No description available.

Molecular fluorophores and semiconductor quantum dots (QDs) have been used as cellular imaging agents for biomedical research, but each class has challenges associated with their use, including poor photostability or toxicity. Silicon is a semiconductor material that is inexpensive and relatively environmental benign in comparison to heavy metal-containing quantum dots. Thus, red-emitting silicon nanoparticles (Si NPs) are desirable to prepare for cellular imaging application to be used in place of more toxic QDs. However, Si NPs currently suffer poorly understood photoinstability, and furthermore, the origin of the PL remains under debate. This dissertation first describes the use of diatomaceous earth as a new precursor for the synthesis of photoluminescent Si NPs. Second, the stabilization of red PL from Si NPs in aqueous solution via micellar encapsulation is reported. Thirdly, red to blue PL conversion of decane-terminated Si NPs in alcohol dispersions is described and the origins (i.e., color centers) of the emission events were studied with a comprehensive characterization suite including FT-IR, UV-vis, photoluminescence excitation, and time-resolved photoluminescence spectroscopies in order to determine size or chemical changes underlying the PL color change. In this study, the red and blue PL was determined to result from intrinsic and surface states, respectively. Lastly, we determined that the blue emission band assigned to a surface state can be introduced by base addition in originally red-emitting silicon nanoparticles, and that red PL can be restored by subsequent acid addition. This experimentally demonstrates blue PL is surface state related and can overcome the intrinsic state related excitonic recombination pathway in red PL event. Based on all the data collected and analyzed, we present a simple energy level diagram detailing the multiple origins of Si NP PL, which are related to both size and surface chemistry.

OPTICAL CHARACTERIZATION OF INGAN HETEROSTRUCTURES FOR BLUE LIGHT EMITTERS AND VERTICAL CAVITY LASERS: EFFICIENCY AND RECOMBINATION DYNAMICS By Serdal Okur, Ph.D. A thesis submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at Virginia Commonwealth University. Virginia Commonwealth University, 2014. Major Director: Ümit Özgür, Associate Professor, Electrical and Computer Engineering This thesis explores radiative efficiencies and recombination dynamics in InGaN-based heterostructures and their applications as active regions in blue light emitters and particularly vertical cavities. The investigations focus on understanding the mechanism of efficiency loss at high injection as well as developing designs to mitigate it, exploring nonpolar and semipolar crystal orientations to improve radiative efficiency, integration of optimized active regions with high reflectivity dielectric mirrors in vertical cavity structures, and achieving strong exciton-photon coupling regime in these microcavities for potential polariton lasing. In regard to active regions, multiple double heterostructure (DH) designs with sufficiently thick staircase electron injection (SEI) layers, which act as electron coolers to reduce the overflow of hot electrons injected into the active region, were found to be more viable to achieve high efficiencies and to mitigate the efficiency loss at high injection. Such active regions were embedded in novel vertical cavity structure designs with full dielectric distributed Bragg reflectors (DBRs) through epitaxial lateral overgrowth (ELO), eliminating the problems associated with semiconductor bottom DBRs having narrow stopbands and the cumbersome substrate removal process. Moreover, the ELO technique allowed the injection of carriers only through the high quality regions with substantially reduced threading dislocation densities compared to regular GaN templates grown on sapphire. Reduced electron-hole wavefunction overlap in polar heterostructures was shown to hamper the efficiency of particularly thick active regions (thicker than 3 nm) possessing three-dimensional density of states needed for higher optical output. In addition, excitation density-dependent photoluminescence (PL) measurements showed superior optical quality of double heterostructure (3 nm InGaN wells) active regions compared to quantum wells (2 nm InGaN wells) suggesting a minimum limit for the active region thickness. Therefore, multiple relatively thin but still three dimensional InGaN active regions separated by thin and low barriers were found to be more efficient for InGaN light emitters. Investigations of electroluminescence from light emitting diodes (LEDs) incorporating multi DH InGaN active regions (e.g. quad 3 nm DH) and thick SEIs (two 20 nm-thick InGaN layers with step increase in In content) revealed higher emission intensities compared to LEDs with thinner or no SEI. This indicated that injected electrons were cooled sufficiently with thicker SEI layers and their overflow was greatly reduced resulting in efficient recombination in the active region. Among the structures considered to enhance the quantum efficiency, the multi-DH design with a sufficiently thick SEI layer constitutes a viable approach to achieve high efficiency also in blue lasers. Owing to its high exciton binding energy, GaN is one of the ideal candidates for microcavities exploiting the strong exciton-photon coupling to realize the mixed quasiparticles called polaritons and achieve ideally thresholdless polariton lasing at room temperature. Angle-resolved PL and cathodoluminescence measurements revealed large Rabi splitting values up to 75 meV indicative of the strong exciton-photon coupling regime in InGaN-based microcavities with bottom semiconductor AlN/GaN and a top dielectric SiO2/SiNxDBRs, which exhibited quality factors as high as 1300. Vertical cavity structures with all dielectric DBRs were also achieved by employing a novel ELO method that allowed integration of a high quality InGaN cavity active region with a dielectric bottom DBR without removal of the substrate while forming a current aperture through the ideally defect-free active region. The full-cavity structures formed as such were shown to exhibit clear cavity modes near 400 and 412 nm in the reflectivity spectrum and quality factors of 500. Although the polar c-plane orientation has been the main platform for the development of nitride optoelectronics, significant improvement of the electron and hole wavefunction overlap in nonpolar and semipolar InGaN heterostructures makes them highly promising candidates for light emitting devices provided that they can be produced with good crystal quality. To evaluate their true potential and shed light on the limitations put forth by the structural defects, optical processes in several nonpolar and semipolar orientations of GaN and InGaN heterostructures were investigated. Particularly, stacking faults were found to affect significantly the optical properties, substantially influencing the carrier dynamics in nonpolar (1-100), and semipolar (1-101) and (11-22)GaN layers. Carrier trapping/detrapping by stacking faults and carrier transfer between stacking faults and donors were revealed by monitoring the carrier recombination dynamics at different temperatures, while nonradiative recombination was the dominant process at room temperature. Although it is evident that nonpolar (1-100)GaN and semipolar (11-22)GaN require further improvement of material quality, steady-state and time-resolved PL measurements support that (1-101)-oriented GaN templates and InGaN active regions exhibit optical performance comparable to their highly optimized polar c-plane counterparts, and therefore, are promising for vertical cavities and light emitting device applications.

Time-resolved photoluminescence (TRPL) measurements paired with steady-state photoluminescence (SSPL) measurements can help to determine the PL lifetime, shape and position of unresolved bands, capture coefficients, and concentrations of free electrons and defects.PL bands that are obscured in the SSPL spectra can be accurately revealed by TRPL measurements. TRPL measurements are able to show if the PL band originates from an internal transition between different states of the same defect. The main defect-related PL bands in high-purity GaN grown by hydride vapor phase epitaxy (HVPE) which have been investigated are the ultraviolet, blue, green, yellow and red luminescence bands (UVL, BL, GL, YL and RL, respectively). The concentration of free electrons can be calculated from these measurements providing a contactless alternative to the Hall effect method. The lifetime of most defect-related PL bands decreases with increasing temperature. However, the lifetime of the GL band, with a maximum at 2.4 eV observed in the SSPL spectra only at high excitation intensity, increases as a function of temperature. By analyzing the PL intensity decay, the origin of the GL can be attributed to an internal transition from an excited state of the CN defect, which behaves as an optically generated giant trap, to the 0/+ level of the same defect. This first observation of an optically generated giant trap was detected by analyzing the cubic temperature dependence of the electron capture coefficient. Excitation intensity and temperature dependent studies on Mg-doped GaN grown by HVPE were performed. The position of the UVL (3.2 eV) peak blue-shifts with increasing excitation intensity, which can be explained by the presence of potential fluctuations. The BL peak (2.8 eV) also blue-shifts with increasing excitation intensity, and red-shifts as a function of temperature. These shifts can be explained by the transitions originating from a deep-donor to the MgGa acceptor, and the corresponding donor-acceptor pair nature.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

This thesis deals with two independent topics. The first is focused on the study of reversible covalent interactions of a carbonyl group with alcohols and water forming hemiacetals (respectively hydrate) derived from pyrazine trifluormethylketone. The main research method in this part is the NMR spectroscopy and experimental results are also supported by quantum chemical calculations. The second topic aims to the preparation and the study of photochemical properties of three dihydropyrazines which exhibit fluorescence both in solution and solid phase. The fluorescence can be influenced by means of complexation by various metal ions. Prepared dihydropyrazines also show interesting values of the Stokes shift. The structure of these new compounds was confirmed by X-ray analysis.

Orientador: Alexandre Mesquita / Resumo: O titanato de cálcio CaTiO3 é um material com estrutura de tipo perovskita que tem sido aplicado como luminóforo. É bem estabelecido que a inserção de íons de terra rara no sítio ocupado pelo Ca2+ provoca mudanças significativas nas suas propriedades estruturais e produz efeitos luminescentes na faixa do visível. Entretanto não existem trabalhos reportando a inserção do La3+ no sítio do Ca2+ no que se refere às características estruturais e luminescentes desses materiais. Portanto, o presente trabalho estuda as propriedades fotoluminescentes apresentadas pela matriz à base de titanato de cálcio dopada com praseodímio, lantânio e alumínio. O material foi sintetizado a partir do método Pechini, que se mostrou um método eficaz na preparação de acordo com a caracterização estrutural realizada. A técnica de difração de raio X permitiu identificar que todas as amostras de CaTiO3 apresentam-se na fase cristalina com simetria ortorrômbica. Através da espectroscopia de absorção de raio X na borda K do Ti4+ constatamos a ocorrência de maior simetria do Ti4+ em relação aos átomos ao seu redor quando aumentamos a temperatura de calcinação e que a substituição de íons no sítio do Ca2+ não altera essa simetria. Em razão do aumento da concentração dos dopantes, tanto no sítio do Ca2+ quanto no sitio do Ti4+, foram observados alterações nos modos de vibração dos espectros Raman. Constatou-se o aumento da torção entre os octaedros de TiO6 em relação ao aumento da concentração dos dopantes. No... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The calcium titanate CaTiO3 is a perovskite structure material which has been used as phosphor. It is well established that the incorporation of rare earth ions in the place occupied by Ca2+ cause significant changes in their structural properties and produce luminescent effects in the visible range. However, there are no studies reporting the insertion of La3+ on the Ca2+ site with respect to structural and luminescent characteristics of these materials. So, this work studies the photoluminescent properties presented by the matrix based on calcium titanate doped with praseodymium, lanthanum and aluminum. The material was synthesized by the Pechini method, which proved an effective method of preparation according to the structural characterization performed. The technique of X-ray diffraction showed that all samples are organized and exhibit orthorhombic symmetry. Using X-ray absorption spectroscopy at the K edge of Ti4+, we found that the occurrence of major symmetry of Ti4+ with respect to the neighbor atoms when the calcination temperature was increased and that the substitution of ions Ca2+ by Pr3+ does not change this symmetry. With the concentration of dopants increasing at the Ca2+ and Ti4+ sites, changes of the vibration modes in the Raman spectra were observed. It was found an increased torque between the TiO6 octahedra as a function of the increase in concentration of dopants. In the luminescence spectra, increasing the structural defect density enhanced the light e... (Complete abstract click electronic access below) / Mestre

Neste trabalho, investigamos a influência da estrutura de energia das minibandas dos estados eletrônicos ocupados no tempo de recombinação em poços quânticos múltiplos (MQW) fracamente acoplados de GaAs / AlGaAs. Um dos melhores métodos para estudar o efeito da estrutura energética consiste em medir o tempo de recombinação eletrônica em função de parâmetros expostas à influência externa que afeta a estrutura energética, por isso, aplicamos um campo magnético externo. O espectro da emissão de fotoluminescência foi composta pelas contribuições das minibandas da banda de condução, Γ – Γ e Γ – XZ. Observou-se um aumento notável do tempo de recombinação quando o campo magnético causou a despopulação da minibanda de maior energia, Γ – XZ. O efeito observado é atribuído à variação induzida pelo campo magnético na densidade dos estados eletrônicos. / In the present work, we investigate the influence of the miniband energy structure of the populated electron states on the recombination time in GaAs/AlGaAs weakly coupled multiple quantum wells (MQW). The best method to study the effect of the energy structure is to measure the recombination time in the same sample subject to external influence which affects the energy structure, therefore, we apply an external magnetic field. The photoluminescence emission was composed of the contributions from the Γ – Γ and Γ – XZ conduction band minibands. Remarkable enhancement of the recombination time was observed when the magnetic field caused depopulation of the higher energy Γ – XZ miniband. The observed effect is attributed to the magnetic field induced variation of the electron density of states.

Neste trabalho, estudamos o crescimento epitaxial por feixe molecular assim como as propriedades ópticas e estruturais de camadas de InGaAs depositadas sobre substratos de GaAs(001) com diferentes ângulos e direções de corte. Um ênfase foi dada à investigação da segregação dos átomos de Índio que modifica consideravelmente o perfil de potencial das heteroestruturas e influencia as características dos dispositivos contendo este tipo de camadas. Um novo método experimental baseado em medidas de difração de elétrons de alta energia (RHEED) possibilitou a determinação in situ e em tempo real do coeficiente de segregação dos átomos de Índio e, conseqüentemente, do perfil de composição das camadas de InGaAs. Medidas de raios X e de fotoluminescência em baixa temperatura foram realizadas em amostras de poços quânticos de InGaAs e confirmaram, a posteriori, os resultados obtidos pela técnica RHEED. Foi também demonstrado que o uso de substratos desorientados podia reduzir levemente o efeito de segregação e melhorar as propriedades ópticas das camadas em baixa temperatura. / In this work, we investigated the molecular-beam-epitaxy growth as well as the optical and structural properties of InGaAs layers deposited on top of GaAs (001) substrates with different miscut angles and directions. We emphasized the investigation of the segregation of In atoms that considerably modifies the potential profile of the heterostructures and influences the characteristics of the devices based on this type of layers. A new experimental method involving the diffraction of high-energy electrons (RHEED) allowed the in-situ and real-time determination of the segregation coefficient of the In atoms and, consequently, of the compositional profile of the InGaAs layers. X-rays and low-temperature photoluminescence measurements were carried out InGaAs quantum wells and confirmed, a posterior, the results obtained by the RHEED method. It was also demonstrated that the use of vicinal substrates slight reduces the segregation effect and improves the optical properties of the layers at low temperature.

A morfologia e dinâmica e filmes de MEH-PPV preparados pela técnica casting com os solventes tolueno e clorofórmio foram estudados utilizando Espalhamento de Raios-X de Alto Ângulo (WAXS) e técnicas de Ressonância Magnética Nuclear do Estado Sólido (RMN), respectivamente. Evidências do aumento da agregação foram obtidas por WAXS, que revelou uma tendência de aumento na ordem molecular sob tratamento térmico. Essas tendências foram suportadas pelas medidas de RMN que mostrou uma diminuição da mobilidade das cadeias laterais do MEH-PPV sob tratamento térmico, principalmente para os filmes feitos com o solvente tolueno. Ainda, a dependência das medidas de WAXS e RMN com a temperatura revelou que as mudanças na fotoluminescência dos filmes de MEH-PPV estão relacionadas às mudanças no ambiente molecular induzidas pelas dinâmicas dos segmentos. As medidas de espectroscopia de fluorescência (PL) com os dois tratamentos térmicos, 90 ºC por 12 horas e 150 ºC por uma hora, revelou que a banda da segunda emissão, relacionada ao aumento na agregação dos filmes, é aumentada sob os tratamentos térmicos, com forte dependência com as temperaturas dos tratamentos térmicos. Ambas as temperaturas foram escolhidas por estarem acima da temperatura de transição vítrea do MEH-PPV (Tg = 75 ºC), assim promovendo total relaxação das cadeias que constituem o polímero. / The morphology and dynamic of MEH-PPV films prepared by casting from toluene and chloroform were studied using Wide-Angle X-ray Scattering (WAXS) and Solid-State Nuclear Magnetic Resonance (NMR) techniques, respectively. Evidences of the increase in the aggregation were obtained by WAXS, which revealed a tendency of increasing in the molecular ordering upon thermal treatment. This tendency was supported by NMR measurements that showed the decrease in the mobility of the MEH-PPV side-chains upon thermal treatment, mainly from films cast from toluene. Moreover, the temperature dependence of the WAXS and NMR signals revealed that the changes in the MEH-PPV photoluminescence films are related to the changes in the molecular environment induced by the segmental dynamics. The Fluorescence Spectroscopy (PL) measured at two different thermal treatments, 90 ºC by 12 hours and 150 ºC by one hour, revealed that the second emission band, related to the increase in the aggregation of the films, is increased upon thermal treatments, with strong dependency with the thermal treatment temperatures. All the temperatures were away from the glass transition temperature of the MEH-PPV (Tg = 75 ºC), thus providing total relaxation stages to the polymer chains.