The goal of this dissertation is to study the photophysics of suspensions of colloidal C₆₀ particles to determine if their nonlinear optical (NLO) response is superior in any way to benchmark NLO materials such as molecular solutions of C₆₀ and carbon black suspensions (CBS). C₆₀ in molecular form is known to exhibit strong reverse saturable absorption (RSA) and it is posited that colloidal particles composed of many C₆₀ molecules would maintain some degree of RSA behavior upon association, although some quenching is to be expected. CBS is known to have an NLO response that is dominated by nonlinear scattering resulting from a phase change due to heating of the carbon black particles by absorbed energy. Colloidal C₆₀ particles that are many nanometers in diameter are similar to CBS, so it is posited that they would also have a nonlinear scattering mechanism contributing to their NLO response. Three samples of C₆₀ colloids are characterized by several techniques, along with two carbon black suspensions and one molecular solution of C₆₀. Transmission electron microscopy is used to determine morphology. Femtosecond pump-probe spectroscopy is used to determine the absorption spectrum and the relaxation kinetics of the first excited singlet state. Nanosecond laser flash photolysis is used to determine the absorption spectrum and the relaxation kinetics of the first excited triplet state. Z-scan is used to determine triplet-triplet absorption cross-sections. An experiment is performed to determine the percentage of the input energy that is transmitted, scattered, or absorbed by each sample. Computer modeling is performed to compare the experimental results to theory. Results show that all materials that exhibit nonlinear scattering have a constant extinction coefficient in the nonlinear regime, implying a characteristic size for the scattering centers that is independent of input energy. Quenching processes in C₆₀ colloids are found to be morphology dependent, with more crystalline structures resulting in stronger quenching and less RSA. C₆₀ colloids with stronger RSA are found to result in less nonlinear scattering than strongly quenched colloids. Highly crystalline C₆₀ colloids were shown to have a stronger NLO response than the benchmark materials at medium to high energies.

Doctor of Philosophy / Department of Physics / Brian R. Washburn / Optical frequency combs produced by mode-locked fiber lasers are useful tools for high precision frequency metrology and molecular spectroscopy in a robust and portable format. We have specifically investigated erbium doped fiber mode-locked lasers that use single-walled carbon nanotubes as a saturable absorber. We have, for the first time, developed and phase- stabilized a carbon nanotube fiber laser (CNFL) frequency comb. The carbon nanotube saturable absorber, which was fabricated using an optically driven deposition method, permits a high repetition frequency (>150 MHz) since an optical nonlinearity of fibers is not used for mode-locking. The CNFL comb combined with a parabolic pulse erbium doped fiber amplifier (EDFA) has shown a compact, robust, and cost-effective supercontinuum source. The amplified pulse from the parabolic pulse EDFA was compressed with a hollow-core photonic bandgap fiber, which produced a wave-breaking-free pulse with an all-fiber set-up. The stabilized comb has demonstrated a fractional instability of 1.2 ×10[superscript]-11 at 1 sec averaging time, the reference-limited instability. We have performed optical frequency metrology with the CNFL comb and have measured an optical frequency, P(13) which is a molecular overtone transition of C2H2. The measured frequency has shown a good agreement with the known value within an uncertainty of 10 kHz. In order to extend the application of the CNFL comb such as multi-heterodyne dual comb spectroscopy, we have investigated the noise of the CNFL comb and particularly, the broad carrier envelope offset frequency (f[subscript]0) linewidth of the CNFL comb. The primary noise source is shown to be white amplitude noise on the oscillator pump laser combined with the sensitivity of the mode-locked laser to pump power fluctuations. The control bandwidth of f[subscipt]0 was limited by the response dynamics of the CNFL comb. The significant reduction of comb noise has been observed by implementing a phase-lead compensation to extend control bandwidth of the comb and by reducing the pump relative intensity noise simultaneously. Therefore the f[subscipt]0 linewidth has been narrower from 850 kHz to 220 kHz. The integrated phase noise for the f[subscipt]0 lock is 1.6 radians from 100 Hz to 102 kHz.

Neste trabalho utilizamos a técnica de mistura de duas ondas quase degeneradas na investigação das propriedades ópticas não lineares, associadas à mudança de índice de refração com a intensidade da luz, em materiais dopados com cromo: Al2O3:Cr3+ (rubi), BeAl2O4:Cr3+ (alexandrita) e GdAlO3:Cr3+ (aluminato de gadolínio dopado com cromo). A não linearidade Kerr para o GdAlO3: Cr3+ é bastante significativa, de modo que neste material o parâmetro de ganho do feixe de prova apresenta um comportamento muito peculiar e que não encontra explicação nos tratamentos teóricos usuais do processo de mistura de duas ondas. Em particular, o ganho do feixe de prova neste material atinge percentuais superiores a 200%. Desta forma, desenvolvemos um tratamento teórico que descreve a mistura de duas ondas quase degeneradas em meios onde o índice de refração depende da intensidade (n= n0+n2I). Esta abordagem teórica leva em consideração os efeitos de saturação da grade de população produzida pela intersecção dos feixes de luz no meio Kerr (não harmonicidades da grade) e o processo de mistura de duas ondas é considerado como um caso particular do fenômeno da auto-difração difração de ordem zero. Os resultados teóricos foram comparados com os resultados experimentais e várias previsões teóricas como, a dependência do parâmetro de ganho do feixe de prova com a intensidade de saturação do meio, a dependência da diferença de freqüência entre os dois feixes incidentes onde o ganho é máximo com a intensidade do feixe de bombeamento, foram confirmadas experimentalmente / In this work nearly degenerate two-wave mixing technique is used in order to investigate nonlinear optical properties, associated to the refractive índex change by incident light, in a few doped crystals: Al2O3:Cr3+ (ruby), BeAl2O4:Cr3+ (alexandrite) e GdAlO3:Cr3+ (gadolinium aluminate chromium doped). The Kerr nonlinearity in GdAlO3:Cr3+ is very high, so that the probe gain parameter has peculiar behavior in this material and this cannot be explained by using the current approach found in the literature. In particular, the probe gain parameter in this material reaches percentuals above 200%. In this way, we develop a theoretical approach which describes nearly degenerate two-wave mixing in media where the refractive índex is intensity dependent. This theoretical approach takes into account the saturation of the travelling population grating produced by two interesting beams (anharmonicities of the population grating) and the two-wave mixing process is regarded as the zero-order self-diffraction of the incident waves in this grating. The theoretical results are compared with the experimental ones and several theoretical predictions such as, the dependence of the probe gain parameter on the médium saturation intensity were experimentally verified

Neste trabalho são estudadas algumas propriedades ópticas de tetrâmeros de anilina em solução, usando o dimetil sulfóxido (DMSO) como solvente. Os espectros de absorção e emissão permitiram uma determinação aproximada dos níveis de energia do tetrâmero. Para a caracterização das propriedades ópticas não lineares foram utilizadas as técnicas de varredura-Z resolvida em freqüência e com trem de pulsos. Com a primeira foram determinados os parâmetros térmicos relacionados ao solvente, enquanto que com a segunda foram caracterizadas as não linearidades eletrônicas associadas aos estados excitados das moléculas. Além disso, foi possível obter a dinâmica das não linearidades presentes nas soluções, que apresentam um processo acumulativo relacionado à formação de uma lente térmica induzida pelo perfil gaussiano do laser. / This work reports on the optical properties of aniline tetramers in dimethyl sulfoxide (DMSO) solutions. Absorption and emission spectra allowed a rough estimate of the energy levels of the aniline tetramers. Nonlinear optical properties were studied with the frequency resolved Z-scan technique and with the Z-scan technique with pulse trains. The former determined the thermal parameters of the solvent, while the latter characterized electronic nonlinearities associated to molecular excited states. Moreover, we could analyze the dynamics of the optical nonlinearities and verify the presence of an accumulative process related to thermal lensing.

Les solitons de cavité (SC) sont des structures spatiales localisées que l'on peut générer dans une cavité optique non-linéaire. Ces structures se présentent sous la forme de pics lumineux de sur-intensité, "posées" sur un fond de lumière homogène. Depuis leur découverte, de nombreuses démonstrations de principe ont été réalisées, mettant en évidence leurs utilisations pour le traitement tout optique de l'information. Néanmoins, l'implémentation de dispositifs capables de générer des solitons de cavité dans le réseau télécom reste à l'heure actuelle improbable. Une simplification mais surtout une miniaturisation, qui passe par l'invention de nouveaux dispositifs, est un objectif majeur de la recherche sur les SC. L'objectif de cette thèse est de montrer qu'un système simple, miniaturisable, appelé Laser à solitons de cavité, permet d'obtenir ce type de structures spatiales localisées. Ce dispositif est obtenu en couplant mutuellement deux lasers de large section transverse. L'un des lasers joue le rôle d'un amplificateur alors que le second sert d'absorbant saturable fournissant le mécanisme de bistabilité. Les structures spatiales localisées obtenues sont indépendamment contrôlables à l'aide d'un faisceau dit d'écriture. La différence fondamentale entre les SCs obtenus avec un laser à SC et les SCs obtenus auparavant est due à la symétrie de phase du système laser. Cette symétrie de phase nous permet de générer des structures composites dont la phase entre les différents constituants n'est pas identique. Nous avons également observé des structures localisées circulaires possédant un défaut de phase en leur centre. Bien que prédit théoriquement, ce type de structure, appelé vortex optique localisé, n'avait jusqu'alors jamais été observé expérimentalement.

Excitabilité et structures localisées sont des phénomènes universels qui ont été observés dans une grande variété de systèmes. Chacun des deux phénomènes a des propriétés intéressante pour des applications potentielles, surtout dans l'optique. L'excitabilité est la propriété intrinsèque du neurone, elle décrit sa réponse à une stimulation: pour des stimulations en-dessous d'un certain seuil, le neurone reste dans son état de repos mais quand la stimulation dépasse ce seuil, il émet une impulsion dont la taille ne dépend pas de la force de la stimulation. Les structures localisées dans les systèmes optiques sont des pics de surintensité qui coexistent avec un fond homogène sur la section transversale spatialement étendue d'une cavité laser. Dans cette thèse nous avons étudié l'apparition de ces deux phénomènes non-linéaires dans des microcavités à semi-conducteur, pour lesquelles les applications dans le traitement tout-optique de l'information sont prometteuse. En outre, nous avons étudié la possibilité de trouver un nouveau phénomène à l'intersection entre les deux: les structures localisées excitables. D'une part nous avons étudié les propriétés des structures localisées qui se forment dans un laser à solitons. Celui-ci est constitué par deux laser à semiconducteur à cavité verticale (VCSEL) mutuellement couplées dans une configuration de laser avec absorbant saturable (LSA). Nous observons l'émissions aléatoire et localisée d'impulsions que nous affirmons être la première évidence expérimentale de structures localisées excitables. D'autre part nous avons démontré le comportement excitable d'un laser avec signal injecté par la possibilité de contrôler les impulsions excitable grâce à une perturbation externe appropriée. Nous avons également réalisé des simulations numériques qui montrent l'existence des structures localisées excitables dans un modèle de VCSEL avec absorbant saturable.

We comprehensively investigated the concentration effect of dispersed single-walled carbon nanotubes (SWCNTs) in polymer films for being a saturable absorber (SA) to stabilize the mode locking performance of the Erbium-doped fiber laser (EDFL) pulse through the diagnosis of its nonlinear properties of SA. The measured modulation depth was 1 to 4.5% as the thickness increased from 18 to 265 £gm. We obtained the stable pulse of the mode-locked EDFL (MLEDFL) when the full-width half-maximum (FWHM) decreased from 3.43 to 2.02 ps as the concentrations of SWCNTs SA increased from 0.125 to 0.5 wt%. At constant concentration of 0.125 wt%, the similar pulse shortening effect of the MLEDFL was also observed when the FWHM decreased from 3.43 to 1.85 ps was the thickness of SWCNTs SA increased from 8 to 100 £gm. In EDFL system, we vary group-velocity dispersion (GVD) with different cavity length to achieve optical pulse compression. We got the shortest pulsewidth was 713 fs, and the time-bandwidth product (TBP) was 0.345. An in-depth study on the stable mode-locked pulse formation employing SWCNTs SA, it is possible to fabricate the SWCNT films for use in high performance MLEDFL and utilization of many other low-cost nanodevices.

The overall efficiency of photovoltaics is dictated by processes occurring within it. These processes include exciton formation, diffusion, dissociation and charge collection. This dissertation will focus around the fundamental issue of charge collection. In organic photovoltaics (OPVs) the rate of charge injection is dominated by the interaction between dissimilar materials, usually organic compound interacting with inorganic ones. In order to improve this rate of injection and, by direct consequence the efficiency of this process, fundamental knowledge of this organic-inorganic interface must be gained. In this work the focus will reside solely on creating molecules capable of probing the interface between the indium tin oxide (ITO) and the donor layer. At this interface, the usual charge transfer being transferred is the hole. Chapters 2 and 3 detail the synthesis and photophysical characterization of porphyrin-perylene diimide (Por-PDI) and porphyrin-fullerene (Por-C₆₀) molecular dyads. The idea behind these moieties is that covalent attachment of these species to ITO should lead to a robust ohmic contact. Since these molecular dyads are capable of producing charge-separated states after photoexcitation, they should have the capacity to produce a radical-cation in close proximity to the ITO. This will translate to a capacity for probing the dynamics of the hole injection at this interface. Studies performed demonstrate that in fact these dyads are capable of producing a charge-separated state upon photo-excitation. The lifetimes of these states were determine to be 35 ps and 3 ns for the Por-PDI and Por-C₆₀ respectively. Chapter 4 takes a different turn. It is focused on the application and extension of a solvent-free synthesis of metallated phthalocyanines (Pcs). Shown in chapter 4 is the synthesis of a series of metallated Pcs using various transition metals and group 3 elements. Photophysical and electrochemical investigation of these materials shows that they have near-infrared absorption and relative high HOMO levels making them potential candidates for OPV applications. In addition, they displayed non-linear optical behavior due to their highly polarizable pi-systems and the presence of axial susbtituents. Finally Chapter 5 describes the synthesis and characterization of porphyrin possessing rigid linkers. This chapter also shows the further directions in which the various ideas presented in this work could be driven.

Neste trabalho utilizamos a técnica de mistura de duas ondas quase degeneradas na investigação das propriedades ópticas não lineares, associadas à mudança de índice de refração com a intensidade da luz, em materiais dopados com cromo: Al2O3:Cr3+ (rubi), BeAl2O4:Cr3+ (alexandrita) e GdAlO3:Cr3+ (aluminato de gadolínio dopado com cromo). A não linearidade Kerr para o GdAlO3: Cr3+ é bastante significativa, de modo que neste material o parâmetro de ganho do feixe de prova apresenta um comportamento muito peculiar e que não encontra explicação nos tratamentos teóricos usuais do processo de mistura de duas ondas. Em particular, o ganho do feixe de prova neste material atinge percentuais superiores a 200%. Desta forma, desenvolvemos um tratamento teórico que descreve a mistura de duas ondas quase degeneradas em meios onde o índice de refração depende da intensidade (n= n0+n2I). Esta abordagem teórica leva em consideração os efeitos de saturação da grade de população produzida pela intersecção dos feixes de luz no meio Kerr (não harmonicidades da grade) e o processo de mistura de duas ondas é considerado como um caso particular do fenômeno da auto-difração difração de ordem zero. Os resultados teóricos foram comparados com os resultados experimentais e várias previsões teóricas como, a dependência do parâmetro de ganho do feixe de prova com a intensidade de saturação do meio, a dependência da diferença de freqüência entre os dois feixes incidentes onde o ganho é máximo com a intensidade do feixe de bombeamento, foram confirmadas experimentalmente / In this work nearly degenerate two-wave mixing technique is used in order to investigate nonlinear optical properties, associated to the refractive índex change by incident light, in a few doped crystals: Al2O3:Cr3+ (ruby), BeAl2O4:Cr3+ (alexandrite) e GdAlO3:Cr3+ (gadolinium aluminate chromium doped). The Kerr nonlinearity in GdAlO3:Cr3+ is very high, so that the probe gain parameter has peculiar behavior in this material and this cannot be explained by using the current approach found in the literature. In particular, the probe gain parameter in this material reaches percentuals above 200%. In this way, we develop a theoretical approach which describes nearly degenerate two-wave mixing in media where the refractive índex is intensity dependent. This theoretical approach takes into account the saturation of the travelling population grating produced by two interesting beams (anharmonicities of the population grating) and the two-wave mixing process is regarded as the zero-order self-diffraction of the incident waves in this grating. The theoretical results are compared with the experimental ones and several theoretical predictions such as, the dependence of the probe gain parameter on the médium saturation intensity were experimentally verified

Neste trabalho são estudadas algumas propriedades ópticas de tetrâmeros de anilina em solução, usando o dimetil sulfóxido (DMSO) como solvente. Os espectros de absorção e emissão permitiram uma determinação aproximada dos níveis de energia do tetrâmero. Para a caracterização das propriedades ópticas não lineares foram utilizadas as técnicas de varredura-Z resolvida em freqüência e com trem de pulsos. Com a primeira foram determinados os parâmetros térmicos relacionados ao solvente, enquanto que com a segunda foram caracterizadas as não linearidades eletrônicas associadas aos estados excitados das moléculas. Além disso, foi possível obter a dinâmica das não linearidades presentes nas soluções, que apresentam um processo acumulativo relacionado à formação de uma lente térmica induzida pelo perfil gaussiano do laser. / This work reports on the optical properties of aniline tetramers in dimethyl sulfoxide (DMSO) solutions. Absorption and emission spectra allowed a rough estimate of the energy levels of the aniline tetramers. Nonlinear optical properties were studied with the frequency resolved Z-scan technique and with the Z-scan technique with pulse trains. The former determined the thermal parameters of the solvent, while the latter characterized electronic nonlinearities associated to molecular excited states. Moreover, we could analyze the dynamics of the optical nonlinearities and verify the presence of an accumulative process related to thermal lensing.