Detailed studies are presented of thin films that self-assemble into the noncentrosymmetric structure required for second order nonlinear optical responses. Second harmonic generation is used as a probe of the second-order nonlinear optical susceptibility (c(2)) of ionic self-assembled monolayer (ISAM) films. Films produced from the ISAM technique are shown to possess significant c(2), with values presently comparable to quartz (c(2)=1.53*10⁹ esu). These films show exceptional stability over time, with negligible decrease in c(2) after 26 months. ISAM films self-assemble from polyelectrolyte solutions due to coulombic interactions between a charged substrate and the charged polymer in solution. This process is self-limiting since charge overcompensation at the surface restricts further deposition as like charges accumulate at the surface. We have found that this 'kinetically hindered equilibrium' occurs quickly for the samples studied, after approximately 45 seconds immersion. Non-centrosymmetry is obtained during deposition as chromophores orient towards the substrate as a strong, localized collection of opposite charge. This net orientation is partially diminished as some amount of chromophore extends in the opposite direction at the film/solution interface. Second harmonic measurements suggest that chromophores at the outermost interface collapse against the film surface when dried, resulting in a larger c(2) than other 'capped' layers. Any polymer which is not located at the interfaces is thought to possess random orientation, and therefore does not contribute to c(2). We have investigated how ionic strength and solution pH affect the structure of ISAM films. These parameters serve to control the electrostatic screening in solution. Low salt concentrations result in low or no electrostatic screening. As a result, charges on a polymer strongly feel one another's presence, and decrease the net electrostatic energy by maximizing their distance from each other. This results in a rod-like conformation, which when adsorbed onto the film surface produces thin layers. Large salt concentrations serve to screen the electrostatic interaction. Because charges do not experience the strong repulsion from their neighbors, the polymer backbone is more likely to loop and coil. If the polymer is weakly soluble (pH near the solubility edge), the polymer will loop about itself and other polymer chains in order to reduce the number of polymer/water contacts. Increased screening results in adsorption of thicker films. We show that this also results in a marginal increase in film density, likely due to an increase in polymer interpenetration of adjacent layers. We can associate an increase in chromophore population at the interface with this increase in density. The reduction in screening also is shown to decrease the chromophore orientation angle, presumably by decreasing the repulsion between charges located on the chromophore ends. The improved orientation leads to an increased non-centrosymmetry in the layer. c(2) is decreased, however, as film thickness (and therefore the population of randomly oriented chromophore between interfaces) increases faster than the improvements to non-centrosymmetry at the interface. We have investigated the thermal stability of ISAM films at elevated temperatures, and have found that these films do not exhibit a permanent decay of c(2) with increased temperature as do poled guest-host polymers. A temperature-dependent decrease is observed for temperatures up to 250°C. This decrease is completely reversible (for films heated to 150C), with c(2) recovering its initial value upon cooling in spite of a glass transition temperature measured as Tg=140°C The decrease in c(2) is thought to be due to a combination of effects. Predominant decrease is thought to be due to disassociation of ionic bonds, which serve to provide noncentrosymmetry in films. A slower, smaller decay due to decrease in moisture content of the films at high temperature is also thought to be present. / Ph. D.

The interaction of a high power, high frequency (HF) pump/electromagnetic (EM) wave transmitted from a ground-based station with the ionosphere, experiments which have been termed "ionospheric heating", produces secondary radiation known as stimulated electromagnetic emissions (SEEs). SEEs have been developed into powerful diagnostics yielding information such as electron temperature, ion species and hydrodynamic evolution of the modified ionospheric plasma. Classic SEEs which exist outside ±1 kHz of the pump wave frequency (ω0) have recently been classified into wideband SEEs (PW-WSEEs) and distinguished from narrowband SEEs (PW-NSEEs) which exist within ±1 kHz of ω0, where the "PW" prefix has been used to indicate that the frequency regimes in the aforementioned classification are relative to the pump wave (PW) frequency. The occurrence of SEEs near 2ω0 is known as second harmonic generation (SHG). SHG is longstanding and well-established in the field of Laser Plasma Interactions (LPI) where SHG has been harnessed to yield diagnostics such as the velocity of the critical region of the plasma, inference of the region in the plasma where the interaction that results in SHG occurs, plasma turbulence and density scale lengths. Past studies of ionospheric heating SHG were limited by the effective radiated power (ERP) available at ionospheric heating facilities and the frequency resolution of receivers/spectrum analyzers of the time. Experimental observations from these past studies reported either SEEs produced as a result of SHG in isolation or compared these SEEs with PW- WSEEs. Moreover, these experiments did not evaluate effects such as transmit ERP, tilt of the transmit antenna beam from the geomagnetic field (B0) and the offset of ω0 from harmonics of the electron gyrofrequency (ωce) on SEEs within a narrowband of twice the pump wave frequency produced as a result of SHG. Also, these studies did not attempt to draw from the knowledge-base on SHG from LPI. The novelty of the experimental observations in this dissertation is the juxtaposition of PW-NSEEs and second harmonic narrowband SEEs (SH-NSEEs), which are SEEs within kHz of 2ω0, measured at the same time. The heating experiments were all performed at HAARP using an O-mode polarized EM pump wave. Additionally, these measurements evaluate the effects on SHG of the transmit ERP, tilt of the transmit station antenna beam from the geomagnetic field (B0) and the offset of ω0 from nωce, n = 2, 3. The experimental observations show, for the first time, a clear association between PW-NSEEs and SH-NSEEs. This association is subsequently used, in conjunction with theories from LPI to propose the non-linear wave-mixing mechanisms responsible for the SH-NSEEs. As a prelude to harnessing the wealth of diagnostics that can be obtained from SHG, initial diagnostics of the velocity of the critical region and the interaction region where SHG occurs are determined using theories from LPI. With the association between PW-NSEEs and SH-NSEEs established, Particle- In-Cell (PIC) simulations are used to investigate the characteristics of a PW- NSEE herein referred to as the "SBS line", produced as a result of stimulated Brillouin scatter (SBS) instability in which the pump EM wave decays into a backscattered EM wave and an ion acoustic wave. The PIC simulations reveal that for high pump powers, the SBS line, which is intense at the onset of the heating experiment, is suppressed within 3 seconds due to the development of cavities in the ionospheric plasma (density) in which the pump wave depletes its energy in heating up electrons. Although, no PIC simulation results of SHG have been presented in this work, the association between PW-NSEEs and SH-NSEEs shown in this work is used to propose that similar mechanisms are responsible for the suppression the SBS line and its associated SH-NSEE for high pump powers. Results from ionospheric heating experiments presented in this dissertation show a rapid suppression of both the SBS line and its associated SH-NSEE for high pump powers. The attribution of the suppression of SH-NSEEs to the development of artificial field-aligned irregularities (AFAIs) in a past study fails to explain the rapid suppression in the experimental observations contained herein since the suppression occurs on a much faster timescale than the development of AFAIs. Thus, the PIC model results have led to a more feasible interpretation of the observed rapid suppression. To re-iterate, the contributions of this dissertation are as follows: 1. First observations of an SH-NSEE named "SH decay line" within 2ω0±30 Hz. The SH decay line occurs at the same transmit power as the SBS line within ω0±30 Hz and both of these SEEs are suppressed for ω0 ≈ 3ωce. Offset of the SH decay line from 2ω0 is twice the offset of the SBS line from ω0. 2. First experimental evaluation of the impact of B0 assessed by stepping the transmit beam offset from B0 and stepping ω0 near 2ωce shows contemporaneous SH-NSEEs and PW-NSEEs both ordered by the O+ ion cyclotron frequency. 3. First experimental observations of suppression of SBS line and SH decay line for high pump powers, which unlike a past study cannot be attributed to AFAIs. 4. First PIC simulation investigation of suppression of SBS line observed during high pump power ionospheric heating, revealing depletion of pump energy in heating electrons in cavities created in the plasma (density) as the mechanism responsible for the suppression. Broadening of SBS line observed in ionospheric heating with high power is also observed in PIC simulation results. This work has laid the foundations to develop SHG into powerful ionospheric diagnostics. / Doctor of Philosophy / When a high power, high frequency radio wave is injected from a ground-based transmit station into the ionosphere, a region of Earth's atmosphere containing charged particles in addition some neutral atoms and molecules, the frequency spectrum measured at a location removed from the transmit station shows emissions at other frequencies in addition to an emission at the transmit frequency. The emissions at these other frequencies are known as stimulated electromagnetic emissions (SEEs). The frequency offsets of SEEs contain information such as the average kinetic energy associated with random motion of electrons, a parameter known as electron temperature and the ion species present in the region of the ionosphere the radio wave is injected into. The occurrence of SEEs near twice the pump wave frequency is known as second harmonic generation. This dissertation presents experimental observations that compare SEEs which exist within ±1 kHz of the transmit frequency with SEEs which exist within a similar frequency range of twice the transmit frequency unlike past studies. This dissertation also investigates effects of varying the transmit frequency, power and the direction of the transmit station antenna beam relative to the local direction of the magnetic field of the Earth. These new studies reveal, for the first time, a similarity in characteristics of the SEEs near the transmit frequency and two times the transmit frequency. This similarity is used in conjunction with theories from studies of Laser Plasma Interaction (LPI), which have corollaries with high power radio wave-ionosphere interaction, to propose the processes that underlie the occurrence of SEEs near twice the transmit frequency. Methods from LPI have also been used for the first time to obtain measurements of some parameters of the ionosphere. High power radio wave-ionosphere interaction experiments are very expensive and moreover, direct measurement of ionospheric parameters/processes require radar facilities which may not be available or sounding rockets or satellites which increase the cost of experiments. Computer simulations offer a facile and an inexpensive means to investigate SEEs and processes internal to the ionosphere. Computer simulations have been used for the first time in this dissertation to investigate the mechanisms responsible for the characteristics of SEEs near the transmit frequency for low and high transmit powers. Since an association has been established in this dissertation between SEEs near the transmit frequency and SEEs near twice the transmit frequency, the mechanisms responsible for the characteristics for the SEEs near the transmit frequency for high transmit power, have been proposed to be the same mechanisms responsible for the characteristics of SEEs near twice the transmit frequency for a similar transmit power regime. The experimental results, computer simulation results and the corollaries drawn between high power radio wave-ionosphere interaction and LPI detailed in this dissertation have opened new doors to develop SEEs near twice the transmit frequency into a powerful tool to study the ionosphere.

Thesis (PhD (Physics))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Silicon/silicon dioxide (Si/SiO2) interface is widely used in microelectronics as the gate between the drain and source of most metal oxide semiconductor field effect transistors (MOSFETs). The functionality, reliability and electrical properties of such transistors are strongly dependent on the quality of the Si/SiO2 structure forming the gate. Characterization of the Si/SiO2 interface is important in understanding device degradation therefore the Si/SiO2 interface is a subject of intensive investigation. Research studies of Si/SiO2 interfaces using optical methods have been reported by many groups around the world but to date many open questions still exist. The physics of photoinduced trap or defect generation processes and the subsequent trapping of charge carriers, the precise role of photoinduced interfacial electric field in altering optical properties of the Si/SiO2 interface and its role in affecting the second harmonic (SH) yield measurements are not well understood. In this work a commercial near infrared femtosecond (fs) laser source [1.55 eV, 75 ± 5 fs, 10 nJ, 80 MHz] is used to study native Si/SiO2 interfaces of free standing single crystalline Si membrane and bulk Si. Optical second harmonic (SH) generated at the Si/SiO2 interfaces of a Si membrane in reflection and for the first time in transmission is demonstrated as well as stationary, single colour, pump-probe reflectivity measurements from the Si/SiO2 interface of bulk n-type Si. The experimental setups for the second harmonic generation (SHG) and pump-probe techniques were designed and implemented, and measurements were recorded by a computer controlled data acquisition system. Free standing Si membrane samples were successfully produced at the Institut f¨ur Photonische Technologien (IPHT) in Jena, Germany from bulk Si using a chemical etching process and were characterised using the z-scan technique. The penetration depth of light with a photon energy of 1.55 eV in silicon allows transmission of the fundamental fs laser pulses through the Si membrane (∼ 10 μm in thickness) and this is exploited to generate a SH signal in transmission from the Si/SiO2 interfaces of the Si membrane. In the presence of sufficiently intense fs laser light defects are created at the interfaces and populated by multiphoton transfer of charges from Si to SiO2 where they are subsequently trapped. The transfer of charge establishes interfacial electric fields across the interfaces of the Si membrane and this enhances SHG. This phenomenon is called electric field induced second harmonic (EFISH) generation. To our knowledge, EFISH measurements from interfaces of Si membrane performed in transmission are demonstrated for the first time in the present study. The demonstration of EFISH in transmission revealed new results which allowed us to provide additional perspectives on the EFISH generation process at Si/SiO2 interfaces never reported before. The temporal response of SH signals from virgin spots were recorded at different incident laser powers for both reflection and transmission geometries. The SH responses measured in transmission were observed to be time dependent and show an increase during irradiation of the sample corresponding to EFISH process. A series of SH measurements were recorded at different laser powers to compare the magnitudes of SH yield in each detection geometry for a single Si/SiO2 interface. The magnitude of the SH yield measured in transmission was higher than expected and surpassed the SH yield measured in reflection. The expectation is based on the fact that the local intensity of the fundamental beam at the second interface where the SH in transmission is generated is low compared to the local intensity at the first interface where the SH in reflection originates. A physical model is developed to consistently interpret the experimental results obtained in this study. In this model we established the origin of EFISH signals in each detection geometry, explain the unexpected high SH signals measured in transmission and provide an analysis of the time constants extracted from SH response in transmission and reflection. In addition, we also report for the first time stationary pump-probe reflectivity measurements from bulk n-type Si(111) samples with native oxide. A strong pump beam was focused on the same spot as a weak probe beam from the same fs laser source. The change in reflectivity of the Si(111)/SiO2 system was recorded by monitoring the change in intensity of the weak reflected probe beam. The temporal evolutions of the reflectivity of the material were recorded at different pump powers. The reflectivity of the material increases over several minutes of irradiation and reaches steady-state after long time irradiation. The change in reflectivity of the material is attributed to a nonlinear process called Kerr effect, and the temporal response arises from the photoinduced interfacial electric field across the Si(111)/SiO2 interface caused by multiphoton charge transfer from bulk Si(111) to the SiO2 layer. The results reported in this study contribute to the understanding of the photoinduced interfacial electric field caused by charge carrier separation across buried solid-solid interfaces. They also reveal nonlinear optical processes such as the Kerr effect caused by charge dynamics across the interface in addition to the well known SHG process. / AFRIKAANSE OPSOMMING: Die silikon/silikon dioksied (Si/SiO2) skeidingsvlak word algemeen gebruik in mikro-elektronika as die hek tussen die put en die bron van die meeste metaaloksied halfgeleier veld-effek transistors (MOSFETs). Die werkverrigting, betroubaarheid en elektriese eienskappe van sulke transistors word grootliks bepaal deur die kwaliteit van die Si/SiO2 struktuur wat die hek vorm. Karakterisering van die Si/SiO2 skeidingsvlak is belangrik om die degradering van die transistor te verstaan en daarom is die Si/SiO2 skeidingsvlak die onderwerp van intensiewe ondersoek. Ondersoek van die Si/SiO2 skeidingsvlak deur van optiese metodes gebruik te maak is geraporteer deur verskeie internasionale groepe, maar daar bestaan tot vandag toe nog n groot aantal onbeantwoorde vrae. Die fisika van die fotogenduseerde generering van defekte en van posisies waarin ladings gevang kan word, asook die daaropvolgende vasvang van ladingsdraers, die presiese rol van die fotoge¨ınduseerde elektriese veld oor die skeidingsvlak in die verandering van die optiese eienskappe van die Si/SiO2 skeidingsvlak en die grootte van die tweede harmoniek (SH) sein word nog nie goed verstaan nie. In hierdie werk word n kommersile naby-infrarooi femtosekonde (fs) laserbron [1.55 eV, 75 ± 5 fs, 10 nJ, 80 MHz] gebruik om natuurlike Si/SiO2 skeidingsvlakke van vrystaande enkelkristallyne Si membrane en soliede Si te bestudeer. Optiese tweede harmoniek (SH) wat by die Si/SiO2 skeidingsvlakke van ’n Si membraan gegenereer word - in refleksie en vir die eerste keer in transmissie - is gedemonstreer, asook stasionˆere, een-golflengte pomp-toets refleksiemetings op die Si/SiO2 skeidingsvlak van soliede n-gedoteerde Si. Die eksperimentele opstellings vir die tweede harmoniek generering (SHG) en pomp-toets tegnieke is ontwerp en uitgevoer en metings is opgeneem deur ’n rekenaarbeheerde dataversamelingstelsel. Vrystaande Si membraan monsters is suksesvol by die Institut f¨ur Photonische Technologien (IPHT) in Jena, Duitsland vervaardig uit soliede Si deur ’n chemiese etsproses en is gekarakteriseer met behulp van die z-skanderingstegniek as deel van hierdie studie. Die diepte waartoe lig met ’n fotonenergie van 1.55 eV in silikon indring laat die transmissie van die fundamentele fs laserpulse deur die Si membraan (met ∼ 10 μm dikte) toe en dit word ontgin om ’n SH sein van die Si/SiO2 skeidingsvlakke van die Si membraan in transmissie te meet. In die teenwoordigheid van fs laserlig met voldoende intensiteit word defekte by die skeidingsvlakke geskep en bevolk deur meer-foton ladingsoordrag van die Si na die SiO2 waar die ladings daaropvolgens vasgevang word. Die oordrag van ladings skep elektriese velde oor die skeidingsvlakke van die Si membraan en dit versterk die SHG. Hierdie verskynsel word elektriese veld ge¨ınduseerde tweede harmoniek (EFISH) generering genoem. Sover ons kennis strek is die meting van EFISH seine van skeidingsvlakke van Si membrane in transmissie vir die eerste keer in hierdie studie gedemonstreer. Die demonstrasie van EFISH in transmissie het nuwe resultate opgelewer wat ons toegelaat het om bykomende perspektiewe op die EFISH genereringsproses by Si/SiO2 skeidingsvlakke te verskaf waaroor nog nooit vantevore verslag gedoen is nie. Die tydafhanklike gedrag van die SH seine van voorheen onbestraalde posisies is gemeet by verskillende drywings van die inkomende laserbundel vir beide die refleksie en transmissie geometrie¨e. Die gedrag van die SH sein in transmissie is waargeneem om tydafhanklik te wees en ’n toename te toon gedurende bestraling van die monster in ooreenstemming met EFISH prosesse. ’n Reeks van SH metings is opgeneem by verskillende laserdrywings om die groottes van die SH opbrengste in elke meetgeometrie vir ’n enkele Si/SiO2 skeidingsvlak te vergelyk. Die grootte van die SH opbrengs wat in transmissie gemeet is was ho¨er as verwag is en het die grootte van die SH opbrengs in refleksie oortref. Die verwagting is gebaseer op die feit dat die lokale intensiteit by die tweede skeidingsvlak waar SH in transmisie gegenereer word relatief laag is in vergelyking met die lokale intensiteit by die eerste skeidingsvlak waar SH in refleksie ontstaan. ’n Fisiese model is ontwikkel om die eksperimentele resultate wat in hierdie studie verkry is op ’n konsekwente wyse te interpreteer. In hierdie model het ons die oorsprong van EFISH seine in elke meetgeometrie vasgestel, die onverwagte ho¨e SH seine wat in transmissie gemeet is verklaar en ’n analise van die tydkonstantes wat uit die SH gedrag in transmissie en refleksie afgelei is gedoen. Verder rapporteer ons ook vir die eerste keer stasionˆere pomp-toets reflektiwiteitsmetings van soliede n-gedoteerde Si(111) monsters met ’n natuurlike oksied. ’n Sterk pompbundel is gefokus op dieselfde posisie as ’n swak toetsbundel van dieselfde laserbron. Die verandering in reflektiwiteit van die Si(111)/SiO2 stelsel is gemeet deur die verandering in die intensiteit van die swak weerkaatste toetsbundel te monitor. Die tydevolusie van die reflektiwiteit van die mate riaal is gemeet by verskillende pompdrywings. Die reflektiwiteit van die materiaal neem toe gedurende etlike minute van bestraling en bereik ’n stasionˆere toestand na ’n lang tyd van bestraling. Die verandering in reflektiwiteit van die materiaal word toegeskryf aan ’n nielini ˆere prosess, naamlik die Kerr effek, en die tydafhanklike gedrag ontstaan as gevolg van die fotoge¨ınduseerde elektriese veld oor die Si(111)/SiO2 skeidingsvlak wat veroorsaak word deur meer-foton ladingsoordrag van die soliede Si(111) na die SiO2 laag. Die resultate wat in hierdie studie gerapporteer word dra by tot die verstaan van die fotoge ¨ınduseerde elektriese veld oor die skeidingsvlak wat veroorsaak word deur die skeiding van ladingsdraers oor die bedekte kristal-kristal skeidingsvlak. Dit lˆe ook nie-liniˆere optiese prosesse soos die Kerr effek bloot wat veroorsaak word deur die dinamika van ladings oor die skeidingsvlak, bykomend tot die bekende SHG proses.

The extraction of high power with high beam quality from semiconductor lasers has long been a goal of semiconductor laser research. Optically pumped vertical-external-cavity surface-emitting lasers (VECSELs) have already shown the potential for their high power high brightness operation. In addition, the macroscopic nature of the external cavity in these lasers makes intracavity nonlinear frequency conversion quite convenient. High-power high-brightness VECSELs with wavelength flexibility enlarge their applica-tions. The drawbacks of the VECSELs are their poor spectral characteristics, thermal-induced wavelength shift and a few-nm-wide linewidth.The objective of this dissertation is to investigate tunable high-power high-brightness VECSELs with spectral and polarization control. The low gain and microcavity reson-ance of the VECSEL are the major challenges for developing tunable high-power VECSELs with large tunability. To overcome these challenges, the V-shaped cavity, where the anti-reflection coated VECSEL chip serves as a folding mirror, and an extremely low-loss (at tuned wavelength) intracavity birefringent filter at Brewster's angle are employed to achieved the high gain, low-loss wavelength selectivity and the elimination of microcavity. This cavity results in multi-watt TEM00 VECSELs with a wavelength tuning range of 20~30 nm about 975 nm. Also the longitudinal mode discrimination introduced by birefringent filter makes the linewidth narrow down to 0.5 nm. After the tunable linearly polarized fundamental beam is achieved, the tunable blue-green VECSELs are demonstrated by using type I intracavity second-harmonic generation. The spectral control of VECSELs makes it possible to apply them as an efficient pump source for Er/Yb codoped single-mode fiber laser and to realize the spectral beam combining for multi-wavelength high- brightness power scaling.In this dissertation, theory, design, fabrication and characterization are presented. Rigorous microscopic many-body theory of the quantum well gain, based on semiconductor Bloch equations and k.p theory, is introduced. The closed loop design tool based on this theory is not only used to design the VECSEL structure, but also used as a precise on-wafer diagnostics tool by the experiment/theory comparison of the photo-luminescence. The characterization of the wafer shows that the modeling is in good agreement with the measured results.The VECSEL high power high brightness performance relies on the fabrication of the chip. The fabrication method of the VECSEL chip, which provides the optically smooth surface and good heat dissipation, is presented. The anti-reflection coating on the chip surface can significantly improve the slope efficiency of VECSEL when high reflectivity output coupler is used. Over 12-W VECSEL cw output power with 43 % slope efficiency is demonstrated at 0 oC. A beam quality factor (M^2 factor) of 1.75 is obtained at 11 W output power.

Konjuguotieji polimerai kaip funkcinės medžiagos gali būti panaudoti įvairiuose prietaisuose: organiniuose šviestukuose, organiniuose lauko tranzistoriuose, organiniuose saulės elementuose. Šio darbo tikslas - nustatyti fotogeneruotų krūvininkų pernašos dėsningumus π – konjuguotuose polimeruose panaudojant naują žadinimo-zondavimo metodą pagrįstą išoriniu elektriniu lauku indukuota antrosios optinės harmonikos generacija. Pagrindinis dėmesys buvo skiriamas pernašos dinamikai. Molekulinių darinių fizikos laboratorijoje buvo įrengta matavimų schema ir įvertintas metodo tinkamumas krūvio pernašos tyrimams. Buvo atlikti krūvio pernašos matavimai trijuose skirtinguose konjuguotuosiuose polimeruose. Nustatyta, kad fotogeneruotų krūvininkų judris tuoj po sužadinimo yra daug didesnis lyginant su stacionaria judrio verte, o krūvio pernašos dinamiką lemia konjuguoto polimero struktūrinė hierarchija, krūvininkų judėjimas yra daugialypis, susidedantis iš greito judėjimo viena polimero grandine ar konjuguotais polimero grandinės segmentais ir lėto šokavimo tarp atskirų polimero grandinių Pirmą kartą detaliai išnagrinėta šviesa sugeneruotų krūvininkų pernašos dinamika konjuguotuose polimeruose. Darbo rezultatai suteikia žinių apie fundamentalius krūvininkų pernašos mechanizmus konjuguotuose polimeruose, kurios gali būti panaudotos kuriant organinius elektronikos prietaisus. / Conjugated polymers are promising candidates for applications in all kinds of organic optoelectronic devices: OLEDs, organic field-effect transistors (OFETs) and organic photovoltaic cells. The main goal of this work was to investigate transport features of photogenerated electrical charge in pi-conjugated polymers by means of novel technique based on time-resolved electric field-induced second harmonic generation (TREFISH). TREFISH measurement setup was implemented in the laboratory of Molecular compounds physics, and applicability of the method has been verified. Measurements were performed on three different model polymers: methyl substituted ladder-type poly(para-phenylene) (MeLPPP), poly(fluorene-co-benzothiadiazole) (F8BT) and poly(spirobifluorene-co-benzothiadiazole) (PSF-BT), having different morphological and chemical structure. It has been found that motion of photogenerated charge carriers in π-conjugated polymer films experiences rapid dynamics after excitation. Different time domains of charge transport were distinguished. Initial fast transport of photogenerated charge carriers corresponds to the carrier motion along the single polymer chain or conjugated segment of the polymer chain. Slowest carrier motion phase is well described by the stochastic drift, which is attributed to interchain jumps and determines the macroscopic equilibrium mobility. Thus, the equilibrium mobility value is not applicable to the transport on nanometer scale up to tens of nanometers... [to full text]

The aim of the project described in this thesis is to synthesise new functional molecules which interact with light for neurophysiological applications. In particular, I describe a family of amphiphilic porphyrins with large first hyperpolarisabilities which are used as SHG contrast agents and voltage-sensitive probes. In addition I detail a methodological microscopy tool and a novel caged form of a neuronal ion-channel antagonist. Chapter 1 introduces the key concepts underlying the use of dyes as SHG contrast agents. In particular it focuses on aspects of molecular design, covering both the amphiphilicity and nolinearity required by the target molecule. It covers quantification of the nonlinear properties of SHG stains, then surveys a number of examples which showcase the flexibility of SHG imaging as a biomedical technique. Chapter 2 describes a family of amphiphilic porphyrins with large first hyperpolarisabilities. Working from the structure-property relationships identified in Chapter 1, we fully characterise these dyes and demonstrate that they can be used in SHG imaging. We demonstrate that these molecules may also be tuned by complexation of a metal ion which can modulate their photophysical and solubility behaviour. Chapter 3 provides a description of how to determine the orientational distribution of dipolar dyes in a membrane by multiphoton microscopy. We measure the signal intensity of the dye in a model membrane system then find distributional moments which lead to the distribution itself. Chapter 4 explores whether off-axis contributions to the first hyperpolarisability tensor can significantly augment the dominant on-axis contribution from the main dipolar charge-transfer band. We synthesise and characterise a series of cis-donor cis-acceptor porphyrin compounds and explore their biophysical characteristics. Chapter 5 is the culmination of this project and after discussing method development, goes on to show how we measure the voltage sensitivity of an amphiphilic porphyrin SHG dye. We compare the archetypal porphyrin dye chromophore with three commercially available styryl dyes and demonstrate that our dye has greater sensitivity and a more rapid response. Chapter 6 describes a side project, the use of a photolabile cage to protect MK801, a neuronal ion-channel antagonist. By developing a water soluble photolabile cage using molecular design techniques, we are able to release MK801 in neurons with precise spatiotemporal control, allowing us to pinpoint the locus of two key neurophysiological processes.

<p>Second harmonic generation (SHG) microscopy and Raman microscopy were used for qualitative and quantitative analysis of pharmaceutical materials. Prototype instruments and algorithms for sampling strategies and data analyses were developed to achieve pharmaceutical materials analysis with low limits of detection and short measurement times<br></p><p>Manufacturing an amorphous solid dispersion (ASD), in which an amorphous active pharmaceutical ingredient (API) within polymer matrix, is an effective approach to improve the solubility and bioavailability of a drug. However, since ASDs are generally metastable materials, they can often transform to produce crystalline API with higher thermodynamic stability. Analytical methods with low limits of detection for crystalline APIs were used to assess the stability of ASDs. With high selectivity to noncentrosymmetric crystals, SHG microscopy was demonstrated as an analytical tool, which exhibited a limit of detection of 10 ppm for ritonavir Form II crystals. SHG microscopy was employed for accelerated stability testing of ASDs, which provided a four-decade dynamic range of crystallinity for kinetic modeling. An established model was validated by investigating nucleation and crystal growth based on SHG images. To achieve <i>in situ</i> accelerated stability testing, controlled environment for in situstability testing (CEiST) was designed and built to provide elevated temperature and humidity, which is compatible with a commercial SHG microscope based on our research prototype. The combination of CEiST and SHG microscopy enabled assessment of individual crystal growth rates by single-particle tracking and nucleation rates for individual fields of view with low Poisson noise. In addition, SHG microscopy coupled with CEiST enabled the study of heterogeneity of crystallization kinetics within pharmaceutical materials.<br></p><p>Polymorphism of APIs plays an important role in drug formulation development. Different polymorphs of identical APIs may exhibit different physiochemical properties, e.g., solubility, stability, and bioavailability, due to their crystal structures. Moreover, polymorph transitions may take place during the manufacturing process and storage. Therefore, analytical methods with high speed for polymorph characterization, which can provide real-time feedback for the polymorphic transition, have broad applications in pharmaceutical materials characterization. Raman spectroscopy is able to determine the API polymorphism, but is hampered by the long measurement times. In this study, two analytical methods with high speed were developed to characterize API polymorphs. One is SHGmicroscopy-guided Raman spectroscopy, which achieved the speed of 10 ms/particle for clopidogrel bisulfate. Initial classification of two different polymorphs was based on SHG images, followed acquisition of Raman spectroscopyat the selected positions to determine the API crystal form. Another approach is implementing of dynamic sampling into confocal Raman microscopy to accelerate Raman image acquisition for 6-folds. Instead of raster scanning, dynamic sampling algorithm enabled acquiring Raman spectra at the most informative locations. The reconstructed Raman image of pharmaceutical materials has <0.5% loss of image quality with 15.8% sampling rate.<br></p>

Apresentamos os resultados de preparação e caracterização de cristais orgânicos (L-arginina fosfatada monohidratada - LAP - e L-lisina monohidroclorada dihidratada - L-Lys.HCl) que possuem propriedades ópticas lineares e não lineares desejáveis para aplicações tecnológicas, incluindo telecomunicações, computação óptica, armazenamento óptico de dados, processamento óptico da imagem, conversão de freqüência, entre outras. Desenvolvemos uma metodologia, simples e barata, para a eliminação de fungos e micróbios que surgem nas soluções destes compostos devido às características dos aminoácidos L-arginina e L-lisina. A adição do fungicida azida de sódio possibilitou-nos manter soluções destes compostos livres de quaisquer microorganismos na câmara de crescimento por um período de seis meses. Usando-se as técnicas de evaporação controlada do solvente a abaixamento da temperatura grandes cristais de LAP e L-Lys.HCl foram obtidos com qualidade óptica adequada para a confecção de dispositivos optoeletrônicos. Cristais de até 6 cm&sup3 de L-Lys.HCl foram pela primeira vez preparados e caracterizados opticamente. A caracterização estrutural permitiu-nos solucionar a divergência existente na indexação do difratograma de pó dos cristais de LAP e indexar os picos de difração de raios-X da L-lisina monohidroclorada dihidratada. / Growth and characterization of organic crystal (L-arginine phosphate monohydrate - LAP - and L-lysine monohydrochloride dihydrate L-Lys. HCl) with desirable linear and nonlinear optical properties for technological application including telecommunications, optical computing, optical data storage, optical image processing, harmonic frequency generation, and others are presented. We developed a simple and cheap method to eliminate fungi and microbes that arises in solution due to characteristics of L-arginine and L-lysine aminoacids. The addition of sodium azide fungicide maintained the solutions of these compounds free of microorganisms in the growth chamber for six months. Using a accurately controlled solvent evaporation technique and slow cooling technique large crystals of LAP and L-Lys.HCI were obtained with optical quality appropriate to the development of optoelectronic devices. L-Lys.HCl crystals up to 6 cm&sup3 were growth and optically characterized for the first time. The divergence in the powder diffraction indexation of LAP crystals was eliminated by structural characterization and the X-ray diffraction peaks of the L-lysine monohydrochloride diliydrate crystals were indexed.

Neste trabalho é feito um estudo da formatação de pulsos ultracurtos de laser de Ti:Safira para a geração de segundo harmônico em cristal de KDP. Para a formatação dos pulsos, é utilizado um aparato que inclui um modulador espacial de luz de cristal líquido (LC SLM), que altera unicamente a fase espectral dos pulsos. Este aparelho tem a vantagem de não introduzir perdas durante a propagação da luz, além de sua ação ser controlada via computador, através de um software em LabVIEW. Utilizando uma função senoidal, é feito um estudo das limitações do controle da geração do segundo harmônico provindas da pixelação do LC SLM, isto é, do fato de que os elementos moduladores possuem tamanhos finitos e produzem uma modulação discreta ao longo das componentes espectrais do pulso. É apresentada a geração de luz sintonizável em torno de 400 nm por duplicação de frequências de pulsos cuja fase espectral é modulada por uma soma de funções senoidais de frequências diferentes. A largura de banda do ultravioleta produzido é da ordem de 1 nm, em contraste com a largura de linha de cerca de 12 nm do segundo harmônico gerado na ausência de modulação do pulso fundamental. A sintonização é feita basicamente através de uma varredura na fase das funções moduladoras do pulso fundamental. Esse tipo de sintonização nessa região do espectro possui algumas aplicações, tais como a microscopia seletiva por dois fótons ou mesmo a espectroscopia de um fóton. Para comprovar a utilidade da geração de segundo harmônico sintonizável, é apresentada uma medida espectroscópica da transmissão em uma amostra de cloreto de európio, sendo que os resultados obtidos concordaram com as medidas da mesma amostra realizadas em um espectrofotômetro, com o mínimo de transmissão em cerca de 394 nm. / This work presents a study on the shaping of ultrashort pulses of a Ti:Sapphire laser for second harmonic generation in KDP crystals. To achieve the pulse shaping, a setup based on a phase-only crystal-based spatial light modulator (LC SLM) is used. This device has the advantage of low loss, and can be computer controlled, by means of a LabVIEW software. The use of a sinusoidal function, allows to study the limitations of the second harmonic generation due to the pixelation of the LC SLM, i. e., due to the fact that the modulating elements have finite sizes and produce a stepwise modulation along the spectral components of the pulse. The generation of tunable light around 400 nm by frequency doubling of laser pulses is presented for the case where the spectral phase is modulated by a sum of sinusoidal functions with different frequencies. The linewidth of the ultraviolet band produced is narrower than 1 nm, in contrast to the 12 nm linewidth of the non-modulated incident spectrum. The tuning is done primarily through a sweep in the phase of the modulating functions of the fundamental pulse. The possibility of tuning in this region of the spectrum has a few applications, such as in selective two-photon microscopy or even in one photon spectroscopy. To demonstrate the usefulness of tunable second harmonic generation, a spectroscopic measurement of the transmission in a sample of europium chloride is presented, and the results agreed with the measures of those performed in a spectrophotometer, with the minimal transmission occurring around 394 nm.

Graduation date: 1995