CN1048569A - Monocrystal lithium uniformly doped with magnesium niobic acid and preparation method thereof - Google Patents
Monocrystal lithium uniformly doped with magnesium niobic acid and preparation method thereof Download PDFInfo
- Publication number
- CN1048569A CN1048569A CN 89104593 CN89104593A CN1048569A CN 1048569 A CN1048569 A CN 1048569A CN 89104593 CN89104593 CN 89104593 CN 89104593 A CN89104593 A CN 89104593A CN 1048569 A CN1048569 A CN 1048569A
- Authority
- CN
- China
- Prior art keywords
- mgo
- linbo
- growth
- crystal
- mole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Lithium uniformly doped with magnesium niobic acid (MgO:LiNbO
3) growth of monocrystalline belongs to the single crystal growing field.Feature of the present invention is: equal 100% by ternary mole total amount and calculate, use Li
2O/Nb
2O
5=(47.2 ± 0.3)/(52.8 ∴ 0.3) (mol ratio), MgO content is the MgO:LiMbO of 4.0-7.0 mole %
3Homogeneous is formed, and under 1220 ℃～1270 ℃ furnace temperature, with 1～3 millimeter/hour pull rate, 10～25 rev/mins speed of rotation is used Czochralski grown MgO:LiNbO
3Single crystal.The crystal that is obtained after polarization is handled has the good optical homogeneity.Adopt the MgO:LiNbO of present method growth
3Monocrystalline, macroscopic defectss such as no striation and inclusion have good chemical constitution homogeneity.
Description
The invention belongs to the single crystal growing field.
Lithium niobium trioxide (LiNbO
3) crystal has excellent piezoelectricity, electro-optical characteristic, high Curie temperature, lower specific inductivity, and more easily grow into large-sized single crystal, therefore be widely used in preparing various devices.In recent years, along with the development of optical waveguide technique, LiNbO
3Be considered to one of best waveguide substrate material.But pure LiNbO in actual applications,
3Under laser radiation, produce light easily and hinder, limited its application aspect optics.Reports such as the secondary state of mounting in 1979 are mixed the LiNbO of 4.6 moles of %MgO
3(write a Chinese character in simplified form MgO:LiNbO
3) crystal, its anti-light ability of hindering improve nearly two orders of magnitude (11th International Quantum Electronics eonference June 23-26,631(1980).From then on, MgO:LiNbO
3Crystal as a kind of modification is applied aspect the optics.But adopt with pure LiNbO both at home and abroad up to now, always
3Binary form the method add magnesium oxide (MgO) with composition and prepare burden, with crystal pulling method (Czochralski) MgO:LiNbO that from the melt of this composition, grows
3Crystal.This distribution has been ignored such fact: since MgO mix MgO:LiNbO
3Same composition point also change thereupon.P.M.Broienbaugh once pointed out: at the LiNbO that forms with composition
3In mix 1 mole of % MgO can cause having in the melt Lithium Oxide 98min surplus (J.cryst.Growth 19,45～52(1973)) of 0.6 mole of %.The state etc. of mounting the second month in a season finds also that when magnesium oxide mixes concentration up to 10 moles of % the Lithium Oxide 98min concentration in the crystal is reduced to the 40%(silicate journal, Vol.12（2），145～48（1984）。The B.C.Grabmaier experimental result also shows: magnesian mix can influence the effective partition ratio of Lithium Oxide 98min in crystal (J.Cryst.Growth, 179,682-88(1986)).Form batching by the binary of common employing with composition and be difficult to make MgO:LiNbO
3Effective partition ratio of each constituent element reaches 1 simultaneously in the crystal, and the crystal of growing from the melt of this composition always exists forms uneven problem.
The objective of the invention is to determine MgO:LiNbO
3Homogeneous form and from its melt, grow and form MgO:LiNbO even, excellent property with crystal pulling method
3Monocrystalline.
Of the present invention to the effect that with specpure MgO(99.99%) and Li
2CO
3(99.99%) and high-purity Nb
2O
5(99.95%) forms batching by the ternary homogeneous, mixing the calcining under middle high temperature of also dry-pressing formed back makes its solid state reaction complete, place platinum crucible to melt again, the rotation and the pull rate of control seed crystal can grow macroscopic defectss such as no striation and inclusion under certain furnace temperature, form uniform high quality MgO:LiNbO
3Single crystal.
Detailed content of the present invention is as follows:
1, with high-purity N b
2O
5(99.95%) raw material is contained in the alumina crucible in 900 ℃ of following roastings, is incubated 10 hours, to reduce the fluorine content in the raw material.
2, press MgO:LiNbO
3Homogeneous form take by weighing specpure MgO(99.99%), Li
2CO
5(99.99%) and through the Nb of roasting
2O
3(99.95%), equals 100% with ternary mole total amount and calculate, make wherein Li
2O/Nb
2O
5=(47.2 ± 0.3)/(52.8 0.3) MgO content is 4.0～7.0 moles of %.The raw material for preparing is after ball milling mixes 24 hours, and dry-pressing becomes the cylindrical block material of φ 55 * 50mm.
3, block raw material is placed in the alumina crucible of liner platinized platinum, under 1150 ℃,, impels in the raw material solid state reaction fully with the volatilization of Lithium Oxide 98min in crystal growing process after reducing through 15 hours calcining.
4, burnt raw material is placed the platinum crucible of φ 55 * 50mm, under 1220～1270 ℃ furnace temperature, use Czochralski grown MgO:LiNbO
3Single crystal.Its growthing process parameter is:
Direction of growth C axle＜00.1〉or X-axis＜11.0 or Y-axis＜01.0
Pull rate 1-3 millimeter/hour
Speed of rotation 10-25 rev/min
The growth atmosphere atmosphere
Speed of cooling≤50 ℃/hour
5, the crystal that growth is good also will be done the poling processing, and its processing condition are as follows:
Embodiment 1: take by weighing Nb respectively
2O
5395.69 gram, Li
2CO
398.33 gram, MgO5.98 gram, after mixing, dry-pressing becomes the cylindrical block material, under 1150 ℃ after calcining in 15 hours, place platinum crucible Czochralski grown monocrystalline.Its growth parameter(s) is as follows:
Direction of growth C axle＜00.1 〉
2.5 millimeters/hour of pull rate
22 rev/mins of speed of rotation
The growth atmosphere atmosphere
Speed of cooling≤50 ℃/hour
Crystalline size φ 30 * 45mm
Table 2 has been listed the Chemical Composition analytical results of this crystal head and afterbody, and wherein bath component is formed calculating by batching and got:
Table 2 crystalline Chemical Composition is analyzed
| Constituent element | Melt (mole %) | Crystal (mole %) | Difference (mole %) end to end | Imitating partition ratio | |
| Head | Afterbody | ||||
| MgO | 5.00 | 5.36 | 5.26 | 0.10 | 1.07 |
| NbO | 50.16 | 49.39 | 49.48 | -0.09 | 0.98 |
| LiO | 44.84 | 45.25 | 45.26 | -0.01 | 1.01 |
Embodiment 2: take by weighing Nb
2O
5393.67 gram, Li
2CO
398.82 gram, the MgO8.51 gram is with the method growth MgO:LiNbO of embodiment 1
3With the crystal of composition, the crystalline chemical analysis results sees Table 3.
Table 3 crystalline Chemical Composition is analyzed
| Constituent element | Melt (mole %) | Crystal (mole %) | Difference (mole %) end to end | Imitating partition ratio | |
| Head | Afterbody | ||||
| MgO | 7.00 | 6.72 | 6.65 | 0.70 | 0.96 |
| NbO | 49.10 | 48.77 | 49.07 | -0.30 | 0.99 |
| LiO | 43.90 | 44.51 | 44.28 | 0.23 | 1.01 |
Embodiment 3: press the processing condition of embodiment 1,2, preparation raw material makes its Li
2O/Nb
2O
5=(47.2 ± 0.3)/(52.8 0.3) (mol ratio), MgO content is 4.0～7.0 moles of %, selects for use＜11.0〉seeded growth MgO:LiNbO
3Monocrystalline, press following technology:
Direction of growth X-axis＜11.0 〉
1.2 millimeters/hour of pull rate
10 rev/mins of speed of rotation
Speed of cooling≤40 ℃/hour
Can obtain the single crystal of X-axis orientation.
60 ℃/hour 1150 ℃-1220 ℃ of room temperatures (insulation half an hour, added electric field:
0.8～1.2V/cm
2，5～8mA/cm
2) 40 ℃ of/hour 1000 ℃～1050 ℃ (removing electric field) 40 ℃ of/hour room temperatures
Adopt the composition of the present invention's narration and the MgO:LiNbO of technology growth3Monocrystalline does not have the gross imperfections such as growth striation and inclusion enclave. The state etc. of mounting the second month in a season has reported the LiNbO that mixes 7 % by mole of MgO3Crystal, its magnesian partition eocfficient is 1, but the end to end content of lithia differs and reaches 0.7 % by mole in the crystal, the shovel distribution coefficient that has of lithia departs from 1(silicate journal Vol.12(2 significantly) (1984)); And the MgO:LiNbO that adopts the present invention to grow5Crystal, MgO and Li2The partition eocfficient of O reaches or simultaneously near 1, thereby forms more even. This crystal is sparkling and crystal-clear transparent, has good optical homogeneity, is processed into the fiber waveguide substrate, has high process consistency, can more effectively improve the qualification rate of product.
The comparison of table 1 the present invention and prior art
| Product MgO:LiNbO | The preparation method for raw material that adopts | Partition eocfficient | Crystal mass | Be processed into the fiber waveguide substrate |
| The present invention | Be 100% to calculate by ternary mole total amount | The partition eocfficient of each constituent element approaches simultaneously or reaches 1 | Sparkling and crystal-clear transparent, the gross imperfections such as no growth striation and inclusion enclave, optical homogeneity is good | Has process consistency |
| Prior art | Binary adds MgO with composition | The partition eocfficient of each constituent element is difficult to approach simultaneously or reach 1 | It is relatively poor to produce easily the growth striation optical homogeneity | Process consistency is relatively poor |
Claims (2)
1, a kind of lithium uniformly doped with magnesium niobic acid (MgO:LiNbO
3) monocrystalline, it is characterized in that:
(1) chemical ingredients is:
Constituent element mole %
MgO 4.0-7.0
Li
2O 43.6-45.6
Nb
2O
548.8-51.0
Effective partition ratio of (2) three constituent elements is approaching or reach 1.
2, a kind of homogeneous is mixed magnesium niobium lithium (MgO:LiNbO
3) growth method of monocrystalline, comprising:
(1) raw material pre-burning (900 ℃ are incubated 10 hours down)
(2) batching, dry-pressing formed
(3) block raw material solid state reaction (1150 ℃ through calcining in 15 hours)
(4) growing crystal, condition is:
1220 ℃～1270 ℃ of furnace temperature
The direction of growth: C axle＜00.1 〉, X-axis＜11.0, Y-axis＜01.0
Pull rate: 1～3 millimeter/hour
Speed of rotation: 10～25 rev/mins
Growth atmosphere: atmosphere
Speed of cooling :≤50 ℃/hour
It is characterized in that:
(1) preparation of raw material employing is 100% calculating by ternary mole total amount, makes its Li
2O/Nb
2O
5=(47.2 ± 0.3)/(52.8 0.3), MgO content are 4.0～7.0 moles of %.
(2) Czochralski grown crystal need adopt poling to handle, and condition is:
1150 ℃～1220 ℃ of furnace temperature
DC electric field intensity is 0.8～1.2 volt/centimetre
Polarizing current is: 5～8 milliamperes/centimetre
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89104593 CN1048569A (en) | 1989-07-03 | 1989-07-03 | Monocrystal lithium uniformly doped with magnesium niobic acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89104593 CN1048569A (en) | 1989-07-03 | 1989-07-03 | Monocrystal lithium uniformly doped with magnesium niobic acid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1048569A true CN1048569A (en) | 1991-01-16 |
Family
ID=4855616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89104593 Pending CN1048569A (en) | 1989-07-03 | 1989-07-03 | Monocrystal lithium uniformly doped with magnesium niobic acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1048569A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092253C (en) * | 1997-09-29 | 2002-10-09 | 南京大学 | Preparing rare-earth ion doped LN, LT optical super lattice material and its application |
| CN103922405A (en) * | 2014-04-18 | 2014-07-16 | 山东大学 | Batch synthesis method of lithium niobate uniformly-doped polycrystal material |
| CN107925399A (en) * | 2016-07-11 | 2018-04-17 | 株式会社山寿瑟拉密克斯 | Acoustic surface wave element substrate and its manufacture method |
| CN111549373A (en) * | 2020-05-14 | 2020-08-18 | 北方民族大学 | Pulling method for growing bismuth silicate (Bi) with uniform components4Si3O12Method for producing BSO) crystals |
-
1989
- 1989-07-03 CN CN 89104593 patent/CN1048569A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092253C (en) * | 1997-09-29 | 2002-10-09 | 南京大学 | Preparing rare-earth ion doped LN, LT optical super lattice material and its application |
| CN103922405A (en) * | 2014-04-18 | 2014-07-16 | 山东大学 | Batch synthesis method of lithium niobate uniformly-doped polycrystal material |
| CN103922405B (en) * | 2014-04-18 | 2015-08-12 | 山东大学 | A kind of mass synthetic method of even mg-doped lithium niobate polycrystal |
| CN107925399A (en) * | 2016-07-11 | 2018-04-17 | 株式会社山寿瑟拉密克斯 | Acoustic surface wave element substrate and its manufacture method |
| CN111549373A (en) * | 2020-05-14 | 2020-08-18 | 北方民族大学 | Pulling method for growing bismuth silicate (Bi) with uniform components4Si3O12Method for producing BSO) crystals |
| CN111549373B (en) * | 2020-05-14 | 2021-12-24 | 北方民族大学 | Pulling method for growing bismuth silicate (Bi) with uniform components4Si3O12Method for producing BSO) crystals |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105220232B (en) | Secondary electro-optic crystal and its preparation and application method with graded index effect | |
| CA2259395A1 (en) | Equipment for crystal growth and crystal-growing method using the same | |
| CN111455453B (en) | Method for growing superlattice lithium niobate crystal | |
| CN1048569A (en) | Monocrystal lithium uniformly doped with magnesium niobic acid and preparation method thereof | |
| US6302956B1 (en) | Langasite wafer and method of producing same | |
| KR0143799B1 (en) | Single crystal growth method for bariumtitanikm oxide using noncrystalline solio growth | |
| EP0569968B1 (en) | Method of producing single crystal of KTiOPO4 | |
| CN114956110A (en) | Compound trihydroxy chlorine cesium triborate and trihydroxy chlorine cesium triborate birefringent crystal, preparation method and application | |
| CN1077504A (en) | Tetragonal tantalum doping potassium niobate crystal and growth technique thereof | |
| JP2507910B2 (en) | Method for producing oxide single crystal | |
| Miyazawa et al. | Preparation of paratellurite TeO2 | |
| CN102021641B (en) | Orientated seed crystal growth method of R2CaB10O19 single crystal | |
| CA1302848C (en) | Process for making homogeneous lithium niobate | |
| CN1052516A (en) | The preparation of lithium niobate monocrystal by erbium and magnesium doping | |
| Deis et al. | Synthesis of lithium tantalate whiskers from metal alkoxide derived gels | |
| JPH05117096A (en) | Method for growing thin film of lithium niobate single crystal | |
| Nakano et al. | Flux growth of LiNdP4O12 single crystals | |
| CN1428464A (en) | Preparation method of chemical metering ratio lithium niobate monocrystal | |
| CN116876074A (en) | Preparation method of symmetrical high-temperature phase barium metaborate (alpha-BBO) crystal, symmetrical high-temperature phase barium metaborate crystal and application | |
| CN1252323C (en) | Process for growing calcium borate mono crystal by melt drawing | |
| Brun et al. | Crystal growth and characterization of lithium metasilicate | |
| JP3013206B2 (en) | Method for producing lithium niobate single crystal | |
| JPS62138396A (en) | Magnetic garnet material for magneto-optical element | |
| KR890004636B1 (en) | Method for producing single-crystal growth in linbo3 | |
| JPH05238892A (en) | Substrate for oxide superconducting thin film and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |