Nanoscale Adhesion and Material Transfer at 2D MoS2-MoS2 Interfaces Elucidated by In Situ Transmission Electron Microscopy and Atomistic Simulations.

Low-dimensional materials, such as MoS2, hold promise for use in a host of emerging applications, including flexible, wearable sensors due to their unique electrical, thermal, optical, mechanical, and tribological properties. The implementation of such devices requires an understanding of adhesive phenomena at the interfaces between these materials. Here, we describe combined nanoscale in situ transmission electron microscopy (TEM)/atomic force microscopy (AFM) experiments and simulations measuring the work of adhesion (Wadh) between self-mated contacts of ultrathin nominally amorphous and nanocrystalline MoS2 films deposited on Si scanning probe tips. A customized TEM/AFM nanoindenter permitted high-resolution imaging and force measurements in situ. The Wadh values for nanocrystalline and nominally amorphous MoS2 were 604 ± 323 mJ/m2 and 932 ± 647 mJ/m2, respectively, significantly higher than previously reported values for mechanically exfoliated MoS2 single crystals. Closely matched molecular dynamics (MD) simulations show that these high values can be explained by bonding between the opposing surfaces at defects such as grain boundaries. Simulations show that as grain size decreases, the number of bonds formed, the Wadh and its variability all increase, further supporting that interfacial covalent bond formation causes high adhesion. In some cases, sliding between delaminated MoS2 flakes during separation is observed, which further increases the Wadh and the range of adhesive interaction. These results indicate that for low adhesion, the MoS2 grains should be large relative to the contact area to limit the opportunity for bonding, whereas small grains may be beneficial, where high adhesion is needed to prevent device delamination in flexible systems.

Effects of -H and -OH Termination on Adhesion of Si-Si Contacts Examined Using Molecular Dynamics and Density Functional Theory.

The contact between nanoscale single-crystal silicon asperities and substrates terminated with -H and -OH functional groups is simulated using reactive molecular dynamics (MD). Consistent with previous MD simulations for self-mated surfaces with -H terminations only, adhesion is found to be low at full adsorbate coverages, be it self-mated coverages of mixtures of -H and -OH groups, or just -OH groups. As the coverage reduces, adhesion increases markedly, by factors of ∼5 and ∼6 for -H-terminated surfaces and -OH-terminated surfaces, respectively, and is due to the formation of covalent Si-Si bonds; for -OH-terminated surfaces, some interfacial Si-O-Si bonds are also formed. Thus, covalent linkages need to be broken upon separation of the tip and substrate. In contrast, replacing -H groups with -OH groups while maintaining complete coverage leads to negligible increases in adhesion. This indicates that increases in adhesion require unsaturated sites. Furthermore, plane-wave density functional theory (DFT) calculations were performed to investigate the energetics of two Si(111) surfaces fully terminated by either -H or -OH groups. Importantly for the adhesion results, both DFT and MD calculations predict the correct trends for the relative bond strengths: Si-O > Si-H > Si-Si. This work supports the contention that prior experimental work observing strong increases in adhesion after sliding Si-Si nanoasperities over each other is due to sliding-induced removal of passivating species on the Si surfaces.

Acceleration of Diels-Alder reactions by mechanical distortion.

Challenges in quantifying how force affects bond formation have hindered the widespread adoption of mechanochemistry. We used parallel tip-based methods to determine reaction rates, activation energies, and activation volumes of force-accelerated [4+2] Diels-Alder cycloadditions between surface-immobilized anthracene and four dienophiles that differ in electronic and steric demand. The rate dependences on pressure were unexpectedly strong, and substantial differences were observed between the dienophiles. Multiscale modeling demonstrated that in proximity to a surface, mechanochemical trajectories ensued that were distinct from those observed solvothermally or under hydrostatic pressure. These results provide a framework for anticipating how experimental geometry, molecular confinement, and directed force contribute to mechanochemical kinetics.

Nanoscale Structure-Property Relations in Self-Regulated Polymer-Grafted Nanoparticle Composite Structures.

Using a model system of poly(methyl methacrylate)-grafted silica nanoparticles (PMMA-NP) and poly(styrene-ran-acrylonitrile) (SAN), we generate unique polymer nanocomposite (PNC) morphologies by balancing the degree of surface enrichment, phase separation, and wetting within the films. Depending on the annealing temperature and time, thin films undergo different stages of phase evolution, resulting in homogeneously dispersed systems at low temperatures, enriched PMMA-NP layers at the PNC interfaces at intermediate temperatures, and three-dimensional bicontinuous structures of PMMA-NP pillars sandwiched between two PMMA-NP wetting layers at high temperatures. Using a combination of atomic force microscopy (AFM), AFM nanoindentation, contact angle goniometry, and optical microscopy, we show that these self-regulated structures lead to nanocomposites with increased elastic modulus, hardness, and thermal stability compared to analogous PMMA/SAN blends. These studies demonstrate the ability to reliably control the size and spatial correlations of both the surface-enriched and phase-separated nanocomposite microstructures, which have attractive technological applications where properties such as wettability, toughness, and wear resistance are important. In addition, these morphologies lend themselves to substantially broader applications, including: (1) structural color applications, (2) tuning optical adsorption, and (3) barrier coatings.

What stress components drive mechanochemistry? A study of ZDDP tribofilm formation.

Zinc dialkyldithiophosphate (ZDDP), the most widely used antiwear additive in engine oils, has been extensively studied over the last few decades to help understand the origin of its effectiveness. Glassy phosphate-based tribofilms, approximately 100 nm thick, are often formed on surfaces sliding in ZDDP-containing oils, which help to prevent or reduce wear. Recent studies reveal that a combination of applied shear and compressive stresses drive mechanochemical reactions that promote tribofilm growth, and that growth is further accelerated by increased temperature. While recent work has shown that compressive stress alone is insufficient to form tribofilms, the individual effects of the shear stress and compressive stress are not fully understood. Here, shear and compressive stresses are studied separately by using different ratios of high-viscosity, high-traction fluids for testing. This allows the areal mean compressive and shear stresses in the fluid when confined at a loaded sliding interface, to be independently controlled while driving tribofilm growth, which is a system we refer to as a stress-controlled mechanochemical reactor. Tribofilms derived from a secondary ZDDP were generated using a tungsten carbide/tungsten carbide ball-on-disk contact in the full elastohydrodynamic lubrication (EHL) regime using a mini-traction machine (MTM), meaning that solid-solid contact is avoided. The MTM was equipped with a spacer layer imaging (SLIM) capability, permitting in situ measurement of the tribofilm thickness during its growth. The well-separated sliding surfaces generated by the high-viscosity fluids confirm that solid-solid contact is not required for tribofilm formation. Under these full fluid film EHL conditions, shear stress and temperature promote tribofilm growth in accordance with stress-augmented thermal activation. In contrast, under constant shear stress and temperature, compressive stress has the opposite effect, inhibiting tribofilm growth. Using the extended Eyring model for shear- and hydrostatic pressure-affected reaction kinetics, an activation energy of 0.54 ± 0.04 eV is found, consistent with prior studies of ZDDPs. The activation volume for shear stress is found to be 0.18 ± 0.06 nm3, while that for the compressive stress component is much smaller, at 0.010 ± 0.004 nm3. This not only confirms prior work supporting that shear stress drives tribofilm growth, but demonstrates and quantifies how compressive stress inhibits growth, consistent with the rate-limiting step in tribofilm growth involving a bond-breaking reaction. Implications of these findings are discussed.

A modified multibond model for nanoscale static friction.

Several key features of nanoscale friction phenomena observed in experiments, including the stick-slip to smooth sliding transition and the velocity and temperature dependence of friction, are often described by reduced-order models. The most notable of these are the thermal Prandtl-Tomlinson model and the multibond model. Here we present a modified multibond (mMB) model whereby a physically-based criterion-a critical bond stretch length-is used to describe interfacial bond breaking. The model explicitly incorporates damping in both the cantilever and the contacting materials. Comparison to the Fokker-Planck formalism supports the results of this new model, confirming its ability to capture the relevant physics. Furthermore, the mMB model replicates the near-logarithmic trend of increasing friction with lateral scanning speed seen in many experiments. The model can also be used to probe both correlated and uncorrelated stick slip. Through greater understanding of the effects of damping and noise in the system and the ability to more accurately simulate a system with multiple interaction sites, this model extends the range of frictional systems and phenomena that can be investigated. This article is part of the theme issue 'Nanocracks in nature and industry'.

Ultrahigh strength and shear-assisted separation of sliding nanocontacts studied in situ.

The behavior of materials in sliding contact is challenging to determine since the interface is normally hidden from view. Using a custom microfabricated device, we conduct in situ, ultrahigh vacuum transmission electron microscope measurements of crystalline silver nanocontacts under combined tension and shear, permitting simultaneous observation of contact forces and contact width. While silver classically exhibits substantial sliding-induced plastic junction growth, the nanocontacts exhibit only limited plastic deformation despite high applied stresses. This difference arises from the nanocontacts' high strength, as we find the von Mises stresses at yield points approach the ideal strength of silver. We attribute this to the nanocontacts' nearly defect-free nature and small size. The contacts also separate unstably, with pull-off forces well below classical predictions for rupture under pure tension. This strongly indicates that shearing reduces nanoscale pull-off forces, predicted theoretically at the continuum level, but not directly observed before.

Hollow Atomic Force Microscopy Cantilevers with Nanoscale Wall Thicknesses.

In atomic force microscopy, the cantilever probe is a critical component whose properties determine the resolution and speed at which images with nanoscale resolution can be obtained. Traditional cantilevers, which have moderate resonant frequencies and high quality factors, have relatively long response times and low bandwidths. In addition, cantilevers can be easily damaged by excessive deformation, and tips can be damaged by wear, requiring them to be replaced frequently. To address these issues, new cantilever probes that have hollow cross-sections and walls of nanoscale thicknesses made of alumina deposited by atomic layer deposition are introduced. It is demonstrated that the probes exhibit spring constants up to ≈100 times lower and bandwidths up to ≈50 times higher in air than their typical solid counterparts, allowing them to react to topography changes more quickly. Moreover, it is shown that the enhanced robustness of the hollow cantilevers enables them to withstand large bending displacements more readily and to be more resistant to tip wear.

Friction and Adhesion Govern Yielding of Disordered Nanoparticle Packings: A Multiscale Adhesive Discrete Element Method Study.

Recent studies have demonstrated that amorphous materials, from granular packings to atomic glasses, share multiple striking similarities, including a universal onset strain level for yield. This is despite vast differences in length scales and in the constituent particles' interactions. However, the nature of localized particle rearrangements is not well understood, and how local interactions affect overall performance remains unknown. Here, we introduce a multiscale adhesive discrete element method to simulate recent novel experiments of disordered nanoparticle packings indented and imaged with single nanoparticle resolution. The simulations exhibit multiple behaviors matching the experiments. By directly monitoring spatial rearrangements and interparticle bonding/debonding under the packing's surface, we uncover the mechanisms of the yielding and hardening phenomena observed in experiments. Interparticle friction and adhesion synergistically toughen the packings and retard plastic deformation. Moreover, plasticity can result from bond switching without particle rearrangements. These results furnish insights for understanding yielding in amorphous materials generally.

Linescan Lattice Microscopy: A Technique for the Accurate Measurement and Mapping of Lattice Spacing and Strain with Atomic Force Microscopy.

Lateral resolution and accuracy in scanning probe microscopies are limited by the nonideality of piezoelectric scanning elements due to phenomena including nonlinearity, hysteresis, and creep. By taking advantage of the well-established atomic-scale stick-slip phenomenon in contact-mode atomic force microscopy, we have developed a method for simultaneously indexing and measuring the spacing of surface atomic lattices using only Fourier analysis of unidirectional linescan data. The first step of the technique is to calibrate the X-piezo response using the stick-slip behavior itself. This permits lateral calibration to better than 1% error between 2.5 nm and 9 µm, without the use of calibration gratings. Lattice indexing and lattice constant determination are demonstrated in this way on the NaCl(001) crystal surface. After piezo calibration, lattice constant measurement on a natural bulk MoS2(0001) surface is demonstrated with better than 0.2% error. This is used to measure nonuniform thermal mismatch strain for chemical vapor deposition (CVD)-grown monolayer MoS2 as small as 0.5%. A spatial mapping technique for the lattice spacing is developed and demonstrated, with absolute accuracy better than 0.2% and relative accuracy better than 0.1%, within a map of 12.5 × 12.5 nm2 pixels using bulk highly oriented pyrolytic graphite (HOPG) and MoS2 as reference materials.

How Hydrogen and Oxygen Vapor Affect the Tribochemistry of Silicon- and Oxygen-Containing Hydrogenated Amorphous Carbon under Low-Friction Conditions: A Study Combining X-ray Absorption Spectromicroscopy and Data Science Methods.

The incorporation of silicon and oxygen into hydrogenated amorphous carbon (a-C:H) is an effective approach to decrease the dependence of the tribological properties of a-C:H on the environment. Here, we evaluate the effect of hydrogen and oxygen partial pressures in vacuum on the tribological response of steel pins sliding against films consisting of silicon- and oxygen-containing a-C:H (a-C:H:Si:O). Experiments are conducted in the low-friction/low-wear regime, where sufficient gas pressure prevents steel from adhering to the a-C:H:Si:O, with the velocity accommodation mode being interfacial sliding between the tribotrack formed in the a-C:H:Si:O film and the carbonaceous tribofilm that is formed on the countersurface. The experiments indicated a decrease (increase) in friction and wear with the hydrogen (oxygen) pressure (hydrogen pressures between 50 and 2000 mbar; oxygen pressures between 10 and 1000 mbar). Characterization by X-ray photoelectron and absorption spectroscopies indicated the occurrence of tribologically induced rehybridization of carbon-carbon bonds from sp3 to sp2. This mechanically induced structural transformation coincided with the dissociative surface reaction between hydrogen (oxygen) gas molecules and sp2 carbon-carbon bonds that are highly strained, which results in the formation of carbon-hydrogen groups (carbonyl or ether groups together with silicon atoms having higher oxidation states). On the basis of variations of the fraction of these surface functional groups with gas pressure, a phenomenological model is proposed for the gas pressure dependence of friction for steel when sliding on a-C:H:Si:O films: while the decrease in friction with hydrogen pressure is induced by an increase in the percentage of carbon-hydrogen groups, the increase in friction with oxygen pressure is caused by a progressive increase in the relative fraction of silicon atoms having higher oxidation states and an increase in surface oxygen concentration.

Unraveling the Friction Evolution Mechanism of Diamond-Like Carbon Film during Nanoscale Running-In Process toward Superlubricity.

Diamond-like carbon (DLC) films are capable of achieving superlubricity at sliding interfaces by a rapid running-in process. However, fundamental mechanisms governing the friction evolution during this running-in processes remain elusive especially at the nanoscale, which hinders strategic tailoring of tribosystems for minimizing friction and wear. Here, it is revealed that the running-in governing superlubricity of DLC demonstrates two sub-stages in single-asperity nanocontacts. The first stage, mechanical removal of a thin oxide layer, is described quantitatively by a stress-activated Arrhenius model. In the second stage, a large friction decrease occurs due to a structural ordering transformation, with the kinetics well described by the Johnson-Mehl-Avrami-Kolmogorov model with a modified load dependence of the activation energy. The direct observation of a graphitic-layered transfer film formation together with the measured Avrami exponent reveal the primary mechanism of the ordering transformation. The findings provide fundamental insights into friction evolution mechanisms, and design criteria for superlubricity.

Origin of Friction in Superlubric Graphite Contacts.

More than thirty years ago, it was theoretically predicted that friction for incommensurate contacts between atomically smooth, infinite, crystalline materials (e.g., graphite, MoS_{2}) is vanishing in the low speed limit, and this corresponding state was called structural superlubricity (SSL). However, experimental validation of this prediction has met challenges, since real contacts always have a finite size, and the overall friction arises not only from the atoms located within the contact area, but also from those at the contact edges which can contribute a finite amount of friction even when the incommensurate area does not. Here, we report, using a novel method, the decoupling of these contributions for the first time. The results obtained from nanoscale to microscale incommensurate contacts of graphite under ambient conditions verify that the average frictional contribution of an inner atom is no more than 10^{-4} that of an atom at the edge. Correspondingly, the total friction force is dominated by friction between the contact edges for contacts up to 10 µm in lateral size. We discuss the physical mechanisms of friction observed in SSL contacts, and provide guidelines for the rational design of large-scale SSL contacts.

Nanoscale Friction Behavior of Transition-Metal Dichalcogenides: Role of the Chalcogenide.

Despite extensive research on the tribological properties of MoS2, the frictional characteristics of other members of the transition-metal dichalcogenide (TMD) family have remained relatively unexplored. To understand the effect of the chalcogen on the tribological behavior of these materials and gain broader general insights into the factors controlling friction at the nanoscale, we compared the friction force behavior for a nanoscale single asperity sliding on MoS2, MoSe2, and MoTe2 in both bulk and monolayer forms through a combination of atomic force microscopy experiments and molecular dynamics simulations. Experiments and simulations showed that, under otherwise identical conditions, MoS2 has the highest friction among these materials and MoTe2 has the lowest. Simulations complemented by theoretical analysis based on the Prandtl-Tomlinson model revealed that the observed friction contrast between the TMDs was attributable to their lattice constants, which differed depending on the chalcogen. While the corrugation amplitudes of the energy landscapes are similar for all three materials, larger lattice constants permit the tip to slide more easily across correspondingly wider saddle points in the potential energy landscape. These results emphasize the critical role of the lattice constant, which can be the determining factor for frictional behavior at the nanoscale.

Friction Anisotropy of MoS2: Effect of Tip-Sample Contact Quality.

Atomic-scale friction measured for a single asperity sliding on 2D materials depend on the direction of scanning relative to the material's crystal lattice. Here, nanoscale friction anisotropy of wrinkle-free bulk and monolayer MoS2 is characterized using atomic force microscopy and molecular dynamics simulations. Both techniques show 180° periodicity (2-fold symmetry) of atomic-lattice stick-slip friction vs. the tip's scanning direction with respect to the MoS2 surface. The 60° periodicity (6-fold symmetry) expected from the MoS2 surface's symmetry is only recovered in simulations where the sample is rotated, as opposed to the scanning direction changed. All observations are explained by the potential energy landscape of the tip-sample contact, in contrast with nanoscale topographic wrinkles that have been proposed previously as the source of anisotropy. These results demonstrate the importance of the tip-sample contact quality in determining the potential energy landscape and, in turn, friction at the nanoscale.

Quantitative determination of the interaction potential between two surfaces using frequency-modulated atomic force microscopy.

The interaction potential between two surfaces determines the adhesive and repulsive forces between them. It also determines interfacial properties, such as adhesion and friction, and is a key input into mechanics models and atomistic simulations of contacts. We have developed a novel methodology to experimentally determine interaction potential parameters, given a particular potential form, using frequency-modulated atomic force microscopy (AFM). Furthermore, this technique can be extended to the experimental verification of potential forms for any given material pair. Specifically, interaction forces are determined between an AFM tip apex and a nominally flat substrate using dynamic force spectroscopy measurements in an ultrahigh vacuum (UHV) environment. The tip geometry, which is initially unknown and potentially irregularly shaped, is determined using transmission electron microscopy (TEM) imaging. It is then used to generate theoretical interaction force-displacement relations, which are then compared to experimental results. The method is demonstrated here using a silicon AFM probe with its native oxide and a diamond sample. Assuming the 6-12 Lennard-Jones potential form, best-fit values for the work of adhesion (W adh) and range of adhesion (z 0) parameters were determined to be 80 ± 20 mJ/m2 and 0.6 ± 0.2 nm, respectively. Furthermore, the shape of the experimentally extracted force curves was shown to deviate from that calculated using the 6-12 Lennard-Jones potential, having weaker attraction at larger tip-sample separation distances and weaker repulsion at smaller tip-sample separation distances. This methodology represents the first experimental technique in which material interaction potential parameters were verified over a range of tip-sample separation distances for a tip apex of arbitrary geometry.

Linear Aging Behavior at Short Timescales in Nanoscale Contacts.

Nanoscale silica-silica contacts were recently found to exhibit logarithmic aging for times ranging from 0.1 to 100 s, consistent with the macroscopic rate and state friction laws and several other aging processes. Nanoscale aging in this system is attributed to progressive formation of interfacial siloxane bonds between surface silanol groups. However, understanding or even data for contact behavior for aging times <0.1 s, before the onset of logarithmic aging, is limited. Using a combination of atomic force microscopy experiments and kinetic Monte Carlo simulations, we find that aging is nearly linear with aging time at short timescales between ∼ 5 and 90 ms. We demonstrate that aging at these timescales requires the existence of a particular range of reaction energy barriers for interfacial bonding. Specifically, linear aging behavior consistent with experiments requires a narrow peak close to the upper bound of this range of barriers. These new insights into the reaction kinetics of interfacial bonding in nanoscale aging advance the development of physically based rate and state friction laws for nanoscale contacts.

Mechanochemical Effects of Adsorbates at Nanoelectromechanical Switch Contacts.

Herein, classical molecular dynamics simulations are used to examine nanoscale adsorbate reactions during the cyclic opening and closing of nanoelectromechanical system (NEMS) switches. We focus upon how reactions change metal/metal conductive contact area, asperity morphology, and plastic deformation. We specifically consider Pt, which is often used as an electrode material for NEMS switches. The structural evolution of asperity contacts in gaseous environments with molecules which can potentially form tribopolymers is determined by various factors, for example, contact forces, partial pressure and molecular weight of gas, and the fundamental reaction rates of surface adsorption and adsorbate linkages. The modeled systems exhibit significant changes during the first few cycles, but as the number of contact cycles increases, the system finds a steady-state where the morphologies, Pt/Pt contact area, oligomer chain lengths, amount of Pt transfer between opposing surfaces, and deformation rate stabilize. The stress generated during asperity contact increases the rate of reactions among the adsorbates in the contact region. This makes the size of the adsorbate molecules increase and thus more exposed metal, which implies higher electrical conductance in the closed contact, but more plastic deformation, metal-metal transfer, and mechanical work expended in each contact cycle.