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Title: Tolerance to structural disorder and tunable mechanical behavior in self-assembled superlattices of polymer-grafted nanocrystals

Large, freestanding membranes with remarkably high elastic modulus ( > 10 GPa) have been fabricated through the self-Assembly of ligand-stabilized inorganic nanocrystals, even though these nanocrystals are connected only by soft organic ligands (e.g., dodecanethiol or DNA) that are not cross-linked or entangled. Recent developments in the synthesis of polymer-grafted nanocrystals have greatly expanded the library of accessible superlattice architectures,which allows superlattice mechanical behavior to be linked to specific structural features. Here, colloidal self-Assembly is used to organize polystyrene-grafted Au nanocrystals at a fluid interface to form ordered solids with sub-10-nm periodic features. We used thin-film buckling and nanoindentation to evaluate the mechanical behavior of polymer-grafted nanocrystal superlattices while exploring the role of polymer structural conformation, nanocrystal packing, and superlattice dimensions. Superlattices containing 3-20 vol % Au are found to have an elastic modulus of ~6-19 GPa, and hardness of ~120-170 MPa. We also found that rapidly self-Assembled superlattices have the highest elastic modulus, despite containing significant structural defects. Polymer extension, interdigitation, and grafting density are determined to be critical parameters that govern superlattice elastic and plastic deformation.
Authors:
ORCiD logo [1] ;  [1] ;  [2] ;  [3] ;  [4] ;  [5]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  3. Hysitron Inc., Minneapolis, MN (United States)
  4. Univ. of California, Berkeley, CA (United States). Dept. of Nuclear Engineering
  5. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry, Dept. of Materials Science and Engineering, Kavli Energy Nanoscience Inst.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 114; Journal Issue: 11; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; elasticity; buckling; nanocomposite; thin film; nanoindentation
OSTI Identifier:
1345069
Alternate Identifier(s):
OSTI ID: 1413721

Gu, X. Wendy, Ye, Xingchen, Koshy, David M., Vachhani, Shraddha, Hosemann, Peter, and Alivisatos, A. Paul. Tolerance to structural disorder and tunable mechanical behavior in self-assembled superlattices of polymer-grafted nanocrystals. United States: N. p., Web. doi:10.1073/pnas.1618508114.
Gu, X. Wendy, Ye, Xingchen, Koshy, David M., Vachhani, Shraddha, Hosemann, Peter, & Alivisatos, A. Paul. Tolerance to structural disorder and tunable mechanical behavior in self-assembled superlattices of polymer-grafted nanocrystals. United States. doi:10.1073/pnas.1618508114.
Gu, X. Wendy, Ye, Xingchen, Koshy, David M., Vachhani, Shraddha, Hosemann, Peter, and Alivisatos, A. Paul. 2017. "Tolerance to structural disorder and tunable mechanical behavior in self-assembled superlattices of polymer-grafted nanocrystals". United States. doi:10.1073/pnas.1618508114.
@article{osti_1345069,
title = {Tolerance to structural disorder and tunable mechanical behavior in self-assembled superlattices of polymer-grafted nanocrystals},
author = {Gu, X. Wendy and Ye, Xingchen and Koshy, David M. and Vachhani, Shraddha and Hosemann, Peter and Alivisatos, A. Paul},
abstractNote = {Large, freestanding membranes with remarkably high elastic modulus ( > 10 GPa) have been fabricated through the self-Assembly of ligand-stabilized inorganic nanocrystals, even though these nanocrystals are connected only by soft organic ligands (e.g., dodecanethiol or DNA) that are not cross-linked or entangled. Recent developments in the synthesis of polymer-grafted nanocrystals have greatly expanded the library of accessible superlattice architectures,which allows superlattice mechanical behavior to be linked to specific structural features. Here, colloidal self-Assembly is used to organize polystyrene-grafted Au nanocrystals at a fluid interface to form ordered solids with sub-10-nm periodic features. We used thin-film buckling and nanoindentation to evaluate the mechanical behavior of polymer-grafted nanocrystal superlattices while exploring the role of polymer structural conformation, nanocrystal packing, and superlattice dimensions. Superlattices containing 3-20 vol % Au are found to have an elastic modulus of ~6-19 GPa, and hardness of ~120-170 MPa. We also found that rapidly self-Assembled superlattices have the highest elastic modulus, despite containing significant structural defects. Polymer extension, interdigitation, and grafting density are determined to be critical parameters that govern superlattice elastic and plastic deformation.},
doi = {10.1073/pnas.1618508114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 11,
volume = 114,
place = {United States},
year = {2017},
month = {2}
}

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