ß-Phase Yb5Sb3Hx: Magnetic and Thermoelectric Properties Traversing from an Electride to a Semiconductor.

An electride is a compound that contains a localized electron in an empty crystallographic site. This class of materials has a wide range of applications, including superconductivity, batteries, photonics, and catalysis. Both polymorphs of Yb5Sb3 (the orthorhombic Ca5Sb3F structure type (ß phase) and hexagonal Mn5Si3 structure type (α phase)) are known to be electrides with electrons localized in 0D tetrahedral cavities and 1D octahedral chains, respectively. In the case of the orthorhombic ß phase, an interstitial H can occupy the 0D tetrahedral cavity, accepting the anionic electron that would otherwise occupy the site, providing the formula of Yb5Sb3Hx. DFT computations show that the hexagonal structure is energetically favored without hydrogen and that the orthorhombic structure is more stable with hydrogen. Polycrystalline samples of orthorhombic ß phase Yb5Sb3Hx (x = 0.25, 0.50, 0.75, 1.0) were synthesized, and both PXRD lattice parameters and 1H MAS NMR were used to characterize H composition. Magnetic and electronic transport properties were measured to characterize the transition from the electride (semimetal) to the semiconductor. Magnetic susceptibility measurements indicate a magnetic moment that can be interpreted as resulting from either the localized antiferromagnetically coupled electride or the presence of a small amount of Yb3+. At lower H content (x = 0.25, 0.50), a low charge carrier mobility consistent with localized electride states is observed. In contrast, at higher H content (x = 0.75, 1.0), a high charge carrier mobility is consistent with free electrons in a semiconductor. All compositions show low thermal conductivity, suggesting a potentially promising thermoelectric material if charge carrier concentration can be fine-tuned. This work provides an understanding of the structure and electronic properties of the electride and semiconductor, Yb5Sb3Hx, and opens the door to the interstitial design of electrides to tune thermoelectric properties.

Thermoelectric Properties of Ba2-xEuxZnSb2, a Zintl Phase with One-Dimensional Covalent Chains.

The compound Ba2ZnSb2 has been predicted to be a promising thermoelectric material, potentially achieving zT > 2 at 900 K due to its one-dimensional chains of edge-shared [ZnSb4/2]4- tetrahedra and interspersed Ba cations. However, the high air sensitivity of this material makes it difficult to measure its thermoelectric properties. In this work, isovalent substitution of Eu for Ba was carried out to make Ba2-xEuxZnSb2 in order to improve the stability of the material in air and to allow characterization of thermal and electronic properties of three different compositions (x = 0.2, 0.3, and 0.4). Polycrystalline samples were synthesized using binary precursors via ball milling and annealing, and their thermoelectric properties were measured. Samples showed low thermal conductivity (<0.8 W/m K), a high Seebeck coefficient (350-550 µV/K), and high charge carrier mobility (20-35 cm2/V) from 300 to 500 K, consistent with predictions of high thermoelectric efficiency. Evaluation of the thermoelectric quality factor suggests that a higher zT can be attained if the carrier concentration can be increased via doping.

Thermoelectricity in transition metal compounds: the role of spin disorder.

At room temperature and above, most magnetic materials adopt a spin-disordered (paramagnetic) state whose electronic properties can differ significantly from their low-temperature, spin-ordered counterparts. Yet computational searches for new functional materials usually assume some type of magnetic order. In the present work, we demonstrate a methodology to incorporate spin disorder in computational searches and predict the electronic properties of the paramagnetic phase. We implement this method in a high-throughput framework to assess the potential for thermoelectric performance of 1350 transition-metal sulfides and find that all magnetic systems we identify as promising in the spin-ordered ground state cease to be promising in the paramagnetic phase due to disorder-induced deterioration of the charge carrier transport properties. We also identify promising non-magnetic candidates that do not suffer from these spin disorder effects. In addition to identifying promising materials, our results offer insights into the apparent scarcity of magnetic systems among known thermoelectrics and highlight the importance of including spin disorder in computational searches.

Effect of extended strain fields on point defect phonon scattering in thermoelectric materials.

The design of thermoelectric materials often involves the integration of point defects (alloying) as a route to reduce the lattice thermal conductivity. Classically, the point defect scattering strength follows from simple considerations such as mass contrast and the presence of induced strain fields (e.g. radius contrast, coordination changes). While the mass contrast can be easily calculated, the associated strain fields induced by defect chemistry are not readily predicted and are poorly understood. In this work, we use classical and first principles calculations to provide insight into the strain field component of phonon scattering from isoelectronic point defects. Our results also integrate experimental measurements on bulk samples of SnSe and associated alloys with S, Te, Ge, Sr and Ba. These efforts highlight that the strength and extent of the resulting strain field depends strongly on defect chemistry. Strain fields can have a profound impact on the local structure. For example, in alloys containing Ba, the strain fields have significant spatial extent (1 nm in diameter) and produce large shifts in the atomic equilibrium positions (up to 0.5 Å). Such chemical complexity suggests that computational assessment of point defects for thermal conductivity depression should be hindered. However, in this work, we present and verify several computational descriptors that correlate well with the experimentally measured strain fields. Furthermore, these descriptors are conceptually transparent and computationally inexpensive, allowing computation to provide a pivotal role in the screening of effective alloys. The further development of point defect engineering could complement or replace nanostructuring when optimizing the thermal conductivity, offering the benefits of thermodynamic stability, and providing more clearly defined defect chemistry.

High Thermoelectric Performance in 2D Sb2Te3 and Bi2Te3 Nanoplate Composites Enabled by Energy Carrier Filtering and Low Thermal Conductivity.

Thermoelectrics are an important class of materials with great potential in alternative energy applications. In this study, two-dimensional (2D) nanoplates of the layered chalcogenides, Sb2Te3 and Bi2Te3, are synthesized and composites of the two are investigated for their thermoelectric properties. The two materials, Sb2Te3 and Bi2Te3, were synthesized as hexagonal, 2D nanoplates via a colloidal polyol route. The as-synthesized Sb2Te3 and Bi2Te3 vary drastically from one another in their lateral and vertical dimensions as revealed by scanning electron microscopy and atomic force microscopy. The single crystalline nanoplate nature is deduced by high-resolution transmission electron microscopy and selected area electron diffraction. Nanoplates have well-defined hexagonal facets as seen in the scanning and transmission electron microscopy images. The nanoplates were consolidated as an anisotropic nanostructured pellet via spark plasma sintering. Preferred orientation observed in the powder X-ray diffraction pattern and scanning electron microscopy images of the fractured pellets confirm the anisotropic structure of the nanoplates. Thermoelectric properties in the parallel and perpendicular directions were measured, revealing strong anisotropy with a significant reduction to thermal conductivity in the perpendicular direction due to increased phonon scattering at nanoplate interfaces. All compositions, except that of the 25% Bi2Te3 nanoplate composite, behave as degenerate semiconductors with increasing electrical resistivity as the temperature increases. The Seebeck coefficient is also increased dramatically in the nanocomposites, the highest reaching 210 µV/K for 15% Bi2Te3. The increase in Seebeck is attributed to energy carrier filtering at the nanoplate interfaces. Overall, these enhanced thermoelectric properties lead to a drastic increase in the thermoelectric performance in the perpendicular direction, with zT ∼ 1.26, for the 15% Bi2Te3 nanoplate composite at 450 K.

Anisotropic proximity-induced superconductivity and edge supercurrent in Kagome metal, K1-xV3Sb5.

Materials with Kagome nets are of particular importance for their potential combination of strong correlation, exotic magnetism, and electronic topology. KV3Sb5 was discovered to be a layered topological metal with a Kagome net of vanadium. Here, we fabricated Josephson Junctions of K1-xV3Sb5 and induced superconductivity over long junction lengths. Through magnetoresistance and current versus phase measurements, we observed a magnetic field sweeping direction-dependent magnetoresistance and an anisotropic interference pattern with a Fraunhofer pattern for in-plane magnetic field but a suppression of critical current for out-of-plane magnetic field. These results indicate an anisotropic internal magnetic field in K1-xV3Sb5 that influences the superconducting coupling in the junction, possibly giving rise to spin-triplet superconductivity. In addition, the observation of long-lived fast oscillations shows evidence of spatially localized conducting channels arising from edge states. These observations pave the way for studying unconventional superconductivity and Josephson device based on Kagome metals with electron correlation and topology.

Study of the Thermoelectric Properties of Bi2Te3/Sb2Te3 Core-Shell Heterojunction Nanostructures.

Thermoelectric materials convert heat energy into electricity, hold promising capabilities for energy waste harvesting, and may be the future of sustainable energy utilization. In this work, we successfully synthesized core-shell Bi2Te3/Sb2Te3 (BTST) nanostructured heterojunctions via a two-step solution route. Samples with different Bi2Te3 core to Sb2Te3 shell ratios could be synthesized by controlling the reaction precursors. Scanning electron microscopy images show well-defined hexagonal nanoplates and the distinct interfaces between Bi2Te3 and Sb2Te3. The similarity of the area ratios with the precursor ratios indicates that the growth of the Sb2Te3 shell mostly took place on the lateral direction rather than the vertical. Transmission electron microscopy revealed the crystalline nature of the as-synthesized Bi2Te3 core and Sb2Te3 shell. Energy-dispersive X-ray spectroscopy verified the lateral growth of a Sb2Te3 shell on the Bi2Te3 core. Thermoelectric properties were measured on pellets obtained from powders via spark plasma sintering with two different directions, in-plane and out-of-plane, showing anisotropic properties due to the nanostructure alignment in the pellets. All samples showed a degenerate semiconducting character with the electrical resistivity increasing with the temperature. Starting from Sb2Te3, the electrical resistivity increases with the increase in amounts of Bi2Te3. Thermal conductivity is lowered due to the increase in interfaces and additional phonon scattering. We show that the out-of-plane direction of the BTST 1-3 sample (where 1-3 indicates the ratio of BT to ST) demonstrates a high Seebeck value of 145 µV/K at 500 K which may be attributed to an energy filtering effect across the heterojunction interfaces. The highest overall zT is observed for the BTST 1-3 sample in the out-of-plane direction at 500 K. The zT values increase continuously over the measured temperature range, indicating a probable higher value at increased temperatures.

Predicted electronic and thermodynamic properties of a newly discovered Zn8Sb7 phase.

A new binary compound, Zn(8)Sb(7), has recently been prepared in nanoparticulate form via solution synthesis. No such phase is known in the bulk phase diagram; instead, one would expect phase separation to the good thermoelectric semiconductors ZnSb and Zn(4)Sb(3). Here, density functional calculations are employed to determine the free energies of formation, including effects from vibrations and configurational disorder, of the relevant phases, yielding insight into the phase stability of Zn(8)Sb(7). Band structure calculations predict Zn(8)Sb(7), much like ZnSb and Zn(4)Sb(3), to be an intermetallic semiconductor with similar thermoelectric properties. If sufficient entropy or surface energy exists to stabilize the bulk material, it would be stable in a limited temperature window at high temperature.

Experimental and computational phase boundary mapping of Co4Sn6Te6.

Binary Co4Sb12 skutterudite (also known as CoSb3) has been extensively studied; however, its mixed-anion counterparts remain largely unexplored in terms of their phase stability and thermoelectric properties. In the search for complex anionic analogs of the binary skutterudite, we begin by investigating the Co4Sb12-Co4Sn6Te6 pseudo-binary phase diagram. We observe no quaternary skutterudite phases and as such, focus our investigations on the ternary Co4Sn6Te6 via experimental phase boundary mapping, transport measurements, and first-principles calculations. Phase boundary mapping using traditional bulk syntheses reveals that the Co4Sn6Te6 exhibits electronic properties ranging from a degenerate p-type behavior to an intrinsic behavior. Under Sn-rich conditions, Hall measurements indicate degenerate p-type carrier concentrations and high hole mobility. The acceptor defect SnTe, and donor defects TeSn and Coi are the predominant defects and rationally correspond to regions of high Sn, Te, and Co, respectively. Consideration of the defect energetics indicates that p-type extrinsic doping is plausible; however, SnTe is likely a killer defect that limits n-type dopability. We find that the hole carrier concentration in Co4Sn6Te6 can be further optimized by extrinsic p-type doping under Sn-rich growth conditions.

Giant, unconventional anomalous Hall effect in the metallic frustrated magnet candidate, KV3Sb5.

The anomalous Hall effect (AHE) is one of the most fundamental phenomena in physics. In the highly conductive regime, ferromagnetic metals have been the focus of past research. Here, we report a giant extrinsic AHE in KV3Sb5, an exfoliable, highly conductive semimetal with Dirac quasiparticles and a vanadium Kagome net. Even without report of long range magnetic order, the anomalous Hall conductivity reaches 15,507 Ω-1 cm-1 with an anomalous Hall ratio of ≈ 1.8%; an order of magnitude larger than Fe. Defying theoretical expectations, KV3Sb5 shows enhanced skew scattering that scales quadratically, not linearly, with the longitudinal conductivity, possibly arising from the combination of highly conductive Dirac quasiparticles with a frustrated magnetic sublattice. This allows the possibility of reaching an anomalous Hall angle of 90° in metals. This observation raises fundamental questions about AHEs and opens new frontiers for AHE and spin Hall effect exploration, particularly in metallic frustrated magnets.

Complex thermoelectric materials.

Thermoelectric materials, which can generate electricity from waste heat or be used as solid-state Peltier coolers, could play an important role in a global sustainable energy solution. Such a development is contingent on identifying materials with higher thermoelectric efficiency than available at present, which is a challenge owing to the conflicting combination of material traits that are required. Nevertheless, because of modern synthesis and characterization techniques, particularly for nanoscale materials, a new era of complex thermoelectric materials is approaching. We review recent advances in the field, highlighting the strategies used to improve the thermopower and reduce the thermal conductivity.

Alloyed Thermoelectric PbTe-SnTe Films Formed via Aerosol Deposition.

The discovery of new thermoelectric materials has the potential to benefit from advances in high-throughput methodologies. Traditional synthesis and characterization routes for thermoelectrics are time-consuming serial processes. In contrast, high-throughput materials discovery is commonly done by thin film growth, which may produce microstructures that are metastable or compositionally graded and, therefore, are challenging to characterize. As a middle ground between bulk synthesis and thin film deposition, we find that the aerosol deposition process can rapidly produce samples that exhibit electronic property trends consistent with those produced by traditional bulk means. We demonstrate rapid growth of discrete thermoelectric thick films of varying chemical compositions (Pb1-xSnxTe) from PbTe and SnTe polydisperse micrometer sized powder feedstocks. The high deposition rate (near 1 µm min-1) and resultant microstructures are advantageous as the diffusion length scales promote rapid thermal treatment and equilibrium phase formation. Room-temperature high-throughput measurements of the Seebeck coefficient and resistivity are compared to traditionally produced bulk materials. The Seebeck coefficient of the films follows the trends of traditional samples, but the resistivity is found to be more sensitive to microstructural effects. Ultimately, we demonstrate a framework for exploratory materials science using aerosol deposition and high-throughput characterization instrumentation.

Template-free routes to porous inorganic materials.

New approaches to solid-state reactivity have allowed us to develop unusual routes to porous inorganic materials. This article describes our recent work on template-free routes involving the selective leaching of one phase from a two-phase composite to form porous oxides. Subsequent reactions have been developed to yield porous metals, conformal coatings, and hierarchically porous materials. Pores can also be generated through simple redox processes in transition-metal oxides; such redox cycling allows mesopores to be produced in a regenerative process in a material which is already macroporous.

Understanding and Control of Bipolar Self-Doping in Copper Nitride.

Semiconductor materials that can be doped both n-type and p-type are desirable for diode-based applications and transistor technology. Copper nitride (Cu3N) is a metastable semiconductor with a solar-relevant bandgap that has been reported to exhibit bipolar doping behavior. However, deeper understanding and better control of the mechanism behind this behavior in Cu3N is currently lacking in the literature. In this work, we use combinatorial growth with a temperature gradient to demonstrate both conduction types of phase-pure, sputter-deposited Cu3N thin films. Room temperature Hall effect and Seebeck effect measurements show n-type Cu3N with an electron density of 1017 cm-3 for low growth temperature (≈ 35 °C) and p-type with a hole density between 1015 cm-3 and 1016 cm-3 for elevated growth temperatures (50 °C to 120 °C). Mobility for both types of Cu3N was ≈ 0.1 cm2/Vs to 1 cm2/V. Additionally, temperature-dependent Hall effect measurements indicate that ionized defects are an important scattering mechanism in p-type films. By combining X-ray absorption spectroscopy and first-principles defect theory, we determined that VCu defects form preferentially in p-type Cu3N while Cui defects form preferentially in n-type Cu3N; suggesting that Cu3N is a compensated semiconductor with conductivity type resulting from a balance between donor and acceptor defects. Based on these theoretical and experimental results, we propose a kinetic defect formation mechanism for bipolar doping in Cu3N, that is also supported by positron annihilation experiments. Overall, the results of this work highlight the importance of kinetic processes in the defect physics of metastable materials, and provide a framework that can be applied when considering the properties of such materials in general.

Measurement of the electrical resistivity and Hall coefficient at high temperatures.

The implementation of the van der Pauw (VDP) technique for combined high temperature measurement of the electrical resistivity and Hall coefficient is described. The VDP method is convenient for use since it accepts sample geometries compatible with other measurements. The technique is simple to use and can be used with samples showing a broad range of shapes and physical properties, from near insulators to metals. Three instruments utilizing the VDP method for measurement of heavily doped semiconductors, such as thermoelectrics, are discussed.

A high temperature apparatus for measurement of the Seebeck coefficient.

A high temperature Seebeck coefficient measurement apparatus with various features to minimize typical sources of error is designed and built. Common sources of temperature and voltage measurement error are described and principles to overcome these are proposed. With these guiding principles, a high temperature Seebeck measurement apparatus with a uniaxial 4-point contact geometry is designed to operate from room temperature to over 1200 K. This instrument design is simple to operate, and suitable for bulk samples with a broad range of physical types and shapes.

Electronic structure and transport in thermoelectric compounds AZn2Sb2 (A = Sr, Ca, Yb, Eu).

The AZn(2)Sb(2) (P3m1, A = Ca, Sr, Eu, Yb) class of Zintl compounds has shown high thermoelectric efficiency (zT approximately 1) and is an appealing system for the development of Zintl structure-property relationships. High temperature transport measurements have previously been conducted for all known compositions except for SrZn(2)Sb(2); here we characterize polycrystalline SrZn(2)Sb(2) to 723 K and review the transport behavior of the other compounds in this class. Consistent with the known AZn(2)Sb(2) compounds, SrZn(2)Sb(2) is found to be a hole-doped semiconductor with a thermal band gap approximately 0.27 eV. The Seebeck coefficients of the AZn(2)Sb(2) compounds are found to be described by similar effective mass (m* approximately 0.6 m(e)). Electronic structure calculations reveal similar m* is due to antimony p states at the valence band edge which are largely unaffected by the choice of A-site species. However, the choice of A-site element has a dramatic effect on the hole mobility, with the room temperature mobility of the rare earth-based compositions approximately double that found for Ca and Sr on the A site. This difference in mobility is examined in the context of electronic structure calculations.

Synthesis, structure, magnetism, and high temperature thermoelectric properties of Ge doped Yb14MnSb11.

The Zintl phase Yb(14)MnSb(11) was successfully doped with Ge utilizing a tin flux technique. The stoichiometry was determined by microprobe analysis to be Yb(13.99(14))Mn(1.05(5))Sb(10.89(16))Ge(0.06(3)). This was the maximum amount of Ge that could be incorporated into the structure via flux synthesis regardless of the amount included in the reaction. Single crystal X-ray diffraction could not unambiguously determine the site occupancy for Ge. Bond lengths varied by about 1% or less, compared with the undoped structure, suggesting that the small amount of Ge dopant does not significantly perturb the structure. Differential scanning calorimetry/thermogravimetry (DSC/TG) show that the doped compound's melting point is greater than 1200 K. The electrical resistivity and magnetism are virtually unchanged from the parent material, suggesting that Yb is present as Yb(2+) and that the Ge dopant has little effect on the magnetic structure. At 900 K the resistivity and Seebeck coefficient decrease resulting in a zT of 0.45 at 1100 K, significantly lower than the undoped compound.

Enhancement of thermoelectric efficiency in PbTe by distortion of the electronic density of states.

The efficiency of thermoelectric energy converters is limited by the material thermoelectric figure of merit (zT). The recent advances in zT based on nanostructures limiting the phonon heat conduction is nearing a fundamental limit: The thermal conductivity cannot be reduced below the amorphous limit. We explored enhancing the Seebeck coefficient through a distortion of the electronic density of states and report a successful implementation through the use of the thallium impurity levels in lead telluride (PbTe). Such band structure engineering results in a doubling of zT in p-type PbTe to above 1.5 at 773 kelvin. Use of this new physical principle in conjunction with nanostructuring to lower the thermal conductivity could further enhance zT and enable more widespread use of thermoelectric systems.

Macroporous manganese oxides with regenerative mesopores.

We demonstrate a simple route to making hierarchically porous MnO. Macropores in Mn3O4 are induced through a process of powder sintering. The loss of volume associated with the reduction of Mn3O4 to MnO results in the formation of mesopores in the walls of a macroporous monolith of MnO. The mesopores are regenerative, in that oxidation closes them up and reduction opens them again.