Propriedades magnéticas de nanoestruturas adsorvidas em superfícies metálicas

Neste trabalho, utilizamos o método de primeiros princípios RS-LMTO-ASA (Real Space – Linear Muffin-Tin Orbital - Atomic Sphere Approximation) baseado na Teoria do Funcional da Densidade (DFT - Density Functional Theory) e implementado para o cálculo de estruturas magnéticas não-colineares, para investigar as propriedades magnéticas de nanoestruturas adsorvidas em superfícies metálicas. Consideramos aglomerados com diferentes geometrias e tamanhos como adátomos, dímeros, trímeros, nanofios e nanoestruturas de geometria triangular de Fe, Fe-Co e Fe-Pt adsorvidos sobre a superfície de Pt(111) e tratamos também nanoestruturas de Mn sobre a superfície de Ag(111). Mostramos que os nanofios de Fe-Co sobre a superfície de Pt(111) apresentam um ordenamento ferromagnético. Devido à redução do número de coordenação presente na superfície, os momentos de spin e orbital nos sítios de Fe e Co mostram-se elevados comparados com os respectivos valores dos momentos destes metais como bulk. Analisamos também como estes momentos variam em função da concentração destes elementos nos nanofios. Para os sistemas compostos por nanofios Fe-Pt adsorvidos em Pt(111), mostramos que é possível sintonizar as interações de troca entre os adátomos magnéticos Fe através da introdução de um diferente número de átomos Pt para ligá-los. Por exemplo, a interação de troca entre os adátomos de Fe pode ser consideravelmente aumentada pela introdução de cadeias de Pt que os conectem e tanto configurações ferromagnéticas, antiferromagnéticas ou não-colineares entre os adátomos de Fe podem ser estabilizadas, dependendo da espessura do espaçador Pt. Para os aglomerados Mn sobre a Ag(111) mostramos que a interação de troca entre os sítios de Mn depende não somente da distância entre os átomos, mas também do número de coordenação de cada sítio. Desta forma, verificamos um magnetismo não-colinear nestas nanoestruturas causado tanto por frustração geométrica, quanto pela competição de interações de curto e longo alcance. Nossos resultados estão em boa concordância com os resultados experimentais da literatura e com os resultados teóricos obtidos por outros métodos, quando existentes.

Propriedades magnéticas de nanoestruturas de metais de transição 3d adsorvidas na superfície de Pt(111)

Neste trabalho, utilizamos o método de primeiros princípios, RS-LMTO-ASA (“Real Space - Linear Muffin-Tin Orbital - Atomic Sphere Approximation”), baseado na Teoria do Funcional da Densidade (DFT) e implementado para o cálculo de estruturas magnéticas não-colineares, para investigar as propriedades magnéticas de nanoestruturas de metais de transição 3d (Cr, Mn, Fe, Co e Ni) adsorvidas na superfície de Pt(111). Diferentes geometrias como adátomos, dímeros, trímeros, fios lineares e zig-zag foram consideradas e, o tamanho dos aglomerados foi variado de 2 a 7 átomos. Mostramos que os aglomerados de Fe, Co e Ni sobre a superfície de Pt(111), para todas as geometrias simuladas, apresentam um ordenamento ferromagnético. Devido à redução do número de coordenação presente na superfície, os momentos de spin e orbital nos sítios de Fe, Co e Ni, para as diferentes geometrias, mostram-se elevados comparados com os respectivos valores dos momentos destes metais como bulk. Para os glomerados de Cr e Mn mostramos que a interação de troca antiferromagnética entre primeiros vizinhos leva a um ordenamento antiferromagnético colinear no caso de geometrias lineares. No entanto, se o antiferromagnetismo é frustrado por restrição geométrica imposta aos aglomerados pela superfície triangular do substrato, obtém-se um comportamento magnético não-colinear para aglomerados de Cr e Mn sobre a Pt(111). Nossos resultados estão em boa concordância com os resultados experimentais da literatura e com os resultados teóricos obtidos por outros métodos, quando existentes.

Ferrimagnetism and spin excitation in a Ni-Mn partially inverted spinel prepared using a modified polymeric precursor method

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

First-principles studies of complex magnetism in Mn nanostructures on the Fe(001) surface

The magnetic properties of Mn nanostructures on the Fe(001) surface have been studied using the noncollinear first-principles real space-linear muffin-tin orbital-atomic sphere approximation method within density-functional theory. We have considered a variety of nanostructures such as adsorbed wires, pyramids, and flat and intermixed clusters of sizes varying from two to nine atoms. Our calculations of interatomic exchange interactions reveal the long-range nature of exchange interactions between Mn-Mn and Mn-Fe atoms. We have found that the strong dependence of these interactions on the local environment, the magnetic frustration, and the effect of spin-orbit coupling lead to the possibility of realizing complex noncollinear magnetic structures such as helical spin spiral and half-skyrmion.

Multiphase transformer-coupled converter: two different strategies for energy conversion

The operation of a multiphase topology, ideally, without energy storage presents the advantage of achieving very high efficiency over a wide load range as well as a fast dynamic response. However, ideal no-energy storage operation also implies a limitation in the regulation capability of the topology, the output voltage can only take discrete values. These features (high efficiency and discrete regulation capability) of the proposed energy conversion strategy enable the topology as a candidate for `DC-DC transformer' applications. The advantages, drawbacks and the operating principle of this concept, implemented with a `closed chain' magnetic structure have been already presented. In this work, the minimum energy storage operation, is applied to two different magnetic structures. These magnetic structures are called `closed chain' and `pyramidal' the main advantage of the `pyramidal' coupling structure is to improve the size of the converter without increasing the operating frequency. Both magnetic structures are analyzed, compared and experimentally implemented.

Novel Inductor‐less Conversion Strategy Based on Multiphase Transformer‐Coupled Converters: Analysis, Design and Applications

There are many the requirements that modern power converters should fulfill. Most of the applications where these converters are used, demand smaller converters with high efficiency, improved power density and a fast dynamic response. For instance, loads like microprocessors demand aggressive current steps with very high slew rates (100A/mus and higher); besides, during these load steps, the supply voltage of the microprocessor should be kept within tight limits in order to ensure its correct performance. The accomplishment of these requirements is not an easy task; complex solutions like advanced topologies - such as multiphase converters- as well as advanced control strategies are often needed. Besides, it is also necessary to operate the converter at high switching frequencies and to use capacitors with high capacitance and low ESR. Improving the dynamic response of power converters does not rely only on the control strategy but also the power topology should be suited to enable a fast dynamic response. Moreover, in later years, a fast dynamic response does not only mean accomplishing fast load steps but output voltage steps are gaining importance as well. At least, two applications that require fast voltage changes can be named: Low power microprocessors. In these devices, the voltage supply is changed according to the workload and the operating frequency of the microprocessor is changed at the same time. An important reduction in voltage dependent losses can be achieved with such changes. This technique is known as Dynamic Voltage Scaling (DVS). Another application where important energy savings can be achieved by means of changing the supply voltage are Radio Frequency Power Amplifiers. For example, RF architectures based on ‘Envelope Tracking’ and ‘Envelope Elimination and Restoration’ techniques can take advantage of voltage supply modulation and accomplish important energy savings in the power amplifier. However, in order to achieve these efficiency improvements, a power converter with high efficiency and high enough bandwidth (hundreds of kHz or even tens of MHz) is necessary in order to ensure an adequate supply voltage. The main objective of this Thesis is to improve the dynamic response of DC-DC converters from the point of view of the power topology. And the term dynamic response refers both to the load steps and the voltage steps; it is also interesting to modulate the output voltage of the converter with a specific bandwidth. In order to accomplish this, the question of what is it that limits the dynamic response of power converters should be answered. Analyzing this question leads to the conclusion that the dynamic response is limited by the power topology and specifically, by the filter inductance of the converter which is found in series between the input and the output of the converter. The series inductance is the one that determines the gain of the converter and provides the regulation capability. Although the energy stored in the filter inductance enables the regulation and the capability of filtering the output voltage, it imposes a limitation which is the concern of this Thesis. The series inductance stores energy and prevents the current from changing in a fast way, limiting the slew rate of the current through this inductor. Different solutions are proposed in the literature in order to reduce the limit imposed by the filter inductor. Many publications proposing new topologies and improvements to known topologies can be found in the literature. Also, complex control strategies are proposed with the objective of improving the dynamic response in power converters. In the proposed topologies, the energy stored in the series inductor is reduced; examples of these topologies are Multiphase converters, Buck converter operating at very high frequency or adding a low impedance path in parallel with the series inductance. Control techniques proposed in the literature, focus on adjusting the output voltage as fast as allowed by the power stage; examples of these control techniques are: hysteresis control, V 2 control, and minimum time control. In some of the proposed topologies, a reduction in the value of the series inductance is achieved and with this, the energy stored in this magnetic element is reduced; less stored energy means a faster dynamic response. However, in some cases (as in the high frequency Buck converter), the dynamic response is improved at the cost of worsening the efficiency. In this Thesis, a drastic solution is proposed: to completely eliminate the series inductance of the converter. This is a more radical solution when compared to those proposed in the literature. If the series inductance is eliminated, the regulation capability of the converter is limited which can make it difficult to use the topology in one-converter solutions; however, this topology is suitable for power architectures where the energy conversion is done by more than one converter. When the series inductor is eliminated from the converter, the current slew rate is no longer limited and it can be said that the dynamic response of the converter is independent from the switching frequency. This is the main advantage of eliminating the series inductor. The main objective, is to propose an energy conversion strategy that is done without series inductance. Without series inductance, no energy is stored between the input and the output of the converter and the dynamic response would be instantaneous if all the devices were ideal. If the energy transfer from the input to the output of the converter is done instantaneously when a load step occurs, conceptually it would not be necessary to store energy at the output of the converter (no output capacitor COUT would be needed) and if the input source is ideal, the input capacitor CIN would not be necessary. This last feature (no CIN with ideal VIN) is common to all power converters. However, when the concept is actually implemented, parasitic inductances such as leakage inductance of the transformer and the parasitic inductance of the PCB, cannot be avoided because they are inherent to the implementation of the converter. These parasitic elements do not affect significantly to the proposed concept. In this Thesis, it is proposed to operate the converter without series inductance in order to improve the dynamic response of the converter; however, on the other side, the continuous regulation capability of the converter is lost. It is said continuous because, as it will be explained throughout the Thesis, it is indeed possible to achieve discrete regulation; a converter without filter inductance and without energy stored in the magnetic element, is capable to achieve a limited number of output voltages. The changes between these output voltage levels are achieved in a fast way. The proposed energy conversion strategy is implemented by means of a multiphase converter where the coupling of the phases is done by discrete two-winding transformers instead of coupledinductors since transformers are, ideally, no energy storing elements. This idea is the main contribution of this Thesis. The feasibility of this energy conversion strategy is first analyzed and then verified by simulation and by the implementation of experimental prototypes. Once the strategy is proved valid, different options to implement the magnetic structure are analyzed. Three different discrete transformer arrangements are studied and implemented. A converter based on this energy conversion strategy would be designed with a different approach than the one used to design classic converters since an additional design degree of freedom is available. The switching frequency can be chosen according to the design specifications without penalizing the dynamic response or the efficiency. Low operating frequencies can be chosen in order to favor the efficiency; on the other hand, high operating frequencies (MHz) can be chosen in order to favor the size of the converter. For this reason, a particular design procedure is proposed for the ‘inductorless’ conversion strategy. Finally, applications where the features of the proposed conversion strategy (high efficiency with fast dynamic response) are advantageus, are proposed. For example, in two-stage power architectures where a high efficiency converter is needed as the first stage and there is a second stage that provides the fine regulation. Another example are RF power amplifiers where the voltage is modulated following an envelope reference in order to save power; in this application, a high efficiency converter, capable of achieving fast voltage steps is required. The main contributions of this Thesis are the following: The proposal of a conversion strategy that is done, ideally, without storing energy in the magnetic element. The validation and the implementation of the proposed energy conversion strategy. The study of different magnetic structures based on discrete transformers for the implementation of the proposed energy conversion strategy. To elaborate and validate a design procedure. To identify and validate applications for the proposed energy conversion strategy. It is important to remark that this work is done in collaboration with Intel. The particular features of the proposed conversion strategy enable the possibility of solving the problems related to microprocessor powering in a different way. For example, the high efficiency achieved with the proposed conversion strategy enables it as a good candidate to be used for power conditioning, as a first stage in a two-stage power architecture for powering microprocessors.

Magnetism and photophysics in supramolecular transition-metal compounds

Based on a synthetic strategy, extended anionic, homo and bimetallic oxalato-bridged transition-metal compounds with two (2D) and three-dimensional (3D) connectivities can be synthesized and crystallized. Thereby, the choice of the templating counterions will determine the crystal chemistry. Since the oxalato bridge is a mediator for both antiferro and ferromagnetic interactions between similar and dissimilar metal ions, long-range magnetic ordering will occur. Examples of the determination of magnetic structures in 2D and 3D compounds by means of elastic neutron scattering methods will be discussed. In addition, due to the possibility of the variation of different metal ions in varying oxidation states, interesting photophysical processes can be observed within the extended three-dimensional host/guest systems.

Strain-induced stabilization of new magnetic spinel structures in epitaxial oxide heterostructures.

We report here on the growth of NiFe2O4 epitaxial thin films of different thickness (3 nm ¿ t ¿ 32 nm) on single crystalline substrates having spinel (MgAl2O4) or perovskite (SrTiO3) structure. Ultrathin films, grown on any of those substrates, display a huge enhancement of the saturation magnetization: we will show that partial cationic inversion may account for this enhancement, although we will argue that suppression of antiparallel collinear spin alignment due to size-effects cannot be excluded. Besides, for thicker films, the magnetization of films on MAO is found to be similar to that of bulk ferrite; in contrast, the magnetization of films on STO is substantially lower than bulk. We discuss on the possible mechanisms leading to this remarkable difference of magnetization.

Hyperfine interactions in the new Fe-based superconducting structures and related magnetic phases

This thesis is devoted to the study of the hyperfine properties in iron-based superconductors and the synthesis of these compounds and related phases. During this work polycrystalline chalcogenide samples with stoichiometry 1:1 (FeTe1-χSχ, FeSe1-x) and pnictide samples with stoichiometry 1:2:2 (BaFe2(As1-χPχ)2, EuFe2(As1-x Px)2) were synthesized by solid-state reaction methods in vacuum and in a protecting Ar atmosphere. In several cases post-annealing in oxygen atmosphere was employed. The purity and superconducting properties of the obtained samples were checked with X-ray diffraction, SQUID and resistivity measurements. For studies of the magnetic properties of the investigated samples Mössbauer spectroscopy was used. Using low-temperature measurements around Tc and various values of the source velocity the hyperfine interactions were obtained and the magnetic and structural properties in the normal and superconducting states could be studied. Mössbauer measurements together with XRD characterization were also used for the detection of impurity phases. DFT calculations were used for the theoretical study of Mössbauer parameters for pnictide-based ᴻsamples BaFe2(As1-xPx)2 and EuFe2(As1-xPx)2.

Fabrication of thin films and nano columnar structures of Fe-Ni amorphous alloys and modification of its surface properties by thermal annealing and swift heavy ion irradiation for tailoring the magnetic properties

Department of Physics, Cochin University of Science and Technology

Syntheses of two new 1D and 3D networks of Cu(II) and Co(II) using malonate and urotropine as bridging ligands: Crystal structures and magnetic studies

Two new metal-organic based polymeric complexes, [Cu-4(O2CCH2CO2)(4)(L)].7H(2)O (1) and [CO2(O2CCH2CO2)(2)(L)].2H(2)O (2) [L = hexamethylenetetramine (urotropine)], have been synthesized and characterized by X-ray crystal structure determination and magnetic studies. Complex 1 is a 1D coordination polymer comprising a carboxylato, bridged Cu-4 moiety linked by a tetradentate bridging urotropine. Complex 2 is a 3D coordination polymer made of pseudo-two-dimensional layers of Co(II) ions linked by malonate anions in syn-anticonformation which are bridged by bidentate urotropine in trans fashion, Complex 1 crystallizes in the orthothombic system, space group Pmmn, with a = 14,80(2) Angstrom, b = 14.54(2) Angstrom, c = 7.325(10) Angstrom, beta = 90degrees, and Z = 4. Complex 2 crystallizes in the orthorhombic system, space group Imm2, a = 7.584(11) Angstrom, b = 15.80(2) Angstrom, c = 6.939(13) Angstrom, beta = 90.10degrees(1), and Z = 4. Variable temperature (300-2 K) magnetic behavior reveals the existence of ferro- and antiferromagnetic interactions in 1 and only antiferromagnetic interactions in 2. The best fitted parameters for complex 1 are J = 13.5 cm(-1), J = -18.1 cm(-1), and g = 2.14 considering only intra-Cu-4 interactions through carboxylate and urotropine pathways. In case of complex 2, the fit of the magnetic data considering intralayer interaction through carboxylate pathway as well as interlayer interaction via urotropine pathway gave no satisfactory result at this moment using any model known due to considerable orbital contribution of Co(II) ions to the magnetic moment and its complicated structure. Assuming isolated Co(II) ions (without any coupling, J = 0) the shape of the chi(M)T curve fits well with experimental data except at very low temperatures.

Two new mu-(1,3-azido)-bridged polymers: alternating single and double bridges in a 1D nickel(II) complex and uniform bridge in a 2D copper(II) complex: Syntheses, single-crystal structures and magnetic studies

Two polymeric azido bridged complexes [Ni2L2(N-3)(3)](n)(ClO4). (1) and [Cu(bpdS)(2)(N-3)],(ClO4),(H2O)(2.5n) (2) [L = Schiff base, obtained from the condensation of pyridine-2-aldehyde with N,N,2,2-tetramethyl-1,3-propanediamine; bpds = 4,4'-bipyridyl disulfide] have been synthesized and their crystal structures have been determined. Complex 1, C26H42ClN15Ni2O4, crystallizes in a triclinic system, space group P1 with a 8.089(13), b = 9.392(14), c = 12.267(18) angstrom, a = 107.28(l), b 95.95(1), gamma = 96.92(1)degrees and Z = 2; complex 2, C20H21ClCuN7O6.5S4, crystallizes in an orthorhombic system, space group Pnna with a = 10.839(14), b = 13.208(17), c = 19.75(2) angstrom and Z = 4. The crystal structure of I consists of 1D polymers of nickel(L) units, alternatively connected by single and double bridging mu-(1,3-N-3) ligand with isolated perchlorate anions. Variable temperature magnetic susceptibility data of the complex have been measured and the fitting,of magnetic data was carried out applying the Borris-Almenar formula for such types of alternating one-dimensional S = 1 systems, based on the Hamiltonian H = -J Sigma(S2iS2i-1 + aS(2i)S(2i+1)). The best-fit parameters obtained are J = -106.7 +/- 2 cm(-1); a = 0.82 +/- 0.02; g = 2.21 +/- 0.02. Complex 2 is a 2D network of 4,4 topology with the nodes occupied by the Cu-II ions, and the edges formed by single azide and double bpds connectors. The perchlorate anions are located between pairs of bpds. The magnetic data have been fitted considering the complex as a pseudo-one-dimensional system, with all copper((II)) atoms linked by [mu(1,3-azido) bridging ligands at axial positions (long Cu...N-3 distances) since the coupling through long bpds is almost nil. The best-fit parameters obtained with this model are J = -1.21 +/- 0.2 cm(-1), g 2.14 +/- 0.02. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

Syntheses, crystal structures and magnetic properties of carboxylato-bridged polymeric networks of Mn-II

Three new carboxylato-bridged polymeric networks of Mn-II having molecular formula [Mn(ox)(dpyo)](n) (1), {[Mn-2(mal)(2)(bpee)(H2O)(2)]center dot 0.5(bpee)center dot 0.5(CH3OH)}n, (2) and {[Mn-3(btc)(2)(2,2'-bipy)(2)(H2O)(6)]center dot 4H(2)O}(n) (3) [dpyo, 4,4'-bipyridine N,N'dioxide; bpee, trans-1,2 bis(4-pyridyl) ethylene; 2,2'-bipy, 2,2'-bipyridine; ox = oxalate dianion; mal = malonate dianion; btc = 1,3,5-benzenetricarboxylate trianion] have been synthesized and characterized by single-crystal X-ray diffraction studies and low temperature magnetic measurements. Structure determination of complex I reveals a covalent bonded 2D network containing bischelating oxalate and bridging dpyo; complex 2 is a covalent,bonded 3D polymeric architecture, formed by bridging malonate and bpee ligands, resulting in an open framework with channels filled by uncoordinated disordered bpee and methanol molecules. Whereas complex 3, comprising btc anions bound to three metal centers, is a 1D chain which further extends its dimensionality to 3D via pi-pi and H-bonding interactions. Low temperature magnetic measurements reveal the existence of weak antiferromagnetic interaction in all these complexes. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).

Influence of counter anions on the structures and magnetic properties of trinuclear Cu(II) complexes containing a mu(3)-OH core and Schiff base ligands

Four trinuclear Cu(II) complexes, [(CuL1)(3)(mu(3)-OH)](NO3)(2) (1), [(CuL2)(3)(mu(3)-OH)](I)(2)center dot H2O (2), [(CuL3)(3)(mu(3)-OH)](I)(2) (3) and [(CuL1)(3)(mu(3)-OH)][(CuI3)-I-1] (4), where HL1 (8-amino-4-methyl-5-azaoct-3-en-2-one), HL2 [7-amino-4-methyl-5-azaoct-3-en-2-one] and HL3 [7-amino-4-methyl-5-azahept-3-en-2- one] are the three tridentate Schiff bases, have been synthesized and structurally characterized by X-ray crystallography. All four complexes contain a partial cubane core, [(CuL)(3)(mu(3)-OH)](2+) in which the three [CuL] subunits are interconnected through two types of oxygen bridges afforded by the oxygen atoms of the ligands and the central OH- group. The copper(II) ions are in a distorted square-pyramidal environment. The equatorial plane consists of the bridging oxygen of the central OH- group together with three atoms (N, N, O) from the Schiff base. The oxygen atom of the Schiff base also coordinates to the axial position of Cu(II) of another subunit to form the cyclic trimer. Magnetic susceptibilities have been determined for these complexes over the temperature range of 2-300 K. The isotropic Hamiltonian, H = -J(12)S(1)S(2) - J(13)S(1)S(3) - J(23)S(2)S(3) has been used to interpret the magnetic data. The best fit parameters obtained are: J = - 54.98 cm(-1) g = 2.24 for 1; J = - 56.66 cm(-1), g = 2.19 for 2; J = -44.39 cm(-1), g = 2.16 for 3; J = - 89.92 cm(-1), g = 2.25 for 4. The EPR data at low temperature indicate that the phenomenon of spin frustration occurs for complexes 1-3. (c) 2007 Elsevier B.V. All rights reserved.