Ceramics International xxx (xxxx) xxx

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Solution-based fabrication of high-entropy Ba(Ti,Hf,Zr,Fe,Sn)O3 films on

fluorine-doped tin oxide substrates and their piezoelectric responses
Yi-Wei Chen, Jr-Jeng Ruan, Jyh-Ming Ting, Yen-Hsun Su, Kao-Shuo Chang *
Department of Materials Science & Engineering, National Cheng Kung University, No.1, University Road, Tainan City, 70101, Taiwan

A R T I C L E I N F O A B S T R A C T

Keywords: This paper reports the first fabrication of high-entropy Ba(Ti,Hf,Zr,Fe,Sn)O3 films on fluorine-doped tin oxide
Ba(Ti,Hf,Zr,Fe,Sn)O3 film substrates through spin coating and hydrothermal synthesis. A homogeneous distribution of all constituent el­
High-entropy oxide ements was observed through energy-dispersive x-ray spectroscopy mapping. High distortion (approximately
Hydrothermal synthesis
1.7%) of the lattice structure was caused by the underlying substrate and partial substitution of Ti with other
Piezoelectric coefficient
Ferroelectricity
larger elements of Hf, Zr, Fe, and Sn on B sites. Two types of Ba(Ti,Hf,Zr,Fe,Sn)O3 films were studied: high-
density and slightly textured polycrystalline particles (Sample A), and randomly distributed [110]-oriented
nanorods with marginal crystallinity (Sample B). In the piezoelectric experiment, Samples A and B substan­
tially outperformed the medium-entropy oxide (MEO) samples and single-crystal ZnO bulk. Sample A also
exhibited the highest piezoelectric coefficient (d33 ~ 60 pm/V) among all studied samples. Its superior perfor­
mance was attributable to a combination of high crystallinity, strong out-of-plane distortion, slightly textured
polycrystalline structures, and cocktail effects. Furthermore, enhanced piezoelectricity was achieved after poling
for the high-entropy oxide (HEO) and MEO samples, indicating their ferroelectric effect. The d33 of Sample A
more than doubled (≈126.7 pm∙V− 1), and the increase was substantially higher than that of Sample B. Our HEO
samples have promise for use in piezoelectric- and ferroelectric-related applications.

1. Introduction to viable applications for engineering.

Typical piezoelectric structures include wurtzite (e.g., AlN, CdS, and
ZnO), perovskite [e.g., Pb(Zr,Ti)O3 (PZT) and BaTiO3 (BTO)], and
quartz (e.g., GeO2, GaAsO4, and AlPO4) [1,2]. Among them, perovskite
PZT has been the most studied and applied since World War II because of
its exceptional spontaneous polarization without external stress. How­
ever, toxic Pb has negative impacts on the environment and human
health; thus, the search for alternatives has persisted.
High-entropy alloys and equiatomic multicomponent alloys were
independently developed by Yeh et al. [3] and Cantor et al. [4] in 2004,
respectively. They comprise at least five principal elements with 5–35 at.
% each. According to Yeh’s theory [3], high-entropy alloys have a
configurational entropy (ΔSconf) greater than 1.5 R (R: gas constant) at a
random state, whereas medium-entropy alloys have ΔSconf between 1
and 1.5 R [5]. The high-entropy effect has been extended to ceramics
[6], which covers a wide range of classes, including oxide, carbide,
nitride, silicide, diboride, and sulfide. The broad compositional space
provides a diversity of unexplored functional properties that could lead
Among high-entropy ceramics, high-entropy oxides (HEOs) are a
particularly promising option because of the ready availability of
manufacturing facilities and the reactive oxygen–related sources used to
produce them. In 2015, Rost et al. first studied entropy-stabilized oxides,
whose properties were driven by configurational disorder [7]. They used
a solid-state reaction to synthesize (Co,Cu,Mg,Ni,Zn)O by mixing equi­
molar CoO, CuO, MgO, NiO, and ZnO. The resulting powders were then
fired in air (700 ◦ C− 1100 ◦ C) and quenched. A single-phase quinary
rock salt (Co,Cu,Mg,Ni,Zn)O was formed at 850 ◦ C− 900 ◦ C, and the
formation of a multiphase mixture of rock salt and tenorite was observed
below that range. The entropy-stabilized (reversible) phase evolution as
a function of temperature indicated the increased (or decreased)
contribution of configurational entropy at high (or low) temperatures.
Furthermore, the removal of any component oxide resulted in multi­
phase states, implying that the decrease in ΔSconf reduced the stability
(increased the Gibbs free energy) of associated quaternary compounds.
The same HEO system has also been investigated by other groups.
Berardan et al. [8] examined dopant-doped (e.g., Li+, In3+, Ga3+, and

* Corresponding author.
E-mail address: kschang@mail.ncku.edu.tw (K.-S. Chang).

https://doi.org/10.1016/j.ceramint.2020.12.272
Received 30 November 2020; Received in revised form 18 December 2020; Accepted 29 December 2020
Available online 5 January 2021
0272-8842/© 2020 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Yi-Wei Chen, Ceramics International, https://doi.org/10.1016/j.ceramint.2020.12.272
 Y.-W. Chen et al.
Ti4+) (Co,Cu,Mg,Ni,Zn)O dielectrics. Only Li+ doping could stabilize a
single-phase structure because of charge compensation mechanisms that
could occur through the oxidation of Co+2 (or Ni+2) to Co+3 (or Ni+3) or
through the formation of oxygen vacancies. Furthermore, Sarkar et al.
[9] employed nebulized spray pyrolisis, flame spray pyrolysis, and
reverse coprecipitation to obtain nanocrystalline (Co,Cu,Mg,Ni,Zn)O.
Other fascinating single-phase HEOs have also been studied,
including perovskite [10–14], rock salt [15–19], spinel [20,21], fluorite
[22,23], and pyrochlore [24,25], produced through various fabrication
approaches, such as solid-state reactions [16,17,21–26], physical vapor
deposition [12,27], solution combustion synthesis [15,18,28], hydro­
thermal synthesis [29,30], and a sonochemical-based method [10].
Certain representative studies are discussed as follows. Braun et al. [19]
reported that the thermal conductivity of rock salt (Mg0.2Ni0.2Cu0.2
Co0.2Zn0.2)O was doubly reduced by the local disorder of ionic charges
without weakening its mechanical stiffness when another element of
equal molarity (e.g., Sc, Sb, Sn, Cr, and Ge) was added to the system.
Sharma et al. [12] observed extremely low thermal conductivity in
single-crystal epitaxial thin films of Ba(Zr0.2Sn0.2Ti0.2Hf0.2Nb0.2)O3
grown on MgO and SrTiO3 substrates. Their respective conductivities
[approximately 0.58 and 0.54 W⋅(m⋅K)− 1] were close to the theoretical
limit for cubic-phase BaTiO3 in an amorphous state [approximately 0.48
W⋅(m⋅K)− 1], which suggests that they may have potential for use in
thermoelectric power generation applications and thermal barrier
coatings. Berardan et al. [17] studied the ionic conductivity of (Co,Cu,
Mg,Ni,Zn)1-xAxO (A = Li, Na, and K) and (Co,Cu,Mg,Ni,Zn)1-2xLixGaxO.
Their results revealed that (Co,Cu,Mg,Ni,Zn)1-xLixO outperformed a
state-of-the-art lithium phosphorous oxynitride solid electrolyte by
more than 2 orders of magnitude at room temperature. The excellent
ionic conductivity (>10− 3 S cm− 1) resulted from oxygen vacancies
induced by Li+ doping because of charge compensation.
Further-enhancement of ionic conductivity could be obtained through
the optimization of oxygen-vacancy concentrations/or ordering and
divalent cation sizes in the system. Sarkar et al. [18] reported that en­
tropy stabilization substantially improved the storage capacity retention
and cycling stability of (Co0.2Cu0.2Mg0.2Ni0.2Zn0.2)O, whereas severe
degradation in capacity was observed for the samples without Zn, Cu, or
Co. Berardan et al. [8] investigated the electrical properties of (Mg,Co,
Ni,Cu,Zn)O, (Mg,Co,Ni,Cu,Zn)0.95Li0.05O, and (Li,Mg,Co,Ni,Cu,Zn)O.
They observed that (Mg,Co,Ni,Cu,Zn)0.95Li0.05O exhibited a high rela­
tive permittivity of 2 × 105 at 20 Hz and 440 K, which was retained in a
wide frequency range (2.3 MHz–100 Hz). The dielectric and electro­
caloric properties of (Na0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3 perovskite powders
at various temperatures were also explored by Pu et al. [13] for appli­
cations in solid-state refrigeration and energy storage. Furthermore,
Zhou et al. [14] reported the fabrication of Ba(Zr0.2Ti0.2Sn0.2Hf0.2Me0.2)
O3 (Me = Y3+, Nb5+, Ta5+, V5+, Mo6+, and W6+) perovskite powders, in
which single-phase Ba(Zr0.2Ti0.2Sn0.2Hf0.2Ta0.2)O3 and Ba
(Zr0.2Ti0.2Sn0.2Hf0.2Nb0.2)O3 respectively exhibited high dielectric con­
stants of approximately 49 and 60 at 2 MHz. Mao et al. [20] studied the
room-temperature magnetic properties of spinel (Cr0.2Fe0.2Mn0.2Co0.2
Ni0.2)3O4, (Cr0.2Fe0.2Mn0.2Ni0.2Zn0.2)3O4, and (Cr0.2Fe0.2Mn0.2
Co0.2Zn0.2)3O4. When Zn2+ was substituted for either Co2+or Ni2+, the
saturation and remanence magnetization and coercivity decreased
because the nonmagnetic Zn2+ ions reduced the number of
super-exchange interactions among their magnetic moments. Further­
more, Meisenheimer et al. [31] reported the existence of
entropy-stabilized antiferromagnetic permalloy− (Mg0.25(1-x)CoxNi0.25
(1-x)Cu0.25(1-x)Zn0.25(1-x))O heterostructures, as confirmed by the obser­
vation of a critical blocking temperature and anisotropic magnetic
exchange.
Although studies on HEOs have gained popularity, most of them
have focused on studying the mechanical strength [31,36], thermal and
ionic conductivity [12,17,19], dielectric properties [13,14], and
magnetism [20,31] of powders fabricated through solid-state reactions.
Few studies have been conducted on HEO films, and most of them have
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been limited to exploring films fabricated on Si or MgO substrates
through physical vapor deposition techniques. Furthermore, studies on
morphology adjustment and piezoelectricity are still lacking. In this
study, a facile spin-coating and hydrothermal approach was developed
to fabricate various Ba(Zr,Hf,Sn,Fe,Ti)O3 films on fluorine-doped tin
oxide (FTO) substrates. The influence of their morphology, film orien­
tation, and crystallinity on the resulting piezoelectricity was investi­
gated to gain insight into their ability to optimize piezoelectric devices.
2. Experimental procedure
FTO/glass substrates were ultrasonically cleaned using acetone,
ethanol, isopropyl alcohol, and deionized (DI) water in sequence for 5
min each to remove both organic and inorganic contaminants before the
experiment. The samples were then prepared through spin coating,
followed by hydrothermal synthesis. To prepare the spin-coating solu­
tion, 0.122 g of BaCl2 2H2O, 0.129 mL of TiCl3, 0.032 g of HfCl4, 0.05 g
of ZrOCl2 8H2O, 0.027 g of FeCl3 6H2O, and 0.035 g of SnCl4 5H2O (Ba:
Ti:Hf:Zr:Fe:Sn = 5:1:1:1:1:1 in molar ratio) were dissolved in 10 mL of
ethanol and stirred for 30 min. Next, 0.25 mL of the solution was spin
coated twice onto a cleaned FTO/glass substrate at 500 rpm for 5 s,
followed by 2000 rpm for 20 s. The substrate was then dried at 150 ◦ C
for 3 min in air and naturally cooled to room temperature. The entire
process was performed 10 times before the substrate was annealed at
400 ◦ C for 2 h on a hot plate to obtain HEO-seed-layer–coated substrates.
The same process was also applied to obtain medium-entropy oxide
(MEO)-seed-layer–coated substrates, in which each of the constituent
elements on the B sites of Ba(Ti,Hf,Zr,Fe,Sn)O3 was excluded through
the removal of associated precursor sources. Hereafter, MEO− Ti and
MEO− Fe indicate Ba(Hf,Zr,Fe,Sn)O3 and Ba(Ti,Hf,Zr,Sn)O3,
respectively.
During hydrothermal synthesis, 0.732 g of BaCl2 2H2O, 0.26 mL of
TiCl3, 0.128 g of HfCl4, 0.1 g of ZrOCl2 8H2O, 0.108 g of FeCl3 6H2O, and
0.14 g of SnCl4 5H2O (Ba:Ti:Hf:Zr:Fe:Sn = 15:1:2:1:2:2 in molar ratio)
were dissolved in 40 mL of DI water. Various complex agents, including
polyvinylpyrrolidone (PVP), hexamethylenetetramine (HMTA), poly
(vinyl alcohol) (PVA), citric acid, and ethylenediaminetetraacetic acid
disodium salt (EDTA− 2Na), were added to the precursor solution under
extensive stirring for 30 min. Suitable amounts of KOH tablets were used
to adjust the pH to approximately 13.5. The prepared solution and a
HEO-seed-layer–coated FTO/glass substrate were subjected to hydro­
thermal reactions at 200 ◦ C for 2 h and then naturally cooled to room
temperature. The substrate was removed from the autoclave and washed
with DI water several times to obtain the Ba(Ti,Hf,Zr,Fe,Sn)O3 films. The
residuals in the autoclave were also collected through centrifugation,
thoroughly washed with DI water and ethanol, and subsequently dried
at 90 ◦ C for 4 h to obtain the Ba(Ti,Hf,Zr,Fe,Sn)O3 powders. In addition,
to enhance the crystallinity of the EDTA− 2Na involved Ba(Ti,Hf,Zr,Fe,
Sn)O3 nanorod films, the samples were further annealed at 600 ◦ C for 3 h
after the hydrothermal process. The same process was followed to obtain
the MEO films and powders, excluding the annealing process at 600 ◦ C
because they already displayed adequate crystallinity.
X-ray diffraction (XRD) and two-dimentional (2D) microdiffraction
(D8 DISCOVER with GADDS, Bruker AXS Gmbh, Karlsruhe, Germany),
equipped with a Cu (Kα) radiation source (λ = 0.154 nm), and scanning
electron microscopy (SEM) were employed to characterize the crystal­
linity, phases, textures, and morphology of the samples. The micro­
structures and crystallinity were further examined using high-resolution
transmission electron microscopy (HRTEM) and selective area electron
diffraction (SAED). Energy-dispersive spectroscopy (EDS) in TEM and
inductively coupled plasma− mass spectrometry (ICP− MS) were per­
formed to determine the elemental distribution and stoichiometric
characteristics of the samples, respectively. The piezoelectric coefficient
(d33) was determined using piezoelectric force microscopy (PFM), which
was performed on the basis of detection of local vibrations induced by an
AC signal (1 kHz) applied between a conductive tip (force of
 Y.-W. Chen et al.
approximately 70 nN) and a bottom electrode of the samples [32]. With
the d33 of approximately 9.93 pm∙V− 1 of the single-crystal ZnO bulk as a
reference, the d33 of the samples can be obtained as follows [Eq. (1)]:
d33,sample = (slopesample/slopeZnO) × 9.93 (1)
where d33,sample is the piezoelectric constant of the samples, and slope
sample and slopeZnO denote the slopes of the samples and ZnO, respec­
tively, in a plot of amplitude against AC voltage. A slow scan rate was
employed to reliably obtain the topography and amplitudes of the
samples. Furthermore, to maximize the piezoelectric response of the
samples, a poling process was used by applying a high DC voltage
(approximately 4.2 kV) across two parallel metal plates (resulting
electric field of approximately 1 kV mm− 1) for 30 min.
3. Results and discussion
The BTO powders were first obtained hydrothermally through the
adjustment of various precursor ratios and pH values (PDF#05-0626)
(red, Fig. 1). The resulting strain (approximately 0.13%) was estimated
using a Williamson–Hall plot of (βhkl cosθ) vs (4 sinθ), where βhkl is the
intensity of the full width at half maximum for hkl (Miller index) and θ is
the diffraction angle [33,34]. The strain was due to size confinement, in
which atomic configurations in the BTO nanocrystals were modulated
relative to those in the BTO bulk. The procedure was then modified to
obtain the Ba(Ti,Hf,Zr,Fe,Sn)O3 powders (green, Fig. 1), whose char­
acteristic peaks shifted toward lower angles relative to those associated
with the BTO powders. This indicated a higher distortion (approxi­
mately 0.15%) of the lattice structure because of the substitution of Ti on
B sites by the larger elements Hf, Zr, Fe, and Sn. Furthermore, the
ICP− MS result revealed nearly equimolar ratios of the constituent ele­
ments on B sites of the Ba(Ti,Hf,Zr,Fe,Sn)O3 powders (Fig. S1).
The same procedure was then applied to the fabrication of the Ba(Ti,
Hf,Zr,Fe,Sn)O3 films on various substrates [e.g., Si, indium tin oxide
(ITO) and FTO] through a single-step hydrothermal route. Our results
confirmed that the films only grew on FTO substrates [red, Fig. 2(a)].
The characteristic peaks at approximately 30.8◦ and 44.2◦ were asso­
ciated with the planes indexed at (110) and (200) of Ba(Ti,Hf,Zr,Fe,Sn)
O3, respectively. Compared with the Ba(Ti,Hf,Zr,Fe,Sn)O3 powders
(green, Fig. 1), no plane indexed at (111) (approximately 38.8◦ ) was
observed, indicating the growth of textured films, which is further dis­
cussed in the section describing PFM measurement results. This dem­
onstrates the first hydrothermal fabrication of HEO films on a
transparent conducting oxide substrate, potentially creating opportu­
nities for use in optoelectronic engineering and devices. No films grew
on Si [blue, Fig. 2(a)] or ITO [green, Fig. 2(a)] substrates because these
substrate were etched under strongly basic conditions (pH ≈ 13.5)
during the hydrothermal reactions.
However, the quality of the resulting Ba(Ti,Hf,Zr,Fe,Sn)O3 film re­
quires improvement to address its nonuniformity and low density, which
Fig. 1. XRD results of hydrothermally fabricated BaTiO3 (red) and Ba(Ti,Hf,Sn,
Zr,Fe)O3 (green) powders. (For interpretation of the references to colour in this
figure legend, the reader is referred to the Web version of this article.)
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Ceramics International xxx (xxxx) xxx
considerably limits their wide applicability for use in next-generation
sensors and piezoelectric devices. Therefore, two strategies were
designed to improve the developed hydrothermal approach: (1) adopt­
ing a two-step hydrothermal route using various complex agents in each
step, and (2) using seed-layer spin coating first, followed by a hydro­
thermal approach (without complex agents). The first approach slightly
improved the growth of the Ba(Ti,Hf,Zr,Fe,Sn)O3 films [Fig. S2(a)] over
the single-step hydrothermal approach [red, Fig. 2(a)]; however, the
film density remained poor [Fig. S2(b)]. By contrast, the second
approach considerably improved both the film crystallinity [orange,
Fig. 2(a)] and density [Fig. 2(b)] (Sample A) compared with the single-
step (Fig. 2) and two-step (Fig. S2) hydrothermal approaches. Further­
more, the resulting substantial strain (approximately 1.7%) relative to
that obtained for the powder samples was attributable to the lattice
mismatch between the film and underlying substrate, in addition to the
lattice distortion, as displayed in Fig. 1. Furthermore, the 2D micro­
diffraction pattern [azimuthal angle (χ) vs 2θ] [Fig. 2(c)] revealed that
the Ba(Ti,Hf,Zr,Fe,Sn)O3 films had a slightly textured polycrystalline
structure because of a nonuniform ring associated with the (110) plane.
To adjust the morphology of Sample A, various amounts and types of
complex agents, including PVP, HMTA, PVA, citric acid, and
EDTA− 2Na, were added to the hydrothermal reaction of the second
approach. However, only the addition of EDTA− 2Na produced dramatic
changes, and the others exhibited ineffective morphological tailoring for
the Ba(Ti,Hf,Zr,Fe,Sn)O3 films [Fig. S3(a)–(d)]. However, the addition
of EDTA− 2Na produced dramatic changes. After the addition of 0.185 g
of EDTA− 2Na, nanorods mixed with irregular particles [Fig. 3(a)] and
exhibiting decent crystallinity [blue, Fig. 3(d)] were observed. When the
amount of EDTA− 2Na was doubled (approximately 0.37 g), high-
density nanorods formed [Fig. 3(b)], possibly because of the resulting
complex species during the hydrothermal reactions. These species could
selectively absorb or desorb onto various facets of Ba(Ti,Hf,Zr,Fe,Sn)O3
crystals to cause anisotropic crystal growth [35]. However, their crys­
tallinity was substantially deteriorated [green, Fig. 3(d)] compared with
that of the of EDTA− 2Na (0.185 g) sample and Sample A. When greater
amounts of EDTA− 2Na (approximately 0.74 g) were involved, both the
nanorod densities [Fig. 3(c)] and their crystallinity [red, Fig. 3(d)] were
substantially reduced. Thus, crystalline Ba(Ti,Hf,Zr,Fe,Sn)O3 nanorods
were not obtained through simple adjustment of the amounts of
EDTA− 2Na. The second approach was then further modified on the
basis of the EDTA− 2Na (0.37 g) sample under various annealing con­
ditions, including heat treatments (<400 ◦ C) during the first-step
spin-coating process or postannealing after the second-step hydrother­
mal reaction. Our results revealed that Ba(Ti,Hf,Zr,Fe,Sn)O3 nanorods
were unfavorably converted to particles at room temperature [Fig. S4
(a)], 200 ◦ C [Fig. S4(b)], and 300 ◦ C [Fig. S4(c)] in the first-step spin
coating without postannealing; however, their crystallinity was
enhanced, particularly at room temperature and 200 ◦ C [blue and red in
Fig. S4(d), respectively]. By contrast, the sample fabricated at 400 ◦ C
during spin coating and postannealed at 600 ◦ C for 3 h (Sample B)
retained the Ba(Ti,Hf,Zr,Fe,Sn)O3 nanorods [Fig. 4(a)] and exhibited
certain, although weak, crystallinity [Fig. 4(b)], which was also
observed in the 2D microdiffraction pattern [Fig. 4(c)]. Its resulting
strain was then analyzed through TEM analysis (Fig. 6).
Because Samples A (excellent-crystallinity particle) and B (marginal-
crystallinity nanorod) exhibited distinct features, they were further
studied using TEM. The SAED pattern [Fig. 5(a)] captured from the
particle (big white circle present in the inset) exhibited multiple and
discrete diffraction spots, indicating that various orientations of Ba(Ti,
Hf,Zr,Fe,Sn)O3 nanoparticles were involved. A d-spacing of approxi­
mately 0.2844 (d110) and 0.2046 (d200) nm was associated with (110)
and (200) planes of Ba(Ti,Hf,Zr,Fe,Sn)O3, respectively. Increases of
approximately 0.7% and 2.4% were observed in comparison with the
nominal d110 (≈0.2825 nm) and d200 (≈0.1997 nm), respectively, for
the BTO bulk. Another SAED pattern [small white circle shown in the
inset of Fig. 5(a)] illustrated strong spot arrays, which were indexed at
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Fig. 2. (a) XRD results of hydrothermally fabricated Ba(Ti,Hf,Zr,Fe,Sn)O3 films on Si (blue), ITO (green), and FTO (red) substrates through a single-step approach as
well as on FTO (orange) substrates through spin coating and a hydrothermal route (Sample A). SEM image (b) and 2D microdiffraction pattern (c) of Sample A. (For
interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

Fig. 3. Various morphologies of Ba(Ti,Hf,Zr,Fe,Sn)O3 films adjusted with various amounts of EDTA− 2Na through spin coating and a hydrothermal route. (a) 0.185 g.
(b) 0.37 g. (c) 0.74 g. (d) XRD results of the three samples.

(211), (102), and (313) planes [Fig. 5(b)], indicating the formation of
single-crystalline Ba(Ti,Hf,Zr,Fe,Sn)O3 nanoparticles. EDS mapping
revealed homogeneous distributions of all constituent elements [Fig. 5
(c)]. The strip-like distribution at the bottom of the Sn and O images is
attributable to FTO substrates. Furthermore, elemental compositions
[lower right, Fig. 5(c)] showed that the Ti content was substantially
higher than the content of other elements because of the mutual con­
tributions of Ba and Ti. The Ti signal was partially contributed by Ba
(Lα1), which was indistinguishable from the Ti (Kα1) peak in the EDS
spectrum.
Fig. 6(a) displays an HRTEM image of Sample B, captured from the
red circle shown in the inset. Predominant and minor fringes associated
with planes indexed at (110) (d110 ≈ 0.2955 nm) and (200) (d200 ≈
0.2060 nm) of Ba(Ti,Hf,Zr,Fe,Sn)O3 were observed, respectively. Sub­
stantial increases of approximately 4.6% and 3.1% were observed
compared with the respective nominal d-spacing values for the BTO

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Fig. 4. Characterizations of Sample B. (a) SEM image. (b) XRD result. (c) 2D microdiffraction pattern.

Fig. 5. TEM results of Sample A. (a) SAED pattern taken from the big circle presented in the inset. (b) SAED pattern taken from the small circle presented in the inset
in (a). (c) EDS mapping. Elemental compositions are presented in the lower-right corner for each element.

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Fig. 6. TEM results of Sample B. (a) High-resolution image captured from a red circle marked in the inset. (b) SAED pattern taken from the same location described in
(a). (c) EDS mapping. Elemental compositions are presented in the lower-right corner for each element. (For interpretation of the references to colour in this figure
legend, the reader is referred to the Web version of this article.)

bulk, which could primarily be attributable to the one-dimensional
growth of nanorods, in addition to the lattice distortion of Ba(Ti,Hf,Zr,
Fe,Sn)O3. Strong diffraction spots observed in the SAED [Fig. 6(b)],
taken from the same region as shown in the inset of Fig. 6(a), were also
associated with the (110) plane of Ba(Ti,Hf,Zr,Fe,Sn)O3. Combined with
the XRD result (Fig. 4), in which poor crystallinity was observed, highly
textured [110]-oriented nanocrystalline nanorods were fabricated. EDS
mapping [Fig. 6(c)] showed a uniform distribution for each constituent
element, confirming the fabrication of high-entropy Ba(Ti,Hf,Zr,Fe,Sn)
O3 nanorod films. The atomic ratio for each element is shown in the

Fig. 7. (a) Plot of amplitude vs AC voltage obtained through PFM of various samples, including Sample A, Sample B, MEO− Ti, MEO− Fe, single-crystal ZnO bulk,
FTO, and a piece of glass. Solid and dashed lines denote before and after poling, respectively. (b) Calculated slopes and d33. (c) Topography of Sample A.

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Y.-W. Chen et al.
lower right corner. The Ti content was also substantially higher than the
content of other elements, as discussed for Sample A.
PFM [32] was performed to determine the d33 of various samples,
including Samples A and B, MEO− Ti, and MEO− Fe. The single-crystal
ZnO bulk, FTO, and a piece of glass were also studied for comparison.
Details are provided in the Experimental section. Fig. 7(a) shows a plot
of amplitude vs AC voltage for the various samples. Negligible slopes
were observed for FTO (solid pink line) and glass (solid brown line),
indicating their expected lack of piezoelectric response. By contrast, a
moderate slope (solid purple line) was observed for single-crystal ZnO,
indicating a piezoelectric response (d33 ≈ 9.9 pm/V). In general, the
piezoelectric performance of the HEO samples [Sample A (solid red line)
and Sample B (solid blue line)] was substantially better than that of the
MEO samples [MEO− Ti (solid black line) and MEO− Fe (solid green
line)]. This might be attributable to the severe lattice distortion and a
cocktail effect [3] of the HEO samples and a partial loss of non­
centrosymmetry in the MEO samples. Furthermore, all of the HEO and
MEO samples exhibited greater slopes than did ZnO, indicating their
excellent piezoelectric response. The calculated d33 for each sample is
presented in Fig. 7(b). Sample A [topography shown in Fig. 7(c)]
exhibited the highest d33 (≈60 pm∙V− 1), followed by Sample B (≈35
pm∙V− 1), MEO− Fe (≈7.9 pm∙V− 1), and MEO− Ti (≈7.5 pm∙V− 1),
respectively. In addition to better crystallinity and slightly textured
polycrystalline structures (Fig. 2) that were effective at improving
piezoelectric response [36], the superior performance of Sample A to
that of Sample B was partially attributable to strong out-of-plane
distortion (spontaneous polarization along a z-direction for perov­
skite). As indicated in the TEM analyses (Figs. 5 and 6), increases in the
in-plane d110 and d200 for Sample A (approximately 0.7% and 2.4%,
respectively) were smaller than those for Sample B (approximately 4.6%
and 3.1%, respectively). Assuming the same volume of Ba(Ti,Hf,Zr,Fe,
Sn)O3 unit cells in Samples A and B, substantial out-of-plane distortion
was expected in Sample A. However, Sample B still exhibited a fairly
high d33 value, despite its overall poor crystallinity because of nano­
scopic polarity in nearly amorphous states [37], as evidenced by the
XRD and TEM analyses. The piezoelectricity of Sample B could be
considerably intensified when [001]-oriented crystalline Ba(Ti,Hf,Zr,Fe,
Sn)O3 nanorod arrays could be fabricated. A poling process was applied
to study the ferroelectricity of the samples. After poling, enhanced
piezoelectricity was observed for most of the piezoelectric samples
(dashed lines), indicating their ferroelectric effect. No apparent varia­
tion was observed for ZnO between before and after poling because of its
lack of ferroelectric response. The d33 of Sample A (dashed red line,
≈126.7 pm∙V− 1) more than doubled after poling. The value was still far
superior to those of all other samples, and the ferroelectric improvement
was substantially greater than that observed for Sample B (dashed blue
line), indicating a predominant factor of crystallinity [38].
4. Conclusions
High-entropy Ba(Ti,Hf,Zr,Fe,Sn)O3 piezoelectric films with various
morphologies on FTO substrates were fabricated through the adjustment
of pH values, complex agents, and annealing temperatures using a facile
spin-coating and hydrothermal method. EDS mapping revealed homo­
geneous distributions of all constituent elements for the fabricated HEO
films. Two distinct types of Ba(Ti,Hf,Zr,Fe,Sn)O3 films were studied:
Sample A, consisting of slightly textured polycrystalline particles, and
Sample B, comprising highly textured [110]-oriented nanorods
(adjusted by EDTA− 2Na) with marginal crystallinity. Sample A
exhibited a superior d33 value (≈60 pm∙V− 1) compared with other
samples, including Sample B (≈35 pm∙V− 1), MEO− Fe (≈7.9 pm∙V− 1),
MEO− Ti (≈7.5 pm∙V− 1), and single-crystal ZnO bulk (≈9.9 pm∙V− 1).
The excellent piezoelectric performance was attributable to the combi­
nation of high crystallinity, strong out-of-plane growth, slightly textured
polycrystalline structures, and cocktail effects. Furthermore, its d33
more than doubled (≈126.7 pm∙V− 1) after poling, and the enhancement
7
Ceramics International xxx (xxxx) xxx
was considerably greater than that for Sample B, indicating a predom­
inant factor of crystallinity for enhancing its ferroelectric response. Our
results indicate the potential of Ba(Ti,Hf,Zr,Fe,Sn)O3 films for piezo­
electric- and ferroelectric-based applications.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This study was partially supported by the Ministry of Science and
Technology, Taiwan, under the grant number MOST 107-2218-E-006-
047.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ceramint.2020.12.272.
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