The 18-electron ternary intermetallic systems TiNiSn and TiCoSb are promising for applications as high-temperature thermoelectrics and comprise earth-abundant, and relatively nontoxic elements. Heusler and half-Heusler compounds are usually prepared by conventional solid state methods involving arc-melting and annealing at high temperatures for an extended period of time. Here, we report an energy-saving preparation route using a domestic microwave oven, reducing the reaction time significantly from more than a week to one minute. A microwave susceptor material rapidly heats the elemental starting materials inside an evacuated quartz tube resulting in near single phase compounds. The initial preparation is followed by a densification step involving hot-pressing, which reduces the amount of secondary phases, as verified by synchrotron X-ray diffraction, leading to the desired half-Heusler compounds, demonstrating that hot-pressing should be treated as part of the preparative process. For TiNiSn, high thermoelectric power factors of 2 mW/mK2 at temperatures in the 700 to 800 K range, and zT values of around 0.4 are found, with the microwave-prepared sample displaying somewhat superior properties to conventionally prepared half-Heuslers due to lower thermal conductivity. The TiCoSb sample shows a lower thermoelectric figure of merit when prepared using microwave methods because of a metallic second phase.

Half-Heusler thermoelectrics offer the possibility to choose from a variety of non-toxic and earth-abundant elements. TiNiSn is of particular interest and - with its relatively high electrical conductivity and Seebeck coefficient - allows for optimization of its thermoelectric figure of merit, reaching values of up to 1 in heavily-doped and/or phase-segregated systems. In this contribution, we used an energy- and time-efficient process involving solid-state preparation in a commercial microwave oven and a fast consolidation technique, Spark Plasma Sintering, to prepare a series of Ni-rich TiNi1+xSn with small deviations from the half-Heusler composition. Spark Plasma Sintering plays an important role in the process by being a part of the synthesis of the material rather than solely a densification technique. Synchrotron powder X-ray diffraction and microprobe data confirm the presence of a secondary TiNi2Sn full-Heusler phase within the half-Heusler matrix. We observe a clear correlation between the amount of full-Heusler phase and the lattice thermal conductivity of the samples, resulting in decreasing total thermal conductivity with increasing TiNi2Sn fraction. This trend shows that phonons are scattered effectively as a result of the microstructure of the materials with full-Heusler inclusions in the size range of microns to tens of microns. The best performing samples with around 5% of TiNi2Sn phase exhibit maximum figures of merit of almost 0.6 between 750 K and 800 K which is an increase of ca. 35% compared to the zT of the parent compound TiNiSn.

Recently it was discovered that van der Waals-bonded magnetic materials retain long range magnetic ordering down to a single layer, opening many avenues in fundamental physics and potential applications of these fascinating materials. One such material is FePS3, a large spin (S=2) Mott insulator where the Fe atoms form a honeycomb lattice. In the bulk, FePS3 has been shown to be a quasi-two-dimensional-Ising antiferromagnet, with additional features in the Raman spectra emerging below the Néel temperature (TN) of approximately 120 K. Using magneto-Raman spectroscopy as an optical probe of magnetic structure, we show that one of these Raman-active modes in the magnetically ordered state is actually a magnon with a frequency of ≈3.7 THz (122 cm -1 ). Contrary to previous work, which interpreted this feature as a phonon, our Raman data shows the expected frequency shifting and splitting of the magnon as a function of temperature and magnetic field, respectively, where we determine the g-factor to be ≈2. In addition, the symmetry behavior of the magnon is studied by polarization-dependent Raman spectroscopy and explained using the magnetic point group of FePS3.

The structural implications of excess Ni in the TiNiSn half-Heusler compound are examined through a combination of synchrotron x-ray and neutron scattering studies, in conjunction with first principles density functional theory calculations on supercells. Despite the phase diagram suggesting that TiNiSn is a line compound with no solid solution, for small x in TiNi 1þx Sn there is indeed an appearance-from careful analysis of the scattering-of some solubility, with the excess Ni occupying the interstitial tetrahedral site in the half-Heusler structure. The analysis performed here would point to the excess Ni not being statistically distributed, but rather occurring as coherent nanoclusters. First principles calculations of energetics, carried out using supercells, support a scenario of Ni interstitials clustering, rather than a statistical distribution. V C 2014 AIP Publishing LLC.

Thermoelectric properties and phase evolution have been studied in biphasic Ti-Ni-Sn materials containing full-Heusler TiNi 2 Sn embedded within half-Heusler thermoelectric TiNiSn. Materials prepared by levitation induction melting followed by annealing were of the nominal starting composition of TiNi 1+x Sn, with x between 0.00 and 0.25. Phases and microstructure were determined using synchrotron X-ray diffraction and optical and electron microscopy. The full-Heusler phase is observed to be semi-coherent with the half-Heusler majority phase. Differential thermal analysis was performed to determine melting temperatures of the ternary compounds and extrapolate a liquidus contour surface for the Ti-Ni-Sn system. The thermal conductivity is reduced in full-Heusler material. This leads to an increased thermoelectric figure of merit, ZT , from 0.35 for the stoichiometric compound to 0.44 for TiNi 1.15 Sn. Density functional theory calculations using hybrid functionals (HSE06) were carried out to determine band alignments between the half-and full-Heusler compounds, as well as comparative energies of formation. The HSE06 band structure of TiNiSn is presented as well.

The effect of phase-segregated Heusler TiNi2Sn on high temperature thermoelectric properties of bulk half-Heusler TiNiSn has been studied. In samples expressed by the composition TiNi1+xSn, a significant decrease in thermal conductivity (between 10% and 30%) is observed for two-phase TiNi1.15Sn, despite the second-phase particles existing at the micrometer scale; a 50% increase in the electrical conductivity is also measured. These result in a maximum figure of merit, ZT, of 0.44 at 800 K, which is 25% greater than is observed for the x = 0 sample. Density functional calculations of TiNiSn and TiNi2Sn suggest that the latter should deplete carriers at 0 K.

We investigate the average structure, local structure, and magnetic behavior of Heusler alloys of the composition Mn 1−x Fe x Ru 2 Sn, between antiferromagnetic (AFM) MnRu 2 Sn and ferromagnetic (FM) FeRu 2 Sn (often written Ru 2 MnSn and Ru 2 FeSn). Using a combination of neutron total scattering, electron microscopy, and 57 Fe Mössbauer spectroscopy, we conclude that true solid solutions are formed across the compositional space investigated, with Fe substituting for Mn on the Heusler lattice, with little or no antisite disorder. Despite the lack of chemical phase separation, magnetic phase separation is present in compositions near x = 0.50, where the coexistence of AFM and FM domains is confirmed by 15 K neutron diffraction. At these intermediate compositions a large increase in magnetic coercivity is observed, in excess of 1 kOe, attributed to local exchange interactions.

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