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Analysis of bipolar thermal conductivity might be very useful in preliminary stages of thermoelectric materials discovery. Using its product---mobility ratio between electrons and holes---it is possible to choose the most promising compound from the series and pave the correct direction of doping. Current work presents positive verification of this approach for $\mathrm{Sc}\mathrm{Ni}\mathrm{Sb}$, which is anticipated to show superior mobility when tuned towards n-type behavior. In agreement with expectation, the mobility increases by an order of magnitude due to rising tellurium content in the ${\mathrm{Sc}\mathrm{Ni}\mathrm{Sb}}_{1\ensuremath{-}x}{\mathrm{Te}}_{x}$ series. The effect is most likely driven by change of the dominant charge carriers' scattering mechanism from ionized impurity influence to point defect and acoustic phonon interaction. Simultaneously, due to a highly anisotropic conduction band, the effective mass of the carriers rises towards the n-type regime. These two effects lead to an improved thermoelectric power factor of electron-doped samples, up to $40\phantom{\rule{0.2em}{0ex}}\ensuremath{\mu}{\mathrm{WK}}^{\ensuremath{-}2}\phantom{\rule{0.2em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$ at 740 K for ${\mathrm{Sc}\mathrm{Ni}\mathrm{Sb}}_{0.85}{\mathrm{Te}}_{0.15}$. Based on this result, we suggest n-type doping for other rare-earth-based half-Heusler compounds. Representatives of this group exhibit the smallest lattice thermal conductivity in the pristine form among any half-Heusler thermoelectrics, and are anticipated to show comparably good electrical properties to ScNiSb due to their high mobility ratio in favor of electrons.

Made available in DSpace on 2021-06-25T10:51:07Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-01-01 New materials discovery is the driving force for progress in solid state physics and chemistry. Here we solve the crystal structure and comprehensively study physical properties of ZnVSb in the polycrystalline form. Synchrotron x-ray diffraction reveals that the compound attains a layered ZrSiS-type structure (P4/nmm, a = 4.09021(2) Å, c = 6.42027(4) Å). The unit cell is composed of a 2D vanadium network separated by Zn-Sb blocks that are slightly distorted from the ideal cubic arrangement. A considerable amount of vacancies were observed on the vanadium and antimony positions; the experimental composition is ZnV0.91Sb0.96. Low-temperature x-ray diffraction shows very subtle discontinuity in the lattice parameters around 175 K. Bonding V-V distance is below the critical separation of 2.97 Å known from the literature, which allows for V-V orbital overlap and subsequent metallic conductivity. From ab initio calculations, we found that ZnVSb is a pseudogap material with an expected dominant vanadium contribution to the density of states at the Fermi level. The energy difference between the antiferromagnetic and nonordered magnetic configurations is rather small (0.34 eV/f.u.). X-ray photoelectron spectroscopy fully corroborates the results of the band structure calculations. Magnetic susceptibility uncovered that, in ZnVSb, itinerant charge carriers coexist with a small, localized magnetic moment of ca. 0.25 μB. The itinerant electrons arise from the ordered part of the vanadium lattice. Fractional localization, in turn, was attributed to V atoms neighboring vacancies, which hinder full V-V orbital overlap. Furthermore, the susceptibility and electrical resistivity showed a large hysteresis between 120 K and 160 K. The effect is not sensitive to magnetic fields up to 9 T. Curie-Weiss fitting revealed that the amount of itinerant charge carriers in ZnVSb drops with decreasing temperature below 160 K, which is accompanied by a concurrent rise in the localized magnetic moment. This observation together with the overall shape of the hysteresis in the resistivity allows for suggesting a plausible origin of the effect as a charge-transfer metal-insulator transition. Ab initio phonon calculations show the formation of a collective phonon mode at 2.8 THz (134 K). The experimental heat capacity reflected this feature by a boson peak with Einstein temperature of 116 K. Analysis of the heat capacity with both an ab initio perspective and Debye-Einstein model revealed a sizable anharmonic contribution to heat capacity, in line with disordered nature of the material. Further investigation of the electron and phonon properties for ZnVSb is likely to provide valuable insight into the relation between structural disorder and the physical properties of transition-metal-bearing compounds. Physics Department Colorado School of Mines Institute of Low Temperature and Structure Research Polish Academy of Sciences University of Illinois at Urbana-Champaign Instituto de Física Teórica São Paulo State University (UNESP) University of California Santa Barbara Max Planck Institute for Chemical Physics of Solids Department of Chemistry and Biochemistry The Ohio State University National Synchrotron Radiation Research Center (NSRRC) Instituto de Física Teórica São Paulo State University (UNESP)

Deeper understanding of electrical and thermal transport is critical for further development of thermoelectric materials. Here we describe the thermoelectric performance of a group of rare-earth-bearing half-Heusler phases determined in a wide temperature range. Polycrystalline samples of $\mathrm{Sc}\mathrm{Ni}\mathrm{Sb}$, $\mathrm{Dy}\mathrm{Ni}\mathrm{Sb}$, $\mathrm{Er}\mathrm{Ni}\mathrm{Sb}$, $\mathrm{Tm}\mathrm{Ni}\mathrm{Sb}$, and $\mathrm{Lu}\mathrm{Ni}\mathrm{Sb}$ are synthesized by arc melting and densified by spark plasma sintering. They are characterized by powder x-ray diffraction and scanning electron microscopy. The physical properties are studied by means of heat-capacity and Hall-effect measurements performed in the temperature range from 2 to 300 K, as well as electrical-resistivity, Seebeck-coefficient, and thermal-conductivity measurements performed in the temperature range from 2 to 950 K. All the materials except $\mathrm{Tm}\mathrm{Ni}\mathrm{Sb}$ are found to be narrow-gap intrinsic $p$-type semiconductors with rather light charge carriers. In $\mathrm{Tm}\mathrm{Ni}\mathrm{Sb}$, the presence of heavy holes with large weighted mobility is evidenced by the highest power factor among the series ($17\phantom{\rule{0.2em}{0ex}}\ensuremath{\mu}\mathrm{W}\phantom{\rule{0.2em}{0ex}}{\mathrm{K}}^{\ensuremath{-}2}\phantom{\rule{0.2em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$ at 700 K). The experimental electronic relaxation time calculated with the parabolic band formalism is found to range from $0.8\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}14}$ to $2.8\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}14}$ s. In all the materials studied, the thermal conductivity is between 3 and $6\phantom{\rule{0.2em}{0ex}}{\mathrm{W m}}^{\ensuremath{-}1}\phantom{\rule{0.2em}{0ex}}{\mathrm{K}}^{\ensuremath{-}1}$ near room temperature (i.e., smaller than in other pristine $d$-electron half-Heusler phases reported in the literature). The experimental observation of the reduced thermal conductivity appears fully consistent with the estimated low sound velocity as well as strong point-defect scattering revealed by Debye-Callaway modeling. Furthermore, analysis of the bipolar contribution to the measured thermal conductivity yields abnormally large differences between the mobilities of $n$-type and $p$-type carriers. The latter feature makes the compounds examined excellent candidates for further optimization of their thermoelectric performance via electron doping.