JP4726138B2 - Quartz glass crucible - Google Patents

Quartz glass crucible Download PDF

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JP4726138B2
JP4726138B2 JP2006356391A JP2006356391A JP4726138B2 JP 4726138 B2 JP4726138 B2 JP 4726138B2 JP 2006356391 A JP2006356391 A JP 2006356391A JP 2006356391 A JP2006356391 A JP 2006356391A JP 4726138 B2 JP4726138 B2 JP 4726138B2
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crucible
single crystal
quartz glass
silicon single
pulling
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JP2008162865A (en
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弘史 岸
稔 神田
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Sumco Corp
Japan Super Quartz Corp
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Japan Super Quartz Corp
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Description

本発明は、シリコン単結晶引上げに用いられ、シリコン単結晶のピンホールが少ない石英ガラスルツボに関する。   The present invention relates to a quartz glass crucible used for pulling a silicon single crystal and having few pinholes in the silicon single crystal.

シリコンウエハーなどの半導体材料として使用されるシリコン単結晶は主にCZ法によって製造されている。この製造方法は、石英ガラスルツボに入れた多結晶シリコンを加熱溶融してシリコン融液とし、高温下、この液面に浸した種結晶を中心にして単結晶を成長させ、これを除々に引き上げて棒状の単結晶に成長させる方法である。   Silicon single crystals used as semiconductor materials such as silicon wafers are mainly manufactured by the CZ method. In this manufacturing method, polycrystalline silicon placed in a quartz glass crucible is heated and melted to form a silicon melt, and at a high temperature, a single crystal is grown around a seed crystal immersed in the liquid surface, and this is gradually pulled up. It is a method of growing into a rod-like single crystal.

引上げ中のシリコン単結晶は、ルツボの中心でシリコン融液に常時浸かっているので、ルツボの内表面から浮き上がってきた気泡がシリコン単結晶とシリコン融液の界面に付着すると、そのままシリコン単結晶にピンホールとして取り込まれる。ピンホールとはシリコン単結晶中に含まれる気泡である。シリコン単結晶のスライス工程において、ピンホールが発見されたウエハーは廃棄されるので、ピンホールは製品歩留り低下の原因の一つになっている。   Since the silicon single crystal being pulled is constantly immersed in the silicon melt at the center of the crucible, if the bubbles floating from the inner surface of the crucible adhere to the interface between the silicon single crystal and the silicon melt, the silicon single crystal remains as it is. Captured as a pinhole. A pinhole is a bubble contained in a silicon single crystal. In the silicon single crystal slicing process, the wafer in which the pinhole is found is discarded, and the pinhole is one of the causes of the product yield reduction.

シリコン単結晶のピンホールを防止する技術として、石英ルツボに入れた多結晶シリコン原料を一定範囲の炉内圧で溶融し、これより高い炉内圧でシリコン単結晶の引上を行う方法が知られている(特許文献1)。また、一定範囲の炉内圧力で原料溶解を行った後に原料溶解に続く単結晶引上げを、溶解時の炉内圧力より低い炉内圧力で行う方法が知られている(特許文献2)。
特開平05−9097号公報 特開2000−169287号公報
As a technique for preventing pinholes in a silicon single crystal, a method is known in which a polycrystalline silicon raw material put in a quartz crucible is melted at a furnace pressure within a certain range, and the silicon single crystal is pulled at a higher furnace pressure. (Patent Document 1). In addition, a method is known in which the single crystal pulling subsequent to the raw material melting is performed at a furnace pressure lower than the furnace pressure at the time of melting after the raw material is melted at a certain range of furnace pressure (Patent Document 2).
Japanese Patent Laid-Open No. 05-9097 JP 2000-169287 A

従来の上記ピンホール防止方法は、何れもシリコン単結晶の引上げを行う際に、多結晶シリコンの溶融時の炉内圧力と引上げ時の炉内圧力を調整して、シリコン単結晶に気泡が巻き込まれるのを防止する方法であるが、原料の多結晶シリコンは石英ガラスルツボ中で溶融され、該ルツボ中の溶融シリコンからシリコン単結晶を引上げるので、石英ガラスルツボの影響は大きい。しかし、従来は石英ガラスルツボの性状がピンホールに与える影響については十分に検討されていない。   In any of the above-mentioned conventional pinhole prevention methods, when pulling up a silicon single crystal, by adjusting the pressure in the furnace when melting polycrystalline silicon and the pressure in the furnace when pulling up, bubbles are involved in the silicon single crystal. The raw material polycrystalline silicon is melted in a quartz glass crucible, and the silicon single crystal is pulled up from the molten silicon in the crucible, so the influence of the quartz glass crucible is great. However, the influence of the properties of the quartz glass crucible on the pinhole has not been sufficiently studied.

本発明は、シリコン単結晶のピンホールを防止する石英ガラスルツボについて、その条件を特定したものであり、シリコン単結晶のピンホールが少ない石英ガラスルツボを提供する。   The present invention specifies the conditions of a quartz glass crucible for preventing pinholes in a silicon single crystal, and provides a quartz glass crucible with few pinholes in a silicon single crystal.

本発明は以下の構成を有する石英ガラスルツボに関する。
(1)シリコン単結晶引上げ用の石英ガラスルツボであって、非晶質シリカが結晶化した結晶質シリカの面積をルツボ内面積の10%以下に抑制することによって、シリコン単結晶のピンホールを防止したことを特徴とする石英ガラスルツボ。
(2)ルツボ内表面の開気泡による凹部の密度を0.01〜0.2個/mm2に制限してシリコン単結晶のピンホールを防止したことを特徴とする石英ガラスルツボ。
(3)上記(1)または上記(2)の石英ガラスルツボを使用し、ルツボ内表面の溶損速度を20μm/hr以下に抑制してシリコン単結晶の引上げを行うことによって、ピンホールを防止したことを特徴とするシリコン単結晶の引き上げ方法。
The present invention relates to a quartz glass crucible having the following configuration.
(1) A quartz glass crucible for pulling up a silicon single crystal, and by suppressing the area of crystalline silica crystallized from amorphous silica to 10% or less of the area inside the crucible, A quartz glass crucible characterized by prevention.
(2) A quartz glass crucible characterized in that pinholes of silicon single crystals are prevented by limiting the density of recesses due to open bubbles on the inner surface of the crucible to 0.01 to 0.2 pieces / mm 2 .
(3) Using the quartz glass crucible of (1) or (2) above, suppressing the melting rate of the inner surface of the crucible to 20 μm / hr or less and pulling up the silicon single crystal prevents pinholes A method for pulling a silicon single crystal characterized by the above.

本発明の第一態様は、非晶質シリカが結晶化した結晶質シリカの面積を少なく(10%以下)した石英ガラスルツボであり、上記結晶質シリカの面積を少なくすることにより、このルツボを使用したときのピンホールの発生を防止したものである。ルツボ内表面に非晶質シリカが結晶化した結晶質シリカが存在すると、多結晶シリコンが溶融され、ルツボにシリコン融液が満たされる際に、ルツボ内表面に雰囲気ガスであるアルゴンガスの気泡が残りやすくなる。このためシリコン融液に上記気泡が混入し、ピンホールの原因になる。そこで、本発明の石英ガラスルツボは、内表面の結晶転位による結晶質シリカの面積を少なくしてルツボ内表面に気泡が付着し難くした。これによってシリコン融液に混入する気泡が少なくなり、ピンホールを防止することができる。   A first aspect of the present invention is a quartz glass crucible in which the area of crystalline silica obtained by crystallizing amorphous silica is reduced (10% or less). By reducing the area of the crystalline silica, the crucible is This prevents pinholes from occurring when used. When crystalline silica in which amorphous silica is crystallized exists on the inner surface of the crucible, when polycrystalline silicon is melted and the silicon melt is filled in the crucible, bubbles of argon gas, which is an atmospheric gas, are formed on the inner surface of the crucible. It becomes easy to remain. For this reason, the bubbles are mixed into the silicon melt, causing pinholes. Therefore, the quartz glass crucible of the present invention reduces the area of crystalline silica due to crystal dislocations on the inner surface and makes it difficult for bubbles to adhere to the inner surface of the crucible. As a result, bubbles mixed in the silicon melt are reduced and pinholes can be prevented.

本発明の第二態様は、ルツボ内表面の開気泡による凹部を一定密度(0.01〜0.2個/mm2)にした石英ガラスルツボであり、上記凹部の存在によって、このルツボを使用したときのピンホールの発生を防止したものである。ルツボ内表面に一定密度の凹部が存在すると、シリカガラスとシリコン融液との反応によって生じたSiOガスの突沸が抑制され、大きな気泡の発生が少なくなるので、シリコン単結晶に取り込まれる気泡量が減少し、ピンホールを防止することができる。 The second aspect of the present invention is a quartz glass crucible in which concave portions due to open bubbles on the inner surface of the crucible have a constant density (0.01 to 0.2 pieces / mm 2 ), and this crucible is used due to the presence of the concave portions. This prevents the generation of pinholes. If there are recesses with a constant density on the inner surface of the crucible, the bumping of SiO gas generated by the reaction between the silica glass and the silicon melt is suppressed, and the generation of large bubbles is reduced, so the amount of bubbles taken into the silicon single crystal is reduced. It can be reduced and pinholes can be prevented.

本発明の第三態様は、上記第一態様ないし第二態様の石英ルツボを使用したシリコン単結晶の引き上げ方法であり、ルツボ内表面の溶損速度を20μm/hr以下に抑制することによってシリコン単結晶のピンホールを防止することができる。   A third aspect of the present invention is a method for pulling a silicon single crystal using the quartz crucible of the first aspect or the second aspect described above. By suppressing the melting rate of the inner surface of the crucible to 20 μm / hr or less, the silicon single crystal is pulled. Crystal pinholes can be prevented.

以下、本発明を実施形態に即し具体的に説明する。
本発明の第一態様の石英ガラスルツボは、シリコン単結晶引上げ用の石英ガラスルツボであって、非晶質シリカが結晶化した結晶質シリカの面積をルツボ内面積の10%以下に抑制することによって、シリコン単結晶のピンホールを防止したことを特徴とする石英ガラスルツボである。
Hereinafter, the present invention will be specifically described in accordance with embodiments.
The quartz glass crucible according to the first aspect of the present invention is a quartz glass crucible for pulling up a silicon single crystal, and the area of crystalline silica crystallized from amorphous silica is suppressed to 10% or less of the area inside the crucible. The quartz glass crucible is characterized by preventing pinholes in the silicon single crystal.

ルツボ内表面に非晶質シリカが結晶化した結晶質シリカが存在すると、多結晶シリコンが溶融され、ルツボにシリコン融液が満たされる際に、ルツボ内表面に雰囲気ガスであるアルゴンガスの気泡が残り易くなる。このためシリコン融液に上記気泡が混入し、ピンホールの原因になる。   When crystalline silica in which amorphous silica is crystallized exists on the inner surface of the crucible, when polycrystalline silicon is melted and the silicon melt is filled in the crucible, bubbles of argon gas, which is an atmospheric gas, are formed on the inner surface of the crucible. It becomes easy to remain. For this reason, the bubbles are mixed into the silicon melt, causing pinholes.

本発明の上記石英ガラスルツボは、非晶質シリカが結晶転位した結晶質シリカの面積を全内表面の10%以下に制限してルツボ内表面に気泡が付着し難くし、これによってシリコン融液に混入する気泡を低減した。上記結晶質シリカの面積が10%を上回ると付着する気泡が増えるので好ましくない。非晶質シリカの結晶転位による結晶質シリカの量を減少するには、石英ガラスの構造を切断・再配列を促進する不純物を減少させれば良い。   The quartz glass crucible of the present invention limits the area of crystalline silica in which amorphous silica has undergone crystal dislocation to 10% or less of the entire inner surface, thereby making it difficult for bubbles to adhere to the inner surface of the crucible. Air bubbles mixed in were reduced. If the area of the crystalline silica exceeds 10%, the number of attached bubbles increases, which is not preferable. In order to reduce the amount of crystalline silica due to crystal dislocation of amorphous silica, impurities that promote cutting and rearrangement of the structure of quartz glass may be reduced.

なお、シリコンとルツボのシリカガラスとの反応によってルツボ内表面に析出する着色斑点(これをブラウンリングと云う)も結晶質シリカであるが、結晶構造が不完全(SiO2−X)であり、上記結晶転位による結晶質シリカとは実質的に異なる。従って、本発明ではブラウンリングの面積は上記10%に含めない。 In addition, although the colored spot (this is called a brown ring) deposited on the inner surface of the crucible by the reaction between silicon and the silica glass of the crucible is also crystalline silica, the crystal structure is incomplete (SiO 2 -X), It is substantially different from crystalline silica by the above crystal dislocation. Therefore, in the present invention, the area of the brown ring is not included in the above 10%.

本発明の第二態様の石英ガラスルツボは、ルツボ内表面の開気泡による凹部の密度を0.01〜0.2個/mm2に制限してシリコン単結晶のピンホールを防止したことを特徴とする石英ガラスルツボである。 The quartz glass crucible according to the second aspect of the present invention is characterized in that the density of recesses due to open bubbles on the inner surface of the crucible is limited to 0.01 to 0.2 pieces / mm 2 to prevent pinholes in the silicon single crystal. It is a quartz glass crucible.

シリコン単結晶の引上げ中に、温度および圧力の変化によってSiOガスの沸騰が生じることがあるが、ルツボ内表面に一定密度の適度な大きさの凹部が存在すると、シリカガラスとシリコン融液との反応によって生じたSiOガスの突沸が抑制される。特にルツボ底面に凹部が一定密度存在するのが好ましい。凹部は主に開気泡によって形成されたものであり、概ね0.2〜2.0mmの大きさを有している。開気泡による凹部の密度が、0.01個/mm2より少ないと、その効果がなく、0.2個/mm2より多いと、気泡の破裂する際に発生するパーティクルが、シリコン単結晶の歩留りを低下させる。 During pulling of the silicon single crystal, boiling of SiO gas may occur due to changes in temperature and pressure, but if there are recesses of moderate size with a certain density on the inner surface of the crucible, silica glass and silicon melt Bumping of SiO gas generated by the reaction is suppressed. In particular, it is preferable that the recesses exist at a constant density on the bottom of the crucible. The concave portion is mainly formed by open bubbles and has a size of about 0.2 to 2.0 mm. If the density of the recesses due to the open bubbles is less than 0.01 / mm 2 , the effect is not effective. If the density is more than 0.2 / mm 2 , the particles generated when the bubbles burst are formed of silicon single crystals. Reduce yield.

ルツボ内表面の開気泡による凹部は、シリコン単結晶引上げ中にルツボ内表面が溶損して内部気泡が表面に現れることによって形成されるので、溶損範囲に含まれる気泡数を上記密度に制御すればよい。気泡数はルツボ製造時の真空引きの条件などを調整して制御することができる。   The recesses due to open bubbles on the inner surface of the crucible are formed by melting the inner surface of the crucible during the pulling of the silicon single crystal and causing the internal bubbles to appear on the surface. Therefore, the number of bubbles included in the melting range is controlled to the above density. That's fine. The number of bubbles can be controlled by adjusting the vacuuming conditions during crucible manufacturing.

本発明は上記石英ガラスルツボを使用し、ルツボ内表面の溶損速度を20μm/hr以下に抑制してシリコン単結晶を引き上げる方法を含む。上記石英ガラスルツボを使用し、ルツボ内表面の溶損速度を20μm/hr以下に抑制してシリコン単結晶を引き上げることによって、シリコン単結晶のピンホールを防止することができる。   The present invention includes a method of pulling up a silicon single crystal by using the above-mentioned quartz glass crucible and suppressing the melting rate of the inner surface of the crucible to 20 μm / hr or less. By using the quartz glass crucible and suppressing the melting rate of the inner surface of the crucible to 20 μm / hr or less and pulling up the silicon single crystal, pinholes in the silicon single crystal can be prevented.

SiOガスは主にシリコン融液とルツボのシリカガラスとの反応によって生じる。従って、ルツボ内表面の溶損速度を上記範囲に制限することによって、SiOガスの発生を抑制し、シリコン単結晶のピンホールを防止することができる。ルツボ内表面の溶損速度が上記範囲より早いと、SiOガスの発生を抑制する効果が不十分である。   The SiO gas is mainly generated by the reaction between the silicon melt and the silica glass of the crucible. Therefore, by limiting the melting rate of the inner surface of the crucible to the above range, generation of SiO gas can be suppressed and pinholes in the silicon single crystal can be prevented. If the melting rate of the inner surface of the crucible is faster than the above range, the effect of suppressing the generation of SiO gas is insufficient.

ルツボ内表面の溶損速度の低いルツボを得るには、石英ガラスの粘度を上げることが重要である。具体的には、より高温で溶融加熱し、OH基濃度を低下させる、あるいは不純物を低減した原料粉を用いるなどの方法によってルツボ内表面の溶損速度の低いルツボを得ることができる。また、ルツボ内表面の溶損速度はシリコン単結晶の引上げ条件によっても異なるが、ルツボ内表面の溶損速度の低いルツボを用い、引上げ条件を調整してルツボ内表面の溶損速度が20μm/hr以下になるようにすればよい。   In order to obtain a crucible with a low melting rate on the inner surface of the crucible, it is important to increase the viscosity of the quartz glass. Specifically, a crucible having a low melting rate on the inner surface of the crucible can be obtained by a method such as melting and heating at a higher temperature to lower the OH group concentration or using raw material powder with reduced impurities. Moreover, although the melting rate of the inner surface of the crucible varies depending on the pulling conditions of the silicon single crystal, a crucible with a lower melting rate of the inner surface of the crucible is used and the pulling condition is adjusted so that the melting rate of the inner surface of the crucible is 20 μm / It should be less than hr.

以下に本発明の実施例を比較例と共に示す。
〔実施例1〜3、比較例1〜6〕
表1に示す性状の石英ガラスルツボ(口径28インチ)を用い、炉内圧力40torr、雰囲気アルゴンガス、引上げ時間100hrとして、シリコン単結晶を引き上げた。この結果を表1に示した。
Examples of the present invention are shown below together with comparative examples.
[Examples 1 to 3, Comparative Examples 1 to 6]
Using a quartz glass crucible having the characteristics shown in Table 1 (with a diameter of 28 inches), the silicon single crystal was pulled at a furnace pressure of 40 torr, an atmospheric argon gas, and a pulling time of 100 hours. The results are shown in Table 1.

なお、表1において、内面結晶化率(%)は非結晶シリコンの結晶化による結晶シリコンのルツボ内表面に占める割合である。開気泡密度(個/mm2)は開気泡による凹部のルツボ内表面密度である。溶解速度(μm/h)はルツボ内表面の肉厚が減少する速度である。ピンホール含有率(%)はウエハー1枚に含まれるピンホール数である。実施例1〜3は本発明の石英ガラスルツボであり、比較例1〜6は本発明の範囲を外れる石英ガラスルツボである。 In Table 1, the inner surface crystallization rate (%) is the ratio of the crystalline silicon to the inner surface of the crucible due to the crystallization of the amorphous silicon. The open cell density (pieces / mm 2 ) is the surface density inside the crucible of the recess due to open cells. The dissolution rate (μm / h) is the rate at which the inner wall thickness of the crucible decreases. The pinhole content (%) is the number of pinholes contained in one wafer. Examples 1 to 3 are quartz glass crucibles of the present invention, and Comparative Examples 1 to 6 are quartz glass crucibles outside the scope of the present invention.

内面結晶化率は、使用前後のルツボ内表面を肉眼観察し、結晶化した面積を測定することにより、算出した。
開気泡密度は、ルツボ内面を偏光顕微鏡観察により測定した。
溶解速度は、使用前後のルツボ重量差あるいは透明層の厚み差などから算出した。
ピンホール含有率は、スライスした全てのシリコンウエハーを肉眼観察し、算出した。
The inner surface crystallization rate was calculated by observing the inner surface of the crucible before and after use with the naked eye and measuring the crystallized area.
The open cell density was measured by observing the inner surface of the crucible with a polarizing microscope.
The dissolution rate was calculated from the difference in crucible weight before and after use or the difference in thickness of the transparent layer.
The pinhole content was calculated by visually observing all sliced silicon wafers.

表1に示すように、本発明の石英ガラスルツボを用いた場合には、シリコン単結晶のピンホールが格段に少なく、シリコン単結晶の製造歩留りが高い。一方、比較例は何れもシリコン単結晶のピンホールが多く、シリコン単結晶の製造歩留りが低い。   As shown in Table 1, when the quartz glass crucible of the present invention is used, the number of silicon single crystal pinholes is remarkably small, and the production yield of the silicon single crystal is high. On the other hand, all of the comparative examples have many silicon single crystal pinholes, and the production yield of the silicon single crystal is low.

Figure 0004726138
Figure 0004726138

Claims (1)

石英ガラスルツボを使用してシリコン単結晶の引上げを行う工程を備え、It includes a process of pulling up a silicon single crystal using a quartz glass crucible,
前記石英ガラスルツボは、使用後における、非晶質シリカが結晶化した結晶質シリカの面積がルツボ内面積の10%以下であり、In the quartz glass crucible, the area of the crystalline silica after the amorphous silica crystallized after use is 10% or less of the area inside the crucible,
前記引き上げ時のルツボ内表面の溶損速度が20μm/hr以下であり、The melting rate of the inner surface of the crucible during the pulling is 20 μm / hr or less,
前記引き上げ時の溶損範囲の全体において、ルツボ内表面の開気泡による凹部の密度が0.01〜0.2個/mmThe density of the recesses due to open bubbles on the inner surface of the crucible is 0.01 to 0.2 pieces / mm in the entire melting range during the pulling. 22 であることを特徴とする、シリコン単結晶の引き上げ方法。A method for pulling a silicon single crystal, characterized in that
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JP5042971B2 (en) * 2008-11-28 2012-10-03 株式会社Sumco Silica glass crucible for pulling silicon single crystal and manufacturing method thereof
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JPH04202086A (en) * 1990-11-29 1992-07-22 Toshiba Ceramics Co Ltd Quartz glass crucible for pulling up silicon single crystal
JPH10338595A (en) * 1997-06-09 1998-12-22 Sumitomo Metal Ind Ltd Quartz crucible and method for evaluating the quartz crucible
JP2001342028A (en) * 2000-05-30 2001-12-11 Mitsubishi Material Quartz Kk Quartz glass crucible and its evaluating method

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
JPH04202086A (en) * 1990-11-29 1992-07-22 Toshiba Ceramics Co Ltd Quartz glass crucible for pulling up silicon single crystal
JPH10338595A (en) * 1997-06-09 1998-12-22 Sumitomo Metal Ind Ltd Quartz crucible and method for evaluating the quartz crucible
JP2001342028A (en) * 2000-05-30 2001-12-11 Mitsubishi Material Quartz Kk Quartz glass crucible and its evaluating method

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