Heterostructures produced from nanosheet-based inks.

The new paradigm of heterostructures based on two-dimensional (2D) atomic crystals has already led to the observation of exciting physical phenomena and creation of novel devices. The possibility of combining layers of different 2D materials in one stack allows unprecedented control over the electronic and optical properties of the resulting material. Still, the current method of mechanical transfer of individual 2D crystals, though allowing exceptional control over the quality of such structures and interfaces, is not scalable. Here we show that such heterostructures can be assembled from chemically exfoliated 2D crystals, allowing for low-cost and scalable methods to be used in device fabrication.

Controlled modification of mono- and bilayer graphene in O2, H2 and CF4 plasmas.

In this work, covalent modification of mono- and bilayer graphene is achieved using tetrafluoromethane (CF4), oxygen and hydrogen RF plasma. Controlled modification of graphene is usually difficult to achieve, in particular with oxygen plasma, which is rather aggressive and usually leads to etching of graphene. Here we use x-ray photoelectron spectroscopy and Raman spectroscopy to show that mild plasma conditions and fine tuning of the number of functional groups can be obtained in all plasmas by varying parameters such as exposure time and sample position inside the chamber. We found that even for the usual harsh oxygen treatment the defect density could be lowered, down to one defect for 3.5 × 104 carbon atoms. Furthermore, we show that CF4 plasma leads to functionalization without etching and that graphene becomes an insulator at saturation coverage. In addition, the reactivity of mono- and bilayer graphene was studied revealing faster modification of monolayer in oxygen and CF4 plasma, in agreement with previous works. In contrast, similar modification rates were observed for both mono- and bilayer during hydrogenation. We attribute this discrepancy to the presence of more energetic species in the hydrogen plasma such as positive ions that could play a role in the functionalization process.

Cascaded optical field enhancement in composite plasmonic nanostructures.

We present composite plasmonic nanostructures designed to achieve cascaded enhancement of electromagnetic fields at optical frequencies. Our structures were made with the help of electron-beam lithography and comprise a set of metallic nanodisks placed one above another. The optical properties of reproducible arrays of these structures were studied by using scanning confocal Raman spectroscopy. We show that our composite nanostructures robustly demonstrate dramatic enhancement of the Raman signals when compared to those measured from constituent elements.

Raman spectroscopy of graphene edges.

Graphene edges are of particular interest since their orientation determines the electronic properties. Here we present a detailed Raman investigation of graphene flakes with edges oriented at different crystallographic directions. We also develop a real space theory for Raman scattering to analyze the general case of disordered edges. The position, width, and intensity of G and D peaks are studied as a function of the incident light polarization. The D-band is strongest for polarization parallel to the edge and minimum for perpendicular. Raman mapping shows that the D peak is localized in proximity of the edge. For ideal edges, the D peak is zero for zigzag orientation and large for armchair, allowing in principle the use of Raman spectroscopy as a sensitive tool for edge orientation. However, for real samples, the D to G ratio does not always show a significant dependence on edge orientation. Thus, even though edges can appear macroscopically smooth and oriented at well-defined angles, they are not necessarily microscopically ordered.

The roughening kinetics of hydrogenated graphene.

The roughness is a common property of all growing surfaces - however, the way the roughness of a growing surface changes with time and space is uniquely related to the underlying growth process, i.e. to how the atoms stick to the surface during the first stage of nucleation. This concept allows getting insights on the nucleation process of a growing surface by measuring two scaling exponents, α and ß, known as roughness and growth exponents, respectively. In this work, we studied hydrogenation of graphene using the roughening kinetics. The coverage of graphene will depend on how the H ions stick on the surface, giving rise to a unique roughness evolution in time and space. We measured a roughness exponent of ~0.5 (derived from a Fourier index of ~3), and a growth exponent of ~0.3. The values of the growth and roughness exponents are close to those reported for clustered carbon, suggesting a roughening mechanism by clustering, in good agreement with the theory. We also compared our coverage data with a different model, used to describe the dynamics of graphene coverage, during chemical vapour deposition. Our data are in agreement with a nucleation-dominated growth, further confirming that hydrogenation is happening by clustering.

Behaviour of the pharmaceutical probiotic preparation VSL#3 in human ileostomy effluent containing its own natural elements.

The pharmaceutical probiotic VSL#3 (300 billion cfu/g lactic acid bacteria & bifidobacteria) was inoculated into human ileostomy effluent (HIE) to assess its behaviour vs the ileo-caecal tract. Separately, yogurt bacteria (yog) and bifidobacteria (Bif) present in VSL#3 were also inoculated into HIE. During 37 degrees C incubation (anaerobic condition) at zero, six and 24 hours, both cell growth in control HIE and indigenous Bif growth in HIE+yog were observed. Cells remained viable and metabolically active as shown by the increase in L(+) lactic acid in HIE+VSL#3 and HIE+yog and the pH decreased (approx. 5.5 compared with the 6.2 of control HIE). Total SCFA Short Chain Fatty Acids decreased in HIE+yog and HIE+VSL#3 at 6h and in all cultures at 24h; butyric acid decreased in HIE+Bif and HIE+VSL#3. Generally in vivo the bacteria remain in the ileo-caecal tract no longer than six h, therefore VSL#3 bacteria seem able to pass this barrier viably, colonizing the large bowel.

Strong light-matter interactions in heterostructures of atomically thin films.

The isolation of various two-dimensional (2D) materials, and the possibility to combine them in vertical stacks, has created a new paradigm in materials science: heterostructures based on 2D crystals. Such a concept has already proven fruitful for a number of electronic applications in the area of ultrathin and flexible devices. Here, we expand the range of such structures to photoactive ones by using semiconducting transition metal dichalcogenides (TMDCs)/graphene stacks. Van Hove singularities in the electronic density of states of TMDC guarantees enhanced light-matter interactions, leading to enhanced photon absorption and electron-hole creation (which are collected in transparent graphene electrodes). This allows development of extremely efficient flexible photovoltaic devices with photoresponsivity above 0.1 ampere per watt (corresponding to an external quantum efficiency of above 30%).

Rayleigh imaging of graphene and graphene layers.

We investigate graphene and graphene layers on different substrates by monochromatic and white-light confocal Rayleigh scattering microscopy. The image contrast depends sensitively on the dielectric properties of the sample as well as the substrate geometry and can be described quantitatively using the complex refractive index of bulk graphite. For a few layers (<6), the monochromatic contrast increases linearly with thickness. The data can be adequately understood by considering the samples behaving as a superposition of single sheets that act as independent two-dimensional electron gases. Thus, Rayleigh imaging is a general, simple, and quick tool to identify graphene layers, which is readily combined with Raman scattering, that provides structural identification.

Raman spectrum of graphene and graphene layers.

Graphene is the two-dimensional building block for carbon allotropes of every other dimensionality. We show that its electronic structure is captured in its Raman spectrum that clearly evolves with the number of layers. The D peak second order changes in shape, width, and position for an increasing number of layers, reflecting the change in the electron bands via a double resonant Raman process. The G peak slightly down-shifts. This allows unambiguous, high-throughput, nondestructive identification of graphene layers, which is critically lacking in this emerging research area.

Dynamic roughening of tetrahedral amorphous carbon.

The roughness of tetrahedral amorphous carbon (ta-C) films grown at room temperature is measured as a function of film thickness by atomic force microscopy, to extract roughness and growth exponents of alpha approximately 0.39 and beta approximately 0-0.1, respectively. This extremely small growth exponent shows that some form of surface diffusion and relaxation operates at a homologous temperature of 0.07, much lower than in any other material. This is accounted for by a Monte Carlo simulation, which assumes a smoothening during a thermal spike, following energetic ion deposition. The low roughness allows ta-C to be used as an ultrathin protective coating on magnetic disk storage systems with approximately 1 Tbit/in.(2) storage density.