Thermoelectric (TE) materials are used to directly interconvert heat and electricity. The semiconductor PbTe with narrow band gap is one of the leading thermoelectric materials in mid-temperature range due to intrinsically low lattice thermal conductivity and large Seebeck coefficient. Recently, various strategies have produced p-type and n-type PbTe-based materials with greatly enhanced TE properties. However, there are still many fascinating features which are needed to be studied. First, phase analysis and TE properties of binary polycrystalline Pb‒Te samples prepared by various heat treatments have been investigated. Since europium with its 4f electrons was expected to have strong influence on the thermoelectric behavior of PbTe, the constitution and thermoelectric behavior of two substitution schemes with possible Eu2+ and Eu3+ in the Pb–Eu–Te ternary system have been examined. As sodium is widely used as substituting element for p-type PbTe-based TE materials, the crystal structural features and TE properties of two series of polycrystalline samples Pb1-yNayTe1-y/2 and Pb1-xNaxTe have been studied. The local atomic arrangement of sodium by different substitution schemes has been revealed by NMR. Finally, we present the reproducibility of TE properties and microstructure evolutions of high-ZT Eu-substituted and Na-substituted PbTe during different heat treatments. From binary PbTe to ternary Pb–Eu–Te and Pb–Na–Te, and final with quaternary Pb–Eu–Na–Te, the comprehensive picture of the structure and TE properties for Pb–Eu–Na–Te system is constructed.

Lead-tin telluride alloy, Pb1-xSnxTe, is a narrow band gap group IV–VI semiconductor with NaCl-like crystalline structure. This material has interesting electronic properties, which makes it suitable for designing infrared photo detectors, diode lasers, and thermo-photovoltaic energy converters. In this project, we used spectroscopic ellipsometry in the spectral range of 0.74–6.5 eV to probe the linear optical response of Pb1-xSnxTe alloys in terms of the complex dielectric function. A strong optical response in the range of 0.7-2.0 eV arising from optical absorption was found. We studied eleven different samples of Pb1-xSnxTe of p-type origin with x values in the range (0 ≤ x ≤ 1). They were prepared by means of molecular beam epitaxy (MBE) on BaF2 substrates with 15mm2 area.

<p>Lead-tin telluride alloy, Pb1-xSnxTe, is a narrow band gap group IV–VI semiconductor with NaCl-like crystalline structure. This material has interesting electronic properties, which makes it suitable for designing infrared photo detectors, diode lasers, and thermo-photovoltaic energy converters. In this project, we used spectroscopic ellipsometry in the spectral range of 0.74–6.5 eV to probe the linear optical response of Pb1-xSnxTe alloys in terms of the complex dielectric function. A strong optical response in the range of 0.7-2.0 eV arising from optical absorption was found. We studied eleven different samples of Pb1-xSnxTe of p-type origin with x values in the range (0 ≤ x ≤ 1). They were prepared by means of molecular beam epitaxy (MBE) on BaF2 substrates with 15mm2 area.</p>

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work properties were studied the structural, electronic and magnetic semiconductors PbSe and PbTe doped with europium (Eu) in the crystalline phase. The investigation is performed within the density functional theory (DFT). We observe that due a strong spin-orbit coupling, relativistic corrections are necessary to describe the PbSe and PbTe. To obtain a good description of crystals where Eu is present (EuSe and EuTe) the standard DFT fails. This fail is due to the fact that the Eu atom presents f electrons in the valence band, which are strongly localized. To describe the localized f electrons an additional procedure from the many body theory is necessary. We observe that using an additional term (the U term) from the Hubbard model, the DFT is able to describe the localized f electrons, such the theory now is called DFT+U. The formation energy results show that the Eu atom is more stable in Pb sites for both PbSe and PbTe. Eu in a Pb site in PbSe introduces electronic levels inside the band gap while the new electronic levels from Eu in a Pb site in PbTe are resonant with the top of the valence band. The analysis from the character of these electronic levels reveled that they come from the 4f electrons from the Eu atom. These results allow us to conclude that Eu is a good dopant to improve the thermoelectric properties of PbTe while the same is not observed for PbSe. Finally, we investigate the magnetic properties for Eu doping PbSe and PbTe, we observe that in both semiconductors there is a magnetic moment of the 1.0 μB localized in the Eu atom. / Neste trabalho foi estudado as propriedades estruturais, eletrônicas e magnéticas dos semicondutores de PbSe e PbTe dopados com európio (Eu) na fase cristalina. Utilizamos cálculos de primeiros princípios dentro do formalismo da teoria do funcional da densidade (DFT). Observamos que para uma boa descrição do PbSe e PbTe dentro da DFT é necessário a inclusão das correções relativísticas através da interação spin-órbita. Para a descrição de cristais onde o európio é um dos constituintes (EuSe e EuTe) se observou a necessidade de correções à DFT para que se possa ter uma boa descrição dos elétrons f provenientes do Eu e que são fortemente localizados. A teoria DFT+U, onde U é proveniente da teoria de muitos corpos dentro do modelo de Hubbard se mostrou eficiente. Com a melhor metodologia estabelecida iniciamos os cálculos das energias de formação. Os resultados mostraram que o Eu é mais estávelr em sítios de Pb, tanto no cristal de PbSe como no cristal de PbTe. Nesses sítios a análise da parte eletrônica diz que no PbSe existem níveis no gap provenientes dos elétrons 4f do Eu, enquanto que no PbTe esses níveis estão ressonantes com o topo da banda de valência. Isso permite concluir que o Eu é um bom dopante para melhorar as propriedades termoelétricas do PbTe, o mesmo não pode ser dito com relação a dopagem com Eu em PbSe. Com relação a parte magnética observa-se um momento magnético de 1,0 μB tanto no cristal de PbSe como no cristal de PbTe. Esse momento magnético é localizado no átomo de európio para ambos semicondutores.

Doctor Educationis / Three questions are central to this thesis: First, can the practice of teaching be made safe from luck through the controlling power of knowledge and reason? Second, even if it can be made safe from luck, should it be? Third, if it is neither possible nor desirable to exclude luck from teaching, what knowledge and personal qualities will put practitioners in the strongest position to face the contingencies of luck and, more especially, to face those conflicts which arise as a consequence of circumstances beyond the practitioner's control? Martha Nussbaum's account of luck and ethics in Greek philosophy and tragedy prompts the questions and provides, with Aristotle, many of the conceptual tools for answering them; Thomas Nagel's work on moral luck provides the categories for a more refined account of luck and its place in teaching. With respect to the first two questions, I argue that as a human practice teaching is open to the vicissitudes of fortune and cannot be made safe from luck, except at the expense of its vitality. Like other human practices, teaching is mutable, indeterminate and particular. Both its primary and secondary agents (teachers and pupils) and the practice itself are vulnerable to luck in four categories: constitutive, circumstantial, causal and consequential. But teaching is not just a matter of luck; it is a public practice in which some people are put into the hands of others for specific purposes, usually at public expense. If we have no way of holding practitioners accountable for their actions, the practice loses credibility. Any money or trust put into it is simply a gamble. For these and other reasons, the drive to exclude luck from practice is strong. Yet strong luck-diminishment projects are themselves a threat to the vitality of the practice. During the twentieth century two strong luck-diminishment projects have been especially detrimental to teaching: one rooted in the science of management, the other in the empirical sciences. Both have resulted in a proliferation of unfruitful and often trivial research projects, to misconceived programmes of teacher education, to distorted notions of knowledge and excellence in teaching, and to self-defeating and impoverished practice. Luck-diminishment projects rooted in logic are more or less threatening to vital practice, depending on how far they are committed to instrumental reasoning and a science of measurement. These are blunt and controversial claims. A central task of the thesis is to refine and defend them. The refinement proceeds by way of a contrastive analysis of strong luck-diminishment projects and others which are more responsive to the indeterminacy of practice. With respect to the final question, I argue that there are at least three sets of necessary conditions for a flourishing practice in the face of luck. One concerns what Aristotle calls the virtues of intellect and character. Central among these are practical rationality (conceived non-instrumentally), situational appreciation, and the knowledge required for an intelligent pursuit of the definitive ends of teaching. A second set concerns enabling institutions. A third concerns the kind of community best able to nurture those qualities necessary for vital and excellent practice. All three sets are themselves vulnerable to reversal. Keeping the practice of teaching alive and ensuring that it remains true to its definitive ends is thus a matter of sustained struggle.

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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.

<div>Inorganic metal chalcogenide materials are of great importance in the semiconducting field for various electronic applications such as photovoltaics, thermoelectrics, sensors, and many others. Compared to traditional vacuum processing routes, solution processing provides an alternate cost-effective route to synthesize these inorganic materials through its ease of synthesis and device fabrication, higher material utilization, mild processing conditions, and opportunity for roll-to-roll manufacturing. One such versatile solution chemistry involving a mixture of amine and thiol species has evolved in the past few years as a common solvent for various precursor dissolutions including metal salts, metal oxides, elemental metals, and chalcogens.</div><div><br></div><div>The amine-thiol solvent system has been used by various researchers for the fabrication of inorganic materials, but without the complete understanding of the chemistry involved in this system, utilizing its full potential, and overcoming any inherent limitations will be difficult. So, to identify the organometallic complexes and their reaction pathways, the precursor dissolutions in amine-thiol solutions, specifically for elemental metals like Cu, In and chalcogens like Se, Te were studied using X-ray absorption, nuclear magnetic resonance, infrared, and Raman spectroscopy along with electrospray ionization mass spectrometry techniques. These analyses suggested the formation of metal thiolate complexes in the solution with the release of hydrogen gas in the case of metal dissolutions confirming irreversibility of the dissolution. Insights gained for chalcogen dissolutions confirmed the formation of different species like monoatomic or polyatomic clusters when different amine-thiol pair is used for dissolution. Results from these analyses also identified the role of each component in the dissolution which allowed for tuning of the solutions by isolating the complexes to reduce their reactivity and corrosivity for commercial applications.</div><div><br></div><div>After identifying complexes in metal dissolution for Cu and In metals, the decomposition pathway for these complexes was studied using X-ray diffraction and gas chromatography mass spectrometry techniques which confirmed the formation of phase pure metal chalcogenide material with a release of volatile byproducts like hydrogen sulfide and thiirane. This allowed for the fabrication of impurity-free thin-film Cu(In,Ga)S2 material for use in photovoltaic applications. The film fabrication with reduced carbon impurity achieved using this solvent system yielded a preliminary promising efficiency beyond 12% for heavy alkali-free, low bandgap CuInSe2 material. Along with promising devices, by utilizing the understanding of the chalcogen complexation, a new method for CuInSe2 film fabrication was developed with the addition of selenide precursors and elemental selenium which enabled first-ever fabrication of a solution-processed CuInSe2 thin film with thickness above 2 μm and absence of any secondary fine-grain layer.</div><div><br></div><div>Along with thin-film fabrication, a room temperature synthesis route for lead chalcogenide materials (PbS, PbSe, PbTe) with controlled size, shape, crystallinity, and composition of nanoparticle self-assemblies was demonstrated. Micro-assemblies formed via this route, especially the ones with hollow-core morphology were subjected to a solution-based anion and cation exchange to introduced desired foreign elements suitable for improving the thermoelectric properties of the material. Adopting from traditional hot injection and heat up synthesis routes, a versatile synthesis procedure for various binary, ternary, and quaternary metal chalcogenide (sulfide and sulfoselenide) nanoparticles from elemental metals like Cu, Zn, Sn, In, Ga, and Se was developed. This new synthesis avoids the incorporation of impurities like O, Cl, I, Br arising from a traditional metal oxide, halide, acetate, or other similar metal salt precursors giving an opportunity for truly impurity-free colloidal metal chalcogenide nanoparticle synthesis.</div>