Article

Cite This: ACS Nano 2019, 13, 3816−3822 www.acsnano.org

Borophene Synthesis on Au(111)

Brian Kiraly,†,‡,⊗ Xiaolong Liu,§,⊗ Luqing Wang,∥,⊗ Zhuhua Zhang,⊥,⊗ Andrew J. Mannix,†,‡
Brandon L. Fisher,† Boris I. Yakobson,*,∥ Mark C. Hersam,*,‡,§,# and Nathan P. Guisinger*,†
†
Center for Nanoscale Materials, Argonne National Laboratory, 9700 South Cass Avenue, Building 440, Argonne, Illinois 60439,
United States
‡
Department of Materials Science and Engineering, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, United
States
§
Applied Physics Graduate Program, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, United States
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∥
Department of Materials Science and NanoEngineering and Department of Chemistry, Rice University, Houston, Texas 77005,
United States
⊥
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State Key Laboratory of Mechanics and Control of Mechanical Structures and Institute of Nano Science, Nanjing University of
Aeronautics and Astronautics, Nanjing 210016, China
#
Department of Chemistry, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, United States
*
S Supporting Information

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. Herein, 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.
KEYWORDS: borophene, two-dimensional materials, Au(111), scanning tunneling microscopy, synthesis, allotrope

A s the lightest valence-three element, boron possesses

chemical properties that tend to favor complex bonding
arrangements.1−8 From computational modeling to
experimental synthesis, the recent discovery of two-dimensional
(2D) boron polymorphs, collectively referred to as borophene,7
has further elaborated the richness of boron chemistry and
ushered in a class of low-dimensional materials.9−17 Borophene
is an elemental 2D metal with superlative theoretical properties
including a tensile strength comparable to graphene and a
relatively high superconducting transition temperature.9,18 The
initial breakthrough for borophene synthesis occurred using
Ag(111) substrates, although theoretical modeling predicts
stable low-energy structures on additional metal surfaces (e.g.,
Au and Cu).11 Here, we present ultrahigh vacuum (UHV)
synthesis and characterization of borophene on Au(111).
Borophene growth begins when boron from the bulk segregates
to the surface, while the sample is cooled. Growth on Au(111) is
in stark contrast to boron limited to the surface on Ag(111).9,11
Furthermore, the energy minimization and strain relief of the
Au(111) surface results in nanoscale templating of borophene
nucleation and growth. Increasing boron coverage results in a
breakdown of the nanoscale templating mechanism, allowing
the borophene to evolve from small ordered islands to larger
sheets.
The Au(111) surface is among the few low-energy metal
surfaces that undergoes a reconstruction to minimize surface
energy. This reconstruction is characterized by a 22 × √3
structure consisting of surface atoms located at the face-centered
cubic (fcc), hexagonal close packing (hcp), and bridge-type
locations with respect to the bulk lattice.19,20 The reconstruction
results in a strain-mediated herringbone pattern of Shockley
Received: December 10, 2018
Accepted: March 7, 2019
Published: March 7, 2019

© 2019 American Chemical Society 3816 DOI: 10.1021/acsnano.8b09339

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Figure 1. (a) STM image of a clean Au(111) surface that shows the herringbone reconstruction (V = −1.5 V, I = 100 pA). (b) Following boron
deposition at 550 °C, the herringbone reconstruction is modified to a trigonal network, where nanoscale borophene islands (one highlighted by
a white dashed line) emerge at the nodes resulting in templated growth across the surface (V = −0.1 V, I = 200 pA). (c) Atomic structure of the
borophene v1/12 computationally modeled and predicted for Au(111) (left, top down view; right, cross-sectional view).

Figure 2. (a) B 1s core-level spectra for room-temperature B deposition (orange), trigonal network with low-dose (green), trigonal network
with high dose (red), and clean Au(111) (blue). (b) Increasing boron dose results in the breakdown of the trigonal network and growth of larger
borophene islands (top panels: V = −2 V, I = 100 pA; bottom panels: V = 3.4 V, I = 60 pA).

partial dislocations with uniform spacing and domain
orientations of 120°. Adsorption experiments reveal that this
surface reconstruction influences the growth of weakly
interacting materials on Au(111), typically leading to nucleation
at the corners of the herringbone reconstruction.21−26 Strongly
interacting adsorbates induce more significant modifications to
the herringbone reconstruction, including altering the symmetry
to a highly ordered trigonal network.27−29
RESULTS AND DISCUSSION
The pristine Au(111) surface, shown in the UHV scanning
tunneling microscopy (STM) image of Figure 1a, possesses the
herringbone surface reconstruction that consists of Shockley
partial dislocations running along the [112] directions that
separate the fcc from hcp striped regions. Deposition of boron
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from an atomic source was studied for a series of substrate
temperatures (see Supporting Figure 1). Low-temperature
deposition results in boron clusters confined to the surface. At
substrate temperatures of ∼550 °C, boron clusters are no longer
present and a transformation is observed from the conventional
herringbone reconstruction to a trigonal network where small
nanoscale borophene islands emerge, as seen in Figure 1b (see
also Supporting Figure 1). Atomic-resolution imaging of the
Au(111) surface confirms that the trigonal strain-relief network
forms within the Au surface, while borophene islands with a
calculated v1/12 structure nucleate at the nodes of the network.11
The total dose of atomic boron needed to observe nanoscale
borophene islands is an order of magnitude greater than what is
needed to form a monolayer on Ag(111), which is the first
indication that boron may be dissolving into the bulk at these
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Figure 3. (a) Schematic illustration of borophene growth dynamics. At low substrate temperature, the boron is predominantly on the surface
and forms boron clusters. For higher temperatures, the boron dissolves into the bulk and then segregates to the surface upon cooling to form 2D
borophene sheets. (b) Minimum energy path for boron diffusion on Au(111) (red), penetration from the fcc site on the surface into the
subsurface (gray), and diffusion in the subsurface (blue). (c) DFT calculations of the free energies of single boron atoms at various locations on
the Au(111) surface and in the Au(111) bulk, as well as boron dimer and trimer in the subsurface. The gold and boron atoms are displayed in
yellow and red, respectively. (d) SIMS spectra show that boron is limited to the surface when deposited at room temperature, but is present ∼30
nm into the subsurface region in the trigonal network sample that was prepared at high temperature.

substrate temperatures. Figure 1c illustrates the computationally
predicted atomic structure model for the borophene v1/12 on a
Au(111) substrate.
The trigonal network has a characteristic periodicity ranging
from 5.5 to 8.0 nm and acts as a growth template for nanoscale
borophene islands. Boron is not expected to form a stable alloy
with Au, and we do not observe direct evidence of alloying.
However, the trigonal network has been observed for clusters
that are incorporated into the surface.27−29 To minimize surface
energy, this reconstruction consists of alternating triangular
regions of fcc and hcp stacked Au atoms,27−29 as indicated by the
triangular dashed regions in Figure 1b. The apparent embedded
nature of the boron islands is likely responsible for the transition
from the normal herringbone surface reconstruction to the
trigonal network.
The chemical properties of the boron-modified Au(111)
surface are investigated by in situ X-ray photoelectron
spectroscopy (XPS) and compared to that of a clean Au(111)
surface, as shown in Figure 2 and Supporting Figure 2. The Au
4f7/2 core-level peak after room-temperature boron deposition
matches that of clean Au. However, the trigonal network
samples show a 0.1 eV redshift (see Supporting Figure 2). This
shift is consistent with 1−2% strain relief induced by the
incorporation of boron into the Au(111) lattice and removal of
Au atoms.30−32 Indeed, the transformation of the strain relief
pattern from the herringbone reconstruction to the trigonal
network indicates a change of strain status of the surface. The Au
surface with boron particles also shows a clear peak in the B 1s
core-level (Figure 2a), which is expected given the limited
solubility of boron in Au at room temperature. However, the
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reduced peak height from the trigonal network samples indicates
that the surface coverage of boron is much lower in these cases,
which suggests that boron diffuses into the subsurface region at
higher substrate temperatures. The absence of an obvious peak
shift of the B 1s core level, albeit low in intensity, suggests
minimum valence changes, in contrast to the case of boron
oxides (peak shifts to 192 eV).9 Increasing the boron dose
eventually results in the breakdown of the trigonal network and
the formation of larger borophene islands that are embedded in
the topmost layer of Au, as illustrated in Figure 2b. The dashed
hexagons in the insets of Figure 2b illustrate the trigonal
network. Borophene sheets increase in size with boron dose,
leading to domains that extend at least several tens of
nanometers at the highest doses in this study as seen in the
bottom two panels of Figure 2b.
Both STM and XPS (Figure 2 and Supporting Figure 2) reveal
that boron clusters form on the surface at low temperature, while
boron appears to dissolve into the bulk at elevated temperatures.
Thus, we suggest that the borophene growth results from surface
segregation of boron from the bulk when the sample is cooled
(illustrated in Figure 3a). This surface segregation of boron to
form borophene on Au(111) is contrary to the surface-only
growth on Ag(111); these two schemes are analogous to the two
primary growth modes observed for graphene on metal
substrates.33
To gain further insight into the mechanisms underlying the
apparent surface segregation and recessed growth modes of
boron on Au(111), we performed density functional theory
(DFT) calculations to quantify the adsorption energetics of
boron atoms on this surface. We do not compute all of the atom-
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Figure 4. (a) STM image of a larger borophene island that shows the herringbone reconstruction from the underlying Au(111) substrate and
atomic-scale periodicity (V = 1 V, I = 100 pA). (b) Atomic-scale periodicity is apparent in larger borophene sheets (V = −0.4 V, I = 80 pA). (c)
FFT of the STM image in (b) reveals that the periodic length scale is ∼0.66 nm. (d) STM image following the initial stages of growth of the
templated borophene nanostructures (V = −0.4 V, I = 200 pA). (e) Histogram of the island sizes with observable peaks corresponding to integer
values of the basic rhombohedral unit.
state sequences, as in the nanoreactor diagram,34 but only key
initial configurations. Figure 3c shows the resulting DFT
predictions of the relaxed energies of boron atoms at different
sites within and on top of Au(111). The calculations indicate
that while both bulk solution and surface locations are
energetically favorable, they are significantly higher in energy
than the near-surface dissolution of boron atoms. In particular,
the most stable configurations of isolated boron atoms are in
subsurface sites in the topmost layer, with sites along Au(111)
step edges being favored by ∼0.3 eV over planar subsurface sites.
These energetics differ significantly from those of boron on
Ag(111).9,11 The surface strain is greater in Au, up to 5.5%,35
than in Ag so that inlayer growth is preferred on Au. Despite
their similar chemical properties, the noble metal surfaces have
strongly differing electronic densities near the Fermi level (Ef),
which leads to the stabilization of distinct boron configurations.
Importantly, subsurface boron possesses reduced steric
constraints from surrounding Au and in turn can form a
stronger Au−B interaction to adopt a more energetically
favorable adsorption site.
Modeling of the boron diffusion energetics within the first
Au(111) layer shows further consistency with the experimental
observation of embedded islands. For example, Figure 3c (right
panel) illustrates the energetics of multiatom boron clusters on
the Au(111) surface. As shown with respect to the energy of a
single subsurface boron atom, the calculations favor the
formation of small boron clusters within the Au(111) subsur-
face. The increasing depth of the potential well for dimers and
subsequently trimers indicates the preference for boron−boron
bond formation within this subsurface environment. Further-
more, the most stable configuration involves a Au atom being
expelled out of the surface to accommodate the boron trimer
cluster, attributed largely to further relief of surface stress on
Au(111). The nucleated boron trimer then extends into 2D
islands upon further docking of boron atoms and the removal of
redundant Au atoms. Again, this behavior marks a significant
difference from the 2D surface growth motif of borophene
overlayers on Ag(111),9,11 confirming our experimental
observations.
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Article
To experimentally confirm that boron is dissolving into the
bulk, the distribution of boron in Au is further investigated via
time-of-flight secondary ion mass spectrometry (ToF-SIMS). In
addition to a trigonal network sample and a boron cluster sample
where boron is deposited on Au held at room temperature, as-
received and UHV-cleaned Au samples are also explored as
control samples. In Figure 3d and Supporting Figure 3, higher
boron signals are seen in the SIMS spectra for the boron cluster
sample compared to the trigonal network sample, suggesting a
higher surface concentration of boron. This observation is in
agreement with the XPS B 1s level results. Depth-profiling of the
four samples reveals that the boron concentration in the trigonal
network sample only decays after ∼30 nm into the bulk, whereas
the boron signals decay more quickly in the three other cases
once the surface is sputtered (Supporting Figure 3). In
agreement with the XPS results, the SIMS data suggest that
boron diffuses deeply into the Au subsurface region at elevated
temperatures. The UHV cleaned Au shows no obvious
differences compared to as-received Au, indicating the negligible
effect of UHV annealing.
On larger borophene islands, STM faintly resolves a
herringbone reconstruction in the Au directly below the 2D
sheets. The zoomed-in image of a borophene island (Figure 4a)
reveals apparent atomic-scale periodicity, while herringbone
stripes concurrently remain visible (black arrows) below the 2D
sheet. The ability to resolve the underlying Au(111)
herringbone reconstruction suggests that the boron islands are
atomically thin. The STM image of Figure 4b further reveals an
apparent atomic-scale periodicity within the borophene sheet.
However, this periodicity is distorted by a larger superstructure
that is likely related to a Moiré pattern between borophene and
Au(111). A fast Fourier transform (FFT) of the STM image in
Figure 4b shows a strong periodicity of ∼0.66 nm as illustrated in
Figure 4c. This ∼0.66 nm periodicity is consistently observed in
the extended borophene sheets.
At the early stages of nucleation and growth, the borophene
islands are templated at the nanoscale. As seen in the STM
images in Figure 1, the specific shape of the borophene islands is
both compact and anisotropic. Closer inspection reveals that
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Figure 5. (a) Series of bias-dependent STM images showing topography (top panels) and dI/dV maps (bottom panels) of the same region at the
biases indicated above each panel. Red and yellow triangles represent fcc and hcp regions of the Au(111) surface, as noted in Figure 1. The
borophene islands appear as depressions in topography at all biases (I = 200 pA). (b) Calculated band structure and electronic density of states
(DOS) for monolayer boron on Au(111) showing metallic characteristics. The red and gray lines represent electronic bands contributed by
borophene and Au, respectively. The thickness represents the weight of the contribution. (c) dI/dV point spectra taken on (gray) Au(111) for
reference, (red) large borophene sheets on Au(111) for comparison, and (dark blue) borophene nanoislands on Au(111). Dashed lines at ±300
mV highlight the boron island spectral features that are discussed in the text.

each island can be approximately decomposed into rhombohe-
dral units, as highlighted in Figure 4d,e. Furthermore, the
coalescence of multiple rhombohedral building blocks can
account for the shape of larger borophene islands. The size of an
individual rhombohedral unit (Figures 4d,e) ranges between 0.9
and 1.4 nm2 with an aspect ratio of 1.5 ± 0.2, where we note that
the accuracy of this measurement is limited by the gold adatoms
that are often found at the edges of the borophene islands. A
histogram generated from over 500 islands (Figure 4e) reveals
clear discretization of island area at integer values of square
nanometers. These rhombohedral units, both in terms of size
and shape, are consistent with investigations of planar size-
selected boron clusters.7,36−39
The smaller borophene islands are often at the single
nanometer length scale, where strong electronic confinement
effects are likely to occur. Furthermore, their discrete
rhombohedral building blocks may show quantum effects. To
further understand the electronic properties of the borophene
islands, a series of bias-dependent images and concurrently
acquired dI/dV tunneling conductance maps (proportional to
the electronic density of states) are presented in Figure 5a. The
bias-dependent conductance maps reveal that not only is the
borophene electronically distinct from the Au but that the fcc
(red dashed triangle) and hcp (yellow dashed triangle) regions
are also distinct, where the contrast inverts between −0.2 and
−0.4 V sample bias. At positive sample bias, the Au surface state
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becomes pronounced as we observe the standing wave reflecting
from the step-edge and interference patterns between the
borophene islands, further confirming the embedded nature of
the borophene islands. The borophene islands themselves
exhibit electronic variation at the nanometer length scale
(particularly at −0.2 or +0.4 V), which could be related to
electronic confinement effects.
DFT calculations reveal that the previously predicted
borophene structure on Au(111) is metallic, as illustrated by
the band structure and density of states (DOS) in Figure 5b.11
Scanning tunneling point spectra verify that the 2D borophene
on Au(111) is indeed metallic as shown in the blue curve in
Figure 5c. It is noteworthy that the spectra for the large
borophene island on Au(111) are similar to the spectra seen for
borophene on Ag(111).9 In contrast, the gray curve is taken on
the clean Au(111) surface and shows the characteristic Shockley
surface state at approximately −0.52 eV.40 Spectra taken on the
borophene nanoislands differ significantly from larger bor-
ophene sheets, with several additional spectral features. For
example, in the black curve in Figure 5c, a shoulder is observed at
approximately +0.3 V in addition to a symmetric inflection at
−0.3 V (indicated by the dashed lines). We believe that these
shoulders are a result of additional electron confinement within
the borophene clusters. Electron confinement in quantum dot
structures has previously been shown to result in symmetric
states around the Fermi level.41,42
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CONCLUSIONS
In conclusion, nanoscale borophene structures have been
synthesized and characterized on Au(111) in UHV. The
observed growth mode is consistent with boron dissolving
into the bulk at high temperatures and segregating to the surface
to form borophene as the sample is cooled. The initial stages of
growth for low concentrations of boron result in nanoscale
templating of the borophene islands across the surface, as the
Au(111) reconstructs in a trigonal network to minimize energy.
At low boron concentration, the borophene islands are
comprised of one to eight rhombohedral units with a
characteristic area of 1 nm2, as observed in statistical analysis
of the island size. The electronic properties of borophene on
Au(111) are confirmed to be metallic, with the nanoscale
borophene islands showing evidence of electron confinement.
Overall, the nanoscale templated growth of borophene on
Au(111) presents opportunities for studying and manipulating
the electronic properties of 2D metals.
METHODS
The Au(111) on mica substrates were commercially purchased from
Keysight Technologies. The Au(111) surface was cleaned in UHV via
repeated sputter/anneal cycles until atomically pristine. Character-
ization was performed using a variable-temperature STM (Scienta
Omicron) and a home-built UHV STM system adopting a Lyding-
design microscope.43,44 STM images and spectroscopy in the main text
were gathered at a sample temperature of 55 K with electrochemically
etched W tips. Borophene was grown via thermal deposition from a
pure boron rod using electron-beam evaporators (Focus EFM and
SPECS EBE-1). The substrate temperature during borophene growth
was ∼550 °C. The evaporation rate is ∼0.02 ML/min (based on
borophene growth on Ag(111) with the same power), and the
deposition time ranges from 30 min to 3 h.
DFT calculations were performed using ultrasoft pseudopotentials
for the core region and generalized gradient approximation of the
Perdew−Burke−Ernzerhof (PBE) functional for describing the
exchange correlation, as implemented in VASP code.45,46 A kinetic
energy cutoff of 400 eV is chosen for the plane-wave expansion. In all
structures, the vacuum region between two adjacent periodic images is
fixed to 10 Å to eliminate spurious interaction. The Brillouin-zone
integration is densely sampled according to the supercell size, ensuring
approximately the same k-point density among different-sized super-
cells. The k-point density is approximately 45 Å−1. For example, for a
supercell with a size of 10 Å × 8.65 Å, the k-point sampling is 5 × 5 × 1,
where “1”indicates the vacuum layer. The metal substrate consists of
four atomic layers, with atoms in the bottom layer being fixed to the
bulk lattice. The positions of all other atoms are relaxed using the
conjugate-gradient method until the force on each atom is less than 0.01
eV/Å. The minimum-energy path was mapped out using the climbing
image-nudged elastic-band method.47
XPS spectra were taken with an Omicron DAR 400 M X-ray source,
XM 500 X-ray monochromator, and EA 125 energy analyzer at a base
pressure of ∼4 × 10−10 Torr. The XPS system is integrated with the
home-built UHV STM system for in situ measurements with an energy
resolution of ∼0.6 eV.
ToF-SIMS spectra were acquired on a PHI TRIFT III ToF-SIMS
(Physical Electronics) system with a liquid metal ion gun in the positive
ion mode. The analysis chamber pressure was ∼1 × 10−9 Torr.
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsnano.8b09339.
Boron-dosing information as a function of temperature,
additional XPS data, and ToF-SIMS data (PDF)
3821
Article
AUTHOR INFORMATION
Corresponding Authors
*E-mail: biy@rice.edu.
*E-mail: m-hersam@northwestern.edu.
*E-mail: nguisinger@anl.gov.
ORCID
Xiaolong Liu: 0000-0002-6186-5257
Zhuhua Zhang: 0000-0001-6406-0959
Mark C. Hersam: 0000-0003-4120-1426
Nathan P. Guisinger: 0000-0001-7437-2331
Author Contributions
⊗
B.K., X.L., L.W., and Z.Z. are co-first authors.
Author Contributions
B.K., A.J.M., M.C.H., and N.P.G. conceived the project; B.K.,
X.L., and A.J.M. carried out the experiments and data analysis.
Z.Z., L.W., and B.I.Y. provided theoretical support and
computational modeling. B.L.F. provided engineering support
for the experiment. N.P.G., B.K., Z.Z., X.L., and M.C.H. wrote
and revised the manuscript. All authors contributed to the
manuscript.
Notes
The authors declare no competing financial interest.
The data sets generated during and/or analyzed during the
current study are available from the corresponding author upon
request.
ACKNOWLEDGMENTS
Use of the Center for Nanoscale Materials, an Office of Science
user facility, was supported by the U.S. Department of Energy,
Office of Science, Office of Basic Energy Sciences, under
Contract No. DE-AC02-06CH11357. M.C.H. and X.L.
acknowledge funding from the Office of Naval Research
(N00014-17-1-2993). Work at Rice (Z.Z. and B.I.Y.) was
supported by DOE Grant No. DE-SC0012547. Work at NUAA
was supported by National Natural Science Foundation of
China (11772153).
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NOTE ADDED AFTER ASAP PUBLICATION
Figure 1 was corrected on March 29, 2019.
DOI: 10.1021/acsnano.8b09339
ACS Nano 2019, 13, 3816−3822