Recently laser cooling of semiconductors has received renewed attention, with the hope that a semiconductor cooler might be able to achieve cryogenic temperatures. In order to study semiconductor laser cooling at cryogenic temperatures, it is crucial that the theory include both the effects of excitons and the electron-hole plasma. In this dissertation, I present a theoreticalanalysis of laser cooling of bulk GaAs based on a microscopic many-particle theory of absorptionand luminescence of a partially ionized electron-hole plasma.This theory has been analyzed from a temperature 10K to 500K. It is shown that at high temperatures (above 300K), cooling can be modeled using older models with a few parameter changes. Below 200K, band filling effects dominate over Auger recombination. Below 30K excitonic effects are essential for laser cooling. In all cases, excitonic effects make cooling easier then predicted by a free carrier model.The initial cooling model is based on the assumption of a homogeneous undoped semiconductor. This model has been systematically modified to include effects that are present in real laser cooling experiments. The following modifications have been performed. 1) Propagation and polariton effects have been included. 2) The effect of p-doping has been included. (n-doping can be modeled in a similar fashion.) 3) In experiments, a passivation layer is required to minimize non-radiative recombination. The passivation results in a npn heterostructure. The effect of the npn heterostructure on cooling has been analyzed. 4) The effect of a Gaussian pump beam was analyzed and 5) Some of the parameters in the cooling model have a large uncertainty. The effect of modifying these parameters has been analyzed.Most of the extensions to the original theory have only had a modest effect on the overall results. However we find that the current passivation technique may not be sufficient to allow cooling. The passivation technique currently used appears to be very good at low densities, but loses some of it's effectiveness at the moderately high densities required for laser cooling. We suggest one possible solution that might enable laser cooling. If the sample can be properly passivated, then we expect laser cooling to be possible.

In photodynamic therapy (PDT), the combination of light, photosensitizer and molecular oxygen generates reactive oxygen species, including singlet oxygen (1O2), which is regarded as the primary cytotoxin and effector with most clinical photosensitizers. PDT has gained some acceptance for the treatment of cancer and other conditions. However, its clinical utility and effectiveness has been limited by variability in treatment response and failure to integrate adequate treatment planning and dosimetry. Direct PDT dosimetry through the detection of ultra-weak near-infrared 1O2 luminescence emission at 1270 nm (SOL) collapses the complexity of PDT into a single parameter, the 1O2 concentration. Prior to the present studies, it was shown that SOL was well correlated with PDT response in vitro and in vivo under controlled experimental conditions. However, SOL detection is technically challenging because of the very low radiative probability of 1O2 (~ 10-8 in biological environments), dynamic background signals and limited sensitivity of suitable photodetectors in this wavelength region. A technologically simpler and less costly PDT dosimetry approach is to use photosensitizer photobleaching to estimate the 1O2 dose. The first objective in this thesis was to characterize the dynamics of SOL measurements, in particular the influence of oxygen depletion, in order to improve the quantification of SOL and its use as an accurate PDT dose metric. Subsequently, direct comparison of SOL and photobleaching-based dosimetry during in vitro PDT treatment with meso-tetra(hydroxyphenyl)chlorin (mTHPC) showed that SOL dosimetry is robust but that photobleaching-based dosimetry can fail under hypoxic conditions. However, the latter can be salvaged through the identification of a previously unreported 613 nm emission from mTHPC that indicates hypoxia. These studies were carried forward into an in vivo dorsal skin-fold window chamber tumor model, which showed promising initial correlation between 1O2 dose and tumor response. This work also identified SOL detection limitations and opportunities for further development. Additionally, SOL measurements were used as a ‘gold standard’ to evaluate novel activatable PDT beacons and a novel “PDT biodosimeter” based on STAT3 cross-linking. Future work includes further tumor dose-response studies, characterization of novel photosensitizing agents, improvement on signal detection and processing, and studies in normal human skin.

In photodynamic therapy (PDT), the combination of light, photosensitizer and molecular oxygen generates reactive oxygen species, including singlet oxygen (1O2), which is regarded as the primary cytotoxin and effector with most clinical photosensitizers. PDT has gained some acceptance for the treatment of cancer and other conditions. However, its clinical utility and effectiveness has been limited by variability in treatment response and failure to integrate adequate treatment planning and dosimetry. Direct PDT dosimetry through the detection of ultra-weak near-infrared 1O2 luminescence emission at 1270 nm (SOL) collapses the complexity of PDT into a single parameter, the 1O2 concentration. Prior to the present studies, it was shown that SOL was well correlated with PDT response in vitro and in vivo under controlled experimental conditions. However, SOL detection is technically challenging because of the very low radiative probability of 1O2 (~ 10-8 in biological environments), dynamic background signals and limited sensitivity of suitable photodetectors in this wavelength region. A technologically simpler and less costly PDT dosimetry approach is to use photosensitizer photobleaching to estimate the 1O2 dose. The first objective in this thesis was to characterize the dynamics of SOL measurements, in particular the influence of oxygen depletion, in order to improve the quantification of SOL and its use as an accurate PDT dose metric. Subsequently, direct comparison of SOL and photobleaching-based dosimetry during in vitro PDT treatment with meso-tetra(hydroxyphenyl)chlorin (mTHPC) showed that SOL dosimetry is robust but that photobleaching-based dosimetry can fail under hypoxic conditions. However, the latter can be salvaged through the identification of a previously unreported 613 nm emission from mTHPC that indicates hypoxia. These studies were carried forward into an in vivo dorsal skin-fold window chamber tumor model, which showed promising initial correlation between 1O2 dose and tumor response. This work also identified SOL detection limitations and opportunities for further development. Additionally, SOL measurements were used as a ‘gold standard’ to evaluate novel activatable PDT beacons and a novel “PDT biodosimeter” based on STAT3 cross-linking. Future work includes further tumor dose-response studies, characterization of novel photosensitizing agents, improvement on signal detection and processing, and studies in normal human skin.

The modern society relies heavily on mankind’s ability to produce light to lengthen the day. Throughout the evolution of artificial lighting lots of light sources were discovered / invented, i.e. burning wood, oil, candles, using incandescent bulbs and fluorescent lamps and, finally, white LEDs. LEDs are superior to other light sources due to their high efficiency. Replacement of conventional light sources by white LEDs what would allow saving huge amounts of electricity consumed for lighting purposes. The main goal of this dissertation was development and investigation of various new materials that could be used in solid state light sources based on near-UV and blue LEDs. One silicate, one molybdate and three garnet structure compounds were selected. Several synthesis methods, i.e. solid state, sol-gel, and sol-gel combustion, were applied in preparation of selected host materials. The host materials were activated by Eu2+, Eu3+, and Ce3+ ions. The phase purity of synthesized samples was evaluated by recording powder XRD patterns. Luminescent properties of the activator ions were investigated by recording reflectance, excitation, emission spectra and decay curves at room temperature. The temperature dependent decay curves and emission spectra were recorded in the range of 77-500 K. Moreover, quantum yields, luminous efficacies and colour points were calculated from the obtained data. / Žmonija jau nuo senų senovės stengiasi prailginti dieną dirbtiniais šviesos šaltiniais. Šviesos šaltiniai vystėsi pamažu – iš pradžių buvo deginama mediena, žibalas ir žvakės, vėliau buvo išrasta kaitrinė lemputė, o dar po kurio laiko fluorescencinė lempa. Jauniausi iš dirbtinių šviesos šaltinių yra šviestukai, kurie yra pranašesni už prieš tai minėtus šaltinius savo dideliu efektyvumu. Pakeitus dabartinius šviesos šaltinius šviestukais, būtų galima sutaupyti milžinišką elektros energijos kiekį, suvartojamą apšvietimui. Pagrindinis disertacijos tikslas buvo buvo naujų liuminescencinių medžiagų, kurios gali būti sužadinamos ultravioletinę arba mėlyną spinduliuotę emituojančiais šviestukais, paieška. Iš viso pasirinktos penkios sistemos – vienas silikatas, vienas molibdatas ir trys granato struktūros junginiai. Medžiagos buvo susintetintos kietafazių reakcijų, zolių-gelių arba zolių-gelių užsiliepsnojimo metodais. Junginiai buvo legiruoti Eu2+, Eu3+ arba Ce3+ jonais. Fazinis junginių grynumas buvo patvirtintas Rentgeno spindulių difrakcijos analize. Junginių optinės savybės buvo įvertintos išmatavus atspindžio, sužadinimo ir emisijos spektrus bei liuminescencijos gesimo trukmes kambario temperatūroje. Taip pat buvo įvertinta junginių liuminescencijos gesimo trukmių ir emisijos spektrų priklausomybė nuo temperatūros, bei apskaičiuoti kvantiniai našumai ir spalviniai taškai.

Žmonija jau nuo senų senovės stengiasi prailginti dieną dirbtiniais šviesos šaltiniais. Šviesos šaltiniai vystėsi pamažu – iš pradžių buvo deginama mediena, žibalas ir žvakės, vėliau buvo išrasta kaitrinė lemputė, o dar po kurio laiko fluorescencinė lempa. Jauniausi iš dirbtinių šviesos šaltinių yra šviestukai, kurie yra pranašesni už prieš tai minėtus šaltinius savo dideliu efektyvumu. Pakeitus dabartinius šviesos šaltinius šviestukais, būtų galima sutaupyti milžinišką elektros energijos kiekį, suvartojamą apšvietimui. Pagrindinis disertacijos tikslas buvo buvo naujų liuminescencinių medžiagų, kurios gali būti sužadinamos ultravioletinę arba mėlyną spinduliuotę emituojančiais šviestukais, paieška. Iš viso pasirinktos penkios sistemos – vienas silikatas, vienas molibdatas ir trys granato struktūros junginiai. Medžiagos buvo susintetintos kietafazių reakcijų, zolių-gelių arba zolių-gelių užsiliepsnojimo metodais. Junginiai buvo legiruoti Eu2+, Eu3+ arba Ce3+ jonais. Fazinis junginių grynumas buvo patvirtintas Rentgeno spindulių difrakcijos analize. Junginių optinės savybės buvo įvertintos išmatavus atspindžio, sužadinimo ir emisijos spektrus bei liuminescencijos gesimo trukmes kambario temperatūroje. Taip pat buvo įvertinta junginių liuminescencijos gesimo trukmių ir emisijos spektrų priklausomybė nuo temperatūros, bei apskaičiuoti kvantiniai našumai ir spalviniai taškai. / The modern society relies heavily on mankind’s ability to produce light to lengthen the day. Throughout the evolution of artificial lighting lots of light sources were discovered / invented, i.e. burning wood, oil, candles, using incandescent bulbs and fluorescent lamps and, finally, white LEDs. LEDs are superior to other light sources due to their high efficiency. Replacement of conventional light sources by white LEDs what would allow saving huge amounts of electricity consumed for lighting purposes. The main goal of this dissertation was development and investigation of various new materials that could be used in solid state light sources based on near-UV and blue LEDs. One silicate, one molybdate and three garnet structure compounds were selected. Several synthesis methods, i.e. solid state, sol-gel, and sol-gel combustion, were applied in preparation of selected host materials. The host materials were activated by Eu2+, Eu3+, and Ce3+ ions. The phase purity of synthesized samples was evaluated by recording powder XRD patterns. Luminescent properties of the activator ions were investigated by recording reflectance, excitation, emission spectra and decay curves at room temperature. The temperature dependent decay curves and emission spectra were recorded in the range of 77-500 K. Moreover, quantum yields, luminous efficacies and colour points were calculated from the obtained data.

No description available.

This work concerns the development of π-conjugated materials for optoelectronic applications, with emphasis on organoboron- and organoplatinum-containing compounds. The preparation of a nonconjugated two-chromophore emissive material is described, containing both organoplatinum and organoboron units. This material exhibits simultaneous fluorescent and phosphorescent emission at ambient temperature. Both emission colours are switchable in the presence of fluoride, giving a dual-emissive compound with multiple observable luminescent colours. The preparation of a nonconjugated donor-acceptor triarylborane containing both Lewis acidic and basic receptor sites is also described. This highly fluorescent compound is reversibly switchable between three emissive states upon addition of acid or fluoride. Furthermore, platinum(II)-acetylacetonates with nonconjugated antenna chromophores were prepared, and their luminescent properties were investigated. A series of directly conjugated platinum(II)-acetylacetonates have been synthesized incorporating a triarylboron group. The presence of boron was found to enhance the electron-transporting capabilities, film-forming properties, and phosphorescent quantum yields of these complexes. Highly efficient OLEDs were prepared incorporating these materials as dopants, including the first example of a Pt(II)-based OLED with an external quantum efficiency >20%. Triarylboron-containing Pt(II) complexes of N-heterocyclic carbenes were also prepared. Using this design, blue to blue-green phosphorescence was achieved with high quantum yield, and their use in OLEDs was demonstrated. A new high-yield synthetic route has been developed to cyclometalated Pt(II)-β-diketonates, requiring stoichiometric reagents and short reaction times at ambient temperature. This methodology has broad substrate scope across a variety of N^C-chelate ligands, as well as P^C-chelate phosphines and C^C-chelate carbenes as well. The preparation of N-heterocyclic carbazole-based host materials for OLEDs is also described. These materials exhibit improved electron-transporting capabilities relative to the more commonly used host 4,4’-N,N’-dicarbazolylbiphenyl (CBP), and were used to fabricate the first single-layer electrophosphorescent devices with efficiencies competitive with conventional multilayer structures. Finally, the discovery of a triarylboron-based vapochromic material is described. This Pt(II)-alkyne complex was shown to change luminescent colour in response to a variety of volatile organic compounds, with distinct responses dependent on the nature of the analyte. The mechanism of vapochromism was investigated in detail by optical and multinuclear solid-state NMR spectroscopy, and differs in origin from all previously reported examples. / Thesis (Ph.D, Chemistry) -- Queen's University, 2012-09-06 12:51:18.363

A series of kinetically stable chiral lanthanide complexes has been developed, with a view to developing responsive probes for use in analysis and in seeking chiral complexes exhibiting selectivity in their interaction with nucleic acids. Firstly a pH sensitive complex has been modified with the aim of tuning the pH range to which it responds to the physiologically useful regime. The synthesis was undertaken of relatively lipophilic 6-butylphenanthridinyl complexes. Their photophysical behaviour was investigated by absorbance and luminescence spectroscopy and the modulation of their emission examined in the pH range 4.5 to 7.5.In addition to their luminescent properties, enantiomerically pure chiral lanthanide complexes permit chiroptical techniques to be used, allowing their interactions with other chiral species to be addressed (e.g. nucleic acids, oligonucleotides).The first series of enantiopure lanthanide complexes has been devised that show several interesting features in binding to oligonucleotides and nucleic acids. These macrocyclic tris-and tetra-amide lanthanide (Eu, Tb or Yb) complexes contain an N-alkyl phenanthridinium unit that allows intercalation between the base pairs of the DNA. Their binding to [(AT)(_6)](_2), [(CG)(_6)](_2) and CT-DNA was monitored by changes in the ligand and metal based luminescence, and in the characteristic CD bands of the oligonucleotides. Binding affinities were assessed using intrinsic methods and the McGhee-von Hippel analysis. Marked differences have been observed in the binding of Eu and Yb complexes as a function of the A and Δ helicity of the complexes, which is itself determined by the configuration of the remote amide substituents. Binding of the A-Eu complex was over 50 times stronger to [(CG)(_6)](_2) compared to [(AT)(_6)](_2), while the left handed Δ-Yb complex showed a different pattern of selectivity. In the europium complex of a related heptadentate tris-amide ligand, the coordination of a DNA phosphate group to the lanthanide centre was suggested by emission and lifetime changes. Another series of chiral tetraamide complexes linked to the 6 position of the phenanthridine moiety was synthesised and studied. An additional stereogenic centre at carbon, alpha to the phenanthridine group was introduced with the aim of tuning the selectivity of binding. A set of four diastereoisomeric ligands was separated and their lanthanide complexes characterised. The binding of their Eu and Yb complexes was evaluated and differences between Eu and Yb complexes persisted. The additional chiral centre did not appear to modify the binding affinity of this series of complexes. Finally, a series of 6-phenanthridinyl complexes was investigated in which the phenanthridine N atom was directly bound to the lanthanide centre. Their affinity for DNA was found to be relatively low, which may be related to their rigid structure.

No description available.

A new approach for studying thermal phase separation in sodium borosilicate glasses using Mn('2+) as a luminescent probe is investigated. Seventy-one samples of glasses activated by Mn('2+) inside and around the Na(,2)O(.)B(,2)O(,3)(.)SiO(,2) miscibility gaps were prepared. These samples were then phase separated by dry thermal treatment. / It is shown that on addition of MnO, the ternary Na(,2)O(.)B(,2)O(,3)(.)SiO(,2) system behaved like other quaternary systems of the type X(,2)O(.)MO(.)B(,2)O(,3)(.)SiO(,2) (X = Na, K; M = Mg, Ca, Ba, Zn). Scanning electron microscopy and X-ray microanalysis demonstrated that manganese concentrates preferentially in the boron-rich phase. This analysis, in conjunction with a comparison of Mn('2+) emission spectra of unheated and heat-treated glasses shows that the glasses are submicroscopically phase separated when prepared. The decay-time analysis of Mn('2+) luminescence indicates that the low energy emission band arises from Mn('2+) in the boron-rich phase while the high energy emission is due to Mn('2+) in the silica-rich phase. The difference in the crystal field parameters obtained from the excitation spectra of the two emission bands shows that the high energy emission band is from Mn('2+) in tetrahedral sites while the low energy emission band is from Mn('2+) in an octahedral environment.