Thickness-Independent Vibrational Thermal Conductance across Confined Solid-Solution Thin Films.

We experimentally show that the thermal conductance across confined solid-solution crystalline thin films between parent materials does not necessarily lead to an increase in thermal resistances across the thin-film geometries with increasing film thicknesses, which is counterintuitive to the notion that adding a material serves to increase the total thermal resistance. Confined thin epitaxial Ca0.5Sr0.5TiO3 solid-solution films with systematically varying thicknesses in between two parent perovskite materials of calcium titanate and (001)-oriented strontium titanate are grown, and thermoreflectance techniques are used to accurately measure the thermal boundary conductance across the confined solid-solution films, showing that the thermal resistance does not substantially increase with the addition of solid-solution films with increasing thicknesses from ∼1 to ∼10 nm. Contrary to the macroscopic understanding of thermal transport where adding more material along the heat propagation direction leads to larger thermal resistances, our results potentially offer experimental support to the computationally predicted concept of vibrational matching across interfaces. This concept is based on the fact that a better match in the available heat-carrying vibrations due to an interfacial layer can lead to lower thermal boundary resistances, thus leading to an enhancement in thermal boundary conductance across interfaces driven by the addition of a thin "vibrational bridge" layer between two solids.

Quasi-Ballistic Thermal Transport Across MoS2 Thin Films.

Layered two-dimensional (2D) materials have highly anisotropic thermal properties between the in-plane and cross-plane directions. Conventionally, it is thought that cross-plane thermal conductivities (κ z) are low, and therefore c-axis phonon mean free paths (MFPs) are small. Here, we measure κ z across MoS2 films of varying thickness (20-240 nm) and uncover evidence of very long c-axis phonon MFPs at room temperature in these layered semiconductors. Experimental data obtained using time-domain thermoreflectance (TDTR) are in good agreement with first-principles density functional theory (DFT). These calculations suggest that ∼50% of the heat is carried by phonons with MFP > 200 nm, exceeding kinetic theory estimates by nearly 2 orders of magnitude. Because of quasi-ballistic effects, the κ z of nanometer-thin films of MoS2 scales with their thickness and the volumetric thermal resistance asymptotes to a nonzero value, ∼10 m2 K GW-1. This contributes as much as 30% to the total thermal resistance of a 20 nm thick film, the rest being limited by thermal interface resistance with the SiO2 substrate and top-side aluminum transducer. These findings are essential for understanding heat flow across nanometer-thin films of MoS2 for optoelectronic and thermoelectric applications.

Direct Visualization of Thermal Conductivity Suppression Due to Enhanced Phonon Scattering Near Individual Grain Boundaries.

Understanding the impact of lattice imperfections on nanoscale thermal transport is crucial for diverse applications ranging from thermal management to energy conversion. Grain boundaries (GBs) are ubiquitous defects in polycrystalline materials, which scatter phonons and reduce thermal conductivity (κ). Historically, their impact on heat conduction has been studied indirectly through spatially averaged measurements, that provide little information about phonon transport near a single GB. Here, using spatially resolved time-domain thermoreflectance (TDTR) measurements in combination with electron backscatter diffraction (EBSD), we make localized measurements of κ within few µm of individual GBs in boron-doped polycrystalline diamond. We observe strongly suppressed thermal transport near GBs, a reduction in κ from ∼1000 W m-1 K-1 at the center of large grains to ∼400 W m-1 K-1 in the immediate vicinity of GBs. Furthermore, we show that this reduction in κ is measured up to ∼10 µm away from a GB. A theoretical model is proposed that captures the local reduction in phonon mean-free-paths due to strongly diffuse phonon scattering at the disordered grain boundaries. Our results provide a new framework for understanding phonon-defect interactions in nanomaterials, with implications for the use of high-κ polycrystalline materials as heat sinks in electronics thermal management.

Extreme tunability in aluminum doped zinc oxide plasmonic materials for near-infrared applications.

Plasmonic materials (PMs), featuring large static or dynamic tunability, have significant impact on the optical properties due to their potential for applications in transformation optics, telecommunications, energy, and biomedical areas. Among PMs, the carrier concentration and mobility are two tunable parameters, which control the plasma frequency of a metal. Here, we report on large static and dynamic tunability in wavelengths up to 640 nm in Al-doped ZnO based transparent conducting degenerate semiconductors by controlling both thickness and applied voltages. This extreme tunability is ascribed to an increase in carrier concentration with increasing thickness as well as voltage-induced thermal effects that eventually diminish the carrier concentration and mobility due to complex chemical transformations in the multilayer growth process. These observations could pave the way for optical manipulation of this class of materials for potential transformative applications.

Protein Thermal Conductivity Measured in the Solid State Reveals Anharmonic Interactions of Vibrations in a Fractal Structure.

Energy processes and vibrations in biological macromolecules such as proteins ultimately dictate biological, chemical, and physical functions in living materials. These energetic vibrations in the ribbon-like motifs of proteins interact on self-similar structures and fractal-like objects over a range of length scales of the protein (a few angstroms to the size of the protein itself, a few nanometers). In fact, the fractal geometries of protein molecules create a complex network of vibrations; therefore, proteins represent an ideal material system to study the underlying mechanisms driving vibrational thermal transport in a dense, fractal network. However, experimental studies of thermal energy transport in proteins have been limited to dispersive protein suspensions, which limits the knowledge that can be extracted about how vibrational energy is transferred in a pure protein solid. We overcome this by synthesizing solid, water-insoluble protein films for thermal conductivity measurements via time-domain thermoreflectance. We measure the thermal conductivity of bovine serum albumin and myoglobin solid films over a range of temperatures from 77 to 296 K. These temperature trends indicate that anharmonic coupling of vibrations in the protein is contributing to thermal conductivity. This first-ever observation of anharmonic-like trends in the thermal conductivity of a fully dense protein forms the basis of validation of seminal theories of vibrational energy-transfer processes in fractal objects.

Crossover from incoherent to coherent phonon scattering in epitaxial oxide superlattices.

Elementary particles such as electrons or photons are frequent subjects of wave-nature-driven investigations, unlike collective excitations such as phonons. The demonstration of wave-particle crossover, in terms of macroscopic properties, is crucial to the understanding and application of the wave behaviour of matter. We present an unambiguous demonstration of the theoretically predicted crossover from diffuse (particle-like) to specular (wave-like) phonon scattering in epitaxial oxide superlattices, manifested by a minimum in lattice thermal conductivity as a function of interface density. We do so by synthesizing superlattices of electrically insulating perovskite oxides and systematically varying the interface density, with unit-cell precision, using two different epitaxial-growth techniques. These observations open up opportunities for studies on the wave nature of phonons, particularly phonon interference effects, using oxide superlattices as model systems, with extensive applications in thermoelectrics and thermal management.

Experimental investigation of size effects on the thermal conductivity of silicon-germanium alloy thin films.

We experimentally investigate the role of size effects and boundary scattering on the thermal conductivity of silicon-germanium alloys. The thermal conductivities of a series of epitaxially grown Si(1-x)Ge(x) thin films with varying thicknesses and compositions were measured with time-domain thermoreflectance. The resulting conductivities are found to be 3 to 5 times less than bulk values and vary strongly with film thickness. By examining these measured thermal conductivities in the context of a previously established model, it is shown that long wavelength phonons, known to be the dominant heat carriers in alloy films, are strongly scattered by the film boundaries, thereby inducing the observed reductions in heat transport. These results are then generalized to silicon-germanium systems of various thicknesses and compositions; we find that the thermal conductivities of Si(1-x)Ge(x) superlattices are ultimately limited by finite size effects and sample size rather than periodicity or alloying. This demonstrates the strong influence of sample size in alloyed nanosystems. Therefore, if a comparison is to be made between the thermal conductivities of superlattices and alloys, the total sample thicknesses of each must be considered.

A frequency-domain thermoreflectance method for the characterization of thermal properties.

A frequency-domain thermoreflectance method for measuring the thermal properties of homogenous materials and submicron thin films is described. The method can simultaneously determine the thermal conductivity and heat capacity of a sample, provided the thermal diffusivity is greater, similar3x10(-6) m(2)/s, and can also simultaneously measure in-plane and cross-plane thermal conductivities, as well the thermal boundary conductance between material layers. Two implementations are discussed, one based on an ultrafast pulsed laser system and one based on continuous-wave lasers. The theory of the method and an analysis of its sensitivity to various thermal properties are given, along with results from measurements of several standard materials over a wide range of thermal diffusivities. We obtain specific heats and thermal conductivities in good agreement with literature values, and also obtain the in-plane and cross-plane thermal conductivities for crystalline quartz.