Effects of co-ordination number on the nucleation behaviour in many-component self-assembly

TL;DR

This study uses lattice Monte Carlo simulations to explore how the co-ordination number of building blocks influences nucleation barriers and self-assembly efficiency in complex, addressable nanostructures, revealing that higher co-ordination numbers require greater driving forces but still enable successful, modular assembly.

Contribution

It demonstrates how changing the co-ordination number affects nucleation behaviour and self-assembly pathways in multi-component structures, extending understanding beyond tetrahedral systems.

Findings

Higher co-ordination numbers increase nucleation free-energy barriers.

Structures with higher co-ordination require greater supersaturation for nucleation.

Successful self-assembly of high co-ordination structures with modular, high-resolution features.

Abstract

We report canonical and grand-canonical lattice Monte Carlo simulations of the self-assembly of addressable structures comprising hundreds of distinct component types. The nucleation behaviour, in the form of free-energy barriers to nucleation, changes significantly as the co-ordination number of the building blocks is changed from 4 to 8 to 12. Unlike tetrahedral structures - which roughly correspond to DNA bricks that have been studied in experiment - the shapes of the free-energy barriers of higher co-ordination structures depend strongly on the supersaturation, and such structures require a very significant driving force for structure growth before nucleation becomes thermally accessible. Although growth at high supersaturation results in more defects during self-assembly, we show that high co-ordination number structures can still be assembled successfully in computer simulations and that they exhibit self-assembly behaviour analogous to DNA bricks. In particular, the self-assembly remains modular, enabling in principle a wide variety of nanostructures to be assembled, with a greater spatial resolution than is possible in low co-ordination structures.