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Title: Determination of nanoparticle collision cross section distribution functions in low pressure plasma synthesis reactors via ion mobility spectrometry

Abstract

Low pressure (< 20 Torr) non-thermal plasma flow tube reactors are often used for the synthesis of high purity nanoparticles (NPs) via nucleation and subsequent growth from vapor phase precursors. In spite of their utility, process monitoring (i.e. output NP size characterization) in such reactors is difficult, as there is a dearth of techniques available for online nanoparticle size distribution function measurement. In this study, we developed and applied an ion mobility spectrometry (IMS) system consisting of a low pressure differential mobility analyzer (LPDMA) and electrical detector to determine the collision cross section distribution functions of Si NPs synthesized in a radiofrequency non-thermal SiH4-Ar plasma operated at ~2 Torr (266 Pa). The collision cross section, roughly proportional to projected area, is a parameter quantifying the size and structure of nanometer scale species in the vapor phase. We introduce the collision cross section distribution function as a metric for potential use in online process monitoring in NP synthesis. Proper inversion of the collision cross section distribution function requires a priori knowledge of the LPDMA transfer function. We utilized a tandem differential mobility analyzer approach, coupled with a Twomey-Markwoski based scheme to determine LPDMA transfer functions. Subsequent application of these transfer functionsmore » in collision cross section distribution function determination showed that at the outlet of the non-thermal plasma flow tube reactor, both negatively and positively charged Si NPs persisted with nearly identical collision cross section distribution functions. NPs were found to have mode “mobility equivalent” diameters near 10 nm, and via TEM analysis were found to persist at the reactor outlet as small aggregates composed of ~5 nm diameter primary particles. Size distributions functions inferred from collision cross section measurements were compared to size distribution functions inferred from TEM images; excellent agreement was found between IMS and TEM for both mean mobility equivalent diameter and distribution function width. In total, this study shows that (1) IMS is a viable approach for process monitoring in non-thermal plasma NP flow tube synthesis systems, (2) although NPs are modestly aggregated at low-pressure plasma reactor outlets, the extent of aggregation is considerably less than observed in most atmospheric pressure and equilibrium NP synthesis systems (e.g. flames), and (3) after exiting the plasma reactor, the decharging of NPs from highly negatively charge states to a bipolar charge distribution likely drives aggregation on the plasma boundary.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Kanazawa Univ. (Japan)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Fusion Energy Sciences (FES)
OSTI Identifier:
1598464
Grant/Contract Number:  
SC0018202
Resource Type:
Accepted Manuscript
Journal Name:
Nano Futures
Additional Journal Information:
Journal Volume: 3; Journal Issue: 1; Journal ID: ISSN 2399-1984
Publisher:
IOP Science
Country of Publication:
United States
Language:
English
Subject:
70 PLASMA PHYSICS AND FUSION TECHNOLOGY

Citation Formats

Chen, Xiaoshuang, Seto, Takafumi, Kortshagen, Uwe R., and Hogan, Christopher J. Determination of nanoparticle collision cross section distribution functions in low pressure plasma synthesis reactors via ion mobility spectrometry. United States: N. p., 2019. Web. https://doi.org/10.1088/2399-1984/aaff97.
Chen, Xiaoshuang, Seto, Takafumi, Kortshagen, Uwe R., & Hogan, Christopher J. Determination of nanoparticle collision cross section distribution functions in low pressure plasma synthesis reactors via ion mobility spectrometry. United States. https://doi.org/10.1088/2399-1984/aaff97
Chen, Xiaoshuang, Seto, Takafumi, Kortshagen, Uwe R., and Hogan, Christopher J. Thu . "Determination of nanoparticle collision cross section distribution functions in low pressure plasma synthesis reactors via ion mobility spectrometry". United States. https://doi.org/10.1088/2399-1984/aaff97. https://www.osti.gov/servlets/purl/1598464.
@article{osti_1598464,
title = {Determination of nanoparticle collision cross section distribution functions in low pressure plasma synthesis reactors via ion mobility spectrometry},
author = {Chen, Xiaoshuang and Seto, Takafumi and Kortshagen, Uwe R. and Hogan, Christopher J.},
abstractNote = {Low pressure (< 20 Torr) non-thermal plasma flow tube reactors are often used for the synthesis of high purity nanoparticles (NPs) via nucleation and subsequent growth from vapor phase precursors. In spite of their utility, process monitoring (i.e. output NP size characterization) in such reactors is difficult, as there is a dearth of techniques available for online nanoparticle size distribution function measurement. In this study, we developed and applied an ion mobility spectrometry (IMS) system consisting of a low pressure differential mobility analyzer (LPDMA) and electrical detector to determine the collision cross section distribution functions of Si NPs synthesized in a radiofrequency non-thermal SiH4-Ar plasma operated at ~2 Torr (266 Pa). The collision cross section, roughly proportional to projected area, is a parameter quantifying the size and structure of nanometer scale species in the vapor phase. We introduce the collision cross section distribution function as a metric for potential use in online process monitoring in NP synthesis. Proper inversion of the collision cross section distribution function requires a priori knowledge of the LPDMA transfer function. We utilized a tandem differential mobility analyzer approach, coupled with a Twomey-Markwoski based scheme to determine LPDMA transfer functions. Subsequent application of these transfer functions in collision cross section distribution function determination showed that at the outlet of the non-thermal plasma flow tube reactor, both negatively and positively charged Si NPs persisted with nearly identical collision cross section distribution functions. NPs were found to have mode “mobility equivalent” diameters near 10 nm, and via TEM analysis were found to persist at the reactor outlet as small aggregates composed of ~5 nm diameter primary particles. Size distributions functions inferred from collision cross section measurements were compared to size distribution functions inferred from TEM images; excellent agreement was found between IMS and TEM for both mean mobility equivalent diameter and distribution function width. In total, this study shows that (1) IMS is a viable approach for process monitoring in non-thermal plasma NP flow tube synthesis systems, (2) although NPs are modestly aggregated at low-pressure plasma reactor outlets, the extent of aggregation is considerably less than observed in most atmospheric pressure and equilibrium NP synthesis systems (e.g. flames), and (3) after exiting the plasma reactor, the decharging of NPs from highly negatively charge states to a bipolar charge distribution likely drives aggregation on the plasma boundary.},
doi = {10.1088/2399-1984/aaff97},
journal = {Nano Futures},
number = 1,
volume = 3,
place = {United States},
year = {2019},
month = {2}
}

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