Lattice thermal conductivity of Tix_xZry_yHf1−x−y_{1-x-y}NiSn half-Heusler alloys calculated from first principles: Key role of nature of phonon modes

In spite of their relatively high lattice thermal conductivity $\kappa_{\ell}$, the XNiSn (X=Ti, Zr or Hf) half-Heusler compounds are good thermoelectric materials. Previous studies have shown that $\kappa_{\ell}$ can be reduced by sublattice-alloying on the X-site. To cast light on how the alloy composition affects $\kappa_\ell$, we study this system using the phonon Boltzmann-transport equation within the relaxation time approximation in conjunction with density functional theory.The effect of alloying through mass-disorder scattering is explored using the virtual crystal approximation to screen the entire ternary Ti$_x$Zr$_{y}$Hf$_{1-x-y}$NiSn phase diagram. The lowest lattice thermal conductivity is found for the Ti$_x$Hf$_{1-x}$NiSn compositions; in particular, there is a shallow minimum centered at Ti$_{0.5}$Hf$_{0.5}$NiSn with $\kappa_l$ taking values between 3.2 and 4.1 W/mK when the Ti content varies between 20 and 80\%. Interestingly, the overall behavior of mass-disorder scattering in this system can only be understood from a combination of the nature of the phonon modes and the magnitude of the mass variance. Mass-disorder scattering is not effective at scattering acoustic phonons of low energy. By using a simple model of grain boundary scattering, we find that nanostructuring these compounds can scatter such phonons effectively and thus further reduce the lattice thermal conductivity; for instance, Ti$_{0.5}$Hf$_{0.5}$NiSn with a grain size of $L= 100$ nm experiences a 42\% reduction of $\kappa_{\ell}$ compared to that of the single crystal

Metal Distributions, Efficient n-Type Doping, and Evidence for in-Gap States in TiNiM_<i>y</i>Sn (M = Co, Ni, Cu) half-Heusler Nanocomposites

XNi1+ySn nanocomposites consisting of a XNiSn half-Heusler (HH) matrix with segregated XNi2Sn Full Heusler (FH) inclusions promise improvements in thermoelectric efficiencies. We extend recent research by reporting on TiNiMySn (0 ≤ y ≤ 1) nanocomposites with M = Co (3d9), Ni (3d10) and Cu (3d104s1). Neutron powder diffraction reveals that the Ni and Cu series produce a matrix of TiNiSn with nanosegregated TiNi2Sn and TiNi1+dCu1–dSn, respectively. For the Co series, the Co inserts into both phases to obtain a TiNi1–yCoySn matrix with nanosegregated TiNi2–yCoySn. Systematic changes in Seebeck coefficient (S) and electrical resistivity (ρ) are observed in all three series. For M = Ni, changes in S and ρ are attributed to in-gap states arising from the nanosegregation. The M = Co composites show a complex interplay between the hole doped TiNi1–yCoySn matrix and similar in-gap states, where the p- to n-type transition temperature increases but the maximum S remains unchanged at +30 μV K–1. The 4s1 electron for M = Cu is delocalized in the HH matrix, leading to metal-like ρ(T) and up to 100% improved thermoelectric power factors compared to TiNiSn (S2/ρ = 2 mW m–1 K–2 at 600–700 K for y = 0.025). These results broaden the range of segregated FH phases that could be used to enhance HH thermoelectric performance

Screening and Fabrication of Half-Heusler phases for thermoelectric applications

Half-Heusler phases have gained recently much interest as thermoelectric materials. Screening of possible systems was performed by ab-initio simulation using VASP-software. The energy-versus-Volume (E(V)) curves were calculated and calibrated. For TiCoSb, NbNiSn, FeMoSb the stability of Half-Heusler phase against concurrent crystal structures like TiNiSi, ZrCoAl, ZrBeSi, FeSiV, ZrNiP and Full Heusler was confirmed. However, the thermo-dynamical driving force as calculated from the difference in lattice energies is less than 0.1eV/atom. Hence, the fabrication of Half Heusler phases is a challenge and requires three steps, surface activation of the raw material by ball milling, arc-melting of pressed pellets and finally long-term annealing treatment in a vacuum furnace. On doped TiCoSb specimens, Seebeck coefficients up to 0.1 mV/K, on NiNbSn 0.16 mV/K were measured, although the microstructure was not yet optimized.Comment: 6 pages, 5 figures, 2 table

Thermoelectric performance of multiphase XNiSn (X = Ti, Zr, Hf) half-Heusler alloys

Quantitative X-ray powder diffraction analysis demonstrates that mixing Ti, Zr and Hf on the ionic site in the half-Heusler structure, which is a common strategy to lower the lattice thermal conductivity in this important class of thermoelectric materials, leads to multiphase behaviour. For example, nominal Ti0.5Zr0.5NiSn has a distribution of Ti1−xZrxNiSn compositions between 0.24 &#8804; x &#8804; 0.70. Similar variations are observed for Zr0.50Hf0.5NiSn and Ti0.5Hf0.5NiSn. Electron microscopy and elemental mapping demonstrate that the main compositional variations occur over micrometre length scales. The thermoelectric power factors of the mixed phase samples are improved compared to the single phase end-members (e.g. S2/ρ = 1.8 mW m−1 K−2 for Ti0.5Zr0.5NiSn, compared to S2/ρ = 1.5 mW m−1 K−2 for TiNiSn), demonstrating that the multiphase behaviour is not detrimental to electronic transport. Thermal conductivity measurements for Ti0.5Zr0.5NiSn0.95 suggest that the dominant reduction comes from Ti/Zr mass and size difference phonon scattering with the multiphase behaviour a secondary effect

Electronic structure of Zr-Ni-Sn systems: role of clustering and nanostructures in Half-Heusler and Heusler limits

Half-Heusler and Heusler compounds have been of great interest for several decades for thermoelectric, magnetic, half-metallic and many other interesting properties. Among these systems, Zr-Ni-Sn compounds are interesting thermoelectrics which can go from semiconducting half-Heusler (HH) limit, ZrNiSn, to metallic Heusler (FH) limit, ZrNi$_2$Sn. Recently Makogo et al. [J. Am. Chem. Soc. 133, 18843 (2011)] found that dramatic improvement in the thermoelectric power factor of HH can be achieved by putting excess Ni into the system. This was attributed to an energy filtering mechanism due to the formation of FH nanostructures in the HH matrix. Using density functional theory we have investigated clustering and nanostructure formation in HH$_{1-x}$FH$_x$ systems near the HH and FH ends and found that excess Ni atoms in HH tend to stay close to each other and form nanoclusters of FH. On the other hand, there is competing interaction between Ni-vacancies in FH which prevent them from forming HH nano clusters. Effects of nano inclusions on the electronic structure at both HH and FH ends will be discussed.Comment: Published in J. Phys.: Condens. Matte