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/cm(2) 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.

Harnessing Topological Band Effects in Bismuth Telluride Selenide for Large Enhancements in Thermoelectric Properties through Isovalent Doping.

Dilute isovalent sulfur doping simultaneously increases electrical conductivity and Seebeck coefficient in Bi2 Te2 Se nanoplates, and bulk pellets made from them. This unusual trend at high electron concentrations is underpinned by multifold increases in electron effective mass attributable to sulfur-induced band topology effects, providing a new way for accessing a high thermoelectric figure-of-merit in topological-insulator-based nanomaterials through doping.

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 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.

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.

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 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.