Rutvik J. Mehta

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 Tuning in Chalcogenide Nanoplate Assemblies by Nanoscale Heterostructuring

Chalcogenide nanostructures offer promise for obtaining nanomaterials with high electrical conductivity, low thermal conductivity, and high Seebeck coefficient. Here, we demonstrate a new approach of tuning the Seebeck coefficient of nanoplate assemblies of single-crystal pnictogen chalcogenides by heterostructuring the nanoplates with tellurium nanocrystals. We synthesized bismuth telluride and antimony telluride nanoplates decorated with tellurium nanorods and nanofins using a rapid, scalable, microwave-stimulated organic surfactant-directed technique. Heterostructuring permits two- to three-fold factorial tuning of the Seebeck coefficient, and yields a 40% higher value than the highest reported for bulk antimony telluride. Microscopy and spectroscopy analyses of the nanostructures suggest that Seebeck tunability arises from carrier-energy filtration effects at the Te-chalcogenide heterointerfaces. Our approach of heterostructuring nanoscale building blocks is attractive for realizing high figure-of-merit thermoelectric nanomaterials.

Raman study of interfacial load transfer in graphene nanocomposites

We tracked the strain-sensitive characteristic Raman G-band shift of graphene platelets in polydimethyl-siloxane (PDMS) nanocomposites revealing the filler-to-matrix interactions. We obtained large debonding strains of ∼7% for graphene in PDMS, with the peak shift rate with strain being ∼2.4 cm−1/composite strain % in comparison to single-walled carbon nanotube composites, where a relatively low rate of ∼0.1 cm−1/composite strain % was obtained, suggesting enhanced load-transfer effectiveness for graphene. A surprising observation was that for large strains (>1.5%) the graphene fillers went into compression under uniaxial tensile deformation and vice versa. We propose that this effect is related to the high mobility of the PDMS chains at room temperature.

High Electrical Conductivity Antimony Selenide Nanocrystals and Assemblies

Antimony selenide is a promising thermoelectric material with a high Seebeck coefficient, but its figure of merit is limited by its low electrical conductivity. Here, we report a rapid and scalable (gram-a-minute) microwave synthesis of one-dimensional nanocrystals of sulfurized antimony selenide that exhibit 10(4)-10(10) times higher electrical conductivity than non-nanostructured bulk or thin film forms of this material. As the nanocrystal diameter increases, the nanowires transform into nanotubes through void formation and coalescence driven by axial rejection of sulfur incorporated into the nanowires from the surfactant used in our synthesis. Individual nanowires and nanotubes exhibit a charge carrier transport activation-energy of <60 meV arising from surface sulfur donor states. Nanocrystal assemblies also show high electrical conductivity, making the nanocrystals attractive building blocks to realize nanostructured thin film and bulk forms of this material for thermoelectric device 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. ...

Nanowire-filled polymer composites with ultrahigh thermal conductivity

Realizing high thermal conductivity nanocomposites is a challenge because of difficulties in incorporating high fractions of uniformly dispersed nanofillers and countering low filler-matrix interfacial conductance. Here, we obviate these issues by using <3 vol. % gold nanowire fillers to obtain a 30-fold increase in polydimethylsiloxane thermal conductivity that is 6-fold higher than any nanocomposite at low nanofiller loadings and exceeds theoretical predictions. The nanowire diameter and aspect ratio are keys to obtaining cold-welded networks that enhance thermal conductivity while fostering low modulus and electrical conductivity. Such nanowire nanocomposites are attractive for many applications in electronics, packaging, and energy devices.

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.