>Magister Scientiae - MSc / TiO2 nanoparticle films are important electron transport layers (ETLs) in photovoltaics such as dye-sensitised, perovskite and polymer hetero-junction solar cells. These films, however, have significant electron trap-sites as a result of the large density of oxygen vacancies present in nanosized TiO2. These trap-sites cause electron-hole recombination and ultimately lower photon-tocurrent conversion efficiency of the underlying cell during operation. Doping the TiO2 lattice with low atomic number elements such as nitrogen is a proven method to overcoming the charge transport inefficiency of TiO2 ETLs; another is the use of one-dimensional (1D) nanowires (NWs), instead of nanoparticles. Modification of TiO2 with non-metals leads to optical bandgap narrowing, improvement in electron conductivity and increased electron lifetime in the ETL layer. However, a lot of scope exists in understanding and fully quantifying the relationship between optical property, for example light transmission and bandgap modification, versus the doping concentration and type. Most doping approaches are in-situ and involve the addition of a dopant precursor (usually a salt) during the synthesis of TiO2 nanostructures – this invariably leads to uncontrolled doping levels, anion contamination and poor-quality materials – a need thus exists to develop simple, controllable doping approaches. One such approach, which forms the basis of this study, is ex-situ doping by means of plasma generated species in a controlled environment. This field of study is fairly novel and not widely studied, requiring more research to understand the doping mechanisms and influence on the optical and electronic properties of the underlying nanomaterials. In particular, controlled doping of TiO2 with nitrogen using radio-frequency generated (RF) plasma requires vigorous experimentation and characterisation. Inaccuracy of the deposition parameters during exposure remains a common drawback for this approach in addition to a lack of understanding of the surface interaction between the N2 species and specimen during irradiation.

This thesis is dealing with nanowires of zinc oxide and of cesium lead bromide. Main goal was a preparation of ZnO nanowires using MBE. This goal was partially achieved and growth of needle-like structures was observed. Another goal was characterization of already prepared ZnO nanowires. We successfully determined polarity of their surfaces, examined the influence of lattice defects and assessed the result of their doping. Side goal of this work was characterization of nanostructures of cesium lead bromide. However, preparation of cesium lead bromide nanowires remains an open issue.

Recent progress in the development of artificial skin concepts is a result of the increased demand for providing environment perception such as touch and flow sensing to robots, prosthetics and surgical tools. Tactile sensors are the essential components of artificial skins and attracted considerable attention that led to the development of different technologies for mimicking the complex sense of touch in humans. This dissertation work is devoted to the development of a bioinspired tactile sensing technology that imitates the extremely sensitive hair-like cilia receptors found in nature. The artificial cilia are fabricated from permanent magnetic, biocompatible and highly elastic nanocomposite material, and integrated on a giant magneto-impedance magnetic sensor to measure the stray field. A force that bends the cilia changes the stray field and is therefore detected with the magnetic sensor, providing high performance in terms of sensitivity, power consumption and versatility. The nanocomposite is made of Fe nanowires (NWs) incorporated into polydimethylsiloxane (PDMS). Fe NWs have a high remanent magnetization, due the shape anisotropy; thus, they are acting as permanent nano-magnets. This allows remote device operation and avoids the need for a magnetic field to magnetize the NWs, benefiting miniaturization and the possible range of applications. The magnetic properties of the nanocomposite can be easily tuned by modifying the NWs concentration or by aligning the NWs to define a magnetic anisotropy. Tactile sensors are realized on flexible and rigid substrates that can detect flow, vertical and shear forces statically and dynamically, with a high resolution and wide operating range. The advantage to operate the sensors in liquids and air has been utilized to measure flows in different fluids in a microfluidic channel. Various dynamic studies were conducted with the tactile sensor demonstrating the detection of moving objects or the texture of objects. Overall, the results confirm the possibility to easily control the sensors’ performance with the cilia arrangement and dimensions. The cost effective mold-based microfabrication process and magnetic operation enable a high degree of integration, which together with the extremely low power consumption make the artificial cilia sensor reported in this dissertation an attractive solution for many applications.

Les matériaux III-nitrures sont des excellents semi-conducteurs qui présentent plusieurs propriétés intéressantes pour les applications photovoltaïques et piézoélectriques. Au même temps, la croissance epitaxiale de ces matériaux sous forme de nanofil (NF) est de tant en plus intéressant, car les NFs nitrures binaires et heterostructurés, ont une qualité cristalline supérieure comparés aux homologues 2D et massifs. Dans ces contextes, ce travail est axé sur la croissance par MBE assistée par plasma (PA-MBE) de NFs InGaN/GaN et leur caractérisation. Trois sujets principaux ont été abordés: l'étude de la croissance d’heterostructures InGaN axiales par PA-MBE, leur caractérisation optique, et l'étude de la croissance sélective de NFs GaN sur graphène transféré. Ces études m’ont permis d’obtenir un control rational sur le mode de croissance d’heterostructures InGaN dans une large gamme de teneurs d’In (jusqu'à ~ 40%) et morphologies, de étudier leur structure de bande axiale, utile pour la conception optimale de la structure p-i-n photovoltaïque, et de démontrer pour le première fois dans la littérature, que l’épitaxie sélective de NFs de GaN sur MCG lithographié est une route possible et très promettent pour améliorer leur homogénéité. Ainsi, des tests préliminaires ont montré que la capacité de piézo-conversion des NFs GaN peut être améliorée d'environ 35% lors de l'intégration d’une insertion InGaN riche en In dans leur volume.Tous ces résultats constituent un ’étape décisive dans le contrôle et la comprension des propriétés de ces nanostructures, et donnent des perspectives très encourageantes pour leur intégrations dans des nano-générateurs à haute efficacité. / III-nitride materials are excellent semiconductors presenting several interesting properties for photovoltaic and piezoelectric applications. At the same time, the epitaxial growth of these materials in the form of nanowires (NW) is even more interesting, because binary and heterostructured III-N NWs have a higher crystalline quality compared to the 2D and bulk counterparts. In these contexts, this work focuses on the plasma-assisted MBE (PA-MBE) growth of InGaN / GaN NWs and their characterization. Three main topics are addressed: the growth of axial InGaN heterostructures by PA-MBE, their optical characterization, and the study of the selective area growth (SAG) of GaN NWs on transferred graphene. These studies allowed me to obtain a rational control on the growth mode of InGaN heterostructures in a wide range of In contents (up to ~ 40%) and morphologies, to study their axial band edge profile, useful for the optimal design of the photovoltaic structure, and to demonstrate for the first time in the literature, that the SAG of GaN NWs on patterned mono-layer graphene is a possible and very promising strategy to improve their homogeneity. Also, preliminary tests have shown that the piezoelectric conversion capacity of GaN NWs can be improved by about 35% when integrating an In-rich InGaN insertion into their volume.All these results constitute a decisive step in the control and the comprehension of the properties of these nanostructures, and establish very encouraging perspectives for their integration in novel and efficient photovoltaic and piezoelectric nano-generators.

Orientador: Rafael Zadorosny / Resumo: Os materiais supercondutores são extremamente promissores a novas aplicações. Podemos encontrar diversos estudos sobre o supercondutor YBCO, porém o tratamento térmico para a formação da fase YBa2Cu3O7-δ (Y123) na forma de nanofibras ainda não é bem definido na literatura. Para estudar de forma sistemática essa questão, e definir uma boa rota de tratamento térmico, fios com diâmetros em torno de 300 nm foram obtidos por Solution Blow Spinning (SBS) a partir de uma solução contendo acetatos metálicos de ítrio, bário e cobre, polímero PVP (polivinilpirrolidona), ácidos acético e propiônico, e metanol. Os fios poliméricos foram submetidos a um tratamento térmico para obtenção da fase Y123. Este tratamento foi dividido em duas partes, a primeira variando a temperatura máxima de sinterização (850°C, 875°C, 900°C e 925°C) por 1 hora. E a segunda variando o tempo em que as fibras ficaram submetidas à temperatura de 925°C (10 min, 30 min, 1h, 3h e 6h). Para analisar a influência da temperatura e do tempo de sinterização foram utilizados Microscopia Eletrônica de Varredura (MEV), Difração de raios-X (DRX) e Magnetometria AC. As análises de DRX indicaram a presença do YBa2Cu3O7-δ em todas as amostras, porém, com fases secundárias. As medidas de susceptibilidade magnética revelaram influência da temperatura de sinterização na blindagem magnética da amostra, indicando que as amostras tratadas a 925°C/1h obtiveram a melhor resposta magnética. Sendo assim, o melhor tratamento térmico foi o... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Although the production of YBa2Cu3O7-δ (Y123) has been extensively reported in the literature, there is still a lack of information concerning the ideal heat-treatment routes applied to Y123 nanowires. Thus, wires with diameters around 300 nm were prepared by Solution Blow Spinning (SBS) from a solution containing yttrium, barium and copper metal acetates, PVP polymer (polyvinylpyrrolidone), acetic and propionic acids, and methanol. The resulting polymer wires were heat-treated to obtain the Y123 ceramic phase. Those treatments were divided into two parts: in the first one, which lasted 1 hour, the maximum sintering temperature was changed (850°C, 875°C, 900°C, and 925°C); in the second one, the time of the plateau at 925°C was altered (10 min, 30 min, 1h, 3h, and 6h). The structural characterization was carried out by Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), and AC Magnetometry. SEM images revealed that all samples yielded wires with an average diameter ranging from 241 nm to 376 nm. XRD analysis indicated the presence of the secondary phase BaCuO2 in all samples, as well as the phase Y123. Magnetic measurements corroborate the other characterizations, and indicate the sample sintered at 925 °C/1h as the one giving the highest magnetic response. / Mestre

Recently, magnetic nanoparticles are finding an increased use in biomedical applications and research. Nanobeads are widely used for cell separation, biosensing and cancer therapy, among others. Due to their properties, nanowires (NWs) are gaining ground for similar applications and, as with all biomaterials, their cytotoxicity is an important factor to be considered before conducting biological studies with them. In this work, the cytotoxic effects of nickel NWs (Ni NWs) were investigated in terms of cell viability and damage to the cellular membrane. Ni NWs with an average diameter of 30-34 nm were prepared by electrodeposition in nanoporous alumina templates. The templates were obtained by a two-step anodization process with oxalic acid on an aluminum substrate. Characterization of NWs was done using X-Ray diffraction (XRD) and energy dispersive X-Ray analysis (EDAX), whereas their morphology was observed with scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Cell viability studies were carried out on human colorectal carcinoma cells HCT 116 by the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) cell proliferation colorimetric assay, whereas the lactate dehydrogenase (LDH) homogenous membrane fluorimetric assay was used to measure the degree of cell membrane rupture. The density of cell seeding was calculated to obtain a specific cell number and confluency before treatment with NWs. Optical readings of the cell-reduced MTT products were measured at 570 nm, whereas fluorescent LDH membrane leakage was recorded with an excitation wavelength of 525 nm and an emission wavelength of 580 - 640 nm. The effects of NW length, cell exposure time, as well as NW:cell ratio, were evaluated through both cytotoxic assays. The results show that cell viability due to Ni NWs is affected depending on both exposure time and NW number. On the other hand, membrane rupture and leakage was only significant at later exposure times. Both cytotoxic assessment assays showed an earlier cytotoxic effect in case of shorter NWs, with longer ones having a more marked toxicity, albeit with a delay in time. These findings demonstrate that different levels of biocompatibility can be obtained with specific doses and properties of Ni NWs and can serve as guideline for future experiments.

>Magister Scientiae - MSc / TiO2 nanoparticle films are important electron transport layers (ETLs) in photovoltaics such as dye-sensitised, perovskite and polymer hetero-junction solar cells. These films, however, have significant electron trap-sites as a result of the large density of oxygen vacancies present in nano-sized TiO2. These trap-sites cause electron-hole recombination and ultimately lower photon-to-current conversion efficiency of the underlying cell during operation. Doping the TiO2 lattice with low atomic number elements such as nitrogen is a proven method to overcoming the charge transport inefficiency of TiO2 ETLs; another is the use of one-dimensional (1D) nanowires (NWs), instead of nanoparticles.

La conversion thermoélectrique a suscité un regain d'intérêt en raison des possibilités d'augmenter l'efficacité tout en exploitant les effets de taille. Par exemple, les nanofils montrent théoriquement une augmentation des facteurs de puissance ainsi qu'une réduction du transport des phonons en raison d'effets de confinement et/ou de taille. Dans ce contexte, le diamètre des nanofils devient un paramètre crucial à prendre en compte pour obtenir des rendements thermoélectriques élevés. Une approche habituelle consiste à réduire la conductivité thermique phononique dans les nanofils en améliorant la diffusion sur les surfaces tout en réduisant les diamètres.Dans ce travail, la caractérisation thermique d'une forêt dense de nanofils de silicium, germanium, silicium-germanium et alliage Bi2Te3 est réalisée par une méthode 3-omega très sensible. Ces forêts de nanofils pour le silicium, le germanium et les alliages silicium-germanium ont été fabriqués selon une technique "bottom-up" suivant le mécanisme Vapeur-Liquide-Solide en dépôt chimique en phase vapeur. La croissance assistée par matrice et la croissance par catalyseurs en or des nanofils à diamètres contrôlés ont été réalisés à l'aide d'alumine nanoporeuse comme matrice. Les nanofils sont fabriqués selon la géométrie interne des nanopores, dans ce cas le profil de surface des nanofils peut être modifié en fonction de la géométrie des nanopores. Profitant de ce fait, la croissance à haute densité de nanofils modulés en diamètre a également été démontrée, où l'amplitude et la période de modulation peuvent être facilement contrôlées pendant la fabrication des matrices. Même en modulant les diamètres pendant la croissance, les nanofils ont été structurellement caractérisés comme étant monocristallins par microscopie électronique à transmission et analyse par diffraction des rayons X.La caractérisation thermique de ces nanofils a révélé une forte diminution de la conductivité thermique en fonction du diamètre, dont la réduction était principalement liée à une forte diffusion par les surfaces. La contribution du libre parcours moyen à la conductivité thermique observée dans ces matériaux "bulk" varie beaucoup, Bi2Te3 ayant une distribution en libre parcours moyen (0,1 nm à 15 nm) très faible par rapport aux autres matériaux. Même alors, des conductivités thermiques réduites (~40%) ont été observées dans ces alliages attribuées à la diffusion par les surfaces et par les impuretés. D'autre part, le silicium et le germanium ont une conductivité thermique plus élevée avec une plus grande distribution de libre parcours moyen. Dans ces nanofils, une réduction significative (facteur 10 à 15 ) a été observée avec une forte dépendance avec la taille des nanofils.Alors que les effets de taille réduisent la conductivité thermique par une meilleure diffusion sur les surfaces, le dopage de ces nanofils peut ajouter un mécanisme de diffusion par différence de masse à des échelles de longueur atomique. La dépendance en température de la conductivité thermique a été déterminée pour les nanofils dopés de silicium afin d'observer une réduction de la conductivité thermique à une valeur de 4,6 W.m-1K-1 dans des nanofils de silicium fortement dopés avec un diamètre de 38 nm. En tenant compte de la conductivité électrique et du coefficient Seebeck calculé, on a observé un ZT de 0,5. Avec l'augmentation significative de l'efficacité du silicium en tant que matériau thermoélectrique, une application pratique réelle sur les appareils n'est pas loin de la réalité. / Thermoelectric conversion has gained renewed interest based on the possibilities of increasing the efficiencies while exploiting the size effects. For instance, nanowires theoretically show increased power factors along with reduced phonon transport owing to confinement and/or size effects. In this context, the diameter of the nanowires becomes a crucial parameter to address in order to obtain high thermoelectric efficiencies. A usual approach is directed towards reducing the phononic thermal conductivity in nanowires by achieving enhanced boundary scattering while reducing diameters.In this work, thermal characterisation of a dense forest of silicon, germanium, silicon-germanium and Bi2Te3 alloy nanowires is done through a sensitive 3ω method. These forest of nanowires for silicon, germanium and silicon-germanium alloy were grown through bottom-up technique following the Vapour-Liquid-Solid mechanism in Chemical vapour deposition. The template-assisted and gold catalyst growth of nanowires with controlled diameters was achieved with the aid of tuneable nanoporous alumina as templates. The nanowires are grown following the internal geometry of the nanopores, in such a case the surface profile of the nanowires can be modified according to the fabricated geometry of nanopores. Benefiting from this fact, high-density growth of diameter-modulated nanowires was also demonstrated, where the amplitude and the period of modulation can be easily tuned during the fabrication of the templates. Even while modulating the diameters during growth, the nanowires were structurally characterised to be monocrystalline through transmission electron microscopy and X-ray diffraction analysis.The thermal characterisation of these nanowires revealed a strong diameter dependent decrease in the thermal conductivity, where the reduction was predominantly linked to strong boundary scattering. The mean free path contribution to the thermal conductivity observed in the bulk of fabricated nanowire materials vary a lot, where Bi2Te3 has strikingly low mean free path distribution (0.1 nm to 15 nm) as compared to the other materials. Even then, reduced thermal conductivities (~40%) were observed in these alloys attributed to boundary and impurity scattering. On the other hand, silicon and germanium have higher thermal conductivity with a larger mean free path distribution. In these nanowires, a significant reduction (10-15 times) was observed with a strong dependence on the size of the nanowires.While size effects reduce the thermal conductivity by enhanced boundary scattering, doping these nanowires can incorporate mass-difference scattering at atomic length scales. The temperature dependence of thermal conductivity was determined for doped nanowires of silicon to observe a reduction in thermal conductivity to a value of 4.6 W.m-1K-1 in highly n-doped silicon nanowires with 38 nm diameter. Taking into account the electrical conductivity and calculated Seebeck coefficient, a ZT of 0.5 was observed. With these significant increase in the efficiency of silicon as a thermoelectric material, a real practical application to devices is not far from reality.

The Leighton group has long been interested in developing strained silanes for their use in polyketide synthesis. Recently, our interests have led us to develop a new type of silicon Lewis acid and catalyst with high levels of reactivity. Upon activation with a thiourea, a stabilized silylium ion is formed allowing for the facile allylation of aldehydes and ketones, in addition to Diels-Alder catalysis. This represents one of the first examples of the merger between anion-binding catalysis and silylium ion catalysis. Our group’s interest in strained silanes has also led us to investigate their conductance properties in molecular break junctions. To further understand the nature of the bond-ruptured species we have proposed new synthetic targets and have described herein our progress towards synthesizing these targets.

A thin film organic/ inorganic hybrid solar cell was fabricated by incorporating ZnO nanowires, n- and p-type organic semiconductors and inorganic quantum dots. The basic cell design involved the electrodeposition of ZnO nanowires grown on a substrate coated with a transparent conductive oxide. The ZnO nanowires were coated with a thin layer of an organic n-type material, followed by a deposition of inorganic quantum dots. A p-type polymer layer was subsequently deposited and the sample was then contacted with gold to form a quantum dot layer sandwiched between a p-n junction of organic conductive materials. Various materials and processing methods were adjusted, using I-V characteristics, photovoltage and/ or photocurrent measurements to determine the performance of the cell. Each constituent material in the basic device design was evaluated in terms of its contribution to the sample characteristics. A variety of deposition techniques were investigated to obtain homogeneous layers. Different annealing procedures were explored with the intent of balancing the time and temperatures required for electrical activation with material constraints such as tendency towards oxidation and low melting points. The effect of time on the sample characteristics was also observed. The evaluation primarily includes data for samples that led to design modifications aimed at improving both electrical properties and quantum efficiencies. This research led to the development of a hybrid solar cell sensitized by the addition of quantum dots. The organic semiconductors were used to form a p-n junction, and the p-type polymer also served as an active absorber layer. The quantum dots were used as the inorganic absorber fayer, and the results show that the range of optical absorption in the cell can be modified by adjusting particle size. In addition, the ZnO nanowires appear to improve charge transfer, when used with materials that have favorable band offsets.