Yanliang Zhang

A new class of doped nanobulk high-figure-of-merit thermoelectrics by scalable bottom-up assembly

Obtaining thermoelectric materials with high figure of merit ZT is an exacting challenge because it requires the independent control of electrical conductivity, thermal conductivity and Seebeck coefficient, which are often unfavourably coupled. Recent works have devised strategies based on nanostructuring and alloying to address this challenge in thin films, and to obtain bulk p-type alloys with ZT>1. Here, we demonstrate a new class of both p- and n-type bulk nanomaterials with room-temperature ZT as high as 1.1 using a combination of sub-atomic-per-cent doping and nanostructuring. Our nanomaterials were fabricated by bottom-up assembly of sulphur-doped pnictogen chalcogenide nanoplates sculpted by a scalable microwave-stimulated wet-chemical method. Bulk nanomaterials from single-component assemblies or nanoplate mixtures of different materials exhibit 25-250% higher ZT than their non-nanostructured bulk counterparts and state-of-the-art alloys. Adapting our synthesis and assembly approach should enable nanobulk thermoelectrics with further increases in ZT for transforming thermoelectric refrigeration and power harvesting technologies.

Al-Doped Zinc Oxide Nanocomposites with Enhanced Thermoelectric Properties

ZnO is a promising high figure-of-merit (ZT) thermoelectric material for power harvesting from heat due to its high melting point, high electrical conductivity σ, and Seebeck coefficient α, but its practical use is limited by a high lattice thermal conductivity κ(L). Here, we report Al-containing ZnO nanocomposites with up to a factor of 20 lower κ(L) than non-nanostructured ZnO, while retaining bulklike α and σ. We show that enhanced phonon scattering promoted by Al-induced grain refinement and ZnAl(2)O(4) nanoprecipitates presages ultralow κ ∼ 2 Wm( -1) K(-1) at 1000 K. The high α∼ -300 μV K(-1) and high σ ∼ 1-10(4) Ω(-1 )m(-1) result from an offsetting of the nanostructuring-induced mobility decrease by high, and nondegenerate, carrier concentrations obtained via excitation from shallow Al donor states. The resultant ZT ∼ 0.44 at 1000 K is 50% higher than that for the best non-nanostructured counterpart material at the same temperature and holds promise for engineering advanced oxide-based high-ZT thermoelectrics for applications.

Seebeck and Figure of Merit Enhancement in Nanostructured Antimony Telluride by Antisite Defect Suppression through Sulfur Doping

Antimony telluride has a low thermoelectric figure of merit (ZT < ∼0.3) because of a low Seebeck coefficient α arising from high degenerate hole concentrations generated by antimony antisite defects. Here, we mitigate this key problem by suppressing antisite defect formation using subatomic percent sulfur doping. The resultant 10-25% higher α in bulk nanocrystalline antimony telluride leads to ZT ∼ 0.95 at 423 K, which is superior to the best non-nanostructured antimony telluride alloys. Density functional theory calculations indicate that sulfur increases the antisite formation activation energy and presage further improvements leading to ZT ∼ 2 through optimized doping. Our findings are promising for designing novel thermoelectric materials for refrigeration, waste heat recovery, and solar thermal applications.

A microprobe technique for simultaneously measuring thermal conductivity and Seebeck coefficient of thin films

We demonstrate a microprobe technique that can simultaneously measure thermal conductivity κ and Seebeck coefficient α of thin films. In this technique, an alternative current joule-heated V-shaped microwire that serves as heater, thermometer and voltage electrode, locally heats the thin film when contacted with the surface. The κ is extracted from the thermal resistance of the microprobe and α from the Seebeck voltage measured between the probe and unheated regions of the film by modeling heat transfer in the probe, sample and their contact area, and by calibrations with standard reference samples. Application of the technique on sulfur-doped porous Bi2Te3 and Bi2Se3 films reveals α=−105.4 and 1.96 μV/K, respectively, which are within 2% of the values obtained by independent measurements carried out using microfabricated test structures. The respective κ values are 0.36 and 0.52 W/mK, which are significantly lower than the bulk values due to film porosity, and are consistent with effective media theory. ...

High-performance and flexible thermoelectric films by screen printing solution-processed nanoplate crystals

Screen printing allows for direct conversion of thermoelectric nanocrystals into flexible energy harvesters and coolers. However, obtaining flexible thermoelectric materials with high figure of merit ZT through printing is an exacting challenge due to the difficulties to synthesize high-performance thermoelectric inks and the poor density and electrical conductivity of the printed films. Here, we demonstrate high-performance flexible films and devices by screen printing bismuth telluride based nanocrystal inks synthesized using a microwave-stimulated wet-chemical method. Thermoelectric films of several tens of microns thickness were screen printed onto a flexible polyimide substrate followed by cold compaction and sintering. The n-type films demonstrate a peak ZT of 0.43 along with superior flexibility, which is among the highest reported ZT values in flexible thermoelectric materials. A flexible thermoelectric device fabricated using the printed films produces a high power density of 4.1 mW/cm2 with 60 °C temperature difference between the hot side and cold side. The highly scalable and low cost process to fabricate flexible thermoelectric materials and devices demonstrated here opens up many opportunities to transform thermoelectric energy harvesting and cooling applications.

Lattice thermal conductivity diminution and high thermoelectric power factor retention in nanoporous macroassemblies of sulfur-doped bismuth telluride nanocrystals

We report ultralow lattice thermal conductivity in the 0.3 ≤ κL ≤ 0.6 W m−1 K−1 range in nanoporous bulk bismuth telluride pellets obtained by sintering chemically synthesized nanostructures, together with single-crystal-like electron mobilities and Seebeck coefficients at comparable charge carrier concentrations. The observed κL is up to 35% lower than classical effective medium predictions, and can be quantitatively explained by increased phonon scattering at nanopores and nanograins. Our findings are germane to tailoring nanoporous thermoelectric materials for efficient solid-state refrigeration, thermal energy harvesting, and thermal management applications.We report ultralow lattice thermal conductivity in the 0.3 ≤ κL ≤ 0.6 W m−1 K−1 range in nanoporous bulk bismuth telluride pellets obtained by sintering chemically synthesized nanostructures, together with single-crystal-like electron mobilities and Seebeck coefficients at comparable charge carrier concentrations. The observed κL is up to 35% lower than classical effective medium predictions, and can be quantitatively explained by increased phonon scattering at nanopores and nanograins. Our findings are germane to tailoring nanoporous thermoelectric materials for efficient solid-state refrigeration, thermal energy harvesting, and thermal management applications.

A noncontact thermal microprobe for local thermal conductivity measurement

We demonstrate a noncontact thermal microprobe technique for measuring the thermal conductivity κ with ∼3 μm lateral spatial resolution by exploiting quasiballistic air conduction across a 10-100 nm air gap between a joule-heated microprobe and the sample. The thermal conductivity is extracted from the measured effective thermal resistance of the microprobe and the tip-sample thermal contact conductance and radius in the quasiballistic regime determined by calibration on reference samples using a heat transfer model. Our κ values are within 5%-10% of that measured by standard steady-state methods and theoretical predictions for nanostructured bulk and thin film assemblies of pnictogen chalcogenides. Noncontact thermal microprobing demonstrated here mitigates the strong dependence of tip-sample heat transfer on sample surface chemistry and topography inherent in contact methods, and allows the thermal characterization of a wide range of nanomaterials.

Scalable solution-phase epitaxial growth of symmetry-mismatched heterostructures on two-dimensional crystal soft template

Lin et al. report 2D layered materials as a soft template for symmetry-mismatched epitaxial growth of PbSe/Bi2Se3 heterostructures. Epitaxial heterostructures with precisely controlled composition and electronic modulation are of central importance for electronics, optoelectronics, thermoelectrics, and catalysis. In general, epitaxial material growth requires identical or nearly identical crystal structures with small misfit in lattice symmetry and parameters and is typically achieved by vapor-phase depositions in vacuum. We report a scalable solution-phase growth of symmetry-mismatched PbSe/Bi2Se3 epitaxial heterostructures by using two-dimensional (2D) Bi2Se3 nanoplates as soft templates. The dangling bond–free surface of 2D Bi2Se3 nanoplates guides the growth of PbSe crystal without requiring a one-to-one match in the atomic structure, which exerts minimal restriction on the epitaxial layer. With a layered structure and weak van der Waals interlayer interaction, the interface layer in the 2D Bi2Se3 nanoplates can deform to accommodate incoming layer, thus functioning as a soft template for symmetry-mismatched epitaxial growth of cubic PbSe crystal on rhombohedral Bi2Se3 nanoplates. We show that a solution chemistry approach can be readily used for the synthesis of gram-scale PbSe/Bi2Se3 epitaxial heterostructures, in which the square PbSe (001) layer forms on the trigonal/hexagonal (0001) plane of Bi2Se3 nanoplates. We further show that the resulted PbSe/Bi2Se3 heterostructures can be readily processed into bulk pellet with considerably suppressed thermal conductivity (0.30 W/m·K at room temperature) while retaining respectable electrical conductivity, together delivering a thermoelectric figure of merit ZT three times higher than that of the pristine Bi2Se3 nanoplates at 575 K. Our study demonstrates a unique epitaxy mode enabled by the 2D nanocrystal soft template via an affordable and scalable solution chemistry approach. It opens up new opportunities for the creation of diverse epitaxial heterostructures with highly disparate structures and functions.

Optimization of Superlattice Thermoelectric Materials and Microcoolers

The performance of thermoelectric (TE) coolers is determined by the figure of merit of the TE materials ZT. In order to obtain the optimal performance of a superlattice microcooler, both the superlattice structure and the device were optimized in the design and the fabrication process. The thermal conductivities of InGaAs/InGaAsP superlattices with different periodic lengths were measured with the 3omega method. The result indicates that the superlattice at a certain periodic length has minimal thermal conductivity, which, in general, corresponds to an enhanced ZT. A 1D model was utilized to investigate the significant parameters in microcoolers. Based on the modeling results, a set of superlattice microcoolers were fabricated. The maximum cooling temperature that was reached is 0.76degC for the optimized cooler at room temperature.

MHD magnetic fluctuation measurements using a heavy ion beam probe

This paper describes a technique for measuring magnetic fluctuations using a heavy ion beam probe (HIBP) and presents the results of the first experiment to measure locally the internal magnetic structure of MHD modes in a hot, tokamak plasma. In these experiments on the TEXT tokamak, the toroidal position of the HIBP beam at the detector is used to measure the toroidal component of the magnetic vector potential fluctuations, Aφ, at a localized position in the plasma. In an axisymmetric system a purely local measurement is possible. However, the detection method employed and the asymmetries in the tokamak introduce path effects. The importance of the path effects is estimated through numerical simulations of the experiment, and it is found that in this experiment the path effects are small throughout much of the plasma. In addition, toroidal asymmetries reduce the signal amplitude, but do not greatly distort the radial profile. The accuracy of the numerical simulations and detection technique is tested i...