Nano Research

DOI 10.1007/s12274-014-0626-5

A density functional theory study of the tunable structure,

magnetism and metal–insulator phase transition in VS2
monolayers induced by in-plane biaxial strain
Min Kan1,2,3, Bo Wang4, Young Hee Lee2,3 (), and Qiang Sun1,5 ()

1
Department of Materials Science and Engineering, Peking University, Beijing 100871, China
2
Center for Integrated Nanostructure Physics, Institute for Basic Science, Sungkyunkwan University, Suwon 440-746, Korea
3
Department of Physics and Department of Energy Science, Sungkyunkwan University, Suwon 440-746, Korea
4
School of Mathematical Sciences, Peking University, Beijing 100871, China
5
Center for Applied Physics and Technology, Peking University, Beijing 100871, China

Received: 18 August 2014 ABSTRACT nêu hẳn mục đích nghiên cứu đầu đoạn luôn
Revised: 7 October 2014 We report a density functional theory study of a phase transition of a VS2
Accepted: 28 October 2014 monolayer that can be tuned by the in-plane biaxial strain. This results in both a
metal–insulator transition and a low spin–high spin magnetic transition. At low Trong ứng
© Tsinghua University Press temperature, the semiconducting H-phase is stable and large strain (>3%) is dụng j
and Springer-Verlag Berlin required to provoke the transition. On the other hand, at room temperature
Heidelberg 2014 (300 K), only a small tensile strain of 2% is needed to induce the phase transition
from the semiconducting H-phase to the metallic T-phase together with the
KEYWORDS magnetic transition from high spin to low spin. The phase diagram dependence
phase transition, on both strain and temperature is also discussed in order to provide a better
biaxial strain, understanding of the phase stability of VS2 monolayers.
phase diagram,
density functional theory
(DFT),
transition metal
dichalcogenide
(TMD) materials

1 Introduction storage, integrated circuits, transparent conducting

electrodes, optoelectronics, and valleytronics [1–5].
Two-dimensional (2D) layered transition metal TMDs materials have the chemical formula MX2,
dichalcogenide (TMD) materials have been intensively where M is a transition metal and X is a chalcogen (X =
studied recently because of their unique properties S, Se, Te). Depending on the combination of chalcogen
that give rise to potential uses in catalysis, energy and transition metal, more than 40 different TMDs

Address correspondence to Young Hee Lee, [email protected]; Qiang Sun, [email protected]

2 Nano Res.

can be realized, which can be metallic, semimetallic, controllable, reversible and experimentally feasible
or semiconducting [6, 7]. Different experimental method to induce the phase transition between H
strategies have been used to synthesize TMD mono- and T phases in TMD materials in order to change
layers successfully, such as mechanical exfoliation the electronic and magnetic properties?
methods, liquid exfoliation methods, and chemical In this study, we show that the electronic and
vapor deposition (CVD) [8–10], which have stimulated magnetic properties of monolayer T-phase and H-phase
the search for unprecedented physical and chemical VS2 are quite different from each other. The T-phase
properties from a theoretical point of view. VS2 is metallic, while the H-phase VS2 is a semicon-
Monolayer TMD materials can in general exhibit ductor with a band gap of 0.187 eV. The magnetic
two polymorphs: Trigonal prismatic (denoted the H- moment of the T-phase per unit cell is 0.43 μB, while
phase) and octahedral coordinated (denoted T-phase) that of the H-phase VS2 is an integer of 1.0 μB. By
_
[11]. The H-phase has the space group P6m2 and simply applying a biaxial compression or tensile strain,
belongs to the D3h point group, while the T-phase we can reversibly tune the phase stability of VS2.
belongs to the D3d point group. It is intriguing to see Previously, in-plane strain has been extensively used
that the electronic and magnetic properties of the two to tune the electronic and magnetic properties of 2D
such polymorphs are quite different from each other. materials. For example, the magnetic moments of
For example, the H-phase MoS2 monolayer is a direct MX2 (M = V, Nb; X = S, Se) can be enhanced significantly
semiconductor with a band gap around 1.90 eV [12], by tensile strain [18, 19]. As far as we know, this is the
while the T-phase MoS2 monolayer is metallic. Thus, first study using the in-plane strain to tune the phase
it will be fascinating if one can reversibly control the stability of 2D TMD materials. For a VS2 sheet at 0 K,
phase transition between H-phase and T-phase TMDs, the H-phase is stable in the biaxial strain range –7% <
since this will have great potential applications in ε < 4.5%, while the T-phase is more stable than the
future electronic devices. H-phase when ε < –7% and ε > 4.5%. By considering
Recently, significant progress has been achieved the temperature effect, a tensile strain less than 2%,
in the synthesis of WS2 nanotubes with octahedral which is accessible in experiments, can reverse the
coordination using rhenium doping [13], which is an phase stability from the H-phase to the T-phase at
irreversible process. More interestingly, it has been room temperature (300 K). We also simulate the phase
recently shown that the T-phase MoS2 monolayer can diagram of monolayer VS2 by including the strain
coexist in a layer of the Re-doped H-phase MoS2 and temperature effects together, which helps to better
under electron beam irradiation at high temperature understand the phase transition of monolayer VS2.
[14]. In this case, chemical doping, electronic beam,
and temperature effects are combined to give partial
2 Computational methods
conversion to the T-phase, which is hard to realize
reversibly in devices. It has been also proposed Our first-principles calculations are based on spin-
theoretically that electron injection with a concentration polarized density functional theory (DFT) with
of 8.33 × 1014 cm–2 or lithium adsorption with a con- the Perdew–Burke–Ernzerhof (PBE) form and the
centration of exactly 20% can also induce the phase generalized gradient approximation (GGA) [20] for
transition for MoS2 monolayers from the H-phase to exchange-correlation potential. Plane-wave basis sets
the T-phase [15]; however, this electron concentration with the projector augmented plane-wave method
is quite high and the extent of lithium adsorption on (PAW) [21] are used as implemented in the Vienna
the surface is uncontrollable in experiments. Very ab initio simulation package (VASP) [22]. Periodic
recently, ultrathin 2D VS2 nanosheets have been boundary conditions are used to simulate 2D monolayer
successfully synthesized by a hydrothermal method VS2 and all the structures are relaxed without any
[16, 17], and demonstrated room temperature fer- symmetry constraints. A vacuum space of 30 Å is
romagnetism and hysteresis in a 2D structure for the used along the c-axis in order to avoid interactions
first time [17]. A question then arises: Can we find a between two neighboring images. The reciprocal

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Nano Res. 3

space is represented by a Monkhorst–Pack special where EVS2 stands for the energy of VS2 per unit cell,
k-point scheme [23] with 25 × 25 × 1 and 9 × 9 × 1 grid and EV and ES are the energy of free V and S atoms,
meshes for a unit cell and a (4 × 4) supercell. For respectively. The calculated cohesive energies are 15.20
geometry optimization, the criteria of convergence and 15.25 eV per VS2 chemical unit for the H- and
for energy and force, as well as energy cutoff are set to T-phase, respectively, indicating strong cohesive bonds
be 1 × 10−8 eV, 1 × 10−6 eV/Å, and 400 eV, respectively. To for two phases; these values should be compared to
properly describe the strongly correlated electrons in the overestimated local-density approximation (LDA)
the partially filled d subshells, we use the GGA + Ueff result (17.5 eV) [32]. The calculated band structure
method introduced by Dudarev et al. [24] with Ueff = using the PBE functional is shown in Figs. 2(a) and
3.0 eV for V atoms, which has been widely used in 2(b), indicating that the T-phase of VS2 monolayer is
previous reports [25–27]. In addition, the state-of-the- metallic which is in agreement with previous theoreti-
art hybrid functional (HSE06) [28, 29] is also employed cal and experimental studies [16, 18, 31, 32], while the
to calculate the band structures. Calculations of the H-phase is an indirect semiconductor with a small
thermal properties are performed using finite dis- band gap of 0.187 eV.
placement method as implemented in the Phonopy Since GGA fails to give an accurate band gap for
program [30] and 4 × 4 supercells containing 48 atoms TMD semiconductors, we use GGA+U and state-of-
are employed. The Helmholtz free energy (F) contains the-art hybrid functional HSE06 to further confirm the
two contributions: Total energy E0 at 0 K and phonon semiconducting property of H-phase VS2 monolayer
free energy Fph, and can be written as F(T) = E0 + Fph(T). in the following. Based on previous studies [25–27],
As written in the manual of Phonopy program, the we use Ueff = 3.0 eV to calculate the band structure, as
phonon free energy Fph is calculated from the following shown in Fig. 2(c). By introducing strong correlation
equations in d subshells of V atoms, the band gap increases to
0.721 eV. In the calculation with HSE06, we also get a
1
Fph (T )  ћ (q, s)  kBT 
2 q ,s q ,s
ln[1 exp(  ћ (q , s)/ kBT )] semiconductor character from the band structure in

where kB and ћ are the Boltzmann constant and the

reduced Planck’s constant, respectively, and ω(q, s)
stands for the sth phonon frequency with a wave vector
q at 0 K. The variations in the temperature-dependent
electron occupation and electron–phonon coupling
are neglected.

3 Result and discussion Figure 1 (a) Top view and (b) side view geometry of T-phase
monolayer VS2; (c) top view and (d) side view geometry of
We first perform fully relaxed structure optimization H-phase monolayer VS2 where V atoms are gray and S atoms are
for both the T-phase and H-phase of a VS2 monolayer. yellow.
The optimized structures and calculated geometric
parameters are shown in Fig. 1 and Table 1, respectively. Table 1 The optimized geometrical parameters, cohesive energy,
and band gap for T-phase and H-phase VS2: Lattice parameter, a0;
For the T-phase (H-phase), the lattice constant, V–S
bond length, dV–S; interlayer distance between vanadium and
bond length, and the distance between the V and S sulfur planes, ΔV–S; V–S–V bond angle, θV–S–V; cohesive energy
atom planes are 3.181 (3.173), 2.351 (2.362) and 1.468 per VS2 unit, EC; band gap calculated from PBE, Eg
(1.491) Å, respectively, which agree very well with a
a0 (Å) dV–S (Å) ΔV–S (Å) θV–S–V (°) EC (eV) Eg (eV)
previous study [31] using the same exchange-correlation
T 3.181 2.351 1.468 85 15.25 0
potential. We also calculate the cohesive energy per
H 3.173 2.362 1.491 84 15.20 0.187
unit cell, which is defined as EC = – (EVS2 – EV – 2ES),

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4 Nano Res.

Figure 2 Calculated band structures of (a) T-phase and (b) H-phase VS2 with the PBE method; the calculated band structure of
H-phase VS2 with (c) GGA+U (U = 3.0 eV) and (d) HSE06 method.

Fig. 2(d), and the band gap is further increased to bands leading to a fractional magnetic moment of less
1.128 eV. This ensures that H-phase VS2 monolayer is than 1.0 μB. On the other hand, the H phase adopts
a semiconductor in spite of some numerical variance a trigonal-prismatic structure, and the d orbitals of
with calculation methods. To get a precise value of the the V atom are divided into three groups, a1’ (dz2), e’
band gap, one needs to use GW calculation methods (dxy and dx2-y2) and e’’ (dyz and dxz) [34, 35]. Previous
[33]. However, due to limited computational resources, calculations indicate that the a1’ orbital is the lowest d
we still used the PBE method in the following to study level [35], and the spin-up and spin-down states are
the phase transition. totally separated as shown in Fig. 2(b). Thus, the single
In addition, we also carry out spin-polarized 3d1 electron will fully occupy one of the two spin
calculations to study the magnetic properties of polarized dz2 orbitals, resulting in a integral magnetic
monolayer T-phase VS2 and H-phase VS2. The calculated moment of 1.0 μB per unit cell and a band gap
magnetic moment of T-phase VS2 per unit cell is between the spin-up and spin-down a1’ orbitals. The
0.43 μB, and that of H-phase VS2 is 1.0 μB, which is iso-surfaces of the spin density (ρ↑– ρ↓) for T-phase
almost twice that for T-phase monolayer VS2. This VS2 and H-phase VS2 are shown in Fig. 3, and indicate
is consist with previous studies [17, 31] and can be that the V atoms in the H-phase are more spin-
understood in terms of the electronic configurations polarized than those in the T-phase.
of T-phase VS2 and H-phase VS2: In the T-phase, both Since the electronic and magnetic properties are
the spin-up and spin-down bands are metallic, and quite different for two phases, as we discussed above,
the 3d1 electron partially occupies the two polarized it will be quite interesting to see if we can realize the

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Nano Res. 5

but failed due to the large energy difference between

the two phases of MoS2.
To check the possibility of potential applications of
monolayer VS2 in spintronic and electronic devices,
we also calculated the variations in band gap and
magnetic moment with different strains. Even though
a low-dimensional material can in general sustain a
larger strain without fracture than a bulk material,
we only simulate the strain between –4% and 4% in
Figure 3 Iso-surface (with value of 0.05 electron/Å3) on (a) top the following, taking into account values that can be
view and (b) side view of spin density of 2D T-phase VS2; realized experimentally. The band gap of the T-phase
iso-surface (with value of 0.05 electron/Å3) on (a) top view and is always 0 eV, independent of the studied strain
(b) side view of spin density of 2D H-phase VS2. In the iso-surface value. On the other hand, the band gap of the H-phase
plot, blue represents positive values. varies as the strain changes. The H-phase retains
semiconducting behavior without an appreciable
phase transition between H-phase and T-phase VS2 in
change in band gap under tensile strain, while it
a tenable way by experiment. Additionally, a previous
converts to a metallic phase with a compressive
study shows that the energy barrier between the two
strain of ≤ –3%. Figure 4(c) shows that the H-phase
phases is 0.62 eV [31], which is much smaller than
possesses an integral magnetic moment of 1 μB when
that in MoS2. These results indicate that the phase
the strain ≥ –2%, while it possesses a fractional
transition in VS2 should be easier to realize. Recent
magnetic moment with a strain ≤ –3%. The T-phase
studies suggest that elastic strain engineering can be always possesses a fractional magnetic moment and
used to manipulate the physical properties of low- the magnetic moment increases monotonically as the
dimensional materials, which allows a much wider strain increases from –4% to 4%, which is consistent
dynamic range of elastic strain to be reached reversibly with a previous study [18]. We also find that the
[18, 19, 36–38]. Thus, we propose that a biaxial tensile magnetic moment of the H-phase is always larger
or compressive strain may induce the phase transition than that of the T-phase for each given strain, so that
between our two phases of monolayer VS2. Here, we the H-phase can be defined as a high magnetic
define the biaxial strain as ε = (a – a0)/a0 × 100%, where moment state, and the T-phase as a low magnetic
a0 (3.173 Å) is the lattice constant of the H-phase VS2 moment state. Our calculations predict that both the
in its equilibrium state, and a is the lattice constant of metal–insulator transition and the high spin–low
the strained monolayer VS2. The smooth variations of spin magnetic transition can occur simultaneously by
total energies per unit cell with biaxial strain from simply tuning the biaxial strain.
–10% to 10% are shown in Fig. 4. The H-phase is more The above DFT simulations of the phase transition
stable than the T-phase in the range –7% < ε < 4.5% as induced by strain above were carried out at 0 K.
marked in green, while the T-phase is more stable However, in reality, the temperature is also an important
than the H-phase in the range –10% < ε < –7% and factor associated with the influence of strain on phase
4.5% < ε < 10%, as marked with yellow in Fig. 4(a). stability. One famous example is the Peierls phase
The phase transition from the H-phase to the T-phase transition, which has already been found in one-,
occurs at a compressive strain of 7% and a tensile strain two- and three-dimensional systems [39–41]. A recent
of 4.5%. To our knowledge, such a strain-induced study showed that when the temperature is increased,
phase transition between the T-phase and H-phase the phase transition in MoS2 is easier to realize [14].
has never been observed in other TMD materials, Hence we also studied the phase transition of our 2D
which can be ascribed to the small energy difference VS2 system by considering the temperature effect.
between two phases of VS2. We also tried to induce First, we simulate the Helmholtz free energy for both
the phase transition for MoS2 with the same method H-phase and T-phase VS2 monolayers without strain

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6 Nano Res.

Figure 4 (a) The dependence of the energy per unit cell on the strain for T-phase and H-phase VS2. The calculated (b) band gap and
(c) the dependence of the magnetic moments for T-phase and H-phase monolayer VS2 on the biaxial strain.

as shown in Fig. 5(a), which shows the typical free ε < 4.5%, while the T-phase is more stable than the
energy curves. At low temperature, the free energy of H-phase when ε < –7% and ε > 4.5%; without strain,
the H-phase is smaller than that of the T-phase and the H-phase is stable from 0 to 502 K, and the
the difference decreases as the temperature increases. T-phase is more stable than the H-phase when the
Interestingly, the stability of the two phases is reversed temperature is higher than 502 K. The next question
at a critical temperature (Tp). To check the critical is whether or not the temperature effect can lower
temperature carefully, we also plot the Helmholtz the critical strain, and what the phase diagram will
free energy difference between H-phase and T-phase look like when both strain and temperature effects
VS2, which is defined as ΔFH–T = FH-phase – FT-phase. From are considered. In the following, we calculate the
Fig. 5(b), we can see that the critical point is 502 K, critical temperature for the 2D monolayer VS2 at each
indicating the H-phase is more stable than the T-phase strain and fit a phase boundary between H-phase
from 0 to 502 K and the T-phase is more stable than the and T-phase VS2. The critical temperature is obtained
H-phase when the temperature is higher than 502 K. when FH-phase (Tp) = FT-phase (Tp).
Thus, the temperature effect is indeed an important The final simulated phase diagram, incorporating
factor that can influence the phase stability of our 2D the dependence on biaxial strain and temperature, of
monolayer VS2. the 2D monolayer VS2 is shown in Fig. 5(c). As we
From the above simulations, we know that at 0 K can see from the phase diagram, there is a distinct
the H-phase is stable in the biaxial strain range –7% < boundary between the H-phase and T-phase, which

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Nano Res. 7

Figure 5 (a) Calculated Helmholtz free energy for H-phase and T-phase VS2 monolayers; (b) the Helmholtz free energy difference
between H-phase and T-phase VS2; (c) simulated dependence of the phase diagram of 2D monolayer VS2 on the biaxial strain and
temperature.

is marked in green and can be fitted to the formula can tune the phase stability from H-phase to T-phase
for monolayer VS2 and vice versa. To our knowledge,
T = exp(–787 + 1,608 × ε – 815 × ε2)
this is the first example where such a small strain
In the low temperature region (< 300 K), most of the can induce a phase transition in 2D monolayer TMD
phase diagram is filled with the H-phase, and the materials. One general conclusion is that the H-phase
T-phase can only be more stable than H-phase when will be more stable as the temperature decreases, while
an appropriate biaxial tensile strain is applied. For the T-phase will be more stable as the temperature
example, a 2% biaxial tensile strain is required to increases, at each strain between –4% and 4% in our
reach the T-phase at 300 K. In the high temperature simulation. Another result associated with the moun-
region (> 700 K), the T-phase is always more stable tain shape of the phase boundary is that the temperature
than H-phase within the biaxial strain range from effect can lower the critical strain in VS2 monolayers.
–4% to 4%. At a typical temperature such as 500 K, This synergetic effect on the phase transition may be
we have the chance to realize the phase transition employed experimentally in areas such as electronic
T→H→T as the biaxial strain increases from –4% to memory devices or CVD growth, where strain always
4%. More importantly, at room temperature (300 K), exists due to the lattice mismatch between the TMD
the H-phase is more stable when the biaxial strain is material and the substrate. Thus, we hope that our
smaller than 2%. This means that a biaxial tensile strain simulation data can guide further experimental studies
of only 2%, which is easily accessible in experiments, of strain sensors and low-wavelength photodetectors.

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8 Nano Res.

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