Hydrodynamic slip characteristics of shear-driven water flow in nanoscale carbon slits.

This paper reports on the effects of shear rate and interface modeling parameters on the hydrodynamic slip length (LS) for water-graphite interfaces calculated using non-equilibrium molecular dynamics. Five distinct non-bonded solid-liquid interaction parameters were considered to assess their impact on LS. The interfacial force field derivations included sophisticated electronic structure calculation-informed and empirically determined parameters. All interface models exhibited a similar and bimodal LS response when varying the applied shear rate. LS in the low shear rate regime (LSR) is in good agreement with previous calculations obtained through equilibrium molecular dynamics. As the shear rate increases, LS sharply increases and asymptotes to a constant value in the high shear regime (HSR). It is noteworthy that LS in both the LSR and HSR can be characterized by the density depletion length, whereas solid-liquid adhesion metrics failed to do so. For all interface models, LHSR calculations were, on average, ∼28% greater than LLSR, and this slip jump was confirmed using the SPC/E and TIP4P/2005 water models. To address the LS transition from the LSR to the HSR, the viscosity of water and the interfacial friction coefficient were investigated. It was observed that in the LSR, the viscosity and friction coefficient decreased at a similar rate, while in the LSR-to-HSR transition, the friction coefficient decreased at a faster rate than the shear viscosity until they reached a new equilibrium, hence explaining the LS-bimodal behavior. This study provides valuable insights into the interplay between interface modeling parameters, shear rate, and rheological properties in understanding hydrodynamic slip behavior.

Thermal transport across flat and curved gold-water interfaces: Assessing the effects of the interfacial modeling parameters.

The present investigation assesses a variety of parameters available in the literature to model gold-water interfaces using molecular dynamics simulations. The study elucidates the challenges of characterizing the solid-liquid affinity of highly hydrophilic gold-water interfaces via wettability. As an alternative, the local pairwise interaction energy was used to describe the solid-liquid affinity of flat and curved surfaces, where for the latter, the calculation of a contact angle becomes virtually impossible. Regarding the heat transfer properties of different interface models (flat and curved), partly conclusive trends were observed between the total pairwise interaction energy and the thermal boundary conductance. It was observed that the solid surface structure, interfacial force field type, and force field parameters created a characteristic bias in the interfacial water molecules (liquid structuring). Consequently, a study of the liquid depletion layer provided better insight into the interfacial heat transfer among different interfaces. By computing the density depletion length, which describes the deficit or surplus of energy carries (water molecules) near the interface, a proper characterization of the thermal boundary conductance was obtained for the different gold-water interfaces. It was observed that the interfacial heat transfer is favored when the water molecules organize in cluster-like structures near the interface, by a surplus of water molecules at the interface, i.e., lower density depletion length, and by the closeness of water to the solid atoms.

Effects of interfacial molecular mobility on thermal boundary conductance at solid-liquid interface.

The effects of interfacial molecular mobility on the thermal boundary conductance (TBC) across graphene-water and graphene-perfluorohexane interfaces were investigated using non-equilibrium molecular dynamics simulations. The molecular mobility was varied by equilibrating nanoconfined water and perfluorohexane at different temperatures. The long-chain molecules of perfluorohexane exhibited a prominent layered structure, indicating a low molecular mobility, over a wide temperature range between 200 and 450 K. Alternatively, water increased its mobility at high temperatures, resulting in an enhanced molecular diffusion that significantly contributed to the interfacial thermal transport, in addition to the increasing vibrational carrier population at high temperatures. Furthermore, the TBC across the graphene-water interface exhibited a quadratic relationship with the rise in temperature, whereas for the graphene-perfluorohexane interface, a linear relationship was observed. The high rate of diffusion in interfacial water facilitated additional low-frequency modes, and a spectral decomposition of the TBC also indicated an enhancement in the same frequency range. Thus, the enhanced spectral transmission and higher molecular mobility of water with respect to perfluorohexane explained the difference in the thermal transport across the interfaces considered herein.

Effects of the Interfacial Modeling Approach on Equilibrium Calculations of Slip Length for Nanoconfined Water in Carbon Slits.

In this investigation, equilibrium molecular dynamics simulations were conducted to assess the influence of the interface modeling approach on the calculation of hydrodynamic slip in carbon nanochannels. A Green-Kubo formalism was implemented for the calculation of the slip length in water confined by graphite layers. The nonbonded interactions between solid and liquid atoms (interface models) were modeled using parameters optimized to represent the wetting behavior and adsorption energy curves from electronic structure calculations. Conventional carbon-oxygen-only interaction models were compared against comprehensive models able to represent the molecular-orientation-dependent energy of interaction. Quasi-universal relationships built under the premise of the slip length dependence on the water-graphite affinity and characterized by macroscopic wettability were critically assessed. It was found that the wetting behavior cannot fully characterize the hydrodynamic slip because interface models that produced the same surface wettability yielded different values of the friction coefficient. Alternatively, the density depletion length, used to characterize the interfacial liquid structuring and the availability of momentum carriers (interfacial water molecules), was able to accurately represent the slip length trends independently of the interface model. These findings reassert the importance of physically sound interface models to study interfacial transport properties and the need of reliable parameters and characterization procedures to support theoretical models that seek to unveil the inconsistencies in hydrodynamic slip calculations.

Water wettability of graphene and graphite, optimization of solid-liquid interaction force fields, and insights from mean-field modeling.

A simple mean-field model of carbon-water interactions was developed to predict the binding energy in classical simulations for graphene and graphite surfaces. Using this model, analytical expressions were derived to link microscopic parameters (such as the binding energy) with macroscopic wetting behavior (work of adhesion). Adding these expressions to an optimized mean-field model of wettability, the empirical relationship between the binding energy and the work of adhesion in classical simulations was formally explained. An orientation dependent mean-field model and the insight gained from mean field modeling of the binding energy were used to develop a method to optimize comprehensive carbon-water interaction potentials, where molecular orientation is taken into account using data from state-of-the-art high-resolution multibody electronic structure methods. This method eliminates the ambiguity of finding a set of four parameters by informing on the bounds for the parameter-search process using physics-informed constraints.

On the wettability transparency of graphene-coated silicon surfaces.

In order to better understand the behavior and governing characteristics of the wetting transparency phenomenon observed in graphene-coated surfaces, molecular dynamics simulations were coupled with a theoretical model. Graphene-coated silicon was selected for this analysis, due to potential applications of hybrid silicon-graphene materials as detectors in aqueous environments. The results indicate good agreement between the theory and simulations at the macroscopic conditions required to observe wetting transparency. A microscopic analysis was also conducted in order to identify the parameters, such as the interaction potential energy landscape and the interfacial liquid structure that govern the wetting behavior of graphene-coated surfaces. The interfacial liquid structure was found to be different between uncoated Si(100) and the graphene-coated version and very similar between uncoated Si(111) and the graphene-coated version. However, the concentration of liquid particles for both silicon surfaces was found to be very similar under transparent wetting conditions.

Wettability of graphitic-carbon and silicon surfaces: MD modeling and theoretical analysis.

The wettability of graphitic carbon and silicon surfaces was numerically and theoretically investigated. A multi-response method has been developed for the analysis of conventional molecular dynamics (MD) simulations of droplets wettability. The contact angle and indicators of the quality of the computations are tracked as a function of the data sets analyzed over time. This method of analysis allows accurate calculations of the contact angle obtained from the MD simulations. Analytical models were also developed for the calculation of the work of adhesion using the mean-field theory, accounting for the interfacial entropy changes. A calibration method is proposed to provide better predictions of the respective contact angles under different solid-liquid interaction potentials. Estimations of the binding energy between a water monomer and graphite match those previously reported. In addition, a breakdown in the relationship between the binding energy and the contact angle was observed. The macroscopic contact angles obtained from the MD simulations were found to match those predicted by the mean-field model for graphite under different wettability conditions, as well as the contact angles of Si(100) and Si(111) surfaces. Finally, an assessment of the effect of the Lennard-Jones cutoff radius was conducted to provide guidelines for future comparisons between numerical simulations and analytical models of wettability.

Effects of Moisture and Synthesis-Derived Contaminants on the Mechanical Properties of Graphene Oxide: A Molecular Dynamics Investigation.

This paper reports on the effects of the chemical composition of graphene oxide (GO) sheets on the mechanical properties of bulk GO. Three key factors were analyzed: (i) the oxygenated functional groups' concentration, (ii) the content of intersheet water (moisture), and (iii) the presence of residual contaminants observed from the synthesis of GO. Molecular dynamics simulations using the reactive force field ReaxFF were conducted to model tensile strength, indentation, and shear stress tests. The structural integrity of the carbon basal plane was the primary variable that determined mechanical behavior of GO slabs. Hydrogen-bond networks played an essential role in the tensile fracture mechanism, delaying the onset of fracture whenever strong hydrogen bonds existed in the intersheet space. The presence of interlayer sulfate ion contaminants negatively impacted the tensile strength, stiffness, and toughness of GO. Moreover, it was observed that intersheet sulfate ions improved the resistance to fracture of GO at low sulfur concentrations, while lower fracture strains were observed beyond a critical concentration. Alike the tensile stress findings, the indentation properties were determined by the integrity of the carbon basal plane. Our findings agree with experimental mechanical property measurements and reveal the importance of considering synthesis-derived contaminants in molecular models of GO.

Thermal Conductivity of ß-Phase Ga2O3 and (AlxGa1-x)2O3 Heteroepitaxial Thin Films.

Heteroepitaxy of ß-phase gallium oxide (ß-Ga2O3) thin films on foreign substrates shows promise for the development of next-generation deep ultraviolet solar blind photodetectors and power electronic devices. In this work, the influences of the film thickness and crystallinity on the thermal conductivity of (2̅01)-oriented ß-Ga2O3 heteroepitaxial thin films were investigated. Unintentionally doped ß-Ga2O3 thin films were grown on c-plane sapphire substrates with off-axis angles of 0° and 6° toward ⟨112̅0⟩ via metal-organic vapor phase epitaxy (MOVPE) and low-pressure chemical vapor deposition. The surface morphology and crystal quality of the ß-Ga2O3 thin films were characterized using scanning electron microscopy, X-ray diffraction, and Raman spectroscopy. The thermal conductivities of the ß-Ga2O3 films were measured via time-domain thermoreflectance. The interface quality was studied using scanning transmission electron microscopy. The measured thermal conductivities of the submicron-thick ß-Ga2O3 thin films were relatively low as compared to the intrinsic bulk value. The measured thin film thermal conductivities were compared with the Debye-Callaway model incorporating phononic parameters derived from first-principles calculations. The comparison suggests that the reduction in the thin film thermal conductivity can be partially attributed to the enhanced phonon-boundary scattering when the film thickness decreases. They were found to be a strong function of not only the layer thickness but also the film quality, resulting from growth on substrates with different offcut angles. Growth of ß-Ga2O3 films on 6° offcut sapphire substrates was found to result in higher crystallinity and thermal conductivity than films grown on on-axis c-plane sapphire. However, the ß-Ga2O3 films grown on 6° offcut sapphire exhibit a lower thermal boundary conductance at the ß-Ga2O3/sapphire heterointerface. In addition, the thermal conductivity of MOVPE-grown (2̅01)-oriented ß-(AlxGa1-x)2O3 thin films with Al compositions ranging from 2% to 43% was characterized. Because of phonon-alloy disorder scattering, the ß-(AlxGa1-x)2O3 films exhibit lower thermal conductivities (2.8-4.7 W/m·K) than the ß-Ga2O3 thin films. The dominance of the alloy disorder scattering in ß-(AlxGa1-x)2O3 is further evidenced by the weak temperature dependence of the thermal conductivity. This work provides fundamental insight into the physical interactions that govern phonon transport within heteroepitaxially grown ß-phase Ga2O3 and (AlxGa1-x)2O3 thin films and lays the groundwork for the thermal modeling and design of ß-Ga2O3 electronic and optoelectronic devices.

Ga2O3-on-SiC Composite Wafer for Thermal Management of Ultrawide Bandgap Electronics.

ß-phase gallium oxide (Ga2O3) is an emerging ultrawide bandgap (UWBG) semiconductor (EG ∼ 4.8 eV), which promises generational improvements in the performance and manufacturing cost over today's commercial wide bandgap power electronics based on GaN and SiC. However, overheating has been identified as a major bottleneck to the performance and commercialization of Ga2O3 device technologies. In this work, a novel Ga2O3/4H-SiC composite wafer with high heat transfer performance and an epi-ready surface finish has been developed using a fusion-bonding method. By taking advantage of low-temperature metalorganic vapor phase epitaxy, a Ga2O3 epitaxial layer was successfully grown on the composite wafer while maintaining the structural integrity of the composite wafer without causing interface damage. An atomically smooth homoepitaxial film with a room-temperature Hall mobility of ∼94 cm2/Vs and a volume charge of ∼3 × 1017 cm-3 was achieved at a growth temperature of 600 °C. Phonon transport across the Ga2O3/4H-SiC interface has been studied using frequency-domain thermoreflectance and a differential steady-state thermoreflectance approach. Scanning transmission electron microscopy analysis suggests that phonon transport across the Ga2O3/4H-SiC interface is dominated by the thickness of the SiNx bonding layer and an unintentionally formed SiOx interlayer. Extrinsic effects that impact the thermal conductivity of the 6.5 µm thick Ga2O3 layer were studied via time-domain thermoreflectance. Thermal simulation was performed to estimate the improvement of the thermal performance of a hypothetical single-finger Ga2O3 metal-semiconductor field-effect transistor fabricated on the composite substrate. This novel power transistor topology resulted in a ∼4.3× reduction in the junction-to-package device thermal resistance. Furthermore, an even more pronounced cooling effect is demonstrated when the composite wafer is implemented into the device design of practical multifinger devices. These innovations in device-level thermal management give promise to the full exploitation of the promising benefits of the UWBG material, which will lead to significant improvements in the power density and efficiency of power electronics over current state-of-the-art commercial devices.

Thermal Transport across SiC-Water Interfaces.

Thermal transport across interfaces made of 3C-type silicon carbide (SiC) and water was investigated by means of nonequilibrium classical molecular dynamics. The effects of different crystallographic planes and atomic surface terminations were studied, as it pertains to interfacial heat transfer. Hydrophilic and hydrophobic conditions were analyzed by modifying the interfacial bonding strength between the solid and liquid phases. The formation of structures in the liquid molecules close to the solid substrate was observed and found that such structures are sensitive to the uppermost atomic layer termination, the wettability condition, and the temperature of the system. It was found that the interfacial heat transfer and the wetting properties are not universally related and to obtain a more comprehensive description, it is required to include the structuring observed in the liquid phase at the interface. A reconciliation of the thermal boundary conductance calculations was found after the density depletion length was utilized as the descripting parameter.

Hydrodynamic slip in silicon nanochannels.

Equilibrium and nonequilibrium molecular dynamics simulations were performed to better understand the hydrodynamic behavior of water flowing through silicon nanochannels. The water-silicon interaction potential was calibrated by means of size-independent molecular dynamics simulations of silicon wettability. The wettability of silicon was found to be dependent on the strength of the water-silicon interaction and the structure of the underlying surface. As a result, the anisotropy was found to be an important factor in the wettability of these types of crystalline solids. Using this premise as a fundamental starting point, the hydrodynamic slip in nanoconfined water was characterized using both equilibrium and nonequilibrium calculations of the slip length under low shear rate operating conditions. As was the case for the wettability analysis, the hydrodynamic slip was found to be dependent on the wetted solid surface atomic structure. Additionally, the interfacial water liquid structure was the most significant parameter to describe the hydrodynamic boundary condition. The calibration of the water-silicon interaction potential performed by matching the experimental contact angle of silicon led to the verification of the no-slip condition, experimentally reported for silicon nanochannels at low shear rates.

Hydrodynamic slip length as a surface property.

Equilibrium and nonequilibrium molecular dynamics simulations were conducted in order to evaluate the hypothesis that the hydrodynamic slip length is a surface property. The system under investigation was water confined between two graphite layers to form nanochannels of different sizes (3-8 nm). The water-carbon interaction potential was calibrated by matching wettability experiments of graphitic-carbon surfaces free of airborne hydrocarbon contamination. Three equilibrium theories were used to calculate the hydrodynamic slip length. It was found that one of the recently reported equilibrium theories for the calculation of the slip length featured confinement effects, while the others resulted in calculations significantly hindered by the large margin of error observed between independent simulations. The hydrodynamic slip length was found to be channel-size independent using equilibrium calculations, i.e., suggesting a consistency with the definition of a surface property, for 5-nm channels and larger. The analysis of the individual trajectories of liquid particles revealed that the reason for observing confinement effects in 3-nm nanochannels is the high mobility of the bulk particles. Nonequilibrium calculations were not consistently affected by size but by noisiness in the smallest systems.

Solid-Liquid Thermal Transport and Its Relationship with Wettability and the Interfacial Liquid Structure.

Experiments and atomistic simulations have suggested the existence of a direct correlation between the wetting properties of a surface and heat transfer across it. In this investigation, molecular dynamics simulations of surface wettability and solid-liquid thermal transport were conducted in order to better understand the relationship between the surface chemistry and thermal transport. The wettability transparency of graphene-coated surfaces was considered in order to investigate heat transfer across a complex interface with similar wettability as a bare surface. The results indicate that the relationship between the interfacial heat transfer and wettability is not universal. The density depletion length was found to reconcile the thermal boundary conductance calculations for different bare and graphene-coated silicon surfaces.