Best thermoelectric efficiency of ever-explored materials.

A thermoelectric device is a heat engine that directly converts heat into electricity. Many materials with a high figure of merit Z T have been discovered in the anticipation of a high thermoelectric efficiency. However, there has been a lack of investigations on efficiency-based material evaluation, and little is known about the achievable limit of thermoelectric efficiency. Here, we report the highest thermoelectric efficiency using 12,645 published materials. The 97,841,810 thermoelectric efficiencies are calculated using 808,610 device configurations under various heat-source temperatures ( T h ) when the cold-side temperature is 300 K, solving one-dimensional thermoelectric integral equations with temperature-dependent thermoelectric properties. For infinite-cascade devices, a thermoelectric efficiency larger than 33% (≈⅓) is achievable when T h exceeds 1400 K. For single-stage devices, the best efficiency of 17.1% (≈1/6) is possible when T h is 860 K. Leg segmentation can overcome this limit, delivering a very high efficiency of 24% (≈1/4) when T h is 1100 K.

International Round Robin Test of Thermoelectric Generator Modules.

The status of metrology for the characterization of thermoelectric generator modules (TEM) is investigated in this work by an international round robin (RR) test including twelve laboratories from nine countries on three continents. Measurements have been performed with three samples of a Bi2Te3-based commercial TEM type, which has prevailed over three competing types during previous tests on the short- and long-term stability. A comparison of temperature-dependent results is provided up to 200 °C hot side temperature for the maximum power output Pmax, the incident heat flow Q˙In (at maximum efficiency conditions), and the maximum efficiency ηmax. Data evaluation from all RR participants reveals maximum standard deviations for these measurands of 27.2% (Pmax), 59.2% (Q˙In), and 25.9% (ηmax). A comparison between RR data sets and reference data from manufacturer specifications shows high deviations of up to 46%, too. These deviations reflect the absence of measurement guidelines and reference samples and confirm the need for improvements in the standardization of TEM metrology. Accordingly, the results of the RR are presented against the background of our own investigations on the uncertainty budgets for the determination of the abovementioned TEM properties using inhouse-developed characterization facilities, which comprise reference and absolute measurement techniques for the determination of heat flow.

Off-Centered Pb Interstitials in PbTe.

Previous calculations have demonstrated that Te vacancies are energetically the major defects in PbTe. However, the Pb interstitials are also important because experiments have shown that the volume of Pb-rich PbTe increases at a higher Pb content. In this study, density functional theory calculations were used to investigate the defect properties of low-symmetry Pb interstitials in PbTe. By breaking the higher symmetry imposed on the on-centered interstitial defects, the lowest ground state of Pb interstitial defects is off-centered along the [1¯1¯1¯] direction. Because of the four multi-stable structures with low defect-formation energies, the defect density of Pb interstitials is expected to be approximately six times higher than previous predictions for PbTe synthesized at 900 K. In contrast to the on-centered Pb interstitials, the off-centered Pb interstitials in PbTe can exhibit long-range lattice relaxation in the [111] direction beyond a distance of 1 nm, indicating the potential formation of weak local dipoles. This result provides an alternative explanation for the emphanitic anharmonicity of PbTe in the high-temperature regime.

Overcoming Asymmetric Contact Resistances in Al-Contacted Mg2(Si,Sn) Thermoelectric Legs.

Thermoelectric generators are a reliable and environmentally friendly source of electrical energy. A crucial step for their development is the maximization of their efficiency. The efficiency of a TEG is inversely related to its electrical contact resistance, which it is therefore essential to minimize. In this paper, we investigate the contacting of an Al electrode on Mg2(Si,Sn) thermoelectric material and find that samples can show highly asymmetric electrical contact resistivities on both sides of a leg (e.g., 10 µΩ·cm2 and 200 µΩ·cm2). Differential contacting experiments allow one to identify the oxide layer on the Al foil as well as the dicing of the pellets into legs are identified as the main origins of this behavior. In order to avoid any oxidation of the foil, a thin layer of Zn is sputtered after etching the Al surface; this method proves itself effective in keeping the contact resistivities of both interfaces equally low (<10 µΩ·cm2) after dicing. A slight gradient is observed in the n-type leg's Seebeck coefficient after the contacting with the Zn-coated electrode and the role of Zn in this change is confirmed by comparing the experimental results to hybrid-density functional calculations of Zn point defects.

Thermoelectric degrees of freedom determining thermoelectric efficiency.

For over half a century, the development of thermoelectric materials has based on the dimensionless figure of merit z T , assuming that the efficiency is mainly determined by this single parameter. Here, we show that the thermoelectric conversion efficiency is determined by three independent parameters, Z gen , τ, and ß, which we call the three thermoelectric degrees of freedom (DoFs). Z gen is the well-defined mean of the traditional z T under nonzero temperature differences. The two additional parameters τ and ß are gradients of material properties and crucial to evaluating the heat current altered by nonzero Thomson heat and asymmetric Joule heat escape. Each parameter is a figure of merit. Therefore, increasing one of the three DoFs leads to higher efficiency. Our finding explains why the single-parameter theory is inaccurate. Further, it suggests an alternative direction in material discovery and device design in thermoelectrics, such as high τ and ß, beyond z T .

Regulating Te Vacancies through Dopant Balancing via Excess Ag Enables Rebounding Power Factor and High Thermoelectric Performance in p-Type PbTe.

Thermoelectric properties are frequently manipulated by introducing point defects into a matrix. However, these properties often change in unfavorable directions owing to the spontaneous formation of vacancies at high temperatures. Although it is crucial to maintain high thermoelectric performance over a broad temperature range, the suppression of vacancies is challenging since their formation is thermodynamically preferred. In this study, using PbTe as a model system, it is demonstrated that a high thermoelectric dimensionless figure of merit, zT ≈ 2.1 at 723 K, can be achieved by suppressing the vacancy formation via dopant balancing. Hole-killer Te vacancies are suppressed by Ag doping because of the increased electron chemical potential. As a result, the re-dissolution of Na2 Te above 623 K can significantly increase the hole concentration and suppress the drop in the power factor. Furthermore, point defect scattering in material systems significantly reduces lattice thermal conductivity. The synergy between defect and carrier engineering offers a pathway for achieving a high thermoelectric performance by alleviating the power factor drop and can be utilized to enhance thermoelectric properties of thermoelectric materials.

Dimension reduction of thermoelectric properties using barycentric polynomial interpolation at Chebyshev nodes.

The thermoelectric properties (TEPs), consisting of Seebeck coefficient, electrical resistivity and thermal conductivity, are infinite-dimensional vectors because they depend on temperature. Accordingly, a projection of them into a finite-dimensional space is inevitable for use in computers. In this paper, as a dimension reduction method, we validate the use of high-order polynomial interpolation of TEPs at Chebyshev nodes of the second kind. To avoid the numerical instability of high order Lagrange polynomial interpolation, we use the barycentric formula. The numerical tests on 276 sets of published TEPs show at least 8 nodes are recommended to preserve the positivity of electrical resistivity and thermal conductivity. With 11 nodes, the interpolation causes about 2% error in TEPs and only 0.4% error in thermoelectric generator module performance. The robustness of our method against noise in TEPs is also tested; as the relative error caused by the interpolation of TEPs is almost the same as the relative size of noise, the interpolation does not cause unnecessarily high oscillation at unsampled points. The accuracy and robustness of the interpolation indicate digitizing infinite-dimensional univariate material data is practicable with tens or less data points. Furthermore, since a large interpolation error comes from a drastic change of data, the interpolation can be used to detect an anomaly such as a phase transition.

Author Correction: A micromechanics-based analytical solution for the effective thermal conductivity of composites with orthotropic matrices and interfacial thermal resistance.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has not been fixed in the paper.

Abnormal Optoelectric Properties of Two-Dimensional Protonic Ruthenium Oxide with a Hexagonal Structure.

Two-dimensional structures can potentially lead to not only modulation of electron transport but also the variations of optical property. Protonic ruthenium oxide, a two-dimensional atomic sheet material, has been synthesized, and its optoelectric properties have been investigated. The results indicate that protonic ruthenium oxide is an excellent candidate for use as a flexible, transparent conducting material. A hydrated-ruthenium-oxide sheet has been first prepared via the chemical exfoliation of sodium intercalated ruthenium oxide (NaRuO2) and, subsequently, converted into a protonic ruthenium oxide sheet using thermal treatment. A thermally activated transport mechanism is dominant in hydrated ruthenium oxide but diminishes in protonic ruthenium oxide; this resulted in a high electrical conductivity of ∼200 S/cm of the protonic sheet. Because of the unique interband and intraband structure, protonic ruthenium oxide has a small optical absorption coefficient of ∼1.62%/L. Consequently, such high conductivity and low absorption coefficient of protonic ruthenium oxide results in excellent transparent conducting properties.

A micromechanics-based analytical solution for the effective thermal conductivity of composites with orthotropic matrices and interfacial thermal resistance.

We obtained an analytical solution for the effective thermal conductivity of composites composed of orthotropic matrices and spherical inhomogeneities with interfacial thermal resistance using a micromechanics-based homogenization. We derived the closed form of a modified Eshelby tensor as a function of the interfacial thermal resistance. We then predicted the heat flux of a single inhomogeneity in the infinite media based on the modified Eshelby tensor, which was validated against the numerical results obtained from the finite element analysis. Based on the modified Eshelby tensor and the localization tensor accounting for the interfacial resistance, we derived an analytical expression for the effective thermal conductivity tensor for the composites by a mean-field approach called the Mori-Tanaka method. Our analytical prediction matched very well with the effective thermal conductivity obtained from finite element analysis with up to 10% inhomogeneity volume fraction.

Enhancing Thermoelectric Performances of Bismuth Antimony Telluride via Synergistic Combination of Multiscale Structuring and Band Alignment by FeTe2 Incorporation.

It has been a difficulty to form well-distributed nano- and mesosized inclusions in a Bi2Te3-based matrix and thereby realizing no degradation of carrier mobility at interfaces between matrix and inclusions for high thermoelectric performances. Herein, we successfully synthesize multistructured thermoelectric Bi0.4Sb1.6Te3 materials with Fe-rich nanoprecipitates and sub-micron FeTe2 inclusions by a conventional solid-state reaction followed by melt-spinning and spark plasma sintering that could be a facile preparation method for scale-up production. This study presents a bismuth antimony telluride based thermoelectric material with a multiscale structure whose lattice thermal conductivity is drastically reduced with minimal degradation on its carrier mobility. This is possible because a carefully chosen FeTe2 incorporated in the matrix allows its interfacial valence band with the matrix to be aligned, leading to a significantly improved p-type thermoelectric power factor. Consequently, an impressively high thermoelectric figure of merit ZT of 1.52 is achieved at 396 K for p-type Bi0.4Sb1.6Te3-8 mol % FeTe2, which is a 43% enhancement in ZT compared to the pristine Bi0.4Sb1.6Te3. This work demonstrates not only the effectiveness of multiscale structuring for lowering lattice thermal conductivities, but also the importance of interfacial band alignment between matrix and inclusions for maintaining high carrier mobilities when designing high-performance thermoelectric materials.

Enhanced thermoelectric properties of AgSbTe2 obtained by controlling heterophases with Ce doping.

We report the enhanced thermoelectric properties of Ce-doped AgSbTe2 (AgSb1-xCexTe2) compounds. As the Ce contents increased, the proportion of heterophase Ag2Te in the AgSbTe2 gradually decreased, along with the size of the crystals. The electrical resistivity and Seebeck coefficient were dramatically affected by Ce doping and the lattice thermal conductivity was reduced. The presence of nanostructured Ag2Te heterophases resulted in a greatly enhanced dimensionless figure of merit, ZT of 1.5 at 673 K. These findings highlight the importance of the heterophase and doping control, which determines both electrical and thermal properties.

Origin of high photoconductive gain in fully transparent heterojunction nanocrystalline oxide image sensors and interconnects.

A technique for invisible image capture using a photosensor array based on transparent conducting oxide semiconductor thin-film transistors and transparent interconnection technologies is presented. A transparent conducting layer is employed for the sensor electrodes as well as interconnection in the array, providing about 80% transmittance at visible-light wavelengths. The phototransistor is a Hf-In-Zn-O/In-Zn-O heterostructure yielding a high quantum-efficiency in the visible range.

Action-derived molecular dynamics simulations for the migration and coalescence of vacancies in graphene and carbon nanotubes.

We report the results of action-derived molecular dynamics simulations for the migration and coalescence processes of monovacancies in graphene and carbon nanotubes with different chiralities. In carbon nanotubes, the migration pathways and barriers of a monovacancy depend on the tube chirality, while there is no preferential pathway in graphene due to the lattice symmetry and the absence of the curvature effect. The probable pathway changes from the axial to circumferential direction as the chirality varies from armchair to zigzag. The chirality dependence is attributed to the preferential orientation of the reconstructed bond formed around each vacancy site. It is energetically more favourable for two monovacancies to coalesce into a divacancy via alternative movements rather than simultaneous movements. The energy barriers for coalescence are generally determined by the migration barrier for the monovacancy, although there are some variations due to interactions between two diffusing vacancies. In graphene and armchair nanotubes, two monovacancies prefer to migrate along different zigzag atomic chains rather than a single atomic chain connecting these vacancies. On the other hand, in zigzag tubes, the energy barrier for coalescence increases significantly unless monovacancies lie on the same circumference.

Defects responsible for the hole gas in Ge/Si core-shell nanowires.

The origin of the ballistic hole gas recently observed in Ge/Si core-shell nanowires has not been clearly resolved yet, although it is thought to be the result of the band offset at the radial interface. Here we perform spin-polarized density-functional calculations to investigate the defect levels of surface dangling bonds and Au impurities in the Si shell. Without any doping strategy, we find that Si dangling bond and substitutional Au defects behave as charge traps, generating hole carriers in the Ge core, while their defect levels are very deep in one-component Si nanowires. The defect levels lie to within 10 meV from or below the valence band edge for nanowires with diameters larger than 33 A and the Ge fractions above 30%. As carriers are spatially separated from charge traps, scattering is greatly suppressed, leading to the ballistic conduction, in good agreement with experiments.