CN112176395A - Device and method for growing high-quality large-size BiBO crystal by molten salt growth method - Google Patents
Device and method for growing high-quality large-size BiBO crystal by molten salt growth method Download PDFInfo
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- CN112176395A CN112176395A CN202011087350.8A CN202011087350A CN112176395A CN 112176395 A CN112176395 A CN 112176395A CN 202011087350 A CN202011087350 A CN 202011087350A CN 112176395 A CN112176395 A CN 112176395A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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Abstract
A device and a method for growing high-quality large-size BiBO crystals by a molten salt growth method adopt ultra-pure Bi2O3And B2O3Preparing according to a proportion, fully grinding and mixing, presintering at a high temperature in a gradient manner to obtain a crystal growth polycrystal material, and selecting a corundum crucible, a material mixing furnace, a seed rod with a pair of smooth stirring rods, a platinum crucible and a molten salt furnace as a growth device. The crystal growth polycrystal material is heated and melted, and the top seed crystal melt method crystal growth process of stirring the growth melt is enhanced by adopting a pair of smooth stirring rods attached to the seed crystal rods in the crystal growth process, so that the problem that the BiBO crystal growth melt with low melting point and high viscosity is easy to nucleate naturally is solved, the quality conveying of the single crystal in the growth process is improved, and the smooth growth of the BiBO crystal with high quality and large size on the surface of the uniform melt or in the melt is facilitated.
Description
Technical Field
The invention relates to the field of crystal growth, in particular to a device and a method for growing a large-size and high-quality BiBO crystal by a molten salt growth method.
Background
The borate crystal occupies an extremely important position in nonlinear optical frequency doubling, especially ultraviolet and deep ultraviolet frequency doubling. Bismuth triborate crystal BiB3O6The (BiBO) is a typical borate nonlinear optical crystal. Many scholars have conducted a lot of researches on growth, structure and performance at home and abroad. The BiBO crystal has large nonlinear optical coefficient (compared with BBO, LBO, KTP and LiIO which are widely used)2The crystal has the advantages of large light transmittance (more than 80%), wide light transmission waveband (270-6250 nm), high light damage threshold (comparable with high-quality LBO), no deliquescence, easy processing (medium hardness) and the like, so the crystal has a good application prospect in the aspect of laser frequency doubling.
At present, BiBO crystals with larger size and higher quality can be grown from high-temperature melt with stoichiometric ratio by adopting a top seed crystal method, but the characteristics of high viscosity and the like of the growing melt due to low symmetry and low melting point of the crystals bring great difficulty to the growth of high-quality large-size bismuth triborate crystals, a plurality of defect problems still exist in the crystal growth process, and the key point of the wide application of the crystals lies in the growth of large-size high-optical-quality single crystals. The crystal growth process is a very complex process, the correct selection of a cosolvent, the enhancement of stirring during melt preparation, the prolongation of melt heat preservation time, the adjustment of the rotation speed of a growing crystal and the like play an important role in the growth of high-quality large-size BiBO single crystals, but the fundamental problem is not solved enough, so that the growth process of the BiBO crystals needs to be researched more widely to obtain the high-quality BiBO crystals.
Aiming at the high-viscosity melt for growing the BiBO crystal, not only natural crystal nuclei are easy to form, but also the quality transportation of the single crystal in the growth process is limited, and a plurality of defects are generated in the growth of the single crystal.
Disclosure of Invention
The invention aims to: provides a device and a method for growing BiBO crystal by a molten salt growth method, and realizes the preparation of large-size BiBO crystal with excellent performance.
To achieve the above objects, the technical operations of the present inventionThe following were used: preparing high-quality large-size bismuth triborate single crystal by adopting a top seed crystal high-temperature solution method. According to Bi2O3—B2O3Binary phase diagram, weighing pure Bi according to stoichiometric ratio2O3And B2O3Adding cosolvent, grinding, mixing, and repeatedly sintering; then placing the polycrystal material into a platinum crucible, then placing a material mixing furnace in the crucible, and heating to 900 ℃ to melt the material; moving the platinum crucible into a molten salt furnace, keeping the temperature for 24 hours, slowly reducing the melt to 3 ℃ above the saturation point, and inoculating seeds; after the seed crystal is slightly melted, the temperature is reduced to the saturation point temperature, and the temperature is kept for 24 hours and then the temperature is slowly reduced. The rotation of the seed rod and the stirring of the crystal growth melt by the stirring rod attached to the seed rod change the rotation speed and the cooling speed with the size of the crystal. The cooling speed is 0.3-1.0 ℃/d, the rotating speed is 30r/min at the beginning, and the cooling speed is reduced along with the increase of the crystal size. After the growth period, the large-size and high-quality bismuth triborate single crystal can be obtained.
Drawings
The figure is a schematic structural diagram of the seed rod of the invention: 1 is a crucible, 2 is a crystal, 3 is a seed rod, and 4 is a stirring rod without a blade on the seed rod.
Detailed Description
1. Weighing the ultra-pure Bi according to the stoichiometric ratio2O3And B2O3，B2O3Excessive by about 5 to 10 percent, grinding, uniformly mixing, putting into a corundum crucible, sintering for 24 hours at 200 ℃, and cooling to room temperature.
2. Smashing the sintered raw materials, repeatedly grinding until the raw materials become uniform powder, filling the powder into a corundum crucible, placing the corundum crucible into a 500-DEG C material mixing furnace for 48 hours, and cooling to room temperature.
3. And (3) smashing the secondarily sintered raw materials again, grinding the materials into uniform powder, filling the powder into a corundum crucible, putting the corundum crucible into a 700-DEG C material mixing furnace, calcining for 72 hours, and carrying out solid-phase reaction to obtain the crystal growth polycrystal material.
4. And putting the prepared polycrystalline material into a platinum crucible built-in material mixing furnace, and heating to 900 ℃ to melt the material.
5. Moving the platinum crucible to a molten salt growth furnace, keeping the temperature of 900 ℃ for 24h, slowly reducing the melt to 3 ℃ above the saturation point, slowly and underground putting the seed crystal on the seed crystal rod without a paddle stirring rod prepared in advance to the surface of the melt, cooling to the temperature of the saturation point after the seed crystal is micro-melted, and slowly cooling after keeping the temperature for 24 h.
6. The seed rod rotates, and the stirring rod without the paddle on the seed rod is connected with the stirring of the melt at the edge of the crucible, so that the double stirring inhibits the natural nucleation of the melt, promotes the quality conveying of the melt, and provides uniform and stable melt for the growth of large-size BiBO crystals with excellent performance.
7. The rotating speed and the cooling speed of the seed rod are changed along with the size of the crystal. The cooling speed is 0.3-1.0 ℃/d, the rotating speed is 30r/min at the beginning, the speed is reduced along with the increase of the crystal size, when the crystal grows to the controlled size, the seed rod is lifted to enable the crystal to be separated from the liquid level, and the temperature is reduced to the room temperature at the rate of 30 ℃/h, so that the BiBO single crystal with excellent performance and large size can be obtained.
Claims (4)
1. High-quality large-size BiB3O6A device and a method for growing (BiBO) crystals by a molten salt growth method adopt ultra-pure bismuth oxide and boron oxide as initial raw materials, a corundum crucible, a material combination furnace, a platinum seed crystal rod, a platinum crucible and a molten salt furnace are selected as growing devices,
the method is characterized by comprising the following operations:
(1) weighing pure bismuth oxide and boron oxide according to stoichiometric ratio, wherein the molar fraction of the boron oxide is about 5-10% excessive, fully grinding, putting into a corundum crucible, putting into a material combination furnace, repeatedly pre-burning, and carrying out solid phase reaction to obtain a crystal growth polycrystal material;
(2) putting the crystal growth polycrystal material into a platinum crucible built-in material mixing furnace for melting to obtain a crystal growth melt;
(3) moving the platinum crucible to a molten salt growth furnace, and searching a crystal growth point by using a seed crystal trial method at the saturation temperature of 3 ℃;
(4) carrying out crystal growth on the surface of the melt or in the melt by adopting a top seed crystal melt method crystal growth process for enhancing melt stirring in the crystal growth process;
(5) after the crystal grows to the controlled size, lifting the crystal to separate from the liquid level, and cooling to room temperature at the speed of 30 ℃/h to obtain the high-quality large-size BiBO crystal.
2. The method of claim 1, wherein the boron oxide of medium grade 1(1) is in molar excess of about 5% to about 10%.
3. The method of claim 1, wherein a pair of smooth stirring rods are attached to the seed rods during the crystal growth by the melt method in the steps 1(1), (4).
4. The method of claim 1, wherein in 1(4), during the crystal growth, the smooth stirring rod on the seed rod stirs the crystal growth melt at all times along with the rotation of the seed rod.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011087350.8A CN112176395A (en) | 2020-10-13 | 2020-10-13 | Device and method for growing high-quality large-size BiBO crystal by molten salt growth method |
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| CN202011087350.8A CN112176395A (en) | 2020-10-13 | 2020-10-13 | Device and method for growing high-quality large-size BiBO crystal by molten salt growth method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115652407A (en) * | 2022-11-16 | 2023-01-31 | 福建福晶科技股份有限公司 | Preparation method of BIBO crystal with high utilization rate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004099333A (en) * | 2002-02-13 | 2004-04-02 | Nikko Materials Co Ltd | Method of manufacturing compound semiconductor single crystal |
| RU2006121411A (en) * | 2006-06-08 | 2008-01-10 | Общество с ограниченной ответственностью "Серафим" (RU) | METHOD FOR GROWING CRYSTALS AND DEVICE FOR ITS IMPLEMENTATION |
| 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 |
| CN104328483A (en) * | 2014-11-13 | 2015-02-04 | 吴晟 | Single crystal growth method and device |
-
2020
- 2020-10-13 CN CN202011087350.8A patent/CN112176395A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004099333A (en) * | 2002-02-13 | 2004-04-02 | Nikko Materials Co Ltd | Method of manufacturing compound semiconductor single crystal |
| RU2006121411A (en) * | 2006-06-08 | 2008-01-10 | Общество с ограниченной ответственностью "Серафим" (RU) | METHOD FOR GROWING CRYSTALS AND DEVICE FOR ITS IMPLEMENTATION |
| 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 |
| CN104328483A (en) * | 2014-11-13 | 2015-02-04 | 吴晟 | Single crystal growth method and device |
Non-Patent Citations (1)
| Title |
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| 滕冰等: "新型非线性光学晶体硼酸铋（BiB3O6）的晶体生长和性能", 《科学通报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115652407A (en) * | 2022-11-16 | 2023-01-31 | 福建福晶科技股份有限公司 | Preparation method of BIBO crystal with high utilization rate |
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