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Register a new userPhonon-glass electron-crystal thermoelectric clathrates: Experiments and theory
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Type-I clathrate compounds have attracted a great deal of interest in connection with the search for efficient thermoelectric materials. These compounds constitute networked cages consisting of nano-scale tetrakaidecahedrons (14 hedrons) and dodecahedrons (12 hedrons), in which the group 1 or 2 elements in the periodic table are encaged as the so-called rattling guest atom. It is remarkable that, though these compounds have crystalline cubic-structure, they exhibit glass-like phonon thermal conductivity over the whole temperature range depending on the states of rattling guest atoms in the tetrakaidecahedron. In addition, these compounds show unusual glass-like specific heats and THz-frequency phonon dynamics, providing a remarkable broad peak almost identical to those observed in topologically disordered amorphous materials or structural glasses, the so-called Boson peak. An efficient thermoelectric effect is realized in compounds showing these glass-like characteristics. This decade, a number of experimental works dealing with type-I clathrate compounds have been published. These are diffraction experiments, thermal and spectroscopic experiments in addition to those based on heat and electronic transport. These form the raw materials for this article based on advances this decade. The subject of this article involves interesting phenomena from the viewpoint of not only physics but also from the view point of the practical problem of elaborating efficient thermoelectric materials. This review presents a survey of a wide range of experimental investigations of type-I clathrate compounds, together with a review of theoretical interpretations of the peculiar thermal and dynamic properties observed in these materials.
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Ion beam irradiation has recently emerged as a versatile approach to functional materials design. We show in this work that patterned defective regions generated by ion beam irradiation of silicon can create a phonon glass electron crystal (PGEC), a longstanding goal of thermoelectrics. By controlling the effective diameter of and spacing between the defective regions, molecular dynamics simulations suggest a reduction of the thermal conductivity by a factor of $approx$20 is achievable. Boltzmann theory shows that the thermoelectric power factor remains largely intact in the damaged material. To facilitate the Boltzmann theory, we derive an analytical model for electron scattering with cylindrical defective regions based on partial wave analysis. Together we predict a figure of merit of ZT$approx$0.5 or more at room temperature for optimally patterned geometries of these silicon metamaterials. These findings indicate that nanostructuring of patterned defective regions in crystalline materials is a viable approach to realize a PGEC, and ion beam irradiation could be a promising fabrication strategy.
Crystalline solids are generally known as excellent heat conductors, amorphous materials or glasses as thermal insulators. It has thus come as a surprise that certain crystal structures defy this paradigm. A prominent example are type-I clathrates and other materials with guest-host structures. They sustain low-energy Einstein-like modes in their phonon spectra, but are also prone to various types of disorder and phonon-electron scattering and thus the mechanism responsible for their ultralow thermal conductivities has remained elusive. While recent ab initio lattice dynamics simulations show that the Einstein-like modes enhance phonon-phonon Umklapp scattering, they reproduce experimental data only at low temperatures. Here we show that a new effect, an all phononic Kondo effect, can resolve this discrepancy. This is evidenced by our thermodynamic and transport measurements on various clathrate single crystal series and their comparison with ab initio simulations. Our new understanding devises design strategies to further suppress the thermal conductivity of clathrates and other related materials classes, with relevance for the field of thermoelectric waste heat recovery but also more generally for phononic applications. More fundamentally, it may trigger theoretical work on strong correlation effects in phonon systems.
In most materials, transport can be described by the motion of distinct species of quasiparticles, such as electrons and phonons. Strong interactions between quasiparticles, however, can lead to collective behaviour, including the possibility of viscous hydrodynamic flow. In the case of electrons and phonons, an electron-phonon fluid is expected to exhibit strong phonon-drag transport signatures and an anomalously low thermal conductivity. The Dirac semi-metal PtSn4 has a very low resistivity at low temperatures and shows a pronounced phonon drag peak in the low temperature thermopower; it is therefore an excellent candidate for hosting a hydrodynamic electron-phonon fluid. Here we report measurements of the temperature and magnetic field dependence of the longitudinal and Hall electrical resistivities, the thermopower and the thermal conductivity of PtSn4. We confirm a phonon drag peak in the thermopower near 14 K and observe a concurrent breakdown of the Lorenz ratio below the Sommerfeld value. Both of these facts are expected for an electron-phonon fluid with a quasi-conserved total momentum. A hierarchy between momentum-conserving and momentum-relaxing scattering timescales is corroborated through measurements of the magnetic field dependence of the electrical and Hall resistivity and of the thermal conductivity. These results show that PtSn4 exhibits key features of hydrodynamic transport.
We describe 27Al NMR experiments on Ba8AlxGe46-x type-I clathrates coupled with ab initio computational studies. For x=16, calculated spectra determined by the ab initio results gave good agreement with the measurements, with best-fitting configurations also corresponding to the computed lowest-energy atomic arrangements. Analysis of the NMR results showed that a distribution of Knight shifts dominates the central portion of the line. Computational results demonstrate that this stems from the large variation of carrier density on different sites. Al-deficient samples with x=12 and 13 exhibited a split central NMR peak, signaling two main local environments for Al ions, which we connected to the presence of vacancies. Modeling of the wide-line spectrum for x=12 indicates a configuration with more Al on the 24k site than for x=16. The results indicate the importance of nonbonding hybrids adjacent to the vacancies in the electronic structure near EF. We also address the static distortions from Pm-3n symmetry in these structures.
Low-dimensional electronic and glassy phononic transport are two important ingredients of highly-efficient thermoelectric material, from which two branches of the thermoelectric research emerge. One focuses on controlling electronic transport in the low dimension, while the other on multiscale phonon engineering in the bulk. Recent work has benefited much from combining these two approaches, e.g., phonon engineering in low-dimensional materials. Here, we propose to employ the low-dimensional electronic structure in bulk phonon-glass crystal as an alternative way to increase the thermoelectric efficiency. Through first-principles electronic structure calculation and classical molecular dynamics simulation, we show that the $pi$-$pi$ stacking Bis-Dithienothiophene molecular crystal is a natural candidate for such an approach. This is determined by the nature of its chemical bonding. Without any optimization of the material parameter, we obtain a maximum room-temperature figure of merit, $ZT$, of $1.48$ at optimal doping, thus validating our idea.
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