Time-domain Thermoreflectance Measurements Research Articles

Spatial Mapping of Thermal Boundary Conductance at Metal-Molybdenum Diselenide Interfaces.

Improving the thermal transport across interfaces is a necessary consideration for micro- and nanoelectronic devices and necessitates accurate measurement of the thermal boundary conductance (TBC) and understanding of transport mechanisms. Two-dimensional transition-metal dichalcogenides (TMDs) have been studied extensively for their electrical properties, including the metal-TMD electrical contact resistance, but the thermal properties of these interfaces are significantly less explored irrespective of their high importance in their electronic devices. We isolate individual islands of MoSe2 grown by chemical vapor deposition using photolithography and correlate the 2D variation of TBC with optical microscope images of the MoSe2 islands. We measure the 2D spatial variation of the TBC at metal-MoSe2-SiO2 interfaces using a modified time-domain thermoreflectance (TDTR) technique, which requires much less time than full TDTR scans. The thermoreflectance signal at a single probe delay time is compared with a correlation curve, which enables us to estimate the change in the signal with respect to the TBC at the metal-MoSe2-SiO2 interface as opposed to recording the decay of the thermoreflectance signal over delay times of several nanoseconds. The results show a higher TBC across the Ti-MoSe2-SiO2 interface compared to Al-MoSe2-SiO2. An image-clustering method is developed to differentiate the TBC for different numbers of MoSe2 layers, which reveals that the TBC in single-layer regions is higher than that in the bilayer. We perform traditional TDTR measurements over a range of delay times and verify that TBC is higher at the Ti-MoSe2-SiO2 interface compared to Al-MoSe2-SiO2, highlighting the importance of the choice of metal for heat dissipation at electrical contacts in TMD devices.

Structure Function Analysis of Temperature-Dependent Thermal Properties of Nm-Thin Nb2O5

A 166-nm-thick amorphous Niobium pentoxide layer (Nb2O5) on a silicon substrate was investigated by using time domain thermoreflectance at ambient temperatures from 25 °C to 500 °C. In the time domain thermoreflectance measurements, thermal transients with a time resolution in (sub-)nanoseconds can be obtained by a pump-probe laser technique. The analysis of the thermal transient was carried out via the established analytical approach, but also by a numerical approach. The analytical approach showed a thermal diffusivity and thermal conductivity from 0.43 mm2/s to 0.74 mm2/s and from 1.0 W/mK to 2.3 W/mK, respectively to temperature. The used numerical approach was the structure function approach to map the measured heat path in terms of a RthCth-network. The structure function showed a decrease of Rth with increasing temperature according to the increasing thermal conductivity of Nb2O5. The combination of both approaches contributes to an in-depth thermal analysis of Nb2O5 film.

Thermal conductivity of GaN, GaN71 , and SiC from 150 K to 850 K

The thermal conductivity (\ensuremath{\Lambda}) of wide-band-gap semiconductors GaN and SiC is critical for their application in power devices and optoelectronics. Here, we report time-domain thermoreflectance measurements of \ensuremath{\Lambda} in GaN, $^{71}\mathrm{GaN}$, and SiC between 150 and 850 K. The samples include bulk $c$- and $m$-plane wurtzite GaN grown by hydride vapor phase epitaxy (HVPE) and ammonothermal methods; homoepitaxial natural isotope abundant GaN and isotopically enriched $^{71}\mathrm{GaN}$ layers with thickness of 6--12 \ensuremath{\mu}m grown on $c$-, $m$-, and $a$-plane GaN substrates grown by HVPE; and bulk crystals of 4H and 6H SiC. In low dislocation density ($l{10}^{7}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}2}$) bulk and homoepitaxial GaN, \ensuremath{\Lambda} is insensitive to crystal orientation and doping concentration (for doping $l{10}^{19}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}3}$); $\mathrm{\ensuremath{\Lambda}}\ensuremath{\approx}200\phantom{\rule{0.16em}{0ex}}\mathrm{W}\phantom{\rule{0.16em}{0ex}}{\mathrm{m}}^{\ensuremath{-}1}\phantom{\rule{0.16em}{0ex}}{\mathrm{K}}^{\ensuremath{-}1}$ at 300 K and $\ensuremath{\approx}50\phantom{\rule{0.16em}{0ex}}\mathrm{W}\phantom{\rule{0.16em}{0ex}}{\mathrm{m}}^{\ensuremath{-}1}\phantom{\rule{0.16em}{0ex}}{\mathrm{K}}^{\ensuremath{-}1}$ at 850 K. In $^{71}\mathrm{GaN}$ epilayers at 300 K, \ensuremath{\Lambda} is $\ensuremath{\approx}15%$ higher than in GaN with natural isotope abundance. The measured temperature dependence of \ensuremath{\Lambda} in GaN is stronger than predicted by first-principles based solutions of the Boltzmann transport equation that include anharmonicity up to third order. This discrepancy between theory and experiment suggests possible significant contributions to the thermal resistivity from higher-order phonon scattering that involve interactions between more than three phonons. The measured \ensuremath{\Lambda} of 4H and 6H SiC is anisotropic, in good agreement with first-principles calculations, and larger than GaN by a factor of $\ensuremath{\approx}1.5$ in the temperature range $300lTl850\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. This paper provides benchmark knowledge about the thermal conductivity in wide-band-gap semiconductors of GaN, $^{71}\mathrm{GaN}$, and SiC over a wide temperature range for their applications in power electronics and optoelectronics.

Thermal conductivity of plasma deposited amorphous hydrogenated boron and carbon rich thin films

Owing to a unique combination of low density, high mechanical stiffness, and high neutron capture cross section, boron rich solids are of interest for a number of applications ranging from fusion shielding and neutron absorbing materials to solid state neutron detection. In many of these applications, the boron containing materials may be exposed to extreme temperatures and thermal gradients where heat dissipation is a significant concern. While there have been several reports of the thermal conductivity for crystalline boron solids, comparitively little is known regarding the thermal conductivity for amorphous boron thin films used in many nuclear applications. In this investigation, we report time-domain thermoreflectance (TDTR) measurements for a series of plasma deposited boron rich thin films with nominal compositions of a-B:H and a-BP:H. The results were compared to additional measurements performed on a-C:H films with similar mass density and which are also utilized as fusion plasma shielding materials. The values of thermal conductivity determined by TDTR for the a-B:H and a-BP:H films ranged from 1 to 2 W/mK. These values are reduced relative to those reported for crystalline boron (4–400 W/mK) but compare well to those obtained for a-C:H (0.5–1.5 W/mK).

Record-Low and Anisotropic Thermal Conductivity of a Quasi-One-Dimensional Bulk ZrTe5 Single Crystal.

Zirconium pentatelluride (ZrTe5) has recently attracted renewed interest owing to many of its newly discovered extraordinary physical properties, such as 2D and 3D topological-insulator behavior, pressure-induced superconductivity, Weyl semimetal behavior, Zeeman splitting, and resistivity anomaly. The quasi-one-dimensional structure of single-crystal ZrTe5 also promises large anisotropy in its thermal properties, which have not yet been studied. In this work, via time-domain thermoreflectance measurements, ZrTe5 single crystals are discovered to possess a record-low thermal conductivity along the b-axis (through-plane), as small as 0.33 ± 0.03 W m-1 K-1 at room temperature. This ultralow b-axis thermal conductivity is 12 times smaller than its a-axis thermal conductivity (4 ± 1 W m-1 K-1) owing to the material's asymmetrical crystalline structure. First-principles calculations are further conducted to reveal the physical origins of the ultralow b-axis thermal conductivity, which can be attributed to: (1) the resonant bonding and strong lattice anharmonicity induced by electron lone pairs, (2) the weak interlayer van der Waals interactions, and (3) the heavy mass of Te atoms, which results in low phonon group velocity. This work sheds light on the design and engineering of high-efficiency thermal insulators for applications such as thermal barrier coatings, thermoelectrics, thermal energy storage, and thermal management.

A new elliptical-beam method based on time-domain thermoreflectance (TDTR) to measure the in-plane anisotropic thermal conductivity and its comparison with the beam-offset method.

Materials lacking in-plane symmetry are ubiquitous in a wide range of applications such as electronics, thermoelectrics, and high-temperature superconductors, in all of which the thermal properties of the materials play a critical part. However, very few experimental techniques can be used to measure in-plane anisotropic thermal conductivity. A beam-offset method based on time-domain thermoreflectance (TDTR) was previously proposed to measure in-plane anisotropic thermal conductivity. However, a detailed analysis of the beam-offset method is still lacking. Our analysis shows that uncertainties can be large if the laser spot size or the modulation frequency is not properly chosen. Here we propose an alternative approach based on TDTR to measure in-plane anisotropic thermal conductivity using a highly elliptical pump (heating) beam. The highly elliptical pump beam induces a quasi-one-dimensional temperature profile on the sample surface that has a fast decay along the short axis of the pump beam. The detected TDTR signal is exclusively sensitive to the in-plane thermal conductivity along the short axis of the elliptical beam. By conducting TDTR measurements as a function of delay time with the rotation of the elliptical pump beam to different orientations, the in-plane thermal conductivity tensor of the sample can be determined. In this work, we first conduct detailed signal sensitivity analyses for both techniques and provide guidelines in determining the optimal experimental conditions. We then compare the two techniques under their optimal experimental conditions by measuring the in-plane thermal conductivity tensor of a ZnO [11-20] sample. The accuracy and limitations of both methods are discussed.

Anisotropic thermal transport in bulk hexagonal boron nitride

Hexagonal boron nitride (h-BN) has received great interest in recent years as a wide bandgap analog of graphene-derived systems. However, the thermal transport properties of h-BN, which can be critical for device reliability and functionality, are little studied both experimentally and theoretically. The primary challenge in the experimental measurements of the anisotropic thermal conductivity of h-BN is that typically sample size of h-BN single crystals is too small for conventional measurement techniques, as state-of-the-art technologies synthesize h-BN single crystals with lateral sizes only up to 2.5 mm and thickness up to 200 {\mu}m. Recently developed time-domain thermoreflectance (TDTR) techniques are suitable to measure the anisotropic thermal conductivity of such small samples, as it only requires a small area of 50x50 {\mu}m2 for the measurements. Accurate atomistic modeling of thermal transport in bulk h-BN is also challenging due to the highly anisotropic layered structure. Here we conduct an integrated experimental and theoretical study on the anisotropic thermal conductivity of bulk h-BN single crystals over the temperature range of 100 K to 500 K, using TDTR measurements with multiple modulation frequencies and a full-scale numerical calculation of the phonon Boltzmann transport equation starting from the first principles. Our experimental and numerical results compare favorably for both the in-plane and through-plane thermal conductivities. We observe unusual temperature-dependence and phonon-isotope scattering in the through-plane thermal conductivity of h-BN and elucidate their origins. This work not only provides an important benchmark of the anisotropic thermal conductivity of h-BN but also develops fundamental insights into the nature of phonon transport in this highly anisotropic layered material.

Anisotropic thermal transport in van der Waals layered alloys WSe2(1-x)Te2x

Transition metal dichalcogenide (TMD) alloys have attracted great interest in recent years due to their tunable electronic properties and the semiconductor-metal phase transition along with their potential applications in solid-state memories and thermoelectrics among others. However, the thermal conductivity of layered TMD alloys remains largely unexplored despite that it plays a critical role in the reliability and functionality of TMD-enabled devices. In this work, we study the composition- and temperature-dependent anisotropic thermal conductivity of the van der Waals layered TMD alloys WSe2(1-x)Te2x in both the in-plane direction (parallel to the basal planes) and the cross-plane direction (along the c-axis) using time-domain thermoreflectance measurements. In the WSe2(1-x)Te2x alloys, the cross-plane thermal conductivity is observed to be dependent on the heating frequency (modulation frequency of the pump laser) due to the non-equilibrium transport between different phonon modes. Using a two-channel heat conduction model, we extracted the anisotropic thermal conductivity at the equilibrium limit. A clear discontinuity in both the cross-plane and the in-plane thermal conductivity is observed as x increases from 0.4 to 0.6 due to the phase transition from the 2H to the Td phase in the layered alloys. The temperature dependence of thermal conductivity for the TMD alloys was found to become weaker compared with the pristine 2H WSe2 and Td WTe2 due to the atomic disorder. This work serves as an important starting point for exploring phonon transport in layered alloys.

Interfacial phonon scattering and transmission loss in >1 µm thick silicon-on-insulator thin films

Scattering of phonons at boundaries of a crystal (grains, surfaces, or solid/solid interfaces) is characterized by the phonon wavelength, the angle of incidence, and the interface roughness, as historically evaluated using a specularity parameter $p$ formulated by Ziman [Electrons and Phonons (Clarendon Press, Oxford, 1960)]. This parameter was initially defined to determine the probability of a phonon specularly reflecting or diffusely scattering from the rough surface of a material. The validity of Ziman's theory as extended to solid/solid interfaces has not been previously validated. To better understand the interfacial scattering of phonons and to test the validity of Ziman's theory, we precisely measured the in-plane thermal conductivity of a series of Si films in silicon-on-insulator (SOI) wafers by time-domain thermoreflectance (TDTR) for a Si film thickness range of 1--10 \ensuremath{\mu}m and a temperature range of 100--300 K. The $\mathrm{Si}/{\mathrm{SiO}}_{2}$ interface roughness was determined to be $0.11\ifmmode\pm\else\textpm\fi{}0.04\phantom{\rule{0.16em}{0ex}}\mathrm{nm}$ using transmission electron microscopy (TEM). Furthermore, we compared our in-plane thermal conductivity measurements to theoretical calculations that combine first-principles phonon transport with Ziman's theory. Calculations using Ziman's specularity parameter significantly overestimate values from the TDTR measurements. We attribute this discrepancy to phonon transmission through the solid/solid interface into the substrate, which is not accounted for by Ziman's theory for surfaces. The phonons that are specularly transmitted into an amorphous layer will be sufficiently randomized by the time they come back to the crystalline Si layer, the effect of which is practically equivalent to a diffuse reflection at the interface. We derive a simple expression for the specularity parameter at solid/amorphous interfaces and achieve good agreement between calculations and measurement values.

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.

Analysis of simplified heat transfer models for thermal property determination of nano-film by TDTR method

Heat transfer in nanostructures is of critical importance for a wide range of applications such as functional materials and thermal management of electronics. Time-domain thermoreflectance (TDTR) has been proved to be a reliable measurement technique for the thermal property determinations of nanoscale structures. However, it is difficult to determine more than three thermal properties at the same time. Heat transfer model simplifications can reduce the fitting variables and provide an alternative way for thermal property determination. In this paper, two simplified models are investigated and analyzed by the transform matrix method and simulations. TDTR measurements are performed on Al–SiO2–Si samples with different SiO2 thickness. Both theoretical and experimental results show that the simplified tri-layer model (STM) is reliable and suitable for thin film samples with a wide range of thickness. Furthermore, the STM can also extract the intrinsic thermal conductivity and interfacial thermal resistance from serial samples with different thickness.

Anisotropic thermal conductivity of 4H and 6H silicon carbide measured using time-domain thermoreflectance

Silicon carbide (SiC) is a wide bandgap (WBG) semiconductor with promising applications in high-power and high-frequency electronics. Among its many useful properties, the high thermal conductivity is crucial. In this letter, the anisotropic thermal conductivity of three SiC samples, n-type 4H-SiC (N-doped 1 × 1019 cm−3), unintentionally doped (UID) semi-insulating (SI) 4H-SiC, and SI 6H-SiC (V-doped 1 × 1017 cm−3), is measured using femtosecond laser based time-domain thermoreflectance (TDTR) over a temperature range from 250 K to 450 K. We simultaneously measure the thermal conductivity parallel to (kr) and across the hexagonal plane (kz) for SiC by choosing the appropriate laser spot radius and the modulation frequency for the TDTR measurements. For both kr and kz, the following decreasing order of thermal conductivity value is observed: SI 4H-SiC > n-type 4H-SiC > SI 6H-SiC. This work serves as an important benchmark for understanding thermal transport in WBG semiconductors.

Probing the Local Heat Transfer Coefficient of Water-Cooled Microchannels Using Time-Domain Thermoreflectance

The demands for increasingly smaller, more capable, and higher power density technologies have heightened the need for new methods to manage and characterize extreme heat fluxes. This work presents the use of an anisotropic version of the time-domain thermoreflectance (TDTR) technique to characterize the local heat transfer coefficient (HTC) of a water-cooled rectangular microchannel in a combined hot-spot heating and subcooled channel-flow configuration. Studies focused on room temperature, single-phase, degassed water flowing at an average velocity of ≈3.5 m/s in a ≈480 μm hydraulic diameter microchannel (e.g., Re ≈ 1850), where the TDTR pump heating laser induces a local heat flux of ≈900 W/cm2 in the center of the microchannel with a hot-spot area of ≈250 μm2. By using a differential TDTR measurement approach, we show that thermal effusivity distribution of the water coolant over the hot-spot is correlated to the single-phase convective heat transfer coefficient, where both the stagnant fluid (i.e., conduction and natural convection) and flowing fluid (i.e., forced convection) contributions are decoupled from each other. Our measurements of the local enhancement in the HTC over the hot-spot are in good agreement with established Nusselt number correlations. For example, our flow cooling results using a Ti metal wall support a maximum HTC enhancement via forced convection of ≈1060 ± 190 kW/m2 K, where the Nusselt number correlations predict ≈900 ± 150 kW/m2 K.

Thermal conductivity of Bi2(SexTe1−x)3 alloy films grown by molecular beam epitaxy

We studied the thermal conductivity of Bi2Se3, Bi2Te3, and their alloy Bi2(SexTe1−x)3 at room temperature using time-domain thermoreflectance measurements. The Bi2(SexTe1−x)3 films with various concentrations of Se and Te prepared by molecular beam epitaxy on GaAs substrates were investigated to study the dependence of thermal conductivity on film composition. We observed that the Bi2(SexTe1−x)3 ternary alloys can have much lower thermal conductivity values compared to those of Bi2Se3 and Bi2Te3. These results may provide useful information for developing and engineering low thermal conductivity materials for thermoelectric applications.

A general model for thermal and electrical conductivity of binary metallic systems

We extended and updated Mott's two-band model for the composition-dependence of thermal and electrical conductivity in binary metal alloys based on high-throughput time-domain thermoreflectance (TDTR) measurements on diffusion multiples and scatterer-density calculations from first principles. Examining Au-Cu, Au-Ag, Pd-Ag, Pd-Cu, Pd-Pt, Pt-Rh, and Ni-Rh binary alloys, we found that the nature of the two dominant scatterer-bands considered in the Mott model changes with the alloys, and should be interpreted as a combination of the dominant element-specific s- and/or d-orbitals. Using orbital and element-resolved density-of-states values calculated with density functional theory as input, we determined the correct orbital mix that dominates electron scattering for all examined alloys and found excellent agreement between fitted models and experimental results. This general model of the composition dependence of the thermal and electrical resistivity can be readily implemented into the CALPHAD framework.

Long delay time study of thermal transport and thermal stress in thin Pt film-glass substrate system by time-domain thermoreflectance measurements

Solid state thermoelectric devices are desirable for various sustainable applications. Most of these thin film devices are multilayered structures which requires thorough understanding of thermal transport and thermal stress in order to solve thermal issues. In this paper the experimental technology as well as theoretical model of long delay time pump-probe study with four different illumination configurations have been developed to comprehensively characterize the thermal transport and thermal stress of thin film, substrate and the interface. Furthermore, 94-nm-thick Pt film-glass substrate system has been studied by applying time-domain thermoreflectance measurements under four illumination configurations with high signal quality. The obtained time-dependent temperature signal is superposed by the effects of multilayered thermal transport and thermal stress spontaneously, and the corresponding theoretical predictions match well with the experimental data in the whole delay time range. The determined thermal conductivity of the Pt film shows significant size effect.

Accurate measurements of cross-plane thermal conductivity of thin films by dual-frequency time-domain thermoreflectance (TDTR).

Accurate measurements of the cross-plane thermal conductivity Λcross of a high-thermal-conductivity thin film on a low-thermal-conductivity (Λs) substrate (e.g., Λcross/Λs > 20) are challenging, due to the low thermal resistance of the thin film compared with that of the substrate. In principle, Λcross could be measured by time-domain thermoreflectance (TDTR), using a high modulation frequency fh and a large laser spot size. However, with one TDTR measurement at fh, the uncertainty of the TDTR measurement is usually high due to low sensitivity of TDTR signals to Λcross and high sensitivity to the thickness hAl of Al transducer deposited on the sample for TDTR measurements. We observe that in most TDTR measurements, the sensitivity to hAl only depends weakly on the modulation frequency f. Thus, we performed an additional TDTR measurement at a low modulation frequency f0, such that the sensitivity to hAl is comparable but the sensitivity to Λcross is near zero. We then analyze the ratio of the TDTR signals at fh to that at f0, and thus significantly improve the accuracy of our Λcross measurements. As a demonstration of the dual-frequency approach, we measured the cross-plane thermal conductivity of a 400-nm-thick nickel-iron alloy film and a 3-μm-thick Cu film, both with an accuracy of ∼10%. The dual-frequency TDTR approach is useful for future studies of thin films.

Understanding and eliminating artifact signals from diffusely scattered pump beam in measurements of rough samples by time-domain thermoreflectance (TDTR).

Time-domain thermoreflectance (TDTR) is a pump-probe technique frequently applied to measure the thermal transport properties of bulk materials, nanostructures, and interfaces. One of the limitations of TDTR is that it can only be employed to samples with a fairly smooth surface. For rough samples, artifact signals are collected when the pump beam in TDTR measurements is diffusely scattered by the rough surface into the photodetector, rendering the TDTR measurements invalid. In this paper, we systemically studied the factors affecting the artifact signals due to the pump beam leaked into the photodetector and thus established the origin of the artifact signals. We find that signals from the leaked pump beam are modulated by the probe beam due to the phase rotation induced in the photodetector by the illumination of the probe beam. As a result of the modulation, artifact signals due to the leaked pump beam are registered in TDTR measurements as the out-of-phase signals. We then developed a simple approach to eliminate the artifact signals due to the leaked pump beam. We verify our leak-pump correction approach by measuring the thermal conductivity of a rough InN sample, when the signals from the leaked pump beam are significant. We also discuss the advantages of our new method over the two-tint approach and its limitations. Our new approach enables measurements of the thermal conductivity of rough samples using TDTR.

Temperature-Dependent Mean Free Path Spectra of Thermal Phonons Along the c-Axis of Graphite.

Heat conduction in graphite has been studied for decades because of its exceptionally large thermal anisotropy. While the bulk thermal conductivities along the in-plane and cross-plane directions are well-known, less understood are the microscopic properties of the thermal phonons responsible for heat conduction. In particular, recent experimental and computational works indicate that the average phonon mean free path (MFP) along the c-axis is considerably larger than that estimated by kinetic theory, but the distribution of MFPs remains unknown. Here, we report the first quantitative measurements of c-axis phonon MFP spectra in graphite at a variety of temperatures using time-domain thermoreflectance measurements of graphite flakes with variable thickness. Our results indicate that c-axis phonon MFPs have values of a few hundred nanometers at room temperature and a much narrower distribution than in isotropic crystals. At low temperatures, phonon scattering is dominated by grain boundaries separating crystalline regions of different rotational orientation. Our study provides important new insights into heat transport and phonon scattering mechanisms in graphite and other anisotropic van der Waals solids.

Covalent bonding modulated graphene-metal interfacial thermal transport.

We report the covalent bonding enabled modulation of the interfacial thermal conductance between graphene and metals Cu, Al, and Pt by controlling the oxidation of graphene. By combining comprehensive X-ray photoelectron spectroscopy (XPS) analysis and time-domain thermoreflectance measurements, we quantify the effect of graphene oxidation on interfacial thermal conductance. It was found that thermal conductance increases with the degree of graphene oxidation until a peak value is obtained at an oxygen/carbon atom percentage of ∼7.7%. The maximum enhancement in thermal conductance was measured to be 55%, 38%, and 49% for interfaces between oxidized graphene and Cu, Al, and Pt, respectively. In situ XPS measurements show that oxygen covalently binds to Cu and graphene simultaneously, forming a highly efficient bridge to enhance the thermal transport. Our molecular dynamics simulations verify that strong interfacial covalent bonds are the key to the thermal conductance enhancement. This work provides valuable insights into the mechanism of functionalization-induced thermal conductance enhancement and design guidelines for graphene-based devices.