skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis of Copper–Silica Core–Shell Nanostructures with Sharp and Stable Localized Surface Plasmon Resonance

Abstract

Copper nanoparticles exhibit intense and sharp localized surface plasmon resonance (LSPR) in the visible region; however, the LSPR peaks become weak and broad when exposed to air due to the oxidation of Cu. In this work, the Cu nanoparticles are successfully encapsulated in SiO 2 by employing trioctyl-n-phosphine (TOP)-capped Cu nanoparticles for the sol–gel reaction, yielding an aqueous Cu–SiO 2 core–shell suspension with stable and well-preserved LSPR properties of the Cu cores. With the TOP capping, the oxidation of the Cu cores in the microemulsion was significantly reduced, thus allowing the Cu cores to sustain the sol–gel process used for coating the SiO 2 protection layer. It was found that the self-assembled TOP-capped Cu nanoparticles were spontaneously disassembled during the sol–gel reaction, thus recovering the LSPR of individual particles. During the disassembling progress, the extinction spectrum of the nanocube agglomerates evolved from a broad extinction profile to a narrow and sharp peak. For a mixture of nanocubes and nanorods, the spectra evolved to two distinct peaks during the dissembling process. The observed spectra match well with the numerical simulations. In conclusion, these Cu–SiO 2 core–shell nanoparticles with sharp and stable LSPR may greatly expand the utilization of Cu nanoparticles inmore » aqueous environments.« less

Authors:
 [1];  [1];  [2];  [2];  [2]; ORCiD logo [1]
  1. Univ. of Arkansas, Fayetteville, AR (United States). Dept. of Chemistry and Biochemistry
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1372432
Report Number(s):
BNL-113905-2017-JA
Journal ID: ISSN 1932-7447; R&D Project: MA015MACA; KC0201010
Grant/Contract Number:
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 10; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Crane, Cameron C., Wang, Feng, Li, Jun, Tao, Jing, Zhu, Yimei, and Chen, Jingyi. Synthesis of Copper–Silica Core–Shell Nanostructures with Sharp and Stable Localized Surface Plasmon Resonance. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.6b11891.
Crane, Cameron C., Wang, Feng, Li, Jun, Tao, Jing, Zhu, Yimei, & Chen, Jingyi. Synthesis of Copper–Silica Core–Shell Nanostructures with Sharp and Stable Localized Surface Plasmon Resonance. United States. doi:10.1021/acs.jpcc.6b11891.
Crane, Cameron C., Wang, Feng, Li, Jun, Tao, Jing, Zhu, Yimei, and Chen, Jingyi. Tue . "Synthesis of Copper–Silica Core–Shell Nanostructures with Sharp and Stable Localized Surface Plasmon Resonance". United States. doi:10.1021/acs.jpcc.6b11891. https://www.osti.gov/servlets/purl/1372432.
@article{osti_1372432,
title = {Synthesis of Copper–Silica Core–Shell Nanostructures with Sharp and Stable Localized Surface Plasmon Resonance},
author = {Crane, Cameron C. and Wang, Feng and Li, Jun and Tao, Jing and Zhu, Yimei and Chen, Jingyi},
abstractNote = {Copper nanoparticles exhibit intense and sharp localized surface plasmon resonance (LSPR) in the visible region; however, the LSPR peaks become weak and broad when exposed to air due to the oxidation of Cu. In this work, the Cu nanoparticles are successfully encapsulated in SiO2 by employing trioctyl-n-phosphine (TOP)-capped Cu nanoparticles for the sol–gel reaction, yielding an aqueous Cu–SiO2 core–shell suspension with stable and well-preserved LSPR properties of the Cu cores. With the TOP capping, the oxidation of the Cu cores in the microemulsion was significantly reduced, thus allowing the Cu cores to sustain the sol–gel process used for coating the SiO2 protection layer. It was found that the self-assembled TOP-capped Cu nanoparticles were spontaneously disassembled during the sol–gel reaction, thus recovering the LSPR of individual particles. During the disassembling progress, the extinction spectrum of the nanocube agglomerates evolved from a broad extinction profile to a narrow and sharp peak. For a mixture of nanocubes and nanorods, the spectra evolved to two distinct peaks during the dissembling process. The observed spectra match well with the numerical simulations. In conclusion, these Cu–SiO2 core–shell nanoparticles with sharp and stable LSPR may greatly expand the utilization of Cu nanoparticles in aqueous environments.},
doi = {10.1021/acs.jpcc.6b11891},
journal = {Journal of Physical Chemistry. C},
number = 10,
volume = 121,
place = {United States},
year = {Tue Feb 21 00:00:00 EST 2017},
month = {Tue Feb 21 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

Save / Share:
  • Multipole spectral expansion based theory of energy transfer interactions between a donor and an acceptor molecule in the vicinity of a core-shell (nanoshell or core@shell) based plasmonic nanostructure is developed. In view of the diverse applications and rich plasmonic features such as tuning capability of surface plasmon (SP) frequencies, greater sensitivity to the change of dielectric environment, controllable redirection of electromagnetic radiation, closed form expressions for Energy Transfer Rate Enhancement Factor (ETREF) near core-shell particle are reported. The dependence of ETREF on different parameters is established through fitting equations, perceived to be of key importance for developing appropriate designs. Themore » theoretical approach developed in the present work is capable of treating higher order multipoles, which, in turn, are also shown to play a crucial role in the present context. Moreover, closed form expressions derived in the present work can directly be used as formula, e.g., for designing SP based biosensors and estimating energy exchange between proteins and excitonic interactions in quantum dots.« less
  • Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu 1.81S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tunedmore » from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ~8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.« less
  • Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu{sub 1.81}S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tunedmore » from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ∼8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.« less
  • Cited by 7
  • Rutile-type vanadium dioxide nanopowders with four different sizes were successfully synthesized by carbothermal reducing V{sub 2}O{sub 5} in KCl-LiCl molten salt. XRD and TEM characterizations suggested that vanadium dioxide particles formed by a broken and reunited process of vanadium oxide. Molten salt and organic carbon sources are crucial to the size of final particles. In the presence of the molten salt, the organic carbon with a shorter chain length would induce smaller particles. The UV-VIS-IR spectral measurements for as-prepared vanadium dioxide announced an obvious localized surface plasmon resonance band in the near infrared region at 90 deg. C. - Graphicalmore » abstract: Schematic illustration of the formation mechanism of VO{sub 2}(M) nanoparticles in molten salt, particles size can be controlled by choosing organic carbon sources with different chain length.« less