Time-domain Thermoreflectance Research Articles

Electronic interfacial thermal conductance between metal nano-films in sub-picosecond non-equilibrium transport process

Interfaces play a critical role in nanoscale thermal transport, and understanding thermal transport mechanisms across metal/metal interfaces at the non-equilibrium states is urgently needed for highly integrated electronic structures or devices. In this work, the electronic interfacial thermal conductance hee of two metal interfaces, Au/Pt and Au/Al, was measured by time domain thermoreflectance (TDTR) at the non-equilibrium states and an extended two-temperature model was applied to well describe the interactions of electrons between the metal films. For the Au/Pt structure, the measured hee is 4.4 ± 1.8 GWm−2K−1, which is consistent with the predicted value by the electronic diffuse mismatch model (DMM). While for the Au/Al structure, the measured hee (0.13±0.05 GWm−2K−1) is an order of magnitude smaller than that of Au/Pt and the predicted value of the electronic DMM. The results indicate that even the extremely thin oxide layer at the Au/Al interface can significantly hinder the electron thermal transport across the metal interface. Overall, our findings contribute to revealing the non-equilibrium interfacial thermal transport mechanisms and pave the way for designing the highly integrated electronic devices.

Anisotropic Fourier Heat Conduction and phonon Boltzmann transport equation based simulation of time domain thermo-reflectance experiments

The anisotropic Fourier Heat Conduction Equation (FHCE) and the multidimensional phonon Boltzmann Transport Equation (BTE) were solved numerically in cylindrical coordinates and in time domain to simulate a Time Domain Thermo-Reflectance (TDTR) experimental silicon/aluminum substrate/transducer setup. The out-of-phase response of the probe laser was predicted at various beam offset distances for a pump laser pulse frequency of 80 MHz and modulation frequency of 10 MHz and compared against experimental measurements for a silicon substrate. The isotropic FHCE was also solved for comparison. Results show that the isotropic FHCE with bulk thermal conductivity of 145 W/m/K significantly underpredicts the out-of-phase temperature difference, particularly at smaller beam offsets. With an isotropic thermal conductivity of 105 W/m/K, the computed results match experimental data at smaller beam offsets well, but overpredicts the experimental data at larger beam offsets. An almost-perfect match is obtained by using an anisotropic thermal conductivity wherein the radial (in-plane) thermal conductivity is set to 85 W/m/K and the axial (through-plane) conductivity is set to 130 W/m/K. The multidimensional frequency and polarization dependent phonon BTE is next solved. The BTE results for the out-of-phase temperature difference match experimental observations well at small and intermediate beam offsets, but overpredicts the experimental data at larger beam offsets. FHCE results are fitted to the BTE predictions, and the extracted (best fit) thermal conductivity is found to be 110 W/m/K.

Greatly Enhanced Radiative Transfer Enabled by Hyperbolic Phonon Polaritons in α‐MoO3

AbstractOrthorhombic molybdenum trioxide (α‐MoO3) is a highly anisotropic hyperbolic material in nature. Within its wide Reststrahlen bands, α‐MoO3 has hyperboloidal dispersion that supports bulk propagation of high‐k phonon polariton modes. These modes can serve as energy transport channels to greatly enhance radiative heat transfer inside the material. In this work, large radiative transfer enabled by phonon polaritons in α‐MoO3 is demonstrated. The study first determines the temperature‐dependent permittivity of α‐MoO3 from polarized Fourier‐Transform Infrared (FTIR) spectroscopy measurements and then uses a many‐body radiative heat transfer model to predict the equivalent radiative thermal conductivity of hyperbolic phonon polariton. Contribution of radiative transfer to the total thermal transport is experimentally determined from the Time‐Domain Thermoreflectance (TDTR) measurements in a temperature range from −100 to 300 °C. It is found that radiative transfer can account for ≈60% of the total thermal transport at a temperature of 300 °C. That is, conductive thermal transport is enhanced by >100% by radiative transfer, or radiation inside α‐MoO3 is greater than that of conduction. These additional energy pathways will have important implications in thermal management in new materials and devices.

Electron–phonon coupling and non-equilibrium thermal conduction in ultra-fast heating systems

A discrete unified gas kinetic scheme is developed to solve the Boltzmann transport equation (BTE) with coupled electron and phonon thermal transport, whose time step is not limited by the relaxation time. The key of the present scheme is that the electron/phonon advection, scattering and electron–phonon interactions are coupled together within one time step by solving the BTE again at the cell interface. Numerical results show that the present scheme can correctly predict the electron–phonon coupling effects, and is in agreement with typical two-temperature model and experimental results in existing literatures and our performed time-domain thermoreflectance technique. It can also capture the ballistic effects when the characteristic length is comparable to or smaller than the mean free path where the two-temperature model fails. In addition, two anomalous heat conduction phenomena are predicted by the present scheme, namely, heat flows from phonon to electron in transient thermal grating geometry and re-rise reflected signal appears in Au/Pt bilayer metal structure. The present work can provide theoretical guidance for the study of electron–phonon coupling and offer a useful tool for multi-scale thermal management.

Propagon boundary scattering relaxed via crystalline host on multiphase germanium telluride

The movement of heat through amorphous solids on an atomic level remains an outstanding question. Recent studies suggest that the primary thermal carrier in amorphous materials, propagons, essentially behaves like phonons. In this work, we provide experimental evidence that shows the interaction between propagons and phonons by utilizing the phase change chalcogenide germanium telluride. A series of ultra-long time-delay time-domain thermoreflectance measurements are used to analyze the scattering of vibrational thermal carriers at the boundaries of amorphous GeTe thin films relative to scattering across a crystalline-amorphous bilayer. We find that amorphous long wavelength propagons that would otherwise scatter can instead be hosted by a crystalline underlayer and its phonon population. This experimental evidence directly demonstrates propagon–phonon interactions in a clear experimental manner.

Impact of swift heavy ion-induced point defects on nanoscale thermal transport in ZnO

Near-surface nanoscale thermal conductivity (k) variation of ion-irradiated single-crystalline ZnO was studied by time-domain thermoreflectance. ZnO was irradiated by 710 MeV Bi swift heavy ions (SHI) in the 1010–1013 ion/cm2 fluence range to investigate the progression of radiation damage both from single ion impacts and ion path overlapping regimes. Structural characterization using X-ray diffraction, Raman spectroscopy, and transmission electron microscopy indicated the absence of amorphization. The degradation in kwas attributed primarily due to phonon scattering on point defects. The results of measured k were used to validate several models including the semi-analytical Klemens-Callaway model, and a novel hybrid modeling approach based on the Monte-Carlo code TREKIS coupled with molecular dynamics simulations which captures the effects of single ion and ion path overlapping regimes, respectively. The findings promote a novel approach to developing radiation-controlled thermally functional materials.

Investigation of interfacial thermal resistance between Bi2Te3 thin films and metal electrodes via TDTR

A challenge on promoting thermoelectric application is the low energy conversion efficiency of thermoelectric devices. Reducing the contact thermal resistance of a thermoelectric device can improve efficiency effectively. However, study on interfacial thermal transport is lack due to the difficulty on contact thermal resistance measurement. Herein, a study on contact thermal resistance between thermoelectric and electrode materials was reported. We prepared various heterostructures of Bi2Te3–Cu and Bi2Te3–Ni via magnetron sputtering, and measured the contact thermal resistance using a time-domain thermoreflectance technique. Our results show that the contact thermal resistance is affected by both chemical and physical properties of interface. The chemical and physical stability of interfaces, the surface roughness and porosity of films, as well as electrical properties of Bi2Te3, are all related to the contact thermal resistance. The contact thermal resistance of Bi2Te3–Ni prepared at 400 °C can be reduced to 3.96 × 10−7 m2KW−1. Our work provides important experimental data and theoretical basis for optimizing the interlayer between thermoelectric materials and electrodes, and improving energy conversion efficiency of thermoelectric devices.

Thermal conductivity of SiC and PyC coatings in spherical nuclear fuel particles measured by nanosecond time domain thermoreflectance

TRi-structural ISOtropic (TRISO) nuclear particle fuels are intended for application in several designs of advanced high temperature nuclear reactors. Nanosecond time domain transient thermoreflectance has been applied to the silicon carbide (SiC) and the inner and outer pyrolytic carbon (PyC) coatings of surrogate TRISO particles, measuring mean thermal conductivities of 166 ± 18 W∙m−1K−1, 11.1 ± 1.9 W∙m−1K−1, and 8.6 ± 2.1 W∙m−1K−1, respectively, for each layer. The applicability of the analytical heat diffusion model used to fit the measured traces was examined and it was found that the boundary effect at the SiC/PyC interface becomes perceptible at a lateral distance approximately equal to the thermal penetration depth of SiC (7.1 µm). In addition, steady-state thermal modelling showed that the radial thermal resistance of the particle is dominated by the porous buffer layer. The thermal resistance will likely increase significantly upon circumferential detachment of the porous buffer carbon coating with irradiation. Implications for fuel design and reactor performance are discussed.

Quasi-ballistic thermal transport in silicon carbide nanowires

Silicon carbide (SiC) is an important industrial material that enables the thermal stability of power electronics. However, the nanoscale phenomenon of ballistic thermal conduction, which may further improve the thermal performance, remains unexplored in SiC. Here, we reveal the length and temperature scales at which SiC exhibits quasi-ballistic thermal conduction. Our time-domain thermoreflectance measurements probe the thermal conductivity of SiC nanowires as a function of their length and temperature. The deviation of the thermal conductivity from the diffusive limit in nanowires shorter than a few micrometers indicates the transition into a quasi-ballistic thermal conduction regime. Naturally, the deviation is greater at lower temperatures, yet the effect persists even above room temperature. Our Monte Carlo simulations of phonon transport support our experimental results and show how phonons with long mean free paths carry a substantial amount of heat, causing quasi-ballistic conduction. These findings show that quasi-ballistic heat conduction can persist at the microscale at operating temperatures of power devices, and thus may help improve the thermal design in electronics based on SiC.

Time-domain thermoreflectance measurement of the thermal diffusivity of Nb thin films

Nb-coated Cu superconducting radiofrequency (SRF) cavities are of interest as a possible alternative to bulk Nb cavities for particle accelerators due to the high thermal conductivity of Cu and its lower cost than Nb. Studying the thermal diffusion properties in Nb thin films on Cu is important for developing Nb-coated Cu SRF cavities. In the present study, the thermal diffusivity of 100‒800 nm Nb films on Cu is measured by time-domain thermoreflectance (TDTR). The thermal diffusivity is obtained from a curve fit of the TDTR signal to a one-dimensional Fourier heat diffusion model over a time extending from 25 to 985 ps after laser-surface interaction. The film was examined by atomic force microscopy and scanning electron microscopy. The grain size and thermal diffusivity increase with film thickness. The thermal diffusivity reaches a value similar to that reported for bulk Nb for the 400 and 800 nm films, for which the average grain size is 47 ± 13 nm and 68 ± 18 nm, respectively. TDTR measurement for the 400-nm film taken over the temperature range of 293 to 40 K showed that the thermal diffusivity increases as the temperature is reduced. The results indicate that grain boundaries reduce the thermal diffusivity of the Nb film and, therefore, must be considered in Nb-coated Cu SRF cavities.

Accurate Thermal Conductivity Measurements of Porous Thin Films by Time-Domain Thermoreflectance.

Accurate measurements of the thermal conductivity (κ) of porous thin films are still limited due to challenges to deposit flat and continuous metal transducers on porous samples, a necessity for many thermal measurement techniques for nanostructures. In this paper, we introduce an approach based on time-domain thermoreflectance (TDTR) to accurately and conveniently measure κ of porous thin films by transferring a flat and smooth metal film unto porous samples as the transducer for TDTR measurements. We demonstrate our approach by measuring κ of a series of microscale holey SiO2 films with diameters of 1-3.5 μm and porosity of 13-50%. To achieve a measurement uncertainty of <12%, we ensure that the metal transducer films are sufficiently stiff and establish good thermal contact with the holey SiO2 samples. Our κ measurements agree well with calculations of κ from effective medium theory. Our approach could provide a convenient way to further investigate the thermal transport properties of porous films.

Effect of the alloyed interlayer on the thermal conductance of Al/GaN interface

Understanding the interfacial phonon transport is essential for optimizing the thermal management of microelectronics, especially for high energy density devices. Some calculations have suggested that introducing interfacial defects or disorders will increase the interfacial thermal conductance, which helps heat dissipation, while some studies suggested otherwise. In this work, we introduced substitutional impurities in GaN by growing a ∼2-nm-thick AlxGa1−xN or InxGa1−xN alloyed interlayer at the Al/GaN interface and measured the interface thermal conductance by time-domain thermoreflectance at room temperature. Our results show that substituting Ga atoms near the interface with either lighter Al atoms or heavier In atoms at a nominal concentration of 20% or less will not necessarily change the thermal conductance of the Al/alloy interface but is detrimental to the thermal transport across the total Al/GaN interface, which provides an experimental guideline for the thermal design of GaN-based devices.

Correlating Young's Modulus with High Thermal Conductivity in Organic Conjugated Small Molecules.

Attaining elevated thermal conductivity in organic materials stands as a coveted objective, particularly within electronic packaging, thermal interface materials, and organic matrix heat exchangers. These applications have reignited interest in researching thermally conductive organic materials. The understanding of thermal transport mechanisms in these organic materials is currently constrained. This study concentrates on N, N'-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8), an organic conjugated crystal. A correlation between elevated thermal conductivity and augmented Young's modulus is substantiated through meticulous experimentation. Achievement via employing the physical vapor transport method, capitalizing on the robust C═C covalent linkages running through the organic matrix chain, bolstered by π-π stacking and noncovalent affiliations that intertwine the chains. The coexistence of these dynamic interactions, alongside the perpendicular alignment of PTCDI-C8 molecules, is confirmed through structural analysis. PTCDI-C8 thin film exhibits an out-of-plane thermal conductivity of 3.1±0.1Wm-1K-1, as determined by time-domain thermoreflectance. This outpaces conventional organic materials by an order of magnitude. Nanoindentation tests and molecular dynamics simulations elucidate how molecular orientation and intermolecular forces within PTCDI-C8 molecules drive the film's high Young's modulus, contributing to its elevated thermal conductivity. This study's progress offers theoretical guidance for designing high thermal conductivity organic materials, expanding their applications and performance potential.

Using transducerless time-domain thermoreflectance technique to measure in- and cross-plane thermal conductivity of nanofilms

Time-domain thermoreflectance (TDTR) and frequency-domain thermoreflectance techniques have been widely used to measure thermal properties. However, the existence of the metal sensor brings some limitations to the experimental measurement, such as temperature limits, disability to measure low in-plane thermal conductivity, in situ measurement cannot be achieved, etc. This paper proposes a transducerless time-domain thermoreflectance method to measure in- and cross-plane thermal conductivity of nanofilms, in which the optical absorption depth and thermal conductivity tensor are considered to establish a new differential equation that can describe the heat conduction process in multilayer structures. This thermal model can also calculate the effects of spot ellipticity and spot offset distance. Then, the analytical solution and relative deviation of this new model and the surface heat flow boundary model used in conventional TDTR are compared by calculating the phase signals. In terms of experimental measurement, this model is successfully used to derive cross- and in-plane thermal conductivity of PdSi and IrNiTa amorphous alloy nanofilms without a metal sensor.

Optical and thermal properties of Ge2Sb2Te5, Sb2Se3, and Sb2S3 for reconfigurable photonic devices [Invited

Phase change materials (PCMs) are one of the most promising materials candidates for reconfigurable optics owing to their two solid-state atomic structures that render distinct optical properties. Recently, there have been growing interests in integrating these materials into photonic devices for achieving reconfigurable optical properties. In this paper, we focus on examining the optical and thermal properties of three essential phase change materials: Ge2Sb2Te5, Sb2Se3, and Sb2S3. The latter two have been specifically tailored for photonic applications, with minimal absorption losses in the near-infrared spectrum. In particular, we report the optical constants, refractive index (n) and extinction coefficient (k), for 300 nm thick Ge2Sb2Te5, Sb2Se3, and Sb2S3 on CaF2 substrate across a wide spectral range of 0.3 μm to 40 μm in amorphous and crystalline states. We observe that while Ge2Sb2Te5 exhibits a larger contrast in the index of refraction upon phase transformation compared to the other two compositions, Sb2Se3 and Sb2S3 demonstrate a substantial reduction in their extinction coefficients within the infrared spectrum. In addition, using time-domain thermoreflectance (TDTR), we report their thermal conductivity as a function of temperature up to 320°C. According to our observation, the room temperature thermal conductivity of Sb2Se3 and Sb2S3 increases by almost a factor of four upon phase transformation from amorphous to crystalline. The findings of this study provides necessary parameters for modeling PCM based photonic devices and emphasize the strong potential of Sb2Se3 and Sb2S3 as promising material candidates for reconfigurable optics due to their low-loss transmission in infrared spectrum, paving the way for their practical implementation in future photonic devices.

The effect of binding energy on optimizing the interfacial thermal transport in metal-MoS2-dielectric nanostructures

The development of MoS2-based devices presents a significant challenge due to the poor interfacial thermal transport of metal-MoS2-dielectric structures, which results in severe thermal dissipation issues. This work aims to investigate the effects of various strategies, including modifying metal electrodes, adjusting the number of MoS2 layers, and incorporating van der Waals heterostructures, on the enhancement of interface thermal conductance (ITC) of metal-MoS2-dielectric structures. The time-domain thermoreflectance method was applied to characterize the ITC and experimental results demonstrate that the effect of regulating metal electrodes depends on the binding energy between the metal-MoS2 interfaces, which is a matter of controversy due to the large dispersion of published results. Furthermore, the increase in the number of MoS2 layers does not necessarily lead to the enhancement of the ITC of metal-MoS2-dielectric structures, as this is a comprehensive reflection of the number of layers' influence on both thermal conductance of MoS2 itself and the ITC between MoS2 and the surrounding materials. The results from the heterostructures of hBN-MoS2 and Gr-MoS2 were then systematically compared, and the results indicate the potential of Gr-MoS2 heterostructures in augmenting ITC. In addition, the nonequilibrium molecular dynamics simulation was effectively employed to gain deeper insights into the effect of binding energy on optimizing the ITC of metal-heterostructures-dielectric nanostructures. Finally, the effectiveness of these strategies in enhancing thermal properties was discussed through an analysis of interfacial binding energy. This finding provides a valuable direction for enhancing the thermal management of MoS2-based devices.

Investigation of gallium oxide thin film hetero-integrated with bulk diamond via atomic layer deposition

In this work, the characteristics of the gallium oxide (Ga2O3)/diamond heterostructure were thoroughly examined after the preparation of Ga2O3 thin film on bulk diamond via atomic layer deposition. The X-ray diffraction (XRD) analysis revealed the Ga2O3 film amorphous and diamond polycrystalline. The atomic force microscopy (AFM) mapping displayed remarkably smooth surfaces of the Ga2O3 film and diamond substrate (RMS of 0.184 and 0.508 nm, respectively). The scanning electron microscopy (SEM) images showed conspicuous grains formed on the diamond, and small crystallites on the surface of the film. The optical characteristics were investigated via spectroscopic ellipsometry (SE) and UV/Vis/NIR spectrophotometer. Raman spectroscopy suggested a sharp diamond-related (sp3) peak and an extremely weak bulge band around 1350–1620 cm−1. X-ray photoelectron spectroscopy (XPS) analysis indicated Ga2O3/diamond heterojunction to be staggered (type II) band alignment with valence band and conduction band offsets of around 1.18 eV and 2.09 eV, respectively. Moreover, according to time-domain thermoreflectance (TDTR) measurements, the thermal conductivity of Ga2O3 and the thermal boundary conductivity of the heterointerface were 5.13 W/(m·K) and 19.22 MW/(m2·K), respectively. These findings not only demonstrate the feasibility of Ga2O3-on-diamond hetero-integration but open up new prospects for the design and physical analysis of Ga2O3/diamond-based devices in the future.

Heat Transport in Clathrate Hydrates Controlled by Guest Frequency and Host-Guest Interaction.

The underlying mechanism of common limited lattice thermal conductivity (κ) in energy-related host-guest crystalline compounds has been an ongoing topic in recent decades. Here, the guest-triggered intrinsic ultralow κ of the representative xenon clathrate hydrate was investigated using the time domain thermoreflectance technique and theoretical calculations. The localized guest modes were observed to hybridize with acoustic branches and severely limit the acoustic κ contribution. Besides, the strong mode coupling enables the reshaping of the overall lattice dynamics, especially for optical branches. More importantly, we identified that guest fillers prompt great phonon scattering in wide frequencies, which originates from both the guest-frequency-controlled enhancement of phase space and the host-guest-interaction-governed lattice anharmonicity. The extremely low guest frequency and strong host-guest interaction and coupling were thereby underlined to play vital but distinct roles in κ minimization. Our results unveil the dominant factors of guest reduction effects and facilitate the design of efficient thermoelectric or other thermal-related materials.

Origins of heat transport anisotropy in MoTe2 and other bulk van der Waals materials

Knowledge of how heat flows anisotropically in van der Waals (vdW) materials is crucial for thermal management of emerging 2D materials devices and design of novel anisotropic thermoelectric materials. Despite the importance, anisotropic heat transport in vdW materials is yet to be systematically studied and is often presumably attributed to anisotropic speeds of sound in vdW materials due to soft interlayer bonding relative to covalent in-plane networks of atoms. In this work, we investigate the origins of the anisotropic heat transport in vdW materials, through time-domain thermoreflectance (TDTR) measurements and first-principles calculations of anisotropic thermal conductivity of three different phases of MoTe2. MoTe2 is ideal for the study due to its weak anisotropy in the speeds of sound. We find that even when the speeds of sound are roughly isotropic, the measured thermal conductivity of MoTe2 along the c-axis is 5–8 times lower than that along the in-plane axes. We derive meaningful characteristic heat capacity, phonon group velocity, and relaxation times from our first principles calculations for selected vdW materials (MoTe2, BP, h-BN, and MoS2), to assess the contributions of these factors to the anisotropic heat transport. Interestingly, we find that the main contributor to the heat transport anisotropy in vdW materials is anisotropy in heat capacity of the dominant heat-carrying phonon modes in different directions, which originates from anisotropic optical phonon dispersion and disparity in the frequency of heat-carrying phonons in different directions. The discrepancy in frequency of the heat-carrying phonons also leads to ∼2 times larger average relaxation times in the cross-plane direction, and partially explains the apparent dependence of the anisotropic heat transport on the anisotropic speeds of sound. This work provides insight into understanding of the anisotropic heat transport in vdW materials.

Temperature-dependent thermal conductivity of MBE-grown epitaxial SrSnO3 films

As an ultrawide bandgap (∼4.1 eV) semiconductor, single crystalline SrSnO3 (SSO) has promising electrical properties for applications in power electronics and transparent conductors. The device performance can be limited by heat dissipation issues. However, a systematic study detailing its thermal transport properties remains elusive. This work studies the temperature-dependent thermal properties of a single crystalline SSO thin film prepared with hybrid molecular beam epitaxy. By combining time-domain thermoreflectance and Debye–Callaway modeling, physical insight into thermal transport mechanisms is provided. At room temperature, the 350-nm SSO film has a thermal conductivity of 4.4 W m−1 K−1, ∼60% lower than those of other perovskite oxides (SrTiO3, BaSnO3) with the same ABO3 structural formula. This difference is attributed to the low zone-boundary frequency of SSO, resulting from its distorted orthorhombic structure with tilted octahedra. At high temperatures, the thermal conductivity of SSO decreases with temperature following a ∼T−0.54 dependence, weaker than the typical T−1 trend dominated by the Umklapp scattering. This work not only reveals the fundamental mechanisms of thermal transport in single crystalline SSO but also sheds light on the thermal design and optimization of SSO-based electronic applications.