JP2006016240A - High viscosity high purity quartz glass material, its manufacturing method and its use - Google Patents

High viscosity high purity quartz glass material, its manufacturing method and its use Download PDF

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JP2006016240A
JP2006016240A JP2004195033A JP2004195033A JP2006016240A JP 2006016240 A JP2006016240 A JP 2006016240A JP 2004195033 A JP2004195033 A JP 2004195033A JP 2004195033 A JP2004195033 A JP 2004195033A JP 2006016240 A JP2006016240 A JP 2006016240A
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quartz
crucible
quartz glass
aluminum
lithium
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JP4526311B2 (en
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Hiroshi Kishi
弘史 岸
Minoru Kanda
稔 神田
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Japan Super Quartz Corp
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Japan Super Quartz Corp
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    • 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

Abstract

<P>PROBLEM TO BE SOLVED: To provide a quartz glass crucible used for a high purity quartz glass material high in viscosity under a high temperature. <P>SOLUTION: In the method of manufacturing a high purity quartz glass material by impressing high voltage to remove metallic impurities in the vitrification of quartz powder, the quartz powder containing aluminum and lithium to increase the viscosity of the glass by aluminum and to decrease the electric resistance to enhance the purification effect by lithium. The method of the quartz glass crucible by a rotary molding method is carried out as one example by using quartz powder having 5-45 ppm aluminum concentration and lithium concentration ≥2% of aluminum concentration at least for the outer peripheral part of the crucible and the quartz glass crucible has ≥9.6×10<SP>9</SP>poise at 1,500°C. A method of pulling a silicon single crystal using the quartz glass crucible is provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、高温下での粘度が高い高純度の石英ガラス材とその製造方法に関する。特に半導体材料のシリコン単結晶を溶融シリコンから引き上げる際に使用される石英ガラスルツボについて、高温下での粘度が高く、かつ高純度の石英ガラスルツボとその製造方法、およびこの石英ガラスルツボを用いた引き上げ方法に関する。 The present invention relates to a high-purity quartz glass material having a high viscosity at a high temperature and a method for producing the same. In particular, a quartz glass crucible used when pulling up a silicon single crystal of a semiconductor material from molten silicon has a high-viscosity and high-purity quartz glass crucible, its manufacturing method, and this quartz glass crucible. It relates to the raising method.

半導体材料として使用されるシリコン単結晶は主に溶融した多結晶シリコンを引き上げて製造されており、溶融シリコンを入れるために石英ガラスルツボが用いられている。この石英ガラスルツボは溶融シリコンに不純物金属が混入しないように高純度のものが求められ、さらに高温下で変形しない強度を有することが求められる。 A silicon single crystal used as a semiconductor material is mainly manufactured by pulling up molten polycrystalline silicon, and a quartz glass crucible is used to put molten silicon. This quartz glass crucible is required to have a high purity so that an impurity metal is not mixed into the molten silicon, and further to have a strength that does not deform at high temperatures.

この石英ガラスルツボの製造方法として回転モールド法が知られている。この方法は、回転するモールドの内表面に石英粉を堆積させ、これをアーク放電等によって高温溶融してガラス化し、ルツボ状に成形する方法であり、原料の石英粉として合成石英粉や天然石英粉が用いられている。 A rotary mold method is known as a method for producing this quartz glass crucible. In this method, quartz powder is deposited on the inner surface of a rotating mold, and this is melted at a high temperature by arc discharge or the like to be vitrified and formed into a crucible. Synthetic quartz powder or natural quartz is used as a raw material quartz powder. Powder is used.

一般に、合成石英粉は不純物が少なく高純度であるが、水酸基が多いために粘度が低く高温下での強度が低いと云う性質があり、一方、天然石英粉は強度が高いがアルカリ金属量が多く純度が低いと云う性質がある。そこで、ルツボ内周層を高純度の合成石英ガラスによって形成すると共に外周層を強度の大きい天然石英によって形成した石英ルツボが製造されている。しかし、シリコン単結晶の大型化に伴って、ルツボも大型化し、引上げ時間が長くなることによって、このような石英ガラスルツボについても高温耐久性や不純物拡散防止の要求がさらに厳しくなっている。 In general, synthetic quartz powder has few impurities and high purity, but because of its many hydroxyl groups, it has the property of low viscosity and low strength at high temperatures, while natural quartz powder has high strength but alkali metal content. It has a property that it is often low in purity. Therefore, a quartz crucible is manufactured in which the inner peripheral layer of the crucible is formed of high-purity synthetic quartz glass and the outer peripheral layer is formed of natural quartz having a high strength. However, as the size of the silicon single crystal is increased, the crucible is also increased in size and the pulling time is increased, so that the requirements for high-temperature durability and prevention of impurity diffusion are becoming more severe for such a quartz glass crucible.

例えば、高温下での使用時間が長くなると、ルツボ外周側の天然石英層に含まれるアルカリ金属、特に拡散速度の速いリチウムが内側の合成石英層に拡散して溶融シリコンに移行して純度を低下させるなどの問題が生じている。これを避けるために内側の合成石英層を厚くすると、機械的強度が低下して変形や座屈などを生じやすくなり、長時間の使用に耐えられない。 For example, if the usage time at high temperature becomes longer, alkali metal contained in the natural quartz layer on the outer peripheral side of the crucible, especially lithium with a high diffusion rate, diffuses into the inner synthetic quartz layer and shifts to molten silicon to lower the purity. Causing problems. If the inner synthetic quartz layer is made thicker in order to avoid this, the mechanical strength is lowered, and deformation and buckling are likely to occur, so that it cannot be used for a long time.

一方、原料の石英粉をアーク溶融して石英ガラス材を製造する際に、電解精製を行って高純度化する方法が知られている。例えば、天然石英粉をアーク溶融して石英ガラスルツボや石英ガラス部材を成形し、ついでこれに高電圧を印加してアルカリ金属や銅を外表面部分に濃集させて除去する方法が知られている（特許文献１、２、３）。これらの石英ガラスルツボ等の電解精製法では、アルカリ金属含有量をそれぞれ０.５ppm以下、０.２ppm以下に低減しているが、高温下でのガラス粘度は１２００℃において４.５×１０12ポイズ〜１４５０℃において１.２×１０11ポイズであり、十分ではない。シリコン単結晶引き上げ時には、石英ガラスルツボは最大１６００℃程度の高温下で使用されるので、これらのルツボは使用時にルツボが自重によって変形する懸念がある。また、石英粉の加熱温度が１２００℃程度では電解精製効果が不十分である。
特公平０７−８０７１６号公報 特公平０７−１４８２２号公報 特公平０６−１０４５７７号公報 On the other hand, there is known a method in which when a raw material quartz powder is arc-melted to produce a quartz glass material, electrolytic purification is performed to increase the purity. For example, a method is known in which natural quartz powder is arc-melted to form a quartz glass crucible or a quartz glass member, and then a high voltage is applied to this to concentrate and remove alkali metal or copper on the outer surface portion. (Patent Documents 1, 2, and 3). In these electrolytic purification methods such as quartz glass crucibles, the alkali metal contents are reduced to 0.5 ppm or less and 0.2 ppm or less, respectively, but the glass viscosity at 1200 ° C. is 4.5 × 10 12. It is 1.2 × 10 11 poise at a poise to 1450 ° C., which is not sufficient. At the time of pulling up the silicon single crystal, the quartz glass crucible is used at a high temperature of about 1600 ° C. at maximum, so that these crucibles may be deformed by their own weight during use. Further, when the heating temperature of the quartz powder is about 1200 ° C., the electrolytic purification effect is insufficient.
Japanese Patent Publication No. 07-80716 Japanese Patent Publication No. 07-14822 Japanese Patent Publication No. 06-104577

本発明は、従来の上記問題を解決したものであり、高温下で変形し難く、かつアルカリ金属等の不純物が少ない高粘度および高純度の石英ガラスルツボとその製造方法等を提供する。 The present invention provides a quartz glass crucible having a high viscosity and a high purity that is difficult to deform at high temperatures and has few impurities such as alkali metals, a method for producing the same, and the like.

本発明は以下の石英ガラス材ないし石英ガラスルツボとその製造方法等に関する。
（１）石英粉を加熱してガラス化する際に、高電圧を印加して金属不純物を負極側に集めて除去することによって高純度の石英ガラス材を得る電解精製による製造方法において、アルミニウムとリチウムを含有した石英粉を用い、アルミニウムによってガラスの粘度を高める一方、リチウムによって電気抵抗を下げて精製効果を高めることを特徴とする高粘度および高純度の石英ガラス材の製造方法。
（２）モールド内表面に堆積した石英原料粉をアーク溶融し、あるいは石英原料粉をモールド内表面に供給しながらアーク溶融して石英ガラスルツボを製造する方法において、アルミニウムとリチウムを含有した石英粉を用い、アーク溶融時に高電圧を印加してガラス化することによって、高粘度および高純度の石英ガラスルツボを製造する上記(1)に記載する製造方法。
（３）少なくともルツボの外周部分がアルミニウム濃度５〜４５ppmおよびリチウム濃度がアルミニウム濃度の２％以上の石英粉を用いて製造されたルツボであって、１５００℃での粘度が９.６×１０9ポイズ以上であることを特徴とする石英ガラスルツボ。
（４）ルツボの外周部分がアルミニウム濃度５〜４５ppmおよびリチウム濃度がアルミニウム濃度の２％以上の石英粉を用い、ルツボ内周部分が合成石英粉を用いて製造された上記(3)の石英ガラスルツボ。
（５）電解精製後のルツボ外周部分のリチウム濃度がアルミニウム濃度の１％以下である上記(3)または(4)に記載する石英ガラスルツボ。
（６）上記(3)〜(5)の何れかに記載する石英ガラスルツボを用いたシリコン単結晶の引き上げ方法。 The present invention relates to the following quartz glass materials or quartz glass crucibles and methods for producing the same.
(1) In the manufacturing method by electrolytic refining to obtain a high-purity quartz glass material by applying high voltage to collect and remove metal impurities on the negative electrode side when the quartz powder is vitrified by heating, A method for producing a high-viscosity and high-purity quartz glass material, characterized in that quartz powder containing lithium is used to increase the viscosity of glass with aluminum, while reducing the electrical resistance with lithium to increase the purification effect.
(2) Quartz powder containing aluminum and lithium in a method for producing a quartz glass crucible by arc melting quartz raw material powder deposited on the inner surface of the mold or arc melting while supplying the quartz raw material powder to the inner surface of the mold The manufacturing method as described in (1) above, wherein a high-viscosity and high-purity quartz glass crucible is manufactured by applying a high voltage during arc melting to form a glass.
(3) A crucible manufactured using quartz powder in which at least the outer periphery of the crucible has an aluminum concentration of 5 to 45 ppm and a lithium concentration of 2% or more of the aluminum concentration, and has a viscosity of 9.6 × 10 9 at 1500 ° C. Quartz glass crucible characterized by being more than a poise.
(4) The quartz glass of the above (3), wherein the outer peripheral part of the crucible is made of quartz powder having an aluminum concentration of 5 to 45 ppm and the lithium concentration is 2% or more of the aluminum concentration, and the inner peripheral part of the crucible is made of synthetic quartz powder. Crucible.
(5) The quartz glass crucible as described in (3) or (4) above, wherein the lithium concentration in the outer periphery of the crucible after electrolytic purification is 1% or less of the aluminum concentration.
(6) A method for pulling a silicon single crystal using the quartz glass crucible described in any of (3) to (5) above.

〔具体的な説明〕
本発明の製造方法は、石英粉を加熱してガラス化する際に、高電圧を印加して金属不純物を負極側に集めて除去することによって高純度の石英ガラス材を得る電解精製による製造方法において、アルミニウムとリチウムを含有した石英粉を用い、アルミニウムによってガラスの粘度を高める一方、リチウムによって電気抵抗を下げて精製効果を高めることを特徴とする高粘度および高純度の石英ガラス材の製造方法である。 [Specific description]
The manufacturing method of the present invention is a manufacturing method by electrolytic refining to obtain a high-purity quartz glass material by applying a high voltage and collecting and removing metal impurities on the negative electrode side when the quartz powder is heated to vitrify. A method for producing a high-viscosity and high-purity quartz glass material, wherein quartz powder containing aluminum and lithium is used to increase the viscosity of the glass with aluminum, while reducing the electrical resistance with lithium to increase the purification effect It is.

石英粉を加熱溶融してガラス化する際に、溶融温度以上の高温下で、数百ボルト〜数十キロボルトの高電圧を印加すると、石英粉に含まれている金属不純物（金属イオン）が負極側に引き寄せられて集まるので、電解後に、この金属不純物濃集部分を除去することによって高純度の石英ガラス材を得ることができる。 When quartz powder is heated to melt and vitrified, applying a high voltage of several hundred volts to several tens of kilovolts at a temperature higher than the melting temperature causes the metal impurities (metal ions) contained in the quartz powder to be negative. Since the metal impurities are concentrated, the high-purity quartz glass material can be obtained by removing the metal impurity concentrated portion after electrolysis.

上記電解精製法において、石英粉に含まれるアルカリ金属量が多いとガラスの粘度が低下し、高温下で石英ガラス材が変形して形状不良を招く。一方、アルミニウム含有量が多いとガラスの粘度が高くなり、高温下での形状安定性が向上する。ただし、アルミニウム含有量が多い石英粉はガラスの粘度が高いので金属イオンの移動が抑制され、特に電解初期の未溶融石英粉の電気抵抗が高くなり、十分な電解精製効果が得られない。 In the electrolytic refining method, when the amount of alkali metal contained in the quartz powder is large, the viscosity of the glass is lowered, and the quartz glass material is deformed at a high temperature to cause a shape defect. On the other hand, when the aluminum content is large, the viscosity of the glass increases, and the shape stability at high temperatures is improved. However, quartz powder with a high aluminum content has high glass viscosity, so that the movement of metal ions is suppressed. In particular, the electric resistance of unmelted quartz powder at the initial stage of electrolysis increases, and a sufficient electrolytic purification effect cannot be obtained.

そこで、本発明の方法は、アルミニウムとリチウムの両方を含有した石英粉を用い、アルミニウムによってガラスの粘度を高める一方、リチウムによって電気抵抗を下げ、金属イオンが移動しやすいようにして精製効果を高める。すなわち、アルミニウムによる電気抵抗の増加分をリチウムによって打ち消し、十分に電解精製効果を高め、高粘度でありながら高純度の石英ガラス材を製造する。 Therefore, the method of the present invention uses quartz powder containing both aluminum and lithium, and increases the viscosity of the glass with aluminum, while lowering the electrical resistance with lithium and enhancing the purification effect by making the metal ions easy to move. . That is, the increase in electrical resistance due to aluminum is canceled out by lithium, the effect of electrolytic purification is sufficiently enhanced, and a high-purity quartz glass material with high viscosity is produced.

本発明の上記製造方法は、回転モールド法による石英ガラスルツボの製造において有用である。すなわち、モールド内表面に堆積した石英原料粉をアーク溶融し、あるいは石英原料粉をモールド内表面に供給しながらアーク溶融して石英ガラスルツボを製造する方法において、アルミニウムとリチウムを含有した石英粉を用い、アーク溶融時に高電圧を印加してガラス化することによって、高粘度および高純度の石英ガラスルツボを製造することができる。 The production method of the present invention is useful in the production of a quartz glass crucible by a rotary mold method. That is, in a method for producing a quartz glass crucible by arc melting the quartz raw material powder deposited on the inner surface of the mold or arc melting while supplying the quartz raw material powder to the inner surface of the mold, the quartz powder containing aluminum and lithium is A high-viscosity and high-purity quartz glass crucible can be produced by vitrification by applying a high voltage during arc melting.

具体的には、例えば、回転モールドの内表面に堆積した石英原料粉をアーク溶融し、あるいは石英原料粉を回転モールドの内表面に供給しながらアーク溶融し、約１７００ ℃以上に加熱して石英粉を溶融ガラス化し、必要に応じてモールドを減圧して溶融ガラス層に含まれる気泡を外部に吸引除去する石英ガラスルツボの製造方法において、アーク溶融時の中ほどから後半にかけて、対地絶縁したモールドに数キロボルト〜２０キロボルトの高電圧を印加し、モールド(負極)に接触するルツボ外表面部分に金属不純物を濃集させる。なお、この高電圧印加の際に対地アーク電極電位を±５００Ｖ以内に保つのが好ましい。この電極電圧がこれより小さいと、モールドとの電位差が小さくなるので金属イオンの移動が鈍くなり、一方、この電極電位が大き過ぎるとモールドの絶縁が難しくなる。 Specifically, for example, the quartz raw material powder deposited on the inner surface of the rotary mold is arc-melted, or the quartz raw material powder is arc-fused while being supplied to the inner surface of the rotary mold, and heated to about 1700 ° C. or higher to produce quartz. In the quartz glass crucible manufacturing method, which melts glass into powder and decompresses the mold as necessary to suck and remove bubbles contained in the molten glass layer to the outside. A high voltage of several kilovolts to 20 kilovolts is applied to the metal, and metal impurities are concentrated on the outer surface portion of the crucible in contact with the mold (negative electrode). In addition, it is preferable to keep the ground electrode potential within ± 500 V when applying this high voltage. If this electrode voltage is smaller than this, the potential difference from the mold becomes smaller, so that the movement of metal ions becomes dull. On the other hand, if this electrode potential is too large, it becomes difficult to insulate the mold.

アーク溶融終了後、冷却して石英ガラスルツボを得る。この石英ガラスルツボの外表面部分は薄い半溶融石英ガラス層であり、この部分に上記電解精製によって引き寄せられた不純物金属イオンが濃集しているので、例えば、高圧洗浄水をルツボ外表面に吹き付けてこの外表面部分を除去し、不純物金属イオンを除去した高純度石英ガラスルツボを得ることができる。 After completion of the arc melting, the quartz glass crucible is obtained by cooling. The outer surface part of this silica glass crucible is a thin semi-melted silica glass layer, and the impurity metal ions attracted by the electrolytic purification are concentrated in this part. For example, high pressure washing water is sprayed on the outer surface of the crucible. By removing the outer surface portion of the lever, a high-purity quartz glass crucible from which impurity metal ions have been removed can be obtained.

上記電解精製において、精製効率を高めるには、モールドの内面に接触するルツボ外周部分の未溶融石英粉の電気抵抗を低くすることが重要である。未溶融石英粉層の電気抵抗が大きいと、印可電圧のほとんどが未溶融石英粉層にかかり、ガラス層の精製効率が低下する。特にアルミニウム含有量が多いと、ガラス粘度が高くなるので金属イオンが移動し難くなり、電気抵抗が高くなるので精製効果が低下する。アルミニウムはガラス粘度を上げるので高温下での形状安定性を高めるには有利であるが、電解精製効果については不利である。 In the electrolytic refining, in order to increase the refining efficiency, it is important to lower the electric resistance of the unmelted quartz powder in the outer peripheral portion of the crucible that is in contact with the inner surface of the mold. When the electric resistance of the unfused quartz powder layer is large, most of the applied voltage is applied to the unfused quartz powder layer, and the purification efficiency of the glass layer is lowered. In particular, when the aluminum content is high, the glass viscosity increases, so that the metal ions are difficult to move, and the electrical resistance is increased, so that the purification effect is lowered. Aluminum increases the glass viscosity, which is advantageous for increasing the shape stability at high temperatures, but is disadvantageous for the effect of electrolytic purification.

そこで、本発明は、アルミニウムと共にリチウムを含有した石英粉を用い、アルミニウムによってガラスの粘度を高める一方、リチウムによって電気抵抗を下げ、アルミニウムによる電気抵抗の増加分をリチウムによって打ち消し、十分に電解精製効果を高め、高粘度でありながら高純度の石英ガラス材を製造する。 Therefore, the present invention uses quartz powder containing lithium together with aluminum, and increases the viscosity of the glass with aluminum, while lowering the electric resistance with lithium, counteracting the increase in electric resistance with aluminum with lithium, and sufficiently effecting electrolytic purification To produce a high-purity quartz glass material with high viscosity.

なお、電解初期の未溶融石英粉の電気抵抗が低下すれば、ガラス間の電位差が大きいのでアルカリ金属等は容易に移動してルツボ外周部分の未溶融ないし半溶融の石英粉層に集まる。この移動したアルカリ金属等によってルツボ外周部分の電気抵抗はさらに下がるので電解効率が向上する。 If the electric resistance of the unmelted quartz powder at the initial stage of electrolysis decreases, the potential difference between the glasses is large, so that alkali metal or the like easily moves and collects in the unmelted or semi-melted quartz powder layer in the outer periphery of the crucible. This moved alkali metal or the like further reduces the electric resistance of the outer periphery of the crucible, so that the electrolysis efficiency is improved.

石英粉に含まれるアルミニウム濃度は５〜４５ppmが適当である。石英粉に含まれるアルミニウムは電解精製時に移動せず、この濃度のアルミニウムを含有することによって、１５００℃で９.６×１０9ポイズ以上のガラス粘度を得ることができる。このアルミニウム濃度が５ppmより少ないとガラス層の粘度が十分ではない。なお、アルミニウム濃度が４５ppmを上回ると電解精製時にアルカリ金属イオンが移動し難くなり、精製効果が低下す。 The aluminum concentration contained in the quartz powder is suitably 5 to 45 ppm. Aluminum contained in the quartz powder does not move during electrolytic purification, and by containing this concentration of aluminum, a glass viscosity of 9.6 × 10 9 poise or more can be obtained at 1500 ° C. When the aluminum concentration is less than 5 ppm, the viscosity of the glass layer is not sufficient. If the aluminum concentration exceeds 45 ppm, it becomes difficult for alkali metal ions to move during electrolytic purification, and the purification effect decreases.

一方、リチウム濃度はアルミニウム濃度の２％以上が適当である。リチウム濃度がアルミニウム濃度の２％より少ないとアルミニウムに起因する電気抵抗の増加分を十分に打ち消すことができない。なお、リチウム濃度はアルミニウムに起因する電気抵抗の増加分を十分に打ち消すことができる濃度であれば良いが、リチウム濃度が多少高くても電解精製によって除去できるのでかまわない。 On the other hand, the lithium concentration is suitably 2% or more of the aluminum concentration. If the lithium concentration is less than 2% of the aluminum concentration, the increase in electrical resistance caused by aluminum cannot be sufficiently canceled out. Note that the lithium concentration may be a concentration that can sufficiently cancel the increase in electrical resistance caused by aluminum, but may be removed by electrolytic purification even if the lithium concentration is somewhat high.

一方、電解精製後のリチウム濃度はアルミニウム濃度の１％以下であることが好ましい。電解精製後のリチウム濃度がこれよりも高いと、ガラスの粘度を下げ、変形量が大きくなる。リチウム濃度がアルミニウム濃度の１％以下になるように電解を行えば良い。リチウムはアルカリ金属のなかでも移動速度が速いので、リチウムを指標としてアルカリ金属残留量の傾向を把握することができる。リチウム濃度がアルミニウム濃度の１％よりも多いときは電解精製が十分ではなく、従って、残留するアルカリ金属によってガラス粘度が低下する傾向を示す。 On the other hand, the lithium concentration after electrolytic purification is preferably 1% or less of the aluminum concentration. If the lithium concentration after electrolytic purification is higher than this, the viscosity of the glass is lowered and the deformation becomes large. Electrolysis may be performed so that the lithium concentration is 1% or less of the aluminum concentration. Since lithium has a high movement speed among alkali metals, the tendency of the remaining amount of alkali metal can be grasped using lithium as an index. When the lithium concentration is higher than 1% of the aluminum concentration, the electrolytic purification is not sufficient, and thus the glass viscosity tends to decrease due to the remaining alkali metal.

上記濃度のアルミニウムとリチウムを含有した石英粉はルツボの外周部分に用いるのが好ましい。ルツボ外周部分に粘度の高いガラス層を形成することにより、高温下で形状不良を生じないルツボを得ることができ、また、電解精製によってルツボ内周部分のアルカリ金属等が除去されるのでルツボ内周部分が高純度のルツボを得ることができる。なお、ルツボ内周部分の純度を高めるには合成石英粉を用いるのが有利である。 Quartz powder containing aluminum and lithium at the above concentrations is preferably used in the outer peripheral portion of the crucible. By forming a glass layer with high viscosity on the outer periphery of the crucible, a crucible that does not cause shape defects at high temperatures can be obtained, and the alkali metal and the like in the inner periphery of the crucible are removed by electrolytic refining. A high-purity crucible can be obtained at the periphery. In order to increase the purity of the inner peripheral portion of the crucible, it is advantageous to use synthetic quartz powder.

本発明の製造方法によれば、高温下での粘度が高く、かつアルカリ金属等の不純物が少ない高純度の石英ガラス材、とくに高純度石英ガラスルツボを得ることができる。具体的には、例えば、ルツボ外周部分の１５００℃での粘度が９.６×１０9ポイズ以上の高粘度および高純度の石英ガラスルツボを得ることができる。このルツボは、シリコン単結晶引き上げ時に１５００℃付近の高温下においても形状不良を生じることがなく、またルツボ内周部分のアルカリ金属含有量が少ないので、結晶転位が少ない高純度のシリコン単結晶を引き上げることができる。従って、引き上げ時間の長い大型ルツボであっても、単結晶化率の高い高純度の単結晶シリコンを引き上げることができる。 According to the production method of the present invention, it is possible to obtain a high-purity quartz glass material, particularly a high-purity quartz glass crucible, which has a high viscosity at a high temperature and has few impurities such as alkali metals. Specifically, for example, a high-viscosity and high-purity quartz glass crucible having a viscosity at 1500 ° C. of the outer peripheral portion of the crucible of 9.6 × 10 9 poises or more can be obtained. This crucible does not cause a shape defect even at a high temperature around 1500 ° C. when pulling up the silicon single crystal, and since the content of alkali metal in the inner peripheral portion of the crucible is small, a high-purity silicon single crystal with few crystal dislocations is used. Can be raised. Therefore, even a large crucible with a long pulling time can pull high-purity single crystal silicon with a high single crystallization rate.

〔実施例〕
以下、本発明を実施例および比較例によって具体的に示す。表１に示す製造条件に従い、回転モールドの内周面に石英粉を堆積し、これをアーク溶融して石英ガラスルツボを製造した。使用した石英粉のアルミニウム濃度とリチウム濃度、および製造した石英ガラスルツボを用いてシリコン単結晶の引き上げを行った。この結果を表１にまとめて示した。 〔Example〕
Hereinafter, the present invention will be specifically described by Examples and Comparative Examples. According to the manufacturing conditions shown in Table 1, quartz powder was deposited on the inner peripheral surface of the rotary mold, and this was arc-melted to produce a quartz glass crucible. The silicon single crystal was pulled up using the aluminum concentration and lithium concentration of the quartz powder used and the quartz glass crucible produced. The results are summarized in Table 1.

表１に示すように、本発明に係る石英ガラスルツボ（No.１〜No.４）は何れも使用時の変形量が格段に小さく、また単結晶化率が何れも８０％以上である。一方、比較試料No.５、No.６は電解精製が不十分であるため、精製後のＬｉ/Ａｌ比が１％より高く、このためガラス粘度が低下して変形量が大きくなる。因みに、単結晶引き上げは高温下で長時間行うので、ガラス粘度が僅かに低下しても変形量は著しく大きくなる。比較試料No.７、No.８は原料石英粉のチウム量が少なく、かつ精製後のＬｉ/Ａｌ比が１％より高いため、変形量が大きい。また、比較試料No.９は原料石英粉のアルミニウム量が少ないため変形量が大きい。変形量が２８mm以上のものは引き上げを中止した。比較試料は何れも変形量が大きく、一部は引き上げを中止し、引き上げを続行したものでも単結晶化率が大幅に低い。   As shown in Table 1, all of the quartz glass crucibles (No. 1 to No. 4) according to the present invention have a remarkably small amount of deformation during use, and all have a single crystallization rate of 80% or more. On the other hand, Comparative Samples No. 5 and No. 6 are insufficiently electrolytically purified, so that the Li / Al ratio after purification is higher than 1%, so that the glass viscosity is lowered and the deformation is increased. Incidentally, since the single crystal pulling is performed at a high temperature for a long time, even if the glass viscosity is slightly lowered, the deformation amount is remarkably increased. Comparative samples No. 7 and No. 8 have a large amount of deformation because the raw material quartz powder has a small amount of thium and the Li / Al ratio after purification is higher than 1%. Further, Comparative Sample No. 9 has a large amount of deformation because the amount of aluminum in the raw material quartz powder is small. Lifting was stopped when the amount of deformation was 28 mm or more. All of the comparative samples have a large deformation amount, and some of the comparative samples have a significantly low single crystallization rate even when the pulling is stopped and the pulling is continued.

Figure 2006016240
Figure 2006016240

Claims (6)

石英粉を加熱してガラス化する際に、高電圧を印加して金属不純物を負極側に集めて除去することによって高純度の石英ガラス材を得る電解精製による製造方法において、アルミニウムとリチウムを含有した石英粉を用い、アルミニウムによってガラスの粘度を高める一方、リチウムによって電気抵抗を下げて精製効果を高めることを特徴とする高粘度および高純度の石英ガラス材の製造方法。
In the manufacturing method by electrolytic refining to obtain high purity quartz glass material by applying high voltage to collect and remove metal impurities on the negative electrode side when quartz powder is heated to vitrify, contains aluminum and lithium A method for producing a high-viscosity and high-purity quartz glass material, characterized in that, using the quartz powder, the viscosity of the glass is increased by aluminum, while the electrical resistance is decreased by lithium and the purification effect is increased.
モールド内表面に堆積した石英原料粉をアーク溶融し、あるいは石英原料粉をモールド内表面に供給しながらアーク溶融して石英ガラスルツボを製造する方法において、アルミニウムとリチウムを含有した石英粉を用い、アーク溶融時に高電圧を印加してガラス化することによって、高粘度および高純度の石英ガラスルツボを製造する請求項１に記載する製造方法。
In a method for producing a quartz glass crucible by arc melting the quartz raw material powder deposited on the inner surface of the mold, or arc melting while supplying the quartz raw material powder to the inner surface of the mold, a quartz powder containing aluminum and lithium is used, The manufacturing method according to claim 1, wherein a high-viscosity and high-purity quartz glass crucible is manufactured by vitrification by applying a high voltage during arc melting.
少なくともルツボの外周部分がアルミニウム濃度５〜４５ppmおよびリチウム濃度がアルミニウム濃度の２％以上の石英粉を用いて製造されたルツボであって、１５００℃での粘度が９.６×１０9ポイズ以上であることを特徴とする石英ガラスルツボ。
A crucible manufactured using quartz powder in which at least the outer peripheral portion of the crucible has an aluminum concentration of 5 to 45 ppm and a lithium concentration of 2% or more of the aluminum concentration, and the viscosity at 1500 ° C. is 9.6 × 10 9 poise or more. A quartz glass crucible characterized by being.
ルツボの外周部分がアルミニウム濃度５〜４５ppmおよびリチウム濃度がアルミニウム濃度の２％以上の石英粉を用い、ルツボ内周部分が合成石英粉を用いて製造された請求項３の石英ガラスルツボ。
The quartz glass crucible according to claim 3, wherein the outer peripheral portion of the crucible is made of quartz powder having an aluminum concentration of 5 to 45 ppm and the lithium concentration is 2% or more of the aluminum concentration, and the inner peripheral portion of the crucible is made of synthetic quartz powder.
電解精製後のルツボ外周部分のリチウム濃度がアルミニウム濃度の１％以下である請求項３または４に記載する石英ガラスルツボ。
The quartz glass crucible according to claim 3 or 4, wherein the lithium concentration in the outer periphery of the crucible after electrolytic purification is 1% or less of the aluminum concentration.
請求項３〜５の何れかに記載する石英ガラスルツボを用いたシリコン単結晶の引き上げ方法。


A method for pulling a silicon single crystal using the quartz glass crucible according to claim 3.


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CN113897669B (en) * 2016-09-13 2023-11-07 胜高股份有限公司 Quartz glass crucible and method for producing same
JP2019094232A (en) * 2017-11-24 2019-06-20 クアーズテック株式会社 Quartz glass crucible and method for manufacturing quartz glass crucible
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