Transforming friction: unveiling sliding-induced phase transitions in CVD-grown WS2 monolayers under single-asperity sliding nanocontacts.

Transition metal dichalcogenides (TMDs) exhibit diverse properties across different phases, making them promising materials for various engineering applications. In the present work, we employed a comprehensive approach, combining experimental investigations and computational simulations to elucidate the remarkable tunable frictional characteristics of chemical vapor deposition (CVD) grown WS2 monolayers through the sliding-induced transitions between the 1H and 1T' phases. Our atomic force microscopy (AFM) measurements reveal a significant contrast in friction between the two phases, with the 1H phase displaying higher friction (∼52%) than the 1T' phase. Surprisingly, under repeated scanning at constant stress, the friction of the 1H phase decreases, eventually matching the lower friction values of the 1T' phase. It was observed that the phase transformation is irreversible and is strongly dependent on contact stresses and is accelerated as the contact stress is increased by increasing the applied normal load. Molecular dynamics (MD) simulations provide further insights into the phase transition mechanism, highlighting the role of localized lateral stress and strain induced by sliding an AFM tip on the 1H phase. The simulations confirm that sliding induced localized lateral strain plays a crucial role in the phase transition, ultimately resulting in a decrease in friction. Moreover, our simulations unveil an intriguing connection between friction, potential energy surfaces, and the localized lateral strain during the phase transformation process. Our findings not only offer insights into the tribological properties of TMD materials but also open new possibilities for tailoring their performance in various applications where reducing friction and wear is crucial.

Superlubricity and Stress-Shielding of Graphene Enables Ultra Scratch-Resistant Glasses.

Glasses, when subjected to scratch loading, incur damages affecting their optical and mechanical integrity. Here, it is demonstrated that silica glasses protected with mechanically exfoliated few-layer graphene sheets can exhibit remarkable improvement in scratch resistance. To this extent, the friction and wear characteristics of silica glasses with exfoliated graphene using atomic force microscopy (AFM) are explored. The friction forces recorded during AFM scratch tests of the graphene-glass surfaces at multiple loads exhibit ∼98% reduction compared to that of the bare silica glass, with the friction coefficient falling in the superlubricity regime. This dramatic reduction in friction achieved by the graphene sheets results in significantly lower wear of the graphene-glass surfaces postscratching. Further investigations employing atomistic simulations reveal that the stress-shielding mechanism is due to the reduced deformation of graphene-glass surfaces, thereby curtailing the overall damage. Altogether, the present work provides a new fillip toward the development of glasses with enhanced scratch resistance exploiting two-dimensional coatings.

Rapid quantification of the adulteration of pomegranate juices by Raman spectroscopy and chemometrics.

The juice drink industry has repeatedly been exposed to adulteration. Unscrupulous producers, for example, use cheap juice for substitution in the pursuit of more significant economic benefits, which presents a tremendous challenge for the control of the quality of drinks. The objective of this study was to apply Raman spectroscopy combined with chemometrics to rapidly quantify the adulteration concentration of apple juice or grape juice in pomegranate juice. Two supervised learning algorithms: partial least squares regression (PLSR) and support vector machine regression (SVR) were used to analyze the Raman spectra of 114 samples. The coefficient of determination (R2), root mean square error (RMSE), and residual prediction deviation (RPD) of the prediction set when using PLSR and SVR to predict the adulterated concentration of apple juice in pomegranate juice were 0.9357 and 0.9465, 6.446% and 5.974%, 3.945 and 4.322, respectively. The R2, RMSE, and RPD of the prediction set when using PLSR and SVR to predict the adulteration concentration of grape juice in pomegranate juice were 0.9501 and 0.9502, 6.334% and 5.571%, and 4.475 and 4.481, respectively. It was concluded that Raman spectroscopy combined with chemometrics has excellent potential for application as a rapid quantitative method to detect adulterated concentrations of pomegranate juice.

Adsorption behavior of long-chain perfluoroalkyl substances on hydrophobic surface: A combined molecular characterization and simulation study.

Hydrophobic interaction is a prevalent sorption mechanism of poly- and perfluoroalkyl substances (PFAS) in natural and engineered environments. In this study, we combined quartz crystal microbalance with dissipation (QCM-D), atomic force microscope (AFM) with force mapping, and molecular dynamics (MD) simulation to probe the molecular behavior of PFAS at the hydrophobic interface. On a CH3-terminated self-assembled monolayer (SAM), perfluorononanoic acid (PFNA) showed ∼2-fold higher adsorption than perfluorooctane sulfonate (PFOS) that has the same fluorocarbon tail length but a different head group. Kinetic modeling using the linearized Avrami model suggests that the PFNA/PFOS-surface interaction mechanisms can evolve over time. This is confirmed by AFM force-distance measurements, which shows that while the adsorbed PFNA/PFOS molecules mostly lay flat, a portion of them formed aggregates/hierarchical structures of 1-10 nm in size after lateral diffusion on surface. PFOS showed a higher affinity to aggregate than PFNA. Association with air nanobubbles is observed for PFOS but not PFNA. MD simulations further showed that PFNA has a greater tendency than PFOS to have its tail inserted into the hydrophobic SAM, which can enhance adsorption but limit lateral diffusion, consistent with the relative behavior of PFNA/PFOS in QCM and AFM experiments. This integrative QCM-AFM-MD study reveals that the interfacial behavior of PFAS molecules can be heterogeneous even on a relatively homogeneous surface.

Nanoscale friction and wear behavior of a CVD-grown aged WS2 monolayer: the role of wrinkles and surface chemistry.

Friction reduction by transition metal dichalcogenide (TMD) monolayers is well documented; however, wrinkle formation on the surface of TMDs takes place due to strain relaxation over time and leads to the deterioration of the tribological properties at a small scale. Herein, we report the role of wrinkles on the wear behavior of a chemical vapor deposition (CVD) grown aged WS2 monolayer and the comparison with wrinkle-free regions. Atomic force microscopy (AFM) was utilized to perform load-dependent experiments, and we noticed that the wear initiated near wrinkles resulted in the disintegration of the monolayer. In contrast, in the wrinkle-free regions, wear occurred at significantly higher loads, similar to that of freshly grown WS2, although the coefficient of friction (COF) was increased due to the changes in surface chemistry as a result of aging, which was confirmed using X-ray photoelectron spectroscopy (XPS). In the presence of wrinkles, a ten-fold reduction in the load-carrying capacity was observed compared to the wrinkle-free regions. Molecular dynamics (MD) simulations were used to corroborate experimental findings, which demonstrate the role of wrinkles in the initiation of wear due to the stress concentration under sliding nanocontacts near the wrinkles. In addition, simulations help establish a relationship between the adsorbed chemical species on the surface and increased COF.

Molecular dynamics study on thermal conductance between a nanotip and a substrate under vertical forces and horizontal sliding.

The heat transfer between a nanotip and its substrate is extremely complex but is a key factor in determining the measurement accuracy in tip-assisted nanomanufacturing and thermometry. In this work, the heat transfer from the nanotip to the substrate during sliding is investigated using molecular dynamics simulations. Interfacial interaction and bond formation are analyzed during the sliding process. The results show that the increase of vertical force would greatly improve the interface thermal conductance between the nanotip and the substrate. It is found that more bonds are formed and there are larger contact areas at the interface. In addition, we found that the thermal conductivity of the nanotip is another obstacle for heat transfer between the tip and substrate and it is greatly limited by the nanotip diameter near contact which is close to or even smaller than the phonon mean free path. Meanwhile, the dynamic formation and breakage of the covalent bonds during the sliding could gradually smoothen the tip apex and enhance the thermal transport at the interface. This work provides guidance for the thermal design of a nanotip-substrate system for nanoscale thermal transport measurements.

Terahertz Emission Spectroscopy of Ultrafast Coupled Spin and Charge Dynamics in Nanometer Ferromagnetic Heterostructures.

Due to its high sensitivity and because it does not rely on the magneto-optical response, terahertz (THz) emission spectroscopy has been used as a powerful time-resolved tool for investigating ultrafast demagnetization and spin current dynamics in nanometer-thick ferromagnetic (FM)/heavy metal (HM) heterostructures. Here, by changing the order of the conductive HM coating on the FM nanometer film, the dominant electric dipole contribution to the laser-induced THz radiation can be unraveled from the ultrafast magnetic dipole. Furthermore, to take charge equilibration into account, we separate the femtosecond laser-induced spin-to-charge converted current and the instantaneous discharging current within the illuminated area. The THz emission spectroscopy gives us direct information into the coupled spin and charge dynamics during the first moments of the light-matter interaction. Our results also open up new perspectives to manipulate and optimize the ultrafast charge current for promising high-performance and broadband THz radiation.

Stochastic Local Breakdown of Oxide Film on Ni from Identical-Location Imaging: One Single Site at a Time.

The electrochemical breakdown of a metal oxide film can directly affect the performance of functional electrochemical devices. However, revealing the structural insight into the breakdown sites is challenging because of heterogeneity: different breakdown sites are spatially distributed over the surface. Herein, we combine scanning electrochemical cell microscopy with identical-location microscopies to reveal the heterogeneity in the breakdown of NiO film on Ni in a site-by-site manner. Local critical breakdown potential varies by ∼500 mV, corresponding to an excess energy of 0.02-0.12 J/m2. Correlative composition imaging using time-of-flight secondary ion mass spectrometry shows Ni crystal grains with thinner NiO films are more resistant to breakdown. This high resistance is explained using classical nucleation theory, where the electrical energy is affected by the film thickness through the local interfacial capacitance. The correlative imaging approach overcomes the issue of heterogeneity, providing conclusive insight into the stability of the electrochemical interfaces.

Photoinduced large polaron transport and dynamics in organic-inorganic hybrid lead halide perovskite with terahertz probes.

Organic-inorganic hybrid metal halide perovskites (MHPs) have attracted tremendous attention for optoelectronic applications. The long photocarrier lifetime and moderate carrier mobility have been proposed as results of the large polaron formation in MHPs. However, it is challenging to measure the effective mass and carrier scattering parameters of the photogenerated large polarons in the ultrafast carrier recombination dynamics. Here, we show, in a one-step spectroscopic method, that the optical-pump and terahertz-electromagnetic probe (OPTP) technique allows us to access the nature of interplay of photoexcited unbound charge carriers and optical phonons in polycrystalline CH3NH3PbI3 (MAPbI3) of about 10 µm grain size. Firstly, we demonstrate a direct spectral evidence of the large polarons in polycrystalline MAPbI3. Using the Drude-Smith-Lorentz model along with the FrÓ§hlich-type electron-phonon (e-ph) coupling, we determine the effective mass and scattering parameters of photogenerated polaronic carriers. We discover that the resulting moderate polaronic carrier mobility is mainly influenced by the enhanced carrier scattering, rather than the polaron mass enhancement. While, the formation of large polarons in MAPbI3 polycrystalline grains results in a long charge carrier lifetime at room temperature. Our results provide crucial information about the photo-physics of MAPbI3 and are indispensable for optoelectronic device development with better performance.

Nanoscale Colocalized Electrochemical and Structural Mapping of Metal Dissolution Reaction.

Understanding the structure-activity relationship in electrochemical metal dissolution reactions is fundamentally important, from designing higher density batteries to mitigating corrosions. The kinetics of metal dissolution reaction is highly dependent on surface structures, including grain boundaries and local defects. However, directly probing the electrochemical activity at these sites is difficult because the conventional bulk electrochemistry measures an averaged kinetics, obscuring the structure-activity correlation. Herein, we report the colocalized mapping of an electrochemical metal dissolution reaction using Ag as a model system. The local dissolution kinetics is voltammetrically mapped via scanning electrochemical cell microscopy (SECCM), which is correlated with local structures obtained via colocalized electron backscattering diffraction (EBSD). Individual pits of ∼200 nm are formed, and their geometries suggest dissolution is fastest in the direction parallel to the {111} planes. Enhanced dissolution kinetics is observed at the high-angle grain boundaries but not at twin boundaries, which are attributed to the different binding energy of Ag atoms. Furthermore, the faster local dissolution correlates with the geometrically necessary dislocation density. The work demonstrates the importance of nanoscale local electrochemical mapping and colocalized microscopic measurement in obtaining the structure-activity relationship for electrochemical reactions at complex interfaces.

Origin of Nanoscale Friction Contrast between Supported Graphene, MoS2, and a Graphene/MoS2 Heterostructure.

Ultralow friction can be achieved with 2D materials, particularly graphene and MoS2. The nanotribological properties of these different 2D materials have been measured in previous atomic force microscope (AFM) experiments sequentially, precluding immediate and direct comparison of their frictional behavior. Here, friction is characterized at the nanoscale using AFM experiments with the same tip sliding over graphene, MoS2, and a graphene/MoS2 heterostructure in a single measurement, repeated hundreds of times, and also measured with a slowly varying normal force. The same material systems are simulated using molecular dynamics (MD) and analyzed using density functional theory (DFT) calculations. In both experiments and MD simulations, graphene consistently exhibits lower friction than the MoS2 monolayer and the heterostructure. In some cases, friction on the heterostructure is lower than that on the MoS2 monolayer. Quasi-static MD simulations and DFT calculations show that the origin of the friction contrast is the difference in energy barriers for a tip sliding across each of the three surfaces.

The role of mechanical force on the kinetics and dynamics of electrochemical redox reactions on graphene.

Electrochemical reactions are a critical class of processes strongly influenced by atomic scale effects, where the relationships between local chemical composition, stress, strain, and reactivity are not well understood. Here we investigate the relationship between applied stress and reaction rates for the oxygen evolution reaction on multi-layered graphene using conductive atomic force microscopy. During the reaction, oxygen groups accumulate on the surface and the oxygenation rate increases with applied load. The results also show that the rate is not uniform across the surface, where local edges and defects are more reactive than the basal plane. The results presented here are interpreted in the context of transition state theory, where applied load over the reaction coordinate linearly modifies the energy landscape. This work motivates the general efficacy of atomic force microscopy as a tool to study relationships between local mechanical surface effects and electrochemical reactivity.

Load-Dependent Friction Hysteresis on Graphene.

Nanoscale friction often exhibits hysteresis when load is increased (loading) and then decreased (unloading) and is manifested as larger friction measured during unloading compared to loading for a given load. In this work, the origins of load-dependent friction hysteresis were explored through atomic force microscopy (AFM) experiments of a silicon tip sliding on chemical vapor deposited graphene in air, and molecular dynamics simulations of a model AFM tip on graphene, mimicking both vacuum and humid air environmental conditions. It was found that only simulations with water at the tip-graphene contact reproduced the experimentally observed hysteresis. The mechanisms underlying this friction hysteresis were then investigated in the simulations by varying the graphene-water interaction strength. The size of the water-graphene interface exhibited hysteresis trends consistent with the friction, while measures of other previously proposed mechanisms, such as out-of-plane deformation of the graphene film and irreversible reorganization of the water molecules at the shearing interface, were less correlated to the friction hysteresis. The relationship between the size of the sliding interface and friction observed in the simulations was explained in terms of the varying contact angles in front of and behind the sliding tip, which were larger during loading than unloading.

Dynamics of atomic stick-slip friction examined with atomic force microscopy and atomistic simulations at overlapping speeds.

Atomic force microscopy (AFM) and atomistic simulations of atomic friction with silicon oxide tips sliding on Au(111) are conducted at overlapping speeds. Experimental data unambiguously reveal a stick-slip friction plateau above a critical scanning speed, in agreement with the thermally activated Prandtl-Tomlinson (PTT) model. However, friction in experiments is larger than in simulations. PTT energetic parameters for the two are comparable, with minor differences attributable to the contact area's influence on the barrier to slip. Recognizing that the attempt frequency may be determined by thermal vibrations of the larger AFM tip mass or instrument noise fully resolves the discrepancy. Thus, atomic stick-slip is well described by the PTT model if sources of slip-assisting energy are accounted for.

Oscillatory motion in layered materials: graphene, boron nitride, and molybdenum disulfide.

Offset-driven self-retraction and oscillatory motion of bilayer graphene has been observed experimentally and is potentially relevant for nanoscale technological applications. In a previous article, we showed that friction between laterally offset graphene layers is controlled by roughness and proposed a simple reduced-order model based on density-functional theory (DFT) and molecular dynamics (MD) data, with which predictions on the experimental size-scale could be made. In this article, we extend our study to other layered materials, with emphasis on boron nitride (BN) and molybdenum disulfide (MoS2). Using MD and DFT simulations of these systems and a generalized version of the reduced-order model, we predict that BN will exhibit behavior similar to graphene (heavily-damped oscillation with a decay rate that increases with roughness) and that MoS2 shows no oscillatory behavior even in the absence of roughness. This is attributed to the higher energy barrier for sliding in MoS2 as well as the surface structure. Our generalized reduced-order model provides a guide to predicting and tuning experimental oscillation behavior using a few parameters that can be derived from simulation data.

Atomistic simulation of the load dependence of nanoscale friction on suspended and supported graphene.

Suspended graphene exhibits distinct behavior in which nanoscale friction first increases and then decreases with load; this is in contrast to the monotonic increase of friction with load exhibited by most materials, including graphene supported by a substrate. In this work, these friction trends are reproduced for the first time using molecular dynamics simulations of a nanoscale probe scanning on suspended and supported graphene. The atomic-scale detail available in the simulations is used to correlate friction trends to the presence and size of a wrinkle on the graphene surface in front of the probe. The simulations also provide information about how frictional load dependence is affected by the size of the graphene, the size of the probe, and the strength of the interaction between graphene and probe.

The role of roughness-induced damping in the oscillatory motion of bilayer graphene.

A multi-scale theoretical model is presented that is the first to offer quantitative agreement with experimental measurements of self-retraction and oscillation of bilayer graphene. The model integrates density-functional theory calculations of the energetics driving flake retraction and molecular-dynamics simulations capturing the dynamic response of laterally-offset rough surfaces. We demonstrate that nanoscale roughness explains self-retraction motion and propose a recipe for tuning that motion by controlling friction.

Thermal conductivity in nanostructured films: from single cellulose nanocrystals to bulk films.

We achieved a multiscale description of the thermal conductivity of cellulose nanocrystals (CNCs) from single CNCs (∼0.72-5.7 W m(-1) K(-1)) to their organized nanostructured films (∼0.22-0.53 W m(-1) K(-1)) using experimental evidence and molecular dynamics (MD) simulation. The ratio of the approximate phonon mean free path (∼1.7-5.3 nm) to the lateral dimension of a single CNC (∼5-20 nm) suggested a contribution of crystal-crystal interfaces to polydisperse CNC film's heat transport. Based on this, we modeled the thermal conductivity of CNC films using MD-predicted single crystal and interface properties along with the degree of CNC alignment in the bulk films using Hermans order parameter. Film thermal conductivities were strongly correlated to the degree of CNC alignment and the direction of heat flow relative to the CNC chain axis. The low interfacial barrier to heat transport found for CNCs (∼9.4 to 12.6 m(2) K GW(-1)), and their versatile alignment capabilities offer unique opportunities in thermal conductivity control.