Heat conduction across monolayer and few-layer graphenes

We report the thermal conductance G of Au/Ti/graphene/SiO(2) interfaces (graphene layers 1 ≤ n ≤ 10) typical of graphene transistor contacts. We find G ≈ 25 MW m(-2) K(-1) at room temperature, four times smaller than the thermal conductance of a Au/Ti/SiO(2) interface, even when n = 1. We attribute this reduction to the thermal resistance of Au/Ti/graphene and graphene/SiO(2) interfaces acting in series. The temperature dependence of G from 50 ≤ T ≤ 500 K also indicates that heat is predominantly carried by phonons through these interfaces. Our findings suggest that metal contacts can limit not only electrical transport but also thermal dissipation from submicrometer graphene devices.     

Vibrational Coupling and Kapitza Resistance at a Solid–Liquid Interface

The rapid development and application of nanotechnologies have promoted an increasing interest in research on heat transfer across the solid/liquid interface. In this study, molecular dynamics simulations are carried out to elucidate the effect of vibrational coupling between the solid and the liquid phases on the Kapitza thermal resistance. This is accomplished by altering the atomic mass and interatomic interaction strength in the solid phase (thus, the vibrational properties), while keeping the solid–liquid interfacial interaction unchanged. In this way, the Kapitza resistance can be altered with a constant work of adhesion between the solid and the liquid phases. The simulation results show that the overlap degree between the vibrational density of states profiles of the interfacial liquid layer and the outermost solid layer, which measures the degree of interfacial vibrational coupling, increases with larger atomic mass and weaker inter-atomic interaction in the solid phase. An inverse relation exists between the Kapitza resistance and the overlap degree of the vibrational density of states profiles. It means that the Kapitza resistance decreases with better interfacial vibrational coupling. The simulations show that the Kapitza resistance is not only affected by the interfacial bonding strength but also the vibrational coupling between the solid and the liquid atoms. The interfaces with better thermal transport efficiency should be the ones with stronger interfacial interaction and preferable vibrational coupling between solid and liquid phases.     

Ultra-High Interfacial Thermal Conductance via Double hBN Encapsulation for Efficient Thermal Management of 2D Electronics

Heat dissipation is a major limitation of high-performance electronics. This is especially important in emerging nanoelectronic devices consisting of ultra-thin layers, heterostructures, and interfaces, where enhancement in thermal transport is highly desired. Here, ultra-high interfacial thermal conductance in encapsulated van der Waals (vdW) heterostructures with single-layer transition metal dichalcogenides MX₂ (MoS₂, WSe₂, WS₂) sandwiched between two hexagonal boron nitride (hBN) layers is reported. Through Raman spectroscopic measurements of suspended and substrate-supported hBN/MX₂/hBN heterostructures with varying laser power and temperature, the out-of-plane interfacial thermal conductance in the vertical stack is calibrated. The measured interfacial thermal conductance between MX₂ and hBN reaches 74 ± 25 MW m⁻² K⁻¹, which is at least ten times higher than the interfacial thermal conductance of MX₂ in non-encapsulation structures. Molecular dynamics (MD) calculations verify and explain the experimental results, suggesting a full encapsulation by hBN layers is accounting for the high interfacial conductance. This ultra-high interfacial thermal conductance is attributed to the double heat transfer pathways and the clean and tight vdW interface between two crystalline 2D materials. The findings in this study reveal new thermal transport mechanisms in hBN/MX₂/hBN structures and shed light on building novel hBN-encapsulated nanoelectronic devices with enhanced thermal management.     

Manipulating thermal conductance at metal-graphene contacts via chemical functionalization

Graphene-based devices have garnered tremendous attention due to the unique physical properties arising from this purely two-dimensional carbon sheet leading to tremendous efficiency in the transport of thermal carriers (i.e., phonons). However, it is necessary for this two-dimensional material to be able to efficiently transport heat into the surrounding 3D device architecture in order to fully capitalize on its intrinsic transport capabilities. Therefore, the thermal boundary conductance at graphene interfaces is a critical parameter in the realization of graphene electronics and thermal solutions. In this work, we examine the role of chemical functionalization on the thermal boundary conductance across metal/graphene interfaces. Specifically, we metalize graphene that has been plasma functionalized and then measure the thermal boundary conductance at Al/graphene/SiO(2) contacts with time domain thermoreflectance. The addition of adsorbates to the graphene surfaces are shown to influence the cross plane thermal conductance; this behavior is attributed to changes in the bonding between the metal and the graphene, as both the phonon flux and the vibrational mismatch between the materials are each subject to the interfacial bond strength. These results demonstrate plasma-based functionalization of graphene surfaces is a viable approach to manipulate the thermal boundary conductance.     

Linking Interfacial Bonding and Thermal Conductivity in Molecularly-Confined Polymer-Glass Nanocomposites with Ultra-High Interfacial Density

Thermal transport in polymer nanocomposites becomes dependent on the interfacial thermal conductance due to the ultra-high density of the internal interfaces when the polymer and filler domains are intimately mixed at the nanoscale. However, there is a lack of experimental measurements that can link the thermal conductance across the interfaces to the chemistry and bonding between the polymer molecules and the glass surface. Characterizing the thermal properties of amorphous composites are a particular challenge as their low intrinsic thermal conductivity leads to poor measurement sensitivity of the interfacial thermal conductance. To address this issue here, polymers are confined in porous organosilicates with high interfacial densities, stable composite structure, and varying surface chemistries. The thermal conductivities and fracture energies of the composites are measured with frequency dependent time-domain thermoreflectance (TDTR) and thin-film fracture testing, respectively. Effective medium theory (EMT) along with finite element analysis (FEA) is then used to uniquely extract the thermal boundary conductance (TBC) from the measured thermal conductivity of the composites. Changes in TBC are then linked to the hydrogen bonding between the polymer and organosilicate as quantified by Fourier-transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopy. This platform for analysis is a new paradigm in the experimental investigation of heat flow across constituent domains.     

Interfacial heat flow in carbon nanotube suspensions

The enormous amount of basic research into carbon nanotubes has sparked interest in the potential applications of these novel materials. One promising use of carbon nanotubes is as fillers in a composite material to improve mechanical behaviour, electrical transport and thermal transport. For composite materials with high thermal conductivity, the thermal conductance across the nanotube-matrix interface is of particular interest. Here we use picosecond transient absorption to measure the interface thermal conductance (G) of carbon nanotubes suspended in surfactant micelles in water. Classical molecular dynamics simulations of heat transfer from a carbon nanotube to a model hydrocarbon liquid are in agreement with experiment. Our findings indicate that heat transport in a nanotube composite material will be limited by the exceptionally small interface thermal conductance (G approximately 12 MW m(-2) K(-1)) and that the thermal conductivity of the composite will be much lower than the value estimated from the intrinsic thermal conductivity of the nanotubes and their volume fraction.     

Thermal conduction across the one-dimensional interface between a MoS<Subscript>2</Subscript> monolayer and metal electrode

The thermal conductance across the one-dimensional (1D) interface between a MoS2 monolayer and Au electrode (edge-contact) has been investigated using molecular dynamics simulations.Although the thermal conductivity of monolayer MoS2 is 2-3 orders of magnitude lower than that of graphene,the covalent bonds formed at the interface enable interfacial thermal conductance (ITC) that is comparable to that of a graphene-metal interface.Each covalent bond at the interface serves as an independent channel for thermal conduction,allowing ITC to be tuned linearly by changing the interfacial bond density (controlling S vacandes).In addition,different Au surfaces form different bonding configurations,causing large ITC variations.Interestingly,the S vacancies in the central region of MoS2 only slightly affect the ITC,which can be explained by a mismatch of the phonon vibration spectra.Further,at room temperature,ITC is primarily dominated by phonon transport,and electron-phonon coupling plays a negligible role.These results not only shed light on the phonon transport mechanisms across 1D metal-MoS2 interfaces,but also provide guidelines for the design and optimization of such interfaces for thermal management in MoS2-based electronicdevices.     

Anisotropic Thermal Boundary Resistance across 2D Black Phosphorus: Experiment and Atomistic Modeling of Interfacial Energy Transport

Interfacial thermal boundary resistance (TBR) plays a critical role in near‐junction thermal management of modern electronics. In particular, TBR can dominate heat dissipation and has become increasingly important due to the continuous emergence of novel nanomaterials with promising electronic and thermal applications. A highly anisotropic TBR across a prototype 2D material, i.e., black phosphorus, is reported through a crystal‐orientation‐dependent interfacial transport study. The measurements show that the metal–semiconductor TBR of the cross‐plane interfaces is 241% and 327% as high as that of the armchair and zigzag direction‐oriented interfaces, respectively. Atomistic ab initio calculations are conducted to analyze the anisotropic and temperature‐dependent TBR using density functional theory (DFT)‐derived full phonon dispersion relation and molecular dynamics simulation. The measurement and modeling work reveals that such a highly anisotropic TBR can be attributed to the intrinsic band structure and phonon spectral transmission. Furthermore, it is shown that phonon hopping between different branches is important to modulate the interfacial transport process but with directional preferences. A critical fundamental understanding of interfacial thermal transport and TBR–structure relationships is provided, which may open up new opportunities in developing advanced thermal management technology through the rational control over nanostructures and interfaces.     

Interfacially engineered liquid-phase-sintered Cu–In composite solders for thermal interface material applications

Cu particle-containing In-matrix composites for thermal interface material (TIM) applications were prepared via liquid phase sintering, following chemical modification of the Cu–In interfaces. The optimized composite TIM possessed 1.5 times the thermal conductivity, and twice the yield strength, of pure In. Joints of the composite TIM between pairs of cylindrical Cu rods were used to measure shear behavior and thermal resistance as functions of three parameters: (i) joint thickness, (ii) thermal excursion history, and (iii) type of interfacial layers between Cu and In. The composite joints showed good shear compliance, with a shear yield strength of 2.7 MPa, as well as substantially lower joint thermal resistance (0.021 cm² K W^?1) than pure In joints, which are commercially used in high-end TIM applications. The thermal resistance of the joints was found to be a sensitive function of the interfacial contact resistance between the Cu particles and In within the TIM, as well as between the TIM and the Cu substrates. The TIM–substrate interfaces, in particular, play an increasingly important role as the joint becomes thinner, limiting the joint thermal resistance. To reduce the interfacial contact resistance, a diffusion barrier of 1–2-nm-thick Al₂O₃ was applied by atomic layer deposition on both the Cu particles and the Cu substrates, followed by a 20-nm-thick Au layer, which served as a wetting enhancer. The engineered interfaces also improved the stability of the composite TIM joints under aging conditions.     

Photothermal Evidence of Laterally Inhomogeneous Interfacial Thermal Resistance in Copper-Coated Carbon Samples

In this study, the heat transport in copper?Ccarbon flat model systems was studied by frequency-dependent photothermal radiometry (PTR). The samples consist of Cu films of about 1???m thickness deposited by magnetron sputtering on vitreous carbon (Sigradur). Particular interest was devoted to the influence of interface defects on the interfacial thermal conductance (or resistance) of the CuC systems. The PTR data were analyzed in the frame of a heat diffusion equation for one- and three-dimensional heat transport. By comparing PTR signals from as-prepared and from heat-treated samples, the lateral inhomogeneities of the interfacial thermal conductance could be quantified. The measured phase differences were analyzed in the scope of a model where a small part of the surface area has a different interfacial thermal conductance than the major part of the surface.     

Phonon Contribution to Thermal Boundary Conductance at Metal Interfaces Using Embedded Atom Method Simulations

The phonon contribution to the thermal boundary conductance (TBC) at metal–metal interfaces is difficult to study experimentally, and it is typically considered negligible. In this study, molecular dynamics simulations (MDS), employing an embedded atom method (EAM) potential, are performed to study the phonon contribution to thermal transport across an Al–Cu interface. The embedded atom method provides a realistic model of atomic behavior in metals, while suppressing the effect on conduction electrons. In this way, measurements on the phonon system may be observed that would otherwise be dominated by the electron contribution in experimental methods. The relative phonon contribution to the TBC is calculated by comparing EAM results to previous experimental results which include both electron and phonon contributions. It is seen from the data that the relative phonon contribution increases with decreasing temperature, possibly accounting for more than half the overall TBC at temperatures below 100 K. These results suggest that neglect of interfacial phonon transport may not be a valid assumption at low temperatures, and may have implications in the future development of TBC models for metal interfaces.     

MoS<Subscript>2</Subscript>-graphene in-plane contact for high interfacial thermal conduction

Recent studies have indicated that two-dimensional (2D) MoS₂ exhibits low in-plane and inter-plane thermal conductivities. This poses a significant challenge to heat management in MoS₂-based electronic devices. To address this challenge, we have designed MoS₂-graphene interfaces that fully utilize graphene, a 2D material that exhibits very high thermal conductivity. First, we performed ab initio atomistic simulations to understand bonding and structural stability at the interfaces. The interfaces that we designed, which were connected via strong covalent bonds between Mo and C atoms, were energetically stable. We then performed molecular dynamics simulations to investigate interfacial thermal conductance in these materials. Surprisingly, the interfacial thermal conductance was high and comparable to those of covalently bonded graphene-metal interfaces. Importantly, each interfacial Mo–C bond served as an independent thermal channel, enabling modulation of the interfacial thermal conductance by controlling the Mo vacancy concentration at the interface. The present work provides a viable heat management strategy for MoS₂-based electronic devices.

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Thermal transport across twin grain boundaries in polycrystalline graphene from nonequilibrium molecular dynamics simulations

We have studied the thermal conductance of tilt grain boundaries in graphene using nonequilibrium molecular dynamics simulations. When a constant heat flux is allowed to flow, we observe sharp jumps in temperature at the boundaries, characteristic of interfaces between materials of differing thermal properties. On the basis of the magnitude of these jumps, we have computed the boundary conductance of twin grain boundaries as a function of their misorientation angles. We find the boundary conductance to be in the range 1.5 × 10(10) to 4.5 × 10(10) W/(m(2) K), which is significantly higher than that of any other thermoelectric interfaces reported in the literature. Using the computed values of boundary conductances, we have identified a critical grain size of 0.1 μm below which the contribution of the tilt boundaries to the conductivity becomes comparable to that of the contribution from the grains themselves. Experiments to test the predictions of our simulations are proposed.     

Effects of chemical bonding on heat transport across interfaces

Interfaces often dictate heat flow in micro- and nanostructured systems. However, despite the growing importance of thermal management in micro- and nanoscale devices, a unified understanding of the atomic-scale structural features contributing to interfacial heat transport does not exist. Herein, we experimentally demonstrate a link between interfacial bonding character and thermal conductance at the atomic level. Our experimental system consists of a gold film transfer-printed to a self-assembled monolayer (SAM) with systematically varied termination chemistries. Using a combination of ultrafast pump-probe techniques (time-domain thermoreflectance, TDTR, and picosecond acoustics) and laser spallation experiments, we independently measure and correlate changes in bonding strength and heat flow at the gold-SAM interface. For example, we experimentally demonstrate that varying the density of covalent bonds within this single bonding layer modulates both interfacial stiffness and interfacial thermal conductance. We believe that this experimental system will enable future quantification of other interfacial phenomena and will be a critical tool to stimulate and validate new theories describing the mechanisms of interfacial heat transport. Ultimately, these findings will impact applications, including thermoelectric energy harvesting, microelectronics cooling, and spatial targeting for hyperthermal therapeutics.     

Micro/nanoscale spatial resolution temperature probing for the interfacial thermal characterization of epitaxial graphene on 4H-SiC

Limited internal phonon coupling and transfer within graphene in the out-of-plane direction significantly affects graphene-substrate interfacial phonon coupling and scattering, and leads to unique interfacial thermal transport phenomena. Through the simultaneous characterization of graphene and SiC Raman peaks, it is possible, for the first time, to distinguish the temperature of a graphene layer and its adjacent 4H-SiC substrate. The thermal probing resolution reaches the nanometer scale with the graphene (≈1.12 nm) and is on the micrometer scale (≈12 μm) within SiC next to the interface. A very high thermal resistance at the interface of 5.30 (-0.46) (+0.46) x 10(-5) Km2 W(-1) is observed by using a Raman frequency method under surface Joule heating. This value is much higher than those from molecular dynamics predictions of 7.01(-1.05) (+1.05) x 10(-1) and 8.47(-0.75) (+0.75) x 10(-10) Km2 w(-1) for surface heat fluxes of 3 × 10(9) and 1 × 10(9) and 1 x 10(10) W m(-2) , respectively. This analysis shows that the measured anomalous thermal contact resistance stems from the thermal expansion mismatch between graphene and SiC under Joule heating. This mismatch leads to interface delamination/separation and significantly enhances local phonon scattering. An independent laser-heating experiment conducted under the same conditions yielded a higher interfacial thermal resistance of 1.01(-0.59) (+1.23) x 10(-4) Km2 W(-1). Furthermore, the peak width method of Raman thermometry is also employed to evaluate the interfacial thermal resistance. The results are 3.52 × 10(-5) and 8.57 × 10(-5) K m2 W(-1) for Joule-heating and laser-heating experiments, respectively, confirming the anomalous thermal resistance between graphene and SiC. The difference in the results from the frequency and peak-width methods is caused by the thermal stress generated in the heating processes.     

Micro‐/Nanostructured Interface for Liquid Manipulation and Its Applications

Understanding the relationship between liquid manipulation and micro‐/nanostructured interfaces has gained much attention due to the wide potential applications in many fields, such as chemical and biomedical assays, environmental protection, industry, and even daily life. Much work has been done to construct various materials with interfacial liquid manipulation abilities, leading to a range of interesting applications. Herein, different fabrication methods from the top‐down approach to the bottom‐up approach and subsequent surface modifications of micro‐/nanostructured interfaces are first introduced. Then, interactions between the surface and liquid, including liquid wetting, liquid transportation, and a number of corresponding models, together with the definition of hydrophilic/hydrophobic, oleophilic/olephobic, the definition and mechanism of superwetting, including superhydrophobicity, superhydrophilicity, and superoleophobicity, are presented. The micro‐/nanostructured interface, with major applications in self‐cleaning, antifogging, anti‐icing, anticorrosion, drag‐reduction, oil–water separation, water collection, droplet (micro)array, and surface‐directed liquid transport, is summarized, and the mechanisms underlying each application are discussed. Finally, the remaining challenges and future perspectives in this area are included.     

Quantum transport through a DNA wire in a dissipative environment

Electronic transport through DNA wires in the presence of a strong dissipative environment is investigated. We show that new bath-induced electronic states are formed within the band gap. These states show up in the linear conductance spectrum as a temperature dependent background and lead to a crossover from tunneling to thermal activated behavior with increasing temperature. Depending on the strength of the electron-bath coupling, the conductance at the Fermi level can show a weak exponential or even an algebraic length dependence. Our results suggest a new environmentally induced transport mechanism. This might be relevant for the understanding of molecular conduction experiments in liquid solution, such as those recently performed on poly(GC) oligomers in a water buffer (B. Xu et al., Nano Lett. 2004, 4, 1105).     

Nanoscale adhesion,friction and wear studies of biomolecules on silane polymer-coated silica and alumina-based surfaces

Proteins on biomicroelectromechanical systems (BioMEMS) confer specific molecular functionalities. In planar FET sensors (field-effect transistors, a class of devices whose protein-sensing capabilities we demonstrated in physiological buffers), interfacial proteins are analyte receptors, determining sensor molecular recognition specificity. Receptors are bound to the FET through a polymeric interface, and gross disruption of interfaces that removes a large percentage of receptors or inactivates large fractions of them diminishes sensor sensitivity. Sensitivity is also determined by the distance between the bound analyte and the semiconductor. Consequently, differential properties of surface polymers are design parameters for FET sensors. We compare thickness, surface roughness, adhesion, friction and wear properties of silane polymer layers bound to oxides (SiO₂ and Al₂O₃, as on AlGaN HFETs). We compare those properties of the film–substrate pairs after an additional deposition of biotin and streptavidin. Adhesion between protein and device and interfacial friction properties affect FET reliability because these parameters affect wear resistance of interfaces to abrasive insult in vivo. Adhesion/friction determines the extent of stickage between the interface and tissue and interfacial resistance to mechanical damage. We document systematic, consistent differences in thickness and wear resistance of silane films that can be correlated with film chemistry and deposition procedures, providing guidance for rational interfacial design for planar AlGaN HFET sensors.     

Differential impedance spectroscopy for monitoring protein immobilization and antibody-antigen reactions

This work describes the theoretical and experimental approaches for monitoring the interfacial biomolecular reaction between immobilized antibody and the antigen binding partner using novel differential impedance spectroscopy. The prerequisite of any biosensor is the immobilization of macromolecules onto the surface of a transducer. It is clear that the function of most macromolecules changes from what is observed in solution once immobilization has occurred. In the worst case, molecules entirely lose their binding activity almost immediately after immobilization. Certain conditions (e.g., denaturation, interfacial effects based on ionic strength, surface charge, dielectric constants, etc.) at interfaces are responsible for alterations of binding activity; it is not clear whether a combination of such processes is understood. However, these processes in combination must be reliably modeled in order to predict the outcome for most macromolecules. This work presents the theoretical and practical means for elucidating the surface reactivity of biomolecular reagents using ion displacement model with antibody-antigen (Ab-Ag) reaction as the test case. The Ab-Ag reaction was directly monitored using a dual-channeled, impedance analyzer capable of 1 measurement/s using covalent immobilization chemistry and polymer-modified electrodes in the absence of a redox probe. The evidence of Ab-Ag binding was revealed through the evolution of differential admittance. The surface loading obtained using the covalent immobilization chemistry was 9.0 x 10(16)/cm2, whereas with polymer-modified electrodes, the surface loading was 9.0 x 10(15)/cm2, representing a 10 times increase in surface reactivity. The proposed approach may be applicable to monitoring other surface interfacial reactions such as DNA-DNA interactions, DNA-protein interactions, and DNA-small molecule interactions.     

Thermal conductivity of Al–SiC composites with monomodal and bimodal particle size distribution

The thermal conductivity of aluminum matrix composites having a high volume fraction of SiC particles is investigated by comparing data for composites fabricated by infiltrating liquid aluminum into preforms made either from a single particle size, or by mixing and packing SiC particles of two largely different average sizes (170 and 16 μm). For composites based on powders with a monomodal size distribution, the thermal conductivity increases steadily from 151 W/m K for particles of average diameter 8 μm to 216 W/m K for 170 μm particles. For the bimodal particle mixtures the thermal conductivity increases with increasing volume fraction of coarse particles and reaches a roughly constant value of 220 W/m K for mixtures with 40 or more vol.% of coarse particles. It is shown that all present data can be accounted for by the differential effective medium (DEM) scheme taking into account a finite interfacial thermal resistance.