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org/JPCC Article

Thermodynamic and Electronic Properties of Two-Dimensional

SrTiO3
Xun-Jian Hu, Yi Yang,* Chunju Hou, and Tong-Xiang Liang*
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ABSTRACT: Perovskite oxides are star materials due to their

particularly rich properties such as superconductivity, ferroelec-
tricity, magnetic property, and photocatalytic activity. A recent
study [Ji, D.et al. Freestanding crystalline oxide perovskites down
Downloaded via NAGALAND UNIV on January 27, 2022 at 16:59:51 (UTC).

to the monolayer limit. Nature 2019, 570, 87 90] showed that

freestanding two-dimensional (2D) perovskite oxides down to the
monolayer limit can prepared. The intrinsic nanoscale of 2D
perovskite oxides may impart them more intriguing properties and
more possibility for their application in nanoscale electronic and
spintronic devices. Taking SrTiO3 as an example, we investigate the
impact of dimension reduction from three-dimension (3D) to 2D
on the thermodynamic and electronic properties of perovskite
oxides. We find that the thermodynamic stability of 2D structures
is termination-dependent. Moreover, 2D SrTiO3, regardless of terminations (SrO- or TiO2-, or both), exhibit abnormal band-gap
trends, with a gap value lower than the bulk limit, suggesting an unusual quantum size effect in 2D SrTiO3. The origin of abnormal
trends can be attributed to the band splitting of conduction bands and surface states of valence bands. Our results provide a clear
picture about the evolution of the electronic properties of materials with the change of dimension in perovskite oxides.

1. INTRODUCTION molecular beam epitaxy (MBE)13−15 and pulsed laser

Perovskite oxides are of great research interest from both
fundamental and application aspects. From basic science, these
materials possess plenty of physical and chemical properties
such as superconductivity, ferroelectricity, magnetic property,
and photocatalytic activity.1−4 These properties promote wide
applications of perovskite oxides in many kinds of devices, e.g.,
multiferroic devices,5 optical devices,6 and flexible devices (e.g.,
flexible ferroelectric memories, sensors, and generators).7
Moreover, in energy and environment fields, perovskite oxides
are promising (photo)electrodes and photocatalytic materials
due to their good (photo)electrochemical stability and tunable
electronic structures.8,9 For example, d0 perovskite oxides such
as SrTiO3 (STO) are widely investigated as photocatalysts
applied in water splitting, and for the degradation of organic
pollutant and CO2 reduction because of their tunable
electronic structures, good stability, and high catalytic
activity.10,11
The extension of perovskite oxides to the two-dimensional
(2D) limit of atomic thickness may impart them more
intriguing properties. For example, an unusual ferroelectricity
appears in 2D perovskite oxides with several unit cells (UC) of
thickness due to the surface effect.12 Recently, Ji et al.
demonstrated that freestanding 2D STO and BiFeO3 down to
1-UC limit can be prepared using water-soluble Sr3Al2O6 as the
sacrificial buffer layer.13 2D STO, PbTiO3, and BaTiO3 have
been synthesized by epitaxial growth methods, mainly
deposition (PLD).16,17 Besides, Zhou et al. synthesized
monoclinic KNbO3 nanosheets by utilizing the solution-
based method18 and found a strong anisotropy of ferroelectric
polarization in 2D KNbO3. However, in contrast to bulk and
film perovskite oxides, the exploration of 2D perovskite oxides
with the thickness of several unit cells remains in its initial
stage.19 For example, the impact of dimension reduction from
3D to 2D on the thermodynamic and electronic properties of
perovskite oxides remains largely unknown, even for the
archetypal perovskite oxide STO. The main aim of this study is
to examine the evolution nature of the properties of perovskite
oxides on varying the geometric dimensions of materials.
Based on the density functional theory (DFT), using STO as
a typical example, we investigate the thermodynamic and
electronic properties of 2D STO (2D-STO) with the thickness
down to 1 UC. We figure out the thermodynamic stability of
2D-STO and build a connection to the stability of STO
surfaces. We find that 2D-STO exhibits abnormal band-gap
Received: August 12, 2021
Revised: December 9, 2021
Published: December 28, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acs.jpcc.1c07159

517 J. Phys. Chem. C 2022, 126, 517−524
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trends with a converged gap value lower than the bulk limit,
implying an unusual quantum confinement effect. We then
elucidate the origin of this abnormal behavior by analyzing the
orbital-projected band structures and decomposed charge
density.
2. METHODS
In the experiments, 2D-STO is prepared by epitaxial growth
methods such as MBE. These 2D structures are grown along
the [001] direction of the STO crystal due to the nonpolar
character of (001) surfaces.13 Along this direction, SrO- or
TiO2-termination appears as a surface layer. The growth of
precise termination can be controlled by reflection high-energy
electron diffraction (RHEED).20 We built 2D-STO models
from bulk STO based on structural information from the
experiments. Two terminations, SrO- and TiO2-, give rise to
three types of 2D-STO: (1) SrO-terminated 2D-STO
(denoted as SrO-2D); (2) TiO2-terminated 2D-STO (TiO2-
2D); (3) stoichiometric 2D-STO with both SrO and TiO2
surface layers (SrO-TiO2-2D). Their structure models are
shown in Figure 1. We investigated all three types of 2D-STO
Figure 1. Structure models of bulk and 2D SrTiO3 (STO): (a) bulk;
(b) SrO-terminated 2D-STO; (c) TiO2-terminated 2D-STO; (d)
stoichiometric 2D-STO. One- and two-unit cell (UC) 2D-STO are
displayed. Thicker 2D-STO can be built in a similar way.
with varying thickness from 1 UC to 8 UC to obtain the trends
of band gaps. The in-plane constants of 2D-STO are fixed to
the theoretical lattice constant of 3.895 Å of the bulk, and
atomic positions are relaxed to equilibrium. We calculated the
thermodynamic and electronic properties based on these 2D
structures. We also consider the effect of full relaxation of the
2D cell on the electronic properties.
We carried out first-principle calculations using the density
functional theory (DFT) via the Vienna ab initio simulation
package (VASP).21,22 The Perdew−Burke−Ernzerhof func-
tional revised for solids (PBEsol) was utilized for atomic
structure calculations.23 The plane-wave kinetic cutoff energy
was set to 500 eV. The convergence criteria of 10−5 eV and
10−2 eV Å−1 were used for the total energy and forces,
respectively. A k-point grid of 8 × 8 × 8 was used for cubic
SrTiO3 bulk and 8 × 8 × 1 for 2D-STO.24 The Heyd-Scuseria-
Ernzerhof (HSE06) hybrid functional25 was used in electronic
structure calculations. We checked the convergence of HSE06
calculations. A vacuum layer of larger than 15 Å is added to
avoid the interaction between the slab and its repeated images.
Electrostatic potential correction was added in asymmetric slab
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calculations to correct the artificial dipole interactions
introduced by the periodic boundary condition.
To assess the thermodynamic stability of 2D-STO, we
calculated their formation energies (Ef) with respect to their
binary phases SrO (rocksalt) and TiO2 (anatase) phases. The
calculation details of the Ef of 3D and 2D perovskites are
presented in the Supporting Information (SI). According to
the definitions given there, a negative Ef indicates that the
formation of 3D or 2D ternary phase is an exothermal process,
which indicates the stability of the ternary phase. The more
negative the Ef, the better the stability of the ternary phase.
Besides, we also calculated the surface energy (Esurf) of STO
(001) surfaces using the method previously adopted by Padilla
and Vanderbilt.26,27 For SrO- or TiO2-terminated STO (001)
surfaces, Esurf is dependent on the chemical potentials of SrO
or TiO2. (A more detailed discussion is available in the SI).
3. RESULTS AND DISCUSSION
3.1. Thermodynamic Properties. We analyze the
intrinsic thermodynamic stability of 2D-STO by calculating
their formation energies (Ef). We first calculate the Ef of the
STO bulk. The PBEsol-calculated Ef of −1.268 eV for the
cubic phase lies between −1.371 eV for LDA and −1.116 eV
for PBE. Moreover, our calculated Ef values from LDA and
PBE are in good agreement with the previously GGA-PBE
calculated value of −1.09 eV and LDA values of −1.39 and
−1.49 eV.28,29 The Ef of the bulk can be a reference to evaluate
the intrinsic stability of 2D-STO. We calculate the Ef of 2D-
STO with a thickness of up to 8 UC.
Figure 2 shows the Ef of 2D-STO with the variation of the
thickness from 1 to 8 UC. It is seen that the Ef values of all
Figure 2. PBEsol-calculated formation energies (Ef) of 2D-STO as a
function of thickness (in the number of unit cells (UC)). The Ef of
STO bulk is calculated to be −1.268 eV, as marked by the dashed line.
three types of 2D-STO decrease gradually with increase in the
thickness and approach the bulk limit, indicating increased
stability for thicker 2D-STO. We first focus on the stability of
thinnest 2D-STO, i.e., 1 and 2 UC. As shown in Figure 2, 1
UC 2D-STO shows thermodynamic instability for TiO2- and
stoichiometric cases. The positive values of Ef suggest the
possibility of the decomposition of 2D-STO into binary oxides,
SrO and TiO2. However, 1 UC cases may be stable because of
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the interaction with the substrate. For 1 UC SrO-2D, a small
negative value implies marginal stability. When they are one
more unit cell thicker, all three cases display enhanced stability.
For example, 2 UC SrO-2D displays an impressively good
stability with an Ef of −0.591 eV, and TiO2- and stoichiometric
cases are also stable with an Ef of −0.174 and −0.22 eV,
respectively. The stability can be enhanced with larger
thickness.
In the experiments, 2−4 UC 2D-STO types were fabricated
and structure-characterized.13 The calculated formation
energies show that 2−4 UC 2D-STO types are thermodynami-
cally stable, which is consistent with the experimental findings.
Based on our calculations, the 1 UC stoichiometric case is not
thermodynamically stable, which implies that it may
decompose into binary compounds SrO and TiO2 in
equilibrium condition. In the experiments, the single-crystalline
form of the 1 UC-thick film was characterized by selected-area
electron diffraction (SAED).13 However, it is difficult to
determine the detailed structure information of 1 UC STO
from cross-sectional high-angle annular dark-field (HAADF)
images due to the damage and radiolysis caused by electron
beams,13 which makes it difficult to have a direct comparison
between theoretical and experimental results.
Notably, the thermodynamic stability of 2D-STO is
termination-dependent. With a similar thickness, SrO-2D
displays the best stability, while TiO2-2D shows the lowest
stability. SrO-TiO2-2D possesses modest stability as it
combines both terminations of SrO and TiO2. It can also be
noted that the Ef values of all 2D-STO types are larger than
that of the bulk. The elevation of Ef for 2D-STO can be
attributed to the presence of two additional surfaces with
broken bonds, which induce excess energy on the surfaces, i.e.,
surface energy (Esurf). Based on the slab model, we calculated
the surface energies of the STO (001) surfaces. For a
nonstoichiometric slab with the same termination (SrO or
TiO2 layer), the surface energy is dependent on the chemical
potential, as shown in Figure S1. The Esurf values at two
extreme conditions, i.e., SrO-rich and TiO2-rich, are listed in
Table S1. Both SrO- and TiO2-terminated surfaces possess
positive surface energies. This illustrates the reason why the Ef
values of 2D-STO are higher than those of the bulk. The
special stability of SrO-2D can also be figured out from the
surface energy. In the wide variation range of the chemical
potential of SrO (ΔμSrO), the SrO surface is more stable than
the TiO2 surface due to the lower surface energy of the former
(Figure S1 in the SI).
3.2. Unusual Band-Gap Trends. Band gap is one of the
most important parameters for semiconducting materials. To
understand the electronic structures of 2D-STO, we
investigated the band-gap trends of these ultrathin films.
Figure 3 presents the band gaps calculated by PBEsol and
HSE06. It is well known that semilocal functionals like PBEsol
usually underestimate the band gap of the solid significantly,
while hybrid functionals such as HSE06 show a much higher
accuracy in predicting the band gap. The calculated band gap
of the STO bulk supports this point. The HSE06-calculated
band gap is 3.34 eV, which is in good agreement with the
experimental value of 3.25 eV.30 Obviously, the PBEsol value
of 1.82 eV significantly underestimates the band gap. These
two theoretical values of bulk are presented in Figure 3 as
references (horizontal dotted lines) for the band-gap trends of
2D-STO.
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Figure 3. Fundamental band gaps of SrO-, TiO2-, and SrO-TiO2-
terminated 2D-STO as a function of thickness. Both PBEsol and
HSE06 functionals are utilized to calculate the band gaps. To make a
comparison of the capability of predicting band-gap trends for these
two functionals, the PBEsol gaps (large open symbols) of SrO- and
TiO2-2D are shifted with the constant ΔEg, which is taken as the
difference between the HSE06 gap and the PBEsol gap of bulk STO.
The shifted band gaps (small open circles and diamonds connected by
blue dashed lines) are presented together with the HSE06 gaps (solid
circles and diamonds). Band gaps of SrO-TiO2-2D are marked with
squares. The calculated band gaps of the bulk are 3.34 eV for HSE06
and 1.82 eV for PBEsol, as marked by the horizontal dotted lines.
We also calculated the quasiparticle (QP) band gap of bulk
STO by using a single-shot G0W0 method based on a PBE
calculation (for the calculation method, see the SI). The
electron−hole interaction is included via the G0W0-BSE
approach to calculate the optical gap. The calculated QP
band gap and optical gap together with HSE06 results are
listed in Table 1. We note that our results are in good
agreement with previous theoretical and experimental values.
For example, the QP direct gap of 4.02 eV is consistent with
the G0W0 value of 4.1 and 3.9 eV in previous works,31,32 and
G0W0-BSE optical gaps are in excellent agreement with
previously calculated values.32 Furthermore, the G0W0-BSE
optical gap is in good agreement with the experimental value of
3.75 eV.30 Notably, HSE06 direct and indirect band gaps are in
excellent agreement with G0W0-BSE and the experimental
results, which indicates the good accuracy of HSE06 in
calculating the gaps of STO.
Similar to the bulk, PBEsol-predicted band gaps of 2D-STO
are also underestimated in comparison with the HSE06 results.
In order to make a comparison of the capability of predicting
band-gap trends for these two methods, the PBEsol-calculated
band gap is shifted with the constant ΔEg, which is taken as the
difference between the HSE06 gap and the PBEsol gap of bulk
STO. The shifted band gaps are presented together with the
HSE06 gaps. Notably, the trends of the shifted band gaps agree
well with those from the hybrid functional. We also calculated
thicker slabs, 10 and 12 UC SrO-2D, by the PBEsol method.
The calculated band gaps of these two structures are 1.59 eV
and the same as that for 8 UC SrO-2D. These results indicate
the reliability of PBEsol in predicting the band-gap trends of
STO ultrathin films, although it underestimates the absolute
gap value. This rule may be useful if a very large supercell is
utilized for the calculations. In the following subsections, we
discuss the band-gap trends and electronic structures
calculated by HSE06.
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Table 1. Γ−Γ Direct and R−Γ Indirect Band Gaps of STO Bulk Calculated by PBEsol, HSE06, G0W0, and G0W0-BSE (shown
in bold)a
band gap (eV) PBEsol HSE06
Γ−Γ direct 2.17 3.72
R−Γ indirect 1.82 3.34
a
The exciton binding energy (Eb), which is the energy difference between the QP direct band gap and direct optical gap, is 0.24 eV. The indirect
optical gap of 3.45 eV is estimated by subtracting the Eb from the G0W0 QP indirect gap. Previously calculated and experimental values are also
listed for a comparison. Experimental direct and indirect band gaps were measured from the optical absorption spectra. bRef 31. cRef 33. dRef 32.
e
Ref 30.
As shown in Figure 3, SrO-2D displays an unexpected band-
gap trend with the variation of thickness (band structures in
Figure S2). For 1−3 UC, the band gaps of SrO-2D are larger
than the bulk value. This can be understood by the quantum
confinement effect, as their thicknesses are in the order of 1
nm. Interestingly, the band gaps decrease with increase in the
thickness of SrO-2D and quickly converge to a value lower
than the bulk value, which implies an abnormal behavior from
the usual quantum confinement effect. There is a noticeable
discontinuity of the band gap between thick SrO-2D and bulk
STO. The value of the gap discontinuity is about 0.18 eV. SrO-
2D exhibits a different behavior from the normal quantum
confinement effect, e.g., that is found in halide perovskites like
CsPbI3, in which Xiao et al. found that the band gaps decrease
with increasing film thickness and gradually approach the bulk
limit.34
From Figure 3, it is seen that TiO2-2D also displays an
interesting band-gap trend (band structures in Figure S3).
First, its band gaps show a weak quantum size effect, i.e., the
gaps vary slightly with change in the thickness. Second, the
band gaps are even smaller than those of SrO-2D and converge
to ∼2.43 eV, a value much smaller than the bulk value. A
previous study also showed that 1−3 UC TiO2-2D possesses
much smaller band gaps in comparison with SrO-2D and the
bulk, although the gap values are significantly underestimated
by using the PBE functional there.35 Such a low band gap shall
be helpful in electronic and photoelectronic applications of
2D-STO.
The calculated band gaps of SrO-TiO2-2D are also
presented in Figure 3 (squares) (band structures in Figure
S4). In this case, the thinnest (1−2 UC) 2D-STO display an
abrupt decrease of band gaps. With larger thickness, the band
gaps converge very quickly at 4 UC, indicating a quantum size
effect. Notably, stoichiometric 2D-STO possesses the smallest
band gap in comparison with SrO-2D and TiO2-2D. The
reduction of band gap from the bulk limit for the
stoichiometric case is due to a synergistic effect from both
SrO- and TiO2-terminations (see the next subsection).
The effects of full relaxation of the 2D cell on band-gap
trends are considered by allowing both in-plane lattice
constants and atomic positions’ relaxation. The band gaps of
the fully relaxed 2D-STO are presented together with the gaps
of cell-fixed 2D-STO in which in-plane lattice constants are
fixed to the bulk value and atomic positions are relaxed to
equilibrium (Figure S5). We find that full relaxation only
makes a small difference to 1 and 2 UC SrO-2D, and 1 UC
TiO2-2D. For thicker 2D-STO of these two types and also the
stoichiometric case, the band gaps of fully relaxed and cell-fixed
2D-STO are close to each other.
We also consider the effect of antiferrodistortive distortions
on the electronic properties. The low-temperature phase of
SrTiO3 has a tetragonal structure with antiferrodistortive
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G0W0 G0W0-BSE expt.
b d
4.02, 4.1 , 3.9 d
3.78, 3.73 3.75e
3.69, 3.65b,3. 69c, 3.57d 3.45, 3.40d 3.25e
distortions. In this phase, TiO6 octahedra rotate to produce a
low-symmetry structure (I4/mcm) from cubic. To elucidate
the effect of antiferrodistortive distortions on the electronic
structures, we built the structure models of 2D-STO from I4/
mcm bulk and calculated their electronic structures. Taking 4
and 6 UC 2D-SrO and 2D-TiO2 as typical examples, we
calculated their band gaps using the PBEsol method and made
a comparison with the corresponding bulk value and those of
the undistorted cases (Table S2). It is seen that antiferrodis-
tortive distortion increases the band gaps of 2D-STO.
Moreover, we find a similar gap discontinuity of 0.17 eV
between the 6 UC distorted SrO-2D and bulk as in the case of
the cubic phase (0.20 eV for 6 UC). Analysis of the orbital
composition of the bottom CB indicates the existence of band
splitting and a low-lying band in the distorted SrO-2D, similar
to the undistorted case. We also find a large band-gap
reduction for TiO2-2D due to the surface state.
We check the reliability of HSE06 in predicting the band gap
of 2D-STO by making a comparison with G0W0-BSE. A
previous study reported that the QP band gaps of 2D materials
show a linear relationship to inverse spatial separation (1/L,
where L is the distance between the repeated 2D structures
along the vacuum layer).36 The band gap of the completely
isolated 2D material can be obtained by extrapolating the gaps
of the 2D material to infinite L. Taking 1 UC TiO2-2D as an
example, we adopted this method to calculate the QP band gap
of this structure. Figure S6 shows a linear relationship between
the QP band gaps and 1/L. By extrapolating to infinite L (1/L
to zero), QP direct and indirect band gaps are calculated to be
4.57 and 3.85 eV, respectively. The direct optical gap obtained
from G0W0-BSE remains at almost a constant value of 3.39 eV,
which does not change with L. The exciton binding energy
(Eb), which is taken as the difference between the QP direct
gap and direct optical gap, is 1.18 eV. By subtracting Eb from
the QP indirect gap (3.85 eV), the indirect optical gap is
estimated to be 2.67 eV. Interestingly, this value is very close to
the HSE06-calculated indirect gap value of 2.58 eV.
This test of TiO2-2D together with the results of bulk
indicate that HSE06 exhibits good accuracy in predicting the
band gaps of STO. A good consistence of HSE06 and G0W0-
BSE in calculating the band gap was also found in the layered
Ruddlesden−Popper (RP) homologous series Srn+1TinO3n+1 by
Reyes-Lillo and co-authors.32 They found that HSE06 band
gaps agree well with experimental and G0W0-BSE optical band
gaps for RP phase Srn+1TinO3n+1, which possess similar
structures to 2D-STO.
3.3. Origin of Unusual Band-Gap Trends. We then
investigated the origin of the abnormal trends of the band gaps.
We first focused on the origin of the band-gap discontinuity in
SrO-2D. The most notable aspect from bulk to 2D-STO is the
reduction of dimension from 3D to 2D. Dimension reduction
implies a lower symmetry. This usually leads to a decrease of
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Figure 4. Orbital-projected band structures calculated by HSE06 for: (a) 8 UC ideal SrO-2D; (b) 8 UC relaxed SrO-2D; (c) 7 UC relaxed TiO2-
2D; (c) 6 UC relaxed SrO-TiO2-2D. Horizontal dashed lines mark the maximum of valence bands. Band weights of Ti 3d and O 2p orbitals are
sized by symbols. The energy difference (λ) between low-lying dxy bands and higher dxy band is marked in (b) and (d).
the degeneracy of bands and may imply the possibility of a
splitting low-lying band. In STO bulk, the conduction band
minimum (CBM) at Γ is triple-degenerate, as required by
symmetry, i.e., t2g bands. In 2D structure, the symmetry is
reduced and thus the triple degeneracy is broken, which results
in the splitting of t2g into double-degenerate and singlet states.
In this case, the dxy band is no longer degenerate with dyz and
dxz bands since the out-of-plane direction (z) is not equivalent
to the in-plane directions (x and y). To demonstrate this
picture, we calculated the orbital-projected band structures of 8
UC SrO-2D. Figure 4a shows the obvious splitting of dxy bands
from the double-degenerate dyz/dxz bands at Γ. However, the
reduction of dimension is not the main reason for the gap
discontinuity, since the band gap of the ideal SrO-2D
converges to the bulk value, as shown in Figure S7. (The
definition of the band gap of the ideal SrO-2D is dicussed
detailedly in SI.) For example, the band gap of the 8 UC ideal
SrO-2D is 3.35 eV, which is close to the bulk value of 3.34 eV.
Therefore, except for dimension reduction-induced band
splitting, other factors also play a crucial role in determining
the band-gap discontinuity.
In comparison with the ideal case, the relaxed SrO-2D
possesses two low-lying dxy conduction bands. The energy
difference (λ) between these two bands and the higher dxy
band is 0.19 eV, as shown in Figure 4b. This value is very close
to the gap discontinuity of 0.18 eV. The decomposed charge
densities of the low-lying dxy bands at Γ localize at Ti atoms
adjacent to the surface SrO layer for the relaxed slab (Figure
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S8c), while the charge densities of the lowest dxy bands spread
widely in the inner layers for the ideal case (Figure S8b). This
indicates that surface relaxation lowers the energy of the dxy
band, which is contributed mainly by the upmost Ti atoms. A
recent study predicted that CBM is mainly composed of Sr-5s
orbitals by using the GGA plus U method,37 which is different
from our results. Therefore, surface relaxation plays a desicive
role in determining the band-gap discontinuity.
Surface relaxation usually leads to ion displacements along
the surface normal of perovskite oxides. The ion displacements
of STO (001) surfaces have been widely studied in previous
experimental38,39 and theoretical works.27,40−42 We analyzed
the rumpling (s) of two near-surface layers and changes in
interlayer distances (Δdij) of three near-surface layers for SrO-
terminated STO (001) based on the 8 UC SrO-2D model (s
and Δdij are listed in Table S3). It is seen that our results are in
good agreement with previous experimental and theoretical
results. The rumpling values of the surface SrO layer and
adjacent TiO2 layer are 5.8 and −1.2 (in percent of bulk lattice
constant), respectively. A similar gap discontinuity of ∼0.2 eV
was predicted in Ruddlesden-Popper (RP) Srn+1TinO3n+1
phases, where the splitting of n-degenerate dxy bands leads to
the decrease of CBM with low-lying dxy bands.32 The gap
discontinuity in the RP phase was attributed to the off-
centering distortion of the Sr in the extra SrO layers and the Ti
adjacent to the extra SrO layers. Notably, the rumpling values
of the extra SrO layer and adjacent TiO2 layer in RP phase are
5 and −1 (in percent of bulk lattice constant), respectively.
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The consistent rumpling in the STO surface and RP interface
agrees with the similar gap discontinuity of these two cases,
although different chemical environments are presented for
them.
The abnormal trend of TiO2-2D has a different origin.
Figure 4c shows the orbital-project band structure of 7 UC
TiO2-2D. As expected, the dxy band is no longer degenerate
with dyz/dxz bands due to the reduction of dimension. CBM is
mainly contributed from dxy bands. Notably, there are surface
states near the top of the valence bands, which are absent in
SrO-2D. These surface states show a large dispersion, which
reduces the band gap largely from the value of 3.34 eV for bulk
to the value of 2.43 eV for thick TiO2-2D (>7 UC). The
decomposed charge densities in real space for the valence band
maximum (VBM) indicate that surface states are mainly
contributed by O atoms in the surface TiO2 layer (Figure S8d).
Surface states-induced gap narrowing was also predicted by
using the LDA method in TiO2-terminated BaTiO3 and
SrTiO3 (001) surfaces (with a relatively thin (3 UC) slab).26,27
This effect was also observed in ZrO2-terminated surfaces and
films of BaZrO3.43
Figure 4d shows the band structure of 6 UC relaxed SrO-
TiO2-2D. It can be seen that both the band splitting at CBM
and the dispersive surface band at VBM appear. This can be
understood in that both SrO- and TiO2-terminations exist in
SrO-TiO2-2D. It produces a synergistic decrease of band gap
from the bulk limit, which results in the smallest band gap for
stoichiometric 2D-STO. Besides, the energy difference (λ)
between the low-lying dxy and higher dxy band is 0.20 eV
(Figure 4d), which is close to that of 0.19 eV in SrO-2D.
Pronounced band-gap narrowing due to the surface states of
valence bands was also predicted in a previous B3PW
calculation with a 4 UC stoichiometric slab model.42
To illustrate the origin of abrupt change of the band gaps
from 1 to 2 UC SrO-TiO2-2D, we calculated the orbital-
projected band structures for 1 and 2 UC three types of 2D-
STO (Figure S9 in SI). From the comparison between 1 and 2
UC SrO-TiO2-2D, it is seen that these two cases show similar
dispersion and band width for the top-valence bands. A
significant difference lies in the conduction bands. The two-
unit-cell SrO-TiO2-2D possesses a low-lying dxy band, which
reduces the band gap largely and thus is responsible for the
abrupt change of the band gaps from 1 to 2 UC. It is more
obvious when the conduction bands of 2 UC SrO-TiO2-2D are
compared with those of 1 UC TiO2-2D and 2 UC SrO-2D,
both of which possess two Ti atoms and thus two dxy bands. In
the latter two cases, there is no significant energy separation
between the two dxy bands. The large energy difference of the
two dxy bands in SrO-TiO2-2D is probably because of the
asymmetry of SrO-TiO2 structure, which is not present in
TiO2- and SrO-2D.
4. CONCLUSIONS
In summary, we investigated the thermodynamic and
electronic properties of 2D-STO using first-principles methods.
We find that, except for 1UC, all other 2D-STO types are
thermodynamically stable and the stability is increased for
thicker 2D-STO types. Besides, the stability of 2D structures is
termination-dependent. 2D-STO with SrO termination shows
the best stability in comparison with TiO2- and stoichiometric
cases, which can be attributed to the low surface energy of the
SrO-terminated surfaces. Moreover, surface termination plays a
crucial role in determining the electronic structures of 2D-
522
pubs.acs.org/JPCC Article
STO. We find that SrO-2D displays an unexpected band-gap
trend on varying the thickness. There is a discontinuity of the
band gap between thick SrO-2D and bulk STO. The origin of
the discontinuity can be attributed to the fact that structural
distortion of the surface induced by relaxation lowers the
energy of the dxy band of surface Ti. The band gaps of TiO2-2D
also show an interesting trend that gap values converge to
∼2.43 eV, which is much smaller than those of SrO-2D and the
bulk. The reason for the large reduction of the band gap is that
O atom-dominated surface bands exhibit a large dispersion,
which reduces the band gap significantly. This study provides
some important insights into understanding the thermody-
namic stability and electronic properties of 2D-STO, especially
at the 2D-3D crossover. Our results will be helpful for further
theoretical and experimental research on the physical proper-
ties and device applications of 2D perovskite oxides.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.1c07159.
Additional calculation details on formation energies,
surface energies, band-decomposed charge density and
G0W0-BSE method; Calculated surface energies, band
gaps of 2D-STO with antiferrodistortive distortions,
surface ions displacements, surface energies as a function
of the chemical potential, HSE06 band structures of
three types of 2D-STO, band gaps of fully relaxed 2D-
STO, Convergence test of QP band gap with respect to
inverse spatial separation, HSE06 band gaps of ideal
SrO- and TiO2-2D, band-decomposed charge density,
orbital-projected band structures of 1−2 UC STO
(PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Yi Yang − Faculty of Materials, Metallurgy and Chemistry and
College of Rare Earths, JiangXi University of Science and
Technology, Ganzhou 341000, China; orcid.org/0000-
0002-0361-5823; Email: yangyisouth@yeah.net
Tong-Xiang Liang − Faculty of Materials, Metallurgy and
Chemistry and College of Rare Earths, JiangXi University of
Science and Technology, Ganzhou 341000, China;
Email: liang_tx@126.com
Authors
Xun-Jian Hu − Faculty of Materials, Metallurgy and
Chemistry and College of Rare Earths, JiangXi University of
Science and Technology, Ganzhou 341000, China
Chunju Hou − School of Science, JiangXi University of Science
and Technology, Ganzhou 341000, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.1c07159
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors are grateful to Dr. Xianxin Wu (Max-Planck-
Institut für Festkörperforschung) and Prof. Yuefeng Nie
(Nanjing University) for their helpful discussions. This work
was supported by the National Natural Science Foundation of
https://doi.org/10.1021/acs.jpcc.1c07159
J. Phys. Chem. C 2022, 126, 517−524
The Journal of Physical Chemistry C
China (Grant No. 11847150) and Jiangxi Provincial Natural
Science Foundation (Grant No. 20202BAB211006). This work
was done using computing resources from the National
Supercomputing Center in LvLiang of China.
■
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