Applied Physics Letters ARTICLE scitation.

org/journal/apl

Ab initio simulation studies on the room-temperature

ferroelectricity in two-dimensional b-phase GeS
Cite as: Appl. Phys. Lett. 114, 192903 (2019); doi: 10.1063/1.5097425
Submitted: 25 March 2019 . Accepted: 6 May 2019 .
Published Online: 17 May 2019

Huabing Yin,1,2 Chang Liu,1 Guang-Ping Zheng,2,a) Yuanxu Wang,1,a) and Fengzhu Ren1

AFFILIATIONS
1
Institute for Computational Materials Science, School of Physics and Electronics, Henan University, Kaifeng 475004, China
2
Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hong Kong 999077, China

a)
Electronic addresses: [email protected] and [email protected]

ABSTRACT
Stable ferroelectricity with an in-plane spontaneous polarization of 2.00  1010 C/m is found in two-dimensional (2D) b-GeS monolayers
from theoretical calculations, which can be effectively tuned by the applied tensile strains. The Curie temperature of the monolayer is evalu-
ated to be 358 K by ab initio molecular dynamics simulations. Remarkably, the 2D ferroelectricity is found to exist in 2D few-layer b-GeS
nanosheets which could be synthesized in experiments. The strong spontaneous polarization and giant pyroelectric coefficient accompanied
by the appearance of phase transition near room temperature facilitate the development of b-GeS monolayers or nanosheets for applications
in ferroelectric, pyroelectric, and piezoelectric devices with superior performance.
Published under license by AIP Publishing. https://doi.org/10.1063/1.5097425

When the thickness of bulk ferroelectrics is reduced to nano- monochalcogenides, including a-SnS, a-GeSe, and a-GeS, with the
meters, such as 1.2  2.4 nm for perovskite compounds,1–3 the unin- theoretical Ps of 2.62  10105.06  1010 C/m, also exhibit signifi-
tended depolarization field may lead to the disappearance of cantly higher Tc than room temperature, i.e., 1200  6400 K.12 Such
ferroelectricity in the material. It is hoped that two-dimensional (2D) high phase transition temperatures possibly restrict the application of
layered materials provide a new perspective to retain the functional those 2D materials in some practical applications, such as pyroelectric
properties of ferroelectrics when thinned to a few atomic layers,4,5 and and electrocaloric devices,19–22 which usually show the best performance
the ferroelectricity is strongly expected to exist in 2D materials. around Tc. Normally, it is hoped that those devices could be operated
Recently, 2D ferroelectric materials have been reported. In experi- near room temperature. Therefore, the 2D ferroelectric materials with
ments, ferroelectricity has been found to exist in 1-unit cell thick SnTe appropriate Ps and Tc are still missing or need to be augmented.
films and 2D CuInP2S6 films with a Curie temperature (Tc) close to In this letter, using first-principles density functional theory
room temperature.6,7 The ferroelectricity of a-In2Se3 has been found (DFT) together with AIMD simulation, we systematically investigate
to exhibit the intercorrelated out-of-plane and in-plane polariza- the ferroelectricity in 2D b-phase GeS, which has the attributes in terms
tions,8,9 confirming the theoretical predictions. Transformed from of crystal structure, stacking form, and electronic properties similar to
b-In2Se3, the b0 phase has been discovered to possess an in-plane fer- the recently synthesized b-GeSe.23 All calculations are performed by
roelectricity stable up to 473 K.10 Meanwhile, based on theoretical using the VASP code,24–26 and the computational details are provided
methods, some atom-thick 2D materials, such as 1T-MoS2,5 group-IV in the supplementary material. Our calculations show that the b-GeS
or III–V binary compounds,11 a-phase group-IV monochalcoge- monolayer has a strong in-plane Ps of 2.00  1010 C/m, which is
nides,12 group-IV tellurides,13 AgBiP2Se6,14 GaTeCl,15 b-GeSe,16 larger than that of monolayer b-GeSe and SnTe and can be enhanced
group-V elemental monolayers,17 and phosphorene-like a-SbN and by the applied tensile strains. Meanwhile, its Tc of 358 K predicted by
a-BiP binary monolayers,18 have been systematically investigated and the AIMD simulations is close to room temperature. The ferroelectric-
some of them are found to exhibit amazing ferroelectricity. ity of b-GeS can be maintained in 2D nanosheets with odd numbers of
Remarkably, the ab initio molecular dynamics (AIMD) simulation monolayers. In addition, monolayer b-GeS exhibits giant pyroelectric
showed that the spontaneous polarization (Ps) of monolayer a-SbN and piezoelectric responses. These extraordinary properties ensure that
can be retained with the increase in temperature until the melting 2D b-GeS has a wide range of applications in ferroelectric, pyroelectric,
point, such as 1700 K.18 In addition, previously reported 2D group-IV and electrocaloric devices.

Appl. Phys. Lett. 114, 192903 (2019); doi: 10.1063/1.5097425 114, 192903-1
Published under license by AIP Publishing
 Applied Physics Letters ARTICLE scitation.org/journal/apl

We focus our attention on the homogeneous monolayer b-GeS,

with a space group Pmn21. Herein, the structural definition of b-phase
GeS follows that of b-GeSe recently synthesized in experiments,23,27
whose structure is exactly identical to that of c-phase phosphorenelike
group-V monolayers.28–30 More structural descriptions can be found
in the supplementary material, and the comparison of the structures
of phosphorene and the GeS monolayer is shown in Fig. S1. The opti-
mized conformation of monolayer b-GeS is displayed in Fig. 1(a),
whose lattice constants a and b are 5.68 Å and 3.51 Å, respectively, in
good agreement with the previously calculated values.27,31 The phonon
spectrum without an appreciable imaginary phonon mode as shown
in Fig. 1(b) confirms the thermodynamic stability of monolayer
FIG. 2. (a) Two distorted degenerate ferroelectric states (phases B and B) and an
b-GeS. Very similar to b-GeSe, bulk layered b-GeS may be experimen- undistorted nonpolar structure (phase A). The in-plane displacements along the x
tally synthesized from its polymorphs and could be stable under ambi- direction of the two nearest neighbor Ge and S atoms are labeled as d1 and d2,
ent conditions. Meanwhile, its monolayer can be possibly obtained respectively. Polarization directions are indicated by red arrows. (b) The free-
through exfoliation, which is usually used to peel thin flakes from lay- energy contour for b-GeS monolayer vs the x direction displacements d1 and d2.
ered bulk crystals, such as graphene and phosphorene.32,33 As shown
in Fig. 1(c), the band structure indicates that monolayer b-GeS is an methods vs the x direction displacements of d1 and d2 is displayed in
indirect bandgap material, and both the conduction band minimum Fig. 2(b), manifesting the stable phases B (with d1 ¼ d2 ¼ 0.306 Å)
(CBM) and the valence band maximum (VBM) are located along the and B (with d1 ¼ d2 ¼ 0.306 Å) with opposite Ps. In a typical polari-
CY line. The energy bandgap in the semilocal PBE functional is zation reversal process, such as that changed from phase B to phase
about 1.77 eV, which is known to be underestimated considerably. B, the reversal path is strictly along the dashed line shown in Fig.
When the HSE hybrid functional is adopted to describe the electronic 2(b), retaining the relation of d1 ¼ d2. Therefore, saddle point A
structure, we obtain a relatively large bandgap of 2.53 eV, close to the between phases B and B is shaped, corresponding to a centrosymmet-
GW result of 3.08 eV.27 It is worth noting that the electronic properties ric nonpolar state. This double-well free-energy in monolayer b-GeS
of this category of monolayer b-phase group-IV monochalcogenides typically indicates the possibility of its application as ferroelectric
have been discussed adequately in previous studies,27,31 such as the materials. Figure 3(a) shows the phonon spectrum of the nonpolar
properties of saddle-point excitons. phase A. Compared with that of the distorted polar phase B or B [see
As shown in Fig. 2(a), phases A, B, and B indicate an undis- Fig. 1(b)], the phonon spectrum exhibits a prominent imaginary
torted nonpolar state and two noncentrosymmetric distorted degener-
ate ferroelectric states of the monolayer, respectively, which were
previously well defined in the investigation of ferroelectricity in other
similar 2D materials.12–17 The free-energy contour calculated by DFT

FIG. 1. (a) Top and side views of the optimized structure of monolayer b-GeS. The
armchair and zigzag directions are defined as the x and y directions, respectively.
The orthogonal unit cell used in calculations is outlined by dashed lines. (b) Phonon FIG. 3. (a) Phonon spectrum of the centrosymmetric phase A of monolayer b-GeS.
spectrum of monolayer b-GeS. (c) Calculated DFT band structure of monolayer (b) Double-well potential vs polarization of monolayer b-GeS. The polarization Ps
b-GeS by using Perdew-Burke-Ernzerhof (PBE) (black lines) and Heyd-Scuseria- and potential barrier EB are all labeled. The fitting curve (red line) is based on the
Ernzerhof (HSE) (red lines) functionals, respectively. The blue arrow indicates the Landau model. (c) EB and (d) Ps under the applied uniaxial (along the armchair or
position of the HSE bandgap, and the valence band maximum is set at zero energy. zigzag direction) and biaxial strains.

Appl. Phys. Lett. 114, 192903 (2019); doi: 10.1063/1.5097425 114, 192903-2
Published under license by AIP Publishing
 Applied Physics Letters ARTICLE scitation.org/journal/apl

frequency of the k mode at the C point for phase A, which is usually a

signature of displacive instability and shows a general tendency of the
phase transition from a centrosymmetric state to a non-centrosymmetric
state below Tc.
As calculated by the Berry phase method (see Fig. S2 in the sup-
plementary material), the in-plane Ps of the b-GeS monolayer is
2.00  1010 C/m along the x axis, which is relatively small compared
to that (5.06  1010 C/m) of the a-GeS monolayer,12 while it is larger
than that of the homogeneous b-GeSe monolayer (1.59  1010 C/m).16
The results can be explained by the correlation between Ps or structure
distortions and the chemical bonding nature such as bond covalency
and cophonicity, as proposed by Fei et al.12 Assuming the effective thick-
ness of 4.12 Å for the monolayer,27 the in-plane Ps value of 0.49 C/m2
can be estimated for the b-GeS monolayer.
Furthermore, we calculated a series of free energies and polariza-
tions P in the process of phase transition along the displacement-
covariant line, d1 ¼ d2 ¼ d, as shown in Fig. 2(b). Based on the phe-
nomenological Landau–Devonshire theory, the free energy U ¼ a2 P2
þ b4 P4 þ 6c P6 with a ¼ 39.66, b ¼ 1.206, and c ¼ 2.894 can be
obtained, where U and P are in units of millielectron volts per cell and
1010 C/m, respectively, as shown in Fig. 3(b). The energy barrier EB
between the ferroelectric and paraelectric states can be found to be
around 53.3 meV, which is larger than that of the b-GeSe monolayer
(11.66 meV). In addition, as shown in Fig. S3 in the supplementary
FIG. 4. (a) Temperature dependence of spontaneous polarization obtained from
material, a perfect double-well potential vs displacement d along the x AIMD simulations for the b-GeS monolayer. (b) Thermal evolution of atomic dis-
direction is also obtained. The energy barrier of such double-well placements along the x direction between adjacent Ge and S atoms. The data are
potential is in good agreement with EB. It is noteworthy that EB is one collected from sampling the AIMD equilibrium structures at 100 K, 300 K, and
order of magnitude smaller than that of other frequently used ferro- 600 K, respectively. (c) Pyroelectric coefficient (dP=dT) of the b-GeS monolayer.
electrics such as PbTiO3,34 suggesting that a rather smaller electric field (d) Piezoelectric response (relaxed-ion e11 coefficient) calculated from the DFT
method. The polarization and uniaxial strain e11 are all along the x direction. The
is required for the polarization reversal. corresponding relaxed-ion piezoelectric coefficient e11 can be obtained from the
The ferroelectricity of monolayer b-GeS under applied in-plane slope of the line.
biaxial and uniaxial tensile strains is further explored. Figures 3(c) and
3(d) present the strain dependent Ps and EB of monolayer b-GeS,
interaction among the neighboring unit cells. Compared with
respectively. Clearly, Ps and EB increase with increasing in-plane
another well-studied allotrope of the a-GeS monolayer with EB
strains, which are attributed to the increase in x direction displace-
¼ 580.77 meV and Tc ¼ 6400 K,12 the obviously smaller Tc ¼ 358 K
ments d1 and d2 between adjacent Ge and S atoms. When a 7% biaxial
near room temperature for b-GeS could mainly result from its much
strain is applied, Ps can be enlarged to 2.47  1010 C/m. Thus, Tc of
smaller energy barrier EB ¼ 53.3 meV. Moreover, Fig. 4(b) presents
the monolayer b-GeS could be effectively tuned since EB is of strong
the thermal effects on the in-plane atomic displacements along the x
strain dependence.
direction, indicating that the probability distribution of displacement
Besides the phenomenological model described above, AIMD
strictly obeys a Gaussian function. At low temperature, 100 K, the
simulations are performed to study the phase transition between ferro-
electric and paraelectric phases of the b-GeS monolayer. From the distribution exhibits a sharp peak with an average displacement d of
AIMD calculations, we can determine the Ps value from the average around 0.306 Å, corresponding to a ferroelectric phase. However,
P PN with increasing temperature, the peak broadens homogeneously.
displacement d obtained by using the formula d ¼ M1 N1 M i¼1 j¼1 Near Tc, the broadened peak will shift to the place with an average
ðdijGe  dijS Þ, where ðdijGe  dijS Þ is the x direction coordinate difference displacement d of around zero, corresponding to a nonpolar phase,
between the nearest neighbor Ge and S ions. M is the number of con- which apparently verifies the occurrence of phase transition between
figuration snapshots extracted from the equilibrium AIMD trajectories ferroelectric and paraelectric phases in the b-GeS monolayer. More
(see Fig. S4 in the supplementary material), and N is the number of GeS importantly, near Tc, the significant broadening of the in-plane
ion pairs in the supercell. The geometric configurations of the b-GeS atomic displacements along the x direction with a root-mean square
monolayer at 100 K, 300 K, and 600 K are shown in Fig. S5 in the sup- (RMS) value close to d implies that the soft-mode phonons related to
plementary material. Figure 4(a) shows Ps as a function of temperature. the lattice vibration along the x direction could also be responsible
At T ¼ 0 K, d ¼ 0.306 Å corresponds to Ps ¼ 2.00  1010 C/m, for the relatively low Tc of b-GeS.
which is maintained up to about 300 K. The Curie temperature Tc The pyroelectric and piezoelectric responses of the b-GeS
¼ 358 K can be determined by fitting Ps vs temperature T as Ps ðT Þ monolayer are quantitatively determined from the AIMD results.35
¼ a=ð1 þ ekðTTc Þ Þ, where a and k are constants. The value of Tc is Figure 4(c) shows the pyroelectric coefficient p ¼ ðdP=dTÞ . Near
usually influenced by the energy barrier EB and the dipole-dipole Tc ¼ 358 K, p could be as high as 7300 lC/Km2 when we considered

Appl. Phys. Lett. 114, 192903 (2019); doi: 10.1063/1.5097425 114, 192903-3
Published under license by AIP Publishing
 Applied Physics Letters ARTICLE scitation.org/journal/apl

the effective thickness of 4.12 Å for monolayer b-GeS.27 Moreover, ferroelectric materials and can also be enhanced by applied tensile
the piezoelectric coefficient e11 is determined by a linear fitting of 2D strains. Meanwhile, the ferroelectricity can be maintained in 2D b-GeS
polarization changes along the x direction with respect to the uniax- nanosheets containing odd numbers of monolayers. As predicted
ial strains e11 along the x direction. As indicated in Fig. 4(d), a linear from ab initio simulations, the strong polarization (0.49 C/m2) and
relation between polarization changes and strains within 61% has giant pyroelectric coefficient (7300 lC/Km2) at room temperature
been found for the b-GeS monolayer. The piezoelectric e11 coefficient shed light on the applications of the b-GeS monolayer in sensors,
is determined to be about 7.51  1010 C/m, which is twice larger actuators, and energy harvesters with superior performance.
than that of the MoS2 monolayer (e11 ¼ 3.64  1010 C/m).36 The
active pyroelectric and piezoelectric responses in the b-GeS mono- See the supplementary material for the computational details,
layer suggest that it has a wide range of applications in sensors and structural definition of b-phase GeS, comparison of the identical struc-
energy conversion devices. Particularly, the giant pyroelectric coeffi- tures of phosphorene and the GeS monolayer in Fig. S1, Berry phase
cient is larger than those of most ferroelectric bulk crystals, sugges- polarization calculation result of the b-GeS monolayer in Fig. S2,
ting that the device containing b-GeS monolayers could have double-well potential vs displacements along the x direction in Fig. S3,
superior pyroelectric performance. temperature variations with time in AIMD calculations in Fig. S4, and
For 2D layered materials, the few-layer nanosheets are easily syn- final geometric configurations of the b-GeS monolayer after perform-
thesized and generally applied in device applications. Herein, we have ing 5000 fs AIMD simulations in Fig. S5.
also studied the ferroelectric behavior of few-layer 2D b-GeS. Very
similar to b-GeSe nanosheets,23 the b-GeS nanosheet shown in Fig. This work was supported by the National Natural Science
5(a) employs a stacking mode of opposite orientation for alternating Foundation of China (Grant Nos. 21603056 and 11674083), the Hong
monolayers, which is verified to possess the lowest free energy by our Kong Scholars Program (No. XJ2016045), the Project of Scientific
theoretical calculation. Figure 5(b) shows Ps as a function of numbers Research Fund in Henan University (No. YQPY20170076), the Henan
of monolayers N. The 2D b-GeS nanosheets with even numbers of International Science and Technology Cooperation Project (No.
layers could be nonferroelectric because of the existence of inversion 182102410096), and a grant from the Research Grants Council of the
symmetry in their structure. In contrast, the spontaneous polarization Hong Kong Special Administrative Region, China (No. PolyU 152190/
can arise naturally in the 2D b-GeS nanosheets with odd numbers of 18E).
monolayers because of the loss of centrosymmetry. Similar N-depen-
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Appl. Phys. Lett. 114, 192903 (2019); doi: 10.1063/1.5097425 114, 192903-5
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Ab initio simulation studies on the room-
temperature ferroelectricity in two-
dimensional β-phase GeS
Cite as: Appl. Phys. Lett. 114, 192903 (2019); https://doi.org/10.1063/1.5097425
Submitted: 25 March 2019 . Accepted: 06 May 2019 . Published Online: 17 May 2019

Huabing Yin , Chang Liu, Guang-Ping Zheng , Yuanxu Wang , and Fengzhu Ren

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 Ab initio simulation studies on the room-temperature ferroelectricity
in two-dimensional β-phase GeS

Huabing Yin,1,2 Chang Liu,1 Guang-Ping Zheng,2,* Yuanxu Wang,1,** and Fengzhu Ren,1

1
Institute for Computational Materials Science, School of Physics and Electronics, Henan
University, Kaifeng 475004, China.

2
Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hong Kong
999077, China.

*
Email: [email protected]

**
Email: [email protected]

Computational details

The first-principles DFT calculations with the generalized gradient approximation (GGA) of
Perdew-Burke-Ernzerhof (PBE) functional are performed by using VASP code.1-4 A plane-wave
basis set along with energy cutoff of 500 eV is used to describe electron wavefunctions. A
10×15×1 Monkhorst-Pack grid has been employed to sample the Brillouin zone.5 The
convergence criteria for electronic and ionic relaxations are set as 10-6 eV and 0.005 eV/Å,
respectively. Moreover, a 20 Å vacuum space along z-direction is added to model the
characteristics of 2D materials. We adopt density functional perturbation theory (DFPT) method
in the PHONOPY code to calculate the phonon dispersion,6 where a 5×5×1 supercell is used. To
be more precise in the prediction of band gap, the Heyd-Scuseria-Ernzerhof (HSE) hybrid
functional is used to determine the band structure.7 Particularly, in the calculations on the few-
layer 2D materials, we employ the DFT-D2 method with inclusion of van der Waals
interactions.8 The modern theory of polarization based on the Berry phase approximation is
carried out to directly calculate the spontaneous electric polarization.9 The AIMD simulation is
performed on a 7×7×1 supercell with 198 atoms, and a NVT ensemble with the Nosé-Hoover
thermostat is chosen to simulate the thermal effects.10 We run AIMD simulations up to 5000 fs

1
with a time step of 1 fs and evaluate the electric polarization for the thermodynamic equilibrium
configuration by statistical average method.

Structural definition of β-phase GeS

There are two viewpoints on the naming of Group-IV Monochalcogenides (SnSe, SnS,
GeSe, and GeS) polymorphs. For the GeS polymorph studied in this work, it was denoted as γ-
phase GeS which followed the definitions of phosphorene-like group-V monolayers (α-, β-, γ-, δ-,
and ε-phase) as described by Zhang et al.;11, 12 Alternatively, it was called β-phase GeS, which
followed the definition on the recently synthesized β-GeSe.13-15 Herein, β-GeS is adopted to
denote the GeS polymorph studied, whose structure is the same as that of γ-phase phosphorene
and other group-V monolayers.11, 16 The comparisons between the structures of α-phase and γ-
phase phosphorenes with those of α-phase and β-phase GeS monolayers are shown in Fig. S1.

Fig. S1. Comparison of the structures of (a) α-phase phosphorene, (b) γ-phase phosphorene, (c)
α-phase GeS monolayer, and (d) β-phase GeS monolayer.

2
Fig. S2. Berry phase polarization calculation of β-GeS monolayer. The undistorted nonpolar
paraelectric phase is with 0% distortion, and two distorted degenerate ferroelectric phases are
with −100% and 100% distortions, respectively. The spontaneous polarization Ps is determined
to be 2.00 × 10-10 C/m. The polarization quanta Pq is 4.56 × 10-10 C/m.

Fig. S3. Double-well potential vs. displacement d along x direction for β-GeS monolayer. Green
points are the DFT-calculated total energy and the red line is the fits from the Landau model.

3
Fig. S4. Temperature variations with time for β-GeS monolayer in AIMD calculations at 100K,
300K, and 600K.

Fig. S5. The geometric configurations of β-GeS monolayer after 5000 fs in AIMD simulations at

(a) 100K, (b) 300K, and (c) 600K.

4
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