Ni3InSb: Synthesis, Crystal Structure, Electronic Structure, and Magnetic Properties.

The ternary phase with the composition Ni3InSb has been synthesized by high-temperature synthesis and structurally characterized by a combination of X-ray analysis, neutron diffraction analysis, and theoretical calculations. The structure of Ni3InSb crystallizes in the orthorhombic space group Pnma with lattice constants a = 7.111(3) Å, b = 5.193(3) Å, and c = 8.2113(2) Å. The crystal structure contains ∼20 atoms in its unit cell, which are distributed over four crystallographically independent positions (two Ni, one In, and one Sb). The crystal structure can be considered as a ternary substitutional variant of Ni3Sn2 (Pnma, no. 62), where a trivalent In and a pentavalent Sb orderly occupy two tetravalent Sn sites of Ni3Sn2. This site decoration pattern of two neighboring elements, In and Sb, is unique and confirmed by first principles total energy calculations. The crystal structure can be described by two building units: Ni2Sb (building unit of Ni2In) and NiIn (NiAs-type). They alternate in the crystal structure and form infinite ac-slabs (puckered), and the slabs are stacked along [010]. A triangular lattice formed by Ni atoms indicates the existence of a geometrically frustrated structure. The calculated density of states and crystal orbital Hamilton population enlighten the stability and bonding characteristics of the structure. The temperature-dependent neutron diffraction study down to 5 K reveals that the crystal structure remains in the same orthorhombic symmetry with a weak anomaly in the lattice parameters at ∼100 K. Detailed temperature- and magnetic field-dependent magnetic properties of the title phase Ni3InSb show spin-glass- or spin-disorder-like behaviors below ∼300 K with an unusual magnetic behavior below 100 K, where an enhancement of magnetization with a decrease of the coercive field has been found.

Structure and Spin-Glass Magnetism of the MnxNi2Zn11-x Pseudobinary γ-Brasses at Low Mn Contents.

The pseudobinary MnxNi2Zn11-x γ-brass-type phases at low Mn dopant levels (x = 0.1-0.5) were investigated. Crystal structures were determined for the two loading compositions of x = 0.3 and 0.5. The structures were solved in the cubic space group of I43m and are described in close analogy to the Ni2Zn11 parent γ-brass that is based on the 26-atom cluster, consisting of inner tetrahedron (IT), outer tetrahedron (OT), octahedron (OH), and cuboctahedron (CO). The refined site occupancies of the MnxNi2Zn11-x (x = 0.3, 0.5) reveal that the cluster center, which is empty in the Ni2Zn11, shows a partial occupation by Zn, with a partial depletion of Zn at the IT sites. The OH sites show a mixed Zn/Mn occupation. The OT and CO sites remain intact with respect to Ni2Zn11. Magnetic properties were studied for the Mn0.3Ni2Zn10.7 composition. The temperature-dependent zero-field-cooled and field-cooled magnetization, the ac susceptibility, the M(H) hysteresis curves, the thermoremanent magnetization, and the memory effect demonstrate typical broken-ergodicity phenomena of a magnetically frustrated spin system below the spin freezing temperature Tf ≈ 16 K. The Mn0.3Ni2Zn10.7 γ-brass phase classifies as a spin glass, originating predominantly from the random distribution of diluted Mn moments on the octahedral partial structure.

Crystal structures of two very similar 2†×†2†×†2 superstructures of γ-brass-related phases in ternary Ir-Cd-Cu system.

A binary phase Ir8Cd41 in the Ir-Cd binary system and novel ternary phases in the Ir-Cd-Cu system have been synthesized from the constituent elements using high-temperature solid-state synthesis. The structure of previously reported Ir8Cd41 and newly found ternary phases in the Ir-Cd-Cu system have been characterized by single crystal X-ray diffraction and EDS analysis. The structural analysis reveals that Ir8Cd41 adopts V8Ga41-type structure and ternary Ir-Cd-Cu phases adopt two 2 × 2 × 2-superstructures of the γ-brass-related phase. The structures of ternary Ir-Cd-Cu phases are associated with structural disorder (vacancies as well as mixed site occupancies). The crystal structures of the ternary phases are viewed using layer description and cluster concept. The 2 × 2 × 2-superstructure of γ-brass-related phases in the Cu-poor region are not isostructural with the phases in the Cu-rich region, and they are consistent with the absence of a continuous phase region between two 2 × 2 × 2-superstructures of γ-brass-related phases. In the Cu-poor region, the structures contain ∼404 atoms per unit cell, whereas in the Cu-rich phases the structures contain ∼411 atoms in their respective unit cells. The crystal structures in the Cu-poor region represent a new type in the 2 × 2 × 2-superstructure of γ-brass-related phases in view of the combination of constituent cluster types, whereas the structures in the Cu-rich region adopt the Rh7Mg44 structure type.

Thermoelectric properties of Se and Zn/Cd/Sn double substituted Co4Sb12 skutterudite compounds.

Double-doped skutterudite Co4Sb12 compounds are reported as a good n-type thermoelectric system which operate in the mid-temperature range. Instead of filling the skutterudite phase to minimize the thermal conductivity, it is proposed to induce disorder in the pnicogen rings by the substitution of Zn/Cd/Sn and Se. Structural analyses of the prepared compounds were carried out by Rietveld refinement process. The compounds show overall reduction in thermal conductivity, particularly the lattice part. Since vibration modes of heat-carrying phonons predominantly fall within the frequency range of the pnicogen rings, double substitutions on those pnicogen rings are particularly helpful in distracting the thermal transport. As larger mass difference and strain fluctuations can more efficiently scatter the heat-carrying phonons through short mean free path, it drastically restrains the thermal transport of the compounds, and this effect has been successfully demonstrated using the Debye-Callaway-Klemens model. Smooth electrical transport behavior is observed in all the samples and the power factor values are quite comparable to reported values. Phonon scattering mechanism and local distortion in the structure of the compounds is also evaluated by Raman analysis. Collectively, a high peak ZT of ∼0.7 and ∼0.65 at 673 K is obtained for Co4Sb11.86Se0.1Zn0.04 and Co4Sb11.86Se0.1Sn0.04 compounds which shows more than 50% enhancement relative to the pristine Co4Sb12 system.