8 0 A7 B7 經濟部中央樣準局員工消費合作杜印" 五、發明説明（1 ) 本發明是有關於單結晶矽的製造裝置及製造方法， 特別是有關於可獲得極低氧氣濃度之單結晶矽的製造裝 置及製造方法。 單結晶矽通常是由CZ方法所製成的。上述CZ法包 括：裝填複晶矽到安裝於單結晶製造裝置中的石英坩堝 ;以環繞於石英坩堝四周的加熱器來加熱及熔化上述原 料（複晶矽）；將安裝於一種晶夾之種晶（Seed)浸入熔液中 ’以及當拉引上述種晶夾以便成長—具有預定直徑及長 度之單結晶矽時，以相同或相反方向旋轉上述種晶夾及 石英掛禍。 當石英坩堝的表面與熔液接觸時，包含在石英坩堝 表面的氧氣f熔入上述熔液中，並且會與此熔液反應成 為氧化矽（SiOx)。大部分的氧化矽會從熔液的表面蒸發 掉，並與導入到單結晶製造裝置中的惰性氧體，如氩氧 ，一起排出。但是一部分的氧化矽會保留在單結晶矽中 在成長單結晶開始時，在單結晶梦中具有高的氧氣濃 度’但是會有隨固化率之上升而減小的趨勢。此外，陷 入單結晶中的氧氣具有内部除氣功能及清除產生在半導 體裝置製程中少量的重金屬污染，當氧氣包含於晶圓表 面上的活動層中時，氧氣會成為氧誘導堆積缺陷之形成 的中心《因而嚴重影嚮半導體裝置的特性。 為了使氧氣能於軸向上均勻地分佈，例如依據揭露 於日本特開平公告6_56571之單結晶之威氣濃度控制方 法，一倒立圓錐形或®柱形熱遮蔽架安裴於熔液上方 本紙張尺度適用中國國家標準（CNS } A4規格（2丨0X297公釐） (請先鬩讀背面之注意事項再填寫本頁j8 0 A7 B7 Consumption Cooperation between Employees of the Central Procurement Bureau of the Ministry of Economic Affairs Du Yin " V. Description of the Invention (1) The present invention relates to a device and method for manufacturing monocrystalline silicon, and particularly to obtaining extremely low oxygen concentration. Device and method for manufacturing single crystal silicon. Single crystalline silicon is usually made by the CZ method. The above-mentioned CZ method includes: filling polycrystalline silicon into a quartz crucible installed in a single crystal manufacturing device; heating and melting the above-mentioned raw materials (polycrystalline silicon) with a heater surrounding the quartz crucible; and installing the seed in a crystal holder Seeds are immersed in the melt 'and when the above seed crystal clips are pulled for growth-single crystal silicon with a predetermined diameter and length, the above seed crystal clips and quartz are rotated in the same or opposite directions. When the surface of the quartz crucible is in contact with the melt, the oxygen f contained in the surface of the quartz crucible is melted into the above-mentioned melt, and reacts with the melt to form silicon oxide (SiOx). Most of the silicon oxide evaporates from the surface of the melt and is discharged together with an inert oxygen gas such as argon oxygen introduced into the single crystal manufacturing apparatus. However, a part of the silicon oxide remains in the single crystal silicon. At the beginning of the growth of the single crystal, it has a high oxygen concentration in the single crystal dream ', but it tends to decrease as the curing rate increases. In addition, the oxygen trapped in the single crystal has an internal degassing function and removes a small amount of heavy metal pollution generated in the semiconductor device process. When the oxygen is contained in the active layer on the wafer surface, the oxygen will form the formation of oxygen-induced stacking defects. The center "thus seriously affects the characteristics of semiconductor devices. In order to make the oxygen evenly distributed in the axial direction, for example, according to the method for controlling the concentration of single crystals disclosed in Japanese Unexamined Patent Publication No. 6_56571, an inverted cone or ® cylindrical thermal shield is placed on the paper scale above the melt. Applicable to China National Standard (CNS) A4 specification (2 丨 0X297 mm) (Please read the precautions on the back before filling in this page j
，1T 線, 1T line
-I -I I 1 442580 經濟部中央標準局員工消費合作社印製 A7 B7 五 '發明説明（2 ) ~~ 改變熔液表面與熱遮蔽架底端間之間隙，以便控制單結 晶的氧氣濃度。 但是，依據上述方法，很難獲得具有少於1〇xl〇ncm3 之極低的氧氣濃度》特別地，在最近這幾年，因為石英 坩堝的尺寸隨單結晶矽之擴大而加大，所以石英坩堝與 熔液接觸之表面積亦隨之增^。並且，因供應到加熱器 上的電力増加，故熱量提供到石英坩堝也因而增加β相 對地，溶入熔液中的氧氣量會增加，所以要製造具有低 氧氣濃度的結晶變得更加因難β 有鑑於上述昔知間題，本發明之目的是提供單結晶 發之製造裝置及製造方法’其可製造具有小於 10xl017aton^cm3及在軸向上具有均勻氧氣濃度的單結 為了達到此目的’本發明之單結晶石夕製造裝置是利 用CZ方法之單結晶碎製造裝置，其特徵在於具有一可 提供磁場的裝置；以一惰性氣體整流筒，其為中空之倒 立圊錐形或圓柱形，並且環繞於成長中的單結晶矽。 本發明之製造方法使用上述製造裝置，其特徵在於 藉由供應磁場來控制溶液對流；以及藉由一惰性氣體整 流筒以增加氧體從熔液表面之排放能力的相乘效應，以 將成長中之單結晶矽的氧氣濃度控制在低於 10xl017atoms/cm3 以下。 基於以上所述，因單結晶矽製造裝置、具有一可供應 磁場的裝置、一環繞單結晶矽的惰性氣體整流筒，所以 4 本紙張尺度適用中國國家標準（CNS ) A4規格（2彳0X297公釐} (請先閩讀背面之注^^項再填寫本頁)-I -I I 1 442580 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 Five 'Explanation (2) ~~ Change the gap between the surface of the melt and the bottom of the heat shield in order to control the oxygen concentration of single crystals. However, according to the above method, it is difficult to obtain an extremely low oxygen concentration of less than 10 × 10 cm3. In particular, in recent years, because the size of a quartz crucible has increased with the expansion of single crystal silicon, so quartz The surface area of the crucible in contact with the melt also increases. In addition, because the electric power supplied to the heater is increased, the heat supplied to the quartz crucible is also increased. In contrast, the amount of oxygen dissolved in the melt will increase, so it is more difficult to produce crystals with low oxygen concentration. β In view of the above-mentioned problems, the purpose of the present invention is to provide a device and method for manufacturing single crystal hair, which can produce single knots with less than 10xl017aton ^ cm3 and a uniform oxygen concentration in the axial direction in order to achieve this purpose. The invented single crystal stone manufacturing device is a single crystal crushing manufacturing device using the CZ method, which is characterized by having a device capable of providing a magnetic field; an inert gas rectifying cylinder, which is a hollow inverted conical or cylindrical shape, and Surrounding growing single crystal silicon. The manufacturing method of the present invention uses the above-mentioned manufacturing device, which is characterized by controlling the convection of the solution by supplying a magnetic field; and a multiplicative effect of increasing the discharge capacity of oxygen from the surface of the melt by an inert gas rectifying cylinder, so as to grow the The oxygen concentration of single crystal silicon is controlled below 10x1017 atoms / cm3. Based on the above, due to the single crystal silicon manufacturing device, a device capable of supplying a magnetic field, and an inert gas rectifier tube surrounding the single crystal silicon, 4 paper sizes are applicable to the Chinese National Standard (CNS) A4 specification (2 彳 0X297 mm).厘} (Please read the note ^^ on the back before filling out this page)
，1T 線 “2580 Λ7 Β7 經濟部中央標準局*； Η消費合作社印製 五、發明説明（3 ) 可同時控制熔液的對流及從熔液蒸發之氧氣排放。 供應磁場至熔液可增加正交於磁力線之導電熔液的 有效動態黏性係數’因而可阻止熔液的對流。當提供一 反磁場時’可阻止沿著石英坩堝之牆面（垂直方向）之熔 液對流’因而可阻止氧氣量從石英坩堝溶於熔液中。因 此，可以減少陷於單結晶矽中之氧氣量。再者，將情性 氣體整流筒之底部至熔液表面間之間隙維持在一適當值 以改善藉由惰性氣體來排放氧化矽（Si〇x)，可進一步減 少陷入單晶矽的氧氣量》藉由上述之相乘效應，可獲得 低氧氣濃度及沿轴向上具均勻氧氣濃度分佈的結晶。 為使本發明前述之目的、特徵和優點能更易明瞭， 以下乃舉一辑佳實施例並配合圖式說明。 圖式之簡單說明： 第1圖顯示出單結晶石夕製造裝置之部分剖面圖；以 及 第2圖顯示出單結晶矽之軸向氧氣濃度之比較圖式 〇 符號說明： 1~主室、la〜排氣孔、4〜石英甜禍、5〜溶液、9〜 氣體整流筒、10〜線圈以及12〜單結晶梦。 實施例： 第1圖係顯示出單結晶矽製造裝置之部分剖面圖。 在主室1的中心部位’石墨坩堝3是安g在可旋轉及提 升之坩堝轴2上。石英坩堝4位於石墨坩堝3 «ι»用來容 {請先閲讀背面之注意事項再填寫本頁) 冬紙浓Κ度通用肀囷國家標準（CNS ) Α4規格（公嫠 經濟部中央標準局員工消費合作社印繁 442580 A7 ______B7 五、發明説明（4 ) 納複晶矽的熔液5。圓柱形加熱器6或圓柱形恒溫筒7 是安裝在上述石墨坩堝3的四周。一氣體整流筒9藉由 支持元件8而安裝在恒溫筒7的頂部。上述氣體整筒9 是一倒立圓錐形筒，其上端的開口大於下端的開口且 由石墨或SiC所製成《主室i的上端是連接到一導引室 (Pull Chamber)(未顯示於圖卞卜在主室i的下端具有一 連接到真空泵（未顯示於圖中）的排氣孔la。再者，環狀 線圈10垂直地設立在主室1的外部。 將塊狀複晶矽裝填入石英坩堝3中，並藉由加熱器6 來加熱及熔化使其變成熔液5 ^之後，將安裝在種晶夾 11上的種晶結晶浸入熔液5中。然後，當拉引種晶夾u 以便成長單_晶矽12時，以相同或相反方向旋轉上述種 晶夾11及石墨坩堝3。當電力供應到線圈1〇時，會在 水平方向上產生磁場而供應到上述熔液5中。因此，可 阻止與磁場線成正交的熔液對流，進而可減少石英坩堝4 之内牆上的氧溶入熔液令。 另外一方面，惰性氣體，如氬氣，從上述導引室向 下導入，並經由成長中的單結晶矽12及氣體整流筒9間 的間隙，然後在石英坩堝4的内牆及氣體整流筒9間上 升。之後，惰性氣體往下流到石墨坩堝3及加熱器6間 的間隙或者加熱器6及恒溫筒7間的間隙，並且從排氣 孔1排出。當通過熔液5表面及氣體整流筒9間的間隙 時’上述惰性氣艘會被加速β因而有利於^從溶液5所蒸 發之氧化碎（SiOx)的排出《但是’如果熔液5表面及整 _ 6 本紙張尺度it财關家絲{ CNS ) A4g ( 2丨Gx 297公楚）' (請先聞讀背面之注意事項再填寫本頁) 訂 -線 442580 五、發明説明（5) 流筒9底部間的間隙太小，則石英坩堝4的輻射熱會被 氣體整流筒9所遮蔽，熔液5的表面溫度下降，因此， 阻止氧化碎（SiOx)的蒸發。結果，增加所陷入之氧氣漠 度°因此’ 50mm大的間隙是所期望的。 況且，相對於900〜2000L容量的主室，惰性氣體的 流速期望為35〜65L/min ’以便維持從熔液5所蒸發之氧 化矽的排放能力，以及阻止從熔液5表面與整流筒9底 部間之間隙通過之惰性氣體的亂流產生。如果惰性氣體 的流速小於35L/min ’則氧化矽無法足量的放出，所以 無法獲得具有極低氧氣濃度的單結晶。如果惰性氣體的 流速超過65L/min，則會發生亂流，因此非晶氧化矽會 附著在氣體#流筒9的外面。 經濟部中央標準局員工消費合作杜印製 (諳先閲讀背面之注意事項再填寫本頁} 第2圖顯示出利用本發明之製造方法及昔知技術所 製成之單結晶發間之軸向氧氣濃度的比較。在此實施例 中，將120Kg的複晶矽裝填入一 24吋石英坩堝中，以用 來成長直徑為8吋的單結晶矽。在第2圖中，A代表本 發明之實施例，其顯示出在磁場強度為4000高斯、主室 内壓力為20Torr、氬氣流量為60i/min以及氣體整流筒 與熔液間的間隙為50mm下之軸向氧氣濃度的變化。B 和C代表昔知技術。在B中，其提供與A中一樣的橫向 磁場，但是不具有氣體整流筒。而在C中，沒有提供橫 向磁場，但具有氣體整流筒。在B與C中，主室中的内 部壓力為20Torr，而氬氣流速為60L/min。除此之外， 在C中氣體整流筒及熔液間的間隙為50mm。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 442580 經濟部中夬標率局員工消費合作社印裝 Α7 Β7 五、發明説明（6) 如第2圖所示’藉由本發明的製造方法所獲得的單 結晶>6夕的氧氣濃度在轴向上的整個長度是少於 10xl017atoms/cm2。再者’在軸向上的氧氣濃度變化是小 的。相反地’藉由昔知技術所獲得的單結晶的氧氣濃度 ’特別疋在結晶體前半段的部分，遠遠超過 10xl017at〇mS/cm2。再者，在轴向上之氧氣濃度的變化很 大。 由上述結果可知’當使用内部大於24吋的坩堝來製 造具有極低氧氣濃度的單結晶矽時，其可藉由相乘效應 ，亦即利用上述磁場的應用來阻止熔液對流，以及利用 氣體整流筒提升從熔液蒸發之氧氣排放能力。 在此實势例中’提供磁場到熱區域(hot zone"並不 止限於此。應用尖端磁場也可產生具有極低氧氣濃度的 單結晶矽》 以上所述，根據本發明，因為使用藉由磁場的應用 來阻止氧氣從坩堝熔入熔液，以及藉由用來控制惰性氣 體流速之整流筒來提升從熔液所蒸發之氧氣排放能力的 的相乘效應來成長單結晶矽，所以可減小炼液中的氧氣 含量，以及可獲得在軸向整個長度上具有極低氧氣濃度 的單結晶矽。此製造裝置及方法是有效的，特別是用來 製造直徑大於8英吋的大尺寸的單結晶矽。 本紙張尺度通用中國國家橾準{ CNS > Α4規格（210Χ297公釐） ---------:------訂------線 --- (請先閱讀背面之注意事項再填寫本頁)1T line "2580 Λ7 Β7 Central Bureau of Standards of the Ministry of Economic Affairs *; 印 Printed by Consumer Cooperatives V. Invention Description (3) It is possible to control both the convection of the melt and the oxygen emission from the melt. Supplying a magnetic field to the melt can increase the positive The effective dynamic viscosity coefficient of the conductive melt that crosses the magnetic lines of force can therefore prevent the convection of the melt. When an anti-magnetic field is provided, it can 'block the melt convection along the wall (vertical direction) of the quartz crucible' and thus prevent The amount of oxygen is dissolved in the melt from the quartz crucible. Therefore, the amount of oxygen trapped in the single crystal silicon can be reduced. Furthermore, the gap between the bottom of the emotional gas rectifier and the surface of the melt is maintained at an appropriate value to improve borrowing. The discharge of silicon oxide (SiOx) by an inert gas can further reduce the amount of oxygen trapped in the single crystal silicon. Through the above-mentioned multiplication effect, crystals with low oxygen concentration and uniform oxygen concentration distribution in the axial direction can be obtained. In order to make the foregoing objects, features, and advantages of the present invention more comprehensible, a series of preferred embodiments are described below in conjunction with the drawings. Brief description of the drawings: Figure 1 shows a single crystal stone Partial cross-sectional view of the manufacturing device; and Figure 2 shows a comparison diagram of the axial oxygen concentration of single crystal silicon. Symbol description: 1 ~ main chamber, la ~ exhaust vent, 4 ~ quartz sweet bane, 5 ~ solution, 9 ~ gas rectifier, 10 ~ coil and 12 ~ single crystal dream. Example: Figure 1 shows a partial cross-sectional view of a single crystal silicon manufacturing device. In the central part of the main chamber 1, the 'graphite crucible 3 is Ang g in The crucible shaft 2 can be rotated and lifted. The quartz crucible 4 is located in the graphite crucible 3 «ι» to accommodate {Please read the precautions on the back before filling in this page.) Winter Paper Concentration κ General 肀 囷 National Standard (CNS) Α4 Specifications (Industrial Consumer Cooperative of the Central Bureau of Standards of the Ministry of Public Economy, Yinfan 442580 A7 ______B7 V. Description of the invention (4) Melt containing polycrystalline silicon 5. A cylindrical heater 6 or a cylindrical thermostat 7 is installed in the above graphite crucible The periphery of 3. A gas rectifying cylinder 9 is installed on the top of the thermostatic cylinder 7 by a supporting element 8. The above-mentioned gas cylinder 9 is an inverted cone-shaped cylinder whose opening at the upper end is larger than the opening at the lower end and is made of graphite or SiC. "The upper end of the main room i is a company To a pull chamber (not shown in Fig. 卞) at the lower end of the main chamber i has an exhaust hole la connected to a vacuum pump (not shown in the figure). Furthermore, the annular coil 10 is set up vertically Outside the main chamber 1. The bulk polycrystalline silicon is filled into the quartz crucible 3, and heated and melted by the heater 6 to make it into a melt 5 ^, the seed mounted on the seed crystal holder 11 The crystals are immersed in the melt 5. Then, when the seed crystal clamp u is pulled to grow the monocrystalline silicon 12, the seed crystal clamp 11 and the graphite crucible 3 are rotated in the same or opposite directions. When power is supplied to the coil 10 A magnetic field is generated in the horizontal direction and supplied to the above-mentioned melt 5. Therefore, the convection of the melt orthogonal to the magnetic field line can be prevented, and the oxygen on the inner wall of the quartz crucible 4 can be reduced into the melt. On the other hand, an inert gas, such as argon, is introduced downward from the above-mentioned guide chamber, and passes through the gap between the growing single crystal silicon 12 and the gas rectifier cylinder 9, and then the inner wall of the quartz crucible 4 and the gas rectifier cylinder. Nine rooms rose. After that, the inert gas flows down to the gap between the graphite crucible 3 and the heater 6 or the gap between the heater 6 and the thermostat 7, and is discharged from the exhaust hole 1. When passing through the gap between the surface of the melt 5 and the gas rectifying cylinder 9, the above-mentioned inert gas vessel will be accelerated β, which is conducive to the discharge of the oxidized debris (SiOx) evaporated from the solution 5, but "if the surface of the melt 5 and _ 6 paper size it papers {CNS) A4g (2 丨 Gx 297 Gongchu) '(Please read the precautions on the back before filling this page) Order-line 442580 V. Description of the invention (5) Flow The gap between the bottoms of the cylinders 9 is too small, the radiant heat of the quartz crucible 4 will be shielded by the gas rectification cylinders 9, and the surface temperature of the melt 5 will decrease, thus preventing the evaporation of oxidized debris (SiOx). As a result, the amount of oxygen trapped is increased, and a gap of '50 mm is desired. Moreover, with respect to the main chamber with a capacity of 900 to 2000 L, the flow rate of the inert gas is desirably 35 to 65 L / min 'in order to maintain the discharge capacity of the silicon oxide evaporated from the melt 5 and prevent the surface of the melt 5 and the rectifier barrel 9 from being discharged. A turbulent flow of inert gas passes through the gap between the bottoms. If the flow rate of the inert gas is less than 35 L / min ', the silicon oxide cannot be released in a sufficient amount, so that a single crystal having an extremely low oxygen concentration cannot be obtained. If the flow rate of the inert gas exceeds 65 L / min, turbulent flow occurs, so that amorphous silicon oxide may adhere to the outside of the gas #flow tube 9. Printed by Du Consumers of the Central Bureau of Standards of the Ministry of Economic Affairs (谙 Please read the notes on the back before filling out this page) Figure 2 shows the axial direction of the single crystal hair made using the manufacturing method of the present invention and the known technology Comparison of oxygen concentration. In this example, 120Kg of polycrystalline silicon is packed into a 24-inch quartz crucible to grow single-crystal silicon with a diameter of 8 inches. In Figure 2, A represents the present invention Example, which shows the change of the axial oxygen concentration at a magnetic field strength of 4000 Gauss, a main chamber pressure of 20 Torr, an argon flow rate of 60 i / min, and a gap between the gas rectifying cylinder and the melt of 50 mm. B and C stands for known technology. In B, it provides the same transverse magnetic field as in A, but without a gas rectifier. In C, it does not provide a transverse magnetic field, but with a gas rectifier. In B and C, the main The internal pressure in the chamber is 20 Torr, and the flow rate of argon gas is 60 L / min. In addition, the gap between the gas rectification cylinder and the melt in C is 50 mm. This paper size applies the Chinese National Standard (CNS) A4 specification ( 210X 297 mm) 442580 Ministry of Economic Affairs Printed by the Standards Bureau employee consumer cooperative A7 B7 V. Description of the invention (6) As shown in Fig. 2 'Single crystal obtained by the manufacturing method of the present invention> The entire length of the oxygen concentration in the axial direction in the axial direction It is less than 10xl017atoms / cm2. Furthermore, the change of the oxygen concentration in the axial direction is small. On the contrary, the oxygen concentration of the single crystal obtained by the conventional technology is particularly large in the first half of the crystal, far exceeding 10xl017at〇mS / cm2. In addition, the oxygen concentration in the axial direction varies greatly. From the above results, it can be seen that when using a crucible larger than 24 inches inside to produce single crystal silicon with extremely low oxygen concentration, it can be borrowed By the multiplication effect, that is, the application of the magnetic field described above is used to prevent the convection of the melt, and the gas rectifier is used to enhance the oxygen discharge capacity of evaporation from the melt. In this example, 'providing the magnetic field to the hot zone (hot zone & Not limited to this. The application of a sharp magnetic field can also produce single crystal silicon with extremely low oxygen concentration. "As described above, according to the present invention, because the application of a magnetic field is used to prevent oxygen from flowing from the crucible The single crystal silicon is grown by the multiplication effect of melting into the molten liquid and the rectifying cylinder used to control the flow rate of the inert gas to increase the oxygen discharge capacity evaporated from the molten liquid, so the oxygen content in the refined liquid can be reduced. And it is possible to obtain single crystal silicon with extremely low oxygen concentration over the entire length in the axial direction. This manufacturing device and method are effective, especially for making large-size single crystal silicon with a diameter larger than 8 inches. China National Standard {CNS > Α4 Specification (210 × 297 mm) ---------: ------ Order ------ Line --- (Please read the precautions on the back first (Fill in this page again)