JP2010280567A - Method for producing silica glass crucible - Google Patents
Method for producing silica glass crucible Download PDFInfo
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- JP2010280567A JP2010280567A JP2010208668A JP2010208668A JP2010280567A JP 2010280567 A JP2010280567 A JP 2010280567A JP 2010208668 A JP2010208668 A JP 2010208668A JP 2010208668 A JP2010208668 A JP 2010208668A JP 2010280567 A JP2010280567 A JP 2010280567A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 238000004017 vitrification Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 11
- 230000003749 cleanliness Effects 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 30
- 229910052710 silicon Inorganic materials 0.000 abstract description 23
- 239000010703 silicon Substances 0.000 abstract description 23
- 239000004065 semiconductor Substances 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 9
- 238000011109 contamination Methods 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Crystals, And After-Treatments Of Crystals (AREA)
- Glass Melting And Manufacturing (AREA)
Abstract
【課題】原料融液が充填された高温下での変形や歪みが抑制され、かつ、ブラウンモールドの発生が抑制され、しかも、ルツボに起因する不純物汚染を招くことなく、シリコン等の半導体単結晶を歩留まりよく引上げるのに好適なシリカガラスルツボの製造方法を提供する。
【解決手段】厚さ方向における外層が天然質シリカガラス、内層が合成シリカガラスからなるルツボの製造方法において、外層および内層を、それぞれ、天然シリカ質原料粉および合成シリカ原料粉を減圧アーク溶融によりガラス化して形成し、少なくとも直胴部における外層と内層の総厚さが６〜１６ｍｍ、内層の厚さが総厚さの５〜４０％、かつ、内層におけるＮａ，Ｋ，Ｌｉ，Ｃａ，Ａｌ，Ｔｉ，Ｆｅ，Ｃｕのいずれの濃度も０．１ｐｐｍ以下、外層におけるＮａ濃度が０．２ｐｐｍ以下、ルツボ内表面から深さ０．５ｍｍ以下の領域において直径２０μｍ以上の気孔が２０個／ｍｍ2以下となる構成とする。
【選択図】なしA semiconductor single crystal such as silicon is suppressed in which deformation and distortion at high temperatures filled with a raw material melt are suppressed, generation of a brown mold is suppressed, and contamination of impurities caused by a crucible is not caused. A method for producing a silica glass crucible that is suitable for pulling up with good yield is provided.
In a method for producing a crucible in which an outer layer in the thickness direction is made of natural silica glass and an inner layer is made of synthetic silica glass, the outer layer and the inner layer are respectively made of natural siliceous raw material powder and synthetic silica raw material powder by reduced-pressure arc melting. It is formed by vitrification, and the total thickness of the outer layer and the inner layer in the straight body portion is 6 to 16 mm, the thickness of the inner layer is 5 to 40% of the total thickness, and Na, K, Li, Ca, Al in the inner layer , Ti, Fe, and Cu are each 0.1 ppm or less, Na concentration in the outer layer is 0.2 ppm or less, and 20 pores / mm 2 having a diameter of 20 μm or more in a region having a depth of 0.5 mm or less from the crucible inner surface. The configuration is as follows.
[Selection figure] None
Description
本発明は、シリコン等の半導体単結晶引上げにおいて、原料を溶融するために好適に用いられるシリカガラスルツボの製造方法に関する。 The present invention relates to a method for producing a silica glass crucible that is suitably used for melting a raw material in pulling a semiconductor single crystal such as silicon.
シリコン等の半導体単結晶は、主に、チョクラルスキー（ＣＺ）法により製造されている。このＣＺ法によるシリコン単結晶の製造は、シリコン単結晶の種結晶を、多結晶シリコンを溶融したシリコン原料融液に着液させて、回転させながら徐々に引上げていき、シリコン単結晶インゴットを成長させることにより行われる。 Semiconductor single crystals such as silicon are mainly manufactured by the Czochralski (CZ) method. In the production of silicon single crystals by this CZ method, a silicon single crystal seed crystal is deposited on a silicon raw material melt obtained by melting polycrystalline silicon, and gradually pulled up while rotating to grow a silicon single crystal ingot. Is done.
上記のようなＣＺ法によるシリコン単結晶の引上げにおいて、原料を加熱溶融するための容器には、一般に、外層が水晶等の天然質原料を溶融ガラス化した天然質シリカガラス、内層が合成シリカガラスからなるシリカガラスルツボが用いられている。
前記シリカガラスルツボは、その中に多結晶シリコンを充填し、シリコンの融点（約１４００℃）以上の温度に加熱されると、通常、該ルツボ内表面に、褐色のリング状のクリストバライト、いわゆるブラウンモールド（ブラウンリングとも言う。）が生成する。
このブラウンモールドは、加熱により徐々に拡大し、該内表面の荒れや剥離が生じ、その結果、シリコン原料融液中に前記剥離片が混入し、シリコン単結晶に転位が発生し、シリコン単結晶の歩留まりの低下を招いていた。
In pulling a silicon single crystal by the CZ method as described above, a container for heating and melting a raw material is generally a natural silica glass obtained by melting and vitrifying a natural raw material such as quartz, and an inner layer is a synthetic silica glass. A silica glass crucible made of is used.
When the silica glass crucible is filled with polycrystalline silicon and heated to a temperature equal to or higher than the melting point of silicon (about 1400 ° C.), a brown ring-shaped cristobalite, so-called brown, is usually formed on the inner surface of the crucible. A mold (also called a brown ring) is generated.
This brown mold gradually expands by heating, and the inner surface is roughened and peeled off. As a result, the peeled pieces are mixed in the silicon raw material melt, and dislocations are generated in the silicon single crystal. The yield of was reduced.
前記ブラウンモールド発生は、一般的には、シリカガラスルツボの内表面における不純物が原因であると考えられ、このため、該ルツボの内層が高純度の合成シリカガラスからなるシリカガラスルツボが使用されていた。
しかしながら、このようなルツボを用いた場合であっても、ブラウンモールドの発生は十分に抑制できていないのが現状である。
The occurrence of the brown mold is generally considered to be caused by impurities on the inner surface of the silica glass crucible. For this reason, a silica glass crucible in which the inner layer of the crucible is made of high-purity synthetic silica glass is used. It was.
However, even in the case where such a crucible is used, the current situation is that the occurrence of brown mold cannot be sufficiently suppressed.
さらに、近年のシリコン単結晶の大口径化に伴い、用いられるルツボも大型化が進み、より高強度であることが求められ、また、シリコン単結晶の引上げに要する時間も長時間化し、その間、シリコン原料融液を充填されたシリカガラスルツボは、１４００℃以上の高温下に曝されることから、より一層のルツボの強度向上が求められている。 Furthermore, with the recent increase in diameter of silicon single crystals, the size of crucibles used has increased, and it is required to have higher strength, and the time required for pulling up silicon single crystals has also become longer, Since the silica glass crucible filled with the silicon raw material melt is exposed to a high temperature of 1400 ° C. or higher, further improvement in the strength of the crucible is required.
上記課題に対しては、例えば、特許文献１に、ルツボ内層の内表面付近に、所定濃度のＡｌとＯＨ基を導入することにより、内層と外層との剥離が抑制され、ルツボの変形も抑制されることが開示されている。 For example, in Patent Document 1, by introducing Al and OH groups at a predetermined concentration near the inner surface of the crucible inner layer, peeling between the inner layer and the outer layer is suppressed, and deformation of the crucible is also suppressed. Is disclosed.
しかしながら、上記特許文献１に記載されているように、内層にＡｌ等の金属を含むルツボは、これと接触するシリコン原料融液の不純物汚染を招くおそれがあり、高純度かつ高品質が求められるシリコン単結晶の引上げには、好ましい態様のルツボとは言い難いものであった。 However, as described in Patent Document 1, the crucible containing a metal such as Al in the inner layer may cause impurity contamination of the silicon raw material melt in contact with the crucible, and high purity and high quality are required. The pulling of the silicon single crystal was difficult to say as a preferred embodiment crucible.
したがって、シリコン等の半導体単結晶の引上げに用いられるルツボは、上記のように、耐熱強度に優れていることに加えて、ルツボ自体が不純物汚染源とならないような構成であることも求められる。 Therefore, a crucible used for pulling up a semiconductor single crystal such as silicon is required to have a structure in which the crucible itself does not become a source of impurity contamination in addition to excellent heat resistance as described above.
本発明は、上記技術的課題を解決するためになされたものであり、原料融液が充填された高温下での変形や歪みが抑制され、かつ、ブラウンモールドの発生が抑制され、しかも、ルツボに起因する不純物汚染を招くことなく、シリコン等の半導体単結晶を歩留まりよく引上げるのに好適なシリカガラスルツボの製造方法を提供することを目的とするものである。 The present invention has been made to solve the above technical problem, and is capable of suppressing deformation and distortion at a high temperature filled with a raw material melt, suppressing the occurrence of a brown mold, and a crucible. An object of the present invention is to provide a method for producing a silica glass crucible suitable for pulling up a semiconductor single crystal such as silicon with a high yield without causing impurity contamination.
本発明に係るシリカガラスルツボの製造方法は、上方から直胴部、コーナー部および底部からなる有底容器状であり、その厚さ方向における外層が天然質シリカガラス、内層が合成シリカガラスからなるルツボの製造方法において、前記外層および内層を、それぞれ、天然シリカ質原料粉および合成シリカ原料粉を減圧アーク溶融によりガラス化して形成し、少なくとも前記直胴部における外層と内層の総厚さが６ｍｍ以上１６ｍｍ以下、内層の厚さが総厚さの５％以上４０％以下であり、かつ、前記内層におけるＮａ，Ｋ，Ｌｉ，Ｃａ，Ａｌ，Ｔｉ，Ｆｅ，Ｃｕのいずれの濃度も０．１ｐｐｍ以下、前記外層におけるＮａ濃度が０．２ｐｐｍ以下であるシリカガラスルツボを得ることを特徴とする。
上記のようにして得られたルツボによれば、単結晶引上げ過程におけるブラウンモールドの発生が抑制され、かつ、変形や歪みが抑制され、さらに、ルツボに起因する不純物汚染も防止されるため、単結晶製造における歩留まり向上を図ることができる。
The method for producing a silica glass crucible according to the present invention has a bottomed container shape consisting of a straight body part, a corner part and a bottom part from above, and the outer layer in the thickness direction is made of natural silica glass and the inner layer is made of synthetic silica glass. In the crucible manufacturing method, the outer layer and the inner layer are formed by vitrifying natural siliceous raw material powder and synthetic silica raw material powder by reduced-pressure arc melting, respectively, and the total thickness of the outer layer and inner layer in at least the straight body portion is 6 mm. 16 mm or less, the thickness of the inner layer is 5% or more and 40% or less of the total thickness, and any concentration of Na, K, Li, Ca, Al, Ti, Fe, Cu in the inner layer is 0.1 ppm. Hereinafter, a silica glass crucible having a Na concentration of 0.2 ppm or less in the outer layer is obtained.
According to the crucible obtained as described above, the occurrence of the brown mold in the single crystal pulling process is suppressed, deformation and distortion are suppressed, and further, impurity contamination due to the crucible is prevented, so that The yield in crystal manufacturing can be improved.
上記製造方法においては、前記外層および内層を、減圧アーク溶融によりガラス化して形成する工程は、純化処理したＮａ濃度が０．２ｐｐｍ以下の天然シリカ質原料粉をルツボ形状に成型し、さらに、前記ルツボ形状の成型体の内表面を覆うように、Ｎａ，Ｋ，Ｌｉ，Ｃａ，Ａｌ，Ｔｉ，Ｆｅ，Ｃｕのいずれの濃度も０．１ｐｐｍ以下であり、平均粒径が１５０μｍ、かつ、最大粒径が２１０μｍの合成シリカ原料粉を導入した後、高清浄度環境下で減圧アーク溶融によりガラス化することにより行うことが好ましい。 In the manufacturing method, the step of forming the outer layer and the inner layer by vitrification by low-pressure arc melting is performed by molding a purified natural siliceous raw material powder having a Na concentration of 0.2 ppm or less into a crucible shape, All the concentrations of Na, K, Li, Ca, Al, Ti, Fe, and Cu are 0.1 ppm or less so as to cover the inner surface of the crucible-shaped molded body, the average particle size is 150 μm, and the maximum particle size After introducing synthetic silica raw material powder having a diameter of 210 μm, it is preferably performed by vitrification by reduced pressure arc melting under a high cleanliness environment.
前記シリカガラスルツボにおいては、内層のルツボ内表面から深さ０．５ｍｍ以下の領域において、直径２０μｍ以上の気孔が２０個／ｍｍ2以下であることが好ましい。
内表面に存在する気孔が上記のように制御されることにより、半導体単結晶引上げ過程において収容される原料融液の液面振動を抑制することができ、また、内層においてブラウンモールドが発生した場合であっても、ルツボ内表面から原料融液に溶出することを防止することができる。
In the silica glass crucible, the number of pores having a diameter of 20 μm or more is preferably 20 / mm 2 or less in a region having a depth of 0.5 mm or less from the inner surface of the inner crucible.
When the pores existing on the inner surface are controlled as described above, the liquid surface vibration of the raw material melt accommodated in the process of pulling up the semiconductor single crystal can be suppressed, and when a brown mold occurs in the inner layer Even so, elution from the inner surface of the crucible into the raw material melt can be prevented.
上述のとおり、本発明に係る製造方法により得られるシリカガラスルツボは、単結晶引上げに長時間要する場合においても、ブラウンモールドの発生が抑制され、かつ、原料融液が充填された高温下においても、変形や歪みが抑制され、しかも、ルツボに起因する不純物汚染を招くことはない。
したがって、本発明に係る製造方法により得られるシリカガラスルツボは、耐熱強度および耐久性に優れており、シリコン等の半導体単結晶を歩留まりよく引上げるのに好適に用いることができる。
As described above, the silica glass crucible obtained by the production method according to the present invention can suppress the occurrence of brown mold even when it takes a long time to pull a single crystal, and also at a high temperature filled with a raw material melt. Deformation and distortion are suppressed, and impurity contamination caused by the crucible is not caused.
Therefore, the silica glass crucible obtained by the production method according to the present invention is excellent in heat resistance strength and durability, and can be suitably used for pulling up semiconductor single crystals such as silicon with high yield.
以下、本発明をより詳細に説明する。
本発明に係る製造方法により得られるシリカガラスルツボは、外層が天然質シリカガラスであり、内層が合成シリカガラスである複層構造からなるものである。
前記ルツボにおいては、外層と内層の総厚さは６ｍｍ以上１６ｍｍ以下とする。
前記総厚さが６ｍｍ未満である場合、シリコン等の半導体単結晶の原料融液の容器として十分な耐熱強度が得られない。
一方、前記総厚さが１６ｍｍを超える場合は、ルツボ自体の重量が重くなり、単結晶製造効率が劣り、また、ルツボ内表面と外表面との温度差による歪みによる破損が生じやすくなる。
前記ルツボの総厚さは１０ｍｍ程度であることが好ましい。
Hereinafter, the present invention will be described in more detail.
The silica glass crucible obtained by the production method according to the present invention has a multilayer structure in which the outer layer is natural silica glass and the inner layer is synthetic silica glass.
In the crucible, the total thickness of the outer layer and the inner layer is 6 mm or more and 16 mm or less.
When the total thickness is less than 6 mm, sufficient heat resistance strength as a container for a raw material melt of a semiconductor single crystal such as silicon cannot be obtained.
On the other hand, when the total thickness exceeds 16 mm, the weight of the crucible itself becomes heavy, the single crystal production efficiency is inferior, and damage due to distortion due to a temperature difference between the inner surface and the outer surface of the crucible tends to occur.
The total thickness of the crucible is preferably about 10 mm.
また、前記ルツボにおける内層の厚さは、総厚さの５％以上４０％以下とする。
前記内層の厚さが５％未満である場合、半導体単結晶の引上げ過程で内表面が溶損し、外層を構成する天然質シリカガラスがルツボ内表面に露出し、ルツボ内の原料融液に不純物が混入したり、液面が振動する等の弊害により、無欠陥状態での単結晶引上げに支障をきたす。
一方、前記内層の厚さが４０％を超える場合、外層の厚さが薄くなるため、ルツボの強度が不十分となり、半導体単結晶引上げ過程におけるルツボ側壁の倒れ込みを生じるおそれがある。また、ルツボの断熱性にも劣る。
前記ルツボの内層の厚さは、１２％以上２８％以下の範囲内であることが好ましい。
Further, the thickness of the inner layer in the crucible is set to 5% or more and 40% or less of the total thickness.
When the thickness of the inner layer is less than 5%, the inner surface is melted during the pulling process of the semiconductor single crystal, the natural silica glass constituting the outer layer is exposed on the inner surface of the crucible, and impurities are contained in the raw material melt in the crucible. The trouble of pulling a single crystal in a defect-free state is hindered due to the adverse effects such as mixing of the liquid and the vibration of the liquid surface.
On the other hand, when the thickness of the inner layer exceeds 40%, the thickness of the outer layer becomes thin, so that the strength of the crucible becomes insufficient, and the side wall of the crucible may collapse during the pulling process of the semiconductor single crystal. Also, the heat insulation of the crucible is inferior.
The thickness of the inner layer of the crucible is preferably in the range of 12% to 28%.
さらに、前記内層においては、Ｎａ，Ｋ，Ｌｉ，Ｃａ，Ａｌ，Ｔｉ，Ｆｅ，Ｃｕのいずれの濃度も０．１ｐｐｍ以下とする。
半導体単結晶の原料融液と接触するルツボ内層側は、原料融液の汚染源となる不純物金属元素が少ないことが好ましいことから、内層を構成するシリカガラス中のＮａ，Ｋ，Ｌｉ，Ｃａ，Ａｌ，Ｔｉ，Ｆｅ，Ｃｕのいずれの濃度もできる限り少ないことが好ましく、０．１ｐｐｍ以下であることが好ましい。
前記Ｎａ，Ｋ，Ｌｉ，Ｃａ，Ａｌ，Ｔｉ，Ｆｅ，Ｃｕの濃度が０．１ｐｐｍを超える場合は、上記のような原料融液の汚染により、高純度かつ高品質の半導体単結晶の歩留まり低下を招く。
Further, in the inner layer, the concentrations of Na, K, Li, Ca, Al, Ti, Fe, and Cu are 0.1 ppm or less.
Since the crucible inner layer side in contact with the raw material melt of the semiconductor single crystal preferably has a small amount of impurity metal elements that are sources of contamination of the raw material melt, Na, K, Li, Ca, Al in the silica glass constituting the inner layer is preferable. , Ti, Fe, Cu are preferably as low as possible, and preferably 0.1 ppm or less.
When the concentration of Na, K, Li, Ca, Al, Ti, Fe, or Cu exceeds 0.1 ppm, the yield of high-purity and high-quality semiconductor single crystals decreases due to contamination of the raw material melt as described above. Invite.
また、前記外層におけるＮａ濃度は０．２ｐｐｍ以下とする。
前記Ｎａ濃度が０．２ｐｐｍを超える場合は、半導体単結晶引上げ過程において、該ルツボが高温に曝されると、前記Ｎａが内層側に拡散し、ルツボ内表面でのブラウンモールドの発生を招き、また、外層の強度が低下する。
The Na concentration in the outer layer is 0.2 ppm or less.
When the Na concentration exceeds 0.2 ppm, when the crucible is exposed to a high temperature in the process of pulling the semiconductor single crystal, the Na diffuses to the inner layer side, leading to the occurrence of a brown mold on the inner surface of the crucible, In addition, the strength of the outer layer is reduced.
また、前記シリカガラスルツボにおいては、内層のルツボ内表面から深さ０．５ｍｍ以下の領域において、直径２０μｍ以上の気孔が２０個／ｍｍ2以下であることが好ましい。
これによって、内層においてブラウンモールドが発生した場合であっても、原料融液側へのブラウンモールドを形成する結晶化したシリカが剥離し、面荒れを生じることによる単結晶化率の低下を抑制することができる。
このような気孔発生が低減化された内層のルツボ内表面は、内層を形成する合成シリカガラス原料の粒度およびアーク溶融温度を適宜調整することにより形成することができる。
Further, in the silica glass crucible, it is preferable that the number of pores having a diameter of 20 μm or more is 20 / mm 2 or less in a region having a depth of 0.5 mm or less from the inner surface of the inner crucible.
As a result, even if a brown mold occurs in the inner layer, the crystallized silica forming the brown mold on the raw material melt side peels and suppresses a decrease in the single crystallization rate due to surface roughness. be able to.
Such a crucible inner surface of the inner layer with reduced generation of pores can be formed by appropriately adjusting the particle size and arc melting temperature of the synthetic silica glass raw material forming the inner layer.
上記のような本発明に係るシリカガラスルツボは、例えば、以下のような製造方法により得ることができる。
まず、Ｎａ濃度を低減化させるために、純化処理として、例えば、塩素ガス雰囲気中、１０００〜１２００℃での熱処理を施したＮａ濃度が０．２ｐｐｍ以下の天然質シリカ原料粉をルツボ形状に成型する。さらに、前記外層の内表面を覆うように、Ｎａ，Ｋ，Ｌｉ，Ｃａ，Ａｌ，Ｔｉ，Ｆｅ，Ｃｕのいずれの濃度も０．１ｐｐｍ以下であり、平均粒径が１５０μｍ（最大粒径２１０μｍ）の合成シリカ原料粉を導入し、高清浄度の環境を維持する。
この中にアーク電極を挿入し、減圧アーク溶融によりガラス化することにより、外層が多数の気孔を含む見かけ上不透明な天然質シリカガラスであり、内層が透明な合成シリカガラスからなる本発明に係るシリカガラスルツボが得られる。
The silica glass crucible according to the present invention as described above can be obtained by, for example, the following production method.
First, in order to reduce the Na concentration, as a purification treatment, for example, natural silica raw material powder having a Na concentration of 0.2 ppm or less subjected to heat treatment at 1000 to 1200 ° C. in a chlorine gas atmosphere is formed into a crucible shape. To do. Further, the concentration of each of Na, K, Li, Ca, Al, Ti, Fe, and Cu is 0.1 ppm or less so as to cover the inner surface of the outer layer, and the average particle size is 150 μm (maximum particle size 210 μm). The synthetic silica raw material powder is introduced to maintain a high clean environment.
According to the present invention, an arc electrode is inserted into this and vitrified by reduced-pressure arc melting, so that the outer layer is an apparently opaque natural silica glass containing a large number of pores, and the inner layer is made of a transparent synthetic silica glass. A silica glass crucible is obtained.
以下、本発明を実施例に基づきさらに具体的に説明するが、本発明は下記の実施例により制限されるものではない。
［実施例１］
純化処理したＮａ濃度が０．１５ｐｐｍ以下の天然質シリカ原料粉をルツボ形状に成型し、さらに、前記外層の内表面を覆うように、Ｎａ，Ｋ，Ｌｉ，Ｃａ，Ａｌ，Ｔｉ，Ｆｅ，Ｃｕのいずれの濃度も０．０５ｐｐｍ以下であり、平均粒径が１５０μｍ（最大粒径２１０μｍ）の合成シリカ原料粉を導入し、高清浄度の環境を維持した。
この中にアーク電極を挿入し、減圧アーク溶融によりガラス化して、外層が厚さ８ｍｍの多数の気孔を含む見かけ上不透明な天然質シリカガラスであり、内層が厚さ２ｍｍの透明な合成シリカガラスからなるシリカガラスルツボを作製した。
得られたルツボについて分析したところ、内層のＮａ，Ｋ，Ｌｉ，Ｃａ，Ｆｅ，Ｃｕのいずれの濃度も０．０５ｐｐｍ以下、Ａｌ，Ｔｉの濃度はいずれも０．１ｐｐｍ以下であり、外層のＮａ濃度は０．２ｐｐｍ以下であった。
また、前記内層の内表面から深さ０．５ｍｍ以下の領域においては、直径２０μｍ以上の気孔が２０個／ｍｍ2以下であった。
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited by the following Example.
[Example 1]
A purified natural silica raw material powder having a Na concentration of 0.15 ppm or less is formed into a crucible shape, and Na, K, Li, Ca, Al, Ti, Fe, Cu are formed so as to cover the inner surface of the outer layer. Each of these concentrations was 0.05 ppm or less, and synthetic silica raw material powder having an average particle size of 150 μm (maximum particle size of 210 μm) was introduced to maintain a high cleanliness environment.
An arc electrode is inserted into this, vitrified by low-pressure arc melting, and the outer layer is an apparently opaque natural silica glass containing many pores having a thickness of 8 mm, and the inner layer is a transparent synthetic silica glass having a thickness of 2 mm. A silica glass crucible made of
When the obtained crucible was analyzed, the concentrations of Na, K, Li, Ca, Fe, and Cu in the inner layer were 0.05 ppm or less, the concentrations of Al and Ti were both 0.1 ppm or less, and the Na in the outer layer was The concentration was 0.2 ppm or less.
Further, in the region having a depth of 0.5 mm or less from the inner surface of the inner layer, the number of pores having a diameter of 20 μm or more was 20 / mm 2 or less.
上記方法により作製した１０個の直径２４インチのシリカガラスルツボを用いて、ＣＺ法でシリコン単結晶の引上げを行った。
引上げ後のルツボ内表面に、ブラウンモールドの発生が、平均０．３個／ｃｍ2程度認められたものの、平均単結晶化率は９８％と高かった。
Using 10 silica glass crucibles having a diameter of 24 inches produced by the above method, the silicon single crystal was pulled by the CZ method.
On the inner surface of the crucible after pulling up, the occurrence of brown mold was found to be about 0.3 / cm 2 on average, but the average single crystallization rate was as high as 98%.
［比較例１］
実施例１において、外層形成時に、Ｎａ濃度が１．２ｐｐｍの天然質シリカ原料粉を用い、また、減圧アーク溶融時における減圧の程度を低く調整し、それ以外については、実施例１と同様にして、シリカガラスルツボを作製した。
得られたルツボについて分析したところ、内層のＮａ，Ｋ，Ｌｉ，Ｃａ，Ｆｅ，Ｃｕのいずれの濃度も０．０５ｐｐｍ以下、Ａｌ，Ｔｉの濃度はいずれも０．１ｐｐｍ以下であったが、外層のＮａ濃度は１．３ｐｐｍであった。
また、前記内層の内表面から深さ０．５ｍｍ以下の領域においては、直径２０μｍ以上の気孔が２０個／ｍｍ2以下であった。
[Comparative Example 1]
In Example 1, natural silica raw material powder having a Na concentration of 1.2 ppm was used at the time of forming the outer layer, and the degree of decompression at the time of reduced-pressure arc melting was adjusted to a low level. Thus, a silica glass crucible was produced.
When the obtained crucible was analyzed, the concentrations of Na, K, Li, Ca, Fe, and Cu in the inner layer were 0.05 ppm or less, and the concentrations of Al and Ti were all 0.1 ppm or less. The Na concentration was 1.3 ppm.
Further, in the region having a depth of 0.5 mm or less from the inner surface of the inner layer, the number of pores having a diameter of 20 μm or more was 20 / mm 2 or less.
得られたシリカガラスルツボを用いて、ＣＺ法でシリコン単結晶の引上げを行った。
引上げ後のルツボ内表面には、ブラウンモールドが平均０．６個／ｃｍ2発生しており、平均単結晶化率は８７％であった。
Using the resulting silica glass crucible, the silicon single crystal was pulled by the CZ method.
On the inner surface of the crucible after pulling up, an average of 0.6 brown molds was generated / cm 2 and the average single crystallization rate was 87%.
［比較例２］
比較例１において、合成シリカ原料粉として、平均粒径２５０μｍ（最大粒径４００μｍ）のものを用い、それ以外については、比較例１と同様にして、内層のルツボ内表面から深さ０．５ｍｍ以下の領域において、直径２０μｍ以上の気孔が３５個／ｍｍ2であるシリカガラスルツボを作製した。
[Comparative Example 2]
In Comparative Example 1, a synthetic silica raw material powder having an average particle size of 250 μm (maximum particle size of 400 μm) was used. Otherwise, in the same manner as in Comparative Example 1, a depth of 0.5 mm from the inner surface of the inner crucible was used. In the following region, a silica glass crucible having 35 pores / mm 2 having a diameter of 20 μm or more was produced.
得られたシリカガラスルツボを用いて、ＣＺ法でシリコン単結晶の引上げを行った。
引上げ後のルツボ内表面には、ブラウンモールドが平均０．７個／ｃｍ2発生しており、平均単結晶化率は８２％であった。
Using the resulting silica glass crucible, the silicon single crystal was pulled by the CZ method.
On the inner surface of the crucible after the pulling, 0.7 pieces / cm 2 of brown molds were generated on average, and the average single crystallization rate was 82%.
Claims (3)
前記外層および内層を、それぞれ、天然シリカ質原料粉および合成シリカ原料粉を減圧アーク溶融によりガラス化して形成し、少なくとも前記直胴部における外層と内層の総厚さが６ｍｍ以上１６ｍｍ以下、内層の厚さが総厚さの５％以上４０％以下であり、かつ、前記内層におけるＮａ，Ｋ，Ｌｉ，Ｃａ，Ａｌ，Ｔｉ，Ｆｅ，Ｃｕのいずれの濃度も０．１ｐｐｍ以下、前記外層におけるＮａ濃度が０．２ｐｐｍ以下であるシリカガラスルツボを得ることを特徴とするシリカガラスルツボの製造方法。 In the manufacturing method of the crucible which is a bottomed container shape consisting of a straight body portion, a corner portion and a bottom portion from above, the outer layer in the thickness direction is natural silica glass, and the inner layer is made of synthetic silica glass.
The outer layer and the inner layer are formed by vitrifying natural siliceous raw material powder and synthetic silica raw material powder by reduced-pressure arc melting, respectively, and the total thickness of the outer layer and inner layer in at least the straight body portion is 6 mm or more and 16 mm or less, The thickness is 5% or more and 40% or less of the total thickness, and the concentration of Na, K, Li, Ca, Al, Ti, Fe, or Cu in the inner layer is 0.1 ppm or less. A method for producing a silica glass crucible, wherein a silica glass crucible having a concentration of 0.2 ppm or less is obtained.
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| WO2015099001A1 (en) | 2013-12-28 | 2015-07-02 | 株式会社Sumco | Quartz glass crucible and strain measurement device therefor |
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| JP2012136400A (en) * | 2010-12-27 | 2012-07-19 | Covalent Materials Corp | Silica glass crucible for pulling silicon single crystal |
| WO2015099001A1 (en) | 2013-12-28 | 2015-07-02 | 株式会社Sumco | Quartz glass crucible and strain measurement device therefor |
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