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Title: Borophene Synthesis on Au(111)

Abstract

Borophene (the first two-dimensional (2D) allotrope of boron) is emerging as a groundbreaking system for boron-based chemistry and, more broadly, the field of low-dimensional materials. Exploration of the phase space for growth is critical because borophene is a synthetic 2D material that does not have a bulk layered counterpart and thus cannot be isolated via exfoliation methods. Furthermore, we report synthesis of borophene on Au(111) substrates. Unlike previously studied growth on Ag substrates, boron diffuses into Au at elevated temperatures and segregates to the surface to form borophene islands as the substrate cools. These observations are supported by ab initio modeling of interstitial boron diffusion into the Au lattice. Borophene synthesis also modifies the surface reconstruction of the Au(111) substrate, resulting in a trigonal network that templates growth at low coverage. This initial growth is composed of discrete borophene nanoclusters, whose shape and size are consistent with theoretical predictions. As the concentration of boron increases, nanotemplating breaks down and larger borophene islands are observed. Spectroscopic measurements reveal that borophene grown on Au(111) possesses a metallic electronic structure, suggesting potential applications in 2D plasmonics, superconductivity, interconnects, electrodes, and transparent conductors.

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [1];  [5];  [3]; ORCiD logo [2]; ORCiD logo [5]
  1. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Rice Univ., Houston, TX (United States)
  4. Nanjing Univ. of Aeronautics and Astronautics, Nanjing (China)
  5. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of the Navy, Office of Naval Research (ONR)
OSTI Identifier:
1532535
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 13; Journal Issue: 4; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; Au(111); allotrope; borophene; scanning tunneling microscopy; synthesis; two-dimensional materials

Citation Formats

Kiraly, Brian, Liu, Xiaolong, Wang, Luqing, Zhang, Zhuhua, Mannix, Andrew J., Fisher, Brandon L., Yakobson, Boris I., Hersam, Mark C., and Guisinger, Nathan P. Borophene Synthesis on Au(111). United States: N. p., 2019. Web. doi:10.1021/acsnano.8b09339.
Kiraly, Brian, Liu, Xiaolong, Wang, Luqing, Zhang, Zhuhua, Mannix, Andrew J., Fisher, Brandon L., Yakobson, Boris I., Hersam, Mark C., & Guisinger, Nathan P. Borophene Synthesis on Au(111). United States. https://doi.org/10.1021/acsnano.8b09339
Kiraly, Brian, Liu, Xiaolong, Wang, Luqing, Zhang, Zhuhua, Mannix, Andrew J., Fisher, Brandon L., Yakobson, Boris I., Hersam, Mark C., and Guisinger, Nathan P. Thu . "Borophene Synthesis on Au(111)". United States. https://doi.org/10.1021/acsnano.8b09339. https://www.osti.gov/servlets/purl/1532535.
@article{osti_1532535,
title = {Borophene Synthesis on Au(111)},
author = {Kiraly, Brian and Liu, Xiaolong and Wang, Luqing and Zhang, Zhuhua and Mannix, Andrew J. and Fisher, Brandon L. and Yakobson, Boris I. and Hersam, Mark C. and Guisinger, Nathan P.},
abstractNote = {Borophene (the first two-dimensional (2D) allotrope of boron) is emerging as a groundbreaking system for boron-based chemistry and, more broadly, the field of low-dimensional materials. Exploration of the phase space for growth is critical because borophene is a synthetic 2D material that does not have a bulk layered counterpart and thus cannot be isolated via exfoliation methods. Furthermore, we report synthesis of borophene on Au(111) substrates. Unlike previously studied growth on Ag substrates, boron diffuses into Au at elevated temperatures and segregates to the surface to form borophene islands as the substrate cools. These observations are supported by ab initio modeling of interstitial boron diffusion into the Au lattice. Borophene synthesis also modifies the surface reconstruction of the Au(111) substrate, resulting in a trigonal network that templates growth at low coverage. This initial growth is composed of discrete borophene nanoclusters, whose shape and size are consistent with theoretical predictions. As the concentration of boron increases, nanotemplating breaks down and larger borophene islands are observed. Spectroscopic measurements reveal that borophene grown on Au(111) possesses a metallic electronic structure, suggesting potential applications in 2D plasmonics, superconductivity, interconnects, electrodes, and transparent conductors.},
doi = {10.1021/acsnano.8b09339},
journal = {ACS Nano},
number = 4,
volume = 13,
place = {United States},
year = {2019},
month = {3}
}

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Works referenced in this record:

β-Rhombohedral Boron: At the Crossroads of the Chemistry of Boron and the Physics of Frustration
journal, March 2013

  • Ogitsu, Tadashi; Schwegler, Eric; Galli, Giulia
  • Chemical Reviews, Vol. 113, Issue 5
  • DOI: 10.1021/cr300356t

Ionic high-pressure form of elemental boron
journal, January 2009

  • Oganov, Artem R.; Chen, Jiuhua; Gatti, Carlo
  • Nature, Vol. 457, Issue 7231
  • DOI: 10.1038/nature07736

Hydrocarbon analogues of boron clusters — planarity, aromaticity and antiaromaticity
journal, November 2003

  • Zhai, Hua-Jin; Kiran, Boggavarapu; Li, Jun
  • Nature Materials, Vol. 2, Issue 12
  • DOI: 10.1038/nmat1012

Understanding Boron through Size-Selected Clusters: Structure, Chemical Bonding, and Fluxionality
journal, February 2014

  • Sergeeva, Alina P.; Popov, Ivan A.; Piazza, Zachary A.
  • Accounts of Chemical Research, Vol. 47, Issue 4
  • DOI: 10.1021/ar400310g

Observation of an all-boron fullerene
journal, July 2014

  • Zhai, Hua-Jin; Zhao, Ya-Fan; Li, Wei-Li
  • Nature Chemistry, Vol. 6, Issue 8
  • DOI: 10.1038/nchem.1999

Planar hexagonal B36 as a potential basis for extended single-atom layer boron sheets
journal, January 2014

  • Piazza, Zachary A.; Hu, Han-Shi; Li, Wei-Li
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4113

Honeycomb Boron Allotropes with Dirac Cones: A True Analogue to Graphene
journal, June 2017


Synthesis of borophenes: Anisotropic, two-dimensional boron polymorphs
journal, December 2015


Experimental realization of two-dimensional boron sheets
journal, March 2016

  • Feng, Baojie; Zhang, Jin; Zhong, Qing
  • Nature Chemistry, Vol. 8, Issue 6
  • DOI: 10.1038/nchem.2491

Two-Dimensional Boron Monolayers Mediated by Metal Substrates
journal, September 2015

  • Zhang, Zhuhua; Yang, Yang; Gao, Guoying
  • Angewandte Chemie International Edition, Vol. 54, Issue 44
  • DOI: 10.1002/anie.201505425

Substrate-Induced Nanoscale Undulations of Borophene on Silver
journal, September 2016


Self-assembly of electronically abrupt borophene/organic lateral heterostructures
journal, February 2017


Probing the Synthesis of Two-Dimensional Boron by First-Principles Computations
journal, January 2013

  • Liu, Yuanyue; Penev, Evgeni S.; Yakobson, Boris I.
  • Angewandte Chemie International Edition, Vol. 52, Issue 11
  • DOI: 10.1002/anie.201207972

Synthesis and chemistry of elemental 2D materials
journal, January 2017

  • Mannix, Andrew J.; Kiraly, Brian; Hersam, Mark C.
  • Nature Reviews Chemistry, Vol. 1, Issue 2
  • DOI: 10.1038/s41570-016-0014

Intermixing and periodic self-assembly of borophene line defects
journal, July 2018


Metal Templates and Boron Sources Controlling Borophene Structures: An Ab Initio Study
journal, January 2018

  • Karmodak, Naiwrit; Jemmis, Eluvathingal D.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 4
  • DOI: 10.1021/acs.jpcc.7b12540

Can Two-Dimensional Boron Superconduct?
journal, March 2016


Preferential island nucleation at the elbows of the Au(111) herringbone reconstruction through place exchange
journal, September 1996


The Self-Assembly Mechanism of Alkanethiols on Au(111)
journal, May 1996


Nucleation of ordered Ni island arrays on Au(111) by surface-lattice dislocations
journal, April 1991


Selective assembly on a surface of supramolecular aggregates with controlled size and shape
journal, October 2001

  • Yokoyama, Takashi; Yokoyama, Shiyoshi; Kamikado, Toshiya
  • Nature, Vol. 413, Issue 6856
  • DOI: 10.1038/35098059

Tailoring molecular layers at metal surfaces
journal, January 2010


Epitaxial growth of thin magnetic cobalt films on Au(111) studied by scanning tunneling microscopy
journal, November 1991


Self-organized growth of nanostructure arrays on strain-relief patterns
journal, July 1998

  • Brune, Harald; Giovannini, Marcella; Bromann, Karsten
  • Nature, Vol. 394, Issue 6692
  • DOI: 10.1038/28804

Au(111)-Based Nanotemplates by Gd Alloying
journal, February 2010

  • Corso, Martina; Fernández, Laura; Schiller, Frederik
  • ACS Nano, Vol. 4, Issue 3
  • DOI: 10.1021/nn901345s

The contribution of lattice strain to core-level binding energy shifts in metal nanoparticles: Generality and origin of the shifts
journal, May 2012


Cluster Core-Level Binding-Energy Shifts: The Role of Lattice Strain
journal, July 2004


X-ray photoemission analysis of clean and carbon monoxide-chemisorbed platinum(111) stepped surfaces using a curved crystal
journal, November 2015

  • Walter, Andrew L.; Schiller, Frederik; Corso, Martina
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9903

Equilibrium at the edge and atomistic mechanisms of graphene growth
journal, September 2012

  • Artyukhov, V. I.; Liu, Y.; Yakobson, B. I.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 38
  • DOI: 10.1073/pnas.1207519109

Local strain analysis of the herringbone reconstruction of Au(111) through atomistic simulations
journal, January 2002


Photoelectron spectroscopy of size-selected boron clusters: from planar structures to borophenes and borospherenes
journal, January 2016


Scanning Tunneling Microscopy Observation of an Electronic Superlattice at the Surface of Clean Gold
journal, February 1998


Scanning tunneling spectroscopy of InAs nanocrystal quantum dots
journal, June 2000


Identification of atomic-like electronic states in indium arsenide nanocrystal quantum dots
journal, August 1999

  • Banin, Uri; Cao, YunWei; Katz, David
  • Nature, Vol. 400, Issue 6744
  • DOI: 10.1038/22979

Cryogenic variable temperature ultrahigh vacuum scanning tunneling microscope for single molecule studies on silicon surfaces
journal, December 2004

  • Foley, E. T.; Yoder, N. L.; Guisinger, N. P.
  • Review of Scientific Instruments, Vol. 75, Issue 12
  • DOI: 10.1063/1.1818871

Inertial tip translator for a scanning tunneling microscope
journal, August 1993

  • Brockenbrough, R. T.; Lyding, J. W.
  • Review of Scientific Instruments, Vol. 64, Issue 8
  • DOI: 10.1063/1.1143965

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Works referencing / citing this record:

The Xenes Generations: A Taxonomy of Epitaxial Single‐Element 2D Materials
journal, September 2019

  • Grazianetti, Carlo; Martella, Christian; Molle, Alessandro
  • physica status solidi (RRL) – Rapid Research Letters, Vol. 14, Issue 2
  • DOI: 10.1002/pssr.201900439

Superconductivity in predicted two dimensional XB 6 (X = Ga, In)
journal, January 2020

  • Yan, Luo; Bo, Tao; Liu, Peng-Fei
  • Journal of Materials Chemistry C, Vol. 8, Issue 5
  • DOI: 10.1039/c9tc05783h

Flat Boron: A New Cousin of Graphene
journal, June 2019

  • Xie, Sheng‐Yi; Wang, Yeliang; Li, Xian‐Bin
  • Advanced Materials, Vol. 31, Issue 36
  • DOI: 10.1002/adma.201900392

2D Boron Sheets: Structure, Growth, and Electronic and Thermal Transport Properties
journal, August 2019

  • Li, Dengfeng; Gao, Junfeng; Cheng, Peng
  • Advanced Functional Materials, Vol. 30, Issue 8
  • DOI: 10.1002/adfm.201904349

2D Elemental Nanomaterials Beyond Graphene
journal, June 2019


Experimental realization of quasicubic boron sheets
journal, January 2020


The Xenes Generations: A Taxonomy of Epitaxial Single‐Element 2D Materials
journal, September 2019

  • Grazianetti, Carlo; Martella, Christian; Molle, Alessandro
  • physica status solidi (RRL) – Rapid Research Letters, Vol. 14, Issue 2
  • DOI: 10.1002/pssr.202070013