CN113818079A - A method for manufacturing a Ho: atmosphere system for BYF single crystal growth - Google Patents
A method for manufacturing a Ho: atmosphere system for BYF single crystal growth Download PDFInfo
- Publication number
- CN113818079A CN113818079A CN202110901333.1A CN202110901333A CN113818079A CN 113818079 A CN113818079 A CN 113818079A CN 202110901333 A CN202110901333 A CN 202110901333A CN 113818079 A CN113818079 A CN 113818079A
- Authority
- CN
- China
- Prior art keywords
- single crystal
- growth
- furnace
- gas
- liquid nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 192
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 96
- 239000007789 gas Substances 0.000 claims abstract description 95
- 239000007788 liquid Substances 0.000 claims abstract description 82
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000001301 oxygen Substances 0.000 claims abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 238000002309 gasification Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 13
- 238000010899 nucleation Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910001369 Brass Inorganic materials 0.000 claims description 6
- 239000010951 brass Substances 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000002109 crystal growth method Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000010583 slow cooling Methods 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
Images
Classifications
-
- 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
- C30B29/12—Halides
-
- 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
- C30B27/00—Single-crystal growth under a protective fluid
- C30B27/02—Single-crystal growth under a protective fluid by pulling from a melt
Abstract
The invention belongs to the field of single crystal growth, and discloses a method for preparing a single crystal of Ho: the atmosphere system for BYF single crystal growth has the structure that: the liquid nitrogen source is connected with the liquid nitrogen gasification device, and the high-purity oxygen source and the liquid nitrogen gasification device are connected with the gas inlet of the gas mixing device; liquid nitrogen in the liquid nitrogen source is gasified by a liquid nitrogen gasification device and then is introduced into a gas mixing device, high-purity oxygen in a high-purity oxygen source is introduced into the gas mixing device, gas in the gas mixing device is introduced into a single crystal furnace to form flowing atmosphere, and oxide gas of nitrogen element generated in the single crystal furnace is introduced into a tail gas treatment device to be treated and then is discharged into the atmosphere. The invention adopts a flowing atmosphere growth system, can utilize the flowing of gas in the furnace to adjust the heat transmission near the growth interface, optimize the temperature field, take away volatile impurities, and further improve the growth quality of the crystal; the system does not need very high vacuum degree, can utilize flowing gas to discharge air out of the system, forms atmosphere protection, and can solve the defects of slow cooling of crystals at medium and low temperature sections and the like.
Description
Technical Field
The invention belongs to Ho: BYF single crystal growth technology field, especially relates to Ho: BYF single crystal material growth technology, in particular to a flowing atmosphere system in a high-temperature environment.
Background
The traditional crystal growth process of the Czochralski method adopts resistance/induction heating, and the heat distribution in a temperature field can not be finely adjusted in the crystal growth process. The crystal growth furnace adopts a high vacuum system before the growth begins, so that the high vacuum degree (10) is kept in the crystal growth furnace-4Pa level) and becomes a closed system after aeration, which is not beneficial to the discharge of volatile matters from the system. In addition, high vacuum degree requires high-demand parts such as vacuum pumps and the like, and has very high requirements on hearth tightness, so that equipment and maintenance cost are increased. Therefore, Ho: the flowing atmosphere control system and the process which require atmosphere and temperature field required by BYF single crystal material Czochralski method growth have important significance for realizing safe and convenient flowing atmosphere operation, high control precision and the like.
Disclosure of Invention
Objects of the invention
The purpose of the invention is: the method has the advantages of safe and convenient operation, high control precision and satisfaction of Ho: a flowing atmosphere control system and a flowing atmosphere control process required by atmosphere and temperature field required by BYF single crystal material Czochralski method growth. Such a Ho: the flowing atmosphere process for BYF single crystal pulling growth aims to solve the technical problems that impurities such as volatile matters and the like cannot be discharged and the temperature distribution cannot be adjusted in the prior growth technology.
(II) technical scheme
In order to solve the above technical problem, the present invention provides a Ho: the atmosphere system for BYF single crystal growth comprises a liquid nitrogen source, a high-purity oxygen source, a liquid nitrogen gasification device, a gas mixing device, a single crystal furnace and a tail gas treatment device; the liquid nitrogen source is connected with the liquid nitrogen gasification device, the high-purity oxygen source and the liquid nitrogen gasification device are connected with the air inlet of the gas mixing device, and the air outlet of the gas mixing device is connected with the single crystal furnace; liquid nitrogen in the liquid nitrogen source is gasified by a liquid nitrogen gasification device and then is introduced into a gas mixing device, high-purity oxygen in a high-purity oxygen source is introduced into the gas mixing device, gas in the gas mixing device is introduced into a single crystal furnace to form flowing atmosphere, and oxide gas of nitrogen element generated in the single crystal furnace is introduced into a tail gas treatment device to be treated and then is discharged into the atmosphere.
The atmosphere system of the present embodiment further includes: two high-precision electronic digital display flow meters, one is arranged on a connecting pipeline of the liquid nitrogen gasification device and the gas mixing device, and the other is arranged on a connecting pipeline of the high-purity oxygen source and the gas mixing device, and is used for accurately measuring and controlling the flow velocity and the flow of gas; the mechanical pump is a high-speed rotary-vane vacuum pump and is connected with the single crystal furnace, a ball valve is arranged on a connecting pipeline between the mechanical pump and the single crystal furnace, the function of exhausting initial air in the single crystal furnace is realized in the process of single crystal growth in an atmosphere system, air is pumped out before nitrogen is introduced, and the vacuum degree in the furnace reaches 10-1Pa。
The gas mixing device is connected with the high-purity oxygen source, the liquid nitrogen gasification device and the single crystal furnace respectively by using a copper tee joint with a ball valve, gas is mixed and then introduced into the furnace body, the switching action on nitrogen, oxygen and mixed gas can be realized respectively, when an atmosphere system carries out single crystal growth, the single crystal furnace is firstly vacuumized, then nitrogen is introduced, finally the mixed gas of nitrogen and oxygen is introduced into the single crystal furnace according to a set proportion, flows out of the single crystal furnace after flowing through a high-temperature heating area, and is discharged into the atmosphere after passing through a tail gas treatment device. The tail gas treatment device is used for treating the oxide gas of nitrogen element, then discharging the tail gas into the atmosphere, and simultaneously playing a role in sealing liquid state and preventing air from flowing back into the furnace body.
Wherein, the liquid nitrogen source is a liquid nitrogen tank storing liquid nitrogen, and the high-purity oxygen source is an oxygen cylinder storing high-purity oxygen.
In the liquid nitrogen gasification device, spiral brass pipelines wound into circles with a set number are arranged, and liquid nitrogen absorbs air heat through the spiral brass pipelines so as to gasify the liquid nitrogen in the pipelines. After the liquid nitrogen is gasified, the liquid nitrogen is filled into the evacuated single crystal furnace in a nitrogen form, so that the air pressure in the furnace reaches a certain positive pressure, and the furnace is kept for a period of time to ensure that the furnace body is sealed completely and does not leak air.
Wherein the purity of the high-purity oxygen is 5N; the display and control precision of the two high-precision electronic digital display flowmeters is +/-0.1L/h.
The tail gas treatment device connects the container filled with NaOH solution and the container filled with purified water through the air pipe, the tail gas passes through the two containers in sequence, and the tail gas isNO and NO of2Absorbed through chemical reaction; the connection mode of the two containers plays a role in sealing liquid state and preventing air and liquid from flowing back into the furnace body.
The atmosphere system adopts a mechanical pump to pump the furnace body of the single crystal furnace to a certain vacuum degree, such as 10-1Pa is horizontal, the furnace body is filled with nitrogen and then discharged, the nitrogen is sealed at an atmosphere outlet of the single crystal furnace connected with a mechanical pump to prevent air from flowing backwards, and mixed gas of nitrogen and oxygen is introduced all the time in the crystal growth process to form flowing atmosphere; in consideration of large nitrogen usage amount and uninterruptible technical process, a method for generating high-purity nitrogen by adopting a liquid nitrogen tank gasification device is adopted; the gas flow is monitored and adjusted in real time by high-precision equipment such as an electronic digital display flowmeter to meet the process requirements of flowing atmosphere, and the technical indexes are as follows: the flow rate of the flowing gas is 3L-8L/Min, and the control precision is as follows: 0.1L.
Based on the atmosphere system for single crystal growth, the invention also provides a single crystal growth method, which comprises the following steps: the pre-crystallized high-purity blocky Yb: YAG powder is filled into a clean iridium crucible and then is filled into a single crystal furnace, a furnace door and a gas pipe valve are closed, a cooling circulation system is started, and a mechanical pump and a ball valve are started for vacuumizing. When the vacuum degree reaches the preset requirement, closing the ball valve and the mechanical pump, opening the air inlet valve to slowly fill nitrogen, stopping filling air when the air pressure in the furnace reaches the set requirement, and closing the air inlet valve. And keeping the air pressure not reduced after the set time, opening a nitrogen inlet valve, opening a furnace body exhaust valve to form a nitrogen flowing atmosphere, further exhausting air in the furnace, starting heating after half an hour, and starting an intermediate frequency power supply for induction heating. And opening a high-purity oxygen inlet valve, and controlling the flow according to the proportion of the oxygen in the total flow to form a mixed flowing atmosphere. When the temperature is raised to observe a melt flow line, the melt flow is observed, the power change is properly finely adjusted, so that the solid-liquid conversion phenomenon of ordered convection just appears on the liquid level, and the time is stably set under the condition to fully dissolve the materials. After the raw materials are melted, the flow of the mixed gas is finely adjusted by matching with the fine adjustment of the power, so that the temperature gradient suitable for the crystal pulling method is formed near the liquid level. Controlling seeding rate, rotating speed and adjusting power reduction rate, entering a shouldering growth process after seeding for hours, adjusting the power reduction rate, entering an equal-diameter growth stage when shouldering till the diameter of the crystal reaches a set value, adjusting the pulling rate and the power reduction rate, adjusting the pulling rate after the equal-diameter growth is set for time, properly increasing the heating power, finishing crystal ending and finishing crystal growth. And in the stage of temperature reduction and cooling, after the temperature is cooled to room temperature, the power supply is turned off, and the circulating cooling system and the flowing atmosphere system are kept for a set time. And finally, opening the furnace, taking out the crystal, and detecting that the Yb/YAG crystal grown by the flowing atmosphere process has no bubbles or cracks visible to naked eyes and has good quality. In the whole crystal growth process, the nitrogen-oxygen mixed flowing atmosphere plays a good role in optimizing the liquid level temperature gradient, reducing oxygen vacancy defects in the crystal and the like.
(III) advantageous effects
Ho provided by the technical scheme: the atmosphere system for BYF single crystal growth adopts a flowing atmosphere growth system, can adjust heat transmission near a growth interface by utilizing the flowing of gas in a furnace, optimizes a temperature field, takes away volatile impurities, and further improves the growth quality of crystals; the system does not require very high vacuum levels (10)-1Pa level), air can be discharged out of the system by utilizing flowing gas to form atmosphere protection, and the defects of slow cooling of the crystal in a medium-low temperature section and the like can be overcome.
Drawings
FIG. 1 is a Ho: the system structure schematic diagram of the flowing atmosphere system and the process for BYF single crystal pulling method growth.
FIG. 2 is a Ho: the flowing atmosphere system for BYF single crystal pulling method growth and the process flow schematic diagram of the process.
Detailed Description
In order to make the objects, contents and advantages of the present invention clearer, the following detailed description of the embodiments of the present invention will be made in conjunction with the accompanying drawings and examples.
Example 1
The invention provides a method for realizing Ho: the atmosphere system for BYF single crystal growth comprises a liquid nitrogen source, a high-purity oxygen source, a liquid nitrogen gasification device, a gas mixing device, a single crystal furnace and a tail gas treatment device; the liquid nitrogen source is connected with the liquid nitrogen gasification device, the high-purity oxygen source and the liquid nitrogen gasification device are connected with the air inlet of the gas mixing device, and the air outlet of the gas mixing device is connected with the single crystal furnace; liquid nitrogen in the liquid nitrogen source is gasified by a liquid nitrogen gasification device and then is introduced into a gas mixing device, high-purity oxygen in a high-purity oxygen source is introduced into the gas mixing device, gas in the gas mixing device is introduced into a single crystal furnace to form flowing atmosphere, and oxide gas of nitrogen element generated in the single crystal furnace is introduced into a tail gas treatment device to be treated and then is discharged into the atmosphere.
The atmosphere system of the present embodiment further includes: two high-precision electronic digital display flow meters, one is arranged on a connecting pipeline of the liquid nitrogen gasification device and the gas mixing device, and the other is arranged on a connecting pipeline of the high-purity oxygen source and the gas mixing device, and is used for accurately measuring and controlling the flow velocity and the flow of gas; the mechanical pump is a high-speed rotary-vane vacuum pump and is connected with the single crystal furnace, a ball valve is arranged on a connecting pipeline between the mechanical pump and the single crystal furnace, the function of exhausting initial air in the single crystal furnace is realized in the process of single crystal growth in an atmosphere system, air is pumped out before nitrogen is introduced, and the vacuum degree in the furnace reaches 10-1Pa。
The gas mixing device is connected with the high-purity oxygen source, the liquid nitrogen gasification device and the single crystal furnace respectively by using a copper tee joint with a ball valve, gas is mixed and then introduced into the furnace body, the switching action on nitrogen, oxygen and mixed gas can be realized respectively, when an atmosphere system carries out single crystal growth, the single crystal furnace is firstly vacuumized, then nitrogen is introduced, finally the mixed gas of nitrogen and oxygen is introduced into the single crystal furnace according to a set proportion, flows out of the single crystal furnace after flowing through a high-temperature heating area, and is discharged into the atmosphere after passing through a tail gas treatment device. The tail gas treatment device is used for treating the oxide gas of nitrogen element, then discharging the tail gas into the atmosphere, and simultaneously playing a role in sealing liquid state and preventing air from flowing back into the furnace body.
Wherein, the liquid nitrogen source is a liquid nitrogen tank storing liquid nitrogen, and the high-purity oxygen source is an oxygen cylinder storing high-purity oxygen.
In the liquid nitrogen gasification device, spiral brass pipelines wound into circles with a set number are arranged, and liquid nitrogen absorbs air heat through the spiral brass pipelines so as to gasify the liquid nitrogen in the pipelines. After the liquid nitrogen is gasified, the liquid nitrogen is filled into the evacuated single crystal furnace in a nitrogen form, so that the air pressure in the furnace reaches a certain positive pressure, and the furnace is kept for a period of time to ensure that the furnace body is sealed completely and does not leak air.
Wherein the purity of the high-purity oxygen is 5N; the display and control precision of the two high-precision electronic digital display flowmeters is +/-0.1L/h.
The tail gas treatment device connects the container filled with NaOH solution and the container filled with purified water through the air pipe, the tail gas passes through the two containers in sequence, and NO in the tail gas2Absorbed through chemical reaction; the connection mode of the two containers plays a role in sealing liquid state and preventing air and liquid from flowing back into the furnace body.
The atmosphere system adopts a mechanical pump to pump the furnace body of the single crystal furnace to a certain vacuum degree, such as 10-1Pa is horizontal, the furnace body is filled with nitrogen and then discharged, the nitrogen is sealed at an atmosphere outlet of the single crystal furnace connected with a mechanical pump to prevent air from flowing backwards, and mixed gas of nitrogen and oxygen is introduced all the time in the crystal growth process to form flowing atmosphere; in consideration of large nitrogen usage amount and uninterruptible technical process, a method for generating high-purity nitrogen by adopting a liquid nitrogen tank gasification device is adopted; the gas flow is monitored and adjusted in real time by high-precision equipment such as an electronic digital display flowmeter to meet the process requirements of flowing atmosphere, and the technical indexes are as follows: the flow rate of the flowing gas is 3L-8L/Min, and the control precision is as follows: 0.1L.
The following examples 2 and 3 are specific embodiments of the present invention, and in the actual growth process, process parameters and the like are formulated according to specific requirements of specific crystals.
Example 2
Loading 4.5Kg of pre-crystallized high-purity blocky Yb/YAG powder into a clean iraurite crucible, loading, closing a furnace door and a gas pipe valve, starting a cooling circulation system, and opening a mechanical pump and a ball valve for vacuumizing. When the vacuum degree reaches 1.0 multiplied by 10-1And closing the ball valve and the mechanical pump when the pressure is Pa. The air inlet and the air outlet of the flowing atmosphere system are respectively positioned at the upper part and the bottom of the furnace body. And opening the air inlet valve to slowly fill nitrogen, controlling the flow rate at 5L/Min, stopping filling air when the air pressure in the furnace reaches 0.11MPa, and closing the air inlet valve. After half an hour, the pressure is not reduced and nitrogen is turned onAnd (3) opening a furnace body exhaust valve by using an air inlet valve to form a nitrogen flowing atmosphere, further exhausting air in the furnace, starting heating after half an hour, and starting an intermediate frequency power supply for induction heating. And opening a high-purity oxygen inlet valve, and controlling the flow according to the proportion of 3 percent of the oxygen in the total flow to form mixed flowing atmosphere. And (3) when the temperature is raised to the state that a melt liquid flow line is observed, observing the melt liquid flow, properly finely adjusting the power change, just leading the solid-liquid conversion phenomenon of ordered convection to appear on the liquid level, stabilizing for 4 hours under the condition, and fully melting the materials. After the raw materials are melted, the flow of the mixed gas is finely adjusted by matching with the fine adjustment of the power, so that the temperature gradient suitable for the crystal pulling method is formed near the liquid level. The seeding rate is controlled to be 1mm/h, the rotating speed is 5r/min, the power is adjusted to be reduced at the speed of 10W/h, the shouldering growth process is carried out after seeding is carried out for 10 hours, and the power reduction rate is adjusted to be 20W/h. When the diameter of the crystal reaches 60mm, the crystal enters an equal-diameter growth stage, the pulling speed is adjusted to be 2mm/h, and the power reduction rate is adjusted to be 15W/h. After the isometric growth is carried out for 50 hours, the pulling speed is adjusted to be 5mm/h, the heating power is properly increased, the crystal ending is finished, and the crystal growth is finished. In the stage of cooling, the temperature is reduced to 1750 ℃ at the speed of 10 ℃/h, annealing is carried out for 15h, then the temperature is reduced to 1250 ℃ at the speed of 20 ℃/h, the temperature is reduced to 600 ℃ again at the speed of 30 ℃/h, and then the temperature is reduced to room temperature at the speed of 40 ℃/h. After cooling to room temperature, the power supply is turned off, and the circulating cooling system and the flowing atmosphere system are kept for 24 h. And finally, opening the furnace, taking out the crystal, and detecting that the Yb/YAG crystal grown by the flowing atmosphere process has no bubbles or cracks visible to naked eyes, and has good quality and the size of phi 60mm multiplied by 100 mm. In the whole crystal growth process, the nitrogen-oxygen mixed flowing atmosphere plays a good role in optimizing the liquid level temperature gradient, reducing oxygen vacancy defects in the crystal and the like.
Example 3
Loading 5.0Kg of pre-crystallized high-purity blocky Yb: YAG powder into a clean iraurite crucible, loading, closing a furnace door and a gas pipe valve, starting a cooling circulation system, and opening a mechanical pump and a ball valve for vacuumizing. When the vacuum degree reaches 1.0 multiplied by 10-1And closing the ball valve and the mechanical pump when the pressure is Pa. The air inlet and the air outlet of the flowing atmosphere system are both positioned in the middle of the furnace body. The air inlet valve is opened to slowly fill nitrogenAnd controlling the flow rate at 4L/Min, stopping inflating when the air pressure in the furnace reaches 0.11MPa, and closing the air inlet valve. And opening a nitrogen inlet valve and a furnace body exhaust valve after half an hour to form a nitrogen flowing atmosphere, further discharging the air in the furnace, starting heating after half an hour, and starting an intermediate frequency power supply for induction heating. And opening a high-purity oxygen inlet valve, and controlling the flow according to the proportion of 3 percent of the oxygen in the total flow to form mixed flowing atmosphere. And (3) when the temperature is raised to the state that a melt liquid flow line is observed, observing the melt liquid flow, properly finely adjusting the power change, just leading the solid-liquid conversion phenomenon of ordered convection to appear on the liquid level, stabilizing for 4 hours under the condition, and fully melting the materials. After the raw materials are melted, the flow of the mixed gas is finely adjusted by matching with the fine adjustment of the power, so that the temperature gradient suitable for the crystal pulling method is formed near the liquid level. The seeding rate is controlled to be 1mm/h, the rotating speed is 5r/min, and the power reduction is adjusted at the speed of 10W/h. And starting an automatic growth control program after seeding for 10 hours, setting the shouldering angle to be 90 degrees and the shouldering height to be 50mm, and starting the shouldering growth process. According to the program setting, when the diameter of the crystal reaches 60mm, the equal diameter growth stage is started. After the isometric growth is carried out for 50h, the heating power is automatically increased by the program, the crystal ending is finished, and the crystal growth is finished. In the stage of cooling, the temperature is reduced to 1750 ℃ at the speed of 10 ℃/h, annealing is carried out for 15h, then the temperature is reduced to 1250 ℃ at the speed of 20 ℃/h, the temperature is reduced to 600 ℃ again at the speed of 30 ℃/h, and then the temperature is reduced to room temperature at the speed of 40 ℃/h. After cooling to room temperature, the power supply is turned off, and the circulating cooling system and the flowing atmosphere system are kept for 24 h. And finally, opening the furnace, taking out the crystal, and detecting that the Yb: YAG crystal grown by the flowing atmosphere process has no bubbles or cracks visible to naked eyes, and has good quality and the size of phi 60mm multiplied by 110 mm. In the whole crystal growth process, the nitrogen-oxygen mixed flowing atmosphere plays a good role in optimizing the liquid level temperature gradient, reducing oxygen vacancy defects in the crystal and the like.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for manufacturing a Ho: an atmosphere system for BYF single crystal growth, comprising: a liquid nitrogen source, a high-purity oxygen source, a liquid nitrogen gasification device, a gas mixing device, a single crystal furnace and a tail gas treatment device; the liquid nitrogen source is connected with the liquid nitrogen gasification device, the high-purity oxygen source and the liquid nitrogen gasification device are connected with the air inlet of the gas mixing device, and the air outlet of the gas mixing device is connected with the single crystal furnace; liquid nitrogen in the liquid nitrogen source is gasified by a liquid nitrogen gasification device and then is introduced into a gas mixing device, high-purity oxygen in a high-purity oxygen source is introduced into the gas mixing device, gas in the gas mixing device is introduced into a single crystal furnace to form flowing atmosphere, and oxide gas of nitrogen element generated in the single crystal furnace is introduced into a tail gas treatment device to be treated and then is discharged into the atmosphere.
2. The Ho: the atmosphere system for BYF single crystal growth is characterized by further comprising: and one of the two high-precision electronic digital display flow meters is arranged on a connecting pipeline of the liquid nitrogen gasification device and the gas mixing device, and the other one is arranged on a connecting pipeline of the high-purity oxygen source and the gas mixing device and is used for accurately measuring and controlling the flow velocity and the flow of the gas.
3. The Ho: the atmosphere system for BYF single crystal growth is characterized by further comprising: the mechanical pump is a high-speed rotary-vane vacuum pump and is connected with the single crystal furnace, a ball valve is arranged on a connecting pipeline between the mechanical pump and the single crystal furnace, the function of exhausting initial air in the single crystal furnace is achieved in the process of single crystal growth in an atmosphere system, air is pumped out before nitrogen is introduced, and the vacuum degree in the furnace reaches the preset requirement.
4. The Ho of claim 3: the atmosphere system for BYF single crystal growth is characterized in that a copper tee joint with a ball valve is used by the gas mixing device to be respectively connected with a high-purity oxygen source, a liquid nitrogen gasification device and a single crystal furnace, the gas is mixed and then introduced into the furnace body, the switching action on nitrogen, oxygen and mixed gas can be respectively realized, when the atmosphere system carries out single crystal growth, the single crystal furnace is firstly vacuumized, then nitrogen is introduced, and finally the mixed gas of nitrogen and oxygen is introduced into the single crystal furnace according to a set proportion.
5. The Ho: the atmosphere system for BYF single crystal growth is characterized in that spiral brass pipelines wound into circles with a set number are arranged in the liquid nitrogen gasification device, and liquid nitrogen absorbs air heat through the spiral brass pipelines so that the liquid nitrogen in the pipelines is gasified.
6. The Ho: the atmosphere system for BYF single crystal growth is characterized in that the purity of the high purity oxygen is 5N; the display and control precision of the two high-precision electronic digital display flowmeters is +/-0.1L/h.
7. The Ho: the atmosphere system for BYF single crystal growth is characterized in that the tail gas treatment device comprises a container filled with NaOH solution and a container filled with purified water which are connected through a gas pipe, tail gas sequentially passes through the two containers, and NO in the tail gas2Absorbed through chemical reaction.
8. A method based on the Ho of claim 7: the single crystal growth method of the atmosphere system for BYF single crystal growth is characterized by comprising the following steps: YAG powder as a pre-crystallization material is filled into a clean iraurita crucible and is filled into a single crystal furnace, a furnace door and a gas pipe valve are closed, a cooling circulation system is started, and a mechanical pump and a ball valve are started for vacuumizing; when the vacuum degree meets the preset requirement, closing the ball valve and the mechanical pump, opening the air inlet valve to fill nitrogen, stopping filling air when the air pressure in the furnace meets the set requirement, and closing the air inlet valve; keeping the air pressure not reduced after the set time, opening a nitrogen inlet valve, opening a furnace body exhaust valve to form a nitrogen flowing atmosphere, further discharging the air in the furnace, then starting heating, starting an intermediate frequency power supply for induction heating, opening a high-purity oxygen inlet valve, and controlling the flow according to the proportion of oxygen in the total flow to form a mixed flowing atmosphere; when the temperature is raised until a melt flow line is observed, observing the melt flow, adjusting the power change to ensure that the solid-liquid conversion phenomenon of ordered convection just appears on the liquid level, and stabilizing the set time under the condition to fully dissolve the materials; after the raw materials are melted, the flow of the mixed gas is finely adjusted by matching with the fine adjustment of the power, so that the temperature gradient suitable for the crystal pulling method is formed near the liquid level; controlling seeding rate, rotating speed and adjusting power reduction rate, entering a shouldering growth process after seeding for hours, adjusting the power reduction rate, entering an equal-diameter growth stage when shouldering till the diameter of the crystal reaches a set value, adjusting the pulling rate and the power reduction rate, adjusting the pulling rate after the equal-diameter growth is set for time, increasing the heating power, finishing crystal ending and finishing crystal growth; in the cooling stage, after cooling to room temperature, the power supply is turned off, and the circulating cooling system and the flowing atmosphere system are kept for a set time; finally, opening the furnace and taking out the crystal.
9. The single crystal growth method according to claim 8, wherein the seeding rate is controlled to 1mm/h, the rotation speed is 5r/min, the power reduction is adjusted at a speed of 10W/h, the shouldering growth process is carried out after 10 hours of seeding, and the power reduction rate is adjusted to 20W/h; shouldering until the diameter of the crystal reaches 60mm, entering an equal-diameter growth stage, adjusting the pulling speed to be 2mm/h, and adjusting the power reduction rate to be 15W/h; after the isometric growth is carried out for 50 hours, the pulling speed is adjusted to be 5mm/h, the heating power is increased, the crystal ending is completed, and the crystal growth is finished; in the stage of cooling, the temperature is reduced to 1750 ℃ at the speed of 10 ℃/h, annealing is carried out for 15h, then the temperature is reduced to 1250 ℃ at the speed of 20 ℃/h, the temperature is reduced to 600 ℃ again at the speed of 30 ℃/h, and then the temperature is reduced to room temperature at the speed of 40 ℃/h.
10. The single crystal growth method according to claim 8, wherein the seeding rate is controlled to 1mm/h, the rotation speed is 5r/min, and the power down is adjusted at a speed of 10W/h; starting an automatic growth control program after seeding for 10 hours, setting a shouldering angle to be 90 degrees and a shouldering height to be 50mm, starting a shouldering growth process, entering an equal-diameter growth stage when the shouldering reaches 60mm in crystal diameter, automatically increasing the heating power by the program after the equal-diameter growth is carried out for 50 hours, finishing the ending of the crystal, and finishing the growth of the crystal; in the stage of cooling, the temperature is reduced to 1750 ℃ at the speed of 10 ℃/h, annealing is carried out for 15h, then the temperature is reduced to 1250 ℃ at the speed of 20 ℃/h, the temperature is reduced to 600 ℃ again at the speed of 30 ℃/h, and then the temperature is reduced to room temperature at the speed of 40 ℃/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110901333.1A CN113818079A (en) | 2021-08-06 | 2021-08-06 | A method for manufacturing a Ho: atmosphere system for BYF single crystal growth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110901333.1A CN113818079A (en) | 2021-08-06 | 2021-08-06 | A method for manufacturing a Ho: atmosphere system for BYF single crystal growth |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113818079A true CN113818079A (en) | 2021-12-21 |
Family
ID=78912917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110901333.1A Pending CN113818079A (en) | 2021-08-06 | 2021-08-06 | A method for manufacturing a Ho: atmosphere system for BYF single crystal growth |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113818079A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115142130A (en) * | 2022-06-30 | 2022-10-04 | 同济大学 | Method and device for growing flaky gallium oxide crystal by micro pull-down zone melting method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5135047A (en) * | 1989-10-05 | 1992-08-04 | Flavio Dobran | Furnace for high quality and superconducting bulk crystal growths |
| JP2003002789A (en) * | 2001-04-09 | 2003-01-08 | Kobe Steel Ltd | Method for manufacturing fluoride single crystal |
| JP2004217469A (en) * | 2003-01-15 | 2004-08-05 | Tokuyama Corp | Apparatus for pulling single crystal |
| CN101055847A (en) * | 2006-03-31 | 2007-10-17 | 硅绝缘体技术有限公司 | Method of revealing crystalline defects in a bulk substrate |
| CN104562183A (en) * | 2014-12-31 | 2015-04-29 | 西南技术物理研究所 | Method for growing large-sized rare-earth-doped barium yttrium fluoride single crystals |
| CN113174628A (en) * | 2021-06-02 | 2021-07-27 | 上海德硅凯氟光电科技有限公司 | Device and method for growing fluoride crystal by crucible rotation and descent method |
-
2021
- 2021-08-06 CN CN202110901333.1A patent/CN113818079A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5135047A (en) * | 1989-10-05 | 1992-08-04 | Flavio Dobran | Furnace for high quality and superconducting bulk crystal growths |
| JP2003002789A (en) * | 2001-04-09 | 2003-01-08 | Kobe Steel Ltd | Method for manufacturing fluoride single crystal |
| JP2004217469A (en) * | 2003-01-15 | 2004-08-05 | Tokuyama Corp | Apparatus for pulling single crystal |
| CN101055847A (en) * | 2006-03-31 | 2007-10-17 | 硅绝缘体技术有限公司 | Method of revealing crystalline defects in a bulk substrate |
| CN104562183A (en) * | 2014-12-31 | 2015-04-29 | 西南技术物理研究所 | Method for growing large-sized rare-earth-doped barium yttrium fluoride single crystals |
| CN113174628A (en) * | 2021-06-02 | 2021-07-27 | 上海德硅凯氟光电科技有限公司 | Device and method for growing fluoride crystal by crucible rotation and descent method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115142130A (en) * | 2022-06-30 | 2022-10-04 | 同济大学 | Method and device for growing flaky gallium oxide crystal by micro pull-down zone melting method |
| CN115142130B (en) * | 2022-06-30 | 2024-02-27 | 同济大学 | Method and device for growing flaky gallium oxide crystals by micro-pull-down zone melting method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110760931B (en) | System for preparing indium phosphide crystal by utilizing indium-phosphorus mixture | |
| WO2021098348A1 (en) | Method for preparing indium phosphide crystal using indium-phosphorus mixture | |
| CN113818079A (en) | A method for manufacturing a Ho: atmosphere system for BYF single crystal growth | |
| CN110257901B (en) | Preparation process of large-diameter efficient N-type monocrystalline silicon | |
| CN104190883B (en) | A kind of electric furnace taps a blast furnace automatic stream inoculation device and current-following inoculation method automatically | |
| CN111607823A (en) | Sapphire single crystal pulling method preparation device and method | |
| CN103103604A (en) | Manufacturing method of large-size C-oriented sapphire crystals | |
| WO2019109366A1 (en) | Method for in-situ injection and synthesis of phosphide by using bearing gas | |
| CN105032306B (en) | Solid-phase atmosphere reaction device | |
| JP4393555B2 (en) | Single crystal growth method | |
| CN113699584A (en) | Czochralski silicon microwave rapid material supplementing continuous production system and production method thereof | |
| CN101397651A (en) | Method for plating carbon film on ampoule internal wall for CdZnTe crystal growth and apparatus thereof | |
| KR100188313B1 (en) | Slush hydrogen production apparatus | |
| CN204052823U (en) | A kind of electric furnace taps a blast furnace automatic stream inoculation device | |
| CN108823357A (en) | A kind of degassing system and its degassing method based on flexible mechanical vacuum pump group | |
| CN106894082B (en) | Monocrystalline silicon growing furnace | |
| CN111442645B (en) | Heating furnace and heating system for preparing liquid chloride | |
| CN220468130U (en) | Quartz crucible film plating device for crystal growth | |
| CN214572369U (en) | Constant-pressure constant-current protective gas device for indium phosphide single crystal growth | |
| CN113201613A (en) | Maintenance method for cooling wall of blast furnace | |
| CN103781950A (en) | Vacuum storage method and device for crystalline material | |
| CN110184662B (en) | Continuous feeding device and method for ceramic precursor polymer melt for melt spinning | |
| CN203128688U (en) | Crystal synthetic furnace for producing crystals | |
| CN216107187U (en) | Gas input device and hot wire chemical vapor deposition equipment | |
| CN215877834U (en) | Preparation facilities of high-purity selenium grain |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |