Ring‐shaped nanostructures can focus, filter, and manipulate electromagnetic waves, but are challenging to incorporate into devices using standard nanofabrication techniques. Directed self‐assembly (DSA) of block copolymers (BCPs) on lithographically patterned templates has successfully been used to fabricate concentric rings and spirals as etching masks. However, this method is limited by BCP phase behavior and material selection. Here, a straightforward approach to generate ring‐shaped nanoparticle assemblies in thin films of supramolecular nanocomposites is demonstrated. DSA is used to guide the formation of concentric rings with radii spanning 150–1150 nm and ring widths spanning 30–60 nm. When plasmonic nanoparticles are used, ring nanodevice arrays can be fabricated in one step, and the completed devices produce high‐quality orbital angular momentum (OAM). Nanocomposite DSA simplifies and streamlines nanofabrication by producing metal structures without etching or deposition steps; it also introduces interparticle coupling as a new design axis. Detailed analysis of the nanoparticle ring assemblies confirms that the supramolecular system self‐regulates the spatial distribution of its components, and thus exhibits a degree of flexibility absent in DSA of BCPs alone, where structures are determined by polymer‐pattern incommensurability. The present studies also provide guidelines for developing self‐regulating DSA as an alternative to incommensurability‐driven methods.
Template‐free fabrication of non‐spherical polymeric nanoparticles is desirable for various applications, but has had limited success owing to thermodynamic favorability of sphere formation. Herein we present a simple way to prepare cubic nanoparticles of block copolymers by self‐assembly from aqueous solutions at room temperature. Nanocubes with edges of 40–200 nm are formed spontaneously on different surfaces upon water evaporation from micellar solutions of triblock copolymers containing a central poly(ethylene oxide) block and terminal trimethylene carbonate/dithiolane blocks. These polymers self‐assemble into 28±5 nm micelles in water. Upon drying, micelle aggregation and a kinetically controlled crystallization of central blocks evidently induce solid cubic particle formation. An approach for preserving the structures of these cubes in water by thiol‐ or photo‐induced crosslinking was developed. The ability to solubilize a model hydrophobic drug, curcumin, was also explored.
more » « less- NSF-PAR ID:
- 10047118
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie
- Volume:
- 129
- Issue:
- 51
- ISSN:
- 0044-8249
- Page Range / eLocation ID:
- p. 16575-16580
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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