The graphene-polymer SA thin film using solution blending method and atomic layer graphene as saturable absorber (SA) used to generate femtosecond laser pulse were measured. Stable soliton-like pulses with the pulsewidth of 403 fs and 432 fs, the spectral linewidth of 6.32 nm and 6.16 nm, and the time-bandwidth product of 0.315 and 0.329 using graphene-PVA film and atomic layer graphene as SA were achieved, respectively, in mode-locked Er-doped fiber ring laser. The graphene-PVA SA suffered from larger loss caused by graphene flake aggregating, while the atomic layer graphene had smaller nonsaturable loss which exhibited lower mode locking threshold power. Atomic layer graphene also had stable fabricated process and controllable modulation depth depended on its layer numbers. To compare the mode locking performance of single wall carbon nanotubes (SWCNTs) and graphene SA, the same solution blending fabricated sample was used. Under similar nonsaturable loss and modulation depth, the SWCNTs SA with optimized concentration of 0.5wt% and thickness of 188£gm had shortest pulsewidth of 440 fs and 3-dB spectral linewidth of 6 nm. The shortest pulsewidth of 403 fs and broad spectral linewidth of 6.32 nm was obtained using graphene SA with concentration of 6.25wt% and thickness of 18£gm. Graphene has broad band absorbance and larger modulation depth, the experimental result indicates that graphene SA can generate shorter pulse and has chance to become the potential candidate of SA.

The dependence of single-wall carbon nanotubes-based saturable absorber (SWCNTs SA) on concentration and thickness for mode-locked laser pulse formation is comprehensively investigated. The peak absorption wavelength of SWCNTs SA is engineered within the gain band-width of erbium-doped fiber centered near 1550 nm. The optima full-width half-maximum (FWHM) of pulses was obtained as the concentrations of SWCNTs SA was 0.05 wt%. This indicates that the laser pulse become shorter as the concentration of SWCNTs SA increases. The result also showed that the FWHM of pulses from 3.43 to 1.85 ps were found as the thickness of SWCNTs SA increased from 8 to 100 um. This also indicates that the laser pulse become shorter as the thickness of SWCNTs SA increases. However, the pulse width significantly broadened as concentration increased to 0.1 wt% and became stable as thickness of SWCNTs SA increased from 100 to 264 um for passively mode-locked lasers. An in-depth study on the optimum fabrication of concentration and thickness of SWCNTs SA for laser pulse formation may allow developing a cost-effective mode-locked laser with high performance as well as broadly benefit to the utilization of many other low-cost nanodevices.

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

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

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. / Excitability and localized structures are universal phenomena, observed in various systems. Both possess interesting properties for potential applications, especially in optics. Excitability is the intrinsic property of the neuron defining its response to an external stimulus: for a sub-threshold stimulus the neuron stays quiescent; for a super-threshold stimulus, it emits a well-calibrated pulse independent on the strength of the stimulus. Localized structures in optics are bright intensity peaks coexisting with a homogeneous low intensity background. They appear in the transverse section of spatially-extended laser resonators. We study the occurrence of these nonlinear phenomena in semiconductor microcavities since the applications in all-optical processing of information are promising. Moreover we investigate the possibility of a novel kind of localized structure which stands at the intersection of these two phenomena: the excitable localized structures. On the one hand we study the properties of localized structures arising from a cavity soliton laser composed of two mutually coupled broad-area VCSELs in a LSA (Laser with Saturable Absorber) configuration . We report on the observation of a random and localized emission of pulses which we claim to be the first experimental evidence of noise-triggered excitable localized structures whose excitability is induced by inhomogeneities and drift. On the other hand we demonstrate the excitability in an optically injected laser by showing the control of excitable pulses by means of an external perturbation. We also perform numerical simulations which reveal the existence of excitable localized structures in a model of broad area VCSEL with saturable absorber.

This dissertation can be divided into two parts project goals. The first one is the synthesis of rhenium (Re) complexes which are potential reverse saturable absorber (RSA) materials. The second one is the polymerization of ruthenium (Ru) polypyridyl monomers to have an oligomer ensemble for solar light harvesting purposes. THE FIRST part starts with an introduction to optical limiting materials (OLM) (chapter 1). The main discussion in chapter 4 is about the photophysical properties and energy-transfer reactions for three series of facial Re(I) tri-carbonyl complexes. The complexes are of the general type fac-[Re(CO)3(N-N)Cl], where Cl is the chloride and N-N are novel mono functionalized aryl-oligo(p-phenylene-vinylene) bipyridine (bpy) ligands. These series is as a result of changing the aryl group of the ligands to either anthracene or pyrene, and di-alkoxy attachments of phenyl ring in anthracene bipyridine ligands. The synthesis of the bpy ligands involved attaching various aryls by utilizing successive multi-step Wittig-Horner reactions (chapter 2). The ligands were later reacted with Re pentacarbonyl chloride to obtain the complexes. Chromium complexes synthesis is also included (chapter 3). The characterization involved 1H NMR, ESI-MS and elemental analysis. There is also another set of ligands where the aryl group is di-methylaminophenyl where the solvatochromic emission properties of the ligands were studied but were not coordinated to metals. The excited-state properties using both the nanosecond (ns) and picosecond (ps) time resolved transient absorption (TA) of Re(I) complexes shows strong positive excited-state absorption signals in 500-800 nm range. From the TA (ps) and time-resolved infrared of the carbonyl region, the excited state forms instantaneously after excitation. Their observed lifetimes are relatively long (2 μs-40 μs range) and they increase as the phenylene-vinylene linker increases. The excited state triplet energies values for the complexes were obtained experimentally using energy transfer method from the simple Sandros relation. They decreases as the π-conjugated phenylene-vinylene linker decreases, this is because the extended backbone bridge serves to lower the energy of the triplet excited state. Lastly, the Re(I) complexes triplet-triplet molar extinction coefficients(δex) were measured by energy transfer to a standard method and their ratios to the ground state molar absorptivity(δg ) are all (δex/δg ≥40) at 530nm which make them potential candidates for RSA. THE SECOND part involves RAFT polymerization of two new acrylamide functionalized Ru(II) polypyridyl monomers. Photoinduced electron transfer reactions for the obtained Ru oligomers and complexes were done using 10-methylphenothiazine (MPT) quencher (chapter 8). The synthesized acrylamide functionalized bipyridine ligand (chapter 6) was reacted with complex precursors cis-[Ru(L)2Cl2] where the ligand (L) is either 2,2’- bipyridine or biquinoline (chapter 7). The obtained Ru(II) photosensitizers acts as energy donating and accepting respectively. The attachment of these Ru complexes to oligomer backbone as side chains is by a C11 alkyl linker. 1H NMR, UV-Vis spectroscopy, and differential pulse voltammetry (DPV) were used to characterize the ligand, monomers and oligomers. The excited state REDOX potentials were determined using the cyclic voltammetry (CV) values and steady state emission values converted to electron volt (eV). Lastly, the TAs (ns) obtained in the presence of MPT electron donating quencher was in agreement with the ones calculated/ predicted from spectroelectrochemistry. These efforts are toward the goal of making a panchromatic solar light collector in the visible region (chapter 5). / acase@tulane.edu

Dans cette thèse, nous avons développé et étudié des miroirs absorbants saturables ultra-rapides, pour des applications au traitement de signaux optiques à très haut débit et la génération d’impulsions laser ultra-courtes à 1.55 µm. Dans une première partie, nous avons développé un miroir absorbant saturable ultra-rapide basé sur le semi-conducteur In₀.₅₃Ga₀.₄₇As soumis à une implantation ionique à température élevée de 300 °C. Des ions Fe ont été utilisés car il a été démontré que les niveaux Fe²⁺/Fe³⁺ peuvent agir comme des centres de recombinaison efficaces pour les électrons et les trous dans In₀.₅₃Ga₀.₄₇As. Nous avons étudié la durée de vie des porteurs en fonction de la dose ionique, la température et le temps de recuit. A part la durée de vie rapide, les caractéristiques de réflectivité non-linéaire, telles que l’absorption linéaire, la profondeur de modulation, les pertes non saturables ont été étudiées dans différentes conditions de recuit. Après un recuit à 600 °C pendant 15 s, un échantillon présentant une grande amplitude de modulation de 53,9 % et une durée de vie de porteurs de 2 ps a été obtenu. Dans une seconde partie, la gravure par faisceau d’ions focalisés (FIB) a été utilisée pour fabriquer une structure en biseau ultrafin sur de l’InP cristallin, pour réaliser un dispositif photonique multi-longueur d’onde à cavité verticale. Les procédures de balayage FIB et les paramètres appropriés ont été utilisés pour contrôler le re-dépôt du matériau cible et pour minimiser la rugosité de surface de la zone gravée. Le rendement de pulvérisation de la cible en InP cristallin a été déterminé en étudiant la relation entre la profondeur de gravure et la dose ionique. En appliquant les conditions de rendement optimales, nous avons obtenu une structure en biseau ultrafin dont la profondeur de gravure est précisément ajustée de 25 nm à 55 nm, avec une pente horizontale de 1:13000. La caractérisation optique de ce dispositif en biseau a confirmé le comportement multi-longueur d’onde de notre dispositif et montré que les pertes optiques induites par le procédé de gravure FIB sont négligeables. Dans une troisième partie, nous avons démontré que la réponse optique non-linéaire du graphène est augmentée de manière résonnante quand une monocouche de graphène est incluse dans une microcavité verticale comportant un miroir supérieur. Une couche mince de Si₃N₄ a été déposée selon un procédé de dépôt par PECVD spécialement développé pour agir comme couche de protection préalable avant le dépôt du miroir supérieur proprement dit, permettant ainsi de préserver les propriétés optiques du graphène. En incluant une monocouche de graphène dans une microcavité appropriée, une profondeur de modulation de 14,9 % a été obtenue pour une fluence incidente de 108 µJ/cm². Cette profondeur de modulation est beaucoup plus élevée que la valeur maximale de 2 % obtenue dans les travaux antérieurs. De plus un temps de recouvrement aussi bref que 0,7 ps a été obtenu. / In this thesis, we focus on the development of ultrafast saturable absorber mirrors for applications to ultra-high speed optical signal processing and ultrashort laser pulse generation at 1.55 μm. In the first part, we have developed an ultrafast In₀.₅₃Ga₀.₄₇As -based semiconductor saturable absorber mirror by heavy ion implantation at the elevated temperature of 300 ºC. Fe ion has been employed as the implant since it has been shown that Fe²⁺/Fe³⁺ level can act as efficient recombination centers for electrons and holes in In₀.₅₃Ga₀.₄₇As. We studied the carrier lifetime of Fe-implanted sample as a function of ion dose, temperature and annealing time. Apart from the fast carrier lifetime, the characteristics of nonlinear reflectivity for the Fe-implanted sample, such as linear absorption, modulation depth, nonsaturable loss, have are also been investigated under different annealing temperature. Under annealing at 600 ºC for 15 s, the Fe-implanted sample with a big modulation depth of 53.9 % and a fast carrier lifetime of 2 ps has been achieved. In the second part, focused ion beam milling has been applied to fabricate an ultra-thin taper structure on crystalline indium phosphide to realize a multi-wavelength vertical cavity photonic device. The appropriate FIB scanning procedures and operating parameters were used to control the target material re-deposition and to minimize the surface roughness of the milled area. The sputtering yield of crystalline indium phosphide target was determined by investigating the relationship between milling depth and ion dose. By applying the optimal experimentally obtained yield and related dose range, we have fabricated an ultra-thin taper structure whose etch depths are precisely and progressively tapered from 25 nm to 55 nm, with a horizontal slope of about 1:13000. The optical characterization of this tapered device confirms the expected multi-wavelength behavior of our device and shows that the optical losses induced by the FIB milling process are negligible. In the third part, we demonstrate that the nonlinear optical response of graphene is resonantly enhanced by incorporating monolayer graphene into a vertical microcavity with a top mirror. A thin Si₃N₄ layer was deposited by a developed PECVD process to act as a protective layer before subsequent top mirror deposition, which allowed preserving the optical properties of graphene. Combining monolayer graphene with a microcavity, a modulation depth of 14.9 % was achieved at an input energy fluence of 108 µJ/cm². This modulation depth is much higher than the value of about 2 % in other works. At the same time, an ultrafast recovery time of 0.7 ps is retained.