Title: Photoluminescence of CdTe crystals Author: Jan Procházka Department: Institute of Physics of Charles University in Prague Supervisor: Doc. RNDr. Pavel Hlídek, CSc. Abstract: Energy levels connected with defects in nominally undoped crystals CdTe, indium- doped crystals and chlorine-doped crystals were studied using low-temperature photoluminescence. The crystals are intended for X- and gamma- ray detectors operated at room temperature. An effect of annealing in cadmium or tellurium vapor on luminescence spectra was investigated. Some changes were interpreted by filling of vacancies not only by atoms coming from gaseous phase but also by impurities from defects like interstitials, precipitates, inclusions, grain boundaries etc. The luminescence bands assigned to defects important for compensation mechanism were examined, namely A-centers (complexes of vacancy in cadmium sublattice and impurity shallow donor) and complexes of two donors bound to a vacancy. It was shown, that temperature dependence of the luminescence bands results from more complicated processes than a simple thermal escape of bound excitons or thermal excitation of electrons (holes) from defects to bands. We observed expressive "selective pair luminescence" bands (SPL) on partially compensated In-doped samples during sub-gap...

Magister Scientiae - MSc / Cancer, the second most common cause of death after heart disease, is a complex and multifactorial disease that up to date is still under extensive research. To achieve early detection of cancer disease the discovery of specific, sensitive and reliable biomarkers is required. Telomerase is a ribonucleo-protein complex that has been identified as an important target for cancer diagnostics and cancer therapy, because 85% of more than 950 primary tumours express telomerase activity. The standard method for the detection and quantification of telomerase activity is the polymerase chain reaction (PCR)-based assay known as the telomeric repeat amplification protocol (TRAP) assay. TRAP and other methods developed for telomerase detection have limitations for example its time consuming, requires complicated machinery, expensive equipment and reagents thus there is a need for a more sensitive, reliable and high-throughput method. Electrochemical biosensors are quickly emerging as an alternative for early detection of cancer because they can be designed to detect developing cancer biomarkers and to allow improved monitoring of cancer growth and patient therapy. This research study reported for the first time the successful fabrication and implementation of highly sensitive 3-mercaptopropionic acid indium telluride quantum dots (3MPA-In2Te3 QDs) based genosensor for detection of telomerase biomarker. The colloidal poly-dispersed 3MPA-In2Te3 QDs introduced into the genosensor system were successfully synthesized by a simple, inexpensive and reproducible aqueous method. The as prepared 3MPA-In2Te3 QDs was characterized by Ultraviolet Visible (UV-VIS) spectroscopy, Fluorescence (FL) spectroscopy, X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy and High Resolution Transmission/Scanning Electron Microscopy (HR TEM/SEM). Electro-analysis of 3MPA-In2Te3 QDs was done by Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). HR-TEM studies revealed formation of small sized QDs about 6 nm in diameter while UV-VIS studies showed presence of iv absorption peaks in the ultraviolet region (100-400 nm) which confirmed the formation of these small sized QDs. The good electrochemical, optical, physical and chemical properties of the 3MPA-In2Te3 QDs allowed them to be used as a mediating platform between deoxyribonucleic acid (DNA) and gold electrode (AuE). The successful detection of telomerase was achieved by hybridization process between the probe single stranded deoxyribonucleic acid (ssDNA) drop coated on the 3MPA-In2Te3 QDs/AuE surface and its complementary ssDNA in biological buffer solution (0.10 M tris-ethylenediamine tetraacetic acid (TE) buffer solution, pH 8.00). The response of the 3MPA-In2Te3 QDs based genosensor towards different concentration of complementary ssDNA was studied by CV, square wave voltammetry (SWV) and EIS. It was observed that all three analytical techniques exhibited good linearity since their linear correlation coefficients (R2) corresponded to 0.99. However, it was observed that EIS was the best technique for the detection of telomerase compared to both CV and SWV since it showed a higher sensitivity (2.44 Ω/nM) towards detecting telomerase with a detection limit as low as 0.00014 ng/mL. Control experiments were also carried out by monitoring the hybridization process in the presence and absence of complementary ssDNA and it was determined that the QDs based genosensor was highly selective towards complementary ssDNA. In view of the attractive analytical characteristics and advantages, the ultimate goal of the developed QDs based genosensor is to apply it in real clinical samples of cancer cells or bodily fluids of cancer patients for the detection of telomerase cancer biomarker.

The growing need of energy worldwide has lead to an increasing demand for alternative sources of power generation. Thermoelectric materials are one of the ‘green energy sources’ which convert directly heat into electricity, and vice–versa. The efficiency of this conversion is dependent on ‘figure of merit’ (z T), which depends on the material’s Seebeck coefficient (S), electrical resistivity (ρ) and thermal conductivity (κ) through the relation z T=S2T/ρκ, where T is the temperature. High values of z T lead to high efficiency, and therefore, z T must be maximized. Lead telluride is well–established thermoelectric material in the temperature range 350 K and 850 K. The aim of this thesis is to improve the z T of the material by adopting two different approaches – (i) doping/alloying and (ii) introducing additional interfaces in bulk i.e. having two phase PbTe. In this thesis, first an introduction about the thermoelectric phenomenon is given, along with the material parameters on which z T depends. A survey of literature associated with PbTe is done and the current status of thermoelectric devices is summarized briefly. This is followed by a description of the synthesis procedure and the measurement techniques adopted in this work. The first approach is the conventional alloying and doping of the material by which carrier concentration of the material is controlled so that maximum power factor Sρ2 is achieved and a simultaneous reduction of thermal conductivity takes place by mass fluctuation scattering. Under this, two systems have been studied. The first system is PbTe1−ySey alloys doped with In (nominal composition: Pb0.999In0.001Te1−ySey, y=0.01, 0.05, 0.10, 0.20, 0.25, 0.30). The compounds were single phase and polycrystalline. Lattice constants obtained from Rietveld refinement of X–ray diffraction (XRD) data showed that Vegard’s law was followed, indicating solid solution formation between PbTe and PbSe. Compositional analysis showed lower indium content than the nominal composition. Temperature dependent Seebeck coefficient showed all the samples to be n–type while Pisarenko plots showed that indium did not act as a resonant dopant. Electrical resistivity increased with temperature, while mobility vs T fitting showed a mixed scattering mechanism of acoustic phonon and ionized impurity scattering. Thermal conductivity followed a T1 dependence, which indicated acoustic phonon scattering. At high temperature, slight bipolar effect was observed, which showed the importance of control-ling carrier concentration for good thermoelectric properties. A z T of 0.66 was achieved at 800 K. The second alloy studied under this approach was Mn doped Pb1−ySnyTe alloy (nominal composition Pb0.96−yMn0.04SnyTe (y=0.56, 0.64, 0.72, 0.80)). All the samples followed Vegard’s law, showing formation of complete solid solution between PbTe and SnTe. Microstructure analysis showed grain size distribution of <1 µm to more than 10 µm. Seebeck coefficient showed all samples were p-type and the role of two valence band conduction in p–type PbTe based materials. Electrical resistivity showed a de-crease possibly due to (i) large carrier concentration or (ii) increased mobility due to Mn2+ ions. Thermal conductivity decreased systematically with decreasing Sn content. Bipolar effect was observed at high temperatures. Accordingly, the highest z T of 0.82 at 720 K was obtained for the sample with Sn (y=0.56) content due to optimum carrier concentration and maximum disorder. The second approach of having additional interfaces in bulk focuses on reducing thermal conductivity by scattering phonons. Under this approach, three systems were studied. The first system is PbTe with bismuth (Bi) secondary phase. The XRD and Ra-man studies showed that bismuth was not a dopant in PbTe, while micrographs showed micrometer–sized Bi secondary phase dispersed in bulk of PbTe. Reduction in Seebeck coefficient showed possible hole donation across PbTe–Bi interfaces, while electrical re-sistivity and thermal conductivity showed that the role of electrons at the interfaces was more important than phonons for the present bismuth concentrations. For the parent PbTe, z T of 0.8 at 725 K was reached, which, however decreased for bismuth added samples. The second system studied under the two phase approach was indium (In) added PbTe. Indium was not found to act as dopant in PbTe, while micrometer sized indium phase was found in PbTe bulk. A decrease in the electronic thermal conductivity ac-companied by a simultaneous increase of the electrical resistivity and Seebeck coefficient throughout the measurement range indicated increased scattering of electrons at PbTe-In interfaces. Higher values of the lattice thermal conductivity showed that the PbTe–In interfaces were ineffective at scattering phonons, which was initially expected due to the lattice mismatch between PbTe and In. For PbTe with 3 at. % In phase, z T value of 0.78 at 723 K was achieved. Under the two phase approach, as a comparative study, PbTe with both micrometer sized Bi and In phases together was prepared, in which no improvement in z T was found. A comparison of both the approaches showed that the alloying approach is better than the two–phase approach. This is because micrometer sized secondary phase scatter the electrons more than the phonons, leading to adverse effect on the transport coef-ficients, and hence, on z T. Alloying, on the other hand, is more beneficial in reducing thermal conductivity by mass fluctuation scattering, along with a simultaneous reduction of electrical resistivity.

The infrared portion of the electro-magnetic spectrum is a challenging region in which to perform optical techniques, limited by both device efficiency and availability. In this dissertation, a new optical technique is introduced to facilitate polarization state measurement across the mid-IR. In addition, cadmium zinc telluride (CZT) is investigated as a potential new material suitable for electro-optic devices which function in the mid-IR, while also being characterized by other optical analysis methods. Thin film interference is discussed as it relates to optical techniques and electronic devices. A Stokes polarimeter is used to study the oxide development on the surface of CZT electronic devices, and the effect of natural thin films on substrates used in optical techniques is discussed. In particular, the impact of thin film interference on sum-frequency generation spectroscopy measurements of methyl group orientation are assessed. An FTIR source operated in step-scan mode is used to create a broadband, IR Stokes polarimeter which measures the polarization state of light from 2.5-11 μm simultaneously. Its design, involving two photo-elastic modulators and an analyzer, and theory are described in detail. This instrument is demonstrated by measuring linearly polarized light, and is applied to the measurement of the refractive index dispersion of quartz from 2.5-4 μm, which goes beyond the limits of literature values. Electro-optic crystals of CZT with electrodes of gold and indium are characterized at each wavelength in the mid-IR in terms of their electro-optic effects and apparent depolarization using the Stokes polarimeter. The material displays high-resistivity, allowing it to be operated with up to 5 kV applied DC voltage. The linear electro-optic effect is observed, but overall properties of the samples are found to be heavily dependent on the choice of metal for the electrodes. With a high-work function electrode material in gold, a large depletion region is created when high voltage is applied, which leads to a gradient in electric field throughout the material. This causes a beam of light transmitted through it to experience a distribution of electro-optic behaviours, which leads to overall depolarization of the light. Indium’s work function is lower than gold’s, and is closer to that of CZT. With indium electrodes, the electric field is found to be more consistent, and behaviour is much closer to ideal. The electro-optic effect of CZT is also characterized with AC applied voltage in order to assess its suitability to AC applied voltage applications. The power supply used for this was limited to 60 Hz, which precludes a complete characterization in this regard, but unexpected behaviour was seen. A methodology utilizing an oscilloscope and FTIR was developed in order to more completely understand the material response, and divergent behaviour with positive and negative voltage was found. / Graduate / 2018-12-18

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22014号 / 工博第4626号 / 新制||工||1721(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 山子 茂, 教授 辻井 敬亘, 教授 竹中 幹人 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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Les nouvelles gamma-caméras à semi-conducteurs utilisant des détecteurs au CZT sont dédiées aux explorations cardiaques. Leurs sensibilité, résolution spatiale et en énergie nettement améliorées comparativement aux gamma-caméras conventionnelles sont une révolution en médecine nucléaire. Ces gamma-caméras utilisent de nouvelles géométries d’acquisition, de nouveaux algorithmes de reconstruction, et ouvrent de nouvelles perspectives dans les études simultanées en double-isotope de l’123I et du 99mTc, dont les pics énergétiques sont proches.Nous avons étudié l’impact de l’amélioration de la résolution en énergie en comparant deux modèles de gamma-caméras à détecteurs semi-conducteurs aux gamma-caméras conventionnelles. A l’aide d’études sur fantômes anthropomorphes et chez des patients porteurs d’insuffisance cardiaque, notre travail s’est concentré sur les acquisitions scintigraphiques (i) de la fonction ventriculaire gauche (99mTc) en présence d’123I, (ii) de la perfusion myocardique (99mTc) en présence d’123I (innervation), et (iii) du rapport cardiomédiastinal de la fixation d’123I- métaiodobenzylguanidine (123I-MIBG) lors d’acquisitions double-isotope (123I-MIBG/99mTc- tétrofosmine) chez les patients souffrant d’insuffisance cardiaque.Nos résultats montrent que la meilleure résolution en énergie des gamma-caméras CZT permet en étude double-isotope (i) une évaluation de la FEVG et du mouvement régional dans les différentes fenêtres d'énergie (123I ou 99mTc) et les types d'acquisition (simple- vs double-isotope), (ii) une évaluation simultanée et combinée de la perfusion (99mTc) et de l’innervation (123I) du myocarde, et (iii) l’évaluation du rapport cardiomédiastinal de la fixation d’123I-MIBG. Chacune de ces trois parties a fait l’objet d’une publication. / New dedicated-cardiac cameras using CZT detectors have dramatically transformed the routine of myocardial perfusion imaging. With a better count detection sensitivity, an improved spatial and energy resolution, they potentially enable combined assessment of myocardial innervation (123I) and perfusion (99mTc) within a single imaging session. These cameras images with different sharpness and contrast-to-noise ratios.Using two CZT cameras with anthropomorphic phantom, and clinical studies in heart failure patients, our work focused on (i) the left ventricular function assessment within the 99mTc window in presence of 123I, (ii) the evaluation of regional myocardial innervation (123I) and perfusion (99mTc) match and mismatch with single- (separate 123I and 99mTc acquisition) and simultaneous dual-isotope acquisitions, and (iii) the late heart-to-mediastinal ratio (HMR) of 123I-MIBG uptake determined using dual-isotope CZT acquisition with that determined using conventional planar imaging in patients with heart failure.Our results found no impact of the acquisition mode (single vs dual) or the type of CZT camera on 123I and 99mTc defect size and mismatch, LVEF, and HMR of 123I-MIBG uptake.This work provides a new step toward simultaneous dual-isotope acquisition for combined innervation, perfusion and ventricular function assessment.

The Björkdal gold deposit is located in the eastern part of the Skellefte district, northern Sweden. Twenty thin sections from four production areas in the open pit and four drifts from the underground mine were analysed for mineral association and grain size distribution of gold. In addition, the texture of gold was investigated in order to find out how that affects the recovery of gold. The overall gold grain size distribution shows an interval from very fine-grained (2 μm) to coarse grained(856 μm) while the overall median size is 7 μm. Gold from the Quartz Mountain production area displays the smallest median size of 4 μm, whereas gold from the sampled drifts at 340m- and 385m- level has the largest median size of 14 μm. Gold at grain boundary is the dominant textural mode of gold from all sampled locations and varies from 62% to 92%. This is followed by intergrown which ranges between 8% and 29%. Of the sulfides, pyrite, chalcopyrite and pyrrhotite are the most common. Galena and was also present in the samples. Gold is significantly and positively correlated with tellurium (Appendix 10.1.1), and weakly positive correlated to silver and mercury. Gold show a close association to bismuth-tellurides in the samples. Apart from native gold, which is the dominant mineral phase of gold, two additional gold-bearing tellurium minerals were detected with SEM-EDS, a Au-Te-mineral and a Ag-Au-Te-mineral. One additional bismuth-telluride mineral aside from the most commonly occurring tsumoite (BiTe) was also detected with SEM, with a elemental composition of Bi-Te-S. Liberated gold in the tailings was optically identified in two thick sections, TB1-02feb-1 and TB1-07feb-1 (Fig. 32A and B), where the flotation circuit failed to float the free gold. One grain of gold was also identified intergrown with bismuth-telluride as an inclusion in silicate (Fig. 33), where the flotation properties of the larger silicate grain likely dominated in the flotation process. This thesis highlights the importance of further quantitative analysis utilizing SEM/QEMSCAN/MLA to retrieve representative mineralogical data to benefit the mineral processing of the ore from the active mine. Keywords: Björkdal gold deposit, gold, gold-telluride, SEM, mineral association, grain size,geometallurgy.

The thermoelectric properties of bismuth telluride based thermoelectric (TE) materials are well-characterized, but comparatively little has been published on the thermomechanical properties. In this paper, dynamic mechanical analysis (DMA) and differential scanning calorimetry data for bismuth telluride based TE materials is presented. The TE materials' tan delta values, indicative of viscoelastic energy dissipation modes, approached that of glassy or crystalline polymers, were greater than ten times the tan delta of structural metals, and reflected the anisotropic nature of TE materials. DMA thermal scans showed changes in mechanical properties versus temperature with clear hysteresis effects. These results showed that the application of DMA techniques are useful for evaluation of thermophysical and thermomechanical properties of these TE materials.

Two-dimensional (2D) materials have properties that are often different from their three-dimensional (3D) bulk form. Many of these materials are stable at ambient conditions, which allows them to be integrated with other 2D- or 3D-materials to form heterostructures. Integration of various dimensional materials attains unique electrical and optical properties that aid in developing novel electronic devices. The interface of the heterogeneous integration of these films can exhibit a weak van der Waals-like bonding. In this thesis, an advanced characterization (from atomic to millimeter resolution) of various dimensional materials with weakly bonded interfaces is developed and employed to understand their behavior at scale. First, a large-area single-crystal cadmium telluride thin film is grown incommensurately and strain-free to a sapphire substrate despite a significant 3.7% lattice mismatch. The film remarkably delaminates as a bulk single crystal film due to an atomically thin tellurium that spontaneously forms at the interface. Aberration-corrected electron microscopy and spectroscopy reveal both the van der Waals-like structure and bonding at the film/substrate interface. Second, a large-area atomically thin gallium is intercalated at the interface of epitaxial graphene. Correlative microscopy workflows are applied to understand the thickness uniformity and area coverage of the 2D–gallium over few millimeters of the sample. Utilizing multiple correlative methods, SEM image contrast is found to be directly related to the presence of the intercalated gallium. The origin of the SEM contrast is investigated as a function of the surface potential. Then, the heterostructure characterization is scaled up over a few square millimeter areas by segmenting SEM images, each acquired with nanometer-scale resolution. Additionally, transmission electron microscopy is applied to investigate the interface of gallium–SiC, the gallium air–stability, and the role of the substrate on the heteroepitaxial growth of 2D–gallium, which charts a path for further development of these materials. / Thesis / Doctor of Philosophy (PhD)