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Engineering grain boundaries (GBs) are effective in tuning the thermoelectric (TE) properties of TE materials, but the role of GB on mechanical properties, which is important for their commercial applications, remains unexplored. In this paper, we apply ab initio method to examine the ideal shear strength and failure mechanism of GBs in TE oxide BiCuSeO. We find that the ideal shear strength of the GB is much lower than that of the ideal single crystal. The atomic rearrangements accommodating the lattice and neighbor structure mismatch between different grains leads to the much weaker GB stiffness compared with grains. Failure of the GBs arises from either the distortion of the Cu–Se layers or the relative slip between Bi–O and Cu–Se layers. This work is crucial to illustrate the deformation of GBs, laying the basis for the development and design of mechanically robust polycrystalline TE materials.

Both n- and p-type lead telluride (PbTe)-based thermoelectric (TE) materials display high TE efficiency, but the low fracture strength may limit their commercial applications. To find ways to improve these macroscopic mechanical properties, we report here the ideal strength and deformation mechanism of PbTe using density functional theory calculations. This provides structure–property relationships at the atomic scale that can be applied to estimate macroscopic mechanical properties such as fracture toughness. Among all the shear and tensile paths that are examined here, we find that the lowest ideal strength of PbTe is 3.46 GPa along the (001)/⟨100⟩ slip system. This leads to an estimated fracture toughness of 0.28 MPa m^(1/2) based on its ideal stress–strain relation, which is in good agreement with our experimental measurement of 0.59 MPa m^(1/2). We find that softening and breaking of the ionic Pb–Te bond leads to the structural collapse. To improve the mechanical strength of PbTe, we suggest strengthening the structural stiffness of the ionic Pb–Te framework through an alloying strategy, such as alloying PbTe with isotypic PbSe or PbS. This point defect strategy has a great potential to develop high-performance PbTe-based materials with robust mechanical properties, which may also be applied to other materials and applications.

Thermoelectric materials require an optimal carrier concentration to maximize electrical transport and thus thermoelectric performance. Element doping and composition off-stoichiometry are the two general and effective approaches for optimizing carrier concentrations, which have been successfully applied in almost all semiconductors. In this study, we propose a new strategy called bonding energy variation to tune the carrier concentrations in Cu2Se-based liquid-like thermoelectric compounds. By utilizing the different bond features in Cu2Se and Cu2S, alloying S at the Se sites successfully increases the bonding energy to fix Cu atoms in the crystal lattice to suppress the formation of Cu vacancies, leading to greatly reduced carrier concentrations toward the optimal value. Via a combination of the lowered electrical and lattice thermal conductivities and the relatively good carrier mobility caused by the weak alloy scattering potential, ultrahigh zT values are achieved in slightly S-doped Cu2Se with a maximal value of 2.0 at 1000 K, 30% higher than that in nominally stoichiometric Cu2Se. © American Chemical Society 2017. This is the authors accepted and refereed manuscript to the article. Locked until 24.7.2018 due to copyright restrictions.

Scandium fluoride (ScF3) exhibits a pronounced negative thermal expansion (NTE), which can be suppressed and ultimately transformed into an isotropic zero thermal expansion (ZTE) by partially substituting Sc with Fe in (Sc0.8Fe0.2)F3 (Fe20). The latter displays a rather small coefficient of thermal expansion of −0.17 × 10–6/K from 300 to 700 K. Synchrotron X-ray and neutron pair distribution functions confirm that the Sc/Fe–F bond has positive thermal expansion (PTE). Local vibrational dynamics based on extended X-ray absorption fine structure indicates a decreased anisotropy of relative vibration in the Sc/Fe–F bond. Combined analysis proposes a delicate balance between the counteracting effects of the chemical bond PTE and NTE from transverse vibration. The present study extends the scope of isotropic ZTE compounds and, more significantly, provides a complete local vibrational dynamics to shed light on the ZTE mechanism in chemically tailored NTE compounds.

The brittle behavior and low strength of CoSb_3/TiCoSb interface are serious issues concerning the engineering applications of CoSb_3 based or CoSb_3/TiCoSb segmented thermoelectric devices. To illustrate the failure mechanism of the CoSb_3/TiCoSb interface, we apply density functional theory to investigate the interfacial behavior and examine the response during tensile deformations. We find that both CoSb_3(100)/TiCoSb(111) and CoSb_3(100)/TiCoSb(110) are energetically favorable interfacial structures. Failure of the CoSb_3/TiCoSb interface occurs in CoSb_3 since the structural stiffness of CoSb_3 is much weaker than that of TiCoSb. This failure within CoSb_3 can be explained through the softening of the Sb–Sb bond along with the cleavage of the Co–Sb bond in the interface. The failure mechanism the CoSb_3/TiCoSb interface is similar to that of bulk CoSb_3, but the ideal tensile strength and failure strain of the CoSb_3/TiCoSb interface are much lower than those of bulk CoSb_3. This can be attributed to the weakened stiffness of the Co–Sb framework due to structural rearrangement near the interfacial region.

To design superior thermoelectric materials the minority carrier blocking effect in which the unwanted bipolar transport is prevented by the interfacial energy barriers in the heterogeneous nanostructures has been theoretically proposed recently. The theory predicts an enhanced power factor and a reduced bipolar thermal conductivity for materials with a relatively low doping level, which could lead to an improvement in the thermoelectric figure of merit (ZT). Here we show the first experimental demonstration of the minority carrier blocking in lead telluride–silver telluride (PbTe–Ag_2Te) nanowire heterostructure-based nanocomposites. The nanocomposites are made by sintering PbTe–Ag_2Te nanowire heterostructures produced in a highly scalable solution-phase synthesis. Compared with Ag_2Te nanowire-based nanocomposite produced in similar method, the PbTe–Ag_2Te nanocomposite containing ∼5 atomic % PbTe exhibits enhanced Seebeck coefficient, reduced thermal conductivity, and ∼40% improved ZT, which can be well explained by the theoretical modeling based on the Boltzmann transport equations when energy barriers for both electrons and holes at the heterostructure interfaces are considered in the calculations. For this p-type PbTe–Ag_2Te nanocomposite, the barriers for electrons, that is, minority carriers, are primarily responsible for the ZT enhancement. By extending this approach to other nanostructured systems, it represents a key step toward low-cost solution-processable nanomaterials without heavy doping level for high-performance thermoelectric energy harvesting.

Inspired by the promising thermoelectric properties of chalcopyrite-like quaternary chalcogenides, here we describe the synthesis and characterization of the solid solution Cu(2)Zn(1-x)Fe(x)GeSe(4). Upon substitution of Zn with the isoelectronic Fe, no charge carriers are introduced in these intrinsic semiconductors. However, a change in lattice parameters, expressed in an elongation of the c/a lattice parameter ratio with minimal change in unit cell volume, reveals the existence of a three-stage cation restructuring process of Cu, Zn, and Fe. The resulting local anisotropic structural disorder leads to phonon scattering not normally observed, resulting in an effective approach to reduce the lattice thermal conductivity in this class of materials.

The first arsenide clathrates A_8Zn_(18)As_(28) (A = K, Rb, Cs) and Cs_8Cd_(18)As_(28) have been synthesized in high yields via a two-step route. These compounds adopt the type-I structure and exhibit structural characteristics different from the recently reported antimonide clathrates Cs_8Zn_(18)Sb_(28) and Cs_8Cd_(18)Sb_(28). In arsenide clathrates, Zn (or Cd) and As atoms are statistically mixed at the three framework sites: 6c, 16i, and 24k; the alkali metals reside inside the cages at the 2a and 6d sites, with the 2a site being only partially filled. Single-crystal X-ray diffraction studies confirm that the Cd atoms preferably occupy the 6c and 24k sites over the 16i site, with more than 80% of Cd found at the former two positions. A unique structural feature is a framework disorder coupled with the partial occupancy of the cage’s 2a site. Optical absorption measurements and electronic property measurements reveal a semimetallic-like behavior for Cs_8Cd_(18)As_(28) and semiconductor-like behavior for A_8Zn_(18)As_(28) (A = Rb, Cs).

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/mK^2 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.

5 páginas, 6 figuras., Films and arrays of 200 and 50 nm diameter wires of Bi2Te3-xSex have been electrodeposited in the following general reaction: 2Bi3+ + (3−y)HTeO2+ + (y)H2SeO3 + (9+y)H+ + 18e- → Bi2Te3-ySey + (6+y)H2O. Films produced from an electrolyte of 0.0075 M Bi, 0.0090 M Te, and 0.0010 M Se in 1 M HNO3 at a potential of 0 V vs Ag/AgCl are single phase with composition Bi2Te2.6Se0.4 as determined by X-ray diffraction, energy-dispersive X-ray spectroscopy, and scanning electron microscopy. Similar conditions yield arrays of 200 and 50 nm Bi2Te3-ySey wires when deposited into porous alumina templates. The wires are single phase, crystalline, and textured, with up to 85% pore filling., This work was funded by the Office of Naval Research under grant number N00014-01-1-1058. Additional support was provided by a Department of Defense ONR-MURI on Thermoelectrics grant, number N00014-97- 1-0516. M.S.M.G thanks MEC/Fulbright for a postdoctoral fellowship and A.L.P. thanks Lucent Technologies, Bell Labs for a CRFP fellowship.