CN118186567B - Quartz crucible with elemental silicon doped layer and preparation method and application thereof - Google Patents
Quartz crucible with elemental silicon doped layer and preparation method and application thereof Download PDFInfo
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- CN118186567B CN118186567B CN202410599871.3A CN202410599871A CN118186567B CN 118186567 B CN118186567 B CN 118186567B CN 202410599871 A CN202410599871 A CN 202410599871A CN 118186567 B CN118186567 B CN 118186567B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 154
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 86
- 239000010703 silicon Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 239000010453 quartz Substances 0.000 title claims abstract description 54
- 239000000126 substance Substances 0.000 claims abstract description 85
- 239000006004 Quartz sand Substances 0.000 claims abstract description 83
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 68
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 229910052788 barium Inorganic materials 0.000 claims description 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004321 preservation Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 120
- 230000000052 comparative effect Effects 0.000 description 24
- 239000013078 crystal Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005554 pickling Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010314 arc-melting process Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
Classifications
-
- 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
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B20/00—Processes specially adapted for the production of quartz or fused silica articles, not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Glass Melting And Manufacturing (AREA)
Abstract
The invention discloses a quartz crucible with an elemental silicon doped layer, and a preparation method and application thereof, and belongs to the technical field of crucibles. The quartz crucible comprises a bubble layer, a simple substance silicon doping layer and a transparent layer which are sequentially arranged from outside to inside; the preparation raw materials of the elemental silicon doped layer comprise first quartz sand and elemental silicon powder; the mass percentage of the simple substance silicon powder in the preparation raw materials of the simple substance silicon doped layer is not more than 15 percent. Through setting up simple substance silicon doped layer between bubble layer and transparent layer, can promote the high temperature resistance and the anti deformability of crucible in monocrystalline silicon drawing process, be favorable to extension crucible live time, in addition, it can also promote the temperature homogeneity of drawing monocrystalline silicon in-process, improves heat preservation effect and heat energy utilization efficiency.
Description
Technical Field
The invention relates to the technical field of crucibles, in particular to a quartz crucible with an elemental silicon doped layer, and a preparation method and application thereof.
Background
The quartz crucible is an important accessory for pulling a single crystal silicon rod by the Czochralski method (CZ method). The quartz crucible has an irreplaceable function as a carrier for the silicon material. In order to meet the production requirement of high-quality monocrystalline silicon, the quartz crucible is generally composed of an outer bubble layer and an inner transparent layer, wherein the inner layer is in direct contact with silicon liquid, and the outer bubble layer is in contact with the graphite crucible, so that a uniform heat conduction effect is achieved. In the long-time and high-temperature (such as about 1500 ℃) use process, the inherent shape of the silicon single crystal cannot be maintained due to the reduction of strength, and the deformation problems such as local bulge and bending are generated, so that the silicon single crystal pulling process is greatly influenced, and finally the production efficiency of the silicon single crystal is greatly reduced.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a quartz crucible with a simple substance silicon doped layer, and a preparation method and application thereof, so as to solve or improve the technical problems.
The invention can be realized as follows:
In a first aspect, the invention provides a quartz crucible, which comprises a bubble layer, a simple substance silicon doping layer and a transparent layer which are sequentially arranged from outside to inside;
The preparation raw materials of the elemental silicon doped layer comprise first quartz sand and elemental silicon powder; the mass percentage of the simple substance silicon powder in the preparation raw materials of the simple substance silicon doped layer is not more than 15 percent.
In an alternative embodiment, the particle size of the first quartz sand is 50-170 μm, and the purity of the first quartz sand is not lower than 99.99%;
and/or the particle size of the elemental silicon powder is 1-50 mu m, and the purity of the elemental silicon powder is not lower than 99.99%.
In an alternative embodiment, the transparent layer is prepared from a second quartz sand, and the bubble layer is prepared from a third quartz sand;
the particle size of the third quartz sand is larger than that of the second quartz sand, and the purity of the third quartz sand is smaller than that of the second quartz sand.
In an alternative embodiment, the particle size of the third quartz sand is 120 μm to 300 μm, and the purity of the third quartz sand is not less than 99.9%.
In an alternative embodiment, the elemental silicon doped layer is prepared from a mixture of first quartz sand and elemental silicon powder.
In an alternative embodiment, the thickness of the transparent layer is 1.2 mm-6 mm, the thickness of the bubble layer is 2 mm-15 mm, and the total thickness of the elemental silicon doped layers is 0.1 mm-1.5 mm.
In an alternative embodiment, the quartz crucible further comprises a barium-containing coating disposed on the inner surface of the transparent layer.
In a second aspect, the present invention provides a method for preparing a quartz crucible according to any of the previous embodiments, comprising the steps of: and (3) paving preparation raw materials of each layer in the mould according to the setting positions of the bubble layer, the simple substance silicon doped layer and the transparent layer, melting the preparation raw materials in an arc melting mode, cooling after forming, and demoulding.
In an alternative embodiment, the conditions of arc melting include at least one of the following features:
characteristic one: the melting current of the transparent layer and the simple substance silicon doping layer is 800A-10000A;
and the second characteristic is: the melting current of the bubble layer is 500A-70000A;
and (3) the following characteristics: the rotation speed of the die is 50 rpm-100 rpm.
In a third aspect, the present invention provides the use of a quartz crucible according to any of the preceding embodiments, for example for the preparation of monocrystalline silicon.
The beneficial effects of the invention include:
According to the invention, the simple substance silicon doping layer is arranged between the bubble layer and the transparent layer, so that the high temperature resistance and the deformation resistance of the crucible in the single crystal silicon drawing process can be improved, and the service time of the crucible can be prolonged. In addition, the temperature uniformity in the process of pulling monocrystalline silicon can be improved, and the heat preservation effect and the heat energy utilization efficiency are improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view showing the structure of a quartz crucible provided in example 1;
FIG. 2 is an SEM image of a doped layer of elemental silicon in a quartz crucible of example 1;
FIG. 3 is an EDS diagram of an elemental silicon doped layer in the quartz crucible of example 1;
Fig. 4 is an XRD pattern of an elemental silicon doped layer in the quartz crucible of example 1.
Icon: 11-a barium-containing coating; 12-a transparent layer; 13-elemental silicon doped layer; 14-bubble layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The quartz crucible with the elemental silicon doped layer, the preparation method and the application thereof provided by the invention are specifically described below.
The invention provides a quartz crucible with an elemental silicon doped layer, which comprises a bubble layer, an elemental silicon doped layer and a transparent layer which are sequentially arranged from outside to inside.
The preparation raw materials of the elemental silicon doped layer comprise first quartz sand and elemental silicon powder; the mass percentage of the simple substance silicon powder in the preparation raw materials of the simple substance silicon doping layer is not more than 15%;
the transparent layer is prepared from a second quartz sand;
The bubble layer is prepared from third quartz sand.
The simple substance silicon doped layer contains Si and SiO 2, and by arranging the simple substance silicon doped layer between the bubble layer and the transparent layer, the high temperature resistance and the deformation resistance of the crucible in the single crystal silicon drawing process can be improved, the service time of the crucible can be prolonged, in addition, the temperature uniformity in the single crystal silicon drawing process can be improved, and the heat preservation effect and the heat energy utilization efficiency can be improved. Furthermore, the simple substance silicon doped layer can play a role in isolating and blocking the inward diffusion of bubbles in the bubble layer, and the conditions of softening, swelling and the like of the crucible in the long-time use process are avoided.
In some embodiments, the elemental silicon doped layer may be prepared from only the first quartz sand and the elemental silicon powder after mixing.
In the present invention, the mass percentage of the elemental silicon powder in the preparation raw material of the elemental silicon doped layer is not more than 15%, for example, the mass percentage of the elemental silicon powder in the preparation raw material of the elemental silicon doped layer may be 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1%, etc., and may be other values within a range of not more than 15%.
If the amount of the simple substance silicon powder is too small, the effects of uniform heat conduction and crucible strength enhancement at high temperature cannot be realized; if the dosage of the simple substance silicon powder is excessive, the silicon simple substances in the crucible are easily connected with each other to form oversized particles, and the crucible is invalid in a long-time thermal field use environment.
In some preferred embodiments, the mass percentage of the elemental silicon powder in the preparation raw materials of the elemental silicon doped layer is 5% -10%, so that the quartz crucible has better deformation resistance, crystallization resistance and high-temperature impact resistance.
In some embodiments, the particle size of the first quartz sand may be 50 μm to 170 μm, such as 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, etc., and may be other values in the range of 50 μm to 170 μm.
In some embodiments, the purity of the first quartz sand is not less than 99.99%.
In some embodiments, the elemental silicon powder may have a particle size of 1 μm to 50 μm, such as 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, or 50 μm, etc., and may have other values in the range of 1 μm to 50 μm. In some preferred embodiments, the elemental silicon powder may have a particle size of 8 μm.
In some embodiments, the elemental silicon powder has a purity of not less than 99.99%.
The quality and specification of the second quartz sand can be referred to the first quartz sand, namely the particle size of the second quartz sand can be 50-170 mu m, and the purity is not lower than 99.99%.
The particle size of the third quartz sand is larger than that of the second quartz sand, and the purity of the third quartz sand is smaller than that of the second quartz sand.
In some embodiments, the particle size of the third quartz sand may be 120 μm to 300 μm, such as 120 μm, 140 μm, 160 μm, 180 μm, 200 μm, 220 μm, 240 μm, 260 μm, 280 μm, 300 μm, etc., and may be other values in the range of 120 μm to 300 μm.
In some embodiments, the purity of the third quartz sand is not less than 99.9%.
In some embodiments, the total thickness of the quartz crucible is no more than 30mm.
In some embodiments, the thickness of the transparent layer may be 1.2mm to 6mm, such as 1.2mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 5.5mm, or 6mm, etc., and may be other values in the range of 1.2mm to 6 mm.
The thickness of the bubble layer may be 2mm to 15mm, such as 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm or 15mm, and the like, and may be other values within the range of 2mm to 15 mm.
The total thickness of the elemental silicon doped layer can be 0.1 mm-1.5 mm, such as 0.1mm, 0.2mm, 0.5mm, 1mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm or 1.5mm, and the like, and can also be other values within the range of 0.1 mm-1.5 mm.
If the total thickness of the simple substance silicon doped layer exceeds 1.5mm, the whole crucible wall is easy to be too thick, and the thermal efficiency is influenced.
Further, the quartz crucible also includes a barium-containing coating disposed on an inner surface of the transparent layer. The relevant content of the barium-containing coating can be found in the prior art and is not excessively limited here.
Correspondingly, the invention also provides a preparation method of the quartz crucible, which comprises the following steps: and (3) paving preparation raw materials of each layer in the mould according to the setting positions of the bubble layer, the simple substance silicon doped layer and the transparent layer, melting the preparation raw materials in an arc melting mode, cooling after forming, and demoulding.
In some embodiments, reference may be made to the following: uniformly paving third quartz sand for preparing a bubble layer in a cavity of a die, paving a preparation raw material for preparing a simple substance silicon doped layer on the inner side of the layer, and paving second quartz sand for preparing a transparent layer on the inner side of the layer. Transferring the whole mould into an arc melting furnace, releasing high-temperature electric arc through a graphite electrode to melt quartz sand, cooling and molding, spraying the quartz sand on the surface of a molded quartz crucible blank by using a spray gun to remove attachments on the surface of the quartz crucible blank, taking out the quartz crucible blank, immersing the quartz crucible blank into an HF pickling tank with the weight percent of 6-8% for pickling, immersing into clean water for washing, and performing high-pressure cleaning and ultrasonic cleaning to remove residual ions on the surface of the quartz crucible blank. And finally, dissolving barium hydroxide powder in water, adding the solution into a barium coating machine, and uniformly spraying the solution on the inner surface of a quartz crucible blank to obtain the quartz crucible.
In some embodiments, the melting current of the transparent layer may be 800A to 10000A, such as 800A, 1000A, 2000A, 3000A, 4000A, 5000A, 6000A, 7000A, 8000A, 9000A, 10000A, or the like, or any other value within a range of 800A to 10000A.
The melting current of the simple substance silicon doped layer can be 800A-10000A, such as 800A, 1000A, 2000A, 3000A, 4000A, 5000A, 6000A, 7000A, 8000A, 9000A or 10000A, and can be any other value within the range of 800A-10000A.
The melting current of the bubble layer may be 500A to 70000A, such as 500A, 800A, 1000A, 2000A, 3000A, 4000A, 5000A, 6000A or 7000, or any other value within the range of 500A to 70000A.
The rotation speed of the mold may be 50rpm to 100rpm, such as 50rpm, 55rpm, 60rpm, 65rpm, 70rpm, 75rpm, 80rpm, 85rpm, 90rpm, 95rpm, 100rpm, or any other value within the range of 50rpm to 100 rpm.
On the premise of bearing, the preparation method of the quartz crucible provided by the invention is simple, the conditions are easy to control, and the quartz crucible can be industrially produced.
In addition, the invention also provides an application of the quartz crucible, for example, the quartz crucible is used for preparing monocrystalline silicon.
The quartz crucible provided by the invention has higher thermal stability and higher rigidity at high temperature, and the simple substance silicon doped layer positioned between the transparent layer and the bubble layer can prevent the gas in the bubble layer from diffusing to the transparent layer so as to reduce the risk of crucible swelling. In addition, the quartz crucible does not introduce impurity atoms, so that the influence on the purity of the crystal bar in the process of drawing the crystal bar with high purity is avoided.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a quartz crucible, please refer to fig. 1, which comprises a bubble layer 14, a simple substance silicon doping layer 13, a transparent layer 12 and a barium-containing coating layer 11, which are sequentially arranged from outside to inside.
Wherein, the bubble layer 14 is prepared from third quartz sand with the particle diameter of 200 μm and the purity of 99.997%. The preparation raw materials of the simple substance silicon doped layer 13 are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 94:6. Wherein the particle size of the first quartz sand is 110 mu m, and the purity is 99.998%; the particle size of the elemental silicon powder is 5 mu m, and the purity is 99.999%. The transparent layer 12 is prepared from a second quartz sand which is identical to the first quartz sand in the elemental silicon doped layer 13.
The thickness of the bubble layer 14 was 7mm, the thickness of the elemental silicon doped layer 13 was 1mm, the thickness of the transparent layer 12 was 5mm, and the thickness of the barium-containing coating layer 11 was 5 μm.
An SEM image of the elemental silicon doped layer 13 is shown in fig. 2, in which small particles are doped Si. The EDS diagram of the elemental silicon doped layer 13 is shown in fig. 3, in which it can also be seen that the elemental silicon powder is present in elemental form of Si. The XRD pattern of the elemental silicon doped layer 13 is shown in fig. 4, where the presence of elemental silicon in a crystalline state in the glassy phase can be seen.
The preparation of the quartz crucible comprises the following steps:
The third quartz sand for preparing the bubble layer 14 is uniformly laid in the cavity of the mold, then the preparation raw material for preparing the elemental silicon doped layer 13 (the first quartz sand and the elemental silicon powder are uniformly mixed in advance) is laid on the inner side of the layer, and then the second quartz sand for preparing the transparent layer 12 is laid on the inner side of the layer. Transferring the whole mould into an arc melting furnace, releasing high-temperature electric arc through a graphite electrode to melt quartz sand, cooling and molding, spraying the quartz sand on the surface of a molded quartz crucible blank by using a spray gun, taking out the quartz crucible blank, immersing the quartz crucible blank into a 7wt% HF pickling tank for pickling, immersing into clean water for water washing, and performing high-pressure cleaning and ultrasonic cleaning. And finally, dissolving barium hydroxide powder in water, adding the solution into a barium coating machine, and uniformly spraying the solution on the inner surface of a quartz crucible blank to form a barium-containing coating 11, thereby obtaining the quartz crucible.
In the arc melting process, the rotating speed of the die is 80rpm, the die is melted for 5min under the condition that the current is 5000A, and then melted for 6min under the condition that the current is 3000A.
Example 2
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 93:7. The particle size of the elemental silicon powder was 8. Mu.m.
Example 3
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 97:3. The particle size of the elemental silicon powder was 10. Mu.m.
Example 4
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 98:2. The particle size of the elemental silicon powder was 12. Mu.m.
Example 5
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 91:9. Wherein the particle size of the first quartz sand is 50 mu m, and the particle size of the simple substance silicon powder is 12 mu m.
Example 6
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 90:10. Wherein the particle size of the first quartz sand is 80 mu m, and the particle size of the simple substance silicon powder is 10 mu m.
Example 7
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 92:8. Wherein the particle size of the first quartz sand is 140 mu m, and the particle size of the simple substance silicon powder is 12 mu m.
Example 8
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 92:8. Wherein the particle size of the first quartz sand is 170 mu m, and the particle size of the simple substance silicon powder is 15 mu m.
Example 9
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 90:10. Wherein the particle size of the elemental silicon powder is 14 μm.
Example 10
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 93:7. Wherein the particle size of the elemental silicon powder is 12 μm.
Example 11
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 91:9. Wherein the particle size of the elemental silicon powder is 10 μm.
Example 12
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 89:11. Wherein the particle size of the elemental silicon powder is 15 μm.
Example 13
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 95:5.
Example 14
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 90:10.
Example 15
This embodiment differs from embodiment 1 in that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 88:12.
Example 16
This embodiment differs from embodiment 1 in that: in the preparation raw materials of the simple substance silicon doped layer, the particle size of the simple substance silicon powder is 1 mu m.
Example 17
This embodiment differs from embodiment 1 in that: in the preparation raw material of the simple substance silicon doped layer, the particle size of the simple substance silicon powder is 3 mu m.
Comparative example 1
The difference between this comparative example and example 1 is that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 90:10. Wherein the particle size of the elemental silicon powder is 60 μm.
Comparative example 2
The difference between this comparative example and example 1 is that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 40:60. Wherein the particle size of the elemental silicon powder is 15 μm.
Comparative example 3
The difference between this comparative example and example 1 is that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 60:40. Wherein the particle size of the first quartz sand is 40 mu m, and the particle size of the simple substance silicon powder is 30 mu m.
Comparative example 4
The difference between this comparative example and example 1 is that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 85:15. Wherein the particle size of the first quartz sand is 180 mu m, and the particle size of the simple substance silicon powder is 20 mu m.
Comparative example 5
The difference between this comparative example and example 1 is that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 80:20. Wherein the particle size of the elemental silicon powder is 0.8 μm.
Comparative example 6
The difference between this comparative example and example 1 is that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 40:60. Wherein the particle size of the elemental silicon powder is 0.2 μm.
Comparative example 7
The difference between this comparative example and example 1 is that: the preparation raw materials of the simple substance silicon doped layer are obtained by mixing first quartz sand and simple substance silicon powder according to the mass ratio of 80:20.
Comparative example 8
The difference between this comparative example and example 1 is that: the particle size of the first quartz sand was 20. Mu.m.
Comparative example 9
The difference between this comparative example and example 1 is that: the particle size of the first quartz sand was 200. Mu.m.
Comparative example 10
The difference between this comparative example and example 1 is that: the particle size of the elemental silicon powder was 60. Mu.m.
Comparative example 11
The difference between this comparative example and example 1 is that: and an elemental silicon doped layer is not arranged between the transparent layer and the bubble layer.
Test examples
The quartz crucibles obtained in examples 1 to 17 and comparative examples 1 to 11 were used at 1450 ℃, and the time for deformation was recorded, and the results are shown in table 1. Wherein the thermal conductivity is tested according to ISO 22007.
Table 1 comparative results
As can be seen from Table 1, the quartz crucible provided by the invention can be used for a long time at high temperature, which is beneficial to prolonging the service life of the crucible and improving the crystal pulling efficiency and quality.
In conclusion, the quartz crucible provided by the invention has the advantages of better deformation resistance, crystallization resistance and high-temperature impact resistance, and is beneficial to prolonging the service life of the crucible and improving the crystal pulling efficiency and quality.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The quartz crucible is characterized by comprising a bubble layer, an elemental silicon doping layer and a transparent layer which are sequentially arranged from outside to inside;
the preparation raw materials of the simple substance silicon doped layer comprise first quartz sand and simple substance silicon powder; the mass percentage of the elemental silicon powder in the preparation raw materials of the elemental silicon doped layer is not more than 15%;
The grain diameter of the first quartz sand is 50-170 mu m, and the purity of the first quartz sand is not lower than 99.99%; the particle size of the elemental silicon powder is 1-50 mu m, and the purity of the elemental silicon powder is not lower than 99.99%;
the simple substance silicon doping layer is prepared by mixing first quartz sand and simple substance silicon powder; the quartz crucible further comprises a barium-containing coating disposed on an inner surface of the transparent layer.
2. The quartz crucible of claim 1, wherein the transparent layer is prepared from a second quartz sand and the bubble layer is prepared from a third quartz sand;
The particle size of the third quartz sand is larger than that of the second quartz sand, and the purity of the third quartz sand is smaller than that of the second quartz sand.
3. The quartz crucible according to claim 2, wherein the particle size of the third quartz sand is 120 μm to 300 μm, and the purity of the third quartz sand is not lower than 99.9%.
4. The quartz crucible of claim 1, wherein the transparent layer has a thickness of 1.2mm to 6mm, the bubble layer has a thickness of 2mm to 15mm, and the elemental silicon doped layer has a total thickness of 0.1mm to 1.5mm.
5. A method for producing a quartz crucible having an elemental silicon doped layer according to any one of claims 1 to 4, comprising the steps of: and (3) paving preparation raw materials of each layer in the mould according to the setting positions of the bubble layer, the simple substance silicon doped layer and the transparent layer, melting the preparation raw materials in an arc melting mode, cooling after forming, and demoulding.
6. The method of claim 5, wherein the arc melting conditions include at least one of the following characteristics:
Characteristic one: the melting current of the transparent layer and the simple substance silicon doping layer is 800A-10000A;
and the second characteristic is: the melting current of the bubble layer is 500A-70000A;
and (3) the following characteristics: the rotation speed of the die is 50 rpm-100 rpm.
7. Use of a quartz crucible with a doped layer of elemental silicon according to any of claims 1 to 4 or a quartz crucible prepared by a preparation method according to any of claims 5 to 6, for preparing single crystal silicon.
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CN109930198A (en) * | 2017-12-18 | 2019-06-25 | 上海新昇半导体科技有限公司 | Heat shielding and monocrystalline silicon growing furnace structure |
CN116377579A (en) * | 2023-04-13 | 2023-07-04 | 锦州佑鑫石英科技有限公司 | Long-life quartz crucible for improving crystallization rate of single crystal silicon first rod |
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JP4987029B2 (en) * | 2009-04-02 | 2012-07-25 | ジャパンスーパークォーツ株式会社 | Silica glass crucible for pulling silicon single crystals |
CN116949556A (en) * | 2023-07-19 | 2023-10-27 | 南昌大学共青城光氢储技术研究院 | Silicon oxynitride-quartz composite material crucible and preparation method thereof |
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CN116377579A (en) * | 2023-04-13 | 2023-07-04 | 锦州佑鑫石英科技有限公司 | Long-life quartz crucible for improving crystallization rate of single crystal silicon first rod |
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