Further improvement of lattice thermal conductivity from bulk crystalline to 1-D-chain polyethylene: A high-yet-finite thermal conductivity using first-principles calculation
We calculate the thermal conductivity (\k{appa}) of both bulk crystalline and single-chain polyethylene (PE) using the first-principles-based anharmonic lattice dynamics. Despite its low \k{appa} in amorphous state, the predicted bulk crystal has high axial \k{appa} (237 W/m-K) at room temperature. The much lower measured \k{appa} is attributed to the small size of nanocrystallites (~10 nm) in synthesized semi-crystalline PE. For the 1-D chain, the predicted \k{appa} is much larger and yet finite (1400 W/m-K at room temperature). The reduction of scattering phase space caused by the diminished interchain van der Waals interactions explains this larger \k{appa}. It is also found that the transverse phonon branches with quadratic dispersion make minor contribution to this, due to their vanishing group velocity in the long-wavelength limit. Moreover, the low-frequency bending and twisting phonon modes are strongly coupled and dominate anharmonic phonon scatterings, leading to the finite \k{appa}. The predicted high \k{appa} of bulk and chain PE crystals enable polymer usage in thermal management and the above phonon scatterings provide guide for their nano-designs.
In this paper, we have studied the effect of short branches on the thermal conductivity of a polyethylene (PE) chain. With a reverse non-equilibrium molecular dynamics method applied, thermal conductivities of the pristine PE chain and the PE-ethyl chain are simulated and compared. It shows that the branch has a positive effect to decrease the thermal conductivity of a PE chain. The thermal conductivity of the PE-ethyl chain decreases with the number density increase of the ethyl branches, until the density becomes larger than about 8 ethyl per 200 segments, where the thermal conductivity satu…
Semi-crystalline polymers have been shown to have greatly increased thermal conductivity compared to amorphous bulk polymers due to effective heat conduction along the covalent bonds of the backbone. However, the mechanisms governing the intrinsic thermal conductivity of polymers remain largely unexplored as thermal transport has been studied in relatively few polymers. Here, we use molecular dynamics simulations to study heat transport in polynorbornene, a polymer that can be synthesized in semi-crystalline form using solution processing. We find that even perfectly crystalline polynorbornene…
Manipulation of the magnetization in heavy-metal/ferromagnetic bilayers via the spin-orbit torque requires high spin Hall conductivity of the heavy metal. We measure inverse spin Hall voltage using a co-planar wave-guide based broadband ferromagnetic resonance set-up in Py/Ta system with varying crystalline phase of Ta. We demonstrate a strong correlation between the measured spin mixing conductance and spin Hall conductivity with the crystalline phase of Ta thin films. We found a large spin Hall conductivity of $-2439~(\hbar/e)~Ω^{-1}$cm$^{-1}$ for low-resistivity (68 $μΩ-$cm) Ta film having …
Prior experimental studies showed that nanowires are promising structures for improving the thermoelectric performance of practical thermoelectric materials due to the strongly induced phonon-boundary scattering. However, few studies examined the impact of phonon-boundary scattering on the thermal conductivity of thermoelectric nanowires from a first-principle approach. In this work, we systematically study the role of phonon-boundary scattering with different boundary specularities on the thermal conductivity of PbSe nanowires by rigorously solving the full phonon Boltzmann transport equation…
Temperature-dependent thermal conductivity of epitaxial silicon nano-crystalline (SiNC) structures composed of nanometer-sized grains separated by ultra-thin silicon-oxide (SiO2) films is measured by the time domain thermoreflectance technique in the range from 50 to 300 K. Thermal conductivity of SiNC structures with grain size of 3 nm and 5 nm is anomalously low at the entire temperature range, significantly below the values of bulk amorphous Si and SiO2. Phonon gas kinetics model, with intrinsic transport properties obtained by first-principles-based anharmonic lattice dynamics and phonon t…
We present the electrical transport characteristics of a batch of nano-crystalline diamond films of varying nitrogen concentrations and explain the conduction mechanism by the disordered quasi-superlattice model applied to semiconductor heterostructures. Synthesized by the hot filament chemical vapour deposition technique, the degree of structural disorder in the films, confirmed from Raman spectroscopy, is found to be controllable, resulting in the transition of conduction mechanism from localized and activated to the metallic conduction regime. Hence through high field magneto-resistance mea…
We study the charge and spin dependent scattering in a set of CoFeB thin films whose crystalline order is systematically enhanced and controlled by annealing at increasingly higher temperatures. Terahertz conductivity measurements reveal that charge transport closely follows the development of the crystalline phase, with increasing structural order leading to higher conductivity. The terahertz-induced ultrafast demagnetization, driven by spin-flip scattering mediated by the spin-orbit interaction, is measurable in the pristine amorphous sample and much reduced in the sample with highest crysta…
We investigate the electrical conductivity and thermoelectric effects in topological crystalline insulators in the presence of short- and long-range impurity interactions. We employ the generalized Boltzmann formalism for anisotropic Fermi surface systems. The conductivity exhibits a local minimum as doping varies owing to the Van Hove singularity in the density of states originated from the saddle point in the surface states band structure. Suppression of the interband scattering of the charge carriers at high-energy Dirac points results in a maximum in the electrical conductivity. Whenever t…
Modifying phonon thermal conductivity in nanomaterials is important not only for fundamental research but also for practical applications. However, the experiments on tailoring the thermal conductivity in nanoscale, especially in two-dimensional materials, are rare due to technical challenges. In this work, we demonstrate in-situ thermal conduction measurement of MoS2 and find that its thermal conductivity can be continuously tuned to a required value from crystalline to amorphous limits. The reduction of thermal conductivity is understood from phonon-defects scatterings that decrease the phon…
Size-dependent quantization of energy spectrum of conducting electrons in solids leads to oscillating dependence of electronic properties on corresponding dimension(s). In conventional metals with typical energy Fermi EF~1 eV and the charge carrier's effective masses m* of the order of free electron mass m0, the quantum size phenomena provide noticeable impact only at nanometer scales. Here we experimentally demonstrate that in single-crystalline semimetal bismuth nanostructures the electronic conductivity non-monotonously decreases with reduction of the effective diameter. In samples grown al…
Aluminum nitride (AlN) plays a key role in modern power electronics and deep-ultraviolet photonics, where an understanding of its thermal properties is essential. Here we measure the thermal conductivity of crystalline AlN by the 3$ω$ method, finding it ranges from 674 ${\pm}$ 56 W/m/K at 100 K to 186 ${\pm}$ 7 W/m/K at 400 K, with a value of 237 ${\pm}$ 6 W/m/K at room temperature. We compare these data with analytical models and first principles calculations, taking into account atomic-scale defects (O, Si, C impurities, and Al vacancies). We find Al vacancies play the greatest role in reduc…
It is textbookly regarded that phonons, i.e., an energy quantum of propagating lattice waves, are the main heat carriers in perfect crystals. As a result, in many crystals, e.g., bulk silicon, the temperature-dependent thermal conductivity shows the classical 1/T relationship because of the dominant Umklapp phonon-phonon scattering in the systems. However, the thermal conductivity of many crystalline metal-organic frameworks is very low and shows no, a weakly negative and even a weakly positive temperature dependence (glass-like thermal conductivity). It has been in debate whether the thermal …
We theoretically investigate a relation between the crystalline symmetry and the transient modulation of optical properties of crystalline dielectrics in pump-probe measurements using intense pump and attosecond probe fields. When the photon energy of the pump field is much below the bandgap energy, the modulation of the optical conductivity is caused by the intraband electronic motion, that is, the dynamical Franz-Keldysh effect. We analytically investigate symmetry properties of the modulated optical conductivity utilizing the Houston function, and derive a formula that relates the temporal …
Detailed structural and electrical properties of ultra-nano-crystalline diamond (UNCD) films grown in H$_\text{2}$/CH$_\text{4}$/N$_\text{2}$ plasma were systematically studied as a function of deposition temperature ($T_d$) and nitrogen content ($\%$ N$_2$) to thoroughly evaluate their effects on conductivity. $T_d$ was scanned from 1000 to 1300 K for N$_2$ fixed at 0, 5, 10 and 20 $\%$. It was found that even the films grown in the synthetic gas mixture with no nitrogen could be made as conductive as 1$-$10$^{-2}$ $Ω$ cm with overall resistivity of all the films tuned over 4 orders of magnit…
The paper examines weak localization (WL) of surface states with a quadratic band crossing in topological crystalline insulators. It is shown that the topology of the quadratic band crossing point dictates the negative sign of the WL conductivity correction. For the surface states with broken time-reversal symmetry, an explicit dependence of the WL conductivity on the band Berry flux is obtained and analyzed for different carrier-density regimes and types of the band structure (normal or inverted). These results suggest a way to detect the band Berry flux through WL measurements.
We study by scanning thermal microscopy the nanoscale thermal conductance of films (40 to 400 nm thick) of [1]benzothieno[3,2-b][1]benzothiophene (BTBT) and 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT-C8). We demonstrate that the out-of-plane thermal conductivity is significant along the interlayer direction, larger for BTBT (0.63 +/- 0.12 W m-1 K-1) compared to C8-BTBT-C8 (0.25 +/- 0.13 W m-1 K-1). These results are supported by molecular dynamics calculations (Approach to Equilibrium Molecular Dynamics method) performed on the corresponding molecular crystals. The calculations…
We have investigated thermal conductivity of graphene laminate films deposited on polyethylene terephthalate substrates. Two types of graphene laminate were studied - as deposited and compressed - in order to determine the physical parameters affecting the heat conduction the most. The measurements were performed using the optothermal Raman technique and a set of suspended samples with the graphene laminate thickness from 9 to 44 micrometers. The thermal conductivity of graphene laminate was found to be in the range from 40 W/mK to 90 W/mK at room temperature. It was found unexpectedly that th…
Molecular simulations of polymer rely on accurate force fields to describe the inter-atomic interactions. In this work, we use first-principles density functional theory (DFT) calculations to parameterize a united-atom force field for polyacetylene (PA), a conjugated polymer potentially of high thermal conductivity. Different electron correlation functionals in DFT have been tested. Bonding interactions for the alternating single and double bonds in the conjugated polymer backbone are explicitly described and Class II anharmonic functions are separately parameterized. Bond angle and dihedral i…
We calculate the electrical conductivity of a thin crystalline strip of atoms confined within a quasi one dimensional channel of fixed width. The conductivity shows anomalous behavior as the strip is deformed under tensile loading. Beyond a critical strain, the solid fails by the nucleation of alternating bands of solid and {\em smectic} like phases accompanied by a jump in the conductivity. Since the failure of the strip in this system is known to be reversible, the onductivity anomaly may have practical use as a sensitive strain transducer.
Black phosphorus (BP) has emerged as a direct-bandgap semiconducting material with great application potentials in electronics, photonics, and energy conversion. Experimental characterization of the anisotropic thermal properties of BP, however, is extremely challenging due to the lack of reliable and accurate measurement techniques to characterize anisotropic samples that are micrometers in size. Here, we report measurement results of the anisotropic thermal conductivity of bulk BP along three primary crystalline orientations, using the novel time-resolved magneto-optical Kerr effect (TR-MOKE…
We report on evaluation of lattice thermal conductivity of GeTe/Sb$_{2}$Te$_{3}$ superlattice (SL) by using femtosecond coherent phonon spectroscopy at various lattice temperatures. The time-resolved transient reflectivity obtained in amorphous and crystalline GeTe/Sb$_{2}$Te$_{3}$ SL films exhibits the coherent $A_{1}$ optical modes at terahertz (THz) frequencies with picoseconds dephasing time. Based on the Debye theory, we calculate the lattice thermal conductivity, including scattering by grain boundary and point defect, umklapp process, and phonon resonant scattering. The results indicate…
We present analytical model and molecular dynamics simulations of phonon heat transport in nanowires and nanoribbons with anharmonic lattices and dynamically rough surfaces and edges. In agreement with recent experiments on heat transport in single-crystalline silicon nanowires with rough surfaces, our model and simulations predict finite and length-independent phonon thermal conductivity in such quasi-one-dimensional systems, in contrast to anomalous phonon thermal conductivity of corresponding momentum-conserving systems with atomically smooth surfaces, divergent with the system length. With…
Solid-state lithium-ion batteries (SSLIBs) are considered to be the new generation of devices for energy storage due to better performance and safety. Poly (ethylene oxide) (PEO) based material becomes one of the best candidate of solid electrolytes, while its thermal conductivity is crucial to heat dissipation inside batteries. In this work, we study the thermal conductivity of PEO by molecular dynamics simulation. By enhancing the structure order, thermal conductivity of aligned crystalline PEO is obtained as high as 60 W/m-K at room temperature, which is two orders higher than the value (0.…
We report that single interatomic potential, developed using Gaussian regression of density functional theory calculation data, has high accuracy and flexibility to describe phonon transport with ab initio accuracy in two different atomistic configurations: perfect crystalline Si and crystalline Si with vacancies. The high accuracy of second- and third-order force constants from the Gaussian approximation potential (GAP) are demonstrated with phonon dispersion, Grüneisen parameter, three-phonon scattering rate, phonon-vacancy scattering rate, and thermal conductivity, all of which are very clo…
In this paper, thermal conductivity of crystalline GaAs is calculated using first-principles lattice dynamics. The harmonic and cubic force constants are obtained by fitting them to the force-displacement data from density functional theory calculations. Phonon dispersion is calculated from dynamical matrix constructed using the harmonic force constants and phonon relaxation times are calculated using Fermi Golden rule. The calculated GaAs thermal conductivity agrees well with experimental data. Thermal conductivity accumulations as a function of phonon mean free path and as a function of wave…
