Skutterudites CoSb3 with multiple cofillers Ba, La, and Yb were synthesized and very high thermoelectric figure of merit ZT = 1.7 at 850 K was realized. X-ray diffraction of the densified multiple-filled bulk samples reveals all samples are phase pure. High-resolution scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDS) analysis confirm that multiple guest fillers occupy the nanoscale-cages in the skutterudites. The fillers are further shown to be uniformly distributed and the Co−Sb skutterudite framework is virtually unperturbed from atomic scale to a few micrometers. Our results firmly show that high power factors can be realized by adjusting the total filling fraction of fillers with different charge states to reach the optimum carrier density, at the same time, lattice thermal conductivity can also be significantly reduced, to values near the glass limit of these materials, through combining filler species of different rattling frequencies to achieve broad-fr...

Multiple-filled skutterudites: high thermoelectric figure of merit through separately optimizing electrical and thermal transports.

Thermoelectric materials: Energy conversion between heat and electricity

This review discusses recent developments and current research in high performance bulk thermoelectric materials, comprising nanostructuring, mesostructuring, band alignment, band engineering and synergistically defining key strategies for boosting the thermoelectric performance. To date, the dramatic enhancements in the figure of merit achieved in bulk thermoelectric materials have come either from the reduction in lattice thermal conductivity or improvement in power factors, or both of them. Here, we summarize these relationships between very large reduction of the lattice thermal conductivity with all-scale hierarchical architecturing, large enhanced Seebeck coefficients with intra-matrix electronic structure engineering, and control of the carrier mobility with matrix/inclusion band alignment, which enhance the power factor and reduce the lattice thermal conductivity. The new concept of hierarchical compositionally alloyed nanostructures to achieve these effects is presented. Systems based on PbTe, PbSe and PbS in which spectacular advances have been demonstrated are given particular emphasis. A discussion of future possible strategies is aimed at enhancing the thermoelectric figure of merit of these materials.

The panoscopic approach to high performance thermoelectrics

Thermoelectric effects enable direct conversion between thermal and electrical energy and provide an alternative route for power generation and refrigeration. Over the past ten years, the exploration of high-performance thermoelectric materials has attracted great attention from both an academic research perspective and with a view to industrial applications. This review summarizes the progress that has been made in recent years in developing thermoelectric materials with a high dimensionless figure of merits (ZT) and the related fabrication processes for producing nanostuctured materials. The challenge to develop thermoelectric materials with superior performance is to tailor the interconnected thermoelectric physical parameters — electrical conductivity, Seebeck coefficient and thermal conductivity — for a crystalline system. Nanostructures provide a chance to disconnect the linkage between thermal and electrical transport by introducing some new scattering mechanisms. Recent improvements in thermoelectric efficiency appear to be dominated by efforts to reduce the lattice thermal conductivity through nanostructural design. The materials focused in this review include Bi–Te alloys, skutterudite compounds, Ag–Pb–Sb–Te quaternary systems, half-Heusler compounds and some high-ZT oxides. Possible future strategies for developing thermoelectric materials are also discussed.

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High-performance nanostructured thermoelectric materials

Recently a significant figure-of-merit (ZT) improvement in the most-studied existing thermoelectric materials has been achieved by creating nanograins and nanostructures in the grains using the combination of high-energy ball milling and a direct-current-induced hot-press process. Thermoelectric transport measurements, coupled with microstructure studies and theoretical modeling, show that the ZT improvement is the result of low lattice thermal conductivity due to the increased phonon scattering by grain boundaries and structural defects. In this article, the synthesis process and the relationship between the microstructures and the thermoelectric properties of the nanostructured thermoelectric bulk materials with an enhanced ZT value are reviewed. It is expected that the nanostructured materials described here will be useful for a variety of applications such as waste heat recovery, solar energy conversion, and environmentally friendly refrigeration.

Enhancement of Thermoelectric Figure-of-Merit by a Bulk Nanostructuring Approach

Composites containing Yb-filled CoSb3 and well-distributed Yb2O3 particles are synthesized by in situ reaction method. The structural, chemical, and transport properties of the composites are studied. Some Yb2O3 particles with microsize locate at the grain boundaries of matrix and others distribute within YbyCo4Sb12 grains as nanoscale inclusions. The combination of the “rattling” of Yb ions inside the voids of CoSb3 and the phonon scattering of the oxide defects results in a remarkable reduction in the lattice thermal conductivity. The thermoelectric performance of the composites is significantly improved, and the maximum figures of merit reach 1.3 for the Yb0.25Co4Sb12∕Yb2O3 and 1.2 for the Yb0.21Co4Sb12∕Yb2O3 composites at 850K.

Synthesis of YbyCo4Sb12∕Yb2O3 composites and their thermoelectric properties

Strontium-filled skutterudites SryCo4Sb12 have been synthesized by a melting method. The filling fraction of Sr in CoSb3 skutterudite is up to y=0.40, closely consistent with the calculated value by density functional theory methods. The lattice parameters increase linearly with the increase of Sr content, and the relative change in lattice parameters is in agreement with theoretical prediction. Hall effect measurements have been performed by Van de Pauw method at room temperature. All samples filled with Sr atom exhibit n-type conduction. The thermal and electrical transport properties have been measured in the temperature range of 300–850K. The lattice thermal conductivity of SryCo4Sb12 is significantly depressed as compared to that of the unfilled CoSb3. The dimensionless thermoelectric figure of merit, ZT, increases with increasing temperature and reaches a maximum value of 0.9 for Sr0.28Co4Sb12 at 850K.

Synthesis and thermoelectric properties of Sr-filled skutterudite SryCo4Sb12

We demonstrate robust soliton crystals generation with a fixed frequency pump laser through a thermoelectric-cooler-based thermal-tuning approach in a butterfly-packaged complementary-metal-oxide-semiconductor-compatible microresonator. Varieties of soliton crystal states, exhibiting "palm-like" optical spectra that result from the strong interactions between the dense soliton ensembles and reflect their temporal distribution directly, are experimentally observed by sweeping one cavity resonance across the pump frequency from the blue-detuned side by reducing the operating temperature of the resonator. Benefitting from the tiny intra-cavity energy change, repeatable interconversion between the chaotic modulation instability and stable soliton crystal states can be successfully achieved via simple tuning of the temperature or pump power, showing the easy accessibility and excellent stability of such soliton crystals. This work could facilitate microresonator-based optical frequency combs towards a portable, adjustable, and low-cost system while avoiding the requirements of delicate frequency-sweeping pump techniques.

Robust soliton crystals in a thermally controlled microresonator.

Multidimensional Manipulation of Photonic Spin Hall Effect with a Single-Layer Dielectric Metasurface

Optical frequency combs, a revolutionary light source characterized by discrete and equally spaced frequencies, are usually regarded as a cornerstone for advanced frequency metrology, precision spectroscopy, high-speed communication, distance ranging, molecule detection, and many others. Due to the rapid development of micro/nanofabrication technology, breakthroughs in the quality factor of microresonators enable ultrahigh energy buildup inside cavities, which gives birth to microcavity-based frequency combs. In particular, the full coherent spectrum of the soliton microcomb (SMC) provides a route to low-noise ultrashort pulses with a repetition rate over two orders of magnitude higher than that of traditional mode-locking approaches. This enables lower power consumption and cost for a wide range of applications. This review summarizes recent achievements in SMCs, including the basic theory and physical model, as well as experimental techniques for single-soliton generation and various extraordinary soliton states (soliton crystals, Stokes solitons, breathers, molecules, cavity solitons, and dark solitons), with a perspective on their potential applications and remaining challenges.

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Wenfu Zhang

Papers

Synthesis of YbyCo4Sb12∕Yb2O3 composites and their thermoelectric properties

Synthesis and thermoelectric properties of Sr-filled skutterudite SryCo4Sb12

Robust soliton crystals in a thermally controlled microresonator.

Multidimensional Manipulation of Photonic Spin Hall Effect with a Single-Layer Dielectric Metasurface

Advances in soliton microcomb generation