An ability to precisely regulate the quantity and location of molecular flux is of value in applications such as nanoscale 3D printing, catalysis, and sensor design. Barrier materials containing pores with molecular dimensions have previously been us
ed to manipulate molecular compositions in the gas phase, but have so far been unable to offer controlled gas transport through individual pores. Here, we show that gas flux through discrete angstrom-sized pores in monolayer graphene can be detected and then controlled using nanometer-sized gold clusters, which are formed on the surface of the graphene and can migrate and partially block a pore. In samples without gold clusters, we observe stochastic switching of the magnitude of the gas permeance, which we attribute to molecular rearrangements of the pore. Our molecular valves could be used, for example, to develop unique approaches to molecular synthesis that are based on the controllable switching of a molecular gas flux, reminiscent of ion channels in biological cell membranes and solid state nanopores.
We present a unique experimental configuration that allows us to determine the interfacial forces on nearly parallel plates made from the thinnest possible mechanical structures, single and few layer graphene membranes. Our approach consists of using
a pressure difference across a graphene membrane to bring the membrane to within ~ 10-20 nm above a circular post covered with SiOx or Au until a critical point is reached whereby the membrane snaps into adhesive contact with the post. Continuous measurements of the deforming membrane with an AFM coupled with a theoretical model allow us to deduce the magnitude of the interfacial forces between graphene and SiOx and graphene and Au. The nature of the interfacial forces at ~ 10 - 20 nm separations is consistent with an inverse fourth power distance dependence, implying that the interfacial forces are dominated by van der Waals interactions. Furthermore, the strength of the interactions is found to increase linearly with the number of graphene layers. The experimental approach can be used to measure the strength of the interfacial forces for other atomically thin two-dimensional materials, and help guide the development of nanomechanical devices such as switches, resonators, and sensors.
We study the mechanics of pressurized graphene membranes using an experimental configuration that allows the determination of the elasticity of graphene and the adhesion energy between a substrate and a graphene (or other two-dimensional solid) membr
ane. The test consists of a monolayer graphene membrane adhered to a substrate by surface forces. The substrate is patterned with etched microcavities of a prescribed volume and when they are covered with the graphene monolayer it traps a fixed number (N) of gas molecules in the microchamber. By lowering the ambient pressure, and thus changing the pressure difference across the graphene membrane, the membrane can be made to bulge and delaminate in a stable manner from the substrate. Here we describe the analysis of the membrane/substrate as a thermodynamic system and explore the behavior of the system over representative experimentally-accessible geometry and loading parameters. We carry out companion experiments and compare them to the theoretical predictions and then use the theory and experiments together to determine the adhesion energy of graphene/SiO2 interfaces. We find an average adhesion energy of 0.24 J/m2 which is lower, but in line with our previously reported values. We assert that this test, which we call the constant N blister test, is a valuable approach to determine the adhesion energy between two-dimensional solid membranes and a substrate, which is an important, but not well-understood aspect of behavior. The test also provides valuable information that can serve as the basis for subsequent research to understand the mechanisms contributing to the observed adhesion energy. Finally, we show how in the limit of a large microcavity, the constant N test approaches the behavior observed in a constant pressure blister test and we provide an experimental observation that suggests this behavior.
Membranes act as selective barriers and play an important role in processes such as cellular compartmentalization and industrial-scale chemical and gas purification. The ideal membrane should be as thin as possible to maximize flux, mechanically robu
st to prevent fracture, and have well-defined pore sizes to increase selectivity. Graphene is an excellent starting point for developing size selective membranes because of its atomic thickness, high mechanical strength, relative inertness, and impermeability to all standard gases. However, pores that can exclude larger molecules, but allow smaller molecules to pass through have to be introduced into the material. Here we show UV-induced oxidative etching can create pores in micrometre-sized graphene membranes and the resulting membranes used as molecular sieves. A pressurized blister test and mechanical resonance is used to measure the transport of a variety of gases (H2, CO2, Ar, N2, CH4, and SF6) through the pores. The experimentally measured leak rates, separation factors, and Raman spectrum agree well with models based on effusion through a small number of angstrom-sized pores.
In this paper, a method is presented to create and characterize mechanically robust, free standing, ultrathin, oxide films with controlled, nanometer-scale thickness using Atomic Layer Deposition (ALD) on graphene. Aluminum oxide films were deposited
onto suspended graphene membranes using ALD. Subsequent etching of the graphene left pure aluminum oxide films only a few atoms in thickness. A pressurized blister test was used to determine that these ultrathin films have a Youngs modulus of 154 pm 13 GPa. This Youngs modulus is comparable to much thicker alumina ALD films. This behavior indicates that these ultrathin two-dimensional films have excellent mechanical integrity. The films are also impermeable to standard gases suggesting they are pinhole-free. These continuous ultrathin films are expected to enable new applications in fields such as thin film coatings, membranes and flexible electronics.
The interaction of graphene with neighboring materials and structures plays an important role in its behavior, both scientifically and technologically. The interactions are complicated due to the interplay between surface forces and possibly nonlinea
r elastic behavior. Here we review recent experimental and theoretical advances in the understanding of graphene adhesion. We organize our discussion into experimental and theoretical efforts directed toward: graphene conformation to a substrate, determination of adhesion energy, and applications where graphene adhesion plays an important role. We conclude with a brief prospectus outlining open issues.
As mechanical structures enter the nanoscale regime, the influence of van der Waals forces increases. Graphene is attractive for nanomechanical systems because its Youngs modulus and strength are both intrinsically high, but the mechanical behavior o
f graphene is also strongly influenced by the van der Waals force. For example, this force clamps graphene samples to substrates, and also holds together the individual graphene sheets in multilayer samples. Here we use a pressurized blister test to directly measure the adhesion energy of graphene sheets with a silicon oxide substrate. We find an adhesion energy of 0.45 pm 0.02 J/m2 for monolayer graphene and 0.31 pm 0.03 J/m2 for samples containing 2-5 graphene sheets. These values are larger than the adhesion energies measured in typical micromechanical structures and are comparable to solid/liquid adhesion energies. We attribute this to the extreme flexibility of graphene, which allows it to conform to the topography of even the smoothest substrates, thus making its interaction with the substrate more liquid-like than solid-like.
