CN114108086A - Crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method - Google Patents
Crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method Download PDFInfo
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- CN114108086A CN114108086A CN202111361482.XA CN202111361482A CN114108086A CN 114108086 A CN114108086 A CN 114108086A CN 202111361482 A CN202111361482 A CN 202111361482A CN 114108086 A CN114108086 A CN 114108086A
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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
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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
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
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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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
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Abstract
The invention discloses a design and preparation method of a crucible for preparing gallium oxide single crystals by a cold crucible method. Has the advantages that: the invention adopts the novel cold crucible and grows the gallium oxide single crystal by the cold crucible method, thereby effectively avoiding the corrosion of high-temperature melt to the crucible, reducing the pollution of the crucible to the melt, avoiding the use of noble metal crucibles such as iridium or platinum rhodium crucibles and the like, greatly reducing the cost of the crucible for preparing the gallium oxide single crystal, and further reducing the production cost of preparing the gallium oxide single crystal.
Description
Technical Field
The invention relates to the technical field of gallium oxide single crystal preparation, in particular to a crucible design and preparation method for preparing gallium oxide single crystal by a cold crucible method.
Background
The beta-Ga 2O3 single crystal is a transparent ultra-wide forbidden band oxide semiconductor material, the forbidden band width is about 4.8eV, the breakdown electric field intensity is up to 8MV/cm, which is far higher than that of semiconductor materials such as silicon, gallium arsenide, silicon carbide, gallium nitride and the like, and the single crystal also has the advantages of unique ultraviolet transmission characteristic (the ultraviolet transmission rate can reach more than 80%), low energy loss, high thermal stability and chemical stability, good controllability, low cost and the like, and is a preferred semiconductor material for manufacturing high-temperature high-frequency high-power microelectronic devices, deep ultraviolet electronic devices and ultraviolet transparent conductive electrodes. High quality single crystal substrates are an important basis for the fabrication of devices.
Because the gallium oxide single crystal has a high melting point (about 1820 ℃), the gallium oxide single crystal is easy to decompose and volatilize in the high-temperature growth process, so that the gallium oxide single crystal is unstable in the growth process, a large number of oxygen vacancies are easy to generate, and further defects such as twin crystals, mosaic structures, screw dislocation and the like are caused; in addition, gases such as GaO, Ga2O and Ga generated by decomposition of gallium oxide at high temperature severely corrode the crucible, the temperature field is difficult to control, defects are easy to generate in the single crystal, and the crystal shape is not well controlled, so that the growth of high-quality large-size beta-Ga 2O3 single crystal is very difficult.
The cold crucible method is a technology for growing crystals from a melt, and can effectively solve the problems of difficult melting, easy volatilization and the like of gallium oxide powder by heating with a high-frequency electromagnetic field. The cold crucible method can ensure that a strong magnetic compression effect exists in the crucible, and the electromagnetic repulsion force ensures that the furnace burden melt and the crucible are kept in a non-contact suspension rolling state, so that the chemical components and the temperature field in the molten pool are kept uniform. Meanwhile, the melt forms an extremely thin layer of skull on the inner wall of the crucible by the intensive cooling of the water, the components of the skull are close to those of the melt, the skull blocks the reaction between the alloy melt and the copper crucible, and the pollution of the crucible to crystals when the ceramic crucible is adopted for smelting in the past is avoided.
The cold crucible method has a plurality of outstanding advantages compared with other methods for growing crystals, the method has stronger applicability, and for most materials, a plurality of proper ignition agents can be found to grow single crystals; the cold crucible method has low growth temperature, many refractory compounds and materials which are extremely volatile at melting point or decompose to release gas due to valence change, and non-homogeneous molten compounds, and it is often impossible to grow complete single crystals directly from their melts, while the ignition method shows unique capability. Crystals grown in this way can be thermally less stressed and more uniformly integrated than melt grown crystals. In addition, the growth temperature of the cold crucible method is low, and the problems of the heating body of the crucible and the single crystal furnace, temperature measurement and temperature control are easy to solve.
At present, the gallium oxide single crystal is grown domestically by a die guide method or a pulling method, the temperature for growing the single crystal is high, used crucibles, dies and the like are made of noble metals such as iridium, rhodium and the like and are single-layer crucibles, the single crystal produced by the die guide method has high requirements on die equipment, complex operation process and high production cost, the phenomena of bubbles, polycrystal and the like are easy to appear in the single crystal, the slice quantity of the single crystal is small, and industrialization is difficult to realize; meanwhile, when the pulling method is used for producing the single crystal, the raw material components are easily influenced by external impurities, and the melting and volatilization phenomena of the raw materials are difficult to control.
Disclosure of Invention
The present invention aims to solve the above problems and provide a crucible design and a method for producing gallium oxide single crystals by the cold crucible method.
The invention realizes the purpose through the following technical scheme:
a design and preparation method of crucible used for preparing gallium oxide single crystal of cold crucible method, this cold crucible is formed by crucible wall, buffer layer and gallium oxide extrusion layer, wherein the said buffer layer attaches inside the said crucible wall and outside the said gallium oxide extrusion layer, the thickness of the said crucible wall is greater than the thickness of the said gallium oxide extrusion layer, the thickness of the said buffer layer is smaller than the thickness of the said gallium oxide extrusion layer; the method for preparing the gallium oxide single crystal by adopting the cold crucible comprises the following specific steps:
step 1: coating a layer of bonding coating slurry on the inner wall of the crucible wall, wherein the bonding coating slurry is used for connecting the crucible wall and the gallium oxide extrusion layer;
step 2: then pressing gallium oxide powder (5N) on the coating, and finally sintering;
and step 3: and annealing the sintered crucible to uniformly connect the interfaces to obtain the gallium oxide single crystal.
Furthermore, the crucible wall is a copper crucible, the buffer layer is high-temperature inorganic glue, the sintered crucible is annealed, the connection quality of two interfaces of the crucible is improved, the crucible is used for pulling gallium oxide single crystals or preparing the gallium oxide single crystals by a Bridgman method, the contact between the crucible wall and gallium oxide melt can be effectively avoided, and the content of impurities in the single crystals and the corrosion of the crucible are reduced.
Further, the sintering temperature in the step 2 is 1800-.
Further, the thickness of the crucible wall is 2-40mm, and the preferable thickness is 2-10 mm.
Further, the thickness of the buffer layer is 0.2-10mm, and the preferable thickness is 0.2-2 mm.
Further, the thickness of the gallium oxide extrusion layer is 0.5-2mm, and the preferred thickness is 0.5-2 mm.
Further, the height of the crucible is 1 to 800mm, preferably 20 to 200 mm.
Further, the heat treatment in the step 3 is performed under a protective atmosphere, the temperature of the heat treatment is 500-950 ℃, preferably 750-850 ℃, the time of the heat treatment is 1-6h, preferably 2-3h, the temperature rise rate is less than 10 ℃/min, preferably the temperature rate is 6-8 ℃/min, and preferably argon or nitrogen is used under the protective atmosphere.
Furthermore, the bottom corner of the cold crucible is connected in a clamping groove connection mode, a right-angle connection mode or an oblique-angle connection mode, the preferred connection mode is the oblique-angle connection mode, and the crucible can be conveniently taken after being used.
Furthermore, the crucible bottom is one of a circle and a polygon, and preferably, the crucible bottom is a circle, so that the crucible can be stably placed conveniently.
The invention has the beneficial effects that:
the invention adopts the novel cold crucible and grows the gallium oxide single crystal by the cold crucible method, thereby effectively avoiding the corrosion of high-temperature melt to the crucible, reducing the pollution of the crucible to the melt, avoiding the use of noble metal crucibles such as iridium or platinum rhodium crucibles and the like, greatly reducing the cost of the crucible for preparing the gallium oxide single crystal, and further reducing the production cost of preparing the gallium oxide single crystal.
Drawings
FIG. 1 is a structural diagram of a crucible used in the design and preparation method of a crucible for preparing gallium oxide single crystal by a cold crucible method according to the present invention.
The reference numerals are explained below:
1. a crucible wall; 2. a buffer layer; 3. and (4) extruding the gallium oxide layer.
Detailed Description
A design and preparation method of crucible used for preparing gallium oxide single crystal of cold crucible method, this cold crucible is formed by crucible wall 1, buffer layer 2 and gallium oxide extrusion layer 3, wherein the said buffer layer 2 attaches inside the said crucible wall 1 and outside the said gallium oxide extrusion layer 3, the thickness of the said crucible wall 1 is greater than the thickness of the said gallium oxide extrusion layer 3, the thickness of the said buffer layer 2 is smaller than the thickness of the said gallium oxide extrusion layer 3; the method for preparing the gallium oxide single crystal by adopting the cold crucible comprises the following specific steps:
step 1: coating a layer of bonding coating slurry on the inner wall of the crucible wall 1, wherein the bonding coating slurry is used for connecting the crucible wall 1 and the gallium oxide extrusion layer 3;
step 2: then pressing gallium oxide powder 5N onto the coating, and finally sintering;
and step 3: and annealing the sintered crucible to uniformly connect the interfaces to obtain the gallium oxide single crystal.
In the embodiment, the crucible wall 1 is a copper crucible, the buffer layer 2 is high-temperature inorganic glue, the sintered crucible is annealed to improve the connection quality of two interfaces of the crucible, and the crucible is used for pulling gallium oxide single crystals or preparing the gallium oxide single crystals by a Bridgman method, so that the contact between the crucible wall 1 and gallium oxide melt can be effectively avoided, and the content of impurities in the single crystals and the corrosion of the crucible are reduced.
In this embodiment, the sintering temperature in step 2 is 1800-.
In this embodiment, the thickness of the crucible wall 1 is 2-40mm, preferably 2-10mm, which facilitates heat conduction.
In this embodiment, the thickness of the buffer layer 2 is 0.2-10mm, and preferably 0.2-2 mm.
In this embodiment, the thickness of the gallium oxide extrusion layer 3 is 0.5-2mm, and preferably 0.5-2 mm.
In the embodiment, the height of the crucible is 1-800mm, preferably 20-200mm, so that the crucible is convenient to operate.
In this embodiment, the heat treatment in step 3 is performed under a protective atmosphere, the temperature of the heat treatment is 500-.
In this embodiment, the bottom corner of the cold crucible is connected in one of a clamping groove connection mode, a right-angle connection mode and an oblique-angle connection mode, and the preferred connection mode is the oblique-angle connection mode, so that the crucible can be conveniently taken after being used.
In this embodiment, the crucible bottom is one of a circle and a polygon, and preferably, the crucible bottom is a circle, which is convenient for stable placement of the crucible.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A design and preparation method of a crucible for preparing gallium oxide single crystal by a cold crucible method is characterized in that: the cold crucible is composed of a crucible wall (1), a buffer layer (2) and a gallium oxide extrusion layer (3), wherein the buffer layer (2) is attached to the inner side of the crucible wall (1) and the outer side of the gallium oxide extrusion layer (3), the thickness of the crucible wall (1) is larger than that of the gallium oxide extrusion layer (3), and the thickness of the buffer layer (2) is smaller than that of the gallium oxide extrusion layer (3); the method for preparing the gallium oxide single crystal by adopting the cold crucible comprises the following specific steps:
step 1: coating a layer of bonding coating slurry on the inner wall of the crucible wall (1) for connecting the crucible wall (1) and the gallium oxide extrusion layer (3);
step 2: then pressing gallium oxide powder (5N) on the coating, and finally sintering;
and step 3: and annealing the sintered crucible to uniformly connect the interfaces to obtain the gallium oxide single crystal.
2. The crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method according to claim 1, characterized in that: the crucible wall (1) is a copper crucible, the buffer layer (2) is high-temperature inorganic glue, and the sintered crucible is annealed to improve the connection quality of two interfaces of the crucible.
3. The crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method according to claim 1, characterized in that: the sintering temperature in the step 2 is 500-1800 ℃, and the preferable temperature is 900-1200 ℃.
4. The crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method according to claim 1, characterized in that: the thickness of the crucible wall (1) is 2-40mm, preferably 2-10 mm.
5. The crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method according to claim 1, characterized in that: the thickness of the buffer layer (2) is 0.2-10mm, and the preferable thickness is 0.2-2 mm.
6. The crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method according to claim 1, characterized in that: the thickness of the gallium oxide extrusion layer (3) is 0.5-2mm, and the preferred thickness is 0.5-2 mm.
7. The crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method according to claim 1, characterized in that: the height of the crucible is 1-800mm, preferably 20-200 mm.
8. The crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method according to claim 1, characterized in that: the heat treatment in the step 3 is carried out in a protective atmosphere, the temperature of the heat treatment is 500-950 ℃, the preferred treatment temperature is 750-850 ℃, the time of the heat treatment is 1-6h, the preferred heat treatment time is 2-3h, the heating rate is less than 10 ℃/min, the preferred temperature rate is 6-8 ℃/min, and argon or nitrogen is preferred in the protective atmosphere.
9. The crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method according to claim 1, characterized in that: the bottom corner of the cold crucible is connected in one of a clamping groove connection mode, a right-angle connection mode and an oblique-angle connection mode, and the preferred connection mode is the oblique-angle connection mode.
10. The crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method according to claim 1, characterized in that: the crucible bottom is one of circular and polygonal, and preferably the crucible bottom is circular.
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| CN202111361482.XA CN114108086A (en) | 2021-11-17 | 2021-11-17 | Crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method |
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| CN202111361482.XA CN114108086A (en) | 2021-11-17 | 2021-11-17 | Crucible design and preparation method for preparing gallium oxide single crystal by cold crucible method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115261973A (en) * | 2022-08-15 | 2022-11-01 | 中国科学院上海光学精密机械研究所 | Growth method of large-size gallium oxide crystal |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115261973A (en) * | 2022-08-15 | 2022-11-01 | 中国科学院上海光学精密机械研究所 | Growth method of large-size gallium oxide crystal |
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Application publication date: 20220301 |