Probing local distortion around structural defects in half-Heusler thermoelectric NiZrSn alloy.

The half-Heusler NiZrSn (NZS) alloy is particularly interesting owing to its excellent thermoelectric properties, mechanical strength, and oxidation resistance. However, the experimentally investigated thermal conductivity of half-Heusler NZS alloys shows discrepancies when compared to the theoretical predictions. This study investigates the crystal structure around atomic defects by comparing experimental and theoretical X-ray absorption fine structure (XAFS) spectra of the crystal structure of a half-Heusler NZS alloy. The results of both Zr and Ni K-edge XAFS spectra verified the existence of atomic defects at the vacancy sites distorting the C1b-type crystal structure. We concluded that the distortion of the atoms around the interstitial Ni disorder could be the probable reason for the observed lower thermal conductivity values compared to that predicted theoretically in half-Heusler alloys. Our study makes a significant contribution to the literature because the detailed investigation of the lattice distortion around atomic defects will pave the way to further reduce the thermal conductivity by controlling this distortion.

Highly Coordinated Iron and Cobalt Nitrides Synthesized at High Pressures and High Temperatures.

Highly coordinated iron and cobalt nitrides were successfully synthesized via direct chemical reaction between a transition metal and molecular nitrogen at pressures above approximately 30 GPa using a laser-heated diamond anvil cell. The synthesized novel transition metal nitrides were found to crystallize into the NiAs-type or marcasite-type structure. NiAs-type FeN could be quenched at ambient pressure, although it was gradually converted to the ZnS-type structure after the pressure was released. On the other hand, CoN was recovered with ZnS-type structure through a phase transition from NiAs-type structure at approximately a few gigapascals during decompression. Marcasite-type CoN2 was also synthesized at pressures above approximately 30 GPa. High-pressure in situ X-ray diffraction measurement showed that the zero-pressure bulk modulus of marcasite-type CoN2 is 216(18) GPa, which is comparable to that of RhN2. This indicates that the interatomic distance of the N-N dimer in marcasite-type CoN2 is short because of weak orbital interaction between cobalt and nitrogen atoms, as in RhN2. Surprisingly, a first-principles electronic band calculation suggests that the NiAs-type FeN and CoN and marcasite-type CoN2 exhibit metallic characteristics with magnetic moments of 3.4, 0.6, and 1.2 µB, respectively. The ferromagnetic NiAs-type structure originates from the anisotropic arrangement of transition atoms stacked along the c axis.

Discovery of the last remaining binary platinum-group pernitride RuN2.

The last remaining marcasite-type RuN2 was successfully synthesized by direct chemical reaction between ruthenium and molecular nitrogen above the pressure of 32 GPa. For the first time, we found that Ru 4d is weakly hybridized with N 2p in the structure by using transmission electron microscopy equipped with electron-energy-loss spectroscopy. Our finding give important knowledge about the platinum-group pernitride with respect to the chemical bonding between platinum-group element and nitrogen.

SAMRAI: a novel variably polarized angle-resolved photoemission beamline in the VUV region at UVSOR-II.

A novel variably polarized angle-resolved photoemission spectroscopy beamline in the vacuum-ultraviolet (VUV) region has been installed at the UVSOR-II 750 MeV synchrotron light source. The beamline is equipped with a 3 m long APPLE-II type undulator with horizontally/vertically linear and right/left circular polarizations, a 10 m Wadsworth type monochromator covering a photon energy range of 6-43 eV, and a 200 mm radius hemispherical photoelectron analyzer with an electron lens of a +/-18 degrees acceptance angle. Due to the low emittance of the UVSOR-II storage ring, the light source is regarded as an entrance slit, and the undulator light is directly led to a grating by two plane mirrors in the monochromator while maintaining a balance between high-energy resolution and high photon flux. The energy resolving power (hnu/Deltahnu) and photon flux of the monochromator are typically 1 x 10(4) and 10(12) photons/s, respectively, with a 100 microm exit slit. The beamline is used for angle-resolved photoemission spectroscopy with an energy resolution of a few meV covering the UV-to-VUV energy range.

High-resolution photoelectron spectroscopy of Heusler-type Fe(2)VAl alloy.

The electronic structure of Heusler-type Fe(2)VAl has been studied by high-resolution photoelectron spectroscopy with the excitation photon energy hnu ranging from 21.2 eV (the He I laboratory light source) to 904 eV (the soft X-ray synchrotron light source) for clean surfaces prepared by scraping or fracturing polycrystalline and single crystalline specimens. Photoelectron spectra recorded for the fractured surfaces show a 10 eV-wide valence band with fine structures and a clear decrease in the intensity towards the Fermi level E(F), while a high intensity at E(F) and no fine structures are observed for the scraped surface. Comparison with the theoretical density of states (DOS) indicates that the vacuum ultraviolet photoelectron spectra emphasize the transition-metal 3d bands but the soft X-ray photoelectron spectra agree remarkably well with the DOS including the fine structures and the pseudogap at E(F). The present results suggest that the electronic structure of Fe(2)VAl is highly sensitive to possible strain and defects induced by scraping. Bulk electronic structures of Fe(2)VAl are discussed in relation to the reported fascinating transport properties.

High-resolution photoemission spectroscopy for the layered antiferromagnetic (La(1-z)Nd(z))(0.46)Sr(0.54)MnO(3).

High-resolution HeI photoemission spectroscopy (UPS), Mn 2p-3d resonant photoemission spectroscopy (RPES) and Mn 2p X-ray absorption spectroscopy (XAS) have been performed to investigate the electronic structure and its effect on the electrical resistivity in (La(1-z)Nd(z))(0.46)Sr(0.54)MnO(3) (z = 0, 0, 2, 0.6 and 1.0). It was found that in the UPS and RPES spectra the Fermi edge persisted over the temperature range 15 < or = T < or = 340 K regardless of the magnetic structure or the composition of the samples. The density of states at the Fermi level [N(E(F))] in the samples where 0 < or = z < or = 0.6 was increased drastically at the Curie temperature (T(C)) with decreasing temperature, but essentially kept unchanged across the Néel temperature (T(N)). A fairly large reduction at T(C) and a small increase at T(N) in the electrical resistivity with decreasing temperature are found to be well accounted for in terms of the temperature dependence of N(E(F)). The presence of a finite N(E(F)) in the insulating Nd(0.46)Sr(0.54)MnO(3) was also found. Thus the origin of the insulating behavior in this sample can be regarded as the Anderson localization associated with the small density of states and the chemical disorder between Nd and Sr.