Organic light-emitting diode (OLED) technology has found multitudinous applications in the development of solid-state lighting, flat-panel displays and flexible screens. Nowadays, the phosphorescent OLEDs based on metallophosphors can reach sufficiently high efficiencies for practical application. Recently, red, green and blue (RGB) platforms of highly efficient phosphorescent emitters have been achieved and OLEDs TV is now commercialized in the marketplace. However, the design and synthesis of innovative emitter materials play an important role in commercialization of the OLED technology. The basic concept of OLED is herein discussed in chapter 1 putting main focus on phosphorescent iridium(III) complexes. In chapter 2, a series of cyclometalated iridium(III) complexes containing 2-(4-benzylphenyl)pyridine have been synthesized and different electron-donating and electron-withdrawing substituents were attached on the pyridyl ring in the ligand. The device D6 doped with 8 wt% B4 gave the excellent OLED performance with a peak of external quantum efficiency (ext) of 21.4%, power efficiency (P) of 51 lm/W and current efficiencyL) of 76.3 cd/A, which is much higher than that of commercial available fac-Ir(ppy)3 under the same operation condition. These findings draw our attention to the fact that a weak electron-donating benzyl group could alleviate intermolecular aggregation in the solid state, thus improving the device performance. The bulky moiety introduced on 2-phenylpyridine through a CH2 spacer in the ligands could suppress the triplet-triplet annihilation in their metal complexes. Cylcometalating ligands and their respective metal complexes have been fully characterized by 1H and 13C NMR spectroscopy and matrix-assisted laser desorption inoization-time of flight (MALDI-TOF) mass spectrometry. In chapter 3, a series of thiazole-based iridium(III) complexes have been synthesized and characterized. It is considered that the thiazole moiety is infrequently used for organic semiconducting materials. To have a better understanding on this functional unit, different hole-transporting groups (eg, carbazole or fluorene) are attached to the thiazole ring in the cyclometalating ligands in order to tune the HOMO and LUMO levels of the complexes. Device D29 doped with 8 wt% T2 gave the highest L of 35.8 cd/A and ext of 11.1%. This result implied that thiazole moiety is an alternative option to afford a new class of cyclometalating ligands for OLED research. In chapter 4, a series of cationic iridium(III) complexes bearing diimine ligand have been synthesized and characterized. The diimine ligands were decorated with the sterically bulky groups. As self-aggregation could deteriorate the device efficiency, this molecular design strategy can diminish the aggregation-caused quenching problems, which has been supported by the aggregation-induced emission enhancement present in complexes E2 and E3. In Chapter 5, a series of bis-tridentate iridium(III) complexes have been synthesized and characterized. Our challenging is to design two types of tridentate chelates (ie. monoanionic and dianionic ligands) for balancing the charge on the metal center. Besides, these chelates should be a good cyclometallate to coordinate with the iridium metal. Four compounds with different dianionic tridentate chelates were designed to achieve distinct color emission. Compound K4 exhibited extremely high quantum yield of 85.5%. This finding revealed that the metal complex featuring two tridentate chelates is a promising phosphorescent dye in OLED. Lastly, the concluding remarks and the experimental details of all the compounds in the previous chapters were included in Chapters 6 and 7.

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Made available in DSpace on 2014-06-11T19:29:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-06-22Bitstream added on 2014-06-13T19:38:14Z : No. of bitstreams: 1 lahoud_mg_me_araiq_parcial.pdf: 168693 bytes, checksum: b5576636cc80e2d28e2ff261bf846325 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho apresenta a síntese e caracterização espectroscópica, estrutural, morfológica e térmica de cinco novos complexos mistos de terras raras contendo os ligantes succinato e 3,5-dicarbóxipirazolato. O foco central foi investigar a interação entre alguns íons de terras raras e esses ligantes dicarboxilatos, com ênfase nas propriedades luminescentes e suas relações com a estrutura dos complexos obtidos. A difração de raios X de monocristal revelou que os compostos são isoestruturais, constituídos de unidades binucleares discretas, de fórmula geral [TR2(dcpz)2(suc)(H2O)8](H2O)1.5 (TR = Eu, Gd, Tb, Dy e Y). Essas unidades crescem tridimensionalmente por meio de ligações de hidrogênio. Investigação espectroscópica dos complexos de Gd3+ e Y3+ mostraram que o nível tripleto dos ligantes está acima do nível emissor dos íons Eu3+, Tb3+ e Dy3+, o que possibilitou a ocorrência de efeito antena nesses sistemas. Sendo assim, emissões nas regiões do vermelho, verde e próxima ao branco foram observadas, respectivamente. As medidas de susceptibilidade magnética, realizadas sob a coordenação do Prof. Dr. Rafael Sá de Freitas do IF/USP de São Paulo, mostraram que o complexo de Y3+ apresentou ser diamagnético à temperatura ambiente. Quanto aos demais compostos da série, estes revelaram ser paramagnetos, com momentos magnéticos compatíveis com o momento dos spins dos íons isolados, o que está de acordo com o fato de serem dímeros isolados, não havendo, portanto, interação entre os spins / This work presents structural, morphological and thermal synthesis and spectroscopic characterization of five new rare earth complexes that contain succinate and 3,5-dicarboxypyrazolate ligands. The main focus was to investigate the interaction between rare earth ions and these dicarboxylate ligands, particularly the luminescence proprieties and their relation with the structure of the obtained complexes. The single crystal X-ray diffraction revealed that the compounds are isostructural, consisting of binuclear discrete units, their general formula being [TR2(dcpz)2(suc)(H2O)8](H2O)1.5 (TR = Eu, Tb, Dy, Gd, Y), These units grow three-dimensionally through hydrogen bonds. Spectroscopic investigation of the complexes Gd3+ and Y3+ showed that the triplet level of the ligands is above the emitting level of the ions Eu3+, Tb3+ e Dy3+, which enabled the occurrence of antenna effect in these systems. Thus, emissions in the red and green regions, as well as the one nexts to the white one, were observed, respectively. The magnetic susceptibility measurements, performed under the supervision of Professor Rafael Sá de Freitas, from IF/USP São Paulo, showed that the Y3+ complex is diamagnetic in room temperature. As to the other compounds of the series, these proved to be paramagnets, with magnetic moments compatible with the time of the spins of the isolated ions. This is consistent with the fact that they are isolated dimers. There is not, therefore, interaction between the spins

Made available in DSpace on 2014-06-11T19:29:10Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-06-01Bitstream added on 2014-06-13T20:59:19Z : No. of bitstreams: 1 monteiro_jhsk_me_araiq.pdf: 1330197 bytes, checksum: 74fd45b28c60d86fcc9d01c96a530f4b (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A síntese e o estudo da luminescência dos complexos [Ln(tta)3(dppmo)], sendo Ln = Sm3+, Eu3+ e Gd3+, tta = tenoiltrifluoroacetonato e dppmo = bis(difenilfosfino)metano dióxido são descritos neste trabalho. O ligante (dppmo) foi obtido através da oxidação do bis(difenilfosfino)metano (dppm) e utilizado como reagente para substituição das moléculas de água do aquo complexo [Ln(tta)3(H2O)2] precursor. A coordenação dos ligantes foi indicada pelo deslocamento para menores energias dos estiramentos dos grupos C=O e P=O. A estequiometria foi confirmada por titulação complexométrica da Ln3+ e análise elementar de carbono e de hidrogênio. A análise termogravimétrica indicou que não há perda de massa relativa a água e que o composto sintetizado possui uma boa estabilidade térmica. Através do espectro de emissão do complexo de gadolínio foi determinado o tripleto mais intenso do sistema em 1,840.104 cm-1. O espectro de emissão do complexo de európio apresenta transições 5D0 _ 7FJ (J = 0; 1; 2; 3 e 4) sendo a transição 5D0 _ 7F0 uma única linha indicando somente um sítio emissor sem centro de inversão. Do espectro de emissão foram determinados os parâmetros de intensidade _2, _4, R02 e Arad e a partir da curva de decaimento do estado emissor o tempo de vida (_) de 0,52 ms. A taxa de emissão total foi calculada a partir do inverso do tempo de vida e a eficiência quântica pela relação entre a taxa de emissão radiativa e não radiativa obtendo-se _ = 47%. O espectro de emissão do complexo de samário apresentou as linhas características 4G5/2 _ 6HJ (J = 5/2; 7/2; 9/2 e 11/2) sendo a transição 4G5/2 _ 6H9/2 de maior intensidade no espectro. O aumento do tempo de vida do estado emissor indica que as perdas por processos não-radiativos são minimizadas em relação ao aquo complexo precursor. Foram determinadas: geometria teórica utilizando o modelo Sparkle / AM1... / The synthesis and the luminescence study of complexes [Ln(tta)3(dppmo)], with Ln = Sm3+, Eu3+ and Gd3+, tta = thenoyltrifluoroacetonate and dppmo = bis(diphenylphosphine)methane dioxide are reported. The ligand (dppmo) was obtained by oxidation of bis(diphenylphosphine)methane and used as reagent to substitute the water molecules of aquo complex precursor [Ln(tta)3(H2O)2]. The ligand coordination was showed by the shift to low wavenumbers of C=O and P=O stretchings. The stoichiometry was confirmed by complexometric titration of Ln3+ and elemental analysis of carbon and hydrogen. The thermogravimetric analysis showed that there is no water molecules weight loss and that the complex has a good thermal stability. The most intense triplet of the system was determined in 1.804x104 cm-1 through the gadolinium emission spectrum. The europium complex emission spectrum presented the transitions 5D0 _ 7FJ (J = 0; 1; 2; 3 and 4) with only one line for transition 5D0 _ 7F0 showing that there is only one noncentrossymetric site. The intensity parameters _2, _4, R02 and Arad were determined from emission spectrum while the lifetime (_) was determined from decay curve and its value is 0.53 ms. The total emission rate was calculated from the inverse of lifetime and the quantum efficiency by relation between radiative emission rate and total emission rate obtaining _ = 47%. The emission spectrum of samarium complex presented the transitions 4G5/2 _ 6HJ (J = 5/2; 7/2; 9/2 and 11/2) with the most intense transition 4G5/2 _ 6H9/2 one. The lifetime increasing compared with that of aquo complex precursor shows that the non-radiative quenching is minimized. The ground state geometry and theoretical UV-vis absorption spectrum were determined using the Sparkle / AM1 implemented in Mopac2009 package. Transfer and back transfer energy rates from ligand to rare earth, the population of fundamental singlet, excited... (Complete abstract click electronic access below)

Made available in DSpace on 2014-06-11T19:29:10Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-04-29Bitstream added on 2014-06-13T20:19:01Z : No. of bitstreams: 1 oliveira_hhs_me_araiq.pdf: 1911814 bytes, checksum: c76bc8905c1967b3e68ff5989a24773e (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Cintiladores são materiais capazes de absorver radiações de alta energia e convertê-las eficientemente em radiações ultravioleta ou visível. Avanços significativos na eletrônica de detecção dessas radiações motivaram as pesquisas visando à busca por novos materiais cintiladores de alta eficiência e à maior compreensão do mecanismo de cintilação. Nesse contexto, os compostos de matriz GdAlO3 e Gd1-xLuxAlO3 dopados com Eu3+, Tb3+ ou Pr3+ são materiais cintiladores promissores, pois apresentam alta densidade, elevados valores de coeficiente de atenuação de massa e propriedades espectroscópicas relevantes como emissão intensa, tempo de vida de mili ou microssegundos e transferência de energia a partir dos íons Gd3+ para os ativadores. Neste trabalho, foi investigada a preparação dos cintiladores GdAlO3 e Gd1-xLuxAlO3 nominalmente puros e dopados com Eu3+, Tb3+ e Pr3+ através do método dos precursores poliméricos (método Pechini) e suas propriedades estruturais e espectroscópicas (fotoluminescência e luminescência com excitação por raios X) foram investigadas. O perfil espectral de emissão das amostras de GdAlO3 dopadas com Eu3+ evidencia a ocupação de dois sítios distintos pelos íons dopantes quando em concentrações superiores a 1,0%-mol, provavelmente devido à distribuição não homogênea dos íons na matriz. A transferência de energia Gd3+→Ln3+ foi evidenciada pela espectroscopia de fotoluminescência e é um processo importante no mecanismo de cintilação desses materiais, como evidenciado pela comparação das medidas espectroscópicas de fotoluminescência e luminescência com excitação por raios X das amostras de GdAlO3:Pr3+. Com a incorporação de Lu3+ na matriz de GdAlO3, a intensidade de emissão aumenta até a concentração de 10%-mol de Lu3+, decrescendo... / Scintillators materials are compounds that can absorb ionizing radiations and efficiently convert them into UV-VIS radiations. Despite of impressive advances in the technology of direct detection, the search for new scintillators materials with high efficiency and for the precise understanding of the scintillation mechanism is still the focus of research in this area. In this context, the compounds GdAlO3 and Gd1-xLuxAlO3 doped with Eu3+, Tb3+ and Pr3+ are promising scintillators materials, since they have high density, high values of mass attenuation coefficient and relevant spectroscopic properties, such as bright emission, lifetime of milli or microseconds and the energy transfer from Gd3+ ions to the activators. This work describes the preparation of GdAlO3 and Gd1-xLuxAlO3 nominally pure and doped with Eu3+, Tb3+ e Pr3+ by the polymeric precursor method (Pechini method) and the study of their structural and spectroscopic (photoluminescence and X-rays excited optical luminescence) properties. Emission spectral profile of Eu3+-doped GdAlO3 indicates the occupation of two different sites by the dopant ions when the concentration is higher than 1.0 mol-%, probably due to inhomogeneous distribution of ions in the host. The energy transfer Gd3+→Ln3+ was evidenced by photoluminescence spectroscopy and is an important process in the scintillation mechanism of these materials, as showed by comparison of spectroscopic measurements of photoluminescence and X-rays excited optical luminescence of GdAlO3:Pr3+ sample. The emission intensity increases by incorporating Lu3+ in the GdAlO3 host until the Lu3+ concentration of 10 mol-%, decreasing at higher concentrations. This behavior is probably assigned to the balance between increasing the absorption of X-rays and the reduction of the transfer process from Gd3+ ions with increasing concentration of... (Complete abstract click electronic access below)

Orientador: Regina Célia Galvão Frem / Coorientador: Marian Rosaly Davolos / Banca: Hermi Felinto de Brito / Banca: Flavia Cavalieri Machado / Resumo: Este trabalho apresenta a síntese e caracterização espectroscópica, estrutural, morfológica e térmica de cinco novos complexos mistos de terras raras contendo os ligantes succinato e 3,5-dicarbóxipirazolato. O foco central foi investigar a interação entre alguns íons de terras raras e esses ligantes dicarboxilatos, com ênfase nas propriedades luminescentes e suas relações com a estrutura dos complexos obtidos. A difração de raios X de monocristal revelou que os compostos são isoestruturais, constituídos de unidades binucleares discretas, de fórmula geral [TR2(dcpz)2(suc)(H2O)8](H2O)1.5 (TR = Eu, Gd, Tb, Dy e Y). Essas unidades crescem tridimensionalmente por meio de ligações de hidrogênio. Investigação espectroscópica dos complexos de Gd3+ e Y3+ mostraram que o nível tripleto dos ligantes está acima do nível emissor dos íons Eu3+, Tb3+ e Dy3+, o que possibilitou a ocorrência de efeito antena nesses sistemas. Sendo assim, emissões nas regiões do vermelho, verde e próxima ao branco foram observadas, respectivamente. As medidas de susceptibilidade magnética, realizadas sob a coordenação do Prof. Dr. Rafael Sá de Freitas do IF/USP de São Paulo, mostraram que o complexo de Y3+ apresentou ser diamagnético à temperatura ambiente. Quanto aos demais compostos da série, estes revelaram ser paramagnetos, com momentos magnéticos compatíveis com o momento dos spins dos íons isolados, o que está de acordo com o fato de serem dímeros isolados, não havendo, portanto, interação entre os spins / Abstract: This work presents structural, morphological and thermal synthesis and spectroscopic characterization of five new rare earth complexes that contain succinate and 3,5-dicarboxypyrazolate ligands. The main focus was to investigate the interaction between rare earth ions and these dicarboxylate ligands, particularly the luminescence proprieties and their relation with the structure of the obtained complexes. The single crystal X-ray diffraction revealed that the compounds are isostructural, consisting of binuclear discrete units, their general formula being [TR2(dcpz)2(suc)(H2O)8](H2O)1.5 (TR = Eu, Tb, Dy, Gd, Y), These units grow three-dimensionally through hydrogen bonds. Spectroscopic investigation of the complexes Gd3+ and Y3+ showed that the triplet level of the ligands is above the emitting level of the ions Eu3+, Tb3+ e Dy3+, which enabled the occurrence of antenna effect in these systems. Thus, emissions in the red and green regions, as well as the one nexts to the white one, were observed, respectively. The magnetic susceptibility measurements, performed under the supervision of Professor Rafael Sá de Freitas, from IF/USP São Paulo, showed that the Y3+ complex is diamagnetic in room temperature. As to the other compounds of the series, these proved to be paramagnets, with magnetic moments compatible with the time of the spins of the isolated ions. This is consistent with the fact that they are isolated dimers. There is not, therefore, interaction between the spins / Mestre

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Climate change has given rise to higher demand of renewable energy. Conventional non-organic solar cells are still seen the most on the market but the last 10-20 years there has been an exponential increase in research about organic solar cells. The research demands measurements done on increasing fast time scales as insights about the topic and technology develops. Here is presented configurations done at the Isaak spectrometer at Freie Universit\"{a}t Berlin. The spectrometer is used for studying charge transport in organic solar cells as well as hybrid solar cells made from organic and inorganic semiconductors. One important feature for the time response is the Q factor property of the resonator in which the sample is placed. The Q factor describes the rate of energy loss relative to the stored energy of the resonator. The Q factor dependency over different temperature was studied in order to gain vital knowledge about the time response of the setup. Further new equipment was been installed at the setup and programmed in FSC2. This in order to increase the sensitivity of the optical setup, secure the personnel from possible dangerous excitation laser and in order to do more automated measurements. As the optical path was modified by installing a new optical fiber a new calibration had to be done. Finally, in order to try the functionality of the new equipment an automated energy dependency measurement was done on the polymer MEH-PPV and the polymer:fullerene blend MEH-PPV:PCBM. The automatic process of measuring was successful.