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Title: Atomistic Interrogation of B–N Co-dopant Structures and Their Electronic Effects in Graphene

Abstract

Chemical doping has been demonstrated to be an effective method for producing high-quality, large-area graphene with controlled carrier concentrations and an atomically tailored work function. Furthermore, the emergent optoelectronic properties and surface reactivity of carbon nanostructures are dictated by the microstructure of atomic dopants. Co-doping of graphene with boron and nitrogen offers the possibility to further tune the electronic properties of graphene at the atomic level, potentially creating p- and n-type domains in a single carbon sheet, opening a gap between valence and conduction bands in the 2-D semimetal. When using a suite of high-resolution synchrotron-based X-ray techniques, scanning tunneling microscopy, and density functional theory based computation we visualize and characterize B–N dopant bond structures and their electronic effects at the atomic level in single-layer graphene grown on a copper substrate. We find there is a thermodynamic driving force for B and N atoms to cluster into BNC structures in graphene, rather than randomly distribute into isolated B and N graphitic dopants, although under the present growth conditions, kinetics limit segregation of large B–N domains. We also observe that the doping effect of these BNC structures, which open a small band gap in graphene, follows the B:N ratio (B >more » N, p-type; B < N, n-type; B=N, neutral). We attribute this to the comparable electron-withdrawing and -donating effects, respectively, of individual graphitic B and N dopants, although local electrostatics also play a role in the work function change.« less

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [3];  [5];  [7];  [4]
  1. Columbia Univ., New York, NY (United States). Materials Research Science and Engineering Center (MRSEC); State Univ. of New York, NY (United States). Dept. of Science and Mathematics
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource
  3. Columbia Univ., New York, NY (United States). Dept. of Chemistry
  4. Columbia Univ., New York, NY (United States). Dept. of Physics
  5. Cornell Univ., Ithaca, NY (United States). Chemistry Dept.
  6. National Inst. of Standards and Technology, Gaithersburg, MD (United States). Materials Measurement Lab.
  7. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1336131
Report Number(s):
BNL-112597-2016-JA
Journal ID: ISSN 1936-0851; R&D Project: 16068; KC0403020
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 10; Journal Issue: 7; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; atomic design; chemical bonding; doping; electronic structure; graphene; scanning tunneling microscopy; work function; X-ray spectroscopy

Citation Formats

Schiros, Theanne, Nordlund, Dennis, Palova, Lucia, Zhao, Liuyan, Levendorf, Mark, Jaye, Cherno, Reichman, David, Park, Jiwoong, Hybertsen, Mark, and Pasupathy, Abhay. Atomistic Interrogation of B–N Co-dopant Structures and Their Electronic Effects in Graphene. United States: N. p., 2016. Web. https://doi.org/10.1021/acsnano.6b01318.
Schiros, Theanne, Nordlund, Dennis, Palova, Lucia, Zhao, Liuyan, Levendorf, Mark, Jaye, Cherno, Reichman, David, Park, Jiwoong, Hybertsen, Mark, & Pasupathy, Abhay. Atomistic Interrogation of B–N Co-dopant Structures and Their Electronic Effects in Graphene. United States. https://doi.org/10.1021/acsnano.6b01318
Schiros, Theanne, Nordlund, Dennis, Palova, Lucia, Zhao, Liuyan, Levendorf, Mark, Jaye, Cherno, Reichman, David, Park, Jiwoong, Hybertsen, Mark, and Pasupathy, Abhay. Tue . "Atomistic Interrogation of B–N Co-dopant Structures and Their Electronic Effects in Graphene". United States. https://doi.org/10.1021/acsnano.6b01318. https://www.osti.gov/servlets/purl/1336131.
@article{osti_1336131,
title = {Atomistic Interrogation of B–N Co-dopant Structures and Their Electronic Effects in Graphene},
author = {Schiros, Theanne and Nordlund, Dennis and Palova, Lucia and Zhao, Liuyan and Levendorf, Mark and Jaye, Cherno and Reichman, David and Park, Jiwoong and Hybertsen, Mark and Pasupathy, Abhay},
abstractNote = {Chemical doping has been demonstrated to be an effective method for producing high-quality, large-area graphene with controlled carrier concentrations and an atomically tailored work function. Furthermore, the emergent optoelectronic properties and surface reactivity of carbon nanostructures are dictated by the microstructure of atomic dopants. Co-doping of graphene with boron and nitrogen offers the possibility to further tune the electronic properties of graphene at the atomic level, potentially creating p- and n-type domains in a single carbon sheet, opening a gap between valence and conduction bands in the 2-D semimetal. When using a suite of high-resolution synchrotron-based X-ray techniques, scanning tunneling microscopy, and density functional theory based computation we visualize and characterize B–N dopant bond structures and their electronic effects at the atomic level in single-layer graphene grown on a copper substrate. We find there is a thermodynamic driving force for B and N atoms to cluster into BNC structures in graphene, rather than randomly distribute into isolated B and N graphitic dopants, although under the present growth conditions, kinetics limit segregation of large B–N domains. We also observe that the doping effect of these BNC structures, which open a small band gap in graphene, follows the B:N ratio (B > N, p-type; B < N, n-type; B=N, neutral). We attribute this to the comparable electron-withdrawing and -donating effects, respectively, of individual graphitic B and N dopants, although local electrostatics also play a role in the work function change.},
doi = {10.1021/acsnano.6b01318},
journal = {ACS Nano},
number = 7,
volume = 10,
place = {United States},
year = {2016},
month = {6}
}

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Works referenced in this record:

Fine Structure Constant Defines Visual Transparency of Graphene
journal, June 2008


Atomic layers of hybridized boron nitride and graphene domains
journal, February 2010

  • Ci, Lijie; Song, Li; Jin, Chuanhong
  • Nature Materials, Vol. 9, Issue 5, p. 430-435
  • DOI: 10.1038/nmat2711

Grains and grain boundaries in highly crystalline monolayer molybdenum disulphide
journal, May 2013

  • van der Zande, Arend M.; Huang, Pinshane Y.; Chenet, Daniel A.
  • Nature Materials, Vol. 12, Issue 6, p. 554-561
  • DOI: 10.1038/nmat3633

Atomically thin p–n junctions with van der Waals heterointerfaces
journal, August 2014

  • Lee, Chul-Ho; Lee, Gwan-Hyoung; van der Zande, Arend M.
  • Nature Nanotechnology, Vol. 9, Issue 9
  • DOI: 10.1038/nnano.2014.150

Van der Waals heterostructures
journal, July 2013

  • Geim, A. K.; Grigorieva, I. V.
  • Nature, Vol. 499, Issue 7459, p. 419-425
  • DOI: 10.1038/nature12385

Binary and Ternary Atomic Layers Built from Carbon, Boron, and Nitrogen
journal, July 2012

  • Song, Li; Liu, Zheng; Reddy, Arava Leela Mohana
  • Advanced Materials, Vol. 24, Issue 36
  • DOI: 10.1002/adma.201201792

Single-layer graphene cathodes for organic photovoltaics
journal, March 2011

  • Cox, Marshall; Gorodetsky, Alon; Kim, Bumjung
  • Applied Physics Letters, Vol. 98, Issue 12
  • DOI: 10.1063/1.3569601

Simultaneous doping of boron and nitrogen into a carbon to enhance its oxygen reduction activity in proton exchange membrane fuel cells
journal, December 2006


Vertically Aligned BCN Nanotubes as Efficient Metal-Free Electrocatalysts for the Oxygen Reduction Reaction: A Synergetic Effect by Co-Doping with Boron and Nitrogen
journal, October 2011

  • Wang , Shuangyin; Iyyamperumal , Eswaramoorthi; Roy, Ajit
  • Angewandte Chemie International Edition, Vol. 50, Issue 49
  • DOI: 10.1002/anie.201105204

Doped Graphene Sheets As Anode Materials with Superhigh Rate and Large Capacity for Lithium Ion Batteries
journal, June 2011

  • Wu, Zhong-Shuai; Ren, Wencai; Xu, Li
  • ACS Nano, Vol. 5, Issue 7
  • DOI: 10.1021/nn2006249

Nitrogen-Doped Graphene for High-Performance Ultracapacitors and the Importance of Nitrogen-Doped Sites at Basal Planes
journal, June 2011

  • Jeong, Hyung Mo; Lee, Jung Woo; Shin, Weon Ho
  • Nano Letters, Vol. 11, Issue 6
  • DOI: 10.1021/nl2009058

Three-Dimensional Nitrogen and Boron Co-doped Graphene for High-Performance All-Solid-State Supercapacitors
journal, July 2012

  • Wu, Zhong-Shuai; Winter, Andreas; Chen, Long
  • Advanced Materials, Vol. 24, Issue 37
  • DOI: 10.1002/adma.201201948

Review on Recent Progress in Nitrogen-Doped Graphene: Synthesis, Characterization, and Its Potential Applications
journal, April 2012

  • Wang, Haibo; Maiyalagan, Thandavarayan; Wang, Xin
  • ACS Catalysis, Vol. 2, Issue 5
  • DOI: 10.1021/cs200652y

Epitaxial Growth of Molecular Crystals on van der Waals Substrates for High-Performance Organic Electronics
journal, January 2014

  • Lee, Chul-Ho; Schiros, Theanne; Santos, Elton J. G.
  • Advanced Materials, Vol. 26, Issue 18
  • DOI: 10.1002/adma.201304973

Controlling the Electronic Structure of Bilayer Graphene
journal, August 2006


Simultaneous Nitrogen Doping and Reduction of Graphene Oxide
journal, November 2009

  • Li, Xiaolin; Wang, Hailiang; Robinson, Joshua T.
  • Journal of the American Chemical Society, Vol. 131, Issue 43
  • DOI: 10.1021/ja907098f

Chemical doping of graphene
journal, January 2011

  • Liu, Hongtao; Liu, Yunqi; Zhu, Daoben
  • J. Mater. Chem., Vol. 21, Issue 10
  • DOI: 10.1039/C0JM02922J

Controllable N-Doping of Graphene
journal, December 2010

  • Guo, Beidou; Liu, Qian; Chen, Erdan
  • Nano Letters, Vol. 10, Issue 12
  • DOI: 10.1021/nl103079j

N-Doping of Graphene Through Electrothermal Reactions with Ammonia
journal, May 2009


Nitrogen-Doped Graphene and Its Application in Electrochemical Biosensing
journal, March 2010

  • Wang, Ying; Shao, Yuyan; Matson, Dean W.
  • ACS Nano, Vol. 4, Issue 4
  • DOI: 10.1021/nn100315s

Visualizing Individual Nitrogen Dopants in Monolayer Graphene
journal, August 2011


Connecting Dopant Bond Type with Electronic Structure in N-Doped Graphene
journal, July 2012

  • Schiros, Theanne; Nordlund, Dennis; Pálová, Lucia
  • Nano Letters, Vol. 12, Issue 8
  • DOI: 10.1021/nl301409h

Growth and electronic structure of boron-doped graphene
journal, April 2013


Raman Spectroscopy of Boron-Doped Single-Layer Graphene
journal, June 2012

  • Kim, Yoong Ahm; Fujisawa, Kazunori; Muramatsu, Hiroyuki
  • ACS Nano, Vol. 6, Issue 7
  • DOI: 10.1021/nn301728j

Local Atomic and Electronic Structure of Boron Chemical Doping in Monolayer Graphene
journal, September 2013

  • Zhao, Liuyan; Levendorf, Mark; Goncher, Scott
  • Nano Letters, Vol. 13, Issue 10
  • DOI: 10.1021/nl401781d

X-Ray Spectroscopic Investigation of Chlorinated Graphene: Surface Structure and Electronic Effects
journal, May 2015

  • Zhang, Xu; Schiros, Theanne; Nordlund, Dennis
  • Advanced Functional Materials, Vol. 25, Issue 26
  • DOI: 10.1002/adfm.201500541

Impact of Chlorine Functionalization on High-Mobility Chemical Vapor Deposition Grown Graphene
journal, July 2013


Electronic Interaction between Nitrogen Atoms in Doped Graphene
journal, January 2015

  • Tison, Yann; Lagoute, Jérôme; Repain, Vincent
  • ACS Nano, Vol. 9, Issue 1
  • DOI: 10.1021/nn506074u

Long-range interactions between substitutional nitrogen dopants in graphene: Electronic properties calculations
journal, July 2012


Designing band gap of graphene by B and N dopant atoms
journal, January 2013


Electronic Structure Modification of Ion Implanted Graphene: The Spectroscopic Signatures of p- and n-Type Doping
journal, October 2015

  • Kepaptsoglou, Demie; Hardcastle, Trevor P.; Seabourne, Che R.
  • ACS Nano, Vol. 9, Issue 11
  • DOI: 10.1021/acsnano.5b05305

Ion Implantation of Graphene—Toward IC Compatible Technologies
journal, September 2013

  • Bangert, U.; Pierce, W.; Kepaptsoglou, D. M.
  • Nano Letters, Vol. 13, Issue 10
  • DOI: 10.1021/nl402812y

Experimental analysis of charge redistribution due to chemical bonding by high-resolution transmission electron microscopy
journal, January 2011

  • Meyer, Jannik C.; Kurasch, Simon; Park, Hye Jin
  • Nature Materials, Vol. 10, Issue 3
  • DOI: 10.1038/nmat2941

Probing the Bonding in Nitrogen-Doped Graphene Using Electron Energy Loss Spectroscopy
journal, July 2013

  • Nicholls, Rebecca J.; Murdock, Adrian T.; Tsang, Joshua
  • ACS Nano, Vol. 7, Issue 8
  • DOI: 10.1021/nn402489v

Stability and Spectroscopy of Single Nitrogen Dopants in Graphene at Elevated Temperatures
journal, November 2014

  • Warner, Jamie H.; Lin, Yung-Chang; He, Kuang
  • ACS Nano, Vol. 8, Issue 11
  • DOI: 10.1021/nn5054798

Doping Graphitic and Carbon Nanotube Structures with Boron and Nitrogen
journal, December 1994


Half-metallicity induced by charge injection in hexagonal boron nitride clusters embedded in graphene
journal, November 2012


Band Gap Engineering of Chemical Vapor Deposited Graphene by in Situ BN Doping
journal, January 2013

  • Chang, Cheng-Kai; Kataria, Satender; Kuo, Chun-Chiang
  • ACS Nano, Vol. 7, Issue 2
  • DOI: 10.1021/nn3049158

BN-Embedded Graphene with a Ubiquitous Gap Opening
journal, September 2012

  • Zhao, Ruiqi; Wang, Jinying; Yang, Mingmei
  • The Journal of Physical Chemistry C, Vol. 116, Issue 39
  • DOI: 10.1021/jp306660x

Electronic structure tuning and band gap opening of graphene by hole/electron codoping
journal, October 2011


Boron-Doped, Nitrogen-Doped, and Codoped Graphene on Cu(111): A DFT + vdW Study
journal, March 2015

  • Ferrighi, Lara; Trioni, Mario Italo; Di Valentin, Cristiana
  • The Journal of Physical Chemistry C, Vol. 119, Issue 11
  • DOI: 10.1021/jp512522m

DFT study of optical properties of pure and doped graphene
journal, August 2014

  • Rani, Pooja; Dubey, Girija S.; Jindal, V. K.
  • Physica E: Low-dimensional Systems and Nanostructures, Vol. 62
  • DOI: 10.1016/j.physe.2014.04.010

Ternary BCN thin films deposited by reactive sputtering
journal, October 2000


Hard BCxNy thin films grown by dual ion beam sputtering
journal, September 2006


Bonding characterization of BC 2 N thin films
journal, May 1996

  • Watanabe, M. O.; Itoh, S.; Mizushima, K.
  • Applied Physics Letters, Vol. 68, Issue 21
  • DOI: 10.1063/1.116369

Nitrogen 1s electron binding energy assignment in carbon nitride thin films with different structures
journal, October 1997

  • Zheng, W. T.; Xing, K. Z.; Hellgren, N.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 87, Issue 1
  • DOI: 10.1016/S0368-2048(97)00083-2

Nitrogen bonding structure in carbon nitride thin films studied by soft x-ray spectroscopy
journal, December 2001

  • Hellgren, Niklas; Guo, Jinghua; Såthe, Conny
  • Applied Physics Letters, Vol. 79, Issue 26
  • DOI: 10.1063/1.1428108

Chemical bonding states and local structures of the oriented hexagonal BCN films synthesized by microwave plasma CVD
journal, June 2008

  • Mannan, Md. Abdul; Noguchi, Hideyuki; Kida, Tetsuya
  • Materials Science in Semiconductor Processing, Vol. 11, Issue 3
  • DOI: 10.1016/j.mssp.2009.04.003

Speciation of BC x N y films grown by PECVD with trimethylborazine precursor
journal, August 2009

  • Baake, Olaf; Hoffmann, Peter S.; Klein, Andreas
  • Analytical and Bioanalytical Chemistry, Vol. 395, Issue 6
  • DOI: 10.1007/s00216-009-3056-6

Orientation of B–C–N hybrid films deposited on Ni (111) and polycrystalline Ti substrates explored by X-ray absorption spectroscopy
journal, January 2011


Synthesis of Few-Layer Hexagonal Boron Nitride Thin Film by Chemical Vapor Deposition
journal, October 2010

  • Shi, Yumeng; Hamsen, Christoph; Jia, Xiaoting
  • Nano Letters, Vol. 10, Issue 10
  • DOI: 10.1021/nl1023707

Mechanical properties of hexagonal boron nitride synthesized from film of Cu/BN mixture by surface segregation
journal, January 2001


X-ray photoelectron spectroscopy investigation of boron carbide films deposited by sputtering
journal, November 2004


Photoemission and x-ray-absorption study of boron carbide and its surface thermal stability
journal, May 1998


π * and σ * Excitons in C 1 s Absorption of Graphite
journal, January 1995


Ab initio study of the interactions between boron and nitrogen dopants in graphene
journal, August 2012

  • Al-Aqtash, Nabil; Al-Tarawneh, Khaldoun M.; Tawalbeh, Tarek
  • Journal of Applied Physics, Vol. 112, Issue 3
  • DOI: 10.1063/1.4742063

Polarization-dependent boron and nitrogen K nexafs of hexagonal BN
journal, June 1996

  • Moscovici, J.; Loupias, G.; Parent, P. H.
  • Journal of Physics and Chemistry of Solids, Vol. 57, Issue 6-8
  • DOI: 10.1016/0022-3697(95)00415-7

Direct observation of defect levels in hexagonal BN by soft X-ray absorption spectroscopy
journal, April 2009


X-ray photoelectron spectroscopic observation on B–C–N hybrids synthesized by ion beam deposition of borazine
journal, May 2005

  • Uddin, Md. Nizam; Shimoyama, Iwao; Baba, Yuji
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 23, Issue 3
  • DOI: 10.1116/1.1894667

Phase stability of boron carbon nitride in a heterographene structure: A first-principles study
journal, April 2009


Atomic Structure, Electronic Properties, and Reactivity of In-Plane Heterostructures of Graphene and Hexagonal Boron Nitride
journal, July 2014

  • Krsmanović, Radisav S.; Šljivančanin, Željko
  • The Journal of Physical Chemistry C, Vol. 118, Issue 29
  • DOI: 10.1021/jp501581g

Atomic subshell photoionization cross sections and asymmetry parameters: 1 ⩽ Z ⩽ 103
journal, January 1985


Self-interaction correction to density-functional approximations for many-electron systems
journal, May 1981


QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Theory and Application for the Scanning Tunneling Microscope
journal, June 1983


Theory of the scanning tunneling microscope
journal, January 1985


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    • Journal of Materials Chemistry C, Vol. 6, Issue 23
    • DOI: 10.1039/c8tc00463c

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    journal, September 2019


    Plasma-induced synthesis of boron and nitrogen co-doped reduced graphene oxide for super-capacitors
    journal, March 2019


    Fluorometric and colorimetric determination of hypochlorite using carbon nanodots doped with boron and nitrogen
    journal, May 2019


    Multiplexed ratiometric photoluminescent detection of pyrophosphate using anisotropic boron-doped nitrogen-rich carbon rugby ball-like nanodots
    journal, January 2018

    • Wang, Zhong-Xia; Yu, Xian-He; Li, Feng
    • Journal of Materials Chemistry B, Vol. 6, Issue 12
    • DOI: 10.1039/c7tb02708g

    Carbon Nano-Onions: A Review of Recent Progress in Synthesis and Applications
    journal, February 2019