CN112898049A - Boron nitride coating evaporation boat and preparation method thereof - Google Patents
Boron nitride coating evaporation boat and preparation method thereof Download PDFInfo
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- 238000001704 evaporation Methods 0.000 title claims abstract description 88
- 230000008020 evaporation Effects 0.000 title claims abstract description 88
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 72
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 57
- 239000010439 graphite Substances 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 40
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052796 boron Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004327 boric acid Substances 0.000 claims abstract description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 16
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
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- 230000009286 beneficial effect Effects 0.000 description 4
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- 230000008569 process Effects 0.000 description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005269 aluminizing Methods 0.000 description 2
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- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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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
-
- 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
- C04B41/5062—Borides, Nitrides or Silicides
- C04B41/5064—Boron nitride
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/342—Boron nitride
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
Abstract
The invention provides a boron nitride coating evaporation boat and a preparation method thereof, wherein the preparation method comprises the following steps: placing a boron source at the bottom of a reaction chamber made of boron nitride, placing a graphite evaporation boat substrate in the reaction chamber, and keeping a distance of 20-50 mm between the graphite evaporation boat substrate and the boron source, wherein the boron source is selected from any one of boron trioxide and boric acid; placing the reaction chamber in a chemical vapor deposition furnace, vacuumizing the chemical vapor deposition furnace, heating to 500-700 ℃, and introducing nitrogen to keep positive pressure in the furnace and continuously introducing nitrogen in the reaction; heating the chemical vapor deposition furnace to 1750-1950 ℃ and keeping the temperature for 1-8 h, and depositing and growing a boron nitride coating on the graphite evaporation boat substrate. The raw materials of the invention are nontoxic and nonflammable, safe and easily available, and the preparation process is more environment-friendly and safer. And the preparation process is easy to control, the reaction chambers can be placed in the chemical vapor deposition furnace in batches, the production efficiency is high, and the method is suitable for large-scale and large-scale production.
Description
Technical Field
The invention relates to the technical field of boron nitride, in particular to a boron nitride coating evaporation boat and a preparation method thereof.
Background
Vacuum evaporation aluminizing technology is used to produce metallic aluminum films, which have numerous applications in a variety of industrial applications. A consumable vessel evaporation boat is used in the vacuum evaporation aluminizing process, and the material for preparing the evaporation boat must be resistant to the corrosion of aluminum liquid due to the great activity of metal aluminum.
In the prior art, boron chloride or boron bromide is generally used as a boron source, and a pyrolytic boron nitride coating is deposited on the surface of a graphite boat by a chemical vapor deposition method under a mixed atmosphere of ammonia gas and nitrogen gas to prepare the graphite/boron nitride coating evaporation boat. However, the inventor finds that the reaction raw material ammonia gas prepared by the preparation method is a toxic gas with pungent smell, is easy to combust when mixed with air and is not beneficial to environmental protection and production safety, and the reaction product contains halogen acid, which raises higher requirement on the hydrochloric acid corrosion resistance of equipment, thus leading to higher equipment purchase and maintenance cost; on the other hand, the production efficiency is low, which results in high production cost of the evaporation boat.
Disclosure of Invention
The invention aims to provide a boron nitride coating evaporation boat and a preparation method thereof, and provides a more environment-friendly preparation process of the boron nitride coating evaporation boat. The specific technical scheme is as follows:
the first aspect of the present invention provides a method for preparing a boron nitride coated evaporation boat, comprising:
placing a boron source at the bottom of a reaction chamber made of boron nitride, placing a graphite evaporation boat substrate in the reaction chamber, and keeping a distance of 20-50 mm between the graphite evaporation boat substrate and the boron source, wherein the boron source is selected from any one of diboron trioxide and boric acid;
placing the reaction chamber in a chemical vapor deposition furnace, vacuumizing the chemical vapor deposition furnace, heating to 500-700 ℃, and introducing nitrogen to keep positive pressure in the chemical vapor deposition furnace and continuously introducing nitrogen in the reaction;
heating the chemical vapor deposition furnace to 1750-1950 ℃ and keeping the temperature for 1-8 h, and depositing and growing a boron nitride coating on the graphite evaporation boat substrate.
In one embodiment of the invention, the relationship between the addition amount of the boron source and the surface area of the substrate of the graphite evaporation boat is 0.2-0.5 g/cm2。
In one embodiment of the invention, the temperature rise rate of the chemical vapor deposition furnace is 1-10 ℃/min.
In one embodiment of the present invention, the reaction temperature is 1800 to 1900 ℃.
In one embodiment of the invention, the heat preservation time is 3-6 h.
In one embodiment of the invention, after nitrogen is introduced, the internal pressure of the chemical vapor deposition furnace is maintained to be 1-1000 Pa higher than the external environment pressure.
In one embodiment of the invention, the distance between the graphite evaporation boat substrates in the reaction chamber is 2-10 mm.
In one embodiment of the present invention, the number of the evaporation boat substrates provided in each reaction chamber is 3 to 50.
In one embodiment of the invention, a plurality of reaction chambers are arranged in a stack in a chemical vapor deposition furnace.
The invention provides a boron nitride coating evaporation boat prepared by the preparation method according to any one of the embodiments, wherein the boron nitride coating of the evaporation boat has the thickness of 0.15-0.3 mm, the thermal conductivity of 30-35W/M.K and the density of 2.0-2.2 g/cm3。
The invention has the beneficial effects that:
the invention provides a boron nitride coating evaporation boat and a preparation method thereof. Compared with the existing evaporation boat boron nitride coating preparation process based on boron chloride and ammonia gas as raw materials, the evaporation boat boron nitride coating preparation process has the advantages that the raw materials are non-toxic and non-flammable, are safe and easily obtained, and the preparation process is more environment-friendly and safer. And the preparation process is easy to control, the reaction chambers can be placed in the chemical vapor deposition furnace in batches, the production efficiency is high, and the method is more suitable for large-scale and large-scale production. Of course, not all of the advantages described above need to be achieved at the same time in the practice of any one product or method of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an exploded schematic view of a reaction chamber according to one embodiment of the present invention;
FIG. 2 is a schematic diagram of the structure of a substrate of a graphite evaporation boat according to one embodiment of the present invention;
FIG. 3 is a schematic view of the arrangement of the substrate of the graphite evaporation boat in the reaction chamber according to one embodiment of the present invention;
FIG. 4 is an exploded schematic view of a reaction chamber according to another embodiment of the present invention;
FIG. 5 is a schematic structural view of a reaction chamber according to another embodiment of the present invention;
FIG. 6 is an X-ray diffraction (XRD) curve of a boron nitride coating on the substrate surface of the graphite evaporation boat prepared in example 2 of the present invention.
In the figure, 1, a reaction chamber, 2, a middle frame, 3, an upper cover plate, 4, a lower bottom plate, 5, a graphite evaporation boat substrate, 6, a middle plate, 20, a clamping groove, 41, a boss, 51 and a groove are arranged.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the disclosure are intended to be within the scope of the disclosure.
The invention provides a preparation method of a boron nitride coating, which comprises the following steps:
placing a boron source at the bottom of a reaction chamber made of boron nitride, placing a graphite evaporation boat substrate in the reaction chamber, and keeping a distance of 20-50 mm between the graphite evaporation boat substrate and the boron source, wherein the boron source is selected from any one of diboron trioxide and boric acid.
And placing the reaction chamber in a chemical vapor deposition furnace, vacuumizing the chemical vapor deposition furnace, heating to 500-700 ℃, and introducing nitrogen, so that positive pressure is kept in the chemical vapor deposition furnace, and nitrogen is continuously introduced in the reaction.
Heating the chemical vapor deposition furnace to 1750-1950 ℃ and keeping the temperature for 1-8 h, and depositing and growing a boron nitride coating on the graphite evaporation boat substrate.
The inventor researches and discovers that boron trioxide (B) is adopted in the preparation method of the evaporation boat with the boron nitride coating2O3) Or boric acid (H)3BO3) As the boron source, the above boron source and nitrogen (N) gas are used2) As a raw material, a boron nitride coating can be deposited and grown on the surface of a graphite evaporation boat substrate by controlling the temperature of a chemical vapor deposition furnace (CVD furnace) to be increased to 1750-1950 ℃ and the heat preservation time to be 1-8 h. The boron nitride coating is hexagonal boron nitride, has excellent heat conductivity, and enables the graphite evaporation boat with the coating to have excellent performance.
When the boron nitride coating is prepared, the reaction temperature is controlled to be 1750-1950 ℃, the temperature is preferably 1800-1900 ℃, and the heat preservation time is 1-8 hours, preferably 3-6 hours. Without being limited to any theory, when the temperature of the reactants is too low (e.g., less than 1750 ℃), the boron nitride coating is not well deposited, and when the temperature of the reactants is too high (e.g., more than 1950 ℃), the energy consumption is too large, resulting in an increase in production costs. By controlling the reaction temperature and the heat preservation time within the range, the boron nitride coating with uniform thickness and excellent performance can be deposited on the graphite evaporation boat substrate, and meanwhile, the production cost is controllable, and the method is more favorable for industrial production.
The type of the chemical vapor deposition furnace is not particularly limited, and may be, for example, a commercially available chemical vapor deposition furnace as long as the requirements of the present invention are satisfied.
The reaction chamber used in the invention is a boron nitride reaction chamber, namely a reaction chamber made of boron nitride. The inventor unexpectedly finds that by using the reaction chamber made of the boron nitride material as the reaction container of the graphite evaporation boat substrate, the boron nitride coating deposited on the surface of the graphite evaporation boat substrate is more uniform and compact, so that the prepared graphite evaporation boat has better performance.
In the process of depositing the boron nitride coating, the graphite evaporation boat substrate is placed in the reaction chamber, and the distance between the graphite evaporation boat substrate and the boron source is kept between 20 and 50mm, so that the boron nitride can be better deposited on the surface of the graphite evaporation boat substrate. In one embodiment, a layer of boron source can be flatly laid at the bottom of the reaction chamber and 20-50 mm away from the graphite evaporation boat substrate, and the flatly laid arrangement mode can further improve the contact area of the boron source and nitrogen, so that the reaction rate is improved.
Before the chemical vapor deposition, the chemical vapor deposition furnace can be vacuumized to exhaust air in the chemical vapor deposition furnace, so that the deposition reaction is prevented from being influenced by gases such as oxygen in the air. And nitrogen is introduced after vacuum pumping, so that the use amount of nitrogen can be saved, and the production cost is reduced. Of course, nitrogen can also be directly introduced into the chemical vapor deposition furnace, as long as the positive pressure in the chemical vapor deposition furnace is maintained during the reaction.
The inventor finds that the boron nitride can be better deposited on the surface of the graphite evaporation boat substrate by pumping the chemical vapor deposition furnace to vacuum, raising the temperature to 500-700 ℃ and then introducing nitrogen, which may be that the nitrogen introduced can be preheated after the chemical vapor deposition furnace is raised to 500-700 ℃, and is more beneficial to the deposition of the boron nitride on the surface of the graphite evaporation boat substrate.
In one embodiment of the invention, the relationship between the addition amount of the boron source and the surface area of the substrate of the graphite evaporation boat is 0.2-0.5 g/cm2. Namely, according to the surface area calculation of the graphite evaporation boat matrix, 0.2-0.5 g of boron trioxide or equivalent boric acid is added per square centimeter. By controlling the addition amount of the boron source within the range, enough boron source can participate in the reaction to generate boron nitride, and the waste of raw materials caused by excessive addition of the boron source can be avoided.
The present invention has no particular limitation on the temperature increase rate of the chemical vapor deposition furnace, as long as the predetermined reaction temperature can be reached and the requirements of the present invention are satisfied. In one embodiment of the invention, the temperature rise rate of the chemical vapor deposition furnace is 1-10 ℃/min, preferably 5-8 ℃/min.
The positive pressure referred to herein may refer to micro positive pressure. In one embodiment of the invention, the pressure inside the reactor is maintained to be 1-1000 Pa higher than the pressure of the external environment by continuously introducing nitrogen. By maintaining the positive pressure inside the reactor, the influence of external air entering the deposition furnace on the boron nitride deposition effect can be effectively avoided.
In one embodiment of the present invention, the reaction chamber 1 has a structure as shown in fig. 1, and comprises a middle frame 2, an upper cover plate 3 and a lower base plate 4, wherein the inner wall of the middle frame 2 is provided with a plurality of slots 20 for fixing the graphite evaporation boat substrate 5. The peripheral edge of the lower plate 4 is provided with bosses 41 which are fitted to the bottom of the middle frame 2, so that the bottom of the middle frame 2 is fixed at the bosses 41. The shape of the graphite evaporation boat substrate 5 is not particularly limited in the present invention, and may be, for example, a rectangular structure as shown in fig. 2, or another structure in which the upper surface of the graphite evaporation boat substrate 5 is provided with a groove 51 for containing aluminum. In the process of preparing the boron nitride coating, the graphite evaporation boat substrate 5 can be reversely placed in the reaction chamber as shown in fig. 3, so that the groove 51 faces downwards, which is more beneficial to uniformly depositing the boron nitride coating on the surface of the graphite evaporation boat substrate 5.
In one embodiment of the invention, the distance between the graphite evaporation boat substrates in the reaction chamber is 2-10 mm. By controlling the interval of the graphite evaporation boat substrates within the range, the evaporation boat substrates can be prevented from being arranged too tightly or sparsely in the reaction chamber, the space utilization rate of the chemical deposition furnace is improved, and the evaporation boat with the boron nitride coating is more suitable for mass production.
In one embodiment of the present invention, the number of the graphite evaporation boat substrates disposed in each reaction chamber is 3 to 50, and accordingly, the number of the clamping grooves 20 disposed on the inner wall of the middle frame 2 is 30 to 50 pairs. By controlling the quantity of the evaporation boat substrates in each reaction chamber, the evaporation boat substrates are not arranged too tightly or sparsely in the reaction chambers, the space utilization rate of the chemical deposition furnace is improved, and the evaporation boat with the boron nitride coating is more suitable for mass production.
In one embodiment of the present invention, as shown in FIGS. 4 and 5, a plurality of reaction chambers 1 may be stacked in a CVD furnace, each reaction chamber 1 being partitioned by an intermediate plate 6, two reaction chambers being stacked to form a stack, and a plurality of stacks being placed in a furnace. By the arrangement method, hundreds or even thousands of evaporation boats with coatings can be produced in one preparation, and the production efficiency is further improved.
The invention provides a boron nitride coating evaporation boat and a preparation method thereof. Compared with the existing evaporation boat boron nitride coating preparation process based on boron chloride and ammonia gas as raw materials, the evaporation boat boron nitride coating preparation process has the advantages that the raw materials are non-toxic and non-flammable, are safe and easily obtained, and the preparation process is more environment-friendly and safer. And the preparation process is easy to control, the reaction chambers can be placed in the chemical vapor deposition furnace in batches, the production efficiency is high, and the method is more suitable for large-scale and large-scale production.
The invention also provides the boron nitride coating evaporation boat prepared by the preparation method, wherein the heat conductivity coefficient of the boron nitride coating on the surface of the boron nitride coating evaporation boat is 30-35W/M.K, and the density is 2.0-2.2 g/cm3And has excellent heat conducting performance.
The thickness of the boron nitride coating layer is not particularly limited in the present invention as long as the requirements of the present invention can be satisfied. In one embodiment of the invention, the thickness of the boron nitride coating on the surface of the boron nitride coating evaporation boat is 0.15-0.3 mm.
The invention adopts diboron trioxide or boric acid as a boron source and nitrogen as a nitrogen source, has low cost of raw materials, adopts a unique combined stacking reaction chamber, greatly improves the yield of the single-furnace evaporation boat, is suitable for batch production, can greatly reduce the cost, and ensures that the cost for manufacturing the graphite/pyrolytic boron nitride coating evaporation boat can be lower than that of a ceramic evaporation boat.
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples. Various tests and evaluations were carried out according to the following methods. Unless otherwise specified, "part" and "%" are based on mass.
Example 1
< addition of raw Material >
Boron nitride (B)2O3) Spreading the powder at the bottom of a reaction chamber made of boron nitride, placing a graphite evaporation boat substrate in the reaction chamber and keeping a distance of 20mm between the graphite evaporation boat substrate and a boron source, wherein B2O3The addition amount is calculated by the surface area of the graphite evaporation boat substrate as follows: 0.2g/cm2。
And placing the reaction chamber in a chemical vapor deposition furnace, vacuumizing the chemical vapor deposition furnace, heating to 500 ℃, and introducing nitrogen to keep positive pressure in the chemical vapor deposition furnace and continuously introducing nitrogen in the reaction.
< growth of boron nitride coating >
Heating the chemical vapor deposition furnace to 1750 ℃ of reaction temperature, keeping the temperature for 8 hours, and depositing and growing a boron nitride coating on the graphite evaporation boat substrate.
Example 2
The procedure of example 1 was repeated except that the preparation parameters were adjusted in accordance with the data shown in Table 1 in < raw material addition >, < growth of boron nitride coating >.
Example 3
The procedure of example 1 was repeated except that the preparation parameters were adjusted in accordance with the data shown in Table 1 in < raw material addition >, < growth of boron nitride coating >.
Example 4
The procedure of example 1 was repeated except that the preparation parameters were adjusted in accordance with the data shown in Table 1 in < raw material addition >, < growth of boron nitride coating >.
Example 5
The procedure of example 1 was repeated except that the preparation parameters were adjusted in accordance with the data shown in Table 1 in < raw material addition >, < growth of boron nitride coating >.
Example 6
The procedure of example 1 was repeated except that the preparation parameters were adjusted in accordance with the data shown in Table 1 in < raw material addition >, < growth of boron nitride coating >.
TABLE 1 preparation data for examples 1-6
The performance parameters of the boron nitride coating on the surface of the graphite evaporation boat prepared in each example are shown in Table 2
TABLE 2 boron nitride coating Performance parameters for graphite evaporator boat surfaces of examples 1-6
It can be seen from examples 1-6 that the distance between the graphite evaporation boat substrate and the boron source, the addition amount of the boron source, the preheating temperature of the CVD furnace, the reaction temperature and the holding time generally affect the deposition thickness of the boron nitride coating on the surface of the graphite evaporation boat substrate, and as long as the above preparation parameters are within the range of the present application, a dense boron nitride coating with appropriate thickness and excellent heat conductivity can be obtained on the surface of the graphite evaporation boat substrate. The preparation method of the invention does not need to use poisonous NH3As a reaction raw material, the method is more environment-friendly and safer.
FIG. 6 is an XRD curve of a boron nitride coating deposited on a substrate of a graphite evaporation boat in example 2 of the present invention. As can be seen from FIG. 6, the product has diffraction peaks around 26.8 degrees and 55.1 degrees, and by comparing with the standard substance card, and referring to FIG. 6, the boron nitride coating on the surface of the substrate of the graphite evaporation boat of the present invention is pure hexagonal BN phase, no boron oxide is detected, and the crystal structure is similar to that of graphite (C).
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A method of making a boron nitride coated evaporation boat, the method comprising:
placing a boron source at the bottom of a reaction chamber made of boron nitride, placing a graphite evaporation boat substrate in the reaction chamber, and keeping a distance of 20-50 mm between the graphite evaporation boat substrate and the boron source, wherein the boron source is selected from any one of diboron trioxide and boric acid;
placing the reaction chamber in a chemical vapor deposition furnace, vacuumizing the chemical vapor deposition furnace, heating to 500-700 ℃, and introducing nitrogen to keep positive pressure in the chemical vapor deposition furnace and continuously introducing nitrogen in the reaction;
heating the chemical vapor deposition furnace to 1750-1950 ℃ and keeping the temperature for 1-8 h, and depositing and growing a boron nitride coating on the graphite evaporation boat substrate.
2. The method according to claim 1, wherein the relationship between the amount of the boron source added and the surface area of the substrate of the graphite evaporation boat is 0.2 to 0.5g/cm2。
3. The method according to claim 1, wherein the temperature rise rate of the CVD furnace is 1-10 ℃/min.
4. The method according to claim 1, wherein the reaction temperature is 1800 to 1900 ℃.
5. The preparation method according to claim 1, wherein the holding time is 3 to 6 hours.
6. The method according to claim 1, wherein the pressure inside the chemical vapor deposition furnace is maintained to be 1-1000 Pa higher than the pressure of the external environment after the nitrogen gas is introduced.
7. The method according to claim 1, wherein the plurality of graphite boat substrates are spaced at intervals of 2 to 10mm in the reaction chamber.
8. The manufacturing method according to claim 7, wherein the number of the evaporation boat substrates provided in each reaction chamber is 3 to 50.
9. The production method according to claim 1, wherein a plurality of reaction chambers are arranged in a stack in the chemical vapor deposition furnace.
10. A boron nitride coated evaporation boat prepared by the preparation method according to any one of claims 1 to 9, wherein the boron nitride coating of the evaporation boat has a thickness of 0.15 to 0.3mm, a thermal conductivity of 30 to 35W/M.K, and a density of 2.0 to 2.2g/cm3。
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| CA2011037A1 (en) * | 1989-10-20 | 1991-04-20 | Takahisa Koshida | Composite material of boron nitride and method for the preparation thereof |
| CN1176317A (en) * | 1996-08-07 | 1998-03-18 | 康塞普特系统设计公司 | Gas injection system for CVD reactors |
| CN102487109A (en) * | 2009-12-22 | 2012-06-06 | 无锡尚德太阳能电力有限公司 | Horizontal graphite boat |
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