WO2017002457A1 - シリコン単結晶引上げ装置内の部材の再生方法 - Google Patents
シリコン単結晶引上げ装置内の部材の再生方法 Download PDFInfo
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- WO2017002457A1 WO2017002457A1 PCT/JP2016/063972 JP2016063972W WO2017002457A1 WO 2017002457 A1 WO2017002457 A1 WO 2017002457A1 JP 2016063972 W JP2016063972 W JP 2016063972W WO 2017002457 A1 WO2017002457 A1 WO 2017002457A1
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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
- C30B15/14—Heating of the melt or the crystallised materials
-
- 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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/20—Controlling or regulating
-
- 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
Definitions
- the present invention relates to a method of regenerating a member by removing SiOx and / or metallic silicon from a member having SiOx and / or metallic silicon adhered to a surface provided in a silicon single crystal pulling apparatus.
- This international application claims priority based on Japanese Patent Application No. 133184 (Japanese Patent Application No. 2015-133184) filed on July 2, 2015. The entire contents of Japanese Patent Application No. 2015-133184 are incorporated herein by reference. Incorporated into this international application.
- the silicon single crystal Ru pulling device in the Czochralski method SiO from the silicon melt surface, SiOx and / or metallic silicon, such as SiO 2 (hereinafter, simply referred to as "silicon or the like".)
- SiO silicon melt surface
- SiOx silicon oxide
- / or metallic silicon such as SiO 2
- SiO 2 SiO 2
- the Silicon or the like adheres to the surfaces of various members such as a heat shielding member and a rectifying cylinder provided in the pulling apparatus and gradually solidifies.
- the silicon or the like thus adhered and solidified may be peeled off from the surface of the member due to a change in the flow rate of the inert gas flowing through the pulling device or a change in the thermal expansion of the member to which the silicon or the like is adhered, and may drop into the silicon melt. It was.
- the dropped silicon or the like becomes an impurity of the silicon melt, and has been a factor that hinders the crystallization of the pulled silicon single crystal.
- the rectifying cylinder provided in the pulling device was made of quartz, silicon or the like adhered to the quartz surface of the rectifying cylinder and gradually turned brown.
- the inside of the furnace is observed through a quartz rectifier tube, there is a problem that the inside of the furnace cannot be observed due to adhesion of silicon or the like.
- the members such as the heat shielding member and the flow straightening cylinder were cleaned with the brush to remove the silicon adhering to the member surface, but the silicon etc. could not be completely removed. .
- the heat shielding member which is a graphite member to which silicon or the like is adhered, is removed by chemical cleaning outside the silicon single crystal pulling device, recycled, and this regeneration is performed at an appropriate cycle, thereby improving the quality of the silicon single crystal rod.
- a method for regenerating a heat shielding member of a single crystal pulling apparatus that suppresses variations is disclosed (for example, see Patent Document 1).
- the heat shielding member to which silicon or the like adheres during pulling is taken out of the silicon single crystal pulling apparatus, and the SiOx solution is stored in a chemical tank storing a mixed acid of hydrofluoric acid and nitric acid and a rinsing tank storing pure water.
- the heat shielding member is regenerated by cleaning and removing the deposits.
- the SiC coated on the surface can be removed uniformly, and there is a method for regenerating a SiC-coated graphite member used as a life end for a member for pulling up a single crystal in a semiconductor manufacturing process or a susceptor for epitaxial growth of a Si wafer.
- a SiC-coated graphite member used as a life end for a member for pulling up a single crystal in a semiconductor manufacturing process or a susceptor for epitaxial growth of a Si wafer.
- SiC coated on the substrate surface of the SiC-coated graphite member is subjected to a pressure of 1700 ° C. or higher and a pressure of 1.33 kPa or lower, an inert gas atmosphere, or a pressure of 1.33 kPa or lower.
- this base material After being removed by sublimation by heat treatment under an inert gas atmosphere, this base material is coated with SiC by the CVD method and reused as a SiC-coated graphite member.
- the metal silicon adheres to the surface of SiC of the susceptor for epitaxial growth used in the semiconductor manufacturing process, the metal silicon is removed together with SiC at the time of the heat treatment, or before the heat treatment.
- metallic silicon may be dissolved with a hydrofluoric acid solution or mechanically removed with a grinding wheel.
- JP 2002-037684 (Abstract, Paragraph [0009])
- the straightening cylinder which is a quartz member
- the chemical cleaning etching method disclosed in Patent Document 1 it takes at least 2 to 3 days for the cycle time to be baked after chemical cleaning, pure water cleaning, drying, and baking.
- the heat shielding member to which silicon or the like is attached cannot be efficiently regenerated.
- the rectifying cylinder is regenerated by etching, the thickness of the rectifying cylinder is reduced by the etching. Therefore, when the rectifying cylinder is regenerated about 100 times, the rectifying cylinder does not satisfy the predetermined thickness due to the thinning, and the life end is reached.
- the heat shielding member is a member in which SiC is coated on the surface of the graphite base material
- this etching regeneration method has a problem that the chemical solution penetrates between the graphite base material and the SiC coating and the SiC coating is peeled off.
- the graphite member is a carbon fiber reinforced carbon composite material knitted with carbon fibers (hereinafter referred to as “CC composite material”)
- the chemical solution is absorbed between the carbon fibers at the time of the chemical solution cleaning, and it takes time to dry and the chemical solution. May remain between the carbon fibers.
- the first object of the present invention is to solve the above-mentioned problem, and can be applied to all members to which silicon or the like in a silicon single crystal pulling apparatus adheres, shortening the time required for regeneration and reducing the thickness of the member.
- An object of the present invention is to provide a method for regenerating a member in a silicon single crystal pulling apparatus by not subliming and fearing deterioration or scratching of the surface of the member without completely sublimating and removing silicon or the like.
- the second object of the present invention is to significantly extend the usable period of the members in the silicon single crystal pulling apparatus, improve the single crystallization rate of the silicon single crystal to be pulled up, and maintain the lifetime quality of this single crystal.
- Another object of the present invention is to provide a method for regenerating a member in a silicon single crystal pulling apparatus.
- a first aspect of the present invention is a method for removing SiOx and / or metal silicon (silicon, etc.) adhering to the surface of a member provided in a silicon single crystal pulling apparatus and regenerating the member, wherein the silicon, etc.
- the surface temperature of the member is equal to or higher than the temperature at which the SiOx and / or metal silicon attached to the surface starts sublimation and the member is heated. It is characterized by sublimating and removing SiOx and / or metal silicon adhering to the surface of the member by heat treatment for at least 2 hours at a temperature lower than the temperature at which deformation and / or thermal alteration starts.
- the second aspect of the present invention is the invention based on the first aspect, characterized in that after the heat treatment, the heat treatment is cooled to room temperature at a rate of 3 to 15 ° C./min.
- a third aspect of the present invention is the invention of the first or second aspect, characterized in that the member is a graphite member and the heat treatment temperature is at least 1700 ° C.
- a fourth aspect of the present invention is the invention according to the third aspect, characterized in that the graphite member is a graphite member subjected to SiC coating treatment, and the heat treatment temperature is 1700 ° C. or higher and 2500 ° C. or lower. To do.
- a fifth aspect of the present invention is the invention of the third aspect, wherein the graphite member is a graphite member coated with a carbon film, and the heat treatment temperature is 1700 ° C. or higher and 2500 ° C. or lower.
- a sixth aspect of the present invention is an invention based on any one of the third to fifth aspects, wherein the graphite member is a heat shielding member.
- a seventh aspect of the present invention is the invention according to the first or second aspect, wherein the member is a quartz member, and the heat treatment temperature is 1400 ° C. or higher and 1700 ° C. or lower.
- the eighth aspect of the present invention is the invention of the seventh aspect, characterized in that the quartz member is a rectifying cylinder.
- a ninth aspect of the present invention is a member provided in a silicon single crystal pulling apparatus regenerated by the method of any one of the first to eighth aspects.
- a tenth aspect of the present invention is a method for producing a silicon single crystal using a member regenerated by the method of any one of the first to eighth aspects.
- the regeneration method of the first aspect of the present invention unlike the regeneration method of Patent Document 1, silicon or the like in the silicon single crystal pulling apparatus adheres because silicon or the like is completely sublimated and removed by heat treatment without using a chemical solution. Applicable to all members. Further, unlike the regeneration methods of Patent Documents 1 and 2, the time required for regeneration can be shortened because no chemical solution is used or SiC is not coated again by CVD. In addition, unlike the regeneration method of Patent Document 1 or 2, silicon or the like is not removed by using a chemical solution or by a grinding wheel, so that the thickness of the member is not reduced and the surface of the member is not deteriorated or scratched. In addition, the usable period of the members in the silicon single crystal pulling apparatus can be greatly extended, the single crystallization rate of the silicon single crystal to be pulled can be improved, and the lifetime quality of the single crystal can be maintained or improved.
- the difference between the thermal expansion coefficient of the member and the thermal expansion coefficient of silicon or the like is obtained by quenching from the heat treatment temperature to room temperature at a rate of 3 to 15 ° C./min. Using this, silicon or the like can be easily peeled off and removed from the member.
- the graphite member when the member is a graphite member, the graphite member can be regenerated by setting the regeneration heat treatment temperature to at least 1700 ° C.
- the upper limit value of the regeneration heat treatment temperature is set to 2500 ° C. to sublimate SiC covering the graphite member.
- the graphite member can be regenerated without making it.
- the upper limit of the regeneration heat treatment temperature is set to 2500 ° C.
- the graphite member can be regenerated without sublimating the film.
- the graphite member is a heat shielding member to which a relatively large amount of evaporate adheres from the silicon melt, the economic effect due to regeneration is high.
- the upper limit value of the regeneration heat treatment temperature is set to 1700 ° C., so that the quartz member does not undergo thermal deformation and / or thermal alteration.
- the member can be regenerated.
- the quartz member is a rectifying cylinder to which a relatively large amount of evaporate adheres from the silicon melt, the economic effect of regeneration is high.
- the member provided in the regenerated silicon single crystal pulling apparatus according to the ninth aspect of the present invention has no risk of dropping silicon or the like into the silicon melt, and improves the single crystallization rate of the silicon single crystal to be lifted, The lifetime quality of the single crystal can be maintained or improved.
- the method of manufacturing a silicon single crystal using the regenerated member according to the tenth aspect of the present invention improves the single crystallization rate of the silicon single crystal to be pulled up, and maintains or improves the quality of the lifetime of the single crystal. can do.
- FIG. 1 is a configuration diagram of an apparatus for regenerating a heat shielding member that is a member in a silicon single crystal pulling apparatus according to a first embodiment of the present invention.
- This reproducing apparatus uses an apparatus for pulling a silicon single crystal by the Czochralski method.
- the reproducing apparatus 10 includes a chamber 11, a heater 12, a heat insulator 13, a graphite crucible 14, and a crucible receiver 15.
- the quartz crucible 16 and the pulling wire 17 used for pulling the silicon single crystal are removed, the silicon melt 18 stored in the quartz crucible 16, the pulling wire 17 and the quartz crucible 16 is indicated by broken lines. Yes.
- the chamber 11 is a container sealed from an external atmosphere having a small diameter at the top and a large diameter at the bottom, and a heater 12, a heat insulator 13, a graphite crucible 14, a crucible receptacle 15 and the like are accommodated in the large diameter bottom.
- An inert gas introduction unit (not shown) for introducing an inert gas into the chamber is provided in the upper part of the chamber 11.
- an inert gas discharge port 19 is provided in the lower portion of the chamber 11 and is connected to a vacuum pump via an exhaust pipe (not shown).
- a viewing window 20 is provided on the shoulder located between the upper portion having a small diameter and the lower portion having a large diameter. The observation window 20 is used to measure the diameter of silicon in the silicon single crystal drawing process when the silicon single crystal is pulled up.
- the surface of the heat shielding member 21 is observed during the regeneration heat treatment. Used to.
- the member that needs to be regenerated is the heat shielding member 21 that is a graphite member.
- the heat shielding member 21 is attached to a support member 22 provided on the heat insulating material 13 in the chamber 11.
- the base material is made of graphite and the surface thereof is coated with SiC
- the base material is made of graphite and the surface thereof is coated with a carbon (C) film or the base material is made of graphite.
- a member whose surface is not coated with SiC or a carbon film is exemplified.
- the heat shielding member 21 is provided to suppress the radiant heat that the single crystal receives from the silicon melt 18 in the quartz crucible 16 when pulling up the silicon single crystal, and has a tapered shape whose diameter narrows downward. The lower end portion extends in the vicinity of the surface of the silicon melt when the silicon single crystal is pulled. For this reason, a relatively large amount of silicon or the like that is evaporated from the silicon melt 18 adheres to the heat shielding member 21.
- the heat shielding member 21 to which silicon or the like has adhered and solidified using the regenerating apparatus 10 will be described.
- the heat shielding member 21 to which silicon or the like is attached and solidified is attached to the support member 22.
- an inert gas is introduced into the chamber 11 from an inert gas introduction unit (not shown), and a vacuum pump (not shown) is operated to lower the pressure in the chamber 11.
- the heat shielding member 21 is heated by the heater 12 simultaneously with the introduction of the inert gas and the decompression of the chamber.
- the heat treatment of the heat shielding member 21 is performed under an inert gas atmosphere and a pressure of 2.67 kPa (20 torr) or less, the surface temperature of the heat shielding member is 1700 ° C. or more, and the heat shielding member is thermally deformed and / or It is carried out for at least 2 hours at a temperature below the temperature at which thermal alteration begins.
- the base material of the heat shielding member 21 is made of graphite and the surface thereof is coated with SiC, or when the base material is made of graphite and the surface thereof is coated with a carbon (C) film, the SiC or carbon film
- the upper limit value of the surface temperature of the heat shielding member 21 is set to 2500 ° C. or lower.
- the surface temperature of the heat shielding member 21 reaches 1000 ° C. or higher, sublimation of silicon or the like starts. However, by setting this temperature to 1700 ° C. or higher, the silicon or the like can be completely removed above the melting point of silicon or the like. .
- a preferable temperature is 1700 to 1800 ° C. from the viewpoint of saving heat energy consumption.
- the surface temperature of the heat shielding member is less than 1700 ° C.
- sublimation of silicon or the like adhering to the surface of the heat shielding member is hardly promoted even under an inert gas atmosphere, and silicon or the like can be completely removed.
- the heat shielding member is coated with SiC or coated with a carbon (C) film
- the regeneration treatment is performed at a temperature exceeding 2500 ° C.
- the film thickness of the SiC film or the carbon film becomes thin due to the sublimation reaction. This causes a problem that the SiC film or the carbon film is peeled off.
- the reason why the pressure in the chamber 11 is reduced to 2.67 kPa or less is to accelerate the sublimation of silicon or the like adhering to the surface of the heat shielding member 21 and to remove silicon or the like more uniformly.
- a preferable pressure is 1.33 kPa (10 torr) or less.
- the pressure exceeds 2.67 kPa sublimation of silicon or the like adhering to the surface of the heat shielding member is hardly promoted, and silicon or the like cannot be completely removed.
- the time for maintaining the temperature is at least 2 hours. If it is less than 2 hours, it becomes difficult to completely remove silicon or the like from the heat shielding member 21.
- a preferable holding time is 3 to 6 hours from the viewpoint of saving heat energy consumption.
- the heat shielding member 21 is removed from the heat treatment temperature by 3 to 3. It is preferable to cool to room temperature at a rate of 15 ° C./min. When the temperature is less than 3 ° C./minute, the difference between the thermal expansion coefficient of the heat shielding member 21 and the thermal expansion coefficient of silicon or the like is not large, and silicon or the like is difficult to peel from the heat shielding member 21. Moreover, when it exceeds 20 degreeC / min, there exists a possibility that a crack may enter into a heat shielding member.
- the heat shielding member 21 is taken out from the reproducing apparatus 10 after the heat shielding member 21 is cooled, a regenerated heat shielding member from which silicon or the like is completely removed is obtained.
- FIG. 2 is a configuration diagram of an apparatus for regenerating a rectifying cylinder which is a member in a silicon single crystal pulling apparatus according to a second embodiment of the present invention.
- this reproducing apparatus uses an apparatus that pulls up a silicon single crystal by the Czochralski method. 2, the same reference numerals as those in FIG. 1 denote the same elements.
- the member requiring regeneration is the rectifying cylinder 25.
- the rectifying cylinder 25 include a member made of quartz, graphite or a base material made of graphite and having a surface coated with SiC or a carbon film.
- the rectifying cylinder 25 is placed on a flat crucible receiver 15 in the reproducing apparatus.
- the rectifying cylinder 25 is a cylindrical member.
- the rectifying cylinder 25 extends from the upper portion having a small diameter of the chamber 11 to the vicinity of the surface of the silicon melt, and the single crystal to be pulled up inside the rectifying cylinder 25. It is arranged to pass. Further, the inert gas introduced from the inert gas introduction part described above passes through the inside of the rectifying cylinder 25 and is guided to the surface of the silicon melt 18. For this reason, a relatively large amount of silicon or the like, which is evaporated from the silicon melt, adheres to the rectifying cylinder 25.
- the regenerator 10 a method for regenerating the flow straightening cylinder 25 to which silicon or the like has adhered and solidified will be described using the regenerator 10.
- the flow straightening cylinder 25 to which silicon or the like is adhered and solidified is placed on the flat crucible receiver 15.
- an inert gas is introduced into the chamber 11 from an inert gas introduction unit (not shown), and a vacuum pump (not shown) is operated to lower the pressure in the chamber 11.
- the rectifying cylinder 25 is heated by the heater 12 simultaneously with the introduction of the inert gas and the decompression of the chamber.
- the heat treatment of the rectifying cylinder 25 is performed at a temperature of 1400 ° C. or more and 2500 ° C. or less under a pressure of 2.67 kPa (20 torr) or less in an inert gas atmosphere.
- the rectifying cylinder 25 is made of a quartz glass material
- the upper limit of the surface temperature of the rectifying cylinder 25 is set to a temperature of 1700 ° C. or lower in order to prevent thermal deformation of the rectifying cylinder 25.
- the rectifying cylinder 25 is made of graphite
- the upper limit of the surface temperature of the rectifying cylinder 25 is set to 2500 ° C. or lower in order to protect the surface coating.
- the surface temperature of the rectifying cylinder 25 becomes 1000 ° C.
- a preferable temperature is 1700 to 1800 ° C. from the viewpoint of saving heat energy consumption.
- the reason why the pressure in the chamber 11 is reduced to 2.67 kPa or less is to accelerate the sublimation of silicon or the like adhering to the surface of the rectifying cylinder 25 and remove the silicon or the like more uniformly.
- a preferable pressure is 1.33 kPa (10 torr) or less.
- a preferable holding time is 3 to 6 hours from the viewpoint of saving heat energy consumption.
- the flow straightening tube 25 After the heat treatment, it is preferable to cool the flow straightening tube 25 from the heat treatment temperature to room temperature at a rate of 3 to 15 ° C./min.
- the temperature is less than 3 ° C./min, the difference between the thermal expansion coefficient of the rectifying cylinder 25 and the thermal expansion coefficient of silicon or the like is not large, and silicon or the like is not easily separated from the rectifying cylinder 25.
- it exceeds 20 degreeC / min there exists a possibility that a rectification
- the heat shielding member is exemplified in the first embodiment
- the rectifying cylinder is exemplified in the second embodiment.
- the members that can be regenerated by the method of the present invention are not limited to these members.
- the support member 22, the graphite seed chuck, the graphite exhaust pipe, or the CC composite material used for the portion supporting the heat shielding member shown in FIG. 1 may be used.
- the CC composite material it is preferable to remove the silicon remaining between the carbon fibers by heat treatment and cooling, and then sucking the surface with a vacuum cleaner or the like.
- Example 1 A heat-shielding member having a base material made of graphite and having a SiC coating on its surface was attached to a specific pulling device, the silicon single crystal was pulled up 10 times, and silicon or the like was adhered to the surface of the heat-shielding member.
- the average adhesion thickness at 10 places where the adhesion amount was relatively large was 610 ⁇ m.
- the heat shielding member 21 with silicon or the like attached thereto was attached to the support member 22 of the regenerator 10 shown in FIG. 1, and argon gas was introduced from the inert gas introduction portion, and the inside of the chamber 11 was placed in an argon atmosphere. Further, the vacuum pump was operated to set the pressure in the chamber 11 to 1.33 kPa.
- the heater 12 was energized until the surface temperature of the heat shielding member 21 reached 1700 ° C. After maintaining at 1750 ° C. for 6 hours, the heater 12 was turned off and cooled to room temperature. The cooling rate was 4.0 ° C./min.
- Example 2 The heater was energized until the surface temperature of the heat shielding member having an average adhesion thickness of 530 ⁇ m reached 2500 ° C. by pulling the silicon single crystal 10 times. After maintaining at 2500 ° C. for 5 hours, the cooling rate was 5.9 ° C./min. Other than that, the heat shielding member coated with the same SiC as in Example 1 was heat-treated in the same apparatus as in Example 1 in the same manner as in Example 1.
- Example 3 A graphite heat-shielding member coated with a carbon film is attached to the same type of pulling device as used in Example 1, and the silicon single crystal is pulled up 10 times, and silicon or the like is adhered to the surface of the heat-shielding member. It was. The average adhesion thickness at 10 locations with a relatively large amount of adhesion was 545 ⁇ m.
- This heat shielding member was heat-treated using the reproducing apparatus 10 shown in FIG. The heater was energized until the surface temperature of the heat shielding member reached 1750 ° C. Maintained at 1750 ° C. for 6 hours. Other than that was carried out similarly to Example 1, and heat-processed the heat-shielding member coat
- Example 4 A heat shielding member that is not coated with SiC or carbon film is attached to the same type of pulling device as that used in Example 1, and the silicon single crystal is pulled up 10 times, and silicon or the like is attached to the surface of the heat shielding member. I let you.
- the average adhesion thickness at 10 places where the adhesion amount was relatively large was 580 ⁇ m.
- This heat shielding member was heat-treated using the reproducing apparatus 10 shown in FIG.
- the heat treatment holding temperature to be regenerated was set to 1700 ° C., the holding time was set to 6 hours, the pressure in the chamber 11 was set to 2.67 kPa, and the cooling rate after the heat treatment was set to 4.0 ° C./min.
- Example 5 A rectifying cylinder made of quartz glass material was attached to a pulling apparatus of the same model as the pulling apparatus used in Example 1, the silicon single crystal was pulled up 10 times, and silicon or the like was adhered to the surface of the rectifying cylinder.
- the average adhesion thickness at 10 locations where the adhesion amount was relatively large was 123 ⁇ m.
- This flow straightening tube was heat-treated using the reproducing apparatus 10 shown in FIG.
- the heat treatment holding temperature for regeneration was set to 1400 ° C., the holding time was set to 3 hours, the pressure in the chamber 11 was set to 1.33 kPa, and the cooling rate after the heat treatment was set to 3.1 ° C./min. Other than that was carried out similarly to Example 1, and heat-treated the rectification
- Example 6 The heater was energized until the surface temperature of the rectifying cylinder having an average deposition thickness of 135 ⁇ m reached 1700 ° C. by pulling the silicon single crystal 10 times. After maintaining at 1700 ° C. for 2 hours, the cooling rate was 3.8 ° C./min. Other than that, the flow straightening tube made of the same quartz glass material as in Example 5 was heat-treated in the same manner as in Example 1 by using the reproducing apparatus 10 shown in FIG.
- Example 7 A rectifier cylinder that is not coated with graphite SiC or carbon film is attached to a puller apparatus of the same model as the puller apparatus used in Example 1, the silicon single crystal is pulled up ten times, and silicon or the like is applied to the surface of the rectifier cylinder. Attached. The average adhesion thickness at 10 places where the adhesion amount was relatively large was 141 ⁇ m.
- This flow straightening tube was heat-treated using the reproducing apparatus 10 shown in FIG. The heat treatment holding temperature for regeneration was set to 1700 ° C., the holding time was set to 4 hours, the pressure in the chamber 11 was set to 1.33 kPa, and the cooling rate after the heat treatment was set to 3.8 ° C./min. Other than that was carried out similarly to Example 1, and heat-treated the rectification
- Example 1 A heat shielding member made of the same graphite as in Example 1 and coated with SiC on the surface thereof is attached to the same type of pulling device as used in Example 1, and the silicon single crystal is pulled up 10 times. Silicon or the like was allowed to adhere to the surface. The average adhesion thickness at 10 locations with a relatively large amount of adhesion was 527 ⁇ m.
- This heat shielding member was heat-treated using the reproducing apparatus 10 shown in FIG. The heat treatment holding temperature for regeneration was set to 1650 ° C., the holding time was set to 4 hours, the pressure in the chamber 11 was set to 1.33 kPa, and the cooling rate after the heat treatment was set to 3.7 ° C./min. Other than that was carried out similarly to Example 1, and heat-processed the heat shielding member by which SiC coating
- Example 2 A heat shielding member made of the same graphite as in Example 1 and coated with SiC on the surface thereof is attached to the same type of pulling device as used in Example 1, and the silicon single crystal is pulled up 10 times. Silicon or the like was allowed to adhere to the surface. The average adhesion thickness at 10 locations with a relatively large amount of adhesion was 582 ⁇ m.
- This heat shielding member was heat-treated using the reproducing apparatus 10 shown in FIG. The heat treatment holding temperature for regeneration was set to 2550 ° C., the holding time was set to 5 hours, the pressure in the chamber 11 was set to 1.33 kPa, and the cooling rate after the heat treatment was set to 6.0 ° C./min. Other than that was carried out similarly to Example 1, and heat-processed the heat shielding member by which SiC coating
- Example 3 A heat shielding member made of the same graphite as in Example 1 and coated with SiC on the surface thereof is attached to the same type of pulling device as used in Example 1, and the silicon single crystal is pulled up 10 times. Silicon or the like was allowed to adhere to the surface. The average adhesion thickness at 10 locations with a relatively large adhesion amount was 560 ⁇ m.
- This heat shielding member was heat-treated using the reproducing apparatus 10 shown in FIG. The heat treatment holding temperature for regeneration was set to 1750 ° C., and the holding time was set to 1.8 hours. Other than that was carried out similarly to Example 1, and heat-processed the heat shielding member by which SiC coating
- Example 4 The same type of pulling apparatus as used in Example 1 is attached to the same heat shielding member that is not coated with SiC or carbon film as in Example 4, and the silicon single crystal is pulled up 10 times. Silicon or the like was adhered to the surface. The average adhesion thickness at 10 locations with a relatively large amount of adhesion was 509 ⁇ m.
- This heat shielding member was heat-treated using the reproducing apparatus 10 shown in FIG. The heat treatment holding temperature for regeneration was set to 1650 ° C., the holding time was set to 6 hours, and the pressure in the chamber 11 was set to 4.0 kPa. Other than that was carried out similarly to Example 1, and heat-processed the heat shielding member in which neither SiC nor a carbon film was coat
- Example 5 A rectifying cylinder made of the same quartz glass material as in Example 5 was attached to a pulling apparatus of the same model as the pulling apparatus used in Example 1, the silicon single crystal was pulled up 10 times, and silicon or the like was adhered to the surface of the rectifying cylinder. .
- the average adhesion thickness at 10 places where the adhesion amount was relatively large was 115 ⁇ m.
- This flow straightening tube was heat-treated using the reproducing apparatus 10 shown in FIG.
- the heat treatment holding temperature for regeneration was set to 1350 ° C., the holding time was set to 2 hours, the pressure in the chamber 11 was set to 1.33 kPa, and the cooling rate after the heat treatment was set to 2.9 ° C./min. Other than that was carried out similarly to Example 1, and heat-treated the rectification
- Example 6 ⁇ Comparative Example 6> The heater was energized until the surface temperature of the rectifying cylinder having an average adhesion thickness of 129 ⁇ m reached 1750 ° C. by pulling the silicon single crystal 10 times. Heat treatment was performed at 1750 ° C. for 3 hours. Otherwise, the same apparatus as in Example 1 was used to heat-treat the rectifying cylinder made of the same quartz glass material as in Example 5 in the same manner as in Example 1.
- Example 7 A heat shielding member made of the same graphite as in Example 1 and coated with SiC on the surface thereof is attached to the same type of pulling device as used in Example 1, and the silicon single crystal is pulled up 10 times. Silicon or the like was allowed to adhere to the surface. The average adhesion thickness at 10 locations with relatively large adhesion amounts was 532 ⁇ m.
- This heat shielding member was regenerated by an etching method according to the method shown in Patent Document 1. First, a mixed solution of hydrofluoric acid and nitric acid, which is a chemical solution, was stored in the chemical solution tank, and then the heat shielding member to which silicon or the like was adhered was immersed in the chemical solution and ultrasonically cleaned.
- the heat shielding member from which silicon or the like was washed and removed was transferred from the chemical solution tank to a rinse tank for storing pure water and immersed therein.
- the heat shielding member was ultrasonically cleaned with this rinsing layer in the same manner as the chemical bath, and then the heat shielding member was pulled up from the rinse bath, dried and regenerated.
- Example 8 A heat shielding member made of the same graphite as in Example 1 and coated with SiC on the surface thereof is attached to the same type of pulling device as used in Example 1, and the silicon single crystal is pulled up 10 times. Silicon or the like was allowed to adhere to the surface. The average adhesion thickness at 10 locations with a relatively large adhesion amount was 590 ⁇ m. The surface of this heat shielding member was polished using a grinding wheel (grain size # 1000) described in Patent Document 2, and silicon or the like adhering to the surface of the heat shielding member was mechanically removed.
- the graphite heat shield member with the SiC coating of Comparative Example 7 regenerated by the chemical cleaning etching method took 326 hours to regenerate. Furthermore, in the graphite heat shielding member with the SiC coating of Comparative Example 8 in which the surface was polished with a grinding wheel and silicon or the like adhering to the surface was mechanically removed, silicon or the like was adhered after the regeneration treatment. In addition, a large number of grinding balls were present on the surface.
- the heat shielding member and the rectifying cylinder regenerated in Examples 1 to 7 had no silicon or the like attached after the regeneration process, and the thickness average change rate of the members was 1 and the thickness There was no change or thermal deformation, and no film peeling or surface flaws occurred.
- the time required for regeneration was relatively short, 9.5 to 13.5 hours, and it was possible to reproduce quickly.
- the two heat shielding members were again attached to the same pulling device, and silicon or the like was similarly attached to the respective surfaces of the two heat shielding members.
- the regeneration of the two heat shielding members and the adhesion of silicon or the like were repeated, and the number of times until the SiC coating of both heat shielding members was peeled was measured.
- the SiC coating started to peel off after 70 times, whereas in the method according to Example 1, the SiC coating began to peel off after 220 times.
- Example 1 the heat shielding member reproduced
- the lifetime of the silicon wafer improved on average by about 18% over the lifetime of the silicon wafer manufactured from the pulling apparatus having the heat shielding member regenerated by the method of Comparative Example 7, and the variation was small. As a result, it was confirmed that the degree of cleaning was higher when the heat shielding member was regenerated by the method of Example 1 than when the heat shielding member was regenerated by the method of Comparative Example 7.
- the regeneration method of the present invention is used for sublimation removal of silicon or the like from a member to which silicon or the like in a silicon single crystal pulling apparatus adheres.
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Abstract
Description
図1は、本発明の第1の実施形態に係るシリコン単結晶引上げ装置内の部材である熱遮蔽部材を再生する装置の構成図である。この再生装置は、チョクラルスキー法でシリコン単結晶を引上げる装置を利用している。この実施の形態では、再生装置10は、チャンバ11と、ヒータ12と、断熱体13と、黒鉛坩堝14、坩堝受け15を備える。この再生装置10では、シリコン単結晶引上げ時に使用する石英坩堝16及び引上げワイヤ17は外してあるため、石英坩堝16、引上げワイヤ17及び石英坩堝16内に貯えるシリコン融液18はそれぞれ破線で示している。
図2は、本発明の第2の実施形態に係るシリコン単結晶引上げ装置内の部材である整流筒を再生する装置の構成図である。この再生装置は、第1の実施形態と同様に、チョクラルスキー法でシリコン単結晶を引上げる装置を利用している。図2において、図1と同一符号は同一要素を示している。この実施の形態では、再生を必要とする部材は整流筒25である。この整流筒25としては、石英製、黒鉛製又は基材が黒鉛製でその表面にSiC又は炭素膜が被覆された部材が例示される。この整流筒25は、再生装置内では平坦な坩堝受け15の上に載置される。
特定の引上げ装置に基材が黒鉛製でその表面にSiC被覆がなされた熱遮蔽部材を取付け、シリコン単結晶を10回引上げ、この熱遮蔽部材の表面にシリコン等を付着させた。付着量が比較的多い10箇所の平均付着厚さは610μmであった。図1に示す再生装置10の支持部材22にシリコン等が付着した上記熱遮蔽部材21を取付け、不活性ガス導入部からアルゴンガスを導入し、チャンバ11内をアルゴン雰囲気下にした。また真空ポンプを作動してチャンバ11内の圧力を1.33kPaにした。この状態で熱遮蔽部材21の表面温度が1700℃になるまでヒータ12を通電した。1750℃で6時間維持した後、ヒータ12を切電して室温まで、冷却した。冷却速度は4.0℃/分であった。
シリコン単結晶の10回の引上げにより平均付着厚さが530μmであった熱遮蔽部材の表面温度を2500℃になるまでヒータを通電した。2500℃で5時間維持した後、冷却速度を5.9℃/分にした。それ以外は、実施例1と同じ装置で実施例1と同じSiC被覆がなされた熱遮蔽部材を実施例1と同様に熱処理した。
実施例1で用いた引上げ装置と同一機種の引上げ装置に炭素膜が被覆された黒鉛製の熱遮蔽部材を取付け、シリコン単結晶を10回引上げ、この熱遮蔽部材の表面にシリコン等を付着させた。付着量が比較的多い10箇所の平均付着厚さは545μmであった。この熱遮蔽部材を図1に示す再生装置10を用いて熱処理した。熱遮蔽部材の表面温度を1750℃になるまでヒータを通電した。1750℃で6時間維持した。それ以外は、実施例1と同様にして、炭素膜が被覆された熱遮蔽部材を熱処理した。
実施例1で用いた引上げ装置と同一機種の引上げ装置にSiCも炭素膜も被覆がなされていない熱遮蔽部材を取付け、シリコン単結晶を10回引上げ、この熱遮蔽部材の表面にシリコン等を付着させた。付着量が比較的多い10箇所の平均付着厚さは580μmであった。この熱遮蔽部材を図1に示す再生装置10を用いて熱処理した。再生する熱処理保持温度を1700℃に、保持時間を6時間に、チャンバ11内の圧力を2.67kPaに、熱処理後の冷却速度を4.0℃/分にそれぞれ設定した。それ以外は、実施例1と同様にして、SiCも炭素膜も被覆がなされていない熱遮蔽部材を熱処理した。
実施例1で用いた引上げ装置と同一機種の引上げ装置に石英ガラス材料からなる整流筒を取付け、シリコン単結晶を10回引上げ、この整流筒の表面にシリコン等を付着させた。付着量が比較的多い10箇所の平均付着厚さは123μmであった。この整流筒を図2に示す再生装置10を用いて熱処理した。再生する熱処理保持温度を1400℃に、保持時間を3時間に、チャンバ11内の圧力を1.33kPaに、熱処理後の冷却速度を3.1℃/分にそれぞれ設定した。それ以外は、実施例1と同様にして、石英ガラス材料からなる整流筒を熱処理した。
シリコン単結晶の10回の引上げにより平均付着厚さが135μmであった整流筒の表面温度を1700℃になるまでヒータを通電した。1700℃で2時間維持した後、冷却速度を3.8℃/分にした。それ以外は、図2に示す再生装置10を用いて、実施例5と同じ石英ガラス材料からなる整流筒を実施例1と同様に熱処理した。
実施例1で用いた引上げ装置と同一機種の引上げ装置に黒鉛製のSiCも炭素膜も被覆がなされていない整流筒を取付け、シリコン単結晶を10回引上げ、この整流筒の表面にシリコン等を付着させた。付着量が比較的多い10箇所の平均付着厚さは141μmであった。この整流筒を図2に示す再生装置10を用いて熱処理した。再生する熱処理保持温度を1700℃に、保持時間を4時間に、チャンバ11内の圧力を1.33kPaに、熱処理後の冷却速度を3.8℃/分にそれぞれ設定した。それ以外は、実施例1と同様にして、黒鉛製のSiCも炭素膜も被覆がなされていない整流筒を熱処理した。
実施例1で用いた引上げ装置と同一機種の引上げ装置に実施例1と同一の黒鉛製でその表面にSiC被覆がなされた熱遮蔽部材を取付け、シリコン単結晶を10回引上げ、この熱遮蔽部材の表面にシリコン等を付着させた。付着量が比較的多い10箇所の平均付着厚さは527μmであった。この熱遮蔽部材を図1に示す再生装置10を用いて熱処理した。再生する熱処理保持温度を1650℃に、保持時間を4時間に、チャンバ11内の圧力を1.33kPaに、熱処理後の冷却速度を3.7℃/分にそれぞれ設定した。それ以外は、実施例1と同様にして、SiC被覆がなされた熱遮蔽部材を熱処理した。
実施例1で用いた引上げ装置と同一機種の引上げ装置に実施例1と同一の黒鉛製でその表面にSiC被覆がなされた熱遮蔽部材を取付け、シリコン単結晶を10回引上げ、この熱遮蔽部材の表面にシリコン等を付着させた。付着量が比較的多い10箇所の平均付着厚さは582μmであった。この熱遮蔽部材を図1に示す再生装置10を用いて熱処理した。再生する熱処理保持温度を2550℃に、保持時間を5時間に、チャンバ11内の圧力を1.33kPaに、熱処理後の冷却速度を6.0℃/分にそれぞれ設定した。それ以外は、実施例1と同様にして、SiC被覆がなされた熱遮蔽部材を熱処理した。
実施例1で用いた引上げ装置と同一機種の引上げ装置に実施例1と同一の黒鉛製でその表面にSiC被覆がなされた熱遮蔽部材を取付け、シリコン単結晶を10回引上げ、この熱遮蔽部材の表面にシリコン等を付着させた。付着量が比較的多い10箇所の平均付着厚さは560μmであった。この熱遮蔽部材を図1に示す再生装置10を用いて熱処理した。再生する熱処理保持温度を1750℃に、保持時間を1.8時間にそれぞれ設定した。それ以外は、実施例1と同様にして、SiC被覆がなされた熱遮蔽部材を熱処理した。
実施例1で用いた引上げ装置と同一機種の引上げ装置に実施例4と同一のSiCも炭素膜も被覆がなされていない熱遮蔽部材を取付け、シリコン単結晶を10回引上げ、この熱遮蔽部材の表面にシリコン等を付着させた。付着量が比較的多い10箇所の平均付着厚さは509μmであった。この熱遮蔽部材を図1に示す再生装置10を用いて熱処理した。再生する熱処理保持温度を1650℃に、保持時間を6時間に、チャンバ11内の圧力を4.0kPaにそれぞれ設定した。それ以外は、実施例1と同様にして、SiCも炭素膜も被覆がなされていない熱遮蔽部材を熱処理した。
実施例1で用いた引上げ装置と同一機種の引上げ装置に実施例5と同じ石英ガラス材料からなる整流筒を取付け、シリコン単結晶を10回引上げ、この整流筒の表面にシリコン等を付着させた。付着量が比較的多い10箇所の平均付着厚さは115μmであった。この整流筒を図2に示す再生装置10を用いて熱処理した。再生する熱処理保持温度を1350℃に、保持時間を2時間に、チャンバ11内の圧力を1.33kPaに、熱処理後の冷却速度を2.9℃/分にそれぞれ設定した。それ以外は、実施例1と同様にして、石英ガラス材料からなる整流筒を熱処理した。
シリコン単結晶の10回の引上げにより平均付着厚さが129μmであった整流筒の表面温度を1750℃になるまでヒータを通電した。1750℃で3時間維持して熱処理した。それ以外は、実施例1と同じ装置で実施例5と同じ石英ガラス材料からなる整流筒を実施例1と同様に熱処理した。
実施例1で用いた引上げ装置と同一機種の引上げ装置に実施例1と同一の黒鉛製でその表面にSiC被覆がなされた熱遮蔽部材を取付け、シリコン単結晶を10回引上げ、この熱遮蔽部材の表面にシリコン等を付着させた。付着量が比較的多い10箇所の平均付着厚さは532μmであった。この熱遮蔽部材を特許文献1に示す方法に準じたエッチング処理方法で再生した。先ず薬液槽内に薬液であるフッ酸と硝酸の混酸を貯え、次いでシリコン等が付着した熱遮蔽部材を薬液に浸漬し、超音波洗浄した。シリコン等が洗浄除去された熱遮蔽部材を薬液槽から純水を貯えるリンス槽に移して浸漬した。このリンス層で薬液槽と同様に熱遮蔽部材を超音波洗浄した後、熱遮蔽部材をリンス槽から引上げ、乾燥して、再生した。
実施例1で用いた引上げ装置と同一機種の引上げ装置に実施例1と同一の黒鉛製でその表面にSiC被覆がなされた熱遮蔽部材を取付け、シリコン単結晶を10回引上げ、この熱遮蔽部材の表面にシリコン等を付着させた。付着量が比較的多い10箇所の平均付着厚さは590μmであった。この熱遮蔽部材の表面を特許文献2に記載の研削砥石(粒度1000番)を用いて研磨し、熱遮蔽部材の表面に付着していたシリコン等を機械的に除去した。
実施例1~7及び比較例1~8で用いた熱遮蔽部材又は整流筒の部材について、再生後におけるシリコン等の付着状況、再生前後における部材肉厚の変化状況、再生後における部材表面の劣化又は疵の有無及び再生に要した時間を調べた。部材の肉厚はノギスで10箇所測定し、再生前を1としたときの再生後の肉厚の平均値を割合(肉厚平均変化率)で示す。再生後におけるシリコン等の付着状況及び部材表面の劣化又は疵の有無は目視により判定した。これらの結果を表1に示す。
同一機種のシリコン単結晶引上げ装置を2台選び、2台の引上げ装置に、同一の製造ロットから選ばれた基材が黒鉛製でその表面にSiC被覆がなされた2つの熱遮蔽部材を各別に取付け、かつ同一のシリコン原料をそれぞれの坩堝に入れ、これをシリコン融液にした後、2台とも同一の引上げ条件でシリコン単結晶を引上げた。2台の引上げ装置の坩堝を交換し、それぞれ同一の引上げ条件でシリコン単結晶を10回繰り返し引上げたところ、2つの熱遮蔽部材の各表面にシリコン等が付着した。1つの熱遮蔽部材を実施例1による方法により、他の1つの熱遮蔽部材を比較例7による方法により、それぞれ再生した。再生後、再び2つの熱遮蔽部材を同一の引上げ装置に取付け、同様に2つの熱遮蔽部材の各表面にシリコン等を付着させた。2つの熱遮蔽部材の再生とシリコン等の付着を繰り返し行い、双方の熱遮蔽部材のSiC被覆が剥がれるまでの回数を測定した。その結果、比較例7による方法では、70回でSiC被覆が剥がれ始めたのに対して、実施例1による方法では、220回でSiC被覆が剥がれ始めた。これにより、実施例1により再生した熱遮蔽部材は、比較例7により再生した熱遮蔽部材よりも、3倍以上長く使用することができ、熱遮蔽部材のライフエンドを大幅に伸ばすことができた。
同一機種のシリコン単結晶引上げ装置を3台選び、3台の引上げ装置に、同一の製造ロットから選ばれた基材が黒鉛製でその表面にSiC被覆がなされた3つの熱遮蔽部材を各別に取付け、かつ同一のシリコン原料をそれぞれの坩堝に入れ、これをシリコン融液にした後、3台とも同一の引上げ条件でシリコン単結晶を引上げた。それぞれ同一の引上げ条件でシリコン単結晶を10回繰り返し引上げたところ、3つの熱遮蔽部材の各表面にシリコン等が付着した。1つの熱遮蔽部材は実施例1の方法により再生した。もう1つの熱遮蔽部材は比較例1の方法により再生した。残りの1つの熱遮蔽部材は再生しなかった。これら3つの熱遮蔽部材を同一の引上げ装置に取付けて、更に続けて同一の引上げ条件でそれぞれ10本シリコン単結晶を引上げた。3台の引上げ装置で引上げたそれぞれ10本のシリコン単結晶の単結晶化率(Disloction Free Ratio)を測定した。その結果、再生しなかった熱遮蔽部材を用いて引上げたシリコン単結晶の単結晶化率を100としたときに、比較例1の方法により再生した熱遮蔽部材を用いて引上げたシリコン単結晶の単結晶化率が100.4であったのに対して、実施例1の方法により再生した熱遮蔽部材を用いて引上げたシリコン単結晶の単結晶化率は、平均102.2であり、単結晶化率が約2%向上した。単結晶化率が向上したのは、熱遮蔽部材からシリコン等がシリコン融液に落下して混入する量が他の2例よりも少なかったためと推察された。
比較例6のエッチング処理方法により再生した熱遮蔽部材を有する引上げ装置で直径200mmのp型で結晶方位が<100>であるシリコン単結晶を295本引上げた。これらの単結晶からそれぞれ切り出したシリコンウェーハの抵抗率を四端子法にて測定した。抵抗率が5Ω・cm以上のシリコンウェーハのライフタイムを10Ω・cmに換算し、これらのライフタイムの平均値を1として各ライフタイムを相対値で求めた。一方、実施例1の方法で再生した熱遮蔽部材以外は上記と同じ引上げ装置で同一原料を用いて同一引上げ方法により直径200mmのp型で結晶方位が<100>であるシリコン単結晶を10本引上げた。これらの単結晶からそれぞれ切り出したシリコンウェーハの各抵抗率を上記と同じ方法で測定し、得られた抵抗率をそれぞれ上記と同様に10Ω・cmに換算した。換算して得られたライフタイムの各相対値を、比較例7の抵抗率のライフタイムの平均値と比較したところ、実施例1の方法で再生した熱遮蔽部材を有する引上げ装置から製造されたシリコンウェーハのライフタイムは、比較例7の方法で再生した熱遮蔽部材を有する引上げ装置から製造されたシリコンウェーハのライフタイムよりも平均で約18%向上し、かつばらつきも小さかった。この結果、比較例7の方法で熱遮蔽部材を再生処理するよりも、実施例1の方法で熱遮蔽部材を再生処理する方が、清浄化の度合いが高いことが確認された。
Claims (10)
- シリコン単結晶引上げ装置内に設けられる部材の表面に付着したSiOx及び/又は金属シリコンを除去して前記部材を再生する方法において、
前記SiOx及び/又は金属シリコンが表面に付着した部材を不活性ガス雰囲気下、2.67kPa以下の圧力下、前記部材の表面温度が表面に付着した前記SiOx及び/又は金属シリコンの昇華を開始する温度以上でかつ前記部材が熱変形及び/又は熱変質を開始する温度未満の温度で少なくとも2時間熱処理して前記部材の表面に付着したSiOx及び/又は金属シリコンを昇華し除去することを特徴とするシリコン単結晶引上げ装置内の部材の再生方法。 - 前記熱処理した後に、前記熱処理温度から3~15℃/分の速度で室温まで冷却する請求項1記載の再生方法。
- 前記部材が黒鉛部材であって、前記熱処理温度が少なくとも1700℃である請求項1又は2記載の再生方法。
- 前記黒鉛部材がSiC被覆処理された黒鉛部材であって、前記熱処理温度が1700℃以上2500℃以下である請求項3記載の再生方法。
- 前記黒鉛部材が炭素膜により被覆処理された黒鉛部材であって、前記熱処理温度が1700℃以上2500℃以下である請求項3記載の再生方法。
- 前記黒鉛部材が熱遮蔽部材である請求項3ないし5のいずれか1項に記載の再生方法。
- 前記部材が石英部材であって、前記熱処理温度が1400℃以上1700℃以下である請求項1又は2記載の再生方法。
- 前記石英部材が整流筒である請求項7記載の再生方法。
- 請求項1ないし8のうちいずれか1項に記載された方法で再生されたシリコン単結晶引上げ装置内に設けられる部材。
- 請求項1ないし8のうちいずれか1項に記載された方法で再生された部材を用いて、シリコン単結晶を製造する方法。
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