Mn-doped II-VI semiconductor nanocrystals exhibit bright dopant photoluminescence that has potential usefulness for light emitting devices, temperature sensing, and biological imaging. The bright luminescence comes from the 4T1→6A1 transition of the Mn2+ d electrons after the exciton-dopant energy transfer, which reroutes the exciton relaxation through trapping processes. The driving force of the energy transfer is the strong exchange coupling between the exciton and Mn2+ due to the confinement of exciton in the nanocrystal. The exciton-Mn spatial overlap affecting the exchange coupling strength is an important parameter that varies the energy transfer rate and the quantum yield of Mn luminescence. In this dissertation, this correlation is studied in radial doping location-controlled Mn-doped CdS/ZnS nanocrystals. Energy transfer rate was found decreasing when increasing the doping radius in the nanocrystals at the same core size and shell thickness and when increasing the size of the nanocrystals at a fixed doping radius. In addition to the exciton-Mn energy transfer discussed above, two consecutive exciton-Mn energy transfers can also occur if multiple excitons are generated before the relaxation of Mn (lifetime ~10^-4 - 10^-2 s). The consecutive exciton-Mn energy transfer can further excite the Mn2+ d electrons high in conduction band and results in the quenching of Mn luminescence. The highly excited electrons show higher photocatalytic efficiency than the electrons in undoped nanocrystals. Finally, the effect of local lattice strain on the local vibrational frequency and local thermal expansion was observed via the temperature-dependent Mn luminescence spectral linewidth and peak position in Mn-doped CdS/ZnS nanocrystals. The local lattice strain on the Mn2+ ions is varied using the large core/shell lattice mismatch (~7%) that creates a gradient of lattice strain at various radial locations. When doping the Mn2+ closer to the core/shell interface, the stronger lattice strain softens the vibrational frequency coupled to the 4T1→6A1 transition of Mn2+ (Mn luminescence) by ~50%. In addition, the lattice strain also increases the anharmonicity, resulting in larger local thermal expansion observed from the nearly an order larger thermal shift of the Mn luminescence compared to the Mn-doped ZnS nanocrystals without the core/shell lattice mismatch.

<p>Fluorochlorozirconate (FCZ) glasses are a member of heavy metal fluoride glasses, and are derived from a well known ZBLAN glass. In this work, halogen salts of europium (Eu²⁺) and samarium (Sm³⁺) are used as dopants in FCZ glasses. FCZ glasses doped with Eu²⁺ and Sm³⁺ can be used in high resolution x-ray imaging for tissue scanning, and have been shown to behave as storage phosphors and/or x-ray scintillators.</p> <p>Glass transition (T_g), heat capacity (C_p) and glass crystallization (T_c) properties of Eu²⁺ and Sm³⁺ doped and undoped FCZ glasses with different amounts of relative Cl concentration, that is, with respect to the total Cl and F concentration have been investigated by conventional differential scanning calorimetry (DSC) and modulated differential scanning calorimetry (MDSC) techniques. MDSC experiments were performed at different heating rates to analyze the complex transitions and to get a better resolution of any overlapping transitions. The crystallization kinetics have also been studied by applying the Kissinger technique to multiple DSC scans in order to determine the thermal stability of FCZ glass samples used in this work. The apparent activation energy for the crystallization process was obtained by the crystallization peak temperature shift method in the conventional DSC mode. The specific heat capacity (C_p) has been measured as a function of composition, and the glass transition temperature (T_g) is evaluated from the smooth change in the heat capacity curve during the glass transformation. The observation of two possible glass transitions points to the presence of two phases in these FCZ glasses with higher relative Cl content.</p> <p>Optical transmission spectra of both doped and undoped FCZ glass samples have been measured by infrared spectroscopy and optical band gaps corresponding to an absorption coefficient of 10³ cm^-1 have been determined. A good correlation between X-ray luminescence and the glass structure is observed. While the integrated photoluminescence intensity increases linearly with the Sm³⁺ concentration, the integrated X-ray luminescence increases sublinearly. The importance of appropriate annealing conditions, such as temperature, time and ambient atmosphere, and their effect on the X-ray luminescence of rare earth (RE) doped FCZ glass samples have been investigated. Annealing conditions influence the formation of BaCl₂ nanocrystals in the glass and the properties of the resulting FCZ glass ceramics.</p>

A self-consistent, full-band, electrothermal ensemble Monte Carlo device simulation tool has been developed. It is used to study charge transport in bulk GaN, and to design, analyze, and improve the performance of AlGaN/GaN high electron mobility transistors (HEMTs) and avalanche photodiodes (APDs). Studies of electron transport in bulk GaN show that both peak electron velocity and saturated electron velocity are higher for transport in the basal plane than along the c-axis. Study of the transient electron velocity also shows a clear transit-time advantage for electron devices exploiting charge transport perpendicular to the c-axis. The Monte Carlo simulator also enables unique studies of transport under the influence of high free carrier densities but with low doping density, which is the mode of transport in AlGaN/GaN HEMTs. Studies of isothermal charge transport in AlGaN/GaN HEMTs operating at high gate bias show a drain current droop with increasing drain-source bias. The cause of the droop is investigated and a design utilizing source- or gate-connected field plate is demonstrated to eliminate the drain current droop. Electrothermal aspects of charge transport in AlGaN/GaN HEMTs are also investigated, and the influence of non-equilibrium acoustic and optical phonons is quantified. The calculated spatial distribution of non-equilibrium phonon population reveals a hot spot in the channel that is localized at low drain-source bias, but expands towards the drain at higher bias, significantly degrading channel mobility. Next, Geiger mode operation of wurtzite GaN-based homojunction APDs is investigated. The influences of dopant profile, active region thickness, and optical absorption profile on single photon detection efficiency (SPDE) are quantified. Simulations of linear mode gain as a function of multiplication region thickness and doping profile reveal that weakly n-type active regions may be exploited to achieve higher avalanche gain, without penalty to either applied bias or active region thickness. A separate absorption and multiplication APD (SAM-APD) utilizing a AlGaN/GaN heterojunction is also investigated. The presence of strong piezo-electric and spontaneous polarization charges at the heterojunction enables favorable electric field profile in the device to reduce dark current, improve excess noise factor, improve quantum efficiency, and improve breakdown probability. To maximize SPDE, a new device structure with a buried absorber is proposed and improved SPDE is demonstrated. Lastly, a new approach for the direct generation of self-sustaining millimeter-wave oscillations is proposed. In contrast to Gunn diodes, which exploit a bulk-like active region, periodic oscillation is achieved in the proposed structures through the creation, propagation and collection of traveling dipole domains supported by fixed polarization charge and the associated two-dimensional electron gas along the plane of a polar heterojunction. Numerical simulation of induced oscillations in a simple triode structure commonly used for AlGaN/GaN HEMTs reveals two distinct modes of self-sustaining millimeter-wave oscillation.

The purpose of this thesis work was to find a way to measure basic light emission properties of nitrogen-and-boron-doped 6H-SiC, which are fabricated with a growth method developed at Linköping University. The research is in its initial phase and the light properties as well as optical measurement techniques are important. The aim is that the results of the measurements will provide feedback to the growth process what quality and doping levels that are required to get the maximum amount of light. The measurements were performed at the Laboratory of Lighting Technology, Technical University of Darmstadt, Germany. Two measuring methods with different excitation sources were tested: a double monochromator and a setup using near UV-filters. While the double monochromator was able to project wavelengths in steps down to 0.5 nm with a high accuracy, the filters were only available in steps of 10 nm where the accuracy of the wavelength values varied. The double monochromator was chosen for the continuing measurements. When using excitation light between 375-390 nm the emitted light was in the visible wavelength region. The light properties measured were the irradiance (measured in W/m2) and the peak wavelength were maximum luminescence occurred. The result showed that sample 2-4 had a peak wavelength at approximately 580‑582 nm for the excitation wavelength 375 nm. For sample 5 the peak wavelength occurred at 582 nm at the excitation wavelength 390 nm. Sample 1, the unintentionally doped, did not show any measurable results as expected. When irradiance of the excitation light was approx. 8 W/m2 the irradiance at the peak of luminescence for the samples varied between 15.03-29.35 mW/m2. The low values are believed to be the result of the emitted light scattering in all directions whereas the measurements are done in one direction and only from a small area of the sample. The measurements has shown that it is possible to measure the light properties of the grown material even though the samples were not finalized (capsulated) LED’s. The results from the measurements are of interest for the continuing development of the material.

Semiconductor-based gas sensors have been used for a wide range of applications over the last few decades. In this thesis, sensing properties of pure ZnO and Ga doped ZnO are investigated. There are three types of tested gas species, H2, O2 and NO, and three test temperatures, 300oC, 400oC and 500oC. After measurements of response to exposure to H2 and O2, it is concluded that Ga doped ZnO and ZnO are both n-type metal oxides. In measurements of NO, two test conditions were considered, the case with background O2 (10%) in the gas flow and the case without background O2. NO can be oxidized to NO2 or reduced to N2 and O2. The resistance of Ga doped ZnO and ZnO sensors always decreases for all exposures to NO except for the case in which the Ga doped ZnO sensor was exposed to NO in a background of O2 at 500 oC. In this special case, the resistance of Ga doped ZnO actually increases during exposure to low concentrations of NO (&lt; 30 ppm). It is not clear whether the change in response direction is due to an n-p transition or different reactions between gas molecules and Ga doped ZnO. Work function measurements were therefore conducted to understand more about the electron transfer during gas exposure. The work function measurements suggest that there are probably several stages of interactions between gas molecules and Ga doped ZnO during each gas pulse exposure.

<p>Fluorochlorozirconate (FCZ) glasses are a member of heavy metal fluoride glasses, and are derived from a well known ZBLAN glass. In this work, halogen salts of europium (Eu²⁺) and samarium (Sm³⁺) are used as dopants in FCZ glasses. FCZ glasses doped with Eu²⁺ and Sm³⁺ can be used in high resolution x-ray imaging for tissue scanning, and have been shown to behave as storage phosphors and/or x-ray scintillators.</p> <p>Glass transition (T_g), heat capacity (C_p) and glass crystallization (T_c) properties of Eu²⁺ and Sm³⁺ doped and undoped FCZ glasses with different amounts of relative Cl concentration, that is, with respect to the total Cl and F concentration have been investigated by conventional differential scanning calorimetry (DSC) and modulated differential scanning calorimetry (MDSC) techniques. MDSC experiments were performed at different heating rates to analyze the complex transitions and to get a better resolution of any overlapping transitions. The crystallization kinetics have also been studied by applying the Kissinger technique to multiple DSC scans in order to determine the thermal stability of FCZ glass samples used in this work. The apparent activation energy for the crystallization process was obtained by the crystallization peak temperature shift method in the conventional DSC mode. The specific heat capacity (C_p) has been measured as a function of composition, and the glass transition temperature (T_g) is evaluated from the smooth change in the heat capacity curve during the glass transformation. The observation of two possible glass transitions points to the presence of two phases in these FCZ glasses with higher relative Cl content.</p> <p>Optical transmission spectra of both doped and undoped FCZ glass samples have been measured by infrared spectroscopy and optical band gaps corresponding to an absorption coefficient of 10³ cm^-1 have been determined. A good correlation between X-ray luminescence and the glass structure is observed. While the integrated photoluminescence intensity increases linearly with the Sm³⁺ concentration, the integrated X-ray luminescence increases sublinearly. The importance of appropriate annealing conditions, such as temperature, time and ambient atmosphere, and their effect on the X-ray luminescence of rare earth (RE) doped FCZ glass samples have been investigated. Annealing conditions influence the formation of BaCl₂ nanocrystals in the glass and the properties of the resulting FCZ glass ceramics.</p>

Developing chemical bonding models in clusters is one of the most challenging tasks of modern theoretical chemistry. There are two reasons for this. The first one is that clusters are relatively new objects in chemistry and have been extensively studied since the middle of the 20th century. The second reason is that clusters require high-level quantum-chemical calculations; while for many classical molecules their geometry and properties can be reasonably predicted by simpler methods. The aim of this dissertation was to study doped clusters and explain their chemical bonding. The research was focused on three classes of compounds: aluminum clusters doped with one nitrogen atom, planar compounds with hypercoordinate central atom, partially mixed carbon-boron clusters, and transition metal clusters. The geometry of the two latter classes of compounds was explained using the concept of aromaticity, previously developed in our group. Also the Coalescence Kick Method for finding global minima structure and low-lying isomers was implemented, tested, and applied to the considered cluster systems. Tests showed that the Kick Method works faster than other methods and provides reliable results. It finds global minima even for such large clusters as B17- and B19- in reasonable time.

The electronic structure of some transition metal compounds, specifically, Ca-doped LaMnO3, fundamental Mn oxides (MnO, Mn2O3, Mn3O4, and MnO2), and Fe-doped ZnO is studied using a combination of soft X-ray spectroscopy and atomic multiplet calculations. X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) are used as experimental tools to probe the unoccupied and occupied partial density of electronic states,respectively.<p> Ca-doped LaMnO3 perovskites have attracted great attention due to their colossal magnetoresistance and a wide range of magnetic and structural transitions. The magnetic and charge transport properties of these perovskites are directly related with Mn 3d-occupancy or Mn-valency and therefore, an investigation of the Mn-valence at Ca-doped LaMnO3 system is important. In this system, the Mn-valency is generally considered as a mixture of Mn3+ and Mn4+. But my research suggests the presence of Mn2+ at the surface of Ca-doped LaMnO3 samples. It is observed that increasing Ca-doping decreases Mn2+ concentration, and conversely, increases Mn3+ concentration. High temperature annealing at 1000 °C in air leads to the full reduction of surface Mn2+. Mechanisms for these observations are proposed in this study.<p> Mn oxides (MnO, Mn2O3, Mn3O4, and MnO2) are often used as reference standards for determining the Mn-valency in Mn-related complex systems and therefore a detailed understanding of their electronic structure is necessary. The Mn L2,3 XAS and O K XAS are measured for the four Mn oxides consisting of three common Mn oxidation states (Mn2+ in MnO, Mn3+ in Mn2O3, mixture of Mn2+ and Mn3+ in Mn3O4, and Mn4+ in MnO2). A significant energy shift with a systematic trend is observed in measured Mn L2,3 and O K absorption edges. These energy shifts are identified as a characteristic shift for different Mn oxidation states. Mn L2,3 Resonant Inelastic X-ray Scattering (RIXS) spectroscopy is demonstrated as a powerful tool in describing low energy excitations, e.g. d-d excitations and charge-transfer excited states in Mn oxides. For the first time, a RIXS study of Mn2O3,Mn3O4, and MnO2 is accomplished. Atomic multiplet calculations are used to successfully reproduce the energy positions and intensity variations of d-d excitation peaks observed in the experiment, and thus to describe the experimental RIXS spectra.<p> Finally, the local electronic structure of Fe implanted ZnO samples, a useful diluted magnetic semiconductor for spintronics, is investigated to shed light on the existing debate about the origin of ferromagnetism in these materials. Fe L2,3 XAS reveals that doped Fe ions are present in both Fe2+ and Fe3+ valence states. A combined theoretical and experimental study shows that doped ions are incorporated into Zn-sites of ZnO in tetrahedral symmetry. Fe L3- RIXS measurements demonstrate that a high Fe-ion dose of 8 × 107 cm-2 causes formation of FeO clusters, while low dose samples exhibit more free carriers.

In this research, the polarization converters were manufactured by impinging intensity-gradient-distribution laser on DDLC (dye-doped liquid crystal) samples, which the gradient distributed light intensity was produced by applying linear variable ND filter. The performances of these polarization converters were demonstrated, which can convert a linear polarized incident light into a circular polarized light or an elliptic polarized light. The influence of cell gap and beam size of probe beam on the DDLC polarization converter has been discussed.

The electronic structures of Mn £_-doped epitaxial GaN films grown on sapphire substrates are studied by scanning tunneling microscopy in this work. Local structural information and the corresponding electronic properties of Mn £_-doped GaN films are probed by the combination of scanning tunneling microscopy and atomic-scale scanning tunneling spectroscopy measurements. According to the electronic local density of states analysis indicates that Mn ions develop an acceptor level in GaN, revealing a gap state located at ~ 1.4 eV above the valence band edge of GaN. Furthermore, the energy position of the charge transfer levels of substitutional MnGa within GaN energy gap is also elucidated and discussed in the work.