Theoretical investigation of electronic and optical properties of andalusite within density functional theory

The electronic and optical properties of andalusite were studied by using quantum-mechanical calculations based on the density functional theory (DFT). The electronic structure shows that andalusite has a direct band gap of 5.01 eV. The complex dielectric function and optical constants, such as extinction coefficient, refractive index, reflectivity and energy-loss spectrum, are calculated. The optical properties of andalusite are discussed based on the band structure calculations. It is shown that the O-2p states and Al-3s states play a major role in optical transitions as initial and final states, respectively. (C) 2010 Elsevier Ltd. All rights reserved.

Propriedades física de molécilas orgânicas e compostos do tipo perovskita CdSiO3 e CaPbO3

In the first part of this work our concern was to investigate the thermal effects in organic crystals using the theory of the polarons. To analyse such effect, we used the Fröhlich s Hamiltonian, that describes the dynamics of the polarons, using a treatment based on the quantum mechanics, to elucidate the electron-phonon interaction. Many are the forms to analyzing the polaronic phenomenon. However, the measure of the dielectric function can supply important information about the small polarons hopping process. Besides, the dielectric function measures the answer to an applied external electric field, and it is an important tool for the understanding of the many-body effects in the normal state of a polaronic system. We calculate the dielectric function and its dependence on temperature using the Hartree-Fock decoupling method. The dieletric function s dependence on the temperature is depicted by through a 3D graph. We also analyzed the so called Arrhenius resistivity, as a functionof the temperature, which is an important tool to characterize the conductivity of an organic molecule. In the second part we analyzed two perovskita type crystalline oxides, namely the cadmium silicate triclinic (CdSiO3) and the calcium plumbate orthorhombic (CaPbO3), respectively. These materials are normally denominated ABO3 and they have been especially investigated for displaying ferroelectric, piezoelectric, dielectrics, semiconductors and superconductors properties. We found our results through ab initio method within the functional density theory (DFT) in the GGA-PBE and LDA-CAPZ approximations. After the geometry optimization for the two structure using the in two approximations, we found the structure parameters and compared them with the experimental data. We still determined further the angles of connection for the two analyzed cases. Soon after the convergence of the energy, we determined their band structures, fundamental information to characterize the nature of the material, as well as their dielectrics functions, optical absorption, partial density of states and effective masses of electrons and holes

Excitações em cristais fotônicos unidimensionais

In this work, we present a theoretical study of the propagation of electromagnetic waves in multilayer structures called Photonic Crystals. For this purpose, we investigate the phonon-polariton band gaps in periodic and quasi-periodic (Fibonacci-type) multilayers made up of both positive and negative refractive index materials in the terahertz (THz) region. The behavior of the polaritonic band gaps as a function of the multilayer period is investigated systematically. We use a theoretical model based on the formalism of transfer matrix in order to simplify the algebra involved in obtaining the dispersion relation of phonon-polaritons (bulk and surface modes). We also present a quantitative analysis of the results, pointing out the distribution of the allowed polaritonic bandwidths for high Fibonacci generations, which gives good insight about their localization and power laws. We calculate the emittance spectrum of the electromagnetic radiation, in THZ frequency, normally and obliquely incident (s and p polarized modes) on a one-dimensional multilayer structure composed of positive and negative refractive index materials organized periodically and quasi-periodically. We model the negative refractive index material by a effective medium whose electric permittivity is characterized by a phonon-polariton frequency dependent dielectric function, while for the magnetic permeability we have a Drude like frequency-dependent function. Similarity to the one-dimensional photonic crystal, this layered effective medium, called polaritonic Crystals, allow us the control of the electromagnetic propagation, generating regions named polaritonic bandgap. The emittance spectra are determined by means of a well known theoretical model based on Kirchoff s second law, together with a transfer matrix formalism. Our results shows that the omnidirectional band gaps will appear in the THz regime, in a well defined interval, that are independent of polarization in periodic case as well as in quasiperiodic case

Cálculos AB initio de propriedades estruturais, eletrônicas e ópticas de colmpostos CaXo3 (X=Si, Ge, Sn)

In this work we present a study of structural, electronic and optical properties, at ambient conditions, of CaSiO3, CaGeO3 and CaSnO3 crystals, all of them a member of Ca-perovskite class. To each one, we have performed density functional theory ab initio calculations within LDA and GGA approximations of the structural parameters, geometry optimization, unit cell volume, density, angles and interatomic length, band structure, carriers effective masses, total and partial density of states, dielectric function, refractive index, optical absorption, reflectivity, optical conductivity and loss function. A result comparative procedure was done between LDA and GGA calculations, a exception to CaSiO3 where only LDA calculation was performed, due high computational cost that its low symmetry crystalline structure imposed. The Ca-perovskite bibliography have shown the absence of electronic structure calculations about this materials, justifying the present work

Polaritons de exciton em super-redes semicondutoras

In this work we study the spectrum (bulk and surface modes) of exciton-polaritons in infinite and semi-infinite binary superlattices (such as, ···ABABA···), where the semiconductor medium (A), whose dielectric function depends on the frequency and the wavevector, alternating with a standard dielectric medium B. Here the medium A will be modeled by a nitride III-V semiconductor whose main characteristic is a wide-direct energy gap Eg. In particular, we consider the numerical values of gallium nitride (GaN) with a crystal structure wurtzite type. The transfer-matrix formalism is used to find the exciton-polariton dispersion relation. The results are obtained for both s (TE mode: transverse electric) and p (TM mode: transverse magnetic) polarizations, using three diferent kind of additional boundary conditions (ABC1, 2 e 3) besides the standard Maxwell's boundary conditions. Moreover, we investigate the behavior of the exciton-polariton modes for diferent ratios of the thickness of the two alternating materials forming the superlattice. The spectrums shows a confinement of the exciton-polariton modes due to the geometry of the superlattice. The method of Attenuated Total Reflection (ATR) and Raman scattering are the most adequate for probing this excitations

Electrical characterization of in situ polymerized polyaniline thin films

The alternating conductivity, sigma*(f) = sigma'(f) + i sigma ''(f), of in situ polymerized polyaniline thin films doped with hydrochloric acid, deposited on top of an interdigitated gold line array previously deposited on glass substrates, were measured in the frequency (f) range between 0.1 Hz to 10 MHz and in the temperature range from 100 to 430 K. The results for sigma'(f) are typical of a disordered solid material: for frequencies lower than a certain hopping frequency gamma(hop), log[sigma'(f)] is frequency-independent rising almost linearly for in logf > gamma(hop). A master curve was thus obtained by plotting the real component of the conductivity using normalized scales sigma'(f)/sigma(dc) and f/gamma(hop) which is indicative of a single process operating in the whole frequency range. An expression encompassing the conduction through a disordered structure taken from previous random free energy barrier model for hopping carriers, as well a dielectric function to represent the capacitive behavior of the PAni was employed to fit the experimental results. The dielectric constant and activation energy for hopping carriers were obtained as function of the polymer doping level. (c) 2007 Elsevier B.V. All rights reserved.

Photoreflectance studies of optical transitions in cubic GaN grown on GaAs(001) substrates

The optical properties of cubic GaN epitaxial layers were investigated by modulated photoreflectance (PR) and photoluminescence in the temperature interval from 5 to 300 K. The epilayers were grown on GaAs(001) substrates by molecular beam epitaxy using a nitrogen RIF-activated plasma source. The PR spectra show a transition which is well fitted using the third-derivative functional form of the unperturbed dielectric function, which we interpret as band-to-band transition. Our results allow determination of the temperature dependence of the main gap of c-GaN and give insights into the residual strain in the film, as well as allow us to estimate the binding energy of the complex formed by an exciton bound to a neutral acceptor. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Determinação de parâmetros ópticos de materiais por análise de Kramers-Kronig de espectros de infravermelho

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Caracterização de propriedades de vidros polarizados do sistema P2O5 – B2O3 – CaO – TiO2

Pós-graduação em Ciência dos Materiais - FEIS

Modelos não-lineares de teoria de campos e mundos-brana

Pós-graduação em Física - FEG

Simulative Investigation on the Electronic, Vibrational and Optical Properties of the Ge2Sb2Te5 Chalcogenide

Chalcogenides are chemical compounds with at least one of the following three chemical elements: Sulfur (S), Selenium (Sn), and Tellurium (Te). As opposed to other materials, chalcogenide atomic arrangement can quickly and reversibly inter-change between crystalline, amorphous and liquid phases. Therefore they are also called phase change materials. As a results, chalcogenide thermal, optical, structural, electronic, electrical properties change pronouncedly and significantly with the phase they are in, leading to a host of different applications in different areas. The noticeable optical reflectivity difference between crystalline and amorphous phases has allowed optical storage devices to be made. Their very high thermal conductivity and heat fusion provided remarkable benefits in the frame of thermal energy storage for heating and cooling in residential and commercial buildings. The outstanding resistivity difference between crystalline and amorphous phases led to a significant improvement of solid state storage devices from the power consumption to the re-writability to say nothing of the shrinkability. This work focuses on a better understanding from a simulative stand point of the electronic, vibrational and optical properties for the crystalline phases (hexagonal and faced-centered cubic). The electronic properties are calculated implementing the density functional theory combined with pseudo-potentials, plane waves and the local density approximation. The phonon properties are computed using the density functional perturbation theory. The phonon dispersion and spectrum are calculated using the density functional perturbation theory. As it relates to the optical constants, the real part dielectric function is calculated through the Drude-Lorentz expression. The imaginary part results from the real part through the Kramers-Kronig transformation. The refractive index, the extinctive and absorption coefficients are analytically calculated from the dielectric function. The transmission and reflection coefficients are calculated using the Fresnel equations. All calculated optical constants compare well the experimental ones.

Nonhydrogenic exciton spectrum in perovskite CH3NH3PbI3

The excitons in the orthorhombic phase of the perovskite CH3NH3PbI3 are studied using the effective mass approximation. The electron–hole interaction is screened by a distance-dependent dielectric function, as described by the Haken potential or the Pollmann–Büttner potential. The energy spectrum and the eigenfunctions are calculated for both cases. The results show that the Pollmann–Büttner model, using the corresponding parameters obtained from ab initio calculations, provides better agreement with the experimental results.

Excitonic properties of transition metal oxide perovskites and workflow automatization of GW schemes

The Many-Body-Perturbation Theory approach is among the most successful theoretical frameworks for the study of excited state properties. It allows to describe the excitonic interactions, which play a fundamental role in the optical response of insulators and semiconductors. The first part of the thesis focuses on the study of the quasiparticle, optical and excitonic properties of \textit{bulk} Transition Metal Oxide (TMO) perovskites using a G$_0$W$_0$+Bethe Salpeter Equation (BSE) approach. A representative set of 14 compounds has been selected, including 3d, 4d and 5d perovskites. An approximation of the BSE scheme, based on an analytic diagonal expression for the inverse dielectric function, is used to compute the exciton binding energies and is carefully bench-marked against the standard BSE results. In 2019 an important breakthrough has been achieved with the synthesis of ultrathin SrTiO3 films down to the monolayer limit. This allows us to explore how the quasiparticle and optical properties of SrTiO3 evolve from the bulk to the two-dimensional limit. The electronic structure is computed with G0W0 approach: we prove that the inclusion of the off-diagonal self-energy terms is required to avoid non-physical band dispersions. The excitonic properties are investigated beyond the optical limit at finite momenta. Lastly a study of the under pressure optical response of the topological nodal line semimetal ZrSiS is presented, in conjunction with the experimental results from the group of Prof. Dr. Kuntscher of the Augsburg University. The second part of the thesis discusses the implementation of a workflow to automate G$_0$W$_0$ and BSE calculations with the VASP software. The workflow adopts a convergence scheme based on an explicit basis-extrapolation approach [J. Klimeš \textit{et al.}, Phys. Rev.B 90, 075125 (2014)] which allows to reduce the number of intermediate calculations required to reach convergence and to explicit estimate the error associated to the basis-set truncation.

Complex natural resonances of conducting planar objects buried in a dielectric half-space

A scheme is presented to incorporate a mixed potential integral equation (MPIE) using Michalski's formulation C with the method of moments (MoM) for analyzing the scattering of a plane wave from conducting planar objects buried in a dielectric half-space. The robust complex image method with a two-level approximation is used for the calculation of the Green's functions for the half-space. To further speed up the computation, an interpolation technique for filling the matrix is employed. While the induced current distributions on the object's surface are obtained in the frequency domain, the corresponding time domain responses are calculated via the inverse fast Fourier transform (FFT), The complex natural resonances of targets are then extracted from the late time response using the generalized pencil-of-function (GPOF) method. We investigate the pole trajectories as we vary the distance between strips and the depth and orientation of single, buried strips, The variation from the pole position of a single strip in a homogeneous dielectric medium was only a few percent for most of these parameter variations.

Dielectric relaxation dynamics of high-temperature piezoelectric polyimide copolymers

Polyimide co-polymers have been prepared based on different diamines as co-monomers: a diamine without CN groups and a novel synthesized diamine with two CN groups prepared by polycondensation reaction followed by thermal cyclodehydration. Dielectric spectroscopy measurements were performed and the dielectric complex function, ac conductivity and electric modulus of the co-polymers were investigated as a function of CN group content in the frequency range from 0.1 Hz to 107 Hz at temperatures from 25 to 260 °C. For all samples and temperatures above 150ºC, the dielectric constant increases with increasing temperature due to increaseing conductivity. The α-relaxation is just detected for the sample without CN groups, being this relaxation overlapped by the electrical conductivity contributions in the remaining samples. For the copolymer samples and the polymer with CN groups an important Maxwell-Wagner-Sillars contribution is detected. The mechanisms responsible for the dielectric relaxation, conduction process and electric modulus response have been discussed as a function of the CN groups content present in the samples.