Revealing the Local Electronic Structure of a Single-Layer Covalent Organic Framework through Electronic Decoupling

Daniel J. Rizzo; Qingqing Dai; Christopher Bronner; Gregory Veber; Brian J. Smith; Michio Matsumoto; Simil Thomas; Giang D. Nguyen; Patrick R. Forrester; William Zhao; Jakob H. Jørgensen; William R. Dichtel; Felix R. Fischer; Hong Li; Jean Luc Bredas; Michael F. Crommie

doi:10.1021/acs.nanolett.9b03998

Revealing the Local Electronic Structure of a Single-Layer Covalent Organic Framework through Electronic Decoupling

Daniel J. Rizzo, Qingqing Dai, Christopher Bronner, Gregory Veber, Brian J. Smith, Michio Matsumoto, Simil Thomas, Giang D. Nguyen, Patrick R. Forrester, William Zhao, Jakob H. Jørgensen, William R. Dichtel, Felix R. Fischer, Hong Li, Jean Luc Bredas, Michael F. Crommie

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

39 Scopus citations

Abstract

Covalent organic frameworks (COFs) are molecule-based 2D and 3D materials that possess a wide range of mechanical and electronic properties. We have performed a joint experimental and theoretical study of the electronic structure of boroxine-linked COFs grown under ultrahigh vacuum conditions and characterized using scanning tunneling spectroscopy on Au(111) and hBN/Cu(111) substrates. Our results show that a single hBN layer electronically decouples the COF from the metallic substrate, thus suppressing substrate-induced broadening and revealing new features in the COF electronic local density of states (LDOS). The resulting sharpening of LDOS features allows us to experimentally determine the COF band gap, bandwidths, and the electronic hopping amplitude between adjacent COF bridge sites. These experimental parameters are consistent with the results of first-principles theoretical predictions.

Original language	English (US)
Pages (from-to)	963-970
Number of pages	8
Journal	Nano Letters
Volume	20
Issue number	2
DOIs	https://doi.org/10.1021/acs.nanolett.9b03998
State	Published - Feb 12 2020
Externally published	Yes

Keywords

2D polymer
Covalent organic frameworks (COFs)
Kagome lattice
biphenyl COF (BP-COF)
density functional theory (DFT)
scanning tunneling microscopy (STM)
scanning tunneling spectroscopy (STS)

ASJC Scopus subject areas

Bioengineering
General Chemistry
General Materials Science
Condensed Matter Physics
Mechanical Engineering

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10.1021/acs.nanolett.9b03998

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Rizzo, D. J., Dai, Q., Bronner, C., Veber, G., Smith, B. J., Matsumoto, M., Thomas, S., Nguyen, G. D., Forrester, P. R., Zhao, W., Jørgensen, J. H., Dichtel, W. R., Fischer, F. R., Li, H., Bredas, J. L., & Crommie, M. F. (2020). Revealing the Local Electronic Structure of a Single-Layer Covalent Organic Framework through Electronic Decoupling. Nano Letters, 20(2), 963-970. https://doi.org/10.1021/acs.nanolett.9b03998

Rizzo, DJ, Dai, Q, Bronner, C, Veber, G, Smith, BJ, Matsumoto, M, Thomas, S, Nguyen, GD, Forrester, PR, Zhao, W, Jørgensen, JH, Dichtel, WR, Fischer, FR, Li, H , Bredas, JL & Crommie, MF 2020, 'Revealing the Local Electronic Structure of a Single-Layer Covalent Organic Framework through Electronic Decoupling', Nano Letters, vol. 20, no. 2, pp. 963-970. https://doi.org/10.1021/acs.nanolett.9b03998

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title = "Revealing the Local Electronic Structure of a Single-Layer Covalent Organic Framework through Electronic Decoupling",

abstract = "Covalent organic frameworks (COFs) are molecule-based 2D and 3D materials that possess a wide range of mechanical and electronic properties. We have performed a joint experimental and theoretical study of the electronic structure of boroxine-linked COFs grown under ultrahigh vacuum conditions and characterized using scanning tunneling spectroscopy on Au(111) and hBN/Cu(111) substrates. Our results show that a single hBN layer electronically decouples the COF from the metallic substrate, thus suppressing substrate-induced broadening and revealing new features in the COF electronic local density of states (LDOS). The resulting sharpening of LDOS features allows us to experimentally determine the COF band gap, bandwidths, and the electronic hopping amplitude between adjacent COF bridge sites. These experimental parameters are consistent with the results of first-principles theoretical predictions.",

keywords = "2D polymer, Covalent organic frameworks (COFs), Kagome lattice, biphenyl COF (BP-COF), density functional theory (DFT), scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS)",

author = "Rizzo, {Daniel J.} and Qingqing Dai and Christopher Bronner and Gregory Veber and Smith, {Brian J.} and Michio Matsumoto and Simil Thomas and Nguyen, {Giang D.} and Forrester, {Patrick R.} and William Zhao and J{\o}rgensen, {Jakob H.} and Dichtel, {William R.} and Fischer, {Felix R.} and Hong Li and Bredas, {Jean Luc} and Crommie, {Michael F.}",

note = "Funding Information: This research was supported by the Army Research Office Multidisciplinary University Research Initiative (MURI) program under Grant No. W911NF-15-1-0447 (STM spectroscopy, DFT analysis) and by the U.S. Department of Energy, Office of Basic Energy Sciences Nanomachine Program, under Contract No. DEAC02-05CH11231 (sample preparation). The work at Georgia Tech was supported in part by a grant of computer time from the DOD High Performance Computing Modernization Program. Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = feb,

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doi = "10.1021/acs.nanolett.9b03998",

language = "English (US)",

volume = "20",

pages = "963--970",

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T1 - Revealing the Local Electronic Structure of a Single-Layer Covalent Organic Framework through Electronic Decoupling

AU - Rizzo, Daniel J.

AU - Dai, Qingqing

AU - Bronner, Christopher

AU - Veber, Gregory

AU - Smith, Brian J.

AU - Matsumoto, Michio

AU - Thomas, Simil

AU - Nguyen, Giang D.

AU - Forrester, Patrick R.

AU - Zhao, William

AU - Jørgensen, Jakob H.

AU - Dichtel, William R.

AU - Fischer, Felix R.

AU - Li, Hong

AU - Bredas, Jean Luc

AU - Crommie, Michael F.

N1 - Funding Information: This research was supported by the Army Research Office Multidisciplinary University Research Initiative (MURI) program under Grant No. W911NF-15-1-0447 (STM spectroscopy, DFT analysis) and by the U.S. Department of Energy, Office of Basic Energy Sciences Nanomachine Program, under Contract No. DEAC02-05CH11231 (sample preparation). The work at Georgia Tech was supported in part by a grant of computer time from the DOD High Performance Computing Modernization Program. Publisher Copyright: Copyright © 2020 American Chemical Society.

PY - 2020/2/12

Y1 - 2020/2/12

N2 - Covalent organic frameworks (COFs) are molecule-based 2D and 3D materials that possess a wide range of mechanical and electronic properties. We have performed a joint experimental and theoretical study of the electronic structure of boroxine-linked COFs grown under ultrahigh vacuum conditions and characterized using scanning tunneling spectroscopy on Au(111) and hBN/Cu(111) substrates. Our results show that a single hBN layer electronically decouples the COF from the metallic substrate, thus suppressing substrate-induced broadening and revealing new features in the COF electronic local density of states (LDOS). The resulting sharpening of LDOS features allows us to experimentally determine the COF band gap, bandwidths, and the electronic hopping amplitude between adjacent COF bridge sites. These experimental parameters are consistent with the results of first-principles theoretical predictions.

AB - Covalent organic frameworks (COFs) are molecule-based 2D and 3D materials that possess a wide range of mechanical and electronic properties. We have performed a joint experimental and theoretical study of the electronic structure of boroxine-linked COFs grown under ultrahigh vacuum conditions and characterized using scanning tunneling spectroscopy on Au(111) and hBN/Cu(111) substrates. Our results show that a single hBN layer electronically decouples the COF from the metallic substrate, thus suppressing substrate-induced broadening and revealing new features in the COF electronic local density of states (LDOS). The resulting sharpening of LDOS features allows us to experimentally determine the COF band gap, bandwidths, and the electronic hopping amplitude between adjacent COF bridge sites. These experimental parameters are consistent with the results of first-principles theoretical predictions.

KW - 2D polymer

KW - Covalent organic frameworks (COFs)

KW - Kagome lattice

KW - biphenyl COF (BP-COF)

KW - density functional theory (DFT)

KW - scanning tunneling microscopy (STM)

KW - scanning tunneling spectroscopy (STS)

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JO - Nano Letters

JF - Nano Letters

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ER -

Revealing the Local Electronic Structure of a Single-Layer Covalent Organic Framework through Electronic Decoupling

Abstract

Keywords

ASJC Scopus subject areas

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