CN110629281A - Preparation method of novel quartz crucible - Google Patents
Preparation method of novel quartz crucible Download PDFInfo
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- CN110629281A CN110629281A CN201910964642.6A CN201910964642A CN110629281A CN 110629281 A CN110629281 A CN 110629281A CN 201910964642 A CN201910964642 A CN 201910964642A CN 110629281 A CN110629281 A CN 110629281A
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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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- 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
- C04B35/64—Burning or sintering processes
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5007—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing
- C04B41/501—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing containing carbon in the anion, e.g. carbonates
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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- C04B41/85—Coating or impregnation with inorganic materials
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- 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
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- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/401—Alkaline earth metals
Abstract
The invention provides a preparation method of a novel quartz crucible, which comprises the following steps of preparing a blank crucible, wherein the blank crucible sequentially comprises a transparent layer and a bubble layer from inside to outside; coating an inner coating on one side of the transparent layer far away from the bubble layer; and coating an outer coating on the side of the bubble layer far away from the transparent layer. The novel preparation method of the quartz crucible designed by the invention can prevent the deformation of the opening at the upper end of the quartz crucible, improve the strength of the quartz crucible and prolong the service life of the quartz crucible; meanwhile, the service life of the tail part of the silicon single crystal rod pulled by the quartz crucible can be prolonged to some extent, the silicon single crystal rod has good crystallization rate and high conversion efficiency, and is used for pulling P-type and N-type silicon single crystal rods, so that the universality is high.
Description
Technical Field
The invention belongs to the technical field of solar-grade Czochralski silicon single crystal furnaces, and particularly relates to a preparation method of a novel quartz crucible.
Background
The quartz crucible is a main consumable material for pulling the monocrystalline silicon, one quartz crucible is needed to be used for producing one furnace of monocrystalline silicon, the development of the solar grade monocrystalline silicon at present mainly develops towards large size, flaking and high conversion efficiency, the quartz crucible is an important material for ensuring the growth of the monocrystalline silicon, and the quality of the quartz crucible directly determines the quality and the service life of the monocrystalline silicon.
In the melting process, the quartz crucible is influenced by high-temperature change, and the upper section part of the quartz crucible is easy to deform, so that the edge curling phenomenon appears on the upper end surface of the quartz crucible, the service life of the quartz crucible is shortened, and the quartz crucible is difficult to separate from the carbon-carbon crucible.
Meanwhile, in the prior art, a layer of barium hydroxide solution is often coated on the inner wall of the quartz crucible, and a crystallization layer is formed on the inner wall of the quartz crucible to improve the strength of the quartz crucible, so that the working process is complex, and if the crystallization layer is easily softened by the silicon solution, the service life of the quartz crucible is further shortened; coating the inner wall with a barium hydroxide solution tends to increase the content of barium ions entering the silicon solution, thereby reducing the service life of the tail of the single crystal silicon rod. Meanwhile, if the position of the silicon single crystal silicon rod is not controlled in the process of preparing the quartz crucible, a plurality of small holes can be formed in the inner wall of the quartz crucible, even metal ions on the inner wall of the quartz crucible can be increased, and in the process of pulling the single crystal silicon rod, the metal ions in the quartz crucible can react with molten silicon liquid at high temperature, so that more impurities are contained in the pulled silicon rod, the service life of the tail part of the single crystal silicon rod is shortened, and the conversion efficiency of the single crystal silicon wafer can be influenced.
Disclosure of Invention
The invention aims to provide a novel preparation method of a quartz crucible, which is suitable for drawing P-type and N-type monocrystalline silicon rods and solves the technical problems that the upper end surface of the quartz crucible is easy to curl and the service life is short in the prior art.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of a novel quartz crucible comprises the steps of preparing a blank crucible, wherein the blank crucible sequentially comprises a transparent layer and a bubble layer from inside to outside; coating an inner coating on one side of the transparent layer far away from the bubble layer; and coating an outer coating on the side of the bubble layer far away from the transparent layer.
Further, vacuum sintering is carried out in a firing furnace to prepare the transparent layer and the bubble layer; the vacuum degree of the firing furnace is not less than 1.55 Pa.
Furthermore, the high-temperature sintering temperature of the firing furnace is 1750-1850 ℃, and the sintering time is 35-45 min.
Further, the transparent layer is prepared by mixing high-purity quartz sand powder with 99.9999% and a small amount of barium powder.
Further, the content of the barium powder is 0.03-0.05 g/kg.
Further, the method also comprises cleaning the blank crucible before applying the inner coating and the outer coating.
Further, the cleaning sequentially comprises acid washing, water washing, high-pressure cleaning and ultrasonic cleaning.
Further, the pickling solution is hydrofluoric acid with the mass ratio of 6-8%.
Further, the inner coating and the outer coating are both formed by spraying barium hydroxide solution.
Further, the barium hydroxide solution is a saturated solution.
The quartz crucible designed by the invention has reasonable structural design, can prevent the upper section of the quartz crucible from curling at the position close to the upper end surface, improves the strength of the inner wall surface and avoids deformation; the service life of the crucible can be prolonged, the crystallization rate of the single crystal silicon rod can be increased, and the service life of the tail part of the single crystal silicon rod can be prolonged; the invention can be used for drawing the P-type silicon single crystal rod and the N-type silicon single crystal rod, the diameter size range of the drawn silicon single crystal rod is 160-320mm, the universality is high, and the popularization and the use are easy.
Drawings
FIG. 1 is a schematic structural view of a method for manufacturing a novel quartz crucible according to an embodiment of the present invention.
In the figure:
10. undercoating 20, clear layer 30, bubble layer
40. Outer coating
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The invention provides a preparation method of a novel quartz crucible, which comprises a straight cylinder part and a bending part arranged below the straight cylinder part, wherein the bending part is of a downward-convex arc-shaped structure, the bending part is symmetrically arranged, a connecting part is arranged between the straight cylinder part and the bending part, the connecting part is also of an arc-shaped structure, the radius R of the connecting part is smaller than the radius R of the bending part, two ends of the connecting part are respectively connected with the straight cylinder part and the bending part in an integrated tangent mode, and the thicknesses of the straight cylinder part, the connecting part and the bending part are the same. Further, an inner coating 10, a transparent layer 20, a bubble layer 30 and an outer coating 40 are sequentially arranged on the straight cylinder part from inside to outside, and the transparent layer 20, the bubble layer 30 and the outer coating 40 are sequentially arranged on the connecting part and the bending part cluster from inside to outside, wherein the inner coating 10 is used for improving the strength of the inner wall of the upper section part of the quartz crucible far away from a solid-liquid interface, reducing the softening phenomenon of the inner wall of the quartz crucible caused by high temperature and preventing the edge curling phenomenon; the transparent layer 20 is used for reducing the bubble density in the contact area with the silicon solution, weakening the intensity of the reaction between the bubbles and the silicon solution, and further reducing the hole density in the single crystal, thereby improving the success rate of single crystal growth and the quality of the single crystal silicon rod; the purpose of the bubble layer 30 is to uniformly conduct the heat radiated from the heater to the inner layer of the quartz crucible; the outer coating 40 is intended to form a dense cristobalite crystal layer on the outer wall of the quartz crucible, thereby not only increasing the strength of the quartz crucible and reducing the phenomenon that the quartz crucible is softened at high temperature, but also improving the service life of the quartz crucible and increasing the tail life and the crystallization rate of the single crystal silicon rod.
Specifically, the transparent layer 20 and the bubble layer 30 are prepared by a vacuum arc method, the transparent layer 20 is prepared by mixing 99.9999% of high-purity quartz sand powder with a small amount of barium powder, wherein the content of the barium powder is 0.03-0.05 g/kg; the bubble layer 30 is made of quartz sand powder having a purity lower than that of the transparent layer 20. Since the quartz sand powder contains air when melted at a high temperature, the air must be removed under a vacuum condition so that there are no bubbles in the transparent layer 20, and the bubbles are diffused into the bubble layer 30 outside the transparent layer 20 under a pressure difference, and since the purity of the quartz sand powder used in the bubble layer 30 is lower than that of the quartz sand powder in the transparent layer 20, many fine bubbles are present during the manufacturing process. Further, when the transparent layer 20 and the bubble layer 30 are prepared, the quartz sand powder in the transparent layer 20, the barium powder and the quartz sand powder in the bubble layer 30 are fully mixed and stirred, and the materials are added into a sintering mold; and vacuumizing for melting, wherein the vacuum degree in the melting furnace is not less than 1.55Pa, and the vacuumizing is gradually performed from top to bottom and from inside to outside. In the process of vacuum pumping, the area at the inner side can completely remove bubbles under the air pressure to form a compact and uniform transparent layer 20 with the thickness of 3-5 mm; the removed bubbles are diffused to the outside of the transparent layer 20 under the air pressure difference to form a region having a thickness of 1.5-3.5mm and a high bubble density, i.e., a bubble layer 30. And after the vacuum pumping is finished, starting electric arc by using a graphite electrode, starting melting and sintering, wherein the high-temperature sintering temperature is 1750-.
In the process, the transparent layer 20 has a smooth and compact surface, and because the transparent layer 20 contains a small amount of barium powder, the barium powder is uniformly stirred and mixed and then sintered at high temperature to form barium oxide (BaO), barium oxide and silicon dioxide (SiO)2) React to generate barium silicate (BaSiO)3). Due to the existence of barium silicate, fine dense cristobalite crystals are uniformly dispersed throughout the transparent layer 20 of the quartz crucible and closely fitted with silicon dioxide in the transparent layer 20, compared with the prior art in which only a layer of barium hydroxide (Ba (OH) is coated on the surface layer of the inner wall2) The effect of forming a surface white silica layer is better, and the white silica obtained in the embodiment can be fused with the silica in the transparent layer 20 into a whole, so that the white silica is difficult to be infiltrated by the silica solution and peeled off, and the inner wall of the white silica can be protected from being corroded easily, thereby not only enhancing the strength of the quartz crucible and improving the deformation resistance of the quartz crucible, but also reducing the high-temperature softening of the quartz crucible and further prolonging the service life of the quartz crucible. Meanwhile, the temperature of the inner wall surface of the quartz crucible can be reduced, and the devitrification phenomenon is prevented; in addition, the bubble density of the contact area of the quartz crucible and the silicon solution can be reduced, the intensity of the reaction between the bubbles and the silicon solution is weakened, and the hole density in the single crystal is further reduced; meanwhile, the structure can be adopted to reduceThe introduction of barium element in the process of single crystal silicon rod crystallization reduces the content of impurities in the process of single crystal growth, thereby achieving the purpose of improving the crystallization rate of single crystal growth and improving the quality of the single crystal silicon rod.
Both the undercoat layer 10 and the overcoat layer 40 are performed after the transparent layer 20 and the bubble layer 30 are completely prepared. Wherein, the inner coating 10 is arranged at the upper section of the inner wall of the transparent layer 20, the upper end surface of the inner coating 10 is arranged in parallel with the upper end surface of the transparent layer 20, and the height of the inner coating 10 is 30-50 mm. The thickness of the inner coating layer 10 and the thickness of the outer coating layer 40 are both smaller than the thickness of the bubble layer 30, and the thickness of the inner coating layer 10 is not greater than the thickness of the outer coating layer 40. Specifically, the thickness of the inner coating 10 is 0.4 to 0.6 mm; the thickness of the outer coating 40 is 0.5-1.5 mm; the thickness of each of the inner and outer coatings 10 and 40 is 1.5-3.5mm less than that of the bubble layer 30, and the thickness of the bubble layer 30 is 3-5mm less than that of the transparent layer 20. The outer coating 40 is disposed on the outer wall of the bubble layer 30, and the inner wall of the outer coating 40 is fitted to the outer wall of the bubble layer 30.
Further, the undercoat layer 10 and the overcoat layer 40 coating solutions are saturated barium hydroxide solutions (Ba (OH))2) Before coating the solution, a blank crucible formed by integrally processing the transparent layer 20 and the bubble layer 30 is cleaned, the blank crucible is firstly immersed into an HF pickling tank with the mass ratio of 6-8% for pickling, then is taken out and enters pure water for washing, and then is sequentially subjected to high-pressure cleaning and ultrasonic cleaning, so that residual metal ions on the inner wall and the outer wall of the blank crucible are removed. Then dissolving barium hydroxide powder in water to form saturated barium hydroxide solution, placing the blank crucible into a coating machine, and respectively spraying the barium hydroxide solution on the inner wall and the outer wall of the blank crucible to finally form an inner coating 10 with the thickness of 0.4-0.6mm and an outer coating 40 with the thickness of 0.5-1.5 mm. The specific applicator and rinse tank are well known to those skilled in the art and are omitted herein. Barium hydroxide is very easy to react with carbon dioxide (CO) in air2) Reacting to produce barium carbonate (BaCO)3) Respectively forming an inner coating 10 of barium carbonate on the upper section of the inner wall of the blank crucible and an outer coating 40 of barium carbonate on the outer wall of the blank crucible, namely respectively forming a section of barium carbonate with the height of 30-50mm and the thickness of barium carbonate on the upper section of the inner wall of the transparent layer 20The barium carbonate inner coating 10 with the degree of 0.4-0.6mm and the barium carbonate outer coating 40 with the thickness of 0.5-1.5mm are formed on the outer wall of the bubble layer 30, and the inner wall structure of the outer coating 40 is matched with the outer wall structure of the bubble layer 30. After the above steps, the quartz crucible having the inner coating layer 10, the transparent layer 20, the bubble layer 30 and the outer coating layer 40 sequentially arranged from the inside to the outside is finally formed.
The inner coating 10 coated within a height of 30-50mm of the upper section of the transparent layer 20 has little influence on the growth of single crystal, and the arrangement of the inner coating 10 enables the upper section of the quartz crucible near the upper edge top surface to be rapidly crystallized to form a dense layer, i.e., the dense layer is formed because the inner coating 10 of barium carbonate is easy to be decomposed at high temperature in the Czochralski single crystal process to generate barium oxide (BaO) and carbon dioxide (CO)2) And carbon dioxide is discharged as a gas. Meanwhile, partial barium oxide reaches the surface of the quartz crucible and is absorbed by the surface of the quartz crucible through the gas phase action to generate quartz crucible split phase, namely, the barium oxide reacts with silicon dioxide to generate barium silicate (BaSiO)3) Due to the existence of barium silicate, a layer of compact and tiny cristobalite crystals is formed on the wall of the quartz crucible. The arrangement of the coating 10 in the upper section of the quartz crucible can not only increase the strength of the quartz crucible, but also reduce the curling risk of the upper section of the quartz crucible; but also can reduce the softening phenomenon caused by high temperature, prolong the service life of the quartz crucible and reduce the production cost; meanwhile, impurity pollution of the inner coating 10 to the silicon solution can not be caused, and the resistivity of the silicon single crystal rod is ensured.
The barium carbonate of the outer coating 40 is closely attached to the carbon-carbon crucible outside the quartz crucible, and changes in the same way as the inner coating 10 when the material is heated to a high temperature, i.e., the barium carbonate and the carbon dioxide are easily decomposed to generate barium oxide and carbon dioxide, and the carbon dioxide is discharged as a gas; and simultaneously, barium oxide reaches the surface of the quartz crucible and is absorbed by the surface of the quartz crucible through the gas phase action, so that split phase of the quartz crucible is generated, namely barium oxide reacts with silicon dioxide to generate barium silicate, and a layer of compact and tiny cristobalite crystals are formed on the wall of the quartz crucible due to the existence of the barium silicate. The cristobalite crystal can reduce the reaction of the carbon-carbon crucible to the outer wall of the quartz crucible, reduce the corrosion of the carbon-carbon crucible to the outer wall of the quartz crucible, enhance the heating uniformity of the quartz crucible, and improve the strength of the outer wall of the quartz crucible, thereby achieving the purpose of improving the service time of the quartz crucible. Furthermore, the service life of the tail part of the single crystal silicon rod is attenuated relative to the content of metal impurities, and the outer coating 40 can reduce the content of barium ions entering the silicon solution, so that the purpose of improving the service life of the tail part of the single crystal silicon rod is achieved.
The quartz crucible provided by the embodiment forms the transparent layer 20 by doping trace barium impurities into quartz sand, so that the speed of the inner surface crystallization reaction can be reduced, the nucleation and growth processes of the dense layer are delayed, and the service life of the crucible is prolonged. Meanwhile, a layer of barium hydroxide solution is uniformly coated on the upper section of the inner wall of the transparent layer 20, so that the strength of the crucible can be enhanced, and the deformation problem can be prevented; the barium hydroxide solution is sprayed on the outer wall of the bubble layer 40, so that the outer wall of the crucible can be promoted to crystallize rapidly, the strength of the outer wall of the quartz crucible can be enhanced, and the outer wall of the quartz crucible is protected from being corroded; and the influence on the heating uniformity of the quartz crucible after the bubble layer of the quartz crucible is corroded can be prevented, so that the service time of the quartz crucible is prolonged.
The quartz crucible with the structure can effectively prevent barium element and other metal ions from entering molten silicon liquid at high temperature, does not generate the phenomenon of barium ion enrichment, not only can improve the crystallization rate of the single crystal silicon rod, but also can improve the service life of the tail part of the single crystal silicon rod. The invention can be used for drawing the P-type silicon single crystal rod and the N-type silicon single crystal rod, the diameter size range of the drawn silicon single crystal rod is 160-320mm, the universality is high, and the popularization and the use are easy.
A preparation method of a novel quartz crucible comprises the following steps:
s1: preparation of a blank crucible consisting of a transparent layer 20 and a bubble layer 30
Specifically, the transparent layer 20 and the bubble layer 30 are prepared by a vacuum arc method, the transparent layer 20 is prepared by mixing 99.9999% of high-purity quartz sand powder with a small amount of barium powder, wherein the content of the barium powder is 0.03-0.05 g/kg; the bubble layer 30 is made of quartz sand powder having a purity lower than that of the transparent layer 20. Since the quartz sand powder contains air when melted at a high temperature, the air must be removed under a vacuum condition so that there are no bubbles in the transparent layer 20, and the bubbles are diffused into the bubble layer 30 outside the transparent layer 20 under a pressure difference, and since the purity of the quartz sand powder used in the bubble layer 30 is lower than that of the quartz sand powder in the transparent layer 20, many fine bubbles are present during the manufacturing process. Further, when the transparent layer 20 and the bubble layer 30 are prepared, the quartz sand powder in the transparent layer 20, the barium powder and the quartz sand powder in the bubble layer 30 are fully mixed and stirred, and the materials are added into a sintering mold; and vacuumizing for melting, wherein the vacuum degree in the melting furnace is not less than 1.55Pa, and the vacuumizing is gradually performed from top to bottom and from inside to outside. In the process of vacuum pumping, the area at the inner side can completely remove bubbles under the air pressure to form a compact and uniform transparent layer 20 with the thickness of 3-5 mm; the removed bubbles are diffused to the outside of the transparent layer 20 under the air pressure difference to form a region having a thickness of 1.5-3.5mm and a high bubble density, i.e., a bubble layer 30. And after the vacuum pumping is finished, starting electric arc by using a graphite electrode, starting melting and sintering, wherein the high-temperature sintering temperature is 1750-.
In the process, the transparent layer 20 has a smooth and compact surface, and because the transparent layer 20 contains a small amount of barium powder, the barium powder is uniformly stirred and mixed and then sintered at high temperature to form barium oxide (BaO), barium oxide and silicon dioxide (SiO)2) React to generate barium silicate (BaSiO)3). Due to the existence of barium silicate, fine dense cristobalite crystals are uniformly dispersed throughout the transparent layer 20 of the quartz crucible and closely fitted with silicon dioxide in the transparent layer 20, compared with the prior art in which only a layer of barium hydroxide (Ba (OH) is coated on the surface layer of the inner wall2) The silica white layer formed on the surface layer has better effect, and the silica white obtained in the embodiment can be fused with the silica in the transparent layer 20 into a whole, is difficult to be penetrated by silicon solution to be peeled off, can also protect the inner wall from being corroded, not only can enhance the strength of the quartz crucible and improve the deformation resistance of the quartz crucible, but also can protect the inner wall from being corrodedCan reduce the high-temperature softening of the quartz crucible, and further prolong the service life of the quartz crucible. Meanwhile, the temperature of the inner wall surface of the quartz crucible can be reduced, and the devitrification phenomenon is prevented; in addition, the bubble density of the contact area of the quartz crucible and the silicon solution can be reduced, the intensity of the reaction between the bubbles and the silicon solution is weakened, and the hole density in the single crystal is further reduced; meanwhile, the structure can reduce the introduction of barium element in the process of single crystal silicon rod crystallization and reduce the content of impurities in the process of single crystal growth, thereby achieving the purpose of improving the crystallization rate of single crystal growth and improving the quality of the single crystal silicon rod.
S2: preparation of the inner coating 10 and the outer coating 40
Specifically, both the undercoat layer 10 and the overcoat layer 40 are started after the preparation of the transparent layer 20 and the bubble layer 30 is completed. Wherein, the inner coating 10 is arranged at the upper section of the inner wall of the transparent layer 20, the upper end surface of the inner coating 10 is arranged in parallel with the upper end surface of the transparent layer 20, and the height of the inner coating 10 is 30-50 mm. The thickness of the inner coating layer 10 and the thickness of the outer coating layer 40 are both smaller than the thickness of the bubble layer 30, and the thickness of the inner coating layer 10 is not greater than the thickness of the outer coating layer 40. Specifically, the thickness of the inner coating 10 is 0.4 to 0.6 mm; the thickness of the outer coating 40 is 0.5-1.5 mm; the thickness of each of the inner and outer coatings 10 and 40 is 1.5-3.5mm less than that of the bubble layer 30, and the thickness of the bubble layer 30 is 3-5mm less than that of the transparent layer 20. The outer coating 40 is disposed on the outer wall of the bubble layer 30, and the inner wall of the outer coating 40 is fitted to the outer wall of the bubble layer 30.
Further, the undercoat layer 10 and the overcoat layer 40 coating solutions are saturated barium hydroxide solutions (Ba (OH))2) Before coating the solution, a blank crucible formed by integrally processing the transparent layer 20 and the bubble layer 30 is cleaned, the blank crucible is firstly immersed into an HF pickling tank with the mass ratio of 6-8% for pickling, then is taken out and enters pure water for washing, and then is sequentially subjected to high-pressure cleaning and ultrasonic cleaning, so that residual metal ions on the inner wall and the outer wall of the blank crucible are removed. Dissolving barium hydroxide powder in water to form saturated barium hydroxide solution, placing the blank crucible into a coating machine, and respectively spraying the barium hydroxide solution on the inner wall and the outer wall of the blank crucible to finally form a product with the thickness of 0.4-0.6mmAnd an outer coating 40 having a thickness of 0.5 to 1.5 mm. The specific applicator and rinse tank are well known to those skilled in the art and are omitted herein. Barium hydroxide is very easy to react with carbon dioxide (CO) in air2) Reacting to produce barium carbonate (BaCO)3) An inner coating 10 of barium carbonate is respectively formed on the upper section of the inner wall of the blank crucible and an outer coating 40 of barium carbonate is respectively formed on the outer wall of the blank crucible, namely, a section of the inner coating 10 of barium carbonate with the height of 30-50mm and the thickness of 0.4-0.6mm is respectively formed on the upper section of the inner wall of the transparent layer 20 and an outer coating 40 of barium carbonate with the thickness of 0.5-1.5mm is formed on the outer wall of the bubble layer 30, and the inner wall structure of the outer coating 40 is matched with the outer wall structure of the bubble layer 30. After the above steps, the quartz crucible having the inner coating layer 10, the transparent layer 20, the bubble layer 30 and the outer coating layer 40 sequentially arranged from the inside to the outside is finally formed.
The inner coating 10 coated within a height of 30-50mm of the upper section of the transparent layer 20 has little influence on the growth of single crystal, and the arrangement of the inner coating 10 enables the upper section of the quartz crucible near the upper edge top surface to be rapidly crystallized to form a dense layer, i.e., the dense layer is formed because the inner coating 10 of barium carbonate is easy to be decomposed at high temperature in the Czochralski single crystal process to generate barium oxide (BaO) and carbon dioxide (CO)2) And carbon dioxide is discharged as a gas. Meanwhile, partial barium oxide reaches the surface of the quartz crucible and is absorbed by the surface of the quartz crucible through the gas phase action to generate quartz crucible split phase, namely, the barium oxide reacts with silicon dioxide to generate barium silicate (BaSiO)3) Due to the existence of barium silicate, a layer of compact and tiny cristobalite crystals is formed on the wall of the quartz crucible. The arrangement of the coating 10 in the upper section of the quartz crucible can not only increase the strength of the quartz crucible, but also reduce the curling risk of the upper section of the quartz crucible; but also can reduce the softening phenomenon caused by high temperature, prolong the service life of the quartz crucible and reduce the production cost; meanwhile, impurity pollution of the inner coating 10 to the silicon solution can not be caused, and the resistivity of the silicon single crystal rod is ensured.
The barium carbonate of the outer coating 40 is closely attached to the carbon-carbon crucible outside the quartz crucible, and changes in the same way as the inner coating 10 when the material is heated to a high temperature, i.e., the barium carbonate and the carbon dioxide are easily decomposed to generate barium oxide and carbon dioxide, and the carbon dioxide is discharged as a gas; and simultaneously, barium oxide reaches the surface of the quartz crucible and is absorbed by the surface of the quartz crucible through the gas phase action, so that split phase of the quartz crucible is generated, namely barium oxide reacts with silicon dioxide to generate barium silicate, and a layer of compact and tiny cristobalite crystals are formed on the wall of the quartz crucible due to the existence of the barium silicate. The cristobalite crystallization not only can reduce the reaction of the carbon-carbon crucible to the outer wall of the quartz crucible, reduce the corrosion of the carbon-carbon crucible to the outer wall of the quartz crucible, but also can enhance the heating uniformity of the quartz crucible and improve the strength of the outer wall of the quartz crucible, thereby achieving the purpose of improving the service time of the quartz crucible. Furthermore, the service life of the tail part of the single crystal silicon rod is attenuated relative to the content of metal impurities, and the outer coating 40 can reduce the content of barium ions entering the silicon solution, so that the purpose of improving the service life of the tail part of the single crystal silicon rod is achieved.
A method for prolonging the tail service life of a single crystal silicon rod adopts the quartz crucible to pull the single crystal silicon rod. After loading, vacuumizing, melting, temperature stabilizing, seeding, shouldering, shoulder rotating, diameter equalizing and ending in sequence, the finished product of the single crystal silicon rod is obtained by drawing, and the diameter of the drawn single crystal silicon rod is 160-320 mm.
The quartz crucible in the embodiment and the existing quartz crucible are used for pulling the single crystal silicon rod with the same feeding amount and the same pulling process until the tail single crystal is seen at the bottom of the quartz crucible, namely the pulling of the last section of single crystal silicon rod is normal ending, wherein the feeding amount is 1132kg, the pulling processes are the same, and the process is omitted. The lengths of the pulled single crystal silicon rods are the same, the rods are taken at the same horizontal position in the length direction, and the obtained passivation life values are shown in table 1. As can be seen from table 1, the median of the passivation life of the tail single crystal silicon rod pulled by using the quartz crucible of the present embodiment is 21.3us, and the median of the passivation life of the tail single crystal silicon rod pulled by using the quartz crucible of the prior art is 19.51, i.e., the passivation life of the tail single crystal silicon rod pulled by using the quartz crucible of the present embodiment is improved by 1.79us and 9.17% compared with the quartz crucible of the prior art, which indicates that the quartz crucible of the present embodiment has better use effect and the service life of the tail single crystal silicon rod is improved.
TABLE 1 comparison of the passivation lifetime value (us) of the quantiles of single crystal silicon rods drawn according to the prior art in this example with those drawn according to the prior art
Meanwhile, the weight of the single crystal silicon rods pulled from the two quartz crucibles which have unqualified service life at the tail part of the crucible bottom is detected and compared, the standard is tested on the basis of 20us, and the result is shown in table 2. As can be seen from Table 2, the total weight of the single crystal silicon rod at the end of the crucible pulled by the quartz crucible of this example was 2110.71Kg, wherein the weight of the failed single crystal silicon rod having a lifetime of less than 20us was 27.9Kg, and the defect rate was 1.3%. The total weight of the tail single crystal silicon rod pulled by the quartz crucible in the prior art is 98121.77Kg, wherein the weight of the unqualified single crystal silicon rod with the service life of less than 20us is 4074.03Kg, and the reject ratio accounts for 4.2%. That is, the weight of the single crystal silicon rod drawn by the quartz crucible of the embodiment with the unqualified rod material at the bottom and the tail of the crucible is less, which shows that the tail service life of the single crystal silicon rod is prolonged.
TABLE 2 weight comparison of end of crucible life of single crystal silicon rod drawn in accordance with the prior art of < 20us for this example
Further, the same number of 20 quartz crucibles of the present embodiment and the same number of 20 quartz crucibles of the prior art were used for pulling until tail single crystals were seen at the bottom of the quartz crucible, that is, the number of the single crystal silicon rods having a normal end of the last stage of pulling was counted, and the number of the single crystal silicon rods having a lifetime of more than 20us among all the normally ended single crystal silicon rods was measured, and the results of the ratio of the number of the single crystal silicon rods to the total pulling number of the normal end were the same as shown in table 3, and the description of the process is omitted here. As can be seen from Table 3, a total of 20 quartz crucibles of this example were used to pull single crystal silicon rods, and a total of 238 single crystal silicon rods with a tail portion at the bottom of the crucible were pulled, that is, 238 single crystal silicon rods with a normal tail end at the last stage of pulling were pulled, wherein 149 silicon rods had a lifetime of more than 20us and a percentage of 62.5%. And pulling the monocrystalline silicon rods by using 20 quartz crucibles in the prior art, and pulling 193 monocrystalline silicon rods with the crucible bottom tail part together, wherein the number of the monocrystalline silicon rods with the service life of more than 20us is 93, and the ratio is 48.2%. Therefore, when the same drawing process parameters are used for drawing, the number of the particles of the silicon single crystal rod which is drawn by the quartz crucible of the embodiment and is normally ended at the last section is large, and the number of the silicon single crystal rods with the service lives of more than 20us is also large, so that the service life of the silicon single crystal rod at the tail part is prolonged, and the service life of the quartz crucible is prolonged.
TABLE 3 comparison of the number of particles in the example with the number of particles in the tail single crystal silicon rod of the prior art having a lifetime of > 20us
The invention has the advantages and positive effects that:
1. the quartz crucible designed by the invention has reasonable structural design, can prevent the upper section of the quartz crucible from curling at the position close to the upper end face, improves the strength of the inner wall surface and avoids deformation.
2. According to the quartz crucible provided by the embodiment, the transparent layer is formed by doping trace barium impurities into quartz sand, so that the speed of the inner surface crystallization reaction can be reduced, the nucleation and growth processes of the compact layer are delayed, and the service life of the crucible is prolonged.
3. Meanwhile, a layer of barium hydroxide solution is uniformly coated on the upper section of the inner wall of the transparent layer, so that the strength of the crucible can be enhanced, and the deformation problem is prevented; the barium hydroxide solution is sprayed on the outer wall of the bubble layer, so that the outer wall of the crucible can be promoted to be rapidly crystallized, the strength of the outer wall of the quartz crucible can be enhanced, and the outer wall of the quartz crucible is protected from being corroded; and the influence on the heating uniformity of the quartz crucible after the bubble layer of the quartz crucible is corroded can be prevented, so that the service time of the quartz crucible is prolonged.
4. The quartz crucible with the structure can effectively prevent barium element and other metal ions from entering molten silicon liquid at high temperature, does not generate the phenomenon of barium ion enrichment, not only can improve the crystallization rate of the single crystal silicon rod, but also can improve the service life of the tail part of the single crystal silicon rod.
5. The invention can be used for drawing the P-type silicon single crystal rod and the N-type silicon single crystal rod, the diameter size range of the drawn silicon single crystal rod is 160-320mm, the universality is high, and the popularization and the use are easy.
The embodiments of the present invention have been described in detail, and the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. The preparation method of the novel quartz crucible is characterized by preparing a blank crucible, wherein the blank crucible sequentially comprises a transparent layer and a bubble layer from inside to outside; coating an inner coating on one side of the transparent layer far away from the bubble layer; and coating an outer coating on the side of the bubble layer far away from the transparent layer.
2. The method for manufacturing a novel quartz crucible according to claim 1, wherein the transparent layer and the bubble layer are manufactured by vacuum sintering in a firing furnace; the vacuum degree of the firing furnace is not less than 1.55 Pa.
3. The method as claimed in claim 2, wherein the sintering temperature of the firing furnace is 1750-.
4. The method for preparing a novel quartz crucible according to claim 3, wherein the transparent layer is prepared by mixing high-purity quartz sand powder of 99.9999% with a small amount of barium powder.
5. The method for preparing a novel quartz crucible according to claim 4, wherein the barium powder content is 0.03-0.05 g/kg.
6. The method as claimed in any one of claims 1 to 5, further comprising cleaning the green crucible before applying the inner and outer coatings.
7. The method for preparing the novel quartz crucible according to claim 7, wherein the cleaning sequentially comprises acid washing, water washing, high-pressure cleaning and ultrasonic cleaning.
8. The method for preparing a novel quartz crucible according to claim 7, wherein the pickling solution is 6-8% by mass of hydrofluoric acid.
9. The method for preparing a novel quartz crucible according to any one of claims 1 to 5 and 7 to 8, wherein the inner coating layer and the outer coating layer are both formed by spraying barium hydroxide solution.
10. The method for preparing a novel quartz crucible according to claim 9, wherein the barium hydroxide solution is a saturated solution.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112011824A (en) * | 2020-07-30 | 2020-12-01 | 英利能源（中国）有限公司 | Method for reducing internal pores of czochralski silicon |
| CN113832537A (en) * | 2021-09-30 | 2021-12-24 | 西安奕斯伟材料科技有限公司 | Quartz crucible and crystal pulling furnace |
| CN115074830A (en) * | 2022-06-28 | 2022-09-20 | 乌海市京运通新材料科技有限公司 | Method for prolonging service life of czochralski monocrystalline quartz crucible and crucible structure |
| CN115677228A (en) * | 2021-07-30 | 2023-02-03 | 内蒙古中环协鑫光伏材料有限公司 | Quartz crucible pretreatment method for improving first-grain crystal formation rate, crucible and crystal pulling process |
| CN115724598A (en) * | 2021-08-31 | 2023-03-03 | 内蒙古中环协鑫光伏材料有限公司 | Quartz crucible pretreatment method for improving first grain crystallization rate |
| WO2023185537A1 (en) * | 2022-03-31 | 2023-10-05 | Tcl中环新能源科技股份有限公司 | Process for increasing single crystal output |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149634A (en) * | 1995-06-14 | 1997-05-14 | Memc电子材料有限公司 | Surface treated crucible for improving undislocation performance |
| CN101956230A (en) * | 2010-10-27 | 2011-01-26 | 杭州先进石英材料有限公司 | Quartz glass crucible and preparation method thereof |
| CN202157142U (en) * | 2011-07-15 | 2012-03-07 | 江苏晶鼎电子材料有限公司 | Quartz crucible |
| US20130015318A1 (en) * | 2010-03-31 | 2013-01-17 | Mitsubishi Materials Electronic Chemicals Co., Ltd. | Layered crucible for casting silicon ingot and method of producing same |
| KR20130060352A (en) * | 2011-05-25 | 2013-06-07 | 세인트-고바인 리서치 (상하이) 코포레이션 리미티드 | Silica crucible and method for fabricating the same |
-
2019
- 2019-10-11 CN CN201910964642.6A patent/CN110629281A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149634A (en) * | 1995-06-14 | 1997-05-14 | Memc电子材料有限公司 | Surface treated crucible for improving undislocation performance |
| US20130015318A1 (en) * | 2010-03-31 | 2013-01-17 | Mitsubishi Materials Electronic Chemicals Co., Ltd. | Layered crucible for casting silicon ingot and method of producing same |
| CN101956230A (en) * | 2010-10-27 | 2011-01-26 | 杭州先进石英材料有限公司 | Quartz glass crucible and preparation method thereof |
| KR20130060352A (en) * | 2011-05-25 | 2013-06-07 | 세인트-고바인 리서치 (상하이) 코포레이션 리미티드 | Silica crucible and method for fabricating the same |
| CN202157142U (en) * | 2011-07-15 | 2012-03-07 | 江苏晶鼎电子材料有限公司 | Quartz crucible |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112011824A (en) * | 2020-07-30 | 2020-12-01 | 英利能源（中国）有限公司 | Method for reducing internal pores of czochralski silicon |
| CN112011824B (en) * | 2020-07-30 | 2021-10-01 | 英利能源（中国）有限公司 | Method for reducing internal pores of czochralski silicon |
| CN115677228A (en) * | 2021-07-30 | 2023-02-03 | 内蒙古中环协鑫光伏材料有限公司 | Quartz crucible pretreatment method for improving first-grain crystal formation rate, crucible and crystal pulling process |
| CN115724598A (en) * | 2021-08-31 | 2023-03-03 | 内蒙古中环协鑫光伏材料有限公司 | Quartz crucible pretreatment method for improving first grain crystallization rate |
| CN113832537A (en) * | 2021-09-30 | 2021-12-24 | 西安奕斯伟材料科技有限公司 | Quartz crucible and crystal pulling furnace |
| WO2023185537A1 (en) * | 2022-03-31 | 2023-10-05 | Tcl中环新能源科技股份有限公司 | Process for increasing single crystal output |
| CN115074830A (en) * | 2022-06-28 | 2022-09-20 | 乌海市京运通新材料科技有限公司 | Method for prolonging service life of czochralski monocrystalline quartz crucible and crucible structure |
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Application publication date: 20191231 |