ARTICLE

Received 13 Dec 2013 | Accepted 27 May 2014 | Published 1 Jul 2014 DOI: 10.1038/ncomms5214

Structural phase transitions in two-dimensional

Mo- and W-dichalcogenide monolayers
Karel-Alexander N. Duerloo1, Yao Li1,2 & Evan J. Reed1

Mo- and W-dichalcogenide compounds have a two-dimensional monolayer form that differs
from graphene in an important respect: it can potentially have more than one crystal
structure. Some of these monolayers exhibit tantalizing hints of a poorly understood struc-
tural metal-to-insulator transition with the possibility of long metastable lifetimes. If con-
trollable, such a transition could bring an exciting new application space to monolayer
materials beyond graphene. Here we discover that mechanical deformations provide a route
to switching thermodynamic stability between a semiconducting and a metallic crystal
structure in these monolayer materials. Based on state-of-the-art density functional and
hybrid Hartree–Fock/density functional calculations including vibrational energy corrections,
we discover that MoTe2 is an excellent candidate phase change material. We identify a range
from 0.3 to 3% for the tensile strains required to transform MoTe2 under uniaxial conditions
at room temperature. The potential for mechanical phase transitions is predicted for all six
studied compounds.

1 Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, USA. 2 Department of Applied Physics, Stanford

University, Stanford, California 94305, USA. Correspondence and requests for materials should be addressed to E.J.R. (email: [email protected]).

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms5214

he discovery of a mechanical exfoliation method1 for two-

T
Results
dimensional (2D) crystals has led to the discovery of Monolayer crystal structures. Under ambient conditions, all
fundamentally new physics, and it was a watershed in the group VI TMDs (except WTe2) are reported to exist in a layered
search for the materials that will take the centre stage in bulk crystal structure composed of monolayers wherein the X
tomorrow’s technology. Among the layered crystals amenable to atoms are in trigonal prismatic coordination around the M
isolation of atomically thin monolayers is a large family of atoms17. The atomic stacking sequence within a single XMX
transition metal dichalcogenides (TMDs) having the chemical monolayer is bAb. In keeping with prior literature, we will refer
formula MX2, where M is some transition metal and X stands for to this as the 2H phase, even though the prefix ‘2’ is irrelevant in
S, Se or Te. The mostly semiconducting2 subset of TMDs where monolayers because it refers to a bulk stacking mode. Group VI
the transition metal M is Mo or W (both in group VI) has MX2 monolayers in the 2H structure are semiconducting with
received the greatest amount of attention in the pursuit of band gaps between 1 and 2 eV (refs 2,33,34). 2H TMDs are
applications, including ultrathin flexible electronics2–8 and promising semiconductors for flexible electronics applications2–8.
valleytronics9,10. In an energy context, these materials hold The 2H structure gives rise to metallic edge states that
promise as hydrogen evolution catalysts when certain features are are associated with electrocatalytic activity11. The primitive unit
exposed to the reacting environment11–16. cell of the 2H phase is hexagonal. For reasons of consistency
A special but often overlooked feature of group VI TMD between different phases, our calculations on 2H use a non-
monolayers is that they have more than one possible 2D crystal primitive rectangular unit cell whose axes align with zigzag and
structure. This polymorphism sets group VI TMD monolayers armchair directions of the structure. These special axes can be
apart from other 2D materials such as graphene and hexagonal experimentally identified using second harmonic generation35,36,
BN17–19. Intriguingly, one of these structural phases is and possibly also using the intrinsic piezoelectricity predicted to
semiconducting, whereas the others are metallic, unlike in the exist in these materials37. Figure 1 shows the 2H structure within
case of group V TMDs, where electrically activated metal-to- a rectangular unit cell having lattice constants a and b.
metal structural phase transitions have been demonstrated in When one of the 2H structure’s X layers is shifted (for instance,
multilayer TaS2 (ref. 20) and TaSe2 (ref. 21). bAb-bAg), the X atoms are in octahedral coordination around
It has been suggested that coexistence of metallic and the M atoms, and the crystal becomes metallic. This phase is
semiconducting regions on a monolithic MX2 nanosheet can be referred to as 1T and is observed in group IV and group V TMD
used to make electronic devices18, and metallic regions have compounds (for example, TiS2 and TaSe2 (ref. 17)). Its atomic
been associated with catalytic activity leading to hydrogen structure is also shown in Fig. 1. We have calculated the atomic
evolution12,16,22. Moreover, materials with dynamic metal-to- vibrational normal modes (!-phonons) within the relaxed
insulator transitions close to ambient conditions are exceedingly rectangular 1T unit cell of all six group VI TMDs. In all cases,
rare and worth pursuing because of their nonvolatile information one of the optical phonon modes has an imaginary vibrational
storage potential. Because the TMD metal-to-insulator transition frequency. This result asserts that the high-symmetry 1T structure
is structural in nature, considerable metastability and hysteresis is unstable (saddle point in 18D atomic potential energy surface),
are expected to occur. This useful feature is absent in approaches at least in the absence of external stabilizing influences.
where band gap closure is achieved by (and conditional on) large The group VI TMDs do have a stable metallic structure with
macroscopic strains to a fixed and normally semiconducting octahedral-like M–X coordination. This lower-symmetry phase,
TMD structural phase23. Phase transitions are even more exciting which we will refer to as 1T0 , is a distorted version of the 1T
in monolayers, which also provide opportunities for flexible, low- structure12,17,38. This phase has recently been shown to enhance
power and transparent electronic devices. electrocatalytic activity in WS2 (ref. 12). A rectangular (as well as
Despite the clear motivation for doing so, it has thus far primitive) 1T0 unit cell is displayed in Fig. 1. The 1T0 phase is
proven to be challenging to transform semiconducting MX2 observed in WTe2 under ambient conditions17, MoTe2 at high
compounds to a stable metallic phase. A process of lithium-based temperature39 and as a metastable phase in instances of
chemical exfoliation of bulk crystals has been shown to be a chemically exfoliated18 and restacked38 MX2 monolayers.
successful route to obtain a metastable metallic phase of the group
VI TMDs18,24–26. It is, however, uncertain that this phase would Phase energetics in the absence of mechanical stress. Figure 2
persist under all realistic operating conditions, and reversible shows the calculated equilibrium (that is, stress-free) relative
switching is not demonstrated in this case. One would like to know
under what thermodynamic conditions (if any) metallic phases of
TMDs are expected to be stable rather than just metastable. This z 2H 1T 1T′
insight would point in a direction of dynamic phase switching and
large-area synthesis of the elusive metallic phase using standard y
chemical growth techniques, such as chemical vapour deposition. a
Chemical growth techniques are an area of rapid progress in recent Mo, W M
years27–32. One would furthermore like to know what TMD S, Se, Te X
compounds are nearest to the phase boundaries at ambient
y b
conditions, and therefore most amenable to applications involving
transformations between phases or mixed-phase regimes.
Here we use density functional theory (DFT) and DFT-based
x
methods to determine the phase diagrams of TMD monolayers as
a function of strain. We find that equibiaxial tensile strains of 10– Figure 1 | The three crystalline phases of 2D group VI TMDs. Each can be
15% are required to observe the metallic phase for most TMDs, represented in a rectangular unit cell with dimensions a  b. All three
but MoTe2 may transform under considerably less tensile strain, phases consist of a metal (Mo/W) atom layer sandwiched between two
o1.5% under appropriate constraints. We further discover that chalcogenide (S/Se/Te) layers. The semiconducting 2H phase is often
mixed-phase regimes can be thermodynamically stable under referred to as the trigonal prismatic structure, and the metallic 1T and 1T0 are
certain thermodynamic constraints that are readily achievable in called octahedral and distorted octahedral, respectively. The 1T0 phase can
the laboratory. be thought of as 1T after a symmetry-reducing distortion.

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms5214 ARTICLE

1
1T 1T′
0.8

WS2
MoS2

Lattice constant b
2H
0.6
U=0 (eV per MX2)

MoSe2

WSe2
1T′
0.4

MoTe2

WTe2
0.2

0 2H
Lattice constant a
–0.2
Figure 3 | Substrate-based application of strain to a TMD monolayer.
Figure 2 | Ground-state energy differences between monolayer phases of One way in which the lattice parameters a and b of an MX2 monolayer may
the six studied materials. The energy U is given per formula unit MX2 for be tuned is by virtue of an underlying substrate (shown in blue). Because
the 2H, 1T0 and 1T phases. Its value is computed at the equilibrium (zero the substrate and the monolayer have a preferred crystallographic
stress, r) lattice parameters for each phase. Because r ¼ 0, these values for alignment, the deformation of the substrate can be transferred to the TMD
U are equivalent to the enthalphy H. Vibrational energy is not included in monolayer. If the values of the lattice constants a and b affect which of the
these values. phases is thermodynamically stable, the application of strain (or chemical
growth of the monolayer on a strained substrate) can be used to select a
particular phase.
energies of the phases (2H, 1T and 1T0 ) of the group VI MX2
monolayer materials. These values are calculated using DFT
under the generalized gradient approximation (GGA) for elec- method:
X  
tronic exchange and correlation effects, using the Perdew–Burke–
Ernzerhof40 (PBE) functional. The results are consistent with the Y ða  ak Þðb  bl Þ
U ða; bÞ ¼ U a i ; bj   ð1Þ
experimental observation for bulk crystals that only WTe2 is 1T0 i;j
k 6¼ i;l 6¼ j ða  a Þ b  b
i k j l
under ambient conditions17. It is also evident from these data that
the energy associated with the 1T to 1T0 relaxation is Lagrange interpolation is chosen because it contains no
considerable: several tenths of an eV per MX2 formula unit. physical assumptions about the shape of the U(a,b) energy
The three phases’ equilibrium lattice constants and energies are surface over a large range of tensile and compressive strains. It
tabulated in Supplementary Table 1. also greatly facilitates the approximation of local derivatives
(which we need later) without suffering from conditioning
problems found in other high-order polynomial methods.
Phase energetics under biaxial strain. Thermodynamics asserts Using this approach, we discover that the 2H and 1T0 U(a,b)
that a system will seek to minimize whichever thermodynamic energy surfaces intersect for sufficiently large strains. Figure 4
potential is appropriate for the prevailing mechanical and thermal shows the contours that follow the intersection of the 2H and 1T0
boundary conditions41. The simplest example of such a energy in (a,b) space. The changes in a and b required to change
thermodynamic potential is the internal energy U. In the low- the relative energies U of the 2H and 1T0 phase range from 13%
temperature limit, any system will seek to minimize U when it is (MoS2) to 3% (MoTe2). Because many bulk materials begin to
constrained to a given shape. Under these conditions, an MX2 dissipate strain energy through fracture or dislocations at strains
monolayer constrained to be described by a rectangular unit cell on the order of 0.1% (roughly 10  5 eV per atom), these threshold
with dimensions a  b is expected to be in the lower-U phase for strains may at first appear to be prohibitively large. However,
those values of a and b. it has been experimentally demonstrated that monolayer TMDs
Experimentally, relevant phase diagrams of monolayers differ are exceedingly strong: Bertolazzi et al.42 have performed atomic
from those of bulk materials at high pressure in at least one force microscopy (AFM) experiments where 2H-MoS2
important respect: the monolayer can be mechanically coupled to monolayers are shown to reversibly withstand in-plane tensile
a substrate with friction, enabling the independent control of a stresses up to 15 Nm  1, corresponding to B10% of the
and b lattice parameters (Fig. 3). Another key distinction is that material’s in-plane Young’s modulus. Such deformations
large elastic deformations in monolayers can be reached through correspond to an elastic energy of order 0.1 eV per atom. From
tensile strain42,43, whereas large elastic deformations in most the local derivatives of the 2H phase’s U(a,b) at the equibiaxial
bulk materials are accessible only under compression. Large transition strain, we find that the 2H stresses (in Nm  1) at this
compressive stresses are problematic in TMD monolayer point are 12.8 (MoS2), 10.8 (MoSe2), 6.9 (MoTe2), 13.6 (WS2) and
materials due to the spontaneous ripple formation that has 10.5 (WSe2). This suggests the possibility that a transition
been studied in MoS2 (refs 44,45). between 2H and 1T0 might be observable below but near the
For the six group VI MX2 monolayers, we use GGA–DFT to breaking threshold.
calculate the energies U(a,b) of the three monolayer crystal From Fig. 4, we can also see that WTe2, which is usually in the
structures on a 7  7 grid in (a,b) space, giving a total of 49 points 1T0 phase, can be pushed into a 2H regime under compression,
of (a,b)-values around the minimum-energy equilibrium lattice which is complementary to all the other cases where one would
constants a0 and b0 (listed in Supplementary Table 1). U is go from 2H to 1T0 through tension. While this is interesting, we
obtained after allowing the ions to relax their positions within will not focus on it since in-plane compression in monolayer
each unit cell. Intermediate values for each phases’ U(a,b) are WTe2 may be experimentally challenging to achieve without
subsequently approximated using the Lagrange46 interpolation incurring any buckling response.

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms5214

20 12
1T′
2H PBE
10
15 No vib.
1 1T 8 0K
2H T′ 2H ′ 1T

Δb/b0 (%)
MoS2 300 K
′
10 2H 6
1T MoSe2
2H ′
Δb/b0 (%)

4 HSE06
WS2
5 No vib.
WSe2 2 0K
300 K
0 MoTe2 0
–10 –5 0 5 10 15 20
WTe2 Δa/a0 (%)
–5 1T′
2H Figure 5 | Vibrational effects and hybrid functionals in MoTe2. This figure
shows the intersections of the MoTe2 2H and 1T0 free energies A(a,b,T)
–10 using different treatments of vibrational (vib.) effects and two exchange–
–10 –5 0 5 10 15 20
correlation functionals. The top curve (GGA–DFT, no vibrational effects)
Δa/a0 (%) corresponds to the MoTe2 countour in Fig. 4. Inclusion of vibrational free
energy at 0 K (that is, only the vibrational zero-point energy) and at 300 K
Figure 4 | Intersection contours of the 2H and 1T0 energy surfaces when
shifts the onset of the 1T0 regime closer to the origin. It can also be seen
varying the rectangular lattice constants a and b. The lattice constants a
from this figure that the use of the HSE06 DFT/Hartree–Fock functional in
and b are represented as percent engineering strains, normalized over the
lieu of PBE has a similar effect.
equilibrium lattice constants a0 and b0 of the lowest energy structure (2H in
all cases except WTe2). The lower-energy (that is, lower-U) phase is
labelled on each side of the contours.
Ucrystal:

From the contours in Fig. 4, it is also apparent that a 2H-1T0 Aða; bÞ ¼ Ucrystal ða; bÞ þ Avib ða; bÞ  Ucrystal ða; bÞ
transition might be most easily accessible in MoTe2 X 15   
1
under tension along the b axis. The remainder of the Results þ ‘ oi ða; bÞ þ kB T ln 1  e  ‘ oi ða;bÞ=kB T
section will find that the predicted phase boundary for MoTe2 i¼1
2
moves even closer to ambient conditions when including ð2Þ
thermal effects, more advanced treatments of electronic
exchange and correlation, and by generalizing the governing Since this approach samples 15 discrete values of oi at !, it does
thermodynamic constraints beyond the case of fixed lattice not take into account the full dispersion of phonon frequencies
constants. for arbitrary wave vectors in the Brillouin zone. Large supercell
calculations that sample the vibrational spectrum more finely (up
to 159 values of oi in a 3  3 supercell) reveal that the use of 15
phonons in equation (2) leads to errors under 3 meV per MoTe2
Thermal corrections in MoTe2. The data shown in Figs 2 and 4
formula unit when comparing 2H and 1T0 free energies
derive from the DFT-calculated potential energy U ¼ Ucrystal,
(Supplementary Fig. 1). This error is significantly smaller than
and therefore omit the vibrational component of free energy.
the 1T0 -2H’ Ucrystal energy difference of 43 meV.
This vibrational component can be important when the
Proceeding with the results of equation (2), the Lagrange
energy difference between phases is o0.1 eV, on the order of
interpolation procedure is carried out again at intermediate values
kBT. Figure 2 shows that the 1T0 -2H energy offset thus
of a and b. The top three curves in Fig. 5 show that the vibrational
calculated for MoTe2 is sufficiently small (43 meV) such that
correction Avib moves the PBE-calculated (a,b)-space free-energy
vibrational effects could have a role in the energetic ordering
crossing in MoTe2 to smaller strains. Indeed, a 0-K zero-point
of phases. For a temperature-controlled experiment, the
free-energy correction lowers the threshold strain by up to 0.01 in
Helmholtz free energy A(a,b,T) replaces U(a,b) as the relevant
some regions, and increasing the temperature from 0 to 300 K
thermodynamic potential. We perform this calculation
produces another shift of up to 0.02 in the same regions.
for MoTe2 by treating the DFT-calculated vibrational normal
modes as quantum mechanical harmonic oscillators47. We
shall see that these effects in MoTe2 have a considerable impact, Kinetic aspects of the MoTe2 phase transition. Thus far, our
even in the idealized T-0 K case because of contributions purely thermodynamic analysis does not provide information
from the vibrational zero-point energy, which can be regarded regarding the timescales required to observe a transition between
as a manifestation of the partially wavelike nature of the the 2H and the 1T0 phase. Experimental observation of a ther-
atomic nuclei. modynamically allowed transformation might not be feasible if a
In the case of 2H- and 1T0 -MoTe2, we calculate a temperature- large kinetic barrier renders it inaccessible. A Climbing-Image
dependent vibrational free-energy correction based on the Nudged Elastic Band48 calculation within GGA–DFT reveals a
frequency spectrum of the 15 nonzero !-point phonons 2H-1T0 energy barrier of 0.88 eV per formula unit in MoTe2 at
the equilibrium lattice constants of the 2H phase. In the
belonging to the rectangular cell of each phase. These phonon
Arrhenius kinetics picture with a characteristic frequency of
frequencies are obtained by applying linear-response theory to 10 THz, the timescale associated with this barrier is 50 s at room
the forces in perturbed unit cell configurations for all 7  7 (a,b) temperature. Although other factors such as interfaces, substrate,
grid points. We then add the quasi-harmonic vibrational free- temperature, strain and impurities are likely to alter the
energy correction Avib ¼ Uvib–TSvib to the potential energy transformation kinetics, this timescale suggests that this

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms5214 ARTICLE

transformation is likely to be observable in the room temperature A very useful constraint applies when one of the principal
laboratory. tensions is zero, for example, when sxx ¼ sxy ¼ 0 and syy is
nonzero. This condition might hold for a ribbon suspended over
Hybrid functional applied to MoTe2. Like many contemporary a trench. Considering the 2H-1T0 energy landscape in Fig. 4, it
computational materials studies, our results presented thus far would appear promising to apply a uniaxial stress along the b axis
rely heavily on the generalized gradient PBE40 functional for of MoTe2 in order to observe a phase transition. We therefore
electronic exchange and correlation effects. The development of study a system that is subjected to a specified uniaxial-load
new exchange–correlation functionals is a highly active field, and Fy ¼ qA/qb along the crystal’s special y axis, whereas the x-face is
a Hybrid PBE/Hartree–Fock approach known as the Heyd– treated as a free surface (that is, qA/qa ¼ 0). Applying the
Scuseria–Ernzerhof HSE06 (ref. 49) functional has recently appropriate Legendre transform to A for this case yields another
shown superior agreement with experimental results in Gibbs-like free energy Gy that acts as the governing thermo-
structural metal–insulator transition phase boundaries in Si50. dynamic potential.
To explore how HSE06- and PBE-based predictions differ in a
MoTe2 context, we recalculate the Ucrystal component of Gy ðFy ; TÞ ¼ A  Fy b ð4Þ
equation (2) using the HSE06 functional on the 7  7 grid of
In our data, the independent variables (Fy,T) can be mapped
PBE-relaxed geometries. The HSE06-based phonon spectrum is
to a uniaxial-load contour {a,b} ¼ {a(Fy,T),b(Fy,T)}, derived from
not recalculated for this work because of the formidable
the interpolated A(a,b,T) surface and its local derivatives. This
computational demands presently posed by high-quality HSE06
approach carries the microscopic assumption that both the 2H
calculations. Instead, the PBE-calculated frequencies are
and the 1T0 phases’ b axes point in the y direction.
reintroduced on top of the HSE06-calculated Ucrystal. The
A closely related case is that of fixed macroscopic uniaxial
bottom three curves in Fig. 5 show that use of the HSE06-
strain. In the macroscopic uniaxial-strain case, one assumes that
calculated Ucrystal brings the 2H-1T0 threshold strains even closer
the lattice constant a remains fixed at the same value for both
to the origin. At 300 K, the transition is predicted to be within 2%
phases, such that strain occurs along both phases’ b axis.
strain of the equilibrium 2H lattice constants.
Macroscopic uniaxial strain allows for two-phase coexistence
regimes with crystallographic coherence between the 2H and 1T0
Alternative thermodynamic constraints. Some careful con- phase. Macroscopic uniaxial strain is also relevant if the
sideration of the relevant thermodynamic constraints is war- substrate–TMD interaction is strongly anisotropic. The strain
ranted here for the case of monolayers. The thermodynamic eyy ¼ /bS/b0  1 is termed macroscopic because b is the
constraint of fixed lattice constants used in Figs 4 and 5 is an weighted average over two different lattice constants /bS when
unusual one (different from constant volume or area) that is strained 2H and 1T0 phases coexist. In an experiment, changes in
perhaps most applicable when crystallographic coherence is b are proportional to the macroscopic extension of the sample.
maintained with a strongly binding substrate. At some fixed Additional thermodynamic ensembles may be applicable for
temperature T, the Helmholtz free energy A(a,b,T) is the ther- monolayers. For example, when a monolayer is weakly bound to a
modynamic potential whose minimization determines which substrate with friction, the atoms are allowed to move to some
crystal phase (or coexistence of phases) will exist in a crystal limited extent and restricted by contact with the surface. The
possessing a rectangular unit cell with dimensions a  b. How- thermodynamic potential of the TMD monolayer will be some
ever, this fixed-cell constraint certainly need not apply when intermediate case between the constant-force case (applicable to a
friction with the substrate is weak, or when the monolayer is frictionless substrate) and the fixed-(a,b) case where friction is
freely suspended. In analogy with the important distinction large enough to inhibit significant movement of the metal atoms.
between constant-pressure and constant volume experiments in
bulk materials, we now show how to generalize our MoTe2 results
Alternative thermodynamic constraints applied to MoTe2. Both
to other thermodynamic constraints with stable two-phase
the hydrostatic and uniaxial-load contours are displayed in Fig. 6a
coexistence regions.
(PBE-calculated Ucrystal) and Fig. 6b (HSE06-calculated Ucrystal).
Perhaps the simplest thermodynamic constraint occurs when
When increasing Fy or s, at some point the Gibbs free energies of
both in-plane principal tensions are equal, such that sxx ¼ syy.
the 2H and 1T0 phases cross. When that happens, the resulting
This isotropic-tension condition is analogous to the isotropic
phase transition can be seen as a discontinuous jump in (a,b)-space
constant-pressure case in three dimensions. The natural thermo-
from the 2H to the 1T0 contour. It is interesting to note that at
dynamic potential governing this isotropic-load system (that is,
precisely this transition load, any mixed-phase coexistence of both
the potential that is minimized) is a ‘hydrostatic’ Gibbs free
phases ranging from 100% 2H to 100% 1T0 is thermodynamically
energy Ghydro, where the surface tensions sxx ¼ syys and
stable. Figure 7 illustrates the general concept of mixed-phase
sxy ¼ 0:
regimes when a monolayer is progressively tensioned, for example,
by increasing Fy or /bS (for the uniaxial stress/strain case), or by
Ghydro ðs; T Þ ¼ A  abs ð3Þ increasing hydrostatic stress s or the unit cell area ab.
In the uniaxial-load case for MoTe2, the calculated strains
The previously independent variables (a,b,T) used in A ¼ A(a,b,T) eyy ¼ b/b0–1 required to enter the 2H end of this transition regime
are now a function of (s,T) through the definition of a 2D are shown in Fig. 8a. It is striking that the choice of exchange–
hydrostatic contour {a,b} ¼ {a(s,T),b(s,T)}. This contour is correlation functional and the treatment of atomic vibrations
determined directly from the interpolated A(a,b,T) surface and have a large impact on this number: eyy ranging from 0.5%
its local derivatives (for example, using sxx ¼ (1/b)qA/qa). (HSE06, 300 K) to 2.4% (PBE, no vibrational free energy).
Another physically relevant constraint is that of constant area. Figure 8b shows that the strain on the 2H end of the hydrostatic
This is closely related to a constant volume constraint for bulk transition is similarly sensitive to temperature and electronic
materials. Such a constraint can lead to mixed-phase regimes. exchange–correlation functional. The discrepancy between PBE
Constant area is a macroscopic constraint that might be and HSE06 shows a clear path towards experimentally addressing
applicable when the edges of a freely suspended monolayer are the question of which functional is better suited for 2D materials
clamped in place to fix the area, independent of stress. studies.

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a 10 b 6
Fy
1T′ 1T′
8
0 0
4

Δb/b0 (%)

Δb/b0 (%)
6 
Fy
4  
2
2 
2H 2H
0 0
–5 0 5 10 –5 0 5 10
Δa/a0 (%) Δa/a0 (%)

Figure 6 | Load-specific trajectories and transitions of MoTe2 at 300 K. Panel a uses the PBE functional to calculate the crystal energy, whereas the
HSE06 functional is used in b. Starting at their stress-free 2H equilibrium values a0 and b0, the lattice constants a and b evolve in response to progressive
application of a uniaxial-load (Fy) or a ‘hydrostatic’ isotropic tension (s). At a certain load, the 2H and 1T0 thermodynamic potentials cross. When this
transition occurs, the lattice constants jump from their 2H to their 1T0 values. A coexistence regime is expected to exist in the dashed regions, where
increasing the b lattice constant while keeping Fx ¼ 0 (uniaxial load) or increasing the area ab under hydrostatic conditions can yield regions of 2H and 1T0 in
the monolayer. Although the solid trajectories appear to be mostly rectilinear, they represent an aggregate of finely sampled data points travelling along the
Lagrange interpolation surface.

a b 2H transition 1T′ transition

strain strain
3
1T′
Free energy

3
2
2H
2H 1T′ 2H Transition
force
1
expanding
2 substrate / gap
c 1T′
3
2 Transition
Force

force
2H
Mixed
1 phase
1

Extension

Figure 7 | Phase coexistence under an applied force or extension. A tensile mechanical deformation (for example, hydrostatic, uniaxial load or uniaxial
strain) expands a region of the TMD monolayer. This strained region can be freely suspended or locally sliding over a low-friction substrate, as shown in a.
The 2H/1T0 Helmholtz free energy landscape b is traversed in this process. In step 1, the 2H phase deforms elastically and no phase transition is observed.
Beyond some critical strain in step 2, the lowest free-energy path is a common tangent between the 2H and 1T0 energy surfaces, manifesting a coexistence
regime where both phases are coexisting in mechanical equilibrium. If the experimental setup is such that the extension is controlled (for example, using a
stiff AFM probe), this region is observed as a plateau in the applied force c. At the strain level of step 3, the lowest energy phase is composed of 100% 1T0,
completing the mechanically induced phase transition.

The accuracy of these predictions of small transition strains These strains are obtained from 1D cubic fits (illustrated in
based on 2D interpolation is validated using additional calcula- Supplementary Fig. 4) on the refined 10  10 grid of DFT-
tions in the case of MoTe2. We run a 10  10 grid of PBE, phonon calculated energies, at fixed lattice constant a ¼ 3.550 Å and
and HSE06 calculations in a region in (a,b)-space with axial varying b. Supplementary Figure 5 summarizes all uniaxial-load
strains ranging from  5 to 10%. This new data set is three times and uniaxial-strain results based on this 10  10 grid.
as fine as the 7  7 grid and also includes PBE-calculated
phonons. Coexistence regimes are extracted from a series of 1D
fits on this refined grid, as illustrated in Supplementary Fig. 2. The Discussion
typical difference between uniaxial-load transition strains from Recent calculations and AFM experiments43 have demonstrated
this approach and the equivalent strains from the 2D Lagrange- that a MoS2 monolayer can be subjected to 20% equibiaxial strain.
interpolating method used throughout the main text is 0.002 for In these experiments, a pre-tensioned MoS2 sheet is pushed into a
HSE06 and 0.005 for PBE (Supplementary Fig. 3). circular cavity by means of an AFM probe. These experiments
In the case of macroscopic uniaxial strain at 300 K (not shown report no evidence of a phase transition, but do report the
in Fig. 8), the HSE06 functional predicts an onset of the presence of sufficiently large equibiaxial deformations (Fig. 4) in
coexistence regime at 1.6% strain, whereas PBE predicts 3.0%. the small region under the AFM tip. The indentation timescale

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms5214 ARTICLE

a b 10
2.5 Fy 

yy(xx = 0) at onset of 2H→1T′ transition (%)

(xx =yy) at onset of 2H→1T′ transition (%)

2 0 0 8  

HSE06
PBE
1.5 Fy 6 

HSE06
PBE

HSE06
1 4

HSE06

PBE

HSE06
PBE

PBE

HSE06
0.5 2

PBE
0 0
No. vib. 0K 300 K No. vib. 0K 300 K
0
Figure 8 | Strain at onset of load-specific 2H to 1T transitions in MoTe2. This figure is closely related to Fig. 6. The application of a uniaxial load or
isotropic tension affects the relative thermodynamic potential of the 2H and 1T0 phases. The strains plotted here are the predicted maximum strains in 2H
before transformation to 1T0 is thermodynamically possible. The chart in a shows the threshold strains eyy ¼ Db/b0 under uniaxial load. The equibiaxial
threshold strains e ¼ Da/a0 ¼ Db/b0 under isotropic tension are shown in b. It can be seen that the choice of exchange–correlation functional as well as the
treatment of vibrational (vib.) free energy have a marked effect on these strain values.

(B1 s) may be too short to observe a transition, perhaps even percentage points. The error in our calculated MoTe2 lattice
more so because the AFM tip may increase the 2H-1T0 transition constants is unknown because no experimental lattice constants
energy barrier. On the other hand, this reference43 does note that for 2H and 1T0 monolayers have been reported (to the best of our
the majority of samples show a significant force–displacement knowledge). Since our research compares crystal structures
hysteresis that is attributed to slipping, but which might indicate a having the same chemical composition, we believe that the DFT
phase transition in light of the present study. error in lattice constants will be systematic across different
Although widely studied today, MoS2 monolayers are not phases, leading to a partial cancellation of errors in transition
ideally suited for phase transitions because MoS2 has the greatest strains.
1T0 -2H energy difference of all group VI TMDs. 2H-1T0 Spontaneous ripple formation has been observed in MoS2
structural phase transitions are closest to ambient conditions in (refs 44,45). These ripples (which are expected to exist in other
the case of MoTe2. This property makes MoTe2 more suitable for TMDs as well) render the presence of significant compressive
technological applications and is hoped to motivate further principal stresses in monolayers unlikely, reducing the possibility
advances in telluride TMD growth techniques. of observing a 1T0 to 2H transition in WTe2 (Fig. 4). Another
In the case of MoTe2, certain classes of strain states are more technical consequence of pre-existing ripples is that some
likely to yield a phase transition than others. Based on the local additional strain may be required before the mechanical stresses
characteristics of the MoTe2 phases’ energy landscape, our needed for a phase transition are present.
research identifies the application of tension along the 2H phase The goal of this study is to investigate the possibility of a
b axis (armchair) as a fertile route to observing a phase transition. mechanical route to thermodynamically driven phase transfor-
As a general trend, the deformations associated with this mations between metal and semiconducting crystal structures in
transition appear to be brought closer to zero with increasing all group VI TMDs. Our results show that these mechanical
temperature. At room temperature, we predict that the lowest transformations are in fact possible and most easily accessible in
strain eyy needed to render the 1T0 phase stable lies between 0.3% the case of MoTe2. With this information, we are optimistic that
(HSE06, uniaxial load) and 3% (PBE, uniaxial strain). The values mechanically induced phase transitions can be achieved using
quoted above are computed from the refined 10  10 grid of DFT flexible substrates, AFM techniques and other standard experi-
calculations. We note that the calculated insulator-to-metal mental approaches. This thorough understanding of phases and
strains in monolayer MoTe2 compare favourably with insulator- phase boundaries in TMD monolayers is a critical step towards
to-insulator transition strains reported for bulk VO2 (ref. 51), building our understanding of the rich physics of 2D materials.
which has no known 2D form. Furthermore, the existence of multiple phases in monolayers is an
Stress and strain could be applied to a TMD monolayer via exciting feature beyond graphene that undoubtedly has broad
deformation of a flexible substrate. Another approach, which implications for electronic, Nanoelectromechanical systems
might yield more quantitative evidence of the transition process, (NEMS), thermal, energy and myriad other devices that can all
is to perform an experiment where an AFM probe pushes down benefit from the flexible, transparent nature of monolayers.
a freely suspended MoTe2 monolayer with its armchair axis
pointing across a trench as shown in Fig. 7.
As with all DFT calculations, the equilibrium 2H and 1T0 Methods
Electronic structure calculations. DFT and hybrid DFT calculations were per-
lattice constants calculated in this work are expected to exhibit formed using the Projector-Augmented Wave52,53 pseudopotential implementation
discrepancies with experimental lattice constants on the order of of the Vienna Ab Initio Simulation Package54, version 5.3.3. In the DFT
1%. For example, our DFT-calculated 2H-MoS2 monolayer lattice calculations, electron exchange and correlation effects are described by the GGA
constant a of 3.18 Å is within 2% of measured values from 3.1 to functional of PBE40. Wave functions are expanded in a plane-wave basis set with a
kinetic energy cutoff of 350 eV on an 18  18  1 Monkhorst-Pack55 k-point grid
3.2 Å in chemically grown MoS2 (ref. 27). A discrepancy in the using a Gaussian smearing of 50 meV. The convergence thresholds were
actual location of energy minima in (a,b)-space will offset the 0.5  10  6 eV per MX2 and 0.5  10  5 eV per MX2 for electronic and ionic
strains needed to achieve phase transitions by a similar amount in relaxations, respectively. The linear-response phonon calculations use an electronic

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms5214

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms5214 ARTICLE

55. Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Author contributions
Phys. Rev. B 13, 5188–5192 (1976). E.J.R. and K.-A.N.D. designed the simulations and the framework for thermodynamic
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Acknowledgements
Our work was supported in part by the US Army Research Laboratory, through the Army
High Performance Computing Research Center, Cooperative Agreement W911NF-07- Additional information
0027, and by computer and software support provided by the U.S. Army Engineer Supplementary Information accompanies this paper at http://www.nature.com/
Research and Development Center, Department of Defense Supercomputing Research naturecommunications
Center (ERDC DSRC). This work was also supported by Defense Advanced Research
Projects Agency Young Faculty Award (DARPA YFA) grant N66001-12-1-4236, and used Competing financial interests: The authors declare no competing financial interests.
resources of the National Energy Research Scientific Computing Center (NERSC), which Reprints and permission information is available online at http://npg.nature.com/
is supported by the Office of Science of the US Department of Energy under contract no. reprintsandpermissions/
DE-AC02-05CH11231. Some calculations were performed in part using the Stanford
NNIN Computing Facility (SNCF), a member of the National Nanotechnology Infra- How to cite this article: Duerloo, K.-A.N. et al. Structural phase transitions in
structure Network (NNIN), supported by the National Science Foundation (NSF). two-dimensional Mo- and W-dichalcogenide monolayers. Nat. Commun. 5:4214
K.-A.N.D. is supported by a Gerhard Casper Stanford Graduate Fellowship. doi: 10.1038/ncomms5214 (2014).

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