No / No Abstract

Present day advanced technologies heavily rely on one particular class of matter, i.e. the crystals. It is the periodic nature of the atoms and the properties arising due to the periodicity in crystals that is exploited to meet various technological feats. The technological revolutions in the semiconductor, optics and communication industries are the examples. The anisotropy in the crystals gives them enhanced properties as required in the field of non-linear optics. The field of non-linear optics became practically a reality after the invention of lasers. The coherent and monochromatic optical beams in the visible and ultraviolet ranges are in high demand due to their application in the fields like material processing, semiconductor lithography, laser micromachining, laser spectroscopy, photochemical synthesis, inertial confinement fusion and other basic scientific studies. In this thesis, work on the growth and characterization of two technologically important non-linear optical crystals has been carried out after developing the necessary instrumentation and some novel techniques for synthesis and growth. Also, studies on the glassy nature of one of the crystals have been carried out. This thesis consists of seven chapters. The first chapter gives a brief introduction to the nonlinear optical phenomenon, crystal growth and glassy state. Instrumentation is the backbone of crystal research technology. Without precision growth equipments large size crystals cannot be grown and without precision characterization instrumentation no conclusion regarding the quality and usefulness of the grown material can be drawn. The work reported in Chapter 2 describes the instrumentation developed for the growth, processing and characterization of crystals grown by solution and melt growth techniques. In low temperature solution growth, crystal growth workstations have been developed using tanks (made of acrylic), heating elements, and stirring propellers. Cooling coils have been inserted into the designed water bath to grow crystals below ambient also. This bath has an advantage to work over a wide range of temperatures, so that maximum retrieval of the material is possible. The growth of large crystals is usually hindered due to spurious nucleation precipitating during the growth process. A novel nucleation-trap crystallizer has been designed and developed that facilitates the continuation of the growth run in spite of extra nucleation precipitating after seeding. In this crystallizer, the spurious nuclei and any other particles generated after the filtration are forced into a well, and the growth of spurious nuclei is arrested by manipulating the temperature of this trap. Achieving adequate heat flow and mass flow profiles is of vital importance for growing good quality crystals. An optimized stirring procedure for the solution or melt is needed for ensuring the desired supply of growth units to the crystal-nutrient interface, and for transporting away any debris of the crystal-growth process. An ACRT set up has been designed and developed. For the growth of crystals by the flux technique and from direct melt, a crystal puller has been designed and developed. The crystal puller consists of a crystal rotation unit, slow and fast pulling mechanisms and a control unit. The pulling assembly is protected from damage caused by possible human errors through interlock mechanisms. The vibration at the shaft of the seed rotation assembly has been minimized by using a dc motor for rotation. A versatile triangular / square wave oscillator has been designed for developing a dc motor control. By implementing this control, the speed of the motor does not vary with supply-voltage variations. A quarter-step switching logic sequence is introduced for stepper motors, which is used for the slow UP/DOWN movement of the puller. This puller can be controlled locally by a control panel provided with the puller, or through a PC remotely by bypassing the local control. Additionally, for the processing and characterization of the grown DKDP crystals, a closed-loop thread-cutter, a ferroelectric loop tracer, and a computer-controlled system for measuring the half-wave voltage have been developed. A novel mercury encapsulant seeding technique that facilitates the processing of solution with immersed seed is invented and has been described in Chapter 3. This technique allows processing of solution with the seed inside the growth chamber, and still avoids contamination of the solution and formation of crystal clusters that are normally generated when seed is inserted after processing of the solution. DKDP and KAP crystal seeds have been used to check the dissolution of seeds, if any, when immersed in pure water for several hours and at high temperatures after introducing the seal. It has been observed that the mercury seal does not allow creeping of water into the seed holder, and there is no dissolution of the seed. This technique has been practically implemented for the growth of crystals from aqueous solution and its usefulness has been demonstrated by growing ammonium acid phthalate, potassium acid phthalate and potassium di-deuterium phosphate crystals. Nonlinear-optical crystals find major use in inertial-confinement fusion (ICF) experiments. For such applications, nonlinear crystals with very large damage-resistance are needed. Alternatively, crystals with moderate damage resistance but large size can be used for frequency-conversion for efficient plasma experiments. Potassium di-hydrogen phosphate, KH2PO4 (KDP) and its deuterated analog, K(DxH1-x)2PO4 (DKDP) are at present the only nonlinear optical crystals which can be grown to large sizes and are suitable for ICF studies. Also, solid-state light valves, light deflectors, and laser communication devices require large and perfect tetragonal DKDP crystals, with high deuterium concentration for easier operation. Chapter 4 describes the growth and characterization of DKDP crystals. DKDP crystals have been grown by all the three techniques i.e. conventional, platform and novel mercury encapsulant seeding techniques. Details about a new approach for the synthesis of DKDP solution have been given. A comparative study of the grown crystals by mercury-encapsulant technique and other techniques is described. Habit modification was observed due to the placement of seed crystals at an off-centre position and orientation in mercury encapsulant seeding technique and has been discussed. The grown crystals have been characterized for homogeneity, dislocations, transmission, DSC, rockng curve, etc. Due to the higher photon energies and the ability to be more tightly focused, coherent radiations of shorter wavelength (deep-UV) are in demand. The photon energies in this region are sufficient for bond-breaking processes in many materials, and find applications in fields like material processing, semiconductor lithography, laser micromachining, laser spectroscopy, photochemical synthesis, etc. Although excimer lasers (XeCl, KrF, ArF etc.) produce significant power in the deep-UV region, these laser systems involve corrosive gases, and are bulky, apart from requiring regular maintenance. A maintenance-free, compact, solid-state laser is preferable. But this, in turn, requires an efficient NLO crystal in that region. CLBO is one such crystal. Growth of CLBO crystals has been carried out by the flux-growth technique using B2O3-deficient flux, as well as from stoichiometric melt and has been discussed in Chapter 5. It was observed that the nucleation of material on platinum wire or spontaneous nucleation was difficult to achieve in spite of high supercooling. After forcing cracks into the mass deposited on platinum wire nucleation could be achieved. The growth of crystals was carried out on seeds with different orientations. Transmission studies, etch-pit studies and harmonic-generation experiments were performed on the grown crystals. The glass-forming tendency of CLBO has been studied and reported in Chapter 6. DTA experiments show that CLBO melt generally transforms to glass on cooling. Even at a cooling rate as low as 1°C/min, the material does not crystallize but transforms into glass. Ergodicity making and glass transition temperatures were determined for glassy CLBO. Since neither the crystallization peak nor the melting peak was observed in DTA experiments during the heating part of thermal cycle for glassy CLBO, a new approach of seeded crystallization was adopted in the calorimetric experiments to achieve crystallization. Since the size of added nuclei is already above the critical radius, the onset of crystallization peaks is independent of the critical-radius energy barrier. Kissenger method was applied to determine the activation energy of seeded- crystallization process. The transformation of glass CLBO to the crystalline phase is mediated by dendrites. Possibility of bulk crystal growth from the glassy state has been discussed, and a novel idea of surface crystallization is proposed. Chapter 7 summarizes the work carried out and projects the scope for future work.

published_or_final_version / Physics / Master / Master of Philosophy

Flexoelectricity in liquid crystals is thought to be due to a coupling between dielectric properties and shape anisotropy of the molecules and described by the fiexoelectric coefficients el and e3. Two experiments are needed to measure el and e3 and it is usual to measure the difference (el - e3) and the sum (el + e3) and then calculate el and e3· The first experiment to measure the difference (el - e3) uses a TN structure with an in-plane applied electric field. Due to the dielectric coupling, the director aligns with the electric field and due to the fiexoelectric effect, the director tilts out of plane. This tilt is measured optically using two laser beams at oblique incidence, e.g. 45°. Using a theoretical model the experimental data is fitted and the difference (el - e3) extracted. The second experiment to measure the sum (el + e3) uses a Pi cell. Applying an ac voltage the transmission through the device is a repeating oscillating signal which contains 1st and 2nd harmonics. The 1st harmonic corresponds to the fiexoelectric effect and the 2nd harmonic to the dielectric effect. Using a lock-in amplifier, the harmonics were measured and the sum (el + e3) extracted using a theoretical model to fit the experimental data. Unfortunately, the data proved the experiment to be unreliable and another method was developed, which uses a BAN cell. The third experiment uses simple pulses in a BAN cell and also measures the sum (el + e3). The big disadvantage of the BAN cell is an internal voltage, which is created by the homeotropic alignment layer and the fiexoelectric polarisation. The internal voltage has the same effect on the director profile as the fiexoelectric effect, which is a big problem in measuring fiexoelectricity. Using a material, which is non ionic and has no fiexoelectricity, the internal bias could be measured and taken into account. Applying short de pulses of opposite sign, the fiexoelectric effect can be observed by the optical response and can be measured. Using these experiments, a number of investigation are being carried out such as the correlation between fiexoelectricity and the molecular structure, ions, elastic properties, molecular orientation, dielectric anisotropy 6E, and order parameter S. The results showed that fiexoelectricity only depends on ions and dielectric properties which was very interesting and surprising at the same time.

The objectives of this thesis were to develop a methodology for the measurement of laser beam characteristics from a single cavity laser and to establish a preliminary guideline that would determine which crystals were acceptable for use in production of laser devices. These objectives were achieved by developing the experimental procedures and by statistical analysis of the data obtained. However, additional future work is needed to independently confirm the results of this thesis. Efficient and reliable operation of a lamp-pumped Nd:YAG laser is highly dependent on the crystal from which the beam is derived. However little attention is given to the quality of the laser beam produced by each crystal. Although many factors influence the output beam, the power dependent focal length is of particular importance. Unfortunately, direct measurement of the crystal focal length is not possible with a Nd:YAG laser beam. This is because the single cavity laser functions as both a resonator and amplifier simultaneously. Therefore, a method was developed that measured the caustic of the laser beam after it had emerged from the resonator and been focused by means of a focusing element. The caustic of the beam was analyzed utilizing a beam analyzer that calculated the beam focusability factor and the beam waist size. From this information, the waist diameter at the outcoupler mirror was calculated using Gaussian beam propagation principles. A resonator model was developed based on the self-repeating ABCD matrix that allowed for the determination of the induced thermal lens based on the input power. Several approaches to model the thermal lensing effect were taken, each with increasing complexity. As a result, three parameters were evaluated with the intention of using one or more as a means to classify good and bad crystals. They were the crystal sensitivity factor, the beam focusability factor, and the beam waist size at the measurement plane. Calculation of the crystal sensitivity factor, M^-1, was based on the developed resonator model and numerous approximations of the crystal behavior. Thus, after calculating the M-1 factor as a function of input power, no distinguishable pattern was seen. However, the beam focusability factor and the beam size, both showed distinct regions that separate good and bad crystals. Statistical analysis performed on the data supports a preliminary conclusion that these two parameters may be used as a quality control measure. These parameters are measured using existing internationally accepted procedures and are therefore the best currently available tools for determination of the quality of Nd:YAG crystals.

Thesis. 1978. Ph.D.--Massachusetts Institute of Technology. Dept. of Materials Science and Engineering. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Includes bibliographical references. / Ph.D.

Thesis (Ph. D.)--Florida State University, 2004. / Advisor: Dr. William G. Moulton, Florida State University, College of Arts and Sciences, Dept. of Physics. Title and description from dissertation home page (viewed June 15, 2004). Includes bibliographical references.

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This thesis uses multiscale computational modelling to find the fundamental principles that govern defects forming during the operation of new electro-optical devices and the processing of spider silk fibers. The generalized approach developed in this thesis bridges engineering devices and biological processes based on liquid crystalline materials. / Three types of defects are encountered: inversion walls, lines and points. Inversion wall defects are found in the electro-optical device when a nematic thin film undergoes a temperature-induced surface anchoring transition. Point defects naturally occur in the tubular extrusion duct of spiders, while line defects present close topological connections with point defects and are widespread in many high-performance industrial fibers. Three models are used in this thesis and their usage is dependent on the characteristics of the defects studied. / In the case of inversion wall defects, computational modelling is used to verify, complement and analyze experimental measurements made with fluorescence confocal polarizing microscopy by our collaborator at the Georgia Institute of Technology. The various simulation results agree and explain very well experimental observations and provide a thorough understanding of the wall defects behavior. A computational technique is developed to enable the precise determination of the interaction between the liquid crystal and the device substrate. Understanding the behavior of wall defects and estimating interfacial properties are indispensable to the development and optimization of the electro-optical device as they affect properties like temperature of operation, switching voltages and response time. / Computational modelling is also used to investigate the behavior of nematic point defects confined in cylindrical cavities as observed along spiders' spinning apparatus, and to examined textural connections with other well know structures seen in industrial fibers. The various scenarios investigated include: interactions between point defects, topological transformations between point, line and ring defects as well as interactions between ring defects. The simulation results agree and complement previous investigations but also offer a new fundamental understanding on the nature and stability of defects in cylindrical cavities. Understanding the behavior of nematic point and line defects in cylindrical geometries is important as they play a fundamental role in the processing of natural and industrial high-performance fibers.