CN116693329A - Preparation method of tantalum carbide coating, graphite crucible and silicon carbide crystal growth device - Google Patents
Preparation method of tantalum carbide coating, graphite crucible and silicon carbide crystal growth device Download PDFInfo
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- CN116693329A CN116693329A CN202310445017.7A CN202310445017A CN116693329A CN 116693329 A CN116693329 A CN 116693329A CN 202310445017 A CN202310445017 A CN 202310445017A CN 116693329 A CN116693329 A CN 116693329A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000010439 graphite Substances 0.000 title claims abstract description 136
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 136
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910003468 tantalcarbide Inorganic materials 0.000 title claims abstract description 117
- 238000000576 coating method Methods 0.000 title claims abstract description 81
- 239000011248 coating agent Substances 0.000 title claims abstract description 79
- 239000013078 crystal Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 17
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000000843 powder Substances 0.000 claims abstract description 65
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 61
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000005245 sintering Methods 0.000 claims abstract description 58
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 25
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000013522 chelant Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- OPZULYDYSMWNFK-UHFFFAOYSA-I butan-1-ol tantalum(5+) pentachloride Chemical compound [Cl-].C(CCC)O.[Ta+5].[Cl-].[Cl-].[Cl-].[Cl-] OPZULYDYSMWNFK-UHFFFAOYSA-I 0.000 claims description 3
- JVOQKOIQWNPOMI-UHFFFAOYSA-N ethanol;tantalum Chemical compound [Ta].CCO JVOQKOIQWNPOMI-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002245 particle Substances 0.000 abstract description 12
- 239000007770 graphite material Substances 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 27
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 230000001680 brushing effect Effects 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- -1 alcohol tantalum compounds Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5057—Carbides
-
- 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
- C30B29/36—Carbides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of third-generation semiconductors, in particular to a preparation method of a tantalum carbide coating, a graphite crucible and a silicon carbide crystal growth device. Comprising the following steps: preparation and utilization of Ta x O y C z The intermediate powder is used for preparing a suspension containing tantalum element, and the suspension is coated on the inner side wall and the inner bottom surface of a graphite crucible to form a precoating layer, and then the precoating layer is sintered for the second time to finally form a tantalum carbide coating. Ta x O y C z The intermediate powder is a mixture of liquid tantalum oxide and solid tantalum carbide formed in the sintering process, the tantalum oxide and graphite react chemically, a tantalum carbide coating is formed on the inner surface of the graphite crucible, so that the tantalum carbide coating is not easy to fall off, the liquid tantalum oxide drives solid tantalum carbide particles to flow on the inner surface of the graphite crucible, so that the tantalum carbide is filled in pores of a graphite material, and the compactness of the tantalum carbide coating on the inner surface of the graphite crucible is improved. At the same time, graphite crucibleThe inner side wall of the tantalum carbide coating is coated in a mode of dividing the inner side wall into an upper section, a middle section and a lower section with different precoat thicknesses, so that the compactness of the tantalum carbide coating is further improved.
Description
Technical Field
The invention relates to the technical field of third-generation semiconductors, in particular to a preparation method of a tantalum carbide coating, a graphite crucible and a silicon carbide crystal growth device.
Background
The third generation of semiconductor material silicon carbide is actively developed in the aspects of communication, photovoltaics, new energy automobiles and the like. Silicon carbide wafers are obtained by means of single crystal growth, the process temperature of the silicon carbide single crystal growth is up to 2300 ℃, a large amount of graphite materials are required to be used as a reaction container, and a graphite crucible is used as a common reaction container, so that the growth of the silicon carbide single crystal has great dependence on the high-purity graphite materials. However, the growth process of silicon carbide involves the reaction of silicon with carbon, resulting in corrosion of the surface of the graphite material in the growth environment of silicon carbide, and typically, the parts of the graphite material have a short life in the growth of silicon carbide crystals, some parts being 1 furnace-to-10 furnace-to-furnace, and some parts being 5 to 10 furnace-to-furnace. If the corroded graphite member is not replaced in time, crystal defects such as carbon inclusion introduced into the crystal are generated.
The research shows that the high-temperature-resistant coating is used for wrapping the graphite component, so that the corrosion of the graphite component in the silicon carbide growth atmosphere and the adverse effect on the single crystal growth are reduced, a high-quality ingot is obtained, the service life of the graphite component is prolonged, and the cost of single crystal growth is reduced.
Tantalum carbide coatings, which are capable of withstanding high temperatures of 2300 c due to their relatively high melting point, are considered to be promising coating materials for use in the growth of silicon carbide single crystals. Common methods for preparing tantalum carbide coatings are: CVD (chemical vapor deposition) method, molten salt method, sol-gel method, and the like. The CVD method needs to adopt a large amount of metal organic gas sources as reaction source materials, and has high risk; the tantalum carbide coating prepared by the molten salt method and the gel-sol method has weak bonding strength with the substrate, and the coating is not compact.
Disclosure of Invention
The invention provides a preparation method of a tantalum carbide coating, which aims to solve the technical problems and comprises the following steps:
preparation of Ta x O y C z An intermediate powder;
by using the Ta x O y C z Preparing a tantalum-containing suspension from the intermediate powder;
providing a graphite crucible with an inner side wall and an inner bottom surface, and coating the suspension containing tantalum element on the inner side wall of the graphite crucible and the inner bottom surface of the graphite crucible to form a precoat, wherein the thickness of the precoat of the inner side wall gradually increases along the direction of the inner bottom surface of the graphite crucible facing a graphite crucible opening;
and (3) performing second sintering on the graphite crucible coated with the precoat, wherein the precoat forms a mixture containing liquid tantalum oxide and solid tantalum carbide in the second sintering process, the tantalum oxide reacts with the graphite crucible, and the tantalum carbide fills pores of the graphite crucible, so that the tantalum carbide coating is finally formed.
Alternatively, ta is prepared x O y C z The step of intermediate powder comprises: preparing a first mixture containing tantalum element; pouring the first mixture into a reaction kettle to perform chelant reaction to obtain first powder containing tantalum; drying the first powder; performing first sintering on the dried first powder, wherein Ta is obtained after the first sintering x O y C z Intermediate powder.
Optionally, the content of tantalum element in the first mixture ranges from 0.2 mol/L to 0.8mol/L, the content of acetylacetone ranges from 0.2 mol/L to 0.8mol/L, and the ratio of the amounts of substances of tantalum element and oxygen element in the first mixture is 1:1 to 10.
Optionally, the temperature range of the first sintering of the dried first powder is 600-1400 ℃, and the time range of the first sintering is 1-10 h.
Optionally, the first mixture containing tantalum element includes: tantalum element-containing powder, acetylacetone and alcohol solution; wherein the tantalum-containing powder comprises: one or more of tantalum powder, tantalum chloride powder and tantalum carbide powder; the alcohol solution comprises one or more of n-butanol tantalum pentachloride solution and ethanol tantalum solution.
Optionally, the step of preparing the tantalum-containing suspension includes: taking a certain amount of Ta x O y C z The method comprises the steps of placing powder, tantalum-containing substances, an organic binder and an alcohol solution in a container, placing the container in an ultrasonic machine for mixing, and obtaining a suspension containing tantalum.
Optionally, the tantalum-containing material includes: one or more of tantalum powder, tantalum oxide powder and tantalum carbide powder; the organic binder is PVB or PVA; the mole ratio of tantalum element, oxygen element and carbon element in the suspension containing tantalum element is 1-10: 1-20: 1.
optionally, the precoating of the inner side wall is divided into an upper section, a middle section and a lower section for coating, wherein the upper section, the middle section and the lower section are the directions from the inner side wall of the graphite crucible to the inner bottom surface of the graphite crucible along the graphite crucible opening; the thickness range of the precoat layer at the upper section of the inner side wall of the graphite crucible is 400-500 mu m, the thickness range of the precoat layer at the middle section is 300-400 mu m, the thickness range of the precoat layer at the lower section is 100-300 mu m, and the thickness of the precoat layer at the inner bottom surface of the graphite crucible is 200-400 mu m.
Optionally, the graphite crucible coated with the precoat is placed in a high-temperature vacuum sintering furnace for second sintering, wherein the second sintering time range is 1-30 h, the second sintering temperature range is 1600-2400 ℃, and the heating rate before the second sintering is more than 20 ℃/min.
The embodiment of the invention also provides a graphite crucible, which comprises the graphite crucible and a tantalum carbide coating positioned on the inner side wall and the inner bottom surface of the graphite crucible, wherein the tantalum carbide coating is prepared by the method of any one of the above.
The embodiment of the invention also provides a silicon carbide crystal growing device comprising the graphite crucible.
In summary, the invention has the advantages that:
the invention provides a preparation method of a tantalum carbide coating, a graphite crucible and a silicon carbide crystal growth device, which comprise the following steps: preparation of Ta x O y C z Intermediate powder, using the Ta x O y C z Preparing a tantalum-containing suspension from the intermediate powder, coating the tantalum-containing suspension on the inner side wall of the graphite crucible and the inner bottom surface of the graphite crucible to form a precoat, wherein the thickness of the precoat on the inner side wall of the graphite crucible is gradually thickened along the direction of the inner bottom surface of the graphite crucible facing the graphite crucible opening, and performing second sintering on the graphite crucible coated with the precoat to finally form the tantalum carbide coating.
Ta in the precoat layer x O y C z The intermediate powder forms tantalum oxide (Ta) during the second sintering to form the tantalum carbide coating 2 O 5 ) And tantalum carbide (TaC), wherein the melting point of the tantalum oxide is 1878 ℃, the tantalum oxide is melted in the second sintering process to form liquid tantalum oxide with fluidity, and the tantalum carbide is solid particles, so that Ta x O y C z The intermediate powder forms a mixture of liquid tantalum oxide and solid tantalum carbide.
The tantalum oxide in the mixture and the graphite crucible are subjected to chemical reaction in the second sintering process, so that tantalum element in the tantalum oxide is fused with crystal bonds of carbon elements on the inner side wall and the inner bottom surface of the graphite crucible, and finally a tantalum carbide coating is formed on the inner side wall and the inner bottom surface of the graphite crucible.
Because the graphite crucible has certain porosity, the liquid tantalum oxide in the mixture drives solid tantalum carbide particles to flow, so that the tantalum carbide is filled in the pores of the graphite crucible and is surrounded by surrounding tantalum carbide, and the compactness of the tantalum carbide coating is improved.
The inventors found that the pre-coating was performed at a temperature below the melting point of tantalum oxideTa in layer x O y C z The intermediate powder still can decompose to generate tantalum oxide and tantalum carbide, and the generated tantalum oxide can react with carbon in the graphite crucible to generate tantalum carbide, however, because the tantalum oxide does not have fluidity, if the duration of the time period below the melting point of the tantalum oxide is too long, the tantalum oxide can only react with the graphite crucible at the position with the tantalum oxide on the one hand, so that generated tantalum carbide particles are intensively generated at the position with the tantalum oxide, and the finally formed tantalum carbide coating is uneven; on the other hand, the generated tantalum carbide particles have gaps and are not easy to fuse, and further the finally formed tantalum carbide coating is uneven and not compact.
In the second sintering process, the temperature rising rate of the high-temperature vacuum sintering furnace is set to be more than 20 ℃/min, so that the high-temperature vacuum sintering furnace is quickly heated, and Ta in the precoating layer x O y C z On the one hand, after the mixture has fluidity, tantalum carbide generated by the reaction of tantalum oxide and a graphite crucible cannot be accumulated, meanwhile, the mixture flows along the direction of the inner bottom surface of the graphite crucible towards the mouth of the graphite crucible, the flowing mixture of tantalum oxide and tantalum carbide is easier to fill gaps between the pores of graphite and generated tantalum carbide particles, the inner side wall of the graphite crucible is flattened, the formed tantalum carbide particles are easy to grow, and a tantalum carbide coating formed on the inner side wall and the inner bottom surface of the graphite crucible is more compact. At the same time, the thickness of the upper section of the precoating layer on the inner side wall of the graphite crucible is set>Thickness of the middle section>Coating the lower section in a thickness mode, and adjusting the temperature, pressure and time of the second sintering to avoid the problem that the thickness and compactness of the tantalum carbide coating formed by the upper section, the middle section and the lower section are different in the flowing process of the mixture, so that the finally formed tantalum carbide coating is more uniform and compact; on the other hand, the high-temperature vacuum sintering furnace is quickly heated, and Ta in the precoat layer x O y C z The intermediate powder is decomposed, the temperature condition of the reaction of tantalum oxide and the graphite crucible is quickly reached, and the speed is increasedThe reaction of tantalum oxide and graphite crucible avoids the upper segment precoating layer flow of graphite crucible inside wall to the middle segment and the lower segment, and the precoating layer flow of middle segment to the lower segment, further promotes the homogeneity and the compactness of graphite crucible inside wall tantalum carbide coating. Meanwhile, the preparation process of the tantalum carbide coating provided by the invention has low requirements on equipment, and the preparation cost is saved.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a tantalum carbide coating according to an embodiment of the invention;
fig. 2 is a schematic view of a precoating layer on the inner side wall of a graphite crucible in a tantalum carbide coating preparation method according to an embodiment of the present invention.
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 invention provides a preparation method of a tantalum carbide coating, which is shown in figure 1 and comprises the following steps:
step S10, preparation of Ta x O y C z An intermediate powder;
step S20, utilizing the Ta x O y C z Preparing a tantalum-containing suspension from the intermediate powder;
step S30, providing a graphite crucible with an inner side wall and an inner bottom surface, and coating the suspension containing tantalum element on the inner side wall of the graphite crucible and the inner bottom surface of the graphite crucible to form a precoat, wherein the thickness of the precoat on the inner side wall of the graphite crucible is gradually thickened along the direction of the inner bottom surface of the graphite crucible facing the graphite crucible opening;
and S40, performing second sintering on the graphite crucible coated with the precoat to form a mixture of liquid tantalum oxide and solid tantalum carbide, wherein the tantalum oxide reacts with graphite, the tantalum carbide is filled in pores of the graphite crucible, and finally the tantalum carbide coating is formed.
Specifically, step S10 is performed to prepare Ta x O y C z Intermediate powder.
In the embodiment of the invention, the preparation method of Ta x O y C z The step of intermediate powder comprises:
preparing a first mixture containing tantalum; pouring the first mixture into a reaction kettle to perform chelant reaction to obtain first powder containing tantalum; drying the first powder; performing first sintering on the dried first powder to obtain Ta x O y C z Intermediate powder.
In the embodiment of the invention, the content range of tantalum element in the first mixture is 0.2-0.8 mol/L, the content range of acetylacetone is 0.2-0.8 mol/L, and the ratio of the amounts of substances of tantalum element and oxygen element in the first mixture is 1:1 to 10.
In the embodiment of the invention, the first mixture is stirred by a magnetic stirrer for 1-10 hours.
In the embodiment of the invention, the temperature range of the first mixture when the chelant reaction occurs in the reaction kettle is 160-220 ℃, and the reaction time range is 1-10 h.
In the embodiment of the invention, the time for drying the first powder is 1 to 5 hours.
In the embodiment of the invention, the dried first powder is placed in a high-temperature vacuum sintering furnace for the first sintering, wherein the temperature range of the first sintering is 600-1400 ℃, and the time range of the first sintering is 1-10 h.
In an embodiment of the present invention, the first mixture containing tantalum element includes: tantalum element-containing powder, acetylacetone and alcohol solution; the tantalum-containing powder comprises: one or more of tantalum powder, tantalum chloride powder and tantalum carbide powder; the alcohol solution comprises one or more of n-butanol tantalum pentachloride solution and ethanol tantalum solution.
The method comprises the steps of utilizing the tantalum-containing powder and alcohol solution as alcohol tantalum compounds and acetylacetone as carbon compounds, and carrying out chelant reaction in a reaction kettle under the conditions of a certain temperature and a certain pressure to obtain first powder, wherein the first powder is sintered to obtain Ta x O y C z The intermediate powder provides raw materials for the subsequent preparation of the tantalum carbide coating.
Step S20 is performed using the Ta x O y C z The intermediate powder is used for preparing a suspension containing tantalum element.
In an embodiment of the present invention, the steps of preparing a tantalum-containing suspension include: taking a certain amount of Ta x O y C z The method comprises the steps of placing intermediate powder, tantalum-containing substances, an organic binder and an alcohol solution in a container, placing the container in an ultrasonic machine for mixing, and obtaining a suspension containing tantalum.
In an embodiment of the present invention, the tantalum-containing material comprises: one or more of tantalum oxide powder, tantalum powder and tantalum carbide powder; the organic binder is PVB (polyvinyl butyral), PVA (polyvinyl alcohol) or other suitable organic binder.
In the embodiment of the invention, the mole ratio of the tantalum element, the oxygen element and the carbon element in the suspension containing the tantalum element is 1-10: 1-20: 1.
and the compactness of the finally formed tantalum carbide coating is further improved by controlling the mole ratio of the tantalum element, the oxygen element and the carbon element in the suspension containing the tantalum element. The inventors found that an excessively high proportion of the carbon element in the tantalum element-containing suspension causes a reaction between a part of the tantalum oxide and the carbon element in the provided tantalum element-containing suspension during the second sintering process, which results in insufficient reaction of the tantalum oxide with carbon atoms on the graphite surface, resulting in a certain loss of the tantalum oxide, and also in a decrease in the compactability of the formed tantalum carbide coating due to insufficient reaction with graphite.
In the embodiment of the invention, the time range of mixing the container in the ultrasonic machine is 0-3 h.
Step S30 is performed, as shown in fig. 2, of providing a graphite crucible having an inner sidewall 12 and an inner bottom surface, and coating the suspension containing tantalum element on the inner sidewall 12 of the graphite crucible and the inner bottom surface of the graphite crucible to form a precoat, wherein the thickness of the precoat on the inner sidewall 12 gradually increases along the direction from the inner bottom surface of the graphite crucible to the graphite crucible opening to form the precoat.
In the embodiment of the invention, the precoating of the inner side wall is divided into an upper section 13, a middle section 14 and a lower section 15 for coating, wherein the upper section 13, the middle section 14 and the lower section 15 are the directions from the inner side wall 12 of the graphite crucible to the inner bottom surface of the graphite crucible along the graphite crucible opening.
In the embodiment of the invention, the thickness of the precoat layer at the upper section 13 of the inner side wall 12 of the graphite crucible is 400-500 μm, the thickness of the precoat layer at the middle section 14 is 300-400 μm, the thickness of the precoat layer at the lower section 15 is 100-300 μm, and the thickness of the precoat layer at the inner bottom surface of the graphite crucible is 200-400 μm.
When the thickness of the precoat is less than 100 mu m, the precoat is lost in the subsequent second sintering process, so that the formed tantalum carbide coating is too thin to achieve a compact effect; when the thickness of the precoat is more than 500 mu m, the tantalum carbide coating formed by the precoat in the subsequent second sintering process is too thick, and the phenomenon of cracking or falling of the tantalum carbide coating cannot achieve a compact effect due to the large stress of the tantalum carbide.
Since the graphite crucible has an inner side wall 12, the tantalum-containing suspension applied during the second sintering process, ta in the precoat layer x O y C z The intermediate powder forms a mixture containing liquid tantalum oxide and solid tantalum carbide, the mixture has certain fluidity, flows along the direction from the graphite crucible opening to the inner bottom surface of the graphite crucible, and the flowing mixture of tantalum oxide and tantalum carbide is easier to fill into the pores of the graphite crucible, so that the inner side wall 12 of the graphite crucible is leveled, and the formed tantalum carbide particles are easy to grow, so that the formed tantalum carbide coating is more compact.
Meanwhile, the mode of setting the thickness of the upper section of the precoating layer of the inner side wall 12 of the graphite crucible to the thickness of the middle section to the thickness of the lower section is adopted for coating and adjusting the temperature, the pressure and the time of the second sintering, so that the problem that the thickness and the compactness of the tantalum carbide coating formed by the upper section 13, the middle section 14 and the lower section 15 are different in the flowing process of the mixture is avoided, and the finally formed tantalum carbide coating is more uniform and compact.
In the embodiment of the invention, the suspension containing tantalum element is coated on the inner side wall and the inner bottom surface of the graphite crucible, and the process of forming the precoating layer is brushing.
The inner side wall and the inner bottom surface of the graphite crucible are brushed by adopting a brushing process, so that the brushing effect is not influenced by the shape of the graphite crucible, and the brushing thickness of the upper section 13, the middle section 14 and the lower section 15 of the inner side wall of the graphite crucible is better controlled.
In other embodiments, the process of forming the pre-coating on the inner sidewall and the inner bottom surface of the graphite crucible is spraying, dipping, sedimentation, leveling, or other suitable process.
Step S40 is executed, the graphite crucible coated with the precoat layer is subjected to second sintering to form a mixture of liquid tantalum oxide and solid tantalum carbide, the tantalum oxide reacts with graphite, and the tantalum carbide fills in pores of the graphite crucible to form a tantalum carbide coating layer.
In the embodiment of the invention, the graphite crucible with the precoating layer is dried and then subjected to the second sintering; the graphite crucible with the precoat was dried for a period of time ranging from 2 to 10 hours.
And (3) placing the graphite crucible coated with the precoat in a high-temperature vacuum sintering furnace for sintering, wherein the second sintering time range is 1-30 h, the second sintering temperature range is 1600-2400 ℃, and the heating rate before the second sintering is more than 20 ℃/min.
In the embodiment of the invention, the second sintering temperature range is 1878-2400 DEG C
Ta in the precoat layer x O y C z The intermediate powder forms tantalum oxide (Ta) during the second sintering to form a tantalum carbide coating 2 O 5 ) And tantalum carbide (TaC), wherein the melting point of the tantalum oxide is 1878 ℃, the tantalum oxide is melted in the second sintering process to form liquid tantalum oxide with fluidity, and the tantalum carbide is solid particles, so that Ta x O y C z The intermediate powder forms a mixture of tantalum oxide in a liquid state and tantalum carbide in a solid state.
The tantalum oxide in the mixture and the graphite crucible are subjected to chemical reaction in the second sintering process, so that tantalum element in the tantalum oxide is fused with crystal bonds of carbon elements on the inner side wall and the inner bottom surface of the graphite crucible, and finally a tantalum carbide coating is formed on the inner side wall and the inner bottom surface of the graphite crucible.
Because the graphite crucible has certain porosity, the liquid tantalum oxide in the mixture drives solid tantalum carbide particles to flow, so that the tantalum carbide is filled in the pores of the graphite material and is surrounded by surrounding tantalum carbide, and the compactness of the tantalum carbide coating is improved.
The inventor finds that when the temperature is lower than the melting point of tantalum oxide, the pre-coating layer still can decompose to generate tantalum oxide and tantalum carbide, and the generated tantalum oxide can react with carbon in the graphite crucible to generate tantalum carbide, however, because the tantalum oxide has no fluidity, if the time period lower than the melting point of tantalum oxide is too long, the tantalum oxide can only react with the graphite crucible at the position with tantalum oxide, so that generated tantalum carbide particles are intensively generated at the position with tantalum oxide, and the finally formed tantalum carbide coating is uneven; on the other hand, the generated tantalum carbide particles have gaps and are not easy to fuse, and further the finally formed tantalum carbide coating is uneven and not compact.
In the second sintering process, the temperature rising rate of the high-temperature vacuum sintering furnace is set to be more than 20 ℃/min, so that the high-temperature vacuum sintering furnace is quickly heated, and Ta in the precoating layer x O y C z The intermediate powder is rapidly decomposed and melted in a short time to form a flowable mixture, and on the one hand, after the mixture has fluidity, the tantalum carbide generated by the reaction of the tantalum oxide and the graphite crucible is not accumulated, and at the same time, the mixture containing the tantalum oxide and the tantalum carbideWill flow along the direction of graphite crucible mouth to graphite crucible inner bottom surface, the mixture that flows is more easy to fill to the hole of graphite and the gap between the tantalum carbide granule that generates for graphite crucible's inside wall becomes level and smooth, and the tantalum carbide granule that forms also grows up easily, makes graphite crucible inside wall and the tantalum carbide coating that inner bottom surface formed are more dense. At the same time, the thickness of the upper section of the precoating layer on the inner side wall of the graphite crucible is set>Thickness of the middle section>Coating the lower section in a thickness mode, and adjusting the temperature, pressure and time of the second sintering to avoid the problem that the thickness and compactness of the tantalum carbide coating formed by the upper section, the middle section and the lower section are different in the flowing process of the mixture, so that the finally formed tantalum carbide coating is more uniform and compact; on the other hand, the high-temperature vacuum sintering furnace is rapidly heated, and Ta in the precoat layer x O y C z The intermediate powder is decomposed, the temperature condition of the reaction of tantalum oxide and the graphite crucible is quickly reached, the reaction of tantalum oxide and the graphite crucible is quickened, the phenomenon that the precoating layer of the upper section 13 of the inner side wall of the graphite crucible flows to the middle section 14 and the lower section 15 and the precoating layer of the middle section 14 flows to the lower section 15 is avoided, and the uniformity and compactness of the tantalum carbide coating of the inner side wall of the graphite crucible are further improved. Meanwhile, the preparation process of the tantalum carbide coating provided by the invention has low requirements on equipment, and the preparation cost is saved.
Based on the same inventive concept, the embodiment of the invention also provides a graphite crucible, which comprises the graphite crucible and a tantalum carbide coating layer positioned on the inner side wall and the inner bottom surface of the graphite crucible, wherein the tantalum carbide coating layer is prepared and formed by the method of any one of the above.
Based on the same inventive concept, the embodiment of the invention also provides a silicon carbide crystal growth device comprising the graphite crucible.
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 (11)
1. A method for producing a tantalum carbide coating, comprising:
preparation of Ta x O y C z An intermediate powder;
by using the Ta x O y C z Preparing a tantalum-containing suspension from the intermediate powder;
providing a graphite crucible with an inner side wall and an inner bottom surface, and coating the suspension containing tantalum element on the inner side wall of the graphite crucible and the inner bottom surface of the graphite crucible to form a precoat, wherein the thickness of the precoat of the inner side wall gradually increases along the direction of the inner bottom surface of the graphite crucible facing a graphite crucible opening;
and (3) performing second sintering on the graphite crucible coated with the precoat, wherein the precoat forms a mixture containing liquid tantalum oxide and solid tantalum carbide in the second sintering process, the tantalum oxide reacts with the graphite crucible, and the tantalum carbide fills in pores of the graphite crucible, so that the tantalum carbide coating is finally formed.
2. A method for producing a tantalum carbide coating according to claim 1 wherein Ta is produced x O y C z The step of intermediate powder comprises: preparing a first mixture containing tantalum element; pouring the first mixture into a reaction kettle to perform chelant reaction to obtain first powder containing tantalum; drying the first powder; performing first sintering on the dried first powder, wherein Ta is obtained after the first sintering x O y C z Intermediate powder.
3. The method of producing a tantalum carbide coating according to claim 2, wherein the content of tantalum element in said first mixture is in the range of 0.2 to 0.8mol/L, the content of acetylacetone is in the range of 0.2 to 0.8mol/L, and the ratio of the amounts of tantalum element and oxygen element in said first mixture is 1:1 to 10.
4. The method of producing a tantalum carbide coating according to claim 2, wherein said first sintering of said dried first powder is carried out at a temperature in the range of 600 to 1400 ℃ for a time in the range of 1 to 10 hours.
5. A method of producing a tantalum carbide coating according to claim 2, wherein said first mixture comprising tantalum comprises: tantalum element-containing powder, acetylacetone and alcohol solution; wherein the tantalum-containing powder comprises: one or more of tantalum powder, tantalum chloride powder and tantalum carbide powder; the alcohol solution comprises one or more of n-butanol tantalum pentachloride solution and ethanol tantalum solution.
6. A method of producing a tantalum carbide coating according to claim 1, wherein the step of producing a tantalum element-containing suspension comprises: taking a certain amount of Ta x O y C z The method comprises the steps of placing powder, tantalum-containing substances, an organic binder and an alcohol solution in a container, placing the container in an ultrasonic machine for mixing, and obtaining a suspension containing tantalum.
7. A method of producing a tantalum carbide coating according to claim 6, wherein said tantalum-containing material comprises: one or more of tantalum powder, tantalum oxide powder and tantalum carbide powder; the organic binder is PVB or PVA; the mole ratio of tantalum element, oxygen element and carbon element in the suspension containing tantalum element is 1-10: 1-20: 1.
8. the method for preparing a tantalum carbide coating according to claim 1, wherein the precoating of the inner side wall is divided into an upper section, a middle section and a lower section for coating, wherein the upper section, the middle section and the lower section are the directions from the inner side wall of the graphite crucible to the inner bottom surface of the graphite crucible along the graphite crucible opening; the thickness range of the precoat layer at the upper section of the inner side wall of the graphite crucible is 400-500 mu m, the thickness range of the precoat layer at the middle section is 300-400 mu m, the thickness range of the precoat layer at the lower section is 100-300 mu m, and the thickness range of the precoat layer at the inner bottom surface of the graphite crucible is 200-400 mu m.
9. The method for preparing a tantalum carbide coating according to claim 1, wherein the graphite crucible coated with the pre-coating is placed in a high-temperature vacuum sintering furnace for second sintering, wherein the second sintering time is 1-30 h, the second sintering temperature is 1600-2400 ℃, and the heating rate before the second sintering is more than 20 ℃/min.
10. A graphite crucible comprising a graphite crucible and a tantalum carbide coating on the inside and bottom surfaces of the graphite crucible, wherein the tantalum carbide coating is formed by the method of any one of claims 1 to 9.
11. A silicon carbide crystal growth apparatus comprising the graphite crucible of claim 10.
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