CN113774484A - Gallium oxide crystal growth method and combined crucible for growing gallium oxide crystal - Google Patents
Gallium oxide crystal growth method and combined crucible for growing gallium oxide crystal Download PDFInfo
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 137
- 239000013078 crystal Substances 0.000 title claims abstract description 128
- 238000002109 crystal growth method Methods 0.000 title claims abstract description 15
- 239000000919 ceramic Substances 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 28
- 229910052741 iridium Inorganic materials 0.000 claims description 19
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000155 melt Substances 0.000 claims description 18
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 14
- 238000011049 filling Methods 0.000 claims description 10
- 229910052582 BN Inorganic materials 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 26
- 230000002829 reductive effect Effects 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 13
- 239000001569 carbon dioxide Substances 0.000 description 13
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 230000006698 induction Effects 0.000 description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 5
- 229910052733 gallium Inorganic materials 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000011449 brick Substances 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- C30B29/16—Oxides
-
- 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
- C30B11/002—Crucibles or containers for supporting the melt
-
- 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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/10—Crucibles or containers for supporting the melt
- C30B15/12—Double crucible methods
-
- 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
- C30B17/00—Single-crystal growth onto a seed which remains in the melt during growth, e.g. Nacken-Kyropoulos method
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention provides a gallium oxide crystal growth method and a combined crucible for growing gallium oxide crystals, and relates to the technical field of gallium oxide crystal growth.
Description
Technical Field
The invention relates to the field of gallium oxide crystal growth, in particular to a gallium oxide crystal growth method and a combined crucible for growing gallium oxide crystals.
Background
Gallium oxide is a semiconductor material with a super-wide forbidden band, the forbidden band width can reach 4.9eV, and the gallium oxide crystal is known as a fourth-generation semiconductor material, compared with a third-generation wide forbidden band semiconductor material, the gallium oxide crystal has the advantages of larger forbidden band width, higher breakdown field strength and larger factor, and in addition, the gallium oxide crystal can be prepared by utilizing the advantages of a melt method, so that the crystal growth cost is greatly reduced, and therefore, the gallium oxide becomes a preferable material for ultrahigh-voltage and ultrahigh-power devices.
At present, in a gallium oxide crystal growth method, a crystal with large size and high quality is prepared mainly by a pulling method, a mold guiding method and the like. The above crystal growth methods all require the use of an iridium crucible. Due to the particularity of the gallium oxide material, the gallium oxide material is very easy to decompose under the condition of high temperature and oxygen deficiency to generate low-valence gallium oxide or even simple gallium, and the decomposition products can seriously corrode the inner surface of the iridium crucible in contact with the gallium oxide material, so that the loss of noble metals is caused. Meanwhile, at high temperature, partial iridium metal enters the melt to influence the crystal quality, so that defects such as dislocation, twin crystal, mosaic and the like are generated in the gallium oxide crystal.
Disclosure of Invention
The invention provides a gallium oxide crystal growth method and a combined crucible for growing gallium oxide crystals, aiming at overcoming the defects of the prior art.
In order to achieve the above object, an embodiment of the present invention provides a gallium oxide crystal growth method, including: installing a combined crucible containing a gallium oxide material block at the center of a thermal field in a crystal growth furnace, evacuating original gas in the furnace and filling protective gas, wherein the combined crucible consists of an iraurita crucible positioned at the outer layer and a ceramic crucible positioned at the inner layer, and a space is formed between the inner wall of the iraurita crucible and the outer wall of the ceramic crucible; heating the combined crucible to melt the gallium oxide blocks into gallium oxide melt; and the gallium oxide melt is subjected to crystal growth by a melt method.
Optionally, when the crystal growth is performed by using a kyropoulos method, a casting method and a vertical bridgeman method, the method further comprises taking out and destroying the ceramic crucible after the crystal growth is finished, so as to obtain a complete gallium oxide crystal.
Optionally, the distance is 0.3mm to 0.8 mm.
Optionally, the wall thickness of the iridium crucible is 2 mm-4 mm.
Optionally, the wall thickness of the ceramic crucible is 2 mm-4 mm.
Optionally, the ceramic crucible is one of a zirconia crucible, a boron nitride crucible, and a pyrolytic boron nitride crucible.
Optionally, the protective gas is carbon dioxide.
The embodiment of the invention also provides a combined crucible, which is used for growing gallium oxide crystals by a melt method and consists of an iraurita crucible positioned at the outer layer and a ceramic crucible positioned at the inner layer, wherein a space is formed between the inner wall of the iraurita crucible and the outer wall of the ceramic crucible.
Optionally, the distance is 0.3mm to 0.8 mm.
Optionally, the wall thickness of the ceramic crucible is 2 mm-4 mm.
Optionally, the ceramic crucible is one of a zirconia crucible, a boron nitride crucible, and a pyrolytic boron nitride crucible.
In conclusion, the beneficial effects of the invention are as follows:
the embodiment of the invention provides a gallium oxide crystal growth method and a combined crucible for growing gallium oxide crystals, which can prevent gallium oxide melt from directly contacting with an iraurita crucible, avoid the situation that iridium element enters the gallium oxide melt to influence the quality of the gallium oxide crystals, inhibit the high-temperature decomposition of the gallium oxide by evacuating original gas in a furnace and filling protective gas, solve the problems that dense corrosion pits can appear on the side wall and the bottom of the crucible when the iraurita crucible is used for growing the gallium oxide crystals, so that the loss of the iraurita crucible is serious, greatly reduce the preparation cost, ensure that the finally prepared gallium oxide single crystals are transparent and have no obvious cracks and bubbles, and have higher crystal crystallization quality compared with the gallium oxide single crystals prepared by the existing method.
In addition, the inner wall of the iraurita crucible and the outer wall of the ceramic crucible are spaced, when the kyropoulos method, the casting method and the vertical Bridgman method are adopted for crystal growth, the ceramic crucible is relatively easy to take out from the iraurita crucible, and finally, the ceramic crucible is damaged to prepare a complete gallium oxide crystal.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is a sectional view of an assembled crucible according to an embodiment of the present invention.
In the figure: 1-ceramic crucible, 2-iridium crucible.
Detailed Description
The present invention will be described in further detail below with reference to specific examples in order to facilitate understanding by those skilled in the art.
The present invention firstly provides a composite crucible for growing a gallium oxide crystal by a gallium oxide crystal growth method.
Referring to fig. 1, a sectional view of a composite crucible according to an embodiment of the present invention is shown, the composite crucible is composed of an iraurita crucible 2 located at an outer layer and a ceramic crucible 1 located at an inner layer, and a space is formed between an inner wall of the iraurita crucible 2 and an outer wall of the ceramic crucible 1. In the present embodiment, the distance between the inner wall of the iraurita crucible 2 and the outer wall of the ceramic crucible 1 is 0.3mm to 0.8 mm.
The invention also provides a gallium oxide crystal growth method, which comprises the steps of installing the combined crucible containing the gallium oxide material block at the center of a thermal field in a crystal growth furnace, evacuating original gas in the furnace and filling protective gas to inhibit the pyrolysis of gallium oxide, wherein the combined crucible consists of an iraurita crucible positioned at the outer layer and a ceramic crucible positioned at the inner layer, and a space is formed between the inner wall of the iraurita crucible and the outer wall of the ceramic crucible; heating the combined crucible to melt the gallium oxide blocks into gallium oxide melt; and the gallium oxide melt is subjected to crystal growth by a melt method.
The first embodiment of the invention adopts a Czochralski method and the combined crucible to grow gallium oxide crystals, and comprises the following specific steps:
a plurality of thermal field components such as heat insulation materials and a combined crucible are arranged in a crystal growth furnace, the thermal field components are ensured to be arranged horizontally and concentrically, the combined crucible is positioned at the center of a thermal field, and a gallium oxide material block is put into a ceramic crucible, wherein the gallium oxide material block is 5N grade and is sintered by a pressure block.
In this embodiment, the material of the ceramic crucible includes and is not limited to zirconia, boron nitride, pyrolytic boron nitride, and the ceramic crucible wall thickness is 2mm ~ 4mm, if the ceramic crucible wall thickness is too thick can be unfavorable for heat transfer, needs additionally to improve the power of response, if the wall thickness is too thin, the intensity variation of crucible thermal shock resistance, the easy fracture of ceramic crucible leads to growing brilliant failure.
In this embodiment, the furnace door of the crystal growth furnace is closed, and the furnace is evacuated by a mechanical pump until the vacuum degree in the furnace is reduced to 1 × 10- 3And (3) after Pa, filling carbon dioxide as a protective gas to ensure that the air pressure in the furnace is one atmosphere, opening the circulating cooling water device, and selecting a zirconium oxide fiber brick as a heat-insulating material. In other embodiments, a mixed gas of carbon dioxide and an inert gas with different pressures or a gas for inhibiting gallium oxide from pyrolysis can be introduced as the protective gas. The high-temperature decomposition of the gallium oxide is inhibited by evacuating the original gas in the furnace and filling the protective gas, so that the problem of iridium crucible loss caused by corrosion of the iridium crucible by low-valence gallium oxide or simple substance gallium generated by gallium oxide decomposition is solved.
Opening the medium-frequency induction heating device, melting the gallium oxide material block in the crucible at a heating power rate of 500W/h, monitoring the temperature of the crucible and the material block by using an infrared thermometer, when the power is added to completely melt the gallium oxide material block, keeping the temperature of the melt at 10 ℃ higher than the melting point of gallium oxide for 1-2 hours, reducing the heating power to reduce the temperature of the melt to the melting point of gallium oxide, and keeping for 1-2 hours.
Maintaining the micro positive pressure state in the furnace, and carrying out crystal growth by a Czochralski method: firstly, crystal seed crystals are loaded on a seed crystal rod, the seed crystal rod is ensured to be positioned at the central position of a crucible, gallium oxide seed crystals slowly descend to the position 3-5 mm above a melt for baking, seeding is started after 10-20 minutes, seeding and necking operation are carried out after the seed crystals are melted down by 3-5 mm, and when the diameter of the seed crystals is narrowed to 1mm, shouldering and isodiametric growth are carried out.
The pulling speed of the crystal is 2mm/h, the rotating speed is 2rpm, the medium frequency induction power is reduced at the rate of 40W/h in the process of equal-diameter growth, the crystal is pulled rapidly to be separated from the melt when the growth of the crystal is finished, the power is reduced at the speed of 400W/h after the growth of the crystal is finished, the crystal is cooled to the room temperature, and when the temperature of the crystal in the crucible is reduced to 1400 ℃, an infrared thermometer is utilized to replace carbon dioxide in the furnace to be argon.
The above parameter conditions are only one preferred embodiment for preparing gallium oxide crystal by Czochralski method, and can be dynamically adjusted within the above parameter ranges as required by those skilled in the art, and thus are not described herein again.
In the embodiment, because the gallium oxide crystal is prepared by adopting the Czochralski method of the combined crucible, the gallium oxide melt is not directly contacted with the iraurita crucible, the problem that the gallium oxide crystal quality is influenced because iridium element enters the gallium oxide melt is solved, and simultaneously, the problem that the iridium crucible is seriously lost due to dense corrosion pits on the side wall and the bottom of the crucible when the iridium crucible is used for growing the gallium oxide crystal is solved, the finally prepared gallium oxide single crystal is transparent and has no obvious cracks and air bubbles, compared with the gallium oxide single crystal prepared by the existing Czochralski method, the gallium oxide single crystal has higher crystal crystallization quality, and the gallium oxide single crystal is cut, ground, polished and the like to obtain the gallium oxide single crystal substrate slice.
In the method for growing a gallium oxide crystal provided by the first embodiment of the invention, the combined crucible composed of the iraurita crucible and the ceramic crucible is used for replacing the traditional iraurita crucible to grow the gallium oxide crystal, the iraurita crucible at the outer layer has good heat conductivity and can conduct the heat of the medium-frequency induction heating device to the ceramic crucible at the inner layer, and the ceramic crucible at the inner layer is used for containing the gallium oxide block and the melted gallium oxide melt, compared with the prior technical scheme for growing the gallium oxide crystal by adopting the iraurita crucible, the method has the function of protecting the iraurita crucible at the outer layer, solves the problem that the iraurita crucible is lost because the low-valence gallium oxide or simple substance gallium generated by decomposing the gallium oxide corrodes the iraurita crucible, simultaneously, the iraurita crucible and the gallium oxide melt are not in direct contact, and solves the problem that the quality of the gallium oxide crystal is influenced because the iridium element enters the gallium oxide melt at high temperature, thereby effectively reducing the internal defects of the gallium oxide crystal and improving the quality of the gallium oxide crystal.
In addition, when crystal growth is performed by the kyropoulos method, the casting method, the vertical bridgeman method among the melt methods, there is an additional step of taking out and breaking the ceramic crucible after the crystal growth is completed.
The second embodiment of the invention adopts the kyropoulos method and the combined crucible to grow the gallium oxide crystal, and comprises the following specific steps:
a plurality of thermal field components such as heat insulation materials and a combined crucible are arranged in a crystal growth furnace, the thermal field components are ensured to be arranged horizontally and concentrically, the combined crucible is positioned at the center of a thermal field, and a gallium oxide material block is put into a ceramic crucible, wherein the gallium oxide material block is 5N grade and is sintered by a pressure block.
In this embodiment, the material of the ceramic crucible includes, but is not limited to, zirconia, boron nitride, and pyrolytic boron nitride, the wall thickness of the ceramic crucible is 2mm to 4mm, and the wall thickness and reasons of the ceramic crucible in this embodiment are the same as those described in the first embodiment, and will not be described herein again.
In the embodiment, the distance between the inner wall of the iraurita crucible and the outer wall of the ceramic crucible is 0.3-0.8 mm, if the distance between the two crucibles is too small, the ceramic crucible is easily extruded and broken due to the difference of the thermal expansion coefficients of the crucibles in the temperature rising and falling process of crystal growth, and the two crucibles are separated once the ceramic crucible is extruded to be not beneficial to later-stage crystal growth; however, if the distance between the two crucibles is too large, heat transfer before the combination of the crucibles is affected, and the thermal efficiency is greatly lowered.
In this embodiment, the furnace door of the crystal growth furnace is closed, and the furnace is evacuated by a mechanical pump until the vacuum degree in the furnace is reduced to 1 × 10- 3And (3) after Pa, filling carbon dioxide as a protective gas to ensure that the air pressure in the furnace is one atmosphere, opening the circulating cooling water device, and selecting a zirconium oxide fiber brick as a heat-insulating material. In other embodiments, a mixed gas of carbon dioxide and inert gas with different pressures or other gases capable of inhibiting gallium oxide from pyrolysis can be introduced as the protective gas. The high-temperature decomposition of the gallium oxide is inhibited by evacuating the original gas in the furnace and filling the protective gas, so that the problem that the iridium crucible is lost due to the fact that the iridium crucible is corroded by low-valence gallium oxide or simple gallium generated by the decomposition of the gallium oxide is solved.
Opening the medium-frequency induction heating device, melting the gallium oxide material block in the crucible at a heating power rate of 500W/h, monitoring the temperature of the crucible and the material block by using an infrared thermometer, when the power is added to completely melt the gallium oxide material block, keeping the temperature of the melt at 10 ℃ higher than the melting point of gallium oxide for 1-2 hours, reducing the heating power to reduce the temperature of the melt to the melting point of gallium oxide, and keeping for 1-2 hours.
Maintaining the micro positive pressure state in the furnace, and carrying out kyropoulos method crystal growth: loading crystal seed crystals on a seed crystal rod, ensuring that the seed crystal rod is positioned at the central position of a crucible, slowly descending gallium oxide seed crystals to a position 3-5 mm above a melt for baking, starting seeding after 10-20 minutes, controlling the seed crystals to melt 3-5 mm, then carrying out seeding and necking operation, and when the diameter of the seed crystals is narrowed to 1mm, carrying out shouldering and isodiametric growth.
Pulling at the speed of 0.4mm/h, pulling at the speed of 0.1mm/h after the crystal grows to 50-80 mm, and adjusting the heating power to ensure that the weight of the crystal can be stably increased until the weight is not increased any more during shouldering and subsequent processes, wherein the crystal is pulled at the speed of 0.4mm/h and then pulled at the speed of 0.1 mm/h. The power is reduced at the speed of 100W/h, when the temperature of the crystal in the crucible is reduced to 1400 ℃ measured by an infrared thermometer, the carbon dioxide in the furnace is replaced by argon, and when the temperature of the gallium oxide crystal measured by the infrared thermometer is lower than 1000 ℃, the power reduction rate can be increased to 250W/h, so that the crystal is gradually cooled.
And when the temperature in the furnace is completely reduced to room temperature, opening the single crystal growth furnace, taking out the crucible, taking out the ceramic crucible from the iraurita crucible, destroying the ceramic crucible, completely taking out the whole gallium oxide single crystal, observing that the single crystal is transparent and has no obvious cracks and bubbles, and performing cutting, grinding, polishing and other processing to obtain the single crystal substrate slice.
The above parameter conditions are only one preferred embodiment for preparing gallium oxide crystal by kyropoulos method, and those skilled in the art can dynamically adjust the above parameter ranges according to the needs, so that the detailed description is omitted here.
In the third embodiment of the invention, a casting method and the combined crucible are adopted to grow gallium oxide crystals, and the method comprises the following specific steps:
a plurality of thermal field components such as heat insulation materials and a combined crucible are arranged in a crystal growth furnace, the thermal field components are ensured to be arranged horizontally and concentrically, the combined crucible is positioned at the center of a thermal field, and a gallium oxide material block which is 5N grade and sintered by a pressure block is put into a ceramic crucible.
In this embodiment, the material of the ceramic crucible includes, but is not limited to, zirconia, boron nitride, and pyrolytic boron nitride, the wall thickness of the ceramic crucible is 2mm to 4mm, and the wall thickness and reasons of the ceramic crucible in this embodiment are the same as those described in the first embodiment, and will not be described herein again.
In this embodiment, the distance between the inner wall of the iraurita crucible and the outer wall of the ceramic crucible is 0.3mm to 0.8mm, and the specific range and reason of the distance between the inner wall of the iraurita crucible and the outer wall of the ceramic crucible in this embodiment are the same as those described in the second embodiment of the present invention, and are not described herein again.
In this embodiment, the furnace door of the crystal growth furnace is closed, and the furnace is evacuated by a mechanical pump until the vacuum degree in the furnace is reduced to 1 × 10-3And (3) after Pa, filling carbon dioxide as a protective gas to ensure that the air pressure in the furnace is one atmosphere, opening the circulating cooling water device, and selecting a zirconium oxide fiber brick as a heat-insulating material. Carbon dioxide was chosen as the shielding gas. In other embodiments, a mixed gas of carbon dioxide and inert gas with different pressures or a mixture of carbon dioxide and inert gas with different pressures can be introducedThe gas for inhibiting the pyrolysis of gallium oxide is used as the protective gas. The high-temperature decomposition of the gallium oxide is inhibited by evacuating the original gas in the furnace and filling the protective gas, so that the problem that the iridium crucible is lost due to the fact that the iridium crucible is corroded by low-valence gallium oxide or simple gallium generated by the decomposition of the gallium oxide is solved.
Opening the medium-frequency induction heating device, melting the gallium oxide material block in the crucible at a heating power rate of 500W/h, monitoring the temperature of the crucible and the material block by using an infrared thermometer, when the power is added to completely melt the gallium oxide material block, keeping the temperature of the melt at 10 ℃ higher than the melting point of gallium oxide for 1-2 hours, reducing the heating power to reduce the temperature of the melt to the melting point of gallium oxide, and keeping for 1-2 hours.
Carrying out casting method crystal growth: cooling at a first target speed to ensure that the melt at the center cold center of the upper surface of the crucible nucleates and grows, and controlling a reasonable temperature gradient to gradually and directionally grow gallium oxide crystals; when the temperature of the gallium oxide crystal in the combined crucible is reduced to a first target temperature, replacing carbon dioxide gas in the furnace with argon; and when the temperature of the gallium oxide crystal in the combined crucible is reduced to a second target temperature, reducing the temperature at a second target speed to enable the temperature in the furnace to reach the room temperature so as to finish the crystal growth.
In this example, the first target rate was 40W/h, the first target temperature was 1400 deg.C, the second target temperature was 1000 deg.C, and the second target rate was 250W/h. The above parameter conditions are only one preferred embodiment of the preparation of gallium oxide crystal by casting method, and those skilled in the art can dynamically adjust the above parameter ranges according to the needs, so that the detailed description is omitted here.
And opening the crystal growth furnace to take out the combined crucible when the temperature in the furnace is completely reduced to room temperature, taking out the ceramic crucible from the iraurita crucible, destroying the ceramic crucible to completely take out the whole gallium oxide single crystal, observing that the gallium oxide single crystal is transparent and has no obvious cracks and bubbles, and performing cutting, grinding, polishing and other processing to obtain the single crystal substrate slice.
The fourth embodiment of the invention adopts the vertical Bridgman method and the combined crucible to grow the gallium oxide crystal, and the specific steps are as follows:
the growth furnace of this embodiment still uses original equipment, and the heating method adopts intermediate frequency induction, so no longer give consideration to repeatedly.
In this embodiment, the material of the ceramic crucible includes, but is not limited to, zirconia, boron nitride, and pyrolytic boron nitride, the wall thickness of the ceramic crucible is 2mm to 4mm, and the wall thickness and reasons of the ceramic crucible in this embodiment are the same as those described in the first embodiment, and will not be described herein again.
In this embodiment, the distance between the inner wall of the iraurita crucible and the outer wall of the ceramic crucible is 0.3mm to 0.8mm, and the specific range and reason of the distance between the inner wall of the iraurita crucible and the outer wall of the ceramic crucible in this embodiment are the same as those described in the second embodiment of the present invention, and are not described herein again.
And driving the combined crucible or the heater to vertically move through the driving device to start crystal growth until the crystal growth is finished. In the process of crystal growth, maintaining the micro-positive pressure state in the furnace, and replacing carbon dioxide in the furnace with argon when the temperature of the crystal in the crucible is reduced to 1400 ℃ by using an infrared thermometer;
when the temperature of the gallium oxide crystal measured by an infrared thermometer is lower than 1000 ℃, the power reduction rate can be increased to 250W/h, so that the crystal is gradually cooled. And opening the single crystal growth furnace and taking out the crucible when the temperature in the furnace is completely reduced to room temperature. And taking the ceramic crucible out of the iraurita crucible, destroying the ceramic crucible to completely take out the whole gallium oxide single crystal, observing that the single crystal is transparent and has no obvious cracks and bubbles, and processing by cutting, grinding, polishing and the like to obtain the single crystal substrate slice.
In the gallium oxide crystal growth methods provided in the second, third, and fourth embodiments of the present invention, the gallium oxide melt and the iraurita crucible are not in direct contact, so that the influence of iridium element entering the gallium oxide melt on the gallium oxide crystal quality is avoided, and simultaneously, the problem that dense corrosion pits occur on the side wall and the bottom of the crucible when the iraurita crucible is used for gallium oxide crystal growth, which causes severe loss of the iraurita crucible, is also solved.
In the gallium oxide crystal growth method provided in the second, third, and fourth embodiments of the present invention, a gap is provided between the inner wall of the iraurita crucible and the outer wall of the ceramic crucible, so that the ceramic crucible can be relatively easily taken out of the iraurita crucible, and finally the complete gallium oxide crystal is prepared by destroying the ceramic crucible.
Finally, it is to be noted that any modifications or equivalent substitutions of some or all of the features may be made by means of the structure of the device according to the invention and the technical solutions of the examples described, without departing from the corresponding technical solutions of the invention, and the obtained essence falls within the scope of the structure of the device according to the invention and the claims of the embodiments described.
Claims (10)
1. A method for growing a gallium oxide crystal, comprising: installing a combined crucible containing a gallium oxide material block at the center of a thermal field in a crystal growth furnace, evacuating original gas in the furnace and filling protective gas to inhibit pyrolysis of gallium oxide, wherein the combined crucible consists of an iraurita crucible positioned at an outer layer and a ceramic crucible positioned at an inner layer, and a space is formed between the inner wall of the iraurita crucible and the outer wall of the ceramic crucible; heating the combined crucible to melt the gallium oxide blocks into gallium oxide melt; and the gallium oxide melt is subjected to crystal growth by a melt method.
2. The method for growing a gallium oxide crystal according to claim 1, wherein, in the case of crystal growth by the kyropoulos method, the casting method, or the vertical bridgeman method, the method further comprises removing and destroying the ceramic crucible after the crystal growth is completed, thereby obtaining a complete gallium oxide crystal.
3. The method for growing a gallium oxide crystal according to claim 1, wherein a distance between an inner wall of the iridium crucible and an outer wall of the ceramic crucible is 0.3mm to 0.8 mm.
4. The method for growing a gallium oxide crystal according to claim 1, wherein the ceramic crucible has a wall thickness of 2mm to 4 mm.
5. The gallium oxide crystal growth method according to claim 1, wherein the ceramic crucible is one of a zirconia crucible, a boron nitride crucible, and a pyrolytic boron nitride crucible.
6. The gallium oxide crystal growth method according to claim 1, wherein the iridium crucible has a wall thickness of 2mm to 4 mm.
7. The combined crucible is used for growing gallium oxide crystals by a melt method and consists of an iraurita crucible positioned at an outer layer and a ceramic crucible positioned at an inner layer, wherein a space is formed between the inner wall of the iraurita crucible and the outer wall of the ceramic crucible.
8. The composite crucible of claim 7, wherein the spacing is 0.3mm to 0.8 mm.
9. The composite crucible of claim 7, wherein the ceramic crucible has a wall thickness of 2mm to 4 mm.
10. The composite crucible of claim 7, wherein the ceramic crucible is one of a zirconia crucible, a boron nitride crucible, and a pyrolytic boron nitride crucible.
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