CN115369475B - Initial re-casting process of Czochralski single crystal - Google Patents
Initial re-casting process of Czochralski single crystal Download PDFInfo
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- CN115369475B CN115369475B CN202110556750.7A CN202110556750A CN115369475B CN 115369475 B CN115369475 B CN 115369475B CN 202110556750 A CN202110556750 A CN 202110556750A CN 115369475 B CN115369475 B CN 115369475B
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- 239000013078 crystal Substances 0.000 title claims abstract description 62
- 238000005266 casting Methods 0.000 title claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000010453 quartz Substances 0.000 claims abstract description 125
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 118
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 118
- 239000010703 silicon Substances 0.000 claims abstract description 118
- 238000002425 crystallisation Methods 0.000 claims abstract description 47
- 230000008025 crystallization Effects 0.000 claims abstract description 47
- 238000002844 melting Methods 0.000 claims abstract description 43
- 230000008018 melting Effects 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000002210 silicon-based material Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 37
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000011241 protective layer Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 102
- 239000010410 layer Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 6
- 238000005336 cracking Methods 0.000 description 3
- 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
- 238000001816 cooling Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052916 barium silicate Inorganic materials 0.000 description 1
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- ZGUQQOOKFJPJRS-UHFFFAOYSA-N lead silicon Chemical compound [Si].[Pb] ZGUQQOOKFJPJRS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910021493 α-cristobalite Inorganic materials 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
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/10—Crucibles or containers for supporting the melt
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
An initial re-casting process of a Czochralski single crystal comprises the following steps: the upper end surface of the quartz crucible carrying the silicon melting raw material has a certain height to the liquid level of the silicon melting; the inner side annular wall surface of the quartz crucible with the certain height is subjected to crystallization phase change, and a quartz body with an alpha-cristobalite structure is obtained; and re-throwing silicon raw materials into the quartz crucible after crystallization. The invention can make the upper edge inner wall of the quartz crucible close to the solid-liquid interface baked fully at high temperature under the premise of not influencing the total loading amount of the quartz crucible, so that the quartz crucible is gradually and completely crystallized to obtain a compact and stable protective layer with an alpha-cristobalite structure, and the corrosion resistance is high, so that the problem that bubbles are not easy to crack or quartz fall off on the inner wall of the quartz crucible in the process of drawing a first single crystal is solved, thereby reducing the content of impurities in the crystal pulling process and further improving the crystallization effect. Compared with the existing initial re-casting process, the re-casting process provided by the invention can improve the crystallization rate of the initial drawn silicon rod by more than 15%.
Description
Technical Field
The invention belongs to the technical field of manufacturing of semiconductor Czochralski crystals, and particularly relates to an initial re-casting process of a Czochralski crystal.
Background
In single crystal pulling, a pre-loading process is adopted at present, namely, a quartz crucible is filled with polycrystalline silicon raw material blocks in the early stage, then the quartz crucible filled with silicon raw materials is placed into a single crystal furnace for material melting, and the initial re-casting is directly carried out after the silicon raw materials in the quartz crucible completely collapse until the maximum loading amount of the quartz crucible is reached.
In addition, in order to reduce the weight of the initial re-cast raw material and save the re-cast time, the initial charge weight is generally maximized during initial charging, so that the liquid level of the molten silicon in the quartz crucible is close to the upper edge of the quartz crucible during initial re-casting, as shown in fig. 1, the liquid level of the molten silicon is always in the high-level quartz crucible from initial charging to initial re-casting, the upper edge inner wall of the quartz crucible cannot be sufficiently high Wen Xijing during the crystal pulling process, or crystallization is insufficient, and the surface of the inner wall of the quartz crucible close to a solid-liquid interface during the drawing of a first single crystal is easy to generate bubble cracking, even quartz falling phenomenon occurs, so that the crystallization quality of the first single crystal is seriously affected.
In addition, the existing method for improving the inner wall characteristics of the quartz crucible is to coat a layer of the existing method for improving the strength of the quartz crucible on the inner wall of the quartz crucible by coating two layers of coatings inside a transparent layer on the inner side, wherein a barium carbonate coating is arranged on one side close to the transparent layer, a barium silicate coating is arranged on one side, far away from the transparent layer, of the barium carbonate coating, and barium carbonate powder is added in the re-casting stage, so that a process method for coating the quartz crucible and the quartz crucible for multiple times is proposed in Chinese published patent CN 109267148A; or a barium hydroxide coating is coated on the inner part of the inner transparent layer and the outer part of the outer bubble layer, as disclosed in Chinese patent publication CN211367806U, a novel quartz crucible is provided; or a barium hydroxide coating is coated on the outer part of the outer bubble layer, such as a quartz crucible proposed in Chinese patent publication No. CN 211367805U. The method has complex working flow, and can increase the content of barium element in the silicon liquid, so that more impurities are caused in the crystal, and the crystal is often required to be formed after being expanded once or to be broken into short buds, so that the successful crystal forming rate of head single crystal pulling is lower.
Disclosure of Invention
The invention provides an initial re-casting process of a Czochralski single crystal, which solves the technical problems that in the prior art, a quartz crucible cannot be sufficiently high Wen Xijing in the crystal pulling process or crystallization is insufficient, so that bubbles are easy to crack on the surface of the inner wall of the quartz crucible, even quartz falls off, and crystallization is seriously influenced.
In order to solve the technical problems, the invention adopts the following technical scheme:
an initial re-casting process of a Czochralski single crystal comprises the following steps:
The upper end surface of the quartz crucible carrying the silicon melting raw material has a certain height to the liquid level of the silicon melting;
The inner side annular wall surface of the quartz crucible with the certain height is subjected to crystallization phase change, and a quartz body with an alpha-cristobalite structure is obtained;
And re-throwing silicon raw materials into the quartz crucible after crystallization.
Further, the certain height is not less than 100mm and not more than 300mm;
Preferably, the certain height is 150-250mm.
Further, the silicon melt raw material is an initial silicon raw material charged into the quartz crucible.
Further, the molten silicon feedstock is a monolithic quantity of the initial silicon feedstock.
Further, the steps before the quartz crucible crystallization include:
Completely melting the initial silicon raw material to a molten state to form the molten silicon liquid;
and the molten silicon is kept at the melting temperature for a period of time, so that the inner wall surface of the quartz crucible with a certain height is covered with a crystallization layer which is the quartz body with the alpha-cristobalite structure.
Further, the melting temperature is 1450-1500 ℃.
Further, the molten silicon is maintained at the melting temperature for at least 0.5h;
Preferably, the molten silicon is maintained at the melting temperature for a period of time ranging from 0.5 to 1 hour.
Further, the molten silicon liquid is cooled to the crystallization temperature after being melted;
Preferably, the crystallization temperature of the silicon melt is 1400-1450 ℃.
Further, carrying out primary re-casting charging to the quartz crucible within a set time after crystallization, and completely mixing and melting the re-casting silicon material and the initial silicon material;
After re-casting, the liquid level of the silicon melt in the quartz crucible is lower than the upper end surface of the quartz crucible;
Preferably, the initial re-feeding of the charge to the quartz crucible is operated within 0.5h after crystallization.
Further, after re-casting, the height from the liquid level of the silicon melt in the quartz crucible to the upper end surface of the quartz crucible is not less than 40mm and not more than 100mm;
preferably, the height from the liquid level of the silicon melt in the quartz crucible to the upper end surface of the quartz crucible after re-casting is not less than 40mm and not more than 70mm.
The initial re-casting process of the Czochralski single crystal designed by the invention can fully bake the inner side wall of the upper edge of the quartz crucible close to the solid-liquid interface at high temperature on the premise of not influencing the total loading amount of the quartz crucible, so that the inner wall of the quartz crucible is completely crystallized to obtain a layer of compact and stable protective layer with an alpha-cristobalite structure, and the corrosion resistance is high, so that the inner wall of the quartz crucible is not easy to generate the problems of bubble cracking or quartz falling in the process of drawing a first single crystal, thereby reducing the content of impurities in the process of pulling the crystal, further improving the crystallization effect and improving the yield of the silicon single crystal. Compared with the existing initial re-casting process, the initial re-casting process provided by the invention can improve the crystallization rate of the initial drawn silicon rod by more than 15%.
Drawings
FIG. 1 is a schematic view of the structure of a prior art initial charge after melting;
FIG. 2 is a schematic illustration of the structure of an embodiment of the present invention after melting of an initial charge;
FIG. 3 is a schematic diagram of the structure after initial re-casting fusion according to an embodiment of the present invention.
In the figure:
10. quartz crucible
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
The embodiment provides an initial re-casting process of a Czochralski single crystal, as shown in fig. 2 and 3, comprising the following steps:
Firstly, the upper end face of a quartz crucible 10 carrying silicon melting raw material is provided with a certain height H1 from the upper end face to the silicon melting liquid level; and the inner side annular wall surface of the quartz crucible 10 with a certain height H1 is subjected to crystallization phase change to obtain a layer of quartz body with an alpha-cristobalite structure; then, the silicon raw material is re-charged into the quartz crucible 10 after the crystallization. The process can lead silicon dioxide on the inner wall of the upper edge of the bare drain of the quartz crucible to be heated to generate crystallization reaction at a high temperature, and continuously perform crystallization in the subsequent high-temperature re-casting and crystal pulling processes, so that a layer of compact and stable alpha-cristobalite with a face-centered cubic structure is obtained on the inner wall of the quartz crucible near the solid-liquid interface accessory of the first single crystal drawing, and the process has corrosion resistance, thereby preventing the problems that bubbles are broken and even quartz is dropped off on the inner wall surface of the quartz crucible near the solid-liquid section during the first single crystal drawing, reducing the probability of peeling metal ions of the quartz crucible, and further improving the crystallization rate of the first single crystal.
Specifically, the silicon melt raw material is an initial silicon raw material charged into the quartz crucible 10, and is a monolithic amount of the initial silicon raw material. That is, initial charging is performed to the quartz crucible 10, and the distance from the initial silicon melt level a after complete charging to the upper end surface of the quartz crucible 10 is set to H1. Completely melting the initial silicon raw material to a molten state to form initial molten silicon liquid; after the initial molten silicon is kept at the melting temperature for a period of time, the inner wall surface of the quartz crucible with a certain height H1 is covered with a crystallization layer which is a quartz body with an alpha-cristobalite structure.
The quartz crucible 10 is initially charged and the initially charged silicon raw material is made to have a height exceeding the upper end surface of the quartz crucible 10, preferably the initially charged silicon raw material has a height exceeding the upper end surface of the quartz crucible 10 by 50 to 100mm. This height allows the initial molten silicon level a obtained after the initial silicon raw material is completely melted to have a certain distance H1 from the upper end surface of the quartz crucible 10. The quartz crucible 10 with the height H1 is exposed outside the high temperature area, and the temperature of the position is higher than that of the conventional process, so that the inner wall surface of the quartz crucible 10 at the position can be fully transformed to obtain a compact and stable crystallization layer, and the crystallization effect of the first single crystal drawing can be improved.
Further, the height H1 from the initial silicon melt level A to the annular bare wall surface of the upper end surface of the quartz crucible 10 after the initial silicon raw material is melted is not less than 100mm and not more than 300mm. This is because if the height H1 is smaller than 100mm, the level of the molten silicon is high, i.e., the height of the molten silicon baked at high temperature is small, the area covered by the crystallization layer is small, and the height requirement of the first single crystal during the drawing cannot be satisfied. If the height H1 is greater than 300mm, the initial silicon raw material in the quartz crucible 10 is too small, and if the weight required for pulling the single crystal silicon rod is desired to be reached, more re-feeding amount is required, and further the re-feeding time is increased, so that the annular bare wall surface softens the crystallization layer due to overlong temperature in a high-temperature heated environment, further the service life of the quartz crucible is affected, and the risk of quartz falling is increased.
Preferably, the height H1 from the initial silicon melt level A to the annular bare wall surface of the upper end surface of the quartz crucible 10 after the initial silicon raw material is melted is 150 to 250mm. The method not only can meet the premise of the total loading amount of the quartz crucible 10, but also can enable the upper edge annular bare wall surface of the quartz crucible 10 to be close to a solid-liquid interface during the first single crystal drawing, and can be fully baked at high temperature, so that the upper edge annular bare wall surface of the quartz crucible 10 is fully crystallized, a compact and stable protective layer of alpha-cristobalite structure is obtained, the corrosion resistance of the inner wall of the quartz crucible 10 is improved, and the crystallization rate of the first single crystal drawing can be improved.
After the initial charge is completed, the initial silicon raw material in the quartz crucible 10 is again charged, and the temperature and time for the charge are the same as those of the conventional process, which is omitted here. The initial silicon feedstock is observed and is not immediately re-thrown after the silicon feedstock collapses, and is ready to be re-thrown after the initial silicon feedstock in the quartz crucible 10 is completely melted to form a molten silicon solution. The method is characterized in that when the initial silicon raw material is collapsed, the silicon raw material is not completely melted, the temperature of a thermal field of the silicon raw material does not reach the crystallization temperature of silicon dioxide, and phase change cannot occur, so that the initial silicon raw material is required to be heated to the melting temperature of 1450-1500 ℃ again, and the molten silicon is kept at the melting temperature of 1450-1500 ℃ for at least 0.5h; preferably, the molten silicon is maintained at the melting temperature for a period of 0.5 to 1 hour, that is, the initial molten silicon is maintained at the melting temperature for 0.5 to 1 hour, and the initial re-casting may be prepared in order to completely melt the initial silicon raw material and to completely crystallize the inner wall of the quartz crucible 10 in a heated state after 0.5 hour.
Further, before the initial re-casting, the initial molten silicon liquid needs to be cooled to the crystallization temperature after being melted, so that the initial molten silicon liquid is crystallized, and the crystallization temperature is 1400-1450 ℃; the re-casting after crystallization is beneficial to preventing silicon raw materials from falling into the initial molten silicon liquid to splash silicon during re-casting.
Further, the first re-charging is performed into the quartz crucible 10 within a set time after crystallization, and the re-charging silicon material and the initial silicon material are completely mixed and melted, and preferably, the first re-charging is performed into the quartz crucible 10 within 0.5h after crystallization. The temperature of the thermal field is gradually increased to 1450-1500 ℃ to enable the re-thrown silicon raw material to be completely melted, and then the subsequent crystal pulling process is carried out; and the liquid level of the silicon melt in the quartz crucible after re-casting is lower than the upper end face of the quartz crucible 10.
Further, the height H2 from the liquid level of the re-cast silicon in the quartz crucible to the upper end face of the quartz crucible 10 after re-casting is not less than 40mm and not more than 100mm. If the height H2 is less than 40mm, the risk of silicon overflow exists; if it is more than 100mm, the charge amount of the quartz crucible 10 does not reach its limit, and the utilization ratio is too low.
Preferably, the height from the level of the re-cast silicon in the quartz crucible 10 to the upper end face of the quartz crucible 10 after re-casting is not less than 40mm and not more than 70mm.
By adopting the process, silicon rods drawn by different quartz crucibles are drawn, and the specific implementation is as follows:
Embodiment one:
the other processes were unchanged when the diameter of the quartz crucible 10 was 28 inches.
Specifically, after the initial silicon raw material is charged into the quartz crucible 10, the height of the silicon raw material exceeds the upper end surface of the quartz crucible 10 by 100mm.
The initial silicon material is firstly melted and then melted at the silicon melting temperature of 1450 ℃, and the height H1 from the initial silicon melting liquid level to the upper end face of the quartz crucible 10 is 150mm.
And cooling after the silicon melting temperature is continued for 1h, so that the temperature of the thermal field is reduced to 1400 ℃, the initial silicon melting is crystallized, and the initial re-feeding of the silicon raw material is started after the crystallization is performed for 0.5 h.
And then the re-casting silicon raw material is melted into the initial silicon melting liquid completely, the temperature of the re-casting silicon melting liquid is the same as that of the initial silicon melting liquid, and the height H2 from the re-casting silicon melting liquid level to the upper end face of the quartz crucible 10 is 50mm.
As compared with the existing crystal pulling process shown in FIG. 1, the crystal pulling rate of the first silicon rod obtained by the process of this example is shown in Table 1, and as can be seen from Table 1, each process was pulled to 10 groups and the other processes were the same, the crystal pulling rate of the first single crystal obtained by the process of this example was 83.3%, and the crystal pulling rate of the first single crystal obtained by the existing crystal pulling process was 67.3%.
TABLE 1 initial single crystal pulling results for the quartz crucible after 28 inch initial re-casting
Embodiment two:
other processes were unchanged when the quartz crucible 10 had a diameter of 32 inches.
Specifically, after the initial silicon raw material is charged into the quartz crucible 10, the height of the silicon raw material exceeds the upper end surface of the quartz crucible 10 by 50mm.
The initial silicon material is firstly melted and then melted at the temperature of 1500 ℃, and the height H1 from the liquid level of the initial silicon melt to the upper end face of the quartz crucible 10 is 200mm.
And cooling after the silicon melting temperature is continued for 1h, so that the temperature of the thermal field is reduced to 1400 ℃, the initial silicon melting is crystallized, and the initial re-feeding of the silicon raw material is started after the crystallization is performed for 0.5 h.
And then the re-casting silicon raw material is melted into the initial silicon melting liquid completely, the temperature of the re-casting silicon melting liquid is the same as that of the initial silicon melting liquid, and the height H2 from the re-casting silicon melting liquid level to the upper end face of the quartz crucible 10 is 70mm.
As compared with the existing crystal pulling process shown in FIG. 2, the crystal pulling rate of the first silicon rod obtained by the process of this example is shown in Table 2, and as can be seen from Table 2, each process was pulled to 10 groups and the other processes were the same, the crystal pulling rate of the first single crystal obtained by the process of this example was 85.5%, and the crystal pulling rate of the first single crystal obtained by the existing crystal pulling process was 69.8%.
TABLE 2 Crystal crucible was the result of pulling the first single crystal after the 32 inch initial re-casting
The initial re-casting process of the Czochralski single crystal designed by the invention can fully bake the inner side wall of the upper edge of the quartz crucible close to the solid-liquid interface at high temperature on the premise of not influencing the total loading amount of the quartz crucible, so that the inner wall of the quartz crucible is completely crystallized to obtain a layer of compact and stable protective layer with an alpha-cristobalite structure, and the corrosion resistance is high, so that the inner wall of the quartz crucible is not easy to generate the problems of bubble cracking or quartz falling in the process of drawing a first single crystal, thereby reducing the content of impurities in the process of pulling the crystal, further improving the crystallization effect and improving the yield of the silicon single crystal. Compared with the existing initial re-casting process, the initial re-casting process provided by the invention can improve the crystallization rate of the initial drawn silicon rod by more than 15%.
The foregoing detailed description of the embodiments of the invention has been presented only to illustrate the preferred embodiments of the invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (8)
1. The initial re-casting process of the Czochralski single crystal is characterized by comprising the following steps of:
The upper end surface of the quartz crucible carrying the silicon melting raw material has a certain height to the liquid level of the silicon melting;
The inner side annular wall surface of the quartz crucible with the certain height is subjected to crystallization phase change, and a quartz body with an alpha-cristobalite structure is obtained;
re-casting silicon raw materials into the quartz crucible after crystallization;
The certain height is not less than 100mm and not more than 300mm;
The steps before the quartz crucible crystallization comprise:
completely melting the initial silicon raw material to a molten state to form molten silicon liquid;
The silicon melt is kept at the melting temperature for a period of time, so that the inner wall surface of the quartz crucible with a certain height is covered with a crystallization layer which is the quartz body with the alpha-cristobalite structure;
the molten silicon liquid is kept at the melting temperature for at least 0.5h;
the molten silicon liquid is cooled to the crystallization temperature after being molten;
Performing primary re-casting charging to the quartz crucible within a set time after crystallization, and completely mixing and melting the re-casting silicon material and the initial silicon raw material;
After re-casting, the liquid level of the silicon melt in the quartz crucible is lower than the upper end surface of the quartz crucible;
the quartz crucible is subjected to primary re-casting and charging operation within 0.5h after crystallization;
And after re-casting, the height from the liquid level of the silicon melt in the quartz crucible to the upper end surface of the quartz crucible is not less than 40mm and not more than 100mm.
2. The initial re-casting process of a Czochralski crystal of claim 1, wherein the height is 150-250mm.
3. An initial re-casting process for Czochralski crystals as claimed in claim 1 or 2, wherein the silicon melt source material is an initial silicon source material charged into the quartz crucible.
4. A czochralski single crystal initiation re-casting process as claimed in claim 3, wherein the molten silicon feedstock is a monolithic quantity of the initial silicon feedstock.
5. An initial re-casting process for a Czochralski crystal according to any one of claims 1-2, 4, wherein the melting temperature is 1450-1500 ℃.
6. The initial re-casting process of Czochralski single crystal of claim 5, wherein the molten silicon is maintained at the melting temperature for a time period of 0.5-1h.
7. The initial re-casting process of czochralski crystal of claim 6, wherein the crystallization temperature of the molten silicon solution is 1400-1450 ℃.
8. The initial re-casting process for Czochralski single crystal according to claim 6 or 7, wherein the height from the molten silicon level in the quartz crucible to the upper end surface of the quartz crucible after re-casting is not less than 40mm and not more than 70mm.
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| CN202157142U (en) * | 2011-07-15 | 2012-03-07 | 江苏晶鼎电子材料有限公司 | Quartz crucible |
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| CN110592663A (en) * | 2019-10-12 | 2019-12-20 | 内蒙古中环光伏材料有限公司 | Use process of quartz crucible for drawing multiple single crystals |
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| CN107460538A (en) * | 2017-07-19 | 2017-12-12 | 内蒙古中环光伏材料有限公司 | It is a kind of to improve the method for throwing monocrystalline silicon crystal forming rate again and the material block for launching barium carbonate |
| CN108374196A (en) * | 2018-04-28 | 2018-08-07 | 烟台同立高科新材料股份有限公司 | A kind of polycrystalline silicon ingot casting fused silica crucible and preparation method thereof |
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