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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Temperature-Dependent Thermal Boundary Conductance at Al/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Pt/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> interfaces

With the ever-decreasing size of microelectronic devices, growing applications of superlattices, and development of nanotechnology, thermal resistances of interfaces are becoming increasingly central to thermal management. Although there has been much success in understanding thermal boundary conductance at low temperatures, the current models applied at temperatures more common in device operation are not adequate due to our current limited understanding of phonon transport channels. In this study, the scattering processes in Al and Pt films on Al₂O₃ substrates are examined by transient thermoreflectance testing at high temperatures. At high temperatures, traditional models predict the thermal boundary conductance to be relatively constant in these systems due to assumptions about phonon elastic scattering. Experiments, however, show an increase in the conductance indicating potential inelastic phonon processes.     

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.     

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.     

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.     

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.     

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.     

掺杂单层MoS_2电子结构的第一性原理计算

采用第一性原理研究Cu,Ag,Au掺杂单层MoS_2的键长畸变、能带结构和态密度。探讨Cu,Ag,Au掺杂对单层MoS_2电子结构的影响。结果表明:Cu,Ag,Au在S位掺杂的杂质能都低于在Mo位掺杂的杂质能,其在S位掺杂的体系的稳定性强于在Mo位掺杂的体系。在S位掺杂时,杂质与最近邻的Mo,S原子的键长都发生了畸变,畸变率最大的是dAu-Mo,达23.8%。与单层MoS_2的超胞相比,掺杂体系的禁带中出现了4条新能级,导带和价带的能量向低能区移动。杂质原子周围存在着电荷聚集,同时也存在电荷损失。     

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.     

A predictive model for interfacial thermal conductance in surface metallized diamond aluminum matrix composites

As promising thermal management materials with tailored thermal expansion and light weight, diamond/aluminum composites have not exhibited desirable thermal conductivity (TC) yet, due to poor interfacial thermal conductance (ITC) between diamond and aluminum. Although some experimental studies have been made to improve the ITC by means of diamond surface metallization, there are no systematic theoretical evaluations of the influences of interface layers’ structures on the ITC yet. In terms of the components of diamond/Al interface layer, a carbide–metal–intermetallic, multi-layered interface model was established in this work, and the effects of different components and structures of interface layers on the ITC and TC of the surface metallized diamond/Al composites were predicted. The calculated results indicate that, basically, an interface layer of nanoscale thickness with high TC and large sound velocity is desirable to achieve high ITC. Under this premise, W and Mo interface layers are proposed to be the most promising candidates to improve the thermal performance of diamond/Al composites.     

Thermal resistance of nanoscopic liquid-liquid interfaces: dependence on chemistry and molecular architecture

Systems with nanoscopic features contain a high density of interfaces. Thermal transport in such systems can be governed by the resistance to heat transfer, the Kapitza resistance (RK), at the interface. Although soft interfaces, such as those between immiscible liquids or between a biomolecule and solvent, are ubiquitous, few studies of thermal transport at such interfaces have been reported. Here we characterize the interfacial conductance, 1/RK, of soft interfaces as a function of molecular architecture, chemistry, and the strength of cross-interfacial intermolecular interactions through detailed molecular dynamics simulations. The conductance of various interfaces studied here, for example, water-organic liquid, water-surfactant, surfactant-organic liquid, is relatively high (in the range of 65-370 MW/m2 K) compared to that for solid-liquid interfaces ( approximately 10 MW/m2 K). Interestingly, the dependence of interfacial conductance on the chemistry and molecular architecture cannot be explained solely in terms of either bulk property mismatch or the strength of intermolecular attraction between the two phases. The observed trends can be attributed to a combination of strong cross-interface intermolecular interactions and good thermal coupling via soft vibration modes present at liquid-liquid interfaces.     

Pt effects in γ-Ni(Al)/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> adhesion

We present a systematic first-principles density-functional theory (DFT) study of the effects of Pt on the adhesion of the γ-Ni(Al)/α-Al₂O₃ interface, in a close comparison with those of Hf and S. Both the thermodynamically preferred Al-rich and the stoichiometric interfaces are considered. S is found to segregate to and substantially weaken both interfaces. Hf can pin S in bulk γ-Ni even at temperatures as high as 1,600 K, effectively inhibiting S segregation, while Pt cannot, due to phonon effects. For the stronger, Al-rich interface, both Hf and Pt have larger heats of segregation than S, inhibiting S segregation through preferential segregation. For the weaker, stoichiometric interface, Hf can significantly strengthen its adhesion to be as large as that of the Al-rich interface, and also inhibit S segregation through preferential segregation. Pt, as a contrast, can neither inhibit S segregation nor directly enhance the interface bonding.     

Transformation of monolayer MoS<Subscript>2</Subscript> into multiphasic MoTe<Subscript>2</Subscript>: Chalcogen atom-exchange synthesis route

Molybdenum ditelluride (MoTe2),which is an important transition-metal dichalcogenide,has attracted considerable interest owing to its unique properties,such as its small bandgap and large Seebeck coefficient.However,the batch production of monolayer MoTe2 has been rarely reported.In this study,we demonstrate the synthesis of large-domain (edge length exceeding 30 μm),monolayer MoTe2 from chemical vapor deposition-grown monolayer MoS2 using a chalcogen atom-exchange synthesis route.An in-depth investigation of the tellurization process reveals that the substitution of S atoms by Te is prevalently initiated at the edges and grain boundaries of the monolayer MoS2,which differs from the homogeneous selenization of MoS2 flakes with the formation of alloyed Mo-S-Se hybrids.Moreover,we detect a large compressive strain (approximately-10％) in the transformed MoTe2 lattice,which possibly drives the phase transition from 2H to 1T'at the reaction temperature of 500 ℃.This phase change is substantiated by experimental facts and first-principles calculations.This work introduces a novel route for the templated synthesis of two-dimensional layered materials through atom substitutional chemistry and provides a new pathway for engineering the strain and thus the intriguing physics and chemistry.     

Quasi-freestanding,striped WS2 monolayer with an invariable band gap on Au(001)

Revealing the structural/electronic features and interfacial interactions of monolayer MoS2 and WS2 on metals is essential to evaluating the performance of related devices.In this study,we focused on the atomic-scale features of monolayer WS2 on Au(001) synthesized via chemical vapor deposition.Scanning tunneling microscopy and spectroscopy reveal that the WS2/Au(001) system exhibits a striped superstructure similar to that of MoS2/Au(001) but weaker interfacial interactions,as evidenced by experimental and theoretical investigations.Specifically,the WS2/Au(001) band gap exhibits a relatively intrinsic value of ～ 2.0 eV.However,the band gap can gradually decrease to ～ 1.5 eV when the sample annealing temperature increases from ～370 to 720 ℃.In addition,the doping level (or Fermi energy) of monolayer WS2/Au(001) varies little over the valley and ridge regions of the striped patterns because of the homogenous distributions of point defects introduced by annealing.Briefly,this work provides an in-depth investigation into the interfacial interactions and electronic properties of monolayer MX2 on metal substrates.     

Electron and phonon transport in Au nanoparticle decorated graphene nanoplatelet nanostructured paper

Monodispersed Au nanoparticles are synthesized on the surface of exfoliated graphene nanoplatelets (GNP) in the presence of polyethyleneimine (PEI) with microwave assisted heating. A highly structured layered Au/GNP "paper" with good flexibility and mechanical robustness is prepared by vacuum assisted self-assembly. The thermal and electrical conductivity of the hybrid paper with and without the Au nanoparticles are investigated after different experimental processing conditions including thermal annealing and cold compaction. Annealing effectively decomposes and removes the adsorbed PEI molecules and improves thermal contact between Au/GNP particles, whereas cold compaction reduces porosity and induces stronger alignment of the Au/GNP within the hybrid paper. Both approaches lead to improvement in electrical and thermal conductivity. It is also found that adjacent GNP particles are electrically connected by the Au nanoparticles but thermally disconnected. It is believed that phonons are scattered at the Au/GNP interfaces, whereas electrons can tunnel across this interface, resulting in a separation of electron and phonon transport within this hybrid paper.     

First-Principles Study of the Polar TiC／Ti Interface

The interface structure, work of adhesion, and bonding character of the polar TiC/Ti interface have been examined by the first-principles density functional plane-wave pseudopotential calculations. Both Ti- and C-terminated interfaces including six different interface structures were calculated, which present quite different features. For the Ti-terminated interface, the interfacial Ti-Ti bond has a strong metallic and weak covalent character; while for the C-terminated interface, the interfacial bond is a strong polar covalent interaction between the Ti-3d and C-2p orbital.The work of adhesion of C-terminated interface is nearly 9 J/m2 stronger than that of the Ti-terminated. It is found that each termination has relatively large work of adhesion, which is consistent with other polar interfaces.     

Lattice Transformation from 2D to Quasi 1D and Phonon Properties of Exfoliated ZrS2 and ZrSe2

Recent reports on thermal and thermoelectric properties of emerging 2D materials have shown promising results. Among these materials are Zirconium-based chalcogenides such as zirconium disulfide (ZrS₂), zirconium diselenide (ZrSe₂), zirconium trisulfide (ZrS₃), and zirconium triselenide (ZrSe₃). Here, the thermal properties of these materials are investigated using confocal Raman spectroscopy. Two different and distinctive Raman signatures of exfoliated ZrX₂ (where X = S or Se) are observed. For 2D-ZrX₂, Raman modes are in alignment with those reported in literature. However, for quasi 1D-ZrX₂, Raman modes are identical to exfoliated ZrX₃ nanosheets, indicating a major lattice transformation from 2D to quasi-1D. Raman temperature dependence for ZrX₂ are also measured. Most Raman modes exhibit a linear downshift dependence with increasing temperature. However, for 2D-ZrS₂, a blueshift for A1g mode is detected with increasing temperature. Finally, phonon dynamics under optical heating for ZrX₂ are measured. Based on these measurements, the calculated thermal conductivity and the interfacial thermal conductance indicate lower interfacial thermal conductance for quasi 1D-ZrX₂ compared to 2D-ZrX₂, which can be attributed to the phonon confinement in 1D. The results demonstrate exceptional thermal properties for Zirconium-based materials, making them ideal for thermoelectric device applications and future thermal management strategies.     

Probing Anisotropic Thermal Conductivity of Transition Metal Dichalcogenides MX2 (M = Mo,W and X = S,Se) using Time‐Domain Thermoreflectance

Transition metal dichalcogenides (TMDs) are a group of layered 2D semiconductors that have shown many intriguing electrical and optical properties. However, the thermal transport properties in TMDs are not well understood due to the challenges in characterizing anisotropic thermal conductivity. Here, a variable‐spot‐size time‐domain thermoreflectance approach is developed to simultaneously measure both the in‐plane and the through‐plane thermal conductivity of four kinds of layered TMDs (MoS₂, WS₂, MoSe₂, and WSe₂) over a wide temperature range, 80–300 K. Interestingly, it is found that both the through‐plane thermal conductivity and the Al/TMD interface conductance depend on the modulation frequency of the pump beam for all these four compounds. The frequency‐dependent thermal properties are attributed to the nonequilibrium thermal resistance between the different groups of phonons in the substrate. A two‐channel thermal model is used to analyze the nonequilibrium phonon transport and to derive the intrinsic thermal conductivity at the thermal equilibrium limit. The measurements of the thermal conductivities of bulk TMDs serve as an important benchmark for understanding the thermal conductivity of single‐ and few‐layer TMDs.     

Methylammonium cation deficient surface for enhanced binding stability at TiO<Subscript>2</Subscript>/CH<Subscript>3</Subscript>NH<Subscript>3</Subscript>PbI<Subscript>3</Subscript> interface

Heterojunction interfaces in perovskite solar cells play an important role in enhancing their photoelectric properties and stability.Till date,the precise lattice arrangement at TiO2/CH3NH3PbI3 heterojunction interfaces has not been investigated clearly.Here,we examined a TiO2/CH3NH3PbI3 interface and found that a heavy atomic layer exists in such interfaces,which is attributed to the vacancies of methylammonium (MA) cation groups.Further,first-principles calculation results suggested that an MA cation-deficient surface structure is beneficial for a strong heterogeneous binding between TiO2 and CH3NH3PbI3 to enhance the interface stability.Our research is helpful for further understanding the detailed interface atom arrangements and provides references for interfacial modification in perovskite solar cells.     

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.