Effect of Amorphous-Crystalline Phase Transition on Superlubric Sliding.

Structural superlubricity describes the state of greatly reduced friction between incommensurate atomically flat surfaces. Theory predicts that, in the superlubric state, the remaining friction sensitively depends on the exact structural configuration. In particular the friction of amorphous and crystalline structures for, otherwise, identical interfaces should be markedly different. Here, we measure friction of antimony nanoparticles on graphite as a function of temperature between 300 and 750 K. We observe a characteristic change of friction when passing the amorphous-crystalline phase transition above 420 K, which shows irreversibility upon cooling. The friction data is modeled with a combination of an area scaling law and a Prandtl-Tomlinson type temperature activation. We find that the characteristic scaling factor γ, which is a fingerprint of the structural state of the interface, is reduced by 20% when passing the phase transition. This validates the concept that structural superlubricity is determined by the effectiveness of atomic force canceling processes.

Nanoscale Friction across the First-Order Charge Density Wave Phase Transition of 1T-TaS2.

Nanotribology using atomic force microscopy (AFM) can be considered as a unique approach to analyze phase transition materials by localized mechanical interaction. In this work, we investigate friction on the lamellar transition metal dichalcogenide 1T-TaS2, which can undergo first-order charge density wave (CDW) phase transitions. Based on temperature-dependent atomic force microscopy under ultrahigh vacuum conditions (UHV), we can characterize the general friction levels across the first-order phase transitions and for the different phases. While structural and electronic properties for different phases appear to be of minor influence on friction, a distinct peak in friction is observed during the phase transition when cooling the sample from the nearly commensurate CDW (NC-CDW) phase to the commensurate CDW (C-CDW) phase. By performing systematic measurements as a function of load, scan velocity, and scan time, a recently proposed friction mechanism can be corroborated, where the AFM tip gradually induces local transformations of the material close to the spinodal point in a thermally activated and shear-assisted process until the surface is fully "harvested". Our results demonstrate that repeated nanomechanical stress can trigger local first-order phase transitions constituting a so far little explored mechanical energy dissipation channel.

Characterization of Vegard strain related to exceptionally fast Cu-chemical diffusion in Cu[Formula: see text]Mo[Formula: see text]S[Formula: see text] by an advanced electrochemical strain microscopy method.

Electrochemical strain microscopy (ESM) has been developed with the aim of measuring Vegard strains in mixed ionic-electronic conductors (MIECs), such as electrode materials for Li-ion batteries, caused by local changes in the chemical composition. In this technique, a voltage-biased AFM tip is used in contact resonance mode. However, extracting quantitative strain information from ESM experiments is highly challenging due to the complexity of the signal generation process. In particular, electrostatic interactions between tip and sample contribute significantly to the measured ESM signals, and the separation of Vegard strain-induced signal contributions from electrostatically induced signal contributions is by no means a trivial task. Recently, we have published a compensation method for eliminating frequency-independent electrostatic contributions in ESM measurements. Here, we demonstrate the potential of this method for detecting Vegard strain in MIECs by choosing Cu[Formula: see text]Mo[Formula: see text]S[Formula: see text] as a model-type MIEC with an exceptionally high Cu chemical diffusion coefficient. Even for this material, Vegard strains are only measurable around and above room-temperature and with proper elimination of electrostatics. The analyis of the measured Vegards strains gives strong indication that due to a high charge transfer resistance at the tip/interface, the local Cu concentration variations are much smaller than predicted by the local Nernst equation. This suggests that charge transfer resistances have to be analyzed in more detail in future ESM studies.

Thermal Activation of Nanoscale Wear.

Nanoscale wear tracks on ionic crystals are created by reciprocating single asperity scratch tests using atomic force microscopy. The wear characteristics are analyzed by the scratch depth as a function of surface temperature from 25 to 300 K. The average wear depth shows a nonmonotonic behavior as a function of temperature, with a transition between two different regimes characterized by the occurrence of quasiperiodic ripple formation. A thermally activated bond breaking model quantitatively explains the wear data in the low temperature, nonripple regime, but fails above the temperature threshold. This discrepancy is resolved with a geometric separation of the ripple mounds from the troughs, leading to full agreement with Arrhenius kinetics over the full temperature range.

Single-asperity sliding friction across the superconducting phase transition.

In sliding friction, different energy dissipation channels have been proposed, including phonon and electron systems, plastic deformation, and crack formation. However, how energy is coupled into these channels is debated, and especially, the relevance of electronic dissipation remains elusive. Here, we present friction experiments of a single-asperity sliding on a high-T c superconductor from 40 to 300 kelvin. Overall, friction decreases with temperature as generally expected for nanoscale energy dissipation. However, we also find a large peak around T c. We model these results by a superposition of phononic and electronic friction, where the electronic energy dissipation vanishes below T c. In particular, we find that the electronic friction constitutes a constant offset above T c, which vanishes below T c with a power law in agreement with Bardeen-Cooper-Schrieffer theory. While current point contact friction models usually neglect such friction contributions, our study shows that electronic and phononic friction contributions can be of equal size.

Lattice Discontinuities of 1T-TaS2 across First Order Charge Density Wave Phase Transitions.

Transition metal dichalcogenides are lamellar materials which can exhibit unique and remarkable electronic behavior due to effects of electron-electron and electron-phonon coupling. Among these materials, 1T-tantalum disulfide (1T-TaS2) has spurred considerable interest, due to its multiple first order phase transitions between different charge density wave (CDW) states. In general, the basic effects of charge density wave formation in 1T-TaS2 can be attributed to in plane re-orientation of Ta-atoms during the phase transitions. Only in recent years, an increasing number of studies has also emphasized the role of interlayer interaction and stacking order as a crucial aspect to understand the specific electronic behavior of 1T-TaS2, especially for technological systems with a finite number of layers. Obviously, continuously monitoring the out of plane expansion of the sample can provide direct inside into the rearrangement of the layer structure during the phase transition. In this letter, we therefore investigate the c-axis lattice discontinuities of 1T-TaS2 by atomic force microscopy (AFM) method under ultra-high vacuum conditions. We find that the c-axis lattice experiences a sudden contraction across the nearly-commensurate CDW (NC-CDW) phase to commensurate CDW (C-CDW) phase transition during cooling, while an expansion is found during the transition from the C-CDW phase to a triclinic CDW phase during heating. Thereby our measurements reveal, how higher order C-CDW phase can favor a more dense stacking. Additionally, our measurements also show subtler effects like e.g. two expansion peaks at the start of the transitions, which can provide further insight into the mechanisms at the onset of CDW phase transitions.

Nanoscale Characterization of Ion Mobility by Temperature-Controlled Li-Nanoparticle Growth.

Detailed understanding of electrochemical transport processes on the nanoscale is considered not only as a topic of fundamental scientific interest but also as a key to optimize material systems for application in electrochemical energy storage. A prominent example is solid-state electrolytes, where transport properties are strongly influenced by the microscopic structure of grain boundaries or interface regimes. However, direct characterization of ionic transport processes on the nanoscale remains a challenge. For a heterogeneous Li+-conducting glass ceramic, we demonstrate quantitative nanoscopic probing of electrochemical properties on the basis of temperature-controlled growth of nanoscopic Li particles with conductive tip atomic force microscopy. The characteristic energy barriers can be derived from the particle growth dynamics and are consistent with simultaneously recorded nanovoltammetry, which can be interpreted as an interplay between overpotentials, ion conductivity, and nanoscale spreading resistance. In the low-temperature limit at around 170 K, where the particle growth speed is slowed down by several orders of magnitude with respect to room temperature, we demonstrate ion-conductivity mapping with lateral resolutions only limited by the effective tip-surface contact radius. Our mapping measurements reveal the insulating character of the AlPO4 phase, whereas any influence of grain boundaries is related to subsurface constrictions of the current paths.

Recent highlights in nanoscale and mesoscale friction.

Friction is the oldest branch of non-equilibrium condensed matter physics and, at the same time, the least established at the fundamental level. A full understanding and control of friction is increasingly recognized to involve all relevant size and time scales. We review here some recent advances on the research focusing of nano- and mesoscale tribology phenomena. These advances are currently pursued in a multifaceted approach starting from the fundamental atomic-scale friction and mechanical control of specific single-asperity combinations, e.g., nanoclusters on layered materials, then scaling up to the meso/microscale of extended, occasionally lubricated, interfaces and driven trapped optical systems, and eventually up to the macroscale. Currently, this "hot" research field is leading to new technological advances in the area of engineering and materials science.

Friction fluctuations of gold nanoparticles in the superlubric regime.

Superlubricity, or alternatively termed structural (super)lubrictiy, is a concept where ultra-low friction is expected at the interface between sliding surfaces if these surfaces are incommensurate and thus unable to interlock. In this work, we now report on sudden, reversible, friction changes that have been observed during AFM-based nanomanipulation experiments of gold nanoparticles sliding on highly oriented pyrolythic graphite. These effects can be explained by rotations of the gold nanoparticles within the concept of structural superlubricity, where the occurrence of ultra-low friction can depend extremely sensitively on the relative orientation between the slider and the substrate. From our theoretical simulations it will become apparent how even miniscule magnitudes of rotation are compatible to the observed effects and how size and shape of the particles can influence the dependence between friction and relative orientation.

Time Strengthening of Crystal Nanocontacts.

We demonstrate how an exponentially saturating increase of the contact area between a nanoasperity and a crystal surface, occurring on time scales governed by the Arrhenius equation, is consistent with measurements of the static friction and lateral contact stiffness on a model alkali-halide surface at different temperatures in ultrahigh vacuum. The "contact ageing" effect is attributed to atomic attrition and is eventually broken by thermally activated slip of the nanoasperity on the surface. The combination of the two effects also leads to regions of strengthening and weakening in the velocity dependence of the friction, which are well-reproduced by an extended version of the Prandtl-Tomlinson model.

Limitations of Structural Superlubricity: Chemical Bonds versus Contact Size.

Structural superlubricity describes the state of virtually frictionless sliding if two atomically flat interfaces are incommensurate, that is, they share no common periodicity. Despite the exciting prospects of this low friction phenomenon, there are physical limitations to the existence of this state. Theory predicts that the contact size is one fundamental limit, where the critical size threshold mainly depends on the interplay between lateral contact compliance and interface interaction energies. Here we provide experimental evidence for this size threshold by measuring the sliding friction force of differently sized antimony particles on MoS2. We find that superlubric sliding with the characteristic linear decrease of shear stress with contact size prevails for small particles with contact areas below 15 000 nm2. Larger particles, however, show a transition toward constant shear stress behavior. In contrast, Sb particles on graphite show superlubricity over the whole size range. Ab initio simulations reveal that the chemical interaction energies for Sb/MoS2 are much stronger than for Sb/HOPG and can therefore explain the different friction properties as well as the critical size thresholds. These limitations must be considered when designing low friction contacts based on structural superlubricity concepts.

Nanotribological Properties of Hexadecanethiol Self-Assembled Monolayers on Au(111): Structure, Temperature, and Velocity.

Self-assembled monolayers (SAM) are promising building blocks for the optimization of a large variety of systems both on the nano- and on the microscale. Among other applications, SAM are often used as protective coating or friction modifiers. In this work, we have used hexadecanethiol SAM on Au(111) as a model system and studied the different mechanisms of energy dissipation during temperature and velocity dependent friction force microscopy (FFM). In a number of cases, the SAM remained stable during atomic force microscopy experiments and friction-velocity isotherms related dissipation to an activation energy. In other cases, friction experiments lead to an irreversible deterioration of the SAM. This can rather be associated with the general SAM structure that was analyzed by scanning tunneling microscopy and showed a large variety of potential breakdown points like, for example, grain boundaries, step edges, or substrate-related holes in the SAM.

Universal Aging Mechanism for Static and Sliding Friction of Metallic Nanoparticles.

The term "contact aging" refers to the temporal evolution of the interface between a slider and a substrate usually resulting in increasing friction with time. Current phenomenological models for multiasperity contacts anticipate that such aging is not only the driving force behind the transition from static to sliding friction, but at the same time influences the general dynamics of the sliding friction process. To correlate static and sliding friction on the nanoscale, we show experimental evidence of stick-slip friction for nanoparticles sliding on graphite over a wide dynamic range. We can assign defined periods of aging to the stick phases of the particles, which agree with simulations explicitly including contact aging. Additional slide-hold-slide experiments for the same system allow linking the sliding friction results to static friction measurements, where both friction mechanisms can be universally described by a common aging formalism.

Influence of contact aging on nanoparticle friction kinetics.

One of the oldest concepts in tribology is stick-slip dynamics, where a disruptive sequence of stick and slip phases determine the overall resistance in sliding friction. While the mechanical energy dissipates in the sudden slip phase, the stick phase has been shown to be characterized by contact strengthening mechanisms, also termed contact aging. We present experiments of sliding nanoparticles, where friction is measured as a function of sliding velocity and interface temperature. The resulting complex interdependence is in good agreement with Monte Carlo simulations, in which the energy barrier for contact breaking increases logarithmically with time, at a rate governed by thermal activation.

Spinning and translational motion of Sb nanoislands manipulated on MoS2.

Antimony nanoislands grown on a MoS2 surface in ultra-high vacuum have been manipulated by atomic force microscopy (AFM) in ambient conditions. The island profiles have been digitized and provided as an input to a collisional algorithm based on classical mechanics. Assuming that the islands are rigid and static friction is high enough to prevent further motion after the passage of the probing tip, the direction of motion and the angle of rotation of the islands have been reproduced numerically. For a given spacing between the scan lines, the angle of deflection with respect to the fast scan direction and the angular speed of the islands are expected to vary with the friction between islands and substrate. From a comparison between model and experiment a shear strength in the order of 0.2 MPa is estimated.

Scaling laws of structural lubricity.

"Structural lubricity" refers to a unique friction state in which two flat surfaces are sliding past each other with ultralow resistance due to incommensurate atomic lattice structures. In this case, theory anticipates sublinear scaling for the area dependence of friction. Here, we experimentally confirm these predictions by measuring the sliding resistance of amorphous antimony and crystalline gold nanoparticles on crystalline graphite. For the amorphous particles a square root relation between friction and contact area is observed. For crystalline gold particles we find a more complex scaling behavior related to variations in particle shape and orientation. These results allow us to link mesoscopic friction to atomic principles.

Tuning the instability in static mode atomic force spectroscopy as obtained in an AFM by applying an electric field between the tip and the substrate.

We have investigated experimentally the role of cantilever instabilities in determination of the static mode force-distance curves in presence of a dc electric field. The electric field has been applied between the tip and the sample in an atomic force microscope working in ultra-high vacuum. We have shown how an electric field modifies the observed force (or cantilever deflection)-vs-distance curves, commonly referred to as the static mode force spectroscopy curves, taken using an atomic force microscope. The electric field induced instabilities shift the jump-into-contact and jump-off-contact points and also the deflection at these instability points. We explained the experimental results using a model of the tip-sample interaction and quantitatively established a relation between the observed static mode force spectroscopy curves and the applied electric field which modifies the effective tip-sample interaction in a controlled manner. The investigation establishes a way to quantitatively evaluate the electrostatic force in an atomic force microscope using the static mode force spectroscopy curves.

Understanding frictional duality and bi-duality: Sb-nanoparticles on HOPG.

Antimony nanoparticles deposited under UHV conditions on HOPG are found to exhibit an intriguing frictional behavior characterized by a distinct clearly separated double dual behavior of dependence of the frictional force on contact area. We present the first realistic simulations, density functional modeling adapted to accommodate van der Waals interactions, of the (double) dual frictional behavior. The simulations provide insights into the physics/chemistry of all the frictional branches in terms of incommensurable interfaces, mobile spacer molecules as well as a novel concept of mobile oxidized multi-nanoasperities.

The effect of intrinsic instability of cantilever on static mode atomic force spectroscopy.

We show that the static force spectroscopy curve taken in an atomic force microscope is significantly modified due to presence of intrinsic cantilever instability which occurs as a result of its movement in a nonlinear force field. This instability acts in tandem with such instabilities as water bridge or molecular bond rupture and makes the static force spectroscopy curve (including 'jump-off-contact') dependent on the step size of data collection. A theoretical model has been proposed to explain the data. We emphasize the necessity of taking care of this fundamental instability of the microcantilever in calculating the adhesive force and also in the interpretation of data taken using an atomic force microscope.

Frictional duality observed during nanoparticle sliding.

One of the most fundamental questions in tribology concerns the area dependence of friction at the nanoscale. Here, experiments are presented where the frictional resistance of nanoparticles is measured by pushing them with the tip of an atomic force microscope. We find two coexisting frictional states: While some particles show finite friction increasing linearly with the interface areas of up to 310 000 nm(2), other particles assume a state of frictionless sliding. The results further suggest a link between the degree of surface contamination and the occurrence of this duality.