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Title: Characterization of the state of nanoparticle aggregation in non-equilibrium plasma synthesis systems

Abstract

Non-equilibrium plasmas offer a unique environment for nanoparticle synthesis. Particles are homogeneously nucleated and grow at near room temperature as a result of non-thermal decomposition of vapor precursors by electrons and other plasma-excited species. Despite their widespread use, several features regarding particle growth in these systems remain poorly understood. In particular, particle aggregation (the formation of non-spherical entities composed of primary particles) is assumed to be negligible because of unipolar particle charging and subsequent Coulombic repulsion, which would hinder collisional growth. Here, we apply ion mobility-mass spectrometry (IM-MS) to a non-thermal, atmospheric pressure DC microplasma to study the state of aggregation of as-synthesized nanoparticles. Under all examined synthesis conditions, we find the presence of highly branched, chain-like aggregates at the reactor outlet, with a primary particle radius below 10 nm that is relatively insensitive to synthesis conditions. The aggregates are polydisperse, with mean masses and mobility diameters increasing with both increasing precursor concentration and increasing flow residence time within the system. TEM structural characterization shows that the aggregates can be described by a quasifractal model, with a fractal dimensions in the 1.6–2.0 range. The mass-mobility relationship inferred from IM-MS and TEM agrees well with Langevin dynamics simulations where coulomb interactionsmore » are not considered. We suggest that particle aggregation occurs either in the plasma volume due to the scavenging of smaller neutral or positively charged particles by growing aggregates or outside the reactor where the plasma density is lower and electrons are not available to maintain high levels of unipolar charge. Furthermore, the methods applied here additionally demonstrate the potential of IM-MS and TEM structural characterization in analyzing gas-phase nanoparticle production processes.« less

Authors:
 [1];  [1];  [1];  [2]; ORCiD logo [1]
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  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Case Western Reserve Univ., Cleveland, OH (United States)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Fusion Energy Sciences (FES)
OSTI Identifier:
1479200
Grant/Contract Number:  
SC0018202
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physics. D, Applied Physics
Additional Journal Information:
Journal Volume: 51; Journal Issue: 33; Related Information: http://iopscience.iop.org/article/10.1088/1361-6463/aad26f/meta; Journal ID: ISSN 0022-3727
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 42 ENGINEERING; 47 OTHER INSTRUMENTATION; Dusty Plasmas; Ion Mobility-Mass Spectrometry; Aggregation; Differential Mobility Analysis; plasma synthesis; structural characterization; multidimensional size distributions

Citation Formats

Chen, Xiaoshuang, Ghosh, Souvik, Buckley, David T., Sankaran, R. Mohan, and Hogan, Jr., Christopher J. Characterization of the state of nanoparticle aggregation in non-equilibrium plasma synthesis systems. United States: N. p., 2018. Web. doi:10.1088/1361-6463/aad26f.
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Chen, Xiaoshuang, Ghosh, Souvik, Buckley, David T., Sankaran, R. Mohan, & Hogan, Jr., Christopher J. Characterization of the state of nanoparticle aggregation in non-equilibrium plasma synthesis systems. United States. https://doi.org/10.1088/1361-6463/aad26f
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Chen, Xiaoshuang, Ghosh, Souvik, Buckley, David T., Sankaran, R. Mohan, and Hogan, Jr., Christopher J. Thu . "Characterization of the state of nanoparticle aggregation in non-equilibrium plasma synthesis systems". United States. https://doi.org/10.1088/1361-6463/aad26f. https://www.osti.gov/servlets/purl/1479200.
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@article{osti_1479200,
title = {Characterization of the state of nanoparticle aggregation in non-equilibrium plasma synthesis systems},
author = {Chen, Xiaoshuang and Ghosh, Souvik and Buckley, David T. and Sankaran, R. Mohan and Hogan, Jr., Christopher J.},
abstractNote = {Non-equilibrium plasmas offer a unique environment for nanoparticle synthesis. Particles are homogeneously nucleated and grow at near room temperature as a result of non-thermal decomposition of vapor precursors by electrons and other plasma-excited species. Despite their widespread use, several features regarding particle growth in these systems remain poorly understood. In particular, particle aggregation (the formation of non-spherical entities composed of primary particles) is assumed to be negligible because of unipolar particle charging and subsequent Coulombic repulsion, which would hinder collisional growth. Here, we apply ion mobility-mass spectrometry (IM-MS) to a non-thermal, atmospheric pressure DC microplasma to study the state of aggregation of as-synthesized nanoparticles. Under all examined synthesis conditions, we find the presence of highly branched, chain-like aggregates at the reactor outlet, with a primary particle radius below 10 nm that is relatively insensitive to synthesis conditions. The aggregates are polydisperse, with mean masses and mobility diameters increasing with both increasing precursor concentration and increasing flow residence time within the system. TEM structural characterization shows that the aggregates can be described by a quasifractal model, with a fractal dimensions in the 1.6–2.0 range. The mass-mobility relationship inferred from IM-MS and TEM agrees well with Langevin dynamics simulations where coulomb interactions are not considered. We suggest that particle aggregation occurs either in the plasma volume due to the scavenging of smaller neutral or positively charged particles by growing aggregates or outside the reactor where the plasma density is lower and electrons are not available to maintain high levels of unipolar charge. Furthermore, the methods applied here additionally demonstrate the potential of IM-MS and TEM structural characterization in analyzing gas-phase nanoparticle production processes.},
doi = {10.1088/1361-6463/aad26f},
journal = {Journal of Physics. D, Applied Physics},
number = 33,
volume = 51,
place = {United States},
year = {Thu Jul 26 00:00:00 EDT 2018},
month = {Thu Jul 26 00:00:00 EDT 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1088/1361-6463/aad26f
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Cited by: 24 works
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Figures / Tables:

Table 1 Table 1: A summary of DC microplasma operating conditions. The particle laden flow rate is the same for both DMA and APM measurements. The gas viscosity and mean free path are needed to link data operating conditions to the mobility diameter via the Stokes Millikan equation. The DMA sheath flowmore » rate was calculated from 125 nm PSL calibration. Also shown are geometric mean diameters (π‘‘π‘š,𝑔) and geometric standard deviations (πœŽπ‘”) for the number based size distributions, inferred from IM-MS measurements.« less
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