The interface of semiconductors plays an important role in all semiconductor devices - often defining the device's properties. Ionic liquids are typically employed as gating dielectrics to achieve high charge densities at semiconductor surfaces. Such ionic liquid/semiconductor interfaces are usually studied using electrical transport techniques, which often have the drawback of requiring modeling to achieve an understanding of the species involved in the devices at the ionic liquid/semiconductor interfaces. Through the use of infra-red and optical spectroscopy this work seeks to uncover the nature of charge carriers surface of both organic semiconductors, specifically rubrene, and two dimensional semiconductors, specifically monolayer MoS2, and how these charges interact in the presence of mobile ions. I show that for rubrene infra-red spectroscopy reveals with the formation of an ionic liquid/rubrene interface the rubrene surface becomes intrinsically hole doped. Additionally, that when rubrene is gated the ionic liquid to achieve high charge densities in rubrene there is a saturation of the conductive species resulting in a lowering of hole mobility. In the case of monolayer MoS2 photoluminescence spectroscopy shows that forming the ionic liquid/MoS2 interface results in mobile ions screen the charged defects in the MoS2 increasing the photoluminescence intensity.

Silicon nanocrystals (NCs), especially Si NCs embedded in SiO₂, have been studied intensely for decades for their potential application in silicon photonics, especially as efficient room temperature light emitters. Despite progress in fabricating photonic devices from Si NCs, the origin of the efficient photoluminescence (PL), the electronic and microscopic structure of the nanocrystals, and the structure of the elusive NC/SiO₂ interfaces for the oxide-embedded nanocrystals, remain controversial. Optical spectroscopy provides a powerful noninvasive tool for probing the structure of the Si NCs, including the active buried NC/SiO₂ interfaces of embedded particles. In this thesis work, oxide-embedded and free-standing alkyl-passivated silicon nanocrystals, prepared by different techniques, have been studied by linear and nonlinear optical spectroscopies. Cross-polarized 2-beam second-harmonic and sum-frequency generation (XP2-SHG/SFG) has been applied spectroscopically to study oxide embedded Si NCs of different sizes (3 to 5 nm diameter) and interface chemistries. The SHG/SFG spectra of silicon nanocrystals (Si NCs) prepared by implanting Si ions uniformly into silica substrates, then annealing, are compared and contrasted to their spectroscopic ellipsometric (SE) and photoluminescence excitation (PLE) spectra. Three resonances--two close in energy to E₁ (3.4 eV) and E2 (4.27 eV) critical-point resonances of crystalline silicon (c-Si), and a broad resonance intermediate in energy between E₁ and E₂--are observed in all three types of spectra. These features are observed in conjunction with a sharp 520 cm⁻¹ Raman peak characteristic of c-Si and an a-Si tail in the Raman spectra. The appearance of bulk-like CP resonances in the parallel PLE, SE and SHG/SFG spectra from Si NCs suggests the basic electronic structure of the bulk c-Si is preserved in nano-particles as small as 3 nm in diameter, albeit with significant size-dependent modification. At the same time, the prominence of a non-bulk-like resonance intermediate in energy between E₁ and E₂ CPs in all three types of spectra demonstrates the important contribution of nano-interfaces to the electronic structure.We also applied Raman spectroscopy to study oxide-embedded and oxide-free alkyl-passivated Si NCs with diameters ranging from 3 nm to greater than 10 nm synthesized by thermal decomposition of hydrogen silsesquioxane (HSQ). While oxide matrix complicates the size-dependence of the Raman peak shift for oxide-embedded nanocrystals, the Raman peak of the free-standing alkyl-passivated Si NCs shifts monotonically with NC size. / text

A study was made of the thermoreflectance spectra of a series of five thin film samples spanning the range of composition of the amorphous Ge(x)Te(1-x) binary semiconductors. The experiment was performed over photon energies ranging from 0.5 ev in the infrared to 6 ev in the ultraviolet. The results are plotted for energies above the absorption edge. In the Ge-rich materials there was little structure in the thermoreflectance spectrum. However, there was the development of two peaks in the spectrum as the Te content was increased beyond a 50:50 mixture. The results are analyzed in terms of optical constants and electronic structure. It was found that the energy separation of the peaks in the thermoreflectance corresponded closely to the separation of peaks in the valence band density of states seen in photoemission experiments. The existence of the two peaks indicates a "lone pair" band of energy levels positioned between the valence and conduction bands. This is aditional evidence of two-fold coordination of the Te atoms in these materials. At energies below the band gap there was strong interference due to increased transimission of the film. This made the analysis more complicated. A procedure is discussed for extracting from the modulated interference the specific changes occurring in the optical constants with temperature modulation.

This thesis describes three investigations, ranging in subject matters, all of which relating to systems capable of photoinduced reactions involving energy or electron transfer. The phenomenon and the effects of environment in the various systems are explored using different methodologies of optical spectroscopy. As the chapters progress, different investigations introduce and build on fundamental concepts encountered and in complexity of the methodologies used to explore the systems. The first chapter introduces the preparation of water-soluble CdSe nanocrystal clusters. The clusters, created using a protein, are 3-D close-packed self-assemblies of nanocrystals. Due to this close-packed nature, electronic interactions between the nanocrystals allow for energy migration within the cluster. The structural and optical properties of the clusters were described. Then using steady-state spectroscopy, properties of the original nanocrystals were compared to that of the cluster to determine the consequence of nanocrystal coupling interactions and their potential use toward the development of artificial light-harvesting systems. In the second chapter, CdSe nanocrystals are functionalized with a unique electro-active polymer, and the electron transfer between the nanocrystal and the electro-active polymer adsorbate is investigated. Using fluorescence decay measurements, the electron transfer reaction inherent to the system with respect to a comprehensive range of dielectric solvents was explored. The study illustrates the high complexity of seemingly typical nanocrystal-based systems and provides general awareness of what factors need to be considered when dealing with such systems. The final chapter starts with an informal review of ultrafast nonlinear spectroscopy, focusing on two methods, three-pulse photon echo peak shift (3PEPS) and two-dimensional photon echo (2DPE) electronic spectroscopy, and how they are related. A straightforward approach for extracting 3PEPS data from 2DPE results is presented in a preliminary case study of a dye in two different solvents, one of which is electron-donating.

This thesis describes three investigations, ranging in subject matters, all of which relating to systems capable of photoinduced reactions involving energy or electron transfer. The phenomenon and the effects of environment in the various systems are explored using different methodologies of optical spectroscopy. As the chapters progress, different investigations introduce and build on fundamental concepts encountered and in complexity of the methodologies used to explore the systems. The first chapter introduces the preparation of water-soluble CdSe nanocrystal clusters. The clusters, created using a protein, are 3-D close-packed self-assemblies of nanocrystals. Due to this close-packed nature, electronic interactions between the nanocrystals allow for energy migration within the cluster. The structural and optical properties of the clusters were described. Then using steady-state spectroscopy, properties of the original nanocrystals were compared to that of the cluster to determine the consequence of nanocrystal coupling interactions and their potential use toward the development of artificial light-harvesting systems. In the second chapter, CdSe nanocrystals are functionalized with a unique electro-active polymer, and the electron transfer between the nanocrystal and the electro-active polymer adsorbate is investigated. Using fluorescence decay measurements, the electron transfer reaction inherent to the system with respect to a comprehensive range of dielectric solvents was explored. The study illustrates the high complexity of seemingly typical nanocrystal-based systems and provides general awareness of what factors need to be considered when dealing with such systems. The final chapter starts with an informal review of ultrafast nonlinear spectroscopy, focusing on two methods, three-pulse photon echo peak shift (3PEPS) and two-dimensional photon echo (2DPE) electronic spectroscopy, and how they are related. A straightforward approach for extracting 3PEPS data from 2DPE results is presented in a preliminary case study of a dye in two different solvents, one of which is electron-donating.

Thesis (M.Sc.). / Written for the Dept. of Bioresource Engineering. Title from title page of PDF (viewed 2009/06/18). Includes bibliographical references.

Thesis (M.Sc.). / Written for the Dept. of Bioresource Engineering. Title from title page of PDF (viewed 2009/06/22). Includes bibliographical references.

Thesis (M.S.)--University of Missouri-Columbia, 2008. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on August 12, 2009) Vita. Includes bibliographical references.

Thesis (Ph. D.)--Michigan State University. Dept. of Chemistry, 2008. / Title from PDF t.p. (viewed Sept. 10, 2009). Includes bibliographical references. Also issued in print.

Thesis (PhD)--Montana State University--Bozeman, 2010. / Typescript. Chairperson, Graduate Committee: Aleksander Rebane. Includes bibliographical references (leaves 126-144).