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Perovskenes: two-dimensional perovskite-type

monolayer materials predicted by first-principles
Cite this: DOI: 10.1039/d3cp04435a
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calculations†
Mosayeb Naseri, *ab Shirin Amirian, b Mehrdad Faraji, c

Mohammad Abdur Rashid, d Maicon Pierre Lourenço, e

Venkataraman Thangadurai f and D. R. Salahub *a

Inspired by the successful transfer of freestanding ultrathin films of SrTiO3 and BiFeO3 onto various
substrates without any thickness limitation, in this study, using density functional theory (DFT), we
assessed the structural stability of a group of two-dimensional perovskite-type materials which we call
perovskenes. Specifically, we analyzed the stability of 2D SrTiO3, SrZrO3, BaTiO3, and BaZrO3
monolayers. Our simulations revealed that the 2D monolayers of SrTiO3, BaTiO3, and BaZrO3 are at least
meta-stable, as confirmed by cohesive energy calculations, evaluation of elastic constants, and
simulation of phonon dispersion modes. With this information, we proceeded to investigate the
electronic, optical, and thermoelectric properties of these perovskenes. To gain insight into their
promising applications, we investigated the electronic and optical properties of these 2D materials and
found that they are wide bandgap semiconductors with significant absorption and reflection in the
ultraviolet (UV) region of the electromagnetic field, suggesting them as promising materials for use in UV
shielding applications. In addition, evaluating their thermoelectric factors revealed that these materials
become better conductors of electricity and heat as the temperature rises. They can, hence, convert
Received 13th September 2023, temperature gradients into electrical energy and transport electrical charges, which is beneficial for
Accepted 17th November 2023 efficient power generation in thermoelectric devices. This work opens a new window for designing a
DOI: 10.1039/d3cp04435a novel family of 2D perovskite type materials termed perovskenes. The vast variety of different perovskite
compounds and their variety of applications suggest deeper studies on the perovskenes materials for
rsc.li/pccp use in innovative technologies.

1. Introduction
The discovery of graphene1 and the determination of its excep-
tional physical properties, such as its remarkably high carrier
mobility2 (B200 000 cm2 V1 s1) and interesting mechanical
a
Department of Chemistry, Department of Physics and Astronomy, CMS – Center
for Molecular Simulation, IQST – Institute for Quantum Science and Technology,
and thermal properties3–5 have generated substantial interest
Quantum Alberta, University of Calgary, 2500 University Drive NW, Calgary,
Alberta, T2N 1N4, Canada. E-mail: [email protected],
in the field of two-dimensional (2D) materials. These remark-
[email protected] able strides have not only facilitated numerous groundbreaking
b
Department of Physics, Kermanshah Branch, Islamic Azad University, discoveries in this field but have also ignited significant enthu-
Kermanshah, Iran siasm for 2D materials in the commercial sector. Consequently,
c
Micro and Nanotechnology Graduate Program, TOBB University of Economics and
a vast number of 2D materials are being designed theoretically
Technology, Sogutozu Caddesi No 43 Sogutozu, 06560 Ankara, Turkey
d
Department of Physics, Jashore University of Science and Technology, Jashore
and/or obtained experimentally,6–25 indicating a high level of
7408, Bangladesh confidence in their subsequent applications.
e
Departamento de Quı́mica e Fı́sica – Centro de Ciências Exatas, Naturais e da In particular, the exploration of 2D structures of large
Saúde – CCENS – Universidade Federal do Espı́rito Santo, Alegre, Espı́rito Santo, families of bulk materials, such as MAX phases and transition
Brazil
f
metal dichalcogenides, shows immense potential for the design
Department of Chemistry, University of Calgary, Calgary, Alberta T2N 1N4,
Canada
of innovative 2D materials and their utilization across a wide
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/ range of technological applications. In more detail, MAX
10.1039/d3cp04435a phases are layered materials with M–A–X layers, in which M

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represents a transition metal, A represents a group A element In 2022, the impact of dimension reduction from three-
(such as aluminum or silicon), and X is either C or N. By dimensional (3D) to 2D on the thermodynamic and electronic
selectively removing the A-layer, a large family of 2D structures properties of 2D SrTiO3 was investigated by Hu et al.44 It was
known as MXenes4 are obtained. These MXenes exhibit remark- found that 2D SrTiO3 exhibits abnormal band-gap trends on
able properties and offer a variety of interesting applications.16–20 varying the thickness, suggesting an unusual quantum size
For the case of transition metal dichalcogenides (TMDs), their 2D effect. In this study, using density functional theory, we first
structures are a class of atomically thin semiconducting com- examined the stability, electronic, optical and thermoelectric
pounds with bandgaps ranging from 1 to 2.5 eV. The chemical properties of 2D SrZrO3, SrTiO3, BaZrO3, BaTiO3 monolayers as
formula of these materials is MX2, where M represents a transi- typical examples of the family of 2D perovskite-type mono-
tion metal and X represents a chalcogen. By decreasing the layers. However, among the considered monolayers, we found
number of layers from a multilayer to a monolayer a transition that only three of them, 2D SrTiO3, BaZrO3, and BaTiO3, are
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from an indirect to a direct bandgap occurs in this class of stable. Then we evaluated their electronic, optical and thermo-
materials which causes a significant enhancement of their elec- electric properties. The results of this study provide motivation
trical and optical characteristics such as their photoluminescence to explore further a vast number of perovskite materials to find
properties.26–32 Therefore, going from the bulk to the 2D limit of new 2D perovskite-type materials.
atomically thin materials may bring more intriguing properties
that may be important technologically.
Over the past few years, the perovskite family of materials
2. Computational details and methods
have attracted considerable interest from researchers, both in We employed density functional theory as implemented in the
computational and experimental domains, owing to their WIEN2k code45 and used the full-potential linear-augmented
exceptional properties. Perovskites, characterized as ternary plane wave plus local orbital (FPLAPW+lo) approach to perform
crystalline structures with the chemical formula ABX3, have atomic force minimization, lattice optimization, and analysis of
emerged as a prominent category in materials research. Their electronic/optical properties. We first applied the Perdew–
crystal structure consists of closely packed X anions, such as Burke–Ernzerhof (PBE) exchange–correlation functional46 in
oxygen or a halide (Cl, Br, I), with two types of cations, ‘A’ the generalized gradient approximation (GGA) form. However,
and ‘B’, which are often of very different sizes. Perovskites can due to the PBE method’s tendency to underestimate the band-
be divided into perovskite halides and oxides. Within perovs- gap, we assessed the electrical properties using the hybrid
kite halides, the A site is typically occupied by either an organic functional (HSE06).47 To ensure accurate sampling of the initial
or an inorganic monovalent cation, while the B site is occupied Brillouin zone, we adopted the Monkhorst–Pack scheme48
by a divalent metal ion such as Sn2+, Ge2+, or Pb2+. Conversely, using 8  8  1 and 16  16  1 k-point meshes for the
in perovskite oxides, the A site is filled with an alkaline-earth assessment of electrical and optical properties, respectively. We
metal (Ca, Sr, or Ba) or a rare-earth metal (La, Ce, or Nd) ion, set the input parameters as RKmax = 7, Gmax = 12 Ry1/2, and
while the B site is occupied by a transition metal (Mn, Fe, or Ti) lmax = 10.
ion. Perovskites exhibit a diversity of properties, including To assess the dynamical stability of the designed structure,
electronic and ionic conductivity, superconductivity, piezoelectri- we conducted phonon dispersion calculations using the QUAN-
city, magnetic properties, and catalytic activity.33–38 These remark- TUM ESPRESSO package.49 In this analysis, we employed
able characteristics make them highly promising for applications the norm-conserving pseudopotential developed by Martin–
in emerging technologies, with the potential to surpass and Troullier.50
enhance conventional, well-established technologies. Additionally, we used energy-strain investigation to evaluate
Exploring the transition of perovskite materials from their the mechanical stability, specifically determining the in-plane
3D form to a 2D limit may uncover the novel properties of these stiffness (Y) and Poisson’s ratio (n) of the material. The model
materials. In 2019, Ji et al. showcased the potential for stabilizing relies on the independent elastic constants C11 and C12. In this
freestanding 2D SrTiO3 and BiFeO3 through the utilization of theory, for a 2D system, the dependence of strain energy U on
water-soluble Sr3Al2O6 as a sacrificial buffer layer.39 Further- strain eij is given as a quadratic polynomial as follows51
more, the successful synthesis of 2D SrTiO3, PbTiO3 and BaTiO3
1 1
has been achieved using epitaxial growth techniques, primarily U ¼ C11 e112 þ C22 e222 þ C12 e11 e22 (1)
2 2
employing molecular beam epitaxy40–42 and pulsed laser deposi-
tion (PLD). In addition, Zhou et al. successfully synthesized Therefore, the in-plane elastic coefficients of 2D materials
monoclinic KNbO3 nanosheets by utilizing a solution-based are given by
method43 and found a strong anisotropy of ferroelectric polar- 1 @2U 1 @2U 1 @2U
ization in 2D KNbO3. Nevertheless, unlike bulk and thin-film C11 ¼ ; C22 ¼ ; 2ð C 12 þ C 11 Þ ¼ (2)
S0 @e112 S0 @e222 S0 @e11 @e22
perovskites, the investigation of 2D perovskites with atomic-scale
thickness is still in its early stage. Theoretical/computational In the above equations, S0 refers to the area of the ground
studies, such as those based on density functional theory, could state unit cell and the strain energy is given by U. The para-
offer valuable insight into the properties and potential applica- meters e11 and e22 indicate the applied external strain in x and y
tions of this intriguing class of materials. directions (armchair and zigzag directions).

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Finally, to evaluate the thermoelectric properties of the Table 1 The structural and energetic properties of 2D SrTiO3, BaTiO3 and
materials, the BoltzTraP52 code within a semi-classical Boltz- BaZrO3
mann theory framework was employed under an approxi- 2D Monolayer BaTiO3 BaZrO3 SrTiO3
mation of constant relaxation time for the evaluation of
a = b (Å) 3.94 4.19 3.91
thermoelectric properties. DABO3 (Å) 1.98 2.01 1.95
A–O (Å) 2.69 2.74 2.53
B–O(in plane)/B–O (out of plane) (Å) 1.83/1.97 1.94/2.09 1.80/1.96
Cohesive energy (eV per atom) 3.70 4.22 3.83
3. Structural properties and the Work function (eV) 4.90 4.60 5.25
stability of 2D perovskites
refers to the energy of a unit cell of 2D perovskene material,
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Our prediction of these 2D perovskite materials was inspired by

the experimental report on the potential to stabilize freestand- EA and EB denote the energies of the cation and anion atoms,
ing 2D SrTiO3 and BiFeO3 using water-soluble Sr3Al2O6 as a respectively, and Eo corresponds to the energy of a free oxygen
sacrificial buffer layer. Previous studies have successfully atom, which is considered half of the oxygen gas energy. Based
synthesized 2D SrTiO3, PbTiO3, and BaTiO3 using epitaxial on our calculations, the cohesive energies were found to be 5.05
growth techniques,39–43 and a recent theoretical study by Hu eV, 5.12 eV, and 5.21 eV for SrTiO3, BaZrO3 and BaTiO3
et al.44 also provides context for our research. Considering the perovskenes respectively. These values indicate that the
crystal configuration of the bulk SrTiO3, SrZrO3, BaTiO3, and proposed materials are strongly bound.
BaZrO3 perovskites, we computationally designed their possible To assess the dynamic stability of SrZrO3, SrTiO3, BaZrO3
2D structures which can maintain the stoichiometry of ABO3 and BaTiO3 perovskenes, we calculated their phonon disper-
with the minimum number of A, B and O atoms. The crystal sion spectra. No imaginary phonon modes were observed in the
structure of the predicted monolayer perovskites (perovskenes) simulated phonon spectrum (Fig. 2) for 2D SrTiO3, BaZrO3 and
is illustrated in Fig. 1. Each unit cell of the designed ABO3 BaTiO3 monolayers, confirming the dynamic stability of
perovskenes consists of five atoms, including a cation A (Ba, Sr), the materials. However, it was found that 2D SrZrO3 is not
an anion B (Zr, Ti), and three oxygen atoms. dynamically stable as an imaginary phonon mode appears in its
Based on our calculation the lattice parameters are 3.94, phonon dispersion which is plotted in Fig. S1 (ESI†). To be
4.19, 3.91 and 4.20 Å for 2D BaTiO3, BaZrO3, SrTiO3 and SrZrO3 more precise, our simulation revealed that the maximum
monolayers respectively. The obtained lattice parameters are phonon frequencies of 2D SrZrO3, SrTiO3, BaZrO3 and BaTiO3
similar to those reported for their bulk BaTiO3 (4.01 Å), BaZrO3 are 849 cm1, 836 cm1, 807 cm1 and 741 cm1, respectively.
(4.19 Å), SrTiO3 (3.91 Å), and SrZrO3 (4.20 Å) perovskites
(however, see below, the latter is unstable, with an imaginary
phonon frequency). These structures have two atomic surfaces
terminated by A–O and B–O bonds. By minimizing the intera-
tomic forces and optimizing the unit cell parameters the
optimized and relaxed unit cell parameters of the designed
structures were obtained (Table 1).
To assess the stability of the predicted structures, we initially
computed the cohesive energies of the proposed perovskene
materials. The cohesive energy (Ecoh) was determined using the
Eperovskene  3Eo  EA  EB
formula Ecoh ¼ , where Eperovskene
5

Fig. 1 A unit cell of a perfectly cubic ABO3 perovskite (a), the crystal
structures of our designed perovskene materials from top view (b) and side Fig. 2 The phonon dispersion spectrum of 2D SrTiO3, BaZrO3 and BaTiO3
view (c). perovskene structures.

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Furthermore, we employed energy-strain analysis to calcu- 4. Electronic, optical and

late the elastic constants of the monolayers and check their thermoelectric properties of 2D SrTiO3,
mechanical stability. Here, the uniaxial strain along x and y
a  a0 b  b0 BaZrO3 and BaTiO3 perovskenes
axes are defined by e11 ¼ , e22 ¼ , and a, b and a0, b0
a0 b0 To gain insight into the electronic properties of the predicted
are the lattice parameters of the strained and strain-free
2D perovskenes, we calculated their band structures and partial
structures. The variation of strain energy of the 2D SrTiO3,
densities of states (PDOS). Fig. 4 illustrates the band structures
BaZrO3 and BaTiO3 monolayers under biaxial and uniaxial
computed using the PBE and HSE06 levels of theory. According
strains is illustrated in Fig. S2 (ESI†). Considering eqn (1) and
to Fig. 4, these monolayer materials exhibit the characteristics
(2), we calculated C11, C22, and C66. However, considering their
of indirect semiconductors, with calculated band gaps of 1.97
symmetries, for our designed structures C11=C22. Moreover, by
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(3.47), 1.88 (3.47), and 3.12 (4.39) eV for SrTiO3, BaZrO3, and
calculating C11, C12, other elastic constants such as the Pois-
BaTiO3 perovskenes, respectively, based on PBE (HSE06).
son’s ratio (u2D) and the Young’s modulus (Y2D), and layer
Furthermore, Fig. 4 demonstrates that the valence band max-
modulus are defined by:
imum (VBM) and the conduction band minimum (CBM) of
C12 2D   1 these materials are situated at the M(R) and gamma points,
u2D ¼ ; Y ¼ C11 1  u2 ; g2D ¼ ðC11 þ C12 Þ (3)
C11 2 respectively. For comparison we further calculated the band
structures of SrTiO3, BaZrO3, and BaTiO3 bulk materials which
For a stable 2D material, the elastic constants need to satisfy are presented in Fig. S3 (ESI†). Based on our calculation the
the stability requirements of C11 4 C22 and C66 = (C11,C22)/2 4 0, band gap values of 2.18 (3.2a8), 3.29 (4.54) and 2.08 (3.20) eV
which are proposed by Born and Huang.53 The obtained elastic were obtained for SrTiO3, BaZrO3, and BaTiO3 perovskites
constants for the 2D perovskenes materials are given in Table 2. which are in very good agreement with the previously reported
Based on our simulation, it can be seen that all three structures data.57 It is worth noting that the use of the PBE functional
are mechanically stable. For validation of our calculation, we tends to underestimate the bandgaps of 2D materials. To
further calculated the elastic constants of SrTiO3, BaZrO3 and obtain more accurate estimation of these bandgaps, different
BaTiO3 perovskites which are also indicated in Table 2, and they methods such as HSE06, mBJ, PBE0 and GW are used with
are in very good agreement with the previously reported theore- varying levels of accuracy and computational cost.58–61 Among
tical and experimental data for these materials.54,55 them, the GW method is the gold standard for achieving the
Additionally, the orientation-dependent Poisson’s ratio and highest accuracy in band gap calculations but comes with a
Young’s modulus can be obtained from the elastic constants as significantly higher computational burden. HSE06 and mBJ are
follows:56 useful for improving band gap predictions in standard DFT
C11 C22  C122 calculations, with mBJ being less computationally expensive.
Y 2D ðyÞ ¼   (4)
C11 C22  C122 The choice of method depends on the specific material, the
C11 s4 þ C22 c4 þ  2C12 c2 s2 desired level of accuracy, and available computational
C66
resources. We used the HSE06 functional for both bandgap
  and band structure calculations. To validate our approach, we
  C11 C22  C122 2 2
C12 s4 þ c4  C11 þ C22  c s applied the same level of theory (HSE06) to calculate the
C66
u2D ðyÞ ¼   ; bandgaps of experimentally synthesized h-BN and MoS2 mono-
4 4
C11 C22  C122 2 2
C11 s þ C22 c þ  2C12 c s layers, yielding values of 5.73 eV and 2.26 eV for their bandgaps
C66
respectively. When comparing these computed values with the
(5)
experimental bandgaps (approximately 6.00 eV for h-BN and
where s = sin(y) and c = cos(y). As indicated in Fig. 3, we found approximately 2.1 eV for MoS2 monolayers), our results demon-
that Y2D(y) and U2D(y) plots are not perfect circles, implying the strate the reliability of our method.62,63
anisotropic elasticity of the monolayers. To be more precise, Furthermore, we conducted additional calculations on the
among these three materials, 2D BaTiO3 demonstrates the partial density of states (PDOS) for the 2D perovskenes, as
lowest anisotropic elastic parameters, whereas 2D BaZrO3 depicted in Fig. 5. From the illustration, it is evident that the
exhibits a greater degree of anisotropy in its elastic constants. valence band maximum (VBM) of these monolayer materials is
The range of elastic constant variations for these materials is predominantly occupied by p-electrons originating from oxygen
presented in Table 2. atoms. On the other hand, the conduction band minimum

Table 2 The 2D elastic constants Cij (N m1), Young modulus g2D (N m1), Poisson ratio ns, and shear modulus G (N m1) of the designed 2D perovskene
materials

Monolayer (bulk) C11 (N m1) C22 (N m1) C12 (N m1) C66 (N m1) g2D (N m1) n2D (N m1) G (N m1)
BaTiO3 169.84 (304.89) 169.84 (304.89) 54.43 (108.21) 53.04 (98.34) 144.03–152.39 0.32–0.36 53.04–57.70
BaZrO3 178.30 (272.48) 178.30 (272.48) 36.93 (78.24) 34.42 (97.12) 104.32–170.65 0.21–0.52 34.42–70.69
SrTiO3 165.10 (356.67) 165.10 (356.67) 41.63(106.55) 45.07 (125.06) 125.54–154.60 0.25–0.39 45.07–61.73

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Fig. 3 The angular dependence of Young’s modulus and the Poisson ratio of 2D SrTiO3, BaZrO3 and BaTiO3 monolayers.

are significant variations in the electrostatic potential even

when no atoms are present for interaction.
Furthermore, the work functions (F) of the monolayers were
calculated by using the computed electrostatic potential. The
work function is defined as the energy difference between the
vacuum energy (Evacuum) and the Fermi energy (Ef) of the system
(F = Evacuum  Ef). It quantifies the energy required to remove
an electron from the material’s surface and transfer it into the
vacuum, representing the minimum energy necessary to over-
come attractive forces and reach the vacuum level.
The computed work function values for 2D BaTiO3, BaZrO3,
and SrTiO3 materials are 4.90 eV, 4.60 eV, and 5.25 eV,
Fig. 4 The band structures of 2D SrTiO3, BaZrO3 and BaTiO3 monolayers
respectively. Comparing these calculated work function values
calculated using PBE and HSE06 levels of theory.
with those obtained for phosphorene (4.50 eV),64 graphene
(4.60 eV),65 BN (4.90 eV),66 MoS2 (5.15 eV)67 and MoSi2N4
(CBM) is primarily composed of d-electrons derived from the
(5.19 eV),68 they exhibit relatively weak tendencies towards
anion atoms (Zr, Ti). These findings suggest that the electronic
electron emission.
properties of these materials can be effectively manipulated by
In addition, the optical properties of 2D perovskites were
employing various processes, such as B-site doping, to engineer
examined. To achieve this, the frequency-dependent complex
their characteristics.
dielectric function of the material was calculated. The complex
Moreover, to gain more insight into the electronic nature of
dielectric function is defined as E(o) = RE(o) + iIE(o), where
the materials, their electron localization function (ELF) was
RE(o) and IE(o) represent the real and imaginary components
calculated as shown in Fig. 6(a). The ELF provides a measure of
of this function, respectively. The imaginary component IE(o) is
electron localization in a system, with a value between 0 and 1,
represented as the elements within the following matrix,69,70
where high ELF values indicate strong electron localization
between atoms or regions. A value of 1 corresponds to perfect
ð
electron localization. In this case, the ELF value between oxygen 4p2 e2 X 2d3 k  2    
IEab ðoÞ ¼ 2 2 3
f hik jPua jfi i fik 1ffk d Efk Eik ho g:
atoms is around the maximum value of 1. This indicates a large m o i;f ð2pÞ
proportion of very strong covalent bonds within the monolayer, (6)
suggesting a high degree of electron localization and strong
bonding.
In addition, the plane-average electrostatic potential is pre- where i and f denote the initial and final states, respectively,
sented in Fig. 6(b). As illustrated in Fig. 6(b), for all the 2D while Eik represents the corresponding eigenvalue, fik refers to
perovskite oxides, there are elastic potential differences the Fermi distribution and Pua signifies the projection of the
between two sides of the monolayers which are due to the elements of the momentum dipole matrix in the u direction of
asymmetric structure of the materials along the z-axis. As seen the electromagnetic field. Using the imaginary component
in Fig. 6(b), the electrostatic potentials of all monolayers show IE(o), the real part of the E(o) can be easily obtained through
non-flat profiles in the vacuum region. This implies that there the application of the Kramers–Kronig theory. This can be

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calculated using the following equation:72

 1
pffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 2
aðoÞ ¼ 2 ðRE ðoÞÞ2 þðIE ðoÞÞ2  ðRE ðoÞÞ (8)

Fig. 7 illustrates the real and imaginary components of the

complex dielectric function for the proposed 2D perovskite materi-
als. The static dielectric constants of 1.62, 1.61, and 1.70 were
calculated for SrTiO3, BaZrO3, and BaTiO3, respectively. These
values indicate that these materials possess favorable dielectric
properties, making them suitable for applications involving high-
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value capacitors. Examining both the real and imaginary compo-

nents of the function, we observe that the first significant peaks
occur at approximately 4.00, 4.80, and 3.90 eV, which reside within
the ultraviolet (UV) light region. These peaks can be attributed to
the optical transitions between O p-states at the valence band
maximum (VBM) and Zr/Ti d-states at the conduction band
minimum (CBM). From Fig. 7(a), it is evident that for all struc-
tures, RE(o) increases with increasing energy, reaching a max-
imum value of about RE(o) = 2.24, 2.47, and 2.26 at E = 4.10, 5.05,
and 3.91 eV for SrTiO3, BaZrO3, and BaTiO3 perovskenes, respec-
tively. Moreover, for incident photons with higher energies, the
real component, RE(o), decreases as the energy increases.
Furthermore, we calculated the optical absorption properties
of the materials across all structures. The resulting absorption
spectra of these materials are depicted in Fig. 8(b), showing the
evolution of the absorption characteristics. It is evident that
these monolayer materials exhibit significant absorption and
reflectivity peaks in the ultraviolet (UV) region. Specifically, they
demonstrate maximum absorption values of 58.24, 38.79 and
54.13  104 cm1 at the energies of 7.31, 6.68 and 7.52 eV for 2D
SrTiO3, BaZrO3, and BaTiO3 perovskenes, respectively. However,
they also display relatively low levels of absorption and reflectiv-
ity in the visible region of the light spectrum. Based on these
observed properties, it can be inferred that these materials hold
potential for applications involving UV shielding.
Fig. 5 The partial density of states for 2D SrTiO3, BaZrO3 and BaTiO3 In recent years bulk perovskite materials have attracted much
monolayers calculated at the HSE06 level of theory. attention for thermoelectric applications.73,74 Therefore, as the final
part of our study, considering the obtained elastic and electronic
properties for the predicted materials, we checked their thermo-
expressed as follows:71 electric properties. Thermoelectricity is a unique property of certain
materials that allows them to convert temperature gradients into
electrical energy and vice versa. Devices, called thermoelectric
ð1
2 IEab ðo0 Þ generators or thermoelectric coolers, have various applications in
Rab
E ðoÞ ¼ dab Pr  dðo0 Þ (7)
p 0 ðo0 Þ2 ðoÞ2 power generation, waste heat recovery, and temperature regulation.
In this study, thermoelectric properties of the studied materials are
investigated using Boltzmann transport theory as implemented in
The nature of interaction between light and a material can the BoltzTraP code for a temperature of up to 1000 K. The thermo-
be characterized by the two components of the complex dielec- electric transport coefficients can be determined as follows:75
tric constant. The absorption of light by the material corre-  
e2 X d e  ei;k
sponds to a positive value of RE(o) indicating the extent to sab ðeÞ ¼ tua ði; j Þ ; (9)
N i;k de
which light is absorbed. On the other hand, the loss of photon
energy is described by IE(o), representing the imaginary com-
where a, b, e, N, e, t and U(i,j) refer to the tensor indices, electronic
ponent of the complex dielectric constant. By having these two
charge, the k-point grid number, band energy, relaxation time and
components for a material, all other optical properties of the  
1 @Eik
material such as the coefficient a(o) can be straightforwardly group velocity uði; j Þ ¼ respectively. The Seebeck co-
h @ka


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Fig. 6 The schematic shows the contour plots of ELF: a visual representation of the electron density distribution in 2D perovskite oxide structures (a). In
these plots, the red regions correspond to areas of high electron density, while the blue regions represent areas of low electron density. Potential average
of the perovskite oxide monolayers of 2D BaTiO3, BaZrO3, and SrTiO3 (b).

efficient, thermal conductivity and the electrical conductivity tensor transport distribution:
as a function of temperature can be obtained by integration of the
1 Ðs @f0 ðT; e; mÞ
sab ðT; mÞ ¼ ðeÞ @e (10)
O ab @e

1 Ðs @f0 ðT; e; mÞ
Sab ðT; mÞ ¼ ðe  m Þ @e (11)
eTsab O ab @e

1 Ðs 2 @f0 ðT; e; mÞ
kelab ðT; mÞ ¼ ab ðe  mÞ @e (12)
O @e

where O, m and f0(T, e, m) are the unit cell volume, chemical

potential, and Fermi distribution function, respectively.
Based on our calculations, for all three systems, the Seebeck
coefficient (S), which is a measure of a material’s ability to
generate a voltage difference when subjected to a temperature
gradient, decreases as the temperature increases over a low
temperature range. However, at higher temperature, above
500 K, for 2D BaTiO3 and SrTiO3 the value of S remains almost
constant. Alternatively, it can be observed that 2D BaZrO3
exhibits a slight increase in the value of the Seebeck coefficient
above 500 K. This means that the effectiveness of the materials
for converting thermal energy into electrical energy is main-
tained for a range of temperatures above 500 K. The character-
istics of Seebeck coefficients of the materials are shown in
Fig. 9(a). The increase in both electrical conductivity (s/t) and
electronic thermal conductivity (ke/t) with temperature, as
shown in Fig. 9(b) and (c), indicates that the material becomes
a better conductor of both electricity and heat as the tempera-
ture rises. Higher electrical conductivity implies that the mate-
rial can more effectively transport electrical charges, which is
Fig. 7 The real (a) and imaginary (b) components of the complex dielec-
beneficial for efficient power generation in thermoelectric
tric function of 2D SrTiO3, BaZrO3 and BaTiO3 monolayers as a function of devices. Additionally, the increase in electronic thermal con-
photon energy. ductivity implies improved heat conduction through the

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Fig. 8 The absorption (a) and the reflectivity (b) components of 2D

SrTiO3, BaZrO3 and BaTiO3 monolayers as a function of photon energy.

material, which can aid in heat dissipation. In our investiga-

tion, it was observed that the power factor (PF), which is the
product of electrical conductivity and the square of the Seebeck
coefficient, increases with increasing temperature. The results Fig. 9 Calculated (a) Seebeck coefficient, (b) thermal conductivity and (c)
are illustrated in Fig. 10(a). This finding indicates that as the electrical conductivity of 2D SrTiO3, BaZrO3 and BaTiO3 monolayers as a
function of temperature.
temperature rises, the material exhibits an enhancement of its
power generation capabilities in thermoelectric applications.
The efficiency of a thermoelectric material is determined by its slightly increasing trend above 600 K. This non-linear trend
thermoelectric figure of merit, also known as the ZT value. The may be attributed to the complex interplay between the materi-
behavior of the ZT (= S2sT/k) value, where S, s, T, and k stand al’s electrical conductivity, thermal conductivity, and Seebeck
for the Seebeck coefficient, electrical conductivity, absolute coefficient with temperature. The estimated values of thermo-
temperature and thermal conductivity, respectively, provides electric features at 300 K for 2D BaTiO3, BaZrO3 and SrTiO3 are
insight into the material’s thermoelectric performance. The given in Table 3.
thermal conductivity depends on electronic and lattice thermal
conductivity. But the BoltzTraP code ignores the lattice part and
works only on the electronic thermal conductivity assuming 5. Conclusion
that the former will be small compared to the latter. The
estimated ZT values of 2D BaTiO3, BaZrO3 and SrTiO3 are Inspired by the recent utilization of reactive molecular beam
presented in Fig. 10(b). The initial decrease in the ZT value epitaxy to produce freestanding ultrathin films of SrTiO3 and
with increasing temperature indicates that the material’s effi- BiFeO3, here, a new family of 2D perovskite type materials termed
ciency in converting heat into electrical energy diminishes at perovskenes are systematically predicted by using first-principles
higher temperatures. However, the subsequent increase in the calculations based on density functional theory (DFT). As exam-
ZT value, for 2D BaZrO3, after reaching a minimum at 500 K ples of the 2D perovskenes, we investigated the stability, electro-
suggests that the material’s thermoelectric performance nic, optical and thermoelectric properties of 2D SrTiO3, BaTiO3
improves again at even higher temperatures. On the other and BaZrO3 monolayers and found that these materials show high
hand, for 2D BaTiO3 the value of ZT remains almost constant stability and interesting properties suggesting them to be con-
above 600 K though for 2D SrTiO3 the value of ZT shows a sidered for a variety of applications. According to our calculations,

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Acknowledgements
This work is supported by the National Research Council of
Canada, Artificial Intelligence for Design program, by the
Natural Sciences and Engineering Research Council of Canada,
Discovery Grant (RGPIN-2019-03976) and by Compute Canada
(now the Digital Research Alliance of Canada). The work is also
supported by TUBITAK ULAKBIM, High Performance and Grid
Computing Center (TR-Grid e-Infrastructure).
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