Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

Orian Elimelech; Jing Liu; Anna M. Plonka; Anatoly I. Frenkel; Uri Banin

doi:10.1002/anie.201702673

Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

Orian Elimelech, Jing Liu, Anna M. Plonka, Anatoly I. Frenkel^*, Uri Banin

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu₂S) NCs through a redox reaction with iodine molecules (I₂), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu₂S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sized NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.

Original language	American English
Pages (from-to)	10335-10340
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	35
DOIs	https://doi.org/10.1002/anie.201702673
State	Published - 21 Aug 2017

Bibliographical note

Funding Information:
The research leading to these results received funding through the NSF-BSF International Collaboration in Chemistry program. O.E., J.L., A.M.P., A.I.F., and U.B. acknowledge support of this work by NSF Grant No. CHE-1719534 and BSF Grant No. 2013/610. Use of the National Synchrotron Light Source II (beamline 28-ID-2) was supported by the U.S. Department of Energy (DOE) under Contract No. DE-SC0012704. XAFS experiments were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and The Dow Chemical Company. XAFS measurements used resources of the APS, a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

copper sulfide nanocrystals
doping
surface plasmon resonance
vacancies

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10.1002/anie.201702673

Cite this

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title = "Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals",

abstract = "Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2S) NCs through a redox reaction with iodine molecules (I2), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu2S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sized NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.",

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note = "Funding Information: The research leading to these results received funding through the NSF-BSF International Collaboration in Chemistry program. O.E., J.L., A.M.P., A.I.F., and U.B. acknowledge support of this work by NSF Grant No. CHE-1719534 and BSF Grant No. 2013/610. Use of the National Synchrotron Light Source II (beamline 28-ID-2) was supported by the U.S. Department of Energy (DOE) under Contract No. DE-SC0012704. XAFS experiments were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and The Dow Chemical Company. XAFS measurements used resources of the APS, a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Banin, Uri

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N2 - Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2S) NCs through a redox reaction with iodine molecules (I2), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu2S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sized NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.

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KW - surface plasmon resonance

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IS - 35

ER -

Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

Abstract

Bibliographical note

Keywords

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