Fullerenes have been shown to constitute a prototypical building block for truly nanometer-sized devices and exotic nanounit-based materials, e.g., high-temperature superconductors. This makes the detailed understanding of fullerene electronic states in compounds and at interfaces of primary importance, since the high symmetry of the molecule greatly simplifies the starting point of the analysis. Carbon nanotubes, which combine one macroscopic with two nanoscopic dimensions, are perhaps of even greater practical interest. Angle-dependent electron spectroscopies have been employed in the present work to study these materials, characterizing their structure, bonding, and electronic states. For solid C60, the photoelectron angular distribution has been found to be essentially that of the free molecule, modified by solid state scattering; a similar distribution is found for K3C60. The surface and bulk electronic structure of K3C60 has been identified by angle-dependent core and valence photoelectron spectroscopy (PES) and x-ray emission spectroscopy. An insulating surface layer has been identified for this high-temperature superconductor. Angle-dependent valence PES is used to investigate the electronic states of C60/Al(110). Electron correlations are found to be the origin of the splitting observed in the molecular orbitals, which is quite sensitive to the molecular orientation. The components of the highest occupied molecular orbital are differentiated according to their overlap with the substrate. A rigid shift of valence- and core-levels has been observed even for ionic and covalent C60 compounds, reflecting the efficient static polarizability screening of the molecule. The alignment of multi-walled carbon nanotubes has been investigated by x-ray absorption spectroscopy, using the spectral intensity ratio of π*- and *-resonances. Core level combined with valence PES shows that the degree of defect structure varies from position to position on the sample. Valence photoelectron spectra of defect-free sample spots closely resembles the total DOS of graphite.

The parallelization and vectorization of Monte Carlo algorithms for modelling charge transport in semiconductor devices are considered. The standard ensemble Monte Carlo simulation of a three parabolic band model for GaAs is first presented as partial verification of the simulation. The model includes scattering due to acoustic, polar-optical and intervalley phonons. This ensemble simulation is extended to a full device simulation by the addition of real-space positions, and solution for the electrostatic potential from the charge density distribution using Poisson's equation. Poisson's equation was solved using the cloud-in-cell scheme for charge assignment, finite differences for spatial discretization, and simultaneous over-relaxation for solution. The particle movement (acceleration and scattering) and the solution of Poisson's are both separately parallelized. The parallelization techniques used in both parts are based on the use of semaphores for the protection of shared resources and processor synchronization. The speed increase results for parallelization with and without vectorization on the Ardent Titan II are presented. The results show saturation due to memory access limitations at a speed increase of approximately 3.3 times the serial case when four processors are used. Vectorization alone provides a speed increase of approximately 1.6 times when compared with the nonvectorized serial case. It is concluded that the speed increase achieved with the Titan II is limited by memory access considerations and that this limitation is likely to plague shared memory machines for the forseeable future. For the program presented here, vectorization is concluded to provide a better speed increase per day of development time than parallelization. However, when vectorization is used in conjunction with parallelization, the speed increase due to vectorization is negligible. / Graduation date: 1993

Photo-induced charge transfer which occurs between molecules or different parts of a large molecule is the pivotal process related to performances of organic electronics. In particular, injection of charge carriers into conjugated polymers and dissociation of photo-generated excitons at the heterojunction between a donor and acceptor system are of great importance in determining the luminescence efficiency of organic light emitting diodes (OLEDs) and solar energy conversion efficiency of organic solar cells, respectively. However, the complex nature of organic semiconductors as well as complicated primary processes involved in the functioning of these devices have prevented us from understanding unique characteristics of these processes and thereby engineering better materials for higher performances. In this dissertation, two different types of photo-induced (or -related) charge transfer processes occurring in organic semiconductors were investigated by using single molecule spectroscopy (SMS) techniques to unravel the complexities of these processes. The carefully designed functioning capacitor-like model devices similar to OLEDs and photovoltaic cells were fabricated where isolated single nanoparticles were introduced as an active medium to mitigate the complexities of these materials. We observed that injection of positively charged carriers (holes) into poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) single nanoparticles from the carbazole hole transport layer does not occur in the absence of light. We denoted the observed hole injection in aid of light as the light-induced hole transfer mechanism (LIHT). It was revealed that the charging dynamics are highly consistent with a cooperative charging effect. In addition, the LIHT was proposed as the possible source for the formation of deep trapped hole in organic devices. Local exciton dissociation yields across a nanostructured domain between poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) single nanoparticles and either poly(9,9- dioctylfluorene - co - bis-N,N- (4 -butylphenyl)-bis-N,N-phenyl-1,4-phenylene diamine) (PFB) or poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB) film in model photovoltaic devices was also investigated. A wide distribution of exciton dissociation yields was observed from each nanodomain due to the device geometry. The observed hysteresis in fluorescence voltage curve was ascribed to accumulated charges following charge separations. The dynamics of charge separation under the applied electric field was described in more detail. / text

Στην παρούσα εργασία ερευνάται η τρίτης τάξης μη γραμμική απόκριση διαφόρων υλικών τα οποία μελετήθηκαν σε μορφή διαλυμάτων ή λεπτών υμενίων. Αρχικά περιγράφονται βασικές έννοιες της μη γραμμικής οπτικής, μερικών σημαντικών φυσικών διαδικασιών που σχετίζονται με αυτή, καθώς και των διαφόρων μηχανισμών που μπορούν να συνεισφέρουν στο μη γραμμικό δείκτη διάθλασης. Στη συνέχεια παρουσιάζεται η μη γραμμική οπτική απόκριση νανοδομών Au, Pd και Ag. Με τη βοήθεια πολυμερών αποτρέπεται η συσσωμάτωση και καθίζηση του μετάλλου και επιτυγχάνεται η δημιουργία μεταλλικών νανοσωματιδίων συγκεκριμένω διαστάσεων. Επίσης μελετάται η μη γραμμικότητα TiO2, φουλλερενικών παραγώγων και μοριακών μηχανών. Η μεγάλη απόκριση των συστημάτων αυτών σε συνδυασμό με την έντονη εξάρτησή της από διάφορες μορφολογικές/δομικές παραμέτρους καθιστά τα συστήματα αυτά πολύ χρήσιμα για φωτονικές εφαρμογές. / In this work the third order nonlinear optical response of several photonic materials, has been investigated. These materials were in the form of solutions, colloids or thin films. Initially some basic concepts of nonlinear optics, the physical processes related with it, as well as the physical mechanisms related to the nonlinear refractive index are presented. Then, the nonlinear optical response of Au, Pd and Ag nanoparticles is presented. By using polymers, formation of nanoparticles exhibiting specific sizes can be achieved. Furthermore the polymer does not allow metal aggregation in the system. The nonlinearity of TiO2 films, fullerene derivatives and molecular engines is also investigate. The large response of these systems, combined with the strong dependence on several morphological/structural parameters makes them very promising candidates for several photonic applications.

Nous investiguons dans ce travail la dynamique des excitons dans une couche mince d’agrégats H autoassemblés hélicoïdaux de molécules de sexithiophène. Le couplage intermoléculaire (J=100 meV) place ce matériau dans la catégorie des semi-conducteurs à couplage de type intermédiaire. Le désordre énergétique et la forte interaction électronsphonons causent une forte localisation des excitons. Les espèces initiales se ramifient en deux états distincts : un état d’excitons autopiégés (rendement de 95 %) et un état à transfert de charge (rendement de 5%). À température de la pièce (293K), les processus de sauts intermoléculaires sont activés et l’anisotropie de la fluorescence décroît rapidement à zéro en 5 ns. À basse température (14K), les processus de sauts sont gelés. Pour caractériser la dynamique de diffusion des espèces, une expérience d’anisotropie de fluorescence a été effectuée. Celle-ci consiste à mesurer la différence entre la photoluminescence polarisée parallèlement au laser excitateur et celle polarisée perpendiculairement, en fonction du temps. Cette mesure nous donne de l’information sur la dépolarisation des excitons, qui est directement reliée à leur diffusion dans la structure supramoléculaire. On mesure une anisotropie de 0,1 après 20 ns qui perdure jusqu’à 50ns. Les états à transfert de charge causent une remontée de l’anisotropie vers une valeur de 0,15 sur une plage temporelle allant de 50 ns jusqu’à 210 ns (période entre les impulsions laser). Ces résultats démontrent que la localisation des porteurs est très grande à 14K, et qu’elle est supérieure pour les espèces à transfert de charge. Un modèle numérique simple d’équations différentielles à temps de vie radiatif et de dépolarisation constants permet de reproduire les données expérimentales. Ce modèle a toutefois ses limitations, notamment en ce qui a trait aux mécanismes de dépolarisation des excitons. / In this work, we investigate exciton dynamics in a thin film of sexithiophene molecules in self-assembled chiral H-aggregate supramolecular stacks. The intermolecular coupling energy J=100 meV places those molecules in the intermediate coupling regime. The energetic disorder and the strong phonon-electron interactions leads to high localization of the photoexcitations. The initial photoexcited species branches into two distinct states : self-trapped exciton (95% yield) and charge-transfer excitons (5% yield). At room temperature (293K), the intermolecular hopping processes are thermaly activated and the fluorescence anisotropy goes to zero within 5 ns. At low temperature (14K), hopping processes are frozen. To characterize exciton diffusion mechanisms, a fluorescence anisotropy experiment has been done. This measurement consists of monitoring the difference between the parallel and perpendicular composants of the photoluminescence (with respect to the laser beam), as a function of time. The fluorescence anisotropy gives us information about the depolarization of the excitons, which is directly connected with their diffusion within the supramolecular stack. We measure an anisotropy of 0,1 after 20 ns which stays constant for 50 ns. Chargetransfer states induce a rise of the anisotropy up to 0,15 between 50 ns and 210 ns (the period between adjacent laser pulses). Those measurements shows that exciton localization is very strong at 14K and higher for the charge-transfer states than the self-trapped ones. A simple mathematical model based on the resolution of a system of differential equations with constants radiative and depolarization lifetimes can reproduce the experimental data. This model has some limitations, especially for the description of the depolarization mechanisms of the self-trapped excitons.

Key issues in improving small molecule organic solar cells (SMOSC) are the need for new absorber materials and optimized active layer morphology. This thesis deals with the improvement of SMOSC on the donor material side. Promising donor materials (D) are provided by dicyanovinyl endcapped oligothiophenes DCV2-nT (n = 3, . . . , 6) synthesized in the group of Prof. Bäuerle at the University of Ulm. Here, DCV2-nT (n = 3, 5) with different alkyl side chains are characterized. Side chain variations mainly influence the aggregation of molecules in pristine films as well as in blend films with the commonly used acceptor (A) fullerene C60. With changes in the layer morphology, important physical properties in thin film like absorption spectra, energy levels, as well as excited state properties are changed. The focus of this work are excited state properties accessed by photoinduced absorption spectroscopy (PIA). PIA probes the long living excited states in pristine and blend films, i. e. triplet excitons, anions, and cations. For a series of four dicyanovinyl-terthiophenes DCV2-3T (without side chains, with two methyl, two butyl, and four butyl side chains) a systematic study of the effect of alkyl side chains on the aggregation in neat and blend film is discussed. In consequence the efficiency of the energy transfer mechanism between DCV2-3T and C60 is affected. It turns out that in solution spectra and cyclic voltammetry (CV) measurements, the variation of alkyl side chains has almost no influence. However, in thin film there is strong impact on the molecular arrangement confirmed by strongly varying absorption spectra, ionization potentials, and surface roughnesses. Furthermore, PIA measurements reveal that the energy transfer efficiency between D and A in general decreases with increasing side chain length, but is most efficient for a compound with methyl side chains. For blends of dicyanovinyl-quinquethiophenes (DCV2-5T) with C60, the layer morphology is influenced by two different methods. On one hand substrate heating is applied while deposition of the active layer, on the other hand DCV2-5Ts with different alkyl side chains (four methyl and four butyl side chains) are used. Deposition on a heated substrate (80°C) results in an improved solar cell performance, assigned to the formation of a sufficient phase separation of D and A phase in the active layer. This leads to reduced recombination losses and closed percolation paths. The morphological change can be correlated to an increased lifetime of cations. In blends deposited on a heated substrate, the donor cation lifetime increases by almost one order of magnitude from around 10 μs to ≈ 80 μs. This increase of carrier lifetime is both detected optically by PIA as well as electrically by impedance spectroscopy. The increase in lifetime is consequently assigned to a better spatial separation of positive and negative charges induced by the phase separation. Comparing DCV2-5T with methyl and butyl side chains results in a similar effect: The dicyanovinyl-quinquethiophene with methyl side chains leads to an improved solar cell device performance compared to devices comprising the compound with butyl side chains as donor. The improved device performance is again accompanied by an increase in cation lifetime detected by PIA. / Die Entwicklung neuer Absorber-Materialien sowie die Morphologie der photo- aktiven Schicht sind zentrale Themen hinsichtlich der Optimierung organischer Solarzellen aus kleinen Molekülen. In der vorliegenden Arbeit werden diese beiden Aspekte von Seiten des Donor-Materials (D) her behandelt. Die Material- klasse der Dicyanovinyl-Oligothiophene DCV2-nT(n=3,...,6) (synthetisiert in der Arbeitsgruppe von Prof. Bäuerle an der Universität Ulm) dient dabei als Ausgangspunkt. Insbesondere werden DCV2-nT-Moleküle (n = 3, 5) mit verschiedenen Alkyl-Seitenketten charakterisiert. Die Variation der Seitenketten beeinflusst in erster Linie die Anordnung der Moleküle in Einzel- sowie in Mischschichten mit dem typischerweise verwendeten Akzeptor-Material Fulleren C60 (A). Als Folge der Schichtmorphologie ändern sich physikalische Eigenschaften wie u. a. Absorptions- spektren, Energieniveaus sowie die Eigenschaften angeregter Zustände. Angeregte Zustände, wie Triplett-Exzitonen, Anionen und Kationen werden in dieser Arbeit mittels photoinduzierter Absorptionsspektroskopie (PIA) charakterisiert. Anhand einer Serie von vier Dicyanovinyl-Tertiophenen DCV2-3T (ohne Seiten- ketten, mit zwei Methyl-, zwei Butyl-, und vier Butyl-Seitenketten) werden systematisch Einflüsse der Seitenketten auf die Aggregation der Moleküle in Einzel- und Mischschichten untersucht. Besonderes Augenmerk liegt dabei auf dem Effekt der Seitenketten auf den Energie-Transfer-Mechanismus zwischen D und A. In Lösungsmittelspektren und Cyclovoltammetrie-Messungen ist fast keine Änderung durch die Seitenketten erkennbar. Im Dünnfilm hingegen besteht ein starker Einfluss auf die molekulare Anordnung, erkennbar in einer starken Variation der Absorptionsspektren, Ionisationspotentiale und Oberflächen-Topographie. PIA- Messungen zeigen weiterhin, dass im Allgemeinen die Effizienz des Energie-Transfer- Mechanismus mit zunehmender Länge der Alkyl-Ketten abnimmt. Der effizienteste Transfer besteht jedoch für die Verbindung mit Methyl-Seitenketten. In Mischschichten aus Dicyanovinyl-Quinquethiophenen (DCV2-5T) und C60 werden hier zwei Methoden zur Beeinflussung der Schichtmorphologie verfolgt. Zum einen wird die aktive Schicht auf einem geheizten Substrat abgeschieden, zum anderen werden DCV2-5T-Moleküle mit Methyl- und Butyl-Seitenketten als Donor verwendet. Das Abscheiden der aktiven Schicht auf einem geheizten Substrat (80 °C) führt zu einer verbesserten Solarzellenleistung, was auf die Bildung einer hin- reichenden Phasenseparation von D- und A-Phasen in der aktiven Schicht zurückzuführen ist. Die Phasenseparation bewirkt eine Reduktion von Rekombinationsverlusten und die Bildung geschlossener Perkolationspfade. Die morphologische Änderung korreliert mit einem Anstieg der Ladungsträger-Lebensdauer um fast eine Größenordnung von etwa 10 μs auf ≈ 80 μs. Der Anstieg kann sowohl optisch durch PIA, als auch elektrisch mittels Impedanz-Spektroskopie detektiert werden. Eine höhere Lebensdauer der Ladungsträger kann letztlich auf eine größere räumlichen Separation der positiven und negativen Ladungsträger zurückgeführt werden, induziert durch die Phasenseparation. Ein Vergleich von DCV2-5T-Molekülen mit Methyl- und Butyl-Seitenketten führt zu ähnlichen Resultaten: Solarzellen mit DCV2-5T substituiert mit Methyl- Seitenketten sind effizienter als die der butyl-substituierten Moleküle. Dies korreliert wiederum mit einer signifikant erhöhten Lebensdauer der Ladungsträger in Mischschichten der methyl-substituierten Verbindung.

Plusieurs processus photo-induits d'énergie et de transfert d'énergie ont été étudiés en solution et dans le film par spectroscopie d'absorption transitoire et de fluorescence pour deux types de cellules solaires. Combinés avec d'autres expériences et par une analyse globale, ces phénomènes ultrarapides avec leur durée de vie ont été observés et les scénarios photo-induits ont été déterminés. La compréhension approfondie des matériaux moléculaires pourrait aider les chimistes à concevoir des cellules solaires efficaces. La première étude sur l'influence des conceptions chimiques sur la formation et la séparation des charges implique différentes fractions donneuses et différents solvants et les résultats ont été expliqués par la théorie de Marcus-Jortner combinée avec le calcul quantique. La deuxième étude porte sur les complexes Fe (II) comme photosensibilisateurs pour les cellules solaires sensibilisées aux colorants. On a étudié une série de complexes de Fe (II) homo et hétérotéptiques avec des ligands de carbène et de terpyridine en solution et dans le film. La durée de vie de l'état de transfert de la charge métal-ligand du triplet d'enregistrement du complexe Fe (II) est obtenue en solution. La compréhension du film est en cours. / Various photo-induced energy and energy transfer processes were investigated in solution and in the film by transient absorption and fluorescence spectroscopies for two types of solar cells. Combined with other experiments and through a global analysis, those ultrafast phenomena with their lifetimes were observed and the photo-induced scenarios were determined. The insight understanding of molecular materials could help chemists to design efficient solar cells.The first study about the influence of chemical designs on charge formation and separation involves different donor moieties and different solvents and the results were explained by Marcus-Jortner theory combined with quantum calculationThe second investigation is about Fe(II) complexes as photosensitizers for dye-sensitized solar cells. A series of homo- and heteroleptic Fe(II) complexes with carbene and terpyridine ligands have been studied in solution and in the film. The record triplet metal-to-ligand charge transfer state lifetime of Fe(II) complex is achieved in solution. The further understanding in the film is in progress.

>Magister Scientiae - MSc / A novel monomer (Phenazine-2,3-diimino(pyrrole-2-yl)–PDP) derived from the condensation reaction between 2,3-diaminophenazine and a pyrrole derivative has been synthesized as a hinge molecule in the design of a zig-zag polymer with actuation possibility. The monomer was polymerized chemically and electrochemically to produce the new polymer material – polymerized Phenazine-2,3-diimino(pyrrole-2-yl) PPDP. Two very crucial properties of a good actuator material, relate specifically to its solubility testing and electrical conductivity. The hinged polymer material was studied intensively in terms of its spectroscopy; Fourier Transform Infrared - FTIR, 1H’NMR, thermal properties (Differential Scanning Calorimetry-DSC and Thermogravimetric Analysis-TGA) as well as voltammetry and conductivity. Conductivity was evaluated using three different approaches including; 4 probe measurements, plotting of I/V curves based on potentiostatic measurements and an electrochemical impedance experiment using a dielectric Solartron interface. Electrochemical kinetics of the polymer prepared as a thin film at glassy carbon electrode (GCE) was also done and it was clear that the thin film conductivity was vastly different from the compressed pellet conductivity (thick film). The zig-zag polymer was then further modified by homogeneous inclusion of gold nanoparticles to improve conductivity and solubility, in the thick film arrangement. Conductivity of the thin film was studied by electrochemical impedance spectroscopy with the relative charge transfer values being determined for unmodified and modified polymer systems. The solubility testing of the material plays an important role as it is required for a wide range of experimental applications. The zig-zag polymer showed great promise for applications; in dye sensitized solar cells and free standing interpenetrating polymer network (IPN), solubility testing and electrical conductivity would need to be improved in order to be used in these applications.

O sucesso de tratamento de câncer depende do seu diagnóstico e tratamento nas etapas iniciais da doença. Isso estimula a busca de novos métodos de diagnóstico e de tratamento sensíveis e tecnicamente simples. Entre esses métodos, o diagnóstico por fluorescência (DPF) e a fotoquimioterapia (FQT) atraem uma atenção especial, sendo não invasivos, sensíveis e fácil de usar. Os fotossensibilizadores (FS) atualmente utilizados em DPF e FQT são corantes orgânicos, os quais possuem algumas desvantagens, tais como instabilidade fotoquímica e baixa seletividade. Os pontos quânticos (PQ) são candidatos promissores para substituírem os FS clássicos por serem fotoestáveis, apresentarem amplo e intenso espectro de absorção óptica e luminescência com alto rendimento quântico. Contudo a iteração entre FS clássicos e os PQ pode aumentar a eficiência de ambos devido a transferência de energia entre eles. O objetivo geral deste trabalho foi estudar os processos da interação de FS orgânicos (as porfirinas PPh, TMPyP e TPPS4) com PQs (CdTe e CdSe/ZnS), funcionalizados com diferentes grupos, em solução aquosa e na presença de modelos nano-organizados de estruturas biológicas com a finalidade de avaliar seu potencial para aplicação em Fotoquimioterapia e Diagnóstico por Fluorescência. Dedicamos especial atenção aos processos de transferência de energia e de carga entre os PQs e os FS. Os PQs interagem efetivamente com as PPh, cuja interação se manifesta pelas mudanças da intensidade e do perfil dos espectros e das curvas de decaimento da luminescência de PQ e da porfirina, do tamanho das partículas espalhadoras na solução, do potencial zeta dentre outros parâmetros espectroscópicos e físico-químicos. Dentro das soluções aquosas homogêneas, o PQ e as PPh podem formar agregados mistos (PQ&PPh&PQ) ou simples (PQ&PPh) e a interação entre eles realiza-se através de mecanismos de curto e/ou longo alcance, dependendo do grupo funcional do PQ. Entretanto, a interação eletrostática repulsiva entre o PQ e outro composto pode estimular a desagregação dos PQs induzindo o aumento na intensidade da sua luminescência e do seu tempo de vida, provocando um aumento na contribuição dos tempos longos do decaimento da luminescência associados com a superfície do PQ. Essas relações entre o tipo de interação do PQ e da PPh podem ser extrapoladas aos sistemas que contêm PQ na presença de estruturas nano-organizadas. / The success of cancer treatment depends on the diagnosis and treatment in the early stages of the disease. This stimulates the research for new methods of sensitive diagnosis and technically simple treatment. Among these methods, the Optical Bioimaging by fluorescence (OBI) and Photochemotherapy (PCT) attract special attention, being non-invasive, sensitive and friendly use. The photosensitizers (PS) currently used in the OBI-PCT are organic dyes, which have some drawbacks such as photochemical instability and low selectivity. Quantum Dots (QD) are promising candidates to replace the classic PS being photostable, present broad and intensive spectrum of optical absorption and luminescence and, high quantum yield. Therefore the interaction between QDPS and the classic PS can increase the efficiency of both due to energy transfer between them. The aim of this work was to study the processes of organic PS interaction (porphyrins PPh, TMPyP and TPPS4) with QDs (CdTe and CdSe/ZnS), functionalized with different groups in aqueous solution and in the presence of nano-organized models of biological structures with order to evaluate its potential for use in Photochemotherapy and Optical Bioimaging. We devote special attention to energy transfer processes and cargo between the QDs and PS. The QDs effectively interact with PPh, whose interaction is manifested by changes in the intensity and profile of spectra and luminescence decay curves of QD and the porphyrin, the linear size of the scattering particles in the solution, the zeta potential among other spectroscopic and physical chemistry parameters. Within the homogeneous aqueous solutions, QD and Pph can form mixed aggregates (QD&PPh&QD) or simple (QD&PPh) and the interaction between them is carried out through short mechanisms and/or long range, depending on the functional group of the QD. However, the repulsive electrostatic interaction between the QD and another compound may stimulate the breakdown of QDs inducing the increase in the intensity of their luminescence and its lifetime, causing an increase in the contribution of long time decay of the luminescence associated with the surface of QD. These relationships between the type of interaction of the QD and PPh can be extrapolated to systems containing QD in the presence of nano-organized structures.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2017-04-27T13:00:02Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese_Euclides_Almeida_Fisica.pdf: 5907240 bytes, checksum: 503a5b57e757a03f24206d4d3d26032c (MD5) / Made available in DSpace on 2017-04-27T13:00:02Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese_Euclides_Almeida_Fisica.pdf: 5907240 bytes, checksum: 503a5b57e757a03f24206d4d3d26032c (MD5) Previous issue date: 2012-07-30 / CNPQ / O principal objetivo deste trabalho foi investigar fenômenos ópticos ultrarrápidos em sistemas nanoestruturados empregando diferentes técnicas espectroscópicas não lineares, tanto no domínio do tempo quanto no domínio da frequência. Para fornecer uma base adequada que permita entender os experimentos feitos nessa tese, os princípios físicos das espectroscopias ópticas não lineares são apresentados. Inicialmente é apresentada uma descrição da função resposta não linear no domínio do tempo. A evolução temporal da polarização óptica, que gera o sinal espectroscópico, é descrita em detalhes usando uma teoria de perturbação diagramática. Técnicas ópticas não lineares são apresentadas, tais como eco de fótons, bombeamento-e-sonda e hole burning, assim como o comportamento dinâmico de um material pode ser interpretado a partir do sinal gerado. A técnica de mistura degenerada de quatro ondas com luz incoerente foi usada para investigar, pela primeira vez, o defasamento ultrarrápido de éxcitons em uma vitrocerâmica contendo nanocristais de niobato de sódio. O tempo de defasamento medido (T2 = 20 fs) indica qu empregada para investigar processos de transferência de carga em colóides com nanopartículas de TiO2 e rodamina 6G. O comportamento do sinal de depleção transiente é comparado com o observado para a rodamina livre suspensa em etanol. A análise dos resultados permitiu atribuir o comportamento de depleção à transferência de carga de estados excitados termalizados das moléculas de corante para a banda de condução do semicondutor e a transferência no sentido inverso do semicondutor para as moléculas. / The main objective of this work was the investigation of ultrafast optical phenomena in selected nanostructured systems employing different nonlinear spectroscopic techniques, either in the time or the frequency domain. To provide an appropriate background to understand the performed experiments the principles of nonlinear optical spectroscopies are presented. Initially a description of the nonlinear optical response function in the time domain is given. The time evolution of the optical polarization, that gives rise to the spectroscopic signal, is described in detail using a diagrammatic perturbation theory. Nonlinear optical techniques are discussed such as photon echoes, pump-and-probe and hole-burning, as well as how the dynamical behavior of a material can be interpreted from the generated signals. The degenerate four-wave mixing technique with incoherent light was used to investigate for the first time the ultrafast dephasing of excitons in a glass-ceramic containing sodium niobate nanocrystals. The short dephasing time measured (T2 = 20 fs) indicates that different dephasing channels contribute for the excitonic dephasing, namely: electron-electron scattering, electron-phonon coupling and fast trapping of electrons in defects on the nanocrystals interface. Low-temperature luminescence experiments were also performed to measure excitonic and trap states lifetimes. The persistent spectral holeburning technique was applied to measure localized surface plasmons dephasing times in colloidal silver nanoparticles capped with different stabilizing molecules. The dependence of T2 with three different stabilizers was demonstrated and theoretically analyzed. The results show that the dephasing times are shorter than the theoretically calculated T2 using the bulk dielectric functions of the metal. This discrepancy is attributed to changes in the electronic density of states at the nanoparticles interface caused by the presence of the stabilizers. Ab-initio calculations based on the Density Functional Theory were performed to further understand the interaction between the nanoparticles and stabilizing agents. The femtosecond transient absorption technique was employed to study the ultrafast dynamics of in-gap states in a glassceramics containing sodium niobate nanocrystals. Two main temporal components were found for the excited state absorption signal: a fast component, with decay time of ≈ 1 ps, and a slower component which is attributed to deep trap states. This slower component is responsible for the excited state absorption contribution in optical limiting experiments previously reported in the literature. The dynamics of the optical limiting in this sample was also studied, in the millisecond range, exciting the sample with a train of femtosecond pulses. The optical limiting behavior reflects the dynamics of population in the excited and trap states and this dynamics was modeled using rate equations for the electronic states’ populations. Finally, the pump-andprobe transient absorption technique was employed to investigate charge-transfer processes in colloids with rhodamine 6G and TiO2 nanoparticles. The transient bleaching signal behavior is compared with the one observed for unlinked rhodamine 6G dissolved in ethanol. The analysis of the results allowed the attribution of the bleaching behavior to charge-transfer from thermalized excited states of the dye molecules to the semiconductor conduction band and to the back charge-transfer from the semiconductor to the molecules.