Although the thermoelectric figure of merit zT above 300 K has seen significant improvement recently, the progress at lower temperatures has been slow, mainly limited by the relatively low Seebeck coefficient and high thermal conductivity. Here we report, for the first time to our knowledge, success in first-principles computation of the phonon drag effect--a coupling phenomenon between electrons and nonequilibrium phonons--in heavily doped region and its optimization to enhance the Seebeck coefficient while reducing the phonon thermal conductivity by nanostructuring. Our simulation quantitatively identifies the major phonons contributing to the phonon drag, which are spectrally distinct from those carrying heat, and further reveals that although the phonon drag is reduced in heavily doped samples, a significant contribution to Seebeck coefficient still exists. An ideal phonon filter is proposed to enhance zT of silicon at room temperature by a factor of 20 to ∼ 0.25, and the enhancement can reach 70 times at 100 K. This work opens up a new venue toward better thermoelectrics by harnessing nonequilibrium phonons.

Heat conduction in semiconductors and dielectrics depends upon their phonon mean free paths that describe the average travelling distance between two consecutive phonon scattering events. Nondiffusive phonon transport is being exploited to extract phonon mean free path distributions. Here, we describe an implementation of a nanoscale thermal conductivity spectroscopy technique that allows for the study of mean free path distributions in optically absorbing materials with relatively simple fabrication and a straightforward analysis scheme. We pattern 1D metallic grating of various line widths but fixed gap size on sample surfaces. The metal lines serve as both heaters and thermometers in time-domain thermoreflectance measurements and simultaneously act as wire-grid polarizers that protect the underlying substrate from direct optical excitation and heating. We demonstrate the viability of this technique by studying length-dependent thermal conductivities of silicon at various temperatures. The thermal conductivities measured with different metal line widths are analyzed using suppression functions calculated from the Boltzmann transport equation to extract the phonon mean free path distributions with no calibration required. This table-top ultrafast thermal transport spectroscopy technique enables the study of mean free path spectra in a wide range of technologically important materials.