Crystalline phase identification for hafnium-based ferroelectrics by diffraction techniques has been elusive. We use density-functional-theory (DFT)-assisted extended X-ray absorption fine-structure spectroscopy (EXAFS) to determine the crystal symmetry of thin hafnium zirconium oxide (Hf0.46Zr0.54O2) films grown by atomic layer deposition. Ferroelectric switching in TiN/Hf0.46Zr0.54O2/TiN metal–insulator–metal capacitors is verified. Grazing-incidence fluorescence-yield mode Hf L3 and Zr K absorption edge EXAFS data are compared with reference data calculated from DFT-based atomic coordinates for various structural phases of Hf0.5Zr0.5O2. Via EXAFS multiphase fitting, we confirm that the frequently invoked polar orthorhombic Pca21 phase is present in ferroelectric hafnium zirconium oxide, along with an equal amount of the nonpolar monoclinic P21/c phase. For comparison, we verify that paraelectric HfO2 films exhibit the P21/c phase.
References
1.
T. S.
Böscke
, J.
Müller
, D.
Bräuhaus
, U.
Schröder
, and U.
Böttger
, Appl. Phys. Lett.
99
, 102903
(2011
).2.
J.
Müller
, P.
Polakowski
, S.
Mueller
, and T.
Mikolajick
, ECS J. Solid State Sci. Technol.
4
, N30
(2015
).3.
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
).4.
U.
Schroeder
, C. S.
Hwang
, and H.
Funakubo
, Ferroelectricity in Doped Hafnium Oxide: Materials, Properties and Devices
, Woodhead Publishing Series in Electronic and Optical Materials (Woodhead Publishing
, Duxford, United Kingdom
, 2019
).5.
F.
Ali
, D.
Zhou
, M.
Ali
, H. W.
Ali
, M.
Daaim
, S.
Khan
, M. M.
Hussain
, and N.
Sun
, ACS Appl. Electron. Mater.
2
, 2301
(2020
).6.
M. H.
Park
, D. H.
Lee
, K.
Yang
, J.-Y.
Park
, G. T.
Yu
, H. W.
Park
, M.
Materano
, T.
Mittmann
, P. D.
Lomenzo
, T.
Mikolajick
, U.
Schroeder
, and C. S.
Hwang
, J. Mater. Chem. C
8
, 10526
(2020
).7.
O.
Ohtaka
, H.
Fukui
, T.
Kunisada
, T.
Fujisawa
, K.
Funakoshi
, W.
Utsumi
, T.
Irifune
, K.
Kuroda
, and T.
Kikegawa
, J. Am. Ceram. Soc.
84
, 1369
(2004
).8.
C.
Wang
, M.
Zinkevich
, and F.
Aldinger
, J. Am. Ceram. Soc.
89
, 3751
(2006
).9.
Y.
Al-Khatatbeh
, K. K. M.
Lee
, and B.
Kiefer
, Phys. Rev. B
82
, 144106
(2010
).10.
S.
Pathak
, G.
Mandal
, P.
Das
, and A. B.
Dey
, Mater. Chem. Phys.
255
, 123633
(2020
).11.
T. D.
Huan
, V.
Sharma
, G. A.
Rossetti
, Jr., and R.
Ramprasad
, Phys. Rev. B
90
, 064111
(2014
).12.
E. H.
Kisi
, C. J.
Howard
, and R. J.
Hill
, J. Am. Ceram. Soc.
72
, 1757
(1989
).13.
R.
Materlik
, C.
Künneth
, and A.
Kersch
, J. Appl. Phys.
117
, 134109
(2015
).14.
S. V.
Barabash
, J. Comput. Electron.
16
, 1227
(2017
).15.
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.
Íñiguez
, B.
Dkhil
, and B.
Noheda
, Nat. Mater.
17
, 1095
(2018
).16.
R.
Ruh
, H. J.
Garrett
, R. F.
Domagala
, and N. M.
Tallan
, J. Am. Ceram. Soc.
51
, 23
(1968
).17.
J. M.
Leger
, P. E.
Tomaszewski
, A.
Atouf
, and A. S.
Pereira
, Phys. Rev. B
47
, 14075
(1993
).18.
S.
Shibayama
, T.
Nishimura
, S.
Migita
, and A.
Toriumi
, J. Appl. Phys.
124
, 184101
(2018
).19.
T.
Shimizu
, K.
Katayama
, T.
Kiguchi
, A.
Akama
, T. J.
Konno
, O.
Sakata
, and H.
Funakubo
, Sci. Rep.
6
, 32931
(2016
).20.
P.
Nukala
, J.
Antoja-Lleonart
, Y.
Wei
, L.
Yedra
, B.
Dkhil
, and B.
Noheda
, ACS Appl. Electron. Mater.
1
, 2585
(2019
).21.
X.
Sang
, E. D.
Grimley
, T.
Schenk
, U.
Schroeder
, and J. M.
LeBeau
, Appl. Phys. Lett.
106
, 162905
(2015
).22.
M.
Lederer
, T.
Kämpfe
, R.
Olivo
, D.
Lehninger
, C.
Mart
, S.
Kirbach
, T.
Ali
, P.
Polakowski
, L.
Roy
, and K.
Seidel
, Appl. Phys. Lett.
115
, 222902
(2019
).23.
P.
Lysaght
, J. C.
Woicik
, M. A.
Sahiner
, B.-H.
Lee
, and R.
Jammy
, Appl. Phys. Lett.
91
, 122910
(2007
).24.
M. A.
Sahiner
, J. C.
Woicik
, P.
Gao
, P.
McKeown
, M. C.
Croft
, M.
Gartman
, and B.
Benapfl
, Thin Solid Films
515
, 6548
(2007
).25.
M. A.
Sahiner
, J. C.
Woicik
, T.
Kurp
, J.
Serfass
, and M.
Aranguren
, Mater. Sci. Semicond. Process.
11
, 245
(2008
).26.
P. S.
Lysaght
, J. C.
Woicik
, M. A.
Sahiner
, B. H.
Lee
, and R.
Jammy
, J. Non-Cryst. Solids
354
, 399
(2008
).27.
M. A.
Sahiner
, P. S.
Lysaght
, J.
Price
, P. D.
Kirsch
, J. C.
Woicik
, A.
Klump
, C.
Reehil
, W. A.
Manners
, and A.
Nabizadeh
, Appl. Phys. A
117
, 93
(2014
).28.
M. E.
McBriarty
, V. K.
Narasimhan
, S. L.
Weeks
, A.
Pal
, H.
Fang
, T. A.
Petach
, A.
Mehta
, R. C.
Davis
, S. V.
Barabash
, and K. A.
Littau
, Phys. Status Solidi B
257
, 2070010
(2020
).29.
T.
Schenk
, A.
Anspoks
, I.
Jonane
, R.
Ignatans
, B. S.
Johnson
, J. L.
Jones
, M.
Tallarida
, C.
Marini
, L.
Simonelli
, P.
Hönicke
, C.
Richter
, T.
Mikolajick
, and U.
Schroeder
, Acta Mater.
180
, 158
(2019
).30.
S. B.
Erenburg
, S. V.
Trubina
, K. O.
Kvashnina
, V. N.
Kruchinin
, V. V.
Gritsenko
, A. G.
Chernikova
, and A. M.
Markeev
, J. Exp. Theor. Phys.
126
, 816
(2018
).31.
S. J.
Kim
, J.
Mohan
, S. R.
Summerfelt
, and J.
Kim
, JOM
71
, 246
(2019
).32.
J. C.
Woicik
, Surf. Sci. Rep.
69
, 38
(2014
); and references therein.33.
G.
Kresse
and J.
Hafner
, Phys. Rev. B
47
, 558
(1993
).34.
G.
Kresse
and J.
Furthmüller
, Comput. Mater. Sci.
6
, 15
(1996
).35.
G.
Kresse
and J.
Furthmüller
, Phys. Rev. B
54
, 11169
(1996
).36.
P. E.
Blöchl
, Phys. Rev. B
50
, 17953
(1994
).37.
G.
Kresse
and J.
Joubert
, Phys. Rev. B
59
, 1758
(1999
).38.
J. P.
Perdew
and Y.
Wang
, Phys. Rev. B
45
, 13244
(1992
).39.
40.
B.
Ravel
and M.
Newville
, J. Synchrotron Rad.
12
, 537
(2005
).41.
M.
Newville
, P.
Livins
, Y.
Yacoby
, J. J.
Rehr
, and E. A.
Stern
, Phys. Rev. B
47
, 14126
(1993
).42.
A. L.
Ankudinov
, B.
Ravel
, J. J.
Rehr
, and S. D.
Conradson
, Phys. Rev. B
58
, 7565
(1998
).43.
N.
Bar-Chaim
, M.
Brunstein
, J.
Grünberg
, and A.
Seidman
, J. Appl. Phys.
45
, 2398
(1974
).44.
D.
Damjanovic
, Rep. Prog. Phys.
61
, 1267
(1998
).45.
J.
Müller
, T. S.
Böscke
, U.
Schröder
, S.
Mueller
, D.
Bräuhaus
, U.
Böttger
, L.
Frey
, and T.
Mikolajick
, Nano Lett.
12
, 4318
(2012
).46.
L.
Xu
, S.
Shibayama
, K.
Izukashi
, T.
Nishimura
, T.
Yajima
, S.
Migita
, and A.
Toriumi
, in IEEE International Electron Devices Meeting (IEDM)
, Technical Digest (IEEE, 2016
), p. 608
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