JP2003292329A - Method for forming barium-containing layer on surface of quartz crucible by cvd method - Google Patents
Method for forming barium-containing layer on surface of quartz crucible by cvd methodInfo
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- JP2003292329A JP2003292329A JP2002094541A JP2002094541A JP2003292329A JP 2003292329 A JP2003292329 A JP 2003292329A JP 2002094541 A JP2002094541 A JP 2002094541A JP 2002094541 A JP2002094541 A JP 2002094541A JP 2003292329 A JP2003292329 A JP 2003292329A
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- barium
- crucible
- containing layer
- forming
- cvd
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- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、単結晶引上げ用石
英ガラスルツボの表面に、ＣＶＤ反応（化学蒸着反応）
によってバリウム含有層を形成する方法と、この方法に
よって形成したバリウム含有層を有する石英ガラスルツ
ボに関する。TECHNICAL FIELD The present invention relates to a CVD reaction (chemical vapor deposition reaction) on the surface of a quartz glass crucible for pulling a single crystal.
And a quartz glass crucible having a barium-containing layer formed by this method.
【０００２】[0002]
【従来の技術】単結晶引上げ用石英ガラスルツボの表面
にバリウム含有層を形成して、ルツボを強化する技術が
開示されており（特開平８-２９３２号、特開平８-１１
０５９０号等）、このルツボを用いた結晶成長方法も開
示されている（特開平９-１１０５７９号）。具体的に
は、これらの方法では石英ガラスルツボの表面に水酸化
バリウム溶液などを塗布し、水酸化バリウムと空気中の
二酸化炭素と反応させて生じた炭酸バリウムをルツボ表
面に沈着させ、これを乾燥することによってルツボ表面
に炭酸バリウム層を形成している。この他に、ジルコニ
ウムや希土類元素などを含む表面層を形成した石英ガラ
スルツボも提案されている（特開2002−29890号）。2. Description of the Related Art A technique for strengthening a crucible by forming a barium-containing layer on the surface of a quartz glass crucible for pulling a single crystal has been disclosed (JP-A-8-2932 and JP-A-8-11).
No. 0590), and a crystal growth method using this crucible is also disclosed (JP-A-9-110579). Specifically, in these methods, a barium hydroxide solution or the like is applied to the surface of the quartz glass crucible, barium carbonate produced by reacting barium hydroxide with carbon dioxide in the air is deposited on the crucible surface, and this is applied. A barium carbonate layer is formed on the surface of the crucible by drying. In addition, a quartz glass crucible having a surface layer containing zirconium or a rare earth element has been proposed (Japanese Patent Laid-Open No. 2002-29890).
【０００３】[0003]
【発明が解決すべき課題】ところが、従来の炭酸バリウ
ム等をルツボ表面に付着させた石英ガラスルツボには次
のような問題がある。すなわち、(イ)ルツボ表面の炭酸
バリウム粉はバインダー等によって固着されているので
はないために剥落しやすく、付着状態が不均一になり、
しかも炭酸バリウム粉が飛散して作業員の健康を害する
惧れがある。また、(ロ)十分な効果を得るために炭酸バ
リウムの付着量が過剰になりやすい。さらに（ハ）洗浄
すると炭酸バリウム粉が洗い流されるので、炭酸バリウ
ム粉の付着後からルツボ使用までの間、表面に汚れが付
いてもルツボを洗浄することができない。However, the conventional quartz glass crucible having barium carbonate or the like attached to the surface of the crucible has the following problems. That is, (a) the barium carbonate powder on the surface of the crucible is not fixed by a binder or the like, so it is easy to peel off, and the adhesion state becomes uneven,
Moreover, the barium carbonate powder may scatter and damage the health of the workers. Further, (b) the amount of barium carbonate attached tends to become excessive in order to obtain a sufficient effect. Furthermore, since the barium carbonate powder is washed away by (c) cleaning, the crucible cannot be cleaned even if the surface is soiled after the barium carbonate powder is attached and before the crucible is used.
【０００４】また、ジルコニウム等を含む表面層を形成
した石英ガラスルツボでは、金属酸化物がゾル状態で分
散されているコーテング液をルツボ表面に塗布し、これ
を大気中１５０℃で乾燥することによって表面層を形成
しているが、この程度の温度下で加熱処理しても、ルツ
ボ表面には焼き付けられた表面層を形成することができ
ず、従って表面層が剥離し易いと云う問題が解消されな
い。さらに、従来の上記何れの方法においても、コーテ
ング液組成の調整やコーティング中のハンドリング、使
用後の廃液処理等において煩雑な作業が避けられない。In a quartz glass crucible having a surface layer containing zirconium or the like, a coating solution in which a metal oxide is dispersed in a sol state is applied to the surface of the crucible and dried at 150 ° C. in the atmosphere. Although the surface layer is formed, the problem that the surface layer is easily peeled off cannot be formed on the crucible surface even if it is heat-treated at this temperature. Not done. Further, in any of the above-mentioned conventional methods, complicated work is inevitable in adjusting the coating liquid composition, handling during coating, waste liquid treatment after use, and the like.
【０００５】本発明は、従来の上記問題を解決したもの
であり、溶液による塗布やスプレイを必要としない気相
熱分解に基づいてルツボ表面にバリウム含有層を形成す
る技術を提供するものであり、本発明の方法によれば、
従来よりもはるかに簡素化された工程によって、しかも
従来よりも均一性に優れたバリウム含有層をルツボ表面
に形成することができる。The present invention solves the above-mentioned problems of the prior art and provides a technique for forming a barium-containing layer on the surface of a crucible based on vapor phase thermal decomposition that does not require coating with a solution or spraying. , According to the method of the present invention,
It is possible to form a barium-containing layer on the surface of the crucible, which has a more uniform process than the conventional one and is more uniform than the conventional one.
【０００６】[0006]
【課題を解決するための手段】すなわち、本発明は
（１）単結晶引上げ用石英ガラスルツボの表面をＣＶＤ
反応が生起するのに十分な温度に加熱しつつ、この加熱
されたルツボ表面にバリウム源化合物を気相で供給して
ＣＶＤ反応を生起させ、ルツボ表面にバリウム含有層を
形成することを特徴とするＣＶＤ法による石英ルツボ表
面のバリウム含有層の形成方法に関する。That is, according to the present invention, (1) the surface of a quartz glass crucible for pulling a single crystal is subjected to CVD.
While heating to a temperature sufficient for the reaction to occur, a barium source compound is supplied to the heated crucible surface in a gas phase to cause a CVD reaction, and a barium-containing layer is formed on the crucible surface. The method for forming a barium-containing layer on the surface of a quartz crucible by the above-mentioned CVD method.
【０００７】本発明のバリウム含有層形成方法は、
（２）ルツボ表面の加熱温度が３００〜１２００℃であ
る形成方法、（３）加熱されたルツボ表面へのバリウム
源化合物の供給がキャリアガスによる気相搬送によって
行われる形成方法、（４）バリウム源化合物がバリウム
の有機酸塩の有機溶媒溶液である形成方法、（５）バリ
ウム源化合物がエチルヘキサン酸バリウム、ビス（ジピ
バロイルメタナト）バリウム、またはビス（ヘキサフル
オロアセチルアセトナト）バリウムの何れかである形成
方法、（６）有機溶媒がトルエンまたはテトラヒドロフ
ランの何れかである形成方法、（７）キャリアガスが窒
素またはアルゴンである形成方法を含む。さらに本発明
は（８）上記何れかにの方法によって形成されたバリウ
ム含有層を表面に有することを特徴とする単結晶引上げ
用石英ガラスルツボに関する。The barium-containing layer forming method of the present invention comprises:
(2) A forming method in which the heating temperature of the crucible surface is 300 to 1200 ° C., (3) A forming method in which the barium source compound is supplied to the heated crucible surface by vapor-phase transfer with a carrier gas, (4) Barium The source compound is a solution of an organic acid salt of barium in an organic solvent, (5) the source compound of barium ethylhexanoate, bis (dipivaloylmethanato) barium, or bis (hexafluoroacetylacetonato) barium Any of the formation methods, (6) the formation method in which the organic solvent is either toluene or tetrahydrofuran, and (7) the formation method in which the carrier gas is nitrogen or argon. Further, the present invention relates to (8) a quartz glass crucible for pulling a single crystal, which has a barium-containing layer formed by the method according to any one of the above on the surface.
【０００８】本発明の形成方法は、ガラスルツボの表面
をＣＶＤ反応が生起するのに十分な温度に加熱し、この
加熱されたルツボ表面にバリウム源化合物を気相で供給
してＣＶＤ反応を生起させることによってルツボ表面に
バリウム含有層を形成するので、溶液による塗布やスプ
レイを必要とせず、従来よりも格段に簡素化された工程
によって均一な組成のバリウム含有層を安定に形成する
ことができる。In the forming method of the present invention, the surface of the glass crucible is heated to a temperature sufficient for the CVD reaction to occur, and the barium source compound is supplied to the heated crucible surface in the vapor phase to cause the CVD reaction. By forming a barium-containing layer on the surface of the crucible by doing so, it is possible to stably form a barium-containing layer having a uniform composition by a process significantly simplified as compared with the prior art, without the need for coating or spraying with a solution. .
【０００９】[0009]
【発明の実施の形態】以下、本発明を実施形態に基づい
て具体的に説明する。本発明において好適なバリウム源
化合物としては、例えば、バリウムの有機酸塩やβ−ジ
ケトン錯体を用いることができる。好適な有機酸塩とし
てカルボン酸塩が挙げられる。カルボン酸塩を形成する
アシルオキシ基は、一般式ＣnＨ2n+1ＣＯＯ（ｎは３〜
７の整数）で表されるものが好適である。具体的には、
n−酪酸、α−メチル酪酸、ｉ−吉草酸、2−エチル酪
酸、2,2−ジメチル酪酸、3,3−ジメチル酪酸、2,3−ジ
メチル酪酸、3−メチルペンタン酸、4−メチルペンタン
酸、2−エチルペンタン酸、3−エチルペンタン酸、2,2
−ジメチルペンタン酸、3,3−ジメチルペンタン酸、2,3
−ジメチルペンタン酸、2−エチルヘキサン酸、3−エチ
ルヘキサン酸等から誘導されるアシルオキシ基が好適に
用いられる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below based on embodiments. As a barium source compound suitable in the present invention, for example, an organic acid salt of barium or a β-diketone complex can be used. Suitable organic acid salts include carboxylates. The acyloxy group forming the carboxylate salt has a general formula of C n H 2n + 1 COO (n is 3 to
Those represented by (an integer of 7) are preferable. In particular,
n-butyric acid, α-methylbutyric acid, i-valeric acid, 2-ethylbutyric acid, 2,2-dimethylbutyric acid, 3,3-dimethylbutyric acid, 2,3-dimethylbutyric acid, 3-methylpentanoic acid, 4-methylpentane Acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, 2,2
-Dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 2,3
An acyloxy group derived from dimethylpentanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid or the like is preferably used.
【００１０】これらの有機酸塩のうち、例えば、２−エ
チルヘキサン酸バリウム、ビス(ジピバロイルメタナト)
バリウム、または、ビス(ヘキサフルオロアセチルアセ
トナト)バリウムなどは特に好適に使用することができ
る。これを双溶性の有機溶媒に混合溶解してキャリアガ
スに随伴させるのが最も簡便である。なお、後者のβ−
ジケトン類は有機溶媒なしで使用することも可能であ
る。Among these organic acid salts, for example, barium 2-ethylhexanoate, bis (dipivaloylmethanato)
Barium or bis (hexafluoroacetylacetonato) barium can be used particularly preferably. The simplest method is to mix and dissolve this in a bi-soluble organic solvent and to accompany it with a carrier gas. The latter β-
The diketones can also be used without an organic solvent.
【００１１】これらの有機酸塩は有機溶剤に溶解して使
用することが好ましい。好適な有機溶剤としてはトルエ
ン、キシレン、へキサン、シクロへキサン等の炭化水素
類、エーテル、エステル及び／又はアルコール、或いは
エステル及び／又はアルコールに更にカルボン酸を混合
した混合溶剤を用いることもできる。有機溶剤のエーテ
ルとしてはテトラヒドロフランのような環状エーテルも
好ましく用いられる。エステルとしては、酢酸エチル、
酢酸プロピル、酢酸n−プチル、酢酸sec−ブチル、酢酸
tert−ブチル、酢酸イソブチル、酢酸n−アミル、酢酸s
ec−アミル、酢酸tert−アミル、酢酸イソアミルが好ま
しい。These organic acid salts are preferably used by dissolving them in an organic solvent. As a suitable organic solvent, hydrocarbons such as toluene, xylene, hexane, and cyclohexane, ether, ester and / or alcohol, or a mixed solvent obtained by mixing ester and / or alcohol with carboxylic acid can also be used. . A cyclic ether such as tetrahydrofuran is also preferably used as the ether of the organic solvent. As the ester, ethyl acetate,
Propyl acetate, n-butyl acetate, sec-butyl acetate, acetic acid
tert-butyl, isobutyl acetate, n-amyl acetate, acetic acid s
Ec-amyl, tert-amyl acetate and isoamyl acetate are preferred.
【００１２】アルコールとしては、メタノール、エタノ
ール、1−プロパノール、2−プロパノール、1−ブタノ
ール、2−ブタノール、イソープチルアルコール、1−ペ
ンタノール、2−ペンタノール、2−メチル−2−ペンタ
ノール、イソ−アミルアルコール等が好適である。アル
コール類にはアルコキシアルコール、すなわちエーテル
基を含有するアルコールを含む。この種のアルコールの
例としては、2−メトキシエタノール、1−メトキシ−21
−プロパノールが挙げられる。他に使用出来る溶媒の例
としては、アセトン、メチルエチルケトン、メチルイソ
ブチルケトン等のケトン類が挙げられる。これらの有機
溶剤は２種以上混合して使用してもよい。Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isoptyl alcohol, 1-pentanol, 2-pentanol, 2-methyl-2-pentanol. , Iso-amyl alcohol and the like are preferable. Alcohols include alkoxy alcohols, ie alcohols containing ether groups. Examples of this type of alcohol are 2-methoxyethanol, 1-methoxy-21
Includes propanol. Other examples of the solvent that can be used include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. You may use these organic solvents in mixture of 2 or more types.
【００１３】バリウムの有機酸塩溶液は、図２に示すよ
うに、キャリアガスによって気相搬送して加熱したルツ
ボ表面に供給する。このとき、キャリアガスに酸素を５
％濃度程度導入すると良い。酸素の導入によってルツボ
表面に残留するカーボンの燃焼揮発が促進され、バリウ
ム含有層の品質を高めることができる。An organic acid salt solution of barium is, as shown in FIG. 2, vapor-phase-conveyed by a carrier gas and supplied to the heated crucible surface. At this time, oxygen is added to the carrier gas as 5
It is good to introduce about% concentration. The introduction of oxygen promotes combustion and volatilization of carbon remaining on the surface of the crucible, and can improve the quality of the barium-containing layer.
【００１４】本発明の実施には、実施例に開示した図１
のＣＶＤ反応炉を好適に用いることができる。炉内にル
ツボをセットするとき、シールド用円筒冶具を使用する
ことによりコーティング面を所望の位置になるように容
易に制御できる。炉内に設置した石英ガラスルツボの表
面がＣＶＤ反応を生起するのに十分な温度になるように
加熱する。この加熱温度は例えば３００〜１２００℃が
適当である。In practicing the present invention, FIG.
The CVD reactor can be preferably used. When setting the crucible in the furnace, it is possible to easily control the coating surface to a desired position by using a cylindrical jig for shielding. The surface of the quartz glass crucible installed in the furnace is heated to a temperature sufficient to cause a CVD reaction. A suitable heating temperature is 300 to 1200 ° C., for example.
【００１５】加熱されたルツボ表面に、上記バリウム源
化合物と酸素とを窒素またはアルゴンなどのキャリアガ
スによって搬送し、この気相供給によってルツボ表面で
ＣＶＤ反応を生起させる。この結果、例えば酸化バリウ
ムがルツボ表面に焼き付けられた状態のバリウム含有層
が形成される。このバリウム含有層はルツボ表面に焼き
付けられた状態であるため、ルツボ表面に接触した程度
では剥離せず、極めて安定である。The above barium source compound and oxygen are carried to a heated crucible surface by a carrier gas such as nitrogen or argon, and a CVD reaction is caused to occur on the crucible surface by this gas phase supply. As a result, a barium-containing layer in which barium oxide is baked on the crucible surface is formed. Since the barium-containing layer is baked on the surface of the crucible, it does not peel off when it comes into contact with the surface of the crucible and is extremely stable.
【００１６】[0016]
【実施例】図１の装置を用い、次の工程に従って、単結
晶引上げ用石英ガラスルツボの表面にバリウム含有層を
ＣＶＤ反応によって形成した。なお、原料のバリウム源
化合物として２−エチルヘキサン酸バリウムのトルエン
溶液（酸化バリウム換算０.１重量％溶液）を用い、キ
ャリアガスとして電子材料グレードの窒素ガスを用い
た。またバリウム含有層の品質を高めるために窒素ガス
に酸素を導入した。EXAMPLE A barium-containing layer was formed by a CVD reaction on the surface of a single crystal pulling quartz glass crucible using the apparatus shown in FIG. 1 according to the following steps. In addition, a toluene solution of barium 2-ethylhexanoate (0.1 wt% solution in terms of barium oxide) was used as a raw material barium source compound, and electronic material grade nitrogen gas was used as a carrier gas. Oxygen was introduced into the nitrogen gas to improve the quality of the barium-containing layer.
【００１７】〔操作〕
（１）炉内に石英ルツボ（口径18インチ）を図示するよう
にセットし、バルブ１〜３を閉じて排気口より真空排気
した。次に、（２）バルブ１を開いてキャリアガス
(Ｎ2:450cc/分、Ｏ2:50cc/分)を導入し、炉内を３torr
に保持した。その後、（３）セラミックヒーターに通電
して昇温を開始し、ルツボ内表面を６００℃に保持し
た。この状態で（４）バルブ１を閉じて、バルブ２、３
を開き、バリウム源化合物ガスを導入した。さらに、
（５）バルブ４を開いて酸素を導入した。（６）２０分
後、バルブ２〜４を閉じて、バルブ１を開き、窒素のみ
の通気に切り替えた。その後、（７）ヒーターをオフに
し、室温に下げてリークした後、ルツボを取り出した。[Operation] (1) A quartz crucible (diameter 18 inches) was set in the furnace as shown, valves 1 to 3 were closed, and vacuum exhaust was performed from the exhaust port. Next, (2) open the valve 1 to open the carrier gas
(N 2 : 450cc / min, O 2 : 50cc / min) was introduced, and 3 torr in the furnace
Held in. Thereafter, (3) the ceramic heater was energized to start the temperature rise, and the inner surface of the crucible was kept at 600 ° C. In this state, (4) close the valve 1 and open the valves 2, 3
Was opened and a barium source compound gas was introduced. further,
(5) The valve 4 was opened to introduce oxygen. (6) After 20 minutes, the valves 2 to 4 were closed, the valve 1 was opened, and the ventilation was switched to nitrogen only. Then, (7) the heater was turned off, the temperature was lowered to room temperature to cause a leak, and then the crucible was taken out.
【００１８】〔検査〕得られたルツボの外観を検査し
た。比較のため、同濃度の２-エチルヘキサン酸バリウ
ムのトルエン溶液を用いて、スプレーコーティング法に
よりバリウム含有層を形成したルツボについても検査し
た。この結果を図３(実施例)、図４(従来例)に示した。
図示するように、従来のスプレー法では液を吹き付ける
ためにコーテング層に跡が残り、均一な組成のコーテン
グ層が形成されない。一方、本発明のＣＶＤ法では吹付
け跡のない均一なコーテング層（バリウム濃度１０μg/
cm2）が得られた。[Inspection] The appearance of the obtained crucible was inspected. For comparison, a crucible having a barium-containing layer formed by a spray coating method was also inspected using a toluene solution of barium 2-ethylhexanoate having the same concentration. The results are shown in FIG. 3 (example) and FIG. 4 (conventional example).
As shown in the figure, in the conventional spraying method, since a liquid is sprayed, a trace remains on the coating layer, and a coating layer having a uniform composition cannot be formed. On the other hand, according to the CVD method of the present invention, a uniform coating layer (barium concentration of 10 μg /
cm 2 ) was obtained.
【００１９】〔失透試験〕上記(１)〜(７)の工程によっ
て製造したバリウム含有層を有する本発明の石英ガラス
ルツボと、従来のスプレー法によってコーテング層を形
成した石英ガラスルツボ（バリウム濃度１０μg/cm2）
についてシリコン単結晶の引上げを行い、引上げ後のル
ツボについて失透層の断面を観察した。この結果を図５
(実施例)、図６(従来例)に示した。図示するように、従
来のスプレー法によって形成したものはバリウムの分府
が不均一であるために失透層に斑が生じている。一方、
本発明に係るバリウム含有層を有する石英ルツボには失
透層の不均一な斑はみられない。またシリコン単結晶引
上げの単結晶化率（単結晶重量／原料の多結晶重量）に
ついては、スプレー法によってバリウム含有層を形成し
た従来の石英ルツボは４０％であるのに対して、本発明
の石英ルツボは７５％であり、単結晶化率についても顕
著な差がみられた。[Devitrification Test] A quartz glass crucible of the present invention having a barium-containing layer produced by the above steps (1) to (7), and a quartz glass crucible having a coating layer formed by a conventional spray method (barium concentration). 10 μg / cm 2 )
The silicon single crystal was pulled, and the cross section of the devitrification layer was observed in the crucible after the pulling. This result is shown in FIG.
(Example) and FIG. 6 (conventional example). As shown in the figure, in the case of the conventional spray method, the devitrification layer has spots due to the uneven distribution of barium. on the other hand,
The quartz crucible having the barium-containing layer according to the present invention does not show uneven devitrification layer unevenness. The single crystallization rate of pulling a silicon single crystal (weight of single crystal / weight of polycrystal of raw material) is 40% in the conventional quartz crucible in which the barium-containing layer is formed by the spray method, whereas The amount of quartz crucible was 75%, and there was a significant difference in the single crystallization rate.
【００２０】[0020]
【発明の効果】本発明によれば、石英ルツボの内面にコ
ーティング液をスプレイし、あるいは塗布する煩雑な操
作が不要であり、組成の均一なバリウム含有層を容易に
形成することができる。また、本発明の方法によって形
成したバリウム含有層はルツボ表面に焼き付けられた状
態であるために、ルツボ表面に接触した程度では剥離せ
ず極めて安定であり、従って、シリコン単結晶の引上げ
において、高い単結晶化率を達成することができる。According to the present invention, the complicated operation of spraying or applying the coating liquid on the inner surface of the quartz crucible is unnecessary, and the barium-containing layer having a uniform composition can be easily formed. Further, since the barium-containing layer formed by the method of the present invention is in a state of being baked on the surface of the crucible, it is extremely stable without peeling when it comes into contact with the surface of the crucible, and therefore, in pulling a silicon single crystal, it is high. A single crystallization rate can be achieved.
【図１】 ＣＶＤ炉の概念図FIG. 1 Conceptual diagram of a CVD furnace
【図２】 実施例において炉内の石英ルツボ表面にバリ
ウム含有層を形成する操作を示す説明図FIG. 2 is an explanatory view showing an operation of forming a barium-containing layer on the surface of a quartz crucible in a furnace in an example.
【図３】 本発明に係る石英ルツボのバリウム含有層の
顕微鏡写真FIG. 3 is a micrograph of a barium-containing layer of a quartz crucible according to the present invention.
【図４】 従来の石英ルツボのバリウム含有層の顕微鏡
写真FIG. 4 is a micrograph of a barium-containing layer of a conventional quartz crucible.
【図５】 本発明に係る石英ルツボの失透層の断面を示
す顕微鏡写真FIG. 5 is a micrograph showing a cross section of the devitrification layer of the quartz crucible according to the present invention.
【図６】 従来の石英ルツボの失透層の断面を示す顕微
鏡写真FIG. 6 is a micrograph showing a cross section of a devitrification layer of a conventional quartz crucible.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 賢 秋田県秋田市茨島５丁目14番３号 ジャパ ンスーパークォーツ株式会社秋田事業所内 Ｆターム(参考） 4G014 AH12 AH14 AH21 4G077 AA02 BA04 CF10 EG02 PD01 4K030 AA11 AA18 BA01 BA42 CA06 CA11 LA11 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Ken Sato 5-14-3 Ibarakijima, Akita City, Akita Japan Super Quartz Co., Ltd. Akita Office F-term (reference) 4G014 AH12 AH14 AH21 4G077 AA02 BA04 CF10 EG02 PD01 4K030 AA11 AA18 BA01 BA42 CA06 CA11 LA11
Claims (8)
を、ＣＶＤ反応が生起するのに十分な温度に加熱しつ
つ、この加熱されたルツボ表面にバリウム源化合物を気
相で供給してＣＶＤ反応を生起させ、ルツボ表面にバリ
ウム含有層を形成することを特徴とするＣＶＤ法による
石英ルツボ表面のバリウム含有層の形成方法。1. A quartz crystal crucible for pulling a single crystal is heated to a temperature sufficient to cause a CVD reaction, and a barium source compound is supplied to the heated crucible surface in a vapor phase to carry out a CVD reaction. And a barium-containing layer is formed on the surface of the crucible by a CVD method.
０℃である請求項１に記載するバリウム含有層の形成方
法。2. The heating temperature of the crucible surface is 300 to 120.
The method for forming a barium-containing layer according to claim 1, which is 0 ° C.
合物の供給がキャリアガスによる気相搬送によって行わ
れる請求項１または２に記載するバリウム含有層の形成
方法。3. The method for forming a barium-containing layer according to claim 1, wherein the barium source compound is supplied to the heated surface of the crucible by vapor-phase transport with a carrier gas.
塩の有機溶媒溶液である請求項１、２または３の何れか
に記載するバリウム含有層の形成方法。4. The method for forming a barium-containing layer according to claim 1, wherein the barium source compound is a solution of an organic acid salt of barium in an organic solvent.
バリウム、ビス（ジピバロイルメタナト）バリウム、ま
たはビス（ヘキサフルオロアセチルアセトナト）バリウ
ムの何れかである請求項１〜４の何れかに記載するバリ
ウム含有層の形成方法。5. The barium source compound is any one of barium ethylhexanoate, bis (dipivaloylmethanato) barium, and bis (hexafluoroacetylacetonato) barium. A method of forming a barium-containing layer.
ロフランの何れかである請求項１〜５の何れかに記載す
るバリウム含有層の形成方法。6. The method for forming a barium-containing layer according to claim 1, wherein the organic solvent is either toluene or tetrahydrofuran.
ある請求項１〜６の何れかに記載するバリウム含有層の
形成方法。7. The method for forming a barium-containing layer according to claim 1, wherein the carrier gas is nitrogen or argon.
形成されたバリウム含有層を表面に有することを特徴と
する単結晶引上げ用石英ガラスルツボ。8. A quartz glass crucible for pulling a single crystal, having a barium-containing layer formed by the method according to claim 1 on the surface.
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|---|---|---|---|
| JP2002094541A JP4096331B2 (en) | 2002-03-29 | 2002-03-29 | Method for forming barium-containing layer on quartz crucible surface by CVD method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005343707A (en) * | 2004-05-31 | 2005-12-15 | Japan Siper Quarts Corp | Quartz glass crucible suppressed in thermal expansion, and method of pulling silicon single crystal |
| JP2010222250A (en) * | 2010-06-07 | 2010-10-07 | Japan Siper Quarts Corp | Quartz glass crucible |
| CN102432189A (en) * | 2011-09-20 | 2012-05-02 | 沈福茂 | Spraying equipment of barium coating on quartz crucible |
-
2002
- 2002-03-29 JP JP2002094541A patent/JP4096331B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005343707A (en) * | 2004-05-31 | 2005-12-15 | Japan Siper Quarts Corp | Quartz glass crucible suppressed in thermal expansion, and method of pulling silicon single crystal |
| JP4726436B2 (en) * | 2004-05-31 | 2011-07-20 | ジャパンスーパークォーツ株式会社 | Method for producing quartz glass crucible |
| JP2010222250A (en) * | 2010-06-07 | 2010-10-07 | Japan Siper Quarts Corp | Quartz glass crucible |
| CN102432189A (en) * | 2011-09-20 | 2012-05-02 | 沈福茂 | Spraying equipment of barium coating on quartz crucible |
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| Publication number | Publication date |
|---|---|
| JP4096331B2 (en) | 2008-06-04 |
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