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Japanese Journal of Applied Physics 58, SLLB14 (2019) REGULAR PAPER
https://doi.org/10.7567/1347-4065/ab3958

Growth of epitaxial (K, Na)NbO3 films with various orientations by hydrothermal

method and their properties
Yoshiharu Ito1, Akinori Tateyama1, Yoshiko Nakamura1, Takao Shimizu1 , Minoru Kurosawa2, Hiroshi Uchida3,
Takahisa Shiraishi4 , Takanori Kiguchi4 , Toyohiko J. Konno4 , Mutsuo Ishikawa5, and Hiroshi Funakubo1*
1
Department of Materials Science and Engineering, Tokyo Institute of Technology, J2–43, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa,
226–8502, Japan
2
Department of Electrical and Electronic Engineering, Tokyo Institute of Technology, G2–32, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa,
226–8502, Japan
3
Department of Materials and Life Sciences, Sophia University, 7–1 Kioi-cho, Tokyo, 102–8554, Japan
4
Institute for Materials Research, Tohoku University, Building 2, 6th Floor, 2–1–1, Katahira, Aobaku, Sendai, Miyagi, 980–8577, Japan
5
Department of Clinical Engineering, Toin University of Yokohama, 1614, Kurogane-cho, Aoba-ku, Yokohama, Japan, 225–8503
*
E-mail: funakubo.h.aa@m.titech.ac.jp
Received June 6, 2019; revised June 26, 2019; accepted August 6, 2019; published online September 2, 2019

{100}c-, {110}c- and {111}c-oriented epitaxial (K, Na)NbO3 thin films were grown at 240 °C on (100)cSrRuO3//(100)SrTiO3, (110)cSrRuO3//
(110)SrTiO3, and (111)cSrRuO3//(111)SrTiO3 substrates by the hydrothermal method. Their film thicknesses increased with the deposition time
and then eventually saturated at longer deposition times. Their saturated film thicknesses were mainly determined by their orientation and the order
was {100}c-, {110}c- and {111}c-orientation regardless of any experimental conditions. These films consisted of grains with characteristic
morphologies. All of the films exhibited similar ferroelectric and piezoelectric properties irrespective of the film orientation. The remnant
polarizations (Pr) and coercive fields (Ec) of the {100}c-, {110}c- and {111}c-oriented films at the maximum electric field of 500 kV cm−1 were
31 μC cm−2 and 111 kV cm−1, 27 μC cm−2 and 94 kV cm−1, and 25 μC cm−2 and 110 kV cm−1, respectively, while their effective values of
piezoelectric coefficient (d33) were approximately 31–33 pm V−1. Similar films are associated with its mixed domain structure.
© 2019 The Japan Society of Applied Physics

ferroelectric and piezoelectric properties of hydrothermally

1. Introduction
Alkaline niobates, tantalates, and their solid solutions have
attracted significant interest owing to their superior ferro-
electric, piezoelectric, pyroelectric, photorefractive, and photo-
catalytic properties.1–7) Among them, the solid-solution of
KNbO3 and NaNbO3, i.e., (K, Na)NbO3 and their related
materials have been proposed as alternative lead-free piezo-
electric materials to Pb(Zr, Ti)O3, because (K, Na)NbO3-based
materials have better piezoelectric properties and higher Curie
temperatures than other lead-free piezoelectric materials.8–11)
These materials are expected to be applied for various
applications including sensors, actuators, and vibration energy
harvesters,12–18) in the form of thin film as well as the sintered
body. The fabrication of (K, Na)NbO3-based materials is
generally challenging owing to the high volatilities of K and
Na components, leading to K- and Na-deficient composition
that degraded their piezoelectric properties. This difficulty was
also reported for films prepared by sputtering, sol-gel, and
chemical vapor deposition techniques.19–25) Therefore, the
preparation method that allows us to depress the volatilizations
of them is highly required.
In the present study, we focused on the depositions of
(K, Na)NbO3 films by the hydrothermal method. The hydro-
thermal method prevents the volatilization of K and Na
components because the films are prepared at a lower tempera-
ture below 300 °C under high pressure. L. S. Wojciech reported
the growth of epitaxial KNbO3 films deposited on SrTiO3 and
LiTaO3 single crystal substrates and Goh et al. the growth on
SrTiO3 by the hydrothermal method.26,27) In our previous study,
the film thickness of hydrothermally grown KNbO3 increased
using conductive bottom layers of SrRuO3 with a perovskite
structure.28) Based on these results, we reported the growth of
epitaxial (K, Na)NbO3 films with various K/(K + Na) ratio on
single-crystal substrates at 240 °C.29–31) In order to enhance the
SLLB14-1
deposited (K, Na)NbO3 films, orientation control is one of the
crucial factors as they strongly depend on the crystal
orientation.31–35) In addition, the orientation can also affect the
film thickness of the resulting films, i.e., the deposition rate, as
frequently observed for other perovskite-based ferroelectric
films such as PZT films.36) However few studies have reported
the dependence of orientation for thin film used by the
hydrothermal technique.
We already reported a successful growth of epitaxial
KNbO3 films on SrRuO3-coated SrTiO3 single-crystal sub-
strates with (100), (110) and (111) cut.33) In this study, we
prepared epitaxial (K, Na)NbO3 films on SrRuO3-coated
SrTiO3 single-crystal substrates with each crystal cuts by the
hydrothermal method. In addition, we investigated the effects
of the crystal orientation on the deposition rate and surface
morphology of the deposited films as well as ferroelectric and
piezoelectric properties of these films.
2. Experimental methods
(K, Na)NbO3 films were deposited on (100)cSrRuO3//
(100)SrTiO3, (110)cSrRuO3//(110)SrTiO3 and (111)cSrRuO3//
(111)SrTiO3 substrates by the hydrothermal method. 50-nm-
thick epitaxial SrRuO3 layers were grown by the radio-
frequency magnetron sputtering method as the bottom electrodes
on single-crystal SrTiO3 substrates.
Aqueous solutions of KOH and NaOH (Kanto Chemical
Co., Inc., 5–7 mol l−1, [KOH]/([KOH] + [NaOH]) = 0.9,
20 cm3) and Nb2O5 powder (Kanto Chemical Co., Inc.,
0.25–2.00 g) were used as starting materials. The materials
and substrates put into a Teflon bottle were sealed in an
autoclave. The substrates were suspended by a Teflon fixture
that is almost the same as reported one by Morita.37) Three
kinds of substrates were put into the same Teflon bottle at one
time. The autoclave was placed in an oven kept at 240 °C for
© 2019 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 58, SLLB14 (2019)
(a)
(b)
(c)
Fig. 1. (Color online) (a) Temperatures of the air and the autoclave surface
in the oven as a function of the deposition time. Film thicknesses as a
function of the deposition time for the films prepared with (b) various
concentrations of the KOH and NaOH mixed solution (green squares, blue
triangles, and red circles represent concentrations of 5, 6, and 7 mol l−1,
respectively) and (c) input mass of Nb2O5 (red closed circles and open
diamonds represent input mass of Nb2O5 of 0.25 and 2.00 g, respectively).
3–24 h for a hydrothermal reaction. The deposition time was
counted from the moment when the autoclave was placed in
the oven. Figure 1(a) shows the temperatures of the air and
the autoclave surface in the oven as a function of the
deposition time. The setting temperature of the oven was
240 °C. It took approximately 2 h to saturate the air and
autoclave temperatures. After the deposition time, the ob-
tained films were ultrasonically cleaned with distilled water,
ethanol, acetone, and methanol, and then dried at 150 °C for
1 h in the dashed air under atmospheric pressure.
In this research, we selected (K0.88Na0.12)NbO3 because
this composition shows the highest deposition rate in our
previous work.29) Also, epitaxial (K0.88Na0.12)NbO3 film
showed a relatively large piezoelectric response together
with relatively low dielectric constant among those of the (K,
Na)NbO3 films that are favorable for the sensor and vibration
harvester applications.38) In addition, no phase separation
was observed in the (K0.88Na0.12)NbO3 film, in contrast to the
two-phase coexistence of the (K0.75Na0.25)NbO3 and
(K0.36Na0.64)NbO3 films.39) Details of the [KOH]/([KOH]+
[NaOH]) dependency on the composition and the crystal
structure of the obtained film were already reported.38)
SLLB14-2
Y. Ito et al.
The thicknesses and chemical compositions of the obtained
films were determined by X-ray fluorescence spectroscopy
(XRF, Panalytical Axios Advance PW4400) calibrated using
standard samples. The film thickness of (K0.88Na0.12)NbO3
films was estimated by the intensity of Nb(Kα) because it
was ascertained to linearly increase with the film thicknesses
by cross-sectional scanning electron microscopy (SEM,
JEOL JEM-6610LA). The crystal structures and preferred
orientations of the films were characterized by X-ray
diffraction (XRD, Philips X’Pert MRD system) with Cu
Kα1 radiation. The pseudo-cubic unit cell denoted by (hkl)c
was employed for SrRuO3 despite their orthorhombic sym-
metry because of the small crystal anisotropy, according to
the previous study.28) The pseudo-cubic cell was also used
for (K, Na)NbO3 in this study. Figure 2(a) shows the
relationships between the orthorhombic unit cell and
pseudo-cubic cell, where the axis of (K, Na)NbO3 orthor-
hombic unit cell is denoted as [hkl]o and [hkl]pc, and their
polar axis is along [001]o, [101]pc, respectively. Figure 2(b)
shows a schematic illustration of orientation relationship of
{100}c-oriented (K, Na)NbO3 epitaxial film deposited on
(100)cSrRuO3//SrTiO3 for the easy understanding of the
relationship between (K, Na)NbO3, and SrRuO3 and
SrTiO3. In this case, the index by a pseudo-cubic cell of (K,
Na)NbO3 denoted as [hkl]c is found to be easier to understand
their crystal structure relationship. The pseudo-cubic cell is
regarded as a special monoclinic lattice reflected in the
orthorhombic symmetry, where the β angle is not equal to
90° but the lattice length of [100] and [001] is equal.40) It is
expected to observe the splitting of diffraction peaks from
(K0.88Na0.12)NbO3 film into 0k0pc and h00pc/00lpc, in view of
XRD studies.
The surface morphologies of the films were observed by
scanning electron microscopy (SEM, JEOL JEM-6610LA).
Pt top electrodes with a diameter of 100 μm were deposited
by electron-beam evaporation to fabricate a capacitor struc-
ture of Pt/(K0.88Na0.12)NbO3/SrRuO3. The ferroelectric and
piezoelectric properties were measured at room temperature
using a ferroelectric tester (Toyo Corp., FCE Fast) and an
atomic force microscope (AFM; SII SPA400) calibrated
using standard samples, respectively.
3. Results and discussion
3.1. Deposition characteristics
Figures 1(b) and 1(c) show the film thickness as a function of
the deposition time for {100}c-oriented (K0.88Na0.12)NbO3
films on (100)cSrRuO3//(100)SrTiO3 substrates prepared with
various source-material conditions. The film deposition
started from the deposition time of 2 h and then the film
thickness increased with the deposition time irrespective of
the source conditions. This time period of 2 h almost
corresponds to the saturation time of the autoclave tempera-
ture as shown in Fig. 1(a). In Fig. 1(b), the film thickness
almost linearly increased with the deposition time. The slopes
of these relations, corresponding to the deposition rate,
decreased with the decrease in the concentration of the
KOH and NaOH mixture, from 7 to 5 mol l−1. The film
thickness was then saturated after a certain time. Also, as
shown in Fig. 1(c), the both of film thickness and time before
saturation were almost independent on the input mass of
Nb2O5 powder. Our previous work clarified that the
© 2019 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 58, SLLB14 (2019)
(a)
Fig. 2. (Color online) (a) Relationships between the orthorhombic unit cell and pseudo-cubic unit cell of (K, Na)NbO3 and (b) the schematic illustration of
orientation relationship of {100}c-(K, Na)NbO3 epitaxial film deposited on (100)cSrRuO3//(100)SrTiO3.
hydrothermal process proceeds with competitive reactions of
film deposition and powder formation and that the saturation
time agreed with the time required for consuming the residual
Nb source.41) The data shown in Fig. 1(b) and 1(c) revealed
that the consumption time of the residual Nb source
decreased when the concentration of the mixture solution
increased. On the other hand, the deposition rate of the film
before saturation time clearly shows that the deposition of the
films was rate-limited by the concentration of the KOH and
NaOH within the limit of the present condition.
Further, the dependences of the film thickness on the
orientation of the substrate, which will correspond to the film
orientation, were evaluated under various hydrothermal condi-
tions. Figure 3(a) shows the film thicknesses as a function of the
deposition time for (K0.88Na0.12)NbO3 films deposited on
(100)cSrRuO3//(100)SrTiO3, (110)cSrRuO3//(110)SrTiO3 and
(111)cSrRuO3//(111)SrTiO3 substrates. The concentration of
the KOH/NaOH solution and input mass of Nb2O5 powder
were fixed at 7 mol l−1 and 0.25 g, respectively. All of the films
deposited on their oriented substrates exhibited similar trends
for their film thicknesses against the deposition time. Their film
thicknesses increased with the deposition time and then
saturated above 4 h. No dependency of the saturation time on
the substrate orientation is reasonable because the saturation
time was mainly determined by the time for consuming the Nb
source in solution. The film thicknesses after saturation time in
Fig. 3(a) were ordered as follows: {100}c-, {110}c- and
{111}c-oriented films. Figure 3(b) shows their film thicknesses
as a function of the deposition time enlarged from 0 to 5 h for
SLLB14-3
Y. Ito et al.
(b)
(K0.88Na0.12)NbO3 films deposited on all oriented substrates.
Each film thicknesses increased almost linearly with the
deposition time within the time range of 2–5 h irrespective of
the film orientation, where their deposition rates depended on
each orientation of their substrates. The order of the deposition
rate agreed well with that of the saturation thickness [see
Fig. 3(a)]. The deposition rates of (K0.88Na0.12)NbO3 films on
(100)cSrRuO3//(100)SrTiO3, (110)cSrRuO3//(110)SrTiO3 and
(111)cSrRuO3//(111)SrTiO3 were 2.9, 2.0 and 1.8 μm h−1,
respectively. The deposition rates of (K0.88Na0.12)NbO3 films on
(100)cSrRuO3//(100)SrTiO3 and (110)cSrRuO3//(110)SrTiO3
substrates were 1.5 and 1.1 times larger than that on
(111)cSrRuO3//(111)SrTiO3 substrate. As discussed later, the
ratios of the deposition rate accord to the ratios of the saturation
thickness. This indicates that the saturated thickness was
determined by the deposition rate of each oriented film. This
is because these times for starting deposition and saturating the
film thickness were almost independent of the film orientation.
Figures 3(c) and 3(d) show the film thicknesses as a
function of the concentration of the KOH/NaOH solution and
input mass of Nb2O5 powder, respectively. Their film
thicknesses increased monotonously with the concentration
of the KOH/NaOH solution in the range of 5–7 mol l−1 for all
oriented films. On the other hand, their film thicknesses
increased with the input mass of Nb2O5 powder up to 1 g and
then decreased with excessive Nb2O5, irrespective of the
orientations of their substrates. The film thicknesses were
ordered as follows: {100}c-, {110}c- and {111}c-oriented
films, similarly to the result in Fig. 3(a). The decrease in the
© 2019 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 58, SLLB14 (2019)
(a)
(b)
(c)
(d)
Fig. 3. (Color online) (a) Film thicknesses as a function of the deposition
time for 0–18 h and (b) the enlarged one for 0–5 h with 7 mol l−1 KOH/
NaOH solution and 0.25 g Nb2O5 powder, together with film thicknesses as a
function of (c) the concentration of KOH/NaOH solution (deposition time:
6 h, Nb2O5 powder: 0.25 g) and (d) input mass of Nb2O5 powder (deposition
time: 6 h, KOH/NaOH solution: 7 mol l−1). The films were simultaneously
deposited at the same batch on (100)cSrRuO3//(100)SrTiO3 (red circles),
(110)cSrRuO3//(110)SrTiO3 (blue triangles), and (111)cSrRuO3//(111)SrTiO3
(green squares) substrates.
film thicknesses at 2 g Nb2O5 in Fig. 3(d) can be attributed to
the homogenous nucleation of the (K0.88Na0.12)NbO3 powder
accelerated by excessive Nb2O5 addition, which consumes
the Nb2O5 source in the reaction system and then suppresses
the film deposition on single crystal substrates.
Figure 4 shows the thicknesses of these films deposited on
(100)cSrRuO3//(100)SrTiO3 and (110)cSrRuO3//(110)SrTiO3
substrates plotted against that of the films deposited on
SLLB14-4
Y. Ito et al.
Fig. 4. (Color online) Film thickness of the {100}c- oriented
(K0.88Na0.12)NbO3 films (red circles) and {110}c-oriented (K0.88Na0.12)NbO3
films (blue triangles) plotted against that of the {111}c-oriented
(K0.88Na0.12)NbO3 films shown in Fig. 3. The dashed black line denotes the
case when the film thickness of {100}c- and {110}c-oriented films are the
same as that of {111}c-oriented films.
(111)cSrRuO3//(111)SrTiO3 substrates, using experimental
data in Fig. 3. These three kinds of films were simultaneously
deposited at the same batch. The dashed (black) line in
Fig. 4 indicates that the film thicknesses deposited on
(100)cSrRuO3//(100)SrTiO3 and (110)cSrRuO3//(110)SrTiO3
substrates were coincident with that on the (111)cSrRuO3//
(111)SrTiO3 substrate, suggesting no dependency on the
crystal orientation. The obtained film thicknesses increased in
the order {100}c-, {110}c- and {111}c-oriented films, irre-
spective of the deposition conditions shown in Fig. 3. In
addition, almost all of the experimental results were almost
on the straight lines across zero, indicating the ratios of the
film thicknesses also independent of the deposition condi-
tions. This means that these film thicknesses of the {100}c-
and {110}c-oriented films were approximately 1.6 and 1.2
times larger than those of the {111}c -oriented film irrespec-
tive of the deposition conditions. Note that the data in Fig. 4
includes not only these thicknesses of films deposited
for a longer time than saturation time but also that for a
shorter time. In fact, these ratios of these film thicknesses
almost agreed with the ratios of the deposition rate shown in
Fig. 3(b); the deposition rates of {100}c- and {110}c-oriented
(K0.88Na0.12)NbO3 film were 1.5 and 1.1 times larger than
that of {111}c-oriented (K0.88Na0.12)NbO3 film. This sug-
gests that the resultant thickness variation by orientations is
caused by the deposition rate that depends on the film
orientations.
The similar tendency, i.e. the anisotropy of the deposition
rate, was reported for Pb(Zr, Ti)O3 films deposited on (100)c,
(110)c, and (111)cSrRuO3//SrTiO3 substrates prepared by
metal organic chemical vapor deposition.42) In that case,
the deposition rates of {100}c- and {110}c-oriented films
were approximately 1.7 and 1.2 times larger than that of the
{111}c-oriented film, similar to the present study for
(K0.88Na0.12)NbO3 films by hydrothermal deposition. This
could be considered to be attributed to the crystal orientation
dependence of the growth rate of the perovskite oxide film,
© 2019 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 58, SLLB14 (2019)
(a) (d)
(e)
(b)
(c) (f)
Fig. 5. (Color online) (a)–(c) XRD θ–2θ profiles and (d)–(f) X-ray pole
figures of the (K0.88Na0.12)NbO3 films grown on [(a), (d)] (100)cSrRuO3//
(100)SrTiO3, [(b), (e)] (110)cSrRuO3//(110)SrTiO3, and [(c), (f)]
(111)cSrRuO3//(111)SrTiO3 substrates. Data shown in (d)–(f) was measured
at fixed 2θ angles corresponding to the (K0.88Na0.12)NbO3{110}c, {100}c,
and {111}c for films deposited on [(a), (d)] (100)cSrRuO3//(100)SrTiO3,
[(b), (e)] (110)cSrRuO3//(110)SrTiO3 and [(c), (f)] (111)cSrRuO3//
(111)SrTiO3 substrates, respectively.
perhaps due to the crystal structure and surface energy
anisotropies.
3.2. Crystal structures and surface morphologies of
the deposited films
In this section, crystal structure and surface morphology were
observed using these films with 3–4 μm in thickness grown
on (100)cSrRuO3//(100)SrTiO3, (110)cSrRuO3//(110)SrTiO3,
and (111)cSrRuO3//(111)SrTiO3 substrates. It must be noted
we cannot detect an obvious change in electrical properties
with the film thickness within the present experimental
conditions.
Figure 5 shows representative XRD θ–2θ patterns and
X-ray pole figures at fixed 2θ angles corresponding to the
(K0.88Na0.12)NbO3 {110}c, {100}c, and {111}c for films
deposited on (100)cSrRuO3//(100)SrTiO3, (110)cSrRuO3//
(110)SrTiO3, and (111)cSrRuO3//(111)SrTiO3 substrates, re-
spectively. These films were deposited by the hydrothermal
method with KOH/NaOH concentration of 7 mol l−1 and
input Nb2O5 mass of 0.25 g. Only {h00}c, {110}c, and
{111}c (K0.88Na0.12)NbO3 peaks were observed in Figs. 5(a)
–5(c), respectively, suggesting that {100}c-, {110}c-, and
{111}c-oriented films were obtained on (100)cSrRuO3//
(100)SrTiO3, (110)cSrRuO3//(110)SrTiO3 and (111)cSrRuO3//
(111)SrTiO3 substrates. Fourfold-, twofold-, and threefold-
symmetry peaks at azimuth ψ angles of 45, 45, and 75° were
exhibited in Figs. 5(d)–5(f), respectively, which indicates in-
plane crystal orientation of these films deposited on
(100)cSrRuO3//(100)SrTiO3, (110)cSrRuO3//(110)SrTiO3 and
(111)cSrRuO3//(111)SrTiO3 substrates. These results certified
that the epitaxial films with three different crystal orientations
of {100}c-, {110}c- and {111}c were grown successfully by
the hydrothermal method.
Figures 6(a)–6(c) show XRD θ–2θ profiles near (K, Na)
NbO3{300}c, (K, Na)NbO3{220}c and (K, Na)NbO3 {222}c for
(K0.88Na0.12)NbO3 films grown on (100)cSrRuO3//(100)SrTiO3,
SLLB14-5
Y. Ito et al.
(a) (b) (c)
Fig. 6. (Color online) XRD θ–2θ profiles near (a) (K, Na)NbO3 {300}c,
(b) (K, Na)NbO3{220}c and (c) (K, Na)NbO3 {222}c, for (K0.88Na0.12)NbO3
films grown on (a) (100)cSrRuO3//(100)SrTiO3, (b) (110)cSrRuO3//
(110)SrTiO3 and (c) (111)cSrRuO3//(111)SrTiO3 substrates, respectively.
(110)cSrRuO3//(110)SrTiO3 and (111)cSrRuO3//(111)SrTiO3
substrates, respectively. These peaks were found to separate
into two or three, suggesting the presence of a multi-domain
structure. {300}c peaks consist of about 82% of (003)pc and
(300)pc and 18% of (030)pc ones in integrated intensities as
shown in Fig. 6(a) for the (K0.88Na0.12)NbO3 films deposited on
(100)cSrRuO3//(100)SrTiO3 substrates, while {220}c peaks
consist of about 23% (202)pc, 34% of (20-2)pc and 43% of
(022)pc, (0–22)pc, (220)pc and (2–20)pc for the films deposited
on (110)cSrRuO3//(110)SrTiO3 substrates. Finally {222}c peaks
consist of 56% (222)pc and (2–22)pc and 44% of (−222)pc and
(22-2)pc for the films on (111)cSrRuO3//(111)SrTiO3 substrates.
Taking account of the fact that (K0.88Na0.12)NbO3 films have an
orthorhombic symmetry,30) splittings of the XRD peaks can be
attributed to the domain structure of these films. In fact, R. M.
Fernando et al., reported that that the (K, Na)NbO3 ceramics
with orthorhombic symmetry have 180°, 90°, 60° and 120°
domains with [101]c polar axis.43) The existence of these multi
orientations affects the ferroelectric and piezoelectric properties
in Sect. 3.3. It must be noted that we confirmed that the shoulder
that exists at the right side of the 003pc and 300pc peak did not
affect these properties.
Figures 7(a)–7(c) show the surface morphologies of the
{100}c-, {110}c- and {111}c-oriented (K0.88Na0.12)NbO3
films. Their films consisted of grains with characteristic
shapes depending on the crystal orientation of the films and
substrates. That is, the {100}-oriented film consisted of
square-shaped grains rotated by 45° from [001] SrTiO3 [in
Fig. 7(a)]. Roof-shaped grains elongated along [001] SrTiO3
were observed for the {110}c-oriented film [Fig. 7(b)].
Finally, triangle-shaped grains with edges along [1–10]
SrTiO3 and flat top surface were observed for the {111}-
oriented film [Fig. 7(c)].
The characteristic shapes of the grains are attributed to the
growth mechanisms of the epitaxial (K, Na)NbO3 films on
the surfaces of single-crystal substrates. Considering that the
{100}c-oriented film grows faster than the {110}c- and
{111}c-oriented films, as shown in Fig. 4, possible scenarios
can be illustrated as described in Figs. 7(d)–7(f). First, initial
© 2019 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 58, SLLB14 (2019)
(a) (d)
(b) (e)
(c) (f)
Fig. 7. (Color online) (a)–(c) Surface SEM images and (d)–(f) possible growth models for the (K0.88Na0.12)NbO3 films grown on [(a), (d)]
(100)cSrRuO3//(100)SrTiO3, [(b), (e)] (110)cSrRuO3//(110)SrTiO3, and [(c), (f)] (111)cSrRuO3//(111)SrTiO3 substrates.
nuclei oriented along the surface normal direction and {111}c
facets grow on all of the substrate surfaces. Subsequently, the
crystal facet grew faster along {100}c. Further studies are
ongoing to clarify the growth mechanism.
3.3. Ferroelectric and piezoelectric properties
Ferroelectric and piezoelectric properties were also evaluated
using the films with 3–4 μm thick grown on (100)cSrRuO3//
(100)SrTiO3, (110)cSrRuO3//(110)SrTiO3, and (111)cSrRuO3//
(111)SrTiO3 substrates shown in Figs. 5–7. Figures 8(a)–8(c)
show room-temperature polarization–electric-field (P–E) hyster-
esis loops measured at 100 kHz for the (K0.88Na0.12)NbO3
films deposited on (100)cSrRuO3//(100)SrTiO3, (110)cSrRuO3//
(110)SrTiO3, and (111)cSrRuO3//(111)SrTiO3 substrates. All of
the films exhibited clear hysteresis loops originating from their
ferroelectricity. Their remnant polarizations (Pr) and coercive
fields (Ec) at the maximum electric field of 500 kV cm−1 were
31 μC cm−2 and 111 kV cm−1, 27 μC cm−2 and 94 kV cm−1,
and 25 μC cm−2 and 110 kV cm−1, respectively. These results
suggest that the ferroelectric properties did not depend on the
orientation considerably. To understand the ferroelectric prop-
erty, we must take into account the effect of the multi-domain
structure as already discussed in Fig. 6. This multi-domain
structure is considered to result in the small anisotropy of
the remnant polarization of these films. The polar axis of
(K, Na)NbO3 with orthorhombic symmetry is 〈101〉c and shows
180°, 90°, 60° and 120° domains, in general. We expect that
saturation polarization of polarization for {100}c-, {110}c- and
{111}c-oriented (K0.88Na0.12)NbO3 films should be 0.57Ps,
0.45Ps, and 0.45Ps, respectively, where Ps is a spontaneous
polarization, taking into account volume fractions estimated
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Y. Ito et al.
from XRD patterns in Fig. 6 and projections with respect to
surface normal directions of these domains. The expected
saturation polarization for the {100}-oriented film is 1.3 times
larger than those for other orientations. This shows almost good
agreement with present experimental results, which show
remanent polarization {100}-oriented film is 1.1 times larger
than that for {110}-oriented film and 1.2 times larger than that
for the {111}-oriented film. Thus, the small orientation variation
can be explained by the formation of multi-domain structures.
Similar small orientation dependency is also reported
for {100}c, {110}c, and {111}c-oriented tetragonal
Pb(Zr0.35Ti0.65)O3 films.44) In this case, the predicted Pr
values based on semi-quantitative estimation using the
projection of the spontaneous polarization to the surface
normal direction for each domain and its volume fraction also
almost agreed with the experimental results.
Figures 8(d)–8(f) show the S–E curves measured at
5.2 Hz. These curves originating from the ferroelectricity
were clearly observed for all of the films. The effective
values of piezoelectric coefficient, d33, of the films
on (100)cSrRuO3//(100)SrTiO3, (110)cSrRuO3//(110)SrTiO3,
and (111)cSrRuO3//(111)SrTiO3 substrates estimated from
the strain curves were 33, 31, and 31 pm V−1, respectively.
These results suggested that the piezoelectricity also did not
depend so strongly on the film orientation. The multi-domain
structure ascertained in Figs. 7(d)–7(f) should contribute to
the piezoelectric response, similar to the ferroelectric polar-
ization. However, the piezoelectric coefficient is more
complicated because it is a third-order tensor. Therefore,
here we discuss them indirectly; that is, generally, the d33 can
© 2019 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 58, SLLB14 (2019)
(a) (b)
(d) (e)
Fig. 8. (Color online) (a)–(c) P–E loops measured at 100 kHz and (d)–(f) strain–electric-field (S–E) loops measured at 5.2 Hz for the (K0.88Na0.12)NbO3
films grown on [(a), (d)] (100)cSrRuO3//(100)SrTiO3, [(b), (e)] (110)cSrRuO3//(110)SrTiO3, and [(c), (f)] (111)cSrRuO3//(111)SrTiO3 substrates.
be described as d33 = 2QPrεrε0, where Q, εr and ε0 are an
electrostrictive coefficient and relative dielectric constant
and dielectric constant of the vacuum, respectively. The
εr values measured for (K0.88Na0.12)NbO3 films grown
on (100)cSrRuO3//(100)SrTiO3, (110)cSrRuO3//(110)SrTiO3
and (111)cSrRuO3//(111)SrTiO3 substrates at 1 kHz were
337, 418 and 453, respectively. The measured εr values are
not so largely varied by the crystal orientation, as well as the
values of remnant polarization, Pr as observed in Figs. 8(a)–
8(c). Therefore, we can consider again that the d33 values in
this study also do not show so marked dependence on the
crystal orientation by assuming the almost constant Q value
for each orientation. Note that the order of the value of
polarization is {100}c > {110}c > {111}c, whereas that of
dielectric constant is {111}c > {110}c > {100}c. These or-
ders in opposite relation would also contribute to the piezo-
electric responses without significant dependency against the
crystal orientation.
4. Conclusions
{100}c-, {110}c- and {111}c-oriented epitaxial (K0.88Na0.12)
NbO3 films were deposited on (100)cSrRuO3//(100)SrTiO3,
(110)cSrRuO3//(110)SrTiO3 and (111)cSrRuO3//(111)SrTiO3
substrates by the hydrothermal method. These film thick-
nesses increased with increasing the deposition time and then
eventually saturated at longer deposition time for all of these
films, independent of the concentration of the KOH/NaOH
solution, and input mass of Nb2O5 powder. However the
deposition rate exhibited significant dependency on the
orientation of the film and substrate; the deposition rate
before saturation increased in the order: {100}c-, {110}c-
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Y. Ito et al.
(c)
(f)
{111}c-oriented films, almost independent on the deposition
conditions within the present study. These films consisted of
grains with characteristic shapes depending on the orienta-
tions of the substrates, which could be explained by the
promoted crystal growth along the {100}c direction.
However, significant orientation dependencies of the ferroe-
lectricity and piezoelectric response were not observed in the
P–E and S–E characteristics, which suggest the strong
contribution of the non-180° domains.
Acknowledgments
This research was partially supported by the Japan Science
and Technology Agency and the Adaptable and Seamless
Technology Transfer Program through Target-driven R&D
(A-STEP) Grant No. JPMJTS1616.
ORCID iDs
Takao Shimizu https://orcid.org/0000-0001-9508-7601
Takahisa Shiraishi https://orcid.org/0000-0002-2154-0589
Takanori Kiguchi https://orcid.org/0000-0003-4541-8761
Toyohiko J. Konno https://orcid.org/0000-0002-3396-
1049
Hiroshi Funakubo https://orcid.org/0000-0002-1106-200X
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