O objetivo do presente trabalho foi avaliar a resposta tecidual em 48 pré- molares (96 raízes) de cães, após obturação dos canais radiculares com diferentes materiais. Os dentes foram submetidos à biopulpectomia, ao preparo biomecânico e divididos em oito grupos, onde os canais radiculares foram obturados com os seguintes materiais: Grupos I e V pasta Calen® espessada com óxido de zinco; Grupos II e VI cimento EndoREZ; Grupos III e VII cimento Sealapex®, e Grupos IV e VIII cimento de óxido de zinco e eugenol. Decorridos os períodos de 30 e 90 dias, os animais foram mortos, as peças removidas e submetidas ao processamento histológico. A avaliação histopatológica foi baseada nos seguintes parâmetros: intensidade do infiltrado inflamatório, espessura do ligamento periodontal, reabsorção do tecido ósseo, limte de obturação e presença ou ausência de selamento apical. Os resultados foram submetidos à análise estatística pelo teste não paramétrico de Kruskal-Wallis, com nível de significância de 5%. Com base nos resultados obtidos e considerando as condições específicas deste trabalho, pôde-se concluir que a pasta Calen® espessada com óxido de zinco foi o material que apresentou a melhor resposta tecidual, seguida pelos cimentos Sealapex® e óxido de zinco e eugenol. O cimento EndoREZ apresentou resposta tecidual desfavorável . / The objective of the present work was evaluate the tissue response in 48 premolars( 96 roots), of dogs teeth, after pulpectomy, with different roots canals filling materials. The teeth were submitted to the biomechanical preparation and divided in eigth groups, where the canals were filled with following materials: Groups I and V - Calen® paste thickened with zinc oxide; Groups II and VI - EndoREZ sealer; Groups III and VII - Sealapex® sealer; and Groups IV and VIII Zinc oxide and eugenol cement. After periods of 30 and 90 days, the animals were killed, the pieces reduced and submitted to the histological processing. The histopathological evaluation was based on the following parameters: intensity of the inflammatory infiltrate, thickness of the periodontal ligament, bone resorption,filling limit and presence or absence of sealed apical. The results were submitted to the statistical analysis by the non parametric test of Kruskal-Wallis, with significance level was 5%. Based on the results obtained in histopathological analysis and methodologies employed in the present work, it may be conclued that: Calen® paste thickened with zinc oxide was the material that showed the better tissue response, following by Sealapex® sealer and zinc oxide and eugenol cement. EndoREZ sealer showed tissue response unfavorable.

Orientador: Ítalo Odone Mazali / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T20:07:38Z (GMT). No. of bitstreams: 1 Oliveira_CristineSantosde_M.pdf: 3527061 bytes, checksum: 7dfe90cc79337811bc7955e8a1531586 (MD5) Previous issue date: 2013 / Resumo: O trabalho consistiu na síntese de sistemas nanoestruturados de ZnO contendo Eu em sílica mesoporosa, o vidro poroso Vycor (PVG), utilizando o método de ciclos de impregnação-decomposição (CIDs). Sistemas de nanopartículas puras de ZnO, na forma PVG/10ZnO mostraram que o ZnO apresentou-se predominantemente na forma de sítios de ZnO monodispersos com absorção em 245-250 nm e na forma de nanopartículas, com tamanho médio em torno de 4,5 nm, para as quais inicialmente não se observou uma absorção característica. Através de espectroscopia de luminescência observou-se transferência de energia do ZnO monodisperso para a matriz, porém nenhuma emissão no visível característica de defeitos. Para o sistema PVG/10Eu observou-se transições f-f características nos espectros de emissão e excitação, e a transferência de carga O¿¿Eu. Os sistemas seguintes sintetizados na forma PVG/ZnO@ZnO/M@ZnO, com M = Eu, Al, Sr, Pr e Yb visaram o estudo do sistema principal PVG/ZnO@ZnO/Eu@ZnO, o qual apresentou emissões do Eu relativamente mais intensas do que no sistema PVG/10Eu além de apresentar o favorecimento do crescimento do ZnO sob a forma de nanopartículas, crescendo sobre os aglomerados de dopante. Nessas condições, surge a banda proibida do ZnO em torno de 360 nm, cuja borda é deslocada para menores energias com o número de CIDs, em acordo com uma equação da literatura, indicando um regime de confinamento quântico. Esta banda é observada na luminescência e também transfere energia para a matriz, ainda não sendo observadas emissões de defeitos do ZnO. Estudos com Sr e Al não confirmaram a formação de defeito do tipo Zni decorrente da inserção do íon Eu na rede do óxido. Os espectros de excitação para os sistemas de ZnO contendo Eu não foram conclusivos quanto à transferência de energia devido à presença de bandas do Eu, e num sistema similar substituindo-se por Yb não foi observada esta transferência. Medidas de tempo de vida mostraram um aumento da estabilidade do Eu no sistema com a presença prévia do ZnO, e também sob seu recobrimento. Através das emissões excitônicas do ZnO observou-se o efeito de confinamento quântico também na luminescência, o qual se deu de forma similar ao observado para a análise por absorção no UV-Vis / Abstract: The work consisted in the synthesis of nanostructured systems of ZnO containing Eu loaded in a mesoporous silica, the porous Vycor glass (PVG), using the impregnation-decomposition cycles method (IDCs). Pure ZnO nanoparticles systems synthesized in the form PVG/10ZnO have shown that ZnO presents itself predominantly as monodisperse ZnO sites with absorption at 245-250 nm, and nanoparticles, with mean size around 4,5 nm, for which initially no characteristic absorption had been observed. Through luminescence spectroscopy an energy transfer from monodisperse ZnO to the matrix was observed, but no defect-related emissions. For the PVG/10Eu system Eu characteristic f-f transitions were observed in both emission and excitation spectra, as well as the O¿¿Eu charge transfer. The following systems synthesized in a PVG/ZnO@ZnO/M@ZnO pattern, with M = Eu, Al, Sr, Pr e Yb sought the study of the main system PVG/ZnO@ZnO/Eu@ZnO, which presented Eu emissions relatively more intense than the PVG/10Eu system, also showing favoring growth of ZnO under the form of nanoparticles, which now grow over dopant clusters. Under such condition the ZnO band gap is now observed in UV-Vis absorption analysis, with peaks around 360 nm, whose edge is displaced towards lower energies with increasing number of IDCs, also in agreement with a theoretical equation from the literature, pointing to a condition of quantum confinement. This band is observed in luminescence, and also transfers energy to the matrix, and yet no defect-related emissions are observed for ZnO. Studies with Sr and Al did not confirm the formation of a Zni defect due to the insertion of Eu ions into the oxidefs structure. Excitation spectra for Eu-containing ZnO systems were not conclusive as to the existence of an energy transfer due to the presence of Eu bands in the same range, and in the similar system exchanging Eu3+ for Yb3+ such transfer was not observed. Lifetime measurements have shown an increase in Eu stability within the system with ZnO presence previous to its insertion, or after its coating layer(s). Quantum confinement effect was also observed for the ZnO excitonic emissions in luminescence, showing a similar behavior to that obtained thru UV-Vis absorption analysis / Mestrado / Quimica Inorganica / Mestre em Química

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In this thesis work, novel planar nanodiodes (PNDs) using an amorphous indium-gallium-zinc oxide (IGZO) film as the active layer have been electrically characterised for the first time. Simulation techniques and experimental methods, such as e-beam lithography (EBL) and nanoimprint lithography (NIL), have been explored for these devices. In addition, a novel approach was realized that produced self-aligned contacts for the nanostructured devices. A preliminary parameter space for experimentation of the PNDs was ascertained by simulating the devices using a technology computer aided design (TCAD) simulator. In this study Silvaco’s ATLAS default IGZO material system was adopted. These simulations showed device performance to be heavily dependent on the carrier concentration of the film, owing to the high leakage current during the off-state of device operation. Furthermore, device geometry had a significant influence on the device’s electrical response. Channel width, length and trench width were all examined. Experimental characterisation of PNDs were attained by fabricating devices using EBL. These devices are the first to exhbit diode-like DC electrical response from an IGZO-based PND. Full current rectification was obtained with a rectification ratio of 10^4 for devices with a long, narrow channel with a width of 50nm and a length of 4μm. This particular device geometry had a turn-on voltage, Von, of 2.2V and did not breakdown within the −10V bias range tested. An output drive current of 0.1μA at 10V was obtained by the single PND device. It was also demonstrated that by increasing the channel width, Von could be reduced; however, rectification also diminished. It is reasoned that the exposed IGZO surface was subject to contamination from the ambient which changed the device’s electrical response after 17 days. An ultraviolet NIL (UV-NIL) technique was developed to produce the PNDs. This fabrication method offers a suitable route towards high-volume manufacture of these nanodevices, which is critical for them to be incorporated into a low-cost RF energy harvester. A novel NIL process was established in which the contact pads were self-aligned to within ~ 200nm of the channel by patterning both metal and semiconductor layers with a single imprint. DC electrical characterisation of the imprinted PNDs produced high rectifications ratios at a lower Von. The greater number of devices tested allowed a coarse parameter space for channel width and length to determined. PNDs with a channel aspect ratio (length divided by width) of more than 20 exhibited the greatest DC rectification of 10^4. An alumina capping layer was found to eliminate hysteresis in the electrical response; however, the greater permittivity value had no noticeable effect on device performance. Finally, a large-signal RF analysis is carried out on a device which suggest no deterioration in device perfromance up to at least 1GHz.

Les cellules solaires en couches minces à base de Cu(In,Ga)(S,Se)2 (CIGS) représentent une technologie à fort potentiel et aux performances photovoltaïques élevées. La couche finale de l'empilement, appelée couche fenêtre, est principalement composée d'une bi-couche d'oxyde de zinc (ZnO) non dopé et dopé de type n - généralement à l'aluminium - et déposée par un procédé sous vide : la pulvérisation cathodique. Cependant, cette technique demande des investissements importants et un intérêt croissant s'est porté sur le développement de techniques alternatives atmosphériques en vue d'une réduction des coûts. L'objectif de ce travail a été d'étudier la réalisation d'une couche fenêtre fonctionnelle de ZnO par un procédé d'électrodépôt photo-assisté en milieu aqueux sur des substrats de grandes dimensions. Pour y parvenir, différentes études ont été réalisées afin de déterminer les propriétés du ZnO électrodéposé et optimiser le procédé de dépôt. Dans un premier temps, l'influence de la composition de trois solutions électrolytiques sur les propriétés et le dopage du ZnO a été étudiée : le milieu chlorure (Cl-), le milieu perchlorate (ClO4-) et un milieu mixte à base de perchlorate et d’acide borique (H3BO3). Dans un second temps, la synthèse électrochimique du ZnO comme couche fenêtre a été réalisée sur des substrats de CIGS/CdS. Son étude a permis de montrer que la réalisation in situ d'une couche d'accroche facilite la croissance d'une couche finale dense et compacte. Cette méthode de synthèse en deux étapes a conduit à l'obtention de performances photovoltaïques élevées sur grandes surfaces avec des rendements allant jusqu'à 14,3 % pour une cellule solaire entièrement réalisée par des procédés atmosphériques. / Cu(In,Ga)(S,Se)2 (CIGS) thin films based solar cells are a promising technology for high efficiency energy conversion. A window layer completes the stack of the cell. It is commonly constituted by an intrinsic and aluminum doped bi-layer of zinc oxide (ZnO) deposited by magnetron sputtering, an expensive vacuum process. Alternative processes, using low cost and atmospheric techniques, have been developed in order to reduce the costs. The aim of this work was to achieve a functional window layer of ZnO by a photo-assisted electrodeposition process on large scale substrates of CIGS/CdS in aqueous medium and replace the sputtered one. For this purpose, several studies have been carried out in order to determine the optoelectronic properties such as doping level and mobilities of the electrodeposited ZnO and optimize the deposition process. Firstly, the effect of three different electrolytes on the zinc oxide properties and doping has been studied on metallic substrate: chloride medium (Cl-), perchlorate medium (ClO4-) and a mixed medium of perchlorate with boric acid (H3BO3). Then, electrochemical synthesis of zinc oxide as window layer has been performed on CIGS/ CdS substrates. This study allowed to establish the need to synthesize an in situ seed layer which promotes the growth and the compactness of the final layer of zinc oxide. This two-step method has led to the achievement of high photovoltaic performances on large scale with promising efficiencies up to 14.3 % for a solar cell made entirely by atmospheric processes.

>Magister Scientiae - MSc / In a quest for low operational and maintenance cost solar cell devices, organic photovoltaics remain a potential source of energy worthy to be explored. In order to generate cost- effective electricity from solar energy, either the efficiency of the solar cells must be improved or alternatively the manufacturing cost must be lowered. The power conversion efficiency (PCE) of organic photovoltaics is influenced by the choice of electron acceptor material, the structure of the polymer, the morphology of the film, the interfaces between the layers and the ratio between the electron acceptor material and the polymer. Nevertheless, efficiency is still limited compared to conventional silicon based PV cells due to low mobility of charge carriers with a short exciton diffusion length in the active layer. Currently, hybrid solar cells have been considered as one of the most promising concepts to address the limited efficiency of organic solar cells. Therefore in this thesis ZnO nanoparticles were synthesized using hydrothermal assisted method. These nanoparticles were incorporated in the poly (3-hexylthiophene) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM), and used as additional acceptors of electrons released from the polymer donor material, with the anticipation to increase the electron mobility, and ultimately the PCE. The thermo-gravimetric analyses revealed improved thermal stability of P3HT upon incorporating ZnO in the polymer matrix. X-ray diffraction analyses revealed that the diffraction peaks shift to higher angles when incorporating the ZnO in the P3HT:PCBM surface and this is consistent with the Raman observation. The photovoltaic properties demonstrated that the addition of ZnO nanoparticles in P3HT:PCBM bulk-heterojunction increases PCE from a baseline of ∼1.0 % in the P3HT:PCBM system to 1.7% in the P3HT:PCBM:ZnO ternary system. The enhanced PCE was due to improved absorption as compared to its counterparts. Upon increasing the addition of ZnO nanoparticles in the P3HT:PCBM matrix, the PCE decreases, due to a large phase separation between the polymer, PCBM and ZnO induced by ZnO agglomerations which resulted in increased surface roughness of the active layer. These findings signify that incorporation of ZnO nanostructures in the P3HT:PCBM polymer matrix facilitates the electron transport in the photoactive layer which results to improved efficiency.

Conception de nanomatériaux à base d'oxyde par ALD : de la détection aux membranes / In this context, the aim of this PhD work is the synthesis of different nanostructured materials based on ALD oxide thin film (Al2O3, ZnO and Al2O3/ZnO nanolaminates) deposited on different types of substrates such as silicon substrate, glass, nanofibers, multipores and monopores membranes, PET and gold coated nickel dogbones. ALD deposition was performed on those substrates with changing the film thickness (number of cycles), the deposition temperature, and the film composition (doping, multilayers etc.). After the ALD deposition chemical, structural, optical, electrical and mechanical characterization were performed on the ALD deposited layer in order to study the influence of the deposition parameters on the thin film properties. The deposited and characterized ALD films were investigated on different fields:• Optical properties for solar cell applications (Chapter 2) • UV detection (Chapter 3)• Protective coating and gas barrier (chapter 4)• Ionic transport, water desalination, Mass spectrometry, DNA sequencing and Gas purification (chapter 5)The atomic layer deposition technique combined with nanostructured templates show several advantages on several application fields that will be reported on this thesis. The structural and properties evolution of the ALD thin film with the deposition parameter evolution leaded to a doped ZnO layer and Al2O3/ZnO multilayer with tunable optical, electrical and mechanical properties that can be interesting for different applications such as solar cell and UV detection. The conformal coating on high aspect ratio template with the angstrom range thickness control offered by the atomic layer deposition technique meted our target on nanopores diameter tuning for different applications on the nanometeric range such as gas purification. Moreover the compatibility of the deposited materials with some biological function leaded to a combination between nanostructure materials and biological function that shows promising results for different applications such as ionic transport, water desalination, mass spectrometry and DNA sequencing.

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Energy harvesting using piezoelectric nanomaterials provides an opportunity for advancement towards self-powered systems. Self-powered systems are a new emerging technology, which allows the use of a system or a device that perform a function without the need for external power source like for example, a battery or any other type of source. This technology can for example use harvested energy from sources around us such as ambient mechanical vibrations, noise, and human movement, etc. and convert it to electric energy using the piezoelectric effect. For nanoscale devices, the size of traditional batteries is not suitable and will lead to loss of the concept of “nano”. This is due to the large size and the relatively large magnitude of the delivered power from traditional sources. The development of a nanogenerator (NG) to convert energy from the environment into electric energy would facilitate the development of some self-powered systems relying on nano- devices. The main objective of this thesis is to fabricate a piezoelectric Zinc Oxide (ZnO) NGs for low frequency (˂ 100 Hz) energy harvesting applications. For that, different types of NGs based on ZnO nanostructures have been carefully developed, and studied for testing under different kinds of low frequency mechanical deformations. Well aligned ZnO nanowires (NWs) possessing high piezoelectric coefficient were synthesized on flexible substrates using the low temperature hydrothermal route. These ZnO NWs were then used in different configurations to demonstrate different low frequency energy harvesting devices. Using piezoelectric ZnO NWs, we started with the fabrication of sandwiched NG for hand writing enabled energy harvesting device based on a thin silver layer coated paper substrate. Such device configurations can be used for the development of electronic programmable smart paper. Further, we developed this NG to work as a triggered sensor for wireless system using foot-step pressure. These studies demonstrate the feasibility of using ZnO NWs piezoelectric NG as a low-frequency self-powered sensor, with potential applications in wireless sensor networks. After that, we investigated and fabricated a sensor on PEDOT: PSS plastic substrate either by one side growth technique or by using double sided growth. For the first growth technique, the fabricated NG has been used as a sensor for acceleration system; while the fabricated NG by the second technique has worked as anisotropic directional sensor. This fabricated configurations showed stability for sensing and can be used in surveillance, security, and auto-mobil applications. In addition to that, we investigated the fabrication of a sandwiched NG on plastic substrates. Finally, we demonstrated that doping ZnO NWs with extrinsic element (such as Ag) will lead to the reduction of the piezoelectric effect due to the loss of crystal symmetry. A brief summary into future opportunities and challenges are also presented in the last chapter of this thesis.

Biomimicry means literally ‘imitation of life’ and is providing sustainable solutions for challenges that are occurring in the human lives. To date, the biomimic research reports that wettability in nature, e.g. self-cleaning effect on a lotus leaf and a striking water strider’s leg, is related to the cooperation between the chemical composition and the topography of the surface. Moreover, this study is developing a textile substrate that goes one step further than biomimic, called ‘Biomimicking beyond nature’. The focus of this study is establishing a 100% polyamide-66 textile substrate that is switchable and reversible between hydrophobic and hydrophilic states under stimulation of UV. In this study the behaviour of a polyamide-66 textile substrate, coated with three individual photoresponsive materials (azobenzene, titanium dioxide and zinc oxide), was investigated, under stimulation of 24 hours UV and one-week of storage period in dark conditions. Silicone was added to enhance the hydrophobicity of a titanium dioxide coated substrate. A switchability effect was detected, but no reversibility effect could be observed. The only organic photoresponsive material, azobenzene, obtained no significant results to conclude that an alternation between hydrophobic and hydrophilic was even present after 24 hours of UV radiation. However, azobenzene obtained more promising results on a 100% polyester textile substrate. Even though, the H0 cannot be rejected for all three individual photoresponsive materials, the zinc oxide coated polyamide-66 substrate, did exhibit the strongest results in switchability and reversibility. Based on the characterization measurements, a switchability effect from a hydrophobic surface (ca. 120°) to a hydrophilic surface (0°) can be observed after 24 hours of UV radiation. Moreover, a reversibility effect was only reported on a zinc oxide coated polyamide-66 substrate. The substrate partially reversed back to its original state with ca. 50%. Fabricating intelligent substrates could enhance many challenges confiscating today’s life. For instance, the development of smarts membranes or microfluidic switches, that alternate their wettability upon light radiation, could improve the exhausting manual labour in watering the harvest good in the agricultural industry. Therefore, it is of great importance that further research will be conducted upon the photoresponsive material, zinc oxide, in order to achieve more stable results. This study can be added to the relatively small area of knowledge around switchability phenomenon on textile substrates and can even been reported as one of the first attempts on developing a textile substrate with switchable and reversible characteristics, by use of a facile and possibly industrialized method.