Ce manuscrit présente le rayonnement de second harmonique provenant de plusieurs milieux diélectriques allant de la réponse interfaciale à la réponse volumique. Ce travail de thèse constitue une première étape dans le but d'étudier une bulle de savon dans un piège optique par génération de second harmonique. Deux axes de recherche sont ainsi explorés : d'une part l'étude de la génération de second harmonique sur deux tensioactifs le TTAB et le SDS, constituants de base d'une bulle de savon, et de l'autre l'élaboration d'un nouveau dispositif expérimental permettant d'allier un piège optique à une excitation de second harmonique par un laser femtoseconde. Dans un premier temps, on explicite le montage optique reposant sur le principe d'un microscope confocal inversé et les mesures associées de la réponse harmonique d'interface air/verre et air/eau. Dans un second temps, on s'intéresse comme objet modèle, en lieu et place de la bulle, à une microparticule de silice. Ainsi, on commence par analyser sa réponse harmonique en microscopie non linéaire quand celle-ci se trouve déposée sur une matrice de verre. L'étude de cet objet met en avant l'interdépendance entre les aspects d'optique linéaire mesurés à la longueur d'onde fondamentale et l'intensité harmonique mesurée. Par la suite, cette microsphère est placée au sein du piège optique réalisé par un second faisceau. Malgré la faible taille et la symétrie de la particule diélectrique, on parvient à mettre en évidence la réponse harmonique d'une particule unique piégée. Enfin, dans une dernière partie, on s'intéresse à caractériser la génération de second harmonique pour des solutions savonneuses, première étape dans la réalisation d'une bulle. Les mesures de diffusion de second harmonique en volume pour des solutions de TTAB et SDS de diverses concentrations montrent un comportement similaire et une singularité lors du passage de la concentration micellaire critique. Lors de l'étude du signal de second harmonique à l'interface air/eau savonneuse en revanche, on mesure des comportements différents pour des tensioactifs anioniques et cationiques, provenant de la charge de surface et de l'orientation de l'eau sous-jacente / This thesis reports an experimental study of harmonic radiation from various dielectric media. We both study second harmonic generation on interfaces and hyper Rayleigh scattering in solutions. We present the first step for the realization of the following project : the study of the second harmonic generation on an optically trapped soapy bubble. To do so, two main axis of investigation are developped. Firstly, we study the harmonic response of two commonly used surfactants such as TTAB, a cationic one and SDS carrying a negative charge. This study consits of understanding the main component of a soapy bubble. We investigate how harmonic intensity is modified with an increase of soap concentration. These experiements are carried both in volume and at the air/water interface. The harmonic scattered intensity shows similar features for SDS and TTAB, as a sudden drop appearing at the critical micelar concentration. However, on the surface, the two oppositely charged surfactants give a radically different evolution of second harmonic signal versus their concentration. Indeed, the water molecules of the surroundings behaves in an opposite manner with negative or positive charged surfactants. The second axis of research that we work on in this thesis, is on a novel experimental development. We combine an optical tweezer to trap microsized particles with a femtosecond laser probe to generate the second harmonic. This is a first step in order to trap a bubble and study it with second harmonic generation. This non linear inverted confocal microscope is used to study harmonic profil of an silica bead stuck on a sample. This study gives a glance of the complexity of the correlation between linear optics effects on the laser probe beam and the created harmonic intensity. We also perform experiments on a trapped particle and we measure the harmonic response of an unique particle

Lasers Raman são dispositivos que proporcionam uma maneira prática de transformar comprimentos de onda fundamentais em novas linhas espectrais via Espalhamento Raman Estimulado (Stimulated Raman Scattering - SRS). Quando combinados com outros processos de conversão não lineares, os lasers Raman fornecem acesso a comprimentos de onda na região do visível no espectro eletromagnético, que de outra maneira seriam de difícil acesso, como o laranja-amarelo, verde-limão e diversas linhas no azul. A grande vantagem dos lasers Raman é a possibilidade de geração de múltiplas frequências a partir de uma mesma combinação de cristais, tornando esse tipo de laser dispositivos baratos e compactos quando comparados a tecnologias como OPO. Neste trabalho um cristal de Nd:YVO4 foi bombeado por diodo, em configuração transversal, sendo o cristal o responsável pela emissão laser e pelo espalhamento Raman. Na primeira parte do trabalho, a cavidade utilizada apresentava alto fator de qualidade para o comprimento de onda fundamental (1064 nm) e foi estudada a operação laser do 1º Stokes (1176 nm) em regimes de operação quase contínua (q-cw) e contínua (cw). Foi explorada a configuração com uma dobra do feixe laser em ângulo rasante na superfície de bombeamento, bem como a configuração com duas dobras nesta mesma superfície (double beam mode controlling - DBMC). Na segunda parte do trabalho, um cristal LBO foi utilizado para a geração do segundo harmônico (SHG) em 588 nm, o que corresponde a um laser laranja-amarelo. Foi utilizada a configuração com uma dobra e operação cw,com a qual a cavidade apresentava alto fator de qualidade tanto para o 1064 nm quanto 1176 nm. Com a configuração de uma dobra, foi demonstrado que o laser Raman opera em multimodo, com uma variedade de modos de Hermite-Gauss que puderam ser selecionados através apenas do alinhamento da cavidade, incluindo o modo TEM00. Com configuração DBMC, o laser apresentou operação estável oscilando o modo TEM00. Em 1176 nm em regime q-cw, foi obtida a potência máxima de 8,2 W por pulso (multimodo) e 11,7% de eficiência óptica de conversão (diodo para o 1º Stokes), e operando em modo TEM00 a potência máxima de 3,7 W por pulso e eficiência de 5,4% foi obtida com a configuração de duas dobras, de maneira que a tecnologia DBMC se mostrou eficiente para geração de um laser robusto e estável operando com o modo TEM00. Em regime cw o melhor resultado em termos de potência e eficiência foi obtido com a configuração de uma dobra, correspondendo a 1,8 W e 7,3% de eficiência com o laser operando em multimodo. Com o laser laranja, foi demonstrada a operação do modo TEM00 para potências de bombeamento abaixo de 14,5 W. A potência máxima obtida em multimodo foi 820 mW correspondendo a 4% de eficiência óptica de conversão. / Raman lasers are devices that provide practical means to shift fundamental laser wavelengths into new spectral lines via Stimulated Raman Scattering (SRS). When combined with other nonlinear conversion processes, Raman lasers permit access to hard-to-reach regions of the visible electromagnetic spectrum, for example, orange-yellow, lime-green and several blue lines. The great advantage of Raman lasers is the possibility of generating multiple wavelengths using the same set of crystals, which make these devices compact and practical when compared to other technologies as OPOs. In this work, the Nd:YVO4 crystal was laterally pumped by a diode laser and this crystal was responsible for laser generation as well as SRS. In the first part of this work, the laser cavity presented a high Q factor for the fundamental laser wavelength (1064 nm) and the laser operation at the first Stokes (1176 nm) was characterized under quasi-continuous wave operation (q-cw) and in continuous wave (cw) operation. The grazing incidence geometry of the cavity with a single bounce of the laser beam at the pumped facet of the crystal was exploited, as well as with the double bounce (double beam mode controlling - DBMC) of the laser beam at this same crystal facet. In the second part of this work, a LBO crystal was utilized for the second harmonic generation (SHG) at 588 nm, which corresponds to an orange-yellow laser. The single bounce cavity configuration was utilized under cw operation, which presented high Q factor at 1176 nm and at 1064 nm. With the single bounce configuration, the laser operated in a variety of Hermite- Gaussian transversal modes that could be selected simply by cavity alignment, including the TEM00 mode. With the DBMC technology, the laser presented stable operation of the TEM00 mode. At 1176 nm, under q-cw regime, the maximum output peak power of 8.2 W (multimode) was achieved, corresponding to an optical conversion efficiency (diode to 1st Stokes) of 11.7%, and operation of the TEM00 mode yielded a maximum output peak power of 3.7 W and 5.4% efficiency with the double bounce configuration, hence the DBMC technology showed to be an efficient method for the generation of a stable and robust laser operating with TEM00 mode. Under cw regime, the best result in terms of power and efficiency was obtained with the single bounce geometry, yielding 1.8 W (multimode) corresponding to 7.3% efficiency. For the orange-yellow laser, operation of the TEM00 laser mode was demonstrated for low pump powers up to 14.5 W. The maximum output power achieved in multimode operation was 820 mW and 4% optical conversion efficiency.

Lasers de estado sólido sintonizáveis com uma estreita largura de linha de emissão na região do vermelho são uma alternativa conveniente aos lasers de corante para aplicações em espectroscopia de alta resolução. Nesse trabalho, foram investigados lasers contínuos de Nd:YLiF4 e Nd:YVO4 operando em frequência única na região de 1,32 - 1,34μm, assim como a geração de segundo harmônico (GSH) desses lasers usando cristais de BiB3O6 (BiBO) e KTiOPO4 com inversão periódica de domínios (ppKTP), para a obtenção da emissão no vermelho (0,65 - 0,67μm). Utilizando um laser de Nd:YVO4 operando em frequência única em uma configuração em anel com um cristal não linear BiBO do tipo I, demonstrou-se o recorde de 680mW no vermelho em 671,1nm, sem a utilizaçãde nenhum elemento seletivo. Uma intonia em todo o ganho (~4 nm) foi obtida atravésda inserção de um etalon com filme refletor (R = 40%) e com 100μm de espessura, o que reduziu a potência de saída no vermelho para 380mW no comprimento de onda de maior ganho (671,15 nm). Em 1342nm foi demonstrada uma potência de saída de 1,5W em frequência única quando utilizado um espelho de saída com transmissão de 2%. Foi demonstrado ainda uma ótima eficiência de conversão de segundo harmônico em um laser em anel de Nd:YLF na polarização π (λ = 1321,5nm) quando usando um cristal de ppKTP. Este laser forneceu 1,4W em frequência única no vermelho em 660,5nm. Essa potência é a máxima que pode ser extraída desse laser no segundo harmônico e no fundamental quando utilizado um espelho com transmissão ótima. Utilizando um etalon com filme refletor (R = 25%), o laser pôde ser sintonizado em Δλ ~ 1,6nm. / All solid-state continuous-wave (cw) narrow emission linewidth and tunable red lasers are convenient alternative sources to bulky and expensive dye-lasers for highprecision laser spectroscopy. Single-frequency operation of diode-pumped Nd:YLiF4 and Nd:YVO4 cw ring lasers were investigated in the 1.32 - 1.34μm range, together with their intracavity second-harmonic generation (SHG) to the red spectral range (0.65 - 0.67μm) using either BiB3O6 (BiBO) or periodically-poled KTiOPO4 (ppKTP) crystals. We report on such a single-end diode-pumped Nd:YVO4 unidirectional red ring laser containing a type-I cut BiBO nonlinear crystal, yielding a record of 680 mW of single-longitudinal mode (SLM) red output power at 671.1nm without any intra-cavity etalon. For smooth SLM wavelength tuning over the full gain bandwidth (4 nm), a partially-coated (R = 40%) 100m-thin etalon was found necessary, reducing the maximum SLM power (at 671.15 nm) to 380 mW. At 1342.5nm and with a T = 2% transmission output coupler, the laser provided an optimal 1.5W of single-frequency power. We demonstrate also optimal intracavity SHG of a Nd:YLF ring laser in the π - polarization ( λ= 1321.5nm) using a ppKTP. The laser yielded 1.4 W of singlefrequency red power at 660.5 nm, as much as the maximum fundamental power that can be extracted from the resonator using an optimal output coupler. With a partiallycoated (R = 25%) thin etalon, the laser was tunable over Δλ ~ 1.6nm.

Cette thèse s’intéresse à une technique de caractérisation particulièrement bien adaptée à l’étude de couches diélectriques ultra-minces sur semiconducteurs. La génération de seconde harmonique (SHG) est une méthode très prometteuse, basée sur l’optique non-linéaire. Un laser est focalisé sur l'échantillon à caractériser et le signal à deux fois la fréquence fondamentale est mesuré. Pour les matériaux centrosymétriques comme c-Si, SiO2 et Al2O3, le signal SHG est dû aux défauts et au champ électrique Edc d’interface (induit par les charges préexistantes Qox et/ou piégées au niveau des pièges d’interface Dit). La SHG donne ainsi accès à la qualité des interfaces entre diélectriques/semiconducteurs. Néanmoins, le signal SHG dépend aussi des phénomènes de propagation optique dans les structures multicouches. Pour cette raison, nous avons développé un programme de simulation qui prend en compte les phénomènes optiques et les champs électriques statiques aux interfaces. Nous avons utilisé la SHG pour analyser la qualité de passivation de structures Al2O3/Si préparées avec des procédés différents et nous avons montré une corrélation entre SHG et mesure de durée de vie des porteurs de charges. Les valeurs de Qox et Dit ont été extraites par des mesures de capacité-tension et elles ont permis de calculer le champ Edc. La simulation optique, avec les valeurs extraites de Edc a permis de reproduire les données expérimentales de SHG dans ces structures. La SHG a été utilisée également pour la caractérisation des substrats Silicium-sur-Isolant (SOI). Pour les structures SOI épaisses, la simulation et les résultats expérimentaux ont montré que la réponse SHG est dominée par les interférences optiques (faible impact de Edc). Pour les structures SOI ultraminces, les interfaces sont couplées électriquement et des valeurs de Edc sont nécessaires pour reproduire les données expérimentales par simulation. Cela implique que pour les SOI ultraminces, la SHG pourrait donner accès aux champs électriques au niveau des interfaces d’une manière non-destructive. / This PhD work was developed in the context of research for novel characterization methods for ultra-thin dielectric films on semiconductors and their interfacial quality. Second harmonic generation (SHG) is a very promising non-invasive technique based on nonlinear optics. A laser emitting at the fundamental frequency is incident upon the sample which responds through its 2nd order polarization, generating a signal at twice the fundamental frequency. For centrosymmetric materials such as c-Si, amorphous SiO2 or Al2O3, the SHG signal is mainly due to the defects and to the static electric field Edc present at the interface (due to pre-existing charges Qox and/or photo-injected charge trapping/detrapping at interface traps Dit). Thus, SHG measurement gives access to the quality of dielectric/semiconductor interfaces. Nevertheless, the SHG signal is also dependent on multilayer optical propagation phenomena. For this reason, we have developed a simulation program which accounts for the optical phenomena and the static electric fields at the interfaces. We have used SHG to monitor the passivation quality of Al2O3/Si structures prepared with different processes and showed a correlation between SHG and minority carrier lifetime measurements. Qox and Dit were extracted from capacitance-voltage measurements and helped calculating the Edc values. The optical simulation, fed with known Edc values reproduced the experimental SHG data in these structures. The SHG was also used for Silicon-on-Insulator (SOI) substrates characterization. In thick SOI structures, both simulations and experimental results show that the SHG response is mainly given by optical interferences (Edc has no impact). In ultrathin SOI, the interfaces are electrically coupled and Edc is needed as input in the simulation in order to reproduce the experimental SHG data. This implies that in ultrathin SOI, SHG can access the interface electric fields in a non-destructive way.

Optical frequency standards with the reference to a narrow electronic transition of a laser-cooled collection of neutral atomic particles are becoming essential tools of research in modern precision physics experiments. In the core of a building block of an optical frequency standard is the optical continuous wave laser that has a good spectral purity of the emitted light. Such a stable optical oscillator is highly desirable in high resolution spectroscopy, if it emits in a good quality beam at a short visible wavelength. This Master thesis explores efficient techniques for building such an optical frequency source intended for use in the cooling and trapping of Calcium atoms scheme. The strong dipole transition at the blue wavelength in the atomic Calcium is needed to reduce the kinetic energy of atoms by nearly six orders of magnitude. A further reduction in the thermal energy of the laser cooled atoms is required to locate with ultra-high precision the 400 Hz narrow clock transition of the stable 40Ca isotope. The experimental methods that achieve this and approach sub-microkelvin temperature of the laser cooled bosonic isotopes of alkaline earths are inspected. The blue laser with a uniform intensity distribution in the beam is useful to maintain the trapped number of cold atoms during these experiments. The spectroscopic properties of the relative transitions in Calcium atom are also reviewed following relevant publications in the area. The constructed blue laser can be used as a primary wavelength source in the lasers network for cooling and trapping of Calcium atoms. These experiments will constitute part of the project to build an optical atom clock referenced to 40Ca narrow linewidth transition. The blue laser is constructed by generating second harmonic in a Potassium Niobate crystal, which is temperature controlled to use a type-I noncritical phase-matching of the optical nonlinear process. The power of the intracavity-generated second harmonic depends on the resonance properties of the optical resonator where this nonlinear crystal is placed. The study is aimed at characterising the designed optical resonator and the experimental parameters that describe it. The formula is derived that relates the resonance power enhancement coefficient with finesse and the power coupling contrast of a passive optical cavity. The obtained relationship is verfied during the experiments. The produced efficiency of the intracavity second harmonic generation is approx. 0.0023 mWblue/(mWred)2. The research work also examines the noise characteristics of the infrared diode laser that is used as a pump source for the intracavity generated second harmonic and determines the spectroscopic precision of the produced blue light. The frequency locking experiment is analysed using the unbalanced scheme of the polarisation stabilisation technique. The designed optical buildup cavity became a part of the unbalanced frequency discriminator in such a scheme. The results demonstrate high gain of frequency noise suppression of the stabilised laser. The unbalanced arrangement of the H}ansch-Couillaud technique has been possible due to a very low amplitude noise of semiconductor lasers.

In this thesis, we report the observations of optical squeezing from second harmonic generation (SHG), optical parametric oscillation (OPO) and optical parametric amplification (OPA). Demonstrations and proposals of applications involving the squeezed light and electro-optic control loops are presented. ¶ In our SHG setup, we report the observation of 2.1 dB of intensity squeezing on the second harmonic (SH) output. Investigations into the system show that the squeezing performance of a SHG system is critically affected by the pump noise and a modular theory of noise propagation is developed to describe and quantify this effect. Our experimental data has also shown that in a low-loss SHG system, intra-cavity nondegenerate OPO modes can simultaneously occur. This competition of nonlinear processes leads to the optical clamping of the SH output power and in general can degrade the SH squeezing. We model this competition and show that it imposes a limit to the observable SH squeezing. Proposals for minimizing the effect of competition are presented. ¶ In our OPO setup, we report the observation of 7.1 dB of vacuum squeezing and more than 4 dB of intensity squeezing when the OPO is operating as a parametric amplifier. We present the design criteria and discuss the limits to the observable squeezing from the OPO.We attribute the large amount of squeezing obtained in our experiment to the high escape efficiency of the OPO. The effect of phase jitter on the squeezing of the vacuum state is modeled. ¶ The quantum noise performance of an electro-optic feedforward control loop is investigated. With classical coherent inputs, we demonstrate that vacuum fluctuations introduced at the beam splitter of the control loop can be completely cancelled by an optimum amount of positive feedforward. The cancellation of vacuum fluctuations leads to the possibility of noiseless signal amplification with the feedforward loop. Comparison shows that the feedforward amplifier is superior or at least comparable in performance with other noiseless amplification schemes. When combined with an injection-locked non-planar ring Nd:YAG laser, we demonstrate that signal and power amplifications can both be noiseless and independently variable. ¶ Using squeezed inputs to the feedforward control loop, we demonstrate that information carrying squeezed states can be made robust to large downstream transmission losses via a noiseless signal amplification. We show that the combination of a squeezed vacuum meter input and a feedforward loop is a quantum nondemolition (QND) device, with the feedforward loop providing an additional improvement on the transfer of signal. In general, the use of a squeezed vacuum meter input and an electro-optic feedforward loop can provide pre- and post- enhancements to many existing QND schemes. ¶ Finally, we proposed that the quantum teleportation of a continuous-wave optical state can be achieved using a pair of phase and amplitude electro-optic feedforward loops with two orthogonal quadrature squeezed inputs. The signal transfer and quantum correlation of the teleported optical state are analysed. We show that a two dimensional diagram, similar to the QND figures of merits, can be used to quantify the performance of a teleporter.

This thesis deals with the fabrication and the characterization of periodically-poled crystals for use in lasers to generate visible and UV radiation by second-harmonic generation (SHG) through quasi-phasematching (QPM). Such lasers are of practical importance in many applications like high-density optical storage, biomedical instrumentation, colour printing, and for laser displays. The main goals of this work were: (1) to develop effective monitoring methods for poling of crystals from the KTiOPO4 (KTP) family, (2) to develop useful non-destructive domain characterization techniques, (3) to try to find alternative crystals to KTP for easier, periodic poling, (4) to investigate the physical mechanisms responsible for optical damage in KTP. The work shows that the in-situ SHG technique used together with electro-optic monitoring, makes it possible to obtain reliable, real-time information regarding the poling quality over the whole crystal aperture during the electric-field poling process. Using this combined monitoring method, both KTP and Rb-doped KTP (RKTP) crystals were successfully poled. By comparing these two crystals, we found that a low-doped KTP has a substantially reduced ionic conductivity and, thus, a high-quality periodic poling can be obtained without otherwise affecting the properties of the crystal. RKTP is a good alternative candidate to KTP for poling purpose. We have also shown that Atomic Force Microscopy (AFM) is an informative tool for investigating domain nucleation, growth, and merging. Furthermore, we have demonstrated a simple technique for 3D characterization of QPM samples. It utilizes a group-velocity mismatched, type-II SHG of femtosecond pulses for layer-by-layer monitoring of the effective nonlinearity along the propagation direction of the beam. The quality of these crystals was finally reflected in a number of SHG experiments with a variety of laser sources. High energies and high efficiencies were thus demonstrated using CW, mode-locked and Q-switched lasers. Gratings with pitches smaller than 3 µm, were demonstrated for first-order UV generation. Type-II QPM SHG was demonstrated as a technique for reducing the fabrication constraints. High intensity light in the visible and the UV leads to modification of the material properties and, eventually, to optical damage. In KTP and its isomorphs, the first sign of material change is an optically-induced absorption. We have used thermal-lens spectroscopy with a common-path interferometer for high-sensitivity measurements of green light-induced infrared absorption dynamics in single-domain and periodically-poled KTP (PPKTP). The saturated, green light-induced absorption has been shown to be consistently higher in periodically-poled crystals, and is attributed to the creation of stoichiometric and interstitial defects in the crystals during the poling process. Finally, irreversible bulk damage thresholds in PPKTP have been determined for pulsed frequency converters. As the characteristics of optical damage are closely related to the material quality, this investigation can provide useful information for crystal manufactures and will help to optimise the crystal growth conditions.

Optical parametric oscillators (OPOs) and optical parametricamplifiers (OPAs) constitute a class of optical frequencyconverting devices that have many possible applications, e.g.in range finding, molecular spectroscopy and medicine. They canconvert the frequency of the incident pump field with highefficiency, and generate two waves at new frequencies that willbe continuously tuneable over a wide spectral range. Virtuallyany wavelengths within the transparency region of the nonlinearmaterial can be generated if the material can bequasi-phasematched (QPM). In addition, QPM gives thepossibility to utilise the largest nonlinear tensor element ofthe material and allows walk-off free interaction between thewaves. The aims of this thesis have been to investigate thepossibility to use QPM KTiOPO4crystals as nonlinear material in nanosecond OPOsand OPAs operating at room-temperature, and to explore theadvantages and shortcomings of these devices. The technique ofelectric field poling has been employed to implement the QPMstructure in flux grown KTiOPO4(KTP). The main conclusion is that periodically poled KTP (PPKTP)is a suitable material to use in nanosecond OPOs and OPAs. Thematerial properties that foremost make KTP into an attractivenonlinear material are: The large value of the nonlinearcoefficient d33, the high resistance to optically inducedbreakdown, the low susceptibility to grey-track formation, theinsensitivity to the photorefractive effect, the widetransparency and the low coercive field. The thesis shows that it is possible to pole large volumesof KTP with a high quality of the QPM structure. Highlyefficient nanosecond OPOs have been constructed during thisproject. Maximum conversion efficiencies have reached 45 % inthe case of a singly resonant OPO (SRO) built around a 3 mmthick PPKTP crystal. Total pulse energies for both the signal(1.72 µm) and the idler (2.8 µm) of up to 18 mJ wasreached and an average output power of 2 W was obtained forthis sample. However, up to 24 W was produced in a doublyresonant OPO operating close to degeneracy. The efficiencyreached 48 % for that case. Truly continuous and very widespectral tuning has also been demonstrated, as well as a narrowbandwidth OPO operating on one single longitudinal mode. <b>Keywords:</b>optical parametric oscillators, opticalparametric amplifiers, quasi-phasematching, KTiOPO4, nonlinear optics, frequency conversion, periodicelectric field poling, ferroelectrics, high-order secondharmonic generation, electro-optic effect.

Ferroelectric crystals are commonly used in nonlinear optics for frequency conversion of laser radiation. The quasi-phase matching (QPM) approach uses a periodically modulated nonlinearity that can be achieved by periodically inverting domains in ferroelectric crystals and allows versatile and efficient frequency conversion in the whole transparency region of the material. KTiOPO4 (KTP) is one of the most attractive ferroelectric non-linear optical material for periodic domain-inversion engineering due to its excellent non-linearity, high resistance for photorefractive damage, and its relatively low coercive field. A periodic structure of reversed domains can be created in the crystal by lithographic patterning with subsequent electric field poling. The performance of the periodically poled KTP crystals (PPKTP) as frequency converters rely directly upon the poling quality. Therefore, characterization methods that lead to a deeper understanding of the polarization switching process are of utmost importance. In this work, several techniques have been used and developed to study domain structure in KTP, both in-situ and ex-situ. The results obtained have been utilized to characterize different aspects of the polarization switching processes in KTP, both for patterned and unpatterned samples. It has also been demonstrated that it is possible to fabricate sub-micrometer (sub-μm) PPKTP for novel optical devices. Lithographic processes based on e-beam lithography and deep UV-laser lithography have been developed and proven useful to pattern sub- μm pitches, where the later has been the most convenient method. A poling method based on a periodical modulation of the K-stoichiometry has been developed, and it has resulted in a sub-μm domain grating with a period of 720 nm for a 1 mm thick KTP crystal. To the best of our knowledge, this is the largest domain aspect-ratio achieved for a bulk ferroelectric crystal. The sub-micrometer PPKTP samples have been used for demonstration of 6:th and 7:th QPM order backward second-harmonic generation with continuous wave laser excitation, as well as a demonstration of narrow wavelength electrically-adjustable Bragg reflectivity. / QC 20100930

This thesis provides an extensive study of the first molecular hyperpolarizability b of charge-transfer chromophores using hyper-Rayleigh scattering (HRS). The charge-transfer chromophores used in present work involve the tricyanohydrofuran¡]TCF¡^group as an electron acceptor, and/or thiophene in the pi-electron bridge. TCF is a very strong electron acceptor and thiophene greatly lowers the resonance energy. Their presence significantly increases the beta value of the chromophore, therefore enhancing potentials in applications. In hyper-Rayleigh scattering experiments, the laser radiation with tunable wavelengths is used as an excitation source for measuring the frequency dependence of beta. The experiment shows beta exhibiting a significant dispersion in the two-photon resonance region. Using the linear absorption spectrum in coordination with theory, we show that it is possible to use Kramers-Kronig (K-K) transform to reproduce the experimental beta value in the two-photon resonance region. The K-K approach provides an extension to the conventional Oudar-Chemla equation, which is invalid in the spectral region in which two-photon resonance occurs. Using the new approach, it is shown that reliable values of intrinsic hyperpolarizabilities beta_zero of charge-transfer chromophores can be extracted. The coordination of beta_zero with molecular structure provides one with an insight for the origin of the enhancement of the first molecular hyperpolarizability of charge-transfer chromophores. This thesis examines the variation of beta_zero with molecular structure. The same technique is also applied to a dendrimer that has charge-transfer nonlinear optical chromophores incorporated in the dendritic structure. The measured frequency dependent hyperpolarizability of the dendrimer is compared with that calculated from the linear absorption spectrum by the KK transform technique. The intrinsic hyperpolarizability beta_zero of the dendrimer obtained is compared with that of the single chromophore having a structure similar to that incorporated in the dendrimer. The comparison shows that the 3D dendritic structure is effective in reducing the interaction between chromophores by providing sufficient space between them, hence avoiding the possibility of aggregation formation due to attractive interactions between chromophores. The topic of two-photon fluorescence (TPF), which is related to HRS, is also investigated. The intensity of TPF is generally proportional to the square of the incident excitation intensity. Careful measurements of the TPF intensity of a nonlinear optical chromophore in conjunction with required auxiliary parameters have been used as a technique for determining the two-photon absorption cross-section. The TPF intensity measurement carried out in this thesis uses a variety of intensities. At low intensity excitation, the TPF intensity follows the usual quadratic intensity law (QIL), whereas deviations from the QIL are observed at higher incident intensities. The observation of similar lineshape associated with one- and two-photon fluorescence spectra suggests a 3-level model for the description of TPF excited by the incident intensity at various strengths. It is shown that by fitting the observed TPF intensity to an equation developed from the three-level model, it is possible to deduce the two-photon absorption cross section of the nonlinear optical chromophore in solution. The new technique developed using the three-level model is tested on a Rhodamine B/Chloroform solution. The two-photon absorption cross-section obtained by using the new technique is found in agreement with that reported in the literature. Having demonstrated the suitability of the new technique, it is used to determine the two-photon absorption cross-section of a novel nonlinear optical chromophore. The two-photon absorption cross-section using the new technique is then compared with that obtained by the nonlinear transmittance method. The two results are in good agreement, indicating the applicability of the new technique. The new technique is more convenient than the conventional low excitation TPF method as it does not require various auxiliary parameters, some of them are difficult to obtain. The second harmonic generation (SHG) of a chromophore/polymer film which is optically poled by using a coherent superposition of a fundamental and its second harmonic beams. The growth rate of the SHG intensity is found to be proportional to the fourth power of the incident intensity of the fundamental beam, and the plateau intensity SHG is proportional to the square of the incident intensity. These observations are not in agreement with the published theory. While the reason for disagreement is yet to be clarified, the information obtained is useful for the development of nonlinear optical devices.