Integrated circuit (IC) technology has evolved rapidly but the continual development of transistors and interconnects (the connection between the transistors) is facing greater and greater challenges, which require new materials and new processes. Research in nano-particles (or nanoscale clusters) creates possibilities for both new materials and new processes. This thesis explores the electrical properties of amorphous antimony clusters and develops a new copper cluster deposition technique for application to transistors and interconnects respectively. For amorphous antimony clusters, an electron diffraction technique was applied to identify the phase of the clusters prior to deposition on electrically contacted samples. The deposition process produced uniform cluster films suitable for electrical measurements. A consistent percolation exponent for conduction (t=1.85) was obtained. After deposition, the resistance of the films continued to increase because of coalescence. Although it was previously reported that amorphous antimony films were semiconducting, from linear I(V) curves, a low temperature coefficient of resistance (10⁻⁴ K⁻¹) and no observable gate effect, it was found that the antimony cluster films in this study were not semiconducting, possibly due to the effect of coalescence. The development of the copper clusters for the interconnects application was very successful. Trenches of sub-200 nm widths, with different diffusion barriers and seed layers, and up to 5:1 aspect ratios have been completely filled with copper clusters. Due to the propensity for reflection of clusters from the planar surfaces between trenches, the process results in selective deposition into the trenches and bottom up filling is demonstrated. After annealing in hydrogen or in vacuum, the clusters sinter into a copper seed layer. The resistivity measured by a thin film four-point probe (1.6 - 2.3 × 10⁻⁸ Ωm) meets the requirement by industry (2.2 × 10⁻⁸ Ωm). The process is therefore promising for industrial application, but further testing and investigation of integration issues is required.

Nanoscale organic particles have gained a prominent role in drug and gene delivery field. As the nature of the nanoparticle’s (NPs) surface plays a major role in their targeting efficiency, bioavailability, and cytotoxicity, membrane-mimic nanoparticles are considered highly attractive materials for in vivo and in vitro applications. Synthetic membrane vesicles (liposomes) and nanoconstructs built with native cancer cellular membrane are excellent scaffolds to improve cellular delivery. Liposomes have been extensively used due to their high loading capacity, biocompatibility and biodegradability. However, modifications with stimuli responsive materials are highly needed to improve their stability and turn them active participants in controlled delivery. Towards a nature inspired approach, reconstructed bilayers from cell membrane are a good candidate to enhance NP’s targeting ability and biocompatibility. The primary focus of this research is to develop smart responsive (lipid) membrane coated NPs with surface modifications for controlled and targeted drug and/or gene delivery for application in cancer therapy. Three approaches have been developed, namely i) liposomes as thermoresponsive nanocarriers for the delivery of genetic material; ii) magnetically photosensitive liposome hybrids and iii) biomimetic periodic mesoporous organo silica engineered for better a biocompatibility and targeting capabilities. In the first project synthetic liposomes were loaded with ammonium bicarbonate salt (ABC) and siRNA. The combination of lipids chosen and the relative ratios allowed the rapid release of the genetic material to the multi drug resistant cancer cells studied, upon external heat trigger. This design has improved the gene silencing efficiency via successful endosomal escape. In the second project, SPIO@Au nanoparticles were imbedded in the lipid bilayer to produce a photo/thermal responsive carrier that could be also used in cell imaging besides gene transfection and drug delivery. For the final project, a nature inspired coating was used in periodic mesoporous organosilica (PMO) NPs. PMOs were functionalized with colorectal cancer cell membrane. The resulting CC@NH2-TSPMOs, holding the diverse cancer cell membrane antigens showed a promising potential towards disease targeting and improved pharmacokinetics. This research confirms the notion of how nanotechnology engineering approaches are effective to improve the quality and effectiveness of cancer therapeutics.

>Magister Scientiae - MSc / Diabetes Mellitus is a major global health issue, affecting over 463 million adults in the world. Metformin is the standard drug administered to most people suffering fromdiabetes; however, this medication is contraindicated in many individuals, like most of the medicines developed to combat diabetes. Many diabetic patients turn to herbal medicines due to their renowned traditional use and fewer side effects.While the beneficial effects of phytotherapy are very evident, separation of nontoxic from toxic phytochemicals is still a challenge. Phytonanotherapy is a branch in nanotechnology that seeks to find the middle ground between the fast-acting mechanism of conventional drugs which also present with long lasting or severe toxic side effects, and the slowacting mechanism of phytotherapy which presents with less severe side effects. As such, the aim of this study was to pioneer the investigation of gold nanoparticles biosynthesized using the Carprobrotus edulis fruit aqueous extract (CeFe-AuNPs) as potential treatment for diabetes mellitus. Previously optimized conditions were used to synthesize CeFe-AuNPs which were concurrently characterized using UV-Vis, dynamic light scattering, High Resolution – Transmission Electron Microscopy and Fourier Transform Infrared Spectroscopy techniques. The physichochemical stability of CeFe-AuNPs in phosphate buffer saline, 0.5 % bovine serum albumin, water and 10 % NaCl was also investigated. The effect of CeFe and CeFe-AuNPs on glucose uptake by yeast cells was investigated using 5, 10 and 25 mM glucose reactions. Acute toxicity of CeFe and CeFe- AuNPs was conducted in female Wistar rats (n = 20) and major organs were analyzed through the haematoxylin-eosin stain. The anti-diabetic effects of the CeFe (200 and 400 mg/kg) and CeFe- AuNPs (100 and 200 mg/kg) were investigated in male Wistar rats divided into seven group (n = 6). Histopathology of the pancreas, and the serum insulin were determined.

The thin film pressure balance (TFPB) technique were used to study the stability of single foam films produced in the presence of n-alkyl polyoxyethylene (CnEOm) homologues. The results showed that films thin faster than predicted by the classical DLVO theory, which considers contributions from the van der Waals-dispersion and double-layer forces to the disjoining pressure of the film. The discrepancy may be attributed to the presence of hydrophobic force, the magnitude of which has been estimated using the Reynolds lubrication approximation. It has been found that the attractive hydrophobic force was substantially larger than the attractive van der Waals force, which may explain the faster film thinning kinetics. With a given non-ionic surfactant, the hydrophobic force decreased with increasing surfactant concentration, which explained the slower kinetics observed at higher concentrations and hence the increased foam stability. At concentrations where the hydrophobic force became comparable to or smaller than the van der Waals force, the foam films were stabilized by the increased elasticity of the foam films. The film elasticity of the surfactant solutions were measured using the oscillating drop analysis technique at different frequencies. The measurements were conducted in the presence of CnEOm surfactants with n=10-14 and m=4-8, and the results were analyzed using the Lucassen and van den Tempel model (1972). There was a reasonable fit between the experiment and the model predictions when using the values of the Gibbs elasticity calculated from the Wang and Yoon model (2006). From this exercise, it was possible to determine the diffusion coefficients (D) of the CnEOm surfactants. The D values obtained for CnEOm surfactants were in the range of 2.5x10-10 to 6x10-9 m2s-1, which are in general agreement with those reported in the literature for other surfactants. The diffusion coefficient decreased with increasing alkyl chain length (n) and increased with increasing chain length (m) of the EO group. These findings are in agreement with the results of the dynamic surface tension measurements conducted in the present work. The TFPB studies were also conducted on the foam films stabilized in the presence of a mixture of C12EO8 and sodium dodecylsulfate (SDS) at different ratios. The results showed that the hydrophobic force increased with increasing C12EO8 to SDS ratio. Thus, the former was more effective than the latter in decreasing the hydrophobic force and hence stabilizing foam films. The C12EO8 was more efficient than SDS in increasing the elasticity of the single foam films and stabilizing foams. The TFPB studies were also conducted in the presence of n-octadecyltimethyl chloride (C18TACl) and polymers, i.e., polyvinylpyrrolidone (PVP) and polystyrene sulfonate (PSS). The effect of polymer on the film elasticity was strongest in the presence of PSS, which can be attributed to the charge-charge interaction. Nano-sized silica and poly methyl methacrylate (PMMA) particles were used as solid surfactants to stabilize foams. It was found that the foam stability was maximum at contact angles just below 90o. The TFPB studies conducted with silica nano-particles showed that the kinetics of foam films became slower as the contact angle was increased from 30o to 77 o , indicating that foam films becomes more stable with more hydrophobic particles. The extra-ordinary stability observed with the hydrophobic silica nano-particles may be attributed to the possibility that the particles adsorbed on bubble surfaces retard the drainage rate and prevent the films to reach the critical rupture thickness (Hc). Confocal microscope and SEM images showed that hydrophobized nano-particles adsorbed on the surfaces of air bubbles, and that some of the nano-particles form aggregates depending on the particle size and hydrophobicity. The dynamic surface tension measurements conducted with PMMA and silica nano-particles showed that the latter has higher diffusion rates than the former, which may be due to the differences in particle size and hydrophobicity. / Ph. D.

Current research in materials science and engineering continues to drive it's attention to systems on the nanoscale. Thin films, nano-particles, quantum dots, nano-wires, etc are just a few of the areas that are becoming important in projects ranging from biomedical transport to nano-gears. Thus, understanding, producing, and creating these system is also becoming an important challenge for scientists and engineers to overcome. Physically manipulating objects on the atomic scale requires more than just "micro tweezers" to arrange them in a particular system. Another concern is that forces and interactions that could be ignored or approximated at larger scales no longer hold in this regime. It is the goal of this project to use computational models to simulate nano-particles interacting with customized, highly tailored surfaces in order to confine and pattern them to desired specifications. The interactions to be considered include electrostatic attraction and repulsion, hamaker forces, steric effects, dielectric effects of the medium, statistical variability, mechanical induced surface vibrations, etc. The goal is to be able to manufacture such systems for experimentation in order to compare results to the models. If the models do not hold, we hope to understand the origin of these discrepancies in order to create more robust models for this length scale. Lithography, CVD, and chemical etching will be the primary methods used to create these surfaces on glass substrates. TEM analysis will be compared to modeling through various MD program packages. / Singapore-MIT Alliance (SMA)

Nickel Nanostrands (NiNS) are nano-particles that are highly branched and have a high aspect ratio. These particles show promise as excellent additives to composites when electrical conductivity is desired. Unfortunately, there is very little research done on dispersing powdered NiNS in various polymer matrices. This thesis covers the research in dispersing NiNS in three separate polymer systems, and related composite processing and characterization. An aromatic polyimide (CP2) is first used as a thermoplastic matrix and attempts to incorporate NiNS via an in-situ processing technique concurrent with in-situ polymerization are detailed. Epoxy is then used as a representative thermoset where the NiNS are dispersed in the resin before a hardener is added. The last polymer tested is thermoplastic Polyvinylidene Fluoride (PVDF). NiNS are introduced to this polymer in a solution mixture. Once dispersed, the PVDF solution is heated until the solvent evaporates leaving a PVDF melt containing NiNS, which is subsequently cooled. Samples of all three polymer nano-composites are created and dispersion is observed with an optical microscope. Using DSC, DMA and dielectric spectroscopy, thermal, mechanical and electrical properties are measured and analyzed. Results for the CP2 nano-composites showed that during the cure phase, the NiNS settled to the bottom of the films resulting in a non-dispersed composite. This result highlighted the difference between NiNS and other more conventional nano-particles, namely that the NiNS are larger and heavier, therefore are not 'locked into' a dispersed state by the polymer chains. Several techniques were investigated for dispersing NiNS in the epoxy matrix. A method without solvent was shown to be the most effective and resulted in a well-dispersed nano-composite that showed increases in electrical conductivity and dielectric constant as NiNS concentration increases. Enhancement in storage modulus was observed above the composite's Tg as well. PVDF nano-composites also showed good dispersion and a general increase in electrical properties. Below Tg, storage modulus decreases at first before a slight recovery with increasing NiNS. Beyond Tg, the opposite effect is observed. FTIR measurements for the PVDF were also taken and showed no significant changes in the polymer morphology with additions of NINS.

The work aims to manufacture AS-4/PEEK APC-2 nano-composite laminates first. We used the prepreg form of AS-4 Graphite/PEEK laminae to make APC-2 laminates of 2 mm thick with two lay-ups of cross-ply and quasi-isotropic totally 16 plies by a hot press via the modified diaphragm curing. The nano-particles SiO2 with the average diameter of 15¡Ó5 nm were uniformly spread in the specific interfaces of laminate. From mechanical testing it is found that the nanocomposite specimens of spreading 10 plies nanoparticles (3% by wt. of matrix) possesses the highest mechanical properties. we see that in cross-ply specimens the ultimate strength increases 10.91 % and stiffness 6.7 %; while in quasi-isotropic specimens the ultimate strength increases 12.48 % and stiffness 19.93 %. Second, repeat the tensile tests at 50, 75, 100, 125, 150¢J to receive respective stress-strain curve , strength and stiffness. At elevated temperatures the ultimate strength decreases slightly below 75¢J and the elastic modulus reduces slightly below 125¢J, however, both properties degrade highly at 150¢J ( Tg) for two layups generally. Finally, the constant stress amplitude tension-tension cyclic testing was conducted. It is found that both the stress-cycles (S-N) curves are very close below 104 cycles for cross-ply laminates w/wo nanoparticles, and the S-N curve of nano-laminate slightly bent down after 105 cycles. Whilst in quasi-isotropic laminates, the S-N curve of nano-laminate is always slightly below that of APC-2 laminate through the life.

No description available.

In this thesis, photo luminescent diodes with the device structure of ITO/PEI/(CdTe/PDDA)*n/Al were fabricated using the method of layer-by-layer self assembly. The film thicknesses were varied from 150 nm to 380 nm. The films were characterized through X-ray diffraction (XRD), optical absorption and photoluminescence (PL) measurements. The XRD results on the film indicated a cubic crystalline structure (111) for the nano-CdTe particles. The band gap of the nano-particles were evaluated to be 2.1 eV in solution and 2 eV in films, which was further confirmed by the PL measurements as the solution exhibited a yellow luminescence while the film exhibited orange luminescence. The J vs. V curves revealed that the diodes exhibited rectifying behavior in both the forward and reverse biasing. Two models of current transport, one based on a Schottky mechanism and the other based on a tunneling mechanism were developed and were compared with the experimental values. The tunneling model developed could simulate the experimental currents up to four orders of magnitude. The tunneling mechanism of charge transport was further proved by the capacitance vs. voltage curves, which were identical to that of ITO/MEH-PPV/Al devices, where tunneling mechanism was the dominant method of charge transport.

L'amélioration des propriétés mécaniques des métaux et des alliages purs peut être obtenue par l'introduction de particules de céramique dispersées de manière appropriée dans le matériau. Ces particules peuvent agir comme sites de germination améliorant la réduction de la taille des cristallites (grains). La dispersion de ces matières nucléantes présente des défis du fait de leur tendance à la sédimentation et à l'agglomération. Des particules de taille nanométrique peuvent également améliorer les propriétés mécaniques par plusieurs mécanismes de renforcement du type Orowan ou aux joints de grains. L'utilisation de l'agitation électromagnétique est un moyen de disperser des particules et de produire des changements dans la microstructure du matériau. L'agitation électromagnétique induite peut augmenter le nombre de sites de nucléation disponibles lors de la solidification en rompant les bras des dendrites nouvellement formées au niveau du front de solidification. Le champ de température dans le matériau fondu peut également être homogénéisé par son action. Le faible gradient de température produit dans le métal liquide peut favoriser la croissance des dendrites équiaxes. Dans cette étude, un four de type Bridgman a été utilisé pour produire des matériaux contenant des raffineurs de grains et des particules de renforcement. Le four a été équipé d'un électro-aimant de Bitter capable de produire un champ magnétique glissant (CMG). Grâce à l'agitation électromagnétique, l’écoulement induit disperse les particules et produit des changements effectifs dans la microstructure des matériaux étudiés. Les expériences ont été confrontées par des simulations numériques réalisées par l'Université de Greenwich et le laboratoire SIMaP. Les expériences effectuées en dispersant les microparticules de SiC dans la matrice de magnésium pur montrent que la distribution des particules dans le matériau est fortement régie par l'orientation verticale du champ magnétique appliqué (vers le haut ou vers le bas). Les résultats de la simulation numérique et des expériences sur la dispersion des particules sont en accord. L’agitation électromagnétique promeut un affinage des grains dans le cas de l’aluminum pur. Une tendance contraire est observée sur les alliages. Le CMG est utilisé pour disperser les particules de taille nanométrique et micrométrique. La dispersion des particules micrométriques utilisées dans les alliages de magnésium et d’aluminium n’ont d’influence ni sur l’affinage des grains ni sur le renforcement mécanique. Cependant, les expériences avec des nanoparticules ont montré une amélioration de la résistance au fluage. / Improvement in mechanical properties of pure metals and alloys can be achieved by the introduction of ceramic particles appropriately dispersed within the material. These particles can act as nucleation sites enhancing the reduction of the crystallite (grain) size. The dispersion of these nucleant materials presents challenges due to their tendency to sediment and to agglomerate. Particles of nanometric size can also produce the improvement of mechanical properties by several reinforcement mechanisms such as Orowan or grain boundary strengthening. The use of electromagnetic stirring can provide a method to disperse particles and produce changes in the microstructure of the material. The induced stirring can increase the number of nucleation points available during solidification breaking the arms of the new formed dendrites at the solidification front. The temperature field in the molten material can be also homogenized by the action of the electromagnetic stirring. The small temperature gradient produced in the liquid metal can promote the growing of equiaxed dendrites. In this study a Bridgman type furnace has been used to produce materials containing grain refiners and reinforcement particles. The furnace has been equipped with a Bitter coil electromagnet capable to produce a travelling magnetic field (TMF). The electromagnetic stirring provides an induced flow which is used to disperse the particles and produced measurable changes in the microstructure of the materials studied. The experiments carried out were supported with numerical simulations performed by University of Greenwich and Simap laboratory. Experiments performed dispersing SiC microparticles into pure magnesium matrix showed that particle concentration patterns in the material are strongly governed by the vertical orientation of the magnetic field applied (upwards vs downwards). The observed patterns of dispersion obtained from the experiments presented a good agreement with the patterns predicted by the numerical simulation. The effects of the electromagnetic stirring in the grain refining of pure aluminium showed positive results whereas the alloys subjected to stirring presented grain growth. The TMF was used to disperse particles of micrometric and nanometric size. The dispersion of microparticles in magnesium and aluminium alloys did not produce improvements in either grain refinement or mechanical properties. However, the experiments performed dispersing nanoparticles in magnesium alloy showed the improvement of creep resistance.