<p>The magnetic properties of transition metal compounds have been studied using SQUID-magnetometry, magnetic force microscopy and Lorentz transmission electron microscopy. New magnetic materials have been found and their magnetic properties have been determined. How the magnetic properties of a material can be changed through e.g. chemical substitution of magnetic and nonmagnetic atoms and shape and size effects have also been studied. Three different sets of samples have been investigated: three new Mn-compounds, two substitution series of layered magnetic structures and ferromagnetic micronsized thin film elements.</p><p>The three Mn-compounds, Mn₃IrSi, IrMnSi and Mn₈Pd₁₅Si₇, show different magnetic ordering. Mn₃IrSi orders 'antiferromagnetically' at 210 K. IrMnSi forms a double cycloidal spin spiral below 460 K. Mn₈Pd₁₅Si₇ only shows short-range magnetic ordering.</p><p>Substituting Se with S in TlCo₂Se_2-xS_x changes the magnetic order from a spin spiral to a colinear ferromagnet for a composition of <i>x</i>=1.75. An intermediate region exists where the compound is neither a pure ferromagnet, nor purely a spin spiral, as evidenced by the magnetization versus field measurements for the <i>x</i>=1.3 and 1.5 samples. This is also seen in the temperature dependent susceptibility measurements. For the TlCu_2-xFe_xSe₂ compounds it was found that the ordering temperature and saturation magnetic moment per Fe-atom changed with composition <i>x</i>.</p><p>Ferromagnetic micronsized thin film elements in permalloy, Fe₂₀Ni₈₀, and epitaxial Fe/Co multilayers were studied. For the Fe/Co multilayer thin film elements it was found that it is possible to change the magnetization reversal process, by aligning the easy shape anisotropy axis with either the easy or the hard magnetocrystalline anisotropy axis. In the permalloy elements the effect of inter-elemental distance was found to determine the interval of fields where multidomain states were stable, so that for shorter inter-elemental distances multidomain states were stable for a shorter interval of fields. The domain structure of permalloy elements in rotating magnetic fields was also studied. Higher applied fields led to a broader interval of angles in which saturated states were stable.</p>

Magnetic force microscopy studies in varying temperature and applied external magnetic field of magnetic thin films of LaCoO₃ under strain and single crystal UMn₂Ge₂ have been performed. In the case of LaCoO₃ thin films the aim is an understanding of the response of the magnetic microstructure to different signs and degrees of strain and a further attempt to distinguish the effect of defects from strain-induced effects. In UMn₂Ge₂ the magnetic microstructure is imaged for the first time and signatures of a possible phase transition at 150 K and crystalline anisotropy are explored. The first portion of this dissertation focuses on the synthesis methods used to produce the samples investigated and the critical role of synthesis in producing high-quality samples. This is followed by a discussion of characterization techniques used to obtain local and global magnetic and structural characteristics, with particular emphasis on magnetic force microscopy including noise characteristics and a discussion of achieving a high force gradient sensitivity by optimizing the fiber-optic interferometer used for cantilever deflection detection. Design elements and features of the multi-mode variable-temperature atomic force microscope used to obtain magnetic force microscopy images are presented and results for LaCoO₃ and UMn₂Ge₂ are discussed. / text

The magnetic properties of transition metal compounds have been studied using SQUID-magnetometry, magnetic force microscopy and Lorentz transmission electron microscopy. New magnetic materials have been found and their magnetic properties have been determined. How the magnetic properties of a material can be changed through e.g. chemical substitution of magnetic and nonmagnetic atoms and shape and size effects have also been studied. Three different sets of samples have been investigated: three new Mn-compounds, two substitution series of layered magnetic structures and ferromagnetic micronsized thin film elements. The three Mn-compounds, Mn3IrSi, IrMnSi and Mn8Pd15Si7, show different magnetic ordering. Mn3IrSi orders 'antiferromagnetically' at 210 K. IrMnSi forms a double cycloidal spin spiral below 460 K. Mn8Pd15Si7 only shows short-range magnetic ordering. Substituting Se with S in TlCo2Se2-xSx changes the magnetic order from a spin spiral to a colinear ferromagnet for a composition of x=1.75. An intermediate region exists where the compound is neither a pure ferromagnet, nor purely a spin spiral, as evidenced by the magnetization versus field measurements for the x=1.3 and 1.5 samples. This is also seen in the temperature dependent susceptibility measurements. For the TlCu2-xFexSe2 compounds it was found that the ordering temperature and saturation magnetic moment per Fe-atom changed with composition x. Ferromagnetic micronsized thin film elements in permalloy, Fe20Ni80, and epitaxial Fe/Co multilayers were studied. For the Fe/Co multilayer thin film elements it was found that it is possible to change the magnetization reversal process, by aligning the easy shape anisotropy axis with either the easy or the hard magnetocrystalline anisotropy axis. In the permalloy elements the effect of inter-elemental distance was found to determine the interval of fields where multidomain states were stable, so that for shorter inter-elemental distances multidomain states were stable for a shorter interval of fields. The domain structure of permalloy elements in rotating magnetic fields was also studied. Higher applied fields led to a broader interval of angles in which saturated states were stable.

This thesis presents experimental results on strongly interacting γ-Fe2O3 magnetic nanoparticles and their collective properties. The main findings are that very dense randomly packed (≈60%) γ-Fe2O3 nanoparticles form a replica of a spin glass. The magnetic properties of the nanoparticle system are in most regards the same as those of an atomic spin glass. The system is therefore proposed as a model superspin glass. In superspin glasses the interacting building blocks that form the collective state are single domain nanoparticles, superspins with a magnetic moment of about 10000 μB, which can be compared to the atomic magnetic moment in spin glasses of approximately 1 μB.  It was found that the relaxation time of the individual nanoparticles impacts the collective properties and governs the superspin dimensionality. Several dense compacts, each prepared with nanoparticles of a specific size, with diameters 6, 8, 9 and 11.5 nm, were studied. All the studied compacts were found to form a superspin glass state. Non-interacting reference samples, consisting of the same particles but coated with a silica shell, were synthesized to determine the single particle magnetic properties.  It was also found that the effects of the nanoparticle size distribution, which lead to a variation of the magnetic properties, can be mitigated by having strong enough interparticle interactions. The majority of the work was carried out using SQUID magnetometry.

Layered crystals with magnetic elements as Co and Fe have been studied. In TlCo2Se2, where Co atoms in one sheet are separated by Tl and Se from the next Co sheet, magnetic interaction within and between the sheets have been studied. Samples doped with 4% 57Fe replaced Co, show a magnetic spiral character with hyperfine fields in a flower shape in the ab-plane. The magnetic moment of 0.46 μB per Co atom derived from the average field is in good agreement with the result from neutron diffraction. In TlCu1.73Fe0.27Se2 the easy axis of magnetisation is the c-axis. The magnetic moment calculated from the Mössbauer data and SQUID magnetrometry is 0.97 μB per Fe atom with TC = 55(5) K. Multilayers of different elements have been studied. The effect of vanadium atoms on iron atoms at the interface of FeNi/V multilayers has been determined and the intermixing at the interface has been calculated to be 2-3 monolayers. For FeNi/Co 1/1 monolayer the magnetic hyperfine field (Bhf) is 45° out-of-plane, while for superlattices containing 2 to 5 monolayers it is in the plane. An study on Fe/Co superlattice were done by experimental, theoretical and simulational methods. The Bhf is highest for the Fe at the second layer next to the interface and gets the bulk value in the centre of thicker Fe layers. Studied magnetic nanoparticles coated with a lipid bilayer (magnetoliposomes) are found to have the magnetite structure but being non-stoichiometric as a result of the manufacturing process. The composition was approximately 32% γ-Fe2O3 and 68% Fe3O4. The oxidation evolution and its effect on magnetic properties of Fe clusters were also studied by means of different techniques. The extraction and insertion mechanism of lithium in the cathode material Li2FeSiO4 has been monitored by in situ x-ray diffraction and Mössbauer spectroscopy during the first two cycles. The relative amount of Fe+3/ Fe+2 at each end state was in good agreement with the results obtained from electrochemical measurements. A possible explanation to the observed lowering of the potential plateau from 3.10 to 2.80 V occurring during the first cycle, involves a structural rearrangement process in which some of the Li ions and the Fe ions are interchanged. The behaviour of small amounts of Fe in brass is investigated using Mössbauer spectroscopy. It was shown that a heat treatment can increase the amount of the precipitates of γ-Fe and ~650° C is the optimal treatment for having the highest amount of this phase.

No description available.

In dieser Arbeit wurde die Ausgangsverbindung der eisenbasierten Supraleiter, LaFeAsO, durch die Synthese und Charakterisierung von poly- und einkristallinen Proben untersucht. Supraleitung kann in den eisenbasierten Supraleitern durch Elektronen- oder Lochdotierung hervorgerufen werden. Die Substitution von Eisen durch Mangan, formal eine Lochdotierung, hat hingegen einen destruktiven Effekt auf die Supraleitung. Dieser ist bei optimal fluordotiertem LaFeAs(O,F) um Größenordnungen stärker ausgeprägt als bei Nd- oder Sm-FeAs(O,F). Indem Lanthan partiell durch das kleinere Yttrium substituiert wurde, konnte gezeigt werden, dass diese unterschiedlich starke Mangantoleranz durch die Unterschiede im Seltenerdmetall-Ionenradius bedingt ist. Weiterhin finden sich Anzeichen, dass die Unterdrückung der Supraleitung durch Mangan mit Elektronenlokalisierung korreliert ist. Das Fehlen von großen dreidimensionalen Einkristallen der SEFeAsO-Verbindungsklasse stellt ein großes Hindernis in der Erforschung der elektronischen Eigenschaften der eisenbasierten Supraleiter dar. Im Rahmen dieser Arbeit konnte gezeigt werden, dass das Verfahren der Festkörper-Einkristallzüchtung ein geeignetes Mittel darstellt, um große, facettierte SEFeAsO-Einkristalle mit ausgeprägtem Wachstum in c-Richtung zu erhalten. Mit diesem neu entwickelten Einkristallzüchtungsverfahren konnte ein aktualisiertes Phasendiagramm von La(Fe,Co)AsO erstellt werden. Die Substitution von Eisen durch Cobalt entspricht einer Elektronendotierung und führt zu Supraleitung mit einer maximalen Sprungtemperatur von 12 K. Die Ausgangsverbindung LaFeAsO zeigt bei etwa 156 K einen strukturellen Phasenübergang von einer tetragonalen zu einer orthorhombischen Struktur, weiterhin tritt unterhalb von etwa 138 K eine Spindichtewelle auf. In Einklang mit dem bekannten Phasendiagramm werden mit Cobaltdotierung die beiden Übergänge unterdrückt, mit höheren Cobaltkonzentrationen kommt es zu Supraleitung. Anders als beim bekannten Phasendiagramm kann eine deutliche Aufspaltung zwischen magnetischem und strukturellen Übergang bei kleinen Cobaltkonzentrationen beobachtet werden. Außerdem findet sich eine Region der Koexistenz zwischen Supraleitung und Spindichtewelle. Bisher konnte ein solcher Zustand im SE(Fe,Co)AsO-System nicht beobachtet werden.

Magnetism of carbon-based materials is a challenging area for both fundamental research and possible applications. We present studies of low-dimensional carbon-based magnetic systems (fullerene-diluted molecular magnets, carbon nanotubes, graphite fluoride, and nanoporous carbon) by means of SQUID magnetometer, X-ray diffraction and vibrational spectroscopy, the latter techniques used as complementary instruments to find a correlation between the magnetic behaviour and the structure of the samples.In the first part of the thesis, characteristic features of the magnetization process in aligned films of carbon nanotubes with low concentration of iron are discussed. It is shown that the magnetism of such structures is influenced by quantum effects, and the anisotropy behaviour is opposite to what is observed in heavily doped nanotubes.In the second part, Mn12-based single molecular magnets with various carboxylic ligands and their 1:1 fullerene-diluted complexes are studied. We prove that magnetic properties of such systems strongly depend on the environment, and, in principle, it is possible to design a magnet with desirable properties. One of the studied compounds demonstrated a record blocking temperature for a single molecular magnet. Both fullerene-diluted complexes demonstrated “magnetization training” effect in alternating magnetic fields and the ability to preserve magnetic moment.The third and the fourth parts of the thesis are dedicated to the analysis of various contributions to the magnetic susceptibility of metal-free carbon-based systems – intercalated compounds of graphite fluorides and nanoporous oxygen-eroded graphite. The magnetic properties of these systems are strongly dependent on structure, and can be delicately tuned by altering the π-electron system of graphite, i. e. by degree of fluorination of intercalated compounds and by introduction of boron impurity to the host matrix of nanoporous graphite. / Magnetism av kolbaserade material är ett utmanande område för både grundforskning och möjliga tillämpningar. Vi presenterar studier med låg-dimensionella kolbaserade magnetiska system (fulleren-utspädda molekylära magneter, kolnanorör, grafit fluorid och nanoporösa kol) med hjälp av SQUID magnetometer, röntgendiffraktion och vibrerande spektroskopi, de senare tekniker som används som komplement instrument för att finna sambandet mellan den magnetiska uppträdande och strukturen hos proven. I den första delen av avhandlingen är egenheter från magnetisering processen i linje filmer av kolnanorör med låg koncentration av järn diskuteras. Det visas att magnetism av sådana strukturer påverkas av kvantmekaniska effekter och anisotropin beteende är motsatsen till vad som observerats i kraftigt dopade nanorör. I den tvåa delen är Mn12-baserade enda-molekyl magneter med olika karboxylsyror ligander och deras 1:1 fulleren-utspädda komplex studeras. Vi visar att magnetiska egenskaperna hos sådana system beror i hög grad på miljön, och i princip är det möjligt att utforma en magnet med önskvärda egenskaper. En av de studerade föreningarna visade en post blockeringstemperaturen för en enda molekylär magnet. Både fulleren-utspädda komplex visade "magnetisering utbildning" effekt i alternerande magnetfält och möjligheten att bevara magnetiskt moment. Den tredje och fjärde delarna av avhandlingen är avsedda för inneboende magnetism av analys av olika bidrag till magnetisk susceptibilitet av metall-fritt kol-baserade system -inskjutna föreningar grafit fluorider och nanoporösa O2-eroderade grafit. Magnetiska egenskaperna hos dessa system är starkt beroende av strukturen, och kan fint avstämmas genom att man ändrar π-elektronsystem av grafit, i. e. med graden av fluorering av inskjutna föreningar och genom införandet av bor föroreningar till värd matris av nanoporösa grafit.

In dieser Arbeit wurde die Ausgangsverbindung der eisenbasierten Supraleiter, LaFeAsO, durch die Synthese und Charakterisierung von poly- und einkristallinen Proben untersucht. Supraleitung kann in den eisenbasierten Supraleitern durch Elektronen- oder Lochdotierung hervorgerufen werden. Die Substitution von Eisen durch Mangan, formal eine Lochdotierung, hat hingegen einen destruktiven Effekt auf die Supraleitung. Dieser ist bei optimal fluordotiertem LaFeAs(O,F) um Größenordnungen stärker ausgeprägt als bei Nd- oder Sm-FeAs(O,F). Indem Lanthan partiell durch das kleinere Yttrium substituiert wurde, konnte gezeigt werden, dass diese unterschiedlich starke Mangantoleranz durch die Unterschiede im Seltenerdmetall-Ionenradius bedingt ist. Weiterhin finden sich Anzeichen, dass die Unterdrückung der Supraleitung durch Mangan mit Elektronenlokalisierung korreliert ist. Das Fehlen von großen dreidimensionalen Einkristallen der SEFeAsO-Verbindungsklasse stellt ein großes Hindernis in der Erforschung der elektronischen Eigenschaften der eisenbasierten Supraleiter dar. Im Rahmen dieser Arbeit konnte gezeigt werden, dass das Verfahren der Festkörper-Einkristallzüchtung ein geeignetes Mittel darstellt, um große, facettierte SEFeAsO-Einkristalle mit ausgeprägtem Wachstum in c-Richtung zu erhalten. Mit diesem neu entwickelten Einkristallzüchtungsverfahren konnte ein aktualisiertes Phasendiagramm von La(Fe,Co)AsO erstellt werden. Die Substitution von Eisen durch Cobalt entspricht einer Elektronendotierung und führt zu Supraleitung mit einer maximalen Sprungtemperatur von 12 K. Die Ausgangsverbindung LaFeAsO zeigt bei etwa 156 K einen strukturellen Phasenübergang von einer tetragonalen zu einer orthorhombischen Struktur, weiterhin tritt unterhalb von etwa 138 K eine Spindichtewelle auf. In Einklang mit dem bekannten Phasendiagramm werden mit Cobaltdotierung die beiden Übergänge unterdrückt, mit höheren Cobaltkonzentrationen kommt es zu Supraleitung. Anders als beim bekannten Phasendiagramm kann eine deutliche Aufspaltung zwischen magnetischem und strukturellen Übergang bei kleinen Cobaltkonzentrationen beobachtet werden. Außerdem findet sich eine Region der Koexistenz zwischen Supraleitung und Spindichtewelle. Bisher konnte ein solcher Zustand im SE(Fe,Co)AsO-System nicht beobachtet werden.

This thesis contains the results of the extensive study into the synthesis of nickel niobate (NiNb2O6) including the formation of what was a previously unreported polymorph of the material, as well as the magnetic properties of both cobalt niobate (CoNb2O6) and nickel niobate using techniques including SQUID magnetometry, powder and single crystal x-ray scattering, powder and single crystal neutron scattering and muon spin rotation/relaxation. In cobalt niobate we found extremely long relaxation times in the heat capacity which showed up strongly in muon spin rotation experiments but not in neutron measurements. Additionally, with field applied to the system we see the emergence of spin-wave like structures in the neutron scattering data. Within cobalt niobate the strongest interaction is ferromagnetic and along the chain. The chains themselves are laid out on a triangular fashion and interact, although far more weakly, in an antiferromagnetic manner. This triangular patterning as well as an antiferromagnetic interaction results in interchain frustration, which protects the quasi-1D nature of the system due to the difficulty generated in creating 3D order. In nickel niobate we found that growth conditions caused highly variable changes, and we were able to create two different polymorphs. One polymorph was in the same space group as cobalt niobate, which gave us an opportunity to explore the magnetic difference between a spin-½ and spin-1 magnetic system and in nickel niobate in the new space group we performed an ab initio characterization solving the unit cell structure, the magnetic structure with neutron scattering as well as a magnetic characterization with SQUID magnetometry and muon spin rotation, allowing us to contrast the significant crystallographic differences. For the new polymorph we were able to determine its magnetic structure, characterized by Ising-like spins arranged in frustrated tetrahedra with three of the four points lying in the same plane as the spin, and for both materials we were able to use zero-field μSR data to estimate behaviour near the critical point and determine a critical exponent near the magnetic transitions. In both polymorphs there is evidence of constrained magnetism or reduced dimensionality, although the evidence for low dimensionality is much stronger in the columbite polymorph. / Thesis / Doctor of Philosophy (PhD) / This thesis examines two different niobium-based compounds: cobalt niobate (CoNb2O6) and nickel niobate (NiNb2O6). In these systems the cobalt and nickel atoms provide interesting magnetic properties. Within a magnetic material, the magnetic atoms tend to have their spins align in certain ways. The atoms themselves are fixed to particular sites by the way the material is assembled; an atomic framework. In the case of cobalt niobate, the magnetic atoms are arranged in well-separated chains so that a magnetic atom interacts strongly with its magnetic neighbours within a chain, and weakly with ones that are further away. This is an example of a material that is called `low dimensional'. The chains themselves form triangular patterns, and the interactions between chains are both weaker and antialigned, which creates a frustrated competition between the chains, protecting the low dimensional state by creating conditions where it is hard for all the spins in the material to order. For nickel niobate, the magnetic moments all want to anti-align, or be pointing in the opposite direction as its nearest neighbour. The magnetism is `frustrated' because each magnetic atom is tetrahedrally connected to three other atoms, so it cannot meet that condition. This can be visualized by drawing a triangle and trying to make each corner have an arrow pointing up or down. The third corner of the triangle cannot satisfy this requirement for its neighbours (one up and one down arrow). Both decreased dimensionality and frustration can lead to the emergence of novel quantum states of matter at low temperature. This thesis explores these materials with that in mind.