Research Article

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Auxetic B4N Monolayer: A Promising 2D Material with in-Plane

Negative Poisson’s Ratio and Large Anisotropic Mechanics
Bing Wang,† Qisheng Wu,† Yehui Zhang, Liang Ma,* and Jinlan Wang*
School of Physics, Southeast University, Nanjing 211189, P. R. China
*
S Supporting Information

ABSTRACT: Auxetic materials, known with negative Poisson’s ratio, are highly
desirable for many advanced applications, but the candidates are rather scarce,
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especially at low dimension. Motivated by the re-entrant structure that often

exposes negative Poisson’s ratio, we predict a two-dimensional (2D) planar B4N
monolayer as a promising auxetic material with unusual in-plane negative Poisson’s
ratio within the framework of density functional theory calculations. B4N
monolayer also exhibits a highly emerged mechanical anisotropy, characterized
by Young’s modulus and Poisson’s ratio. In addition, this monolayer shows
superior mechanical flexibility in ideal tensile strength and critical strain values. The
phonon dispersion calculations and ab initio molecular dynamics simulations
further demonstrate that this monolayer also owns excellent dynamical and thermal
stabilities. The fantastic mechanical properties coupled with robust structural
stability render the auxetic B4N monolayer promising for future nanomechanical
devices.
KEYWORDS: auxetic materials, re-entrant structure, mechanical property, B4N monolayer, first-principles method

■ INTRODUCTION
Poisson’s ratio (ν) of a material is defined as the ratio of the
transverse contraction strain to the longitudinal extension
strain, which measures the fundamental mechanical responses
of solids against external loads.1 Most materials expose positive
Poisson’s ratio, which means that they will become thinner (or
thicker) in the lateral directions when experiencing a
longitudinal tension (or compression).2,3 In contrast, a small
group of materials with negative Poisson’s ratio (NPR),
namely, auextics or auxetic materials, exhibit a counterintuitive
behavior in contrast to that of conventional materials, which
expand when stretched and contract when compressed.4 The
first auxetic material was discovered in 1982,5 and since then,
auxetic materials have attracted worldwide attention because of
their unique mechanical properties5−8 and high demand in
many advanced applications, such as tissue engineering,9
medicine,10 tougher composites,11 fasteners,12 bulletproof
vests, aircraft,13 national security, and so on.14−16 Within the
last 30 years, a variety of NPR materials and structures have
been discovered, synthesized, or fabricated, ranging from
macroscopic down to molecular levels.17
Although most reported auxetic materials are in bulk form,
the negative Poisson’s ratio is possible in two-dimensional
(2D) structures according to the theory of Gibson.5 As the
blooming of 2D family, several systems with NPR have been
predicted theoretically,18−29 and only one of them, black
phosphorus,19,20 has been observed experimentally. To date,
the intrinsic 2D auxetic materials are still rather limited, far
from meeting the wide range of needs in practice. Seeking new
2D auextic materials is still a pressing task for modern
nanoscale devices. Re-entrant structure is one of the typical
auxetic structures that has been widely used to model the
deformation of auxetic foam by many researchers.2,5,15,30−36
Lakes et al.33 reported the first manmade auxetic material with
a re-entrant foam structure. Wang et al.30 designed a novel re-
entrant auxetic honeycomb with the in-plane impact responses
computationally. Jin et al.34 and Chang et al.35 used the re-
entrant structure as sandwich structure core to improve the
blast resistance and dynamic response. Although this structure
is allowable in traditional engineered materials, to the best of
our knowledge, 2D auxetic material with re-entrant structure
has yet to come.
Very recently, various 2D boron monolayers (BMs) were
predicted theoretically,37−41 and the χ3 phase (χ3-BM) was
successfully synthesized on Ag(111) substrate by two different
groups.42 It is interesting to note that a re-entrant-like structure
can be extracted from the χ3-BM. However, the expected NPR
is actually absent without negative inclined and vertical strut
angle. In this work, we predict a new planar auxetic 2D B4N
monolayer, which can be viewed as nitrogen-embedded χ3-BM.
Our density functional theory (DFT) computations show that
the B4N monolayer exposes large anisotropic NPR and high in-
plane Young’s modulus. It also owns ultrahigh tensile strains
(19 and 18% along x and y directions, respectively), which are
comparable to those of graphene. Moreover, the planar B4N
Received: June 15, 2019
Accepted: August 22, 2019
Published: August 22, 2019

© 2019 American Chemical Society 33231 DOI: 10.1021/acsami.9b10472

ACS Appl. Mater. Interfaces 2019, 11, 33231−33237
ACS Applied Materials & Interfaces Research Article

monolayer shows excellent thermal, dynamic, and mechanical hexagonal honeycomb hole in-between (Figure 1c). Geometri-
stabilities as well. cally, the angle θ for χ3-BM is always positive due to its

■ RESULTS AND DISCUSSION

The typical hexagonal and re-entrant honeycomb structures, as
shown in Figure 1a, b, respectively, can be numerically
Figure 1. Sketch for the (a) hexagonal and (b) re-entrant honeycomb
structure. The lengths (in angstroms) of (c) the representative
chemical bonds of χ3-BM and (d) the atomic configuration for B4N
monolayer. The unit cells are denoted with the black lines. The blue
and green balls represent N and B atoms, respectively.
distinguished by the length of the horizontal strut h, the length
of the inclined strut l, and the angle θ (ϵ[-π/2, π/2]) between
the inclined and vertical strut. In such a representation, the
Poisson’s ratio along x direction (νx) for both hexagonal and
re-entrant honeycomb structure with mechanical loading along
y-direction, as an example, can be expressed by the eq 1:43−45
hexagonal honeycomb structure. Thus, only positive Poisson’s
ratio is expected for the χ3-BM monolayer. It is known that B
and N atoms can also form strong B−N bonds but their
lengths (∼1.45 Å in h-BN) would be much shorter than the
B−B bonds. It would be very interesting to figure out whether
the honeycomb structure can be altered by introducing shorter
B−N bonds into the 2D χ3-BM monolayer and even give rise
to the negative angle θ with charming NPR. To this end, we
design a planar 2D re-entrant structure by injecting N atoms
into χ3-BM, namely B4N monolayer, as shown in Figure 1d.
After structure relaxation, it is shown that the length of B−N
bonds (1.33 Å) in B4N monolayer is much shorter than the B−
B bonds in χ3-BM (1.64−1.72 Å, Figure 1c) and even shorter
than that in h-BN (∼ 1.45 Å), which is able to convert the
honeycomb structure into a stable re-entrant structure with
NPR. More detailed discussion will be given in the following
sections. The structure exposes Cmmm symmetry (space group
No. 65) with orthogonal lattice. The optimized lattice
parameters are a = 2.9693 Å and b = 10.7035 Å with B1 at
4j (0, 0.2212, 1/2), B2 at 4j (1/2, 0.1246, 1/2), and N at 2c
(1/2, 0, 1/2), respectively. N atoms act as “bridges” by
bonding with two B atoms in B4N monolayer.
Young’s modulus (E), reflecting the flexibility or rigidity of
materials, and Poisson’s ratio (ν), reflecting the mechanical
responses of solids against external loads, are two main
mechanical parameters of a material. For 2D linear elastic solid
materials, E and ν along x and y directions can be derived from
the elastic constants as below:
Ex = (C11C22 − C12C21)/C22 (2)
Ey = (C11C22 − C12C21)/C11
(3)

εy (h + l sin θ )sin θ νx = C21/C22 (4)

νx = − =
εx l(cos θ )2 (1)
Markedly, the sign of νx is determined by the sin θ term in the
numerator, and negative angle θ (ϵ [−π/2, 0]) will produce
negative νx, that is, the NPR effect. As can be clearly seen from
Figure 1, the angle θ is always positive for the typical hexagonal
structure but negative for the re-entrant structure, which means
that the NPR effect would definitely appear in the re-entrant
structure of B4N monolayer but not the regular hexagonal
structure.
The synthesized χ3-BM consists of waved and double-
chained boron atoms that connect to each other with a regular
νy = C12/C11 (5)
The calculated mechanical properties of B4N monolayer are
shown in Table 1, together with those of other well-studied 2D
materials for comparison. The calculated results for known 2D
materials are in good agreement with previous experimental/
theoretical reports,26,38,46−48 demonstrating the reliability of
our present theoretical method. Based on eqs 2 and 3, the in-
plane Young’s moduli along x (Ex) and y (Ey) directions of
B4N monolayer are calculated to be 153 N/m and 268 N/m,
respectively, exposing strong anisotropy. To gain a compre-

Table 1. Elastic Constants Cij(N/m), Young’s Modulus E(N/m), and Poisson’s Ratio ν of B4N, χ3-BM, Graphene, h-BN, and
MoS2a
structures reference C11 C22 C12 C66 Ex Ey νx νy
B4N our work 153 267 −4.9 28 153 268 −0.018 −0.032
χ3-BM ref 38 196 208 0.11 0.12
graphene our work 349 349 72 138 334 334 0.206 0.206
ref 46 340 340
ref 26 343 343 62 332 332
h-BN our work 290 290 64 112 276 276 0.22 0.22
ref 47 289.8 289.8 63.7 113.1 275.8 275.8 0.22 0.22
MoS2 our work 128.8 127.9 28.8 50 122.3 121.5 0.224 0.225
ref 48 123 123 0.25

a
The present results are also compared with previous literature. Ref 46, experiment; refs 26, 38, 47, and 48, theory.

33232 DOI: 10.1021/acsami.9b10472

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Figure 2. Calculated orientation-dependent (a) Young’s modulus E(α) in N/m and (b) Poisson’s ratio ν(α). (c) Total energy with respect to
lattice response of the other direction when the B4N monolayer lattice is under 5% tensile strain along x and y directions, respectively. The arrows
indicate the equilibrium magnitude of εx and εy, respectively. (d) Stress−strain relationship of B4N/graphene along x (0°)/zigzag and y (90°)/
armchair directions. The arrows denote the strain at the maximum stress.

Figure 3. (a) Lengths (in angstroms) of the representative chemical bonds of B4N monolayer. (b) Charge density of B4N monolayer with the iso-
surface of 0.99 e/Å3. (c) Explanation of negative Poisson’s ratio via hinging of ribs in response to applied stretching in x direction. (d) Band
structure and 2D Brillouin zone of B4N monolayer.

hensive description of the anisotropic mechanical properties of
B4N monolayer, the in-plane Young’s moduli as functions of
the arbitrary direction α (α is the angle relative to the positive
33233
x direction in this monolayer) were calculated and presented in
2D polar representation curve (Figure 2a). Obviously, the
Young’s moduli of B4N monolayer are highly anisotropic in the
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Figure 4. (a) Phonon dispersion of B4N monolayer. (b) Fluctuation of total energy during AIMD simulation of B4N monolayer at 500 K. The inset
is the structure of B4N monolayer at the end of the AIMD simulation after 5 ps. (c) Schematic illustration of preparing B4N.
whole plane. The Young’s modulus E(α) first decreases to its
minimum value of 80 N/m at α = 45° from a value of 153 N/
m at α = 0°(x direction) and then increases to a maximum
value of 268 N/m at α = 90°(y direction). The maximum value
(268 N/m) is comparable to that of h-BN monolayer (275.8
N/m)47 and graphene (340 N/m)46 and is about two times of
that of MoS2 (123 N/m).48
The diagram of calculated Poisson’s ratio as functions of the
arbitrary direction shows that the Poisson’s ratio of B4N
monolayer is also spatially varying and highly anisotropic
(Figure S1). More remarkably, an intriguing unconventional
NPR phenomenon is observed in this Figure for B4N
monolayer along both x and y directions. Due to the small
values of negative Poisson’s ratio, a zoom of Figure S1 near the
center point is plotted in Figure 2b. According to eqs 4 and 5,
the NPRs of B4N monolayer along x and y direction are
−0.018 and −0.032, respectively, due to the negative value of
C12. The Poisson’s ratio calculated according to the uniaxial
strain method is also in good agreement with the results
obtained through elastic constants (Figure S2). To confirm
this interesting point, we also applied a uniaxial strain of 5% in
the x and y directions of the B4N monolayer, respectively. Just
as expected, we find that the equilibrium lattice constants of y
and x directions are expanded by ∼0.28% and 0.52% (Figure
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2c), respectively. The calculated values of NPR are comparable
to that of Pmmn-borophene21 (νx = −0.04, νy = −0.02) and
black phosphorus19 (−0.027 along the z direction). Along the
directions other than x and y, B4N monolayers expose the
normal positive Poisson’s ratio. The NPR value indicates that
the B4N monolayer will actually expand in the transverse
direction when stretched along the x/y direction.
In addition to Young’s modulus and Poisson’s ratio, the ideal
strength is another important mechanical property of material.
We thus investigate the ideal strength of B4N monolayer by
calculating the stress−strain curves of x and y directions as
depicted in Figure 2d. With applied small strains, the sheet
exhibits linear stress−strain relationship with notable elastic
anisotropy. As the strain increases, the stress−strain behavior
becomes more and more nonlinear and shows enhanced
anisotropy. The maximum stress along the y direction is higher
than that along x direction. The peak stress reaches 25 N/m
along the ridges at εy = 18% and 11 N/m at εx = 19% across
the ridges, which is secondary only to graphene (34 N/m)38
but higher than black phosphorus (16 N/m). 49 For
comparison, our calculated maximum tensile strains for
graphene is 19 and 25% along the armchair and zigzag
directions, respectively, in good agreement with the previous
report50 (19.4 and 26.6% along the armchair and zigzag
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directions), further confirming the reliability of our computa-
tional method.
To probe the origin of the NPR, we further analyze the bond
lengths of B4N monolayer (Figure 3a). Take the left part of
B4N monolayer as an example, the bond lengths of B4−B5
(1.65 Å), B2−B5 (1.61 Å) and B2−B7 (1.65 Å) are shorter
than those of B4−B2 (1.81 Å) and B5−B7 (1.81 Å) by ∼9−
11%. The shorter lengths indicate the B4−B5, B2−B5, and
B2−B7 B−B bonds are stronger than those B4−B2 and B5−
B7 B−B bonds. These bonding strength differences can give
rise to the typical re-entrant honeycomb-like structure with
negative angle θ and the NPR phenomenon (ν < 0). The
charge density of B4N monolayer is also plotted to elucidate its
bond properties shown in Figure 3b. The higher charge density
between B4−B5, B5−B2, and B2−B7 also indicate stronger
bond strength than that between B4−B2 and B5−B7 bonds,
which is in good agreement with the analysis of bond lengths.
Figure 3c displays the detailed structure deformation along the
hinging of the diagonal ribs for re-entrant structure in response
to an applied uniaxial load in the x direction. Under a global
tensile loading in the x direction (red arrows), atoms B5 and
B6 of this re-entrant structure move apart, whereas atoms B2
and B1 maintain their separation. Meanwhile, the tensile strain
(red arrows) in the x direction of B4N monolayer causes the
ribs (B2−B5−B2 and B1−B6−B1 chains) aligned along y
direction to separate more (black arrows). As a result, the
overall structure expands in the y direction, and its area is also
apparently expanded while the structure is stretched, leading to
negative Poisson’s ratio. Our analyses show that the auxeticity
of our novel B4N monolayer is mainly originated from its
particular atomic arrangement.
We also calculate the projected band structures and partial
density of states to probe the electronic properties of B4N
monolayer. As shown in Figure 3d, the band lines of B4N
monolayer travel across its Fermi level, indicating that it is a
nonmagnetic metal. The PDOS analysis shows that the B-p
states and N-p states dominate around the Fermi level, which is
the principal cause of metallicity (Figure S3). The revealed
apparent hybridization between both B-p and N-p states are
consistent with the strong B−N bonds. The orbital electronic
band structure shows the main contribution to the states
around the Fermi level arises from B_pz and N_px orbitals.
The metallic property is also maintained and the band
structures change slightly under the different external strains
(Figure S4).
To assess the dynamical stability of B4N monolayer, we
examined its phonon dispersion as shown in Figure 4a. The
absence of imaginary modes confirms dynamically stability of
the B4N monolayer. The highest frequency of B4N monolayer
reaches up to 50.84 THz (1695 cm−1), which is comparable to
that of graphene (1586 cm−1),51 indicating the robust B−B
and B−N interactions in the B4N monolayer. Ab initio
molecular dynamics (AIMD) simulations were also conducted
to probe the thermal stability of B4N monolayer. Figure 4b
shows that the average value of the total potential energy
during the AIMD simulations is oscillating within a narrow
range and the integral configuration of B4N monolayer is well
maintained after 5 ps AIMD simulation, confirming its thermal
stability. The mechanical stability was also investigated by
using the strain−stress method. For a mechanically stable
orthorhombic 2D sheet, the elastic constants need to satisfy
that C11C22-C12C21> 0 and C66> 0.47 Considering the symmetry
of B4N, we have C12=C21. Table 1 shows that the calculated
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elastic constants of B4N monolayer satisfy stability criteria,
confirming the mechanical stability of this sheet. Therefore, we
can conclude that the B4N monolayer has very good
dynamical, thermal, and mechanical stability.
Although the demonstrated dynamical and thermal
stabilities have already suggested great feasibility to synthesize
B4N monolayers, it would be much greater to propose any
practical synthesis approach. The χ3-BM was successfully
synthesized on Ag(111) surface by molecular beam epitaxy.27
In the experimental process, one-dimensional boron chains or
nanoribbons were also realized in the process of BM
synthesis.17,39,41,21,52 If the N atoms are injected among the
boron chains or nanoribbons, the strong interaction between B
and N atoms may form the B4N monolayer with re-entrant
structure. A possible synthesis route for 2D B4N monolayer is
therefore proposed in Figure 4c. To evaluate the relative
stability between the χ3-BM sheet and B4N monolayer, we
calculated the formation energy, which is defined as Ef = (EB4N
− 4μχ3B − 1/2 μN2)/5. EB4N is the total energy per formula
unit, and μχ3B and μN2 are chemical potentials of 2D χ3-BM
and nitrogen, respectively. The calculated formation energy for
B4N monolayer is −0.16 eV per atom. The negative formation
energy suggests that the synthesis of the B4N monolayer is
exothermic. We also performed a global search for the lowest-
energy stable structure for B4N monolayer by using the
particle-swarm optimization method as implemented in
CALYPSO code.53 The results show that our predicted 2D
monolayer is the metastable state which has very close energy
to the most stable one (only 18 meV/atom high). More details
are given in Figure S5. Considering the excellent dynamical
and thermal stability, the experimental fabrication of B4N
monolayer might be feasible, although it would be very
challenging.
■
CONCLUSIONS
To summarize, we have successfully predicted a 2D auxetic
B4N monolayer material with attractive negative Poisson’s ratio
by using first-principles calculations. It is revealed that the
auxeticity of B4N monolayer mainly originates from its
particular re-entrant structure. The intriguing robust in-plane
NPR and high Young’s modulus of auxetic B4N monolayer are
both highly anisotropic. Besides, B4N monolayer can sustain
tensile strains of up to 19 and 18% with maximum stresses of
11 and 25 N/m in the x and y directions, respectively, which is
comparable to that of graphene. The thermal, dynamical, and
mechanical stability evaluations demonstrate the feasibility of
the synthesis of this 2D B4N monolayer and a viable
experimental route for the synthesis of B4N monolayer is
proposed as well. In view of the novel properties, we wish this
new monolayer could be synthesized in the near future and
applied to the nanomechanical devices.
■ COMPUTATIONAL METHODS
The structure relaxations and self-consistent energy calculations were
carried out by using Perdew−Burke−Ernzerhof parametrization of the
generalized gradient approximation (PBE-GGA)54 as implemented in
the Vienna ab initio simulation package (VASP).55 The projector-
augmented plane wave (PAW) approach56 was used to describe the
ion-electron interaction. The energy cutoff of the plane wave was set
to 500 eV with the energy precision of 10−6 eV and the force precision
of 10−2 eV/Å. The Brillouin zone was sampled with a 21 × 7 × 1 Γ-
centered k point grid. Phonon dispersions were calculated based on
density functional perturbation theory (DFPT) as embedded in
phonopy program.57 van der Waals interactions were considered by
DOI: 10.1021/acsami.9b10472
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ACS Applied Materials & Interfaces Research Article

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■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.9b10472.
Details about the derivation process of eq 1; calculated
orientation-dependent Poisson’s ratio ν (θ) in the xy
plane (Figure S1); correlations between applied strain
along the x (y) direction and the resultant transverse
strains along the y (x) direction (Figure S2); projected
of density of state for B4N monolayer (Figure S3); band
structure of B4N monolayer under different strains
(Figure S4); structure phonon dispersion and B4N
monolayer (Figure S5) (PDF)
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AUTHOR INFORMATION Dimensional β-Phase GeS. Appl. Phys. Lett. 2019, 114, 192903.
Corresponding Authors (17) Evans, K. E.; Alderson, A. Auxetic Materials: Functional
*Email: jlwang@seu.edu.cn. Materials and Structures from Lateral Thinking! Adv. Mater. 2000, 12,
*Email: liang.ma@seu.edu.cn. 617−628.
ORCID (18) Zhang, C.; He, T.; Matta, S. K.; Liao, T.; Kou, L.; Chen, Z.; Du,
Liang Ma: 0000-0003-4747-613X A. Predicting Novel 2D MB2 (M= Ti, Hf, V, Nb, Ta) Monolayers
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B.W. and Q.W. contributed equally to this work. (19) Jiang, J. W.; Park, H. S. Negative Poisson’s Ratio in Single-
Notes Layer Black Phosphorus. Nat. Commun. 2014, 5, 4727.
The authors declare no competing financial interest. (20) Du, Y.; Maassen, J.; Wu, W.; Luo, Z.; Xu, X.; Ye, P. D. Auxetic

■
ACKNOWLEDGMENTS
This work is supported by the National Key Research and
Development Program of China (2017YFA0204800), Natural
Science Funds of China (21773027,21525311), Jiangsu 333
project (BRA2016353), the Fundamental Research Funds for
the Central Universities (2242019R10021), the Scientific
Research Foundation of Graduate School of Southeast
University (YBJJ1773). The authors thank the computational
resources at the SEU and National Supercomputing Center in
Tianjin.
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