ABSTRACT: A fundamental understanding of phonon transport in stanene is crucial to predict the thermal performance in potential stanene-based devices. By combining first-principle calculation and phonon Boltzmann transport equation, we obtain the lattice thermal conductivity of stanene. A much lower thermal conductivity (11.6 W/mK) is observed in stanene, which indicates higher thermoelectric efficiency over other 2D materials. The contributions of acoustic and optical phonons to the lattice thermal conductivity are evaluated. Detailed analysis of phase space for three-phonon processes shows that phonon scattering channels LA + LA/TA/ZA ↔ TA/ZA are restricted, leading to the dominant contributions of high-group-velocity LA phonons to the thermal conductivity. The size dependence of thermal conductivity is investigated as well for the purpose of the design of thermoelectric nanostructures.
Project description:By using first-principles calculations combined with the phonon Boltzmann transport equation, we systematically investigate the phonon transport of monolayer WSe2. Compared with other 2D materials, the monolayer WSe2 is found to have an ultralow thermal conductivity due to the ultralow Debye frequency and heavy atom mass. The room temperature thermal conductivity for a typical sample size of 1 μm is 3.935 W/m K, which is one order of magnitude lower than that of MoS2. And the room temperature thermal conductivity can be further decreased by about 95% in 10 nm sized samples. Moreover, we also find the ZA phonons have the dominant contribution to the thermal conductivity, and the relative contribution is almost 80% at room temperature, which is remarkably higher than that for monolayer MoS2. This is because the ZA phonons have longer lifetime than that of LA and TA phonons in monolayer WSe2.
Project description:Low thermal conductivity is favorable for preserving the temperature gradient between the two ends of a thermoelectric material, in order to ensure continuous electron current generation. In high-performance thermoelectric materials, there are two main low thermal conductivity mechanisms: the phonon anharmonic in PbTe and SnSe, and phonon scattering resulting from the dynamic disorder in AgCrSe2 and CuCrSe2, which have been successfully revealed by inelastic neutron scattering. Using neutron scattering and ab initio calculations, we report here a mechanism of static local structure distortion combined with phonon-anharmonic-induced ultralow lattice thermal conductivity in ?-MgAgSb. Since the transverse acoustic phonons are almost fully scattered by the compound's intrinsic distorted rocksalt sublattice, the heat is mainly transported by the longitudinal acoustic phonons. The ultralow thermal conductivity in ?-MgAgSb is attributed to its atomic dynamics being altered by the structure distortion, which presents a possible microscopic route to enhance the performance of similar thermoelectric materials.
Project description:To minimize the lattice thermal conductivity in thermoelectrics, strategies typically focus on the scattering of low-frequency phonons by interfaces and high-frequency phonons by point defects. In addition, scattering of mid-frequency phonons by dense dislocations, localized at the grain boundaries, has been shown to reduce the lattice thermal conductivity and improve the thermoelectric performance. Here we propose a vacancy engineering strategy to create dense dislocations in the grains. In Pb1-xSb2x/3Se solid solutions, cation vacancies are intentionally introduced, where after thermal annealing the vacancies can annihilate through a number of mechanisms creating the desired dislocations homogeneously distributed within the grains. This leads to a lattice thermal conductivity as low as 0.4?Wm-1?K-1 and a high thermoelectric figure of merit, which can be explained by a dislocation scattering model. The vacancy engineering strategy used here should be equally applicable for solid solution thermoelectrics and provides a strategy for improving zT.
Project description:Phonons in condensed matter materials transmit energy through atomic lattices as coherent vibrational waves. Like electronic and photonic properties, an improved understanding of phononic properties is essential for the development of functional materials, including thermoelectric materials. Recently, an Einstein rattling mode was found in thermoelectric material Na0.8CoO2, due to the large displacement of Na between the [CoO2] layers. In this work, we have realized a different type of rattler in another thermoelectric material Ca3Co4O9 by chemical doping, which possesses the same [CoO2] layer as Na0.8CoO2. It remarkably suppressed the thermal conductivity while enhancing its electrical conductivity. This new type of rattler was investigated by inelastic neutron scattering experiments in conjunction with ab-initio molecular dynamics simulations. We found that the large mass of dopant rather than the large displacement is responsible for such rattling in present study, which is fundamentally different from skutterudites, clathrates as well as Na analogue. We have also tentatively studied the phonon band structure of this material by DFT lattice dynamics simulation, showing the relative contribution to phonons in the distinct layers of Ca3Co4O9.
Project description:Conventional strategies for advancing thermoelectrics by minimizing the lattice thermal conductivity focus on phonon scattering for a short mean free path. Here, a design of slow phonon propagation as an effective approach for high-performance thermoelectrics is shown. Taking Ag8SnSe6 as an example, which shows one of the lowest sound velocities among known thermoelectric semiconductors, the lattice thermal conductivity is found to be as low as 0.2 W m-1 K-1 in the entire temperature range. As a result, a peak thermoelectric figure of merit zT > 1.2 and an average zT as high as ?0.8 are achieved in Nb-doped materials, without relying on a high thermoelectric power factor. This work demonstrates not only a guiding principle of low sound velocity for minimal lattice thermal conductivity and therefore high zT, but also argyrodite compounds as promising thermoelectric materials with weak chemical bonds and heavy constituent elements.
Project description:Lead halide perovskites are strong candidates for high-performance low-cost photovoltaics, light emission, and detection applications. A hot-phonon bottleneck effect significantly extends the cooling time of hot charge carriers, which thermalize through carrier-optic phonon scattering, followed by optic phonon decay to acoustic phonons and finally thermal conduction. To understand these processes, we adjust the lattice dynamics independently of electronics by changing isotopes. We show that doubling the mass of hydrogen in methylammonium lead iodide by replacing protons with deuterons causes a large 20 to 50% softening of the longitudinal acoustic phonons near zone boundaries, reduces thermal conductivity by ~50%, and slows carrier relaxation kinetics. Phonon softening is attributed to anticrossing with the slowed libration modes of the deuterated molecules and the reduced thermal conductivity to lowered phonon velocities. Our results reveal how tuning the organic molecule dynamics enables control of phonons important to thermal conductivity and the hot-phonon bottleneck.
Project description:A fundamental understanding of the phonon transport mechanism is important for optimizing the efficiency of thermoelectric devices. In this study, we investigate the thermal transport properties of the oxidized form of phosphorene called phosphorene oxide (PO) by solving phonon Boltzmann transport equation based on first-principles density functional theory. We reveal that PO exhibits a much lower thermal conductivity (2.42-7.08?W/mK at 300?K) than its pristine counterpart as well as other two-dimensional materials. To comprehend the physical origin of such low thermal conductivity, we scrutinize the contribution of each phonon branch to the thermal conductivity by evaluating various mode-dependent quantities including Grüneisen parameters, anharmonic three-phonon scattering rate, and phase space of three-phonon scattering processes. Our results show that its flexible puckered structure of PO leads to smaller sound velocities; its broken-mirror symmetry allows more ZA phonon scattering; and the relatively-free vibration of dangling oxygen atoms in PO gives rise to additional scattering resulting in further reduction in the phonon lifetime. These results can be verified by the fact that PO has larger phase space for three-phonon processes than phosphorene. Furthermore we show that the thermal conductivity of PO can be optimized by controlling its size or its phonon mean free path, indicating that PO can be a promising candidate for low-dimensional thermoelectric devices.
Project description:Strain engineering is a practical method to tune and improve the physical characteristics and properties of two-dimensional materials, due to their large stretchability. Tensile strain dependence of electronic, phonon, and thermoelectric properties of InSe monolayer are systematically studied. We demonstrate that the lattice thermal conductivity can be effectively modulated by applying tensile strain. Tensile strain can enhance anharmonic phonon scattering, giving rise to the enhanced phonon scattering rate, reduced phonon group velocity and heat capacity, and therefore lattice thermal conductivity decreases from 25.9 to 13.1 W/mK when the strain of 6% is applied. The enhanced figure of merit indicates that tensile strain is an effective way to improve the thermoelectric performance of InSe monolayer.
Project description:Efficiency in generation and utilization of energy is highly dependent on materials that have the ability to amplify or hinder thermal conduction processes. A comprehensive understanding of the relationship between chemical bonding and structure impacting lattice waves (phonons) is essential to furnish compounds with ultralow lattice thermal conductivity (<i>?</i> <sub>lat</sub>) for important applications such as thermoelectrics. Here, we demonstrate that the n-type rock-salt AgPbBiSe<sub>3</sub> exhibits an ultra-low <i>?</i> <sub>lat</sub> of 0.5-0.4 W m<sup>-1</sup> K<sup>-1</sup> in the 290-820 K temperature range. We present detailed analysis to uncover the fundamental origin of such a low <i>?</i> <sub>lat</sub>. First-principles calculations augmented with low temperature heat capacity measurements and the experimentally determined synchrotron X-ray pair distribution function (PDF) reveal bonding heterogeneity within the lattice and lone pair induced lattice anharmonicity. Both of these factors enhance the phonon-phonon scattering, and are thereby responsible for the suppressed <i>?</i> <sub>lat</sub>. Further optimization of the thermoelectric properties was performed by aliovalent halide doping, and a thermoelectric figure of merit (<i>zT</i>) of 0.8 at 814 K was achieved for AgPbBiSe<sub>2.97</sub>I<sub>0.03</sub> which is remarkable among n-type Te free thermoelectrics.
Project description: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.