High target utilisation sputtering (HiTUS) is a relatively new thin film deposition technique that generates a high density plasma remotely from the sputter target. This method has been employed firstly to investigate FePt and FePtN thin films for high density data storage media applications and secondly to investigate the production of a GMR/PZT hybrid structure (multi-ferroism) for improvements to magneto-resistive read-sensor devices in hard disk drives and potentially for other novel multi-ferroic applications. The magnetic and structural properties of FePt and FePtN films, prepared by the HiTUS method, on both silicon and glass substrates have been investigated before and after annealing at temperatures in the range of 300 to 800 ◦C. It is shown that during thermal annealing there is a degradation in magnetic properties of the FePt films at around 400 ◦C due to the formation of silicides as the thermal processing promotes the reaction of the film with the substrate. However, in the FePtN samples coercivity values continue to rise with annealing temperatures above 400 ◦C. XRD analysis confirms that silicide formation is suppressed in films containing nitrogen up to 800 ◦C. Using the HiTUS technique, there is evidence that L10 ordering of FePt has occured at annealing temperature of 400 ◦C with in plane and out of plane coercivities of 7180 Oe and 6300 Oe respectively. Finally, it is shown that HiTUS is capable of depositing ultra thin multilayer GMR structures onto a variety of substrates; silicon, glass, flexible kapton film and PZT. It is interesting to find that the GMR ratio obtained on kapton film (14.39 %) is almost as high as that on silicon (16.15 %), with much scope for improve- ment. Multi-ferroic composite films consisting of the GMR multilayer structure [Co(8 °A)/Cu(21 °A)]×20/Co(12 °A) on PZT substrates were fabricated and magneto- electric coupling effects explored. It was found that AC voltages applied across the composite GMR/PZT structure produced a marked decrease in the coercivity of the GMR layer. However, DC voltages did not produce any measurable magnetic effects. Careful investigation revealed that the reduction in coercivity observed during AC measurements was, in fact, due to sample heating effects.

Nanomateriais de fct-FePt, SmCo e Carbeto de Cobalto têm sido bastante estudados para a aplicação em gravação magnética e imãs de elevado desempenho, devido as suas energias magnetocristalinas e coercividades elevadas. Nanopartículas de FePt unidimensionais foram propostas na tentativa de obter melhora no alinhamento magnético das estruturas auto-organizadas. Neste trabalho, a formação de nanobastão e nanofios de FePt foi estudada através da presença de oleilamina e pequena quantidade de monóxido de carbono liberado pelo pentacarbonilferro(0). Estes dois parâmetros foram estudados a fim de analisar a influência no alongamento das nanopartículas e verificou-se que ambos atuam sinergicamente. Foram obtidos tanto nanofios de FePt ramificados de comprimento de 20-100 nm quanto nanobastões de FePt de 20-60 nm de comprimento, ambos com diâmetro de 2-3 nm. Todas as nanopartículas sintetizadas foram obtidas na fase cúbica de face centrada e o processo de tratamento térmico nas temperaturas de 450 oC e 560 oC levou a conversão para a fase tetragonal de face centrada, com custo da sinterização das nanopartículas. Os nanobastões, entretanto, apresentaram maior estabilidade térmica se comparado com o nanofio ramificado, obtendo propriedade ferromagnética na amostra. Alternativamente, têm sido obtidos satisfatoriamente nanobastões de platina para posterior recobrimento com ferro para a formação da liga FePt após o processo de recozimento. Na síntese de SmCo, foi estudada a formação da liga diretamente por via química através do uso de redutores comumente utilizandos em síntese de nanopartículas, porém foi possível observar apenas uma pequena quantidade da liga Sm2Co17 quando se utiliza o boroidreto de sódio. Isto se deve, principalmente, ao alto potencial de redução de Sm3+ e a sua instabilidade química. Entretanto, foram desenvolvidos métodos promissores para a obtenção de nanopartículas de CoO e SmCoO com tamanho e forma controlada. Além destes sistemas, tem sido obtidas diretamente através de síntese química nanopartículas de carbeto de cobalto com coercividade de até 2,3 kOe e magnetização de 45 emu/g, além de desenvolver um método geral de síntese de carbetos de outros metais. / SmCo, fct-FePt and CoC nanomaterials have been studied for application in magnetic recording and permanent magnets due to theirs high coercivity and magnetocrystalline anisotropy. One-dimensional FePt nanoparticles were proposed to improve the magnetic alignment of self-assembled system. In this work, the formation of FePt nanorods and nanowires was studied by using a small amount of carbon monoxide from the precursor pentacarbonyliron(0) and oleylamine. Both parameters of synthesis were studied and was verified that they influence the one-dimensional growth of FePt. In fact, branched FePt nanowires with 20 - 100 nm of length and nanorods with 20 - 60 nm were obtained, both with 2-3 nm of diameters. The FePt nanoparticles were obtained in face centered cubic phase and the transformation to face centered tetragonal phase was carry out in the temperatures of 450 oC and 560 oC, which led the formation of sintered nanoparticles. FePt nanorods have better thermal stability than nanowires according the results obtained. The platinum nanorods covered with iron oxide also were obtained to formation of FePt by thermal treatment. In concern of SmCo syntheses, the formation of SmCo phase directly by chemical synthesis was investigated by using some reduction agent, but was obtained a small amount of smco phase only if the sodium borohydrate was used in the synthesis. This could be occurred due to high reducing potential of Sm3+ and its chemical instability. However, some methods were obtained to obtain CoO and SmCoO nanoparticles with size and shape control. Furthermore, cobalt carbide nanoparticles were well obtained with coercivity of 2,3 kOe and magnetization of 45 emu/g, and a new general method to obtain metals carbides was developed.

The L10 FePt phase belongs to the most promising hard ferromagnetic materials for high density recording media. The main challenges for thin FePt films are: (i) to lower the process temperature for the transition from the soft magnetic A1 to the hard magnetic L10 phase, (ii) to realize c-axes preferential oriented layers independently from the substrate nature and (iii) to control layer morphology supporting the formation of FePt - L10 self-organized isolated nanoislands towards an increase of the signal-to-noise ratio. In this study, dc magnetron sputtered FePt thin films on amorphous substrates were inve-stigated. The work is focalized on the correlation between structural and magnetic properties with respect to the influence of deposition parameters like growth mode (co-sputtering vs. layer – by - layer) and the variation of the deposition gas (Ar, Xe) or pressure (0.3 - 3 Pa). In low-pressure Ar discharges, high energetic particle impacts support vacancies formation during layer growth lowering the phase transition temperature to (320 +/- 20)°C. By reducing the particle kinetic energy in Xe discharges, highly (001) preferential oriented L10 - FePt films were obtained on a-SiO2 after vacuum annealing. L10 - FePt nano-island formation was supported by the introduction of an Ag matrix, or by random ballistic aggregation and atomic self shadowing realized by FePt depositions at very high pressure (3 Pa). The high coercivity (1.5 T) of granular, magnetic isotropic FePt layers, deposited in Ar discharges, was measured with SQUID magnetometer hysteresis loops. For non-granular films with (001) preferential orientation the coercivity decreased (0.6 T) together with an enhancement of the out-of- plane anisotropy. Nanoislands show a coercive field close to the values obtained for granular layers but exhibit an in-plane easy axis due to shape anisotropy effects. An extensive study with different synchrotron X-ray scattering techniques, mainly performed at the ESRF, BM-20 (ROBL-Beamline), pointed out the importance of in-situ investigations to clearly understand the kinetic mechanism of the A1 to L10 transition and ordering and to control FePt nanoclusters evolution.

Nanomateriais de fct-FePt, SmCo e Carbeto de Cobalto têm sido bastante estudados para a aplicação em gravação magnética e imãs de elevado desempenho, devido as suas energias magnetocristalinas e coercividades elevadas. Nanopartículas de FePt unidimensionais foram propostas na tentativa de obter melhora no alinhamento magnético das estruturas auto-organizadas. Neste trabalho, a formação de nanobastão e nanofios de FePt foi estudada através da presença de oleilamina e pequena quantidade de monóxido de carbono liberado pelo pentacarbonilferro(0). Estes dois parâmetros foram estudados a fim de analisar a influência no alongamento das nanopartículas e verificou-se que ambos atuam sinergicamente. Foram obtidos tanto nanofios de FePt ramificados de comprimento de 20-100 nm quanto nanobastões de FePt de 20-60 nm de comprimento, ambos com diâmetro de 2-3 nm. Todas as nanopartículas sintetizadas foram obtidas na fase cúbica de face centrada e o processo de tratamento térmico nas temperaturas de 450 oC e 560 oC levou a conversão para a fase tetragonal de face centrada, com custo da sinterização das nanopartículas. Os nanobastões, entretanto, apresentaram maior estabilidade térmica se comparado com o nanofio ramificado, obtendo propriedade ferromagnética na amostra. Alternativamente, têm sido obtidos satisfatoriamente nanobastões de platina para posterior recobrimento com ferro para a formação da liga FePt após o processo de recozimento. Na síntese de SmCo, foi estudada a formação da liga diretamente por via química através do uso de redutores comumente utilizandos em síntese de nanopartículas, porém foi possível observar apenas uma pequena quantidade da liga Sm2Co17 quando se utiliza o boroidreto de sódio. Isto se deve, principalmente, ao alto potencial de redução de Sm3+ e a sua instabilidade química. Entretanto, foram desenvolvidos métodos promissores para a obtenção de nanopartículas de CoO e SmCoO com tamanho e forma controlada. Além destes sistemas, tem sido obtidas diretamente através de síntese química nanopartículas de carbeto de cobalto com coercividade de até 2,3 kOe e magnetização de 45 emu/g, além de desenvolver um método geral de síntese de carbetos de outros metais. / SmCo, fct-FePt and CoC nanomaterials have been studied for application in magnetic recording and permanent magnets due to theirs high coercivity and magnetocrystalline anisotropy. One-dimensional FePt nanoparticles were proposed to improve the magnetic alignment of self-assembled system. In this work, the formation of FePt nanorods and nanowires was studied by using a small amount of carbon monoxide from the precursor pentacarbonyliron(0) and oleylamine. Both parameters of synthesis were studied and was verified that they influence the one-dimensional growth of FePt. In fact, branched FePt nanowires with 20 - 100 nm of length and nanorods with 20 - 60 nm were obtained, both with 2-3 nm of diameters. The FePt nanoparticles were obtained in face centered cubic phase and the transformation to face centered tetragonal phase was carry out in the temperatures of 450 oC and 560 oC, which led the formation of sintered nanoparticles. FePt nanorods have better thermal stability than nanowires according the results obtained. The platinum nanorods covered with iron oxide also were obtained to formation of FePt by thermal treatment. In concern of SmCo syntheses, the formation of SmCo phase directly by chemical synthesis was investigated by using some reduction agent, but was obtained a small amount of smco phase only if the sodium borohydrate was used in the synthesis. This could be occurred due to high reducing potential of Sm3+ and its chemical instability. However, some methods were obtained to obtain CoO and SmCoO nanoparticles with size and shape control. Furthermore, cobalt carbide nanoparticles were well obtained with coercivity of 2,3 kOe and magnetization of 45 emu/g, and a new general method to obtain metals carbides was developed.

Etude de matériaux nanostructurés préparés par faisceaux d'ions

The L10 FePt phase belongs to the most promising hard ferromagnetic materials for high density recording media. The main challenges for thin FePt films are: (i) to lower the process temperature for the transition from the soft magnetic A1 to the hard magnetic L10 phase, (ii) to realize c-axes preferential oriented layers independently from the substrate nature and (iii) to control layer morphology supporting the formation of FePt - L10 self-organized isolated nanoislands towards an increase of the signal-to-noise ratio. In this study, dc magnetron sputtered FePt thin films on amorphous substrates were inve-stigated. The work is focalized on the correlation between structural and magnetic properties with respect to the influence of deposition parameters like growth mode (co-sputtering vs. layer – by - layer) and the variation of the deposition gas (Ar, Xe) or pressure (0.3 - 3 Pa). In low-pressure Ar discharges, high energetic particle impacts support vacancies formation during layer growth lowering the phase transition temperature to (320 +/- 20)°C. By reducing the particle kinetic energy in Xe discharges, highly (001) preferential oriented L10 - FePt films were obtained on a-SiO2 after vacuum annealing. L10 - FePt nano-island formation was supported by the introduction of an Ag matrix, or by random ballistic aggregation and atomic self shadowing realized by FePt depositions at very high pressure (3 Pa). The high coercivity (1.5 T) of granular, magnetic isotropic FePt layers, deposited in Ar discharges, was measured with SQUID magnetometer hysteresis loops. For non-granular films with (001) preferential orientation the coercivity decreased (0.6 T) together with an enhancement of the out-of- plane anisotropy. Nanoislands show a coercive field close to the values obtained for granular layers but exhibit an in-plane easy axis due to shape anisotropy effects. An extensive study with different synchrotron X-ray scattering techniques, mainly performed at the ESRF, BM-20 (ROBL-Beamline), pointed out the importance of in-situ investigations to clearly understand the kinetic mechanism of the A1 to L10 transition and ordering and to control FePt nanoclusters evolution.

Dank der hohen uniaxialen Kristallanisotropie der L10-geordneten Phase gelten nanopartikuläre FePt+C-Schichten als aussichtsreiche Kandidaten zukünftiger Datenspeichersysteme. Aus diesem Grund werden in der vorliegenden Arbeit in Kooperation mit HGST- A Western Digital Company Prototypen solcher Medien strukturell bis hin zu atomarer Auflösung charakterisiert. Anhand von lokalen Messungen der Gitterparameter der FePt-Partikel wird gezeigt, dass die Partikel dünne, zementitartige Verbindungen an ihrer Oberfläche aufweisen. Zusätzlich werden große Partikel mit kleinem Oberfläche-Volumen-Verhältnis von kontinuierlichen Kohlenstoffschichten umschlossen, was die Deposition weiteren Materials verhindert. Eine Folge davon ist die Entstehung einer zweiten Lage statistisch orientierter Partikel, die sich negativ auf das magnetische Verhalten der FePt-Schicht auswirkt. Weiterhin wird die besondere Bedeutung des eingesetzten Substrats sowie seiner Gitterfehlpassung zur L10-geordneten Einheitszelle nachgewiesen. So lässt sich das Auftreten fehlorientierter ebenso wie das L12-geordneter Kristallite im Fall großer Fehlpassung und einkristalliner Substrate unterdrücken, was andererseits jedoch zu einer stärkeren Verkippung der [001]-Achsen der individuellen FePt-Partikel führt. Abschließend wird mithilfe der Elektronenholographie nachgewiesen, dass die Magnetisierungsrichtungen der FePt-Partikel aufgrund von Anisotropieschwankungen von den [001]-Achsen abweichen können. / Highly textured L10-ordered FePt+C-films are foreseen to become the next generation of magnetic data storage media. Therefore prototypes of such media (provided by HGST- A Western Digital Company) are structurally investigated down to the atomic level by HR-TEM and the observed results are correlated to the magnetic performance of the film. In a first study the occurrence of a strongly disturbed surface layer with a lattice spacing that corresponds to cementite is observed. Furthermore the individual particles are surrounded by a thin carbon layer that suppresses the deposition of further material and leads, therefore, to the formation of a second layer of particles. Without a contact to the seed layer these particles are randomly oriented and degrade the magnetic performance of the media. A further study reveals, that a selection of single-crystalline substrates with appropriate lattice mismatch to the L10-ordered unit cell can be applied to avoid the formation of in-plane oriented and L12-ordered crystals. Unfortunately, the required large mismatch results in a broadening of the texture of the [001]-axes of the individual grains. As electron holography studies reveal, the orientation of the magnetization of the individual grains can differ from the structural [001]-axis due to local fluctuations of the uniaxial anisotropy.

Recentemente, nanopartículas (NP) de FePt de fase tetragonal de face centrada (fct) em sistemas auto-organizados tem sido sintetizados como potenciais candidatos para gravação magnética de ultra-alta densidade (UHMR), devido a sua elevada anisotropia magnetocristalina. Entretanto, o alinhamento magnético de NP esféricas tem sido constantemente um problema, pois os eixos de fácil magnetização das NP permanecem randomicamente orientados nas três direções. Na tentativa de superar os problemas decorrentes da falta de alinhamento magnético, trabalhos recentes sugerem que NP alongadas em sistemas auto-organizados orientados perpendicularmente a superfície do substrato como possível solução para a textura e alinhamento magnético. Até o presente momento, as sínteses de nanobastões (NB) e de nanofios (NF) de FePt reportadas na literatura levam a obtenção de NP na fase cúbica de face centrada (fcc), a qual possui baixa anisotropia magnetocristalina e se mostrou termicamente instável, resultando em NP esferoidais após o processo de recozimento para a transformação da fase fcc para fct. Neste trabalho, NP de Fe55Pt55 com tamanho e composição química controlada e morfologia de nanofios e nanobastões foram sintetizadas através da adequação do método do poliol modificado. Além disso, as condições de sínteses foram ajustadas para a obtenção direta das NP na fase fct. Sistemas auto-organizados de NB orientados longitudinalmente ou perpendicularmente em arranjos hexagonais compactos foram obtidos utilizando, respectivamente, ácido oléico (AO) e oleilamina (Oam) ou hexadecilamina (HDA) como agentes espaçadores. Sistemas de NB orientados perpendicularmente com alinhamento magnético devido à anisotropia de forma combinado com as propriedades magnéticas resultantes da fase parcialmente tetragonal obtida sugerem um forte candidato a aplicação em UHMR com densidade de gravação magnética na ordem de terabits/pol2. / Recently, self-assembled FePt nanoparticles (NP) in face-centered tetragonal phase (fct) has been synthesizes as potential candidates for Ultra-High Magnetic Recording Systems (UHMR) due to high magnetocrystalline anisotropy. However, the magnetic alignment of these self-assembled fct-FePt nanoparticles also has been a constant limiting factor, since the axes of easy magnetization of spherical nanoparticles are presented randomly oriented in three directions. Concerning to avoid these restrictions arising from magnetic alignment, one-dimensional NP perpendicularly oriented on the magnetic medium surface has been reported as a possible solution for texture and magnetic alignment. To date, the reported nanorods (NR) and nanowires (NW) synthesized in the literature showed face centered cubic phase (fcc) which present poor magnetocrystalline anisotropy, instead the fct desirable phase, and were found to be thermally unstable resulting in spheroidal NP after annealing required to phase transformation from fcc to fct. In this work, Fe55Pt45 NP with morphologies varying from nanospheres, NR with different lengths up to NW were synthesized by a modified polyol process. Furthermore, the synthesis conditions were adjusted to obtain FePt NP directly in fct phase. Either longitudinal or perpendicular self-assembled NR systems in a hexagonal compact array were obtained using oleic acid (OA) and oleylamine (Oam) or hexadecylamine (HAD), respectively, as molecular organic spacers. Perpendicularly oriented NR system led to magnetic alignment due to shape anisotropy and combined with the magnetic properties due to partial tetragonal phase suggest a strong future candidate to ultra-high magnetic density recording applications capable to achieve density of Terabits/in2.

The large magneto-crystalline anisotropy energy of the L10 phase has pushed the interest to the FePt nanoparticles to get smallest possible not superparamagnetic particles for magnetic data storage media. The DC magnetron sputtering process, in an inert gas atmosphere and subsequently ejection into high vacuum via differential pumping in addition with a newly constructed light furnace, allows us to have a predeposition annealing of FePt nanoparticles. The advantage compared to wet chemical process route is, that we can prevent the growing of particles on a substrate. In order to determine the experimentally hardly accessible temperature of the particles, the thermal history of the particles is rather calculated from the interaction with the light field along the flight path through the light furnace used for the in-flight annealing. The results obtained for the particle temperature are corroborated by experimental findings on the sintering of agglomerated particles and change in magnetic properties due to heating over the L10 stability temperature. The experiments reveal that the effect of the thermal treatment on both the structural and magnetic properties of the FePt nanoparticles strongly depends on the particles’ crystal structure. The magnetic behavior shows a size depending effective uniaxial magnetic anisotropy constant. This behavior is strongly correlated to the structure of the 5 nm to 8 nm L10 FePt particle.

Nous nous proposons d'étudier l'interaction au niveau de l'interface entre un matériau antiferromagnétique et un ferromagnétique par un ensemble de techniques expérimentales qui utilisent le rayonnement synchrotron. Nous sommes particulièrement intéressés par l'effet de couplage d'échange dans les couches minces magnétiques avec anisotropie hors du plan. Les systèmes que nous avons étudiés sont les couches ordonnées chimiquement, FePt et MnPt sur Pt(001), et Fe/Ag(001), éventuellement couplée à CoO. Notre approche consiste à trouver de surfaces adaptées et d'étudier, pour chaque bicouche, la croissance individuelle de chaque élément, alliage ou oxyde. A travers le contrôle d'un certain nombre des paramètres, comme la structure de la surface, la propreté, le taux et la température de déposition, nous avons obtenus une bonne connaissance du processus de croissance. Les systèmes obtenus ont été étudiés in situ par la diffraction de surfaces et ex situ par l'effet Kerr magnéto-optique, le dichroïsme circulaire magnétique de rayons X et la spectroscopie d'absorption de rayons X. La relation entre le couplage d'échange, qui se manifeste par l'augmentation de la coercivité et par un champ de décalage, et la structure des couches est discutée pour les interfaces MnPt/FePt and CoO/Fe. / Our aim is to study the interaction of antiferromagnetic and ferromagnetic materials with well-defined interface by combining structural, electronic and magnetic techniques using synchrotron light. Our interest is guided by the exchange bias effect in thin ferromagnetic films with perpendicular magnetic anisotropy. The main systems studied in this work were ultra-thin layers of chemically-ordered alloys of FePt and MnPt on Pt(001) and of Fe/Ag(001), eventually coupled to CoO. Our strategy was to find an appropriate surface and, for each coupled bilayer, study the individual growth of each element, alloy or oxide. By controlling a variety of parameters, such as surface structure, cleanliness, deposition rate and temperature, we have got a good understanding of the growth process. The coupled systems obtained were studied in situ by grazing incidence X-ray diffraction and ex situ by magneto-optic Kerr effect, X-ray magnetic circular dichroism and X-ray absorption spectroscopy. The relation between the exchange coupling, which manifests itself by an increase in coercivity and a bias field, and the structural characteristics was discussed for the MnPt/FePt and CoO/Fe interfaces.Keywords: exchange bias, chemically ordered alloy, MnPt, FePt, Fe/Ag(001), surface X-ray diffraction, X-ray absorption, MOKE, synchrotron.