Instituto de Ciencia de Materiales de Madrid

In this work we briefly describe the most relevant features of WSXM, a freeware scanning probe microscopy software based on MS-Windows. The article is structured in three different sections: The introduction is a perspective on the importance of software on scanning probe microscopy. The second section is devoted to describe the general structure of the application; in this section the capabilities of WSXM to read third party files are stressed. Finally, a detailed discussion of some relevant procedures of the software is carried out.

We demonstrate that the electronic gap of a graphene bilayer can be controlled externally by applying a gate bias. From the magnetotransport data (Shubnikov-de Haas measurements of the cyclotron mass), and using a tight-binding model, we extract the value of the gap as a function of the electronic density. We show that the gap can be changed from zero to midinfrared energies by using fields of less, approximately < 1 V/nm, below the electric breakdown of SiO2. The opening of a gap is clearly seen in the quantum Hall regime.

This review is focused on describing state-of-the-art synthetic routes for the preparation of magnetic nanoparticles useful for biomedical applications. In addition to this topic, we have also described in some detail some of the possible applications of magnetic nanoparticles in the field of biomedicine with special emphasis on showing the benefits of using nanoparticles. Finally, we have addressed some relevant findings on the importance of having well-defined synthetic routes to produce materials not only with similar physical features but also with similar crystallochemical characteristics.

Linking organic molecules by covalent bonds into extended solids typically generates amorphous, disordered materials. The ability to develop strategies for obtaining crystals of such solids is of interest because it opens the way for precise control of the geometry and functionality of the extended structure, and the stereochemical orientation of its constituents. Covalent organic frameworks (COFs) are a new class of porous covalent organic structures whose backbone is composed entirely of light elements (B, C, N, O, Si) that represent a successful demonstration of how crystalline materials of covalent solids can be achieved. COFs are made by combination of organic building units covalently linked into extended structures to make crystalline materials. The attainment of crystals is done by several techniques in which a balance is struck between the thermodynamic reversibility of the linking reactions and their kinetics. This success has led to the expansion of COF materials to include organic units linked by these strong covalent bonds: B-O, C-N, B-N, and B-O-Si. Since the organic constituents of COFs, when linked, do not undergo significant change in their overall geometry, it has been possible to predict the structures of the resulting COFs, and this advantage has facilitated their characterization using powder X-ray diffraction (PXRD) techniques. It has also allowed for the synthesis of COF structures by design and for their formation with the desired composition, pore size, and aperture. In practice, the modeled PXRD pattern for a given expected COF is compared with the experimental one, and depending on the quality of the match, this is used as a starting point for solving and then refining the crystal structure of the target COF. These characteristics make COFs an attractive class of new porous materials. Accordingly, they have been used as gas storage materials for energy applications, solid supports for catalysis, and optoelectronic devices. A large and growing library of linkers amenable to the synthesis of COFs is now available, and new COFs and topologies made by reticular synthesis are being reported. Much research is also directed toward the development of new methods of linking organic building units to generate other crystalline COFs. These efforts promise not only new COF chemistry and materials, but also the chance to extend the precision of molecular covalent chemistry to extended solids.

Recent theoretical proposals suggest that strain can be used to engineer graphene electronic states through the creation of a pseudo-magnetic field. This effect is unique to graphene because of its massless Dirac fermion-like band structure and particular lattice symmetry (C3v). Here, we present experimental spectroscopic measurements by scanning tunneling microscopy of highly strained nanobubbles that form when graphene is grown on a platinum (111) surface. The nanobubbles exhibit Landau levels that form in the presence of strain-induced pseudo-magnetic fields greater than 300 tesla. This demonstration of enormous pseudo-magnetic fields opens the door to both the study of charge carriers in previously inaccessible high magnetic field regimes and deliberate mechanical control over electronic structure in graphene or so-called "strain engineering."

We have grown an atom-thin, ordered, two-dimensional multi-phase film in situ through germanium molecular beam epitaxy using a gold (111) surface as a substrate. Its growth is similar to the formation of silicene layers on silver (111) templates. One of the phases, forming large domains, as observed in scanning tunneling microscopy, shows a clear, nearly flat, honeycomb structure. Thanks to thorough synchrotron radiation core-level spectroscopy measurements and advanced density functional theory calculations we can identify it as a √3 × √3 R(30°) germanene layer in conjunction with a √7 × √7 R(19.1°) Au(111) supercell, presenting compelling evidence of the synthesis of the germanium-based cousin of graphene on gold.

Two-dimensional carbon, or graphene, is a semimetal that presents unusual low-energy electronic excitations described in terms of Dirac fermions. We analyze in a self-consistent way the effects of localized (impurities or vacancies) and extended (edges or grain boundaries) defects on the electronic and transport properties of graphene. On the one hand, point defects induce a finite elastic lifetime at low energies with the enhancement of the electronic density of states close to the Fermi level. Localized disorder leads to a universal, disorder independent, electrical conductivity at low temperatures, of the order of the quantum of conductance. The static conductivity increases with temperature and shows oscillations in the presence of a magnetic field. The graphene magnetic susceptibility is temperature dependent (unlike an ordinary metal) and also increases with the amount of defects. Optical transport properties are also calculated in detail. On the other hand, extended defects induce localized states near the Fermi level. In the absence of electron-hole symmetry, these states lead to a transfer of charge between the defects and the bulk, the phenomenon we call self-doping. The role of electron-electron interactions in controlling self-doping is also analyzed. We also discuss the integer and fractional quantum Hall effect in graphene, the role played by the edge states induced by a magnetic field, and their relation to the almost field independent surface states induced at boundaries. The possibility of magnetism in graphene, in the presence of short-range electron-electron interactions and disorder is also analyzed.

We study the electronic states of narrow graphene ribbons (``nanoribbons'') with zigzag and armchair edges. The finite width of these systems breaks the spectrum into an infinite set of bands, which we demonstrate can be quantitatively understood using the Dirac equation with appropriate boundary conditions. For the zigzag nanoribbon we demonstrate that the boundary condition allows a particlelike and a holelike band with evanescent wave functions confined to the surfaces, which continuously turn into the well-known zero energy surface states as the width gets large. For armchair edges, we show that the boundary condition leads to admixing of valley states, and the band structure is metallic when the width of the sample in lattice constant units has the form $3M+1$, with $M$ an integer, and insulating otherwise. A comparison of the wave functions and energies from tight-binding calculations and solutions of the Dirac equations yields quantitative agreement for all but the narrowest ribbons.

We present a detailed study of static and dynamic magnetic behavior of Fe3O4 nanoparticles with average particle sizes 〈d〉 ranging from 5 to 150 nm. Bulk-like properties such as saturation magnetization, hyperfine parameters, coercive field, and Verwey transition are observed in 150 nm particles. For decreasing particle size, the Verwey temperature, TV, shifts down to ∼20 K for 〈d〉=50 nm and is no longer observable for smaller particles. The smallest particles (〈d〉=5 nm) display superparamagnetic behavior at room temperature, with transition to a blocked state at TB∼45 K, which depends on the applied field. The existence of surface spin disorder can be inferred from the decrease of saturation magnetization MS at low temperatures, as the average particle size is reduced. This disordered surface did not show effects of exchange coupling to the particle core, as observed from hysteresis loops after field cooling in a 7 T magnetic field. For particles with 〈d〉=5 nm, dynamic ac susceptibility measurements show a thermally activated Arrhenius–Néel dependence of the blocking temperature with applied frequency. The interparticle interactions are found to influence the energy barriers yielding an enhancement of the estimated magnetic anisotropy. From the calculus of the magnetic anisotropy, it is inferred that there is no structural transition from cubic to triclinic symmetry for 〈d〉=5 nm, in agreement with the absence of the Verwey transition. A value K1=4.68×105 erg/cm3 is obtained for the magnetocrystalline anisotropy constant of the cubic phase.

In this review an overview about biological applications of magnetic colloidal nanoparticles will be given, which comprises their synthesis, characterization, and in vitro and in vivo applications. The potential future role of magnetic nanoparticles compared to other functional nanoparticles will be discussed by highlighting the possibility of integration with other nanostructures and with existing biotechnology as well as by pointing out the specific properties of magnetic colloids. Current limitations in the fabrication process and issues related with the outcome of the particles in the body will be also pointed out in order to address the remaining challenges for an extended application of magnetic nanoparticles in medicine.

Controlling the bandstructure through local-strain engineering is an exciting avenue for tailoring optoelectronic properties of materials at the nanoscale. Atomically thin materials are particularly well-suited for this purpose because they can withstand extreme nonhomogeneous deformations before rupture. Here, we study the effect of large localized strain in the electronic bandstructure of atomically thin MoS2. Using photoluminescence imaging, we observe a strain-induced reduction of the direct bandgap and funneling of photogenerated excitons toward regions of higher strain. To understand these results, we develop a nonuniform tight-binding model to calculate the electronic properties of MoS2 nanolayers with complex and realistic local strain geometries, finding good agreement with our experimental results.

Abstract Semiconductors are the basis of many vital technologies such as electronics, computing, communications, optoelectronics, and sensing. Modern semiconductor technology can trace its origins to the invention of the point contact transistor in 1947. This demonstration paved the way for the development of discrete and integrated semiconductor devices and circuits that has helped to build a modern society where semiconductors are ubiquitous components of everyday life. A key property that determines the semiconductor electrical and optical properties is the bandgap. Beyond graphene, recently discovered two-dimensional (2D) materials possess semiconducting bandgaps ranging from the terahertz and mid-infrared in bilayer graphene and black phosphorus, visible in transition metal dichalcogenides, to the ultraviolet in hexagonal boron nitride. In particular, these 2D materials were demonstrated to exhibit highly tunable bandgaps, achieved via the control of layers number, heterostructuring, strain engineering, chemical doping, alloying, intercalation, substrate engineering, as well as an external electric field. We provide a review of the basic physical principles of these various techniques on the engineering of quasi-particle and optical bandgaps, their bandgap tunability, potentials and limitations in practical realization in future 2D device technologies.

Carbon-based structures are the most versatile materials used in the modern field of renewable energy (i.e., in both generation and storage) and environmental science (e.g., purification/remediation). However, there is a need and indeed a desire to develop increasingly more sustainable variants of classical carbon materials (e.g., activated carbons, carbon nanotubes, carbon aerogels, etc.), particularly when the whole life cycle is considered (i.e., from precursor "cradle" to "green" manufacturing and the product end-of-life "grave"). In this regard, and perhaps mimicking in some respects the natural carbon cycles/production, utilization of natural, abundant and more renewable precursors, coupled with simpler, lower energy synthetic processes which can contribute in part to the reduction in greenhouse gas emissions or the use of toxic elements, can be considered as crucial parameters in the development of sustainable materials manufacturing. Therefore, the synthesis and application of sustainable carbon materials are receiving increasing levels of interest, particularly as application benefits in the context of future energy/chemical industry are becoming recognized. This review will introduce to the reader the most recent and important progress regarding the production of sustainable carbon materials, whilst also highlighting their application in important environmental and energy related fields.

The problem of electron-electron interactions in graphene is reviewed. Starting from the screening of long-range interactions in these systems, the existence of an emerging Dirac liquid of Lorentz invariant quasiparticles in the weak-coupling regime is discussed, as well as the formation of strongly correlated electronic states in the strong-coupling regime. The analogy and connections between the many-body problem and the Coulomb impurity problem are also analyzed. The problem of the magnetic instability and Kondo effect of impurities and/or adatoms in graphene is also discussed in analogy with classical models of many-body effects in ordinary metals. Lorentz invariance is shown to play a fundamental role and leads to effects that span the whole spectrum, from the ultraviolet to the infrared. The effect of an emerging Lorentz invariance is also discussed in the context of finite size and edge effects as well as mesoscopic physics. The effects of strong magnetic fields in single layers and some of the main aspects of the many-body problem in graphene bilayers are briefly reviewed. In addition to reviewing the fully understood aspects of the many-body problem in graphene, a plethora of interesting issues are shown to remain open, both theoretically and experimentally, and the field of graphene research is still exciting and vibrant.

Carbon nanotubes and graphene are some of the most intensively explored carbon allotropes in materials science. This interest mainly resides in their unique properties with electrical conductivities as high as 10(4) S cm(-1), thermal conductivities as high as 5000 W m(-1) K and superior mechanical properties with elastic moduli on the order of 1 TPa for both of them. The possibility to translate the individual properties of these monodimensional (e.g. carbon nanotubes) and bidimensional (e.g. graphene) building units into two-dimensional free-standing thick and thin films has paved the way for using these allotropes in a number of applications (including photocatalysis, electrochemistry, electronics and optoelectronics, among others) as well as for the preparation of biological and chemical sensors. More recently and while recognizing the tremendous interest of these two-dimensional structures, researchers are noticing that the performance of certain devices can experience a significant enhancement by the use of three-dimensional architectures and/or aerogels because of the increase of active material per projected area. This is obviously the case as long as the nanometre-sized building units remain accessible so that the concept of hierarchical three-dimensional organization is critical to guarantee the mass transport and, as consequence, performance enhancement. Thus, this review aims to describe the different synthetic processes used for preparation of these three-dimensional architectures and/or aerogels containing either any or both allotropes, and the different fields of application in which the particular structure of these materials provided a significant enhancement in the efficacy as compared to their two-dimensional analogues or even opened the path to novel applications. The unprecedented compilation of information from both CNT- and graphene-based three-dimensional architectures and/or aerogels in a single revision is also of interest because it allows a straightforward comparison between the particular features provided by each allotrope.

The polarization of graphene is calculated exactly within the random phase approximation for arbitrary frequency, wave vector, and doping. At finite doping, the static susceptibility saturates to a constant value for low momenta. At $q=2 k_{F}$ it has a discontinuity only in the second derivative. In the presence of a charged impurity this results in Friedel oscillations which decay with the same power law as the Thomas Fermi contribution, the latter being always dominant. The spin density oscillations in the presence of a magnetic impurity are also calculated. The dynamical polarization for low $q$ and arbitrary $\omega $ is employed to calculate the dispersion relation and the decay rate of plasmons and acoustic phonons as a function of doping. The low screening of graphene, combined with the absence of a gap, leads to a significant stiffening of the longitudinal acoustic lattice vibrations.

A previously unreported ferroelectric phase has been discovered in a highly homogeneous sample of PbZr0.52Ti0.48O3 by high-resolution synchrotron x-ray powder diffraction measurements. At ambient temperature the sample has tetragonal symmetry (at=4.037 Å, ct=4.138 Å), and transforms below ∼250 K into a phase which, unexpectedly, has monoclinic symmetry (am=5.717 Å, bm=5.703 Å, cm=4.143 Å, β=90.53°, at 20 K). The intensity data strongly indicate that the polar axis lies in the monoclinic ac plane close to the pseudocubic [111] direction, which would be an example of the species m3m(12)A2Fm predicted on symmetry grounds by Shuvalov.

A continuum model for the effective spin-orbit interaction in graphene is derived from a tight-binding model which includes the $\ensuremath{\pi}$ and $\ensuremath{\sigma}$ bands. We analyze the combined effects of the intra-atomic spin-orbit coupling, curvature, and applied electric field, using perturbation theory. We recover the effective spin-orbit Hamiltonian derived recently from group theoretical arguments by Kane and Mele. We find, for flat graphene, that the intrinsic spin-orbit coupling ${\ensuremath{\Delta}}_{\mathrm{int}}\ensuremath{\propto}{\ensuremath{\Delta}}^{2}$ and the Rashba coupling due to a perpendicular electric field $\mathcal{E}$, ${\ensuremath{\Delta}}_{\mathcal{E}}\ensuremath{\propto}\ensuremath{\Delta}$, where $\ensuremath{\Delta}$ is the intra-atomic spin-orbit coupling constant for carbon. Moreover we show that local curvature of the graphene sheet induces an extra spin-orbit coupling term ${\ensuremath{\Delta}}_{\mathrm{curv}}\ensuremath{\propto}\ensuremath{\Delta}$. For the values of $\mathcal{E}$ and curvature profile reported in actual samples of graphene, we find that ${\ensuremath{\Delta}}_{\mathrm{int}}&lt;{\ensuremath{\Delta}}_{\mathcal{E}}\ensuremath{\lesssim}{\ensuremath{\Delta}}_{\mathrm{curv}}$. The effect of spin-orbit coupling on derived materials of graphenelike fullerenes, nanotubes, and nanotube caps, is also studied. For fullerenes, only ${\ensuremath{\Delta}}_{\mathrm{int}}$ is important. Both for nanotubes and nanotube caps ${\ensuremath{\Delta}}_{\mathrm{curv}}$ is in the order of a few Kelvins. We reproduce the known appearance of a gap and spin-splitting in the energy spectrum of nanotubes due to the spin-orbit coupling. For nanotube caps, spin-orbit coupling causes spin-splitting of the localized states at the cap, which could allow spin-dependent field-effect emission.

Atomic vacancies have a strong impact in the mechanical, electronic, and magnetic properties of graphenelike materials. By artificially generating isolated vacancies on a graphite surface and measuring their local density of states on the atomic scale, we have shown how single vacancies modify the electronic properties of this graphenelike system. Our scanning tunneling microscopy experiments, complemented by tight-binding calculations, reveal the presence of a sharp electronic resonance at the Fermi energy around each single graphite vacancy, which can be associated with the formation of local magnetic moments and implies a dramatic reduction of the charge carriers' mobility. While vacancies in single layer graphene lead to magnetic couplings of arbitrary sign, our results show the possibility of inducing a macroscopic ferrimagnetic state in multilayered graphene just by randomly removing single C atoms.

We study the magnetic properties of nanometer-sized graphene structures with triangular and hexagonal shapes terminated by zigzag edges. We discuss how the shape of the island, the imbalance in the number of atoms belonging to the two graphene sublattices, the existence of zero-energy states, and the total and local magnetic moment are intimately related. We consider electronic interactions both in a mean-field approximation of the one-orbital Hubbard model and with density functional calculations. Both descriptions yield values for the ground state total spin S consistent with Lieb's theorem for bipartite lattices. Triangles have a finite S for all sizes whereas hexagons have S=0 and develop local moments above a critical size of approximately 1.5 nm.