type conduction after Nb doping. Meanwhile, the conduction type gradually changed from semiconductor to degenerated semiconductor. The electrical properties were distinctly improved by Nb doping systematically from the reduced bandgap and the enhanced carrier concentration and mobility. The lattice thermal conductivity was reduced by point defects and grain/phase boundaries generating from Nb doping. Maximum zT of 0.17 at 873 K was obtained for Nb0.04Mo0.96Se2, which is among the highest values for Te-free Mo dichalcogenides. The strategy of chemical doping and high-pressure synthesis provides an alternative route to achieve MoSe2 bulk materials with a controllable 2H/3R phase ratio for potential applications, which can be extended to other TMDs. [ABSTRACT FROM AUTHOR]