Title page, abstract and table of contents only. The complete thesis in print form is available from the University of Adelaide Library. / With the increasing use of lasers it is necessary to develop materials that can provide protection to eyes and other sensitive devices. This thesis reports on an investigation into optical limiting of Transition Metal Acetylides (TMAs) that transmit ambient light levels of light but block high energy (laser) light across the visible part of the spectrum. A standard optical limiting testbed is used to measure opt~callimiting at 470, 532 and 630 om for a wide range of Pt:ethynyl related TMAs. I report the effect on optical limiting of altering the central bridge, heavy metal, terminal group, solubilising group and oligomerisation. Most of these materials showed poor optical limiting, especially in the red. Two dimers of Pt:ethynyl, however, have clamping levels at 532 om better than that for Pt:ethynyl. I therefore describe a detailed spectroscopic investigation of two series of oligomers and discuss their structure/property relationships. This investigation also includes a precursor ofPtethynyl, PEPE, which shows remarkable limiting. I also report modelling of optical limiting using a 5-level model constructed using the spectroscopic data. I show that the 5-level model can be validated and accurately predicts the limiting for PEPE against both ps and ns pulses. It can also be used to predict ps limiting for Pt:ethynyl and its oligomers. For ns pulses, however, it predicts much less limiting than that observed. I therefore propose a new mechanism that is important for ns limiting by TMAs. Finally I discuss the broadband limiting of these materials and from analysis of the measurements· I describe structures of materials that may show promising broadband optical limiting. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1320307 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008

Title page, abstract and table of contents only. The complete thesis in print form is available from the University of Adelaide Library. / With the increasing use of lasers it is necessary to develop materials that can provide protection to eyes and other sensitive devices. This thesis reports on an investigation into optical limiting of Transition Metal Acetylides (TMAs) that transmit ambient light levels of light but block high energy (laser) light across the visible part of the spectrum. A standard optical limiting testbed is used to measure opt~callimiting at 470, 532 and 630 om for a wide range of Pt:ethynyl related TMAs. I report the effect on optical limiting of altering the central bridge, heavy metal, terminal group, solubilising group and oligomerisation. Most of these materials showed poor optical limiting, especially in the red. Two dimers of Pt:ethynyl, however, have clamping levels at 532 om better than that for Pt:ethynyl. I therefore describe a detailed spectroscopic investigation of two series of oligomers and discuss their structure/property relationships. This investigation also includes a precursor ofPtethynyl, PEPE, which shows remarkable limiting. I also report modelling of optical limiting using a 5-level model constructed using the spectroscopic data. I show that the 5-level model can be validated and accurately predicts the limiting for PEPE against both ps and ns pulses. It can also be used to predict ps limiting for Pt:ethynyl and its oligomers. For ns pulses, however, it predicts much less limiting than that observed. I therefore propose a new mechanism that is important for ns limiting by TMAs. Finally I discuss the broadband limiting of these materials and from analysis of the measurements· I describe structures of materials that may show promising broadband optical limiting. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1320307 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008

Title page, abstract and table of contents only. The complete thesis in print form is available from the University of Adelaide Library. / With the increasing use of lasers it is necessary to develop materials that can provide protection to eyes and other sensitive devices. This thesis reports on an investigation into optical limiting of Transition Metal Acetylides (TMAs) that transmit ambient light levels of light but block high energy (laser) light across the visible part of the spectrum. A standard optical limiting testbed is used to measure opt~callimiting at 470, 532 and 630 om for a wide range of Pt:ethynyl related TMAs. I report the effect on optical limiting of altering the central bridge, heavy metal, terminal group, solubilising group and oligomerisation. Most of these materials showed poor optical limiting, especially in the red. Two dimers of Pt:ethynyl, however, have clamping levels at 532 om better than that for Pt:ethynyl. I therefore describe a detailed spectroscopic investigation of two series of oligomers and discuss their structure/property relationships. This investigation also includes a precursor ofPtethynyl, PEPE, which shows remarkable limiting. I also report modelling of optical limiting using a 5-level model constructed using the spectroscopic data. I show that the 5-level model can be validated and accurately predicts the limiting for PEPE against both ps and ns pulses. It can also be used to predict ps limiting for Pt:ethynyl and its oligomers. For ns pulses, however, it predicts much less limiting than that observed. I therefore propose a new mechanism that is important for ns limiting by TMAs. Finally I discuss the broadband limiting of these materials and from analysis of the measurements· I describe structures of materials that may show promising broadband optical limiting. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1320307 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008

Title page, abstract and table of contents only. The complete thesis in print form is available from the University of Adelaide Library. / With the increasing use of lasers it is necessary to develop materials that can provide protection to eyes and other sensitive devices. This thesis reports on an investigation into optical limiting of Transition Metal Acetylides (TMAs) that transmit ambient light levels of light but block high energy (laser) light across the visible part of the spectrum. A standard optical limiting testbed is used to measure opt~callimiting at 470, 532 and 630 om for a wide range of Pt:ethynyl related TMAs. I report the effect on optical limiting of altering the central bridge, heavy metal, terminal group, solubilising group and oligomerisation. Most of these materials showed poor optical limiting, especially in the red. Two dimers of Pt:ethynyl, however, have clamping levels at 532 om better than that for Pt:ethynyl. I therefore describe a detailed spectroscopic investigation of two series of oligomers and discuss their structure/property relationships. This investigation also includes a precursor ofPtethynyl, PEPE, which shows remarkable limiting. I also report modelling of optical limiting using a 5-level model constructed using the spectroscopic data. I show that the 5-level model can be validated and accurately predicts the limiting for PEPE against both ps and ns pulses. It can also be used to predict ps limiting for Pt:ethynyl and its oligomers. For ns pulses, however, it predicts much less limiting than that observed. I therefore propose a new mechanism that is important for ns limiting by TMAs. Finally I discuss the broadband limiting of these materials and from analysis of the measurements· I describe structures of materials that may show promising broadband optical limiting. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1320307 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008

Two experimental methods, optical limiting and degenerate four-wave mixing, are employed to study the nonlinear optical properties of various novel fullerenes structures. Optical limiting refers to decreased transmittance of a material with increased incident light intensity. Detailed measurements of the wavelength-dependence of fullerene optical limiters have illustrated several key features of reverse saturable absorption. Most important among these is the requirement of weak but non-negligible ground state absorption. We have shown that the optical limiting performance of C₆₀ can be extended into the near infrared range by appropriate modifications of the structure such as higher cage fullerenes or derivatization of the basic C₆₀ molecule. The higher cage fullerene C₇₆ shows improved optical limiting behavior compared to C₆₀, for wavelengths higher than 650 nm, but becomes a weak limiter in the 800 nm range. C₈₄, even at high concentrations in [alpha]-chloronaphthalene, does not reach the good performance of C₆₀, but instead shows weak optical limiting in the 800 nm range. We also demonstrate that by attaching various groups to the C₆₀ molecule, we can extend the optical limiting performance in the near infrared regime. The C₆₀ derivatives studied, (C₆₀ cyclic ketone, C₆₀ secondary amine, C₆₀CHC₆H₄CO₂H, and C₆₀C₄H₄(CH₃)CH₂O₂C(CH₂)CO₂H), have a similar characteristic: the attached groups cause a symmetry-breaking of the C₆₀ sphere and, therefore, there are new allowed transitions that appear as absorption features up to 750 nm. The optical limiting measurements show that these materials, even for low input energies, have an exceptionally strong optical limiting response in the 640 to 750 nm spectral region. For wavelengths higher than 800 nm, however, they become transparent and no optical limiting is observed. Excited state absorption cross-sections obtained from analysis of the optical limiting data reveal that the C₆₀ derivatives have a maximum triplet-triplet absorption cross-section at 700 nm, which is shifted from the 750 nm value for the C₆₀ molecule. For the first time, optical limiting measurements are performed on five separate C₈₄ isomers. These intriguing results show that the optical limiting behavior is strongly dependent on the cage symmetry. It is also found that the most abundant isomer does not have the strongest optical limiting performance, but is in fact one of the weaker optical limiters of the isomers isolated so far. The endohedral metallofullerenes are a unique class of fullerene materials and consist of one or more metal atoms encapsulated inside the buckyball cage. An important characteristic of these materials is the charge-transfer from the dopant atoms to the fullerene cage, which has a high electron affinity. The charge-transfer is similar to the optical excitation in a material, but although the electrons are placed in the lowest unoccupied molecular orbital (LUMO), there are no holes produced in the highest occupied molecular orbital (HOMO). This is an important analogy, since it has been previously shown that optical excitation enhances the nonlinear optical properties of a material. The nonresonant degenerate four-wave mixing experiments performed on the endohedral metallofullerene Er₂@C₈₂, at 1064 nm, show that the third order nonlinear susceptibility value is increased by orders of magnitude relative to the empty cage fullerenes, thus, confirming the charge-transfer process from the encapsulated atoms to the fullerene cage. We obtain a value [gamma]_xyyx⁽³⁾( &#173 [omega]; [omega], [omega], &#173 [omega])= &#173 8.65 &#215 10⁻³² esu for the molecular second order hyperpolarizability, which is almost three orders of magnitude larger than the values reported in literature for an empty cage fullerene. / Ph. D.

I have conducted detailed experimental and theoretical studies of the nonlinear optical properties of semiconductor materials useful for optical limiting. I have constructed optical limiters utilizing two-photon absorption along with photogenerated carrier defocusing as well as the bound electronic nonlinearity using the semiconducting material ZnSe. I have optimized the focusing geometry to achieve a large dynamic range while maintaining a low limiting energy for the device. The ZnSe monolithic optical limiter has achieved a limiting energy as low as 13 nJ (corresponding to 300W peak power) and a dynamic range as large as 105 at 532 nm using psec pulses. Theoretical analysis showed that the ZnSe device has a broad-band response covering the wavelength range from 550 nm to 800 nm. Moreover, I found that existing theoretical models (e.g. the Auston model and the band-resonant model using Boltzmann statistics) adequately describe the photo-generated carriers refractive nonlinearity in ZnSe. Material nonlinear optical parameters, such as the two-photon absorption coefficient β_2=5.5cm/GW, the refraction per unit carrier density σ_n=-0.8∗10^-21cm^3 and the bound electronic refraction n_2=-4∗10^-11esu, have been measured via time-integrated beam distortion experiments in the near field. A numerical code has been written to simulate the beam distortion in order to extract the previously mentioned material parameters. In addition, I have performed time-resolved distortion measurements that provide an intuitive picture of the carrier generation process via two-photon absorption. I also characterized the optical nonlinearities in a ZnSe Fabry-Perot thin film structure (an interference filter). I concluded that the nonlinear absorption alone in the thin film is insufficient to build an effective optical limiter, as it did not show a net change in refraction using psec pulses. An innovative numerical program was developed to simulate the nonlinear beam propagation inside the Fabry-Perot structure. For comparison, pump-probe experiments were performed using both thin film and bulk ZnSe. The results showed relatively long carrier lifetimes (>300 psec) in both samples. A numerical code was written to fit the pump-probe experimental results. The fitting yielded that carrier lifetimes (recombination through traps), radiative decay rate, two-photon absorption coefficient as well as the free carrier absorption coefficient for ZnSe bulk material.

Limitadores ópticos são dispositivos que apresentam alta transmitância para baixas intensidades de luz incidente e, inversamente, baixa transmitância para altas intensidades, sendo usados como protetores contra danos em sensores ópticos e olhos humanos. Com o objetivo de estudarmos novos materiais com mecanismos não lineares eficientes para o processo de limitação, bem como novas geometrias ópticas, apresentamos neste trabalho o desenvolvimento de um limitador óptico baseado na absorção saturada reversa de porfirinas e metaloporfirinas. Construímos também um dispositivo baseado na configuração óptica bifocal, usando porfirina como absorvedor saturável reverso. Além disso, obtivemos parâmetros espectroscópicos do estado excitado pelos ajustes teóricos das curvas de transmitância, através da resolução de equações de taxa. / Optical limiters are devices with a high transmittance in the presence of low intensity light, and a considerable lower transmittance otherwise, been used as protectors against damage in optical sensors and human eyes. Aiming at searching for new materials and optical geometries efficient for optical limiting. We report on the development of an optical limiter based on the reverse saturable absorption in porphyrin and metalioporphyrins. We also built a device-based .on a cascade focus configuration, using free base porphyrin as the absorber. Besides, we obtain the excited state spectroscopy parameters by the theoretical fitting of transmittance curves, by solving a set of rate equations.

>Magister Scientiae - MSc / Recent research shows that the study of optical properties of organic material natural dyes has gained much consideration. The specific functional groups in several natural dyes remain essential for the large nonlinear absorption expressed in terms of nonlinear optical susceptibilities or other mechanism of absorption such as two photon absorption (TPA), reverse saturable absorption (RSA) or intensitydependent refractive index characteristic. In this thesis we highlight the optical limiting responses of selected natural dyes as nonlinear response in the femtosecond regime. This technique refers to the decrease of the transmittance of the material with the increased incident light intensity.Three dyes derived from beetroot, flame flower and mimosa flower dyes were investigated. The results showed a limiting behaviour around 795 mW for the beetroot and the flame dye while there is total transmission in the flame dye sample. The performance of the nonlinearity i.e. the optical limiting is related to the existence of alternating single and double bonds(i.e. C-C and C=C bonds) in the molecules that provides the material with the electron delocalization, but also it is related to the light intensity.Beside nonlinearity study, crystallographic investigation was carried out for more possible applicability of the selected dyes and this concerned only the mimosa and flame flower dye thin film samples since the beetroot thin film was very sensitive to strong irradiation (i.e. immediately destroyed when exposed to light with high intensity). For more stability,dye solutions were encapsulated in gels for further measurements.

The overall efficiency of photovoltaics is dictated by processes occurring within it. These processes include exciton formation, diffusion, dissociation and charge collection. This dissertation will focus around the fundamental issue of charge collection. In organic photovoltaics (OPVs) the rate of charge injection is dominated by the interaction between dissimilar materials, usually organic compound interacting with inorganic ones. In order to improve this rate of injection and, by direct consequence the efficiency of this process, fundamental knowledge of this organic-inorganic interface must be gained. In this work the focus will reside solely on creating molecules capable of probing the interface between the indium tin oxide (ITO) and the donor layer. At this interface, the usual charge transfer being transferred is the hole. Chapters 2 and 3 detail the synthesis and photophysical characterization of porphyrin-perylene diimide (Por-PDI) and porphyrin-fullerene (Por-C₆₀) molecular dyads. The idea behind these moieties is that covalent attachment of these species to ITO should lead to a robust ohmic contact. Since these molecular dyads are capable of producing charge-separated states after photoexcitation, they should have the capacity to produce a radical-cation in close proximity to the ITO. This will translate to a capacity for probing the dynamics of the hole injection at this interface. Studies performed demonstrate that in fact these dyads are capable of producing a charge-separated state upon photo-excitation. The lifetimes of these states were determine to be 35 ps and 3 ns for the Por-PDI and Por-C₆₀ respectively. Chapter 4 takes a different turn. It is focused on the application and extension of a solvent-free synthesis of metallated phthalocyanines (Pcs). Shown in chapter 4 is the synthesis of a series of metallated Pcs using various transition metals and group 3 elements. Photophysical and electrochemical investigation of these materials shows that they have near-infrared absorption and relative high HOMO levels making them potential candidates for OPV applications. In addition, they displayed non-linear optical behavior due to their highly polarizable pi-systems and the presence of axial susbtituents. Finally Chapter 5 describes the synthesis and characterization of porphyrin possessing rigid linkers. This chapter also shows the further directions in which the various ideas presented in this work could be driven.

This thesis descibes a theoretical study of nonlinear self-focusing as applied to the metrology of the nonlinear optical parameters of a medium. It also studies the phe- nomenon of optical power limiting which utilizes self-focusing e ects. As an analytical tool, a mode decomposition method which uses an orthogonal and complete set of Gaussian-Laguerre modes as a basis set is used to treat these problems. Nonlinear media both in the thin and thick limits are investigated. For thin media, a closed form expression is derived which describes the optical eld of an initally Gaussian beam that is perturbed by a thin nonlinear material which exhibits nonlinear absorption as well as nonlinear refraction. This result is valid for any regime of nonlinearity in the thin medium approximation. Thick media are treated using a numerical extension of the Gaussian-Laguerre Mode Decomposition technique. Spatial scanning techniques such as the Z-scan that rely on self-focusing e ects and that are used to measure the nonlinear optical parameters of a material are studied in detail. Optical limiting in both thick and thin media is also investigated.