Abstract Gyroid optical metamaterials consist of triply periodic chiral networks that are attractive photonic structures due to the combination of intriguing optical properties and spontaneous self‐assembly‐based fabrication routes using materials such as block copolymers. A previous experimental investigation found that gyroid metamaterials support strong circular dichroism, beyond what simulations only considering bulk interactions predict. In this work, simulations are used to unravel the contributions of bulk and surface interactions on the circular dichroism spectra of silver‐infilled gyroid metamaterial films. It is found that surface interactions have a significant, often dominating, contribution to circular dichroism. The relative strength of bulk and surface contributions can be tuned by controlling the crystallographic orientation, termination plane of the film, thickness, metal volume fraction, and defect density. Importantly, the dominance of surface interactions allows double gyroids, which are achiral in the bulk, to support strong circular dichroism responses withg‐factor magnitudes as large as 0.25.
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Flexible Block Copolymer Metamaterials Featuring Hollow Ordered Nanonetworks with Ultra‐High Porosity and Surface‐To‐Volume Ratio
Abstract By utilizing bicontinuous and nanoporous ordered nanonetworks, such as double gyroid (DG) and double diamond (DD), metamaterials with exceptional optical and mechanical properties can be fabricated through the templating synthesis of functional materials. However, the volume fraction range of DG in block copolymers is significantly narrow, making it unable to vary its porosity and surface‐to‐volume ratio. Here, the theoretically limited structural volume of the DG phase in coil‐coil copolymers is overcome by enlarging the conformational asymmetry through the association of mesogens, providing fast access to achieving flexible structured materials of ultra‐high porosities. The new materials design, dual‐extractable nanocomposite, is created by incorporating a photodegradable block with a solvent‐extractable mesogen (m) into an accepting block, resulting in a new hollow gyroid (HG) with the largely increased surface‐to‐volume ratio and porosity of 77 vol%. The lightweight HG exhibits a low refractive index of 1.11 and a very high specific reduced modulus, almost two times that of the typical negative gyroid (porosity≈53%) and three times that of the positive gyroid (porosity≈24%). This novel concept can significantly extend the DG phase window of block copolymers and the corresponding surface‐to‐volume ratio, being applicable for nanotemplate‐synthesized nanomaterials with a great gain of mechanical, catalytic, and optoelectronic properties.
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- Award ID(s):
- 2105296
- PAR ID:
- 10612279
- Publisher / Repository:
- Wiley-VCH
- Date Published:
- Journal Name:
- Small
- Edition / Version:
- 1
- Volume:
- 20
- Issue:
- 14
- ISSN:
- 1613-6810
- Page Range / eLocation ID:
- 22-32
- Subject(s) / Keyword(s):
- dual-extractable, gyroid, hollow nanonetworks, metamaterials, nanoporous
- Format(s):
- Medium: X Size: 3.4MB Other: csv
- Size(s):
- 3.4MB
- Sponsoring Org:
- National Science Foundation
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