High-Temperature Atomic Diffusion and Specific Heat in Quasicrystals.

A quasicrystal is an ordered but nonperiodic structure understood as a projection from a higher-dimensional periodic structure. Some physical properties of quasicrystals are different from those of conventional solids. An anomalous increase in heat capacity at high temperatures has been discussed for over two decades as a manifestation of a hidden high dimensionality of quasicrystals. A plausible candidate for this origin has been the phason, which has excitation modes originating from the additional atomic rearrangements introduced by the quasiperiodic order, which can be understood in terms of shifting a higher-dimensional lattice. However, most theoretical studies of phasons have used toy models. A theoretical study of the heat capacity of realistic quasicrystals or their approximants has yet to be conducted because of the huge computational complexity. To bridge this gap between experiment and theory, we show experiments and molecular simulations on the same material, an Al-Pd-Ru quasicrystal, and its approximants. We show that at high temperatures, aluminum atoms diffuse with discontinuouslike jumps, and the diffusion paths of the aluminum can be understood in terms of jumps corresponding to hyperatomic-fluctuations-associated atomic rearrangements of the phason degrees of freedom. It is concluded that the anomaly in the heat capacity of quasicrystals arises from the hyperatomic fluctuations that play a role in diffusive Nambu-Goldstone modes.

Thermoelectric Properties of Co-Substituted Al-Pd-Re Icosahedral Quasicrystals.

The practical application of quasicrystals (QCs) as thermoelectric materials makes icosahedral (i-) Al-Pd-Re QC attractive because of its moderate electrical conductivity (~280 Ω-1 cm-1), relatively high Seebeck coefficient (~100 µV K-1), and low thermal conductivity (~1.3 W m-1 K-1) at room temperature. To develop a thermoelectric Π-shaped power generation module, we need both p- and n-type thermoelectric materials. In this work, we aimed to develop an n-type i-Al-Pd-Re-based QC and investigated the effect of Co substitution for Re on the thermoelectric properties, i.e., the electron-doping effect. We synthesized dense bulk samples with nominal compositions of Al71Pd20(Re1-xCox)9 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) via arc-melting, annealing, and sintering methods. We found that Co can produce n-type carriers in dilute substitution amounts of x = 0.1 and 0.2; however, the Seebeck coefficient at 300 K showed an n- to p-type transition with increasing x. This indicates that a simple rigid-band approximation is not applicable for i-Al-Pd-Re QC, which makes it difficult to synthesize an n-type i-Al-Pd-Re-based QC. Although the thermal conductivity was reduced from 1.28 (x = 0) to 1.08 W m-1 K-1 (x = 0.3) at 373 K by lowering of the electron thermal conductivity (electrical conductivity) and the alloying effect via Co substitution, the dimensionless figure of merit was not enhanced because of lowering of the power factor for all samples. The elastic moduli of i-Al-Pd-Re QC decreased by Co substitution, indicating that i-Al-Pd-Re-Co QC had a more ionic and brittle character.

Reduction of Thermal Conductivity for Icosahedral Al-Cu-Fe Quasicrystal through Heavy Element Substitution.

Icosahedral Al-Cu-Fe quasicrystal (QC) shows moderate electrical conductivity and low thermal conductivity, and both p- and n-type conduction can be controlled by tuning the sample composition, making it potentially suited for thermoelectric materials. In this work, we investigated the effect of introducing chemical disorder through heavy element substitution on the thermal conductivity of Al-Cu-Fe QC. We substituted Au and Pt elements for Cu up to 3 at% in a composition of Al63Cu25Fe12, i.e., Al63Cu25-x(Au,Pt)xFe12 (x = 0, 1, 2, 3). The substitutions of Au and Pt for Cu reduced the phonon thermal conductivity at 300 K (κph,300K) by up to 17%. The reduction of κph,300K is attributed to a decrease in the specific heat and phonon relaxation time through heavy element substitution. We found that increasing the Pt content reduced the specific heat at high temperatures, which may be caused by the locked state of phasons. The observed glass-like low values of κph,300K (0.9-1.1 W m-1 K-1 at 300 K) for Al63Cu25-x(Au,Pt)xFe12 are close to the lower limit calculated using the Cahill model.

Fe-Al-Si Thermoelectric (FAST) Materials and Modules: Diffusion Couple and Machine-Learning-Assisted Materials Development.

To lower the introduction and maintenance costs of autonomous power supplies for driving Internet-of-things (IoT) devices, we have developed low-cost Fe-Al-Si-based thermoelectric (FAST) materials and power generation modules. Our development approach combines computational science, experiments, mapping measurements, and machine learning (ML). FAST materials have a good balance of mechanical properties and excellent chemical stability, superior to that of conventional Bi-Te-based materials. However, it remains challenging to enhance the power factor (PF) and lower the thermal conductivity of FAST materials to develop reliable power generation devices. This forum paper describes the current status of materials development based on experiments and ML with limited data, together with power generation module fabrication related to FAST materials with a view to commercialization. Combining bulk combinatorial methods with diffusion couple and mapping measurements could accelerate the search to enhance PF for FAST materials. We report that ML prediction is a powerful tool for finding unexpected off-stoichiometric compositions of the Fe-Al-Si system and dopant concentrations of a fourth element to enhance the PF, i.e., Co substitution for Fe atoms in FAST materials.

First-principles study of electronic structures and elasticity of Al2Fe3Si3.

Al2Fe3Si3intermetallic compound shows promising application in low-cost and non-toxic thermoelectric device because of its relatively high power factor of ∼700µW m-1 K-2at 400 K. Herein we performed the first-principles calculations with the projector augmented-wave (PAW) method to study the formation energies, elastic constants, electronic structures, and electronic transport properties of Al2Fe3Si3. We discussed the thermodynamical stability of Al2Fe3Si3against other ternary crystalline compounds in Al-Fe-Si phase. The band gap of Al2Fe3Si3was particularly examined using the semilocal and hybrid functionals and the on-site Hubbard correction, which were also applied to ß-FeSi2to calibrate the prediction reliability of our employed computational methods. Our calculations show that Al2Fe3Si3is a narrow-gap semiconductor. The semilocal functional within generalized gradient approximation (GGA) shows an exceptional agreement between the predicted band gap of Al2Fe3Si3and the available experiment data, which is in contrast to the typical trend and rationally understood through a comprehensive comparison. We found that both HSE06 and PBE0 hybrid functionals with a standard setup overestimated the band gaps of Al2Fe3Si3and ß-FeSi2too much. The underlying reasons may be ascribed to a large electronic screening, which arises from the unique characteristics of Fe 3dstates appearing in both sides of band gaps of Al2Fe3Si3and ß-FeSi2, and to a reduced delocalization error thanks to the covalent Fe-Si and Si-Si bonding nature. The chemical bonding and elasticity of Al2Fe3Si3were compared with those of ß-FeSi2and FeAl2. In Al2Fe3Si3the Fe-Al bonding is more ionic and the Fe-Si bonding is more covalent. The elastic moduli of Al2Fe3Si3are comparable to those of ß-FeSi2and larger than those of FeAl2. Our calculation results indicate that the mechanical strength of Al2Fe3Si3could be strong enough for the practical application in thermoelectric device.

Earth-Abundant Fe-Al-Si Thermoelectric (FAST) Materials: from Fundamental Materials Research to Module Development.

To develop an autonomous power generation technology to support an internet-of-things (IoT) society, we proposed low-cost and nontoxic Fe-Al-Si-based thermoelectric (FAST) materials consisting of an Fe3Al2Si3 phase. Because of the cost-effectiveness and easy disposal of FAST materials, they are attractive for autonomous power supplies to drive IoT sensors and devices. While bismuth-tellurium-based thermoelectric power generation modules have been commercialized, the discovery of FAST materials opens an additional route to generate power from waste heat at room temperature under a small temperature difference, which will expand the diversity of applications of thermoelectric power generation modules. This paper reports the thermoelectric properties of FAST materials synthesized by conventional laboratory-scale synthesis and mass production processes, enhancement of power factor less than 600 K through homogenization and removal of metallic precipitations, development of thermoelectric power generation modules, and the results of power generation tests. The operation of temperature/humidity sensors and wireless transmission by Bluetooth low energy communication using FAST materials-based modules under a small temperature difference at room temperature was demonstrated.

Na Doping in PbTe: Solubility, Band Convergence, Phase Boundary Mapping, and Thermoelectric Properties.

Many monumental breakthroughs in p-type PbTe thermoelectrics are driven by optimizing a Pb0.98Na0.02Te matrix. However, recent works found that x > 0.02 in Pb1-xNaxTe further improves the thermoelectric figure of merit, zT, despite being above the expected Na solubility limit. We explain the origins of improved performance from excess Na doping through computation and experiments on Pb1-xNaxTe with 0.01 ≤ x ≤ 0.04. High temperature X-ray diffraction and Hall carrier concentration measurements show enhanced Na solubility at high temperatures when x > 0.02 but no improvement in carrier concentration, indicating that Na is entering the lattice but is electrically compensated by high intrinsic defect concentrations. The higher Na concentration leads to band convergence between the light L and heavy Σ valence bands in PbTe, suppressing bipolar conduction and increasing the Seebeck coefficient. This results in a high temperature zT nearing 2 for Pb0.96Na0.04Te, ∼25% higher than traditionally reported values for pristine PbTe-Na. Further, we apply a phase diagram approach to explain the origins of increased solubility from excess Na doping and offer strategies for repeatable synthesis of high zT Na-doped materials. A starting matrix of simple, high performing Pb0.96Na0.04Te synthesized following our guidelines may be superior to Pb0.98Na0.02Te for continued zT optimization in p-type PbTe materials.

Machine-Learning-Assisted Development and Theoretical Consideration for the Al2Fe3Si3 Thermoelectric Material.

Chemical composition alteration is a general strategy to optimize the thermoelectric properties of a thermoelectric material to achieve high-efficiency conversion of waste heat into electricity. Recent studies show that the Al2Fe3Si3 intermetallic compound with a relatively high power factor of ∼700 µW m-1 K-2 at 400 K is promising for applications in low-cost and nontoxic thermoelectric devices. To accelerate the exploration of the thermoelectric properties of this material in a mid-temperature range and to enhance its power factor, a machine-learning method was employed herein to assist the synthesis of off-stoichiometric samples (namely, Al23.5+ xFe36.5Si40- x) of the Al2Fe3Si3 compound by tuning the Al/Si ratio. The optimal Al/Si ratio for a high power factor in the mid-temperature range was found rapidly and efficiently, and the optimal ratio of the sample at x = 0.9 was found to increase the power factor at ∼510 K by about 40% with respect to that of the initial sample at x = 0.0. The possible mechanism for the enhanced power factor is discussed in terms of the precipitations of the metallic secondary phases in the Al23.5+ xFe36.5Si40- x samples. Furthermore, the maximum achievable thermal conductivity of Al2Fe3Si3 estimated by the Slack model is ∼10 W m-1 K-1 at the Debye temperature. An avoided-crossing behavior of the acoustic and the low-lying optical modes along several crystallographic directions is found in the phonon dispersion of Al2Fe3Si3 calculated by ab initio density functional theory method. These preliminary results suggest that Al2Fe3Si3 can have a low thermal conductivity. The calculated formation energies of point defects suggest that the antisite defects between Al and Si are likely to cause the Al and Si off-stoichiometries in Al2Fe3Si3. The theoretically obtained insight provides additional information for the further understanding of Al2Fe3Si3.

Thermoelectric properties and electronic structure of the Zintl phase Sr5Al2Sb6.

The Zintl phase Sr5Al2Sb6 has a large, complex unit cell and is composed of relatively earth-abundant and non-toxic elements, making it an attractive candidate for thermoelectric applications. The structure of Sr5Al2Sb6 is characterized by infinite oscillating chains of AlSb4 tetrahedra. It is distinct from the structure type of the previously studied Ca5M2Sb6 compounds (M = Al, Ga or In), all of which have been shown to have promising thermoelectric performance. The lattice thermal conductivity of Sr5Al2Sb6 (~0.55 W mK(-1) at 1000 K) was found to be lower than that of the related Ca5M2Sb6 compounds due to its larger unit cell (54 atoms per primitive cell). Density functional theory predicts a relatively large band gap in Sr5Al2Sb6, in agreement with the experimentally determined band gap of E(g) ~ 0.5 eV. High temperature electronic transport measurements reveal high resistivity and high Seebeck coefficients in Sr5Al2Sb6, consistent with the large band gap and valence-precise structure. Doping with Zn(2+) on the Al(3+) site was attempted, but did not lead to the expected increase in carrier concentration. The low lattice thermal conductivity and large band gap in Sr5Al2Sb6 suggest that, if the carrier concentration can be increased, thermoelectric performance comparable to that of Ca5Al2Sb6 could be achieved in this system.

Metallic-covalent bonding conversion and thermoelectric properties of Al-based icosahedral quasicrystals and approximants.

In this article, we review the characteristic features of icosahedral cluster solids, metallic-covalent bonding conversion (MCBC), and the thermoelectric properties of Al-based icosahedral quasicrystals and approximants. MCBC is clearly distinguishable from and closely related to the well-known metal-insulator transition. This unique bonding conversion has been experimentally verified in 1/1-AlReSi and 1/0-Al12Re approximants by the maximum entropy method and Rietveld refinement for powder x-ray diffraction data, and is caused by a central atom inside the icosahedral clusters. This helps to understand pseudogap formation in the vicinity of the Fermi energy and establish a guiding principle for tuning the thermoelectric properties. From the electron density distribution analysis, rigid heavy clusters weakly bonded with glue atoms are observed in the 1/1-AlReSi approximant crystal, whose physical properties are close to icosahedral Al-Pd-TM (TM: Re, Mn) quasicrystals. They are considered to be an intermediate state among the three typical solids: metals, covalently bonded networks (semiconductor), and molecular solids. Using the above picture and detailed effective mass analysis, we propose a guiding principle of weakly bonded rigid heavy clusters to increase the thermoelectric figure of merit (ZT) by optimizing the bond strengths of intra- and inter-icosahedral clusters. Through element substitutions that mainly weaken the inter-cluster bonds, a dramatic increase of ZT from less than 0.01 to 0.26 was achieved. To further increase ZT, materials should form a real gap to obtain a higher Seebeck coefficient.

Thermoelectric properties and electronic structure of the zintl-phase Sr(3)AlSb(3).

The Zintl-phase Sr3 AlSb3 , which contains relatively earth-abundant and nontoxic elements, has many of the features that are necessary for good thermoelectric performance. The structure of Sr3 AlSb3 is characterized by isolated anionic units formed from pairs of edge-sharing tetrahedra. Its structure is distinct from previously studied chain-forming structures, Ca3 AlSb3 and Sr3 GaSb3 , both of which are known to be good thermoelectric materials. DFT predicts a relatively large band gap in Sr3 AlSb3 (Eg ≈1 eV) and a heavier band mass than that found in other chain-forming A3 MSb3 phases (A=Sr, Ca; M=Al, Ga). High-temperature transport measurements reveal both high resistivity and high Seebeck coefficients in Sr3 AlSb3 , which is consistent with the large calculated band gap. The thermal conductivity of Sr3 AlSb3 is found to be extremely low (≈ 0.55 W mK(-1) at 1000 K) due to the large, complex unit cell (56 atoms per primitive cell). Although the figure of merit (zT) has not been optimized in the current study, a single parabolic band model suggests that, when successfully doped, zT≈ 0.3 may be obtained at 600 K; this makes Sr3 AlSb3 promising for waste-heat recovery applications. Doping with Zn(2+) on the Al(3+) site has been attempted, but does not lead to the expected increase in carrier concentration.