CN103290466A - YAB (Yttrium Aluminum Borate) crystal growth fluxing agent and YAB crystal growing method - Google Patents
YAB (Yttrium Aluminum Borate) crystal growth fluxing agent and YAB crystal growing method Download PDFInfo
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- CN103290466A CN103290466A CN201210047053XA CN201210047053A CN103290466A CN 103290466 A CN103290466 A CN 103290466A CN 201210047053X A CN201210047053X A CN 201210047053XA CN 201210047053 A CN201210047053 A CN 201210047053A CN 103290466 A CN103290466 A CN 103290466A
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Abstract
The invention relates to a YAB (Yttrium Aluminum Borate) crystal growth fluxing agent and a YAB crystal growing method. The YAB crystal growth fluxing agent is an Al2O3-boride-lithium-metal fluoride mixture system, wherein the mole ratio of Al2O3 to boride to lithium to metal fluoride is (5-8):(2-4):(0.5-2):(0.5-1.5); the boride is B2O3 or H2BO3; the lithium is Li2O or Li2CO3; and the metal fluoride comprises monovalent metal fluorides and divalent metal fluorides. By utilizing the YAB crystal growth fluxing agent and the YAB crystal growing method provided by the invention, the crystal stability in the crystal growing process is effectively improved, and crystals of large size are obtained.
Description
Technical field
The present invention relates to a kind of YAB crystal growth fusing assistant and YAB growing method, be specifically related to a kind of YAB non-linear optic crystal growth fusing assistant and growing method thereof.
Background technology
Yttrium aluminum borate crystal (YAl
3(BO
3)
4, be called for short YAB) and be a kind of non-linear optical crystal material of finding the sixties in 20th century.The congruent fusion of YAB crystal right and wrong is 1280 ℃ of decomposition.Advantages such as this crystal has that nonlinear factor is big, stable chemical performance, nonhygroscopic and hardness are big.YAl
3(BO
3)
4The growth method of crystal is flux method.At present, flux method adopts the fusing assistant system that K is arranged
2Mo
3O
10, K
2Mo
3O
10-B
2O
3, PbO
2-B
2O
3And Li
2O-B
2O
3Deng.The main drawback of these fusing assistants: the molybdate fusing assistant causes molybdenum to enter in the lattice easily, had a strong impact on crystal mass, there is saturation point temperature height in other several fusing assistants, and volatilization is big, shortcomings such as viscosity height are difficult to grow the big high YAB crystal of quality of size.Also have with Al at present
2O
3-LiF is cosolvent system, but LiF is lighter, and has the big shortcoming of volatilization, so should not adopt.So be necessary to seek the YAB crystal of new suitable fusing assistant to grow good.
Summary of the invention
In order to overcome above-mentioned defective, the invention provides a kind of YAB crystal growth fusing assistant and YAB growing method, to improve crystal growth system stability, obtain than the big scale monocrystalline.
YAB crystal growth fusing assistant of the present invention is Al
2O
3-boride-lithiumation thing-metal fluoride mixed system;
Wherein, Al
2O
3: boride: lithiumation thing: the mol ratio of metal fluoride is (5～8): (2～4): (0.5～2): (0.5～1.5).
In addition, described boride is B
2O
3Or H
3BO
3Described lithiumation thing is Li
2O or Li
2CO
3
In addition, the preferred B of described boride
2O
3
In addition, the preferred Li of described lithiumation thing
2O.
In addition, described metal fluoride is monovalence metal fluoride or divalent metal fluorochemical.
In addition, described metal fluoride is MgF
2, CaF
2, SrF
2, BaF
2, among NaF, the KF one or more.
The present invention also provides a kind of YAB growing method of described fusing assistant, and it comprises the steps:
(1) according to Y
2O
3: fusing assistant is after 1: 1 molar ratio mixes, and is warming up to 1200～1300 ℃ of fusions, obtains the material of growing;
(2) treat the complete fusion of grower material, be cooled to 950～1050 ℃, attempt seed crystal with YAB and find YAB crystal growth temperature of saturation;
(3) be cooled to the growth temperature of saturation, put into the YAB seed crystal and grow, growth is lowered the temperature with the speed rotating crystal of 20～40rpm and with 0.1～2.0 ℃/day simultaneously;
(4) treat that crystal growth breaks away from the growth material to required yardstick, be down to room temperature with 20～80 ℃/h speed, get the YAB crystal.
Wherein, in described step (1), be that container takes up molten mass with the platinum crucible.
In addition, in step (3), the seed crystal direction of putting into is any direction.
In addition, crystal rotates to be unidirectional rotation or two-way rotation in the described step (3).
In addition, attempt seed crystal with YAB and find YAB crystal growth temperature of saturation, refer to the YAB seed crystal is put into cosolvent system, find YAB crystal growth temperature numerical value accurately, i.e. YAB crystal growth temperature of saturation.Different seed crystals is in the solubility promoter of different proportionings, its growth temperature of saturation difference, when being higher than the growth temperature of saturation when putting into seed crystal, the seed crystal melt-off can not normal growth, and when being lower than the growth temperature of saturation and putting into seed crystal, then the crystal ramp becomes polycrystalline, the result who can not get wanting, therefore, the present invention finds accurately with the trial seed crystal and puts into formal YAB seed crystal again behind the YAB crystal growth temperature, makes its growth.
In addition, described YAB seed crystal does not have particular determination, namely can select the commercially available prod for use, can be synthetic in the laboratory high temperature solid-state by following formula I yet.
Y
2O
3+ 3Al
2O
3+ 8H
3BO
3=2YAl
3(BO
3)
4+ 12H
2O formula I
In addition, seed crystal adds the mode of growth material does not have particular determination, and it is medium for example can to add material by seed rod, and the mode that seed crystal is fixed on the seed rod can be selected arbitrarily.
In addition, described crystal rotation can be unidirectional rotation or two-way rotation, two-way rotation can be the two-way rotation according to the rotation of following swing circle: accelerating successively on first direction rotate, at the uniform velocity rotates, slows down rotates and stops the rotation, afterwards, on the second direction opposite with first direction, accelerate successively again rotate, at the uniform velocity rotate, slow down and rotate and stop the rotation.In above-mentioned two-way choice, swing circle does not have particular determination, preferred 1～10 minute of the rotational time of each direction, two-way rotation preferred 0.5～1 minute at interval.
Beneficial effect of the present invention
The solubility promoter growth method of YAB crystal provided by the invention has been used Al
2O
3The cosolvent system of-boride-lithiumation thing-metal fluoride.Compared with prior art, the advantage of this method is:
1) effectively reduce the growth temperature of saturation of crystal, its temperature range is between 950～1050 ℃.
2) can greatly reduce the volatility of system, improve the stability of system in the crystal growing process, prevent that stray crystal from forming, and improved the speed of growth of crystal.
3) can obviously reduce the viscosity of solution, lower viscosity is conducive to the solute transmission, is easy to the growth of crystal and has improved the growth quality of crystal.
4) the bigger high-quality YAB monocrystalline of a series of sizes of can stably growing.If use the large size crucible, the proper extension growth cycle can also obtain corresponding larger sized single crystal.
Embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
With 112.90g Y
2O
3, 254.90g Al
2O
3, 61.8g H
3BO
3, 18.47g Li
2CO
3With 15.58g MgF
2Grinding the back in the agate mill evenly mixes, pack in the platinum crucible of φ 80 * 70mm, put into monocrystal growing furnace, temperature rise rate with 70 ℃/h is heated to 1200 ℃, after above-mentioned crucible material is melted fully, slow cooling temperature to 960 ℃ is lowered to then and attempts seed crystal and seek saturation point temperature accurately.Temperature is controlled to be saturation point temperature accurately, is lowered to the position of formal seed crystal 5mm under the solution surface, the beginning crystal growth.Seed rotation rate is that per minute 40 changes, and rate of temperature fall is 0.2～2 ℃ of every day.Finish through crystal growth in 72 days, crystal lifted from 25mm place on the liquid level, with per hour 45 ℃ slowly cool to room temperature, obtaining size at last is 12 * 12 * 20mm
3The YAB monocrystalline, the transparent no inclusion of crystal.
Embodiment 2
With 90.32g Y
2O
3, 244.70g Al
2O
3, 98.88g H
3BO
3, 29.56g Li
2CO
3With 15.58g MgF
2In the agate mill, grind the back and evenly mix, in the platinum crucible of the φ 90 * 80mm that packs into, put into monocrystal growing furnace, be heated to 1300 ℃ with the temperature rise rate of 60 ℃/h, make above-mentioned crucible material melt fully full and uniform after, slow cooling temperature to 980 ℃.Be lowered to the trial seed crystal then and seek saturation point temperature accurately.Temperature is controlled to be saturation point temperature accurately, is lowered to the position of formal seed crystal 30mm under the solution surface, the beginning crystal growth.Seed rotation rate is that per minute 35 changes, and rate of temperature fall is 0.1～0.7 ℃/day.Finish through crystal growth in 50 days, crystal lifted from 20mm place on the liquid level, with per hour 20 ℃ slowly cool to room temperature, obtaining size at last is 10 * 10 * 18mm
3The YAB monocrystalline of unit, the transparent no inclusion of crystal.
Embodiment 3
With 67.74g Y
2O
3, 244.70g Al
2O
3, 55.62g H
3BO
3, 44.33g Li
2CO
3In the agate mill, grind the back with 18.90g NaF and evenly mix, in the platinum crucible of the φ 80 * 70mm that packs into, put into monocrystal growing furnace, be heated to 1300 ℃ with the temperature rise rate of 30 ℃/h, above-mentioned crucible material is melted fully after, slow cooling temperature to 1020 ℃.Be lowered to the trial seed crystal then and seek saturation point temperature accurately.Temperature is controlled to be saturation point temperature accurately, is lowered to the position of formal seed crystal 5mm under the solution surface, the beginning crystal growth.Seed rotation rate is that per minute 25 changes, and rate of temperature fall is 0.2～1.6 ℃ of every day.Finish through crystal growth in 76 days, crystal lifted from 30mm place on the liquid level, with per hour 60 ℃ slowly cool to room temperature, obtaining size at last is 13 * 15 * 22mm
3The YAB monocrystalline, the transparent no inclusion of crystal.
Embodiment 4:
With 67.74g Y
2O
3, 244.70g Al
2O
3, 41.76g B
2O
3, 8.94g Li
2O, 26.15gKF grind the back in the agate mill evenly mixes, and in the platinum crucible of the φ 90 * 80mm that packs into, puts into monocrystal growing furnace, is heated to 1250 ℃ with the temperature rise rate of 30 ℃/h, above-mentioned crucible material is melted fully after, slow cooling temperature to 990 ℃.Be lowered to the trial seed crystal then and seek saturation point temperature accurately.Temperature is controlled to be saturation point temperature accurately, is lowered to the position of formal seed crystal 5mm under the solution surface, the beginning crystal growth.Seed rotation rate is that per minute 25 changes, and rate of temperature fall is 0.4～2.0 ℃ of every day.Finish through crystal growth in 80 days, crystal lifted from 30mm place on the liquid level, with per hour 20 ℃ slowly cool to room temperature, obtaining size at last is 15 * 16 * 24mm
3The YAB monocrystalline, the transparent no inclusion of crystal.
Embodiment 5:
With 79.03g Y
2O
3, 214.12g Al
2O
3, 97.44g B
2O
3, 20.86g Li
2O and 27.33g CaF
2In the agate mill, grind the back and evenly mix, in the platinum crucible of the φ 80 * 70mm that packs into, be heated to 1250 ℃ with the temperature rise rate of 30 ℃/h, above-mentioned crucible material is melted fully after, slow cooling temperature to 980 ℃.Be lowered to the trial seed crystal then and seek saturation point temperature accurately.Temperature is controlled to be saturation point temperature accurately, is lowered to the position of formal seed crystal 5mm under the solution surface, the beginning crystal growth.Seed rotation rate is that per minute 20 changes, and rate of temperature fall is 0.1～0.9 ℃ of every day.Finish through crystal growth in 68 days, crystal lifted from 25mm place on the liquid level, with per hour 30 ℃ slowly cool to room temperature, obtaining size at last is 12 * 14 * 17mm
3The YAB monocrystalline, the transparent no inclusion of crystal.
Embodiment 6:
With 90.32g Y
2O
3, 203.92g Al
2O
3, 83.52g B
2O
3, 17.88g Li
2O and 50.25g SrF
2In the agate mill, grind the back and evenly mix, in the platinum crucible of the φ 90 * 80mm that packs into, put into monocrystal growing furnace, be heated to 1300 ℃ with the temperature rise rate of 50 ℃/h, make above-mentioned crucible material melt slowly cooling temperature to 1050 ℃ of back fully.Be lowered to the trial seed crystal then and seek saturation point temperature accurately.Temperature is controlled to be saturation point temperature accurately, is lowered to the position of formal seed crystal 5mm under the solution surface, the beginning crystal growth.Seed rotation rate is that per minute 30 changes, and rate of temperature fall is 0.3～1.0 ℃ of every day.Finish through crystal growth in 60 days, crystal lifted from 30mm place on the liquid level, with per hour 80 ℃ slowly cool to room temperature, obtaining size at last is 17 * 18 * 18mm
3The YAB monocrystalline, the transparent no inclusion of crystal.
Embodiment 7:
With 135.49g Y
2O
3, 305.88g Al
2O
3, 148.39g H
3BO
3, 88.67g Li
2CO
3With 157.79g BaF
2In the agate mill, grind the back and evenly mix, in the platinum crucible of the φ 80 * 70mm that packs into, put into monocrystal growing furnace, be heated to 1200 ℃ with the temperature rise rate of 50 ℃/h, above-mentioned crucible material is melted fully after, slow cooling temperature to 1030 ℃.Be lowered to the trial seed crystal then and seek saturation point temperature accurately.Temperature is controlled to be saturation point temperature accurately, is lowered to the position of formal seed crystal 5mm under the solution surface, the beginning crystal growth.Seed rotation rate is that per minute 30 changes, and rate of temperature fall is 0.3～1.9 ℃ of every day.Finish through crystal growth in 84 days, crystal lifted from 30mm place on the liquid level, with per hour 70 ℃ slowly cool to room temperature, obtaining size at last is 26 * 26 * 30mm
3The YAB monocrystalline, the transparent no inclusion of crystal.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the technology of the present invention principle; can also make some improvement and replacement, these improvement and replacement also should be considered as protection scope of the present invention.
Claims (10)
1. a YAB crystal growth fusing assistant is characterized in that, described fusing assistant is Al
2O
3-boride-lithiumation thing-metal fluoride mixed system;
Wherein, Al
2O
3: boride: lithiumation thing: the mol ratio of metal fluoride is (5～8): (2～4): (0.5～2): (0.5～1.5).
2. fusing assistant according to claim 1 is characterized in that, described boride is B
2O
3Or H
3BO
3Described lithiumation thing is Li
2O or Li
2CO
3
3. fusing assistant according to claim 2 is characterized in that, described boride is B
2O
3
4. fusing assistant according to claim 2 is characterized in that, described lithiumation thing is Li
2O.
5. fusing assistant according to claim 1 is characterized in that, described metal fluoride is monovalence metal fluoride or divalent metal fluorochemical.
6. fusing assistant according to claim 5 is characterized in that, described metal fluoride is MgF
2, CaF
2, SrF
2, BaF
2, among NaF, the KF one or more.
7. the YAB growing method according to the arbitrary described fusing assistant of claim 1～6 is characterized in that, comprises the steps:
(1) according to Y
2O
3: fusing assistant is after 1: 1 molar ratio mixes, and is warming up to 1200～1300 ℃ of fusions, obtains the material of growing;
(2) treat the complete fusion of grower material, be cooled to 950～1050 ℃, attempt seed crystal with YAB and find YAB crystal growth temperature of saturation;
(3) be cooled to the growth temperature of saturation, put into the YAB seed crystal and grow, growth is lowered the temperature with the speed rotating crystal of 20～40rpm and with 0.1～2.0 ℃/day simultaneously;
(4) treat that crystal growth breaks away from the growth material to required yardstick, be down to room temperature with 20～80 ℃/h speed, get the YAB crystal.
8. method according to claim 7 is characterized in that, in described step (1), is that container takes up molten mass with the platinum crucible.
9. method according to claim 7 is characterized in that, in step (3), the seed crystal direction of putting into is any direction.
10. method according to claim 7 is characterized in that, crystal rotates to be unidirectional rotation or two-way rotation in the described step (3).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105350083A (en) * | 2015-11-20 | 2016-02-24 | 中国科学院理化技术研究所 | (Bi1-x-yLnxCey)3TeBO9 compound, (Bi1-x-yLnxCey)3TeBO9 nonlinear optical crystal, (Bi1-x-yLnxCey)3TeBO9 scintillation crystal, preparation method and application thereof |
| CN108893778A (en) * | 2018-07-16 | 2018-11-27 | 苏州四海常晶光电材料有限公司 | A kind of ABO3Mixed crystal and growing method |
| CN114262932A (en) * | 2021-11-25 | 2022-04-01 | 天津理工大学 | Cesium lithium borate crystal fluxing agent and crystal growth method |
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| CN105350083A (en) * | 2015-11-20 | 2016-02-24 | 中国科学院理化技术研究所 | (Bi1-x-yLnxCey)3TeBO9 compound, (Bi1-x-yLnxCey)3TeBO9 nonlinear optical crystal, (Bi1-x-yLnxCey)3TeBO9 scintillation crystal, preparation method and application thereof |
| CN105350083B (en) * | 2015-11-20 | 2017-10-10 | 中国科学院理化技术研究所 | Boric acid tellurium bismuth compound, boric acid tellurium bismuth nonlinear optical crystal, boric acid tellurium bismuth scintillation crystal and preparation method and application |
| CN108893778A (en) * | 2018-07-16 | 2018-11-27 | 苏州四海常晶光电材料有限公司 | A kind of ABO3Mixed crystal and growing method |
| CN114262932A (en) * | 2021-11-25 | 2022-04-01 | 天津理工大学 | Cesium lithium borate crystal fluxing agent and crystal growth method |
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