The field of low-dimensional quantum magnets has received lot of attention owing to the possibility of studying phenomena associated with the quantum nature of matter. Many materials that realize low-dimensional spin arrangements in their structure have been synthesized in the past twenty years due to the emergence and development of crystal growth techniques. These materials have been studied using various experiments in order to explore the wide range of interesting properties predicted theoretically for low-dimensional systems. In this pursuit, novel properties have been observed and many open questions have been raised. One such property that is typically observed in many low-dimensional quantum magnets is heat transport via magnetic excitations. Large magnitudes of magnetic heat conductivity has been found experimentally in materials belonging to this class in addition to the conventionally known phononic heat conduction, and interesting theoretical predictions like the divergence of heat conductivity in certain spin models exist, that have stimulated research in this field. This experimental work mainly deals with the crystal growth and heat transport properties of low-dimensional quantum magnets that include one-dimensional (1D) spin chain systems Sr$_2$CuO$_3$ and SrCuO$_2$, two-dimensional (2D) Heisenberg antiferromagnet La$_2$CuO$_4$, and a five-leg spin ladder La$_8$Cu$_7$O$_{19}$, with a view to understand propagating low-energy magnetic excitations and their interaction amongst themselves, other quasiparticles and impurities present in the systems. These interactions result in scattering processes that govern the magnitude and temperature dependence of heat conductivity. In spite of considerable theoretical and experimental work in the field of heat transport, a complete understanding of the scattering mechanisms is lacking. The work tries to add to the experimental knowledge about magnetic heat transport in such systems and presents cases which motivate the need for theoretical understanding of aspects of heat transport. The focus of this work was twofold. One part focusses on the single crystal growth using the travelling-solvent floating zone (TFSZ) method of materials which realize low-dimensional spin systems in their structure. The TFSZ method is indispensable for growing large single crystals of extraordinary purity, which can be used for investigations using neutrons and other techniques like heat conductivity measurements that probe anisotropic properties. The other part deals with the experimental results on heat transport and other thermodynamic properties of these materials. In order to study the behaviour of the magnetic heat conductivity at high temperatures, and the effect of small amount of magnetic and non-magnetic impurities on the heat transport of 2D Heisenberg antiferromagnet La$_2$CuO$_4$, single crystals of pure La$_2$CuO$_4$, and Ni- and Zn-doped versions, La$_2$Cu$_x$Ni$_{1-x}$O$_4$ and La$_2$Cu$_x$Zn$_{1-x}$O$_4$ for $x$ = 0.001 and 0.003, were grown using the TFSZ method. Heat transport in the pure compound was experimentally investigated for the first time up to very high temperatures of 813 K using two methods, namely the steady state method for low temperatures and the dynamic flash method for measuring high temperature conductivity. Analysis of the magnon mean-free path using empirical models based on semi-classical theories, and qualitative comparison to theoretical calculations seems to suggest that scattering between magnons might play an important role in addition to scattering of magnons with phonons and defects, and that the spin-spin correlation length could be crucial in limiting the mean free path of magnons at high temperatures. These experimental results and indications of probable scattering mechanisms based on non-rigorous analyses and comparisons, strongly motivate the need for theoretical studies. Heat conductivity measurements on the Ni- and Zn- doped versions of La$_2$CuO$_4$ are still incomplete and inconclusive, and hence have not been reported in this work. Heat transport experiments on Ni- and Ca-doped Sr$_2$CuO$_3$ were performed, with a motivation to investigate the role of disorder induced by impurities lying within the spin chains (Ni) and those lying outside the spin chains (Ca), on the heat transport in this system. In both the cases, the magnetic heat transport is observed to be strongly suppressed upon doping. Empirical analysis of the data seems to suggest that in the temperature regime of 100-300 K, the temperature dependence of the mean-free path of magnetic excitations for the Ni- and Ca-doped samples can be described by scattering with defects (Ni and Ca impurities) and phonons alone. However, surprisingly, a strong increase of phononic conductivity is observed perpendicular and parallel to the spin chains of the Ni-doped compounds compared to the pure compounds, whose explanation seems to lie in the existence of an additional dissipative scattering mechanism present in the pure compounds that is lifted upon doping, possibly due to the presence of a spin gap in the doped compounds. The effect of Ni on the Sr$_2$CuO$_3$ and SrCuO$_2$ was also investigated by studying the low energy regime of the spin excitation spectrum using other microscopic probes like nuclear magnetic resonance (NMR) and inelastic neutron scattering (INS). Large single crystals of SrCu$_x$Ni$_{1-x}$O$_2$, with $x$ = 0.01 were grown and used in these experiments that observed the presence of a spin gap in the Ni-doped sample. Further theoretical investigations are however required to understand the possible role of the spin gap in influencing the spin-phonon scattering mechanism, and its relevance to the observed enhancement in phononic conduction. Although we observe that in the case of both 1D and 2D systems, a semi-classical kinetic model for heat transport along with empirical models of scattering processes describe the temperature dependence of the measured heat conductivity surprisingly well in the temperature regime up to 300 K and 800 K respectively, interpretations based on these analyses must be treated as only preliminary, and as a step towards understanding microscopically the scattering mechanisms involved in low-dimensional systems such as the ones discussed in this work. In the direction of exploratory research towards synthesis of novel low-dimensional materials, two cuprate compounds were synthesized in the form of single crystals using the floating zone method for the first time, namely, a five leg $S=tfrac{1}{2}$ antiferromagnetic spin ladder compound La$_8$Cu$_7$O$_{19}$ and an insulating delafossite LaCuO$_{2}$. A bulk 3D antiferromagnetic ordering is observed in La$_8$Cu$_7$O$_{19}$. Heat conductivity of La$_8$Cu$_7$O$_{19}$ is observed to be purely phononic and no contribution from magnetic excitations seem to exist, although the measurements indicates that there is a large anisotropy in heat transport. However, detailed diffraction experiments using x-rays and neutrons indicate that both the crystal and magnetic structures are complicated, and that the details of the structure prevent La$_8$Cu$_7$O$_{19}$ from being a perfect realization of a five-leg spin ladder.

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.

In der vorliegenden Arbeit werden wissenschaftlich-technologische Untersuchungen zur wandabgelösten VGF-Züchtung von Germanium präsentiert. Dazu wurden zwei Varianten mit Hinblick auf die Etablierung und Stabilisierung bestimmter Druckverhältnisse angewendet: (i) Beim passiven dVGF-Verfahren erfolgt die Erzeugung der Druckdifferenz über die thermische Beeinflussung des Inertgases Ar, und (ii) beim erstmals gezeigten aktiven dVGF-Verfahren über eine temperaturkontrollierte, separate Zn-Dampfdruckquelle. Ge-Einkristalle mit einem Durchmesser bis zu 3 Zoll wurden nahezu vollständig ohne Tiegelkontakt gezüchtet. Der Effekt der Wandablösung wird anhand der mikroskopischen Charakterisierung der Kristalloberfläche, der Durchbiegung der Phasengrenze sowie der etch pit density (EPD), ein Maß für die Versetzungsdichte gezeigt. Im Vergleich zu konventionell gezüchteten VGF-Kristallen zeigen die detached gezüchteten Kristalle eine hohe strukturelle Qualität. Dies wird auf reduzierte thermische und thermo-mechanische Spannungen bei der wandabgelösten Züchtung zurückgeführt.

This experimental work focusses on the magnetic thermal conductivity, κ_mag, of the one-dimensional two-leg spin ladder system Sr_14Cu_24O_41 and the spin chain system SrCuO_2. These two S = 1/2 antiferromagnetic Heisenberg compounds possess enormous magnetic contributions to the heat transport which in some cases exceed the phonon contributions by more than one order of magnitude. Despite of intense ongoing experimental and theoretical investigations, the underlying mechanism of the magnetic heat transport remains unclear. The study of κ_mag aims a better understanding of the basic physics which determine mobility, scattering and dissipation of the dispersing magnetic excitations. The most important tool used in this study is to selectively influence the structure and the electronic and magnetic properties of the compounds through doping. For this purpose single crystalline samples were produced using the Traveling Solvent Floating Zone technique, a crucible-free technology, which allows the growth of centimeter sized single crystals of high quality. In particular, the successful growth of large quantities of the hole-free ladders La_4Sr_10Cu_24O_41 allowed the realization of inelastic neutron scattering and, for the first time, the acquisition of the complete magnetic excitation spectrum of the spin ladder, composed not only by the triplon band, but also by the two-triplon continuum, permitting an accurate determination of the coupling constants in this system. The importance of the cyclic-exchange, previously unclear, was asserted. In order to study the scattering mechanisms of the magnetic excitations (triplons) off static defects in the two-leg ladder Sr_14Cu_24O_41, this compound was doped with tiny amounts of Zn. Occupying the Cu site in the ladders, the Zn plays the role of a non-magnetic defect, imposing an upper limit to the mean free path of the triplons. The thermal conductivity of Sr_14Cu_(14−z)Zn_zO_41, with z = 0, 0.125, 0.25, 0.5 and 0.75, shows a strong decrease of both the phononic and magnetic contributions with increasing z value. In particular, the decrease of the magnetic part indicates an increased scattering of the triplons off Zn defects. The analysis of κ_mag, using a kinetic model, allows the extraction of the triplon mean free path l_mag. This quantity was successfully correlated to the mean Zn-Zn distance along the ladders, confirming the validity of the employed kinetic model and corroborating results of previous works. In SrCuO_2, the magnetic contribution to the thermal conductivity appears as a hump-like anomaly on the high-T back of the low-T phonon peak. In order to better separate the magnetic contribution from the phononic background, small amounts of Sr were substituted by the smaller and lighter Ca, leading, on the one hand, to an increased scattering of the phonons and consequently to a suppression of the phononic thermal conductivity. On the other hand, since Ca is isovalent to Sr, no significant changes of the magnetic properties of the system are expected: a magnetic peak belonging to κ_mag should appear. Measurements of the thermal conductivity of Sr_(1−x)Ca_xCuO_2 for x = 0, 0.0125, 0.025, 0.05 and 0.1 show indeed a systematic decrease of the phonon thermal conductivity with increasing x. However, against initial expectations, no magnetic peak appears. Instead, the magnetic thermal conductivity decreases at intermediate and low temperatures with increasing doping level, indicating a strong influence of the Ca dopant on the magnetic system. Surprisingly, no changes of κ_mag occur at higher temperatures, where κ_mag remains constant for all doping levels. To explain this intriguing temperature and doping dependence of κ_mag, three scenarios are proposed. One of the scenarios is based on the phenomenon of mutual spinon and phonon heat transport, the so called spin-phonon-drag mechanism. Another scenario assumes an effective scattering of spinons off Ca defects. In a third scenario, the appearance of a gap in the doped compounds is considered. The obvious effect of the Ca dopant on the magnetic thermal conductivity motivated a more detailed investigation of the doping dependence of electronic and magnetic properties in Sr_(1−x)Ca_xCuO_2. NMR data reveal the presence of a magnetic gap for the x = 0.1 compound. The doping dependent evolution of the specific heat at low-T is consistent with this result. Furthermore, susceptibility data may be explained within a segmentation of the spin chains, which in turn can be also related to the opening of a gap. These results strongly support that the reduction of κ_mag in the Ca doped compounds is related to a smaller number of magnetic excitations participating in the heat transport due to the presence of the gap. A possible reduction of the chain length, as suggested by the susceptibility data, is also consistent with the scenario of a reduced κ_mag due to an increased scattering of magnetic excitations. In spite of these partially consistent results, there are still no clear-cut explanations for the evolution of κ_mag upon doping. In particular, it cannot be completely ruled out that a fraction of the Ca dopant goes into the chains, a point which has to be urgently clarified in order to allow a correct interpretation of the data.

Title: Study of indium doped shape-memory alloy Ni2MnGa Author: Petr Cejpek Department: Department of Condensed Matter Physics Supervisor: RNDr. Milan Dopita, PhD., Department of Condensed Matter Physics Abstract: The alloys related to Ni-Mn-Ga system exhibit effects connected to the magnetic shape-memory and martensitic transformation and therefore attract attention of researchers for their application potential. Properties and especially transformation temperatures are strongly dependent on composition, doping and also on external conditions as a magnetic field or pressure. The main aim of the work was to prepare own single crystals of Ni2MnGa1−xInx and to study their properties with respect to the temperature and applied fields in dependence on a various indium doping. The transformation temperatures obtained from the measurement of electrical resistivity and magnetisation re- vealed the systematic decrease of martensitic transformation temperature TM , pre-martensitic transformation temperature TP and Curie temperature TC. The martensitic transformation should vanish at indium concentration of x ≈ 0.10. The decrease with indium content is much faster than in the study published previously on the polycrystalline samples (vanishing at x ≈ 0.20). This dis- crepancy is probably caused by the residual stress...

Le travail a consisté, dans une première partie, à modéliser la dynamique des défauts ponctuels dans les mono-cristaux de silicium. Il s'est agi en premier lieu d'analyser en profondeur le modèle physique, pour introduire et comprendre le rôle de la thermodiffusion dans le modèle de transport-diffusion et recombinaison des interstitiels et des lacunes. Par une analyse asymptotique, nous sommes parvenus à prédire la composition du cristal en termes des densités de lacunes ou d'interstitiels. Nous avons également proposé un nouvel ensemble de paramètres matériels tenant compte de résultats d'expériences récentes sur la diffusivité des lacunes. Enfin, nous avons simulé numériquement le calcul des défauts ponctuels dans le procédé Czochralski de croissance de cristaux de silicium et l'avons validé par comparaison avec des résultats expérimentaux. Le travail principal dans cette thèse a consisté en l'élaboration d'une théorie mathématique permettant de décrire de manière rigoureuse la géométrie des dislocations dans les mono-cristaux. Par nature, ces défauts sont concentrés sur des lignes qui sont libres de former des réseaux complexes interagissant à leur tour avec les défauts ponctuels. Il s'est agi de proposer une théorie à l'échelle mésoscopique qui tienne compte à la fois de la multiformité des champs de déplacement et rotation tout en admettant que les effets non-élastiques soient concentrés dans la ligne. Les principaux champs intervenant dans cette théorie sont des densités de dislocations et de disclinations représentés par des tenseurs d'ordre 2 tenant compte à la fois de l'orientation de la ligne et des vecteurs de Frank et Burgers, qui sont des invariants caractérisant respectivement les défauts de rotation et de déplacement dans le cristal. Ces champs sont reliés à l'incompatibilité de la déformation élastique par l'intermédiaire de termes concentrés sur les lignes, qu'il a fallu décrire et formaliser dans un cadre mathématique rigoureux et cohérent. La description de la physique des dislocations a été rendue possible par l'application à la théorie des dislocations de certains nouveaux outils mathématiques tels, par exemple, la théorie des distributions, la théorie géométrique de la mesure, et la géométrie non-riemannienne. Enfin, l'homogénéisation de l'échelle mésoscopique vers l'échelle macroscopique des densités de dislocations, représentées par des tenseurs d'ordre 2, a permis de poser le problème à l'échelle du cristal, où les champs sont réguliers, obéissent à des lois de conservation, de constitution et d'évolution. Le travail de thèse s'est arrêté précisément au moment de modéliser l'échelle macroscopique, notamment les lois de constitution des densités de dislocations. / This thesis comprises two main parts and provides contributions to the fields of point- and line defects in single crystals. The point-defect transport, diffusion and recombination mechanisms are modeled in silicon crystals, whereas a theoretical approach is developped for the description of the geometry of dislocations. Therefore, plasticity, which is caused by the motion of dislocations, is not the topic of the present work. Dislocations are typical line-defects. Once generated during the growth of a silicon or other crystal, they can instantaneously multiply and generate dislocation networks, that render the material unusable for device manufacturing. We develop a theory to represent dislocated single crystals at the mesoscopic scale by considering concentrated effects along the dislocation line, as governed by the distribution theory combined with multiple-valued kinematic fields. Fundamental 2D identities relating the incompatibility tensor to the Frank and Burgers vectors are proved under global assumptions on the elastic strain, relying on the geometric measure theory, thereby giving rise to rigorous homogenisation from mesoscopic to macroscopic scale. The class of point-defects comprises the monoatomic defects which form the fundamental building blocks for grown-in defects in silicon crystals. A general model is build to conduct fully time-dependent and global simulations in order to predict the distribution of point-defects in a growing silicon crystal. Furthermore, the defect governing model is adapted in order to better agree with available measurements of self-interstitial and vacancy diffusion coefficients while respecting the V/G criterion, which characterises the interstitial-vacancy transition in the crystal. It is shown that introducing a thermal drift effect can facilitate the construction of a relevant model satisfying both conditions.

Fe chalcogenides : The discovery of superconductivity in Fe based compounds trig- gered an intense research activity in this field with significant importance given to material synthesis. As a result, numerous materials falling into four major classes and sharing similarities in physical properties were synthesized and investigated. In spite of subtle differences, all of them share many common features like crystal symmetry, magnetic ground state, close resemblance in phase diagram etc. Fe super- conductors are broadly classified into Fe pnictides (with Fe − pnictogen layer) and Fe chalcogenides (with Fe − chalcogen layer) in which the binary Fe chalcogenides possess the simplest crystal structure. The distinct magnetic and superconducting properties make them interesting candidates for research. Detailed study on such systems demand high quality single crystals. This thesis discusses single crystal growth and properties of Fe1+yTe1−xSex. Struc- tural, magnetic, superconducting and thermal properties of pristine and substituted compounds are explored. A characteristic feature associated with binary chalco- genides is the presence of excess Fe in the interstitial sites represented by y in the chemical formula. By fine tuning the composition, the effect of interstitial Fe on various physical properties can be analyzed. The current work deals with the influence of interstitial excess Fe on the structural, magnetic and superconducting properties of the parent compound Fe1+yTe and Se substituted Fe1+yTe1−xSex. The results are organized into eight chapters; an outline of each chapter is given below. Chapter 1 gives an introduction to the broad field of Fe superconductors. A de- tailed literature review providing comparison of Fe pnictides with chalcogenides is included. The background of the current work is discussed with reference to the im- portant aspects of crystal structure and its relation to the ordered ground states. An overview of the important theories on magnetic ordering and superconducting pair- ing is provided. In the later part, a generic phase diagram along with the individual phase diagrams of important systems are discussed. This is followed by a discus- sion of the characteristic properties of iron chalcogenides and different methods of bulk synthesis. The chapter is concluded with a note on the motivation behind the present work. Chapter 2 discusses the crystal growth techniques and experimental methods used in the present work. The basic working principles are briefly explained. Chapter 3 provides a detailed discussion of the single crystal growth procedure, its customization and basic characterization. Single crystals of all compositions un- der discussion are grown by a modified horizontal Bridgman method. Material preparation, growth parameters and overall temperature profile of crystal growth process are described. Single crystalline nature of the as-grown crystals is con- firmed with Laue scattering technique. All crystals show tetragonal symmetry at room temperature. The approximate crystal orientation is deduced by indexing the X-ray diffraction pattern of the cleaved crystals. The diffraction patterns exhibit a set of (00l) peaks. A detailed composition analysis is performed on the samples. The sample properties are very sensitive to composition and careful estimation is per- formed by conducting repeated measurements at multiple points on the samples under study. Chapter 4 deals with superconducting and magnetic properties of Fe1+yTe0.5Se0.5. Single crystals of two different Fe concentration, y=0.04 and 0.09 are grown in which the concentration of Se and Te are maintained close to 0.5. Among binary Fe chalcogenides, half substituted iron telluride shows the highest TC (15 K) at ambient pressure. Accordingly, this composition is chosen to evaluate the role of Fe concentration in modulating the superconducting behavior. Two different batches of both the samples are grown, one set containing small amounts of impurity phases and the other, representing a pure primary phase. Resistivity measurements performed on both compositions, y=0.04 and 0.09, show onset of superconductivity near 15 K. In the normal state above TC, the temperature derivative of resistivity dρ/dT changes from positive to negative as the excess Fe concentration rises. At higher Fe concentrations, a log 1/T divergence is discernible in the normal state. The contribution of interstitial Fe to superconductivity has been analyzed using magnetization measurement techniques. An increase in the width of superconducting transition is seen in all measurements as the Fe content increases. The superconducting volume fraction estimated from susceptibility data demonstrates that high concentration of Fe is not favorable to superconductivity. The upper and lower critical field are esti- mated from electric resistivity data (in applied magnetic field) and magnetization isotherms respectively. Comparison of the lower critical field between two compo- sitions strengthens the argument that higher excess Fe leads to suppression of super- conductivity. The second set of crystals with impurity phases reveals an anomalous magnetization peak near 125 K. The results from resistivity, DC magnetization and ac susceptibility are compared. Chapter 5 addresses the influence of excess Fe on the ordered ground state. The antiferromagnetic parent compound, Fe1+yTe single crystals, are also grown using the same procedure. It is proposed that excess Fe occupying the interstitial sites possess local moments which could interact with the magnetic phases. In an at- tempt to understand their magnetic properties in detail, single crystals are grown with y=0.06, 0.09, 0.11, 0.12, 0.13 and 0.15. Fe1+yTe undergoes magnetostructural transition at TN=67 K. As the concentration of Fe varies from 0.06 to 0.13, a marked suppression of TN occurs from 67 K to 56 K. Moreover, a single first order transi- tion is seen to split into two at the critical concentration, y=0.12. The derivative plot of magnetization and specific heat data clearly illustrate two well-separated peaks. The two transitions are denoted as TN=57 K and TS=46 K. TN here is identified as a second order transition and TS as a first order transition. The second order transi- tion is evident from the λ-like nature of the peak in the specific heat measurement. The first order transition is associated with a large thermal hysteresis in the heat- ing and cooling cycle. Raw data from the heat capacity calorimeter gives a clear hint towards the first order nature of TS. As the composition of Fe rises further, the multiple transitions subside and disappear. For higher concentration, y=0.15, a sin- gle continuous phase transition is observed. Impurity free, pure phase is noticed in most of the samples as evident in powder X-ray diffraction and bulk magneti- zation measurements. The thermal data of various compositions are analyzed and compared. Electrical resistivity data clearly reveals the shift in phase transition and the presence of multiple transitions. Unlike Fe1+yTe1−xSex, all compositions here display similar behavior above TN, irrespective of the concentration of excess Fe. Chapter 6 devotes special emphasis to the evolution of structural and magnetic properties of the critical composition, Fe1.12Te where multiple transitions are ob- served. The low temperature structure of the crystal is studied in detail using syn- chrotron powder X-ray diffraction. The data in the vicinity of the two transitions, TN and TS are carefully analyzed. The room temperature crystal structure belongs to tetragonal symmetry with P4/nmm space group, where it is paramagnetic. As the sample is cooled to just below TN, a magnetostructural transition occurs from tetragonal to orthorhombic space group Pmmn. Below TN, the XRD pattern of the tetragonal (200) peak splits into (200) and (020) representing an orthorhombic distortion. The second transition is observed at TS where the orthorhombic struc- ture undergoes a monoclinic distortion, to P21/m. Below TS, a mixed phase of or thorhombic and monoclinic structures are present. The powder diffraction studies are supplemented with thermodynamic measurements. From specific heat analy- sis, the different contributions and the change in entropy across the transitions are estimated. Linear thermal expansion study has confirmed the two structural transi- tions. The changes occurring in lattice parameters, bond distances, bond angles and unit cell volume as a function of temperature are calculated using powder pattern refinement. Synchrotron data, linear thermal expansion and thermodynamic mea- surement results all point to strong magnetostructural coupling in this material. A temperature-composition phase diagram is formulated using results obtained from different Fe compositions. Transition temperature is plotted as a function of excess Fe content, highlighting its role in determining the structural and magnetic phases in Fe1+yTe. Chapter 7 deals with the magnetic and superconducting properties of Se substi- tuted Fe1+yTe1−xSex. Single crystals are grown by carefully varying the concen- tration of Se from x=0.02 to 0.25 while keeping the nominal composition of excess Fe more or less same. In this work, focus is given to Fe-rich, selenium substituted compositions. The intention is to explore how Se substitution affects the multiple transitions observed in Fe1.12Te. At 2% Se substitution, the split peaks are evident with a slight shift in temperature. The temperature interval between the two tran- sitions decreases in comparison to the pristine compound. For further increases in Se concentration, instead of two well separated peaks, a weak broad hump is ob- served. For compositions with x >0.10, long range magnetic ordering is suppressed. As x increases above 0.15 the electrical resistivity drops indicating the onset of su- perconductivity. However, in the composition range 0.15 ≤ x ≤ 0.25, neither long range magnetic order nor bulk superconductivity is present. Alternately, weak magnetic transitions above the superconducting transition are visible. The transport and magnetic properties are similar to that observed in Fe1.09Te0.5Se0.5. By tuning the Se composition in Fe-rich samples, the magnetic and structural transitions, originally seen in the parent compound are suppressed. The emergence of superconductivity is also discussed. The last section of the chapter provides the modified phase diagram as a function of Se concentration, combining all compositions discussed in the thesis. This gives a detailed description of Fe chalcogenides in the composition range, x=0 to 0.5 with special emphasis on Fe rich samples. The different regions in the phases diagram describe the peculiar properties of Fe chalcogenides. Chapter 8 concludes the thesis with general conclusions pertaining to various observations made in the different chapters. Prospects for future work are briefly outlined.

Im Rahmen dieser Arbeit wurden die Kondo-Gitter YbT2Si2 (T = Rh, Ir, Co) und CeTPO (T = Ru, Os, Fe, Co) untersucht. In diesen Systemen treten starke ferromagnetische Korrelationen der 4f-Momente zusammen mit ausgeprägter Kondo-Wechselwirkung auf, deren theoretische Beschreibung bislang sehr kontrovers diskutiert wird. Diese Arbeit liefert damit einen essentiellen experimentellen Beitrag zur Physik von ferromagnetischen Kondo-Gittern. So konnten qualitativ hochwertige Einkristalle von YbRh2Si2 hergestellt und erstmalig an einem Schwere-Fermion-System deren kritische Fluktuationen um den magnetischen Phasenübergang analysiert werden. Weiterhin konnte das bis dahin unverstandene Auftreten einer Elektron-Spin-Resonanz (ESR)-Linie in YbT2Si2 auf ferromagnetische Korrelationen zurückgeführt werden. Außerdem wurde mit CeFePO ein neues Schwere-Fermion-System mit starken ferromagnetischen Korrelationen entdeckt sowie mit dem isoelektronischen CeRuPO der seltene Fall eines ferromagnetisch geordneten Kondo-Gitters realisiert. / Within the context of this thesis the Kondo lattices YbT2Si2 (T = Rh, Ir, Co) and CeTPO (T = Ru, Os, Fe, Co) were investigated. In these systems strong ferromagnetic correlations of the 4f-moments together with pronounced Kondo interactions are present, whose theoretical description are pres-ently controversial discussed. Therefore, this work gives an essential experimental contribution to the physics of ferromagnetic Kondo lattices. The main results include the growth of high-quality single crystals of YbRh2Si2 and the first analysis of the critical fluctuations around the magnetic phase transition in a heavy fermion system. Furthermore, the unexpected observation of an electron spin resonance in YbT2Si2 could be ascribed to ferromagnetic correlations. Moreover, a new heavy fermion system CeFePO with strong ferromagnetic correlations was found and with the isoelec-tronic CeRuPO the rare case of a ferromagnetic Kondo-lattice discovered.

Im Rahmen dieser Arbeit wurden die Kondo-Gitter YbT2Si2 (T = Rh, Ir, Co) und CeTPO (T = Ru, Os, Fe, Co) untersucht. In diesen Systemen treten starke ferromagnetische Korrelationen der 4f-Momente zusammen mit ausgeprägter Kondo-Wechselwirkung auf, deren theoretische Beschreibung bislang sehr kontrovers diskutiert wird. Diese Arbeit liefert damit einen essentiellen experimentellen Beitrag zur Physik von ferromagnetischen Kondo-Gittern. So konnten qualitativ hochwertige Einkristalle von YbRh2Si2 hergestellt und erstmalig an einem Schwere-Fermion-System deren kritische Fluktuationen um den magnetischen Phasenübergang analysiert werden. Weiterhin konnte das bis dahin unverstandene Auftreten einer Elektron-Spin-Resonanz (ESR)-Linie in YbT2Si2 auf ferromagnetische Korrelationen zurückgeführt werden. Außerdem wurde mit CeFePO ein neues Schwere-Fermion-System mit starken ferromagnetischen Korrelationen entdeckt sowie mit dem isoelektronischen CeRuPO der seltene Fall eines ferromagnetisch geordneten Kondo-Gitters realisiert. / Within the context of this thesis the Kondo lattices YbT2Si2 (T = Rh, Ir, Co) and CeTPO (T = Ru, Os, Fe, Co) were investigated. In these systems strong ferromagnetic correlations of the 4f-moments together with pronounced Kondo interactions are present, whose theoretical description are pres-ently controversial discussed. Therefore, this work gives an essential experimental contribution to the physics of ferromagnetic Kondo lattices. The main results include the growth of high-quality single crystals of YbRh2Si2 and the first analysis of the critical fluctuations around the magnetic phase transition in a heavy fermion system. Furthermore, the unexpected observation of an electron spin resonance in YbT2Si2 could be ascribed to ferromagnetic correlations. Moreover, a new heavy fermion system CeFePO with strong ferromagnetic correlations was found and with the isoelec-tronic CeRuPO the rare case of a ferromagnetic Kondo-lattice discovered.