Surface coordination chemistry of germanium nanocrystals synthesized by microwave-assisted reduction in oleylamine
Abstract
As surface ligands play a critical role in the colloidal stability and optoelectronic properties of semiconductor nanocrystals, we used solution NMR experiments to investigate the surface coordination chemistry of Ge nanocrystals synthesized by a microwave-assisted reduction of GeI2 in oleylamine. The as-synthesized Ge nanocrystals are coordinated to a fraction of strongly bound oleylamide ligands (with covalent X-type Ge–NHR bonds) and a fraction of more weakly bound (or physisorbed) oleylamine, which readily exchanges with free oleylamine in solution. The fraction of strongly bound oleylamide ligands increases with increasing synthesis temperature, which also correlates with better colloidal stability. Thiol and carboxylic acid ligands bind to the Ge nanocrystal surface only upon heating, suggesting a high kinetic barrier to surface binding. These incoming ligands do not displace native oleylamide ligands but instead appear to coordinate to open surface sites, confirming that the as-prepared nanocrystals are not fully passivated. Furthermore, these findings will allow for a better understanding of the surface chemistry of main group nanocrystals and the conditions necessary for ligand exchange to ultimately maximize their functionality.
- Authors:
-
[1];
[1];
[2];
[1]
- Univ. of Southern California, Los Angeles, CA (United States)
- Univ. of California, Davis, CA (United States)
- Publication Date:
- Research Org.:
- Univ. of Southern California, Los Angeles, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1728701
- Alternate Identifier(s):
- OSTI ID: 1592505
- Grant/Contract Number:
- FG02-11ER46826; SC0006812
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nanoscale
- Additional Journal Information:
- Journal Volume: 12; Journal Issue: 4; Journal ID: ISSN 2040-3364
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Smock, Sara R., Tabatabaei, Katayoon, Williams, Travis J., Kauzlarich, Susan M., and Brutchey, Richard L. Surface coordination chemistry of germanium nanocrystals synthesized by microwave-assisted reduction in oleylamine. United States: N. p., 2020.
Web. doi:10.1039/c9nr09233a.
Smock, Sara R., Tabatabaei, Katayoon, Williams, Travis J., Kauzlarich, Susan M., & Brutchey, Richard L. Surface coordination chemistry of germanium nanocrystals synthesized by microwave-assisted reduction in oleylamine. United States. https://doi.org/10.1039/c9nr09233a
Smock, Sara R., Tabatabaei, Katayoon, Williams, Travis J., Kauzlarich, Susan M., and Brutchey, Richard L. Mon .
"Surface coordination chemistry of germanium nanocrystals synthesized by microwave-assisted reduction in oleylamine". United States. https://doi.org/10.1039/c9nr09233a. https://www.osti.gov/servlets/purl/1728701.
@article{osti_1728701,
title = {Surface coordination chemistry of germanium nanocrystals synthesized by microwave-assisted reduction in oleylamine},
author = {Smock, Sara R. and Tabatabaei, Katayoon and Williams, Travis J. and Kauzlarich, Susan M. and Brutchey, Richard L.},
abstractNote = {As surface ligands play a critical role in the colloidal stability and optoelectronic properties of semiconductor nanocrystals, we used solution NMR experiments to investigate the surface coordination chemistry of Ge nanocrystals synthesized by a microwave-assisted reduction of GeI2 in oleylamine. The as-synthesized Ge nanocrystals are coordinated to a fraction of strongly bound oleylamide ligands (with covalent X-type Ge–NHR bonds) and a fraction of more weakly bound (or physisorbed) oleylamine, which readily exchanges with free oleylamine in solution. The fraction of strongly bound oleylamide ligands increases with increasing synthesis temperature, which also correlates with better colloidal stability. Thiol and carboxylic acid ligands bind to the Ge nanocrystal surface only upon heating, suggesting a high kinetic barrier to surface binding. These incoming ligands do not displace native oleylamide ligands but instead appear to coordinate to open surface sites, confirming that the as-prepared nanocrystals are not fully passivated. Furthermore, these findings will allow for a better understanding of the surface chemistry of main group nanocrystals and the conditions necessary for ligand exchange to ultimately maximize their functionality.},
doi = {10.1039/c9nr09233a},
journal = {Nanoscale},
number = 4,
volume = 12,
place = {United States},
year = {Mon Jan 13 00:00:00 EST 2020},
month = {Mon Jan 13 00:00:00 EST 2020}
}
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