Low-Symmetry Rhombohedral GeTe Thermoelectrics

High-symmetry thermoelectric materials usually have the advantage of very high band degeneracy, while low-symmetry thermoelectrics have the advantage of very low lattice thermal conductivity. If the symmetry breaking of band degeneracy is small, both effects may be realized simultaneously. Here we demonstrate this principle in rhombohedral GeTe alloys, having a slightly reduced symmetry from its cubic structure, to realize a record figure of merit (zT ∼ 2.4) at 600 K. This is enabled by the control of rhombohedral distortion in crystal structure for engineering the split low-symmetry bands to be converged and the resultant compositional complexity for simultaneously reducing the lattice thermal conductivity. Device ZT as high as 1.3 in the rhombohedral phase and 1.5 over the entire working temperature range of GeTe alloys make this material the most efficient thermoelectric to date. This work paves the way for exploring low-symmetry materials as efficient thermoelectrics. Thermoelectric materials enable a heat flow to be directly converted to a flow of charge carriers for generating electricity. The crystal structure symmetry is one of the most fundamental parameters determining the properties of a crystalline material including thermoelectrics. The common belief currently held is that high-symmetry materials are usually good for thermoelectrics, leading to great efforts having historically been focused on GeTe alloys in a high-symmetry cubic structure. Here we show a slight reduction of crystal structure symmetry of GeTe alloys from cubic to rhombohedral, enabling a rearrangement in electronic bands for more transporting channels of charge carriers and many imperfections for more blocking centers of heat-energy carriers (phonons). This leads to the discovery of rhombohedral GeTe alloys as the most efficient thermoelectric materials to date, opening new possibilities for low-symmetry thermoelectric materials. Cubic GeTe thermoelectrics have been historically focused on, while this work utilizes a slight symmetry-breaking strategy to converge the split valence bands, to reduce the lattice thermal conductivity and therefore realize a record thermoelectric performance, all enabled in GeTe in a rhombohedral structure. This not only promotes GeTe alloys as excellent materials for thermoelectric power generation below 800 K, but also expands low-symmetry materials as efficient thermoelectrics

First-principles calculations and experimental studies of: XYZ 2 thermoelectric compounds: Detailed analysis of van der Waals interactions

First-principles calculations can accelerate the search for novel high-performance thermoelectric materials. However, the prediction of the thermoelectric properties is strongly dependent on the approximations used for the calculations. Here, thermoelectric properties were calculated with different computational approximations (i.e., PBE-GGA, HSE06, spin-orbit coupling and DFT-D3) for three layered XYZ2 compounds (TmAgTe2, YAgTe2, and YCuTe2). In addition to the computations, the structural, electrical and thermal properties of these compounds were measured experimentally and compared to the computations. An enhanced prediction of the crystal structure and heat capacity was achieved with the inclusion of van der Waals interactions due to more accurate modeling of the interatomic forces. In particular, a large shift of the acoustic phonons and low-frequency optical phonons to lower frequencies was observed from the dispersion-optimized structure. From the phonon dispersion curves of these compounds, the ultralow thermal conductivity in the investigated XYZ2 compounds could be described by a recent developed minimum thermal conductivity model. For the prediction of the electrical conductivity, a temperature-dependent relaxation time was used, and it was limited by acoustic phonons. While HSE06 has only a small influence on the electrical properties due to a computed band gap energy of >0.25 eV, the inclusion of both van der Waals interactions and spin-orbit coupling leads to a more accurate band structure, resulting in better prediction of electrical properties. Furthermore, the experimental thermoelectric properties of YAgTe2, TmAg0.95Zn0.05Te2 and TmAg0.95Mg0.05Te2 were measured, showing an increase in zT of TmAg0.95Zn0.05Te2 by more than 35% (zT = 0.47 ± 0.12) compared to TmAgTe2

Graphene/Strontium Titanate: Approaching Single Crystal–Like Charge Transport in Polycrystalline Oxide Perovskite Nanocomposites through Grain Boundary Engineering

Grain boundaries critically limit the electronic performance of oxide perovskites. These interfaces lower the carrier mobilities of polycrystalline materials by several orders of magnitude compared to single crystals. Despite extensive effort, improving the mobility of polycrystalline materials (to meet the performance of single crystals) is still a severe challenge. In this work, the grain boundary effect is eliminated in the perovskite strontium titanate by incorporating graphene into the polycrystalline microstructure. An effective mass model provides strong evidence that polycrystalline graphene/strontium titanate nanocomposites approach single crystal-like charge transport. This phenomenological model reduces the complexity of analyzing charge transport properties so that a quantitative comparison can be made between the nanocomposites and strontium titanate single crystals. In other related works, graphene composites also optimize the thermal transport properties of thermoelectric materials. Therefore, decorating grain boundaries with graphene appears to be a robust strategy to achieve “phonon glass–electron crystal” behavior in oxide perovskites.This work has received the funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie individual Fellowship programme No 800031. The authors gratefully acknowledge the support provided by the EPSRC (awards: EP/I036230/1, EP/L014068/1, EP/L017695/1). The authors would also like to acknowledge funding from the National Science Foundation (DMREF-1729487 and DMREF-1333335). As the Research Chair in Carbon Materials, IAK gratefully acknowledges support from Morgan Advanced Materials/ Royal Academy of Engineering. All research data supporting this publication are directly available within the publication

Comparison of the tetrahedron method to smearing methods for the electronic density of states

The electronic density of states (DOS) highlights fundamental properties of materials that oftentimes dictate their properties, such as the band gap and Van Hove singularities. In this short note, we discuss how sharp features of the density of states can be obscured by smearing methods (such as the Gaussian and Fermi smearing methods) when calculating the DOS. While the common approach to reach a "converged" density of states of a material is to increase the discrete k-point mesh density, we show that the DOS calculated by smearing methods can appear to converge but not to the correct DOS. Employing the tetrahedron method for Brillouin zone integration resolves key features of the density of states far better than smearing methods

Expression of interfacial Seebeck coefficient through grain boundary engineering with multi-layer graphene nanoplatelets

Expression of energy filtering to boost thermoelectric performance through grain boundary engineering utilising graphene.</p

Perspective from a Younger Generation -- The Astro-Spectroscopy of Gisbert Winnewisser

Gisbert Winnewisser's astronomical career was practically coextensive with the whole development of molecular radio astronomy. Here I would like to pick out a few of his many contributions, which I, personally, find particularly interesting and put them in the context of newer results.Comment: 14 pages. (Co)authored by members of the MPIfR (Sub)millimeter Astronomy Group. To appear in the Proceedings of the 4th Cologne-Bonn-Zermatt-Symposium "The Dense Interstellar Medium in Galaxies" eds. S. Pfalzner, C. Kramer, C. Straubmeier, & A. Heithausen (Springer: Berlin

A linear nonequilibrium thermodynamics approach to optimization of thermoelectric devices

Improvement of thermoelectric systems in terms of performance and range of applications relies on progress in materials science and optimization of device operation. In this chapter, we focuse on optimization by taking into account the interaction of the system with its environment. For this purpose, we consider the illustrative case of a thermoelectric generator coupled to two temperature baths via heat exchangers characterized by a thermal resistance, and we analyze its working conditions. Our main message is that both electrical and thermal impedance matching conditions must be met for optimal device performance. Our analysis is fundamentally based on linear nonequilibrium thermodynamics using the force-flux formalism. An outlook on mesoscopic systems is also given.Comment: Chapter 14 in "Thermoelectric Nanomaterials", Editors Kunihito Koumoto and Takao Mori, Springer Series in Materials Science Volume 182 (2013

Giant Anharmonic Phonon Scattering in PbTe

Understanding the microscopic processes affecting the bulk thermal conductivity is crucial to develop more efficient thermoelectric materials. PbTe is currently one of the leading thermoelectric materials, largely thanks to its low thermal conductivity. However, the origin of this low thermal conductivity in a simple rocksalt structure has so far been elusive. Using a combination of inelastic neutron scattering measurements and first-principles computations of the phonons, we identify a strong anharmonic coupling between the ferroelectric transverse optic (TO) mode and the longitudinal acoustic (LA) modes in PbTe. This interaction extends over a large portion of reciprocal space, and directly affects the heat-carrying LA phonons. The LA-TO anharmonic coupling is likely to play a central role in explaining the low thermal conductivity of PbTe. The present results provide a microscopic picture of why many good thermoelectric materials are found near a lattice instability of the ferroelectric type

The Characteristics of Seebeck Coefficient in Silicon Nanowires Manufactured by CMOS Compatible Process

Silicon nanowires are patterned down to 30 nm using complementary metal-oxide-semiconductor (CMOS) compatible process. The electrical conductivities of n-/p-leg nanowires are extracted with the variation of width. Using this structure, Seebeck coefficients are measured. The obtained maximum Seebeck coefficient values are 122 μV/K for p-leg and −94 μV/K for n-leg. The maximum attainable power factor is 0.74 mW/m K2 at room temperature