Ziel dieser Arbeit ist es, das Verständnis der durch plasmonische und Komposit-Nanomaterialien verursachten Verstärkung der Hyper-Raman Streuung zu vertiefen. Diese Nanostrukturen werden in oberflächenverstärkten Hyper-Raman-Streuung (surface enhanced hyper Raman scattering, SEHRS) Experimenten, die durch den nichtlinearen parametrischen Prozess der Frequenzverdopplung (SHG) und der oberflächenverstärkten Raman-Streuung (SERS) ergänzt werden, zur umfassenden Untersuchung organischer Moleküle und Materialien angewendet. Die SEHRS-Verstärkung von Goldnanopartikeln unterschiedlicher Form und Größe sowie von Metallfilmen bestehend aus periodisch angeordneten Hohlräumen (Nanovoids) wurde in Experimenten mit dem Farbstoff Kristallviolett bei einer Anregungswellenlänge von 1064 nm und durch numerische Simulationen untersucht. Die Ergebnisse zeigen, dass Aggregate von großen kugelförmigen Goldnanopartikeln und Nanostäbchen in Lösung eine sehr hohe elektromagnetische SEHRS-Verstärkung bewirken. Darüber hinaus können die Homogenität des Signals, die Reproduzierbarkeit in Bezug auf die Herstellung und die Substratstabilität im Vergleich zu früheren Ansätzen durch Verwendung von Nanovoids signifikant verbessert werden. Die Weiterentwicklung von Nanostrukturen für die multimodale Mehrphotonen-Spektroskopie ist hier anhand der Synthese und der optischen Charakterisierung von plasmonischen Bariumtitanat-Nanokompositen demonstriert. Eine systematische Studie der Wechselwirkung von Aminosäuren und aromatischen Thiolen mit Gold- und Silbernanopartikeln wurde mit SEHRS bei einer Anregungswellenlänge von 1064 nm und mit SERS bei Anregungswellenlängen im sichtbaren Spektralbereich durchgeführt. Zusammenfassend wurde in dieser Arbeit gezeigt, dass ein tieferes Verständnis und ein rationales Design verbesserter plasmonischer Nanostrukturen ermöglichen, SEHRS mit anderen Mehrphotonen-angeregten Effekten zu kombinieren und diese in der analytischen Chemie und Biophysik einzusetzen. / The aim of this work is to extend the understanding of the enhancement in surface enhanced hyper Raman scattering (SEHRS) generated by plasmonic and composite nanomaterials, and to apply these nanostructures in SEHRS experiments complemented by the non-linear parametric process of second harmonic generation (SHG) and by surface enhanced Raman scattering (SERS), for the comprehensive probing of organic molecules and materials. The enhancement from gold nanoparticles with different sizes and shapes as well as from metal films comprised of periodically arranged voids was investigated in SEHRS experiments at 1064 nm excitation using the crystal violet dye and by numerical simulations. The results indicate that aggregates of large spherical gold nanoparticles and nanorods in solution provide very strong electromagnetic enhancement of HRS. Moreover, the homogeneity of the signal, reproducibility in terms of fabrication, and substrate stability can be significantly improved compared to previous approaches by using nanovoid arrays. Further developments of enhancing nanostructures towards multimodal multiphoton spectroscopic applications are demonstrated here by the synthesis and optical characterization of plasmonic-barium titanate nanocomposites. A systematic study on the interaction of amino acids and aromatic thiols with gold and silver nanoparticles was conducted with 1064 nm-excited SEHRS and SERS excited in the visible spectral range. In conclusion, this work underlines that a better understanding and a rational design of improved plasmonic nanostructures allow to combine SEHRS and other multiphoton excited effects, and to use them in analytical chemistry and biophysics.

Diode lasers are a convenient and economical source of near-infrared radiation, which may usefully be applied to a host of different sensitive detection methods; this thesis presents novel extensions of these methods, making use of the favourable characteristics of this type of light source. The first part of this thesis details the development of an optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) apparatus, including the development of the optical system, the sample handling, and the electronics for feedback phase control. A preliminary demonstration of the system is reported, presenting the detection of atmospheric water absorptions close to 1596 nm. Optimisation and application of the OF-CEAS spectrometer are then demonstrated, after which the spectrometer is applied to the sensitive detection of carbon dioxide absorptions suitable as a diagnostic aid in identifying Heliobacter pylori infection. A time-normalised α-min value of 5.8 × 10⁻⁹ cm⁻¹s^1/2 was measured for these spectra. Further optimisation of the system leads to an ultimate detection sensitivity of 1.42 × 10⁻⁹ cm⁻¹s^1/2, measured on absorption transitions in acetylene close to 1532 nm. In order further to characterise the performance of the OF-CEAS system, analogous experiments are presented using the OF-CEAS setup and a standard diode-laser cavity-enhanced absorption spectroscopy (CEAS) apparatus. Detection is carried out on the P(6) line of the ν₁ + ν₃ vibrational band of the mixed isotopologue of acetylene, ¹²-C¹³-CH₂. Direct comparison is made between the sensitivities of the two methods, and in light of this the suitability of each technique for detection in different environments is considered. The well-characterised and consistent frequency scale which is inherent to the OF-CEAS technique is then applied to a line shape analysis for the presented absorption spectra. Pressure-broadening coefficients are determined for selected absorptions in the ν₁ + ν₃ band of acetylene. In spite of the low resolution associated with this technique, this accurate frequency scaling allows observation of subtle line shape effects such as Dicke collisional narrowing using the data presented in Chapter 3 for the R(60) line in the 3ν₁ + ν₃ vibrational band of CO₂. These effects are quantified through use of a Galatry fit to each absorption spectrum. The statistical significance associated with the use of such a model, and the physical meaning of the results, are examined and discussed. An alternative strategy for increasing the sensitivity of a diode-laser-based gas monitoring technique lies in moving detection to the mid-infrared region, where the absorption cross-sections are generally larger. With this motivation, difference frequency generation is presented, to produce radiation close to 3.5 µm which is then applied to a series of different enhanced spectroscopy techniques. The optimal sensitivity, of 32 ppb NO2 at 45 Torr total sample pressure, was achieved using wavelength modulation spectroscopy. The different techniques are compared and possible improvements to them are put forward. Finally, proof-of-principle work is presented seeking to combine the enhanced circulating power associated with the optical-feedback-locked techniques and non-linear optical techniques to move detection to a more favourable spectral region. Light close to 429 nm is generated by second harmonic generation in a crystal of potassium niobate, with resonance-enhancement afforded by a feedback V-cavity of the sort employed in OF-CEAS. The potential of such a system for diode-laser-based generation of blue and ultraviolet light is demonstrated and discussed, along with improvements that might be implemented to increase the efficiency of the system.

Ce travail contribue à l’évaluation de la technique de génération de seconde harmonique induite par un champ électrique quasi statique, ou technique EFISHG, appliquée au domaine de la microélectronique. Une description du principe de la technique EFISHG, basé sur l’optique non linéaire, permet d’appréhender l’origine physique de cette méthode. Un état de l’art a permis d’identifier deux champs d’applications liés à la microélectronique : l’analyse de défaillance, via la mesure en temps de réelle des variations de champs électriques internes dans les circuits intégrés, et la fiabilité par l’étude du piégeage de charges à l’interface Si/SiO2 et de la dégradation dite de « Negative Bias Temperature Instability » ou NBTI. Ce manuscrit présente les différentes étapes qui ont permis l’élaboration d’un banc de test en vue de l’évaluation de l’applicabilité de la technique EFISHG à ces problématiques. Les résultats expérimentaux obtenus avec ce montage ont permis de mettre en avant les possibilités qu’offre la technique EFISHG à caractériser et à accélérer le vieillissement NBTI. / This work concerns the elaboration of an industrial method for Single Event Effect (SEE) sensitivity testing on integrated circuits. The concerned SEEs are those produced by heavy ions and are mainly Single Event Upset (SEU) and Single Event Latchup (SEL). The original test approach chosen in this study relies on the use of infrared laser pulses striking the backside of the tested device. Laser pulse and heavy ion interaction with semiconductor materials are described and a presentation of the particle accelerator test and some former laser test methods is also given. Advantages and drawbacks of those two techniques are discussed. The developed experimental setup uses a near infrared fiber coupled Neodyme/YAG pulsed laser. Its different elements are described. Using this tool to characterise the SEU sensitivity of several modern SRAMs has allowed to define a test methodology. Its efficiency is discussed and illustrated by different experimental results.

Le but de ce travail de thèse est de contrôler via un traitement de polarisation les propriétés physico-chimiques de surface des verres. Pour cela, l'implémentation d'une charge d'espace au sein de différents verres silicates et borosilicates a été caractérisée. Ces études comparatives ont montré que la déplétion des cations de l’anode vers la cathode induit l’apparition d’un champ électrique et des modifications structurales localisées. De plus, nous avons démontré que la formation d’un plasma entre l’anode et le verre pouvait être à l’origine de phénomènes d'échanges ioniques conduisant notamment à la formation d’entités azotées NO2/N2O4 piégées dans le verre. Par la suite, une étude des propriétés physico-chimiques des surfaces polarisées a été conduite. Les résultats préliminaires obtenus concernent l'influence de la charge d'espace sur (i) la mouillabilité, (ii) la chimie de surface et (iii) les réponses optiques de molécules adsorbées. / The purpose of this work is to control physicochemical properties of glasses surfaces using a thermal polarization treatment. For this, the implementation of a space charge layer has been characterized for various silicates and borosilicates glasses. These comparative studies have shown that cations depletion from anode toward cathode induces both an electric field and structural local changes. To go further, we demonstrated that there is a plasma formation between anode and glass surfaces which could be the cause of ionic exchange phenomena leading to the formation of nitrogen NO2/N2O4 entities entrapped inside glass network. Subsequently, physicochemical properties studies of polarized surfaces were performed. Preliminary results concerning the space charge influence on (i) surface wettability, (ii) surface chemistry and (iii) optical responses of adsorbed molecules on poled glass surface have been obtained.

Saccharides, a class of organic materials, are potential candidates for nonlinear optical applications. Ascorbic acid is a sugar acid and is classified as a monosaccharide. The molecule of ascorbic acid has two chiral centers and, therefore, four stereoisomers. Among them, two are naturally occurring compounds; L-ascorbic acid and D-isoascorbic acid. From these two acids various salts and other derivatives could be synthesized. In this thesis, four compounds of the ascorbic acid family were selected for detailed study based on their nonlinearity, chemical and physical stability and their crystallization characteristics. The thesis is organized into seven chapters. The first chapter covers the theoretical background of nonlinear optics, especially, second harmonic generation. Second chapter details the experimental techniques and methodology adopted. Chapter 3 discusses the crystal structure, growth, physical and nonlinear optical properties of Lithium Disoascorbate monohydrate (LDAM). Detailed analysis of refractive index measurements employing Brewsters angle method and determination of phase matching curves, effective nonlinear coefficient, walk off angle etc are given. In Chapter 4, investigations on Sodium D-isoascorbate monohydrate (NDAM) are presented. Detailed characterization of the crystals including thermal, optical, dielectric properties are carried out. Analyses of dielectric dispersion based on Cole-Cole equation are discussed. Comprehensive studies on laser damage of the crystals are discussed. Chapter 5 discusses the nonlinear optical properties of the monoclinic D-isoascorbic acid (DIA). Chapter 6 presents studies on the triclinic Lithium L-ascorbate dihydrate (LLA) crystals. The crystals exhibit intense non-collinear second harmonic rings as they possesses large birefringence coupled with high second order nonlinear coefficients. The SHG conversion efficiency of these crystals is 15 times that of KDP. In the final chapter, a comprehensive summary of the work carried out is presented along with scope for further investigations.

The thesis entitled "Phase Behaviour in Crystalline Solids: Exploring the Structure Guiding Factors via Polymorphism, Phase Transitions and Charge Density Studies" consists of five chapters divided into two parts. A basic introductory section describes the topics relevant to the work and the methods and techniques utilized. Part A contains two chapters that discuss the structural aspects related to polymorphism, solvatomorphism, conformational preferences and phase transitions exhibited by active pharmaceutical ingredients (APIs). It also discusses the structure-property correlations in API crystal forms and the possible utility of second harmonic generation (SHG) for their bulk characterization. Part B has three chapters that discuss experimental and theoretical charge density analyses of intra-and intermolecular interactions that play structure guiding roles in some of the APIs discussed in Part A. The main focus of the present work is to characterize the interaction patterns devoid of strong classical hydrogen bonds. The case studies include multifurcated C - H …O hydrogen bonds, the “carbon bonding” and chalcogen interactions involving Se and S atoms. In addition to charge density studies, in situcryocrystallography and molecular complexation experiments have been employed to examine structural consequences of chalcogen bonding. Further, Appendices 1 and 2 describe phase transition studies on the inorganic mineral kröhnkite and its high temperature phase transitions leading to novel inorganic structural types. Part A: Polymorphism and phase behaviour in Active Pharmaceutical Ingredients (APIs) Chapter 1 discusses case studies of polymorphism, supramolecular preference sand phase transitions exhibited by active pharmaceutical ingredients (APIs). Section 1.1 deals with the polymorphism of an anti-oxidant drug candidate ebselen and its hydroxyl derivative. The potential of organoselenium compounds to form a Se…O chalcogen bonded supramolecular recognition unit (synthon) has been established in these polymorphs and its generality is substantiated with the help of a Cambridge Structural Database (CSD) analysis. Section 1.2 demonstrates the utility of the ‘chalcogen bonded supramolecularsynthon’ in generating molecular complexes of APIs. A series of salts and co-crystals of the amyotrophic lateral sclerosis drug Riluzole have been synthesized in order to evaluate the structure directing role of S…O chalcogen bonded synthon in their crystal structures. Section 1.3adescribes the generation of polymorphs and solvatomorphs of the antidepressant drug candidate fenobamand associated phase transitions. The tautomeric preference in this molecule has been rationalized from the crystal structure analysis and abinitioenergy calculations. Further, section 1.3b utilizes chemical derivatization as a means to experimentally simulate thetautomeric preference and molecular conformations in several derivatives of fenobam and thiofenobam. Section 1.4 describes the issue of solvatomorphism and the generation of the fifth solvatomorph of gallic acid, its structural complexity and temperature induced phase transitions. The ability of solvent water molecules to drive structural diversity, by forming ‘hydration synthons’,is demonstrated in this case. Chapter 2 presents a novel methodology for the detection of polymorphic impurities in APIs based on second harmonic generation (SHG).The SHG based method has been employed to polymorphic mixtures of fenobam, hydrochlorothiazide, pyrazinamide, tolbutamide, curcumin, febuxostat and nimesulide.The conventional methods such as powder X-ray diffraction (profile fitting analysis), FT-IR, Raman spectroscopy and thermal analysesto detect the presence of polymorphic impuritiesin bulk API samples are employed on the mixtures of these API samples and the impurity detection limits are compared with the proposed SHG methodology. The APIs used in these case studies were screened for their SHG efficiency using quantum chemical calculations of hyperpolarizability and HOMO-LUMO charge redistribution behaviour. Further, a correlation with the crystal symmetry, relative packing arrangement of molecules and the observed SHG efficiency have been discussed in of some of these cases. Part B: Exploring the nature and structural consequences of nonbonding interactions in molecular crystals Chapter 3 discusses the electron density features of quasi-trifurcated CH…Cl/CH…O interaction motifs leading to ‘carbon bonding’ and a trifurcated CH…O hydrogen bond motif. Section 3.1 describes the experimental and theoretical charge density analyses of quasi-trifurcated CH…Cl and CH…O motifsand investigates the existence of “carbon bonding” in solid state. The experimental charge density evidence for “carbon bonding” have been analyzed in cases of fenobam and dimethylamine: 4-hydroxybenzoic acid complex. The existence of this unconventional interaction, which roughly mimics the transition state geometry of SN2 (bimolecular nucleophilic substitution) reaction, is further established by a CSD analysis. Section 3.2 describes the experimental and theoretical charge density analyses of ferulic acid and compares the topological features associated with a trifurcated CH…O hydrogen bond motif, with corresponding strong classical OH…O hydrogen bonds. The study demonstrates the “Gulliver effect” of weak interactions in charge density terms. Charge density based interaction energy calculations via EPMM and EML methods have been utilized in this context to evaluate the relative strength of such interactions. Chapter 4 discusses the charge density features of intermolecular chalcogen bonding interactions involving selenium and sulphur atoms.Section 4.1 describes the experimental and theoretical charge density analyses of ebselen and its hydroxyl derivative. The charge density characterization of the conserved chalcogen bond synthon (discussed in chapter 1, section 1.1) has been carried out and electronic nature and geometric dependence of Se…O interactions have been explored. The mechanism of drug action of ebselen has been correlated with the experimentally observed charge density distribution around the intramolecular SeC and SeN bonds. Section 4.2 explores the homochalcogen interactions such as S…SandSe…Se in phenol analogues. In situ cryocrystallographic studies on thiophenol, selenophenol and their solid solutions are described. Veggard’s law-like behaviour observed in these solid solutions have been rationalized and the S…S and Se…Sehomochalcogen interactions have been evaluated in these liquid systems which are devoid of any other packing forces such as strong hydrogen bonds. Chapter 5 discusses the conformation locking potential of intramolecular S…O chalcogen bonding in sulfadrugs. Section 5.1 discusses conformation locking in the antibioticdrugsulfamethizole. A two pronged approach has been adopted in the study; a) generation of cocrystals and salts of sulfamethizole for the ‘experimental simulation’ of the molecular conformation, b) evaluation of charge density distribution around the intramolecular S…O interaction region in sulfamethizole. Section 5.2 describes the effect of ‘simple hybridized orbital geometry’ in the formation of intramolecular S…O chalcogen bonding. The experimental charge density analysis of the carbonic anhydrase inhibitor drug acetazolamide has been carried out and the two different intramolecular S…O geometries have been compared in terms of the charge density topology. The analysis highlights the advantage of “orbital geometry” consideration over the conventional distance-angle criteria in assessing nonbonded interactions.

Les nano-antennes optiques constituent un élément clé pour le contrôle et l’intéraction lumière/matière à l’échelle nanométrique. Ces systèmes opèrent dans le domaine de l’optique visible et proche infrarouge. Les propriétés de ces composants sont contrôlées en modifiant la taille, la forme et le matériau utilisé. Ces paramètres sont ajustés par les processus de fabrication de l’antenne. Dans le domaine des radio-fréquences, le tuner permet d’ajuster la fréquence de résonance de l’antenne de façon dynamique. Nous avons dans le cadre de cette thèse voulu adapter ce concept de tuner au domaine de l’optique. Le principe employé consiste à changer la résistance de charge de l’antenne, c’est-à-dire l’indice du milieu électrique environnant. Pour cela, nous avons utilisé un matériau anisotrope constitué de molécules de cristaux liquides. L’indice optique est alors modifié par l ’application d’un champ électrique statique. Le changement des propriétés spectrales ainsi que de diffusion d’une antenne de type dimère sont ici démontrées.Toujours en analogie avec les antennes radio-fréquences, nous avons étudié la propriété de transduction électron-photon dans le cas des antennes optiques. Dans ce but, nous avons considéré deux configurations. La première concerne l’utilisation de nanotubes de carbone placés dans une configuration de transistor à effet de champ. Ces objets émettent de la lumière par une recombinaison de paires électrons-trous dans le domaine des longueurs d’ondes Télécom. La seconde configuration emploie des jonctions tunnels fabriquées par électro-migration. Dans ce cas là, la jonction est assimilée à une antenne à interstice. A cause des faibles dimensions des jonctions (autour de 1 nm), nous nous sommes intéressés à la réponse en optique non linéaire de ses objets. Cette technique permet de localiser la jonction tunnel grâce à une forte exaltation du signal. L’etude des différentes caractérisques de ses jonctions sont ici présentées. Une fois la transduction du signal réalisée par l’antenne radiofréquence, celui-ci est acheminé via une ligne de transmission. A l’ échelle nanométrique, les guides plasmoniques s’avèrent être un type de structure approprié. Dans ce cas, les guides peuvent à la fois servir d’´electrode mais aussi de guide. Dans le cadre de cette thèse, nous avons étudié par microscopie à fuites radiatives, dans l’espace direct et réciproque, la plus simple des géométries : le guide ruban métallique. Nous avons cherché à comprendre, pourquoi ce type de structure présente une largeur de coupure. / Optical nano-antennae are the new class of components to control light/matterinteraction at the nanoscale. These devices are operating in the visible to near infraredpart of the spectrum. The properties of these nano objects are controlled by theform, the size and the material.In the radio frequency domain, the tuner changes dynamically the operatingwavelength of the antenna. In this thesis work, we search to transfer this conceptto the nanoscale. The principle is to change the load impedance of the antenna, i.e.changing the optical index of the dielectric medium around the nano-object. Forthat we used anisotropic liquid cristal molecules. The value of the optical index iscontrolled by applying an external electrical static field. The effects on the spectraland scattering properties are demonstrated on a single dimer nano-antenna.However with the microwave antennae, we were interesting to the electronsphotonstransduction with an optical antenna. In this mind, we studied two differentsconfigurations. The first one concerns the use of carbon nanotubes placedin a field effect transistor configuration. These nano-objects emit light in the Telecomwavelength range by a radiative combination of electrons and holes. the secondconfiguration used planar tunnel junctions made by electromigration. In this case,the junctions are view as an optical gap antenna. Because the gap are very small(around 1 nm), we have studied the nonlinear optical response of these objects. Thisnonlinear optical characterization allows to determined the location of the tunneljunctions by an enhancement of the optical signal. The results about the properties(electrical and optical) of these tunnel junctions are presented.Once the transduction by the radio frequency antenna is achieved, this signalis transporting by a transmission line. By transposition at the nanoscale, the plasmonicswaveguides prove to be the most appropriate structure. In this case, theycould be used as an electrode or a waveguide. In this thesis work, we have studiedby leakage radiation microscopy, in the direct and reciprocal space, the simplestgeometry : plasmonic metal strips. We search to understand why these structureshave a cut-off width.

La génération de seconde harmonique magnétique (mSHG pour magnetic Second Harmonic Generation) est un phénomène physique très sensible apparaissant grâce aux brisures de symétrie aux niveaux des surfaces et interfaces des structures métalliques magnétiques. Elle constitue donc un outil puissant pour explorer ce type d'interfaces et des nanostructures. Dans ce travail, nous nous intéressons aux couplages et interactions entre la mSHG et les ondes électromagnétiques pouvant se propager en surface des matériaux. Un intérêt spécifique est porté sur l’ excitation de (i) plasmon polaritons de surfaces (SPP) dans des films métalliques en structures multicouches, (ii) d'anomalies de diffraction (dîtes de Wood) dans des nanostructures métalliques périodiques. Pour étudier l'influence de l'excitation linéaire et non-linéaire des SPP sur la mSHG, l'intensité du signal réfléchi par génération de seconde harmonique (SH) et le contraste magnétique lié à ce signal ont été mesurés par la technique de l'effet Kerr magnéto-optique transverse (MOKE) en fonction de l'angle d'incidence. Via l'utilisation de sources lasers femtosecondes émettant dans le proche infrarouge, domaine spectral où les variations de la dispersion des SPP et du coefficient d'amortissement sont significatives, nous avons pu distinguer les différentes contributions linéaires et non-linéaires aux processus d'excitation. Ce travail de thèse a ainsi permis de montrer que l’accord de phase entre la mSHG et les ondes électromagnétiques de surface peuvent contribuer très efficacement à l'augmentation des signaux SH et de contraste magnétique associé. / Owing to surface and interface sensitivity, the magnetic Second Harmonic Generation (mSHG) represents a useful tool to probe magnetic interfaces and nanostructures. This work investigates the coupling and interaction of the mSHG with electromagnetic waves propagating along the surface. Two types of surface waves have been studied: (i) surface plasmon polaritons (SPP) at surfaces of metallic thin films and multilayers, and (ii) the diffraction anomaly at the surface of periodically arranged metallic nanostructures. To study influence of linear and nonlinear excitation of surface waves on the mSHG, the reflected second harmonic (SH) intensity and the magnetic SH contrast in the transverse magneto-optical geometry were measured as a function of the angle of incidence. The use of different femtosecond light sources in the near-infrared optical range, where the SPP dispersion and damping exhibit significant variations, made it possible to disentangle linear and nonlinear contributions to the excitation of surface waves. In this thesis, it is proven that phase-matching of the mSHG and surface electromagnetic waves can lead to the enhancement of both the SH yield and the nonlinear magneto-optical signal. These results are important for controlling of the nonlinear magneto-optical response and could impact the development of magnetic storage devices, label-free biosensors and nonlinear magneto-optical switches.

This dissertation presents the novel creation of a hybrid D-fiber electro-optic polymer electric field sensor. The sensor is made by removing a portion of the cladding from a D-shaped optical fiber, thus exposing the core to interaction with external stimulus. Then, an electro-optic polymer is deposited, partially replacing the core of the fiber. Next, the polymer is poled to endow it with electro-optic properties. This sensor is packaged in order to restore its mechanical strength. Because D-fiber is not intrinsically compatible with standard optical equipment it is fusion spliced to standard polarization maintaining fiber. Finally the sensor is tested for electro-optic sensitivity. The hybrid D-fiber electric field sensors designed and fabricated in this work meet the requirements of mechanical strength, temporal stability, minimal perturbation of the electric field by the sensor, and a small and flexible cross-sectional area so that it can be embedded into the device under test. A fully packaged hybrid electro-optic polymer D-fiber electric field sensor which is capable of detecting electric fields of 50 V/m at a frequency of 6 GHz is produced. The sensor's electro-optic response is shown to be temporally stable. Additionally, the sensor is physically robust, and physically and electrically non-intrusive. This work also adds a thorough understanding of the design and fabrication of D-fiber waveguides with a polymer material deposited in the core. Several new fabrication techniques are developed and presented. A path to greater electric field sensitivity is outlined for future research.

[pt] O objetivo deste trabalho foi desenvolver métodos eficientes e reprodutíveis de crescimento de monocamadas de WS2, MoS2 e outras heteroestruturas verticais por deposição química em fase de vapor à pressão atmosférica (APCVD). A monocamada separada destes materiais tem grande importância na fabricação de novos dispositivos óticos e Nano eletrônicos. Dispositivos finos e de baixo custo necessitam temperaturas em torno de 800 graus celsius, o que é um problema para aplicações mencionadas acima. Nesta tese, nós propusemos uma nova rota usando APCVD para crescer monocamadas de MoS2 a 550 graus celsius, usando sódio como catalisador. Nós produzimos monocristais e poli cristais controlando a razão de precursores NaNO3/MoO3 e tempo de crescimento. Usando cálculos de primeiros princípios, mostramos que o sódio atua como centro de nucleação para o processo de síntese. A razão de precursores é crucial para diminuir a energia de formação e a temperatura de síntese. Cálculos de primeiros princípios e experimentos concordam que uma razão ideal é em torno de 0.3, proporcionando uma queda de 250 graus celsius na temperatura de crescimento. Nós investigamos as amostras crescidas por APCVD usando espectroscopia de fotoelétrons induzidos por raios-X, microscopia de força atômica, espectroscopia Raman, fotoluminescência e mediadas de transporte. Dicalcogenetos de metais de transição (TMD) dispostos em poucas camadas permitem-nos criar materiais e estudar novos fenômenos físicos. A sequência de empilhamento dos TMDs pode modificar suas propriedades opticas e elétricas. Também sintetizamos poucas camadas de MoS2 e WS2 usando APCVD. Duas e três camadas de WS2, MoS2 e suas heteroestruturas verticais foram caracterizadas através de geração de segundo harmônico (SHG). SHG mostra que as bicamadas crescidas com ângulos de rotação relativos de 0 grau e 60 graus possuem diferentes fases de empilhamento. O SHG do empilhamento bicamada com ângulo relativo de 0 graus aumentos, enquanto para amostras com empilhamento de 60 graus foi zerado. Este comportamento do SHG sugere que duas camadas de MoS2 ou WS2, quando empilhados a 0 graus não possuem simetria de inversão para 3R(AB) entre as camadas inferiores e superiores, enquanto as camadas de 60 graus possuem simetria de inversão (centrossimétricas) e possuem empilhamento na forma 2H(AA). Finalmente, dispositivos foram fabricados em amostras de boa qualidade para a investigação de sua performance elétrica. Os dispositivos mostram comportamento típico tipo-n e sua mobilidade foi estimada a partir das curvas de transporte. A dependência dos modos Raman das nossas amostras de heteroestruturas também foi estudada. Aplicando uma tensão nos dispositivos, o modo A1 mostrou um desvio para o azul e um novo modo surge em 410 cm-1, atribuídos defeitos (D) no cristal. / [en] The aim of this work was to develop reliable and repeatable methods for growing high-quality monolayer MoS2, WS2, and their vertical heterostructure by atmospheric pressure chemical vapor deposition (APCVD) technique. The monolayer of these materials have vital importance in the fabrication of new optical and nanoelectronic devices. Thin and low-cost devices have increased the demand for new synthesis processes. Usually, the synthesis requires temperatures around 800 Celsius degrees, which is an issue for applications mentioned above. In this thesis, we propose a new route using the APCVD technique to grow monolayers of MoS2 at 550 Celsius degrees mediated by sodium as a catalyst. We have produced single crystals and polycrystals by controlling the NaNO3/MoO3 precursor s ratio and growth time. Using first-principles calculations, we find out that sodium is the nucleation site of the growth process. The precursor s ratio is crucial to decrease the energy formation and the synthesis temperature. Firstprinciples calculations and experiments agree with the ideal precursor s rate of 0.3 and with the decrease of the synthesis temperature of 250 Celsius degrees. We investigated the CVD grown sample with X-ray photoelectron spectroscopy, atomic force microscopy, Raman spectroscopy, photoluminescence spectroscopy, and transport experiments. Few layers of TMDs allow us to create new materials and find new physical phenomena. The stacking sequence in few-layer TMDs can significantly impact on their electrical and optical properties.We also synthesized few layers of MoS2 and WS2 via APCVD. Two and three layers of MoS2, WS2, and their vertical heterostructures were characterized by second harmonic generation (SHG). The SHG shows that the layers in bilayers grow with 0 degrees or 60 degrees has different phase stacking. The SHG from 0 degrees stacked bilayer has increased when compared to monolayer, while the generated signal from bilayer with 60 degrees stacking is zero. This behavior of SHG suggests that the two layers of MoS2 or WS2 when stacked at 0 degrees have no inversion symmetry to 3R(AB) phase stacking between the top layer and the bottom layer. While when stacked with 60 degrees has inversion symmetry (Centrosymmetric) and have 2H(AA0) phase stacking. Finally, the devices were fabricated on good quality samples to investigate their electrical performance. The fabricated devices show typical n-type behavior and mobility was estimated by measuring transport curves. The dependence of Raman modes of our heterostructure device with electron doping was also studied. By applying a voltage across our device the A1 mode shows blueshift and a new mode emerges at ~ 410 cm-1, which is attributed to the defects (D) in the crystal.