Nematic liquid crystals possess large optical nonlinearities owing to their large refractive index anisotropy coupled with the collective molecular reorientation. Doping absorbing dyes into liquid crystals increases their optical responses significantly due to increased absorption in the visible region, absorption-induced intermolecular torque, cis-trans photoisomerization, and other guest-host effects. The guest-host mixtures can be employed in display applications, optical storage devices, and others. In this dissertation, nonlinear optical studies were carried out on dye-doped nematic liquid crystal cells. The main objectives of the studies were to distinguish and characterize the several processes that can lead to the formation of dynamic gratings of different types in the samples, and to study the photorefractive and the orientational responses of these samples. Furthermore, we tried to explain and model the dynamical behaviors of the observed grating formations. The experimental techniques employed in this study include asymmetric two-beam coupling, forced light scattering, and polarization holographic method. The asymmetric two-beam coupling experiments revealed that the induced grating was a photorefractive phase grating created by the nematic director reorientation within the plane of incidence. The dynamics of the beam coupling showed that two different mechanisms with different temporal responses were involved. The grating translation technique identified both gratings as pure photorefractive index gratings with phase shifts of ~ p/2 between the grating and the interference pattern. In addition, the dynamical behavior of the grating formation, obtained from forced light scattering experiments, also exhibited a two-time constant response. The dynamical behaviors of the build-up and decay of the photocurrent were investigated. The two dynamics exhibited both a two-time constant behavior, suggesting that the origin of the two-time constant dynamics observed in the two-beam coupling and the forced light scattering experiments resides in the process of photo-charge generation. The photorefractive gain coefficients were found to be in the range of 100 – 400 cm-1. The values of the nonlinear optical Kerr index (~ 0.08 cm2/W) measured in samples with certain dye/liquid crystal combinations are higher than what has been observed in other dye-doped nematics and other liquid crystal/polymer systems. All the samples showed a threshold behavior with respect to the magnitude of the applied electric field. This threshold behavior was observed both in forced light scattering experiments and polarization holographic experiments. We believe that the origin of this threshold lies in the process of photogeneration, which was found to exhibit the same threshold behavior at the same value of the applied voltage. An asymmetry of the photorefractive gain with respect to the direction of the applied electric field was observed in samples with high dye concentration. This was attributed to the beam fanning effect, which has also been observed in other high-gain photorefractive materials. Polarization holographic measurements showed that the dye enhancement effect is primarily due to the intermolecular interaction between the dye molecules and the liquid crystal host, and that the trans-cis photoisomerization plays a lesser role. The photoinduced orientational response was also studied using polarization holographic experiments. A number of observations confirmed that the birefringent grating is due to the nematic director reorientation within the plane of incidence, under the combined effect of the applied electric field and the optical field. The diffraction efficiency was found to depend linearly on the writing beam power, while the dependence of the self-diffraction efficiency on the writing beam power roughly assumes a cubic relationship. The dynamical behavior of the birefringent grating formation was investigated. The build-up dynamics was found to be best modeled as a double-time constant response, while the decay is best fitted by a single exponential. The response of the samples to an oscillating electric field was studied as a function of the modulation frequency. Very interesting and reproducible dynamics was observed, revealing the complex dynamical response of the liquid crystal director to the magnitude and rate of change of an applied electric field. The small signal response was also measured, but did not reveal any sign of a resonance behavior. The conductivity and the photoconductivity of the samples were measured. The relationship between the measured current and the applied voltage was found to be cubic at low applied voltage, and to become linear at higher applied voltage. We could explain this behavior using a double-charge-injection-in-a-weak-electrolyte model, but this is only one of the possible mechanisms that could explain this behavior. The photocurrent was found to increase linearly with the illumination power, which indicates that the charge carrier recombination rate is proportional to the carrier density. The measured electrical conductivity was found to be proportional to the square root of the dye concentration, confirming the validity of the proposed charge-injection model. / Ph. D.

This thesis presents a novel technique named "Core Suction" for fabricating optical fiber preforms for manufacturing highly doped fibers (HDFs) for optical amplification (Raman effect based or Erbium fiber based). The technique involves drawing the molten non-conventional core glass material into the silica cladding tube to form the preform. The developed technique is simple, inexpensive and shows great potential for fabricating preforms of highly nonlinear non-conventional multi-component glasses as the core material. Preforms were made with various core glasses such as Schott SF6, Lead-Tellurium-Germanate, Lead-Tellurium-Germanate- Neodymium -Erbium and MM2 in silica cladding tubes and then pulled into fibers. The fabricated fibers were measured for refractive index profile, loss spectrum and spontaneous Raman spectra. Elemental analysis of the fiber samples was also performed using an electron microprobe. Erbium doped fiber amplifiers (EDFAs) were setup using 30 cm, 5cm and 1 cm lengths of fabricated erbium doped fibers and their gain spectra measured. The distributed gain spectrum for an EDFA was also measured using an optical frequency domain reflectometery (OFDR) technique. Commercial dispersion compensated fiber (DCF) with very high GeO2 doping was used to setup a Raman amplifier and the gain spectrum measured. One of the needs of Raman amplification in optical fibers is to predict an accurate Raman gain, based on the fiber's refractive index profile. A method of predicting Raman gain in GeO2 doped fibers is presented and the predicted Raman gain values are compared with the measured ones in the same fibers. Raman gain issues like the dependence of the Raman gain on the GeO2 concentration, polarization dependence were taken into account for the gain calculations. An experimental setup for Raman gain measurements was made and measurement issues addressed. Polarization dependence of the Raman gain in one kilometer of polarization maintaining fiber was also measured. / Ph. D.

Optical studies of heavily-doped GaAs:C grown at low temperature by molecular beam epitaxy were performed using room-temperature photoluminescence, infrared transmission, and Raman scattering measurements. The photoluminescence experiments show that in LT-GaAs:C films grown at temperatures below 400 °C, nonradiative recombination processes dominate and photoluminescence is quenched. When the growth temperature exceeds 400 °C, band-to-band photoluminescence emission appears. We conclude that the films change in character from LT-GaAs:C to normal GaAs:C once the growth temperature reaches 400 °C. Annealing, however, shows a different behavior. Once grown as LT-GaAs:C, this material retains its nonconducting nonluminescing LT characteristics even when annealed at 600 °C. The Raman-scattering measurements showed that the growth temperature and the doping concentration influence the position, broadening, and asymmetry of the longitudinal-optical phonon Raman line. We attribute these effects to changes in the concentration of interstitial carbon in the films. Also, the shift of the Raman line was used to estimate the concentration of arsenic-antisite defects in undoped LT-GaAs. The infrared transmission measurements on the carbon-doped material showed that only a fraction of the carbon atoms occupy arsenic sites, that this fraction increases as the growth temperature increases, and that it reaches about 100% once the growth temperature reaches 400 °C. The details of all these measurements are discussed. Infrared transmission and photoluminescence measurements were also carried out on heavily-doped GaAs:C films grown by molecular beam epitaxy at the standard 600 C temperature. The infrared results reveal, for dopings under 5 x 10⁹ cm⁻³, a linear relation between doping concentration and the integrated optical absorption of the carbon localized-vibrational-mode band. At higher dopings, the LVM integrated absorption saturates. Formation of C_As-C_As clusters is proposed as the mechanism of the saturation. The photoluminescence spectra were successfully analyzed with a simple model assuming thermalization of photoelectrons to the bottom of the conduction band and indirect-transition recombination with holes populating the degenerately doped valence band. The analysis yields the bandgap reduction and the Fermi-level-depth increase at high doping. / Ph. D.

The interactions between different components of solid oxide cells (SOCs) are critical issues for achieving the tens of thousands of hour's goal for long-term performance stability and lifetime. The interactions between the ceramic electrolyte, porous ceramic air electrode, and metallic interconnect materials — including solid state interfacial reactions and vaporization/deposition of some volatile elements — have been investigated in the simulated SOC operating environment. The interactions demonstrate the material degradation mechanisms of the cell components and the effects of different factors such as chemical composition and microstructure of the materials, as well as atmosphere and current load on the air electrode side. In the aspect of materials, this work contributes to the degradation mechanism on the air electrode side and provides practical material design criteria for long-term SOC operation. In this research, an yttria-stabilized zirconia electrolyte (YSZ)/strontium-doped lanthanum manganite electrode (LSM)/AISI 441 stainless steel interconnect tri-layer structure has been fabricated in order to simulate the air electrode working environment of a real cell. The tri-layer samples have been treated in dry/moist air atmospheres at 800°C for up to 500 h. The LSM air electrode shows slight grain growth, but the growth is less in moist atmospheres. The amount of Cr deposition on the LSM surface is slightly more for the samples thermally treated in the moist atmospheres. At the YSZ/LSM interface, La enrichment is significant while Mn depletion occurs. The Cr deposition at the YSZ/LSM interface is observed. The stoichiometry of the air electrode is an important factor for the interactions. The air electrode composition has been varied by changing the x value in (La0.8Sr0.2)xMnO₃ from 0.95 to 1.05 (LSM95, LSM100, and LSM105). The enrichment of La at the YSZ/LSM interface inhibits the Cr deposition. The mechanisms of Cr poisoning and LSM elemental surface segregation are discussed. A 200 mA·cm-2 current load have been applied on the simulated cells. Mn is a key element for Cr deposition under polarization. Excessive Mn in the LSM lessens the formation of La-containing phases at the YSZ/LSM interface and accelerates Cr deposition. Deficient Mn in LSM leads to extensive interfacial reaction with YSZ forming more La-containing phase and inhibiting Cr deposition. / Ph. D.

Yes / The gadolinium-doped iron oxide nanoparticles (GdIONP) with greater specific power adsorption rate (SAR) than Fe3O4 was developed and its potential application in tumour therapy and particle tracking were demonstrated in transgenic adenocarcinoma of the mouse prostate C1 (TRAMP-C1) tumours. The GdIONPs accumulated in tumour region during the treatment could be clearly tracked and quantified by T2-weighted MR imaging. The therapeutic effects of GdIONP-mediated hyperthermia alone or in combination with radiotherapy (RT) were also evaluated. A significant increase in the tumour growth time was observed following the treatment of thermotherapy (TT) only group (2.5 days), radiation therapy only group (4.5 days), and the combined radio-thermotherapy group (10 days). Immunohistochemical staining revealed a reduced hypoxia region with vascular disruption and extensive tumour necrosis following the combined radio-thermotherapy. These results indicate that GdIONP-mediated hyperthermia can improve the efficacy of RT by its dual functions in high temperature (temperature greater than 45 °C)-mediated thermal ablation and mild-temperature hyperthermia (MTH) (temperature between 39 and 42 °C)-mediated reoxygenation.

Yes / The fabrication of osmium nanoclusters from single atoms has been studied in real-time on B-doped and B-free graphitic surfaces. The dynamics of nucleation on both surfaces are identified, captured, and reported. The nucleation is ca. 2× faster on B-doped surface compared to the B-free surface (38 pm min−1versus 18 pm min−1), suggesting osmium–boron interactions within the nanomaterials.

The goal of this research was the fabrication of thin films with magneto-optic (MO) properties. Accomplishment of this task was achieved via sol-gel processing of rare-earth and aluminum substituted yttrium-iron garnet (RxY3-xAlyFe5-yO12, R,Al:YIG), where R= Bi, Gd, Er, Ho. Detailed are the processing conditions, parameters and results leading to R,Al:YIG films with MO response. Success was attained with a 0.25M Gd,Al:YIG solution spin coated for 120 seconds at 3500rpm onto a (111) gadolinium gallium garnet (GGG) substrate and calcinated at 900°C for 4 hours. Samples were characterized via x-ray diffraction (XRD), magneto-optical loop tracer, scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), profilometry and optical microscopy. / Master of Science

This dissertation focuses on two aspects of integrating near-infrared plasmonics with electronics with the intent of developing the platform for future photonics. The first aspect focuses on fabrication by introducing and developing a simple, single reflective optical element capable of high–throughput, large scale fabrication of micro- and nano-sized structure templates using holographic lithography. This reflective optical element is then utilized to show proof of concept in fabricating three dimensional structures in negative photoresists as well as tuning subwavelength features in two dimensional compound lattices for the fabrication of dimer and trimer antenna templates. The second aspect focuses on the study of aluminum zinc oxide (AZO), which belongs to recently popularized material class of transparent conducting oxides, capable of tunable plasmonic capabilities in the near-IR regime. Holographic lithography is used to pattern an AZO film with a square lattice array that are shown to form standing wave resonances at the interface of the AZO and the substrate. To demonstrate device level integration the final experiment utilizes AZO patterned gratings and measures the variation of diffraction efficiency as a negative bias is applied to change the AZO optical properties. Additionally efforts to understand the behavior of these structures through optical measurements is complemented with finite difference time domain simulations.

Scandia doped zirconia has been considered a candidate for electrolyte material in intermediate temperature Solid Oxide Fuel Cells (SOFCs) due to its high ionic conductivity, chemical stability and good electrochemical performance. The aim of this study is to determine the mechanical properties of SCZ, ie. zirconia (ZrO₂) doped with Scandia (Sc₂O₃) and small amount of ceria (CeO₂) that are important for reliability and durability of the components manufactured from SCZ. The SCZ was prepared from powder by uniaxiall cold pressing at subsequent sintering at 1550 ºC for 4 hours. The density and porosity of the sintered samples was measured following the ASTM Standard C20-00 for alcohol immersion method. A pure cubic phase of SCZ sample was identified by X-ray diffraction (XRD) at room temperature. Quantitative compositional analyses for Zr, Sc, Ce, Hf and Ti were carried out on a Cameca SX50 electron microprobe with wavelength-dispersive spectroscopy (WDS) and energy-dispersive spectroscopy (EDS). Scanning Electron Microscopy (SEM) images were acquired using both secondary electron (SE) and back-scattered electron (BSE) detectors. WDS and EDS analysis also revealed that Zr, Sc, Ce, Hf and Ti are relatively homogeneously distributed in the structure. The average grain size of sintered SCZ samples was measured to be 4 μm. Thermal expansion at different temperatures for the SCZ ceramic was determined using Thermal Mechanical Analyzer, and the instantaneous Coefficient of Thermal Expansion (CTE) was found to be 8.726х10⁻⁶ 1/°C in the in 25-400 °C temperature range. CTE increases monotonically with temperature above 400 ºC to 1.16х10⁻⁵ at 890 °C, most likely as a result of thermo-chemical expansion due to an increase in oxygen vacancy concentration. Room temperature Vickers hardens of 12.5 GPa was measured at loads of 1000 g, while indentation fracture toughness was found to vary from 2.25 to 4.29 MPa m¹⁄², depending on the methodology that was used to calculate fracture toughness from the length of the median corner cracks. Elastic moduli, namely Young and shear moduli were determined using Resonance Ultrasound Spectroscopy (RUS). It was found that elastic moduli decreases with temperature in non-linear manner, with significant drop in the 300-600 °C temperature range, the same temperature range in which loss modulus determined by Dynamic Mechanical Analyzer exhibits frequency dependant peaks. The high loss modulus and significant drop in elastic moduli in that temperature regime is attributed to the relaxation of doping cation-oxygen vacancies clusters. The flexural strength in 4-point bending was measured at room temperature, 400 °C, 600 °C and 800 °C. and the results were analyzed using Weibull statistics. It was found that flexural strength changes with temperature in a sigmoidal way, with the minimum strength at around 600 °C. Non-linear decrease in strength with temperature can be traced back to the changes in elastic moduli that are caused predominately by relaxation of oxygen vacancies.

High dielectric constant materials have tremendous impact on miniaturization of devices that are used in various applications like wireless communication systems, microelectronics, global positioning systems, etc. To store electric charge in a very small space necessarily needs a capacitor with very high dielectric constant. Thus, these materials are very important in fabricating capacitors, or metal oxide semiconductor filed effect transistor (MOSFET). Among the existing commercially available devices, silicon-based microelectronic devices are commonly used based on the moderately stable dielectric constants of silicon with low losses and minimal temperature and frequency dependence. However, now-a-days, the perovskite based transition metal oxides have drawn attention that have the ability to fulfill all the requirements for being a good dielectric material in all the industrial applications. In this thesis we have studied a few selected perovskite based transition metal oxide systems in terms of their dielectric and magnetic behaviour. In Chapter 1, we have have given brief introductions about the some application of dielectric materials and the origin of dielectric and magnetic properties in the materials. We have also discussed about the polarisation in the dielectric materials to understand it’s frequency dependence and also to formalise different relaxation behaviour with the help of physical and mathematical explanation. In Chapter 2, we describe the various methodologies adopted in this thesis. In Chapter 3, we have studied the dielectric behaviour of Nd2NiMnO6, a rare earth based double perovskite ferromagnetic insulator. We successfully synthesised and characterised the compounds, settled the valency issues with the help of temperature dependent XAS of the transition metal atom in contrast to the existing controversy available in literature. We have found that this material shows relaxor kind behaviour with a colossal dielectric constant value. We have studied in details the origin of the colossal dielectric constant and the relaxation behaviour along with the a.c and d.c. transport properties. We have shown the origin of the ferromagnetism (TC ∼ 200 K) with a low temperature antiferromagnetic ordering (TN ∼ 55 K) with the help of detailed studies of temperature dependent d.c., a.c. magnetism and their XMCD. We have also investigated the isothermal variation of magnetodielectric and magnetoresistance behaviour as a function of magnetic field and their origin. In Chapter 4,we study the effect of cation anti-site disorder on the magnetic, dielectric and transport properties of another rare earth based ferromagnetic double perovskite insulator La2NiMnO6 by controlling different extent of anti-site disordered. We have confirmed the valency of the transition metal cations using XAS technique and followed by shown, different types of magnetic interaction between the transition metal cations using d.c magnetic, quantitative XMCD analysis and the origin of large dielectric response, a.c. transport & dielectric relaxation using temperature variation dielectric measurement as an experimental evidence in contrast of our previous speculation published in literature. We further have studied, the coupling between the magnetic and electric spin through isothermal magnetodielectric measurement. In Chapter 5, we have successfully synthesised and characterised a solid solution of YMnxIn1−xO3 series via different mol % of In doping in the multiferroic YMnO3 system. YMnO3 is a well known multiferroic material studied rigorously during past few decades. We have seen, YMnO3 which has a antiferromagnetic ordering temperature of ∼ 75 K suppressed with increasing the dopant concentration In. We have figured out the effect of In doping in the suppression of multiferroic phase and extended it to the dielectric properties. We have found that, the temperature dependence of dielectric constant shows an anomaly at the magnetic ordering temperature and studied magnetodielectric coupling. We have also investigated the temperature variation of dielectric relaxation and a.c. transport behaviour as a function of composition. In Chapter 6, we have identified the phase seperation and proposed a phase diagram as function of Gd doping in the Ho2−xGdxCuTiO6 double perovskite, where two end member, namely Ho2CuTiO6 and Gd2CuTiO6 are found to be in two different crystallographic phase as, hexagonal (P63cm) and orthorhombic (Pnmm), respectively. We have characterised the valency of the transition metal cations using XAS.We have seen very less temperature and frequency dependence of dielectric constant in hexagonal phase in compare to the orthorhombic phase and tried to figuring out from experimental analysis by performing temperature dependence dielectric const measurement. We also have shown the effect of doping in the origin of dielectric relaxation, a.c transport and magnetic behaviour of this system. In Chapter 7, we have synthesised and characterised successfully two different rare earth based layered perovskite La3Cu2VO9 and La4Cu3MoO12 compounds are of centrosymmetric space group. We have figured it of the valency of the different atoms present in the compound using XAS. We also do have observed the good temperature stability of dielectric constant of these materials and explored origin of mechanism in the dielectric relaxation, a.c. transport property by performing the temperature dependance dielectric measurement. The magnetic structure also have shown with the help of d.d. magnetic measurements. In Appendix A, we have seen the very stable dielectric constant constant from very low to above room temperature of the 2D nano PbS. The frequency stability of dielectric constant is also remarkable in compare to bulk PbS values available in literature. We have explored the origin of the conductivity and relaxation mechanism performing dielectric constant measurement. In conclusion, we investigate, in this thesis, dielectric properties of different transition metal oxides system and the mechanism of dielectric relaxation, a.c, d.c transport and their origin of magnetic response.