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Made available in DSpace on 2018-08-01T22:29:36Z (GMT). No. of bitstreams: 1 tese_6204_.pdf: 978406 bytes, checksum: 35fdd2440f55189141563a7d979919e3 (MD5) Previous issue date: 2012-10-30 / Usando o método Teoria do Funcional da Densidade (DFT Density Funcional Theory), realizamos um estudo sistemático das propriedades estruturais, eletrônicas e magnéticas do composto Ni2MnGa quando átomos de Ga são substituídos gradativamente por átomos de Sn. Como principais resultados, observamos que nas ligas Heusler Ni2MnGa1-xSnx (0 ≤ x ≤ 1), a substituição de Sn influencia diretamente no volume da célula da fase cúbica L21. Particularmente, observamos que, do ponto de vista de uma única célula convencional, há uma distorção tipo tetragonal da célula unitária devido ao tamanho do átomo de Sn, mas, em média (em todas as direções de ocupações), o que observamos é um aumento linear do parâmetro de rede (ou do volume da célula L21) reduzindo as tensões internas, responsáveis pela transformação de fase martensítica observada na liga Heusler Ni2MnGa. A substituição de Sn favorece, por um lado, um aumento no momento magnético dos átomos de Mn nos sítios 4(a) da fase L21, mas, por outro lado, leva a uma diminuição dos momentos magnéticos dos átomos de Ni. Esses comportamentos dos momentos magnéticos do Ni e do Mn geram uma redução gradual no momento magnético total das ligas Heusler Ni2MnGa1-xSnx em acordo com a observação experimental de que a magnetização da fase L21 decresce com o aumento da concentração de Sn. Levando em conta efeitos de desordens químicas entre os átomos de Mn e Ga (ou Sn) nos compostos puros Ni2MnZ (Z = Ga ou Sn), determinamos a configuração de spins mais provável para os estados antiferromagnéticos (AF-BII). Além disso, demonstramos que na liga Heusler Ni2MnGa os estados antiferromagnéticos são energeticamente mais favoráveis do que no composto Ni2MnSn, explicando talvez a existência da transformação de fase martensítica observada no composto com Ga e ausência no composto com Sn.

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Depuis les cinquante dernières années, les préoccupations d’ordre énergétique sont au cœur de l’actualité. Or, une grande partie de l’énergie produite est rejetée et perdue sous forme de chaleur. Ainsi, la récupération d’énergie par des générateurs thermoélectriques apparaît comme une solution pour le mixe énergétique de demain.La thermoélectricité est la conversion directe et réciproque entre énergie thermique et électrique. Les générateurs thermoélectriques sont constitués d’un assemblage de plots de semi-conducteurs de type n et p. Un gradient de température appliqué entre les deux faces du générateur entraîne une migration des charges du matériau qui génère un courant électrique.Les systèmes thermoélectriques ont attiré l’attention du monde scientifique grâce à leurs avantages comparativement aux moyens de récupération d’énergie plus conventionnels. Ce sont des dispositifs compacts, statiques, silencieux et fiables, qui possèdent une longue durée de vie sans nécessiter de maintenance et impactant peu l’environnement.Pour la récupération d'énergie, le challenge actuel est la perte d’énergie thermique des automobiles et des camions ainsi que la chaleur perdue générée dans les industries de la métallurgie ou du nucléaire, par exemple. Ces deux segments nécessitent l’utilisation de modules thermoélectriques ayant un rendement optimum dans la gamme de température 300-600 °C.La performance d’un matériau thermoélectrique est exprimée par le facteur de mérite ZT, donné par l’expression : ZT=S2σT/к. Un ZT élevé peut être obtenu en optimisant les propriétés de transport du matériau. Le coefficient de Seebeck (S), et la conductivité électrique (σ), doivent être le plus élevé possible, alors que la conductivité thermique (κ) doit rester faible.Afin d’être viable pour une production industrielle, un matériau thermoélectrique doit répondre à un certain nombre de critères. Premièrement, ses composants doivent être non toxiques, peu chers et abondants. Ensuite, la voie de fabrication doit être robuste et compatible avec une production en grand volume. Enfin, les matériaux élaborés doivent posséder des propriétés thermoélectriques satisfaisantes dans la gamme de température de l’application visée. Ils doivent également être stables selon les environnements liés à l’application et avoir une bonne tenue mécanique.Les matériaux de type half-Heusler apparaissent comme prometteurs pour la génération de puissance thermoélectrique dans la gamme de température 300-600 °C. En effet, ils possèdent un coefficient de Seebeck et une conductivité électrique élevés. Cependant, leur conductivité thermique est relativement haute comparée aux autres matériaux thermoélectriques.Ce travail de thèse s’est donc focalisé sur l’étude des relations microstructure-propriétés thermoélectriques de matériaux half-Heusler de composition générique (Hf,Zr,Ti)Ni(Sb,Sn) et (Hf,Zr,Ti)Co(Sb,Sn) et de leurs possibles variantes. Les compositions testées ont toutes été synthétisées de la même manière : une fusion par induction permet d’obtenir des lingots qui sont ensuite réduits en poudre par broyage, celle-ci est ensuite frittée par frittage SPS (spark plasma sintering) afin d’obtenir une pastille dense et polycristalline. Les propriétés thermoélectriques et la microstructure de ces échantillons sont ensuite caractérisées et discutées.Un des objectifs de ce travail de thèse était également de réduire coût au kilogramme de ces matériaux half-Heusler, sans impacter de manière négative leurs propriétés thermoélectriques. Nous y sommes parvenus, d’une part, en réduisant la concentration en hafnium incorporé dans les formulations, et d’autre part, en simplifiant le processus de fabrication. En effet, nous avons observé qu’une synthèse sous air des poudres half-Heusler permettait la formation in-situ de précipités d’oxydes, agissant comme source de diffusion des phonons et donc favorisant la diminution de la conductivité thermique. / The search for alternative energy technologies has taken an accelerated pace in the last 50 years due to an increasing concern about climate change. In this quest to find new energy sources, it is interesting to point out that a lot of energy is wasted as heat released into the environment. As a potential solution, thermoelectric power generators could be used to transform the waste heat into useful electrical energy.Thermoelectric generators are converting directly heat into electricity and vice versa. They consist in an assembly of n and p-type semiconducting legs connected electrically in series and thermally in parallel. An applied temperature difference between n and p-sides drives charge carriers displacement in the material from the hot side to the cold one. Therefore a current flow is generated through the circuit. Thermoelectric devices have attracted interest because of their advantages over conventional power generator: no moving part, no liquid involved, reliability, noiseless, long life time without maintenance and also low environmental impact.Over the last several decades, the increased energy demand combined to the environmental concerns, leads to another potential use of thermoelectricity as an alternative energy source by recovering the huge amount of heat lost in industrial or domestic applications. Presently, wasted-heat recovery in cars and trucks and wasted-heat in industry (metallurgy/nuclear…) are becoming a major concern. Both recovery problematics may be addressed using thermoelectric devices efficient in the 300-500 °C temperature range.Numerous thermoelectric materials couples have been investigated and developed over the last 20 years. Most of the already known class of thermoelectric materials have been improved and new classes have been developed, leading to a significant improvement of ZT values being optimum in different temperature ranges. In order to be efficient and to be viable for large scale manufacturing of power generators, a thermoelectric material has to fulfill several requirements. First, the raw materials chosen have to be non-toxic, cheap and abundant. Secondly, the manufacturing process should be robust and compatible to the production of a high volume of materials per day. Last but not least, the elaborated materials have to exhibit acceptable thermoelectric properties in the temperature range of interest for the final application. They must also have a long-term thermal stability in different kinds of environments and good mechanical properties.Half-Heusler materials have been shown to be good candidates in the 300 to 600 °C temperature range. Indeed, due to their semiconductor like band structure, they exhibit a large Seebeck coefficient and high electrical conductivity. Unfortunately, half-Heusler’s thermal conductivity is rather high when compared to other thermoelectric materials. Therefore, the main research efforts on half-Heusler formulations, devoted to be used for thermoelectric applications, have been focused on decreasing the thermal conductivity, while keeping a good electronic transport.Accordingly the main objective of the PhD thesis was to investigate the link between the microstructure and the thermoelectric properties of n and p-type half-Heusler alloys from the generic compositions MNiSn (n-type) and MCoSb (p-type), with M being Ti, Zr and Hf. All investigated compositions have been elaborated by a three step process: (i) ingots synthesis using cold crucible levitation melting, (ii) subsequent ball milling to obtain a calibrated powder and (iii) sintering by spark plasma sintering to obtain dense polycrystalline pellets that are characterized regarding their microstructure and thermoelectric properties from room temperature to 500-600 °C.

Corrélation entre les propriétés structurales et magnétiques des couches minces et nanostructures de Co₂FeAl Co₂FeAl (CFA) est un alliage Heusler très attractif pour les applications en spintronique. Ses propriétés magnétiques et structurales dépendent fortement des orientations cristallines et de la qualité des interfaces. Ce travail de thèse a porté sur les effets de l'épaisseur (dCFA), du type de substrat (MgO, Si et SrTiO₃ (STO)) ainsi que de la température de recuit (Ta) sur ces propriétés. Les analyses structurales ont montré que les couches déposées sur les substrats MgO et STO croissent avec épitaxie contrairement au cas de Si. Lorsque dCFA et Ta diminuent, l’ordre chimique évolue de la phase moyennement ordonnée B2 vers la phase plus désordonnée A2, quel que soit le substrat. Les mesures de résonance ferromagnétique (FMR) révèlent que les couches sur MgO et STO présentent une superposition d'anisotropies planaires uniaxiale et d’ordre 4, alors que seule une faible anisotropie uniaxiale est présente pour les couches CFA déposées sur Si. Cette anisotropie d’ordre 4 a été directement reliée à la structure cristalline de ces couches. Les mesures FMR et de diffusion Brillouin de la lumière ont mis en évidence la présence d’une grande anisotropie uniaxiale perpendiculaire négative, liée à l’interface CFA/MgO, qui augmente avec 1/dCFA et avec Ta. Les mécanismes de relaxation de l’aimantation ont été soigneusement étudiés et des coefficients d'amortissement de Gilbert de 0.0011 ont été mesurés, validant ainsi l’intérêt porté à ces alliages pour les applications dans les dispositifs à base de transfert de spin. Enfin, l’étude de réseaux de lignes submicroniques à base des couches minces de CFA a révélé une quantification des ondes de spin liée à la largeur finie des lignes. / ACorrelation between structural and magnetic properties of Co₂FeAl thin films and nanostructures Co₂FeAl (CFA) is a very attractive Heusler alloy for spintronic applications. Their structural and magnetic properties depend strongly on the crystalline orientations and the interfaces quality. Therefore, the aim of this thesis is the study effects of the film thickness (dCFA), the substrate (MgO, Si and SrTiO₃(STO)) as well as the annealing temperature (Ta) on these properties. The structural analysis revealed a good epitaxial growth for films deposited on MgO and STO, in contrast to the Si substrate. The chemical order varies from the partially ordered B2 phase to the disordered A2 phase as dCFA or Ta decreases, regardless of the substrate. The ferromagnetic resonance (FMR) measurements show the superposition of a uniaxial and fourfold anisotropies for films grown on MgO and STO and only a weak uniaxial anisotropy for the samples grown on Si. The fourfold anisotropy is directly correlated to the crystal structure of the samples. The FMR and Brillouin light scattering measurements reveal the presence of a large negative perpendicular uniaxial anisotropy induced by CFA/MgO interface, which increases with 1/dCFA and with Ta. The relaxation mechanisms have carefully been studied and Gilbert damping coefficients of 0.0011 have been measured making CFA as a potential candidate for spin transfer torque-based devices. Finally, the study of submicron arrays of stripe obtained by patterning of the continuous CFA films reveals a spin waves quantization due to the finite stripes width.

The resonance frequency and the damping constant are interesting parametersrelated to the ferromagnetic spin resonance phenomenon. In this study theseparameters have been investigated for a number of Heusler multilayer film samplesusing a vector network analyzer ferromagnetic resonance setup. The complexsusceptibility of the samples is extracted from the transmittance scattering parameterS12 measured by the network vector analyzer. The ferromagnetic resonance ismirrored by a maximum in the imaginary part of the complex susceptibility. Theagreement between the theoretically calculated resonance frequency and theresonance frequency measured varied between samples. These differences originatefrom several sources, one of them is, the uncertainty in the internal magnetic field.This is due to irregularities and repeated interfaces between each layer in the Heuslersamples.

Ultraviolet photoemission spectroscopy has been employed to investigate the electronic density of states of Heusler and Cu3Au-type intermetallic compounds. Cooper minima and resonant photoemission effects have been utilised to determine the contribution of the constituent elements to the valence band spectra. For the Mn-based Heusler alloys Co2MnSn, Cu2MnAl and Pd2MnSn, the Mn 3d-derived states disperse across the full width of the valence band.

Spintronics or spin-electronics attempt to utilize the electronic spin degree of freedom to make advanced materials and devices for the future. Heusler materials are considered very promising for spintronics applications as many highly spin-polarized materials potentially exist in this family. To accelerate materials discovery and development, The Materials Genome Initiative (https://www.mgi.gov/) was undertaken in 2011 to promote theory-driven search of new materials. In this thesis work, we outline our effort to develop several new materials that are predicted to be 100% spin-polarized (half-metallic) and thermodynamically stable by theory. In particular, two Mn-based Heusler families were investigated: Mn2CoZ (Z= Ga, Sb, Ge) and Mn2FeZ (Z=Si,Ge), where the latter is potentially a new Heusler family. These materials were synthesized using the arc-melting technique and their crystal structure was investigated using the X-ray diffraction (XRD) method before and after appropriate annealing of the samples. Preliminary magnetometry measurements are also reported. We first developed a heat-treatment procedure that could be applied to all the Mn-based compounds mentioned above. Mn2CoGa was successfully stabilized in the cubic inverse-Heusler phase with a=5.869 Å and magnetic moment of 2.007 /fu. This is in good agreement with prior literature reports [1]. However, cubic phases of Mn2CoSb and Mn2CoGe could not be stabilized within the annealing temperature range that is accessible in our lab. We successfully synthesized a cubic Mn2FeSi phase using an annealing procedure similar to Mn2CoGa. The measured cubic lattice parameter of Mn2FeSi was 5.682 Å. This is the first experimental report of this material to the best of our knowledge. Detailed analysis of relative intensities of different X-ray peaks revealed that the structure is most likely in an inverse Heusler phase, in agreement with theory. However, a substantial atomic-level disorder was also uncovered from XRD analysis that requires further investigation to understand its effect on its magnetism and half-metallicity. Mn2FeGe showed the existence of non-cubic phases that substantially weakened at high annealing temperatures.

Made available in DSpace on 2016-08-29T15:35:49Z (GMT). No. of bitstreams: 1 tese_3661_.pdf: 5418768 bytes, checksum: 2d9a9bb7eaa948706569d9d0c6d5f0ef (MD5) Previous issue date: 2009-05-29 / Resultados reportados na literatura mostram que uma transição de fase martensítica (TFM) pode ser ativada na liga Heusler Ni50Mn25Sn25 quando há um excesso de Mn nos sítios de Sn1 e que a substituição parcial de Fe na liga martensítica Ni50Mn36Sn14 produz redução da temperatura da TFM, com desaparecimento desta transição de fase estrutural para concentrações de Fe superiores a 10% atômico. 19 Neste trabalho preparamos, por fusão a arco voltaico, duas séries distintas de amostras onde estudamos (i) a localização e o magnetismo dos átomos de 57Fe e também a origem da redução da temperatura da TFM reportada na literatura quando ocorre substituição parcial de átomos de Mn por Fe na liga Heusler martensítica Ni50Mn36Sn14 (Série-A) e (ii) a possibilidade de ocorrência da TFM na liga Heusler Ni50Mn25Sn25 quando átomos de Sn são substituídos por Cr ou por Fe (Série-B). Caracterizamos as amostras das Séries-A e B por meio de medidas de magnetização, microscopia eletrônica de varredura e espectroscopia Mössbauer do 57Fe. Mostramos que existe um limite de solubilidade nas substituições parciais tanto de Mn por 57Fe (Série-A) como de Sn por Cr ou por Fe (Série-B), sendo que a solubilidade é mais limitada na Série-B, já que em todo o intervalo de composição estudado (até ~ 3% atômico) observamos segregações de fases em todas as amostras. Esta segregação de fases explica a ausência da TFM, pois as fases segregadas estão em regiões de concentração de Mn fora daquela onde é observada a TFM nas ligas Ni-Mn-Sn. Além disso, na Série-B, cristais de Cr, com formatos poligonais e tamanhos de aproximadamente 2 a 5, são produzidos durante a segregação das fases em todas as amostras com Cr. O desaparecimento da TFM na Série-A está correlacionado com a ausência das interações antiferromagnéticas de curto alcance, conforme reportado na literatura, mas também com o efeito de segregação de fases discutido. A solubilidade estimada na Série-A é de aproximadamente 2% atômico de Fe, nos sítios de Mn. Constatamos que estes átomos de 57Fe na fase L21 das amostras da Série-A são magnéticos e têm momento .

Made available in DSpace on 2018-08-01T21:59:49Z (GMT). No. of bitstreams: 1 tese_10751_Tese_Jhone Ramsay - PPGFis.pdf: 11993441 bytes, checksum: 587e0b722c1833d4e5be8aba827a929d (MD5) Previous issue date: 2017-02-23 / Neste trabalho, nós investigamos as propriedades estruturais e magnéticas da liga Heusler 𝐹𝑒2𝑀𝑛𝐺𝑎, preparada por fusão a arco voltaico, que posteriormente foi submetida a esforços mecânicos para fabricação na forma de pó e fita, onde a mudanças nas propriedades devido à estes esforços também foram investigadas (com e sem tratamento térmico). As técnicas de análise utilizadas foram difratometria de raios-X, medidas de magnetização 𝐷𝐶 em função do campo aplicado [𝑀(𝐻)] e da temperatura [𝑀(𝑇)], e também a técnica local de Espectroscopia Mössbauer com campo externo nulo. A caracterização estrutural indica que a liga 𝐹𝑒2𝑀𝑛𝐺𝑎 se estabiliza na estrutura 𝐿12, e não há indícios de transformação de fase martensítica na faixa de temperatura estudada. Do ponto de vista magnético, a análise dos resultados sugerem que, enquanto os momentos magnéticos dos átomos de 𝑀𝑛 se ordenam acima de 300 𝐾, os momentos magnéticos dos átomos de 𝐹𝑒 se ordenam abaixo de 300 𝐾, se acoplando de forma antiparalela com a sub-rede de 𝑀𝑛, tornando o magnetismo em baixas temperaturas mais complexo. O esforço mecânico sobre a liga induz redução do tamanho de grão e aumento das tensões internas na estrutura 𝐿12, favorecendo desordens químicas. Os resultados mostram que a liga 𝐹𝑒2𝑀𝑛𝐺𝑎 tem suas propriedades magnéticas muito sensíveis aos processos de fabricação e ao grau das desordens atômicas na estrutura 𝐿12. Os resultados mostram que os esforços mecânicos favorecem estas desordens. As desordens químicas favorecem competições entre interações antiferromagnéticas e ferromagnéticas, que consequentemente leva a um estado magnético frustrado quando as sub-redes de 𝐹𝑒 e 𝑀𝑛 se ordenam magneticamente. Devido as desordens químicas intrinsicamente encontradas na fabricação das amostras e o aumento no grau dessas desordens quando as amostras são submetidas a esforços mecânicos, mostramos que: (𝑖) a transição metamagnética do acoplamento antiparalelo dos átomos de 𝐹𝑒 e 𝑀𝑛 para um estado magnético não colinear quando a intensidade do campo magnético é aumentada (curva em forma de 𝑆) e (𝑖𝑖) a característica do loop em forma de vespa (wasp-waisted magnetic loop) é consequência da frustração das interações magnéticas entre os átomos de 𝐹𝑒 e 𝑀𝑛 vizinhos. Nós também mostramos que mesmo em semelhantes condições experimentais de tratamento térmico, as desordens químicas na liga preparada, na fita e no pó são diferentes, produzindo propriedades magnéticas distintas no produto final. Deslocamento vertical (eixo de magnetização) e horizontal (eixo do campo magnético) são observados nas curvas de magnetização em função do campo aplicado (𝑀(𝐻)) no processo field cooling, e esse efeito pode estar associado com um estado magneticamente frustrado que ocorre devido a interação de duas sub-redes magnéticas.