Template-Stripped Ultra-Smooth Aluminum Films (0.2 nm RMS) for the Surface Forces Apparatus.

We present a method for the fabrication of ultra-smooth (0.2 nm RMS), aluminum substrates through template stripping (TS). The method relies on the use of mica as a template in combination with thermal evaporation of Al at high (>10 nm/s) rates under vacuum (≤1 × 10-7 Torr). As a reactive metal, Al is usually not considered a viable option for TS off oxide templates. However, under these conditions, the adhesion between the Al film and mica is poor, enabling the removal of the template under water without any mica residue. We verify the absence of mica using atomic force microscopy, X-ray photoelectron spectroscopy, and contact angle measurements. We establish the suitability of these films for surface forces measurements. Multiple-bean interferometry in transmission yields high quality fringes allowing for the measurement of force-distance curves. The adhesion the films to mica is significantly higher than the adhesion of thermally evaporated Al (0.9 nm RMS). Preliminary results suggest that the TS-Al surface displays a higher corrosion resistance. The fabrication method will enable important experiments on this widely used material.

Direct Measurement of the Surface Energy of Graphene.

Graphene produced by chemical vapor deposition (CVD) is a promising candidate for implementing graphene in a range of technologies. In most device configurations, one side of the graphene is supported by a solid substrate, wheras the other side is in contact with a medium of interest, such as a liquid or other two-dimensional material within a van der Waals stack. In such devices, graphene interacts on both faces via noncovalent interactions and therefore surface energies are key parameters for device fabrication and operation. In this work, we directly measured adhesive forces and surface energies of CVD-grown graphene in dry nitrogen, water, and sodium cholate using a modified surface force balance. For this, we fabricated large (∼1 cm2) and clean graphene-coated surfaces with smooth topography at both macro- and nanoscales. By bringing two such surfaces into contact and measuring the force required to separate them, we measured the surface energy of single-layer graphene in dry nitrogen to be 115 ± 4 mJ/m2, which was similar to that of few-layer graphene (119 ± 3 mJ/m2). In water and sodium cholate, we measured interfacial energies of 83 ± 7 and 29 ± 6 mJ/m2, respectively. Our work provides the first direct measurement of graphene surface energy and is expected to have an impact both on the development of graphene-based devices and contribute to the fundamental understanding of surface interactions.

Complex chiral colloids and surfaces via high-index off-cut silicon.

Silicon wafers are commonly etched in potassium hydroxide solutions to form highly symmetric surface structures. These arise when slow-etching {111} atomic planes are exposed on standard low-index surfaces. However, the ability of nonstandard high-index wafers to provide more complex structures by tilting the {111} planes has not been fully appreciated. We demonstrate the power of this approach by creating chiral surface structures and nanoparticles of a specific handedness from gold. When the nanoparticles are dispersed in liquids, gold colloids exhibiting record molar circular dichroism (>5 × 10(9) M(-1) cm(-1)) at red wavelengths are obtained. The nanoparticles also present chiral pockets for binding.

A graphene surface force balance.

We report a method for transferring graphene, grown by chemical vapor deposition, which produces ultraflat graphene surfaces (root-mean-square roughness of 0.19 nm) free from polymer residues over macroscopic areas (>1 cm(2)). The critical step in preparing such surfaces involves the use of an intermediate mica template, which itself is atomically smooth. We demonstrate the compatibility of these model surfaces with the surface force balance, opening up the possibility of measuring normal and lateral forces, including friction and adhesion, between two graphene sheets either in contact or across a liquid medium. The conductivity of the graphene surfaces allows forces to be measured while controlling the surface potential. This new apparatus, the graphene surface force balance, is expected to be of importance to the future understanding of graphene in applications from lubrication to electrochemical energy storage systems.

Cooperative Tridentate Hydrogen-Bonding Interactions Enable Strong Underwater Adhesion.

Multidentate hydrogen-bonding interactions are a promising strategy to improve underwater adhesion. Molecular and macroscale experiments have revealed an increase in underwater adhesion by incorporating multidentate H-bonding groups, but quantitatively relating the macroscale adhesive strength to cooperative hydrogen-bonding interactions remains challenging. Here, we investigate whether tridentate alcohol moieties incorporated in a model epoxy act cooperatively to enhance adhesion. We first demonstrate that incorporation of tridentate alcohol moieties leads to comparable adhesive strength with mica and aluminum in air and in water. We then show that the presence of tridentate groups leads to energy release rates that increase with an increase in crack velocity in air and in water, while materials lacking these groups do not display rate-dependent adhesion. We model the rate-dependent adhesion to estimate the activation energy of the interfacial bonds. Based on our data, we estimate the lifetime of these bonds to be between 2 ms and 6 s, corresponding to an equilibrium activation energy between 23kBT and 31kBT. These values are consistent with tridentate hydrogen bonding, suggesting that the three alcohol groups in the Tris moiety bond cooperatively form a robust adhesive interaction underwater.

Contact-free calibration of an asymmetric multi-layer interferometer for the surface force balance.

The Surface Force Balance (SFB, also known as Surface Force Apparatus, SFA) has provided important insights into many phenomena within the field of colloid and interface science. The technique relies on using white light interferometry to measure the distance between surfaces with sub-nanometer resolution. Up until now, the determination of the distance between the surfaces required a so-called "contact calibration," an invasive procedure during which the surfaces are brought into mechanical contact. This requirement for a contact calibration limits the range of experimental systems that can be investigated with SFB, for example, it precludes experiments with substrates that would be irreversibly modified or damaged by mechanical contact. Here we present a non-invasive method to measure absolute distances without performing a contact calibration. The method can be used for both "symmetric" and "asymmetric" systems. We foresee many applications for this general approach including, most immediately, experiments using single layer graphene electrodes in the SFB which may be damaged when brought into mechanical contact.

Ultraviolet Plasmonic Chirality from Colloidal Aluminum Nanoparticles Exhibiting Charge-Selective Protein Detection.

Chiral aluminum nanoparticles, dispersed in water, are prepared, which provide strong ultraviolet plasmonic circular dichroism, high-energy superchiral near-fields, and charge-selective protein detection.