Manipulation and Characterization of Submillimeter Shearing Contacts in Graphite by the Micro-Dome Technique.

Manipulation techniques are the key to measuring fundamental properties of layered materials and their monolayers (2D materials) on the micro- and nanoscale as well as a necessity to the solution of relevant existing challenges. An example is the challenge against upscaling structural superlubricity, a phenomenon of near-zero friction and wear in solid contacts. To date, the largest single structural superlubric contact only has a size of a few tens of micrometers, which is achieved on graphite mesa, a system that has shown microscale superlubricity. The first obstacle against extending the contact size is the lack of suitable manipulation techniques. Here, a micro-dome technique is demonstrated on graphite mesas by shearing contacts 2500 times larger in area than previously possible. With this technique, submillimeter graphite mesas are opened, characterized for the first time, and compared to their microscale counterparts. Interfacial structures, which are possibly related to the failure of superlubricity, are observed: commensurate grains, external steps, and carbon aggregates. Furthermore, a proof-of-concept mechanical model is developed to understand how the micro-dome technique works and to predict its limits. Finally, a dual-axis force measuring device is developed and integrated with the micro-dome technique to measure the normal and lateral forces when shearing submillimeter mesas. These results provide a platform technique for future research on structural superlubricity on different scales and manipulation of structures of layered materials in general.

Anisotropic Fracture of Graphene Revealed by Surface Steps on Graphite.

The anisotropic fracture toughness G(θ) is an intrinsic feature of graphene and is fundamental for fabrication, functioning, and robustness of graphene-based devices. However, existing results show significant discrepancies on the anisotropic factor, i.e., the ratio between zigzag (ZZ) and armchair (AC) directions, G_{ZZ}/G_{AC}, both qualitatively and quantitatively. Here, we investigate the anisotropic fracture of graphene by atomic steps on cleaved graphite surfaces. Depending on the relation between the peeling direction and local lattice orientation, two categories of steps with different structures and behaviors are observed. In one category are straight steps well aligned with local ZZ directions, while in the other are steps consisting of nanoscale ZZ and AC segments. Combined with an analysis on fracture mechanics, the microscale morphology of steps and statistics of their directions provides a measurement on the anisotropic factor of G_{ZZ}/G_{AC}=0.971, suggesting that the ZZ direction has a slightly lower fracture toughness. The results provide an experimental benchmark for the widely scattered existing results, and offer constraints on future models of graphene fracture.

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.

Characterization of a Microscale Superlubric Graphite Interface.

Direct characterizations of the two component surfaces of a solid-solid interface are essential for understanding its various interfacial mechanical, physical, and electrical behaviors. Particularly, the fascinating phenomenon termed structural superlubricity, a state of nearly zero friction and wear, is sensitively dependent on the interface structure. Here we report a controllable pick-and-flip technique to separate a microscale contact pair for the characterization of its two component surfaces for van der Waals layered materials. With this technique, the interface of a graphite superlubric contact is characterized with resolution from microscale down to the atomic level. Imaging of the graphite lattice provides direct proof that this superlubric interface consists of two monocrystalline surfaces incommensurate with each other. More importantly, the structure-property relationship for this contact is investigated. Friction measurements combined with fully atomistic molecular dynamics reveal that internal structures [internals steps, pits, and bulges buried underneath the topmost graphene sheet(s)] have negligible contribution to the total friction; in contrast, external defects lead to a high friction. These results help us to better understand the structure of highly oriented pyrolytic graphite and the fundamental mechanisms of structural superlubricity, as well as to guide the design of superlubricity-based devices.

Negative friction coefficient in microscale graphite/mica layered heterojunctions.

The friction of a solid contact typically shows a positive dependence on normal load according to classic friction laws. A few exceptions were recently observed for nanoscale single-asperity contacts. Here, we report the experimental observation of negative friction coefficient in microscale monocrystalline heterojunctions at different temperatures. The results for the interface between graphite and muscovite mica heterojunction demonstrate a robust negative friction coefficient both in loading and unloading processes. Molecular dynamics simulations reveal that the underlying mechanism is a synergetic and nontrivial redistribution of water molecules at the interface, leading to larger density and more ordered structure of the confined subnanometer-thick water film. Our results are expected to be applicable to other hydrophilic van der Waals heterojunctions.

Load-induced dynamical transitions at graphene interfaces.

The structural superlubricity (SSL), a state of near-zero friction between two contacted solid surfaces, has been attracting rapidly increasing research interest since it was realized in microscale graphite in 2012. An obvious question concerns the implications of SSL for micro- and nanoscale devices such as actuators. The simplest actuators are based on the application of a normal load; here we show that this leads to remarkable dynamical phenomena in microscale graphite mesas. Under an increasing normal load, we observe mechanical instabilities leading to dynamical states, the first where the loaded mesa suddenly ejects a thin flake and the second characterized by peculiar oscillations, during which a flake repeatedly pops out of the mesa and retracts back. The measured ejection speeds are extraordinarily high (maximum of 294 m/s), and correspond to ultrahigh accelerations (maximum of 1.1×1010 m/s2). These observations are rationalized using a simple model, which takes into account SSL of graphite contacts and sample microstructure and considers a competition between the elastic and interfacial energies that defines the dynamical phase diagram of the system. Analyzing the observed flake ejection and oscillations, we conclude that our system exhibits a high speed in SSL, a low friction coefficient of 3.6×10-6, and a high quality factor of 1.3×107 compared with what has been reported in literature. Our experimental discoveries and theoretical findings suggest a route for development of SSL-based devices such as high-frequency oscillators with ultrahigh quality factors and optomechanical switches, where retractable or oscillating mirrors are required.

Structural Superlubricity Based on Crystalline Materials.

Herein, structural superlubricity, a fascinating phenomenon where the friction is ultralow due to the lateral interaction cancellation resulted from incommensurate contact crystalline surfaces, is reviewed. Various kinds of nano- and microscale materials such as 2D materials, metals, and compounds are used for the fabrication. For homogeneous frictional pairs, superlow friction forces exist in most relative orientations with incommensurate configuration. Heterojunctions bear no resemblance to homogeneous contact, since the lattice constants are naturally mismatched which leads to a robust structural superlubricity with any orientation of the two different surfaces. A discussion on the perspectives of this field is also provided to meet the existing challenges and chart the future.

Generalized Scaling Law of Structural Superlubricity.

Structural superlubricity, which promises an ultralow sliding friction due to the cancellation of the lateral force between two incommensurate interfaces, is a fundamental phenomenon in modern tribology. Achieving macroscale superlubricity is critical to its practical application, and the key is understanding how friction scales with real contact area, that is, the scaling law, especially for kinetic friction which accounts for most of the energy dissipation during sliding. Here, inspired by extensive molecular dynamics simulations we introduce an analytical general theory for the scaling law of structural superlubricity, which could well explain existing experimental measurements on the nanoscale. On the microscale, the scaling law is validated by measuring the friction of several microscale superlubric graphite/hexagonal boron nitride heterojunctions. The proposed theory predicts a characteristic size D = O(100 nm) above which the scaling transits from sublinear to linear. Our results provide insights in the origin of friction for structural superlubricity and benefit its application on macroscale.

Strain Engineering Modulates Graphene Interlayer Friction by Moiré Pattern Evolution.

The sliding friction of a graphene flake atop strained graphene substrates is studied using molecular dynamics simulation. We demonstrate that in this superlubric system, friction can be reduced nonmonotonically by applying strain, which differs from previously reported results on various 2D materials. The critical strain needed for significant reduction in friction decreases drastically when the flake size increases. For a 250 nm flake, a 0.1% biaxial strain could lead to a more than 2-order-of-magnitude reduction. The underlying mechanism is revealed to be the evolution of Moiré patterns. The area of the Moiré pattern relative to the flake size plays a central role in determining friction in strain engineering and other scenarios of superlubricity as well. This result suggests that strain engineering could be particularly efficient for friction modification with large contacts.

Rotational Instability in Superlubric Joints.

Surface and interfacial energies play important roles in a number of instability phenomena in liquids and soft matter, but rarely have similar effects in solids. Here, a mechanical instability is reported which is controlled by surface and interfacial energies and is valid for a large class of materials, in particular two-dimensional layered materials. When sliding a top flake cleaved from a square microscale graphite mesa by using a probe acting on the flake through a point contact, it was observed that the flake moved unrotationally for a certain distance before it suddenly transferred to a rotating-moving state. The theoretical analysis was consistent with the experimental observation and revealed that this mechanical instability was an interesting effect of the structural superlubricity (a state of nearly zero friction). Further analysis showed that this type of instability was applicable generally for various sliding joints on different scales, as long as the friction was ultralow. Thus, the uncovered mechanism provides useful knowledge for manipulating and controlling these sliding joints, and can guide the design of future superlubricity-based devices.

Design and optimization of the diamagnetic lateral force calibration method.

The lateral force calibration is a key procedure for applications of atomic force microscopes. Among different calibration methods, the diamagnetic lateral force calibration (DLFC) method has been widely used due to its ease of use as well as being able to estimate the cross talk conversion factor and achieve very small stiffness. The lateral stiffness of the system is the only parameter in the DLFC method; however, its dependence on the properties and parameters of the DLFC system remains unexplored. In this paper, a theoretical formulation of such dependence is developed and experimentally verified. These results provide a guidance to design and optimize future DLFC systems with better applicability and precision in calibrations. As an example, we optimized a DLFC system such that it is robust against normal load, which is previously assumed impossible.