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Large piezoelectric properties in KNN-based lead-free single crystals grown by a seed-free solid-state crystal
growth method
Applied Physics Letters 108, 182904 (2016); 10.1063/1.4948642
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- wave form at 10 Hz. The coercive electric field Ec and the
tetragonal and tetragonal-cubic phase transitions. This rapid remanent polarization Pr were 2.2 kV/ mm average value
increase of loss with temperature seems to result from the and about 9.05 C / cm2 average value, respectively. The
increase of conductance accompanying the generation and 0.95KNN0.05LN single crystal does not show a typical
movement of oxygen and potassium vacancies. Because the ferroelectric polarization hysteresis loop Fig. 6. The loop is
crystal is grown in a sealed and anoxic atmosphere and po- round shaped and not saturated, which suggests that the leak-
tassium oxide severely volatilizes at high temperature, potas- age current induced by oxide vacancies is large. The result is
sium and oxygen vacancies easily engender. Since the radius in good agreement with the loop of Na0.5K0.5NbO3 ceram-
of potassium ion being small occupies the center of the oxy- ics with insufficient annealing time.14 Some growth modifi-
gen octahedra, ionic conduction formed by potassium vacan- cation and annealing process should be done in future work
cies is not evident in low temperature. When oxygen ions to decrease the oxide vacancies.
being relatively large occupy the corners of the octahedra, Optimum piezoelectric constant d33, dielectric constant
ionic conduction formed by oxygen vacancies is high even at and dielectric loss tan , Curie temperature TC and the elec-
room temperature. The rapid increase of loss factor after TC tromechanical coupling factor kt of 0.95KNN0.05LN single
is due to the conduction effect of both oxygen and potassium crystal at room temperature are shown in Table I. For com-
vacancies. Similar phenomena are found in some perovskite parison, the same parameters of some other lead-free
structure systems such as 1 xPbIn1/2Nb1/2O3 xPbTiO3 perovskite-type ferroelectric materials, ceramics or crystals,
single crystal and PbZn1/3Nb2/30.5Zr0.47Ti0.53O3 ce- are listed as well. It can be seen that the main piezoelectric
ramics annealed in Ar atmosphere.12,13 properties of 0.95KNN0.05LN crystals are superior to those
Ferroelectric measurement is carried out at a maximum of other lead-free piezoelectric single crystals. Compared
electric field of 25 kV/ cm applied using an amplified bipolar 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
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.
2
piezoelectric parameters are not given here because of the Y. P. Guo, K. Kakimoto, and H. Ohsato, Appl. Phys. Lett. 85, 4121 2004.
3
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ous special shapes and orientations. 4
G. Shiarane, R. Newnham, and R. Pepinsky, Phys. Rev. 96, 581 1954.
5
L. E. Cross, Nature London 181, 178 1958.
6
IV. CONCLUSION M. Ahtee and A. M. Glazer, Acta Crystallogr., Sect. A: Cryst. Phys.,
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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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K. Uchino and S. Nomura, Ferroelectr., Lett. Sect. 44, 55 1982.
10
sition at about 190 C, and the phase transition from tetrag- G. A. Smolenski and A. I. Agranovskaya, Sov. Phys. Tech. Phys. 3, 1380
1958.
onal to cubic phase at 426 C. The curves of temperature 11
G. A. Smolenski, J. Phys. Soc. Jpn. 28, 26 1970.
dependence of dielectric constants show that crystals are 12
H. Q. Fan, G. T. Park, J. J. Choi, and H. E. Kim, Appl. Phys. Lett. 79,
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Y. P. Guo, H. S. Luo, T. H. He, X. M. Pan, and Z. W. Yin, Mater. Res.
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14
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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X. J. Yin, H. C. Chen, W. W. Cao, M. L. Zhao, D. M. Yang, G. P. Ma, C.
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G. S. Xu, Z. Q. Duan, X. F. Wang, and D. F. Yang, J. Cryst. Growth 275,
high d33 405 pC/ N as well as a high kt61%. Considering 113 2005.