Improving the thermoelectric figure of merit.

The efficiency of a thermoelectric generator and the coefficient of performance (COP) of a thermoelectric heat pump are related to the hot and cold junction temperatures and a quantity known as the figure of merit, zT. During the second half of the twentieth century the figure of merit has gradually improved. This has come about through the selection of semiconducting materials with improved electronic properties and a small lattice thermal conductivity. Further advancements have been achieved by enhancing the scattering of phonons. There is also the possibility of improving the so-called power factor, that is the part of the figure of merit that contains the Seebeck coefficient and the electrical conductivity. However, it appears that it will be increasingly difficult to make further advances because of the manner in which these quantities vary with the Fermi energy. It is shown that this may set a practical limit on zT. Nevertheless, it may be possible to reach an efficiency or COP of about 40% of that of an ideal thermodynamic machine.

Simultaneous harvesting of radiative cooling and solar heating for transverse thermoelectric generation.

For any thermoelectric effects to be achieved, a thermoelectric material must have hot and cold sides. Typically, the hot side can be easily obtained by excess heat. However, the passive cooling method is often limited to convective heat transfer to the surroundings. Since thermoelectric voltage is proportional to the temperature difference between the hot and cold sides, efficient passive cooling to increase the temperature gradient is of critical importance. Here, we report simultaneous harvesting of radiative cooling at the top and solar heating at the bottom to enhance the temperature gradient for a transverse thermoelectric effect which generates thermoelectric voltage perpendicular to the temperature gradient. We demonstrate this concept by using the spin Seebeck effect and confirm that the spin Seebeck device shows the highest thermoelectric voltage when both radiative cooling and solar heating are utilized. Furthermore, the device generates thermoelectric voltage even at night through radiative cooling which enables continuous energy harvesting throughout a day. Planar geometry and scalable fabrication process are advantageous for energy harvesting applications.

Thermoelectric materials taking advantage of spin entropy: lessons from chalcogenides and oxides.

The interplay between charges and spins may influence the dynamics of the carriers and determine their thermoelectric properties. In that respect, magneto-thermoelectric power MTEP, i.e. the measurements of the Seebeck coefficient S under the application of an external magnetic field, is a powerful technique to reveal the role of magnetic moments on S. This is illustrated by different transition metal chalcogenides: CuCrTiS4 and CuMnTiS4 magnetic thiospinels, which are compared with magnetic oxides, Curie-Weiss (CW) paramagnetic misfit cobaltites, ruthenates, either ferromagnetic perovskite or Pauli paramagnet quadruple perovskites, and CuGa1-x Mn x Te2 chalcopyrite telluride and Bi1.99Cr0.01Te3 in which diluted magnetism is induced by 3%-Mn and 1%-Cr substitution, respectively. In the case of a ferromagnet (below TC) and CW paramagnetic materials, the increase of magnetization at low T when a magnetic field is applied is accompanied by a decrease of the entropy of the carriers and hence S decreases. This is consistent with the lack of MTEP in the Pauli paramagnetic quadruple perovskites. Also, no significant MTEP is observed in CuGa1-x Mn x Te2 and Bi1.99Cr0.01Te3, for which Kondo-type interaction between magnetic moments and carriers prevails. In contrast, spin glass CuCrTiS4 exhibits negative MTEP like in ferromagnetic ruthenates and paramagnetic misfit cobaltites. This investigation of some chalcogenides and oxides provides key ingredients to select magnetic materials for which S benefits from spin entropy.

Control of anisotropic conduction of carbon nanotube sheets and their use as planar-type thermoelectric conversion materials.

The large anisotropic thermal conduction of a carbon nanotube (CNT) sheet that originates from the in-plane orientation of one-dimensional CNTs is disadvantageous for thermoelectric conversion using the Seebeck effect since the temperature gradient is difficult to maintain in the current flow direction. To control the orientation of the CNTs, polymer particles are introduced as orientation aligners upon sheet formation by vacuum filtration. The thermal conductivities in the in-plane direction decrease as the number of polymer particles in the sheet increases, while that in the through-plane direction increases. Consequently, a greater temperature gradient is observed for the anisotropy-controlled CNT sheet as compared to that detected for the CNT sheet without anisotropy control when a part of the sheet is heated, which results in a higher power density for the planar-type thermoelectric device. These findings are quite useful for the development of flexible and wearable thermoelectric batteries using CNT sheets.

High-performance flexible thermoelectric modules based on high crystal quality printed TiS2/hexylamine.

Printed electronics implies the use of low-cost, scalable, printing technologies to fabricate electronic devices and circuits on flexible substrates, such as paper or plastics. The development of this new electronic is currently expanding because of the emergence of the internet-of-everything. Although lot of attention has been paid to functional inks based on organic semiconductors, another class of inks is based on nanoparticles obtained from exfoliated 2D materials, such as graphene and metal sulfides. The ultimate scientific and technological challenge is to find a strategy where the exfoliated nanoparticle flakes in the inks can, after solvent evaporation, form a solid which displays performances equal to the single crystal of the 2D material. In this context, a printed layer, formed from an ink composed of nano-flakes of TiS2 intercalated with hexylamine, which displays thermoelectric properties superior to organic intercalated TiS2 single crystals, is demonstrated for the first time. The choice of the fraction of exfoliated nano-flakes appears to be a key to the forming of a new self-organized layered material by solvent evaporation. The printed layer is an efficient n-type thermoelectric material which complements the p-type printable organic semiconductors The thermoelectric power factor of the printed TiS2/hexylamine thin films reach record values of 1460 µW m-1 K-2 at 430 K, this is considerably higher than the high value of 900 µW m-1 K-2 at 300 K reported for a single crystal. A printed thermoelectric generator based on eight legs of TiS2 confirms the high-power factor values by generating a power density of 16.0 W m-2 at ΔT = 40 K.

Thermally enhanced polyolefin composites: fundamentals, progress, challenges, and prospects.

The low thermal conductivity of polymers is a barrier to their use in applications requiring high thermal conductivity such as electronic packaging, heat exchangers, and thermal management devices. Polyolefins represent about 55% of global thermoplastic production, and therefore improving their thermal conductivity is essential for many applications. This review analyzes the advances in enhancing the thermal conductivity of polyolefin composites. First, the mechanisms of thermal transport in polyolefin composites and the key parameters that govern conductive heat transfer through the interface between the matrix and the filler are discussed. Then, the advantage and limitations of the current methods for measuring thermal conductivity are analyzed. Moreover, the progress in predicting the thermal conductivity of polymer composites using modeling and simulation is discussed. Furthermore, polyolefin composites and nanocomposites with different thermally conductive fillers are reviewed and analyzed. Finally, the key challenges and future directions for developing thermally enhanced polyolefin composites are outlined.

Substitutional and interstitial impurity p-type doping of thermoelectric Mg2Si: a theoretical study.

The narrow-gap magnesium silicide semiconductor Mg2Si is a promising mid-temperature (600-900 K) thermoelectric material. It intrinsically possesses n-type conductivity, and n-type dopants are generally used for improving its thermoelectric performance; however, the synthesis of p-type Mg2Si is relatively difficult. In this work, the hole doping of Mg2Si with various impurity atoms is investigated by performing first principles calculations. It is found that the Ag-doped systems exhibit comparable formation energies ΔE calculated for different impurity sites (Mg, Si, and interstitial 4b ones), which may explain the experimental instability of their p-type conductivity. A similar phenomenon is observed for the systems incorporating alkali metals (Li, Na, and K) since their ΔE values determined for Mg (p-type) and 4b (n-type) sites are very close. Among boron group elements (Ga and B), Ga is found to be favorable for hole doping because it exhibits relatively small ΔE values for Si (p-type) sites. Furthermore, the interstitial insertion of Cl and F atoms into the crystal lattice leads to hole doping because of their high electronegativity.

Thermoelectric properties of sorted semiconducting single-walled carbon nanotube sheets.

Single-walled carbon nanotubes (SWNTs), especially their semiconducting type, are promising thermoelectric (TE) materials due to their high Seebeck coefficient. In this study, the in-plane Seebeck coefficient (S), electrical conductivity (σ), and thermal conductivity (κ) of sorted semiconducting SWNT (s-SWNT) free-standing sheets with different s-SWNT purities are measured to determine the figure of merit ZT. We find that the ZT value of the sheets increases with increasing s-SWNT purity, mainly due to an increase in Seebeck coefficient while the thermal conductivity remaining constant, which experimentally proved the superiority of the high purity s-SWNT as TE materials for the first time. In addition, from the comparison between sorted and unsorted SWNT sheets, it is recognized that the difference of ZT between unsorted SWNT and high-purity s-SWNT sheet is not remarkable, which suggests the control of carrier density is necessary to further clarify the superiority of SWNT sorting for TE applications.

Tuning phonon transport spectrum for better thermoelectric materials.

The figure of merit of thermoelectric materials can be increased by suppressing the lattice thermal conductivity without degrading electrical properties. Phonons are the carriers for lattice thermal conduction, and their transport can be impeded by nanostructuring, owing to the recent progress in nanotechnology. The key question for further improvement of thermoelectric materials is how to realize ultimate structure with minimum lattice thermal conductivity. From spectral viewpoint, this means to impede transport of phonons in the entire spectral domain with noticeable contribution to lattice thermal conductivity that ranges in general from subterahertz to tens of terahertz in frequency. To this end, it is essential to know how the phonon transport varies with the length scale, morphology, and composition of nanostructures, and how effects of different nanostructures can be mutually adopted in view of the spectral domain. Here we review recent advances in analyzing such spectral impedance of phonon transport on the basis of various effects including alloy scattering, boundary scattering, and particle resonance.

Thermoelectric materials and applications for energy harvesting power generation.

Thermoelectrics, in particular solid-state conversion of heat to electricity, is expected to be a key energy harvesting technology to power ubiquitous sensors and wearable devices in the future. A comprehensive review is given on the principles and advances in the development of thermoelectric materials suitable for energy harvesting power generation, ranging from organic and hybrid organic-inorganic to inorganic materials. Examples of design and applications are also presented.

Organic π-type thermoelectric module supported by photolithographic mold: a working hypothesis of sticky thermoelectric materials.

To examine the potential of organic thermoelectrics (TEs) for energy harvesting, we fabricated an organic TE module to achieve 250 mV in the open-circuit voltage which is sufficient to drive a commercially available booster circuit designed for energy harvesting usage. We chose the π-type module structure to maintain the temperature differences in organic TE legs, and then optimized the p- and n-type TE materials' properties. After injecting the p- and n-type TE materials into photolithographic mold, we eventually achieved 250 mV in the open-circuit voltage by a method to form the upper electrodes. However, we faced a difficulty to reduce the contact resistance in this material system. We conclude that TE materials must be inversely designed from the viewpoints of the expected module structures and mass-production processes, especially for the purpose of energy harvesting.

Phonon and heat transport control using pillar-based phononic crystals.

Phononic crystals have been studied for the past decades as a tool to control the propagation of acoustic and mechanical waves. Recently, researchers proposed that nanosized phononic crystals can also control heat conduction and improve the thermoelectric efficiency of silicon by phonon dispersion engineering. In this review, we focus on recent theoretical and experimental advances in phonon and thermal transport engineering using pillar-based phononic crystals. First, we explain the principles of the phonon dispersion engineering and summarize early proof-of-concept experiments. Next, we review recent simulations of thermal transport in pillar-based phononic crystals and seek to uncover the origin of the observed reduction in the thermal conductivity. Finally, we discuss first experimental attempts to observe the predicted thermal conductivity reduction and suggest the directions for future research.

Data-driven exploration of new pressure-induced superconductivity in PbBi2Te4.

Candidate compounds for new thermoelectric and superconducting materials, which have narrow band gap and flat bands near band edges, were exhaustively searched by the high-throughput first-principles calculation from an inorganic materials database named AtomWork. We focused on PbBi2Te4 which has the similar electronic band structure and the same crystal structure with those of a pressure-induced superconductor SnBi2Se4 explored by the same data-driven approach. The PbBi2Te4 was successfully synthesized as single crystals using a melt and slow cooling method. The core level X-ray photoelectron spectroscopy analysis revealed Pb2+, Bi3+ and Te2- valence states in PbBi2Te4. The thermoelectric properties of the PbBi2Te4 sample were measured at ambient pressure and the electrical resistance was also evaluated under high pressure using a diamond anvil cell with boron-doped diamond electrodes. The resistance decreased with increasing of the pressure, and pressure-induced superconducting transitions were discovered at 2.5 K under 10 GPa. The maximum superconducting transition temperature increased up to 8.4 K at 21.7 GPa. The data-driven approach shows promising power to accelerate the discovery of new thermoelectric and superconducting materials.

Strongly correlated oxides for energy harvesting.

We review recent advances in strongly correlated oxides as thermoelectric materials in pursuit of energy harvesting. We discuss two topics: one is the enhancement of the ordinary thermoelectric properties by controlling orbital degrees of freedom and orbital fluctuation not only in bulk but also at the interface of correlated oxides. The other topic is the use of new phenomena driven by spin-orbit coupling (SOC) of materials. In 5d electron oxides, we show some SOC-related transport phenomena, which potentially contribute to energy harvesting. We outline the current status and a future perspective of oxides as thermoelectric materials.

Selective laser melting of high-performance pure tungsten: parameter design, densification behavior and mechanical properties.

Selective laser melting (SLM) additive manufacturing of pure tungsten encounters nearly all intractable difficulties of SLM metals fields due to its intrinsic properties. The key factors, including powder characteristics, layer thickness, and laser parameters of SLM high density tungsten are elucidated and discussed in detail. The main parameters were designed from theoretical calculations prior to the SLM process and experimentally optimized. Pure tungsten products with a density of 19.01 g/cm3 (98.50% theoretical density) were produced using SLM with the optimized processing parameters. A high density microstructure is formed without significant balling or macrocracks. The formation mechanisms for pores and the densification behaviors are systematically elucidated. Electron backscattered diffraction analysis confirms that the columnar grains stretch across several layers and parallel to the maximum temperature gradient, which can ensure good bonding between the layers. The mechanical properties of the SLM-produced tungsten are comparable to that produced by the conventional fabrication methods, with hardness values exceeding 460 HV0.05 and an ultimate compressive strength of about 1 GPa. This finding offers new potential applications of refractory metals in additive manufacturing.

Thickness-dependent thermoelectric power factor of polymer-functionalized semiconducting carbon nanotube thin films.

The effects of polymer structures on the thermoelectric properties of polymer-wrapped semiconducting carbon nanotubes have yet to be clarified for elucidating intrinsic transport properties. We systematically investigate thickness dependence of thermoelectric transport in thin films containing networks of conjugated polymer-wrapped semiconducting carbon nanotubes. Well-controlled doping experiments suggest that the doping homogeneity and then in-plane electrical conductivity significantly depend on film thickness and polymer species. This understanding leads to achieving thermoelectric power factors as high as 412 µW m-1 K-2 in thin carbon nanotube films. This work presents a standard platform for investigating the thermoelectric properties of nanotubes.

Miniaturized planar Si-nanowire micro-thermoelectric generator using exuded thermal field for power generation.

For harvesting energy from waste heat, the power generation densities and fabrication costs of thermoelectric generators (TEGs) are considered more important than their conversion efficiency because waste heat energy is essentially obtained free of charge. In this study, we propose a miniaturized planar Si-nanowire micro-thermoelectric generator (SiNW-µTEG) architecture, which could be simply fabricated using the complementary metal-oxide-semiconductor-compatible process. Compared with the conventional nanowire µTEGs, this SiNW-µTEG features the use of an exuded thermal field for power generation. Thus, there is no need to etch away the substrate to form suspended SiNWs, which leads to a low fabrication cost and well-protected SiNWs. We experimentally demonstrate that the power generation density of the SiNW-µTEGs was enhanced by four orders of magnitude when the SiNWs were shortened from 280 to 8 µm. Furthermore, we reduced the parasitic thermal resistance, which becomes significant in the shortened SiNW-µTEGs, by optimizing the fabrication process of AlN films as a thermally conductive layer. As a result, the power generation density of the SiNW-µTEGs was enhanced by an order of magnitude for reactive sputtering as compared to non-reactive sputtering process. A power density of 27.9 nW/cm2 has been achieved. By measuring the thermal conductivities of the two AlN films, we found that the reduction in the parasitic thermal resistance was caused by an increase in the thermal conductivity of the AlN film and a decrease in the thermal boundary resistance.

Nanostructure design for drastic reduction of thermal conductivity while preserving high electrical conductivity.

The design and fabrication of nanostructured materials to control both thermal and electrical properties are demonstrated for high-performance thermoelectric conversion. We have focused on silicon (Si) because it is an environmentally friendly and ubiquitous element. High bulk thermal conductivity of Si limits its potential as a thermoelectric material. The thermal conductivity of Si has been reduced by introducing grains, or wires, yet a further reduction is required while retaining a high electrical conductivity. We have designed two different nanostructures for this purpose. One structure is connected Si nanodots (NDs) with the same crystal orientation. The phonons scattering at the interfaces of these NDs occurred and it depended on the ND size. As a result of phonon scattering, the thermal conductivity of this nanostructured material was below/close to the amorphous limit. The other structure is Si films containing epitaxially grown Ge NDs. The Si layer imparted high electrical conductivity, while the Ge NDs served as phonon scattering bodies reducing thermal conductivity drastically. This work gives a methodology for the independent control of electron and phonon transport using nanostructured materials. This can bring the realization of thermoelectric Si-based materials that are compatible with large scale integrated circuit processing technologies.

Thermoelectric La-doped SrTiO3 epitaxial layers with single-crystal quality: from nano to micrometers.

High-quality thermoelectric La0.2Sr0.8TiO3 (LSTO) films, with thicknesses ranging from 20 nm to 0.7 µm, have been epitaxially grown on SrTiO3(001) substrates by enhanced solid-source oxide molecular-beam epitaxy. All films are atomically flat (with rms roughness < 0.2 nm), with low mosaicity (<0.1°), and present very low electrical resistivity (<5 × 10-4 Ω cm at room temperature), one order of magnitude lower than standard commercial Nb-doped SrTiO3 single-crystalline substrate. The conservation of transport properties within this thickness range has been confirmed by thermoelectric measurements where Seebeck coefficients of approximately -60 µV/K have been recorded for all films. These LSTO films can be integrated on Si for non-volatile memory structures or opto-microelectronic devices, functioning as transparent conductors or thermoelectric elements.

Composites of aluminum alloy and magnesium alloy with graphite showing low thermal expansion and high specific thermal conductivity.

High thermal conductivity, low thermal expansion and low density are three important features in novel materials for high performance electronics, mobile applications and aerospace. Spark plasma sintering was used to produce light metal-graphite composites with an excellent combination of these three properties. By adding up to 50 vol.% of macroscopic graphite flakes, the thermal expansion coefficient of magnesium and aluminum alloys was tuned down to zero or negative values, while the specific thermal conductivity was over four times higher than in copper. No degradation of the samples was observed after thermal stress tests and thermal cycling. Tensile strength and hardness measurements proved sufficient mechanical stability for most thermal management applications. For the production of the alloys, both prealloyed powders and elemental mixtures were used; the addition of trace elements to cope with the oxidation of the powders was studied.