Non-equivalent Atomic Vibrations at Interfaces in a Polar Superlattice.

In heterostructures made from polar materials, e.g., AlN-GaN-AlN, the non-equivalence of the two interfaces has long been recognized as a critical aspect of their electronic properties, in that they host different two-dimensional carrier gases. Interfaces play an important role in the vibrational properties of materials, where interface states enhance thermal conductivity and can generate unique infrared-optical activity. The non-equivalence of the corresponding interface atomic vibrations, however, has not been investigated so far due to a lack of experimental techniques with both high spatial and high spectral resolution. Herein we experimentally demonstrate the non-equivalence of AlN-(Al0.65Ga0.35)N and (Al0.65Ga0.35)N-AlN interface vibrations using monochromated electron energy-loss spectroscopy in the scanning transmission electron microscope (STEM-EELS) and employ density-functional-theory (DFT) calculations to gain insights in the physical origins of observations. We demonstrate that STEM-EELS possesses sensitivity to the displacement vector of the vibrational modes as well as the frequency, which is as critical to understanding vibrations as polarization in optical spectroscopies. The combination enables direct mapping of the non-equivalent interface phonons between materials with different phonon polarizations. The results demonstrate the capacity to carefully assess the vibrational properties of complex heterostructures where interface states dominate the functional properties. This article is protected by copyright. All rights reserved.

Validation of the Wiedemann-Franz Law in Solid and Molten Tungsten above 2000 K through Thermal Conductivity Measurements via Steady-State Temperature Differential Radiometry.

We measure the thermal conductivity of solid and molten tungsten using steady state temperature differential radiometry. We demonstrate that the thermal conductivity can be well described by application of Wiedemann-Franz law to electrical resistivity data, thus suggesting the validity of Wiedemann-Franz law to capture the electronic thermal conductivity of metals in their molten phase. We further support this conclusion using ab initio molecular dynamics simulations with a machine-learned potential. Our results show that at these high temperatures, the vibrational contribution to thermal conductivity is negligible compared to the electronic component.

Interlayer Coupling Controlled Ordering and Phases in Polar Vortex Superlattices.

The recent discovery of polar topological structures has opened the door for exciting physics and emergent properties. There is, however, little methodology to engineer stability and ordering in these systems, properties of interest for engineering emergent functionalities. Notably, when the surface area is extended to arbitrary thicknesses, the topological polar texture becomes unstable. Here we show that this instability of the phase is due to electrical coupling between successive layers. We demonstrate that this electrical coupling is indicative of an effective screening length in the dielectric, similar to the conductor-ferroelectric interface. Controlling the electrostatics of the superlattice interfaces, the system can be tuned between a pure topological vortex state and a mixed classical-topological phase. This coupling also enables engineering coherency among the vortices, not only tuning the bulk phase diagram but also enabling the emergence of a 3D lattice of polar textures.

Enhanced Thermal Boundary Conductance across GaN/SiC Interfaces with AlN Transition Layers.

Heat dissipation plays a crucial role in the performance and reliability of high-power GaN-based electronics. While AlN transition layers are commonly employed in the heteroepitaxial growth of GaN-on-SiC substrates, concerns have been raised about their impact on thermal transport across GaN/SiC interfaces. In this study, we present experimental measurements of the thermal boundary conductance (TBC) across GaN/SiC interfaces with varying thicknesses of the AlN transition layer (ranging from 0 to 73 nm) at different temperatures. Our findings reveal that the addition of an AlN transition layer leads to a notable increase in the TBC of the GaN/SiC interface, particularly at elevated temperatures. Structural characterization techniques are employed to understand the influence of the AlN transition layer on the crystalline quality of the GaN layer and its potential effects on interfacial thermal transport. To gain further insights into the trend of TBC, we conduct molecular dynamics simulations using high-fidelity deep learning-based interatomic potentials, which reproduce the experimentally observed enhancement in TBC even for atomically perfect interfaces. These results suggest that the enhanced TBC facilitated by the AlN intermediate layer could result from a combination of improved crystalline quality at the interface and the "phonon bridge" effect provided by AlN that enhances the overlap between the vibrational spectra of GaN and SiC.

Thermal Conductivity of Covalent-Organic Frameworks.

Covalent-organic frameworks (COFs) are a highly promising class of materials that can provide an excellent platform for thermal management applications. In this Perspective, we first review previous works on the thermal conductivities of COFs. Then we share our insights on achieving high, low, and switchable thermal conductivities of future COFs. To obtain the desired thermal conductivity, a comprehensive understanding of their thermal transport mechanisms is necessary but lacking. We discuss current limitations in atomistic simulations, synthesis, and thermal conductivity measurements of COFs and share potential pathways to overcoming these challenges. We hope to stimulate collective, interdisciplinary efforts to study the thermal conductivity of COFs and enable their wide range of thermal applications.

Ultrafast and Nanoscale Energy Transduction Mechanisms and Coupled Thermal Transport across Interfaces.

The coupled interactions among the fundamental carriers of charge, heat, and electromagnetic fields at interfaces and boundaries give rise to energetic processes that enable a wide array of technologies. The energy transduction among these coupled carriers results in thermal dissipation at these surfaces, often quantified by the thermal boundary resistance, thus driving the functionalities of the modern nanotechnologies that are continuing to provide transformational benefits in computing, communication, health care, clean energy, power recycling, sensing, and manufacturing, to name a few. It is the purpose of this Review to summarize recent works that have been reported on ultrafast and nanoscale energy transduction and heat transfer mechanisms across interfaces when different thermal carriers couple near or across interfaces. We review coupled heat transfer mechanisms at interfaces of solids, liquids, gasses, and plasmas that drive the resulting interfacial heat transfer and temperature gradients due to energy and momentum coupling among various combinations of electrons, vibrons, photons, polaritons (plasmon polaritons and phonon polaritons), and molecules. These interfacial thermal transport processes with coupled energy carriers involve relatively recent research, and thus, several opportunities exist to further develop these nascent fields, which we comment on throughout the course of this Review.

Blended Conjugated Host and Unconjugated Dopant Polymers Towards N-type All-Polymer Conductors and High-ZT Thermoelectrics.

N-Type thermoelectrics typically consist of small molecule dopant+polymer host. Only a few polymer dopant+polymer host systems have been reported, and these have lower thermoelectric parameters. N-type polymers with high crystallinity and order are generally used for high-conductivity ( σ ${\sigma }$ ) organic conductors. Few n-type polymers with only short-range lamellar stacking for high-conductivity materials have been reported. Here, we describe an n-type short-range lamellar-stacked all-polymer thermoelectric system with highest σ ${\sigma }$ of 78 S-1 , power factor (PF) of 163 µW m-1 K-2 , and maximum Figure of merit (ZT) of 0.53 at room temperature with a dopant/host ratio of 75 wt%. The minor effect of polymer dopant on the molecular arrangement of conjugated polymer PDPIN at high ratios, high doping capability, high Seebeck coefficient (S) absolute values relative to σ ${\sigma }$ , and atypical decreased thermal conductivity ( κ ${\kappa }$ ) with increased doping ratio contribute to the promising performance.

A few-layer covalent network of fullerenes.

The two natural allotropes of carbon, diamond and graphite, are extended networks of sp3-hybridized and sp2-hybridized atoms, respectively1. By mixing different hybridizations and geometries of carbon, one could conceptually construct countless synthetic allotropes. Here we introduce graphullerene, a two-dimensional crystalline polymer of C60 that bridges the gulf between molecular and extended carbon materials. Its constituent fullerene subunits arrange hexagonally in a covalently interconnected molecular sheet. We report charge-neutral, purely carbon-based macroscopic crystals that are large enough to be mechanically exfoliated to produce molecularly thin flakes with clean interfaces-a critical requirement for the creation of heterostructures and optoelectronic devices2. The synthesis entails growing single crystals of layered polymeric (Mg4C60)∞ by chemical vapour transport and subsequently removing the magnesium with dilute acid. We explore the thermal conductivity of this material and find it to be much higher than that of molecular C60, which is a consequence of the in-plane covalent bonding. Furthermore, imaging few-layer graphullerene flakes using transmission electron microscopy and near-field nano-photoluminescence spectroscopy reveals the existence of moiré-like superlattices3. More broadly, the synthesis of extended carbon structures by polymerization of molecular precursors charts a clear path to the systematic design of materials for the construction of two-dimensional heterostructures with tunable optoelectronic properties.

Direct Visualization of Localized Vibrations at Complex Grain Boundaries.

Grain boundaries (GBs) are a prolific microstructural feature that dominates the functionality of a wide class of materials. The functionality at a GB results from the unique atomic arrangements, different from those in the grain, that have driven extensive experimental and theoretical studies correlating atomic-scale GB structures to macroscopic electronic, infrared optical, and thermal properties. In this work, a SrTiO3 GB is examined using atomic-resolution aberration-corrected scanning transmission electron microscopy and ultrahigh-energy-resolution monochromated electron energy-loss spectroscopy, in conjunction with density functional theory. This combination enables the correlation of the GB structure, nonstoichiometry, and chemical bonding with a redistribution of vibrational states within the GB dislocation cores. The new experimental access to localized GB vibrations provides a direct route to quantifying the impact of individual boundaries on macroscopic properties.

Direct Measurement of Ballistic and Diffusive Electron Transport in Gold.

We experimentally show that the ballistic length of hot electrons in laser-heated gold films can exceed ∼150 nm, which is ∼50% greater than the previously reported value of 100 nm inferred from pump-probe experiments. We also find that the mean free path of electrons at the peak temperature following interband excitation can reach upward of ∼45 nm, which is higher than the average value of 30 nm predicted from our parameter-free density functional perturbation theory. Our first-principles calculations of electron-phonon coupling reveal that the increase in the mean free path due to interband excitation is a consequence of drastically reduced electron-phonon coupling from lattice stiffening, thus providing the microscopic understanding of our experimental findings.

Control of Charge Carrier Relaxation at the Au/WSe2 Interface by Ti and TiO2 Adhesion Layers: Ab Initio Quantum Dynamics.

Phonon-mediated charge relaxation plays a vital role in controlling thermal transport across an interface for efficient functioning of two-dimensional (2D) nanostructured devices. Using a combination of nonadiabatic molecular dynamics with real-time time-dependent density functional theory, we demonstrate a strong influence of adhesion layers at the Au/WSe2 interface on nonequilibrium charge relaxation, rationalizing recent ultrafast time-resolved experiments. Ti oxide layers (TiOx) create a barrier to the interaction between Au and WSe2 and extend hot carrier lifetimes, creating benefits for photovoltaic and photocatalytic applications. In contrast, a metallic Ti layer accelerates the energy flow, as needed for efficient heat dissipation in electronic devices. The interaction of metallic Ti with WSe2 causes W-Se bond scissoring and pins the Fermi level. The Ti adhesion layer enhances the electron-phonon coupling due to an increased density of states and the light mass of the Ti atom. The conclusions are robust to presence of typical point defects. The atomic-scale ab initio analysis of carrier relaxation at the interfaces advances our knowledge in fabricating nanodevices with optimized electronic and thermal properties.

Exceptionally Enhanced Thermal Conductivity of Aluminum Driven by Extreme Pressures: A First-Principles Study.

Extreme pressure conditions reveal fundamental insights into the physical properties of elemental metals that are otherwise not evident under ambient conditions. Herein, we use the density functional perturbation theory to demonstrate that the change in thermal conductivity as a result of large hydrostatic pressures at room temperature for aluminum is the largest of any known material. More specifically, in comparison to ambient conditions, we find that the change in thermal conductivity for aluminum is greater than the relative changes in thermal conductivities of diamond and cubic boron nitride combined, which are two of the most thermally conductive bulk materials known to date. We attribute this to the relatively larger increase in mean free paths and lifetimes of electrons in aluminum as a result of weaker electron-phonon coupling at higher pressures. Our work reveals direct insights into the exceptional electronic transport properties of pressurized aluminum and advances a broad paradigm for understanding thermal transport in metals under extreme pressure.

Electron-phonon relaxation at the Au/WSe2 interface is significantly accelerated by a Ti adhesion layer: time-domain ab initio analysis.

Thermal transport at nanoscale metal-semiconductor interfaces via electron-phonon coupling is crucial for applications of modern microelectronic, electro-optic and thermoelectric devices. To enhance the device performance, the heat flow can be regulated by modifying the interfacial atomic interactions. We use ab initio time-dependent density functional theory combined with non-adiabatic molecular dynamics to study how the hot electron and hole relaxation rates change on incorporating a thin Ti adhesion layer at the Au/WSe2 interface. The excited charge carrier relaxation is much faster in Au/Ti/WSe2 due to the enhanced electron-phonon coupling, rationalized by the following reasons: (1) Ti atoms are lighter than Au, W and Se atoms and move faster. (2) Ti has a significant contribution to the electronic properties in the relevant energy range. (3) Ti interacts strongly with WSe2 and promotes its bond-scissoring which causes Fermi-level pinning, making WSe2 contribute to electronic properties around the Fermi level. The changes in the relaxation rates are more pronounced for excited electrons compared to holes because both relative and absolute Ti contributions to the electronic properties are larger above than below the Fermi level. The results provide guidance for improving the design of novel and robust materials by optimizing the heat dissipation at metal-semiconductor interfaces.

Pore-Confined Polymers Enhance the Thermal Conductivity of Polymer Nanocomposites.

Molecularly confined polymer fillers in nanopores were found to give superior mechanical properties of polymer nanocomposites. In this work, we study the thermal conductivity of such nanocomposites and unveil the effect of polymer confinement on thermal conductivity. Using the time-domain thermoreflectance method, we measure the cross-plane thermal conductivity of polymer nanocomposites that consist of polystyrene fillers confined within a nanoporous organosilicate matrix. Compared to unconfined bulk polystyrene fillers, we find that pore-confined polystyrene fillers enhance the thermal conductivity of the polymer nanocomposites. This enhancement is attributed to the better aligned and less entangled chains in the confined phase, where chain-chain phonon scatterings are reduced. Our work provides essential insights into the thermal conductivity of polymer nanocomposites for multifunctional thermal and mechanical applications.

Vacancy-Induced Temperature-Dependent Thermal and Magnetic Properties of Holmium-Substituted Bismuth Ferrite Nanoparticle Compacts.

Multiferroics have gained widespread acceptance for room-temperature applications such as in spintronics, ferroelectric random access memory, and transistors because of their intrinsic magnetic and ferroelectric coupling. However, a comprehensive study, establishing a correlation between the magnetic and thermal transport properties of multiferroics, is still missing from the literature. To fill the void, this work reports the temperature-dependent thermal and magnetic properties of holmium-substituted bismuth ferrite (BiFeO3) and their dependencies on oxygen vacancies and structural modifications. Two distinct magnetic transitions on temperature-dependent magnetic and heat capacity responses are identified. Experimental analysis suggests that the excess of oxygen vacancies shifts the magnetic transition temperature by ∼64 K. The holmium substitution-induced structural modification increases BiFeO3 heat capacity by 30% up to the antiferromagnetic phase transition temperature. Furthermore, an unsaturated heat capacity even at temperatures as high as 850 K is observed and is ascribed to anharmonicity and partial densification of the nanoparticles used during heat capacity measurements. The room-temperature thermal conductivity of BiFeO3 is ∼0.33 ± 0.11 W m-1 K-1 and remains unchanged at high temperatures due to defect scattering from porosities.

Plasma-induced surface cooling.

Plasmas are an indispensable materials engineering tool due to their unique ability to deliver a flux of species and energy to a surface. This energy flux serves to heat the surface out of thermal equilibrium with bulk material, thus enabling local physicochemical processes that can be harnessed for material manipulation. However, to-date, there have been no reports on the direct measurement of the localized, transient thermal response of a material surface exposed to a plasma. Here, we use time-resolved optical thermometry in-situ to show that the energy flux from a pulsed plasma serves to both heat and transiently cool the material surface. To identify potential mechanisms for this 'plasma cooling,' we employ time-resolved plasma diagnostics to correlate the photon and charged particle flux with the thermal response of the material. The results indicate photon-stimulated desorption of adsorbates from the surface is the most likely mechanism responsible for this plasma cooling.

A New Polystyrene-Poly(vinylpyridinium) Ionic Copolymer Dopant for n-Type All-Polymer Thermoelectrics with High and Stable Conductivity Relative to the Seebeck Coefficient giving High Power Factor.

A novel n-type copolymer dopant polystyrene-poly(4-vinyl-N-hexylpyridinium fluoride) (PSpF) with fluoride anions is designed and synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. This is thought to be the first polymeric fluoride dopant. Electrical conductivity of 4.2 S cm-1 and high power factor of 67 µW m-1 K-2 are achieved for PSpF-doped polymer films, with a corresponding decrease in thermal conductivity as the PSpF concentration is increased, giving the highest ZT of 0.1. An especially high electrical conductivity of 58 S cm-1 at 88 °C and outstanding thermal stability are recorded. Further, organic transistors of PSpF-doped thin films exhibit high electron mobility and Hall mobility of 0.86 and 1.70 cm2 V-1 s-1 , respectively. The results suggest that polystyrene-poly(vinylpyridinium) salt copolymers with fluoride anions are promising for high-performance n-type all-polymer thermoelectrics. This work provides a new way to realize organic thermoelectrics with high conductivity relative to the Seebeck coefficient, high power factor, thermal stability, and broad processing window.

Supramolecular Interactions Lead to Remarkably High Thermal Conductivities in Interpenetrated Two-Dimensional Porous Crystals.

The design of innovative porous crystals with high porosities and large surface areas has garnered a great deal of attention over the past few decades due to their remarkable potential for a variety of applications. However, heat dissipation is key to realizing their potential. We use systematic atomistic simulations to reveal that interpenetrated porous crystals formed from two-dimensional (2D) frameworks possess remarkable thermal conductivities at high porosities in comparison to their three-dimensional (3D) single framework and interpenetrated 3D framework counterparts. In contrast to conventional understanding, higher thermal conductivities are associated with lower atomic densities and higher porosities for porous crystals formed from interpenetrating 2D frameworks. We attribute this to lower phonon-phonon scattering and vibrational hardening from the supramolecular interactions that restrict atomic vibrational amplitudes, facilitating heat conduction. This marks a new regime of materials design combining ultralow mass densities and ultrahigh thermal conductivities in 2D interpenetrated porous crystals.

Observation of solid-state bidirectional thermal conductivity switching in antiferroelectric lead zirconate (PbZrO3).

Materials with tunable thermal properties enable on-demand control of temperature and heat flow, which is an integral component in the development of solid-state refrigeration, energy scavenging, and thermal circuits. Although gap-based and liquid-based thermal switches that work on the basis of mechanical movements have been an effective approach to control the flow of heat in the devices, their complex mechanisms impose considerable costs in latency, expense, and power consumption. As a consequence, materials that have multiple solid-state phases with distinct thermal properties are appealing for thermal management due to their simplicity, fast switching, and compactness. Thus, an ideal thermal switch should operate near or above room temperature, have a simple trigger mechanism, and offer a quick and large on/off switching ratio. In this study, we experimentally demonstrate that manipulating phonon scattering rates can switch the thermal conductivity of antiferroelectric PbZrO3 bidirectionally by -10% and +25% upon applying electrical and thermal excitation, respectively. Our approach takes advantage of two separate phase transformations in PbZrO3 that alter the phonon scattering rate in different manners. In this study, we demonstrate that PbZrO3 can serve as a fast (<1 second), repeatable, simple trigger, and reliable thermal switch with a net switching ratio of nearly 38% from ~1.20 to ~1.65 W m-1 K-1.