- freely available
Crystals 2014, 4(3), 241-261; doi:10.3390/cryst4030241
Published: 8 July 2014
Abstract: Rare-earth calcium oxyborate crystals, ReCa4O(BO3)3 (ReCOB, Re = Er, Y, Gd, Sm, Nd, Pr, and La ), are potential piezoelectric materials for ultrahigh temperature sensor applications, due to their high electrical resistivity at elevated temperature, high piezoelectric sensitivity and temperature stability. In this paper, different techniques for ReCOB single-crystal growth are introduced, including the Bridgman and Czochralski pulling methods. Crystal orientations and the relationships between the crystallographic and physical axes of the monoclinic ReCOB crystals are discussed. The procedures for dielectric, elastic, electromechanical and piezoelectric property characterization, taking advantage of the impedance method, are presented. In addition, the maximum piezoelectric coefficients for different piezoelectric vibration modes are explored, and the optimized crystal cuts free of piezoelectric cross-talk are obtained by rotation calculations.
High temperature sensors are desirable in aerospace and automotive industries for monitoring component conditions to optimize the propulsion system, with operations at temperatures up to 1000 °C, to enable safer, more fuel-efficient and more reliable vehicles; in addition, they are important for nondestructive in situ inspection of the structure health of the furnace component or systems in electric generation plants, to improve the safety and reduce life-cycle costs. Compared with the commercial strain gauge and optical fiber sensors, etc., piezoelectric sensors have greater potentials in realizing high temperature (>600 °C) sensing with the merits of high accuracy, fast response time and ease of integration [1,2,3,4].
Of all the investigated high temperature piezoelectric materials up to date, crystals in trigonal, tetragonal and monoclinic systems have been extensively investigated. Among these materials, the trigonal lithium niobate (LiNbO3, LN) crystals with 3m symmetry were reported to possess high piezoelectric coefficient, being on the order of 6–70 pC/N at room temperature, approximately 3–30 times that of commercial α-quartz (SiO2) (2–3 pC/N). However, the maximum operating temperature of LN-based piezoelectric devices, restricted by their low electrical resistivity (a requirement of >106 Ohm·cm was proposed for comparison, where the materials with low resistivity yet can be used for high frequency applications ) at elevated temperature is limited to <600 °C, though the Curie temperature is above 1150 °C . Other important trigonal piezoelectric crystals include the langasite family with the general formula of A3BC3D2O14 [6,7,8,9,10,11,12] and gallium orthophosphate GaPO4, in the point group of 32 [13,14,15,16,17,18,19], these crystals were reported to show modest piezoelectric coefficients (5–7 pC/N) and high melting points (1300–1500 °C for langasite family crystals and ~1670 °C for GaPO4), prior to which, there are no phase transitions observed for langasite family crystals (the phase transition for GaPO4 is about 970 °C). However, the costly component Ga2O3 restricted their further implements. The newly developed Ca3TaAl3Si2O14 (CTAS) crystals, substituting the Ga with Al elements, were found to possess improved higher temperature properties than La3Ga5SiO14 (LGS) and to significantly decrease the cost of raw materials; nevertheless, the crystal quality needs to be improved, due to the core defect observed inside the crystals . The tetragonal melilite crystals (point group 42m, such as SrLaGa3O7 (SLG), Ca2Al2SiO7 (CAS), etc.) and fresnoite crystals (point group 4mm, such as Ba2TiSi2O8) were investigated for piezoelectric applications. These crystals show the merits of high melting points (1400–1700 °C) and high effective piezoelectric coefficients deff (5–18 pC/N) [20,21,22,23,24,25,26]; the evaluations of the temperature dependence of dielectric, piezoelectric and electromechanical properties, however, are limited. Of particular significance is that the monoclinic rare-earth calcium oxyborate crystals (ReCa4O(BO3)3, ReCOB, Re: rare earth), which have been extensively investigated for nonlinear optical applications in the last two decades [27,28,29,30,31,32,33], were reported to exhibit good piezoelectric properties and high electrical resistivity at an elevated temperature of 1000 °C, with no phase transition prior to their melting points (~1400–1520 °C) [1,2,3,34,35,36,37,38].
Table 1 summarizes the basic characteristics of various high temperature piezoelectric crystals in monoclinic, trigonal and tetragonal systems, where the monoclinic ReCOB crystals were found to exhibit relatively high melting points, as well as relatively large piezoelectric coefficients, promising high temperature piezoelectric sensor applications.
In this review article, crystal growth, dielectric, elastic and piezoelectric property characterizations of the monoclinic ReCOB crystals are surveyed. Different crystal growth techniques, including the Bridgman and Czochralski (Cz) pulling methods, are discussed in Section 2. The crystal orientation related to the physical axes and crystallographic axes for electro-elastic property investigations is studied in Section 3. In Section 4, characterizations of the dielectric, elastic and piezoelectric properties of ReCOB crystals are reviewed. In Section 5, the maximum piezoelectric coefficients for different crystal cuts and the optimized crystal cuts free of cross-talk are discussed. Finally, the significance and challenges of ReCOB crystals are summarized; future research is proposed in Section 6.
|Table 1. A comparison of different high temperature piezoelectric crystals. LGS, La3Ga5SiO14; CTGS, Ca3TaGa3Si2O14; CTAS, Ca3TaAl3Si2O14; SLG, SrLaGa3O7; CAS, Ca2Al2SiO7; BTS, Ba2TiSi2O8; ReCOB, ReCa4O(BO3)3.|
|Symmetry||Crystals||Growth Method||Tc/Tm (°C)||deff (pC/N)|
|GaPO4||Flux/hydrothermal||970  #||~5|
|Tetragonal||SLG||Cz||~1650 ||~14 |
Notes: Cz, Czochralski pulling method; # α–β phase transition temperature.
2. Crystal Growth
2.1. Polycrystalline Preparation
The ReCOB polycrystalline materials were prepared by high purity (99.99%) CaCO3, Re2O3 (Pr6O11) and H3BO3 powders. They were weighed according to their nominal compositions. Considering the evaporation of B2O3 during crystal growth, an excess of H3BO3 (1–3 wt%) was added to the starting components, which will benefit the crystal growth [38,45,46]. The starting materials were mixed completely, followed by the calcination ~1000 °C for 5–10 h to decompose the H3BO3 and CaCO3, after which, the calcined powders were ground, remixed and then pressed into tablets to fabricate ReCOB polycrystalline components at 1100–1200 °C for 10–20 h; the solid state reaction follows the equation below:
2.2. Approaches for ReCOB Crystal Growth
Different techniques have been applied for ReCOB crystal growth, including the high temperature flux, Bridgman and Cz approaches [47,48,49]. At the early stage of ReCOB crystal studies, the high temperature flux method was adopted for the crystal growth, where the selection of appropriate flux agent (high temperature solvent) is vital, especially for the crystals with incongruent features. Among ReCOB crystals (except CeCOB and YbCOB), ErCOB, YCOB, GdCOB, SmCOB, NdCOB, PrCOB and LaCOB are congruent melting compounds, while TbCOB and TmCOB were found to possess a very narrow congruent region. Lead oxide was firstly selected as the flux agent for ReCOB crystal growth, with limited success, where the grown crystals were at centimeter scale . Later, the Bridgman and Cz methods, which are favorable for growing crystals with congruent melting features, were utilized. In the following, the growth of ReCOB crystals by the Bridgman and Cz methods is introduced.
2.2.1. Bridgman Method
The Bridgman method, which is also called the Bridgman-Stockbarger method, involves heating polycrystalline materials in a platinum or iridium crucible above its melting point and slowly cooling it from one end, where an oriented seed crystal is located. The crucible is translated from the high temperature region to the low temperature region at a special designed speed; the single crystal is progressively formed along the length of the crucible. Figure 1 shows a schematic set-up of the Bridgman growth system.
By the Bridgman method , the feed materials were prepared by thoroughly mixing the stoichiometric oxides, which were charged into a cylindrical platinum crucible. The material was heated to about 50 °C above its melting point, maintained for more than 10 h to make a homogeneous melt. The seeding process (along the <010> or <001> orientation) was performed by adjusting the crucible position and furnace temperature gradient, so that only the top part of the seed was melted. Growth was then driven by lowering the crucible at a rate of 0.2–0.6 mm/h, and the temperature gradient near the solid/liquid interface was normally kept at 30–50 °C/cm. Recently, large YCOB crystals with a diameter up to 3–4 inches have been reported, using the modified Bridgman furnace .
2.2.2. Cz Pulling Method
Cz method is named after Polish scientist, Jan Czochralski, who invented this method in 1916. In the Cz pulling technique, iridium, platinum, molybdenum and graphite crucibles are generally selected and heated in a low–medium radio-frequency furnace. Particularly, for ReCOB crystal growth, an iridium crucible is mostly utilized, due to its high melting point (~2450 °C) and chemical inertia to the raw materials. Figure 2 gives the schematic set-up of the Cz pulling system.
YCOB and GdCOB single crystals have been grown by the Cz method [27,33,49]. ReCOB materials were melted and kept 30–80 °C above their respective melting points for more than 10 h to ensure the homogeneity of the melts. A <010>-oriented crystal seed was selected for the growth, which will benefit the large diameter crystals. The pulling speed was controlled at 0.4–2.0 mm/h, and the rotation speed was varied from 10 to 30 rpm during the crystal growth. When the growth was finished, the crystal was cooled down to room temperature at a low rate of 10–50 °C/h, to avoid the crystal cracks induced by inner thermal stress. Figure 3 shows the large YCOB single crystals grown by the Cz method (Figure 3a,c) and the Bridgman method (Figure 3b) with a diameter being on the order of 3–4 inches. The obtained crystals were reported to possess X-ray diffraction with a very low full-width at half maximum (FWHM) (~30ʺ)  and high optical homogeneity (10−6) , exhibiting high crystal quality.
3. Orientation of Monoclinic ReCOB Crystals
ReCOB are monoclinic biaxial crystals belonging to the point group m. Therefore, three different orientation systems exist due to the crystal symmetry, including the crystallographic, optical and physical systems. For piezoelectric characterizations, the relationship between the crystallographic and physical axes should be determined, where the physical Y-axis is parallel to the crystallographic b-axis, Z- to the c-axis, and the X-axis is perpendicular to the Y and Z axes to form a right-hand orthogonal system according to the IEEE Standard on Piezoelectricity , as shown in Figure 4.
The initial orientation step is to verify the (010), (201) an (101) faces using X-ray analysis, possessing relatively strong diffraction peaks, from which, the crystallographic axes, a, b and c, can be determined according to the relationships between the interfacial angle and crystallographic plane. Then, the physical axes can be easily determined based on the IEEE standards. Taking YCOB crystals, for example, the angle between the Z-axis and (101) face was calculated to be around 57.1°, while the angle between the X-axis and (201) face was close to 34.6° (Figure 4). It is noteworthy that these angles (interfacial angles, etc.) are varied for different ReCOB crystals, due to their different lattice parameters (Table 2). After the orientation of the X, Y and Z axes, the positive X and positive Z axes can be further confirmed by using a quasi-static piezoelectric d33 meter, according to the IEEE Standard on Piezoelectricity .
|Table 2. Unit cell parameters and interfacial angles for different ReCOB crystals in space group Cm.|
|Parameters (Å/Å3/°) *||a||8.068||8.075||8.078||8.072||8.104||8.114||8.145||8.177||8.173|
|Formula weight *||521.33||519.74||441.65||511.33||509.99||502.78||496.98||493.33||491.68|
|∠1 (°) #||112.59||112.45||112.46||112.41||112.26||111.99||111.78||111.66||111.62|
|∠2 (°) #||34.74||34.70||34.77||34.75||34.85||34.94||35.08||35.14||35.14|
|∠3 (°) #||45.85||46.13||45.96||46.00||46.10||46.32||46.45||46.54||46.57|
* PDF #: 00-050-0403 (YCOB); 01-077-0951 (GdCOB); 01-079-1378 (SmCOB); 00-050-0399 (NdCOB); 01-070-7385 (LaCOB); TmCOB ; TbCOB ; PrCOB ; # ∠1: the interfacial angle between (101) and (201); ∠2: the interfacial angle between (201) and the X-axis; ∠3: the interfacial angle between (201) and (001).
4. Electro-Elastic Material Constants Determination
Due to the crystal symmetry, there are two different sets of electro-elastic component matrix for monoclinic crystal, relating to point group m and point group 2. The piezoelectric crystals in point group 2 possess eight independent piezoelectric strain coefficients dij, while crystals in point group m exhibit ten independent piezoelectric strain coefficients dij, four dielectric permittivities εij and thirteen elastic compliances sij. The electro-elastic component matrix for piezoelectric crystals in point group m can be written as:
Taking advantage of the impedance method based on the IEEE standard, all of the electro-elastic parameters for ReCOB crystals can be determined. Meanwhile, the elastic stiffness cij and piezoelectric stress coefficient eij can be obtained based on the determined elastic compliance sij and piezoelectric strain coefficient dij, following the equations below:
Based on the IEEE standard , the dielectric permittivities εii (i = 1, 2 and 3) can be evaluated by measuring the capacitance of X-, Y- and Z-cut square plates, respectively. Piezoelectric d11 and d33 can be obtained by measuring the longitudinal vibration mode of the X and Z rods, while elastic compliances sii (i = 1–6) can be calculated from the extensional and shear vibration modes, relating to the piezoelectric coefficient d12, d13, d15, d24, d26, d31, d32, d33 and d35. On the contrary, the dielectric cross permittivity ε13 and elastic cross compliances sij (i ≠ j; i, j = 1–6) can be evaluated by employing oblique crystal cuts that do not lie along or normal to any of the three physical axes. Figure 5 presents different crystal cuts designed for the electro-elastic parameter determination, including the dielectric permittivities, elastic compliances and piezoelectric coefficients. The aspect ratios of the samples (X-, Y- and Z-square plates) for dielectric measurement ranged from 1:8:8 to 1:10:10, whereas for elastic measurement, rectangular samples were used with aspect ratios, t (thickness):w (width):l (length), ranging from 1:2:10 to 1:3:15 and an orientation accuracy <30ʺ. For each crystal cut, 3–5 pieces of samples were prepared for parameter determination.
4.1. Dielectric Permittivity
ReCOB crystals possess four independent dielectric permittivities, where the dielectric permittivities ε11, ε22, ε33 can be determined from X-, Y-, and Z-cut samples (k, l and j), while for the determination of ε13, sample (g) was used (Table 3), following the formulae below:
|Table 3. A summary of different crystal cuts for material constants’ determination, reprinted with permission from . Copyright 2014 Wiley-VCH.|
|Crystal Cuts||Modes||Material constants|
|X rod (a)||longitudinal extension||d11|
|Z rod (b)||d33|
|ZX plate (f)||transverse extension||s11, d31,|
s22, d12, d32,
|XY plate (d)|
|ZY plate (e)|
|XZ plate (c)|
|XZ plate (c)||width shear *||s44, d24|
|ZX plate (f)||s66, d26|
|XZ plate (c)||thickness shear||s55, d15, d35|
|ZX plate (f)|
|(XZw)45° (g)||transverse extension||s13, s15, s35|
|(XYt)45° (m)||transverse extension||s12, s23, s25|
|X cut (k)||–||ε11, ε22, ε33, ε13|
|Y cut (l)|
|Z cut (j)|
* d24 (d223) and d26 (d212) are thickness shear vibration modes; however, XZ and ZX cut samples with electrodes on the Y faces were used to determine their values, due to the achievable clean d24/d26 vibration modes using the impedance method.
4.2. Piezoelectric Coefficients and Elastic Compliances
For determining the complete set of elastic compliances, piezoelectric coefficients, as well as electromechanical coupling factors, crystal cuts with different orientations were designed, as given in Figure 5. In addition, different crystal cuts with corresponding piezoelectric vibration modes and electro-elastic parameters are summarized in Table 3.
4.2.1. Piezoelectric Coefficients d11 and d33
Piezoelectric coefficients d11, d33 and elastic compliances s11 and s33 were determined using the longitudinal mode of X and Z rods (samples (a) and (b)), relating to the equations below:
4.2.2. Piezoelectric Coefficients d12, d13, d31, and d32
Using the transverse extensional mode of XY, XZ, ZX and ZY crystal cuts (samples (c)–(e)), piezoelectric coefficients d12, d13, d31 and d32 and elastic compliances s22, s33 and s11 were calculated by Equations (9)–(11).
4.2.3. Piezoelectric Coefficients d15, d35, d24, and d26
d15, d35, d24 and d26 are thickness shear piezoelectric coefficients; thus, XZ and ZX crystal cuts (samples (c) and (f)) with electrodes on the X and Z faces, respectively, were designed for piezoelectric d15 and d35 and elastic compliance s55 evaluation. However, for the piezoelectric d24 and d26 and elastic compliance s44 and s66 determinations, XZ and ZX cut samples with an electrode on the Y faces were used (equivalent to YZ and YX cut samples with an electrode on Y faces), due to the fact that clean width shear vibrations can be obtained. The shear piezoelectric coefficients d15, d35, d24 and d26 and elastic compliances of s55, s44 and s66 can be determined by using Equations (8), (9), (12) and (13).
4.2.4. Elastic Compliances s12, s13, s15, s23, s25, s35 and s46
Except the dielectric, piezoelectric and elastic constants above, there are cross-elastic compliances s12, s13, s15, s23, s25, s35 and s46 remaining unsolved, requiring the oblique crystal cuts. Crystal cuts (g–i) with transverse extensional modes were employed to determine the elastic compliances s13, s15 and s35, based on Equations (10) and (14), while for the compliance s23, s12 and s25 evaluations, crystal cuts (m–o) were designed, combining Equations (10) and (15)–(17). Particularly, the elastic compliance s46 was obtained using Equations (13) and (18) by measuring the shear vibration mode of sample (g).
|Table 4. Dielectric, piezoelectric and elastic constants of ReCOB (Re = Er, Y, Gd, Nd, Pr and La) crystals.|
|Elastic Compliances sEij (pm2/N)|
|Relative Dielectric Permittivities εTij/ε0|
|Piezoelectric Coefficients dij (pC/N)|
|PrCOB||2.5 *||3.9||−5.2||−1.9||3.1||15.8||−1.5||−2.5||2.0 *||3.3|
|LaCOB||2.4 *||4.7||–||–||4.0||11.8||–||–||2.0 *||–|
4.2.5. Determination of the Sign of the Piezoelectric Coefficients
According to the IEEE standard , the longitudinal piezoelectric d11 and d33 are positive, while the transverse and shear piezoelectric coefficients are either positive or negative. Therefore, more crystal cuts (rotated around physical axes) are desired to discuss the sign of the piezoelectric coefficient dij (i ≠ j) for ReCOB crystals. In this subsection, piezoelectric coefficients for YCOB a in Table 4 are discussed.
It is noticed that the piezoelectric d35 is a function of d11, d13, d31, d33 and d15 when rotated around the Y-axis, as expressed below:
Figure 6 shows the variation of piezoelectric d35 for YCOB crystals as a function of the rotation angle around the Y-axis (curve (a) in Figure 6). For verification, the experimental shear piezoelectric d35 values measured from rotated crystal cuts (ZXw)θ (θ = −60°, −30°, 30° and 60°) were plotted and found to be in good agreement with the calculations, from which, the maximum d35 value was determined to be on the order of 6.4 pC/N for (ZXw)−55° crystal cuts. In addition, different d35 curves plotted by presuming the opposite sign of the related piezoelectric coefficients in Equation (19) were given as curves (b)–(g), where large discrepancies were observed. The consistency between the calculation and measurement of d35 values for YCOB crystals indicates the validity of the reported piezoelectric coefficients d11, d13, d31, d33, d15 and d35.
Similarly, the variations of piezoelectric d31, d32, d33 and d35 for different crystal cuts rotated around the Y-axis were plotted and compared in Figure 7, where piezoelectric d31 was selected for verifications by measuring the transverse extensional modes of different (ZXw)θ crystal cuts (θ = −60°, −45°, −30°, 30° and 60°). The piezoelectric coefficients were determined by Equations (9)–(11), and the results were plotted in Figure 7. It is noted that the measured for different crystal cuts is in good agreement with the calculated results (Equation (20)).
5. The Investigation of Optimum Crystal Cuts
According to the crystal symmetry, ReCOB crystals possess two independent longitudinal piezoelectric coefficients (d11 and d33), four transverse piezoelectric coefficients (d12, d13, d31 and d32) and four thickness shear piezoelectric coefficients (d15, d35, d24 and d26). For piezoelectric sensing applications, various crystal cuts with different piezoelectric vibration modes might be utilized, including the longitudinal (compression) and shear vibration modes, etc. Therefore, it is necessary to discuss the optimum crystal cuts with a high piezoelectric coefficient and free of piezoelectric cross-talk.
5.1. Rotated Crystal Cuts with Maximized Values
It is noticed that the maximum values of longitudinal piezoelectric d11 and d33 for ReCOB crystals should be equal, due to the fact that the Z rods (d33) can be obtained by the rotation of X rods around the Y-axis for −90°, analogous to the thickness shear piezoelectric d15 (d35) and d26 (d24). Similarly, the transverse piezoelectric d12 and d13, d31 and d32 should be equal from the viewpoint of crystal cut rotation. Equations (21)–(25) reveal the relationships between d11 and d33, d15 and d35, d26 and d24, d12 and d13 and d31 and d32. Evidently, the effective piezoelectric coefficients , and equal to d33, d35 and d24, respectively, when rotated around the Y-axis for ±90°. Meanwhile, when rotated around the X- and Z-axes for ±90°, and equal to d13 and d32, respectively.
Therefore, the orientation dependence of the longitudinal piezoelectric d11, transverse piezoelectric d12 and d31 and thickness shear piezoelectric coefficients d15 and d26 for YCOB crystals were discussed (data refer to YCOB a in Table 4). The maximum d11 (4.9 pC/N) was obtained from the X plate rotated 1° around the X-axis and then rotated 52° around the Z-axis, whereas the maximum d12 and d31 were observed for (XYl)33° and (ZXlt)90°/123°, respectively, being on the order of ~4.6 pC/N. Meanwhile, the highest piezoelectric d15 (9.0 pC/N) was obtained for (XZlt)90°/60° crystal cuts, and the maximum piezoelectric d26 (9.0 pC/N) was achieved in (YXlt)180°/30° [(YXt)-30°] crystal cut, as reported in . The crystal cuts with maximum d11, d12, d31 and d15 (the same as d26) values are illustrated in Figure 8a–d, respectively.
For comparison, the maximum values of shear piezoelectric coefficient d26 for different ReCOB crystals were studied based on the determined piezoelectric d24 and d26 values; results are given in Table 5, where PrCOB crystals were found to possess the maximum shear piezoelectric d26 value, being on the order of 16.1 pC/N, nearly two times that of ErCOB crystals. The increase of the piezoelectric coefficient for ReCOB crystals was reported to be associated with the difference of the diameter of rare-earth cations (Re3+) and the disorder distribution of Ca2+ and Re3+ ions in ReCOB crystals [34,47].
|Table 5. Optimum crystal cuts (d26 mode) obtained for ReCOB crystals at room temperature.|
|Crystals||d24 (pC/N)||d26 (pC/N)||Crystal Cuts||Maximum d26 (pC/N)|
5.2. Rotated Crystal Cuts without Piezoelectric Cross-Talk
For ideal piezoelectric sensors, only the output (charge, current or voltage) is desired when they are loaded (such as force, vibration, pressure or acceleration) along their sensitivity axis; meanwhile, the load normal to that axis should not produce any output. However, real sensors may give an output also to a force normal to their sensitive axis, which may have significant influence on the accuracy of the measuring results, this is called cross-talk (transverse sensitivity) . The cross-talk effect can be weakened or reduced by device structure design; however, minimizing the piezoelectric cross-talk by using the crystal cut design is desirable for improving the accuracy of the sensors. In the following subsection, piezoelectric cross-talk for the longitudinal modes (d11) and thickness shear modes (d15 and d26) were discussed, based on the piezoelectric coefficients of YCOB crystals (YCOB a in Table 4).
The X plates or X rods with the first 130° rotation angle around the Y-axis and the second 225° rotation angle around the X-axis exhibit a relatively good longitudinal piezoelectric response, giving an effective piezoelectric coefficient d11 being on the order of ~3.0 pC/N, while other coefficients were found to be −0.8~−1.2 pC/N.
Interestingly, the thickness shear piezoelectric d15 and d26 were found to possess optimal crystal cuts with negligible piezoelectric cross-talk. Figure 9 presents the variation of piezoelectric coefficients d1j (j = 1–6) for (XZlw)45°/θ crystal cuts, where the optimal crystal cut was achieved for (XZlw)45°/35°, of which, the shear piezoelectric coefficient d15 was determined to be on the order of 8.8 pC/N, with minimized d11, d12, and d13 being close to zero, d14 and d16 < 2.0 pC/N.
Figure 10 gives the variation of piezoelectric coefficients d24 and d26 as a function of rotation angle around the Y-axis, based on the determined piezoelectric coefficients d24 (4.4 pC/N) and d26 (7.9 pC/N) for YCOB listed in Table 5. It was found that the (YXt)330° crystal cut, which equals to the crystal cut (YXt)−30°, possess the maximum d26 value, being around 9.0 pC/N, with zero piezoelectric d24 value, demonstrating free piezoelectric cross-talk. On the contrary, the highest piezoelectric d24 (9.0 pC/N) was achieved from the (YXt)60° crystal cut, with the d26 value being zero. Of particular importance is that these crystal cuts were found to possess the maximum thickness shear piezoelectric coefficients, without the interference from other piezoelectric vibrations, due to the fact that the monoclinic symmetry plane is vertical to the Y-axis.
6. Summary and Future Research
6.1. Significance of ReCOB Crystals
The monoclinic ReCOB crystals are promising materials for high temperature piezoelectric sensing. The desirable material merits include the low-cost, reproducible crystals with high quality and large dimension, high piezoelectric coefficient, high electrical resistivity, as well as the high thermal stability of the piezoelectric and electromechanical properties, etc. Relevant to this paper, crystal growth and piezoelectric characterization were discussed. Then Bridgman and Cz methods for ReCOB crystal growth were introduced. The relationship between the crystallographic axes and physical axes for ReCOB was discussed for piezoelectric property determination. In addition, procedures for the characterization of the dielectric, elastic and piezoelectric parameters were established, the independent electro-elastic constants were determined, where the highest piezoelectric coefficients d26 were achieved, being on the order of 7.6, 7.9, 11.5, 12.7, 15.0, 15.8 and 11.8 pC/N for ErCOB, YCOB, GdCOB, SmCOB, NdCOB, PrCOB and LaCOB, respectively. Of particular significance is that (YXt)θ crystal cuts not only possess maximum d26 coefficients, but also exhibit no cross-talk from other piezoelectric vibrations.
6.2. Future Research
ReCOB piezoelectric crystals are potential materials for high temperature sensor applications. However, several challenges remain for future investigations, including: (1) temperature stability evaluation of the electro-elastic properties, to explore the optimized ReCOB crystals with high thermal stability; (2) structure-property investigation of ReCOB crystals for further improving of the properties at elevated temperatures; and (3) reliability testing of the electro-elastic properties under harsh environments, including high temperature, hard radiation (Gamma and neutron radiations), low oxygen partial pressure, high/low pressure and corrosive/erosive conditions, etc.
Thomas R. Shrout from Pennsylvania State University is acknowledged for the helpful discussions. Shiyi Guo from Shandong University is thanked for his kind helps during ErCOB crystal growth. Fapeng Yu and Xian Zhao would like to thank the National Natural Science Foundation of China (Grant Nos. 91022034, 51202129, 51372168) and the Natural Science Foundation of Shandong Province (ZR2012EMQ004). This work is also supported by the China postdoctoral Science Foundation (2012M511019).
Fapeng Yu grew the ReCOB single crystals and evaluated their dielectric and piezoelectric properties. Xiulan Duan studied the crystal structures. Qingming Lu prepared the crystal cuts of different ReCOB crystals for property characterization. Shujun Zhang and Xian Zhao directed this research. Fapeng Yu and Xiulan Duan prepared the manuscript. All the authors contributed to revising the manuscript.
Conflicts of Interest
The authors declare no conflict of interest.
- Zhang, S.J.; Yu, F.P. Piezoelectric materials for high temperature sensors. J. Am. Ceram. Soc. 2011, 94, 3153–3170. [Google Scholar] [CrossRef]
- Zhang, S.J.; Jiang, X.N.; Lapsley, M.; Moses, P.; Shrout, T.R. Piezoelectric accelerometers for ultrahigh temperature application. Appl. Phys. Lett. 2010, 96. [Google Scholar] [CrossRef]
- Zhang, S.J.; Frantz, E.; Xia, R.; Everson, W.; Randi, J.; Snyder, D.W.; Shrout, T.R. Gadolinium calcium oxyborate piezoelectric single crystals for ultrahigh temperature (>1000 °C) applications. J. Appl. Phys. 2008, 104. [Google Scholar] [CrossRef]
- Jiang, X.N.; Kim, K.; Zhang, S.J.; Johnson, J.; Sakazar, G. High-temperature piezoelectric sensing. Sensors 2014, 14, 144–169. [Google Scholar]
- Shrout, T.R.; Eitel, R.; Randall, R.A. High performance, high temperature perovskite piezoelectric ceramics. In Piezoelectric Materials in Devices; EPFL Swiss Federal Institute of Technology: Lausanne, Switzerland, 2002. [Google Scholar]
- Fritze, H.; Schneider, O.; She, H.; Tuller, H.L.; Borchardt, G. High temperature bulk acoustic wave properties of langasite. Phys. Chem. Chem. Phys. 2003, 5, 5207–5214. [Google Scholar] [CrossRef]
- Zhang, S.J.; Zheng, Y.Q.; Kong, H.K.; Xin, J.; Frantz, E.; Shrout, T.R. Characterization of high temperature piezoelectric crystals with an ordered langasite structure. J. Appl. Phys. 2009, 105. [Google Scholar] [CrossRef]
- Yu, F.P.; Zhao, X.; Pan, L.H.; Yuan, D.R.; Zhang, S.J. Investigation of zero temperature compensated cuts in langasite-type piezocrystals for high temperature applications. J. Phys. D Appl. Phys. 2010, 43. [Google Scholar] [CrossRef]
- Hornsteiner, J.; Born, E.; Riha, E. Langasite for high temperature surface acoustic wave applications. Phys. Status Solidi A 1997, 163, R3–R4. [Google Scholar] [CrossRef]
- Sauerwald, J.; Richter, D.; Ansorge, E.; Schmidt, B.; Fritze, H. Langasite based miniaturized functional structures: Preparation, high-temperature properties and applications. Phys. Status Solidi A 2011, 208, 390–403. [Google Scholar]
- Yu, F.P.; Zhang, S.J.; Zhao, X.; Yuan, D.R.; Qin, L.F.; Wang, Q.M.; Shrout, T.R. Investigation of Ca3TaGa3Si2O14 piezoelectric crystals for high temperature sensors. J. Appl. Phys. 2011, 109. [Google Scholar] [CrossRef]
- Xin, J.; Zheng, Y.Q.; Kong, H.K.; Chen, H.; Tu, X.N.; Shi, E.W. Growth of a new ordered langasite structure crystal Ca3TaAl3Si2O14. Cryst. Growth Des. 2008, 8, 2617–2619. [Google Scholar]
- Fritze, H. High-temerature bulk acoustic wave sensors. Meas. Sci. Technol. 2011, 22. [Google Scholar] [CrossRef]
- Fritze, H. High-temerature piezoelectric crystals and devices. J. Electroceram. 2011, 26, 122–161. [Google Scholar] [CrossRef]
- Li, J.; Liang, X.M.; Xu, G.G.; Zhao, H.Y.; Wang, J.Y. Flux growth of GaPO4 crystal. Piezoelectr. Acoustrooptocs. 2007, 29, 695–696. [Google Scholar]
- Philippot, E.; Ibanez, A.; Goiffon, A.; Cochez, M.; Zarka, A.; Capelle, B.; Schwartzel, J.; Détaint, J. A quartz-like material: Gallium phosphate (GaPO4): Crystal growth and characterization. J. Cryst. Growth 1993, 130, 195–208. [Google Scholar] [CrossRef]
- Millichamp, J.; Ali, E.; Brandon, N.P.; Brown, R.J.C.; Hodgson, D.; Kalyvas, C.; Manos, G.; Brett, D.J.L. Application of a GaPO4 crystal microbalance for the detection of coke formation in high-temperature reactors and solid oxide fuel cells. Ind. Eng. Chem. Res. 2011, 50, 8371–8375. [Google Scholar] [CrossRef]
- Schiopu, P.; Cristea, I.; Grosu, N.; Cracium, A. Development of SAW filters based on GaPO4. In Proceedings of the 2011 IEEE 17th International Symposium for Design and Technology in Electronic Packaging (SIITME), Timisoara, Romania, 20–23 October 2011.
- Traon, O.L.; Masson, S.; Chartier, C.; Janiaud, D. LGS and GaPO4 piezoelectric crystals: New results. Solid State Sci. 2010, 12, 318–324. [Google Scholar] [CrossRef]
- Zhang, Y.Y.; Zhang, H.J.; Yu, H.H.; Sun, S.Q.; Wang, J.Y.; Jiang, M.H. Characterization of disordered melilite Nd:SrLaGa3O7 crystal. IEEE J. Quantum Electron. 2011, 47, 1506–1513. [Google Scholar] [CrossRef]
- Hagiwara, M.; Noguchi, H.; Hoshina, T.; Takeda, H.; Fujihara, S.; Kodama, N.; Tsurumi, T. Growth and characterization of Ca2Al2SiO7 piezoelectric single crystals for high temperature sensor applications. Jpn. J. Appl. Phys. 2013, 52. [Google Scholar] [CrossRef]
- Takeda, H.; Hagiwara, M.; Noguchi, H.; Hoshina, T.; Takahashi, T.; Kodama, N.; Tsurumi, T. Calcium aluminate silicate Ca2Al2SiO7 single crystal applicable to piezoelectric sensors at high temperature. Appl. Phys. Lett. 2013, 102. [Google Scholar] [CrossRef]
- Shen, C.; Wang, J.Y.; Zhang, H.J.; Yin, X.; Zhang, Y.Y.; Xu, H.H.; Han, S.J. Growth and determination of electro-elastic constants of Ba2TiSi2O8 crystal. J. Chin. Ceram. Soc. 2012, 40, 1311–1315. [Google Scholar]
- Kimura, M.; Fujino, Y.; Kawanura, T. New piezoelectric crystals: Synthetic fresnoite (Ba2Si2TiO8). Appl. Phys. Lett. 1976, 29, 227–228. [Google Scholar] [CrossRef]
- Halliyal, A.; Bhalla, A.S.; Markgraf, S.A.; Cross, L.E.; Newnham, R.E. Unusual pyroelectric and piezoelectric properties of fresoite (Ba2TiSi2O8) single crystal and polar glass-ceramics. Ferroelectrics 1985, 62, 27–38. [Google Scholar] [CrossRef]
- Kimura, M. Elastic and piezoelectric properties of Ba2Si2TiO8. J. Appl. Phys. 1977, 48, 2850–2856. [Google Scholar] [CrossRef]
- Mockel, R.; Reuther, C.; Gotze, J. REECOB: 20 years of rare earth element calcium oxoborates crystal growth research. J. Cryst. Growth 2013, 371, 70–76. [Google Scholar] [CrossRef]
- Furuya, H.; Yoshimura, M.; Kobayashi, T.; Murase, K.; Mori, Y.; Sasaki, T. Crystal growth and characterization of GdxY1−xCa4O(BO3)3 crystal. J. Cryst. Growth 1999, 198–199, 560–563. [Google Scholar] [CrossRef]
- Zhang, S.J.; Cheng, Z.X.; Lu, J.H.; Li, G.M.; Lu, J.R.; Shao, Z.S.; Chen, H.C. Studies on the effective nonlinear coefficient of GdCa4O(BO3)3 crystal. J. Cryst. Growth 1999, 205, 453–456. [Google Scholar] [CrossRef]
- Zhang, S.J.; Cheng, Z.X.; Zhang, S.J.; Han, J.R.; Sun, L.K.; Chen, H.C. Growth and noncritical phase-matching third-harmonic-generation of GdxY1−xCa4O(BO3)3 crystal. J. Cryst. Growth 2000, 213, 415–418. [Google Scholar] [CrossRef]
- Zhang, H.J.; Jiang, H.D.; Wang, J.Y.; Hu, X.B.; Yu, G.W.; Yu, W.T.; Gao, L.; Liu, J.A.; Zhang, S.J.; Jiang, M.H. Growth and characterization of a LaCa4O(BO3)3 crystal. Appl. Phys. A Mater. Sci. Proc. 2004, 78, 889–893. [Google Scholar] [CrossRef]
- Adams, J.J.; Ebbers, C.A.; Schaffers, K.I.; Payne, S.A. Nonlinear optical properties of LaCa4O(BO3)3. Opt. Lett. 2001, 26, 217–219. [Google Scholar] [CrossRef]
- Aka, G.; Kahn-Harari, A.; Mougel, F.; Vivien, D.; Salin, F.; Coquelin, P.; Colin, P.; Pelenc, D.; Damelet, J.P. Linear- and nonlinear-optical properties of a new gadolinium calcium oxoborate crystal, Ca4GdO(BO3)3. J. Opt. Soc. Am. B 1997, 14, 2238–2247. [Google Scholar] [CrossRef]
- Yu, F.P.; Zhang, S.J.; Zhao, X.; Guo, S.Y.; Duan, X.L.; Yuan, D.R.; Shrout, T.R. Investigation of the dielectric and piezoelectric properties of ReCa4O(BO3)3 crystals. J. Phys. D Appl. Phys.. [CrossRef]
- Kim, K.; Zhang, S.J.; Huang, W.B.; Yu, F.P.; Jiang, X.N. YCa4O(BO3)3 (YCOB) high temperature vibration sensor. J. Appl. Phys. 2011, 109. [Google Scholar] [CrossRef]
- Sotnikov, A.; Schmidt, H.; Weihnacht, M.; Zhang, S.J.; Shrout, T.R.; Yu, F.P. Elastic constants of YCa4O(BO3)3 and NdCa4O(BO3)3 single crystals by the pulse-echo ultrasonic method. In Proceedings of the 2012 IEEE International Ultrasonics Symposium (IUS), Dresden, Germany, 7–10 October 2012.
- Nakao, H.; Nishida, M.; Shikida, T.; Shimizu, H.; Takeda, H.; Shiosaki, T. Growth and SAW properties of rare-earth calcium oxoborate crystals. J. Alloys Compd. 2006, 408–412, 582–585. [Google Scholar]
- Yu, F.P.; Zhang, S.J.; Cheng, X.F.; Duan, X.L.; Ma, T.F.; Zhao, X. Crystal growth, structure and thermal properties of noncentrosymmetric single crystals PrCa4O(BO3)3. CrystEng Comm 2013, 15, 5226–5231. [Google Scholar] [CrossRef]
- Shimamura, K.; Takeda, H.; Kohnp, T.; Fukuda, T. Growth and characterization of lanthanum gallium silicate La3Ga5SiO14 single crystals for piezoelectric applications. J. Cryst. Growth 1997, 163, 388–392. [Google Scholar] [CrossRef]
- Wang, Z.M.; Yuan, D.R.; Cheng, Z.X.; Duan, X.L.; Sun, H.Q.; Shi, X.Z.; Wei, X.C.; Lü, Y.Q.; Xu, D.; Lü, M.K.; et al. Growth of a new ordered langasite structure compound Ca3TaGa3Si2O14 single crystal. J. Cryst. Growth 2003, 253, 398–403. [Google Scholar] [CrossRef]
- Armand, P.; Beaurain, M.; Ruffle, B.; Menaert, B.; Balitsky, D.; Clement, S.; Papet, P. Characterizations of piezoelectric GaPO4 single crystals grown by the flux method. J. Cryst. Growth 2008, 310, 1455–1459. [Google Scholar] [CrossRef]
- Warner, A.W.; Onoe, M.; Coquin, G.A. Determine elastic piezoelectric and dielectric properties of class 3m. J. Acoust. Soc. Am. 1967, 42, 1223–1231. [Google Scholar] [CrossRef]
- Terentiev, A.V.; Prokoshin, P.V.; Yumashev, K.V.; Mikhailov, V.P.; Ryba-Romanowski, W.; Golab, S.; Pisarski, W. Passive mode locking of a Nd3+:SrLaGa3O7 laser. Appl. Phys. Lett. 1995, 67, 2442–2444. [Google Scholar] [CrossRef]
- Zhang, Y.Y.; Yin, X.; Yu, H.H.; Cong, H.J.; Zhang, H.J.; Wang, J.Y.; Boughton, R.I. Growth and piezoelectric properties of melilite ABC3O7 crystals. Cryst. Growth Des. 2012, 12, 622–628. [Google Scholar] [CrossRef]
- Liu, Y.Q.; Wei, L.; Yu, F.P.; Wang, Z.P.; Zhao, Y.G.; Han, S.; Zhao, X.; Xu, X.G. Crystal growth and efficient second-harmonicgeneration of the monoclinic LaCa4O(BO3)3 crystal. CrystEng Comm 2013, 15, 6035–6039. [Google Scholar]
- Pan, Z.B.; Zhang, H.J.; Yu, H.H.; Wang, J.Y. Czochralski growth of large aperture YCOB crystal. J. Chin. Ceram. Soc. 2013, 41, 55–57. [Google Scholar]
- Ilyukhin, A.B.; Dzhurinskii, B.F. Crystal structures of binary oxoborates LnCa4O(BO3)3 (Ln = Gd, Tb, and Lu) and Eu2CaO(BO3)2. Russ. J. Inorg. Chem. 1993, 38, 917–920. [Google Scholar]
- Wu, A.H.; Jiang, L.W.; Qian, G.X.; Zheng, Y.Q.; Xu, J.; Shi, E.W. Bridgman growth of large-aperture yttrium calcium oxyborate crystal. Mater. Res. Bull. 2012, 47, 2689–2691. [Google Scholar] [CrossRef]
- Aka, G.; Kahn-Harari, A.; Vivien, D.; Benitez, J.M.; Salin, F.; Godard, J. A new nonlinear and neodymium laser self-frequency doubling crystal with congruent melting Ca4GdO(BO3)3, (GdCOB). Eur. J. Solid State Inorg. Chem. 1996, 33, 723–736. [Google Scholar]
- Luo, J.; Fan, S.J.; Xie, H.Q.; Xiao, K.C.; Qian, S.X.; Zhong, Z.W.; Qian, G.X.; Sun, R.Y.; Xu, J.Y. Thermal and nonlinear optical properties of Ca4YO(BO3)3. Cryst. Res. Technol. 2001, 36, 1215–1221. [Google Scholar] [CrossRef]
- Yu, F.P.; Duan, X.L.; Zhang, S.J.; Yu, Y.G.; Ma, T.F.; Zhao, X. Temperature dependence of electro-elastic properties of yttrium calcium oxyborate single crystals. In Proceedings of the 2012 Symposium on Piezoelectricity, Acoustic Waves and Device Applications, Shanghai, China, 23–25 November 2012.
- Zheng, Y.Q.; Wu, A.H.; Gao, P.; Tu, X.N.; Liang, X.Y.; Hou, J.; Yang, L.M.; Wang, T.; Qian, L.J.; Shi, E.W. Laser damage threshold and nonlinear optical properties of large aperture elements of YCOB crystal. In Proceedings of Pacific Rim Laser Damage 2011: Optical Materials for High Power Lasers, Shanghai, China, 12 January 2012.
- Fei, Y.T.; Chai, B.H.T.; Ebbers, C.A.; Liao, Z.M.; Schaffers, K.I.; Thelin, P. Large-aperture YCOB crystal growth for frequency conversion in the high average power laser system. J. Cryst. Growth 2006, 290, 301–306. [Google Scholar] [CrossRef]
- IEEE Standard on Piezoelectricity; ANSI/IEEE Standard. IEEE: New York, NY, USA, 1987.
- Liu, Y.Q.; Yu, F.P.; Wang, Z.P.; Hou, S.; Yang, L.; Xu, X.G.; Zhao, X. Bulk growth and nonlinear optical properties of thulium calcium oxyborate single crystals. CrystEng Comm 2014. [Google Scholar] [CrossRef]
- Yuan, D.S.; Jia, Z.T.; Wang, J.; Gao, Z.L.; Zhang, J.J.; Fu, X.W.; Shu, J.; Yin, Y.R.; Hu, Q.Q.; Tao, X.T. Bulk growth, structure, and characterization of the new monoclinic TbCa4O(BO3)3 crystal. CrystEngComm 2014, 16, 4008–4015. [Google Scholar] [CrossRef]
- Yu, F.P.; Hou, S.; Zhang, S.J.; Lu, Q.M.; Zhao, X. Electro-elastic properties of YCa4O(BO3)3 piezoelectric crystals. Phys. Status Solidi A 2014, 211, 574–579. [Google Scholar] [CrossRef]
- Shimizu, H.; Nishida, T.; Takeda, H.; Shiosaki, T. Dielectric, elastic and piezoelectric properties of RCa4O(BO3)3 (R = rare-earth elements) crystals with monoclinic structure of point group m. J. Cryst. Growth 2009, 311, 916–920. [Google Scholar] [CrossRef]
- Pawlaczyk, C.; Markiewiz, E.; Kłos, A.; Hofman, W.; Pajaczkowska, A. Elastic and piezoelectric properties of gadolinium calcium oxoborate GdCa4O(BO3)3 crystal. Phys. Status Solidi A 2006, 203, 2103–2118. [Google Scholar]
- Yu, F.P.; Zhang, S.J.; Zhao, X.; Yuan, D.R.; Wang, C.M.; Shrout, T.R. Characterization of neodymium calcium oxyborate piezoelectric crystal with monoclinic phase. Cryst. Growth Des. 2010, 10, 1871–1877. [Google Scholar] [CrossRef]
- Karaki, T.; Adachi, M.; Kuniyoshi, Y. Evaluation of material constants in NdCa4O(BO3)3 piezoelectric single crystal. J. Electroceram. 2008, 21, 823–826. [Google Scholar] [CrossRef]
- Shimizu, H.; Kodama, K.; Takeda, H.; Nishida, T.; Shikida, T.; Okamura, S.; Shiosaki, T. Evaluation of material constants and temperature properties in lanthanum calcium oxoborate LaCa4O(BO3)3 single crystals. Jpn. J. Appl. Phys. 2004, 43, 6716–6720. [Google Scholar] [CrossRef]
- Yu, F.P.; Zhang, S.J.; Zhao, X.; Yuan, D.R.; Wang, Q.M.; Shrout, T.R. High temperature piezoelectric properties of yttrium calcium oxyborate single crystals. Phys. Status Solidi R 2010, 4, 103–105. [Google Scholar]
- Gautschi, G. Piezoelectric Sensorics: Force, Strain, Pressure, Acceleration and Acoustic Emission Sensors, Materials and Amplifiers, 2nd ed.; Springer-Verlag: Berlin, Germany, 2002. [Google Scholar]
© 2014 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/3.0/).