La recherche présentée dans cette thèse traite de la synthèse, propriétés et applications optoélectroniques de matériaux nanohybrides basés sur le greffage d’une porphyrine donneur d’électron et d’un dérivé du fullerène sur des nanoparticules de ZnO.Ces molécules sont accrochées à la surface de l’oxyde métallique grâce à une fonction acide carboxylique. L'effet du rapport molaire porphyrine / fullerène, de la polarité du solvant et la forme des nanoparticules sur les propriétés optiques des nanohybrides ont été étudiés. Les interactions porphyrine / fullerène à l’échelle moléculaire apparaissent pour un rapport de 1:2 à l'état co-greffé sur des nanobâtonnets de ZnO. Cela est indiqué par le fort décalage bathochrome du pic de Soret des porphyrines et de l’extinction de sonémission de fluorescence. Toutefois, à cette valeur du rapport, le complexe de transfert de charge n'est pas détectable. La formation de ce complexe requiert à la fois les molécules donneur et accepteur d’électron d'être d’être maintenues à proximité, ce qui est réalisableen augmentant le rapport stoechiométrique à 1:3 et au-delà. Dans l’acétonitrile, une bande d’absorption de transfert de charge de faible intensité apparaît vers 700-800 nm, ainsi qu’une bande d'émission à 800 nm, caractérisant la complexation supramoléculaire à la surface de l’oxyde métallique. Lorsqu'ils sont utilisés pour la fabrication de la couche active dans une cellule solaire à hétérojonction hybride, les nanobâtonnets de ZnO fonctionnalisés montrent une efficacité de conversion lumineuse pour des valeurs faibles du rapport porphyrine / fullerène, mais l’augmentation du taux de fullerène tend à diminuer le rendement de conversion photovoltaïque. Cet effet a été relié à l’apparition de défauts morphologiques dans les films minces induite par l’agrégation des nanotubeslié au taux et rapport de greffage des molécules organiques. / The research presented in this dissertation deals with the synthesis, properties andoptoelectronic applications of the nanohybrids based on dye and fullerene functionalizedZnO nanoparticles. These molecules being acid functionalized, were co-grafted on thesurface of ZnO nanoparticles. The effect of changing ratio of donor to acceptor, polarityof the solvent and shapes of the nanoparticles on porphyrin/fullerene interaction werestudied. The molecules were found appreciably interacting at a ratio of 1:2 under the cograftedstate on ZnO nanorods. This was indicated by the strong bathochromic shift of thesoret peak of porphyrin and quenching of its fluorescence however, at this ratio chargetransfer complex is not detectable. The complex formation requires both the donors andacceptors to be enough close to each other to undergo Van der Waal’s type interactionwhich is achievable by raising the stoichiometric ratio to 1:3 and beyond. Weak CTabsorption (700-800 nm) and emission bands (800 nm) characterizing supramolecularcomplexation, were noticed only in polar solvent acetonitrile. When applied as acomponent of the active layer in bulk heterojunction hybrid solar cells, the dyefunctionalized ZnO nanoprods raised the efficiency of the solar cells at lowconcentrations but addition of fullerene had an inverse effect. This was investigated to bedue to the morphological defects induced by the clusterization of nanorods.

In situ Raman spectroscopy was used to explore etching of carbon nanotubes as well as their growth from C60. The thesis is in three parts: (1) C60 seed particles were partially oxidized in air and were used to grow carbon nanotubes and other nanocarbon structures. Seed oxidization was characterized by monitoring the evolution of the Raman Ag(2) peak and the D band, and oxidation temperature was found to be critical to nanotube growth. (2) To further explore oxidation, carbon nanotubes were thermally oxidized in air at different temperatures, while the evolution of different Raman bands was tracked. Etching dynamics and band intensity evolution were tracked in situ. Notably, metallic species were found to etch much more rapidly than semiconducting species of similar diameter. (3) To confirm and expand on this, a novel, simultaneous two-laser Raman spectroscopy setup was used to track the thermal oxidation of carbon nanotubes in O2 and CO2 gases at different temperatures. Metallic species were resonant with one laser line, while semiconducting species were resonant with the other, so changes to sample metallicity could be tracked unambiguously in two separate spectra. Again, metals were found to etch more rapidly. In situ Raman spectroscopy can track the evolution of nanotubes in real time and provide insight into processing. In general, detailed process monitoring like this can help in the development of selective synthesis and processing.

Orientador: Fernando Alvarez / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-04T02:14:03Z (GMT). No. of bitstreams: 1 DroppaJunior_Roosevelt_D.pdf: 3953569 bytes, checksum: 5a007bee5cd4c884e234f80f9cc54757 (MD5) Previous issue date: 2004 / Resumo: A proposta deste trabalho é sintetizar e caracterizar química e estruturalmente nanotubos e fulerenos contendo nitrogênio. A síntese tanto das amostras de nanotubos como das amostras de fulerenos foi feita pela técnica de arco elétrico em atmosferas contendo nitrogênio gasoso. A análise das amostras de nanotubos nitrogenados por microscopia eletrônica mostra que a concentração de nitrogênio gasoso durante a síntese influencia na incorporação de átomos desse elemento por estruturas de carbono que dão origem aos nanotubos. Estes, quando contêm átomos de nitrogênio na sua composição, têm forma de bambu, diferentemente dos nanotubos gerados na ausência de nitrogênio. Análises por Espectroscopia de Elétrons Fotoemitidos (XPS) indicam que amostras de nanotubos assim produzidas de fato contêm nitrogênio e que parte dos átomos desse elemento estão ligados substitucionalmente em redes grafíticas. Dados de Espectroscopia de Elétrons Inelasticamente Espalhados (EELS) mostram que os átomos de nitrogênio se concentram nas paredes dos nanotubos com forma de bambu e simulações computacionais mostram o papel do nitrogênio na formação dessas estruturas. Amostras de nanotubos nitrogenados também foram submetidas a análise por espectroscopia Raman. Ao mesmo tempo em que essas amostras foram irradiadas com laser de potências variadas, espectros Raman foram coletados fornecendo informações a respeito da ordem estrutural e da pureza relativa das amostras. Tais informações complementam de modo coerente os dados de microscopia eletrônica. Ainda em relação aos nanotubos, foram realizadas medidas de eletroemissão em um sistema com geometria de capacitor plano. Verificou-se que os nanotubos nitrogenados são tão bons emissores quanto aqueles de parede única (não-nitrogenados). Observou-se ainda que o nitrogênio influencia o comportamento do fator de estrutura dos nanotubos, no entanto, a razão disso ainda não está muito clara. Relativamente aos fulerenos, foram obtidos dados de espectrometria de massas que indicam a presença de fulerenos nitrogenados, ou nitrofulerenos, nas amostras sintetizadas em presença de nitrogênio. Suas massas moleculares estão em torno de 523 u.m.a.. Cálculos teóricos [ 30 ] indicam que é possível a existência de tais moléculas (cuja massa prevista é de 522 u.m.a.), já que possuem calor de formação comparável ao dos fulerenos C60. Dados de XPS confirmam a presença de nitrogênio também nessas amostras. A coerência dos resultados experimentais e teóricos sugere fortemente que estamos na direção certa na busca dos heterofulerenos / Abstract: This thesis work aims to synthesize and to characterize structural and chemically nanotubes and fullerenes containing nitrogen. Both nanotubes and fullerenes syntheses were performed using an arc-discharge system filled with gaseous mixtures of He e N2. Electron microscopy samples analysis shows that N2 concentration inside the arc-discharge chamber influences the nitrogen incorporation into the carbon structures that give rise to the nanotubes. Those ones containing N atoms in their composition have a bamboo-like aspect in contrast to those generated in absence of nitrogen gas. XPS analyses indicate that nanotube samples generated in N rich atmospheres in fact have nitrogen in their composition and part of N atoms are substitutionally bonded in graphitic sites. EELS data show that N atoms are preferentially bonded in the bamboo-like nanotubes and computational simulations show the role these N atoms play in the formation of these structures. Nitrogenated nanotube samples were also analyzed by Raman spectroscopy. As the samples were irradiated by the Raman laser at different powers, Raman spectra were collected. Such spectra gave information about the structural order and relative purity of the samples. This information coherently complements the electron microscopy data. It was also performed field emission measurements of the nitrogenated nanotube samples. It was verified that such structures are as good emitters as single wall nanotubes (non-nitrogenated ones). It was also observed that nitrogen influences the behavior of the nanotubes structure factor, however, it was not clear yet why this is so. Finally, it was obtained mass spectrometry data of the fullerenes samples. These data indicate the presence of nitrogenated fullerenes or "nitrofullerenes" in the samples generated in nitrogen rich atmosphere. Their molecular masses are around 523 a.m.u.. Theoretical calculations [ 30] also indicate that the existence of such molecules (whose molecular mass is 522 a.m.u.) is possible, since their heat of formation is comparable to that of the C 60fullerenes. XPS data also confirm that there is nitrogen in these samples. The coherence of the experimental as well as the theoretical results strongly suggests that our quest for the heterofullerenes is in the right direction / Doutorado / Física / Doutor em Ciências

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Conjugated polymer architecture and morphology are two of the key factors that determine corresponding opto-electronic device performance. It is well-known that conjugated polymers display a variety of conformations and exhibit aggregation in their materials and even for individual polymer chains. The intrinsic structural heterogeneity of conjugated polymers strongly complicates the active layer morphology and phase separation, which are crucial for photoinduced charge generation and transport in polymer based bulk heterojunction-organic photovoltaics device (BHJ-OPVs). Aiming to probe the molecular level correlations between conjugated polymer architecture, morphology and optoelectronic properties, single molecule spectroscopy (SMS) and single particle spectroscopy (SPS) were employed. The molecular level folding properties of conjugated polymers were studied and correlated to the chemical architecture and rigidness of the polymer backbones by means of SMS and single molecule polarization anisotropy imaging. First, a block copolymer consisting of poly(3-hexylthiophene) (P3HT) and (60)fullerene (C₆₀) was investigated due to its potential for forming active layers in OPV devices that exhibit long-term phase stability and efficient exciton dissociation into free charge carriers. It was demonstrated that the grafting of the C₆₀-containing block does not significantly affect the conformation of the backbone of the P3HT block. Next, a series of thiophene based polymers showing different macroscale crystallization behavior were investigated. The rigidness of the conjugated polymer backbones was found to be correlated with the chemical architecture of the molecules. However, even the polymers that show no folding in their respective crystals and are thus expected to be the most rigid, still exhibit folding at the single molecule level. From this work it is clear that besides chemical architecture, intermolecular interactions in the crystal structure also need to be considered. For conjugated polymer materials, in this dissertation specifically the blends of conjugated polymers with fullerenes as found in the active layer of OPVs, the investigation of the molecular level correlations between conjugated polymer architecture, morphology and optoelectronic properties can be prohibitively complex due to the presence of a large number of molecules. Furthermore, in the research presented herein, as well as in the literature, it has been clearly shown that the polymer molecules themselves exhibit severe heterogeneity in their properties (chain morphology, aggregation, optical and electronic properties). Therefore, in order to simplify the structure-property investigations concerning nanodomains in BHJ-OPVs, we developed P3HT/PC₆₀BM (PC₆₀BM: (6,6)-phenyl-C₆₁-butyric acid methyl ester) composite nanoparticles (NPs). The size of the nanoparticles corresponds with a few polymer and fullerene domains when considering a similarly sized volume in the active layer of OPVs. Single particle spectroscopy combined with this unique nanoparticle material system reveals variations in molecular conformation and aggregation of the conjugated polymer chains upon doping with different weight percentages of fullerene. These newly developed NPs were embedded in a hole-injection device to study the exciton-hole polaron interactions and the charge transfer processes at the interface between a hole-transporting layer and the NPs. Pronounced charge trapping was observed for donor-acceptor blend NPs due to the large amount of photogenerated free charge carriers. Besides fundamental studies on morphology-property relations for thiophene based conjugated polymers, fabrication of BHJ-OPVs based on P3HT and PC₆₀BM was also completed. Low band gap polymer PTB-7 (poly((4,8-bis((2-ethylhexyl)oxy)benzo (1,2-b:4,5-b')dithiophene-2,6-diyl)(3-fluoro-2-((2-ethylhexyl)carbonyl)thieno(3,4-b) thiophenediyl))) and a near-infrared (NIR) small dye molecule were incorporated into active layers of these P3HT/PC₆₀BM BHJ-OPVs to expand the photoresponse of the devices. The effects of doping the P3HT/PC₆₀BM BHJ-OPVs with PTB-7 and NIR dye on the device performance and film morphology were investigated. The doping of PTB-7 can efficiently extend the photoresponse of the resultant devices into the NIR regime and improve the device performance with respect to the reference (undoped) devices, demonstrating an elegant and pragmatic approach in improving light-harvesting efficiency in BHJ-OPVs.

Carbon nanomaterials, such as carbon nanotubes and graphene, have attracted significant interest over the past several years due to their outstanding and unusual combination of physical properties. These properties can be modified in a controllable way by chemical functionalization in order to enable specific technological applications. One example is hydrogenation, achieved by the exposure of these materials to a source of atomic hydrogen. This process has been considered for hydrogen storage purposes and for the control of the band gap of these materials for applications in carbon-based electronics. Hydrogen atoms are chemisorbed onto the surface of these materials, introducing sp3-hybridized C–C bonds in a structure originally formed by delocalized sp2 C–C bonding. This bonding transition causes severe structural and morphological changes to the graphene layers/walls. Also, it has been demonstrated that the exposure of multi-walled carbon nanotubes (MWCNTs) to a H2 plasma leads to the formation of diamond nanocrystals embedded within the nanotube walls. This thesis presents a computational analysis of the effects of hydrogen chemisorption on the structure and morphology of graphene and single-walled carbon nanotubes (SWCNTs), as well as of the different nanostructures that can be generated upon formation of inter-shell and inter-layer sp3 C–C bonds in MWCNTs and few-layer graphene (FLG), respectively. The analysis is based on a synergistic combination of atomic-scale modeling tools, including first-principles density functional theory (DFT) calculations and classical molecular-dynamics (MD) and Monte Carlo (MC) simulations. The results demonstrate that SWCNTs and graphene swell upon hydrogenation and provide interpretations to experiments reported in the literature; this swelling depends strongly on the hydrogen surface coverage. A MC/MD-based compositional relaxation procedure generates configurations whose arrangements of H atoms are in excellent agreement with experimental observations. Detailed structural analysis of the hydrogenated surfaces is carried out, providing information which cannot be extracted easily from conventional experimental techniques. The findings of the analysis are used to explain the limitations on the maximum H storage capacity of SWCNT bundles upon their exposure to an atomic H flux. Furthermore, it is demonstrated that the structures resulting from formation of inter-shell or inter-layer C-C bonds are stable and provide seeds for the nucleation of crystalline carbon phases embedded into the shells and layers of the MWCNT and FLG structures, respectively. The key parameter that determines the type and size of the generated nanocrystals is the chiral-angle difference between adjacent layers/walls in the original structure. A novel type of carbon structure, consisting of fullerene-like caged configurations embedded within adjacent graphene layers, has been discovered for the case where the graphene layers are rotated with respect to each other; interestingly, one class of these structures retains the unique and desired electronic properties of single-layer graphene.

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Yes / Thermoplastic polyurethane (TPU)/multi-walled carbon nanotubes (CNT) nanocomposites were prepared by twin-screw extrusion and micro injection molding. The electrical conductivity of micro injection molded polymer nanocomposites exhibits a low value and uneven distribution in the micromolded samples. Real-time tracing of electrical conductivity was conducted to investigate the post thermal treatment on the electrical conductivity of microinjection molded composites. The results show that postmolding thermal treatment leads to a significant increase in the electrical conductivity by over three orders of magnitude for 5 wt % CNT-filled TPU composites. In-situ Transmission electron microscopy confirms the conductive CNT network does not change at the micron/sub-micron scale during thermal treatment. TEM image analysis by a statistical method was used to determine the spatial distribution of CNT in the sample and showed that the average distance between adjacent CNT reduced slightly at the nanometer scale after postmolding thermal treatment. A new conductive mechanism is proposed to explain the enhancement of electrical conductivity after thermal treatment, i.e. micro-contact reconstruction of adjacent CNT in the polymer matrix through annealing-induced relaxation of interfacial residual stress and strain. Raman spectra and small angle X-ray scattering curve of annealed samples provide supporting evidence for the proposed new conductive mechanism. The electron tunneling model was used to understand the effect of inter-particle distance on the conductivity of polymer composites. / Chinese Ministry of Education. Grant Number: 313036; National Natural Science Foundation of China. Grant Number: 51433006

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