CN110093660B - Growth device and process capable of growing bubble-free crystal material at high speed - Google Patents
Growth device and process capable of growing bubble-free crystal material at high speed Download PDFInfo
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- CN110093660B CN110093660B CN201910415638.4A CN201910415638A CN110093660B CN 110093660 B CN110093660 B CN 110093660B CN 201910415638 A CN201910415638 A CN 201910415638A CN 110093660 B CN110093660 B CN 110093660B
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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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/003—Heating or cooling of the melt or the crystallised material
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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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
- C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
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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
- C30B29/12—Halides
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Abstract
The invention discloses a growth device and a growth process capable of growing bubble-free crystal materials at high speed, which relate to the technical field of production processes of vacuum coating crystal materials and overcome the defects that the growth speed of crystals is low, the crystal interface is small and unstable, and a large amount of bubbles are generated once the growth speed of the crystals is too high; a through hole is formed in the center of the annular crucible, a heat exchange tube is arranged in the through hole, a temperature measuring device is arranged on the furnace body, and supporting plates which are abutted against the bottom of the annular crucible are arranged on the periphery of the heat exchange tube. The invention has the innovation that the crucible is annular, the middle part of the crucible is hollow and can accommodate the heat exchange tube, and crystal materials basically without bubbles can grow at high speed by increasing the cooling medium in the heat exchange tube to provide crystallization driving force during crystal growth.
Description
Technical Field
The invention relates to the technical field of production processes of vacuum coating crystal materials, in particular to a growth device and a growth process capable of growing bubble-free crystal materials at a high speed.
Background
The vacuum coating crystal material, especially the electronic grade vacuum coating crystal material, is required to have high purity and few internal bubbles so as to ensure stable vacuum, no air leakage and no collapse during the vacuum coating process and ensure good coating effect and coating efficiency.
At present, a vacuum coating crystal material is mainly formed by rapidly cooling after high-temperature vacuum melting, a crucible is not changed in position when a crystal grows, the growth can be controlled only by power/temperature, the temperature gradient on the distribution of a thermal field is very small, the crystal is not crystallized when the temperature is too high, the rapid crystallization cannot be controlled when the temperature is slightly low, the inside single crystal particles are small, and the crystallization direction is integrally from outside to inside, so that a large amount of bubbles, various crucible pollutants and the like are easily mixed in the material, the purity is greatly influenced, the phenomena of air release, collapse point, flash explosion and the like are easily generated in the coating process, the coating quality is greatly influenced, and particularly, the use effect on coating with high requirements such as electronic grade and the like is poor.
The large single crystal material has high purity and no bubbles due to the directional solidification and impurity removal effects, is very suitable for being used as a high-end coating material, but has long growth period, very high price, small production energy and unacceptable market.
Disclosure of Invention
Aiming at the defects that the crystal growth speed is low, the crystal interface is small and unstable, and a large amount of bubbles are generated once the crystal growth speed is too high in the prior art, the invention aims to provide the bubble-free crystal material growth device capable of growing at high speed.
In order to achieve the first purpose, the invention provides the following technical scheme:
a growth device capable of growing bubble-free crystal materials at high speed comprises a support and a furnace body positioned on the support, wherein an annular crucible used for containing raw materials is arranged in the furnace body, a cover body is arranged on the annular crucible, a heating body used for heating the crucible and a heat insulation layer playing a role in heat insulation are arranged in the furnace body; a through hole is formed in the center of the annular crucible, a heat exchange tube is arranged in the through hole, a temperature measuring device is arranged on the furnace body, and supporting plates which are abutted against the bottom of the annular crucible are arranged on the periphery of the heat exchange tube.
Through adopting above-mentioned technical scheme, locate to set up hot exchange pipe at annular crucible center, low, the high low temperature gradient down in the outer height of formation inside the fuse-element for the fuse-element can carry out controllable one-way solidification growth with great interface propulsion speed, can grow the polycrystal material of bubble-free at a high speed, inside bubble and various pollutants get rid of the crystal material outward flange through interface unidirectional movement simultaneously, crystal material purity is high, simultaneously because the growth interface is showing the increase, make the volume solidification speed of fuse-element also very big, production efficiency increases substantially. The large single crystal material produced by the device has high purity and no air bubbles due to the directional solidification and impurity removal effect, is very suitable for being used as a high-end coating material, has short period, high capacity and good market applicability, and is particularly suitable for the requirements of electronic-grade high-end markets.
More preferably, the heat exchange tube is in contact with the outer side wall of the crucible at the through hole, and the contact area can be as high as 50-500cm2。
By adopting the technical scheme, in the existing heat exchange Hem method, the top of the heat exchange tube is in contact with the bottom of the cylindrical crucible, the contact area (generally 10-15cm2) is very small, the cooling capacity is limited, and the crystal growth speed is about 1-5 mm/hr. In the invention, the contact area can be as high as 50-500cm2It can provide strong cooling capacity, form very large temperature gradient, increase the crystal growth rate to 15-30mm/hr, and grow polycrystal material without bubble.
Further preferably, the heat exchange tube comprises an inner tube and an outer tube sleeved on the periphery of the inner tube, the top end of the outer tube is closed, and the top end of the inner tube is communicated with the inside of the outer tube.
Through adopting above-mentioned technical scheme, coolant rises from the inner tube and gets into the outer tube behind the top, and liquid can rise from the outer tube and get into the inner tube behind the top, and the outer tube exchanges heat with the crucible to the heat transfer area of increase coolant and crucible, the heat transfer is even moreover, makes the crystallization interface big and stable, is favorable to improving crystal production efficiency.
The second purpose of the invention is to provide a growth process of bubble-free crystal material capable of growing at high speed, and the crystal material prepared by the process has high purity, no bubbles and high production efficiency.
In order to achieve the second purpose, the invention provides the following technical scheme, which comprises the following specific steps:
step one, loading raw materials into a cavity of a crucible, covering a cover body, starting heating by a heating body, heating the raw materials until the temperature exceeds a melting point, completely melting the raw materials, clarifying at high temperature, keeping constant power for several hours, and maintaining the flow of a cooling medium in a heat exchange tube at an initial flow, wherein the initial flow is approximately 0.2-0.5L/min;
step two, the flow rate of the cooling medium is increased gradually from the initial flow rate to the flow rate required by crystal growth within a certain time, the flow rate of the cooling medium is increased at 0.5-23(L/min)/h, the certain time depends on the size of the crucible and is generally about 10-30 hours, the flow rate required by crystal growth depends on the type and the charging amount of the crystal material and is 250L/min at 150-;
and step three, keeping the flow of the cooling medium unchanged, synchronously reducing the flow introduction speed and power of the cooling medium to 0 after the crystal growth is finished, and taking out the crystal after cooling.
By adopting the technical scheme, the cooling medium is introduced into the heat exchange tube, and meanwhile, the temperature gradient with high outside, low inside, high top and low bottom is formed inside the melt by controlling the flow of the cooling medium, so that the melt can be subjected to controllable unidirectional solidification growth at a higher interface advancing speed, the melt is gradually directionally solidified from the center and the bottom of the crucible upwards, a large-particle single crystal can be obtained, internal bubbles and various pollutants are removed to the outer edge of the material through unidirectional movement of the interface, and the material is internally bubble-free and high in purity; meanwhile, the growth interface is obviously increased, so that the volume solidification speed of the melt is high, the production efficiency is improved by more than 50 percent, and the method has good production and application effects.
More preferably, the raw material is fluoride crystal powder, and the raw material is any one of calcium fluoride, magnesium fluoride, barium fluoride, lithium fluoride, sodium fluoride, and the like.
By adopting the technical scheme, the magnesium fluoride, the barium fluoride, the lithium fluoride and the sodium fluoride belong to halide single crystals, and the fluoride single crystals have higher transmittance, low refractive index and low light reflection coefficient in ultraviolet, visible and infrared band spectral regions and have good chemical stability.
More preferably, the rate of the temperature rise of the raw materials in the first step is 50-100 ℃/h.
More preferably, the temperature of the raw materials heated to the melting point or higher in the second step is 50-200 ℃.
By adopting the technical scheme, the raw materials are ensured to be fully melted, and the formation of the single crystal with high purity at the later stage is facilitated.
Further preferably, the cooling medium is an inert gas, mainly helium, argon or nitrogen.
Through adopting above-mentioned technical scheme, adopt inert gas, when receiving high temperature heating, can not cause the erosion to the cooling rod, improve the cooling life-span of cooling tube, guarantee the cooling effect.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the heat exchange tube is arranged at the center of the crucible, so that a large temperature gradient with high outside, low inside, high outside and low inside, high top and low bottom is formed in the melt, the melt can be subjected to controllable unidirectional solidification growth at a high interface advancing speed, a bubble-free polycrystalline material can be grown at a high speed, and the production efficiency is improved;
(2) meanwhile, in the production process, bubbles and various pollutants in the annular crucible are removed to the outer edge of the material through interface one-way movement, the purity of the material is high, no bubbles exist, and the obtained crystal has high quality.
Drawings
FIG. 1 is a schematic structural view of a crystal material growing apparatus according to the present invention;
reference numerals: 1. a support; 2. a furnace body; 3. a movable hole; 4. a crucible; 5. a heating element; 6. a heat-insulating layer; 7. a cover body; 8. a heat exchange tube; 81. an air inlet inner pipe; 82. an air outlet outer pipe; 9. a support plate; 10. a heat preservation block; 11. a through hole; 12. a temperature measuring device.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Example 1: as shown in figure 1, the growth device for bubble-free crystal materials capable of growing at high speed comprises a rectangular frame-shaped support 1 and a furnace body 2 positioned on the support 1, wherein the furnace body 2 is rectangular, a rectangular movable hole 3 is formed in the bottom of the furnace body 2, a cylindrical annular crucible 4 is arranged in the furnace body 2, and a matched cover body 7 is arranged on the annular crucible 4. A heating body 5 used for heating the crucible 4 and a heat preservation layer 6 playing a role of heat preservation are arranged in the furnace body 2, the heating body 5 comprises four silicon-molybdenum rods, the four silicon-molybdenum rods penetrate through the side wall of the furnace body 2 and are respectively positioned at two sides of the annular crucible 4, and asbestos is selected as a material in the heat preservation layer 6. Meanwhile, a temperature measuring device 12 is arranged in the furnace body 2, and the temperature measuring device 12 can be a laser infrared temperature sensor.
A through hole 11 is formed at the center of the annular crucible 4,and a heat exchange tube 8 is arranged in the through hole 11, the heat exchange tube 8 comprises an inner tube 81 and an outer tube 82 sleeved on the peripheral side of the inner tube 81, the top end of the outer tube 82 is closed, and the top end of the inner tube 81 is communicated with the interior of the outer tube 82. The heat exchange tube 8 is in contact with the outer side wall of the crucible 4 at the through hole 11, and the contact area can be as high as 50-500cm according to the production scale and the equipment size2。
The supporting plate 9 abutted to the bottom of the annular crucible 4 is arranged on the periphery of the heat exchange tube 8, the heat preservation block 10 clamped with the sealing movable hole 3 is arranged on one side, away from the annular crucible 4, of the supporting plate 9, the heat preservation block 10 is fixed on the side wall of the heat exchange tube 8, and the heat preservation block 10 and the heat preservation layer 6 are made of the same heat preservation material.
The heat exchange tube 8 is arranged at the center of the annular crucible 4, and a temperature gradient with high outside and low inside, high top and low bottom is formed inside the melt, so that the melt can be subjected to controllable unidirectional solidification growth at a high interface advancing speed, and a bubble-free polycrystalline material can be grown at a high speed. Meanwhile, the large single crystal material produced by the device has high purity and no air bubbles due to the directional solidification and impurity removal effect, is very suitable for being used as a high-end coating material, has short period, high capacity and good market applicability, and is particularly applied to the requirements of electronic-grade high-end markets.
During operation, raw materials are put into a cavity of a crucible 4, a cover body 7 is covered, a heating body 5 starts to generate heat, the raw materials are heated until the temperature exceeds a melting point, the raw materials are completely melted and are clarified at high temperature, then the flow of a cooling medium in a heat exchange pipe 8 is gradually increased from the initial flow and gradually increased to the flow required by crystal growth, then the flow of the cooling medium is kept unchanged, the flow introduction speed and power of the cooling medium are synchronously reduced to 0 after the crystal growth is finished, and the crystal is taken out after cooling.
Example 2: a growth process for bubble-free crystal material capable of growing at high speed specifically comprises the following steps:
step one, putting magnesium fluoride powder into a cavity of a crucible, covering a cover body, starting heating by a heating body, heating the raw material until the temperature exceeds a melting point, completely melting the raw material, wherein the heating rate of the raw material is 75 ℃/h, the temperature is 50 ℃, clarifying at high temperature and constant power is 2h, the flow rate of helium in a heat exchange tube is maintained at an initial flow rate, and the initial flow rate is approximately 0.2L/min;
step two, gradually increasing the introduction speed of helium flow, gradually increasing the flow of helium from the initial flow to the flow required by crystal growth within a certain time, wherein the rising rate of the helium flow is 0.5(L/min)/h, generally 10 hours, and the flow required by the crystal growth is 150L/min;
and step three, keeping the flow of the helium gas unchanged, synchronously reducing the flow speed and power of the helium gas to 0 after the crystal grows, and taking out the crystal after cooling.
Example 3: a growth process for bubble-free crystal material capable of growing at high speed specifically comprises the following steps:
step one, lithium fluoride powder is filled into a cavity of a crucible, a cover body is covered, a heating body starts to generate heat, the raw material is heated until the temperature exceeds the melting point, the raw material is completely melted, the heating rate of the raw material is 75 ℃/h, the temperature is 200 ℃, high-temperature clarification is carried out, the power is constant for 5h, the flow rate of helium in a heat exchange tube is maintained at the initial flow rate, and the initial flow rate is approximately 0.5L/min;
step two, gradually increasing the introduction speed of helium flow, gradually increasing the flow of helium from the initial flow to the flow required by crystal growth within a certain time, wherein the rising speed of the helium flow is 23(L/min)/h, generally within 30 hours, and the flow required by the crystal growth is 250L/min;
and step three, keeping the flow of the helium gas unchanged, synchronously reducing the flow speed and power of the helium gas to 0 after the crystal grows, and taking out the crystal after cooling.
Example 4: a growth process for bubble-free crystal material capable of growing at high speed specifically comprises the following steps:
step one, sodium fluoride powder is filled into a cavity of a crucible, a cover body is covered, a heating body starts to generate heat, the raw material is heated until the temperature exceeds a melting point, the raw material is completely melted, the heating rate of the raw material is 75 ℃/h, the temperature is 125 ℃, high-temperature clarification is carried out, the power is constant for 3.5h, the flow rate of helium in a heat exchange pipe is maintained at an initial flow rate, and the initial flow rate is approximately 0.35L/min;
step two, gradually increasing the introduction speed of helium flow, gradually increasing the flow of helium from the initial flow to the flow required by crystal growth within a certain time, wherein the rising speed of the helium flow is 11.75(L/min)/h, generally within 20 hours, and the flow required by the crystal growth is 200L/min;
and step three, keeping the flow of the helium gas unchanged, synchronously reducing the flow speed and power of the helium gas to 0 after the crystal grows, and taking out the crystal after cooling.
Example 5: a growth process for bubble-free crystal material capable of growing at high speed specifically comprises the following steps:
step one, barium fluoride powder is filled into a cavity of a crucible, a cover body is covered, a heating body starts to generate heat, the raw material is heated until the temperature exceeds a melting point, the raw material is completely melted, the heating rate of the raw material is 75 ℃/h, the temperature is 120 ℃, high-temperature clarification is carried out, the power is constant for 3h, the flow rate of helium in a heat exchange tube is maintained at an initial flow rate, and the initial flow rate is approximately 0.2L/min;
step two, gradually increasing the introduction speed of helium flow, gradually increasing the flow of helium from the initial flow to the flow required by crystal growth within a certain time, wherein the rising speed of the helium flow is 10(L/min)/h, generally 15 hours, and the flow required by the crystal growth is 190L/min;
and step three, keeping the flow of the helium gas unchanged, synchronously reducing the flow speed and power of the helium gas to 0 after the crystal grows, and taking out the crystal after cooling.
Example 6: the growth process of bubble-free crystal material capable of growing at high speed is different from that of the embodiment 1 in that the growth process specifically comprises the following steps:
step one, putting magnesium fluoride powder into a cavity of a crucible, covering a cover body, starting heating by a heating body, heating raw materials until the temperature exceeds a melting point, completely melting the raw materials, wherein the heating rate of the raw materials is 75 ℃/h, the temperature is 160 ℃, clarifying at a high temperature, the power is constant for 3.5h, the argon flow in a heat exchange tube is maintained at an initial flow, and the initial flow is approximately 0.4L/min;
step two, gradually increasing the flow rate of argon gas from the initial flow rate to the flow rate required by crystal growth within a certain time, wherein the rising rate of the flow rate of argon gas is 10(L/min)/h, generally within 22 hours, and the flow rate required by crystal growth is 210L/min;
and step three, keeping the flow of the argon gas unchanged, synchronously reducing the flow of the argon gas and introducing the speed and the power to 0 after the crystal growth is finished, and taking out the crystal after cooling.
Example 7: the growth process of bubble-free crystal material capable of growing at high speed is different from that of the embodiment 1 in that the growth process specifically comprises the following steps:
step one, putting magnesium fluoride powder into a cavity of a crucible, covering a cover body, starting heating by a heating body, heating raw materials until the temperature exceeds a melting point, completely melting the raw materials, wherein the heating rate of the raw materials is 75 ℃/h, the temperature is 180 ℃, clarifying at high temperature and constant power is 4h, the nitrogen flow in a heat exchange tube is maintained at an initial flow, and the initial flow is approximately 0.4L/min;
step two, gradually increasing the flow rate of nitrogen from the initial flow rate to the flow rate required by crystal growth within a certain time, wherein the rising rate of the flow rate of nitrogen is 19(L/min)/h, generally within 24 hours, and the flow rate required by crystal growth is 210L/min;
and step three, keeping the nitrogen flow unchanged, synchronously reducing the nitrogen flow introduction speed and power to 0 after the crystal growth is finished, and taking out the crystal after cooling.
Example 8: the growth process of bubble-free crystal material capable of growing at high speed is different from that of the embodiment 1 in that the growth process specifically comprises the following steps:
step one, putting magnesium fluoride powder into a cavity of a crucible, covering a cover body, starting heating by a heating body, heating the raw material until the temperature exceeds a melting point, completely melting the raw material, wherein the heating rate of the raw material is 50 ℃/h, the temperature is 90 ℃, clarifying is carried out at a high temperature, the power is constant for 1.8h, the flow rate of helium in a heat exchange pipe is maintained at an initial flow rate, and the initial flow rate is approximately 0.3L/min;
step two, gradually increasing the flow rate of helium gas from the initial flow rate to the flow rate required by crystal growth within a certain time, wherein the rising rate of the flow rate of helium gas is 3.6(L/min)/h, generally within 20 hours, and the flow rate required by crystal growth is 160L/min;
and step three, keeping the flow of the helium gas unchanged, synchronously reducing the flow speed and power of the helium gas to 0 after the crystal grows, and taking out the crystal after cooling.
Example 9: the growth process of bubble-free crystal material capable of growing at high speed is different from that of the embodiment 1 in that the growth process specifically comprises the following steps:
step one, putting magnesium fluoride powder into a cavity of a crucible, covering a cover body, starting heating by a heating body, heating the raw material until the temperature exceeds a melting point, completely melting the raw material, wherein the heating rate of the raw material is 100 ℃/h, the temperature is 120 ℃, clarifying at high temperature and constant power is 4h, the flow rate of helium in a heat exchange tube is maintained at an initial flow rate, and the initial flow rate is approximately 0.3L/min;
step two, gradually increasing the introduction speed of helium flow, gradually increasing the flow of helium from the initial flow to the flow required by crystal growth within a certain time, wherein the rising speed of the helium flow is 20(L/min)/h, generally within 25 hours, and the flow required by the crystal growth is 180L/min;
and step three, keeping the flow of the helium gas unchanged, synchronously reducing the flow speed and power of the helium gas to 0 after the crystal grows, and taking out the crystal after cooling.
Comparative example 1: the first embodiment of the heat exchange crystal growth system, the cooling gas flow control method and the device disclosed in the chinese patent application publication No. CN105369349A is selected.
Comparative example 2: the second embodiment of the heat exchange crystal growth system, the cooling gas flow control method and the apparatus disclosed in the chinese patent application publication No. CN105369349A is selected.
Comparative example 3: the third embodiment of the heat exchange crystal growth system, the cooling gas flow control method and the device disclosed in the chinese patent application publication No. CN105369349A is selected.
Comparative example 4: the fourth embodiment of the heat exchange crystal growth system, the cooling gas flow control method and the apparatus disclosed in the chinese patent application publication No. CN105369349A is selected.
Comparative example 5: the fifth embodiment of the heat exchange crystal growth system, the cooling gas flow control method and the apparatus disclosed in the chinese patent application publication No. CN105369349A is selected.
Test of
The test method comprises the following steps: the time required for producing crystalline materials of the same quality as those of examples 2 to 9 and comparative examples 1 to 5 was recorded, respectively, and the crystalline materials produced in examples 2 to 9 and comparative examples 1 to 5 were cut and the cut surface was observed with a magnifying glass for the presence of bubbles or impurities.
And (3) test results: the results of the test tests of examples 2 to 9 and comparative examples 1 to 5 are shown in Table 1. As is apparent from Table 1, it is understood from Table 1 that the time required for producing the same quality of the crystal materials of examples 2 to 9 is much shorter than that of comparative examples 1 to 5, the production efficiency is improved by more than 50%, and the produced crystal materials have no bubbles or impurities therein and improved purity.
TABLE 1 test tests of examples 2-9 and comparative examples 1-5
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (7)
1. A growth device capable of growing bubble-free crystal materials at a high speed comprises a support (1) and a furnace body (2) positioned on the support (1), and is characterized in that an annular crucible (4) used for containing raw materials is arranged in the furnace body (2), a cover body (7) is arranged on the annular crucible (4), a heating body (5) used for heating the crucible (4) and adhering the crucible (4) is arranged in the furnace body (2), and a heat preservation layer (6) playing a role in heat preservation is arranged in the furnace body; a through hole (11) is formed in the center of the annular crucible (4), a heat exchange tube (8) is arranged in the through hole (11), a temperature measuring device (12) is arranged on the furnace body (2), and a supporting plate (9) which is abutted against the bottom of the annular crucible (4) is arranged on the peripheral side of the heat exchange tube (8);
heat exchange tube (8) and crucible (4) are located the lateral wall of through-hole (11) department and contact, heat exchange tube (8) include inner tube (81) and cover establish outer tube (82) of inner tube (81) week side, and the top of outer tube (82) is sealed, the top of inner tube (81) and the inside intercommunication of outer tube (82).
2. The growth device capable of growing bubble-free crystalline material at high speed according to claim 1, characterized in that the contact area of the heat exchange tube (8) with the outer sidewall of the crucible (4) located at the through hole (11) is 50-500 cm.
3. A growth process of bubble-free crystal material capable of growing at high speed, which is characterized by using the growth device of bubble-free crystal material capable of growing at high speed according to claim 1 or 2, and comprises the following steps:
step one, loading raw materials into a cavity of a crucible, covering a cover body, starting heating by a heating body, heating the raw materials until the temperature exceeds a melting point, completely melting the raw materials, clarifying at high temperature, keeping constant power for several hours, and maintaining the flow of a cooling medium in a heat exchange tube at an initial flow, wherein the initial flow is approximately 0.2-0.5L/min;
step two, the flow rate of the cooling medium is increased gradually from the initial flow rate to the flow rate required by crystal growth within a certain time, the flow rate of the cooling medium is increased at 0.5-23(L/min)/h, the certain time depends on the size of the crucible and is generally about 10-30 hours, the flow rate required by crystal growth depends on the type and the charging amount of the crystal material and is 250L/min at 150-;
and step three, keeping the flow of the cooling medium unchanged, synchronously reducing the flow introduction speed and power of the cooling medium to 0 after the crystal growth is finished, and taking out the crystal after cooling.
4. The growth process of bubble-free crystal material capable of growing at high speed according to claim 3, wherein the raw material is fluoride crystal material powder, and the raw material is any one of calcium fluoride, magnesium fluoride, barium fluoride, lithium fluoride, sodium fluoride, etc.
5. The growth process of bubble-free crystal material capable of high-speed growth according to claim 3, wherein the temperature raising rate of the raw material in the first step is 50-200 ℃/h.
6. The growth process of bubble-free crystal material capable of high-speed growth according to claim 3, wherein the temperature of the raw material heated to above the melting point in the first step is 50-200 ℃.
7. The growth process of bubble-free crystal material capable of high-speed growth according to claim 3, wherein the cooling medium is an inert gas, mainly helium or argon.
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| CN114086240A (en) * | 2021-11-09 | 2022-02-25 | 北京华卓精科科技股份有限公司 | Annular crucible, and crystal transverse directional growth device and method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202460667U (en) * | 2012-01-17 | 2012-10-03 | 吉林省赛尔光电技术有限公司 | Annular crucible |
| CN104790025A (en) * | 2015-04-14 | 2015-07-22 | 营口市荣兴达科技实业有限公司 | Preparation device and preparation technology for magnesium fluoride single crystal coating material |
| CN105369349A (en) * | 2014-08-29 | 2016-03-02 | 苏州恒嘉晶体材料有限公司 | Heat exchange crystal growth system and cooling gas flow control method and device |
| CN106149051A (en) * | 2015-04-03 | 2016-11-23 | 中国科学院上海硅酸盐研究所 | The thermal control Bridgman method single-crystal growing apparatus of fluoride single crystal body and method |
-
2019
- 2019-05-18 CN CN201910415638.4A patent/CN110093660B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202460667U (en) * | 2012-01-17 | 2012-10-03 | 吉林省赛尔光电技术有限公司 | Annular crucible |
| CN105369349A (en) * | 2014-08-29 | 2016-03-02 | 苏州恒嘉晶体材料有限公司 | Heat exchange crystal growth system and cooling gas flow control method and device |
| CN106149051A (en) * | 2015-04-03 | 2016-11-23 | 中国科学院上海硅酸盐研究所 | The thermal control Bridgman method single-crystal growing apparatus of fluoride single crystal body and method |
| CN104790025A (en) * | 2015-04-14 | 2015-07-22 | 营口市荣兴达科技实业有限公司 | Preparation device and preparation technology for magnesium fluoride single crystal coating material |
Non-Patent Citations (1)
| Title |
|---|
| NUMERICAL SIMULATION OF TIN SOLIDIFICATION UNDER THE INFLUENCE OF NATURAL CONVECTION IN A THICK WALLED ANNULAR CRUCIBLE;A.D. Brent*;《INTERNATIONAL COMMUNICATIONS IN HEAT AND MASS TRANSFER》;19891231;第694页第2段和图1 * |
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