The dimensionless thermoelectric figure of merit (ZT) in bismuth antimony telluride (BiSbTe) bulk alloys has remained around 1 for more than 50 years. We show that a peak ZT of 1.4 at 100 degrees C can be achieved in a p-type nanocrystalline BiSbTe bulk alloy. These nanocrystalline bulk materials were made by hot pressing nanopowders that were ball-milled from crystalline ingots under inert conditions. Electrical transport measurements, coupled with microstructure studies and modeling, show that the ZT improvement is the result of low thermal conductivity caused by the increased phonon scattering by grain boundaries and defects. More importantly, ZT is about 1.2 at room temperature and 0.8 at 250 degrees C, which makes these materials useful for cooling and power generation. Cooling devices that use these materials have produced high-temperature differences of 86 degrees , 106 degrees , and 119 degrees C with hot-side temperatures set at 50 degrees, 100 degrees, and 150 degrees C, respectively. This discovery sets the stage for use of a new nanocomposite approach in developing high-performance low-cost bulk thermoelectric materials.

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Coherent Heat Flow Typically, heat in solids is transported incoherently because phonons scatter at interfaces and defects. Luckyanova et al. (p. 936 ) grew super-lattice films made from one to nine repeats of layers of GaAs and AlAs, each 12-nm thick. Thermal conductivity through this sandwich structure increased linearly with the number of superlattice repeats, which is consistent with theoretical simulations of coherent heat transport.

Recently a significant figure‐of‐merit (ZT) improvement in the most‐studied existing thermoelectric materials has been achieved by creating nanograins and nanostructures in the grains using the combination of high‐energy ball milling and a direct‐current‐induced hot‐press process. Thermoelectric transport measurements, coupled with microstructure studies and theoretical modeling, show that the ZT improvement is the result of low lattice thermal conductivity due to the increased phonon scattering by grain boundaries and structural defects. In this article, the synthesis process and the relationship between the microstructures and the thermoelectric properties of the nanostructured thermoelectric bulk materials with an enhanced ZT value are reviewed. It is expected that the nanostructured materials described here will be useful for a variety of applications such as waste heat recovery, solar energy conversion, and environmentally friendly refrigeration.

Size effects in heat conduction, which occur when phonon mean free paths (MFPs) are comparable to characteristic lengths, are being extensively explored in many nanoscale systems for energy applications. Knowledge of MFPs is essential to understanding size effects, yet MFPs are largely unknown for most materials. Here, we introduce the first experimental technique which can measure MFP distributions over a wide range of length scales and materials. Using this technique, we measure the MFP distribution of silicon for the first time and obtain good agreement with first-principles calculations.

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We introduce the concept of modulation doping in three-dimensional nanostructured bulk materials to increase the thermoelectric figure of merit. Modulation-doped samples are made of two types of nanograins (a two-phase composite), where dopants are incorporated only into one type. By band engineering, charge carriers could be separated from their parent grains and moved into undoped grains, which would result in enhanced mobility of the carriers in comparison to uniform doping due to a reduction of ionized impurity scattering. The electrical conductivity of the two-phase composite can exceed that of the individual components, leading to a higher power factor. We here demonstrate the concept via experiment using composites made of doped silicon nanograins and intrinsic silicon germanium grains.