Squeezed nanocrystals: equilibrium configuration of metal clusters embedded beneath the surface of a layered material

Julien, Scott E.; Lii-Rosales, Ann; Wan, Kai-Tak; Han, Yong; Tringides, Michael C.; Evans, James W.; Thiel, Patricia A.

doi:10.1039/C8NR10549A

Title: Squeezed nanocrystals: equilibrium configuration of metal clusters embedded beneath the surface of a layered material

Journal Article · Thu Mar 28 00:00:00 EDT 2019 · Nanoscale

DOI:https://doi.org/10.1039/C8NR10549A· OSTI ID:1501745

Julien, Scott E. ^[1];

^[2]; Wan, Kai-Tak ^[1];

^[3]; Tringides, Michael C. ^[3];

^[3];

^[2]

Mechanical and Industrial Engineering, Northeastern University, Boston, USA
Ames Laboratory, Ames, USA, Department of Chemistry, Iowa State University
Ames Laboratory, Ames, USA, Department of Physics and Astronomy, Iowa State University

Shapes of functional metallic nanocrystals, typically synthesized either free in solution or supported on surfaces, are key for controlling properties. Here, we consider a novel new class of metallic nanocrystals, copper clusters embedded near the surface of graphite, which can be considered a model system for metals embedded beneath surfaces of layered materials, or beneath supported membranes. We develop a continuum elasticity (CE) model for the equilibrium shape of these islands, and compare its predictions with experimental data. The CE model incorporates appropriate surface energy, adhesion energies, and strain energy. The agreement between the CE model and the data is—with one exception—excellent, both qualitatively and quantitatively, and is achieved with a single adjustable parameter. The model predicts that the embedded island shape is invariant with size, manifest both by constant side slope and by constant aspect ratio. This prediction is rationalized by dimensional analysis of the relevant energetic contributions. The aspect ratio (width : height) of an embedded Cu cluster is much larger than that of a supported but non-embedded Cu cluster, due to resistance of the graphene membrane to deformation. Experimental data diverge from the model predictions only in the case of the aspect ratio of small islands, below a critical height of ~10 nm. The divergence may be due to bending strain, which is treated only approximately in the model. Strong support for the CE model and its interpretation is provided by additional data for embedded Fe clusters. As a result most of these observations and insights should be generally applicable to systems where a metal cluster is embedded beneath a layered material or supported membrane, provided that shape equilibration is possible.

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Research Organization:: Ames Lab., Ames, IA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-05CH11231; AC02-07CH11358; 70NANB15H235

OSTI ID:: 1501745

Alternate ID(s):: OSTI ID: 1502871; OSTI ID: 1542913

Report Number(s):: IS-J-9899; NANOHL

Journal Information:: Nanoscale, Journal Name: Nanoscale Vol. 11 Journal Issue: 13; ISSN 2040-3364

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

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Cited by: 12 works

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Cited By (1)

Shapes of Fe nanocrystals encapsulated at the graphite surface Lii-Rosales, Ann; Han, Yong; Julien, Scott E. New Journal of Physics, Vol. 22, Issue 2 https://doi.org/10.1088/1367-2630/ab687a	journal	February 2020