Master of Science / Department of Chemistry / Takashi Ito / Solvent swelling of block copolymer microdomains plays an essential role in the improvement of microdomain alignment by solvent vapor annealing and in chemical separations using block copolymer monoliths. Here, investigation of the effects of solvent swelling on the molecular permeability and dimensions of cylindrical microdomains in polystyrene-block-poly(ethylene oxide) (PS-b-PEO) films is done by using single molecule tracking. These films are prepared by sandwiching benzene (with/without methanol) or THF (with/without methanol) solutions containing 5 nM sulforhodamine B (SRB) between two glass substrates. The PEO microdomains are aligned in the solution flow direction during the film preparation. The diffusional motions of individual SRB molecules are measured at different drying times to assess the microdomain radius and permeability. These parameters, on average, gradually decrease with an increase in drying time; however the trend differs slightly from one solvent system to another. A sharp decrease of microdomain radius is observed for benzene, benzene-methanol, THF and THF-methanol swollen films at initial drying condition (for example 2 days). In contrast, microdomain permeability does not decrease sharply; instead a gradual decreasing trend is seen for all solvent systems. In addition, mixing of a small amount of methanol (14% in PEO microdomains) either with benzene or with THF does not produce noticeable difference in the swelling of PEO microdoamins. Importantly, both benzene and THF offer similar microdomain swelling behavior at the same drying temperature, which is evident from the microdomain radius values, however THF shows comparatively larger microdomain permeability and better correlation between permeability and microdomain radius compared with benzene.

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Laser lithography was used to create novel patterns in thin diblock copolymer films. These patterns were characterized and an examination of their formation and growth was conducted. The patterns occurred only in diblock films, due to the interaction between thermal gradient induced Marangoni flow and the self assembly of the molecules. Growth of the patterns was found to be strongly dependent on absorbed power. The impact of film thickness on pattern growth was mainly due to the corresponding changes in sample reflectance, however a periodic patterning was observed suggesting that growth is also dependent on the amount of 'excess' material (over that required to form complete lamella) available. It was also shown that the pattern growth can occur independently of laser lithography and the Marangoni effect, though laser lithography was required to direct this growth. / Thesis / Master of Applied Science (MASc)

Indium tin oxide is a transparent conductive oxide electrode which is widely used for organic electronics. Morphology of ITO plays an important role in the performance of organic electronics. To understand the influence of the substrate morphology in device performance, a controllable route for producing periodic and aperiodic roughness of ITO surfaces are necessary. In this thesis, this was attempted by using various approaches to forming ITO nanostructures. Initially, ITO was deposited by a traditional sputtering procedure. However, the roughness distribution of the sputtered ITO resulted in a s Gaussian distribution, unsuitable to further studies of roughness. ITO nanostructures can also be formed by depositing ITO nanoparticles on an ITO sub- strates. Using acetate and chloride precursors, ITO films were produced from solution and formed into nanoparticles using the reverse micelles deposition approach. The acetate route (InAc+SnCl2+ethanol), was the most successful prior to the nanoparticle formation, showing high quality ITO with bixbyte crystal structure and Sn percentages of 20%, low enough to form a conductive film. Nanoparticles were fabricated with diblock copolymer reverse micelles(PS-b-P2VP). Reverse micelles were found to act as a nano reactor, restricting the size of nanoparticles by having hydrophilic reactants undergo chemical reactions inside the micelles. However, nanoparticles from the reverse micelles revealed Sn percentages much above 20%. This was attributed to the solubility difference of the precursors leading to displacing or preventing of pre- cursor loading into the reverse micelles. The change of the stirring time, the micelles concentration, the sequence of precursors loading, and the weight of precursors were not found to affect the Sn concentration; moreover, large variations in Sn concentrations were observed. From quantitative nano mechanical testing of the micelles, a maximum load amount for the precursors was observed, confirming that the high concentration of Sn was likely due to the solubility differences between the precursors and their ability to penetrate the micelle. By manipulating the nanoparticles distribution through spin coating speeds, micelles concentration, and deposited volume, several degrees of order were obtained, though hexagonal packing was not observed. In general, even though Sn concentration were found to be above 20%, nanoparticles were successfully fabricated with reverse micelles, confirming that the reverse micelle technique is a good strategy for future studies of roughness. / Thesis / Master of Applied Science (MASc)

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Doctor of Philosophy / Department of Chemistry / Takashi Ito / This dissertation describes the fabrication and characterization of nanoscale structures in commercially available polymers via multiphoton ablation and bottom-up self assembly techniques. High-resolution surface imaging techniques, such as atomic force microscopy (AFM) and chemical force microscopy (CFM) were used to characterize the physical features and chemical properties, respectively, of these nanoscale structures. Fabrication using both top-down and bottom-up methods affords flexibility in that top-down allows random, user-defined patterning whereas bottom-up self assembly produces truly nanoscale (1-100nm) uniform features. Multiphoton induced laser ablation, a top-down method, was used to produce random sub-micron scale features in films of poly(methylmethacrylate) (PMMA), polystyrene (PS), poly(butylmethacrylate) (PBMA) and poly[2-(3-thienyl)ethyloxy-4-butylsulfonate] (PTEBS). Features with 120-nm lateral resolution were obtained in a PMMA film which was concluded to be the best polymer for use with this method. It was also found that etching resolution was highest for polymers having high glass transition temperatures, low molecular weights and no visible absorption. Bottom-up self assembly of polystyrene-poly (methylmethacrylate) (PS-b-PMMA) diblock copolymer and UV/acetic acid treatment produced nanoscale cylindrical domains supported by a substrate. AFM imaging at the free surface showed metastable vertical PMMA domain orientation on gold substrates. In contrast, horizontal orientation was obtained on oxide-coated silicon regardless of surface roughness and annealing conditions. The horizontal domain orientation on silicon substrates was ideal to probe simultaneously the difference in surface charge and hydrophilicity of the two distinct nanoscale domains of UV/AcOH treated PS-b-PMMA films. CFM on UV/acetic acid etched PS-b-PMMA revealed the presence of –COO- groups which were found to be more abundant inside the etched trenches than on the unetched PS matrix as shown by ferritin adsorption onto etched PS-b-PMMA. Lastly, the PS-b-PMMA was cast as a free-standing monolith at the end of a quartz micropipette. AFM revealed circular PMMA dots at the free surface, indicating alignment parallel to the long axis of capillary. Ion conductance within nanochannels indicated surface –charge governed ion transport at low KCl concentrations and flux of negatively-charged sulphorhodamine dye demonstrated the permselective nature of nanochannels.

Doctor of Philosophy / Department of Chemistry / Takashi Ito / We have investigated the orientation of cylindrical domains in thin films of a polystyrene–poly(methylmethacrylate) diblock copolymer (PS-b-PMMA) on planar substrates having different surface roughnesses and hydrophilicities. The research in this dissertation covers the substrate surface modifications, the enhancement of the diblock copolymer film coating, and the refinement of the treatments leading to nanoporous material. Treatment of the substrate with organic mercaptans forming self-assembled-monolayer (SAM), leading to various hydrophilicities of the surfaces, was inconclusive as far as orienting the PMMA domains in the PS matrix due to thermal instability of some thiols. This directed us to a different approach involving substrate roughness. PS-b-PMMA films of 20~200 nm thick were prepared via spin-coating on silicon, gold or indium tin oxide (ITO) substrates, and annealed in vacuum at 170 °C for 60 hours to induce the formation of cylindrical PMMA domains. Atomic force microscopy (AFM) images indicated the domain orientation at the free surface. In PS-b-PMMA films much thicker than the domain periodicity (L0), the domains were oriented perpendicularly to the free surface regardless of underlying substrates, reflecting the balanced interactions of PS and PMMA blocks at the polymer–vacuum interface. In films having thickness similar to L0, vertically oriented domains were observed on the Au and ITO surfaces that are covered with nanoscale grains, whereas horizontal domains were observed on the smooth Si substrates. In particular, the cylindrical PMMA domains were efficiently perpendicularly aligned when the grain size nearly was equal to L0. The perpendicular domain alignment induced by the substrate roughness was corroborated using cyclic voltammetry (CV) for gold substrates coated with PS-b-PMMA films whose PMMA domains were removed by UV and subsequent acetic acid treatments. The CV data also suggested that the PMMA domains were successfully removed, leaving a nanoporous stable PS matrix on the substrate.

Crosslinkable and pH-sensitive amphiphilic block copolymers are promising candidates to establish pH-stable and permeable vesicles for synthetic biology. Here, we report the fabrication of crosslinked and pH-stable polymersomes as swellable vesicles for the pH-dependent loading and release of small dye molecules. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

La nanochimie et l’auto-assemblage sont des voies prometteuses de fabrication de matériaux nanostructurés aux propriétés optiques innovantes dans le domaine visible. Dans cette étude, des nanocomposites plasmoniques anisotropes sont formulés en introduisant sélectivement des nanoparticules métalliques dans des phases ordonnées de copolymères diblocs symétriques selon différentes stratégies d’incorporation. Pour la stratégie de post-incorporation, des nanoparticules d’or présynthétisées en milieu aqueux sont introduites sélectivement dans des phases pré-ordonnées d’un copolymère dibloc amphiphile. L’incorporation directe consiste àmélanger des nanoparticules d’or présynthétisées et un copolymère dibloc dans un solvant commun.La synthèse in situ de nanoparticules consiste à réduire des précurseurs métalliques préalablement introduits dans un des deux blocs d’un copolymère via une étape de réduction. Nous étudions, en particulier, comment la taille des nanoparticules d’or et leur fraction volumique influencent la nanostructure et les propriétés optiques de ces films nanocomposites. La morphologie des films macroscopiques est étudiée par microscopie électronique à transmission et diffusion des rayons Xaux petits angles. Les films minces de nanocomposites sont caractérisés structurellement parmicroscopie à force atomique, microscopie électronique à transmission et réflectivité des rayons X. Les indices optiques déterminés par ellipsométrie spectroscopique peuvent être décrits par un modèle de Maxwell-Garnett, prenant éventuellement en compte de façon phénoménologique les effets de couplage entre nanoparticules d’or. / Nanochemistry and self-assembly are promising ways to fabricate nanostructuredmaterials with innovative optical properties for visible light. In this work, anisotropic plasmonicnanocomposites are formulated by selectively introducing metallic nanoparticles in ordered phasesof symmetric dibloc copolymers with different strategies. For the strategy of post-incorporation, presynthesizedgold nanoparticles in aqueous medium are selectively introduced in pre-ordered phasesof an amphiphilic dibloc copolymer. Direct incorporation consists in mixing pre-synthesized goldnanoparticles and dibloc copolymer in a common solvent. In situ synthesis of nanoparticles consistsin reducing metallic precursors previously introduced in one of two blocks of a copolymer via areduction step. The influence of the size and the volume fraction of gold nanoparticles on thenanostructure and the optical properties of the nanocomposite films have been particularly studied.Morphology of macroscopic films is studied by transmission electron microscopy and small angle Xrayscattering. The nanocomposite thin films are structurally characterized by force atomicmicroscopy, transmission electron microscopy and X-ray reflectivity. The optical indices obtained byspectroscopic ellipsometry can be described with Maxwell-Garnett models, which can take intoaccount phenomenologically the effects of coupling between gold nanoparticles.