CN111593398A - Gallium nitride single crystal growth device and growth method - Google Patents
Gallium nitride single crystal growth device and growth method Download PDFInfo
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- CN111593398A CN111593398A CN202010557426.2A CN202010557426A CN111593398A CN 111593398 A CN111593398 A CN 111593398A CN 202010557426 A CN202010557426 A CN 202010557426A CN 111593398 A CN111593398 A CN 111593398A
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- 239000013078 crystal Substances 0.000 title claims abstract description 75
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 46
- 239000010959 steel Substances 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000005260 corrosion Methods 0.000 claims abstract description 19
- 238000005192 partition Methods 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 238000005242 forging Methods 0.000 claims description 20
- 239000010410 layer Substances 0.000 claims description 20
- 238000007789 sealing Methods 0.000 claims description 17
- 239000010931 gold Substances 0.000 claims description 16
- 239000010948 rhodium Substances 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 13
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 8
- 238000005536 corrosion prevention Methods 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 239000002356 single layer Substances 0.000 claims description 7
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- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
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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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
- C30B7/105—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes using ammonia as solvent, i.e. ammonothermal processes
-
- 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
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
- C30B29/406—Gallium nitride
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The application discloses a gallium nitride single crystal growth device and a growth method, which are used for realizing ammonothermal growth of high-quality and large-size gallium nitride single crystals. The gallium nitride single crystal growth device comprises a growth container, a machine frame arranged outside the growth container and a heating device arranged in the growth container. The growth container barrel consists of an inner barrel and a flat steel wire or a flat steel belt wound on the outer wall of the inner barrel; the frame is used for supporting the growth container and fixing the end cover of the growth container to counteract the axial force caused by ultrahigh pressure in the container; the heating device is used for heating the ammonia solvent in the growth container; all parts of the growth container which are contacted with the ammonia solvent are provided with an anti-corrosion lining or an anti-corrosion layer. According to the gallium nitride single crystal growth method, the partition plate is arranged in the growth container, the growth container is divided into the growth area and the raw material area, and the heating device respectively heats the growth area and the raw material area, so that the temperature difference exists between the growth area and the raw material area, and the supercritical ammonia solvent generates convection in the growth container to promote the gallium nitride single crystal to continuously grow. The gallium nitride single crystal growth container can break through the limitation of the prior art, the inner diameter reaches phi 300mm and above, and the large-scale production of gallium nitride single crystals of 4' and above can be realized, so that the cost of the gallium nitride single crystals is greatly reduced.
Description
Technical Field
The invention relates to the technical field of crystal growth, in particular to a gallium nitride single crystal growth device and a gallium nitride single crystal growth method.
Background
Gallium nitride (GaN) has the properties of large forbidden band width, high breakdown electric field, large thermal conductivity, high electron saturation drift velocity, small dielectric constant and the like, so that the GaN has great application potential in the aspects of optoelectronic devices, power electronics, radio frequency microwave devices, lasers, detectors and the like.
The method for manufacturing the GaN single crystal comprises an HVPE (hydride vapor phase epitaxy) method, a sodium melting method, an ammonothermal method and the like, the method for growing the GaN single crystal by the ammonothermal method has the characteristics of low crystal defect density (high quality), high yield and omnibearing crystal growth, is similar to the principle of growing artificial crystals by the hydrothermal method, and the ammonothermal method has the industrial production prospect of high-quality GaN single crystal.
Similar to a crystal kettle needed by growing artificial crystals by a hydrothermal method, a growth container is also needed for growing GaN single crystals by an ammonothermal method, the difference is that the design parameters of the growth container needed for growing the GaN single crystals by the ammonothermal method are higher and are 200MPa and 650 ℃, the GaN single crystal growth container is manufactured by adopting high-temperature nickel-based alloy in the prior art and is limited by the maximum weight and processing level of high-temperature nickel-based alloy ingots, the inner diameter of the GaN single crystal growth container at the present stage can only reach less than 300mm, the batch production of GaN single crystals with 4' specifications can only be realized, the cost is higher, and the industrial production of the GaN single crystals, particularly the large-size GaN single crystals.
Disclosure of Invention
In view of the above, the present invention provides a gallium nitride single crystal growth apparatus and a gallium nitride single crystal growth method, so as to realize large-scale production of 4 ″ or more gallium nitride single crystals, thereby greatly reducing the cost of the gallium nitride single crystals.
A gallium nitride single crystal growth device comprises a growth container, a machine frame arranged outside the growth container and a heating device arranged in the growth container.
The growth container comprises an end cover and a cylinder body, and a closed space formed by the end cover and the cylinder body provides a growth environment for the gallium nitride single crystal;
the frame is used for supporting the growth container and fixing the end cover of the growth container so as to counteract the axial force caused by ultrahigh pressure in the growth container;
the heating device is used for heating the ammonia solvent in the growth container to enable the ammonia solvent to be in a subcritical/supercritical state;
all parts of the growth container which are contacted with the ammonia solvent are provided with an anti-corrosion lining or an anti-corrosion layer.
Optionally, the growth container cylinder comprises an inner cylinder and a prestressed flat steel wire or a flat steel band wound on the outer wall of the inner cylinder, the inner cylinder is made of a high-strength gun steel forging, a low-alloy steel forging or steel plate, a stainless steel forging or steel plate, or a stainless steel composite plate, and the flat steel wire is made of spring steel and the flat steel band is made of low-alloy steel.
Optionally, the growth container end cover is made of a high-strength gun steel forging, a low-alloy steel forging or steel plate, a stainless steel forging or steel plate, or a stainless steel composite plate.
Optionally, the growth container inner cylinder and the end cover are provided with water cooling grooves or water cooling plates to cool the growth container cylinder and the end cover, and the metal temperature of the growth container cylinder and the end cover does not exceed 425 ℃.
Optionally, the sealing structure adopts a sealing form of O-ring, B-ring, C-ring, Bridgman seal, Grayloc seal, wedge-shaped ring seal, or a combination of more than one of the above seals, or a combination of two or more of the above seals, the sealing structure ensures the sealing performance of the growth container under vacuum, high temperature and ultrahigh pressure conditions, and the leakage rate is not more than 1.0 × 10-12Pa·m3/s。
Optionally, the rack is a component formed by winding prestressed flat steel wires such as an upright column and a semicircular beam.
Optionally, the heating body is a resistance wire heating body, a heating sleeve is arranged in the growth container, and the heating body connecting wire is led out from an end cover of the growth container.
Optionally, the anticorrosion liner or the anticorrosion layer is of a single-layer or double-layer structure, and one side of the single-layer or double-layer structure, which is in contact with the ammonia solvent, is made of precious metals such as platinum Pt, iridium Ir, gold Au, silver Ag, palladium Pd, rhodium Rh, ruthenium Ru, and the like, or alloys thereof.
Alternatively, the noble metal such as platinum Pt, iridium Ir, gold Au, silver Ag, palladium Pd, rhodium Rh, ruthenium Ru, or an alloy thereof may be disposed by one or a combination of more than one of lining, welding, and plating.
A method for growing a gallium nitride single crystal, using the growing apparatus according to any one of claims 1 to 8, the method comprising:
arranging a partition plate in the growth container, and dividing the growth container into a growth area and a raw material area;
seed crystals are placed in the growth area, gallium nitride polycrystalline raw materials are placed in the raw material area, and mineralizers are placed in the growth container;
sealing the growth container, and filling the growth container with an ammonia solvent after vacuumizing;
respectively heating the growth area and the raw material area by adopting a heating device, providing a first temperature for the growth area, providing a second temperature for the raw material area, and enabling a temperature difference to exist between the growth area and the raw material area; the ammonia solvent in the growth container generates convection flow between the growth area and the raw material area, and the gallium nitride seed crystals are spontaneously generated in the growth area or the gallium nitride seed crystals in the growth area are promoted to continuously grow;
after the growth of the gallium nitride single crystal is completed, the gallium nitride single crystal is taken out, the growth container is cleaned and dried, and then the process returns to step S01 to grow the gallium nitride single crystal again.
According to the technical scheme, the GaN single crystal growth device is different from a crystal kettle or the conventional GaN single crystal growth container, the GaN single crystal growth device adopts a heating mode in the growth container, the cylinder body of the growth container adopts a prestressed flat steel wire or a flat steel strip wound cylinder body, at the moment, the inner diameter of the growth container can be phi 1500mm or more and is far larger than the size of the conventional GaN single crystal growth container, and the heating device is arranged in the growth container, so that the heating efficiency of the heating device can be improved, the temperature of each temperature zone in the growth container can be accurately controlled, and the stable growth of the GaN single crystal can be promoted.
In addition, the failure mode of the growth container wound by the prestressed flat steel wire or the flat steel strip is 'leakage and explosion only', the risk of integral brittle failure of the existing GaN single crystal growth container is avoided, and the safety of the growth container is higher.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a GaN single crystal growing apparatus according to an embodiment of the invention;
FIG. 2 is a schematic structural diagram of another GaN single crystal growing apparatus according to an embodiment of the present invention;
FIG. 3 is a schematic structural view of an anticorrosion lining of a GaN single crystal growing device, which is disclosed by the embodiment of the invention;
FIG. 4 is a flow chart of a GaN single crystal growing method disclosed in an embodiment of the invention;
FIG. 5 is a schematic diagram showing the temperature distribution in a GaN single crystal growth vessel according to an embodiment of the present invention.
Reference numerals:
10-a growth vessel; 11-end cap; 12-a cylinder body; 121-inner cylinder; 122-prestressed flat steel wire or flat steel strip winding layer;
20-a frame;
30-seed crystal zone heating device (comprising a thermocouple temperature measuring device);
40-a separator;
50-seed crystal;
60-a raw material zone heating device (comprising a thermocouple temperature measuring device);
70-raw material;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the embodiment of the invention discloses a gallium nitride single crystal growth device, which comprises a growth container 10, a frame 20 arranged outside the growth container, and heating devices 30 and 60 arranged in the growth container.
The growth container 10 includes an end cap 11, a cylinder 12 and a sealing structure (not shown in the figure), the closed space formed by the end cap 11, the cylinder 12 and the sealing structure provides a growth environment for the gallium nitride single crystal, the number of the end caps 11 can be one or two, when the cylinder 12 is provided with a hole at one end, one end cap is provided, and when the cylinder 12 is provided with a hole at two ends, two end caps are provided.
As the growth environment of the ammonia thermal method for growing the GaN single crystal is 200MPa and 650 ℃, in the prior art, the nickel-based alloy is adopted to manufacture the growth container, but the maximum diameter and the maximum weight of the nickel-based alloy ingot casting at the present stage are usually less than phi 1000mm and 10 tons, the maximum inner diameter of the manufactured growth container is not more than phi 300mm, and the size of the grown GaN single crystal is limited. The growth container cylinder body consists of an inner cylinder body 121 and a prestressed flat steel wire or flat steel belt 122 wound on the outer wall of the inner cylinder body, heating devices 30 and 60 are arranged inside a growth container 10, and water cooling grooves or water cooling plates are arranged in an end cover 11 and the inner cylinder body 121 to cool the growth container cylinder body and the end cover, so that the metal temperature of the growth container cylinder body and the end cover is not more than 425 ℃, and at the moment, the inner cylinder body 121 and the end cover 11 are made of high-strength gun steel forgings, low-alloy steel forgings or steel plates, stainless steel forgings or steel plates, or stainless steel composite plates. Preferably, the high-strength gun steel forging can be selected from 22Cr2Ni4MoV、35CrNi3MoVR、36CrNi3MoVR and the like; the low-alloy steel forgings or steel plates are selected from 16Mn, 20MnMo, Cr-Mo steel forgings and the like; the stainless steel forgings or steel plates are selected from 304, 304L, 316L and the like; the stainless steel composite board base material adopts a low alloy steel plate, the composite material adopts a stainless steel plate and the like; the steel forgings or the steel plates are all made of mature materials, the weight of the cast ingots can reach dozens of tons or even hundreds of tons, and at the moment, the inner diameter of the growth container can reach phi 1500mm or more, which is far larger than the size of the existing GaN single crystal growth container. The prestressed flat steel wire material is 65Mn spring steel; the prestressed flat steel strip is made of low alloy steel such as Q345R, and the flat steel wire or the flat steel strip is also made of mature materials and is widely applied.
Sealing joint of end cover 11 and cylinder 12The structure (not shown in the figure) adopts O-ring, B-ring, C-ring, Bridgman seal, Grayloc seal, wedge-shaped ring seal, or the combination of more than one of the above seal structures, the seal structure ensures the sealing performance of the growth container under the working conditions of vacuum, high temperature and ultrahigh pressure, the leakage rate is less than or equal to 1.0 × 10-12Pa·m3/s。
The frame 20 is formed by winding pre-stressed flat steel wires such as columns and semicircular beams, and the main purpose of the frame 20 is to support a growth container, fix an end cover of the growth container and counteract axial force caused by ultrahigh pressure in the growth container.
Because the ammonia solvent is in a subcritical/supercritical state in the GaN single crystal growth environment, the ammonia can decompose hydrogen at the moment, the hydrogen can generate hydrogen embrittlement on steel materials under high temperature and ultrahigh pressure to cause brittle failure, in addition, because the growth container is filled with a mineralizer, the mineralizer has certain corrosivity and can corrode the steel materials, and corrosion products can pollute the GaN single crystal, therefore, all parts in the growth container 10, which are in contact with the ammonia solvent, are provided with anti-corrosion linings or anti-corrosion layers, and the parts in contact with the ammonia solvent comprise the inner wall of the inner cylinder body; secondly, the inner side of the end cover; ③ structural members in the growth container, such as heating device sleeves (30 and 60), partition plates 40, raw material baskets (not shown), seed crystal shelves (not shown) and mineralizer capsule containers (not shown); and fourthly, sealing structure and the like. The corrosion protection lining or the corrosion protection layer has a single-layer or double-layer structure, and as shown in fig. 1, in the present embodiment, the corrosion protection layer has a single-layer structure. One side of the single-layer or double-layer structure, which is in contact with the ammonia solvent, is made of precious metals such as platinum Pt, iridium Ir, gold Au, silver Ag, palladium Pd, rhodium Rh, ruthenium Ru and the like or alloys thereof. Noble metals such as platinum Pt, iridium Ir, gold Au, silver Ag, palladium Pd, rhodium Rh, ruthenium Ru, and the like, or alloys thereof are arranged by one or a combination of more than one of lining, welding, and plating. The presence of the corrosion-resistant liner or layer protects the growth vessel from corrosion by hydrogen or corrosive mineralizers and ensures the cleanliness of the GaN single crystal.
Alternatively, as shown in fig. 2, the heating means may be introduced into the growth container from the upper cap and the lower cap, respectively.
Optionally, as shown in fig. 3, the corrosion prevention bushing is a double-layer structure, and includes a corrosion prevention bushing and a corrosion prevention layer, where the corrosion prevention bushing and the partition plate 40 may be connected into a whole by welding, and the corrosion prevention bushing uses austenitic stainless steel or nickel-based alloy, etc. which is more excellent in corrosion resistance than the inner cylinder, and preferably, the austenitic stainless steel uses 316L, and the nickel-based alloy uses Inconel 625 alloy; the anti-corrosion layer is made of precious metals or alloys thereof, such as platinum Pt, iridium Ir, gold Au, silver Ag, palladium Pd, rhodium Rh, ruthenium Ru and the like. Precious metals such as platinum Pt, iridium Ir, gold Au, silver Ag, palladium Pd, rhodium Rh, ruthenium Ru, and alloys thereof are disposed inside the corrosion prevention bush by one or a combination of one or more of bush, welding, and plating. The anti-corrosion lining and the anti-corrosion layer are arranged on the inner side of the inner cylinder body together in a sleeving manner. Optionally, a water cooling groove may be provided on the outside of the erosion protection lining.
The embodiment of the invention also discloses a gallium nitride single crystal growth method, based on the growth container 10 provided by the embodiment of the invention, as shown in fig. 4, the growth method comprises the following steps:
step S01: a partition plate 40 is provided in the growth container 10 to divide the growth container into a growth region and a raw material region. Preferably, the thickness of the partition 40 is 50mm or more, so that a temperature gradient is generated between the temperature fields of the growth zone and the raw material zone, as shown in fig. 5;
step S02: placing seed crystals 50 in the growth area, placing gallium nitride polycrystalline raw materials 70 in the raw material area, and placing mineralizers in the growth container;
step S03: sealing the growth container, and filling the growth container with an ammonia solvent after vacuumizing;
step S04: respectively heating the growth area and the raw material area by adopting a heating device, providing a first temperature for the growth area, providing a second temperature for the raw material area, and enabling a temperature difference to exist between the growth area and the raw material area; under the first temperature and the second temperature, the ammonia solvent in the growth container is in a subcritical/supercritical state, convection flow is generated between the growth area and the raw material area, gallium nitride seed crystals are spontaneously generated in the growth area, or gallium nitride seed crystals in the growth area are promoted to continuously grow;
step S05: after the growth of the gallium nitride single crystal is completed, the gallium nitride single crystal is taken out, the growth container is cleaned and dried, and then the process returns to step S01 to grow the gallium nitride single crystal again.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the method disclosed by the embodiment, the method corresponds to the product disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the product part for description.
In this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, the use of the verb "comprise a" to define an element does not exclude the presence of another, identical element in a process, method, article, or apparatus that comprises the element.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the embodiments. Thus, the present embodiments are not intended to be limited to the embodiments shown herein but are to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The gallium nitride monocrystal growing apparatus includes one growth container, one frame outside the growth container, and one heater inside the growth container.
The growth container comprises an end cover, a cylinder and a sealing structure, and a closed space formed by the end cover, the cylinder and the sealing structure provides a growth environment for the gallium nitride single crystal;
the frame is used for supporting the growth container and fixing the end cover of the growth container so as to counteract the axial force caused by ultrahigh pressure in the growth container;
the heating device is used for heating the ammonia solvent in the growth container to enable the ammonia solvent to be in a subcritical/supercritical state;
all parts of the growth container which are contacted with the ammonia solvent are provided with an anti-corrosion lining or an anti-corrosion layer.
2. The growth vessel of claim 1, wherein the growth vessel cylinder is composed of an inner cylinder body and a prestressed flat steel wire or flat steel belt wound on the outer wall of the inner cylinder body, the inner cylinder body is made of a high-strength gun steel forging, a low-alloy steel forging or steel plate, a stainless steel forging or steel plate, or a stainless steel composite plate, and the flat steel wire is made of spring steel, and the flat steel belt is made of low-alloy steel.
3. The growth vessel of claim 1 wherein the growth vessel end closure is fabricated from a high strength gun steel forging, a low alloy steel forging or plate, a stainless steel forging or plate, or a stainless steel composite plate.
4. The growth vessel of claim 1 wherein the growth vessel inner cylinder and end caps are provided with water cooling channels or plates to cool the growth vessel cylinder and end caps, the growth vessel cylinder and end caps metal temperature not exceeding 425 ℃.
5. The growth vessel of claim 1 wherein the sealing structure is an O-ring, B-ring, C-ring, Bridgman seal, Grayloc seal, wedge ring seal, or the like, or any one or more of the foregoing sealsThe sealing structure ensures the sealing performance of the growth container under the working conditions of vacuum, high temperature and ultrahigh pressure, and the leakage rate is less than or equal to 1.0 × 10-12Pa·m3/s。
6. The frame according to claim 1, wherein the frame is a member formed by winding prestressed flat steel wires around vertical columns, semicircular beams, or the like.
7. The heating device according to claim 1, wherein the heating body is a resistance wire heating body, a heating sleeve is arranged in the growth container, and the heating body connecting wire is led out from an end cover of the growth container.
8. The growth apparatus according to claim 1, wherein the corrosion prevention lining or the corrosion prevention layer has a single-layer or double-layer structure, and the side of the single-layer or double-layer structure which is in contact with the ammonia solvent is made of a noble metal such as platinum Pt, iridium Ir, gold Au, silver Ag, palladium Pd, rhodium Rh, ruthenium Ru, or an alloy thereof.
9. The corrosion protection lining or layer of claim 7 wherein said precious metal or alloy thereof is selected from the group consisting of platinum Pt, iridium Ir, gold Au, silver Ag, palladium Pd, rhodium Rh, ruthenium Ru, and combinations thereof by lining, welding, and plating.
10. A method for growing a gallium nitride single crystal, using the growing apparatus according to any one of claims 1 to 9, the method comprising:
arranging a partition plate in the growth container, and dividing the growth container into a growth area and a raw material area;
seed crystals are placed in the growth area, gallium nitride polycrystalline raw materials are placed in the raw material area, and mineralizers are placed in the growth container;
sealing the growth container, and filling the growth container with an ammonia solvent after vacuumizing;
respectively heating the growth area and the raw material area by adopting a heating device, providing a first temperature for the growth area, providing a second temperature for the raw material area, and enabling a temperature difference to exist between the growth area and the raw material area; the ammonia solvent in the growth container generates convection flow between the growth area and the raw material area, and the gallium nitride seed crystals are spontaneously generated in the growth area or the gallium nitride seed crystals in the growth area are promoted to continuously grow;
after the growth of the gallium nitride single crystal is completed, the gallium nitride single crystal is taken out, the growth container is cleaned and dried, and then the process returns to step S01 to grow the gallium nitride single crystal again.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114438582A (en) * | 2022-01-11 | 2022-05-06 | 武汉大学 | Reaction kettle structure for improving growth speed of ammonothermal gallium nitride crystal |
| CN117253773A (en) * | 2023-11-10 | 2023-12-19 | 雅安宇焜芯材材料科技有限公司 | Heating preparation system for semiconductor manufacturing |
| WO2024103009A1 (en) * | 2022-11-11 | 2024-05-16 | Slt Technologies, Inc. | Direct heating and temperature control system for crystal growth |
| WO2024103027A1 (en) * | 2022-11-11 | 2024-05-16 | Slt Technologies, Inc. | Apparatus for retrograde solvothermal crystal growth, method of making, and method of use |
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2020
- 2020-06-18 CN CN202010557426.2A patent/CN111593398A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114438582A (en) * | 2022-01-11 | 2022-05-06 | 武汉大学 | Reaction kettle structure for improving growth speed of ammonothermal gallium nitride crystal |
| WO2024103009A1 (en) * | 2022-11-11 | 2024-05-16 | Slt Technologies, Inc. | Direct heating and temperature control system for crystal growth |
| WO2024103027A1 (en) * | 2022-11-11 | 2024-05-16 | Slt Technologies, Inc. | Apparatus for retrograde solvothermal crystal growth, method of making, and method of use |
| CN117253773A (en) * | 2023-11-10 | 2023-12-19 | 雅安宇焜芯材材料科技有限公司 | Heating preparation system for semiconductor manufacturing |
| CN117253773B (en) * | 2023-11-10 | 2024-01-23 | 雅安宇焜芯材材料科技有限公司 | Heating preparation system for semiconductor manufacturing |
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