592945 A7 B7 五、發明説明（1 ) 產業上之利用領域 本發明係有關石英玻璃坩鍋及其製造方法，更詳細而 言係有關具有以結晶化劑經予滲雜一層以上的壁層之多層 壁的石英坩鍋及其製造方法。 習知技術 切克勞斯基法（c z法）用作製造半導體工業使用的 矽晶圓之單晶矽鑄錠的製造技術係爲人所知的。於c Z法 方面，多晶矽係予塡充於經予收容在承受器內的坩鍋內， 經予熔融、矽單晶被由熔融矽提拉起。 近年，半導體工業有要求較大口徑之晶圓，例如直徑 3 0 0 m m之晶圓的傾向，爲使此大口徑之矽鑄錠成長， 有時有增加C Z法之作業時間至1 〇 〇小時以上的必要。 加上有延遲結晶之提拉速度，延長C Z之實行時間並降低 矽結晶之構造缺陷的頻度之必要，惟加上以改善坩鍋之有 效壽命即可。 發明欲解決的課題 於矽製造矽鑄錠之中，C Z法中亦有 ''提拉〃多層矽 晶之方法。於相關的使用，坩鍋之側壁部係於熔液或熔液 水平之降低引起的交互曝露呈大氣中，再者成爲使其次的 矽塡充物之熔融引起的使曝露至熔液。在如此的使用法， 坩鍋表面內表面由於長期遭受較強的應力，內表面之保養 性即成爲較重要的。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -裝·592945 A7 B7 V. Description of the invention (1) Industrial application field The present invention relates to a quartz glass crucible and a method for manufacturing the same, and more specifically to a multilayer having a wall layer pre-doped with a crystallization agent. -Walled quartz crucible and its manufacturing method. Known technology The manufacturing technique of the single crystal silicon ingot used for the manufacture of the silicon wafers used in the semiconductor industry by the Czochralski method (cz method) is known. In the cZ method, polycrystalline silicon is filled in a crucible that is contained in a receiver, and after melting, the silicon single crystal is pulled up by the molten silicon. In recent years, the semiconductor industry has a tendency to require larger caliber wafers, such as 300 mm diameter wafers. In order to grow this large caliber silicon ingot, the operating time of the CZ method is sometimes increased to 1,000 hours. The above is necessary. It is necessary to add the pulling speed with delayed crystallization, extend the implementation time of C Z and reduce the frequency of structural defects of silicon crystals, but only to improve the effective life of the crucible. The problem to be solved is in the manufacture of silicon ingots from silicon, and there is also a method of `` lifting multi-layer silicon '' in the CZ method. For related applications, the side wall of the crucible is exposed to the atmosphere due to the cross-exposure caused by the melt or the decrease in the level of the melt, and it is also exposed to the melt caused by the melting of the next silicon filling. In such a use method, since the inner surface of the crucible surface is subjected to strong stress for a long time, the maintainability of the inner surface becomes more important. This paper size applies to Chinese National Standard (CNS) Α4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)
、1T 經濟部智慧財產局員工消費合作杜印製 -4- 94經濟部智慧財產局員工消費合作社印製 2 9 A7 _________B7_ 五、發明説明（2 ) 於操作溫度，習用的石英坩鍋之內部係與矽熔液反應 。坩鍋之內表面係典型的接受型態學上的變化，於c Z作 業中引起粗糙。加上c Z法之高熱使坩鍋壁變軟，亦引起 坩鍋之構造性變形。由於坩鍋內表面之粗糙被提拉的鑄錠 內會發生結晶缺陷。若坩鍋內表面之大部分爲粗糙時，則 結晶構造在結晶-熔液界面崩壤，須中止矽單晶提拉。因 此’粗糙係在矽鑄錠之製造方面係使坩鍋之連續使用成爲 不適當者。 失透亦即結晶化係在坩鍋之最內部的滲層引起。通常 的坦鍋之石英玻璃係體積與結晶同時變化，於玻璃相及結 晶相之界面發生應力。此應力係因坩鍋之玻璃層的小規模 變形引起開放，但內表面之平滑度會惡化。坩鍋之失透係 以於坩鍋最內部典型的發展的環狀圖案而引起的。由環狀 圖案可得知係以方英石包圍著。環狀圖案之中心係具有未 以方英石包覆或以非常薄的方英石層包覆的粗糙表面。 c Z法中，環狀圖案係予以形成於坩鍋內表面上，環狀圖 案之中心的表面係粗糙的。環狀圖案成長、熔合，粗糙領 域擴大著。 加上上述，坩鍋之內層係於C Z法中部分的溶解於矽 熔液內。矽及氧，此等係石英坩鍋之主成分，惟對成長的 矽鑄錠而言並不成爲有害的。然而，內層之雜質在此步驟 中會移行至矽熔液中，引起混入矽單晶內。至於控制坩鍋 內表面之失透的嘗試，例如於美國專利第5 9 7 6 2 4 7 號內正予揭示著含有結晶促進劑之被膜的形成。於此例’ (請先閱讀背面之注意事項再填寫本頁)、 1T Consumption cooperation by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Du Yin-4-94 Printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 9 A7 _________B7_ V. Description of the invention (2) At operating temperature, the internal system of the conventional quartz crucible Reacts with silicon melt. The inner surface of the crucible is a typical acceptance morphological change, which causes roughness in the cZ operation. In addition, the high heat of the c Z method makes the crucible wall soft, and also causes the structural deformation of the crucible. Crystal defects occur in the ingot that is pulled up due to the rough surface of the crucible. If most of the inner surface of the crucible is rough, the crystal structure collapses at the crystal-melt interface, and the silicon single crystal pulling must be stopped. Therefore, the 'roughness' makes the continuous use of the crucible inappropriate in the manufacture of silicon ingots. Devitrification, that is, crystallization, is caused by the permeation layer in the innermost part of the crucible. The volume of the quartz glass system of ordinary pans changes simultaneously with the crystal, and stress occurs at the interface between the glass phase and the crystal phase. This stress is caused by the small-scale deformation of the glass layer of the crucible, but the smoothness of the inner surface is deteriorated. The devitrification of the crucible is caused by the circular pattern typically developed in the innermost part of the crucible. It can be seen from the ring pattern that it is surrounded by cristobalite. The center of the ring pattern has a rough surface that is not clad with cristobalite or with a very thin layer of cristobalite. In the c-Z method, a ring pattern is formed on the inner surface of the crucible, and the surface at the center of the ring pattern is rough. The ring pattern grows and fuses, and the rough area expands. In addition to the above, the inner layer of the crucible is partially dissolved in the silicon melt in the CZ method. Silicon and oxygen, which are the main components of quartz crucibles, are not harmful to growing silicon ingots. However, the impurities in the inner layer migrate into the silicon melt during this step, causing the silicon single crystal to mix. As for attempts to control the devitrification of the inner surface of the crucible, for example, the formation of a film containing a crystallization accelerator is disclosed in U.S. Patent No. 5,997,274. In this example ’(Please read the notes on the back before filling this page)
本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5- 592945 經濟部智慧財產局員工消費合作社印製 該坩鍋係具 層分布著含 結晶化劑分 鍋壁之光滑 種操作方法 表面上形成 導入內部用 內層可予製 A7 B7 五、發明説明（3 ) 失透促進溶液係予適用於市售的ί甘鍋之表面上。以加熱至 6 0 0 °C以上’內表面可被說是有某種程度結晶化。然而 ，於此表面被覆技術有若干缺點。亦即，僅石英之結晶化 經予促進。在被覆坩鍋未能獲得結晶化之防止，坩鍋內表 面之玻璃的保護。被覆技術係又未能控制坩鍋之結晶化的 深度及速度。以不注意的接觸有結晶化促進用被膜係由內 表面經予去除，故需有特別的處理。 解決課題而採的手段 本發明之坩鍋係被使用於矽單晶之製造。 有於其壁之內部方向上已形成的內層。於其內 有由鋇、鋁、鈦及緦而成之群體選出的元素之 布著。揭示的坩鍋之內層係於加熱時，維持坩 內表面雖強化壁之構造性剛性，惟因此藉由三 之任一種方法可進行結晶化。 本發明之坩鍋係一般於旋轉的坩鍋型之內 主體粉末層，將內部腔孔內設成高溫雰圍後， 粉末及結晶化劑，熔融內部用粉末，形成滲雜 造白勺。 發明之實施形態 以下詳細記載本發明之坩鍋的構造、製造方法及操|乍 力法’惟本發明並非受此等所限定者。 (請先閲讀背面之注意事項再填寫本頁)This paper size applies to China National Standard (CNS) A4 (210X297 mm) -5- 592945 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy The method of forming an inner layer for introduction into the surface on the surface can be prepared A7 B7 V. Description of the invention (3) The devitrification promoting solution is suitable for the surface of a commercially available Gan pot. It can be said that the inner surface is crystallized to some extent when heated to above 600 ° C. However, there are several disadvantages to this surface coating technique. That is, crystallization of only quartz is promoted. The coating of the crucible failed to prevent crystallization, and the glass inside the crucible was protected. The coating technology failed to control the depth and speed of crystallization of the crucible. The coating for crystallization promotion is removed from the inner surface by inadvertent contact, so special treatment is required. Means for solving the problem The crucible of the present invention is used for the production of silicon single crystal. There is an inner layer formed in the inner direction of its wall. Inside it is a cloth made of elements selected from the group consisting of barium, aluminum, titanium and hafnium. The inner layer of the disclosed crucible is heated to maintain the structural rigidity of the inner surface of the crucible, but it can be crystallized by any of three methods. The crucible of the present invention is generally a rotating crucible-type inner body powder layer. After the internal cavity holes are set in a high-temperature atmosphere, the powder and the crystallization agent melt the internal powder to form a hybrid spoon. Embodiments of the Invention The structure, manufacturing method, and operation of the crucible of the present invention are described in detail below. However, the present invention is not limited by these. (Please read the notes on the back before filling this page)
- 592945 A7 B7 經濟部智慧財產局員工消費合作社印製 五 、發明説明 ( 4 ) 1 I 具 有 滲 雜 層 的 坦 鍋 之構造 1 石 英 玻 璃 坩 鍋 之 一 種 態 樣 示 於 第 1 圖 、 第 2 圖 〇 石 英 1 I 玻 璃 坩 鍋 1 係 具 有 固 定 內 部 腔 孔 1 2 之 壁 2 〇 壁 2 係 由 側 V 1 I 壁 4 及 底 部 6 而 成 〇 本 態 樣 之 側 壁 部 4 係 由 石 英 之 主 體 層 請 先、 1 1 I 1 4 及 經 予 形 成 作 側 壁 4 及 底 部 6 之 內 部 構 造 的 內 層 1 6 讀 背 1 1 而 成 〇 主 體 層 1 4 係 實 質 上 由 石 英 而 成 之 透 明 玻 璃 層 〇 內 TfiJ ’ 5. 1 1 層 1 6 係 由 實 質 上 熔 融 滲 雜 石 灰 玻 璃 層 而 成 厚 度 〇 • 2 思 事 項 I m m 1 2 m m 〇 內 層 宜 爲 Μ J \ \\ 氣 泡 即 可 〇 經 予 封 閉 入 內 再^ 填（ 1 _ 會 寫 本 裝 層 內 的 氣 泡 係 於 其 層 結 晶 化 時 發 生 微 枚 〇 此 微 粒 係 隨 著 頁 1 I 坩 鍋 膨 脹 由 內 表 面 分 離 或 脫 離 侵 蝕 內 表 面 j 溶 入 矽 熔 1 1 液 內 〇 此 等 的 微 粒 係 成 爲 矽 鑄 銳 之 單 晶 構 造 的 缺 陷 之 原 因 1 〇 結 晶 化 劑 係 分 布 於 內 層 1 6 內 5 惟 該 結 晶 化 劑 係 由 鋁 > 1 訂 1 I 鋇 緦 、 鈦 及 該 等 的 混 合 物 而 成 之 群 體 選 出 〇 結 晶 化 劑 可 爲 元 素 ( 例 如 A 1 ) 或 氧 化 物 、 氫 氧 化 物 過 氧 化 物 、 1 1 I 碳 酸 酯 - 矽 酸 鹽 、 草 酸 鹽 甲 酸 鹽 、 乙 酸 酯 、 丙 酸 酯 、 柳 1 ! 酸 鹽 、 硬 脂 酸 酯 Λ 酒 石 酸 鹽 氟 、 氯 類 有 機 或 Μ j \\\ 機 化 合 物 1 等 多 種 化 學 形 態 即 可 0 使 結 晶 化 劑 分 散 於 內 層 1 6 內 可 使 1 內 層 1 6 之 結 晶 化 促 進 〇 內 層 1 6 含 有 的 結 晶 化 劑 爲 5 0 1 1 5 0 0 P P m 宜； 爲 8丨 0， 1 6 0 ρ ρ η ]， ， 更宜 :爲 1 1 1 1 0 0 1 2 0 Ρ Ρ m 〇 以 未 滿 約 5 0 Ρ Ρ m 之 滲 雜 水 準 Ί 製 作 的 坩 鍋 係 在 典 型 的 C Z 法 之 期 間 中 內 層 1 6 於 內 層 1 1 6 內 未 引 起 較 佳 的 部 分 二 氧 化 矽 之 結 晶 化 〇 相 反 的 若 1 1 於 內 層 1 6 內 經 予 滲 雜 超 m 約 5 0 〇 Ρ Ρ m 之 鋁 時 1 則 僅 1 1 可 得 並 不 重 要 的 附: 加 利益 0 1 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） /f 2 9 A7 _______B7 ______ 五、發明説明（5 ) 於其他態樣，內層1 6係予形成於中間層1 8之上° 後者係由合成石英玻璃或純粹的石英玻璃製作的（胃3 ® )。本態樣之側壁4係由主體層1 4、中間層1 8及內層 1 6而成。如第1圖、第2圖之態樣所示般，主體層1 4 係典型的半透明之石英玻璃，內層1 6係經予滲雜@石英 玻璃層。中間層1 8係以天然或合成的石英粉製作的非滲 雜的石英玻璃即可，惟亦可包圍各種材料於中間層1 8內 ，又亦可爲滲雜層。存在的結晶化劑係可爲與內層1 6使 用者相同，亦可爲不同。 於第4圖所示的坩鍋之其他態樣，外部層1 9係又予 形成於側壁部4之外側的外部位上。於一種態樣’外部層 1 9係以厚度約0 · 5〜2 · 5 m m，鋁、鋇、緦、鈦或 此等的混合物可予滲雜的。相同的亦可有效的使用此等的 試藥之混合物。外部層內的結晶化劑之含有量係約5 0〜 5 Ο Ο ρ p m。 於第4圖所示的坩鍋，側壁部4係典型的具有約 10 · Omm之厚度，主體層14係由6 · 5〜9 · 4 mm，內層16係由0 · 2〜1 · 2mm，加上外層19 係由其餘的0 . 5〜2 · 5 m m而成。底部6係經予形成 於與第2圖〜第4圖之側壁部4類似的構造上，惟宜爲非 以外部層1 9所形成即可。底部6係典型上具有約 10 · 0mm之厚度，其約0 · 2〜1 . Omm係由內層 1 6而成。本態樣之坩鍋係成爲由具有內層1 6 ，中間層 1 8、主體層1 4及外層1 9之構成則爲顯而可知的。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) ;衣· 訂 經濟部智慧財產局員工消費合作社印製 -8 - 592945-592945 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (4) 1 I Structure of a pan with an impregnated layer 〇Quartz 1 I Glass crucible 1 is a wall 2 with a fixed internal cavity hole 12 〇Wall 2 is formed by the side V 1 I wall 4 and the bottom 6 〇The side wall portion 4 of this aspect is made of quartz , 1 1 I 1 4 and the inner layer 16 formed as the internal structure of the side wall 4 and the bottom 6 are read from the back 1 1. The main body layer 1 4 is a transparent glass layer substantially made of quartz. TfiJ ′ 5. 1 1 layer 1 6 is a thickness made by melting and impregnating the lime glass layer. ○ 2 considerations I mm 1 2 mm 〇 The inner layer should be Μ J \ \\ Bubbles can be sealed. ^ Fill (1 _ will write the bubbles in the packaging layer when the layer is crystallized The micro-particles are separated from the inner surface with the expansion of the crucible on the inner surface. The micro-particles are dissolved into the molten silicon 1 1 solution. These micro-particles become defects of the silicon single crystal structure. Reason 1. The crystallizer is distributed in the inner layer 16 and 5. However, the crystallizer is selected from the group consisting of aluminum> 1, 1 barium, hafnium, titanium, and mixtures thereof. The crystallizer may be an element. (E.g. A 1) or oxide, hydroxide peroxide, 1 1 I carbonate-silicate, oxalate formate, acetate, propionate, salicylate, stearic acid Ester Λ tartrate fluorine, chlorine organic or MH j \ organic compound 1 and other chemical forms can be 0. Dispersing the crystallization agent in the inner layer 1 6 can promote the crystallization of 1 inner layer 16 6 inner layer 1 6 The crystallization agent should be 5 0 1 1 5 0 0 PP m; it is 8 丨 0, 1 6 0 ρ ρ η],, more suitable: 1 1 1 1 0 0 1 2 0 Ρ Ρ m 〇 The crucible produced at a level of penetration less than about 50 ρ ρ m is the middle and inner layer during the typical CZ method 16 In the inner layer 1 1 6 does not cause a better partial crystallization of silicon dioxide. On the contrary, if 1 1 is pre-doped with ultra-m about 50 0 〇 ΡΡm in the inner layer 1 1 then Only 1 1 can be obtained with no important attachments: plus benefits 0 1 1 1 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) / f 2 9 A7 _______B7 ______ 5. Description of the invention (5) to others In appearance, the inner layer 16 is pre-formed on the middle layer 18 °. The latter is made of synthetic quartz glass or pure quartz glass (Stomach 3 ®). The side wall 4 in this aspect is formed by a main layer 14, an intermediate layer 18 and an inner layer 16. As shown in Figures 1 and 2, the main layer 1 4 is a typical translucent quartz glass, and the inner layer 16 is pre-doped @Quartz glass layer. The intermediate layer 18 may be a non-impregnated quartz glass made of natural or synthetic quartz powder, but it may also surround various materials in the intermediate layer 18, and may also be an impurity layer. The existing crystallization agent may be the same as the user of the inner layer 16 or may be different. In another aspect of the crucible shown in Fig. 4, the outer layer 19 is formed on the outer position on the outer side of the side wall portion 4. In one aspect, the outer layer 19 is made of aluminum, barium, hafnium, titanium, or a mixture thereof with a thickness of about 0.5 to 2.5 mm. The same can also be effectively used as a mixture of these reagents. The content of the crystallization agent in the outer layer is about 50 to 5 0 ρ p m. In the crucible shown in Fig. 4, the side wall portion 4 is typically about 10 · Omm thick, the main layer 14 is composed of 6 · 5 ~ 9 · 4 mm, and the inner layer 16 is composed of 0 · 2 ~ 1 · 2 mm. , Plus the outer layer 19 is formed by the remaining 0.5 to 2.5 mm. The bottom portion 6 is formed in a similar structure to the side wall portion 4 in Figs. 2 to 4, but it is preferable that the bottom portion 6 is not formed with the outer layer 19. The bottom 6 typically has a thickness of about 10.0 mm, and the thickness of the bottom 6 is about 0.2 mm to 1.0 mm. It is obvious that the crucible in this aspect is composed of an inner layer 16, an intermediate layer 18, a main layer 14 and an outer layer 19. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page); Clothes and Orders Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -8-592945
發明説明 具有滲雜層之坩鍋的製造方法 在此表示c Z步驟中形成已適於失透的滲雜內層之方 法。第5圖，第6圖所示方法係製作出第1圖、第2圖所 示的態樣之坩鍋者。熔融石英玻璃坩鍋之一般的製造方法 係經予教示於美國專利第5，1 7 4，8 0 1號（松村等 人）。在該方法，於旋轉的模具（第5圖）內製作由石英 粉而成的坩鍋體（第5圖），由其內部腔孔至少加熱坩鍋 體至呈部分的熔融，製作坩鍋之基體。 於坩鍋基體之內部腔孔內形成著高溫雰圍，內部用石 英粉係予供給至此高溫雰圍內（第6圖）。內部用石英粉 係予至少部分熔融並使堆積於坩鍋基體之內壁面，事先予 以決定厚度之透明合成玻璃內層乃予形成。 至於適於矽單晶之形成的使用之坩鍋之製造方法，有 具有結晶化劑已滲雜的內層1 6之坩鍋之形成。爲製作第 1圖、第2圖所示的態樣之坩鍋，最初用主體石英粉料斗 2 2 a介由流量控制閥2 6 a及供給管2 4將主體石英粉 3 1導入旋轉的模具2 0內，形成主體石英粉末層3 6 ( 第5圖）。主體石英粉3 1宜爲純粹的水晶粉即可。主體 石英粉料斗之攪拌葉片2 8 a係供攪拌料斗2 2 a內之主 體石英粉3 1而予使用，使其流動良好。刮刀3 2係予賦 形成可刮平模具之內表面，供使用於經予導入的主體石英 粉之整形。如此主體粉末層3 6係予形成至經予選擇的厚 度。在本方法熔融所形成的主體粉末層3 6 (第6圖）。 (請先閱讀背面之注意事項再填寫本頁) 裝· -訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X 297公釐） · 9 - 94 2 9 A7 B7 五、發明説明（7 ) 含有電源3 7及電極3 8 a、3 8 b之電極組合係予部分 的配置於模具2 0之內部腔孔內。供給例如2 5 0〜 350V，約180 0 A之直流使於電極38a 、38b 間發生電弧。於主體粉末層3 6之內側高溫雰圍4 2。在 此高溫雰圍4 2內溶融已形成於模具之主體粉末層3 6。 熔融係由對電極3 8 a、3 8 b較接近的側進行至終端。 由此技術而得的主體粉末層進行之熔融機構係爲熟習該項 技術者所知悉的，例如內田等人之美國專利第 4，935 ，046 號，第 4，956 ，208 號所揭示 〇 與經予形成的主體粉末層3 6之表面熔融之同時，由 內部用石英粉料斗2 2 c經過供給管4 0使內部用石英粉 4 4流入高溫雰圍4 2中。內部用粉末流量控制閥2 6 c 係供控制內部用石英粉末4 4之流速使用。料斗攪拌葉片 2 8 c係與上述同樣的使用。至於內部用石英粉4 4係可 使污染物質經予淸洗去除以由結晶化劑已摻雜的天然石英 粉之本質的純粹石英粉而成即可。又已滲雜結晶化劑之合 成石英粉亦可使用。 以電極弧製作的高溫雰圍4 2係製作非常強的電漿場 至少部分的熔融內部用石英粉。至少部分的熔融的內部用 石英粉4 4係予擠壓向外側，予以熔著至使於已形成的主 體粉末層3 6 /熔融主體層1 4之側壁及底部上形成內層 16。 於第6圖，主體層爲權宜計係以3 6之數字表示。在 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） _ 1〇 _ (請先閱讀背面之注意事項再填寫本頁) -裝· 訂 經濟部智慧財產局員工消費合作社印製 592945 經濟部智慧財產局員工消費合作社印製 A7 _____B7_五、發明説明（8 ) 此階段，當然，層係成爲未熔融的主體粉末層3 6與已熔 融的主體層之組合。內部用石英粉4 4係予流入高溫雰圍 4 2內並於主體層1 4熔著之間連接形成內層1 6。如此 已形成的內層係本質上透明且無氣泡。內層1 6之厚度係 藉由內部用石英粉之導入速度及熔融時內部用粉末的流動 時間予以控制。 具有內層1 6及中間層1 8之坩鍋的製造方法示於第 5圖及第7、8圖。形成主體粉末層36 (第5圖）後， 電極組合係予配置於坩鍋之內部腔孔內。中間層用石英粉 4 8係由中間粉末料斗2 2 c通過流量控制閥2 6 c予以 供給。料斗之攪拌葉片2 8 c係如同攪拌葉片2 8 a、 2 8 b般予以使用。中間層用石英粉4 8係在高溫雰圍 4 2內予以至少部分的熔融，於經予形成的主體粉末層/ 熔融主體層之上熔著並形成中間層1 8。中間層1 8之厚 度係可予控制管制中間層用石英粉4 8之流量速度及時間 〇 形成中間層1 8後，內部用石英粉係予導入高溫雰圍 4 2內（第8圖）。內部用石英粉4 4係予至少部分的熔 融，堆積於中間層1 8上並成爲內層1 6。 結晶化劑滲雜內層係予形成於各種的透明中間層上。 例如中間層1 6係可爲純粹的石英層或滲雜層。結晶化劑 滲雜內層係堆積於合成石英粉或純粹的石英粉（亦即純化 的天然水晶製作的透明層上予以形成）。 同樣的方法亦被使用於具有外部層1 9之坩鍋的構築 (請先閱讀背面之注意事項再填寫本頁) 裝· 、11 教Description of the Invention A method for manufacturing a crucible having an impregnated layer is shown here as a method of forming an impregnated inner layer suitable for devitrification in step cZ. The methods shown in Figs. 5 and 6 are those who have produced the crucible in the state shown in Figs. 1 and 2. The general manufacturing method of a fused silica glass crucible is taught in U.S. Patent No. 5,174,801 (Matsumura et al.). In this method, a crucible body (Fig. 5) made of quartz powder is produced in a rotating mold (Fig. 5), and at least the crucible body is heated from its internal cavity to a partial melting to produce a crucible. Substrate. A high-temperature atmosphere is formed in the inner cavity of the crucible base, and the inside is supplied with quartz powder to this high-temperature atmosphere (Figure 6). The internal quartz powder is at least partially melted and deposited on the inner wall surface of the crucible base. A transparent synthetic glass inner layer having a predetermined thickness is formed in advance. As for a method of manufacturing a crucible suitable for the formation of a silicon single crystal, there is a crucible having an inner layer 16 in which a crystallization agent has been doped. In order to make the crucible in the state shown in Figures 1 and 2, the main body of quartz powder hopper 2 2 a was first introduced into the rotating mold through the flow control valve 2 6 a and the supply pipe 2 4. Within 20, a bulk quartz powder layer 3 6 is formed (Figure 5). The main quartz powder 31 should be pure crystal powder. The stirring blade 2 8 a of the main body quartz powder hopper is used for the main body quartz powder 31 in the stirring hopper 2 2 a to make it flow well. The scraper 32 is preformed to form the inner surface of the mold which can be scraped, and is used for shaping the main quartz powder introduced. The main powder layer 36 is thus formed to a selected thickness. The main powder layer 3 6 formed by this method is melted (FIG. 6). (Please read the precautions on the back before filling out this page.) Installation · -Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives. The paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) · 9-94 2 9 A7 B7 V. Description of the invention (7) The electrode combination containing the power source 3 7 and the electrodes 3 8 a, 3 8 b is partially arranged in the internal cavity of the mold 20. For example, a DC voltage of about 250 to 350 V and a voltage of about 180 0 A causes an arc to occur between the electrodes 38a and 38b. A high-temperature atmosphere 4 2 is inside the main powder layer 36. In this high-temperature atmosphere 4 2, the main powder layer 36 formed on the mold is melted. The melting is performed from the sides closer to the counter electrodes 3 8 a and 3 8 b to the end. The melting mechanism of the main powder layer obtained by this technology is known to those skilled in the art, such as disclosed in U.S. Patent Nos. 4,935,046 and 4,956,208 of Uchida et al. Simultaneously with the melting of the surface of the preformed body powder layer 36, the internal quartz powder hopper 2 2c passes the supply pipe 40 through the internal quartz powder hopper 4 into the high-temperature atmosphere 42. Internal powder flow control valve 2 6 c is used to control the flow rate of internal quartz powder 4 4. The hopper stirring blade 2 8 c is used in the same manner as described above. As for the internal quartz powder 4 4, it can be made of pure quartz powder which can make the contaminated material be washed and washed, and is made of natural quartz powder doped with crystallization agent. Synthetic quartz powder that has been doped with a crystallization agent can also be used. The high temperature atmosphere produced by electrode arc 4 2 series makes a very strong plasma field. At least part of the molten quartz powder is used for the interior. At least a part of the molten interior is extruded with quartz powder 4 4 and is fused so that an inner layer 16 is formed on the side wall and the bottom of the formed main powder layer 36 / molten main layer 14. In Figure 6, the expedient of the main layer is represented by a number of 36. Applicable to China Paper Standard (CNS) A4 (210X 297mm) on this paper scale _ 1〇_ (Please read the precautions on the back before filling out this page)-Binding and printing 592945 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____B7_ V. Description of Invention (8) At this stage, of course, the layer system is a combination of the unmelted body powder layer 36 and the melted body layer. The internal quartz powder 4 4 flows into the high-temperature atmosphere 4 2 and is connected between the main layer 14 and the inner layer 16 to form an inner layer 16. The inner layer thus formed is essentially transparent and free of bubbles. The thickness of the inner layer 16 is controlled by the introduction speed of the quartz powder for internal use and the flow time of the internal powder during melting. A method for manufacturing a crucible having an inner layer 16 and an intermediate layer 18 is shown in Figs. 5 and 7 and 8. After the main body powder layer 36 (FIG. 5) is formed, the electrode assembly is arranged in the inner cavity of the crucible. The quartz powder for the intermediate layer 4 8 is supplied from the intermediate powder hopper 2 2 c through the flow control valve 2 6 c. The stirring blades 2 8 c of the hopper are used like the stirring blades 2 8 a and 2 8 b. The quartz powder for the intermediate layer 48 is at least partially melted in a high-temperature atmosphere 4 2, and is melted on the preformed main powder layer / fused main layer to form the intermediate layer 18. The thickness of the intermediate layer 18 can be controlled to control the flow rate and time of the quartz powder 48 for the intermediate layer. After the intermediate layer 18 is formed, the internal quartz powder is introduced into the high-temperature atmosphere 4 2 (Figure 8). The internal quartz powder 4 4 is at least partially fused and is deposited on the intermediate layer 18 and becomes the inner layer 16. The crystallization agent-impregnated inner layer is formed on various transparent intermediate layers. For example, the intermediate layer 16 series may be a pure quartz layer or a doped layer. Crystallizing agent Impregnated inner layer is deposited on synthetic quartz powder or pure quartz powder (that is, formed on a transparent layer made of purified natural crystal). The same method is also used in the construction of crucibles with an outer layer of 19 (please read the precautions on the back before filling this page).
本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ H 592945 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（9 ) (第4圖）。外部粉末層4 9係最初予形成於旋轉模具內 (第9圖），外部粉末料斗2 2 d係介由供給管2 4並通 入模具2 0之內部。爲管制由料斗2 2 d送至模具之內部 的外部石英粉4 6之流量，於供給管2 4使用閥2 6 d。 外部粉末層4 9之厚度係以使用刮刀4 7可予控制。如此 進行坩鍋之製造。外部層1 9係不可滲雜結晶化劑。滲雜 外部層1 9係予以構成至使容易的結晶化連影響矽熔液亦 在不污染下可改善在局溫之i甘鍋的尺度安定性。外部層 1 9係以約1 00〜500ppm滲雜，宜爲以1 2〇〜 5 0 0 p ρ m之結晶化劑滲椎即可。在未滿1 〇 〇 p p m 之滲雜並未見均勻的結晶化，以超過5 〇 〇 p p m之水準 的滲雜在本發明之坩鍋並未能得更佳的優點。 鋁較其他化合物在成本上較廉價，且未熔融鋁滲雜外 部石英粉之處理亦環境上簡便，因此，以較其他的滲雜劑 或混合粉純粹的石英粉及鋁滲雜石英粉4 6之混合物的使 用爲宜。至於前述鋁化合物，可舉出硝酸鋁（Al(NO)3)39H2〇) 、氫氧化鋁（Al(OH)3、氯化鋁（AlCh)、碳酸氫鋁（A1(HC〇2)3) 等。 結晶化劑導入法 於本發明之態樣，內部用石英粉4 4係以結晶化劑滲 雜的。如前述般，結晶化劑係含有鋁、鋇、緦、鈦或該等 混合物作爲元素形態或化合物。化合物形態之中宜爲氧化 物及氮化物之二種。限於可得經予選擇的最終劑含有量， (請先閲讀背面之注意事項再填寫本頁) i裝·This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ H 592945 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) (Figure 4). The outer powder layer 49 is initially formed in the rotary mold (Fig. 9), and the outer powder hopper 2 2 d passes through the supply pipe 24 and passes into the mold 20. In order to control the flow rate of the external quartz powder 46, which is sent from the hopper 2d to the inside of the mold, a valve 26d is used for the supply pipe 24. The thickness of the outer powder layer 49 can be controlled using a doctor blade 47. In this way, the crucible is manufactured. The outer layer 19 is an impervious crystallization agent. Impregnation The outer layer 19 is structured so that it can be easily crystallized and affects the silicon melt without contamination, which can improve the stability of the scale at the local temperature. The outer layer 19 is impregnated at about 100 to 500 ppm, and it is preferable that the outer layer 19 is impregnated with a crystallizing agent of 120 to 500 p ρ m. Impurities of less than 1000 p pm did not show uniform crystallization. Impurities of more than 500 p p m in the crucible of the present invention did not provide better advantages. Aluminum is cheaper than other compounds, and the treatment of unfused aluminum doped with external quartz powder is also environmentally simple. Therefore, pure quartz powder and aluminum doped quartz powder are compared with other dopants or mixed powders. 4 6 The use of the mixture is suitable. Examples of the aforementioned aluminum compounds include aluminum nitrate (Al (NO) 3) 39H2〇), aluminum hydroxide (Al (OH) 3, aluminum chloride (AlCh), and aluminum bicarbonate (A1 (HC〇2) 3) Etc. The crystallization agent introduction method is in the aspect of the present invention, and the inside is quartz powder 4 4 mixed with a crystallization agent. As mentioned above, the crystallization agent contains aluminum, barium, hafnium, titanium, or a mixture thereof. Elemental form or compound. Among the compound forms, oxides and nitrides are preferred. Limited to the content of the final agent that can be selected. (Please read the precautions on the back before filling out this page.)
、1T 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -12- 592945 A7 B7 五、發明説明（1〇) (請先閲讀背面之注意事項再填寫本頁) 亦可使用滲雜石英粉及未滲雜石英粉之混合物。於合成石 英粉被使用作混合物之未滲雜石英粉時、結晶化劑之結晶 化促進強度會增加。以合成石英製作的玻璃係較天然石英 玻璃（亦即熔融水晶玻璃）柔軟。合成石英玻璃之柔軟基 質係程度上非常良好。由不定形石英玻璃層轉換成方英石 類結晶化石英玻璃時，引起體積變化且剛性（亦即減少的 構造電阻）增大。結果合成石英粉經予包入熔融內層1 6 或外部層1 9內時，即使較低的滲雜水準亦可得相同的變 形。 以準備含有結晶化劑之石英溶膠，可得均勻的滲雜的 二氧化矽凝膠。此凝膠亦爲滲雜粉末之另一例。凝膠宜爲 轉換成純粹的二氧化物而予烘烤。 經濟部智慧財產局員工消費合作社印製 再者’爲石英粉之滲雜，以結晶化劑被覆石英粉或形 成劑含有二氧化矽凝膠，並亦可使擔持於石英粉上。被覆 石英粉末係亦可以有機材料例如醇鹽被覆純粹的石英粉。 至於其他可選擇的導入法，係混合結晶化劑及天然或合成 石英粉等未滲雜石英粉，亦有同時導入的例子。例如碳酸 鋇（BaC03)或硝酸鋁係在料斗2 2 b中被加入內部用石英粉 4 4內。以混合葉片2 8均勻的混合碳酸鋇或硝酸鋁與內 部用石英粉。內部用石英粉及碳酸鋇或硝酸鋁之混合物係 接著如前述般被導入高溫雰圍4 2中。 內部用石英粉4 4之熔融中，結晶化劑係以無機粉末 例如氧化物（BaO)、（AhCh)、氫氧化物（A1(0H)3、碳酸氫化 物（A1(HC〇2)3、複合氧化物（TiBaCh)、氮化物（BaN2)、氣化物 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -13- 592945 A7 __—_B7 五、發明説明（11 ) (BaCh)、（A1C1)3或前述化合物之多數混合物被供給至高溫 分S 4 2中。在ί甘鍋熔融之筒溫’亦可同樣的使用可轉化 成前述化合物之任一者的有機化合物。 (請先閲讀背面之注意事項再填寫本頁) 於本發明之其他態樣’由指定的料斗同時與內部用石 英粉4 4分別可導入結晶化劑至高溫雰圍4 2中。控制由 內部粉末料斗2 2劑料斗流出的閥係與前述的閥同樣的兩 者可同時流出般予以開口。 再者，於其他例，結晶化劑例如亦可爲氫氧化鋇（ Ba(OH)2 )或氯化鋇（BaCh )等的液狀物。液狀溶液係於 咼溫雰圍4 2中於導入內部用石英粉4 4之前或同時可予 導入內部用石英粉4 4中。 經濟部智慧財產局員工消費合作社印製 液狀溶液係可於導入內部用石英粉4 4至高溫雰圍中 的同時可予直接導入。例如鄰近高溫雰圍4 2的流量管 4 0之終端附近配置的注射器可予導入。液狀溶液係可予 選擇的溶劑在限於不成爲鑄錠之潛在的污染源下可爲水溶 液亦可爲有機溶液，液狀溶液中的結晶化劑係又可供給至 熔融前已形成的粉末層內。結晶化劑之有機化合物，有機 溶液或水溶液係可噴佈於已形成的粉末層4 9上。此劑之 適用優點係於層之特定的領域上可配置結晶化劑。例如僅 於側壁部中或底部6之內側、側壁4或底部6之全內面（ 側及底）或已預期的熔融線以下的側壁4之內側（熔融線 係熔融矽在熔融後與坩鍋內部壁接觸的線）可適用結晶化 劑。 結晶化劑雖係與內部用石英粉同時，但是於分別導入 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 592945 經濟部智慧財產局員工消費合作社印製 A7 _ _ ___B7_五、發明説明（12 ) 的上述方法，中間層用石英粉4 8係又可使用作內部用石 英粉4 4。例如中間層用石英粉4 8如前述般由於形成中 間層1 8 ，可予導入高溫雰圍4 2中。停止中間層粉末料 .斗之流動，以將中間層用石英粉4 8及鋇化合物或鋁化合 物同時導入高溫雰圍4 2中可形成內層1 6。 於同樣的態樣，純粹的內部用石英粉4 4係如最初所 述般予以導入，其次碳酸鋇或硝酸鋁導入中的內部用石英 粉4 4同時予以流入，具有碳酸鋇或硝酸鋁之內層1 6經 予形成。碳酸鋇或硝酸鋁之流量速度係由內表面至主體層 1 4使碳酸鋇或硝酸鋁之量可以成梯度般變動。相關的態 樣之坩鍋係成爲與具有主體層1 4、中間層1 8及內層 1 6之坩鍋同等。因此，內層1 6係在主體層之附近劑之 含有量低，以在坩鍋之內部腔孔1 2之附近的領域變高的 梯度可含有碳酸鋇或硝酸鋁。具有滲雜層的坩鍋之操作法 〇 在內層1 6使用的滲雜元素之選擇係依所期待的操作 法予以決定。各自的結晶化劑係具有特有的結晶化促進力 ，因應劑之滲雜水準，內層1 6中的石英結晶化速度之程 度係可控制。至於操作法之說明及由而的各種劑之使用法 係由調整以C Z法使用的坩鍋之內表面所具的環狀圖案現 象開始。於矽鑄錠之形成方面使用坩鍋時，以先將與熔 '液 接觸的內層之表面事先設成平滑狀較佳。因此，於以下的 說明，坩鍋之''內層〃及 ''內表面〃係在操作上應予注意 於以內層最重要的部份上。 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 丨翁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 592945 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（13 ) 更詳細而言，環狀圖案現象係經予觀察於第1 〇圖〜 第1 4圖所示的先行技術之坩鍋之內表面上。第1 〇圖係 表示與矽熔液接觸，內表面上多數的環狀圖案已形成的坦 鍋之內表面5 0。環狀圖案係通常具有環5 2，環及環內 之領域係方英石5 6。 C Z法中，環狀圖案係增加其面積，如第1 1圖所見 般，擴散至內層表面5 0上並增加其比例。隨著環狀圖案 增加，粗糙的表面集合組織5 4係出現於中央。環狀圖案 之境界內的粗糙表面集合組織域5 4係擴展於坩鍋之內表 面上。第1 2圖係表示由習用的C Z法而得的典型坩鍋之 內表面。環狀圖案熔合，增大粗糙的表面集合組織域5 4 。如前述般，粗糙的內表面係對成長的矽鑄錠之結晶構造 給予強烈的影響。 先前技術之環狀圖案的放大上面圖及截面圖示於第 1 3圖、第1 4圖。環狀圖案之中心係具有以方英石（結 晶質二氧化矽）5 6包圍的粗糙表面集合組織5 4，可具 由內表面5 0擴展至坩鍋壁。方英石5 2係以茶色的物質 予以裝飾，通常係以使用坩鍋之內表面的茶色環予以觀察 。於先彳了技術之環狀圖案之中小且光滑的表面境界5 5係 存在於較粗的領域5 4及環5 2之內緣之間者。 關於附隨環狀圖案而引起的表面之粗糙度，本發明在 以下因提供適於完全法、電暈法及平滑法之所謂三種結晶 化法而引起的操作之坩鍋內層，採用下述的各自要素之組 合。於此等的任一方法，坩鍋係適於在擴張C Z法之使用 (請先閱讀背面之注意事項再填寫本頁) ;裝· 、11 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16- 592945 A7 B7 五、發明説明（14 ) ，內表面係無粗糙又亦無重大的熔解。 (請先閲讀背面之注意事項再填寫本頁) ''完全〃法，係在此方法垠鍋之內表面係予加熱，與 矽熔液接觸之前，使坩鍋之內表面結晶化。在此方法，環 狀圖案之發生經予抑制，環狀圖案係在c Z步驟中或後未 予觀察出。因此，完全法之坩鍋的內表面係加熱後矽在熔 融之前以/3 -方英石被覆著。結果環狀圖案係未有由於矽 熔液及結晶化二氧化矽間之反應予以形成。由於未有使內 表面粗糙的環狀圖案之形成’坩鍋內表面係保持平滑狀。 經濟部智慧財產局員工消費合作社印製 ''電暈〃法：平滑的保持坩鍋內表面之第二方法係可 抑制環狀圖案之擴張（第1 5圖、第1 6圖）。環狀圖案 之環5 2係方英石，作用成使內層1 6之石英玻璃中的結 晶質二氧化矽5 6成長之核生成位置。然而，於環狀圖案 之中心域及環5 2之周圍的電暈之間在相轉移放大的速度 上有差異。方英石電暈或暈係較方英石環5 2之成長早成 長，環5 2係成爲以結晶質二氧化矽56包圍。以環5 2爲 結晶質二氧化矽5 6所拘束，環狀圖案之成長速度至少減 少5 0 %。發揮此結晶化速度之不均衡’以電暈狀結晶層 、、電暈〃包圍環’停止環之成長。結果’內層1 6至yS — 方英石之相移轉係由石英玻璃緩慢進行（亦即，如完全法 般未引起急速的結晶化）’最初的玻璃之大部分可長期保 持。 、、電暈〃坩鍋係與較大且光滑的表面徐緩成長的光滑 方英石表面5 6之連—由通常的甘鍋經較長的期間可維持 玻璃質之內層’不致如先:前技術般:急;速的劣化。 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公釐）-17 - 592945 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（15 ) ''平滑〃法：維持坩鍋之有用性的第三方法係防止粗 糙的表面集合組織域5 4之發生。與先前技術之坩鍋（與 第1 0圖間之比較）之壁上形成的環狀圖案同樣的於、、平 滑〃法之坩鍋（第1 7圖）之內表面上亦使環狀圖案可形 成。 ''平滑〃法之坩鍋的環狀圖案係與於先行技術之坩鍋 的內表面5 0同樣的成長，繼續熔合（第1 8圖、第1 9 圖）。儘管如此，內層1 6中的石英玻璃之結晶化係較' 完全〃法或 ''電暈〃法之坩鍋的任一者徐緩的進行。由於 內層1 6不進行急速的相移轉，玻璃質石英層係不進行習 用的不宜的失透（亦即粗糙度及潛在性的劣化）。 平滑 〃法之坩鍋內表面6 0係保持平滑的表面集合組織6 2。 第2 0圖、第2 1圖係於 ''平滑〃法之坩鍋的內表面上成 長的環狀圖案之平面圖及放大截面圖。環狀圖案係由環狀 圖案之外界面的環5 2而成，其中可看到方英石5 6。方 英石5 6係於內層1 6亦成長著。於先前技術之坩鍋內表 面5 0 (第1 3圖、第1 4圖）及對象內， ''平滑〃法之 坩鍋係亦於環5 2及環狀圖案內亦保持平滑的表面。即於 覆蓋於 '、平滑〃法之坩鍋表面已合體的環上，粗糙度係亦 與習用的坩鍋比較，可予阻止。 操作法之選擇及控制 本發明係由上述三個方法之中選擇所期待的方法。祖 鍋結晶化係★完全〃且最快速，其次係''電暈〃法’最後 爲 '、平滑法〃。於石英玻璃之結晶化促進的強度’周期表 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐）-18 - (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 d 592945 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（16) 之2 A族的元素係最強，接著3 b族元素，4 a族元素。 然而’在相同滲雜水準的前述結晶化劑之強度係最強爲緦 (3 B族），接著鋇（2 A族）、鋁（3 B族）、鈦4 A 族。此等元素之二種以上的混合物或多層坩鍋之組合亦予 使用。鹼元素（亦即L i 、N a 、K等的1 A族）係可使 用’惟容易擴散並非予限定於滲雜層內，故並不佳。於平 滑法，結晶化劑係以鈦或鋁即可。分布於內層之鈦係以 5〇〜13〇PPm之範圍，宜爲7〇〜130ppm之 範圍即可。又，鋁係5 0〜1 5 0 p p m之範圍，7 5〜 1 5 0 p p m之範圍即可。石英之結晶化係又受結晶化劑 之水準所影響。通常，在較高的滲雜水準，以方英石之成 長速度變快。舉一例，若使用鋁時，則方英石之形成係於 2 5 〇 p p m滲雜的層遠較2 5 0 P P m滲雜的層快速進 行。方英石之成長速度以採用較薄的層可增大。已形成 0 · 2 m m厚度之內層1 6的坩鍋係相移轉較具有1 . 2 m m厚度之層的坩鍋快速進行。快速的方英石之成長係通 常由不均勻的滲雜而得。尤其無寧以使用合成石英粉（不 定形）之混合物較結晶質之石英粉（石英）的不均勻滲雜 係較顯著的。 如上述般，上述因子係於由''完全〃法， ''電暈〃法 或''平滑〃法之任一種方法而得的坩鍋之製造方面受限制 。爲簡單之故，在下例雖表示內層1 6之例子，惟至於外 部層1 9亦可應用相同的原理。 (請先閱讀背面之注意事項再填寫本頁) •裝. 訂 d 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-19 - 592945 經濟部智慧財產局員工消費合作社印製 A7 __ _ B7_五、發明説明（17 ) 〔實施例〕 實施例1 : ''完全〃法之坩鍋 於以''完全〃法操作的典型坩鍋，使用較強的結晶化 劑或較高的滲雜水準。例如以鋇滲雜天然內部用石英粉 4 4，導入至使形成約7 0 p P hi之結晶化劑水準的內層 1 6。反之，混合鋇滲雜天然內部用石英粉及純粹的合成 石英粉，形成分散約2 Ο ρ ρ ηι之鋇的內層。 '、完全〃法 之坩鍋的內層1 6係具有典型的厚度0 · 2〜1 . 2mm 。內層1 6之正確厚度係須以石英粉，特定的結晶化劑及 其導入法間之關聯予以決定。於''完全〃法之坩鍋，熔融 已被覆的內部用石英粉4 4並可予製造以取代摻雜結晶化 劑。需以使用被覆內部用石英粉4 4，於內層1 6內使結 晶化劑以不均勻的分布。同樣的，於實質上同時流動內部 用石英粉4 4及結晶化劑時，於熔融層1 6中使結晶化劑 呈不均勻的分布。 實施例2 : 電暈〃法之坩鍋 以''電暈〃法操作的典型坩鍋，係爲使滲雜水準安穩 ’使內層含有在較低位準具有中位的結晶化促進力之結晶 化劑。例如以已滲雜鋁之天然石英粉4 4形成內層1 6。 較宜的內層1 6內的含鋁量係5 0〜1 5 0 p pm。滲雜 層之厚度爲約0 · 2〜1 · 2 m m。於此方法，於全內層 內作成不給予急速的結晶化力，以使用具有鋇或緦類較強 的結晶化促進力之劑並不佳。相同的，至於內層用石英粉 (請先閲讀背面之注意事項再填寫本頁) 裝·、 1T This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -12- 592945 A7 B7 V. Description of invention (1〇) (Please read the precautions on the back before filling this page) Can also be used A mixture of doped quartz powder and undoped quartz powder. When the synthetic quartz powder is used as the unimpregnated quartz powder of the mixture, the crystallization promoting strength of the crystallization agent increases. Glass made of synthetic quartz is softer than natural quartz glass (that is, fused crystal glass). The soft matrix of synthetic quartz glass is very good. When an amorphous quartz glass layer is converted into a cristobalite-type crystallized quartz glass, it causes a volume change and an increase in rigidity (that is, a reduced structural resistance). As a result, when the synthetic quartz powder is pre-encapsulated in the molten inner layer 16 or the outer layer 19, the same deformation can be obtained even at a lower level of doping. In order to prepare a silica sol containing a crystallization agent, a uniformly doped silica gel can be obtained. This gel is another example of an impregnated powder. The gel should preferably be baked for conversion to pure dioxide. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. It is also an impurity of quartz powder. The quartz powder is coated with a crystallization agent or the forming agent contains silica gel, and it can also be supported on quartz powder. The coated quartz powder may be coated with pure quartz powder with an organic material such as an alkoxide. As for other optional introduction methods, it is a mixture of crystallizing agent and un-doped quartz powder such as natural or synthetic quartz powder. There are also examples of simultaneous introduction. For example, barium carbonate (BaC03) or aluminum nitrate is added in the hopper 2 2 b to the internal quartz powder 4 4. Barium carbonate or aluminum nitrate was uniformly mixed with quartz powder for the inside by mixing blades 28. The mixture of the internal quartz powder and barium carbonate or aluminum nitrate is then introduced into the high-temperature atmosphere 42 as described above. During the melting of the internal quartz powder 44, the crystallization agent is inorganic powder such as oxide (BaO), (AhCh), hydroxide (A1 (0H) 3, hydrogen carbonate (A1 (HC〇2) 3, Compound oxides (TiBaCh), nitrides (BaN2), and gaseous materials The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -13- 592945 A7 __—_ B7 V. Description of the invention (11) (BaCh) , (A1C1) 3 or a mixture of most of the foregoing compounds is supplied to the high-temperature fraction S 4 2. At the temperature of the melting pot of the sweet pot, organic compounds that can be converted into any of the foregoing compounds can also be used in the same way. (Please Read the notes on the back before filling this page) In other aspects of the present invention, the crystallizer can be introduced into the high-temperature atmosphere 4 2 from the specified hopper and the internal quartz powder 4 4 at the same time. Controlled by the internal powder hopper 2 The valve system that flows out of the two-agent hopper can be opened like the above-mentioned two valves at the same time. Moreover, in other examples, the crystallization agent may be barium hydroxide (Ba (OH) 2) or barium chloride, for example. (BaCh) and other liquid materials. The liquid solution is in a high temperature atmosphere 4 2 in The internal quartz powder 44 can be introduced before or at the same time. The liquid solution printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be introduced into the internal quartz powder 4 4 at high temperature. It can be directly introduced. For example, a syringe arranged near the end of the flow tube 40 in a high-temperature atmosphere 4 2 can be introduced. The liquid solution is a solvent that can be selected. It can be an organic solution, and the crystallization agent in the liquid solution can be supplied to the powder layer formed before melting. The organic compound, organic solution or aqueous solution of the crystallization agent can be sprayed on the formed powder layer 4 9 The suitable advantage of this agent is that the crystallizing agent can be arranged on a specific area of the layer. For example, only in the side wall portion or the inner side of the bottom 6, the entire inner surface (side and bottom) of the side wall 4 or the bottom 6 A crystallizing agent can be applied to the inside of the side wall 4 below the melting line (the melting line is a line where the molten silicon contacts the inner wall of the crucible after melting). Although the crystallizing agent is the same as the quartz powder for the interior, It was imported into this paper standard to apply Chinese National Standard (CNS) A4 specification (210X 297 mm) 592945 Printed by A7 _ _ _B7_5, the above-mentioned method of invention description (12), middle The layer of quartz powder 4 8 can be used as the inner quartz powder 4 4. For example, the quartz powder for intermediate layer 4 8 can be introduced into the high-temperature atmosphere 4 2 because the intermediate layer 1 8 is formed as described above. Stop the intermediate layer powder The flow of the bucket to introduce the quartz powder 48 for the intermediate layer and the barium compound or aluminum compound into the high-temperature atmosphere 4 2 at the same time can form the inner layer 16. In the same state, pure quartz powder 4 4 for internal use is introduced as described above, followed by internal quartz powder 4 4 during the introduction of barium carbonate or aluminum nitrate. Layer 16 is preformed. The flow rate of barium carbonate or aluminum nitrate is such that the amount of barium carbonate or aluminum nitrate can be changed in a gradient from the inner surface to the main body layer. The related crucible is equivalent to a crucible having a main layer 14, an intermediate layer 18 and an inner layer 16. Therefore, the inner layer 16 has a low content of the agent near the main layer, and a gradient that becomes high in the area near the internal cavity 12 of the crucible may contain barium carbonate or aluminum nitrate. How to operate a crucible with a doped layer 〇 The choice of doped elements used in the inner layer 16 is determined according to the expected operating method. Each crystallization agent has a unique crystallization promoting force, and the degree of crystallization speed of the quartz in the inner layer 16 can be controlled in accordance with the level of doping of the agent. As for the description of the operation method and the method of using the various agents, it begins by adjusting the ring pattern on the inner surface of the crucible used in the CZ method. When using a crucible in the formation of silicon ingots, it is better to set the surface of the inner layer in contact with the melt to a smooth shape in advance. Therefore, in the following description, the "inner layer" and "inner surface" of the crucible should be handled with attention to the most important part of the inner layer. (Please read the precautions on the back before filling this page.) Binding and binding 丨 Wo Ben paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 592945 A7 B7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Description of the invention (13) More specifically, the ring pattern phenomenon is observed on the inner surface of the prior art crucible shown in Figs. 10 to 14. Fig. 10 shows the inner surface of the pan 50, which is in contact with the silicon melt, and most of the circular patterns on the inner surface have been formed. The ring pattern usually has a ring 5 2, and the ring and the area inside the ring are cristobalite 5 6. In the CZ method, the circular pattern increases its area, as shown in Fig. 11, diffuses to the inner surface 50 and increases its proportion. With the increase of the circular pattern, the rough surface gathering structure 5 4 series appeared in the center. The rough surface in the realm of the ring-shaped pattern gathers the tissue domains 5 and 4 to expand on the inner surface of the crucible. Fig. 12 shows the inner surface of a typical crucible obtained by the conventional CZ method. The ring pattern is fused, increasing the rough surface to gather the tissue domain 5 4. As mentioned above, the rough inner surface strongly influences the crystal structure of the grown silicon ingot. An enlarged top view and a cross-sectional view of a loop pattern of the prior art are shown in FIGS. 13 and 14. The center of the ring pattern has a rough surface aggregate structure 5 4 surrounded by cristobalite (crystalline silicon dioxide) 5 6, which can extend from the inner surface 50 to the crucible wall. Cristobalite 5 2 is decorated with brown material, usually observed with a brown ring on the inner surface of the crucible. The small and smooth surface realm 5 5 in the circular pattern of the previous technology exists between the thicker area 5 4 and the inner edge of the ring 5 2. Regarding the roughness of the surface caused by the ring pattern, the present invention adopts the following inner layer of a crucible for providing operations suitable for the so-called three crystallization methods of the complete method, the corona method, and the smoothing method. A combination of the respective elements of the In any of these methods, the crucible is suitable for the use of the extended CZ method (please read the precautions on the back before filling out this page); installation, 11 This paper size applies the Chinese National Standard (CNS) A4 specification ( 210X297 mm) -16- 592945 A7 B7 5. Description of the invention (14), the inner surface is free of rough and no major melting. (Please read the precautions on the back before filling this page.) '' Complete method. In this method, the inner surface of the pot is preheated, and the inner surface of the crucible is crystallized before it comes into contact with the silicon melt. In this method, the occurrence of a ring-shaped pattern is suppressed, and the ring-shaped pattern is not observed during or after step cZ. Therefore, the inner surface of the crucible of the complete method is that after heating, the silicon is coated with / 3 -cristobalite before melting. As a result, the ring pattern was not formed due to the reaction between the silicon melt and the crystallized silicon dioxide. Since there is no formation of a circular pattern with a roughened inner surface, the inner surface of the crucible remains smooth. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs '' Corona method: The second method to keep the inner surface of the crucible smoothly is to suppress the expansion of the ring pattern (Figures 15 and 16). The ring 5 2 of the ring pattern is cristobalite and acts as a nucleation site for the growth of the crystalline silicon dioxide 56 in the quartz glass of the inner layer 16. However, there is a difference in the speed of phase transfer amplification between the central region of the ring pattern and the corona around the ring 52. The cristobalite corona or halo system grows earlier than the cristobalite ring 52, which is surrounded by crystalline silicon dioxide 56. Restricted by ring 5 2 as crystalline silicon dioxide 56, the growth rate of the ring pattern is reduced by at least 50%. Taking advantage of this imbalance in the crystallization rate, the ring growth is stopped by a corona-like crystal layer and a corona ring surrounding the ring. As a result, the phase transition of the inner layer 16 to yS-cristobalite was performed slowly by quartz glass (i.e., no rapid crystallization was caused as a complete method). Most of the original glass could be maintained for a long time. The corona crucible is connected to the large and smooth surface of the smooth cristobalite surface which grows slowly. The inner layer of glassy can be maintained by the ordinary gan pan for a long period of time. General: rapid; rapid deterioration. This paper size applies to China National Standard (CNS) A4 (210x297 mm) -17-592945 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (15) '' Smooth method: maintaining the crucible A useful third method is to prevent the rough surface from gathering tissue regions 54. Similar to the circular pattern formed on the wall of the prior art crucible (compared with Fig. 10), a circular pattern is also formed on the inner surface of the crucible (Fig. 17) which is smooth and smooth. Can be formed. The loop pattern of the crucible in the smooth method grows the same as the inner surface of the crucible of the prior art 50, and continues to fuse (Figures 18 and 19). Nonetheless, the crystallization of the quartz glass in the inner layer 16 proceeds more slowly than any of the crucibles of the 'complete' method or the 'corona method'. Because the inner layer 16 does not undergo a rapid phase shift, the glassy quartz layer system does not perform the customary undesired devitrification (ie, roughness and potential degradation). Smoothing The inner surface of the crucible 6 0 is a smooth surface that gathers tissue 6 2. Figures 20 and 21 are a plan view and an enlarged cross-sectional view of a ring-shaped pattern formed on the inner surface of the crucible of the smoothing method. The ring pattern is formed by the ring 5 2 at the interface other than the ring pattern, among which the cristobalite 56 can be seen. Fang Yingshi 5 6 is growing on the inner layer 16. In the crucible inner surface of the prior art 50 (Figures 13 and 14) and the object, the crucible of the "smoothing method" also maintains a smooth surface in the ring 52 and the ring pattern. That is, on the ring that covers the surface of the crucible which is smooth and smooth, the roughness is also compared with the conventional crucible, which can be prevented. Selection and Control of Operation Methods The present invention selects a desired method from among the three methods described above. The ancestral pot crystallization system is completely complete and the fastest, followed by the "corona method" and finally the "smooth method". The strength of crystallization promoted by quartz glass' periodic table The paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -18-(Please read the precautions on the back before filling this page) 592945 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (2) Group A elements are the strongest, followed by Group 3 b elements and Group 4 a elements. However, the strength of the aforementioned crystallization agent at the same doping level is the strongest of rhenium (Group 3 B), followed by barium (Group 2 A), aluminum (Group 3 B), and titanium Group 4 A. Mixtures of two or more of these elements or combinations of multilayer crucibles are also used. Alkali elements (i.e., Group 1 A of Li, Na, K, etc.) are usable, but are easy to diffuse and are not limited to the doped layer, so they are not good. In the smoothing method, the crystallizing agent may be titanium or aluminum. The titanium distributed in the inner layer is in the range of 50 to 13 PPm, preferably in the range of 70 to 130 ppm. The aluminum range is 50 to 150 p p m, and the range is 75 to 150 p p m. The crystallization of quartz is affected by the level of crystallization agent. Generally, at higher levels of infiltration, the growth rate of cristobalite becomes faster. For example, if aluminum is used, the formation of cristobalite is much faster than the layer doped with 250 p p m than the layer doped with 250 p p m. The growth rate of Fang Yingshi can be increased by using thinner layers. The phase shift of the crucible which has formed the inner layer 16 with a thickness of 0.2 mm is faster than that of a crucible with a layer with a thickness of 1.2 mm. The rapid growth of cristobalite is usually obtained by uneven infiltration. In particular, the use of synthetic quartz powder (unshaped) mixtures is more noticeable than the heterogeneous impermeability of crystalline quartz powder (quartz). As mentioned above, the above factors are limited in the manufacture of crucibles obtained by any one of the `` complete method, '' the `` corona method '', or the `` smooth method ''. For simplicity, although the inner layer 16 is shown in the following example, the same principle can be applied to the outer layer 19 as well. (Please read the precautions on the back before filling out this page) • Binding. Order d This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -19-592945 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs __ _ B7_ V. Description of the invention (17) [Example] Example 1: A `` complete crucible crucible is a typical crucible operated with a `` complete crucible method, using a strong crystallization agent or a Level of penetration. For example, natural quartz powder 4 4 is impregnated with barium, and introduced into the inner layer 16 to a crystallizing agent level of about 70 p P hi. On the contrary, the mixed barium is mixed with natural internal quartz powder and pure synthetic quartz powder to form an inner layer of barium dispersed by about 20 ρ ρ η η. ', The inner layer 16 of the crucible with complete method has a typical thickness of 0.2 mm to 1.2 mm. The correct thickness of the inner layer 16 must be determined by the relationship between the quartz powder, the specific crystallization agent and its introduction method. In the "completely crucible" method, the coated interior quartz powder 44 is melted and can be manufactured to replace the doped crystallizer. It is necessary to use a coating of internal quartz powder 4 4 to unevenly distribute the crystallization agent in the inner layer 16. Similarly, when the internal quartz powder 44 and the crystallizing agent are flowed substantially simultaneously, the crystallizing agent is unevenly distributed in the molten layer 16. Example 2: A crucible with a corona method. A typical crucible operated by the `` corona method '' is to stabilize the doping level, so that the inner layer contains a medium-level crystallization promotion force at a lower level. Crystallization agent. For example, the inner layer 16 is formed of natural quartz powder 44 which has been doped with aluminum. The preferable aluminum content in the inner layer 16 is 50 to 150 p pm. The thickness of the doped layer is about 0 · 2 ~ 1 · 2 m. In this method, it is not good to prepare an agent that does not give a rapid crystallization force in the entire inner layer, and to use a strong crystallization promoting force of barium or osmium. The same, as for the inner layer of quartz powder (Please read the precautions on the back before filling this page)
、1T 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇Χ 297公釐） -20 - 592945 A7 _ B7 五、發明説明（18) 44 ’以天然石英法較合成石英法優越，故較宜。然而， 以於滲雜內層用粉4 4 (或滲雜合成石英粉之使用）加入 合成石英粉使較弱的結晶化劑之使用成爲可能。 同樣的’滲雜石英粉係結晶化促進劑均勻的分布於內 層1 6之中，故由被覆石英粉或同時導入較宜的。此優點 係如前述般，結晶化劑具有梯度予以分布的情形亦可。 實施例3 : ''平滑〃法之坩鍋’ 以此方法操作的坩鍋係側壁4及底部6之內側的石英 玻璃之結晶化徐緩進行、殘存在平滑的表面。 '平滑〃法 之坩鍋的內層1 6係採用以結晶化促進力爲中庸的較弱的 結晶化劑即可。至於結晶化劑，例如鈦係以1 0 0 P P m 分布於熔融天然內部用石英粉而得的滲雜層內即可。由經 予選擇的特定結晶化劑及合成內部用石英粉4 4之使用’ 可有效的操作之薄內層可形成。坩鍋之設計應與預定的 C Z法之條件，尤其製程之加熱計劃配合。 實施例4 :鋁滲雜坩鍋 以同樣大小的製造本發明之坩鍋A、B、C及D四個 。坩鍋P係由先前技術予以製造。各坩鍋之大小爲2 2英 吋。 坩鍋A之內層1 6係以與己滲雜鋁之內部用石# $ @ 混合物製作的。混合已滲雜1 〇 5 p p m之含量水準的內 部用石英粉及天然的鋁含量約8 p p m之純粹的內部用石 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇><297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝· —參 經濟部智慧財產局員工消費合作社印製 592945 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（19) 英粉。已混合的內部用石英粉4 4係5 4 : 4 6之比例的 石，含有5 0 P Pm之平均鋁。 坩鍋B係同樣的予以製作成具有已滲雜的內層1 6 ° 製作此坩鍋之內層1 6時所使用的混合物係由1 〇 5 ρ ρ γπ之銘慘雜內部用石央粉及純粹的合成石央粉而成’ 後者的鋁含有量係〇 · 5 P p m以下。已滲雜及純粹的內 部用石英粉係以1 : 2之比例予以混合。結果，此混合物 之平均鋁含有量成爲3 5 p pm。 坩鍋C之已滲雜鋁的內層1 6係採用鋁被覆之轉粗的 天然石英粉予以製造。此內部用粉末之平均鋁含有量係以 8 5 p pm粉末之4 2%爲較2 0 0 //m大的尺度。 採用上述完全法、電暈法、平滑法，製作具有已摻雜 銘之內層1 6之祖鍋A〜C。取出三個堪鍋並在最終步驟 之前在模具內冷卻5分鐘。 先前技術之坩鍋P係直徑2 2英吋。在製造方法方面 使用純粹的天然石英粉以取代鋁滲雜內部用石英粉。此天 然石英粉係大致含有8 p pm之鋁。 採用坩鍋A〜P之坩鍋並使用於1 2 0小時之c Z法 。亦即’於矽基板之熔融後的選擇溫度使用1 2 0小時。 此寺結果不於表1。 (請先閲讀背面之注意事項再填寫本頁) .裝· 、11 d 本紙張尺度剌 t ( CNS ) A4i|F^X297^¥) -2Z- 592945、 1T This paper size applies Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) -20-592945 A7 _ B7 V. Description of the invention (18) 44 'The natural quartz method is superior to the synthetic quartz method, so it is more suitable . However, the addition of synthetic quartz powder to the powder for impregnating the inner layer 4 (or the use of impregnated synthetic quartz powder) makes the use of weaker crystallization agents possible. The same 'doped quartz powder-based crystallization accelerator is uniformly distributed in the inner layer 16; therefore, it is preferable to introduce the coated quartz powder or simultaneously. This advantage may be the case where the crystallizing agent is distributed with a gradient as described above. Example 3: "Crucible for smoothing" The crucible operated in this way was slowly crystallized from quartz glass inside the side walls 4 and bottom 6 and remained on a smooth surface. 'Smoothing method The crucible's inner layer 16 should use a weaker crystallization agent whose crystallization promoting force is moderate. As for the crystallization agent, for example, the titanium system may be distributed at 100 P P m in the impurity layer obtained by melting the natural internal quartz powder. A thin inner layer can be formed by using a specific selected crystallizing agent and the use of synthetic internal quartz powder 44, which can be effectively handled. The design of the crucible should match the conditions of the predetermined CZ method, especially the heating plan of the process. Example 4: Aluminum impregnated crucible Four crucibles A, B, C and D of the present invention were manufactured with the same size. The crucible P is manufactured by the prior art. The size of each crucible is 22 inches. The inner layer 16 of crucible A is made with a mixture of aluminum and aluminum that has been impregnated with aluminum. Mixed with internal quartz powder with a level of 105 ppm and pure internal stone paper with a natural aluminum content of about 8 ppm. The size of the paper is applicable to the Chinese National Standard (CNS) A4 (21〇 > < 297). (Please read the notes on the back before filling out this page.) Installation · — Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 592945 A7 B7 Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs powder. The mixed internal quartz powder 4 4 series 5 4: 4 6 ratio stone contains an average aluminum of 50 P Pm. Crucible B is similarly made with an impregnated inner layer 16 ° The mixture used when making the inner layer 16 of this crucible is based on the inscription of 1 0 05 ρ ρ γπ And pure synthetic stone powder. The latter has an aluminum content of 0.5 P pm or less. The doped and pure internal quartz powder is mixed at a ratio of 1: 2. As a result, the average aluminum content of this mixture became 3 5 p pm. The inner layer 16 of the crucible C, which has been doped with aluminum, is made of aluminum-coated and coarse natural quartz powder. The average aluminum content of this internal powder is 4 2% of 85 p pm powder, which is larger than 2 0 0 // m. Using the above-mentioned complete method, corona method, and smoothing method, the ancestral pots A to C with the inner layer 16 with doped inscriptions were produced. Remove three pans and cool in the mold for 5 minutes before the final step. The prior art crucible P is 22 inches in diameter. In terms of manufacturing method, pure natural quartz powder is used instead of quartz powder for aluminum doping. This natural quartz powder contains approximately 8 p pm of aluminum. The crucibles A to P were used and the c Z method was used for 120 hours. That is, the selected temperature after melting of the silicon substrate is used for 120 hours. The results of this temple are not shown in Table 1. (Please read the precautions on the back before filling out this page). Packing, 11 d This paper size 剌 t (CNS) A4i | F ^ X297 ^ ¥) -2Z- 592945
A B 五、發明説明（2G ) 【表1】 坩鍋 方法 初期內表面 120時間CZ 環狀圖案 集合組織 法後的內部 之形成 集合組織 A 電暈法 平滑玻璃 平滑 少量 B 平滑法 平滑玻璃 平滑 合體 C 電暈法 平滑玻璃 平滑 少量 D 完全法 平滑方英石 平滑 Μ P 習用法 平滑玻璃 粗糙 合體 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 環狀圖案5 2係可具於坩鍋A之內表面5 0及內層1 6內 。此等環狀圖案並非被覆坩鍋A之內表面程度的較高比例 。因此，此例之ί甘鍋係以阻止二氧化砂結晶之擴展，可使 內表面之平滑度保持著。 於坩鍋Α及C之內表面5 0上所具的環狀圖案係於環 狀圖案環之側面及中間之兩側（第2 0圖、第2 1圖）爲 以方英石所包圍著。環狀圖案內之內表面5 0係平滑度經 予維持著。 同樣的使用坩鍋B於1 2 0小時之C Z法上。環狀圖 案係經予形成於內層1 6上，擴展至覆蓋內表面5 0之大 部分，予以熔合。儘管最初的表面上幾乎未殘留著環狀圖 案中的內表面係具有平滑的面。C Z法中，經予提拉的矽 晶鑄錠係未受已形成於此態樣之內層1 6中的環狀圖案或 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23- 592945 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（21 ) 其擴展所阻礙° D坩鍋係以本發明之完全法予以製作，坦鍋D係在 1 4 0 0〜1 6 0 0°C予以保持1分鐘’其後與上述同法 冷卻，亦即除進行約5分鐘之冷卻外’與坩鍋C同法製作 〇 適用坩鍋D於1 2 0小時之C Z法後’檢查內層1 6 。內表面5 0係由結晶質二氧化砂以本質上形成’環狀圖 案並未明確的看出。 將先前技術之坩鍋P同樣的使用於1 2 0小時之c Z 法。然而，在約8 0小時於初期的矽鑄錠上會引起破壞結 晶構造之粉末境界缺陷。以此缺陷強制的制止C Z法，未 能製得符合期待的用途之矽晶。 檢查坩鍋P之內表面時，幾乎整體爲環狀圖案所被覆 ，得知未殘存最初的玻璃質之表面。環狀圖案環中表面係 以較粗的集合組織而成爲砂晶干擾之原因。 上述方法，係以失透促進劑由被覆坩鍋內表面而可分 布結晶化劑於坩鍋內層內者，滲雜層係與通常的被覆法相 較具有若干優點。 在本發明係可詳細的控制內層1 6或外部層1 9之結 晶化劑水準。於前述的態樣，內部用石英粉4 4係於其導 入，熔融前經予滲雜鋁或鋇。滲雜粉末內所含的結晶化劑 之量係以先前已進行的分析可予正確的決定。內層1 6內 的結晶化劑之含有量係在料斗內混合例如滲雜石英粉及純 粹的石英粉並可正確的控制。 C請先閱讀背面之注意事項再填寫本頁} •裝- 訂· 4 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -24- 592945 A7 B7 五、發明説明（22) (請先閱讀背面之注意事項再填寫本頁) 以可改變內層1 6之厚度或內部石英粉之導入速度及 時間可操作。並無製造時的結晶化促進劑之損失’例如由 昇華引起的損失。實質上經予導入的劑全部爲內層1 6內 所固定。加上在三維層之滲雜亦與先行技術相較’可較減 少結晶化劑。經予導入高溫雰圍雰圍或坩鍋之內表面域內 的結晶化劑之量係可計算的。由本發明之方法所構築的祖 鍋係以先行技術之表面被覆坩鍋所使用的 ''失透促進劑" 之約1 0分之1以數據上判明係可有效的操作。 結晶化劑係分布於石英玻璃內並使熔融之故，坩鍋又 呈尺度上安定，可以與淸淨或蝕刻等通常純粹的石英坩鍋 同樣的處理。亦不需要追加的製造法或坩鍋之特定的處理 。例如於通常的坩鍋之外側殘存的未熔融粉末係可以噴砂 法良好的去除，可以水洗淨。將i甘鍋切割成特定的大小後 ，以稀氫氟酸蝕刻，以純水淸洗可予良好的去除。坩鍋係 接著在淸淨空氣浴中乾燥，並予包裝，供出貨用而可予裝 入箱內。 以本發明之方法所構築的坩鍋係由內層1 6或外部層 1 9在不移動結晶化劑下可予容易處理。 經濟部智慧財產局員工消費合作杜印製 若爲熟習此項技藝人士依本文獻之記載或可實施。爲 理解本發明並不多作說明。至於其他例方面，爲人已知的 特徵由於不需使本發明弄混淆而不作詳細記載。 以本發明較佳的形態所揭示的同時，特定的態、樣，經予 揭示、說明，並不可解釋成限定性意義。原本，本發明可 以多種方法進行修正，但目前的記載對熟習此項技藝人士 -25- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 592945 A7 B7 五、發明説明（23 ) 而言爲顯而可知的。本發明人，以發明之主題可考慮成含 有各種要件、特徵、功能及/或性質之全部結合及次結合 者。 (請先閲讀背面之注意事項再填寫本頁) 發明之功效 本發明之坩鍋係具有內層、主體層，結晶化層係分布 於其內層並呈結晶化，內層即使與矽熔液接觸，但亦可維 持坩鍋內表面之平滑度，又由於結晶化使坩鍋之尺度安定 性提高，可長期的提拉矽單晶。該坩鍋係採用向來公知的 製造方法以於主體層之內表面上形成已滲雜結晶化劑之內 層的方法可予製造，係工業上利用價値極高者。 圖式之簡單說明 第1圖爲本發明之石英玻璃坩鍋之截面圖。 第2圖爲第1圖之石英玻璃坩鍋的壁部之放大部分截 面圖。 第3圖爲本發明之石英玻璃坩鍋之最初的態樣之壁部 的放大部分截面圖。 經濟部智慧財產局員工消費合作社印製 第4圖爲本發明之石英玻璃坩鍋之第二態樣之壁部的 放大部分截面圖。 第5圖〜第9圖係本發明之石英玻璃坩鍋的製造方法 之說明圖。 第1 0圖〜第1 2圖係表示由C Z法中引起的環狀圖 案之發生的習用石英玻璃坩鍋之內表面的部分平面圖。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） · 26 - 592945 A7 B7 五、發明説明（24) 第1 3、第1 4圖係第1 0圖表示的習用坩鍋壁之放 大部分上面及截面圖。 第1 5圖、第1 6圖係由本發明之電暈法而得的石英 玻璃坩鍋之內表面的放大部分上面及截面圖。 第1 7圖〜第1 9圖係由本發明之平滑法而得的石英 玻璃坩鍋之內表面的放大部分上面及截面圖。 第2 0圖、第2 1圖係第1 7圖所示的放大部分上面 及截面圖’說明環狀圖案之發生。 (請先閲讀背面之注意事項再填寫本頁) 圖 4 6 經濟部智慧財產局員工消費合作社印製 2 2 2 2 號之說明 :石英玻璃坩鍋 :坩鍋壁 :側壁 :底部 4 :主體層 6 :內層 8 :過渡層 9 :外部層 〇 :坩鍋模具 2 a 〜2 2 d ： 6 a 〜2 6 d : 8 a 〜2 8 d : 2、4 7 :刮刀 7 :電極組合 料斗 控制料斗 攪拌機 -27- 本紙張尺度適用中國國家標準（CNS ) A4規格（2i〇X297公釐） 592945 A7 _B7 五、發明説明（25 ) 42 :高溫雰圍雰圍 5 0 :坩鍋內表面 5 2 :環狀圖案環 5 4 :表面集合組織 5 6 :方英石 6 2 :平滑的表面集合組織 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）AB V. Description of the invention (2G) [Table 1] The inner surface of the crucible method at the beginning of the 120-year time CZ ring pattern collection organization internal formation after the organization structure A corona smooth glass smoothing a small amount B smooth smooth glass smooth composite C Corona smooth glass smooth a small amount D full smooth smooth cristobalite smooth MP custom smooth glass rough fit (please read the precautions on the back before filling this page) The Ministry of Economic Affairs Intellectual Property Bureau employee consumer cooperative prints a ring pattern 5 2 series It can be contained in the inner surface 50 and the inner layer 16 of the crucible A. These circular patterns do not cover the inner surface of crucible A to a high degree. Therefore, the gancao pot in this example is to prevent the expansion of sand dioxide crystals, and to maintain the smoothness of the inner surface. The ring pattern on the inner surface 50 of crucibles A and C is on the side and middle sides of the ring-shaped pattern ring (Fig. 20, Fig. 21) surrounded by cristobalite. The smoothness of the inner surface 50 in the circular pattern is maintained. The crucible B was also used in the CZ method for 120 hours. The ring pattern is formed on the inner layer 16 and extended to cover a large part of the inner surface 50 to be fused. Although the original surface hardly left the inner surface of the circular pattern with a smooth surface. In the CZ method, the lifted silicon ingot system is not subject to the ring pattern already formed in the inner layer 16 of this state or the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -23- 592945 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (21) The expansion is hindered ° D The crucible is made by the complete method of the present invention, and the pan D is in 1 4 0 0 ~ 16 0 0 ° C for 1 minute 'and then cooled in the same way as above, that is, except for about 5 minutes of cooling' Manufactured in the same way as crucible C. Applicable to CZ of crucible D at 120 hours After the method 'check the inner layer 16. The inner surface 50 is formed by crystalline sand dioxide in a substantially 'ring pattern', which is not clearly recognized. The crucible P of the prior art was also used in the c Z method for 120 hours. However, in the initial silicon ingot of about 80 hours, a powder boundary defect that destroys the crystal structure is caused. The C Z method was forcibly suppressed by this defect, and silicon crystals meeting the intended use could not be produced. When the inner surface of the crucible P was inspected, almost the entire surface was covered with a ring pattern, and it was found that the original glassy surface did not remain. The surface of the ring-shaped patterned ring is structured with coarse aggregates, which is the cause of sand crystal interference. In the above method, the devitrification promoter is used to cover the inner surface of the crucible and the crystallization agent can be distributed in the inner layer of the crucible. The impregnated layer has several advantages compared with the ordinary coating method. In the present invention, the level of the crystallization agent in the inner layer 16 or the outer layer 19 can be controlled in detail. In the aforementioned state, the inside is introduced with quartz powder 4 4, and aluminum or barium is pre-doped before melting. The amount of crystallizing agent contained in the impregnated powder can be accurately determined based on the analysis previously performed. The content of the crystallizing agent in the inner layer 16 is mixed in the hopper, such as doped quartz powder and pure quartz powder, and can be accurately controlled. CPlease read the notes on the back before filling in this page} • Binding-Binding · 4 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -24- 592945 A7 B7 V. Description of the invention (22) ( (Please read the precautions on the back before filling this page) to change the thickness of the inner layer 16 or the introduction speed and time of the inner quartz powder. There is no loss of the crystallization accelerator at the time of manufacture ', such as loss due to sublimation. Substantially all the pre-introduced agents are fixed in the inner layer 16. In addition to the inclusion in the three-dimensional layer, compared with the prior art ', the crystallizing agent can be reduced. The amount of the crystallization agent introduced into the high-temperature atmosphere or the inner surface area of the crucible can be calculated. The ancestral pot constructed by the method of the present invention is about 1/10 of the "devitrification enhancer" used in the prior art to coat the crucible with the surface, and it is judged that the operation is effective. Because the crystallizing agent is distributed in the quartz glass and melted, the crucible is stable on a scale, and can be treated in the same way as a pure quartz crucible such as cleaning or etching. Nor does it require additional manufacturing methods or specific treatments for crucibles. For example, the unmelted powder remaining on the outside of a normal crucible can be removed by sand blasting and washed with water. After cutting the i-gam pot to a specific size, it is etched with dilute hydrofluoric acid and washed with pure water to remove it well. The crucible is then dried in a clean air bath and packaged for shipment and can be placed in a box. The crucible constructed by the method of the present invention can be easily handled by the inner layer 16 or the outer layer 19 without moving the crystallization agent. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs for consumer cooperation Du printed If you are familiar with this skill, it may be implemented according to the records in this document. To understand the present invention, it is not described in detail. As for other examples, well-known features are not described in detail because they do not need to confuse the present invention. At the same time as being disclosed in the preferred form of the present invention, specific states and patterns, after being disclosed and explained, cannot be interpreted in a limiting sense. Originally, the present invention can be modified in a variety of ways, but the current record is for those skilled in the art. 25- This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 592945 A7 B7 V. Description of the invention (23 ) Is obvious. The inventor can consider all combinations and sub-combinations of the subject matter of the invention with various elements, features, functions, and / or properties. (Please read the precautions on the back before filling in this page) The effect of the invention The crucible of the present invention has an inner layer and a main body layer. The crystallization layer is distributed in the inner layer and is crystallized. Contact, but can also maintain the smoothness of the crucible's inner surface, and because of crystallization, the crucible's dimension stability is improved, and the silicon single crystal can be pulled up for a long time. This crucible can be manufactured by a conventionally well-known manufacturing method to form an inner layer doped with a crystallizing agent on the inner surface of the main body layer, and it is industrially extremely expensive. Brief Description of Drawings Fig. 1 is a sectional view of a quartz glass crucible of the present invention. Fig. 2 is an enlarged sectional view of a wall portion of the quartz glass crucible of Fig. 1; Fig. 3 is an enlarged partial cross-sectional view of a wall portion of the first embodiment of the quartz glass crucible of the present invention. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. Figure 4 is an enlarged partial cross-sectional view of the second aspect of the quartz glass crucible of the present invention. 5 to 9 are explanatory diagrams of a method for manufacturing a quartz glass crucible of the present invention. Fig. 10 to Fig. 12 are partial plan views showing the inner surface of a conventional quartz glass crucible in which a ring pattern is caused by the CZ method. This paper size applies to China National Standard (CNS) A4 (210X297 mm) · 26-592945 A7 B7 V. Description of the invention (24) Figures 1 and 3 are the walls of the conventional crucible shown in Figure 10 Enlarge part of the top and cross-sectional views. Figures 15 and 16 are enlarged and cross-sectional views of the inner surface of the quartz glass crucible obtained by the corona method of the present invention. Figures 17 to 19 are enlarged and sectional views of the inner surface of the quartz glass crucible obtained by the smoothing method of the present invention. Fig. 20 and Fig. 21 are the top and cross-sectional views of the enlarged portion shown in Fig. 17 to illustrate the occurrence of the circular pattern. (Please read the precautions on the back before filling out this page) Figure 4 6 Description printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs No. 2 2 2 2: Quartz glass crucible: Crucible wall: Side wall: Bottom 4: Body layer 6: Inner layer 8: Transition layer 9: Outer layer 0: Crucible mold 2a ~ 2 2d: 6a ~ 2 6d: 8a ~ 2 8d: 2, 4 7: Scraper 7: Electrode combination hopper control Hopper mixer-27- This paper size is in accordance with Chinese National Standard (CNS) A4 (2i × 297mm) 592945 A7 _B7 V. Description of the invention (25) 42: High temperature atmosphere 5 0: Crucible inner surface 5 2: Ring Shaped pattern ring 5 4: Surface collection organization 5 6: Fang Yingshi 6 2: Smooth surface collection organization (please read the precautions on the back before filling this page) Printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economy This paper applies to China Standard (CNS) A4 size (210X 297 mm)