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.

The aim of the present work is to clarify the interplay between the complex technological chain of crystal preparation, chemical and structural perfection of grown crystals of intermetallic compounds and oxides and their physical properties. This technological chain includes detailed studies of unknown or insufficiently known phase diagrams, their correlation with growth conditions and optimisation of process parameters for obtaining single crystals with high chemical and physical perfection. The measurements of the physical properties of the grown crystals such as superconductivity, thermoelectric or dielectric properties not only show new features and properties for application of the materials obtained, but also allow conclusions of the crystal perfection. The studies are focused on the following systems: RENi2B2C borocarbides (RE=Y, Tb or Ho) displaying superconductivity, magnetic order and a strong interplay between magnetic and superconducting properties for YNi2B2C, TbNi2B2C, HoNi2B2C, respectively; CeSi2-?Ô and Ru2Si3 as examples of systems with magnetic and promising thermoelectric properties, respectively; MgB2 and LiBC to test of theoretical predictions of the new superconducting intermetallic compounds discovered in the last years; SrTiO3 and SrZrO3 oxide compounds with special dielectric and optical properties. For this wide spectrum of substances necessarily different growth techniques were applied. That is mainly the floating zone (FZ) or travelling solvent floating zone (TSFZ) techniques with optical heating. Flux techniques were used if the vapour pressure of composing elements is high such as for Mg and Li. The crucible free FZ technique is very attractive for the crystal growth of these intermetallic and oxide compounds to avoid contamination with the crucible material, if the melts have very high chemical reactivity, high melting temperatures and if a large crystal size (at least 3-5 mm) is desired for corresponding physical measurements. One special aim in the presented work is the optimisation of the preparation and growth process features with respect to crystal perfection, establishing new relationships between process parameters, crystal perfection, crystallographic structure, composition of grown crystals and the related physical properties. Optimisation of crystal growth process requires own constitutional studies of growth relevant parts of corresponding multicomponent phase diagrams. Therefore, parts of the phase diagrams were experimentally revealed by differential thermal analysis (DTA), optical metallography and EPMA and partially combined with CALPHAD calculations.

Die Dissertation beschreibt Untersuchungen der intermetallischen Verbindungen TbxY1-xNi2B2C bzw. TbxEr1-xNi2B2C, Tb2PdSi3 sowie Dy2PdSi3, die sich auszeichnen durch physikalische Erscheinungen, die durch die Wechselwirkung der magnetischen Momente der Seltenerd (SE)-Ionen mit den Leitungselektronen hervorgerufen werden. Sie umfasst Beiträge zur Konstitution der Legierungssysteme, methodische Untersuchungen zur Einkristallzüchtung, zur Charakterisierung der Homogenität und Perfektion der Kristalle und zu physikalischen Eigenschaften (Supraleitung, Magnetismus). Die für das Erstarrungs- und Schmelzverhalten der intermetallischen Phasen relevanten quasi-binären Schnitte der Tb-(Y, Er)-Ni-B-C bzw. Tb(Dy)-Pd-Si-Phasendiagramme, die bisher noch nicht bekannt waren, konnten bestimmt werden. Damit wurden die Prozessparameter der Einkristallzüchtung durch tiegelfreies Zonenschmelzen optimiert. Die unterschiedlichen Erstarrungstypen, peritektische Erstarrung (SENi2B2C) bzw. kongruentes Erstarren (SE2PdSi3), wurden durch unterschiedliche Ziehgeschwindigkeiten bei der Einkristallzüchtung berücksichtigt. An den massiven Einkristallen wurden Homogenitätsuntersuchungen hinsichtlich Elementkonzentration und physikalischer Eigenschaften (Tc, Tn, RRR) als Funktion der Längskoordinate durchgeführt, die geringe Eigenschaftsunterschiede der einkristallinen Proben nachweisen. Aus der Zusammensetzungsänderung über die Kristalllänge konnte in Verbindung mit in-situ Messungen der Zonentemperatur ein einfaches Prozessmodell des Zonenschmelzens der untersuchten Verbindungen entwickelt werden. Die Korrelation von magnetischen und supraleitenden Eigenschaften der Borokarbidmischreihen werden primär vom Verhältnis der Seltenen Erden bestimmt aber auch durch die Konzentration der weiteren Elemente. An Einkristallen konnte eine Anisotropie des oberen kritischen Feldes der Supraleitung von TbxY1-xNi2B2C gezeigt werden, die durch die magnetischen Tb-Ionen bestimmt wird. Die Untersuchungen der Tb2PdSi3- und Dy2PdSi3-Einkristalle ergaben eine Anisotropie der magnetoelektrischen Eigenschaften. / In this thesis investigations of the intermetallic compounds TbxY1-xNi2B2C, TbxEr1-xNi2B2C, Tb2PdSi3 and Dy2PdSi3 are presented. These compounds exhibit interesting physical phenomena caused by the interaction of the rare earth (RE) magnetic moments on the conduction electrons. Moreover, contributions on the constitution of the alloy systems, basic investigations of crystal growth process, homogeneity, microstructure and physical properties (superconductivity, magnetism) of the crystals are given. The quasi-binary sections of the Tb-(Y, Er)-Ni-B-C and Tb(Dy)-Pd-Si-phase diagrams which are relevant for the crystallisation of the different intermetallic phases have been determined for the first time. They were utilised for optimisation of the process parameters of single crystal growth by floating-zone melting. Because of the different solidification modes of RENi2B2C (peritectic solidification) and RE2PdSi3 (congruent solidification) different growth velocities have been employed in crystal growth. The composition and the physical properties (Tc, Tn, RRR) have been investigated as function of the crystal axis co-ordinate. As these properties show only a slight shift over the crystal length samples are representative for the whole crystal. From the slight composition shift over the crystal length a process model of the floating zone growth has been developed utilising the in-situ measurements of the zone-temperature. The correlation of magnetic and superconducting properties of the borocarbide solid solution compounds are mainly governed by the RE-fraction but they are also influenced by the concentration of the other elements. For TbxY1-xNi2B2C single crystals an anisotropic upper critical field of superconductivity has been detected which is induced by the magnetic Tb-ions. The investigations of Tb2PdSi3 and Dy2PdSi3 revealed an anisotropy of the magnetoresistive properties.

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.

Die Dissertation beschreibt Untersuchungen der intermetallischen Verbindungen TbxY1-xNi2B2C bzw. TbxEr1-xNi2B2C, Tb2PdSi3 sowie Dy2PdSi3, die sich auszeichnen durch physikalische Erscheinungen, die durch die Wechselwirkung der magnetischen Momente der Seltenerd (SE)-Ionen mit den Leitungselektronen hervorgerufen werden. Sie umfasst Beiträge zur Konstitution der Legierungssysteme, methodische Untersuchungen zur Einkristallzüchtung, zur Charakterisierung der Homogenität und Perfektion der Kristalle und zu physikalischen Eigenschaften (Supraleitung, Magnetismus). Die für das Erstarrungs- und Schmelzverhalten der intermetallischen Phasen relevanten quasi-binären Schnitte der Tb-(Y, Er)-Ni-B-C bzw. Tb(Dy)-Pd-Si-Phasendiagramme, die bisher noch nicht bekannt waren, konnten bestimmt werden. Damit wurden die Prozessparameter der Einkristallzüchtung durch tiegelfreies Zonenschmelzen optimiert. Die unterschiedlichen Erstarrungstypen, peritektische Erstarrung (SENi2B2C) bzw. kongruentes Erstarren (SE2PdSi3), wurden durch unterschiedliche Ziehgeschwindigkeiten bei der Einkristallzüchtung berücksichtigt. An den massiven Einkristallen wurden Homogenitätsuntersuchungen hinsichtlich Elementkonzentration und physikalischer Eigenschaften (Tc, Tn, RRR) als Funktion der Längskoordinate durchgeführt, die geringe Eigenschaftsunterschiede der einkristallinen Proben nachweisen. Aus der Zusammensetzungsänderung über die Kristalllänge konnte in Verbindung mit in-situ Messungen der Zonentemperatur ein einfaches Prozessmodell des Zonenschmelzens der untersuchten Verbindungen entwickelt werden. Die Korrelation von magnetischen und supraleitenden Eigenschaften der Borokarbidmischreihen werden primär vom Verhältnis der Seltenen Erden bestimmt aber auch durch die Konzentration der weiteren Elemente. An Einkristallen konnte eine Anisotropie des oberen kritischen Feldes der Supraleitung von TbxY1-xNi2B2C gezeigt werden, die durch die magnetischen Tb-Ionen bestimmt wird. Die Untersuchungen der Tb2PdSi3- und Dy2PdSi3-Einkristalle ergaben eine Anisotropie der magnetoelektrischen Eigenschaften. / In this thesis investigations of the intermetallic compounds TbxY1-xNi2B2C, TbxEr1-xNi2B2C, Tb2PdSi3 and Dy2PdSi3 are presented. These compounds exhibit interesting physical phenomena caused by the interaction of the rare earth (RE) magnetic moments on the conduction electrons. Moreover, contributions on the constitution of the alloy systems, basic investigations of crystal growth process, homogeneity, microstructure and physical properties (superconductivity, magnetism) of the crystals are given. The quasi-binary sections of the Tb-(Y, Er)-Ni-B-C and Tb(Dy)-Pd-Si-phase diagrams which are relevant for the crystallisation of the different intermetallic phases have been determined for the first time. They were utilised for optimisation of the process parameters of single crystal growth by floating-zone melting. Because of the different solidification modes of RENi2B2C (peritectic solidification) and RE2PdSi3 (congruent solidification) different growth velocities have been employed in crystal growth. The composition and the physical properties (Tc, Tn, RRR) have been investigated as function of the crystal axis co-ordinate. As these properties show only a slight shift over the crystal length samples are representative for the whole crystal. From the slight composition shift over the crystal length a process model of the floating zone growth has been developed utilising the in-situ measurements of the zone-temperature. The correlation of magnetic and superconducting properties of the borocarbide solid solution compounds are mainly governed by the RE-fraction but they are also influenced by the concentration of the other elements. For TbxY1-xNi2B2C single crystals an anisotropic upper critical field of superconductivity has been detected which is induced by the magnetic Tb-ions. The investigations of Tb2PdSi3 and Dy2PdSi3 revealed an anisotropy of the magnetoresistive properties.

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.

The aim of the present work is to clarify the interplay between the complex technological chain of crystal preparation, chemical and structural perfection of grown crystals of intermetallic compounds and oxides and their physical properties. This technological chain includes detailed studies of unknown or insufficiently known phase diagrams, their correlation with growth conditions and optimisation of process parameters for obtaining single crystals with high chemical and physical perfection. The measurements of the physical properties of the grown crystals such as superconductivity, thermoelectric or dielectric properties not only show new features and properties for application of the materials obtained, but also allow conclusions of the crystal perfection. The studies are focused on the following systems: RENi2B2C borocarbides (RE=Y, Tb or Ho) displaying superconductivity, magnetic order and a strong interplay between magnetic and superconducting properties for YNi2B2C, TbNi2B2C, HoNi2B2C, respectively; CeSi2-?Ô and Ru2Si3 as examples of systems with magnetic and promising thermoelectric properties, respectively; MgB2 and LiBC to test of theoretical predictions of the new superconducting intermetallic compounds discovered in the last years; SrTiO3 and SrZrO3 oxide compounds with special dielectric and optical properties. For this wide spectrum of substances necessarily different growth techniques were applied. That is mainly the floating zone (FZ) or travelling solvent floating zone (TSFZ) techniques with optical heating. Flux techniques were used if the vapour pressure of composing elements is high such as for Mg and Li. The crucible free FZ technique is very attractive for the crystal growth of these intermetallic and oxide compounds to avoid contamination with the crucible material, if the melts have very high chemical reactivity, high melting temperatures and if a large crystal size (at least 3-5 mm) is desired for corresponding physical measurements. One special aim in the presented work is the optimisation of the preparation and growth process features with respect to crystal perfection, establishing new relationships between process parameters, crystal perfection, crystallographic structure, composition of grown crystals and the related physical properties. Optimisation of crystal growth process requires own constitutional studies of growth relevant parts of corresponding multicomponent phase diagrams. Therefore, parts of the phase diagrams were experimentally revealed by differential thermal analysis (DTA), optical metallography and EPMA and partially combined with CALPHAD calculations.