Mechanism of Piezoelectricity for Langasite Based on the Framework Crystal Structure
Mechanism of Piezoelectricity for Langasite Based on the Framework Crystal Structure
Transactions on Electrical and Electronic Materials. 2012. Apr, 13(2): 51-59
Copyright ©2012, The Korean Institute of Electrical and Electronic Material Engineers
This is an open-access article distributed under the terms of the Creative Commons Attribution Non-Commercial License ( which permits unrestricted noncommercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
  • Published : April 25, 2012
Export by style
Cited by
About the Authors
Tsuyoshi Iwatak
Hiroki Morikoshi
Piezoelectric langasite crystals have superior properties such as high temperature performance and high quality Q and can be applied in combustion pressure sensors and surface acoustic wave (SAW) filters. Crystal growth,crystal structure and properties of langasite group are reviewed, and the mechanism of piezoelectricity of langasite is presented based on the crystal structure and deformation under high pressure. Finally, for the discovery of new piezoelectric materials, this paper presents the role of the framework, and recommends the search of framework crystal structure, because the characteristic of the mechanism exists on the framework of the crystal structure.
Langasite (La 3 Ga 5 SiO 14 (LGS)) is piezoelectric crystal named according to its composition, that is, La, Ga and Silicate mineral is named langasite with "ite" as the ending of a mineral name. Over one hundred langasite group compounds have been found with the structural formula A3BC3D2O14 [1 - 3] . Here, A, B, C and D are element name in different sites. The piezoelectric properties have been compared with quartz SiO 2 , as the structure of langasite is trigonal, point group 32 same as quartz [4 - 7] . This compound is one of the lead-free piezoelectric materials which have been researched because the toxin Pb has been excluded for health reasons by the RoHs directive [8] .
The special characteristic of langasite is high temperature performance based on its lack of Curie point and lack of phase transition until melting point around 1500℃, and a lack of pyroelectricity, depending on whether or not the point group 32 is the same as quartz, which will be described later. The application for high temperature has been used for combustion (burning) pressure sensors in combusting engines as shown in Fig. 1 (a) [9] . And, as the piezoelectric constant and the pass band filter characteristics are about 3 times that of quartz crystal, and because of near-zero TCf , langasite is a candidate for surface acoustic wave (SAW) filters as shown in Fig. 1 (b) [7] .
Moreover, langasite crystals have good points for single crystal growth. Single crystals are easily grown because of a low temperature melting point of about 1500℃ allowed use of Pt-crucible, none-phase transition, and congruent melting. And many kinds of methods can be used for crystal growth.
In this review paper, crystal growth, crystal structure, the properties, the mechanism of piezoelectricity, and the crystal structure under high pressure are presented.
Lager Image
(a) Combustion pressure sensor installed in cylinder for control of combustion. (b) SAW filter using langasite with low dielectric losses.
Langasite group single crystals have been grown by many growing methods such as Czochralski (Cz) technique, Bridgeman method, floating zone (FZ) method, and micro-pulling down (μ-PD) technique, as these crystals grow easily [10 - 12] .
LGS, Pr 3 Ga 5 SiO 14 (PGS) and Nd 3 Ga 5 SiO 14 (NGS) single crystals shown in this chapter were grown by a conventional radiation frequency (RF)-heating Cz-method with an output power of 60kW by Sato et al. [12] . Starting melts formed from single-phase powder of langasite sintered at 1300℃ using high purity 99.99% raw materials were applied at a height of 40 mm in a platinum and iridium crucible that was 50 mm in diameter and 50 mm in height. The growth atmosphere was a mixture of Ar with 1 vol% of O 2 gas in order to avoid the evaporation of gallium oxide from the melt during growth. The heating of melts was performed by Pt-crucible induction heating. The crucible was isolated by ZrO 2 granules. Before seeding, the melts were clarified for at least 1 h. The pulling velocity and the crystal rotation rates were 1.0-1.5 mm/h and 10 rpm, respectively. The seeds used were small <001> oriented LGS single crystal rods. The growing crystals were kept at temperature by a passive double after-heating system made of alumina ceramics.
Defect-free LGS, PGS and NGS single crystals with constant diameter of 22 mm and lengths up to 145 mm were grown as shown in Figs. 2 (a), (b) and (c), respectively [12] . These ingot diameters were highly consistent over the whole length. The optimum pulling rates are lower than 1.5 mm/h for inclusion-free perfect single crystals, and a higher temperature gradient at the growing interface controls the growth, preventing distinct facet enlargement and asymmetrical growth leading to spiral morphology.
LGS compounds with congruent melting are grown easily because of the same composition of growth crystals and liquid. In the case of solid solutions, the composition of the precipitated crystal gradually changes during crystal growth as shown in Fig. 3 (a). Takeda & Tsurumi [13] presented crystal growth with homogeneous composition from quasi-congruent melt [14 , 15] . In the case of Al-substituted La 3 Ga 5-x Al x SiO 14 (LGAS x ), as the limitation of the solid solutions is located at x = 0.9 as shown in Fig. 3 (b), the endmember of the solid solutions produces congruent melt. At x = 0.9 composition, good quality single crystals of LGAS0.9
Lager Image
Single crystals of langasite (a)-(c) and (d) grown by Cz-method, and by μ-PD technique, respectively.
Lager Image
Crystal growth from quasi-congruent melt. (a) crystal growth of solid solutions: composition of precipitated should be changed gradually. (b) formation of quasi-congruent melt at x = 0.9 due to precipitated secondary phase LaAlO3.
are grown as quasi-congruent melt growth.
Langasite crystal structure was analyzed originally by Mill et al. [2] . The crystal structure is isostructural to Ca 3 Ga 2 Ge 4 O 14 presented by Belokoneva et al. [1] . The crystal system is trigonal, point group 32, space group P 321 (No.150), with lattice constants of approximately a = 8.1, c = 5.1 Å, Z = 1, which is similar to quartz SiO 2 . Iwataki et al. [16] and Takeda et al. [17] determined the three langasite-groups, LGS, PGS and NGS crystals, using the initial atomic parameters presented by Mill et al. [2] . Table 1 shows the crystallographic data and experimental conditions for X-ray single crystal diffraction (XRSD) analysis.
The crystal structure figures projected from [001] and [120] are shown in Fig. 4 (a) and 4 (b), respectively. The structure represented by the structural formula, A3BC3D2O14 , is constructed from four sites: A-, B-, C-, and D- site projected in two ways as shown in Fig. 4. A -site is a decahedron with a coordination number (c.n.) of eight, known as twisted Thomson cube; B -site is an octahedron with a c.n. of six; and C - and D -sites are tetrahedra with a c.n. of four, as shown in Fig. 4 (c). The size of D -site is slightly smaller than that of C -site. Rare earth La 3+ , Pr 3+ and Nd 3+ occupy the A -site, Ga 3+ occupies the B, C and half of the D -sites, and Si 4+
Crystallographic data of NGS, PGS and LGS.
Lager Image
Crystallographic data of NGS, PGS and LGS.
Lager Image
Crystal structure of Langasite. (a) a1-a2 plane and (b) a1-c plane are viewed from [001] and [120], respectively. (c) four kinds of cation of cation polyhedra. is four kinds of cation polyhedra.
half of the D -sites, respectively. This structure is constructed by a framework layer structure: B-C-D-C-D-C six-membered rings around A -site as shown in Fig. 4 (a) projected from [001]. Tetrahedra C - and D -sites, and decahedra, octahedra, and open-space, form a layer structure as shown in Fig. 4 (b). Large cation sites A - and B -sites, and open-spaces, makes one layer. The open-space plays an important role for piezoelectric properties as described in section 5.
The crystal structures among LGS, PGS and NGS differ mostly in the shape of each site. In particular, the change of the A -site is remarkable. The decahedral A -site expands with the increase of ionic radius of rare earth ( R ) that occupies the A -site. The A -site expands greatly in [100] directions compared to the expansion in [120], which is perpendicular to [100], with the increase of the ionic radius of R .
- 4.1 Electric properties based on point group
The point group of langasite is 32, which is the same as quartz,
Point group and properties.
Lager Image
Point group and properties.
and has no inversion symmetry i . These piezoelectric materials without i are included in 20 point groups (except O = 432) of the 2nd to 7th columns shown in Table 2 [18] . Here, the 1st column is the Laue group with i , and the 3rd to 6th are for optical activity, the 5th to 7th are for pyroelectricity, and the 4th and 5th are for enantiomorphism. Ferroelectric materials are the ones with spontaneous polarization in pyroelectricity, the 5th to 7th columns. All ferroelectric materials show piezoelectricity, but the reverse is not true, that is, not all piezoelectric materials show ferroelectricity. So, the point group of piezoelectricity could be divided into two groups: one is for non-polar piezoelectricity and another is for polar piezoelectricity. It is worth pointing out that langasite in the 32 point group shows no polar piezoelectricity, that is, no pyroelectricity.
- 4.2 Polarity direction by point group
As langasite is a non-polar piezoelectric crystal, poling treatment is not necessary. However ceramics that are polycrystals show isotropic properties as a whole because each orientation of grains can turn to any direction. So, non-polar piezoelectric materials should be used as a single crystal. For a single crystal, the knowledge of the directions of piezoelectricity is very important. As the directions are the same as for polar, they could be derived based on the point group.
Figure 5 shows the stereographic projection of general positions in the point group. Figure 5 (a) shows the [001] direction without polarity because of the same number of ○ and × positions on the opposite sides of [001]. The [210] direction ( Fig. 5 (c)) is also non-polar by the same manner. Only the [100] direction shows polarity as shown in Fig. 5 (b). The configurations of a typical crystal of the point group 32 are shown along the stereographic projections, with crystal surfaces plotted on the stereo projections. The crystal structures along [120] and [100] as shown in Fig. 5 (d) and (e) show asymmetry and symmetry, respectively, along the left and right directions. Now, Fig. 6 shows a Y -cut of a crystal. Here, X, Y, and Z are Cartesian coordination, and hexagonal axis a and c also are shown.
- 4.3 Piezoelectric properties of langasite
Piezoelectric strain constants d11 of RGS ( R = La, Pr and Nd) crystals are shown as a function of the ionic radius of R in Fig. 7 (a) [12 , 16] . The d11 is dependent on the ionic radius of R, and LGS has the best piezoelectric properties among RGS ( R = La, Pr and Nd) crystals. The d11 value of LGS is -6.16 × 10 -12 C/N, which is 3 times that of quartz -2.3 × 10 -12 C/N. Figure 7 (b) shows the electromechanical coupling factor k12 as a function of the piezoelectric constant -d11 of the langasite group, including that of LGS, PGS, NGS and so on, compared to a quartz single crystal. In
Lager Image
Determination of piezoelectricity direction based on point group 32. Stereo graphs (a), (b) and (c) with equivalent points are projected from [001], [100], and [210], respectively. x:upper points, o: opposite points. Configurations of a crystal with point group 32 also are drawn for supporting the stereo projections. (d) and (e) show the crystal structure along [100] and [120] showing asymmetry and symmetry, respectively. Dipole moment will appear in (d).
Lager Image
Y-cut for langasite single crystal for piezoelectric measurements.
the A -site, cations with a larger ionic radius than La, such as Ba and Sr, are expected to have large d11 . Langasite with Ba in the A -site could not be obtained as transparent crystal.
On the other hand, Sr 3 Ga 2 Ge 4 O 14 with Sr in the A -site has been studied by Wu et al. [19] . They produced transparent single crystal with a large d11 of -7.41 × 10 -12 C/N, which is larger than that of LGS, as shown in Fig. 7 (b). The d11 and k12 of RGS (R = La, Pr and Nd) show just a linear relationship ( Fig. 8 (a)) with crystal structure AL/BL ( Fig. 8 (b)), which is the size ratio of A - and B - polyhedra along the a-axis.
Figure 9 shows the electromechanical coupling factor k2 as a function of TCf of the piezoelectric materials for a communica-
Lager Image
(a) Piezoelectric constant d11 of LGS, RGS and NGS as a function of ionic radius. (b) electromechanical coupling factor k12 of langasite series as a function of d11.
Lager Image
(a) Piezoelectric constant d11/electromechanical coupling factor k12 of LGS, PGS and NGS as a function of AL/BL which is shown in (b).
tion system. Langasite has been expected for use as a SAW filter to replace quartz and LiTaO 3 because of its wide bandwidth and near-zero TCf . Quartz has low TCf , but narrow bandwidth. On the other hand, LiTaO 3 has wide bandwidth but large TCf . AlPO 4 and Li 2 B 4 O 7 have good properties such as high k2 and near-zero TCf , but they have weak points for crystal growth. AlPO 4 has growth problems such as twinning, and Li 2 B 4 O 7 has weak points such as deliquescence and low growth rate [4] .
Figure 10 (a) shows the temperature dependence of frequency and the equivalent series resistance of a filter made of Y-cut LGS single crystal [11] . The temperature dependence of frequency shows a secondary curve with good values of 1-2 ppm/℃. In the range of -20 to 70℃, the dependence of temperature shows good values of 100 to 150 ppm/℃. Figure 10 (b) shows the equivalent series resistance as a function of vibration modes of resonators on the LGS and quartz single crystals [11] . The resistance of
Lager Image
Electromechanical coupling factor vs. temperature coefficient of frequency of piezeelectric materials.
Lager Image
(a) Frequency variation/equivalent series resistance as a function of temperature on the La3Ga5SiO14 filter. (b) equivalent series resistance of quartz and langasite single crystals as a function of resonator vibration modes.
LGS is one order smaller than that of quartz. So, as if the surface roughness of LGS is large, high frequency oscillation is easy. Moreover, as the equivalent series resistances at the 7th and 9th modes are small, the LGS filter is useful as a high frequency wave area filter.
Figure 11 shows pass band characteristic of a filter made of Ycut LGS single crystal [4 , 11] . Y-cut LGS single crystal has a very wide pass band characteristic width of 45 KHz at 3 dB attenuation,which is 3-times that of quartz with 15 KHz band width.This means the electromechanical coupling constant k12 of LGS is about 3-times larger than that of quartz.
Table 3 shows the properties comparing some piezoelectric crystals such as LiTaO 3 , LGS, quartz, and La 3 Ga 5.5 Nb 0.5 O 14 (LGN) [4] . The properties of LGS are between LiTaO 3 and quartz. The electro-mechanical coupling factor k of LGS is 15 to 25%, located
Lager Image
Filter properties of La3Ga5SiO14 single crystal.
Comparison of properties of each crystal.
Lager Image
Comparison of properties of each crystal.
between that of LiTaO 3 at 43%, and quartz at 7%. The temperature frequency variation of LGS is 100 to 150 ppm/℃, located between that of LiTaO 3 at 200 to 400 ppm/℃, and quartz at 50 to 80 ppm/℃. Here, LGN single crystal substituted for Nb 5+ and Ga 3+ for Si 4+ has superior piezoelectric properties.
- 4.4 Ordered crystal structure and properties
LGS, PGS and NGS are compositionally disordered crystals. The structural formulae are [R 3 ] A [Ga] B [Ga 3 ] C [GaSi] D O 14 (R = La, Pr and Nd). Here, as the D -site is occupied disorderly by Ga and Si, these crystals are disordered. Ordered langasite structural formulas such as Sr 3 TaGa 3 Si 2 O 14 (STGS), Sr 3 TaGa 3 Ge 2 O 14 (STGG), Sr 3 NbGa 3 Si 2 O 14 (SNGS), Ca 3 NbGa 3 Si 2 O 14 (CNGS), and Ca 3 TaGa 3 Si 2 O 14 (CTGS) are presented and characterized by Mill et al. [20] and Takeda et al. [21] . The structural formula is [Sr/Ca 3 ] A [Nd/Ta] B [Ga 3 ] C [Ge/Si] D O 14 ; the large A -decahedron is occupied by Sr or Ca cations, the middle size B -octahedron by Nd or Ta cations, and C - and D -tetrahedra by the larger Ga and the smaller Ge or Si cations, respectively. The ordering should be called "compositional ordering," compared with ordering based on the order-disorder transition.
Table 4 shows the characterization of disordered and ordered langasite-type piezoelectric single crystals at room temperature and 500℃ [22] . Though the ordered crystals possess lower piezoelectric coefficients than disordered ones at room temperature as shown in Fig. 12 [23] , they possess much higher mechanical quality factor and electrical resistivity at an elevated temperature of 500℃. The high mechanical quality factor and the high electrical resistivity have been expected for use in a hightemperature bulk acoustic wave (BAW) and SAW resonator and ignition pressure sensor, respectively. The density and dielectric constant of ordered crystals are lower than those of disordered ones, which contribute to the high acoustic velocity in high frequency devices. LTGA and LNGA disordered crystals in Table 4 have substituted Al for Ga in La 3 R 0.5 Ga 5.5-x Al x O 14 (L R GA x , R = Ta or Nb), which contributes to the low raw material cost. Takeda et al. [24] presented LTG, LTGA0.3 and LTGA0.5 in which d14 values were increased to 3.68, 4.03 and 4.19 pC/N in that order, and resistivity increased to 2.2 × 10 7 , 4.6 × 10 7 and 7.1 × 10 8 Ω · cm
Characterization of disordered and ordered langasitetype piezoelectric single crystals at room temperature and 500℃. LTG:La3Ta0.5Ga5.5O14; LNG:La3Nb5GaO14; LTGA: La3Ta0.5Ga5.3Al0.2O14; LNGA: La3Nb0.5Ga5.3Al0.2O14; SNGS: Sr3NbGa3Si2O14; STGS: Sr3TaGa3Si2O14; CNGS: Ca3NbGa3Si2O14; CTGS: Ca3TaGa3Si2O14; CTAS: Ca3TaAl3Si2O14.
Lager Image
Characterization of disordered and ordered langasitetype piezoelectric single crystals at room temperature and 500℃. LTG:La3Ta0.5Ga5.5O14; LNG:La3Nb5GaO14; LTGA: La3Ta0.5Ga5.3Al0.2O14; LNGA: La3Nb0.5Ga5.3Al0.2O14; SNGS: Sr3NbGa3Si2O14; STGS: Sr3TaGa3Si2O14; CNGS: Ca3NbGa3Si2O14; CTGS: Ca3TaGa3Si2O14; CTAS: Ca3TaAl3Si2O14.
Lager Image
(a) Piezoelectric constant d11 as a function of lattice constant for langasite series crystals.
in that order, at 400℃ as shown in Fig. 13 [24] . The resistivity of LTGA0.5 increased to about 30 times that of LTG. Al-substituted LGS (La 3 Ga 5-x Al x SiO 14 : LGASx) were also studied for high resistivity at elevated temperature and low cost, which was presented by Kumatoriya et al. [15] and Takeda et al. [24] . The piezoeoectric properties d11 and resistivity of LGAS0.9 were improved from 6.075 to 6.188 pC/N and 5.9 × 10 7 to 7.6 × 10 8 Ω · cm, respectively. The Al-substitution is effective for high resistivity and also reduces the raw material cost. The CTAS in Table 4 substituted Al for Ga completely and has a high resistivity of 2.7 × 10 9 Ω · cm. On the other hand, Fe-substituted langasite-type crystals are expected for use as multiferroic materials [25] .
- 5.1 Crystal structure under pressure
In this section, the mechanism of the piezoelectricity has been presented based on the crystal structure and deformation under applied pressure. Pressures applied to the single crystals using a diamond anvil cell (DAC) as shown in Fig. 14 were calibrated by the ruby fluorescence technique. The DAC was set on the four-circle diffractometer. The unit cell parameters were refined by using the 2Θ-ω step scan technique. Table 5 shows crystallographic data of LGS and NGS including the lattice parameters measured at various pressures.
The pressure dependence of lattice parameters ( a 1 and c ) and unit cell volume are plotted in Fig. 15. Both lattice parameters along a 1 - and c -directions shrunk linearly with an increase of applied pressure. Noteworthy is that the a1 -axis is preferentially shrunk compared to the c -axis. This indicates that the compression of langasite crystals occurs preferentially in the a1-a2 plane. Table 6 compares the variation polyhedra sizes along the [100]
Lager Image
Resistivity of LTG LTGA0.3 and LTGA0.5 at elevated temperature. Al-substituted LTGA0.5 was improved by about 30 times at 400℃. Higher resistivity is expected.
Lager Image
Schematic cross section of diamond anvil cell.
Crystallographic data of LGS and NGS under pressure.
Lager Image
Crystallographic data of LGS and NGS under pressure.
direction of AL, BL and SL , which are presented in Fig. 16 , based on the crystal structures obtained at an atmospheric pressure of around 3 and 6 GPa [26] . Lattice parameter a1 equals the sum of AL+BL+SL . Therefore, we can consider that the preferential shrinkage observed along the a1 -axis is also divided into three kinds of lengths. As seen in Table 6 , the change in SL is much larger than the other lengths of AL and BL , indicating a larger contribution to shrinkage of an open-space. The open-space is surrounded by the A -, B - and C -polyhedra shared corners. In contrast, A - and B -polyhedra make shared edges with each other. When the pressure is induced in the [100] direction, it can be speculated that the corner-shared open-space is easily distorted compared with the edge-shared A - and B -polyhedra.
- 5.2 Mechanism of piezoelectricity of langasite
Iwataki et al. [16] presented the mechanism of piezoelectricity
Lager Image
Lattice parameters of LGS and NGS as a function of pressure.
A- and B-polyhedra size ALand BL, and open-space size SLalong a-axis and AL/BLfor LGS and NGS. Atm.: atmosphere pressure.
Lager Image
A- and B-polyhedra size AL and BL, and open-space size SL along a-axis and AL/BL for LGS and NGS. Atm.: atmosphere pressure.
Lager Image
Sizes of A-, B-site and open space S, and atomic distances of ML, NL and OL between atoms. Position X is the center of oxygen atoms on A-polyhedron.
of langasite based on the deformation of the A -site. Piezoelectricity originates from polarization caused by the destruction of charge balance depending on the displacement of ions when pressure is induced. The piezoelectricity of langasite is known to be generated in the [100] direction. From the rule of symmetrical operation, langasite should have polarization in A - and C -polyhedra in contrast with no polarization in B - and D -polyhedra. And also, the reason for La-langasite having larger piezoelectricity than Nd-langasite is clarified.
Figure 17. Mechanism of piezoelectricity on langasite projected from [120]. Position X is the center of oxygen atoms on A-polyhedron. Under pressure, ML does not change and NL shrinks because of the role of open-space as a damper.
With an induced pressure, the distance ML between A and B
Atomic distances (MLNL) center position X-B ion distance (OL) dipole moment (ML- OL) and lattice constant ofa1of LGS and NGS along [100] direction under the pressure. Atm.: atmosphere pressure.
Lager Image
Atomic distances (ML NL) center position X-B ion distance (OL) dipole moment (ML - OL) and lattice constant of a1 of LGS and NGS along [100] direction under the pressure. Atm.: atmosphere pressure.
Lager Image
Mechanism of piezoelectricity on langasite projected from [120]. Position X is the center of oxygen atoms on A-polyhedron. Under pressure, ML does not change and NL shrinks because of the role of open-space as a damper.
Lager Image
The difference ML-OL (dipole moment P) for LGS and NGS as a function of pressure.
cations as shown in Fig. 16 and Table 7 is not changed around 3.4 Å, and the distances of NL ( A ion-[open-space]- B ion) in LGS and NGS are shrunk from 4.75 to 4.65, and 4.70 to 4.58 Å, respectively. On the other hand, A -polyhedron is distorted to the [-100] direction. The distortion is clarified by the shortening of the distance OL between the center position X on A-polyhedron and B-ion as shown in Figs. 16 and 17. The OL lengths of LGS and NGS are shortened from 3.27 to 3.21 Å, and 3.23 to 3.17Å, respectively. As a result, a dipole moment P appeared from moving the centers of mass of positive and negative charges to produce piezoelectricity. Here, the differences ( ML - OL ) between center positions X and A -ion positions on the LGS and NGS calculated based on crystal structure are equivalent to polarization as shown in Table 7 and Fig. 18. The values of LGS and NGS as a function of pressure are increased from 0.147 to 0.177 Å (at 6.1 GPa) and 0.143 to 0.178 Å (at 6.8 GPa), respectively. The value increases with pressure. So, the mechanism of piezoelectricity on the langasite structure series is presented as follows: though the A -polyhedron is deformed to [-100] with applied force, A -ion stays in the same position by repulsion force from B -ion under the existence of open-space, which has no atoms in the center and is working as a damper. The difference between A -cation and center position X should make a net dipole moment P along the a -axis. Dipole moment should be enhanced if the distance between the charge centers of cations and anions becomes large. Therefore, the enhancement of piezoelectric properties is related with the shrinkage of open-space in langasite crystal structure, and it is clear that the increase of polarization is caused by the induced pressure in the [100] direction of langasite structure.
The reason for La-langasite having larger piezoelectricity than Nd-langasite is clarified by the difference of the ML - OL (dipole moments P ). As shown in Fig. 18 , the dipole moments P for LGS are larger than that for NGS.
Langasite is a kind of materials formed a framework structure without inversion symmetry i . Quartz and BeO also have framework structures formed mainly by a covalent bond such as SiO 4 , AlO 4 , ZnO 4 . Especially, silicates including langasite make many framework structures by connection of SiO 4 tetrahedra as cyclo-, ino-, phyllo-, and tecto-silicates. These framework structures have been noticed recently for many kinds of properties, such as zeolite for optical properties by absorption of special compounds.
Recently, Hosono [27] presented that Ca 12 Al 14 O 32 (C 12 A 7 ) clinker compound with big cages including O 2- in a [Ca 24 Al 28 O 64 ] 4+ framework shows specific properties such as electride, transparent electride, transparent p-type conducting oxides, transparent semiconductor, super conductor, and other properties. The crystal structure has 12 cages of 4.4 Å in diameter in a unit cell of a 12 Å cube, and 2 cages of those 12 include oxygen ion (O 2- ) as shown in Fig. 19 (a). As this O 2- is bonding weakly with the framework, this ion could be removed or exchanged with other anions easily. Transparent metal oxide (C 12 A 7 :H - ) transformed to electro conductor by photon-induced phase transition, C 12 A 7 compound including much active oxygen O - atoms [28 , 29] , and C 12 A 7 : e-electride stable in room temperature and air-condition [30] are presented by Hosono group. C 12 A 7 crystal grown by Cockayne & Lent [31] is expected for use in SAW, because of the high SAW velocity and reasonable bulk electromechanical coupling by Whatmore (to be published). Two space groups are reported such as I 43 d by Cockayne & Lent [31] and I 42 m by Kurashige et al. [32] . The point groups are 43m and 42m , respectively. Both point groups without i show piezoelectricity, and the latter shows additional rotatory power. Moreover, additional atoms grouped in the cages of the frame structure are expected to be designed for SAW-suitable properties.
Here, we will present a candidate for piezoelectric materials. Nepheline (KNa 3 Al 4 Si 4 O 16 ) is one of the alumino-silicates with framework as shown in Fig. 19 (b). The crystal structure has a hexagonal ring framework without i based on the space group P 6 3 (No. 173), the point group 6. When stress is added to the ring, the ring will deform and cations located in tetrahedra and near the center of the ring will shift. If the center of cations and anions will become different, piezoelectricity will occur.
Lager Image
(a) Crystal structure of aluminate calcium C12A7 with framework crystal structure. New-type superior properties such as superconductor were designed from this structure. (b) nepheline structure as an example of alumino-silicates with framework.
This review paper is presented about the crystal structure and mechanism of piezoelectricity of langasite. The mechanism of piezoelectricity was derived based on the crystal structure and deformation of crystal structure under high pressure. Openspace in the langasite framework structure plays a key role in the mechanism of piezoelectricity. So, the framework structure should be noticed from the point of view of the piezoelectricity. And general knowledge for properties is presented based on the point groups which are applied for derivation of the piezoelectricity direction. Moreover, there are two important aspects for applications of langasite: one is the easy crystal growth based on a low melting point of 1,470℃ resulting in no phase transition and congruent melting; another is the high performance piezoelectricity properties such as high temperature performance based on the lack of phase transition and better piezoelectric properties compared to quartz. This reviewed paper is written based on "Origin of Piezoelectricity on Langasite" [33] .
The author would like to thank Dr. Katsumi Kawasaki and Dr. Jun Sato of TDK Co. for the presenting single crystal LGS, PGS and NGS, Professor Hiroaki Takeda of the Tokyo Institute of Technology for supporting writing, also, M. Eng. Nobukazu Araki of NIT for studying crystal structure analysis and experiments under high pressure, Professors Yasuhiro Kudo and Dr. Takahiro Kuribayashi of Tohoku University for supporting crystal structure analysis under high pressure, Professors Cheon Chae-Il and Kim Jeong-Seog of Hoseo University Korea for discussion of the contents, and Professors Ken-ichi Kakimoto and Isao Kagomiya of NIT for supporting experimental conditions, moreover, Ms. Keiko Ohsato for supporting health conditions. A part of this paper was supported by A Grant-in Aid for Science Research (c) from the Ministry of Education, Science, Sports and Culture, Japan.
Belokoneva E. L , Simonov M. A , Butashin A. V , Mill B. V , Belov N. V 1980 Sov. Phys. Dokl. 25 954 -
Mill B. V , Buntashin A. V , Khodzhabagyan G. G , Belokoneba E. L , Belov N. V 1982 Dokl. Akad. Nauk USSR 264 1385 -
Mill B. V , Pisarevsky Y. V 2000 Proc. 2000 IEEE/EIA Inter. Freq. Control Sympo. 133 -
Fukuda T , Shimamura K , Kohno T , Takeda H , Sato M 1995 J. Jap. Asso. Crystal Growth (Japanese) 22 (5) 358 -
Gotalskaya A. N , Drezin D. I , Bezdelkin V. V , Stassevich V. N 1993 Proc. 1993 IEEE Inter. Freq. Control Sympo. 339 -
Silvestrova I. M , Bezdelkin V. V , Senyushenkov P. A , Pisarevsky Yu. V 1993 Proc. 1993 IEEE Inter. Freq. Control Sympo. 348 -
Silvestrova I. M , Pisarevsky Yu. V , Bezdelkin V. V , Senyushenkov P. A 1993 Proc. 1993 IEEE Inter. Freq. Control Sympo. 351 -
European Commission - Environment - Waste - WEEE []
Kaminskii A. A , Mill B. V , Khodzhabagyan G. G , Konstantinova A. F , Okorochkov A. I , Silvestrova I. M 1983 Physicastatus solidi (a) 80 (1) 387 -
Shimamura K , Takeda H , Kohno T , Fukuda T 1996 J. Crystal Growth 63 388 -
Sato J , Takeda H , Morikoshi H , Shimamura K , Rudolph P , Fukuda T 1988 J. Crystal Growth 191 746 -
Takeda H , Tsurumi T 2011 Bull. Ceram. Soc. Japan 46 (8) 657 -
Takeda H 1998 Tohoku University
Kumatoriya M , Sato H , Nakanishi J , Fujii T , Kadota M , Sakabe Y 2001 J. Cryst. Growth 229 289 -
Iwataki T , Ohsato H , Tanaka K , Morikoshi H , Sato J , Kawasaki K 2001 J. Eur. Ceram. Soc. 21 1409 -
Takeda H , Shimizu S , Nishida H , Okamura S , Shiosaki T 2005 Trans. Mater. Res. Soc. Jpn. 30 63 -
Shono Y. , Tokonami, M. 2002 Introduction of Crystal Chemistry Uchida Rokakuho Tokyo 53 -
Wu, A. , Xu, J. , Qian G. , Wu, X. (2005) J. Crystal Growth 275 e703 -
Mill, B. V. , Belokoneva E. L. , Fukuda, T. (1998) Russian J. Inorg. 43 1168 -
Takeda, H. , Sato, J. , Kato, T. , Kawasaki, K. , Morikoshi, H. , Shimamura K. , Fukuda, T. (2000) Material Research Bulletin 35 245 -
Zhang, S. , Zheng, Y. , Kong, H. , Xin, J. , Frantz E. , Shrout T. R. (2009) J. Appl. Phys. 105 114107 -
Takeda, H. , Kato, T. , Chani V. I. , Morikoshi, H. , Shimamura K. , Fukuda, T. (1999) J. Alloys Com. 290 79 -
Takeda, H. , Kumatoria M. , Shiosaki, T. (2002) Key Eng. 216 43 -
Lee, C. , Kan, E. , Xiang H. , Whangbo, M. H. (2010) Chem. Mater. 22 (18) 5290 -
Araki, N. , Ohsato, H. , Kakimoto, K. , Kuribayashi, T. , Kudoh Y. , Morikoshi, H. (2007) J. Eur. Ceram. Soc. 27 4099 -
Hosono, H. , Ginley, D. , Hosono, H. , Paine, D. 2010 Handbook of Transparent Conductors Springer Chap. 10
Hayashi, K. , Hirano, M. , Matsuishi, S. , Hosono, H. (2002) J. Am. Chem. Soc. 124 738 -
Hayashi, K. , Matsuishi, S. , Kamiya, T. , Hirano, M. (2002) Nature 419 462 -
Matsuishi, S , Toda, Y. , Miyakawa, M. , Hayashi, K. , Kamiya, T. , Hirano, M. , Tanaka I. , Hosono, H. (2003) Science 301 626 -
Cockayne B. , Leat, B. (1979) J. Crystal Growth 46 (2) 467 -
Kurashige, K. , Toda, Y. , Matstuishi, S. , Hayashi, K. , Hirano M. , Hosono, H. (2006) Cryst. Growth Design 6 1602 -
Ohsato, H. , Hutagalung S.D. 2012 Materials Science and Technology Intech Croatia Chapter 2. [A free online edition:]