Numerical study of homogeneous and heterogeneous crystal nucleation in colloidal systems

Im Rahmen dieser Arbeit wurden Computersimulationen von Keimbildungs- und Kris\-tallisationsprozessen in rnkolloidalen Systemen durchgef\"uhrt. rnEine Kombination von Monte-Carlo-Simulationsmethoden und der Forward-Flux-Sampling-Technik wurde rnimplementiert, um die homogene und heterogene Nukleation von Kristallen monodisperser Hart\-kugeln zu untersuchen. rnIm m\"a\ss{ig} unterk\"uhlten Bulk-Hartkugelsystem sagen wir die homogenen Nukleationsraten voraus und rnvergleichen die Resultate mit anderen theoretischen Ergebnissen und experimentellen Daten. rnWeiterhin analysieren wir die kristallinen Cluster in den Keimbildungs- und Wachstumszonen, rnwobei sich herausstellt, dass kristalline Cluster sich in unterschiedlichen Formen im System bilden. rnKleine Cluster sind eher l\"anglich in eine beliebige Richtung ausgedehnt, w\"ahrend gr\"o\ss{ere} rnCluster kompakter und von ellipsoidaler Gestalt sind. rn rnIm n\"achsten Teil untersuchen wir die heterogene Keimbildung an strukturierten bcc (100)-W\"anden. rnDie 2d-Analyse der kristallinen Schichten an der Wand zeigt, dass die Struktur der rnWand eine entscheidende Rolle in der Kristallisation von Hartkugelkolloiden spielt. rnWir sagen zudem die heterogenen Kristallbildungsraten bei verschiedenen \"Ubers\"attigungsgraden voraus. rnDurch Analyse der gr\"o\ss{ten} Cluster an der Wand sch\"atzen wir zus\"atzlich den Kontaktwinkel rnzwischen Kristallcluster und Wand ab. rnEs stellt sich heraus, dass wir in solchen Systemen weit von der Benetzungsregion rnentfernt sind und der Kristallisationsprozess durch heterogene Nukleation stattfindet. rn rnIm letzten Teil der Arbeit betrachten wir die Kristallisation von Lennard-Jones-Kolloidsystemen rnzwischen zwei ebenen W\"anden. rnUm die Erstarrungsprozesse f\"ur ein solches System zu untersuchen, haben wir eine Analyse des rnOrdnungsparameters f\"ur die Bindung-Ausrichtung in den Schichten durchgef\"urt. rnDie Ergebnisse zeigen, dass innerhalb einer Schicht keine hexatische Ordnung besteht, rnwelche auf einen Kosterlitz-Thouless-Schmelzvorgang hinweisen w\"urde. rnDie Hysterese in den Erhitzungs-Gefrier\-kurven zeigt dar\"uber hinaus, dass der Kristallisationsprozess rneinen aktivierten Prozess darstellt.

RF-sputter fabrication of magnetic garnet thin films and simulation modeling for 1-D magnetic photonic crystal waveguide devices

One dimensional magnetic photonic crystals (1D-MPC) are promising structures for integrated optical isolator applications. Rare earth substituted garnet thin films with proper Faraday rotation are required to fabricate planar 1D-MPCs. In this thesis, flat-top response 1D-MPC was proposed and spectral responses and Faraday rotation were modeled. Bismuth substituted iron garnet films were fabricated by RF magnetron sputtering and structures, compositions, birefringence and magnetooptical properties were studied. Double layer structures for single mode propagation were also fabricated by sputtering for the first time. Multilayer stacks with multiple defects (phase shift) composed of Ce-YIG and GGG quarter-wave plates were simulated by the transfer matrix method. The transmission and Faraday rotation characteristics were theoretically studied. It is found that flat-top response, with 100% transmission and near 45o rotation is achievable by adjusting the inter-defect spacing, for film structures as thin as 30 to 35 μm. This is better than 3-fold reduction in length compared to the best Ce-YIG films for comparable rotations, thus allows a considerable reduction in size in manufactured optical isolators. Transmission bands as wide as 7nm were predicted, which is considerable improvement over 2 defects structure. Effect of repetition number and ratio factor on transmission and Faraday rotation ripple factors for the case of 3 and 4 defects structure has been discussed. Diffraction across the structure corresponds to a longer optical path length. Thus the use of guided optics is required to minimize the insertion losses in integrated devices. This part is discussed in chapter 2 in this thesis. Bismuth substituted iron garnet thin films were prepared by RF magnetron sputtering. We investigated or measured the deposition parameters optimization, crystallinity, surface morphologies, composition, magnetic and magnetooptical properties. A very high crystalline quality garnet film with smooth surface has been heteroepitaxially grown on (111) GGG substrate for films less than 1μm. Dual layer structures with two distinct XRD peaks (within a single sputtered film) start to develop when films exceed this thickness. The development of dual layer structure was explained by compositional gradient across film thickness, rather than strain gradient proposed by other authors. Lower DC self bias or higher substrate temperature is found to help to delay the appearance of the 2nd layer. The deposited films show in-plane magnetization, which is advantageous for waveguide devices application. Propagation losses of fabricated waveguides can be decreased by annealing in an oxygen atmosphere from 25dB/cm to 10dB/cm. The Faraday rotation at λ=1.55μm were also measured for the waveguides. FR is small (10° for a 3mm long waveguide), due to the presence of linear birefringence. This part is covered in chapter 4. We also investigated the elimination of linear birefringence by thickness tuning method for our sputtered films. We examined the compressively and tensilely strained films and analyze the photoelastic response of the sputter deposited garnet films. It has been found that the net birefringence can be eliminated under planar compressive strain conditions by sputtering. Bi-layer GGG on garnet thin film yields a reduced birefringence. Temperature control during the sputter deposition of GGG cover layer is critical and strongly influences the magnetization and birefringence level in the waveguide. High temperature deposition lowers the magnetization and increases the linear birefringence in the garnet films. Double layer single mode structures fabricated by sputtering were also studied. The double layer, which shows an in-plane magnetization, has an increased RMS roughness upon upper layer deposition. The single mode characteristic was confirmed by prism coupler measurement. This part is discussed in chapter 5.

Optical properties and defect structure of Sr2+ co-doped LaBr3:5%Ce scintillation crystals

Sr2+ co-doped LaBr3:5%Ce scintillators show a record low energy resolution of 2% at 662 keV and a considerably better proportional response compared to standard LaBr3:5%Ce. This paper reports on the optical properties and time response of Sr co-doped LaBr3:5%Ce. Multiple excitation and emission bands were observed in X-ray and optically excited luminescence measurements. Those bands are ascribed to three different Ce3+ sites. The first is the unperturbed site with the same luminescence properties as those of standard LaBr3:Ce. The other two are perturbed sites with red-shifted 4f-5d1 Ce3+ excitation and emission bands, longer Ce3+ decay times, and smaller Stokes shifts. The lowering of the lowest 5d level of Ce3+ was ascribed to larger crystal field interactions at the perturbed sites. Two types of point defects in the LaBr3 matrix were proposed to explain the observed results. No Ce4+ ions were detected in Sr co-doped LaBr3:5%Ce by diffuse reflectance measurements.

Morphological ripening of fluid inclusions and coupled zone-refining in quartz crystals revealed by cathodoluminescence imaging: Implications for CL-petrography, fluid inclusion analysis and trace-element geothermometry

Cathodoluminescence (CL) studies have previously shown that some secondary fluid inclusions in luminescent quartz are surrounded by dark, non-luminescent patches, resulting from fracture-sealing by late, trace-element-poor quartz. This finding has led to the tacit generalization that all dark CL patches indicate influx of low temperature, late-stage fluids. In this study we have examined natural and synthetic hydrothermal quartz crystals using CL imaging supplemented by in-situ elemental analysis. The results lead us to propose that all natural, liquid-water-bearing inclusions in quartz, whether trapped on former crystal growth surfaces (i.e., of primary origin) or in healed fractures (i.e., of pseudosecondary or secondary origin), are surrounded by three-dimensional, non-luminescent patches. Cross-cutting relations show that the patches form after entrapment of the fluid inclusions and therefore they are not diagnostic of the timing of fluid entrapment. Instead, the dark patches reveal the mechanism by which fluid inclusions spontaneously approach morphological equilibrium and purify their host quartz over geological time. Fluid inclusions that contain solvent water perpetually dissolve and reprecipitate their walls, gradually adopting low-energy euhedral and equant shapes. Defects in the host quartz constitute solubility gradients that drive physical migration of the inclusions over distances of tens of μm (commonly) up to several mm (rarely). Inclusions thus sequester from their walls any trace elements (e.g., Li, Al, Na, Ti) present in excess of equilibrium concentrations, thereby chemically purifying their host crystals in a process analogous to industrial zone refining. Non-luminescent patches of quartz are left in their wake. Fluid inclusions that contain no liquid water as solvent (e.g., inclusions of low-density H2O vapor or other non-aqueous volatiles) do not undergo this process and therefore do not migrate, do not modify their shapes with time, and are not associated with dark-CL zone-refined patches. This new understanding has implications for the interpretation of solids within fluid inclusions (e.g., Ti- and Al-minerals) and for the elemental analysis of hydrothermal and metamorphic quartz and its fluid inclusions by microbeam methods such as LA-ICPMS and SIMS. As Ti is a common trace element in quartz, its sequestration by fluid inclusions and its depletion in zone-refined patches impacts on applications of the Ti-in-quartz geothermometer.

Tight-Binding Approximations in 1D and 2D Coupled-Cavity Photonic Crystal Structures

Light confinement and controlling an optical field has numerous applications in the field of telecommunications for optical signals processing. When the wavelength of the electromagnetic field is on the order of the period of a photonic microstructure, the field undergoes reflection, refraction, and coherent scattering. This produces photonic bandgaps, forbidden frequency regions or spectral stop bands where light cannot exist. Dielectric perturbations that break the perfect periodicity of these structures produce what is analogous to an impurity state in the bandgap of a semiconductor. The defect modes that exist at discrete frequencies within the photonic bandgap are spatially localized about the cavity-defects in the photonic crystal. In this thesis the properties of two tight-binding approximations (TBAs) are investigated in one-dimensional and two-dimensional coupled-cavity photonic crystal structures We require an efficient and simple approach that ensures the continuity of the electromagnetic field across dielectric interfaces in complex structures. In this thesis we develop \textrm{E} -- and \textrm{D} --TBAs to calculate the modes in finite 1D and 2D two-defect coupled-cavity photonic crystal structures. In the \textrm{E} -- and \textrm{D} --TBAs we expand the coupled-cavity \overrightarrow{E} --modes in terms of the individual \overrightarrow{E} -- and \overrightarrow{D} --modes, respectively. We investigate the dependence of the defect modes, their frequencies and quality factors on the relative placement of the defects in the photonic crystal structures. We then elucidate the differences between the two TBA formulations, and describe the conditions under which these formulations may be more robust when encountering a dielectric perturbation. Our 1D analysis showed that the 1D modes were sensitive to the structure geometry. The antisymmetric \textrm{D} mode amplitudes show that the \textrm{D} --TBA did not capture the correct (tangential \overrightarrow{E} --field) boundary conditions. However, the \textrm{D} --TBA did not yield significantly poorer results compared to the \textrm{E} --TBA. Our 2D analysis reveals that the \textrm{E} -- and \textrm{D} --TBAs produced nearly identical mode profiles for every structure. Plots of the relative difference between the \textrm{E} and \textrm{D} mode amplitudes show that the \textrm{D} --TBA did capture the correct (normal \overrightarrow{E} --field) boundary conditions. We found that the 2D TBA CC mode calculations were 125-150 times faster than an FDTD calculation for the same two-defect PCS. Notwithstanding this efficiency, the appropriateness of either TBA was found to depend on the geometry of the structure and the mode(s), i.e. whether or not the mode has a large normal or tangential component.

Photoelectronic properties of zinc phosphide crystals, films and heterojunctions : quarterly progress report no. 6 for the period July 1 - September 30, 1980 /

The purpose of this research program is to investigate the photoelectronic properties of zinc phosphide (Zn₃P₂ in single crystal form, in thin-film form, and in heterojunctions in which Zn₃P₂ forms one of the elements. This research will be directed toward understanding the role of crystalline defects and impurities in Zn₃P₂, the nature of the electronic charge transport in single crystal and thin-film material, and the properties of photovoltaic heterojunctions involving Zn₃P₂. The scope of the program extends from basic investigations of materials properties on single crystals to the preparation and characterization of all-thin-film heterojunction divices. One of the principal motivations behind this research program is the realization that Zn₃P₂ is a relatively uninvestigated yet ideal component for photovoltaic heterojunction use in solar energy conversion. The proposed program will concentrate on the basic materials problems involved with Zn₃P₂, providing the kind of information needed for other more developmental programs directed toward actual practical cells.

The relationships between microstructure and crystal structure in zincite solid solutions

Single phase (Zn,Fe)(1-x) O zincite solid solution samples have been prepared by high temperature equilibration in air and in reducing atmospheres, followed by quenching to room temperature. The Fe2+/Fe3+ concentrations in the samples have been determined using wet chemical and XPS techniques. Iron is found to be present in zincite predominantly in the form of Fe3+ ions. The transition from an equiaxed grain morphology to plate-like zincite crystals is shown to be associated with increasing Fe3+ concentration, increasing elongation in < 001 > of the hexagonal crystals and increasing anisotropic strain along the c-axis. The plate-like crystals are shown to contain planar defects and zincite polytypes at high iron concentrations.

Creep and fatigue of a single crystal nickel base superalloy

The introduction of single crystal casting techniques has led to the development of existing nickel-base superalloys to produce materials with optimum mechanical properties in the single crystal condition. As single crystals are known to be anisotropic, a study is needed to determine the general mechanical properties of these materials, and determine the effects of crystal orientation upon them. A study has been carried out to identify the effect of orientation and temperature on the creep and fatigue properties of a development single crystal superalloy, SRR 99. Creep testing and crystal rotation experiments have been made on SRR 99 and an earlier development alloy, SRR 9. Fatigue experiments at elevated temperatures have been carried out on both notched and un-notched specimens of alloy SRR 99. To aid in this analysis, several analytical techniques have been employed including Laue x-ray orientation analysis, measurement of strain by photographic methods and microstructural examination. Crystal rotation experiments have indicated that shear of 1 precipitates by lbrace111rbrace< 112> slip systems is operative during primary creep deformation at temperatures of 750oC and 850oC. The effect of orientation variation obtained by standard casting practices was not found to be significant. Creep rupture was found to be associated with multiple crack initiation from micropores. Fatigue crack initiation in un-notched specimens was found to be related to microporosity and microstructural defects. Failure was predominantly by crystallographic crack growth on lbrace111rbrace planes. The use of linear elastic fracture mechanics to describe fatigue crack propagation in alloy SRR 99 was found to be acceptable at temperatures up to 850oC. Variation of temperature, frequency and crystal orientation was found to have only moderate effect upon crack propagation rates.

Dynamics of cholesteric liquid crystals in the presence of a random magnetic field:stochastic dynamics of cholesteric liquid crystal

Based on dynamic renormalization group techniques, this letter analyzes the effects of external stochastic perturbations on the dynamical properties of cholesteric liquid crystals, studied in presence of a random magnetic field. Our analysis quantifies the nature of the temperature dependence of the dynamics; the results also highlight a hitherto unexplored regime in cholesteric liquid crystal dynamics. We show that stochastic fluctuations drive the system to a second-ordered Kosterlitz-Thouless phase transition point, eventually leading to a Kardar-Parisi-Zhang (KPZ) universality class. The results go beyond quasi-first order mean-field theories, and provides the first theoretical understanding of a KPZ phase in distorted nematic liquid crystal dynamics.

Tight-Binding Approximations in 1D and 2D Coupled-Cavity Photonic Crystal Structures

Light confinement and controlling an optical field has numerous applications in the field of telecommunications for optical signals processing. When the wavelength of the electromagnetic field is on the order of the period of a photonic microstructure, the field undergoes reflection, refraction, and coherent scattering. This produces photonic bandgaps, forbidden frequency regions or spectral stop bands where light cannot exist. Dielectric perturbations that break the perfect periodicity of these structures produce what is analogous to an impurity state in the bandgap of a semiconductor. The defect modes that exist at discrete frequencies within the photonic bandgap are spatially localized about the cavity-defects in the photonic crystal. In this thesis the properties of two tight-binding approximations (TBAs) are investigated in one-dimensional and two-dimensional coupled-cavity photonic crystal structures We require an efficient and simple approach that ensures the continuity of the electromagnetic field across dielectric interfaces in complex structures. In this thesis we develop \textrm{E} -- and \textrm{D} --TBAs to calculate the modes in finite 1D and 2D two-defect coupled-cavity photonic crystal structures. In the \textrm{E} -- and \textrm{D} --TBAs we expand the coupled-cavity \overrightarrow{E} --modes in terms of the individual \overrightarrow{E} -- and \overrightarrow{D} --modes, respectively. We investigate the dependence of the defect modes, their frequencies and quality factors on the relative placement of the defects in the photonic crystal structures. We then elucidate the differences between the two TBA formulations, and describe the conditions under which these formulations may be more robust when encountering a dielectric perturbation. Our 1D analysis showed that the 1D modes were sensitive to the structure geometry. The antisymmetric \textrm{D} mode amplitudes show that the \textrm{D} --TBA did not capture the correct (tangential \overrightarrow{E} --field) boundary conditions. However, the \textrm{D} --TBA did not yield significantly poorer results compared to the \textrm{E} --TBA. Our 2D analysis reveals that the \textrm{E} -- and \textrm{D} --TBAs produced nearly identical mode profiles for every structure. Plots of the relative difference between the \textrm{E} and \textrm{D} mode amplitudes show that the \textrm{D} --TBA did capture the correct (normal \overrightarrow{E} --field) boundary conditions. We found that the 2D TBA CC mode calculations were 125-150 times faster than an FDTD calculation for the same two-defect PCS. Notwithstanding this efficiency, the appropriateness of either TBA was found to depend on the geometry of the structure and the mode(s), i.e. whether or not the mode has a large normal or tangential component.

Azo-linked corner porphyrin systems: synthesis, crystal structures and spectroscopic investigation

1,2-Bis[10,15-di(3,5-di-tert-butyl)phenylporphyrinatonickel(II)-5-yl]diazene was synthesised via copper catalysed coupling of aminated nickel(II) 5,10-diarylporphyrin (“corner porphyrin”) and its X-ray crystal structure was determined. Two different crystals yielded different structures, one with the free meso positions in a trans-like orientation, and the other with a cis-like disposition. The free meso positions of the obtained dimer have been further functionalised while the synthesis of a zinc analogue has so far been unsuccessful. The X-ray crystal structure of the dinitro derivative of the dinickel(II) azoporphyrin was determined, and the structure showed a cis-like disposition of the nitro groups.

Order and disorder in the structures of two crystal polymorphs of the adduct bis(quinolinium-2-carboxylate) DL-malic acid

The structures of two polymorphs of the anhydrous cocrystal adduct of bis(quinolinium-2-carboxylate) DL-malic acid, one triclinic the other monoclinic and disordered, have been determined at 200 K. Crystals of the triclinic polymorph 1 have space group P-1, with Z = 1 in a cell with dimensions a = 4.4854(4), b = 9.8914(7), c = 12.4670(8)Å, α = 79.671(5), β = 83.094(6), γ = 88.745(6)deg. Crystals of the monoclinic polymorph 2 have space group P21/c, with Z = 2 in a cell with dimensions a = 13.3640(4), b = 4.4237(12), c = 18.4182(5)Å, β = 100.782(3)deg. Both structures comprise centrosymmetric cyclic hydrogen-bonded quinolinic acid zwitterion dimers [graph set R2/2(10)] and 50% disordered malic acid molecules which lie across crystallographic inversion centres. However, the oxygen atoms of the malic acid carboxylic groups in 2 are 50% rotationally disordered whereas in 1 these are ordered. There are similar primary malic acid carboxyl O-H...quinaldic acid hydrogen-bonding chain interactions in each polymorph, extended into two-dimensional structures but in l this involves centrosymmetric cyclic head-to-head malic acid hydroxyl-carboxyl O-H...O interactions [graph set R2/2(10)] whereas in 2 the links are through single hydroxy-carboxyl hydrogen bonds.

Effect of heating rate on the crystal composition of ferroelectric lithium niobate crystallites

A series of lithium niobate powders were synthesized by the combustion method at different heating rates. The effect of heating rate on the crystal composition of lithium niobate powders was investigated by powder X-ray diffraction measurements. It has been found that the lithium content in the as-synthesized lithium niobate powders increases with decreasing the heating rate. On the basis of the existed structure-property relationship of lithium niobate single crystals, it was concluded that high quality lithium niobate powders can be effectively synthesized at a lower heating rate (in the range of 5-10 C/min) by the combustion method.