Equilibrium and Non-Equilibrium Lattice Dynamics of Anharmonic Systems.

In this review, motivated by the recent interest in high-temperature materials, we review our recent progress in theories of lattice dynamics in and out of equilibrium. To investigate thermodynamic properties of anharmonic crystals, the self-consistent phonon theory was developed, mainly in the 1960s, for rare gas atoms and quantum crystals. We have extended this theory to investigate the properties of the equilibrium state of a crystal, including its unit cell shape and size, atomic positions and lattice dynamical properties. Using the equation-of-motion method combined with the fluctuation-dissipation theorem and the Donsker-Furutsu-Novikov (DFN) theorem, this approach was also extended to investigate the non-equilibrium case where there is heat flow across a junction or an interface. The formalism is a classical one and therefore valid at high temperatures.

Nanophotonic control of thermal emission under extreme temperatures in air.

Nanophotonic materials offer spectral and directional control over thermal emission, but in high-temperature oxidizing environments, their stability remains low. This limits their applications in technologies such as solid-state energy conversion and thermal barrier coatings. Here we show an epitaxial heterostructure of perovskite BaZr0.5Hf0.5O3 (BZHO) and rocksalt MgO that is stable up to 1,100 °C in air. The heterostructure exhibits coherent atomic registry and clearly separated refractive-index-mismatched layers after prolonged exposure to this extreme environment. The immiscibility of the two materials is corroborated by the high formation energy of substitutional defects from density functional theory calculations. The epitaxy of immiscible refractory oxides is, therefore, an effective method to avoid prevalent thermal instabilities in nanophotonic materials, such as grain-growth degradation, interlayer mixing and oxidation. As a functional example, a BZHO/MgO photonic crystal is implemented as a filter to suppress long-wavelength thermal emission from the leading bulk selective emitter and effectively raise its cutoff energy by 20%, which can produce a corresponding gain in the efficiency of mobile thermophotovoltaic systems. Beyond BZHO/MgO, computational screening shows that hundreds of potential cubic oxide pairs fit the design principles of immiscible refractory photonics. Extending the concept to other material systems could enable further breakthroughs in a wide range of photonic and energy conversion applications.

Theory of Non-Equilibrium Heat Transport in Anharmonic Multiprobe Systems at High Temperatures.

We consider the problem of heat transport by vibrational modes between Langevin thermostats connected by a central device. The latter is anharmonic and can be subject to large temperature difference and thus be out of equilibrium. We develop a classical formalism based on the equation of motion method, the fluctuation-dissipation theorem and the Novikov theorem to describe heat flow in a multi-terminal geometry. We show that it is imperative to include a quartic term in the potential energy to insure stability and to properly describe thermal expansion. The latter also contributes to leading order in the thermal resistance, while the usually adopted cubic term appears in the second order. This formalism paves the way for accurate modeling of thermal transport across interfaces in highly non-equilibrium situations beyond perturbation theory.

Thermomagnetic properties of Bi2Te3 single crystal in the temperature range from 55 K to 380 K.

Magneto-thermoelectric transport provides an understanding of coupled electron-hole-phonon current in topological materials and has applications in energy conversion and cooling. In this work, we study the Nernst coefficient, the magneto-Seebeck coefficient, and the magnetoresistance of single-crystalline Bi2Te3 under external magnetic field in the range of -3 T to 3 T and in the temperature range of 55 K to 380 K. Moreau's relation is employed to justify both the overall trend of the Nernst coefficient and the temperature at which the Nernst coefficient changes sign. We observe a non-linear relationship between the Nernst coefficient and the applied magnetic field in the temperature range of 55 K to 255 K. An increase in both the Nernst coefficient and the magneto-Seebeck coefficient is observed as the temperature is reduced which can be attributed to the increased mobility of the carriers at lower temperatures. First-principles density functional theory calculations were carried out to physically model the experimental data including electronic and transport properties. Simulation findings agreed with the experiments and provide a theoretical insight to justify the measurements.

Novel MAB phases and insights into their exfoliation into 2D MBenes.

Considering the recent breakthroughs in the synthesis of novel two-dimensional (2D) materials from layered bulk structures, ternary layered transition metal borides, known as MAB phases, have come under scrutiny as a means of obtaining novel 2D transition metal borides, the so-called MBenes. Here, based on a set of phonon calculations, we show the dynamic stability of many Al-containing MAB phases, MAlB (M = Ti, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc), M2AlB2 (Sc, Ti, Zr, Hf, V, Cr, Mo, W, Mn, Tc, Fe, Rh, Ni), M3Al2B2 (M = Sc, T, Zr, Hf, Cr, Mn, Tc, Fe, Ru, Ni), M3AlB4 (M = Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe), and M4AlB6 (M = Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo). By comparing the formation energies of these MAB phases with those of their available competing binary M-B and M-Al, and ternary M-Al-B phases, we find that some of the Sc-, Ti-, V-, Cr-, Mo-, W-, Mn-, Tc-, and Fe-based MAB phases could be favorably synthesized under appropriate experimental conditions. In addition, by examining the strengths of various bonds in MAB phases via crystal orbital Hamilton population and spring constant calculations, we find that the B-B and then M-B bonds are stiffer than the M-Al and Al-B bonds. The different strengths between these bonds imply the etching possibility of Al atoms from MAB phases, consequently forming various 2D MB, M2B3, and M3B4 MBenes. Furthermore, we employ the nudged elastic band method to investigate the possibility of the structural phase transformation of the 2D MB MBenes into graphene-like boron sheets sandwiched between transition metals and find that the energy barrier of the transformation is less than 0.4 eV per atom.

Semi-metals as potential thermoelectric materials.

The best thermoelectric materials are believed to be heavily doped semiconductors. The presence of a band gap is assumed to be essential to achieve large thermoelectric power factor and figure of merit. In this work, we propose semi-metals with large asymmetry between conduction and valence bands as an alternative class of thermoelectric materials. To illustrate the idea, we study semi-metallic HgTe in details experimentally and theoretically. We employ ab initio calculations with hybrid exchange-correlation functional to accurately describe the electronic band structure in conjunction with the Boltzmann Transport theory to investigate the electronic transport properties. We calculate the lattice thermal conductivity using first principles calculations and evaluate the overall figure of merit. To validate our theoretical approach, we prepare semi-metallic HgTe samples and characterize their transport properties. Our first-principles calculations agree well with the experimental data. We show that intrinsic HgTe, a semimetal with large disparity in its electron and hole masses, has a high thermoelectric power factor that is comparable to the best known thermoelectric materials. Finally, we propose other possible materials with similar band structures as potential candidates for thermoelectric applications.

High-Performance Solid-State Thermionic Energy Conversion Based on 2D van der Waals Heterostructures: A First-Principles Study.

Two-dimensional (2D) van der Waals heterostructures (vdWHs) have shown multiple functionalities with great potential in electronics and photovoltaics. Here, we show their potential for solid-state thermionic energy conversion and demonstrate a designing strategy towards high-performance devices. We propose two promising thermionic devices, namely, the p-type Pt-G-WSe2-G-Pt and n-type Sc-WSe2-MoSe2-WSe2-Sc. We characterize the thermionic energy conversion performance of the latter using first-principles GW calculations combined with real space Green's function (GF) formalism. The optimal barrier height and high thermal resistance lead to an excellent performance. The proposed device is found to have a room temperature equivalent figure of merit of 1.2 which increases to 3 above 600 K. A high performance with cooling efficiency over 30% of the Carnot efficiency above 450 K is achieved. Our designing and characterization method can be used to pursue other potential thermionic devices based on vdWHs.

Insights into exfoliation possibility of MAX phases to MXenes.

Chemical exfoliation of MAX phases into two-dimensional (2D) MXenes can be considered as a major breakthrough in the synthesis of novel 2D systems. To gain insight into the exfoliation possibility of MAX phases and to identify which MAX phases are promising candidates for successful exfoliation into 2D MXenes, we perform extensive electronic structure and phonon calculations, and determine the force constants, bond strengths, and static exfoliation energies of MAX phases to MXenes for 82 different experimentally synthesized crystalline MAX phases. Our results show a clear correlation between the force constants and the bond strengths. As the total force constant of an "A" atom contributed from the neighboring atoms is smaller, the exfoliation energy becomes smaller, thus making exfoliation easier. We propose 37 MAX phases for successful exfoliation into 2D Ti2C, Ti3C2, Ti4C3, Ti5C4, Ti2N, Zr2C, Hf2C, V2C, V3C2, V4C3, Nb2C, Nb5C4, Ta2C, Ta5C4, Cr2C, Cr2N, and Mo2C MXenes. In addition, we explore the effect of charge injection on MAX phases. We find that the injected charges, both electrons and holes, are mainly received by the transition metals. This is due to the electronic property of MAX phases that the states near the Fermi energy are mainly dominated by d orbitals of the transition metals. For negatively charged MAX phases, the electrons injected cause swelling of the structure and elongation of the bond distances along the c axis, which hence weakens the binding. For positively charged MAX phases, on the other hand, the bonds become shorter and stronger. Therefore, we predict that the electron injection by electrochemistry or gating techniques can significantly facilitate the exfoliation possibility of MAX phases to 2D MXenes.

Thermal management and non-reciprocal control of phonon flow via optomechanics.

Engineering phonon transport in physical systems is a subject of interest in the study of materials, and has a crucial role in controlling energy and heat transfer. Of particular interest are non-reciprocal phononic systems, which in direct analogy to electric diodes, provide a directional flow of energy. Here, we propose an engineered nanostructured material, in which tunable non-reciprocal phonon transport is achieved through optomechanical coupling. Our scheme relies on breaking time-reversal symmetry by a spatially varying laser drive, which manipulates low-energy acoustic phonons. Furthermore, we take advantage of developments in the manipulation of high-energy phonons through controlled scattering mechanisms, such as using alloys and introducing disorder. These combined approaches allow us to design an acoustic isolator and a thermal diode. Our proposed device will have potential impact in phonon-based information processing, and heat management in low temperatures.

Cross-Plane Seebeck Coefficient Measurement of Misfit Layered Compounds (SnSe)n(TiSe2)n (n = 1,3,4,5).

We report cross-plane thermoelectric measurements of misfit layered compounds (SnSe)n(TiSe2)n (n = 1,3,4,5), approximately 50 nm thick. Metal resistance thermometers are fabricated on the top and bottom of the (SnSe)n(TiSe2)n material to measure the temperature difference and heat transport through the material directly. By varying the number of layers in a supercell, n, we vary the interface density while maintaining a constant global stoichiometry. The Seebeck coefficient measured across the (SnSe)n(TiSe2)n samples was found to depend strongly on the number of layers in the supercell (n). When n decreases from 5 to 1, the cross-plane Seebeck coefficient decreases from -31 to -2.5 µV/K, while the cross-plane effective thermal conductivity decreases by a factor of 2, due to increased interfacial phonon scattering. The cross-plane Seebeck coefficients of the (SnSe)n(TiSe2)n are very different from the in-plane Seebeck coefficients, which are higher in magnitude and less sensitive to the number of layers in a supercell, n. We believe this difference is due to the different carrier types in the n-SnSe and p-TiSe2 layers and the effect of tunneling on the cross-plane transport.

Molecular Dynamics Study of Cubic Boron Nitride Nanoparticles: Decomposition with Phase Segregation during Melting.

The relative stability and melting of cubic boron nitride (c-BN) nanoparticles of varying shapes and sizes are studied using classical molecular dynamics (MD) simulation. Focusing on the melting of octahedral c-BN nanoparticles, which consist solely of the most stable {111} facets, decomposition is observed to occur during melting, along with the formation of phase segregated boron clusters inside the c-BN nanoparticles, concurrent with vaporization of surface nitrogen atoms. To assess this MD prediction, a laser-heating experiment of c-BN powders is conducted, manifesting boron clusters for the post-treated powders. A general analysis of the geometrical and surface dependence of the nanoparticle ground-state energy using a Stillinger-Weber potential determines the relative stability of cube-shaped, octahedral, cuboctahedral, and truncated-octahedral c-BN nanoparticles. This stability is further examined using transient MD simulations of the melting behavior of the differently shaped nanoparticles, providing insights and revealing the key roles played by corner and edge initiated disorder as well as surface reconstruction from {100} to the more stable {111} facets in the melting process. Finally, the size dependence of the melting point of octahedral c-BN nanoparticles is investigated, showing the well-known qualitative trend of depression of melting temperature with decreasing size, albeit with different quantitative behavior from that predicted by existing analytical models.

First principles calculations of solid-state thermionic transport in layered van der Waals heterostructures.

This work aims at understanding solid-state energy conversion and transport in layered (van der Waals) heterostructures in contact with metallic electrodes via a first-principles approach. As an illustration, a graphene/phosphorene/graphene heterostructure in contact with gold electrodes is studied by using density functional theory (DFT)-based first principles calculations combined with real space Green's function (GF) formalism. We show that for a monolayer phosphorene, quantum tunneling dominates the transport. By adding more phosphorene layers, one can switch from tunneling-dominated transport to thermionic-dominated transport, resulting in transporting more heat per charge carrier, thus, enhancing the cooling coefficient of performance. The use of layered van der Waals heterostructures has two advantages: (a) thermionic transport barriers can be tuned by changing the number of layers, and (b) thermal conductance across these non-covalent structures is very weak. The phonon thermal conductance of the present van der Waals heterostructure is found to be 4.1 MW m(-2) K(-1) which is one order of magnitude lower than the lowest value for that of covalently-bonded interfaces. The thermionic coefficient of performance for the proposed device is 18.5 at 600 K corresponding to an equivalent ZT of 0.13, which is significant for nanoscale devices. This study shows that layered van der Waals structures have great potential to be used as solid-state energy-conversion devices.

Ab initio optimization of phonon drag effect for lower-temperature thermoelectric energy conversion.

Although the thermoelectric figure of merit zT above 300 K 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 to our knowledge, success in first-principles computation of the phonon drag effect--a coupling phenomenon between electrons and nonequilibrium 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 the major phonons contributing to the phonon drag, which are spectrally distinct from those carrying heat, and further reveals that although the phonon drag is reduced in heavily doped samples, a significant contribution to Seebeck coefficient still exists. An ideal phonon filter is proposed to enhance zT of silicon at room temperature by a factor of 20 to ∼ 0.25, and the enhancement can reach 70 times at 100 K. This work opens up a new venue toward better thermoelectrics by harnessing nonequilibrium phonons.

Transition from near-field thermal radiation to phonon heat conduction at sub-nanometre gaps.

When the separation of two surfaces approaches sub-nanometre scale, the boundary between the two most fundamental heat transfer modes, heat conduction by phonons and radiation by photons, is blurred. Here we develop an atomistic framework based on microscopic Maxwell's equations and lattice dynamics to describe the convergence of these heat transfer modes and the transition from one to the other. For gaps >1 nm, the predicted conductance values are in excellent agreement with the continuum theory of fluctuating electrodynamics. However, for sub-nanometre gaps we find the conductance is enhanced up to four times compared with the continuum approach, while avoiding its prediction of divergent conductance at contact. Furthermore, low-frequency acoustic phonons tunnel through the vacuum gap by coupling to evanescent electric fields, providing additional channels for energy transfer and leading to the observed enhancement. When the two surfaces are in or near contact, acoustic phonons become dominant heat carriers.

Significant reduction of lattice thermal conductivity by the electron-phonon interaction in silicon with high carrier concentrations: a first-principles study.

The electron-phonon interaction is well known to create major resistance to electron transport in metals and semiconductors, whereas fewer studies are directed to its effect on phonon transport, especially in semiconductors. We calculate the phonon lifetimes due to scattering with electrons (or holes), combine them with the intrinsic lifetimes due to the anharmonic phonon-phonon interaction, all from first principles, and evaluate the effect of the electron-phonon interaction on the lattice thermal conductivity of silicon. Unexpectedly, we find a significant reduction of the lattice thermal conductivity at room temperature as the carrier concentration goes above 10(19) cm(-3) (the reduction reaches up to 45% in p-type silicon at around 10(21) cm(-3)), a range of great technological relevance to thermoelectric materials.

Hydrodynamic phonon transport in suspended graphene.

Recent studies of thermal transport in nanomaterials have demonstrated the breakdown of Fourier's law through observations of ballistic transport. Despite its unique features, another instance of the breakdown of Fourier's law, hydrodynamic phonon transport, has drawn less attention because it has been observed only at extremely low temperatures and narrow temperature ranges in bulk materials. Here, we predict on the basis of first-principles calculations that the hydrodynamic phonon transport can occur in suspended graphene at significantly higher temperatures and wider temperature ranges than in bulk materials. The hydrodynamic transport is demonstrated through drift motion of phonons, phonon Poiseuille flow and second sound. The significant hydrodynamic phonon transport in graphene is associated with graphene's two-dimensional features. This work opens a new avenue for understanding and manipulating heat flow in two-dimensional materials.

Resonant bonding leads to low lattice thermal conductivity.

Understanding the lattice dynamics and low thermal conductivities of IV-VI, V2-VI3 and V materials is critical to the development of better thermoelectric and phase-change materials. Here we provide a link between chemical bonding and low thermal conductivity. Our first-principles calculations reveal that long-ranged interaction along the 〈100〉 direction of the rocksalt structure exist in lead chalcogenides, SnTe, Bi2Te3, Bi and Sb due to the resonant bonding that is common to all of them. This long-ranged interaction in lead chalcogenides and SnTe cause optical phonon softening, strong anharmonic scattering and large phase space for three-phonon scattering processes, which explain why rocksalt IV-VI compounds have much lower thermal conductivities than zincblende III-V compounds. The new insights on the relationship between resonant bonding and low thermal conductivity will help in the development of better thermoelectric and phase change materials.

High thermoelectric performance by resonant dopant indium in nanostructured SnTe.

From an environmental perspective, lead-free SnTe would be preferable for solid-state waste heat recovery if its thermoelectric figure-of-merit could be brought close to that of the lead-containing chalcogenides. In this work, we studied the thermoelectric properties of nanostructured SnTe with different dopants, and found indium-doped SnTe showed extraordinarily large Seebeck coefficients that cannot be explained properly by the conventional two-valence band model. We attributed this enhancement of Seebeck coefficients to resonant levels created by the indium impurities inside the valence band, supported by the first-principles simulations. This, together with the lower thermal conductivity resulting from the decreased grain size by ball milling and hot pressing, improved both the peak and average nondimensional figure-of-merit (ZT) significantly. A peak ZT of ∼1.1 was obtained in 0.25 atom % In-doped SnTe at about 873 K.

Enhancing the thermoelectric power factor by using invisible dopants.

Nanoparticle dopants that are invisible to conduction electrons and have sharp dips in their electron scattering rate versus electron energy close to the Fermi level. Replacement of such dopants with traditional impurities results in simultaneous enhancement of the Seebeck coefficient and the electron mobility and therefore a large enhancement in the thermoelectric power factor can be achieved.

Coherent phonon heat conduction in superlattices.

The control of heat conduction through the manipulation of phonons as coherent waves in solids is of fundamental interest and could also be exploited in applications, but coherent heat conduction has not been experimentally confirmed. We report the experimental observation of coherent heat conduction through the use of finite-thickness superlattices with varying numbers of periods. The measured thermal conductivity increased linearly with increasing total superlattice thickness over a temperature range from 30 to 150 kelvin, which is consistent with a coherent phonon heat conduction process. First-principles and Green's function-based simulations further support this coherent transport model. Accessing the coherent heat conduction regime opens a new venue for phonon engineering for an array of applications.