arXiv subjects

Patrick E. Hopkins

Publications and source records attributed to Patrick E. Hopkins.

At least 19 recordsLinked to original sources

arXiv2026

A Transport Framework for Evaluating Nanoscale Interconnect Materials

As CMOS technology continues to scale, metallic interconnects increasingly limit circuit performance through rising resistivity, self-heating, and reliability degradation. Although several alternative metals have been proposed, a quantitative framework for evaluating their transport performance under nanoscale confinement remains unavailable. Here, we establish a transport framework by combining independently measured thermal and electrical conductivities with normalized and unnormalized transport figures of merit. We apply this framework to Cu, Ru, W, Co, Ir, and Mo thin films using new steady-state thermoreflectance measurements of Mo, Co, and Ir together with previously reported Cu, Ru, and W data. While Cu exhibits the highest intrinsic transport performance, its effective performance is substantially reduced by thickness scaling and Ta liner resistance. In contrast, Ru and Mo maintain favorable transport properties while enabling barrierless integration, identifying them as promising candidates for next-generation CMOS interconnects

cond-mat.mtrl-sci↗

arXiv2026

Synthesis and Characterization of Compositionally Complex (Gd/Ho/Er/Dy)2Zr2O7 Thin Film Combinatorial Library

High-throughput synthesis and characterization of novel ceramic materials with improved thermomechanical properties and phase stability are needed to accelerate the discovery of next-generation thermal barrier materials. A combinatorial thin film material library of (GdDyHoEr)2Zr2O7 were created via combinatorial magnetron reactive sputtering with rare-earth/zirconium alloy targets. Structural, chemical, and thermal property characterization mapping across the four component composition space was performed and correlated with thermal transport measurements. Steady state thermoreflectance mapping identifies a pronounced minimum in thermal conductivity within the Dy/Gd-rich quadrant. This minimum does not coincide with either the equiatomic composition or the region predicted to exhibit maximum cation size disorder. Instead, it corresponds to the largest experimentally observed lattice parameter, despite deviating from Vegard-like chemical averaging, and is independent of grain size and whole-pattern microstrain. These observations suggest that the way the fluorite lattice accommodates compositional complexity, rather than cation size disorder alone, provides a more informative descriptor of thermal transport. Overall, this work establishes a high-throughput workflow for combinatorial thin-film synthesis and multimodal characterization, enabling the rapid identification of previously inaccessible structure-property relationships in compositionally complex ceramics.

cond-mat.mtrl-sci↗

arXiv2026

Lock-In Infrared Thermography: Phase Analysis for Rapid, Wide-Range Thermal Conductivity Measurements

We report on a phase-based lock-in thermography approach, combined with a multilayered thermal model (often employed in thermoreflectance analysis), to measure the thermal conductivity of bulk materials and layered structures. The spatial distribution of the material's thermal phase is monitored with an infrared camera, which is locked into the frequency of a modulated laser used to heat the material. This phase distribution is then fit with a thermal model, in which properties such as thermal conductivity are extracted as fit parameters. This approach enables non-contact, front-side measurements, which are insensitive to surface roughness. The technique does not strictly require the application of a transducer layer, but we highlight the practical benefits of applying a removable adhesive layer to serve as a near-surface absorber. We demonstrate the efficacy of the method by measuring materials with thermal conductivities that span over three orders of magnitude (approximately 1 W/m/K to > 2000 W/m/K).

cond-mat.mtrl-sci↗

arXiv2026

Crystal growth and characterization of the ultra-high temperature substrate $\mathrm{Ta_{1-x}Hf_{x}C_{0.5}}$

Incorporation of $\mathrm{Al_{y}Ga_{1-y}N}$ (AGN) semiconductors into high power electronics offers efficiency improvements in power transmission, generation, and use, if approaches to eliminate the defects arising from film-lattice mismatch can be established. Here, we report the optical floating zone crystal growth of $\mathrm{Ta_{1-x}Hf_{x}C_{0.5}}$ (x = 0.2), a new metallic substrate material family lattice matched to the ultra-wide-band-gap, Al-rich side (y = 0.91) of the AGN solid solution. Laue diffraction demonstrates large single crystal domains in the as-grown boule. Single crystal x-ray diffraction at T = 213 K in conjunction with first principles calculations shows that the material adopts a layered crystal structure with AA-type stacking of (Ta/Hf)-C-(Ta/Hf) trilayers described in the trigonal space group P-3m1 (#164), with a = 3.1168(4) Å, c = 4.9644(4) Å, and $β$ = 120.0°. X-ray photoelectron spectroscopy (XPS) measurements show the Hf:Ta ratio to be close to the nominal value of 0.8:0.2 in the grown crystal. Density Functional Theory calculations reveal that this structure is stabilized by the low energy of carbon-vacancy formation of a hypothetical $\mathrm{(Ta/Hf)_{1}C_{1}}$ anti-NiAs structure type, and imply flexibility in interface structure with an overlayer nitride film. A surface preparation/polishing procedure is developed that reduces root mean square (RMS) surface roughness from as-cut 130 nm to 7 nm as measured by atomic force microscopy. Scanning electron microscopy shows the presence of a native surface oxide, removed by polishing, along with carbon-rich pits. Time-domain thermoreflectance measurements show a room temperature thermal conductivity of $κ$ = 18.1(4) W m-1 K-1. These results provide key first steps for utilizing metallic, lattice matched, substrates for the growth of Al-rich AGN semiconductors.

cond-mat.mtrl-sci↗

arXiv2026

Infrared Phonon Thermoreflectance in Polar Dielectrics

In this work, we investigate dielectric materials for thermoreflectance-based thermal sensing by extracting key optical parameters using temperature-dependent spectroscopic ellipsometry in the mid-infrared regime. Leveraging optical phonon resonances, we demonstrate that the thermoreflectance coefficients in polar dielectrics rival, and in some cases exceed by an order of magnitude, those observed in commonly used metals that are typically used as temperature transducers in thermoreflectance measurements. We introduce a transducer figure of merit (FOM) that combines pump absorption and probe reflectance modulation at different wavelengths, serving as a design-oriented screening metric for comparing thermoreflectance transducer performance across materials and spectral regions. Our results show that polar materials can exhibit performance up to eight times greater than that of metal transducers. To demonstrate practical capability, we perform transient thermoreflectance measurements on a 100 nm thermally grown SiO2 film on silicon. These results position dielectric materials as compelling candidates for next-generation thermal metrology, broadening the design space for optical thermometry, with strong implications for high-resolution thermal mapping and characterization of layered device structures based on phonon probing.

physics.optics↗

arXiv2026

Closing the ultrahigh temperature metrology gap: non-contact thermal conductivity ($\mathrm{k}$) and spectral emittance ($\mathrm{\varepsilon_λ}$) of molybdenum up to 3200 K

Advances in next-generation hypersonic hot structures, high heat-flux fusion or fission components, and laser based additive manufacturing depend on reliable solid state thermal conductivity data at high and ultrahigh temperatures, where conventional measurements become increasingly sensitive to contact resistances, uncertain boundary conditions, and nonlinear radiative losses. Building on our initial demonstration of ultrahigh temperature steady-state temperature differential radiometry (SSTDR), we present a substantially more robust platform aimed at making high temperature thermal and radiative property measurements more routine. The method integrates lock-in infrared thermography with a spatially localized, modulated perturbation laser to form a conduction dominant differential observable along with hyperspectral pyrometry and a validated 2D axisymmetric steady state heat transfer model. Using high purity molybdenum as a benchmark, we report solid state thermal conductivity k(T) from 1500 - 3000 K (to the onset of melting) with uncertainties of 7.9-11 % enabled by comprehensive uncertainty propagation, sensitivity analysis, and bounding studies. We additionally provide normal spectral emittance of molybdenum in both solid and liquid states over 500-1000 nm. These advances establish SSTDR as an accurate, non-contact route for closing the high temperature k(T) data gap while simultaneously producing much needed phase dependent radiative property data for melt adjacent and extreme heat-flux applications. Note: This is a shortened abstract; full version in manuscript.

cond-mat.mtrl-sci↗

arXiv2026

Phonon selection and interference in momentum-resolved electron energy loss spectroscopy

As momentum-resolved Electron Energy Loss Spectroscopy (q-EELS) becomes more widely used for phonon measurements, better understanding of the intricacies of the acquired signal is necessary. Selection rules limit the allowed scattering, which may prohibit the appearance of specific phonon branches in some measurements. Simultaneous sampling of the lattice across all basis atoms also warrants a coherent treatment of phonons, which yields a reciprocal-space repeating unit cell that is larger than the standard Brillouin zone. We thus introduce the concept of the ``interferometric Brillouin zone'' where phonons are observed, which is closely related to the Dynamic Structure Factor. These effects follow from our new mathematical formalism for waves and vibrations, and we demonstrate calculations of q-EELS experiments using molecular dynamics and lattice dynamics. Results are compared to established q-EELS simulation methods in well-studied material systems, including the utilization of scattering selection rules to acquire a polarization-selective vibrational density of states. Finally, we note the analysis involved is directly applicable to any wave phenomena, such as plasmons or polaritons.

cond-mat.mtrl-sci↗

arXiv2026

Tailoring phonon-driven responses in α-MoO3 through isotopic enrichment

The implementation of polaritonic materials into nanoscale devices requires selective tuning of parameters to realize desired spectral or thermal responses. One robust material is α-MoO3, which as an orthorhombic crystal boasts three distinct phonon dispersions, providing three polaritonic dispersions of hyperbolic phonon polaritons (HPhPs) across the mid-infrared (MIR). Here, the tunability of both optical and thermal responses in isotopically enriched α-MoO3 (98MoO3, Mo18O3 and 98Mo18O3) are explored. A uniform ~5 % spectral redshift from 18O enrichment is observed in both Raman- and IR-active TO phonons. Both the in- and out-of-plane thermal conductivities for the isotopic variations are reported. Ab initio calculations both replicate experimental findings and analyze the select-mode three-phonon scattering contributions. The HPhPs from each isotopic variation are probed with s-SNOM and their Q- factors are reported. A Q-factor maxima increase of ~50 % along the [100] in the RB2 and ~100 % along the [001] in the RB3 are reported for HPhPs supported in 98Mo18O3. Observations in both real and Fourier space of higher-order HPhP modes propagating in single slabs of isotopically enriched α-MoO3 without the use of a subdiffractional surface scatterer are presented here. This work illustrates the tunability of α-MoO3 for thermal and nanophotonic applications.

cond-mat.mtrl-sci↗

arXiv2025

Epitaxial growth and semiconductor properties of NiGa2O4 spinel for Ga2O3/NiO interfaces

Unintentionally formed interfacial layers are ubiquitous in semiconductor devices that operate at extreme conditions. However, these layers' structure and properties often remain unknown due to the thinness of these naturally formed interphases. Here, we report on the intentional epitaxial growth and semiconductor properties of NiGa2O4 spinel layers that form at Ga2O3/NiO interfaces used in high-power and high-temperature electronic devices. Cubic spinel NiGa2O4 films of 10-50 nm thicknesses and low surface roughness (~ 2 nm) were grown using pulsed laser deposition at a substrate temperatures in the 300-900 °C range on α-Al2O3 and β-Ga2O3 substrates of different orientation. The optical absorption onset (3.6-3.9 eV) and thermal conductivity (4-9 W m-1 K-1) vary systematically with substrate temperature, consistent with theoretical predictions of varying Ni and Ga cation ordering on the spinel lattice. The valence band offset between NiGa2O4 and β-Ga2O3 is determined to be 1.8 eV. The NiGa2O4-based p-n heterojunction devices on Ga2O3 (001) substrates exhibit a rectification ratio of 10^8 (for +/-2V) and a turn-on voltage of 1.4 V, maintaining diode behavior up to 600 °C. These results highlight the potential of NiGa2O4 as a p-type interlayer in Ga2O3-based devices and shows a new approach to investigate such interfacial layers.

cond-mat.mtrl-sci↗

arXiv2025

Rapid synthesis of dual-element isotope-enriched alpha-MoO3 crystals by reactive vapor transport

In this work, we develop a rapid reactive vapor transport technique to efficiently utilize limited isotopically pure precursors, particularly gaseous 18O2, and synthesize mm-scale, high-quality crystals within few-minute growth durations. We unlock this capability by using metallic molybdenum precursors with high source temperatures (900 C) and total pressures (1 atm) to maximize precursor efficiency and yield. Subsequently, we grow MoO3 single crystals with high and uniform enrichment levels of 98Mo and 18O isotopes in several different permutations. As probed by Raman spectroscopy, modest and significant phonon energy redshifts occur following 98Mo and 18O enrichment, respectively. By demonstrating control over both molybdenum and oxygen isotopic fractions, we establish a powerful tool to advance nanophotonics and thermal management goals using MoO3. This work is motivated by the possibility to enhance and engineer lattice vibrational mode phenomena including thermal conduction and hyperbolic phonon polariton (HPhP) dispersion, with particular interest in comparing the effects of light and heavy element enrichment.

cond-mat.mtrl-sci↗

arXiv2025

Topology-Driven Vibrations in a Chiral Polar Vortex Lattice

The ordering of magnetic or electric dipoles leading to real-space topological structures is at the forefront of materials research as their quantum mechanical nature often lends itself to emergent properties. Atomic lattice vibrations (phonons) are often a key contributor to the formation of long-range dipole textures based on ferroelectrics and impact the properties of the emergent phases. Here, using monochromated, momentum-resolved electron energy-loss spectroscopy (qEELS) with nanometer spatial resolution and meV-spectral-precision, we demonstrate that polar vortex lattices in PbTiO$_3$ spatially modulate the material's vibrational spectrum in patterns that directly reflect the overlying symmetry of the topological patterns. Moreover, by combining experiments with molecular dynamics simulations using machine learned potentials we reveal how these structures modify phonon modes across the vibrational spectrum. Beyond simple intensity modulation, we find that the chirality of the vortex topology imparts its unique symmetry onto phonons, producing a distinctive asymmetrical spectral shift across the vortex unit cell. Finally, the high spatial resolution of the technique enables topological defects to be probed directly, demonstrating a return to trivial PbTiO$_3$ modes at vortex dislocation cores. These findings establish a fundamental relationship between ferroelectric-ordering-induced topologies and phonon behavior, opening new avenues for engineering thermal transport, electron-phonon coupling, and other phonon-mediated properties in next-generation nanoscale devices.

cond-mat.mtrl-sci↗

arXiv2025

Unveiling Phonon Contributions to Thermal Transport and the Failure of the Wiedemann-Franz Law in Ruthenium and Tungsten Thin Films

Thermal transport in nanoscale interconnects is dominated by intricate electron-phonon interactions and microstructural influences. As copper faces limitations at the nanoscale, tungsten and ruthenium have emerged as promising alternatives due to their substantial phonon contributions to thermal conductivity. Metals with stronger phonon-mediated thermal transport are particularly advantageous in nanoscale architectures, where phonons are less sensitive to size effects than electrons. Here, we show that phonons play a comparable role to electrons in the thermal transport of ruthenium and tungsten thin films, evidenced by deviations from the classical Wiedemann-Franz law. Elevated Lorenz numbers-1.9 and 2.7 times the Sommerfeld value for ruthenium and tungsten, respectively-indicate phonon contributions of 45% and 62% to total thermal conductivity. Comparisons of in-plane thermal conductivity from steady-state thermoreflectance and electron relaxation times from infrared ellipsometry reveal that phonon-mediated transport is insensitive to microstructural variations and scaling. Ultrafast infrared pump-probe measurements show that ruthenium exhibits a higher electron-phonon coupling factor than tungsten, consistent with the differing contributions of carriers to thermal transport. Molecular dynamics simulations and spectral energy density analysis confirm substantial phonon-driven thermal transport and mode-dependent phonon lifetimes. These results offer insights into phonon-driven thermal transport and provide design principles for selecting interconnects with enhanced thermal management.

cond-mat.mtrl-sci↗

arXiv2025

Interfacial Heat Transport via Evanescent Radiation by Hot Electrons

We predict an additional thermal transport pathway across metal/non-metal interfaces with large electron-phonon non-equilibrium via evanescent radiative heat transfer. In such systems, electron scattering processes vary drastically and can be leveraged to guide heat across interfaces via radiative heat transport without engaging the lattice directly. We employ the formalism of fluctuational electrodynamics to simulate the spectral radiative heat flux across the interface of a metal film and a non-metal substrate. We find that the radiative conductance can exceed 300 MW m$^{-2}$ K$^{-1}$ at an electron temperature of 5000 K for an emitting tungsten film on a hexagonal boron nitride substrate, becoming comparable to its conductive counterpart. This allows for a more holistic approach to the heat flow across interfaces, accounting for electron-phonon non-equilibrium and ultrafast near-field phonon-polariton coupling.

cond-mat.mes-hall↗

arXiv2024

Ruddlesden-Popper chalcogenides push the limit of mechanical stiffness and glass-like thermal conductivity in single crystals

Insulating materials featuring ultralow thermal conductivity for diverse applications also require robust mechanical properties. Conventional thinking, however, which correlates strong bonding with high atomic-vibration-mediated heat conduction, led to diverse weakly bonded materials that feature ultralow thermal conductivity and low elastic moduli. One must, therefore, search for strongly-bonded single crystals in which heat transport is impeded by other means. Here, we report intrinsic, glass-like, ultralow thermal conductivity and ultrahigh elastic-modulus/thermal-conductivity ratio in single-crystalline Ruddlesden-Popper Ban+1ZrnS3n+1, n = 2,3, which are derivatives of BaZrS3. Their key features are strong anharmonicity and intra-unit-cell rock-salt blocks. The latter produce strongly bonded intrinsic superlattices, impeding heat conduction by broadband reduction of phonon velocities and mean free paths and concomitant strong phonon localization. The present study initiates a paradigm of mechanically stiff phonon glasses.

cond-mat.mtrl-sci↗

arXiv2024

Experimental observation of ballistic to diffusive transition in AlN thin films

Bulk AlN possesses high thermal conductivity due to long phonon mean-free-paths, high group velocity, and long lifetimes. However, the thermal transport scenario becomes very different in a thin AlN film due to phonon-defect and phonon-boundary scattering. Herein, we report experimental observation of ballistic to diffusive transition in a series of AlN thin films (1.6 - 2440 nm) grown on sapphire substrates. The ballistic transport is characterized by constant thermal resistance as a function of film thickness due to phonon scattering by defects and boundaries. In this transport regime, phonons possess very small group velocities and lifetimes. The lifetime of the optical phonons increases by more than an order of magnitude in the diffusive regime, however, remains nearly constant afterwards. Our study is important for understanding the details of nano and microscale thermal transport in a highly conductive material.

physics.app-ph↗

arXiv2024

Electronic vs. phononic thermal transport in Cr-doped V2O3 thin films across the Mott transition

Understanding the thermal conductivity of chromium doped V2O3 is crucial for optimizing the design of selectors for memory and neuromorphic devices. We utilized the time-domain thermoreflectance technique to measure the thermal conductivity of chromium doped V2O3 across varying concentrations, spanning the doping induced metal-insulator transition. In addition, different oxygen stoichiometries and film thicknesses were investigated in their crystalline and amorphous phases. Chromium doping concentration (0%-30%) and the degree of crystallinity emerged as the predominant factors influencing the thermal properties, while the effect of oxygen flow (600-1400 ppm) during deposition proved to be negligible. Our observations indicate that even in the metallic phase of V2O3, the lattice contribution is the dominant factor in thermal transport with no observable impact from the electrons on heat transport. Finally, the thermal conductivity of both amorphous and crystalline V2O3 was measured at cryogenic temperatures (80-450 K). Our thermal conductivity measurements as a function of temperature reveal that both phases exhibit behavior similar to amorphous materials, indicating pronounced phonon scattering effects in the crystalline phase of V2O3.

cond-mat.str-el↗

arXiv2024

Ultrafast evanescent heat transfer across solid interfaces via hyperbolic phonon polaritons in hexagonal boron nitride

The efficiency of phonon-mediated heat transport is limited by the intrinsic atomistic properties of materials, seemingly providing an upper limit to heat transfer in materials and across their interfaces. The typical speeds of conductive transport, which are inherently limited by the chemical bonds and atomic masses, dictate how quickly heat will move in solids. Given that phonon-polaritons, or coupled phonon-photon modes, can propagate at speeds approaching 1 percent of the speed of light - orders of magnitude faster than transport within a pure diffusive phonon conductor - we demonstrate that volume-confined, hyperbolic phonon-polariton(HPhP) modes supported by many biaxial polar crystals can couple energy across solid-solid interfaces at an order of magnitude higher rates than phonon-phonon conduction alone. Using pump-probe thermoreflectance with a mid-infrared, tunable, probe pulse with sub-picosecond resolution, we demonstrate remote and spectrally selective excitation of the HPhP modes in hexagonal boron nitride in response to radiative heating from a thermally emitting gold source. Our work demonstrates a new avenue for interfacial heat transfer based on broadband radiative coupling from a hot spot in a gold film to hBN HPhPs, independent of the broad spectral mismatch between the pump(visible) and probe(mid-IR) pulses employed. This methodology can be used to bypass the intrinsically limiting phonon-phonon conductive pathway, thus providing an alternative means of heat transfer across interfaces. Further, our time-resolved measurements of the temperature changes of the HPhP modes in hBN show that through polaritonic coupling, a material can transfer heat across and away from an interface at rates orders of magnitude faster than diffusive phonon speeds intrinsic to the material, thus demonstrating a pronounced thermal transport enhancement in hBN via phonon-polariton coupling.

cond-mat.mes-hall↗

arXiv2024

Disorder controlled sound speed and thermal conductivity of hybrid metalcone films

The multifaceted applications of polymers are often limited by their thermal conductivity. Therefore, understanding the mechanisms of thermal transport in polymers is of vital interest. Here, we leverage molecular layer deposition to grow three types of hybrid metalcone (i.e., alucone, zincone, and tincone) films and study their thermal and acoustic properties. The thermal conductivity of the hybrid polymer films ranges from 0.43 to 1.14 W/mK. Using kinetic theory, we trace the origin of thermal conductivity difference to sound speed change, which is dictated by the structural disorder within the films. Changing the disorder has negligible impacts on volumetric heat capacity and vibrational lifetimes. Our findings provide means to improve the thermal conductivity of organic, hybrid, and inorganic polymer films.

physics.app-ph↗