Properties arising from ordered periodic mesostructures are often obscured by small, randomly oriented domains and grain boundaries. Bulk macroscopic single crystals with mesoscale periodicity are needed to establish fundamental structure–property correlations for materials ordered at this length scale (10–100 nm). A solvent‐evaporation‐induced crystallization method providing access to large (millimeter to centimeter) single‐crystal mesostructures, specifically bicontinuous gyroids, in thick films (>100 µm) derived from block copolymers is reported. After in‐depth crystallographic characterization of single‐crystal block copolymer–preceramic nanocomposite films, the structures are converted into mesoporous ceramic monoliths, with retention of mesoscale crystallinity. When fractured, these monoliths display single‐crystal‐like cleavage along mesoscale facets. The method can prepare macroscopic bulk single crystals with other block copolymer systems, suggesting that the method is broadly applicable to block copolymer materials assembled by solvent evaporation. It is expected that such bulk single crystals will enable fundamental understanding and control of emergent mesostructure‐based properties in block‐copolymer‐directed metal, semiconductor, and superconductor materials.
Mesoscale order can lead to emergent properties including phononic bandgaps or topologically protected states. Block copolymers offer a route to mesoscale periodic architectures, but their use as structure directing agents for metallic materials has not been fully realized. A versatile approach to mesostructured metals via bulk block copolymer self‐assembly derived ceramic templates, is demonstrated. Molten indium is infiltrated into mesoporous, double gyroidal silicon nitride templates under high pressure to yield bulk, 3D periodic nanocomposites as free‐standing monoliths which exhibit emergent quantum‐scale phenomena. Vortices are artificially introduced when double gyroidal indium metal behaves as a type II superconductor, with evidence of strong pinning centers arrayed on the order of the double gyroid lattice size. Sample behavior is reproducible over months, showing high stability. High pressure infiltration of bulk block copolymer self‐assembly based ceramic templates is an enabling tool for studying high‐quality metals with previously inaccessible architectures, and paves the way for the emerging field of block‐copolymer derived quantum metamaterials.
more » « less- NSF-PAR ID:
- 10450863
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 31
- Issue:
- 23
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Superconducting quantum metamaterials are expected to exhibit a variety of novel properties, but have been a major challenge to prepare as a result of the lack of appropriate synthetic routes to high‐quality materials. Here, the discovery of synthesis routes to block copolymer (BCP) self‐assembly‐directed niobium nitrides and carbonitrides is described. The resulting materials exhibit unusual structure retention even at temperatures as high as 1000 °C and resulting critical temperature,
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