We analyze, through molecular dynamics simulations, the temperature dependence of the thermal conductivity (k) of chain-oriented amorphous polyethylene (PE). We find that at increasing levels of orientation, the temperature corresponding to a peak k progressively decreases. Un-oriented PE exhibits the peak k at 350 K, while aligned PE under an applied strain of 400% shows a maximum at 100 K. This transition of peak k to lower temperatures with increasing alignment is explained in terms of a crossover from disorder to anharmonicity dominated phonon transport in aligned polymers. Evidence for this crossover is achieved by manipulating the disorder in the polymer structure and studying the resulting change in temperature corresponding to peak k. Disorder is modified through a change in the dihedral parameters of the potential function, allowing a change in the relative fraction of trans and gauche transformations. The results shed light on the underlying thermal transport processes in aligned polymers and hold importance for low temperature applications of polymer materials in thermal management technologies.
The poor thermal conductivity of bulk polymers may be enhanced by combining them with high thermal conductivity materials such as carbon nanotubes. Different from random doping, we find that the aligned carbon nanotube-polyethylene composites (ACPCs) has a high thermal conductivity by non-equilibrium molecular dynamics simulations. The analyses indicate that the aligned structure can not only take advantage of the high thermal conduction of carbon nanotubes, but enhance thermal conduction of polyethylene (PE) chains. Our predictions may inspire manufacturing aligned polymer-based composites fo…
The upper limit of the thermal conductivity and the mechanical strength are predicted for the polyethylene chain, by performing the {\it ab initio} calculation and applying the quantum mechanical non-equilibrium Green's function approach. Specially, there are two main findings from our calculation: (1). the thermal conductivity can reach a high value of 310 W/K/m in a 100 nm polyethylene chain at room temperature; (2). the Young's modulus in the polyethylene chain is as high as 374.5 GPa, and the polyethylene chain can sustain $32.85% \pm 0.05%$ (ultimate) strain before undergoing structural p…
Recently, some reports show that the ultra-low thermal conductivity of bulk polymers can be enhanced along one direction, which limits its applications. Here, we proposed paved crosswise laminate methods which can enhance the thermal conductivity of bulk polyethylene (PE) along two directions. We find that the thermal conductivity of paved crosswise polyethylene laminate (PPEL) reaches as high as 181 W/m-K along two in-plane directions, which is three orders of magnitude larger than bulk amorphous polyethylene and even more than two times larger than PE single chain (54 W/m-K). The analyses of…
The thermal transport properties of oriented polymers are of fundamental and practical interest. High thermal conductivities ($\gtrsim 50$ Wm$^{-1}$K$^{-1}$) have recently been reported in disentangled ultra-high molecular weight polyethylene (UHMWPE) films, considerably exceeding prior reported values for oriented films. However, conflicting explanations have been proposed for the microscopic origin of the high thermal conductivity. Here, we report a characterization of the thermal conductivity and mean free path accumulation function of disentangled UHMWPE films (draw ratio $\sim 200$) using…
Polymer simulations routinely employ models with different molecular resolutions. United atom (UA) models are one such example, where groups of certain atoms in a molecule are clustered into superatoms. Although their computational simplicity makes them particularly attractive for studying a wide range of polymer properties, the missing degrees of freedom in UA models can impact certain properties that are intimately linked to localized vibrations, such as the heat capacity and the thermal transport coefficient $κ$. In contrast, the numerically exhausting all atom (AA) models produce results t…
Molecular dynamics simulations are increasingly being used to investigate the structural evolution of polymers during mechanical deformation, but relatively few studies focus on the influence of boundary conditions on this evolution, in particular the dissipation of both heat and pressure through the periodic boundaries during deformation. The research herein explores how the tensile deformation of amorphous polyethylene, modelled with a united atom method potential, is influenced by heat and pressure dissipation. The stress-strain curves for the pressure dissipation cases (uniaxial tension) a…
Low thermal conductivity of polymers, which is one of the considerable drawbacks of commonly used composite structures, has been the focus of many researchers aiming to achieve high-performance polymer-based nanocomposites through the inclusion of highly thermally conductive fillers inside the polymer matrices. Thus, in the present study, a multiscale scheme using non-equilibrium molecular dynamics (NEMD) and finite element (FE) method is developed to explore the impact of different nano-sized fillers (carbon-nitride and graphene) on the effective thermal conductivity of polyethylene-based nan…
We present an ab initio calculation of the DC conductivity of amorphous silicon and hydrogenated amorphous silicon. The Kubo-Greenwood formula is used to obtain the DC conductivity, by thermal averaging over extended dynamical simulation. Its application to disordered solids is discussed. The conductivity is computed for a wide range of temperatures and doping is explored in a naive way by shifting the Fermi level. We observed the Meyer-Neldel rule for the electrical conductivity with E_MNR = 0.06 eV and a temperature coefficient of resistance, TCR ~ -2.0% K^-1 for a-Si:H. In general, experime…
Quantifying the correlation between the complex structures of amorphous materials and their physical properties has been a long-standing problem in materials science. In amorphous Si, a representative covalent amorphous solid, the presence of a medium-range order (MRO) has been intensively discussed. However, the specific atomic arrangement corresponding to the MRO and its relationship with physical properties, such as thermal conductivity, remain elusive. Here, we solve this problem by combining topological data analysis, machine learning, and molecular dynamics simulations. By using persiste…
Thermal conductivity is an important property for almost all applications involving heat transfer, ranging from energy and microelectronics to food processing and textiles. The theory and modeling of crystalline materials is in some sense a solved problem, where one can now calculate the thermal conductivity of any crystalline line compound from first principles [1,2] using expressions based on the phonon gas model (PGM)[3,4]. However, modeling of amorphous materials still has many open questions, because the PGM itself becomes questionable when one cannot rigorously define the phonon velociti…
The dependence of initial magnetic permeability μi of based on the Fe-Si-B amorphous and nanocrystalline alloys on the γ-irradiation dose was investigated by the method of inductance factor determination. It was determined that the alloying of amorphous Fe-Si-B alloys by nickel and molybdenum increases the radiation sensitivity of the μi. Initial magnetic permeability of nanocrystalline magnetic alloys is less sensitive to the action of γ-irradiation as compared with the alloyed amorphous alloys. Has been suggested that radiation influence on the initial magnetic permeability are caused by cre…
Thermally conductive polymers are of fundamental interest and can also be exploited in thermal management applications. Recent studies have shown stretched polymers can achieve high thermal conductivity. However, the transport mechanisms of heat in thermally conductive polymers have yet to be elucidated. Here we report a method for scalable fabrication of polyethylene films with a high thermal conductivity of 62 W/m-K. The achieved thermal conductivity is over two orders-of-magnitude greater than that of typical polymers (~0.1 W/m-K), and exceeds those of many metals and ceramics used as tradi…
In this letter we derive a new method for direct calculation of the modal contributions to thermal conductivity, which is termed Green-Kubo modal analysis (GKMA). The GKMA method combines the lattice dynamics formalism with the Green-Kubo formula for thermal conductivity, such that the thermal conductivity becomes a direct summation of modal contributions, where one need not define the phonon velocity. As a result the GKMA method can be applied to any material/group of atoms where the atoms vibrate around stable equilibrium positions, which includes not only crystalline line compounds, but als…
Thermal transport properties bear a pivotal role in influencing the performance of phase change memory (PCM) devices, in which the PCM operation involves fast and reversible phase change between amorphous and crystalline phases. In this paper, we present a systematic experimental and theoretical study on the thermal conductivity of GeTe at high temperatures involving fast change from amorphous to crystalline phase upon heating. Modulated photothermal radiometry (MPTR) is used to experimentally determine thermal conductivity of GeTe at high temperatures in both amorphous and crystalline phases.…
The impact of Bi implantation on the conductivity and the thermopower of amorphous chalcogenide films is investigated. Incorporation of Bi in Ge-Sb-Te and GeTe results in enhanced conductivity. The negative Seebeck coefficient confirms onset of the electron conductivity in GeTe implanted with Bi at a dose of 2x1016 cm-2. The enhanced conductivity is accompanied by defect accumulation in the films upon implantation as is inferred by using analysis of the space-charge limited current. The results indicate that native coordination defects in lone-pair semiconductors can be deactivated by means of…
The realization of phononic computing is held hostage by the lack of high performance thermal devices. Here we show through theoretical analysis and molecular dynamics simulations that unprecedented thermal rectification factors (as large as 1.20) can be achieved utilizing the phase dependent thermal conductivity of polyethylene nanofibers. More importantly, such high thermal rectifications only need very small temperature differences (< 20 oC) across the device, which is a significant advantage over other thermal diodes which need temperature biases on the order of the operating temperature. …
Amorphous Si (a-Si) nanostructures are ubiquitous in numerous electronic and optoelectronic devices. Amorphous materials are considered to possess the lower limit to the thermal conductivity (k), which is ~1 W/m-K for a-Si. However, recent work suggested that k of micro-thick a-Si films can be greater than 3 W/m-K, which is contributed by propagating vibrational modes, referred to as "propagons". However, precise determination of k in a-Si has been elusive. Here, we used novel structures of a-Si nanotubes and suspended a-Si films that enabled precise in-plane k measurement within a wide thickn…
The value measured in the amorphous structure with the same chemical composition is often considered as a lower bound for the thermal conductivity of any material: the heat carriers are strongly scattered by disorder, and their lifetimes reach the minimum time scale of thermal vibrations. An appropriate design at the nano-scale, however, may allow one to reduce the thermal conductivity even below the amorphous limit. In the present contribution, using molecular-dynamics simulation and the Green-Kubo formulation, we study systematically the thermal conductivity of layered phononic materials (su…
Covalent amorphous semiconductors, such as amorphous silicon (a-Si) and germanium (a-Ge), are commonly believed to have localized electronic states at the top of the valence band and the bottom of the conduction band. Electrical conductivity is thought to be by the hopping mechanism through localized states. The carrier mobility of these materials is usually very low, in the order of ~10^-3 - 10^-2 cm^2/(Vs) at room temperature. In this study, we present the Hall effect characterization of a-Ge prepared by self-ion implantation of Ge ions. The a-Ge prepared by this method is highly homogenous …
We study an insulator-metal transition in a ternary chalcogenide glass (GeSe$_3$)$_{1-x}$Ag$_x$ for $x$=0.15 and 0.25. The conducting phase of the glass is obtained by using "Gap Sculpting" (Prasai et al, Sci. Rep. 5:15522 (2015)) and it is observed that the metallic and insulating phases have nearly identical DFT energies but have a conductivity contrast of ~10$^8$. The transition from insulator to metal involves growth of an Ag-rich phase accompanied by a depletion of tetrahedrally bonded Ge(Se$_{1/2}$)$_4$ in the host network. The relative fraction of the amorphous Ag$_2$Se phase and GeSe$_…
Thermal Conductivity and Temperature-Induced Band Gap Renormalization in Crystalline and Amorphous Ga$_2$O$_3$
Skolkovo Institute of Science and Technology（斯科尔科沃科学技术研究所）；Institute of Nuclear and New Energy Technology, Tsinghua University（清华大学核能与新能源技术研究院）；Digital Materials LLC（数字材料有限责任公司）；Moscow Engineering Physics Institute（莫斯科工程物理学院）
The relationship between effective conductivity and cell structure of polyethylene/carbon composites as well as between effective conductivity and spatial distribution of carbon black are discussed. Following Yoshida's model both structures can, in a way, be said to be intermediate between the well known Maxwell-Garnett (MG) and Bruggeman (BR) limiting structures. Using TEM photographs on composites with various carbon blacks we have observed that the larger is Garncarek's inhomogeneity measure H of two-dimensional (2D) representative distribution of the carbon black, the smaller is the effect…
Thermal conductivities $Λ$ of amorphous carbon thin films are measured in the temperatures range 80--400 K using the $3ω$ method. Sample films range from soft a-C:H prepared by remote-plasma deposition ($Λ= 0.20$ W m$^{-1}$ K$^{-1}$ at room temperature) to amorphous diamond with a large fraction of $sp^3$ bonded carbon deposited from a filtered-arc source ($Λ= 2.2$ W m$^{-1}$ K$^{-1}$). Effective-medium theory provides a phenomenological description of the variation of conductivity with mass density. The thermal conductivities are in good agreement with the minimum thermal conductivity calcula…
Using direct atomic simulations, the vibration scattering time scales are characterized, and then the nature and the quantitative weight of thermal excitations are investigated in an example system Li2S from its amorphous solid state to its partial-solid partial-liquid and, liquid states. For the amorphous solid state at 300 K, the vibration scattering time ranges a few femtoseconds to several picoseconds. As a result, both the progagons and diffusons are the main heat carriers and contribute largely to the total thermal conductivity. The enhancement of scattering among vibrations and between …
First-principles based modeling on phonon dynamics and transport using density functional theory and Boltzmann transport equation has proven powerful in predicting thermal conductivity of crystalline materials, but it remains unfeasible for modeling complex crystals and disordered solids due to the prohibitive computational cost to capture the disordered structure, especially when the quasiparticle "phonon" model breaks down. Recently, machine-learning regression algorithms show great promises for building high-accuracy potential fields for atomistic modeling with length and time scales far be…
Proper consideration of anharmonicity is important for the calculation of the thermal conductivity. However, how the anharmonicity influences the thermal conduction in amorphous materials is still an open question. In this work, we uncover the role of anharmonicity on the thermal conductivity of amorphous silica (a-SiO2) by comparing the thermal conductivity predicted from the harmonic theory and the anharmonic theory. Moreover, we explore the effect of anharmonicity-induced frequency shift on the prediction of the thermal conductivity. It is found that the thermal conductivity calculated by t…
We model electrical conductivity in metastable amorphous $Ge_{2}Sb_{2}Te_{5}$ using independent contributions from temperature and electric field to simulate phase change memory devices and Ovonic threshold switches. 3D, 2D-rotational, and 2D finite element simulations of pillar cells capture threshold switching and show filamentary conduction in the on-state. The model can be tuned to capture switching fields from ~5 to 40 MV/m at room temperature using the temperature dependent electrical conductivity measured for metastable amorphous GST; lower and higher fields are obtainable using differe…
We deposit intrinsic hydrogenated amorphous silicon (a-Si:H) thin films by reactive pulsed laser deposition, for various hydrogen pressures in the 0-20 Pa range, at a low deposition temperature of 120C, and investigate the hydrogen incorporation, structural, optical, and electrical properties of the films, as a function of the ambient hydrogen pressure. The film thickness decreases linearly as the hydrogen pressure increases. The hydrogen content of the films is determined by infrared spectroscopy and the optical bandgap from UV-Vis-NIR transmittance and reflectance measurements. Electric meas…
Boron doped amorphous conducting carbon films show MI transition induced by doping. In this paper we discuss the ac conductivity of the films, which lie on the insulating side of MI transition. The ac conductivity data is analyzed as a function of frequency as well as temperature for both real as well as imaginary part of the conductivity data. The ac conductivity of these samples shows enhanced interaction effect at low temperature. The conduction mechanism at high frequency and at low temperature is due to the tunneling mechanism. At intermediate temperatures and at moderate frequencies, the…
Two-dimensional (2D) materials like graphene and h-BN usually show high thermal conductivity, which enables rich applications in thermal dissipation and nanodevices. Disorder, on the other hand, is often present in 2D materials. Structural disorder induces localization of electrons and phonons and alters the electronic, mechanical, thermal, and magnetic properties. Here we calculate the in-plane thermal conductivity of both monolayer carbon and monolayer boron nitride in the amorphous form, by reverse nonequilibrium molecular dynamics simulations. We find that the thermal conductivity of both …
All-solid-state batteries using sodium are promising candidates for next-generation rechargeable batteries due to the limited lithium resources. A practical sodium battery requires an electrolyte with high conductivity. Cubic Na$_3$PS$_4$ exhibiting high conductivity of over 10$^{-4}$ S cm$^{-1}$ is obtained by crystallizing amorphous Na$_3$PS$_4$ synthesized by ball milling. Amorphous Na$_3$PS$_4$ crystallizes in a cubic structure and then is transformed into a tetragonal phase upon heating. In this study, in situ observation by transmission electron microscopy demonstrates that the crystalli…
The conductivity of $α$-polyvinylidene fluoride ($α$-PVDF) is obtained from dielectric measurements performed in the frequency domain at several temperatures. At temperatures above the glass-transition, the conductivity can be interpreted as an ionic conductivity, which confirms earlier results reported in the literature. Our investigation shows that the observed ionic conductivity is closely related to the amorphous phase of the polymer.
Ferromagnetism above room temperature was observed in Cr-doped hydrogenated amorphous silicon films deposited by rf magnetron-sputtering. Structure analysis reveals that films are amorphous without any detectable precipitates up to the solubility limit 16 atomic percentages of Cr. Experimental results suggest that hydrogenation has a dramatic influence on magnetic properties, electrical conductivity and carrier concentration in the thin films. Pronounced anomalous Hall effect and magnetization curve both suggest the origin of the ferromagnetism may arises from percolation of magnetic polarons.
The ability to engineer the thermal conductivity of materials allows us to control the flow of heat and derive novel functionalities such as thermal rectification, thermal switching, and thermal cloaking. While this could be achieved by making use of composites and metamaterials at bulk scales, engineering the thermal conductivity at micro- and nano-scale dimensions is considerably more challenging. In this work we show that the local thermal conductivity along a single Si nanowire can be tuned to a desired value (between crystalline and amorphous limits) with high spatial resolution through s…
Glasses usually represent the lower limit for the thermal conductivity of solids, but a fundamental understanding of lattice heat transport in amorphous materials can provide design rules to beat such a limit. Here we investigate the role of mass disorder in glasses by studying amorphous silicon-germanium alloy (a-Si$_{1-x}$Ge$_x$) over the full range of atomic concentration from $x=0$ to $x=1$, using molecular dynamics and the quasi-harmonic Green-Kubo lattice dynamics formalism. We find that the thermal conductivity of a-Si$_{1-x}$Ge$_x$ as a function of $x$ exhibits a smoother U-shape than …
The ultra-low thermal conductivity (~0.3 Wm-1K-1) of amorphous epoxy resins significantly limits their applications in electronics. Conventional top-down methods e.g. electrospinning usually result in aligned structure for linear polymers thus satisfactory enhancement on thermal conductivity, but they are deficient for epoxy resin polymerized by monomers and curing agent due to completely different cross-linked network structure. Here, we proposed a bottom-up strategy, namely parallel-linking method, to increase the intrinsic thermal conductivity of bulk epoxy resin. Through equilibrium molecu…
Machine-Learning-Guided Insights into Solid-Electrolyte Interphase Conductivity: Are Amorphous Lithium Fluorophosphates the Key?
Bakar Institute of Digital Materials for the Planet, UC Berkeley（加州大学伯克利分校巴卡尔数字材料行星研究所）；Materials Sciences Division, Lawrence Berkeley National Laboratory（劳伦斯伯克利国家实验室材料科学部）；Department of Materials Science and Engineering, National University of Singapore（新加坡国立大学材料科学与工程系）
Amorphous samples of Al-Cu-Fe were crystallized to the icosahedral phase under the control of electrical conductivity and thermopower at a rather small temperature of T=720 K. A comparison between different annealing states of the amorphous and the resulting quasicrystalline phase done on the same sample shows aston-ishing parallels in conductivity and large differences in thermopower.
Amorphous silicon (a-Si) is an important thermal-management material and also serves as an ideal playground for studying heat transport in strongly disordered materials. Theoretical prediction of the thermal conductivity of a-Si in a wide range of temperatures and sample sizes is still a challenge. Herein we present a systematic investigation of the thermal transport properties of a-Si by employing large-scale molecular dynamics (MD) simulations with an accurate and efficient machine-learned neuroevolution potential (NEP) trained against abundant reference data calculated at the quantum-mechan…
We developed a capacitor type heat flow switching device, in which electron thermal conductivity of the electrodes is actively controlled through the carrier concentration varied by an applied bias voltage. The devices consist of an amorphous p-type Si-Ge-Au alloy layer, an amorphous SiO$_2$ as the dielectric layer, and a n-type Si substrate. Both amorphous materials are characterized by very low lattice thermal conductivity, less than 1 Wm-1K-1. The Si-Ge-Au amorphous layer with 40 nm in thickness was deposited by means of molecular beam deposition technique on the 100 nm thick SiO$_2$ layer …
Recrystallization of glasses is important in a wide range of applications including electronics and reactive materials. Molecular dynamics (MD) has been used to provide an atomic picture of this process, but prior work has neglected the thermal transport role of electrons, the dominant thermal carrier in metallic systems. We characterize the role of electronic thermal conductivity on the velocity of recrystallization in Ni using MD coupled to a continuum description of electronic thermal transport via a two-temperature model. Our simulations show that for strong enough coupling between electro…
By invoking the microscopic response method in conjunction with a reasonable set of approximations, we obtain new explicit expressions for the electrical conductivity and temperature coefficient of resistivity (TCR) in amorphous semiconductors, especially a-Si:H and a-Ge:H. The predicted TCR for n-doped a-Si:H and a-Ge:H is in agreement with experiments. The conductivity from the transitions from a localized state to an extended state (LE) is comparable to that from the transitions between two localized states (LL). This resolves a long-standing anomaly, a "kink" in the experimental $\log_{10}…
We report on evaluation of lattice thermal conductivity of GeTe/Sb$_{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…
