Robert W. Carpick

Frictional Characteristics of Atomically Thin Sheets

Thin Friction The rubbing motion between two surfaces is always hindered by friction, which is caused by continuous contacting and attraction between the surfaces. These interactions may only occur over a distance of a few nanometers, but what happens when the interacting materials are only that thick? Lee et al. (p. 76; see the Perspective by Müser and Shakhvorostov) explored the frictional properties of a silicon tip in contact with four atomically thin quasi–two dimensional materials with different electrical properties. For all the materials, the friction was seen to increase as the thickness of the film decreased, both for flakes supported by substrates and for regions placed above holes that formed freely suspended membranes. Placing graphene on mica, to which it strongly adheres, suppressed this trend. For these thin, weakly adhered films, out-of-plane buckling is likely to dominate the frictional response, which leads to this universal behavior. A universal trend is observed for the friction properties of thin films on weakly adhering substrates. Using friction force microscopy, we compared the nanoscale frictional characteristics of atomically thin sheets of graphene, molybdenum disulfide (MoS2), niobium diselenide, and hexagonal boron nitride exfoliated onto a weakly adherent substrate (silicon oxide) to those of their bulk counterparts. Measurements down to single atomic sheets revealed that friction monotonically increased as the number of layers decreased for all four materials. Suspended graphene membranes showed the same trend, but binding the graphene strongly to a mica surface suppressed the trend. Tip-sample adhesion forces were indistinguishable for all thicknesses and substrate arrangements. Both graphene and MoS2 exhibited atomic lattice stick-slip friction, with the thinnest sheets possessing a sliding-length–dependent increase in static friction. These observations, coupled with finite element modeling, suggest that the trend arises from the thinner sheets’ increased susceptibility to out-of-plane elastic deformation. The generality of the results indicates that this may be a universal characteristic of nanoscale friction for atomically thin materials weakly bound to substrates.

CALIBRATION OF FRICTIONAL FORCES IN ATOMIC FORCE MICROSCOPY

The atomic force microscope can provide information on the atomic‐level frictional properties of surfaces, but reproducible quantitative measurements are difficult to obtain. Parameters that are either unknown or difficult to precisely measure include the normal and lateral cantilever force constants (particularly with microfabricated cantilevers), the tip height, the deflection sensor response, and the tip structure and composition at the tip‐surface contact. We present an in situ experimental procedure to determine the response of a cantilever to lateral forces in terms of its normal force response. This procedure is quite general. It will work with any type of deflection sensor and does not require the knowledge or direct measurement of the lever dimensions or the tip height. In addition, the shape of the tip apex can be determined. We also discuss a number of specific issues related to force and friction measurements using optical lever deflection sensing. We present experimental results on the latera...

Recent advances in single-asperity nanotribology

As the size of electronic and mechanical devices shrinks to the nanometre regime, performance begins to be dominated by surface forces. For example, friction, wear and adhesion are known to be central challenges in the design of reliable micro- and nano-electromechanical systems (MEMS/NEMS). Because of the complexity of the physical and chemical mechanisms underlying atomic-level tribology, it is still not possible to accurately and reliably predict the response when two surfaces come into contact at the nanoscale. Fundamental scientific studies are the means by which these insights may be gained. We review recent advances in the experimental, theoretical and computational studies of nanotribology. In particular, we focus on the latest developments in atomic force microscopy and molecular dynamics simulations and their application to the study of single-asperity contact.

Lateral stiffness: A new nanomechanical measurement for the determination of shear strengths with friction force microscopy

We present a technique to measure the lateral stiffness of the nanometer-sized contact formed between a friction force microscope tip and a sample surface. Since the lateral stiffness of an elastic contact is proportional to the contact radius, this measurement can be used to study the relationship between friction, load, and contact area. As an example, we measure the lateral stiffness of the contact between a silicon nitride tip and muscovite mica in a humid atmosphere (55% relative humidity) as a function of load. Comparison with friction measurements confirms that friction is proportional to contact area and allows determination of the shear strength.

Measurement of interfacial shear (friction) with an ultrahigh vacuum atomic force microscope

We have studied the variation of frictional force with externally applied load for a Pt‐coated atomic force microscope tip in contact with the surface of mica cleaved in ultrahigh vacuum. At low loads, the frictional force varies with load in almost exact proportion to the area of contact as predicted by the Johnson–Kendall–Roberts (JKR) theory [K. L. Johnson, K. Kendall, and A. D. Roberts, Proc. R. Soc. London Ser. A 324, 301 (1971)] of elastic adhesive contacts. The friction‐load relation for a deliberately modified tip shape was proportional to an extended JKR model that predicts the area‐load relation for nonparabolic tips. The tip shape was determined experimentally with a tip imaging technique and was consistent with the predicted friction behavior. This demonstrates that the frictional force is proportional to the area of contact between the tip and sample. Using the JKR/extended JKR model, interfacial surface energies and shear strengths can be estimated.

Polydiacetylene films: a review of recent investigations into chromogenic transitions and nanomechanical properties

Polydiacetylenes (PDAs) form a unique class of polymeric materials that couple highly aligned and conjugated backbones with tailorable pendant sidegroups and terminal functionalities. They can be structured in the form of bulk materials, multilayer and monolayer films, polymerized vesicles, and even incorporated into inorganic host matrices to form nanocomposites. The resulting materials exhibit an array of spectacular properties, beginning most notably with dramatic chromogenic transitions that can be activated optically, thermally, chemically, and mechanically. Recent studies have shown that these transitions can even be controlled and observed at the nanometre scale. These transitions have been harnessed for the purpose of chemical and biomolecular sensors, and on a more fundamental level have led to new insights regarding chromogenic phenomena in polymers. Other recent studies have explored how the strong structural anisotropy that thes em aterials possess leads to anisotropic nanomechanical behaviour. These recen ta dvances suggest that PDAs could be considered as a potential component in nanostructured devices due to the large number of tunable properties. In this paper, we provide a succinct review of the latest insights and applications involving PDA. We then focus in more detail on our work concerning ultrathin films, specifically structural properties, mechanochromism, thermochromism, and in-plane mechanical anisotropy of PDA monolayers. Atomic force microscopy (AFM) and fluorescence microscopy confirm that films 1–3 monolayers thick can be organized into highly ordered domains,with the conjugated backbones parallel to the substrate. The number of stable layers is controlled by the head-group functionality. Local mechanical stress applied by AFM an dn ear-field optical probes induces the chromogenic transition in the film at the nanometre scale. The transition

Ultralow nanoscale wear through atom-by-atom attrition in silicon-containing diamond-like carbon

Understanding friction and wear at the nanoscale is important for many applications that involve nanoscale components sliding on a surface, such as nanolithography, nanometrology and nanomanufacturing. Defects, cracks and other phenomena that influence material strength and wear at macroscopic scales are less important at the nanoscale, which is why nanowires can, for example, show higher strengths than bulk samples. The contact area between the materials must also be described differently at the nanoscale. Diamond-like carbon is routinely used as a surface coating in applications that require low friction and wear because it is resistant to wear at the macroscale, but there has been considerable debate about the wear mechanisms of diamond-like carbon at the nanoscale because it is difficult to fabricate diamond-like carbon structures with nanoscale fidelity. Here, we demonstrate the batch fabrication of ultrasharp diamond-like carbon tips that contain significant amounts of silicon on silicon microcantilevers for use in atomic force microscopy. This material is known to possess low friction in humid conditions, and we find that, at the nanoscale, it is three orders of magnitude more wear-resistant than silicon under ambient conditions. A wear rate of one atom per micrometre of sliding on SiO(2) is demonstrated. We find that the classical wear law of Archard does not hold at the nanoscale; instead, atom-by-atom attrition dominates the wear mechanisms at these length scales. We estimate that the effective energy barrier for the removal of a single atom is approximately 1 eV, with an effective activation volume of approximately 1 x 10(-28) m.

Accounting for the JKR-DMT transition in adhesion and friction measurements with atomic force microscopy

Over the last 15 years, researchers have applied theories of continuum contact mechanics to nanotribology measurements to determine fundamental parameters and processes at play in nanometer-scale contacts. In this paper we discuss work using the atomic force microscope to determine nanoscale adhesion and friction properties between solids. Our focus is on the role that continuum contact mechanics plays in analyzing these measurements. In particular, we show how the JKR-to-DMT transition is taken into account, as well as limitations involved in using these models of contact in the presence of adhesion.

Lateral force calibration in atomic force microscopy : A new lateral force calibration method and general guidelines for optimization

Proper force calibration is a critical step in atomic and lateral force microscopies (AFM/LFM). The recently published torsional Sader method [C. P. Green et al., Rev. Sci. Instrum. 75, 1988 (2004)] facilitates the calculation of torsional spring constants of rectangular AFM cantilevers by eliminating the need to obtain information or make assumptions regarding the cantilever’s material properties and thickness, both of which are difficult to measure. Complete force calibration of the lateral signal in LFM requires measurement of the lateral signal deflection sensitivity as well. In this article, we introduce a complete lateral force calibration procedure that employs the torsional Sader method and does not require making contact between the tip and any sample. In this method, a colloidal sphere is attached to a “test” cantilever of the same width, but different length and material as the “target” cantilever of interest. The lateral signal sensitivity is calibrated by loading the colloidal sphere laterall...

Mechanisms of antiwear tribofilm growth revealed in situ by single-asperity sliding contacts

Additive explanation for anti-wear Additives in oil are vital for protecting engines from wear by forming films at sliding interfaces. Zinc dialkydithiophosphate (ZDDP) has been used for decades to reduce engine wear. Now there is a strong incentive for finding a replacement for ZDDP: Its breakdown products shorten catalytic converter lifetime. Gosvami et al. examined exactly how ZDDP produces an anti-wear film under high stress or elevated temperature (see the Perspective by Schwarz). Understanding these mechanisms will help in the development of higher-performance and more effective additives. Science, this issue p. 102; see also p. 40 Antiwear properties of an oil additive stem from tribofilms that develop under elevated stresses and temperatures. [Also see Perspective by Schwarz] Zinc dialkyldithiophosphates (ZDDPs) form antiwear tribofilms at sliding interfaces and are widely used as additives in automotive lubricants. The mechanisms governing the tribofilm growth are not well understood, which limits the development of replacements that offer better performance and are less likely to degrade automobile catalytic converters over time. Using atomic force microscopy in ZDDP-containing lubricant base stock at elevated temperatures, we monitored the growth and properties of the tribofilms in situ in well-defined single-asperity sliding nanocontacts. Surface-based nucleation, growth, and thickness saturation of patchy tribofilms were observed. The growth rate increased exponentially with either applied compressive stress or temperature, consistent with a thermally activated, stress-assisted reaction rate model. Although some models rely on the presence of iron to catalyze tribofilm growth, the films grew regardless of the presence of iron on either the tip or substrate, highlighting the critical role of stress and thermal activation.