Ce travail s’inscrit dans le cadre général de la recherche de nouveaux matériaux nanocomposites durs/doux dont le domaine d’application concerne les aimants permanents performants. Ces nanocomposites présentent des propriétés magnétiques intéressantes grâce à leur forte rémanence combinée à une grande coercivité. Ceci permet d’augmenter considérablement l’énergie spécifique de l’aimant. Dans ce contexte, nous avons élaboré et étudié de nouveaux nanocomposites à base de phases dures hors équilibre Sm(Fe,Si)9C et Sm(Fe,Ga)9C et des phases douces _-Fe et FeCo. Pour les nanocomposites intrinsèques, SmFeSiC /_-FeFe, la formation de la phase douce est contrôléeà partir des conditions d’élaboration de la phase dure en agissant sur l’excès de samarium. La microscopie électronique à transmission montre des nanograins de forme pseudo-sphérique et de diamètre moyen de l’ordre de 20 nm. La valeur maximale du produit d’énergie spécifique (BH) max est obtenue pour l’échantillon avec environ 15% de _-Fe, elle est égale à 11.7 MGOe (93.6kJ/m3). Pour les nanocomposites extrinsèques, les phases dures (Sm-Fe-Si-C) et douces (FeCo) ont été élaborées séparément puis mélangées dans des conditions appropriées. Un record d’aimantation à saturation de 235 emu/g a été enregistré pour la composition Fe55Co45 élaboré par la méthode polyol. Les nanocomposites SmFeSiC /FeCo et SmFeGaC/FeCo, ont révélé une amélioration de l’aimantation avec le taux de la phase douce mais avec une diminution du champ coercitif. L’énergie spécifique atteint des valeurs maximales de l’ordre de 13.5 MGOe (108 m3) et 12.4 MGOe(99.2 kJ/m3), pour les échantillons SmFeGaC/20%FeCo et SmFeSiC/10%FeCo, respectivement. D’autre part, nous avons étudié la structure locale des alliages Pr2(Co,Fe)7, un autre cas de phase dure, par spectroscopie EXAFS et nous avons montré que le site préférentiel du Fe dans ces composés est le site 12k / This work focuses on the synthesis and the study of new hard / soft nanocomposites. These nanocomposites exhibit interesting magnetic properties thanks to their high remanence combined with a high coercivity Hc. This allows a huge increase of the specific energy of the magnet. In this context, we have developed and studied new nanocomposites based on the out of equilibrium hard phases Sm (Fe, Si) 9C and Sm (Fe, Ga) 9C and soft phases _-Fe and FeCo. For the intrinsic nanocomposites SmFeSiC /_-Fe, we have shown by transmission electron microscopy, an average grain size of about 20 nm for the studied samples. The maximum value of (BH) max is obtained for the nanocomposite with about 15 % of _-Fe, it is equal to 11.7 MGOe (93.6 kJ/m3). For the extrinsic nanocomposites SmFeSiC/FeCo et SmFeGaC/FeCo, we have shown that the energy product (BH) max reaches a maximum and then decreases with increasing the rate of FeCo. The maximum values obtained are about 13.5 MGOe (108 kJ/m3) and 12.4 MGOe (99.2 kJ/m3) for SmFeGaC / 20% FeCo and SmFeSiC/ 10% FeCo samples, respectively. Finally, we have investigated the local structure of Pr2 (Co,Fe) 7 alloys by EXAFS spectroscopy and we have shown that the preferential site Fe in these compounds is the 12k site

The X-band FMR has been employed to investigate the angular variation of resonance Fields of DC sputtered Co-Cr Films with different substrate temperatures. This angular variation has been Fitted with the classical uniaxial anisotropy crystal model and yields the values of 2K₁/M-4πM=-4∼-7 KOe, 4K₂ =-0.8∼0.8 KOe and g-factor = 2.3~2.8. The FMR measurments of the first anisotropy constant are quite different from the counterparts measured with VSM. This discrepancy is interpreted as a result of the formation of two ferromagnetic phases. With this simple model, the substrate temperature dependence of First anisotropy is explained and it is predicted that a lower substrate temperature will improve the Co-Cr Films for their potential application in perpendicular magnetic recording devices. The angular dependence of the FMR linewidth is discussed. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

ESR results for DEM(TCNQ)₂ and for MEM(TCNQ)₂ are presented as examples of TCNQ salts with and without level crossing effects. In the case of DEM(TCNQ)₂ we are performing ESR on a system with two types of spins. The latter are due to the two kinds of stacks of the acceptor TCNQ molecules in DEM(TCNQ)₂. The level crossing occurs when the g value of these two kinds of electrons are the same. This is compared to the case of MEM(TCNQ)₂ where there is only one kind of TCNQ stack and consequently no level crossing effect. It is found that g values and susceptibilities of the ESR spectra for DEM(TCNQ)₂ can be fitted very well to an interaction between the stacks of the form J ∑i,j,Si,Sj; with J > 0. This gives an antiferromagnetic coupling between every spin on one type of stack with every spin on the other type of stack. This type of interaction is also in qualitative agreement with the published results for HMM(TCNQ)₂. The experimental results in DEM(TCNQ)₂ and MEM(TCNQ)₂ also show that there are small but significant differences in the g tensors when the temperature or the crystalline environment are changed, and consequently the g tensor in these compounds does not depend only on the orientation of TCNQ molecule in the magnetic field as previously assumed. These differences in g are typically less than 2 x 10⁻⁴. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

Ph.D. / Spin—density—wave (SDW) effects are investigated in four dilute Cr—Ir alloy single crystals. The Ir concentrations in these crystals were chosen to cover all four magnetic phases existing on the magnetic phase diagram of the Cr—Ir system. Thermal expansion, electrical resistivity, elastic constants and ultrasonic attenuation are studied as functions of temperature and alloy concentration. The elastic constants are also studied as a function of applied hydrostatic pressure. The SDW effects in the Cr—Ir system are compared with those in other Cr alloys. The full temperature—concentration and temperature—pressure magnetic phase diagrams of the Cr—Ir system are determined. Existing theories are used to discuss the observations. The following major observations are made: Magnetoelastic interactions in Cr—Ir alloys are very large, resulting in well defined magnetic anomalies in the elastic constants and thermal expansion at all magnetic phase transition temperatures. Elastic constant measurements as a function of temperature appear to be a very sensitive tool to determine the magnetic phase transition temperatures of the Cr—Ir alloy system. Below TN of Cr—Ir alloys, where TN is the transition temperature from the incommensurate transverse spin—density-wave (TISDW) magnetic phase to the paramagnetic phase, elastic constant and thermal expansion measurements show the existence of hysteresis effects, which are probably due to a redistribution of antiferromagnetic domains. These hysteresis effects are the first evidence of such effects in Cr alloys. Spin fluctuation effects are shown to exist to temperatures well above the Neel temperatures of the Cr—Ir alloys. Analyses of the data for electrical resistivity measurements of Cr—Ir alloys show that the fraction of the electron and hole Fermi surface sheets that nests is roughly the same in the ISDW and CSDW (commensurate spin—density—wave) phases, making the resistivity anomaly near the ISDW—CSDW transition temperature very small or non—existing. Measurements of elastic constants as a function of applied pressure at different constant temperatures are shown to be a very powerful tool for an investigation of the interaction of the SDW with the acoustic phonons in dilute Cr—Ir alloys. It is found that the SDW in Cr—Ir alloys couples mainly with the longitudinal—mode acoustic phonons. Coupling to the shear—mode phonons is relatively small. Empirical correspondence is found between the temperature—concentration and temperature— pressure magnetic phase diagrams of the dilute Cr—Ir alloy system by using a linear scaling between pressure and concentration. Existing thermodynamic models fit the experimental results for the elastic constants and magnetovolume of the Cr—Ir alloys well. The main features of the temperature—concentration and temperature—pressure magnetic phase diagrams of the Cr—Ir alloy system are resonably well predicted by existing microscopic theories.

M.Sc. / Spin-density-wave (SDW) effects are investigated in a Cr + 1.9 at.% Fe alloy single crystal, where the Fe concentration lies just below the triple point found in the temperatureconcentration magnetic phase diagram of the Cr-Fe alloy system. The crystal is expected to undergo a commensurate (C) SDW to an incommensurate (I) SDW phase transition at a temperature Tc, and an ISDW-P (paramagnetic) phase transition at the Neel temperature, TN. The magnetoelastic properties and the anharmonic behaviour of this crystal were studied with the aid of velocity of sound measurements as function of temperature and pressure. Electrical transport measurements were carried out using the standard fourprobe method. In order to determine the various phases present in the crystal a preliminary neutron-diffraction study was also done. Fe belongs to the group-8 magnetic transition metals, possessing localized magnetic moments. The SDW effects in the Cr + 1.9 at.% Fe crystal are therefore compared with that of Cr-Ru and Cr-Ir alloys, as Ru and Ir also belong to the group-8 transition metals, however these impurities are nonmagnetic. The following observations were made: The longitudinal mode elastic constants and the bulk modulus show a prominent change in the slope at Tc, and a sharp, deep minimum at TN. For the c' shear propagation mode peaks were seen at Tcl as well as TN and the c4 4 propagation mode showed no anomalies at either phase transition temperatures. The longitudinal ultrasonic wave velocities for the cL propagation mode were measured as a function of temperature at different constant pressures. TN obtained from these measurements varies linearly with increasing pressure. High-pressure ultrasonic wave velocity measurements were taken at various constant temperatures in the range of 230 K to 350 K for the C L, c44 and c' propagation modes of the Cr + 1.9 at.% Fe alloy single crystal. This was used to determine the pressure derivatives of the second order adiabatic elastic constants (acu /ap). The pressure derivatives of the second order adiabatic elastic constant are shown to be a very powerful tool for investigating the interaction of the SDW with the acoustic phonons in the Cr-Fe crystal. II The long-wavelength acoustic-mode Gitmeisen parameters, calculated from (acu/ap), showed that the SDW in the Cr + 1.9 at.% Fe alloy single crystal couples mainly with the longitudinal acoustic phonons. Coupling to the shear modes is relatively small. The mean acoustic-mode GrOneisen parameter shows a small maximum between Tc, and TN. It increases on heating through TN, reaching a large maximum value above TN, and then decreases with further increase in the temperature. The electrical resistivity was measured_in the temperature region of 4 Kt() 900 K in order to obtain the nonmagnetic component of the resistivity at all temperatures. Only the Neel phase transition was observed in these measurements with no resistivity anomalies taking place at -Va. The experimental results on the resisitivity were analyzed according the model of Chui et al.. The magnetic component of the electrical resistivity was calculated from the model with and without the inclusion of the effects of resonant impurity scattering of the conduction electrons by the local impurity states lying in the SDW energy gap. The magnetic contributions were found to be appreciable above TN, even up to temperatures as high as 1.5TN. The neutron-diffraction experiments show that the Cr + 1.9 at.% Fe crystal remains in the ISDW phase at all temperatures below TN. This is an unexpected result as a CSDW-ISDW phase transition is expected at To, the temperature of the observed anomaly in elastic constant and thermal expansion measurements on the crystal

Orientador: Marcelo Knobel / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-04T01:56:42Z (GMT). No. of bitstreams: 1 Brandl_AnaLucia_D.pdf: 5290468 bytes, checksum: 32290a7675f89cf9c2a2ea53be70c6fb (MD5) Previous issue date: 2004 / Resumo: Sistemas magnéticos granulares são constituídos de pequenas partículas magnéticas imersas numa matriz não magnética. Essas partículas têm formas e tamanhos variados, eixos de anisotropia variados e orientados aleatoriamente e, dependendo do tipo de matriz (isolante ou condutora) e da concentração do material magnético, diferentes tipos de interações magnéticas podem estar presentes. Esses materiais apresentam diversas propriedades físicas interessantes, como magneto-resistência gigante e efeito Hall gigante. Devido à complexidade desses sistemas, a sua magnetização só pode ser calculada analiticamente em dois casos limites: quando a temperatura é zero (modelo Stoner-Wohlfarth) ou quando a temperatura é alta (modelo de Langevin). Embora o modelo de Langevin seja aplicado com bastante sucesso para temperaturas acima da temperatura de bloqueio média (TB) do sistema, mostramos nesse trabalho que os resultados podem ser enganosos, fornecendo parâmetros estruturais muito diferentes dos reais. Essas discrepâncias podem ser atribuídas a efeitos de interações magnéticas e a efeitos de anisotropia, ambos desconsiderados no formalismo de Langevin. Os principais resultados experimentais apresentados nesta dissertação foram obtidos de um conjunto de filmes granulares do tipo metal-isolante, com partículas nanocristalinas de Co imersas numa matriz amorfa de SiO2, fabricados por evaporação catódica. A caracterização magnética foi realizada através de medidas de magnetização em função do campo, susceptibilidade resfriada com e sem campo magnético aplicado e magnetização termo-remanente. A caracterizção estrutural foi realizada através de medidas de microscopia de transmissão de elétrons, difração de raio-x e espalhamento de raio-x a baixo ângulo / Abstract: Granular magnetic systems are formed by magnetic grains whose size is of the order of a few nanometers, embedded in a non-magnetic (insulating or metallic) matrix. These ultrafine particle systems present size, shape, and anisotropy distributions, besides randomly orientated easy directions. Magnetic interactions always exist, being stronger or weaker according to the volume concentration and the matrix type. These systems have shown interesting magnetotransport properties, as giant magnetoresistance and giant Hall effect. Owing to the inherent complexity of the nanostructure, the magnetization can be analytically calculated only in two limiting cases: when T = 0 (Stoner-Wohlfarth model) or for high temperatures (Langevin model). The Langevin model presents very good results when applied at temperatures higher than the mean blocking temperature (TB) of the system. However this adequacy can be just apparent: the obtained structural parameters are very different from the real ones, as we show in this work. These discrepancies can be attributed to magnetic interactions andanisotropy effects, both unconsidered in the Langevin formalism. The main results presented in this thesis were obtained from a set of metal-insulator granular films, composed of Co nanoparticles immersed in an amorphous SiO2 matrix. The films were produced by magnetron co-sputtering. The magnetic characterization was perfomed with magnetization loops, zero-field cooled and field cooled susceptibilities, and thermoremanent magnetization. The microstructural characterization was done by transmission electron microscopy, x-ray diffraction, and small angle x-ray scattering / Doutorado / Física / Doutor em Ciências

1.1\xMagnetic nanoparticles (NPs) with sizes ranging from 2 to 20 nm in diameter represent an important class of artificial nanostructured materials, since the NP size is comparable to the size of a magnetic domain. They have potential applications in data storage, catalysis, permanent magnetic nanocomposites, and biomedicine.;1.2\xTo begin with, a brief overview on the background of Fe-based bimetallic NPs and their applications for data-storage and catalysis was presented in Chapter 1.;1.3\xIn Chapter 2, L10-ordered FePt NPs with high coercivity were directly prepared from a novel bimetallic acetylenic alternating copolymer P3 by a one-step pyrolysis method without post-thermal annealing. The chemical ordering, morphology and magnetic properties were studied. Magnetic measurements showed that a record coercivity of 3.6 T (1 T = 10 kOe) was obtained in FePt NPs. By comparison of the resultant FePt NPs synthesized under Ar and Ar/H2, the characterization proved that the incorporation of H2 would affect the nucleation and promote the growth of FePt NPs. The L10 FePt NPs were also successfully patterned on Si substrate by nanoimprinting lihthography (NIL). The highly ordered ferromagnetic arrays on a desired substrate for bit-patterned media (BPM) were studied and promised bright prospects for the progress of data-storage.;1.4\xFuthermore, we also reported a new FePt-containing metallopolymer P4 as the single-source precursor for metal alloy NPs synthesis, where the metal fractions were on the side chain and the ratio could be easily controlled. This polymer was synthesized from random copolymer poly(styrene-4-ethynylstyrene) PES-PS and bimetallic precursor TPy-FePt ([Pt(4-ferrocenyl-(NN̂N̂))Cl]Cl) by Sonogashira coupling reaction. After pyrolysis of P4, the stoichiometry of Fe and Pt atoms in the synthesized NPs (NPs) is nearly close to 1:1, which is more precise than using TPy-FePt as precursor. Polymer P4 was also more favorable for patterning by high throughout NIL as compared to TPy-FePt. Ferromagnetic nanolines, potentially as bit-patterned magnetic recording media, were successfully fabricated from P4 and fully characterized.;1.6\xBesides, a bimetallic complex TPy-FePd-2 was prepared and used as a single-source precursor to synthesize ferromagnetic FePd NPs by one-pot pyrolysis. The resultant FePd NPs have a mean size of 19.8 nm and show the coercivity of 1.02 kOe. In addition, the functional group (-NCMe) in TPy-FePd-2 was easily substituted by a pyridyl group. A random copolymer PS-P4VP was used to coordinate with TPy-FePd-2, and the as-synthesized polymer made the metal fraction disperse evenly along the flexible chain. Fabrication of FePd NPs from the polymers was also investigated, and the size could be easily controlled by tuning the metal fraction in polymer. FePd NPs with the mean size of 10.9, 14.2 and 17.9 nm were prepared from the metallopolymer with 5 wt%, 10 wt% and 20wt% of metal fractions, respectively.;1.7\xIn Chapter 4, molybdenum disulfide (MoS2) monolayers decorated with ferromagnetic FeCo NPs on the edges were synthesized through a one-step pyrolysis of precursor molecules in an argon atmosphere. The FeCo precursor was spin coated on the MoS2 monolayer grown on Si/SiO2 substrate. Highly-ordered body-centered cubic (bcc) FeCo NPs were revealed under optimized pyrolysis conditions, possessing coercivity up to 1000 Oe at room temperature. The FeCo NPs were well-positioned along the edge sites of MoS2 monolayers. The vibration modes of Mo and S atoms were confined after FeCo NPs decoration, as characterized by Raman shift spectroscopy. These MoS2 monolayers decorated with ferromagnetic FeCo NPs can be used for novel catalytic materials with magnetic recycling capabilities. The sizes of NPs grown on MoS2 monolayers are more uniform than from other preparation routines. Finally, the optimized pyrolysis temperature and conditions provide receipts for decorating related noble catalytic materials.;1.8\xFinally, Chapters 5 and 6 present the concluding remarks and the experimental details of the work described in Chapters 2-4.

This thesis is a study of the structural, electrical and magnetic properties of indium antimonide (InSb) nanowires (NWs), that were synthesized by a template-assisted ordered growth technique via electrochemical deposition. InSb was chosen for this study because of its intrinsic properties that make it a material of choice for applications in high channel mobility, infrared (IR) sensing, thermoelectrics, and magnetoresistive sensing martials. This work has four main components: (i) Growth in commercially available anodic aluminum oxide (AAO) template, where hole-dominated conduction was observed, following NW growth in a low pH electrolyte. The challenge in using these AAO templates was in covering the back surface of the pores with a metal film. Uncovered pores resulted in electrolyte leakage and non-reproducible results. (ii) Growth in flexible polycarbonate membranes, where the flexibility of the membranes resulted in polycrystalline or high defect density NW growth. (iii) Fabrication of an AAO template, where the barrier layer thinning technique was found to be efficient in removal of the think aluminum oxide barrier that exists at the interface between the template and the aluminum metal. This allows for direct growth of NWs into the template pores without the need for metal evaporation. (iv) Fabrication of a heterostructure comprising of an InSb layer sandwiched between two ferromagnetic contacts. Preliminary results show evidence of inverse spin-valve effect at the low temperature of 4K.

This work presents the preparation and physical properties of spinel nanoparticles and nanocomposites. All nanocomposites in diamagnetic matrix like chromites CoCr2O4, CuCr2O4, NiCr2O4, ZnCr2O4 and ferrite MgFe2O4 were prepared using sol-gel method. On the other hand, isolated nanoparticles such as MgCr2O4, MnCr2O4, CuCr2O4, NiCr2O4, and FeCr2O4, were prepared using autocombustion a co-precipitation methods. CoFe2O4 and MgFe2O4 were prepared by microemulsion alkoxide method. This microemulsion method was used for the spinel nanoparticles preparation for the first time. This work describes the influence of heat treatment temperature on the final particle size and influence of particle size on physical properties of material. The study of the influence of twovalent cationt in the spinel structure on the magnetic properties of chromites was also carried out. The final samples were characterized by XRD powder diffraction, Mössbauer spectroscopy, infrared and Raman spectroscopy, and HRTEM. The dependence of magnetization on applied magnetic field at constant temperature and ZFC (zero-field cooling) - FC (field cooling) measurement was carried out on the prepared sample.

The magnetic properties of axially confined, hydrogenated single-walled carbon nanotubes (SWCNTs) of the (n,0)-type with n=5-24 are systematically explored by density functional theory. Emphasis is placed on the relation between the ground-state magnetic moments of SWCNTs and zigzag graphene nanoribbons (ZGNRs). Comparison between the SWCNTs considered here and ZGNRs of equal length gives rise to two basic questions: 1) how does the nanotube curvature affect the antiferromagnetic order known to prevail for ZGNRs, and 2) to what extent do the magnetic moments localized at the SWCNT edges deviate from the zero-curvature limit of n/3 μB? In response to these questions, it is found that systems with n≥7 display preference for antiferromagnetic order at any length investigated, whereas for n=5, 6 the magnetic phase varies with tube length. Furthermore, elementary patterns are identified that describe the progression of the magnitude of the magnetic moment with n for the longest tubes explored in this work. The spin densities of the considered SWCNTs are analyzed as a function of the tube length L, with L ranging from 3 to 11 transpolyene rings for n≥7 and from 3 to 30 rings for n=5 and 6. Magnetic carbon nanostructures are explored by density functional theory calculations on axially confined, single-walled carbon nanotubes (SWCNTs) of the (n,0)-type with n=5-24. For SWCNTs with n≥7, antiferromagnetic (AFM) order is favored energetically over ferromagnetic (FM) order for all lengths L investigated, whereas for n=5, 6 the magnetic phase varies with tube length (see picture).