Symmetry-Breaking-Induced Frequency Combs in Graphene Resonators.

Nonlinearities are inherent to the dynamics of two-dimensional materials. Phenomena-like intermodal coupling already arise at amplitudes of only a few nanometers, and a range of unexplored effects still awaits to be harnessed. Here, we demonstrate a route for generating mechanical frequency combs in graphene resonators undergoing symmetry-breaking forces. We use electrostatic force to break the membrane's out-of-plane symmetry and tune its resonance frequency toward a one-to-two internal resonance, thus achieving strong coupling between two of its mechanical modes. When increasing the drive level, we observe splitting of the fundamental resonance peak, followed by the emergence of a frequency comb regime. We attribute the observed physics to a nonsymmetric restoring potential and show that the frequency comb regime is mediated by Neimark bifurcation of the periodic solution. These results demonstrate that mechanical frequency combs and chaotic dynamics in 2D material resonators can emerge near internal resonances due to symmetry-breaking.

Growth of Graphene on a Liquified Copper Skin at Submelting Temperatures.

In chemical vapor deposition of graphene, crossing over the melting temperature of the bulk catalyst is an effective approach to heal the defects and thus improve the crystallinity of the lattice. Here, electromagnetic absorption (the capability of metals to absorb radiated thermal energy) yields a thin skin of liquid metal catalyst at submelting temperatures, allowing the growth of high quality graphene. In fact, a chromium film initially deposited on one side of a copper foil absorbs the thermal energy radiated from a heating stage several times more effectively than a plain copper foil. The resulting migration of the chromium grains to the other side of the foil locally melts the copper, improving the crystalline quality of the growing graphene, confirmed by Raman spectroscopy. The process duration is therefore dramatically minimized, and the crystallinity of the graphene is maximized. Remarkably, the usual annealing step is no more necessary prior to the growth which together with unlocking the direct healing of defects in the growing graphene, will unify growth strategies between a range of catalysts.

Supramolecular Multilayered Templates for Fabricating Nanometer-Precise Spacings: Implications for the Next-Generation of Devices Integrating Nanogap/Nanochannel Components.

Molecular transistors, electromagnetic waveguides, plasmonic devices, and novel generations of nanofluidic channels comprise precisely separated gaps of nanometric and subnanometric spacing. Nonetheless, fabricating a nanogap/nanochannel is a technological challenge, currently tackled by several approaches such as breakdown electromigration and lithography. The aforementioned techniques, though, are limited, respectively, in terms of gap stability and ultimate resolution. Here, nanogaps/nanochannels are templated via the microtomy of metallic thin films embedded in a polymer matrix and precisely separated by a nanometric, sacrificial layer of polyelectrolytes grown via the layer-by-layer (LbL) approach. The versatility of the LbL technique, both in terms of the number of layers and composition of polyelectrolytes, allows to finely tune the spacing across the gap; the LbL template can further be removed by plasma etching. Our findings pave the path toward the realization of molecularly defined functional spacings at the nanometer-scale for the modular implementation of devices integrating nanogap/nanochannel components.

Encapsulation of Graphene in the Hydrophobic Core of a Lipid Bilayer.

Theoretical simulations have predicted that a lipid bilayer forms a stable superstructure when a sheet of graphene is inserted in its hydrophobic core. We experimentally produced for the first time a lipid-graphene-lipid assembly by combining the Langmuir-Blodgett and the Langmuir-Schaefer methods. Graphene is sandwiched and remains flat within the hydrophobic core of the lipid bilayer. Using infrared spectroscopy, ellipsometry, and neutron reflectometry, we characterized the superstructure at every fabrication step. The hybrid superstructure is mechanically stable and graphene does not disturb the natural lipid bilayer structure.

Correction to "Molecular Caging of Graphene with Cyclohexane: Transfer and Electrical Transport".

[This corrects the article DOI: 10.1021/acscentsci.6b00236.].

Lateral Non-covalent Clamping of Graphene at the Edges Using a Lipid Scaffold.

Developing a clean handling and transfer process, capable of preserving the integrity of two-dimensional materials, is still a challenge. Here, we present a flexible, dynamic, and lipid-based scaffold that clamps graphene at the edges providing a practical, simple, and clean graphene manipulation and transfer method. Lipid films with different surface pressures are deposited at the air/copper-etchant interface immediately after placing the graphene samples. We show that at surface pressures above 30 mN/m, the lateral support prevents graphene movement and cracking during all etching and transfer. The method provides new insights into the handling of graphene and can yield efficient, sensitive, and clean graphene-based devices.

Zero-Depth Interfacial Nanopore Capillaries.

High-fidelity analysis of translocating biomolecules through nanopores demands shortening the nanocapillary length to a minimal value. Existing nanopores and capillaries, however, inherit a finite length from the parent membranes. Here, nanocapillaries of zero depth are formed by dissolving two superimposed and crossing metallic nanorods, molded in polymeric slabs. In an electrolyte, the interface shared by the crossing fluidic channels is mathematically of zero thickness and defines the narrowest constriction in the stream of ions through the nanopore device. This novel architecture provides the possibility to design nanopore fluidic channels, particularly with a robust 3D architecture maintaining the ultimate zero thickness geometry independently of the thickness of the fluidic channels. With orders of magnitude reduced biomolecule translocation speed, and lowered electronic and ionic noise compared to nanopores in 2D materials, the findings establish interfacial nanopores as a scalable platform for realizing nanofluidic systems, capable of single-molecule detection.

Water-Dispersible Silica-Coated Upconverting Liposomes: Can a Thin Silica Layer Protect TTA-UC against Oxygen Quenching?

Light upconversion by triplet-triplet annihilation (TTA-UC) in nanoparticles has received considerable attention for bioimaging and light activation of prodrugs. However, the mechanism of TTA-UC is inherently sensitive for quenching by molecular oxygen. A potential oxygen protection strategy is the coating of TTA-UC nanoparticles with a layer of oxygen-impermeable material. In this work, we explore if (organo)silica can fulfill this protecting role. Three synthesis routes are described for preparing water-dispersible (organo)silica-coated red-to-blue upconverting liposomes. Their upconversion properties are investigated in solution and in A549 lung carcinoma cells. Although it was found that the silica offered no protection from oxygen in solution and after uptake in A549 cancer cells, upon drying of the silica-coated liposome dispersion in an excess of (organo)silica precursor, interesting liposome-silica nanocomposite materials were obtained that were capable of generating blue light upon red light excitation in air.

Single molecule detection with graphene and other two-dimensional materials: nanopores and beyond.

Graphene and other two dimensional (2D) materials are currently integrated into nanoscaled devices that may - one day - sequence genomes. The challenge to solve is conceptually straightforward: cut a sheet out of a 2D material and use the edge of the sheet to scan an unfolded biomolecule from head to tail. As the scan proceeds - and because 2D materials are atomically thin - the information provided by the edge might be used to identify different segments - ideally single nucleotides - in the biomolecular strand. So far, the most efficient approach was to drill a nano-sized pore in the sheet and use this pore as a channel to guide and detect individual molecules by measuring the electrochemical ionic current. Nanoscaled gaps between two electrodes in 2D materials recently emerged as powerful alternatives to nanopores. This article reviews the current status and prospects of integrating 2D materials in nanopores, nanogaps and similar devices for single molecule biosensing applications. We discuss the pros and cons, the challenges, and the latest achievements in the field. To achieve high-throughput sequencing with 2D materials, interdisciplinary research is essential.

Chemistry at the Edge of Graphene.

The selective functionalization of graphene edges is driven by the chemical reactivity of its carbon atoms. The chemical reactivity of an edge, as an interruption of the honeycomb lattice of graphene, differs from the relative inertness of the basal plane. In fact, the unsaturation of the pz orbitals and the break of the π conjugation on an edge increase the energy of the electrons at the edge sites, leading to specific chemical reactivity and electronic properties. Given the relevance of the chemistry at the edges in many aspects of graphene, the present Review investigates the processes and mechanisms that drive the chemical functionalization of graphene at the edges. Emphasis is given to the selective chemical functionalization of graphene edges from theoretical and experimental perspectives, with a particular focus on the characterization tools available to investigate the chemistry of graphene at the edge.

Molecular Caging of Graphene with Cyclohexane: Transfer and Electrical Transport.

Transfer of large, clean, crack- and fold-free graphene sheets is a critical challenge in the field of graphene-based electronic devices. Polymers, conventionally used for transferring two-dimensional materials, irreversibly adsorb yielding a range of unwanted chemical functions and contaminations on the surface. An oil-water interface represents an ideal support for graphene. Cyclohexane, the oil phase, protects graphene from mechanical deformation and minimizes vibrations of the water surface. Remarkably, cyclohexane solidifies at 7 °C forming a plastic crystal phase molecularly conforming graphene, preventing the use of polymers, and thus drastically limiting contamination. Graphene floating at the cyclohexane/water interface exhibits improved electrical performances allowing for new possibilities of in situ, flexible sensor devices at a water interface.