Bernardo R. A. Neves

Modulating the electronic properties along carbon nanotubes via tube-substrate interaction.

We study single wall carbon nanotubes (SWNTs) deposited on quartz. Their Raman spectrum depends on the tube-substrate morphology, and in some cases, it shows that the same SWNT-on-quartz system exhibits a mixture of semiconductor and metal behavior, depending on the orientation between the tube and the substrate. We also address the problem using electric force microscopy and ab initio calculations, both showing that the electronic properties along a single SWNT are being modulated via tube-substrate interaction.

Dynamic Negative Compressibility of Few-Layer Graphene, h-BN, and MoS2

We report a novel mechanical response of few-layer graphene, h-BN, and MoS(2) to the simultaneous compression and shear by an atomic force microscope (AFM) tip. The response is characterized by the vertical expansion of these two-dimensional (2D) layered materials upon compression. Such effect is proportional to the applied load, leading to vertical strain values (opposite to the applied force) of up to 150%. The effect is null in the absence of shear, increases with tip velocity, and is anisotropic. It also has similar magnitudes in these solid lubricant materials (few-layer graphene, h-BN, and MoS(2)), but it is absent in single-layer graphene and in few-layer mica and Bi(2)Se(3). We propose a physical mechanism for the effect where the combined compressive and shear stresses from the tip induce dynamical wrinkling on the upper material layers, leading to the observed flake thickening. The new effect (and, therefore, the proposed wrinkling) is reversible in the three materials where it is observed.

Two-Dimensional Molecular Crystals of Phosphonic Acids on Graphene

The synthesis and characterization of two-dimensional (2D) molecular crystals composed of long and linear phosphonic acids atop graphene is reported. Using scanning probe microscopy in combination with first-principles calculations, we show that these true 2D crystals are oriented along the graphene armchair direction only, thereby enabling an easy determination of graphene flake orientation. We have also compared the doping level of graphene flakes via Raman spectroscopy. The presence of the molecular crystal atop graphene induces a well-defined shift in the Fermi level, corresponding to hole doping, which is in agreement with our ab initio calculations.

The use of a Ga+ focused ion beam to modify graphene for device applications

In this work, we clarify the features of the lateral damage of line defects in single layer graphene. The line defects were produced through well-controlled etching of graphene using a Ga(+) focused ion beam. The lateral damage length was obtained from both the integrated intensity of the disorder induced Raman D band and the minimum ion fluence. Also, the line defects were characterized by polarized Raman spectroscopy. It was found that graphene is resilient under the etching conditions since the intensity of the defect induced Raman D peak exhibits a dependence on the direction of the lines relative to the crystalline lattice and also on the direction of the laser polarization relative to the lines. In addition, electrical measurements of the modified graphene were performed. Different ion fluences were used in order to obtain a completely insulating defect line in graphene, which was determined experimentally by means of charge injection and electric force microscopy measurements. These studies demonstrate that a Ga+ ion column combined with Raman spectroscopy is a powerful technique to produce and understand well-defined periodic arrays of defects in graphene, opening possibilities for better control of nanocarbon devices.

X-ray method to study temperature-dependent stripe domains in MnAs∕GaAs(001)

MnAs films grown on GaAs (001) exhibit a progressive transition between hexagonal (ferromagnetic) and orthorhombic (paramagnetic) phases at wide temperature range instead of abrupt transition during the first-order phase transition. The coexistence of two phases is favored by the anisotropic strain arising from the constraint on the MnAs films imposed by the substrate. This phase coexistence occurs in ordered arrangement alternating periodic terrace steps. We present here a method to study the surface morphology throughout this transition by means of specular and diffuse scattering of soft x rays, tuning the photon energy at the Mn2p resonance. The results show the long-range arrangement of the periodic stripe-like structure during the phase coexistence and its period remains constant, in agreement with previous results using other techniques.

Characterization of Metal Oxide-Based Gas Nanosensors and Microsensors Fabricated via Local Anodic Oxidation Using Atomic Force Microscopy

This work reports on nanoscale and microscale metal oxide gas sensors, consisting of metal-semiconductor-metal barriers designed via scanning probe microscopy. Two distinct metal oxides, molybdenum and titanium oxides, were tested at different temperatures using CO2 and H2 as test gases. Sensitivities down to ppm levels are demonstrated, and the influence of dry and humid working atmospheres on these metal oxide conductivities was studied. Furthermore, the activation energy was evaluated and analyzed within working sensor temperature range. Finally, full morphological, chemical, and structural analyses of the oxides composites are provided allowing their identification as MoO3 and Ti.

In vitro exposure to fullerene C60 influences redox state and lipid peroxidation in brain and gills from Cyprinus carpio (Cyprinidae)

Studies concerning the impact of nanomaterials, especially fullerene (C(60) ), in fresh water environments and their effects on the physiology of aquatic organisms are still scarce and conflicting. We aimed to assess in vitro effects of fullerene in brain and gill homogenates of carp Cyprinus carpio, evaluating redox parameters. A fullerene suspension was prepared by continued stirring under fluorescent light during two months. The suspension concentration was measured by total carbon content and ultraviolet-visible spectroscopy nephelometry. Characterization of C(60) aggregates was performed with an enhanced dark-field microscopy system and transmission electronic microscopy. Organ homogenates were exposed during 1, 2, and 4 h under fluorescent light. Redox parameters evaluated were reduced glutathione and oxidized glutathione, cysteine and cystine, total antioxidant capacity; activity of the antioxidant enzymes glutathione S-transferase and glutathione reductase (GR), and lipid peroxidation (TBARS assay). Fullerene induced a significant increase (p < 0.05) in lipid peroxidation after 2 h in both organs and reduced GR activity after 1 h (gills) and 4 h (brain) and antioxidant capacity after 4 h (brain). Levels of oxidized glutathione increased in the brain at 1 h and decreased at 2 h as well. Given these results, it can be concluded that C(60) can induce redox disruption via thiol/disulfide pathway, leading to oxidative damage (higher TBARS values) and loss of antioxidant competence.

Mixed self-assembled layers of phosphonic acids.

Self-assembled monolayers, bilayers, and other structures of mixed phosphonic acids were investigated using atomic force microscopy. Octadecylphosphonic acid (OPA, 18 carbon atoms in the alkyl chain) was mixed in solution, with different ratios, with octylphosphonic acid (OcPA, 8 carbon atoms in the alkyl chain) and deposited onto mica substrates. Self-assembled monolayers were formed, with no evidence of phase separation, from pure OPA up to 5:10 OPA/OcPA ratio (despite the large alkyl chain length difference). It was found that water plays a crucial role in the morphology of the self-assembled structures and their time evolution. The formation of bilayers instead of monolayers (OcPA-type behavior) is dominant for high water content (both in solution and/or the atmosphere). Mechanical and thermal resistance tests were performed on mixed and pure samples and revealed different properties that can be correlated to their composition.

Raman evidence for pressure-induced formation of diamondene

Despite the advanced stage of diamond thin-film technology, with applications ranging from superconductivity to biosensing, the realization of a stable and atomically thick two-dimensional diamond material, named here as diamondene, is still forthcoming. Adding to the outstanding properties of its bulk and thin-film counterparts, diamondene is predicted to be a ferromagnetic semiconductor with spin polarized bands. Here, we provide spectroscopic evidence for the formation of diamondene by performing Raman spectroscopy of double-layer graphene under high pressure. The results are explained in terms of a breakdown in the Kohn anomaly associated with the finite size of the remaining graphene sites surrounded by the diamondene matrix. Ab initio calculations and molecular dynamics simulations are employed to clarify the mechanism of diamondene formation, which requires two or more layers of graphene subjected to high pressures in the presence of specific chemical groups such as hydroxyl groups or hydrogens.The synthesis of two-dimensional diamond is the ultimate goal of diamond thin-film technology. Here, the authors perform Raman spectroscopy of bilayer graphene under pressure, and obtain spectroscopic evidence of formation of diamondene, an atomically thin form of diamond.

Nanoscale lateral switchable rectifiers fabricated by local anodic oxidation

Scanning probe lithography as a mean to pattern, implement, and discover new devices in different materials systems provides an elevated degree of flexibility, permitting one to tailor device geometries and structures at will, in particular by virtue of modification of the local chemistry. Here we define metal-insulator-metal junctions exhibiting a switchable rectifier behavior by patterning titanium channels through local anodic oxidation techniques. The nanoscale TiO2 junctions thus formed exhibit IV characteristics with non-volatile switchable rectification and memristive behavior due to ionic motion through the metal-semiconductor interfaces.