Letter

Cite This: J. Phys. Chem. Lett. 2019, 10, 3922−3928 pubs.acs.org/JPCL

2D Magnetic Janus Semiconductors with Exotic Structural and

Quantum-Phase Transitions
Jingyun Jiao,†,‡ Naihua Miao,*,†,‡ Zhen Li,†,‡ Yu Gan,†,‡ Jian Zhou,† and Zhimei Sun*,†,‡
†
School of Materials Science and Engineering, Beihang University, Beijing 100191, China
‡
Center for Integrated Computational Materials Engineering, International Research Institute for Multidisciplinary Science, Beihang
University, Beijing 100191, China
*
S Supporting Information
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ABSTRACT: 2D magnetic semiconductors are intriguing for their great potential

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applications in spintronic nanodevices. Despite intensive research for decades,

intrinsically 2D magnetic Janus semiconductors are scarce, and their design
guidelines remain elusive. Herein we propose new 2D Janus Cr2O2XY (X = Cl, Y =
Br/I) ferromagnets with asymmetric out-of-plane structural configurations from ab
initio calculations. Abnormally, 2D Janus Cr2O2XY crystals with Pmm2 structures
derived from pristine CrOX compounds are dynamically metastable. By introducing
novel structural phase transitions, we generated new Pma2 phases with lower total
energy and great dynamical stability. These new Janus Cr2O2XY monolayers are
intrinsically ferromagnetic semiconductors and could be easily synthesized from
experiment. Most interestingly, exotic quantum-phase transitions from the
ferromagnetic semiconductor to the antiferromagnetic metal/semiconductor
could be achieved in the Cr2O2ClI monolayer by applying compressive strains.
Our study provides an alternative strategy to design new Janus Cr2O2XY monolayers and will inspire further investigations on
relevant materials for electronic and spintronic applications.

T wo-dimensional (2D) materials have received the

considerable attention of researchers since the discovery
of graphene.1 Despite the great deal of work2−9 that has been
performed to study the various exotic properties of 2D
materials, few 2D semiconductors with intrinsic magnetism
have been found experimentally, until the successful synthesis
of 2D CrI310 and Cr2Ge2Te611 ferromagnets. The lack of
intrinsic magnetism greatly hinders the nanoscale spintronic
applications of 2D materials. Hence it is urgent for researchers
to seek new 2D materials with long-range spin ordering and
high Curie temperature. Recently, 2D ferromagnetic metals
(single-layer MBene12,13 and Fe3P14), half-metals (transition-
metal dihydride MH215 and MnX (X = P/As)16 monolayers),
and ferromagnetic semiconductors, such as CrSX (X = Cl/Br/
I), 17,18 CrWI 6 , 19 CrWGe 2 Te 6 , 19 C 6 N 8 H, 20 CrSiTe 3 , 21
CrSnTe3,22 CrX3 (X = Cl/Br/I),23,24 and MnX2 (X = S/
Se)25 monolayers, have been explored from both theory and
experiment. To obtain room-temperature ferromagnets,
various approaches have also been proposed to further enhance
the Curie temperature, including strain engineering,14,19,25 hole
doping,24 functionalization,12 isoelectronic substitution,17 and
the construction of ferromagnetic semiconductors in 2D metal
organic frameworks.26 Recently, we found that the CrOCl and
CrOBr monolayers27 are promising candidates for spintronic
devices on the nanoscale due to their intrinsic ferromagnetism,
large spin polarization, and high Curie temperature. More
emerging 2D ferromagnets combined with rich electronic
properties are highly desirable and could open the door to the
exploration of promising magnetic and magnetoelectric
applications.
2D Janus materials displays unique physical and chemical
properties due to structural symmetry breaking,28 inspiring
researchers’ increasing interest. Tremendous efforts have been
devoted to the extensive investigation of their improved
properties. 2D Janus monolayers have been well demonstrated
to show significantly enhanced piezoelectric coefficients, easily
induced intrinsic ferromagnetism, better hydrogen evolution
reaction (HER) efficiencies, and a controllable band gap. For
instance, in Janus Ga2SSe, piezoelectric coefficients were
increased up to over four times of the maximum value of
perfect monolayers.29 Intrinsic ferromagnetism could be
induced in the 2D Janus NbSeH2 monolayer.30 Janus
SeMoS31 and WSSe32 exhibit better HER efficiencies. A
tunable band gap is achieved in Janus In2SSe33 monolayers.
Obviously, 2D Janus monolayers with an asymmetric out-of-
plane structural configuration could lead to numerous
opportunities for magnetic, catalytic, piezoelectric, and
electronic applications. However, intrinsically 2D magnetic
Janus semiconductors are still scarce, and their design
guidelines remain elusive.
Herein we first propose a novel series of 2D Janus Cr2O2XY
(X = Cl, Y = Br/I) ferromagnets derived from the pristine
Received: May 30, 2019
Accepted: June 28, 2019
Published: June 28, 2019

© 2019 American Chemical Society 3922 DOI: 10.1021/acs.jpclett.9b01543

J. Phys. Chem. Lett. 2019, 10, 3922−3928
The Journal of Physical Chemistry Letters Letter

Figure 1. Crystal structures of (a) the top view of the in-plane planar layers and (b) the side view of the supercell along the y axis and the
corresponding (c) phonon dispersions and (d) density of states of the Janus Cr2O2ClI monolayer with Pmm2 symmetry. Crystal structures of (e)
the top view of the in-plane planar layers and (f) the side view of the supercell from the y axis and the corresponding (g) phonon dispersions and
(h) density of states of the Janus Cr2O2ClI monolayer with Pma2 symmetry. Calculated AIMD evolutions of total energy and magnetic moments
for Pmm2 (i) Cr2O2ClI and (j) Cr2O2ClBr monolayers. The insets shows the snapshots of single-layer Cr2O2ClI and Cr2O2ClBr structures at 300 K
after 10 ps AIMD simulations.

CrOX monolayers by replacing the top layer of X with Y
atoms, including Cr2O2ClBr and Cr2O2ClI. It is surprising to
observe that Cr2O2XY (X = Cl, Y = Br/I) monolayers with the
original Pmm2 structures as the pristine compounds are
metastable, and thus we generate new stable Pma2 structures
with lower total energy and great dynamical stability, as
3923
demonstrated by the phonon dispersion curves and ab initio
molecular dynamic simulations. We then investigate the
magnetic and electronic properties of single-layer Pma2
Cr2O2XY by comparing with the CrOX and CrOY monolayers
from first-principle calculations. Both the Cr2O2ClBr and
Cr2O2ClI monolayers are intrinsically ferromagnetic semi-
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The Journal of Physical Chemistry Letters
conductors with tunable band gaps through strain engineering.
Novel quantum-phase transitions from the ferromagnetic
semiconductor to the antiferromagnetic metal/semiconductor
could be controlled in the Cr2O2ClI monolayer by applying
compressive uniaxial strains along x, inspiring potential
applications of functional 2D Janus materials in future
electronics and spintronics.
First-principles calculations were mainly performed with the
Vienna ab initio Simulations Package (VASP)34 based on spin-
polarized density functional theory (DFT), using the
generalized gradient approximation (GGA) with the Per-
dew−Burke−Ernzerhof (PBE) parametrization.35 The projec-
tor-augmented wave (PAW) method36 were employed to
describe interactions between nuclei and electrons. The U
correction (GGA+U) was applied to treat the strong
correlation of the Cr-3d electrons proposed by Dudarev et
al.37 To account for van der Waals (vdW) interactions, the
density functional theory long-range dispersion correction
(DFT-D3) method of Grimme38 was adopted. The cutoff
energy was set to be 450 eV. The convergence criteria of the
residual force on atoms and the energy difference in the
electronic self-consistent loop were 1 × 10−2 eV/Å and 1 ×
10−6 eV, respectively. The K-meshes for the 2D monolayer and
the 1 × 2 × 1 supercell were 7 × 11 × 1 and 7 × 5 × 1,
respectively. A vacuum of 20 Å was constructed perpendicular
to the layer plane to avoid the interlayer interactions. We
obtained electronic band structures, densities of states, and
magnetic properties using the GGA+U method, unless stated
otherwise. The phonon spectra were calculated through the
density functional perturbation theory (DFPT) using a 4 × 4 ×
1 supercell.39,40 Ab initio molecular dynamics (AIMD)
simulations were performed for 5 × 6 × 1 supercells at 300
K to assess the thermal stability using a canonical ensemble
(NVT) with a Nosé−Hoover thermostat.41,42 The total
simulation time was 10 ps with a time step of 2 fs.
2D CrOX (X = Cl/Br) crystals with an orthorhombic
structure have been testified to be intrinsic ferromagnetic
semiconductor.27 Here we obtained several crystal config-
urations of Janus Cr2O2XY (X = Cl, Y = Br/I) (space group
Pmm2) monolayers with a rectangle sublattice in the xy plane
and sandwiched by X and Y along the z direction via
substituting Y for the top layer X of CrOX (Figure 1a,b). The
phonon dispersion curves were calculated to study the
dynamical stability of the Janus Cr2O2XY monolayers, as
presented in Figure 1c,d and Figure S1a,b. Apparently, single-
layer Cr2O2ClI and Cr2O2ClBr with Pmm2 structures are
dynamically metastable, with imaginary frequencies in the
range of −40 and −5 cm−1. These imaginary modes are mainly
contributed by the I atoms, as demonstrated by the phonon
density of states (Figure 1d), indicating that the I atoms tend
to vibrate to a local minimum, and thus the introduction of
additional structural distortions and atomic displacements is
helpful to stabilize the crystal structures. Herein ab initio
molecular dynamic (AIMD) simulations have been performed
at 300 K for the 5 × 6 × 1 supercells of single-layer Cr2O2ClI
and Cr2O2ClBr to assess their room-temperature thermal
stability. According to the AIMD trajectories (Figure 1i,j),
lattice distortion occurred in both Cr2O2ClI and Cr2O2ClBr
monolayers within 10 ps at 300 K, especially for the single-
layer Cr2O2ClI. We optimized the distorted structure from
AIMD simulations and obtained a new stable Pma2 structure
of Janus Cr2O2XY, as illustrated in Figure 1e,f, which shows
lower total energy and better stability than the previous Pmm2
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Letter
phase. Therefore, by inducing structural phase transitions and
including the reversed displacements of outer anions (like I/Br
atoms), the stability of these Janus Cr2O2XY monolayers has
been improved. As far as we know, this abnormal symmetry
broken behavior owing to the reversed displacement of
halogen atoms has never been reported before, which may
be beneficial for the development of new Janus materials. The
structural parameters of Janus Cr2O2XY with different space
groups are summarized in Table 1. To further demonstrate the
Table 1. Calculated Lattice Parameters and Formation
Energies Ef1 and Ef2 (eV) of Metastable and Stable Janus
Cr2O2XY Monolayers Using Two Different Synthetic
Schemes
2D crystal a (Å) b (Å) Ef1 Ef2
Cr2O2ClI (Pmm2) 3.960 3.382 2.109 −1.794
Cr2O2ClBr (Pmm2) 3.941 3.310 0.780 −0.735
Cr2O2ClI (Pma2) 6.711 3.965 2.082 −1.820
Cr2O2ClBr (Pma2) 6.628 3.944 0.779 −0.737
stability of Janus Cr2O2XY monolayers with the new Pma2
structure, we again calculated the phonon dispersion curves, as
presented in Figure 1g,h and Figure S1c,d. Obviously, these
Pma2 phases of the Cr2O2XY monolayers are dynamically
stable, as no imaginary mode is observed. Because the Pma2
structures are more stable, we focused on these stable
Cr2O2XY monolayers in the following work, unless stated
otherwise.
Janus SMoSe flakes have already been obtained exper-
imentally by the well-controlled sulfurization of single-layer
MoSe2 to replace the top layer Se,31 and hence we wonder how
Janus Cr2O2XY monolayers can be fabricated from experiment.
To evaluate the feasibility of synthesizing Janus Cr2O2XY
monolayers, we proposed two different synthetic schemes, as
illustrated in Figure 2, and calculated the corresponding
formation energies Ef1 and Ef2 (Table 1) of these Janus
structures
Scheme 1:
4CrOX + Y2 → 2Cr2O2 XY + X 2
Scheme 2:
4CrOY + X 2 → 2Cr2O2 XY + Y2
The X and Y refer to the third and fourth elements of Janus
Cr2O2XY structures, respectively. Therefore, the corresponding
formation energy can be obtained by
Ef1 = 2E(Cr2O2 XY) + E(X 2) − 4E(CrOX) − E(Y2) (1)
Ef2 = 2E(Cr2O2 XY) + E(Y2) − 4E(CrOY) − E(X 2) (2)
As shown in Table 1, the formation energies of the same
structures are very different from those of the two synthetic
approaches. Fortunately, there is always negative formation
energy for 2D Janus Cr2O2XY structures, demonstrating that
Scheme 2 is very favorable for synthesizing Janus Cr2O2XY
monolayers from experiments.
To probe the preferred magnetic order of these new Janus
Cr2O2XY monolayers, we have considered four magnetic
configurations, including one ferromagnetic (FM) state and
three antiferromagnetic (AFM) states (Figure S2). The ground
states of CrOX, CrOY, and Cr2O2XY monolayers are
determined by comparing the total energies of ferromagnetic
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Figure 2. Scheme diagram for the preparation of Janus Cr2O2XY monolayers. Ef1 and Ef2 refer to the formation energies of Schemes 1 and 2,
respectively.
and antiferromagnetic states. Interestingly, among all of the
CrOX and CrOY monolayers, only single-layer CrOI is
antiferromagnetic, whereas the others are ferromagnetic.
Furthermore, we found that both the Cr2O2ClI and Cr2O2ClBr
monolayers possess a ferromagnetic ground state. It also
noticed that the much stronger ferromagnetic exchange in the
Cl−Cr−Cl (than that in the Br−Cr−Br and I−Cr−I)
dominates the magnetic effects in these Janus crystals and
thus results in a moderately negative EFM‑AFM in these Janus
Cr2O2XY monolayers, as indicated by Table 2. All of the
Table 2. Total Energy Difference of Ferromagnetic (FM)
States and Antiferromagnetic (AFM) States, EFM‑AFM (meV/
TM), Ground-State Configurations (G.S.), and Magnetic
Moments μ (μB/TM) of the CrOX, CrOY, and Cr2O2XY
Monolayersa
2D crystal EFM‑AFM G.S. μ
CrOCl −12.1 FM 3.00
CrOBr −9.5 FM 3.00
CrOI 10.8 AFM 0.00
Cr2O2ClBr −11.0 FM 3.00
Cr2O2ClI −5.0 FM 3.00
a
TM refers to the transition-metal atoms.
structures with ferromagnetic ground states in CrOX, CrOY,
and Cr2O2XY monolayers have a net magnetic moment of ∼3
μB/TM, indicating a large spin polarization in these new 2D
Janus crystals.
Strain engineering is one of the most effective approaches to
tune the electronic structure of bulk and 2D materials.43−46 To
study the magnetic and electronic responses to strains, we
apply uniaxial strains along the x and y axes of Janus Cr2O2XY
monolayers. We first investigated the ground states of these
monolayers and found that both the Cr2O2ClI and Cr2O2ClBr
monolayers remain to be ferromagnetic under various small
strains (Figure 3a,b). It was also noticed that the energy
difference between ferromagnetic and antiferromagnetic states
of the Cr2O2ClI monolayer is small (−2 meV/TM) at a
compressive strain of 5% along x. We wondered if the ground
state of Cr2O2ClI monolayer could turn to be antiferromag-
netic, so larger compressive strains along x were applied on it.
Surprisingly, the ferromagnetic Cr2O2ClI monolayer turns to
be antiferromagnetic under a compressive uniaxial strain of
3925
Letter
∼7% along x, which indicates the possibility of strain-
controllable magnetism (Table S1).
The tunable band gaps of Cr2O2ClI and Cr2O2ClBr
monolayers under strains along the x (Figure 3c,d) and y
axes (Figure S3) are also presented. Here we discussed the
results from strains along the x axis as an example. Obviously,
both of them are semiconductors with band gaps of 0.70
(Cr2O2ClI) and 1.63 eV (Cr2O2ClBr) without strains,
respectively. They also show a similar trend as the band gaps
of the majority spin increase with the increase in tensile strain,
whereas the band gaps of the minority spin suggest an opposite
tendency. The band gaps of single-layer Cr2O2ClI under larger
compressive uniaxial strain (6−10%) along x were also
calculated. Interestingly, quantum-phase transitions from FM
semiconductor to AFM semiconductor (∼7% stain) and then
to AFM metal (∼8% stain) could be achieved in Cr2O2ClI
monolayer with the increase in compressive uniaxial strains
(Table S1), indicating the potential applications of these 2D
Janus crystals in ultrathin magnetic strain sensors.
To gain a further insight into the understanding of magnetic
properties, we have calculated the spin-dependent electronic
band structures and projected densities of states. As depicted
in Figure 4, the Cr2O2ClI monolayer is a ferromagnetic
semiconductor with an indirect band gap of 0.70 eV, as the
valence band maximum is between the Γ and X points,
whereas the conduction band minimum locates at the Y point.
Its conduction band minimum is dominated by the majority
spins, which are mainly contributed by the Cr-3d and I-5p
orbitals, whereas the valence band maximum is dominated by
minority spins, which predominantly contain the I-5p orbitals
(Figure 4a−c). We observed 1D-like van Hove singularities
near the Fermi energy in both the Cr2O2ClI and Cr2O2ClBr
(Figure S4a−c)) monolayers, which have also been reported in
some other 2D materials.9,47,48 Under compressive uniaxial
strains along x, quantum-phase transitions from FM semi-
conductor to AFM semiconductor (∼7% stain) or to AFM
metal (∼8% strain) could be achieved in Cr2O2ClI monolayer,
as discussed and summarized Table S1. The electronic band
structure and projected densities of states of Cr2O2ClI
monolayers under 7 and 8% compressive uniaxial strains are
also presented in Figure S5 and Figure S6, respectively. As for
this 8% strained Cr2O2ClI monolayer, there are finite
electronic states at the Fermi level, indicating its metallic
behavior, which are also primarily contributed by the I-5p and
Cr-3d orbitals.
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Figure 3. Calculated total energy difference of ferromagnetic (FM) and antiferromagnetic (AFM) states EFM‑AFM (meV/TM) of single-layer (a)
Cr2O2ClI and (b) Cr2O2ClBr under uniaxial strains (±5%) along the x and y axes. Electronic band gap Eg (eV) of majority and minority spins for
(c) Cr2O2ClI and (d) Cr2O2ClBr monolayers under uniaxial strains (±5%) along the x axis.

Figure 4. Calculated electronic band structure with (a) majority and (c) minority spins and (b) the spin-resolved projected densities of states of
Cr2O2ClI monolayers without strain. The dashed lines at 0 eV denote the Fermi energy.

3926 DOI: 10.1021/acs.jpclett.9b01543

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The Journal of Physical Chemistry Letters
In summary, we have theoretically predicted two new Janus
Cr2O2XY monolayers with Pma2 structure that display
extraordinary magnetic and electronic properties via inducing
structural phase transitions and including the reversed
displacements of outer halogen anions. These Janus Cr2O2ClI
and Cr2O2ClBr monolayers show great dynamical stability and
feasibility to be synthesized experimentally by replacing the top
layer atoms. Remarkably, Janus Cr2O2XY monolayers are
intrinsically ferromagnetic semiconductors with indirect band
gaps of 0.70 (Cr2O2ClI) and 1.63 eV (Cr2O2ClBr), which can
be tuned easily by strain engineering. Most interestingly, novel
quantum-phase transitions from FM semiconductor to AFM
semiconductor (∼7% stain) and to AFM metal (∼8% strain)
could be achieved in the Cr2O2ClI monolayer under
compressive uniaxial strains, which are primarily contributed
by the I-5p and Cr-3d orbitals, as indicated by the electronic
structures. These unique properties render Janus Cr2O2XY
monolayers promising candidates for future nanoscale
electronic, magnetic, and spintronic applications. We believe
our work will stimulate further investigation of 2D Janus
magnetic materials as well as relevant electronic and spintronic
devices.
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jp-
clett.9b01543.
Tables and figures for 2D Cr2O2XY Janus crystals:
phonon dispersions, electronic structures, and magnetic
properties as well as optimized structures (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*N.M.: E-mail: nhmiao@buaa.edu.cn; nhmiao@gmail.com.
*Z.S.: E-mail: zmsun@buaa.edu.cn.
ORCID
Naihua Miao: 0000-0002-5383-9008
Zhimei Sun: 0000-0002-4438-5032
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We greatly acknowledge the support from the National Key
Research and Development Program of China
(2017YFB0701700) and the National Natural Science
Foundation of China (61874146 and 21803005).
■
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3928 DOI: 10.1021/acs.jpclett.9b01543

J. Phys. Chem. Lett. 2019, 10, 3922−3928