Article

Cite This: J. Am. Chem. Soc. 2017, 139, 17181-17185 pubs.acs.org/JACS

Two-Dimensional Boron Polymorphs for Visible Range Plasmonics: A

First-Principles Exploration
Yuefei Huang,‡ Sharmila N. Shirodkar,‡ and Boris I. Yakobson*
Department of Materials Science and NanoEngineering, Rice University, Houston, Texas 77005, United States
*
S Supporting Information

ABSTRACT: Recently discovered two-dimensional (2D) boron

polymorphs, collectively tagged borophene, are all metallic with
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high free charge carrier concentration, pointing toward the possibility

of supporting plasmons. Ab initio linear response computations of the
dielectric function allow one to calculate the plasmon frequencies (ω)
in the selected example structures of boron layers. The results show
that the electrons in these sheets indeed mimic a 2D electron gas, and
their plasmon dispersion in the small wavevector (q) limit accurately
follows the signature dependence ω ∝ √q. The plasmon frequencies
that are not damped by single-particle excitations do reach the near-
infrared and even visible regions, making borophene the first material
with 2D plasmons at such high frequencies, notably with no necessity for doping. The existence of several phases (polymorphs),
with varying degree of metallicity and anisotropy, can further permit the fine-tuning of plasmon behaviors in borophene,
potentially a tantalizing material with utility in nanoplasmonics.

■ INTRODUCTION
Plasmons as collective excitations of electrons are an important
ingredient of a material’s optical properties. Plasmons restricted
to two dimensions only, in surfaces or layers, exhibit ultra-
subwavelength confinement with phase velocities reduced up to
∼100 times relative to the speed of light1 and enhanced light−
matter interaction.2 This plasmon restriction to the nanometer
scale has been explored for a wide range of applications of two-
dimensional (2D) materials, such as enhanced sensing of
biomolecules,3,4 nanoimaging,5 waveguides,6 tunable lasing,7
light harvesting,8 and nanoantennas.9,10
Not only does reduction in dimensionality change the
plasmon confinement, but it also qualitatively changes the
plasmon dispersion, to ∼√q (q is plasmon wavevector, q = |q|)
as opposed to nondispersive plasmons in 3D.11 This trait of 2D
electron gas12 has been observed in several 2D materials, viz.,
graphene,13−16 black phosphorus,17 and transition metal
dichalcogenides (TMDCs).18 The plasmon frequency in these
materials scales as √n with their free carrier concentration n
(with the exception of graphene’s ∼n1/4 dependence,14,16 due
to its linear dispersion at the Dirac point), implying that
plasmon frequencies are tunable by the carrier concentration.
All these materials are either semiconducting or metallic with
low n, requiring a gate- or chemical-doping to increase the
carrier concentration to tune the plasmonic response. Doping
via gating has been reported to induce carriers to densities of
∼1013 cm−2 (1017 m−2) in graphene15,19 and black phospho-
rus,17 reaching plasmonic frequencies in the mid infrared. The
plasmonic response of metallic TaSe2 compound18 is also
restricted to the near-infrared regime (NIR), with carrier
concentrations of ∼1 × 1015 cm−2 (1 × 1019 m−2). To date,
there has only been one report of 2D plasmons in the visible
frequency range20 at a very high level of doping in a Li-
graphene intercalation compound.
Boron is the neighbor of carbon in the periodic table and has
shown similarity to carbon in forming planar clusters,21−23
cage-like fullerenes,24−26 and 1D nanotubes.27−29 The boron
analogue of graphene,30 2D boron (borophene), has been
recently explored, and its properties have been probed
theoretically as well.31−33 First-principles studies predict 2D
boron polymorphism with large number of possible low-energy
structures.34 These polymorphs differ from their parent
structure, the buckled triangular boron, via concentration of
vacant B sites. This rich polymorphism in 2D boron has been
confirmed by experimental synthesis of triangular boron by
Mannix et al.35 and two other polymorphs, β12 and χ3, by Feng
et al.36,37 on the Ag(111) surface by molecular beam epitaxy.
Unlike β12, free-standing triangular boron and χ3 have been
predicted to be dynamically unstable.38 However, the adhesion
that is accompanied by charge transfer39 on the Ag(111)
surface makes them thermodynamically stable and experimen-
tally synthesizable, with a stability order of χ3 > β12 > triangular
boron.36 We would like to note that although triangular boron
is metastable/energetically higher than the other polymorphs, it
can be synthesized under specific conditions.35,36
It has been shown that 2D boron is a metal,35−37,40 in
contrast to its 3D crystal, being a semiconductor. It is one of
the very few 2D materials that are intrinsically metallic/
semimetallic such as the 1T polymorphs of MX2 com-
Received: September 27, 2017
Published: November 1, 2017

© 2017 American Chemical Society 17181 DOI: 10.1021/jacs.7b10329

J. Am. Chem. Soc. 2017, 139, 17181−17185
Journal of the American Chemical Society
pounds.18,41−43 Moreover, 2D boron has a much higher density
of electronic states at the Fermi level,38 compared to 1T- MX2
compounds,44,45 eliminating the need to dope or gate it to
increase charge carrier density. Interestingly, the 2D boron
form has been theoretically38 as well as experimentally shown
to exhibit Dirac cones37 and has also been predicted to possibly
become superconducting around ∼10−20 K.38
The existence of several polymorphs, structural anisotropy,
and inherent metallic conductivity of 2D boron motivate us to
explore if plasmons are feasible, especially in the visible range of
frequencies. Using first-principles calculations we explore the
plasmonic properties of three example polymorphs of 2D
boron. Our calculations show that the free charge density in 2D
boron behaves like a 2D gas of electrons and exhibits
anisotropic plasmons with √q dispersion at small q and long
wavelength. Most importantly, we find that at larger q values
plasmons in 2D boron do reach the infrared to visible range
frequencies, depending on the structure of the specific
polymorph.
■
COMPUTATIONAL DETAILS
We carry out density functional theory (DFT) calculations as
implemented in the GPAW electronic structure code.46 The
interaction between the ions and electrons is described by the
projector augmented wave method,47 and the exchange−correlation
energy of electrons is approximated by the Perdew−Burke−Ernzerhof
(PBE) functional.48 The 2D layers are modeled in periodic cells with
10 Å vacuum in the direction normal to the layer, to reduce the
interaction between periodic images (see Supporting Information for
details). The Kohn−Sham wave functions are represented using a
plane wave basis set with an energy cutoff of 340 eV. The 2D Brillouin
zone (BZ) is sampled using 256 × 128 × 1 k-points for B△ and 256 ×
256 × 1 k-points for B□ and for B◇ (Figure 1a−c).
At the nanometer length scale, the local electromagnetic field effects
are non-negligible, affecting the material response considerably, which
is not captured by the Drude model. A full quantum mechanical
description of the dielectric function, i.e., microscopic dielectric
function, accounting for the local field effects, is necessary to accurately
describe plasmons in 2D materials. 49 Using linear response
Figure 1. Atomic structures (top view) (a)−(c) and electronic band
structures (d)−(f) of B△, B□, and B◇, respectively. At the bottom of
(a) is the side view of buckled B△. The red arrows in the BZ represent
the direction of q of the plasmon modes in our calculations. The green
vertical arrows in the band structures show the minimum energy SPEs
(with non-negligible threshold transition momentum >0.1 au) that
damp plasmons.
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calculations50 as implemented in the GPAW code, the microscopic
dielectric function ϵG,G′(ω, q) is determined in the Fourier space as a
function of wavevector q and frequency ω of the incident wave, for the
GG′ (q, ω) = δGG′
reciprocal lattice vectors G and G′. It is calculated as ϵRPA
− (4π/|q + G|2)χ0GG′(q, ω), under the random phase approximation
(RPA), where χ0GG′(q, ω) is the Fourier transform of the non-
interacting density response function χ0GG′(r, r′, ω). We use a plane-
wave cutoff of 100 eV for reciprocal lattice vectors. All the other
parameters were converged within 0.1 eV of plasmon frequencies
calculated using methodology developed by Anderson et al.51
At the frequency of a self-sustained charge-density oscillationa
plasmonthe real part of the dielectric function must go to zero from
a negative value, Re[ϵ(ω = ωp)] = 0. The plasmon resonance, at
frequency ωp, can also be identified as the local maximum/peak
appearing in the loss function, −Im[ϵ(ω, q)−1], while the area under
the loss function peak represents the strength of the plasmon
mode.17,18 The ωp determined in our materials appears independent of
the two methods described above, since Im[ϵ] is negligibly small at the
zeros of Re[ϵ].
An important measure of a plasmon in a material is the wave
localization or shrinkage, quantified as λair/λp (λair is the electro-
magnetic wavelength at frequency ωp in a vacuum, and λp = 2π/q).
This estimates the confinement of the wavelength of electromagnetic
radiation in a plasmon. A plasmon is damped by single-particle
excitations (SPEs), i.e., formation of electron−hole pairs. These SPEs
are determined as poles (peaks) in the real (imaginary) part of the
response function χ, and the threshold non-negligible transition
momentum is chosen as >0.1 au The damping regions due to SPEs
occurring at ωSPE frequencies can be approximated as bounded by
ℏωSPE ± ℏνFq + ℏ2q2/2m, where νF is the Fermi velocity14,52 (as q →
0, ℏ2q2/2m is negligible as compared with ℏνFq).
■
RESULTS AND DISCUSSION
A 2D boron sheet exhibits various polymorphs, conveniently
described as a pseudoalloy, B1−xVx for x = 0.1−0.15, where V is
a vacant site in the underlying triangular B lattice.34 Among the
large number of such polymorphs, we select only examples that
are energetically preferable or have fewer atoms per unit cell,
for computational feasibility. Hence, we explore the same three
structures of single-layer 2D boron, B△, B□ (known as β12),
and B◇ (known as χ3) (Figure 1), which were studied by Penev
et al.38 Even if only B□ is stable in free-standing form, the other
two polymorphs are stabilized by the Ag(111) substrate35,36
and hence is instructive to study the properties of all three
polymorphs, as they provide crucial insights into the potential
applicability of 2D boron in nanoplasmonics. B△ (x = 0) is a
buckled triangular lattice (Figure 1a) with GGA-optimized
lattice constants a = 1.62 Å and b = 2.85 Å and atomic
coordination of 6. The distance between the two sublayers
(degree of buckling) is 0.86 Å, greater than the buckling in 2D
silicene (0.44 Å) and germanene (0.64 Å).53 Its electronic band
structure is shown in Figure 1d, with the smallest allowed SPE
marked by the green arrow. In comparison to the band
structure of VS2 or TaSe218 where only one band crosses the
Fermi level, we find that B shows many more crossings by
highly dispersed (almost parabolic) bands.38 This suggests that
2D boron has a larger free charge carrier concentration as
compared to metallic MX2 compounds.
Removing some B atoms, up to x = 1/6 (B□ in Figure 1b,
with maximum atomic coordination of 6), turns the lattice
planar and its primitive cell larger, with lattice constants a =
2.92 Å and b = 5.08 Å (GGA values). This is known as the most
stable structure, free-standing34 as well as grown on a silver
substrate.35,37 We note that the band structure (Figure 1e) has
several band crossings at the Fermi level. Interestingly, the
Dirac cone appears at ∼2 eV above the Fermi level along the
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Figure 2. Plasmon dispersion of (a) B△, (b) B□, and (c) B◇. The gray areas are the regions damped by single-particle excitations (SPEs). Blue
(circles) and red (squares) curves are for plasmon dispersion (i.e., q) along the Γ−X and Γ−Y directions, respectively. Fitting to classical 2D electron
gas plasmon dispersion relation 2 is shown by solid lines. The strength of the plasmon mode is directly proportional to the thickness of the circles/
squares. The SPEs are at 3.4, 1.7, and 0.95 eV for B△, B□, and B◇, respectively.

Figure 3. Wave shrinkage (a−c) of B△, B□, and B◇, respectively. The shaded regions correspond to areas that are damped by interband and
intraband (SPEs) transitions. Blue (circles) and red (squares) curves are for plasmon dispersion (i.e., q) along the Γ−X and Γ−Y directions. Blue-
and red-shaded regions correspond to damping regions for plasmons along the Γ−X and Γ−Y directions (estimated as the lowest frequency at which
plasmon dispersion cuts the damping region in Figure 2), respectively.

Γ−X direction in the BZ (while free-standing), which has been
reported to get filled by electrons donated by the Ag
substrate.37 The last polymorph, B◇, which corresponds to x
= 1/5 (Figure 1c), is a planar structure with a maximum atomic
coordination of 5. The primitive cell, however, is non-
orthogonal, with lattice constants a = b = 4.55 Å and an
angle of 141.7° between them. Similar to the above-discussed
polymorphs, the band structure of B◇ (Figure 1f) shows highly
dispersed bands crossing the Fermi level. We calculated the
plasmon dispersion along the high-symmetry lines denoted by
red arrows in the BZ in Figure 1d−f, i.e., the plasmon
wavevector q parallel to these directions. The plasmon
dispersion curves for B△, B□, and B◇ are shown in Figure 2.
We note that the plasmons differ along different directions of
the BZ; this anisotropy can be traced back to the anisotropy in
the electronic structure and of the lattice. For all three
structures, the dispersion looks similar to that of 2D electron
σe 2q
gas,54 ωp = , where σ is the number of charge carriers
2m * ϵ 0
per unit area and m* is the effective mass of the carriers. The
outer electronic configuration of B is 2s2, 2p1, and assuming one
free charge carrier from the p orbital per B atom, the free carrier
density per unit area for B△, B□, and B◇ is 4.3 × 1015 cm−2
(4.3 × 1019 m−2), 3.4 × 1015 cm−2 (3.4 × 1019 m−2), and 3.3 ×
1015 cm−2 (3.3 × 1019 m−2), respectively, all much higher than
any of the free carrier densities previously reported for doped
or undoped 2D materials. Since distinguishing the electronic
excitations that contribute to the plasmonic resonance is
nontrivial (due to the large number of band crossings),
assigning the m* values for those particular bands may also be
ambiguous. Instead, we proceed by fitting an expression for 2D
electron gas (solid lines in Figure 2) to our computed plasmon
dispersion data and evaluating m* as a fitting parameter (m0 is
17183
electron mass): for B△ m* = 1.4m0 and 5.2m0, and for B□ m* =
3.5m0 and 3.7m0 along the Γ−X and Γ−Y directions,
respectively, whereas for B◇ m* = 1.4m0 and 3.8m0 along the
Γ−X and Γ−Y directions, respectively. As we see, the plasmon’s
anisotropy in each structure is also reflected in the effective
mass differences of the carriers, similar to anisotropic plasmons
in black phosphorus.17 We note that the deviation of the
computed plasmon dispersion from that of a 2D electron gas at
larger q values is related to nonparabolicity of bands and
screening by interband transitions,18 although distinguishing
between these different effects is nontrivial.
As mentioned before, plasmons are damped by SPEs, which
are both intraband and interband (also known as Landau
damping). Damping regions in Figure 2 are determined by the
methods discussed above. The poles in the response function
(SPEs) were identified at 3.4, 1.7, and 0.95 eV for B△, B□, and
B◇, respectively. These symmetry-allowed interband excita-
tions between the occupied and unoccupied states, shown by
green arrows in the band structure in Figure 1d−f, damp the
plasmons in borophene. To map the damping regions, the
Fermi velocity (νF) on the Fermi surface (in Γ−X and Γ−Y) of
all three phases was calculated, and the maximum value of νF
was chosen. Our estimates of maximum νF in B△, B□, and B◇
are 1.4 × 106, 0.9 × 106, and 1.3 × 106 m/s in Γ−X and 0.95 ×
106, 0.86 × 106, and 0.95 × 106 m/s in Γ−Y, respectively. Due
to damping, only the plasmons with frequencies up to 3.0 eV
and q < 0.05 Å−1 along Γ−X and up to 2.3 eV for q < 0.21 Å−1
along Γ−Y survive in B△. Notably, this appears to be the first
material with 2D plasmons in the visible range with no need of
doping.
In B□ the plasmons are undamped until 1.5 eV (q < 0.03
Å−1) along Γ−X and Γ−Y and 0.9 eV (q < 0.01 Å−1) for B◇
along both Γ−X and Γ−Y directions. Note that the jump in the
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Journal of the American Chemical Society
plasmon dispersion around q = 0.05 Å−1 along Γ−X in B◇ is
probably due to the coupling to another plasmon mode. Hence,
we find that the plasmon response of the experimentally
synthesized35,37 polymorph of 2D boron B□ can reach the NIR
range. We also notice that the SPE energies decrease with a
larger number of vacant B-sites in the 2D boron “alloy”,
perhaps because the number of states and symmetry-allowed
transitions across the Fermi level increase, thus increasing the
chance of having SPE at lower energy. Accordingly, increasing
the B-vacancy concentration (x) tends to lower the frequency
range of undamped plasmons.
Although the main loss mechanism is Landau damping due
to SPE discussed above, one should keep in mind other ever-
present losses caused by defects and electron−electron and
electron−phonon scattering, which introduce finite relaxation
time, τ. Its value, not available for boron, can be, for the sake of
estimates, based on graphene conductivity measurements. In
the Supporting Information we present propagation length,
commonly used to quantify the overall losses. The maximum
wave shrinkage λair/λp (Figure 3a−c) is ∼30 for B△ and B□
and ∼15 for B◇ (by extrapolation) for undamped plasmons
determined at the border of damped and undamped regions for
Γ−X, whereas the maximum subwavelength confinement (wave
shrinkage) for Γ−Y is 150, 50, and 25 for B△, B□, and B◇,
respectively. We note that these wave shrinkage values are
larger for Γ−Y than for Γ−X; that is, the plasmonic properties
improve for plasmons with smaller frequencies or larger
effective masses. Large shrinkage finds applications in
subdiffraction-limited imaging and drastic miniaturization of
plasmonic devices. In comparison, graphene exhibits a
maximum wave shrinkage of 100−20055 for doping of 1012
cm−2 (1016 m−2, EF = 0.135 eV), which is considerably larger
than in 2D boron, since the plasmon in graphene is also at a
lower frequency. However, the wave shrinkage in 2D boron
could be increased by application of a gate,1 improving its
performance in nanoplasmonics.
As already mentioned, the plasmons in 2D semiconducting
materials, graphene and black phosphorus, appear in the mid/
near-infrared frequencies and only with doping. Black
phosphorus exhibits plasmons up to 150 meV if doped to n
= 5 × 1013 cm−2 (5 × 1017 m−2),17 while the experimental
doping level is n ≈ 5.5 × 1012 cm−2 (5.5 × 1016 m−2),56
implying that plasmons must actually be below 150 meV.
Graphene experimentally shows undamped plasmons up to its
Fermi level,13,14 typically 100 meV.15 A recent theoretical study
by Shirodkar et al.20 showed undamped plasmons in the visible
frequencies, for multilayered graphene intercalated with
lithium, at large doping concentrations. On the other hand,
one metallic 2D TMDC TaSe218 exhibits plasmons in the NIR
regime, due to smaller charge carrier concentration (≈1 × 1015
cm−2, 1019 m−2). We note that in all these instances of 2D
plasmons (except for TaSe2) the material is doped in order to
increase the carrier concentration. Chemical doping increases
disorder and gate doping may cause leakages in devices, which
can alter the plasmonic properties of the material. In contrast,
2D boron is intrinsically metallic with a higher concentration of
carriers up to 4 × 1015 cm−2 (4 × 1019 m−2), enabling the
plasmons in the visible range for B△ and NIR regions for B□
and B◇, respectively.
■
CONCLUSIONS
In conclusion, using first-principles calculations we have
determined the plasmon dispersion along the high symmetry
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directions for three polymorphs of 2D boron, B△, B□, and B◇.
We find that 2D boron has a strong potential to exhibit
plasmons in the visible and NIR range of frequencies with no
need of doping. Further, the plasmons display strong
anisotropy, a result of difference in effective mass of the charge
carriers in the different directions of BZ, hence indicating that
the frequency of plasmons is a function of the polarization of
exciting radiation. We also note that the plasmons in 2D boron
do not show a subwavelength confinement as high as that in
graphene. Recent experiments have reported substrate doping
where silver (substrate) transfers electrons to the 2D boron; in
such a case, due to increased free charge carrier concentration,
one expects that the plasmon frequencies in 2D boron may
further increase. As for the special case of B□, if the Fermi level
shifts by ∼2.0 eV up in energy, which fills the previously
unoccupied linearly dispersive bands, the Dirac point appears
0.25 eV below the Fermi level;37 this way, B□ may exhibit
graphene-like plasmons in the mid infrared range of
frequencies, with larger subwavelength confinement (wave
shrinkage) as compared to the undoped structure. Our results
show that the metastable B△ polymorph exhibits visible
frequency plasmons, whereas the other two reach the NIR.
Since our findings for 2D boron look promising, it is very likely
that other polymorphs may support plasmons in the visible
range. Overall, with such a high frequency range for plasmonic
response with essentially no doping, 2D boron emerges as a
strong candidate for exploration and possibly applications in
photonic and plasmonic devices. One should of course
appreciate that to realize this tantalizing potential, borophene
should be transferred or grown on insulating substrates, which
is a subject of focused effort in experimental laboratories.57
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/jacs.7b10329.
Cohesive energies and optimized coordinates of B△, B□,
and B◇; convergence of plasmon dispersion with respect
to vacuum length; variation in plasmon propagation vs
relaxation time (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*biy@rice.edu
ORCID
Sharmila N. Shirodkar: 0000-0002-9040-5858
Author Contributions
‡
Y. Huang and S. N. Shirodkar contributed equally to this work.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the Army Research Office Grant
W911NF-16-1-0255 and by the Robert Welch Foundation (C-
1590). We thank Alex Kutana and Henry Yu for helpful
discussions. We used computational resources on the DAVinCI
cluster at Rice University.
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