This work focuses on binary chemical nano-patterning and on aspects related to the self-organization and stability during and after dewetting of thin block-copolymer films on chemically nano-patterned substrates. Regarding surface functionalization with thiols, the exchange of thiols in both liquid and gas phase was first investigated. The aim was to control thiols-assembly on gold and thus to fabricate unscrambled binary chemical nano-patterns. The systems gold-thiols are considered as alternatives to silicon oxide-silanes systems in the chemical nano-patterning processes because of fabrication simplicity reasons. The strategy developed to avoid thiol exchange was used to fabricate unscrambled binary chemical nano-patterns combining a top-down approach, Electron Beam Lithography (EBL), and a bottom-up approach based on the self-assembly of thiols on gold. Than, using the chemically nano-patterned surfaces previously developed, the organization processes of thin block-copolymer films were studied. Thin symmetric and asymmetric diblock copolymer films were deposited on engineered substrates consisting of alternating less and more wettable stripes. By locally tuning the chemical properties of the substrate, the interaction potential between the polymer and the substrate can be manipulated. It was thus possible to force a liquid film to dewet or to self-organize in a variety of configurations through phase preparation, specific interactions, confinement.

Bubbles are commonly found in the world around us, from industrial products to carbonated beverages. This thesis will discuss three processes involving of bubbles, from applications to fundamental phenomena. In the first portion of this thesis, I describe the use of bubbles to prevent the formation of marine biofilms and other colonizing organisms onto built structures, collectively referred to as biofouling. Biofouling detrimentally affects the structures upon which they grow, increasing drag and fuel consumption of moving vessels, reducing performance of acoustic sensors, and enhancing degradation of static structures. With recent international bans placed on common biocidal coatings, there is a demand for environmentally friendly antifouling technologies with strong performance. Bubbles rising along a submerged surface have been shown to inhibit biofouling growth, but little work has been done to determine the primary mechanisms responsible for their antifouling behavior. In this thesis I discuss a combination of field and laboratory experiments as well as a theoretical approach used to gain insight into the dominant mechanisms at play, thus laying a foundation for optimization of this antifouling technique. We find that biofouling is inhibited by shear stresses generated throughout the flow, and the degree of biofouling prevention relates to the distribution of bubbles which locally alters the shear stress. Inspired by the potential for direct interactions between bubbles and biofouling, the second topic of this thesis considers the process by which a bubble dewets, or "sticks to", a solid surface. As a bubble approaches a solid surface, the liquid between the gas and solid begins to drain until it resembles a thin film. Upon rupture of this thin film, the air dewets the surface as a contact line is formed and expands. Previous work regarding this contact line motion assumes viscous effects dominate the spreading dynamics while inertial effects are neglected. Studying the early-time dynamics of dewetting bubbles, we find viscosity to be negligible while inertia and capillarity govern the motion of a newly established contact line, suggesting early stages of dewetting are more rapid than anticipated. In the final portion of this thesis, I discuss the fundamental stability of bubbles in volatile liquids. When a bubble arrives at a free surface, we typically expect the film of the bubble cap to thin over some period of time until it ruptures. Traditionally, the drainage of this film has been considered inevitable with evaporation only hastening the film rupture. Here I show air bubbles at the free surface of liquids which appear to defy traditional drainage rules and can avoid rupture, persisting for hours until dissolution. Using pure, volatile liquids free of any surfactants, we highlight and model a thermocapillary phenomenon in which liquid surrounding the bubble is continuously drawn into the bubble cap, effectively overpowering the drainage effects. / 2020-09-28T00:00:00Z

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This Thesis explores physical phenomena characteristic for thin liquid films and small droplets of simple and complex liquids on solid substrates for which wettability and capillarity control their statical and dynamical properties. We start by discussing the general concepts of wettability and capillarity and introduce the common mathematical framework of the lubrication approximation for studies of thin liquid films and small contact angle drops. We demonstrate the derivation of the generic equation describing the evolution of a film of simple liquid from the Navier-Stokes equations. We show how this model can be further extended to incorporate various effects relevant to the case of complex liquids. The results described in the Thesis comprise three projects with the common main theme of the influence of wettability and capillarity on the statics and dynamics of the studied systems, namely (i) Evaporating sessile droplets fed through the solid substrate - a geometry that allows us to discuss steady states of the system and their role in the time evolution of freely evaporating droplets without influx in an isothermal case; (ii) The influence of a solute--dependent wettability on the stability, static and dynamical properties of thin films and drops of non-volatile mixtures, suspensions and solutions; (iii) A parameter-passing scheme between particle-based Molecular Dynamics simulations and the continuum lubrication model which allows us to discuss equilibrium properties of small polymeric droplets. We present the physical questions arising in the three systems and discuss approaches and results as well as possible extensions.

Controlling and predicting rupture and dewetting of quiescent thin water films, hundreds of microns thick, was studied experimentally. Wax, polycarbonate, steel and aluminium surfaces were immersed in water; the water level was lowered to form thin films above the surfaces. Spontaneous film rupture only occurred on wax, a low-energy surface. Films ruptured at the edges of the other—high-energy—surfaces. Increased surface roughness decreased chances of rupture and dewetting in the film. Introducing large wax or steel protrusions (on the order of millimetres) on smooth surfaces showed films rupturing above the protrusions and adhering to them; further thinning caused rupture and dewetting away from the protrusions. Entrapped air bubbles, injected through the surface and into the film, ruptured as they breached the film surface to form stable holes in the film if it was sufficiently thin. Entrapped air was the best means of rupturing films on all surfaces.

Controlling and predicting rupture and dewetting of quiescent thin water films, hundreds of microns thick, was studied experimentally. Wax, polycarbonate, steel and aluminium surfaces were immersed in water; the water level was lowered to form thin films above the surfaces. Spontaneous film rupture only occurred on wax, a low-energy surface. Films ruptured at the edges of the other—high-energy—surfaces. Increased surface roughness decreased chances of rupture and dewetting in the film. Introducing large wax or steel protrusions (on the order of millimetres) on smooth surfaces showed films rupturing above the protrusions and adhering to them; further thinning caused rupture and dewetting away from the protrusions. Entrapped air bubbles, injected through the surface and into the film, ruptured as they breached the film surface to form stable holes in the film if it was sufficiently thin. Entrapped air was the best means of rupturing films on all surfaces.

In this work, the structural and optical properties of metal nanoparticles fabricated on various substrates have been investigated. The particles were fabricated by electron beam lithography (EBL) and dewetting of a thin metal film. The advantages and disadvantages of these two fabrication techniques are discussed by considering the properties of the nanoparticles and the applicability to large area substrates. Being a practical fabrication method, dewetting can be applied to any substrate with either small or large surfaces. For comparison between different sample types, some process parameters such as film thickness, annealing temperature and duration were fixed during the whole study. Gold (Au) and silver (Ag) were preferred for nanoparticle formation because of their superior optical properties for solar cell applications. We used silicon (Si), silicon nitride (Si3N4), silicon dioxide (SiO2) and indium tin oxide (ITO) on glass, and textured Si as the substrate for the particle formation. These substrates are commonly used in solar cell technology for different purposes. The formation of the metal nanoparticles, their size and size distribution were monitored by Scanning Electron Microscope (SEM). We performed a dimension analysis on the SEM images using a program called Gwyddion. We observed that the substrate type greatly affects particle mean size, suggesting a dependence of the dewetting process on the interface properties. Moreover, the effect of the annealing temperature was found to be a function of the substrate type. Scattering measurements have been carried out in order to observe the localized surface plasmon resonance (LSPR) conditions. The effect of the particle size and the dielectric environment was observed as a shift in the plasmon resonance peak position along the wavelength axis. As expected from the theory, the resonance peaks shift to longer wavelengths with increasing particle size and dielectric constant. In order to compare the experimental results with the theory, Mie theory was applied to calculate the plasmon resonance peaks. We obtained fairly well agreement between the experimental and theoretical results. In this study, nanoparticles were assumed to be in contact with more than one medium, namely air and the underlying substrate. Finally, we have reached a successful methodology and knowledge accumulation for the metal particle formation on variety of substrates by the dewetting technique. It is clear that this knowledge can form basis for the photovoltaic applications.

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In an age in which the microchip is ubiquitous, the rewards for novel methods of microfabrification are great, and the vast possibilities of nanotechnology lie just a little ahead. Various methods of microlithography offer differing benefits, and even as older techniques such as optical lithography are being refined beyond what were once considered their upper limits of resolution, new techniques show great promise for going even further once they reach their technological maturity. Recent developments in optical lithography may allow it to break the 100-nm limit even without resorting to x-rays.