Thermoelectric Transport Properties Research Articles

High-Pressure Synthesis of Te-Ge Double-Substituted Skutterudite with Enhanced Thermoelectric Properties.

We synthesized Co4Sb11TexGe1-x (x = 0.5-0.8) using high-pressure, high-temperature conditions at ∼2 GPa and ∼900 K. The microstructure, morphology, and components were characterized via X-ray diffraction, scanning electron microscopy, and electron backscatter diffraction (EBSD). EBSD indicated that the average grain size of Co4Sb11Te0.8Ge0.2 was 1 μm. Electrical conductivity, Seebeck coefficient, and thermal conductivity were measured from 300 to 800 K. The minimum lattice thermal conductivity of Co4Sb11Te0.8Ge0.2 was 0.72 W m-1 K-1, 74% lower than that at 300 K. The introduction of Te and Ge effectively enhanced point effects scattering and location scattering, notably decreasing lattice thermal conductivity. Therefore, the maximum zT value of Co4Sb11Te0.8Ge0.2 was 1.13 at 800 K. These results indicate that high pressure combined with multielement substitution optimized the thermoelectric transport properties of skutterudites.

Compositionally restricted atomistic line graph neural network for improved thermoelectric transport property predictions

Graph neural networks (GNNs) have evolved many variants for predicting the properties of crystal materials. While most networks within this family focus on improving model structures, the significance of atomistic features has not received adequate attention. In this study, we constructed an atomistic line GNN model using compositionally restricted atomistic representations which are more elaborate set of descriptors compared to previous GNN models, and employing unit graph representations that account for all symmetries. The developed model, named as CraLiGNN, outperforms previous representative GNN models in predicting the Seebeck coefficient, electrical conductivity, and electronic thermal conductivity that are recorded in a widely used thermoelectric properties database, confirming the importance of atomistic representations. The CraLiGNN model allows optional inclusion of additional features. The supplement of bandgap significantly enhances the model performance, for example, more than 35% reduction of mean absolute error in the case of 600 K and 1019 cm−3 concentration. We applied CraLiGNN to predict the unrecorded thermoelectric transport properties of 14 half-Heusler and 52 perovskite compounds, and compared the results with first-principles calculations, showing that the model has extrapolation ability to identify the thermoelectric potential of materials.

Insight into Carrier and Phonon Transports of PbSnS2 Crystals.

The simultaneous optimization of n-type and p-type thermoelectric materials is advantageous to the practical application of the device. As an emerging thermoelectric material, PbSnS2 exhibits highly competitive thermoelectric properties due to its unique carrier and phonon transport characteristics. To promote the utilization of this low-cost thermoelectric material, p-type PbSnS2 crystals are synthesized and optimized through Na doping and Se alloying. The resulting thermoelectric transport properties differ significantly from those reported for n-type crystals, prompting us to compare and analyze both n-type (Cl-doped) and p-type (Na-doped) PbSnS2 crystals from various perspectives. Cl doping is subject to weaker "Fermi pinning" and lower impurity ionization energy compared with Na doping, leading to higher doping efficiency. The different optimal performance directions in n-type and p-type crystals can be attributed to the distinct charge density distributions near the conduction band minimum (CBM) and the valence band maximum (VBM). Additionally, both n-type and p-type crystals exhibit ultralow lattice thermal conductivity due to the low symmetry of their twisted NaCl structure combined with the strong anharmonicity. This comprehensive analysis of PbSnS2 crystals provides a solid foundation for further performance optimization and device assembly, while also sheds light on the investigation of layered thermoelectric materials.

Thermoelectric and electrical transport properties of mixed-conducting multicomponent oxides based on Ba(Zr,Ce)O3-δ

In this work, the chosen physicochemical properties of single-phase multicomponent oxides BaTi1/8Fe1/8Co1/8Y1/8Zr1/8Sn1/8Ce1/8Hf1/8O3-δ and BaTi1/9Fe1/9Co1/9Y1/9Zr1/9Sn1/9Ce1/9Hf1/9Bi1/9O3-δ were studied. The microstructure of the compounds strongly depended on the presence of bismuth in the structure. The electrical transport studies showed a level of electrical conductivity of ∼10-3 - 10-2 S/cm in the temperature range 673 – 1073 K. Electrical conductivity was thermally activated and the dominant conduction mechanism was the hopping of small polarons. Moreover, total electrical conductivity changes in the dry and humidified atmosphere at lower temperatures due to the presence of protonic defects in the structure. Thermoelectric measurements showed a relatively high value of the Seebeck coefficient for studied ceramics. Its values ranged between 50 and 250 μV/K depending on the sample and temperature. The Seebeck coefficient sign was positive, meaning that electron holes and/or oxygen vacancies were predominant charge carriers in oxidising atmospheres. Additionally, the Seebeck coefficient was found to be different in the humidified atmosphere which indicates an influence of protonic defects on thermoelectric transport. The obtained power factor Pf turned out to be low and dependent on the presence of protonic defects in the structure. This indicates, that the efficiency of the MOs-based operating thermoelectric generators can be controlled by changing the partial pressure of water vapor.

Computational insights into structural, electronic, optical and thermoelectric features of ternary chalcogenide Ca2GeX4 (X=S, Se, Te) compounds

The advancements in materials engineering for clean energy and greenhouse gas reduction has attracted global attention. Furthermore, the distinct electrical and optical properties of ternary chalcogenides are critical for their application in solar energy conversion. In this study, the electronic, optical, thermodynamic, and thermoelectric transport properties of the ternary chalcogenide Ca2GeX4 (X = S, Se, and Te) compounds are comprehensively investigated using the density functional theory-based WIEN2k package. The findings indicate that ternary chalcogenide Ca2GeX4 compounds possess substantial band gaps and display strong covalent bonding characteristics. Analysis of the density of states reveals minimal impact from S-s and S-p states, while highlighting the significance of Ca-s and Ge-s states. The investigated materials show significant UV absorption with reflectance between 30 and 40 % which peaks at 13.5 eV at about 65 %, confirming the optical properties of the ternary chalcogenide Ca2GeX4. The positive Seebeck coefficient suggests that holes are the primary charge carriers in tested materials, with thermal energy rising in accordance with the chalcogenide's atomic number. Several thermoelectric properties that demonstrate the suitability of these materials for thermoelectric applications were also discussed. Overall, the findings confirm the thermoelectric and optoelectronic properties of Ca2GeX4 materials, which may facilitate the creation and development of effective optoelectronic devices.

Influence behavior and mechanism of double-layer Gr stacking configuration on mechanical strength and thermoelectric transport properties of Cu/Gr composites

The mechanical strength, electrical conductivity, and thermal conductivity of Cu/graphene (Gr) composites with Cu (111)/double-layer Gr/Cu (111) structure were investigated by using density functional theory and semi-classical Boltzmann transport theory. The results indicate that, the chemical bonds were generated between the two layers of Gr film, and the maximum charge densities of Gr-Top stacking configuration and Gr-Hollow stacking configuration are 0.104 and 0.118 e/Å3, respectively. Gr-Hollow stacking configuration has the larger mechanical strength and plasticity than Gr-Top stacking configuration. Although the covalent characteristic for the two stacking configurations is identical, the ionic characteristic of Gr-Top stacking configuration is stronger than Gr-Hollow stacking configuration. Therefore, the electron localization of Gr-Top stacking configuration is much stronger, leading to the smaller number of free electrons. The electrical conductivity and thermal conductivity of Gr-Hollow stacking configuration are 2.55 times and 1.63 times those of Gr-Top stacking configuration was achieved. Moreover, as the external longitudinal strain from 0 % to 15 % applied on Cu (111)/double-layer Gr/Cu (111) structure, the thermoelectric transport properties of Gr-Hollow stacking configuration are greater than Gr-Top stacking configuration, while as the strain are 20 % and 25 %, Gr-Top stacking configuration has the larger electric conductivity and thermal conductivity instead.

Prediction of X2AuYZ6 (X = Cs, Rb; Z = Cl, Br, I) double halide perovskites for photovoltaic and wasted heat management device applications

We used density functional theory to study the phase stability, the opto-electronic properties, and the thermo-electric behavior of X2AuYZ6 (where X = Cs, Rb, and Z = Cl/Br/I) double halide perovskites. The compounds belong to the cubic perovskite arrangement and are verified by the tolerance and octahedral factor. Formation enthalpy and binding energy primarily meet the requirements for structural stability. The positive frequency of phonon dispersion shows that all compounds are dynamically stable except for Rb2AuYI6. The negative formation energy considering the competing phase also confirmed that all compounds are thermodynamically stable. The Pugh's ratio, Poisson's ratio, and Cauchy pressure validated their ductile nature in the analysis of thermo-mechanical behavior. The electronic characteristics of Cs2AuYZ6 (Rb2AuYZ6) [Z = Cl, Br, I] double halide perovskites (DHP) have been investigated using the TB-mBJ technique, yielding band gap values of 2.85 (2.91), 2.35 (2.40), and 1.74 (1.78) eV, in that order. The optical properties are calculated, revealing the maximum absorption coefficients with respect to wavelength in the visible range of the titled compounds are 0.23 (0.35) × 105 cm−1, 1.01 (1.06) × 105 cm−1, and 1.42 (1.48) × 105 cm−1, respectively, indicating their potential for photovoltaic applications. The thermo-electric transport properties were also studied. The investigated compounds [Cs (Rb)-based] exhibit ZT values of 0.51 (0.55), 0.53 (0.62), and 0.58 (0.75) at room temperature with Cl, Br, and I, respectively. As a result, the studied compounds, particularly those Rb-based with halides, have significantly greater potential than Cs in thermoelectric fields. So, among the compounds, X2AuYI6 (X = Cs, Rb) shows the most promise for the technological applications mentioned above due to its lower band gap, high absorption coefficient, and high ZT value.

Universality and the thermoelectric transport properties of a double quantum dot system: Seeking for conditions that improve the thermoelectric efficiency

Employing universal relations for the Onsager coefficients in the linear regime at the symmetric point of the single impurity Anderson model, we calculate the conditions under which the quantum scattering phase shift should satisfy to produce the asymptotic Carnot’s limit for the thermoelectric efficiency. We show that a single quantum dot connected by metallic leads at the Kondo regime cannot achieve the best thermoelectric efficiency. We study a serial double quantum dot system, with the quantum dots immersed in ballistic conduction channels. Each QD exhibits a strong but finite local electronic correlation UU. We show that maintaining one dot in the electron-hole symmetric point and allowing charge fluctuations in the other QD makes it possible to drive the system to the maximum thermoelectric efficiency. We also show that the bound states in the continuum (BICs) and quasi-BICs associated with the quantum scattering interference process drive the DQD to the maximum thermoelectric efficiency. We identify two types of quasi-BICs that occur at low and high temperatures: The first is associated with single Fano resonances, and the last is with several Fano processes. We also discussed possible temperature values and conditions that could be linked with the experimental realization of the results.

Enhanced Thermoelectric Transport Properties of Electronegative-Element-Filled and (Ni, Te) Co-Doped Skutterudites through S Filling

Enhanced Thermoelectric Transport Properties of Electronegative-Element-Filled and (Ni, Te) Co-Doped Skutterudites through S Filling

Excellent thermoelectric performance of Fe2NbAl alloy induced by strong crystal anharmonicity and high band degeneracy

Full-Heusler alloys with earth-abundant elements exhibit high mechanical strength and favorable electrical transport behavior, but their high intrinsic lattice thermal conductivity limits potential thermoelectric application. Here, the thermoelectric transport properties of Fe-based Full-Heusler Fe2MAl (M = V, Nb, Ta) alloys are comprehensively investigated utilizing density functional theory. The results suggest that Fe2NbAl exhibits exceptionally low lattice thermal conductivity due to low phonon velocities and weakly bound Nb atoms. In Fe2NbAl, the underbonding of the Nb atoms leads large Grüneisen parameters and high anharmonic scattering rates of low-frequency acoustic phonon. Meanwhile, the high band degeneracy and large electrical conductivity lead to a maximum p-type power factor of 255.6 μW·K−2·cm−1 at 900 K. The combination of low lattice thermal conductivity and favorable electrical transport properties leads a maximum p-type dimensionless figure of merit of 1.7. Our work indicates Fe2NbAl, as a low-cost, environmentally friendly, is a potential high-performance p-type thermoelectric material.

Reduced thermal conductivity and enhanced TE performance in CrSb2 via Fe-Bi co-substitution

The efficiency of thermoelectric (TE) technology relies on the performance of TE materials. Substitution with heavy elements is an effective strategy in TE for enhancing phonon scattering without much affecting electrical transport properties. However, selecting suitable dopants to achieve a high TE figure-of-merit (ZT) poses a significant challenge. Thus, in this study, the efficacy of combined (Fe and Bi) co-substitution in CrSb2 is investigated as a promising strategy to enhance ZT by lowering thermal conductivity. A series of co-substituted Cr1−x Fe x BiySb2−y (x = 0, 0.25, 0.50, 0.75, 1 and y = 0.10, 0.15, 0.20,0.25) samples were synthesized via furnace reaction followed by spark plasma sintering technique. Phase analysis and temperature dependence TE transport properties were systematically studied on synthesized samples. Furthermore, to analyze the impact of disorder induced by Bi/Fe substitution, electronic structure calculation was performed using the projector augmented-wave method. Notably, Cr0.75Fe0.25Bi0.15Sb1.85 exhibited a low thermal conductivity of ∼2.5 W m−1 K−1 at 300 K, which reduced to half compared to that of pristine CrSb2 (∼5 W m−1 K−1). This reduction is attributed to the introduction of significant mass fluctuations and point defects along with the presence of Bi at grain boundaries by co-substitution. Consequently, a remarkable 90% enhancement in ZT (∼0.021) at 350 K was achieved for Cr0.75Fe0.25Bi0.15Sb1.85 compared to that of pristine CrSb2 (ZT ∼ 0.012). This study can provide valuable insights into the rational design of effective dopants in other TE materials also.

First-principles study of the effect of Dirac phonons on the thermoelectric properties in monolayer Ge2H2

The Dirac phonons have been widely attention due to their unique edge or surface states. However, research on their influence in the realm of thermoelectric transport in semiconductor materials remains limited. Here, we have systematically investigated the geometric structure, stability, electronic, thermal conductivity, and thermoelectric properties of the monolayer Ge2H2 and Ge2 based on density functional theory and the Boltzmann transport equation (BTE). The phonon spectrum of monolayer Ge2H2 exhibits both Hourglass-type and Dirac-type phonon dispersion curves. The band structure of monolayer Ge2H2 reveals a relatively large band gap of 1.02 eV (1.75 eV for HSE), indicating that it is a direct band gap semiconductor. These two features make monolayer Ge2H2 an ideal material for exploring the effect of Dirac phonons on thermoelectric transport properties. In this paper, we determined that the lattice thermal conductivity (κl) in Ge2H2 is 0.59 Wm−1K−1 at 300 K, but undergoes a sharp increase upon removal of H atoms. This is mainly attributed to the disappearance of the Dirac phonons and the change of lattice vibration modes by removing the H atoms. While also exhibiting high carrier mobilities (134.86 cm2/Vs for holes) and extended scattering time (4.22 × 10−14 s for holes), indicative of excellent thermoelectric performance. With increasing temperature, the ZTmax of p-type doping reaches 0.63 at 700 K in Ge2H2. Remarkably, at 300K, the Hourglass-type phonon contributes only 5.94 % to κl, while the Dirac phonon contributes 3.44 %. Further analysis reveals that the Dirac phonon within Hourglass-type in monolayer Ge2H2 contributes 2.5 % to the ZTmax at 300K. Our investigation elucidates the impact of Dirac phonons on thermoelectric properties, providing valuable insights for future design and exploration of high-ZT thermoelectric materials.

Insights into enhanced thermoelectric performance of the n-type Mg3Sb2-based materials by amphoteric Al doping

Doping has the potential to alter the levels of anharmonicity in compounds by attenuating bonding strength. In this study, we explore the efficacy of amphoteric Al doping for stimulating anharmonicity in n-type Mg3.25AlxSb1.48Bi0.48Te0.04 to attain enhanced phonon scattering and thermoelectric performance. First-principles calculations and experimental data reveal the occupation of both Sb and Mg2 sites by amphoteric Al atoms in the anionic framework of Mg3.25AlxSb1.48Bi0.48Te0.04. A marginal variation in both carrier concentration and mobility sustains the high power factor without affecting the Seebeck coefficient, implying amphoteric doping induced charge compensation. While phonon velocity, Grüneisen parameter, and crystal orbital Hamilton population calculations results indicate that phonon softening and bond weakening are realized via Al doping, leading to an enhanced lattice anharmonicity and a reduced lattice thermal conductivity. A remarkable enhancement ∼16% in the peak figure of merit ZTpeak and the average ZTavg, was attained for the x = 0.015 sample, when compared with the un-doped sample. Hence, the amphoteric doping can serve as an effective means to optimize ZT values by decoupling the intertwined thermoelectric transport properties.

Thermoelectric transport properties in Janus Rashba semiconductors of monolayer Si2AsSb and Si2SbBi

Thermoelectric transport properties in Janus Rashba semiconductors of monolayer Si2AsSb and Si2SbBi

High In-Plane Thermoelectric Performance of Layered Bi4O4SeCl2.

The van der Waals semiconductor Bi4O4SeCl2 has recently attracted great interest due to its extremely small lattice thermal conductivity, which may find possible application in the field of energy conversion. Herein, we accurately predict the thermoelectric transport properties of Bi4O4SeCl2 using first-principles calculations and Boltzmann transport theory, where the carrier relaxation time is obtained by fully considering the electron-phonon coupling. It is found that a maximum p-type ZT value of 3.1 can be reached at 1100 K along the in-plane direction, which originates from increased Seebeck coefficient induced by multivalley band structure, as well as enhanced electrical conductivity caused by relatively stronger intralayer bonding. Besides, it is interesting to note that comparable p- and n-type ZT values can be realized in certain temperature regions, which is very desirable in the fabrication of thermoelectric modules.

Evolution of thermoelectric transport properties of Sb2Te3–Sb2Se3 solid-solution alloys depending on phase formation behavior

Sb2Te3-based alloys exhibit decent thermoelectric transport properties in the mid-temperature range above 550 K. However, the study on Sb2Te3 alloys has been limited in simple doping approach. Herein, evolution in the thermoelectric transport properties associated with the phase formation of solid solution alloys of Sb2(Te1−xSex)3 (x = 0, 0.25, 0.33, 0.5, 0.75, and 1.0) compositions is investigated to widen the strategy to solid solution alloying. A single phase of the Sb2Te3 rhombohedral structure formed from x = 0 to 0.5, whereas mixed phases with an orthorhombic structure of Sb2Se3 was observed at x = 0.75. The electrical conductivity weighted mobility were gradually decreased as Se content increases to x = 0.75. Consequently, the power factor was decreased gradually and significantly to 0.076 mW/mK2 for x = 0.75 (Sb2(Te0·25Se0.75)3) compared with 2.6 mW/mK2 of the pristine sample. The total thermal conductivity of 2.0 W/mK for the Sb2Te3 was significantly reduced gradually to 0.64 W/mK for x = 0.75 owing to simultaneous decrease in electrical and lattice thermal conductivities. The reduction in lattice thermal conductivity is mainly owing to the addition point defect scattering caused by the Se addition. Nevertheless, thermoelectric figure of merit zT of Sb2Te3 is gradually decreased from 0.64 to 0.11 for x = 0.75 at 650 K due to the degradation in electrical transport properties. Furthermore, the theoretical zT was estimated for all samples with varying carrier concentration based on single parabolic band model.

Comparison of the excellent thermoelectric properties of the half-Heusler compounds RbMgSb with a host-guest structure and LiMgSb

In this work, we systematically studied the thermoelectric (TE) transport properties of the half-Heusler compounds AMgSb (A = Li, Rb) based on an incorporation of first-principles calculations with self-consistent phonon theory and Boltzmann transport equations. We noted significant changes in the vibrational behavior of alkali metal atoms with a substantial increase in atomic mass. This alteration led to the formation of a host-guest structure in RbMgSb. In contrast, the stronger harmonic vibrations in LiMgSb results in it maintaining a Half-Heusler structure, without the pronounced anharmonicity found in RbMgSb. The calculation results reveal that RbMgSb has ultra-low lattice thermal conductivity κL, which is ten times lower than LiMgSb. We show that rattlers cause tenfold reductions in the thermal conductivity by increasing the phonon–phonon scattering probability, occurred in a wide frequency range. In addition, after careful consideration of multiple scattering mechanisms, the multiple valleys, high dispersion, flat band edges and band asymmetry near the Fermi level give both materials excellent electron transport properties. At the same time, LiMgSb itself already has a very low electron thermal conductivity κe, but the κe of RbMgSb is ten times smaller than that. As a consequence, remarkable ZT values of 2.51 and 3.45 at 900 K are captured in n-type LiMgSb and p-type RbMgSb, respectively. These findings reveal the promising potential of AMgSb in TE applications.

Advancing Heteroanionicity in Zintl Phases: Crystal Structures, Thermoelectric and Magnetic Properties of Two Quaternary Semiconducting Arsenide Oxides, Eu8Zn2As6O and Eu14Zn5As12O.

Two novel quaternary oxyarsenides, Eu8Zn2As6O and Eu14Zn5As12O, were synthesized through metal flux reactions, and their crystal structures were established by single-crystal X-ray diffraction methods. Eu8Zn2As6O crystallizes in the orthorhombic space group Pbca, featuring polyanionic ribbons composed of corner-shared triangular [ZnAs3] units, running along the [100] direction. The structure of Eu14Zn5As12O crystallizes in the monoclinic space group P2/m and its anionic substructure can be described as an infinite "ribbonlike" chain comprised of [ZnAs3] trigonal-planar units, although the structural complexity here is greater and also amplified by disorder on multiple crystallographic positions. In both structures, the O2- anion occupies an octahedral void with six neighboring Eu2+ cations. Formal electron counting, electronic structure calculations, and transport properties reveal the charge-balanced semiconducting nature of these heteroanionic Zintl phases. High-temperature thermoelectric transport properties measurements on Eu14Zn5As12O reveal relatively high resistivity (ρ500K = 8 Ω·cm) and Seebeck coefficient values (S500K = 220 μV K-1), along with a low concentration and mobility of holes as the dominant charge-carriers (n500K = 8.0 × 1017 cm-3, μ500K = 6.4 cm2/V s). Magnetic studies indicate the presence of divalent Eu2+ species in Eu14Zn5As12O and complex magnetic ordering, with two transitions observed at T1 = 21.6 K and T2 = 9 K.

Electronic, thermoelectric and electrical transport properties of single layer γ-graphyne

Recently, graphyne has emerged as the sole two-dimensional carbon material exhibiting both sp and sp2 hybridization. It’s remarkable attributes have ignited considerable interest, particularly in the realm of optoelectronics, driven by its narrow band gap, signifying its vast potential in this field. In this paper we investigated electronic, thermoelectric and electrical transport properties of single layer γ-graphyne systematically and comparatively by using density functional theory (DFT). Our findings reveal that γ-graphyne displays pronounced absorption peaks within both the infrared (IR) and visible regions (VR), indicating its robust optical characteristics. Additionally, γ-graphyne showcases exceptional thermoelectric performance. The insights gained from this study elucidate the properties of γ-graphyne and suggest its applicability across various domains, including optical sensing and thermoelectric energy conversion devices.

Synergistically optimizing thermoelectric transport properties of Te via Se and S co-alloying

Elemental tellurium has been considered as a potential thermoelectric candidate due to its simple chemical composition and lack of segregation. Meanwhile, the simplicity of the materials is accompanied by a restricted freedom to tune the chemical composition and transport properties. Based on the solid solubility between Te with IV-group Se and S elements, this work attempts to forming atomic-disordered solid solution (Te1-x-ySexSy)0.98Sb0.02, with antimony (Sb) acting as p-type dopants. The X-ray diffraction confirms that the alloying not only enables a solid solubility within 6 at % but also enhances the effectiveness of Sb doping. The appropriate alloying concentration are demonstrated to be beneficial in achieving a higher power factor owing to the weaker electron-phonon coupling and optimized carrier concentration. The 6 at% S/Se alloying in Te enables a 50 % reduction in lattice thermal conductivity at room temperature by enhanced phonon scattering. A maximum figure of merit (zT) value of 0.81 at 600 K were realized in 2 at% Se and S/Se alloyed samples. This work highlights the impact of alloying on thermoelectric performance of Te elemental materials.