Limitadores ópticos são dispositivos que apresentam alta transmitância para baixas intensidades de luz incidente e, inversamente, baixa transmitância para altas intensidades, sendo usados como protetores contra danos em sensores ópticos e olhos humanos. Com o objetivo de estudarmos novos materiais com mecanismos não lineares eficientes para o processo de limitação, bem como novas geometrias ópticas, apresentamos neste trabalho o desenvolvimento de um limitador óptico baseado na absorção saturada reversa de porfirinas e metaloporfirinas. Construímos também um dispositivo baseado na configuração óptica bifocal, usando porfirina como absorvedor saturável reverso. Além disso, obtivemos parâmetros espectroscópicos do estado excitado pelos ajustes teóricos das curvas de transmitância, através da resolução de equações de taxa. / Optical limiters are devices with a high transmittance in the presence of low intensity light, and a considerable lower transmittance otherwise, been used as protectors against damage in optical sensors and human eyes. Aiming at searching for new materials and optical geometries efficient for optical limiting. We report on the development of an optical limiter based on the reverse saturable absorption in porphyrin and metalioporphyrins. We also built a device-based .on a cascade focus configuration, using free base porphyrin as the absorber. Besides, we obtain the excited state spectroscopy parameters by the theoretical fitting of transmittance curves, by solving a set of rate equations.

"Hydroxyl ions are a common contaminant in optical fibers, and are responsible for strong absorption centered at 1380 nm that becomes significant over long optical path lengths. Recently, however, special fabrication methods have been developed that minimize the hydroxyl ion contamination, permitting use of the entire 1300-1700 nm spectral region for telecommunications. There is therefore interest in examining the Nd 4F3/2 to 4I13/2 transition for a potential optical amplifier at 1400 nm. In this thesis, the excited state absorption cross section and the overall gain/loss spectrum of neodymium in a silica glass fiber were determined for the 1200-1500 nm wavelength region using the pump-probe method. The ground state absorption cross section was also determined from transmission measurements, and the stimulated emission cross section was calculated using the fluorescence spectrum and the McCumber relation. Oscillator strengths for absorption and emission transitions were calculated in the 800-1600 nm wavelength range using the Judd-Ofelt method. The above procedures were followed for both the Nd-doped fiber, as well as an erbium-doped silica fiber. The shape of the Nd emission spectrum is also noteworthy, since the characteristic Nd peak at 1064 nm is not observed, although there is strong emission at 1092 nm. The pump-probe measurements revealed significant excited state absorption loss between 1200 and 1350 nm, due to excitation from the 4F3/2 to the higher 4G9/2 and 4G7/2 states. Between 1350 and 1475 nm, there was no net gain or loss that could be observed beyond the level of the noise. For the glass fibers studied, it appears that in the spectral region of interest for an optical amplifier, the stimulated emission and excited state absorption cancel one another out."

In this study, we study the polarization dependence, gain property, and amplified spontaneous emission in Cr4+: YAG crystal fibers. Cr4+: YAG crystal has an ultra-wide bandwidth of 300 nm. Cr4+: YAG crystal fibers fabricated through laser heated pedestal growth technique are suitable for the applications of fiber amplifiers, fiber lasers, and broadband light sources. The experiment results showed that the polarization-dependent loss has a severe variation as the optical wavelength change. The maximum polarization-dependent loss was up to 18 dB. The main reason of such a large polarization-dependent loss is the combination of multimode interference and the birefringence induced by the non-uniformity of optical waveguide structure and residue strain in Cr4+: YAG crystal fibers. Thus, the results of polarization-dependent loss can be used as a feedback parameter to improve the fabrication process. In the experiment of gain property, bi-directional pump and double-pass transmission scheme was adopted and a 0.2 dB net gain was obtained for the first time at signal wavelength of 1400 nm, pumping wavelength of 1060 nm, and total pumping power of 2.8 W. It shows that Cr4+: YAG crystal fiber has potential to be developed as a broadband fiber amplifier. In the measurement of amplified spontaneous emission spectrum, a wide bandwidth of amplified spontaneous emission of 300 nm with total power of 50 £gWwas obtained at 0.2W pumping power condition. The coupling efficiencies from amplified spontaneous emission to single mode fibers and multimode fibers were 1.5 % and 9.9 %, respectively. This result reveals that it has potential to be developed as a broadband light source. To improve the optical properties of Cr4+: YAG crystal fiber in the future, improving the uniformity of optical fiber waveguide and reducing the residue strain in Cr4+: YAG crystal fiber may suppress the polarization-dependent loss; increasing the fiber length, decreasing the mode number, and employing a cladding pump technique with a well-distributed pump power in the crystal fiber to alleviate the excited state absorption may raise the gain performance and the amplified spontaneous emission power.

In this work, interference and coherence phenomena, appearing in atomic and molecular ensembles interacting with coherent light sources, as electromagnetically induced transparency (EIT), coherent population trapping (CPT), and slow group velocity of light are investigated. The goal of the project is to make the steps towards various applications of these phenomena, first, by studying them in solid media (which are the most advantageous for applications), second, by suggesting some novel applications such as CPT-based plasma diagnostics, and realization of new types of solid-state lasers (based on suppression of excited-state absorption via EIT). The third goal of the project is extension of coherence and interference effects well-known in optics to the gamma-ray range of frequencies and, correspondingly, from atomic to nuclear transitions. A particular technique of chirped pulse compression applied to M??ossbauer transitions is considered and the possibility of compression of M??ossbauer radiation into ultrashort gamma-ray pulses is analyzed. The theoretical treatment of the interference and coherence effects is based on the semiclassical description of atom-light interaction, which is sufficient for correct analysis of the phenomena considered here. Coherent media are considered in two-, three-, and four-level approximations while their interaction with light is studied both analytically and numerically using the Maxwell-Bloch set of equations.

Magister Scientiae - MSc (Chemistry) / Nanoscience and nanotechnology are known to be interdisciplinary, crossing and combining various fields and disciplines in pursuit of desirable outcomes. This has brought about applications of nanoscience and nanotechnology in multitudes of industries, spanning from the health, pharmaceutical to industrial industry. Within the health industry, the medical field has seen much advancement through nanoscience and nanotechnology. The importance of finding cures to diseases is top priorities within the medical field, along with advancements in understanding and diagnosing diseases. Due to these outcomes, we see the emergence of imaging techniques playing a crucial role. The work covered in this thesis looks at a prospective luminescent agent applicable in the medical field for bio-imaging, but also at a possible phthalocyanine sensitizer for treatment of cancer through photodynamic therapy. Another area where nanoscience and nanotechnology are found is in industry, where nanoparticles are utilised as catalysts in many synthetic reactions. Highly desirable catalysts in industry are those involved in oxidative reactions where we explore a metal nanoparticle catalyst within this work.

Limitadores ópticos são dispositivos que apresentam alta transmitância para baixas intensidades de luz incidente e, inversamente, baixa transmitância para altas intensidades, sendo usados como protetores contra danos em sensores ópticos e olhos humanos. Com o objetivo de estudarmos novos materiais com mecanismos não lineares eficientes para o processo de limitação, bem como novas geometrias ópticas, apresentamos neste trabalho o desenvolvimento de um limitador óptico baseado na absorção saturada reversa de porfirinas e metaloporfirinas. Construímos também um dispositivo baseado na configuração óptica bifocal, usando porfirina como absorvedor saturável reverso. Além disso, obtivemos parâmetros espectroscópicos do estado excitado pelos ajustes teóricos das curvas de transmitância, através da resolução de equações de taxa. / Optical limiters are devices with a high transmittance in the presence of low intensity light, and a considerable lower transmittance otherwise, been used as protectors against damage in optical sensors and human eyes. Aiming at searching for new materials and optical geometries efficient for optical limiting. We report on the development of an optical limiter based on the reverse saturable absorption in porphyrin and metalioporphyrins. We also built a device-based .on a cascade focus configuration, using free base porphyrin as the absorber. Besides, we obtain the excited state spectroscopy parameters by the theoretical fitting of transmittance curves, by solving a set of rate equations.

<p> </p><p>The interaction between light and organometallic chromophores has been investigated theoretically in a strive for fast optical filters. The main emphasis is on two-photon absorption and excited state absorption as illustrated in the Jablonski diagram. We stress the need for relativistic calculations and have developed methods to address this issue. Furthermore, we present how quantum chemical calculations can be combined with Maxwell's equations in order to simulate propagation of laser pulses through a materials doped with chromophores with high two-photon absorption cross sections. Finally, we also discuss how fast agile filters using spin-transition materials can be modeled in order to accomplish theoretical material design.</p> / Report code: LIU-TEK-LIC-2006:55. On the day of the defence date the status on article III was Manuscript, article IV was Accepted and article V was Submitted.

The interaction between light and organometallic chromophores has been investigated theoretically in a strive for fast optical filters. The main emphasis is on two-photon absorption and excited state absorption as illustrated in the Jablonski diagram. We stress the need for relativistic calculations and have developed methods to address this issue. Furthermore, we present how quantum chemical calculations can be combined with Maxwell's equations in order to simulate propagation of laser pulses through a materials doped with chromophores with high two-photon absorption cross sections. Finally, we also discuss how fast agile filters using spin-transition materials can be modeled in order to accomplish theoretical material design. / <p>Report code: LIU-TEK-LIC-2006:55. On the day of the defence date the status on article III was Manuscript, article IV was Accepted and article V was Submitted.</p>

La limitation optique (LO) est un processus de protection des détecteurs optiques (yeux, caméras…) vis-à-vis des agressions laser. Le développement rapide de ces derniers aux fréquences des télécommunications a encouragé l’ingénierie moléculaire pour la LO dans cette fenêtre spectrale, en particulier à 1500 nm. Un des principaux mécanismes de la LO est l’absorption multiphotonique et plus particulièrement l’absorption à deux photons (ADP). Il s’agit d’un phénomène d’optique non-linéaire du troisième ordre au cours duquel un électron est promu de l’état fondamental vers l’état excité par absorption simultanée de deux photons. De plus, des travaux récents ont mis en évidence que le phénomène de LO peut être exalté par des processus d’absorption à l’état excité (AEE) induits par ADP. Dans ce contexte, cette thèse décrit la synthèse d’une nouvelle famille de chromophores de type aza-dipyrrométhène de bore (Aza-Bodipy), fonctionnalisés par des groupements donneur ou accepteur d’électrons. Ces molécules ont un comportement de limiteur optique sur toute la gamme spectrale voulue, avec un maximum d’efficacité vers 1300 nm. Les résultats ont été interprétés sur la base de deux phénomènes : l’ADP, suivie de l’AEE pour un procédé d’absorption globale à trois photons. Ces deux processus ont été mesurés séparément et des relations structure-activité ont été établies, afin de rationnaliser les données de LO. L’importance du transfert de charge et la superposition spectrale des deux phénomènes sont alors apparues comme les paramètres clefs à optimiser. En vue d’une application dans un dispositif optique réel, il est nécessaire que les chromophores soient incorporés dans un matériau solide, qui peut être poli et transformé. Ainsi, les composés synthétisés ont été insérés avec succès dans une matrice sol-gel. Pour la première fois, des matériaux de qualité optique ont été réalisés, possédant des propriétés de LO dans l’infra-rouge très performantes et meilleures qu’en solution. / The optical power limiting (OPL) is a protection process of detectors (eyes, cameras…) against laser aggression. The rapid development of frequency-tunable pulsed lasers up to telecommunication wavelengths led to the design of new materials for nonlinear absorption in this spectral range, in particular at 1500 nm. Mutiphotonic absorption, such as the two-photon absorption (TPA) is one of the mechanisms involved in the OPL. TPA is a third order nonlinear phenomenon that promotes a molecule to an excited state by the simultaneous absorption of two photons. Moreover, the overall OPL efficiency can be enhanced by excited state absorption (ESA). In this context, this thesis describes the synthesis of a new family of versatile near infra-red dyes, namely aza-borondipyrromethene (Aza-Bodipy) featuring several sites of functionalization by electro-donating or electro-withdrawing moieties. These molecules present the typical behavior of optical limiters at telecommunication wavelengths, with a maximal efficiency around 1300 nm. OPL curves were interpreted on the basis of two phenomena: TPA, followed by ESA for an overall 2+1 photons absorption. These two processes have been measured independently and structure-activity relationships have been established in order to rationalize OPL experiments. The charge transfer effect and the spectral overlap between TPA and ESA are therefore the key parameters. For practical use of OPL functions, it is required for the chromophores to be introduced into a solid material, which enables polishing and other post-processing. Therefore, Aza-Bodipy dyes have been successfully incorporated to a solid matrix using the sol-gel technique. For the first time, optical quality materials have been prepared featuring OPL properties in the infra-red, which are better than the ones in solution.

Neste trabalho, são estudadas as alterações das propriedades ópticas lineares e não lineares de soluções de azocompostos devidas aos mecanismos de isomerização e às alterações das propriedades estruturais com a temperatura. A dependência da transição pipi* com a estrutura linear dos azocompostos é notada já nas medidas dos espectros de absorção em função da temperatura para o isômero trans. Através do conhecimento dos níveis de energia e dos tempos de relaxação via isomerização, foi possível obter a dinâmica entre os isômeros cis e trans. As medidas não lineares forneceram propriedades interessantes associadas aos estados de energia dos compostos. Por exemplo, através de experimentos de varredura-z e de excitação e prova, foi possível ver que os azocompostos apresentam uma alta transparência quando excitados, a qual desaparece com o término da isomerização. Medidas em função do comprimento de onda mostraram que a transparência observada está presente em toda a banda pipi* e não ocorre na banda npi* . Também foi observado que o tempo de isomerização muda de acordo com o comprimento de onda de excitação, o que pode estar relacionado com a superposição das duas bandas. Os resultados obtidos em femtossegundos foram essenciais para descrever o processo dinâmico de fotoisomerização, observado, por completo, através de medidas com varredura-Z em picossegundos e nanossegundos. Essas medidas forneceram os valores das seções de choque dos isômeros cis, que são difíceis de serem quantificadas devido ao curto tempo de vida desse isômero. Além dos resultados ressonantes, foram feitos experimentos de absorção de dois fótons em femtossegundos usando a técnica de varredura-Z. Esses estudos mostraram a dependência das seções de choque de absorção de dois fótons com características estruturais das moléculas, tais como comprimento de conjugação, grupos push-pull e planaridade. Os resultados ressonantes e não ressonantes obtidos em femtossegundos serviram de base para a calibração da técnica de varredura-Z com pulsos de luz branca. Essa técnica se mostrou adequada para a obtenção dos espectros das não linearidades ópticas ressonantes e não ressonantes em uma única medição (de 5 minutos), diminuindo assim flutuações do laser durante o experimento. / This work reports on the temperature dependence of linear and nonlinear properties of azocompounds solutions due to isomerization mechanisms. The dependence of pipi* transitions on the linear structure of azocompounds is already noticeble in the measurements of absorption spectra as function of the temperature for the trans isomer. Knowing the energy levels and the relaxation times through isomerization, it was possible to obtain the exchange dynamics between cis and trans conformations. Nonlinear measurements provided interesting properties associated with the energy levels of de compounds. For exemple, through Z-scan and pumpprobe experiments, it was possible to verify that azocompounds present a high transparency when excited and that this transparency disapears when the izomerization ends. The wavelength change has shown that the observed transparency is present along the complete pipi* band, but not in the npi* band. It was also observed that the isomerization time changes with the exciting wavelength, which may be related to the superposition of both bands. The results obained with femtoseconds pulses were essential to completily describe the photoisomerization process observed with Z-scan measurements using picoseconds and nanoseconds pulses. These measurements provided values of the crosssection of the cis conformation, which are difficult to be quantified due to the short lifetime of this isomer. Besides ressonant results, experiments of two-photon absorption in the femtosecond regime using the Z-scan technique were made. These studies shown the dependence of the two photons absorption cross-section on structural features of molecules such as conjugation length, push-pull groups and planarity. The ressonant and nonressonant results obteined with femtoseconds have provide the calibration of the Z-scan technique with white light pulses. This technique has been found able to obtain the spectra of ressonat and nonressonant nonlinearities in a single measurement (about 5 minutes), diminishing laser fluctuation during the experiment.