The Seebeck coefficient and electrical conductivity are two critical quantities to optimize simultaneously in designing thermoelectric materials, and they are determined by the dynamics of carrier scattering. We uncover a new regime where the co-existence at the Fermi level of multiple bands with different effective masses leads to strongly energy-dependent carrier lifetimes due to intrinsic electron-phonon scattering. In this anomalous regime, electrical conductivity decreases with carrier concentration, Seebeck coefficient reverses sign even at high doping, and power factor exhibits an unusual second peak. We discuss the origin and magnitude of this effect using first-principles Boltzmann transport calculations and simplified models. We also identify general design rules for using this paradigm to engineer enhanced performance in thermoelectric materials.
Band convergence is considered a clear benefit to thermoelectric performance because it increases the charge carrier concentration for a given Fermi level, which typically enhances charge conductivity while preserving the Seebeck coefficient. However, this advantage hinges on the assumption that interband scattering of carriers is weak or insignificant. With first-principles treatment of electron-phonon scattering in CaMg$_{2}$Sb$_{2}$-CaZn$_{2}$Sb$_{2}$ Zintl system and full Heusler Sr$_{2}$SbAu, we demonstrate that the benefit of band convergence can be intrinsically negated by interband sca…
We report on the elaboration of germanium manganese nanostructured thin films and the measurement of their thermoelectric properties. We investigate the growth of Ge:Mn layers along with a thorough structural characterization of this materials at the nanoscale. The room temperature thermoelectric properties of these layers containing spherical inclusions are discussed regarding their potential as a model of "electron crystal phonon glass material". We show that the thermal conductivity can be decreased by a factor of 30, even if the electronic properties can be conserved as in the bulk. The th…
For high efficiency thermoelectric power conversion not only improvement of materials properties but also prediction and synthesis of new thermoelectric materials is needed. Here we have carried out a systematic investigation on thermoelectric performance of newly predicted two dimensional (2D) semiconducting SiS2 and SiSe2 monolayers of group IVA-VIA family using density functional theory (DFT) and Boltzmann transport equation (BTE). Our computed values of lattice thermal conductivity (kph) are ultralow which result very high thermoelectric figure of merit (ZT) value of 0.78 (0.80) at 500K in…
Low-dimensional electronic and glassy phononic transport are two important ingredients of highly-efficient thermoelectric material, from which two branches of the thermoelectric research emerge. One focuses on controlling electronic transport in the low dimension, while the other on multiscale phonon engineering in the bulk. Recent work has benefited much from combining these two approaches, e.g., phonon engineering in low-dimensional materials. Here, we propose to employ the low-dimensional electronic structure in bulk phonon-glass crystal as an alternative way to increase the thermoelectric …
While the thermoelectric figure of merit zT above 300K has seen significant improvement recently, the progress at lower temperatures has been slow, mainly limited by the relatively low Seebeck coefficient and high thermal conductivity. Here we report, for the first time, success in first-principles computation of the phonon drag effect - a coupling phenomenon between electrons and non-equilibrium phonons - in heavily doped region and its optimization to enhance the Seebeck coefficient while reducing the phonon thermal conductivity by nanostructuring. Our simulation quantitatively identifies th…
We present a first principles based model of electron-phonon scattering mechanisms and thermoelectric transport at the L and $Σ$ valleys in <200b>$p$-type PbTe, accounting for their thermally induced shifts. Our calculated values of all thermoelectric transport parameters at room temperature are in very good agreement with experiments for a wide range of doping concentrations. Scattering due to longitudinal optical phonons is the main scattering mechanism in $p$-type PbTe, while scattering due to transverse optical modes is the weakest. The L valleys contribute most to thermoelectric transport…
Using a first-principles cluster expansion, we shed light on the solid-state phase diagram and structure of the recently discovered high-performance thermoelectrics, Pb-Ag-Sb-Te alloys. The observed nanoscale inhomogeneities are shown to be coherent precipitates of ordered (Ag)m(Sb)n(Te)m+n phases, such as AgSbTe2, all immiscible with rocksalt PbTe. The solubility is high for PbTe in AgSbTe2 and low for (Ag,Sb)Te in PbTe (8% vs. 0.6% at 850 K). The differences in the phonon spectra of PbTe and AgSbTe2 confirm that the inhomogeneities enhance the thermoelectric performance.
It is generally assumed in the thermoelectric community that the lattice thermal conductivity of a given material is independent of the electronic properties. This perspective is however questionable since the electron-phonon coupling could have certain effects on both the carrier and phonon transport, which in turn will affect the thermoelectric properties. Using SiGe compound as a prototypical example, we give an accurate prediction of the carrier relaxation time by considering scattering from all the phonon modes, as opposed to the simple deformation potential theory. It is found that the c…
We report calculations of the electronic structure, vibrational properties and transport for the p-type semiconductors, SrAg$Ch$F ($Ch$=S, Se and Te). We find soft phonons with low frequency optical branches intersecting the acoustic modes below 50 $cm^{-1}$, indicative of a material with low thermal conductivity. The bands at and near the valence band maxima are highly two dimensional, which leads to high thermopowers even at high carrier concentrations, which is a combination that suggests good thermoelectric performance. These materials may be regarded as bulk realizations of superlattice t…
The anharmonic lattice dynamics of rock-salt thermoelectric compounds SnTe and PbTe are investigated with inelastic neutron scattering (INS) and first-principles calculations. The experiments show that, surprisingly, although SnTe is closer to the ferroelectric instability, phonon spectra in PbTe exhibit a more anharmonic character. This behavior is reproduced in first-principles calculations of the temperature-dependent phonon self-energy. Our simulations reveal how the nesting of phonon dispersions induces prominent features in the self-energy, which account for the measured INS spectra and …
We estimate the contribution of the long-wavelength el-TO-ph interaction and discuss the effect it has on electron pairing in doped polar systems like SrTiO3 and PbTe. The analytical and numerical results presented in the study indicate that the el-TO-ph interaction tends to contribute little to the total strength of electron-phonon coupling in these and related materials. To explain this fact we consider possible reasons why the effect of the polar long-wavelength transverse optical phonons on the coupling constant "lambda" is far less than one might suppose.
Inelastic neutron scattering measurements are utilized to explore relative changes in the generalized phonon density of states of nanocrystalline Si1xGex thermoelectric materials prepared via ball milling and hot-pressing techniques. Dynamic signatures of Ge clustering can be inferred from the data by referencing the resulting spectra to a density functional theoretical model assuming homogeneous alloying via the virtual-crystal approximation. Comparisons are also presented between as-milled Si nanopowder and bulk, polycrystalline Si where a preferential low-energy enhancement and lifetime bro…
We have investigated the effect of unconventional pairing mechanism in MgB2 using a two-band model within the framework of Bogoliubov-Valatin formalism. The approach incorporates the intra- band s-wave interaction in the s- and p-bands, as well as interband s-wave interaction between them. The analysis assumes the pairing interaction matrix comprises of attractive electron-phonon, charge fluctuation and repulsive electron-electron (Coulomb) interactions to account for superconductivity in MgB2. The model is used to estimate the transition temperature and isotope effect exponent as well as to e…
The first order standard perturbation theory combined with ab initio projector augmented wave operator challenges the realization of the standard Sternheimer equation with linear computational efficiency. This efficiency motivates us to describe the electron-phonon interaction in two-dimensional (2D) black phosphorous monolayer using generalized density functional perturbation theory (DFPT) with Boltzmann transport theory (BTE). Subsequently, linear response phonon dynamic behaviour in terms of conductivities, seebeck coefficients and transport properties are focused for its thermoelectric app…
One of the key requirements for good thermoelectric materials is a low lattice thermal conductivity. Here we present a combined neutron scattering and theoretical investigation of the lattice dynamics in the type I clathrate system Ba-Ge-Ni, which fulfills this requirement. We observe a strong hybridization between phonons of the Ba guest atoms and acoustic phonons of the Ge-Ni host structure over a wide region of the Brillouin zone which is in contrast with the frequently adopted picture of isolated Ba atoms in Ge-Ni host cages. It occurs without a strong decrease of the acoustic phonon lifet…
We present a fully ab initio based scheme to compute transport properties, i.e. the electrical conductivity σ and thermopower S, in the presence of electron-phonon interaction. Therefore, we explicitly investigate the k-dependent structure of the Eliashberg spectral function , the coupling strength, the linewidth and the relaxation time τ. We obtain a state-dependent τ and show its necessity to reproduce the increased thermopower at temperatures below the Debye temperature, without accounting for the phonon-drag effect. Despite the detailed investigations of various k and q dependencies, the p…
Engineering of thermoelectric materials requires an understanding of thermal conduction by lattice and electronic degrees of freedom. Filled skutterudites denote a large family of materials suitable for thermoelectric applications where reduced lattice thermal conduction attributed to localized low-frequency vibrations (rattling) of filler cations inside large cages of the structure. In this work, a multi-wavelength method of exploiting X-ray dynamical diffraction in single crystals of CeFe$_4$P$_{12}$ is presented and applied to resolve the atomic amplitudes of vibrations. The results suggest…
Since 2014 the layered semiconductor SnSe in the high-temperature Cmcm phase is known to be the most efficient thermoelectric material. Making use of first-principles calculations we show that its vibrational and thermal transport properties are determined by huge non-perturbative anharmonic effects. We show that the transition from the Cmcm phase to the low-symmetry Pnma is a second-order phase transition driven by the collapse of a zone border phonon, whose frequency vanishes at the transition temperature. Our calculations show that the spectral function of the in-plane vibrational modes are…
Local modes caused by defects play a significant role in the thermal transport properties of thermoelectrics. Of particular interest are charge-neutral defects that suppress thermal conductivity, without significantly reducing electrical transport. Here we report a temperature dependent Raman study, that identifies such a mode in a standard thermoelectric material, Bi2Te2Se. One of the modes observed, whose origin has been debated for decades, was shown mostly likely to be an antisite defect induced local mode. The anomalous temperature independent broadening of the local mode is ascribed to t…
Intervalley collisions, which scatter electrons from one valley or band to another, can be detrimental to thermoelectric performance in materials with multiple valleys/bands. In this study, density functional theory is used to investigate the electron-phonon scattering characteristics of three lead chalcogenides (PbS, PbSe, PbTe) and three half-Heuslers (ScNiBi, ScPdSb, ZrNiSn), which all possess multiple equivalent conduction valleys, in order to characterize and analyze their intravalley/intervalley components. To elucidate what controls the degree of intravalley and intervalley transitions,…
The electronic and phonon transport properties of graphene-like boron phosphide (BP), boron arsenide (BAs), and boron antimonide (BSb) monolayers are investigated using first-principles calculations and Boltzmann theory. By considering both the phonon-phonon and electron-phonon scatterings, we demonstrate that the strong bond anharmonicity in the BAs and BSb monolayers can dramatically suppress the phonon relaxation time but hardly affects that of electrons. As a consequence, both systems exhibit comparable power factors with that of the BP monolayer but much lower lattice thermal conductiviti…
The mean-free-paths (MFPs) of energy carriers are of critical importance to the nano-engineering of better thermoelectric materials. Despite significant progress in the first-principles-based understanding of the spectral distribution of phonon MFPs in recent years, the spectral distribution of electron MFPs remains unclear. In this work, we compute the energy dependent electron scatterings and MFPs in silicon from first-principles. The electrical conductivity accumulation with respect to electron MFPs is compared to that of the phonon thermal conductivity accumulation to illustrate the quanti…
Electron-crystal and phonon-glass are regarded as two essential factors for ideal thermoelectric materials, which require both an enhanced electronic transport and a depressed phononic transport. These two characteristics usually can not coexist in complete bulk semiconductors because of the strong interaction between electrons and phonons. Introducing nanostructures into bulk thermoelectric materials has long been applying to allow for diverse phonon scattering mechanisms to reduce lattice thermal conductivity while keeping the electrical conductivity intact. However, some two-dimensional mat…
Recently published discoveries of acoustic and optical mode inversion in the phonon spectrum of certain metals became the first realistic example of non-interacting topological bosonic excitations in existing materials. However, the observable physical and technological use of such topological phonon phases remained unclear. In this work we provide a strong theoretical and numerical evidence that for a class of metallic compounds (known as triple point topological metals), the points in the phonon spectrum, at which three (two optical and one acoustic) phonon modes (bands) cross, represent a w…
Determining defect types and concentrations remains a big challenge of semiconductor materials science. By using ab-initio thermal conductivity calculations we reveal that Ni/vacancy antisites, and not the previously claimed Sn/Zr antisites, are the dominant defects affecting thermal transport in half-Heusler compound ZrNiSn. Our calculations correctly predict the thermal conductivity dependence with temperature and concentration, in quantitative agreement with published experimental results. Furthermore, we find a characteristic proportionality between phonon-antisite scattering rates and the…
Phonon properties of $\mathrm{Mo_3Sb_{7-x}Te_x}$ ($x=0,1.5, 1.7$), a potential high-temperature thermoelectric material, have been studied with inelastic neutron and x-ray scattering, and with first-principles simulations. The substitution of Te for Sb leads to pronounced changes in the electronic structure, local bonding, phonon density of states (DOS), dispersions, and phonon lifetimes. Alloying with tellurium shifts the Fermi level upward, near the top of the valence band, resulting in a strong suppression of electron-phonon screening, and a large overall stiffening of interatomic force-con…
The paper shows by calculation that the diffusion of nickel even for 50 years does not lead to degradation of thermoelectric generator modules. In the process, we used the theory of composites to calculate the electrical contact resistance, our own diffusion theory of electrical contact resistance, as well as the method for approximating the temperature dependences of thermoelectric material characteristics from the experimental data. When using the above method, it was assumed that the main mechanism of scattering of free charge carriers in a thermoelectric material is their scattering on the…
We calculate the phonon-dispersion relations of several two-dimensional materials and diamond using the density-functional based tight-binding approach (DFTB). Our goal is to verify if this numerically efficient method provides sufficiently accurate phonon frequencies and group velocities to compute reliable thermoelectric properties. To this end, the results are compared to available DFT results and experimental data. To quantify the accuracy for a given band, a descriptor is introduced that summarizes contributions to the lattice conductivity that are available already in the harmonic approx…
The thermoelectric properties of n type nanoscale three dimensional (3D) Si phononic crystals (PnCs) with spherical pores are studied. Density functional theory and Boltzmann transport equation under the relaxation time approximation are applied to study the electronic transport coefficients, electrical conductivity, Seebeck coefficient and electronic thermal conductivity. We found that the electronic transport coefficients in 3D Si PnC at room temperature (300 K) change very little compared with that of Si, for example, electrical conductivity and electronic thermal conductivity is decreased …
We investigate the role of rattling guest atoms on the lattice thermal-conductivity of a type-I clathrate Ba$_{8}$Ga$_{16}$Ge$_{30}$ by first-principles lattice dynamics. Comparing phonon properties of filled and empty clathrates, we show that rattlers cause 10-fold reductions in the relaxation time of phonons by increasing the phonon-phonon scattering probability. Contrary to the resonant scattering scenario, the reduction in the relaxation time occurs in a wide frequency range, which is crucial for explaining unusually low thermal-conductivities of clathrates. We also find that the impact of…
By converting waste heat into electricity through the thermoelectric power of solids without producing greenhouse gas emissions, thermoelectric generators could be an important part of the solution to today's energy challenge. There has been a resurgence in the search for new materials for advanced thermoelectric energy conversion applications. In this paper, we will review recent efforts on improving thermoelectric efficiency. Particularly, several novel proof-of-principle approaches such as phonon disorder in phonon-glasselectron crystals, low dimensionality in nanostructured materials and c…
Electron-phonon interaction (EPI) is presumably detrimental for thermoelectric performance in semiconductors because it limits carrier mobility. Here we show that enhanced EPI with strong energy dependence offers an intrinsic pathway to significant increase in the Seebeck coefficient and the thermoelectric power factor, particularly in the context of two-dimensional (2D) graphene-like Dirac bands. The increase is realized by enabling electron energy filtering through preferential scattering of electron/hole carriers. We prove this concept by implementing state-of-the-art first-principles compu…
Ion beam irradiation has recently emerged as a versatile approach to functional materials design. We show in this work that patterned defective regions generated by ion beam irradiation of silicon can create a phonon glass electron crystal (PGEC), a longstanding goal of thermoelectrics. By controlling the effective diameter of and spacing between the defective regions, molecular dynamics simulations suggest a reduction of the thermal conductivity by a factor of $\approx$20 is achievable. Boltzmann theory shows that the thermoelectric power factor remains largely intact in the damaged material.…
SnSe is a layered material that currently holds the record for bulk thermoelectric efficiency. The primary determinant of this high efficiency is thought to be the anomalously low thermal conductivity resulting from strong anharmonic coupling within the phonon system. Here we show that the nature of the carrier system in SnSe is also determined by strong coupling to phonons by directly visualizing polaron formation in the material. We employ ultrafast electron diffraction and diffuse scattering to track the response of phonons in both momentum and time to the photodoping of free carriers acros…
We calculate the lattice thermal conductivities of the pyrite-type ZnSe2 at pressures of 0 and 10 GPa using the linearized phonon Boltzmann transport equation. We obtain a very low value [0.69 W/(mK) at room temperature at 0 GPa], comparable to the best thermoelectric materials. The vibrational spectrum is characterized by the isolated high-frequency optical phonon modes due to the stretching of Se-Se dimers and low-frequency optical phonon modes due to the rotation of Zn atoms around these dimers. The low-frequency optical phonon modes are characterized by a strong anharmonicity and will subs…
We study the thermoelectric properties of bulk $MoSe_2$ within relaxation time approximation including electron-phonon and ionized impurity interactions using first-principles calculations at room temperatures. The anisotropy of this two-dimensional layered metal dichalcogenide is studied by calculations of electron mobility in the cross-plane and the in-plane directions. We show that the cross-plane mobility is two orders of magnitude smaller than the in-plane one. The inclusion of van der Waals interactions further lowers the carrier mobility in the cross-plane direction but minimally affect…
Bismuth oxyselenide (Bi$_2$O$_2$Se) attracts great interest as a potential n-type complement to p-type thermoelectric oxides in practical applications. Previous investigations were generally focused on polycrystals. Here, we performed a study on the thermoelectric properties of Bi$_2$O$_2$Se single crystals. Our samples exhibit electron mobility as high as 250 cm$^2.$V$^{-1}$.s$^{-1}$ and thermal conductivity as low as $2$ W.m$^{-1}$.K$^{-1}$ near room temperature. The maximized figure of merit is yielded to be 0.188 at 390 K, higher than that of polycrystals. Consequently, a rough estimation …
The electronic structure and thermoelectric properties of ZrRuTe-based Half-Heusler compounds are studied using density functional theory (DFT) and Boltzmann transport formalism. Based on rigorous computations of electron relaxation time $τ$ considering electron-phonon interactions and lattice thermal conductivity $κ_l$ considering phonon-phonon interactions, we find ZrRuTe to be an intrinsically good thermoelectric material. It has a high power factor of $\sim 2\times 10^{-3}$ W/m-K$^{2}$ and low $κ_l\sim 10$ W/m-K at 800 K. The thermoelectric figure of merit $ZT \sim 0.13$ at 800 K is higher…
Electron-hole dichotomy and enhancement of thermoelectric power factor by electron-hole-asymmetric relaxation time: a model study on a two-valley system with strong intervalley scattering
Direct and phonon-assisted tunneling currents in InAlGaAs-InGaAs bulk and double quantum well interband tunnel heterojunctions are simulated rigorously using the non-equilibrium Green's function formalism for coherent and dissipative quantum transport in combination with a simple two-band tight-binding model for the electronic structure. A realistic band profile and associated built-in electrostatic field is obtained via self-consistent coupling of the transport formalism to Poisson's equation. The model reproduces experimentally observed features in the current-voltage characteristics of the …
Thermoelectric properties of graphene nanoribbons with periodic edge vacancies and antidot lattice are investigated. The electron-phonon interaction is taken into account in the framework of the Hubbard-Holstein model with the use of the Lang-Firsov unitary transformation scheme. The electron transmission function, the thermopower and the thermoelectric figure of merit are calculated. We have found that the electron-phonon interaction causes a decrease in the peak values of the thermoelectric figure of merit and the shift of the peak positions closer to the center of the bandgap. The effects a…
A composite material is considered which consists of conducting nanoparticles separated by tunneling dielectric barriers. The influence of the phonon thermal conductivity of dielectric matrix on the thermoelectric figure of merit of this composite material is theoretically in-vestigated. The range of values and barrier parameters that can lead to the thermoelectric figure of merit greater than unity is estimated. The influence of space charge and nonlinearity of current-voltage relations of tunneling barrier are also discussed.
Using first-principles pseudopotential method and Boltzmann transport theory, we give a comprehensive understanding of the electronic and phonon transport properties of thermoelectric material BiCuSeO. By choosing proper hybrid functional for the exchange-correlation energy, we find that the system is semiconducting with a direct band gap of ~0.8 eV, which is quite different from those obtained previously using standard functionals. Detailed analysis of a three-dimensional energy band structure indicates that there is a valley degeneracy of eight around the valence band maximum, which leads to…
Type-I clathrate compounds have attracted a great deal of interest in connection with the search for efficient thermoelectric materials. These compounds constitute networked cages consisting of nano-scale tetrakaidecahedrons (14 hedrons) and dodecahedrons (12 hedrons), in which the group 1 or 2 elements in the periodic table are encaged as the so-called rattling guest atom. It is remarkable that, though these compounds have crystalline cubic-structure, they exhibit glass-like phonon thermal conductivity over the whole temperature range depending on the states of rattling guest atoms in the tet…
The unique structure of Zintl phase makes it an ideal system to realize the concept of phonon-glass and electron-crystal in the thermoelectric community. In this work, by combining first-principles calculations and Boltzmann transport theory for both electrons and phonons, we demonstrate that the ZT value of Zintl compound KSnSb can reach ~2.6 at 800 K. Such extraordinary thermoelectric performance originates from the large Seebeck coefficient due to multi-valley band structures and particularly very small lattice thermal conductivity caused by mixed-bond characteristics.
In typical thermoelectric energy harvesters and sensors, the Seebeck effect is caused by diffusion of electrons or holes in a temperature gradient. However, the Seebeck effect can also have a phonon drag component, due to momentum exchange between charge carriers and lattice phonons, which is more difficult to quantify. Here, we present the first study of phonon drag in the AlGaN/GaN two-dimensional electron gas (2DEG). We find that phonon drag does not contribute significantly to the thermoelectric behavior of devices with ~100 nm GaN thickness, which suppress the phonon mean free path. Howev…
In most materials, transport can be described by the motion of distinct species of quasiparticles, such as electrons and phonons. Strong interactions between quasiparticles, however, can lead to collective behaviour, including the possibility of viscous hydrodynamic flow. In the case of electrons and phonons, an electron-phonon fluid is expected to exhibit strong phonon-drag transport signatures and an anomalously low thermal conductivity. The Dirac semi-metal PtSn4 has a very low resistivity at low temperatures and shows a pronounced phonon drag peak in the low temperature thermopower; it is …
Based on the concept of band bending at metal/semiconductor interfaces as an energy filter for electrons, we present a theory for the enhancement of the thermoelectric properties of semiconductor materials with metallic nanoinclusions. We show that the Seebeck coefficient can be significantly increased due to a strongly energy-dependent electronic scattering time. By including phonon scattering, we find that the enhancement of ZT due to electron scattering is important for high doping, while at low doping it is primarily due to a decrease in the phonon thermal conductivity.
The demand for green energy increases day by day due to environmental concern and thermoelectric (TE) materials are one of the eco-friendly energy resources. Few authors reported high TE performance in TmCu$_3$Ch$_4$, reaching the figure of merit (ZT) above 2 at 1000K, from first-principles calculations neglecting electron-phonon scattering, spin-orbit coupling effect (SOC), and energy-dependent carrier lifetime. Here, thermoelectric transport properties of TmCu$_3$Ch$_4$ are reinvestigated through considering these parameters, and significant discrepancies are found. The ZT of p-type TaCu$_3$…
Recent discovery of new materials for thermoelectric energy conversion is enabled by efficient prediction of materials' performance from first-principles, without empirically fitted parameters. The novel simplified approach for computing electronic transport properties is described, which achieves good accuracy and transferability while greatly reducing complexity and computation cost compared to the existing methods. The first-principles calculations of the electron-phonon coupling demonstrate that the energy dependence of the electron relaxation time varies significantly with chemical compos…
