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Title: Gelation of plasmonic metal oxide nanocrystals by polymer-induced depletion attractions

Abstract

Gelation of colloidal nanocrystals emerged as a strategy to preserve inherent nanoscale properties in multiscale architectures. However, available gelation methods to directly form self-supported nanocrystal networks struggle to reliably control nanoscale optical phenomena such as photoluminescence and localized surface plasmon resonance (LSPR) across nanocrystal systems due to processing variabilities. Here, we report on an alternative gelation method based on physical internanocrystal interactions: short-range depletion attractions balanced by long-range electrostatic repulsions. The latter are established by removing the native organic ligands that passivate tin-doped indium oxide (ITO) nanocrystals while the former are introduced by mixing with small PEG chains. As we incorporate increasing concentrations of PEG, we observe a reentrant phase behavior featuring two favorable gelation windows; the first arises from bridging effects while the second is attributed to depletion attractions according to phase behavior predicted by our unified theoretical model. Our assembled nanocrystals remain discrete within the gel network, based on X-ray scattering and high-resolution transmission electron microscopy. The infrared optical response of the gels is reflective of both the nanocrystal building blocks and the network architecture, being characteristic of ITO nanocrystals’ LSPR with coupling interactions between neighboring nanocrystals.

Authors:
; ; ; ; ; ORCiD logo; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1465254
Grant/Contract Number:  
AC02CH11231
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 36; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Saez Cabezas, Camila A., Ong, Gary K., Jadrich, Ryan B., Lindquist, Beth A., Agrawal, Ankit, Truskett, Thomas M., and Milliron, Delia J. Gelation of plasmonic metal oxide nanocrystals by polymer-induced depletion attractions. United States: N. p., 2018. Web. doi:10.1073/pnas.1806927115.
Saez Cabezas, Camila A., Ong, Gary K., Jadrich, Ryan B., Lindquist, Beth A., Agrawal, Ankit, Truskett, Thomas M., & Milliron, Delia J. Gelation of plasmonic metal oxide nanocrystals by polymer-induced depletion attractions. United States. doi:10.1073/pnas.1806927115.
Saez Cabezas, Camila A., Ong, Gary K., Jadrich, Ryan B., Lindquist, Beth A., Agrawal, Ankit, Truskett, Thomas M., and Milliron, Delia J. Mon . "Gelation of plasmonic metal oxide nanocrystals by polymer-induced depletion attractions". United States. doi:10.1073/pnas.1806927115.
@article{osti_1465254,
title = {Gelation of plasmonic metal oxide nanocrystals by polymer-induced depletion attractions},
author = {Saez Cabezas, Camila A. and Ong, Gary K. and Jadrich, Ryan B. and Lindquist, Beth A. and Agrawal, Ankit and Truskett, Thomas M. and Milliron, Delia J.},
abstractNote = {Gelation of colloidal nanocrystals emerged as a strategy to preserve inherent nanoscale properties in multiscale architectures. However, available gelation methods to directly form self-supported nanocrystal networks struggle to reliably control nanoscale optical phenomena such as photoluminescence and localized surface plasmon resonance (LSPR) across nanocrystal systems due to processing variabilities. Here, we report on an alternative gelation method based on physical internanocrystal interactions: short-range depletion attractions balanced by long-range electrostatic repulsions. The latter are established by removing the native organic ligands that passivate tin-doped indium oxide (ITO) nanocrystals while the former are introduced by mixing with small PEG chains. As we incorporate increasing concentrations of PEG, we observe a reentrant phase behavior featuring two favorable gelation windows; the first arises from bridging effects while the second is attributed to depletion attractions according to phase behavior predicted by our unified theoretical model. Our assembled nanocrystals remain discrete within the gel network, based on X-ray scattering and high-resolution transmission electron microscopy. The infrared optical response of the gels is reflective of both the nanocrystal building blocks and the network architecture, being characteristic of ITO nanocrystals’ LSPR with coupling interactions between neighboring nanocrystals.},
doi = {10.1073/pnas.1806927115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 36,
volume = 115,
place = {United States},
year = {2018},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1073/pnas.1806927115

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