CN115233287A - beta-BBO crystal growth method using cesium fluoride as fluxing agent - Google Patents
beta-BBO crystal growth method using cesium fluoride as fluxing agent Download PDFInfo
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- CN115233287A CN115233287A CN202210959833.5A CN202210959833A CN115233287A CN 115233287 A CN115233287 A CN 115233287A CN 202210959833 A CN202210959833 A CN 202210959833A CN 115233287 A CN115233287 A CN 115233287A
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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
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- Crystallography & Structural Chemistry (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to the technical field of crystal growth, in particular to a beta-BBO crystal growth method taking cesium fluoride as a fluxing agent, which comprises the steps of taking barium carbonate and boric acid as raw materials, taking cesium fluoride as a fluxing agent, putting the raw materials and the fluxing agent into a platinum crucible, putting the platinum crucible into a crystal growth furnace, heating to a first temperature to melt the materials, cooling to a second temperature, then adding seed crystals into a melt, starting crystal growth, continuing cooling to the end of crystal growth, lifting the crystal away from a liquid level, and cooling to room temperature to obtain the beta-BBO crystal. According to the method for growing the beta-BBO crystal by taking the cesium fluoride as the fluxing agent, the cesium fluoride is used as the fluxing agent, so that the viscosity of a melt can be reduced, the saturation point of the beta-BBO crystal can be reduced, and the high-quality beta-BBO crystal can be obtained; the beta-BBO crystal growth method using cesium fluoride as a fluxing agent can prepare single crystals with the size of 80mm multiplied by 30mm, and the crystal size is large.
Description
Technical Field
The invention relates to the technical field of crystal growth, in particular to a beta-BBO crystal growth method taking cesium fluoride as a fluxing agent.
Background
The beta-BBO crystal has wide light transmission range, very low absorption coefficient and weak piezoelectric ringing effect, and compared with other electro-optical modulation crystals, the beta-BBO crystal has higher extinction ratio, larger phase matching angle, higher light damage resistance threshold, wide-band temperature matching and excellent optical uniformity, is favorable for improving the stability of laser output power, and has wide application particularly for triple frequency multiplication of an N/: YAG laser.
With the increasing application of the beta-BBO crystal in the field of solid laser frequency conversion, the requirements on the large size and high quality of the beta-BBO crystal are improved at present.
Disclosure of Invention
Aiming at the problems of small size, low quality and the like in the prior art, the invention provides a beta-BBO crystal growth method using cesium fluoride as a fluxing agent, and the prepared beta-BBO crystal has the advantages of large size and high quality.
The invention provides a beta-BBO crystal growth method taking cesium fluoride as a fluxing agent, which comprises the steps of taking barium carbonate and boric acid as raw materials, taking cesium fluoride as the fluxing agent, putting the raw materials and the fluxing agent into a platinum crucible, placing the platinum crucible into a crystal growth furnace, heating to a first temperature for melting, cooling to a second temperature, then putting seed crystals into a melt, starting crystal growth, continuously cooling to the end of crystal growth, lifting the crystals off a liquid surface, and cooling to room temperature to obtain the beta-BBO crystal.
Further, a reaction product of barium carbonate and boric acid (BaB) 2 O 4 ) The molar ratio of the fluxing agent to the dosage of the fluxing agent is 0.5-2: 1.
furthermore, the first temperature is 800-900 ℃, and the material melting time is 12-24 h.
Further, the second temperature is the melt saturation point temperature +5 ℃.
Furthermore, the position of the seed crystal which is put in is 3mm below the liquid level of the melt.
Further, the crystal growth cooling rate is 0.5-3 ℃//.
Further, the crystal is rotated and pulled in the growth process, the rotation direction is bidirectional rotation, the rotation speed is 15-30 r/min, and the pulling speed is 0.4mm//. The method of rotary pulling in the upper part can increase the fluidity of high-temperature melt, reduce the inclusion of grown crystal, improve the quality of the crystal and shorten the growth period of the crystal.
Furthermore, the cooling rate is 10 ℃/h after the crystal is lifted from the liquid level.
Further, the method for growing the beta-BBO crystal by using cesium fluoride as a fluxing agent specifically comprises the following steps:
(1) Barium carbonate and boric acid are used as raw materials, cesium fluoride is used as a fluxing agent, the raw materials with the molar ratio of 0.5-2 and the fluxing agent are put into a platinum crucible and placed in a crystal growth furnace, the temperature is raised to 800-900 ℃ for melting, and the melting time is 12-24 hours, so that a melt is obtained;
(2) Cooling the melt to the temperature of the saturation point plus 5 ℃, putting seed crystals, wherein the putting position is 3mm below the melt liquid level, the crystal starts to grow, the temperature is continuously reduced at the speed of 0.5-3℃// until the crystal growth is finished, and the crystal is rotationally pulled in the growth process, wherein the rotational direction is bidirectional rotation, the rotational speed is 15-30 r/min, and the pulling speed is 0.4mm//;
(3) And (4) lifting the crystal away from the liquid level of the melt, and cooling to room temperature at the speed of 10 ℃/h to obtain the beta-BBO crystal.
The invention has the beneficial effects that:
(1) According to the method for growing the beta-BBO crystal by taking cesium fluoride as the fluxing agent, the cesium fluoride is taken as the fluxing agent, so that the viscosity of a melt can be reduced, the saturation point of the beta-BBO crystal can be reduced, and the high-quality beta-BBO crystal can be obtained;
(2) The method for growing the beta-BBO crystal by using the cesium fluoride as the fluxing agent can prepare the single crystal with the size of 80mm multiplied by 30mm, and the crystal size is large.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Will analyze the pure grade of BaCO 3 、H 3 BO 3 2364g, 1483g and 1823g of CsF are respectively weighed, uniformly mixed, put into a platinum crucible and placed in the platinum crucibleSetting a temperature rise program in a crystal growth furnace, heating to 850 ℃, and burning the material at constant temperature for 18 hours to completely melt the material to form a melt;
(2) Cooling the melt to a temperature of between the saturation point temperature and 5 ℃, then putting seed crystals, trying to find the accurate saturation point temperature of 665 ℃, putting the seed crystals to a position 3mm below the liquid level of the melt, starting crystal growth, continuously cooling at a speed of 0.5 ℃ per square inch until the crystal growth is finished, wherein the crystal growth period is 120 days, the crystal is rotationally lifted in the growth process, the rotation direction is bidirectional rotation, the rotational speed is 20r/min, and the lifting speed is 0.4mm per square inch;
(3) And (4) lifting the crystal away from the liquid level of the melt, and cooling to room temperature at the speed of 10 ℃/h to obtain the beta-BBO crystal single crystal.
The single crystal of β -BBO crystal obtained in example 1 was measured to have a size of 80mm × 30mm, a weight of 560g, and good quality.
Example 2
(1) Will analyze the pure grade of BaCO 3 、H 3 BO 3 2364g, 1483g and 3684g are respectively weighed by the CsF, evenly mixed, put into a platinum crucible, put into a crystal growth furnace, set up a temperature rise program, heated to 800 ℃, and sintered for 12 hours at constant temperature, so that the materials are completely melted to form a melt;
(2) Cooling the melt to a temperature of between the saturation point temperature and 5 ℃, then putting seed crystals, trying to find the accurate saturation point temperature of 685 ℃, putting the seed crystals to a position 3mm below the liquid level of the melt, starting crystal growth, continuously cooling at a speed of 3 ℃// (m) until the crystal growth is finished, wherein the crystal growth period is 120 days, the crystal growth process is carried out by rotary pulling, the rotation direction is bidirectional rotation, the rotary rotation speed is 15r/min, and the pulling speed is 0.4 mm/;
(3) And (4) lifting the crystal away from the liquid level of the melt, and cooling to room temperature at the speed of 10 ℃/h to obtain the beta-BBO crystal single crystal.
Example 3
(1) Will analyze the pure grade of BaCO 3 、H 3 BO 3 2364g, 1483g and 912g of CsF are respectively weighed, evenly mixed, put into a platinum crucible, put into a crystal growth furnace, set up a temperature rise program, heated to 900 ℃ and kept constantThe materials are heated for 24 hours to be completely melted to form a melt;
(2) Cooling the melt to a temperature of a saturation point plus 5 ℃, then putting seed crystals, trying to find an accurate saturation point temperature of 650 ℃, putting the seed crystals to a position 3mm below the liquid level of the melt, starting crystal growth, continuously cooling at a speed of 2 ℃///until the crystal growth is finished, wherein the crystal growth period is 120 days, the crystal is rotationally pulled in the process of growing, the rotational direction is bidirectional rotation, the rotational speed is 30r/min, and the pulling speed is 0.4 mm/;
(3) And (4) lifting the crystal away from the liquid level of the melt, and cooling to room temperature at the speed of 10 ℃/h to obtain the beta-BBO crystal single crystal.
Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention.
Claims (9)
1. A method for growing beta-BBO crystals by taking cesium fluoride as a fluxing agent is characterized by comprising the steps of taking barium carbonate and boric acid as raw materials and cesium fluoride as the fluxing agent, putting the raw materials and the fluxing agent into a platinum crucible, putting the platinum crucible into a crystal growth furnace, heating to a first temperature to melt the materials, cooling to a second temperature, then putting seed crystals into a melt, starting crystal growth, continuously cooling until the crystal growth is finished, and lifting the crystals away from a liquid level to cool to room temperature to obtain the beta-BBO crystals.
2. The method for growing a β -BBO crystal using cesium fluoride as a flux according to claim 1, wherein the molar ratio of the reaction product of barium carbonate and boric acid to the amount of flux is 0.5 to 2:1.
3. the method for growing a β -BBO crystal using cesium fluoride as a flux according to claim 1, wherein the first temperature is 800 to 900 ℃, and the melting time is 12 to 24 hours.
4. The method for growing a β -BBO crystal using cesium fluoride as a flux according to claim 1, wherein said second temperature is a melt saturation point temperature +5 ℃.
5. The method for growing a β -BBO crystal using cesium fluoride as a flux according to claim 1, wherein the seed crystal is lowered at a position 3mm below the melt level.
6. The method for growing a β -BBO crystal using cesium fluoride as a flux according to claim 1, wherein the crystal growth cooling rate is 0.5 to 3 ℃//.
7. The method for growing a β -BBO crystal using cesium fluoride as a flux according to claim 1, wherein a spin-pulling is performed during the crystal growth, the rotation direction is bidirectional rotation, the rotation speed is 15 to 30r/min, and the pulling speed is 0.4mm//.
8. The method for growing a β -BBO crystal using cesium fluoride as a flux according to claim 1, wherein the cooling rate after the crystal is lifted off the liquid surface is 10 ℃/h.
9. The method for growing a beta-BBO crystal by using cesium fluoride as a flux according to claim 1, comprising the following steps:
(1) Barium carbonate and boric acid are used as raw materials, cesium fluoride is used as a fluxing agent, the raw materials with the molar ratio of 0.5-2 and the fluxing agent are put into a platinum crucible and placed in a crystal growth furnace, the temperature is raised to 800-900 ℃ for melting, and the melting time is 12-24 hours, so that a melt is obtained;
(2) Cooling the melt to the temperature of the saturation point plus 5 ℃, putting seed crystals, wherein the putting position is 3mm below the melt liquid level, the crystal starts to grow, the temperature is continuously reduced at the speed of 0.5-3℃// until the crystal growth is finished, and the crystal is rotationally pulled in the growth process, wherein the rotational direction is bidirectional rotation, the rotational speed is 15-30 r/min, and the pulling speed is 0.4mm//;
(3) And (4) lifting the crystal away from the liquid level of the melt, and cooling to room temperature at the speed of 10 ℃/h to obtain the beta-BBO crystal.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210959833.5A CN115233287A (en) | 2022-08-11 | 2022-08-11 | beta-BBO crystal growth method using cesium fluoride as fluxing agent |
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| CN202210959833.5A CN115233287A (en) | 2022-08-11 | 2022-08-11 | beta-BBO crystal growth method using cesium fluoride as fluxing agent |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4793894A (en) * | 1987-03-10 | 1988-12-27 | North American Philips Corporation | Process for crystal growth from solution |
| 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 |
| CN110886013A (en) * | 2019-11-27 | 2020-03-17 | 福建福晶科技股份有限公司 | High-quality BBO crystal growth method |
-
2022
- 2022-08-11 CN CN202210959833.5A patent/CN115233287A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4793894A (en) * | 1987-03-10 | 1988-12-27 | North American Philips Corporation | Process for crystal growth from solution |
| 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 |
| CN110886013A (en) * | 2019-11-27 | 2020-03-17 | 福建福晶科技股份有限公司 | High-quality BBO crystal growth method |
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