WO2003033780A1 - Method of growing piezoelectric lanthanide gallium crystals - Google Patents

Method of growing piezoelectric lanthanide gallium crystals Download PDF

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Publication number
WO2003033780A1
WO2003033780A1 PCT/CA2001/001450 CA0101450W WO03033780A1 WO 2003033780 A1 WO2003033780 A1 WO 2003033780A1 CA 0101450 W CA0101450 W CA 0101450W WO 03033780 A1 WO03033780 A1 WO 03033780A1
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Prior art keywords
group
elements selected
exceeding
lanthanide
value
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PCT/CA2001/001450
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French (fr)
Inventor
Iouri D. Zavartsev
Serguei A. Koutovoi
Alexander I. Zagoumenny
Pavel A. Studenikin
A. Faouzi Zerrouk
Damien G. Loveland
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Utar Scientific Inc.
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Priority to PCT/CA2001/001450 priority Critical patent/WO2003033780A1/en
Publication of WO2003033780A1 publication Critical patent/WO2003033780A1/en

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/20—Controlling or regulating
    • C30B15/22—Stabilisation or shape controlling of the molten zone near the pulled crystal; Controlling the section of the crystal
    • C30B15/24—Stabilisation or shape controlling of the molten zone near the pulled crystal; Controlling the section of the crystal using mechanical means, e.g. shaping guides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/28—Complex oxides with formula A3Me5O12 wherein A is a rare earth metal and Me is Fe, Ga, Sc, Cr, Co or Al, e.g. garnets
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/34—Silicates

Definitions

  • the present invention relates to a method of growing large diameter piezoelectric
  • the SAW devices are currently used, for example, as bandpass filters, resonators, delay lines and converters, in a broad range of wireless applications, cellular communication devices and cable TV
  • Piezoelectric material based on lanthanide gallium crystals including the langasite family of crystals, i.e La 3 Ga 3 S ⁇ O ⁇ 4 , referred to as langasite (LGS), La 3 Ga 5 5 Nb 0 5 ⁇ 4 , referred to as langanite (LGN), and langatate La 3 Ga 5 5 Ta 0 5 ⁇ 4 (LGT) are known to be useful for piezoelectric applications
  • LGS langasite
  • LGN La 3 Ga 5 5 Nb 0 5 ⁇ 4
  • LGT langatate La 3 Ga 5 5 Ta 0 5 ⁇ 4
  • a SAW device having a LGS single crystal substrate is disclosed in U S Pat No 5,821 ,673, U K Pat No 2,328,815, RU Pat No 2073952, and U S Pat No 5,917,265
  • a LGT single crystal substrate having a prescribed range of Euler angles for substrate and crystal orientation to improve signal processing in a SAW device is disclosed in U S Pat No 6,097,131
  • a SAW device comprising a wafer constructed of a trigonal langasite crystal cut at predominated cut angles is disclosed in U S Pat No 5,981 ,673
  • An optimal cut for SAW devices made from langatate crystals is disclosed in U S Pat No 6,097, 131
  • a substrate for piezoelectric device and SAW devices composed of a single crystal of langanite is proposed in JP Pat No 11106294A
  • the method of oriented crystallization from a melt, eliminating any contact with the side faces of a growing crystal with solid walls, are now well known and increasingly becoming widespread. These are the Czochralski (conventional Czochralski), Stepanov, Verneuil and floating zone techniques, characterized by a fixed orientation of crystallization at a fixed position of the solid - liquid interface.
  • a Stepanov crystal growth method based on a capillary formed pole of melt by means of a special mould and the crystallization of the pole outside the container is generally described in "Capillary shaping in crystal growth from melts" V.A. Tatarchenko, Journal of Crystal Growth 37 (1977) 272-284 and “Crystallization stability during capillary shaping” G,l Babkin, E A Brener and V.A. Tatarchenko, Journal Crystal Growth 50 (1980) 45-50
  • Another crystal growth method, the EFG crystal growth method is a method of profiled crystal growth or a method of edge defined film fed growth.
  • the capillary action shaping technique, CAST differs from the EFG technique in the construction of the forming mould and a presence of forced inert gas cooling
  • the Stepanov, EFG and CAST methods are described in the publication "Growth the profiled single crystals by Stepanov technique" P I Antonov, L.M. Zatulovskn, A.C. Kostyugov, (eds) Leningrad “Nauka” (1981) 280 pp
  • the method proposed for growing a piezoelectric material based on lanthanide gallium crystals is the conventional Czochralski crystal growth method
  • the growth of the langasite family of crystals by the Czochralski method is accurately described in "Investigation of trigonal (La ⁇ -x Nd x ) 3 Ga 2 SiO 14 crystals" A.A Kaminskn, B V Mill, G G
  • a method of growing single crystals of lanthanum-gallium silicate is disclosed in
  • the essence of the method consists in the selection of the orientation of the seed crystal ensuring growth by the Czochralski method of single crystals of lanthanum-gallium silicate along the directions ⁇ 01.1>, ⁇ 02.1>, ⁇ 02.3>, ⁇ 03.2> or at 54 degrees to the "Y" axis.
  • a method of growing of lanthanum gallium tantalum single crystal (LGT) is disclosed in JP Pat. No 11322495A and JP Pat. No 11199392A in which langatate crystals are doped with Pr, Nd, Ce, Sm and Eu impurities are grown by the Czochralski method.
  • the lanthanide gallium melt needs to be held (soaked) at a certain temperature for a considerable time (4 - 20 hours).
  • An appropriate thermal treatment of the melt is needed in order to obtain stable physical properties, which then permits further precise control of the melt temperature.
  • An associated problem is the duration of the growth process and therefore its cost increases by up to 30%.
  • the present invention provides a method for producing lanthanide gallium crystals in which, to control heat and mass transfer and to maintain a steady state of crystal melt interface, the growing crystal is pulled through a forming mould dipped into the melt contained in a crucible. While a lanthanide gallium single crystal is growing, a mixed oxide charge of the same composition as the melt may be continuously added to the melt such that the quantity of melt is maintained substantially stable. Crystals produced by this method exhibit less variability in piezoelect ⁇ c properties.
  • the shape of the solid-liquid interface is determined by the shape of the freezing isotherm. Consequently, the objects of the invention are achieved by controlling the shape of the freezing isotherm during the main part of the crystal growth. There may be some va ⁇ ation from the desired conditions at the beginning and the end of the growth.
  • the thermal conditions are determined by the crucible and forming mould sizes and their location in the heating environment as well as the furnace design and the insulating material employed.
  • the preferred embodiments of the present invention also provide an optimal growth direction for the crystal aligned with axis perpendicular to such a crystallographic plane of lanthanide gallium crystal that an improved temperature stability, lower power flow angle, and reduced diffraction are present in a SAW device cut in this plane. Consequently, the other objects of the invention are achieved by choosing an optimum growth direction for piezoelectric applications independently of the crystallization rate. Optimal orientation allows the cutting of wafers at an angle of 90 degrees to growth axis to ensure minimal losses of material. This also means that the temperature coefficient of frequency in the wafer is close to zero.
  • the optimally oriented lanthanum gallium crystals which are grown are more suitable for the mass-production slicing of crystals into wafers for SAW devices, suitable sizes of which may be 2 inches or more in diameter.
  • Fig. 1 shows a schematic view of the different furnaces used to produce different sizes of piezoelectric lanthanum gallium single crystals
  • Fig. 2a is a schematic showing the seed crystal oriented along the crystallographic z-axis and the optimally oriented wafers cut from grown boule;
  • Fig. 2b is a schematic showing the seed crystal oriented at ⁇ degrees to the "Y" axis and the optimally oriented wafers cut from grown boule;
  • Fig. 3 shows the different constructions of forming moulds; and Figs. 4a and 4b are tables of the results of growing crystals using various compositions and the parameters used in the growing operation.
  • Crystal growth is accomplished with a crystal grower machine (Kristall-3M) which includes a furnace as shown in FIG.1.
  • the furnace comprises a housing 10 formed from refractory and insulating materials and having a crucible 11 located therein.
  • the crucible 11 holds a forming mould 14 dipped into a melt 15.
  • the housing includes an aperture for insertion of a seed crystal 12.
  • An RF inductive heating coil 13 surrounds the housing 10 at the level of the crucible 11.
  • Ln 3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd
  • Me 2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb
  • Me 4+ is at least one of the elements selected from the group consisting of Ti, Zr, Hf, Sn, Ce, Pr, Si and Ge
  • Me 5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V
  • x is a value not exceeding one
  • y is a value not exceeding (2 - x); 0.86 ⁇ a ⁇ 1.1 ; 0.85 ⁇ b ⁇ 1.3; and 0.94 ⁇ c ⁇ 1.08
  • Ln 3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd
  • Me 2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb
  • Me 3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In
  • Me 4+ is at least one of the elements selected from the group consisting of Si, Ge, and Sn
  • x is a value not exceeding two; 0.86 ⁇ a ⁇ 1 1 ; 0.85 ⁇ b ⁇ 1.3; and 0.94 ⁇ c ⁇ 1.08
  • Ln 3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd
  • Me + is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb
  • Me 3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In
  • Me 4+ is at least one of the elements selected from the group consisting of Si and Ge
  • Me 5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V
  • D represents oxygen vacancies of quantity z not exceeding 0.2 formula units
  • x is a value not exceeding one
  • y is a value not exceeding (2 - x); 0.92 ⁇ a ⁇ 1.07; 0.9 ⁇ b ⁇ 1.1 ; and 0.99 ⁇ c ⁇ 1.02
  • Ln 3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd
  • Me 2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb
  • Me 4+ is at least one of the elements selected from the group consisting of Ti, Zr, Hf, Sn, Ce, Pr, Si and Ge
  • Me 5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V
  • D represents oxygen vacancies of quantity z not exceeding 0.2 formula units
  • x is a value not exceeding one
  • y is a value not exceeding (2 - x); 0.86 ⁇ a ⁇ 1.1 ; 0.85 ⁇ b ⁇ 1.3; and 0.94 ⁇ c ⁇ 1.08
  • Ln 3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd
  • Me 2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb
  • Me 3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In
  • Me 4+ is at least one of the elements selected from the group consisting of Si, Ge, and Sn
  • D represents oxygen vacancies of quantity z not exceeding 0.2 formula units
  • x is a value not exceeding a two; 0,86 ⁇ a ⁇ 1 1 ; 0.85 ⁇ b ⁇ 1 3; and 0.94 ⁇ c ⁇ 1.08
  • Ln 3 . x . y Me x+y a Me 0 5(1+x)b [M ⁇ 0 5(1-x) Me y Ga 5 . y ] c Oo 5[(9-x-y)a+2 5 (H x )b * (1 6 5- 1 5x + y ) c] 05zF z
  • Ln 3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd
  • Me 2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb
  • Me 3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In
  • Me 4+ is at least one of the elements selected from the group consisting of Si and Ge
  • Me 5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V
  • F 2 is fluorine of quantity z not exceeding 0.2 formula units
  • x is
  • Ln 3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd
  • Me 2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb
  • Me 4+ is at least one of the elements selected from the group consisting of Ti, Zr, Hf, Sn, Ce, Pr, Si and Ge
  • Me 5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V
  • F z is fluorine of quantity z not exceeding 0.2 formula units
  • x is a value not exceeding unit
  • y is a value not exceeding (2 - x); 0.86 ⁇ a ⁇ 1.1 ; 0.85 ⁇ b ⁇ 1.3; and 0.94 ⁇ c ⁇ 1.08.
  • Ln 3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd
  • Me 2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb
  • Me 3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In
  • Me 4+ is at least one of the elements selected from the group consisting of Si, Ge, and Sn
  • F z is fluorine of quantity z not exceeding 0.2 formula units
  • x is a value not exceeding two; 0.86 ⁇ a ⁇ 1.1 ; 0.85 ⁇ b ⁇ 1.3; and 0.94 ⁇ c ⁇ 1 .08.
  • the raw oxide powder materials mentioned in formulae (1) - (9) are dried at 1000°C then mixed in the appropriate proportions and pressed into pellets (where appropriate), and loaded into the crucible.
  • the materials are then melted and the melt 15 may be doped with the oxides of micro additions of the chemical elements Li, Be, B, Na, Mg, Al, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, As, Se, Rb, Sr, Y, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, Ce, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, U,Th at a quantity between 1 ⁇ 10 17 atom/cm 3
  • the seed crystal 12 may be arbitrary orientated, including orientation coinciding with the Z-axis (see Fig. 2a) or o ⁇ entation aligned with the ⁇ -Y axis perpendicular to a crystallographic plane of lanthanum gallium crystal (Fig 2b) Crystals sliced along the crystallographic plane have an optimized combination of a minimal power flow angle, a minimal temperature coefficient of frequency, negligible diffraction, and high electromechanical coupling factor. With an ⁇ -Y axis orientation it is possible to cut wafers 30 at an angle of 90 degrees to the growth axis to ensure minimal losses of material and a crystal temperature coefficient of frequency close to zero.
  • the seed crystal 12 oriented at ⁇ degrees to the "Y" axis or having another optimal orientation or an arbitrary orientation, is brought in contact with the surface of the melt 15 Using the seed crystal 12 the growing crystal 16 is drawn from the melt 15 through the forming mould 14 dipped in the melt 15
  • the forming moulds 14 are fixed independently of the crucible 11 to facilitate mould replacement and prevent deformation on the melt 15 solidification
  • the forming mould is set in crucible 11 to control heat and mass transfer and to maintain a steady state of the crystal melt interface
  • the main task to solve is the creation of a temperature distribution near the solid-liquid interface such that the profile of isotherms in the melt 15 define geometrical form of the pulling crystal
  • the forming mould 14 has an arbitrary cross-sectional form including round or square, and a height less than the crucible 11 height Different constructions of forming moulds 14 used in Stepanov's, EFG and CAST crystal growth methods are presented in FIG 3
  • the capillary moulds for types 31 and 32 comprise two or more parajlel vertical plates 38 of equal length and 1 mm thickness, with a 1 mm-space to provide the capillary action.
  • the multi-capillary moulds 33 have from 20 to 120 channels with 0.1 mm deep grooves on the surface of the plates. While the crystal is drawn through a forming mould the melt 15 moves up in capillary channels 34 under action of surface tension forces as a result of wetting 35 of the walls.
  • the crystals are grown in an argon atmosphere, in a mixture of argon and oxygen (the content of oxygen is up to 20 vol%), in a mixture of argon and carbon dioxide (the content of carbon dioxide is up to 20 vol%), in a mixture of argon and fluorine (the content of fluorine is up to 3 vol%), in a nitrogen atmosphere, in a mixture of nitrogen and oxygen (the content of oxygen is up to 20 vol%), or in a mixture of nitrogen and fluorine (the content of fluorine is up to 3 vol%)
  • the crystals grown varied from colourless, through pale yellow and dark orange, to oxblood red in colour, depending on the oxygen content in the atmosphere in the growth chamber
  • a high oxygen content (approximately 8 - 20 vol% of oxygen) yields the oxblood red colour, whereas an oxygen content of about 2-8 vol% yields the darker orange colour
  • the crystals grown in an oxygen free atmosphere were colourless This shading colour is caused by oxygen vacancies formed, the quantity of which depends on the amount
  • the crystal is drawn through a forming mould when the pulling speed is in the range 0.1 mm per hour - 3 mm per hour
  • the crystal growth is actualized both with and without rotation of the seed crystal
  • a crystal 16 has an approximately round cross-section profile when it is pulled from a melt 15 with rotation.
  • the rotation rate may be varied between 1 and 30 revolutions per minute.
  • melt-crystal interface 36 An increased amount of crystal and a reduced quantity of melt in the crucible alters the thermal conditions in the melt-crystal interface 36. This alteration may result in interface instability, and degradation of crystal quality.
  • a mixed oxide charge having a composition of the melt 15 is continuously added to the melt 15 while a crystal 16 is drawn from the melt 15.
  • annealing and cooling of the crystal is accomplished at an average rate of 10 - 40 °C/hour.
  • a single crystal of La 3 Ga 5 5 Nbo 5 ⁇ 4 was grown by a drawing seed crystal 12 from a melt 15 through a dipped forming mould 14 as shown in FIG. 1 .
  • the starting materials were prepared by drying and mixing 99.999% pure La 2 O 3 , Ga 2 O 3 , and Nb 2 Os powders in a stoichiometric ratio, pressing, and then melting in several steps in a cylindrical indium crucible 11 of 150 mm diameter and 150 mm height with a wall thickness 2.0 mm.
  • the thermal unit 10 of the CRYSTAL-3M growth machine Mounted in the thermal unit 10 of the CRYSTAL-3M growth machine, the iridium crucible 11 containing a 120-mm diameter forming mould was heated by a conventional RF heating method. Growth was performed in an atmosphere of mixed argon and oxygen the oxygen content of which was 1.5 vol%.
  • the revolving seed crystal 12 oriented at 54 deg to the "Y" axis was brought in contact with the surface of melt 15 at a frequency of rotation of 3-18 1 /minute.
  • the crystal growth process continued until the solidified fraction g was approximately 0.48.
  • the pulling rate was 0.5 mm/hour.
  • After-growth annealing of the 100-mm diameter crystal was performed at average rate of cooling of 25° C/hour.
  • the grown crystal was an ochre color.
  • the method ensures growing of high-quality crystals which may be used for manufacture of crystal elements of SAW filters.
  • the cutting of the grown langanite boule is effected perpendicularly relative to axis of growth, thus reducing the cost of crystal wafers and thus enhancing efficiency.
  • a single crystal of La 3 Ga 5 SiOu was grown by drawing a seed crystal 12 from a melt 15 through a dipped forming mould 14 as shown in FIG. 1.
  • the starting materials were prepared by drying, mixing 99.999% pure La 2 O 3 , Ga 2 O 3 , and SiO 2 powders in a stoichiometric ratio, pressing, and then melting these powders in several steps in a cylindrical iridium crucible 11 having 120 mm in diameter and 120 mm in height with a wall thickness 2.0 mm.
  • a cylindrical iridium crucible 11 Mounted in the thermal unit 10 of the CRYSTAL-3M growth machine the iridium crucible 11 containing a 90-mm diameter forming mould was heated by a conventional RF heating method. Growth was performed in an argon atmosphere.
  • the revolving seed crystal 12 oriented at 54 deg to the "Y" axis was brought in contact with the surface of the melt 15 at a frequency of rotation of 3-18 1/minute.
  • the crystal growth process was continued until the solidified fraction g was approximately 0.7.
  • the pulling rate was 0.7 mm/hour.
  • After- growth annealing of the 83-mm diameter crystal was performed at average rate of cooling of 35° C/hour.
  • the grown crystal was a colorless.
  • the method ensures growing high- quality crystals which may be used for manufacture of crystal elements of SAW filters.
  • the cutting of the grown langasite boule is effected perpendicularly relative to axis of growth, thus reducing the cost of crystal wafers and thus enhancing efficiency.
  • a single crystal of La 3 Ga 5 . 5 Tao .5 O ⁇ was grown by drawing a seed crystal 12 from a melt 15 through a dipped forming mould 14 as shown in FIG. 3.
  • the starting materials were prepared by drying and mixing 99.999% pure La 2 O 3 , Ga 2 O 3 , and Ta 2 O 5 powders in a stoichiometric ratio, pressing, and then melting these powders in several steps in a cylindrical iridium crucible 11 having 120 mm diameter and 120 mm height with a wall thickness 2.0 mm.
  • a cylindrical iridium crucible 11 having 120 mm diameter and 120 mm height with a wall thickness 2.0 mm.
  • the thermal unit 10 of the CRYSTAL-3M growth machine the iridium crucible 11 containing a 88-mm x 88-mm forming mould was heated by a conventional RF heating method. Growth was performed in a mixture of nitrogen and oxygen (the content of oxygen is up to 20 vol%).
  • the revolving seed crystal 12 oriented along the crystallographic Z-axis was brought in contact with the surface of the melt 15 at frequency of rotation of 1-7 1 /minute.
  • the crystal growth process was continued until the solidified fraction g was approximately 0.6.
  • the pulling rate was 0.7 mm/hour.
  • After- growth annealing of the 80-mm diameter crystal was performed at an average rate of cooling of 35° C/hour.
  • the grown crystal was a dark red color. The method ensures growing high-quality crystals which may be used for the manufacture of crystal elements of SAW filters.
  • a single crystal of La 2 ggsCao oosSio 995 Tao.oo5GasO ⁇ 3 gDo ⁇ was grown by drawing a seed crystal 12 from a melt 15 through a dipped forming mould 14 as shown in FIG. 3.
  • the starting materials were prepared by drying and mixing 99.999% pure oxide powders of lanthanum, gallium, silicon, calcium and tantalum.
  • the pressed mixture was melted in several steps in a cylindrical iridium crucible 11 100 mm in diameter and 100 mm in height with a wall thickness 2.0 mm.
  • the metallic gallium in the preset range of concentration was added to the melt.
  • Mounted in the thermal unit 10 of the CRYSTAL-3M growth machine the iridium crucible 11 containing a 75-mm x 75-mm forming mould was heated by a conventional RF heating method. Growth was performed in an argon atmosphere.
  • a seed crystal 12 oriented along the crystallographic Z-axis was brought into contact with the surface of melt 15 without rotation of the crystal holder.
  • the pulling rate was 1 mm/hour.
  • the crystal growth process was continued until the solidified fraction g was approximately 0.45.
  • After- growth annealing of 75-mm x 75-mm cross- section crystal was performed at average rate of cooling of 30° C/hour.
  • the grown crystal was colorless. The method ensures the growing of high-quality crystals which may be used for manufacture of crystal elements for surface acoustic wave filters.
  • a single crystal of La 2 5 Ba 2+ 0 5 ScGe ⁇ 5V 0 5Ga 3 Oi39 7 5Fo 5 was grown by drawing a seed crystal 12 from a melt 15 through a dipped forming mould 14 as shown in FIG. 3.
  • the starting materials were prepared by drying and mixing 99.999% pure oxide powders of lanthanum, gallium, barium, scandium, germanium and vanadium in the preset range of concentration.
  • the pressed mixture was melted in several steps in a cylindrical iridium crucible 11 having 100 mm diameter and 100 mm height with a wall thickness 2.0 mm.
  • thermal unit 10 of the CRYSTAL-3M growth machine the iridium crucible 11 containing a 75-mm x 75-mm forming mould was heated by a conventional RF heating method. Growth was performed in a mixture of argon and fluorine (the content of fluorine was 0.5 vol%).
  • the revolving seed crystal 12 oriented at 54 deg to the "Y" axis was brought into contact with the surface of the melt 15 at frequency of rotation of 2-1 1 1 /minute.
  • the pulling rate was 1.2 mm/hour.
  • the crystal growth process was continued until the solidified fraction g was approximately 0.5
  • After-growth annealing of the 75-mm diameter crystal was performed at an average rate of cooling of 30° C/hour.
  • the grown crystal was colorless.
  • the method ensures growing' high-quality crystals which may be used for manufacture of crystal elements for surface acoustic wave filters. Further results of growing with still different technological parameters are presented in Figs 4a and 4b.

Abstract

A method for producing piezoelectric lanthanide gallium crystals includes pulling a crystal through a forming mould dipped into a crucible containing a melt, which controls a heat and mass transfer, as the crystal is grown. While a lanthanide gallium single crystal is growing, a charge of mixed oxides, having a composition of the melt may be continuously added to the melt such that the quantity of melt is maintained substantially stable. Crystals produced by this method exhibit less variability in piezoelectric properties. The growth direction of the crystal is aligned along an axis perpendicular to such a crystallographic plane of lanthanide gallium crystal that an improved temperature stability, lowered power flow angle, and reduced diffraction would be present in surface acoustic wave (SAW) devices made in this crystallographic plane. Such crystals are more suitable for the mass-production slicing wafers, for example over 2 inches in diameter, for SAW devices.

Description

METHOD OF GROWING PIEZOELECTRIC LANTHANIDE GALLIUM CRYSTALS
FIELD
The present invention relates to a method of growing large diameter piezoelectric
Ln3Ga5 5Meo 5θι (Ln=La, Pr, Nd and Me=Nb,Ta) and Ln3Ga5M'Oι4 (Ln=La, Pr, Nd M -Si, Ti, Zr, Hf) single crystals and solid solutions on this basis and more particularly to a method of growing such crystals for use as wafers in bulk acoustic wave (BAW), surface acoustic wave (SAW), and pseudo surface acoustic wave (PSAW) devices, having an excellent temperature characteristic and a large electromechanical coupling factor The SAW devices are currently used, for example, as bandpass filters, resonators, delay lines and converters, in a broad range of wireless applications, cellular communication devices and cable TV
DESCRIPTION OF THE PRIOR ART
Piezoelectric material based on lanthanide gallium crystals, including the langasite family of crystals, i.e La3Ga3SιOι4, referred to as langasite (LGS), La3Ga5 5Nb05θι4, referred to as langanite (LGN), and langatate La3Ga5 5Ta0 5θι4 (LGT) are known to be useful for piezoelectric applications A SAW device having a LGS single crystal substrate is disclosed in U S Pat No 5,821 ,673, U K Pat No 2,328,815, RU Pat No 2073952, and U S Pat No 5,917,265 A LGT single crystal substrate having a prescribed range of Euler angles for substrate and crystal orientation to improve signal processing in a SAW device, is disclosed in U S Pat No 6,097,131
A SAW device comprising a wafer constructed of a trigonal langasite crystal cut at predominated cut angles is disclosed in U S Pat No 5,981 ,673 An optimal cut for SAW devices made from langatate crystals is disclosed in U S Pat No 6,097, 131 A substrate for piezoelectric device and SAW devices composed of a single crystal of langanite is proposed in JP Pat No 11106294A The method of oriented crystallization from a melt, eliminating any contact with the side faces of a growing crystal with solid walls, are now well known and increasingly becoming widespread. These are the Czochralski (conventional Czochralski), Stepanov, Verneuil and floating zone techniques, characterized by a fixed orientation of crystallization at a fixed position of the solid - liquid interface. Each of these techniques has a predominant field of application with the common feature of the elimination of contact between the crystal and a solid wall. As a result, both the shape and the size of a growing crystal are essentially determined by capillary forces, which form a meniscus in the interface boundary zone. In addition, the crystallization process also depends on the conditions of heat and mass exchange in the crystal-melt system, which is generally described in the publication "Some aspects of the macroscopic theory of oriented crystallization from the melt", E.A. Brener and V.A. Tatarchenko, Acta Physica Academias scientiarum Hungahcas, 47 (1-3) (1979) 133-138. A Stepanov crystal growth method based on a capillary formed pole of melt by means of a special mould and the crystallization of the pole outside the container is generally described in "Capillary shaping in crystal growth from melts" V.A. Tatarchenko, Journal of Crystal Growth 37 (1977) 272-284 and "Crystallization stability during capillary shaping" G,l Babkin, E A Brener and V.A. Tatarchenko, Journal Crystal Growth 50 (1980) 45-50 Another crystal growth method, the EFG crystal growth method, is a method of profiled crystal growth or a method of edge defined film fed growth. The capillary action shaping technique, CAST differs from the EFG technique in the construction of the forming mould and a presence of forced inert gas cooling The Stepanov, EFG and CAST methods are described in the publication "Growth the profiled single crystals by Stepanov technique" P I Antonov, L.M. Zatulovskn, A.C. Kostyugov, (eds) Leningrad "Nauka" (1981) 280 pp
The method proposed for growing a piezoelectric material based on lanthanide gallium crystals is the conventional Czochralski crystal growth method The growth of the langasite family of crystals by the Czochralski method is accurately described in "Investigation of trigonal (Laι-xNdx)3Ga2SiO14 crystals" A.A Kaminskn, B V Mill, G G
Khodzhabagyan, A F Konstantinova, A.I Okorochkov, and I M Silvestrova, Physics Status Solid (A) 80 (1983) 387-398 and "Czochralski growth and characterization of piezoelectric single crystals with langasite structure: La3Ga5SiO1 (LGS), La3Ga5.5Nbo.5Oι4 (LGN) and La3Ga5.5Ta0.5θι4 (LGT), Part I." J. Bohm, R.B. Heimann, M'. Hengst, R. Roewer, J. Schindler, Journal of Crystal Growth 204 (1999) 128-136 and "Czochralski growth and characterization of piezoelectric single crystals with langasite structure: La3Ga5SiO14 (LGS), La3Ga5.5Nbo.5θι4 (LGN) and La3Ga5.5Tao.5O14 (LGT), Part II. Piezoelectric and elastic propeties" J. Bohm, E. Chilla, C. Flannery, H.-J. Frohlich, T. Hauke, R.B. Heimann, M. Hengst, U. Strauber, J. Schindler, Journal of Crystal Growth 216 (2000) 293-298. The Czochralski growth method of solid solutions of piezoelectric lanthanum gallium silicate single crystals is presented in the publication "Czochralski growth of RE3Ga5SiOu (RE = La, Pr, Nd) single crystals for the analysis of the influence of rare earth substitution on piezoelectricity" J. Sato, H. Takeda, H. orikoshi, K. Shimamura, P. Rudolph, T. Fukuda, Journal Crystal Growth 191 (1998) 746-753.
The successful growth of 1 or 2 inch diameter and 130 mm length La3GasSiOι4 single crystal using the conventional Czochralski technique is described in "Growth and characterization of lanthanum gallium silicate La3Ga5SiOι4 single crystals for piezoelectric applications" Kiyoshi Shimamura, Hiroaki Takeda, Tsuguo Fukuda, Journal of Crystal Growth 163 (1996) 388-392. The Czochralski method for growth of a langasite crystal of 3-inch diameter with a 90 mm length cylindrical part along the Z-axis is described in the publications "Growth of a 3" langasite crystal with clear faceting" Satoshi Uda, O. Buzanov, Journal of Crystal Growth, 211 (2000) p. 318-324, "Growth of 3-inch langasite single crystal and its application to substrate for surface acoustic wave filters", Satoshi Uda, Akihiro Bungo, Chunyun Jian, Japan Journal Applied Physics, 38 (1999) 5516-5519. Growth of langatate La3Tao.5Ga5.5Ou crystals by the Czochralski method is described in "Growth and characterization of La3Tao.5Ga5.5Ou single crystals" Hiroyuki Kawanaka, Hiroaki Takeda, Kiyoshi Shimamura, Tsuguo Fukuda, Journal of Crystal Growth 183 (1998) 274-277.
A method of growing single crystals of lanthanum-gallium silicate is disclosed in
RU Pat. No 2126064, RU Pat. No 2143015, RU Pat. No 2126063, RU Pat. No 2108417, RU Pat. No 2108418, and W.O. Pat. No 9961686A1. The essence of the method consists in the selection of the orientation of the seed crystal ensuring growth by the Czochralski method of single crystals of lanthanum-gallium silicate along the directions <01.1>, <02.1>, <02.3>, <03.2> or at 54 degrees to the "Y" axis. A method of growing of lanthanum gallium tantalum single crystal (LGT) is disclosed in JP Pat. No 11322495A and JP Pat. No 11199392A in which langatate crystals are doped with Pr, Nd, Ce, Sm and Eu impurities are grown by the Czochralski method.
While these methods can be used to make piezoelectric crystals, which are useful in certain applications, there is a variability of the piezoelectric behavior of different wafers cut from the same boule of lanthanide gallium crystal. The growth of langasite is characterized by distinct faceting along the (0001 ), (01Ϊ0 ) and (01Ϊ1) planes. Facet growth requires a greater supercooling than growth with a rough surface and hence the interface advances periodically rather than continuously.
Further, greater supercooling often leads to the presence of secondary or polycrystalline phases, resulting in scattering and/or cracking which is another problem of the conventional Czochralski method.
According to all the above-mentioned methods of growth, the lanthanide gallium melt needs to be held (soaked) at a certain temperature for a considerable time (4 - 20 hours). An appropriate thermal treatment of the melt is needed in order to obtain stable physical properties, which then permits further precise control of the melt temperature. An associated problem is the duration of the growth process and therefore its cost increases by up to 30%.
As described above, a bulk piezoelectric lanthanum gallium single crystal of good quality cannot presently be obtained with a high yield using a conventional Czochralski method. It is an object of the present invention to provide a method for producing material, based on the lanthanide gallium crystals for use as piezoelectric, which displays substantially uniform piezoelectric properties throughout the crystal, a reproducibility of properties, a high yield, and resulting in a low manufacturing cost of BAW and SAW devices.
It is another object of the present invention to provide an improved Czochralski crystal growth method for producing piezoelectric material based on the lanthanide gallium crystals.
SUMMARY OF THE INVENTION
To overcome the problems described above, the present invention provides a method for producing lanthanide gallium crystals in which, to control heat and mass transfer and to maintain a steady state of crystal melt interface, the growing crystal is pulled through a forming mould dipped into the melt contained in a crucible. While a lanthanide gallium single crystal is growing, a mixed oxide charge of the same composition as the melt may be continuously added to the melt such that the quantity of melt is maintained substantially stable. Crystals produced by this method exhibit less variability in piezoelectπc properties.
The shape of the solid-liquid interface is determined by the shape of the freezing isotherm. Consequently, the objects of the invention are achieved by controlling the shape of the freezing isotherm during the main part of the crystal growth. There may be some vaπation from the desired conditions at the beginning and the end of the growth. The thermal conditions are determined by the crucible and forming mould sizes and their location in the heating environment as well as the furnace design and the insulating material employed.
The preferred embodiments of the present invention also provide an optimal growth direction for the crystal aligned with axis perpendicular to such a crystallographic plane of lanthanide gallium crystal that an improved temperature stability, lower power flow angle, and reduced diffraction are present in a SAW device cut in this plane. Consequently, the other objects of the invention are achieved by choosing an optimum growth direction for piezoelectric applications independently of the crystallization rate. Optimal orientation allows the cutting of wafers at an angle of 90 degrees to growth axis to ensure minimal losses of material. This also means that the temperature coefficient of frequency in the wafer is close to zero. The optimally oriented lanthanum gallium crystals which are grown are more suitable for the mass-production slicing of crystals into wafers for SAW devices, suitable sizes of which may be 2 inches or more in diameter.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing summary, as well as the following detailed description of the preferred embodiments of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention there is shown in the drawings embodiments which are presently preferred. It should be understood, however, that the present invention is not limited to the particular arrangements and instrumentalities shown. In the drawings:
Fig. 1 shows a schematic view of the different furnaces used to produce different sizes of piezoelectric lanthanum gallium single crystals;
Fig. 2a is a schematic showing the seed crystal oriented along the crystallographic z-axis and the optimally oriented wafers cut from grown boule;
Fig. 2b is a schematic showing the seed crystal oriented at α degrees to the "Y" axis and the optimally oriented wafers cut from grown boule;
Fig. 3 shows the different constructions of forming moulds; and Figs. 4a and 4b are tables of the results of growing crystals using various compositions and the parameters used in the growing operation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION
While this invention can have many different embodiments, the drawings and description will detail several specific embodiments. It should be understood, however, that the present disclosure is to be considered as exemplification of the principles of the invention and is not intended to limit the invention to any specific embodiment.
Crystal growth is accomplished with a crystal grower machine (Kristall-3M) which includes a furnace as shown in FIG.1. The furnace comprises a housing 10 formed from refractory and insulating materials and having a crucible 11 located therein. The crucible 11 holds a forming mould 14 dipped into a melt 15. The housing includes an aperture for insertion of a seed crystal 12. An RF inductive heating coil 13 surrounds the housing 10 at the level of the crucible 11.
In general the class of piezoelectric lanthanum gallium crystals covered by this invention can be described by the following chemical formulae:
Formula (1):
[Ln 3_x.y Me x+y]a Me o so+xjb [Me o sα-xj e y Ga5.y]c O05[(g.x.y)a+25(n-X)b+(i65-1 5x+y)c].
.3+ where Ln is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me + is at least one of the elements selected from the group consisting of Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V; x is a value not exceeding one; y is a value not exceeding (2 - x); 0.92<a<1.07; 0.9<b<1.1 ; and 0.99<c<1.02 Formula (2):
[Ln + 3.χ-y Me x+y]a [Mβ ι.x+y Me x]b Ga(5.y)c Oo 5[(9-x-y)a+(4+x+4y)b+3(5-y)c].
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me4+ is at least one of the elements selected from the group consisting of Ti, Zr, Hf, Sn, Ce, Pr, Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V; x is a value not exceeding one; y is a value not exceeding (2 - x); 0.86<a<1.1 ; 0.85<b<1.3; and 0.94<c<1.08
Formula (3):
[Ln3+ 3.x Me2\]a Me3+ b [Me4+ 2.x Vx Ga3]c O05[(9-X)a+3b+(i7+X)c],
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si, Ge, and Sn; x is a value not exceeding two; 0.86<a<1 1 ; 0.85<b<1.3; and 0.94<c<1.08
Formula (4):
[Ln 3.x.y Me x+y]a Me o 5(1+x)b [Mθ 05(1- ) Me y Gas.y]c O05[(9-x-y)a+25( x)b+065-1 5x+y)c|-zQz
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me + is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V; D represents oxygen vacancies of quantity z not exceeding 0.2 formula units; x is a value not exceeding one; y is a value not exceeding (2 - x); 0.92<a<1.07; 0.9<b<1.1 ; and 0.99<c<1.02
Formula (5):
[Ln 3_x_y Me x+y]a [Me ι_x+y Me x]b Ga(5-y)C Oo 5[(9-x-y)a+(4+x+4y)b+3(5-y)c]-zOz,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me4+ is at least one of the elements selected from the group consisting of Ti, Zr, Hf, Sn, Ce, Pr, Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V; D represents oxygen vacancies of quantity z not exceeding 0.2 formula units; x is a value not exceeding one; y is a value not exceeding (2 - x); 0.86<a<1.1 ; 0.85<b<1.3; and 0.94<c<1.08
Formula (6):
[Ln3Yx Me2*x]a Me3+ b [Me4+ 2.x Vx Ga3]c O0 5[<9-X)a+3b+(i7+X)c]-zπz,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si, Ge, and Sn; D represents oxygen vacancies of quantity z not exceeding 0.2 formula units; x is a value not exceeding a two; 0,86<a<1 1 ; 0.85<b<1 3; and 0.94<c<1.08
Formula (7):
[Ln 3.x.y Me x+y]a Me 0 5(1+x)b [Mβ 0 5(1-x) Me y Ga5.y]c Oo 5[(9-x-y)a+2 5(Hx)b*(16 5-1 5x+y)c] 05zFz where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V; F2 is fluorine of quantity z not exceeding 0.2 formula units; x is a value not exceeding one; y is a value not exceeding (2 - x); 0.92<a<1.07; 0.9<b<1.1 ; and 0.99<c<1.02.
Formula (8):
[Ln 3.x.y Me x+y]a [Me ι.χty Me χ]b Ga(5.y)C Oo 5[(9-x-y)a+(4+x+4y)b+3(5-y)c]-05zFz,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me4+ is at least one of the elements selected from the group consisting of Ti, Zr, Hf, Sn, Ce, Pr, Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V; Fz is fluorine of quantity z not exceeding 0.2 formula units; x is a value not exceeding unit, y is a value not exceeding (2 - x); 0.86<a<1.1 ; 0.85<b<1.3; and 0.94<c<1.08.
Formula (9):
[Ln3+ 3.x Me2+ X]a Me3*b [Me4\x Vx Ga3]c O05[(9-X)a*3b-(i7*x)c]-0 5zF2,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si, Ge, and Sn; Fz is fluorine of quantity z not exceeding 0.2 formula units; x is a value not exceeding two; 0.86<a<1.1 ; 0.85<b<1.3; and 0.94<c<1 .08. In use, the raw oxide powder materials mentioned in formulae (1) - (9) are dried at 1000°C then mixed in the appropriate proportions and pressed into pellets (where appropriate), and loaded into the crucible. The materials are then melted and the melt 15 may be doped with the oxides of micro additions of the chemical elements Li, Be, B, Na, Mg, Al, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, As, Se, Rb, Sr, Y, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, Ce, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, U,Th at a quantity between 1χ1017 atom/cm3
Figure imgf000013_0001
The seed crystal 12 may be arbitrary orientated, including orientation coinciding with the Z-axis (see Fig. 2a) or oπentation aligned with the α-Y axis perpendicular to a crystallographic plane of lanthanum gallium crystal (Fig 2b) Crystals sliced along the crystallographic plane have an optimized combination of a minimal power flow angle, a minimal temperature coefficient of frequency, negligible diffraction, and high electromechanical coupling factor. With an α-Y axis orientation it is possible to cut wafers 30 at an angle of 90 degrees to the growth axis to ensure minimal losses of material and a crystal temperature coefficient of frequency close to zero.
The seed crystal 12, oriented at α degrees to the "Y" axis or having another optimal orientation or an arbitrary orientation, is brought in contact with the surface of the melt 15 Using the seed crystal 12 the growing crystal 16 is drawn from the melt 15 through the forming mould 14 dipped in the melt 15 The forming moulds 14 are fixed independently of the crucible 11 to facilitate mould replacement and prevent deformation on the melt 15 solidification The forming mould is set in crucible 11 to control heat and mass transfer and to maintain a steady state of the crystal melt interface The main task to solve is the creation of a temperature distribution near the solid-liquid interface such that the profile of isotherms in the melt 15 define geometrical form of the pulling crystal The forming mould 14 has an arbitrary cross-sectional form including round or square, and a height less than the crucible 11 height Different constructions of forming moulds 14 used in Stepanov's, EFG and CAST crystal growth methods are presented in FIG 3 The single-capillary 31 , double-capillary 32, and multi-capillary 33 forming mould designs are presented as examples. The capillary moulds for types 31 and 32 comprise two or more parajlel vertical plates 38 of equal length and 1 mm thickness, with a 1 mm-space to provide the capillary action. The multi-capillary moulds 33 have from 20 to 120 channels with 0.1 mm deep grooves on the surface of the plates. While the crystal is drawn through a forming mould the melt 15 moves up in capillary channels 34 under action of surface tension forces as a result of wetting 35 of the walls.
The crystals are grown in an argon atmosphere, in a mixture of argon and oxygen (the content of oxygen is up to 20 vol%), in a mixture of argon and carbon dioxide (the content of carbon dioxide is up to 20 vol%), in a mixture of argon and fluorine (the content of fluorine is up to 3 vol%), in a nitrogen atmosphere, in a mixture of nitrogen and oxygen (the content of oxygen is up to 20 vol%), or in a mixture of nitrogen and fluorine (the content of fluorine is up to 3 vol%) The crystals grown varied from colourless, through pale yellow and dark orange, to oxblood red in colour, depending on the oxygen content in the atmosphere in the growth chamber A high oxygen content (approximately 8 - 20 vol% of oxygen) yields the oxblood red colour, whereas an oxygen content of about 2-8 vol% yields the darker orange colour The crystals grown in an oxygen free atmosphere were colourless This shading colour is caused by oxygen vacancies formed, the quantity of which depends on the amount of oxygen in the growth atmosphere
The crystal is drawn through a forming mould when the pulling speed is in the range 0.1 mm per hour - 3 mm per hour
The crystal growth is actualized both with and without rotation of the seed crystal
When the crystal is grown from the melt 15 without rotation, its cross-section is determined by the shape of the melt column, because the cross-section of the pulled crystal 16 is determined by inter-section of the melt column and the melt-crystal interface 36. A crystal 16 has an approximately round cross-section profile when it is pulled from a melt 15 with rotation. The rotation rate may be varied between 1 and 30 revolutions per minute.
An increased amount of crystal and a reduced quantity of melt in the crucible alters the thermal conditions in the melt-crystal interface 36. This alteration may result in interface instability, and degradation of crystal quality. To maintain a quantity and a substantially stable level of melt 15 in crucible 11 a mixed oxide charge having a composition of the melt 15 is continuously added to the melt 15 while a crystal 16 is drawn from the melt 15.
After growth, annealing and cooling of the crystal is accomplished at an average rate of 10 - 40 °C/hour.
Specific examples of crystal growth to which the present invention is applied will be described below but the present invention is not limited to the specific examples.
(EMBODIMENT 1)
A single crystal of La3Ga5 5Nbo 5θι4, was grown by a drawing seed crystal 12 from a melt 15 through a dipped forming mould 14 as shown in FIG. 1 .
The starting materials were prepared by drying and mixing 99.999% pure La2O3, Ga2O3, and Nb2Os powders in a stoichiometric ratio, pressing, and then melting in several steps in a cylindrical indium crucible 11 of 150 mm diameter and 150 mm height with a wall thickness 2.0 mm. Mounted in the thermal unit 10 of the CRYSTAL-3M growth machine, the iridium crucible 11 containing a 120-mm diameter forming mould was heated by a conventional RF heating method. Growth was performed in an atmosphere of mixed argon and oxygen the oxygen content of which was 1.5 vol%. The revolving seed crystal 12 oriented at 54 deg to the "Y" axis was brought in contact with the surface of melt 15 at a frequency of rotation of 3-18 1 /minute. The crystal growth process continued until the solidified fraction g was approximately 0.48. The pulling rate was 0.5 mm/hour. After-growth annealing of the 100-mm diameter crystal was performed at average rate of cooling of 25° C/hour. The grown crystal was an ochre color. The method ensures growing of high-quality crystals which may be used for manufacture of crystal elements of SAW filters. The cutting of the grown langanite boule is effected perpendicularly relative to axis of growth, thus reducing the cost of crystal wafers and thus enhancing efficiency.
(EMBODIMENT 2)
A single crystal of La3Ga5SiOu, was grown by drawing a seed crystal 12 from a melt 15 through a dipped forming mould 14 as shown in FIG. 1.
The starting materials were prepared by drying, mixing 99.999% pure La2O3, Ga2O3, and SiO2 powders in a stoichiometric ratio, pressing, and then melting these powders in several steps in a cylindrical iridium crucible 11 having 120 mm in diameter and 120 mm in height with a wall thickness 2.0 mm. Mounted in the thermal unit 10 of the CRYSTAL-3M growth machine the iridium crucible 11 containing a 90-mm diameter forming mould was heated by a conventional RF heating method. Growth was performed in an argon atmosphere. The revolving seed crystal 12 oriented at 54 deg to the "Y" axis was brought in contact with the surface of the melt 15 at a frequency of rotation of 3-18 1/minute. The crystal growth process was continued until the solidified fraction g was approximately 0.7. The pulling rate was 0.7 mm/hour. After- growth annealing of the 83-mm diameter crystal was performed at average rate of cooling of 35° C/hour. The grown crystal was a colorless. The method ensures growing high- quality crystals which may be used for manufacture of crystal elements of SAW filters. The cutting of the grown langasite boule is effected perpendicularly relative to axis of growth, thus reducing the cost of crystal wafers and thus enhancing efficiency. (EMBODIMENT S)
A single crystal of La3Ga5.5Tao.5Oι , was grown by drawing a seed crystal 12 from a melt 15 through a dipped forming mould 14 as shown in FIG. 3.
The starting materials were prepared by drying and mixing 99.999% pure La2O3, Ga2O3, and Ta2O5 powders in a stoichiometric ratio, pressing, and then melting these powders in several steps in a cylindrical iridium crucible 11 having 120 mm diameter and 120 mm height with a wall thickness 2.0 mm. Mounted in the thermal unit 10 of the CRYSTAL-3M growth machine the iridium crucible 11 containing a 88-mm x 88-mm forming mould was heated by a conventional RF heating method. Growth was performed in a mixture of nitrogen and oxygen (the content of oxygen is up to 20 vol%). The revolving seed crystal 12 oriented along the crystallographic Z-axis was brought in contact with the surface of the melt 15 at frequency of rotation of 1-7 1 /minute. The crystal growth process was continued until the solidified fraction g was approximately 0.6. The pulling rate was 0.7 mm/hour. After- growth annealing of the 80-mm diameter crystal was performed at an average rate of cooling of 35° C/hour. The grown crystal was a dark red color. The method ensures growing high-quality crystals which may be used for the manufacture of crystal elements of SAW filters.
(EMBODIMENT 4)
A single crystal of La2 ggsCao oosSio 995 Tao.oo5GasOι3 gDo ι was grown by drawing a seed crystal 12 from a melt 15 through a dipped forming mould 14 as shown in FIG. 3.
The starting materials were prepared by drying and mixing 99.999% pure oxide powders of lanthanum, gallium, silicon, calcium and tantalum. The pressed mixture was melted in several steps in a cylindrical iridium crucible 11 100 mm in diameter and 100 mm in height with a wall thickness 2.0 mm. To produce oxygen vacancies in the quantity of 0.1 formula units the metallic gallium in the preset range of concentration was added to the melt. Mounted in the thermal unit 10 of the CRYSTAL-3M growth machine the iridium crucible 11 containing a 75-mm x 75-mm forming mould was heated by a conventional RF heating method. Growth was performed in an argon atmosphere. A seed crystal 12 oriented along the crystallographic Z-axis was brought into contact with the surface of melt 15 without rotation of the crystal holder. The pulling rate was 1 mm/hour. The crystal growth process was continued until the solidified fraction g was approximately 0.45. After- growth annealing of 75-mm x 75-mm cross- section crystal was performed at average rate of cooling of 30° C/hour. The grown crystal was colorless. The method ensures the growing of high-quality crystals which may be used for manufacture of crystal elements for surface acoustic wave filters.
(EMBODIMENT 5)
A single crystal of La25 Ba2+ 0 5ScGeι 5V05Ga3Oi3975Fo 5 was grown by drawing a seed crystal 12 from a melt 15 through a dipped forming mould 14 as shown in FIG. 3.
The starting materials were prepared by drying and mixing 99.999% pure oxide powders of lanthanum, gallium, barium, scandium, germanium and vanadium in the preset range of concentration. The pressed mixture was melted in several steps in a cylindrical iridium crucible 11 having 100 mm diameter and 100 mm height with a wall thickness 2.0 mm. Mounted in thermal unit 10 of the CRYSTAL-3M growth machine the iridium crucible 11 containing a 75-mm x 75-mm forming mould was heated by a conventional RF heating method. Growth was performed in a mixture of argon and fluorine (the content of fluorine was 0.5 vol%). The revolving seed crystal 12 oriented at 54 deg to the "Y" axis was brought into contact with the surface of the melt 15 at frequency of rotation of 2-1 1 1 /minute. The pulling rate was 1.2 mm/hour. The crystal growth process was continued until the solidified fraction g was approximately 0.5 After-growth annealing of the 75-mm diameter crystal was performed at an average rate of cooling of 30° C/hour. The grown crystal was colorless. The method ensures growing' high-quality crystals which may be used for manufacture of crystal elements for surface acoustic wave filters. Further results of growing with still different technological parameters are presented in Figs 4a and 4b.
Thus, it will be appreciated that various modifications, alternatives, variations, etc., may be made without departing from the spirit and scope of the invention as defined in the appended claims. It is, of course, intended to cover by the appended claims all such modifications as fall within the scope of the claims.

Claims

We claim:
1. A method of growing piezoelectric lanthanide gallium crystals comprising:
forming a lanthanide-gallium melt;
drawing a crystal of predetermined crystallographic orientation from said melt while the growing crystal is pulled through a dipped forming mould in order to control a heat and mass transfer and to maintain a crystal melt interface in a steady state.
2. The method of claim 1 , including continuously adding to the melt a mixed oxide charge of the same composition as the melt such that the quantity of melt is maintained substantially stable.
3. A method as claimed in claim 1 , wherein said method of growing is a Czochralski crystal growth method.
4. A method as claimed in claim 1 , wherein said method of growing is a Stepanov crystal growth method.
5. A method as claimed in claim 4, wherein said Stepanov crystal growth method includes an edge-defined, film-fed (EFG) crystal growth method.
6. A method as claimed in claim 4, wherein said Stepanov crystal growth method includes a capillary action shaping technique (CAST) crystal growth method.
7. A method as claimed in claim 1 , wherein a direction of crystal growth is aligned along an axis perpendicular to a crystallographic plane of said crystal having an optimized combination of minimal power flow angle, minimal temperature coefficient of frequency, negligible diffraction and high electromechanical coupling factor.
8. A method as claimed in claim 1 , wherein a direction of crystal growth is aligned along an axis perpendicular to a crystallographic plane of said crystal having simultaneously zero power flow angle, zero temperature coefficient of frequency, negligible diffraction, and high electromechanical coupling factor.
9 A method according to claim 1 , wherein the piezoelectric lanthanide gallium crystals have a composition represented by the chemical formula
[Ln 3.x.y Me x+y]a Me 05(1+x)b [Me 05(1-x) Me y Ga5-y]c Oo 5[(9-x-y)a+2 5(1+x)b+(165-1 5x+y)c],
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd, Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V, x is a value not exceeding one, y is a value not exceeding (2 - x); 0.92<a<1.07, 0.9<b<1 1 ; and 0 99<c<1 02
10 A method according to claim 1 , wherein the piezoelectric lanthanide gallium crystals have a composition represented by the chemical formula
[Ln 3-χ.y Me x+y]a [Me ι-x+y Me χ]b Ga(5-y)c Oθ 5[(9-x-y)a+(4+x+4y)b+3(5-y)c]1
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd, Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb, Me4+ is at least one of the elements selected from the group consisting of Ti, Zr, Hf, Sn, Ce, Pr, Si and Ge, Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V, x is a value not exceeding one, y is a value not exceeding (2 - x), 0 86<a<1 1 , 0 85<b<1 3, and 0 94<c<1 08
11. A method according to claim 1 , wherein the piezoelectric lanthanide gallium crystals contain vanadium (V) and have a composition represented by the chemical formula
[Ln3+ 3-x Me2+ X]a Me3+ b [Me + 2.x Vx Ga3]c O05[(9-x)a+3b+(i7+x)c],
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd, Me + is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si, Ge, and Sn; x is a value not exceeding two, 0.86<a<1.1 , 0 85<b<1 3, 0.94<c<1.08.
12 A method according to claim 1 , wherein the piezoelectric lanthanide gallium crystals contain oxygen vacancies D of quantity z not exceeding 0 2 formula units and have a composition represented by the chemical formula
[Ln 3.x.y Me x+y]a Me o 5(i+ ) [Me 0 5(1 x) Me y Gas.y]c Oo 5[(9- y)a+25(n- )b+o65 1 5X+y)ci zQ∑,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd, Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb, Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In, Me + is at least one of the elements selected from the group consisting of Si and Ge, Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V, x is a value not exceeding one, y is a value not exceeding (2 - x), 0 92<a<1 07, 0 9<b<1 1 , 0 99<c<1 02
13 A method according to claim 1 , wherein the piezoelectric lanthanide gallium crystals contain oxygen vacancies D of quantity z not exceeding 0 2 formula units and have a composition represented by the chemical formula [Ln + 3-x-y Me + x+y]a [Me +ι-x+y Me +χ]b Ga(5-y)c Oo.5[(9-x-y)a+(4+x+4y)b+3(5-y)c]-zDz,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me4+ is at least one of the elements selected from the group consisting of Ti, Zr, Hf, Sn, Ce, Pr, Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V; x is a value not exceeding one, y is a value not exceeding (2 - x); 0.86<a<1.1 ; 0.85<b<1.3; 0.94<c<1.08.
14. A method according to claim 11 , wherein the lanthanide gallium crystals contain oxygen vacancies D of quantity z not exceeding 0.2 formula units and have a composition represented by the chemical formula
[Ln3+ 3-x Me2+ X]a Me3+ b [Me4+ 2-x Vx Ga3]c O0 5[(9- )a+3b+(i7+x)c]-zDz,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si, Ge, and Sn; x is a value not exceeding two; 0.86<a<1.1 ; 0.85<b<1.3; and 0.94<c<1.08.
15. A method according to claim 1 , wherein the piezoelectric lanthanide gallium crystals contain fluorine F of quantity z not exceeding 0.2 formula units and are represented by the chemical formula
[Ln 3.x.y Me x+y]a Me 05(1+x)b [Me 0 5(i.x) Me y Gas.y]c Oo 5((9-x-y)a+2 5( x)b+(16 5-l 5x+y)c]-0 5zFz,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of
Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V; x is a value not exceeding one; y is a value not exceeding (2 - x); 0.92<a<1.07; 0.9<b<1.1 ; and 0.99<c<1.02.
16. A method according to claim 1 , wherein the piezoelectric lanthanide gallium crystals contain fluorine F of quantity z not exceeding 0.2 formula units and have a composition represented by the chemical formula
[Ln 3-x-y Me x+y]a [Me ι-x+y Me χ]b Ga(5-y)C Oo.5[(9-x-y)a+(4+χ+4y>b+3(5-y)c]-o 5zFz,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me4+ is at least one of the elements selected from the group consisting of Ti, Zr, Hf, Sn, Ce, Pr, Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V; x is a value not exceeding one; y is a value not exceeding (2 - x); 0.86<a<1.1 ; 0.85<b<1.3; and 0.94<c<1.08.
17. A method according to claim 1 , wherein the piezoelectric lanthanide gallium crystals contain fluoπne F of quantity z not exceeding 0.2 formula units and have a composition represented by the chemical formula
[Ln3+ 3-x Me2+ X]a Me3+ b [Me4+ 2.x Vx Ga3]c O0 5[(9-x)a+3b+(i7+x)c]-0 5zFz,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si, Ge, and Sn; x is a value not exceeding two; 0.86<a<1.1 ; 0.85<b<1.3; and 0.94<c<1.08.
18. A method according to claim 9, wherein the lanthanide gallium crystals have a composition represented by the chemical formula
Ln3+ 3-x-y Me2+ x+y Me3+ 05(i-x) Me4+ y Me5+ 0 5(1+X) Ga5-y Oi4,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd, Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V, x is a value not exceeding one, y is a value not exceeding (2 - x).
19. A method according to claim 10, wherein the lanthanide gallium crystals have a composition represented by the chemical formula
Ln3+ 3.x-y Me2+ x+y Me \x+y Me5+ X Ga5-y O1 ,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd, Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb, Me4+ is at least one of the elements selected from the group consisting of Ti, Zr, Hf, Ge, Sn, Ce, Pr, Si and Ge, Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V, x is a value not exceeding one, y is a value not exceeding (2 - x)
20 A method according to claim 1 1 , wherein the lanthanide gallium crystals have a composition represented by the chemical formula
Ln3+ 3.χ Me2+ X Me3+ Me4+ 2-x Vx Ga3 O14, where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2* is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si, Ge, and Sn; x is a value not exceeding two.
21. A method according to claim 12, wherein the lanthanide gallium crystals contain oxygen vacancies D of quantity z not exceeding 0.2 formula units and have a composition represented by the chemical formula
Ln3+ 3-x-y Me2+ x+y Me3+o.5(ι-X) Me + y Me5+ 0.5(i+x) Ga5-y Ou-zDz,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me + is at least one of the elements selected from the group consisting of Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V; x is a value not exceeding one, y is a value not exceeding (2 - x).
22. A method according to claim 13, wherein the lanthanide gallium crystals contain oxygen vacancies D of quantity z not exceeding 0.2 formula units and have a composition represented by the chemical formula
Ln3+ 3.x-y Me + x+y Me4Yx+y Me5+ X Ga5.y Ou-zDz,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce,
Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of
Ca, Sr, Ba, and Pb; Me + is at least one of the elements selected from the group consisting of Ti, Zr, Hf, Sn, Ce, Pr, Si and Ge; Me5+ is at least one of the elements I 25
selected from the group consisting of Nb, Ta, Sb, and V; x is a value not exceeding one, y is a value not exceeding (2 - x).
23. A method according to claim 14, wherein the lanthanide gallium crystals contain oxygen vacancies D of quantity z not exceeding 0.2 formula units and have a composition represented by the chemical formula
Ln3+ 3-x Me2+ X Me3+ Me4+ 2-x Vx Ga3 Ou-zDz,
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si, Ge, and Sn; x is a value not exceeding two.
24. A method according to claim 15, wherein the lanthanide gallium crystals contain fluorine of quantity z not exceeding 0.2 formula units and have a composition represented by the chemical formula
Ln3+ 3.x.y Me2+ x+y Me3+ 0 5(i-x) Me4+ y Me5+ 0 5(ι+ ) Ga5.y Ou-o 5zFz
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In; Me4+ is at least one of the elements selected from the group consisting of Si and Ge; Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V; x is a value not exceeding one, y is a value not exceeding (2 - x).
25. A method according to claim 16, wherein the lanthanide gallium crystals have a composition represented by the chemical formula Ln3+ 3-x-y Me2+ x+y Me4+ι-x+y Me5+ X Ga -y Ou-0 5zFz
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd; Me + is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me4+ is at least one of the elements selected from the group consisting of Ti, Zr, Hf, Ge, Sn, Ce, Pr, Si and Ge, Me5+ is at least one of the elements selected from the group consisting of Nb, Ta, Sb, and V, x is a value not exceeding one, y is a value not exceeding (2 - x) and z < 0 2
26 A method according to claim 17, wherein the lanthanide gallium crystals contain a fluoπne F of quantity of quantity z not exceeding 0 2 formula units and have a composition represented by the chemical formula
Ln3+ 3-x Me2+ X Me3+ Me + 2 x Vx Ga3 O14-0 5zFz
where Ln3+ is at least one of the elements selected from the group consisting of La, Ce, Pr, and Nd, Me2+ is at least one of the elements selected from the group consisting of Ca, Sr, Ba, and Pb; Me3+ is at least one of the elements selected from the group consisting of Ga, Sc, and In, Me4+ is at least one of the elements selected from the group consisting of Si, Ge, and Sn, x is a value not exceeding two
27 A method according to claim 9, wherein the lanthanide gallium crystals have a composition represented by the chemical formula
La3a Gas 5C Nbo 5b O(4 sa+l 25b+825c),
wherein 0 92<a<1 07, 0 9<b<1 1 , 0 99<c<1 02
28 A method according to claim 9, wherein the lanthanide gallium crystals have a composition represented by the chemical formula La3a Gas sc Tao 5 O(4 sa+ι 25b+β 25c),
wherein 0.92<a<1.07, 0.9<b<1.1, 0.99<c<1.02.
29. A method according to claim 10, wherein the lanthanide gallium crystals have a composition represented by the chemical formula
La3a Gasc Sib O( 5a+2b+75c).
wherein 0.86<a<1.1 , 0.85<b<1.3, 0.94<c<1.08.
30. A method according to claim 10, wherein the lanthanide gallium crystals have a composition represented by the chemical formula
La3a Gasc Ti O(45a+2b+75c),
wherein 0.86<a<1.1 , 0.85<b<1.3, 0.94<c<1.08.
31. A method as claimed in claim 1 , wherein the lanthanum gallium melt is doped with the micro additions of chemical elements selected from the group consisting of Li, Be, B, Na, Mg, Al, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, As, Se, Rb, Sr, Y, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, Ce, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, U, and Th at the quantity from 1 χ1017 atom/cm3 to 5x1019 atom/cm3.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012229134A (en) * 2011-04-25 2012-11-22 Fujikura Ltd Method for producing oxide eutectic body
WO2017121024A1 (en) * 2016-01-11 2017-07-20 中国科学院福建物质结构研究所 K3ba3li2al4b6o20f compound, nonlinear optical crystal thereof, and preparation method therefor and use thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2019243A (en) * 1978-04-24 1979-10-31 Mobil Tyco Solar Energy Corp Die for EFG crystal growth
US4944925A (en) * 1985-06-10 1990-07-31 Sumitomo Electric Industries, Ltd. Apparatus for producing single crystals
JPH11186870A (en) * 1997-12-18 1999-07-09 Shin Etsu Chem Co Ltd Langasite single crystal wafer
JPH11199392A (en) * 1998-01-13 1999-07-27 Victor Co Of Japan Ltd Photorefractive crystal and its production
WO1999061686A1 (en) * 1998-05-22 1999-12-02 Tovarischestvo S Ogranichennoi Otvetstvennostiju Firma 'fomos' Method for producing monocrystals of lanthanum and gallium silicate
JP2000007499A (en) * 1998-06-16 2000-01-11 Nec Corp Method for growing langasite single crystal
EP0989212A1 (en) * 1997-03-12 2000-03-29 Rafida Developments Incorporated Lanthanum gallium silicate disc and its preparation method
WO2001048276A1 (en) * 1999-12-28 2001-07-05 Mitsubishi Materials Corporation Langasite single crystal ingot, substrate for piezoelectric device and method for manufacture thereof, and surface acoustic wave device
JP2002003293A (en) * 2000-06-16 2002-01-09 Victor Co Of Japan Ltd Method for preparing langacite-type crystal

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2019243A (en) * 1978-04-24 1979-10-31 Mobil Tyco Solar Energy Corp Die for EFG crystal growth
US4944925A (en) * 1985-06-10 1990-07-31 Sumitomo Electric Industries, Ltd. Apparatus for producing single crystals
EP0989212A1 (en) * 1997-03-12 2000-03-29 Rafida Developments Incorporated Lanthanum gallium silicate disc and its preparation method
JPH11186870A (en) * 1997-12-18 1999-07-09 Shin Etsu Chem Co Ltd Langasite single crystal wafer
JPH11199392A (en) * 1998-01-13 1999-07-27 Victor Co Of Japan Ltd Photorefractive crystal and its production
WO1999061686A1 (en) * 1998-05-22 1999-12-02 Tovarischestvo S Ogranichennoi Otvetstvennostiju Firma 'fomos' Method for producing monocrystals of lanthanum and gallium silicate
JP2000007499A (en) * 1998-06-16 2000-01-11 Nec Corp Method for growing langasite single crystal
WO2001048276A1 (en) * 1999-12-28 2001-07-05 Mitsubishi Materials Corporation Langasite single crystal ingot, substrate for piezoelectric device and method for manufacture thereof, and surface acoustic wave device
JP2002003293A (en) * 2000-06-16 2002-01-09 Victor Co Of Japan Ltd Method for preparing langacite-type crystal

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
ANTONOV: "Physical Problems in crystal growth by the stepanov technique", JOURNAL OF CRYSTAL GROWTH., vol. 50, NORTH-HOLLAND PUBLISHING CO. AMSTERDAM., NL, XP002202216, ISSN: 0022-0248 *
BOHM J ET AL: "Czochralski growth and characterization of piezoelectric single crystals with langasite structure: La3Ga5SiO14 (LGS), La3Ga5.5Nb0.5O14 (LGN), and La3Ga5.5Ta0.5O14 (LGT) - Part I", JOURNAL OF CRYSTAL GROWTH, NORTH-HOLLAND PUBLISHING CO. AMSTERDAM, NL, vol. 204, no. 1-2, 1 July 1999 (1999-07-01), pages 128 - 136, XP004179725, ISSN: 0022-0248 *
CHAI B ET AL: "GROWTH AND EVALUATION OF LARGE SIZE LGS (LA3GA5SIO14), LGN (LA3GA5.5NB0.5O14) & LGT (LA3GA5.5TAO.5O14) SINGLE CRYSTALS", PROCEEDINGS OF THE 1998 IEEE INTERNATIONAL FREQUENCY CONTROL SYMPOSIUM. PASADENA, CA, MAY 27 - 29, 1998, IEEE INTERNATIONAL FREQUENCY CONTROL SYMPOSIUM, NEW YORK, NY: IEEE, US, vol. CONF. 52, 27 May 1998 (1998-05-27), pages 748 - 760, XP000847139, ISBN: 0-7803-4374-3 *
IVLEVA: "The growth of multicomponent oxide single crystals by Stepanov's technique", JOURNAL OF CRYSTAL GROWTH., vol. 82, 1987, NORTH-HOLLAND PUBLISHING CO. AMSTERDAM., NL, pages 168 - 176, XP002202215, ISSN: 0022-0248 *
KAMINSKII A A ET AL: "SPECTROSCOPY OF DISORDERED LA3GA5SIO14 CRYSTALS ACTIVATED WITH PR+3,HO+3,AND ER+3 IONS1)", OPTICS AND SPECTROSCOPY, AMERICAN INSTITUTE OF PHYSICS. WASHINGTON, US, vol. 68, no. 4, 1 April 1990 (1990-04-01), pages 520 - 525, XP000260994, ISSN: 0030-400X *
MING-HSIEN LIN ET AL: "CRYSTAL PULLING WITH FLOATING WETTED SHAPERS", JOURNAL OF CRYSTAL GROWTH, NORTH-HOLLAND PUBLISHING CO. AMSTERDAM, NL, vol. 132, no. 3/4, 2 September 1993 (1993-09-02), pages 467 - 470, XP000474802, ISSN: 0022-0248 *
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 12 29 October 1999 (1999-10-29) *
PATENT ABSTRACTS OF JAPAN vol. 2000, no. 04 31 August 2000 (2000-08-31) *
PATENT ABSTRACTS OF JAPAN vol. 2002, no. 05 3 May 2002 (2002-05-03) *
TAKEDA H ET AL: "CRYSTAL GROWTH AND STRUCTURAL CHARACTERIZATION OF NEW PIEZOELECTRICMATERIAL LA3TA0.5GA5.5O14", JAPANESE JOURNAL OF APPLIED PHYSICS, PUBLICATION OFFICE JAPANESE JOURNAL OF APPLIED PHYSICS. TOKYO, JP, vol. 36, no. 7B, PART 2, 15 July 1997 (1997-07-15), pages L919 - L921, XP000737963, ISSN: 0021-4922 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012229134A (en) * 2011-04-25 2012-11-22 Fujikura Ltd Method for producing oxide eutectic body
WO2017121024A1 (en) * 2016-01-11 2017-07-20 中国科学院福建物质结构研究所 K3ba3li2al4b6o20f compound, nonlinear optical crystal thereof, and preparation method therefor and use thereof

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