Ligand-Mediated Phase Control in Colloidal AgInSe2 Nanocrystals
Abstract
Synthetic studies of colloidal nanoparticles that crystallize in metastable structures represent an emerging area of interest in the development of novel functional materials, as metastable nanomaterials may exhibit unique properties when compared to their counterparts that crystallize in thermodynamically preferred structures. Herein, we demonstrate how phase control of colloidal AgInSe2 nanocrystals can be achieved by performing reactions in the presence, or absence, of coordinating ligands that can act as cation exchange mediators (i.e., oleylamine or 1-dodecanethiol). These coordinating ligands play a crucial role in formation of metastable AgInSe2 nanocrystals, as they mediate in-situ topotactic conversion of an orthorhombic Ag2Se intermediate to a metastable orthorhombic phase of AgInSe2. We pro-vide a detailed mechanistic crystal chemistry description of this process to structurally elucidate how the orthorhombic phase of AgInSe2 forms. Density functional theory calculations suggest that the metastable orthorhombic phase of AgInSe2 is metastable by a small margin, at 10 meV/atom above the thermodynamic ground state. In the absence of oleylamine or 1-dodecanethiol, Ag2Se nanocrystal intermediates convert through kinetically slow, non-topotactic conversion processes to yield the thermodynamically preferred chalcopyrite structure of AgInSe2. Furthermore, on the basis of these discoveries, we offer new insight into the prediction of novel metastable multinary nanocrystal phasesmore »
- Authors:
-
[2];
[1]
- Univ. of Southern California, Los Angeles, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, 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). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1728695
- Grant/Contract Number:
- FG02-11ER46826; SC0006812
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 32; Journal Issue: 7; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cancer; Chemical structure; Phase transitions; Materials; Nanocrystals
Citation Formats
Tappan, Bryce A., Horton, Matthew K., and Brutchey, Richard L. Ligand-Mediated Phase Control in Colloidal AgInSe2 Nanocrystals. United States: N. p., 2020.
Web. doi:10.1021/acs.chemmater.9b05163.
Tappan, Bryce A., Horton, Matthew K., & Brutchey, Richard L. Ligand-Mediated Phase Control in Colloidal AgInSe2 Nanocrystals. United States. https://doi.org/10.1021/acs.chemmater.9b05163
Tappan, Bryce A., Horton, Matthew K., and Brutchey, Richard L. Thu .
"Ligand-Mediated Phase Control in Colloidal AgInSe2 Nanocrystals". United States. https://doi.org/10.1021/acs.chemmater.9b05163. https://www.osti.gov/servlets/purl/1728695.
@article{osti_1728695,
title = {Ligand-Mediated Phase Control in Colloidal AgInSe2 Nanocrystals},
author = {Tappan, Bryce A. and Horton, Matthew K. and Brutchey, Richard L.},
abstractNote = {Synthetic studies of colloidal nanoparticles that crystallize in metastable structures represent an emerging area of interest in the development of novel functional materials, as metastable nanomaterials may exhibit unique properties when compared to their counterparts that crystallize in thermodynamically preferred structures. Herein, we demonstrate how phase control of colloidal AgInSe2 nanocrystals can be achieved by performing reactions in the presence, or absence, of coordinating ligands that can act as cation exchange mediators (i.e., oleylamine or 1-dodecanethiol). These coordinating ligands play a crucial role in formation of metastable AgInSe2 nanocrystals, as they mediate in-situ topotactic conversion of an orthorhombic Ag2Se intermediate to a metastable orthorhombic phase of AgInSe2. We pro-vide a detailed mechanistic crystal chemistry description of this process to structurally elucidate how the orthorhombic phase of AgInSe2 forms. Density functional theory calculations suggest that the metastable orthorhombic phase of AgInSe2 is metastable by a small margin, at 10 meV/atom above the thermodynamic ground state. In the absence of oleylamine or 1-dodecanethiol, Ag2Se nanocrystal intermediates convert through kinetically slow, non-topotactic conversion processes to yield the thermodynamically preferred chalcopyrite structure of AgInSe2. Furthermore, on the basis of these discoveries, we offer new insight into the prediction of novel metastable multinary nanocrystal phases that do not exist on bulk phase diagrams.},
doi = {10.1021/acs.chemmater.9b05163},
journal = {Chemistry of Materials},
number = 7,
volume = 32,
place = {United States},
year = {Thu Mar 19 00:00:00 EDT 2020},
month = {Thu Mar 19 00:00:00 EDT 2020}
}
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