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.

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.

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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.

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