Tunnelmagnetowiderstandselemente (MTJ) mit einer kristallinen MgO Tunnelbarriere zwischen amorphen CoFeB-Elektroden haben Aufgrund ihres hohen Tunnelmagnetowiderstandes (TMR) und der guten Integrationsmöglichkeit in bestehende Prozesse viel Aufmerksamkeit bekommen. Dabei zeigten vorherige Berechnungen, dass die strukturellen und chemischen Eigenschaften der Grenzfläche einen signifikanten Einfluss auf den TMR aufweisen, weshalb diese Grenzfläche im Rahmen dieser Arbeit mittels quantitativer, hochauflösender und analytischer Transmissionselektronenmikroskopie analysiert wurde. Um einen hohen TMR in die diesen Systemen zu erzielen ist ein kristalliner Übergang zwischen der Tunnelbarriere und den Elektroden notwendig. Berechnungen zeigten, dass bereits wenige Monolagen kristallinen Materials an der Grenzfläche ausreichen, um einen hohen TMR in diesen Systemen zu erzielen. Ausgehend von diesen Berechnungen wurde die Mikrostruktur auf der Subnanometer-Skala an der kristallin/amorphen Grenzfläche von MgO-CoFeB in dieser Arbeit untersucht. Die experimentellen Daten wurden hierfür mittels aberrationskorrigierter, hochauflösender Transmissionselektronenmikroskopie (HRTEM) an Modellsystemproben erstellt und die vom MgO induzierte kristalline Ordnung an der Grenzfläche zum CoFeB mittels iterativen Bildserienvergleichs mit simulierten Daten quantifiziert. Zur Simulation der HRTEM-Grenzflächenabbildungen wurde die „Averaged-Projected-Potential“-Näherung genutzt, welche im Rahmen dieser Arbeit um die Berücksichtigung von monoatomaren Stufen entlang der Strahlrichtung des Mikroskops erweitert wurde. Es zeigte sich, dass mit dieser Methode die Ordnung an der MgO-CoFeB-Grenzfläche von nicht ausgelagerten Systemen gut beschrieben werden kann. In ausgelagerten Systemen kommt es dagegen zu einer Bor-diffusion aus dem a-CoFeB heraus um damit eine Kristallisation am MgO zu ermöglichen. Im zweiten Teil dieser Arbeit werden die Bordiffusion und die Kristallisation in Abhängigkeit von der Deckschicht als auch der MgO-Depositionsmethode sowohl an Modellsystemproben als auch an funktionsfähigen MTJs untersucht. Elektronen-Energie-Verlustspektroskopie (EELS) an diesen Proben konnten zeigen, dass sowohl die Deckschicht also auch die MgO-Depositionsmethode einen entscheidenden Einfluss auf die Bor-Diffusion in diesen Systemen ausüben.

Orientador: Mônica Alonso Cotta / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-17T22:17:37Z (GMT). No. of bitstreams: 1 NietoGonzalez_Luis_D.pdf: 3428571 bytes, checksum: 13775c720d8ebcf8c855b532ae715b49 (MD5) Previous issue date: 2007 / Resumo: Neste trabalho estudamos os mecanismos de crescimento durante a epitaxia por feixe químico de nanoestruturas III-V baseadas no sistema InAs/InP. Particularmente, foram estudados nanofios e ilhas de InAs sobre uma camada buffer InP(001) e nanofios de InAs sobre uma matriz de InGaAs/InP (com mesmo parâmetro de rede). Apresentaremos, nesta tese, as diferenças e similaridades destes sistemas quanto a condições de crescimento, distribuição de tamanho, forma e os efeitos de volume da camada de InGaAs sobre as nanoestruturas de InAs quando comparadas ao sistema InAs/InP. Nossa escolha do InGaAs/InP como camada buffer para a nucleação dos fios de InAs, foi feita porque facilitaria a utilização deste sistema em diversas aplicações, proporcionando maior flexibilidade no desenho dos dispositivos. Por outro lado, este material abre a possibilidade de controlar as características das nanoestruturas através das propriedades de bulk e superficiais da liga ternária InGaAs. Além disso, ligas ternárias podem exibir efeitos de volume que afetam suas propriedades superficiais. Estes fenômenos podem afetar a nucleação dos fios quânticos e por isso foram objeto de nosso estudo. Para isso utilizamos e correlacionamos medidas in situ de difração de elétrons de alta energia (RHEED), microscopia de força atômica (AFM) e eletrônica de transmissão (TEM), com os resultados obtidos por difração de raios X com incidência rasante (GIXD). Verificamos, deste modo, tanto a influência das condições de crescimento, como o comportamento da relaxação da energia elástica nas nanoestruturas. Com todos estes resultados mostramos como acontece a evolução da deformação nos nanofios e pontos quânticos de InAs/InP e como acontecem as transições de forma entre estes dois tipos de nanoestruturas, em função das condições de crescimento e tipo de superfície do substrato utilizado. Mostramos, também que a introdução de um composto ternário (InGaAs) entre o InAs e o InP não afeta significativamente a forma e tamanho das nanoestruturas quando comparadas ao caso InAs/InP. Em particular, a interdifusão gerada por variações locais da composição na camada buffer em nanofios de InAs pode ser minimizada através de mudanças nas condições de crescimento do InGaAs / Abstract: In this work we study the growth mechanisms of III-V nanostructures by chemical beam epitaxy (CBE) based on the InAs/InP materials system. Particularly, nanowires and nanodots of InAs on InP (001) and InAs nanowires on InGaAs/InP (lattice matched) buffer layers were studied. The differences and similarities of these systems are presented in this text, as a function of growth conditions, size distribution, as well as the bulk effects of the InGaAs layer on InAs nanostructures when compared to the InAs/InP system. Our choice of InGaAs/InP buffer layer for InAs nanowire nucleation was due to the possible use of this system in many applications, providing greater flexibility in device design. Furthermore, this material opens up the possibility of controlling nanostructures characteristics through bulk and surface properties of the InGaAs ternary alloy. In other hand, ternary alloys may present volume effects that affect their surface properties. These phenomena can affect quantum wires nucleation and thus became one of the subjects of our study. With these goals in mind, we have correlated in situ high-energy electrons diffraction (RHEED) measurements, atomic force microscopy (AFM) and transmission electron microscopy (TEM) images with the results obtained by grazing incidence X-ray diffraction (GIXD). We report here the influence of the growth conditions on nanostructure shape as well as the behavior of elastic energy relaxation within the nanostructures. Our results show how the evolution of deformation within InAs/InP nanowires and quantum dots occur and how the shape transition between these two types of nanostructures depend on the growth conditions and the substrate surface type used. We also show that the introduction of a ternary compound (InGaAs) between InAs and InP does not significantly affect the shape and size of nanostructures as compared to the InAs / InP case. In particular, the interdifusion generated in InAs nanowires by local variations in the buffer layer composition can be minimized through changes in InGaAs growth conditions / Doutorado / Estrutura de Líquidos e Sólidos; Cristalografia / Doutor em Ciências

Silicon technologyhas been seekingfor a monolithic solution for a chip where data processing and data communication is performed in the CMOS part and the photonic component, respectively. Traditionally, silicon has been widely considered for electronic applications but not for photonic applications due to its indirect bandgap nature. However, band structure engineering and manipulation through alloying Si with Ge and Sn has opened new possibilities. Theoretical calculations show that it is possible to achieve direct transitions from Ge ifit is alloyed with Sn. Therefore, a GeSn system is a choice to get a direct bandgap. Extending to ternary GeSnSi and quaternary GeSnSiCstructures grown on Si wafers not only makes the bandgap engineering possible but also allowsgrowing lattice matched systems with different strain and bandgaps located in the infrared region. Different heterostructures can be designed and fabricated for detecting lightas photonic sensing oremitting the light as lasers. Alloying not only makes engineering possible but it also induces strain which plays an important role for electronic applications. Theoretical and experimental works show that tensile strain could increase the mobility, which is promising for electronic devices where high mobility channels for high performance MOSFETs is needed to speed up the switching rate. On the other hand, high n-doping in tensile strains in p-i-n structures makesΓ band transitions most probable which is promising for detection and emission of the light. As another benefit of tensile strain, the direct bandgap part shrinks faster than the indirect one if the strain amount is increased. To get both electronic and photonic applications of GeSn-based structures, two heterostructures (Ge/GeSn(Si)/GeSi/Ge/Si and Ge/GeSn/Si systems), including relaxed and compressive strained layers used to produce tensile strained layers, were designed in this thesis. The low temperature growth is of key importance in this work because the synthesis of GeSn-based hetrostructures on Si wafers requires low thermal conditions due tothe large lattice mismatch which makes them metastable. RPCVD was used to synthesize theseheterostructures because not only it offers a low temperature growth but also because it is compatible with CMOS technology. For utilization of these structures in devices, n-type and p-type doping of relaxed and compressive strained layers were developed. HRRLMs, HRTEM, RBS, SIMS, and FPP techniques were employed to evaluatestrain, quality, Sn content and composition profile of the heterostructures. The application of GeSn-based heterostructures is not restricted to electronics and photonics. Another application investigated in this work is photovoltaics. In competition with Si-based solar cells, which have, or areexpected to have,high stability and efficiency, thirdgeneration solar cells offer the use of low cost materials and production and can therefore be an alternative for future light energy conversion technology. Particularly, quantum dot sensitized solar cells are associated with favorable properties such as high extrinsic coefficients, size dependent bandgaps and multiple exciton generation and with a theoretical efficiencyof 44%. In this work, two categories of QDs, Cd-free and Cd-based QDs were employed as sensitizers in quantum dot sensitized solar cells (QDSSCs). Cd-based QDs have attracted large interest due to high quantum yield,however, toxicityremains still totheir disadvantage. Mn doping as a bandgap engineering tool for Cd-based type IIZnSe/CdS QDs wasemployed to boostthe solar cell efficiency. Theoretical and experimental investigations show that compared to single coreQDSSCs,typeII core-shells offer higher electron-hole separation due to efficient band alignment where the photogenerated electrons and holes are located in the conduction band of the shell and valence band of the core, respectively. This electron-hole separation suppresses recombination and by carefully designing the band alignment in the deviceit can increase the electron injection and consequently the power conversion efficiency of the device. Considering eco-friendly and commercialization aspects, three different “green” colloidal nanostructures having special band alignments, which are compatible for sensitized solar cells, were designed and fabricated by the hot injection method. Cu2GeS3-InP QDs not only can harvest light energy up to the infraredregion but can also be usedastypeII QDs. ZnS-coating was employed as a strategy to passivate the surface of InP QDs from interaction with air and electrolyte. In addition, ZnS-coating and hybrid passivation was applied for CuInS2QDs to eliminate surface traps. / <p>QC 20151125</p>

Magister Scientiae - MSc / In this study multilayer graphene nanosheets was synthesize by oxidizing graphite to graphene oxide using H2SO4 and KMnO4 followed by reduction of graphene oxide to graphene using NaBH4. The graphene nanosheets were characterized by Fourier Transform Infrared (FTIR) and Raman spectroscopy, high resolution transmission electron microscopy (HRTEM), Scanning electron microscopy (SEM) and X-ray diffraction (XRD). HRTEM images showed that the multilayer graphene were obtained. The graphene was immobilized directly onto a glassy carbon electrode using the drop coating technique followed by the in situ deposition of mercury, bismuth or antimony thin films to afford graphene modified glassy carbon metal film electrodes (Gr-GC-MEs). The experimental parameters (deposition potential, deposition time, rotation speed, frequency and amplitude) were optimized, and the applicability of the modified electrode was investigated towards the individual and simultaneous determination of Zn2+, Cd2+ and Pb2+ at the low concentration levels (μg L-1) in 0.1 M acetate buffer (pH 4.6) using square wave anodic stripping voltammetry (SWASV). The detection limits values for the Gr-GC-HgE was 0.08, 0.05 and 0.14 μg L-1 for Zn2+, Cd2+ and Pb2+, respectively. The Gr-GC-BiE the detection limits for was 0.12, 0.22 and 0.28 μg L-1 for Zn2+, Cd2+ and Pb2+ while the detection limits for the Gr-GC-SbE was 0.1, 0.3 and 0.3 μg L-1 for Zn2+, Cd2+ and Pb2+, respectively. A Gr-GCE prepared without any binding agents or metal film had detection limits for Zn2+, Cd2+ and Pb2+ of 3.9, 0.8 and 0.2 μg L-1 for Zn2+, Cd2+ and Pb2+. Real sample analysis of which was laboratory tap water was performed using the Gr-GCMEs. Only Gr-GC-HgE was sensitive enough to detect metal ions in the tap water samples at the 3ppb level whereas, the GC-BiE and GC-SbE detected the metal ions at the 10 μg L-1 to 30 μg L-1 level.

[pt] A presente tese tem como objetivo estudar a estabilidade microestrutural da superliga 625 a base de Ni pelas suas propriedades mecânicas e suas várias aplicações na indústria, em três condições distintas: maciça (placa forjada industrialmente), partículas de pó precursora da peça 3D e uma peça produzida por impressão a laser (Deposição Direta de Metais - DMD). Amostras destas condições foram submetidas a tratamentos de solubilização e envelhecimento isotérmico a 650 graus Celsius e 750 graus Celsius durante 10 horas e 100 horas, de modo a promover fenômeno de precipitação e, assim, correlacionar com as propriedades mecânicas do material. A caracterização microestrutural foi realizada por microscopia ótica (MO), microscopia eletrônica de varredura (MEV), microscopia eletrônica de transmissão (MET) no modo convencional utilizando contraste de difração, na modalidade analítica de transmissão/varredura (STEM), e em alta resolução (HRTEM). Espectroscopias de raios X por dispersão em energia (EDS) e de perdas de energia de elétrons (EELS) foram utilizadas para analisar a composição local da matriz e das fases presentes. Foram realizados ensaios de microdureza para avaliar o efeito dos tratamentos térmicos. A análise microestrutural da amostra maciça na condição como recebida apresentou grãos equiaxiais com fases NbTiC e M6C. Com o tratamento térmico de solubilização a 1100 graus Celsius por 40 minutos houve uma dissolução parcial dos carbetos. O envelhecimento a 650 graus Celsius por 10 horas resultou em carbetos de NbTiC e um aumento da dureza em 5 porcento em relação a amostra como solubilizada. Entretanto no tratamento de envelhecimento a 100 horas ocorreu precipitação homogênea da fase gama aumentando a dureza do material em 45 porcento, se comparada à mesma como solubilizada. A liga maciça envelhecida a 750 graus Celsius por 10 horas apresentou os carbetos NbTiC e M23C6 nos contornos de grãos e dispersos na matriz. Já a liga maciça envelhecida por 100 horas a esta mesma temperatura, apresentou a fase δ dispersa na matriz. A análise microestrutural do pó precursor mostrou ser policristalino constituído predominantemente de grãos colunares da matriz austenítica. Análises das amostras produzidas por DMD como recebida revelou estrutura dendrítica com carbetos de Nb e fase Laves nas regiões interdendríticas. A solubilização das amostras DMD durante 40 minutos por 1100 graus Celsius e 1200 graus Celsius mostrou ser insuficientes para a dissolução dos precipitados. A fim de melhorar a difusão do Nb e a dissolução dos carbetos e da fase Laves, foi realizado o tratamento de solubilização a 1200 graus Celsius por 100 horas. Esta amostra tratada a 650 graus Celsius por 100 horas apresentou carbetos M23C6 precipitados nos contornos de grão e nas interfaces entre matriz CFC e a fase Laves. Entretanto, no envelhecimento a 750 graus Celsius durante 100 horas ocorreu à precipitação dos carbetos M23C6 e M6C nos contornos de grão e dispersos na matriz, aumentando assim a dureza do material em 18 porcento, se comparada à mesma como solubilizada. O aumento da microdureza em 12 porcento após o tratamento térmico está relacionado à precipitação dos carbetos nos contornos de grão e dispersos na matriz resultado dos tratamentos térmicos de envelhecimento. / [en] This thesis studies the microstructural stability of Ni-base Super alloy 625 for its mechanical properties and its varieties of applications in the industry, in three different conditions: bulk (industrially forged plate), precursor powder particles for 3D printing process and a sample produced by laser Direct Metal Deposition (DMD). Aiming at promoting precipitation processes and, therefore, correlate with the mechanical properties of the material, samples of these conditions were submitted to solution annealing and isothermal aging treatments at 650 Celsius degrees and 750 Celsius degrees for 10 hours and 100 hours. Characterization of the microstructure was performed by optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), in the conventional diffraction contrast mode, scanning/transmission (STEM) analytical mode, and high resolution microscopy (HRTEM). Energy dispersive X-ray spectrometry (EDXS) and electron energy loss spectroscopy (EELS) were used to analyze the local composition of the matrix and precipitated phases. Micro hardness measurements were performed to evaluate the effect of thermal treatments. The microstructural analysis of the bulk sample in the as-received condition showed an equiaxial grain structure with NbTiC and M6C precipitated phases. Solid solution treatment at 1100 Celsius degrees for 40 minutes allowed partial dissolution of the carbides. Aging at 650 Celsius degrees for 10 hours showed NbTiC carbides and a hardness increase of 5 percent compared to the as-solubilized sample. However, aging at this temperature for 100 hours promoted the homogeneous precipitation of the gama phase, thus increasing the material s hardness by 45 percent, when compared to it as solubilized. The bulk sample aged at 750 Celsius degrees for 10 hours showed grain boundary and homogeneous precipitation of NbTiC and M23C6 carbides. This sample condition upon aging at this temperature for 100 hours shows δ phase homogeneously precipitated in the matrix. The microstructural analysis of the precursor powder showed micrometer size individual particles as polycrystalline, consisting predominantly of columnar grains of the austenitic matrix. Analysis of samples produced by DMD in the as-received condition revealed dendritic microstructure with carbides of Nb and Laves phase in the interdendritic regions. The solution treatment of the DMD samples for 40 minutes at 1100 Celsius degrees and 1200 Celsius degrees proved to be insufficient for the dissolution of the precipitate. In order to enhance diffusion of Nb and so carbide and Laves phase dissolution, a solution anneal was carried out at 1200 Celsius degrees for 100 hours. This sample treated at 650 Celsius degrees for 100 hours showed M23C6 carbides precipitated at grain boundaries and also at the Laves phase/matrix interfaces. However, upon aging at 750 Celsius degrees for 100 hours the precipitation of M23C6 and M6C takes place at the grain boundary and in the austenitic matrix, thus increasing the material s hardness by 18 percent, when compared to it as solubilized. The increase of the hardness by 12 percent after the heat treatment is related to the precipitation of the carbides in the grain boundaries and dispersed in the matrix resulting from the aging thermal treatments.

Aluminiumschichten werden durch Kaltgasspritzen auf fünf verschiedene poly- und monokristalline keramische Werkstoffe (Al2O3 , AlN, SiC, Si3N4 , MgF2 ) appliziert. Dabei erfolgt eine Variation der Substrattemperatur und der Partikelgröße. Ausgewählte Proben werden einer nachfolgenden Wärmebehandlung unterzogen. Die im Fokus der Arbeit stehende Erforschung der an der Grenzfläche zwischen Aluminium und Keramik wirkenden Haftmechanismen erfolgt sowohl mithilfe einer mechanischen Charakterisierung (Stirnzugversuche) als auch durch verschiedene mikroskopische, spektroskopische und hochauflösende Methoden. Die Bewertung der Untersuchungsergebnisse zeigt, dass im Allgemeinen ein Anstieg der Haftzugfestigkeit mit steigender Substrat- und Wärmebehandlungstemperatur sowie mit zunehmender thermischer Effusivität des Substratwerkstoffs zu verzeichnen ist. Eine vergleichbare Auswirkung hat innerhalb bestimmter Grenzen die Zunahme der Partikelgröße. Mit der Heteroepitaxie wird neben der mechanischen Verklammerung ein weiterer wichtiger Haftmechanismus kaltgasgespritzter metallischer Schichten auf keramischen Substraten identifiziert. Die Ausbildung von quasiadiabatischen Scherbändern und statische Rekristallisationsprozesse wirken dabei als wichtige begleitende Mechanismen. Als Nachweis für heteroepitaktisches Wachstum ist die Existenz von (annähernd) parallelen, senkrecht oder geneigt zur Grenzfläche stehenden Ebenenpaaren, die eine geringe Gitterfehlanpassung aufweisen, zu werten. Der Vergleich mit PVD-Schichten zeigt, dass in Bezug auf die Orientierung von Gitterebenen verschiedene Mechanismen der Heteroepitaxie existieren, die von der atomaren Mobilität des Beschichtungswerkstoffs bestimmt werden.

Aluminiumschichten werden durch Kaltgasspritzen auf fünf verschiedene poly- und monokristalline keramische Werkstoffe (Al2O3 , AlN, SiC, Si3N4 , MgF2 ) appliziert. Dabei erfolgt eine Variation der Substrattemperatur und der Partikelgröße. Ausgewählte Proben werden einer nachfolgenden Wärmebehandlung unterzogen. Die im Fokus der Arbeit stehende Erforschung der an der Grenzfläche zwischen Aluminium und Keramik wirkenden Haftmechanismen erfolgt sowohl mithilfe einer mechanischen Charakterisierung (Stirnzugversuche) als auch durch verschiedene mikroskopische, spektroskopische und hochauflösende Methoden. Die Bewertung der Untersuchungsergebnisse zeigt, dass im Allgemeinen ein Anstieg der Haftzugfestigkeit mit steigender Substrat- und Wärmebehandlungstemperatur sowie mit zunehmender thermischer Effusivität des Substratwerkstoffs zu verzeichnen ist. Eine vergleichbare Auswirkung hat innerhalb bestimmter Grenzen die Zunahme der Partikelgröße. Mit der Heteroepitaxie wird neben der mechanischen Verklammerung ein weiterer wichtiger Haftmechanismus kaltgasgespritzter metallischer Schichten auf keramischen Substraten identifiziert. Die Ausbildung von quasiadiabatischen Scherbändern und statische Rekristallisationsprozesse wirken dabei als wichtige begleitende Mechanismen. Als Nachweis für heteroepitaktisches Wachstum ist die Existenz von (annähernd) parallelen, senkrecht oder geneigt zur Grenzfläche stehenden Ebenenpaaren, die eine geringe Gitterfehlanpassung aufweisen, zu werten. Der Vergleich mit PVD-Schichten zeigt, dass in Bezug auf die Orientierung von Gitterebenen verschiedene Mechanismen der Heteroepitaxie existieren, die von der atomaren Mobilität des Beschichtungswerkstoffs bestimmt werden.