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Title: A Combined SAXS/SANS Study for the in Situ Characterization of Ligand Shells on Small Nanoparticles: The Case of ZnO

Abstract

ZnO nanoparticles (NPs) have great potential for their use in, e.g., thin film solar cells due to their electro-optical properties adjustable on the nanoscale. Therefore, the production of well-defined NPs is of major interest. For a targeted production process, the knowledge of the stabilization layer of the NPs during and after their formation is of particular importance. For the study of the stabilizer layer of ZnO NPs prepared in a wet chemical synthesis from zinc acetate, only ex situ studies have been performed so far. An acetate layer bound to the surface of the dried NPs was found; however, an in situ study which addresses the stabilizing layer surrounding the NPs in a native dispersion was missing. By the combination of small angle scattering with neutrons and X-rays (SANS and SAXS) for the same sample, we are now able to observe the acetate shell in situ for the first time. In addition, the changes of this shell could be followed during the ripening process for different temperatures. With increasing size of the ZnO core (dcore) the surrounding shell (dshell) becomes larger, and the acetate concentration within the shell is reduced. For all samples, the shell thickness was found to bemore » larger than the maximum extension of an acetate molecule with acetate concentrations within the shell below 50 vol %. Furthermore, there is not a monolayer of acetate molecules that covers the NPs but rather a swollen shell of acetate ions. This shell is assumed to hinder the growth of the NPs to larger macrostructures. In addition, we found that the partition coefficient μ between acetate in the shell surrounding the NPs and the total amount of acetate in the solution is about 10% which is in good agreement with ex situ data determined by thermogravimetric analysis.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [4];  [5]
+ Show Author Affiliations
  1. Friedrich-Alexander-Univ. Erlangen-Nürnberg (Germany)
  2. Forschungszentrum Jülich GmbH, Garching (Germany)
  3. Helmholt Zentrum Geesthacht (Germany)
  4. Technische Univ. München, Garching (Germany)
  5. Staudtstraße, Erlangen (Germany)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
German Research Foundation (DFG)
OSTI Identifier:
1346218
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 31; Journal Issue: 37; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; oxides; layers; molecules; metal oxide nanoparticles; organic compounds

Citation Formats

Schindler, T., Schmiele, M., Schmutzler, T., Kassar, T., Segets, D., Peukert, W., Radulescu, A., Kriele, A., Gilles, R., and Unruh, Tobias. A Combined SAXS/SANS Study for the in Situ Characterization of Ligand Shells on Small Nanoparticles: The Case of ZnO. United States: N. p., 2015. Web. doi:10.1021/acs.langmuir.5b02198.
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Schindler, T., Schmiele, M., Schmutzler, T., Kassar, T., Segets, D., Peukert, W., Radulescu, A., Kriele, A., Gilles, R., & Unruh, Tobias. A Combined SAXS/SANS Study for the in Situ Characterization of Ligand Shells on Small Nanoparticles: The Case of ZnO. United States. https://doi.org/10.1021/acs.langmuir.5b02198
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Schindler, T., Schmiele, M., Schmutzler, T., Kassar, T., Segets, D., Peukert, W., Radulescu, A., Kriele, A., Gilles, R., and Unruh, Tobias. Tue . "A Combined SAXS/SANS Study for the in Situ Characterization of Ligand Shells on Small Nanoparticles: The Case of ZnO". United States. https://doi.org/10.1021/acs.langmuir.5b02198. https://www.osti.gov/servlets/purl/1346218.
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@article{osti_1346218,
title = {A Combined SAXS/SANS Study for the in Situ Characterization of Ligand Shells on Small Nanoparticles: The Case of ZnO},
author = {Schindler, T. and Schmiele, M. and Schmutzler, T. and Kassar, T. and Segets, D. and Peukert, W. and Radulescu, A. and Kriele, A. and Gilles, R. and Unruh, Tobias},
abstractNote = {ZnO nanoparticles (NPs) have great potential for their use in, e.g., thin film solar cells due to their electro-optical properties adjustable on the nanoscale. Therefore, the production of well-defined NPs is of major interest. For a targeted production process, the knowledge of the stabilization layer of the NPs during and after their formation is of particular importance. For the study of the stabilizer layer of ZnO NPs prepared in a wet chemical synthesis from zinc acetate, only ex situ studies have been performed so far. An acetate layer bound to the surface of the dried NPs was found; however, an in situ study which addresses the stabilizing layer surrounding the NPs in a native dispersion was missing. By the combination of small angle scattering with neutrons and X-rays (SANS and SAXS) for the same sample, we are now able to observe the acetate shell in situ for the first time. In addition, the changes of this shell could be followed during the ripening process for different temperatures. With increasing size of the ZnO core (dcore) the surrounding shell (dshell) becomes larger, and the acetate concentration within the shell is reduced. For all samples, the shell thickness was found to be larger than the maximum extension of an acetate molecule with acetate concentrations within the shell below 50 vol %. Furthermore, there is not a monolayer of acetate molecules that covers the NPs but rather a swollen shell of acetate ions. This shell is assumed to hinder the growth of the NPs to larger macrostructures. In addition, we found that the partition coefficient μ between acetate in the shell surrounding the NPs and the total amount of acetate in the solution is about 10% which is in good agreement with ex situ data determined by thermogravimetric analysis.},
doi = {10.1021/acs.langmuir.5b02198},
journal = {Langmuir},
number = 37,
volume = 31,
place = {United States},
year = {Tue Sep 01 00:00:00 EDT 2015},
month = {Tue Sep 01 00:00:00 EDT 2015}
}
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https://doi.org/10.1021/acs.langmuir.5b02198
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