Simulação computacional de materiais bidimensionais: funcionalização de defeitos extensos no grafeno e retenção de contaminantes por argilominerais

In this work are considered two bidimensional systems, with distints chacacteristcs and applicabilitys. Is studied the adsorption of transition metals (MT) Fe, Co, Mn and Ru in extended defects, formed by graphene grain boundaries. First in pristine graphene The hollow site of carbon hexagon, in pristine graphene, are the most stable for MT adsorption. The Dirac cone in eletronic structure of graphene was manteined with the presence of MT. For the considered grain boundaries the MT has a greater stability for absorption in the grain boundaries sites in comparison with pristine graphene. Through the energy barrier values, are observed diffusion chanels for MT localized on the grain boundaries. This diffusion chanels indicate a possible formation of nanolines of MT in graphene. For the first stage of the nanolines, ate observed a better stability for the system with greater MT concentration, due to MT-MT interactions. Also, due to the magnetic moment of the MT, the nanolines show a magnetization. For the most stable configurations the system are metallics, particularly for Fe the band structure indicates an anisotropic spin current. In a second study, are considereted the retention capacity for metallic contaminants Cd and Hg in clayminerals, kaolinite (KAO) and montmorillonite (MMT). Through the adsorption energies of contaminantes in the clayminerals, was observed a increase in stability with the increase of contaminants concentration, due to the interaction Cd-Cd and Hg-Hg. Also, was observed that KAO has a strong interaction beteween monolayers than MMT. In this sence, for the adsoption process of contaminantes in the natural form of KAO and MMT, the latter has a better retention capacity, due to the small net work for contaminant intercalation. However, when the modification of clayminerals, with molecules that increase the spacing between monolayers, exist a optimal condition, which the contaminant absorption are more stable in KAO system than in MMT. In the Langmuir adsorption model for the clayminerals in the optimal monolayer spacing, the retention capacity for Cd and Hg in KAO system are 21% greater than in MMT system. Also, for the X-ray Absorption Near Edge Spectroscopy (XANES) for the K edge of Cd and Hg, are found a positive shift of absorption edge with the decreasing of monolayer spacing. This result indicates a possible way to determine the concentration of adsorbed contaminats in relation to unabsorbed ones, from the decomposition of experimental XANES in the obteined spectras.

Antimony-based type-II superlattice infrared detectors

Numerous applications within the mid- and long-wavelength infrared are driving the search for efficient and cost effective detection technologies in this regime. Theoretical calculations have predicted high performance for InAs/GaSb type-II superlattice structures, which rely on mature growth of III-V semiconductors and offer many levels of freedom in design due to band structure engineering. This work focuses on the fabrication and characterization of type-II superlattice infrared detectors. Standard UV-based photolithography was used combined with chemical wet or dry etching techniques in order to fabricate antinomy-based type-II superlattice infrared detectors. Subsequently, Fourier transform infrared spectroscopy and radiometric techniques were applied for optical characterization in order to obtain a detector's spectrum and response, as well as the overall detectivity in combination with electrical characterization. Temperature dependent electrical characterization was used to extract information about the limiting dark current processes. This work resulted in the first demonstration of an InAs/GaSb type-II superlattice infrared photodetector grown by metalorganic chemical vapor deposition. A peak detectivity of 1.6x10^9 Jones at 78 K was achieved for this device with a 11 micrometer zero cutoff wavelength. Furthermore the interband tunneling detector designed for the mid-wavelength infrared regime was studied. Similar results to those previously published were obtained.

Atomic resolution studies of oxide superlattices and ultrathin films

The ability to grow ultrathin films layer-by-layer with well-defined epitaxial relationships has allowed research groups worldwide to grow a range of artificial films and superlattices, first for semiconductors, and now with oxides. In the oxides thin film research community, there have been concerted efforts recently to develop a number of epitaxial oxide systems grown on single crystal oxide substrates that display a wide variety of novel interfacial functionality, such as enhanced ferromagnetic ordering, increased charge carrier density, increased optical absorption, etc, at interfaces. The magnitude of these novel properties is dependent upon the structure of thin films, especially interface sharpness, intermixing, defects, and strain, layering sequence in the case of superlattices and the density of interfaces relative to the film thicknesses. To understand the relationship between the interfacial thin film oxide atomic structure and its properties, atomic scale characterization is required. Transmission electron microscopy (TEM) offers the ability to study interfaces of films at high resolution. Scanning transmission electron microscopy (STEM) allows for real space imaging of materials with directly interpretable atomic number contrast. Electron energy loss spectroscopy (EELS), together with STEM, can probe the local chemical composition as well as local electronic states of transition metals and oxygen. Both techniques have been significantly improved by aberration correctors, which reduce the probe size to 1 Å, or less. Aberration correctors have thus made it possible to resolve individual atomic columns, and possibly probe the electronic structure at atomic scales. Separately, using electron probe forming lenses, structural information such as the crystal structure, strain, lattice mismatches, and superlattice ordering can be measured by nanoarea electron diffraction (NED). The combination of STEM, EELS, and NED techniques allows us to gain a fundamental understanding of the properties of oxide superlattices and ultrathin films and their relationship with the corresponding atomic and electronic structure. In this dissertation, I use the aforementioned electron microscopy techniques to investigate several oxide superlattice and ultrathin film systems. The major findings are summarized below. These results were obtained with stringent specimen preparation methods that I developed for high resolution studies, which are described in Chapter 2. The essential materials background and description of electron microscopy techniques are given in Chapter 1 and 2. In a LaMnO3-SrMnO3 superlattice, we demonstrate the interface of LaMnO3-SrMnO3 is sharper than the SrMnO3-LaMnO3 interface. Extra spectral weights in EELS are confined to the sharp interface, whereas at the rougher interface, the extra states are either not present or are not confined to the interface. Both the structural and electronic asymmetries correspond to asymmetric magnetic ordering at low temperature. In a short period LaMnO3-SrTiO3 superlattice for optical applications, we discovered a modified band structure in SrTiO3 ultrathin films relative to thick films and a SrTiO3 substrate, due to charge leakage from LaMnO3 in SrTiO3. This was measured by chemical shifts of the Ti L and O K edges using atomic scale EELS. The interfacial sharpness of LaAlO3 films grown on SrTiO3 was investigated by the STEM/EELS technique together with electron diffraction. This interface, when prepared under specific conditions, is conductive with high carrier mobility. Several suggestions for the conductive interface have been proposed, including a polar catastrophe model, where a large built-in electric field in LaAlO3 films results in electron charge transfer into the SrTiO3 substrate. Other suggested possibilities include oxygen vacancies at the interface and/or oxygen vacancies in the substrate. The abruptness of the interface as well as extent of intermixing has not been thoroughly investigated at high resolution, even though this can strongly influence the electrical transport properties. We found clear evidence for cation intermixing through the LaAlO3-SrTiO3 interface with high spatial resolution EELS and STEM, which contributes to the conduction at the interface. We also found structural defects, such as misfit dislocations, which leads to increased intermixing over coherent interfaces.

Optical properties of semiconductor quantum wires

This thesis presents theoretical investigations of the sub band structure and optical properties of semiconductor quantum wires. For the subband structure, we employ multiband effective-mass theory and the effective bond-orbital model both of which fully account for the band mixing and material anisotropy. We also treat the structure geometry in detail taking account of such effects as the compositional grading across material interfaces. Based on the subband structure, we calculate optical properties of quantum-wire structures. A recuring theme is the cross-over from one- to ~wo-dimensional behavior in these structures. This complicated behavior procludes the application of simple theoretical models to obtain the electronic structure. In particular, we calculate laser properties of quantum wires grown in V-grooves and find enhanced performance compared with quantum-well lasers. We also investigate optical anisotropy in quantum-wire arrays and propose an electro-optic device based on such structures.

Superlattice structures in twisted bilayers of folded graphene

The electronic properties of bilayer graphene strongly depend on relative orientation of the two atomic lattices. Whereas Bernal-stacked graphene is most commonly studied, a rotational mismatch between layers opens up a whole new field of rich physics, especially at small interlayer twist. Here we report on magnetotransport measurements on twisted graphene bilayers, prepared by folding of single layers. These reveal a strong dependence on the twist angle, which can be estimated by means of sample geometry. At small rotation, superlattices with a wavelength in the order of 10 nm arise and are observed by friction atomic force microscopy. Magnetotransport measurements in this small-angle regime show the formation of satellite Landau fans. These are attributed to additional Dirac singularities in the band structure and discussed with respect to the wide range of interlayer coupling models.

First-Principles Calculations of the Electronic and Structural Properties of GaSb

In this paper, we carried out first-principles calculations in order to investigate the structural and electronic properties of the binary compound gallium antimonide (GaSb). This theoretical study was carried out using the Density Functional Theory within the plane-wave pseudopotential method. The effects ofexchange and correlation (XC) were treated using the functional Local Density Approximation (LDA), generalized gradient approximation (GGA): Perdew–Burke–Ernzerhof (PBE), Perdew-Burke-Ernzerhof revised for solids (PBEsol), Perdew-Wang91 (PW91), revised Perdew–Burke–Ernzerhof (rPBE), Armiento–Mattson 2005 (AM05) and meta-generalized gradient approximation (meta-GGA): Tao–Perdew– Staroverov–Scuseria (TPSS) and revised Tao–Perdew–Staroverov–Scuseria (RTPSS) and modified Becke-Johnson (MBJ). We calculated the densities of state (DOS) and band structure with different XC potentials identified and compared them with the theoretical and experimental results reported in the literature. It was discovered that functional: LDA, PBEsol, AM05 and RTPSS provide the best results to calculate the lattice parameters (a) and bulk modulus (B0); while for the cohesive energy (Ecoh), functional: AM05, RTPSS and PW91 are closer to the values obtained experimentally. The MBJ, Rtpss and AM05 values found for the band gap energy is slightly underestimated with those values reported experimentally.

Analytical and numerical study of polarons

The aim of this thesis is to introduce the polaron concept and to perform a DFT numerical calculation of a small polaron in the rutile phase of TiO2. In the first chapters, we present an analytical study of small and large polarons, based on the Holstein and Fröhlich Hamiltonians. The necessary mathematical formalism and physics fundamentals are briefly reviewed in the first chapter. In the second part of the thesis, Density Functional Theory (DFT) is introduced together with the DFT+U correction and its implementation in the Vienna Ab-Initio Simulation Package (VASP). The calculation of a small polaron in rutile is then described and discussed at a qualitative level. The polaronic solution is compared with the one of a delocalized electron. The calculation showed how the polaron creates a new energy level 0.70 eV below the conduction band. The energy level is visible both in the band structure diagram and in the density of states diagram. The electron is localized on a titanium atom, distorting the surrounding lattice. In particular, the four oxygen atoms closer to the titanium atom are displaced by 0.085 Å outwards, whereas the two further oxygen atoms by 0.023 Å. The results are compatible, at a qualitative level, with the literature. Further developments of this work may try to improve the precision of the results and to quantitatively compare them with the literature.

Two-dimensional photonic crystals in antimony-based films fabricated by holography

In this work, we demonstrated the fabrication of two-dimensional (2D) photonic crystals layers (2D-PCLs) by combining holographic recording and the evaporation of antimony-based glasses. Such materials present high refractive indices that can be tuned from 1.8 to 2.4, depending on the film composition; thus, they are interesting dielectric materials for fabrication of 2D-PCLs. The good quality of the obtained samples allowed the measurement of their PC properties through the well-defined Fano resonances that appear in the transmittance spectrum measurements at different incidence angles. The experimental results are in good agreement with the calculated band diagram for the hexagonal asymmetric structure. (C) 2008 American Institute of Physics.

Theory of multidimensional parametric band-gap simultons

Multidimensional spatiotemporal parametric simultons (simultaneous solitary waves) are possible in a nonlinear chi((2)) medium with a Bragg grating structure, where large effective dispersion occurs near two resonant band gaps for the carrier and second-harmonic field, respectively. The enhanced dispersion allows much reduced interaction lengths, as compared to bulk medium parametric simultons. The nonlinear parametric band-gap medium permits higher-dimensional stationary waves to form. In addition, solitons can occur with lower input powers than conventional nonlinear Schrodinger equation gap solitons. In this paper, the equations for electromagnetic propagation in a grating structure with a parametric nonlinearity are derived from Maxwell's equation using a coupled mode Hamiltonian analysis in one, two, and three spatial dimensions. Simultaneous solitary wave solutions are proved to exist by reducing the equations to the coupled equations describing a nonlinear parametric waveguide, using the effective-mass approximation (EMA). Exact one-dimensional numerical solutions in agreement with the EMA solutions are also given. Direct numerical simulations show that the solutions have similar types of stability properties to the bulk case, providing the carrier waves are tuned to the two Bragg resonances, and the pulses have a width in frequency space less than the band gap. In summary, these equations describe a physically accessible localized nonlinear wave that is stable in up to 3 + 1 dimensions. Possible applications include photonic logic and switching devices. [S1063-651X(98)06109-1].

High resolution optogalvanic spectrum of N2-rotational structure of (11, 7) band in the first positive system

High resolution optogalvanic spectrum of the (11, 7) band in the first positive system of nitrogen molecule has been recorded from 17179 to 17376 cm- 1. Assignment of 432 rotational lines belonging to the 27 branches of this band has been carried out.

Band-edge states of the zero(th)-order gap in quasi-periodic photonic superlattices

The photonic modes of Thue-Morse and Fibonacci lattices with generating layers A and B, of positive and negative indices of refraction, are calculated by the transfer-matrix technique. For Thue-Morse lattices, as well for periodic lattices with AB unit cell, the constructive interference of reflected waves, corresponding to the zero(th)-order gap, takes place when the optical paths in single layers A and B are commensurate. In contrast, for Fibonacci lattices of high order, the same phenomenon occurs when the ratio of those optical paths is close to the golden ratio. In the long wavelength limit, analytical expressions defining the edge frequencies of the zero(th) order gap are obtained for both quasi-periodic lattices. Furthermore, analytical expressions that define the gap edges around the zero(th) order gap are shown to correspond to the = 0 and = 0 conditions.

Band edge states of the < n >=0 gap of Fibonacci photonic lattices

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Two-dimensional photonic crystals in antimony-based films fabricated by holography

In this work, we demonstrated the fabrication of two-dimensional (2D) photonic crystals layers (2D-PCLs) by combining holographic recording and the evaporation of antimony-based glasses. Such materials present high refractive indices that can be tuned from 1.8 to 2.4, depending on the film composition; thus, they are interesting dielectric materials for fabrication of 2D-PCLs. The good quality of the obtained samples allowed the measurement of their PC properties through the well-defined Fano resonances that appear in the transmittance spectrum measurements at different incidence angles. The experimental results are in good agreement with the calculated band diagram for the hexagonal asymmetric structure. (C) 2008 American Institute of Physics.

A puzzling solar cell structure: an exercise to get insight on intermediate band solar cells

We introduce one trivial but puzzling solar cell structure. It consists of a high bandgap pn junction (top cell) grown on a substrate of lower bandgap. Let us assume, for example, that the bandgap of the top cell is 1.85 eV (Al 0.3Ga 0.7As) and the bandgap of the substrate is 1.42 eV (GaAs). Is the open-circuit of the top cell limited to 1.42 V or to 1.85 V? If the answer is ldquo1.85 Vrdquo we could then make the mind experiment in which we illuminate the cell with 1.5 eV photons (notice these photons would only be absorbed in the substrate). If we admit that these photons can generate photocurrent, then because we have also admitted that the voltage is limited to 1.85 V, it might be possible that the electron-hole pairs generated by these photons were extracted at 1.6 V for example. However, if we do so, the principles of thermodynamics could be violated because we would be extracting more energy from the photon than the energy it initially had. How can we then solve this puzzle?

Enhanced optical properties of the GaAsN/GaAs quantum-well structure by the insertion of InAs monolayers

Microstructural and optical properties of InAs-inserted and reference single GaAsN/GaAs quantum-well (QW) structures grown by metalorganic chemical vapor deposition were investigated using cross-sectional transmission electron microscopy and photoluminescence (PL). Significant enhancement of PL intensity and a blueshift of PL emission were observed from the InAs-inserted GaAsN/GaAs QW structure, compared with the single GaAsN/GaAs QW structure. Strain compensation and In-induced reduction of N incorporation are suggested to be two major factors affecting the optical properties. (C) 2004 American Institute of Physics.