Controlling the orientation of liquid crystal molecules in LC displays is extremely important for optimizing device performance. The method most commonly used in industry today involves rubbing the surface of the polymer-coated glass substrates used in the displays with a velvet cloth to create microscopic grooves. Berreman theory states that the liquid crystal molecules then align along the direction of the grooves. Alternatively, some literature shows that the friction caused by rubbing aligns the polymer chains in the surface layer which then attract and align the liquid crystal molecules along the direction of the chains. Even now, it is still unclear exactly how the process of rubbing the surface causes the liquid crystal molecules to align in an orderly manner. This thesis describes a systematic study of the physical and chemical influence of the substrate on the alignment and orientation of liquid crystal molecules. We used Fourier Transform Infrared spectroscopy (FTIR) to identify surface chemistry, contact angle measurements to determine the surface energy, and atomic force microscopy (AFM) to observe the alignment of liquid crystal on the surfaces. In the course of this study, we have gained insight into how the physical and chemical properties of the surface affect the molecular arrangement in the solid-liquid interface. Our results can be applied not only to LCD technology, but more generally to biochips and biosensor devices.

Atomic force microscopy (AFM) is an important technology that allows researchers to probe local surface properties at nanometer length scales. In addition to surface topography, the AFM can probe many types of tip-surface interactions (including adhesion and friction) to gain a better understanding of the chemical properties of surfaces. This thesis contains two experiments which utilize AFM to in addition to several other techniques to study (1) Self Assembled Monolayer (SAM) formation and corrosion and (2) intermolecular and surface/molecular effects on gramicidin film formation and molecular orientation. In the first experiment, N-octadecyltrichlorosilane (OTS) molecules were self-assembled onto silicon samples. We observed that OTS required a very short time (about 15 seconds) to complete the formation of the monolayer on surface. However, this SAM film was highly susceptible to corrosion by the strong oxidant (KMnO4), resulting in a chemical change to the film from hydrophobic functional groups (CH3) to hydrophilic functional groups (OH). In subsequent experiments, we observed that if the SAMs were formed using longer exposure times (about 24 hours), they were highly resistant to corrosion. Fourier Transform Infrared Spectroscopy (FTIR) and X-Ray Photoelectron Spectroscopy (XPS) also showed that the 24 hour growth SAM films were densely packed. These results indicate that SAM films based on organosilane molecules can protect the surface from corrosion, and further that more densely packed SAMs exhibit better anti-corrosion performance than less dense films. In the second experiment, the antibacterial peptide Gramicidin was used to study how intermolecular and surface energy properties can influence the aggregation and film formation of molecules on several surfaces. Gramicidin has a unique physical and chemical structure with hydrophobic side chain and hydrophilic ends. Here, we have used three different substrates (Silicon, Mica, and Graphite) to study intermolecular interactions, aggregation, and orientation of Gramicidin peptide. Langmuir-Blodgett methods were also used to study aggregation and molecular orientation at the solid-liquid interface.

Self assembled monolayer films (SAMs) deposited on silicon surfaces have gained considerable interest due to their ability to modify surface properties for advanced applications in sensors, MEMS, and NEMS devices. These molecular films are typically deposited on silicon surfaces from solution using a variety of solvents, which can influence the molecular packing and quality of the films. To better understand these effects, we have performed a systematic solvent effect study of the growth of n-Octadecyltrichlorosilane (OTS) on silicon substrates using chloroform, dichloromethane, toluene, benzene and hexadecane. The films were characterized using contact angle measurements, Fourier Transform Infrared Spectroscopy (FTIR), and Atomic Force Microscopy (AFM) to evaluate the SAM growth rate and film quality. Lateral Force Microscopy (LFM) and transmission FTIR were used to characterize the molecular packing. Finally, we used AFM to make adhesion measurements on the films and correlated these results with friction data. These techniques provide a means to characterize the local nanoscale packing of the films. The Hertzian contact model was used to model and describe the adhesion and friction result. Our results show that using hexadecane as the solvent produced OTS films with the highest density molecular packing. By comparing to Langmuir-Blodgett SAM film deposition methods, we show that it is the intermolecular interaction between the solvent molecules and OTS that determines this density. Thus, the structure and chemical properties of the solvent molecule strongly influences the molecular packing, quality, and performance of the SAM film.

No description available.

Alkanethiols spontaneously assembles from solution or vapour on oxide free metal surfaces resulting in a close-packed molecular stuctures with a high degree of orientation and molecular order. In this study, inkjet printing technique is used to immobilize monolayers of alkanethiols on gold electrodes. The quality of the inkjetted monolayers are analyzed by electrochemical methods, i.e. cyclic voltammetry and electrochemical impedance spectroscopy, and by Polarization Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRRAS) which show a similar molecular quality to those produced by immersion technique, the standard technique. The kinetic and mass transfer behaviours of micro-scale structures of inkjetted monolayers, e.g. bands and dots array electrodes, are explored by electrochemical methods. The microscale inkjetted structures of monolayers are of interest in the fields of microelectronic devices (e.g. chemical and biosensors) and optoelectronic devices. Taking benefits from multichannel existing in the printhead, mixtures of SAMs are demonstrated. Mixing of monolayers differing in functional groups provides a model surface to study interface phenomena at molecular level such as ion permeation, selective chemical binding, and electron transfer kinetic.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第17886号 / 工博第3795号 / 新制||工||1580(附属図書館) / 30706 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 杉村 博之, 教授 酒井 明, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

No description available.

No description available.

This study describes the covalent and the electrostatic attachment of molecules, nano-particles, and proteins to patterned self-assembled monolayers. A scanning probe nanografting technique was employed to produce patterns of various sizes, down to 10 nm. Thus, we are able to demonstrate a degree of surface patterning which is an order of magnitude smaller than that used in the semiconductor industry. One efficient strategy for creating chemically specific nanostructures is to use the extraordinary catalytic properties of enzymes. However, as the dimension of a catalyst patch is reduced down to nanometer scale, it is difficult to detect the very low concentration of product. This study resolves the problem by developing a new strategy: the surface trapping of a product generated by a nanometer-scale patch of surface-bound enzyme. An array of proteins finds use when the array contains a number of different proteins. Toward this end, a new and convenient method for immobilizing enzymes is developed, which will allow the preparation of thin films containing several different catalytically-active enzymes on the nanoscale. The disadvantage of scanning probe nanografting technique is that the AFM tip loses resolution through wear during the patterning procedure. This study examines the possibility of developing a new AFM lithographic method to avoid wear: the use of enzymes covalently attached to a tip as a site-specific catalyst. / Ph. D.

The compounds 12-phenoxy-dodecane-1-thiol, 4-dodecyloxymercaptophenol and 3-dodecyloxymercaptophenol have been synthesized using a novel synthesis to investigate the effect that the orientation of the functional group has on surface acidity. 3-dodeycloxymercaptophenol and 4-dodecyloxymercaptophenol differ in that the hydroxyl group is substituted on different carbons of the benzene ring. The difference in substitution patterns should present the hydroxyl group in different orientations in the interface between a self-assembled monolayer of the compound and aqueous solutions buffered over a pH range of 3-13. By preparing self-assembled monolayers of these molecules on gold substrates, the ability of the hydroxyl group to donate its proton was shown to depend on the hydroxyl group substitution pattern on the benzene ring through contact angle titration experiments. 3-dodecyloxymercaptophenol clearly showed plateaus at low and high pH with a broad transition between the two plateaus. 4-dodecyloxymercaptophenol showed a clear plateau at low pH but not at high pH, although a transition was observed. Using infrared spectroscopy, it was further shown that the long molecular axis of the benzene ring in 3-dodecyloxymercaptophenol was tilted from the surface normal by 55°. The short molecular axis of the ring was twisted out of the plane of the surface by 28° for self-assembled monolayers of this molecule on gold substrates. In contrast, the tilt angle of 4-dodecyloxymercatophenol was measured to be 46° and was twisted out of the surface plane by 36°. It was also found from cyclic voltammetry experiments in 0.5 M KOH, that the ionized monolayers of 4-dodecyloxymercaptophenol were 2.3 kJ/mol less stable than monolayers of 3-dodecyloxymercaptophenols. This finding suggests that hydrogen bonding and other intermolecular interactions in 4-dodecyloxymercaptophenol are greater than in 3-dodecyloxymercaptophenol. / Ph. D.