868

IEEE TransacTIons on UlTrasonIcs, FErroElEcTrIcs, and FrEqUEncy conTrol ,

vol. 58, no. 4,

aprIl

2011

Correspondence
Dielectric and Electromechanical Properties of Rare Earth Calcium Oxyborate Piezoelectric Crystals at High Temperatures Fapeng yu, shujun Zhang, Senior Member, IEEE, Xian Zhao, duorong yuan, lifeng qin, qing-Ming Wang, Member, IEEE, and Thomas r. shrout, Senior Member, IEEE
AbstractThe electrical resistivity, dielectric, and electromechanical properties of ReCa4O(BO3)3 (ReCOB; Re = Er, Y, Gd, Sm, Nd, Pr, and La) piezoelectric crystals were investigated as a function of temperature up to 1000C. Of the studied crystals, ErCOB and YCOB were found to possess extremely high resistivity (): > 3 107 cm at 1000C. The property variation in ReCOB crystals is discussed with respect to their disordered structure. The highest electromechanical coupling factor k26 and piezoelectric coefficient d26 at 1000C, were achieved in PrCOB crystals, with values being on the order of 24.7% and 13.1 pC/N, respectively. The high thermal stability of the electromechanical properties, with variation less than 25%, together with the low dielectric loss (<46%) and high mechanical quality factor (>1500) at elevated temperatures of 1000C, make ErCOB, YCOB, and GdCOB crystals promising for ultrahigh temperature electromechanical applications.

I. Introduction ecause of their fast response time and easy integration, high-temperature piezoelectric crystals have been extensively investigated for ultrahigh temperature (~1000c) sensing applications. structural health monitoring of high-temperature furnace components and reactor systems are desirable in coal-fired electric generation plants and nuclear plants, and engine health monitoring is another industrial application which benefits from hightemperature sensing technology [1][6]. High-temperature piezoelectric sensors require minimal temperature dependence of dielectric/electromechanical properties and high electrical resistivity () over a wide temperature range. currently, quartz (-sio2) and lithium niobate (linbo3; ln) piezoelectric crystals are widely employed in sensing applications. However, the maximum operating temperature of quartz-based devices is limited to 350c as a result
Manuscript received december 14, 2010; accepted February 4, 2011. This work was supported by nsF under grant number Eccs09-25586 and the national nature science Foundation of china (nsFc no. 50902089). F. yu thanks the china scholarship council for their support. F. yu, X. Zhao, and d. yuan are with the state Key laboratory of crystal Materials and Institute of crystal Materials, shandong University, Jinan, p. r. china. F. yu, s. Zhang, and T. r. shrout are with the Materials research Institute, pennsylvania state University, University park, pa (e-mail: soz1@psu.edu). l. qin and q.-M. Wang are with the department of Mechanical Engineering and Materials science, University of pittsburgh, pittsburgh, pa. digital object Identifier 10.1109/TUFFc.2011.1881 08853010/$25.00

of crystal twinning, and the low resistivity of ln crystals restricts its implementation to less than 600c, though the curie temperature is above 1140c [7]. The langasite family of crystals (general formula a3Bc3d2o14), exhibit no phase transformation before their respective melting temperatures (~1500c) and can be readily grown using the czochralski (cz) method. The piezoelectric coefficient d11 can reach values of ~7 pc/n, two to three times that of quartz. However, low resistivity and high dielectric loss limit their usage to less than 800c. an analogue to quartz, hydrothermally grown Gapo4, was reported to possess relatively high resistivity and low dielectric loss, but the operational temperature was <970c, because of the phase transformation [8][12]. recently, piezoelectric crystals with high resistivity and strong electromechanical properties, operational up to 1000c, have been investigated [2][6]. oxyborate crystals reca4o(Bo3)3 (re = rare earth, abbreviated as recoB) with monoclinic symmetry offer piezoelectric coefficients d33 on the order of 6 to 7 pc/n, similar to langasite crystals. The electrical resistivity of ycoB and GdcoB crystals have been reported to be > 106 cm at 1000c, one to three orders of magnitude higher than langasite family crystals [2], [3], [5], providing the possibilities of exploring recoB crystals for ultrahigh temperature electromechanical applications. recently, the dielectric and electromechanical properties of recoB (re: Er, y, Gd, sm, pr, nd, and la) piezoelectric crystals were investigated as a function of re3+ radius at room temperature. The relative dielectric perT E mittivity e22/e 0, elastic compliance s 66, electromechanical coupling factor k26, and piezoelectric coefficient d26 were found to increase with increasing re3+ ionic radius, from Er (rEr(+3) = 0.890 ) to la (rla(+3) = 1.032 ), with maximum values being observed for prcoB (rpr(+3) = 0.990 ) crystals (ionic radius after [13]). Mechanical q values, however, exhibited minimum values, as summarized in Table I [14]. The relationship between crystal structure and property was established, based on the disorder level and rare earth cation radius [15]. The purpose of this paper is to provide a comprehensive study of the properties of recoB crystals as a function of temperature up to 1000c, to establish the relationship(s) between crystal structure and temperature-dependent behavior. II. Experimental recoB piezoelectric crystals, including ErcoB, ycoB, GdcoB, smcoB, ndcoB, prcoB, and lacoB, were grown by the conventional rF-heating cZ method in a nitrogen atmosphere containing 4 vol% oxygen. asgrown crystals were oriented along the crystallographic

2011 IEEE

yu et al.: properties of rare earth calcium oxyborate crystals at high temperature

869

directions 010, 201, and 101 using X-ray diffraction, from which the crystallographic axes a, b, and c could be confirmed. according to the IEEE Piezoelectric Standard [16], the physical y- and Z- axes for piezoelectric crystals with space group Cm are parallel to the crystallographic b and c axes, respectively; the X- axis is perpendicular to the yZ plane to form the right-hand orthogonal system. The positive directions of the Z- and X- axes were further confirmed by measuring the piezoelectric coefficients d33 and d11, which are positive values. The dimensional ratio of y- square plates used for dielectric and resistance measurements was 1:10:10; for electromechanical measurements, (ZXw)0 cut samples (width shear vibration mode) were used with dimensional ratios, t (thickness): w (width): l (length) ranging from 1: 2:10 to 1:3:15. all of the samples were polished using 15-m sic powder and electroded by vacuum-sputtered pt thin films (300 nm) on the parallel faces. all of the measurements were performed from room temperature up to 1000c; at temperatures above 1000c, the pt electrodes were found to degrade. The relative dielectric permittivity eT /e 0 was 22 determined from capacitance measurements using a multifrequency lcr meter (Hp4284a, agilent Technologies Inc., santa clara, ca). The electromechanical coupling E factor k26 and elastic compliance s 66 were calculated based on the resonance/anti-resonance frequencies, measured using an agilent Hp 4294a impedance network analyzer, connected to a specially designed sample holder in a hightemperature furnace. The piezoelectric coefficient d26 was calculated using dielectric, elastic, and coupling parameters. The mechanical q values given in this paper were calculated based on the Butterworth-Van dyke equivalent circuit. III. results and discussion A. Resistivity at Elevated Temperatures High-temperature piezoelectric devices require crystals to possess high sensitivity (high piezoelectric coefficients), high electrical resistivity, and rc time constants (r is electrical resistance and c the capacitance of the device). The higher the rc time constant, the longer the induced

Fig. 1. Electrical resistivity () of y-cut recoB (re = Er, y, Gd, sm, nd, pr, and la) crystals at room temperature (small inset) and elevated temperatures.

charge is maintained. The minimum useful frequency of a sensor, known as the lower limiting frequency (fll), is inversely proportional to the rc time constant, below which the charge will drain off before it can be detected [7]. Thus, for potential high-temperature electromechanical applications, it is necessary to evaluate both the hightemperature electrical resistivity and dielectric property of recoB crystals. The electrical resistivities of y-cut recoB samples as a function of temperature are given in Fig. 1, with room-temperature resistivity extrapolated and given in the small inset. as shown in Fig. 1, the electrical resistivity was found to decrease with increasing re3+ ionic radius, with the exception of lacoB. The resistivity values for different recoB crystals at 1000c were determined to be in the range = 1.0 106 to 1.0 108 cm. The activation energies (Ea) were calculated from the slope of the resistivity curves, according to the arrhenius equation, and found to be 0.55 to 0.83 eV for all of the investigated recoB crystals (Table I). The variation of resistivity values for recoB crystals is believed to relate to the degree of disordered structure in the crystals, because of the disorder distribution of cat-

TaBlE I. physical and Electrical properties of Various recoB crystals at room Temperature. piezocrystal radius ()* (cm)** Ea (eV) T22/0 dielectric loss sE66 (pm2/n) k26 (%) d26 (pc/n) q26 re3+ ErcoB 0.890 3 1017 0.83 11.8 0.5 <0.1% 16.5 0.3 18.5 2.0 7.6 0.6 ~9000 ycoB 0.900 1 1017 0.83 12.0 0.5 <0.1% 16.3 0.3 19.0 1.8 7.8 0.6 ~9000 GdcoB 0.938 2 1015 0.62 13.5 0.6 <0.1% 18 0.5 24.7 2.2 11.5 0.6 ~5000 smcoB 0.958 8 1014 0.55 13.9 0.7 <0.1% 18.4 0.4 27.0 2.0 12.7 0.8 ~4500 ndcoB 0.983 5 1014 0.55 15.5 0.4 <0.1% 18.5 0.6 30.0 1.5 15.0 1.5 ~4000 prcoB 0.99 1 1014 0.60 15.3 0.6 <0.1% 19.0 0.6 31.5 1.5 15.8 1.0 ~3800 lacoB 1.032 8 1014 0.80 15.0 0.4 <0.1% 17.0 0.4 25.0 1.5 11.8 0.8 ~5000

*after [13]. **Extrapolated room temperature electrical resistivity ().

870

IEEE TransacTIons on UlTrasonIcs, FErroElEcTrIcs, and FrEqUEncy conTrol ,

vol. 58, no. 4,

aprIl

2011

T Fig. 2. Variation of dielectric permittivities e22/e 0 and dielectric loss for various recoB (re = Er, y, Gd, sm, nd, pr, and la) crystals up to 1000c.

Fig. 3. Impedance modulus in the vicinity of the resonance frequency for different recoB crystals at 900c (small insets present the mechanical quality factor for recoB at room temperature and the phase angles for recoB at 900c).

ions in oxyborate crystals. a high level of disorder was reported to induce phonon scattering and decrease electrical resistivity [17], [18]. The electron-hole pairs will form upon the random occupations of re3+ and ca2+ ions on octahedral sites in the crystals, according to the defect equation (taking lacoB for example): La La + Ca Ca La Ca +
Ca La .

ture coefficient of permittivity Tc can be evaluated from (3) [18], [19], TC e = (e - 1)(e + 2) (A + B + C ) + 0.05 tan d e TC e = constant - ae, (2) (3)

(1)

The electron-hole pairs in recoB crystals, together with the disordered structure, account for the increased conductivity. It was reported that recoB crystals with re3+ radius closer to ca2+ (1.0 ) will provide a higher possibility of re3+ and ca2+ disorder distribution, leading to lower resistivity and higher dielectric loss at elevated temperatures [15]. From this perspective, the high resistivity values for ErcoB and ycoB crystals were attributed to the relatively large difference in ionic radius between re3+ (Er3+ and y3+) and ca2+. B. Temperature-Dependent Dielectric Properties The dielectric behavior as function of temperature up to 1000c for the recoB crystals is presented in Fig. 2. The dielectric permittivity for ErcoB and ycoB was found to increase from room temperature to 1000c, with temperature coefficients of permittivity (Tc) being on the order of 130 to 180 ppm/c, whereas GdcoB and smcoB crystals exhibit lower Tc values, being 60 to 100 ppm/c over the same temperature range. For ndcoB, prcoB, and lacoB crystals, however, the dielectric perT mittivity e22/e 0 was found to decrease slightly and then increase with increasing temperature, showing an inflexion around 600c. according to the clausius-Mosotti equation (2), materials with dielectric permittivities 50 > T e22/e 0 > 10 and dielectric loss tan < 0.1%, the tempera-

where (A + B) indicates the effect of volume expansion with increasing temperature, and C gives the temperature dependence of the polarizability of the intrinsic ions and electrons with constant volume; is the linear thermal expansion coefficient. Thus, Tc decreases with increasing dielectric permittivity [18][21]. as expected, ErcoB, ycoB, GdcoB, and smcoB exhibited positive Tc, beT cause of their low permittivity, e22/e 0 < 14, whereas the negative Tc for ndcoB, prcoB, and lacoB, can be T attributed to their relatively high value of e22/e 0 > 15. For materials with tan > 0.1%, however, the Tc is dominated by dielectric loss. as observed in Fig. 2, the dielectric loss for ndcoB, prcoB, and lacoB crystals was found to increase significantly for temperatures above 600c, thus, a positive Tc was expected in the temperature range of 600 to 1000c, according to TC e = 0.05 tan d - ae. (4)

The high dielectric loss for ndcoB, prcoB, and lacoB crystals was believed to be associated with their relatively high conductivity (low resistivity) at elevated temperatures, as discussed previously. C. Temperature-Dependent Electromechanical and Piezoelectric Properties Fig. 3 gives the impedance modulus for recoB crystals at 900c, from which the electromechanical coupling fac-

yu et al.: properties of rare earth calcium oxyborate crystals at high temperature

871

Fig. 4. Variation of electromechanical coupling factor (k26) for various recoB (re = Er, y, Gd, sm, nd, pr, and la) crystals as a function of temperature (small inset shows the room-temperature k26 values).

E Fig. 5. Elastic compliance (s 66) for various recoB crystals as a function of temperature (small inset gives the room-temperature elastic compliances).

tor and mechanical quality factor q were determined. The highest coupling k26 was found to be 25.0% for prcoB crystals, which had the lowest mechanical quality factor q, on the order of <1000 (mechanical q at room temperature and phase angle at 900c are presented in small insets). The minimum value of k26 was found for the lacoB crystals (19.5%), with a q value of >1600. Interestingly, ErcoB, ycoB, and GdcoB crystals were found to possess high q values (>1500) at 900c and high electromechanical coupling factors. The small inset in Fig. 3 shows room temperature mechanical quality factors q, as a function of re3+ ionic radius. High q values were observed for ErcoB and ycoB crystals, being on the order of ~9000; relatively low q values were observed for ndcoB and prcoB (< 4500) because of the high disorder level of ca2+ and re3+ distribution [12], [22]. The mechanical q values were found to decrease with increasing temperature, which was evident from the rounding of resonance and anti-resonance frequency peaks. The temperature dependent coupling factor k26 for varied recoB crystals is presented in Fig. 4. It was found that k26 for prcoB crystals decreased from 31.5% to 24.7% as the temperature increased from room temperature to 1000c, giving a variation of 21.6%. similar trends were observed for GdcoB, smcoB, ndcoB, and lacoB crystals, with the variations being on the order of 15 to 27%. Interestingly, the coupling factor k26 for ErcoB and ycoB crystals was found to maintain similar values in the temperature range of 20 to 1000c, exhibiting excellent thermal stability. E Fig. 5 shows the variation of elastic compliance s 66 with temperature up to 1000c, with room temperature values E given in the small inset. as shown, all of the s 66 values for various recoB crystals were found to increase with inE creasing temperature. The elastic compliance s 66 for ErcoB, ycoB, and GdcoB crystals increased linearly as a

Fig. 6. Variation of resonance frequency of (ZXw)0-cut recoB crystals as a function of temperature.

function of temperature, with temperature coefficients beE ing on the order of 180 to 130 ppm/c. In contrast, s 66 values for ndcoB and prcoB crystals exhibited a quadric behavior with temperature. Fig. 6 gives the resonance frequency variation as function of temperature, for (ZXw)0-cut recoB crystals. as can be seen, ErcoB, ycoB, and GdcoB crystals exhibited a linear frequency temperature behavior up to 1000c, with temperature coefficient of frequency (TcF) being on the order of 60 to 80 ppm/c; ndcoB and prcoB crystals exhibited turnover temperatures around 80 to 100c, indicating the existence of zero-TcF cuts, which have been confirmed in previous studies [23], [24]. T Based on the relative dielectric permittivities e22/e 0, E elastic compliances s 66, and electromechanical coupling

872

IEEE TransacTIons on UlTrasonIcs, FErroElEcTrIcs, and FrEqUEncy conTrol ,

vol. 58, no. 4,

aprIl

2011

the high thermal stability of electromechanical properties, make ErcoB, ycoB, and GdcoB promising materials for high-temperature electromechanical applications.

references
[1] M. J. schulz, M. J. sundaresan, J. McMichael, d. clayton, r. sadler, and B. nagel, piezoelectric materials at elevated tempearture, J. Intell. Mater. Syst. Struct., vol. 14, no. 11, pp. 693705, 2003. [2] s. J. Zhang, E. Frantz, r. Xia, W. Everson, J. randi, d. W. snyder, and T. r. shrout, Gadolinium calcium oxyborate piezoelectric single crystals for ultrahigh temperature (>1000c) applications, J. Appl. Phys., vol. 104, no. 8, art. no. 084103, 2008. [3] s. J. Zhang, y. T. Fei, B. H. T. chai, E. Frantz, d. W. snyder, X. n. Jiang, and T. r. shrout, characterization of piezoelectric single crystal yca4o(Bo3)3 for high temperature applications, Appl. Phys. Lett., vol. 92, no. 20, art. no. 202905, 2008. [4] F. p. yu, s. J. Zhang, X. Zhao, d. r. yuan, q. M. Wang, and T. r. shrout, High temperature piezoelectric properties of yttrium calcium oxyborate single crystals, Phys. Status Solidi-RRL, vol. 4, no. 56, pp. 103105, 2010. [5] s. J. Zhang, y. T. Fei, E. Frantz, d. W. snyder, B. H. T. chai, and T. r. shrout, High-temperature piezoelectric single crystal reca4o(Bo3)3 for sensor applications, IEEE Trans. Ultrason. Ferroelectr. Freq. Control, vol. 55, no. 12, pp. 27032708, 2008. [6] s. J. Zhang, X. n. Jiang, M. lapsley, p. Moses, and T. r. shrout, piezoelectric accelerometers for ultrahigh temperature application, Appl. Phys. Lett., vol. 96, no. 1, art. no. 013506, 2010. [7] T. r. shrout, r. Eitel, and c. a. randall, High performance, high temperature perovskite piezoelectric ceramics, in Piezoelectric Materials in Devices, n. setter, Ed. lausanne, switzerland: EpFl swiss Federal Institute of Technology, 2002, pp. 413432. [8] H. Fritze and H. l. Tuller, langasite for high temperature bulk acoustic wave applications, Appl. Phys. Lett., vol. 78, no. 7, pp. 976978, 2001. [9] H. ogi, n. nakamura, K. sato, M. Hirao, and s. Uda, Elastic, anelastic and piezoelectric coefficients of langasite: resonance ultrasound spectroscopy with laser-doppler interferometry, IEEE Trans. Ultrason. Ferroelectr. Freq. Control, vol. 50, no. 2, pp. 553560, Feb. 2003. [10] H. Fritz, High temperature piezoelectric materials: defect chemistry and electromechanical properties, J. Electroceram., vol. 17, no. 24, pp. 625630, 2006. [11] E. philippot, a. Ibanez, a. Goiffon, M. cochez, a. Zarka, B. capell, J. schwartzel, and J. detaint, a quartz-like material: Gallium phosphate Gapo4: crystal growth and characterization, J. Cryst. Growth, vol. 130, no. 12, pp. 195208, 1993. [12] p. Krempl, G. schleinzer, and W. Wallnofer, Gallium phosphate, Gapo4: a new piezoelectric crystal material for high temperature sensors, Sens. Actuators A, vol. 61, no. 13, pp. 361363, 1997. [13] r. d. shannon, revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides, Acta Crystallogr. A, vol. 32, no. 5, pp. 751767, 1976. [14] F. p. yu, s. J. Zhang, X. Zhao, s. y. Guo, X. l. duan, d. r. yuan, and T. r. shrout, Investigation of the dielectric and piezoelectric properties of reca4o(Bo3)3 crystals, submitted for publication. [15] F. p. yu, s. J. Zhang, X. Zhao, d. r. yuan, c. M. Wang, and T. r. shrout, characterization of neodymium calcium oxyborate piezoelectric crystal with monoclinic phase, Cryst. Growth Des., vol. 10, no. 4, pp. 18711877, 2010. [16] IEEE Standard on Piezoelectricity, ansI/IEEE standard 176, 1987. [17] B. H. T. chai, a. n. p. Bustamante, and M. chou, a new class of ordered langasite structure compounds,in IEEE Int. Frequency Control Symp., 2000, pp. 163168. [18] s. J. Zhang, y. q. Zheng, H. K. Kong, J. Xin, E. Frantz, and T. r. shrout, characterization of high temperature piezoelectric crystals with an ordered langasite structure, J. Appl. Phys., vol. 105, no. 11, art. no. 114107, 2009. [19] a. G. cockbain and p. J. Harrop, The temperature coefficient of capacitance, Br. J. Appl. Phys., vol. 1, no. 9, pp. 11091115, 1968.

Fig. 7. piezoelectric coefficient (d26) for various recoB crystals as a function of temperature (small inset gives the room-temperature d26 values).

factors k26, the piezoelectric coefficients d26 were calculated and plotted as function of temperature, given in Fig. 7. The largest d26 value (15.8 pc/n at room temperature) was found for prcoB crystals, decreasing with increasing temperature up to 1000c, showing a variation of 17%. relatively low d26 values were determined for ErcoB (7.6 pc/n) and ycoB (7.8 pc/n) crystals, slightly increasing with increasing temperature, exhibiting variations of 20 to 25% over the temperature range. of particular significance is that the piezoelectric coefficient (d26) of GdcoB crystals was found to be nearly temperature independent, being on the order of 11.5 pc/n at room temperature, with less than 5% variation at 1000c. IV. summary The electrical resistivity, dielectric, and electromechanical properties of recoB (re: Er, y, Gd, sm, nd, pr, and la) piezoelectric crystals as a function of temperature were investigated up to 1000c. The highest resistivity was observed for ErcoB and ycoB crystals, being on the order of > 3.0 107 cm at 1000c. ndcoB exhibited high electromechanical coupling factor k26 (24.6%) and piezoelectric coefficient d26 (12.6 pc/n at 1000c). prcoB also exhibited high electromechanical coupling factor k26 (24.7%) and piezoelectric coefficient d26 (13.1 pc/n at 1000c). Their usable temperature ranges were limited by their low resistivity and high dielectric loss at elevated temperature, induced by their disordered crystal structure. compared with smcoB, ndcoB, prcoB, and lacoB crystals, ErcoB, ycoB, and GdcoB were found to offer greater stability of the electromechanical properties over the temperature range of 20 to 1000c. The low dielectric loss (<46%), high mechanical quality factor (>1500) and electrical resistivity at 1000c, together with

yu et al.: properties of rare earth calcium oxyborate crystals at high temperature [20] d. K. Kwon, Ultra-low temperature processing of barium tellurate dielectrics, ph.d. dissertation, Materials science and Engineering dept.,The pennsylvania state University, 2006. [21] p. J. Harrop, Temperature coefficients of capacitance of solids, J. Mater. Sci., vol. 4, no. 4, pp. 370374, 1969. [22] a. B. Ilyukhin and B. F. dzhurinskii, crystal structure of binary oxoborates lnca4o(Bo3)3 (ln=Gd, Tb, and lu) and Eu2cao(Bo3)2, Russ. J. Inorg. Chem., vol. 38, no. 6, pp. 917920, 1993.

873

[23] F. p. yu, s. J. Zhang, X. Zhao, d. r. yuan, q. M. Wang, and T. r. shrout, Zero temperature coefficient of frequency crystal cuts in monoclinic ndca4o(Bo3)3 piezoelectric crystals, Phys. Status SolidiRRL, vol. 4, no. 89, pp. 185187, 2010. [24] F. p. yu, s. J. Zhang, X. Zhao, d. r. yuan, q. M. Wang, and T. r. shrout, 6 MHz BaW resonators fabricated using new piezoelectric crystals prca4o(Bo3)3 and ndca4o(Bo3)3, Phys. Status Solidi RRL, vol. 5, no. 23, pp. 4749, 2011.