Solid State Communications 141 (2007) 675679 www.elsevier.

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Characterization of lead free (K0.5Na0.5)NbO3LiSbO3 piezoceramic

Shujun Zhang a, , Ru Xia a , Thomas R. Shrout a , Guozhong Zang b , Jinfeng Wang b
a Materials Research Institute, Pennsylvania State University, University Park, PA, 16802, USA b School of Physics and Microelectronics, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, PR China

Received 25 October 2006; received in revised form 12 December 2006; accepted 10 January 2007 by J.W.P. Hsu Available online 17 January 2007

Abstract (K0.5 Na0.5 )NbO3 (KNN) based lead free ceramics have been fabricated by a solid state reaction. In this work, LiSbO3 (LS) modied KNN based ceramics were sintered at atmospheric pressure and high density (>96% theoretical) was obtained. The detailed elastic, dielectric, piezoelectric and electromechanical properties were characterized by using the resonance technique combined with the ultrasonic method. The full set of material constants for the obtained polycrystalline ceramics were determined and compared to the pure hot pressed KNN counterpart. KNN-LS polycrystalline ceramic was found to have higher elastic compliance, dielectric permittivity and piezoelectric strain coefcients, but lower mechanical quality factor, when compared to pure KNN, exhibiting a softening behavior. However, a high coercive eld (17 kV/cm) was found for the LS modied KNN material. The properties as a function of temperature were determined in the range of 50250 C, showing a polymorphic phase transition near room temperature, giving rise to improved piezoelectric behavior. c 2007 Elsevier Ltd. All rights reserved.
PACS: 77.84.s; 77.84.Dy; 77.65.Bn; 77.80.Bh; 77.80.Dj Keywords: A. Ferroelectrics; D. Piezoelectricity

1. Introduction Lead based piezoelectric ceramics Pb(Zr1x Tix )O3 (PZT) have dominated the commercial market for more than half a century since its discovery in the 1950s. PZTs are widely used for various applications, such as medical transducers, actuators, sensors and high power piezoelectric transformers due to their good piezoelectric, dielectric and mechanical properties [1,2]. However, lead free piezoelectric materials have been desired from the viewpoint of environmental issues over the last few years, arising from draft directives on waste from electrical and electronic equipment (WEEE) and restriction of hazardous substances (RoHS) [3]. Many lead free piezoelectric ceramic families, such as bismuth layer structure ferroelectrics (BLSFs) [47], modied BaTiO3 (BT) [1,2,8], (Na0.5 Bi0.5 )TiO3 (NBT) [918] or (K0.5 Na0.5 )NbO3 (KNN) [1936] based compounds have been intensively studied. The BLSF based materials possess
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E-mail address: soz1@psu.edu (S. Zhang). 0038-1098/$ - see front matter c 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.ssc.2007.01.007

ultrahigh Curie temperature (TC > 500 C), exhibit low dielectric and piezoelectric properties, while BT ceramics show relatively high properties, however, the usage temperature range is limited to 100 C near their Curie temperature. NBT based solid solutions are attractive because of their strong ferroelectricity with large remnant polarization and coercive eld. NBT ceramics have Curie temperatures of 320 C, forming a morphotropic phase boundary with other end members like (K0.5 Bi0.5 )TiO3 (KBT) [13] or BT [10] or a ternary system with KBT-BT [1618], with depolarization temperature (ferroelectric to anti-ferroelectric phase transition) around 200 C. However, for the KNN family, it was reported to be difcult to get high density ceramic by using the conventional solid state method and hot-pressed (HP) pure KNN exhibits a piezoelectric coefcient d33 on the order of 130 pC/N, with a Curie temperature and polymorphic phase transition temperature around 420 C and 200 C, respectively [2,1922]. Recently, it has been reported that the (Li, Ta, Sb)-modied KNN (LF4) materials (in textured form) exhibit a d33 value on the order of 400 pC/N, comparable to the piezoelectric behavior of hard PZT4 materials [23], attracting

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a lot of interest in modication studies on KNN systems. However, the high piezoelectric properties of the LF4 ceramics sacrice the Curie temperature, which was only about 253 C. More recent researchers have shown that different additives in KNN materials, like Li+ , LiNbO3 (LN), LiTaO3 (LT), LiSbO3 (LS), SrTiO3 (ST) and BT [2431], can help improve the sintering behavior of KNN (95% of the theoretical density), which enhance the piezoelectric (200300 pC/N) and dielectric properties when compared to pure KNN. The LS modied KNN lead free piezoceramic was reported to have desirable dielectric and piezoelectric behavior, with T dielectric 33 /0 > 1300, d33 > 260 pC/N and k p 50%, while still keep high Curie temperature around 370 C, revealing a promising candidate for transducer or sensor applications [30,32]. In order to further study the theoretical and practical applications of the KNN-LS material, it is desirable to have a full set of elastic, piezoelectric and dielectric constants. In this paper, the material constants were measured by a combination of resonance [37,42] and ultrasonic methods [3841], and compared to the pure hot-pressed KNN counterpart. The electromechanical and piezoelectric properties were also studied as a function of temperature, exhibiting strong temperature dependence near room temperature. 2. Experimental The solid state reaction method was used to prepare the modied KNN composition. Na2 CO3 (99.9%), K2 CO3 (99.9%), Li2 CO3 (99.9%), Nb2 O5 (99.5%) and Sb2 O5 (99.9%) were used as starting materials. All of the materials were dried at 200 C to remove any moisture, and then weighed according to the formulation. The powders were vibratory milled in anhydrous ethanol for 24 h, dried and subsequently calcined at 850 C for 2 h. The calcined powders were granulated and pressed into desired blocks and sintered at 11601200 C for 2 h in air. The density of the block was carefully measured by Archimedes method and found to be 4.3 g/cm3 , about 95% of the theoretical [30,32]. The obtained samples were cut and polished with different sizes and aspect ratios according to the desired mode of resonance, as given in Ref. [37], and the samples for ultrasonic velocity measurements were 4 mm by 6 mm by 6 mm cubic. All the samples were electroded using gold-sputtering and poled at 60 kV/cm electric eld at room temperature. High eld polarization was measured by using a modied SawyerTower circuit and linear variable differential transducer (LVDT) driven by a lock-in amplier (Stanford Research Systems, Model SR 830). The resonance method was performed using a HP4194A impedance/gain phase analyzer. The resonance and antiresonance frequencies, corresponding to the minimum and maximum values of the impedance frequency spectrum, were used to calculate the corresponding electromechanical coupling factors and elastic compliances [42]. For the ultrasonic measurements, a 15 MHz longitudinal wave transducer and a 5 MHz shear wave transducer excited by a Panametrics 200 MHz pulser/receiver were used to determine the velocity

of longitudinal and shear waves, respectively, and the timeof-ight between echoes was recorded by a Tektronix 460A digital oscilloscope [3841]. The temperature dependence of dielectric and electromechanical properties was determined using HP4284A LCR meter and HP4194A impedance/gainphase analyzer connected with a multi-functional furnace, respectively. 3. Results and discussion The phase velocities of longitudinal and shear waves with displacement along and perpendicular to the poling direction of samples (with dimension of 4 6 6 mm3 ) were measured using the pulse-echo method. Four corresponding D E D E elastic constants (= 2 ) c33 , c11 , c44 and c66 were determined from the measured velocities, it should be noticed that the effective elastic constants are related to the poling direction in the polycrystalline ceramic, different from single crystals or E textured ceramics. The elastic stiffness c12 was then calculated following the equation:
E E E c12 = c11 2c66 .

(1)

The resonance and antiresonance frequencies for samples with different aspect ratios were determined [37] and the corresponding electromechanical coupling (k p , kt , k33 , k31 , k15 ) D D E D and elastic constants (c33 , s33 , s11 and c44 ) were calculated according to IEEE standard [42]. Poissons ratio was calculated according to the following formulae: E =
E (c11

1 1 1= E E 1 E )s E c12 11 2c66 s11

(2)

and found to be 0.32, very close to the values of other perovskite piezoelectric ceramics [37]. Poissons ratio calculated from the values of elastic constants (which were obtained by the combination of ultrasonic pulse-echo and resonance methods) was deemed to be more accurate compared to the value obtained by the direct resonance measurement (using a thin disk sample with a large diameter to thickness ratio /t 50 and Poissons ratio was calculated from the value of the rst resonant frequency and second resonant frequency of the planar mode [37]), owing to the difculties in fabricating samples with large aspect ratios and perfect parallelism. The measured and derived complete set of material constants for KNN-LS piezoceramic was listed in Tables 13, and compared to the pure counterpart (data for hot-pressed KNN materials from Ref. [2,1922]). The errors in the measured material constants mainly arise from the imperfect parallelism, inaccuracy of the density measurements, sample dimension and aspect ratio, and also the polarization status of the samples. To ensure the self-consistency of the material constants, several batches of samples have been used to measure the material constants by the resonance and ultrasonic methods. From Table 1, the KNN-LS materials were found to have higher elastic compliance and lower elastic stiffness constants, exhibiting a softening effect by the modication of LS in the KNN material, which was conrmed by the higher piezoelectric strain coefcients (Table 2) and dielectric constant (Table 3).

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Table 1 Measured and derived elastic compliance constants, si j (1012 m2 /N), and elastic stiffness constants, ci j (1010 N/m2 ), for KNN-LS5.2, compared to pure KNN counterpart (hot pressed) Material KNN-LS KNN Material KNN-LS KNN
E s11 E s12 E s13 E s33 E s44 E s66 D s11 D s12 D s13 D s33 D s44 D s66

12.06 8.20
E c11

3.86 2.54
E c12

5.45 3.43
E c13

15.00 10.10
E c33

33.30 27.00
E c44

31.84 21.48
E c66

11.01 7.60
D c11

4.91 3.14
D c12

2.99 1.96
D c13

9.23 6.40
D c33

22.90 15.80
D c44

31.84 21.48
D c66

14.20 19.67

7.97 10.36

8.56 10.20

12.54 16.80

3.00 3.70

3.14 4.66

14.27 19.88

8.04 10.57

8.13 9.35

15.90 21.40

4.40 6.33

3.14 4.66

Table 2 Piezoelectric coefcients, di j (pC/N), ei j (C/m2 ), gi j (103 V m/N), h i j (108 V/m), and electromechanical coupling factors, ki j , for KNN-LS5.2, compared to pure KNN counterpart (hot pressed) Material KNN-LS KNN Material KNN-LS KNN Material KNN-LS KNN d33 265 127 g33 21.70 29.00 k33 0.62 0.61 d31 114 51 g31 9.33 11.60 k31 0.30 0.27 d15 340 306 g15 32.02 36.90 k15 0.57 0.64 e33 13.71 9.80 h 33 18.66 36.21 kt 0.46 0.46 e31 2.28 2.36 h 31 3.10 8.72 kp 0.50 0.46 e15 10.20 11.30 h 15 14.23 23.37 d33 (m) 275 / Fig. 1. Polarization hysteresis and strain loop for LS modied KNN materials measured at 30 kV/cm electric eld and 1 Hz frequency.

Table 3 Dielectric constants, i j (0 ), and dielectric impermeability constants, (104 /0 ), for KNN-LS5.2, compared to pure KNN counterpart (hot pressed) Material KNN-LS KNN
T 33 T 11 S 33 S 11 T 33 T 11 S 33 S 11

the dynamics of domain wall motions will contribute to the effective elastic compliance. The phase velocity of the shear E wave v6 is related to elastic compliance:
E E E v6 = 1/ 2(s11 s12 ) = E c66 /.

1380 496

1200 938

830 306

810 545

7.2 20.2

8.3 10.7

12.0 32.7

12.3 18.3

(3)

Fig. 1 presents the polarization hysteresis and strain loop measured at electric eld of 30 kV/cm and 1 Hz frequency. The remnant polarization (Pr ) was found to be 23 C/cm2 with a coercive eld (E C ) on the order of 17.2 kV/cm at room temperature. The detailed electrical properties of KNNLS were listed in Table 4 and compared to the pure hot-pressed KNN lead free material and lead based PZT5A ceramic. It is obvious that the LS modication in KNN shifts both the Curie temperature (TC ) and the orthorhombic to tetragonal polymorphic phase transition temperature (TOT ) downwards, especially the latter value, which were found to be around room temperature and deemed to play an important role in the enhancement of the piezoelectric behavior [32,33]. The low mechanical quality factor Q and high dielectric loss also indicate softening behavior, like the soft PZT5A material. However, it is worth noting that the coercive eld of KNNLS ceramic (17 kV/cm) is higher than the value of the pure hot-pressed KNN material (5 kV/cm [43]), demonstrating a hardening effect, which was thought to relate to the polymorphic phase transition [33]. The shear wave mode with both the propagation and displacement perpendicular to the poling direction is related to domain wall motion, since

Experimental results imply that the domain wall motion results E E in a very large effective (s11 s12 ), and, therefore, a slower sound velocity [38]. From Table 4, the phase velocity of KNNLS was found to be lower than the value of pure hot-pressed KNN, while larger than the soft PZT5A ceramic. It is known that the domain wall motion makes a big extrinsic contribution to the piezoelectric coefcient in soft PZT materials [1,2]. So the KNN-LS material was thought to have more extrinsic contribution in the piezoelectric coefcient, when compared to pure KNN, indicating soft behavior. Figs. 2 and 3 give the temperature behavior of the electromechanical and piezoelectric properties for KNN-LS materials, respectively. As shown in Fig. 2, the longitudinal electromechanical coupling k33 was found to be 62% at 50 C, slightly increasing to 62.7% at 0 C, and then gradually decreasing to 51.6% with the temperature reaching 250 C. Similar to k33 , the extensional electromechanical coupling k31 was found to be 29.4% at 50 C, reaching 30% at room temperature, and then decreasing to a value of 19.3% at 250 C. The piezoelectric coefcients d33 and d31 were found to reach their peak values of 265 pC/N and 116 pC/N near room temperature, as can be seen in Fig. 3, a similar tendency as for the electromechanical properties,

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Table 4 Detailed electrical properties of KNN-LS, compared to pure KNN (hot pressed) and lead based PZT5A ceramics Material KNN-LS KNN PZT5A TC ( C) 368 420 368 TOT ( C) 35 195 / E C (kV/cm) 17.2 5 15 Pr (C/cm2 ) 23 33 35
T 33 /0

Loss (%) 2 1.5 2

d33 (pC/N) 265 127 370

Q 40 240 70

D v3 (m/s)

E v6 (m/s)

1380 496 1700

6080 6930 4350

2700 3230 1720

of the domain engineering process in lead free materials. The strong temperature dependence of the properties offers the chance for further studies on improving the temperature stability while maintaining the high piezoelectric properties of KNN based lead free materials [33]. Acknowledgments This work supported by Ofce of Naval Research (ONR) and National Institutes of Health (NIH) under grant number P41-RR11795. References
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Fig. 3. Temperature dependence of the piezoelectric coefcients for KNN-LS lead-free materials.

showing a strong temperature dependent behavior at room temperature, as expected. 4. Conclusion In summary, the full set of material constants for KNN-LS materials were measured and calculated, and compared to the pure counterpart and lead based PZT5A materials. The LS modication in KNN materials softens the materials, meanwhile, shifting the orthorhombic to tetragonal polymorphic phase transition downward to near room temperature, which play an important role in the improvement of the dielectric and piezoelectric properties. The shear wave mode is associated with domain wall motions, the phase velocity revealing a less extrinsic contribution from the domain wall to the piezoelectric properties for KNN-LS, when compared to the soft PZT5A material, while having a more extrinsic contribution when compared to pure hot-pressed KNN. This will provide bases for theoretical investigation

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