Thesis (Ph.D. 1978) from the Deaprtment of Physical and Inorganic Chemistry, University of Adelaide.

Thesis (Ph. D.)--Michigan State University. Dept. of Physics and Astronomy, 2006. / Title from PDF t.p. (viewed on June 19, 2009) Includes bibliographical references (p. 73-76). Also issued in print.

Thesis (M.S.)--Virginia Polytechnic Institute and State University, 1991. / Vita. Abstract. Includes bibliographical references (leaves 44-46). Also available via the Internet.

Thesis (M. Phil.)--University of Hong Kong, 1993.

Thesis (Ph.D.) - University of St Andrews, June 2009. / Restricted until 1st June 2010.

The kinetics of the free exciton, bound exciton and multi-exciton complexes have been investigated for Si(B) by using the rate equations to analyze the experimental transient responses of these luminescent species. From this analysis, the B capture cross section for an exciton to bind upon a neutral impurity has been determined, as well as the B capture cross sections ratios for higher order complexes. Furthermore, the lifetimes for the BE, BMEC-2 and BMEC-3 have been determined. From the low temperature lifetimes, the BMEC-m/BE lifetime ratio appears to form a simple integer series for increasing m. The computer programs used to analyze the experimental data and generate the theoretical transient responses, along with technical information concerning the experiment, are listed in the appendices. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

The photoluminescence spectrum of phosphorus-doped silicon at 17 _ 3 19-3 dopant concentrations ranging from 1.2 x 10¹⁷ cm⁻³ to 4.0 x 10¹⁹ cm⁻³ is studied as a function of excitation intensity. The spectra are interpreted tn terms of two types of recombination events', one' attributed to the recombination of oppositely charged carriers inside an electron-hole droplet and the other outside due to the recombination -of free holes with electrons in the impurity band. The latter type of event gives rise to a new photoluminescence peak observed for the first time. The line shape of this peak compares very well with a first principle calculation of the impurity band density of states within the Hubbard model. Existing theories for the ground state energy of an electron-hole droplet in n-type heavily doped silicon are reviewed and new numerical results are presented. However, within the present model droplets are not theoretically understood at this time in heavily-doped silicon. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

The crux of all modern semiconductor technology is the exciton, the bound electron-hole pair that drives everything from photovoltaics to light emitting diodes to transistors. This dissertation explores how we can develop materials that are able to control the energetics of excitons, by splitting them and combining them. Also explored are the applications allowed by the control of exciton energetics. The topics covered in this thesis are singlet exciton fission, and triplet fusion upconversion. Chapter 1 will introduce these concepts, and provide an overview of these fields. Chapter 2 discusses the singlet fission properties of a fully conjugated tetracene polymer and its derivatives. This chapter includes the synthesis of these materials, their photophysical properties, as well as their incorporation into bilayer semiconducting devices and their properties under an applied magnetic field. Chapter 3 explores the study of an organic-inorganic hybrid singlet fission triplet acceptor complex. A singlet fission capable pentacene dimer was covalently linked to an iron-oxo cluster with an electron affinity appropriate to accept triplets generated from singlet fission. This chapter explores the synthesis and photophysical properties of this hybrid complex, as well as the nature of the triplet pair state generated from intramolecular singlet fission. In Chapter 4, a new design rule for intramolecular singlet fission is studied, the energy sink. A series of pentacene dimers spaced by tetracene bridges are synthesized, and their singlet fission properties are explored via transient absorption spectroscopy and time resolved electron spin resonance spectroscopy. Chapter 5 begins the portion of the thesis focused on triplet fusion upconversion. The lessons learned from previous work in intramolecular singlet fission are applied to synthesize more efficient annihilators for upconversion. A series of tetracene dimers are synthesized, and their upconversion properties are explored. The work demonstrates intramolecular triplet fusion as a method to enhance the performance of existing annihilators. Chapter 6 details the discovery that diketopyrrolopyrroles can be used as upconversion annihilators. The advantages of these materials relative to existing annihilators are explained. Energetic design rules for upconversion annihilators are also discussed. Finally, in Chapter 7 a new application of triplet fusion upconversion is explored: infrared light sensitized photoredox catalysis.

No description available.

Neste trabalho foram estudados os processos de migração e transferência de energia em derivados de polifluoreno, de estrutura totalmente conjugada e de conjugação confinada. A dinâmica de estado excitado dos derivados PF-BNI, PFOPPV e PFPPV foi estudada em solução diluída de diferentes solventes através de espectroscopia eletrônica de alta resolução temporal. O derivado PF-BNI, contendo N-(2-benzotiazol)-1,8-naftalimida (BNI) como terminador da cadeia de poli(9,9\'dioctilfluoreno), foi sintetizado pela rota de Yamamoto. O material apresenta alto rendimento quântico de fluorescência e suas propriedades de emissão são moduladas pela polaridade do solvente. As medidas de fluorescência resolvida no tempo mostraram a migração do exciton singlete ao longo da cadeia polimérica e a formação de um estado excitado de transferência de carga intracadeia (ICCT). Os derivados PFOPPV e PFPPV são copolímeros de fluoreno contendo unidades fluoreno-vinileno-fenileno no segmento cromofórico. No PFOPPV o segmento cromofórico é confinado entre segmentos alifáticos (-(CH2)8-) flexíveis, no PFPPV a cadeia principal é totalmente conjugada. A dinâmica de estado excitado dos derivados, PFOPPV e PFPPV, é caracterizada pela presença de segmentos cromofóricos contendo isômeros cis e trans. No PFOPPV, a sua estrutura segmentada permite a transferência de energia entre os segmentos cromofóricos, via interações dipolo-dipolo. A transferência acarreta a depolarização da emissão de fluorescência. No caso do PFPPV a migração de energia ocorre em menos de 20 ps e o decaimento de fluorescência decorre da emissão de segmentos contendo isômeros cis e trans, já na condição estacionária. / This work reports the study of energy transfer and migration processes in fully conjugated and segmented polyfluorene derivatives. The excited-state dynamics of the derivatives, PF-BNI, PFOPPV and PFPPV was studied in diluted solution of different solvents by means of ultrafast time-resolved spectroscopy. Poly(9,9\'-dioctylfluorene) end-capped with N-(2-benzothiazole)-1,8-naphthalimide, named PF-BNI, was prepared via Yamamoto-coupling reaction. This derivative is a highly fluorescence material with emission modulated by solvent polarity. Time-resolved fluorescence measurements showed the singlet exciton migration through the polymer backbone and the formation of an intrachain charge transfer excited-state (ICCT). PFOPPV and PFPPV are both fluorene copolymers containing fluorene-vinylene-phenylene moieties in the backbone. Whereas the PFPPV backbone is fully conjugated, the chromophore segment in PFOPPV backbone is confined between aliphatic (-(CH2)8-) flexible segments. The excited-state dynamics of both copolymers is characterized by the presence of conjugated moieties containing cis and trans isomers. The segmented structure of PFOPPV allows the resonant energy transfer between the chromophores, which is provided by dipole-dipole interactions. The energy transfer process leads to the depolarization of PFOPPV fluorescence emission. For PFPPV the energy migration occurs in less than 20 ps and the fluorescence decay is ascribed to the emission of chromophore segments containing cis and trans, already in a photostationary condition.