CN113774484B - 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
- Publication number
- CN113774484B CN113774484B CN202111069487.5A CN202111069487A CN113774484B CN 113774484 B CN113774484 B CN 113774484B CN 202111069487 A CN202111069487 A CN 202111069487A CN 113774484 B CN113774484 B CN 113774484B
- Authority
- CN
- China
- Prior art keywords
- gallium oxide
- crucible
- iridium
- crystal growth
- melt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—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
-
- 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
Abstract
The invention provides a gallium oxide crystal growth method and a combined crucible for growing gallium oxide crystals, which relate to the technical field of gallium oxide crystal growth, and the gallium oxide crystals are prepared by adopting the combined crucible, so that gallium oxide melt and an iridium crucible are not in direct contact, the problem that the quality of the gallium oxide crystals is affected because iridium element enters the gallium oxide melt is avoided, the high-temperature decomposition of gallium oxide is inhibited by evacuating original gas in a furnace and filling protective gas, meanwhile, the problem that dense corrosion pits appear on the side wall and the bottom of the crucible when the gallium oxide crystals are grown by adopting the iridium crucible, so that the loss of the iridium crucible is serious is solved, and finally, the prepared gallium oxide single crystal is transparent, has no obvious cracking and bubbles, and has the advantage of higher crystal crystallization quality compared with the gallium oxide single crystal prepared by adopting the existing method.
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 an ultra-wide band-gap semiconductor material, the band gap width can reach 4.9eV, and is known as a fourth-generation semiconductor material, compared with the third-generation wide band-gap semiconductor material, gallium oxide crystals have the advantages of larger band gap width, higher breakdown field strength and larger factor, and in addition, gallium oxide crystals can be prepared by using a melt method, so that the crystal growth cost is greatly reduced, and therefore, gallium oxide becomes a preferable material of an ultra-high voltage and ultra-high power device.
In the current gallium oxide crystal growth method, large-size high-quality crystals are mainly prepared by methods such as a pulling method, a guided mode method and the like. The above-described crystal growth methods all require the use of an iridium crucible. Due to the particularity of the gallium oxide material, the oxide of low-valence gallium and even simple substance gallium are easily decomposed under the condition of high temperature and oxygen deficiency, and the decomposition products can severely corrode the inner surface of the contacted iridium crucible, so that the noble metal is lost. Meanwhile, at high temperature, partial iridium metal enters into the melt and can influence the crystal quality, so that defects such as dislocation, twin crystal, mosaic and the like are generated in gallium oxide crystals.
Disclosure of Invention
The invention provides a gallium oxide crystal growth method and a combined crucible for growing gallium oxide crystals, which aims to overcome 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 provided with 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 iridium crucible positioned at the outer layer and a ceramic crucible positioned at the inner layer, and a space is reserved between the inner wall of the iridium crucible and the outer wall of the ceramic crucible; heating the combined crucible to melt the gallium oxide block into a gallium oxide melt; the gallium oxide melt adopts a melt method to carry out crystal growth.
Optionally, when the crystal growth is performed by a kyropoulos method, a casting method or a vertical Bridgman method, the method further comprises taking out and damaging the ceramic crucible after the crystal growth is finished, so that the complete gallium oxide crystal is obtained.
Optionally, the interval is 0.3 mm-0.8 mm.
Optionally, the iridium crucible has a wall thickness of 2-4 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 iridium crucible positioned at the outer layer and a ceramic crucible positioned at the inner layer, wherein a space is reserved between the inner wall of the iridium crucible and the outer wall of the ceramic crucible.
Optionally, the interval is 0.3 mm-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 summary, 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 enable gallium oxide melt and an iridium crucible not to be in direct contact, avoid that iridium element enters the gallium oxide melt to influence the quality of the gallium oxide crystals, inhibit high-temperature decomposition of gallium oxide by evacuating original gas in a furnace and charging protective gas, solve the problem that dense corrosion pits appear on the side wall and the bottom of the crucible when the gallium oxide crystals are grown by adopting the iridium crucible, cause serious loss of the iridium crucible, greatly reduce the preparation cost, and finally obtain gallium oxide single crystals which are transparent and have no obvious cracks and bubbles.
In addition, the space is reserved between the inner wall of the iridium crucible and the outer wall of the ceramic crucible, so that the ceramic crucible is relatively easy to take out from the iridium crucible when the crystal growth is carried out by adopting a kyropoulos method, a casting method and a vertical Bridgman method, and finally, the ceramic crucible is damaged to prepare complete gallium oxide crystals.
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of preferred embodiments, as illustrated in the accompanying drawings.
Drawings
Fig. 1 is a cross-sectional view showing a composite crucible provided by 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 with reference to specific examples for the purpose of facilitating understanding to those skilled in the art.
The present invention first provides a combination crucible for growing gallium oxide crystals by a gallium oxide crystal growth method.
Referring to fig. 1, a sectional view of a combined crucible according to an embodiment of the present invention is shown, wherein the combined crucible is composed of an iridium crucible 2 positioned at an outer layer and a ceramic crucible 1 positioned at an inner layer, and a space is provided between an inner wall of the iridium crucible 2 and an outer wall of the ceramic crucible 1. In this embodiment, the distance between the inner wall of the iridium crucible 2 and the outer wall of the ceramic crucible 1 is 0.3mm to 0.8mm.
The invention also provides a gallium oxide crystal growth method, which comprises the steps of installing the combined crucible provided with a gallium oxide 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 iridium crucible positioned at the outer layer and a ceramic crucible positioned at the inner layer, and a space is reserved between the inner wall of the iridium crucible and the outer wall of the ceramic crucible; heating the combined crucible to melt the gallium oxide block into a gallium oxide melt; the gallium oxide melt adopts a melt method to carry out crystal growth.
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:
and installing a plurality of thermal field components such as a thermal insulation material, a combined crucible and the like in the crystal growth furnace, ensuring that the thermal field components are horizontally and concentrically installed, arranging the combined crucible in the center of the thermal field, and placing a gallium oxide block into the ceramic crucible, wherein the gallium oxide block is 5N-level and sintered through a pressing block in the embodiment.
In this embodiment, the materials of the ceramic crucible include, but are not limited to, zirconia, boron nitride, pyrolytic boron nitride, and the wall thickness of the ceramic crucible is 2 mm-4 mm, if the wall thickness of the ceramic crucible is too thick, heat transfer is unfavorable, inductive power needs to be additionally improved, and if the wall thickness is too thin, the heat shock resistance of the crucible is poor, and the ceramic crucible is easy to crack, so that crystal growth failure occurs.
In this example, the furnace door of the crystal growth furnace was closed, and the vacuum in the furnace was reduced to 1X 10 by mechanical pumping - 3 And after Pa, filling carbon dioxide as protective gas to make the air pressure in the furnace be one atmosphere, and opening a circulating cooling water device, wherein the heat-insulating material is zirconia fiber brick. In other embodiments, a mixed gas of carbon dioxide and inert gas with different gas pressures or a gas for inhibiting pyrolysis of gallium oxide may be introduced as the shielding gas. The original gas in the furnace is pumped out and protective gas is filled in to inhibit the high-temperature decomposition of gallium oxide, so that the problem of iridium crucible loss caused by corrosion of low-valence gallium oxide or simple substance gallium generated by the decomposition of gallium oxide to the iridium crucible is solved.
And (3) turning on an intermediate frequency induction heating device, melting a gallium oxide block in the crucible at a heating power rate of 500W/h, monitoring the temperature of the crucible and the temperature of the block by using an infrared thermometer, and when the power is added to the gallium oxide block to be completely melted, keeping the temperature of the melt 10 ℃ higher than the melting point of gallium oxide for 1-2 hours, reducing the heating power to cool the melt to the melting point of gallium oxide and keeping the temperature for 1-2 hours.
Maintaining the micro positive pressure state in the furnace, and performing Czochralski crystal growth: firstly, loading a crystal seed on a seed rod, ensuring that the seed rod is positioned at the center of a crucible, slowly descending the gallium oxide seed to a position 3-5 mm above a melt for baking, starting seeding after 10-20 minutes, controlling seeding necking operation after 3-5 mm of the seed is melted, and carrying out shouldering and equal-diameter growth when the diameter of the seed is reduced to 1 mm.
The pulling speed of the crystal is 2mm/h, the rotating speed is 2rpm, the medium frequency induction power is reduced at the speed of 40W/h in the process of constant diameter growth, the crystal is rapidly pulled to separate from the melt when the crystal growth is finished, the power is reduced at the speed of 400W/h after the crystal growth is finished, the temperature is cooled to the room temperature, and the infrared thermometer is used for measuring that the temperature of the crystal in the crucible is reduced to 1400 ℃, and the carbon dioxide in the furnace is replaced with argon when the temperature of the crystal in the crucible is reduced.
The above parameter conditions are only a preferred embodiment of preparing gallium oxide crystals by adopting the czochralski method, and those skilled in the art can dynamically adjust the above parameter ranges as required, so that the description thereof is omitted herein.
In this embodiment, the gallium oxide crystal is prepared by using the Czochralski method with the combined crucible, so that the gallium oxide melt is not in direct contact with the iridium crucible, the problem that the quality of the gallium oxide crystal is affected because iridium element enters the gallium oxide melt is avoided, meanwhile, the problem that when the gallium oxide crystal is grown by using the iridium crucible, dense corrosion pits appear on the side wall and the bottom of the crucible, so that the loss of the iridium crucible is serious is solved, the finally prepared gallium oxide single crystal is transparent, no obvious cracking or bubbles exist, and compared with the gallium oxide single crystal prepared by the existing Czochralski method, the gallium oxide single crystal has higher crystal quality, and then the gallium oxide single crystal is subjected to cutting, grinding, polishing and other processing to obtain the gallium oxide single crystal substrate slice.
In the gallium oxide crystal growth method provided by the first embodiment of the invention, the combined crucible consisting of the iridium crucible and the ceramic crucible is adopted to replace the traditional iridium crucible for gallium oxide crystal growth, the outer iridium crucible has good heat conductivity, the heat of the intermediate frequency induction heating device can be conducted to the inner ceramic crucible, and the inner ceramic crucible is used for containing a gallium oxide block and melted gallium oxide melt.
In addition, when the crystal growth is performed by the kyropoulos method, the casting method and the vertical Bridgman method in the melt method, the additional steps of taking out and destroying the ceramic crucible are included after the crystal growth is completed.
The second embodiment of the invention adopts a kyropoulos method and the combined crucible to grow gallium oxide crystals, and comprises the following specific steps:
and installing a plurality of thermal field components such as a thermal insulation material, a combined crucible and the like in the crystal growth furnace, ensuring that the thermal field components are horizontally and concentrically installed, arranging the combined crucible in the center of the thermal field, and placing a gallium oxide block into the ceramic crucible, wherein the gallium oxide block is 5N-level and sintered through a pressing block in the embodiment.
In this embodiment, the materials of the ceramic crucible include, but are not limited to, zirconia, boron nitride, pyrolytic boron nitride, and the wall thickness of the ceramic crucible is 2 mm-4 mm, and the wall thickness and reasons of the ceramic crucible in this embodiment are the same as those described in the first embodiment, and are not described herein again.
In the embodiment, the interval between the inner wall of the iridium crucible and the outer wall of the ceramic crucible is 0.3-0.8 mm, if the interval between the two crucibles is too small, the ceramic crucible is easily crushed and broken due to the difference of the thermal expansion coefficients between the crucibles in the process of raising and lowering the temperature of crystal growth, and meanwhile, once the ceramic crucible is not easy to be crushed and separated after the later crystal growth is finished; however, if the distance between the two crucibles is too large, the heat transfer before combining the crucibles is affected and the thermal efficiency is greatly reduced.
In this example, the furnace door of the crystal growth furnace was closed, and the vacuum in the furnace was reduced to 1X 10 by mechanical pumping - 3 And after Pa, filling carbon dioxide as protective gas to make the air pressure in the furnace be one atmosphere, and opening a circulating cooling water device, wherein the heat-insulating material is zirconia fiber brick. In other embodiments, a mixed gas of carbon dioxide and inert gas with different gas pressures or other gases capable of inhibiting pyrolysis of gallium oxide can be introduced as the shielding gas. The original gas in the furnace is pumped out and protective gas is filled in to inhibit the high-temperature decomposition of gallium oxide, so that the problem of iridium crucible loss caused by corrosion of low-valence gallium oxide or simple substance gallium generated by the decomposition of gallium oxide to the iridium crucible is solved.
And (3) turning on an intermediate frequency induction heating device, melting a gallium oxide block in the crucible at a heating power rate of 500W/h, monitoring the temperature of the crucible and the temperature of the block by using an infrared thermometer, and when the power is added to the gallium oxide block to be completely melted, keeping the temperature of the melt 10 ℃ higher than the melting point of gallium oxide for 1-2 hours, reducing the heating power to cool the melt to the melting point of gallium oxide and keeping the temperature for 1-2 hours.
Maintaining the micro-positive pressure state in the furnace, and carrying out kyropoulos crystal growth: loading a crystal seed on a seed rod, ensuring that the seed rod is positioned at the center of a crucible, slowly descending the gallium oxide seed to a position 3-5 mm above a melt for baking, starting seeding after 10-20 minutes at a rotating speed of 2rpm, controlling the seed to melt off 3-5 mm, performing seeding necking operation, and performing shouldering and equal-diameter growth when the diameter of the seed is reduced to 1 mm.
Firstly, pulling at a speed of 0.4mm/h, after the crystal grows to 50-80 mm, pulling at a speed of 0.1mm/h, stopping rotating the crystal in the shouldering and subsequent processes, and adjusting the heating power to ensure that the weight of the crystal can steadily increase until the weight is not increased, wherein the crystal growth is ended. The power is reduced at the speed of 100W/h, when the temperature of the crystal in the crucible is measured by an infrared thermometer and is reduced to 1400 ℃, the carbon dioxide in the furnace is replaced by argon, and when the temperature of the gallium oxide crystal is measured by the infrared thermometer and is lower than 1000 ℃, the power reduction speed can be increased to 250W/h, so that the crystal is gradually cooled.
When the temperature in the furnace is completely reduced to room temperature, the single crystal growth furnace is opened to take out the crucible, the ceramic crucible is taken out from the iridium crucible, the ceramic crucible is damaged, a whole gallium oxide single crystal can be completely taken out, the single crystal can be observed to be transparent, obvious cracking and bubbles are avoided, and the single crystal substrate slice can be obtained through cutting, grinding, polishing and other processing.
The above parameter conditions are only a preferred embodiment of preparing gallium oxide crystals by using a kyropoulos method, and those skilled in the art can dynamically adjust the above parameter ranges as required, so that the description thereof will not be repeated here.
In a third embodiment of the invention, gallium oxide crystals are grown by a casting method and the combined crucible, and the method comprises the following specific steps:
and installing a plurality of thermal field components such as a thermal insulation material, a combined crucible and the like in the crystal growth furnace, ensuring that the thermal field components are horizontally and concentrically installed, arranging the combined crucible in the center of the thermal field, and placing a gallium oxide block which is 5N-level and is sintered by a pressing block into a ceramic crucible.
In this embodiment, the materials of the ceramic crucible include, but are not limited to, zirconia, boron nitride, pyrolytic boron nitride, and the wall thickness of the ceramic crucible is 2 mm-4 mm, and the wall thickness and reasons of the ceramic crucible in this embodiment are the same as those described in the first embodiment, and are not described herein again.
In this embodiment, the distance between the inner wall of the iridium 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 iridium 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 will not be described here again.
In this example, the furnace door of the crystal growth furnace was closed, and the vacuum in the furnace was reduced to 1X 10 by using a mechanical pump -3 And after Pa, filling carbon dioxide as protective gas to make the air pressure in the furnace be one atmosphere, and opening a circulating cooling water device, wherein the heat-insulating material is zirconia fiber brick. Carbon dioxide is selected as the shielding gas. In other embodiments, a mixed gas of carbon dioxide and inert gas with different gas pressures or a gas for inhibiting pyrolysis of gallium oxide may be introduced as the shielding gas. The original gas in the furnace is pumped out and protective gas is filled in to inhibit the high-temperature decomposition of gallium oxide, so that the problem of iridium crucible loss caused by corrosion of low-valence gallium oxide or simple substance gallium generated by the decomposition of gallium oxide to the iridium crucible is solved.
And (3) turning on an intermediate frequency induction heating device, melting a gallium oxide block in the crucible at a heating power rate of 500W/h, monitoring the temperature of the crucible and the temperature of the block by using an infrared thermometer, and when the power is added to the gallium oxide block to be completely melted, keeping the temperature of the melt 10 ℃ higher than the melting point of gallium oxide for 1-2 hours, reducing the heating power to cool the melt to the melting point of gallium oxide and keeping the temperature for 1-2 hours.
Crystal growth by casting method is carried out: cooling at a first target rate to enable the melt at the center of the upper surface of the crucible to form nuclei for growth, and gradually and directionally growing gallium oxide crystals by controlling a reasonable temperature gradient; when the temperature of gallium oxide crystals in the combined crucible is reduced to a first target temperature, replacing carbon dioxide gas in the furnace with argon gas; when the temperature of the gallium oxide crystal in the combined crucible is reduced to the second target temperature, the temperature in the furnace is reduced at the second target rate to reach the room temperature, so that the crystal growth is finished.
In this example, the first target rate is 40W/h, the first target temperature is 1400 ℃, the second target temperature is 1000 ℃, and the second target rate is 250W/h. The above parameters are only one preferred embodiment of preparing gallium oxide crystals by casting, and those skilled in the art can dynamically adjust the above parameters according to need, so they will not be described herein.
When the temperature in the furnace is completely reduced to room temperature, the crystal growth furnace is opened to take out the combined crucible, then the ceramic crucible is taken out of the iridium crucible, the ceramic crucible is damaged, a whole gallium oxide single crystal can be completely taken out, the gallium oxide single crystal can be observed to be transparent, obvious cracking and bubbles are avoided, and a single crystal substrate slice can be obtained through cutting, grinding, polishing and other processing.
The fourth embodiment of the invention adopts the vertical Bridgman method and the combined crucible to grow gallium oxide crystals, and comprises the following specific steps:
the growth furnace of the embodiment also uses the original equipment, and the heating mode adopts the medium frequency induction, so that the description is omitted.
In this embodiment, the materials of the ceramic crucible include, but are not limited to, zirconia, boron nitride, pyrolytic boron nitride, and the wall thickness of the ceramic crucible is 2 mm-4 mm, and the wall thickness and reasons of the ceramic crucible in this embodiment are the same as those described in the first embodiment, and are not described herein again.
In this embodiment, the distance between the inner wall of the iridium 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 iridium 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 will not be described here again.
And driving the combined crucible or the heater to vertically move by a driving device to start crystal growth until the crystal growth is finished. In the crystal growth process, 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 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 the room temperature, opening the single crystal growth furnace to take out the crucible. The ceramic crucible is taken out from the iridium crucible, the ceramic crucible is damaged, a whole gallium oxide single crystal can be completely taken out, the single crystal can be observed to be transparent, obvious cracking and bubbles are avoided, and the single crystal substrate slice can be obtained through cutting, grinding, polishing and other processing.
In the gallium oxide crystal growth methods provided by the second, third and fourth embodiments of the present invention, the gallium oxide melt and the iridium crucible are not in direct contact, so that the phenomenon that the quality of the gallium oxide crystal is affected by the iridium element entering the gallium oxide melt is avoided, and meanwhile, the problem that when the gallium oxide crystal is grown by using the iridium crucible, dense corrosion pits occur on the side wall and the bottom of the crucible, so that the loss of the iridium crucible is serious is solved, and finally, the prepared gallium oxide single crystal has higher crystal quality compared with the gallium oxide single crystal prepared by the technical scheme in the prior art.
In the gallium oxide crystal growing method provided by the second, third and fourth embodiments of the present invention, a space is provided between the inner wall of the iridium crucible and the outer wall of the ceramic crucible, so that the ceramic crucible can be relatively easily taken out from the iridium crucible, and finally, the ceramic crucible is damaged to obtain complete gallium oxide crystals.
Finally, any modification or equivalent replacement of some or all of the technical features by means of the structure of the device according to the invention and the technical solutions of the examples described, the resulting nature of which does not deviate from the corresponding technical solutions of the invention, falls within the scope of the structure of the device according to the invention and the patent claims of the embodiments described.
Claims (5)
1. A gallium oxide crystal growth method, characterized by comprising: installing a combined crucible provided with a gallium oxide 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 high-temperature decomposition of gallium oxide, wherein the combined crucible consists of an iridium crucible positioned at the outer layer and a ceramic crucible positioned at the inner layer, and a space is reserved between the inner wall of the iridium crucible and the outer wall of the ceramic crucible; heating the combined crucible to melt the gallium oxide block into a gallium oxide melt; the gallium oxide melt adopts a melt method for crystal growth, and the melt method is a casting method or a vertical Bridgman method; and after the crystal growth is finished, taking out and damaging the ceramic crucible, so as to obtain the complete gallium oxide crystal.
2. The gallium oxide crystal growing method according to claim 1, wherein a distance between the inner wall of the iridium crucible and the outer wall of the ceramic crucible is 0.3mm to 0.8mm.
3. The gallium oxide crystal growing method according to claim 1, wherein the ceramic crucible has a wall thickness of 2mm to 4mm.
4. The gallium oxide crystal growing 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.
5. The gallium oxide crystal growing method according to claim 1, wherein the iridium crucible has a wall thickness of 2mm to 4mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111069487.5A CN113774484B (en) | 2021-09-13 | 2021-09-13 | Gallium oxide crystal growth method and combined crucible for growing gallium oxide crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111069487.5A CN113774484B (en) | 2021-09-13 | 2021-09-13 | Gallium oxide crystal growth method and combined crucible for growing gallium oxide crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113774484A CN113774484A (en) | 2021-12-10 |
| CN113774484B true CN113774484B (en) | 2023-05-02 |
Family
ID=78843180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111069487.5A Active CN113774484B (en) | 2021-09-13 | 2021-09-13 | Gallium oxide crystal growth method and combined crucible for growing gallium oxide crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113774484B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114561701B (en) * | 2021-06-07 | 2022-08-19 | 浙江大学杭州国际科创中心 | Method for growing gallium oxide single crystal by casting method and semiconductor device containing gallium oxide single crystal |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH062637B2 (en) * | 1987-07-13 | 1994-01-12 | 東洋炭素株式会社 | Single crystal pulling device |
| JPH06293588A (en) * | 1993-04-07 | 1994-10-21 | Komatsu Electron Metals Co Ltd | Production of semiconductor single crystal |
| JP3234711B2 (en) * | 1994-04-14 | 2001-12-04 | 住友電気工業株式会社 | Method for holding oxide melt and method for producing oxide crystal |
| JP2001261481A (en) * | 2000-01-11 | 2001-09-26 | Toyo Tanso Kk | Sheet for protecting inner surface of carbonaceous crucible |
| JP2008007353A (en) * | 2006-06-28 | 2008-01-17 | Sumitomo Metal Mining Co Ltd | Apparatus for growing sapphire single crystal and growing method using the same |
| CN103047860A (en) * | 2011-10-14 | 2013-04-17 | 重庆四联光电科技有限公司 | Double-crucible induction heating furnace |
| CN202390568U (en) * | 2011-12-19 | 2012-08-22 | 元亮科技有限公司 | Sapphire crucible for growing garnet type single crystal |
| WO2014148157A1 (en) * | 2013-03-21 | 2014-09-25 | 株式会社アライドマテリアル | Crucible for use in growing sapphire single crystal and method for growing sapphire single crystal |
| JP6606638B2 (en) * | 2014-07-14 | 2019-11-20 | 株式会社福田結晶技術研究所 | Method and apparatus for growing Fe-Ga based alloy single crystal |
| CN104152983A (en) * | 2014-08-01 | 2014-11-19 | 北京雷生强式科技有限责任公司 | Crucible for growing cadmium selenide crystal and growing method of cadmium selenide crystal |
| CN104372408B (en) * | 2014-12-15 | 2017-03-22 | 山东大学 | Large size gallium oxide single crystal Czochralski growing method under normal pressure |
| CN108823638A (en) * | 2018-09-10 | 2018-11-16 | 孟静 | The preparation method of large scale silicon ingot used for solar batteries |
-
2021
- 2021-09-13 CN CN202111069487.5A patent/CN113774484B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113774484A (en) | 2021-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101323978B (en) | Large size sapphire crystal preparing technology and growing apparatus thereof | |
| WO2021008159A1 (en) | Coil-movable temperature field structure suitable for czochralski method, and single crystal growth method | |
| US20110017124A1 (en) | Method and equipment for producing sapphire single crystal | |
| CN114232070B (en) | Double-cavity structure and method for growing gallium oxide crystal by Czochralski method | |
| JP6302192B2 (en) | Single crystal growth apparatus and method | |
| CN104372408A (en) | Large size gallium oxide single crystal Czochralski growing method under normal pressure | |
| CN102758249A (en) | Method for preparing colorless corundum monocrystal | |
| CN103806100B (en) | A kind of terraced method growing method of vertical temperature of five oxidation Tritanium/Trititanium polycrystalline | |
| CN113774484B (en) | Gallium oxide crystal growth method and combined crucible for growing gallium oxide crystal | |
| CN114059162B (en) | Gallium oxide crystal growth device and crystal growth method | |
| CN114164493A (en) | Growth structure and growth method for liquid-phase growth of aluminum nitride | |
| CN112501690A (en) | Growth method of sapphire single crystal | |
| CN113638048B (en) | Method for growing indium phosphide single crystal by VGF method | |
| CN215440759U (en) | Growth device for growing gallium oxide single crystal by Bridgman method | |
| CN113445125B (en) | Growing device and method for growing gallium oxide single crystal by crucible descent method | |
| CN110484965A (en) | A kind of gallium oxide crystal and its growing method and grower | |
| CN114737253B (en) | Single crystal furnace thermal field structure and method for growing large-size sapphire single crystal plate | |
| CN109280973B (en) | Temperature field structure for inhibiting garnet structure scintillation crystal from cracking and growth method thereof | |
| CN116657251A (en) | Device and method for growing silicon carbide crystals for multiple times by liquid phase method single furnace | |
| JP2017222537A (en) | Crucible, and single crystal growing unit and growing method | |
| CN114108083A (en) | Spliced crucible and gallium oxide crystal growth method | |
| CN101760774A (en) | Post-heater for reduction of internal thermal stress of crystal grown in Czochralski method | |
| CN103266346B (en) | The growth apparatus of a kind of crystal Pulling YVO4 crystal and growing method based on this growth apparatus | |
| CN110396719A (en) | A method of improving silicon ingot minority carrier life time | |
| JP2010265150A (en) | Method for producing sapphire single crystal and method for producing seed crystal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230316 Address after: 205-62, Building 1, Phase 5, Information Port, No. 733, Jianshe 3rd Road, Ningwei Street, Xiaoshan District, Hangzhou, Zhejiang Province, 311202 Applicant after: Hangzhou Garen Semiconductor Co.,Ltd. Address before: 310000 5th floor, No. 99, Shixin North Road, Xiaoshan District, Hangzhou City, Zhejiang Province Applicant before: Hangzhou International Science and technology innovation center of Zhejiang University |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |