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.
Iron oxide nanocrystals (IONCs) are appealing heat mediator nanoprobes in magnetic-mediated hyperthermia for cancer treatment. Here, specific absorption rate (SAR) values are reported for cube-shaped water-soluble IONCs prepared by a one-pot synthesis approach in a size range between 13 and 40 nm. The SAR values were determined as a function of frequency and magnetic field applied, also spanning technical conditions which are considered biomedically safe for patients. Among the different sizes tested, IONCs with an average diameter of 19 ± 3 nm had significant SAR values in clinical conditions and reached SAR values up to 2452 W/g(Fe) at 520 kHz and 29 kAm(-1), which is one of the highest values so far reported for IONCs. In vitro trials carried out on KB cancer cells treated with IONCs of 19 nm have shown efficient hyperthermia performance, with cell mortality of about 50% recorded when an equilibrium temperature of 43 °C was reached after 1 h of treatment.
We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a ‘hands-on’ approach, providing practical details and procedures as derived from literature as well as from the authors’ experience, in order to enable the reader to reproduce the results. Section is devoted to ‘bottom up’ approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section covers ‘top down’ techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers’ and modified Hummers’ methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by ...
A colloidal nonaqueous approach to semiconductor-magnetic hybrid nanocrystals (HNCs) with selectable heterodimer topologies and tunable geometric parameters is demonstrated. Brookite TiO(2) nanorods, distinguished by a curved shape-tapered profile with richly faceted terminations, are exploited as substrate seeds onto which a single spherical domain of inverse spinel iron oxide can be epitaxially grown at either one apex or any location along their longitudinal sidewalls in a hot surfactant environment. The topologically controlled arrangement of the component material lattices, the crystallographic relationships holding between them, and strain distribution across individual heterostructures have been studied by combining X-ray diffraction and absorption techniques with high-resolution transmission electron microscopy investigations. Supported by such structural knowledge, the synthetic achievements are interpreted within the frame of various mechanistic models offering complementary views of HNC formation. The different HNC architectures are concluded to be almost equivalent in terms of surface-interface energy balance associated with their formation. HNC topology selection is rationalized on the basis of a diffusion-limited mechanism allowing iron oxide heterogeneous nucleation and growth on the TiO(2) nanorods to switch from a thermodynamically controlled to a kinetically overdriven deposition regime, in which the anisotropic reactivity offered by the uniquely structured seeds is accentuated under high spatially inhomogeneous monomer fluxes. Finally, the multifunctional capabilities of the heterostructures are highlighted through illustration of their magnetic and photocatalytic properties, which have been found to diverge from those otherwise exhibited by their individual material components and physical mixture counterparts.
Ti-doped BiFeO3 ceramics prepared by a mixed-oxide route were structurally characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM), giving evidence of the formation of an inner structure at the nanometric scale. The observed nanograins are separated by Ti-rich areas that originate due to the tendency of the titanium dopant to segregate from the perovskite lattice. Such a peculiar nanostructure is responsible for the changes produced in both the electrical and the magnetic properties of BiFeO3 upon titanium doping: the Ti-rich interfaces act as resistive layers that increase the direct-current (dc) resistivity of the material, while the existence of structural domains in the scale of tens of nanometers causes a ferrimagnetic-like behavior with a huge coercive field (on the order of 20 kOe), even at room temperature.
We present very low-temperature scanning tunneling microscopy (STM) experiments on single-crystalline samples of the superconductor β-Bi 2 Pd. We find a single superconducting gap from the zero-field tunneling conductance. However, the magnetic field dependence of the intervortex tunneling conductance is higher than the one expected in a single-gap superconductor. Such an increase in the intervortex tunneling conductance has been found in superconductors with multiple superconducting gaps. We also find that the hexagonal vortex lattice is locked to the square atomic lattice as expected in crystalline superconductors with anisotropic Fermi surfaces. Moreover, we compare the upper critical field H c2 (T ) obtained in our sample with previous measurements and find that H c2 (T ) does not increase by reducing the mean free path. We fit H c2 (T ) and show that multiband Fermi surface is needed to explain the observed behavior. We propose that β-Bi 2 Pd is a single-gap multiband superconductor. We anticipate that single-gap superconductivity might often occur in compounds with anisotropic multiband Fermi surfaces.
The peculiar features of domain walls observed in ferroelectrics make them promising active elements for next-generation non-volatile memories, logic gates and energy-harvesting devices. Although extensive research activity has been devoted recently to making full use of this technological potential, concrete realizations of working nanodevices exploiting these functional properties are yet to be demonstrated. Here, we fabricate a multiferroic tunnel junction based on ferromagnetic LaSrMnO electrodes separated by an ultrathin ferroelectric BaTiO tunnel barrier, where a head-to-head domain wall is constrained. An electron gas stabilized by oxygen vacancies is confined within the domain wall, displaying discrete quantum-well energy levels. These states assist resonant electron tunnelling processes across the barrier, leading to strong quantum oscillations of the electrical conductance.
The detection of true magnetocapacitance (MC) as a manifestation of magnetoelectric coupling (MEC) in multiferroic materials is a nontrivial task, because pure magnetoresistance (MR) of an extrinsic MaxwellWagner-type dielectric relaxation can lead to changes in capacitance [G. Catalan, Appl. Phys. Lett. 88, 102902 (2006)]. In order to clarify such difficulties involved with dielectric spectroscopy on multiferroic materials, we have simulated the dielectric permittivity ε of two dielectric relaxations in terms of a series of one intrinsic film-type and one extrinsic Maxwell-Wagner-type relaxation. Such a series of two relaxations was represented in the frequency-(f -) and temperature-(T -) dependent notations ε vs f and ε vs T by a circuit model consisting in a series of two ideal resistor-capacitor (RC) elements. Such simulations enabled rationalizing experimental f -, T-, and magnetic field-(H -) dependent dielectric spectroscopy data from multiferroic epitaxial thin films of BiMnO 3 (BMO) and BiFeO 3 (BFO) grown on Nb-doped SrTiO 3 . Concomitantly, the deconvolution of intrinsic film and extrinsic Maxwell-Wagner relaxations in BMO and BFO films was achieved by fitting f -dependent dielectric data to an adequate equivalent circuit model. Analysis of the H -dependent data in the form of determining the H -dependent values of the equivalent circuit resistors and capacitors then yielded the deconvoluted MC and MR values for the separated intrinsic dielectric relaxations in BMO and BFO thin films. Substantial intrinsic MR effects up to 65% in BMO films below the magnetic transition (T C ≈ 100 K) and perceptible intrinsic MEC up to − 1.5% near T C were identified unambiguously.
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