Friction Force Microscopy Research Articles

Nonmonotonic Velocity Dependence of Atomic Friction Induced by Multiple Slips.

The transition from single to multiple atomic slips, theoretically expected and important in atomic-scale friction, has never been demonstrated experimentally as a function of velocity. Here we show by high-resolution friction force microscopy on monolayer MoS_{2}/Au(111) that multiple slips leave a unique footprint-a frictional velocity weakening. Specifically, in a wide velocity interval from 10 to 100 nm/s, friction surprisingly decreases. Model simulations show a similar nonmonotonic behavior at velocities in quantitative agreement with experiment. Results suggest a velocity-corrugation phase diagram, whose validity is proposed more generally.

Role of Trapped Molecules at Sliding Contacts in Lattice-Resolved Friction.

Understanding atomic friction within a liquid environment is crucial for engineering friction mechanisms and characterizing surfaces. It has been suggested that the lattice resolution of friction force microscope in liquid environments stems from a dry contact state, with all liquid molecules expelled from the area of closest approach between the tip and substrate. Here, we revisit this assertion by performing in-depth friction force microscopy experiments and molecular dynamics simulations of the influence of surrounding water molecules on the dynamic behavior of the nanotribological contact between an amorphous SiO2 probe and a monolayer MoS2 substrate. An analysis of simulation and experimental stick-slip patterns demonstrates the entrapment of water molecules at the contact interface. These trapped water molecules behave as an integral component of the probe and participate in its interaction with the substrate, affecting the dynamics of the probe and preventing long slips. Significantly, surrounding water from the capillary or layer exhibits a replenishing effect, acting as a water reservoir during sliding. This phenomenon facilitates the preservation of lattice-scale resolution across a range of applied normal loads.

Friction Force Mapping of Molecular Ordering and Mesoscopic Phase Transformations in Layered-Crystalline Organic Semiconductor Films.

It is critical to understand molecular ordering processes in small-molecule organic semiconductor (OSC) films in optimizing electronic device applications, although it is difficult to observe and investigate the ordering characteristics at a mesoscopic or device scale. Here, we report that friction force microscopy (FFM) allows visualizing the ordering transformation process from a thermodynamically metastable phase to a stable phase at a mesoscopic scale. We utilized 2-octyl-benzothieno[3,2-b]naphtho[2,3-b]thiophene (2-C8-BTNT) as a typical highly layered-crystalline OSC. We found that the friction force between an AFM tip and spin-coated OSC films significantly depends on whether local film states are in metastable monolayer phase or stable bilayer-type herringbone (b-LHB) phase that exhibits high carrier mobility. The formation of the stable b-LHB phase leads to lower friction than the metastable monolayer phase, clearly visualizing the molecular order. Force map (Fmap) analysis indicates that the lower friction in the b-LHB phase should be associated with the reduction of interfacial adhesion force. Notably, the observed results demonstrate that the spin-coated thin film changes from continuous film with the monolayer phase to rugged microcrystal grains with the b-LHB phase when left at ambient conditions. By contrast, an appropriate post-thermal annealing process facilitates the phase transformation without inducing such morphological changes. The technique provides a unique and effective tool for revealing the relationship between processing conditions and device performance in polycrystalline OSC films.

Observation of the early stages of environmental contamination in graphene by friction force.

Exposure to ambient air contaminates the surface of graphene sheets. Contamination may arise from different sources, and its nature alters the frictional behavior of the material. These changes in friction enable the observation of the early stages of contaminants' adsorption in graphene. Using a friction force microscope, we show that molecular adsorption initiates at the edges and mechanical defects in the monolayer. Once the monolayer is covered, the contaminants spread over the additional graphene layers. With this method, we estimate the contamination kinetics. In monolayer graphene, the surface area covered with adsorbed molecules increases with time of air exposure at a rate of 10-14m2/s, while in bilayer graphene, it is one order of magnitude smaller. Finally, as the contaminants cover the additional graphene layers, friction no longer has a difference concerning the number of graphene layers.

Dual Friction Force/Fluorescence Microscopy.

Friction force microscopy (FFM) is a mode of atomic force microscopy (AFM) that quantifies both normal and horizontal forces against substrates. Recent improvement in its accuracy at nanonewton ranges and the possibility of combining AFM with fluorescence microscopy enabled the simultaneous characterization by FFM and fluorescence microscopy. This Tutorial describes the operation principle of the dual friction force/fluorescence microscopy setup and highlights its emerging applications in mechanochromic materials.

Insight into the hydration friction of lipid bilayers.

Hydration layers formed on charged sites play crucial roles in many hydration lubrication systems in aqueous media. However, the underlying molecular mechanism is not well understood. Herein, we explored the hydration friction of lipid bilayers with different charged headgroups at the nanoscale through a combination of frequency-modulation atomic force microscopy and friction force microscopy. The nanoscale friction experiments showed that the hydration friction coefficient and frictional energy dissipation of a cationic lipid (DPTAP) were much lower than those of zwitterionic (DPPE) and anionic (DPPG) lipids. The hydration layer probing at the surfaces of different lipid bilayers clearly revealed the relationship between the charged lipid headgroups and hydration layer structures. Our detailed analysis demonstrated that the cationic lipid had the largest hydration force in comparison with zwitterionic and anionic lipids. These friction and hydration force results indicated that the difference of the lipid headgroup charge resulted in different hydration strengths which led to the difference of hydration friction behaviors. The findings in this study provide molecular insights into the hydration friction of lipid bilayers, which has potential implications for the development of efficient hydration lubrication systems with boundary lipid bilayers in aqueous media.

Single-Polymer Friction Force Microscopy of dsDNA Interacting with a Nanoporous Membrane.

Surface-grafted polymers can reduce friction between solids in liquids by compensating the normal load with osmotic pressure, but they can also contribute to friction when fluctuating polymers entangle with the sliding counter face. We have measured forces acting on a single fluctuating double-stranded DNA polymer, which is attached to the tip of an atomic force microscope and interacts intermittently with nanometer-scale methylated pores of a self-assembled polystyrene-block-poly(4-vinylpyridine) membrane. Rare binding of the polymer into the pores is followed by a stretching of the polymer between the laterally moving tip and the surface and by a force-induced detachment. We present results for the velocity dependence of detachment forces and of attachment frequency and discuss them in terms of rare excursions of the polymer beyond its equilibrium configuration.

Nanostructural Characterization of Luminescent Polyvinyl Alcohol/Graphene Quantum Dots Nanocomposite Films.

This study focuses on the fabrication of polymer nanocomposite films using polyvinyl alcohol (PVA)/graphene quantum dots (GQDs). We investigate the relationship between the structural, thermal, and nanoscale morphological properties of these films and their photoluminescent response. Although according to X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and differential thermal analysis (DTA), the incorporation of GQDs does not significantly affect the percentage crystallinity of the PVA matrix, for a range of added GQD concentrations, atomic force microscopy (AFM) showed the formation of islands with apparent crystalline morphology on the surface of the PVA/GQD films. This observation suggests that GQDs presumably act as nucleating agents for island growth. The incorporation of GQDs also led to the formation of characteristic surface pores with increased stiffness and frictional contrast, as indicated by ultrasonic force microscopy (UFM) and frictional force microscopy (FFM) data. The photoluminescence (PL) spectra of the films were found to depend both on the amount of GQDs incorporated and on the film morphology. For GQD loads >1.2%wt, a GQD-related band was observed at ~1650 cm-1 in FT-IR, along with an increase in the PL band at lower energy. For a load of ~2%wt GQDs, the surface morphology was characterized by extended cluster aggregates with lower stiffness and friction than the surrounding matrix, and the PL signal decreased.

Triboelectrification and Unique Frictional Characteristics of Germanium-Based Nanofilms.

In this study, germanium arsenide (GeAs) is investigated as apromising nanomaterial for application in triboelectric nanogenerators and green energy harvesting. The mechanical and electrical properties of mechanically exfoliated GeAs on silica substrates are evaluated through friction force microscopy and Kelvin probe force microscopy, respectively. First, it is observed that the surface potential/work function of GeAs varied with thickness. Second, thickness-dependent friction on GeAs films is found. However, the variation of friction with GeAs thickness followed an inverse trend typically observed for most other 2D material systems: larger friction is measured on thicker GeAs films. The higher friction is attributed to the higher surface potential of thicker GeAs, resulting from the accumulation of electrons on the GeAs surface that also resulted in higher adhesion between GeAs surface and the tip. Finally, history-dependent friction is observed and resulted from a continual increase in the friction force as the surface is scanned and originated from the triboelectrification of the surface. The dynamic triboelectrification behavior of thick GeAs during the scanning process is further verified and visualized by a serial experiment, where the GeAs is tribo-electrified through scanning and gradually de-electrified/discharged upon ceasing the scan.

Nanoscopic Force Sensitivity of Polydiacetylene 2D Layered Composites with Guest Molecules

Abstract2D polydiacetylene (PDA) layered composites with added guest molecules have demonstrated an excellent tunable mechanochromic properties toward the development of mechanochromic force sensors in energy‐related and medical applications. However, its force sensitivity at the nanoscale is left uncharacterized due to a lack of technique to conveniently apply forces to the 2D films in different directions, limiting the quantitative understanding of the sensitivity‐tuning mechanism. In this work, the quantitative friction force microscopy combined with fluorescence microscopy is introduced to measure the force sensitivity of the PDA layered composites with guest organic amines at the nanoscale. Intercalating nonylamine and 1‐aminodecane increase the sensitivity of 10,12‐pentacosadiynoic acid by 127% and 111%, respectively, whereas adding n‐tridecaylamine and stearylamine reduce it by 77% and 86%. This force sensitivity at the nanoscale is inversely correlated to the thermochromic temperature and the Young's moduli of the films, suggesting that the softer film has both higher force‐ and thermo‐sensitivity.

Nano-scale wear: A critical review on its measuring methods and parameters affecting nano-tribology

This paper presents a critical review on the measuring methods and parameters affecting nano-tribology in the context of nano-scale wear. Nano-scale wear phenomena play a crucial role in various industries, including micro/nano-systems, electronics, and biotechnology. The review begins by discussing the significance of nano-scale wear and its impact on device performance, lifespan, durability, energy efficiency, cost savings, and environmental sustainability. It then delves into the measuring methods employed to assess nano-scale wear, including scanning probe microscopy (SPM) techniques such as atomic force microscopy (AFM) and friction force microscopy (FFM). The capabilities of AFM and FFM in studying the roughness of surface, adhesion, friction, scratch, abrasion, and nano-scale material transfer are highlighted. Additionally, the review explores the parameters affecting nano-wear, such as lubrication strategies, stress levels, sliding velocity, and atomic-scale reactions. The article concludes by emphasizing the importance of advanced microscopy techniques in understanding tribological mechanisms at different scales, bridging the gap between macro and nano-tribology studies.

Atomic Friction Processes of Two-Dimensional Materials.

In this Perspective, we present the recent advances in atomic friction measured of two-dimensional materials obtained by friction force microscopy. Starting with the atomic-scale stick-slip behavior, a beautiful highly nonequilibrium process, we discuss the main factors that contribute to determine sliding friction between single asperity and a two-dimensional sheet including chemical identity of material, thickness, external load, sliding direction, velocity/temperature, and contact size. In particular, we focus on the latest progress of the more complex friction behavior of moiré systems involving 2D layered materials. The underlying mechanisms of these frictional characteristics observed during the sliding process by theoretical and computational studies are also discussed. Finally, a discussion and outlook on the perspective of this field are provided.

Comparison of micro- and macro-tribological properties of carbon composites reinforced by vapor-grown carbon fibers

Carbon composites were prepared from furan resins filled with vapor-grown carbon fibers (VGCFs). The resistances and densities of the composites, affected by the adhesion between the matrix and VGCFs, remained almost constant with VGCF concentration. The micro- and macro-friction coefficients of the composites were measured using a friction force microscope and pin-on-drum tribology apparatus, respectively. With increasing VGCF concentration, the micro-friction coefficients of the matrix increased, thereby reflecting an increase in roughnesses. In contrast, the micro-friction coefficients of the interfaces between the matrix and VGCF, with changes strongly correlated with the macro-friction coefficients of the composites, remained almost constant.

Investigation of Programmable Friction with Ionic Liquid Mixtures at the Nano- and Macroscales

Non-mechanical stimuli are used to directly control or program the friction properties of tribosystems. For this purpose, an ionic liquid is used as a lubricant that affects and controls the friction in the presence of external triggers. Here, it is shown that the friction behavior of two surfaces in sliding contact can be controlled and permanently changed by applying an electrical potential to an ionic liquid mixture (ILM). This change in the friction properties was demonstrated both at the nanoscale using an atomic force microscopy (AFM)-based friction force microscopy (FFM) and at the macroscale using a specially designed tribo-setup cell. In tribology, the linking of these two scales of magnitude represents one of the greatest obstacles between basic research and the step towards application-oriented system development and is therefore of fundamental importance. In addition, other parameters affecting the tribological behavior of the system, such as roughness, lubricant film thickness, and wear behavior, were investigated as a function of the electrical potentials. The correlation between the structure of surface-bound ionic liquid layers and the friction behavior can be used to control friction, thus enabling a first step towards tribosystems that automatically adapt to changing conditions.

Relaxation Times of Ionic Liquids under Electrochemical Conditions Probed by Friction Force Microscopy.

Ionic liquids (ILs) represent an important class of liquids considered for a broad range of applications such as lubrication, catalysis, or as electrolytes in batteries. It is well-known that in the case of charged surfaces, ILs form a pronounced layer structure that can be easily triggered by an externally applied electrode potential. Information about the time required to form a stable interface under varying electrode potentials is of utmost importance in many applications. For the first time, probing of relaxation times of ILs by friction force microscopy is demonstrated. The friction force is extremely sensitive to even subtle changes in the interfacial configuration of ILs. Various relaxation processes with different time scales are observed. A significant difference dependent on the direction of switching the applied potential, i.e., from a more cation-rich to a more anion-rich interface or vice versa, is found. Furthermore, variations in height immediately after the potential step and the presence of trace amounts of water are discussed as well.

Phase-dependent Friction on Exfoliated Transition Metal Dichalcogenides Atomic Layers.

The fundamental aspects of energy dissipation on 2-dimensional (2D) atomic layers are extensively studied. Among various atomic layers, transition metal dichalcogenides (TMDs) exists in several phases based on their lattice structure, which give rise to the different phononic and electronic contributions in energy dissipation. 2H and 1T' (distorted 1T) phase MoS2 and MoTe2 atomic layers exfoliated on mica substrate are obtained and investigated their nanotribological properties with atomic force microscopy (AFM)/ friction force microscopy (FFM). Surprisingly, 1T' phase of both MoS2 and MoTe2 exhibits ≈10 times higher friction compared to 2H phase. With density functional theory analyses, the friction increase is attributed to enhanced electronic excitation, efficient phonon dissipation, and increased potential energy surface barrier at the tip-sample interface. This study suggests the intriguing possibility of tuning the friction of TMDs through phase transition, which can lead to potential application in tunable tribological devices.

Adsorption of Aldehyde-Functional Diblock Copolymer Spheres onto Surface-Grafted Polymer Brushes via Dynamic Covalent Chemistry Enables Friction Modification.

Dynamic covalent chemistry has been exploited to prepare numerous examples of adaptable polymeric materials that exhibit unique properties. Herein, the chemical adsorption of aldehyde-functional diblock copolymer spherical nanoparticles onto amine-functionalized surface-grafted polymer brushes via dynamic Schiff base chemistry is demonstrated. Initially, a series of cis-diol-functional sterically-stabilized spheres of 30-250 nm diameter were prepared via reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization. The pendent cis-diol groups within the steric stabilizer chains of these precursor nanoparticles were then oxidized using sodium periodate to produce the corresponding aldehyde-functional spheres. Similarly, hydrophilic cis-diol-functionalized methacrylic brushes grafted from a planar silicon surface using activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) were selectively oxidized to generate the corresponding aldehyde-functional brushes. Ellipsometry and X-ray photoelectron spectroscopy were used to confirm brush oxidation, while scanning electron microscopy studies demonstrated that the nanoparticles did not adsorb onto a cis-diol-functional precursor brush. Subsequently, the aldehyde-functional brushes were treated with excess small-molecule diamine, and the resulting imine linkages were converted into secondary amine bonds via reductive amination. The resulting primary amine-functionalized brushes formed multiple dynamic imine bonds with the aldehyde-functional diblock copolymer spheres, leading to a mean surface coverage of approximately 0.33 on the upper brush layer surface, regardless of the nanoparticle size. Friction force microscopy studies of the resulting nanoparticle-decorated brushes enabled calculation of friction coefficients, which were compared to that measured for the bare aldehyde-functional brush. Friction coefficients were reasonably consistent across all surfaces except when particle size was comparable to the size of the probe tip. In this case, differences were ascribed to an increase in contact area between the tip and the brush-nanoparticle layer. This new model system enhances our understanding of nanoparticle adsorption onto hydrophilic brush layers.

Investigating the effect of interatomic distance on friction force through MEMS-AFM based experiment

Investigations on the influence of the interatomic distance (IAD) on friction are crucial for gaining a better understanding of friction and comprehending the essential nature of graphene friction. We obtained friction force microscopy (FFM) images of strained surfaces to examine how the IAD affects the friction force. First, using microelectromechanical system (MEMS) fabrication techniques, we fabricated a strain-generating microdevice that can generate surface strain on its Si surface by an electrostatic comb actuator. The microdevice was installed in a high vacuum atomic force microscope. Next, FFM measurements were performed on the stress concentration section of the microdevice using a Si cantilever. The driving voltage on the comb actuator was switched on/off for each scan line during a single raster scan. This procedure allowed us to obtain FFM images representing the surface strain (i.e., the IAD variation) by excluding friction/wear-induced disturbances. The FFM images agreed well with the strain distribution calculated by the elastic finite element method analysis. The relative reduction of the friction was approximately 9% against the calculated strain of 1.2%.

Influence of structural disorder on the elastic, frictional, and electrical properties in functionalized polyaniline thin films at the nanoscale investigated by atomic force microscopy

We investigated the influence of structural order on the elastic, frictional, and electrical properties of butylthio-functionalized PANI (PANI-SBu) films by atomic force microscopy (AFM)-based techniques, including PeakForce quantitative nanomechanical mapping, friction force microscopy, and conductive AFM. The PANI-SBu films were prepared by the drop-cast method from the solution of PANI-SBu in N-methyl-2-pyrrolidone that was continuously stirred. The PANI-SBu films were fabricated after different solution stirring times. The shear force during the mechanical stir will disentangle the highly-coiled PANI-SBu polymer chains in the solution. Therefore, the polymer chains in solution cast on the substrates will progressively self-assemble into a more organized structure when solvents evaporate, leading to PANI-SBu films with improved structural order. Our AFM studies discovered that more structurally-ordered PANI-SBu films have substantially larger out-of-plane elastic moduli and charge mobility but smaller kinetic friction coefficients. The denser packing of polymer molecules increases film elasticities and promotes chain-to-chain charge transport. In addition, stiffer PANI-SBu film surfaces are more difficult to deform when sheared by the sliding AFM probe, resulting in less energy dissipation during AFM friction measurements. Thus, smaller kinetic friction coefficients were found. Conversely, more structurally-disordered PANI-SBu films have smaller elasticity and charge mobility but larger kinetic friction coefficients. Our results demonstrate that it is possible to manipulate the elastic, frictional, and electrical properties of PANI-SBu films by controlling their structural order, which can be essential for developing polymer-based composite materials and flexible electronic devices.

Separating anisotropic and isotropic friction between atomic force microscope tips and atomically flat surfaces

Layered materials are the most important class of solid lubricants. Friction on their surfaces has complex origins. Most experimental methods so far only give total friction force and cannot separate contributions from different origins. Here, we report a method to separate anisotropic and isotropic friction forces on atomically flat surfaces such as ${\mathrm{MoS}}_{2}$, graphite, h-BN, and mica by combining a two-dimensional friction force microscope technology and a two-dimensional friction model. We found that the friction force of most atomically flat surfaces is anisotropic, the total force on the tip misaligns with the scan direction, and the friction anisotropy vanishes under low sliding velocity. Our two-dimensional friction model explains experimental observations. It reveals the existence of elemental hopping combinations and the isotropic component in total friction. The misalignment angle can be used to calculate the ratio of anisotropic and isotropic friction components and the ratio of resistance forces from different lattice directions. The separation of anisotropic and isotropic friction forces will offer an avenue for studying the properties of individual friction components, which can boost the study of friction mechanisms in the future and benefit the application of solid lubricants.