CN1042575A - The Bridgman-Stockbarge method for growing of lithium tetraborate (LBO) monocrystalline - Google Patents
The Bridgman-Stockbarge method for growing of lithium tetraborate (LBO) monocrystalline Download PDFInfo
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- CN1042575A CN1042575A CN 88105599 CN88105599A CN1042575A CN 1042575 A CN1042575 A CN 1042575A CN 88105599 CN88105599 CN 88105599 CN 88105599 A CN88105599 A CN 88105599A CN 1042575 A CN1042575 A CN 1042575A
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Abstract
Lithium tetraborate single crystal (Li
2B
4O
7: falling crucible method LBO) (Bridgman) growth belongs to the single crystal growing field.Feature of the present invention is: LBO crystal seed and the density of cross-sectional area P (=S crystal seed/S crystal) 〉=15% are 0.9～1.4 gram per centimeter
3The LBO briquetting, put into wall thickness and be 0.08～0.15 millimeter platinum crucible, fusing briquetting and crystal seed top under 950～1100 ℃ of furnace temperature, again the speed of platinum crucible with≤0.3 millimeter hour is descended, can grow water white transparency, integrity is good, is difficult for rimose LBO single crystal.Present method temperature field is stable, and processing unit is simple, and is easy to operate, many crucibles can be put into the Bridgman single crystal growing furnace, the monocrystalline of the different shapes of growing simultaneously and size.
Description
The invention belongs to the single crystal growing field.
Up to now, lithium tetraborate (Li
2B
4O
7: LBO or LTB) single crystal growing, all adopt crystal pulling method (Czochralski) both at home and abroad.The essential characteristic of this growth method is in the crystal pulling method single crystal growing furnace, is melted in lithium tetraborate raw material in the platinum crucible by high frequency or resistive heating, again through sowing, operations such as necking down, rotary pulling, grow the LBO monocrystalline of certain orientation and certain size.This monocrystalline has high surface acoustic wave (SAW) effective electro-mechanical couple factor (k
2≈ 1%), zero-lag temperature factor (TCD=0) tangential, the high velocity of sound, light specific gravity need not polarize, the advantage that cold-forming property is good.Therefore, the LBO mono-crystalline piezoelectric materials is a kind of promising SAW and BAW(bulk acoustic wave) the temperature compensation substrate material of device.Because the LBO melt viscosity is big, the anisotropy of crystal thermal expansion during with the pulling method for growing LBO monocrystalline, is easy to occur white thread wrap, bubble, growth crackle, and component is crossed macroscopic defects and cracking fragmentations such as cold striped.This method unit per unit area yield adds because of the quick complete growth of the impossible greatly realization of LBO melt viscosity.Therefore, this process efficiency is low.Still the suitability for industrialized production of LBO monocrystalline in the world is unrealized.(day disclosure special permission communique (A), clear and 62-108800; Clear and 62-162693; Clear and 62-36098; Clear and 62-96398.
Jpn.J.Appl.Phys.1985，24（Suppl.24-3）
72-75;J.Material Soci.17（1982）1729-1738;
J.Crystal Growth 41（1977）225-227;
" artificial lens " 14(1985) 92.
The growth method that the purpose of this invention is to provide a kind of reliable and stable high quality LBO monocrystalline is to realize the suitability for industrialized production of LBO novel piezoelectric monocrystalline.It is the Bridgman method of growing LBO piezoelectric monocrystal.
Major technique content of the present invention is: high-purity (99.9%, as follows) LBO raw material briquetting is inserted the bottom lay in the crucible of certain size and direction crystal seed; Platinum crucible places the Bridgman single crystal growing furnace, and dropping speed of the crucible is controlled in melt raw material and crystal seed top under certain furnace temperature, can grow the high quality LBO single crystal that does not have macroscopic view and microscopic defect.
Detailed content of the present invention is as follows:
1. raw material compound stalk forming
With of the size and dimension requirement of high-purity LBO powder, do hydrostaticpressure or compression molding by platinum crucible.The density of LBO briquetting is 0.9～1.4 gram per centimeter
3
2. holding the LBO melt is 0.08～0.15 millimeter with the platinum crucible wall thickness of laying crystal seed, and near airtight, to prevent the volatilization of LBO melt composition.
3.LBO the crystal seed direction is＜100 〉,＜001,＜110,＜210 etc., perpendicular to the crystal seed cross-sectional area (S of the direction of growth
Crystal seed) with the cross-sectional area (S of growing crystal
Crystal) ratio P(=(S crystal seed)/(S crystal)) 〉=15%.
4. fusing LBO raw material briquetting and crystal seed top in the Bridgman single crystal growing furnace in furnace temperature is 950～1100 ℃ of scopes, descend with≤0.3 millimeter/hour speed, can obtain the complete LBO monocrystalline identical with the platinum crucible shape.
5. many platinum crucibles can be laid in the Bridgman single crystal growing furnace, the LBO monocrystalline of grow simultaneously different shapes, different size.(being platinum crucible shape, controllable number).
The present invention compares with crystal pulling method, and its advantage is: the temperature field is stable, and the lbo crystal integrity of growth is good, no macroscopic view and microscopic defect; The yield rate height; Crystalline size and profile are controlled easily, and be not easy to crack.Processing unit is simple, and is easy to operate, and energy consumption obviously reduces, and helps realizing suitability for industrialized production (seeing Table 1).
The comparison of table 1 the present invention and pulling method for growing LBO
| Method | Processing condition | Crystal mass | Production level |
| Crystal pulling method | The growth parameter(s) complexity, crystalline form is single, apparatus expensive | The thread wrap of white, constitutional supercooling striped, bubble, fragmentation easy to crack | The unit per unit area yield, efficient is low, energy consumption height, not industrialization |
| The present invention | The temperature field is stable, and crystalline form is variable, and equipment is simple, and is easy to operate | No macroscopic view and microscopic defect, integrity is good, and is not easy to crack | The unit fecund, the yield rate height, energy consumption and cost are low, can realize industrialized mass production. |
With widely used high-melting-point piezoquartz LN(LiNbO on the modern industry
3, 1250 ℃) and LT(LiTaO
3, 1670 ℃) and compare LBO monocrystalline fusing point low (917 ℃), congruent melting growth, and the processing that need not polarize.Its density only is about 1/2 of LN, 1/3 of LT.The lbo crystal piece rate of same weight will be about 2 times of LN, 3 times of LT, and this will reduce the cost of substrate greatly.LBO has high SAW k
2Tangential with TCD=0, this design to the improvement of SAW and BAW device performance and arrowband band logical SAW wave filter, resonator or very high frequency(VHF) device is extremely important.
As seen from Table 2, LBO can replace LT, the LN application at SAW and BAW device, helps the update of this class device.
At present, LT, LN are widely used in colour, black and white television set in the world, video tape recorder intermediate-frequency filter, the rf-resonator of video tape recorder, satellite broadcasting, special telephone, mobile radio unit etc.Its output value had been 7,800,000,000 yen in 1985.The production of the domestic LT of China, LN is in ton, and (produce the LN5 ton per year with 87 is example to the millions of approximately units of annual value of production, the output value
Being 6,000,000 yuan) the wave filter output value made with this material then is after tens million of units (seeing Table 2) LBO single crystal industrial is produced, can obtain more considerable economic.
The suitability for industrialized production because this crystal still is unrealized in the world uses method of the present invention to realize suitability for industrialized production, not only can obtain economic benefit, also will produce positive social benefit.
The embodiment of the invention is as follows:
With high-purity (99.9%) LBO powder through hydrostaticpressure or to be molded into density be 0.9 gram per centimeter
3Briquetting, and to put into wall thickness be 0.08 millimeter platinum crucible.＜100〉rectangular cylindricality crystal seed, its cross-sectional area S
Crystal seed/ S
Crystal(being P) is 15% to place the briquetting bottom.In the Bridgman single crystal growing furnace, fusing briquetting and crystal seed top were incubated after 4 hours under 950 ℃ of temperature, with 0.3 millimeter/hour speed decline crucible, and the water white LBO perfect crystal of growing.
2. with density 1.2 gram per centimeters
3Briquetting, P is 25%＜001〉garden shape crystal seed, puts into wall thickness and be 0.1 millimeter platinum crucible, on 1050 ℃ of following fusing briquettings and crystal seed top, then with 0.2 millimeter/hour speed decline crucible, gives birth to oval LBO perfect crystal.
3. be 1.4 gram per centimeters with density
3Briquetting, P be 30%＜to put into wall thickness be 0.15 millimeter platinum crucible to 110〉Polygons crystal seeds, under 1100 ℃ of temperature, melt raw material and welding crystal seed are with 0.15 millimeter/hour speed decline crucible, growing LBO perfect crystal.
4. press example 1,2,3 described processing condition will＜001 〉,＜100,＜110 〉,＜210 etc. the crystal seed of different orientation put into 10 platinum crucibles, 10 lbo crystals of growing simultaneously.
Claims (2)
1, a kind of growth lithium tetraborate single crystal (Li
2B
4O
7: falling crucible method LBO) (Bridgman) comprising:
(1) crystal seed is along＜001 〉,＜100,＜110 〉,＜210 etc. orientation;
(2) powder is through hydrostaticpressure or compression molding;
(3) briquetting is put in the platinum crucible 950～1100 ℃ of fusings down;
It is characterized in that:
1. compact density is the 0.9-1.4 gram per centimeter
3
2. used platinum crucible wall thickness is the 0.08-0.15 millimeter;
3. perpendicular to the crystal seed cross-sectional area and the growing crystal of the direction of growth, the ratio of cross-sectional area is 〉=15%;
4. making crucible with≤0.3 millimeter/hour speed descends.
2,, it is characterized in that described platinum crucible shape and controllable number according to the LBO method for monocrystal growth of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105599 CN1015920B (en) | 1988-11-05 | 1988-11-05 | Single crystal growth of lithium tetra borate (lbo) using the method of descending crucible |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105599 CN1015920B (en) | 1988-11-05 | 1988-11-05 | Single crystal growth of lithium tetra borate (lbo) using the method of descending crucible |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1042575A true CN1042575A (en) | 1990-05-30 |
| CN1015920B CN1015920B (en) | 1992-03-18 |
Family
ID=4833778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105599 Expired CN1015920B (en) | 1988-11-05 | 1988-11-05 | Single crystal growth of lithium tetra borate (lbo) using the method of descending crucible |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1015920B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393923C (en) * | 2005-06-22 | 2008-06-11 | 广州锐鑫锂能新材料科技有限公司 | Production of high-purity lithium tetraborate crystal by industrial lithium hydroxide and boric acid |
| CN104264225A (en) * | 2014-09-05 | 2015-01-07 | 中国科学院理化技术研究所 | Seed crystal rod used for growth of large-size LBO crystals and growth method of large-size LBO crystals |
| CN105624781A (en) * | 2016-01-14 | 2016-06-01 | 福建福晶科技股份有限公司 | Lithium tetraborate crystal preparation method and growth device |
| CN104264225B (en) * | 2014-09-05 | 2017-01-04 | 中国科学院理化技术研究所 | A kind of for large scale lbo crystal growing method |
| CN106835263A (en) * | 2017-02-20 | 2017-06-13 | 中国科学院新疆理化技术研究所 | The preparation method and purposes of lithium fluoroborate nonlinear optical crystal |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322174C (en) * | 2004-04-02 | 2007-06-20 | 中国科学院上海硅酸盐研究所 | Technique for developing crystal of bismuth boric acid through falling curcible method |
-
1988
- 1988-11-05 CN CN 88105599 patent/CN1015920B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393923C (en) * | 2005-06-22 | 2008-06-11 | 广州锐鑫锂能新材料科技有限公司 | Production of high-purity lithium tetraborate crystal by industrial lithium hydroxide and boric acid |
| CN104264225A (en) * | 2014-09-05 | 2015-01-07 | 中国科学院理化技术研究所 | Seed crystal rod used for growth of large-size LBO crystals and growth method of large-size LBO crystals |
| CN104264225B (en) * | 2014-09-05 | 2017-01-04 | 中国科学院理化技术研究所 | A kind of for large scale lbo crystal growing method |
| CN105624781A (en) * | 2016-01-14 | 2016-06-01 | 福建福晶科技股份有限公司 | Lithium tetraborate crystal preparation method and growth device |
| CN106835263A (en) * | 2017-02-20 | 2017-06-13 | 中国科学院新疆理化技术研究所 | The preparation method and purposes of lithium fluoroborate nonlinear optical crystal |
| CN106835263B (en) * | 2017-02-20 | 2020-01-03 | 中国科学院新疆理化技术研究所 | Preparation method and application of lithium fluoroborate nonlinear optical crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1015920B (en) | 1992-03-18 |
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Assignee: Pilot base of Shanghai Silicate Research Institute Assignor: Shanghai Silicates Institute, the Chinese Academy of Sciences Contract fulfillment period: Contract performance period from March 27, 2003 to November 5, 2008 Contract record no.: Contract filing No. 033100030009 Denomination of invention: Growth of a single crystal of lithium borate (LBO) four by the method of crucible descent Granted publication date: 19921021 License type: Common License Record date: 20030408 |
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