Plenty of Room at the Top: A Multi‐Scale Understanding of nm‐Resolution Polymer Patterning on 2D Materials

Abstract

Lamellar phases of alkyldiacetylenes in which the alkyl chains lie parallel to the substrate represent a straightforward means for scalable 1‐nm‐resolution interfacial patterning. This capability has the potential for substantial impacts in nanoscale electronics, energy conversion, and biomaterials design. Polymerization is required to set the 1‐nm functional patterns embedded in the monolayer, making it important to understand structure–function relationships for these on‐surface reactions. Polymerization can be observed for certain monomers at the single‐polymer scale using scanning probe microscopy. However, substantial restrictions on the systems that can be effectively characterized have limited utility. Here, using a new multi‐scale approach, we identify a large, previously unreported difference in polymerization efficiency between the two most widely used commercial diynoic acids. We further identify a core design principle for maximizing polymerization efficiency in these on‐surface reactions, generating a new monomer that also exhibits enhanced polymerization efficiency.

Nanometer-scale patterning of hard and soft interfaces: from photolithography to molecular-scale design

“…12,120 Characterizing chemistry at soft, porous interfaces is an ongoing challenge; however, the sPDA transfer approach benefits from the ability to readily extract information regarding nm-scale interface structure on HOPG prior to transfer, and correlate with interface properties on the soft material after transfer. 121,122 For instance, individual polymerization events on HOPG can be characterized by AFM, based on Å-scale topographical protrusion of the sPDA backbone following polymerization. Correlating nanoscale extent of polymerization on HOPG (Fig.…”