Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-06-07T19:30:35Z No. of bitstreams: 1 alisonarantesgoncalves.pdf: 3160281 bytes, checksum: b3f8a1585b5f5884a5571e6857646b8b (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-06-26T17:46:44Z (GMT) No. of bitstreams: 1 alisonarantesgoncalves.pdf: 3160281 bytes, checksum: b3f8a1585b5f5884a5571e6857646b8b (MD5) / Made available in DSpace on 2017-06-26T17:46:44Z (GMT). No. of bitstreams: 1 alisonarantesgoncalves.pdf: 3160281 bytes, checksum: b3f8a1585b5f5884a5571e6857646b8b (MD5) Previous issue date: 2012-03-08 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Apresentamos uma teoria para obtenção da seção de choque de espalhamento inelástico de luz, espalhamento Raman, a temperatura de T = OK em um gás de elétrons quasi-bidimensional formado pela heteroestrutura semicondutora de A1GaAs-GaAs dopada seletivamente. Os cálculos de estrutura eletrônica foram baseados na Teoria do Funcional Densidade dentro da aproximação de densidade local. Os cálculos para a seção de choque foram realizados em geometria de retroespalhamento e em regime de ressonância do laser incidente com o gap ótico de spin-órbita do GaAs. Estudamos os mecanismos de excitações de densidade de carga e excitações de densidade de spin. Os resultados obtidos foram [1]: 1) a observação do colapso do termo de Hartree nas excitações de densidade de carga para baixas densidades, observado experimentalmente por Ernst et al. [2]; 2) a observação de um cruzamento anômalo entre as excitações de densidade de carga e densidade de spin, em virtude dos funcionais de exchange-correlação. Este efeito constitui um teste de validade para as parametrizações adotadas; 3) a predição da existência de excitações de mais alta energia, ainda não observadas experimentalmente. Finalmente, demonstramos que o formalismo desenvolvido permite mapear as excitações eletrônicas na teoria BCS. / We present a theory for obtaining the inelastic light scattering cross section, Raman scattering, at T = OK temperature in a quasi-bidimensional electron gas formed by the GaAs-A1GaAs semiconductor heterostructure doped selectively. The electronic structure calculations were based on Density Functional Theory within the local density approximation. The calculations for the cross section were performed in backscattering geometry and resonant regime of the incident laser with the spin-orbit optical gap of GaAs . We study charge density excitations mechanism and spin density excitations mechanism. Our results were as follows [1] 1) the observation of the collapse of the Hartree term in the charge density excitation for low densities, observed experimentally by Ernst et al. [2], 2) the observation of an anomalous cross between charge density and spin density excitations, due to the exchange-correlation functional. This effect is a validity test for the adopted parameterizations; 3) the prediction of the existence of excitations of higher energy, not yet observed experimentally. Finally, we demonstrate that the formalism developed enables mapping the electronic excitations in the BCS theory, which describes the normal superconducting state.

With recent trends in miniaturization in the electronics sector, ferroelectrics have gained popularity due to their applications in non-volatile RAM. Taking one step further researchers are now exploring multiferroic devices that overcome the drawbacks of ferroelectric (FE) and ferromagnetic (FM) RAM’s while retaining the advantages of both. The work presented in this dissertation focuses on the growth of FE and FM thin film structures. The primary goals of this work include, (1) optimization of the parameters in the pulsed laser deposition (PLD) of FE and FM films and their heterostructures, (2) development of a structure-property relation that leads to enhancements in electric and magnetic polarizations of these structures, (3) investigation of doping on further enhancement of polarizations and coupling between the FE and FM layers. The materials of choice are La0.7Sr0.3MnO3 (LSMO) as the ferromagnetic and PbZr0.52Ti0.48O3 (PZT) as the ferroelectric component. Epitaxial thin film capacitors were grown using PLD. The work starts with the establishment of the optimum deposition conditions for PZT and goes on to describe results of attempts at performance enhancement and tuning using two methods. It is demonstrated that ferroelectric and ferromagnetic properties can be tuned by inserting a ferromagnetic buffer layer of CoFe2O4 (CFO) between PZT and LSMO. One of the key findings of this work was the anomalously high ferroelectric polarizations produced by lanthanum (La) doped PZT films. This work attempts to shine light on a possible mechanism that leads to such high enhancements in polarization.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Using the formalism of Density Functional Theory with spin polarization and the Generalized Gradient Approximation for exchange and correlation term, we studied the stability and electronic properties of substitutional impurities of C, Si and Ge in GaN, AlN and InN nanowires and the variation of the band offset with the diameter variation in AlN/GaN nanowires heterojunctions. For the study of substitutional impurities we use AlN, GaN and InN nanowires in the wurtzite phase with diameter of 14.47 Å, 14.7 Å and 16.5 Å, respectively. For the study of variation of the band offset with the diameter of the nanostructure, we use nanowires in the wurtzite phase with a mean diameter ranging from 0.99 nm to 2.7 nm and the zinc blende phase with an average diameter ranging from 0.75 nm to 2.1 nm. The electronic structure calculations show that of GaN, AlN and InN nanowires are semiconductors with direct band gap at point Γ. To study the substitutional impurities, we consider that the impurity can occupy the cation or anion sites in non-equivalent positions that are distributed from the center to the surface of the nanowire. For the C impurities, in GaN nanowires, we find that when the C atom is substituted in the N site, it will be uniformly distributed along the diameter of the nanowire. When substituted at the Ga site, it will be preferably find on the surface of the nanowire. In this case, the formation energy of CGa is almost identical to the CN, thus can occur formation of the auto-compensed CN-CGa pair. In AlN nanowires, when the C atom occupying the N site, it is also observed an almost uniform distribution along the diameter of the nanowire with a small preference (less energy formation) to the surface sites. Since the formation energy of the CN is lower than CAl in all regions of the nanowires, taking thus more likely to form CN. For InN nanowires, in the center sites, the formation energy of the CN and CIn is very similar, and the CN will have a uniform distribution along the diameter, but on the surface of the CIn is more stable and band structure show that this configuration has shallow donor levels. For Ge substitutional impurities in GaN nanowires, we observed that the center of the nanowire, the Ge atom is more likely to be found located in the Ga site, but in surface to find the most likely of N site, this being the most stable configuration. For AlN nanowires, the center of nanowire is possible to find the Ge atom at the N or Al sites, as the formation energy is practically the same. On the surface the more likely it is to find the Ge atom of the N site, which also is the most stable configuration. As for InN nanowires, the Ge atom will be found preferably at the In site with uniform distribution along the diameter of the nanowire. Analyzing the band structure of GeIn observed shallow donor levels. For the Si substitutional impurities, we obtain that in GaN and InN nanowires of the most stable configuration, the Si atom is to be found at the cation (Ga and In) sites in the central sites of the nanowire and analyzing the band structure of SiGa and SiIn, we also observed shalow donor levels. However, for AlN nanowires in the centerof the nanowire is greater the probability of finding the Si atom at the Al site, but the surface is greater the probability of finding the Si atom at the N site which is the most stable configuration. Finally, we analyze the variation of the band offset to the change in diameter of the nanowires forming the heterostructure. We consider heterostructure on yhe wurtzite and zinc blende phases, therefore during the synthesis the two phases are obtained. We found that the result is similar for the two phases and the extent that the diameter increases the value of the band offset also increases, tending to the value obtained for the bulk. / Usando o formalismo da Teoria do Funcional da Densidade com polarização de spin e a aproximação do gradiente generalizado para o termo de troca e correlação, estudamos a estabilidade e as propriedades eletrônicas de impurezas substitucionais de C, Si e Ge em nanofios de GaN, AlN e InN e a variação do band offset com o diâmetro em heteroestruturas da nanofios AlN/GaN. Para o estudo de impurezas substitucionais utilizamos nanofios de AlN, GaN e InN na fase da wurtzita e com diâmetros de 14,47 Å, 14,7 Å e 16,5 Å, respectivamente. Já para o estudo da variação do band offset com o diâmetro da nanoestrutura, utilizamos nanofios que formam a heteroestrutura na fase wurtzita com diâmetro médio variando 0,99 nm até 2,7 nm e na fase blenda de zinco com diâmetro médio variando de 0,75 nm até 2,1 nm. Os cálculos de estrutura eletrônica apresentam que os nanofios de AlN, GaN e InN são semicondutores com gap direto no ponto Γ. Para o estudo das impurezas substitucionais, consideramos que a impureza pode ocupar o sítio do cátion ou do aniôn, em posições não equivalentes que estão distribuídas do centro até a superfície do nanofio. Para a impureza de C, em nanofios de GaN, obtemos que, quando o átomo de C for substituído no sítio do N, o mesmo vai estar distribuído uniformemente ao longo do diâmetro do nanofio. Já quando substituído no sítio do gálio, o mesmo vai ser encontrado preferencialmente na superfície do nanofio, sendo que, na superfície do nanofio a energia do formação do CGa é praticamente a mesma do CN, assim pode ocorre a formação de pares autocompensados CN-CGa. Em nanofios de AlN, quando o átomo de C ocupar o sítio do N, também vai ter uma distribuição quase uniforme ao longo do diâmetro do nanofio com uma pequena preferência (menor energia de formação) para os sítios da superfície. Sendo que a energia de formação do CN é menor que do CAl em todas as regiões do nanofios, tendo assim, probabilidade maior de formar CN. Para nanofios de InN, nos sítios do centro, a energia de formação do CN e CIn é muito próxima, sendo que o CN vai ter distribuição uniforme ao longo do diâmetro, mas na superfície o CIn ser torna mais estável e a estrutura de bandas mostra que esta configuração apresenta níveis doadores rasos. Para impurezas substitucionais de Ge, em nanofios de GaN, observamos que no centro do nanofio, o átomo de Ge tem uma probabilidade maior de ser encontrado no síto do Ga, mas nos sítios da superfície a probabilidade é maior de encontrar no sítio do N, sendo essa a configuração mais estável. Para nanofios de AlN, no centro do nanofio, é possível encontrar o átomo de Ge no sítio do N ou Al, já que a energia de formação é práticamente a mesma. Na superfície a probabilidade maior é de encontrar o átomo de Ge no sítio do N, sendo, também, esta a configuração mais estável. Já para nanofios de InN, o átomo de Ge vai ser encontrado preferencialmente no sítio do In com distribuição uniforme ao longo do diâmetro do nanofio. Analisando a estrutura de bandas do GeIn observamos níveis doadores rasos. Para a impureza substitucional de Si, obtemos que em nanofios de GaN e InN a configuração mais estável, é o Si ser encontrado no sítio do cátion (Ga ou In) nos sítios centrais do nanofio e analizando a estrutura de bandas do SiGa e do SiIn, também observamos níveis doadores rasos. Entratanto, para nanofios de AlN, no centro do nanofio a probabilidade é maior de encontrar o átomo de Si no sítio do Al, mas na superfície a probabilidade é maior de encontrar o átomo de Si no sítio do N, sendo esta a configuração mais estável. Por fim, analisamos a variação do band offset com a variação do diâmetro do nanofios que forma a heteroestrutura. Consideramos heteroestruturas na fase wurtzita e blenda de zinco, pois nos processos de síntese as duas fases são obtidas. Observamos que o resultado é similar para as dias fases e, a medida, que o diâmetro aumenta o valor do band offset também aumenta, tendendo para o valor obtido para o cristal.

Dans ce travail de recherche, des oxydes mixtes dopés par des métaux nobles ont été préparés et mis en œuvre dans la réaction d'oxydation catalytique du chlorure de vinyle (VC). Les catalyseurs d'oxyde composite de Co-Ce ont été préparés par des procédés sol-gel et testés pour l'activité d'oxydation du VC. L'analyse XPS a certifié que l'introduction de Ce favorisait la présence d'espèces de Co2 + et de Ce3 +, ce qui modifie l'environnement de coordination du réseau d'oxygène et génère plus de vacations d'oxygène. Les oxydes de cobalt modifiés par Ru ont été préparés et étudiés pour l'oxydation du VC. L'analyse XPS montre que le Ru4 + et le Co2 + modifie la concentration des espèces oxygènes sur la surface. Une proportion relative élevée de Co2+ et de Ru4+ perturbe également les lacunes en oxygène. Cela impacte l'activité catalytique et diminue la quantité de sous-produits chlorés. Des mousses cellulaires mésostructurées de phosphate de cobalt-SiO2 (CoPO-MCFs) ont été synthétisées avec succès par la méthode de croissance in situ. Les analyses XPS confirment une augmentation d'espèces d'oxygène de surface pour ce système catalytique. L'énergie apparente d'activation confirme cette tendance. L'influence de la morphologie des particules de Co3O4, sur l'activité catalytique du méthyl benzène et du chlorure de vinyle a été étudiée. Le Co3O4 cubique a montré une meilleure activité et une meilleure stabilité que celle de Co3O4 sphérique. La structure cubique, avec Co2 + exposée à la surface, est le site actif de l'oxydation / In this research works, composite oxides, noble metal supported oxides and noble supported MCFs were prepared, and their catalytic performances were investigated for the catalytic oxidation of vinyl chloride (VC). The Co-Ce composite oxide catalysts were prepared by citrate sol-gel methods, and tested for the activity of VC oxidation. The catalyst with high performance is the molar ratio of Co/Ce=7:3. The XPS analyse certified that the Ce introduction favored the presence of Co2+ and Ce3+ species, which changed the coordination environment of the oxygen lattice and generated more oxygen vacancies. At last, this catalyst exhibited a good performance and stability during 110 h of time on stream at 300 oC. Ru-modified cobalt oxides were prepared and studied for the VC oxidation. The XPS analyse certified that the Ru4+ will be in synergy with Co2+ concentration and this would also change the chemical coordination of oxygen on the surface. High relative proportion of Co2+ and Ru4+ will also devote to oxygen defects or vacancies. This would increased the catalytic activity and decrease the amount of chlorinated by-products.A novel heterostructured material, cobalt phosphate-SiO2 mesostructured cellular foams (CoPO-MCFs), was successfully synthesized by the in-situ growth method. The XPS confirmed a higher amount of surface oxygen species. The activation energy calculated from Arrhenius plots showed a lower value for VC oxidation. The influence of Co3O4 morphology, including cube and sphere, on catalytic activity of methylbenzene and vinyl chloride was studied. The Co3O4 cube had shown better activity and stability than that of the Co3O4 sphere. The cube structure, with Co2+ exposed on the surface, acted as the active site of the oxidation

Au delà du graphène, de nouveaux semiconducteurs 2D tels que MoS2, GaS, GaSe et InSe deviennent pertinents pour les applications et dispositifs émergents. Dans cette thèse, nous fabriquons des échantillons de quelques feuillets atomiques de ces matériaux pour des dispositifs de photo-détecteurs et les caractérisons par microscopie optique, AFM et TEM. L'interaction de la lumière avec le substrat et le dispositif ultra-mince étant critique pour son fonctionnement, nous calculons et mesurons le contraste et l'intensité de la lumière diffusée par le dispositif. Nous caractérisons également la réponse Raman et la photoluminescence en fonction du nombre de couches pour étudier les propriétés vibrationnelles et électroniques. Plusieurs dispositifs ont été fabriqués et analysés. Nous examinons d'abord les dispositifs homogènes basés sur MoS2, GaSe ou InSe, et trouvons une excellente photosensibilité pour notre photo-détecteur MoS2. Nous examinons ensuite plusieurs hétéro-structures pour combiner les propriétés de chaque matériau et atteindre de meilleures performances. Le premier exemple est un photo-détecteur graphène/InSe dont la photosensibilité augmente de quatre ordres de grandeur par rapport à un dispositif basés sur InSe seul. Nous montrons également que la couche supérieure de graphène prévient la dégradation de couches atomiques ultra-minces dans l'air. Des hétéro-structures plus complexes graphène/InSe/graphène et graphène/InSe/Au montrent un effet photovoltaïque. Enfin, nous combinons InSe avec MoS2 et obtenons un dispositifs avec photo-réponse rapide, un comportement de type photo-diode, une distribution de photo-courant uniforme et un fort effet photovoltaïque. / Novel two dimensional (2D) semiconductors beyond graphene such as MoS2, GaS, GaSe and InSe are increasingly relevant for emergent applications and devices. In this thesis, we fabricate these 2D samples for photo-detector applications and characterize them with optical microscopy, atomic force microscopy, Raman and photoluminescence (PL) spectroscopy and transmission electron microscopy. Since the interaction of light with the substrate and the ultra-thin photodetector device is critical for its functioning we calculate and measure optical contrast and intensity of light scattered from the device. We also characterize the Raman and PL response as a function of number of layers to study both vibrational properties and the band gap transition. For the device application, we first examine homogenous devices based on few-layer MoS2, GaSe and InSe respectively and find an excellent photoresponsivity in our few-layer MoS2 photo-detector. We then examine several geometries for heterostructure devices, which have the advantage of combining favorable properties of each material to reach better performances. The first example is a graphene/InSe photo-detector where the photoresponsivity increases by four orders of magnitude with respect to a few-layer InSe device while the top graphene layer is also shown to prevent degradation of ultra-thin atomic layers in air. Still more complex graphene/InSe/graphene and graphene/InSe/Au heterostructures show a photovoltaic effect. Finally for the first time, we combine InSe with MoS2 and obtain a high performance device with fast photo-response, photodiode like behavior, uniform photocurrent distribution and high photovoltaic effect.

Orientador: José Antônio Brum / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-28T23:45:16Z (GMT). No. of bitstreams: 1 Andriolo_HelderFaria_M.pdf: 2066347 bytes, checksum: c0835c5528aa09df816a2dfb45249e5f (MD5) Previous issue date: 2015 / Resumo: Nesse trabalho estudamos um sistema de GaAs/In_{0.27}Ga_{0.73} As/Al_{0.3}Ga_{0.7}As, intencionalmente dopado com material do tipo-n, em que ocorre a transferência de elétrons, provenientes da dopagem, para o poço quântico de In_{0.27}Ga_{0.73}As, formando um gás de elétrons bidimensional no poço. A seguir o efeito da introdução de pontos quânticos auto-organizados de InAs na estrutura foi analisado. Nossos resultados mostram uma pequena mudança no perfil de potencial da estrutura. O que ocorre após a introdução dos pontos quânticos é, basicamente, uma redistribuição dos elétrons, que agora passam a ocupar o poço quântico e o ponto quântico. Estudamos também as propriedades ópticas, espectros de absorção e emissão, de pontos quânticos acoplados com gás de portadores. Para isso foi necessário estabelecer um método na qual discretizamos o contínuo de níveis energéticos do gás de portadores (elétrons), o método através da cadeia de Wilson foi o utilizado nos cálculos, embora outros dois métodos também tenham sido mostrados. Introduzimos, por fim, um íon de manganês no centro do ponto quântico e calculamos espectros de emissão desse sistema com os níveis do gás elétrons discretizados através da cadeia de Wilson / Abstract: In this work, we study a GaAs/In_{0.27}Ga_{0.73}As/Al_{0.3} Ga_{0.7}As system intentionally doped n-type material, which occurs a transfer of electrons from the doping into In_{0.27}Ga_{0.73}As quantum well, forming a two-dimensional electron gas in the well. Next, the effect of introducing self-assembled InAs quantum dots in the structure was analyzed. Our results show little change in potential profile of the structure. What happens after the introduction of quantum dots is basically a redistribution of electrons, that now occupy the quantum well and quantum dot. We also studied the optical properties, absorption and emission, of quantum dots coupled with carrier gas. This required establishing a method in which discretize the continuous energy levels of the carrier gas (electrons), the method by Wilson chain was used in the calculations, although other two methods also have been shown. Introduced, finally, a manganese ion in the center of the quantum dot, and we calculated emission spectra of this system, with the electron gas levels discretized by Wilson chain / Mestrado / Física / Mestre em Física / 131432/2013 / 2013/25371-1 / CNPQ / FAPESP

Orientador: Leinig Antônio Perazolli / Resumo: O presente trabalho buscou desenvolver fotocatalisadores cerâmicos por meio da produção de heterojunções inovadoras à base de SrTiO3, TiO2 e CaO, que tiveram suas fotoatividades avaliadas pela descoloração do corante Rodamina B (RhB) e pela obtenção de biodiesel, utilizando luz ultravioleta. As amostras TiO2, CaO e SrTiO3 foram obtidas pelo método de precursores poliméricos, método Pechini, e as heterojunções TiO2/SrTiO3, CaO/SrTiO3 e CaO/CaTiO3 foram preparados por rota sol-gel. Após síntese e tratamento térmico, as amostras foram caracterizadas por difração de Raios-X (DRX) para verificar as fases cristalinas formadas, por espectroscopia de infravermelho com transformada de fourier (FT-IR) e termogravimetria/análise térmica diferencial (TG/DTA) para verificar e quantificar a formação de CaCO3 e Ca(OH)2, por espectroscopia de refletância difusa (UV/Vis/NIR DRS) para determinar a energia de band gap, por Brunauer, Emmett e Teller (B.E.T.) para determinar a área específica, por microscopia eletrônica de varredura acoplada a espectroscopia de energia dispersiva de Raios-X (FE-SEMEDS) para estimar o tamanho das partículas, sua morfologia e composição elementar, por espectroscopia de fotoelétrons excitados por Raios-X (XPS) para conhecer a composição elementar presente na superfície da amostra e seus estados de oxidação, por espectroscopia de fotoluminescência (PL) para verificar a formação de defeitos estruturais, por microscopia eletrônica de transmissão de alta resolução (HRTE... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The present work aimed to develop ceramic photocatalysts through the production of innovative SrTiO3, TiO2 and CaO based heterojunctions, which had their photoactivities evaluated by the discoloration of Rhodamine B (RhB) dye and by obtaining biodiesel using UV light. TiO2, CaO and SrTiO3 samples were obtained by polymeric precursor method, Pechini method, and TiO2/SrTiO3, CaO/SrTiO3 and CaO/CaTiO3 heterojunctions were prepared by sol-gel route. After synthesis and heat treatment, the samples were characterized by X-ray diffraction (XRD) to verify the crystalline phases formed, fourier transform infrared spectroscopy (FT-IR) and thermogravimetry/differential thermal analysis (TG/DTA) to verify and quantify the formation of CaCO3 and Ca(OH)2, diffuse reflectance spectroscopy (UV/Vis/NIR DRS) to determine band gap energy, Brunauer, Emmett e Teller (B.E.T.) to determine specific area, field emission scanning electron microscopy coupled X-ray dispersive energy spectroscopy (FE-SEM-EDS) to estimate particle size, morphology and elemental composition, X-ray photoelectron spectroscopy (XPS) to know the elemental composition present on the sample surface and oxidation states, photoluminescence spectroscopy (PL) to verify the formation structural defects, high resolution transmission electron microscopy (HRTEM) to confirm the formation of heterojunction. Rhodamine B discoloration was measured by UV/Vis molecular absorption spectroscopy and the conversion of oil to biodiesel was analyz... (Complete abstract click electronic access below) / Doutor

Molecular self-assembly or ligand-metal assembly is a process in which several individual molecules and metal ions organize themselves into an ordered arrangement without external stimuli, the defined structures can lead to distinctive electronic and photonic performances. In the meantime, as the scale of materials decreases, various unique properties arise from their minute scaled dimensions, such as surface effect, volume effect, quantum effect and dielectric confinement effect, etc. Therefore, the design and fabrication of the micro- and nanomaterial via the technique of molecular self-assembly or ligand-metal assembly is becoming an emerging research field, for the purpose of meeting the increased demands of multi-functional materials. Chapter 1 gives an overview of the advanced materials prepared by either molecular self-assembly or ligand-metal assembly. We described the interaction nature in detail, and enumerated the applications as well as developments of this scientific field. Furthermore, the detailed classifications as well as previous work of these advanced materials we researched on, such as two dimensional nanosheets, hetero-structured materials and cyclometalated iridium(Ⅲ) complexes were also amply summarized. Two-dimensional nanosheets have always been a research hotspot since graphene was discovered and isolated. In contrast, molecule-based organometallic nanosheets through bottom-up method exhibit more inner structures. In Chapter 2, we constructed two classes of organometallic nanosheets with different intermolecular forces, one is metal-ligand coordination, while the other one is the aromatic (π-π) interaction. Two-dimensional nanosheets with Hg-acetylide linkages, bis(dipyrrinato)metal linkages as well as bis(terpyridine)metal linkages were synthesized and characterized by UV-Vis absorption spectroscopy, FT-IR spectroscopy, optical and electron microscopy, photoluminescence spectroscopy, thermal gravimetric analysis, X-ray photoelectron spectroscopy and so on. In addition, the potential applications were explored as well, including the tests of charge mobility and current capacitance. Meanwhile we also investigated the two-dimensional nanosheets self-assembled by aromatic (π-π) interaction. The morphology characterizations, crystal form measurements, besides elemental analyses were conducted. By means of surface control, the hybrid nanosheets could achieve many superior performances, like super hydrophobicity, high conductivity and soft magnetism. In Chapter 3, we firstly mentioned that organic hetero-structured micro- or nanomaterials are widely attractive on account of its extensive applications in lasers, bipolar transistors, field effect transistors and solar cells. In our work, we focus on the diverse microrods assembled from π-conjugated small molecules, especially in the construction of heterogeneous organic heterojunction materials with specific components distribution. Two novel kinds of heterostructure, multilayer core-shell structured heterojunction and heterogeneous rod-tail helix were fabricated and developed both via a stepwise seeded-growth route, in which the different constituents possess different colors of luminescence. Through the media of fluorescence microscopy and confocal microscopy, the core-shell hetero- structures can be observed, testified and recorded quite distinctly. Furthermore, the prepared method by employing seeded-precursor could give us a revelation about constructing more sophisticated and functional organic luminescent heterogeneous materials. Chapter 4 focuses on the syntheses and characterization of eight cyclometalated iridium(Ⅲ) complexes, Ir(TPY)2(Dipyrrinato), Ir(PIQ)2(Dipyrrinato), Ir(Ligand 1)2(Dipyrrinato), Ir(Ligand 2)2(Dipyrrinato), Ir(Ligand 3)2(Dipyrrinato), Ir(PPY)2 (Dipyrrinato), Ir(m-PPY)2(Dipyrrinato) and Ir(PPY-m)2(Dipyrrinato). As is known, iridium(Ⅲ) complexes can exploit the energy of both 25% singlet and 75% triplet excited states. Due to their highly efficient applications in phosphorescent OLEDs, these materials are considered as one of the potential candidates for flexible display screen as well as clearing luminary. Among those full-color light-emitting iridium(Ⅲ) phosphors, near-infrared (NIR) phosphors are broadly utilized in phototherapy as well as biosensors. Herein, our eight synthetic cyclometalated iridium(Ⅲ) complexes all gave photoluminescence at 680 - 700 nm in solution, which could be attributed to the NIR region. We continuously tune the extensive conjugation on the C^N ligands in order to make longer wavelength emitting phosphors. The HOMO and LUMO of eight synthetic iridium(Ⅲ) phosphors were also calculated according to their cyclic voltamograms (CV). The design and preparation strategy in this thesis can inspire us to develop near-infrared as well as higher-performance organometallic phosphors.

This master thesis is focused on characterization of electrical transport properties of one-dimensional nanostructures. First section of this work deals with theoretical description of the experimental approaches to realization of such measurements. This section involves also a detail discussion of preparation of contacts using e-beam lithography. Next, theoretical description of characterization of nanostructures using photoluminescence measurements is given. Second section describes practical application of the aforementioned electrical transport measurements. Presented results include transport and photoluminescence measurements of WS2 nanotubes, InAs and WO2.72 nanowires. The last section of this thesis deals with nanowire quantum well heterostructures. The section provides both a deeper theoretical view of the problem and results of the photoluminescence measurements are shown.

Ce travail s’est articulé autour de la modulation des propriétés électroniques du graphène. Un des objectifs visés étant la conception d’électrodes transparentes pour des applications photovoltaïques. Différentes techniques de dopage ont été utilisées pour la modulation du travail de sortie (WF) et de la mobilité électronique comme l’incorporation d’azote in-situ lors de la croissance, l’incorporation d’azote ex-situ par acide nitrique et acide aurique. Diverses techniques de caractérisation ont été employées notamment la microscopie à force atomique AFM/CPAFM, la spectroscopie Raman, la spectroscopie photoélectronique (XPS et UPS), les mesures de transport électrique par effet Hall et effet de champ. Ces techniques nous ont permis de déterminer l’homogénéité, la qualité cristalline, la variation de densité de charges électronique, la résistance électrique et la mobilité électronique des différents matériaux intrinsèques et dopés. Par ailleurs, nous avons montré qu’il était possible de moduler le travail de sortie du graphène CVD en déposant par PECVD du silicium amorphe dopé N ou P sans endommager le graphène. Cette approche présente un intérêt particulier pour la substitution de l’ITO par le graphène en tant qu’électrode transparente. Les mesures de transport électronique ont mis en évidence un transfert de charges à l’interface de l’hétérojonction graphène/silicium amorphe. Cette variation dépend non seulement du type du dopage du silicium amorphe mais aussi de la cristallinité de ce dernier, ainsi peut-on espérer réduire la résistivité d’une électrode pour cellule photovoltaïque. / This work was structured around the modulation of the electronic properties of graphene obtained via the CVD growth on copper substrate and/or the graphitization of the carbon atoms in the SiC substrate. One of the objectives was the design of electrodes (front or rear) for photovoltaic cells, among other applications. Different doping techniques have been implemented for modulating the work function (WF) and the electron mobility i.e. the incorporation of nitrogen in-situ during the growth, ex-situ incorporation by nitric acid and/or nano gold colloids (AuCl3). In this work, various characterization techniques were employed including atomic force microscopy (AFM), Raman spectroscopy, photoelectron spectroscopy (XPS and UPS), electrical transport measurements by Hall and field effect. These techniques have enabled us to determine the homogeneity , thecrystalline quality of the material, the carrier density, the electrical resistance and the electron mobility of different intrinsic and doped samples. Furthermore, we showed that it is possible to modulate the WF graphene by fabricating a heterostructure composed of PECVD amorphous silicon doped N or P deposited onto the graphene. This approach is of particular interest for replacement of ITO with graphene as transparent electrode. This result was confirmed by the study detailed spectra of the XPS and Raman vibrational states. The electronic transport measurements showed a charge transfer at the interface of the heterojunction graphene/amorphous silicon. The variation observed depends not only on the type of doping of the amorphous silicon but also on the crystallinity of the latter. This approach can readily be adapted to photovoltaic devices.