This thesis is sub-divided into two parts. Part (i) is entitled 'Structure / Property Relationships in Non-linear Optical Materials' (chapters 1-8) whilst part (ii) is entitled 'Structural Studies of imido, (bis)imido and aryloxide group VA and VIA transition metal complexes' (chapters 9-10).Chapters 1, 2 and 3 provide an introduction to non-linear optics, X-ray and neutron experimental techniques used in this thesis and charge density studies respectively. Chapters 4 to 8 describe the investigations of the part (i) topic. These include bond length alternation studies on a series of tetracyanoquinodimethane derivatives and a charge density study of one of these compounds in chapter 4. Several other charge density studies are reported in chapters 5 and 6 which concentrate on methyl- nitropyridine and nitroaniline derivatives and the compound, 3-( 1,1 -dicyanoethenyl)-l-phenyl-4,5- dihydro-1 H-pyrazole (DCNP) respectively. Chapter 5 also deals with the effect of intermolecular interactions on the non-linear optical phenomenon whilst in chapter 6, a detailed analysis of the thermal motion present in DCNP is also given. Investigations on intermolecular interactions are also reported in chapters 7 and 8 which studies the compounds, N-methylurea and zinc(tris)thiourea sulphate respectively. In the former case, the neutron derived structure of N-methylurea is reported at two temperatures and it is revealed that disorder is present at the higher temperature. In the latter case, neutron results from an instrument presently in the testing stages of its development are reported and contrasted with those obtained using a well established instrument. Chapters 9 and 10 describe the investigations of the part (ii) topic. These concentrate on the structural features of two series of organometallic compounds which have potential use as polymerization catalysts. Relationships between structure and reactivity are reported.

Some basic concepts and principles of optical dielectric slab waveguiding and experimental methodology involving characterisation of waveguide films are introduced, Results from the characterisation of thin polymeric waveguide films and measurements of refractive indices of the films are presented. The birefringence of some polymer films is analysed and discussed. The photostabilities of several dopants (DEMI, Ultra-DEMI, Dicyclohexyl-DEMI, Mor2, Morpip and DCM) are investigated in a polymer matrix (PMMA), and their measured photostabilities are presented. These organic chromophores change their properties in the course of photodegradation. Degradation experiments are carried out by exposing the doped waveguide films to light in air, vacuum and nitrogen environments. The degradation mechanisms of these chromophores are discussed. It is found that the degradation of the DEMI, Ultra-DEMI, Dicyclohexyl-DEMI and DCM are due to photooxidation, their photostabilities are much higher in vacuum than in air. The Mor2 and Morpip degrade by direct photodecomposition, their photostabilities are in the same order when exposed to light in their main absorption bands. The oxygen free environment (e.g. vacuum) is essential to increase their photostabilities. A beam branching effect in DCM doped waveguide film is observed. Stacked multi-layer waveguides are investigated as possible humidity sensors. Symmetric structure (PMMA/P-4VP/PMMA/P-4VP/PMMA) (P4VP-I) and unsymmetric structure (Si02/P-4VP/Zeonex/P-4VP/Air) (P4VP-II) are studied. Special procedures and process have been developed to fabricate multi-layer waveguide structures in experiments. It is found that both structures have good reversibilities and show reasonable stabilities. 30 ppm concentrations of water vapour can be detected by the P4VP-II structure. The experimental results show that the overall response of P4VP-II structure exhibits good linearity with increase of the concentration of water vapour. The structures can not only measure the phase shift of interference, but also can measure the direction of fringe movement. The sensitivity of the structure can be further improved by using different combinations of polymers in the structure.

No description available.

<p>Quantum chemical computations provide convenient and effective ways for molecular design using computers. In this dissertation, the molecular designs of optimal nonlinear optical (NLO) materials were investigated through three aspects. First, an inverse molecular design method was developed using a linear combination of atomic potential approach based on a Hückel-like tight-binding framework, and the optimizations of NLO properties were shown to be both efficient and effective. Second, for molecules with large first-hyperpolarizabilities, a new donor-carbon-nanotube paradigm was proposed and analyzed. Third, frequency-dependent first-hyperpolarizabilities were predicted and interpreted based on experimental linear absorption spectra and Thomas-Kuhn sum rules. Finally, molecular interferometers were designed to control charge-transfer using vibrational excitation. In particular, an ab initio vibronic pathway analysis was developed to describe inelastic electron tunneling, and the mechanism of vibronic pathway interferences was explored.</p> / Dissertation

Short optical pulses and engineered nonlinear media is a powerful combination. Mode locked pulses exhibit high peak powers and short pulse duration and the engineered ferro-electric KTiOPO4 facilitates several different nonlinear processes. In this work we investigate the use of structured, second-order materials for generation, characterization and frequency conversion of short optical pulses. By cascading second harmonic generation and difference frequency generation the optical Kerr effect was emulated and two different Nd-based laser cavities were mode locked by the cascaded Kerr lensing effect. In one of the cavities 2.8 ps short pulses were generated and a strong pulse shortening took place through the interplay of the cavity design and the group velocity mismatch in the nonlinear crystal. The other laser had a hybrid mode locking scheme with active electro-optic modulation and passive cascaded Kerr lensing incorporated in a single partially poled KTP crystal. The long pulses from the active modulation were shortened when the passive mode locking started and 6.9 ps short pulses were generated. High-efficiency frequency conversion is not a trivial task in periodically poled materials for short pulses due to the large group velocity mismatch. Optimization of parameters such as the focussing condition and the crystal temperature allowed us to demonstrate 64% conversion efficiency by frequency doubling the fs pulses from a Yb:KYW laser in a single pass configuration. Quasi phase matching also offers new possibilities for nonlinear interactions. We demonstrated that it is possible to simultaneously utilize several phase matched second harmonic interactions, resulting in a dual-polarization second harmonic beam. Short pulse duration of the fundamental wave is a key parameter in the novel method that we demonstrated for characterization of the nonlinearity of periodically poled crystals. The method utilizes the group velocity mismatch between the two polarizations in a type II second harmonic generation configuration. The domain walls of PPKTP exhibit second order nonlinearities that are forbidden in the bulk material. This we used in a single shot frequency resolved optical gating arrangement. The spectral resolution came from Čerenkov phase matching, a non-collinear phase matching scheme that exhibits a substantial angular dispersion. The second harmonic light was imaged upon a CCD camera and with the spectral distribution on one axis and the temporal autocorrelation on the other. From this image we retrieved the full temporal profile of the fundamental pulse, as well as the phase. The spectral dispersion provided by the Čerenkov phase matching was large enough to characterize optical pulses as long as ~200 fs in a compact setup. The Čerenkov frequency resolved optical gating method samples a thin stripe of the beam, i.e. the area close to the domain wall. This provides the means for high spatial resolution measurements of the spectral-temporal characteristics of ultrafast optical fields. / QC 20100831

No description available.

This dissertation investigates two long standing issues in nonlinear optics: complete characterization of the ultrafast dynamics of simple molecules, and the potential of a two-photon laser using a bulk semiconductor gain medium. Within the Born-Oppenheimer approximation, nonlinear refraction in molecular liquids and gases can arise from both bound-electronic and nuclear origins. Knowledge of the magnitudes, temporal dynamics, polarization and spectral dependences of each of these mechanisms is important for many applications including filamentation, white-light continuum generation, all-optical switching, and nonlinear spectroscopy. In this work the nonlinear dynamics of molecules are investigated in both liquid and gas phase with the recently developed beam deflection technique which measures nonlinear refraction directly in the time domain. Thanks to the utility of the beam deflection technique we are able to completely determine the third-order response function of one of the most important molecular liquids in nonlinear optics, carbon disulfide. This allows the prediction of essentially any nonlinear refraction or two-photon absorption experiment on CS2. Measurements conducted on air (N2 and O2) and gaseous CS2 reveal coherent rotational revivals in the degree of alignment of the ensemble at a period that depends on its moment of inertia. This allows measurement of the rotational and centrifugal distortion constants of the isolated molecules. Additionally, the rotational contribution to the beam deflection measurement can be eliminated thanks to the particular polarization dependence of the mechanism. At a specific polarization, the dominant remaining contribution is due to the bound-electrons. Thus both the bound-electronic nonlinear refractive index of air, and second hyperpolarizability of isolated CS2 molecules, are measured directly. The later agrees well with liquid CS2 measurements, where local field effects are significant. The second major portion of this dissertation addresses the possibility of using bulk semiconductors as a two-photon gain medium. A two-photon laser has been a goal of nonlinear optics since shortly after the original laser*s development. In this case, two-photons are emitted from a single electronic transition rather than only one. This processes is known as two-photon gain (2PG). Semiconductors have large two-photon absorption coefficients, which are enhanced by ~2 orders of magnitude when using photons of very different energies, e.g., ћωa≈10ћωb. This enhancement should translate into large 2PG coefficients as well, given the inverse relationship between absorption and gain. Here, we experimentally demonstrate both degenerate and nondegenerate 2PG in optically excited bulk GaAs via pump-probe experiments. This constitutes, to my knowledge, the first report of nondegenerate two-photon gain. Competition between 2PG and competing processes, namely intervalence band and nondegenerate three-photon absorption (ND-3PA), in both cases are theoretically analyzed. Experimental measurements of ND-3PA agree with this analysis and show that it is enhanced much more than ND-2PG. It is found for both degenerate and nondegenerate photon pairs that the losses dominate the two-photon gain, preventing the possibility of a two-photon semiconductor laser.

Nonlinear optics and ferroelectrics have been recognized for several decades as promising fields with important applications in the area of opto-electronics, photonics, memory devices, etc. High performance electro-optical switching elements for telecommunications and optical information processing are based on the material properties. Hence, there is always a continuous search for new and better materials. In this thesis we have investigated the growth and physical properties of four crystals viz. two NLO and two ferroelectric crystals. This thesis consists of eight chapters. The first chapter gives an overview of historical perspectives of nonlinear optical phenomenon, ferroelectricity and materials developed therein. The second chapter gives a brief description of the underlying theories of crystal growth, nonlinear optics and ferroelectricity. A major portion of this chapter consists of gist of the earlier work carried out on compounds of our interest viz. urea L-malic acid, sodium p-nitrophenolate dihydrate, glycine phosphite and lithium niobate. Synthesis, growth, crystal structure details and some physical properties of these materials are briefed. The third chapter describes the experimental techniques needed to grow as well as characterize these crystals. The experiments are performed on single crystals grown in the laboratory using the solution growth setup and Czochralski crystal puller. These growth units are described in detail. Preliminary characterization techniques like powder Xray diffraction, optical transmission, scanning electron microscopy, Vickers and Knoop hardness are described briefly. Various experimental methods viz. dielectric, polarization reversal, photoacoustic spectroscopy and laser induced damage for characterizing the grown crystals are explained. Urea L-malic acid (ULMA) is a new NLO organic material which is reported to exhibit second harmonic efficiency three times that of the widely used inorganic crystal, KDP. Hence, this material is selected for detailed investigation and the results obtained are discussed in chapter 4. This chapter contains details of single crystal growth and characterization of ULMA. The crystals are grown by slow cooling technique. The complete morphology of the crystal is evaluated using optical goniometry. The grown crystals are characterized for their optical and thermal properties. The defect content in the grown crystal is evaluated by chemical etching. As the surface damage of the crystal by high power lasers limits its performance in NLO applications, a detailed laser induced damage studies are performed on ULMA. Both single shot and multiple shot damage threshold values for 1064 nm and 532 nm laser radiation are determined and correlated with the mechanical hardness. In addition, the thermal diffusivity and thermal conductivity of ULMA along various crystallographic orientations are evaluated using laser induced photoacoustic spectroscopy and the results are interpreted in terms of crystal bonding environment. Another NLO crystal taken up for study is sodium p-nitrophenolate dihydrate (NPNa 2H2O), a semiorganic material. This crystal is a very efficient NLO material and has the advantages of both organics and inorganics. Earlier investigations on growth of NPNa.2H2O in various solvents have shown methanol as the most suitable solvent for growth. Growth from aqueous solution was discarded as it did not yield crystals which are stable. In the present investigation, stable, NLO active NPNa.2H2O crystals are obtained using aqueous solution itself by varying the crystallization conditions and exploring the suitable temperature range. The details of growth and characterization form the subject of fifth chapter. The grown crystals are characterized using optical transmission, XRD and thermo gravimetric analysis. Later, laser induced damage threshold is evaluated for both 1064 nm and 532 nm laser radiation and compared wit the methanol grown ones. A possible mechanism of damage is given. The sixth and seventh chapters deal with growth and characterization of ferroelectric materials namely glycine phosphite and lithium niobate respectively. Glycine phosphite is a low temperature ferroelectric crystal which is well studied in terms of its dielectric and ferroelectric properties. But very few radiation damage studies are reported. The effect of ionizing radiation on ferroelectrics is of considerable interest as it significantly modifies the physical properties of these materials. In the present investigation, effects of X-ray irradiation (_ = 1.5418 °A) on the lattice parameters, dielectric constant, loss tangent, polarization switching characteristics and domain dynamics of glycine phosphite are investigated. X-ray irradiation is performed in the non-polar phase of the sample. The effect as a function of duration of exposure is studied. X-ray irradiation in GPI has resulted in drastic reduction in _ values and shift in transition temperature towards lower temperatures. X-ray irradiation on polarization switching properties of the crystal are also investigated. The activation energy and threshold field of switching increase with the irradiation time. The behaviour of domain wall mobility is quite different from that exhibited by other well known ferroelectrics. These results are discussed in chapter 6 and a possible explanation for the unusual behaviour of domain wall mobility is given. The defect generated is identified as PO32− radical by electron paramagnetic measurement. Lithium niobate (LiNbO3) is an extensively studied material in terms of its NLO and ferroelectric properties. This material has high piezoelectric coupling coefficients along certain directions which makes it suitable for wide band surface acoustic wave applications. Hence there is a demand for good quality, single domain YZ-LiNbO3 substrates. Chapter 7 describes the growth of Z-pulled congruent LiNbO3 using Czochralski technique. Large single crystals of diameter 30 mm and length 80 mm are grown from congruent composition employing Czochralski technique. The grown crystals are multidomain and hence electric field poling is performed to get single domain crystals. Their subsequent characterization for SAW devices upto 200 MHz was performed and compared with the imported substrate. The general conclusions are given in chapter 8 along with possible future work that could be performed on these crystals.

We develop a theory of vectorial wave coupling in cubic photorefractive crystals placed in an alternating ac-field to enhance the nonlinear response. First we analytically and numerically investigate the dependences of the first Fourier harmonics of the space-charge field, induced in an AC-biased sillenite crystal by a light-interference pattern, on the light contrast m. The data obtained was used to extend the vectorial beam-coupling theory on the whole contrast region. In particular, we proved in the general case that despite of essential differences between thediffusion and AC nonlocal responses the later keeps the light interference fringes straight during the interaction. This fundamental feature allows, under certain restrictions, to reduce the nonlinear problem of vectorial coupling to the known linear problem of vectorial Bragg diffraction from a spatially uniform grating, which admits an exact solution. As a result, the nonlinear vectorial problem can be effectively solved for a number of practically important cases.The developed theory was applied to describe the transformation of a momentary phase changes of one of the input beams into the output intensity modulation (so-called grating translation technique). In contrast to the previous studies, we take into account the change of the space-charge field amplitude across the crystal (the coupling effects). The theory developed is employed to optimize the conditions for the linear signal detection under polarization filtering for the transverse and longitudinal optical configurations. We also analyze the possibility of the linear detection without polarization filtering.Illumination of AC-biased photorefractive BTO crystals with a coherent light beam results in development of strong nonlinear scattering. We investigate the angular and polarization characteristics of the scattered light for the diagonal optical configuration and different polarization states of the pump.

In der vorliegenden Arbeit werden die nichtlinearen optischen Eigenschaften der Materialien Lithiumniobat und Di-Zinn-Hexathiohypodiphosphat aufgrund der Suszeptibilität 3. Ordnung und kleiner Polaronen untersucht. Zudem wird gezeigt, dass die Interferenz verschiedenfarbiger Laserpulse die Aufzeichnung von statischen und dynamischen holographischen Gittern ermöglicht. Ein Teil dieser Arbeit ist in den im Anhang angegebenen 6 Publikationen bereits veröffentlicht. Lithiumniobat wird mit einer Erweiterung des Z-Scan Experiments untersucht, welches die Pulslängenabhängige Messung der nichtlinearen Absorption und der nichtlinearen Brechungsindexänderung ermöglicht. Dabei konnte festgestellt werden, dass bei sehr kurzen Pulslängen von 70 fs ein Effekt der Polaronen auf die nichtlineare Absorption vernachlässigbar ist und die Zwei-Photonen-Absorption die nichtlineare Absorption dominiert. Mit größerer Pulslänge gibt es allerdings Abweichungen zwischen der Theorie der Zwei-Photonen-Absorption und den Messergebnissen. Mit der Entwicklung eines Polaronen-Anregungs-Modells, welches eine polaronische Absorption aufgrund wiederholtem optisch induziertem Hopping annimmt, konnte dieser Effekt konsistent erklärt werden. Die Messungen der nichtlinearen Brechungsindexänderung lassen darauf schließen, dass sowohl freie Ladungsträger als auch kleine Polaronen neben der Suszeptibilität 3. Ordnung einen Einfluss auf die Brechungsindexänderung haben, da eine nichtlineare Abhängigkeit von der Intensität auch bei Pulslängen von 70 fs festgestellt werden konnte. Analog dazu konnte in Di-Zinn-Hexathiohypodiphosphat ein großer Zwei-Photonen-Absorptionskoeffizient festgestellt werden, welcher für Photonenenergien nahe der Bandkante Werte zeigt, die größer sind als theoretischen Überlegungen zeigen. Eine transiente Absorption nach optischer Anregung, gemessen durch ein Anreg-Abtast-Experiment, sowie Literatur legen nahe, dass in Di-Zinn-Hexathiohypodiphosphat gebundene Lochpolaronen durch optische Anregung entstehen können. Durch den hohen Zwei-Photonen-Absorptionskoeffizienten konnte das Aufzeichnen eines kontrastreichen, dynamischen Amplitudengitters mittels Femtosekundenpulsen gezeigt und nachgewiesen werden. Die Kürze der Femtosekundenpulse ermöglicht aber nicht nur das Aufzeichnen eines Zwei-Photonen-Absorptionsgitters aufgrund der hohen Intensitäten, sondern erlaubt zudem die Beobachtung von Interferenz zwischen verschiedenfarbigen Pulsen. In der Zeitspanne der Pulslänge beträgt die Bewegung der Interferenzstreifen, welche in der Größenordnung der Lichtgeschwindigkeit liegt, nur ein Bruchteil der Streifendistanz, sodass das Interferenzmuster eingefroren und beobachtbar erscheint. Somit lassen sich statische Hologramme in holographischen Filmen, wie auch dynamische Hologramme aufzeichnen. Über ein dynamisches holographisches Gitter mittels Zwei-Photonen-Absorption konnte so eine Frequenzkonversion durch Dopplerverschiebung in Lithiumniobat gezeigt werden.