Orientadores: Munemasa Machida, José Helder Facundo Severo / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-23T20:24:15Z (GMT). No. of bitstreams: 1 Nascimento_Fellypedo_D.pdf: 5773174 bytes, checksum: 260b32bb9f860cd7cda3a4c349ce7817 (MD5) Previous issue date: 2013 / Resumo: Este trabalho tinha como objetivo desenvolver um diagnostico para medir temperaturas e densidades de elétrons (Te e ne) em plasmas de tokamaks, utilizando espectroscopia no visível de emissões de impurezas presentes no plasma. Foram obtidos resultados para medidas locais de temperaturas e densidades de elétrons no plasma dos tokamaks NOVA-UNICAMP e TCABR, a partir de medidas de emissões espectrais de íons de carbono e oxigênio. Para este propósito foi utilizada a relação entre o fluxo de partículas de impurezas e as emissões espectrais provenientes delas. Esta relação foi combinada com um método interativo para obter valores de Te e ne. Tais resultados foram alcançados baseados na teoria de que o fluxo de partículas de um determinado elemento presente no plasma não depende do comprimento de onda em que seus íons estão emitindo radiação, no regime de equilibrio colisional-radiativo. No tokamak NOVA-UNICAMP foram obtidos resultados utilizando emissões espectrais de carbono e oxigênio, porem apenas em um nível de ionização de tais elementos (C1+ e O1+). Nesta maquina, as medidas de três linhas de emissão provenientes de cada íon foram efetuadas de forma simultânea, ou seja, em um único disparo. Já no tokamak TCABR foram gerados resultados com emissões de três níveis de ionização do carbono (C1+, C2+ e C5+), mas as aquisições de dados nesta maquina foram realizadas em descargas diferentes, tendo sido medido um comprimento de onda emitido por um dado íon em cada disparo. Para todos os íons utilizados, e nas duas maquinas em que foram feitas medidas, os valores obtidos para as temperaturas de elétrons estão de acordo com os esperados para as regiões do plasma onde e maior a probabilidade de que cada íon em questão emita radiação. No caso especifico do TCABR, onde foram feitas medidas de emissões de três níveis de ionização do carbono, isto fica mais evidente, pois valores mais elevados de temperatura foram observados para maiores níveis de ionização. As densidades de elétrons que foram obtidas concordam em ordem de grandeza com os valores esperados, para todos os íons utilizados no trabalho, nos dois tokamaks. Porem os valores medidos estão acima do esperado, exceto para os resultados obtidos no TCABR com emissões de C5+. No tokamak TCABR foi possível comparar os resultados de ne obtidos pelo nosso método com os que são medidos por interferometria de micro-ondas. Na comparação, notou-se que o perfil temporal de ne medido com o nosso método esta em bom acordo com que foi obtido com o interferômetro. De um modo geral, os resultados obtidos foram bons, e podemos considerar que os objetivos deste trabalho de tese foram cumpridos / Abstract: In this work we got results for measurements of local electron temperatures and densities (Te and ne) at NOVA-UNICAMP and TCABR tokamak plasmas, by using visible spectroscopy of line emissions from carbon and oxygen ions, which are impurities in the plasma. For this purpose, we used the relationship between the particle flux and the photon flux emitted by an element (or an ion) at a fixed wavelength. That relationship was combined with an interactive method in order to determine Te e ne values. Such results were achieved based on the theory that the particle flux of a given ion specie in the plasma does not depend on the wavelength of the light emitted by the ion. For NOVA-UNICAMP tokamak we got results using spectral emissions of carbon and oxygen for only one ionization stage of these elements (C1+ and O1+). In this machine, we have made simultaneous measurements of each set of three spectral emissions from each ion specie in the same tokamak shot. For TCABR tokamak we got results using spectral emissions from three ionization stages of carbon (C1+, C2+ and C5+). But the data acquisition in this machine were made in different tokamak discharges, where we measured one spectral emission per time for each ion. The electron temperatures obtained with all ion emissions used in this work and in both machines are in good agreement with the expected values at the plasma position where each kind of ion has larger probability of be radiating. This fact become more evident in the TCABR tokamak, where we have emissions measurements of three carbon ionization stages, because higher Te values were measured for ions at higher ionization stages. All results obtained for electron densities agree in magnitude order, for both machines, with the expected values for this parameter. But the measured values are higher than the expected, except for the results obtained using C5+ emissions at TCABR tokamak. In TCABR was possible to compare the ne results obtained in our method with measurements made using a microwave interferometer. In that comparison we noted that the temporal profile of both diagnostics are in good agreement. The general conclusion is that the results obtained with our method were good and we consider that the objectives of this work were fulfilled / Doutorado / Física / Doutor em Ciências

Ce travail de thèse s’inscrit dans un contexte industriel. Il consiste en la caractérisation de lots bruts de SG1 : le N-tert-butyl-N- (1-diethylphosphono-2,2-dimethylpropyl)-N-oxyle. La spécificité de cette espèce est son caractère radicalaire stable. La première partie de ce travail consistait à développer une méthode d’analyse, facilement applicable en laboratoire d’analyse de contrôle sur site industriel pour la caractérisation de la pureté en SG1 dans des lots synthétisés. La méthode choisie a été développée par chromatographie liquide haute performance (HPLC). Pour ce faire, un étalon de SG1 a été préparé par purification de SG1 brut industriel en utilisant la technique séparative chromatographique de partage centrifuge (CPC). L’identification des impuretés suspectées majoritaires dans les lots de SG1 bruts a ensuite été réalisée par spectroscopie RMN ou par l’étude des fragments obtenus par spectrométrie de masse en tandem par ionisation electrospray. A l’aide de ces techniques, quinze impuretés majori- taires ont été identifiées. Des méthodes de quantification ont ensuite été développées pour douze de ces impuretés par diverses techniques analytiques chromatographiques : par HPLC-UV, HPLC-MS ou GC-MS ou par des techniques spectroscopiques Infra-Rouge ou encore par conductimétrie. / This PhD study has been carried out within an industrial context. It deals with the characterization of industrial batches of N-tert-butyl-N- (1-diethylphosphono-2,2-dimethylpropyl)-N-oxyle also called SG1. The distinctive feature of this molecule lies in its specific stability which is uncommon for radical species. The first part of this study consists in developping an analytical method, easy to implement in a QC laboratory for the determination of SG1 purity. The chosen analytical method has been developped by High Performances Liquid Chromatography (HPLC). This method requires the use of a standard sample of SG1, which has been obtained after purification of industrial batches of SG1 by the use of an innovative separative technology, the Centrifugal Partition Chromatography (CPC). The identification of the impurities, suspected as the major impurities in the industrial batches of SG1, has been carried out by NMR spectroscopy or by the study of their fragmentation observed by Tandem Mass Spectrometry – Electrospray Ionization. The use of these techniques enabled the identification of fifteen major impurities. Quantification methods by various techniques (HPLC-UV, HPLC-MS, GC-MS, other direct spectroscopic techniques like Infra-Red or other types of techniques like conductimetry) have been developped for twelve impurities.

Orientador: Guillermo Gerardo Cabrera Oyarzún / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-30T18:12:28Z (GMT). No. of bitstreams: 1 Hernandez_FabioHernandez_M.pdf: 2178317 bytes, checksum: 00e18623b835112b2aa5c348e4651b65 (MD5) Previous issue date: 2016 / Resumo: A descrição da dinâmica quântica de sistemas de muitos corpos é um ingrediente chave para computação e simulações quânticas. No presente projeto, estudamos a dinâmica de cadeias de spin na presença de impurezas ou defeitos. O sistema de Ising quantico (Ising com campo transverso) com uma impureza foi solucionado de forma exata. Este sistema de spins pode ser simulado de forma analítica por partículas quânticas (transformação de Jordan-Wigner). Caracterizamos o espectro, as autofunções e a evolução temporal da magnetização para estados iniciais particulares, focando no papel desempenhado pelos estados de impureza. Finalmente observamos oscilações remanescentes na magnetização, após a relaxação do sistema, para alguns valores dos parâmetros da impureza nos quais existem dois estados ligados no espectro de energias / Abstract: The description of dynamics of quantum many-body systems is a key ingredient to perform quantum computation and/or simulations of quantum behavior. In the present proposal, we study the time evolution of quantum spin chains with impurities at one of the boundaries, in order to understand the role of defects in relaxation properties. The quantum (transverse) Ising model with an impurity has been solved in exact form, using the Jordan-Wigner transformation, where spins are mapped onto spinless fermions, thus simulating analytically a spin system with particles. We completely characterize the spectrum, with the presence of bound states depending on values of the impurity parameters. We calculate the local magnetization and observe its relaxation for particular non-homogeneous initial states. Surprisingly, remanent Rabi oscillations are observed at asymptotically long times, when the spectrum displays two bound states / Mestrado / Física / Mestre em Física / 1247646/2013 / CAPES

Die Entwicklung der Mikroelektronik wird durch eine fortschreitende Miniaturisierung der Bauelemente geprägt. Infolge einer Reduzierung der Querschnittflächen von Leitbahnstrukturen erhöht sich die elektrische Leistungsdichte und das Metallisierungssystem bestimmt zunehmend die Übertragungsgeschwindigkeiten. Kupfer repräsentiert hierbei das verbreitetste Leitbahnmaterial und wird vorwiegend mittels elektrochemischer Abscheidung in vergrabene Damaszen-Strukturen eingebracht. Die vorliegende Dissertation beschreibt Möglichkeiten für eine Optimierung von Kupferleitbahnen für höchstintegrierte Schaltkreise. Von besonderem Interesse sind hierbei die Gefügequalität und der Reinheitsgrad. Es erfolgen umfangreiche werkstoffanalytische und elektrochemische Untersuchungen zur Charakterisierung von Depositionsmechanismen, des Einbaus von Fremdstoffen, des Mikrogefüges nach der Abscheidung und der Mikrogefügeumwandlung. In einem abschließenden Forschungsschwerpunkt werden Kupfer-Damaszen-Teststrukturen mit unterschiedlichen Gehalten nichtmetallischer Verunreinigungen hergestellt und entsprechenden Lebensdauerexperimenten unterzogen. Hierdurch gelingt eine Evaluierung des Einflusses jener Verunreinigungen auf die Elektromigrationsbeständigkeit von Kupferleitbahnen. Die Arbeit umfasst daher das gesamte Spektrum von der Grundlagenforschung bis zur Applikation von elektrochemisch abgeschiedenen Kupferdünnschichtmetallisierungen.

Hyperdoping of Si with deep-level impurities has attracted renewed interest for its unique physical properties, such as the broad sub-bandgap absorption in the infrared wavelength at room temperature. In this thesis, tellurium (Te) hyperdoped Si has been prepared by ion implantation and pulsed laser melting with the Te doping concentration several orders of magnitude above the solid solubility limit. The structural, electrical and optical properties were systematically investigated. A strong room-temperature broadband infrared absorption down to 0.048 eV (25 μm) is observed in the resulting Te-hyperdoped Si layers. The room-temperature operation of a mid-infrared photodetector is demonstrated based on Te-hyperdoped Si. In addition, an impurity-induced insulator-to-metal transition in Te-hyperdoped Si has been identified via the electrical transport measurements. Besides, the electron concentration in Te-hyperdoped Si layers is approaching 1021 cm-3 and does not show saturation. Combining density functional calculations and Rutherford backscattering/channeling measurements, the microscopic mechanism for yielding the outstanding physical properties listed above has been unveiled. The Te-dimer complex sitting on adjacent Si lattice sites has the smallest formation energy and is thus the preferred configuration at high doping concentration. Those substitutional Te are effective donors, leading to the non-saturating carrier concentration as well as to the insulator to metal transition. Finally, a comprehensive study regarding the thermal stability has been performed and the Te-hyperdoped Si layers exhibits thermal stability up to 400 °C with a duration of at least 10 minutes. Therefore, Te-hyperdoped Si opens two perspectives for opto/micro-electronics. One is realization of broadband infrared photodetection at room temperature by using only Si materials, which may be integrated into on-chip Si-based photonic systems. The second is to achieve ultra-high n-type carrier concentrations for nano-electronics by forming Te-dimer dopants, which can overcome the saturation problem of conventional shallow n-type dopants.

“La vie ne produit pas de corps symétrique”L. Pasteur. Briser la symétrie-miroir est un sujet fascinant qui revêt un rôle crucial en physique, en chimie et en biologie.Le but ultime de cette étude est de démontrer expérimentalement la conjecture de Curie de-Gennes. Cette hypothèse a été proposée pour la première fois par P. Curie 1894 et plus tard développée par De-Gennes. Elle indique qu’il est possible de générer une dissymétrie (excès énantiomérique (e.e.)) en soumettant un mélange racémique à l'influence combinée de champs magnétique et électrique colinéaires. Une telle influence modifie la cinétique du système : selon l'orientation relative des champs magnétique et électrique, l'un des énantiomères est formé plus rapidement que l'autre en raison d’une énergie d'activation inférieure (Ea). Une telle influence a été ultérieurement appelée « faussement chirale » par Barron. Pour démontrer expérimentalement cette conjecture, deux expériences différentes ont été développées :1) La cristallisation énantiosélective d'un réseau de coordination chiral sous des influences physiques externes (champ magnétique ou force de rotation) par diffusion lente. Un petit e.e. est supposé être créé puis amplifié par la croissance des cristaux à l'interface solvant/vapeur d'éthanol. Dans cette expérience, nous avons constaté que la démonstration de conjecture de Curie de Gennes est difficile à atteindre en raison de la forte dispersion de la moyenne des valeurs du e.e. obtenues et de la faiblesse de l'effet attendu.2) La création d'un e.e. dans un atropisomère racémique d’un cristal liquide à base de biphényle en appliquant des champs magnétique et électrique (anti) parallèles. Un arrangement supramoléculaire hélicoïdal des molécules de biphényles dans la phase nématique augmentera le signal lié à la présence d’un e.e. à un niveau mesurable. Au cours de cette seconde expérience, nous avons observé expérimentalement un e.e des dérivés à base de biphényle induit par une combinaison (anti)parallèle de champs magnétique et électrique. Cet excès dépend linéairement du produit des champs magnétique et électrique et l’ordre de grandeur des résultats observés expérimentalement correspond aux estimations théoriques. Compte tenu des résultats obtenus, sous réserve d’ultimes vérifications, cette expérience constitue une démonstration expérimentale convaincante de la conjecture Curie de-Gennes. / “La vie ne produit pas de corps symétrique” L. Pasteur Mirror symmetry breaking is an ever-fascinating topic that plays a crucial role in physics, chemistry, and biology. The ultimate goal of this study is to demonstrate experimentally the so-called Curie de-Gennes conjecture. It was proposed for the first time by P. Curie (1894) and later developed by de-Gennes. It stipulates that it is possible to generate dissymmetry (enantiomeric excess (e.e.)) by submitting a racemic mixture to the combined influence of collinear magnetic and electric fields. Such influence modifies the kinetics of the system: depending on the relative orientation of the magnetic and electric fields, one of the enantiomers is formed faster than the other because of a lower activation energy (Ea),. This influence was later named by Barron as « falsely chiral ». To demonstrate this conjecture, two different experiments were developed:1) The enantioselective crystallization of a chiral metal-organic framework under external physical influence (magnetic field or rotation force) by slow diffusion. The small e.e. is expected to be created and amplified by crystal growth at the interface aqueous solution / ethanol-saturated vapors. In this experiment, we have found that the Curie de-Gennes conjecture demonstration is difficult to achieve due to high dispersion of the average of the observed e.e. and the weakness of the expected effect. 2) Creating an e.e. in a racemic atropisomeric biphenyl based liquid crystal by applying (anti)parallel magnetic and electric fields. The helical twisting power of biphenyls molecules in the nematic phase will enhance the dichroic signal related to the expected e.e. to a measurable level. During this second experiment we have experimentally observed an e.e. in biphenyl-based nematic liquid crystals induced by (anti)parallel combination of magnetic and electric fields. This excess was linearly dependent on the product of magnetic and electric fields and, within one order of magnitude, its absolute value corresponds to the theoretical estimation. Ultimate checks shall confirm that these results constitute a convincing experimental demonstration of the Curie de Gennes conjecture.

Intermediate band (IB) materials have attracted considerable research interest since they can dramatically enhance the near infrared light absorption and lead to applications in the fields of so-called intermediate band solar cells or infrared photodetectors. Hyperdoping Si with deep level impurities is one of the most effective approaches to form an IB inside Si. In this thesis, titanium (Ti) or chalcogen doped Si with concentrations far exceeding the Mott transition limits (~ 5×10^19 cm-3 for Ti) are fabricated by ion implantation followed by pulsed laser annealing (PLA) or flash lamp annealing (FLA). The structural and electrical properties of the implanted layer are investigated by channeling Rutherford backscattering spectrometry (cRBS) and Hall measurements. For Si supersaturated with Ti, it is shown that Ti-implanted Si after liquid phase epitaxy shows cellular breakdown at high doping concentrations during the rapid solidification, preventing Ti incorporation into Si matrix. However, the out-diffusion and the cellular breakdown can be effectively suppressed by solid phase epitaxy during FLA, leading to a much higher Ti incorporation. In addition, the formed microstructure of cellular breakdown also complicates the interpretation of the electrical properties. After FLA, the samples remain insulating even with the highest Ti implantation fluence, whereas the sheet resistance decreases with increasing Ti concentration after PLA. According to the results from conductive atomic force microscopy (C-AFM), the decrease of the sheet resistance after PLA is attributed to the percolation of Ti-rich cellular walls, but not to the insulator-to-metal transition due to Ti-doping. Se-hyperdoped Si samples with different Se concentrations are fabricated by ion implantation followed by FLA. The study of the structural properties of the implanted layer reveals that most Se atoms are located at substitutional lattice sites. Temperature-dependent sheet resistance shows that the insulator-to-metal transition occurs at a Se peak concentration of around 6.3 × 10^20 cm-3, proving the formation of an IB in host semiconductors. The correlation between the structural and electrical properties under different annealing processes is also investigated. The results indicate that the degrees of crystalline lattice recovery of the implanted layers and the Se substitutional fraction depend on pulse duration and energy density of the flash. The sample annealed at short pulse durations (1.3 ms) shows better conductivity than long pulse durations (20 ms). The electrical properties of the hyperdoped layers can be well-correlated to the structural properties resulting from different annealing processes.:Chapter 1 Introduction 1 1.1 Shallow and Deep level impurities in semiconductors 1 1.2 Challenges for hyperdoping semiconductors with deep level Impurities 2 1.3 Solid vs. liquid phase epitaxy 5 1.4 Previous work 7 1.4.1 Transition metal in Si 7 1.4.2 Chalcogens in Si 10 1.5 The organization of this thesis 15 Chapter 2 Experimental methods 18 2.1 Ion implantation 18 2.1.1 Basic principle of ion implantation 18 2.1.2 Ion implantation equipment 19 2.1.3 Energy loss 20 2.2 Pulsed laser annealing (PLA) 23 2.3 Flash lamp annealing (FLA) 24 2.4 Rutherford backscattering and channeling spectrometry (RBS/C) 27 2.4.1 Basic principles 27 2.4.2 Analysis of the elements in the target 28 2.4.3 Channeling and RBS/C 29 2.4.4 Analysis of the impurity lattice location 31 2.5 Hall measurements 31 2.5.1 Sample preparation 32 2.5.2 Resistivity 32 2.5.3 Hall measurements 33 Chapter 3 Suppressing the cellular breakdown in silicon supersaturated with titanium 34 3.1 Introduction 34 3.2 Experimental 35 3.3 Results 36 3.4 Conclusions 42 Chapter 4 Titanium-implanted silicon: does the insulator-to-metal transition really happen? 44 4.1 Introduction 44 4.2 Experimental section 45 4.3 Results 47 4.3.1 Recrystallization of Ti-implanted Si 47 4.3.2 Lattice location of Ti impurities 48 4.3.3 Electrical conduction 50 4.3.4 Surface morphology 52 4.3.5 Spatially resolved conduction 53 4.4 Discussion 55 4.5 Conclusion 56 Chapter 5 Realizing the insulator-to-metal transition in Se hyperdoped Si via non-equilibrium material processing 57 5.1 Introduction 57 5.2 Experimental 59 5.3 Results 60 5.4 Conclusions 65 Chapter 6 Structural and electrical properties of Se-hyperdoped Si via ion implantation and flash lamp annealing 67 6.1 Introduction 67 6.2 Experimental 68 6.3 Results 69 6.4 Conclusions 76 Chapter 7 Summary and outlook 78 7.1 Summary 78 7.2 Outlook 81 References 83 Publications 89

Galliumnitrid (GaN) ist ein Schlüsselmaterial zur Produktion von elektronischen Hochfrequenz- und Hochleistungsbauelementen sowie Leuchtdioden. Zum Erreichen der optimalen Bauelementleistung ist ein tiefgreifendes Verständnis sowie die Kontrolle von Punktdefekten unabdingbar um die elektrischen und optischen Substrateigenschaften präzise einzustellen. Im Rahmen dieser Arbeit wurden Punktdefekte in GaN mittels Photolumineszenz (PL)-spektroskopie untersucht. Häufige Übergangsmetallverunreinigungen (Fe, Mn und Cr) wurden anhand ihrer internen Übergänge, die sich durch scharfe Lumineszenz- und Absorptionslinien im nahen Infrarot auszeichnen, identifiziert. Mn und Cr wurden als Ursprung für ungewollte Substratfärbungen bestimmt. Teilweise Entfärbung konnte durch Mn-Si-Kodotierung erreicht werden. Der Zusammenhang zwischen Absorption und Emission des Cr-Zentrums wurde durch polarisationsabhängige PL-Anregungsspektroskopie analysiert. Weiterhin wurde der Einfluss von Kohlenstoffdotierung auf die Eigenschaften von GaN-Substraten durch PL- und PL-Anregungsspektroskopie untersucht. Eine neue Emissionsbande um 1,62 eV, die am effizientesten bei 2,7 eV angeregt wird, wurde für hochdotiertes GaN:C beobachtet und einem internen Übergang C_N-C_Ga-C_N-Komplexen zugeschrieben. / Gallium nitride (GaN) is a key material for the production of high frequency and high power electronics as well as light emitting diodes. Optimum device performance requires a profound understanding and control of the point defect formation in order to determine the electrical and optical substrate properties. Within this thesis, photoluminescence (PL) spectroscopy was applied to analyze point defects in GaN. Common transition metal impurities (Fe, Mn and Cr) were identified by their internal transitions characterized by sharp luminescence and absorption lines in the near infrared region. Among them, Mn and Cr were shown to be the origin of undesirable substrate coloration. Partial decoloration was achieved by an Mn-Si codoping approach. The relationship of absorption and emission processes of the Cr impurity center was further analyzed by polarization dependent PL excitation spectroscopy. Furthermore, the impact of C-doping on GaN substrate properties was investigated by PL and PL excitation spectroscopy. A new emission band around 1.6 eV, most efficiently excited at 2.7 eV, was reported for highly C-doped GaN and proposed to originate from an internal transition of C_N-C_Ga-C_N complexes.

In this study unintentionally doped GaN grown by hydride vapor phase epitaxy that exhibits a sharply delimited region of green color was investigated. Optical analysis was performed by absorption and photoluminescence spectroscopy. An absorption band between 1.5 and 2.0 eV was found to be responsible for the green color and was related to a sharp emission at 1.193 eV by luminescence and excitation spectroscopy. The appearance of both optical signatures in the region of green color was related to an increase of Cr contamination detected by secondary ion mass spectrometry. We propose that the origin of green color as well as the emission line at 1.193 eV is attributed to internal transitions of Cr⁴⁺.

Recently simulation groups have reported the lanthanide series elements as the dopants that have the strongest effect on the stabilization of the ferroelectric non-centrosymmetric orthorhombic phase in hafnium oxide. This finding confirms experimental results for lanthanum and gadolinium showing the highest remanent polarization values of all hafnia-based ferroelectric films until now. However, no comprehensive overview that links structural properties to the electrical performance of the films in detail is available for lanthanide-doped hafnia. La:HfO₂ appears to be a material with a broad window of process parameters, and accordingly, by optimization of the La content in the layer, it is possible to improve the performance of the material significantly. Variations of the La concentration leads to changes in the crystallographic structure in the bulk of the films and at the interfaces to the electrode materials, which impacts the spontaneous polarization, internal bias fields, and with this the field cycling behavior of the capacitor structure. Characterization results are compared to other dopants like Si, Al, and Gd to validate the advantages of the material in applications such as semiconductor memory devices.