Many of the recent advances in enhancing the thermoelectric figure of merit are linked to nanoscale phenomena found both in bulk samples containing nanoscale constituents and in nanoscale samples themselves. Prior theoretical and experimental proof‐of‐principle studies on quantum‐well superlattice and quantum‐wire samples have now evolved into studies on bulk samples containing nanostructured constituents prepared by chemical or physical approaches. In this Review, nanostructural composites are shown to exhibit nanostructures and properties that show promise for thermoelectric applications, thus bringing together low‐dimensional and bulk materials for thermoelectric applications. Particular emphasis is given in this Review to the ability to achieve 1) a simultaneous increase in the power factor and a decrease in the thermal conductivity in the same nanocomposite sample and for transport in the same direction and 2) lower values of the thermal conductivity in these nanocomposites as compared to alloy samples of the same chemical composition. The outlook for future research directions for nanocomposite thermoelectric materials is also discussed.
A dimensionless thermoelectric figure-of-merit (ZT) of 0.95 in p-type nanostructured bulk silicon germanium (SiGe) alloys is achieved, which is about 90% higher than what is currently used in space flight missions, and 50% higher than the reported record in p-type SiGe alloys. These nanostructured bulk materials were made by using a direct current-induced hot press of mechanically alloyed nanopowders that were initially synthesized by ball milling of commercial grade Si and Ge chunks with boron powder. The enhancement of ZT is due to a large reduction of thermal conductivity caused by the increased phonon scattering at the grain boundaries of the nanostructures combined with an increased power factor at high temperatures.
Thermoelectric power sources have consistently demonstrated their extraordinary reliability and longevity for deep space missions and small unattended terrestrial systems. However, more efficient bulk materials and practical devices are required to improve existing technology and expand into large‐scale waste heat recovery applications. Research has long focused on complex compounds that best combine the electrical properties of degenerate semiconductors with the low thermal conductivity of glassy materials. Recently it has been found that nanostructuring is an effective method to decouple electrical and thermal transport parameters. Dramatic reductions in the lattice thermal conductivity are achieved by nanostructuring bulk silicon with limited degradation in its electron mobility, leading to an unprecedented increase by a factor of 3.5 in its performance over that of the parent single‐crystal material. This makes nanostructured bulk (nano‐bulk) Si an effective high temperature thermoelectric material that performs at about 70% the level of state‐of‐the‐art Si0.8Ge0.2 but without the need for expensive and rare Ge.
The concept of using "self-assembled" and "force-engineered" nanostructures to enhance the thermoelectric figure of merit relative to bulk homogeneous and composite materials is presented in general terms. Specific application is made to the Si-Ge system for use in power generation at high temperature. The scientific advantages of the nanocomposite approach for the simultaneous increase in the power factor and decrease of the thermal conductivity are emphasized along with the practical advantages of having bulk samples for property measurements and a straightforward path to scale-up materials synthesis and integration of nanostructured materials into thermoelectric cooling and power generation devices.
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