<p>Melanin is a biological pigment that is ubiquitous in nature and generally produced within melanosomes, specialized organelles. Typically, melanin is categorized into two distinct classes, based on color and molecular precursor: eumelanin (brown-black) and pheomelanin (yellow-red). Whereas much is known regarding the molecular precursors to the two pigments, an understanding of their resulting molecular structure remains elusive. Despite this lack of knowledge, several functions are attributed to the pigments, including photoprotection and photosensitization. Epidemiological data for skin and ocular cancers have observed an increased incidence for increased relative concentrations of pheomelanin. Furthermore, eumelanin is generally identified as photoprotective and antioxidant, whereas pheomelanin is generally identified as photoreactive and pro-oxidant. This thesis describes the photophysical properties of the naturally-occuring melanin pigments and presents new insights into their roles within the context of skin and ocular cancers.</p><p> Photoemission electron microscopy provides a unique opportunity to probe the complex photoproperties of melanins contained within intact melanosomes isolated from tissues of bovine and human eyes. Photoionization threshold potentials characteristic of eumelanin and pheomelanin have been determined and are used to investigate the molecular architecture of the pigments within the melanosome. Furthermore, a novel approach to photoemission electron microscopy is used to obtain the first direct measurements of the absorption coefficients from intact melanosomes. </p><p> Human iridal stroma melanosomes are comprised of both eumelanin and pheomelanin in various ratios according to iris color; dark brown and blue-green iris melanosomes are characterized by a eumelanin:pheomelanin ratio of 14.8 and 1.3, respectively. Despite the significant difference in the overall pigment composition, a common eumelanin surface photoionization threshold is obtained for both melanosomes. This data indicates that within the melanosome, the phototoxic pheomelanin pigment is encased by eumelanin. This structure mitigates the adverse photochemical properties of pheomelanin. However, damage to the eumelanic exterior and or significant reduction in the amount of eumelanin present could compromise the protective ability of eumelanin, providing mechanisms for exposure of pheomelanin and consequently contributing to oxidative stress.</p><p> The absorption spectra of intact melanosomes of varying melanin compositions were determined over the spectral range from 244 to 310 nm. The absorption spectra of eumelanic melanosomes are similar regardless of monomer composition or embryonic origin. Furthermore, the absorption spectra of melanosomes containing a mixture of pigments were similar to those containing pure eumelanin, arguing that the absorption properties of the melanosome are maintained regardless of increased pheomelanin composition. Therefore, the correlation between epidemiological data and the eumelanin:pheomelanin ratio is not predicted to be a reflection of the melanosome's decreased ability to attenuate biologically relevant wavelengths, but instead is predicted to be a reflection of the different photoreactivities of the melanin pigments contained within.</p> / Dissertation

In this dissertation, I present the results of my research regarding hybrid semiconductor interfaces between organic and inorganic semiconductors. Using photoemission spectroscopy, I elucidate the important role of defect-induced electronic states within the inorganic semiconductor phase. These states significantly affect both the energy level alignment and the charge carrier dynamics at the hybrid interface. I demonstrate that the behavior of these hybrid semiconductor interfaces is complex and not well characterized by current models for organic semiconductor interfaces. Specifically, I show that hybrid interfaces host unique electronic phenomena that depend sensitively on the surface structure of the inorganic semiconductor. I also demonstrate new applications of photoemission spectroscopies that enable the direct analysis of important properties of inorganic semiconductors, including charge carrier behavior near hybrid interfaces and the electronic character of defect-induced energy levels. The research presented here focuses on two different n-type inorganic semiconductors, tin disulfide (SnS₂) and zinc oxide (ZnO). SnS₂ is a layered transition metal dichalcogenide that presents an atomically flat and inert surface, ideal for sensitively probing electronic interactions at the hybrid interface. To probe the electronic structure of the SnS₂ surface, I used a variety of organic molecules, including copper phthalocyanine, vanadyl naphthalocyanine, chloro-boron subphthalocyanine, and C₆₀. ZnO has a complex surface structure that can be modified by simple experimental procedures; it was therefore used as a tunable semiconductor substrate where the effects of altered electronic structure can be observed. By carefully studying the origin of hybrid interfacial interactions, these research projects provide a first step in explicitly elucidating the fundamental mechanisms that determine the electronic properties of hybrid interfaces.

In this dissertation, I present the results of my research on a prototypical interface of the metal oxide ZnO and the organic semiconductor C₆₀. I establish that the physics at such oxide / organic interfaces is complex and very different from the extensively investigated case of organic semiconductor / metal interfaces. The studies presented in this dissertation were designed to address and improve the understanding of the fundamental physics at such hybrid organic / inorganic interfaces. Using photoemission spectroscopies, I show that metal oxide defect states play an important role in determining the interfacial electronic properties, such as energy level alignment and charge carrier dynamics. In particular, I show that for hybrid interfaces, electronic phenomena are sensitive to the surface electronic structure of the inorganic semiconductor. I also demonstrate applications of photoemission spectroscopies which are unique in that they allow for a direct comparison of ultrafast charge carrier dynamics at the interface and the electronic structure of defect levels. The research presented here focuses on a achieving a significant understanding of the realistic and device relevant C₆₀ / ZnO hybrid interface. I show how the complex surface structure of ZnO can be modified by simple experimental protocols, with direct and dramatic consequences on the interfacial energy level alignment, carrier dynamics and carrier collection and injection efficiencies. As a result of this careful study of the electronic structure and dynamics at the C₆₀ / ZnO interface, a greater understanding of the role of gap states in interface hybridization and charge carrier localization is obtained. This dissertation constitutes a first step in achieving a fundamental understanding of hybrid interfacial electronic properties.

This thesis addresses the electronic structure of molecules and solids using resonant X-ray emission and photoemission spectroscopy. The use of monochromatic synchrotron radiation and the improved performance of the instrumentation have opened up the possibility of detailed analyses of the response of the electronic systems under interaction with X-rays. The experimental studies are accompanied by numerical ab initio calculations in the formalism of resonant inelastic scattering. The energy selectivity has made it possible for the first time to study how the chemical bonds in a molecule break up during resonant inelastic X-ray scattering. In the conjugated polymer systems, the element selectivity of the X-ray emission process made it possible to probe the different atomic elements separately. The X-ray emission technique proved to be useful for extracting isomeric information, and for measuring the change in the valence levels at different degrees of doping. In this thesis, spectral satellite features in transition metals were thoroughly investigated for various excitation energies around a core-level threshold. By measuring the relative spectral intensity of the satellites it was possible to extract information on the partial core-level widths. Using the nickel metal system as an example, it was shown that it is possible to probe the different core-excited states close toshake-up thresholds by measuring the relative spectral intensity variation of the Auger emission.Resonant photoemission measurements showed unambiguous evidence of interference effects. Theseeffects were also thoroughly probed using angle-dependent measurements. The combination of X-rayemission and absorption were useful for studying buried layers and interfaces due to the appreciable penetration depth of soft X-rays. X-ray scattering was further found to be useful for studying low-energy excited states of rare earth metallic compounds and transition metal oxides.

Darmstadt, Techn. University, Diss., 2006.

Photoemission Electron Microscopy (PEEM) is a versatile tool that relies on the photoelectric effect to produce high-resolution electron images. Ultrafast pulse lasers allow for multi-photon PEEM where multiple visible or IR photons excite a single electron in a nonlinear process. The photoelectron yield in both cases is related to the near-field region of electromagnetic fields at the surface of the sample. We use this ability here to analyze wave propagation in a linear dielectric waveguide with wavelengths of 410 nm and 780 nm. The propagation constant of the waveguide can be extracted from interference patterns created by light propagating in the waveguide and incident light. Various properties like the polarization dependence of the propagation can be analyzed. The electromagnetic field interaction at the boundaries can then be deduced, which is essential to understand power flow in wave guiding structures. These results match well with simulations using finite element techniques as well as electromagnetic theory.

Cette thèse étudie l'interaction de nanopointes avec des impulsions laser ultracourtes pour observer l'émission photo-assistée d'électrons. Plusieurs mécanismes physiques entrent en jeu, chacun ayant une signature unique identifiable dans le spectre d'énergie des électrons. Nous avons développé une nouvelle expérience pour observer et identifier ces mécanismes d'émission. Ceci inclut le développement complet d'un système laser flexible (notamment un amplificateur optique non colinéaire (NOPA) haute cadence), une chambre ultra-vide avec détecteur d'électrons (mesure de spectre d'électrons et carte 2D de l'émission) et un dispositif de nanopositionnement de la pointe dans le foyer du laser, et enfin la fabrication et caractérisation de pointes diverses (en collaboration avec les laboratoires CEMES (Toulouse) et GPM (Rouen)). Nous avons observé l'émission photo-induite d'électrons à partir de nanopointes de différents matériaux (tungstène, argent, et une nouvelle pointe formée autour d'un nanotube de carbone unique). Nous avons confirmé l'observation de pics ATP (signature de la photoémission au dessus du seuil) sur une pointe de tungstène. Nous avons détecté la première émission induite par laser à partir de nanocône de carbone unique. Enfin, nous avons observé un plateau dans le spectre d'énergie des électrons d'une pointe d'argent, signature de la recollision et rediffusion des électrons sur la pointe. Pour identifier et caractériser ces mécanismes, des études variées ont été faites en fonction de la tension appliquée sur la pointe, du taux de répétition du laser, de sa polarisation, de sa puissance et de sa longueur d'onde. En étudiant la forme du spectre des photoélectrons, nous avons pu extraire des informations sur l'interaction: le facteur d'amplification du champ laser proche de la nanopointe et la probabilité d'absorption d'un photon au dessus du seuil. / This thesis concerns the interaction of a sharp nanotip with an ultrashort laser pulse for the observation of emission of photoelectrons. An electron can be emitted from a sharp nanotip system by many different mechanisms. Each mechanism gives a unique signature that can be identified by the photoelectron energy spectrum. We developed a new experiment to observe and identify these emission mechanisms. This consists of a flexible laser system (including the development of a high repetition rate, variable repetition rate noncollinear optical parametric amplifier (NOPA)), ultra high vacuum chamber, electron detector (electron spectrometer with 2D resolution), nanopositioning of a sharp nanotip in the focus of the laser, and fabrication of these nanotip samples in a variety of materials (in collaboration with CEMES (Toulouse) and GPM (Rouen)). We observed the emission of photoelectrons from various nanotips based on different materials: tungsten, silver, and a new type of carbon-based nanotip formed around a single carbon nanotube. We confirm the observation of above threshold photoemission (ATP) peaks from a tungsten nanotip. We detected the first laser induced electron emission from a carbon cone based on a single carbon nanotube. We observed a plateau in the electron spectra from a silver nanotip, the signature of electron recollision and rescattering in the tip. Various studies were performed in function of the voltage applied, repetition rate of the laser, laser polarization, energy and wavelength of the laser in order to understand these phenomena. From spectral features we were able to extract information about the system such as the enhancement factor of the laser electric field near the nanotip and the probability of above threshold photon absorption. Comparisons of the various spectra observed allowed us to spectrally identify the mechanisms for photoemission for tip based systems.

This dissertation explores the effect of nanometer-scale changes in structure on the energetics of photocatalytic and photovoltaic materials. Of particular interest are semiconductor nanocrystals (NCs), which have interesting chemical properties that lead to novel structures and applications. Chief among these properties are quantum confinement and the high surface area-to-volume ratio, which allow for chemical tuning of the energetics and structure of NCs. This tunable energetic landscape has led to increasing application of NCs in various areas of research, including solar energy conversion, light-emitting diode technologies, and photocatalysis. However, spectroscopic methods to determine the energetics of NCs have not been well developed, due to chemical complexities of relevant NCs such as polydispersity, capping ligand effects, core-shell structures, and other chemical modifications. In this work, we demonstrate and expand the utility of photoelectron spectroscopy (PES) to probe the energetics of NCs by considering the physical processes that lead to background and secondary photoemission to enhance photoemission from the sample of interest. A new methodology for the interpretation of UP spectra was devised in order to emphasize the minute changes to the UP spectra line shape that arise from nanoscopic changes to the NCs. We applied various established subtractions that correct for photon source satellites, secondary photoelectrons, and substrate photoemission. We then investigated the effect of ligand surface coverage on the surface chemistry and density of states at the top of valence band (VB). We systematically removed ligands by increasing numbers of purification steps for two diameters of NCs and found that doing so increased photoemission density at the top of the VB, which is due to undercoordinated surface atoms. Deeper VB structure was also altered, possibly due to reorganization of the atoms in the NC. Using the new UPS interpretation methodology, we examined the evolution of the valence band energy (EVB) of CdSe NCs as it was modified from spherical NC to rod to Au-NP tipped nanorod (NR). We also employed potential-modulated attenuated total reflectance spectroscopy (PM-ATR) to probe the conduction band energy (ECB) of the series. The EVB decreased with each modification, which is predicted with a band-bending model. This trend was also observed in the ECB, as revealed by spectroelectrochemistry, along with the appearance of new metal-semiconductor states in the band gap. UPS was finally used to investigate the even more complex Pt-NP tipped CdSe@CdS core@shell NR heterostructure. The addition of the CdS shell decreases the EVB relative to CdSe, as expected from common cation II-VI compounds. The Pt-NC increases the EVB, which, like the Au-CdSe NR, is predicted by employing a band-bending model. XPS revealed that PtSx-like chemical states were formed near the CdS-Pt interface. These experiments, along with the improved UP spectra interpretation methodology, demonstrate the wealth of information regarding surface chemistry and energetics that can be obtained with PES which can be applied to not only NCs, but also to metal oxide or molecular thin films.

Organic semiconductor interfaces are promising materials for use in next-generation electronic and optoelectronic devices. Current models for metal-organic interfacial electronic structure and dynamics are inadequate for strongly hybridized systems. This work aims to address this issue by identifying the factors most important for understanding chemisorbed interfaces with an eye towards tuning the interfacial properties. Here, I present the results of my research on chemisorbed interfaces formed between thin-films of phthalocyanine molecules grown on monocrystalline Cu(110). Using atomically-resolved nanoscale imaging in combination with surface-sensitive photoemission techniques, I show that single-molecule level interactions control the structural and electronic properties of the interface. I then demonstrate that surface modifications aimed at controlling interfacial interactions are an effective way to tailor the physical and electronic structure of the interface. This dissertation details a systematic investigation of the effect of molecular and surface functionalization on interfacial interactions. To understand the role of molecular structure, two types of phthalocyanine (Pc) molecules are studied: non-planar, dipolar molecules (TiOPc), and planar, non-polar molecules (H2Pc and CuPc). Multiple adsorption configurations for TiOPc lead to configuration-dependent self-assembly, Kondo screening, and electronic energy-level alignment. To understand the role of surface structure, the Cu(110) surface is textured and passivated by oxygen chemisorption prior to molecular deposition, which gives control over thin-film growth and interfacial electronic structure in H2Pc and CuPc films. Overall, the work presented here demonstrates a method for understanding interfacial electronic structure of strongly hybridized interfaces, an important first step towards developing more robust models for metal-organic interfaces, and reliable, predictive tuning of interfacial properties.

We use quantum electrodynamics (QED) to investigate the possibility of radiative interference from a single laser-driven electron wave packet. Intuition gleaned from classical electrodynamics suggests that radiation from a large electron wave packet might interfere destructively when different regions of the packet oscillate out of phase with each other. We show that when the incident light is represented with a multi-mode coherent state, the relative phases of the electron's constituent momenta have no influence of the amount of scattered light. Hence, the radiation does not depend on the amount of free-particle spreading experienced by the electron before the interaction. This result is shown to hold to all orders of perturbation theory. We extend our conclusions using the Furry picture of QED, where the (now-classical) incident light pulse is treated non-perturbatively with Volkov functions. We connect our results to a first-quantized picture by comparing transition probabilities between QED and semiclassical models. We are able to match these probabilities by choosing the classical scattered light field to be a single mode with energy hω'.