No description available.

No description available.

abstract: Group III-nitride semiconductors have wide application in optoelectronic devices. Spontaneous and piezoelectric polarization effects have been found to be critical for electric and optical properties of group III-nitrides. In this dissertation, firstly, the crystal orientation dependence of the polarization is calculated and in-plane polarization is revealed. The in-plane polarization is sensitive to the lateral characteristic dimension determined by the microstructure. Specific semi-polar plane growth is suggested for reducing quantum-confined Stark effect. The macroscopic electrostatic field from the polarization discontinuity in the heterostructures is discussed, b ased on that, the band diagram of InGaN/GaN quantum well/barrier and AlGaN/GaN heterojunction is obtained from the self-consistent solution of Schrodinger and Poisson equations. New device design such as triangular quantum well with the quenched polarization field is proposed. Electron holography in the transmission electron microscopy is used to examine the electrostatic potential under polarization effects. The measured potential energy profiles of heterostructure are compared with the band simulation, and evidences of two-dimensional hole gas (2DHG) in a wurtzite AlGaN/ AlN/ GaN superlattice, as well as quasi two-dimensional electron gas (2DEG) in a zinc-blende AlGaN/GaN are found. The large polarization discontinuity of AlN/GaN is the main source of the 2DHG of wurtzite nitrides, while the impurity introduced during the growth of AlGaN layer provides the donor states that to a great extent balance the free electrons in zinc-blende nitrides. It is also found that the quasi-2DEG concentration in zinc-blende AlGaN/GaN is about one order of magnitude lower than the wurtzite AlGaN/GaN, due to the absence of polarization. Finally, the InAlN/GaN lattice-matched epitaxy, which ideally has a zero piezoelectric polarization and strong spontaneous polarization, is experimentally studied. The breakdown in compositional homogeneity is triggered by threading dislocations with a screw component propagating from the GaN underlayer, which tend to open up into V-grooves at a certain thickness of the InxAl1-xN layer. The V-grooves coalesce at 200 nm and are filled with material that exhibits a significant drop in indium content and a broad luminescence peak. The structural breakdown is due to heterogeneous nucleation and growth at the facets of the V-grooves. / Dissertation/Thesis / Ph.D. Physics 2012

In dieser Dissertation wird die spektrale und örtliche Verteilung der Lumineszenz von Heterostrukturen in selbstorganisierten Nanodrähten (ND) mit Hilfe von Kathodolumineszenz-Spektroskopie (KL) im Rasterelektronenmikroskop untersucht. Diese Methode wird ergänzt durch Messungen der kontinuierlichen und zeitaufgelösten Mikro-Photolumineszenz. Drei verschiedene Strukturen werden behandelt: (i) GaAs-ND bestehend aus Segmenten der Wurtzit (WZ) bzw. Zinkblende (ZB) Kristallstrukturen, (ii) auf GaN-ND überwachsene GaN-Mikrokristalle und (iii) (In,Ga)N Einschlüsse in GaN-ND. Die gemischte Kristallstruktur der GaAs-ND führt zu komplexen Emissionsspektren. Dabei wird entweder ausschließlich Lumineszenz bei Energien unterhalb der ZB Bandlücke, oder aber zusätzlich bei höheren Energien, gemessen. Diese Differenz wird durch unterschiedliche Dicken der ZB und WZ Segmente erklärt. Messungen bei Raumtemperatur zeigen, dass die Bandlücke von WZ-GaAs mindestens 55 meV größer als die von ZB-GaAs ist. Die Lumineszenz-Spektren der GaN-Mikrokristalle enthalten verschiedene Emissionslinien, die auf Stapelfehler (SF) zurückzuführen sind. SF sind ZB Quantentöpfe verschiedener Dicke in einem WZ-Kristall und es wird gezeigt, dass ihre Emissionsenergie durch die spontane Polarisation bestimmt wird. Aus einer detaillierten statistischen Analyse der Emissionsenergien der verschiedenen SF-Typen werden Emissionsenergien von 3.42, 3.35 und 3.29 eV für die intrinsischen (I1 und I2) sowie für extrinsische SF ermittelt. Aus den entsprechenden Energiedifferenzen wird -0.022C/m² als experimenteller Wert für die spontane Polarisation von GaN bestimmt. Die Bedeutung sowohl der piezoelektrischen Polarisation als auch die der Lokalisierung von Ladungsträgern wird für (In,Ga)N-Einschlüsse in GaN-ND gezeigt. Hierbei spielt nicht nur die Lokalisierung von Exzitonen, sondern auch die individueller Elektronen und Löcher an unterschiedlichen Potentialminima eine Rolle. / In this thesis, the spectral and spatial luminescence distribution of heterostructures in self-induced nanowires (NWs) is investigated by cathodoluminescence spectroscopy in a scanning electron microscope. This method is complemented by data from both continuous and time-resolved micro-photoluminescence measurements. Three different structures are considered: (i) GaAs NWs containing segments of the wurtzite (WZ) and zincblende (ZB) polytypes, (ii) GaN microcrystals overgrown on GaN NWs, and (iii) (In,Ga)N insertions embedded in GaN NWs. The polytypism of GaAs NWs results in complex emission spectra. The observation of luminescence either exclusively at energies below the ZB band gap or also at higher energies is explained by differences in the distribution of ZB and WZ segment thicknesses. Measurements at room temperature suggest that the band gap of WZ GaAs is at least 55 meV larger than that of the ZB phase. The luminescence spectra of the GaN microcrystals contain distinct emission lines associated with stacking faults (SFs). SFs essentially constitute ZB quantum wells of varying thickness in a WZ matrix and it is shown that their emission energy is dominated by the spontaneous polarization. Through a detailed statistical analysis of the emission energies of the different SF types, emission energies of 3.42, 3.35 and 3.29 eV are determined for the intrinsic (I1 and I2) as well as the extrinsic SFs, respectively. From the corresponding energy differences, an experimental value of -0.022C/m² is derived for the spontaneous polarization of GaN. The importance of both carrier localization and the quantum confined Stark effect induced by the piezoelectric polarization is shown for the luminescence of (In,Ga)N insertions in GaN NWs. Not only localized excitons, but also electrons and holes individually localized at different potential minima contribute to the observed emission.

Made available in DSpace on 2017-07-24T19:38:04Z (GMT). No. of bitstreams: 1 Alan Rogerio Ferreira Lima.pdf: 4210754 bytes, checksum: 82a7a7898a00633ad3aa474df848f207 (MD5) Previous issue date: 2011-02-28 / This work aimed the study of the effect of transition metals (Ni, Fe, Co) on the spontaneous polarization of the ferroelectric oxides of tetragonal tungsten bronze (TTB)-type structure of potassium strontium niobate (KSr2Nb5O15) and of the KSr2(FeNb4)O15-d, KSr2(NiNb4)O15-d and KSr2(CoNb4)O15-d solid solutions. All systems investigated were prepared by mechanical mixture of oxide/carbonates by high-energy ball milling. The calcination temperature was performed to obtain nanoparticles and the nanostructured particles were evaluated. The evolution of mass loss, chemical bonds, crystalline structure and the electrical behavior were evaluated using the thermal analysis (thermogravimetric Analysis (TGA) and Differential Scanning Calorimeter (DSC), infrared absorption spectroscopy (FTIR), X-ray diffraction (XRD) and impedance spectroscopy, respectively. From the impedance spectroscopy technique were studied the dielectric properties of the nanoparticles and the dielectric permittivity of the KSr2Nb5O15, KSr2(FeNb4)O15-d, KSr2(NiNb4)O15-d and KSr2(CoNb4)O15-d systems was determined. The highest permittivity value was obtained for KSr2(FeNb4)O15-d. The determination of crystallographic parameters of nanopowders was performed using the Rietveld method. From the crystallographic parameters was simulated the crystalline structure and determined the spontaneous polarization for KSr2Nb5O15, KSr2(FeNb4)O15-d, KSr2(NiNb4)O15-d and KSr2(CoNb4)O15-d systems based on the atomic displacement (Dz) of Nb (niobium) atom, in the z plane, from the central position of the [NbO6] octahedron. The variation of spontaneous polarization of the nanoparticles with the addition of transition metals in the KSr2Nb5O15 host structure confirmed the existence of ferroelectricity in the systems investigated. / O objetivo deste trabalho foi estudar o efeito de metais de transição (Ni, Fe, Co), sobre a polarização espontânea, dos óxidos ferroelétricos de estrutura tungstênio bronze (TB) de niobato de potássio e estrôncio (KSr2Nb5O15) e das soluções sólidas de KSr2(FeNb4)O15-d, KSr2(NiNb4)O15-d e KSr2(CoNb4)O15-d. Todos os sistemas investigados foram preparados por mistura de óxidos/carbonatos pelo do método de ativação mecânica por moagem de alta energia. A temperatura de calcinação necessária à obtenção de nanopartículas foi otimizada e as partículas nanoestruturadas foram avaliadas. A evolução dos parâmetros de perda de massa, ligações químicas, estrutura cristalina e o comportamento elétrico, foram avaliados utilizando as técnicas de análise térmicas (análise termogravimétrica (ATG) e calorimetria diferencial exploratória (DSC), espectroscopia de absorção na região do infravermelho, difração de raios X e espectroscopia de impedância, respectivamente. A partir da técnica de espectroscopia de impedância foram estudadas as propriedades dielétricas das nanopartículas em suspensão, determinando a permissividade dielétrica dos sistemas KSr2Nb5O15, KSr2(FeNb4)O15-d, KSr2(NiNb4)O15-d e KSr2(CoNb4)O15-d. O maior valor de permissividade foi obtido para o KSr2(FeNb4)O15-d. A determinação dos parâmetros cristalográficos dos nanopós foi realizada utilizando o método de Rietveld de refinamento e/ou ajuste de estrutura cristalina. A partir dos parâmetros cristalográficos foi simulada a estrutura cristalina e determinada a polarização espontânea para os sistemas KSr2Nb5O15, KSr2(FeNb4)O15-d, KSr2(NiNb4)O15-d e KSr2(CoNb4)O15-d com base no deslocamento atômico (Dz) do átomo de Nb (nióbio), no plano z, da posição central do octaedro [NbO6]. A variação da polarização espontânea das nanopartículas, com a adição de metais de transição na estrutura hospedeira do KSr2Nb5O15, confirmou a existência de ferroeletricidade nos sistemas investigados.

Ce manuscrit est consacré à l’analyse théorique et expérimentale d’oxydes Ln2Ti2O7 (Ln = La, Nd, Sm, Gd) et BiFeO3.Les propriétés physiques de La2Ti2O7 et Nd2Ti2O7 ont été investiguées au moyen de calculs ab initio, confirmant ainsi leur ferroélectricité. D’autres oxydes de la famille Ln2Ti2O7, Sm2Ti2O7 et Gd2Ti2O7, ont ensuite été étudiés selon les mêmes méthodes théoriques. Nos calculs ont révélé une meilleure amplitude de polarisation pour ces composés par rapport au La2Ti2O7 et au Nd2Ti2O7. La deuxième partie de ce travail est consacrée aux propriétés structurales, électroniques et ferroélectriques du BiFeO3. L’évolution de ses propriétés lorsqu’il est soumis à une contrainte épitaxiale ont été investiguées au moyen de calculs ab-initio et de mesures en microscopie à champ proche réalisées sur des couches minces déposées sur un substrat de SrTiO3(001). Nos résultats mettent en évidence une modification de la structure interne du matériau sous effet de contrainte, qui se traduit par une réorientation progressive de la polarisation spontanée suivant la direction [001]. Notre étude s’est ensuite tournée vers l’élaboration et l’analyse des propriétés structurales et ferroélectriques de superréseaux (SrTiO3)n(BiFeO3)m. Nos calculs ont mis en évidence que la contrainte épitaxiale imposée au superréseau offrait un contrôle accru des propriétés du BiFeO3 par rapport à son comportement lorsqu’il est déposé seul en couches minces. Les analyses en microscopie à champ proche ont montré une réduction de la tension coercitive de tels films par rapport à celle mesurée sur des bicouches SrTiO3/BiFeO3 ou sur une couche mince de BiFeO3. / In this work, first-principles calculations and experimental measurements have been done in order to investiguate the structural, electroniq and ferroelectric properties of Ln2Ti2O7 (Ln = La, Nd, Sm, Gd) and BiFeO3 oxydes. Calculations on La2Ti2O7 and Nd2Ti2O7 confirmed their ferroelectricity. Other oxydes belonging to the Ln2Ti2O7 family have also been investigated. The results showed an enhancement of the spontaneous polarization within these compounds compared to that of La2Ti2O7 and Nd2Ti2O7. The second part of this work is related to the structural and ferroelectric properties of bismuth ferrite BiFeO3. The evolution of its properties when undergoing an epitaxial strain have been investigated by ab initio calculations and piezoresponse force microscopy measurements on thin films deposited on a (001)-SrTiO3 substrate. Our results showed a modification of the inner structure of BiFeO3 under stain, leading to a continuous reorientation of the spontaneous polarization vector towards [001]. The third part of our study consists in the computational design and synthesis of (SrTiO3)n(BiFeO3)m superlattices. Our calculations showed that epitaxial strain imposed to the superlattice brings a further control of physical properties of BiFeO3 as compared with its behaviour when deposited alone in a thin film. PFM analysis showed a decrease of the coercive field for STO/LNO/(STO)n(BFO)m superlattices as compared with those measured on STO/BFO bi-layers and on BiFeO3 thin films.