JPH05124889A - Quartz glass crucible for pulling up silicon single crystal and its production - Google Patents

Quartz glass crucible for pulling up silicon single crystal and its production

Info

Publication number
JPH05124889A
JPH05124889A JP34929291A JP34929291A JPH05124889A JP H05124889 A JPH05124889 A JP H05124889A JP 34929291 A JP34929291 A JP 34929291A JP 34929291 A JP34929291 A JP 34929291A JP H05124889 A JPH05124889 A JP H05124889A
Authority
JP
Japan
Prior art keywords
quartz glass
glass crucible
hydrogen
crucible
pulling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP34929291A
Other languages
Japanese (ja)
Other versions
JP2747856B2 (en
Inventor
Fujio Iwatani
富士雄 岩谷
Toshiyuki Kato
俊幸 加藤
Takeo Tsuburaya
健男 円谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Quartz Products Co Ltd
Original Assignee
Shin Etsu Quartz Products Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shin Etsu Quartz Products Co Ltd filed Critical Shin Etsu Quartz Products Co Ltd
Priority to JP3349292A priority Critical patent/JP2747856B2/en
Publication of JPH05124889A publication Critical patent/JPH05124889A/en
Application granted granted Critical
Publication of JP2747856B2 publication Critical patent/JP2747856B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/09—Other methods of shaping glass by fusing powdered glass in a shaping mould
    • C03B19/095—Other methods of shaping glass by fusing powdered glass in a shaping mould by centrifuging, e.g. arc discharge in rotating mould
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/007—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in gaseous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/80—Glass compositions containing bubbles or microbubbles, e.g. opaque quartz glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2203/00—Production processes
    • C03C2203/50—After-treatment
    • C03C2203/52—Heat-treatment
    • C03C2203/54—Heat-treatment in a dopant containing atmosphere

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

PURPOSE:To provide the quartz glass crucible, the wall surfaces of which are less expandable and deformable under a reduced pressure and heating, i.e., have excellent durability and good soaking characteristics and which is usable over a long period of time and the process for production of thereof which can inexpensively produce such quartz glass crucible. CONSTITUTION:This crucible for pulling up a silicon single crystal has the inside surface which is formed of a transparent layer and the outside surface which is formed of a foam-contg. layer. The above-mentioned transparent layer is a transparent layer subjected to a hydrogen heat diffusion treatment. Such crucible is produced by producing the quartz glass crucible, the inside surface of which is formed of the transparent layer by an arc rotational melting method and by heating the inside surface of the quartz glass crucible produced in such a manner for 0.5 to 5 hours at 300 to 1200 deg.C in hydrogen or hydrogen-contg. atmosphere.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、シリコン単結晶の減圧
引上げ及びマルチプーリングに適した耐熱性の高いアー
ク回転溶融法によるシリコン単結晶引上げ用の石英ガラ
スルツボ及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a quartz glass crucible for pulling a silicon single crystal by an arc rotary melting method having high heat resistance, which is suitable for pulling a silicon single crystal under reduced pressure and for multi-pooling, and a method for producing the same.

【０００２】[0002]

【従来の技術】シリコン単結晶引上げ用石英ガラスルツ
ボは、シリコン単結晶の高純度化に伴い、石英ガラスル
ツボは高純度のものが要求されており、この要求に対処
するために、ゾルゲル法による高純度な合成石英ガラス
粉や合成クリストバライト粉がシリコン単結晶引上げ用
石英ガラスルツボの原料として使用されている。このよ
うなゾルゲル法による石英ガラス粉をアーク回転溶融法
によって成形することにより、成形性の良好な石英ガラ
スルツボを得ることができる。シリコン単結晶の引上げ
用石英ガラスルツボは、シリコン単結晶の引上げに際
し、単結晶化率を向上させるために、石英ガラスルツボ
の内表面を形成する内層、できるだけ泡の少ない層に形
成されることが必要とされている。そこで、シリコン単
結晶の引上用ルツボは、アーク回転溶融法により、内層
が透明もしくは微気泡に形成され、外層が気泡入りに形
成されており、所謂２層構造石英ガラスルツボとなって
いる。2. Description of the Related Art A quartz glass crucible for pulling a silicon single crystal has been required to have a high purity as the silicon single crystal has been highly purified. To meet this requirement, a sol-gel method is used. High-purity synthetic quartz glass powder and synthetic cristobalite powder are used as raw materials for a quartz glass crucible for pulling a silicon single crystal. By molding the quartz glass powder by the sol-gel method by the arc rotary melting method, a quartz glass crucible having good moldability can be obtained. A quartz glass crucible for pulling a silicon single crystal is formed in an inner layer forming the inner surface of the quartz glass crucible, a layer having as few bubbles as possible, in order to improve the single crystallization rate when pulling a silicon single crystal. is necessary. Therefore, the pulling crucible for pulling a silicon single crystal has a so-called two-layer structure quartz glass crucible in which the inner layer is formed into transparent or fine bubbles and the outer layer is formed into bubbles by the arc rotary melting method.

【０００３】[0003]

【発明が解決しようとする課題】しかしながら、大気圧
下のアーク回転熔融法で作られた２層構造石英ガラスル
ツボは、減圧下の引き上げに際し、透明層内に気泡が発
生又は膨張し、内表面が***して凹凸になり、シリコン
メルトの流れに乱れを生じて、シリコン単結晶の形成上
好ましくなく、また石英ガラスルツボ内表面が局部的に
溶損して、強度が低下して好ましくない。更にこの内表
面の***部は、早く溶けて泡が開いて破片がシリコンメ
ルトの中に入り、結晶の欠陥を作る要因となり好ましく
ない。このような石英ガラスルツボ内表面の気泡膨張
は、減圧下で使用する石英ガラスルツボを大気圧下で作
るために、発生するものと考えられている。しかし乍
ら、石英ガラスルツボを使用時の圧力下で製造するのは
極めて困難である。However, the two-layer structure quartz glass crucible made by the arc rotary melting method under the atmospheric pressure has a problem that the bubbles are generated or expanded in the transparent layer during the pulling under the reduced pressure and the inner surface Are raised and become uneven, which disturbs the flow of the silicon melt and is not preferable for the formation of a silicon single crystal. Further, the inner surface of the quartz glass crucible is locally melted and damaged, which is not preferable. Furthermore, this raised portion on the inner surface is not preferable because it melts quickly and bubbles open, and fragments enter the silicon melt to cause crystal defects. It is considered that such bubble expansion on the inner surface of the quartz glass crucible occurs because the quartz glass crucible used under reduced pressure is produced under atmospheric pressure. However, it is extremely difficult to manufacture a quartz glass crucible under the pressure during use.

【０００４】また天然産の石英粉から製造される従来の
石英ガラスルツボにおいても、長時間の使用、特に減圧
下のシリコン単結晶引上げを行う場合には、しばしばル
ツボ壁面の膨張により変形を生じるので問題とされてい
る。このような減圧下のシリコン単結晶引上げにおい
て、使用される石英ガラスルツボの壁面の膨張による変
形は、シリコン単結晶の大径化に伴って石英ガラスルツ
ボを大型化する上で大きな問題となってきている。Further, even in a conventional quartz glass crucible manufactured from naturally occurring quartz powder, when used for a long time, particularly when pulling a silicon single crystal under reduced pressure, deformation often occurs due to expansion of the crucible wall surface. It is a problem. In such pulling of a silicon single crystal under reduced pressure, the deformation of the wall surface of the silica glass crucible used due to expansion becomes a major problem in enlarging the silica glass crucible as the diameter of the silicon single crystal increases. ing.

【０００５】このような石英ガラスルツボが、減圧下の
シリコン単結晶の引上げにおいて使用できるようにする
ために、外周に減圧を適用してアーク回転溶融法により
石英ガラスルツボを製造する方法が提案されている。し
かし、この減圧アーク回転溶融法により石英ガラスルツ
ボを製造する場合は、従来の製造方法により製造された
石英ガラスルツボに比べて、コストが高くなり、しか
も、ルツボの気泡数が少なくなるために、均熱特性が悪
くなり問題である。大気圧下で作られた透明内層を有す
る石英ガラスルツボを減圧使用において透明内層に気泡
膨張を起こさないこと。本発明は、以上のようなシリコ
ン単結晶引上げ用の石英ガラスルツボについての問題点
を解決することを目的としている。In order to use such a quartz glass crucible in pulling a silicon single crystal under a reduced pressure, a method has been proposed in which a reduced pressure is applied to the outer circumference to produce a quartz glass crucible by an arc rotary melting method. ing. However, in the case of producing a quartz glass crucible by this reduced pressure arc rotary melting method, as compared with a quartz glass crucible produced by a conventional production method, the cost becomes higher, and moreover, because the number of bubbles in the crucible decreases, This is a problem because the soaking property deteriorates. Do not cause bubble expansion in the transparent inner layer when using a quartz glass crucible having a transparent inner layer made under atmospheric pressure under reduced pressure. An object of the present invention is to solve the above-mentioned problems with the quartz glass crucible for pulling a silicon single crystal.

【０００６】[0006]

【課題を解決するための手段】本発明は、シリコン単結
晶の長時間引き上げ、マルチプーリング、特に減圧引き
上げに使用できるように、減圧加熱下において、石英ガ
ラスルツボ壁面の膨張及び変形が少なく、即ち、耐久性
が高く、その上均熱特性が良く、さらに長時間使用可能
な石英ガラスルツボを、安価に製造することができる新
規な石英ガラスルツボの製造方法を提供することを目的
としている。この目的を達成するために、本発明者ら
は、アーク回転溶融法で作られた石英ガラスルツボを、
水素雰囲気下で加熱保持した石英ガラスルツボについて
検討したところ、例えば、１０−２の真空中、１６００
℃で２時間加熱するという減圧下のシリコン単結晶引上
げのシミュレーションテストにおいて、著しく低い膨張
率を示すことを見い出した。According to the present invention, there is little expansion and deformation of the wall surface of a quartz glass crucible under reduced pressure heating so that it can be used for long-time pulling of a silicon single crystal, multi-pooling, especially reduced pressure pulling, that is, An object of the present invention is to provide a novel method for producing a quartz glass crucible which has high durability, good soaking characteristics, and can be produced for a long time at low cost. In order to achieve this object, the present inventors have proposed a quartz glass crucible made by the arc rotary melting method,
When a quartz glass crucible heated and maintained in a hydrogen atmosphere was examined, for example, in a vacuum of 10 −2 , 1600
In a simulation test of pulling a silicon single crystal under reduced pressure of heating at 0 ° C. for 2 hours, it was found that a significantly low expansion coefficient was exhibited.

【０００７】そこで、本発明者らは、石英ガラスルツボ
の原料に、天然石英粉、合成クリストバライト粉又は合
成非晶質シリカ粉を使用して、アーク回転溶融法により
石英ガラスルツボを成形した後、この成形した石英ガラ
スルツボを水素雰囲気中に加熱保持して、熱処理し、こ
の熱処理された石英ガラスルツボを、シリコン単結晶引
き上げ、特に減圧下でのシリコン単結晶引上げに使用し
たところ、ルツボ壁面の膨張も少なく従って変形を起こ
すことなく、シリコン単結晶を製造することを確認し、
本発明に至った。Therefore, the inventors of the present invention used natural quartz powder, synthetic cristobalite powder or synthetic amorphous silica powder as the raw material of the quartz glass crucible, and after molding the quartz glass crucible by the arc rotary melting method, This molded quartz glass crucible was heated and held in a hydrogen atmosphere and heat-treated, and the heat-treated quartz glass crucible was used for pulling a silicon single crystal, particularly for pulling a silicon single crystal under reduced pressure. Confirmed that a silicon single crystal was produced without causing expansion and thus deformation,
The present invention has been reached.

【０００８】即ち、本発明は、内面が透明層で形成さ
れ、外面が泡入り層で形成されているシリコン単結晶引
上げ用石英ガラスルツボにおいて、前記透明層が水素熱
拡散処理された透明層であることを特徴とするシリコン
単結晶引上げ用石英ガラスルツボにあり、また本発明
は、アーク回転溶融法で、透明層で内面が形成されてい
る石英ガラスルツボを製造し、この製造された石英ガラ
スルツボの内面を、水素又は水素含有雰囲気中で、３０
０℃乃至１２００℃の範囲内の温度に、０．５時間乃至
５時間の間加熱することを特徴とするシリコン単結晶引
上げ用石英ガラスルツボの製造方法にある。にある。That is, according to the present invention, in a quartz glass crucible for pulling up a silicon single crystal having an inner surface formed of a transparent layer and an outer surface formed of a bubble-containing layer, the transparent layer is a transparent layer subjected to hydrogen heat diffusion treatment. A quartz glass crucible for pulling a silicon single crystal, which is characterized in that the present invention is an arc rotary melting method to produce a quartz glass crucible having an inner surface formed with a transparent layer. The inner surface of the crucible is exposed to hydrogen or a hydrogen-containing atmosphere for 30
A method for producing a quartz glass crucible for pulling a silicon single crystal is characterized by heating to a temperature in the range of 0 ° C. to 1200 ° C. for 0.5 hours to 5 hours. It is in.

【０００９】本発明において、ルツボ内面を形成する透
明層は、透明な層であり、実質的に無気泡の透明層を包
含する。本発明においては、アーク回転溶融法で成形さ
れた石英ガラスルツボを、水素又は水素含有雰囲気内で
加熱処理することにより、従来の石英ガラスルツボに比
して低膨張の石英ガラスルツボとするものである。本発
明における単結晶引上げ用の石英ガラスルツボは、アー
ク回転溶融法により製造された石英ガラスルツボを、炉
に入れ、炉内を水素雰囲気又は主としてアルゴン（Ａ
ｒ）若しくは窒素（Ｎ２）含有の水素雰囲気に保ち加熱
して、石英ガラスルツボ内面から、水素ガスを、石英ガ
ラスルツボ壁内に、透明層を越えて拡散させることによ
り製造される。In the present invention, the transparent layer forming the inner surface of the crucible is a transparent layer and includes a substantially bubble-free transparent layer. In the present invention, the quartz glass crucible formed by the arc rotary melting method is subjected to heat treatment in hydrogen or a hydrogen-containing atmosphere to obtain a quartz glass crucible having a low expansion as compared with a conventional quartz glass crucible. is there. The quartz glass crucible for pulling a single crystal according to the present invention is a quartz glass crucible manufactured by an arc rotary melting method, and the quartz glass crucible is placed in a furnace and a hydrogen atmosphere or mainly argon (A
It is manufactured by diffusing hydrogen gas from the inner surface of the quartz glass crucible into the wall of the quartz glass crucible across the transparent layer while heating in a hydrogen atmosphere containing r) or nitrogen (N 2 ).

【００１０】本発明におけるシリコン単結晶引上げ用石
英ガラスルツボにおいては、水素拡散層は透明層に形成
されるが、透明層及びそれに続く泡入り層の少なくとも
一部に形成されるのが好ましい。この場合において、石
英ガラスルツボ全体を、炉内の水素雰囲気又は主として
アルゴン（Ａｒ）若しくは窒素（Ｎ２）含有の水素雰囲
気に曝して、加熱し、石英ガラスルツボ内面から、水素
ガスを、石英ガラスルツボ壁内に拡散させると、水素拡
散層は、内面側から形成されて、シリコン単結晶引上げ
用石英ガラスルツボを製造することができる。本発明に
おいて、水素拡散領域の透明層は、気泡が僅かに存在す
る変形の少ない層であり、減圧下のシリコン単結晶引上
げのシミュレーションテストにおいて、密度変化率が測
定できないほど気泡の膨張が小さい領域となる。In the quartz glass crucible for pulling up a silicon single crystal according to the present invention, the hydrogen diffusion layer is formed in the transparent layer, but it is preferably formed in at least a part of the transparent layer and the bubble-containing layer subsequent thereto. In this case, the entire quartz glass crucible is exposed to a hydrogen atmosphere in the furnace or a hydrogen atmosphere mainly containing argon (Ar) or nitrogen (N 2 ) and heated to supply hydrogen gas from the inner surface of the quartz glass crucible to the quartz glass crucible. When diffusing into the crucible wall, the hydrogen diffusion layer is formed from the inner surface side, and the quartz glass crucible for pulling a silicon single crystal can be manufactured. In the present invention, the transparent layer of the hydrogen diffusion region is a layer with little deformation in which bubbles are slightly present, and in a simulation test of pulling a silicon single crystal under reduced pressure, a region where the expansion of bubbles is so small that the density change rate cannot be measured. Becomes

【００１１】本発明において、石英ガラスルツボは、水
素又は水素含有雰囲気内で、３００℃乃至１２００℃の
範囲内の加熱温度に加熱して製造されるのが好ましい。
この石英ガラスルツボの加熱温度を３００℃以下とする
と、ルツボ内への水素の拡散又は反応が遅くなるので好
ましくない。また、加熱温度を１２００℃以上とする
と、ルツボの変形が生じるので好ましくない。本発明に
おいて、石英ガラスルツボを加熱するのは、水素の拡散
又は反応を高めるためである。In the present invention, the quartz glass crucible is preferably manufactured by heating in a hydrogen or hydrogen-containing atmosphere to a heating temperature in the range of 300 ° C to 1200 ° C.
If the heating temperature of the quartz glass crucible is set to 300 ° C. or lower, the diffusion or reaction of hydrogen in the crucible becomes slow, which is not preferable. Further, if the heating temperature is 1200 ° C. or higher, the crucible is deformed, which is not preferable. In the present invention, the heating of the quartz glass crucible is to enhance the diffusion or reaction of hydrogen.

【００１２】石英ガラスルツボに対する水素の拡散又は
反応は、加熱時間に影響されるために、本発明において
は、石英ガラスルツボの加熱時間は、０．５〜５時間が
適当とされる。０．５時間未満の短時間でばルツボ壁内
部への水素の拡散又は反応が不十分であり、また、該加
熱時間が５時間を越える長時間になるとコスト的に好ま
しくない。しかし、水素の拡散又は反応は、水素又は水
素含有雰囲気の圧力に影響されるので、大気圧の水素又
は水素含有雰囲気においては、石英ガラスルツボの加熱
時間は４〜５時間とするのが更に好ましい。Since the diffusion or reaction of hydrogen with respect to the quartz glass crucible is affected by the heating time, the heating time of the quartz glass crucible is suitably 0.5 to 5 hours in the present invention. If the heating time is less than 0.5 hours, the diffusion or reaction of hydrogen into the crucible wall is insufficient, and if the heating time is longer than 5 hours, the cost is not preferable. However, since the diffusion or reaction of hydrogen is affected by the pressure of hydrogen or a hydrogen-containing atmosphere, it is more preferable that the heating time of the quartz glass crucible is 4 to 5 hours in the atmospheric pressure of hydrogen or the hydrogen-containing atmosphere. ..

【００１３】石英ガラスルツボの加熱保持時の水素又は
水素含有雰囲気の圧力は、高い程、石英ガラスルツボ内
の水素の拡散又は反応を早めるので好ましい。水素又は
水素含有雰囲気の圧力を高くすれば加熱保持温度を低く
でき、また加熱保持時間を短時間に設定できるが、水素
又は水素含有雰囲気の圧力を高くすると、炉の仕様に影
響するので好ましくない。本発明において、水素含有雰
囲気は水素を含有する雰囲気であり、水素含有雰囲気内
の水素分圧は大きいのが好ましい。したがって水素含有
雰囲気は、主として水素ガスで組成することが好まし
い。しかし、水素含有雰囲気は、組成する主たる成分と
して、水素に対し不活性で拡散し難いアルゴン及び窒素
を使用することができる。この場合、水素含有雰囲気の
水素濃度は、５％以上であるのが好ましい。The higher the pressure of hydrogen or the hydrogen-containing atmosphere when the quartz glass crucible is heated and held, the more preferable it is because the diffusion or reaction of hydrogen in the quartz glass crucible is accelerated. If the pressure of hydrogen or hydrogen-containing atmosphere is increased, the heating / holding temperature can be lowered, and the heating / holding time can be set to a short time.However, if the pressure of hydrogen or hydrogen-containing atmosphere is increased, the specifications of the furnace are affected. .. In the present invention, the hydrogen-containing atmosphere is an atmosphere containing hydrogen, and the hydrogen partial pressure in the hydrogen-containing atmosphere is preferably large. Therefore, the hydrogen-containing atmosphere is preferably composed mainly of hydrogen gas. However, the hydrogen-containing atmosphere can use argon and nitrogen, which are inert to hydrogen and difficult to diffuse, as the main components of the composition. In this case, the hydrogen concentration in the hydrogen-containing atmosphere is preferably 5% or more.

【００１４】[0014]

【作用】本発明において、シリコン単結晶引上げ用石英
ガラスルツボは、その内面を形成する透明層、好ましく
は透明層とそれに続く泡入り層の一部に水素を拡散又は
反応させて製造するので、減圧下のシリコン単結晶引き
上げ時において、石英ガラスルツボの泡入り層中の気泡
の膨張を抑止でき、気泡膨張に伴う石英ガラスルツボの
内表面の凹凸の形成を抑止して、石英ガラスルツボの内
面における溶損の一様化でき、泡の開裂による酸化ケイ
素の破片のシリコンメルトへの流入を防止し、シリコン
メルトの流れの乱れを防止することができる。したがっ
て、本発明の石英ガラスルツボを使用することにより常
圧及び減圧下で安定したシリコン単結晶の引き上げを行
うことができる。In the present invention, the quartz glass crucible for pulling a silicon single crystal is produced by diffusing or reacting hydrogen in a transparent layer forming the inner surface thereof, preferably a transparent layer and a part of the bubbled layer which follows the transparent layer. When pulling a silicon single crystal under reduced pressure, it is possible to suppress the expansion of bubbles in the bubble-containing layer of the quartz glass crucible, and to prevent the formation of irregularities on the inner surface of the quartz glass crucible due to the bubble expansion, and thus the inner surface of the quartz glass crucible. It is possible to equalize the melting loss in the above, prevent the inflow of silicon oxide fragments into the silicon melt due to the opening of bubbles, and prevent the disturbance of the flow of the silicon melt. Therefore, by using the quartz glass crucible of the present invention, it is possible to stably pull up the silicon single crystal under normal pressure and reduced pressure.

【００１５】[0015]

【実施例】以下、例をあげて本発明の実施の態様を説明
するが、本発明は以下の説明及び例示によって、何等の
制限を受けるものではない。 例１ 天然石英粉体を原料とし、直径１８インチ（４５７．２
ｍｍ）用回転成形型を使用して、天然石英粉体を焼結成
形し、大気圧下でアーク回転熔融法により溶融成形し、
例えば、特開平１−１４８７８２、１４８７８３、１４
８７１８に開示されるような方法を使用して、内層に
１．２ｍｍの透明層を作り、該ルツボを４個製造した。
その中の１個は水素１００％下で６００℃で５時間加熱
し、更にもう１個を４００℃の温度で５時間加熱した。The embodiments of the present invention will be described below with reference to examples, but the present invention is not limited by the following description and examples. Example 1 Using natural quartz powder as a raw material, a diameter of 18 inches (457.2)
mm) rotation molding die, sinter molding of natural quartz powder, and melt molding by arc rotary melting method under atmospheric pressure,
For example, JP-A-1-148782, 148783, 14
Using the method as disclosed in 8718, a 1.2 mm transparent layer was formed on the inner layer to produce four crucibles.
One of them was heated under hydrogen 100% at 600 ° C. for 5 hours, and another was heated at a temperature of 400 ° C. for 5 hours.

【００１６】例１において得られたルツボについて、夫
々その側胴部から２０×２０ｍｍ（厚さ＝９ｍｍ）のル
ツボ片を各々切り出し、更に未処理のルツボについても
同様に切り出した。これらの切り出したルツボ片を、１
０−２トールの圧力、１６００℃の温度で、２時間の条
件で、いわゆるシリコン単結晶の減圧下の引き上げの加
速シュミレーションテストを行った。テストを行ったル
ツボ片の断面を観察したところ、透明内層の変化は次の
表１のようであった。With respect to the crucible obtained in Example 1, crucible pieces of 20 × 20 mm (thickness = 9 mm) were cut out from the side body of the crucible, and the untreated crucible was similarly cut out. Cut these crucible pieces into 1
An accelerated simulation test of pulling a so-called silicon single crystal under reduced pressure was performed under the condition of a pressure of 0 -2 Torr and a temperature of 1600 ° C for 2 hours. When the cross section of the tested crucible was observed, changes in the transparent inner layer were as shown in Table 1 below.

【００１７】[0017]

【表１】 この実施例から、水素雰囲気下で加熱することにより、
透明内層内に減圧下の加熱しても、気泡の発生が殆んど
無く、発生しても極めて小径のものである。４００℃の
処理では水素が拡散した深さまでは透明であるから、更
に水素加熱時間を延長する必要があり、より低温になる
程長時間に、高温になる程短時間で済むが、これは透明
層の厚さで条件を設定し、最適な条件が必要となる。[Table 1] From this example, by heating under a hydrogen atmosphere,
Even if the transparent inner layer is heated under reduced pressure, almost no bubbles are generated, and even if they are generated, the diameter is extremely small. Since it is transparent at the depth at which hydrogen diffuses at the temperature of 400 ° C, it is necessary to further extend the hydrogen heating time. The lower the temperature, the longer the time, and the higher the temperature, the shorter the time. The conditions are set by the thickness of the layer, and optimum conditions are required.

【００１８】前記シリコン単結晶の減圧下の引き上げの
加速シュミレーションテストを行ったルツボ片につい
て、その表面粗さを、触針式の表面粗さ測定機により、
触針をルツボ内面の湾曲する側に沿って移動させて測定
した。その結果は図１乃至図３に示されている。図１乃
至図３において、垂直方向の矢印の長さは０．５ｍｍで
あり、水平方向の矢印の長さは２ｍｍである。図１は、
６００℃の温度において５時間加熱されたルツボについ
ての測定結果を示し、図２は、４００℃の温度において
５時間加熱されたルツボについての測定結果を示してい
る。図３は水素未処理のルツボについての測定結果であ
り、比較例である。比較例においては、ルツボ内面の粗
さを示す曲線に細かい凹凸がみられ、ルツボ内面が粗く
なっていることを示している。The surface roughness of the crucible piece subjected to the accelerated simulation test of pulling up the silicon single crystal under reduced pressure was measured by a stylus type surface roughness measuring machine.
The measurement was performed by moving the stylus along the curved side of the inner surface of the crucible. The results are shown in FIGS. 1 to 3, the length of the vertical arrow is 0.5 mm, and the length of the horizontal arrow is 2 mm. Figure 1
The measurement result about the crucible heated at the temperature of 600 degreeC for 5 hours is shown, and the measurement result about the crucible heated at the temperature of 400 degreeC for 5 hours is shown. FIG. 3 shows the measurement results of a hydrogen-untreated crucible, which is a comparative example. In the comparative example, fine irregularities are seen in the curve showing the roughness of the inner surface of the crucible, which shows that the inner surface of the crucible is rough.

【００１９】[0019]

【実施例２】高純度合成クリストバライト粉体を用いて
実施例１と同様な方法で透明内層０．９ｍｍを有する石
英ルツボを３個作成した。その中の１個を、水素８０容
量％、アルゴン２０容量％の水素アルゴン混合ガス雰囲
気下で、８００℃の温度で、２時間加熱し、透明内層に
水素を拡散又は反応させた。次いで、水素未処理のルツ
ボと水素の拡散又は反応処理したルツボから２５×２５
ｍｍ（厚さ＝９ｍｍ）のルツボ片を側胴部から切り出
し、１０−２トールの圧力下に、１６００℃の温度で、
２時間の間加熱し、加熱後の試料を２５×５ｍｍの大き
さに切り取り、透明層の変化を観察した。 水素処理品 泡の膨張小 水素未処理品 泡の膨張大Example 2 By using the high-purity synthetic cristobalite powder, three quartz crucibles having a transparent inner layer of 0.9 mm were prepared in the same manner as in Example 1. One of them was heated for 2 hours at a temperature of 800 ° C. in a hydrogen-argon mixed gas atmosphere of 80% by volume of hydrogen and 20% by volume of argon to diffuse or react hydrogen in the transparent inner layer. Next, from the crucible not treated with hydrogen and the crucible subjected to the diffusion or reaction treatment of hydrogen, 25 × 25
mm (thickness = 9 mm) crucible pieces were cut out from the side body part, under a pressure of 10 −2 Torr and at a temperature of 1600 ° C.,
After heating for 2 hours, the sample after heating was cut into a size of 25 × 5 mm, and the change of the transparent layer was observed. Hydrogen-treated product Bubble expansion small Hydrogen-untreated product Bubble expansion large

【００２０】実施例１及び２において切り出したルツボ
片をシリコン単結晶引上機においてシリコン融液に浸漬
した。 （引上機条件） 炉内圧 ：３５ｍｂ ルツボ回転数：１０ｒ．
ｐ．ｍ． 浸漬時間：１２時間 引上機より取り出した試料はシリコンメルトにより浸食
を受けていたが、透明層部は、水素を拡散又は反応した
ルツボ片と水素を拡散又は反応したルツボ片とでは、断
面写真及び断面の画像解折により大きな差異が認められ
た。これらの例においては、水素雰囲気は、水素ガスを
補充しながら行われているが、水素ガスの補充を行わな
くとも同様の結果を得ることができた。また、これらの
例については、水素気流中で行っても同様の結果を得る
ことができた。The crucible pieces cut out in Examples 1 and 2 were immersed in a silicon melt in a silicon single crystal pulling machine. (Pulling machine conditions) Furnace pressure: 35 mb Crucible rotation speed: 10 r.
p. m. Immersion time: 12 hours The sample taken out from the pulling machine was corroded by the silicon melt, but the transparent layer section was a cross-sectional photograph of the crucible piece that diffused or reacted hydrogen and the crucible piece that diffused or reacted hydrogen. A big difference was recognized by the image analysis of the cross section. In these examples, the hydrogen atmosphere was supplemented with hydrogen gas, but similar results could be obtained without supplementing hydrogen gas. Also, for these examples, similar results could be obtained even when the process was carried out in a hydrogen stream.

【００２１】[0021]

【発明の効果】本発明において、シリコン単結晶引上げ
用石英ガラスルツボは、その内面を形成する透明層及び
泡入り層の一部に水素を拡散又は反応させて製造するの
で、従来の石英ガラスルツボに比して、減圧下のシリコ
ン単結晶引き上げ時において、石英ガラスルツボの内面
に凹凸の形成が少なく、石英ガラスルツボの内面におけ
る溶損の一様化でき、石英ガラスルツボを長時間に亙っ
て使用することができ、製造されるシリコン単結晶の歩
留まりの向上を図ることができる。本発明は、アーク回
転溶融法で製造された石英ガラスルツボを水素又は水素
含有雰囲気中で加熱してルツボ壁内に水素を拡散させ
て、石英ガラスルツボの壁面の膨張を抑制するので、従
来法のように、シリコン単結晶の減圧引上げ時の石英ガ
ラスルツボの壁面の膨張を抑えるために、減圧アーク回
転溶融法によるルツボ壁中の気泡数を減少させる必要が
なくなり、減圧下のシリコン単結晶引上げ用の石英ガラ
スルツボを簡単な工程で製造することができる。本発明
による石英ガラスルツボは、多くの泡を含んでいるの
で、従来の減圧下のシリコン単結晶引上げ用の石英ガラ
スルツボに比して、安価であり、均熱性にも優れてい
る。According to the present invention, the quartz glass crucible for pulling up a silicon single crystal is manufactured by diffusing or reacting hydrogen with a part of the transparent layer and the bubble-containing layer forming the inner surface of the quartz glass crucible. Compared with the above, when pulling a silicon single crystal under reduced pressure, there is less unevenness on the inner surface of the quartz glass crucible, and the melting loss on the inner surface of the quartz glass crucible can be made uniform. It can be used as a product, and the yield of the produced silicon single crystal can be improved. The present invention heats a quartz glass crucible manufactured by the arc rotary melting method in hydrogen or a hydrogen-containing atmosphere to diffuse hydrogen in the crucible wall and suppress expansion of the wall surface of the quartz glass crucible. It is not necessary to reduce the number of bubbles in the crucible wall by the low pressure arc rotary melting method in order to suppress the expansion of the wall of the quartz glass crucible when pulling the silicon single crystal under reduced pressure, as shown in Fig. It is possible to manufacture a quartz glass crucible for use in a simple process. Since the quartz glass crucible according to the present invention contains many bubbles, it is inexpensive and excellent in heat uniformity as compared with the conventional quartz glass crucible for pulling a silicon single crystal under reduced pressure.

【図面の簡単な説明】[Brief description of drawings]

【図１】水素１００％下で６００℃の温度において５時
間加熱されたルツボから切り出したルツボ片について、
シリコン単結晶の減圧下の引き上げの加速シュミレーシ
ョンテストを行い、そのテスト後のルツボ片の表面粗さ
を測定した結果を示すグラフである。FIG. 1 shows a crucible piece cut out from a crucible heated for 5 hours at a temperature of 600 ° C. under 100% hydrogen.
It is a graph which shows the result of having measured the surface roughness of the crucible piece after the accelerated simulation test of pulling up the silicon single crystal under reduced pressure.

【図２】水素１００％下で４００℃の温度において５時
間加熱されたルツボから切り出したルツボ片について、
シリコン単結晶の減圧下の引き上げの加速シュミレーシ
ョンテストを行い、そのテスト後のルツボ片の表面粗さ
を測定した結果を示すグラフである。FIG. 2 shows a crucible piece cut out from a crucible heated for 5 hours at a temperature of 400 ° C. under 100% hydrogen,
It is a graph which shows the result of having measured the surface roughness of the crucible piece after the accelerated simulation test of pulling up the silicon single crystal under reduced pressure.

【図３】水素未処理のルツボから切り出したルツボ片に
ついて、シリコン単結晶の減圧下の引き上げの加速シュ
ミレーションテストを行い、そのテスト後のルツボ片の
表面粗さを測定した結果を示すグラフである。FIG. 3 is a graph showing the results of measuring the surface roughness of a crucible piece after the accelerated simulation test of pulling a silicon single crystal under reduced pressure was performed on a crucible piece cut out from a hydrogen-untreated crucible. ..

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 内面が透明層で形成され、外面が泡入り
層で形成されているシリコン単結晶引上げ用石英ガラス
ルツボにおいて、前記透明層が水素熱拡散処理された透
明層であることを特徴とするシリコン単結晶引上げ用石
英ガラスルツボ。1. A quartz glass crucible for pulling a silicon single crystal, the inner surface of which is formed of a transparent layer, and the outer surface of which is formed of a bubble-containing layer, wherein the transparent layer is a hydrogen thermal diffusion-treated transparent layer. A quartz glass crucible for pulling a silicon single crystal. 【請求項２】 石英ガラスルツボが、シリコン単結晶減
圧引上げに使用されるものであることを特徴とする請求
項１に記載のシリコン単結晶引上げ用石英ガラスルツ
ボ。2. The quartz glass crucible for pulling a silicon single crystal according to claim 1, wherein the quartz glass crucible is used for pulling a silicon single crystal under reduced pressure. 【請求項３】 アーク回転溶融法で、透明層で内面が形
成されている石英ガラスルツボを製造し、この製造され
た石英ガラスルツボの内面を、水素又は水素含有雰囲気
中で、３００℃乃至１２００℃の範囲内の温度に、０．
５時間乃至５時間の間加熱することを特徴とするシリコ
ン単結晶引上げ用石英ガラスルツボの製造方法。3. A quartz glass crucible having an inner surface formed of a transparent layer is manufactured by an arc rotary melting method, and the inner surface of the manufactured quartz glass crucible is heated to 300 ° C. to 1200 ° C. in hydrogen or a hydrogen-containing atmosphere. Temperatures within the range of 0.
A method for producing a quartz glass crucible for pulling a silicon single crystal, which comprises heating for 5 hours to 5 hours.
JP3349292A 1991-10-31 1991-10-31 Quartz glass crucible for pulling silicon single crystal and method for producing the same Expired - Lifetime JP2747856B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP3349292A JP2747856B2 (en) 1991-10-31 1991-10-31 Quartz glass crucible for pulling silicon single crystal and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3349292A JP2747856B2 (en) 1991-10-31 1991-10-31 Quartz glass crucible for pulling silicon single crystal and method for producing the same

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Publication Number Publication Date
JPH05124889A true JPH05124889A (en) 1993-05-21
JP2747856B2 JP2747856B2 (en) 1998-05-06

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999061685A1 (en) * 1998-05-25 1999-12-02 Shin-Etsu Quartz Products Co., Ltd. Quartz glass crucible for pulling silicon monocrystal and method of manufacturing the same
JP2002211997A (en) * 2001-01-10 2002-07-31 Kusuwa Kuorutsu:Kk Crucible for pulling semiconductor silicon
US6652934B1 (en) 1999-06-01 2003-11-25 Toshiba Ceramics Co., Ltd. Silica glass crucible and method of fabricating thereof
US7074731B2 (en) * 2002-05-17 2006-07-11 Heraeus Quarzglas Gmbh & Co. Kg Method for producing hydrogen-doped silica powder, hydrogen-doped silica powder obtained from that method for use in a quartz glass crucible
JP2007191392A (en) * 1998-05-25 2007-08-02 Shinetsu Quartz Prod Co Ltd Method for production of quartz glass crucible for pulling silicon single crystal
JP2007326780A (en) * 2007-09-18 2007-12-20 Shinetsu Quartz Prod Co Ltd Method for producing quartz glass crucible for pulling up silicon single crystal

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999061685A1 (en) * 1998-05-25 1999-12-02 Shin-Etsu Quartz Products Co., Ltd. Quartz glass crucible for pulling silicon monocrystal and method of manufacturing the same
JP2007191392A (en) * 1998-05-25 2007-08-02 Shinetsu Quartz Prod Co Ltd Method for production of quartz glass crucible for pulling silicon single crystal
JP4482567B2 (en) * 1998-05-25 2010-06-16 信越石英株式会社 Method for producing quartz glass crucible for pulling silicon single crystal
US6652934B1 (en) 1999-06-01 2003-11-25 Toshiba Ceramics Co., Ltd. Silica glass crucible and method of fabricating thereof
JP2002211997A (en) * 2001-01-10 2002-07-31 Kusuwa Kuorutsu:Kk Crucible for pulling semiconductor silicon
US7074731B2 (en) * 2002-05-17 2006-07-11 Heraeus Quarzglas Gmbh & Co. Kg Method for producing hydrogen-doped silica powder, hydrogen-doped silica powder obtained from that method for use in a quartz glass crucible
JP2007326780A (en) * 2007-09-18 2007-12-20 Shinetsu Quartz Prod Co Ltd Method for producing quartz glass crucible for pulling up silicon single crystal
JP4702898B2 (en) * 2007-09-18 2011-06-15 信越石英株式会社 Method for producing quartz glass crucible for pulling silicon single crystal

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