CN118109895B - Silicon nitride/fused quartz composite crucible and preparation method and application thereof - Google Patents
Silicon nitride/fused quartz composite crucible and preparation method and application thereof Download PDFInfo
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- CN118109895B CN118109895B CN202410532593.XA CN202410532593A CN118109895B CN 118109895 B CN118109895 B CN 118109895B CN 202410532593 A CN202410532593 A CN 202410532593A CN 118109895 B CN118109895 B CN 118109895B
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 153
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 151
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000005350 fused silica glass Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010453 quartz Substances 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims description 75
- 239000011230 binding agent Substances 0.000 claims description 39
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000005121 nitriding Methods 0.000 claims description 33
- 239000012298 atmosphere Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 26
- 239000003292 glue Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 24
- 238000007599 discharging Methods 0.000 claims description 23
- 239000011863 silicon-based powder Substances 0.000 claims description 22
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000009694 cold isostatic pressing Methods 0.000 claims description 12
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 12
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 12
- 238000000280 densification Methods 0.000 claims description 11
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 238000000429 assembly Methods 0.000 claims description 3
- 230000000712 assembly Effects 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 description 22
- 239000000843 powder Substances 0.000 description 21
- 239000000377 silicon dioxide Substances 0.000 description 20
- 239000010410 layer Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 13
- 238000000576 coating method Methods 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 10
- 238000003754 machining Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011361 granulated particle Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910021493 α-cristobalite Inorganic materials 0.000 description 1
- 229910021494 β-cristobalite Inorganic materials 0.000 description 1
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- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/10—Crucibles or containers for supporting the melt
- C30B15/12—Double crucible methods
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
- C04B35/591—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by reaction sintering
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- C30B28/00—Production of homogeneous polycrystalline material with defined structure
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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Abstract
The invention discloses a silicon nitride/fused quartz composite crucible and a preparation method and application thereof, and relates to the technical field of crucibles, wherein the silicon nitride/fused quartz composite crucible comprises a silicon nitride crucible with an inner layer and a fused quartz crucible layer coated on the outer layer of the silicon nitride crucible, the silicon nitride crucible is assembled by a plurality of silicon nitride components, and the fused quartz crucible layer is hooped inwards to form compressive stress on the silicon nitride crucible with the inner layer; according to the invention, the silicon nitride component is hooped to form an integral structure by utilizing the characteristic that quartz and silicon nitride have different thermal expansion coefficients at high temperature, and the fused quartz layer forms compressive stress on the internal silicon nitride crucible, so that the structural strength of the silicon nitride crucible is improved, and the crucible has a longer service life.
Description
Technical Field
The invention relates to the technical field of crucibles, in particular to a silicon nitride/fused quartz composite crucible, and a preparation method and application thereof.
Background
Fused silica ceramic crucibles are critical metallurgical vessels necessary for producing monocrystalline or polycrystalline silicon. However, the following problems frequently occur in actual production:
1. The fused quartz is subjected to high-temperature crystal transformation (amorphous quartz, beta-cristobalite, alpha-cristobalite), so that the fused quartz ceramic crucible is easy to crack, and the yield of silicon ingots is influenced.
2. In the process of casting single crystal silicon or polysilicon, the main factor affecting the quality of a polysilicon ingot or a single crystal silicon rod is impurities, one main source of which is a quartz crucible used in melting the polysilicon ingot or drawing the single crystal silicon rod, liquid silicon severely erodes the quartz crucible at high temperature, and the reaction equation is as follows:
Si+SiO2→2SiO
Part of SiO volatilizes from the surface of the silicon melt, and part of SiO is decomposed in the silicon melt, and the reaction equation is as follows:
SiO→Si+O
The oxygen decomposed by the quartz enters the melt and finally introduces silicon crystals, which become harmful substances affecting the quality of the polycrystalline silicon ingot or the monocrystalline silicon rod. An increase in oxygen content will reduce the conversion efficiency of the solar photovoltaic cell.
3. The polycrystalline silicon cast ingot is easy to adhere to the fused quartz ceramic crucible, so that the silicon ingot cannot be completely separated.
In view of the above problems, a variety of solutions have been proposed by those skilled in the art:
(1) Adopts a quartz crucible and graphite crucible mode. The quartz crucible is used as the lining of the graphite crucible, so that the problem that the quartz crucible is easy to soften at high temperature is solved, the mode supports continuous drawing of large-diameter single crystal silicon rods at high temperature, and the usability of the crucible can not be changed basically. The service life of the composite crucible is about 400 hours, and the composite crucible still belongs to a frequently-replaced consumable product, so that the production of monocrystalline silicon, especially N-type monocrystalline silicon, not only causes resource waste and increases cost, but also can not reduce the oxygen content of the crystalline silicon.
(2) And (3) spraying an alpha-silicon nitride coating on the inner wall of the fused quartz ceramic crucible so that the silicon ingot and the fused quartz ceramic crucible do not adhere after the polysilicon ingot is cast. However, because more auxiliary agents are often needed to be added in the silicon nitride coating to realize sintering, the coating is thinner, the purity of the sintered silicon nitride coating is lower, more pores are formed, and the high-temperature silicon melt often completely penetrates through the silicon nitride coating, so that the crucible with the silicon nitride coating is often used for polycrystalline silicon ingot casting and cannot be used for single crystal silicon pulling rods.
(3) The fused silica material was discarded and a silicon nitride crucible was prepared using a silicon nitride material. In theory, the silicon nitride crucible can overcome the problems of crystallization, permeation and low heat conductivity of the original fused quartz material, and can be reused. However, due to the relatively high sintering temperatures (at 1700 ℃ C.) of silicon nitride, technicians often add large amounts of sintering aids in order to reduce the sintering temperatures, which inevitably results in contamination. In addition, unlike the arc fusion method of quartz crucible and the rotary molding method, the existing sintering of large-size integrally molded compact silicon nitride ceramic crucible requires various large-sized professional molding equipment such as a large-caliber high-pressure cold isostatic press, a gas pressure sintering furnace with a large-sized furnace body inner cavity, and the like. Such equipment is expensive, and the preparation process involves high-temperature and high-pressure operation, which is dangerous. Even so, the maximum firing size of the equipment is about 30cm in diameter, the size of the traditional quartz crucible (the maximum diameter is more than 100 cm) cannot be achieved, the crucible after integral molding occupies a large space in a sintering furnace, and the sintering efficiency is low.
The publication CN101479410a 'method and crucible for directional solidification of semiconductor grade polycrystalline silicon ingots' uses an assembly method to assemble silicon nitride ceramic elements into square crucibles and uses a sealing paste containing silicon for nitriding, so that the gaps between the silicon nitride ceramic elements are sealed. However, since the sealing paste is not subjected to high-pressure treatment and has a porous structure, there still exist problems similar to those of the silicon nitride coating; on the other hand, because the compactness of the silicon nitride ceramic element is different from that of the silicon nitride at the gap, uneven stress exists in the repeated use process, and cracks can appear at the gap.
Disclosure of Invention
The invention aims to solve the technical problem of providing a silicon nitride/fused quartz composite crucible and a preparation method thereof, wherein sealing materials are not needed to be adopted among gaps of the composite crucible, and the preparation method is simple and low in risk.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
The invention aims to provide a silicon nitride/fused quartz composite crucible, which comprises a silicon nitride crucible with an inner layer and a fused quartz crucible layer coated on the outer layer of the silicon nitride crucible, wherein the silicon nitride crucible is formed by assembling a plurality of plate-shaped silicon nitride components, and the fused quartz crucible layer is hooped inwards to form compressive stress on the silicon nitride crucible with the inner layer.
The second object of the present invention is to provide a method for preparing the silicon nitride/fused quartz composite crucible, comprising the following steps:
step S1, mixing silicon powder, a sintering aid and a binder solution into uniform slurry, obtaining a blank body through cold isostatic pressing, and discharging glue from the blank body;
step S2, sintering the blank in a sintering furnace after the glue discharging is completed to obtain a silicon nitride component with a compact structure;
and S3, assembling a plurality of plate-shaped silicon nitride assemblies into a complete silicon nitride crucible, and hooping the fused quartz crucible layer on the outer surface of the silicon nitride crucible to obtain the silicon nitride/fused quartz composite crucible.
It is a further object of the present invention to provide the use of the aforementioned silicon nitride/fused silica composite crucible in single crystal silicon pulling rod or in polycrystalline silicon casting.
The beneficial effects of the invention are as follows:
(1) Compared with the conventional silicon nitride coating, the silicon nitride component obtained by cold isostatic pressing is more compact.
(2) According to the invention, the silicon nitride component is hooped to form an integral structure by utilizing the characteristic that quartz and silicon nitride have different thermal expansion coefficients at high temperature, and the quartz layer forms compressive stress on the silicon nitride crucible in the crucible, so that the structural strength of the crucible is improved, and the crucible has a longer service life;
(3) Compared with the existing integrally formed silicon nitride crucible (with the diameter of 30 cm), the composite crucible obtained by adopting the assembly of the sheet-shaped silicon nitride component and the hooping of fused quartz has the maximum diameter of 100cm and high space utilization rate in the furnace in the firing process.
Drawings
FIG. 1 is a schematic view showing the structure of a silicon nitride/fused quartz composite crucible according to the present invention;
wherein, 1-silicon nitride crucible; 2-a fused silica crucible layer;
Fig. 2 is an XRD pattern of a silicon nitride assembly prepared according to example 1 of the present invention.
Detailed Description
The invention is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
The invention provides a silicon nitride/fused quartz composite crucible, which comprises a silicon nitride crucible with an inner layer and a fused quartz crucible layer coated on the outer layer of the silicon nitride crucible, wherein the silicon nitride crucible is formed by assembling a plurality of plate-shaped silicon nitride components, and the fused quartz crucible layer is hooped inwards to form compressive stress on the silicon nitride crucible with the inner layer.
The invention also provides a preparation method of the silicon nitride/fused quartz composite crucible, which comprises the following steps:
step S1, mixing silicon powder, a sintering aid and a binder solution into uniform slurry, obtaining a blank body through cold isostatic pressing, and discharging glue from the blank body;
step S2, sintering the blank in a sintering furnace after the glue discharging is completed to obtain a silicon nitride component with a compact structure;
and S3, assembling a plurality of plate-shaped silicon nitride assemblies into a complete silicon nitride crucible, and hooping the fused quartz crucible layer on the outer surface of the silicon nitride crucible to obtain the silicon nitride/fused quartz composite crucible.
In the invention, the average grain diameter of the silicon powder is 0.5-1.5 mu m. The preparation cost of the silicon powder with smaller grain size is higher, and the silicon powder with larger grain size is difficult to be nitrided completely, so that the grain size of the silicon powder needs to be controlled in a proper range.
As the preferable technical scheme, the silicon powder is selected from silicon powder with the average particle size of 0.6-0.7 mu m and 1.3-1.4 mu m, and the silicon powder is combined according to the mass ratio of 1 (2-3), so that the obtained composite crucible has longer service life.
In the invention, the binder solution is prepared by dissolving a binder in an organic solvent, and the content of the binder is 1-3wt%.
In the present invention, the organic solvent includes, but is not limited to, at least one of ethanol, methanol, and acetone. As long as an organic solvent which can dissolve the binder and has low toxicity is selected.
In the present invention, the binder includes, but is not limited to, at least one of polyvinyl butyral (PVB), polyethylene glycol (PEG). An organic binder may be used, or an inorganic binder may be used. When inorganic binder is used, water is used to replace organic solvent to prepare slurry.
In the present invention, the sintering aid includes, but is not limited to, at least one of yttria, alumina, lanthana, zirconia.
In the invention, the usage amount of the sintering aid is 0-5wt% of the total amount of the silicon powder and the sintering aid. I.e. sintering aids may or may not be added.
In the invention, the solid content of the slurry is 40-55%. If the solids content is too small or too large, the viscosity of the slurry will vary and the size of the granulated particles will vary.
In the present invention, the slurry is spray granulated prior to cold isostatic pressing. The granules obtained by spray granulation are advantageous for subsequent shaping and the solvent can also be removed during granulation.
In the invention, the pressure of the cold isostatic pressing is 180-250 MPa. And through the cold isostatic pressing process, the structural density of the silicon nitride blank is improved.
In the invention, the glue discharge is vacuum glue discharge at 400-600 ℃. The function of the glue discharging is to decompose and remove organic matters, and the vacuum glue discharging avoids the oxidation of silicon.
In the present invention, the nitriding sintering includes pre-nitriding sintering and complete nitriding sintering.
As a preferred technical scheme, the sintering comprises pre-nitriding sintering, complete nitriding sintering and densification sintering; preferably, the pre-nitriding sintering is performed in nitrogen and/or ammonia atmosphere, the temperature is 1200-1300 ℃, the time is 4-8 hours, and the pressure is 1 atmosphere; the complete nitriding sintering is performed in nitrogen and/or ammonia atmosphere, firstly, the temperature is 1300-1400 ℃ and the pressure is 1 atmosphere, the heat preservation sintering is performed for 24-36 hours, and then the temperature is 1400-1480 ℃ and the pressure is 1 atmosphere, the heat preservation sintering is performed for 12-24 hours; the densification sintering is performed in a nitrogen atmosphere, the temperature is 1650-1800 ℃, the time is 1-4 h, and the pressure is 5-10 MPa.
In order to improve the precision of the silicon nitride crucible assembly, the silicon nitride crucible assembly can be mechanically processed (such as turning, milling and planing) between the pre-nitriding sintering and the complete nitriding sintering. By adopting fractional nitridation, the size change of the blank is small in the nitriding process, and the hardness of the pre-nitrided blank is small, so that the blank is easier to machine.
For the silicon nitride crucible assembly, before the assembly into a complete silicon nitride crucible, the silicon nitride crucible assembly can be subjected to fine machining, so that the dimensional accuracy is further improved, and gaps are reduced. The two-step process is because the hardness of the pre-nitrided blank is relatively small and the blank is easy to process, and at this time, rough processing is performed first and fine processing is performed after complete nitriding.
In the invention, the tightening temperature of the fused quartz crucible layer is 1650-1750 ℃.
As an optimal technical scheme, the hooping is to place the silicon nitride crucible in the quartz crucible, and the quartz crucible generates compressive stress on the silicon nitride crucible after being heated, so that hooping of the inner silicon nitride crucible is realized.
As the preferable technical scheme, the hooping is to back-buckle the silicon nitride crucible, heat the silicon nitride crucible to soften the quartz, and the fused quartz is coated on the outer wall of the silicon nitride crucible under the action of gravity.
Because the thermal expansion coefficient of quartz is smaller than that of silicon nitride, the quartz on the outer layer can generate compressive stress on the silicon nitride crucible on the inner layer after being heated, the structural strength of the crucible is improved, and the service life of the crucible is prolonged.
The invention also provides application of the silicon nitride/fused quartz composite crucible in casting monocrystalline silicon or polycrystalline silicon.
Example 1
Step S1, PVB is dissolved in ethanol to prepare binder solution, and PVB content is 1wt%; silica powder (average particle size of 0.5 μm) and yttria were uniformly mixed with a binder solution to form a slurry having a solid content of 40wt% (mass ratio of silica powder to yttria: 95:5), and then spray-granulated (average particle size of 60 μm), and cold isostatic press-molded to obtain a green body, which was subjected to paste ejection at 400 ℃ under vacuum.
S2, after the glue discharging is completed, pre-nitriding sintering (nitrogen atmosphere) is carried out on the green body in a sintering furnace, wherein the temperature is 1200 ℃, the time is 8 hours, and the pressure is 1 atmosphere; machining the silicon nitride crucible assembly; carrying out complete nitriding sintering (nitrogen atmosphere) on the machined silicon nitride crucible assembly, firstly preserving heat for 36h under the conditions of 1300 ℃ and 1 atmosphere pressure, and then preserving heat for 24h under the conditions of 1400 ℃ and 1 atmosphere pressure; and finally, carrying out densification sintering (nitrogen atmosphere) at the temperature of 1650 ℃ for 4 hours and the pressure of 10MPa to obtain the silicon nitride crucible assembly with a compact structure.
And S3, finely processing the silicon nitride crucible assembly, then assembling the silicon nitride crucible assembly into a complete silicon nitride crucible (with the outer diameter of 42 inches), placing the silicon nitride crucible in a fused silica crucible (with the inner diameter of 42 inches plus 0.1 inches), and heating to 1650 ℃ to enable the fused silica crucible to be clamped on the outer surface of the silicon nitride crucible, thereby obtaining the composite crucible.
Example 2
Step S1, PVB is dissolved in ethanol to prepare binder solution, and PVB content is 2wt%; silica powder (average particle size of 1.1 μm) and yttria were uniformly mixed with a binder solution to form a slurry having a solid content of 40wt% (mass ratio of silica powder to yttria of 98:2), then spray-granulated (average particle size of 80 μm), and cold isostatic press-molded to obtain a green body, and the green body was subjected to paste ejection at 500 ℃ under vacuum.
S2, after the glue discharging is completed, pre-nitriding sintering (nitrogen atmosphere) is carried out on the green body in a sintering furnace, wherein the temperature is 1250 ℃, the time is 6 hours, and the pressure is 1 atmosphere; machining the silicon nitride crucible assembly; carrying out complete nitriding sintering (nitrogen atmosphere) on the machined silicon nitride crucible assembly, firstly preserving heat for 30 hours under the conditions of 1350 ℃ and 1 atmosphere pressure, and then preserving heat for 20 hours under the conditions of 1450 ℃ and 1 atmosphere pressure; and finally, carrying out densification sintering (nitrogen atmosphere) at 1700 ℃ for 2 hours and under the pressure of 8MPa to obtain the silicon nitride crucible assembly with compact structure.
And S3, finely processing the silicon nitride crucible assembly, then assembling the silicon nitride crucible assembly into a complete silicon nitride crucible (with the outer diameter of 42 inches), placing the silicon nitride crucible in a fused silica crucible (with the inner diameter of 42 inches plus 0.1 inches), and heating to 1700 ℃ to enable the fused silica crucible to be clamped on the outer surface of the silicon nitride crucible, thereby obtaining the composite crucible.
Example 3
Step S1, PVB is dissolved in ethanol to prepare binder solution, and PVB content is 3wt%; silicon powder (average grain size of 1.5 μm) and a binder solution are uniformly mixed to form slurry with solid content of 50wt%, then spray granulation (average grain size of 100 μm) is carried out, a green body is obtained through cold isostatic pressing, and the green body is subjected to glue discharging under the vacuum condition of 600 ℃.
S2, after the glue discharging is completed, pre-nitriding sintering (nitrogen atmosphere) is carried out on the green body in a sintering furnace, wherein the temperature is 1300 ℃, the time is 4 hours, and the pressure is 1 atmosphere; machining the silicon nitride crucible assembly; carrying out complete nitriding sintering (nitrogen atmosphere) on the machined silicon nitride crucible assembly, firstly preserving heat for 24 hours under the conditions of 1400 ℃ and 1 atmosphere pressure, and then preserving heat for 12 hours under the conditions of 1480 ℃ and 1 atmosphere pressure; and finally, carrying out densification sintering (nitrogen atmosphere) under the conditions of 1800 ℃ and 1h of time and 5MPa of pressure to obtain the silicon nitride crucible assembly with compact structure.
And S3, finely processing the silicon nitride crucible assembly, then assembling the silicon nitride crucible assembly into a complete silicon nitride crucible (with the outer diameter of 42 inches), placing the silicon nitride crucible in a fused silica crucible (with the inner diameter of 42 inches plus 0.1 inches), and heating to 1750 ℃ to enable the fused silica crucible to be clamped on the outer surface of the silicon nitride crucible, so as to obtain the composite crucible.
Example 4
Step S1, dissolving PEG4000 in ethanol to prepare a binder solution, wherein the PVB content is 1wt%; silica powder (average particle size of 0.5 μm) and yttrium oxide, aluminum oxide were uniformly mixed with a binder solution to form a slurry having a solid content of 40wt% (mass ratio of silica powder to yttrium oxide, aluminum oxide: 95:2:3), and then spray-granulated (average particle size of 60 μm), and a green body was obtained by cold isostatic press molding, and was subjected to paste ejection at 400 ℃ under vacuum.
S2, after the glue discharging is completed, pre-nitriding and sintering the blank in a sintering furnace (50% nitrogen+50% ammonia atmosphere) at 1230 ℃ for 8 hours under 1 atmosphere; machining the silicon nitride crucible assembly; carrying out complete nitriding sintering (50% nitrogen+50% ammonia atmosphere) on the machined silicon nitride crucible assembly, firstly preserving heat for 36h under the conditions of 1350 ℃ and 1 atmosphere pressure, and then preserving heat for 24h under the conditions of 1420 ℃ and 1 atmosphere pressure; and finally, carrying out densification sintering (nitrogen atmosphere) at the temperature of 1650 ℃ and the pressure of 8MPa for 4 hours to obtain the silicon nitride crucible assembly with a compact structure.
Step S3, same as in example 1.
Example 5
Step S1 is the same as in example 1.
Step S2 is the same as in example 1.
And S3, finely processing the silicon nitride crucible assembly, then assembling the silicon nitride crucible assembly into a complete silicon nitride crucible (the outer diameter is 42 inches), reversely buckling the silicon nitride crucible, heating to 1650 ℃ to soften quartz, and coating the fused quartz on the outer wall of the silicon nitride crucible under the action of gravity to obtain the composite crucible.
Comparative example 1 (one-step nitriding, difficult machining)
Step S1 is the same as in example 1.
Step S2, after the glue discharging is completed, nitriding and sintering the blank in a sintering furnace (nitrogen atmosphere), firstly preserving heat for 36h under the conditions of 1300 ℃ and 1 atmosphere pressure, and then preserving heat for 24h under the conditions of 1400 ℃ and 1 atmosphere pressure; and finally, carrying out densification sintering (nitrogen atmosphere) at the temperature of 1650 ℃ for 4 hours and the pressure of 10MPa to obtain the silicon nitride crucible assembly with a compact structure.
Step S3, same as in example 1.
Comparative example 2 (preparation directly from silicon nitride powder)
Step S1, PVB is dissolved in ethanol to prepare binder solution, and PVB content is 1wt%; silicon nitride powder (average grain size of 0.5 μm) and yttrium oxide are uniformly mixed with a binder solution to form slurry with solid content of 40wt% (mass ratio of silicon nitride to yttrium oxide is 95:5), then spray granulation (average grain size of 60 μm) is carried out, a green body is obtained through cold isostatic pressing, and the green body is subjected to glue discharging under the vacuum condition of 400 ℃.
Step S2 is the same as in example 1.
Step S3, same as in example 1.
Comparative example 3 (silica fume having an average particle diameter of less than 0.5 μm)
Step S1, PVB is dissolved in ethanol to prepare binder solution, and PVB content is 1wt%; silica powder (average particle size of 0.2 μm) and yttria were uniformly mixed with a binder solution to form a slurry having a solid content of 40wt% (mass ratio of silica powder to yttria: 95:5), and then spray-granulated (average particle size of 60 μm), and cold isostatic press-molded to obtain a green body, which was subjected to paste ejection at 400 ℃ under vacuum.
S2, after the glue discharging is completed, pre-nitriding sintering (nitrogen atmosphere) is carried out on the green body in a sintering furnace, wherein the temperature is 1200 ℃, the time is 8 hours, and the pressure is 1 atmosphere; machining the silicon nitride crucible assembly; carrying out complete nitriding sintering (nitrogen atmosphere) on the machined silicon nitride crucible assembly, firstly preserving heat for 30h under the conditions of 1300 ℃ and 1 atmosphere pressure, and then preserving heat for 24h under the conditions of 1400 ℃ and 1 atmosphere pressure; and finally, carrying out densification sintering (nitrogen atmosphere) at the temperature of 1650 ℃ for 4 hours and the pressure of 10MPa to obtain the silicon nitride crucible assembly with a compact structure.
Step S3, same as in example 1.
Comparative example 4 (silica fume having an average particle diameter of greater than 1.5 μm)
Step S1, PVB is dissolved in ethanol to prepare binder solution, and PVB content is 1wt%; silica powder (average particle size of 2.0 μm) and yttria were uniformly mixed with a binder solution to form a slurry having a solid content of 40wt% (mass ratio of silica powder to yttria: 95:5), and then spray-granulated (average particle size of 60 μm), and cold isostatic press-molded to obtain a green body, which was subjected to paste ejection at 400 ℃ under vacuum.
S2, after the glue discharging is completed, pre-nitriding sintering (nitrogen atmosphere) is carried out on the green body in a sintering furnace, wherein the temperature is 1200 ℃, the time is 8 hours, and the pressure is 1 atmosphere; machining the silicon nitride crucible assembly; carrying out complete nitriding sintering (nitrogen atmosphere) on the machined silicon nitride crucible assembly, firstly preserving heat for 40h under the conditions of 1300 ℃ and 1 atmosphere pressure, and then preserving heat for 24h under the conditions of 1400 ℃ and 1 atmosphere pressure; and finally, carrying out densification sintering (nitrogen atmosphere) at the temperature of 1650 ℃ for 4 hours and the pressure of 10MPa to obtain the silicon nitride crucible assembly with a compact structure.
Step S3, same as in example 1.
Comparative example 1 uses one-step nitriding and comparative example 2 uses silicon nitride powder as raw materials, the crucible assembly has large hardness, machining is difficult, and finally, the fine machining has large workload and high difficulty. Comparative example 3 uses small-sized silicon powder, the nitriding time is shortened, but the manufacturing difficulty of small-sized silicon powder is greater. Comparative example 4 uses silicon powder with large particle size, and the nitriding time is prolonged.
Example 6
Step S1, PVB is dissolved in ethanol to prepare binder solution, and PVB content is 1wt%; silica powder (two specifications of average particle size of 0.6 μm and 1.3 μm, mass ratio of 1:2) and yttrium oxide are uniformly mixed with binder solution to form slurry with solid content of 40wt% (mass ratio of silica powder to yttrium oxide is 95:5), then spray granulation (average particle size of 60 μm) is carried out, a green body is obtained through cold isostatic pressing, and the green body is subjected to glue discharging under the vacuum condition of 400 ℃.
Step S2 is the same as in example 1.
Step S3, same as in example 1.
Example 7
Step S1, PVB is dissolved in ethanol to prepare binder solution, and PVB content is 1wt%; silica powder (two specifications of average particle size of 0.7 μm and 1.4 μm, mass ratio of 1:3) and yttrium oxide are uniformly mixed with binder solution to form slurry with solid content of 40wt% (mass ratio of silica powder to yttrium oxide is 95:5), then spray granulation (average particle size of 60 μm) is carried out, a green body is obtained through cold isostatic pressing, and the green body is subjected to glue discharging under the vacuum condition of 400 ℃.
Step S2 is the same as in example 1.
Step S3, same as in example 1.
Example 8
Step S1, PVB is dissolved in ethanol to prepare binder solution, and PVB content is 1wt%; silica powder (average particle size of 0.6 μm) and yttria were uniformly mixed with a binder solution to form a slurry having a solid content of 40wt% (mass ratio of silica powder to yttria: 95:5), and then spray-granulated (average particle size of 60 μm), and cold isostatic press-molded to obtain a green body, which was subjected to paste ejection at 400 ℃ under vacuum.
Step S2 is the same as in example 1.
Step S3, same as in example 1.
Example 9
Step S1, PVB is dissolved in ethanol to prepare binder solution, and PVB content is 1wt%; silica powder (average particle size of 1.4 μm) and yttria were uniformly mixed with a binder solution to form a slurry having a solid content of 40wt% (mass ratio of silica powder to yttria: 95:5), and then subjected to granulation (average particle size of 60 μm), and a green body was obtained by cold isostatic press molding, and the green body was subjected to paste ejection at 400 ℃ under vacuum.
Step S2 is the same as in example 1.
Step S3, same as in example 1.
Comparative example 5 (lowering the pinch temperature of a fused silica crucible layer)
Step S1 is the same as in example 1.
Step S2 is the same as in example 1.
And S3, finely processing the silicon nitride crucible assembly, then assembling the silicon nitride crucible assembly into a complete silicon nitride crucible (with the outer diameter of 42 inches), placing the silicon nitride crucible in a fused silica crucible (with the inner diameter of 42 inches plus 0.1 inches), and heating to 1550 ℃ to enable the fused silica crucible to be clamped on the outer surface of the silicon nitride crucible, so as to obtain the composite crucible.
Comparative example 6
See example 1 of CN101479410 a.
Comparative example 7 (silicon nitride coating process)
Dissolving PVB in ethanol to prepare a binder solution, wherein the PVB content is 1wt%; silicon powder (average grain diameter is 0.5 μm) and yttrium oxide are uniformly mixed with a binder solution to form slurry with solid content of 40wt% (mass ratio of silicon powder to yttrium oxide is 95:5), then the slurry is sprayed on the inner wall of a quartz crucible (coating thickness is 10 filaments), the glue discharging is carried out under the vacuum condition of 400 ℃, and after the glue discharging is completed, the sintering is carried out for 0.5h at 1300 ℃.
The composite crucibles prepared in the above examples and comparative examples were subjected to performance tests, and the test results are shown in table 1.
The density was measured by archimedes' displacement method.
The service life is determined by long-time silicon melting experiment in an argon atmosphere furnace at 1450 ℃.
TABLE 1
As can be seen from table 1:
The embodiment 6-7 adopts two silicon powders with different specifications (average particle size is 0.6-0.7 μm and 1.3-1.4 μm), which can obviously improve the density of the crucible and prolong the service life of the crucible.
Comparative example 5 although the compounding of the quartz crucible and the silicon nitride crucible was also achieved at a heating temperature of 1550 c, the quartz crucible crystallized and became brittle and cracked, resulting in a great reduction in the service life of the crucible.
Comparative example 6 because the density of silicon nitride ceramic element is different from that of silicon nitride at the sealing part, the problem of uneven stress exists in the repeated use process, and cracks can appear at the sealing part, so that the service life of the crucible is shortened.
Comparative example 7 the silicon nitride coating sprayed on the inner wall of the quartz crucible has the advantage of simple operation, but the obtained composite crucible has poor density and short service life. This is because when the silicon liquid penetrates through the coating layer, the silicon dioxide in the quartz crucible at the outer layer participates in the reaction, and the quality of the product is affected, and the crucible cannot be used.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A silicon nitride/fused quartz composite crucible, characterized in that: the silicon nitride crucible comprises an inner silicon nitride crucible and a fused silica crucible layer coated on the outer layer of the silicon nitride crucible, wherein the silicon nitride crucible is formed by assembling a plurality of plate-shaped silicon nitride components, the fused silica crucible layer is hooped inwards, and compressive stress is formed on the inner silicon nitride crucible;
the hooping is to place the silicon nitride crucible in the quartz crucible, and the quartz crucible generates compressive stress on the silicon nitride crucible after being heated, so that hooping of the inner silicon nitride crucible is realized;
Or;
The hooping is to back-buckle the silicon nitride crucible, heat the silicon nitride crucible to soften the quartz, and the fused quartz is coated on the outer wall of the silicon nitride crucible under the action of gravity.
2. The method for preparing a silicon nitride/fused quartz composite crucible according to claim 1, comprising the steps of:
step S1, mixing silicon powder, a sintering aid and a binder solution into uniform slurry, obtaining a blank body through cold isostatic pressing, and discharging glue from the blank body;
step S2, sintering the blank in a sintering furnace after the glue discharging is completed to obtain a silicon nitride component with a compact structure;
and S3, assembling a plurality of plate-shaped silicon nitride assemblies into a complete silicon nitride crucible, and hooping the fused quartz crucible layer on the outer surface of the silicon nitride crucible to obtain the silicon nitride/fused quartz composite crucible.
3. The preparation method according to claim 2, characterized in that: the average grain diameter of the silicon powder is 0.5-1.5 mu m;
the silicon powder is prepared from silicon powder with an average particle size of 0.6-0.7 mu m and two specifications of 1.3-1.4 mu m according to a mass ratio of 1 (2-3).
4. The preparation method according to claim 2, characterized in that: the binder solution is prepared by dissolving a binder in an organic solvent, and the content of the binder is 1-3wt%;
The organic solvent is at least one selected from ethanol, methanol and acetone;
The binder is at least one selected from polyvinyl butyral and polyethylene glycol.
5. The preparation method according to claim 2, characterized in that: the sintering aid is at least one selected from yttrium oxide, aluminum oxide, lanthanum oxide and zirconium oxide;
The usage amount of the sintering aid is 0-5wt% of the total amount of the silicon powder and the sintering aid.
6. The preparation method according to claim 2, characterized in that: the pressure of the cold isostatic pressing is 180-250 MPa.
7. The preparation method according to claim 2, characterized in that: and the glue discharging is vacuum glue discharging at 400-600 ℃.
8. The preparation method according to claim 2, characterized in that: the sintering includes pre-nitriding sintering, complete nitriding sintering and densification sintering; the pre-nitriding sintering is performed in a nitrogen and/or ammonia atmosphere, the temperature is 1200-1300 ℃, the time is 4-8 hours, and the pressure is 1 atmosphere; the complete nitriding sintering is performed in nitrogen and/or ammonia atmosphere, firstly, the temperature is 1300-1400 ℃ and the pressure is 1 atmosphere, the heat preservation sintering is performed for 24-36 hours, and then the temperature is 1400-1480 ℃ and the pressure is 1 atmosphere, the heat preservation sintering is performed for 12-24 hours; the densification sintering is performed in a nitrogen atmosphere, the temperature is 1650-1800 ℃, the time is 1-4 h, and the pressure is 5-10 MPa.
9. The preparation method according to claim 2, characterized in that: the tightening temperature of the fused quartz crucible layer is 1650-1750 ℃.
10. Use of a silicon nitride/fused silica composite crucible according to claim 1 or obtained by the production method according to any one of claims 2 to 9 in single crystal silicon or polycrystalline silicon casting.
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| CN111253162A (en) * | 2019-02-22 | 2020-06-09 | 中国科学院上海硅酸盐研究所苏州研究院 | Method for preparing high-strength high-toughness high-thermal-conductivity silicon nitride ceramic |
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| US4741925A (en) * | 1987-09-14 | 1988-05-03 | Gte Products Corporation | Method of forming silicon nitride coating |
| US6165425A (en) * | 1997-02-06 | 2000-12-26 | Bayer Aktiengesellschaft | Melting pot with silicon protective layers, method for applying said layer and the use thereof |
| JP4217844B2 (en) * | 1998-06-18 | 2009-02-04 | ジャパンスーパークォーツ株式会社 | Composite crucible and manufacturing method and regeneration method thereof |
| CN201395646Y (en) * | 2009-03-11 | 2010-02-03 | 周宇 | Silicon nitride ceramic integral crucible |
| CN104060324A (en) * | 2014-06-17 | 2014-09-24 | 江西赛维Ldk太阳能高科技有限公司 | Demolding layer applied to polycrystalline silicon ingot casting, polycrystalline silicon ingot casting method and crucible for ingot casting |
| TW201816200A (en) * | 2016-08-03 | 2018-05-01 | 法商維蘇威法國公司 | Crucible for crystallization of molten silicon, process for its manufacture and use thereof |
| CN116514579A (en) * | 2023-03-31 | 2023-08-01 | 徐州协鑫太阳能材料有限公司 | Black sand full-melting efficient crucible for polycrystalline ingot casting and preparation method |
| CN116815300A (en) * | 2023-04-28 | 2023-09-29 | 常州轶梵科技有限公司 | Combined crucible for pulling single crystal bar by single crystal furnace |
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| JPS6241793A (en) * | 1985-08-12 | 1987-02-23 | Toshiba Ceramics Co Ltd | Crucible for pulling up silicon single crystal |
| CN101555014A (en) * | 2009-05-11 | 2009-10-14 | 福建丰力机械科技有限公司 | Combined polysilicon purification and solidification crucible |
| CN111253162A (en) * | 2019-02-22 | 2020-06-09 | 中国科学院上海硅酸盐研究所苏州研究院 | Method for preparing high-strength high-toughness high-thermal-conductivity silicon nitride ceramic |
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