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    Sitting Phase Monolayers of Polymerizable Phospholipids Create Dimensional, Molecular-Scale Wetting Control for Scalable Solution Based Patterning of Layered Materials

    Year: 2017

    Journal: ACS Appl. Mater. Interfaces, Volume 9, JUN 7, page 19326–19334

    Authors: Choong, Shi Wah; Russell, Shane R.; Bang, Jae Jin; Patterson, Justin K.; Claridge, Shelley A.

    Organizations: NSF CAREER award [NSF-CHE 1555173]; W. Brooks Fortune Predoctoral Fellowship; Frederick N. Andrews Predoctoral Fellowship; NSF-CHE REU [1560244]; NSF MRI [NSF-CHE 1531767]

    Keywords: self-assembly; noncovalent functionalization; layered materials; anisotropic wetting; diynoic phospholipid; directional wetting; nanoscale wetting; self-assembled monolayer

    The use of dimensionally ordered ligands on layered materials to direct local electronic structure and interactions with the environment promises to streamline integration into nanostructured electronic, optoelectronic, sensing, and nanofluidic interfaces. Substantial progress has beers made in using ligands to control substrate electronic structure. Conversely, using the exposed face of the ligand layer to structure wetting and binding interactions, particularly with scalable solution- or spray processed materials, remains a significant challenge. However, nature routinely utilizes wetting control at scales from nanometer to micrometer to build interfaces of striking geometric-precision and functional complexity, suggesting the possibility Of leveraging similar control in synthetic materials. Here, we assemble striped "sitting" phases of polymerizable phospholipids on highly Oriented pyrolytic graphite, producing a surface consisting of 1 nm wide hydrophilic stripes alternating with 5 rim wide hydrophobic stripes. Protruding, strongly wetting headgroup chemistries in these monolayers enable formation of rodlike wetted patterns with widths as little as similar to 6 nm and lengths up to 100 nm from high-surface-tension liquids (aqueous solutions, of glycerol) commonly utilized to assess interfacial wetting properties at larger length scales. In contrast, commonly used lying down phases of diynoic acids with in-plane headgroups do not promote droplet sticking or directional spreading. These results point to a broadly applicable strategy for achieving high-resolution solution-based patterning on layered materials, utilizing nanometer-wide patterns of protruding charged functional groups in a noncovalent monolayer to define pattern edges.
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