title: Controlled hierarchical assembly of gold nanoparticles in macroscopic films: from densely packed monolayers to networks of micropores and nanobundles.
abstract: The present study demonstrates the ability of excess, weakly amphiphilic n-alkanethiols (n = 4, 12, 18) and solvent composition to tune through a wide range of large-scale, macroscopic architectures formed by alkanethiol-capped Au nanoparticles (NPs). Both the alkanethiols and NPs are significantly hydrophobic species and compete for surface area at an air-water interface. When solutions of the two species are spread on a large (50 cm2) water surface in a Teflon well, a thin film forms and exhibits co-existing macroscopic regions with various distinct NP self-assembled architectures, namely a close packed monolayer, a network phase characterized by micron-sized pores (micropores) surrounded by quasi-linear bundles of nanoparticles, and finally aggregates. We hypothesize that the co-existence of various NP architectures results from fast, non-uniform evaporation across the large water surface. When solutions are instead deposited on a smaller (5 cm2) water surface contained within a Teflon ring to control the water surface curvature and the evaporation rate is slowed, we show for the first time that NPs form macroscopically uniform self-assemblies whose architectures can be tuned from monolayers → monolayers with micropores → extended micropore/NP bundle networks by varying excess alkanethiol concentration and solvent composition. We propose that competition between NPs and excess alkanethiols for water surface area, and alkanethiol self-assembly as well as solvent dewetting play important roles in the formation of the network phase, and discuss a potential mechanism for its formation.
authors.affiliation: Department of Chemistry, University of Toronto, Editor: 80 St. George St, Toronto, Ontario M5S 3H6, Canada. adhirani@chem.utoronto.ca.
authors.forename: Steven
authors.initials: S
authors.lastname: Gravelsins
authors.affiliation: Department of Chemistry, University of Toronto, Editor: 80 St. George St, Toronto, Ontario M5S 3H6, Canada. adhirani@chem.utoronto.ca.
authors.forename: Minhal
authors.initials: M
authors.lastname: Hasham
authors.affiliation: Department of Chemistry, University of Toronto, Editor: 80 St. George St, Toronto, Ontario M5S 3H6, Canada. adhirani@chem.utoronto.ca.
authors.forename: Yi
authors.initials: Y
authors.lastname: Lin
authors.affiliation: Department of Chemistry, University of Toronto, Editor: 80 St. George St, Toronto, Ontario M5S 3H6, Canada. adhirani@chem.utoronto.ca.
authors.forename: Kevin
authors.initials: K
authors.lastname: Yu
authors.affiliation: Department of Chemistry, University of Toronto, Editor: 80 St. George St, Toronto, Ontario M5S 3H6, Canada. adhirani@chem.utoronto.ca.
authors.forename: Monique
authors.initials: M
authors.lastname: Tie
authors.affiliation: Department of Chemistry, University of Toronto, Editor: 80 St. George St, Toronto, Ontario M5S 3H6, Canada. adhirani@chem.utoronto.ca.
authors.forename: Cynthia
authors.initials: C
authors.lastname: Goh
authors.affiliation: Department of Chemistry, University of Toronto, Editor: 80 St. George St, Toronto, Ontario M5S 3H6, Canada. adhirani@chem.utoronto.ca.
authors.forename: Al-Amin
authors.identifier: http://orcid.org/0000-0003-3257-4327
authors.initials: AA
authors.lastname: Dhirani