PHYSICAL REVIEW B 109, L220101 (2024)

Letter

Oxygen tilt driven polar superorders in BiFeO3 -based superlattices

Ran Xu ,1,* Francesco Delodovici,1 Brahim Dkhil,1 and Charles Paillard 2,1,†
1
Université Paris-Saclay, CentraleSupélec, CNRS, Laboratoire SPMS, 91190 Gif-sur-Yvette, France
2
Smart Ferroic Materials Center, Institute for Nanoscience and Engineering and Department of Physics,
University of Arkansas, Fayetteville, Arkansas 72701, USA

(Received 21 February 2024; revised 17 April 2024; accepted 20 May 2024; published 4 June 2024)

Ferroelectric-dielectric superlattices have attracted renewed interest for their ability to frustrate the polar order,
leading to the emergence of exotic polar textures. The electrostatic depolarization, thought to be responsible
for the complex polar textures in these superlattices, can be alleviated by replacing the dielectric layer with a
metallic one. One would thus expect that a close to uniform polarization state be recovered in the ferroelectric
layer. However, here we show, using density-functional theory calculations, that metastable antipolar motions
may still appear in superlattices combining multiferroic BiFeO3 and metallic SrRuO3 perovskite layers. We find
that a complex oxygen octahedra tilt order, a so-called nanotwin phase, exists in BiFeO3 /SrRuO3 superlattices
and competes with a more conventional phase. It leads to a doubling of the chemical period along the out-of-
plane direction, owing to the presence of an oxygen octahedra tilt-wave pattern and antipolar motions caused by
trilinear energy couplings. We also show that out-of-plane polar displacements in the BiFeO3 layer may reverse
the (anti)polar displacements thanks to a strong quadrilinear coupling term. The oxygen tilt-driven couplings
identified here may open new ways to engineer and control polar displacements in superlattice-based polar
metals and hybrid improper (anti)ferroelectrics.

DOI: 10.1103/PhysRevB.109.L220101

Ferroelectric superlattices (SLs) are repeated stacking of In this regard, we mostly focus on BiFeO3 /SrRuO3 SLs.
alternating ferroelectric nanolayers and dielectric or metal- BiFeO3 (BFO) is a prototypical multiferroic with large spon-
lic layers. SL architectures allow to control both mechanical taneous polarization, antiferromagnetic order superimposed
and electrical boundary conditions felt by the ferroelectric with a cycloidal spin modulation and strong a− a− a− oxy-
nanolayers. Intriguing new physics has resulted from explor- gen octahedra tilt pattern in Glazer notation [19] at room
ing ferroelectric SLs and nanostructures, such as the presence temperature [20–23]. Recent works have reported emerging
of polar, topologically protected quasiparticles [1–7], often complex phases in BFO-based superlattices, such as antiferro-
emerging as low-energy metastable states [5,8,9]. In fact, electric phases in BiFeO3 /LaFeO3 [24] and BiFeO3 /NdFeO3
metastable phases have been wildly evidenced in ferroelectric [25] SLs. Perhaps most strikingly, BiFeO3 /TbScO3 SLs have
nanostructures and manipulated, for instance with strain, elec- shown the room-temperature coexistence of a complex polar
tric fields [10,11] or optical excitation [12,13] to achieve new phase and an antiferroelectric Pnma phase as well as their
exotic properties such as negative capacitance [14–16] when electrical control [10]. In addition, BFO has a rich polymor-
reaching these hidden phases. phic playground, with for instance a low-energy lying Pnma
In most ferroelectric/dielectric SLs, a uniformly out-of-
phase [26,27] with a− a− c+ tilts. It can thus be hoped that a
plane polarized ferroelectric nanolayer would experience a
large number of phases, and properties, can be addressed even
large depolarizing electric field, resulting from poor elec-
in BFO/metal SLs if one manages to frustrate its octahedra
trostatic screening of the polarization-bound charges by the
rotation pattern, for instance by associating BFO with a per-
dielectric layer. Electrostatic frustration was thus put forward
as an explanation of the resulting structure, and thus func- ovskite metal having an a− a− c+ tilt pattern such as SrRuO3
tional properties [3,17,18] of ferroelectric SLs. It is however (SRO) [28,29].
legitimate to ask whether other degrees of freedom, such as The present work uses density-functional theory (DFT)
oxygen octahedra tilts in perovskite oxides, play an important calculations to explore the impact of oxygen octahedra tilt
role in the formation of complex structural phases in SLs. One rotation on the emergence of complex phases in BFO-based
way to test this hypothesis is to employ a metallic spacing SLs. We show that, despite the metallic nature of SRO, which
layer rather than a dielectric one, thus limiting or canceling limits depolarizing effects, unexpected in-plane antipolar mo-
electrostatic depolarizing effects. tions may be retained in the SL in a competing superordered
phase. We attribute this result to the strong trilinear coupling
between Bi cations motion and oxygen octahedra tilts. Con-
currently, polar displacements in the out-of-plane direction
*
ran.xu@centralesupelec.fr are retained in the BFO layer due to screening of the polar-
†
paillard@uark.edu ization charges by the metallic SRO layer. We show that this

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XU, DELODOVICI, DKHIL, AND PAILLARD PHYSICAL REVIEW B 109, L220101 (2024)

(a) (b) (c)

(a)

FIG. 1. Phonon instabilities in high-symmetry superlattices

[BiFeO3 ]1 /[SrRuO3 ]1 superlattices. (a) Sketch of the 2 × 2 × 2
supercell with atoms in their cubiclike, high-symmetry positions.
(b) (d)
(b) Phonon dispersion in the cubiclike phase (high-symmetry points
in the first Brillouin zone are defined in the Supplemental Material
[43]).

out-of-plane polar displacement may help control the di-

rection of (anti)polar in-plane atomic motions thanks to
quadrilinear coupling involving oxygen octahedra tilts.
DFT calculations were performed using the Vienna ab FIG. 2. Atomic patterns in conventional and superordered
initio simulation package (VASP) [30–33] with the projector phases. (a) Ground-state relaxed structure and (b) its projection on
augmented waves method [33,34]. Our pseudopotentials in- phonon modes of the high-symmetry structure; (c) superordered
clude valence electrons from Bi 5d, 6s, and 6p, Fe 3s, 3p, 3d, relaxed structure and (d) its projection on phonon modes of the high-
and 4s, Sr 4s, 4p, 5s, Ru 4s, 4p, 4d, 5s, and O 2s, 2p states. symmetry structure. Arrows on the left of each structure depict A-site
We employ the PBESol exchange-correlation functional [35]. cation displacements, while rotating arrows on the structure depict
Following the literature, we apply a Hubbard correction [36] M5 -related oxygen tilts. Right side rotating arrows depict clockwise
of 4 eV and 0.6 eV on the d orbitals of Fe [26] and Ru [37,38] (blue) or anticlockwise oxygen octahedra rotation associated with M2
atoms. Collinear magnetism is assumed. The plane-wave cut- (a) and A2 (c) modes.
off is 500 eV, meanwhile a 5 × 5 × 5 Monkhorst-Pack mesh
[39] is employed. Total energy is converged below 10−7 eV
in self-consistent cycles. Structural convergence is achieved out-of-plane direction (see Supplemental Material [43]). We
when the forces are smaller than 2 meV/Å. To mimic the adopt a Glazer-like notation a−/+ b−/+ c−/+ for each pseu-
effect of epitaxial strain imposed by a cubic SrTiO3 substrate, docubic perovskite cell, where −/+ indicates anticlockwise
we fix the in-plane lattice constants of the SLs to 3.895 Å, and clockwise rotation of the oxygen octahedron. We can
as calculated from DFT. At the SrTiO3 in-plane lattice con- then describe the lowest unstable M mode by the sequence
stant (and in general reasonable strains in the range −2% 00c+ /00c+ for the BFO1 /SRO1 SL. The unstable mode at
to +2%), we do not expect strained BiFeO3 and SrRuO3 to the A point, which has A2 symmetry [43], corresponds to
exhibit markedly different structural properties from the bulk a complex wavelike arrangement of oxygen octahedra tilts,
according to the literature [40,41]. Phonon band structures leading to doubling of the SL period [see Fig. 2(c) and Fig. 3].
for high-symmetry (cubiclike) BFO/SRO SLs were obtained In our Glazer-like notation, this mode corresponds to a tilt
using density-functional perturbation theory as implemented pattern 00c− /00c− /00c+ /00c+ . Concurrently, less unstable
in VASP and the PHONOPY package [42]. modes at  [see Fig. 1(b)] show polar displacements car-
We start by calculating the phonon dispersion of ried by off-centering of the Bi ions in plane (5 symmetry)
[BiFeO3 ]1 /[SrRuO3 ]1 SL (subsequently noted BFO1 /SRO1 ), and out of plane (1 symmetry), respectively. Interestingly,
with all ions fixed in the high-symmetry positions of the cubic the -Z lowest unstable branch is flat, indicating that polar
perovskite structure [see Fig. 1(a)]. The high-symmetry struc- motions of the Bi ions between two BFO layers separated
ture has P4mm space group due to the chemical arrangement. by a SRO layer do not carry an additional electrostatic cost
The phonon dispersion, shown in Fig. 1(b), shows strong compared to their antipolar displacement. The metallic na-
imaginary frequencies (depicted as negative), a hallmark of ture of the SRO, therefore, likely screens the electrostatic
major structural instabilities. The most prominent instabilities dipolar energy cost associated with in-plane polar motions,
exist at the M (1/2, 1/2, 0) and A (1/2, 1/2, 1/2) points in and thus effectively decouples the in-plane polar motions of
the Brillouin zone. The lowest-frequency unstable M mode successive BFO layers. Note that the -Z branch flatness also
corresponds to antiphase oxygen octahedra tilts along the suggests the possibility to access polar states which combine

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our calculated value for bulk octahedra rotation in BFO and

(a) (b) SRO are respectively 12.6◦ and 7◦ .
Surprisingly, our relaxation evidenced a second structure
with very close energy to the ground state (9 meV/perovskite
cell), depicted in Fig. 2(c). We observe that the structural
period is doubled out of plane with respect to the superlattice
chemical period. We refer to this structure as superordered.
The superordered structure has similar M5 -symmetry a− a− 0
tilt pattern and amplitude as the ground-state structure [see
Fig. 3(a)]. It possesses, as well, similar out-of-plane polar
motions of the Bi ions, albeit with smaller amplitude than
the conventional phase. The main differences between the
conventional and superordered structure arise from the con-
densation of a tilt-wavelike pattern of A2 symmetry [see
Fig. 2(c) and Fig. 3] and in-plane antipolar displacements
of Z5 symmetry. The Z5 displacements resemble the 5 dis-
placements of the conventional phase, but reverse sign every
SL chemical period [see Fig. 2(c)]. They account for 60%
of the superordered structure distortions. The A2 mode, a
tilt-wavelike pattern where rotations around the out-of-plane
FIG. 3. Complex tilt patterns in BFO/SRO superlattices. axis alternate between clockwise and anticlockwise every pe-
(a) BFO1 /SRO1 in-plane tilt angle (yellow diamonds) associated riod [see Figs. 2(c) and 3(a)], represents about 14% of the
with the M5 mode and out-of-plane tilts (circles) associated total distortions [Fig. 2(d)]. It is an instance of the nanotwin
with the M2 (yellow) and A2 (orange) modes. The conventional
phases predicted to occur in BFO at high temperature [47]
and superordered phase are depicted by dashed and plain lines,
or in BiFeO3 /NdFeO3 solid solutions [48], and generates
respectively. (b) Oxygen octahedra tilt angles in the conventional
the antipolar displacement pattern Z5 arising from trilinear
(dashed lines) and superordered (plain lines) phase of BFO2 /SRO2 ,
with the same color code as (a).
couplings in the free-energy landscape of the form M5 A2 Z5
(see below, and Ref. [46]).
Whether combining perovskites with competing tilt sys-
multiple k points, as can be the case for polar skyrmions or tems in superlattices universally leads to the existence of
vortices [1,2]. (meta)stable superordered phases likely relies on the relative
Next, we relax the full BFO1 /SRO1 superlattice in a strength of the tilt instabilities in the high-symmetry phase
2 × 2 × 4 pseudocubic supercell (effectively simulating a of the perovskites composing each nanolayer. Yet, our work
BFO1 /SRO1 /BFO1 /SRO1 arrangement in the out-of-plane shows that BFO-based SLs are an interesting playground
direction), thus allowing the significant A and Z instabilities to to engineer such superordered phases, as recent experimen-
develop and double the chemical wavelength. After exploring tal reports have found some evidence of their existence via
various atomic distortions starting points, we eventually find high-resolution transmission electron microscopy [49] or x-
two structures with minimal energy. The first one, the ground ray diffraction [50,51]. In addition, we predict that (i) larger
state, is depicted in Fig. 2(a). It is characterized by (i) an SLs, such as BFO2 /SRO2 , also exhibit metastable superorder
a− a− c+ general tilt system in Glazer notation and (ii) out- tilt-wavelike patterns associated with antipolar features (see
of-plane and in-plane polar motions in the BFO layer along Fig. 3(b) and Supplemental Material [43]); (ii) BFO/dielectric
the [001̄] and [110] directions, respectively. Out-of-plane SLs, such as BiFeO3 /LaFeO3 (BFO/LFO), also harbor such
polar motions show displacements of the Bi ions towards metastable superordered phases (see Supplemental Material
FeO2 planes, and have 1 symmetry. They represent ≈40% [43]), consistent with recent observations [49] indicating com-
of the distortions [Fig. 2(b)]. In-plane polar motions, of 5 peting conventional and superordered phases in BFOn /LFOn
symmetry, consist mostly of opposite motions of Bi and O up to n = 5.
along the [110] direction and represent 40% of the distortions. Since the conventional [Fig. 2(a)] and superordered
Small Sr and O motions, opposite to the BiO plane motions, [Fig. 2(c)] phases are so close in energy (9 meV/p.u.), it
are also present, a feature reminiscent of hybrid improper is possible that they coexist at room temperature ( kB2T ≈
ferroelectrics [44,45], and whose origin can be traced back 12.5 meV at room temperature), as coexisting metastable
to known atomistic couplings between dipolar displacements phases have already been observed in some BFO-based su-
and oxygen octahedra tilts in perovskite oxides [46]. Of perlattices [10,49]. It is also known that external stimuli such
course, the present SLs are metallic in the RuO2 planes (see as THz or visible excitation [52], thermal quenching [53],
Supplemental Material [43]). Thus the ground state (which we or electric field application [10] (for dielectric superlattices
coin conventional phase) is not ferroelectric but exhibits polar such as BFO/LFO) may be employed to access close in en-
features. Octahedra tilts account for the remaining 20% of the ergy metastable states. We now set out to understand the
structural distortions, with M5 [a− a− 0 tilts of amplitude 6–8◦ , atomistic energy landscape explaining the emergence of this
see Fig. 3(a)] and M2 (00c+ tilts with typical amplitude of superordered phase in BFO1 /SRO1 using symmetry-relevant
11.5◦ in the BFO layer and 4◦ in the SRO layer) modes each modes and a Taylor expansion of the energy around the high-
contributing to about 10% of the distortion. In comparison, symmetry structure of Fig. 1(a). Such approach has been

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Subsequently, once the 1 and M5 modes are condensed, only

the oxygen octahedra rotation along the out-of-plane direction
lower the energy, with the M2 and A2 modes slightly lowering
the energy further. Only then, once the modes 1 , M5 , and
either M2 or A2 are condensed, can the energy be further
lowered by condensing the in-plane polar 5 mode (when M2
is condensed) or the in-plane antipolar mode Z5 (when A2 is
condensed) as plotted in Fig. 4(b). Interestingly, Figs. 4(b)–
4(d) show that the energy curve is asymmetric; symmetry
analysis of possible energy couplings (see Supplemental Ma-
terial [43]) reveals that it is the result of trilinear coupling
terms of the form φM2 φM5 u5 and φA2 φM5 uZ5 . Quite surpris-
ingly, the out-of-plane polar mode 1 significantly alters these
trilinear couplings: without it [u1 = 0, see dashed lines in
Fig. 4(b)] the minimum of energy for the Z5 or 5 mode
is reversed compared to the case u1 = 1. This quadrilinear
coupling with out-of-plane polar displacements creates new
opportunities to use BFO-based SLs to engineer switchable
hybrid-improper polar displacements. Polarization is noto-
riously difficult to switch in hybrid-improper ferroelectrics.
Since we have indications that the features exposed in this
FIG. 4. Energetics and potential for polar displacement switch- work apply to other BFO-based SLs [49], one may envi-
ing. (a) Energy with respect to the high-symmetry phase, when sion new pathways to switch polarization in hybrid-improper
modes are condensed. (b) Energy with respect to the high-symmetry ferroelectrics. In particular, in BFO/dielectric superlattices,
phase when uZ5 (red) is condensed while φM5 , φA2 = 1 and when 5 one could imagine to manipulate u1 via electric fields or
(blue) is condensed while φM2 , φM5 = 1. Dashed lines indicate no optical excitation, and leverage the mechanisms demonstrated
out-of-plane polar displacement (u1 = 0), while plain lines indicate in Fig. 4(b) to eventually switch the in-plane polarization.
u1 = 1; (c) and (d) are (φM2 , φ5 ) and (φA2 , φZ5 ) energy maps when In fact, we show in the Supplemental Material [43] that u1
u1 = 1 and φM5 = 1. can indeed control the direction of in-plane polar moments in
[BiFeO3 ]1 /[LaFeO3 ]1 SLs.
The present work, by means of ab initio calculations,
successfully applied over the years to derive effective Hamil- reveals that tilt-induced nanotwin superorders can be engi-
tonians in complex perovskite oxides such as BiFeO3 [54] and neered in multiferroic BiFeO3 -based SLs. We also show that,
related superlattices [55] providing excellent agreement with even in BFO/metal SLs, one may generate antipolar dis-
experimental observations [56,57]. Based on the projection placements due to trilinear couplings acting in the nanotwin
of the atomic displacements onto the phonon calculated in phase. Furthermore, the coupling between the out-of-plane
Fig. 1, we were able to construct a set of six symmetry- polar displacements, in-plane (anti)polar, and tilts may be a
adapted characteristic displacement patterns: u1 represents step towards control of the polarization in hybrid-improper
polar displacements of the Bi sublattice in the [001] direction; ferroelectrics of hybrid-improper polar metals, for instance
u5 represent antipolar motions of Bi and Sr ions along the via electrical or optical means, or THz manipulation using
[110] direction and it is akin to polar displacements found in the squeezing effect to reduce the out-of-plane polarization
hybrid improper ferroelectrics [44]. Meanwhile uZ5 indicates [58]. Future works will investigate how to further stabilize
that these latter displacements change sign every chemical these superordered phases and manipulate the polar order in
period along the out-of-plane direction; φM2 and φA2 represent various BFO-based superlattices. A promising prospect is the
the oxygen tilting pattern around [001] summarized in Fig. 3; use of tensile biaxial strain, as shown in the Supplemental
φM5 represents an a− a− 0 pattern of oxygen octahedra rota- Material [43].
tions. Both the conventional and superordered phases show
the M5 tilts with similar magnitude (see Fig. 3), as well as the R.X. and C.P. thank the China Scholarship Council (CSC).
1 polar out-of-plane polar motion of the Bi ions towards the C.P. acknowledges financial support from Agence Nationale
FeO2 plane. de la Recherche (ANR) under Grant No. ANR-21-CE24-
To further elucidate the origin of the structural features of 0032 (SUPERSPIN). We thank the European Unions Horizon
BFO/SRO SLs, we condense individually the displacement 2020 research and innovation program under Grant Agree-
patterns of different symmetry to understand the energy cou- ment No. 964931 (TSAR). This work was performed thanks
plings at play. Clearly, the 1 out-of-plane polar mode and to the Mesocentre Ruche computing center from Univer-
M5 in-plane tilt modes are the strongest instabilities, leading sité Paris-Saclay and the TGCC high-performance computing
each to a lowering of the energy from the high-symmetry center through Grant No. A0130912877. We thank Prof.
structure by about 250 meV/p.u. each [see Fig. 4(a)]. L. Bellaiche for insightful comments on this manuscript.

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