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 vibrations and free ions flow due to the increase of temperature, will lead to a large reduction of the scattering time scale and the acoustic vibrational thermal conductivity, i.e., 0.8 W/mK at 300 K to 0.56 W/mK in the partial solid partial liquid Li2S at 700 K. In this latter state, the thermal conductivity contributed by convection increases to the half of the total, as a result of the usually neglected cross-correlation between the virial term and the free ions' flow. The vibrational scattering time can be as large as ~ 1.5 picoseconds yet, and the vibrational conductivity is reduced to a still significant 0.42 W/mK highlighting the unexpected role of acoustic transverse and longitudinal vibrations in liquid Li2S at 1100 K. At this same temperature, the convection heat transfer takes overreaching 0.63 W/mK. Our study provides a fundamental understanding of the thermal excitations at play in amorphous materials from solid to liquid.
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 effects of the finite size of the simulation box in equilibrium molecular dynamics simulations are investigated for prototypical superionic conductors of different types, namely the fluorite-structure materials PbF2, CaF2, and UO2 (type-II), and the α phase of AgI (type I). Largely validated empirical force-fields are employed to run ns-long simulations and extract general trends for several properties, at increasing size and in a wide temperature range. This work shows that, for the considered type-II superionic conductors, the diffusivity dramatically depends on the system size and that …
We present the investigations on atomic dynamics and Li+ diffusion in crystalline and amorphous Li2Si2O5 using quasielastic (QENS) and inelastic neutron scattering (INS) studies supplemented by ab-initio molecular dynamics simulations (AIMD). The QENS measurements in the amorphous phase of Li2Si2O5 show a narrow temperature window (700 < T < 775 K), exhibiting significant quasielastic broadening corresponding to the fast Li+ diffusion and relaxation of SiO4 units to the crystalline phase. Our INS measurements clearly show the presence of large phonon density of states (PDOS) at low energy (low…
$β$- Eucryptite (LiAlSiO4) is a potential electrolyte for Li- ion battery due to its high Li- ion conductivity and very small volume thermal expansion coefficient. We have performed ab-initio molecular dynamics simulations of $β$- Eucryptite to study the origin of high temperature superionic phase transition in this material. The simulations are able to provide the microscopic understanding of the one -dimensional superionicity that occurs along the hexagonal c-axis and is associated with the order-disorder nature of the phase transition. The Li ionic conductivity is found to enhance due to th…
The synthesis of xAgI(1-x)[Ag2O.B2O3] amorphous superionic conductors is done via mechanochemical synthesis route (for x = 0.5 and 0.7). Ionic conductivities of 3 mOhm-1cm-1 for x = 0.5 sample and 5mOhm-1cm-1 for x = 0.7 sample at room temperature, are observed, which are higher than those of the melt quenched glassy samples. Impedance plots (Nyquist plots) are found to be depressed semicircles with a tail at low frequency end. The corresponding equivalent circuit is postulated and each circuit element is related to a physical process. The ac conductivity is analyzed in view of the universal d…
Sulfide-based glasses and glass-ceramics showing high ionic conductivities and excellent mechanical properties are considered as promising solid-state electrolytes. Nowadays, the computational material techniques with the advantage of low research cost are being widely utilized for understanding, effectively screening and discovering of battery materials. In consideration of the rising importance and contributions of computational studying on the glassy SSE materials, here, this work summarizes the common computational methods utilized for studying the amorphous inorganic materials, review the…
Recently, the superionic thermoelectrics, which typify the novel `phonon-liquid electron-crystal' concept, have attracted enormous attention due to their ultralow thermal conductivity and high figure-of-merit (zT). However, their high zT is generally obtained deep inside the superionic phase, e.g., near 1000~K in the Cu$_2$X (X: chalcogen atom) family where the superionic transition is close to 400~K. At such high temperatures, the liquid-like flow of the metal ions under an electric field or a temperature gradient, both of which are integral to the working of a thermoelectric device, results …
Thermoelectric materials create an electric potential when subject to a temperature gradient and vice versa hence they can be used to harvest waste heat into electricity and in thermal management applications. However, finding highly efficient thermoelectrics with high figures of merit, zT$\geq$1, is very challenging because the combination of high power factor and low thermal conductivity is rare in materials. Here, we use first-principles methods to analyze the thermoelectric properties of Li$_2$Sn$X_3$ ($X$=S,Se), a recently synthesized class of lithium fast-ion conductors presenting high t…
The thermal properties of amorphous and crystalline phases in chalcogenide phase change materials (PCM) play a key role in device performance for non-volatile random-access memory. Here, we report the nanothermal morphology of amorphous and crystalline phases in laser pulsed GeTe and Ge2Sb2Te5 thin films by scanning thermal microscopy (SThM). By performing SThM measurements and applying quantitative physical models to two film thicknesses, the PCM thermal conductivities and thermal boundary conductances between the PCM and SThM probe are independently estimated for the amorphous and crystallin…
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…
Using very long molecular dynamics simulation runs, temperature protocols spanning up to five orders of magnitude in time-scales are performed to investigate thermally activated structural relaxation in a model amorphous solid. The simulations demonstrate significant local structural excitations as a function of increasing temperature and show that enthalpy rather than energy is primarily responsible for relaxation. The observed enthalpy changes are of the order seen in experiment, and can be correlated with the level of internal hydrostatic stress homogenization and icosahedral content within…
Here we examine the role of the amorphous insulating substrate in the thermal relaxation in thin NbN, InO$_x$, and Au/Ni films at temperatures above 5 K. The studied samples are made up of metal bridges on an amorphous insulating layer lying on or suspended above a crystalline substrate. Noise thermometry was used to measure the electron temperature $T_e$ of the films as a function of Joule power per unit of area $P_{2D}$. In all samples, we observe the dependence $P_{2D}\propto T_e^n$ with the exponent $n\simeq 2$, which is inconsistent with both electron-phonon coupling and Kapitza thermal r…
The structural relaxation of pure amorphous silicon (a-Si) and hydrogenated amorphous silicon (a-Si:H) materials, that occurs during thermal annealing experiments, has been analysed by Raman spectroscopy and differential scanning calorimetry. Unlike a-Si, the heat evolved from a-Si:H cannot be explained by relaxation of the Si-Si network strain, but it reveals a derelaxation of the bond angle strain. Since the state of relaxation after annealing is very similar for pure and hydrogenated materials, our results give strong experimental support to the predicted configurational gap between a-Si an…
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…
An approach is presented for the atomistic study of phonon transport in real dielectric nanowires via Green functions. The formalism is applied to investigate the phonon flow through nanowires coated by an amorphous material. Examples for a simple model system, and for real Si nanowires coated by silica are given. New physical results emerge for these systems, regarding the character of the transition from ballistic to diffusive transport, the low temperature thermal conductance, and the influence of the wire-coating interface on the thermal transport. An efficient treatment of phonon scatteri…
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.…
Building on the recent discovery of tough nanocrystalline Cu-Zr alloys with amorphous intergranular films, this paper investigates ternary nanocrystalline Cu-Zr-Hf alloys with a focus on understanding how alloy composition affects the formation of disordered complexions. Binary Cu-Zr and Cu-Hf alloys with similar initial grain sizes were also fabricated for comparison. The thermal stability of the nanocrystalline alloys was evaluated by annealing at 950 °C (>95% of the solidus temperatures), followed by detailed characterization of the grain boundary structure. All of the ternary alloys exhibi…
A method to investigate anharmonicity, vibrational anisotropy and thermal expansion using correlated mean-square relative displacements (MSRD) parallel and perpendicular to the interatomic bonds obtained only from Extended X-ray Absorption Fine Structure (EXAFS) analysis based on cumulant expansion is suggested and applied to an amorphous Ni$_{46}$Ti$_{54}$ alloy produced by mechanical alloying. From EXAFS measurements taken on Ni and Ti K edges at several temperatures, the thermal behavior of $\text{MSRD}_\parallel$, $\text{MSRD}_\perp$ and of the cumulants $C_1^*$, $C_2^*$ and $C_3^*$ of the…
The preferentially (220) orientated polycrystalline silicon films have been fabricated by performing photon-involved rapid thermal annealing upon amorphous silicon films. In contrast, conventional thermal annealing of the silicon amorphous films results in the preference of (111) orientated crystallization. This difference reveals the overlooked impaction of photons upon silicon atoms, which results in the preferential orientation of lattice plans with the smallest density of atoms on their projection plane rather than the lowest energies.
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…
Normal mode decomposition of atomic vibrations has been used to provide microscopic under-standing of thermal transport in amorphous solids for decades. In normal mode methods, it is naturally assumed that atoms vibrate around their equilibrium positions and that individual normal modes are the fundamental vibrational excitations transporting heat. With the abundance of predictions from normal mode methods and experimental measurements now available, we care-fully analyze these calculations in amorphous silicon, a model amorphous solid. We find a number of discrepancies, suggesting that treati…
The magnetization processes in binary magnetic/nonmagnetic amorphous alloy Hf_{57}Fe_{43} are investigated by the detailed measurements of magnetic hysteresis loops, temperature dependence of magnetization, relaxation of magnetization and magnetic ac susceptibility, including a nonlinear term. Blocking of magnetic moments at lower temperatures is accompanied with the slow relaxation of magnetization and magnetic hysteresis loops. All of the observed properties are explained with the superparamagnetic behaviour of the single domain magnetic clusters inside the nonmagnetic host, their blocking b…
From Amorphous to Amorphous-Crystalline Mixed-Phase Boron Nitride: Evolution of the Thermal and Elastic Properties
Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and BIST（加泰罗尼亚纳米科学与纳米技术研究所）；Faculty of Physics, Autonomous University of Barcelona（巴塞罗那自治大学物理系）；Universite Claude Bernard Lyon 1, CNRS, LMI, UMR 5615（里昂第一大学）；Faculty of Physics and Astronomy, Adam Mickiewicz University（亚当密茨凯维奇大学物理与天文学院）；International Iberian Nanotechnology Laboratory（伊比利亚纳米技术国际实验室）；ICREA（加泰罗尼亚高级研究院）
Interfacial thermal transport in Si/SiC and SiC/diamond heterostructures: effects of amorphous interlayers and SiC polytypes
K. N. Toosi University of Technology（K.N.托辛理工大学）；Institute for Research in Fundamental Sciences（基础科学研究所）；Imam Khomeini International University（伊玛目霍梅尼国际大学）
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 th…
Amorphous tantala (a-Ta2O5) is an important technological material that has wide ranging applications in electronics, optics and the biomedical industry. It is used as the high refractive index layers in the multi-layer dielectric mirror coatings in the latest generation of gravitational wave interferometers, as well as other precision interferometers. One of the current limitations in sensitivity of gravitational wave detectors is Brownian thermal noise that arises from the tantala mirror coatings. Measurements have shown differences in mechanical loss of the mirror coatings, which is directl…
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）
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…
We report on the synthesis and characterization of nanocrystalline delta-MoN by crystallization of amorphous thin films grown on (100) Si by reactive sputtering at room temperature. Films with chemical composition MoN were grown using a deposition pressure of 5mTorr with a reactive mixture of Ar/(Ar+N2)=0.5. The as-grown films display mostly amorphous structure. Nanocrystalline delta-MoN phase is obtained after annealing at temperatures above 600 °C. The superconducting critical temperature Tc depends on film thickness. Thick films (170 nm) annealed at 700 °C for 30 min display a Tc = 11.2 K (…
We extend our earlier shear-transformation-zone (STZ) theory of amorphous plasticity to include the effects of thermally assisted molecular rearrangements. This version of our theory is a substantial revision and generalization of conventional theories of flow in noncrystalline solids. As in our earlier work, it predicts a dynamic transition between jammed and flowing states at a yield stress. Below that yield stress, it now describes thermally assisted creep. We show that this theory accounts for the experimentally observed strain-rate dependence of the viscosity of metallic glasses, and that…
Recently (C.-T. Toh et al., Nature 577, 199 (2020)), the first synthesis of free-standing monolayer amorphous carbon (MAC) was achieved. MAC is a pure carbon structure composed of five, six, seven and eight atom rings randomly distributed. MAC proved to be surprisingly stable and highly fracture resistant. Its electronic properties are similar to boron nitride. In this work, we have investigated the mechanical properties and thermal stability of MAC models using fully-atomistic reactive molecular dynamics simulations. For comparison purposes, the results are contrasted against pristine graphen…
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…
Amorphous films of tantalum oxide (Ta2O5) are widely applied to build highly reflective mirrors used in interferometric gravitational wave detectors, such as the Laser Interferometer Gravitational Wave Observatory (LIGO). Despite a large number of studies, the structural properties of amorphous Ta2O5 at the local scale still deserve several further investigations. Such information is essential to any attempt to understand the properties of this important material and no property modelling efforts can be expected to yield reliable information until the local structure in the amorphous phase is …
Historically, the design of hybrid solar photovoltaic thermal (PVT) systems has focused on cooling crystalline silicon (c-Si)-based photovoltaic (PV) devices to avoid temperature-related losses. This approach neglects the associated performance losses in the thermal system and leads to a decrease in the overall exergy of the system. Consequently, this paper explores the use of hydrogenated amorphous silicon (a-Si:H) as an absorber material for PVT in an effort to maintain higher and more favourable operating temperatures for the thermal system. Amorphous silicon not only has a smaller temperat…
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…
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…
It is shown that the well-known blue-shift of the fundamental absorption edge in as-deposited compositionally modulated amorphous Si/Ge and As6Se94/Se80Te20 multilayers (with periods of 4-8 nm) is further enhanced due to the thermal or laser-induced intermixing of adjacent layers. The laser-induced intermixing process, as supported by experiments and model calculations, can be attributed to both the local heating and photo-effects in As6Se94/Se80Te20 multilayers, while only the thermal effects were observed for Si/Ge multilayers. Structural transformations, based on this enhanced interdiffusio…
Thermal stability of hydrogenated amorphous Si/Ge multilayers has been investigated by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Small-Angle X-Ray Diffraction (SAXRD) techniques. Amorphous H-Si/Ge multilayers were prepared by RF sputtering with 1.5 and 6 ml/min H2 flow-rate. It is shown by Elastic Recoil Detection Analysis (ERDA) that the hydrogen concentration increased by increasing H2 flow-rate. Annealing of the samples was carried out at 400 and 450 oC for several hours. It has been observed that samples prepared with 6 ml/min flow-rate at both annealin…
In this work, we investigate the correlation between morphology, composition, and the mechanical properties of metallic amorphous tungsten-oxygen and amorphous tungsten-oxide films deposited by Pulsed Laser Deposition. This correlation is investigated by the combined use of Brillouin Spectroscopy and the substrate curvature method. The stiffness of the films is strongly affected by both the oxygen content and the mass density. The elastic moduli show a decreasing trend as the mass density decreases and the oxygen-tungsten ratio increases. A plateaux region is detected in correspondence of the …
There is a renewed interest in photovoltaic solar thermal (PVT) hybrid systems, which harvest solar energy for heat and electricity. Typically, a main focus of a PVT system is to cool the photovoltaic (PV) cells to improve the electrical performance, however, this causes the thermal component to under-perform compared to a solar thermal collector. The low temperature coefficients of amorphous silicon (a-Si:H) allow for the PV cells to be operated at higher temperatures and are a potential candidate for a more symbiotic PVT system. The fundamental challenge of a-Si:H PV is light-induced degrada…
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…
In this paper we discuss the application of current it ab initio computer simulation techniques to hydrogenated amorphous silicon (a-Si:H). We begin by discussing thermal fluctuation in the number of coordination defects in the material, and its temperature dependence. We connect this to the ``fluctuating bond center detachment" mechanism for liberating H bonded to Si atoms. Next, from extended thermal MD simulation, we illustrate various mechanisms of H motion. The dynamics of the lattice is then linked to the electrons, and we point out that the squared electron-lattice coupling (and the the…
The short and intermediate range order of an amorphous Ge$_{30}$Se$_{70}$ alloy produced by Mechanical Alloying were studied by Reverse Monte Carlo simulations of its x-ray total structure factor, Raman scattering and differential scanning calorimetry. The simulations were used to compute the $G^{\text{RMC}}_{\text{Ge-Ge}}(r)$, $G^{\text{RMC}}_{\text{Ge-Se}}(r)$ and $G^{\text{RMC}}_{\text{Se-Se}}(r)$ partial distribution functions and the ${\cal S}^{\text{RMC}}_{\text{Ge-Ge}}(K)$, ${\cal S}^{\text{RMC}}_{\text{Ge-Se}}(K)$ and ${\cal S}^{\text{RMC}}_{\text{Se-Se}}(K)$ partial structure factors.…
While two-terminal HfOX (x<2) memristor devices have been studied for ion transport and current evolution, there have been limited reports on the effect of the long-range thermal environment on their performance. In this work, amorphous-HfOX based memristor devices on two different substrates, thin SiO2(280 nm)/Si and glass, with different thermal conductivities in the range from 1.2 to 138 W/m-K were fabricated. Devices on glass substrates exhibit lower reset voltage, wider memory window and, in turn, a higher performance window. In addition, the devices on glass show better endurance than th…
