Cílem této práce bylo studium Heuslrových sloučenin pomocí optických a magneto-optických (MO) metod. V případě první sloučeniny, Co2FeGa0.5Ge0.5, jsme studovali výskyt strukturálního disorderu za pomoci spektroskopické elipsometrie, MO spektroskopie a MO Kerrovy magnetome- trie. Experimentální výsledky jsme poté porovnali s teoretickými modely. Doplnili jsme také výsledky našich spolupracovník·, a to včetně X-ray difrakce, atomic-force mikroskopie a ab initio výpočt·, abych potvrdili naši interpretaci naměřených výsledk·. Bylo zjištěno, že strukturální disorder je vskutku pozorovatelný pomocí metod, kterých jsme využili. Jeho výskyt se projevil změnou elektronové struktury vzork·. V případě druhé sloučeniny, Fe2MnGa, jsme vyšetřovali vliv obsahu Fe složky na optické a MO vlastnosti tohoto materiálu. Zjistili jsme, že atomy Fe ovlivňují koncentraci volných elektron·, čímž dodávají sloučenině kovový charakter (v porovnání s Ni2MnGa). Zároveň zvyšují optickou a MO odezvu v blízké infra-červené oblasti spektra. Dále bylo zjištěno, že vzorek s nejvyšším obsahem Fe má nulovou magnetizaci. 1

The overall goal of this thesis is the development of wearable flexible optical imaging systems (We-FOISs) that can be used for diffuse optical spectroscopy (DOS) and tomography (DOT). The advantages of We-FOISs lie in their low-cost, portability, and simple patient-interface compared to current DOS and DOT systems. A flexible form factor provides conformal attachment even in cases where the targets such as fingers and toes have a strongly curved surface. We-FOIS technology is a scalable and expandable. Each system can be designed with multiple pairs of light sources and photodetectors depending on the needs and size of the target. The We-FOISs presented in this thesis were developed based on a modular design. The two main modules are a sensing unit and a control unit (a.k.a. sensing band and control band). Two different types of sensing units have been developed. The first type is based on inorganic optoelectronic components such as light emitting diode (LED) and silicon-photodiode (Si-PD). The second type is made with organic components such as organic light emitting diodes (OLEDs), quantum-dot light emitting diodes (QD-LED), and organic photodiodes (OPDs). The flexible control units operate the light sources, read the intensity of the light transmitted through biological tissue, and send data to the computer. Depending on the number of pairs of light sources and photodiodes placed on the flexible sensing bands, the control units have different designs. Furthermore, a small integrating sphere system (SISS) was developed to measure the optical properties (absorption and scattering coefficients, μa and μs) of biological tissue samples and tissue-mimicking phantoms, which were to be used to calibrate the We-FOISs. The accuracy of the SISS as a function of the sample thickness was investigated by comparing a widely used inverse-adding-doubling (IAD) program and inverse-Monte-Carlo (IMC) simulations. Finally, the performance of the different We-FOISs were tested in various pre-clinical and clinical applications, including epilepsy monitoring in rat brains, monitoring of peripheral artery disease (PAD) in human feet, diagnosing systemic lupus erythematosus (SLE) in human fingers, and characterizing tumors in breast cancer patients. The results demonstrated the potentials of the We-FOISs for monitoring of symptoms of various diseases and for applications in point of care.

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ABSTRACT Erythema is a well-documented early indicator of tissue injury resulting from exposure to high doses of ionizing radiation. Close monitoring of radiation-induced injury to the skin can help identify opportunities for early interventions that may prevent or reduce more severe reactions. The gold standard for monitoring erythema is visual assessment (VA) by a trained clinician. This method has been criticized for being subjective and designed with very broad categorical descriptors. This work introduces a newly developed VA scale called the clinician erythema assessment for radiation therapy (CEA-RT).The reliability and accuracy of the CEA-RT scale was tested among 20 radiation therapists who trained to use the scale on digital images of radiation induced erythema. CEA-RT demonstrated to be highly reliable when therapist’s grades were compared to themselves, but moderately accurate when therapist’s grades were compared to each. A follow-up study with real patients and fewer but more extensively trained raters was proposed to demonstrate the grading accuracy of the CEA-RT scale. As an alternatively to VA, spectroscopy has the ability to monitor erythema by measuring the change in concentration of hemoglobin (Hb) within the vessels of the skin. These changes in Hb concentration are linked to the degree of erythema. This thesis also investigated the use of hyperspectral imaging (HSI) and diffuse reflectance spectroscopy (DRS) as potential technological alternatives for evaluating erythema. In a second study, Erythema was artificially induced in 3 volunteers who participated in a pilot study designed to assess the ability of an experimental HSI camera to detect skin changes. The data extracted from the hyperspectral images was found to effectively yield spectral profiles and Dawson’s erythema indices (EI) in agreement with the erythema grades assigned by the gold standard therefore showing HSI to be a viable alternative of assessing erythema. Finally, a third study compared DRS measurements to VA using the CEA-RT scale. The DRS system was previously used to measure in vivo erythema but did not compare spectral measurements to an accepted standard. Ten patient volunteers received daily DRS and VA evaluations for a period of 2 to 4 weeks. The results demonstrated that the Dawson’s EI calculated from the spectral data correlated well with the gold standard (VA grades) and that DRS is able to detect changes in the skin throughout the course of radiation treatments. / Thesis / Master of Science (MSc)

Aerosol particles are important in air quality, climate, and human health. They can affect the earth’s energy budget directly by scattering and absorbing solar radiation and serve as cloud condensation nuclei (CCN), thus influencing cloud properties and lifetime. Atmospheric aerosols are formed through a wide variety of natural and anthropogenic sources. This dissertation presents a comprehensive investigation into the behavior of water-soluble organic molecules on atmospheric aerosol surfaces using Second Harmonic Scattering (SHS). The study focuses on understanding the partitioning of these molecules at the aerosol surface, a crucial aspect in atmospheric chemistry impacting cloud formation, radiation balance, and air quality. The research is divided into three main parts. Initially, the study explores the disposition of organic molecules on aerosol surfaces, utilizing a modified Langmuir model to describe their behavior. This part emphasizes the predominant residence of these molecules on the aerosol surface, highlighting the surface's significant role in atmospheric reactions. The second part examines the interactions between salts and organic molecules on the aerosol surface. A series of experiments with varying salts reveal how different ions influence the partitioning behavior of organic molecules, underscoring the importance of ionic species in governing aerosol surface dynamics. The final part of the study reveals a significant difference between the aerosol and planar air-water interfaces. The equilibrium rate constant for aerosols is found to be tenfold faster, indicating a larger Gibbs free energy, contrasting with the planar air-water interface scenario. And aerosol surfaces exhibit lower molecular density due to the finite availability of organic molecules. These findings highlight aerosol surfaces' unique kinetic and thermodynamic behaviors compared to their planar counterparts. This work significantly advances our understanding of aerosols, their surfaces, and the various factors influencing their behavior in the atmosphere. The findings have crucial implications for our comprehension of climate change, air quality, and aerosols' environmental and health impacts. The introduction of a novel in-situ technique for detecting organic molecules at aerosol surfaces marks a breakthrough in aerosol research, offering insights into the distribution and interactions of these molecules within atmospheric particles. / Chemistry

Doctor of Philosophy / Department of Physics / Jingyu Lin / Time-resolved deep ultraviolet (DUV) Photoluminescence (PL) spectroscopy system has been employed to systematically monitor crystalline quality, identify the defects and impurities, and investigate the light emission mechanism in III-nitride semiconducting materials and photonic structures. A time correlated single photon counting system and streak camera with corresponding time resolutions of 20 and 2 ps, respectively, were utilized to study the carrier excitation and recombination dynamics. A closed cycle He-flow cryogenic system was employed for temperature dependent measurements. This system is able to handle sample temperatures in a wide range (from 10 to 900 K). Structural, electrical, and morphological properties of the material were monitored by x-ray diffraction (XRD), Hall-effect measurement, and atomic force microscopy (AFM), respectively. Most of the samples studied here were synthesized in our laboratory by metal organic chemical vapor deposition (MOCVD). Some samples were bulk AlN synthesized by our collaborators, which were also employed as substrates for homoepilayer growth. High quality AlN epilayers with (0002) XRD linewidth as narrow as 50 arcsec and screw type dislocation density as low as 5x10[superscript]6 cm[superscript]-2 were grown on sapphire substrates. Free exciton transitions related to all valence bands (A, B, and C) were observed in AlN directly by PL, which allowed the evaluation of crystal field (Δ[subscript]CF) and spin-orbit (Δ[subscript]SO) splitting parameters exerimentally. Large negative Δ[subscript]CF and, consequently, the difficulties of light extraction from AlN and Al-rich AlGaN based emitters due to their unique optical polarization properties have been further confirmed with these new experimental data. Due to the ionic nature of III-nitrides, exciton-LO phonon Frohlich interaction is strong in these materials, which is manifested by the appearance of phonon replicas accompanying the excitonic emission lines in their PL spectra. The strength of the exciton-phonon interactions in AlN has been investigated by measuring the Huang-Rhys factor. It compares the intensity of the zero phonon (exciton emission) line relative to its phonon replica. AlN bulk single crystals, being promising native substrate for growing nitride based high quality device structures with much lower dislocation densities (<10[superscript]4 cm[superscript]-2), are also expected to be transparent in visible to UV region. However, available bulk AlN crystals always appear with an undesirable yellow or dark color. The mechanism of such undesired coloration has been investigated. MOCVD was utilized to deposit ~0.5 μm thick AlN layer on top of bulk crystal. The band gap of strain free AlN homoepilayers was 6.100 eV, which is ~30 meV lower compared to hetero-epitaxial layers on sapphire possessing compressive strain. Impurity incorporation was much lower in non-polar m-plane growth mode and the detected PL signal at 10 K was about an order of magnitude higher from a-plane homo-epilayers compared to that from polar c-plane epilayers. The feasibility of using Be as an alternate p-type dopant in AlN has been studied. Preliminary studies indicate that the Be acceptor level in AlN is ~330 meV, which is about 200 meV shallower than the Mg level in AlN. Understanding the optical and electronic properties of native point defects is the key to achieving good quality material and improving overall device performance. A more complete picture of optical transitions in AlN and GaN has been reported, which supplements the understanding of impurity transitions in AlGaN alloys described in previous reports.

This thesis reassigns the OTe-VCd complex in CdTe and the OSe-VCd complex in CdSe to a sulfur-dioxygen complex SO2*, and the OCd defect in CdSe to a VCdH2 complex using Fourier transformed infrared absorption spectroscopy. The publications of the previous complexes were investigated by theoreticians who performed first-principle calculations of theses complexes. The theoreticians ruled out the assignments and proposed alternative defects, instead. The discrepancy between the experimentally obtained and theoretically proposed defects was the motivation of this work. Two local vibrational modes located at 1096.8 (v1) and 1108.3 cm-1 (v2) previously assigned to an OTeV_Cd complex are detected in CdTe single crystals doped with CdSO4 powder. Five weaker additional absorption lines accompanying v1 and v2 could be detected. The relative intensities of the absorption lines match a sulfur-dioxygen complex SO2* having two configurations labeled v1 and v2. A binding energy difference of 0.5+-0.1meV between the two configurations and an energy barrier of 53+-4 meV separating the two configurations are determined. Uniaxial stress applied to the crystal leads to a splitting of the absorption lines which corresponds to an orthorhombic and monoclinic symmetry for v1 and v2, respectively. In virgin and oxygen-doped CdSe single crystals, three local vibrational modes located at 1094.1 (gamma_1), 1107.5 (gamma_2), and 1126.3 cm-1 (gamma_3) previously attributed to an OSe-VCd complex could be observed. The signals are accompanied by five weaker additional absorption features in their vicinity. The additional absorption lines are identified as isotope satellites of a sulfur-dioxygen complex SO2* having three configurations gamma_1, gamma_2, and gamma_3. IR absorption measurements with uniaxial stress applied to the CdSe crystal yield a monoclinic C1h symmetry for gamma_1 and gamma_2. The SO2* complex is stable up to 600 C. This thesis assigns the v- lines in CdTe and gamma-lines in CdSe to local vibrational modes of a sulfur-dioxygen complex SO2*. A hydrogen-doped CdSe single crystal exhibits two absorption lines at 1992 (SeH$_\\parallel$) and 2001 cm-1 (SeH$_\\perp$). Both signals show a red-shift in frequency to 1454 (SeD$_\\parallel$) and 1461 cm-1 (SeD$_\\perp$) when hydrogen is replaced by deuterium. This frequency shift in combination with the fine structure of the absorption lines arising from Se isotopes yields a VCdH2 defect giving rise to SeH$_\\parallel$ and SeH$_\\perp$. This contradicts the previously assignment of the two absorptions lines to an OCd defect. The SeH$_\\parallel$ and SeH$_\\perp$ vibrational modes are found to be aligned parallel and perpendicular to the c-axis of the crystal, respectively. The VCdH2 defect is stable up to a temperature of 525 C.

Recently developed two-dimensional colloidal semiconductor nanocrystals, or nanoplatelets (NPLs), extend the palette of solution-processable free-standing 2D nanomaterials of high performance. Growing CdSe and CdS parts subsequently in either side-by-side or stacked manner results in core–crown or core/shell structures, respectively. Both kinds of heterogeneous NPLs find efficient applications and represent interesting materials to study the electronic and lattice excitations and interaction between them under strong one-directional confinement. Here, we investigated by Raman and infrared spectroscopy the phonon spectra and electron–phonon coupling in CdSe/CdS core/shell and core–crown NPLs. A number of distinct spectral features of the two NPL morphologies are observed, which are further modified by tuning the laser excitation energy Eexc between in- and off-resonant conditions. The general difference is the larger number of phonon modes in core/shell NPLs and their spectral shifts with increasing shell thickness, as well as with Eexc. This behaviour is explained by strong mutual influence of the core and shell and formation of combined phonon modes. In the core–crown structure, the CdSe and CdS modes preserve more independent behaviour with only interface modes forming the phonon overtones with phonons of the core. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Espectros de absorção, fluorescência e excitação do íon Eu+3 em GdAlO3 na região do visível são mostrados neste trabalho. Todos os níveis 7Fj (j= 0, 1, 2 e 4) e 5Dj (j= 0 a 2) foram medidos e quase todas as transições do íon, na região do visível, foram identificadas nos espectros. A abertura dos níveis de energia verificada está de acordo com a simetria C5 do campo cristalino. Medidas de absorção polarizada foram feitas com o intuito de verificar a natureza das transições de dipolo e para determinar as representações irredutíveis dos níveis de energia 7F0, 7F1 e 5Dj (j= 0 a 2). Linhas da impureza Er+3 (não intencional) foram identificadas no espectro de absorção e sua presença no cristal foi verificada através dos valores conhecidos dos níveis de energia do íon Er+3 em GdAlO3 [III-4]. Além disso, medidas dos níveis de energia 7F2 do íon Eu+3 através da técnica espectroscópica não linear CARS, foram tentadas. Medidas preliminares destes níveis e dos níveis vibracionais do benzeno e da calcita são mostrados no final da dissertação. / Absorption, fluorescence and excitation of the Eu+3 íon in GdAlO3 in the visible region are presented in this work. All of the 7Fj (j= 0, 1, 2 and 4) and 5Dj (j= 0 to 2) energy levels were measured and almost all of the transitions in the visible region of the ion were seen in the spectra. The splitting of energy levels verified is according to the C5 symmetry of the crystal field. Polarized absorption techniques are used to check the nature of the dipole transitions and to determine the irreducible representations of the 7F0, 7F1 and 5Dj (j= 0 to 2) energy levels. Unintentional Er+3 impurities lines were identified in the absorption spectra and its presence in our crystal was checked through the known values of energy levels of GdAlO3:Er+3 [III-4]. Besides it we began to measure the 7F2 energy levels of them Eu+3 ion by using the nonlinear optical spectroscopy technique known as CARS firsts measurements of these energy levels and of the vibrational mode of benzene and calcite are shown in the end of the dissertation.