<p>During the past two decades, soft lithographic techniques that circumvent the limitations of photolithography have emerged as important tools for the transfer of patterns with sub-micron dimensions. Among these techniques, microcontact printing (uCP) has shown special promise. In uCP, an elastomeric stamp is first inked with surface-reactive molecules and placed in contact with an ink-reactive surface, resulting in pattern transfer in the form of self-assembled monolayers in regions of conformal contact. The resolution in uCP is ultimately limited to the diffusion of ink and the elastomechanical properties of the bulk stamping material. </p> <p>One way to improve resolution is to eliminate diffusion by using inkless methods for pattern transfer. Inkless catalytic-uCP uses a chemical reaction between a stamp-immobilized catalyst and surface bearing cognate substrate to transfer pattern in the areas of conformal contact. By using pre-assembled cognate surfaces, the approach extends the range of surfaces readily amenable to patterning while obviating diffusive resolution limits imposed by traditional uCP. </p> <p>In this thesis, we report two methods using inkless catalytic uCP: biocatalytic-uCP utilizes an immobilized enzyme as a catalyst whereas catalytic-uCP utilizes an immobilized small molecule as a catalyst, such as an acid or base. Both catalytic techniques demonstrate pattern transfer at the microscale while using unconventional, acrylate-based stamp materials. Previous results produced with catalytic-uCP have shown pattern transfer with sub-50 nm edge resolution. In this demonstration of catalytic-uCP, we use the technique to demonstrate a bi-layered patterning technique for H-terminated silicon, the foremost material in semi-conductor fabrication. This technique simultaneously protects the underlying silicon surface from degradation while a highly-reactive organic overlayer remains patternable by acidic-functionalized PU stamps. Lines bearing widths as small as 150 nm were reproduced on the reactive SAM overlayer, which would not be possible without circumvention of diffusion. Before and after patterning, no oxidation of the underlying silicon was observed, preserving desired electronic properties throughout the whole process. This bi-patterning technique could be extended to other technologically-relevant surfaces for further application in organic-based electronic devices and other related technologies.</p> / Dissertation

Printing ink is a main component of the modern printer, and it has always been throughout the history of printing. Ink and toners are expensive replaceable components that inkjet and laser printers cannot function without. The digital printing industry, which is majorly composed of monochrome printing, is expected to increase by 225% by 2024 from a 2013 baseline (Smithers et al., 2014). Expenses aside, toner cartridges and ink cartridges pose an overlooked threat to the environment. Manufacturing, packaging, transporting, and waste disposal of printer ink and toners result in carbon dioxide emissions. The complete elimination of ink in monochrome printing is potentially viable with the patented new discoloration technique. The patent studies a discoloration method by carbonizing a paper’s surface (Alhashem et al., 2015). The printing method optimizes surface paper pyrolysis via laser heating. The aim is obtaining the darkest possible shade without compromising paper quality. The challenge is in creating a printed area from the paper material itself, rather than depositing ink on paper. A 75-watt CO2 laser engraving machine emitting a 10.6 μm wavelength beam for heating is used with low power settings to carbonize a fraction of the paper surface. The carbonization is essentially a combustion reaction. Solid fuel burns in three stages: drying, devolatilization (pyrolysis, or distillation phase), and lastly, the char (charcoal) combustion. These stages are driven by heat from the CO2 laser. Moving the laser rapidly above the paper surface arrests the reaction at the second stage, after the formation of blackened char. The control variables in the experimental method are laser power, speed, and the vertical position that affects the laser intensity. Computer software controls these variables. The discoloration of paper is quantified by measuring the light absorptivity using a UV-Vis-IR Spectrometer.