The archetypical antiferroelectric, PbZrO3, is currently attracting a lot of interest, but no consensus can be clearly established on the nature of its ground state as well as on the influence of external stimuli over its physical properties. Here, the antiferroelectric state of 45-nm-thick epitaxial thin films of PbZrO3 is established by observing the characteristic structural periodicity of antiparallel dipoles at the atomic scale, combined with clear double hysteresis of the polarization-electric field response related to antiferroelectric–to–ferroelectric phase transitions. Surprisingly, while the antiferroelectric state is identified as the ground state, temperature-dependent measurements show that a transition to a ferroelectric-like state appears in a large temperature window (100 K). Atomistic simulations further confirm the existence, and provides the origin, of such ferroelectric state in the films. Electric-field-induced ferroelectric transitions are also detected by the divergence of the piezoresponse force microscopy response. Using this technique, we further reveal the signature of a ferroelectric ground state for 4-nm-thick PbZrO3 films. Compared with bulk crystals, these results suggest a more complex competition between ferroelectric and antiferroelectric phases in epitaxial thin films of PbZrO3.
REFERENCES
1.
C.
Kittel
, “
Theory of antiferroelectric crystals
,” Phys. Rev.
82
(5
), 729
–732
(1951
).2.
K. M.
Rabe
, in Functional Metal Oxides
, 1st ed.,
edited by
S. B.
Ogale
,
T. V.
Venkatesan
, and
M. G.
Blamire
(
Wiley
, 2013
), pp. 221
–244
.3.
K.
Shapovalov
and
M.
Stengel
, “
Tilt-driven antiferroelectricity in PbZrO3
,” arXiv:2112.12167 (2021
).4.
E.
Sawaguchi
,
H.
Maniwa
, and
S.
Hoshino
, “
Antiferroelectric structure of lead zirconate
,” Phys. Rev.
83
(5
), 1078
–1078
(1951
).5.
M.
Ye
,
Q.
Sun
,
X.
Chen
,
Z.
Jiang
, and
F.
Wang
, “
Effect of Eu doping on the electrical properties and energy storage performance of PbZrO3 antiferroelectric thin films
,” J. Am. Ceram. Soc.
94
(10
), 3234
–3236
(2011
).6.
S.-T.
Zhang
,
A. B.
Kounga
,
W.
Jo
,
C.
Jamin
,
K.
Seifert
,
T.
Granzow
,
J.
Rödel
, and
D.
Damjanovic
, “
High-strain lead-free antiferroelectric electrostrictors
,” Adv. Mater.
21
(46
), 4716
–4720
(2009
).7.
Y.
Liu
,
J. F.
Scott
, and
B.
Dkhil
, “
Direct and indirect measurements on electrocaloric effect: Recent developments and perspectives
,” Appl. Phys. Rev.
3
(3
), 031102
(2016
).8.
J.
Parui
and
S. B.
Krupanidhi
, “
Electrocaloric effect in antiferroelectric PbZrO3 thin films
,” Phys. Status Solidi RRL
2
(5
), 230
–232
(2008
).9.
A.
Pérez-Tomás
,
M.
Lira-Cantú
, and
G.
Catalan
, “
Above-bandgap photovoltages in antiferroelectrics
,” Adv. Mater.
28
(43
), 9644
–9647
(2016
).10.
S.
Roberts
, “
Dielectric properties of lead zirconate and barium-lead zirconate
,” J Am. Ceram. Soc.
33
(2
), 63
–66
(1950
).11.
A. K.
Tagantsev
,
K.
Vaideeswaran
,
S. B.
Vakhrushev
,
A. V.
Filimonov
,
R. G.
Burkovsky
,
A.
Shaganov
,
D.
Andronikova
,
A. I.
Rudskoy
,
A. Q. R.
Baron
,
H.
Uchiyama
,
D.
Chernyshov
,
A.
Bosak
,
Z.
Ujma
,
K.
Roleder
,
A.
Majchrowski
,
J.-H.
Ko
, and
N.
Setter
, “
The origin of antiferroelectricity in PbZrO3
,” Nat. Commun.
4
(1
), 2229
(2013
).12.
P.
Tolédano
and
M.
Guennou
, “
Theory of antiferroelectric phase transitions
,” Phys. Rev. B
94
(1
), 014107
(2016
).13.
B. A.
Scott
and
G.
Burns
, “
Crystal growth and observation of the ferroelectric phase of PbZrO3
,” J Am. Ceram. Soc.
55
(7
), 331
–333
(1972
).14.
O. E.
Fesenko
,
R. V.
Kolesova
, and
Y.
Sindeyev
, “
The structural phase transitions in lead zirconate in super-high electric fields
,” Ferroelectrics
20
(1
), 177
–178
(1978
).15.
K.
Roleder
,
G. E.
Kugel
,
J.
Handerek
,
M. D.
Fontana
,
C.
Carabatos
,
M.
Hafid
, and
A.
Kania
, “
The first evidence of two phase transitions in PbZrO3 crystals derived from simultaneous Raman and dielectric measurements
,” Ferroelectrics
80
(1
), 161
–164
(1988
).16.
K.
Roleder
and
J.
Dee
, “
The defect-induced ferroelectric phase in thin PbZrO3 single crystals
,” J. Phys.: Condens. Matter
1
(8
), 1503
–1510
(1989
).17.
Z.
Xu
,
X.
Dai
,
D.
Viehland
,
D. A.
Payne
,
Z.
Li
, and
Y.
Jiang
, “
Ferroelectric domains and incommensuration in the intermediate phase region of lead zirconate
,” J Am. Ceram. Soc.
78
(8
), 2220
–2224
(1995
).18.
R.
Faye
,
H.
Liu
,
J.-M.
Kiat
,
B.
Dkhil
, and
P.-E.
Janolin
, “
Non-ergodicity and polar features of the transitional phase in lead zirconate
,” Appl. Phys. Lett.
105
(16
), 162909
(2014
).19.
J.
Zhai
and
H.
Chen
, “
Direct current field and temperature dependent behaviors of antiferroelectric to ferroelectric switching in highly (100)-oriented PbZrO3 thin films
,” Appl. Phys. Lett.
82
(16
), 2673
–2675
(2003
).20.
P.
Ayyub
,
S.
Chattopadhyay
,
R.
Pinto
, and
M. S.
Multani
, “
Ferroelectric behavior in thin films of antiferroelectric materials
,” Phys. Rev. B
57
(10
), R5559
–R5562
(1998
).21.
L.
Pintilie
,
K.
Boldyreva
,
M.
Alexe
, and
D.
Hesse
, “
Coexistence of ferroelectricity and antiferroelectricity in epitaxial PbZrO3 films with different orientations
,” J. Appl. Phys.
103
(2
), 024101
(2008
).22.
S. E.
Reyes-Lillo
and
K. M.
Rabe
, “
Antiferroelectricity and ferroelectricity in epitaxially strained PbZrO3 from first principles
,” Phys. Rev. B
88
(18
), 180102
(2013
).23.
R. I.
Eglitis
and
D.
Vanderbilt
, “
Ab initio calculations of BaTiO3 and PbTiO3 (001) and (011) surface structures
,” Phys. Rev. B
76
(15
), 155439
(2007
).24.
K. M.
Rabe
and
P.
Ghosez
, “Ferroelectricity in PbTiO3 thin films: A first principles approach,” J. Electroceramics
4
(2/3
), 379
–383
(2000
).25.
J. S.
Baker
and
D. R.
Bowler
, “
Polar morphologies from first principles: PbTiO3 films on SrTiO3 Substrates and the p(2×Λ) surface reconstruction
,” Adv. Theory Simul.
3
(11
), 2000154
(2020
).26.
B. K.
Mani
,
C.-M.
Chang
,
S.
Lisenkov
, and
I.
Ponomareva
, “
Critical thickness for antiferroelectricity in PbZrO3
,” Phys. Rev. Lett.
115
(9
), 097601
(2015
).27.
K.
Patel
,
B.
Xu
,
S.
Prosandeev
,
R.
Faye
,
B.
Dkhil
,
P.-E.
Janolin
, and
L.
Bellaiche
, “
Temperature-dependent properties of the antiferroelectric model PbZrO3: An effective Hamiltonian study
,” Phys. Rev. B
106
, 214108
(2022
).28.
A.
Roy Chaudhuri
,
M.
Arredondo
,
A.
Hähnel
,
A.
Morelli
,
M.
Becker
,
M.
Alexe
, and
I.
Vrejoiu
, “
Epitaxial strain stabilization of a ferroelectric phase in PbZrO3 thin films
,” Phys. Rev. B
84
(5
), 054112
(2011
).29.
L.
Qiao
,
C.
Song
,
Q.
Wang
,
Y.
Zhou
, and
F.
Pan
, “
Polarization evolution in nanometer-thick PbZrO3 Films: Implications for energy storage and pyroelectric sensors
,” ACS Appl. Nano Mater.
5
(5
), 6083
–6088
(2022
).30.
K.
Boldyreva
,
L.
Pintilie
,
A.
Lotnyk
,
I. B.
Misirlioglu
,
M.
Alexe
, and
D.
Hesse
, “
Thickness-driven antiferroelectric-to-ferroelectric phase transition of thin PbZrO3 layers in epitaxial PbZrO3∕Pb(Zr0.8Ti0.2)O3 multilayers
,” Appl. Phys. Lett.
91
(12
), 122915
(2007
).31.
G.
Apachitei
,
J. J. P.
Peters
,
A. M.
Sanchez
,
D. J.
Kim
, and
M.
Alexe
, “
Antiferroelectric tunnel junctions
,” Adv. Electron. Mater.
3
(7
), 1700126
(2017
).32.
R.
Gao
,
S. E.
Reyes-Lillo
,
R.
Xu
,
A.
Dasgupta
,
Y.
Dong
,
L. R.
Dedon
,
J.
Kim
,
S.
Saremi
,
Z.
Chen
,
C. R.
Serrao
,
H.
Zhou
,
J. B.
Neaton
, and
L. W.
Martin
, “
Ferroelectricity in Pb1+δZrO3 thin films
,” Chem. Mater.
29
(15
), 6544
–6551
(2017
).33.
H.
Fujishita
and
S.
Katano
, “
Crystal structure of perovskite PbZrO3 re-investigated by high resolution powder neutron diffraction
,” Ferroelectrics
217
(1
), 17
–20
(1998
).34.
M. P.
Moret
,
J. J.
Schermer
,
F. D.
Tichelaar
,
E.
Aret
, and
P. R.
Hageman
, “
Structure and morphology of epitaxial PbZrO3 films grown by metalorganic chemical vapor deposition
,” J. Appl. Phys.
92
(7
), 3947
–3957
(2002
).35.
X.-K.
Wei
,
A. K.
Tagantsev
,
A.
Kvasov
,
K.
Roleder
,
C.-L.
Jia
, and
N.
Setter
, “
Ferroelectric translational antiphase boundaries in nonpolar materials
,” Nat. Commun.
5
(1
), 3031
(2014
).36.
A. M.
Glazer
, “
The classification of tilted octahedra in perovskites
,” Acta Crystallogr., Sect. B
28
(11
), 3384
–3392
(1972
).37.
K.
Yamakawa
,
S.
Trolier‐McKinstry
,
J. P.
Dougherty
, and
S. B.
Krupanidhi
, “
Reactive magnetron co‐sputtered antiferroelectric lead zirconate thin films
,” Appl. Phys. Lett.
67
(14
), 2014
–2016
(1995
).38.
H.
Lu
,
S.
Glinsek
,
P.
Buragohain
,
E.
Defay
, and
J.
Iñiguez
, “
Probing antiferroelectric-ferroelectric phase transitions in PbZrO3 capacitors by piezoresponse force microscopy
,” Adv. Funct. Mater.
30
, 2003622
(2020
).39.
M. D.
Nguyen
and
G.
Rijnders
, “
Electric field-induced phase transition and energy storage performance of highly-textured PbZrO3 antiferroelectric films with a deposition temperature dependence
,” J. Eur. Ceram. Soc.
38
(15
), 4953
–4961
(2018
).40.
T.
Ma
,
Z.
Fan
,
B.
Xu
,
T.-H.
Kim
,
P.
Lu
,
L.
Bellaiche
,
M. J.
Kramer
,
X.
Tan
, and
L.
Zhou
, “
Uncompensated polarization in incommensurate modulations of perovskite antiferroelectrics
,” Phys. Rev. Lett.
123
(21
), 217602
(2019
).41.
Y.
Yao
,
A.
Naden
,
M.
Tian
,
S.
Lisenkov
,
Z.
Beller
,
A.
Kumar
,
J.
Kacher
,
I.
Ponomareva
, and
N.
Bassiri-Gharb
, “
Ferrielectricity in the archetypal antiferroelectric, PbZrO3
,” Adv. Mater.
35
(3
), 2206541
(2023
).42.
X.-K.
Wei
,
K.
Vaideeswaran
,
C. S.
Sandu
,
C.-L.
Jia
, and
N.
Setter
, “
Preferential creation of polar translational boundaries by interface engineering in antiferroelectric PbZrO3 thin films
,” Adv. Mater. Interfaces
2
(18
), 1500349
(2015
).43.
W.
Zhong
,
D.
Vanderbilt
, and
K. M.
Rabe
, “
First-principles theory of ferroelectric phase transitions for perovskites: The case of BaTiO3
,” Phys. Rev. B
52
(9
), 6301
–6312
(1995
).© 2023 Author(s). Published under an exclusive license by AIP Publishing.
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