ISSN 1063-7834, Physics of the Solid State, 2019, Vol. 61, No. 2, pp. 244–248. © Pleiades Publishing, Ltd.

, 2019.
Russian Text © A.V. Pavlenko, L.I. Ivleva, D.V. Stryukov, A.P. Kovtun, A.S. Anokhin, P.A. Lykov, 2019, published in Fizika Tv erdogo Tela, 2019, Vol. 61, No. 2, pp. 376–380.

SURFACE PHYSICS
AND THIN FILMS

Synthesis, Structure, and Dielectric Characteristics

of Sr0.61Ba0.39Nb2O6 Single Crystals and Thin Films
A. V. Pavlenkoa, b, *, L. I. Ivlevac, D. V. Stryukova, A. P. Kovtuna, A. S. Anokhina, and P. A. Lykovc
a
Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia
b Southern Federal University, Rostov-on-Don, Russia
c
Prokhorov Institute of General Physics, Russian Academy of Sciences, Moscow, Russia
*e-mail: Antvpr@mail.ru
Received July 18, 2018; revised September 7, 2018

Abstract—The structure, lattice dynamics, and dielectric characteristics of Sr0.61Ba0.39Nb2O6 (SBN-61) sin-
gle crystals and SBN-61/(001)MgO thin films have been studied. The analysis of temperature and frequency
dependences of permittivity and dielectric loss tangents in a range of 10–500 K for a SBN-61 crystal has
allowed one to establish the phase transition temperatures. The SBN-61/(001)MgO films are found to pos-
sess the tetragonal symmetry, characteristic of a SBN-61 crystal, but their lattice parameters are different
from the latter.

DOI: 10.1134/S1063783419020185

1. INTRODUCTION 2. SAMPLES, SYNTHESIS,

Ferroelectric (FE) solid solutions (SSs) with a
SrxBa1– xNb2O6 (SBNx) composition have become
one of the most promising materials for applications in
microelectronics, nonvolatile memory elements, and
nonlinear optics, and are well studied in the forms of
powder, ceramics, and single crystals [1]. The higher
the Sr content in these systems, the lower is the tem-
perature of phase transition (PT) from tetragonal FE
phase to paraelectric (PE) and the stronger is the
relaxor behavior, which is determined by the statistical
settlement of channels A1 and A2 by Sr and Ba cations
in a structure of tetragonal tungsten bronzes (TTBs)
[1]. As shown in work [2], structures formed upon
switching from a single-domain state to SBN are qual-
itatively different from classical domains, being the
quasi-coagular ensembles of isolated wedge-shaped
nanodomains with charged domain boundaries.
According to work [3], the smaller the Sr/Ba content
ratio, the lower is the population in the pentagonal
structural channels and the higher is the splitting of Ba
and Sr atomic positions in them. In recent years, great
attention has been paid to experimental and theoreti-
cal research of the properties of heterostructures based
on SBNx thin films. This is due to the fact that exten-
sively developing directions, such as micro- and nano-
electronics, as well as microelectromechanical systems
(MEMSs), prefer FEs in the form of thin films [4].
This work aims at the characterization of the struc-
ture, lattice dynamics, and dielectric characteristics
(in a temperature range of 10–600 K) of SBN-61 sin-
gle crystal and SBN-61/(001)MgO thin films.
AND CHARACTERIZATION METHODS
Single crystals with a Sr0.61Ba0.39Nb2O6 (SBN-61)
composition were grown via the modified Stepanov
method at the Prokhorov Institute of General Physics
(Russian Academy of Sciences). A SBN-61 solid solu-
tion was prepared by the solid-phase synthesis at a
temperature of 1473K using precursors, such as
SrCO3, BaCO3 and Nb2O5 (“high purity substance”).
A ceramic target was made at the Department of Intel-
lectual Materials and Nanotechnologies (Research
Institute of Physics, Southern Federal University).
The gas-discharge RF-sputtering of 300-nm SBN-
61 films in the high-pressure pure oxygen environment
onto the single-crystal (001)MgO substrates was per-
formed on a Plasma-50-SE setup [5] (Center for
Shared Use, Research Institute of Physics, Southern
Federal University). The onset temperature of a sub-
strate was ~673 K, the oxygen pressure in a chamber
was 0.5 Torr, and the microwave power was 110 W.
The degree of structural perfection of films, the
out-of-plane unit lattice parameters, as well as the ori-
entation ratios between the film and the substrate,
were determined by the X-ray diffraction on a DRON-
4-07 diffractometer using the /2 mode (CuK radi-
ation) (Center for Shared Use, Research Institute of
Physics, Southern Federal University).
The relative permittivity, '/0, (0 is the dielectric
constant) and dielectric loss tangent, tan, of samples
as the functions of temperature at T = 20–700 K and
frequencies f = 103–106 Hz were measured on an

244
 SYNTHESIS, STRUCTURE, AND DIELECTRIC CHARACTERISTICS 245

Agilent 4980A LCR-meter. Before measurements, the

crystal faces were covered with an auromal 38 20 000
(DODUCO GmBH) paste. 1 kHz
10 kHz
The Raman spectra were acquired in a range of 50–
1000 cm–1 using the polarized argon laser excitation 100 kHz
15 000
( = 514.5 nm) on a micro-Raman Renishaw inVia 1500

'/0
spectrometer equipped with an edge-filter that enables
one to record spectra starting from 50 cm–1. The 1000

'/0
10 000
Raman spectra were obtained in the back-scattering
geometry by means of a Leica optical microscope 500
(with a ×50 objective); the laser spot on a sample sur-
face was about 2 m in diameter. The Raman spectra 5000
0 100 200
were corrected for the Bose–Einstein temperature T, K
factor. The measurements were made at the Labora-
tory of Raman spectroscopy (the Department of Nan- 0
otechnology, Southern Federal University).
700

3. RESULTS AND DISCUSSION

Figures 1 and 2, as well as Table 1, display the 600
gauged dielectric characteristics (temperature and fre-
quency dependences of permittivity measured along
'/0
the ('||/0) and perpendicular to the (' /0) polar axis
c of a SBN-61 single crystal). A decrease in tempera- 500
ture in a range of T = 300–500 K exhibits an increase
in '||/0 (no dispersion of '||/0( f ) is observed at T =
360–500 K) and the formation of maxima, Tm1, shift- 400
ing towards higher temperatures with rising f and
associated with a FE  PE PT (P4bm  P4b2) [1, 6].
One can also observe a hump arising at T ~ 335–340 K 0 100 200 300 400 500
(Fig. 2b), whose position is independent of f. A fur- T, K
ther decrease in temperature leads to the monotonic
decline in '||/0, as well as to the dielectric dispersion Fig. 1. Relative permittivity as a function of temperature
for SBN-61 single crystal at measuring electric field fre-
loss (the dispersion f vanishes at T < 100 K over a quencies of 1, 10, and 100 kHz along and perpendicular to
range analyzed; see inset in Fig. 1a). the polar axis c.
As found from ('|| /0)–1(T) dependences obeying
the Curie–Weiss law (Fig. 2a), the Burns temperature,
Td, (the temperature of nucleation of polar nano- As mentioned in works [1, 8], the relaxor properties
domains in FE-relaxors) is 360 K. The best approxi- of a SrxBa1– xNb2O6 SS are due to microstructural dis-
mation of the Tm( f ) dependence was achieved at using ordering of their structure. A SBNx structure is com-
the Vogel–Fulcher ratio (insert in Fig. 2a): posed of two types of crystallographically independent
NbO6 octahedra pooled by the oxygen vertices in a
f  f0 exp(Eact /(k(Tm  Tf ))), three-dimensional frame. The narrowest channels of a
where f0 is a frequency of attempts to overcome a
potential barrier Eact, k is the Bolzmann constant, and
Tf is the Fogel–Fulcher temperature interpreted as a Table 1. Characteristics of SBN-61 single crystal
“static freezing” temperature of electric dipoles or the
transition into the dipole glass state. '||/0 (T = 300 K) 1165
The Eact and f0 values (0.0121 eV and 1012 Hz, '/0 (T = 300 K) 447
respectively) are close to those observed in FE-relax- 20228
'||/0 (T = Tm)
ors, whereas the value of Tf = 335.6 K allows the above
'/0 (T = Tm) 614
highlighted anomalies in '|| /0(T) curves in this tem-
perature range to be attributed to the transition of Tm( f = 1 kHz), K 345
SBN-61 from the relaxor (nanopolar) into the macro- T d, K 360
domain state, where the “ordinary” bulk FE-domains
coexist with near-surface nanodomains [7]. Tf , K 335.6

PHYSICS OF THE SOLID STATE Vol. 61 No. 2 2019

246 PAVLENKO et al.

1.6 channels of a pentagonal section (A2) are occupied by

0.08 (a) Ba and Sr atoms.
According to work [3], the population of the chan-
0.06
1.2 nel A1 by Sr atoms depends weakly on the composi-
(ln( f/f0))1 0.04
tion, and the relaxor characteristics of SBNx are
mainly determined by the level of settlement of chan-
(0/')  104

0.02
Tf = 335.6 K nels A2 by Ba and Sr atoms. The close values of Tf, Tm1,
0.8 Ea = 0.012 eV
f0 = 1012 Hz
and Td indicate that the PT of SBN-61 becomes
0 blurred in a temperature range narrower than for other
335 340 345 350 355 FE-relaxors.
0.4 T, K The analysis of ' / (T) curves reveals that regu-
 0
Td larities in a sample at T = 200–500 K are entirely sim-
ilar, but the dielectric characteristics exhibit a pro-
0 nounced anisotropy in a range of PE  FE PT (see
300 325 350 375 400 425 450
Table 1), which is characteristic of SBNx. By analogy
T, K
3 with work [8], the '/0(T) dependences at T < 200 K
(b) manifest the blurred frequency-dependent maxima
(Tm2) that are shifted towards the higher temperatures
with increasing f (Tm2( f = 1 kHz) = 53 K, Tm2( f =
200 Hz 100 kHz) = 101 K). As follows from results divulged in
works [9, 10] devoted to studies of the acoustic param-
2 eters, structure, and pyroeffect in SBNx, the emer-
gence of these anomalies is owing to the blurred low-
Tf Td
(0/')  103

temperature FE  FE phase transition from the

tetragonal to a monoclinic phase. The latter is charac-
terized by spontaneous polarization perpendicular to
100 Hz the axis c in SBNx [8]. In accordance with data [8], its
1
clusters may exist and make contribution to the dielec-
tric response even at T > 200 K.
Thus, the dielectric characteristics established in
SBN-61 single crystals reveal a quite complex
sequence of phase transitions in a sample exposed to
temperatures of 10–500 K. This should be considered
in the prediction of the properties of SBN-61 thin
0 films, because the deformation fields arising upon the
0.2 heterostructure formation may alter the PT tempera-
tures in specimens or induce the new phase states that
never occur in single crystals [4]. Taking the aforesaid
tan 

into account, the structure and lattice dynamics of

0.1
0 reflexes from the film and the substrate, meaning a
325 330 335 340 345 350 355 360 365
T, K
Fig. 2. (a) ('|| /0)–1(T) dependence at f = 105 Hz of SBN-
61 single crystal; a straight line illustrates the Curie–Weiss
law. The inset shows the (ln( f/f0))–1(T) dependence; a
straight line is calculated from the Vogel–Fulcher rela-
tionship. (b) '|| /0(T) and tan(T) dependences of SBN-61
single crystal at f = (200–105) Hz and T = (325–365) K.
triangular section (C channels) in SBNx are empty; the
channels of a rectangular section (A1) with average
diameters are filled by only Sr atoms, and the largest
SBN-61 single crystals were compared with those of
thin films.
The –2 X-ray spectrograms of a SBN-
61/(001)MgO heterostructure exhibit only (00l)
lack of impurity phases (Fig. 3a). Epitaxial growth was
proven from the -scanning of (113) reflexes from the
substrate and (221) reflexes of the SBN-61 film
(Fig. 3b). -Scanning of the (221) reflexes of the film
evidence the presence of eight peaks that correspond
to two orientation domains in the film. The [001] crys-
tallographic axes of these orientation domains are
rotated by ±18.4 relatively the [001] axis of the sub-
strate. The peak positions were used in the determina-
tion of the unit cell parameters. It is worth mentioning
that lattice parameters are identical for both orienta-
tion domains; furthermore, their a and b parameters
are equal to each other in the conjugation plane.

PHYSICS OF THE SOLID STATE Vol. 61 No. 2 2019

 SYNTHESIS, STRUCTURE, AND DIELECTRIC CHARACTERISTICS 247

002MgO (a) (221) SBN-61 (b)

Intensity, arb. units

001SBN-61

001SBN-61
SBN-61
0021
Intensity, arb. units

Intensity, arb. units

SBN-61
0022

(113) MgO

Intensity, arb. units

45.5 46.0 46.5
2, deg

20 25 30 35 40 45 50 0 60 120 180 240 300 360

2, deg , deg

Fig. 3. (a) –2 X-ray spectrogram of SBN-61/(001)MgO film; the inset displays the (002) reflection of film; (b) -scans of (113)
reflexes of MgO substrate and (221) ref lexes of SBN-61 film; squares and circles correspond to orientation domains +18.4 and
‒18.4, respectively.

Thus, the unit cell parameters of the SBN-

637 cm1 (a) 61/(001)MgO film are c = 0.3954 ± 0.0001 nm; a =
b = 1.245 ± 0.001 nm. A comparison of the unit cells
parameters with those of a single crystal sample (ab =
Intensity, arb. units

1.2456 nm, cb = 0.3936 nm) reveals that the film

254 cm1 remains almost unstrained in the conjugation plane,
but is strongly stretched in along the [001] polar axis
(two-dimensional strains of the unit cell are 33 = (c –
cb)/cb × 100% = 0.45%). As established from the oscil-
lation curve, the vertical misorientation is less than 1,
while the -scans give the azimuthal misorientation
below 2.7, which means the high quality of the het-
erostructure obtained.
(b) Figure 4 displays the Raman spectra of the SBN-61
crystal and the SBN-61/(001)MgO film. In order to
641 cm1 evaluate the peak parameters, data were approximated
with a set of Lorentzians. According to the Raman
Intensity, arb. units

282 cm1 selection rules, there are 135 vibrational modes (3 ×

45) for SBNx SSs, including three acoustic modes.
Among the five irreducible representations of A1,
A2, B1, B2, and E, only A2 is inactive in both the
Raman and IR-spectra. The modes of B symmetry are
Raman-active, while the A1 and E modes are allowed
in both the Raman and IR spectra. However, the
appropriate lines observed in the experimental spectra
1000 of SBNx [11] are quite broad, and their amount is infe-
0 200 400 600 800
rior to that of theoretically predicted modes [12]. This
Wavenumber, cm1 is first of all explained by the cationic disordering in
the TTB structure [6], followed by the selection rule
Fig. 4. Raman spectra of (a) SBN-61 crystal and (b) SBN- violation with respect to the wave number at the center
61/(001)MgO film. of the Brillouin zone [13]. Moreover, the modes with

PHYSICS OF THE SOLID STATE Vol. 61 No. 2 2019

248 PAVLENKO et al.
close frequencies are prone to degeneration into one
band that makes the addition contribution to the
broadening of the Raman spectrum. All this allows
one to study only a small amount of spectral peculiar-
ities. The MgO crystal has no active first-order
Raman-active modes, but may give the second-order
spectrum [14]. The line at 900 cm–1 in a spectrum of
SBN-61/(001)MgO is referred to a second-order
Raman feature of the MgO substrate.
As seen in Fig. 4, all the vibrational characteristics
of TTB structures are also preserved in the Raman
spectra of the SBN-61/(001)MgO film, which indi-
cates the retention of the tetragonal symmetry in films.
However, some lines are shifted relative to the appro-
priate peaks in a SBN-61 crystal. The greatest contri-
bution to the Raman spectrum intensity of a SBN-61
crystal comes from three broad lines at 254, 637, and
846 сm–1. The first two intensive lines, typical of other
ferroelectric crystals [15], are the A1 phonons and
attributed to the internal vibrations of the
NbO3(NbO6) octahedron, corresponding to the
movement of ions along the axis Z. The line at
846 сm–1 can be attributed to B1 and B2 phonons that
make zero contribution to the polarization [13]. For
the SBN-61/(001)MgO film, there is some redistribu-
tion between the intensities of lines and their broaden-
ing, but also the shift of the first two intensive bands
towards frequencies of 282 and 641 cm–1, respectively.
With that, the band at 846 cm–1 remains almost
unshifted.
In our opinion, the shift and broadening of these
Raman lines are likely due to the lattice deformation
and the additional structural disordering in the SBN-
61 film.
4. CONCLUSIONS
A study of the dielectric characteristics of SBN-61
single crystals in a range of 10–500 K enabled one to
establish the temperature ranges of two blurred phase
transitions, such as the low-temperature ferro  fer-
roelectric phase transition in the varying crystal struc-
ture and the phase transition from the ferroelectric to
a paraelectric phase (345–355 K).
The examination of structure and lattice dynamics
of a SBN-61/(001)MgO heterostructure revealed the
tetragonal symmetry of the unit cell in the SBN-61
film grown via the one-stage synthesis at high oxygen
pressures. Unlike a single crystal, the SBN-
61/(001)MgO lattice remained almost unstrained in
the conjugation plane with a substrate, but was
stretched along the polar axis. As is shown earlier, the
lower deformation effects in oriented SBN-
50/Pt/Al2O3 films favor an increase in Td and a
decrease in refractive index of the beam [16]. In this
respect, one can expect the amplified optical anisot-
ropy and the shift of the SE  PE phase transition
PHYSICS OF THE SOLID STATE
towards higher temperatures in SBN-61/(001)MgO
heterostructures.
The results of this work are applicable for the syn-
thesis and study of the properties of heterostructures
based on barium–strontium niobate solid solutions.
ACKNOWLEDGMENTS
This work was performed within the framework of
the State Task of the Southern Scientific Center (Rus-
sian Academy of Sciences) (topic no. 01201354247),
with partial support of Volkswagen Foundation Az.:
90261 of 29th February 2017, the Ministry of the Edu-
cation and Science of the Russian Federation (project
no. 3.6371.2017/8.9) and within the Program of the
President of the Russian Federation (grant no. MK-
4100.2018.2).
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Translated by O. Maslova
Vol. 61 No. 2 2019