Size effects in the temperatures of phase transitions in KNbO3 nanopowder

I. S. Golovina, V. P. Bryksa, V. V. Strelchuk, I. N. Geifman, and A. A. Andriiko

Citation: Journal of Applied Physics 113, 144103 (2013); doi: 10.1063/1.4801794
View online: http://dx.doi.org/10.1063/1.4801794
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JOURNAL OF APPLIED PHYSICS 113, 144103 (2013)

Size effects in the temperatures of phase transitions in KNbO3 nanopowder

I. S. Golovina,1,a) V. P. Bryksa,1 V. V. Strelchuk,1 I. N. Geifman,2 and A. A. Andriiko3
1

Institute of Semiconductor Physics of NAS of Ukraine, pr. Nauki 41, 03028 Kyiv, Ukraine
Quality Engineering Education, Inc., Buffalo Grove, Illinois 60089, USA
3
National Technical University of Ukraine KPI, pr. Peremogy 37, 03056 Kyiv, Ukraine
2

(Received 25 February 2013; accepted 28 March 2013; published online 12 April 2013)
The paper reports on thorough Raman-scattering study of newly synthesized nanoscale powders of
potassium niobate (KNbO3) aimed at evaluating the possible modification of the phase transition
temperatures versus the corresponding bulk values. We register a significant expansion of the
temperature ranges of all phase transitions, which is attributed to a wide distribution of particle
sizes. An average temperature of each phase transition shifts to the high-temperature region
differently, namely by 10 , 25 , and 40 , as compared with corresponding transition temperature in
bulk crystals of KNbO3 and amounts 0, 248, and 475  C, respectively. In the range from 100 to
110  C, we also find the features, which could be associated with an additional rearrangement of
C 2013 AIP Publishing LLC [http://dx.doi.org/10.1063/1.4801794]
the structure. V
I. INTRODUCTION

Due to the high electro-optical and nonlinear optical

coefficients, potassium niobate (KNbO3) is an attractive optical material, in particular, for optical waveguides, frequency
multipliers, holographic memory systems, etc.13 Since this
material does not contain lead, it is also an alternative for the
replacement of lead-containing materials, such as widely
used lead zirconate titanate (PZT) system, that are currently
used in most ultrasonic applications.46 Recently, special
attention has been paid to the study of size effects observed
both in film and in powder samples of KNbO3.713 These
effects are manifested primarily in a shift of phase transition
temperatures. Note that single-crystal potassium niobate
experiences the following sequence of phase transitions with
increasing temperature: Rhombohedral (R) !(10  C)!
Orthorhombic (O) !(225  C) ! Tetragonal (T) !(435  C)!
Cubic (C), where P-, O-, and T-phases are ferroelectric, while
the C-phase is paraelectric. How exactly the temperature of
each phase transition changes in low-dimensional system?
Examining the crushed single crystals of KNbO3, Baier
et al.11 found that even at particle sizes of about 50 lm the
temperatures of all three phase transitions are shifted to the
high-temperature area. The authors suggest that this shift is
caused by residual strain in the crystallites formed during
grinding of the samples. However, Chen et al.12 in the study
of KNbO3 powders, obtained by the sol-gel method and having different particle sizes, from 40 to 80 nm, found that in
this size range a change in the Curie temperature does not
occur. At the same time, in films of KNbO3, authors of Ref. 8
reported the reduction of Tc by 30 . These films had an average thickness of 20 to 150 nm and had grain-like structure
with a longitudinal grain size of about 250 nm. Finally, an unusual effect was observed by Louis et al.13 in KNbO3 nanowires, having an average diameter of 50 nm and a length of
about 5 lm. It was found that the lowest-temperature phase in
this material is not with rhombohedral but with monoclinic

a)

Electronic mail: golovina@isp.kiev.ua

0021-8979/2013/113(14)/144103/5/$30.00

symmetry. On the other hand, the temperatures of all three

transitions are the same as in macrocrystals. The works show
a quite contradictory picture of the influence of particle size,
both on the phase transition temperature and on the symmetry
of nanoscale KNbO3. Therefore, there is a need for further
study of size effects on this object.
In addition, until now theoretical estimates have not been
performed on the effect that crystal size has on the Curie temperature in potassium niobate. However, it should be mentioned, that the authors of Ref. 14 made the calculations for
the virtual ferroelectrics SrTiO3 and KTaO3. The results of
that work indicate that the Curie temperature increases with
decreasing size of the crystal.
Recently, the group of Dr. Andriiko developed a new
technology for the synthesis of nanoscale powders of
KTaO3.15 Dielectric and spectroscopic properties of this material were studied in detail.16,17 In particular, temperature
dependent Raman scattering spectra were investigated. From
those data, the sizes of the polar nanoregions were obtained.
In the present paper, a similar technology was used to
synthesize KNbO3 for the first time. It is established that the
powder particles have dimensions less than 100 nm. So, the
material is a nanosize object. First of all, we were tasked
with determining the temperatures of phase transitions in the
resulting nanopowder. To solve this problem, the method of
Raman scattering was chosen. This technique is most suitable for powder nanoscale object, because it does not require
the high-density ceramics, in contrast to dielectric spectroscopy, while it is quite informative. We conducted a detailed
study of the temperature dependence of Raman spectra and
found that the temperatures of three phase transitions are
higher than the corresponding temperatures observed in bulk
material. The other features in the spectra related to the size
effects are also detected.
II. MATERIAL AND EXPERIMENTAL TECHNIQUES

A technique for the synthesis of KTaO3 by oxidation of

metallic tantalum in molten potassium nitrate with the addition of potassium hydroxide was recently developed. As was
113, 144103-1

C 2013 AIP Publishing LLC

V

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Golovina et al.

J. Appl. Phys. 113, 144103 (2013)

shown in Ref. 15, this synthesis method can be used to obtain

nanoscale powders. By a similar procedure, the synthesis
of KNbO3 powders was carried out in the present work.
Weighed portions of the initial components were mixed and
ground. Then, the mixture was kept in a furnace at a temperature of 600  C for 1.5 h. The resulting melt was cooled in
air and decanted in water. The precipitate was dried at a temperature of 100  C in open air.
The product was investigated by an X-ray diffraction
(XRD) method on a diffractometer DRON-3 M with CuKa
radiation. The results of XRD confirmed the formation of
pure KNbO3 phase (JCPDS No. 32-0822) (Fig. 1).
The dimensions of the crystallites were estimated using
the Debye-Scherrer formula
0; 9k
;
(1)
d
Bcos H
where k 0.1542 nm the wavelength of X-ray radiation, B
the half-width of the diffraction peak in radians, H the
angle that corresponds to the position of the diffraction line
on the XRD pattern. The calculations showed that an average
crystallite size equals 80 nm.
Electron microscopic analysis was performed by transmission electron microscopy (TEM) method with a MET
JEOL-2000 EX-II microscope operating at 200 kV. TEM
investigation confirmed the XRD data. Figure 2 shows the
well-formed cubic crystals with dimensions from 30 to
130 nm. Thus, TEM data clearly demonstrate that there is a
considerable variation of particle size in our samples.
Micro-Raman measurements were performed using JobinYvon/Horiba T64000 Raman triple spectrometer equipped
with a thermoelectrically cooled charge-coupled device
(CCD) detector. The 514.5 nm line of an Ar/Kr laser was
used as the excitation source with power of 3 mW. An
Olympus BX41 microscope equipped with a 50 long focus
objective with NA 0.60 was used to focus the laser light on
the sample and collect the scattered light into the spectrometer. Micro-Raman spectra were measured by using a Linkam
TMS 94 controller and a THMS 600 stage to vary the sample
temperature between 190  C and 600  C with a precision of
60.1  C. The temperature was varied in step 5  C with heating rate of 10  C/min.

FIG. 1. XRD pattern of KNbO3 powder.

FIG. 2. TEM image of KNbO3 powder.

III. RESULTS AND DISCUSSION

Figure 3 shows Raman spectra characteristic for the

different structural states of KNbO3 powder. In the lowtemperature rhombohedral phase, fairly narrow lines of transverse and longitudinal phonon modes B1(TO2), B1(TO1),
B1(TO4), A1(TO1), B1(TO3), A1(TO3), B2(TO3), and A1(LO3)
are observed at 188.5, 230.1, 267.0, 288.5, 530.0, 596.2,
623.9, and 834.6 cm1, respectively (Fig. 3). Similar phonon
modes were observed in KNbO3 samples in Refs. 18 and 19.
For further analysis, three transverse optical phonon modes
B1(TO2), A1(TO1), and B1(TO3) were selected.
It is known that the lowest-frequency TO phonon, the
soft mode, involves the same atomic displacements as those
responsible for the appearance of spontaneous polarization.
When the temperature approaches the Curie temperature, Tc,
the soft-mode frequency tends to zero, becoming frozen in

FIG. 3. Micro-Raman spectra of KNbO3 powder measured at different

temperatures.

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Golovina et al.

the crystal, which transforms to the ferroelectric phase, thus

the soft-mode instability at Tc causes the ferroelectric phase
transition.20 In the investigated object, a ferroelectric phase
transition is monitored by the behavior of the soft mode
B1(TO2). Two low-temperature structural transitions are
determined, as shown below, by softening the modes
A1(TO1) and B1(TO3). As seen in Fig. 3, the lines of these
modes are quite narrow at low temperatures and broadened
(along with a change in frequency) with increasing temperature. However, unlike the modes B1(TO2) and A1(TO1), the
change in width and frequency of the B1(TO3) line is difficult to trace due to the overlap of the lines with those of
A1(TO3) and B2(TO3). Therefore, before analyzing the temperature dependence of the spectrum, we have carried out
the expansion of this part of the spectrum into three single
Lorentzians, which correspond to the modes B1(TO3),
A1(TO3), and B2(TO3) (Fig. 4). The inset of Fig. 4 shows an
algorithm for the decomposition of a complex experimental
contour to separate Lorentz components. In the first phase of
this expansion, an interval of expected values for the frequencies (xn) and linewidths (Cn) of the phonon bands was
set up. After this, by tabulating xn and Cn in the range of
variation, the standard deviation value of modulation sum of
contours from the experimental data was calculated. At the
end of the algorithm, we searched for such a decomposition
of a complex contour for which the standard deviation is
minimal throughout the tabulated ranges of xn and Cn. The
decomposition of complex contour of the Raman spectra was
carried out for each temperature as described above, which
makes it possible to find the temperature dependences of the
spectral parameters of the phonon bands.

FIG. 4. The decomposition of the experimental wide band at 450750 cm1

for three Lorentzian components corresponding to phonon modes B1(TO3),
A1(TO3), B2(TO3). The inset schematically presents the algorithm for the
decomposition of a complex circuit to separate Lorentz bands.

J. Appl. Phys. 113, 144103 (2013)

Figure 5 shows the temperature dependences of the integrated intensity (An), width (Cn), and frequency (xn) of every Lorentzian. Let us analyze the dependences presented in
Fig. 5. First, we note that the condensation of the B1(TO3)
line leads to its complete disappearance (its intensity
becomes zero) at a temperature of about 248  C. Above this
temperature, this mode becomes unobservable. The linewidth
increases monotonically by a negligible amount with increasing temperature. The frequency remains almost unchanged in
the range from 200 to 0  C, then begins to decline from
528.7 to 527.1 cm1, and from 200  C increases somewhat,
reaching 534.8 cm1 at 248  C. The A1(TO3) line is observed
throughout the temperature range from 200 to 600  C, not
significantly changing in intensity. In the temperature dependence of the width of this line, there are some noticeable
inflections at the temperatures of 0, 100110, 275, and
450  C. The frequency monotonically decreases from 593.3
to 579.2 cm1 in the region from 200 to 100  C. A significant change is observed in the 400500  C range, where the
scattering intensity increases strongly. The B2(TO3) line is
also observed over the entire temperature range, but its integrated intensity varies non-monotonically, experiencing
slight inflections at 0, 100110, and 245  C. Significant fluctuations in the intensity of this line start at 300  C and continue up to 600  C. A particularly strong jump is observed at

FIG. 5. Temperature dependences of the intensity (An), width (Cn), and frequency (xn) of the transverse optical modes: B1(TO3) (squares), A1(TO3)
(circles), and B2(TO3) (triangles).

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Golovina et al.

245  C. Probably, this mode is strongly associated with the

restructuring upon ferroelectric phase transition. Of the
remaining temperatures at which there are marked nonmonotonic changes in the spectral characteristics of the phonon lines, two points of about 0 and 250  C evidently belong
to two structural phase transitions. As mentioned above, potassium niobate in its single-crystal state undergoes a phase
transitions R ! O and O ! T at the temperatures of 10 and
225  C, respectively. We cannot say with certainty that similar phases are realized in the investigated nanopowder,
because, as we see, in the region of 100110  C a marked
structural change is also observed. To determine which phase
(or possibly a mixture of phases) is (are) definitely realized
below the ferroelectric phase transition, it is necessary to conduct a separate XRD (or neutron diffraction) study.
Now we consider the temperature behavior of the
B1(TO2) and A1(TO1) lines. The dependences of the integrated intensity and frequency of these lines on the temperature are presented in Figure 6. First, let us trace the progress
of the condensation of the B1(TO2) line. In a change of the
integrated intensity of this line, we note several inflections in
the ranges from 20 to 50  C and from 190 to 280  C. At
about 400  C, the rate of decrease of the intensity slows
down and becomes almost zero above 475500  C. All three
features are obviously related to the restructuring of the material and those ranges are quite broad. Separately, there
should be focus on a high-temperature region, i.e., on the ferroelectric phase transition. We can definitely say that the
temperature interval of the phase transition is quite broad,
covering almost 100 , from about 425  C to 525  C. We
believe that this wide variation of the phase transition temperatures reflects the variation in particle size of the nanopowder. In other words, this interval indicates to the effect of
particle size on the Curie temperature, so we have a number
of the Curie temperatures, each of which refers to the particles of a certain size. The average Curie temperature

J. Appl. Phys. 113, 144103 (2013)

corresponded to the average particle size can be expected to

be defined as Tc 475  C. Accounting that the average particle size, defined from the XRD data, is 80 nm, it can be
assumed that the Tc 475  C refers to the particles of this
size. In the temperature dependence of the frequency of the
B1(TO2) line, it should be noted the inflections, associated
with structural phase transitions, in three ranges, from 40
to 40  , from 90 to 140  , and from 220 to 280  . At the
temperatures above 300  C, monitoring the change in frequency is almost impossible due to the overlap of this line
with other lines of the spectrum. Also, the soft mode
becomes highly overdamped and its frequency does not
extrapolate to zero at Tc. Finally, within the behavior of the
1(TO1) line, we can say the following. The integrated intensity of this line decreases rapidly with increasing temperature and at about 0  C, it reaches zero. It is obvious that this
band of the spectrum reflects the dynamics of the structural
elements of the lattice, which are involved in the lowtemperature phase transition.
We consider separately the longitudinal optical A1(LO3)
mode at 830 cm1. We followed up this peak up to
T 585  C. Since this temperature is considerably above Tc,
we assume that this mode is associated with disordering
effects, which break the cubic symmetry. Taking into
account that the particles (<100 nm) are much less than the
excited laser spot (d  1 lm), frequency changes of the longitudinal optical mode in the Raman spectra can be associated either with surface charges or with broken-symmetry
effects within polar microregions. These two factors of disorder are likely to be linked. Further investigation of this problem would be beyond the scope of this work. Let us focus on
the temperature dependent features in the spectral parameters
of the A1(LO3) line. Figure 7 shows the temperature dependences of intensity, linewidth, and frequency of the mode.
Non-monotonic change in all the parameters is observed.
Inflections in the temperature behavior of the intensity,

FIG. 6. Temperature dependences of the intensity (a) of B1(TO2), B1(TO3), and A1(TO1) lines and the frequency (b) of B1(TO2) mode of the phonon spectrum
of KNbO3 nanopowder.

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Golovina et al.

J. Appl. Phys. 113, 144103 (2013)

compared with the relevant temperatures in bulk crystals and

amount 0, 248, and 475  C. The manifestation of the size
effect is especially significant with respect to the Curie temperature, i.e., for the ferroelectric phase transition. There is a
clear influence of the surface, which has a determining affect
in nanoscale systems. In addition to the three known phase
transitions, we register a change in the structure at about
100110  C. We also conclude that the temperature ranges
of the phase transitions are quite broad, covering 80 100 .
We believe that such an extended width of the temperature
ranges reflects the variation in size of the nanopowder.
ACKNOWLEDGMENTS

The authors wish to thank Dr. Khainakov for providing

XRD and TEM data and L. V. Chernenko for the synthesis.

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FIG. 7. Temperature dependences of intensity, linewidth, and frequency of

A1(LO3) mode.

width, and frequency of the A1(LO3) line occur in three

regions, around 34, 248, and 460  C. These regions correspond to the structural phase transitions. As for the temperature region between 100 and 110  C, there are profound
irregularities in the graph. Although non-monotonic changes
in the intensity and linewidth are relatively insignificant
here, they should be noted. It can therefore be concluded that
all the inflections reflect relevant lattice restructurings.
IV. CONCLUSIONS

The analysis of the temperature behavior of the parameters of the transverse optical modes B1(TO2), A1(TO1),
B1(TO3), and longitudinal optical mode A1(LO3) of the
Raman spectra of KNbO3 nanopowder allows us to make the
following conclusions. The temperatures of all phase transitions shift to a high-temperature region by 10 , 25 , and 40

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