515008 Α7 Β7 五、發明説明（1) 〔技術領域〕 (請先閲讀背面之注意事項再填寫本頁) 本發明爲最適合於製造矽晶圓（或退火晶圓）之矽晶 圓之製造方法，其係對由摻入氮而拉晶之切克勞斯基法（ c Z法）生長之單晶砂所製作之砂晶圓施予熱處理（ annealing)，以製造晶圓表層部有無缺陷層，而在基體部 形成內在除氣（Intrinsic gettering，簡稱I G )層之矽晶 圓（或稱退火晶圓）。 〔技術背景〕 隨著半導體裝置之高積體化，細微化，人們強烈要求 晶圓表層之整層之完整性與基體中之除氣能力之強化。對 此要求，最近藉由對摻入氮之C Z法製成之矽晶圓實施熱 處理而開發了同時滿足上述兩項要求之晶圓。 經濟部智慧財產局員工消費合作社印製 亦即，藉由C Z法製成之單晶矽摻入氮，剛生長（as grown)結晶中之內部生長（grown-in)缺陷（主要在原子 空孔之聚集體所形成之空隙缺陷）之尺寸變小，因此藉由 後工程之高溫退火，晶圓表層部之無缺陷化變得容易，而 且在基體部由於氮具有之氧析出促進效果，經過析出熱處 理與裝置熱處理工程，而形成具有高密度之有助予除氣（ gettering )之氧析出物等之缺陷（以下有時稱爲B M D，即 Bulk micro defects ) 〇 可是，形成於C Z法矽晶之基體部，而有助於除氣之 B M D之密度與影響表層部之無缺陷層之形成之內部生長 缺陷之尺寸通常具有面內分布爲習知，尤其在晶圓之中心 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） -4 - 經濟部智慧財產局員工消費合作社印製 515008 Α7 Β7 五、發明説明（2) 附近，B M D密度與內部生長（grown_in)缺陷尺寸皆大’ 在晶周邊，兩者有慢慢降低之傾向。 此種傾向在摻入氮結晶也相同，雖然B M D密度與內 部生長缺陷之尺寸之絕對値會變化，但在具有面內分布這 一點是不變的。因此，在對表層部施予用於形成無缺陷層 之高溫退火之後，在退火晶圓之中心部分特別容易留下內 部生長缺陷。515008 Α7 Β7 V. Description of the Invention (1) [Technical Field] (Please read the precautions on the back before filling out this page) The present invention is a silicon wafer manufacturing method most suitable for manufacturing silicon wafers (or annealed wafers) , Which is an annealing process for sand wafers made from single crystal sand grown by the Czochralski method (cZ method) doped with nitrogen and pulling crystals to produce wafers with or without defective layers A silicon wafer (or annealed wafer) with an intrinsic outgassing (IG) layer is formed in the base portion. [Technical Background] As semiconductor devices become more integrated and miniaturized, the integrity of the entire surface layer of the wafer and the enhancement of the outgassing ability in the substrate are strongly demanded. To meet this requirement, a silicon wafer made by the CZ method doped with nitrogen has recently been thermally processed to develop a wafer that meets both of the above requirements. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, that is, single crystal silicon made by the CZ method is doped with nitrogen, and grown-in defects in the as-grown crystal (mainly in atomic pores) The size of the void defects formed by the aggregates becomes smaller, so by post-processing high-temperature annealing, the defect-freeness of the surface layer portion of the wafer becomes easy, and in the base portion, the oxygen precipitation promotion effect due to nitrogen has been precipitated. Heat treatment and device heat treatment engineering to form defects (such as BMD, sometimes referred to as BMD, or Bulk micro defects) that have high density of oxygen precipitates that help gettering. However, they are formed in the CZ method silicon crystals. The density of the substrate, and the density of the BMD that contributes to degassing, and the size of the internal growth defects that affect the formation of the defect-free layer on the surface layer, usually have an in-plane distribution, especially in the center of the wafer. This paper size is applicable to China Standard (CNS) Α4 specification (210 × 297 mm) -4-Printed by the Consumer Consumption Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 515008 Α7 Β7 V. Description of the invention (2) Near the BMD density and Growth portion (grown_in) defect size Jietai 'surrounding the crystal, the two tends to decrease gradually. This tendency is also the same when crystals are doped with nitrogen. Although the absolute density of the B M D density and the size of the internal growth defects may change, the point of having the in-plane distribution is constant. Therefore, after the surface layer portion is subjected to high-temperature annealing for forming a defect-free layer, it is particularly easy to leave internal growth defects in the center portion of the annealed wafer.
另外，關於決定本體之除氣能力之析出熱處理之後之 B M D密度，經過本發明者之諷查，在晶圓周邊部B M D 密度降低之傾向特別對摻入氮之晶圓更顯著一事超於明確 〇 如上所述，退火晶片所要求之形成於晶圓表層部之無 缺陷層，以及析出處理或裝置熱處理後之B M D密度之任 何特性現在尙存在不均勻之問題。 〔發明之揭示〕 因此，本發明係爲解決此種問題而完成者，其目的在 提供一種適合製造退火晶圓之矽晶圓之製造方法以及該項 矽晶圓，該退火晶圓可以抑制熱處理後之退火晶圓所見之 無缺陷層之面內分散（亦即，內部缺陷尺寸之面內分散） ，以及析出熱處理或裝置熱處理等熱處理後之BMD密度 之面內分散，並在面內均勻地具有充分之無缺陷層與 B M D密度。 爲達成上述目的，與本發明之矽晶圓之製造方法有關 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 -5- 515008 Α7 Β7 五、發明説明（3) 之發明係由切克勞斯基法摻入氮而拉起之單晶矽製作矽晶 圓，再對該矽晶圓施予熱處理之矽晶圓之製造方法，其特 徵爲拉起上述單晶矽時之拉晶速度V ( m m /分鐘）與固 液界面之溫度梯度G (K/mm)之比V/G係在拉起結 昌之直徑方向之90%以上之範圍內成爲0.175至 0 . 2 2 5mm2/K ·πι;ί η爲條件培養之。 由摻入此種條件下培養久氮之單晶矽切下之矽晶圓在 內部生長（groron-in)缺陷尺寸之面內分布與BMD密度 之面內分布皆可以成爲均勻。因此，如對其進行高溫熱處 理，即可獲及無晶圓表層部之無缺陷層之面內分散，而本 體部之BMD密度在面內均勻而高密度之I G能力強之退 火晶圓。In addition, regarding the BMD density after the precipitation heat treatment which determines the degassing ability of the body, after the inventor's irony, the tendency of the BMD density to decrease in the peripheral portion of the wafer is particularly significant for a wafer doped with nitrogen. As described above, the non-defective layer formed on the surface layer of the wafer required for annealing the wafer and any characteristics of the BMD density after the precipitation treatment or the device heat treatment are now uneven. [Disclosure of Invention] Therefore, the present invention was made to solve such a problem, and its purpose is to provide a method for manufacturing a silicon wafer suitable for manufacturing an annealed wafer and the silicon wafer, which can suppress heat treatment The in-plane dispersion of the non-defective layer seen in the subsequent annealed wafer (that is, the in-plane dispersion of the internal defect size), and the in-plane dispersion of the BMD density after heat treatment such as precipitation heat treatment or device heat treatment, and uniformly in the plane With sufficient defect-free layer and BMD density. In order to achieve the above purpose, the paper size related to the method for manufacturing the silicon wafer of the present invention applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page) Order-5- 515008 Α7 Β7 V. Description of the invention (3) The invention is a silicon wafer made of single crystal silicon which is pulled up by adding nitrogen into the Chkralski method, and the silicon wafer is heat-treated. The method is characterized in that the ratio V / G of the pulling speed V (mm / min) and the temperature gradient G (K / mm) of the solid-liquid interface when pulling up the above single crystal silicon is 90% of the diameter direction of the pulling junction. In the range of more than%, it is 0.175 to 0.2 2 5mm2 / K · ι; η is cultured under conditions. Both the in-plane distribution of groron-in defect sizes and the in-plane distribution of BMD density can be made from silicon wafers cut from single-crystal silicon grown under this condition. Therefore, if it is subjected to high-temperature heat treatment, the in-plane dispersion of the defect-free layer without the surface layer portion of the wafer can be obtained, and the BMD density of the body portion is uniform and high-density in the plane.
此時，上述矽晶圓中之氮濃度以1 X 1 〇 1 3至5 X 1 0 1 5個/ c m 3爲理想。 如將氮濃度侷限於上述範圍，內部生長缺陷之尺寸變 小之效果充分，另外，也不致對單晶之培養有不良影響， 所以容易利用後工程之高溫退火進行晶圓表層部之無缺陷 化，同時由於基體部之具有氮之氧析出之促進效果，經過 析出熱處理與裝置熱處理即可形成具有高密度有助於除氣 之B M D之I D層。 而依據本發明即可提供一種矽晶圓，其可以抑制熱處 理後之退火晶圓所見之無缺陷層之面內分散，以及析出熱 處理或裝置熱處理等之熱處理後之B MD密度之面內分散 ，並在面內具有均勻而充分之無缺陷層與BMD密度之退 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 、11 %·. 經濟部智慧財產局員工消費合作社印製 -6- 515008 A7 B7 五、發明説明（4) 火晶圓。 依據本發明，即可形成內部生長缺陷尺寸之面內分布 及BMD密度之面內分布均勻之摻入氮之矽晶圓。因此， 如對其實施高溫熱處理，即可製造無晶圓表層部之無缺陷 層之面內分散，而本體部具有BMD密度在面內均勻之I G層之退火晶圓。 圖式之簡單說明 第1圖爲表示本發明之V/G與BMD之關係之圖。 第2圖爲表示本發明之V/G與內部生長缺陷尺寸之 關係之圖。 第3圖係有關於實施例1 ，比較例1與比較例2之結 晶拉起時之結晶方向之V/ G之分布圖。 第4圖係有關於實施例1，比較例1與比較例2之拉 起結晶之結晶直徑方向之內部缺陷尺寸之分布圖。 第5圖係有關於實施例1 ，比較例1與比較例2之拉 起結晶之結晶直徑方向之BMD密度之分布圖。 第6圖爲本發明所使用之C Z法所使用單晶拉晶裝置 之槪略說明圖。 主要元件對照表 1 :單晶棒 2 :矽熔液 5 :晶種 本紙張尺度適用中.國國家標準（CNS ) A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁)At this time, the nitrogen concentration in the silicon wafer is preferably from 1 X 103 to 5 X 105 per cm3. If the nitrogen concentration is limited to the above range, the effect of reducing the size of internal growth defects is sufficient, and it will not adversely affect the cultivation of single crystals, so it is easy to use the post-process high temperature annealing to defect-free the surface layer of the wafer. At the same time, due to the promotion effect of nitrogen and oxygen precipitation in the base portion, an ID layer having a high density of BMD can be formed after the precipitation heat treatment and the device heat treatment. According to the present invention, a silicon wafer can be provided, which can suppress the in-plane dispersion of defect-free layers seen in the annealed wafer after heat treatment, and the in-plane dispersion of B MD density after heat treatment such as precipitation heat treatment or device heat treatment. And it has a uniform and sufficient defect-free layer and BMD density in the plane. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page). 11% ·. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-6- 515008 A7 B7 V. Description of the invention (4) Fire wafer. According to the present invention, a silicon-doped silicon wafer having an in-plane distribution of internal growth defect sizes and an in-plane distribution of BMD density can be formed. Therefore, if high-temperature heat treatment is performed on it, an annealed wafer can be manufactured in which the defect-free layer of the wafer-free surface layer portion is dispersed in-plane, and the body portion has an I G layer with a uniform BMD density in the plane. Brief Description of the Drawings Fig. 1 is a diagram showing the relationship between V / G and BMD of the present invention. Fig. 2 is a graph showing the relationship between V / G and the size of internal growth defects in the present invention. Fig. 3 is a graph showing the distribution of V / G in the crystalline direction when the crystals of Example 1 and Comparative Examples 1 and 2 were pulled up. Fig. 4 is a diagram showing the distribution of the size of the internal defects in the crystal diameter direction of the pulled-up crystals of Example 1, Comparative Example 1 and Comparative Example 2. Fig. 5 is a graph showing the distribution of BMD densities in the crystal diameter direction of the pulled-up crystals of Example 1, Comparative Example 1 and Comparative Example 2. Fig. 6 is a schematic explanatory diagram of a single crystal pulling device used in the CZ method used in the present invention. Main component comparison table 1: single crystal rod 2: silicon melt 5: seed crystal This paper size is applicable. National National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling in this page)
、1T 經濟部智慧財產局員工消費合作社印製 515008 A7 B7 五、發明説明（5 ) ' 6 :種晶夾頭 7 :鋼絲 (請先閲讀背面之注意事項再填寫本頁) 8 ··固液界面斷熱材料 9 :上部圍繞隔熱材料 1 0 ··空隙 3 0 :單晶拉晶裝置 3 1 : k晶室 3 2 :坩堝 3 3 :坩堝保持軸 3 4 :加熱器 3 5 :斷熱材料 3 6 :冷卻裝置 實施發明之最佳形態 以下就本發明再詳細說明。 經濟部智慧財產局員工消費合作社印製 本發明人發現要製作在面內具有均勻而充分之無缺陷 層與B M D密度之退火晶圓，必須準備之矽晶圓不具有形 成於基體部（bulk )而有助於BMD之密度，以及影響表層 部之無缺陷層之形成之內部生長缺陷之尺寸之面內分布。 亦即，本發明人針對現狀製造成退火晶圓之用之摻入 氮之C Z法矽晶圓施加高溫退火後之晶圓表層部之內部缺 陷密度，以及追加熱處理後之B M D密度進行銳意調查。Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 515008 A7 B7 V. Description of the invention (5) '6: Seed chuck 7: Steel wire (Please read the precautions on the back before filling this page) 8 ·· Solid Interface thermal insulation material 9: The upper part surrounds the thermal insulation material 1 0 ·· void 3 0: single crystal pulling device 3 1: k crystal chamber 3 2: crucible 3 3: crucible holding shaft 3 4: heater 3 5: thermal insulation Material 36: Best Mode for Implementing the Invention of the Cooling Device The present invention will be described in detail below. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The inventor found that to produce an annealed wafer with a uniform and sufficient defect-free layer and BMD density in the surface, the silicon wafer that must be prepared does not have a bulk formed on the substrate (bulk) This contributes to the in-plane distribution of the BMD density and the size of internal growth defects that affect the formation of defect-free layers in the surface layer portion. That is, the present inventors conducted an intensive investigation on the density of internal defects in the surface layer portion of the wafer after the high temperature annealing was applied to the nitrogen-doped CZ method silicon wafers that are currently manufactured as annealed wafers, and the BMD density after additional heat treatment.
結果，知道在晶圓中心部分殘留之缺陷數多，B M D 密度也高，但是在晶圓周邊部分殘留之缺陷數少，B M D 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -8- 515008 A7 B7 五、發明説明（6) 密度也低。另外，在其中間之位置（以下簡稱R / 2位置 ，R爲晶圓之半徑），殘留缺陷普通地少，B M D密度也 (請先閱讀背面之注意事項再填寫本頁) 普通地高。 在此三處之中，R/2位置在表層部之完整性與基體 中之除氣能力之平衡最好。亦即，如能將該R / 2位置之 狀態擴充至晶圓面內，即可獲及面內均勻而高品質之晶圓 〇 於是，爲了擴大該R / 2位置之狀態，調查了 B M D 與內部生長（grown-in)缺陷之分布與C Ζ法單晶矽之拉晶 法之相互關係。 經濟部智慧財產局員工消費合作社印製 結果，發見了內部生長缺陷尺寸與BMD密度之面內 分布變成不均勻之原因至少由於結晶培養時之控晶速度V (m m /分鐘）與由矽之熔點到1 4 0 0 °C之範圍內之拉 晶軸方向之固液界面之溫度梯度G ( K /m m )之比V / G在面內具有分布，亦即V/ G在面內變動所致。因此， 不管晶圓面內之位置，爲了將內部生長缺陷與BMD密度 設成企望之値，將目標定爲求取必要之具體之V / G値。 以下就此加以說明。 內部生長缺陷會受V / G之影響已屬周知，所以利用 拉晶裝置之特定之熱區（hot zone，簡稱HZ，爐內構造） 將捲入拉牽結晶中之氮濃度設定爲1 X 1 〇 1 3個/ c m 3， 以由1.0至1·4mm/分鐘之範圍內選出之拉晶速度 進行多個結果之培養，以調查各V / G之面內分布與內音[5 生長缺陷之尺寸之關係及與8 0 0 CTC X 4小時+ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ' ' ' -9 - 515008 A7 B7 五、發明説明（7) 1 0 0 0°Cxl 6小時之熱處理後之BMD密度之關係。 其結果如第1圖及第2圖所示。 (請先閱讀背面之注意事項再填寫本頁) 第1圖爲表示就晶圓面內之中央部，R/2部，周邊 部（由晶圓外周起算1 〇 m m之位置）所測定之B M D密 度之全部資料與V/G之關係，顯示BMD密度與V/G 有直接關係。當V/G小於〇 . 19〇mm2/K.mi η 時，即下降至除氣能力不充分之1 χ 1 〇 9個/ c m 3以下 。亦即，爲獲得高密度之B M D，不管晶圓面內之位置， 只要將V/G設成大於〇 · 1 75mm2/K ·ιηί η即可 ο 另一方面，第2圖爲表示利用〇Ρ Ρ ( optional precipitate profiler)相對評估內部生長缺陷之尺寸，以調 經濟部智慧財產局員工消費合作社印製 查與V / G之關係之結果。與第1圖相同，表示針對晶圓 之面內中央部，R/2部，周邊部所測定之〇PP尺寸之 全部資料與V/G之關係，表示0PP尺寸與V/G有直 接關係。亦即，首先發現當V / G小於〇 . 2 2 5 m m 2 / Κ ·ιηί η時，內部生長缺陷之尺寸急劇變小，在超過 0 · 225mm2/K.mi η之範圍時，內部生長缺陷之 尺寸之値大到傾向飽和。因此，爲使成爲以熱處理容易消 滅之小尺寸之內部生長缺陷（grown_in defect)，不拘晶圓 面內之位置，將V / G設成小於0 . 2 2 5 m m 2 / K · m i η即可。 由以上第1圖及第2圖之結果來看，要將摻雜氮氣之 C Ζ法單晶砂拉牽上來時’如果將V/ G製造成爲結晶之 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐) " -10- 515008 A7 B7 五、發明説明（8) 直徑方之0 . 175至0 . 225mm2/K*mi η之範 (請先閱讀背面之注意事項再填寫本頁) 圍內，則在晶圓面內不致成爲不均勻，因爲內部生長缺陷 尺寸小至恰到好處，所以可以製得在晶圓整面可以充分消 滅內部生長缺陷，且形成有適當之BMD密度之退火晶圓 〇 在此，拉牽結晶之外周部具有決定內部生長缺陷之尺 寸與B M D密度之點缺陷（point defect )在結晶培養中向 外部擴散。因此，在拉牽結晶之外周端到半徑之5 %左右 爲止之區域（例如拉起直徑2 0 0 m m之結晶時，由外周 端起算1 0mm爲止）中，內部生長缺陷之尺寸與BMD 密度與V / G之關係變鬆。亦即，在本發明適用V / G之 範圍係除去拉牽結晶之直徑方向之兩外周部各5 %之至少 9 0 %之區域，該區域中，視拉晶條件而在9 0至1 0 0 %之範圍內變動。 以下，一邊參照圖式，一邊詳細說明本發明。 經濟部智慧財產局員工消費合作社印製 首先，根據第6圖說明本發明所使用之C Z法之單晶 抽晶裝置之構造例。如第6圖所示，該單晶拉晶裝置3 0 係由抽晶室3 1 ，設置於拉晶室3 1中之坩堝3 2，配置 坩堝3 2之周圍之加熱器3 4，使坩堝3 2旋轉之坩堝保 持軸3 3以及捲取機構（未圖示），保持矽之晶種（seed crystal) 5之晶種夾頭（seed chuck) 6，拉牽晶種夾頭6 之鋼線7，以及旋轉或捲取鋼線7之捲取機構（未圖示） 。坩堝3 2在收容矽熔液2之內側之一側設有石英坩堝， 其外側設有石墨坩堝，而在加熱器3 4之外側周圍配置隔 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -11 - 515008 A7 ___B7 _ 五、發明説明（9) 熱材料3 5。 (請先閱讀背面之注意事項再填寫本頁) 另外，本發明之製造方法有關之製造條件，即將V / G之適當範圍擴大到直徑方向及軸方向之方法可以習知方 法進行。亦即，例如結晶之固液界面之外周設置固液界面 隔熱材料8，並其上面設置有上部圍繞隔熱材料9之HZ ’俾將結晶周邊之溫度梯度（G e )與結晶中心之溫度梯 度（G c )之差（G e - G c )縮小以致固液界面溫度梯 度G在面內成爲平坦化。該固液界面隔熱材料8係設置成 其下端與矽熔液2之液面之間留有3至5公分之空隙1 0 。上部圍繞隔熱材料9視條件有時不使用。另外，也可以 設置勁吹冷卻氣體或絕斷輻射熱以冷卻單晶之圓柱形冷卻 裝置3 6 〇 另外，最近常有人利用在抽晶室3 1之水平方向之外 側設置未圖示之磁鐵並對矽熔液2施加水平方向或垂直方 向等之磁場以抑制熔液之對流並求單晶之穩定成長之所謂 M C Z 法。 接著要就利用上述之單晶拉晶裝置培養方法加以說明 〇 經濟部智慧財產局員工消費合作社印製 首先在坩堝3 2內將矽之高純度結晶原料加熱至熔點 (約1 4 2 0 °C )以上熔融之。氮摻雜可藉由例如在矽原 料中投入附有氮化膜之矽晶圓實施之。然後，藉由捲出鋼 絲7使晶種（seed crystal ) 5之前端接觸或浸漬於溶液2 之表面靠中心部分。然後，將坩堝保持軸3 3旋轉至適當 之方向，同時，一邊捲出鋼絲7 —邊拉牽捲取晶種5以開 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -12- 515008 A7 B7 五、發明説明（ 始單晶培養。嗣後，藉由調節拉晶速度與溫度即可製得大 致上圓柱形狀之單晶棒1。 (請先聞讀背面之注意事項再填寫本頁) 所製得之單晶棒可以利用一般之方法，以鋼鋸等切割 ，並施予倒稜，拋光，蝕刻，硏磨等而製成摻雜氮之矽晶 圓。 接著，本發明中再對所製得之矽晶圓實施熱處理。如 此一來，在表面即均勻地形成無缺陷層，而在基體部會高 密度地發生BMD。具體之熱處理條件係使用一般之加熱 器之分批式爐，而在氬等之惰性氣體，氫，或該等之混合 氣氛下進行1 0 0 0至1 3 5 0 °C，1小時以上之熱處理 (例如，1 2 0 0 °C，1小時；或1 1 5 0 °C，4小時等 )。另外，也可以利用燈泡加熱等之快速熱退火裝置（ R T A ) (Rapid thermal annealing device)進行快速加熱 •快速冷卻之熱處理，或並用分批式爐與RTA裝置之熱 處理 以下，要提出本發明之實施例與比較例具體地說明本 發明，惟本發明並不侷限於該等例子。 經濟部智慧財產局員工消費合作社印製 (實施例1 ) 實施例1係利用結晶中心溫度梯度G c = 3 · 5 4 3 〔K/mm〕，結晶周邊溫度梯度Ge = 3 . 933 〔K /mm] ，Ge— Gc = 0 . 390 〔K/mm〕之具有 比較上G e - G c之値較小之Η Z之單晶拉晶裝置，將拉 晶速度調整爲約〇 . 7 4 m m /分鐘，而拉出直徑6吋之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -13 - 515008 A7 B7 五、發明説明（1》 (請先閲讀背面之注意事項再填寫本頁) 摻入氮之單晶矽。氮摻雜法係將矽原料中投入附有氮化膜 之矽晶圓，而使拉牽結晶之肩部（shoulder)之位置之氮濃 度（計算値）成爲2 X 1 0 1 3 / c m 3。此外，氧濃度則調 整爲1 4至1 5 ppma 〔 J E I DA (日本電子工業振 興協會）規格。 第3圖表示結晶拉牽時之V / G之結晶直徑方向之分 布。V/ G之直徑方向整體皆位於約〇 . 1 8 0至 0 . 223mm2/K.mi n 之範圍內。 由被拉牽之結晶製成了矽晶圓，並以〇P P法測定內 部生長缺陷之尺寸後，施加8 0 0 °C，4小時+ 1 0 0 0 °C，1 6小時之析出熱處理以形成B M D，並以〇P P法 測定B M D密度。內部生長缺陷尺寸之測定結果表示於第 4圖，而B M D密度之測定結果表不於第5圖。 經濟部智慧財產局員工消費合作社印製 內部生長缺陷爲可藉由1 2 0 0 °C，1小時之氬氣氛 充分地消滅之尺寸（小於1 . 5 )(第4圖），面內分布 也小。另外，B M D密度在晶圓面內任何位置皆爲約2至 5χ 1 09/cm3，獲得了高密度而均勻之面內分布（第 5圖）。 (比較例1，比較例2 ) 做爲比較例1 ，2，使用了 G c = 3 · 7 7 8 〔 K / mm〕，Ge = 4.904〔K/mm〕，Ge— Gc = 1.126 〔K/mm〕之具有比較上Ge-Gc之値較 大之Η Z之單晶拉晶裝置，在比較例1將拉晶速度調整爲 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） " "" -14- 515008 經濟部智慧財產局員工消費合作社印製 A7 B7 _五、發明説明（ 約0 · 8 4 m m /m i η，在比較例2調整爲約0 · 8 7 m m /m i η而拉上直徑6吋之摻氮單晶矽。氮摻雜係在 矽原料中投入附有氮化膜之矽晶圓’並使拉牽結晶之肩部 位置之氮濃度（計算値）成爲2x 1 013/cm3。另外’ 氧濃度調整爲14至15ppma 〔JEIDA〕。 比較例1 ，比較例2之拉晶吋之V / G之結晶直徑方 向之分布附記於第3圖。在比較例1中V / G位於 0 · 175至0 · 225mm2/K*mi η之範圍內者爲 由結晶之中心起算到約6 2 m m之範圍爲止之約8 3 % ’ 而比較例2之情形爲由結晶之中心起算向外周方向之約 3 0 m m之位置到約6 6 m m之位置爲止之約4 8 %。 由被拉牽之結晶製作了矽晶圓並以〇P P法測定內部 .生長缺陷之尺寸後，施加8 0 0 °C，4小時+ 1 0 0 0 °C ，：L 6小時之析出熱處理而形成B M D，並以Ο P P法測 定B M D之密度。 內部生長缺陷之尺寸之測定結附記於第4圖，B M D 密度之測定結果附記於第5圖。 在比較例1之晶圓中心，內部生長缺陷尺寸較小，在 晶圓周邊部成爲很小，缺陷尺寸之面內分布固然廣大，但 是整體上爲不易以退火消滅之尺寸之缺陷。可是，關於析 出熱處理後之B M D密度卻發現在V / G値低之晶圓周邊 部BMD密度降低至2x 1 08/cm3左右，在周邊部之 除氣能力低，而面內布大。 在比較例2中，關於B M D密度，在面內雖達約1 X 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） ^ -15- (請先閲讀背面之注意事項再填寫本頁) ·«· 訂 %·. 515008 A7 B7 五、發明説明（1全 (請先閲讀背面之注意事項再填寫本頁) 1 〇9/cm 3以上，但因內部生長缺陷尺寸之面內分布大 ，特別是晶圓中心之尺寸相當大，所以即使進行1 2 0 0 °C，1小時之氬氣氛之退火，中心部分之內部生長缺陷也 會殘留一部分。 由此等結果可知，在比較例1 ，2所使用之拉晶裝置 之Η Z時，爲使內部生長缺陷之尺寸與BMD密度雙方在 面內分布均勻，即使將拉晶速度控制於0 . 8 4至 〇 . 8 7 mm/分鐘之有限範圍內也非常困難。 另外，本發明並不侷限於上述實施形態。上述實施形 態僅爲例，凡具有與本發明之申請專利範圍所記載之技術 思想與實質上相同之構造而發揮相同之作用效果者，不拘 任何形式皆包含於本發明之技術範圍 例如，在上述實施形態中，係針對培養直徑6吋之單 晶矽之情形舉例說明，但本發明並不侷限於此，也可應用 於直徑8至1 6吋或更大之單晶矽。 經濟部智慧財產局員工消費合作社印製 另外，本發明也可適用於在矽熔液中施加水平磁場， 縱磁場，尖端磁場（cusp magnetic field)等之所謂M C Z 法，自不得言。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -16-As a result, I know that the number of defects remaining in the center of the wafer is large, and the density of BMD is also high, but the number of defects remaining in the periphery of the wafer is small. The paper size of BMD applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm)- 8- 515008 A7 B7 5. Description of the invention (6) The density is also low. In addition, in the middle position (hereinafter referred to as R / 2 position, R is the radius of the wafer), the residual defects are generally small, and the B M D density is also high (please read the precautions on the back before filling this page). Among these three places, the balance between the integrity of the R / 2 position in the surface layer portion and the outgassing ability in the matrix is the best. That is, if the state of the R / 2 position can be expanded into the wafer surface, a uniform and high-quality wafer can be obtained. Therefore, in order to expand the state of the R / 2 position, BMD and The relationship between the distribution of grown-in defects and the pulling method of CZ single crystal silicon. The results of printing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs found that the in-plane distribution of the size of internal growth defects and BMD density became non-uniform, at least due to the crystal-controlling speed V (mm / minute) and The ratio V / G of the temperature gradient G (K / mm) of the solid-liquid interface in the direction of the crystal pulling axis in the range of melting point to 14 0 ° C has a distribution in the plane, that is, V / G varies within the plane. To. Therefore, regardless of the position within the wafer surface, in order to set the internal growth defect and BMD density as desired, the goal is to obtain the necessary specific V / G 値. This is explained below. It is well known that internal growth defects are affected by V / G, so a specific hot zone (HZ, furnace structure) of the crystal pulling device is used to set the nitrogen concentration in the drawn crystal to 1 X 1 〇1 3 cells / cm 3, and cultivated multiple results at a pulling speed selected from 1.0 to 1.4 mm / min to investigate the in-plane distribution and internal sound of each V / G [5 The relationship between the size and the 8 0 0 CTC X 4 hours + This paper size applies the Chinese National Standard (CNS) A4 size (210X297 mm) '' '-9-515008 A7 B7 V. Description of the invention (7) 1 0 0 0 ° Cxl BMD density after heat treatment for 6 hours. The results are shown in Figs. 1 and 2. (Please read the precautions on the back before filling in this page.) Figure 1 shows the BMD measured on the central part, R / 2 part, and peripheral part (the position from the outer periphery of the wafer of 10 mm) in the wafer surface. The relationship between all data of density and V / G shows that BMD density is directly related to V / G. When V / G is less than 190 mm2 / K.mi η, it is decreased to 1 x 109 / cm3 or less due to insufficient gas removal capability. That is, in order to obtain a high-density BMD, regardless of the position in the wafer surface, as long as V / G is set to greater than 0.175mm2 / K · ιηί η On the other hand, the second figure shows the use of 〇 Ρ (optional precipitate profiler) relatively evaluates the size of internal growth defects, in order to adjust the results of printing and checking the relationship with V / G by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Same as in Fig. 1, showing the relationship between all data of 0PP size measured on the central portion of the wafer, R / 2, and the peripheral portion and V / G, indicating that the 0PP size is directly related to V / G. That is, it was first found that when V / G is less than 0.225 mm2 / K, the size of the internal growth defect becomes drastically smaller, and when it exceeds the range of 0.225 mm2 / K.mi η, the internal growth defect The size is so large that it tends to be saturated. Therefore, in order to make it a small-sized internal growth defect that can be easily eliminated by heat treatment, V / G can be set to less than 0.2 25 mm 2 / K · mi η regardless of the position in the wafer surface. . From the results in Figures 1 and 2 above, when drawing a C Zn single crystal doped sand doped with nitrogen, 'if V / G is made into a crystalline paper, the Chinese paper standard (CNS) is applicable. Α4 specifications (210 × 297 mm) " -10- 515008 A7 B7 V. Description of the invention (8) The range of the diameter of 0. 175 to 0. 225mm2 / K * mi η (Please read the precautions on the back before filling in this Page), it will not become uneven in the wafer surface. Because the size of the internal growth defects is just small enough, it can be made to anneal the internal growth defects on the entire surface of the wafer and form an appropriate BMD density. Here, the wafer has a point defect that determines the size of the internal growth defect and the BMD density on the outer periphery of the drawn crystal. The point defect diffuses to the outside during the crystal culture. Therefore, in the area from the outer peripheral end of the drawn crystal to about 5% of the radius (for example, when pulling up a crystal with a diameter of 200 mm, up to 10 mm from the outer peripheral end), the size of the internal growth defect and the BMD density are The V / G relationship becomes loose. That is, in the range of V / G to which the present invention is applicable, a region excluding at least 90% of 5% of each of the two outer peripheral portions of the diameter direction of the drawn crystal is excluded. In this region, depending on the crystal pulling conditions, it is between 90 and 10. Change within 0%. Hereinafter, the present invention will be described in detail with reference to the drawings. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs First, a structure example of the single crystal extraction device of the C Z method used in the present invention will be described with reference to FIG. 6. As shown in FIG. 6, the single crystal pulling device 30 is composed of a crystal extraction chamber 3 1, a crucible 32 disposed in the crystal pulling chamber 31, and a heater 3 4 arranged around the crucible 32 to make the crucible. 3 2 Rotating crucible holding shaft 3 3 and coiling mechanism (not shown), holding seed crystals of silicon 5 seed chuck 6, pulling steel wire of seed chuck 6 7, and a winding mechanism (not shown) for rotating or winding the steel wire 7. The crucible 32 is provided with a quartz crucible on one side of the inner side containing the silicon melt 2 and a graphite crucible on the outer side, and the outer side of the heater 34 is provided with a paper sheet in accordance with Chinese National Standard (CNS) A4 specifications ( 210X 297 mm) -11-515008 A7 ___B7 _ V. Description of the invention (9) Thermal material 3 5. (Please read the precautions on the back before filling this page.) In addition, the manufacturing conditions related to the manufacturing method of the present invention, that is, the method of expanding the appropriate range of V / G to the diameter direction and axis direction can be performed by conventional methods. That is, for example, a solid-liquid interface heat insulating material 8 is provided on the outer periphery of the solid-liquid interface of the crystal, and HZ 'of the upper part surrounding the heat-insulating material 9 is provided thereon. The temperature gradient (G e) around the crystal and the temperature of the crystal center are provided. The difference (G e-G c) of the gradient (G c) is reduced so that the solid-liquid interface temperature gradient G becomes flat in the plane. The solid-liquid interface thermal insulation material 8 is arranged such that a gap 10 of 3 to 5 cm is left between the lower end and the liquid surface of the silicon melt 2. The upper surrounding heat insulation material 9 may not be used depending on conditions. In addition, a cylindrical cooling device 36 that blows a cooling gas or cuts off radiant heat to cool a single crystal may also be installed. In addition, recently, it is often used to provide a magnet (not shown) outside the horizontal direction of the extraction chamber 31 and The silicon melt 2 is a so-called MCZ method in which a magnetic field such as a horizontal direction or a vertical direction is applied to suppress convection of the melt and to obtain stable growth of a single crystal. Next, we will explain the cultivation method using the single crystal pulling device described above. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, firstly heat the high-purity crystalline raw material of silicon in the crucible 32 to a melting point (about 1420 ° C). ) Melted above. Nitrogen doping can be performed, for example, by putting a silicon wafer with a nitride film in a silicon raw material. Then, the front end of the seed crystal 5 is brought into contact with or immersed in the center portion of the surface of the solution 2 by winding out the steel wire 7. Then, rotate the crucible holding shaft 3 3 to an appropriate direction, and at the same time, take out the steel wire 7-draw the seed 5 while pulling it to open the paper. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -12- 515008 A7 B7 V. Description of the invention (Initial single crystal cultivation. After that, by adjusting the crystal pulling speed and temperature, a single crystal rod 1 with a substantially cylindrical shape can be obtained. (Please read the precautions on the back before reading) (Fill in this page) The obtained single crystal rod can be cut by hacksaw and other methods, and be chamfered, polished, etched, honed, etc. to make a silicon wafer doped with nitrogen. In the invention, heat treatment is performed on the obtained silicon wafer. In this way, a defect-free layer is uniformly formed on the surface, and BMD occurs at a high density in the base portion. The specific heat treatment conditions are those using ordinary heater Batch furnace, and heat treatment at 1 000 to 1 350 ° C in an inert gas such as argon, hydrogen, or a mixture of these for more than 1 hour (for example, 1 200 ° C, 1 hour; or 1 150 ° C, 4 hours, etc.) Alternatively, it can be used Rapid thermal annealing device (RTA) (rapid thermal annealing device) for rapid heating and rapid cooling heat treatment, or heat treatment using a batch furnace and RTA device. The following are specific examples of the present invention and comparative examples. The present invention is illustrated, but the present invention is not limited to these examples. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Example 1) Example 1 uses the temperature gradient of crystal center G c = 3 · 5 4 3 [K / mm], crystal temperature gradient Ge = 3.933 [K / mm], Ge-Gc = 0. 390 [K / mm], which has a smaller Ge-Gc than Z, a single crystal The crystal pulling device adjusts the crystal pulling speed to about 0.74 mm / min, and the paper size of the 6-inch diameter is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -13-515008 A7 B7 5 2. Description of the invention (1) (Please read the precautions on the back before filling this page) Nitrogen-doped single crystal silicon. The nitrogen doping method is to put silicon raw materials into a silicon wafer with a nitride film and pull the silicon wafer. Concentration of nitrogen at the position of the shoulder of the crystal (calculated 値It becomes 2 X 1 0 1 3 / cm 3. In addition, the oxygen concentration is adjusted to 14 to 15 ppma [JEI DA (Japan Electronics Industry Promotion Association) specification. Fig. 3 shows the crystal of V / G when the crystal is pulled. Distribution in the diameter direction. The diameter direction of V / G as a whole lies within a range of about 0.180 to 0.223mm2 / K.min. A silicon wafer was made from the pulled crystal, and the size of the internal growth defect was measured by the OPP method, followed by applying 800 ° C, 4 hours + 100 ° C, 16 hours of precipitation heat treatment to BMD was formed and the BMD density was measured by the OPP method. The measurement results of the internal growth defect size are shown in Fig. 4, and the measurement results of the B M D density are shown in Fig. 5. The internal growth defect printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is a size (less than 1.5) that can be fully eliminated by an argon atmosphere at 12000 ° C for 1 hour (Figure 4), and the in-plane distribution is also small. In addition, the B M D density is approximately 2 to 5 × 10 09 / cm3 at any position in the wafer surface, and a high-density and uniform in-plane distribution is obtained (FIG. 5). (Comparative Example 1, Comparative Example 2) As Comparative Examples 1 and 2, G c = 3 · 7 7 8 [K / mm], Ge = 4.904 [K / mm], and Ge—Gc = 1.126 [K / mm] has a single-crystal pulling device that is larger than Ge-Gc and larger than Z. In Comparative Example 1, the pulling speed is adjusted to the paper size to apply the Chinese National Standard (CNS) A4 specification (210X297 mm) " " " -14- 515008 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy / mi η and pull up a 6-inch diameter nitrogen-doped single-crystal silicon. Nitrogen doping is the silicon concentration of the silicon wafer with a nitride film placed in the silicon raw material, and the nitrogen concentration at the shoulder position of the pull crystal (calculated 値) Is 2x 1 013 / cm3. In addition, the oxygen concentration is adjusted to 14 to 15 ppma [JEIDA]. Comparative Example 1 and Comparative Example 2 The distribution of the crystal diameter direction of V / G in the drawn crystal is shown in Figure 3. In comparison V / G in the range of 0.175 to 0.225mm2 / K * mi η in Example 1 is compared with about 8 3% from the center of the crystal to the range of about 62 mm. In the case of 2, it is about 48% from the center of the crystal to the position of about 30 mm to the position of about 66 mm in the outer peripheral direction. A silicon wafer was produced from the pulled crystal and measured by the OPP method. Internal. After the size of the growth defect, apply 800 ° C, 4 hours + 100 ° C, L: 6 hours of precipitation heat treatment to form BMD, and measure the density of BMD by the 0 PP method. The measurement results are shown in Figure 4 and the BMD density measurement results are shown in Figure 5. In the wafer center of Comparative Example 1, the size of the internal growth defect is small, and the surface of the wafer becomes very small, and the surface of the defect size is small. Although the internal distribution is vast, it is a size defect that cannot be easily eliminated by annealing as a whole. However, it is found that the BMD density after the precipitation heat treatment is reduced to about 2x 1 08 / cm3 at the periphery of the wafer where the V / G 热处理 is low. In the comparative example 2, the density of BMD is about 1 X in the plane. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). ) ^ -15- (Please read the note on the back first Please fill in this page for the matters needing attention). «Order% ·. 515008 A7 B7 V. Description of the invention (1 full (please read the notes on the back before filling in this page) 1 〇9 / cm 3 or more, but due to internal growth defects The in-plane distribution of dimensions is large, especially the size of the wafer center is quite large, so even if annealing at 12000 ° C for 1 hour in the argon atmosphere, some internal growth defects in the central portion will remain. From these results, it can be known that, in the case of Z, the crystal pulling device used in Comparative Examples 1 and 2, in order to make the size of the internal growth defect and the BMD density evenly distributed in the plane, even if the crystal pulling speed is controlled at 0.8 It is also very difficult in a limited range of 4 to 0.87 mm / min. The present invention is not limited to the embodiments described above. The above-mentioned embodiment is merely an example. Those who have the same technical idea and substantially the same structure and effect as those described in the scope of patent application of the present invention are included in the technical scope of the present invention in any form. In the embodiment, the case of culturing single crystal silicon with a diameter of 6 inches is exemplified, but the present invention is not limited to this, and can also be applied to single crystal silicon with a diameter of 8 to 16 inches or larger. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs In addition, the present invention can also be applied to the so-called M C Z method of applying a horizontal magnetic field, a longitudinal magnetic field, and a cusp magnetic field to a silicon melt, which is self-evident. This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) -16-