PHYSICAL REVIEW B 101, 024411 (2020)

Electronic and magnetic properties of van der Waals ferromagnetic semiconductor VI3
*
Yun-Peng Wang and Meng-Qiu Long
School of Physics and Electronics, Hunan Key Laboratory for Super-micro Structure and Ultrafast Process,
Central South University, 932 South Lushan Road, Changsha 410083, People’s Republic of China

(Received 25 September 2019; revised manuscript received 27 November 2019; published 15 January 2020)

Magnetic van der Waals materials with intrinsic magnetic properties provide the ideal platform for exploring
magnetism in the low-dimensional limit. In this work, we investigate the electronic and magnetic properties of
the VI3 material, a new member of the ferromagnetic van der Waals materials. First-principles results confirm
the Mott-insulator state as its electronic ground state. The half-metallic state as reported in the literature is a
metastable state, with a total energy 0.2–0.3 eV per VI3 higher than the Mott-insulator state. Magnetocrystalline
anisotropy calculations confirm an out-of-plane magnetic easy axis of the VI3 monolayer. We predict the
interlayer exchange coupling of the VI3 bilayer to be determined by the interlayer stacking order, ferromagnetic
at the most stable and antiferromagnetic at the metastable stacking orders, respectively, reminiscent of the CrI3
material.

DOI: 10.1103/PhysRevB.101.024411

I. INTRODUCTION magnetic moment scatters between 1.3μB and 2.5μB per V

ion. The magnetic easy axis is along the out-of-plane direction
Two-dimensional van der Waals (2D vdW) materials with
[5–7]. The structural, electronic, and magnetic properties of
ferromagnetic order have gained extensive attention recently
VI3 are similar to those of CrI3 . A systematic theoretical
[1]. Low-temperature ferromagnetism was discovered in var-
investigation of the VI3 material is still lacking.
ious 2D vdW materials such as few-layer CrGeTe3 , CrI3 , and
In this work, we present a systematic study on the elec-
Fe3 GeTe2 [2–4]. VI3 is a new member of the ferromagnetic
tronic and magnetic properties of the VI3 material using a
2D vdW material family [5–7]. In the VI3 material, each V
first-principles approach. We found that the electronic ground
ion resides at the center of the octahedron formed by six
state of VI3 is the Mott-insulator state. The half-metallic
neighboring I ions. Each van der Waals monolayer is formed
state as reported in the literature has a higher total energy.
by edge-connecting VI6 octahedra; see Fig. 1.
Magnetocrystalline anisotropy calculations confirm the out-
The studies on the VI3 material have emerged very re-
of-plane magnetic easy axis. The magnetic coupling across
cently. Controversies still remain with regard to its crystal
the vdW gap is dependent on the stacking order. The results
and electronic structure. Off-center distortions of the V ions
indicate that VI3 has very similar properties to those of CrI3 .
with respect to the iodine octahedra were reported in Ref. [5],
The rest of the paper is organized as follows. The computa-
but they were not observed by other experiments [6,7] or
tional details are presented in Sec. II. The electronic structure
theoretical simulations [8,9]. Structural phase transition at
of the VI3 monolayer is discussed in Sec. III A. Section III B
around 80 K involves the stacking ordering of vdW mono-
presents the magnetic properties of the VI3 monolayer and
layers [5,6], reminiscent of the structural phase transition in
bilayer. A conclusion is given in Sec. IV.
the CrI3 crystal [10]. The high-temperature crystal structure
was attributed to different space groups in the literature: P3̄1c
(Ref. [5]), C2/m (Ref. [6]), or R3 (Ref. [7]). The crystal
structure at low temperatures was described as C2/c (Ref. [5]) II. COMPUTATIONAL DETAILS
or R3̄ (Ref. [6]). As a reference, bulk CrI3 possesses a mono-
First-principles calculations were carried out using the den-
clinic lattice with C2/m symmetry at room temperature, and
sity functional theory (DFT) in the projector augmented-wave
a rhombohedral lattice with R3̄ space-group symmetry at low
framework as implemented in the VASP code [11–15]. We use
temperatures [10].
the Perdew-Burke-Ernzerhof [16] parametrization of the gen-
The VI3 material was reported to be a semiconductor with
eralized gradient approximation for the exchange-correlation
an optical gap between 0.6 and 0.7 eV [5,7]. Theoretical
functional.
studies predicted VI3 as a Mott insulator with an energy
The semiempirical D2 van der Waals correction of Grimme
gap of 0.9–1.0 eV [5,6], in agreement with the experimental
[17] was added for calculating the total energy of the bilayers.
results. However, theoretical studies in Refs. [7–9] predicted a
The Coulomb correlation among V-d orbitals was taken into
half-metallic state without an energy gap. The transition to fer-
account using the DFT + U method [18]. The cutoff energy
romagnetic phase occurs at about 50 K [5–7]. The measured
is set to 260 eV for the plane-wave basis set. The two-
dimensional first Brillouin zone was sampled by a 10 × 10
uniform Monkhorst-Pack mesh. The integrations over the first
*
yunpengwang@csu.edu.cn Brillouin zone were carried out using the Methfessel-Paxton

2469-9950/2020/101(2)/024411(5) 024411-1 ©2020 American Physical Society

YUN-PENG WANG AND MENG-QIU LONG
FIG. 1. The atomic structure of a VI3 monolayer with its unit
cell (black lines). The octahedra formed by six neighboring I ions
surrounding V ions are shown.
smearing [19] for structural optimizations, and the tetrahedron
method with Blöchl correction [20] for the total energies.
Test calculations show that the accuracy of the calculated
magnetocrystalline energy is better than 0.01 meV per V
ion. The dipole-dipole magnetic interactions favor an in-plane
magnetic configuration. The total dipole-dipole interaction
energy is expressed as
 
μ0  Mi · M j (M0 · ri j )(M j · ri j )
Edip = − −3 ,
8π i j ri3j ri5j
where i and j are indices of sites, and Mi and M j are local
magnetic moments on sites. The vector ri j connects sites i and
j; its length is equal to ri j . Putting one V ion at the origin and
considering a uniform magnetic configuration (either in-plane
or out-of-plane), the magnetic anisotropy energy per V ion
due to the dipole-dipole interaction is
μ0 (2SμB )2  3(m · r j )2
0
Eani = , total energy than the half-metallic state. This conclusion holds
8π j
r 5j
where S = 1 is the spin quantum number of each V ion,
μB is the Bohr magneton, and m is a unit vector in the
0
plane. The Eani is positive, thus it favors an in-plane magnetic
configuration over the out-of-plane configuration. A direct
0
summation giving Eani is equal to 5.505/a03 (meV) per V ion,
where a0 is the lattice constant in angstroms; for instance,
0
Eani = 0.016 meV per V ion for a0 = 7 Å.
III. RESULTS
A. The electronic structure
In the VI3 material, the I6 octahedron provides an octahe-
dral crystal field to the V ion at the center. In the absence
of any distortions, the octahedral crystal field splits the V-d
orbitals into triply degenerate t2g and doubly degenerate eg
orbitals. With a nominal valent state of +3, each V ion in
VI3 holds two d-electrons occupying the lower-lying triply
degenerate t2g orbitals. The ground-state high-spin electronic
2↑
configuration (t2g ) is thus degenerate. As a result, the band
theory predicts VI3 to be a magnetic metal due to the partial
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PHYSICAL REVIEW B 101, 024411 (2020)
occupations. This conclusion holds true in the presence of
small distortions in the I6 octahedron, because the broadening
due to hybridization with I-p orbitals is generally larger than
the splitting due to the octahedron distortions. Taking into
account the Coulomb repulsion among d-electrons residing on
the same V ion, the partial occupations of d-orbitals become
unfavored. The d-d Coulomb repulsion competes with the p-d
hybridization, or equivalently, it competes with the kinetic
energy of electrons. If the Coulomb repulsion wins, each of
the V-t2g orbitals is either fully occupied or fully empty; this
leads to the Mott-insulator phase. Otherwise the V-t2g orbitals
would remain degenerate and partially occupied to maximize
the hybridizations with I-p orbitals. In the oxides of late
transition metals, it is the Coulomb repulsion that completely
wins the competition. As we will show later, the Coulomb
repulsion wins in the VI3 material as well, but only by a
narrow margin.
The above discussion indicates two possible electronic
states of VI3 : the half-metallic state from the band theory,
and the Mott-insulator state favored by the intra-atomic cor-
relations. The optical gaps of 0.6 and 0.7 eV as reported
in recent experiments [5,7] support the Mott-insulator state
as the electronic ground state. We successfully obtained the
half-metallic and Mott-insulator states from DFT + U calcu-
lations. Comparison of their total energies gives the electronic
ground state.
We extracted a VI6 monolayer from the experimental crys-
tal structure [6] as attributed to the R3̄ space group with a
lattice constant of 6.835 Å. By setting different mixing and
smearing parameters, the DFT self-consistent-field calcula-
tions produce two distinct electronic states, corresponding to
the Mott-insulator and half-metallic states, respectively, as re-
ported in the literature [5–9]. Technically, the Mott-insulating
state is produced by setting a large mixing parameter, while
the half-metallic state can be produced with a small mixing
parameter and a small smearing width.
We found that the Mott-insulator state always has a lower
for the values of the Hubbard U between 1.7 and 4.7 eV.
We thus verify that the electronic ground state of VI3 is
semiconducting, in agreement with experiments [5,7], but the
half-metallic state is not, as predicted by Refs. [7–9]. The half-
metallic state has a total energy that is higher by 0.2–0.4 eV
per VI3 than the Mott-insulator state; see Fig. 3. This small
total energy difference explains why both states are accessible
by self-consistent-field calculations.
The spin-resolved density of states (DOS) of the two
different electronic states are plotted in Figs. 2(a) and 2(b).
The energy of the highest occupied Bloch state is set to zero.
The value of the Hubbard U is set to 3.7 eV. The DOS of
the Mott-insulator state [Fig. 2(a)] shows that the conduction
band at around 1.0 eV is completely contributed by the V-d
orbital. The charge density contributed by the states within
this narrow conduction band, as shown in Fig. 2(c), indicates
little hybridization between the V-d orbital and the orbitals
on the neighboring I ions. The occupied V-d orbitals reside
below −1.0 eV and hybridize strongly with I-p orbitals. The
DOS of the half-metallic state, as show in Fig. 2(b), is quite
different from the Mott-insulator state. The V-d orbitals make
a significant contribution to the spin-up channel of the DOS
ELECTRONIC AND MAGNETIC PROPERTIES OF VAN DER WAALS …
FIG. 2. The spin-resolved density of states (DOS) of (a) the
Mott-insulating state and (b) the half-metallic state. A Hubbard U
of 3.7 eV is used in the DOS calculations. (c) The charge density
contributed by the states within the narrow conduction band at 1.0 eV
of the Mott-insulating state.
between −0.5 and 0.2 eV. These V-d orbitals are strongly
hybridized with the I-p orbitals in this energy range.
The difference between these two states is also reflected in
the atomic-site resolved charges and spin moments, as listed
in Table I. Taking the Mott-insulating state as reference, a
small amount of electrons transfer from the I ions to the V
ions in the half-metallic state. The extra electrons transferred
to the V ions align their spin moment along the local magnetic
moment and enhance the spin moment of V ions from 1.97μB
to 2.29μB .
As a Mott insulator, the calculated electronic structure of
VI3 is sensitive to the value of the Hubbard U parameter,
as shown in Fig. 3. The value of the empirical Hubbard U
of V ions was estimated to be between 3 and 4 eV [8,21].
Within this range of Hubbard U , the calculated band gap is
between 0.7 and 1.0 eV, in good agreement with previous
experimental and theoretical results [5–7]. Figure 3 shows
that the calculated band gap increases linearly as U increases;
the increasing rate is similar to that in transition-metal oxides
[22]. Figure 3 also shows the total energy difference per V ion
between the Mott-insulator state and the half-metallic state.
The total energy difference is roughly a linear function of the
Hubbard U . Note that the electrical gap energy (0.32 eV) as
extracted from the temperature dependence of the electrical
resistivity [5] is within the same range of the calculated total
energy difference. We postulate that the electronic transport in
TABLE I. Calculated atom-resolved charges and spin moments
on V and I ions. Calculations were done with the experimental
structure and with inclusion of the Hubbard U of 3.7 eV.
Half-metallic state Mott insulating state
charge of V-d 2.98 2.89
charge of I-p 2.77 2.82
spin on V-site 2.29 1.97
spin on I-site −0.14 −0.05
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FIG. 3. The calculated energy gap of the Mott-insulating state
(circles) and the energy difference between the half-metallic state
and the Mott-insulating state (squares) vs the value of the Hubbard
U parameter.
VI3 may involve the local excitations from the Mott-insulator
state to the half-metallic state.
B. The magnetic properties
Next we study the magnetic properties of the VI3 material.
Bulk VI3 is ferromagnetic below 50 K, and the shape of
the magnetic hysteresis loop suggests an out-of-plane mag-
netic easy axis [5–7]. By including the spin-orbital coupling
term, we calculated the magnetocrystalline anisotropy energy
(MAE) of the VI3 monolayer. The MAE is defined as the total
energy with an out-of-plane magnetic moment configuration
minus in-plane. Negative MAE thus corresponds to the out-of-
plane easy magnetic axis. Here we assumed that the interlayer
coupling has little effect on the magnetocrystalline anisotropy.
The dots in Fig. 4(a) show the calculated MAE using the
monolayer structure extracted from experimental bulk struc-
ture. The calculated MAE ranges from −0.4 to −0.05 meV
per unit cell, depending on the value of the Hubbard U . The
negative MAE is consistent with the out-of-plane easy axis
as observed in experiments [5–7]. The value of the Hubbard
U has a significant effect on the calculated MAE. The MAE
drops from −0.4 to −0.1 meV as the Hubbard U increases
from 2 to 3 eV. The dependence of the calculated MAE
on the Hubbard U can be traced back to the band gap. In
the second-order perturbation theory, the MAE is inversely
proportional to the energies of virtual excitations. The band
gap increases linearly as the Hubbard U increases (Fig. 3), and
as a result the MAE decreases reciprocally as the Hubbard U
increases.
The calculated value of the MAE is sensitive to the atomic
structure. We optimized the atomic structure using various
Hubbard U ’s, and we calculated the MAE using the same
YUN-PENG WANG AND MENG-QIU LONG
FIG. 4. The calculated magnetocrystalline anisotropy energy
(MAE) of VI3 monolayer. (a) The calculated MAE using the ex-
perimental and the relaxed structure vs the value of Hubbard U .
The experimental lattice constant is used. (b) The calculated MAE
as a function of lattice constant by using different Hubbard U . The
optimal lattice constant is about 7.15 Å.
Hubbard U for the relaxation. The circles in Fig. 4(a) show
the results when the lattice constant is constrained to the
experimental value (a0 = 6.835 Å). The calculated MAE
using the relaxed structure is stronger in magnitude than the
experimental structure when using a small Hubbard U , but
it decays faster as the Hubbard U increases. The calculated
MAE becomes positive at a larger Hubbard U , corresponding
to an in-plane easy magnetic axis.
The strong dependence on the atomic structure suggests a
tunable MAE by mechanical strains. The mechanical strain
is an efficient route for engineering the material properties
[23,24]. Figure 4(b) shows the calculated MAE using relaxed
structures with different lattice constants. The same Hubbard
U is used for the structural relaxation and the MAE calcu-
lations. The optimal lattice constant is about 7.15 Å, with a
weak dependence on the value of the Hubbard U . The cal-
culated lattice constant is longer than the experimental value
by 4.6%. Figure 4(b) indicates that the MAE is enhanced by
tensile strains, but is weakened by compressive strains. This
result points to a strain-tunable MAE of VI3 .
Next we explored the magnetic exchange coupling across
the van der Waals gap. The exotic interlayer antiferromagnetic
(AFM) coupling has been investigated in a similar material
CrI3 . The interlayer stacking pattern was theoretically pre-
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PHYSICAL REVIEW B 101, 024411 (2020)
FIG. 5. Stacking-order-dependent interlayer magnetic exchange
coupling in VI3 bilayer. Top view of VI3 bilayer with (a) the AB
stacking order and (b) the AB stacking order; only V ions are
shown for clarity. (c) The calculated total energies and the interlayer
magnetic coupling energies of the VI3 bilayer with AB and AB
stacking orders. The interlayer distance is measured as the distance
between I ions across the van der Waals gap.
dicted as the key for determining the sign of the interlayer cou-
pling [ferromagnetic (FM) or AFM] [25–28]. The interlayer
stacking pattern in few-layer CrI3 at low temperatures is not
the one in bulk CrI3 at low temperature, but it is the one in bulk
CrI3 at high temperatures. This prediction was later confirmed
by the second-harmonic-generation experiment [29].
Given the similarity with CrI3 , one expects a stacking-
order dependence of the interlayer magnetic coupling in the
VI3 material. We considered a VI3 bilayer and calculated
the interlayer magnetic coupling following Ref. [25]. There
are two interlayer stacking patterns in VI3 with the lowest
total energies. The two stacking patterns are denoted as AB
and AB following the terms used in Ref. [25] for the CrI3
bilayers. The two stacking orders are schematically shown
in Fig. 5. By adding an empirical van der Waals energy
correction, we calculated the total energies of the VI3 bilayer
in the FM configuration versus the interlayer distance. The
optimal interlayer distance is about 3.4 Å for both AB and
AB stacking patterns. The total energy of the AB stacking
pattern is higher by ∼15 meV than the AB pattern. The AB
stacking pattern is the most stable state while the AB pattern
is metastable according to the calculation, which is similar to
the CrI3 case. The magnetic interlayer coupling was calculated
as the total energy difference between the FM and the AFM
configurations. The FM configuration is favored by the AB
stacking pattern, while the magnetic interlayer coupling is
AFM with the AB stacking. The magnitude of the interlayer
coupling decays as the interlayer distance increases. At the
optimal interlayer distance, the AFM coupling strength is
about 1.5 meV per unit cell.
We predict a stacking-order dependence of the interlayer
magnetic coupling, namely a FM coupling in the most stable
stacking order but AFM coupling in the metastable stacking
order. The situation of VI3 is the same as in CrI3 [25–28]. The
ELECTRONIC AND MAGNETIC PROPERTIES OF VAN DER WAALS …
metastable stacking order can be realized in few-layer CrI3
samples, or by applying external pressures on CrI3 thin films
[30,31]. We expect the same phenomenon can be observed in
the VI3 thin films.
IV. CONCLUSIONS
We have conducted first-principles investigations of the
electronic and magnetic properties of the VI3 material. We
have found that the VI3 material exhibits properties that are
very similar to those of the CrI3 material. The VI3 possesses
a Mott-insulator state as the ground state, which is lower
by 0.2–0.4 eV than the metastable half-metallic state. The
VI3 monolayer exhibits an out-of-plane magnetic axis, and
the magnetocrystalline anisotropy is tunable by mechanical
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