Noncoherent upconversion in multimolecular organic systems

The dissertation is devoted to the investigation of the process of triplet-triplet annihilation assisted upconversion (TTA – UC). The current state of the art of the used nowadays emitters and sensitizers was overviewed. The new emitters, synthesized mainly on the base of perylene, were created and analyzed for the applicability for TTA – UC in the combination with the sensitizers from tetrabenzo- and tetranaphtoporphyrin families. A strong influence of the excitation beam parameters on UC efficiency was shown. The new strategy of an effective UC emitter’s creation by comprising the functions of two chromophors in a dyad, where the function of the triplet-triplet transfer (TTT) and the triplet-triplet annihilation (TTA) are attributed to different parts of the molecule, was represented. The successful transfer of an UC medium into the water environment by the encapsulation of hydrophobic UC dyes into the micelles, formed by the PTS surfactant, was done. Resulting quantum efficiency is comparable with that in an organic solvent. An extremely strong dependence of the efficiency of the TTA – UC process on temperature in such micellar structures was obtained

Photonen-Aufkonversion in Nanokapseln

Die vorliegende Dissertation zeigt eine erfolgreiche Verknüpfung der Triplett-Triplett-Annihilations-Aufkonversion (TTA-UC) mit möglichen biologischen Anwendungen. Die Grundlage für solche Anwendungen ist ein Transfer der TTA-UC aus seinem üblicherweise verwendeten organischen Medium in eine wässrige Umgebung. Um diesen Transfer zu realisieren, wurden, unter Anwendung der Technik des Miniemulsionsprozesses, in Wasser dispergierte Nanokapseln herstellt. Der Kern dieser Nanokapseln besteht aus einem flüssigen hydrophoben Medium (meist Hexadekan oder Phenylheptadekan), in dem die zur TTA-UC notwendigen Farbstoffe gelöst sind. Dieser flüssige Kern ist vollständig von einer festen Polymerhülle umschlossen und somit isoliert von seiner wässrigen Umgebung. Es wurden insgesamt drei Generationen solcher Nanokapseln hergestellt, die sich hauptsächlich im Herstellungsprozess, aber auch beim Material von Kern und Hülle unterscheiden. Mittels dieser Variationen konnten die Nanokapseln in Bezug auf Effizienz, Anregungswellenlänge und Sauerstoffempfindlichkeit optimiert werden. Bei der ersten Generation wurde die radikalische Miniemulsionspolymerisation zur Kapselbildung verwendet. Die zweite Generation wurde durch die Kombination des Lösungsmittelverdampfungsprozesses mit dem Miniemulsionsprozess entwickelt und liefert somit eine alternative Möglichkeit der Kapselbildung unter milden Reaktionsbedingungen, was eine uneingeschränkte Auswahl der UC-Farbstoffpaare ermöglicht. Durch den Einsatz unterschiedlicher Sensitizer konnte die Anregungswellenlänge der TTA-UC in den roten und in den nahen Infrarot-Bereich des sichtbaren Spektrums verschoben werden. Diese Verschiebung ist im biologischen Anwendungsbereich von enormer Bedeutung, da dort eine Überlappung mit dem natürlichen optischen Fenster von menschlicher Haut und Gewebe stattfindet. Dies reduziert die Streuung der Anregungsquelle im zu untersuchende Medium und ermöglicht hohe Eindringtiefen. Mit den Kapseln der zweiten Generation wurde zum ersten Mal TTA-UC in lebenden HeLa-Zellen (Krebszellen) und MSCs (Mesenchymale Stammzellen) nachgewiesen. Die verzögerte Fluoreszenz aus den Zellen wurde mit biologischen Standardverfahren, sowohl mit der Durchflusszytometrie (FACS) als auch am cLSM nachgewiesen. Besondere Vorteile gegenüber direkter Fluoreszenz konnten bei der Bildgebung von Zellen erreicht werden. Die relativ energiearme Anregungswellenlänge und die dazu anti-Stokes verschobene, detektierte verzögerte UC-Fluoreszenz lieferte eine bessere Bildqualität und eine sehr geringe Phototoxizität der Zellen. Die Kapseln der dritten Generation zeichnen sich durch ihre anorganische, tetraedrisch verknüpfte SiO2-Hülle aus und wurden mittels einer Grenzflächenreaktion (Sol-Gel-Prozess) in Miniemulsion hergestellt. Diese Kapseln weisen im Vergleich zu den Polymernanokapseln eine bessere UC-Effizienz auf und sind zusätzlich stabiler und robuster.

Electronic energy transfer processes and charge carrier transport in pi-conjugated polymers

Conjugated polymers have attracted tremendous academical and industrial research interest over the past decades due to the appealing advantages that organic / polymeric materials offer for electronic applications and devices such as organic light emitting diodes (OLED), organic field effect transistors (OFET), organic solar cells (OSC), photodiodes and plastic lasers. The optimization of organic materials for applications in optoelectronic devices requires detailed knowledge of their photophysical properties, for instance energy levels of excited singlet and triplet states, excited state decay mechanisms and charge carrier mobilities. In the present work a variety of different conjugated (co)polymers, mainly polyspirobifluorene- and polyfluorene-type materials, was investigated using time-resolved photoluminescence spectroscopy in the picosecond to second time domain to study their elementary photophysical properties and to get a deeper insight into structure-property relationships. The experiments cover fluorescence spectroscopy using Streak Camera techniques as well as time-delayed gated detection techniques for the investigation of delayed fluorescence and phosphorescence. All measurements were performed on the solid state, i.e. thin polymer films and on diluted solutions. Starting from the elementary photophysical properties of conjugated polymers the experiments were extended to studies of singlet and triplet energy transfer processes in polymer blends, polymer-triplet emitter blends and copolymers. The phenomenon of photonenergy upconversion was investigated in blue light-emitting polymer matrices doped with metallated porphyrin derivatives supposing an bimolecular annihilation upconversion mechanism which could be experimentally verified on a series of copolymers. This mechanism allows for more efficient photonenergy upconversion than previously reported for polyfluorene derivatives. In addition to the above described spectroscopical experiments, amplified spontaneous emission (ASE) in thin film polymer waveguides was studied employing a fully-arylated poly(indenofluorene) as the gain medium. It was found that the material exhibits a very low threshold value for amplification of blue light combined with an excellent oxidative stability, which makes it interesting as active material for organic solid state lasers. Apart from spectroscopical experiments, transient photocurrent measurements on conjugated polymers were performed as well to elucidate the charge carrier mobility in the solid state, which is an important material parameter for device applications. A modified time-of-flight (TOF) technique using a charge carrier generation layer allowed to study hole transport in a series of spirobifluorene copolymers to unravel the structure-mobility relationship by comparison with the homopolymer. Not only the charge carrier mobility could be determined for the series of polymers but also field- and temperature-dependent measurements analyzed in the framework of the Gaussian disorder model showed that results coincide very well with the predictions of the model. Thus, the validity of the disorder concept for charge carrier transport in amorphous glassy materials could be verified for the investigated series of copolymers.

Perylene derivatives with large two-photon-absorption cross-sections for application in optical limiting and upconversion lasing

Perylene tetracarboxylic derivatives (PTCDs) display exceptionally high two-photon absorption (2PA) cross-sections (6, see Figure). In addition, the 2PA saturation behavior and strong two-photon-pumped fluorescence suggest that PTCD compounds may be attractive candidates for applications in optical limiting and two-photon-pumped upconversion lasing.

Intense upconversion and infrared emissions in Er3+;Yb3+ codoped Lu2 Si O5 and (Lu0.5 Gd0.5)2 Si O5 crystals

High optical quality Lu2SiO5 (LSO) and (Lu0.5Gd0.5)(2)SiO5 (LGSO) laser crystals codoped with Er3+ and Yb3+ have been fabricated by the Czochralski method. Intense upconversion (UC) and infrared emission (1543 nm) are observed under excitation of 975 nm. The luminescence processes are explained and the emission efficiencies are quantitatively obtained by measuring the UC efficiency and calculating the emission cross section. The temperature-dependent optical properties of the crystals are also investigated. Our study indicates that Er3+-Yb3+ : LSO and Er3+-Yb3+: LGSO crystals are promising gain media for developing the solid-state 1.5 mu m optical amplifiers and tunable UC lasers. (c) 2008 American Institute of Physics.

Controllable Red, Green, Blue (RGB) and Bright White Upconversion Luminescence of Lu2O3:Yb3+/Er3+/Tm3+ Nanocrystals through Single Laser Excitation at 980 nm

Lu2O3:Yb3+/Er3+/Tm3+ nanocrystals have been successfully synthesized by a solvothermal process followed by a subsequent heat treatment at 800 degrees C. Powder X-ray diffraction, transmission electron microscopy, upconversion photoluminescence spectra, and kinetic decay were used to characterize the samples. Under single-wavelength diode laser excitation of 980 nm, the bright blue emissions of Lu2O3:Yb3+, Tm3+ nanocrystals near 477 and 490 nm were observed due to the (1)G(4)-> H-3(6) transition of Tm3+. The bright green UC emissions of Lu2O3:Er3+ nanocrystals appeared near 540 and 565 nm were observed and assigned to the H-2(11/2)-> I-4(15/2) and S-4(3/2)-> I-4(15/2) transitions, respectively, of Er3+. The ratio of the intensity of green luminescence to that of red luminescence decreases with an increase of concentration of Yb3+ in Lu2O3:Er3+ nanocrystals.

Upconversion luminescence in Er3+ doped and Er3+/Yb3+ codoped zirconia and hafnia nanocrystals excited at 980 nm

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Infrared-to-visible upconversion in Yb3+/Er3+ co-doped PbO-GeO2 glass with silver nanoparticles

Enhanced frequency upconversion (UC) emission was studied in Yb3+/Er3+ co-doped PbO-GeO2 glass containing silver nanoparticles (NPs). Optical excitation was achieved with a laser operating at 980 nm in resonance with the Yb3+ transition F-4(5/2)-> F-4(7/2). The intensity of the whole UC spectrum from 400 to 700 nm was intensified due to the influence of silver NPs. The green and red emissions were enhanced by more than 300%. Emission bands centered at 408 nm and 480 nm were also detected corresponding to the H-2(9/2)-> I-4(15/2) and F-4(7/2)-> I-4(15/2) transitions of Er3+ ion. An intensity enhancement of approximate to 150% due to the NPs was measured. For the first time the influence of silver NPs on the blue emission of Yb3+/Er3+ co-doped PbO-GeO2 glass is reported. The large enhancement in the whole UC spectrum is due to the increased local field in the Er3+ ions locations and the proximity between the luminescence wavelengths and the NPs surface plasmon resonance. (C) 2010 Elsevier B.V. All rights reserved.

Frequency upconversion properties of Tm3+ doped TeO2-ZnO glasses containing silver nanoparticles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Optical spectroscopy and upconversion luminescence in Nd3+ doped Ga10Ge25S65 glass

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Frequency upconversion in a Pr(3+) doped chalcogenide glass containing silver nanoparticles

We report on orange-to-blue frequency upconversion (UC) in Pr(3+) doped chalcogenide glass (Ga(10)Ge(25)S(65)) doped with Ag(2)S and heat treated under different conditions to nucleate silver nanoparticles (NPs). The experiments were performed using 7 ns pulses from a dye laser that operates at similar to 590 nm, in resonance with the (3)H(4)->(1)D(2) transition of Pr(3+) ions. The enhancement observed in the UC emission at similar to 494 nm, ascribed as (3)P(0)->(3)H(4) transition of the Pr(3+) ion, is attributed to the large local field acting on the emitting ions due to the presence of the metallic NPs. (C) 2008 American Institute of Physics.

Phonon-assisted cooperative energy transfer and frequency upconversion in a Yb3+/Tb3+ codoped fluoroindate glass

Phonon-assisted cooperative energy transfer and frequency upconversion (UC) in Yb3+/Tb3+ codoped fluoroindate glass were investigated. Anti-Stokes quasiresonant excitation of Yb3+ ions was used to study the influence of multiphonon transitions in the UC process. A rate equation model was used to describe the temperature dependence of the UC emission intensities and the theoretical results are in good agreement with the experimental data.

Dynamics of energy transfer and frequency upconversion in Tm3+ doped fluoroindate glass

The spectroscopic properties of Tm3+-doped fluoroindate glasses (FIG) were described by single wavelength pumping in the red region. The Judd-Ofelt (J-O) theory was used to obtain the quantum efficiency of the 4f-4f transitions and other spectroscopic parameters. The dynamics of the fluorescence was investigated and energy transfer (ET) processes among Tm3+ ions were studied. The results indicate that a two-step one-photon absorption process is responsible for the ultraviolet upconversion (UC) emissions, and dipole-dipole interaction provides the main contribution for ET rate is equal to the decay rate of noninteracting among active ions.

Energy transfer and frequency upconversion involving triads of Pr3+ ions in (Pr3+, Gd3+) doped fluoroindate glass

Blue and ultraviolet luminescence in (Pr3+, Gd3+) doped fluoroindate glass is studied for excitation in the red region (≈590 nm). Frequency upconversion (UC) is observed due to energy transfer (ET) among three Pr3+ ions initially excited to the D21 state corresponding to the ET process D21 + D21 + D21 → S01 + H53 + H53. Additionally, UC luminescence from states P 72 6 and I 72 6 of Gd3+ is observed for an excitation wavelength resonant with transitions of the Pr3+ ions. The characterization of the luminescence signals allowed to determine ET rate among the Pr3+ ions and provides evidence of interconfigurational ET between Gd3+ and Pr3+ ions. © 2006 American Institute of Physics.

Frequency upconversion involving triads and quartets of ions in a Pr3+/Nd3+ codoped fluoroindate glass

Frequency upconversion (UC) processes involving energy transfer (ET) among Nd 3+ and Pr 3+ ions in a fluoroindate glass are reported. In a first experiment, the excitation of Pr 3+ [transition 3H 4→ 1D 2] and of Nd 3+ [transition 4I 9/2→( 2G 7/2+ 4G 5/2)] was achieved with a dye laser operating in the 575-590 nm range. In a second experiment, the Nd 3+ ions were excited with the second harmonic of a Nd: YAG laser at 532 nm. The ET processes leading to UC in both experiments were studied by monitoring the blue fluorescence decay at 480 nm due to the transition 3P 0→ 3H 4 in Pr 3+. In the more relevant UC process, quartets of ions (Nd-Nd-Pr-Pr) are excited due to absorption of three laser photons by two Nd 3+ ions which transfer their energy to two Pr 3+ ions. Each Pr 3+ ion promoted to the 3P 0 level decays to the ground state emitting one photon in the blue region. This conclusion was achieved investigating the dependence of the UC fluorescence intensity as a function of laser intensity, samples concentrations, and temporal behavior of the UC signal. Other UC processes involving nonisoionic groups of three ions are also reported. © 2002 American Institute of Physics.