Steven N. Girard

High Performance Na-doped PbTe–PbS Thermoelectric Materials: Electronic Density of States Modification and Shape-Controlled Nanostructures

Thermoelectric heat-to-power generation is an attractive option for robust and environmentally friendly renewable energy production. Historically, the performance of thermoelectric materials has been limited by low efficiencies, related to the thermoelectric figure-of-merit ZT. Nanostructuring thermoelectric materials have shown to enhance ZT primarily via increasing phonon scattering, beneficially reducing lattice thermal conductivity. Conversely, density-of-states (DOS) engineering has also enhanced electronic transport properties. However, successfully joining the two approaches has proved elusive. Herein, we report a thermoelectric materials system whereby we can control both nanostructure formations to effectively reduce thermal conductivity, while concurrently modifying the electronic structure to significantly enhance thermoelectric power factor. We report that the thermoelectric system PbTe-PbS 12% doped with 2% Na produces shape-controlled cubic PbS nanostructures, which help reduce lattice thermal conductivity, while altering the solubility of PbS within the PbTe matrix beneficially modifies the DOS that allow for enhancements in thermoelectric power factor. These concomitant and synergistic effects result in a maximum ZT for 2% Na-doped PbTe-PbS 12% of 1.8 at 800 K.

On the origin of increased phonon scattering in nanostructured PbTe based thermoelectric materials.

We have investigated the possible mechanisms of phonon scattering by nanostructures and defects in PbTe-X (X = 2% Sb, Bi, or Pb) thermoelectric materials systems. We find that among these three compositions, PbTe-2% Sb has the lowest lattice thermal conductivity and exhibits a larger strain and notably more misfit dislocations at the precipitate/PbTe interfaces than the other two compositions. In the PbTe-Bi 2% sample, we infer some weaker phonon scattering BiTe precipitates, in addition to the abundant Bi nanostructures. In the PbTe-Pb 2% sample, we also find that pure Pb nanoparticles exhibit stronger phonon scattering than nanostructures with Te vacancies. Within the accepted error range, the theoretical calculations of the lattice thermal conductivity in the three systems are in close agreement with the experimental measurements, highlighting the important role of misfit dislocations, nanoscale particles, and associated interfacial elastic strain play in phonon scattering. We further propose that such particle-induced local elastic perturbations interfere with the phonon propagation pathway, thereby contributing to further reduction in lattice thermal conductivity, and consequently can enhance the overall thermoelectric figure of merit.

In situ nanostructure generation and evolution within a bulk thermoelectric material to reduce lattice thermal conductivity

We show experimentally the direct reduction in lattice thermal conductivity as a result of in situ nanostructure generation within a thermoelectric material. Solid solution alloys of the high-performance thermoelectric PbTe-PbS 8% can be synthesized through rapid cooling and subsequent high-temperature activation that induces a spontaneous nucleation and growth of PbS nanocrystals. The emergence of coherent PbS nanostructures reduces the lattice thermal conductivity from approximately 1 to approximately 0.4 W/mK between 400 and 500 K.

Strong Phonon Scattering by Layer Structured PbSnS2 in PbTe Based Thermoelectric Materials

The incorporation of PbSnS(2) in PbTe results in a tremendous reduction of the lattice thermal conductivity to 0.8 W/mK at room temperature, a reduction of almost 60% over bulk PbTe. Transmission electron microscopy reveals very high density displacement layers, misfit dislocations, and phase boundaries. Our thermal transport calculations based on modified Debye-Callaway model, well in agreement with the experimental measurements, reveal that the layer structured PbSnS(2) plays an important role in reducing the lattice thermal conductivity.

Morphology Control of Nanostructures: Na-Doped PbTe–PbS System

The morphology of crystalline precipitates in a solid-state matrix is governed by complex but tractable energetic considerations driven largely by volume strain energy minimization and anisotropy of interfacial energies. Spherical precipitate morphologies are favored by isotropic systems, while anisotropic interfacial energies give energetic preference to certain crystallographically oriented interfaces, resulting in a faceted precipitate morphology. In conventional solid-solution precipitation, a precipitates morphological evolution is mediated by surface anchoring of capping molecules, which dramatically alter the surface energy in an anisotropic manner, thereby providing exquisite morphology control during crystal growth. Herein, we present experimental evidence and theoretical validation for the role of a ternary element (Na) in controlling the morphology of nanoscale PbS crystals nucleating in a PbTe matrix, an important bulk thermoelectric system. The PbS nanostructures formed by phase separation from a PbI(2)-doped or undoped PbTe matrix have irregular morphologies. However, replacing the iodine dopant with Na (1-2 mol %) alters dramatically the morphology of the PbS precipitates. Segregation of Na at PbTe/PbS interfaces result in cuboidal and truncated cuboidal morphologies for PbS. Using analytical scanning/transmission electron microscopy and atom-probe tomography, we demonstrate unambiguously that Na partitions to the precipitates and segregates at the matrix/precipitate interfaces, inducing morphological anisotropy of PbS precipitates. First-principles and semiclassical calculations reveal that Na as a solute in PbTe has a higher energy than in PbS and that Na segregation at a (100) PbTe/PbS interface decreases the total energy of matrix/precipitate system, resulting in faceting of PbS precipitates. These results provide an impetus for a new strategy for controlling morphological evolution in matrix/precipitate systems, mediated by solute partitioning of ternary additions.

Anomalous electronic transport in dual-nanostructured lead telluride

The Pb- and Sb- dual nanostructured PbTe system exhibits anomalous electronic transport behavior wherein the carrier mobility first increases and then decreases with increase in temperature. By combining in situ transmission electron microscopy observations and theoretical calculations based on energy filtering of charge carriers, we propose a plausible mechanism of charge transport based on interphase potential that is mediated by interdiffusion between coexisting Pb and Sb precipitates. These findings promise new strategies to enhance thermoelectric figure of merit via dual and multinanostructuring of miscible precipitates.

On the Study of PbTe-Based Nanocomposite Thermoelectric Materials

We Report on the Structural and Vibrational Properties of the X = 0.11 and X = 0.33 Compositions of a New Class of Nanostructured Thermoelectric System (PbTe)1-X(PbSnS2)x by Means of X-Ray Diffraction, Scanning and Transmission Electron Microscopy and Infrared Reflectivity. both Compositions Are Phase Separated, where Pbsns2 Self-Segregates from Pbte to Form Features with Dimensions Ranging from Tens of Micrometers to Tens of Nanometers. Effective Medium Approximation Was Used in Order to Determine the Volume Fraction and the Dielectric Function of the Nanoscale Pbsns2 Embedded in Pbte. by Comparing the Phonon Parameters of the Nanoscale Pbsns2 and Bulk Pbsns2 Single Crystals, we Concluded that Phonon Confinement Effects and Bilayer Thickness Anisotropy within the Pbsns2 Nanostructures Embedded within Pbte Are Responsible for the Observed Variations in the Frequencies of the Shear and the Compression Modes Not Observed in Pure Crystals of Pbsns2.

Investigation of solid-state immiscibility and thermoelectric properties of the system PbTe - PbS

We have shown that (Pb 1-m Sn m Te) 1-x (PbS) x where m = 0.05 and x = 0.08 exhibits a ZT of ˜1.4 at 700 K. This system incorporates two thermoelectric systems: PbS x Te 1-x and Pb 1-x Sn x Te. Here we report the thermoelectric properties of PbS x Te 1-x (x = 0.08 and 0.30). The material PbS 0.08 Te 0.92 exhibits nucleation and growth of PbS precipitates, while PbS 0.30 Te 0.70 exhibits PbS precipitation through spinodal decomposition phase separation. We report the thermoelectric properties of this system as a result of the differing precipitation phenomena.

Electron-beam activated thermal sputtering of thermoelectric materials

Thermoelectricity and Seebeck effect have long been observed and validated in bulk materials. With the development of advanced tools of materials characterization, here we report the first observation of such an effect in the nanometer scale: in situ directional sputtering of several thermoelectric materials inside electron microscopes. The temperature gradient introduced by the electron beam creates a voltage-drop across the samples, which enhances spontaneous sputtering of specimen ions. The sputtering occurs along a preferential direction determined by the direction of the temperature gradient. A large number of nanoparticles form and accumulate away from the beam location as a result. The sputtering and re-crystallization are found to occur at temperatures far below the melting points of bulk materials. The sputtering occurs even when a liquid nitrogen cooling holder is used to keep the overall temperature at −170 °C. This unique phenomenon that occurred in the nanometer scale may provide useful clues...

Thermoelectric properties of composite PbTe - PbSnS2 materials

The thermoelectric (Pb 1-m Sn m Te) 1-x (PbS) x where m = 0.05 and x = 0.08 has been shown to produce PbS nanostructures that effectively scatter phonons, enhancing ZT. As Sn substitution is increased, a new phase of PbSnS 2 precipitates. We find that incorporation of PbSnS 2 in PbTe results in a significant reduction in lattice thermal conductivity around 0.6 W/mK at room temperature. We present preliminary characterization and thermoelectric properties.