Neste trabalho, aplicamos técnicas de óptica não-linear de segunda ordem, em particular a Espectroscopia por Geração de Soma de Freqüências (SFG) e a Geração de Segundo Harmônico (SHG), para investigar a adsorção e o ordenamento molecular de filmes automontados de polieletrólitos variando-se os parâmetros que influenciam a adsorção (pH, força iônica, densidade de carga), além de investigar a estabilidade térmica e possíveis transições de fases nesses filmes multicamadas como função do pH das soluções e o do número de camadas. A espectroscopia SFG de filmes dos polieletrólitos poly(allylamine hydrochloride) (PAH) e poly(styrene sulfonate) (PSS) permitiu acompanhar a adsorção das camadas pelo monitoramento do campo elétrico na interface (substrato+filme adsorvido)/solução. As medidas de fase do sinal SFG confirmaram a supercompensação de cargas em todos os valores de pH estudados, exceto a pH 12, onde a adsorção foi possível devido a interações eletrostáticas locais. Os filmes secos mostraram grande ordenamento e homogeneidade quando a secagem era espontânea (sem a ação de jato de N2), independentemente do pH. Nestes filmes, observou-se pela primeira vez que as camadas adsorvidas podem alterar o ordenamento e a conformação das cadeias previamente adsorvidas. A espectroscopia SFG também apontou para a redução da densidade de carga e do ordenamento molecular quando a força iônica era aumentada, devido ao efeito de blindagem eletrostática. Os filmes tornaram-se mais inomogêneos e desordenados em virtude da compensação extrínseca. O efeito da força iônica foi o de reduzir a densidade de carga e assim o ordenamento molecular, mesmo se a secagem fosse espontânea. A técnica de SHG foi aplicada a filmes automontados de PAH e PS-119 para confirmar sua estabilidade térmica em função do pH e do número de camadas, além de verificar o ordenamento molecular antes e após o tratamento térmico. Os resultados mostraram que os filmes não são termicamente estáveis: o sinal é completamente destruído à temperatura de 150oC aproximadamente, ao contrário do que relata a literatura. As medidas SHG também confirmaram a isotropia dos filmes no plano das amostras, independente do pH ou do número de camadas. Comparando-se o sinal SHG antes e depois do aquecimento, comprovou-se que após o resfriamento lento, o sinal era restituído a quase o mesmo valor que antes, mostrando que o processo de desordem térmica é reversível. Entretanto, nenhuma transição de fase foi observada, pois a redução do sinal SHG foi lenta e gradual, sem nenhuma variação brusca que caracterizasse uma transição vítrea. Enfim, nossas medidas do sinal SHG em função do número de camadas também discordaram dos resultados da literatura, pois a susceptibilidade de segunda ordem não cresceu linearmente com o número de bicamadas. Isso indica que as moléculas não adsorvem com mesmo ordenamento em cada bicamada. Desse modo, podemos concluir que as técnicas SFG e SHG fornecem informação a nível microscópico que podem levar ao aprimoramento das aplicações dos filmes automontados, e que seriam difíceis de obter com técnicas tradicionais. / In this study, we have applied second-order nonlinear optical techniques, in particular Sum-Frequency Generation (SFG) and Second-Harmonic Generation (SHG), to investigate the adsorption and the molecular ordering of self-assembled polyelectrolyte films varying the parameters which are relevant to polyelectrolyte adsorption (pH, ionic strength, charge density), besides investigating the thermal stability and possible phase transistions in these multilayer films as function of pH of the solutions and of the number of layers. SFG spectroscopy of films fabricated with the polyelectrolytes PAH and PSS allowed us to monitor the adsorption of each layer by the electric field at the (substrate+adsorbed film)/solution interface. Phase-measurements of the SFG signal confirmed that charge supercompensation occurred at all pH values investigated, except at pH 12, where the adsorption was possible by local electrostatic interactions. Dry films have shown great order and homogeneity if the drying was spontaneous (without blow-drying with N2), independently of pH. In these films, it was observed for the first time that layer adsorption can modify the order and the conformation of previously adsorbed chains. SFG spectroscopy also pointed to the reduction of the charge density and of the molecular order if the ionic strength was increased, due to the electrostatic screening effect. The films were more inhomogeneous and disordered due to extrinsic charge compensation. The effect of the ionic strength was to reduce the charge density and the molecular order, even if the drying were slow (spontaneous). The SHG technique was applied to LBL films of PAH and PS-119 to confirm their thermal stability as a function of pH of the solutions and the number of layers, besides comparing the molecular order before and after the thermal treatment. The results have shown that the films are not thermally stable, with the SHG signal nearly vanished if the temperature of 150 oC is reached, in contrast of what is reported in the literature. SHG measurements have also confirmed that the films are isotropic in the plan of the samples, independent of pH or the number of layers. Comparing the SHG signal before and after heating, it was found that the SHG signal was considerably reduced at high temperatures, but after slow cooling it was recovered to almost the same value as before heating, showing that the thermal disorder is reversible. However, no phase transistion was observed, since the SHG signal reduction was slow and gradual, without any sudden change that would characterize a glass transition. At last, our SHG measurements as a function of the number of layers also disagreed with results in the literature, therefore the second order susceptibility did not grow linearly with the number of bilayers. This indicates that the molecules do not adsorb with same order in each bilayer. Therefore, we can conclude that SFG and SHG techniques provide information on the film arrangement at the microscopic level which could be difficult to get with traditional techniques and could also lead to the improvement of applications of LBL films.

Neste trabalho, aplicamos técnicas de óptica não-linear de segunda ordem, em particular a Espectroscopia por Geração de Soma de Freqüências (SFG) e a Geração de Segundo Harmônico (SHG), para investigar a adsorção e o ordenamento molecular de filmes automontados de polieletrólitos variando-se os parâmetros que influenciam a adsorção (pH, força iônica, densidade de carga), além de investigar a estabilidade térmica e possíveis transições de fases nesses filmes multicamadas como função do pH das soluções e o do número de camadas. A espectroscopia SFG de filmes dos polieletrólitos poly(allylamine hydrochloride) (PAH) e poly(styrene sulfonate) (PSS) permitiu acompanhar a adsorção das camadas pelo monitoramento do campo elétrico na interface (substrato+filme adsorvido)/solução. As medidas de fase do sinal SFG confirmaram a supercompensação de cargas em todos os valores de pH estudados, exceto a pH 12, onde a adsorção foi possível devido a interações eletrostáticas locais. Os filmes secos mostraram grande ordenamento e homogeneidade quando a secagem era espontânea (sem a ação de jato de N2), independentemente do pH. Nestes filmes, observou-se pela primeira vez que as camadas adsorvidas podem alterar o ordenamento e a conformação das cadeias previamente adsorvidas. A espectroscopia SFG também apontou para a redução da densidade de carga e do ordenamento molecular quando a força iônica era aumentada, devido ao efeito de blindagem eletrostática. Os filmes tornaram-se mais inomogêneos e desordenados em virtude da compensação extrínseca. O efeito da força iônica foi o de reduzir a densidade de carga e assim o ordenamento molecular, mesmo se a secagem fosse espontânea. A técnica de SHG foi aplicada a filmes automontados de PAH e PS-119 para confirmar sua estabilidade térmica em função do pH e do número de camadas, além de verificar o ordenamento molecular antes e após o tratamento térmico. Os resultados mostraram que os filmes não são termicamente estáveis: o sinal é completamente destruído à temperatura de 150oC aproximadamente, ao contrário do que relata a literatura. As medidas SHG também confirmaram a isotropia dos filmes no plano das amostras, independente do pH ou do número de camadas. Comparando-se o sinal SHG antes e depois do aquecimento, comprovou-se que após o resfriamento lento, o sinal era restituído a quase o mesmo valor que antes, mostrando que o processo de desordem térmica é reversível. Entretanto, nenhuma transição de fase foi observada, pois a redução do sinal SHG foi lenta e gradual, sem nenhuma variação brusca que caracterizasse uma transição vítrea. Enfim, nossas medidas do sinal SHG em função do número de camadas também discordaram dos resultados da literatura, pois a susceptibilidade de segunda ordem não cresceu linearmente com o número de bicamadas. Isso indica que as moléculas não adsorvem com mesmo ordenamento em cada bicamada. Desse modo, podemos concluir que as técnicas SFG e SHG fornecem informação a nível microscópico que podem levar ao aprimoramento das aplicações dos filmes automontados, e que seriam difíceis de obter com técnicas tradicionais. / In this study, we have applied second-order nonlinear optical techniques, in particular Sum-Frequency Generation (SFG) and Second-Harmonic Generation (SHG), to investigate the adsorption and the molecular ordering of self-assembled polyelectrolyte films varying the parameters which are relevant to polyelectrolyte adsorption (pH, ionic strength, charge density), besides investigating the thermal stability and possible phase transistions in these multilayer films as function of pH of the solutions and of the number of layers. SFG spectroscopy of films fabricated with the polyelectrolytes PAH and PSS allowed us to monitor the adsorption of each layer by the electric field at the (substrate+adsorbed film)/solution interface. Phase-measurements of the SFG signal confirmed that charge supercompensation occurred at all pH values investigated, except at pH 12, where the adsorption was possible by local electrostatic interactions. Dry films have shown great order and homogeneity if the drying was spontaneous (without blow-drying with N2), independently of pH. In these films, it was observed for the first time that layer adsorption can modify the order and the conformation of previously adsorbed chains. SFG spectroscopy also pointed to the reduction of the charge density and of the molecular order if the ionic strength was increased, due to the electrostatic screening effect. The films were more inhomogeneous and disordered due to extrinsic charge compensation. The effect of the ionic strength was to reduce the charge density and the molecular order, even if the drying were slow (spontaneous). The SHG technique was applied to LBL films of PAH and PS-119 to confirm their thermal stability as a function of pH of the solutions and the number of layers, besides comparing the molecular order before and after the thermal treatment. The results have shown that the films are not thermally stable, with the SHG signal nearly vanished if the temperature of 150 oC is reached, in contrast of what is reported in the literature. SHG measurements have also confirmed that the films are isotropic in the plan of the samples, independent of pH or the number of layers. Comparing the SHG signal before and after heating, it was found that the SHG signal was considerably reduced at high temperatures, but after slow cooling it was recovered to almost the same value as before heating, showing that the thermal disorder is reversible. However, no phase transistion was observed, since the SHG signal reduction was slow and gradual, without any sudden change that would characterize a glass transition. At last, our SHG measurements as a function of the number of layers also disagreed with results in the literature, therefore the second order susceptibility did not grow linearly with the number of bilayers. This indicates that the molecules do not adsorb with same order in each bilayer. Therefore, we can conclude that SFG and SHG techniques provide information on the film arrangement at the microscopic level which could be difficult to get with traditional techniques and could also lead to the improvement of applications of LBL films.

O diagnóstico preciso das características morfológicas e metabólicas de um tecido e/ou órgão com a finalidade de identificar alterações patológicas, ou avaliar um determinado tratamento, é de grande importância nas áreas de biologia e medicina. Uma excelente alternativa para este diagnóstico, e que permite uma visualização com resolução celular, são imagens de microscopia óptica. Tradicionalmente, analisam-se as características celulares através de processos histológicos; contudo, mais recentemente essa mesma análise tornou-se possível em tecidos sem a necessidade deste preparo histológico. Fenômenos de óptica não-linear, como a fluorescência devido à absorção de dois fótons e a geração de segundo harmônico, são exemplos de processos que podem ser realizados sem preparo histológico com o objetivo de se obter imagens microscópicas em diferentes profundidades com resolução celular. Este projeto teve por objetivo desenvolver um microscópio óptico de varredura a laser baseado em processos ópticos não lineares, para adquirir imagens de tecidos e órgãos, nas condições in vitro, in vivo e ex vivo. O microscópio óptico montado é composto por: um laser de pulsos ultracurtos sintonizável (Ti:Safira), um sistema de varredura espacial (dois espelhos conectados a galvanômetros e conjugados por dois espelhos esféricos, para varredura lateral, e uma plataforma piezoelétrica para varredura axial), uma lente objetiva (20X, abertura numérica de 1,0, imersão em água e distância funcional de 2,0 mm) e um sistema de aquisição e controle. A resolução lateral obtida foi de (0,8±0,1) μm e axial de (4,4±1,5) μm, suficiente para a realização de imagens com resolução subcelular de tecidos biológicos. Imagens de fluorescência e por geração de segundo harmônico foram obtidas com sucesso a partir de tecido ex vivo de pele e fígado de rato, pele de porco e de membrana corioalantóica. Estas imagens revelaram aspectos tidos como relevantes na análise morfo-histopatológica – como estruturas nucleares e de membrana, e a presença de colágeno, e com vantagens como coleta de informação vinda de diferentes camadas do tecido. A montagem desse sistema apresenta potencial para contribuir em estudos em diagnóstico e tratamento de lesões sejam feitos de modo que, no futuro, essa análise resulte em diagnósticos mais precisos e tratamentos mais efetivos. / Accurate diagnosis of the morphological and metabolic conditions of a tissue and/or an organ is essential to define the presence of pathological changes, and to evaluate the response during a number of treatments. The use of optical techniques for biological tissue imaging is an excellent alternative for this purpose. Such techniques allow non-invasive diagnostic procedures, with cellular resolution, and usually provide almost instantaneous response. The use of nonlinear optical techniques such as fluorescence promoted by two-photon absorption is one example of optical technique in which we obtain images of living tissue with spatial resolution at cellular level. The purpose of this study is the assembly and characterization of a custom-made non-linear microscope. This microscope allows customized adjustment for in vitro, in vivo and ex vivo imaging of biological samples. The excitation is done using a tunable femtosecond Ti:Sapphire laser. Two galvanometer mirrors conjugated by two spherical mirrors are used for the lateral scan and for the axial scan a piezoeletric stage is utilized. The light is focused in tissue by an 20X objective lens, in water immersion, numerical aperture of 1.0, and working distance of 2.0 mm. The lateral resolution obtained was (0.8 ± 0.1) μm and (4.4 ± 1.5) μm for axial resolution, which is sufficient for images with sub-cellular resolution to be achieved in biological tissues. Fluorescence and second harmonic generation images were performed using epithelial and hepatic tissue. Those images revealed aspects considered relevant in morpho-histopathology – such as nuclear and citoplasm membrane structures, and the presence of collagen. By means of the microscope it is possible to have images in different depths of tissues with sub-cellular resolution. The assembly of such an equipment shall represent a potential contribution to diagnostics and lesion treatment fields, so that it may result in more precise detection of diseases and more effective treatments in the future.

Polarization specific measurements are advancing the capabilities of scientific instruments looking for ever smaller effects and material parameters. For example, the magneto-optical nonlinear Faraday effect can be used to characterize various electric and magnetic polarizability parameters of an individual molecule. Another major application is detection of desired particles in a highly scattering environment, the physical effect of which has been extensively researched, and is being overcome by using time-gated and polarization techniques. The polarimeter sensitivity is limited by the extinction-ratio obtained from polarizers. Of available polarizer materials, naturally occurring Calcite crystals provide the best extinction ratios because of their good optical homogeneity and high birefringence. However, there is a need for polarization determination with higher sensitivities, and thus a necessity to find better polarizing materials and methods. I developed a next-generation polarimeter in an attempt to sensitively detect the second-order Faraday effect, along with a substance s chirality and Verdet constant. Also, I developed a device uniquely able to sensitively detect chiral signatures in the presence of massive depolarizing scattering. In addition, I begun developing a novel type of polarimeter based on the highly-polarization-sensitive nonlinear-optical process of harmonic generation, whose required crystals can be grown with extremely high quality.

Nonlinearities in quantum cascade lasers (QCL¡¯s) have wide applications in wavelength tunability and ultra-short pulse generation. In this thesis, optical nonlinearities in InGaAs/AlInAs-based mid-infrared (MIR) QCL¡¯s with quadruple resonant levels are investigated. Design optimization for the second-harmonic generation (SHG) of the device is presented. Performance characteristics associated with the third-order nonlinearities are also analyzed. The design optimization for SHG efficiency is obtained utilizing techniques from supersymmetric quantum mechanics (SUSYQM) with both material-dependent effective mass and band nonparabolicity. Current flow and power output of the structure are analyzed by self-consistently solving rate equations for the carriers and photons. Nonunity pumping efficiency from one period of the QCL to the next is taken into account by including all relevant electron-electron (e-e) and longitudinal (LO) phonon scattering mechanisms between the injector/collector and active regions. Two-photon absorption processes are analyzed for the resonant cascading triple levels designed for enhancing SHG. Both sequential and simultaneous two-photon absorption processes are included in the rate-equation model. The current output characteristics for both the original and optimized structures are analyzed and compared. Stronger resonant tunneling in the optimized structure is manifested by enhanced negative differential resistance. Current-dependent linear optical output power is derived based on the steady-state photon populations in the active region. The second-harmonic (SH) power is derived from the Maxwell equations with the phase mismatch included. Due to stronger coupling between lasing levels, the optimized structure has both higher linear and nonlinear output powers. Phase mismatch effects are significant for both structures leading to a substantial reduction of the linear-to-nonlinear conversion efficiency. The optimized structure can be fabricated through digitally grading the submonolayer alloys by molecular beam epitaxy (MBE). In addition to the second-order nonlinearity, performance characteristics brought by the third-order nonlinearities are also discussed, which include third-harmonic generation (THG) and intensity dependent (Kerr) refractive index. Linear to third-harmonic (TH) conversion efficiency is evaluated based on the phase-mismatched condition. The enhanced self-mode-locking (SML) effect over a typical three-level laser is predicted, which will stimulate further investigations of pulse duration shortening by structures with multiple harmonic levels.

¡@¡@We integrated the laser-heated pedestal growth (LHPG) system with accurately controlled electrodes to build up our in situ poling system. The ZnO and MgO doped periodically poled lithium niobate crystal fiber were fabricated with the poling system. This poling system has the advantage of convenience and fast growth, but the ¡§screen effect¡¨ caused by free charges which exist near the molten zone must be eliminated. The micro swing resulted from the electric force is a feasible solution, because it can disarrange the free charges and reduce the ¡§screen effect¡¨. However, without excellently controlled micro swing, the uniformity of the poled domain pitch will loose and the conversion efficiency can not be improved. After analysis of the measured current data, the approximate system current model was presented and the proportional dependence between system current and micro swing was verified. Thus the system current was applied as the micro swing feedback signal, with that the variation of the micro swing was reduced from 25% to 15%. The stability of CO2 laser power is also a dominant factor to determine the quality of poled crystal fiber. The variation of the CO2 laser power was controlled within 1%. All the complicated works and precise control during the crystal fiber growth were accomplished with the LabVIEW program. ¡@¡@A novel and simple self-cascaded SHG + SFG scheme is presented for the generation of tunable blue/green light using ZnO doped periodically poled lithium niobate crystal fiber (PPLNCF) with a single designed pitch. A PPLNCF with a uniform period of 15.45£gm, the maximum conversion efficiency for the second harmonic generation and the cascaded SHG + SFG blue light can reach up to -9.2 dB and -31.9 dB, respectively. The 3 dB bandwidth of the tunable blue light is 3 nm (475-478 nm). In order to expand the tuning bandwidth range, a QPM gradient periodical structure was designed and can provide a 3 dB bandwidth of 65 nm for the tunable blue/green light output by simulation. We have successfully grown a crystal fiber with the domain pitch of 18.9 £gm for the C-band wavelength converter. The crystal length is 1.8 mm, the effective nonlinear coefficient of the lithium niobate crystal fiber is 18.2 pm/V that equals 0.53¡Ñdideal (34.4 pm/V). The conversion efficiency for converting the CW laser in C-band is about -59.3 dB.

The nonlinear optical properties of semiconductor heterostructures, such as GaAsAl/GaAs alloys, are studied with analytic and numerical methods on the basis of quantum mechanics. Particularly, second and third-order nonlinear optical properties of quantum wells described by the various types of confining potentials are considered within the density matrix formalism. We consider a P&ouml / schl-Teller type potential which has been rarely considered in this area. It has a tunable asymmetry parameter, making it a good candidate to investigate the effect of the asymmetry on the nonlinear optical properties. The calculated nonlinear quantities include nonlinear absorption coefficient, second-harmonic generation, optical rectification, third-harmonic generation and the intensity-dependent refractive index. The effects of the DC electric field on the corresponding nonlinearities are also studied. The results are in good agreement with the results obtained in other types of quantum wells, such as square and parabolic quantum wells. The effects of the Coulomb interaction among the electrons on the nonlinear intersubband absorption are considered within the rotating wave approximation. The result is applied to a Si-delta-doped, square quantum well in which the Coulomb interaction among the electrons are relatively important, since there has been no work on the nonlinear absorption spectrum of the Si-delta-doped quantum well. The results are found to be new and interesting, especially when a DC electric field is included in the calculations.

In this study, we have developed a high performance multi-photon microscopic system to perform second- harmonic (SH) imaging on a tooth and a KTP crystal . The high sensitivity of the system allows acquisition rate of 300 seconds/frame with resolution at 512¡Ñ512 pixels. The surface SH signal generated from the tooth and the KTP crystal is also carefully verified through micro-spectroscopy, polarization rotation and wavelength tuning. In this way, we can ensure the authenticity of the signal. KTP crystal and the enamel that encapsulates the dentine is known to possess highly ordered structures. The anisotropy of the structure is revealed in the microscopic SH images of the tooth and the KTP crystal samples.

In this study, we have successfully developed a high performance transmission mode Laser scanning for SHG imaging. This setup is capable of acquiring images of size 512¡Ñ512 pixels at a rate of 5.4 seconds/frame. The of samples can thus be imaged, which reflects the samples¡¦ structure and symmetry.

In this study we demonstrate the use of third harmonic (TH) and second harmonic (SH) generation in imaging dental sections. Teeth are the hardest and most indestructible part in human body. The TH and SH greatly facilitate observation of porous structures and collagen within the dental sections, respectively. Strong SH has been found on various biological specimens, such as collagen, potato starch, and skeletal muscles. These materials all possess periodical nano-structures that are often referred as (nonlinear) bio-photonic structures. In particular, collagen is an extra-cellular structural protein and is a major component of bone, cartilage, skin, and other tissues. Collagen fibrils have a triple-helical structure and it is believed that this structure enables collagen to generate SH signal from a wide range of wavelengths in the infrared region. For comparison, microtubule structures within dentin, due to its large index mismatch with surrounding, can be clearly seen with THG imaging. The THG also facilitate observation of prismatic structures in enamel. The successful construction of a multi-photon laser scanning microscope that can operate in both reflection and transmission modes is the key for this study. A femtosecond, sync-pumped optical parametric oscillator (OPO) is used to generate second and third harmonics from dental sections. Dental sections have large index of refraction¡]n~1.68¡^and scatter visible light severely. The employment of excitation wavelength at 1260 nm greatly reduces scattering and absorption within the sample. Its corresponding SH and TH wavelengths are at 630 nm and 420 nm, respectively. Additionally, 3-D structural views are also reconstructed from the optically sectioned images by the use of specialized 3D image processing software.