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Crystal Phase Distribution and Ferroelectricity in Ultrathin

HfO2–ZrO2 Bilayers
Martin E. McBriarty,* Vijay K. Narasimhan, Stephen L. Weeks, Ashish Pal,
Huazhi Fang, Trevor A. Petach, Apurva Mehta, Ryan C. Davis, Sergey V. Barabash,
and Karl A. Littau

but requires a ferroelectric memory ele-

(Hf,Zr)O2 ultrathin films are used as ferroelectric layers in emerging digital logic ment.[2] To make these devices reliable
and nonvolatile memory devices. The ferroelectric properties of (Hf,Zr)O2 can be and cost effective, ferroelectric materials
improved by interface engineering, such as the formation of nanolaminates which are compatible with standard semi-
conductor processing technology are needed.
with distinct HfO2 and ZrO2 layers. Herein, the ferroelectric performance of
HfO2 and ZrO2 are of particular interest
HfO2–ZrO2 ultrathin bilayer devices is shown to depend on the stacking order of as ferroelectric materials for these applica-
HfO2 and ZrO2, which affects the quantity of the noncentrosymmetric ortho- tions.[3,4] These oxides are widely used as
rhombic Pca21 crystal phase. By combining X-ray diffraction with a novel dielectrics in microelectronics thanks to
extended X-ray absorption fine structure (EXAFS) analysis procedure, the their high permittivity, wide band gap,
and ease of fabrication of conformal,
orthorhombic, tetragonal, and monoclinic phase fractions are quantified for
high-quality ultrathin films by atomic layer
bilayers composed of 3 nm HfO2 and 3 nm ZrO2. A significantly larger ortho- deposition (ALD). The functional proper-
rhombic ZrO2 phase fraction is found when ZrO2 has an unconstrained surface ties of these oxides are linked to their crys-
during annealing, whereas the presence of a ZrO2 interface with the substrate tal structure.[3] Pca21 (orthorhombic, oFE)
results in a substantial tetragonal ZrO2 phase fraction and a 2.4
smaller and the recently discovered R3 (rhombohe-
remanent polarization. HfO2 is found to be less susceptible than ZrO2 to crystal dral, rFE) crystal structures are noncentro-
symmetric and demonstrate ferroelectric
phase templating. The methods presented herein enable mechanistic studies of
behavior.[5–10] However, the ferroelectric
ferroelectric wake-up, fatigue, and processing effects in (Hf,Zr)O2 films, accel- crystal phases are unstable in pure bulk
erating the development of electronic devices that rely on ferroelectric oxides. HfO2 and ZrO2 at room temperature,
requiring dopants, defects, or interface
engineering to produce functioning devi-
ces.[3,8,10–12] Other technologically interest-
1. Introduction ing polymorphs, including the P42/nmc (tetragonal, t) and Fm3̄m
(cubic, c) phases, are also unstable in pure bulk HfO2 and ZrO2
Ferroelectric materials are key components of emerging electronic relative to the P21/c (monoclinic, m) phase at standard tempera-
devices. Negative capacitance field-effect transistors (NC-FETs) ture and pressure. Thus, the desirable properties of (Hf,Zr)O2
rely on a ferroelectric gate insulator in combination with a standard films must be unlocked by altering the composition, thickness,
dielectric to enable <60 mV decade1 subthreshold slopes and processing conditions, and choice of substrate or capping layer to
lower operating voltages, yielding smaller logic devices operating favor a particular crystal structure.
HfxZr1-xO2 films with x  0.5 show good ferroelectric perfor-
at a lower power.[1] Ferroelectric random access memory (FeRAM)
mance, with a maximum remanent polarization (2Pr) of about
offers faster switching than conventional nonvolatile memory
34 μC cm2 for a 9 nm film.[13] ZrO2/HfO2 nanolaminate struc-
tures yield even larger remanent polarization than (Hf,Zr)O2
Dr. M. E. McBriarty, Dr. V. K. Narasimhan, Dr. S. L. Weeks, Dr. A. Pal, solid solutions of the same overall composition.[14,15] The
Dr. H. Fang, Dr. S. V. Barabash, Dr. K. A. Littau presence of solid–solid interfaces between amorphous HfO2
Technology Group
Intermolecular, Inc. or ZrO2 films can either arrest[16] or template[17] crystallization
3011 N. 1st Street, San Jose, CA 95134, USA during annealing, depending on the structure of the adjacent
E-mail: martin.mcbriarty@intermolecular.com material. Thus, the interfaces between HfO2 or ZrO2 and a
Dr. T. A. Petach, Dr. A. Mehta, Dr. R. C. Davis substrate, electrode, or annealing gas (i.e., an unconstrained
Stanford Synchrotron Radiation Lightsource surface) affect the final distribution of crystal phases, and there-
SLAC National Accelerator Center fore the ultimate ferroelectric performance, in a nanolaminate.
Menlo Park, CA 94025, USA
Ultrathin ALD HfO2 films are amorphous as deposited on tech-
The ORCID identification number(s) for the author(s) of this article nologically relevant substrates at deposition temperatures at or
can be found under https://doi.org/10.1002/pssb.201900285. below 300  C.[14,17,18] ZrO2 is more prone to crystallization than
DOI: 10.1002/pssb.201900285 HfO2, and thin ZrO2 films readily crystallize to the t phase.[16,17]

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Developing robust devices based on (Hf,Zr)O2 ferroelectrics Martin E. McBriarty earned his
demands an understanding of the links between the crystal degrees in Materials Science and
structure, processing/annealing conditions, and changes to the Engineering (B.S., University of
material during electrical cycling.[15,19,20] In previous studies on Florida, 2008; Ph.D., Northwestern
(Hf,Zr)O2, a predictor of ferroelectric performance has been the University, 2014). His doctoral
suppression of the m crystal phase as indicated by grazing inci- research focused on heterogeneous
dence X-ray diffraction (GIXRD),[12,21,22] but this measurement catalysis, and in 2011 he won a
does not uniquely reveal the presence or abundance of the oFE Fulbright fellowship to study at the
phase attributed to the ferroelectric performance of these devices. Fritz Haber Institute. In 2014, he
Although the m phase has a distinctive double diffraction peak cor- began postdoctoral research on
responding to the {111} and {1̄11} families of diffracting planes, interfacial geochemistry at Pacific Northwest National
the t and oFE phases have similar diffraction patterns which can Laboratory. In 2018, he joined Intermolecular, Inc. as a
only be distinguished when films are sufficiently thick or when the scientist, where he investigates atomic layer deposition
substrate composition is well controlled.[10,13,23] Real devices may processes for electronic devices.
use films thinner than 10 nm deposited on crystalline electrodes
such as TiN, which interfere further with peak discrimination and Vijay K. Narasimhan is a senior staff
phase identification. Although attempts have been made to decom- research engineer at Intermolecular,
pose the diffraction features of the oFE and t phases of doped Inc., where he develops deposition,
HfO2[10] and (Hf,Zr)O2[24] films, crystal phase distributions have characterization, and integration
not been measured for ferroelectric (Hf,Zr)O2 films thinner than processes for emerging electronic
10 nm. Even under conditions in which these crystal phases can be materials, including ferroelectrics,
distinguished by GIXRD, the contributions of each material in a chalcogenides, and III–V
HfO2/ZrO2 nanolaminate are probably indistinguishable. semiconductors. Previously, he was an
Despite their similar diffraction patterns, the t and oFE international Fulbright Science and
structures of HfO2 and ZrO2 have distinct cation coordination Technology Fellow at Stanford
structures. The oFE phase has a similar local structure to the m University, where he completed a Ph.D. in Materials
phase, with seven metal–oxygen bonds with different lengths Science and Engineering in 2015. His doctoral research
within the first coordination shell. In contrast, the t local structure focused on the optical and electrical properties of
consists of two distorted tetrahedra, with four short bonds and nanostructured surfaces. He earned an M.Phil in Micro-
four long bonds in the first coordination shell. Methods sensitive and Nanotechnology Enterprise from the University of
to local structure instead of periodicity, such as extended X-ray Cambridge and a B.A.Sc. in Computer Engineering from
absorption fine structure (EXAFS) spectroscopy, can better resolve the University of Ottawa in Canada.
these crystal phases. An EXAFS spectrum encodes the coordina- Karl A. Littau is a physical chemist
tion structure(s) of one element in a sample as an oscillation in the with expertise in thin-film deposition,
X-ray absorption caused by photoelectron scattering from neigh- ALD, CVD, surface and gas phase
boring atoms. EXAFS is typically analyzed using shell-by-shell fit- chemistry, and solid state physics. He
ting, in which the atoms surrounding an absorbing atom are holds a B.S. in Chemistry from UC
modeled as coordination shells described by an average bond Berkeley and a Ph.D. in Physical
length, coordination number, and disorder parameter. Such an Chemistry from Stanford University.
approach works well for structures with high local symmetry, He has held positions at AT&T Bell
but statistical limitations hinder the accurate fitting of EXAFS Laboratories, Applied Materials, Inc.,
spectra which encode a complex local structure or spectral contri- and Xerox’s Palo Alto Research
butions from multiple coexisting phases.[25] Previous studies used Center, Stanford University, and is currently CTO at
EXAFS linear combination fitting to discriminate phases of HfO2 Intermolecular Inc. where he has been directing research
based on photoelectron scattering contributions from Hf–Hf inter- and development of new materials and methods for
actions,[26] but these fits mostly neglected the useful structural advanced IC devices and emerging technologies.
information in the first Hf–O shell and used basis spectra which
did not account for thermal disorder, inspiring the development of
more accurate approaches to (Hf,Zr)O2 phase identification. and oFE phases of ZrO2 and HfO2, providing a new route for
Here, a novel EXAFS analysis method is shown to distinguish accurate nondestructive characterization and ferroelectric prop-
the t and oFE phases of 3 nm ZrO2 / 3 nm HfO2 bilayers grown erty prediction for these technologically important materials.
by ALD, and the measured crystal phase distribution is linked to
ferroelectric performance. EXAFS “fingerprints” for different
crystal structures were simulated for known phases, validated 2. Results
by comparison with experimental spectra, and then added in lin-
ear combination to fit experimental data encoding unknown crys- 2.1. Thin Film Characterization
tal phase distributions. GIXRD results were used to further
distinguish the m-HfO2 and oFE-HfO2 phases. This combined Bilayer stacks of ZrO2 and HfO2 were grown by ALD on Si(100)
approach reliably determines the phase fractions of the m, t, substrates with native oxide. The target thickness for each bilayer

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component was 30 Å, and growth proceeded as substrate/HfO2/
ZrO2 (sample SHZ) and substrate/ZrO2/HfO2 (sample SZH).
Samples selected for further study were annealed at 500  C
for 10 min in N2.[15] The thickness, density, and interface mixing
of the HfO2–ZrO2 bilayers were determined by X-ray reflectivity
(XRR). XRR data and fits are shown in Figure S1 and Table S1,
Supporting Information. The measured densities agree with
bulk values. Film thicknesses for sample SZH were 29.7 Å
(ZrO2) and 29.0 Å (HfO2) and for sample SHZ were 27.3 Å
(HfO2) and 31.5 Å (ZrO2), all close to the target thicknesses of
30 Å. The interface roughness values of about 3 Å indicate mini-
mal intermixing between the ZrO2 and HfO2 layers.
GIXRD patterns for the as-deposited and annealed bilayer
stacks are shown in Figure S2, Supporting Information. The
as-deposited films show no evidence of crystallinity (an artifact
at 2θ ¼ 44.5 is present for all samples). The annealed films show
several peaks which can correspond to either the t or oFE phase of
ZrO2 and HfO2 or some combination thereof. There is a small
contribution of the m phase which is apparent as the 1̄11m and
111m shoulders surrounding the 111o/011t peak. XRD peaks
were fit over 20 < 2θ < 42 as Gaussian curves atop a decaying
exponential background. Five peaks were fit, labeled in Figure 1.
The widths of the 1̄11m, 111m, and 111o/011t peaks were kept
equal. The 111m/1̄11m intensity ratio was fixed to 0.744, which
is the theoretical ratio based on the calculated structure, Lorentz,
and polarization factors (see Table S2 and S4, Supporting
Information). Temperature factors are assumed to be the same
for the analyzed reflections.
XRD fit results are shown in Table S2, Supporting
Information. Using the Scherrer equation with a shape factor
of 0.9, a characteristic crystallite size of about 6 nm is estimated,
which matches the total bilayer thickness and supports previous
findings of crystalline continuity between HfO2 and ZrO2.[15,17]
The monoclinic phase fraction is higher for sample SZH.
Because of the strong overlap between the 111o and 011t peaks
of both ZrO2 and HfO2, as well as the overlap between each
monoclinic peak ([1]11m) of both materials, the contributions
Figure 1. Fits (aqua dashed lines) to the GIXRD patterns in the vicinity of 2θ ¼ 30 for samples SHZ (red dots) and SZH (blue dots). Both samples were
annealed at 500  C in N2 for 10 min.
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for each crystal phase from each material cannot be resolved
by XRD alone.
2.2. X-Ray Absorption Spectroscopy
2.2.1. X-ray Absorption Near Edge Structure
For some oxides, phase fractions can be measured by analyzing
features in the X-ray absorption near edge structure (XANES). Zr
K-edge and Hf L3-edge XANES spectra for samples SHZ and
SZH, as well as reference spectra, are shown in Figure S4,
Supporting Information. Each HfO2 XANES spectrum features
a strong white line, but they are difficult to distinguish from
m-HfO2, regardless of whether the samples had been annealed.
ZrO2 XANES are more clearly distinguishable, but linear combi-
nations of m-ZrO2 and t-ZrO2 standard spectra did not match the
salient features of annealed SHZ or SZH. To the authors’ knowl-
edge, no XANES spectra for the oFE phases of HfO2 or ZrO2 have
been published, and the accurate simulation of XANES spectra is
beyond the scope of this work. Further analysis focuses on the
EXAFS region of the X-ray absorption spectra.
2.2.2. EXAFS Simulation
EXAFS linear combination fitting (LCF) is used to determine the
phase fraction distribution of the 3 nm ZrO2 and HfO2 films
comprising the bilayers of interest. LCF assumes that an
unknown experimental spectrum consists of a weighted sum
of basis spectra, where each spectrum in the basis set corre-
sponds to a unique crystal phase. The basis set of EXAFS spectra
may be simulated starting from experimental or theoretical crys-
tal structures. The details of EXAFS simulation are covered else-
where,[27–29] but a key point is that physically reasonable EXAFS
simulations need to include accurate disorder parameters (σ2)
and amplitude reduction factors (S02). Disorder damps the ampli-
tudes of photoelectron scattering paths in proportion to the width
of the time-averaged path length distribution, which includes
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both thermal and configurational contributions. Thermal disor-
der can be simulated directly and accurately using first-principles
molecular dynamics[25,30]; however, these simulations can be
prohibitively expensive. Configurational disorder due to strain
fields or interface effects can further dampen the EXAFS of nano-
materials.[31] S02 accounts for many-body electronic relaxation
effects, but since it is difficult to calculate ab initio, it is typically
treated as an EXAFS fit parameter.[27]
In this work, σ2 is parameterized as a linear function of the
photoelectron scattering path length, with S02 as a scale factor
(see Section 5 for details). A key assumption is that the same
disorder parameterization and S02 may be used for the m, t,
and oFE crystal phases for the same material, crystallite size,
and measurement temperature. Thus, separate disorder param-
eterizations must be established for nanoscale ZrO2 and
nanoscale HfO2 by comparison with experimental standard
spectra.
ZrO2 thermal disorder parameters were determined in two
steps. First, simulated m-ZrO2 spectra were fit to an experimental
spectrum for μm-scale m-ZrO2,[32] yielding σ2 ¼ 0.0012*R þ
0.0003 Å2 for bulk m-ZrO2. The fitted S02 value (0.92) is higher
than reported values of around 0.75,[33] although successful
EXAFS fits to ZrO2 have also been obtained with S02 ¼ 1.[34]
Using this initial parameterization, LCFs to sample SHZ with
the lowest R-factor included contributions from oFE-ZrO2
(73%–74%) and the EXAFS spectrum from the nominally
amorphous as-deposited SHZ or SZH samples (26%–27%)
(Figure S5, Supporting Information). Because the amorphous
phase fraction has a small EXAFS amplitude, the primary
effect of including a significant amorphous component in the
LCF is to dampen the amplitude of the fitted spectrum.
However, it is likely that the smaller amplitude of the experi-
mental spectrum actually indicates configurational disorder,
Figure 2. k3-weighted EXAFS spectra (a) and phase-uncorrected Fourier transforms over 3.5 < k < 11.0 Å1 (b) for m (top), oFE (center), and t (bottom)
phases of HfO2. Simulated spectra with the nanoscale disorder parameterization are shown as black solid lines; the red dashed lines correspond to
experimental spectra for the 9.6 nm >90% m-HfO2 film.
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which is typical for nanophase materials below 10 nm.[31]
Thus, to parameterize disorder for nanoscale ZrO2, simulated
oFE-ZrO2 spectra were fit against the Zr EXAFS spectrum for
sample SHZ. Keeping S02 ¼ 0.92, the resulting disorder para-
meterization was σ2 ¼ 0.0016*R þ 0.0002 Å2. LCFs to sample
SHZ with other ZrO2 phases using the nanoscale disorder para-
meterization yielded a 91%  2% oFE-ZrO2 phase fraction
(see Section 2.2.3); therefore, the systematic error on the
EXAFS-derived ZrO2 phase fractions is assumed to be 9%.
Disorder parameters for HfO2 were determined by fitting sim-
ulated EXAFS spectra to an experimental spectrum for a 9.6 nm
m-HfO2 film. This sample was grown by ALD on TiN and then
capped by ALD TiN at 430  C, yielding a m-HfO2 fraction of
90%  1% and a (t þ oFE)-HfO2 fraction of 10%  1% according
to XRD (Figure S3, Supporting Information). The consequences
of this minority phase fraction on the m-HfO2 EXAFS spectrum
depend on its identity as t-, oFE-, or some phase combination
thereof. The local structure of oFE is similar to that of m, so,
a minority oFE phase fraction would barely affect the EXAFS
spectrum; however, the introduction of a minority t phase would
dampen the EXAFS spectrum, resulting in larger σ2 or smaller
S02 than would be obtained for a pure m-HfO2 film. Indeed, the
fitted S02 ¼ 0.80 is somewhat smaller than prior values,[35] and
σ2 ¼ 0.0013*R  0.0011 Å2. However, the smaller S02 value does
not definitively establish a t-HfO2 minority phase; therefore, a
systematic error of 10% is included in all EXAFS-derived phase
fraction measurements for HfO2.
Figure 2 shows simulated and experimental reference EXAFS
spectra for the m, oFE, and t phases of HfO2. The simulated
m-HfO2 spectrum closely matches the experimental spectrum
to which it was calibrated. Discrepancies at k < 2 Å1 may be
attributed to artifacts in the experimental spline fit, and
χ(k) ¼ 0 below k ¼ 1.0 Å1 because of the positive ΔE0 offset
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in the simulation (þ4 eV). The differences between m and oFE
spectra are subtle. While the nodes and antinodes of the EXAFS
occur at similar k values, there are differences in the peak ampli-
tudes, particularly at higher k values, where the amplitude enve-
lope is larger for oFE. The t-HfO2 EXAFS shows more structure
at low k, but at high k the amplitude is much larger than that
for the m or oFE phase. The differences are also clear in the
real-space EXAFS Fourier transforms (FTs), especially in
the Hf–Hf shell (2.9 < R < 4.0 Å) as previously observed.[26]
The larger magnitude of this shell for t-HfO2 indicates its greater
local order. Note that the EXAFS FTs do not directly represent
radial distributions of atoms. Features in the FTs are offset by
a few tenths of an Å negative of the real coordination distances
due to photoelectron wave phase shifts, and destructive interfer-
ence between photoelectron scattering contributions may
dampen features which would otherwise have larger magnitudes
in a radial distribution function.[25]
Similar trends are observed between phases of ZrO2. Simulated
spectra with the nanoscale disorder parameterization and a bind-
ing energy offset ΔE0 ¼ 8 eV are shown in Figure 3 along
with spectra simulated using the bulk disorder parameterization,
which agree well with experimental spectra for bulk m-ZrO2 and
t-ZrO2. The m and oFE phases have an overall similar structure,
although broader features around 7.8 < k < 10.0 Å1 distinguish
m-ZrO2 from oFE-ZrO2. The t-ZrO2 spectrum is characterized by
a large amplitude at high k. In the EXAFS FTs, the m and oFE
phases are characterized by two relatively narrow peaks signify-
ing the Zr–O and Zr–Zr coordination shells. In contrast, the
t-ZrO2 EXAFS FT has a small magnitude in the region corre-
sponding to Zr–O bonding and a large magnitude for the
Zr–Zr shell. The small Zr–O peak magnitude is due to the
destructive interference of photoelectron scattering contribu-
tions[25] from four short (2.10 Å) and four long (2.35 Å) Zr–O
bonds in the first coordination shell.[36] This differs from the
broad, higher magnitude first coordination shell feature for
t-HfO2 (Figure 2b); the larger path length difference between
Hf–O subshells (2.06 and 2.40 Å) results in more constructive inter-
ference in the sum of their scattering contributions. The experi-
mental t-ZrO2 spectrum[33] shows a somewhat different first-
shell structure than the simulated spectrum, with a larger peak
at 1.5 Å but a smaller feature at 2.0–2.2 Å. This could be attributed
to a significantly larger degree of disorder for the longer Zr–O sub-
shell[34] which is not captured in the linear parameterization of the
disorder as a function of the photoelectron path length. Low static
disorder in the Zr–Zr shell leads to a significantly larger magnitude
of the EXAFS FT relative to the m and oFE phases.
2.2.3. EXAFS Fitting
EXAFS LCF results are given in Table 1, and fits for the HfO2 and
ZrO2 components are shown in Figure 4 and 5, respectively.
These results were selected as the set of best fits, i.e., their
R-factors are within 1.25
the minimum (absolute best fit)
R-factor from all permutations of LCFs using the m, t, and/or
oFE crystal phases and with all included phases contributing
phase fractions of at least 5%. For every experimental spectrum,
the fits reveal a significant oFE phase fraction. The ZrO2 compo-
nent of sample SHZ is nearly completely oFE; good fits can be
achieved with about 9% of either m- or t-ZrO2. There are also two
fits of similar quality for the HfO2 component of sample SHZ,
which both include a minority t-HfO2 phase. While the fit to this
spectrum with the lowest R-factor includes all three phases, there
is another fit slightly higher in R-factor which only includes t- and
oFE-HfO2. These two fits highlight the strong similarity in the
Hf L3 EXAFS spectra of the m and oFE phases. While fits were

Figure 3. k3-weighted EXAFS spectra (a) and phase-uncorrected Fourier transforms over 3.5 < k < 11.0 Å1 (b) for m (top), oFE (center), and t (bottom)
phases of ZrO2. Simulated spectra with the nanoscale disorder parameterization are shown as black solid lines. Simulated spectra with the bulk disorder
parameterization (blue dotted lines) are shown along with experimental spectra (red dashed lines) for bulk m-ZrO2[32] and t-ZrO2.[33]

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Table 1. Phase Fraction Results from EXAFS LCFs.

Element Sample R-factor Monoclinic Orthorhombic (FE) Tetragonal

f a)
ΔE0 [eV]b)
f ΔE0 [eV] f ΔE0 [eV]

Hf SZH 0.0379 0.27  0.11 4 0.64  0.11 6 0.09  0.11 12

SHZ 0.0772 0.19  0.11 4 0.67  0.12 6 0.15  0.10 8
0.0848 – – 0.84  0.10 6 0.16  0.10 8
Zr SZH 0.0722 – – 0.59  0.09 6 0.41  0.09 6
SHZ 0.0544 – – 0.92  0.09 8 0.09  0.09 0
0.0610 0.09  0.09 4 0.91  0.09 10 – –

a)
Phase fraction errors include the error from the nonlinear least-squares fit added in the quadrature with systematic errors determined from the disorder parameterization for
each material; b)Best-fit binding energy offset.

Figure 4. Experimental Hf L3 EXAFS spectra (a) and Fourier transforms (b), as well as best fits corresponding to those in Table 1, for the HfO2 component
of bilayer samples SZH and SHZ.

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Figure 5. Experimental Zr K EXAFS spectra (a) and Fourier transforms (b), as well as best fits corresponding to those in Table 1, for the ZrO2 component
of component of bilayer samples SZH and SHZ.

performed only over 3.5 < k < 11.0 Å1, the fits and data gener- 3. Discussion
ally agree at k values higher than the fitted range.
3.1. Structural Analysis

2.2.4. Ferroelectric Performance
HfO2–ZrO2 bilayers were grown using the same procedures as
samples SHZ and SZH on a conductive TiN layer (samples
STHZ and STZH, respectively) and annealed at 500  C in N2
for 10 min, followed by deposition of TiN top contacts at
250  C. Electric polarization curves for these samples, following
mild wake-up cycling, are shown in Figure 6. Both samples show
clear ferroelectric behavior: sample STHZ has a remanent polar-
ization 2Pr of 24.5 μC cm2, whereas sample STZH’s 2Pr is
10.2 μC cm2.
Phase fraction ranges, given in Table 2, were determined as the
upper and lower limits of the uncertainty bounds of each phase
fraction in Table 1. The oFE-ZrO2 phase is clearly dominant in
sample SHZ, whereas there is a significant phase fraction of
t-ZrO2 in sample SZH. All other measurements reveal a
small-to-nonexistent t phase fraction. The conservative formula-
tion of uncertainty used here leads to large phase fraction ranges
for m- and oFE-HfO2 in sample SHZ, as expected because the
EXAFS signals from these two phases are nearly degenerate.
Statistically significant differences in the HfO2 phase fraction
between samples are therefore unresolvable by EXAFS alone,

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20
10
Polarization [ µC cm-2 ]
0 immediately crystallized into the tetragonal phase, whereas
-10
-20
-4 -3 -2 -1
Electric Field [MV cm-1]
Figure 6. Ferroelectric polarization curves for HfO2/ZrO2 bilayers with
different stacking orders.
although more careful choices of reference spectra can improve
the precision of future measurements by reducing systematic
error.
To better distinguish oFE-HfO2 from m-HfO2, quantitative
XRD analysis is constrained using the more clearly resolved
t-HfO2 and m-, oFE-, and t-ZrO2 phase fractions from EXAFS.
The analysis is discussed in detail in the Section S3,
Supporting Information, and results are shown in square brack-
ets in Table 2. This analysis yields a much smaller uncertainty
range on the m-HfO2 phase fraction and subsequently refines
the oFE-HfO2 phase fraction ranges. Considering the aggregate
phase fractions of ZrO2 and HfO2, sample SHZ has a signifi-
cantly larger oFE phase fraction than sample SZH, which in turn
correlates with the improved ferroelectric performance of sample
STHZ (Figure 6). This matches the expectation that the noncen-
trosymmetric oFE phase is primarily responsible for ferroelectric
performance.[13]
3.2. Interfacial Effects on Crystallization
Table 2 shows that the surface ZrO2 layer is almost completely
(82%–100%) composed of the oFE phase for sample SHZ,
whereas there is 32%–50% t-ZrO2 in sample SZH, where
ZrO2 contacts the underlying Si. The oFE phase fraction of
HfO2 is less dramatically affected by deposition order, although
there is a somewhat larger minority m-HfO2 phase for sample
Table 2. Summary of Crystal Phase Distributions.
Sample
fma)
c)
SZH 16–38 [28–32]
SHZ 0–30 [5–12]
a)
Phase fraction ranges are given as percentage values for the monoclinic ( fm), ferroelectric orthorhombic ( foFE), and tetragonal ( ft) phases of HfO2 and ZrO2; b)Total bilayer
phase fractions are given as sums of HfO2 and ZrO2 ranges weighted by the thickness of each layer; c)Values in square brackets are from XRD-constrained analysis.
Phys. Status Solidi B 2020, 257, 1900285
www.pss-b.com
SZH. To understand these phenomena, prior work is surveyed
to relate interfacial phenomena and ferroelectricity in ultrathin
(Hf,Zr)O2 films prepared under conditions in which interfaces
dominate the crystallization behavior (i.e., few-nm films proc-
essed at or below 500  C).
In an early study of HfO2–ZrO2 bilayers, Kim et al.[17] found
that ZrO2 deposited by ZrCl4/H2O ALD onto SiOx at 300  C
HfO2 deposited by HfCl4/H2O remained amorphous. Zhao
et al.’s[37] systematic study of ultrathin film crystallization with
annealing temperature also proved that ZrO2 crystallizes at sig-
nificantly lower temperatures than HfO2. Figure S2, Supporting
STZH
STHZ Information, shows nearly identical diffraction patterns with no
detectable crystallinity for both bilayer samples as deposited at
260  C, indicating an amorphous initial condition for both
bilayer configurations. Thus, the propensity of ZrO2 to crystallize
0 1 2 3 4
more readily than HfO2 is expected to play a significant role in
the crystal phase distribution after annealing.
In their detailed study on HfO2–ZrO2 bilayers, Lu et al.[14]
found that increasing the thickness of a ZrO2 capping layer from
1.5 to 6 nm atop a 6 nm HfO2 layer on Pt led to an increasing total
bilayer phase fraction of t and/or oFE versus m. Similarly, this
work shows a much larger fraction of m-HfO2 when HfO2
has an unconstrained surface (sample SZH) versus an interface
with underlying Si (sample SHZ). Although Lu et al.[14] sug-
gested that the confinement of HfO2 enhances the oFE phase
fraction in HfO2, their electron microscopy analysis neglected
the ZrO2 phase, which is implicated in the enhanced ferroelectric
performance of the substrate/HfO2/ZrO2 stack. The larger
t-ZrO2 phase fraction for sample SZH has no apparent templat-
ing effect on the t-HfO2 phase fraction, which is small for both
samples.
By correlating Hf0.5Zr0.5O2 crystallite size and strain with fer-
roelectric performance, Park et al.[38] found that a higher density
of randomly oriented crystallites provides appropriate strain to
form the oFE phase. Such a condition can be expected from
nucleation at a free surface, as is the case for ZrO2 in sample
SHZ, which is nearly completely in the oFE phase after anneal-
ing. Replacing the free interface of ZrO2 (sample SHZ) by an
interface with native SiOx (sample SZH) results in greater sus-
ceptibility to form the more stable t phase.
A consequence of the different deposition orders of samples
SHZ and SZH is that the bottom layer was held at the ALD tem-
perature (260  C) for a longer time (3200 s for SZH, 5400 s for
SHZ) than the top layer. Under these conditions, few-nm seed
nuclei (likely t-ZrO2) might form, which would influence
crystallization during subsequent annealing.[39–41] At a higher
ALD temperature (300  C), the formation of a crystalline ZrO2
HfO2 ZrO2 Bilayer, totalb)
foFE ft fm foFE ft fm foFE ft
54–75 [50–70] 0–20 0–9 50–68 32–50 8–23 [14–20] 52–71 [50–69] 16–35
54–94 [65–88] 5–26 0–18 82–100 0–18 0–24 [2–15] 67–97 [73–93] 2–22
1900285 (8 of 10) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
“seed layer” was shown to improve 2Pr of a 10 nm Hf0.43Zr0.57O2
film, indicating a higher oFE crystal phase fraction.[42] However,
the EXAFS spectra of the as-deposited 3 nm HfO2 and ZrO2
films in the present work are approximately identical between
samples SHZ and SZH (Figure S5, Supporting Information),
yielding no evidence of a difference in nucleation during depo-
sition. In summary, this analysis suggests that the interfacial
nucleation of ZrO2 crystallites during annealing is key to the final
crystal phase distribution, and therefore the ferroelectric perfor-
mance, of ultrathin HfO2–ZrO2 bilayers grown by ALD at 260  C.
4. Conclusions
A larger Pca21 orthorhombic phase fraction is linked to a
2.4
larger remanent polarization for a HfO2–ZrO2 bilayer with
an unconstrained ZrO2 surface during annealing. Crystal phase
fractions were measured using a combined XRD and EXAFS
analysis method which distinguishes signals for different crystal
phases that are nearly degenerate in either measurement alone.
By providing an accurate measurement of the ferroelectric phase
fraction in ultrathin (Hf,Zr)O2 films, this analysis resolves a cru-
cial problem in the evidence-directed development of devices that
rely on ferroelectric materials.
EXAFS measurements are element-selective and can pene-
trate several μm of material; therefore, they can be used to probe
whole devices without interference from materials such as
TiN.[13] Measurements may be performed quickly over a limited
k range,[30] enabling fast screening of ultrathin films or even in
situ mechanistic studies of devices under processing[43] or oper-
ating[44] conditions. The “fingerprinting” method described
herein enables the interpretation of complex or mixed-phase
materials which were previously inscrutable by EXAFS analysis
and can be extended to other spectroscopies which encode the
unique structural signatures of different crystal phases.[45,46]
5. Experimental Section
Sample Preparation: To deposit 3 nm of HfO2 [ZrO2], 24 [41] ALD
cycles of Hf[N(CH3)2]4 (TDMA-Hf, Air Liquide) [(tris(dimethylamino)cyclo-
pentadienyl)-zirconium (ZyALD), Air Liquide] and 4% ozone / 96% O2
were run with a substrate temperature of 260  C. After ALD on
300 mm Si(100) wafers with a native oxide overlayer, the wafers were
cleaved into 45 mm squares, of which some were set aside (the “as-depos-
ited” condition) and some were annealed at 500  C for 10 min in N2 in an
Allwin21 rapid thermal processing tool. Two additional bilayer samples
were prepared for electrical testing on a Si wafer with 300 nm thermal
oxide coated with 5 nm TiN by physical vapor deposition (PVD). Using
the same ALD recipes as earlier, 3 nm HfO2 was deposited atop 3 nm
ZrO2 (sample STZH) or vice versa (sample STHZ), then annealed at
500  C for 10 min in N2. TiN top contacts (100 nm thick) were then depos-
ited by PVD at 250  C. The circular contacts (0.305 mm diameter;
0.073 mm2 area) were defined by a shadow mask.
Electrical Characterization: Polarization curves were collected using a
Radiance Precision II ferroelectric tester and a Cascade probe station.
Polarization–voltage scans were collected with a triangular waveform
(0.25 kHz) after applying a mild wake-up stress of 2.5 V at 1 kHz for 1 s.
X-Ray Measurements: XRR was measured at beamline 2-1 at the
Stanford Synchrotron Radiation Lightsource (SSRL) at SLAC National
Accelerator Laboratory using an 8.00 keV X-ray beam (43 μm wide).
Prior to analysis, the specular XRR measurement was corrected by sub-
tracting the background scattering (measured with an incident beam angle
Phys. Status Solidi B 2020, 257, 1900285 1900285 (9 of 10)
www.pss-b.com
of (2θ)/2  0.5 and averaged). GIXRD measurements were performed on
a Bruker D8 Discover diffractometer using a monochromated Cu X-ray
tube (Cu Kα, λ ¼ 1.5418 Å).The incident beam angle was fixed at 0.7 ,
and XRD patterns were collected over the range 20 < 2θ < 110 in
0.05 steps using a position-sensitive detector. XRD peaks were fit using
the lmfit package[47] in Python 3.6.
GIXAS measurements were performed at SSRL beamline 11-2.
Monochromatic X-ray energies were selected by a Si (220) double-crystal
monochromator calibrated to 9560.7 eV (Hf L3 edge) and 17997.6 eV
(Zr K edge) using the maximum of the first inflection point of the first deriv-
ative of spectra collected using Hf and Zr metal foils. Harmonic rejection
and collimation of the beam was done upstream of the monochromator
with a Rh-coated silicon mirror set with a 21 keV cut-off. The monochro-
mated beam was focused with a toroidal silicon mirror and in-hutch slits
to achieve a vertical focus of 100 μm and a nominal spot width of
1 mm. Fluorescence signal was collected with a monolithic 100-element
Canberra germanium detector mounted at a 90 angle to the incident beam.
A Huber two-circle goniometer independently controlled the grazing
incidence angle, which was selected to be sufficiently high to minimize
self-absorption effects. The samples were azimuthally spun during measure-
ments to smear out sharp diffraction peaks from the Si substrate.
EXAFS Analysis: EXAFS spectra were analyzed by LCF using a basis set
of simulated “fingerprint” spectra corresponding to single-phase (m, oFE,
or t) ZrO2 or HfO2 (Figure 2 and 3). These spectra were simulated from
static average atomic positions (structures described in Section S2,
Supporting Information) using FEFF8-lite software[28,29] by summing
the EXAFS contributions of photoelectron scattering paths up to a cutoff
radius of 6.0 Å. The disorder σ2 for each photoelectron scattering path was
parameterized as a linear function of the effective photoelectron scattering
path length, Reff (σ2 ¼ aReff þ b). The best-fit coefficients a [Å] and b [Å2]
were determined by simulating an ensemble of EXAFS spectra for a crystal
phase (χs(k)) with different a and b values, then fitting each spectrum to an
experimental EXAFS spectrum of a sample with the same crystal phase
(χe(k)) The best-fit coefficients were determined by minimizing an R-factor
between experimental and simulated k3-weighted EXAFS spectra over
3.5 < k < 11.0 Å1 (Equation (1)). The amplitude reduction parameter
S02 was simultaneously fitted as an amplitude scaling factor for the
simulated spectrum.
P
k ðk
3
χ ðkÞ  k3 S20 χ s ðkÞÞ2
R¼ Pe 3 (1)
k ðk χ e ðkÞÞ
2
Spectra for the m, oFE, and t crystal structures were simulated using the
best-fit a, b, and S02 parameters, and binding energy offsets ΔE0 were
applied in increments of 2 eV to generate a basis set for LCF. Treating
ΔE0 as a variable accommodates uncertainty in defining k ¼ 0 Å1 during
the initial spline fit to the raw X-ray absorption spectrum μ(E). The under-
lying assumption of the LCF method is that the structures used to generate
the basis set of spectra provide accurate distributions of bond lengths and
coordination numbers, so these are not treated as fit parameters (as is
typically done in shell-by-shell EXAFS analysis). However, due to the strong
correlation between ΔE0 and bond length,[48] ΔE0 acts as an ad hoc param-
eter for isotropic distortions[25] such as strain or the 1% overestimation
of the simulated HfO2 lattice parameter due to PBE-GGA approximation.
P
LCFs were performed using Athena software[49] by fitting i f i k3 χ s,i ðkÞ
to k χ(k) measured for films with an unknown crystal phase composition,
3
yielding the phase fractions fi for 2–3 simulated basis spectra χ s,i ðkÞ
included in each fit. Fits were constrained such that 0 ≤ fi ≤ 1 and
Σfi ¼ 1, and fit quality was assessed by an R-factor evaluated over the fitting
region of 3.5 < k < 11.0 Å1. Additional fits which included EXAFS spectra
from the amorphous as-deposited films were attempted during the initial
disorder calibration, but the final fits assume a completely crystallized film.
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Acknowledgements
The authors thank Prof. Oscar Juan Dura and Prof. Georges Calas for pro-
viding ZrO2 EXAFS reference spectra. Use of the Stanford Synchrotron
Radiation Lightsource, SLAC National Accelerator Laboratory, was sup-
ported by the US Department of Energy, Office of Science, Office of
Basic Energy Sciences under Contract No. DE-AC02-76SF00515.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
extended X-ray absorption fine structure analyses, ferroelectrics, hafnium
oxide, nonvolatile memories, zirconium oxide
Received: May 20, 2019
Revised: August 8, 2019
Published online: September 11, 2019
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