CN103290466B - A kind of YAB crystal growth flux and YAB growing method - Google Patents
A kind of YAB crystal growth flux and YAB growing method Download PDFInfo
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- CN103290466B CN103290466B CN201210047053.XA CN201210047053A CN103290466B CN 103290466 B CN103290466 B CN 103290466B CN 201210047053 A CN201210047053 A CN 201210047053A CN 103290466 B CN103290466 B CN 103290466B
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Abstract
The present invention relates to a kind of YAB crystal growth cosolvent and YAB growing method, the YAB crystal growth cosolvent of the present invention is Al2O3-boride-lithiumation thing-metal fluoride mixed system; Wherein, Al2O3: boride: lithiumation thing: the mol ratio of metal fluoride is (5～8): (2～4): (0.5～2): (0.5～1.5); Described boride is B2O3Or H3BO3; Described lithiumation thing is Li2O or Li2CO3; Described metal fluoride includes monovalent metal fluoride and divalent metal fluoride. The crystal stability in crystal growing process can be effectively improved, it is thus achieved that large-size crystals by the YAB crystal growth cosolvent of the present invention and YAB growing method.
Description
Technical field
The present invention relates to a kind of YAB crystal growth flux and YAB growing method, be specifically related to a kind of YAB nonlinear optical crystal growth flux and growing method thereof.
Background technology
Yttrium aluminum borate crystal (YAl3(BO3)4, it is called for short YAB) and it is a kind of non-linear optical crystal material found the sixties in 20th century. YAB crystal is that off-congruent melts, 1280 DEG C of decomposition. The advantages such as this crystal has that nonlinear factor is big, stable chemical performance, nonhygroscopic and hardness are big. YAl3(BO3)4The growing method of crystal is flux growth metrhod. At present, flux growth metrhod adopts flux system to have K2Mo3O10、K2Mo3O10-B2O3、PbO2-B2O3And Li2O-B2O3Deng. The major defect of these fluxs: molybdate flux is easily caused molybdenum and enters in lattice, having had a strong impact on crystal mass, it is high to there is saturation point temperature in other several fluxs, and volatilization is big, the shortcomings such as viscosity is high, are difficult to grow the YAB crystal that quality larger in size is high. Currently also have with Al2O3-LiF is cosolvent system, but LiF is relatively light, and has the shortcoming that volatilization is big, so should not adopt. Therefore be necessary to find new suitable flux to grow excellent YAB crystal.
Summary of the invention
In order to overcome drawbacks described above, the present invention provides a kind of YAB crystal growth flux and YAB growing method, to improve crystal growth system stability, it is thus achieved that large scale monocrystalline.
The YAB crystal growth flux of the present invention is Al2O3-boride-lithiumation thing-metal fluoride mixed system;
Wherein, Al2O3: boride: lithiumation thing: the mol ratio of metal fluoride is (5～8): (2～4): (0.5～2): (0.5～1.5).
It addition, described boride is B2O3Or H3BO3; Described lithiumation thing is Li2O or Li2CO3。
It addition, the preferred B of described boride2O3。
It addition, the described preferred Li of lithiumation thing2O。
It addition, described metal fluoride is monovalent metal fluoride or divalent metal fluoride.
It addition, described metal fluoride is MgF2、CaF2、SrF2、BaF2, one or more in NaF, KF.
The present invention also provides for the YAB growing method of a kind of described flux, and it comprises the steps:
(1) according to Y2O3: flux is after the molar ratio mix homogeneously of 1: 1, is warming up to 1200～1300 DEG C and melts, and obtains growth material;
(2) treat that growth-gen material is completely melted, be cooled to 950～1050 DEG C, attempt seed crystal with YAB and find YAB crystal growth saturation temperature;
(3) being cooled to growth saturation temperature, put into YAB seed crystal and grow, growth is simultaneously with the speed rotating crystal of 20～40rpm and with 0.1～2.0 DEG C/day cooling;
(4) after crystal growth to required yardstick, depart from growth material, be down to room temperature with 20～80 DEG C/h speed, obtain YAB crystal.
Wherein, in described step (1), molten mass is taken up with platinum crucible for container.
It addition, in step (3), the seed crystal direction put into is any direction.
It addition, Crystal Rotation is single direction rotation or bidirectional rotation in described step (3).
It addition, attempt seed crystal with YAB to find YAB crystal growth saturation temperature, refer to and YAB seed crystal is put in cosolvent system, find YAB crystal growth temperature numerical value accurately, i.e. YAB crystal growth saturation temperature. Different seed crystals is in the cosolvent of different ratio, its growth saturation temperature is different, when being higher than growth saturation temperature and putting into seed crystal, seed crystal melt-off can not normal growth, lower than growth saturation temperature put into seed crystal time, then crystal quickly grows into polycrystalline, can not get the result wanted, therefore, the present invention finds and places into formal YAB seed crystal after YAB crystal growth temperature accurately attempting seed crystal so that it is growth.
It addition, described YAB seed crystal is without particular determination, commercially available prod namely can be selected, it is also possible to by following formula I at laboratory high temperature process heat.
Y2O3+3Al2O3+8H3BO3=2YAl3(BO3)4+12H2O Formulas I
It addition, seed crystal adds the mode of growth material without particular determination, for instance can passing through seed rod addition material medium, seed crystal is fixed on the mode on seed rod can arbitrarily be selected.
Additionally, described Crystal Rotation can be single direction rotation or bidirectional rotation, bidirectional rotation can be the bidirectional rotation rotated according to following swing circle: accelerate successively in a first direction to rotate, at the uniform velocity rotate, be rotated in deceleration and stop the rotation, afterwards, then accelerate successively in a second direction that is opposite the first direction to rotate, at the uniform velocity rotate, be rotated in deceleration and stop the rotation. In above-mentioned two-way choice, swing circle without particular determination, the rotational time in each direction preferably 1～10 minute, preferably 0.5～1 minute, bidirectional rotation interval.
Beneficial effects of the present invention
The cosolvent growing method of YAB crystal provided by the invention, employs Al2O3The cosolvent system of-boride-lithiumation thing-metal fluoride. Compared with prior art, the advantage of the method is in that:
1) effectively reducing the growth saturation temperature of crystal, its temperature range is between 950～1050 DEG C.
2) volatility of system can be greatly reduced, improve the stability of system in crystal growing process, it is prevented that stray crystal is formed, and improves the speed of growth of crystal.
3) can substantially reducing the viscosity of solution, relatively low viscosity is conducive to solute transport, it is easy to the growth quality growing and improve crystal of crystal.
4) a series of high-quality YAB monocrystalline larger in size can stably be grown. If using large scale crucible, proper extension growth cycle, it is also possible to obtain corresponding larger sized monocrystal.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
Embodiment 1
By 112.90gY2O3、254.90gAl2O3、61.8gH3BO3、18.47gLi2CO3With 15.58gMgF2Homogeneous phase mixing after grinding in Achates dismembyator, load in the platinum crucible of φ 80 × 70mm, put in monocrystal growing furnace, heat to 1200 DEG C with the heating rate of 70 DEG C/h, after making above-mentioned crucible material be completely melt, Slow cooling temperature to 960 DEG C, then enters to attempt down seed crystal and seeks saturation point temperature accurately.Temperature is controlled for saturation point temperature accurately, under enter formal seed crystal to the position of 5mm under solution surface, start crystal growth. Seed rotation rate is 40 turns per minute, and rate of temperature fall is every day 0.2～2 DEG C. Terminating through 72 days crystal growth, 25mm place on crystal lift-off liquid level, be slow cooling to room temperature with per hour 45 DEG C, finally obtaining size is 12 × 12 × 20mm3YAB monocrystalline, crystal is transparent in inclusion enclave.
Embodiment 2
By 90.32gY2O3、244.70gAl2O3、98.88gH3BO3、29.56gLi2CO3With 15.58gMgF2Homogeneous phase mixing after grinding in Achates dismembyator, loads in the platinum crucible of φ 90 × 80mm, puts in monocrystal growing furnace, heats to 1300 DEG C with the heating rate of 60 DEG C/h, make above-mentioned crucible material be completely melt full and uniform after, Slow cooling temperature to 980 DEG C. Then enter to attempt down seed crystal and seek saturation point temperature accurately. Temperature is controlled for saturation point temperature accurately, under enter formal seed crystal to the position of 30mm under solution surface, start crystal growth. Seed rotation rate is 35 turns per minute, and rate of temperature fall is 0.1～0.7 DEG C/day. Terminating through 50 days crystal growth, 20mm place on crystal lift-off liquid level, be slow cooling to room temperature with per hour 20 DEG C, finally obtaining size is 10 × 10 × 18mm3The YAB monocrystalline of unit, crystal is transparent in inclusion enclave.
Embodiment 3
By 67.74gY2O3、244.70gAl2O3、55.62gH3BO3、44.33gLi2CO3Homogeneous phase mixing after grinding in Achates dismembyator with 18.90gNaF, loads in the platinum crucible of φ 80 × 70mm, puts in monocrystal growing furnace, heats to 1300 DEG C with the heating rate of 30 DEG C/h, after making above-mentioned crucible material be completely melt, and Slow cooling temperature to 1020 DEG C. Then enter to attempt down seed crystal and seek saturation point temperature accurately. Temperature is controlled for saturation point temperature accurately, under enter formal seed crystal to the position of 5mm under solution surface, start crystal growth. Seed rotation rate is 25 turns per minute, and rate of temperature fall is every day 0.2～1.6 DEG C. Terminating through 76 days crystal growth, 30mm place on crystal lift-off liquid level, be slow cooling to room temperature with per hour 60 DEG C, finally obtaining size is 13 × 15 × 22mm3YAB monocrystalline, crystal is transparent in inclusion enclave.
Embodiment 4:
By 67.74gY2O3、244.70gAl2O3、41.76gB2O3、8.94gLi2O, 26.15gKF grind in Achates dismembyator after Homogeneous phase mixing, load in the platinum crucible of φ 90 × 80mm, put in monocrystal growing furnace, heat to 1250 DEG C with the heating rate of 30 DEG C/h, after making above-mentioned crucible material be completely melt, Slow cooling temperature to 990 DEG C. Then enter to attempt down seed crystal and seek saturation point temperature accurately. Temperature is controlled for saturation point temperature accurately, under enter formal seed crystal to the position of 5mm under solution surface, start crystal growth. Seed rotation rate is 25 turns per minute, and rate of temperature fall is every day 0.4～2.0 DEG C. Terminating through 80 days crystal growth, 30mm place on crystal lift-off liquid level, be slow cooling to room temperature with per hour 20 DEG C, finally obtaining size is 15 × 16 × 24mm3YAB monocrystalline, crystal is transparent in inclusion enclave.
Embodiment 5:
By 79.03gY2O3、214.12gAl2O3、97.44gB2O3、20.86gLi2O and 27.33gCaF2Homogeneous phase mixing after grinding in Achates dismembyator, loads in the platinum crucible of φ 80 × 70mm, heats to 1250 DEG C with the heating rate of 30 DEG C/h, after making above-mentioned crucible material be completely melt, and Slow cooling temperature to 980 DEG C. Then enter to attempt down seed crystal and seek saturation point temperature accurately. Temperature is controlled for saturation point temperature accurately, under enter formal seed crystal to the position of 5mm under solution surface, start crystal growth.Seed rotation rate is 20 turns per minute, and rate of temperature fall is every day 0.1～0.9 DEG C. Terminating through 68 days crystal growth, 25mm place on crystal lift-off liquid level, be slow cooling to room temperature with per hour 30 DEG C, finally obtaining size is 12 × 14 × 17mm3YAB monocrystalline, crystal is transparent in inclusion enclave.
Embodiment 6:
By 90.32gY2O3、203.92gAl2O3、83.52gB2O3、17.88gLi2O and 50.25gSrF2Homogeneous phase mixing after grinding in Achates dismembyator, loads in the platinum crucible of φ 90 × 80mm, puts in monocrystal growing furnace, heats to 1300 DEG C with the heating rate of 50 DEG C/h, makes above-mentioned crucible material be completely melt rear Slow cooling temperature to 1050 DEG C. Then enter to attempt down seed crystal and seek saturation point temperature accurately. Temperature is controlled for saturation point temperature accurately, under enter formal seed crystal to the position of 5mm under solution surface, start crystal growth. Seed rotation rate is 30 turns per minute, and rate of temperature fall is every day 0.3～1.0 DEG C. Terminating through 60 days crystal growth, 30mm place on crystal lift-off liquid level, be slow cooling to room temperature with per hour 80 DEG C, finally obtaining size is 17 × 18 × 18mm3YAB monocrystalline, crystal is transparent in inclusion enclave.
Embodiment 7:
By 135.49gY2O3、305.88gAl2O3、148.39gH3BO3、88.67gLi2CO3With 157.79gBaF2Homogeneous phase mixing after grinding in Achates dismembyator, loads in the platinum crucible of φ 80 × 70mm, puts in monocrystal growing furnace, heats to 1200 DEG C with the heating rate of 50 DEG C/h, after making above-mentioned crucible material be completely melt, and Slow cooling temperature to 1030 DEG C. Then enter to attempt down seed crystal and seek saturation point temperature accurately. Temperature is controlled for saturation point temperature accurately, under enter formal seed crystal to the position of 5mm under solution surface, start crystal growth. Seed rotation rate is 30 turns per minute, and rate of temperature fall is every day 0.3～1.9 DEG C. Terminating through 84 days crystal growth, 30mm place on crystal lift-off liquid level, be slow cooling to room temperature with per hour 70 DEG C, finally obtaining size is 26 × 26 × 30mm3YAB monocrystalline, crystal is transparent in inclusion enclave.
The above is only the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the technology of the present invention principle; can also making some improvement and replacement, these improve and replace and also should be regarded as protection scope of the present invention.
Claims (8)
1. a YAB crystal growth flux, it is characterised in that described flux is Al2O3-boride-lithiumation thing-metal fluoride mixed system;
Wherein, Al2O3: boride: lithiumation thing: the mol ratio of metal fluoride is (5～8): (2～4): (0.5～2): (0.5～1.5);
Described metal fluoride is MgF2、CaF2、SrF2、BaF2, one or more in NaF, KF.
2. flux according to claim 1, it is characterised in that described boride is B2O3Or H3BO3; Described lithiumation thing is Li2O or Li2CO3。
3. flux according to claim 2, it is characterised in that described boride is B2O3。
4. flux according to claim 2, it is characterised in that described lithiumation thing is Li2O。
5. the YAB growing method adopting the arbitrary described flux of Claims 1 to 4, it is characterised in that comprise the steps:
(1) according to Y2O3: flux is after the molar ratio mix homogeneously of 1:1, is warming up to 1200～1300 DEG C and melts, and obtains growth material;
(2) treat that growth-gen material is completely melted, be cooled to 950～1050 DEG C, attempt seed crystal with YAB and find YAB crystal growth saturation temperature;
(3) being cooled to growth saturation temperature, put into YAB seed crystal and grow, growth is simultaneously with the speed rotating crystal of 20～40rpm and with 0.1～2.0 DEG C/day cooling;
(4) after crystal growth to required yardstick, depart from growth material, be down to room temperature with 20～80 DEG C/h speed, obtain YAB crystal.
6. method according to claim 5, it is characterised in that in described step (1), contain molten mass with platinum crucible for container.
7. method according to claim 5, it is characterised in that in step (3), the seed crystal direction put into is any direction.
8. method according to claim 5, it is characterised in that in described step (3), Crystal Rotation is single direction rotation or bidirectional rotation.
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| 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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| CN86101971A (en) * | 1986-03-22 | 1987-10-07 | 山东大学 | Crystal growth of combined-functional crystal aluminium yttrium neodymium tetraborate |
| CN101831706A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Growth method of low ultraviolet absorption YA13(BO3)4 crystal |
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| CN101245490B (en) * | 2007-02-15 | 2010-08-18 | 中国科学院理化技术研究所 | Flux growth method for CsLiB6O10 crystal |
| CN101307228B (en) * | 2008-02-29 | 2011-11-30 | 中国计量学院 | Chlorine-aluminosilicate fluorescent powder and method for preparing same |
| CN101787558B (en) * | 2009-01-23 | 2012-02-15 | 中国科学院理化技术研究所 | Fluxing agent growing method of K2Al2B2O7 crystal |
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| CN86101971A (en) * | 1986-03-22 | 1987-10-07 | 山东大学 | Crystal growth of combined-functional crystal aluminium yttrium neodymium tetraborate |
| CN101831706A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Growth method of low ultraviolet absorption YA13(BO3)4 crystal |
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