(764f) Exploring the Limit of Self-Assembly: High-? Block Oligomers

Block polymer-based templates with strongly incompatible segments and short chain lengths have gathered much attention due to their micro-phase separations and resulting domains with extremely small feature sizes. Nanopatterning using directed self-assembly of such materials is under consideration as a cost-effective route to achieving sub-10 nm feature sizes, targeted for microelectronic devices with faster processing speed and higher storage density.¹ Motivated by further miniaturization of domain size, our recent work utilizing atomistic-scale molecular dynamics simulations identified a class of amphiphilic oligomers capable of forming ordered lamellar and cylindrical morphologies with domain periods as small as 3 nm.² We integrated theoretical and experimental work focusing on a sugar-derived amphiphile with an alkyl tail, and found a lamellar morphology induced by thermotropic self-assembly with a 3.5 nm period and 1.1 nm domains. In addition, structural details from simulations are in remarkable agreement with the experimental results.

1. Sinturel, C.; Bates, F. S.; Hillmyer, M. A. High χ-Low N Block Polymer: How Far can We Go? ACS Macro Lett. 2015, 4, 1044−1050.
2. Chen, Q. P.; Barreda, L.; Oquendo, L. E.; Hillmyer, M. A.; Lodge, T. P.; Siepmann. J. I. Computational Design of High-χ Block Oligomers for Accessing 1 nm Domains. ACS Nano, 2018, 12, 4351–4361.