Approaching lower bound of lattice thermal conductivity by simultaneously suppressing diagonal and off-diagonal phonon contributions

Phonon and electronic transport of buckled structured SiGe monolayer and halogenated SiGe monolayers (X2-SiGe, X = F, Cl, and Br) are investigated for the first-time using ab initio density functional theory (DFT). The phonon calculations reveal complete dynamical stability of SiGe and fluorinated (F2-SiGe) monolayers in contrast to earlier reported works, where a small magnitude of imaginary frequency in SiGe monolayer near the zone centre of the Brillouin zone (BZ) is observed. The phonon calculations of chlorinated and brominated SiGe reveal no dynamical stability even with very high convergence parameters and better computational accuracy. The lower value of lattice thermal conductivity in the case of F2-SiGe is attributed to the strong phonon anharmonic scattering and larger contribution of the three phonon process to anharmonic scattering. The semimetallic nature of the SiGe monolayer turns to semiconducting after halogenation. We have also calculated the electron relaxation time to study their precise thermoelectric parameters. The enhancement of the Seebeck coefficient and reduction in lattice thermal conductivity in the SiGe monolayer is observed after halogenation which results in the improvement of the thermoelectric figure of merit (ZT). The room temperature figure of merit, ZT, which is 0.112 for the SiGe monolayer, enhances significantly to 0.737 after addition of fluorine atoms. Our study suggests that the halogenation of two-dimensional materials can improve their thermoelectric properties.

Reducing lattice thermal conductivity (κl) that reflects the material’s heat-carrying capacity through lattice phonon vibrations is crucial for optimizing the figure of merit (zT). Using density functional theory (DFT) and density functional perturbation theory (DFPT), present work considers the structural, electronic, magnetic, and phonon properties of the XNiSn (X=Ti, Zr, Hf ) half Heusler (hH) compounds. TiNiSn, ZrNiSn, and HfNiSn are identified as semiconductors with indirect band gaps of 0.43 eV, 0.47 eV and 0.39 eV, respectively, exhibiting dynamical stability. The temperature- dependent κl of hH XNiSn are compared using Slack’s model with two approaches for analyzing phonon velocity: elastic constants from quasi- harmonic approximation (QHA) as implemented in the Thermo_pw code and slope of phonon bands based on DFPT. At room temperature, TiNiSn, ZrNiSn and HfNiSn have κl values of 28.61 Wm−1K−1, 34.61 Wm−1K−1 and 29.85 Wm−1K−1 respectively using phonon velocity from slopes of phonon bands based on DFPT. These values show deviation of 1.48%, 6.29%, and 5.82% to those κl values 29.01 Wm−1K−1’, 36.79 Wm−1K−1 and 31.59 Wm−1K−1 for TiNiSn, ZrNiSn and HfNiSn respectively using QHA.

ABSTRACTOver the last decade, there has been a great enhancement in efficiency of bulk thermoelectric materials by reducing lattice thermal conductivity with internal nanostructures. This includes sintered nanostructures, which has merit in applicability and scalability. While the material development so far has been rather empirical, for further improvement of the bulk nanostructured materials, the need for material design based on prediction of lattice thermal conductivity is growing. This paper reviews recently developed multiscale method to calculate lattice thermal conductivity of bulk crystalline nanostructures. The method seamlessly combines first-principles calculations of interatomic force constants, lattice dynamics calculations of intrinsic phonon transport properties, and Monte Carlo simulation of phonon Boltzmann transport through nanostructures. The method can handle phonon transport through a large system with randomly placed and shaped nanostructures, and thus it is sufficient to quantify how reduction of thermal conductivity of polycrystalline nanostructures depends on mean size and distribution of nano-grains. The results for sintered polycrystalline silicon nanostructure are presented.

Quaternary chalcogenides have garnered considerable interest within the field of thermoelectric due to their intrinsic low thermal conductivity, wide bandgap and high element enrichment advantages. In this work, the thermoelectric performance of Cu2MnSnSe4 was enhanced by co-optimizing the carrier concentration and lattice thermal conductivity through self-doping with Cu and doping with Te. A series of Cu2MnSnSe4 and Cu2.1Mn0.9SnSe4-x Tex (x = 0, 0.01, 0.05, 0.10) samples were prepared by ball-milling and hot-pressing methods. The carrier concentration of the samples was significantly increased after Cu self-doping, leading to optimized electrical transport performance. The notable reduction in lattice thermal conductivity was attributed to the scattering effect caused by Te substitution-induced point defects. At 673 K, the lattice thermal conductivity of the Cu2.1Mn0.9SnSe3.9Te0.1 sample obtained the lowest value of 0.62 W m-1K-1. Finally, it achieved a maximum zT ~ 0.5 at 673 K in the Cu2.1Mn0.9SnSe3.9Te0.1 sample, roughly twice that of the Cu2MnSnSe4 sample.

Uranium mononitride (UN) is a promising nuclear fuel with a high melting point, high thermal conductivity, and low coefficient of thermal expansion. Theoretical studies of UN can provide insights on its thermal transport mechanism, which is of great significance for the design and application of UN fuel. During the processing and operation, crystal defects and impurities, such as vacancies and carbon impurities, potentially arise in the nuclear fuel, which probably affect the thermomechanical properties of UN. To figure out the effect of vacancy defects and carbon impurities on the thermal conductivity of UN, density functional theory and Boltzmann transport theory are applied to conduct a theoretical investigation on the mechanical and thermal properties of ideal and defective UN. The calculated results show that in the case of UN with a U or N vacancy, both the lattice and electronic thermal conductivity are decreased, compared with the ideal case. With a carbon atom occupying the N site in the lattice, the electronic thermal conductivity is reduced but the lattice thermal conductivity is increased. Combining the results of lattice and electronic thermal conductivity, the total thermal conductivities of three defective states are lower than the ideal UN. The thermal conductivities of UN with a U vacancy (13.91 W/mK), N vacancy (15.36 W/mK), and a carbon atom occupying the N site (15.14 W/mK) are, respectively, reduced by 25.7%, 18.0%, and 19.2%, in comparison with ideal result (18.73 W/mK) at 1000 K.

Thermoelectric materials enables the harvest of waste heat and directly conversion into electricity. In search of high efficient thermoelectric materials, low thermal conductivity of a material is essential and critical. Here, we have theoretically investigated the lattice thermal conductivity and thermoelectric properties of layered intermetallic Na$_2$MgSn and Na$_2$MgPb based on the density functional theory and linearized Boltzmann equation with the single-mode relaxation-time approximation. It is found that both materials exhibit very low and anisotropic intrinsic lattice thermal conductivity. Despite of the very low mass density and simple crystal structure of Na$_2$MgSn, its lattice thermal conductivities along $a$ and $c$ axes are only 1.75 and 0.80 W/m$\cdot$K respectively at room temperatures. When Sn is replaced by the heavier element Pb, its lattice thermal conductivities decrease remarkably to 0.51 and 0.31 W/m$\cdot$K respectively along $a$ and $c$ axes at room temperatures. We show that the low lattice thermal conductivities of both materials are mainly due to their very short phonon lifetimes, which are roughly between 0.4 to 4.5 ps. Combined with previous experimental measurements, the metallic Na$_2$MgPb can not be a good thermoelectric material. However, we predict that the semiconducting Na$_2$MgSn is a potential room-temperature thermoelectric material with a considerable $ZT$ of 0.34 at 300 K. Our calculations not only imply that the intermetallic Na$_2$MgSn is a potential thermoelectric material, but also can motivate more theoretical and experimental works on the thermoelectric researches in simple layered intermetallic compounds.

The fundamental challenge for enhancing the thermoelectric performance of n-type PbTe to match p-type counterparts is to eliminate the Pb vacancy and reduce the lattice thermal conductivity. The Cu atom has shown the ability to fill the cationic vacancy, triggering improved mobility. However, the relatively higher solubility of Cu2Te limits the interface density in the n-type PbTe matrix, leading to a higher lattice thermal conductivity. In particular, a quantitative relationship between the precipitate scattering and the reduction of lattice thermal conductivity in the n-type PbTe with low solubility of Cu2Te alloys still remains unclear. In this work, trivalent Sb atoms are introduced, aiming at decreasing the solubility of Cu in PbTe for improving the precipitate volumetric density and ensuring n-type degenerate conduction. Benefiting from the multiscale hierarchical microstructures by Sb and Cu codoping, the lattice thermal conductivity is considerably decreased to 0.38 W m-1 K-1. The Debye-Callaway model quantifies the contribution from point defects and nano/microscale precipitates. Moreover, the mobility increases from 228 to 948 cm2 V-1 s-1 because of the elimination of cationic vacancies. Consequently, a high quality factor is obtained, enabling a superior peak figure of merit ZT of ∼1.32 in n-type Pb0.975Sb0.025Te by alloying with only ∼1.2% Cu2Te. The present finding demonstrates the significant role of low-solubility Cu2Te in advancing thermoelectrics in n-type PbTe.

Striving for improvements of the thermoelectric (TE) properties of the technologically important lead telluride (PbTe) compound, we investigate the influence of different doping elements on the thermal conductivity, Seebeck coefficient, and electrical conductivity applying density functional theory calculations. Our approach combines total-energy calculations yielding lattice vibrational properties with the Boltzmann transport theory to obtain electronic transport properties. We find that doping with elements from the 1st and 3rd columns of the periodic table reduces the sound velocity and, consequently, the lattice thermal conductivity, while 2nd column dopants have no such influence. Furthermore, 1.6 at. % doping with 4th and 5th column elements provides the highest reduction of lattice thermal conductivity. Out of this group, Hf doping results in maximum reduction of the sound velocity from 2030 m s−1 for pure PbTe to 1370 m s−1, which is equivalent to ca. 32% reduction of lattice thermal conductivity. The highest power factor values calculated for 1.6 at. % doping range between 40 and 56 μW cm−1 K−2, and are obtained for substitution with dopants having the same valence as Pb or Te, such as those located at the 2nd, 14th, and 16th columns of the periodic table. We demonstrate how this method may be generalized for dopant-selection-oriented materials design aimed at improving TE performance of other compounds.

Alloy scattering to optimize carrier and phonon transport properties in PbBi2S4 thermoelectric

Inspired by recent experimental synthesis of prototypical Sn(1−x)Pb(x)O under ambient and high-temperature conditions, we systematically construct layered Sn(1−x)Pb(x)O alloys across a range of compositions. Herein, we study the thermoelectric properties of layered Sn(1−x)Pb(x)O compositions using the first-principles-based density functional theory and density functional perturbation theory calculations. Our results show that Sn(1−x)Pb(x)O compositions exhibit very low lattice thermal conductivity (κl) of 2.94 and 1.83 W/m K for x = 0.5 and 1, respectively, at 300 K. Such remarkably low κl of Sn0.5Pb0.5O and PbO primarily originates from pronounced phonon softening and coupling of phonon branches driven by the presence of mass anisotropy and symmetry breaking induced by Pb substitution. Furthermore, in our present study, the inclusion of Fröhlich interaction addresses limitations in the conventional deformation potential theory formalism, allowing for a more rigorous and accurate assessment of carrier mobility. Interestingly, Sn0.5Pb0.5O reveals superior Seebeck values for both charge types, with 1127.4 μV/K (p-type) and −1078.4 μV/K (n-type) at 300 K, compared to SnO and PbO, attributed to its higher band effective mass and moderate carrier concentration within the system. Moreover, our results reveal that Pb substitution in Sn0.5Pb0.5O benefits n-type transport by increasing carrier concentrations; however, it adversely affects p-type conductivity due to heavier hole effective masses and reduced mobility. Henceforth, leveraged by the superior phononic and electronic transport properties, Sn0.5Pb0.5O composition emerges as a superior n-type thermoelectric material that outperforms the other two systems, as its ZT reaches a significant maximum value of 3.19 at 900 K.

Surface and strain engineering are among the cheaper ways to modulate structure property relations in materials. Due to their compositional flexibilities, MXenes, the family of two-dimensional materials, provide enough opportunity for surface engineering. In this work, we have explored the possibility of improving thermoelectric efficiency of MXenes through these routes. The Janus MXenes obtained by modifications of the transition metal constituents and the functional groups passivating their surfaces are considered as surface engineered materials on which bi-axial strain is applied in a systematic way. We find that in the three Janus compounds Zr2COS, ZrHfCO2and ZrHfCOS, tensile strain modifies the electronic and lattice thermoelectric parameters such that the thermoelectric efficiency can be maximised. A remarkable reduction in the lattice thermal conductivity due to increased anharmonicity and elevation in Seebeck coefficient are obtained by application of moderate tensile strain. With the help of first-principles electronic structure method and semi-classical Boltzmann transport theory we analyse the interplay of structural parameters, electronic and dynamical properties to understand the effects of strain and surface modifications on thermoelectric properties of these systems. Our detailed calculations and in depth analysis lead not only to the microscopic understanding of the influences of surface and strain engineering in these three systems, but also provide enough insights for adopting this approach and improve thermoelectric efficiencies in similar systems.

Sb2Si2Te6 is a promising 2D material for medium-temperature thermoelectric applications, with the thermoelectric figure of merit zT approaching 1 at 823 K. However, its widespread use has been limited by relatively low power factor values. In this study, we successfully enhanced the performance of Sb2Si2Te6 by introducing Yttrium nanocomposites. This modification fine-tuned the carrier concentration and electrical conductivity, and increased the power factor up to 946 μW K-1 at 570 K. Jonker plot analysis revealed that increased carrier concentration did not affect the intrinsic electronic properties. SEM and TEM analyses revealed that Y nano-compositing introduced secondary phases, reducing the lattice thermal conductivity to values close to simulated ones using the Debye-Callaway model. Sb1.98Y0.02Si2Te6 exhibited the highest zT of 1.49 at 773 K due to the ultralow lattice thermal conductivity of 0.29 W m-1 K-1 and a moderate power factor of 858 μW K-1 at the same temperature. The single parabolic band (SPB) model suggests that with further optimization of the Fermi level and additional reduction in lattice thermal conductivity, the zT value could potentially increase to 1.55. These results demonstrate the potential of Y nanocompositing for enhancing Sb2Si2Te6 as an efficient medium-temperature thermoelectric material.

This review discusses recent developments and current research in high performance bulk thermoelectric materials, comprising nanostructuring, mesostructuring, band alignment, band engineering and synergistically defining key strategies for boosting the thermoelectric performance. To date, the dramatic enhancements in the figure of merit achieved in bulk thermoelectric materials have come either from the reduction in lattice thermal conductivity or improvement in power factors, or both of them. Here, we summarize these relationships between very large reduction of the lattice thermal conductivity with all-scale hierarchical architecturing, large enhanced Seebeck coefficients with intra-matrix electronic structure engineering, and control of the carrier mobility with matrix/inclusion band alignment, which enhance the power factor and reduce the lattice thermal conductivity. The new concept of hierarchical compositionally alloyed nanostructures to achieve these effects is presented. Systems based on PbTe, PbSe and PbS in which spectacular advances have been demonstrated are given particular emphasis. A discussion of future possible strategies is aimed at enhancing the thermoelectric figure of merit of these materials.

Highly dense pore structure was generated by simple sequential routes using NaCl and PVA as porogens in conventional PbTe thermoelectric materials, and the effect of pores on thermal transport properties was investigated. Compared with the pristine PbTe, the lattice thermal conductivity values of pore-generated PbTe polycrystalline bulks were significantly reduced due to the enhanced phonon scattering by mismatched phonon modes in the presence of pores (200 nm–2 μm) in the PbTe matrix. We obtained extremely low lattice thermal conductivity (~0.56 W m−1 K−1at 773 K) in pore-embedded PbTe bulk after sonication for the elimination of NaCl residue.

Enhanced thermoelectric performance in Cu2GeSe3 via (Ag,Ga)-co-doping on cation sites