Metastable rhombohedral hafnia-based ferroelectric films are emerging as a promising candidate in ferroelectric nonvolatile memory technologies, but the limited critical thickness impedes their applications. Herein, a 35-nm-thick rhombohedral Hf0.5Zr0.5O2 epilayer was stabilized on ZnO(0001) under an oxygen-deficient condition. Domain matching epitaxy, which facilitates the accommodation of misfit strain, allows the epitaxial growth of the (111)-oriented rhombohedral Hf0.5Zr0.5O2 film. We propose that a strong symmetry constraint is imposed on the epilayer at the initial epitaxial growth stage, i.e., the plane adjacent to ZnO(0001) should have a threefold symmetry. Although the bulk monoclinic phase is much more stable than the rhombohedral phase, our first principles calculations reveal that these two phases are energetically comparable with each other when this symmetry constraint is considered. Moreover, our results show that the incorporation of doubly charged oxygen vacancies is also powerful in shifting the energy balance between competing phases, making the metastable rhombohedral phase more stable.

1.
X.
Xu
,
F.-T.
Huang
,
Y.
Qi
,
S.
Singh
,
K. M.
Rabe
,
D.
Obeysekera
,
J.
Yang
,
M.-W.
Chu
, and
S.-W.
Cheong
,
Nat. Mater.
20
,
826
(
2021
).
2.
J.
Hoffman
,
X.
Pan
,
J. W.
Reiner
,
F. J.
Walker
,
J. P.
Han
,
C. H.
Ahn
, and
T. P.
Ma
,
Adv. Mater.
22
,
2957
(
2010
).
3.
T.
Mikolajick
,
S.
Slesazeck
,
M. H.
Park
, and
U.
Schroeder
,
MRS Bull.
43
,
340
(
2018
).
4.
T. S.
Boscke
,
J.
Muller
,
D.
Brauhaus
,
U.
Schroder
, and
U.
Bottger
,
Appl. Phys. Lett.
99
,
102903
(
2011
).
5.
R.
Materlik
,
C.
Kunneth
, and
A.
Kersch
,
J. Appl. Phys.
117
,
134109
(
2015
).
6.
M. H.
Park
,
Y. H.
Lee
,
H. J.
Kim
,
Y. J.
Kim
,
T.
Moon
,
K. D.
Kim
,
J.
Müller
,
A.
Kersch
,
U.
Schroeder
,
T.
Mikolajick
, and
C. S.
Hwang
,
Adv. Mater.
27
,
1811
(
2015
).
7.
M. A.
Sahiner
,
R. J. V.
Valk
,
J.
Steier
,
J.
Savastano
,
S.
Kelty
,
B.
Ravel
,
J. C.
Woicik
,
Y.
Ogawa
,
K.
Schmidt
,
E. A.
Cartier
,
J. L.
Jordan-Sweet
,
C.
Lavoie
, and
M. M.
Frank
,
Appl. Phys. Lett.
118
,
092903
(
2021
).
8.
Z.
Zhang
,
S.-L.
Hsu
,
V. A.
Stoica
,
H.
Paik
,
E.
Parsonnet
,
A.
Qualls
,
J.
Wang
,
L.
Xie
,
M.
Kumari
,
S.
Das
,
Z.
Leng
,
M.
McBriarty
,
R.
Proksch
,
A.
Gruverman
,
D. G.
Schlom
,
L.-Q.
Chen
,
S.
Salahuddin
,
L. W.
Martin
, and
R.
Ramesh
,
Adv. Mater.
33
,
2006089
(
2021
).
9.
Y.
Wei
,
P.
Nukala
,
M.
Salverda
,
S.
Matzen
,
H. J.
Zhao
,
J.
Momand
,
A. S.
Everhardt
,
G.
Agnus
,
G. R.
Blake
,
P.
Lecoeur
,
B. J.
Kooi
,
J.
Iniguez
,
B.
Dkhil
, and
B.
Noheda
,
Nat. Mater.
17
,
1095
(
2018
).
10.
J.
Lyu
,
I.
Fina
,
R.
Solanas
,
J.
Fontcuberta
, and
F.
Sanchez
,
Appl. Phys. Lett.
113
,
082902
(
2018
).
11.
L.
Begon-Lours
,
M.
Mulder
,
P.
Nukala
,
S.
De Graaf
,
Y. A.
Birkholzer
,
B.
Kooi
,
B.
Noheda
,
G.
Koster
, and
G.
Rijnders
,
Phys. Rev. Mater.
4
,
043401
(
2020
).
12.
J.
Lyu
,
I.
Fina
, and
F.
Sanchez
,
Appl. Phys. Lett.
117
,
072901
(
2020
).
13.
J. P. B.
Silva
,
R. F.
Negrea
,
M. C.
Istrate
,
S.
Dutta
,
H.
Aramberri
,
J.
Iniguez
,
F. G.
Figueiras
,
C.
Ghica
,
K. C.
Sekhar
, and
A. L.
Kholkin
, e-print arXiv:2011.02728.
14.
P.
Nukala
,
Y.
Wei
,
V.
de Haas
,
Q.
Guo
,
J.
Antoja-Lleonart
, and
B.
Noheda
,
Ferroelectrics
569
,
148
(
2020
).
15.
Y.
Zhang
,
Q.
Yang
,
L.
Tao
,
E. Y.
Tsymbal
, and
V.
Alexandrov
,
Phys. Rev. Appl.
14
,
014068
(
2020
).
16.
Y.
Qi
,
S.
Singh
,
C.
Lau
,
F.-T.
Huang
,
X.
Xu
,
F. J.
Walker
,
C. H.
Ahn
,
S.-W.
Cheong
, and
K. M.
Rabe
,
Phys. Rev. Lett.
125
,
257603
(
2020
).
17.
P.
Nukala
,
J.
Antoja-Lleonart
,
Y.
Wei
,
L.
Yedra
,
B.
Dkhil
, and
B.
Nohedra
,
ACS Appl. Electron. Mater.
1
,
2585
(
2019
).
18.
S.
Estandía
,
N.
Dix
,
J.
Gazquez
,
I.
Fina
,
J.
Lyu
,
M. F.
Chisholm
,
J.
Fontcuberta
, and
F.
Sanchez
,
ACS Appl. Electron. Mater.
1
,
1449
(
2019
).
19.
I.
Fina
and
F.
Sanchez
,
ACS Appl. Electron. Mater.
3
,
1530
(
2021
).
20.
P.
Nukala
,
M.
Ahmadi
,
Y.
Wei
,
S.
De Graaf
,
E.
Stylianidis
,
T.
Chakrabortty
,
S.
Matzen
,
H. W.
Zandbergen
,
A.
Bjorling
,
D.
Mannix
,
D.
Carbone
,
B.
Kooi
, and
B.
Noheda
,
Science
372
,
630
(
2021
).
21.
P. E.
Blochl
,
Phys. Rev. B
50
,
17953
(
1994
).
22.
G.
Kresse
and
D.
Joubert
,
Phys. Rev. B
59
,
1758
(
1999
).
23.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
).
24.
M.
Dogan
,
N.
Gong
,
T.-P.
Ma
, and
S.
Ismail-Beigi
,
Phys. Chem. Chem. Phys.
21
,
12150
(
2019
).
25.
S.
Choopun
,
R. D.
Vispute
,
W.
Yang
,
R. P.
Sharma
,
T.
Venkatesan
, and
H.
Shen
,
Appl. Phys. Lett.
80
,
1529
(
2002
).
26.
R.
People
and
J. C.
Bean
,
Appl. Phys. Lett.
47
,
322
(
1985
).
27.
J.
Narayan
and
B. C.
Larson
,
J. Appl. Phys.
93
,
278
(
2003
).
28.
J. D.
Budai
,
W.
Yang
,
N.
Tamura
,
J.
Chuang
,
J. Z.
Tischler
,
B. C.
Larson
,
G. E.
Ice
,
C.
Park
, and
D. P.
Norton
,
Nat. Mater.
2
,
487
(
2003
).
29.
S.
Estandia
,
N.
Dix
,
M. F.
Chisholm
,
I.
Fina
, and
F.
Sanchez
,
Cryst. Growth Des.
20
,
3801
(
2020
).
30.
Y. Z.
Zhu
,
G. D.
Chen
,
H.
Ye
,
A.
Walsh
,
C. Y.
Moon
, and
S.-H.
Wei
,
Phys. Rev. B
77
,
245209
(
2008
).
31.
Y.
Zhou
,
Y. K.
Zhang
,
Q.
Yang
,
J.
Jiang
,
P.
Fan
,
M.
Liao
, and
Y. C.
Zhou
,
Comput. Mater. Sci.
167
,
143
(
2019
).
32.
T.
Mikolajick
,
S.
Slesazeck
,
H.
Mulaosmanovic
,
M. H.
Park
,
S.
Fichtner
,
P. D.
Lomenzo
,
M.
Hoffmann
, and
U.
Schroeder
,
J. Appl. Phys.
129
,
100901
(
2021
).
33.
C.
Kunneth
,
R.
Materlik
,
M.
Falkowski
, and
A.
Kersch
,
ACS Appl. Nano Mater.
1
,
254
(
2018
).
34.
E.
Hildebrandt
,
J.
Kurian
, and
L.
Alff
,
J. Appl. Phys.
112
,
114112
(
2012
).
35.
D. R.
Islamov
,
V. A.
Gritsenko
,
C. H.
Cheng
, and
A.
Chin
,
Appl. Phys. Lett.
105
,
222901
(
2014
).
36.
A.
Padovani
,
L.
Larcher
,
G.
Bersuker
, and
P.
Pavan
,
IEEE Electron Device Lett.
34
,
680
(
2013
).
37.
P.
Nukala
,
M.
Ahmadi
,
J.
Antoja-Lleonart
,
S.
De Graaf
,
Y.
Wei
,
H. W.
Zandbergen
,
B. J.
Kooi
, and
B.
Noheda
,
Appl. Phys. Lett.
118
,
062901
(
2021
).
38.
C.
Freysoldt
,
B.
Grabowski
,
T.
Hickel
,
J.
Neugebauer
,
G.
Kresse
,
A.
Janotti
, and
C. G. V.
De Walle
,
Rev. Mod. Phys.
86
,
253
(
2014
).

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