經濟部智慧財產局員工消費合作社印製 526298 A7 B7____ 五、發明説明（1 ) 〔技術領域〕 本發明係關於一種石英坩堝以及使用該坩堝之單結晶 製造方法者。更詳言之，係關於抑制撈起單結晶時之石英 坩堝之變形，抑制石英坩堝內表面之變形所引起之劣化， 以求其長W叩化，问時，維持較筒之單結晶之無轉位化率 之狀態下，能夠長時間撈起單晶體之石英坩堝，以及使用 該石央ί甘渦之單結晶製造方法者。 〔背景技術〕 茲以矽作爲單結晶爲例來說明如下。 近年來，隨著砂晶圓之大口徑化，要撈起大口徑之矽 單結晶所使用之坩堝也一直大口徑化，現時是坩堝之□徑 在2 2〜24英寸（558 · 8〜609 · 6mm)之範 圍者成爲主流。隨著近年來石英ί甘渦之大口徑化，石英ί甘 堝之熱負荷也變大，例如，要撈上8英寸結晶時，其接觸 熔化液體面之溫度比6英寸結晶高出攝氏5度以上，石英 坩堝內表面之熔損速度增加5 0 %以上等，增加熔損量， 其結果石英增堝內表面受到破壞，難以長時間使用石英坩 堝。 製造矽單結晶用之坩堝必需要避免阻害單結晶品質之 不純物之混入，因此必然要使用石英。然後，石英坩堝則 因製造方法之不同而有透明石英玻璃坩堝及半透明石英玻 璃坩堝（以下簡稱爲透明或不透明坩堝）。半透明坩堝係 相較於透明坩堝，因含有微小的氣泡的關係，有其強度高 I紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ^ -4 - (請先閲讀背面之注意事項再填寫本頁) 、11 526298 A7 _B7 一 五、發明説明（2 ) 而容易製造大尺寸之石英坩堝，以及熱分布均勻而使溫度 均勻等之優點。由於該理由，實用上廣泛地使用半透明坩 (請先閲讀背面之注意事項再填寫本頁) 堝。 然而，矽單結晶之撈起中之石英坩堝之溫度係高達約 攝氏1 5 0 0度，如從石英之熱平衡狀態圖可明白，該溫 度區域係結晶性物質之方英石之生成區域的關係，石英係 因熱變態而容易發生方英石。據說該結晶化之原因係存在 於石英中之微量之不純物及存在於半透明玻璃坩堝中之氣 泡者。關於該氣泡部分，隨著石英坩堝之溶解，當到達內 表面時膨脹而破裂，石英片進入熔融液中，同時，在氣泡 破裂之部分發生微細的突起，成爲石英坩堝內表面變粗糙 ，而該等成爲結晶核而形成斑點狀之方英石。方英石之起 源尙未明確，然而，據說是首先形成缺氧之S i 0 2 — 5之 中間層，在其擴大之同時從其中心部開始進行方英石化， 而在高溫下，該方英石化之速度爲更快。 又按，該物質係一旦生成之後其熔點可高達攝氏 1 7 2 0度，在該矽單結晶之榜起溫度是無法使其熔化， 經濟部智慧財產苟員工消費合作社印製 變成固形物而在熔融液中漂流。撈起矽單結晶時所產生之 各種缺點係由於石英坩堝內表面之熔化導致不純物之混入 ，以及所生成之方英石爲微結晶的關係，會脫離石英坩堝 內表面所致者。然後，脫離在矽熔融液中之方英石會使所 撈起之單結晶成爲有轉位化之問題爲眾所皆知。 由於前述之理由，石英坩堝的壽命較短的關係，從生 產性及成本之兩面成爲工業上的大問題，導致單結晶之高 本紙^度適用中國國家標準（CNS ) A4規格（210X297公釐1 : 526298 A7 B7 五、發明説明（3 ) 成本。 (請先閱讀背面之注意事項存填寫本頁) 爲解決上述問題點，在日本專利申請案特開平 6 - 7 2 7 9 3號公報中有控制半透明坩堝內表面區域之 氣泡含有率的提議，然而，本質上並未消除因石英坩堝之 熔解及生成方英石結晶所引起之各種缺點。 相對之，在日本專利申請案特開平8 — 2 9 3 2號公 報中有提議在石英坩堝之內表面之厚度1 mm以內形成含 有結晶化促進劑塗敷膜或固熔層而結晶化的石英坩堝，再 者，在日本專利申請案特開平1 1 — 2 1 1 9 6號公報中 有關於在矽熔融液中添加C a 0或B a〇而育成矽單結晶 之提議。然而，兩者均爲對石英坩堝或矽熔融液混入添加 劑來成長單結晶，而添加劑係其偏析係數非常小的關係， 雖然是說被取進單結晶中，然而在所剩下之矽熔融液中之 添加劑之濃度變高，例如，用多重法所撈上之後面之單結 晶中，所取進之添加劑成爲不純物而有降低品質的可能性 〇 經濟部智慧財產局員工消費合作社印製 所謂多重法係指在撈起單結晶之後，不關掉加熱器之 電源之狀態下對所剩.下之矽熔融液追加放進多結晶原料而 撈起下一個單結晶，重復該怍業而撈起複數個單結晶而言 者。 再者，在日本專利申請案特開平9 一 5 2 7 9 1號公 報中有提議將高純度石英在攝氏1 7 5 0度以上之溫度中 予以熔融後凝固以1 0 0 %方英石化之石英材質之石英坩 堝。然而，因爲需要特殊的製造技術的關係，會發生石英 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 526298 A7 _ B7 五、發明説明（4 ) 坩堝之成本極端地上昇的問題。 (請先閱讀背面之注意事項再填寫本頁) 另一方面，關於使用石英玻璃之雙層構造之坩堝，在 曰本專利申請案特開平6 _ 9 2 7 7 9號公報中有提議， 將坩堝內表面實質上無氣泡而使表面層平滑，外層爲半透 明玻璃來控制氣泡之徑及氣泡之存在密度的使用石英玻璃 之雙層構造之坩堝。該石英坩堝係在撈起單結晶時，可以 把外部加熱器之熱能量均勻地傳達至石英坩堝內面全域之 同時，石英坩堝內表面之局部侵鈾所致之表面粗糙之發生 極小，且顯著地增加石英坩堝之耐熱強度。其結果，相較 於以往的石英坩堝，據說可以維持較高的單結晶化率。然 而，長時間使用時.，尤其是超過8 0小時之後，有無法維 持單結晶化率的問題存在。 〔發明之揭示〕 有鑑於上情，本發明者等經銳意硏究之結果，發現經 長時間作業時之單結果之無轉位化率與石英坩堝之小R部 之壁厚有關係，以完成本發明者。 經濟部智慧財產局員工消費合作社印製 本發明係在撈起單結晶之際，儘量抑制石英坩堝從加 熱器所受到之熱，以及所塡充之結晶原料之重及本身重量 所致之變形，以防止石英坩堝內表面之劣化，以求石英坩 堝之長壽命化爲目的。 又，本發明之目的，在於提供一種在維持單結晶之高 度無轉位化之狀態下，可長時間撈上單結晶之大口徑石英 坩堝以及使用該石英坩堝而能夠長時間撈起單結晶之單結 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 526298 A7 __B7 五、發明説明（5 ) 晶之製造方法者。 (請先閱讀背面之注意事項再填寫本頁) 本發明係爲達成前述目的所成，如第1圖所示，利用 捷克勞斯基法撈起單結晶之際所使用之石英坩堝1中，在 該石英坩堝中之直形軀幹圓筒部3之1/2部5之壁厚6 ，及連繫該直形軀幹圓筒部3與底部2之曲線部分之小R 部4之壁厚7之比率爲，在其尺寸規格中心部位呈直形軀 幹圓筒部3之壁厚6之1·5〜1.8倍爲其特徵之石英 坩堝者。 如果使用上述本發明之石英坩堝時，在長時間作業來 撈起單結晶之時間超過8 0小時以上之長時間作業中，例 如用多重法撈起之自最初之單結晶至最後之單結晶之直形 軀幹部及彎曲部爲止之無轉位化率可以維持在7 0 %以上 〇 經濟部智慧財產局員工消費合作社印製 該時，由每1立方公分含有直徑1 0〜2 5 0 //m之 氣泡2 0，0 0 0個以上之半透明石英玻璃層，及一體熔 合形成在該層內表面之無氣泡而其厚度〇 . 3 mm以上之 透明石英玻璃層所成，在前述半透明石英玻璃層中有結晶 質石英成分存在的石英坩堝爲宜。 在本發明中，形成爲上述之雙層構造之石英坩堝之結 果，能夠更可抑制坩堝內表面之侵蝕等所致之劣化而宜。 再者，該時，使用本發明之石英坩堝而撈起單結晶之 單結晶製造方法者。 如上述，使用本發明之石英ί甘渦之結果，可穩定地撈 起單結晶。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） -8 · 526298 A7 B7 五、發明説明（6 ) (請先閲讀背面之注意事項再填寫本頁) 然後，本發明之製造方法係在利用捷克勞斯基法製造 單結晶之方法中，以多重法製造複數個單結晶之際，使用 石英坩堝之直形軀幹圓筒部之1/2部之壁厚，及連繫該 直形軀幹圓筒部與底部之曲線部分之小R部之壁厚之比率 爲，在尺寸規格中心部位呈該直形軀幹圓筒部壁厚之 1 · 5〜1 · 8倍之石英坩堝，以8 0小時以上之作業時 間來撈起單·結晶爲特徵之單結晶製造方法。 如上述，本發明之製造方法爲，以多重法製造單結晶 時，雖然作業時間超過8 0小時以上也可將單結晶之無轉 位化率維持在7 0 %以上之單結晶製造方法。 如上述，本發明之石英坩堝係在使用時可提高其耐熱 性而可抑制其變形，可防止變形所致之石英坩堝內表面之 粗糙，維持平滑度，容易延長石英坩堝之壽命之同時，可 提供以維持高度之單結晶之無轉位化率之狀態下，在8 0 小時以上之長時間可撈起單結晶之大口徑石英坩堝者。 經濟部智慧財產¾員工消費合作社印製 再者，使用本發明之石英坩堝製造單結晶之結果，可 圖長時間之安定作業與生產性之提高，在工業方面而言， 非常有利的製造方法。 〔圖式之簡單說明〕 第1圖係顯示本發明之石英坩堝之槪略剖視圖。 〔元件編號之說明〕 1 石英坩堝 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9- 526298 A7 B7 五、發明説明（7 ) 6， 7 壁 厚 5 1 / 2 部 3 直 形 軀 幹圓筒部 2 底 部 4 小 尺 部 (請先閲讀背面之注意事項再填寫本頁) 〔實施發明之最佳形態〕 以往，在撈起矽單結晶時所產生之問題點爲，如前述 之石英ί甘渦內表面之溶化及方央石之生成所致，尤其是在 多重法中，撈起單結晶之後，爲撈起下一個單結晶而重復 地塡充多結晶原料，但注意到在實行該多重法期間中，矽 熔融液經常接觸於石英坩堝之底部及小R部之情形，藉由 控制小R部之壁厚來消除以往所產生之缺點者。 本發明者等爲，關於以捷克勞斯基法成長矽單結晶， 檢討長時間使用石英坩堝用之各種方法之結果，發現將石 英坩堝之小R部之厚度設定成在直形軀'幹圓筒部之1 / 2 部之厚度之約1 · 5〜Ί · 8倍時則可抑制石英坩堝內表 經濟部智慧財產局員工消費合作社印製 面之石英之方英石化及剝離者。 以下，就本發明更詳細說明如下。石英坩堝之內表面 爲，具有與矽熔融液接觸，與矽反應而熔化，或將外部之 碳加熱器之熱傳達至矽熔融液之功能。關於作業中之石英 坩堝之作業中之石英坩堝之溫度分布，通過以黑鉛加熱器 加熱之黑鉛坩堝而把熱傳達至石英坩堝的關係，小r部係 在從矽熔融液中撈起單結晶時，比底部較高溫。又按，來 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -10 - 526298 A7 B7 五、發明説明（8 ) 注意小R部係相較於石英坩堝直形軀幹圓筒部，其與矽熔 融液接觸之時間較長如前述。 (請先閲讀背面之注意事項再填寫本頁) 例如，以1 4 5 0 °C之高溫長時間使用石英坩堝時， 如果石英坩堝發生局部性變形及畸變時，在該變形部分之 對石英坩堝內面之導熱爲與其他的部分不同。因此，熔融 液係在石英坩堝內面之部分受到不同的熱歷程，其結果， 熔融液之對流發生紊亂，撈起單結晶變成不穩定。又按， 石英坩堝之變形本身會對單結晶之撈起發生不良影響是眾 所周知者。本發明之石英增渦爲可大幅度地減輕該變形所 導致之問題。 經濟部智慧財產局員工消費合作社印製 換言之，本發明之石英坩堝爲，接觸矽熔融液之時間 較長的小R部之壁厚變厚，熱應力或熱緩和力變成適當的 強度的關係，尤其是內壁附近之氣泡之膨脹速度較慢的關 係，認爲向熔融液側解放之確率變低。又按，因長時間作 業之結果，石英坩渦發生變形，因本身之重量等而直形軀 幹圓筒部向下方下沉之際會發生壓縮之力量，但小R部之 厚度之厚度較厚的關係小R部本身之變形較小。其結果， 認爲內側不易剝離。然後，可延長石英坩堝之壽命，在 8 0小時以上之長時間作業時也可維持單結晶之無轉位化 率爲7 0 %以上，成功地撈起阻害品質之不純物極少的矽 單結晶，確立諸條件而完成本發明者。 在以往之石英坩堝中，其壁厚爲從上端部至底部大致 上相同，但由於石英坩堝之製法的關係，小R部之壁厚有 稍厚之傾向，通常是小R部之比率係在其尺寸規格中心， 張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 526298 A7 _B7 ___ 五、發明説明（9 ) (請先閱讀背面之注意事項再填寫本頁) 1·3倍於直形軀幹圓筒部之1/2部之壁厚。然而，以 往之石英坩堝爲，長時間作業時，如上述該小R部分之熱 應力或熱緩和力受到助長性的影響之結果，在小R部分之 內表面容易發生表面粗糙性，進行方英石化及剝離，其結 果結晶爲有轉位化。 再者，本發明石英坩堝係將石英粉末投進旋轉的壓模 內，沿著壓模堆積層狀之際，將小R部堆積成比以往之坩 堝較厚，然後，使壓模旋轉之同時，從內面加熱及熔融石 英粉末層則可，大致上與以往相同的方法可製造之。 因此，採用本發明之構成則可儘量抑制石英坩堝因受 到加熱器之熱及大口徑用而塡充之結晶原料之重量及石英 坩堝之本身重量所致之變形，以防止石英坩堝內表面之劣 化。其結果，可抑制矽熔融液所致之石英坩堝之劣化，侵 鈾，方英石化，剝離，延長石英坩堝之壽命之同時，也延 長撈起矽結晶之時間的關係，能夠實行長時間之穩定作業 及提高生產性，可解決前述之問題。 經濟部智慧財產局員工消費合作社印製 茲舉實施例來說明本發明之實施形態如下，然而本發 明並非限定於該等實施例。 〔實施例 1〕 矽之多結晶原料7 0 k g裝入直徑1 8英寸之石英增 堝內並熔化，第1條是撈起4 8 k g之矽單結晶，對剩下 之矽熔融、液追加4 8 k g的多結晶原料並熔化，撈起第2 條4 8 k g之矽單結晶，再對矽熔融液追加3 8 k g之多 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ' ^ -12 - 526298 B7 五、發明説明（1〇) (請先閲讀背面之注意事項再填寫本頁) 結晶原料並熔化，撈起第3條4 8 k g之矽單結晶，接著 ，檢查所撈起的矽單結晶之無轉位化率。將該等作爲第1 批，實行至第2 0批。將所使用之石英坩堝之小R部之壁 厚予以變化時之結果顯示於表1。在此撈起之矽單結晶之 直徑爲6英寸，平均作業時間約爲1 〇 〇小時。 (表1 ) 壁厚比（小R部/直形軀幹部） 無轉位批數 無轉位化率 1.20 10 5 0 % 1.30 11 5 5 % 1.40 11 5 5 % 1.50 14 7 0 % 1.60 16 8 0 % 1.70 18 9 0 % 1.80 16 8 0 % 1.90 13 6 5 % 經濟部智慧財產局員工消費合作社印製 〔實施例 2〕 矽之多結晶原料1 2 0 k g裝入直徑2 2英寸之石英 坩堝內並熔化，第1條是撈起8 0 k g之矽單結晶，對剩 下之砂熔融液追加8 0 k g的多結晶原料並熔化，榜起第 2條8 0 k g之矽單結晶，再對矽熔融液追加5 0 k g之 多結晶原料並熔化，撈起第3條7 0 k g之矽單結晶，接 著，檢查所撈起的矽單結晶之無轉位化率。將該等作爲第 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -13- 526298 A7 B7 五、發明説明（彳1 ) (請先閱讀背面之注意事項再填寫本頁) 1批，實行至第2 0批。將所使用之石英坩堝之小R部之 壁厚予以變化時之結果顯示於表2。在此撈起之矽單結晶 之直徑爲8英寸，平均作業時間約爲1 〇 〇小時。 (表2 ) 壁厚比（小R部/直形軀幹部） 無轉位批數 無轉位化率 1.20 10 5 0 % 1.30 10 5 0 % 1.40 10 5 0 % 1.50 14 7 0 % 1.60 16 7 5 % 1.70 17 8 5 % 1.80 14 7 0 % 1.90 11 5 5 % 經濟部智慧財產局員工消費合作社印製 茲就實施例1及實施例2所使用之石英坩堝說明如下 。首先，如前述，控製小R部之壁厚而製造石英坩堝。該 石英坩堝係每1立方公分含有其直徑1 0〜2 5 0 // m的 氣泡2 0，0 0 〇個以上之半透明石英玻璃，以此爲外層 ，在該外層之直形軀幹圓筒部之1/2部之壁厚形成爲約 1 0 m m。關於小R部之厚度，控制在約1 3 m m〜約 1 9 mm之範圍內。再者，該石英坩堝之內表面一體熔合 地形成實質上年氣泡且表面平滑之厚度1〜2 mm之透明 石英玻璃。如上述，使用雙層構造之石英坩堝者。 準 標 家 國 國 中 用 適 尺 張 紙 本Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 526298 A7 B7____ V. Description of the Invention (1) [Technical Field] The present invention relates to a quartz crucible and a method for manufacturing a single crystal using the crucible. In more detail, it is about suppressing the deformation of the quartz crucible when the single crystal is picked up, and suppressing the deterioration caused by the deformation of the inner surface of the quartz crucible, so as to make it longer and more stable. In the state of indexing rate, it is possible to pick up a single crystal quartz crucible for a long time, and a method for manufacturing a single crystal using the stone central vortex. [Background Art] The following description uses silicon as a single crystal as an example. In recent years, with the increase in the diameter of sand wafers, the crucibles used to pick up large-caliber silicon single crystals have also become larger. At present, the crucible diameter is 2 2 to 24 inches (558 · 8 to 609). 6mm) has become mainstream. With the recent increase in the diameter of the quartz eddy vortex, the thermal load of the quartz eddy pot has also increased. For example, when 8 inches of crystals are to be picked up, the temperature of the surface that contacts the molten liquid is 5 degrees Celsius higher than that of 6 inches of crystals. Above, the melting loss rate of the inner surface of the quartz crucible is increased by 50% or more, and the amount of the melting loss is increased. As a result, the inner surface of the quartz crucible is damaged, and it is difficult to use the quartz crucible for a long time. Crucibles for the production of silicon single crystals must avoid the incorporation of impurities that impede the quality of the single crystals, so quartz must be used. Then, quartz crucibles include transparent quartz glass crucibles and translucent quartz glass crucibles (hereinafter referred to as transparent or opaque crucibles) depending on the manufacturing method. Compared with transparent crucibles, translucent crucibles have high strength due to the inclusion of tiny air bubbles. I paper size applies Chinese National Standard (CNS) Α4 specifications (210 × 297 mm) ^ -4-(Please read the notes on the back first Please fill in this page again for details), 11 526298 A7 _B7 One, five, description of the invention (2) It is easy to manufacture large-sized quartz crucibles, and the advantages of uniform heat distribution and uniform temperature etc. For this reason, translucent crucibles are widely used in practice (please read the precautions on the back before filling this page). However, the temperature of the quartz crucible during the silicon single crystal pick-up is as high as about 150 ° C. As can be understood from the thermal equilibrium state diagram of quartz, this temperature region is the relationship between the cristobalite production regions of crystalline materials. Due to thermal metamorphosis, cristobalite is prone to occur. It is said that the cause of the crystallization is trace amounts of impurities in the quartz and bubbles in the translucent glass crucible. With regard to the bubble portion, as the quartz crucible dissolves, it expands and ruptures when it reaches the inner surface, and the quartz plate enters the molten liquid. At the same time, fine protrusions occur in the portion where the bubble is broken, and the inner surface of the quartz crucible becomes rough. When it becomes a crystal nucleus, speckle cristobalite is formed. The origin of Fang Yingshi is not clear. However, it is said that the middle layer of Si 0 2-5, which is deoxygenated, was first formed. At the same time, it expanded from its central part. At high temperature, the Fang Ying petrified The speed is faster. Once again, the melting point of this substance is as high as 1720 degrees Celsius once it is formed. The temperature of the silicon single crystal cannot be melted. The intellectual property of the Ministry of Economic Affairs and the employee consumer cooperative print it into a solid substance. Drift in the melt. Various shortcomings that occur when the silicon single crystal is picked up are caused by the melting of the inner surface of the quartz crucible, the inclusion of impurities, and the relationship between the generated cristobalite is microcrystalline, which will be separated from the inner surface of the quartz crucible. Then, it is well known that the cristobalite released from the silicon melt can cause the transferred single crystal to become transposed. Due to the foregoing reasons, the short life of the quartz crucible has become a major industrial problem from both the productivity and cost aspects. As a result, the high degree of single crystal paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm1). : 526298 A7 B7 V. Description of the invention (3) Costs (Please read the precautions on the back and fill in this page first) To solve the above problems, it is disclosed in Japanese Patent Application Laid-Open No. 6-7 2 7 9 The proposal to control the bubble content in the inner surface area of the translucent crucible, however, does not essentially eliminate the various disadvantages caused by the melting of the quartz crucible and the formation of cristobalite crystals. In contrast, in Japanese Patent Application Laid-Open No. 8 — 2 9 3 Japanese Patent No. 2 proposes to form a quartz crucible containing a crystallization accelerator coating film or a solid solution layer to crystallize the inner surface of the quartz crucible within a thickness of 1 mm. Furthermore, in Japanese Patent Application Laid-open No. Hei 11 — No. 2 1 196 has proposed a silicon single crystal by adding Ca 0 or B a0 to a silicon melt. However, both are mixed into a quartz crucible or a silicon melt. Additives grow single crystals, and additives have a very small segregation coefficient. Although they are taken into single crystals, the concentration of additives in the remaining silicon melt increases. For example, using a multiple method In the single crystals that are recovered, the added additives may become impure and there is a possibility of reducing the quality. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the so-called multiple method means that after the single crystals are picked up, they are not turned off. In the state of the power supply of the heater, the remaining silicon melt is added into the polycrystalline raw material to pick up the next single crystal, and repeat the process to pick up a plurality of single crystals. Furthermore, in Japan Japanese Patent Application Laid-Open No. Hei 5-2 7 9 1 proposes to melt high-purity quartz at a temperature of 1750 ° C or higher and solidify the quartz crucible made of 100% cristobalite quartz. However, because of the need for special manufacturing technology, it will happen that the quartz paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 526298 A7 _ B7 V. Description of the invention (4) Crucible The problem of extremely high cost. (Please read the precautions on the back before filling out this page.) On the other hand, regarding the crucible with double-layer structure using quartz glass, Japanese Patent Application Laid-open No. 6_9 2 7 7 9 There is a proposal in the gazette that the inner surface of the crucible is substantially free of bubbles and the surface layer is smooth, and the outer layer is a translucent glass to control the diameter and the density of the bubbles, and a double-layered crucible using quartz glass. The quartz crucible is When the single crystal is picked up, the thermal energy of the external heater can be evenly transmitted to the entire area of the inner surface of the quartz crucible. At the same time, the occurrence of surface roughness caused by local uranium invasion on the inner surface of the quartz crucible is extremely small, and the quartz crucible is significantly increased. Its heat resistance. As a result, it is said that compared with the conventional quartz crucible, it is said that the single crystallinity rate can be maintained high. However, when used for a long time, especially after more than 80 hours, there is a problem that the single crystallization rate cannot be maintained. [Disclosure of the Invention] In view of the above, the inventors and other researchers have deliberately investigated the results and found that the non-transposition rate of the single result after long-term operation is related to the wall thickness of the small R portion of the quartz crucible. The inventors have completed. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This invention is to suppress as much as possible the heat that the quartz crucible receives from the heater and the deformation caused by the weight of the crystal material and its own weight when the single crystal is picked up. The purpose is to prevent the deterioration of the inner surface of the quartz crucible and to increase the life of the quartz crucible. Another object of the present invention is to provide a large-caliber quartz crucible that can hold a single crystal for a long time while maintaining the high degree of non-transposition of the single crystal, and a single crystal that can be picked up for a long time using the quartz crucible. The size of the single paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) 526298 A7 __B7 V. Description of the invention (5) The method of manufacturing crystals. (Please read the precautions on the back before filling this page) The present invention is made to achieve the aforementioned purpose. As shown in Figure 1, the quartz crucible 1 used when the Czech Lauszki method is used to lift single crystals, In the quartz crucible, the wall thickness 6 of the 1/2 part 5 of the straight trunk cylindrical part 3 and the wall thickness 7 of the small R part 4 connecting the curved part of the straight trunk cylindrical part 3 and the bottom 2 The ratio is a quartz crucible with a characteristic of 1.5-5 to 1.8 times the wall thickness 6 of the straight trunk cylindrical portion 3 at the center of its dimensions. If the quartz crucible of the present invention is used, in a long-term operation in which the time for picking up a single crystal exceeds 80 hours or more, such as from the initial single crystal to the last single crystal The non-transformation rate up to the straight trunk and curved parts can be maintained at more than 70%. It is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. At this time, it contains a diameter of 1 0 ~ 2 5 0 per 1 cubic centimeter. m bubbles of more than 200,000 translucent quartz glass layers, and a transparent quartz glass layer with a thickness of 0.3 mm or more formed by integrally forming no bubbles on the inner surface of the layer, in the aforementioned translucent A quartz crucible in which a crystalline quartz component is present in the quartz glass layer is preferred. In the present invention, as a result of the quartz crucible having the double-layered structure described above, it is possible to further suppress deterioration caused by erosion of the inner surface of the crucible and the like. In this case, a single crystal manufacturing method using a quartz crucible of the present invention to pick up a single crystal is used. As described above, as a result of using the quartz vortex of the present invention, single crystals can be stably picked up. This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -8 · 526298 A7 B7 V. Description of the invention (6) (Please read the precautions on the back before filling this page) Then, the The manufacturing method is a method of manufacturing a single crystal by the Czech Lowski method. When a plurality of single crystals are manufactured by a multiplex method, a wall thickness of 1/2 of a straight trunk cylindrical portion of a quartz crucible is used, and the connection is made. The ratio of the wall thickness of the cylindrical portion of the straight trunk to the small R portion of the curved portion at the bottom is a quartz crucible that is 1 · 5 ~ 1 · 8 times the wall thickness of the cylindrical portion of the straight trunk at the center of the size specification. A single crystal manufacturing method characterized by picking up single crystals with an operating time of 80 hours or more. As described above, the production method of the present invention is a single crystal production method that can maintain the non-transformation rate of the single crystal at 70% or more even when the operation time exceeds 80 hours when the single crystal is produced by a multiplex method. As mentioned above, the quartz crucible of the present invention can improve its heat resistance and suppress its deformation during use. It can prevent the roughness of the inner surface of the quartz crucible caused by deformation, maintain smoothness, and easily prolong the life of the quartz crucible. Provide a large-caliber quartz crucible with a single crystal that can be picked up for a long period of 80 hours or more while maintaining a high degree of single crystal without translocation rate. Printed by the Intellectual Property of the Ministry of Economy ¾ Employee Consumer Cooperatives. Furthermore, as a result of using the quartz crucible of the present invention to produce single crystals, it is possible to perform stable operations for a long time and improve productivity. Industrially, it is a very advantageous manufacturing method. [Brief Description of Drawings] FIG. 1 is a schematic sectional view showing a quartz crucible of the present invention. [Explanation of component number] 1 Quartz crucible The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -9- 526298 A7 B7 V. Description of the invention (7) 6, 7 Wall thickness 5 1/2 Part 3 Straight torso cylindrical part 2 Bottom 4 Small ruler (please read the precautions on the back before filling this page) [The best form of implementing the invention] In the past, the problems that occurred when picking up the silicon single crystal were: The above-mentioned melting of the inner surface of the quartz vortex vortex and the formation of the siderite, especially in the multiple method, after picking up the single crystal, repeatedly filling the polycrystalline raw material to pick up the next single crystal, but note that In the case where the multi-method was implemented, the silicon melt often contacted the bottom of the quartz crucible and the small R portion, and by controlling the wall thickness of the small R portion, the disadvantages caused in the past were eliminated. The present inventors have examined the results of various methods used for the long-term use of quartz crucibles on the growth of silicon single crystals by the Czech Lauszki method, and found that the thickness of the small R portion of the quartz crucible is set to be in the shape of a straight circle. When the thickness of the 1/2 part of the tube is about 1 · 5 ～ Ί · 8 times, it can inhibit the crust and the peeling of quartz on the surface of the quartz crucible. Hereinafter, the present invention will be described in more detail as follows. The inner surface of the quartz crucible has the function of contacting with the silicon melt, melting it by reacting with silicon, or transmitting the heat of an external carbon heater to the silicon melt. Regarding the temperature distribution of the quartz crucible in operation, the relationship between the heat transfer to the quartz crucible by the black lead crucible heated by the black lead heater, and the small r part is a single piece picked from the silicon melt. During crystallization, it is warmer than the bottom. According to the standard, the paper size applies the Chinese National Standard (CNS) A4 (210 × 297 mm) -10-526298 A7 B7 V. Description of the invention (8) Note that the small R part is compared with the straight crucible cylindrical part of the quartz crucible. The contact time with the silicon melt is longer as described above. (Please read the precautions on the back before filling this page.) For example, when using the quartz crucible for a long time at a high temperature of 1 450 ° C, if the quartz crucible is locally deformed and distorted, the quartz crucible in the deformed part The thermal conductivity of the inner surface is different from other parts. Therefore, portions of the molten liquid system on the inner surface of the quartz crucible are subjected to different thermal histories. As a result, convection of the molten liquid is disturbed, and single crystals picked up become unstable. It is also known that the deformation of the quartz crucible itself will adversely affect the pick-up of the single crystal. The quartz vortex increase of the present invention can greatly reduce the problems caused by the deformation. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics. In other words, the quartz crucible of the present invention is a relationship in which the wall thickness of the small R part that has been in contact with the molten silicon for a long time becomes thick, and the thermal stress or thermal relaxation force becomes an appropriate strength relationship. In particular, it is considered that the expansion rate of bubbles near the inner wall is relatively slow, and it is considered that the rate of liberation to the molten liquid side is low. According to the results of long-term operation, the quartz crucible is deformed, and the compression force occurs when the straight trunk cylindrical portion sinks downward due to its own weight, but the thickness of the small R portion is thicker. The small part of the relationship is that the deformation of the R part is small. As a result, it is considered that the inner side is difficult to peel off. Then, the life of the quartz crucible can be extended, and the non-translocation rate of the single crystal can be maintained at 70% or more during the long-term operation of more than 80 hours. The silicon single crystal with very few impurities impeding quality has been successfully retrieved. The inventors have established the conditions and completed the present invention. In the conventional quartz crucible, the wall thickness is almost the same from the upper end to the bottom. However, due to the manufacturing method of the quartz crucible, the wall thickness of the small R portion tends to be slightly thicker. Generally, the ratio of the small R portion is between At the center of its size specifications, the Zhang scale is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) 526298 A7 _B7 ___ V. Description of the invention (9) (Please read the precautions on the back before filling this page) 1.3 times as much The wall thickness of 1/2 of the cylindrical part of the straight trunk. However, in the conventional quartz crucible, when the long-term operation is performed, as a result of the thermal stress or thermal relaxation force of the small R portion described above being affected by the promotion property, the surface roughness of the small R portion is prone to occur, and Fang Ying As a result of petrification and peeling, the crystals were transformed. Furthermore, in the quartz crucible of the present invention, the quartz powder is poured into a rotating mold, and when the layer is stacked along the mold, the small R portions are stacked to be thicker than the conventional crucible, and then the mold is rotated while the mold is rotated. It can be heated from the inner surface and a fused silica powder layer, and it can be produced in the same manner as in the past. Therefore, the structure of the present invention can minimize the deformation of the quartz crucible due to the weight of the crystalline raw material filled by the heat of the heater and the large caliber and the weight of the quartz crucible, so as to prevent the deterioration of the inner surface of the quartz crucible. . As a result, it is possible to suppress the deterioration of the quartz crucible caused by the molten silicon, uranium invasion, cristobalite, peeling, and prolong the life of the quartz crucible. At the same time, the relationship between the time to pick up the silicon crystal can be extended, and long-term stability can be implemented. Operation and improving productivity can solve the aforementioned problems. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The following examples are used to explain the implementation of the present invention, but the present invention is not limited to these embodiments. [Example 1] 70 kg of polycrystalline silicon raw material was put into a 18-inch diameter quartz pot and melted. The first one was to pick up 48 kg of silicon single crystal, and melt the remaining silicon and add liquid. 4 8 kg of polycrystalline raw materials are melted, pick up the second 2 8 kg silicon single crystal, and then add an additional 3 8 kg to the silicon melt. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). ） ^ -12-526298 B7 V. Description of the invention (1〇) (Please read the precautions on the back before filling this page) Crystallize the raw materials and melt them. Take out Article 3 of the 4 8 kg silicon single crystal, then check No translocation rate of the recovered silicon single crystal. These will be regarded as the first batch and implemented to the 20th batch. Table 1 shows the results when the wall thickness of the small R portion of the quartz crucible used was changed. The silicon single crystals picked up here have a diameter of 6 inches and the average operating time is about 1,000 hours. (Table 1) Wall thickness ratio (small R section / straight torso section) No indexing batches No indexing rate 1.20 10 5 0% 1.30 11 5 5% 1.40 11 5 5% 1.50 14 7 0% 1.60 16 8 0% 1.70 18 9 0% 1.80 16 8 0% 1.90 13 65% The inner part is melted, the first one is to pick up 80 kg of silicon single crystal, add 80 kg of polycrystalline raw material to the remaining sand melt and melt, and list the second 80 kg silicon single crystal, and then An additional 50 kg of polycrystalline raw material was added to the silicon melt and melted, and the silicon single crystal of Article 3 70 kg was taken out. Then, the non-translocation rate of the silicon single crystal was checked. Use these as the first paper size to apply Chinese National Standard (CNS) A4 specifications (210X297 mm) -13- 526298 A7 B7 V. Description of invention (彳 1) (Please read the notes on the back before filling this page) 1 Approved, implemented to the 20th batch. Table 2 shows the results when the wall thickness of the small R portion of the quartz crucible used was changed. The silicon single crystals picked up here have a diameter of 8 inches and the average operating time is about 1000 hours. (Table 2) Wall thickness ratio (small R section / straight torso section) No indexing batches No indexing rate 1.20 10 5 0% 1.30 10 5 0% 1.40 10 5 0% 1.50 14 7 0% 1.60 16 7 5% 1.70 17 8 5% 1.80 14 7 0% 1.90 11 5 5% Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy The quartz crucibles used in Examples 1 and 2 are described below. First, as described above, the wall thickness of the small R portion is controlled to manufacture a quartz crucible. The quartz crucible contains more than 20,000 translucent quartz glass with a diameter of 1 to 2 5 0 // m per 1 cubic centimeter. This is the outer layer, and a straight trunk cylinder in the outer layer. The wall thickness of 1/2 of the part is formed to about 10 mm. Regarding the thickness of the small R portion, it is controlled within a range of about 13 mm to about 19 mm. Furthermore, the inner surface of the quartz crucible is integrally fused to form a transparent quartz glass having a thickness of 1 to 2 mm with substantially annual bubbles and a smooth surface. As described above, a double-layered quartz crucible is used. Appropriate sized paper on quasi-standard countries
A4 \—/ S N 瘦 公 97 2 526298 A7 B7 五、發明説明（12 ) (請先閲讀背面之注意事項再填寫本頁) 從上述之實施例1及實施例2之結果可明白，石英堪 渦之小R部之壁厚之效果係當小R部之壁厚/直形軀幹圓 筒部之壁厚之比率在1·50以上時可認定，可確實延長 實質上之石英坦渦壽命的結果。又按，超過1 · 8〇時單 結晶之無轉位化率有降低，因此在1 · 5 0〜1 · 8 〇之 範圍內爲宜。 在小R部之壁厚/直形軀幹圓筒部之壁厚之比率爲 1 · 9 0時，無轉位化率降低的原因被認爲是由於小R部 之壁厚增加之結果，需要更提高加熱器的電力的關係而加 快石英坩堝的劣化，或者，由於石英坩堝之壁厚不均勻而 無法完全緩和熱膨脹所引起的內壓之差而產生石英坩堝內 表面之剝離的關係。 再者，本發明並非限定於上述實施形態。上述實施形 態應被視爲舉例性而非限制性者，且具有與本發明之申請 專利範圍所記載之技術的思想實質上同樣的構成，發揮同 樣作用效果者，無論是如何應包含在本發明之技術範圍者 〇 經濟部智慧財產苟員工消費合作社印製 例如，在上述實施形態中，以撈起直徑6英寸及8英 寸之矽單結晶之情形爲例而說明，但本發明並非限定於此 ，可適用於撈起其直徑1 2〜1 6英寸或以上之單結晶時 也可適用之。 又按，本發明當然可適用於對矽熔融液施加水平磁場 ，縱磁場，歧點磁場等之所謂M C Z法也可適用者。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -15-A4 \ — / SN thin male 97 2 526298 A7 B7 V. Description of the invention (12) (Please read the precautions on the back before filling in this page) From the results of the above Examples 1 and 2, it can be understood that the quartz is vortex The effect of the wall thickness of the small R section is that when the ratio of the wall thickness of the small R section to the wall thickness of the cylindrical body of the straight trunk is 1.50 or more, it can be determined that the life of the quartz vortex can be substantially extended. . In addition, when the ratio of non-translocation of the single crystal decreases when it exceeds 1.80, it is preferable to be in the range of 1.50 to 1.80. When the ratio of the wall thickness of the small R portion to the wall thickness of the straight torso cylindrical portion is 1.90, the reason for the reduction in the rate of no transposition is considered to be the result of the increase in the wall thickness of the small R portion, which requires Increasing the relationship between the electric power of the heater and accelerating the deterioration of the quartz crucible, or the non-uniform wall thickness of the quartz crucible could not completely alleviate the difference in the internal pressure caused by the thermal expansion, which caused the peeling relationship of the inner surface of the quartz crucible. The present invention is not limited to the embodiments described above. The above-mentioned embodiments should be regarded as illustrative rather than restrictive, and have substantially the same configuration as the idea of the technology described in the scope of patent application of the present invention, and those exhibiting the same function and effect should be included in the present invention in any case. The technical scope is printed by the Intellectual Property of the Ministry of Economic Affairs and the Consumer Cooperative. For example, in the above-mentioned embodiment, the case of picking up a silicon single crystal with a diameter of 6 inches and 8 inches is taken as an example, but the present invention is not limited to this. It can also be used when picking up a single crystal with a diameter of 12 to 16 inches or more. According to another aspect, the present invention is naturally applicable to a so-called M C Z method in which a horizontal magnetic field, a longitudinal magnetic field, and a bifurcated magnetic field are applied to a silicon melt. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -15-