CN110552056A - Method for improving Czochralski single crystal formation - Google Patents

Method for improving Czochralski single crystal formation Download PDF

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Publication number
CN110552056A
CN110552056A CN201910963840.0A CN201910963840A CN110552056A CN 110552056 A CN110552056 A CN 110552056A CN 201910963840 A CN201910963840 A CN 201910963840A CN 110552056 A CN110552056 A CN 110552056A
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CN
China
Prior art keywords
single crystal
barium
silicon
quartz crucible
czochralski single
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Pending
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CN201910963840.0A
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Chinese (zh)
Inventor
吴树飞
徐强
高润飞
王林
谷守伟
王建平
周泽
杨志
赵国伟
刘振宇
王鑫
刘学
皇甫亚楠
杨瑞峰
郭志荣
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Inner Mongolia Central Xiexin Photovoltaic Material Co Ltd
Inner Mongolia Zhonghuan Solar Material Co Ltd
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Inner Mongolia Central Xiexin Photovoltaic Material Co Ltd
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Priority to CN201910963840.0A priority Critical patent/CN110552056A/en
Publication of CN110552056A publication Critical patent/CN110552056A/en
Pending legal-status Critical Current

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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
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/02—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt
    • C30B15/04—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt adding doping materials, e.g. for n-p-junction
    • 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

Abstract

The invention provides a method for improving Czochralski single crystal growth, which comprises the following steps: sequentially filling silicon raw materials and barium carbonate powder into a quartz crucible in the initial charging stage of pulling the monocrystal; the quartz crucible comprises a body, wherein the body comprises a transparent layer and a bubble layer, and the transparent layer and the bubble layer are sequentially arranged from inside to outside; and an outer coating is arranged on the outer wall of the body. The invention provides a crystallization method for improving and being suitable for pulling a P-type and N-type monocrystalline silicon rod, which solves the technical problem that the crystallization rate of Czochralski single crystal is low because the content of barium in silicon liquid is increased by repeatedly scattering barium carbonate powder when materials are repeatedly fed in the prior art, not only can the crystallization rate of single crystal pulling be improved, but also the content of barium in the silicon liquid can be effectively controlled, the process is simplified, the production efficiency is improved, and the production cost is reduced.

Description

Method for improving Czochralski single crystal formation
Technical Field
The invention belongs to the technical field of czochralski silicon single crystals, and particularly relates to a method for improving the crystallization of the czochralski silicon single crystals.
Background
The quartz crucible used traditionally has a coating on the inner wall, and the crucible with the coating has the defects of increasing the crucible manufacturing process, wasting labor hour and increasing cost, and the coating is easy to fall off along with long-time high-temperature operation, and trace Ba element still enters silicon liquid along with the growth of crystals, so that the crystal structure in growth is changed, dislocation is generated, and poor crystallization is caused. And meanwhile, the outer wall in contact with the carbon-carbon crucible is easily softened, and the service life is short.
The patent application of the applicant, published by CN109267147A, proposes that barium carbonate powder is added in the drawing process to improve the single crystal crystallization method, but the method adds the barium carbonate powder once in each repeated feeding, and the method of repeated feeding not only increases the content of the barium carbonate powder, but also increases the content of barium element in silicon liquid and reduces the conversion efficiency of the single crystal silicon rod; and the adding mode also increases the time for re-putting and the production cost.
Disclosure of Invention
The invention aims to provide a method for improving Czochralski single crystal formation, which is particularly suitable for drawing P-type and N-type single crystal silicon rods, solves the technical problem of low Czochralski single crystal formation rate caused by the fact that barium carbonate powder is repeatedly scattered into silicon liquid when materials are repeatedly fed in the prior art, not only can improve the single crystal drawing formation rate, but also can effectively control the content of barium in the silicon liquid, simplify the process, improve the production efficiency and reduce the production cost.
In order to solve the technical problems, the invention adopts the technical scheme that:
An improved Czochralski single crystal growing method, comprising: sequentially filling silicon raw materials and barium carbonate powder into a quartz crucible in the initial charging stage of pulling the monocrystal; the quartz crucible comprises a body, wherein the body comprises a transparent layer and a bubble layer, and the transparent layer and the bubble layer are sequentially arranged from inside to outside; and an outer coating is arranged on the outer wall of the body.
Further, the body and the outer coating both comprise a straight cylinder part and a bending part arranged below the straight cylinder part, a connecting part is arranged between the straight cylinder part and the bending part, and the straight cylinder part, the connecting part and the bending part are integrally arranged.
Further, the silicon raw material fills at least the bent portion.
Furthermore, the lowest position of the upper end surface of the silicon raw material is the connecting position of the connecting part and the straight cylinder part.
Further, the barium carbonate powder is scattered on the upper end face of the silicon raw material along the periphery of the straight cylinder part.
further, the weight of the barium carbonate powder is 0.2-1 g.
Further, the weight of the barium carbonate powder is 0.05 g.
Further, the barium carbonate powder is weighed by a balance.
Further, the silicon raw material is fine-grain polysilicon, and the grain size of the silicon raw material ranges from 80 mm to 120 mm. Further, the transparent layer is prepared by mixing 99.9999% of high-purity quartz sand powder with a small amount of barium powder; the content of the barium powder is 0.03-0.05 g/kg.
By adopting the method designed by the invention, a certain amount of barium carbonate powder is put along the periphery of the inner wall of the quartz crucible at one time in the initial charging stage of pulling the single crystal, so that the complex procedure of repeatedly putting the barium carbonate powder in multiple times of repeated feeding is avoided, and the crystal forming rate of pulling the single crystal can be improved; during the drawing process, barium carbonate powder can form barium ions in the silicon solution, and the barium carbonate powder can convey the barium ions to the quartz crucible for a long time, so that the quartz crucible can be continuously repaired, and the single crystal crystallization effect is improved.
Drawings
FIG. 1 is a schematic structural view of a quartz crucible according to an embodiment of the present invention;
FIG. 2 is a schematic view showing the position of barium carbonate powder charged in the initial charging of a quartz crucible according to an embodiment of the present invention.
In the figure:
10. Body 11, transparent layer 12, bubble layer
20. Outer coating
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The invention provides a quartz crucible, as shown in fig. 1, which comprises a body 10, wherein the body 10 comprises a transparent layer 11 and a bubble layer 12, and the transparent layer 11 and the bubble layer 12 are sequentially arranged from inside to outside; an outer coating 20 is arranged on the outer wall of the body 10, and the structure of the outer coating 20 is matched with that of the bubble layer 12. Further, the body 10 and the outer coating 20 each include a straight cylinder portion and a curved portion disposed below the straight cylinder portion, the curved portion is of a downwardly convex arc-shaped structure, the curved portion is symmetrically disposed, a connecting portion is disposed between the straight cylinder portion and the curved portion, the connecting portion is also of an arc-shaped structure, a radius R of the connecting portion is smaller than a radius R of the curved portion, two ends of the connecting portion are respectively connected with the straight cylinder portion and the curved portion in an integrated tangent manner, a thickness of the straight cylinder portion is smaller than a thickness of the connecting portion, and the thickness of the connecting portion is smaller. The transparent layer 11 is to reduce the density of bubbles in the contact area with the silicon solution, reduce the reaction intensity of the bubbles and the silicon solution, and further reduce the density of holes in the single crystal, thereby improving the success rate of the single crystal growth and the quality of the single crystal silicon rod. The purpose of the bubble layer 12 is to uniformly conduct the heat radiated from the heater to the inner layer of the quartz crucible. The purpose of the outer coating 20 is to form a dense cristobalite crystal layer on the outer wall of the quartz crucible, which not only increases the strength of the quartz crucible and reduces the phenomenon that the quartz crucible is softened at high temperature, but also improves the service life of the quartz crucible and the tail life and the crystallization rate of the single crystal silicon rod.
The body 10 is prepared by a vacuum arc process and includes a transparent layer 11 and a bubble layer 12. Further, the transparent layer 11 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 12 is made of quartz sand powder having a purity lower than that of the transparent layer 11. 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 11, and the bubbles are diffused into the bubble layer 12 outside the transparent layer 11 under a pressure difference, and since the purity of the quartz sand powder used in the bubble layer 12 is lower than that of the quartz sand powder in the transparent layer 11, many fine bubbles are present during the manufacturing process. Further, when the transparent layer 11 and the bubble layer 12 are prepared, quartz sand powder in the transparent layer 11, barium powder and quartz sand powder in the bubble layer 12 are fully mixed and stirred, and 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 air bubbles under the air pressure to form a transparent layer 11 with a compact and uniform straight cylinder part with the thickness of 4 +/-0.5 mm, the thickness of the connecting part is 4 +/-1 mm, and the thickness of the bending part is 4.5 +/-1 mm larger than that of the straight cylinder part. The removed bubbles are diffused to the outside of the transparent layer 11 under the difference of the air pressure to form a region having a thickness of 1.5-3.5mm and a high bubble density, i.e., the bubble layer 12, preferably having a thickness of 2.5 mm. After the vacuum pumping is finished, an electric arc is started by using a graphite electrode, melting and sintering are carried out, the high-temperature sintering temperature is 1750-.
In the process, the transparent layer 11 has smooth and uniform surface, the transparent layer 11 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), the barium oxide reacts with silicon dioxide (SiO 2) to generate barium silicate (BaSiO 3), the existence of the barium silicate enables fine and dense white silica crystals to be uniformly dispersed on the whole layer of the transparent layer 11 of the quartz crucible and to be closely matched and connected with the silicon dioxide in the transparent layer 11, compared with the prior art that only a layer of barium hydroxide (Ba (OH) 2) is coated on the surface layer of the inner wall to form a white silica layer on the surface layer, the white silica obtained in the embodiment can be integrally fused with the silicon dioxide in the transparent layer 11 and is difficult to be infiltrated into the silicon solution to be peeled off, the inner wall can be protected from being corroded easily, the strength of the quartz crucible can be enhanced, the deformation resistance of the quartz crucible can be improved, the high-temperature softening of the inner wall of the quartz crucible can be reduced, the phenomenon of the inner wall of the quartz crucible can be prevented from being severely corroded, the silicon solution, the silicon crucible can be reduced, the silicon crystal density of the silicon crystal grown in addition, the silicon single crystal can be reduced, the silicon crystal grown in the silicon crucible, the silicon crystal growing process can be reduced, the silicon crystal silicon.
The outer coating 20 is carried out after the preparation of the body 10 is completed, the thickness of the outer coating 20 being 0.5-1.5 mm; the thickness of the outer coating 20 is smaller than that of the bubble layer 12 with the thickness of 1.5-3.5mm, the thickness of the bubble layer 12 is smaller than that of the transparent layer 11 with the thickness of 3-5mm, the outer coating 20 is arranged on the outer wall of the bubble layer 12, and the inner wall of the outer coating 20 is matched with the outer wall of the bubble layer 12.
further, the coating solution of the outer coating 20 is a saturated barium hydroxide solution (ba (oh) 2), before the coating solution is applied, the body 10 is cleaned, the body 10 is immersed in a hydrofluoric acid (HF) pickling tank with a mass ratio of 6-8% for pickling, then taken out and put into pure water for washing, and then sequentially subjected to high pressure cleaning and ultrasonic cleaning in order to remove residual metal ions on the inner and outer walls of the body 10, barium hydroxide powder is dissolved in water to form a saturated barium hydroxide solution, the body 10 is put into the coating machine, the barium hydroxide solution is sprayed on the outer wall of the body 10, and finally the outer coating 20 with a thickness of 0.5-1.5mm is formed, and the specific coating machine and the washing tank are well known to those skilled in the art, and the barium hydroxide is omitted, and is very easily reacted with carbon dioxide (CO 2) in the air to produce barium carbonate (BaCO 3), the outer coating 20 of barium carbonate is formed on the outer wall of the body 10, that is formed on the outer wall of the outer coating 12, and the outer coating 20 is formed into a bubble structure of the quartz crucible by the outer coating layer 12 and the quartz crucible 12.
The barium carbonate of the outer coating 20 is closely attached to the carbon-carbon crucible outside the quartz crucible, and is easy to generate decomposition reaction when melting materials at high temperature to generate barium oxide (BaO) and carbon dioxide (CO 2), and the carbon dioxide is discharged as gas, meanwhile, through gas phase action, part of the barium oxide reaches the surface of the quartz crucible and is absorbed by the surface of the quartz crucible to generate quartz crucible split phase, namely, the barium oxide reacts with the silicon dioxide to generate barium silicate (BaSiO 3), and due to the existence of the barium silicate, a layer of compact and tiny cristobalite crystals are formed on the wall of the quartz crucible, the cristobalite crystals not only can reduce the reaction of the carbon-carbon crucible to the outer wall of the quartz crucible and 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.
The quartz crucible provided by the embodiment forms the transparent layer 11 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, barium hydroxide solution is sprayed on the outer wall of the air 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 quartz crucible comprises the following steps:
S1: a body 10 is prepared.
Specifically, the body 10 is prepared by a vacuum arc method, and includes a transparent layer 11 and a bubble layer 12. Further, the transparent layer 11 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 12 is made of quartz sand powder having a purity lower than that of the transparent layer 11. 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 11, and the bubbles are diffused into the bubble layer 12 outside the transparent layer 11 under a pressure difference, and since the purity of the quartz sand powder used in the bubble layer 12 is lower than that of the quartz sand powder in the transparent layer 11, many fine bubbles are present during the manufacturing process. Further, when the transparent layer 11 and the bubble layer 12 are prepared, quartz sand powder in the transparent layer 11, barium powder and quartz sand powder in the bubble layer 12 are fully mixed and stirred, and 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 air bubbles under the air pressure to form a transparent layer 11 with a compact and uniform straight cylinder part with the thickness of 4 +/-0.5 mm, the thickness of the connecting part is 4 +/-1 mm, and the thickness of the bending part is 4.5 +/-1 mm larger than that of the straight cylinder part. The removed bubbles are diffused to the outside of the transparent layer 11 under the difference of the air pressure to form a region having a thickness of 1.5-3.5mm and a high bubble density, i.e., the bubble layer 12, preferably having a thickness of 2.5 mm. After the vacuum pumping is finished, an electric arc is started by using a graphite electrode, melting and sintering are carried out, the high-temperature sintering temperature is 1750-.
In the process, the transparent layer 11 has smooth and uniform surface, the transparent layer 11 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), the barium oxide reacts with silicon dioxide (SiO 2) to generate barium silicate (BaSiO 3), the existence of the barium silicate enables fine and dense white silica crystals to be uniformly dispersed on the whole layer of the transparent layer 11 of the quartz crucible and to be closely matched and connected with the silicon dioxide in the transparent layer 11, compared with the prior art that only a layer of barium hydroxide (Ba (OH) 2) is coated on the surface layer of the inner wall to form a white silica layer on the surface layer, the white silica obtained in the embodiment can be integrally fused with the silicon dioxide in the transparent layer 11 and is difficult to be infiltrated into the silicon solution to be peeled off, the inner wall can be protected from being corroded easily, the strength of the quartz crucible can be enhanced, the deformation resistance of the quartz crucible can be improved, the high-temperature softening of the inner wall of the quartz crucible can be reduced, the phenomenon of the inner wall of the quartz crucible can be prevented from being severely corroded, the silicon solution, the silicon crucible can be reduced, the silicon crystal density of the silicon crystal grown in addition, the silicon single crystal can be reduced, the silicon crystal grown in the silicon crucible, the silicon crystal growing process can be reduced, the silicon crystal silicon.
S2: an outer coating 20 is applied to the outer wall of the body 10.
Further, cleaning of the body 10 prior to applying the topcoat 20 may include, in order, acid cleaning, water cleaning, high pressure cleaning, and ultrasonic cleaning.
Specifically, topcoat 20 is carried out after the preparation of body 10 is complete, topcoat 20 having a thickness of 0.5 to 1.5 mm; the thickness of the outer coating 20 is smaller than that of the bubble layer 12 with the thickness of 1.5-3.5mm, the thickness of the bubble layer 12 is smaller than that of the transparent layer 11 with the thickness of 3-5mm, the outer coating 20 is arranged on the outer wall of the bubble layer 12, and the inner wall of the outer coating 20 is matched with the outer wall of the bubble layer 12.
Further, the coating solution of the outer coating 20 is a saturated barium hydroxide solution (ba (oh) 2), before the coating solution is applied, the body 10 is cleaned, the body 10 is immersed in a hydrofluoric acid (HF) pickling tank with a mass ratio of 6-8% for pickling, then taken out and put into pure water for washing, and then sequentially subjected to high pressure cleaning and ultrasonic cleaning in order to remove residual metal ions on the inner and outer walls of the body 10, barium hydroxide powder is dissolved in water to form a saturated barium hydroxide solution, the body 10 is put into the coating machine, the barium hydroxide solution is sprayed on the outer wall of the body 10, and finally the outer coating 20 with a thickness of 0.5-1.5mm is formed, and the specific coating machine and the washing tank are well known to those skilled in the art, and the barium hydroxide is omitted, and is very easily reacted with carbon dioxide (CO 2) in the air to produce barium carbonate (BaCO 3), the outer coating 20 of barium carbonate is formed on the outer wall of the body 10, that is formed on the outer wall of the outer coating 12, and the outer coating 20 is formed into a bubble structure of the quartz crucible by the outer coating layer 12 and the quartz crucible 12.
The barium carbonate of the outer coating 20 is closely attached to the carbon-carbon crucible outside the quartz crucible, and is easy to generate decomposition reaction when melting materials at high temperature to generate barium oxide (BaO) and carbon dioxide (CO 2), and the carbon dioxide is discharged as gas, meanwhile, through gas phase action, part of the barium oxide reaches the surface of the quartz crucible and is absorbed by the surface of the quartz crucible to generate quartz crucible split phase, namely, the barium oxide reacts with the silicon dioxide to generate barium silicate (BaSiO 3), and due to the existence of the barium silicate, a layer of compact and tiny cristobalite crystals are formed on the wall of the quartz crucible, the cristobalite crystals not only can reduce the reaction of the carbon-carbon crucible to the outer wall of the quartz crucible and 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.
An improved Czochralski single crystal growing method, comprising: the silicon raw material and the barium carbonate powder are sequentially filled into the quartz crucible in the initial charging stage of the Czochralski single crystal, namely, part of the silicon raw material is filled into the quartz crucible firstly and then the barium carbonate powder is sprinkled into the quartz crucible. The quartz crucible comprises a body 10, wherein the body 10 comprises a transparent layer 11 and a bubble layer 12, and the transparent layer 11 and the bubble layer 12 are sequentially arranged from inside to outside; an outer coating 20 is provided on the outer wall of the body 10.
Further, the body 10 and the outer coating 20 each include a straight cylinder portion and a curved portion disposed below the straight cylinder portion, the curved portion is of a downwardly convex arc-shaped structure, the curved portion is symmetrically disposed, a connecting portion is disposed between the straight cylinder portion and the curved portion, the connecting portion is also of an arc-shaped structure, a radius R of the connecting portion is smaller than a radius R of the curved portion, two ends of the connecting portion are respectively connected with the straight cylinder portion and the curved portion in an integrated tangent manner, a thickness of the straight cylinder portion is smaller than a thickness of the connecting portion, and the thickness of the connecting portion is smaller.
The body 10 is prepared by a vacuum arc method, and includes a transparent layer 11 and a bubble layer 12, further, the transparent layer 11 is prepared by mixing 99.9999% of high purity quartz sand powder with a small amount of barium powder, wherein the content of barium powder is 0.03-0.05g/kg, the bubble layer 12 is prepared by quartz sand powder having a purity lower than that of the transparent layer 11, since the transparent layer 11 contains a small amount of barium powder, the barium powder is uniformly stirred and mixed, and then sintered at a high temperature to form barium oxide (BaO), the barium oxide reacts with silicon dioxide (SiO 2) to form barium silicate (BaSiO 3), due to the presence of barium silicate, fine dense white silica crystals are uniformly dispersed over the entire layer of the transparent layer 11 of the quartz crucible, and are closely fit with silicon dioxide in the transparent layer 11 to form a surface white silica layer, the white silica layer can be integrally fused with silicon dioxide in the transparent layer 11, and hardly fall off by infiltration of a silicon solution, thereby protecting the inner wall from being corroded, and simultaneously, the temperature of the inner wall surface of the quartz crucible can be reduced, the phenomenon of the quartz crucible inner wall can be prevented from contact with silicon dioxide, and the silicon dioxide in addition, the silicon single crystal growth of the crucible can be reduced, the silicon single crystal growth of the quartz crucible, the silicon single crystal silicon crystal growth can be reduced, the silicon crystal growth rate can be increased, the silicon crystal growth rate can be increased, the silicon crystal growth of the silica crucible can be increased, the silica.
Further, a certain amount of barium carbonate powder is weighed by a balance scale, the weight of the barium carbonate powder is ensured to be 0.2-1g, and then the weighed barium carbonate powder is filled into a measuring cup.
Furthermore, during the initial charging stage of the czochralski single crystal, the fine-particle polycrystalline silicon raw material is charged firstly, and the large silicon raw material is charged later, wherein the particle size range of the initial fine-particle polycrystalline silicon raw material is 80-120mm, the fine-particle polycrystalline silicon raw material is easy to melt, so that the large silicon raw material placed on the upper part can be prevented from extruding the bottom of the R corner of the bending part, the edge hanging phenomenon of the large silicon raw material on the inner wall of the quartz crucible can be prevented, and the silicon liquid after the material is normally melted at the bottom of the crucible can support the continuous material melting of the large silicon raw material on the upper part; meanwhile, the melting time of the silicon raw material is favorably shortened, the silicon raw material firstly forms a compact crystallization layer within the R angle of the bending part, and the crystallization layer can protect the bottom of the quartz crucible, prevent the bottom from being softened and prolong the service life of the quartz crucible due to higher temperature of the bottom of the quartz crucible in the melting and melting process. In the initial stage of charging, the charged silicon raw material fills at least the curved portion of the quartz crucible, preferably, the silicon raw material is spread over the curved portion and the connecting portion, as shown in fig. 2, and the lowest position of the upper end surface of the silicon raw material is a connecting position of the connecting portion and the straight cylinder portion, that is, the silicon raw material fills the bottom of the quartz crucible, and the lowest position of the upper end surface of the silicon raw material is a lower end of a connecting position H of the connecting portion and the straight cylinder portion. Then, barium carbonate powder with the weight of 0.2-1g, preferably 0.5g, is uniformly scattered on the upper end surface of the silicon raw material along the periphery of the straight cylinder part. The barium carbonate powder slides along the inner wall of the quartz crucible along the gap of the silicon raw material to the R-corner of the connecting part or the R-corner of the bending part. And continuously filling the polycrystalline silicon raw material into the quartz crucible until the quartz crucible is filled.
Then, the quartz crucible is placed into a single crystal furnace, and a silicon raw material is melted in the single crystal furnace by using a heater; and then, after vacuum pumping, material melting, temperature stabilization, seeding, shouldering, shoulder rotating, diameter equalization and ending in sequence, the silicon single crystal rod is drawn into a finished product, and the diameter of the drawn silicon single crystal rod is 160-320 mm.
3 2 2+ 2+ 2In the silicon solution, because of the rapid adsorption of barium ions on the inner surface of the quartz crucible, a barium-poor area is formed near the inner surface of the quartz crucible, a diffusion gradient is formed from the central position of the silicon solution to the edge of the quartz crucible, and a large amount of barium ions finally migrate to the surface of the quartz crucible.
A certain amount of barium carbonate powder is put along the periphery of the inner wall of the quartz crucible at one time in the initial charging stage of the Czochralski single crystal pulling, preferably, the content of the barium carbonate powder is 0.5g, so that the complex procedure of repeatedly putting the barium carbonate powder in multiple times of repeated feeding is avoided, and the crystal forming rate of the single crystal pulling can be improved. During the drawing process, barium ions can be formed in the silicon solution by the barium carbonate powder, and the barium ions can be conveyed to the quartz crucible by the barium carbonate powder for a long time, so that the quartz crucible can be continuously repaired, the single crystal crystallization effect is improved, the product quality is ensured, and the generation cost is reduced.
The invention has the advantages and positive effects that:
The quartz crucible designed by the invention has simple structure, can improve the strength of the quartz crucible, prevent the quartz crucible from softening, prolong the service life, reduce the production cost and reduce the waste of crucible manufacturing working hours. The invention puts forward that a certain amount of barium carbonate powder is put in one time along the periphery of the inner wall of the quartz crucible in the initial charging stage of pulling the single crystal, thereby avoiding the complex procedure of repeatedly putting in the barium carbonate powder when repeatedly putting in, and improving the crystal forming rate of pulling the single crystal. During the drawing process, barium carbonate powder can form barium ions in the silicon solution, and the barium carbonate powder can convey the barium ions to the quartz crucible for a long time, so that the quartz crucible can be continuously repaired, and the single crystal crystallization effect is improved.
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. An improved Czochralski single crystal growing method, comprising: sequentially filling silicon raw materials and barium carbonate powder into a quartz crucible in the initial charging stage of pulling the monocrystal; the quartz crucible comprises a body, wherein the body comprises a transparent layer and a bubble layer, and the transparent layer and the bubble layer are sequentially arranged from inside to outside; and an outer coating is arranged on the outer wall of the body.
2. An improved Czochralski single crystal growing method as set forth in claim 1, wherein each of the body and the outer coating comprises a straight tube portion and a curved portion disposed below the straight tube portion, and a connecting portion is provided between the straight tube portion and the curved portion, the straight tube portion, the connecting portion and the curved portion being integrally provided.
3. An improved Czochralski single crystal growing method as set forth in claim 2, wherein the silicon feedstock at least fills the bend.
4. an improved Czochralski single crystal growing method as set forth in claim 3, wherein the lowest position of the upper end surface of the silicon raw material is a position where the connecting portion is connected to the straight portion.
5. An improved Czochralski single crystal growing method as set forth in claim 4, wherein the barium carbonate powder is sprinkled along a peripheral edge of the straight portion on an upper end surface of the silicon raw material.
6. An improved Czochralski single crystal growing method as set forth in any one of claims 1 to 5, wherein the barium carbonate powder is present in an amount of 0.2 to 1g by weight.
7. An improved Czochralski single crystal growing method as set forth in claim 6, wherein the barium carbonate powder is present in an amount of 0.05g by weight.
8. An improved Czochralski single crystal growing method as set forth in claim 7, wherein the barium carbonate powder is weighed by a balance.
9. An improved Czochralski single crystal growing method as set forth in any one of claims 1-5 and 7-8, wherein the silicon feedstock is fine grained polysilicon and the silicon feedstock has a grain size in the range of 80-120 mm.
10. An improved Czochralski single crystal growing method as set forth in claim 9, wherein the transparent layer is made of 99.9999% high purity quartz sand powder mixed with a small amount of barium powder; the content of the barium powder is 0.03-0.05 g/kg.
CN201910963840.0A 2019-10-11 2019-10-11 Method for improving Czochralski single crystal formation Pending CN110552056A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6641663B2 (en) * 2001-12-12 2003-11-04 Heracus Shin-Estu America Silica crucible with inner layer crystallizer and method
JP2004352580A (en) * 2003-05-30 2004-12-16 Japan Siper Quarts Corp Quartz glass crucible for pulling silicon single crystal and method for pulling silicon single crystal
CN104831350A (en) * 2015-05-26 2015-08-12 江西旭阳雷迪高科技股份有限公司 Method of distributing seeding material to bottom of quartz ceramic crucible for ingot casting
CN107099842A (en) * 2017-05-10 2017-08-29 宁夏协鑫晶体科技发展有限公司 The preparation method of monocrystalline silicon

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6641663B2 (en) * 2001-12-12 2003-11-04 Heracus Shin-Estu America Silica crucible with inner layer crystallizer and method
JP2004352580A (en) * 2003-05-30 2004-12-16 Japan Siper Quarts Corp Quartz glass crucible for pulling silicon single crystal and method for pulling silicon single crystal
CN104831350A (en) * 2015-05-26 2015-08-12 江西旭阳雷迪高科技股份有限公司 Method of distributing seeding material to bottom of quartz ceramic crucible for ingot casting
CN107099842A (en) * 2017-05-10 2017-08-29 宁夏协鑫晶体科技发展有限公司 The preparation method of monocrystalline silicon

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