There has been a renaissance of interest in exploring highly efficient thermoelectric materials as a possible route to address the worldwide energy generation, utilization, and management. This review describes the recent advances in designing high-performance bulk thermoelectric materials. We begin with the fundamental stratagem of achieving the greatest thermoelectric figure of merit ZT of a given material by carrier concentration engineering, including Fermi level regulation and optimum carrier density stabilization. We proceed to discuss ways of maximizing ZT at a constant doping level, such as increase of band degeneracy (crystal structure symmetry, band convergence), enhancement of band effective mass (resonant levels, band flattening), improvement of carrier mobility (modulation doping, texturing), and decrease of lattice thermal conductivity (synergistic alloying, second-phase nanostructuring, mesostructuring, and all-length-scale hierarchical architectures). We then highlight the decoupling of th...

Rationally Designing High-Performance Bulk Thermoelectric Materials

Semiconductor nanowires represent an important class of nanostructure building block for photovoltaics as well as direct solar-to-fuel application because of their high surface area, tunable bandgap and efficient charge transport and collection. In this talk, I will highlight several recent examples in this lab using semiconductor nanowires and their heterostructures for the purpose of solar energy harvesting. In addition, we have also discovered that the thermoconductivity of the silicon nanowires can be significantly reduced due to phonon scattering, pointing to a very promising approach to design better thermoelectrical materials. It is important to note that the engines that generate most of the world's power typically operate at only 30–40 per cent efficiency, releasing roughly 15 terawatts of heat to the environment. If this “wasted heat” could be recycled, the impact globally would be enormous. Our silicon nanowire thermoelectric technology could have a significant impact in alternative energy generation.

Semiconductor nanowires for energy conversion.

Layered MAX phases are exfoliated into 2D single layers and multilayers, so-called MXenes. Using fi rst-principles calculations, the formation and electronic properties of various MXene systems, M 2 C (M = Sc, Ti, V, Cr, Zr, Nb, Ta) and M 2 N (M = Ti, Cr, Zr) with surfaces chemically functionalized by F, OH, and O groups, are examined. Upon appropriate surface functionalization, Sc 2 C, Ti 2 C, Zr 2 C, and Hf 2 C MXenes are expected to become semiconductors. It is also derived theoretically that functionalized Cr 2 C and Cr 2 N MXenes are magnetic. Thermoelectric calculations based on the Boltzmann theory imply that semiconducting MXenes attain very large Seebeck coeffi cients at low temperatures.

Novel Electronic and Magnetic Properties of Two‐Dimensional Transition Metal Carbides and Nitrides

The field of thermoelectrics has progressed enormously and is now growing steadily because of recently demonstrated advances and strong global demand for cost-effective, pollution-free forms of energy conversion. Rapid growth and exciting innovative breakthroughs in the field over the last 10-15 years have occurred in large part due to a new fundamental focus on nanostructured materials. As a result of the greatly increased research activity in this field, a substantial amount of new data--especially related to materials--have been generated. Although this has led to stronger insight and understanding of thermoelectric principles, it has also resulted in misconceptions and misunderstanding about some fundamental issues. This article sets out to summarize and clarify the current understanding in this field; explain the underpinnings of breakthroughs reported in the past decade; and provide a critical review of various concepts and experimental results related to nanostructured thermoelectrics. We believe recent achievements in the field augur great possibilities for thermoelectric power generation and cooling, and discuss future paths forward that build on these exciting nanostructuring concepts.

Nanostructured Thermoelectrics: Big Efficiency Gains from Small Features

Extraordinary electron systems can be generated at well-defined interfaces between complex oxides. In recent years, progress has been achieved in exploring and making use of the fundamental properties of such interfaces, and it has become clear that these electron systems offer the potential for possible future devices. We trace the state of the art of this emerging field of electronics and discuss some of the challenges and pitfalls that may lie ahead.

http://science.sciencemag.org/content/sci/327/5973/1607.full.pdf

Oxide Interfaces—An Opportunity for Electronics

Enhancement of the Seebeck coefficient (S ) without reducing the electrical conductivity (sigma) is essential to realize practical thermoelectric materials exhibiting a dimensionless figure of merit (ZT=S2 x sigma x T x kappa-1) exceeding 2, where T is the absolute temperature and kappa is the thermal conductivity. Here, we demonstrate that a high-density two-dimensional electron gas (2DEG) confined within a unit cell layer thickness in SrTiO(3) yields unusually large |S|, approximately five times larger than that of SrTiO(3) bulks, while maintaining a high sigma2DEG. In the best case, we observe |S|=850 microV K-1 and sigma2DEG=1.4 x 10(3) S cm-1. In addition, by using the kappa of bulk single-crystal SrTiO(3) at room temperature, we estimate ZT approximately 2.4 for the 2DEG, corresponding to ZT approximately 0.24 for a complete device having the 2DEG as the active region. The present approach using a 2DEG provides a new route to realize practical thermoelectric materials without the use of toxic heavy elements.

Giant thermoelectric Seebeck coefficient of a two-dimensional electron gas in SrTiO3

Electron and thermal transport properties, i.e., electrical conductivity, carrier concentration, Hall mobility, Seebeck coefficient, thermal conductivity, of heavily La- or Nb-doped SrTiO3 (STO) bulk single crystals were measured at high temperatures, (300–1050K) to clarify the influence of doping upon the thermoelectric performance of STO. The temperature dependence of Hall mobility and Seebeck coefficient changed at ∼750K in all samples because the dominant mechanism for carrier scattering changed with increasing temperature from coupled scattering by polar optical phonons and acoustic phonons to mere acoustic phonon scattering. The density-of-states effective mass of Nb-doped STO, which was estimated from the carrier concentration and Seebeck coefficient, was larger than that of La-doped STO. Thermal conductivity of the samples, which was similar to that of undoped STO single crystal, decreased proportionally to T−1, indicating that the phonon conduction takes place predominantly and the electronic con...

High-temperature carrier transport and thermoelectric properties of heavily La- or Nb-doped SrTiO3 single crystals

Carrier concentration dependence of the thermoelectric figure of merit, ZT of SrTiO3 at high-temperature (1000 K) is clarified using heavily Nb-doped SrTiO3 epitaxial films, which were grown on insulating (100)-oriented LaAlO3 single-crystalline substrates by a pulsed-laser deposition method. Carrier concentration, Hall mobility, Seebeck coefficient, and thermal conductivity of Nb-doped SrTiO3 epitaxial films were experimentally evaluated at 1000 K with an aid of theoretical analysis. ZT of Nb-doped SrTiO3 increases with Nb concentration and it reaches ∼0.37 (20% Nb doped), which is the largest value among n-type oxide semiconductors ever reported.

Large thermoelectric performance of heavily Nb-doped SrTiO3 epitaxial film at high temperature

Helical polypeptides have a highly rigid conformation. In order to control self-assembling structure in nanoscale, the rigidity of the stabilizing molecules, which is working as scaffolds, is highly important. Furthermore, the molecular lengths of polypeptides can be readily controlled by using their unique polymerization methods. In this study, we have used helical polypeptides as the stabilizing reagent of metal nanoparticles. As for rigid helical polypeptides, poly(gamma-benzyl-L-glutamate) (PBLG) was selected, and was synthesized by N-carboxylic acid anhydride (NCA) polymerization. Preparation of helical polypeptide-stabilized gold nanoparticles using a two-phase reduction process from the corresponding metal salts with NaBH4 is therefore introduced. PBLG itself did not have good stabilizing ability for metal nanoparticles and a terminal attaching ligand was indispensable for nanoparticle stabilization and, for this purpose, lipoic acid was selected. It is estimated that lipoic acid functionalized polypeptide molecules were attached perpendicularly to the particle surface by lipoic acid group. The size and structure, as well as assembling will be discussed in this manuscript.

Preparation and characterization of polypeptide-stabilized gold nanoparticles.

To clarify the potential of n-type conductive SrTiO/sub 3/ as a high temperature thermoelectric material, carrier concentration dependence of the thermoelectric figure of merit, ZT of SrTiO/sub 3/ at high-temperature (1000 K) is clarified using heavily Nb- or La-doped SrTiO/sub 3/ epitaxial films, which were grown on insulating (100)-oriented LaAlO/sub 3/ single-crystalline substrates by a pulsed-laser deposition method. Carrier concentration, Hall mobility, Seebeck coefficient and thermal conductivity of Nb- or La-doped SrTiO/sub 3/ epitaxial films were experimentally evaluated at 1000 K with an aid of theoretical analysis. The maximum ZT value was obtained ZT = 0.37 for 4 /spl times/ 10/sup 21/ cm/sup -3/ Nb-doped SrTiO/sub 3/ at 1000 K, which is the largest value among n-type oxide semiconductors ever reported.

http://ieeexplore.ieee.org/iel5/10188/32527/01519914.pdf

Takashi Nomura

Papers

Giant thermoelectric Seebeck coefficient of a two-dimensional electron gas in SrTiO3

High-temperature carrier transport and thermoelectric properties of heavily La- or Nb-doped SrTiO3 single crystals

Large thermoelectric performance of heavily Nb-doped SrTiO3 epitaxial film at high temperature

Preparation and characterization of polypeptide-stabilized gold nanoparticles.

Electron transport and thermoelectric response of Nb- or La-doped SrTiO/sub 3/ epitaxial film at high-temperature