Syntheses of Colloidal F:In                         2                         O                         3                          Cubes: Fluorine-Induced Faceting and Infrared Plasmonic Response

Shin Hum Cho; Sandeep Ghosh; Zachariah J. Berkson; Jordan A. Hachtel; Jianjian Shi; Xunhua Zhao; Lauren C. Reimnitz; Clayton J. Dahlman; Yujing Ho; Anni Yang; Yuanyue Liu; Juan Carlos Idrobo; Bradley F. Chmelka; Delia J. Milliron

doi:10.1021/acs.chemmater.9b00906

Syntheses of Colloidal F:In ₂ O ₃ Cubes: Fluorine-Induced Faceting and Infrared Plasmonic Response

Shin Hum Cho, Sandeep Ghosh, Zachariah J. Berkson, Jordan A. Hachtel, Jianjian Shi, Xunhua Zhao, Lauren C. Reimnitz, Clayton J. Dahlman, Yujing Ho, Anni Yang, Yuanyue Liu, Juan Carlos Idrobo, Bradley F. Chmelka, Delia J. Milliron

electron Microscopy and Microanalysis

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

48 Scopus citations

Abstract

Cube-shaped nanocrystals (NCs) of conventional metals like gold and silver generally exhibit localized surface plasmon resonance (LSPR) in the visible region with spectral modes determined by their faceted shapes. However, faceted NCs exhibiting LSPR response in the infrared (IR) region are relatively rare. Here, we describe the colloidal synthesis of nanoscale fluorine-doped indium oxide (F:In ₂ O ₃ ) cubes with LSPR response in the IR region, wherein fluorine was found to both direct the cubic morphology and act as an aliovalent dopant. Single-crystalline 160 nm F:In ₂ O ₃ cubes terminated by (100) facets and concave cubes were synthesized using a colloidal heat-up method. The presence of fluorine was found to impart higher stabilization to the (100) facets through density functional theory calculations that evaluated the energetics of F-substitution at surface oxygen sites. These calculations suggest that the cubic morphology results from surface binding of F atoms. In addition, fluorine acts as an anionic aliovalent dopant in the cubic bixbyite lattice of In ₂ O ₃ , introducing a high concentration of free electrons leading to LSPR. We confirmed the presence of lattice fluorine dopants in these cubes using solid-state ¹⁹ F and ¹¹⁵ In nuclear magnetic resonance spectroscopy. The cubes exhibit narrow, shape-dependent multimodal LSPR extinction peaks due to corner- and edge-centered modes. The spatial origin of these different contributions to the spectral response is directly visualized by electron energy loss spectroscopy in a scanning transmission electron microscope.

Original language	English
Pages (from-to)	2661-2676
Number of pages	16
Journal	Chemistry of Materials
Volume	31
Issue number	7
DOIs	https://doi.org/10.1021/acs.chemmater.9b00906
State	Published - Apr 9 2019

Funding

S.H.C., S.G., L.C.R., C.J.D, and D.J.M. acknowledge the support from the National Science Foundation (NSF, CHE-1609656, CBET-1704634, NASCENT, an NSF ERCEEC-1160494, and CDCM, an NSF MRSECDMR-1720595), the Welch Foundation (F-1848), and Fulbright Program (IIE-15151071). We thank A. Dolocan, K. Jarvis, and H. Celio in the Texas Materials Institute (TMI) for user facility assistance. Y.L. and X.Z. acknowledge support from the Welch Foundation (Grant No. F-1959-20180324). Y.L. thanks the startup support from UT Austin. This work used computational resources sponsored by the Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy located at the National Renewable Energy Laboratory (NREL) and the Texas Advanced Computing Center (TACC) at UT Austin. Z.J.B. was supported by a grant from the BASF Corporation. The solid-state NMR measurements made use of the MRL Shared Experimental Facilities of the University of California, Santa Barbara, which are supported by the MRSEC Program of the NSF under Award No. DMR 1720256; a member of the NSF-funded Materials Research Facilities Network (www.mrfn.org). We thank Drs. Z. Gan, I. Hung, and X. Wang for assistance with the solid-state 115In NMR measurements of the F:In2O3 NCs conducted at the National High Magnetic Field Laboratory, which is supported by the National Science Foundation Cooperative Agreement No. DMR-1644779 and the State of Florida. Some microscopy research was performed as part of a user proposal at Oak Ridge National Laboratory’s (ORNL) the Center for Nanophase Materials Sciences (CNMS), which is a U.S. Department of Energy, Office of Science User Facility (J.A.H., J.-C.I.). This research was conducted, in part, using instrumentation within ORNL’s Materials Characterization Core provided by UT-Battelle, LLC, under contract No. DE-AC05-00OR22725 with the DOE. L.C.R. acknowledges the MMRRSA School at ORNL.

Funders	Funder number
CDCM	MRSECDMR-1720595
Fulbright program	IIE-15151071
NSF ERC	EEC-1160494
Texas Advanced Computing Center
National Science Foundation	CHE-1609656, 1704634, CBET-1704634
U.S. Department of Energy
Welch Foundation	F-1848
Office of Energy Efficiency and Renewable Energy
National Renewable Energy Laboratory
University of California, Santa Barbara
BASF Corporation
University of Texas at Austin

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10.1021/acs.chemmater.9b00906

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Cho, S. H., Ghosh, S., Berkson, Z. J., Hachtel, J. A., Shi, J., Zhao, X., Reimnitz, L. C., Dahlman, C. J., Ho, Y., Yang, A., Liu, Y., Idrobo, J. C., Chmelka, B. F., & Milliron, D. J. (2019). Syntheses of Colloidal F:In ₂ O ₃ Cubes: Fluorine-Induced Faceting and Infrared Plasmonic Response. Chemistry of Materials, 31(7), 2661-2676. https://doi.org/10.1021/acs.chemmater.9b00906

@article{145e057ef89b43418953d9e944c472c7,

title = "Syntheses of Colloidal F:In 2 O 3 Cubes: Fluorine-Induced Faceting and Infrared Plasmonic Response",

abstract = " Cube-shaped nanocrystals (NCs) of conventional metals like gold and silver generally exhibit localized surface plasmon resonance (LSPR) in the visible region with spectral modes determined by their faceted shapes. However, faceted NCs exhibiting LSPR response in the infrared (IR) region are relatively rare. Here, we describe the colloidal synthesis of nanoscale fluorine-doped indium oxide (F:In 2 O 3 ) cubes with LSPR response in the IR region, wherein fluorine was found to both direct the cubic morphology and act as an aliovalent dopant. Single-crystalline 160 nm F:In 2 O 3 cubes terminated by (100) facets and concave cubes were synthesized using a colloidal heat-up method. The presence of fluorine was found to impart higher stabilization to the (100) facets through density functional theory calculations that evaluated the energetics of F-substitution at surface oxygen sites. These calculations suggest that the cubic morphology results from surface binding of F atoms. In addition, fluorine acts as an anionic aliovalent dopant in the cubic bixbyite lattice of In 2 O 3 , introducing a high concentration of free electrons leading to LSPR. We confirmed the presence of lattice fluorine dopants in these cubes using solid-state 19 F and 115 In nuclear magnetic resonance spectroscopy. The cubes exhibit narrow, shape-dependent multimodal LSPR extinction peaks due to corner- and edge-centered modes. The spatial origin of these different contributions to the spectral response is directly visualized by electron energy loss spectroscopy in a scanning transmission electron microscope.",

author = "Cho, {Shin Hum} and Sandeep Ghosh and Berkson, {Zachariah J.} and Hachtel, {Jordan A.} and Jianjian Shi and Xunhua Zhao and Reimnitz, {Lauren C.} and Dahlman, {Clayton J.} and Yujing Ho and Anni Yang and Yuanyue Liu and Idrobo, {Juan Carlos} and Chmelka, {Bradley F.} and Milliron, {Delia J.}",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = apr,

day = "9",

doi = "10.1021/acs.chemmater.9b00906",

language = "English",

volume = "31",

pages = "2661--2676",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

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Cho, SH, Ghosh, S, Berkson, ZJ, Hachtel, JA, Shi, J, Zhao, X, Reimnitz, LC, Dahlman, CJ, Ho, Y, Yang, A, Liu, Y, Idrobo, JC, Chmelka, BF & Milliron, DJ 2019, 'Syntheses of Colloidal F:In ₂ O ₃ Cubes: Fluorine-Induced Faceting and Infrared Plasmonic Response', Chemistry of Materials, vol. 31, no. 7, pp. 2661-2676. https://doi.org/10.1021/acs.chemmater.9b00906

Syntheses of Colloidal F:In ₂ O ₃ Cubes: Fluorine-Induced Faceting and Infrared Plasmonic Response. / Cho, Shin Hum; Ghosh, Sandeep; Berkson, Zachariah J. et al.
In: Chemistry of Materials, Vol. 31, No. 7, 09.04.2019, p. 2661-2676.

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

TY - JOUR

T1 - Syntheses of Colloidal F:In 2 O 3 Cubes

T2 - Fluorine-Induced Faceting and Infrared Plasmonic Response

AU - Cho, Shin Hum

AU - Ghosh, Sandeep

AU - Berkson, Zachariah J.

AU - Hachtel, Jordan A.

AU - Shi, Jianjian

AU - Zhao, Xunhua

AU - Reimnitz, Lauren C.

AU - Dahlman, Clayton J.

AU - Ho, Yujing

AU - Yang, Anni

AU - Liu, Yuanyue

AU - Idrobo, Juan Carlos

AU - Chmelka, Bradley F.

AU - Milliron, Delia J.

PY - 2019/4/9

Y1 - 2019/4/9

N2 - Cube-shaped nanocrystals (NCs) of conventional metals like gold and silver generally exhibit localized surface plasmon resonance (LSPR) in the visible region with spectral modes determined by their faceted shapes. However, faceted NCs exhibiting LSPR response in the infrared (IR) region are relatively rare. Here, we describe the colloidal synthesis of nanoscale fluorine-doped indium oxide (F:In 2 O 3 ) cubes with LSPR response in the IR region, wherein fluorine was found to both direct the cubic morphology and act as an aliovalent dopant. Single-crystalline 160 nm F:In 2 O 3 cubes terminated by (100) facets and concave cubes were synthesized using a colloidal heat-up method. The presence of fluorine was found to impart higher stabilization to the (100) facets through density functional theory calculations that evaluated the energetics of F-substitution at surface oxygen sites. These calculations suggest that the cubic morphology results from surface binding of F atoms. In addition, fluorine acts as an anionic aliovalent dopant in the cubic bixbyite lattice of In 2 O 3 , introducing a high concentration of free electrons leading to LSPR. We confirmed the presence of lattice fluorine dopants in these cubes using solid-state 19 F and 115 In nuclear magnetic resonance spectroscopy. The cubes exhibit narrow, shape-dependent multimodal LSPR extinction peaks due to corner- and edge-centered modes. The spatial origin of these different contributions to the spectral response is directly visualized by electron energy loss spectroscopy in a scanning transmission electron microscope.

AB - Cube-shaped nanocrystals (NCs) of conventional metals like gold and silver generally exhibit localized surface plasmon resonance (LSPR) in the visible region with spectral modes determined by their faceted shapes. However, faceted NCs exhibiting LSPR response in the infrared (IR) region are relatively rare. Here, we describe the colloidal synthesis of nanoscale fluorine-doped indium oxide (F:In 2 O 3 ) cubes with LSPR response in the IR region, wherein fluorine was found to both direct the cubic morphology and act as an aliovalent dopant. Single-crystalline 160 nm F:In 2 O 3 cubes terminated by (100) facets and concave cubes were synthesized using a colloidal heat-up method. The presence of fluorine was found to impart higher stabilization to the (100) facets through density functional theory calculations that evaluated the energetics of F-substitution at surface oxygen sites. These calculations suggest that the cubic morphology results from surface binding of F atoms. In addition, fluorine acts as an anionic aliovalent dopant in the cubic bixbyite lattice of In 2 O 3 , introducing a high concentration of free electrons leading to LSPR. We confirmed the presence of lattice fluorine dopants in these cubes using solid-state 19 F and 115 In nuclear magnetic resonance spectroscopy. The cubes exhibit narrow, shape-dependent multimodal LSPR extinction peaks due to corner- and edge-centered modes. The spatial origin of these different contributions to the spectral response is directly visualized by electron energy loss spectroscopy in a scanning transmission electron microscope.

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U2 - 10.1021/acs.chemmater.9b00906

DO - 10.1021/acs.chemmater.9b00906

M3 - Article

AN - SCOPUS:85063383072

SN - 0897-4756

VL - 31

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JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 7

ER -

Syntheses of Colloidal F:In ₂ O ₃ Cubes: Fluorine-Induced Faceting and Infrared Plasmonic Response

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