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Raman spectroscopy, laser-induced fluorescence, and sum-frequency generation (SFG) spectroscopy are used to investigate the behavior of compressible mobile phases and stationary phases under a variety of chromatographic conditions. Efforts to understand and optimize separations employing compressible mobile phases have been limited by a lack of understanding of the mobile phase density gradient. Mobile phase compressibility leads to gradients in linear velocity and solute retention and affects separation speed and efficiency, especially in packed columns. This work describes on-column density measurement of CO2, a common carrier fluid for SFC and SGC, in packed capillary columns using Raman microspectroscopy. On-column detection by laser-induced fluorescence is used to observe the effect of the mobile phase density gradient on separation speed and efficiency, and experimental efficiency is compared to a theoretical model. Additionally, SFG spectroscopy allows for probing the structure of model monomeric and polymeric C18 stationary phases under pressure; this provides a basis for correlating selectivity with pressure-induced structural changes in stationary phase materials. Together, this work provides a more complete understanding of the role of column pressure and fluid compressibility on the speed, efficiency, and selectivity of chemical separations.

Esta Tese aborda o estudo de transistores por efeito de campo orgânicos (OFETs do inglês, Organic Feld-Effect Transistors). Entender o comportamento da carga acumulada no canal do OFET, a qual é responsável pelo processo de condução elétrica no dispositivo, é de grande importância para ajudar a melhorar sua eficiência ou a propor um modelo teórico que descreva o comportamento do transistor em todos os seus regimes de operação. Vários trabalhos na literatura investigam o campo elétrico na camada semicondutora do transistor (ao longo do canal) gerado pela acumulação de cargas, porém nenhum investiga o campo na camada dielétrica de OFETs, que é diretamente proporcional à carga acumulada no canal. Investigou-se inicialmente o campo elétrico na camada dielétrica do dispositivo por meio da espectroscopia vibracional por Geração de Soma de Frequências (espectroscopia SFG do inglês, Sum-Frequency Generation). Espectros SFG obtidos nos dispositivos polarizados exibiram uma banda em ~1720 cm-1, devido ao grupo carbonila da camada dielétrica orgânica (PMMA – poli(metil metacrilato)), cuja a amplitude foi proporcional à voltagem de porta aplicada, indicando que esses grupos polares foram orientados sob ação do intenso campo elétrico no dispositivo. Esse sinal SFG induzido pelo campo pode ser devido a duas contribuições, um termo não linear de segunda ordem (devido à reorientação molecular) e outro de terceira ordem (interação entre os campos ópticos e o campo estático no volume do material). Observamos uma redução quase completa do sinal SFG em altas temperaturas (próximas da Tg do polímero dielétrico), indicando que o mecanismo de reorientação molecular é o responsável pelo sinal SFG gerado. Foram realizadas então medidas preliminares de microscopia SFG para mapear esse sinal SFG ao longo do canal de OFETs a base dos polímeros N2200 (semicondutor) e PMMA (dielétrico). Os resultados conseguem demonstrar a variação da densidade de carga acumulada no canal quando o dispositivo está polarizado e próximo à saturação. Usando Microscopia por Modulação de Carga (microscopia CMM do inglês, Charge Modulation Microscopy), que é outro método não invasivo para investigar a acumulação de cargas em um dispositivo operando, mapeamos a distribuição de carga no canal desses OFETs com alta resolução espacial (sub-micrométrica). Além disso, uma simulação da densidade de carga esperada e dos perfis de CMM foi realizada usando um modelo ambipolar para OFETs. Com base nessas simulações, propusemos uma modulação de onda quadrada do OFET, que permite uma comparação mais direta dos perfis de CMM com o perfil de densidade de carga ao longo do canal do transistor. Usando o esquema proposto, esses perfis foram medidos e comparados com o esperado com base no modelo ambipolar. Em geral os perfis de densidade de carga obtidos concordam bem com o modelo, usando apenas um único parâmetro global ajustável, exceto muito próximo do eletrodo de dreno e no regime de saturação profunda, quando os experimentos apresentam um artefato devido à eletro-absorção e não permitem uma comparação precisa com o modelo. Portanto, espera-se que esta Tese tenha contribuído para o avanço de técnicas de caracterização da distribuição de carga em OFETs, e assim melhorar o entendimento de seus mecanismos de funcionamento. / This Thesis deals with the study of Organic Field Effect Transistors (OFETs). Understanding the behavior of the accumulated charge along the OFET channel, which is responsible for the electrical conduction process in the device, is of great importance for improving its efficiency or proposing a theoretical model that describes the behavior of the transistor in all its operating regimes. Several studies in the literature investigate the electric field in the semiconductor layer of the transistor (along the channel) generated by the charge accumulation, but none investigates the field in the OFET dielectric layer, which is directly proportional to the charge accumulated in the channel. The electric field in the dielectric layer of the device was initially investigated by Sum-Frequency Generation (SFG) vibrational spectroscopy. SFG spectra obtained in the polarized devices exhibited a band at ~ 1720 cm-1, due to the carbonyl group of the organic dielectric layer (PMMA - poly (methyl methacrylate)), whose amplitude was proportional to the applied gate voltage, indicating that these polar groups were oriented by the intense electric field in the device. This field-induced SFG signal may be due to two contributions, a second order non-linear term (due to molecular reorientation) and a third order term (interaction between the optical fields and the static field in the material volume). We observed an almost complete reduction of the SFG signal at high temperatures (close to the Tg of the dielectric polymer), indicating that the molecular reorientation mechanism is responsible for the generated SFG signal. Preliminary SFG microscopy measurements were performed to map this SFG signal along the channel of OFET fabricated with N2200 (semiconductor) and PMMA (dielectric) polymers. The results demonstrate the variation of the accumulated charge density along the channel when the device is polarized and close to saturation. Using Charge Modulation Microscopy (CMM), which is another noninvasive method to investigate the accumulation of charges in an operating device, we mapped the charge distribution in the channel of these OFETs with high spatial resolution (sub-micrometer). In addition, a simulation of the expected charge density and CMM profiles was performed using an ambipolar model for OFETs. Based on these simulations, we proposed a square-wave modulation of the OFET, which allows a more direct comparison of the CMM profiles with the charge density profile. Using the proposed scheme, these profiles along the transistor channel were measured and compared with those expected from the ambipolar model. In general, the obtained charge density profiles agree well with the model, using only a single global adjustable parameter, except very close to the drain electrode and in the deep saturation regime, when the experiments have an artifact due to the electro-absorption and do not allow a precise comparison with the model. Therefore, it is expected that this Thesis has contributed to the advancement of techniques to characterize the charge distribution in OFETs, and thus improve the understanding of its operating mechanisms. Keywords: Field-effect transistors. Organic electronics. Nonlinear optics. Sum-frequency generation. Polarization of dielectrics. Charge modulation microscopy. Metal-insulator-semiconductor capacitor.

Estudos de interface têm presenciado um recente crescimento devido as novas propriedades físico-químicas, que puderam ser explorados com o advento de técnicas com resolução ao nível molecular/atômico. Dessas técnicas, dois ramos que merecem destaque são as Microscopias de Varredura por Ponta de Prova e Espectroscopias Óticas. Neste trabalho fazemos uso de algumas destas técnicas (o Microscópio de Tunelamento de Elétrons e Espectroscopia Vibracional por Geração de Soma de Freqüências) para estudar a adsorção de moléculas alifáticas e aromáticas em Au. Dois casos são abordados: como a rugosidade do substrato influencia no mecanismo de automontagem de monocamadas de alcanotióis e a automontagem de derivados de uracil em interfaces eletroquímicas. No primeiro caso, mostra-se que a quantidade de defeitos moleculares na monocamada adsorvida e extremamente sensível a rugosidade do substrato utilizado. Unem-se os resultados das técnicas acima aos resultados de sondas eletroquímica para se chegar a um modelo. Também e estudado a dependência das etapas de fisisorção e quimisorção em função da concentração da solução de alcanotiól. Para o segundo caso, um derivado halogenado do uracil (5-fluorouracil), mostra-se como a substituição química na base nitrogenada leva a diferentes mecanismos de formação de monocamadas na interface eletroquímica. Imagens de Microscopia de Tunelamento de Elétrons com resolução atômica e molecular mostram que em densidade de cargas negativas as moléculas estão fisisorvidas, porém não formam estruturas periódicas em contraste com uracil e timina, entretanto em densidades de cargas positivas formam estruturas periódicas quimisorvidas, assim como uracil e timina. E discutido como são diferentes os mecanismos de interação intermolecular: no caso dos alcanotiois preponderando às interações de van der Waals e no caso dos derivados de uracil pelas ligações via pontes de hidrogênio são dominantes. / Interface science has experienced a new rebirth since the development of new probes with atomic/molecular resolution, giving new insights about the physical-chemical properties, which differ substantially from the bulk. Among these techniques, two branches deserve special attention: the Scanning Probe Microscopies and Optical Spectroscopy. In this work, two derivatives of theses techniques (the Scanning Tunnelling Microscopy and Vibrational Spectroscopy by Sum-Frequency Generation) are combined giving new insights about the molecular adsorption onto Au. Two examples are focused: how roughness plays a key role in the structure of self-assembled alkanethiol monolayer and the uracil derivatives self-assembling at electrochemical interfaces. For the former, it has been shown that the amount of defects on the adsorbed monolayer is highly sensitive to substrate roughness. Combining the results of each technique with a well-known electrochemical probe, a physical model is proposed. The physisorbed and chemisorbed states are studied as a function of alkanethiol solution concentration as well. For the later case, the chemical substitution of uracil leads to drastically different results for the physisorbed phase (negative charge densities), compared to uracil and thymine. In the chemisorbed phase (positive charge densities) imaging with molecular resolution is achieved showing a quasi-hexagonal structure, similar to the structure of thymine and uracil. It is discussed what are the main driving forces for the self-assembling mechanism: van der Waal interactions for the alkanethiols and hydrogen bonding for uracil derivatives.

In this thesis the structure and hydration of small organic and amphipilic compounds adsorbed at the air-liquid interface, have been studied using the nonlinear optical technique Vibrational Sum Frequency Spectroscopy (VSFS). The second order nature of the sum frequency process makes this technique particularly surface sensitive and very suitable for interfacial studies, as molecules at the surface can be distinguished even in the presence of a vast excess of the same molecules in the bulk. Particular emphasis was given to the surface water structure and how it is affected by the presence of small model compounds such as acetic acid and formic acid, and also non-ionic surfactants with sugar based and ethylene oxide based polar headgroups. Understanding the structure of water at these interfaces is of considerable fundamental importance, and here VSFS provided unique information. Upon addition of tiny amounts of these surface active compounds, the ordered surface structure of water was found to be significantly perturbed, as revealed by the changes observed in the characteristic spectroscopic signature of the dangling OH bond of water molecules, which vibrate free in air and are present in the top monolayer. Dramatic differences between the different compounds were also observed in the bonded OH region, providing a valuable insight into the hydration of polar groups at interfaces. Additionally, by employing different polarization combinations of the laser beams involved in the sum frequency process, information about the different water species present at the surface and their average orientation were extracted. In particular an unusual state of water was found with a preferred orientation in a non-donor configuration in close proximity to the hydrophobic region formed by the hydrocarbon tails of the surfactant molecules. The conformation and orientation of the different adsorbates were also characterized, targeting their specific vibrational frequencies. Noteworthy is the orientation of the fluorocarbon chain of ammonium perfluorononanoate (APFN), which in contrast to the hydrocarbon chains of the other surfactant molecules studied, remained constant over a wide range of surface densities. This behaviour was also observed for the anionic headgroup of sodium dodecyl sulphate (SDS). Other interesting findings were the formation of a cyclic dimer bilayer at the surface of concentrated aqueous solutions of acetic acid and the water structuring effect induced by poly(ethylene-oxide) headgroups, in spite of being themselves disordered at the air-liquid interface.

<p>In this thesis the structure and hydration of small organic and amphipilic compounds adsorbed at the air-liquid interface, have been studied using the nonlinear optical technique Vibrational Sum Frequency Spectroscopy (VSFS). The second order nature of the sum frequency process makes this technique particularly surface sensitive and very suitable for interfacial studies, as molecules at the surface can be distinguished even in the presence of a vast excess of the same molecules in the bulk. Particular emphasis was given to the surface water structure and how it is affected by the presence of small model compounds such as acetic acid and formic acid, and also non-ionic surfactants with sugar based and ethylene oxide based polar headgroups. Understanding the structure of water at these interfaces is of considerable fundamental importance, and here VSFS provided unique information. Upon addition of tiny amounts of these surface active compounds, the ordered surface structure of water was found to be significantly perturbed, as revealed by the changes observed in the characteristic spectroscopic signature of the dangling OH bond of water molecules, which vibrate free in air and are present in the top monolayer. Dramatic differences between the different compounds were also observed in the bonded OH region, providing a valuable insight into the hydration of polar groups at interfaces. Additionally, by employing different polarization combinations of the laser beams involved in the sum frequency process, information about the different water species present at the surface and their average orientation were extracted. In particular an unusual state of water was found with a preferred orientation in a non-donor configuration in close proximity to the hydrophobic region formed by the hydrocarbon tails of the surfactant molecules.</p><p>The conformation and orientation of the different adsorbates were also characterized, targeting their specific vibrational frequencies. Noteworthy is the orientation of the fluorocarbon chain of ammonium perfluorononanoate (APFN), which in contrast to the hydrocarbon chains of the other surfactant molecules studied, remained constant over a wide range of surface densities. This behaviour was also observed for the anionic headgroup of sodium dodecyl sulphate (SDS). Other interesting findings were the formation of a cyclic dimer bilayer at the surface of concentrated aqueous solutions of acetic acid and the water structuring effect induced by poly(ethylene-oxide) headgroups, in spite of being themselves disordered at the air-liquid interface.</p>