The thesis is aimed to the study of spiropyrane behavior in polymeric matrix of poly(N-vinylkarbazole) (PVK) and poly[2-methoxy-5-(3´,7´-dimethyloctyloxy)-1,4-fenylenvinylene)] (MDMO-PPV). The photochromic transformation of spiropyrane to its isomeric merocyanine form (SPMC) was studied by absorption and emission spectroscopy. It was found, that photochromic reaction is markedly dependent on the environment. In the PVK polymer, which don’t absorb in the visible region, a high yield of photochromic reaction was achieved. Both, absorption and emission spectrums were observed for this system. From the measurement of time dependencies of the fotochromic reaction, the activation energy of the reverse reaction was determined. A different behavior, particularly in emissive spectrums, was found for the MDMO-PPV polymer doped with spiropyrane. Instead of formation of new band of merocyanine, decrease of the polymer fluorescence was observed. Subsequently, we studied the interaction between the polymeric matrix and the photochromic spiropyrane using fluorescence quenching method. On the basis of energy transfer theory, a critical radius of the fluorescence quenching sphere in solution and in solid was determined.

The purpose of this work was to recover uranium from residue originating from the production of molybdenum -99. Carbonate solutions containing hydrogen peroxide or oxygen gas as oxidants were used as leachants. Experimental parameters included: different peroxide and carbonate concentrations, dissolution time and temperature. Results indicate complete dissolution of the residue at 60 oC, after thirty minutes, in ammonium carbonate solution enriched with hydrogen peroxide. Almost two hours were needed to achieve the same extent in the presence of oxygen. The yield and rate of uranium extraction were found to increase as a function of both temperature, in the range of 25-60 oC, and hydrogen peroxide concentration. The leaching kinetics were determined for various leaching conditions and the activation energy was found to be 45.5kJ/mol. The order of reaction with respect to uranium concentration was found to be unity. / Dissertation (MSc)--University of Pretoria, 2013. / gm2014 / Materials Science and Metallurgical Engineering / unrestricted

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Here we investigate the organic ionic plastic crystal (OIPC) 1,2-bis[N-(N\'-hexylimidazolium-d2(4,5))]C2H4 2PF6- in one of its solid plastic crystal phases by means of multi-nuclear solid-state (SS) NMR and pulsed-field-gradient (PFG) NMR. We quantify distinct cation and anion diffusion coefficients as well as the diffusion activation energies (Ea) in this dicationic imidazolium-based OIPC. Our studies suggest a change in transport mechanism for the cation upon varying thermal and magnetic treatment (9.4 T), evidenced by changes in cation and anion Ea. Moreover, variable temperature 2H SSNMR lineshapes further support a change in local molecular environment upon slow cooling in B0. Additionally, we quantify the percentage of mobile anions as a function of temperature from variable temperature 19F SSNMR, where two distinct spectral features are present. We also comment on the pre-exponential factor (D0), giving insight into the number of degrees of freedom for both cation and anion as a function of thermal treatment. In conjunction with previously reported conductivity values for this class of OIPCs and the Stokes-Einstein relation, we propose that ion conduction is dominated by anion diffusion between crystallites (i.e., grain boundaries). Using our experimentally determine diffusion coefficient and previously reported PF6- hydrodynamic radius (rH), viscous (" = 4.1 Pa " s) ionic liquid (IL) is present with a cation rH of 0.34 nm. NMR measurements are very powerful in elucidating fundamental OIPC properties and allow a deeper understanding of ion transport within such materials. / Master of Science

In this master thesis, electrical characterization of thin film CuInxGa(1−x)Se2 solar cells produced by Midsummer AB were performed with the aim of determining the dominant recombination path of these cells. Current-Voltage (IV), Quantum Effinciency (QE), temperature dependent IV (IVT) and Drive-Level Capacitance Profiling (DLCP) was used with the objective to investigate the dominant recombination path as well as provide some insight of the solar cells in order to create a baseline model using the modelling software SCAPS (Solar cell CAPacitance Simulator). The IV produced mostly consistent results with slight variation, most likely due to non uniformity of equipment. The QE showed consistent results between all cells indicating a stable process for the sample preparation. Using IVT measurements were taken from a temperature of 115K −300K in order to obtain the activation energy for the dominant recombination path. By comparing it with the band gap energy from the QE measurement, it was found that the dominant recombination path is in either the space charge region or in the bulk of the CIGS and not at the hetero interface. DLCP measurement were made at both low temperature and at room temperature and revealed that the cells had a similar doping as other comparable cells at 7×1016cm−3 . The initial baseline model created in SCAPS show a good agreement with the measured IV and currently indicates a spike in the band alignment, supporting the results for the IVT measurement.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24633号 / 工博第5139号 / 新制||工||1982(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 阿部 竜, 教授 作花 哲夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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Silicon carbide is a very promising semiconductor material for high-power, highrequency, and high-temperature applications. SiC distinguishes from traditional narrow bandgap semiconductors, such as silicon, in that common doping impurities in SiC have activation energies larger than the thermal energy kT even at room temperature. This causes incomplete ionization of such impurities, which leads to strong temperature and frequency dependence of the semiconductor junction differential admittance and, if carrier freeze-out effects are not taken into account, errors in doping profiles calculated from capacitance-voltage data. Approaches commonly used to study the influence of incomplete impurity ionization on the junction admittance are based on the truncated space charge approximation and/or the small-signal approximation. The former leads to impurity ionization time constant and occupation number errors, while the latter fails if the measurement ac signal amplitude is larger than kT/q. In this work, a new reverse bias Schottky junction admittance model valid for the general case of an arbitrary temperature, measurement signal frequency and amplitude, and doping occupation number and time constant distributions is developed. Results of junction admittance calculations using the developed model are compared with the results of traditional models. Based on the general model, a new method of admittance spectroscopy data analysis is created and used to determine impurity parameters more accurately than allowed by traditional approaches. Incomplete impurity ionization is investigated for the case of nitrogen donors and aluminum and boron acceptors in 4H- and 6H-SiC. It is shown that the degree of carrier freeze-out is significant in heavily N-doped 6H-SiC and in Al- and B-doped SiC. Frequency dispersion of the junction admittance is shown to be significant at room temperature in N- and B-doped SiC. Junction capacitance calculations as a function of applied dc bias show that calculated doping profiles deviate from the actual impurity concentration profiles if the impurity ionization time constant is comparable with the ac signal period. This is the case for N- and B-doped SiC with certain values of the impurity activation energy and capture cross-section. Validity of the new model and its predictions are successfully tested on experimental admittance data for N- and B-doped SiC Schottky diodes.

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