JPH0729871B2 - Quartz crucible for pulling single crystals - Google Patents
Quartz crucible for pulling single crystalsInfo
- Publication number
- JPH0729871B2 JPH0729871B2 JP62304625A JP30462587A JPH0729871B2 JP H0729871 B2 JPH0729871 B2 JP H0729871B2 JP 62304625 A JP62304625 A JP 62304625A JP 30462587 A JP30462587 A JP 30462587A JP H0729871 B2 JPH0729871 B2 JP H0729871B2
- Authority
- JP
- Japan
- Prior art keywords
- crucible
- quartz
- bubbles
- quartz glass
- single crystal
- 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.)
- Expired - Lifetime
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 137
- 239000010453 quartz Substances 0.000 title claims description 73
- 239000013078 crystal Substances 0.000 title claims description 56
- 239000000843 powder Substances 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000003181 co-melting Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 70
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 20
- 229910052710 silicon Inorganic materials 0.000 description 20
- 239000010703 silicon Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Glass Melting And Manufacturing (AREA)
- Surface Treatment Of Glass (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、単結晶ケイ素のような単結晶物質の成長に使
用される石英ガラス容器すなわち石英るつぼに関する。Description: FIELD OF THE INVENTION The present invention relates to a quartz glass container or quartz crucible used for growing a single crystal material such as single crystal silicon.
従来、単結晶半導体材料のような単結晶物質の製造に
は、いわゆるチョクラルスキー法と呼ばれる方法が広く
採用されている。この方法は、多結晶ケイ素を容器内で
溶融させ、この溶融浴内に種結晶の端部を漬けた回転さ
せながら引き上げるもので、種結晶上に同一の結晶方位
を持つ単結晶が成長する。この単結晶の引き上げの容器
には、石英るつぼが一般的に使用されている。石英るつ
ぼは、製造方法により生じる外観の相違から、透明るつ
ぼと、半透明るつぼとに分類される。BACKGROUND ART Conventionally, a so-called Czochralski method has been widely adopted for producing a single crystal substance such as a single crystal semiconductor material. In this method, polycrystalline silicon is melted in a container, and the end of the seed crystal is immersed in the molten bath and pulled up while rotating, and a single crystal having the same crystal orientation grows on the seed crystal. A quartz crucible is generally used as a container for pulling the single crystal. Quartz crucibles are classified into transparent crucibles and semi-transparent crucibles due to the difference in appearance caused by the manufacturing method.
半透明るつぼは、石英粉末を回転している型に投入し、
型の内面に沿って層状に堆積させたのち、さらに型を回
転させながら石英粉末層を内面から加熱して、気泡を含
む石英ガラス製品とすることにより製造される。この半
透明石英るつぼは、透明石英るつぼと比較したとき、強
度が高いこと、および大きな寸法のるつぼの製造が容易
なこと、等の利点を有する。さらに、半透明石英るつぼ
に含まれる微小な気泡が熱の分布を均一にする傾向があ
るため、透明るつぼに比べて温度が均一になる、という
利点もある。このような理由から、半透明石英るつぼが
実用上広く使用されている。The semi-transparent crucible puts quartz powder into a rotating mold,
It is manufactured by depositing layers along the inner surface of the mold and then heating the quartz powder layer from the inner surface while further rotating the mold to obtain a quartz glass product containing bubbles. This semi-transparent quartz crucible has advantages such as high strength and easy production of a crucible having a large size when compared with the transparent quartz crucible. Further, since minute bubbles contained in the semi-transparent quartz crucible tend to make the heat distribution uniform, there is also an advantage that the temperature becomes uniform as compared with the transparent crucible. For this reason, the semitransparent quartz crucible is widely used in practice.
しかし、半透明石英るつぼは、単結晶の製造過程におい
て、結晶化が不安定になり、収率が低下する、という問
題がある。この結晶化が不安定になる理由は幾つか考え
られるが、その一つとしては、高温度のもとでの溶融ケ
イ素と石英ガラスとの間の反応のためにるつぼの内面が
浸食され、るつぼの内面に荒れが生じることが挙げられ
る。浸食が進行すると、るつぼに含まれていた気泡が溶
融ケイ素に露出され、るつぼ内面の肌荒れの原因となる
が、溶融ケイ素がこの肌荒れしたるつぼ内面に接触する
と、溶融ケイ素の湯面は、溶融ケイ素の量の減少に伴っ
て円滑に低下することができなくなる。さらに、るつぼ
内面の肌荒れにより生じた微細な突起が、石英ガラスの
結晶化の核となり、斑点状のクリストバライトを形成す
る。このようにして形成されたクリストバライトは、る
つぼから離脱して溶融ケイ素内に落ち込み、引き上げら
れる単結晶の成長に悪影響を与える。However, the semi-transparent quartz crucible has a problem that the crystallization becomes unstable and the yield is lowered in the process of manufacturing the single crystal. There are several possible reasons for this unstable crystallization, one of which is that the inner surface of the crucible is eroded due to the reaction between molten silicon and quartz glass at high temperature. Roughness may occur on the inner surface of the. As the erosion progresses, the bubbles contained in the crucible are exposed to the molten silicon, which causes rough skin on the inner surface of the crucible. It becomes impossible to decrease smoothly with the decrease of the amount. Further, the fine protrusions generated by the rough surface of the inner surface of the crucible serve as nuclei for crystallization of the quartz glass to form speckled cristobalite. The cristobalite thus formed separates from the crucible and falls into the molten silicon, adversely affecting the growth of the pulled single crystal.
他の問題としては、主として石英粉末の中に含まれた金
属不純物が、石英粉末の加熱溶融による石英ガラスの形
成後、内在する気泡の近傍に析出し、石英るつぼの結晶
引き上げの過程で特にその内表面近傍における析出金属
不純物がその内表面におけるクリストバライトの形成を
促進し斑点状のクリストバライトを形成することがあ
る。またるつぼの製造時に、るつぼの内表面に微小な突
起や掻き傷が形成されると、その周辺に金属不純物の析
出が起き、同様な理由で好ましくない。Another problem is that metal impurities mainly contained in the quartz powder are deposited in the vicinity of the internal bubbles after the formation of the quartz glass by heating and melting the quartz powder, and especially in the process of pulling the crystal of the quartz crucible. Precipitated metal impurities in the vicinity of the inner surface may promote the formation of cristobalite on the inner surface to form spotted cristobalite. Further, when minute projections or scratches are formed on the inner surface of the crucible during the production of the crucible, metal impurities are precipitated around the projections, which is not preferable for the same reason.
従来の石英るつぼにおける上述の問題を解決するため
に、特開昭59−213697号公報には、石英るつぼの内面の
うち、少なくとも溶融ケイ素に接触する部分に、約1mm
以上の厚さの透明石英ガラス層を形成することが教示さ
れている。この公開特許公報の教示によれば、この透明
石英ガラス層は、半透明石英ガラスるつぼの内面を長時
間にわたり加熱することにより形成される。この方法
は、るつぼ内面の加熱により、るつぼ内面に近接する層
内の気泡を膨張させ、破裂させて気泡の消去を行うもの
であるが、この方法では気泡の除去はほとんど不可能で
あり、得られる透明石英ガラス層は気泡含有量が十分に
低くなく、或る程度の気泡を依然として含有する点で満
足できるものではない。単結晶引き上げの最近の技術で
は、引き上げが低圧雰囲気のもとで行われるので、この
公開特許公報に開示された技術を採用すると、依然とし
てるつぼ内に含まれる気泡が低圧雰囲気のもとで膨張
し、溶融ケイ素との接触により、るつぼ表面が浸食さ
れ、肌荒れが大きくなり、従来のるつぼで経験されてい
たと同様な問題を生じる。上記公開公報には、別な方法
として、単結晶引き上げ時にシリコン湯面と接触するる
つぼ部分に、リング状の透明石英ガラスを挟み込み、溶
着することが教示されている。しかし、この方法は製造
が面例であるだけでなく、るつぼ内面がリング状の透明
石英ガラスと他の部分との接合部で十分に滑らかでな
く、かつ強度低下の問題も生じる。In order to solve the above-mentioned problems in the conventional quartz crucible, JP-A-59-213697 discloses that at least a portion of the inner surface of the quartz crucible that is in contact with molten silicon has a thickness of about 1 mm.
It is taught to form a transparent quartz glass layer having the above thickness. According to the teaching of this publication, the transparent quartz glass layer is formed by heating the inner surface of the semitransparent quartz glass crucible for a long time. This method expands bubbles in a layer close to the inner surface of the crucible by heating the inner surface of the crucible and causes the bubbles to explode to eliminate the bubbles, but it is almost impossible to remove the bubbles by this method. The resulting transparent silica glass layer is not sufficiently low in bubble content and is still unsatisfactory in that it still contains some bubbles. In the recent technique for pulling a single crystal, the pulling is performed in a low pressure atmosphere. Therefore, when the technique disclosed in this publication is adopted, the bubbles contained in the crucible still expand under the low pressure atmosphere. The contact with molten silicon causes the surface of the crucible to be eroded, resulting in rough skin and causing the same problems as those experienced in conventional crucibles. As another method, the above-mentioned publication teaches that a ring-shaped transparent quartz glass is sandwiched and welded to a crucible portion that comes into contact with the molten silicon surface when pulling a single crystal. However, this method is not only an example of manufacturing, but also the inner surface of the crucible is not sufficiently smooth at the joint between the ring-shaped transparent quartz glass and other portions, and there is a problem of strength reduction.
米国特許第4,528,163号明細書は、るつぼ基体を外層と
内層との２層に形成し、外層を天然石英の粉末により、
内層を人造石英の粉末によりそれぞれ形成することを教
示する。この米国特許の教示によれば、このようにして
形成したるつぼ基体の内面を加熱して、非結晶質の滑ら
かな薄い内面を形成する。しかし、前述の公開特許公報
により形成されたるつぼの場合と同様に、この米国特許
の教示に基づいて形成された非結晶質の層も多量の気泡
や空洞を含むもので、満足に使用できるものではない。U.S. Pat. No. 4,528,163 discloses that a crucible substrate is formed into two layers, an outer layer and an inner layer, and the outer layer is made of natural quartz powder.
It is taught that the inner layers are each made of artificial quartz powder. According to the teachings of this U.S. Patent, the inner surface of the crucible substrate thus formed is heated to form a smooth, amorphous thin inner surface. However, as in the case of the crucible formed according to the above-mentioned published patent publication, the amorphous layer formed according to the teachings of this U.S. patent also contains a large amount of bubbles and cavities and is satisfactory for use. is not.
米国特許第4,416,680号明細書および同第4,632,686号明
細書は、石英るつぼを加熱しながら外側から負圧を作用
させて気泡含有量を減少させることを教示している。し
かし、気泡は石英ガラスの層を通過する過程で大きな抵
抗を受けるので、この米国特許に教示された方法では気
泡含有量を低くすることが最も望まれる内面層の気泡含
有量を十分に低下させることができない。U.S. Pat. Nos. 4,416,680 and 4,632,686 teach the application of negative pressure from the outside while heating a quartz crucible to reduce bubble content. However, since the bubbles are subjected to a large resistance as they pass through the layer of quartz glass, the method taught in this U.S. Patent is sufficient to reduce the bubble content of the inner surface layer where it is most desirable to have a low bubble content. I can't.
さらに、単結晶引き上げ工程では、工程の安定化だけで
なく、るつぼから単結晶に与えられる酸素の量を正確に
制御することも重要であるが、従来の方法により製造さ
れた石英るつぼは、内面が十分に均一でなく、るつぼに
多量の気泡が含まれることから、引き上げ工程中に内面
の荒れを生じるので、るつぼから溶融ケイ素内に溶け込
む石英の量が不安定になり、酸素量を正確に制御するこ
とが困難になる。Furthermore, in the single crystal pulling process, it is important not only to stabilize the process but also to accurately control the amount of oxygen given to the single crystal from the crucible. Is not sufficiently uniform and the crucible contains a large amount of bubbles, which causes roughening of the inner surface during the pulling process, which makes the amount of quartz that melts into the molten silicon from the crucible unstable and makes it possible to accurately measure the oxygen amount. It becomes difficult to control.
従来の半透明るつぼを使用する単結晶引き上げにおいて
遭遇する他の問題は、るつぼ壁に存在する気泡により、
透明るつぼに比べて熱の分布が一様になるのではある
が、その気泡の大きさ及び分布が適正でないために、外
部加熱源からの熱の伝達が均一でなくなることである。
その結果、単結晶の引き上げが不安定になる。Another problem encountered in single crystal pulling using a conventional translucent crucible is the presence of air bubbles in the crucible wall.
Although the heat distribution is more uniform than in a transparent crucible, the heat transfer from the external heating source is not uniform due to the improper size and distribution of the bubbles.
As a result, pulling of the single crystal becomes unstable.
その他にも、従来の石英るつぼでは、引き上げ工程中に
るつぼが長時間高温に曝されたとき、該るつぼに変形を
生じる、という問題がある。この問題は、前述したいず
れの公知技術によっても解消できない。In addition, the conventional quartz crucible has a problem that when the crucible is exposed to a high temperature for a long time during the pulling process, the crucible is deformed. This problem cannot be solved by any of the known techniques described above.
したがって、本発明は、単結晶引き上げに使用される石
英るつぼの改良された構造を提供することを解決すべき
課題とする。The present invention therefore makes it a problem to be solved to provide an improved structure of a quartz crucible used for pulling single crystals.
もっと詳細に述べると、本発明が解決しようとする課題
の一つは、熱の伝達が均一に行われ、しかも単結晶引き
上げに際しても内壁面の肌荒れが極めて少なく、安定し
た単結晶引き上げを行うことができる石英るつぼを提供
することである。More specifically, one of the problems to be solved by the present invention is that heat transfer is performed uniformly, and even when pulling a single crystal, the inner wall surface is extremely rough, and stable pulling of the single crystal is performed. It is to provide a quartz crucible capable of
上記課題を解決するため、本発明においては、石英るつ
ぼを外層と内層とから構成する。外層は気泡を含む半透
明石英ガラス層であり、その気泡は、直径10ないし250
μｍで、1cm3あたり20,000個以上70,000個以下の範囲で
含まれる。内層は実質的に無気泡で、るつぼの内面とな
る表面が平滑である。この内層は、0.3mm以上の厚さで
形成される。そして、外層と内層とは、一体融合的に接
合されている。In order to solve the above problems, in the present invention, a quartz crucible is composed of an outer layer and an inner layer. The outer layer is a semi-transparent quartz glass layer containing bubbles, the bubbles having a diameter of 10 to 250.
It is contained in the range of 20,000 or more and 70,000 or less per 1 cm 3 in μm. The inner layer is substantially bubble-free and the inner surface of the crucible is smooth. This inner layer is formed with a thickness of 0.3 mm or more. The outer layer and the inner layer are integrally fused and joined together.
本発明の好ましい態様においては、気泡は半透明石英ガ
ラス層の厚さ方向の60％以上の部分で40,000ないし70,0
00個含まれる。In a preferred embodiment of the present invention, the bubbles are 40,000 to 70,0 at 60% or more in the thickness direction of the semitransparent quartz glass layer.
00 is included.
本発明において、るつぼが実質的に無気泡である、とい
うことは、肉眼で観察できる大きさの気泡は一切含まな
いことは勿論であるが、肉眼で観察できない気泡でも、
直径20μｍより大きい気泡の含有量は、平均値で1cm2当
たり５個以下である。なお直径20μｍより小さい気泡
は、光の散乱によっても測定が困難である。In the present invention, the crucible is substantially bubble-free, that of course does not include any bubbles of a size that can be observed with the naked eye, but even bubbles that cannot be observed with the naked eye,
The average content of bubbles larger than 20 μm in diameter is 5 or less per 1 cm 2 . Bubbles smaller than 20 μm in diameter are difficult to measure due to light scattering.
通常の透明石英ガラスるつぼは、肉眼で観察できる大き
さの100μｍの気泡をある程度含有し、かつ肉眼で観察
できないが、光の散乱による観察で検出できる微細な気
泡を大量に含んでいる。本発明の石英るつぼは、このよ
うな通常の半導体単結晶の引き上げに使用される透明石
英ガラスるつぼに比べて、含有する気泡が極めて少ない
点に特徴がある。An ordinary transparent quartz glass crucible contains a certain amount of bubbles of 100 μm that can be observed by the naked eye, and although it cannot be observed by the naked eye, it contains a large amount of fine bubbles that can be detected by observation by light scattering. The quartz crucible of the present invention is characterized in that it contains extremely few bubbles as compared with the transparent quartz glass crucible used for pulling such a usual semiconductor single crystal.
従来の半透明石英るつぼにおいては、気泡含有量は、1c
m3あたり１万個から数万個まで広い範囲のばらつきを示
していた。このために、るつぼ壁における熱の伝達が均
一でなくなり、シリコン単結晶の引き上げ工程が不安定
になっていた。本発明においては、外層の構造を直径10
〜250μｍの気泡を1cm3あたり20,000個以上含む半透明
石英ガラス層とすることにより、電熱ヒータ部及びるつ
ぼを支えるカーボンサセプターの構造により石英るつぼ
内壁面への熱の不均一伝達という問題点が解消され、結
果として、熱の伝達が従来の半透明るつぼに比べて飛躍
的に均一化される。また、内層は実質的に無気泡で、内
面が平滑であるので、シリコン単結晶の引き上げによっ
ても肌荒れを生じることがなく、単結晶引き上げを安定
して行うことができる。In a conventional translucent quartz crucible, the bubble content is 1c
It showed a wide range of variation from 10,000 to tens of thousands per m 3 . For this reason, the heat transfer through the crucible wall is not uniform, and the pulling process of the silicon single crystal becomes unstable. In the present invention, the outer layer structure has a diameter of 10
By using a semi-transparent quartz glass layer containing 20,000 or more bubbles of ~ 250 μm per cm 3, the problem of uneven heat transfer to the inner wall surface of the quartz crucible is solved by the structure of the carbon susceptor supporting the electric heater and the crucible. As a result, the heat transfer is dramatically made uniform as compared with the conventional translucent crucible. In addition, since the inner layer is substantially bubble-free and the inner surface is smooth, roughening of the silicon single crystal does not occur and the single crystal can be pulled up stably.
以下、本発明の実施例について説明する。 Examples of the present invention will be described below.
第１図において、本発明の石英るつぼ１は、外側の半透
明石英ガラス層２と、この層の内表面に実質的に無気泡
の完全溶融層を連続的に成長せしめ一体融合的に形成さ
れた薄い透明石英ガラス層３とからなる。半透明石英ガ
ラス層２内には、直径10〜250μｍの多数の気泡４が1cm
3当たり20,000個以上、好ましくはその円筒部の当該半
透明ガラス層２の厚さ方向の60％以上の部分で1cm3当た
り40,000〜70,000個の存在密度で分布している。In FIG. 1, a quartz crucible 1 of the present invention is formed integrally and integrally by forming an outer semitransparent quartz glass layer 2 and an essentially bubble-free completely melted layer on the inner surface of this layer. And a thin transparent quartz glass layer 3. Within the semi-transparent quartz glass layer 2, a large number of bubbles 4 with a diameter of 10 to 250 μm are 1 cm.
It is distributed at a density of 40,000 to 70,000 per 1 cm 3 in 20,000 or more per 3 , preferably 60% or more in the thickness direction of the semitransparent glass layer 2 of the cylindrical portion.
このような半透明石英ガラス層２における多数の気泡４
の存在により、外部ヒーターからのるつぼ内面への熱エ
ネルギーの伝達が均一となり、熱源のむら、あるいはる
つぼの肉厚のバラツキによりるつぼ内壁面に生じる温度
むらを低減することができる。A large number of bubbles 4 in such a semi-transparent quartz glass layer 2
Due to the presence of the heat exchanger, the heat energy can be uniformly transferred from the external heater to the inner surface of the crucible, and the unevenness of the heat source or the uneven temperature of the inner wall surface of the crucible due to the variation in the thickness of the crucible can be reduced.
この結果、単結晶引き上げ時において、原料多結晶溶液
が、るつぼに内面全域において一定した熱履歴を受け、
単結晶引き上げが極めて安定して行われる。As a result, at the time of pulling the single crystal, the raw material polycrystalline solution receives a constant thermal history in the entire inner surface of the crucible,
Single crystal pulling is extremely stable.
半透明石英ガラス層２中の気泡４の数が上述の範囲を外
れた場合、すなわち気泡の数が少なすぎる場合は、熱の
拡散が不充分となり、るつぼ１の内壁面に温度むらを生
ずる。気泡４の数に特に上限はないが、気泡が多くなり
すぎるとガラス自体の強度の低下をもたらすばかりでな
く、高温下での気泡同志の融着による巨大の気泡の発生
等の不都合を生ずることがあるので、気泡の数はこの点
で制限がある。最大値が1cm3当り70,000個の場合におい
て、上記不具合がなく、且つ本発明の目的を達成するこ
とが可能である。If the number of bubbles 4 in the semi-transparent quartz glass layer 2 is out of the above range, that is, if the number of bubbles is too small, the heat is not sufficiently diffused and uneven temperature occurs on the inner wall surface of the crucible 1. There is no particular upper limit to the number of bubbles 4, but if the number of bubbles is too large, not only will the strength of the glass itself be reduced, but also inconveniences such as the generation of huge bubbles due to fusion of the bubbles at high temperatures will occur. Therefore, the number of bubbles is limited in this respect. In the case where the maximum value is 70,000 per cm 3 , the above problems do not occur and the object of the present invention can be achieved.
透明石英ガラス層３における実質的に無気泡であるとい
う基準は、前述したとおり、通常の石英ガラスるつぼ例
えば特開昭59−213697号公報に開示の石英るつぼにおけ
る透明石英ガラス層に比べて、その含有する気泡が極め
て少ないということである。通常の半導体用石英ガラス
るつぼは、肉眼で観察しうる大きさの100μｍ〜1mmの気
泡をある程度含み、肉眼では観察できないが、光を当て
て気泡による散乱によって観察が可能な程度の微小な気
泡を大量に含んでいる。本発明における無気泡の具体的
な例としては、倍率30倍の顕微鏡の視野約8mm2の範囲
で、６個の未使用の石英るつぼを各るつぼにつき側壁表
面４ケ所、底部１ケ所の計５ケ所で総計30ケ所について
観察した結果、直径20μｍ以上の気泡が２ないし３ケ所
でわずかに認められる程度である。その１例として、こ
の30ケ所の測定点で直径20μｍ以上の気泡が２個見られ
たのは１ケ所、１個見られたのは２ケ所であり、気泡の
存在密度は0.13個/8mm2（1cm2に換算すると約1.6個/c
m2）であり、極めて気泡の少ない均質性の高い層となっ
ている。As described above, the criterion that the transparent quartz glass layer 3 is substantially free of bubbles is as compared with the ordinary quartz glass crucible, for example, the transparent quartz glass layer in the quartz crucible disclosed in JP-A-59-213697. This means that it contains very few bubbles. Ordinary quartz glass crucibles for semiconductors contain some bubbles of 100 μm to 1 mm that are observable to the naked eye and cannot be observed with the naked eye, but tiny bubbles that are observable by shining light and scattering by the bubbles Contains a large amount. Specific examples of bubble-free in the present invention is in the range 30X magnification of a microscope field of view about 8 mm 2, six unused quartz crucible each crucible per sidewall surface 4 places, the bottom one place five As a result of observing a total of 30 places, air bubbles having a diameter of 20 μm or more are slightly recognized at 2 or 3 places. As one example, at these 30 measurement points, two bubbles with a diameter of 20 μm or more were found in one place, one was seen in two places, and the density of bubbles was 0.13 bubbles / 8 mm 2 (Approximately 1.6 pieces / c when converted to 1 cm 2
m 2 ), which is a highly homogeneous layer with very few bubbles.
この透明石英ガラス層としては、上記の通りガラスの組
織的にも極めて均質な物が使用されている。この透明石
英ガラス層の存在によりシリコン融液との接触界面にお
いて、るつぼ内表面が反応によって侵食された場合に
も、透明層自体が活性中心や反応を促進しうる構造的な
要因を持っていない為、均一かつ遅い反応しか起こら
ず、クリストバライトが僅かしか生じないで新たに生成
する表面の平滑性を維持しており、常に安定したシリコ
ン融液とるつぼの界面を得ることが可能である。この
為、長時間に亙る引き上げでも安定した品質を保証する
ことができる。この重要な意味を持つ透明石英ガラス層
はるつぼの使用が完全に終了するまで必要であり、この
ためには少なくとも0.3mm、実際には0.8〜1mm以上であ
ることが望ましい。又、るつぼの各部分においてはシリ
コン融液と接触する時間が異なるので、例えば、円筒部
の上の方は薄く底へ向かって厚さが増すなどこれに合わ
せた透明石英ガラス層の厚さの分布を設けることも可能
である。As the transparent quartz glass layer, an extremely homogeneous glass is used as described above. Even if the inner surface of the crucible is eroded by the reaction at the contact interface with the silicon melt due to the presence of this transparent quartz glass layer, the transparent layer itself has no active center or structural factor that can promote the reaction. For this reason, only a uniform and slow reaction occurs, the cristobalite is slightly generated, and the smoothness of the newly generated surface is maintained, and it is possible to always obtain a stable interface between the silicon melt and the crucible. Therefore, it is possible to guarantee stable quality even when pulling up for a long time. A layer of transparent quartz glass of this significance is necessary until the end of the use of the crucible, for which purpose it is desirable that it is at least 0.3 mm, in fact 0.8-1 mm or more. In addition, since the time of contact with the silicon melt is different in each part of the crucible, for example, the upper part of the cylindrical part becomes thinner toward the bottom, and the thickness of the transparent quartz glass layer is adjusted accordingly. It is also possible to provide a distribution.
半透明石英ガラス層２中には、結晶質石英成分が混在す
ることが好ましい。この結晶質石英成分は、半透明石英
ガラス層中の外表面近傍に偏在するようにすることが、
さらに好ましい。A crystalline quartz component is preferably mixed in the semitransparent quartz glass layer 2. This crystalline quartz component may be unevenly distributed near the outer surface of the semitransparent quartz glass layer,
More preferable.
結晶質石英成分は、半透明石英ガラス層２中に粒子状に
分散して存在し、これによってるつぼの使用時、例えば
シリコンの融点である1450℃近辺での耐変形性が大幅に
向上する。もし、るつぼとこれを支えるカーボンサセプ
ターとの間に隙間が有った場合でもるつぼ内に装入され
た原料シリコンの荷重によってるつぼが変形するという
ことがなくなる。The crystalline quartz component is dispersed and present in the semitransparent quartz glass layer 2 in the form of particles, which greatly improves the deformation resistance when the crucible is used, for example, at around 1450 ° C. which is the melting point of silicon. Even if there is a gap between the crucible and the carbon susceptor supporting the crucible, the crucible will not be deformed by the load of the raw material silicon charged in the crucible.
1450℃のような高温でるつぼを長時間使用していると
き、るつぼに局部的な変形やゆがみがもたらされると、
その変形部分でるつぼ内面への熱エネルギーの伝達が他
の部分と異なってくる。そのため、原料融液はるつぼ内
面の部分で異なった熱履歴を受けることとなり、その結
果融液の対流に乱れを生じ、単結晶引き上げが不安定に
なる。また、るつぼの変形自体単結晶引き上げに支障を
与える。本発明によるるつぼでは、このような変形に伴
なう問題を大巾に軽減することができる。When using the crucible at a high temperature such as 1450 ° C for a long time, if the crucible is locally deformed or warped,
At the deformed portion, the transfer of thermal energy to the inner surface of the crucible becomes different from other portions. Therefore, the raw material melt is subjected to different thermal histories at the inner surface of the crucible, and as a result, convection of the melt is disturbed and the single crystal pulling becomes unstable. Further, the deformation of the crucible itself hinders the pulling of the single crystal. With the crucible according to the present invention, the problems associated with such deformation can be greatly reduced.
次に本発明の半石英るつぼを製造する一例を以下に説明
する。まず、使用する原料粉としては天然水晶等の精製
された粉体が使用される。この粉体を回転しているるつ
ぼ製造用型内に供給し、遠心力によって所定の厚さに層
を形成した後、内側からアーク放電等の手段によって溶
融を開始する。この段階で、半透明石英ガラス層２が形
成されるが、この時、溶融条件を制御して形成した粉体
層全体をガラス化することなく、又、必要に応じて型の
外部を冷却することによって余分な熱を奪い前記半透明
石英ガラス層２の外表面近傍に結晶質石英成分を残留さ
せることが可能である。Next, an example of producing the semi-quartz crucible of the present invention will be described below. First, as the raw material powder used, purified powder such as natural crystal is used. This powder is supplied into a rotating crucible manufacturing mold, a layer is formed to a predetermined thickness by centrifugal force, and then melting is started from the inside by means such as arc discharge. At this stage, the semi-transparent quartz glass layer 2 is formed. At this time, the entire powder layer formed by controlling the melting conditions is not vitrified, and the outside of the mold is cooled if necessary. As a result, it is possible to remove excess heat and leave the crystalline quartz component near the outer surface of the semitransparent quartz glass layer 2.
本発明に於いては、気泡の大きさ及び存在密度が前述の
範囲、すなわち直径10ないし250μｍの気泡が20,000個/
cm3以上の密度で含まれることが必要である。できれ
ば、半透明石英ガラス層の厚さ方向の60％以上の部分で
40,000ないし70,000個/cm3の範囲で気泡を含むことが望
ましいが、これは原料粉として結晶水を含まない結晶質
石英の粉体を使用し、その粒度分布を300ないし100μｍ
の範囲に制御して、加熱溶融条件を制御することによっ
て達成できる。In the present invention, the size and the existing density of the bubbles are in the above range, that is, 20,000 bubbles having a diameter of 10 to 250 μm /
It must be contained at a density of at least cm 3 . If possible, use 60% or more of the translucent quartz glass layer in the thickness direction.
It is desirable to contain bubbles in the range of 40,000 to 70,000 cells / cm 3 , but this uses crystalline quartz powder that does not contain water of crystallization as the raw material powder, and its particle size distribution is 300 to 100 μm.
It can be achieved by controlling the heating and melting conditions by controlling the temperature in the range.
本発明における半透明石英ガラスるつぼ内表面の透明石
英ガラス層は、粉体の追加溶融によって一体融合的に形
成することができる。この様にして形成された透明層
は、気泡の痕跡も存在しない為減圧下で膨張することも
無い。特に水晶粉末を回転金型内に供給して遠心力によ
って型の壁に外壁石英粉末層の予備成形体を作り、次い
で石英粉末をアーク放電等の高温ガス雰囲気中を通過さ
せて半溶融状態の粉末を放電エネルギーによって外壁石
英粉末層の内面に連続的に付着せしめ実質的に無気泡の
完全溶融層を設層すれば、外壁石英粉末層とその内面の
透明層とが同時溶融により付着し合うので所望の厚さを
有する無気泡の透明石英ガラス層がしっかりと半透明石
英ガラス層上に形成される。The transparent quartz glass layer on the inner surface of the semitransparent quartz glass crucible in the present invention can be integrally formed by additional melting of powder. The transparent layer thus formed does not expand under reduced pressure because there are no traces of bubbles. In particular, quartz powder is fed into a rotary mold to create a preform of the outer wall quartz powder layer on the wall of the mold by centrifugal force, and then the quartz powder is passed through a high temperature gas atmosphere such as arc discharge to form a semi-molten state. If the powder is continuously adhered to the inner surface of the outer wall quartz powder layer by a discharge energy and a completely molten layer having substantially no bubbles is formed, the outer wall quartz powder layer and the inner transparent layer adhere to each other by simultaneous melting. Therefore, a bubble-free transparent quartz glass layer having a desired thickness is firmly formed on the semitransparent quartz glass layer.
実施例 次に本発明の実施例について説明する。Example Next, an example of the present invention will be described.
先ず、前述の方法により、原料粉体を調製して、直径14
インチの本発明の石英るつぼを作製し本発明試料１、２
とした。First, the raw material powder was prepared by the above-mentioned method, and the diameter 14
Inventive quartz crucibles of the present invention were prepared and the present invention samples 1 and 2 were prepared.
And
また、比較のため直径14インチの半透明石英るつぼを作
製し比較試料１、２、３とした。For comparison, 14-inch diameter semitransparent quartz crucibles were prepared and used as Comparative Samples 1, 2, and 3.
この比較試料としての半透明石英るつぼは、本発明の内
表面の透明層の形成を行なわず、また半透明ガラス層２
の外表面に結晶性石英粉を残留させない条件を除いて、
本発明試料を使用する石英粉末ならびに製造方法は全く
同じである。The semitransparent quartz crucible as the comparative sample did not form the transparent layer on the inner surface of the present invention, and the semitransparent glass layer 2 was used.
Except the condition that crystalline quartz powder does not remain on the outer surface of
The quartz powder and the manufacturing method using the sample of the present invention are exactly the same.
これらの石英るつぼの気泡直径、気泡存在密度および半
透明石英ガラス層中の結晶質石英成分の有無を表１示
す。Table 1 shows the bubble diameter, bubble existing density, and presence / absence of crystalline quartz component in the semitransparent quartz glass layer of these quartz crucibles.
また、石英るつぼの外表面および厚さ方向に1mm研削し
た箇所のＸ線回折の結果を第２図に示す。The results of X-ray diffraction of the outer surface of the quartz crucible and the portion ground by 1 mm in the thickness direction are shown in FIG.
上記の試料について、以下の実験を行なった。 The following experiments were conducted on the above samples.
（実施例１） 気泡の存在の効果を調べるため、通常の単結晶引き上げ
装置は本発明試料１、２、３、比較試料１、２の各るつ
ぼをセットし、空焼きを行ってるつぼ内面の温度のバラ
ツキを調べた。(Example 1) In order to investigate the effect of the presence of air bubbles, a normal single crystal pulling apparatus was set with each crucible of Samples 1, 2 and 3 of the present invention and Comparative Samples 1 and 2, and the inner surface of the crucible was baked. The temperature variation was investigated.
その結果、設定温度に対して、本発明試料１及び２では
±３℃、本発明試料２では±５℃の範囲に入っていたの
に対し、比較試料１では±10℃、比較試料２では±13℃
のバラツキがみられた。これにより、本発明のるつぼは
全体的に均一に加熱され、すなわち均一な熱伝達が行な
われることが判る。As a result, in comparison with the set temperature, the samples of the present invention 1 and 2 were within ± 3 ° C, and the samples of the present invention 2 were within ± 5 ° C. ± 13 ° C
There was some variation. From this, it can be seen that the crucible of the present invention is uniformly heated, that is, uniform heat transfer is performed.
特に、比較試料２では、その温度変化は、他の３試料が
緩やかな曲線状に連続的な変化を示したのと対照的に、
急激な温度変化がみられた。これは、比較試料２の気泡
密度が13,000個/cm3から60,000個/cm3の範囲で大きなバ
ラツキがあり、熱伝達が均一に行なわれていないからで
ある。In particular, in the comparative sample 2, the temperature change, in contrast to the other three samples, which showed a continuous change in a gentle curve,
A sudden temperature change was observed. This is because there is a large variation in the bubble density of the comparative sample 2 in the range of 13,000 cells / cm 3 to 60,000 cells / cm 3 , and heat transfer is not performed uniformly.
（実施例２） 半透明石英ガラス層中の結晶質石英成分の効果を調べる
ため、本発明試料１、２および比較試料１、２について
耐熱性の比較を行った。この比較試料は、るつぼを円筒
部と底部の変曲部分で10mmの隙間ができるカーボンサセ
プターに入れ、るつぼ内に10kgの多結晶シリコンを入れ
1450℃で溶解し20時間保持した。(Example 2) In order to investigate the effect of the crystalline quartz component in the semi-transparent quartz glass layer, the heat resistance of Samples 1 and 2 of the present invention and Comparative Samples 1 and 2 were compared. In this comparative sample, the crucible was placed in a carbon susceptor with a 10 mm gap between the cylindrical part and the inflexion part at the bottom, and 10 kg of polycrystalline silicon was placed in the crucible.
It was melted at 1450 ° C and kept for 20 hours.
その結果、本発明試料１および２は変形が小さく、るつ
ぼとカーボンサセプターとの間の隙間は、それぞれ8mm
および7mmになっただけであるが、比較試料１および２
は底部の変形が大きく、前記隙間が2mmおよび1mmとな
り、大きく変形した。As a result, the samples 1 and 2 of the present invention showed small deformation, and the gap between the crucible and the carbon susceptor was 8 mm each.
And only 7 mm, but comparative samples 1 and 2
The deformation of the bottom was large, and the gap was 2 mm and 1 mm, and the deformation was large.
また、本発明試料１、２、比較試料１、２について、る
つぼ外径を150mmとなるように作製し、これらを輪切り
にして長さ2cmの管状とし、電気炉内に壁面を下にして
立て、1300℃で18時間加熱して、管の直径の変化を調べ
た結果、比較試料１および２はつぶれて直径が約30mmお
よび約35mm変化したが、本発明試料１では約7mm、本発
明試料２では約8mm小さくなったのみであり、結晶質石
英成分はるつぼの強度を著しく増大させることが判る。Inventive Samples 1 and 2 and Comparative Samples 1 and 2 were prepared so that the crucible had an outer diameter of 150 mm, and these were sliced into a tube with a length of 2 cm, and the wall surface was placed inside the electric furnace with the wall facing down. As a result of examining the change in the diameter of the tube after heating at 1300 ° C. for 18 hours, Comparative Samples 1 and 2 were crushed and the diameters were changed by about 30 mm and about 35 mm. In No. 2, it was only about 8 mm smaller, and it can be seen that the crystalline quartz component remarkably increases the strength of the crucible.
（実施例３） 本発明に係る透明石英ガラス層の効果を調べるため、単
結晶引き上げによるるつぼ内表面の表面粗さの変化を測
定した。すなわち、本発明試料１および比較試料１を使
用して50時間の単結晶成長を行った後のるつぼの内表面
の粗さを測定した。(Example 3) In order to investigate the effect of the transparent quartz glass layer according to the present invention, a change in surface roughness of the inner surface of the crucible due to pulling a single crystal was measured. That is, the roughness of the inner surface of the crucible after the single crystal growth was performed for 50 hours using the present invention sample 1 and the comparative sample 1 was measured.
測定は触針式表面粗さ計（（株）小坂研究所製）で行っ
た。第３図には、使用前の本発明料１の表面粗さ、第４
図には、単結晶成長を行った後の本発明試料１の表面粗
さ、第５図には、単結晶成長を行った後の比較試料１の
表面粗さの測定結果を示す。The measurement was performed with a stylus type surface roughness meter (manufactured by Kosaka Laboratory Ltd.). FIG. 3 shows the surface roughness of the material 1 of the present invention before use,
The figure shows the measurement results of the surface roughness of the sample 1 of the present invention after the single crystal growth, and FIG. 5 shows the measurement results of the surface roughness of the comparative sample 1 after the single crystal growth.
各図から明らかなように、本発明の石英ガラスるつぼは
使用後においても最大粗さ29μｍとかなり平滑な内表面
を維持しているが、従来のるつぼではその粗さが本発明
るつぼの約３倍になり、これによって本発明のるつぼに
おいてはシリコンの溶融面の乱れが生じにくくなること
が判る。As is clear from each figure, the quartz glass crucible of the present invention maintains a fairly smooth inner surface with a maximum roughness of 29 μm even after use, but in the conventional crucible, the roughness is about 3 of that of the crucible of the present invention. It is found that the melting surface of silicon is less likely to be disturbed in the crucible of the present invention.
また、結晶成長終了後のるつぼ内表面の点失透の状態を
第6A図および第6B図に示す。The state of point devitrification on the inner surface of the crucible after completion of crystal growth is shown in FIGS. 6A and 6B.
第6A図は本発明試料１の内表面、第6B図は比較試料１の
内表面を示すものである。これによれば、装置のるつぼ
の内表面には、クリストバライトの発生が従来のものに
比較して著しく少なくなることが判る。すなわち、本発
明の石英るつぼの内面は極めて均質であり、結晶化反応
の核となる突起等が少ないため、クリストバライトによ
る点失透の発生が少ない。FIG. 6A shows the inner surface of the sample 1 of the present invention, and FIG. 6B shows the inner surface of the comparative sample 1. According to this, it can be seen that the generation of cristobalite on the inner surface of the crucible of the apparatus is significantly reduced as compared with the conventional one. That is, the inner surface of the quartz crucible of the present invention is extremely uniform, and since there are few protrusions or the like that serve as nuclei for the crystallization reaction, point devitrification due to cristobalite is less likely to occur.
（実施例４） 次に本発明の石英るつぼを使用した場合のシリコン単結
晶製造の成績を示す。(Example 4) Next, the results of silicon single crystal production using the quartz crucible of the present invention will be shown.
製造条件は、アルゴン雰囲気下で減圧（10mb）で直径15
0mm、長さ70cmの単結晶インゴットを各るつぼで２本ず
つ連続して製造した。Manufacturing conditions are as follows: diameter 15 at reduced pressure (10mb) under argon atmosphere.
Two single crystal ingots each having a length of 0 mm and a length of 70 cm were continuously produced in each crucible.
製造した単結晶インゴットについて、その単結晶化率の
平均値を求めた。その結果を表２に示す。With respect to the manufactured single crystal ingot, the average value of the single crystallization rate was obtained. The results are shown in Table 2.
表２に示される結果より、本発明のるつぼは常に安定し
た単結晶製造をもたらすことが明らかである。 From the results shown in Table 2, it is clear that the crucible of the present invention always results in stable single crystal production.
次に上記のシリコン単結晶の引き上げに用いた、本発明
の石英るつぼおよび従来の石英るつぼの内表面から厚さ
方向0.3mmまでの内層部についての直径20μｍ以上の気
泡数を表３に示し、また、直胴部と底部の縦断面の状態
を第７図および第８図に示す。Next, Table 3 shows the number of bubbles having a diameter of 20 μm or more for the inner layer portion from the inner surface of the quartz crucible of the present invention and the conventional quartz crucible to the thickness direction of 0.3 mm used for pulling the above silicon single crystal. Further, the state of the vertical section of the straight body portion and the bottom portion is shown in FIGS. 7 and 8.
ここで注意を要するのは、石英るつぼは約1450℃の高温
で長時間、しかも減圧状態で加熱されているため、たと
えその使用前に無気泡とみなされても、この個々の気泡
が石英ガラスの軟化のために膨張し、観察が容易になる
ことである。すなわち、石英るつぼ製造時に石英ガラス
層に溶封されている気泡は、大気圧下の雰囲気ガス（石
英るつぼ製造が空気中で行われる場合には空気）で充填
されており、高温度減圧下では当然ながら膨張する。し
かしながら、表３および第7A図、第7B図に示されるよう
に本発明による石英るつぼは、使用後においてもその内
表面に明瞭な無気泡の透明石英ガラス層を有している。
一方、従来法による石英るつぼは、シリコン単結晶の引
き上げ前には内表面にある程度無気泡の薄い透明石英ガ
ラス層を有しているがシリコン単結晶の引き上げ時に気
泡が膨張し、これらが相互に融合して粗大化し、このた
め、シリコン単結晶の引き上げ後の石英るつぼ内表面に
明瞭な気泡の密集状態がみられる（表３および第8A図、
第8B図）。 It is important to note that the quartz crucible is heated at a high temperature of approximately 1450 ° C for a long time and in a decompressed state. Swells due to the softening of the powder and facilitates observation. That is, the bubbles sealed in the quartz glass layer at the time of manufacturing the quartz crucible are filled with the atmospheric gas under atmospheric pressure (air when the quartz crucible is manufactured in air), and are kept under high temperature and reduced pressure. Naturally expands. However, as shown in Table 3 and FIGS. 7A and 7B, the quartz crucible of the present invention has a clear bubble-free transparent quartz glass layer on the inner surface thereof even after use.
On the other hand, a conventional quartz crucible has a thin transparent quartz glass layer with no bubbles on the inner surface before pulling the silicon single crystal, but the bubbles expand when pulling the silicon single crystal, and these mutually expand. As a result of fusion and coarsening, a clear cluster of bubbles is observed on the inner surface of the quartz crucible after pulling the silicon single crystal (Table 3 and Fig. 8A,
(Fig. 8B).
本発明の石英るつぼによれば、単結晶引き上げ時に、外
部ヒーターからの熱エネルギーをるつぼ内面全域に均一
に伝達できるとともに、るつぼ内表面の部分的な侵食に
よる表面粗さの発生がきわめて小さくなる。このため、
複数回の単結晶引き上げを行なっても、従来のるつぼに
比べ高い単結晶化率を維持できる。また、半透明石英ガ
ラス層中に結晶質石英成分を存在せしめればるつぼの耐
熱強度を著しく増大させることができる。さらに、大気
圧下での単結晶引き上げはもちろんのこと、減圧下での
単結晶引き上げでも安定した高い単結晶化率を維持する
ことができる。According to the quartz crucible of the present invention, when pulling a single crystal, the heat energy from the external heater can be uniformly transferred to the entire inner surface of the crucible, and the generation of surface roughness due to partial erosion of the inner surface of the crucible becomes extremely small. For this reason,
Even if the single crystal is pulled a plurality of times, a higher single crystallization rate can be maintained as compared with the conventional crucible. Further, the presence of a crystalline quartz component in the semitransparent quartz glass layer can remarkably increase the heat resistance strength of the crucible. Further, a stable high single crystallization rate can be maintained not only when pulling the single crystal under atmospheric pressure but also when pulling the single crystal under reduced pressure.
第１図は本発明の石英るつぼの断面図、第２図は単結晶
成長前の石英るつぼのＸ線回折の結果を示す図面であ
り、第2A図は本発明のるつぼの外表面、第2B図は本発明
のるつぼの外表を1mm研削した面、第2C図は従来のるつ
ぼの外表面、第2D図は従来のるつぼの外表を1mm研削し
た面のそれぞれのＸ線回折の結果を示し、第３図は本発
明の石英るつぼ単結晶成長前の内表面に粗さを示すグラ
フ、第４図は本発明の石英るつぼの単結晶成長後の内表
面の粗さを示すグラフ、第５図は従来の石英るつぼの単
結晶成長後の内表面の粗さを示すグラフ、第6A図および
第6B図は単結晶成長後のるつぼ内表面の点失透の状態を
示す図面であり、第6A図は本発明のるつぼの内表面を、
第6B図は従来のるつぼの内表面をそれぞれ示し、第7A図
および第7B図は本発明のるつぼの壁の縦断面の状態を示
す図面、第8A図および第8B図は従来のるつぼの壁の縦断
面の状態を示す図面である。 １……石英るつぼ、２……半透明石英ガラス層、３……
透明石英ガラス層、４……気泡。FIG. 1 is a cross-sectional view of the quartz crucible of the present invention, FIG. 2 is a drawing showing the result of X-ray diffraction of the quartz crucible before single crystal growth, and FIG. 2A is the outer surface of the crucible of the present invention, FIG. 2B. Figure is a surface of the outer surface of the crucible of the present invention ground 1mm, Figure 2C is an outer surface of a conventional crucible, Figure 2D shows the result of each X-ray diffraction of the surface of the outer surface of the conventional crucible ground 1mm, FIG. 3 is a graph showing the roughness on the inner surface of the quartz crucible of the present invention before the single crystal growth, FIG. 4 is a graph showing the roughness of the inner surface of the quartz crucible of the present invention after the single crystal growth, FIG. FIG. 6 is a graph showing the roughness of the inner surface of a conventional quartz crucible after single crystal growth, and FIGS. 6A and 6B are drawings showing the state of point devitrification on the inner surface of the crucible after single crystal growth. The figure shows the inner surface of the crucible of the present invention,
FIG. 6B shows the inner surface of a conventional crucible, FIGS. 7A and 7B are drawings showing the state of the longitudinal section of the wall of the crucible of the present invention, and FIGS. 8A and 8B are the walls of the conventional crucible. 2 is a drawing showing a state of a vertical section of FIG. 1 ... Quartz crucible, 2 ... Semi-transparent quartz glass layer, 3 ...
Transparent quartz glass layer, 4 ... Bubbles.
フロントページの続き (72)発明者 福岡 敏人 福井県武生市北府２丁目13番60号 信越石 英株式会社武生工場内 (72)発明者 松村 光男 福井県武生市北府２丁目13番60号 信越石 英株式会社武生工場内 (72)発明者 松井 宏 福井県武生市北府２丁目13番60号 信越石 英株式会社武生工場内 (72)発明者 佐藤 恭彦 福島県郡山市田村町金屋字川久保88番地 株式会社福島信越石英内 (72)発明者 青山 雅明 福島県郡山市田村町金屋字川久保88番地 株式会社福島信越石英内 (72)発明者 篠宮 英一 福島県郡山市田村町金屋字川久保88番地 株式会社福島信越石英内 (72)発明者 藤ノ木 朗 福島県郡山市田村町金屋字川久保88番地 信越石英株式会社石英技術研究所内 (56)参考文献 特開 昭59−213697（ＪＰ，Ａ) 実開 昭62−175077（ＪＰ，Ｕ)Front Page Continuation (72) Inventor Toshito Fukuoka 2-13-60 Kitafu, Takefu City, Fukui Prefecture Shin-Etsuishi Hide Hideshi Takefu Co., Ltd. (72) Inventor Mitsuo Matsumura 2-13-60 Kitafu, Takefu City, Fukui Prefecture Shinetsu Ishihide Co., Ltd., Takefu Factory (72) Inventor Hiroshi Matsui, 2-13-60 Kitafu, Takefu City, Fukui Prefecture Shin-Etsu Ishihide Co., Ltd., Takefu Factory (72) Inventor, Yasuhiko Sato 88 Kawakubo Kawakubo, Tamura Town, Koriyama City, Fukushima Prefecture Address Fukushima Shin-Etsu Quartz Co., Ltd. (72) Inventor Masaaki Aoyama 88 Kawakubo, Kinya, Tamura-cho, Koriyama-shi, Fukushima Prefecture 72 Fukushima Shin-Etsu Quartz Co., Ltd. Eiichi Shinomiya 88, Kawakubo, Kaneya, Tamura-cho, Koriyama-shi, Fukushima Prefecture Fukushima Shin-Etsu Quartz Co., Ltd. (72) Inventor Akira Fujinoki 88, Kawakubo, Kanaya, Tamura-cho, Koriyama-shi, Fukushima Prefecture Quartz Research Laboratory, Shin-Etsu Quartz Co., Ltd. (56) Reference JP 59-213697 (JP, A) 62-175077 (JP, U)
Claims (3)
0,000個ないし70,000個含む半透明石英ガラス層と、こ
の層の内表面に一体融合的に形成された実質的に無気泡
な厚さ0.3mm以上の透明石英ガラス層とからなることを
特徴とする単結晶引き上げ用石英るつぼ。1. Bubbles having a diameter of 10 to 250 μm are 2 per 1 cm 2.
It is characterized by comprising a semi-transparent quartz glass layer containing 0,000 to 70,000 pieces and a substantially quartz-free transparent quartz glass layer having a thickness of 0.3 mm or more integrally formed on the inner surface of this layer. Quartz crucible for pulling single crystals.
層の予備成形体上に石英粉末を高温ガス雰囲気中を通し
て付着させ予備成形体と同時溶融により形成されたもの
であることを特徴とする特許請求の範囲第１項記載の単
結晶引き上げ用石英るつぼ。2. The transparent quartz glass layer is formed by co-melting the quartz glass powder on the preform of the semitransparent quartz glass layer through a high temperature gas atmosphere. A quartz crucible for pulling a single crystal according to claim 1.
ぼ円筒部の半透明石英ガラス層の厚さ方向の60％以上の
部分で1cm2当たり40,000〜70,000個であることを特徴と
する特許請求の範囲第１項ないし第２項のいずれかに記
載の単結晶引き上げ用石英るつぼ。3. The number of bubbles in the semitransparent quartz glass layer is 40,000 to 70,000 per 1 cm 2 in a portion of 60% or more in the thickness direction of the semitransparent quartz glass layer of the crucible cylindrical portion. A quartz crucible for pulling a single crystal according to any one of claims 1 and 2.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62304625A JPH0729871B2 (en) | 1987-12-03 | 1987-12-03 | Quartz crucible for pulling single crystals |
| US07/278,591 US4935046A (en) | 1987-12-03 | 1988-12-01 | Manufacture of a quartz glass vessel for the growth of single crystal semiconductor |
| EP19880120166 EP0319031B1 (en) | 1987-12-03 | 1988-12-02 | Manufacture of a quartz glass vessel for the growth of single crystal semiconductor |
| DE3888797T DE3888797T2 (en) | 1987-12-03 | 1988-12-02 | Process for the production of a quartz glass vessel for semiconductor single crystal growth. |
| US07/376,136 US4956208A (en) | 1987-12-03 | 1989-07-06 | Manufacture of a quartz glass vessel for the growth of single crystal semiconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62304625A JPH0729871B2 (en) | 1987-12-03 | 1987-12-03 | Quartz crucible for pulling single crystals |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4107530A Division JPH0742193B2 (en) | 1992-04-27 | 1992-04-27 | Quartz crucible for pulling single crystals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01148782A JPH01148782A (en) | 1989-06-12 |
| JPH0729871B2 true JPH0729871B2 (en) | 1995-04-05 |
Family
ID=17935279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62304625A Expired - Lifetime JPH0729871B2 (en) | 1987-12-03 | 1987-12-03 | Quartz crucible for pulling single crystals |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0729871B2 (en) |
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| JP2630649B2 (en) * | 1989-07-05 | 1997-07-16 | 東芝セラミックス株式会社 | Quartz glass crucible for single crystal pulling |
| JPH0742193B2 (en) * | 1992-04-27 | 1995-05-10 | 信越半導体株式会社 | Quartz crucible for pulling single crystals |
| WO2002014587A1 (en) * | 2000-08-15 | 2002-02-21 | Shin-Etsu Handotai Co., Ltd. | Quartz crucible and method for producing single crystal using the same |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59213697A (en) * | 1983-05-20 | 1984-12-03 | Toshiba Ceramics Co Ltd | Pulling device for single crystal semiconductor |
| JPH0431254Y2 (en) * | 1986-04-28 | 1992-07-28 |
-
1987
- 1987-12-03 JP JP62304625A patent/JPH0729871B2/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH01148782A (en) | 1989-06-12 |
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