Dielectric and piezoelectric properties of lead-free

crystals grown by the Bridgman method

Kai Chen, , Guisheng Xu, , Danfeng Yang, and , Xiaofeng Wang, and Junbao Li

Citation: Journal of Applied Physics 101, 044103 (2007); doi: 10.1063/1.2562464

View online: http://dx.doi.org/10.1063/1.2562464
View Table of Contents: http://aip.scitation.org/toc/jap/101/4
Published by the American Institute of Physics

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 JOURNAL OF APPLIED PHYSICS 101, 044103 2007

Dielectric and piezoelectric properties of lead-free

0.95K0.5Na0.5NbO3 0.05LiNbO3 crystals grown
by the Bridgman method
Kai Chen, Guisheng Xu,a Danfeng Yang, and Xiaofeng Wang
R&D Center of Synthetic Crystals, Shanghai Institute of Ceramics, Chinese Academy of Sciences,
Shanghai 201800, Peoples Republic of China
Junbao Li
Institute of Acoustics, Chinese Academy of Sciences, Beijing 100080, Peoples Republic of China
Received 9 October 2006; accepted 2 January 2007; published online 22 February 2007
Lead-free potassium sodium niobate piezoelectric single crystals substituted with lithium
0.95K0.5Na0.5NbO3 0.05LiNbO3 have been grown by Bridgman method and their dielectric and
piezoelectric properties were studied. The orthorhombic-tetragonal and tetragonal-cubic phase
transition temperatures of the single crystal appear at 192 and 426 C according to the dielectric
constant versus temperature loops, respectively, and the 001 plates show good piezoelectric
properties with piezoelectric constant d33 as high as 405 pC/ N, large thickness electromechanical
coupling factor kt = 61%, and low dielectric constant of 185 at room temperature. These excellent
properties show that the 0.95K0.5Na0.5NbO3 0.05LiNbO3 single crystal is a good lead-free
piezoelectric material. 2007 American Institute of Physics. DOI: 10.1063/1.2562464

I. INTRODUCTION orientation and domain engineering can be realized in single

Lead-based ferroelectric and piezoelectric materials such
as PbTiO3 PbZrO3 PZT are most used in acoustic trans-
ducers, medical ultrasonic probes, solid actuators, and other
electromechanical fields. However, the increase in attention
to environment protection results in an urgent demand to find
some lead-free materials to replace PZT ceramics in different
applications due to their high content 60%70% of toxic
lead oxide. With higher piezoelectric response, good ferro-
electricity, and high Curie temperature, alkaline niobate
K , NaNbO3 KNN-based solid solutions are considered to
be an excellent candidate for lead-free piezoelectric materi-
als. However, it is difficult to obtain compacted ceramics of
alkaline niobate in conventional oxide sintering method be-
cause of their severe volatility at high temperature.
Recently, a great breakthrough was made in alkaline nio-
bate ceramics.13 Saito et al. and Guo et al. used different
methods to synthesize compacted Na, K , LiNbO3 ceramics.
The obtained ceramics show excellent piezoelectric proper-
ties, d33 245 pC/ N, kt 48%, and TC 460 C, where the
compositions are at the vicinity of the morphotropic phase
boundary MPB of K0.5Na0.5NbO3 and LiNbO3 binary
solid solution system.2 Meanwhile, they found that much
better piezoelectric and ferroelectric properties could be
achieved when the ceramics were textured and/or Ta doped.
Some textured Ta:KNN ceramics even exhibit the strong pi-
ezoelectricity very similar to those available from some PZT
ceramics PZT-4, d33 416 pC/ N, k p 61%, and TC
253 C.1 It is anticipated that KNN-based single crystals
might have piezoelectricity that is even better than their tex-
tured ceramics counterpart since the optimal crystallographic
a
Author to whom correspondence should be addressed; electronic mail:
gshxu@mail.sic.ac.cn
crystals. However, until now, most studies of alkaline niobate
materials have concentrated on the ceramic form, and the
single crystal form of these materials is reported rarely.
Though some Kx , Na1xNbO3 single crystals were grown
using flux methods,48 the x value did not surpass 40 mol %,
no dopants were added to establish a composition with MPB
features, and the obtained KNN crystals were always below
3 mm in size. On the other hand, previous researches on
KNN crystals mostly focused on their structures or optical
properties while their piezoelectricity has never been inves-
tigated. The purpose of this paper is to grow 1 x
K0.5Na0.5NbO3 xLiNbO3 1 xKNN-xLN single crys-
tals with the compositions near the MPB by using the Bridg-
man growth technique and to investigate their dielectric and
piezoelectric properties.
II. EXPERIMENT
The oxide powders with purities better than 99.9%, com-
prising Na2CO3, K2CO3, Li2CO3, and Nb2O5, were used as
starting materials for crystal growth. These materials were
mixed according to the composition formula of
0.95K0.5Na0.5NbO3 0.05LiNbO3 that is near the MPB x
= 0.05 0.07 Ref. 2 of 1 xKNN-xLN system. The pow-
ders were calcined in air at 830 C for 2 h before being
pressed at cold isostatic of 200 MPa. Then, they were
charged in the platinum crucibles, which were sealed to sup-
press the volatilization of melts. In the Bridgman method
growth of 1 xKNN-xLN crystals, the platinum crucibles
were maintained at 1330 C for more than 10 h and then
descended at the rate of 0.4 0.6 mm/ h. The temperature
gradient of 30 50 C / cm was used near the solid-liquid in-
terface in the growth furnace.

0021-8979/2007/1014/044103/4/$23.00 101, 044103-1 2007 American Institute of Physics

044103-2 Chen et al. J. Appl. Phys. 101, 044103 2007

FIG. 1. Color online Typical unpoled 001 oriented 0.95KNN0.05LN

FIG. 2. X-ray diffraction pattern of the 0.95KNN0.05LN single crystal
single crystal plates.
powder.

The crystal structures were determined by x-ray powder Therefore, it can be said that 0.95KNN0.05LN crystals are
diffraction analysis using a Cu K filter. For electrical char- transitional ferroelectrics between typical normal ones and
acterization, samples were polished and painted with silver typical relaxor ones. In order to determine which ones are
paste on the sample surfaces. Their dielectric properties were predominant, an empirical expression was employed,9
measured using an Agilent 4294A precision impedance ana-
lyzer in the temperature range from 30 to 450 C. Before 1 1 T Tm
= ,
piezoelectric measurements, the samples were poled by max C
40 kV/ cm dc field at 140 C for 30 min within silicon oil.
where and C are all constants, and the value is between
The piezoelectric constant d33 is measured with Berlincourt-
1 and 2. The limiting values = 1 and = 2 correspond to the
type quasistatic meter of ZJ-4A type made by Institute of
Curie-Weiss law valid for the case of normal ferroelectric
Acoustics, Chinese Academy of Sciences. The electrome-
and to the quadratic law valid for an ideal relaxor ferroelec-
chanical coupling factor kt was determined by a resonance
tric, respectively.10,11 The logarithm of 1 / 1 / max was
and antiresonance method with Agilent 4294A impedance
plotted against the logarithm of T tm and the curves are
analyzer. The ferroelectric hysteresis loops were measured at
shown in Fig. 4. The value of 0.95KNN0.05LN crystals is
room temperature by using a ferroelectric tester Trek 664
1.24, which shows that the normal ferroelectric property is
system at 10 Hz.
primary.
Besides, the dielectric loss at room temperature of the
III. RESULT AND DISCUSSION crystals is as low as 1.1% at 100 kHz and does not exceed
2.3% below the temperature TO-T, slowly increases from the
We obtained some 001-cut crystal plates Fig. 1 from
temperature TO-T to TC, and reaches a peak near the Curie
crystal boules. These plates, with the size of about 4 6
temperature, after TC increases rapidly especially at low fre-
0.5 mm3, were milk white and semitransparent before pol-
quencies Fig. 5. The two dielectric loss peaks appearing at
ing and become transparent after poling. The x-ray diffrac-
tion XRD results Fig. 2 show that the crystals have pure
perovskite structures and have an orthorhombic phase with-
out second phase. Lattice parameters a = 3.939 , b
= 3.919 , and c = 3.941 are calculated from the Bragg for-
mula.
The curves of the temperature dependence of dielectric
constants for unpoled 0.95KNN0.05LN crystals are shown
in Fig. 3. Two dielectric peaks appear at 192 and 426 C at
all frequencies 100 Hz, 1 kHz, 10 kHz, and 100 kHz. The
peaks at 192 and 426 C should be attributed to the phase
transition of orthorhombic-tetragonal at TO-T and
tetragonal-cubic at TC, respectively, which is approximately
consistent with the state of their unpoled ceramics
counterpart.3 The crystals behave like relaxor ferroelectrics
in that the dielectric constants decrease with the increase of
frequencies. On the other hand, they are not typical relaxor
ferroelectrics. It can be seen that the position and half-width FIG. 3. Colr online Temperature dependence of the dielectric constant of
of the transition peak at TC do not vary with frequencies. the unpoled 0.95KNN0.05LN single crystals at different frequencies.
044103-3 Chen et al. J. Appl. Phys. 101, 044103 2007

FIG. 4. The log1 / 1 / max as a function of logT Tm at 100 kHz for FIG. 6. Hysteresis loops of 0.95KNN0.05LN single crystal at room
0.95KNN0.05LN. temperature.

180 and 410 C can be correlated to the orthorhombic-
tetragonal and tetragonal-cubic phase transitions. This rapid
increase of loss with temperature seems to result from the
increase of conductance accompanying the generation and
movement of oxygen and potassium vacancies. Because the
crystal is grown in a sealed and anoxic atmosphere and po-
tassium oxide severely volatilizes at high temperature, potas-
sium and oxygen vacancies easily engender. Since the radius
of potassium ion being small occupies the center of the oxy-
gen octahedra, ionic conduction formed by potassium vacan-
cies is not evident in low temperature. When oxygen ions
being relatively large occupy the corners of the octahedra,
ionic conduction formed by oxygen vacancies is high even at
room temperature. The rapid increase of loss factor after TC
is due to the conduction effect of both oxygen and potassium
vacancies. Similar phenomena are found in some perovskite
structure systems such as 1 xPbIn1/2Nb1/2O3 xPbTiO3
single crystal and PbZn1/3Nb2/30.5Zr0.47Ti0.53O3 ce-
ramics annealed in Ar atmosphere.12,13
Ferroelectric measurement is carried out at a maximum
electric field of 25 kV/ cm applied using an amplified bipolar
wave form at 10 Hz. The coercive electric field Ec and the
remanent polarization Pr were 2.2 kV/ mm average value
and about 9.05 C / cm2 average value, respectively. The
0.95KNN0.05LN single crystal does not show a typical
ferroelectric polarization hysteresis loop Fig. 6. The loop is
round shaped and not saturated, which suggests that the leak-
age current induced by oxide vacancies is large. The result is
in good agreement with the loop of Na0.5K0.5NbO3 ceram-
ics with insufficient annealing time.14 Some growth modifi-
cation and annealing process should be done in future work
to decrease the oxide vacancies.
Optimum piezoelectric constant d33, dielectric constant
and dielectric loss tan , Curie temperature TC and the elec-
tromechanical coupling factor kt of 0.95KNN0.05LN single
crystal at room temperature are shown in Table I. For com-
parison, the same parameters of some other lead-free
perovskite-type ferroelectric materials, ceramics or crystals,
are listed as well. It can be seen that the main piezoelectric
properties of 0.95KNN0.05LN crystals are superior to those
of other lead-free piezoelectric single crystals. Compared
with the best results of the ceramics counterpart with the
same compositions, the crystals exhibit better piezoelectric
properties, d33 405 240 pC/ N, kt 61% 51%, and
tan 1.1% 8.4%. The crystals present the excellent pi-
ezoelectric properties that are almost comparable with the

TABLE I. Dielectric and piezoelectric properties of 0.95KNN0.05LN

single crystals in comparison with other fine lead-free materials.

Single crystal Ceramic

Constant KNN-LN BNTK30a BNT-BTb KNN-LNc LF4Td

TC C 426 365 330 460 253

d33 pC/N 405 160 160 240 416
kt % 61 49 51 kp 61
Loss % 1.1 8.4
a
Reference 15.
b
Reference 16.
c
Reference 3.
FIG. 5. Color online Loss of the unpoled 0.95KNN0.05LN single crystal d
Reference 1, where LF4T: textured K0.44Na0.52Li0.04
measured at different frequencies and temperatures. Nb0.86Ta0.10Sb0.04O3.
044103-4 Chen et al. J. Appl. Phys. 101, 044103 2007

best results of the textured ceramics doped with Ta and Sb their high Curie temperature of 426 C, these lead-free ma-
K0.44Na0.52Li0.04Nb0.86Ta0.10Sb0.04O3, but the former have terials are suitable for some electromechanical applications
the Curie temperature of 174 C higher than the latter. The to replace the PZT ceramics.
above data indicate that 0.95KNN0.05LN single crystals
1
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candidates to replace PZT ceramics even though the entire Nagaya, and M. Nakamura, Nature London 42, 84 2004.
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IV. CONCLUSION M. Ahtee and A. M. Glazer, Acta Crystallogr., Sect. A: Cryst. Phys.,
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0.95KNN0.05LN single crystals near MPB composi- 7
M. Badurski and K. Stroz, J. Cryst. Growth 46, 274 1979.
tion were grown directly from their melt by the Bridgman 8
I. P. Raevski et al., Crystallogr. Rep. 48, 486 2003.
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10
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onal to cubic phase at 426 C. The curves of temperature 11
G. A. Smolenski, J. Phys. Soc. Jpn. 28, 26 1970.
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oxygen vacancies. Pr 9.05 C / cm2 and Ec 2.2 kV/ mm are J. F. Li, K. Wang, B. P. Zhang, and L. M. Zhang, J. Am. Ceram. Soc. 89,
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