Graphene Blisters Research Articles

Valley filters using graphene blister defects from first principles

Valleytronics, which makes use of the two valleys in graphenes, attracts considerable attention and a valley filter is expected to be the central component in valleytronics. We propose the application of the graphene valley filter using blister defects to the investigation of the valley-dependent transport properties of the Stone–Wales and blister defects of graphenes by density functional theory calculations. It is found that the intervalley transition from the K valley to the valleys is completely suppressed in some defects. Using a large bipartite honeycomb cell (BHC) including several carbon atoms in a cell and replacing atomic orbitals with molecular orbitals in the tight-binding model, we demonstrate analytically and numerically that the symmetry between the A and B sites of the BHC contributes to the suppression of the intervalley transition. In addition, the universal rule for the atomic structures of the blisters suppressing the intervalley transition is derived. Furthermore, by introducing additional carbon atoms to graphenes to form blister defects, we can split the energies of the states at which resonant scattering occurs on the and channel electrons. Because of this split, the fully valley-polarized current will be achieved by the local application of a gate voltage.

Graphene Nano-Blister in Graphite for Future Cathode in Dual-Ion Batteries: Fundamentals, Advances, and Prospects.

The intercalating of anions into cost-effective graphite electrode provides a high operating voltage, therefore, the dual-ion batteries (DIBs) as novel energy storage device has attracted much attention recently. The "graphene in graphite" has always existed in the graphite cathode of DIBs, but has rarely been researched. It is foreseeable that the graphene blisters with the intact lattice structure in the shell can utilize its ultra-high elastic stiffness and reversible lattice expansion for increasing the storage capacity of anions in the batteries. This review proposes an expected "blister model" by introducing the high elasticity of graphene blisters and its possible formation mechanism. The unique blisters composed of multilayer graphene that do not fall off on the graphite surface may become indispensable in nanotechnology in the future development of cathode materials for DIBs.

Hoop compression driven instabilities in spontaneously formed multilayer graphene blisters over a polymeric substrate

The blistering of elastic membranes is prone to elastic-solid as well as substrate-based mechanical instabilities. The solid-based instabilities have been well-explored in the mechanically indented blisters of elastic membranes over the rigid/solid substrates, but an integrated study illustrating the underlying mechanism for the onset of solid as well as substrate-based instabilities in the spontaneous blistering of a 2D material is still lacking in the literature. In this article, an extensive experimental as well as analytical analysis of the spontaneous blister-formation in the multilayer graphene (MLG) flakes over a polymeric substrate is reported, which elucidates the involved mechanism and the governing parameters behind the development of elastic-solid as well as viscoelastic-substrate based instabilities. Herein, a ‘blister-collapse model’ is proposed, which infers that the suppression of the hoop compression, resulting from the phase-transition of the confined matter, plays a crucial role in the development of the instabilities. The ratio of blister-height to flake-thickness is a direct consequence of the taper-angle of the MLG blister and the thickness-dependent elasticity of the upper-bounding MLG flake, which shows a significant impact on the growth-dynamics of the viscous fingering pattern (viscoelastic-substrate based instability) under the MLG blister.

Polymer curing assisted formation of optically visible sub-micron blisters of multilayer graphene for local strain engineering

The local or global straining techniques are used to modulate the electronic, vibrational and optical properties of the two-dimensional (2D) materials. However, manipulating the physical properties of a 2D material under a local strain is comparatively more challenging. In this work, we demonstrate an easy and efficient polymer curing assisted technique for the formation of optically visible multilayer graphene (MLG) blisters of different shapes and sizes. The detailed spectroscopic and morphological analyses have been employed for exploring the dynamics of the confined matter inside the sub-micron blisters, which confirms that the confined matter inside the blister is liquid (water). From further analyses, we find the nonlinear elastic plate model as an acceptable model under certain limits for the mechanical analyses of the MLG blisters over the (poly)vinyl alcohol (PVA) polymer film to estimate the MLG-substrate interfacial adhesion energy and confinement pressure inside the blisters. The findings open new pathways for exploiting the technique for the formation of sub-micron blisters of the 2D materials for local strain-engineering applications, as well as the temperature-controlled release of the confined matter.

Dynamic, Spontaneous Blistering of Substrate-Supported Graphene in Acidic Solutions.

We report that for monolayer and few-layer graphene on common silicon and glass substrates, acidic solutions induce fast, spontaneous generation of solution-enclosing blisters/bubbles. Using interference reflection microscopy, we monitor the blister-generating process in situ and show that at pH < ∼2, nanoscale to micrometer-sized graphene blisters, up to ∼100 nm in height, are universally generated with high surface coverages on hydrophilic, but not hydrophobic, surfaces. The spontaneously generated blisters are highly dynamic, with growth, merging, and reconfiguration occurring at second-to-minute time scales. Moreover, we show that in this dynamic system, graphene behaves as a semipermeable membrane that allows the relatively free passing of water, impeded passing of the NaCl solute, and no passing of large dye molecules. Consequently, the blister volumes can be fast and reversibly modulated by the solution osmotic pressure.

Nanostructuring of CVD graphene by high-energy heavy ions

In this study, CVD graphene with a typical set of structural features (domains, folds and blisters) is used to see the relation between the effects of its nanostructuring by high-energy ion irradiation (Xe and Kr with energies 26–167 MeV) and the graphene structure. The pore size was found to depend on the domain size and the ion energy, and equal to 10–30 nm and 60–80 nm for domains of 1–3 μm and ~10 μm, respectively. The pore density was estimated as ~10% from the ion fluence. The maximum pore density, approximately equal to the ion dose, was found in the strained graphene blisters. The formation of more complex structural defects (presumably, ultrashort nanotubes covered with a graphene monolayer on the top) is also revealed after the ion irradiation in few-layer graphene. The top layer preservation after irradiation was justified by the molecular dynamics simulation and caused by lower energy losses (absence of the electrons knocked out of the previous layers). The possibility of forming vertical wells in ultrashort nanotubes, due to interlayer covalent bonds at the edges of some pores, is very attractive for applications. The use of CVD graphene provides ample opportunities for controlling the structure and properties of nanostructured materials.

Improved Graphene Blisters by Ultrahigh Pressure Sealing.

Graphene is a very attractive material for nanomechanical devices and membrane applications. Graphene blisters based on silicon oxide microcavities are a simple but relevant example of nanoactuators. A drawback of this experimental setup is that gas leakage through the graphene-SiO2 interface contributes significantly to the total leak rate. Here, we study the diffusion of air from pressurized graphene drumheads on SiO2 microcavities and propose a straightforward method to improve the already strong adhesion between graphene and the underlying SiO2 substrate, resulting in reduced leak rates. This is carried out by applying controlled and localized ultrahigh pressure (>10 GPa) with an atomic force microscopy diamond tip. With this procedure, we are able to significantly approach the graphene layer to the SiO2 surface around the drumheads, thus enhancing the interaction between them, allowing us to better seal the graphene-SiO2 interface, which is reflected in up to ∼ 4 times lower leakage rates. Our work opens an easy way to improve the performance of graphene as a gas membrane on a technological relevant substrate such as SiO2.

A Mock Gas Molecules Model for Accurately Simulating Pressure Load at Micro- and Nanoscales

At micro- and nanoscales, the gas pressure load is generally simulated by the thermal motion of gas molecules. However, the pressure load can hardly be produced or controlled accurately, because the effects of the wall thickness and the atomic weight of the gas molecules are not taken into account. In this paper, we propose a universal gas molecules model for simulating the pressure load accurately at micro- and nanoscales, named mock gas molecules model. Six scale-independent parameters are established in this model, thus the model is applicable at both micro- and nanoscales. To present the validity and accuracy of the model, the proposed model is applied into the coarse-grained molecular dynamics simulation of graphene blister, and the simulation results agree well with experimental observations from the graphene blister test, indicating that the model can produce and control the pressure load accurately. Furthermore, the model can be easily implemented into many simulators for problems about the solid–gas interaction, especially for membrane gas systems.

Laser-Based Texturing of Graphene to Locally Tune Electrical Potential and Surface Chemistry.

A simple procedure of producing three-dimensional blisters of graphene through irradiation of the visible range laser by Raman spectrometer has been presented. Fabrication of different volumes of the blisters and their characterization were carried out with Raman spectroscopy by tuning the irradiation dose. The produced blisters showed a consistency in altitude and a remarkable change in functionality, adhesion force map and local contact potential difference as compared to untreated monolayer graphene and naturally occurred graphene nanobubbles. Nevertheless, bilayer graphene is unaffected in the applied laser doses. The laser irradiation led to lattice expansion of carbon atoms and introduced oxygenic functional groups with the structural disorder. The internal pressure of the gaseous molecules was evaluated by monitoring the shape of the graphene blisters and nanobubbles. High-resolution Raman mapping showed the impact of laser-affected area and the defect density (nd) is reported as a function of displacement. Our results reveal ease of applicability of the Raman laser for the imaging and texturing of graphene pointing toward the possibility of the desirable and cost-effective laser writing at the submicron scale by tuning photochemistry of graphene which is pivotal for numerous applications.

Extended Hencky solution for the blister test of nanomembrane

The blister test has been extensively used as a simple and effective approach to measure the elastic modulus and the interface adhesion energy of two-dimensional nanomembrane. However, the conventional blister test model is commonly based on the Hencky solution in which the clamped boundary is assumed without consideration of sliding, and consequently, it can hardly obtain the stress distribution outside the blister region. Therefore, in this paper, the clamped boundary condition is removed, and the Hencky solution is extended based on the Lame solution to account for both the sliding displacement and the stress and strain fields outside the blister region. The expression of the extended Hencky solution is as simple as the original one, but it provides a more accurate description for both the blister configuration and the stress and strain fields of nanomembrane, which are proved by molecular dynamics (MD) simulations of graphene blister test. Our theoretical model is further validated by the experimental results regarding the blister test of a monolayer graphene membrane, where a higher accuracy can be observed in the interpretation of the data.

Snap Transitions of Pressurized Graphene Blisters

Blister tests are commonly used to determine the mechanical and interfacial properties of thin film materials with recent applications for graphene. This paper presents a numerical study on snap transitions of pressurized graphene blisters. A continuum model is adopted combining a nonlinear plate theory for monolayer graphene with a nonlinear traction–separation relation for van der Waals interactions. Three types of blister configurations are considered. For graphene bubble blisters, snap-through and snap-back transitions between pancake-like and dome-like shapes are predicted under pressure-controlled conditions. For center-island graphene blisters, snap transitions between donut-like and dome-like shapes are predicted under both pressure and volume control. Finally, for the center-hole graphene blisters, growth is stable under volume or N-control but unstable under pressure control. With a finite hole depth, the growth may start with a snap transition under N-control if the hole is relatively deep. The numerical results provide a systematic understanding on the mechanics of graphene blisters, consistent with previously reported experiments. Of particular interest is the relationship between the van der Waals interactions and measurable quantities in corresponding blister tests, with which both the adhesion energy of graphene and the equilibrium separation for the van der Waals interactions may be determined. In comparison with approximate solutions based on membrane analyses, the numerical method offers more accurate solutions that may be used in conjunction with experiments for quantitative characterization of the interfacial properties of graphene and other two-dimensional (2D) membrane materials.

Analyzing the temperature sensitivity of Fabry-Perot sensor using multilayer graphene diaphragm.

A miniature Fabry-Perot interferometric sensor with an ultra-high temperature sensitivity was constructed by using an approximate 8-layer graphene diaphragm. The extremely thin diaphragm was transferred onto the endface of a ferrule with an inner diameter of 125 μm, and van der Waals interactions between the graphene diaphragm and its substrate created a low finesse Fabry-Perot interferometer with a cavity length of 42.86 μm. Temperature testing demonstrated a temperature-induced cavity length change of 352 nm/°C with a good linearity in the range of 20-60 °C. The result conformed well to the proposed analytical models relating to thermal expansion of trapped gas, thermal-optical property of graphene diaphragm and deflection behavior of bulged graphene blister. However, the ultra-thin diaphragm exhibited a small deflection deformation characteristic due to the applied higher loads.

Doping- and interference-free measurement of I2D/IG in suspended monolayer graphene blisters

We report on strong interference effects on the ratio of the integrated intensities of the Raman 2D- and G-mode features (herein denoted ) in suspended graphene monolayers. Free from substrate-induced doping and residual charge inhomogeneity, suspended samples are an ideal platform to study the intrinsic properties of graphene. Here, we demonstrate that , measured on a pressurized suspended graphene blister, depends very sensitively on the distance between the bulged graphene membrane and the underlying substrate. The data obtained on three different samples are fit to theoretically predicted Raman enhancement factors and allow to extract an intrinsic, i.e., doping- and interference-free, value of for undoped, unscreened graphene at a laser photon energy of .

Effect of initial tension on mechanics of adhered graphene blisters

The effect of initial tension on mechanics of adhered graphene blisters is investigated by extending Hencky’s solution to cases with an initial tension. The system parameters including maximum blister deflection, pressure difference across the membrane, and critical delamination pressure under various initial tensions are modeled and calculated. The dependences of critical pressure on the radius and depth of etched microcavity are also demonstrated and compared with the previous work which does not consider the initial tension. The results show that the added adhesion energy between monolayer graphene membrane and SiO2 substrate can reach 0.0954 J/m2 with a reported maximum initial tension of 2.4 N/m taken into account, which accounts for 21.2 % of the measured average value 0.45 J/m2. Thus, the initial tension should be considered in further adhesion energy measurements of graphene/substrate interfaces.

Inflating Graphene with Atomic Scale Blisters

Using 80 kV electron beam irradiation we have created graphene blister defects of additional carbon atoms incorporated into a graphene lattice. These structures are the antithesis of the vacancy defect with blister defects observed to contain up to six additional carbon atoms. We present aberration-corrected transmission electron microscopy data demonstrating the formation of a blister from an existing divacancy, together with further examples that undergo reconfiguration and annihilation under the electron beam. The relative stability of the observed variations of blister are discussed and considered in the context of previous calculations. It is shown that the blister defect is seldom found in isolation and is more commonly coupled with dislocations where it can act as an intermediate state, permitting dislocation core climb without the atom ejection from the graphene lattice required for nonconservative motion.

Graphene Blisters with Switchable Shapes Controlled by Pressure and Adhesion

We created graphene blisters that cover and seal an annular cylinder-shaped microcavity in a SiO2 substrate filled with a gas. By controlling the pressure difference between the gas inside and outside of the microcavity, we switch the graphene membrane between multiple stable equilibrium configurations. We carried out experiments starting from the situation where the pressure of the gas inside and outside of the microcavity is set equal to a prescribed charging pressure, p0 and the graphene membrane covers the cavity like an annular drum, adhered to the central post and the surrounding substrate due to van der Waals forces. We decrease the outside pressure to a value, pe which causes it to bulge into an annular blister. We systematically increase the charging pressure by repeating this procedure causing the annular blister to continue to bulge until a critical charging pressure pc(i) is reached. At this point the graphene membrane delaminates from the post in an unstable manner, resulting in a switch of graphene membrane shape from an annular to a spherical blister. Continued increase of the charging pressure results in the spherical blister growing with its height increasing, but maintaining a constant radius until a second critical charging pressure pc(o) is reached at which point the blister begins to delaminate from the periphery of the cavity in a stable manner. Here, we report a series of experiments as well as a mechanics and thermodynamic model that demonstrate how the interplay among system parameters (geometry, graphene stiffness (number of layers), pressure, and adhesion energy) results in the ability to controllably switch graphene blisters among different shapes. Arrays of these blisters can be envisioned to create pressure-switchable surface properties where the difference between patterns of annular versus spherical blisters will impact functionalities such as wettability, friction, adhesion, and surface wave characteristics.

Mechanics of Adhered, Pressurized Graphene Blisters

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) membrane. 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. This is in contrast to the more common scenario of a constant pressure membrane blister test, where membrane delamination is unstable, and so this is not an appealing test to determine adhesion energy. 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.

Hydrogen accumulation in graphite and etching of graphite on hydrogen desorption

Studies of Atomic Hydrogen accumulation in highly oriented pyrolytical graphite (HOPG) have been performed using scanning tunnelling microscope (STM) and atomic force microscope (AFM). It is found that after intercalation atomic hydrogen is stored among graphene layers in H2 gas form, captured inside graphene blisters. On desorption of hydrogen, some lateral etching of upper graphene layers takes place. Significant information about intake, retention and possibility of manifold accumulation of hydrogen in HOPG has been found.