A adição de sais de lítio à líquidos iônicos gera mudanças em propriedades físicas relevantes, que comprometem sua possível aplicação em baterias de lítio, como aumento de viscosidade e redução da condutividade iônica. Possíveis causas para tais efeitos foram estudadas através da utilização de Espectroscopia Raman e Espectroscopia de Efeito Óptico Kerr. Foram estudadas as misturas dos liquídos iônicos: 1-butil-3metilimidazólio, N-(3- etóxietil)-N-metilmorfolínio e cátion 1-(3-etóxietil)-2,3-dimetilimidazólio possuindo em comum o contra-íon bis(trifluorometanosulfonil)imideto com diferentes concentrações de bis(trifluorometanosulfonil)imideto de lítio. O trabalho se dividiu em duas etapas principais, na primeira utilizou-se a espectroscopia Raman e observou-se o desdobramento da banda referente ao ânion em aproximadamente 740 cm-1, em dois diferentes picos, após a adição de lítio ao sistema. Esta observação forneceu indícios da ocorrência de mudanças estruturais possivelmente relacionadas a formação de agregados entre os ânions e o Li+. A partir destes resultados a obtenção de um valor aproximado para o número de coordenação médio dos cátions Li+ foi possível através da comparação da intensidade relativa dos dois picos para diferentes concentrações de sal. Foi ainda estudado o efeito da adição de água no sistema, causando o desaparecimento do pico Raman formado após a adição do sal de lítio, o que evidencia a capacidade da mesma de reduzir o efeito de agregação dos ânions ao redor do Li+. Na segunda etapa do trabalho, a técnica de espectroscopia de efeito óptico Kerr via detecção heterodina foi utilizada para a observação do perfil de relaxação orientacional nos sistemas descritos acima, a fim de examinar mudanças nos processos dinâmicos presentes após a adição sal inorgânico ao sistema. Os resultados foram analisados no contexto da teoria de acoplamento de modos, de maneira que utilizou-se um modelo fenomenológico desenvolvido através da observação de diferentes sistemas e da aplicação das equações propostas no modelo esquemático de Sjögren para a descrição da função de correlação polarizabilidade-polarizabilidade obtida pelo experimento. Os parâmetros encontrados demonstraram um alto grau de concordância com as observações estruturais observadas na primeira etapa, fornecendo evidências de que o lítio é capaz de afetar as estruturas locais presentes no líquido iônico puro de uma maneira similar ao efeito Chemla. O trabalho demonstrou que os mesmos princípios necessários para a síntese de líquidos iônicos a temperatura ambiente, primando a redução das interações atrativas entre os cátion e ânions para a estabilização da fase líquida, possui como efeito colateral o fato de que diversas moléculas apresentam interações mais fortes com seus íons alterando suas propriedades, neste caso prejudicando a utilização de líquidos iônicos como solventes alternativos em baterias de lítio. / The introduction of lithium salts to room temperature ionic liquids causes unwanted changes to the electrochemically relevant properties of these compounds, such as increase in viscosity and the reduction of ionic conductivity. Possible causes for these effects were studied with spectroscopic techniques such as Raman spectroscopy and Optical Kerr Effect spectroscopy. Mixtures of three different ionic liquids containing the cations: 1-butyl-3- methylimidazolium, N-(3-etoxyethyl)-N-methylmorfolinium and cátion 1-(3-etoxyethyl)-2,3- dimethylimidazolium and possessing the common counter ion bis(trifluoromethane sulfonyl)imide with lithium bis(trifluoromethane sulfonyl)imide. This work was divided in two parts, the first consisting of the use of Raman spectroscopy and the observation of the changes in the 740 cm-1 peak, pertaining to anion vibration after the introduction of lithium to the system, shown as the appearance of a new peak at higher frequencies. The approximate average lithium coordination number was determined by comparison of the relative intensities for different salt concentrations. The effect of water absorption in this system was also observed, showing that water molecules tend to hinder the formation of aggregates between the anion and Li+. The second step was carried out with the use of optically heterodyne detected optical Kerr effect spectroscopy to the analysis of the orientational relaxation profile for the systems described above. Results were analyzed through the application of Mode Coupling Theory models, both a phenomenological model obtained by the observation of different classes of liquids and the Mode Coupling Schematic model proposed by Sjögren were used to describe the polarizability-polarizabilty correlation function obtained from the experiments. The parameters obtained showed a high degree of correlation with the results obtained in the first part indicating that the introduction of a highly polarizing cation to the pure ionic liquid causes an effect similar to the Chemla effect observed in inorganic salt mixtures. The work showed evidences that the same principles used for the synthesis of room temperature ionic liquids, i.e. the reduction of attractive interactions between cation and anion or the addition of alkyl chains to reduce symmetry, result in various different compounds showing stronger interactions with the different ions resulting in changing properties, in this case hindering the use of ionic liquids as alternative green solvents for lithium ion batteries.

A adição de sais de lítio à líquidos iônicos gera mudanças em propriedades físicas relevantes, que comprometem sua possível aplicação em baterias de lítio, como aumento de viscosidade e redução da condutividade iônica. Possíveis causas para tais efeitos foram estudadas através da utilização de Espectroscopia Raman e Espectroscopia de Efeito Óptico Kerr. Foram estudadas as misturas dos liquídos iônicos: 1-butil-3metilimidazólio, N-(3- etóxietil)-N-metilmorfolínio e cátion 1-(3-etóxietil)-2,3-dimetilimidazólio possuindo em comum o contra-íon bis(trifluorometanosulfonil)imideto com diferentes concentrações de bis(trifluorometanosulfonil)imideto de lítio. O trabalho se dividiu em duas etapas principais, na primeira utilizou-se a espectroscopia Raman e observou-se o desdobramento da banda referente ao ânion em aproximadamente 740 cm-1, em dois diferentes picos, após a adição de lítio ao sistema. Esta observação forneceu indícios da ocorrência de mudanças estruturais possivelmente relacionadas a formação de agregados entre os ânions e o Li+. A partir destes resultados a obtenção de um valor aproximado para o número de coordenação médio dos cátions Li+ foi possível através da comparação da intensidade relativa dos dois picos para diferentes concentrações de sal. Foi ainda estudado o efeito da adição de água no sistema, causando o desaparecimento do pico Raman formado após a adição do sal de lítio, o que evidencia a capacidade da mesma de reduzir o efeito de agregação dos ânions ao redor do Li+. Na segunda etapa do trabalho, a técnica de espectroscopia de efeito óptico Kerr via detecção heterodina foi utilizada para a observação do perfil de relaxação orientacional nos sistemas descritos acima, a fim de examinar mudanças nos processos dinâmicos presentes após a adição sal inorgânico ao sistema. Os resultados foram analisados no contexto da teoria de acoplamento de modos, de maneira que utilizou-se um modelo fenomenológico desenvolvido através da observação de diferentes sistemas e da aplicação das equações propostas no modelo esquemático de Sjögren para a descrição da função de correlação polarizabilidade-polarizabilidade obtida pelo experimento. Os parâmetros encontrados demonstraram um alto grau de concordância com as observações estruturais observadas na primeira etapa, fornecendo evidências de que o lítio é capaz de afetar as estruturas locais presentes no líquido iônico puro de uma maneira similar ao efeito Chemla. O trabalho demonstrou que os mesmos princípios necessários para a síntese de líquidos iônicos a temperatura ambiente, primando a redução das interações atrativas entre os cátion e ânions para a estabilização da fase líquida, possui como efeito colateral o fato de que diversas moléculas apresentam interações mais fortes com seus íons alterando suas propriedades, neste caso prejudicando a utilização de líquidos iônicos como solventes alternativos em baterias de lítio. / The introduction of lithium salts to room temperature ionic liquids causes unwanted changes to the electrochemically relevant properties of these compounds, such as increase in viscosity and the reduction of ionic conductivity. Possible causes for these effects were studied with spectroscopic techniques such as Raman spectroscopy and Optical Kerr Effect spectroscopy. Mixtures of three different ionic liquids containing the cations: 1-butyl-3- methylimidazolium, N-(3-etoxyethyl)-N-methylmorfolinium and cátion 1-(3-etoxyethyl)-2,3- dimethylimidazolium and possessing the common counter ion bis(trifluoromethane sulfonyl)imide with lithium bis(trifluoromethane sulfonyl)imide. This work was divided in two parts, the first consisting of the use of Raman spectroscopy and the observation of the changes in the 740 cm-1 peak, pertaining to anion vibration after the introduction of lithium to the system, shown as the appearance of a new peak at higher frequencies. The approximate average lithium coordination number was determined by comparison of the relative intensities for different salt concentrations. The effect of water absorption in this system was also observed, showing that water molecules tend to hinder the formation of aggregates between the anion and Li+. The second step was carried out with the use of optically heterodyne detected optical Kerr effect spectroscopy to the analysis of the orientational relaxation profile for the systems described above. Results were analyzed through the application of Mode Coupling Theory models, both a phenomenological model obtained by the observation of different classes of liquids and the Mode Coupling Schematic model proposed by Sjögren were used to describe the polarizability-polarizabilty correlation function obtained from the experiments. The parameters obtained showed a high degree of correlation with the results obtained in the first part indicating that the introduction of a highly polarizing cation to the pure ionic liquid causes an effect similar to the Chemla effect observed in inorganic salt mixtures. The work showed evidences that the same principles used for the synthesis of room temperature ionic liquids, i.e. the reduction of attractive interactions between cation and anion or the addition of alkyl chains to reduce symmetry, result in various different compounds showing stronger interactions with the different ions resulting in changing properties, in this case hindering the use of ionic liquids as alternative green solvents for lithium ion batteries.

This thesis aims to explore the effect of in situ ion gun etching on magnetic proper- ties, such as perpendicular magnetic anisotropy, of Pt/Co/Pt multilayers. Perpendicular magnetic anisotropy is of interest due to its importance in spintronic application. Calibration spectroscopic ellipsometry measurements of Pt and Co layers to obtain sputter yields of respective magnetron targets were performed as a first step. After that, ten Pt/Co/Pt multilayers with different Co and top Pt layer thicknesses were prepared. Five of these samples were etched by the ion gun, mounted inside of the magnetron chamber, during different stages of the deposition. To characterize the prepared samples, experimental and modeled Kerr rotation spectra were confronted. This provided an insight into the cross-sections of the investigated samples. Magnetic hysteresis loops measured by vibrating sample magnetometer and Kerr rotation setup demonstrated higher coercive field and change of the slope of the loop induced by ion etching. When compared to the obtained cross-sections, a correlation between the change of magnetic loops and intermixing of Pt and Co at the interface was visible. This intermixing was higher in samples treated by the ion gun. 1

This thesis examines second-order optical nonlinear wave mixing processes in domain-disordered quasi-phase matching waveguides and evaluates their potential use in compact, monolithically integrated wavelength conversion devices. The devices are based on a GaAs/AlGaAs superlattice-core waveguide structure with an improved design over previous generations. Quantum-well intermixing by ion-implantation is used to create the quasi-phase matching gratings in which the nonlinear susceptibility is periodically suppressed. Photoluminescence experiments showed a large band gap energy blue shift around 70 nm after intermixing. Measured two-photon absorption coefficients showed a significant polarization dependence and suppression of up to 80% after intermixing. Similar polarization dependencies and suppression were observed in three-photon absorption and nonlinear refraction. Advanced modeling of second-harmonic generation showed reductions of over 50% in efficiency due to linear losses alone. Self-phase modulation was found to be the dominant parasitic nonlinear effect on the conversion efficiency, with reductions of over 60%. Simulations of group velocity mismatch showed modest reductions in efficiency of less than 10%. Experiments on second-harmonic generation showed improvements in efficiency over previous generations due to low linear loss and improved intermixing. The improvements permitted demonstration of continuous wave second-harmonic generation for the first time in such structures with output power exceeding 1 µW. Also, Type-II phase matching was demonstrated for the first time. Saturation was observed as the power was increased, which, as predicted, was the result of self-phase modulation when using 2 ps pulses. By using 20 ps pulses instead, saturation effects were avoided. Thermo-optically induced bistability was observed in continuous wave experiments. Difference frequency generation was demonstrated with wavelengths from the optical C-band being converted to the L- and U-bands with continuous waves. Conversion for Type-I phase matching was demonstrated over 20 nm with signal and idler wavelengths being separated by over 100 nm. Type-II phase matched conversion was also observed. Using the experimental data for analysis, self-pumped conversion devices were found to require external amplification to reach practical output powers. Threshold pump powers for optical parametric oscillators were calculated to be impractically large. Proposed improvements to the device design are predicted to allow more practical operation of integrated conversion devices based on quasi-phase matching superlattice waveguides.

Die vorliegende Arbeit untersucht ultraschnelle Rotations- und Translationsbewegungen in molekularen Flüssigkeiten. Dazu wurde deren Optischer Kerr-Effekt/Raman-Induzierter Kerr-Effekt (OKE/RIKE) zeitaufgelöst mithilfe der Pump/Probetechnik gemessen. Die erzielte Zeitauflösung betrug 30 fs. Langzeitschwankungen des Signals konnten zusätzlich mit einer Echtzeit-Meßtechnik eliminiert werden. In der transienten Doppelbrechung wurde so ein Signal/Rausch Verhältnis von 10^7 erreicht. Das Ziel war eine möglichst genaue Beschreibung der Responsfunktion für den Optischen Kerr-Effekt der Flüssigkeiten Chloroform, Acetonitril, Trichloracetonitril, Tetrachlorkohlenstoff, Methylchloroform und Fluoroform. Die Fourier-Transformation dieser Responsfunktion entspricht dem depolarisierten Raman Spektrum der Flüssigkeit. Die Responsfunktion wurde auf zwei Wegen aus dem gemessenen OKE Signal erhalten: a) in der Zeitdomäne durch Anpassung empirisch gewählter Terme und b) in der Frequenzdomäne durch Anpassung von Brownschen Oszillatormoden. Die Analyse bezieht den gesamten Datenumfang ein, ohne numerisch problematische Entfaltungsverfahren nutzen zu müssen. In den untersuchten Systemen erfolgt die elektronische Antwort instantan auf den anregenden Laserimpuls. Innerhalb der ersten halben Pikosekunde beobachtet man eine intermolekulare Dynamik, die auf Librationen und kollisionsinduzierte Translationsbewegungen zurückgeht. Diese nur schwer unterscheidbare Dynamik verschwindet typischerweise mit Zeitkonstanten bis 250 fs. Die Langzeitrelaxation in den isotropen Zustand wird der diffusiven Reorientierung zugeordnet. Es werden hierfür Zeitkonstanten tau zwischen 1.2 (Methylchloroform) und 3 ps (Chloroform) beobachtet. Durch die hohe Bandbreite des Laserimpulses werden außerdem niederfrequente Raman-Linien (bis ca. 750 cm^-1) angeregt. Diese äußern sich durch untergedämpfte Signaloszillationen (RIKE). Erstmals wird der OKE von flüssigem Fluoroform untersucht. Aufgrund seiner Eigenschaften kommt CHF3 der Modellvorstellung einer polaren harten Kugel sehr nahe. Das beobachtete Signal ist ca. 110 mal schwächer als in Chloroform. Die diffusive Reorientierung verläuft auß erdem deutlich schneller (tau = 0.8 ps). Der (intermolekulare) OKE wächst nun mit steigender Polarisierbarkeitsanisotropie, während der (intramolekulare) RIKE von der änderung der Polarisierbarkeitsanisotropie mit der Schwingungskoordinate des Moleküls abhängt. Durch vergleichende Messungen mit isotropen Tetrachlorkohlenstoff kann auch prinzipiell der Einfluß der kollisionsinduzierten Effekte (CI) in den untersuchten Flüssigkeiten abgeschätzt werden. Rotations- und Translationsbewegungen korrelieren allerdings miteinander. Die daraus resultierenden Kreuzterme sind dann aus den Responsfunktionen allein nicht mehr zu ermitteln. Sie sind nur aus weiterführenden moleküldynamischen Simulationen erhältlich. Für Acetonitril wird eine übereinstimmung zwischen experimenteller und theoretisch vorhergesagter OKE Responsfunktion gefunden. Die OKE Responsfunktionen sind mit den Relaxationsfunktionen der dielektrischen Relaxation und der Solvatation von polaren Sondenmolekülen verknüpft. Die Messungen des zeitaufgelösten Optischen Kerr-Effektes sollen hier künftig dazu dienen, die reinen Flüssigkeitsbeiträge zur polaren und nichtpolaren Solvatation zu erkennen. / Within this work the ultrafast rotational and translational motions of molecular liquids are investigated. Therefore their Optical Kerr effect/Raman induced Kerr effect (OKE/RIKE) was measured time-resolved with the pump/probe technique. Achieved time resolution was 30 fs. Long-time fluctuations of the signal might be eliminated by an additional realtime measurement technique. Hence a signal/noise ratio of ca. 10^7 in the transient birefringence was obtained. A detailed description of the response function derived from Optical Kerr effect was targeted for the liquids chloroform, acetonitrile, trichloroacetonitrile, carbon tetrachloride, 1,1,1-trichloroethane and fluoroform. The Fourier-Transformation of the response functions of the liquids is eqivalent to their depolarized Raman spectra. The response function is obtained from measured signals in two ways: a) by fitting empirical terms in time domain and b) fitting Brownian oscillator modes in frequency domain. Analysis includes complete data range without using numerical deconvolution techniques. In all investigated systems an electronical response follows to the stimulating laser pulse instantaneously. Within the first half pico second one observes intermolecular dynamics due to librational and collision-induced translational motions. These (hard to distinguish) dynamics disappear with typical time-constants of up to 250 fs. The long-time relaxation into an isotropic distribution of molecules is termed diffusive reorientation. Here time-constants tau between 1.2 (CCl3CH3) and 3 ps (CHCl3) are observed. Additionally low-frequent Raman lines (up to 750 cm^-1) may be stimulated due to the high pulse bandwidth, resulting in underdamped signal oscillations (RIKE). The OKE of liquid fluoroform is investigated for the first time. It comes closest to the Mean Spherical Approximation model for a fluid composed of polar, nonpolarizable hard spheres. The observed signal is ca. 110 times weaker than in chloroform. The diffusional reorientation occurs also faster (tau = 0.8 ps). Generally (intermolecular) OKE rises with growing polarizability anisotropy, while (intramolecular) RIKE depends from the change of polarizability anisotropy with the vibrational coordinate. Influence of collision-induced effects (CI) is derived in principle from compared measurements in isotropic carbon tetrachloride. However a correlation exists between rotational and translational motion. Resulting cross-terms cannot be obtained from response functions alone. These are only available in molecular-dynamic simulations in literature. In acetonitril one finds similar response functions derived from OKE measurements and predicted theoretical simulation. The OKE respons functions are related to relaxation functions of the dielectrical relaxation and the solvation of polar molecules. Time-resolved measurements of the OKE reveal here contributions of the pure liquid in polar and nonpolar solvation.

In der vorliegenden Arbeit wird eine einheitliche und allumfassende Theorie der Nicht-linearen Polarisationsspektroskopie in der Frequenzdomäne (NLPF) aufgestellt. Dies Methode basiert auf der in einer isotropen Farbstofflösung durch ein polarisiertes, monochromatisches Laserfeldes (pump) erzeugten Anisotropie, die mittels eines weiteren monochromatischen Laserfeldes (probe), mit einer um 45° gegenüber dem Pumpfeld gedrehten Polarisationsrichtung geprobt wird. Ausgehend von den grundlegenden Gleichungen für den nichtlinearen Respons molekularer Systeme auf elektromagnetische Felder wird das zweidimensional NLPF-spektrum hergeleitet, und zwar sowohl in der niedrigsten Ordnung Störungstheorie als auch unter Verwendung eines selbstkonsistenten Ansatzes für beliebige Pumpfeldstärken. In der niedrigsten Ordnung Störungstheorie können drei in ihrer Frequenzabhängigkeit sich unterscheidende Arten von Ausdrücke explizit angegeben werden. Diese sind drei Areten von Peaks im NLPF-spektrum zuzuordnen: Den T2-peaks, dem T1-peaks und den Zweiphotonen-peaks. Letztere sind unter Normalbedingungen im allgemeinen nicht beobachtbar und wurden daher nicht weiter behandelt. Die in dieser Arbeit erstmals gelungene, allgemeine und einheitliche theoretische Beschreibung der T1- und T2-peaks in NLPF-spektren von Mehrniveausystemen stellt einen Durchbruch hin zu einer allumfassenden Subbandenanalyse mittels NLPF dar. Durch Einbeziehung der teilweise bereits bekannten Auswirkungen homogener und inhomogener Linienverbreiterung und spektraler Diffusion auf NLPF-spektren, sowie deren Verallgemeinerung im Ramen der Theorie nichtmarkowscher Dissipationsprozesse, konnte eine Methodik entwickelt werden, die es erlaubt, NLPF-spektren molekularer und supramolekularer Systeme in Bezug auf das ihnen zugrundeliegende Termschema mit Übergangsfrequenzen und -dipolen, die homogenen und inhomogenen Linienbreiten, sowie dem zugeordneten Energierelaxations- und -transferpfad mitsamt zugehörigen Raten zu analysieren. Die in dieser Arbeit vorgestellte und über frühere rudimentäre Ansätze weit hinausgehende Theorie der NLPF bei starken Pumpfeldern, die auf einem selbstkonsistenten Ansatz für den Fourier-transformierten statistischen Operator beruhen, eröffnet ein komplett neues Feld von Anwendungen der NLPF. Für Zweiniveausysteme konnten die selbstkonsistenten Gleichung vollständig analytisch gelöst werden. Dabei konnten die Querverbindungen zur nichtlinearen Absorption und zum optischen Starkeffekt aufgezeigt werden. Aus der resultierenden Sättigungskurve für das NLPF-signal kann die Sättigungsintensität mit hoher Genauigkeit bestimmt werden. Diese kann unter Heranziehen der aus Analyse des T1-peaks bei niedrigen Intensitäten gewonnen Energierelaxationsrate und der analog aus T2-peakanalyse erhaltenen homogenen Linienbreite zur Bestimmung der Dipolstärke des Übergangs ohne Bestimmung der Farbstoffkonzentration verwendet werden. Dies erweist sich insbesondere bei der Analyse molekularer Aggregation als vorteilhaft. Durch Abbildung auf das gelöste Zweiniveauproblem konnte die Methodik auch auf spezielle Mehrniveausysteme übertragen werden. Eine analytische Lösung für allgemeine Mehrniveausysteme scheiterte jedoch an der komplizierten Orientierungsmittelung über die isotrope Verteilung der Übergangsdipole. Beide oben beschriebenen Methoden, Subbandanalyse bei niedrigen und Bestimmung der Übergangsdipolstärke bei hohen Pumpintensitäten, wurden in der vorliegenden Arbeit zur Untersuchung der Natur der angeregten Zustände in photosynthetischen Antennen von Purpurbakterien und höheren Pflanzen eingesetzt. Für die periphere lichtsammelnde Antenne LH2 des Purpurbakteriums Rhodobacter sphaeroides ergab die T2-peakanalyse der B850-absorptionsbande überraschenderweise zwei Subbanden, die im Absorptionsspektrum selbst bei tiefsten Temperaturen nicht aufzufinden gewesen wären. Eine Erklärung für die in Bezug auf die Oszilatorstärke asymmetrische Aufspaltung der B850-bande konnte allerdings nicht gefunden werden. Für den LH2 des sehr ähnliche Purpurbakterium Rhodospirillium molischianum konnte keine Aufspaltung der B850-bande festgestellt werden. Vielmehr liegt eine überwiegend homogen verbreiterte Bande mit einer homogener Linienbreite (FWHM) von 474±10 cm-1 und einem oberen limit für die inhomogene Linienbreite von 120 cm-1 vor. Daher wurde Rhodospirillium molischianum ausgewählt, um Delokalisation der Anregung im B850-aggregat mittels pumpintensitätsabhängiger NLPF zu untersuchen. Die Frage nach der Delokalisationslänge im B850-aggregat gab und gibt teilweise immer noch Anlass zu hitzigen Debatten. Das Ergebnis einer Ausdehnung der Anregung über 3-4 Bakteriochlorophylle des B850-aggregats der vorliegenden Arbeit unterstützt die aus Exciton-Exciton gewonnen Resultate. Weder eine vollständig lokalisierte noch vollständig delokalisierte Beschreibung war mit dem hier präsentierten Ergebnis in Übereinstimmung zu bringen. Auch im Hauptlichtsammelkomplex höherer Pflanzen LHC II konnte mittels pumpintensitätsabhängiger NLPF-spektren Delokalisation der Anregung über mindestens ein Chlì¥Á / In the work be presented a standard theory of non-linear polarization spectroscopy in the frequency domain (NLPF) will be established. The NLPF technique based on anisotropy induced in a dye-solution, which is isotropic elsewhere, by a polarized monochromatic pump laser field. This is probed by a second laser field, which polarization direction is turned of 45 degree in respect to that of the pump. From the fundamental equations describing the non-linear response of molecular systems on electromagnetic fields, the two-dimensional NLPF spectrum is deduced for arbitrary pump-intensities. At low pump-intensities a subband analysis by NLPF has been established. This allows one to study the term scheme and energy relaxation path of molecular and supra-molecular systems by their NLPF-spectra. This includes the determination of transition-frequencies and -dipole orientations, homogeneous and inhomogeneous linewidths, as well as energy relaxation rates. Furthermore, using a self-connsistent approach, the pump-fieled dependence of the NLPF-spectrum has been deduced for the two-level system in general and also for specific multi-level systems. This method allows one to determine the oscillator strength without knowledge of the concentration, what is quite useful for studying molecular aggregates. Applications are presented to the peripheral light harvesting antenna LH2 of purple bacteria and the light harvesting complexes LHC II and CP 29 of higher plants.

Magneto-optical materials such as permalloy can be used to create artificial spin- ice (ASI) lattices with antiferromagnetic ordering. Magneto-optical materials used to create diffraction lattices are known to exhibit magnetic scattering at the half- order Bragg peak while in the ground state. The significant drawbacks of studying the magneto-optical generation of OAM using x-rays are cost, time, and access to proper equipment. In this work, it is shown that the possibility of studying OAM and magneto-optical materials in the spectrum of visible light at or around 2 eV is viable. Using spectroscopic ellipsometry it is possible to detect a change in the magnetization of thin permalloy films with thicknesses between 5 and 20 nm. Patterns consistent with OAM were found at 1.95 eV using a square lattice with a 4𝜋 radial phase shift in the antiferromagnetic ground state. Evidence of magnetic scattering at the half-order Bragg peak using 1.95 eV was also found.

This thesis examines second-order optical nonlinear wave mixing processes in domain-disordered quasi-phase matching waveguides and evaluates their potential use in compact, monolithically integrated wavelength conversion devices. The devices are based on a GaAs/AlGaAs superlattice-core waveguide structure with an improved design over previous generations. Quantum-well intermixing by ion-implantation is used to create the quasi-phase matching gratings in which the nonlinear susceptibility is periodically suppressed. Photoluminescence experiments showed a large band gap energy blue shift around 70 nm after intermixing. Measured two-photon absorption coefficients showed a significant polarization dependence and suppression of up to 80% after intermixing. Similar polarization dependencies and suppression were observed in three-photon absorption and nonlinear refraction. Advanced modeling of second-harmonic generation showed reductions of over 50% in efficiency due to linear losses alone. Self-phase modulation was found to be the dominant parasitic nonlinear effect on the conversion efficiency, with reductions of over 60%. Simulations of group velocity mismatch showed modest reductions in efficiency of less than 10%. Experiments on second-harmonic generation showed improvements in efficiency over previous generations due to low linear loss and improved intermixing. The improvements permitted demonstration of continuous wave second-harmonic generation for the first time in such structures with output power exceeding 1 µW. Also, Type-II phase matching was demonstrated for the first time. Saturation was observed as the power was increased, which, as predicted, was the result of self-phase modulation when using 2 ps pulses. By using 20 ps pulses instead, saturation effects were avoided. Thermo-optically induced bistability was observed in continuous wave experiments. Difference frequency generation was demonstrated with wavelengths from the optical C-band being converted to the L- and U-bands with continuous waves. Conversion for Type-I phase matching was demonstrated over 20 nm with signal and idler wavelengths being separated by over 100 nm. Type-II phase matched conversion was also observed. Using the experimental data for analysis, self-pumped conversion devices were found to require external amplification to reach practical output powers. Threshold pump powers for optical parametric oscillators were calculated to be impractically large. Proposed improvements to the device design are predicted to allow more practical operation of integrated conversion devices based on quasi-phase matching superlattice waveguides.

Title: Magnetic nanostructures for recording and optical sensors Author: Eva Lišková Department: Institute of Physics, Charles University Supervisor: Prof. Ing. Štefan Višňovský, DrSc. Abstract: Magneto-optical (MO) spectra of multilayered structures with enhanced MO effect were studied using the polar and longitudinal Kerr spectroscopy with oblique angle of light incidence in the photon energy range 1.2 eV to 5 eV. The samples with Fabry- Perot cavity like architecture, were modeled using Yeh matrix formalism. Two sets of samples, with composition FeF2/Fe/FeF2 and AlN/Fe/AlN, were prepared by molecular beam epitaxy and sputtering. The relations were studied between the position of the enhanced peak in the MO spectra and the structure. Second part of this work was devoted to the Pt/Co/Pt structures and the influence of the ion implantation on MO spectra and structural composition. The studied multilayer structures present interest for MO sensor and memory applications. Keywords: Magneto-optical Kerr effect, Magneto-optical sensor, Fabry-Perot resonator, Ion implantation

Made available in DSpace on 2014-12-17T15:14:57Z (GMT). No. of bitstreams: 1 EdimilsonFS_DISSERT.pdf: 2546760 bytes, checksum: 08525df56e96d75f8d221757342883b4 (MD5) Previous issue date: 2012-02-17 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In this work, we investigated the magnetic properties of a monocrystalline Fe thin film and of Fe(80 ?)/Cr(t)/Fe(80 ?) tri-layers, with the nonmagnetic metallic Cr spacer layer thickness varying between 9 ? < t < 40 ?. The samples were deposited by the DC Sputtering on Magnesium Oxide (MgO) substrates, with (100) crystal orientation. For this investigation, experimental magneto-optical Kerr effect (MOKE) magnetometry and ferromagnetic resonance (FMR) techniques were employeed. In this case, these techniques allowed us to study the static and dynamical magnetization properties of our tri-layers. The experimental results were interpreted based on the phenomenological model that takes into account the relevant energy terms to the magnetic free energy to describe the system behavior. In the case of the monocrystalline Fe film, we performed an analytical discussion on the magnetization curves and developed a numerical simulation based on the Stoner-Wohlfarth model, that enables the numerical adjustment of the experimental magnetization curves and obtainment of the anisotropy field values. On the other hand, for the tri-layers, we analyzed the existence of bilinear and biquadratic couplings between the magnetizations of adjacent ferromagnetic layers from measurements of magnetization curves. With the FMR fields and line width angular dependencies, information on the anisotropy in three layers was obtained and the effects of different magnetic relaxation mechanisms were evidenced. It was also possible to observe the dependence of the epitaxy of the multilayers with growth and sputtering parameters. Additionally it was developed the technique of AC magnetic susceptibility in order to obtain further information during the investigation of magnetic thin films / Nesta disserta??o investigamos as propriedades magn?ticas de um filme monocristalino de ferro e tricamadas com a composi??o Fe(80?)/Cr(t)/Fe(80?), variando as espessuras da camada met?lica n?o magn?tica separadora (Cr) entre 9? < t < 40?. As amostras foram depositadas pela t?cnica Sputtring DC sobre substrato de ?xido de Magn?sio (MgO) com orienta??o cristalina (100). Para esta investiga??o foram utilizadas as t?cnicas experimentais de magnetometria por efeito Kerr Magneto-?ptico (MOKE) e Resson?ncia Ferromagn?tica (FMR). Estas t?cnicas permitiram o estudo das propriedades est?ticas e din?micas da magnetiza??o das multicamadas. Os resultados experimentais foram interpretados com base no modelo fenomenol?gico que leva em considera??o os termos mais relevantes da energia livre magn?tica para descrever o comportamento do sistema. Para o filme monocristalino de ferro, realizamos uma discuss?o anal?tica das informa??es das curvas de magnetiza??o e desenvolvemos uma simula??o num?rica baseada no modelo de Stoner-Wohlfarth, possibilitando o ajuste num?rico das curvas de magnetiza??o experimentais e a obten??o do valor de campo de anisotropia. Para as tricamadas, analisamos a presen?a dos acoplamentos bilinear e biquadr?tico entre as magnetiza??es das camadas ferromagn?ticas adjacentes a partir das medidas das curvas de magnetiza??o. Com as depend?ncias angulares do campo de FMR e da largura de linha obtivemos informa??es sobre as anisotropias presentes nas tricamadas e evidenciamos os efeitos de diversos mecanismos de relaxa??o magn?tica. Tamb?m foi poss?vel observar a depend?ncia da epitaxia das multicamadas com os par?metros de crescimento do Sputtering. Adicionalmente foi desenvolvida, durante o per?odo do mestrado, a t?cnica de susceptibilidade magn?tica AC com o objetivo de obter resultados inovadores na investiga??o de filmes finos magn?ticos