M J S Matos

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.

Graphene–boron nitride superlattices: the role of point defects at the BN layer

We investigate, by means of first-principles calculations, the role of hBN point defects on the energetical stability and electronic structure of heterostructures composed of graphene atop hBN, rotated at angles of 13.17°, 9.43° and 7.34°. We consider, as possible point defects, boron and nitrogen vacancies and antisites, substitutional oxygen at the nitrogen site ON, substitutional carbon dimers, and nitrogen interstitials. The electronic and structural properties of all defects were analyzed. Among these, the most stable is ON, with negative formation energies at several possible rotation angles and chemical environments. Under such conditions, ON doping can raise the Fermi level of the neutral system by as much as 1 eV relative to graphenes Dirac point, reaching the band crossing between adjacent Dirac cones at the M point of the heterostructure Brillouin zone. This could lead to interesting electronic transport properties without the need for electrostatic doping.

Correlation between (in)commensurate domains of multilayer epitaxial graphene grown on SiC(

A systematic study of the evolution of the electronic behavior and atomic structure of multilayer epitaxial graphene (MEG) as a function of growth time was performed. MEG was obtained by sublimation of a 4H-SiC(0001(-)) substrate in an argon atmosphere. Raman spectroscopy and x-ray diffraction were carried out in samples grown for different times. For 30 min of growth the sample Raman signal is similar to that of graphite, while for 60 min the spectrum becomes equivalent to that of exfoliated graphene. Conventional x-ray diffraction reveals that all the samples have two different (0001) lattice spacings. Grazing incidence x-ray diffraction shows that thin films are composed of rotated (commensurate) structures formed by adjacent graphene layers. Thick films are almost completely disordered. This result can be directly correlated to the single layer electronic behavior of the films as observed by Raman spectroscopy. Finally, to understand the change in lattice spacings as a result of layer rotation, we have carried out first principles calculations (using density functional theory) of the observed commensurate structures.

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Long-range order evolution of self-assembled phosphonic acid multilayers as a function of temperature is studied here for two molecules with different alkyl chain length. By using synchrotron conventional diffraction, distinct order configurations are retrieved on phosphonic acid multilayers and their thermodynamic behavior monitored by energy-dispersive diffraction. This later technique allows us to observe the system behavior near order-disorder temperatures, as well as to determine the most stable configurations in the range from room temperature up to 120 °C. Planar order is also addressed by wide-angle X-ray scattering (WAXS) transmission experiments. Order parameter phase diagrams are built based on the experimental results, showing the dominant configuration at each temperature. The multilayer molecular long-range order retrieved from the experiments is corroborated by first principles calculations based on the Density Functional Theory. The bulk configurations depicted in this work are produced by molecule-molecule interactions and allow for future comparisons with the behavior of ordered molecules in few-monolayers configurations, commonly used in organic devices, where the presence of surfaces and interfaces strongly affects the molecule packing.

) and single layer electronic behavior

In this paper, we address the challenge of identifying grain boundaries on the molybdenum disulphide (MoS2) surface at the nanometre scale using a simple self-assembled monolayer (SAM) decoration method. Combined with atomic force microscopy, octadecylphosphonic acid monolayers readily reveal grain boundaries in MoS2 at ambient conditions, without the need of atomic resolution measurements under vacuum. Additional ab initio calculations allow us to obtain the preferred orientation of the SAM structure relative to the MoS2 beneath, and therefore, together with the experiments, the MoS2 crystalline orientations at the grain boundaries. The proposed method enables the visualization of grain boundaries with sub-micrometer resolution for nanodevice investigation and failure analysis.

Thermal Stability and Ordering Study of Long- and Short-Alkyl Chain Phosphonic Acid Multilayers

In this work, we make use of an atomic layer deposition (ALD) surface reaction based on trimethyl-aluminum (TMA) and water to modify O-H terminated self-assembled layers of octadecylphosphonic acid (OPA). The structural modifications were investigated by X-ray reflectivity, X-ray diffraction, and atomic force microscopy. We observed a significant improvement in the thermal stability of ALD-modified molecules, with the existence of a supramolecular packing structure up to 500 °C. Following the experimental observations, density functional theory (DFT) calculations indicate the possibility of formation of a covalent network with aluminum atoms connecting OPA molecules at terrace surfaces. Chemical stability is also achieved on top of such a composite surface, inhibiting further ALD oxide deposition. On the other hand, in the terrace edges, where the covalent array is discontinued, the chemical conditions allow for oxide growth. Analysis of the DFT results on band structure and density of states of modified OPA molecules suggests that besides the observed thermal resilience, the dielectric character of OPA layers is preserved. This new ALD-modified OPA composite is potentially suitable for applications such as dielectric layers in organic devices, where better thermal performance is required.