Vincenzo Palermo

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.

Local Current Mapping and Patterning of Reduced Graphene Oxide

Conductive atomic force microscopy (C-AFM) has been used to correlate the detailed structural and electrical characteristics of graphene derived from graphene oxide. Uniform large currents were measured over areas exceeding tens of micrometers in few-layer films, supporting the use of graphene as a transparent electrode material. Moreover, defects such as electrical discontinuities were easily detected. Multilayer films were found to have a higher conductivity per layer than single layers. It is also shown that a local AFM-tip-induced electrochemical reduction process can be used to pattern conductive pathways on otherwise-insulating graphene oxide. Transistors with micrometer-scale tip-reduced graphene channels that featured ambipolar transport and an 8 order of magnitude increase in current density upon reduction were successfully fabricated.

Nanoscale Quantitative Measurement of the Potential of Charged Nanostructures by Electrostatic and Kelvin Probe Force Microscopy: Unraveling Electronic Processes in Complex Materials

In microelectronics and biology, many fundamental processes involve the exchange of charges between small objects, such as nanocrystals in photovoltaic blends or individual proteins in photosynthetic reactions. Because these nanoscale electronic processes strongly depend on the structure of the electroactive assemblies, a detailed understanding of these phenomena requires unraveling the relationship between the structure of the nano-object and its electronic function. Because of the fragility of the structures involved and the dynamic variance of the electric potential of each nanostructure during the charge generation and transport processes, understanding this structure-function relationship represents a great challenge. This Account discusses how our group and others have exploited scanning probe microscopy based approaches beyond imaging, particularly Kelvin probe force microscopy (KPFM), to map the potential of different nanostructures with a spatial and voltage resolution of a few nanometers and millivolts, respectively. We describe in detail how these techniques can provide researchers several types of chemical information. First, KPFM allows researchers to visualize the photogeneration and splitting of several unitary charges between well-defined nano-objects having complementary electron-acceptor and -donor properties. In addition, this method maps charge injection and transport in thin layers of polycrystalline materials. Finally, KPFM can monitor the activity of immobilized chemical components of natural photosynthetic systems. In particular, researchers can use KPFM to measure the electric potential without physical contact between the tip and the nanostructure studied. These measurements exploit long-range electrostatic interactions between the scanning probe and the sample, which scale with the square of the probe-sample distance, d. While allowing minimal perturbation, these long-range interactions limit the resolution attainable in the measurement of potentials. Although the spatial resolution of KPFM is on the nanometer scale, it is inferior to that of other related techniques such as atomic force or scanning tunneling microscopy, which are based on short-range interactions scaling as d(-7) or e(-d), respectively. To overcome this problem, we have recently devised deconvolution procedures that allow us to quantify the electric potential of a nano-object removing the artifacts due to its nanometric size.

Charge transport in graphene–polythiophene blends as studied by Kelvin Probe Force Microscopy and transistor characterization

Blends of reduced graphene oxide (RGO) and poly(3-hexylthiophene) (P3HT) are used as the active layer of field-effect transistors (FETs). By using sequential deposition of the two components, the density of RGO sheets can be tuned linearly, thereby modulating their contribution to the charge transport in the transistors, and the onset of charge percolation. The surface potential of RGO, P3HT and source–drain contacts is measured on the nanometric scale with Kelvin Probe Force Microscopy (KPFM), and correlated with the macroscopic performance of the FETs. KPFM is also used to monitor the potential decay along the channel in the working FETs.

Evidencing the mask effect of graphene oxide: a comparative study on primary human and murine phagocytic cells

Graphene oxide (GO) is attracting an ever-growing interest in different fields and applications. Not much is known about the possible impact of GO sheet lateral dimensions on their effects in vitro, especially on human primary cells. In an attempt to address this issue, we present a study to evaluate, how highly soluble 2-dimensional GO constituted of large or small flakes affects human monocyte derived macrophages (hMDM). For this purpose, the lateral size of GO was tuned using sonication and three samples were obtained. The non sonicated one presented large flakes (~1.32 μm) while sonication for 2 and 26 hours generated small (~0.27 μm) and very small (~0.13 μm) sheets of GO, respectively. Cell studies were then conducted to evaluate the cytotoxicity, the oxidative stress induction, the activation potential and the pro-inflammatory effects of these different types of GO at increasing concentrations. In comparison, the same experiments were run on murine intraperitoneal macrophages (mIPM). The interaction between GO and cells was further examined by TEM and Raman spectroscopy. Our data revealed that the GO sheet size had a significant impact on different cellular parameters (i.e. cellular viability, ROS generation, and cellular activation). Indeed, the more the lateral dimensions of GO were reduced, the higher were the cellular internalization and the effects on cellular functionality. Our data also revealed a particular interaction of GO flakes with the cellular membrane. In fact, a GO mask due to the parallel arrangement of the graphene sheets on the cellular surface was observed. Considering the mask effect, we have hypothesized that this particular contact between GO sheets and the cell membrane could either promote their internalization or isolate cells from their environment, thus possibly accounting for the following impact on cellular parameters.

Dispersibility‐Dependent Biodegradation of Graphene Oxide by Myeloperoxidase

Understanding human health risk associated with the rapidly emerging graphene-based nanomaterials represents a great challenge because of the diversity of applications and the wide range of possible ways of exposure to this type of materials. Herein, the biodegradation of graphene oxide (GO) sheets is reported by using myeloperoxidase (hMPO) derived from human neutrophils in the presence of a low concentration of hydrogen peroxide. The degradation capability of the enzyme on three different GO samples containing different degree of oxidation on their graphenic lattice, leading to a variable dispersibility in aqueous media is compared. hMPO fails in degrading the most aggregated GO, but succeeds to completely metabolize highly dispersed GO samples. The spectroscopy and microscopy analyses provide unambiguous evidence for the key roles played by hydrophilicity, negative surface charge, and colloidal stability of the aqueous GO in their biodegradation by hMPO catalysis.

Tuning the Work‐Function Via Strong Coupling

The tuning of the molecular material work-function via strong coupling with vacuum electromagnetic fields is demonstrated. Kelvin probe microscopy extracts the surface potential (SP) changes of a photochromic molecular film on plasmonic hole arrays and inside Fabry-Perot cavities. Modulating the optical cavity resonance or the photochromic film effectively tunes the work-function, suggesting a new tool for tailoring material properties.

Large Work Function Shift of Gold Induced by a Novel Perfluorinated Azobenzene-Based Self-Assembled Monolayer

Tune it with light! Self-assembled monolayers on gold based on a chemisorbed novel azobenzene derivative with a perfluorinated terminal phenyl ring are prepared. The modified substrate shows a significant work function increase compared to the bare metal. The photo-conversion between trans and cis isomers chemisorbed on the surface shows great perspectives for being an accessible route to tune the gold properties by means of light.

Harnessing the Liquid‐Phase Exfoliation of Graphene Using Aliphatic Compounds: A Supramolecular Approach

The technological exploitation of the extraordinary properties of graphene relies on the ability to achieve full control over the production of a high-quality material and its processing by up-scalable approaches in order to fabricate large-area films with single-layer or a few atomic-layer thickness, which might be integrated in working devices. A simple method is reported for producing homogenous dispersions of unfunctionalized and non-oxidized graphene nanosheets in N-methyl-2-pyrrolidone (NMP) by using simple molecular modules, which act as dispersion-stabilizing compounds during the liquid-phase exfoliation (LPE) process, leading to an increase in the concentration of graphene in dispersions. The LPE-processed graphene dispersion was shown to be a conductive ink. This approach opens up new avenues for the technological applications of this graphene ink as low-cost electrodes and conducting nanocomposite for electronics.

Temperature-Enhanced Solvent Vapor Annealing of a C-3 Symmetric Hexa-peri-Hexabenzocoronene: Controlling the Self-Assembly from Nano- to Macroscale

Temperature-enhanced solvent vapor annealing (TESVA) is used to self-assemble functionalized polycyclic aromatic hydrocarbon molecules into ordered macroscopic layers and crystals on solid surfaces. A novel C3 symmetric hexa-peri-hexabenzocoronene functionalized with alternating hydrophilic and hydrophobic side chains is used as a model system since its multivalent character can be expected to offer unique self-assembly properties and behavior in different solvents. TESVA promotes the molecules long-range mobility, as proven by their diffusion on a Si/SiO(x) surface on a scale of hundreds of micrometers. This leads to self-assembly into large, ordered crystals featuring an edge-on columnar type of arrangement, which differs from the morphologies obtained using conventional solution-processing methods such as spin-coating or drop-casting. The temperature modulation in the TESVA makes it possible to achieve an additional control over the role of hydrodynamic forces in the self-assembly at surfaces, leading to a macroscopic self-healing within the adsorbed film notably improved as compared to conventional solvent vapor annealing. This surface re-organization can be monitored in real time by optical and atomic force microscopy.