Functionalization and Patterning of Self-Assembled Monolayers and Polymer Brushes Using Microcontact Chemistry.

Because the surface connects a material to its environment, the functionalization, modification, and patterning of surfaces is key to a wide range of materials applied in microelectronics, displays, sensing, microarrays, photovoltaics, catalysis, and other fields. Self-assembled monolayers (SAMs), which can be deposited on a wide range of inorganic materials, are only a few nanometers thick, yet they can radically change the properties of the resulting interface. Alternatively, thin polymer films composed of polymer brushes grown from the surface provide a more robust molecular modification of inorganic materials. For many applications, patterned SAMs or polymer brushes are desired. Over the past decade, our group has shown that both SAMs as well as polymer brushes can be patterned very efficiently using microcontact printing. In microcontact printing, a molecular "ink" is deposited on a suitable substrate using a microstructured elastomer stamp, which delivers the ink exclusively in the area of contact between stamp and substrate. In contrast to most types of lithography, microcontact printing does not require expensive equipment. Our work has shown that "microcontact chemistry" is a powerful additive surface patterning method, in which molecular inks react with a precursor SAM during printing so that surfaces can be modified with various orthogonal functional groups or molecular recognition sites in microscale patterns. Functional groups include reactive groups for click chemistry or photochemistry and initiators for radical polymerization. Molecular recognition sites include host-guest chemistry as well as biochemical ligands such as carbohydrates and biotin. In this Account, we present an overview of our research in this area including selected examples of work by other groups. In the first part, we review our work on the patterning of SAMs using microcontact chemistry, with a focus on click chemistry and photochemistry. We will show how cycloadditions, thiol-ene reactions, and tetrazole chemistry can be used to obtain versatile surface patterns. In the second part, we demonstrate that microcontact chemistry can be used to pattern polymer brushes. Among others, initiators for surface-induced nitroxide-mediated polymerization and atom transfer polymerization were printed and used to grow patterned polymer brushes with molecular recognition groups suitable for responsive surface adhesion. In the third part, we describe how SAMs and polymer brushes can be printed on microparticles instead of flat substrates so that Janus particles with functional patches can be obtained. Finally, we present a brief outlook on further developments expected in this field.