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Nanomanufacturing is an active research area in academia and industry due to the ever-growing demands for precision surface modifications of thin films or substrates with nanoscale features. Conventional lithographic techniques face many challenges as they approach their fundamental limits. Consequently, new nanomanufacturing tools, fabrication techniques, and precision instruments are being explored and developed to meet these challenges. It has been hypothesized that direct-write nanolithography might be achieved by using a field-emitted electron beam for nanomachining. This dissertation moves this research one step closer by developing a precision instrument that can enable the integration of direct-write nanolithography by a field-emitted electron beam with dimensional metrology by scanning tunneling microscopy. First, field emission from two prospective electron sources, a carbon nanotube field emitter and a sharp tungsten field emitter, is characterized at distances ranging from sub-micrometer to a few micrometers. Also, the design and construction of a low thermal drift piezoelectric linear motor is described for tip-sample approach. Experiments indicate that: the step size is highly repeatable with a standard deviation of less than 1.2 nm and the thermal stability is better than 40 nm/◦C. Finally, the design and construction of the instrument are presented. Experiments indicate that: the instrument is operating properly in scanning tunneling microscope mode with a resolution of less than 2 Å.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

This research comprehensively reviews the properties of regular micro and nano structures fabricated by laser interference lithography and reports on their applications in the antireflection and self‐cleaning surface. The research systematically investigates the laser interference lithography technology taking into account its advantages and abilities to realize various potential applications. Multiple‐beam interference lithography systems are constructed. Laser interference interaction with silicon wafer is analysed and the optical and hydrophobic properties are obtained via measurements. In order to fabricate the extremely low reflection and very large contact angle for solar cells, fabrication methods of antireflection and self‐cleaning are surveyed and their advantages and disadvantages compared. The research investigates the effect of heat transfer and the radiation of laser interference plasma on silicon wafer surfaces and proposes equations of heat flow and radiation effects of laser plasma of interfering patterns in a four‐beam laser interference distribution. Following the irradiation, the silicon wafer surface is covered with a periodic array of micrometer and nanometer‐sized structures, which have the shape of grating, cone and hole. The research also investigates the effect of different laser parameters on the optical and hydrophobic properties of the structured silicon wafer surface. The results of periodic hexagonally‐distributed hole structures fabricated by three‐beam laser interference reveals excellent design guidelines for obtaining an extremely low solar‐weighted reflection, (SWR, 1.86%) and relatively large contact angle (140°) which can provide a strong self‐cleaning capability on the solar cell surface. In addition, the research creates a novel dual structure with antireflection and superhydrophobic properties fabricated by three‐beam laser interference lithography. The fabrication method is three‐beam laser interference combined with focused laser processing interacting on the silicon wafer surface. This kind of structure has a very low SWR (3.6 %) and extremely large contact angle which is more than 150° in the wavelength range from 380 nm to 780 nm. The research shows that the laser interference lithography technology can be employed and further developed to fabricate micro and nano structures of strong antireflection and self‐cleaning functions for applications in solar cells.

Les procédés lithographiques sont de nos jours très utilisés au sein de l’industrie de la microélectronique pour réaliser des matériaux fonctionnels de taille nanométrique. L’obtention de composants de taille de plus en petite (<100 nm) nécessite la mise en œuvre de nouveaux procédés de fabrication. Les travaux de recherches réalisés dans cette thèse portent sur l’étude d’un nouveau concept de lithographie par microcopie à force atomique (AFM). L'objectif principal est d'utiliser la pointe d’un AFM comme outil pour promouvoir des réactions catalysées sur une zone bien définie d’une surface greffée. De cette manière, diverses molécules ont pu être greffées sélectivement et spatialement pour conduire à des objets finis en 3 dimensions. Afin de mieux comprendre le mécanisme réactionnel, différents paramètres physico-chimiques ont été étudiés dans la première partie : vitesse de balayage de la pointe, force appliquée, distance interligne lors de la gravure du motif, largeur de lignes limites, durée de vie de la pointe catalytique et influence de la flexibilité du catalyseur présent sur la pointe. La deuxième partie consiste à la réalisation de nanostructures avec des molécules aux propriétés physico-chimiques particulières (optique, électrique, catalytique) ainsi qu’à la construction de nanostructures tridimensionnelles. Quelques résultats marquants sont l’obtention d’une largeur de ligne limite de 25 nm, d’une surface de greffage minimum de 480 µm² et d’une structure de forme pyramidale composée de trois niveaux moléculaires distincts. / Lithography processes are widely used in the microelectronics industry for the realization of functional materials of nanometric size. To obtain components increasingly small (<100 nm) the development of new manufacturing processes is requires. The research presented in this thesis concerns the study of a new concept of lithography by Atomic Force Microscopy (AFM). The main objective is to use the tip of an AFM as a tool to promote catalysed reactions on a well defined zone of a grafted surface. In this way, diverse molecules could be grafted selectively and spatially to form three dimensioned objects. To better understand the reaction mechanism, different physico-chemical parameters were studied in the first part: the scanning speed of the tip, the strength applied, the interline spacing during the engraving pattern, the width lines limits, the life time of the catalytic tip and the influence of the catalyst flexibility coated to the tip. The second part consists in the realization of nanostructures with molecules that have particular physico-chemical properties (optical, electric, catalytic) and the construction of three-dimensional nanostructures. Some pertinent results are the achievement of line width of 25 nm, a minimum grafted surface of 480 µm² and the formation of a structure of pyramidal shape constituted of three different molecular levels.

[pt] Neste trabalho foi estudada a deformação mecânica em semicondutores III-V resultante da nanolitografia por microscopia de força atômica (AFM). O AFM, equipado com uma ponta de diamante de raio de curvatura de 80 nm, foi usado para riscar a superfície do InP com forças da ordem de dezenas de mN ao longo de direções cristalográficas específicas. O padrão litografado na superfície foi caracterizado com o uso do AFM, enquanto uma análise da microestrutura do material foi feita com o uso da microscopia eletrônica de transmissão (MET). Foi realizado um estudo da deformação mecânica ao riscarmos o InP (100) com o uso do AFM utilizando forças normais variando de 7 uN a 120 uN e em direções cristalográficas das famílias <110> e <100>. Foi visto por MET, que é mais fácil produzir deformação plástica para riscos feitos na direção <110> do que na direção <100>, o que associamos à diferença na orientação dos vetores de Burgers ativados para os planos de escorregamento do InP para riscos ao longo das diferentes direções. Foi realizado também um estudo da influência da distância entre dois riscos consecutivos, feitos com o uso do AFM com força normal de 30 uN, no endurecimento por deformação plástica. Um significante endurecimento foi observado para distâncias entre riscos menores que 80 nm indicando que ocorre travamento entre discordâncias geradas por sucessivos riscos a distâncias menores que 80 nm. / [en] In this work, the mechanical deformation of III-V semiconductors resulting from atomic force microscopy (AFM) nanolithography was studied. The AFM, equipped with a diamond tip with 80nm radius, was used to scratch the InP surface with forces in the order of tens of mN along specific crystallographic directions. The pattern lithographed at the surface was characterized by AFM, while the material microstructure analyzes was performed by transmission electron microscopy (TEM). We studied the mechanical deformation of InP (100) produced by the AFM with forces in the range of 7uN to 120 uN along directions from the <110> and <100> families. It was observed by TEM that, it is easier to produce plastic deformation for scratches along the <110> than along the <100> directions, which was associated to the different orientations of the Burgers vectors activated for the InP slip planes for the scratches along the different directions. The influence of the distance between two scratches, performed with a normal force of 30 uN on the materials hardening process was performed as well. Significant hardening was observed at distances between scratches of 80nm or less suggesting that locking due to dislocation interaction is occurring at parallel scratches at distances smaller than 80nm.

<p>Ferroelectric thin films (FETFs) offer a promising new platform for advancing liquid-phase interfacial sensing devices. FETFs are capable of expressing surface charge densities that are an order of magnitude higher than those of traditional charged surfaces in liquid environments (e.g., common oxides, self-assembled monolayers, or electrets). Furthermore, the switchable polarization state of FETFs enables patterning of charge-heterogeneous surfaces whose charge patterns persist over a range of environmental conditions. Integration of FETFs into liquid-phase interfacial sensing devices, however, requires the fabrication of films with nanometer-scale surface roughness, high remnant polarization values, and interfacial stability during prolonged exposure. The objectives of my research were to i) fabricate ferroelectric ultra-smooth lead zirconium titanate (US-PZT) thin films with nanometer-scale surface roughness, ii) establish the interfacial stability of these films after prolonged exposure to aqueous environments, iii) measure the interfacial forces as a function of film polarization and ionic strength, iv) calculate the surface potential of the US-PZT surface using electric double layer (EDL) theory, and v) demonstrate the guided deposition of charged colloidal particles onto locally polarized US-PZT thin films from solution. </p><p>I demonstrate the use of ferroelectric US-PZT thin films to manipulate EDL interaction forces in aqueous environments. My work conclusively shows that the polarization state of US-PZT controls EDL formation and can be used to induce the guided deposition of charged colloidal particles in solution. </p><p>I present a robust fabrication scheme for making ferroelectric US-PZT thin films from a sol-gel precursor. By optimizing critical thermal processing steps I am able to minimize the in-plane stress of the film and reliably produce US-PZT thin films on the wafer-scale with mean surface roughness values of only 2.4 nm over a 25 &#956;m2 area. I then establish US-PZT film stability in water by measuring changes in film topography, crystallinity, surface chemistry, and electrical properties as a function of exposure duration. My results show that fabrication of crack-free US-PZT thin film is critical for long-term film fidelity in aqueous environments. Furthermore, I found no change in film topography or bulk composition with increasing exposure duration. Prolonged exposure to aqueous environments, however, gradually oxidizes the surface of the US-PZT wich results in a decrease in film resistivity and polarization saturation. Next, I used colloidal probe force microscopy (CPFM) to measure the EDL interaction force as a function of separation distance between polarized US-PZT thin films and a clean borosilicate probe. CPFM measurements were performed on oppositely polarized US-PZT thin films, which expressed either a positive or negative surface charge, and over a range of ionic strengths. The inner-Helmholtz plane (IHP) potential of the US-PZT was determined by fitting the CPFM force-separation data to number of EDL models, including; an analytical EDL model using a constant potential boundary condition with a Stern layer, a charge regulation EDL model, and a numerical EDL model using the non-linear Poisson-Boltzmann equation. Each model provides good agreement with the experimentally measured and predict high IHP surface potential for the polarized US-PZT thin films in solution. Finally, I demonstrate the use of polarized US-PZT to induce the guided deposition of positively or negatively charged colloidal particles from aqueous environments. I explore the effects of ionic strength, particle size, surface roughness, and pH on particle deposition. </p><p>Overall, this work demonstrates, for the first time, that FETFs can be used as a platform to manipulate colloidal particles in aqueous environments. The experimental results demonstrate that the surface charge of the FETF is reduced by charge shielding and perform similarly to traditional, charged surfaces in aqueous environments.</p> / Dissertation

Nanolithography is a rapidly evolving field that requires new combinations of techniques to improve patterning and to assist in fabricating electromechanical devices. An increasing number of applications require surfaces with defined regions of different chemical functionality. In our previous project optimum conditions for lithographic patterning were determined and potential blockers were identified to reduce force on the tip. This work is focused on identifying good chemical modifications that will allow better control of basic patterning and to investigate the minimum force of patterning required while using each chemical system. The primary aim is to gain better control of basic pattern techniques in order to create more intricate patterns such as interdigitated arrays, which can subsequently be used in sensors. An atomic force microscope (AFM) is used to pattern the prepared colloid-coated glass slides. Several compounds were used in the investigation, including sodium sulphate, potassium sulphate, magnesium sulphate, sodium fluoride, sodium chloride, sodium bromide, and sodium iodide, potassium chloride, potassium bromide, potassium iodide, potassium dihydrogen phosphate, and potassium hydrogen phosphate. In Summary, the following were found as a result of this work:  The groups of sulphates were determined to require minimum patterning forces as indicated. Sodium sulphate took a force of 49 n Potassium sulphate took a force of 45 nN Magnesium sulphate took a force of 744.4 nN  The group of sodium and potassium halides were determined the minimum patterning forces as indicated. Sodium fluoride took a force of 8.42 nN Sodium chloride and potassium chloride took a force of 20.19 and 61.9nN Sodium bromide and potassium bromide took a force of 601.4 nN and 37.2 nN, respectively Sodium iodide and potassium iodide took a force of 953.7 nN and 47.2 nN, respectively  The phosphates were determined to require the minimum patterning forces as indicated. Potassium hydrogen phosphate took a force of 25nN Potassium dihydrogen phosphate took a force of 43 nN

In this work, Poly (diallyldimethylammonium) chloride - (PDDA) was used as a base layer for developing colloid displacement lithography platforms for sensor applications. Previous work shows that glass coated with PDDA and exposed to gold acts as a good platform for colloid displacement lithography. However, for actual sensor applications, electrical isolation of individual sensor sections must be achieved. This is attempted by laying down a 40 μm stripe of PDDA on a cleaned substrate and coating that stripe with gold colloid. The size of 40 μm or less in width is set as the target to fit within the scan window of the AFM. Stripes wider than about 40 μm would be difficult to efficiently pattern with colloid displacement lithography. While the goal of 40 μm wide stripes was achieved with sufficiently diluted PDDA solution, it was found to be difficult to adsorb sufficient amounts of gold colloid on those stripes before the stripes were lost from the glass substrate. Further, electroless deposition was found to produce only a small amount of gold on the PDDA surface without colloid nucleation sites being present.

Self-assembling peptides have emerged as new nanobiomaterials and received considerable attention in the areas of nanoscience and biomedical engineering. In this category are ionic-complementary peptides, which contain a repeating charge distribution and alternating hydrophobic and hydrophilic residues in the amino acid sequence, leading to the unusual combination of amphiphilicity and ionic complementarity. Although their self-assembled nanostructures have been successfully applied as scaffoldings for tissue engineering, novel materials for regenerative medicine and nanocarriers for drug and gene/siRNA delivery, aspects of the assembly process remain unclear. Since many of these applications involve peptide-modified interfaces and surfaces, a better understanding and control of the peptide assembly on a surface are very crucial for future development of peptide-based applications in nano-biotechnology. This thesis contains two major parts: (i) fundamental study of the assembly of a model ionic-complementary peptide EAK16-II on surfaces and (ii) potential applications of such a peptide in surface modification and nanofabrication. In the fundamental study, EAK16-II assembly on negatively charged mica was first investigated via in-situ Atomic Force Microscopy (AFM). It was found that EAK16-II nanofiber growth on mica is surface-assisted and follows a nucleation and growth mechanism involving two steps: (i) adsorption of nanofibers and fiber clusters (from the bulk solution) on the surface to serve as the seeds and (ii) fiber elongation from the active ends of the seeds. Such a process can be controlled by adjusting the solution pH since it modulates the adsorption of the seeds and the growth rates. Unlike what is observed on mica, EAK16-II formed well-ordered nanofiber patterns with preferential orientations at angles of 60° or 120° to each other on hydrophobic highly ordered pyrolytic graphite (HOPG) surfaces, resembling the crystallographic structure of the graphite. Nanofiber formation on HOPG is also surface-assisted and adopts a nucleation and growth mechanism that can be affected by solution pH. The pH-dependent adsorption of peptides to HOPG is attributed to the resulting changes in peptide hydrophobicity. It was also found that EAK16-II assembly can be induced by the mechanical force of a tapping AFM tip. It occurs when the tip cuts the adsorbed EAK16-II nanofibers into segments that then serve as seeds for new nanofiber growth. This finding allows one to locally grow nanofibers at specific regions of the surface. The tip cutting has been combined with the effect that solution pH has on peptide assembly to develop a new AFM lithography method to fabricate local patterned peptide nanostructures on HOPG. To study the use of EAK16-II for surface modification applications, the wettability and stability of the peptide-modified surfaces were characterized. EAK16-II-modified mica becomes slightly hydrophobic as the water contact angle increases from <10° to 20.3 ± 2.9°. However, the hydrophobicity of the HOPG surface is significantly reduced, as reflected in a contact angle change from 71.2 ± 11.1° to 39.4 ± 4.3°. The EAK16-II-modified mica surface is stable in acidic solution, while the modified HOPG surface is stable in both acidic and alkaline solutions. The peptide-modified HOPG shows potential as a biocompatible electrode for (bio)molecular sensing. The ability of EAK16-II to form nanofibers on surfaces has also promoted research on peptide-based metallic nanowire fabrication. Our approach is to provide EAK16-II with metal ion binding ability by adding a GGH motif to the C-terminus. This new peptide EAK16(II)GGH has been found to form one-dimensional nanofibers while binding to Cu2+ ions. The dimensions of the nanofibers were significantly affected by the nature of the anions (SO42-, Cl- and NO3-) in the copper salt solution. This work demonstrates the potential usage of EAK16-II for nanowire fabrication.