Vittorio Morandi

Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems

We present the science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems, targeting an evolution in technology, that might lead to impacts and benefits reaching into most areas of society. This roadmap was developed within the framework of the European Graphene Flagship and outlines the main targets and research areas as best understood at the start of this ambitious project. We provide an overview of the key aspects of graphene and related materials (GRMs), ranging from fundamental research challenges to a variety of applications in a large number of sectors, highlighting the steps necessary to take GRMs from a state of raw potential to a point where they might revolutionize multiple industries. We also define an extensive list of acronyms in an effort to standardize the nomenclature in this emerging field.

A supramolecular strategy to leverage the liquid-phase exfoliation of graphene in the presence of surfactants: unraveling the role of the length of fatty acids.

Achieving the full control over the production as well as processability of high-quality graphene represents a major challenge with potential interest in the field of fabrication of multifunctional devices. The outstanding effort dedicated to tackle this challenge in the last decade revealed that certain organic molecules are capable of leveraging the exfoliation of graphite with different efficiencies. Here, a fundamental understanding on a straightforward supramolecular approach for producing homogenous dispersions of unfunctionalized and non-oxidized graphene nanosheets in four different solvents is attained, namely N-methyl-2-pyrrolidinone, N,N-dimethylformamide, ortho-dichlorobenzene, and 1,2,4-trichlorobenzene. In particular, a comparative study on the liquid-phase exfoliation of graphene in the presence of linear alkanes of different lengths terminated by a carboxylic-acid head group is performed. These molecules act as graphene dispersion-stabilizing agents during the exfoliation process. The efficiency of the exfoliation in terms of concentration of exfoliated graphene is found to be proportional to the length of the employed fatty acid. Importantly, a high percentage of single-layer graphene flakes is revealed by high-resolution transmission electron microscopy and Raman spectroscopy analyses. A simple yet effective thermodynamic model is developed to interpret the chain-length dependence of the exfoliation yield. This approach relying on the synergistic effect of a ad-hoc solvent and molecules to promote the exfoliation of graphene in liquid media represents a promising and modular strategy towards the rational design of improved dispersion-stabilizing agents.

Surfactant-free single-layer graphene in water

Dispersing graphite in water to obtain true (single-layer) graphene in bulk quantity in a liquid has been an unreachable goal for materials scientists in the past decade. Similarly, a diagnostic tool to identify solubilized graphene in situ has been long awaited. Here we show that homogeneous stable dispersions of single-layer graphene (SLG) in water can be obtained by mixing graphenide (negatively charged graphene) solutions in tetrahydrofuran with degassed water and evaporating the organic solvent. In situ Raman spectroscopy of these aqueous dispersions shows all the expected characteristics of SLG. Transmission electron and atomic force microscopies on deposits confirm the single-layer character. The resulting additive-free stable water dispersions contain 400 m2 l-1 of developed graphene surface. Films prepared from these dispersions exhibit a conductivity of up to 32 kS m-1.

Folded Graphene Membranes: Mapping Curvature at the Nanoscale

While the unique elastic properties of monolayer graphene have been extensively investigated, less knowledge has been developed so far on folded graphene. Nevertheless, it has been recently suggested that fold-induced curvature (without in-plane strain) could possibly affect the local chemical and electron transport properties of graphene, envisaging a material-by-design approach where tailored membranes are used in enhanced nanoresonators or nanoelectromechanical devices. In this work we propose a novel method combining apparent strain analysis from high-resolution transmission electron microscopy (HREM) images and theoretical modeling based on continuum elasticity theory and tight-binding atomistic simulations to map and measure the nanoscale curvature of graphene folds and wrinkles. If enough contrast and resolution in HREM images are obtained, this method can be successfully applied to provide a complete nanoscale geometrical and physical picture of 3D structure of various wrinkle and fold configurations.

Light-Enhanced Liquid-Phase Exfoliation and Current Photoswitching in Graphene-Azobenzene Composites

Multifunctional materials can be engineered by combining multiple chemical components, each conferring a well-defined function to the ensemble. Graphene is at the centre of an ever-growing research effort due to its combination of unique properties. Here we show that the large conformational change associated with the trans–cis photochemical isomerization of alkyl-substituted azobenzenes can be used to improve the efficiency of liquid-phase exfoliation of graphite, with the photochromic molecules acting as dispersion-stabilizing agents. We also demonstrate reversible photo-modulated current in two-terminal devices based on graphene–azobenzene composites. We assign this tuneable electrical characteristics to the intercalation of the azobenzene between adjacent graphene layers and the resulting increase in the interlayer distance on (photo)switching from the linear trans-form to the bulky cis-form of the photochromes. These findings pave the way to the development of new optically controlled memories for light-assisted programming and high-sensitive photosensors.

Regenerable Resistive Switching in Silicon Oxide Based Nanojunctions

A nanomemristor based on SiO(2) is fabricated in situ with spatial control at the nanoscale. The proposed system exhibits peculiar properties such as the possibility to be regenerated after being stressed or damaged and the possibility to expose the metal and the oxide interfaces by removing the top electrodes.

Solutions of fully exfoliated individual graphene flakes in low boiling point solvents

Graphenide solutions (solutions of negatively charged graphene flakes) have been prepared in low boiling point solvents such as tetrahydrofuran (THF) by dissolution of the graphite intercalation compound (GIC) KC8. The presence of two-dimensional objects in solution, with an average lateral size of over one micron, is evidenced by light scattering analysis. High resolution transmission electron microscopy analysis shows that the solubilized graphene flakes are exclusively single and double layers with no evidence for thicker species. Molecular dynamics simulations support the graphene folding, observed in TEM, and suggest it is triggered by solvent nanodrops.

Contrast and resolution versus specimen thickness in low energy scanning transmission electron microscopy

A theoretical and experimental investigation of contrast and resolution versus specimen thickness in scanning transmission electron microscopy at low energy is reported. Due to absence of postspecimen imaging lenses it is possible to have images with a resolution defined by the probe size using very wide collection angles and independent of the energy loss of the transmitted electrons. The fundamental limitation in observable specimen thickness is represented by the signal to noise ratio, i.e., the intensity of the beam current. The investigated specimens are semiconductor multilayers and Sb precipitates in a Si implanted specimen. The observations of layers crossing the whole specimens parallel to the electron beam point out that only a small portion of them, the one close to the surface, causes the image contrast, while the portion below, where the probe diameter, as a consequence of the broadening, is larger than the layer itself, reduces the contrast. A similarity with recent results, achieved in scan...

Liquid-Phase Exfoliation of Graphite into Single- and Few-Layer Graphene with α-Functionalized Alkanes

Graphene has unique physical and chemical properties, making it appealing for a number of applications in optoelectronics, sensing, photonics, composites, and smart coatings, just to cite a few. These require the development of production processes that are inexpensive and up-scalable. These criteria are met in liquid-phase exfoliation (LPE), a technique that can be enhanced when specific organic molecules are used. Here we report the exfoliation of graphite in N-methyl-2-pyrrolidinone, in the presence of heneicosane linear alkanes terminated with different head groups. These molecules act as stabilizing agents during exfoliation. The efficiency of the exfoliation in terms of the concentration of exfoliated single- and few-layer graphene flakes depends on the functional head group determining the strength of the molecular dimerization through dipole-dipole interactions. A thermodynamic analysis is carried out to interpret the impact of the termination group of the alkyl chain on the exfoliation yield. This combines molecular dynamics and molecular mechanics to rationalize the role of functionalized alkanes in the dispersion and stabilization process, which is ultimately attributed to a synergistic effect of the interactions between the molecules, graphene, and the solvent.

Graphene–organic hybrids as processable, tunable platforms for pH-dependent photoemission, obtained by a new modular approach

We describe a new approach to attach organic dyes to graphene oxide (GO) sheets with high loading and minimal perturbation of the electronic and optical properties of the dye. The dye unit used (a pH-sensitive terthiophene) is grafted to GO using a new modular synthetic approach, passing through a C6-aminic linker which makes GO more soluble in different organic solvents and allows straightforward attachment at high yield not only of terthiophene but of many commercially available amino-reactive dyes. The covalent engraftment to GO does not perturb the absorption and emission properties of the dye, and in particular the pH sensing capability through amidic group reversible protonation. This approach can allow (i) high solubility of the GO intermediate in organic solvents, (ii) convenient coupling with commercial, stable amino-reactive dyes under mild conditions, (iii) easy control of the spacer length between the GO and oligothiophene dye and finally (iv) high (up to 5 wt%) dye functionalization loadings.