CN115231909A - Preparation method of quartz crucible air bubble layer - Google Patents
Preparation method of quartz crucible air bubble layer Download PDFInfo
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- CN115231909A CN115231909A CN202110437862.0A CN202110437862A CN115231909A CN 115231909 A CN115231909 A CN 115231909A CN 202110437862 A CN202110437862 A CN 202110437862A CN 115231909 A CN115231909 A CN 115231909A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000010453 quartz Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000006004 Quartz sand Substances 0.000 claims abstract description 61
- 239000013078 crystal Substances 0.000 claims abstract description 43
- 239000012535 impurity Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 16
- 238000012216 screening Methods 0.000 claims abstract description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000007689 inspection Methods 0.000 claims abstract description 6
- 238000009417 prefabrication Methods 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims description 65
- 230000008018 melting Effects 0.000 claims description 65
- 239000002131 composite material Substances 0.000 claims description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 14
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- -1 calcium nitride Chemical class 0.000 claims description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 5
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- 230000005855 radiation Effects 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 description 9
- 230000002035 prolonged effect Effects 0.000 description 8
- 230000007547 defect Effects 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000010891 electric arc Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/10—Crucibles or containers for supporting the melt
-
- 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
- C30B29/02—Elements
- C30B29/06—Silicon
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
Abstract
The invention relates to the technical field of quartz crucible bubble layers, and discloses a preparation method of a quartz crucible bubble layer, which comprises the following steps: s1: preparing raw materials, weighing quartz sand which is qualified in quality inspection and meets production requirements, classifying and screening by using a vibration screening machine, and removing metal impurities, hydroxyl compounds and other alkane gases in the quartz sand to obtain high-purity quartz sand; s2: debugging before prefabrication, and debugging the included angle and the rotating speed of a crucible mold; s3: prefabricating an outer layer of the thin bubble, and adding quartz sand raw materials into a metal alloy mould for rotary forming. The quartz sand crystal puller can avoid the reaction of metal impurities and crystals during crystal pulling, improve the crystal pulling quality, reduce the density of bubbles near a contact solution, reduce the influence of expansion and breakage of the bubbles on crystal pulling after long-time high-temperature operation, uniformly radiate a radiation source provided by a heater, quickly remove the metal impurities in quartz sand raw materials and greatly reduce the production cost.
Description
Technical Field
The invention relates to the technical field of quartz crucible bubble layers, in particular to a preparation method of a quartz crucible bubble layer.
Background
The quartz crucible is essential basic equipment in the process of pulling the monocrystalline silicon, the conventional arc quartz crucible for pulling the monocrystalline consists of an inner layer and an outer layer, the inner layer is a transparent layer, and the content of bubbles is low; the outer layer is a bubble composite layer, the content of bubbles is high, and the bubble composite layer is a part for supporting the deformation strength of the crucible and ensuring the uniform radiation of a heat source.
In the process of long-time and high-temperature use, bubbles on the outer layer of the quartz crucible expand and break, liquid and other impurities released in the broken bubbles and the inner surface of the quartz crucible chemically react to cause the outer wall of the quartz crucible to have a crystallization layer, the crystallization layer gradually thickens along with the increase of crystal pulling time, the crystallization layer becomes thicker along with the increase of the crystal pulling time, the deformation resistance and the heat radiation efficiency of the quartz crucible are gradually reduced, finally, the abnormal rate and the crystallization rate of crystal pulling are increased, and the requirements of a crystal pulling process can not be met.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of a quartz crucible bubble layer, which mainly aims to solve the problems that the existing quartz crucible is easy to deform and the heat radiation efficiency is reduced when in use, so that the crystal pulling quality is influenced.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a quartz crucible bubble layer comprises the following steps:
s1: preparing raw materials, weighing quartz sand which is qualified in quality inspection and meets production requirements, classifying and screening by adopting a vibration screening machine, and then removing metal impurities, hydroxyl compounds and other alkane gases in the quartz sand to obtain high-purity quartz sand;
s2: debugging before prefabrication, and debugging the included angle and the rotating speed of a crucible mold;
s3: prefabricating an outer layer of the thin bubble, adding quartz sand raw materials into a metal alloy mould, and rotationally molding;
s4: prefabricating a composite inner layer, mixing at least one of silicon nitride, aluminum nitride, calcium nitride and lithium nitride with quartz sand to add a certain content of nitrogen, and then placing the mixture in a metal alloy mold for internal rotation forming;
s5: melting, namely melting a prefabricated bubble layer in the mould at high temperature by using a vacuum arc, firstly melting a composite inner layer, and then melting a thin bubble outer layer;
s6: cooling and demoulding, namely naturally cooling the melted quartz crucible for demoulding;
s7: and detecting the diameter of the quartz crucible, the thicknesses of the transparent layer and the opaque layer and the bubble content.
Further, the sieving machine in the S1 adopts 50-150 meshes of vibration, then hydrogen chloride gas is introduced at the temperature of 1000-1400 ℃ to remove hydroxyl compounds, other alkane gases and metal impurities in the quartz sand crystals, and the hydrogen chloride gas is introduced at a stable high temperature, so that the total content of the impurities in the high-purity quartz sand is less than or equal to 20ppm.
On the basis of the scheme, the crucible mold in the S2 is inclined to the position where the included angle between the crucible mold and the horizontal plane is 60-95 degrees, and the rotating speed of the mold is 55-130r/min.
As a further aspect of the present invention, the vacuum degree in the metal alloy mold in S3 is 0.01pa to 0.1pa.
Further, the content of nitrogen added in the S4 is about 1 to 15 atomic percent, and the composite inner layer comprises a transparent layer (bubble depletion layer) and a bubble composite layer.
On the basis of the scheme, when the bubble composite layer is melted in the S5, firstly, the vacuum degree in a melting furnace is set to be-0.03 Mpa to-0.09 Mpa, the melting is finished after 1-9min by the power of 300KW to 2000KW, then the vacuum is closed, the melting is finished after 4-20min by the power of 350KW to 1850KW, the vacuum degree of the melted thin bubble layer is set to be-0.052 Mpa to-0.076 Mpa, the melting is finished after 1-12min by the power of 380-1800KW, the melting temperature is controlled to be 2200 ℃ to 2600 ℃, and the arc striking voltage of a graphite electrode rod in the melting furnace is 130V to 150V.
In a further scheme of the invention, in the step S6, the mold can be removed after being cooled to 40-50 ℃.
Further, the microbubbles that the transparent layer of bubble contains in S7 are 11-15/mm, the microbubbles that the bubble composite bed contains are 35-55/mm, the microbubbles that the thin bubble outer layer contains are 10-12/mm, the content of microbubbles that the transparent layer and the thin bubble outer layer contain is all less than the bubble composite bed, the thickness of thin bubble outer layer 2 is 1-2mm, compound inlayer 3-5mm.
(III) advantageous effects
Compared with the prior art, the invention provides a high-density combined coating material for a quartz crucible and a preparation method thereof, and the high-density combined coating material has the following beneficial effects:
1. in the invention, during crystal pulling, the high-purity quartz sand can avoid the reaction of metal impurities and crystals, the crystal pulling quality is improved, the hydrogen chloride gas is used for purifying the quartz sand, the purity of the quartz sand is further refined and improved, the viscosity of the quartz crucible is improved, and the service life of the quartz crucible is prolonged.
2. In the invention, the transparent layer in the composite inner layer aims at reducing the density of bubbles near the contact solution, reducing the influence of expansion and rupture of the bubbles on crystal pulling after long-time high-temperature operation and avoiding the direct contact of silicon liquid with a crucible body to react during crystal pulling, and the bubble composite layer aims at providing a radiation source for a uniform radiation heater.
3. In the invention, the graphite electrode is used for generating electric arc, strong current is led into a smelting area of the smelting furnace through the electrode, so that electric energy is converted into heat energy, the purpose of smelting or reacting is achieved, the smelting temperature is increased to over 2200 ℃, metal impurities such as lithium, aluminum, potassium, sodium and the like in the quartz sand raw material are rapidly removed, the defect that the raw material only depends on imported quartz sand is overcome, and the production cost is greatly reduced.
4. According to the invention, the crucible body can be conveniently taken out after being cooled to a certain temperature for demoulding, the crucible is prevented from deforming when being taken out, the demoulding quality of the quartz crucible is improved, the bubble composite layer with more micro-bubble content is arranged between the transparent layer with less micro-bubble content and the thin bubble outer layer, so that the uniform radiation of a heat source of the quartz crucible during crystal pulling work is ensured, the bubbles in the bubble composite layer are prevented from expanding and cracking in the crystal pulling process, the reduction of the heat radiation efficiency is avoided, the service life of the quartz crucible is prolonged, and the normal operation of crystal pulling is ensured.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a high-density combined coating material for a quartz crucible, which is provided by the invention.
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, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
Referring to fig. 1, the preparation method of the bubble layer of the quartz crucible comprises the following steps:
s1: preparing raw materials, weighing quartz sand which is qualified in quality inspection and meets production requirements, classifying and screening by using a vibration screening machine, and removing metal impurities, hydroxyl compounds and other alkane gases in the quartz sand to obtain high-purity quartz sand;
s2: debugging before prefabrication, and debugging the included angle and the rotating speed of a crucible mold;
s3: prefabricating an outer layer of the thin bubble, adding quartz sand raw materials into a metal alloy mould, and carrying out rotary molding;
s4: prefabricating a composite inner layer, mixing at least one of silicon nitride, aluminum nitride, calcium nitride and lithium nitride with quartz sand to add a certain content of nitrogen, then placing the mixture in a metal alloy mold for spin forming, wherein the added nitrogen element can prevent the crucible from generating oxidation reaction at high temperature and is beneficial to melting the crucible;
s5: melting, namely melting the prefabricated bubble layer in the mold at high temperature by using a vacuum arc, melting the composite inner layer firstly, and then melting the thin bubble outer layer;
s6: cooling and demoulding, namely naturally cooling the melted quartz crucible for demoulding;
s7: and detecting the diameter of the quartz crucible, the thicknesses of the transparent layer and the opaque layer and the bubble content.
In the invention, a sieving machine in S1 vibrates by 50-150 meshes, hydrogen chloride gas is introduced at 1000-1400 ℃ to remove hydroxyl compounds, other alkane gases and metal impurities in quartz sand crystals, the hydrogen chloride gas is introduced at stable high temperature, the total impurity content of high-purity quartz sand is less than or equal to 20ppm, the high-purity quartz sand can avoid the metal impurities from reacting with the crystals during crystal pulling, the crystal pulling quality is improved, the quartz sand is further refined by hydrogen chloride gas to improve the quartz sand purity so as to improve the quartz crucible viscosity, the service life of the quartz crucible is prolonged, a crucible mold in S2 is inclined to a position with an included angle of 60-95 degrees with the horizontal plane, the rotating speed of the mold is 55-130r/min, the vacuum degree in the metal alloy mold in S3 is 0.01-0.1paS4, the content of nitrogen is about 1-15% of atoms, a composite inner layer comprises a transparent layer (a bubble depletion layer) and a bubble composite layer, the purpose of reducing the bubble density near a contact solution, reducing the influence of expansion after long-time operation on the contact of the silicon crystal pulling after the high-temperature operation, and avoiding the radiation of a crucible body during crystal pulling reaction, and providing a uniform radiation composite layer of the crucible.
It should be particularly noted that when the bubble composite layer is melted in S5, firstly, the vacuum degree in the melting furnace is set to-0.03 Mpa to-0.09 Mpa, the melting is finished after 1-9min with the power of 300KW to 2000KW, then the vacuum is closed, the melting is finished after 4-20min with the power of 350KW to 1850KW, the vacuum degree of the melted thin bubble layer is-0.052 Mpa to-0.076 Mpa, the melting is finished after 1-12min with the power of 380-1800KW, the melting temperature is controlled to 2200 ℃ -2600 ℃, the arcing voltage of a graphite electrode rod in the melting furnace is 130V-150V, a graphite electrode is used, strong current is led into the melting zone of the melting furnace through the electrode to generate electric arc, electric energy is converted into heat energy, thereby achieving the purpose of melting or reaction, the melting temperature is increased to over 2200 ℃, metal impurities such as lithium, aluminum, potassium, sodium and the like in the quartz sand raw material are rapidly removed, the defect that raw materials only depend on imported quartz sand is overcome, the production cost is greatly reduced, demoulding can be carried out when the raw materials are cooled to 40-50 ℃ in S6, demoulding can be carried out when the raw materials are cooled to a certain temperature, the crucible body can be conveniently taken out, the deformation of the crucible when the crucible is taken out is prevented, the demoulding quality of the quartz crucible is improved, the number of micro bubbles contained in the transparent layer of the bubbles in S7 is 11-15/mm, the number of micro bubbles contained in the bubble composite layer is 35-55/mm, the number of micro bubbles contained in the outer layer of the thin bubbles is 10-12/mm, the content of the micro bubbles contained in the transparent layer and the outer layer of the thin bubbles is smaller than that of the bubble composite layer, the thickness of the outer layer of the thin bubbles is 1-2mm, the composite inner layer is 3-5mm, the bubble composite layer with more content of the micro bubbles is arranged between the transparent layer with less content of the micro bubbles and the outer layer of the thin bubbles, and the uniform radiation of a heat source of the quartz crucible during crystal pulling work is ensured, and the bubbles in the bubble composite layer are prevented from expanding and cracking in the crystal pulling process, so that the reduction of the heat radiation efficiency is avoided, the service life of the quartz crucible is prolonged, and the normal operation of crystal pulling is ensured.
Example 2
Referring to fig. 1, the preparation method of the bubble layer of the quartz crucible comprises the following steps:
s1: preparing raw materials, weighing quartz sand which is qualified in quality inspection and meets production requirements, classifying and screening by using a vibration screening machine, and removing metal impurities, hydroxyl compounds and other alkane gases in the quartz sand to obtain high-purity quartz sand;
s2: debugging before prefabrication, and debugging the included angle and the rotating speed of a crucible mold;
s3: prefabricating an outer layer of the thin bubble, adding quartz sand raw materials into a metal alloy mould, and rotationally molding;
s4: prefabricating a composite inner layer, mixing at least one of silicon nitride, aluminum nitride, calcium nitride and lithium nitride with quartz sand to add a certain content of nitrogen, then placing the mixture in a metal alloy mold for spin forming, and adding nitrogen elements to prevent the crucible from generating oxidation reaction at high temperature and facilitate the melting of the crucible;
s5: melting, namely melting a prefabricated bubble layer in the mould at high temperature by using a vacuum arc, firstly melting a composite inner layer, and then melting a thin bubble outer layer;
s6: cooling and demolding, namely naturally cooling the melted quartz crucible for demolding;
s7: and detecting the diameter of the quartz crucible, the thicknesses of the transparent layer and the opaque layer and the bubble content.
In the invention, a sieving machine in S1 vibrates by adopting a 60-180 meshes sieve, then hydrogen chloride gas is introduced at 1000-1200 ℃ to remove hydroxyl compounds, other alkane gases and metal impurities in quartz sand crystals, the hydrogen chloride gas is introduced at a stable high temperature, the total content of the impurities in high-purity quartz sand is less than or equal to 20ppm, when the quartz is pulled, the high-purity quartz sand can prevent the metal impurities from reacting with the crystals, the quality of the pulled crystals is improved, the quartz sand is further refined by using the hydrogen chloride gas to improve the purity of the quartz sand so as to improve the viscosity of the quartz crucible, the service life of the quartz crucible is prolonged, a crucible mold in S2 is inclined to a position with an included angle of 55-85 degrees between the crucible mold and the horizontal plane, the rotating speed of the mold is 60-150r/min, the vacuum degree in a metal alloy mold in S3 is 0.01-0.1paS4, the content of nitrogen is about 1-15% of atoms, a composite inner layer comprises a transparent layer (a bubble depletion layer) and a bubble composite layer, the transparent layer aims to reduce the bubble density near a contact solution, reduce the influence of the bubble on the expanded and the influence of the pulled crystals after the high-temperature operation, and avoid the direct radiation of a silicon crystal composite layer generated when the crucible body is subjected to react, and the crucible body is uniformly radiated when the crucible body.
It should be specially noted that when the bubble composite layer is melted in S5, firstly, the vacuum degree in the melting furnace is set to-0.02 Mpa-0.08 Mpa, the melting is finished after 5-10min with the power of 300KW-2000KW, then the vacuum is closed, the melting is finished after 5-15min with the power of 300KW-1800KW, the vacuum degree of the melted thin bubble layer is-0.052 Mpa-0.076 Mpa, the melting is finished after 2-8min with the power of 380-1800KW, the melting temperature is controlled to 2200 ℃ -2400 ℃, the arc striking voltage of the graphite electrode bar in the melting furnace is 120V-150V, a graphite electrode is used, strong current is led into the melting area of the melting furnace through the electrode to generate electric arc, electric energy is converted into heat energy, thereby achieving the purpose of melting or reaction, the melting temperature is increased to over 2200 ℃, metal impurities such as lithium, aluminum, potassium, sodium and the like in the quartz sand raw material are rapidly removed, the defect that raw materials only depend on imported quartz sand is overcome, the production cost is greatly reduced, demoulding can be carried out when the raw materials are cooled to 35-45 ℃ in S6, demoulding can be carried out when the raw materials are cooled to a certain temperature, the crucible body can be conveniently taken out, the deformation of the crucible when the crucible is taken out is prevented, the demoulding quality of the quartz crucible is improved, the number of micro bubbles contained in the transparent layer of the bubbles in S7 is 11-15/mm, the number of micro bubbles contained in the bubble composite layer is 35-50/mm, the number of micro bubbles contained in the outer layer of the thin bubbles is 8-12/mm, the content of the micro bubbles contained in the transparent layer and the outer layer of the thin bubbles is smaller than that of the bubble composite layer, the thickness of the outer layer of the thin bubbles is 1-2mm, the composite inner layer is 3-5mm, the bubble composite layer with more content of the micro bubbles is arranged between the transparent layer with less content of the micro bubbles and the outer layer of the thin bubbles, and the uniform radiation of a heat source of the quartz crucible during the crystal pulling work is ensured, and the bubbles in the bubble composite layer are prevented from expanding and cracking in the crystal pulling process, so that the reduction of the heat radiation efficiency is avoided, the service life of the quartz crucible is prolonged, and the normal operation of crystal pulling is ensured.
Example 3
Referring to fig. 1, a method for preparing a bubble layer of a quartz crucible comprises the following steps:
s1: preparing raw materials, weighing quartz sand which is qualified in quality inspection and meets production requirements, classifying and screening by using a vibration screening machine, and removing metal impurities, hydroxyl compounds and other alkane gases in the quartz sand to obtain high-purity quartz sand;
s2: debugging before prefabrication, and debugging the included angle and the rotating speed of a crucible mold;
s3: prefabricating an outer layer of the thin bubble, adding quartz sand raw materials into a metal alloy mould, and rotationally molding;
s4: prefabricating a composite inner layer, mixing at least one of silicon nitride, aluminum nitride, calcium nitride and lithium nitride with quartz sand to add a certain content of nitrogen, then placing the mixture in a metal alloy mold for spin forming, wherein the added nitrogen element can prevent the crucible from generating oxidation reaction at high temperature and is beneficial to melting the crucible;
s5: melting, namely melting the prefabricated bubble layer in the mold at high temperature by using a vacuum arc, melting the composite inner layer firstly, and then melting the thin bubble outer layer;
s6: cooling and demolding, namely naturally cooling the melted quartz crucible for demolding;
s7: and detecting the diameter of the quartz crucible, the thicknesses of the transparent layer and the opaque layer and the bubble content.
In the invention, a sieving machine in S1 vibrates by adopting a 60-140 meshes, then hydrogen chloride gas is introduced at 1000-1400 ℃ to remove hydroxyl compounds, other alkane gases and metal impurities in quartz sand crystals, the hydrogen chloride gas is introduced at stable high temperature, the total content of the impurities in high-purity quartz sand is less than or equal to 18ppm, when the quartz is pulled, the high-purity quartz sand can prevent the metal impurities from reacting with the crystals, the quality of the pulled crystals is improved, the quartz sand is further refined by using the hydrogen chloride gas to improve the purity of the quartz sand so as to improve the viscosity of the quartz crucible, the service life of the quartz crucible is prolonged, a crucible mold in S2 is inclined to a position with an included angle of 55-90 degrees between the crucible mold and the horizontal plane, the rotating speed of the mold is 60-150r/min, the vacuum degree in a metal alloy mold in S3 is 0.05-0.1paS4, the content of nitrogen is about 1-15% of atoms, a composite inner layer comprises a transparent layer (a bubble depletion layer) and a bubble composite layer, the transparent layer aims to reduce the density of bubbles near a contact solution, reduce the influence of the bubbles after the high-temperature operation, and avoid the direct radiation reaction of a silicon pulling liquid composite layer when the crucible body occurs, and the crucible is uniform radiation of the crucible.
It should be particularly noted that when the bubble composite layer is melted in S5, firstly, the vacuum degree in the melting furnace is set to-0.05 Mpa-0.09 Mpa, the melting is finished after 2-8min by 400KW-2000KW, then the vacuum is closed, the melting is finished after 5-20min by 350KW-1850KW, the vacuum degree of the melted thin bubble layer is-0.05 Mpa-0.07 Mpa, the melting is finished after 1-12min by 380-1600KW, the melting temperature is controlled to 2200 ℃ -2500 ℃, the arc striking voltage of a graphite electrode rod in the melting furnace is 130V-150V, a graphite electrode is used, strong current is led into the melting area of the melting furnace through the electrode to generate electric arc, so that the electric energy is converted into heat energy, thereby achieving the purpose of melting or reacting, the melting temperature is increased to over 2200 ℃, and metal impurities such as lithium, aluminum, potassium, sodium and the like in the quartz sand raw material are rapidly removed, the defect that raw materials only depend on imported quartz sand is overcome, the production cost is greatly reduced, demoulding can be carried out when the raw materials are cooled to 38-55 ℃ in S6, demoulding can be carried out when the raw materials are cooled to a certain temperature, the crucible body can be conveniently taken out, the deformation of the crucible when the crucible is taken out is prevented, the demoulding quality of the quartz crucible is improved, micro bubbles contained in a transparent layer of the bubbles in S7 are 10-18/mm, micro bubbles contained in a bubble composite layer are 30-55/mm, micro bubbles contained in an outer layer of the thin bubbles are 10-12/mm, the content of the micro bubbles contained in the transparent layer and the outer layer of the thin bubbles is smaller than that of the bubble composite layer, the thickness of the outer layer of the thin bubbles is 1-2mm, the composite inner layer is 4-5mm, the bubble composite layer with more content of the micro bubbles is arranged between the transparent layer with less content of the micro bubbles and the outer layer of the thin bubbles, and the uniform radiation of a heat source of the quartz crucible during crystal pulling work is ensured, and the bubbles in the bubble composite layer are prevented from expanding and cracking in the crystal pulling process, so that the reduction of the heat radiation efficiency is avoided, the service life of the quartz crucible is prolonged, and the normal operation of crystal pulling is ensured.
In the description herein, it is noted that relational terms such as first and second, and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of a quartz crucible bubble layer is characterized by comprising the following steps:
s1: preparing raw materials, weighing quartz sand which is qualified in quality inspection and meets production requirements, classifying and screening by adopting a vibration screening machine, and then removing metal impurities, hydroxyl compounds and other alkane gases in the quartz sand to obtain high-purity quartz sand;
s2: debugging before prefabrication, and debugging the included angle and the rotating speed of a crucible mold;
s3: prefabricating an outer layer of the thin bubble, adding quartz sand raw materials into a metal alloy mould, and carrying out rotary molding;
s4: prefabricating a composite inner layer, mixing at least one of silicon nitride, aluminum nitride, calcium nitride and lithium nitride with quartz sand to add a certain content of nitrogen, and then placing the mixture in a metal alloy mold for internal rotation forming;
s5: melting, namely melting a prefabricated bubble layer in the mould at high temperature by using a vacuum arc, firstly melting a composite inner layer, and then melting a thin bubble outer layer;
s6: cooling and demolding, namely naturally cooling the melted quartz crucible for demolding;
s7: and detecting the diameter of the quartz crucible, the thicknesses of the transparent layer and the opaque layer and the bubble content.
2. The preparation method of the bubble layer of the quartz crucible as claimed in claim 1, wherein the sieving machine in S1 is vibrated by 50-150 meshes, then hydrogen chloride gas is introduced at 1000-1400 ℃ to remove hydroxyl compounds, other alkane gases and metal impurities in quartz sand crystals, and the hydrogen chloride gas is introduced at a stable high temperature, so that the total content of impurities in high-purity quartz sand is less than or equal to 20ppm.
3. The method for preparing the bubble layer of the quartz crucible as claimed in claim 1, wherein the crucible mold in S2 is inclined to the position where the included angle between the crucible mold and the horizontal plane is 60-95 degrees, and the rotating speed of the mold is 55-130r/min.
4. The method for preparing a bubble layer of a quartz crucible according to claim 1, wherein the degree of vacuum in the metal alloy mold in S3 is 0.01pa to 0.1pa.
5. The method for preparing a bubble layer in a quartz crucible according to claim 1, wherein the content of nitrogen added in S4 is about 1 to 15 atomic%, and the composite inner layer comprises a transparent layer (bubble depletion layer) and a bubble composite layer.
6. The method for preparing the bubble layer of the quartz crucible according to claim 1, wherein when the bubble composite layer is melted in the S5, the vacuum degree in the melting furnace is firstly set to be-0.03 Mpa to-0.09 Mpa, the melting is finished after 1-9min by the power of 300KW to 2000KW, then the vacuum is closed, the melting is finished after 4-20min by the power of 350KW to 1850KW, the vacuum degree of the melted thin bubble layer is-0.052 MPa to-0.076 MPa, the melting is finished after 1-12min by the power of 380-1800KW, the melting temperature is controlled to be 2200 ℃ to 2600 ℃, and the arc starting voltage of the graphite electrode rod in the melting furnace is 130V to 150V.
7. The method for preparing a bubble layer of a quartz crucible as claimed in claim 1, wherein the mold is released when the temperature in S6 is cooled to 40-50 ℃.
8. The method as claimed in claim 1, wherein the transparent layer of the quartz crucible contains 11-15 microbubbles/mm, the composite layer of the bubbles contains 35-55 microbubbles/mm, the outer layer of the thin bubbles contains 10-12 microbubbles/mm, the transparent layer and the outer layer of the thin bubbles both contain microbubbles less than the composite layer, the outer layer 2 of the thin bubbles has a thickness of 1-2mm, and the composite inner layer has a thickness of 3-5mm.
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Application publication date: 20221025 |