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Title: Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

Abstract

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 (Cu1.81S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tuned 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 concentrationmore » 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

Authors:
 [1];  [1];  [2];  [1]
  1. Cornell Univ., Ithaca, NY (United States). Dept. of Materials Science and Engineering
  2. Cornell Univ., Ithaca, NY (United States). School of Applied and Engineering Physics
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Materials Center at Cornell (EMC2)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1370406
Alternate Identifier(s):
OSTI ID: 1224265
Grant/Contract Number:  
SC0001086
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 16; Related Information: Emc2 partners with Cornell University (lead); Lawrence Berkeley National Laboratory; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Caldwell, Andrew H., Ha, Don-Hyung, Ding, Xiaoyue, and Robinson, Richard D. Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals. United States: N. p., 2014. Web. doi:10.1063/1.4897635.
Caldwell, Andrew H., Ha, Don-Hyung, Ding, Xiaoyue, & Robinson, Richard D. Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals. United States. https://doi.org/10.1063/1.4897635
Caldwell, Andrew H., Ha, Don-Hyung, Ding, Xiaoyue, and Robinson, Richard D. 2014. "Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals". United States. https://doi.org/10.1063/1.4897635. https://www.osti.gov/servlets/purl/1370406.
@article{osti_1370406,
title = {Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals},
author = {Caldwell, Andrew H. and Ha, Don-Hyung and Ding, Xiaoyue and Robinson, Richard D.},
abstractNote = {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 (Cu1.81S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tuned 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.},
doi = {10.1063/1.4897635},
url = {https://www.osti.gov/biblio/1370406}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 16,
volume = 141,
place = {United States},
year = {Thu Oct 30 00:00:00 EDT 2014},
month = {Thu Oct 30 00:00:00 EDT 2014}
}

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Cited by: 13 works
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Works referenced in this record:

Tuning the Excitonic and Plasmonic Properties of Copper Chalcogenide Nanocrystals
journal, January 2012

  • Kriegel, Ilka; Jiang, Chengyang; Rodríguez-Fernández, Jessica
  • Journal of the American Chemical Society, Vol. 134, Issue 3, p. 1583-1590
  • https://doi.org/10.1021/ja207798q

Plasmonics for improved photovoltaic devices
journal, February 2010


Plasmonic Properties of Copper Nanoparticles Fabricated by Nanosphere Lithography
journal, July 2007


Optical absorption of small metallic particles
journal, June 1985


Formation of Silver Nanoprisms with Surface Plasmons at Communication Wavelengths
journal, April 2006


Plasmonic Cu 2− x S Nanocrystals: Optical and Structural Properties of Copper-Deficient Copper(I) Sulfides
journal, April 2009


Reversible Tunability of the Near-Infrared Valence Band Plasmon Resonance in Cu 2– x Se Nanocrystals
journal, July 2011


Cation exchange synthesis and optoelectronic properties of type II CdTe–Cu2−xTe nano-heterostructures
journal, January 2014


Influence of Dielectric Anisotropy on the Absorption Properties of Localized Surface Plasmon Resonances Embedded in Si Nanowires
journal, March 2014


Fluorescence Enhancement by Au Nanostructures: Nanoshells and Nanorods
journal, February 2009


The crystal structures of low chalcocite and djurleite *
journal, January 1979


Engineering Multimodal Localized Surface Plasmon Resonances in Silicon Nanowires
journal, June 2013


Alloy Formation of Gold−Silver Nanoparticles and the Dependence of the Plasmon Absorption on Their Composition
journal, May 1999


Plasmonics: Metal-worthy methods and materials in nanophotonics
journal, August 2012


Quantum plasmon resonances of individual metallic nanoparticles
journal, March 2012


Localized surface plasmon resonances arising from free carriers in doped quantum dots
journal, April 2011


Synthesis and Characterization of Monodisperse Nanocrystals and Close-Packed Nanocrystal Assemblies
journal, August 2000


Sequential Cation Exchange in Nanocrystals: Preservation of Crystal Phase and Formation of Metastable Phases
journal, November 2011


Localized Surface Plasmon Resonances of Anisotropic Semiconductor Nanocrystals
journal, November 2011


Optical Absorption Spectra of Nanocrystal Gold Molecules
journal, May 1997


Charge-Tunable Quantum Plasmons in Colloidal Semiconductor Nanocrystals
journal, December 2013


Plasmonics in heavily-doped semiconductor nanocrystals
journal, April 2013


Monodisperse Platinum Nanospheres with Adjustable Diameters from 10 to 100 nm: Synthesis and Distinct Optical Properties
journal, December 2008


Surface-Plasmon Resonances in Single Metallic Nanoparticles
journal, May 1998


Solid–Solid Phase Transformations Induced through Cation Exchange and Strain in 2D Heterostructured Copper Sulfide Nanocrystals
journal, November 2014


Effects of Carrier Density and Shape on the Localized Surface Plasmon Resonances of Cu 2– x S Nanodisks
journal, September 2012


Spontaneous Superlattice Formation in Nanorods Through Partial Cation Exchange
journal, July 2007


Tunable Mid-Infrared Localized Surface Plasmon Resonances in Silicon Nanowires
journal, September 2012


Theory, Production and Mechanism of Formation of Monodispersed Hydrosols
journal, November 1950


Plasmonic Optical Properties and Applications of Metal Nanostructures
journal, September 2008


Selective Facet Reactivity during Cation Exchange in Cadmium Sulfide Nanorods
journal, April 2009


Morphology evolution of Cu2−xS nanoparticles: from spheres to dodecahedrons
journal, January 2011


Tunable Localized Surface Plasmon Resonances in Tungsten Oxide Nanocrystals
journal, February 2012


Overlayers on Silver Nanotriangles:  Field Confinement and Spectral Position of Localized Surface Plasmon Resonances
journal, August 2006


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