Xuezhi Ke

Part-crystalline part-liquid state and rattling-like thermal damping in materials with chemical-bond hierarchy

Significance Materials with chemical-bond hierarchy may have a specially mixed part-crystalline part-liquid state and show nontraditional thermal transports beyond the traditional “small-parameter” lattice dynamics approach, especially the rattling-like thermal damping and thus an unusual lattice thermal conductivity that can only be described by including an effective “resonant” phonon scattering. Understanding thermal and phonon transport in solids has been of great importance in many disciplines such as thermoelectric materials, which usually requires an extremely low lattice thermal conductivity (LTC). By analyzing the finite-temperature structural and vibrational characteristics of typical thermoelectric compounds such as filled skutterudites and Cu3SbSe3, we demonstrate a concept of part-crystalline part-liquid state in the compounds with chemical-bond hierarchy, in which certain constituent species weakly bond to other part of the crystal. Such a material could intrinsically manifest the coexistence of rigid crystalline sublattices and other fluctuating noncrystalline sublattices with thermally induced large-amplitude vibrations and even flow of the group of species atoms, leading to atomic-level heterogeneity, mixed part-crystalline part-liquid structure, and thus rattling-like thermal damping due to the collective soft-mode vibrations similar to the Boson peak in amorphous materials. The observed abnormal LTC close to the amorphous limit in these materials can only be described by an effective approach that approximately treats the rattling-like damping as a “resonant” phonon scattering.

Equation of state of TiH2 up to 90 GPa: A synchrotron x-ray diffraction study and ab initio calculations

We performed high-pressure studies and ab initio calculations of titanium hydride (TiH2), an important compound in hydrogen storage research. In situ, synchrotron x-ray diffraction studies were carried out in two separate compression runs: the first up to 19 GPa in quasihydrostatic conditions and the second up to 90 GPa in nonhydrostatic conditions, and followed by the subsequent decompression to ambient conditions. The pressure evolution of the diffraction patterns revealed a cubic [face-centered-cubic (fcc), Fm-3m] to tetragonal (body-centered-tetragonal (bct), I4/mmm) phase transition in TiH2 occurring at or below 0.6 GPa. The high-pressure tetragonal phase persisted up to 90 GPa. Upon decompression to ambient conditions the observed phase transition appeared irreversible. A third order Birch–Murnaghan fit of the unit cell volume as a function of pressure for all experimental points, yielded a zero pressure bulk modulus K0=142(7) GPa, and its pressure derivative K0′=3.3(0.2) for the high-pressure tetra...

Diverse lattice dynamics in ternary Cu-Sb-Se compounds.

Searching and designing materials with extremely low lattice thermal conductivity (LTC) has attracted considerable attention in material sciences. Here we systematically demonstrate the diverse lattice dynamics of the ternary Cu-Sb-Se compounds due to the different chemical-bond environments. For Cu3SbSe4 and CuSbSe2, the chemical bond strength is nearly equally distributed in crystalline bulk, and all the atoms are constrained to be around their equilibrium positions. Their thermal transport behaviors are well interpreted by the perturbative phonon-phonon interactions. While for Cu3SbSe3 with obvious chemical-bond hierarchy, one type of atoms is weakly bonded with surrounding atoms, which leads the structure to the part-crystalline state. The part-crystalline state makes a great contribution to the reduction of thermal conductivity that can only be effectively described by including a rattling-like scattering process in addition to the perturbative method. Current results may inspire new approaches to designing materials with low lattice thermal conductivities for high-performance thermoelectric conversion and thermal barrier coatings.

Structural Phase Transition of ThC Under High Pressure

Thorium monocarbide (ThC) as a potential fuel for next generation nuclear reactor has been subjected to its structural stability investigation under high pressure, and so far no one reported the observation of structure phase transition induced by pressure. Here, utilizing the synchrotron X-ray diffraction technique, we for the first time, experimentally revealed the phase transition of ThC from B1 to P4/nmm at pressure of ~58 GPa at ambient temperature. A volume collapse of 10.2% was estimated during the phase transition. A modulus of 147 GPa for ThC at ambient pressure was obtained and the stoichiometry was attributed to the discrepancy of this value to the previous reports.

Strain-controlled interface engineering of binding and charge doping at metal-graphene contacts

Strain effects on tuning the interface binding as well as the charge doping at metal-graphene contacts have been investigated by using density functional theory calculations. A realizable tensile strain is found to be very effective in enhancing the interface binding as well as shifting the Fermi level. Particularly, an enhancement of the binding energy up to 315% can be achieved because of the dipole-dipole interaction. Our results presented here show that strain is an efficient way to overcome the weak binding problem at metal-graphene interface, and will motivate active experimental efforts in improving the performance of graphene-based devices.

Pressure-induced structural transformations and polymerization in ThC 2

Thorium-carbon systems have been thought as promising nuclear fuel for Generation IV reactors which require high-burnup and safe nuclear fuel. Existing knowledge on thorium carbides under extreme condition remains insufficient and some is controversial due to limited studies. Here we systematically predict all stable structures of thorium dicarbide (ThC2) under the pressure ranging from ambient to 300 GPa by merging ab initio total energy calculations and unbiased structure searching method, which are in sequence of C2/c, C2/m, Cmmm, Immm and P6/mmm phases. Among these phases, the C2/m is successfully observed for the first time via in situ synchrotron XRD measurements, which exhibits an excellent structural correspondence to our theoretical predictions. The transition sequence and the critical pressures are predicted. The calculated results also reveal the polymerization behaviors of the carbon atoms and the corresponding characteristic C-C bonding under various pressures. Our work provides key information on the fundamental material behavior and insights into the underlying mechanisms that lay the foundation for further exploration and application of ThC2.