Article

Cite This: J. Phys. Chem. C 2019, 123, 17459−17465 pubs.acs.org/JPCC

Two-Dimensional CuO Inside the Supportive Bilayer Graphene

Matrix
D. G. Kvashnin,*,†,‡ A. G. Kvashnin,§ E. Kano,*,∥,⊥ A. Hashimoto,∥,⊥ M. Takeguchi,∥ H. Naramoto,#
S. Sakai,∥,# and P. B. Sorokin†,‡,#,∇
†
National University of Science and Technology MISiS, 4 Leninskiy Prospekt, Moscow 119049, Russian Federation
‡
Emanuel Institute of Biochemical Physics of RAS, 4 Kosygin Street, Moscow 119334, Russian Federation
§
Skolkovo Innovation Center, Skolkovo Institute of Science and Technology, 3 Nobel Street, Moscow 121205, Russian Federation
∥
National Institute for Materials Science, 1-2-1 Sengen, Tsukuba 305-0047, Japan
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⊥
Graduate School of Pure and Applied Science, University of Tsukuba, 1-2-1 Sengen, Tsukuba 305-0047, Japan
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National Institutes for Quantum and Radiological Science and Technology QST, 1233 Watanuki, Takasaki 370-1292, Japan
∇
Technological Institute for Superhard and Novel Carbon Materials, 7a Centralnaya Street, Troitsk, Moscow 108840, Russian
Federation
*
S Supporting Information

ABSTRACT: New two-dimensional (2D) copper monoxide

located at the pore in a bilayer graphene matrix is investigated
in both theoretical and experimental ways. Strict analysis of
the lattice stability with respect to the magnetic state reveals
that the CuO monolayer displays an antiferromagnetic
rectangular structure as a favorable state. It is shown that
2D CuO can be confined in a bilayered graphene pore
terminated with Cu atoms forming spin-polarized states on
the graphene/CuO interface. It is found that the co-presence
of Cu and O atoms around the bilayered graphene edge plays
an essential role in the 2D CuO formation process.

S uccessful synthesis and investigation of graphene estab-

lished a wide family of two-dimensional (2D) materials
containing compounds of different compositions and atomic
structures with various sorts of physical and chemical
properties. Such a family may even consist of 2D films without
layered bulk counterparts, which allows one to suggest the
expandability of the family on new 2D materials with unusual
atomic structures. For example, 2D metal oxide and carbide
films can form monolayer structure like graphene and h-BN
but also exhibit an ordered magnetic structure and specific
rectangular lattice.1−4
Recently, much effort has been made to synthesize 2D metal
oxide films, which were successfully cleaved from the surface of
bulk layered oxides.5−8 Theoretical and experimental studies
on Fe,9 FeO,3 CuO,2 and ZnO10 monolayers suspended in a
graphene pore suggest the possibility of formation of
monolayered lateral heterostructures made of 2D metal oxide
and graphene matrix. Herein, copper oxide is especially
important due to possible high-temperature superconductiv-
ity11−14 and promising applications in catalytic substrates,15
solar cells,16 thin-film transistors,17 and others.
To design new 2D heterostructures with tunable electronic
and magnetic properties, it is highly desirable to produce pores
in graphene in a controlled manner. However, the trend of
graphene defects to heal with restoring a perfect graphitic
structure18 may complicate the formation of monolayers inside
the graphene pore. In contrast to the defects in graphene
monolayers, pores in bilayer graphene (BG) have a stable
geometry of the edges and no healing was observed.19−21
Indeed, the free edges of the neighbored graphene layers tend
to connect with each other to minimize the edge energy as was
shown in ref 22. Such a process was shown to be energetically
favorable and the connection of the edges proceeds without
any energy barrier accompanying the formation of stable and
chemically inert boundaries.
Here, we present a comprehensive investigation of a two-
dimensional copper oxide monolayer inside a bilayered
graphene pore (BGP) by employing experimental and
theoretical approaches. The atomic structures of both free-
standing CuO and implemented CuO in BG were studied and
discussed in comparison with the experimental data. The
density functional theory methods were used to calculate the
thermal stability and electronic and magnetic properties. The
binding energy for each possible type of interface was
calculated. We also performed the investigation of the growth
Received: June 5, 2019
Published: June 14, 2019

© 2019 American Chemical Society 17459 DOI: 10.1021/acs.jpcc.9b05353

J. Phys. Chem. C 2019, 123, 17459−17465
The Journal of Physical Chemistry C
process of 2D CuO in BGP using the evolutionary algorithm
USPEX.
■ METHODS
Calculations of the atomic structure, stability, and spin-
dependent electronic properties were carried out using the
DFT + U method23 describing transition-metal compounds
within general gradient approximation24 and using the
augmented plane-wave method25 implemented in VASP
software.26−28 First, we defined the parameters U−J for the
correct description of electronic properties, in particular, the
value of the band gap of bulk (three-dimensional) CuO by
taking into account the intra-atomic Coulombic and exchange
interactions. The U−J parameter was found to be 8.5 eV to
obtain the band gap of about 1.5 eV.14 Due to the large size of
the considered supercells (more than 250 atoms), the energy
cutoff was set at 250 eV. Atomic structure relaxation was
carried out until the interatomic forces became less than 0.001
eV/Å. To avoid spurious interactions caused by periodic
images of the considered supercells, the lattice vector in the
nonperiodic direction was set at ∼15 Å. Behaviors of Cu and
CuO clusters in BG nanopores under constant temperature
were described by means of the molecular dynamics (MD)
method using the Nosé−Hoover thermostat.29,30 The total
simulation time varied from 0.15 to 0.35 ns with the time step
of 0.1 fs. The simulation of the formation of the CuO layer
between the two edges of BG was carried out using the first-
principles fixed-composition evolutionary algorithm as imple-
mented in the USPEX code adapted for the surfaces.31−34
Search for the stable crystal structure of a free-standing two-
dimensional CuO monolayer was performed using the USPEX
code as well. In both cases, the evolutionary searches were
combined with structure relaxations using density functional
theory (DFT)35,36 also within the generalized gradient
approximation24 (spin-polarized generalized gradient approx-
imation in the case of free-standing CuO) and the projector
augmented plane-wave method 25 implemented in the
VASP26−28 package. The plane-wave energy cutoff of 500 eV
and the k-mesh of 0.05 × 2π/Å−1 resolution ensure an
excellent convergence of total energies. For the isolated slabs,
the monopole, dipole, and quadrupole corrections were taken
into account using a method discussed in refs 37 and 38.
During the structure search, the first generation (80 structures
for prediction of the interface and 120 structures for the
isolated monolayer) was produced randomly; the successive
generations were obtained by applying 40% heredity, 10% soft
mutation, 20% transmutation operations and 30% of the
generation was produced using symmetry random generators.
Each of the considered supercells contained a vacuum layer of
20 Å.
The unusual two-dimensional nature of CuO is different
from its bulk counterpart,14 requiring detailed investigation of
its atomic structure. We performed an evolutionary search for a
stable free-standing CuO monolayer using the USPEX
code.31,32,39 The predicted lowest-energy structures were
then relaxed with ferromagnetic and antiferromagnetic spin
ordering to define the favorable magnetic state. In Figure 1, the
atomic structures of several predicted CuO monolayers are
shown. It was found that all predicted monolayers are magnetic
with preliminary antiferromagnetic spin ordering, except for
the fourth predicted structure with ferromagnetic ordering
(Figure 1). The experimentally observed1 CuO layer with a
rectangular lattice displays the lowest energy. The lattice
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Figure 1. Energy difference between predicted 2D CuO structures
and corresponding bulk antiferromagnetic counterpart. Yellow, blue,
and red bars correspond to antiferromagnetic, ferromagnetic, and
nonmagnetic states of 2D CuO, respectively. The corresponding
atomic structures with an energetically favorable spin configuration
are presented. Cu and O atoms are shown in brown and red colors,
respectively.
parameters of the predicted structure with a rectangular lattice
are a = 5.468 Å and b = 5.457 Å. The CuO structure
containing 8-membered rings is less energetically favorable and
may be considered as a defective orthorhombic CuO observed
experimentally.1 The graphene-like structure with a hexagonal
symmetry (h-CuO) has a higher energy, and the sublattice
atoms in the unit cell tend to leave the plane, forming a
silicene-like corrugated structure. It is worth noting that h-
CuO is energetically unfavorable without the corrugation even
compared to the latter structure. The atomic structure with the
highest energy among considered ones belongs to the
orthorhombic CuO containing Cu−O−Cu chains with a
ferromagnetic order different from the other predicted CuO
structures.
We used a partially bilayered graphene common to both the
experiments in ref 1 and this report. The graphene sheet was
synthesized by chemical vapor deposition under the condition
determined from ref 40 to make AB-stacked BG. The number
of layers of graphene in each area was confirmed by dark-field
transmission electron microscopy (TEM) and high-resolution
TEM techniques (see pp 29−32 in ref 41). In ref 1, we
confirmed the structure and composition of a 2D CuO
monolayer at the atomic level by annular dark-field scanning
TEM (ADF-STEM) combined with electron energy-loss
spectroscopy (EELS). We used TEM-EELS for this report
instead, and the result suggested that the sample was
composed of C, Cu, and O, although the TEM-EELS spectra
are not only from 2D CuO in graphene but also from a wide
area of the sample.
Figure 2a shows the experimentally observed TEM image of
2D CuO in a graphene pore. Figure 2b−d shows the selected
magnified and filtered TEM images obtained from the same
area in a TEM movie. Before taking the movie, we irradiated a
strong electron beam in a wide area to make a pore (BGP) in a
bilayered graphene area. The microscope was operated at 80
kV at room temperature. Graphene is much stable when
heated at around 500 °C, while it can be easily etched away at
room temperature under electron beam irradiation because of
oxygen-based contaminants remaining on the graphene
surface.42 The TEM movie was then acquired at a speed of
1 frame/s. The area of bilayered graphene was partially etched
away, and the 2D CuO surrounded by not only BG but also
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Figure 2. Experimental TEM image of 2D CuO inside BGP. The
image was taken under over-focus so that the metal atoms appeared
bright. (b−d) Filtered TEM images of the 2D CuO region. When Cu
atoms at the edge migrated (from (b) to (c)), the 2D CuO changed
its orientation (from (c) to (d)) while preserving the rectangular
lattice.
monolayer graphene was generated (see Figure S1 in the
Supporting Information). In the images of Figure 2b−d, one
can clearly see the rectangular arrangement of atoms, with the
same feature as observed in the previous report.1 The 2D CuO
in ref 1 was on monolayer graphene, while the 2D CuO in the
present images is arranged in the graphene pore with a
diameter of ∼2 nm. The atoms especially at the edge of the
graphene pore are unstable, and they may migrate away every
few seconds under electron beam irradiation,43 which leads to
the orientation change of the 2D CuO as seen in Figure 2b−d.
Interestingly, even after such a reorientation, CuO maintained
its 2D rectangular lattice structure in the graphene pore. We
obtained a value of the Cu−Cu distance of 2.78 ± 0.03 Å in
this report (using the graphene lattice constant as a reference),
similar to that of 2.83 ± 0.06 Å in ref 1. According to the TEM
data, we can conclude that a part of the edges is BG, which
motivates us to investigate the effect of a BG matrix on the
structure and stability of the copper-based monolayers formed
therein.
To provide a theoretical foundation for the presence of a
Cu-based monolayer in BGP, we first studied the stability of
the orthorhombic monolayer consisting of only Cu atoms
inside the pore with the AA and AB graphene stacking (see
Figures 2a and S2 in the Supporting Information, respectively).
The Cu monolayer was placed in BGP in a rectangular shape.
This simple model provides an opportunity to study the
features of the interface between the Cu monolayer and
zigzag/armchair edges of BG. The geometry relaxation
simulation clearly shows that the Cu monolayer with a
rectangular lattice tends to transform to the hexagonal one.
This represents the fact that even under the confined
condition, the pure metallic structure favors the “hexagonal
close packing” in the two-dimensional state regardless of the
graphene stacking. The obtained results show the possibility of
stabilization of the hexagonal Cu monolayer in BGP. In
contrast to this, our calculation in ref 1 showed that a small
two-dimensional copper cluster placed on the graphene surface
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tends to buckle, indicating its instability as a two-dimensional
free-standing substance.
Previous experimental and theoretical works1−3,44 showed
that transition metals can form two-dimensional stable
structures with rectangular lattice only by combining with
oxygen or carbon. According to the reported data,1 we suggest
that the observed structure is a 2D copper oxide. Taking into
account the recent studies of the 2D Fe,9 ZnO,10 and FeO3
monolayers inside graphene nanopores, we simulated the
simple models of CuO monolayers within the BGP with the
AA and AB graphene stacking (see Figures 3 and S3 in the
Figure 3. Simulation of atomic structure of the pure Cu monolayer
inside BGP with AA stacking of graphene layers before and after
geometry relaxation. (b) MD simulations of the CuO monolayer
inside the BGP at T = 600 K for 0 and 3 ps time steps. Copper,
oxygen, and carbon atoms are depicted by brown, red, and green
colors, respectively.
Supporting Information, respectively). We found that the CuO
monolayer undergoes small changes in the atomic structure in
the confined state for both stacking cases. The relaxed atomic
structures of the CuO monolayers are shown in Figures 3b and
S3a in the Supporting Information for the AA and AB stacking
BGs, respectively. Ab initio molecular dynamic (MD)
simulation at high temperature (600 K) for 3 ps showed the
stability of the 2D CuO in BGP (see Figures 3b and S3b).
During the MD simulation, the rectangular lattice of CuO
remains stable and the interface between the CuO monolayer
and BGP does not change. It was found that difference in the
stacking of BG does not impact significantly the interface
between the BGP edges and CuO monolayer. Since the
graphene stacking merely affects the stability of the 2D CuO in
BGP, only AA stacking was studied further.
The interface between copper oxide and graphene is of
particular interest from both fundamental and practical points
of view because it has a crucial impact on the properties of the
confined CuO monolayer. Due to the rectangular symmetry of
the 2D CuO, its edges can be named in the same manner as in
ref 45. The edges oriented parallel to the lattice vectors and
containing both Cu and O atoms were defined as a linear (LN)
type. The edges including only one atomic type could be
named as zigzag (ZZ), according to its atomic arrangement
(Figure 4a). It should be noted that the latter edge could be
terminated by copper and oxygen, but in the presented work,
only the termination with metallic atoms was studied. In the
case of BG, two types of edges: zigzag and armchair (AC),
were considered. Due to the mismatch and special mutual
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Figure 4. Schematic representation of 2D CuO with denotations of the edges. (b) Atomic structures and the corresponding names of four
considered CuO/BG interfaces.
orientation between graphene and the CuO monolayer, several
possible types of interfaces can be considered: ZZ−LN, ZZ−
ZZ, AC−LN, and AC−ZZ (the first and second parts label the
type of the BG and CuO edge, respectively) (Figure 4b).
The binding energy of the interface was calculated using the
equation
ECuO/BG − E BG − ECuO
Eb =
2L (1)
where ECuO/BG, EBG, and ECuO are the total energy of the
interface and the individual components (BG and CuO) and L
is the length of the interface within the unit cell, which was
multiplied by 2 due to the presence of the two interfaces in the
considered CuO/BG supercell (Figure 4b). The calculated
values of the binding energies are presented in Table 1.
Table 1. Calculated Values of Binding Energies of CuO/BG
Interfaces
interface configuration ZZ−LN AC−LN ZZ−ZZ AC−ZZ
binding energy (eV/Å) 1.04 −0.078 −2.63 −0.52
Termination of the bilayered graphene edges by chemically
active copper atoms leads to the energy preference of the
interfaces with the AC−ZZ and ZZ−ZZ configurations;
however, the relative stability of the considered interfaces
mainly comes from their geometry. The most energetically
favorable ZZ−ZZ interface (−2.63 eV/Å) represents the
almost perfect connection of two undistorted layers of BG and
CuO by Cu termination. The Cu atoms on the edges make a
strong connection with the ZZ edge of BG due to the small
lattice mismatch (less than 1%) between the corresponding
CuO and the graphene superlattices. In the case of the AC−ZZ
interface, the presence of a Cu termination also leads to the
formation of a low-energy interface between CuO and the AC
edges of BG. However, the presence of the mixed edges (ZZ−
LN and AC−LN) in BGP does not allow the formation of a
smooth interface between the bilayered graphene edge and
CuO like in the case of the AC−ZZ interface. Cu and O atoms
on the edge tend to move in the bridge position between two
graphene layers, which causes a local corrugation of the CuO
lattice near the interface (see Figure 4b). Copper and oxygen
atoms move out from the plane of the CuO monolayer toward
different graphene layers. In both the ZZ and AC edges of BG,
oxygen atoms prevent the formation of the C−C bonds
between two graphene layers in the bilayered edge, which leads
to the increase of the whole interface energy.
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We studied how the CuO/BG interface can influence the
spin-dependent electronic properties of the 2D CuO. The
calculations were performed for the most stable CuO/BG
interfaces (ZZ−ZZ and AC−ZZ) as shown in Figure 5. A
detailed analysis through the comparison between the spin-
resolved densities of states (DOS) of the CuO/BG interface
and of its individual components (Sections (i)−(iv) in Figure
5) reveals that the formation of the CuO/BG interfaces
changes the electronic properties of BG significantly. Visual-
ization of the electron density distribution (top panels of
Figure 5) suggests that in both the energetically preferable
interfaces (ZZ−ZZ and AC−ZZ), the electron density in CuO
is mostly redistributed at the region close to the interface. The
individual BG component displays a DOS that is symmetric
with respect to the majority and minority spin states (Figure 5,
Section (i)), while the connection with the CuO component
(Figure 5, Section (ii)) leads to the appearance of spin density
on the interface carbon and copper atoms. Spin polarization
(SP) of the interface atoms derived from the interfacial DOS
(Figure 5, Sections (iii)−(iv)) varies depending on the type of
the CuO/BG interface. It was found that the ZZ−ZZ interface
displays a small SP in carbon and copper atoms at the Fermi
energy (about 1%, see Sections (v) and (vi) in Figure 5a),
while the less energetically preferable AC−ZZ interface
displays a higher SP value (about 4 and 8%) at the Fermi
energy for carbon and copper atoms, respectively (Sections (v)
and (vi) in Figure 5b). On the other hand, the interface effect
on the spin properties of the CuO region has the opposite
character. The isolated 2D CuO region displays a pronounced
spin asymmetry originating from the presence of the
chemically active edges terminated by Cu (see Figure 5,
Section (ii)). After the formation of the CuO/BG interfaces,
the spin asymmetry on copper atoms drastically decreases
through the spin redistribution between CuO and the edges of
BG (see Figure 5, Section (iv)). The similar effect was
observed in both interfaces considered. The above results allow
us to discuss the prospects of forming the interfaces of this
kind for potential use in spintronics.
The formation process of the CuO monolayer in BGP was
investigated in a step-by-step manner using the evolutionary
algorithm USPEX.31−34 The supercell comprising two
bilayered graphene edges containing 64 carbon atoms was
used as a substrate. Structural evolution in the region between
BG edges was observed by depositing a certain amount of Cu
and O atoms on the substrate. The simulations were
performed under three different conditions of the Cu:O ratios
of 10:8, 12:12 and 14:12. The obtained results are shown in
Figure 6a−c for Cu:O = 10:8 (a), 12:12 (b) and 14:12 (c).
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Figure 5. Electron density distribution after the formation of ZZ−ZZ (a) and AC−ZZ (b) interfaces. DOS of individual BG and CuO edges
partially resolved for C (i) and Cu (ii) atoms, respectively. DOS of the CuO/BG interface partially resolved for C (iii) and Cu (iv) atoms. Energy
dependence of spin polarization of C (v) and Cu (vi) atoms on the CuO/BG interface. The majority and minority spin states are shown as red and
blue lines, respectively.

Figure 6. Atomic structure of the CuO monolayer formed between the bilayered graphene edges predicted by evolutionary algorithm USPEX. The
Cu:O ratio was chosen as (a) 10:8, (b) 12:12 and (c) 14:12 to consider the structural evolution depending on the deposited amounts of copper
and oxygen atoms. Carbon atoms are shown in brown color, copper atoms in blue, and oxygen atoms in red.

During the evolutionary search in the first generation, the Cu
and O atoms were deposited randomly between the edges of
the BG components. The evolution algorithm was used to
perform a global optimization to find a stable structure of the
CuO/BG interface. The distance between the graphene edges,
which is equivalent to the pore size, was chosen to be 11.5 Å.
The result of the simulations with deficiency of O atoms
(Cu:O = 10:8) is shown in Figure 6a. A small amount of Cu
and O atoms initiates the early step of the interface growing
process, which begins at the bilayered graphene edges and then
two Cu−O parts move toward each other (Figure 6a).
Increasing the number of deposited atoms (Cu:O = 12:12)
leads to the connection of the two Cu−O parts on each of the
bilayered graphene edges (Figure 6b). Further increase of the
number of deposited atoms (Cu:O = 14:12) induces the
interface formation with Cu2O2 square units (highlighted by
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blue) as a dominant structural motif (Figure 6c). Due to the
lattice mismatch between BG and the orthorhombic CuO
monolayer, the formation of a uniform interface is not possible
and the O−O bond with the length of 1.49 Å is formed as seen
in Figure 6b,c. The distance between the neighboring Cu
atoms at the boundary of the two CuO monolayers is ∼2.3 Å.
Such an interface contains equal amounts of O−O and Cu−Cu
bonds along the boundary. The obtained results claim the
possibility of the formation of an atomically thick rectangular
CuO monolayer as well as the possible appearance of a mirror
symmetry one-dimensional topological defect therein.
In the present work, the atomic structure and electronic
properties of a novel CuO monolayer were investigated in both
theoretical and experimental ways. The systematic study of
atomic geometry unambiguously revealed that the 2D CuO in
the ground state displays a rectangular atomic structure and
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antiferromagnetic spin ordering. Experimental observation of
the 2D CuO in the bilayered graphene pore motivated us to
study such heterostructure in detail. The analysis of the
formation process of the 2D CuO in BGP using the
evolutionary algorithm allowed us to reveal the structural
features of the interface-growing process, whereas stability
analysis allowed us conclude that even a small nanometer-sized
2D CuO patch in BGP displays stability at high temperature of
up to 600 K.
The investigation of spin-dependent electronic properties of
the 2D CuO/bilayered graphene interface revealed noticeable
spin polarization in the vicinity of the Fermi energy. Our
findings testify that the bilayered graphene pore can be
considered as a promising template for the synthesis of new 2D
materials with specific electronic properties therein.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.9b05353.
TEM images of CuO and graphene; simulation of
atomic structure of the pure Cu monolayer; and results
of geometry relaxation of the CuO monolayer (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: dgkvashnin@misis.ru (D.G.K.).
*E-mail: e.kano0727@gmail.com (E.K.).
ORCID
D. G. Kvashnin: 0000-0003-3320-6657
A. G. Kvashnin: 0000-0002-0718-6691
S. Sakai: 0000-0002-0367-9106
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge Dr. Shiro Entani (QST), Dr.
Songtian Li (QST), and the members of QST for fruitful
discussion. TEM observation was supported by the “Nano-
technology Platform project” sponsored by MEXT, Japan. This
work was partially supported by JSPS KAKENHI, Japan
(Grant No. 15J04118 for E.K., 25390035 for A.H., and
16H03875 for S.S). A.H. acknowledges the Global Research
Center for Environment and Energy based on Nanomaterials
Science, MEXT, Japan. S.S. acknowledges the QST Advanced
Study Laboratory (Res. Gr. For Advanced Quantum Func-
tional Materials). The features of stability and atomic
structures 2D Cu and CuO layer was supported by the
Russian Science Foundation (Project identifier: 17-72-20223).
The analysis of bilayered graphene atomic structure was
supported by RFBR 17-02-01095. The study of interface
effects was supported by Increase Competitiveness Program of
NUST “MISiS” No. K2-2019-016 and Grant of President of
Russian Federation for government support of young DSc.
(MD-1046.2019.2). We are grateful to the supercomputer
cluster provided by the Materials Modelling and Development
Laboratory at NUST “MISIS” (supported via the grant from
the Ministry of Education and Science of the Russian
Federation No. 14.Y26.31.0005), and to the Joint Super-
computer Center of the Russian Academy of Sciences and the
Arkuda supercomputer of Skolkovo Foundation.
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17465 DOI: 10.1021/acs.jpcc.9b05353

J. Phys. Chem. C 2019, 123, 17459−17465