Structural Complexity and Tuned Thermoelectric Properties of a Polymorph of the Zintl Phase Ca2CdSb2 with a Non-centrosymmetric Monoclinic Structure.

The Zintl phase Ca2CdSb2 was found to be dimorphic. Besides the orthorhombic Ca2CdSb2 (-o), here we report on the synthesis, the structural characterization, and the thermoelectric transport properties of its monoclinic form, Ca2CdSb2 (-m), and its Lu-doped variant Ca2-xLuxCdSb2 (x ≈ 0.02). The monoclinic structure exhibits complex structural characteristics and constitutes a new structure type with the non-centrosymmetric space group Cm (Z = 30). The electrical resistivity ρ(T) measured on single crystals of both phases portrays a transition from a semiconductor to a degenerate p-type semiconductor upon doping with Lu and with an attendant change in the Hall carrier concentration nH from 7.15 × 1018 to 2.30 × 1019 cm-3 at 300 K. The Seebeck coefficient S(T) of both phases are comparable and indicate a hole-dominated carrier transport mechanism with magnitudes of 133 and 116 µV/K at 600 K for Ca2CdSb2 (-m) and Ca2-xLuxCdSb2, respectively. The convoluted atomic bonding with an attendant large unit cell volume of ∼4365 Å3 drives a putative low thermal conductivity in these materials resulting in a power factor PF of 1.63 µW/cm K2 and an estimated thermoelectric figure of merit zT of ∼0.5 for Ca2-xLuxCdSb2 at 600 K. Differential scanning calorimetry results reveal the stability of these phases up to about 960 K, making them candidates for moderate temperature thermoelectric materials.

Giant Thermoelectric Power Factor Anisotropy in PtSb1.4Sn0.6.

We report on the giant anisotropy found in the thermoelectric power factor (S2σ) of marcasite structure-type PtSb1.4Sn0.6 single crystal. PtSb1.4Sn0.6, synthesized using an ambient pressure flux growth method upon mixing Sb and Sn on the same atomic site, is a new phase different from both PtSb2 and PtSn2, which crystallize in the cubic Pa3̅ pyrite and Fm3̅m fluorite unit cell symmetry, respectively. The large difference in S2σ for heat flow applied along different principal directions of the orthorhombic unit cell stems mostly from anisotropic Seebeck coefficients.

Two Polymorphs of BaZn2P2: Crystal Structures, Phase Transition, and Transport Properties.

The novel α-BaZn2P2 structural polymorph has been synthesized and structurally characterized for the first time. Its structure, elucidated from single crystal X-ray diffraction, indicates that the compound crystallizes in the orthorhombic α-BaCu2S2 structure type, with unit cell parameters a = 9.7567(14) Å, b = 4.1266(6) Å, and c = 10.6000(15) Å. With ß-BaZn2P2 being previously identified as belonging to the ThCr2Si2 family and with the precedent of structural phase transitions between the α-BaCu2S2 type and the ThCr2Si2 type, the potential for the pattern to be extended to the two different structural forms of BaZn2P2 was explored. Thermal analysis suggests that a first-order phase transition occurs at ∼1123 K, whereby the low-temperature orthorhombic α-phase transforms to a high-temperature tetragonal ß-BaZn2P2, the structure of which was also studied and confirmed by single-crystal X-ray diffraction. Preliminary transport properties and band structure calculations indicate that α-BaZn2P2 is a p-type, narrow-gap semiconductor with a direct bandgap of 0.5 eV, which is an order of magnitude lower than the calculated indirect bandgap for the ß-BaZn2P2 phase. The Seebeck coefficient, S(T), for the material increases steadily from the room temperature value of 119 µV/K to 184 µV/K at 600 K. The electrical resistivity (ρ) of α-BaZn2P2 is relatively high, on the order of 40 mΩ·cm, and the ρ(T) dependence shows gradual decrease upon heating. Such behavior is comparable to those of the typical semimetals or degenerate semiconductors.

Robust three-dimensional type-II Dirac semimetal state in SrAgBi.

Topological semimetals such as Dirac, Weyl or nodal line semimetals are widely studied for their peculiar properties including high Fermi velocities, small effective masses and high magnetoresistance. When the Dirac cone is tilted, exotic phenomena could emerge whereas materials hosting such states are promising for photonics and plasmonics applications. Here we present evidence that SrAgBi is a spin-orbit coupling-induced type-II three-dimensional Dirac semimetal featuring tilted Dirac cone at the Fermi energy. Near charge compensation and Fermi surface characteristics are not much perturbed by 7% of vacancy defects on the Ag atomic site, suggesting that SrAgBi could be a material of interest for observation of robust optical and spintronic topological quantum phenomena.

Materials design, synthesis, and transport properties of disordered rare-earth Zintl bismuthides with the anti-Th3P4 structure type.

The synthesis, structural elucidation, and transport properties of the extended series Ca4-xRExBi3 (RE = Y, La-Nd, Sm, Gd-Tm, and Lu; x ≈ 1) and Ca4-xRExBi3-δSbδ (RE = La, Ho, Er, and Lu; x ≈ 1, δ ≈ 1.5) are presented. Structural elucidation is based on single-crystal X-ray diffraction data and confirms the chemical drive of Ca4Bi3 with the cubic anti-Th3P4 structure type (space group I4̄3d, no. 220, Z = 4) into a Zintl phase by the introduction of trivalent rare-earth atoms. The structure features complex bonding, heavy elements, and electron count akin to that of valence-precise semiconductors, making it an ideal target for thermoelectrics development. Introducing crystallographic site disorders at the cation site for the Ca4-xRExBi3 phase and both the cation and anion sites for the Ca4-xRExBi3-δSbδ phase brings about additional desirable characteristics for thermoelectric materials in the context of tuning knobs for lowering thermal conductivity. Electronic structure calculations of idealized Ca3YBi3 and Ca3LaBi3 compounds indicate the opening of indirect bandgaps at the Fermi level with magnitudes Eg = 0.38 eV and 0.57 eV, respectively. The electrical resistivity ρ(T) of some of the investigated phases measured on single crystals evolve in a metallic manner with magnitudes of order 1.4 mΩ cm near 500 K, thus supporting the notion of a degenerate semiconducting state, with the temperature dependence of the Seebeck coefficient α(T) suggesting the p-type behavior. The low electrical resistivity and the realization of a degenerate semiconducting state in the title phases present a window of opportunity for optimizing their carrier concentrations for enhanced thermoelectric performance.

The Zintl phases AIn2As2 (A = Ca, Sr, Ba): new topological insulators and thermoelectric material candidates.

Recently, there has been a lot of interest in topological insulators (TIs), being electronic materials, which are insulating in their bulk but with the gapless exotic metallic state on their surface. The surface states observed in such materials behave as a perfect conductor thereby making them more suited for several cutting-edge technological applications such as spintronic devices. Here, we report the synthesis and structural characterization of the Zintl phases AIn2As2 (A = Ca, Sr, Ba), which could become a new class of TIs. Crystal structure elucidation by single-crystal X-ray diffraction reveals that CaIn2As2 and SrIn2As2 are isostructural and crystallize in the EuIn2P2 structure type (space group P63/mmc, no. 194, Z = 2) with unit cell parameters a = 4.1482(6) Å, c = 17.726(4) Å; and a = 4.2222(6) Å, c = 18.110(3) Å, respectively. Their hexagonal structure is made up of alternating [In2As2]2- layers separated by slabs of A2+ cations. BaIn2As2 on the other hand crystallizes in the monoclinic EuGa2P2 structure type (space group P2/m, no. 10, Z = 4) with unit cell parameters a = 10.2746(11) Å, b = 4.3005(5) Å, c = 13.3317(14) Å and ß = 95.569(2)°. This structure is also layered, and it is made up of different type of polyanionic [In2As2]2- units and Ba2+ cations. The valence electron count for all three compounds adheres to the Zintl-Klemm formalism, and all elements achieve closed-shell electronic configurations. Bulk electronic structure calculations indicate the opening of a bandgap Eg ∼ 0.03 eV (CaIn2As2 and Sr2In2As2), and Eg ∼0.21 eV (BaIn2As2) in the absence of strain and spin-orbit coupling (SOC). These results argue in favor of the realization of a nontrivial topological insulator state under the influence of tensile strain and SOC. Preliminary transport properties on BaIn2As2 are suggestive of a degenerate p-type semiconductor-a behavior which is sought after in thermoelectric (TE) materials. Since both TIs and excellent TE materials are known to favor the same material properties such as narrow bandgap, heavy elements, and strong SOC, these three Zintl phases are also projected as candidates TE materials.

Promising thermoelectric properties of heavy-fermion semimetal Pr3Os4Ge13.

Here we report the magnetic, electronic and thermal transport properties of the heavy-fermion semimetal Pr3Os4Ge13 with a cage-like structure by means of magnetic susceptibility, χ(T), isothermal magnetization, M(B, T), electrical resistivity, ρ(B, T), Hall coefficient, R H(T), specific heat, C p(T), thermal conductivity, κ(T) and thermoelectric power, S(T). ρ(T) and R H(T) show semimetallic features in a manner that mimics a thermal activated behaviour with an activation energy, Δ/k B = 6.5 K indicating the opening of a small energy gap in the material. At low temperatures, a Sommerfeld coefficient, γ = 128 mJ (mol-1 K-2) observed indicates a mass enhancement of the quasiparticles at low temperatures which bears witness to a heavy fermion state in Pr3Os4Ge13. A Wilson-Sommerfeld ratio, W R and the dimensionless ratio, S/γT of 1.01 and 0.62 ± 0.018 observed, respectively, are in good agreement with the Fermi liquid scenario. S(T) and R H(T) reveal hole dominated transport (p-type material) with a relatively large room temperature value of S(T) = 32.85 ± 0.98 µV K-1. A room temperature low value of κ(T) = 1.61 W K-1 m-1 leads to a thermoelectric figure of merit, ZT = 0.03 ± 0.001 which is comparable to values achieved in several clathrates around the same temperature. Features from S(T) and ρ(T) favour the realization of a higher ZT value at elevated temperatures.

Magnetism and spin-gap behaviour in the layered Pr3 T 4Al12 (T = Fe, Ru, Os) compounds with the distorted Kagomé lattice.

We have investigated the physical and magnetic properties of the distorted Kagomé lattice structure compounds; Pr[Formula: see text]Al12 (T = Fe, Ru, Os) which crystallize in the hexagonal Gd3Ru4Al12-type structure with space group P63/mmc (No. 194). The three compounds show long-range magnetic orderings of FM type at T C = 36.5 K (Fe), 39 K (Ru) and 37 K (Os) as indicated by the temperature dependences of magnetic susceptibility, [Formula: see text], specific heat, C p (T) and electrical resistivity, [Formula: see text]. Pr3Ru4Al12 shows an additional anomaly at 7 K which is associated to possible spin reorientation of some of the Pr moments. We also observed an additional anomaly in Pr3Fe4Al12 at 132 K which might be associated to the formation of a spin density wave. The Sommerfeld coefficient, [Formula: see text] extracted from C p (T) in the temperature range immediately above T C indicate heavy fermion behaviours in Pr[Formula: see text]Al12 (T = Fe, Ru, Os). [Formula: see text] of the three compounds show spin-gap behaviours below T C of comparable energy gaps magnitude.

Absence of a long-range ordered magnetic ground state in Pr3Rh4Sn13 studied through specific heat and inelastic neutron scattering.

Signatures of absence of a long-range ordered magnetic ground state down to 0.36 K are observed in magnetic susceptibility, specific heat, thermal/electrical transport and inelastic neutron scattering data of the quasi-skutterudite compound Pr3Rh4Sn13 which crystallizes in the Yb3Rh4Sn13-type structure with a cage-like network of Sn atoms. In this structure, Pr3+ occupies a lattice site with D 2d point symmetry having a ninefold degeneracy corresponding to J = 4. The magnetic susceptibility of Pr3Rh4Sn13 shows only a weak temperature dependence below 10 K; otherwise remaining paramagnetic-like in the range, 10 K-300 K. From the inelastic neutron scattering intensity of Pr3Rh4Sn13 recorded at different temperatures, we identify excitations at 4.5(7) K, 5.42(6) K, 10.77(5) K, 27.27(5) K, 192.28(4) K and 308.33(3) K through a careful peak analysis. However, no signatures of long-range magnetic order are observed in the neutron data down to 1.5 K, which is also confirmed by the specific heat data down to 0.36 K. A broad Schottky-like peak is recovered for the magnetic part of the specific heat, C 4f, which suggests the role of crystal electric fields of Pr3+ . A crystalline electric field model consisting of 7 levels was applied to C 4f which leads to the estimation of energy levels at 4.48(2) K, 6.94(4) K, 11.23(8) K, 27.01(5) K, 193.12(6) K and 367.30(2) K. The CEF energy levels estimated from the heat capacity analysis are in close agreement with the excitation energies seen in the neutron data. The Sommerfeld coefficient estimated from the analysis of magnetic specific heat is [Formula: see text] mJ K-2 mol-Pr which suggests the formation of heavy itinerant quasi-particles in Pr3Rh4Sn13. Combining inelastic neutron scattering results, analysis of the specific heat data down to 0.36 K, magnetic susceptibility and, electrical and thermal transport, we establish the absence of long-range ordered magnetic ground state in Pr3Rh4Sn13.

Pr-magnetism in the quasi-skutterudite compound PrFe2Al8.

The intermetallic compound PrFe2Al8 that possesses a three-dimensional network structure of Al polyhedra centered at the transition metal element Fe and the rare earth Pr is investigated through neutron powder diffraction and inelastic neutron scattering in order to elucidate the magnetic ground state of Pr and Fe and the crystal field effects of Pr. Our neutron diffraction study confirms long-range magnetic order of Pr below [Formula: see text] K in this compound. Subsequent magnetic structure estimation reveals a magnetic propagation vector [Formula: see text] with a magnetic moment value of [Formula: see text]/Pr along the orthorhombic c-axis and evidence the lack of ordering in the Fe sublattice. The inelastic neutron scattering study reveals one crystalline electric field excitation near 19 meV at 5 K in PrFe2Al8. The energy-integrated intensity of the 19 meV excitation as a function of [Formula: see text] follows the square of the magnetic form factor of [Formula: see text] thereby confirming that the inelastic excitation belongs to the Pr sublattice. The second sum rule applied to the dynamic structure factor indicates only 1.6(2) [Formula: see text] evolving at the 19 meV peak compared to the 3.58 [Formula: see text] for free [Formula: see text], indicating that the crystal field ground state is magnetic and the missing moment is associated with the resolution limited quasi-elastic line. The magnetic order occurring in Pr in PrFe2Al8 is counter-intuitive to the symmetry-allowed crystal field level scheme, hence, is suggestive of exchange-mediated mechanisms of ordering stemming from the magnetic ground state of the crystal field levels.