Symmetry in Seeded Metal Nanocrystal Growth
Abstract
Symmetry underpins the structure and function of the world around us and is also captured in modern nanomaterials, where changing the symmetry of a nanocrystal or the interparticle spacing and orientation of nanocrystal building blocks in a superlattice can give new function. However, the synthesis and assembly of nanocrystals have been limited largely to simple compositions and structures. It remains a grand challenge to achieve nanocrystals with compositional and structural complexity while maintaining the monodispersity required for their use. This Account will illustrate through recent examples that seeded methods enable the synthesis of compositionally and structurally complex multimetallic crystals with defined and predictable symmetries for applications in plasmonics and catalysis. This outcome arises because the barrier for heterogeneous nucleation (i.e., seeded) is lower than that of homogeneous nucleation, where seeds can serve as preferential sites for the growth of complex structures and crystal phases. Our analysis begins by considering metal overgrowth from single-crystalline seeds of different shapes and symmetries, where the kinetics of adatom addition to seeds relative to their diffusion across seeds accounts for the expressed nanocrystal shapes. These results are then compared to overgrowth from seeds with different internal structures (i.e., planar defects), where the relationships between nanocrystalmore »
- Authors:
-
- Indiana Univ., Bloomington, IN (United States)
- Publication Date:
- Research Org.:
- Indiana Univ., Bloomington, IN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1814826
- Alternate Identifier(s):
- OSTI ID: 1817369
- Grant/Contract Number:
- SC0018961
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Accounts of Materials Research
- Additional Journal Information:
- Journal Volume: 2; Journal Issue: 8; Journal ID: ISSN 2643-6728
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Group theory; Palladium; Gold; Deposition; Nanocrystals
Citation Formats
Skrabalak, Sara E. Symmetry in Seeded Metal Nanocrystal Growth. United States: N. p., 2021.
Web. doi:10.1021/accountsmr.1c00077.
Skrabalak, Sara E. Symmetry in Seeded Metal Nanocrystal Growth. United States. https://doi.org/10.1021/accountsmr.1c00077
Skrabalak, Sara E. Sat .
"Symmetry in Seeded Metal Nanocrystal Growth". United States. https://doi.org/10.1021/accountsmr.1c00077. https://www.osti.gov/servlets/purl/1814826.
@article{osti_1814826,
title = {Symmetry in Seeded Metal Nanocrystal Growth},
author = {Skrabalak, Sara E.},
abstractNote = {Symmetry underpins the structure and function of the world around us and is also captured in modern nanomaterials, where changing the symmetry of a nanocrystal or the interparticle spacing and orientation of nanocrystal building blocks in a superlattice can give new function. However, the synthesis and assembly of nanocrystals have been limited largely to simple compositions and structures. It remains a grand challenge to achieve nanocrystals with compositional and structural complexity while maintaining the monodispersity required for their use. This Account will illustrate through recent examples that seeded methods enable the synthesis of compositionally and structurally complex multimetallic crystals with defined and predictable symmetries for applications in plasmonics and catalysis. This outcome arises because the barrier for heterogeneous nucleation (i.e., seeded) is lower than that of homogeneous nucleation, where seeds can serve as preferential sites for the growth of complex structures and crystal phases. Our analysis begins by considering metal overgrowth from single-crystalline seeds of different shapes and symmetries, where the kinetics of adatom addition to seeds relative to their diffusion across seeds accounts for the expressed nanocrystal shapes. These results are then compared to overgrowth from seeds with different internal structures (i.e., planar defects), where the relationships between nanocrystal size and volumetric strain energy and surface energy are discussed. A major finding from this analysis is that often the underlying symmetry of seeds can be predictably transferred to the final crystals during overgrowth processes. Consequences of this finding are the predictable syntheses of crystals with different hierarchies akin to snowcrystals as well as nanocrystals with complex compositions (e.g., quaternary nanoparticles). Yet, there are subtle aspects to seeded growth that pave a path toward examples where nanocrystal symmetry has been reduced compared to the original seeds in a controlled manner. As we found, both the concentrations of metal precursors and capping agents can impact whether symmetry is transferred or reduced during overgrowth. Examples from our laboratory will be placed in context to other reported strategies for symmetry breaking. As will be argued, understanding what conditions favor symmetry preservation versus symmetry reduction during seeded crystal growth is central to accessing next-generation crystal forms. The Account concludes by outlining synthetic challenges associated with forming nanoscale heterostructures with precise 3-D placement of different materials within a given nanocrystal as well as facet control within different material domain and interface engineering. Furthermore, we envision meeting these challenges through regioselective and chemoselective seeded syntheses for which a foundation is outlined herein.},
doi = {10.1021/accountsmr.1c00077},
journal = {Accounts of Materials Research},
number = 8,
volume = 2,
place = {United States},
year = {Sat Jul 17 00:00:00 EDT 2021},
month = {Sat Jul 17 00:00:00 EDT 2021}
}
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