CN1086552A - Improved growing low temperature phase-deviation barium borate monocrystal by smelting salt crystal method - Google Patents

Improved growing low temperature phase-deviation barium borate monocrystal by smelting salt crystal method Download PDF

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CN1086552A
CN1086552A CN 92112921 CN92112921A CN1086552A CN 1086552 A CN1086552 A CN 1086552A CN 92112921 CN92112921 CN 92112921 CN 92112921 A CN92112921 A CN 92112921A CN 1086552 A CN1086552 A CN 1086552A
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crystal
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seed crystal
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CN1032072C (en
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江爱栋
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Fujian Castech Crystals Inc
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

About the method for improved growing low temperature phase-deviation barium borate monocrystal by smelting salt crystal method, belong to crystal growth technique.Its growth method comprises batching, following seed crystal, grows and comes out of the stove four steps.The used seed crystal centre-drilling hole of this law, and seed rod screwed in or insert in the hole with fixing seed crystal, seed orientation is for becoming 0-60 angles of spending with the C axle, and rate of temperature fall is 0.01 ℃-0.1 ℃/hour, Crystal Rotation speed is 0-30 rev/mins, and the mode of coming out of the stove can be with directly mentioning annealing or the converter method of falling liquid.Improve one's methods with this, can stably grow Φ 80-150mm, center thickness reaches the transparent large single crystal of high-quality of 25-35mm.

Description

Improved growing low temperature phase-deviation barium borate monocrystal by smelting salt crystal method
The invention belongs to crystal growth technique.
Low-temperature phase barium metaborate monocrystalline is multifunctional materials such as a kind of good nonlinear optics, thermoelectricity, in recent years in nonlinear optics, especially aspect the ultraviolet frequency double, be made into Laser Devices and be used widely.About the growth method of low-temperature phase barium metaborate monocrystalline, mainly contain fused salt seed crystal method and crystal pulling method etc.In 1981 river likes that a people such as grade is with Na 2O is a fusing assistant, adopts fused salt seed crystal method to grow transparent, fine low-temperature phase barium metaborate monocrystalline; They were fusing assistant with NaF in 1984, were the orientation of seed crystal with the C axle; With 0.03 ℃/hour-0.2 ℃/hour cooling rate, 5-70 rev/min rotating speed and BaB 2O 4/ Na 2The O=73-78/27-22(mole percent) or BaB 2O 4/ NaF=64-67/36-33(mole percent) ratio grows the large single crystal that size reaches ∮ 67 * 15mm, and (seeing patent 85101617.0) makes this crystal move towards industrial application from the laboratory demonstration.In 1990, Shanghai silicate fused salt pulling method patent application (application number: 90102894), this crystalline growth method has been carried out new discussion about barium metaborate monocrystalline proposed again.
Existing growth method can not adapt to the requirement of device on quantity, quality, size of on the industrial production this crystal being made.Seeking a kind of better method, make it can stably grow large size, high-quality low-temperature phase barium metaborate monocrystalline, is purpose of the present invention.Fujian structure of matter institute passes through further investigation for many years, has invented a kind of improved fused salt seed crystal method, has in the past few years cultivated many fine large single crystals with this method, has satisfied the demand of domestic and international market fully, remarkable in economical benefits.
The crystal growth experimental arrangement is as follows: press BaB 2O 4/ NaF=66.5/33.5(mole percent) the best proportioning weighing GR or the barium carbonate of AR purity, boric acid, each raw material of Sodium Fluoride, place agate mortar, ground and mixed is even, the platinum crucible (melt is filled crucible 3/4 or 4/5 volume) of after fusion repeatedly, packing into, and place the growth stove.Be rapidly heated to the temperature that is higher than the about 50-100 of liquidus temperature ℃ with the specified maximum power of growth furnace, under this temperature constant temperature 15-48 hour, measure temperature of saturation with attempting the seed crystal method down then, its precision should reach ± and 1 ℃.Under about 10-30 ℃ of temperature more than the temperature of saturation, the seed crystal that will fix is down to the molten surface center lentamente.Seed crystal can be garden post, tetragonal prism or polygon cylindricality, and square file one ditch is tied up below seed rod with platinum filament then thereon, perhaps seed crystal centre-drilling hole, the hole can be bored or is not saturating, with Threading mode or platinum filament colligation mode, fixes with seed rod lower end screw-in or between inserting in the hole.Seed orientation is perpendicular to horizontal liquid level, becomes the angle (that is: if be oriented to the C axle, then the C axle is perpendicular to horizontal liquid level) of 0-60 degree with the C axle, is preferably the C direction of principal axis.Constant temperature is after half an hour, and fast cooling is to the above 3-10 of temperature of saturation ℃.
Crystal begins growth.In whole growth process, can control the crystalline speed of growth by regulating rate of temperature fall or Crystal Rotation speed or their combination.As: the following period of time after beginning to grow, visual crystal growth situation, or cooling or constant temperature or heat up with control crystalline primary growth, after waiting to enter normal condition, (rate of temperature fall is decided by the crucible size size with 0.01 ℃/hour-0.1 ℃/hour speed cooling, if crucible size is big, then rate of temperature fall falls within the low rate interval, otherwise then falls within the two-forty interval).In the growth, Crystal Rotation speed can be regulated between 0-30 rev/min, can adopt different rotating speeds (being that brilliant commentaries on classics of whole process is speed change) according to circumstances in different steps.When the cooling amount reaches 10-30 ℃, stop Crystal Rotation, continue to be cooled to about 800 ℃, so far growth ending with above-mentioned speed.
After crystal growth finished, its mode of coming out of the stove can directly be lifted from molten surface with crystal, reduces to room temperature with the speed about 50 ℃/hour.If crystal comes off with seed rod in lifting from process, then adopt the converter method of falling liquid, crystal is separated with remaining liquation, its step is as follows: open bell rapidly, the crucible of adorning crystal and liquation is clipped to rapidly in the converter that has been warmed up to relevant temperature, rotate stove to the sea line a little less than rotation axis, pouring melt, the crystal that grows into is stayed in the crucible, is annealed to room temperature with converter with about 50 ℃/hour speed.
Adopt above-mentioned growth technique, can stably grow ∮ 80-150mm, center thickness 25-35mm is the transparent large single crystal of high-quality of bowl.If crucible size strengthens, and prolong vegetative period, can obtain bigger monocrystalline.
Embodiment 1:
Take by weighing BaCO 3789.6 gram, H 3BO 3494.4 gram, the NaF86.5 gram places the agate mortar ground and mixed even these three kinds of raw materials together, by repeatedly adding ∮ 80 * 80mm after the fusion 3Platinum crucible in, and with crucible place the growth stove, be warming up to 980 ℃, constant temperature 18 hours, then under temperature about 10 ℃ more than the temperature of saturation, will be fixed on seed crystal on the seed rod in advance lentamente down to molten surface, seed orientation is and C axle clamp angle 60 degree.Constant temperature was lowered the temperature 7 ℃ after half an hour, and crystal begins growth, at early growth period, or rose or permanent or cooling, waited to enter under the normal condition, lowered the temperature with 0.1 ℃/hour speed, and accompanied by 30 rev/mins speed rotation crystal.When cooling about 30 ℃ the time, stop brilliant the commentaries on classics, static growth, and continue to be cooled to about 800 ℃ by above speed.Growth ending is mentioned crystal, is annealed to room temperature with 50 ℃/hour speed, obtains ∮ 80 * 25mm 3The transparent large single crystal of high-quality.
Embodiment 2:
Take by weighing BaCO 31579.2 gram, H 3BO 3988.8 gram, the NaF173.1 gram places the agate mortar ground and mixed even these three kinds of raw materials together, by repeatedly adding ∮ 100 * 100mm after the fusion 3Platinum crucible in, and with crucible place the growth stove, be warming up to 980 ℃, constant temperature 24 hours, then under temperature about 15 ℃ more than the temperature of saturation, will be fixed on seed crystal on the seed rod in advance lentamente down to molten surface, seed orientation is and C axle clamp angle 30 degree.Constant temperature was lowered the temperature 10 ℃ after half an hour, and crystal begins growth, at early growth period, or rose or permanent or cooling, waited to enter under the normal condition, lowered the temperature with 0.06 ℃/hour speed, and accompanied by 20 rev/mins speed rotation crystal.When cooling about 20 ℃ the time, stop brilliant the commentaries on classics, static growth, and continue to be cooled to about 800 ℃ by above speed.Growth ending is mentioned crystal, is annealed to room temperature with 50 ℃/hour speed, obtains ∮ 100 * 28mm 3The transparent large single crystal of high-quality.
Embodiment 3:
Take by weighing BaCO 32664.9 gram, H 3BO 31668.6 grams, the NaF292.1 gram places the agate mortar ground and mixed even these three kinds of raw materials together, by repeatedly adding ∮ 120 * 110mm after the fusion 3Platinum crucible in, and with crucible place the growth stove, be warming up to 990 ℃, constant temperature 36 hours, then under temperature about 20 ℃ more than the temperature of saturation, will be fixed on seed crystal on the seed rod in advance lentamente down to molten surface, seed orientation is and C axle clamp angle 20 degree.Constant temperature was lowered the temperature 13 ℃ after half an hour, and crystal begins growth, at early growth period, or rose or permanent or cooling, waited to enter under the normal condition, lowered the temperature with 0.03 ℃/hour speed, and accompanied by 10 rev/mins speed rotation crystal.When cooling about 15 ℃ the time, stop brilliant the commentaries on classics, static growth, and continue to be cooled to about 800 ℃ growth ending by above speed.
When mentioning crystal, crystal and seed rod break away from, adopt the converter method of falling liquid, bell is opened rapidly, the crucible of adorning crystal and liquation is clipped to rapidly in the converter that has been warmed up to relevant temperature, rotate stove to the sea line a little less than rotation axis, pouring melt, the crystal that generates is stayed in the crucible, is annealed to room temperature with converter with about 50 ℃/hour speed.Can obtain 120 * 32mm 3The transparent large single crystal of high-quality.
Embodiment 4:
Take by weighing BaCO 34342.8 gram, H 3BO 32719.2 gram, the NaF476.0 gram places the agate mortar ground and mixed even these three kinds of raw materials together, by repeatedly adding ∮ 150 * 130mm after the fusion 3Platinum crucible in, and with crucible place the growth stove, be warming up to 1000 ℃, constant temperature 48 hours, then under temperature about 30 ℃ more than the temperature of saturation, will be fixed on seed crystal on the seed rod in advance lentamente down to molten surface, seed orientation is and C axle clamp angle 0 degree.Constant temperature was lowered the temperature 20 ℃ after half an hour, and crystal begins growth, at early growth period, or rose or permanent or cooling, waited to enter under the normal condition, lowered the temperature with 0.01 ℃/hour speed, and accompanied by 5 rev/mins speed rotation crystal.When cooling about 10 ℃ the time, stop brilliant the commentaries on classics, static growth, and continue to be cooled to about 800 ℃ growth ending by above speed.
When mentioning crystal, crystal and seed rod break away from, adopt the converter method of falling liquid, bell is opened rapidly, the crucible of adorning crystal and liquation is clipped to rapidly in the converter that has been warmed up to relevant temperature, rotate stove to the sea line a little less than rotation axis, pouring melt, the crystal that generates is stayed in the crucible, is annealed to room temperature with converter with about 50 ℃/hour speed.Can obtain 150 * 35mm 3The transparent large single crystal of high-quality.

Claims (13)

1, a kind of method of improved growing low temperature phase-deviation barium borate monocrystal by smelting salt crystal method, its step comprise batching, seed crystal, cooling are grown and come out of the stove down, select Na during batching for use 2O or NaF make fusing assistant, ratio of components BaB 2O 4/ Na 2O=73-78/27-22 (mole percent) or BaB 2O 4/ NaF=64～67/36-33 (mole percent) the invention is characterized in:
(1) seed crystal centre-drilling hole screws in the seed rod lower end or insert in the hole and fixes;
(2) in the crystal growing process, its rate of temperature fall is 0.01 ℃/hour--0.1 ℃/hour;
(3) in the crystal growing process, the crystal rotating speed is 0--30 rev/min;
When (4) descending seed crystal, seed crystal is positioned at the molten surface center, and it is oriented to perpendicular to horizontal liquid level, becomes 0-60 degree angle with the C axle;
When (5) crystal growth finishes,, then adopt the converter method of falling liquid, with liquation and crystal separation if can not lift from liquid level.
2, according to claim 1(1) described growing method, it is characterized in that seed crystal centre-drilling hole can bore;
3, according to claim 1(1) described growing method, it is characterized in that seed crystal centre-drilling hole can not bore;
4, according to claim 2,3 described growing methods, the fixed form car that it is characterized in that seed crystal and seed rod be threaded into fixing;
5,, it is characterized in that the fixed form of seed crystal and seed rod can be fixed with the platinum filament colligation according to claim 2,3 described growing methods;
6, according to claim 1(4) described growing method, it is characterized in that the orientation of seed crystal is preferably the C axle;
7, according to claim 1(3) described growing method, it is characterized in that crystal stops operating after crystal growth for some time, the static growth ending that grows to.
8, according to claim 1(4) described growing method, it is characterized in that down seed crystal is more than the temperature of saturation approximately under 10-30 ℃ the temperature, with seed crystal lentamente down to molten surface.
9, according to the said growing method of claim 1, it is characterized in that then rate of temperature fall falls within the low rate interval if crucible size is big, otherwise, then fall within the two-forty interval.
10, growing method according to claim 1 is characterized in that the crystal growth initial stage, can adopt the intensification control growing;
11, growing method according to claim 1 is characterized in that the crystal growth initial stage, can adopt the thermostatic control growth;
12, growing method according to claim 1 is characterized in that the crystal growth initial stage, can adopt the cooling control growing.
13, growing method according to claim 1 is characterized in that the original components optimum proportion than being BaB 2O 4/ NaF=66.5/33.5(mole percent).
CN 92112921 1992-11-04 1992-11-04 Low temperature phase barium metaborate single crystal grown by improved fusedsalt seed crystal method Expired - Lifetime CN1032072C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6146553A (en) * 1998-05-14 2000-11-14 University Of Science And Technology Of China Nonlinear optical crystal of compound R2 MB10 O19 and producing method and producing method and uses thereof
WO2010009597A1 (en) * 2008-07-25 2010-01-28 中国科学院福建物质结构研究所 Doped low temperature phase bab2o4 single crystal, the manufacturing method thereof and wave changing elements therefrom
CN102383182A (en) * 2011-10-23 2012-03-21 福建福晶科技股份有限公司 Molten-salt growth method for reducing central envelope of BBO(Barium Boron Oxide) crystals
CN102965723A (en) * 2012-12-06 2013-03-13 福建福晶科技股份有限公司 Method for inhibiting radial rapid growth of BBO (Barium Boron Oxide) crystal
CN103225108A (en) * 2013-04-07 2013-07-31 福建福晶科技股份有限公司 Method for rapid growth of large-size BBO crystal
CN109112626A (en) * 2018-10-25 2019-01-01 莱芜职业技术学院 Non-linear optical crystal material β-BaB2O4Growing method
CN110071410A (en) * 2011-07-22 2019-07-30 科磊股份有限公司 Laser with high quality, the nonlinear crystal for stablizing output beam and long-life high conversion efficiency
CN110923812A (en) * 2019-11-27 2020-03-27 福建福晶科技股份有限公司 Low-temperature phase barium metaborate crystal growth method

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6146553A (en) * 1998-05-14 2000-11-14 University Of Science And Technology Of China Nonlinear optical crystal of compound R2 MB10 O19 and producing method and producing method and uses thereof
WO2010009597A1 (en) * 2008-07-25 2010-01-28 中国科学院福建物质结构研究所 Doped low temperature phase bab2o4 single crystal, the manufacturing method thereof and wave changing elements therefrom
US8514483B2 (en) 2008-07-25 2013-08-20 Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences Doped low-temperature phase barium metaborate single crystal, the manufacturing method thereof and wave changing elements therefrom
US9260798B2 (en) 2008-07-25 2016-02-16 Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences Doped low-temperature phase barium metaborate single crystal, the manufacturing method thereof and wave changing elements therefrom
CN110071410A (en) * 2011-07-22 2019-07-30 科磊股份有限公司 Laser with high quality, the nonlinear crystal for stablizing output beam and long-life high conversion efficiency
CN110071410B (en) * 2011-07-22 2022-02-01 科磊股份有限公司 Laser with nonlinear crystal with high quality, stable output beam, long service life and high conversion efficiency
CN102383182A (en) * 2011-10-23 2012-03-21 福建福晶科技股份有限公司 Molten-salt growth method for reducing central envelope of BBO(Barium Boron Oxide) crystals
CN102965723A (en) * 2012-12-06 2013-03-13 福建福晶科技股份有限公司 Method for inhibiting radial rapid growth of BBO (Barium Boron Oxide) crystal
CN102965723B (en) * 2012-12-06 2016-03-09 福建福晶科技股份有限公司 A kind of method suppressing the radial too fast growth of bbo crystal
CN103225108B (en) * 2013-04-07 2016-04-06 福建福晶科技股份有限公司 A kind of method of rapid growth of large-size BBO crystal
CN103225108A (en) * 2013-04-07 2013-07-31 福建福晶科技股份有限公司 Method for rapid growth of large-size BBO crystal
CN109112626A (en) * 2018-10-25 2019-01-01 莱芜职业技术学院 Non-linear optical crystal material β-BaB2O4Growing method
CN110923812A (en) * 2019-11-27 2020-03-27 福建福晶科技股份有限公司 Low-temperature phase barium metaborate crystal growth method

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