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

Sistemas Nanoestruturados: Heteroestruturas Quasi-Periódicas de Nitretos e Cálculos Ab initio em Polimorfos CaCO3

The physical properties and the excitations spectrum in oxides and semiconductors materials are presented in this work, whose the first part presents a study on the confinement of optical phonons in artificial systems based on III-V nitrides, grown in periodic and quasiperiodic forms. The second part of this work describes the Ab initio calculations which were carried out to obtain the optoeletronic properties of Calcium Oxide (CaO) and Calcium Carbonate (CaCO3) crystals. For periodic and quasi-periodic superlattices, we present some dynamical properties related to confined optical phonons (bulk and surface), obtained through simple theories, such as the dielectric continuous model, and using techniques such as the transfer-matrix method. The localization character of confined optical phonon modes, the magnitude of the bands in the spectrum and the power laws of these structures are presented as functions of the generation number of sequence. The ab initio calculations have been carried out using the CASTEP software (Cambridge Total Sequential Energy Package), and they were based on ultrasoft-like pseudopotentials and Density Functional Theory (DFT). Two di®erent geometry optimizations have been e®ectuated for CaO crystals and CaCO3 polymorphs, according to LDA (local density approximation) and GGA (generalized gradient approximation) approaches, determining several properties, e. g. lattice parameters, bond length, electrons density, energy band structures, electrons density of states, e®ective masses and optical properties, such as dielectric constant, absorption, re°ectivity, conductivity and refractive index. Those results were employed to investigate the confinement of excitons in spherical Si@CaCO3 and CaCO3@SiO2 quantum dots and in calcium carbonate nanoparticles, and were also employed in investigations of the photoluminescence spectra of CaCO3 crystal

High-energy transitions of shallow magnetodonors in a GaAs/Al0.3Ga0.7As multiple quantum well

The high-energy states of a shallow donor in a GaAs/Ga0.7Al0.3As multiple-quantum-well structure subjected to a magnetic field in the growth direction are studied both theoretically and experimentally. Effects due to higher confinement subbands as well as due to the electron-phonon interaction are investigated. We show that most of the peaks in the infrared photoconductivity spectrum are due to direct transitions from the ground state to the m = +/-1 magnetodonor states associated with the first subband, but transitions to the m = +/-1 states of the third subband are also apparent. The remaining photoconductivity peaks are explained by phonon-assisted impurity transitions.

Espectroscopia óptica de vidros fluoroindatos dopados com íons Er3+ e Yb3+

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Intersubband excitations at finite temperatures and their roles in different quasi-one-dimensional systems

We theoretically study many-body excitations in three different quasi-one-dimensional (Q1D) electron systems: (i) those formed on the surface of liquid Helium; (ii) in two coupled semiconductor quantum wires; and (iii) Q1D electrons embedded in polar semiconductor-based quantum wires. Our results show intersubband coupling between higher subbands and the two lowest subbands affecting even the lower energy intersubband plasmons on the liquid Helium surface. Concerning the second system, we show a pronounced extra peak appearing in the intersubband impurity spectral function for temperatures as high as 20 K. We finally show coupled intersubband plasmon-phonon modes surviving for temperatures up to 300 K.

Surface morphology and optical characterization of OC1 OC6-PPV films

We report optical and morphological properties of poly(2-methoxy-5-hexyloxy-p-phenylenevinylene) (OC1OC6-PPV) films processed by casting, spin-coating (SC) and Langmuir-Blodgett (LB) techniques. The absorption spectra are practically the same, with an absorption maximum at approximately at 500 nm. For the photoluminescence (PL) spectra at low temperature (T=10K), a small but significant difference was noted in the cast film, in comparison with the LB and SC films. The zero-phonon transition shifted from 609 nm for the LB film to 615 and 621 nm for the SC and cast films, respectively. At room temperature, the PL spectra are similar for all films, and blue shifted by ca. 25 nm in comparison with the spectra at low temperature due to thermal disorder. Using atomic force microscopy (AFM) we inferred that the distinctive behavior of the cast film, probably associated with structural defects, is related to the large thickness of this film. The surface roughness, which was surprisingly higher for the LB film, apparently played no role in the emission properties of OC1OC6-PPV films.

Ashcroft model potential study of lattice dynamics of α-iron and barium

Ashcroft model potential has been used to compute phonon dispersion relations along the three principal symmetry directions, i.e. [k00], [kk0] and [kkk] for alpha-iron and barium. The computed phonons gave a reasonable agreement with the experimental ones in all the three principal summetry directions expect for the T-2 branch in [KK0] direction where the present study failed to reproduce the experimental findings.

Red-green-blue upconversion emission and energy-transfer between Tm3+ and Er3+ ions in tellurite glasses excited at 1.064 mu m

Red, green, and blue emission through frequency upconversion and energy-transfer processes in tellurite glasses doped with Tm3+ and Er3+ excited at 1.064 mum is investigated. The Tm3+/Er3+-codoped samples produced intense upconversion emission signals at around 480, 530, 550 and 660 nm. The 480 nm blue emission was originated from the (1)G(4)-->H-3(6) transition of the Tm3+ ions excited by a multiphoton stepwise phonon-assisted excited-state absorption process. The 5 30, 5 50 nm green and 660 mn red upconversion luminescences were identified as originating from the H-2(11/2), S-4(3/2) --> I-4(15/2) and F-4(9/2) --> I-4(15/2) transitions of the Er3+ ions, respectively, populated via efficient cross-relaxation processes and excited-state absorption. White light generation employing a single infrared excitation source is also examined. (C) 2003 Elsevier B.V. (USA). All rights reserved.

Local Er(III) environment in luminescent titanosilicates prepared from microporous precursors

The local environment of Er3+ ions in microporous titanosilicate ETS-10 and in synthetic narsarsukite and glassy materials obtained by calcination of ETS-10 has been investigated by EXAFS, Raman and photoluminescence spectroscopies. Er L-III-edge EXAFS studies of Er3+-doped ETS-10 support the view that the exchanged Er3+ ions reside close to the (negatively charged) TiO6 octahedra. In ETS-10, Er3+ is partially bonded to framework oxygen atoms and hydration water molecules. The Er...Ti distance (3.3 Angstrom) is similar to the Na...Ti distances (3.15-3.20 Angstrom) reported previously for Na-ETS-10. Although the exact location of the ErO6 units within the host structure of Er3+-doped synthetic narsarsukite is still an open question, it is most likely that Er3+ substitutes Ti4+ rather than Na+ ions. EXAFS spectroscopy indicates that no significant clustering of erbium atoms occurs in the titanosilicate samples studied. Evidence for the insertion of Er3+ ions in the framework of narsarsukite has been obtained by Raman spectroscopy. This is indicated by the increasing full-width at half-maximum (FWHM) of the 775 cm(-1) peak and the increasing intensity of the anatase peaks as the erbium content increases. In addition, as the narsarsukite Er3+ content increases a band at ca. 515 cm(-1) firstly broadens and subsequently a new peak appears at ca. 507 cm(-1).Er3+-doped narsarsukite exhibits a characteristic local vibrational frequency, (h) over bar omega ca. 330 cm(-1), with an electron-phonon coupling, g ca. 0.2, which constitutes additional evidence for framework Er3+ insertion. The number of lines in the infrared emission spectrum of synthetic narsarsukite indicates the presence of two optically-active erbium centres with very similar local environments and an average I-4(13/2) lifetime of 7.8 +/- 0.2 ms.

Intense red upconversion emission in infrared excited holmium-doped PbGeO3-PbF2-CdF2 transparent glass ceramic

Intense red upconversion emission around 650 nm in PbGeO3-PbF2-CdF2 transparent glass ceramic containing beta-PbF2:Ho3+ nanocrystals, is presented. The holmium-doped vitroceramic samples were excited by a 980 nm diode laser source. The 650 nm upconversion signal was assigned to the F-5(5) --> I-5(8) transition of holmium ions. Very low intensity signals around 490 and 540 nm corresponding to the F-5(2,3) --> I-5(8) and S-4(2), F-5(4) --> I-5(8) transitions, respectively, were also detected. The upconversion excitation mechanism was achieved through a combination of stepwise phonon-assisted multiphoton absorption, cross-relaxation processes involving pairs of holmium ions, and excited-state absorption. Using a diode laser pump source around 850 nm green upconversion emission around 540 nm was the observed predominant signal. (C) 2004 Elsevier B.V. All rights reserved.

Characterization of BaTi1-xZrxO3 thin films obtained by a soft chemical spin-coating technique

Single-phase perovskite structure BaZrxTi1-xO3 (BZT) (0.05less than or equal toxless than or equal to0.25) thin films were deposited on Pt-Ti-SiO2-Si substrates by the spin-coating technique. The structural modifications in the thin films were studied using x-ray diffraction and micro-Raman scattering techniques. Lattice parameters calculated from x-ray data indicate an increase in lattice (a axis) with the increasing content of zirconium in these films. Such Zr substitution also result in variations of the phonon mode wave numbers, especially those of lower wave numbers, for BaZrxTi1-xO3 thin films, corroborate to the structural change caused by the zirconium doping. on the other hand, Raman modes persist above structural phase transition, although all optical modes should be Raman inactive in the cubic phase. The origin of these modes must be interpreted as a function of a local breakdown of the cubic symmetry, which could be a result of some kind of disorder. The BZT thin films exhibited a satisfactory dielectric constant close to 181-138, and low dielectric loss tan delta<0.03 at the frequency of 1 kHz. The leakage current density of the BZT thin films was studied at elevated temperatures and the data obey the Schottky emission model. Through this analysis the Schottky barrier height values 0.68, 1.39, and 1.24 eV were estimated to the BZT5, BZT15, and BZT25 thin films, respectively. (C) 2004 American Institute of Physics.

Relaxation and tunnelling of structural units within the LTO phase of La2CuO4

The anelastic relaxation (elastic energy loss and Young modulus) of nearly stoichiometric La2CuO4+delta with LTO structure was measured. Extraordinarily intense effects are present below room temperature in the elastic dynamic susceptibility, indicating relaxational dynamics of a relevant fraction of the lattice. The involved degrees of freedom are identified as rotations of the CuO6 octahedra. Two distinct processes are found at frequencies around 1 kKz: one is observed around 150 K and is characterized by a mean activation energy of 2800 K; the second one occurs below 30 K and is governed by atomic tunnelling. Two explanations are proposed for the faster process: i) formation of fluctuating LTT domains on a scale of few atomic cells; ii) the LTO phase is a dynamical Jahn-Teller phase with all the octahedra tunneling between two LTT-like tilts. In both cases there would be important implications regarding the mechanisms giving rise to charge nanophase separation and strong electron-phonon coupling.

Field-dependent conductivity at low electric fields in pressed pellets of doped poly (3-methylthiophene): evidence of charge-density wave depinning

Field-dependent conductivity at low electric fields was observed from low to room temperature in pressed pellets of doped poly(3-methylthiophene). The room temperature data showed good agreement with Bardeen's theory of charge-density wave depinning and the values of the parameters obtained are consistent with a strong electron-phonon interaction as expected for quasi-one dimensional systems. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Two-phase separation observed in thermally treated pellets of ClO4- doped poly(3-methylthiophene) from electron spin resonance measurements

A pressed pellet of CIO (-)(4) poly (3-methylthiophene) (P3MT) was heated for two hours at 85 degrees C and suddenly dropped in liquid nitrogen. A change was observed around 220 K in the Electron Spin Resonance (ESR) spectra when the sample was slowly cooled from room temperature. ESR line asymmetry parameter (A/B) showed two spatially separated phases. One was identified as a small metallic-like phase. The other phase, the larger one, makes a transition to a semiconducting Charge-Density Wave (CDW) state.