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. Thermal boundary resistances are accurately taken into account for experimental consideration. To develop a concrete understanding of the underlying physical mechanism, rigorous and in-depth theoretical exercises are carried out. For this, first-principles density functional methods and linearized Boltzmann transport equations (LBTE) are employed using both direct and relaxation time based approach (RTA) and compared with that of the phenomenological Slack model. The amorphous phase experimental data has been described using the minimal thermal conductivity model with sufficient precision. The theoretical estimation involving direct solution and RTA method are found to retrieve well the trend of the experimental thermal conductivity for crystalline GeTe at high temperatures despite being slightly overestimated and underestimated, respectively, compared to the experimental data. A rough estimate of vacancy contribution has been found to modify the direct solution in such a way that it agrees excellently with the experiment. Umklapp scattering has been determined as the significant phonon-phonon scattering process. Umklapp scattering parameter has been identified for GeTe for the whole temperature range which can uniquely determine and compare Umklapp scattering processes for different materials.

Phonon hydrodynamics is an exotic phonon transport phenomenon that challenges the conventional understanding of diffusive phonon scattering in crystalline solids. It features a peculiar collective motion of phonons with various unconventional properties resembling fluid hydrodynamics, facilitating non Fourier heat transport. Hence, it opens up several new avenues to enrich the knowledge and implementations on phonon physics, phonon engineering, and micro and nanoelectronic device technologies. This review aims at covering a comprehensive development as well as the recent advancements in this field via experiments, analytical methods, and state-of-the-art numerical techniques. The evolution of the topic has been realized using both phenomenological and material science perspectives. Further, the discussions related to the factors that influence such peculiar motion, illustrate the capability of phonon hydrodynamics to be implemented in various applications. A plethora of new ideas can emerge from the topic considering both the physics and the material science axes, navigating toward a promising outlook in the research areas around phonon transport in non-metallic solids.

The existence of the Frenkel line in the supercritical regime of a Lennard-Jones (LJ) fluid shown through molecular dynamics (MD) simulations initially and later corroborated by experiments on argon opens up possibilities of understanding the structure and dynamics of supercritical fluids in general and of the Frenkel line in particular. The location of the Frenkel line, which demarcates two distinct physical states, liquidlike and gaslike within the supercritical regime, has been established through MD simulations of the velocity autocorrelation (VACF) and radial distribution function (RDF). We, in this article, explore the changes in the structural features of supercritical LJ fluid under partial confinement using atomistic walls. The study is carried out across the Frenkel line through a series of MD simulations considering a set of thermodynamics states in the supercritical regime ($P=5000$ bar, $240\mathrm{K}\le T\le 1500\mathrm{K}$) of argon well above the critical point. Confinement is partial, with atomistic walls located normal to $z$ and extending to “infinity” along the $x$ and $y$ directions. In the “liquidlike” regime of the supercritical phase, particles are found to be distributed in distinct layers along the $z$ axis with layer spacing less than one atomic diameter and the lateral RDF showing amorphous-like structure for specific spacings (packing frustration) and non-amorphous-like structure for other spacings. Increasing the rigidity of the atomistic walls is found to lead to stronger layering and increased structural order. For confinement with reflective walls, layers are found to form with one atomic diameter spacing and the lateral RDF showing close-packed structure for the smaller confinements. Translational order parameter and excess entropy assessment confirms the ordering taking place for atomistic wall and reflective wall confinements. In the “gaslike” regime of the supercritical phase, particle distribution along the spacing and the lateral RDF exhibit features not significantly different from that due to normal gas regime. The heterogeneity across the Frenkel line, found to be present both in bulk and confined systems, might cause the breakdown of the universal scaling between structure and dynamics of fluids necessitating the determination of a unique relationship between them.

Particle motion and correlations in fluids within confined domains promise to provide challenges and opportunities for experimental and theoretical studies. We report molecular dynamics simulations of a Lennard-Jones gas mimicking argon under partial confinement for a wide range of densities at a temperature of $300\mathrm{K}$. The isotropic behavior of velocity autocorrelation function (VACF) and mean squared displacement (MSD), seen in the bulk, breaks down due to partial confinement. A distinct trend emerges in the ${\text{VACF}}_{\perp }$ and ${\text{MSD}}_{\perp }$, corresponding to the confined direction, while the trends in ${\text{VACF}}_{\parallel }$ and ${\text{MSD}}_{\parallel }$, corresponding to the other two unconfined directions are seen to be unaffected by the confinement. ${\text{VACF}}_{\perp }$ displays a minimum, at short timescales, that correlates with the separation between the reflective walls. The effect of partial confinement on ${\text{MSD}}_{\perp }$ is seen to manifest as a transition from diffusive to subdiffusive motion with the transition time correlating with the minimum in the ${\text{VACF}}_{\perp }$. When compared to the trends shown by MSD and VACF in the bulk, the ${\text{MSD}}_{\perp }$ exhibits subdiffusive behavior, and the ${\text{VACF}}_{\perp }$ features rapid decay, suggesting that confinement suppresses the role of thermal fluctuations significantly. Repetitive wall-mediated collisions are identified to give rise to the minima in ${\text{VACF}}_{\perp }$ and in turn a characteristic frequency in its frequency spectrum. The strong linear relation between the minima in ${\text{VACF}}_{\perp }$ and wall-spacing suggests the existence of collective motion propagating at the speed of sound. These numerical experiments can offer interesting possibilities in the study of confined motion with observable consequences.

A first-principles density functional method along with the direct solution of linearized Boltzmann transport equations are employed to systematically analyze the low-temperature thermal transport in crystalline GeTe. The extensive thermal transport simulations, ranging from room temperature to cryogenic temperatures, reveal the emergence of a phonon hydrodynamic regime in GeTe at low temperature. The reduction of grain boundary scattering is found to play a crucial role along with the divergent trend of umklapp and normal scattering at low temperatures in accommodating the hydrodynamic regime. Average scattering rates for normal, umklapp, and other resistive processes are distinguished for a wide range (4–300 K) of temperatures and used for identifying various phonon transport regimes. Therefore, the variations of lattice thermal conductivity, phonon propagation length, and thermal diffusivity with temperature, related to these transport regimes (ballistic, hydrodynamic, and kinetic), have been thoroughly investigated. The modewise decomposition of lattice thermal conductivity and the distinction of thermal diffusivity according to different scattering processes reveal rich information on the dominant phonon modes and phonon scattering processes in GeTe at low temperature. Further, the kinetic-collective model is used to elucidate the hydrodynamic behavior of phonon scattering through the relative study of collective and kinetic contributions to the thermal transport properties. In this context, the Knudsen number is estimated through the characteristic nonlocal length and the grain size, which further quantifies the consistent hydrodynamic behavior of phonon thermal transport for GeTe. Finally, phonon-vacancy scattering for GeTe is realized, and vacancies are found strongly to influence the hydrodynamic window while incorporating the other resistive scattering mechanisms.

This article presents three photothermal methods dedicated to the measurement of the thermal properties of chalcogenide alloys, used as a central element in the new generations of non-volatile memory. These materials have two phases, amorphous and crystalline, possessing a sharp contrast in their electrical and thermal properties. In the crystalline phase, the properties also change very significantly with temperature. The control of the temperature of the samples, the choice of transducers, and the time or frequency characteristic values of the photothermal excitation are thoroughly discussed. Each photothermal technique is described from the experimental point of view as well as from the inverse method, performed to identify the parameters of interest. The identified thermal properties mainly concern the thermal conductivity and the thermal resistance at the interfaces between the phase-change materials and the materials in contact as encountered in the production of the microelectronic memory device. Assessing various photothermal techniques, the study suggests that pulsed photothermal radiometry is the most effective method for sensitive high-temperature measurements of thermal properties of the phase-change materials.