The deposition of hydrocarbons on silicon substrates is a topic of wide interest. This is generally related to the technological importance of silicon carbide (SiC) and a growing interest in graphene and graphitic materials. Methods for producing these materials predominantly involve high processing temperatures. In the case of SiC, these high processing temperatures often result in the formation of surface defects, which compromise the electronic properties of the material. In an effort to grow SiC films at low temperatures, a technique known as electron-beam chemical vapor deposition (EBCVD) has been developed. Most electron beam deposition techniques employ a focused beam of high-energy (20-30 keV) electrons to form nanometer-sized solid deposits on a surface. However, in an effort to deposit macroscale films, a broad beam of low-energy electrons was used. In addition to investigating the applications of low-energy electrons in semiconductor film growth, the fundamental chemical and physical processes induced by the bombardment of adsorbate-covered surfaces with low-energy electrons were examined. Specifically, the electron-stimulated desorption of various adsorbate-substrate systems such as acetylene adsorbed on silicon, graphene oxide on silicon, and ultrathin graphite films on silicon carbide have been investigated. The yields of cation and neutral desorbates as a function incident electron energy were measured, appearance thresholds were determined and mechanisms of desorption were proposed.

Neste trabalho investigamos a dinâmica de formação de nanopartículas de Au por pulsos de femtossegundos formatados (800 nm, 30 fs, 1 kHz e 2 mJ), induzida pela ionização da molécula de quitosana. Inicialmente desenvolvemos um sistema de formatação de pulsos ultracurtos que faz uso de um modulador espacial de luz, constituído por um arranjo linear de cristais líquidos, com o qual somos capazes de impor distintas modulações de fase ao pulso laser. Para monitorar o processo de produção de nanopartículas, montamos um sistema de excitação (pulsos de femtossegundos) e prova (luz branca), o qual permite a observação em tempo real do aparecimento da banda de plásmon e, consequentemente, da dinâmica de formação das nanopartículas. Resultados obtidos para pulsos não formatados (limitados por Transformada de Fourier) demonstraram que a formação de nanopartículas deve-se à ionização não linear da quitosana, a qual está relacionada à oxidação do grupo hidroxila para o grupo carbonila. Medidas de microscopia eletrônica de transmissão forneceram os tamanhos (entre 20 e 100 nm) e formatos (esferas, pirâmides, hexágonos, bastões, etc) das nanopartículas geradas. Ainda, nossos resultados revelaram que esta ionização é iniciada por absorção multifotônica, mais especificamente por absorção de 4 fótons. Utilizando pulsos formatados com fase espectrais constante, degrau e cossenoidal com diferentes frequências, investigamos a influência destes na formação de nanopartículas. Concluímos que os pulsos mais longos são mais favoráveis ao processo de ionização, e consequente redução dos íons de Au para a formação de nanopartículas metálicas. Este comportamento se deve, provavelmente, à redistribuição da energia absorvida para os modos vibracionais, o que é mais provável para pulsos mais longos. Assim, o método apresentado pode abrir novas maneiras para a formação de nanopartículas de metálicas, as quais podem ser mais exploradas dos pontos de vista aplicado e fundamental. / In this work we have studied the synthesis of Au nanoparticles using shaped ultrashort pulses (800 nm, 30 fs, 1 kHz and 2 mJ), induced by the ionization of the chitosan. Initially we developed a pulse shaping setup that uses a spatial light modulator (liquid crystals array), with which we are able to impose distinct phase mask to the laser pulse. In order to monitor the nanoparticles production process, we used a pump-probe system, consisting of femtosecond pulses (pump) and white light (probe), which allows the observation of the plasmon band enhancement and hence the nanoparticles formation dynamics. The results obtained by Fourier Transform limited pulses have shown that the nanoparticles formation is due to the nonlinear ionization of chitosan, which is related to hydroxyl group oxidation to the carbonyl group. Transmission electron microscopy measurements provided the sizes (20-100 nm) and shapes (spheres, pyramids, hexagons, rods, etc.) of the produced nanoparticles. Moreover, our results revealed that ionization is initiated by multiphoton absorption, more specifically by four photons absorption. Using pulses shaped with constant, step and cossenoidal (with different frequencies) spectral phase masks, we investigated their influence in the nanoparticles formation. We conclude that longer pulses are more favorable to the ionization process and, consequently, to the gold ions reduction for the synthesis of the metallic nanoparticles. This behavior is probably due to the redistribution of the absorbed energy to the vibrational modes, which is more likely for longer pulses. Therefore, the approach presented here can open new ways to produce metallic nanoparticles, which can be further explored from applied and fundamental points of view.

Processes at the air-water/ice interface are known to play a very important role in the release of reactive halogen species with atmospheric aerosols serving as catalysts. The ability to make different types of ice with various morphologies, hence, different adsorption and surface properties in vacuum, provide a useful way to probe the catalytic effect of ice in atmospheric reactions. Also, the use of the liquid jet technique provides the rare opportunity to probe liquid samples at the interface; hitherto impossible to investigate with traditional surface science techniques. Studies of reactions on both ice and liquid surfaces at ambient conditions are usually complicated by the rapid desorption and adsorption processes due to the high evaporation rates at the surface. To gain a better understanding and improve modeling of several atmospheric relevant reactions, it is therefore important to develop laboratory techniques that provide an opportunity to investigate non-thermal reactions on both ice and liquid surfaces. Detailed investigation of the interactions of atmospheric relevant molecules (methyl iodide and hydrogen chloride) on water ice at low temperature in UHV conditions has been carried out. These interactions were studied using different techniques such as temperature programmed desorption (TPD), electron stimulated desorption (ESD) and resonance enhanced multiphoton ionization (REMPI). Unlike probing reactions on ice surfaces, investigating air/liquid interfaces present several challenges. This is because traditional surface science techniques require an ultra high vacuum environment to prevent distortion of information due to interference from equilibrium vapor above the liquid surface during data acquisition. The liquid jet technique facilitates the direct study of continually renewed liquid surfaces in high vacuum, thereby preventing the constant changing of the properties and composition of the liquid surface due to the aging process (diffusion of impurities or liquid constituent). A linear time-of-flight mass spectrometer has been used to monitor ion ejection during laser irradiation of liquid jet containing aqueous solutions and pure water. Since these ions are ejected exclusively from the surface of the liquid and the cluster distributions observed are influenced by the local structure, these experiments provide a sensitive probe of the liquid vacuum interface of these solutions. Though the research is fundamental, the results obtained from these investigations indicate how the discontinuity of bulk properties on the surface of both ice and aqueous solutions affects interfacial reactions.