Understanding the role of crosslink density and linear viscoelasticity on the shear failure of pressure-sensitive-adhesives.

Pressure-sensitive-adhesives (PSAs) are ubiquitous in electronic, automobile, packaging, and biomedical applications due to their ability to stick to numerous surfaces without undergoing chemical reactions. Although these materials date back to the 1850s with the development of surgical tapes based on natural rubber, their resistance to shear loads remains challenging to predict from molecular design. This work investigates the role of crosslink density on the shear resistance of model PSAs based on poly(2-ethylhexyl acrylate-co-acrylic acid) physically crosslinked with aluminum acetylacetonate. The key result is that crosslinking PSAs leads to notable stress concentrations ahead of the peel front, as well as a transition from cohesive to adhesive failure. The shear stress distributions, as evaluated by means of a linearly viscoelastic shear lag model, suggest that this transition is related to the evolution of the ratio of the load transfer length to the bond length as dictated by the mechanical properties of the backing and adhesive layers, and the geometry of the tape.

Controlling the number of layers in graphene using the growth pressure.

Monolayer graphene is commonly grown on Cu substrates due to the self-limiting nature of graphene synthesis by chemical vapor deposition (CVD). Consequently, the growth of multilayer graphene by CVD has proven to be relatively difficult. This study demonstrates that the number of layers in graphene synthesized on a copper substrate can be precisely set by controlling the partial pressure of hydrogen gas used in the CVD process. This study also shows that a pressure threshold exists for a distinct transition from monolayer to multilayer graphene growth. This threshold is shown to be the boundary where the graphene growth process on Cu by CVD is no longer a self-limiting process. In addition, the multilayer graphene synthesized through the pressure control method forms in the Volmer-Weber mode with an AB stacking structure.

Large-Area Dry Transfer of Single-Crystalline Epitaxial Bismuth Thin Films.

We report the first direct dry transfer of a single-crystalline thin film grown by molecular beam epitaxy. A double cantilever beam fracture technique was used to transfer epitaxial bismuth thin films grown on silicon (111) to silicon strips coated with epoxy. The transferred bismuth films retained electrical, optical, and structural properties comparable to the as-grown epitaxial films. Additionally, we isolated the bismuth thin films on freestanding flexible cured-epoxy post-transfer. The adhesion energy at the bismuth/silicon interface was measured to be ∼1 J/m2, comparable to that of exfoliated and wet transferred graphene. This low adhesion energy and ease of transfer is unexpected for an epitaxially grown film and may enable the study of bismuth's unique electronic and spintronic properties on arbitrary substrates. Moreover, this method suggests a route to integrate other group-V epitaxial films (i.e., phosphorus) with arbitrary substrates, as well as potentially to isolate bismuthene, the atomic thin-film limit of bismuth.

Extending the resolution limits of nanoshape imprint lithography using molecular dynamics of polymer crosslinking.

Emerging nanoscale applications in energy, electronics, optics, and medicine can exhibit enhanced performance by incorporating nanoshaped structures (nanoshape structures here are defined as shapes enabled by sharp corners with radius of curvature < 5 nm). Nanoshaped fabrication at high-throughput is well beyond the capabilities of advanced optical lithography. Although the highest-resolution e-beams and large-area e-beams have a resolution limit of 5 and 18 nm half-pitch lines or 20 nm half-pitch holes, respectively, their low throughput necessitates finding other fabrication techniques. By using nanoimprint lithography followed by metal-assisted chemical etching, diamond-like nanoshapes with ~3 nm radius corners and 100 nm half-pitch over large areas have been previously demonstrated to improve the nanowire capacitor performance (by ~90%). In future dynamic random-access memory (DRAM) nodes (with DRAM being an exemplar CMOS application), the implementation of nanowire capacitors scaled to <15 nm half-pitch is required. To scale nanoshape imprint lithography down to these half-pitch values, the previously established atomistic simulation framework indicates that the current imprint resist materials are unable to retain the nanoshape structures needed for DRAM capacitors. In this study, the previous simulation framework is extended to study improved shape retention by varying the resist formulations and by introducing novel bridge structures in nanoshape imprinting. This simulation study has demonstrated viable approaches to sub-10 nm nanoshaped imprinting with good shape retention, which are matched by experimental data.

Mechanical probing of icelike water monolayers.

Direct measurements of the normal force interactions between a mica-tungsten contact pair at various humidity levels reveal the presence of repulsive forces at about 0.5 nm before intimate contact. Such repulsive interactions begin to appear above 20% RH and are fully developed in the range of 38-45% RH. Using the DMT model of contact, a reduced elastic modulus of approximately 6.7 GPa is extracted from these repulsive interactions and attributed to the presence of icelike water on mica at room temperature. The collapse of such structures was also inferred from the measurements.

On scale dependence in friction: transition from intimate to monolayer-lubricated contact.

Scale dependence in friction is studied in the present paper using the newly developed mesoscale friction tester (MFT). A transition in frictional shear strength from several hundreds of MPa to several tens of MPa was observed over a very limited range of contact radii (20-30 nm) in both ambient and dry environments. Thus, a single apparatus has been able to establish these two limits which are consistent with the values previously obtained from friction experiments using atomic force microscopy (AFM) and the surface force apparatus (SFA), respectively. Consequently, it is hypothesized here that a shear strength in the hundreds of MPa results from intimate contact (solid-solid) and a shear strength in the tens of MPa results from a monolayer-lubricated contact. Furthermore, both the probe size and the normal pressure govern the interfacial conditions in the contact zone and it is these conditions, rather than the nominal environment, which in turn determine the resulting shear strengths. A continuum analysis based on the Lifshitz theory for van der Waals interactions is used to explain the quantized shear strengths which were obtained from our experiments and previous AFM and SFA friction experiments. This quantized friction behavior [J.N. Israelachvili, P.M. McGuiggan, A.M. Homola, Science 240 (1988) 189] results from the discrete separation due to the different interfacial conditions that can arise between two sliding surfaces. The consistency between the analysis and the experimental results shows that this analysis is applicable for nonwear friction with single asperity contact.

On the modified Tabor parameter for the JKR-DMT transition in the presence of a liquid meniscus.

The JKR, DMT, Maugis models and Tabor parameter for contact under normal loading have been developed based mainly on solid-solid (van der Waals) interactions. In this case, the characteristic length scale for the adhesive forces in the Tabor parameter is the equilibrium interatomic spacing. However, for contact in humid environments, where a liquid meniscus may be present, capillary forces with a longer force range related to the Kelvin radius dominate. Fogden and White [J. Colloid Interface Sci. 138 (1990) 414] introduced a parameter that includes the Kelvin radius for the JKR-DMT transition. This topic was also addressed by Maugis and Gauthier-Manuel [J. Adhes. Sci. Technol. 8 (1994) 1311] who included capillary effects within the frame work that Maugis had previously established. The parameters introduced by Fogden and White and Maugis and Gauthier-Manuel can be viewed as a modified Tabor parameter for the JKR-DMT transition. In the present work, the Kelvin equation linking the Kelvin radius and the relative humidity was explicitly included in the modified Tabor parameter. This provided a quantitative description of the JKR-DMT transition in terms of the relative humidity. This parameter was examined via load and contact radius measurements, where the latter were obtained from Bowden and Tabor's assumption that the friction force f=tauA. The friction experiments were conducted at two different humidity levels using a newly-developed mesoscale friction tester (MFT), which provides a very wide range of contact radii. The modified Tabor parameter was used to reexamine data from pull-off experiments in water and cyclohexane vapor environments [L.R. Fisher, J.N. Israelachvili, Colloids Surf. 3 (1981) 303 and H.K. Christenson, J. Colloid Interface Sci. 121 (1988) 170]. Finally, guidelines are presented for the appropriate choice of contact mechanics models to be used in interpreting data from SFA and AFM experiments in humid environments.

Mesoscale scanning probe tips with subnanometer rms roughness.

Surface smoothness of probe tips is critical for applications, such as measuring surface tension of various liquids, oscillatory hydration forces, and interfacial shear strengths from friction experiments. In this study we establish conditions for fabricating tips with smooth surfaces by controlling the electrochemical polishing process throughout the tip evolution rather than following the current practice of producing tips by the drop-off method. Polishing is conducted under a constant voltage, with the wire immersed below the nominal air/electrolyte interface by no more than one-half of the wire diameter and stopping the etching at different current levels. This process provides a tip radius range of approximately 100 nm to 5 microm for a tungsten wire with a 0.2 mm diameter. Alternatively, the wire can be placed above the nominal air/electrolyte interface but within the meniscus until the current drops to zero. In this case, the tip radii range from 5 to 50 microm. In both cases, atomic force microscopy scans of these tips show that the surface rms roughness is about 0.3 nm.

Adhesion and Self-Healing between Monolayer Molybdenum Disulfide and Silicon Oxide.

The adhesion interactions of two-dimensional (2D) materials are of importance in developing flexible electronic devices due to relatively large surface forces. Here, we investigated the adhesion properties of large-area monolayer MoS2 grown on silicon oxide by using chemical vapor deposition. Fracture mechanics concepts using double cantilever beam configuration were used to characterize the adhesion interaction between MoS2 and silicon oxide. While the interface between MoS2 and silicon oxide was fractured under displacement control, force-displacement response was recorded. The separation energy, adhesion strength and range of the interactions between MoS2 and silicon oxide were characterized by analytical and numerical analyses. In addition to the fundamental adhesion properties of MoS2, we found that MoS2 monolayers on silicon oxide had self-healing properties, meaning that when the separated MoS2 and silicon oxide were brought into contact, the interface healed. The self-healing property of MoS2 is potentially applicable to the development of new composites or devices using 2D materials.

Cracking of Polycrystalline Graphene on Copper under Tension.

Roll-to-roll manufacturing of graphene is attractive because of its compatibility with flexible substrates and its promise of high-speed production. Several prototype roll-to-roll systems have been demonstrated, which produce large-scale graphene on polymer films for transparent conducting film applications.1-4 In spite of such progress, the quality of graphene may be influenced by the tensile forces that are applied during roll-to-roll transfer. To address this issue, we conducted in situ tensile experiments on copper foil coated with graphene grown by chemical vapor deposition, which were carried out in a scanning electron microscope. Channel cracks, which were perpendicular to the loading direction, initiated over the entire graphene monolayer at applied tensile strain levels that were about twice the yield strain of the (annealed) copper. The spacing between the channel cracks decreased with increasing applied strain, and new graphene wrinkles that were parallel to the loading direction appeared. These morphological features were confirmed in more detail by atomic force microscopy. Raman spectroscopy was used to determine the strain in the graphene, which was related to the degradation of the graphene/copper interface. The experimental data allowed the fracture toughness of graphene and interfacial properties of the graphene/copper interface to be extracted based on classical channel crack and shear-lag models. This study not only deepens our understanding of the mechanical and interfacial behavior of graphene on copper but also provides guidelines for the design of roll-to-roll processes for the dry transfer of graphene.

Selective mechanical transfer of graphene from seed copper foil using rate effects.

A very fast, dry transfer process based on mechanical delamination successfully effected the transfer of large-area, CVD grown graphene on copper foil to silicon. This has been achieved by bonding silicon backing layers to both sides of the graphene-coated copper foil with epoxy and applying a suitably high separation rate to the backing layers. At the highest separation rate considered (254.0 µm/s), monolayer graphene was completely transferred from the copper foil to the target silicon substrate. On the other hand, the lowest rate (25.4 µm/s) caused the epoxy to be completely separated from the graphene. Fracture mechanics analyses were used to determine the adhesion energy between graphene and its seed copper foil (6.0 J/m(2)) and between graphene and the epoxy (3.4 J/m(2)) at the respective loading rates. Control experiments for the epoxy/silicon interface established a rate dependent adhesion, which supports the hypothesis that the adhesion of the graphene/epoxy interface was higher than that of the graphene/copper interface at the higher separation rate, thereby providing a controllable mechanism for selective transfer of graphene in future nanofabrication systems such as roll-to-roll transfer.

Ultra long-range interactions between large area graphene and silicon.

The wet-transfer of graphene grown by chemical vapor deposition (CVD) has been the standard procedure for transferring graphene to any substrate. However, the nature of the interactions between large area graphene and target substrates is unknown. Here, we report on measurements of the traction-separation relations, which represent the strength and range of adhesive interactions, and the adhesion energy between wet-transferred, CVD grown graphene and the native oxide surface of silicon substrates. These were determined by coupling interferometry measurements of the separation between the graphene and silicon with fracture mechanics concepts and analyses. The measured adhesion energy was 357 ± 16 mJ/m(2), which is commensurate with van der Waals interactions. However, the deduced traction-separation relation for graphene-silicon interactions exhibited a much longer range interaction than those normally associated with van der Waals forces, suggesting that other mechanisms are present.

Self-assembled silane monolayers: fabrication with nanoscale uniformity.

Illustrating direct connections between surface chemical events and mechanical and topological characteristics of self-assembled monolayers derived from octadecyltrichlorosilane (OTS) adsorption on Si(100), layers prepared in the presence and absence of moisture have been characterized. Uniform and robust self-assembled monolayers are demonstrated provided the Si(100) surface is fully hydroxylated by treatment in piranha solution and the dried surface is exposed to OTS under strict anhydrous conditions. With nanoscale resolution, the uniform mechanical properties are confirmed by interfacial force microscopy while the uniform topological properties are evident in atomic force microscopy images. The monolayer character of the OTS coverage is confirmed by X-ray photoelectron spectroscopy, ellipsometry, and patterning experiments. Analogous surfaces, prepared in the presence of moisture, exhibit nonuniform topological and mechanical properties.