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Two-dimensional honeycomb-kagome V2X3

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(X = O, S, Se) with half-metallicity, high Curie

Cite this: J. Mater. Chem. C,
2024, 12, 14172 temperature, and large magnetic anisotropic
energy†
Sai Ma,‡ Xiangyan Bo, ‡ Lei Fu, Xiaoyu Liu, Suen Wang, Mengxian Lan,
Shasha Li, Tian Huang, * Feng Li * and Yong Pu*

Searching for intrinsic two-dimensional (2D) half-metal materials is a significant challenge for advanced
spintronic applications. Here, we predict a series of stable 2D V2X3 (X = O, S, Se) monolayers with
honeycomb-kagome (HK) structure with first-principles calculations, which exhibit intrinsic ferromagnetic
(FM) ordering and considerably large magnetic anisotropy energy (MAE) of 130, 100, and 110 meV per V
atom for V2O3, V2S3, and V2Se3 monolayers, respectively. The first-principles linear response (FPLR)
approach combined with Monte Carlo simulations suggests high Curie temperatures (TC) of 459, 557, and
496 K for V2X3 (X = O, S, Se) monolayers, respectively. In addition, the 2D V2X3 (X = O, S, Se) monolayers
expose highly desired half-metallicity wide band gaps in the spin-down channel of over 1 eV. Moreover,
Received 1st April 2024, we investigate the effects on their MAE and magnetic ground state changes under the biaxial strain.
Accepted 8th August 2024 Remarkably, all these monolayers are ferromagnetic in the ground state but undergo antiferromagnetic
DOI: 10.1039/d4tc01315h (AFM) phase transition under the influence of 2.8%, 2.3%, and 3.4% compressive strain for V2X3
(X = O, S, Se) monolayers, respectively. Overall, our prediction of such intrinsic 2D FM half-metal V2X3
rsc.li/materials-c (X = O, S, Se) monolayers may serve as a good candidate for high-performance spintronic nanodevices.

Introduction materials with intrinsic ferromagnetism at room temperature

are still rare. Half-metals are a class of magnetic materials with
The exploration of two-dimensional (2D) magnetic materials unique electronic structures, with one spin channel being
has been a hot topic in order to advance the development of metallic while the other being semiconducting or insulating.
spintronics. Two-dimensional materials are regarded as pro- Therefore, they could provide 100% spin-polarized current,
mising candidates for the development of high performance which makes them attractive for pure spin generation, injec-
spintronic devices due to their nanoscale thickness and ease of tion, and transport.9 Besides, two-dimensional topological
stacking. At the nanoscale, two-dimensional materials exhibit magnets have sparked extensive attention because of their
many novel characteristics, such as magnetoelectric effects,1,2 intriguing properties,10 such as XMnY (X = Sr and Ba, Y = Sn
valley spintronics,3 and ferroelectric effects.4 In addition, two- and Pb),11 2D honeycomb ferromagnets 2H-RuCl2 and Janus
dimensional magnetic materials possess ultra-high electrical VSSe monolayers.12
conductivity5 and magnetic permeability,6 which makes them Tuning the magnetic order is an important concern for the
have potential applications for the purposes of data storage and applications of two-dimensional materials in spintronic devices,
transmission. Previous studies have shown that long-range such as magnetic memories and sensors.13–15 Strain engineer-
ferromagnetic ordering was observed in 2D materials CrI37 ing has been widely used to adjust the electronic structure and
and Cr2Ge2Te6.8 However, these 2D magnetic semiconductors magnetic properties of 2D materials, because of the flexibility
have rather low Curie temperatures (TC) (45 K for CrI3 mono- and ease of ductility of two-dimensional materials.16–18 For
layer and 30 K for Cr2Ge2Te6 bilayer); two-dimensional example, the MnPSe3 monolayer can cause a magnetic phase
transition from AFM to FM under biaxial tensile strain.19 By
School of Science & New Energy Technology Engineering Laboratory of Jiangsu using tensile strain, the magnetic phase of the MoN2 monolayer
Province, Nanjing University of Posts and Telecommunications (NJUPT), Nanjing
can be adjusted from FM to AFM.20
210046, China. E-mail: [email protected], [email protected]
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/
In this work, we systematically studied the geometric, mag-
10.1039/d4tc01315h netic, and electronic properties of the V2X3 (X = O, S, Se)
‡ Sai Ma and Xiangyan Bo contributed equally to this manuscript. monolayers with the honeycomb-kagome (HK) lattice structure

14172 | J. Mater. Chem. C, 2024, 12, 14172–14179 This journal is © The Royal Society of Chemistry 2024
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Paper Journal of Materials Chemistry C

based on first-principles calculations. Our calculations show that within 5 ps by the Nosé–Hoover method.27 The VASPKIT28 tool and
the V2X3 (X = O, S, Se) monolayers are stable and intrinsically the VESTA29 software were also used for the pre-processing and
ferromagnetic, with large MAEs of 130, 100, and 110 meV per V post-processing of the calculations.
atom, respectively. Using the first principles linear response We use the first-principles linear response (FPLR) method to
(FPLR) approach, we calculated the magnetic exchange con- calculate the exchange interaction constants J, which are imple-
stants. Based on the obtained magnetic exchange constants, mented in the WIENJ30 code, as an interface to WIEN2K.31 The
the Curie temperatures are estimated by Monte Carlo simula- linear response method and the magnetic force theorem32 serve
tions. The magnetic transition temperatures of the V2X3 (X = O, S, as the foundation for the FPLR approach.33 The second variation
Se) monolayers are predicted to be 459, 557, and 496 K, respec- of total energy, with a tiny departure of the magnetic moment, is
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tively, which are higher than room temperature. Besides, these calculated to get the exchange interaction constant. The precise
materials are demonstrated to be half-metals with large band computation of long-range exchange interactions is made simple
gaps. Furthermore, we found that the V2X3 (X = O, S, Se) by this method, which computes the lattice Fourier transform J(q)
monolayers could be changed from the FM phase to the AFM of the exchange interaction J(Rl). This method has recently been
phase by applying biaxial compressive strain. Our study suggests applied with success to assess magnetic interactions in a range
that the V2X3 (X = O, S, Se) monolayers could be promising 2D of materials.34–43 Utilizing the computed magnetic exchange
materials for spintronic devices. interactions as a foundation, the Curie temperatures TC were
determined through the implementation of Monte Carlo simula-
tion and the Metropolis algorithm, employing the MCSOLVER
Methods code.44
All the calculations of the V2X3 (X = O, S, Se) monolayers are
obtained from the first-principles calculations on the basis of Results and discussion
density functional theory (DFT)21 as implemented in the Vienna
ab initio simulation package (VASP).22 The projector-augmented 1. Structure and stability
wave (PAW)23 potentials were used along with the generalized The crystal structures of the V2X3 (X = O, S, Se) monolayers are
gradient approximation (GGA). The generalized gradient approxi- shown in Fig. 1 with a planar HK lattice, which belongs to the P6/
mation with the Perdew–Burke–Ernzerhof (PBE)24 exchange–corre- mmm space group. The optimized lattice constants are 6.19, 7.57,
lation functional was used. To consider the strong correlation and 8.00 Å for V2O3, V2S3, and V2Se3, respectively. The bond angle
effects of the transition metal V element, the Hubbard U value of of the X–V–X bond is 1201, and the V–X bond lengths of each
the V atom was set to 3.0 eV based on the previous study.25 Unless monolayer are summarized in Table 1. To verify the dynamic
otherwise stated, the electronic structure and magnetic properties stability of the V2X3 (X = O, S, Se) monolayers, the phonon
are calculated using the structure relaxed by the PBE+U method, dispersion spectra were evaluated by the finite displacement
and the energy is calculated using the DFT+U generalization method. As shown in Fig. 1(c)–(e), the absence of imaginary
function. The plane-wave cutoff energy is set at 500 eV, and the phonon modes confirms their kinetic stability. The elastic con-
vacuum layer of 15 Å was used to avoid interlayer interactions. The stants of the V2X3 (X = O, S, Se) monolayers were calculated to
convergence criteria for electronic self-consistence and the ionic check their mechanical stability. By virtue of symmetry, there are
residual forces are 106 eV and 103 eV Å1, respectively. The only two independent stiffness constants, C11 and C22, and we
Monkhorst–Pack scheme is chosen to sample the Brillouin zone disregard the contribution of out-of-plane bending to the elastic
integration with 11  11  1 G-centered K-points. The phonon energy density, whereby the vertical weight of the stiffness con-
calculations were performed using a 2  2  1 supercell in the stants becomes negligible. The elastic constants C11 and C12 are
PHONOPY codes.26 To assess the thermal stability, ab initio also summarized in Table 1. According to the Born–Huang
molecular dynamics (AIMD) simulation was performed at 300 K criterion45 for 2D hexagonal systems, i.e., C11 4 0 and

Fig. 1 V2X3 (X = O, S, Se) monolayers and their phonon dispersion. (a) Top and (b) side views of the structures. V and X (X = O, S, Se) atoms are
represented by purple and green spheres. The definitions of the magnetic exchange interactions J1, J2, J3, and J4 are indicated. Phonon band structures
for (c) V2O3, (d) V2S3, and (e) V2Te3 monolayers, confirming their dynamic stability.

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Table 1 The optimized lattice constants (L, Å), the V–X bond lengths (d, 2. Magnetic properties
Å), the stiffness constants (C, N m1), the Young’s modulus (E), and the
Poisson’s ratio (u) of V2X3 (X = O, S, Se) monolayers To determine the magnetic ground state of the V2X3 (X = O, S,
Se) monolayers, a 2  2  1 supercell is adopted, in which five
L d C11 C12 E u collinear magnetic configurations can be defined: FM, AFM-ZZ,
V2O3 6.19 1.79 69.277 53.122 28.543 0.767 AFM-N-ST, AFM-ST, and AFM-N, as shown in Fig. 2. The energy
V2S3 7.57 2.18 37.074 30.493 11.995 0.822 differences of these magnetic configurations are listed in
V2Se3 8.00 2.31 32.102 26.976 9.435 0.840
Table 2. The energy of the four AFM states is higher than the
energy of the FM state, indicating that the V2X3 (X = O, S, Se)
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monolayers are in the FM ground state.

C11 4 |C12|, the mechanical stability of the V2X3 (X = O, S, Se) Next, we investigated one of the critical factors in the
monolayers is confirmed. Based on E = (C112  C122)/C11, the stability of long-range FM ordering in 2D systems, namely
calculated Young’s modulus of V2X3 are 28.543, 11.995, and magnetic anisotropy energy (MAE).46 MAE is defined as the
9.435 N m1 for X = O, S, and Se, respectively. The softer materials energy requisite to rotate the magnetization from the easy axis
of V2X3 (X = O, S, Se) exhibit commendable ductility, rendering to the hard axis of a ferromagnetic material. Usually, MAE
them amenable to strain engineering. mainly includes two parts: (1) magnetocrystalline anisotropy
Additionally, the formation energy is also estimated to (MCA) originated from the SOC and (2) magnetic shape aniso-
investigate the energetic stability of the V2X3 (X = O, S, Se) tropy (MSA) induced by the magnetic dipole–dipole (D–D)
monolayers, which is defined as Ef = (EV2O3  2EV  3/2mO2) for interaction:47,48
V2O3 and Ef = (EV2X3  2EV  3EX) for V2S3 and V2Se3, where EV2O3
 
and EV2X3 are the total energy of V2X3 (X = O, S, Se) monolayers, 1 m0 X 1 ~ ~ 3~ 
~j  ~
EDD ¼ M i  M j  M i  ~
r ij M r ij (1)
EV and EX are the energies of the V and X (X = S, Se) atoms, and 2 4p iaj rij3 rij2
mO2 is the chemical potential of oxygen gas, respectively. The Ef
- -
was estimated as 2.53, 0.67, and 0.19 eV per atom for V2O3, where m0 is the vacuum permeability, Mi and Mj are the local
-
V2S3, and V2Se3, respectively. The negative formation energies magnetic moments of the V atom, and rij is the vector of V
suggest that the monolayers are energetically favorable. To atoms on i and j sites. MSA depends on the magnetic moment
check whether the V2X3 (X = O, S, Se) becomes buckled, we on V atoms and the distance between Vi and Vj. In most
construct the buckled V2X3 (X = O, S, Se) lattice. The calculated materials, the MSA is small compared with the MCA.49 In our
energy differences between different buckled and planar struc- calculations, the MSA are 10.09, 8.40, and 12.67 meV for V2O3,
tures are shown in Fig. S1 (ESI†). The energies of V2X3 (X = O, S, V2S3, and V2Se3, respectively, which are smaller than the MCA
Se) increase monotonically with the buckled height from 0 to (260 meV for V2O3 monolayer, 200 meV for V2S3 monolayer, and
1.8 Å, which suggests that the stable structure is planar rather 220 meV for V2Se3 monolayer). Thus, the calculated MAE is
than buckled. Furthermore, AIMD simulation was conducted equal to the MCA. We performed spin–orbit coupling (SOC)
by using 4  4  1 supercells of the V2X3 (X = O, S, Se) calculations on the V2X3 (X = O, S, Se) monolayers to obtain the
monolayers at 300 K for 5 ps to evaluate the thermal stability. energy along the (001) and (100) directions. The MAE of the
As shown in Fig. S2 (ESI†), the corresponding fluctuations of V2X3 (X = O, S, Se) monolayers along the (001) direction is lower
the total energies are oscillating in a narrow range, which in energy than that along the (100) directions by 130, 100, and
indicates the thermal stability of the V2X3 (X = O, S, Se) 110 meV per V atom, respectively, which are similar to the MnP
monolayers. (166 meV per Mn atom) monolayer.50 As with CrI3, the easy axes

Fig. 2 Top view of five possible magnetic configurations considered for V2X3 (X = O, S, Se) monolayers, including (a) one FM state and (b–e) four AFM
states. The spin orientations are depicted by red (up) and blue (down) arrows on the V atoms.

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Table 2 The relative energies (in eV) of different magnetic configurations we use the FPLR method to calculate the accurate magnetic
for V2X3 (X = O, S, Se) monolayers, where the lowest ferromagnetic (FM) exchange constants of V2X3 (X = O, S, Se) monolayers. Four
state is set to zero
kinds of magnetic exchange interactions are considered, as
V 2 O3 V2S3 V2Se3 shown in Fig. 1(a), and the results are shown in Table 3. Among
FM 0 0 0 them, J1 is much larger than the others, which determines the
AFM-ZZ 0.16 0.22 0.22 FM order in the V2X3 (X = O, S, Se) monolayers.
AFM-N-ST 0.21 0.28 0.35 Based on the calculated magnetic exchange constants, we
AFM-ST 0.18 0.40 0.42
AFM-N 0.34 0.56 0.58 use the 2D anisotropic Heisenberg model and perform Monte
Carlo simulations to estimate the Curie temperatures for V2X3
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(X = O, S, Se) monolayers
of the V2X3 (X = O, S, Se) monolayers are along the out-of-plane. X X 2
The result may be attributed to the robust SOC effect induced H¼ Jij Si  Sj þ A Siz
ioj i
by the strong electronic correlations among the 3d electrons in
the V3+ ions. The observed large MAEs will be sufficient to
where Jij is the exchange interaction parameters explained in
prevent the heat fluctuation from disturbing the ferromagnetic
Fig. 1(a), A is the single-ion magnetic anisotropy energy parameter,
ordering at certain temperatures.
and Si and Sj are the spin operators on i and j sites. As illustrated in
In general, the mechanism of the MAE correlates with the
Fig. 3, the TC of the V2X3 (X = O, S, Se) monolayers is obtained to be
SOC interaction between the occupied and unoccupied states of
459, 557, and 496 K, respectively, which is much higher than room
the orbitals around the Fermi level.51,52 Based on the second-
temperature. The high magnetic transition temperatures indicate
order perturbation theory, the MAE comes from SOC and is
that the V2X3 (X = O, S, Se) monolayers have potential applications
expressed as53
for room-temperature spintronic devices.
DE ## ¼ E ## ðxÞ  E ## ðzÞ
    3. Electronic structure
X  o# jLz ju# 2  o# jLx ju# 2 (2)
2 Now we further investigate the electronic properties of V2X3 (X = O,
¼x
o# ;u# Eu#  Eo# S, Se) monolayers. The calculated band structures of V2X3 (X = O, S,
Se) monolayers with FM states using the PBE+U method are
DE "# ¼ E "# ðxÞ  E "# ðzÞ displayed in Fig. 4(a)–(c). They all exhibit typical half-metallic
    characteristics, where the spin-up bands cross the Fermi levels,
X  o" jLz ju# 2  o" jLx ju# 2 (3) demonstrating metallic behaviors, while band gaps appear in the
¼ x2
o" ;u# Eu"  Eo# spin-down bands, resulting in 100% spin polarization. In the V2X3
(X = O, S, Se) monolayers, the band gaps of the spin-down channels
where x is the SOC constant, Lz and Lx are angular momentum from the G point to the K point are 4.85, 1.89, and 1.76 eV,
operators. o and u are the energy levels of the occupied states and respectively. The large spin-down band gaps help to prevent spin–
the unoccupied states, whose energy is Eo and Eu, respectively. k flip transitions due to thermal excitation, thus ensuring the half-
and m are the spin-minority states and spin-majority states, metallicity of V2X3 (X = O, S, Se) monolayers is preserved. The
respectively. Eqn (2) is the spin-conservation term; eqn (3) is electronic band structures show two features: a Dirac cone at the K
the spin–flip term. According to the expression, the MAE is points and the existence of two flat bands at about 1 eV. Besides,
determined by the spin-orbital matrix element differences as well the total density of states (TDOS) and the projected density of states
as the energy interval between occupied and unoccupied states. (PDOS) of the V2X3 (X = O, S, Se) monolayers were drawn in
The relative contributions of the nonzero Lz and Lx matrix Fig. 4(d)–(f). It can be seen that the total density of states around
  pffiffiffi
elements are hdxz|Lz|dyzi = 1 and dz2 jLx jdyz ¼ 3.54 For the the Fermi level is contributed by the 3d orbitals of the V atoms and
spin-conservation term, the MAE contributed by dxz and dyz the 2p orbitals of the O, S, and Se atoms. The PDOS can help us
orbitals is positive, while the MAE contributed by dz2 and dyz further understand the origin of strong ferromagnetic coupling in
orbitals is negative. For the spin–flip term, the MAE contributed the V2X3 (X = O, S, Se) monolayers.
by dxz and dyz orbitals is negative, while the MAE contributed by Because of the threefold symmetry of the V site, the V 3dx2–y2
dz2 and dyz orbitals is positive. and V 3dxy states are doubly degenerate, the V 3dxz and V 3dyz
As shown in Fig. S3 (ESI†), the projected density of states
(PDOS) of the dxz, dyz, and dz2 orbitals of the V atoms is Table 3 Calculated magnetic exchange constants (in meV) for V2X3 (X =
calculated. It can be observed that the dxz and dyz orbitals of O, S, Se) monolayers. J1, J2, J3, and J4 correspond to the first, second, third,
V are degenerate. By comparing the energy differences, we find and fourth nearest neighbor V–V couplings, as defined in Fig. 1(a)
that positive contributions are larger than negative contribu-
NN V2O3 V2S3 V2Se3
tions, resulting in the easy axes of the V2X3 (X = O, S, Se)
monolayers being along the out-of-plane direction. J1 3 26.5024 30.1288 26.7471
J2 6 0.3409 0.3734 0.1164
Magnetic coupling is a crucial part of understanding the J3 3 0.0500 0.1012 0.0029
magnetic properties of the V2X3 (X = O, S, Se) monolayers. Here, J4 6 0.0791 0.1010 0.0852

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(dx2–y2, dxy) orbitals hold the highest energy. The high-spin V3+
ion with two valence electrons results in a magnetic moment of
2mB per V atom. One electron occupies the spin-up dz2 orbital,
and the other half occupies the spin-up (dxz, dyz) orbital, which
leads to the strong ferromagnetism in the V2X3 (X = O, S, Se)
monolayers.
As shown in Fig. 5(a), the spin-up (dxz, dyz) orbital of a V3+
ion can interact with the neighboring V3+ ion through the
shared O atom. This interaction results in a doubly degenerate
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high-lying antibonding state and another doubly degenerate low-

lying bonding state. When the spin directions of the two V ions are
parallel to each other, the two electrons occupy the doubly degen-
erate bonding state, resulting in an energy lowering [DEFM N t,
where t is the effective hopping between the (dxz, dyz) orbitals of the
two V ions]. This is similar to the widely recognized double-
exchange mechanism in ferromagnetism. When the spin directions
of the two V ions are antiparallel to each other, there is a usual
Fig. 3 Monte Carlo simulation results for V2X3 (X = O, S, Se) monolayers. energy lowering [DEAFM N t2/U]. Since t is far smaller than U, DEFM
The temperature dependence of the magnetic moment is represented by
is much larger than DEAFM. This situation can be further confirmed
green, red, and blue, respectively.
by the first principles calculations, as shown in Fig. 5(b), the energy
difference between the Néel AFM state and the FM state increases
with the Hubbard U value. We have also noted that there are many
are also doubly degenerate; and the V 3dz2 orbital is nonde-
sharp peaks in the density of states. It has been demonstrated that
generate. The V3+ ions exhibit a high spin configuration; the
in certain 2D materials, sharp van Hove singularities lead to
energies of the 3d orbitals decrease in the order of (dx2–y2, dxy),
magnetic instabilities and induce magnetic phase transitions.55–57
(dxz, dyz), dz2. The orbital interactions between O/S/Se 2p
orbitals and V 3d orbitals lead to the energy order and hint at
the bonding characteristics. The interaction between the V dz2 4. Biaxial strain
orbital and the O/S/Se p orbitals can be ignored since the V dz2 The potential magnetic phase transition resulting from van
orbital has the lowest energy. The V (dx2–y2, dxy) orbitals form s Hove singularities is under consideration, so we have carried
bonds with O (px, py) orbitals, while the V (dxz, dyz) orbitals form out a biaxial strain study on the V2X3 (X = O, S, Se) monolayers.
p bonds with O pz orbitals. The strength of the s bonds The atomic positions were optimized for all biaxial strain
is higher than that of the p bonds, which explains why the configurations, ranging from 6% to +6%. From Fig. 6(a)–(c), it

Fig. 4 Electronic structure of V2X3 (X = O, S, Se) monolayers calculated using the PBE+U method with U = 3.0 eV. (a)–(c) Band structures with spin-up
and spin-down channels are shown in red and blue, respectively. The Fermi level is set to zero. (d)–(f) Total DOS (TDOS) and projected DOS (PDOS) onto
the 3d orbitals of V atoms. Positive and negative PDOS represent the spin-up and spin-down channels.

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Fig. 5 (a) Plot of the magnetic exchange mechanism for the FM state. (b) The energy difference between the Néel AFM state and the FM state of the
V2O3 monolayer as a function of the Hubbard U value.

Fig. 6 (a)–(c) MAE of the V2X3 (X = O, S, Se) monolayers as a function of the strain. The red area indicates that the material is in the AFM state and the
white area indicates that the material is in the FM state. (d)–(f) The energy difference between AFM and FM as a function of the strain. The phase change
points were 2.8%, 2.3% and 3.4% respectively.

can be observed that the MAE of V2O3 decreases under the of the V2X3 (X = O, S, Se) monolayers with HK lattice structure
influence of tensile strain, whereas it exhibits a continuous based on the first-principle calculations. Our calculations
increase in response to compressive strain. Conversely, in the case reveal that the V2X3 (X = O, S, Se) monolayers are dynamically
of V2S3 and V2Se3, the MAE continues to increase as the material is stable and intrinsic ferromagnetic half-metals with sizable
stretched. This phenomenon is especially conspicuous in V2Se3, MAE. Using the first principles linear response method, we
where the MAE can augment to 83% under a 6% tensile strain. studied the magnetic interactions. Monte Carlo simulations
In Fig. 6(d)–(f), we present the energy difference (DE = EFM  based on the calculated magnetic exchange constants show
EAFM) between the two magnetic orders of V2O3, V2S3, and V2Se3 as that the Curie temperatures of the V2X3 (X = O, S, Se) mono-
a function of biaxial strain e. As e decreases (i.e., the compressive layers were higher than room temperature. Moreover, the
strain increases), the energy difference increases. When the energy magnetic phase transition from the FM phase to the AFM
difference between the FM and AFM orderings is greater than zero, phase occurs when compressive strain is applied. These find-
there is a phase transition to the AFM phase. For V2O3, V2S3, and ings indicate that the V2X3 (X = O, S, Se) monolayers could be a
V2Se3, near the compression strain of 2.8%, 2.3% and 3.4%, promising material for room-temperature spintronic devices.
DE changes from a positive value to a negative value, indicating a
magnetic phase transition from FM to AFM state.

Data availability
Conclusion
The data that support the findings of this study are available
In summary, we have theoretically investigated the geometrical with the corresponding author and can be obtained upon
structure, dynamic stability, magnetic and electronic properties reasonable request.

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Conflicts of interest Mixed topological semimetals driven by orbital complexity

in two-dimensional ferromagnets, Nat. Commun., 2019,
The authors declare that they have no known competing 10, 3179.
financial interests or personal relationships that could have 11 C. Niu, H. Wang, N. Mao, B. Huang, Y. Mokrousov and
appeared to influence the work reported in this paper. Y. Dai, Antiferromagnetic Topological Insulator with Non-
symmorphic Protection in Two Dimensions, Phys. Rev. Lett.,
Acknowledgements 2020, 124, 066401.
12 R. Li, N. Mao, X. Wu, B. Huang, Y. Dai and C. Niu, Robust
This work was supported by the National Natural Science Second-Order Topological Insulators with Giant Valley
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Foundation of China (Grant No. 12104234), Natural Science Polarization in Two-Dimensional Honeycomb Ferromag-
Foundation of Jiangsu Province (Grant No. BK20210578, nets, Nano Lett., 2023, 23, 91.
21KJD140005), and the Foundation of Nanjing University of 13 P. Barla, V. K. Joshi and S. Bhat, Spintronic devices: a
Posts and Telecommunications ‘1311 Talent Program’. The promising alternative to CMOS devices, J. Comput. Electron.,
authors gratefully acknowledge the computing time granted 2021, 20, 805.
by the Shanghai Supercomputer Center. 14 S. Jiang, J. Shan and K. F. Mak, Electric-field switching of
two-dimensional van der Waals magnets, Nat. Mater., 2018,
17, 406.
References
15 H. Ye, Y. Zhu, D. Bai, J. Zhang, X. Wu and J. Wang, Spin
1 S. Jiang, L. Li, Z. Wang, K. F. Mak and J. Shan, Controlling valve effect in VN/GaN/VN van der Waals heterostructures,
magnetism in 2D CrI3 by electrostatic doping, Nat. Nano- Phys. Rev. B, 2021, 103, 035423.
technol., 2018, 13(7), 549. 16 H. J. Conley, B. Wang, J. I. Ziegler, R. F. Haglund, S. T. Pantelides
2 P. Jiang, L. Li, Z. Liao, Y. X. Zhao and Z. Zhong, Spin Direction- and K. I. Bolotin, Bandgap Engineering of Strained Monolayer
Controlled Electronic Band Structure in Two-Dimensional Fer- and Bilayer MoS2, Nano Lett., 2013, 13(8), 3626.
romagnetic CrI3, Nano Lett., 2018, 18(6), 3844. 17 R. Peng, H. C. Xu, S. Y. Tan, H. Y. Cao, M. Xia, X. P. Shen,
3 S. Bhalla, D. T. Melnekoff, A. Aleman, V. Leshchenko, Z. C. Huang, C. H. P. Wen, Q. Song, T. Zhang, B. P. Xie,
P. Restrepo, J. Keats, K. Onel, J. R. Sawyer, D. Madduri, X. G. Gong and D. L. Feng, Tuning the band structure and
J. Richter, S. Richard, A. Chari, H. J. Cho, J. T. Dudley, superconductivity in single-layer FeSe by interface engineer-
S. Jagannath, A. Laganà and S. Parekh, Patient similarity ing, Nat. Commun., 2014, 5(1), 5044.
network of newly diagnosed multiple myeloma identifies 18 P. Zhang, X. L. Peng, T. Qian, P. Richard, X. Shi, J. Z. Ma,
patient subgroups with distinct genetic features and clinical B. B. Fu, Y. L. Guo, Z. Q. Han, S. C. Wang, L. L. Wang,
implications, Sci. Adv., 2021, 7(47), 9551. Q. K. Xue, J. P. Hu, Y. J. Sun and H. Ding, Observation of
4 S. Li and T. Birol, Suppressing the ferroelectric switching high-Tc superconductivity in rectangular FeSe/SrTiO3(110)
barrier in hybrid improper ferroelectrics, npj Comput. monolayers, Phys. Rev. B, 2016, 94, 104510.
Mater., 2020, 6(1), 168. 19 Q. Pei, X. C. Wang, J. J. Zou and W. B. Mi, Tunable electronic
5 W. Sun, A. Du, G. Gao, J. Shen and G. Wu, Graphene- structure and magnetic coupling in strained two-dimensional
templated carbon aerogels combining with ultra-high elec- semiconductor MnPSe3, Front. Phys., 2018, 13, 137105.
trical conductivity and ultra-low thermal conductivity, 20 Y. Wang, S. S. Wang, Y. Lu, J. Jiang and S. A. Yang, Strain-
Microporous Mesoporous Mater., 2017, 253, 71. Induced Isostructural and Magnetic Phase Transitions in
6 A. Radkovskaya, P. Petrov, S. Kiriushechkina, A. Satskiy, Monolayer MoN, Nano Lett., 2016, 16, 4576.
M. Ivanyukovich, A. Vakulenko, V. Prudnikov, O. Kotelnikova, 21 J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson,
A. Korolev and P. Zakharov, Magnetic metamaterials: Coupling M. R. Pederson, D. J. Singh and C. Fiolhais, Atoms, mole-
and permeability, J. Magn. Magn. Mater., 2018, 459, 187. cules, solids, and surfaces: Applications of the generalized
7 B. Huang, G. Clark, E. Navarro-Moratalla, D. R. Klein, gradient approximation for exchange and correlation, Phys.
R. Cheng, K. L. Seyler, D. Zhong, E. Schmidgall, Rev. B: Condens. Matter Mater. Phys., 1992, 46, 6671.
M. A. McGuire, D. H. Cobden, W. Yao, D. Xiao, P. Jarillo- 22 G. Kresse and J. Furthmuller, Efficient iterative schemes for ab
Herrero and X. Xu, Electrical control of 2D magnetism in initio total-energy calculations using a plane-wave basis set, Phys.
bilayer CrI3, Nature, 2017, 546, 270. Rev. B: Condens. Matter Mater. Phys., 1996, 54, 11169.
8 C. Gong, L. Li, Z. Li, H. Ji, A. Stern, Y. Xia, T. Cao, W. Bao, 23 P. E. Blochl, Projector augmented-wave method, Phys. Rev.
C. Wang, Y. Wang, Z. Q. Qiu, R. J. Cava, S. G. Louie, J. Xia B: Condens. Matter Mater. Phys., 1994, 50, 17953.
and X. Zhang, Discovery of intrinsic ferromagnetism in two- 24 J. P. Perdew, K. Burke and M. Ernzerhof, Generalized Gradient
dimensional van der Waals crystals, Nature, 2017, 546, 265. Approximation Made Simple, Phys. Rev. Lett., 1996, 77, 3865.
9 X. Li and J. Yang, Low-dimensional half-metallic materials: 25 D. Grieger and M. Fabrizio, Low-temperature magnetic ordering
theoretical simulations and design, Comput. Mol. Sci., 2017, and structural distortions in vanadium sesquioxide V2O3, Phys.
7, e1314. Rev. B: Condens. Matter Mater. Phys., 2015, 92, 075121.
10 C. Niu, J. P. Hanke, P. M. Buhl, H. Zhang, L. Plucinski, 26 A. Togo and I. Tanaka, First principles phonon calculations
D. Wortmann, S. Blügel, G. Bihlmayer and Y. Mokrousov, in materials science, Scr. Mater., 2015, 108, 1.

14178 | J. Mater. Chem. C, 2024, 12, 14172–14179 This journal is © The Royal Society of Chemistry 2024
 View Article Online

Paper Journal of Materials Chemistry C

27 G. J. Martyna, M. L. Klein and M. Tuckerman, Nosé-Hoover 43 X. Bo, F. Li, X. Yin, Y. Chen, X. Wan and Y. Pu, Magnetic
Chains: The Canonical Ensemble Via Continuous Dynamics, structure and exchange interactions of the van der Waals
J. Chem. Phys., 1992, 97, 2635. CrPS4 monolayer under strain: A first-principles study, Phys.
28 V. Wang, N. Xu, J. C. Liu, G. Tang and W. T. Geng, VASPKIT: Rev. B, 2023, 108, 024405.
A user-friendly interface facilitating high-throughput com- 44 L. Liu, X. Ren, J. Xie, B. Cheng, W. Liu, T. An, H. Qin and
puting and analysis using VASP code, Comput. Phys. Com- J. Hu, Magnetic switches via electric field in BN nanorib-
mun., 2021, 267, 1–33. bons, Appl. Surf. Sci., 2019, 480, 300.
29 K. Momma and F. Izumi, VESTA 3 for three-dimensional 45 M. Born and K. Huang, Dynamic Theory of Crystal Lattice,
visualization of crystal, volumetric and morphology data, Clarendon, Oxford (1954).
Published on 12 August 2024. Downloaded by NANJING UNIVERSITY on 12/3/2024 9:35:33 AM.

J. Appl. Crystallogr., 2011, 44, 1272. 46 N. D. Mermin and H. Wagner, Absence of Ferromagnetism
30 D. Wang, X. Bo, F. Tang and X. Wan, First-principles study or Antiferromagnetism in One- or Two-Dimensional Isotro-
of spin-orbit coupling contribution to anisotropic magnetic pic Heisenberg Model, Phys. Rev. Lett., 1966, 17(22), 1133.
interaction, Phys. Rev. B, 2023, 108, 085140. 47 J. C. Tung and G. Y. Guo, ab initio, Phys. Rev. B: Condens.
31 P. Blaha, K. Schwarz, G. K. Madsen, D. Kvasnicka and Matter Mater. Phys. 76, 094413 (2007).
J. Luitz, Vienna WIEN2k, An Augmented Plane Wave+ Local 48 S. Ji, Y. Wang, R. Yao, C. Quan, J. Yang and X. Li,
Orbitals Program for Calculating Crystal Properties, Tech- Dimension-dependent magnetic anisotropy for tunable
nische Universität Wien, Vienna, 2001. anomalous Hall effect in transition metal dichalcogenides,
32 A. I. Liechtenstein, M. I. Katsnelson, V. P. Antropov and Phys. Rev. B, 2023, 107, 035438.
V. A. J. Gubanov, Magn, Local spin density functional approach 49 R. B. Griffiths, Free energy of interacting magnetic dipoles,
to the theory of exchange interactions in ferromagnetic metals Phys. Rev., 1968, 176, 655.
and alloys, J. Magn. Magn. Mater., 1987, 67, 65. 50 B. Wang, Y. Zhang, L. Ma, Q. Wu, Y. Guo, X. Zhang and
33 X. Wan, Q. Yin and S. Y. Savrasov, Calculation of Magnetic J. Wang, MnX (X = P, As) monolayers: a new type of two-
Exchange Interactions in Mott-Hubbard Systems, Phys. Rev. dimensional intrinsic room temperature ferromagnetic
Lett., 2006, 97, 266403. half-metallic material with large magnetic anisotropy, Nano-
34 V. V. Mazurenko and V. I. Anisimov, Weak ferromagnetism scale, 2019, 11(10), 4204.
in antiferromagnets: a-Fe2O3 and La2CuO4, Phys. Rev. B: 51 J. Li, Q. Yao, L. Wu, Z. Hu, B. Gao, X. Wan and Q. Liu,
Condens. Matter Mater. Phys., 2005, 71, 184434. Designing light-element materials with large effective spin-
35 X. Wan, T. A. Maier and S. Y. Savrasov, Calculated magnetic orbit coupling, Nat. Commun., 2022, 13, 919.
exchange interactions in high-temperature superconductors, 52 Q. Yao, Y. Xue, B. Zhao, Y. Zhu, Z. Li and Z. Yang,
Phys. Rev. B: Condens. Matter Mater. Phys., 2009, 79, 155114. Orbital-Selectivity-Induced Robust Quantum Anomalous
36 M. I. Katsnelson, Y. O. Kvashnin, V. V. Mazurenko and Hall Effect in Hund’s Metals MgFeP, Nano Lett., 2024,
A. I. Lichtenstein, Correlated band theory of spin and orbital 24, 1563.
contributions to Dzyaloshinskii-Moriya interactions, Phys. 53 S. Yan, W. Qiao, D. Jin, X. Xu, W. Mi and D. Wang, Role of
Rev. B: Condens. Matter Mater. Phys., 2010, 82, 100403(R). exchange splitting and ligand-field splitting in tuning the
37 X. Wan, J. Dong and S. Y. Savrasov, Mechanism of magnetic magnetic anisotropy of an individual iridium atom on TaS2
exchange interactions in europium monochalcogenides, substrate, Phys. Rev. B, 2021, 103, 224432.
Phys. Rev. B: Condens. Matter Mater. Phys., 2011, 83, 205201. 54 D. Wang, R. Wu and A. J. Freeman, First-principles theory of
38 D. Wang, X. Bo, F. Tang and X. Wan, Calculated magnetic surface magnetocrystalline anisotropy and the diatomic-
exchange interactions in the Dirac magnon material pair mode, Phys. Rev. B: Condens. Matter Mater. Phys.,
Cu3TeO6, Phys. Rev. B, 2019, 99, 035160. 1993, 47, 14932.
39 X. Bo, D. Wang, B. Wan and X. G. Wan, Calculated magnetic 55 M. U. Farooq, A. Hashmi and J. Hong, Manipulation of
exchange interactions in the quantum spin chain materials Magnetic State in Armchair Black Phosphorene Nanoribbon by
K2CuSO4Cl2 and K2CuSO4Br2, Phys. Rev. B, 2020, 101, 024416. Charge Doping, ACS Appl. Mater. Interfaces, 2015, 7(26), 14423.
40 X. Bo, D. Wang and X. Wan, Calculated magnetic exchange 56 T. Cao, Z. Li and S. G. Louie, Tunable Magnetism and Half-
interactions in brownmillerite Ca2Fe2O5, Phys. Lett. A, 2021, Metallicity in Hole-Doped Monolayer GaSe, Phys. Rev. Lett.,
394, 127202. 2015, 114(23), 236602.
41 Z. X. Shen, X. Bo, K. Cao, X. Wan and L. He, Magnetic 57 G. R. Bhimanapati, Z. Lin, V. Meunier, Y. Jung, J. Cha,
ground state and electron-doping tuning of Curie tempera- S. Das, D. Xiao, Y. Son, M. S. Strano, V. R. Cooper, L. Liang,
ture in Fe3GeTe2: First-principles studies, Phys. Rev. B, 2021, S. G. Louie, E. Ringe, W. Zhou, S. S. Kim, R. R. Naik, B. G.
103, 085102. Sumpter, H. Terrones, F. Xia, Y. Wang, J. Zhu, D. Akinwande,
42 X. Bo, F. Li, X. Xu, X. Wan and Y. Pu, Calculated magnetic N. Alem, J. A. Schuller, R. E. Schaak, M. Terrones and
exchange interactions in the van der Waals layered magnet J. A. Robinson, Recent Advances in Two-Dimensional Mate-
CrSBr, New J. Phys., 2023, 25, 013026. rials beyond Graphene, ACS Nano, 2015, 9(12), 11509.

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