CN116240623A - Downward-growth guided-mode crystal growth method and application - Google Patents
Downward-growth guided-mode crystal growth method and application Download PDFInfo
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- CN116240623A CN116240623A CN202211670370.7A CN202211670370A CN116240623A CN 116240623 A CN116240623 A CN 116240623A CN 202211670370 A CN202211670370 A CN 202211670370A CN 116240623 A CN116240623 A CN 116240623A
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- 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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/34—Edge-defined film-fed crystal-growth using dies or slits
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Abstract
The application relates to a downward-growth guided-mode crystal growth method and application. The method comprises the following steps: s1, placing a mold in a crucible filled with raw materials, enabling the use surface of the mold to be downward, and then heating the crucible to enable the raw materials in the crucible to be melted into a melt; s2, lifting the seed rod vertically below the using surface of the die until the seed crystal contacts with the using surface of the die, and moving the seed rod downwards after welding to finish seeding; s3, cooling the crucible until the growth area of the crystal is covered with the die, and shouldering is completed; s4, cooling the crucible continuously to enable crystals to grow in an equal diameter mode until the raw materials are exhausted; s5, after the crystal is demoulded, stopping moving the seed rod, and cooling and annealing the crystal to finish crystal growth. The method adopts a crystal growth method of downward growth, effectively solves the problem of poor quality of the grown crystal in the prior art, and ensures that the quality of the grown crystal is higher.
Description
Technical Field
The application relates to the technical field of crystal preparation, in particular to a downward-growth guided-mode crystal growth method and application.
Background
The process of forming crystals with specific linear dimensions by converting a substance from a gas phase, a liquid phase, a solid phase under certain conditions of temperature, pressure, concentration, medium, pH and the like is called crystal growth. The crystal growth method mainly comprises a flame method, a pulling method, a guided mode method, a crucible descending method, a kyropoulos method, a directional solidification method and the like.
The guided mode method, also known as edge defined-film fed (EFG) method, is mainly used for growing crystals of a specific shape, and is actually a variation of the czochralski method. The guided mode method can directly grow crystals such as sheets, wires, tubes, rods, plates and the like from the melt, has high crystal growth speed and can accurately control the size, greatly simplifies the processing procedure of the crystals, saves materials, time and energy, reduces the production cost and submits economic benefit, thus being more and more valued by people.
The traditional mould guiding method is to put the raw materials for growth in a crucible provided with a mould, heat the raw materials to melt the raw materials, then conduct crystal guiding growth on the upper side of the mould, and then conduct technological processes of shoulder placement, equal diameter, ending and the like. But in the process of crystal growth by adopting the traditional guided mode method, volatile matters are generated and are influenced by gas convection, and the volatile matters move upwards along with the air flow; when the crystal is grown by the traditional guided mode method, the seed crystal is arranged on the upper side of the melt, volatile matters are easily adhered to the seed crystal along with air flow, so that impurity phases are introduced into the crystal, and finally the crystal is failed to grow or the crystal quality is poor. In addition, in the traditional guided mode method, the heating area is a crucible area, the upper side of the crucible is only provided with a heat insulation material, and the temperature difference between the crucible and the upper side of the crucible is large, so that the temperature gradient of the growth area is overlarge, and the quality of crystallization is further reduced.
Therefore, improvements to the conventional guided mode method are required to produce high quality crystals.
Disclosure of Invention
In order to solve the defects in the prior art, the application provides a downward-growth guided-mode crystal growth method, which effectively solves the problem that in the crystal growth process, volatile matters volatilize upwards and adhere to seed crystals to cause failure of crystal growth or poor crystal quality, so that the quality of the grown crystals is higher.
To this end, a first aspect of the present application provides a downward-growing guided-mode crystal growth method, the method comprising the steps of:
s1, placing a mold in a crucible filled with raw materials, enabling the use surface of the mold to be downward, and then heating the crucible to enable the raw materials in the crucible to be melted into a melt;
s2, lifting the seed rod vertically below the using surface of the die until seed crystals at the top ends of the seed rods are in contact with the using surface of the die, and moving the seed rods downwards after welding to finish seeding;
s3, cooling the crucible until the growth area of the crystal is covered with the die, and shouldering is completed;
s4, cooling the crucible continuously to enable crystals to grow in an equal diameter mode until the raw materials are exhausted;
s5, after the crystal is demoulded, stopping moving the seed rod, and cooling and annealing the crystal to finish crystal growth.
In the crystal growth method, the use surface of the mold is downward to enable the crystal to grow in a downward growth mode, so that the phenomenon that volatile matters generated in the growth process adhere to seed crystals along with air flow is effectively avoided, and further the phenomenon that impurity phases are introduced into the crystal is avoided; and the crystal grows downwards, the bubbles in the melt can move upwards, and the bubbles can not move downwards to the crystallization surface, so that defects such as bubbles and the like can not be generated in the crystal, and finally, the high-quality crystal is obtained. Meanwhile, in the method, the growing area of the crystal is inside the heating area of the crucible, obvious temperature mutation points do not exist around the growing area, the temperature gradient is small, and the quality of the grown crystal is higher.
In some embodiments, the crucible includes a feedstock zone that is not located vertically below the use face of the mold.
The seed crystal is positioned vertically below the using surface of the die, so that the volatile matters in the melt generated by melting the raw materials in the raw material area of the crucible can be further prevented from being adhered to the seed crystal through the arrangement.
In some embodiments, the mold has a mold bridge disposed thereon, the mold bridge being disposed in the feed region of the crucible; capillary slits are arranged in the die and the die bridge, the capillary slits in the die and the die bridge are communicated, and melt melted by raw materials flows to the using surface of the die through capillary action of the capillary slits.
Because the die bridge is placed in the raw material area of the crucible, the die bridge can be in contact with the melt of the raw material, so that the melt can flow to the use surface of the die through the capillary action of the die bridge and the capillary joints arranged in the die and the die bridge.
In some embodiments, the components used in the crystal growth method include a crucible (the height of the outer crucible edge of the crucible can be higher than the height of the whole die), a die provided with a die bridge, a seed crystal, a seed rod, a heating device and the like; the crucible, the die provided with the die bridge and the seed rod are all made of high-temperature resistant materials, and the heating mode of the heating device can be electromagnetic induction heating or resistance heating; the mold shape can be various shapes such as square, round, etc. When the assembly is used for crystal growth, a mold provided with a mold bridge is placed in a crucible, wherein the mold is used face down, the mold bridge arranged on the mold is placed in a raw material area of the crucible, and a heating device is used for heating the crucible.
In some embodiments, the angle α of the use face of the mold is 30 to 90 °. In some embodiments, the angle α of the use face of the mold may be 30 °, 45 °, 60 °, 75 °, 90 °, or the like. In some preferred embodiments, the angle α of the use face of the mold is 45 to 75 °. In some most preferred embodiments, the angle α of the die use face is 60 °.
In this application, the angle α of the use surface of the die is an included angle between the capillary outlet and the horizontal plane in the die at the use surface of the die, as shown in fig. 1. When the crystal grows, the shape of the crystal depends on the shape of the using surface of the mold, and meanwhile, the quality of the crystal also depends on the shape of the using surface of the mold to a great extent; wherein the angle alpha of the use face of the mold has a large influence on the heat and mass transfer of the crystal. When the angle alpha of the using surface of the die is controlled to be 45-75 degrees, particularly 60 degrees, the possibility that Mao Xifeng is filled by melt is effectively reduced, the stress and the impurity phase are easy to discharge, and the quality of the finally prepared crystal is further improved.
In some embodiments, the outside of the crucible is coated with a thermal insulation material, and the thermal insulation material is zirconia fiber bricks with the thickness of 30-50 mm.
In the application, the thermal insulation material is coated on the outer side of the crucible to be favorable for maintaining the temperature field environment of crystal growth, and the radial temperature gradient of the melt is reduced as much as possible, so that the quality of the crystal is improved. The melting point of the zirconia reaches 2700 ℃, is one of the best known refractory materials, and the zirconia is adopted as a heat insulation material and cannot react with melt raw materials, and has good heat insulation effect. In addition, the thickness of the heat insulation material has a larger influence on the quality of the crystal, the heat insulation effect cannot be achieved due to the fact that the thickness of the heat insulation material is too small, the cost of crystal growth can be increased due to the fact that the thickness is too large, meanwhile, the heat dissipation process inside the crystal is hindered, and adverse effects are caused on the crystal. The zirconia fiber brick with the thickness of 30-50 mm is selected as the heat insulation material, so that the quality of crystals is improved.
In some embodiments, in step S2, the seed rod is moved downward at a rate of 5 to 25mm/h.
In some embodiments, the seed rod may move downward at a rate of 5mm/h, 10mm/h, 15mm/h, 20mm/h, 25mm/h, or the like. In some preferred embodiments, the seed rod moves downward at a rate of 10 to 20mm/h. In some most preferred embodiments, the seed rod moves downward at a rate of 15mm/h.
The downward movement rate of the seed rod is one of the key technologies in crystal growth, and excessive downward movement rate can cause lattice breakage, and unstable movement rate can cause a large number of serious growth stripes in the crystal. According to the method, the moving speed of the seed rod is controlled in real time through the morphological characteristics of the crystal during crystal growth, and the downward moving speed of the seed rod is controlled to be 5-25 mm/h, so that the inherent quality of the grown crystal can be improved.
In some embodiments, in step S3, the cooling rate of the cooling is 2-5 ℃/h. In some specific embodiments, in step S3, the cooling rate of the cooling may be 2 ℃/h, 3 ℃/h, 4 ℃/h, 5 ℃/h, or the like. In some preferred embodiments, in step S3, the cooling rate of the cooling may be 3 to 4 ℃/h.
In some embodiments, in step S4, the cooling rate of the cooling is 0.5 to 2 ℃/h. In some specific embodiments, in step S4, the crystal growth morphology is kept unchanged, the cooling rate, the movement speed of the seed rod and the expected movement speed of the seed rod are controlled by series PID, and the cooling rate of the cooling is controlled within the range of 0.5-2 ℃/h. In some preferred embodiments of the present application, the cooling rate of the cooling is 1 to 1.5 ℃/h.
The intrinsic quality of the grown crystal can be further improved by controlling the cooling rate in the shouldering process and the constant diameter growth process.
In some embodiments, in step S5, the cooling rate of the cooling annealing is 150-250 ℃/h, and the temperature after the cooling annealing is 20-25 ℃ (normal temperature).
In some specific embodiments, in step S5, the cooling rate of the cooling annealing may be 150 ℃/h, 180 ℃/h, 200 ℃/h, 230 ℃/h, 250 ℃/h, or the like. In some preferred embodiments, the cooling rate of the cooling anneal is 180 to 230 ℃/h. In some most preferred embodiments, the cool down rate of the cool down anneal is 200 ℃/h.
In the application, the grown crystal is subjected to cooling annealing under the parameter condition, so that the complex internal stress in the crystal can be effectively eliminated, and the quality of the crystal is improved.
The growth of crystals in the present application may be performed under a protective atmosphere. Different protective atmospheres may be selected for different grown crystals. For example, when the grown crystal is β -gallium oxide crystal, the protective atmosphere may be a mixture of oxygen and inert gas, and the pressure ratio of the oxygen to the inert gas may be, for example, 1: (19-99) and the like; when the grown crystal is a sapphire crystal, the protective atmosphere is an inert gas. In this application, the inert gas may be any one or more of nitrogen, argon, helium, neon, and xenon.
A second aspect of the present application provides the use of a method as described in the first aspect of the present application for the preparation of β -gallium oxide crystals and sapphire crystals.
The crystal growth method can effectively improve the quality of crystals, so that the method can be well applied to the preparation of beta-gallium oxide crystals and sapphire crystals.
In summary, the beneficial technical effects of the application are: in the crystal growth method, the growth direction of the crystal is downward growth, so that the phenomenon that volatile matters generated in the growth process adhere to seed crystals along with air flow is effectively avoided, and further, the introduction of impurity phases into the crystal is avoided; and the crystal grows downwards, the bubbles in the melt can move upwards, and the bubbles can not move downwards to the crystallization surface, so that defects such as bubbles and the like can not be generated in the crystal, and finally, the high-quality crystal is obtained. Meanwhile, the growing area of the crystal is inside the heating area of the crucible, obvious temperature mutation points do not exist around the growing area, the temperature gradient is small, the quality of the grown crystal is higher, the method can be well applied to the preparation of beta-gallium oxide crystals and sapphire crystals, and the application prospect is excellent.
Drawings
Fig. 1 is a schematic view of the angle α of the die-use surface described in the present application.
Fig. 2 is a schematic diagram showing the assembled structure of the components used in the beta-gallium oxide crystal growth in example 1.
Fig. 3 is a cross-sectional view showing the assembled structure of the components used for the β -gallium oxide crystal growth in example 1.
Detailed Description
In order that the present application may be more readily understood, the following examples are presented in conjunction with the following detailed description, which are intended to be illustrative only and are not intended to limit the scope of application of the present application. The starting materials or components used in the present application may be prepared by commercial or conventional methods unless specifically indicated.
Example 1: growth of beta-gallium oxide crystals
The components used for crystal growth: the crucible (the height of the outer crucible edge of the crucible is higher than the whole height of the mould), the mould provided with the mould bridge, the seed crystal rod, the heating device and the heat insulation material. The mould is square, the size is 20mm x 12mm, the angle alpha of the mould using surface is 90 degrees, and capillary slits which are communicated are arranged in the mould and the mould bridge. When the crystal grows, the assembly structure of each component is schematically shown in fig. 2, and the cross-section of the assembly structure of each component is shown in fig. 3; the mold with the mold bridge is placed in the crucible, wherein the mold is used face down, and the mold bridge arranged on the mold is placed in the raw material area of the crucible; the heating device is an intermediate frequency induction coil for heating a crucible (not shown in the figure), the heat insulation material is zirconia fiber bricks with the thickness of 40mm, and the heat insulation material is wrapped on the outer side of the crucible (not shown in the figure); the seed crystal is arranged at the top end of the seed rod, and the seed crystal and the seed rod are arranged vertically below the using surface of the die.
The growth process is as follows:
1. 300 g of high purity gallium oxide feedstock (purity 6N) was placed in the feedstock zone of a crucible;
2. heating the crucible by using an intermediate frequency induction coil under the protective atmosphere of 99% argon and 1% oxygen at 0.5MPa, and heating to the melting point of gallium oxide (1840 ℃) until the gallium oxide raw material is melted into a melt, wherein the volatile matters can be seen to move upwards at the moment, but the volatile matters are not contacted with the seed crystal, and the surface of the seed crystal is free from mixed crystals;
3. lifting the gallium oxide seed crystal through the seed rod until the gallium oxide seed crystal contacts the using surface of the die;
4. after the front end remelting part of the gallium oxide seed crystal is welded, slowly moving a seed rod downwards at a speed of 15mm/h, and driving the seed crystal to grow downwards by the seed rod;
5. slowly cooling the crucible at a cooling rate of 3 ℃, gradually amplifying the crystal until the whole mould is fully paved in a crystal growth area, and finishing shouldering;
6. observing the morphology features of the crystal, and on the premise of keeping the morphology features unchanged, setting the cooling rate within the range of 1-1.5 ℃ to slowly cool the crucible, and growing the crystal in an equal diameter mode until the gallium oxide raw material in the crucible is exhausted; the bubbles move upwards in the growth process, so that the equal-diameter part almost has no bubbles;
7. after the crystal is separated from the die, the movement of the seed rod is stopped, and then slow cooling annealing is carried out at a cooling rate of 200 ℃/h until the temperature is restored to normal temperature (25 ℃), and the growth of the beta-gallium oxide crystal is finished.
Example 2: growth of beta-gallium oxide crystals
The growth process was essentially the same as in example 1, except that the die was used with an angle α of 60 ° in the assembly used for crystal growth.
Example 3: growth of beta-gallium oxide crystals
The growth process was essentially the same as in example 1, except that the assembly used for crystal growth was such that the angle α of the die use face was 45 °.
Example 4: growth of beta-gallium oxide crystals
The growth process was essentially the same as in example 1, except that the die was used with an assembly having a face angle α of 30 ° for crystal growth.
Example 5: growth of beta-gallium oxide crystals
The growth process was essentially the same as in example 1, except that the thermal insulation material used in the assembly for crystal growth was zirconia fiber brick having a thickness of 30 mm.
Example 6: growth of beta-gallium oxide crystals
The growth process was essentially the same as in example 1, except that the thermal insulation material used in the assembly for crystal growth was zirconia fiber brick having a thickness of 50 mm.
Example 7: growth of beta-gallium oxide crystals
The growth process was basically the same as that of example 1, except that in step 4 of the crystal growth process, after the front end remelting portion of the gallium oxide seed crystal was further welded, the seed rod was slowly moved downward at a speed of 5mm/h, and the seed rod drove the seed crystal to grow downward.
Example 8: growth of beta-gallium oxide crystals
The growth process was basically the same as that of example 1, except that in step 4 of the crystal growth process, after the front end remelting portion of the gallium oxide seed crystal was further welded, the seed rod was slowly moved downward at a speed of 25mm/h, and the seed rod drove the seed crystal to grow downward.
Example 9: growth of beta-gallium oxide crystals
The growth process was basically the same as example 1, except that in step 5 of the crystal growth process, the crucible was slowly cooled at a cooling rate of 5 ℃ and the crystal was gradually enlarged until the crystal growth area was spread over the entire mold, completing the shouldering.
Example 10: growth of beta-gallium oxide crystals
The growth process was basically the same as example 1, except that in step 5 of the crystal growth process, the crucible was slowly cooled at a cooling rate of 2 ℃, and the crystal was gradually enlarged until the crystal growth area was spread over the entire mold, completing the shouldering.
Example 11: growth of beta-gallium oxide crystals
The growth process is basically the same as that of example 1, except that in step 6 of the crystal growth process, the morphology features of the crystal are observed, the crucible is slowly cooled at a cooling rate set within a range of 0.5-2 ℃ on the premise that the morphology features are kept unchanged, and the crystal grows in a constant diameter until the gallium oxide raw material in the crucible is exhausted.
Example 12: growth of beta-gallium oxide crystals
The growth process was substantially the same as example 1, except that in step 6 of the crystal growth process, the crucible was slowly cooled at a cooling rate of 2 ℃ until the gallium oxide raw material in the crucible was exhausted, and the crystal was grown in constant diameter.
Example 13: growth of beta-gallium oxide crystals
The growth process was substantially the same as in example 1, except that in step 7 of the crystal growth process, after the crystal was separated from the mold, the movement of the seed rod was stopped, and then slow cooling annealing was performed at a cooling rate of 150 ℃/h until the temperature was restored to normal temperature (25 ℃), and the growth of the β -gallium oxide crystal was completed.
Example 14: growth of beta-gallium oxide crystals
The growth process was substantially the same as in example 1, except that in step 7 of the crystal growth process, after the crystal was separated from the mold, the movement of the seed rod was stopped, and then the slow cooling annealing was performed at a cooling rate of 230 ℃/h until the temperature was restored to normal temperature (25 ℃), and the growth of the β -gallium oxide crystal was completed.
Example 15: growth of beta-gallium oxide crystals
The growth process was substantially the same as in example 1, except that in step 7 of the crystal growth process, after the crystal was separated from the mold, the movement of the seed rod was stopped, and then slow cooling annealing was performed at a cooling rate of 250 ℃/h until the temperature was restored to normal temperature (25 ℃), and the growth of the β -gallium oxide crystal was completed.
Example 16: growth of sapphire crystals
The components used for crystal growth: substantially the same as in example 2, except that the heating device was a tungsten molybdenum resistance heater for heating the crucible.
The growth process is as follows:
1. 300 g of high-purity alumina raw material (with the purity of 6N) is placed in a raw material area of a crucible after being subjected to isostatic pressing and high-temperature sintering;
2. heating the crucible by a tungsten-molybdenum resistance heater under the protective atmosphere of pure argon of 0.5MPa, and heating to the melting point of alumina (2050 ℃) until the alumina raw material is melted into a melt; at the moment, the volatile matters can be seen to move upwards, but the volatile matters cannot contact with the seed crystal, and the surface of the seed crystal is free from mixed crystals;
3. lifting the sapphire seed crystal through the seed rod until the sapphire seed crystal contacts with the using surface of the die;
4. after the front end remelting part of the sapphire seed crystal is welded, slowly moving the seed rod downwards at the speed of 20mm/h, and driving the seed crystal to grow downwards by the seed rod;
5. slowly cooling the crucible at a cooling rate of 4 ℃, gradually amplifying the crystal until the whole mould is fully paved in a crystal growth area, and finishing shouldering;
6. observing the morphology features of the crystal, and on the premise of keeping the morphology features unchanged, setting the cooling rate within the range of 1-1.5 ℃ to slowly cool the crucible, and growing the crystal in an equal diameter mode until the alumina raw material in the crucible is exhausted, and growing the crystal in an equal diameter mode; the bubbles move upwards in the growth process, so that the equal-diameter part almost has no bubbles;
7. and automatically separating the crystal from the die, stopping moving the seed rod, and then slowly cooling and annealing at a cooling rate of 180 ℃/h until the temperature is restored to normal temperature (25 ℃), and ending the growth of the sapphire crystal.
Test case
Sample treatment to be measured: the β -gallium oxide crystals prepared in examples 1 to 15 and the sapphire crystal prepared in example 16 were processed into single crystal wafers of 10mm×10mm×1mm specifications, and the single crystal wafers were subjected to the following performance tests by the following test methods, and the presence or absence of bubbles in the crystals was observed, and the test results are shown in table 1:
half-peak width of rocking curvature: respectively detecting half peak widths of rocking curves of different single crystal wafers by adopting an X-ray diffractometer;
dislocation density: and adopting a phosphoric acid corrosion method to characterize dislocation density of different single crystal wafers.
TABLE 1
As can be seen from the test results in Table 1, the beta-gallium oxide crystals prepared in examples 1 to 15 and the sapphire crystal prepared in example 16 of the present application all have no bubble generation on the crystal surface, the rocking curve half-peak widths of the crystals are all substantially within 50 arcsec, and the dislocation densities are all 500 bars/cm 2 About, the crystal quality is excellent. The method for growing the crystal by adopting downward growth can effectively avoid that volatile matters adhere to seed crystals along with air flow in the growth process, so that impurity phases are introduced into the crystal, and further the crystal growth failure or poor crystal quality is caused; simultaneously, the growth area is in the heating area by downward growth, obvious temperature mutation points do not exist around the growth area, the temperature gradient is small, and the quality of the grown crystal is higher; and the crystal grows downwards, and bubbles in the melt move upwards, so that the bubbles do not move downwards to a crystal face, and defects such as bubbles are not generated in the crystal.
From the detection results of the beta-gallium oxide crystals prepared in examples 1 to 15, the adjustment of the angle alpha of the use surface of the mold, the thickness of the heat insulation material, the downward movement rate of the seed rod, the cooling rate in the shouldering process, the cooling rate in the isodiametric growth process and the cooling rate in the cooling and annealing process all have influences on the quality of the finally prepared crystal; and the quality of the finally produced crystal can be made better by adopting the relevant crystal growth conditions in example 2.
It should be noted that the above-described embodiments are only for explaining the present application, and do not constitute any limitation to the present application. The present application has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the present application as defined within the scope of the claims of the present application, and the invention may be modified without departing from the scope and spirit of the present application. Although the present application is described herein with reference to particular methods, materials and embodiments, the present application is not intended to be limited to the particular examples disclosed herein, but rather, the present application is intended to extend to all other methods and applications having the same functionality.
Claims (10)
1. A method of crystal growth by a downward-growing guided-mode method, the method comprising the steps of:
s1, placing a mold in a crucible filled with raw materials, enabling the use surface of the mold to be downward, and then heating the crucible to enable the raw materials in the crucible to be melted into a melt;
s2, lifting the seed rod vertically below the using surface of the die until seed crystals at the top ends of the seed rods are in contact with the using surface of the die, and moving the seed rods downwards after welding to finish seeding;
s3, cooling the crucible until the growth area of the crystal is covered with the die, and shouldering is completed;
s4, cooling the crucible continuously to enable crystals to grow in an equal diameter mode until the raw materials are exhausted;
s5, after the crystal is demoulded, stopping moving the seed rod, and cooling and annealing the crystal to finish crystal growth.
2. The crystal growth method of claim 1, wherein the crucible includes a feedstock zone that is not located vertically below a use face of the mold.
3. The crystal growing method according to claim 1 or 2, wherein a mold bridge is provided on the mold, the mold bridge being placed in a raw material region of the crucible; capillary slits are arranged in the die and the die bridge, the capillary slits in the die and the die bridge are communicated, and melt melted by raw materials flows to the using surface of the die through capillary action of the capillary slits.
4. The crystal growth method according to claim 1 or 2, wherein the angle α of the use surface of the mold is 30 to 90 °.
5. The crystal growth method according to claim 1 or 2, wherein the outside of the crucible is coated with a thermal insulation material, and the thermal insulation material is zirconia fiber bricks with a thickness of 30-50 mm.
6. The crystal growth method according to claim 1 or 2, wherein in step S2, the downward movement rate of the seed rod is 5 to 25mm/h.
7. The crystal growth method according to claim 1 or 2, wherein in step S3, the cooling rate of the cooling is 2 to 5 ℃/h.
8. The crystal growth method according to claim 1 or 2, wherein in step S4, the cooling rate of the cooling is 0.5-2 ℃/h.
9. The crystal growth method according to claim 1 or 2, wherein in step S5, the cooling rate of the cooling annealing is 150 to 250 ℃/h, and the temperature after the cooling annealing is 20 to 25 ℃.
10. Use of a method according to any one of claims 1-9 for the preparation of β -gallium oxide crystals and sapphire crystals.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117888183A (en) * | 2024-03-15 | 2024-04-16 | 北京铭镓半导体有限公司 | Crystal growth method combining pulling method and guided mode method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117888183A (en) * | 2024-03-15 | 2024-04-16 | 北京铭镓半导体有限公司 | Crystal growth method combining pulling method and guided mode method |
| CN117888183B (en) * | 2024-03-15 | 2024-06-07 | 北京铭镓半导体有限公司 | Crystal growth method combining pulling method and guided mode method |
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