經濟部智慧財產局員工消費合作社印製 575696 A7 B7 五、發明説明（i ) 【技術領域】 本發明係關於磊晶層之結晶缺陷極少，且，具有除氣（ gettenng )效果之磊晶晶圓及作爲其基板之矽晶圓之製造方 法，以及具有如其等特性之磊晶晶圓。 【背景技術】 存在於使用捷克勞斯基法（Czochralski method )( C Z 法）所拉起之C Z單晶矽中之成長缺陷（Gi'own-in缺陷） ，係使晶圓之氧化膜耐壓特性劣化，或於裝置製程已知會引 起絕緣不良等，爲了避免此現象提案有各種方法。例如使用 C Z法拉起單結晶中減低成長缺陷之方法，或對於晶圓在氫 或氬環境中施加高溫退火以去除表面缺陷之方法，或使用使 其成長磊晶層之磊晶晶圆之方法等。並且，隨著近年之半導 體元件之高積體化，半導體中之結晶缺陷，尤其減低表面及 表面附近之結晶缺陷已成爲重要之事。因此，在上述晶圓表 面形成優異結晶性之磊晶層之磊晶晶圓之需求逐年增高。 然而，使用磊晶晶圓製作裝置時，除了磊晶成長之外通 常進行各種熱處理。在這些工程之中若有重金屬雜質等汙染 時裝置特性會明顯地劣化，所以必須將這種汙染物等從磊晶 層儘量排除。因此，作爲磊晶成長用之基板，要求除氣效果 高之基板。 除氣係有附加性除氣（e X11. i n s i c g e 11 e r i n g ) ( E G )與Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 575696 A7 B7 V. Description of the Invention (i) [Technical Field] The present invention is an epitaxial wafer with very few crystal defects in the epitaxial layer and has a gettenng effect And a method for manufacturing a silicon wafer as a substrate thereof, and an epitaxial wafer having such characteristics. [Background Art] Growth defects (Gi'own-in defects) in CZ monocrystalline silicon pulled up by the Czochralski method (CZ method) are used to make the oxide film of the wafer withstand voltage Various methods have been proposed in order to avoid the deterioration of characteristics or the occurrence of poor insulation due to the device manufacturing process. For example, using the CZ method to pull up single crystals to reduce growth defects, or applying high temperature annealing to a wafer in a hydrogen or argon environment to remove surface defects, or using epitaxial wafers to grow epitaxial layers. . In addition, with the increasing accumulation of semiconductor devices in recent years, it has become important to reduce crystal defects in semiconductors, especially to reduce crystal defects on and near the surface. Therefore, the demand for epitaxial wafers that form epitaxial layers with excellent crystallinity on the wafer surface is increasing year by year. However, when an epitaxial wafer manufacturing apparatus is used, various heat treatments are usually performed in addition to epitaxial growth. In these projects, if there is contamination by heavy metal impurities, etc., the device characteristics will be significantly degraded, so it is necessary to exclude such pollutants from the epitaxial layer as much as possible. Therefore, as a substrate for epitaxial growth, a substrate having a high degassing effect is required. The degassing system has additional degassing (e X11. I n s i c g e 11 e r i n g) (E G) and
固有性除氣（i η t r i n s i c g e U e l. i n g ) ( I G )。代表性之E G 手法，係在基板背面堆積聚砂膜之Polyback seal (登錄商標 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------4衣------tT------0 (請先閱讀背面之注意事項再填寫本頁) -4- 經濟部智慈財產局員工消費合作社印製 575696 A7 B7 五、發明説明（2) )，或在背面給與機械性損傷之手法，但是這些手法不僅有 發生塵埃等問題，並且因需要特別之工程所以成本上變成非 常不利。 另者，I G係藉對於包含氧之c Z法矽晶圓進行熱處理 將成爲除氣側之氧澱積物發生在基板之體（bulk )中者。但 是，磊晶晶圓時，原本存在於基板之氧澱積核，爲在高溫之 磊晶晶圓成長中消滅，在其後之裝置熱處理因不容易形成、 成長氧澱積物，所以有除氣能力變成不充分之問題。 於是，於以往之磊晶晶圓之製造，利用含有高濃度硼之 基板（P +基板）爲具有除氣效果，在P +基板上使用形成低 硼濃度（P -)之磊晶層之P P +磊晶晶圓爲居多。然而 ，若在P +基板進行磊晶成長時就在磊晶成長中摻雜高濃度 硼爲從基板氣化而取入於磊晶層之自動摻雜，或硼爲從基板 表面在磊晶層內有由固相外方擴散取入之問題。又，最近作 爲C Μ〇S裝置用使用P -基板之磊晶晶圓之需求日益殷切 ，除氣能力不足成爲問題。 並且，極最近，作爲得到減低c Ζ法表面附近之成長缺 陷晶圓之方法，爲了提升高溫退火時之缺陷容易消滅’在結 晶摻雜氮，藉使成長孔隙（void )缺陷尺寸變小，可更到深 部藉退火以消滅缺陷之技術，或於磊晶晶圓，藉摻雜氮之結 晶作爲基板使用，促進裝置熱處理中形成氧澱積物，製造增 加BMD (Bulk Micro Defect)以提局I G能力之晶晶圓之 技術，活用摻雜氮之結晶特性之有效利用正在盛行。 作爲將這種摻雜氮結晶使用於磊晶成長用基板之一例’ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------抑衣------、玎------^ (請先閱讀背面之注意事項再填寫本頁) -5- 575696 Α7 _ Β7 經濟部智慧財產局8工消費合作社印製 五、發明説明（3) 曰本專利特開平1 1 一 1 8 9 4 9 3號公報所記載之技術， 將摻雑氮1 0 1Μ固/ c m 3以上所培養之單晶矽使用於磊晶晶 圓用者。此係’依據使用C Z法之單結晶拉起條件包括成環 狀發生之〇 S F ( Oxidation induced Stacking Faults :氧化感 應疊層缺陷）之基板上形成磊晶層時，〇S F環領域之氧澱 極核將不會消失，於磊晶形成後之裝置製程，將成爲有效之 除氣側發揮功能之見解，與培養單結晶時藉摻雜氮就可擴大 〇S F環寬度，將所摻雜之氮量成爲1 〇 13個/ c m 3以上時 ，就可將對於除氣有效之〇S F核可均勻地分散於整個單結 晶之見解所完成者。 然而，依據本發明人等所調查時，在經摻雜氮之晶圓上 形成磊晶層時，曉得了在磊晶層容易發生稱爲L P D ( Light Point Defect :使用雷射光之晶圓表面檢查裝置所觀察之亮點 缺陷之總稱）對於裝置成爲有害之缺陷。又，曉得了此 L P D係尤其氮濃度高時（1 X 1 〇 14個/ c m 3以上）顯著 地被觀察到。像這樣氮濃度愈高在裝置製程中所發生之體（ bulk)中之BMD密度就變高雖然也具有I G能力變高之益 處，但是在磊晶層表面所觀察之缺陷爲以直徑2 0 0 m m之 晶圓發生數十〜數百個，有損及磊晶層完全性之問題。 因此作爲其對策雖然可想到使氮濃度成爲1 X 1 〇 14個 / c m以下’但是’此時’嘉晶表面之缺陷爲少雖然表層 之完全性會增高，但是因氧澱積之促進I G能力之提升效果 會變成減弱之結果。尤其於晶圓之外周部B M D變少，不能 說除氣能力爲不足。 (請先閱讀背面之注意事項再填寫本頁) 裝· 、\ST» 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -6 - 575696 經濟部智慈財產局Μ工消費合作社印製 A7 ______B7 五、發明説明（4 ) 【發明之揭示】 於是本發明係鑑於這種問題所完成者，其目的係提供一 種在摻雜氮之C Z矽單結晶晶圓進行磊晶成長時，抑制發生 於晶晶層之結晶缺陷（以下，有時稱爲嘉晶缺陷），並且具 有優異I G能力之磊晶晶圓用基板及使用其基板之磊晶晶圓 ，以及其等製造方法。 爲了解決上述問題，關於本發明之矽晶圓之製造方法， 係培養使用C Z法摻雜氮之單晶矽，於從該單晶矽製造矽晶 圓之方法，其特徵爲：將摻雜之氮濃度成爲1 x 1 〇 Μ個/ c m 3以下，設定培養上述單晶矽時之拉起速度ν與固液界 面温度坡度G之比（V / G )使發生於所製造之矽晶圓之 B M D爲能夠成爲既定密度。 像這樣，欲製造磊晶缺陷之發生極少，且得到具有充分 除氣效果之磊晶晶圓所需之矽晶圓時，將氮濃度成爲1 χ 1 0 14個/ c m 3以下來抑制磊晶缺陷之發生，並且，在磊晶 成長後’設定單結晶培養時之V / G爲充分高時，施加 8〇0 °C ’ 4小時及1 0 〇 〇 °C，1 6小時之熱處理時所發 生之B M D爲能夠變成既定密度，曉得了於裝置製程產生可 得到充分除氣效果所需B M D密度之B M D核。亦即，於摻 雜氮結晶，發現了屬於單結晶培養條件之V / G値與晶晶成 長後之後處理所發生之B M D密度大有關係。 於此，所謂既定之B M D密度，係依所製作之裝置種類 所需之密度雖然不同，但是，至少具有1 χ 1 〇 8個/ c m 3 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -- -7- 批衣-------1T—--------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慈財產局資工消費合作社印製 575696 A7 _ _ B7 五、發明説明（5) 較佳。因此’ β M D爲能夠變成1 x 1 〇 s個/ c ηΊ 3以上之 所需密度而設定V/G値。具體上爲將氮濃度成爲1 X 1 〇 14個/ c m 3以下，從種種ν / G條件下所拉起之結晶製 作砂晶圓’對於這些形成所需磊晶層之後藉測定B M D密度 所求取之B M D密度與ν / g之相關關係預先求取，依據此 相關關係設定V / G即可。其時，爲了欲充分得到因摻雜氮 之氧丨殿積促進效果，氮濃度爲具1 X 1 〇 12個/ c m 3以上較 佳。 此時’將V / G所培養之單晶矽徑向之至少在9 〇 %範 圍成爲0 · 3 m m 2/ κ · m i η以上較佳。 像這樣，將欲設定之V / G成爲〇 . 3 mm2/K.min以上 時，於裝置製程就可得到顯示充分除氣效果之B M D密度。 並且此時’ V / G之偏差爲於所培養單晶矽徑向可成爲 位於 ± 0 . Ο 1 5 m m 2 / K · m i η 之範圍。 像這樣，設計V / G之面內分布成爲均勻之η Ζ (熱區 ’爐內構造）藉培養結晶，就可製造B M D之面內分布爲均 勻之矽晶圓。亦即，在晶圓面內可製造具有除氣效果之晶圓 〇 並且，此情形時，就可將摻雜之氮濃度成爲1 X 1〇13 個/ c m 3以上。 像這樣，於某裝置製程作爲顯示具充分除氣效果之指標 ，於晶圓全面需要5 X 1 0 8個/ c m 3以上之b M D密度時 ，將摻雜之氮濃度成爲1 X 1 0 13個/ c m 3以上較佳。 並且，關於本發明之嘉晶晶圓之製造方法，其特徵爲： 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------批衣------、玎--------線 (請先閱讀背面之注意事項再填寫本頁) -8- 經濟部智慧財產局Μ工消費合作社印製 575696 Α7 Β7 五、發明説明（6 ) 對於上述製造方法所製造之矽晶圓，形成磊晶層。 這樣做時，磊晶表面之缺陷爲少，不僅表層之完全性增 高，並且，促進氧之澱積而增大BMD密度可製造I G能力 極高之磊晶晶圓。 並且，依據本發明，就可提供由上述製造方法所製造無 磊晶缺陷形成磊晶層之I G能力極高之磊晶晶圓。 並且，在依據本發明形成磊晶層之矽晶圓，其特徵爲： 施加8 0 0 °C，4小時及1 0 0 0 °C，1 6小時之熱處理時 ，在屬於基板之矽晶圓之體（bulk)中發生5 X 1〇8 個/ c m 3以上之B M D之磊晶晶圓，磊晶晶圓之表層部之 結晶缺陷爲0 · 0 6 4個/ c m 2以下。 ，按，在此粒子計數器所觀察之磊晶層表層部之結晶缺陷 ，至少包含轉位環（ring )及磊晶疊層缺陷（S F )。 此情形時，就可將矽晶圓中之氮濃度成爲1 X 1 〇 13χ 1 X 1 〇 14個 / c m 3。 像這樣，若規定矽晶圓之氮濃度時，就可提供不僅 I G能力爲高並且形成磊晶缺陷少之磊晶層之磊晶晶圓。 又，若依據本發明，因提供在成爲基板之矽晶圓表面之 轉位環之密度爲2 0個/ c m 2以下之矽晶圓形成磊晶層之 磊晶晶圓，所以，可確實得到磊晶缺陷少之磊晶晶圓。 並且，將成爲基板之砂晶圓表面之〇S F密度藉成爲未 滿1 0 0個/ c m 2，儘管成爲〇S F發生之核之氧澱積物 爲少之矽晶圓，具有高密度之B M D，具有高除氣能力’並 且，提供磊晶缺陷極少之磊晶晶圓。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ---------辦衣------1Τ-----i—0 (請先閱讀背面之注意事項再填寫本頁) -9- 575696 A7 ____ B7_ 一 五、發明説明（7 ) 如以上所說明，若依據本發明，在摻雜氮之c Z法單晶 矽晶圓進行磊晶成長時，儘量抑制磊晶層所發生之結晶缺陷 ，並且可提供具有優異I G能力之磊晶晶圓用基板及使用其 基板之晶晶晶圓’以及其等之製造方法。 【實施發明之最佳形態】 茲關於本發明之形態詳細說明如下。Intrinsic outgassing (i η t r i n s i c g e U e l. I n g) (I G). The representative EG method is a Polyback seal (registered trademark) on which the poly-sand film is deposited on the back of the substrate. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) --------- 4 clothing- ---- tT ------ 0 (Please read the precautions on the back before filling this page) -4- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575696 A7 B7 V. Description of Invention (2)) , Or the method of giving mechanical damage to the back, but these methods not only have problems such as dust generation, but also require a special project, so the cost becomes very unfavorable. In addition, I G is a heat treatment of a silicon wafer containing cZ method containing oxygen, and the oxygen deposition on the outgas side will occur in the bulk of the substrate. However, in epitaxial wafers, the oxygen deposition nuclei that originally existed on the substrate were eliminated during the growth of epitaxial wafers at high temperatures. The subsequent device heat treatment is not easy to form and grow oxygen deposits. Qi has become a problem of inadequacy. Therefore, in the manufacture of conventional epitaxial wafers, a substrate (P + substrate) containing a high concentration of boron was used to have a degassing effect, and a PP forming an epitaxial layer with a low boron concentration (P-) was used on the P + substrate. + Epitaxial wafers are mostly. However, if the P + substrate undergoes epitaxial growth, high concentration boron is doped in the epitaxial growth for automatic doping to be taken into the epitaxial layer from the substrate for vaporization, or boron is deposited on the epitaxial layer from the substrate surface. There is a problem of taking in from the outside of the solid phase. In addition, recently, epitaxial wafers using P-substrates for CMOS devices have become increasingly demanding, and insufficient degassing capacity has become a problem. And, very recently, as a method to reduce the growth defect wafer near the surface of the cZ method, in order to improve the defects during high temperature annealing, it is easy to eliminate the defects. Doping nitrogen in the crystal can reduce the size of the growth void (void) defect. In the deep part, the technique of eliminating defects by annealing, or the use of nitrogen-doped crystals as substrates in epitaxial wafers, promotes the formation of oxygen deposits during device heat treatment, and adds BMD (Bulk Micro Defect) to improve IG. The technology of capable wafers is making effective use of nitrogen-doped crystalline characteristics. As an example of using such doped nitrogen crystals for epitaxial growth substrates, 'this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) --------- Inhibit clothes ---- -、 玎 ------ ^ (Please read the notes on the back before filling in this page) -5- 575696 Α7 _ Β7 Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) According to the technique described in Japanese Patent Laid-Open No. 11-11 8 9 4 93, a single crystal silicon cultured with erbium-doped nitrogen at 101 M / cm 3 or more is used for epitaxial wafers. This is based on the single crystal pull-up conditions using the CZ method, including the formation of an epitaxial layer on a substrate of 0SF (Oxidation induced Stacking Faults) occurring in the form of rings. The core will not disappear, and the device process after the epitaxial formation will become an effective insight into the function of the outgassing side. When the single crystal is cultivated, the width of the SF ring can be expanded by doping nitrogen, and the doped nitrogen When the amount is 1013 particles / cm 3 or more, it is possible to disperse the 0SF nucleus effective for degassing evenly throughout the single crystal. However, according to the investigation by the present inventors, when forming an epitaxial layer on a wafer doped with nitrogen, it was known that the epitaxial layer is prone to occur called LPD (Light Point Defect: wafer surface inspection using laser light). The general name of the bright spot defects observed by the device) becomes a harmful defect to the device. It was also found that this L P D system was noticeably observed particularly when the nitrogen concentration was high (1 × 10 14 cells / cm 3 or more). As such, the higher the nitrogen concentration, the higher the BMD density in the bulk that occurs during the device manufacturing process. Although it also has the benefit of higher IG capabilities, the defect observed on the surface of the epitaxial layer is a diameter of 2 0 0 There are dozens to hundreds of wafers of mm, which will damage the integrity of the epitaxial layer. Therefore, as a countermeasure, although it is conceivable to reduce the nitrogen concentration to 1 × 10 14 / cm or less, but at this time, the surface defect of the Jiajing is small. Although the completeness of the surface layer will be increased, the IG ability is promoted by oxygen deposition. The promotion effect will become a weakened result. In particular, there is less B M D in the outer peripheral portion of the wafer, and it cannot be said that the outgassing capability is insufficient. (Please read the precautions on the back before filling in this page.) The size of the paper on the paper is suitable for China National Standard (CNS) A4 (210X 297 mm) -6-575696 Printed by Consumer Cooperative A7 ______B7 V. Description of Invention (4) [Disclosure of Invention] The present invention was made in view of this problem, and its purpose is to provide epitaxial growth on a nitrogen-doped CZ silicon single crystal wafer At the same time, substrates for epitaxial wafers with excellent IG capability and epitaxial wafers using the substrates, as well as manufacturing methods thereof, are suppressed from crystal defects (hereinafter sometimes referred to as Jiajing defects) occurring in the crystal layer. . In order to solve the above-mentioned problems, the method for manufacturing a silicon wafer of the present invention is a method of cultivating a single crystal silicon doped with nitrogen by using the CZ method, and manufacturing a silicon wafer from the single crystal silicon, which is characterized by: The nitrogen concentration becomes 1 x 10 μm / cm 3 or less, and the ratio (V / G) of the pull-up speed ν to the solid-liquid interface temperature gradient G when the above-mentioned single crystal silicon is cultivated is set so that it occurs in the silicon wafer produced. BMD is capable of becoming a given density. In this way, when silicon wafers required to produce epitaxial wafers with minimal occurrence of epitaxial defects are obtained, and an epitaxial wafer with sufficient outgassing effect is obtained, the nitrogen concentration is controlled to 1 χ 1 0 14 pieces / cm 3 or less to suppress epitaxy. Defects occurred, and when the V / G during single crystal cultivation was set to be sufficiently high after epitaxial growth, it was subjected to a heat treatment of 8000 ° C for 4 hours and 100 ° C for 16 hours. The BMD that occurs can be changed to a predetermined density, and it is known that the BMD kernel that produces the BMD density required to obtain a sufficient degassing effect in the device manufacturing process. That is, in doped nitrogen crystals, it was found that V / G 値, which is a single crystal culture condition, is strongly related to the B M D density that occurs after processing after the crystals grow. Here, the so-called BMD density means that although the density required by the type of device is different, it must have at least 1 x 108 pcs / cm3. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297). Mm)--7- Approval ------- 1T —-------- ^ (Please read the precautions on the back before filling out this page) Consumption of Industrial Workers, Intellectual Property Office, Ministry of Economic Affairs Printed by the cooperative 575696 A7 _ _ B7 V. Invention description (5) is better. Therefore, 'β M D is set to V / G 値 to a desired density capable of becoming 1 x 10 s / c ηΊ 3 or more. Specifically, a sand wafer was made from the crystals pulled up under various conditions of ν / G under a nitrogen concentration of 1 × 10 14 pieces / cm 3 or less. For these, the required epitaxial layer was formed by measuring the BMD density. The correlation between the BMD density and ν / g is obtained in advance, and V / G can be set according to this correlation. At this time, in order to fully obtain the nitrogen-doped oxygen promotion effect, it is better to have a nitrogen concentration of 1 × 10 12 / cm 3 or more. At this time, it is preferable that the radial direction of the single crystal silicon cultured by V / G is at least 90 m in a range of 0 · 3 m 2 / κ · m i η or more. In this way, when the V / G to be set is 0.3 mm2 / K.min or more, a B M D density exhibiting a sufficient outgassing effect can be obtained in the device manufacturing process. At this time, the deviation of 'V / G' is such that the radial direction of the cultured single crystal silicon can be located within a range of ± 0.5 m 2 / K · m i η. In this way, the in-plane distribution of V / G is designed to be uniform ηZ (the structure of the hot zone's furnace). By cultivating crystals, silicon wafers with uniform in-plane distribution of B M D can be manufactured. That is, a wafer having a degassing effect can be manufactured within the wafer surface. In this case, the doped nitrogen concentration can be 1 × 1013 pieces / cm3 or more. In this way, when a certain device process is used as an indicator of sufficient degassing effect, when the wafer needs a b MD density of 5 X 108 or more per cm 3 or more, the doped nitrogen concentration is 1 X 1 0 13 More than / cm 3 is preferred. In addition, the manufacturing method of the Jiajing wafer of the present invention is characterized in that: the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) --------- batch of clothing ---- -、 玎 -------- line (please read the notes on the back before filling this page) -8- Printed by the Intellectual Property Bureau of the Ministry of Economy, M Industrial Consumer Cooperative, 575696 Α7 Β7 V. Description of Invention (6) For the silicon wafer manufactured by the above manufacturing method, an epitaxial layer is formed. In doing so, the epitaxial surface has fewer defects, which not only increases the completeness of the surface layer, but also promotes the deposition of oxygen and increases the BMD density to produce epitaxial wafers with extremely high I G capabilities. In addition, according to the present invention, it is possible to provide an epitaxial wafer having an extremely high IG capability for forming an epitaxial layer without an epitaxial defect manufactured by the above-mentioned manufacturing method. In addition, the silicon wafer forming the epitaxial layer according to the present invention is characterized in that: when a heat treatment of 800 ° C, 4 hours, and 100 ° C, 16 hours is applied, a silicon wafer belonging to a substrate is applied; An epitaxial wafer with a BMD of 5 X 108 pieces / cm 3 or more occurred in a bulk, and the crystal defect of the surface layer part of the epitaxial wafer was 0 · 0 6 4 pieces / cm 2 or less. According to this, the crystal defects in the surface layer of the epitaxial layer observed in this particle counter include at least an index ring (ring) and an epitaxial stacking defect (S F). In this case, the nitrogen concentration in the silicon wafer can be set to 1 X 1 〇 13χ 1 X 1 〇 14 / c m 3. In this way, if the nitrogen concentration of the silicon wafer is specified, an epitaxial wafer having not only a high I G capability but an epitaxial layer with few epitaxial defects can be provided. In addition, according to the present invention, since an epitaxial wafer having an epitaxial layer formed on a silicon wafer having a density of 20 or less cm / cm 2 on the surface of a silicon wafer serving as a substrate is provided, it is possible to obtain An epitaxial wafer with few epitaxial defects. In addition, the SF density of the surface of the sand wafer that becomes the substrate is reduced to less than 100 pieces / cm 2, although the silicon oxide that is the core of the SF generation is a small silicon wafer, which has a high density of BMD. , Has a high outgassing capability ', and provides epitaxial wafers with few epitaxial defects. This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) --------- Doing clothing ------ 1T ----- i—0 (Please read the Please fill in this page again for attention) -9- 575696 A7 ____ B7_ One or five. Description of the invention (7) As explained above, according to the present invention, when epitaxial growth is performed on a nitrogen-doped cZ method single crystal silicon wafer As far as possible, suppress the crystal defects that occur in the epitaxial layer, and provide substrates for epitaxial wafers with excellent IG capabilities, and crystal wafers using the substrates, and manufacturing methods thereof. [Best Mode for Carrying Out the Invention] The mode of the present invention is described in detail below.
欲兼顧本發明作爲目的之磊晶層表層部之無結晶缺陷之 完全性與體（bulk )中之I G能力時，可構想2種手法。亦 即，使其成爲高氮濃度充分發生B M D，以另外方法減低磊 晶缺陷，或在低氮濃度抑制磊晶缺陷以另外方法增大B M D 之任一。 其中，首先關於成爲前者之高氮濃度之方法說明如下。 如本申請人先前所申請之w〇 0 1 / 2 7 3 6 2 A 1所記 載，曉得了在磊晶層表面出現之磊晶缺陷具有轉位環與S F (Stacking Fault)之2種。又，因其磊晶缺陷之許多爲轉位 環，所以作爲減低轉位環之方法提案了先前之W〇 01/ 2 7 3 6 2 A 1。因此，依據此方法，因可儘量減低磊晶缺 陷爲大多數之轉位環，所以結果來說減低了在磊晶層表面所 .見到之磊晶缺陷之L P D ( Light Point Defect :使用雷射光 之晶圓表面檢查裝置所觀察之亮點缺陷之總稱）。 但是，這種方法適用於對於矽塊錠（snkon mgot)之 總長並不一定爲容易之事，在成本上也具有不利之層面。又 ，當然磊晶缺陷爲儘量近於全無較佳，爲此，不只是需要減 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） (請先閱讀背面之注意事項再填寫本頁)When considering the completeness of the surface layer of the epitaxial layer without crystal defects and the IG capability in the bulk of the present invention, two methods can be conceived. That is, the B M D is sufficiently generated at a high nitrogen concentration, and the epitaxial defect is reduced by another method, or the B M D is suppressed by a low nitrogen concentration, and the B M D is increased by another method. Among them, a method for achieving a high nitrogen concentration of the former is described below. As described in the previous application by the applicant, w0 0 1/2 7 3 6 2 A 1, it is known that the epitaxial defect appearing on the surface of the epitaxial layer has two types of indexing ring and S F (Stacking Fault). In addition, since many of the epitaxial defects are indexed loops, a method of reducing the indexed loops as previously proposed is W01 / 2 7 3 6 2 A 1. Therefore, according to this method, since the epitaxial defect can be reduced as much as possible, so as a result, the epitaxial layer on the surface of the epitaxial layer can be reduced. The LPD (Light Point Defect: Laser light) (General name of bright spot defects observed by wafer surface inspection equipment). However, it is not necessarily easy to apply this method to the total length of the silicon ingot (snkon mgot), and it is also disadvantageous in terms of cost. Also, of course, the epitaxial defect is better to be as close to nothing as possible. For this reason, it is not only necessary to reduce the paper size to apply the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) (please read the precautions on the back first) (Fill in this page)
經濟部智慧財產局員工消費合作社印製 -10- 575696 Α7 _ Β7 五、發明説明（8) 低轉位環，也需要抑制s F之發生。 因而，本發明人等係依後者之方法，亦即，以低氮濃度 減少兩者之磊晶缺陷（轉位環及S F )，是否可將B M D使 用其他方法加以增加’努力進行檢討之結果，發現了對於屬 於單晶矽拉起條件之V / G (培養單晶矽時之拉起速度ν與 從砂熔點到1 4 0 0 °C間之成長軸方向之固液界面溫度坡度 G之比）之面內分布與磊晶成長後之BMD密度之面內分布 有很大的相關關係，淸查各種條件終於完成本發明。 第1圖係表示使用某拉起裝置拉起摻雜2 X 1 0 13 個/ c m 3氮（在拉起結晶之肩位置之計算値）之c Z單晶 矽時之V / G之面內分布例之圖（拉起速度係1 . 1 m m /m i η與1 · 3 m m/m i η之2條件）。從第1圖 就可淸楚，於此拉起速度，V / G係向拉起結晶周邊降低。 按，結晶之氧濃度爲1 2〜1 5 p p m a ( ：! ΕID A :日本電 子工業振興協會規格）之範圍。Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -10- 575696 Α7 _ Β7 V. Description of the invention (8) The low index ring also needs to suppress the occurrence of s F. Therefore, the present inventors have followed the method of the latter, that is, reducing the epitaxial defects (the index ring and the SF) of the two at a low nitrogen concentration, and whether it is possible to increase BMD using other methods. The ratio of V / G (the pull-up speed ν during the cultivation of single-crystal silicon to the solid-liquid interface temperature gradient G in the direction of the growth axis from the melting point of the sand to 14 0 ° C) was found for the single-crystal silicon pull-up conditions. The in-plane distribution of) has a great correlation with the in-plane distribution of BMD density after epitaxial growth. After examining various conditions, the present invention is finally completed. Figure 1 shows the in-plane V / G of c Z single crystal silicon doped with 2 X 1 0 13 / cm 3 nitrogen (calculated at the shoulder position of the pulled crystal) using a pull-up device. An example of the distribution (the pull-up speed is a condition of 1.1 mm / mi η and 1.3 mm / mi η). It can be seen from Fig. 1 that the pulling speed is reduced, and the V / G system decreases toward the periphery of the pulling crystal. The oxygen concentration of the crystal is in the range of 12 to 15 p p m a (:! ΕID A: Japan Electronics Industry Association Standards) range.
另一方面，第2圖係表示從依第1圖之拉起條件所拉起 之單晶矽塊錠製作矽鏡面晶圓之後，在1 1 2 5 °C形成5 // m磊晶層之後，爲了將B M D成長到可檢測之尺寸施加 8〇〇°C ，4小時及1〇0〇t：，1 6小時之熱處理，使用 〇 P P ( Optical Precipitate Profiler)裝置測定面內之 B M D密度之結果者。從第2圖就可淸楚，即使氮爲1 3次 方之較低濃度，晶圓中心附近爲具有某程度之高B M D密度 ，而成爲周邊下降之分布。亦即，V / G面內分布與磊晶成 長後之B M D之面內分布趨向爲相符，闡明了成爲高V / G 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -¾衣-- (請先閱讀背面之注意事項再填寫本頁) 、^1 線 經濟部智慧財產局S工消費合作社印製 -11 - 575696 Α7 Β7 五、發明説明（9 ) 4 高 B M D 〇 (請先閱讀背面之注意事項再填寫本頁) 又，從這些第1圖，第2圖，爲了表示具有充分除氣效 果一個指標之B M D密度達成5 X 1 0 8個/ c m 3以上，就 曉得V / G爲大槪具0 · 3 m m 2/ K · m i η以上即可。 爲了確認此事，拉起裝置之爐內構造（Η Ζ :熱區）及 調節拉起速度成爲V / G在約〇 . 4 3 nim2/K · min，面內 分布成爲扁平（0· 43 土 0.015) (〇爲約2_8 K /m m，拉起速度爲1 . 2 m m/m i η )，摻雜氮使在 肩位置能夠成爲2 X 1 0 13個/ c m 3進行結晶之培養，將磊 晶成長後之B M D與上述同樣方法觀察時，B M D密度爲約 2 X 1 〇 9個/ c m 3而面內分布爲大致成爲均勻。 線 像這樣所以欲將V / G成爲〇 . 3 m m 2/ K · m 1 η 以上時，首先，例如G之面內分布爲使用扁平Η Ζ，有將拉 起速度變成高速之方法。此情形時，與通常之C Ζ法，或欲 施加te場之所謂M C Ζ法無關就可達成。於此方法，裔晶成 長後之BMD之面內分布也會變成安定者。 經濟部智慈財產局員工消費合作社印製 又，即使G之面內分布並非扁平，認爲總之V / G之最 小値超過0 . 3即可，即使使用成爲那種G分布之Η Ζ，將 捲起速度成爲更高速，總之只要V / G能夠超過0，3 m m 2 / Κ · m 1 η拉起即可。此方法之情形時，M C Ζ法 者較更容易達成。其理由係拉起結晶不至於變形可培養之最 大拉起速度，爲MC Ζ法較通常之C Ζ法也對於G成爲高速 所致。但是，這種情形時，V / G爲與具有面內分布者同樣 地磊晶成長後之B M D也成爲具有面內分布。但是，依據拉 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -12- 575696 Α7 ___ Β7 五、發明説明（10) 起條件就可將B M D之最低密度成爲約5 X 1 0 s ( 裝-- (請先閱讀背面之注意事項再填寫本頁) 個/ c m 3 ) ’在晶圓之約略全面將具有充分之I G能力。 按’對於摻雜氮基板上進行磊晶成長時，磊晶成長後之 BMD密度’係不太依存磊晶成長前之基板氧濃度，只要具 有：L1〜16ppma (JEIDA)左右就不會出現太大 差異。 按’如上述V / G値雖然較0 · 3 m m 2 / K · m i η 愈大愈好’但是若太大時結晶就會變形，所以通常〇 · 5 5 m m2/ Κ · m i η左右爲界限。 茲就本發明所使用之單結晶拉起裝置參照圖式說明如下 〇 經濟部智慧財產局8工消費合作社印製 首先，於本發明爲了使V / G在面內變成扁平（亦即， 固液界面溫度坡度G在徑向爲扁平）所需之單結晶拉起裝置 之構成例使用第7圖說明。如第7圖所示，此單結晶拉起裝 置3 0，係具有：拉起室3 1，與設於拉起室3 1中之坩堝 3 2，與配置於坩堝3 2周圍之加熱器3 4，與迴轉坩堝 3 2之坩堝保持軸3 3及其迴轉機構（未圖示），與保持矽 之種結晶5之種結晶夾具6，與拉起種結晶夾具6之鋼索7 ，與迴轉或捲繞鋼索7之捲取機構（未圖示）所構成。坩堝 3 2係在收容其內側之矽熔液2側設有石英坩堝，在其外側 設有石墨坩堝。又，在加熱器3 4外側周圍配置有隔熱材 3 5 ° 又，爲了設定關於本發明之製造條件（在面內爲扁平之 G )，在結晶之固液界面外周設置環狀固液界面隔熱材8， 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -13- 經濟部智慈財產局肖工消費合作社印製 575696 Α7 Β7 五、發明説明（n) 在其上配置有上部圍繞隔熱材9。此固液界面隔熱材8係在 其下端與矽熔液2之熔液面之間設有3〜5 c m間隙1〇。 上部圍繞隔熱材9係依條件有時爲不使.用。並且，噴吹冷氣 ，或也可設遮蔽幅射熱以冷卻卓結晶之筒狀冷卻裝置3 6 ° 另外，最近如第8圖所視在拉起室3 1之水平方向外側 ，設置常傳導或超電導線圏等所成之磁鐵3 8，對於矽熔液 2藉施加水平方向或垂直方向等磁場以抑制熔液之對流’力 求單結晶之安定成長，使用所謂M C Z法之情形爲多。施加 於熔液之磁場方向，係依磁鐵配置可簡單地變更。例如，將 一個線圈配置成如向水平方向圍繞拉起室3 1時，對於熔液 將施加垂直方向之磁場（縱磁場），對向配置二個線圈在拉 起室3 1之水平方向外側诗，將對於熔液施加水平方向之磁 場（橫磁場）。並且，即使於本發明，如上述使用此M C Ζ 法時，就不至於發生拉起結晶之變形將可培養之最大拉起速 度，較通常之CZ法成爲局速。 另外，即使G並非扁平只要V / G之最小値爲超過 〇.3 m m 2/ Κ · m 1 η即可時，即使使用成爲那一種G 分布之Η Ζ因只要使拉起速度變成更高即可，所以可使用第 9圖所示通常所使用之單結晶拉起裝置。關於基本構造，雖 然與第7圖之拉起裝置相同，但是並無裝備固液界面隔熱材 8或上部圍繞隔熱材9。也可以在第9圖之裝置配備磁鐵使 用M C Ζ法以高V / G拉起結晶。 茲就使用上述第7圖之單結晶拉起裝置3 0之單結晶培 養方法說明如下。首先，在坩堝3 2內將矽之高純度多結晶 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)On the other hand, Figure 2 shows that after making a silicon mirror wafer from a single crystal silicon ingot pulled up according to the pulling conditions of Figure 1, after forming a 5 // m epitaxial layer at 1 1 2 5 ° C In order to grow BMD to a detectable size, 800 ° C, 4 hours and 1000 t: 16 hours of heat treatment were used, and the results of measuring the in-plane BMD density using 〇PP (Optical Precipitate Profiler) device By. It can be seen from Figure 2 that even if the nitrogen concentration is lower than the 13th power, the wafer center has a certain high B M D density near the center of the wafer, and it becomes a distribution of peripheral decline. That is, the in-plane distribution of V / G is in line with the in-plane distribution of BMD after epitaxial growth, which clarifies that it becomes a high V / G paper standard applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -¾ Clothing-(Please read the precautions on the back before filling this page), ^ 1 Printed by S Industrial Consumer Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs -11-575696 Α7 Β7 V. Description of Invention (9) 4 High BMD 〇 (Please Please read the precautions on the back before filling in this page.) Also, from these 1st and 2nd figures, in order to show that the BMD density of one index with sufficient degassing effect reaches 5 X 1 0 8 / cm 3 or more, we know V / G is a large harness of 0 · 3 mm 2 / K · mi η or more. In order to confirm this, the furnace structure of the pull-up device (: 调节: hot zone) and the adjustment of the pull-up speed became V / G at about 0.4 3 nim2 / K · min, and the in-plane distribution became flat (0 · 43 soil 0.015) (0 is about 2-8 K / mm, pull-up speed is 1.2 mm / mi η), nitrogen is doped so that the shoulder position can be 2 X 1 0 13 pieces / cm 3 for culturing crystals, and epitaxial When the grown BMD was observed in the same manner as described above, the BMD density was about 2 × 10 9 pieces / cm 3 and the in-plane distribution was approximately uniform. When the line is like this, so that V / G should be 0.3 m m 2 / K · m 1 η or more, first, for example, the flat surface GZ is used to distribute G, and there is a method of changing the pull-up speed to a high speed. In this case, it can be achieved regardless of the usual C Z method or the so-called M C Z method in which a te field is to be applied. In this method, the in-plane distribution of the BMD after the crystal grows will also become stable. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, even if the in-plane distribution of G is not flat, it is considered that the minimum value of V / G is more than 0.3, even if it is used as the distribution of G. The winding speed becomes higher. In short, as long as V / G can exceed 0, 3 mm 2 / κ · m 1 η, it can be pulled up. In the case of this method, the MCZ method is easier to achieve. The reason is that the maximum pulling speed at which the crystals can be pulled without being deformed can be caused by the fact that the MC ZO method is faster than G for the C ZO method. However, in this case, B / D after V / G is epitaxially grown similarly to those having an in-plane distribution also has an in-plane distribution. However, according to the Chinese standard (CNS) A4 specification (210X297 mm) according to the size of the drawn paper, -12- 575696 Α7 ___ B7 V. Description of the invention (10) The minimum density of BMD can be about 5 X 1 0 s (mounting-(Please read the notes on the back before filling out this page) pcs / cm3) 'Approximately comprehensive in wafers will have full IG capabilities. Press 'For epitaxial growth on a doped nitrogen substrate, the BMD density after epitaxial growth' is not very dependent on the substrate oxygen concentration before epitaxial growth, as long as it has: L1 ~ 16ppma (JEIDA) or so Big difference. Press 'As above V / G 値, although it is larger than 0 · 3 mm 2 / K · mi η, the bigger the better', but if it is too large, the crystal will deform, so it is usually about 0.5 5 m m2 / Κ · mi η is about limit. The single crystal pull-up device used in the present invention is described below with reference to the drawings. Printed by the 8th Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs First, in the present invention, in order to make V / G flat in the surface (that is, solid-liquid An example of the configuration of the single crystal pull-up device required for the interface temperature gradient G is flat in the radial direction is described with reference to FIG. 7. As shown in FIG. 7, the single crystal pulling device 30 includes: a pulling chamber 3 1; a crucible 32 provided in the pulling chamber 31; and a heater 3 arranged around the crucible 32. 4, with the crucible holding shaft 3 2 of the rotating crucible 3 2 and its rotating mechanism (not shown), with a crystal holder 6 holding silicon seed crystal 5, and a steel cable 7 pulling up the crystal holder 6, and rotating or A coiling mechanism (not shown) for winding the steel cable 7 is formed. The crucible 32 is provided with a quartz crucible on the side of the silicon melt 2 containing the inside, and a graphite crucible on the outside. A heat insulating material 3 5 ° is arranged around the outside of the heater 34, and in order to set the manufacturing conditions of the present invention (flat G in the plane), a ring-shaped solid-liquid interface is provided on the outer periphery of the solid-liquid interface of the crystal. Insulation material 8, this paper size applies Chinese National Standard (CNS) Α4 specification (210X297 mm) -13- Printed by Xiaogong Consumer Cooperative of Intellectual Property Bureau of Ministry of Economy 575696 Α7 Β7 V. Description of invention (n) The upper part surrounds the heat insulating material 9. This solid-liquid interface heat insulating material 8 is provided with a gap of 3 to 5 cm between the lower end and the molten surface of the silicon melt 2. The upper part surrounds the heat-insulating material 9 and may not be used depending on conditions. In addition, it is also possible to provide a cylindrical cooling device that shields the radiant heat to cool the crystals by injecting cold air 36 °. In addition, as shown in FIG. Magnets 38 formed by superconducting wires 圏 etc., for the silicon melt 2 by applying a horizontal or vertical magnetic field to suppress the convection of the melt, and strive for the stable growth of single crystal, the so-called MCZ method is often used. The direction of the magnetic field applied to the melt can be easily changed depending on the magnet arrangement. For example, when one coil is arranged so as to surround the pull-up chamber 31 in a horizontal direction, a vertical magnetic field (longitudinal magnetic field) is applied to the melt, and two coils are oppositely arranged outside the horizontal direction of the pull-up chamber 31. A horizontal magnetic field (transverse magnetic field) will be applied to the melt. Furthermore, even in the present invention, when the M C Z method is used as described above, the maximum pull-up speed that can be cultivated without deformation of the pull-up crystals becomes a local speed compared with the ordinary CZ method. In addition, even if G is not flat, as long as the minimum 値 of V / G is more than 0.3 mm 2 / κ · m 1 η, even if it is used as the Η of the G distribution, it is only necessary to make the pull-up speed higher. Yes, so the single crystal pull-up device commonly used in Fig. 9 can be used. Regarding the basic structure, although it is the same as the pull-up device of Fig. 7, it is not equipped with the solid-liquid interface heat-insulating material 8 or the upper surrounding heat-insulating material 9. It is also possible to equip the apparatus of Fig. 9 with a magnet and use the M C Z method to pull up the crystal at a high V / G. The single crystal cultivation method using the single crystal pulling device 30 of the above-mentioned FIG. 7 will be described below. First, the high purity polycrystalline silicon is crystallized in the crucible 32. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page)
-14 - 經濟部智慧財產局員工消費合作社印製 575696 A7 B7 五、發明説明（12) 原料加熱至熔點（約1 4 2 0 °c )以上加以熔解。之後，藉 捲出鋼索7在熔液2之表面約略中心部接觸或浸漬種結晶5 先端。其後，將坩堝保持軸3 3向適當方向迴轉，並且，邊 迴轉鋼索7藉拉起捲取種結晶5，就開始單結晶之培養。以 後，藉適當地調節拉起速度與溫度就可得到約略圓柱形狀之 單結晶棒1。 如第7圖在液面之正上方位置設既定間隙配置隔熱材， 藉成爲再在此隔熱材上部裝設冷卻結晶裝置之構造，在結晶 成長界面附近由輻射熱可得到保溫效果，在結晶上部因可遮 蔽來自加熱器等之輻射熱，所以，結晶周邊部之溫度坡度 G e將變小。其結果，在結晶中心部之溫度坡度G c之差値 就消失，可得到扁平溫度坡度G之面內分布。按，作爲結晶 之冷卻裝置，與上述筒狀冷卻裝置3 6之外，也可以裝設圍 繞結晶周圍之空冷導管或水冷蛇管等以確保所需溫度坡度。 茲列舉本發明之實施例與比較例具體地說明本發明，但 是本發明係並非限定於這些者。 (實施例1 ) 使用與第8圖同樣之單結晶拉起裝置，在直徑1 8英吋 C 4 5 0 m m )之石英堪堝喂給既定量之原料多結晶砂與附 氮化膜矽晶圓，拉起（使用M C Z法有施加磁場）結晶方位 (10 0)，導電型？型，氮濃度3乂1013個/(：1113(在 拉起結晶之肩位置之計算値）之矽單結晶塊錠，從此單結晶 塊銳之肩附近切出晶圓，製作了電阻率爲1 〇 Ω · c m而直 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------t衣------、玎~------線 (請先閱讀背面之注意事項再填寫本頁) -15- 575696 A7 B7 五、發明説明（13) 徑爲1 5 0 m m之矽鏡面晶圓。氧濃度爲1 2〜1 5 Ppma (JEIDA) 〇 拉起速度係在1 . 2 m m / m i η與1 . 〇 mm/min之 2條件進行’將結晶拉起中之V / G之結晶徑向之面內分布 表示於第3圖。按，V / G之計算係使用綜合傳熱解析軟體 F E M A G ( F.Duoret,P.Nicodeme,Y.RycKmans. P.Wouters and M.J.Crochet，Int.J.Heat Mass Transfer，33,1849 ( 1990)) 考慮拉起裝置之Η Z進行。 由第3圖就可淸楚，V / G之面內分布係得到均句數値 ，拉起速度爲1 · 0 m m/m i η時，位於約〇 · 3 6 土 0 · 0 1 m m ζ/ Κ · m i η 之範圍，1 · 2 mm/min 時，位 於約 0 . 4 3 土 0 ·〇 1 5 m m 2/ K · m i η 之範圍。 對於所製作之矽晶圓在1 1 2 5 °C形成5 // m之磊晶層 之後，使用K L A Tencol公司製之表面檢查裝置S P - 1 測定了具有尺寸爲0 . 1 1 // m以上之缺陷（L P D )。被 觀察之L P D任何晶圓之情形時都爲數個/晶圓左右，得到 極低之缺陷。 並且，對於這些磊晶晶圓施加8 0 0 °C，4小時+ 1〇0 0 °C，1 6小時之熱處理，使氧澱積物成長爲可檢測 之尺寸之後，使用Bio-Rad公司製〇P P裝置測定了 B M D 密度。將測定結果表示於第4圖。如第4圖所示，所得到之 B M D密度爲面內均勻，並且，都超過5 X 1 〇 8個/ c m : ，曉得了具有充分除氣效果。 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) 、了 線 經濟部智慧財產局員工消費合作社印製 -16- 經濟部智慧財產局負工消費合作社印製 575696 A7 ___B7 五、發明説明（14) (實施例2〜5，比較例1，2 ) 使用Η Z相異之3種單結晶拉起裝置（裝置a (無施加 fe場），裝置B C (施加磁場））拉起6種類之摻雜氮石夕 單結晶（結晶方位〈1 0 0〉，導電型P型），從這些單結 晶塊錠之肩附近切出晶圓，製作了電阻率爲1 〇 Ω . c m而 直徑2 0 〇 m m之矽鏡面晶圓。任一晶圓之氧濃度都位於 1 1 〜1 6 P P m a ( J E I D A )之範圍。 裝置A，B，C之各個結晶拉起時之g之結晶徑向之面 內分布係如第5圖所示，關於裝置A係將拉起速度以3條件 (1 · 3 ，1 . 1 ，1 .〇 m m/m i η )拉起 3 條結晶（ 分別成爲實施例2，實施例5，比較例1 )，關於裝置Β， C係拉起時以結晶不變形之最大速度拉起（分別成爲實施例 3 ，實施例4 )。又，與實施例2其氮濃度爲不同之外以同 一條件拉起者視爲比較例2。將這些6種類之結晶拉起時之 V/G之面內分布表示於第6圖。 並且，於表1彙集表示這些6種類之結晶拉起條件，與 所製作基板及磊晶層之品質之評價結果。各品質之評價手法 雖然與實施例1相同，但是基板之轉位環，係將基板進行二 次蝕刻之後使用光學顯微鏡觀察，磊晶層之S F，係將作爲 L P D被觀察之缺陷使用光學顯微鏡加以觀察所計測者。 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇><297公| ) ---------批衣------1Τ-------線 (請先閲讀背面之注意事項再填寫本頁) -17 - 575696 A7 B7 五、發明説明（15) 經濟部智慧財產局員工消費合作社印製 品質 嘉晶層 j SF [個/晶圓] 摧 進 進 捱 壊 LPD [個/晶圓] <20 <20 <20 <20 100 170 基板 BMD[/cm3] 1 周邊 10mm I 1 5E8 1Ε9 3Ε9 3Ε8 1Ε8 7E8 中心 2E9 4Ε9 2Ε9 9Ε8 5Ε8 3E9 Γ 轉位環 [/cm2] 鹿 捱 壊 壊 周邊3 0 周邊30 拉起條件 V/G ^ 0.3 的比例 [%] 100 100 〇 〇 s V / g [ m m2 / K m i η ] I I i周邊10 mm 1_ ο m Ο ON m ο m 寸 Ο \〇 〇 CO 〇 ο m ο 中央 τ ·Ή 寸 Ο r—Η ο CO 寸 ο 寸 m 〇 m CN ο r—Η 寸 Ο 氮濃度 [/cm3] (肩部） 3Ε13 3Ε 1 3 3Ε13 3E 1 3 3Ε13 2Ε14 Vi g 例 Ν ο . \ 實施例2 實施例3 實施例4 比較例2 (請先閱讀背面之注意事項再填寫本頁)-14-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575696 A7 B7 V. Description of the invention (12) The raw materials are heated to a melting point (approximately 1420 ° c) and melted. Thereafter, the steel wire 7 is rolled out to contact or impregnate the seed crystal 5 at the approximate center portion of the surface of the melt 2. Thereafter, the crucible holding shaft 33 is rotated in an appropriate direction, and the steel wire 7 is pulled up to take up the seed crystal 5 to start the single crystal cultivation. Thereafter, by appropriately adjusting the pull-up speed and temperature, a single-crystal rod 1 having a substantially cylindrical shape can be obtained. As shown in Fig. 7, a predetermined gap is arranged at a position directly above the liquid surface to arrange a heat insulating material. By constructing a cooling crystallization device above the heat insulating material, a heat preservation effect can be obtained by radiant heat near the crystal growth interface. Since the upper portion can shield radiant heat from a heater or the like, the temperature gradient G e of the crystal peripheral portion becomes small. As a result, the difference in the temperature gradient G c at the center of the crystal disappears, and an in-plane distribution of the flat temperature gradient G can be obtained. In addition, as a cooling device for the crystal, in addition to the above-mentioned cylindrical cooling device 36, an air-cooled duct or a water-cooled coiled pipe surrounding the crystal may be installed to ensure a desired temperature gradient. Examples and comparative examples of the present invention will be specifically described below, but the present invention is not limited to these. (Example 1) Using the same single crystal pulling device as in Fig. 8, feed a predetermined amount of raw material polycrystalline sand and silicon nitride film with silicon crystal in a quartz can of 18 inches in diameter (C 4 50 mm). Circle, pull up (with magnetic field applied by MCZ method) crystal orientation (100), conductive type? Silicon monocrystalline ingot with a nitrogen concentration of 3 乂 1013 pcs / (: 1113 (calculated at the position of the shoulder where the crystal is pulled up)), a wafer was cut out from the sharp shoulder of this single crystal block, and the resistivity was 1 〇Ω · cm and the size of the straight paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) --------- t-shirt ------, 玎 ~ ------ line (Please read the precautions on the back before filling this page) -15- 575696 A7 B7 V. Description of the invention (13) Silicon mirror wafer with a diameter of 150 mm. The oxygen concentration is 1 2 ~ 1 5 Ppma (JEIDA) 〇The pull-up speed is performed under the conditions of 1.2 mm / mi η and 1.0 mm / min. The in-plane distribution of the crystal radial direction of V / G during crystal pull-up is shown in Fig. 3. Press, The calculation of V / G is based on the comprehensive heat transfer analysis software FEMAG (F. Duoret, P. Nicodeme, Y. RycKmans. P. Wouters and MJCrochet, Int. J. Heat Mass Transfer, 33, 1849 (1990)). Starting from the device Z. From Figure 3, we can see that the in-plane distribution of V / G is the average sentence number 値, when the pulling speed is 1.0 mm / mi η, it is located at about 0.36 soil 0 · 0 1 mm ζ / Κ · mi η At 1 · 2 mm / min, it is located in the range of about 0.4 3 to 0 · 0 1 5 mm 2 / K · mi η. For the fabricated silicon wafer, 5 // m is formed at 1 1 2 5 ° C After the epitaxial layer was used, a surface inspection device SP-1 manufactured by KLA Tencol Corporation was used to measure defects (LPDs) with a size of 0.1 1 // m or more. The number of cases of any wafers under LPD observed was counted. The number of wafers / wafers is very low, and the epitaxial wafers are heat treated at 800 ° C, 4 hours + 100 0 ° C, and 16 hours, so that the oxygen deposits grow to After the detectable size, the BMD density was measured using a PP-device made by Bio-Rad. The measurement result is shown in Fig. 4. As shown in Fig. 4, the obtained BMD density was uniform in-plane, and all exceeded 5 X 1 08 pieces / cm: I know that it has a sufficient degassing effect. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-16 Printed by the agency 575696 A7 ___B7 V. Description of the invention (14) (Examples 2 to 5, Comparative Examples 1, 2) Using three kinds of single crystal pull-up devices with different ΗZ (device a (no fe field applied), The device BC (applied magnetic field) pulled up 6 kinds of doped nitrogenstone single crystals (crystal orientation <100>, conductive P type), cut out wafers from the shoulders of these single crystal ingots, and produced A silicon mirror wafer with a resistivity of 10 Ω. Cm and a diameter of 200 mm. The oxygen concentration of any wafer is in the range of 1 1 to 16 P P m a (J E I D A). The in-plane distribution of the crystalline radial direction of g when the crystals of each of the devices A, B, and C are pulled up is shown in FIG. 5. Regarding the device A, the pull-up speed is controlled under 3 conditions (1 · 3, 1.1, 1.0 mm / mi η) to pull up three crystals (respectively as Example 2, Example 5, and Comparative Example 1), regarding device B and C, when pulling up, the crystals were pulled up at the maximum speed at which the crystals did not deform (respectively Example 3, Example 4). In addition, it was regarded as Comparative Example 2 except that the nitrogen concentration was different from that of Example 2 under the same conditions. The in-plane distribution of V / G when these six types of crystals are pulled up is shown in FIG. In addition, Table 6 summarizes the evaluation results of the six types of crystal pulling conditions and the quality of the substrate and the epitaxial layer produced. Although the evaluation method of each quality is the same as that in Example 1, the indexing ring of the substrate is observed by using an optical microscope after the substrate is etched twice. The SF of the epitaxial layer is used as the defect of the LPD to be observed using an optical microscope. Observe the person being measured. This paper size is applicable to China National Standard (CNS) Α4 specification (21〇 > < 297) |------ Batch ------ 1T ------- line ( Please read the precautions on the back before filling out this page) -17-575696 A7 B7 V. Description of the invention (15) Printed quality Jiajing layer j SF [piece / wafer] by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs LPD [unit / wafer] < 20 < 20 < 20 < 20 100 170 substrate BMD [/ cm3] 1 periphery 10mm I 1 5E8 1E9 3E9 3Ε8 1E8 7E8 center 2E9 4E9 2E9 9E8 5E8 3E9 Γ index Ring [/ cm2] Deer is surrounded by perimeters 3 0 Perimeters 30 Percentage of pull-up conditions V / G ^ 0.3 [%] 100 100 〇〇s V / g [m m2 / K mi η] II i Perimeter 10 mm 1_ ο m Ο ON m ο m inch 0 \ 〇〇CO 〇ο m ο central τ · Ή inch Ο r—Η ο CO inch ο inch m 〇m CN ο r—Η inch 0 nitrogen concentration [/ cm3] (shoulder) 3Ε13 3Ε 1 3 3Ε13 3E 1 3 3Ε13 2E14 Vi g Example N ο. Example 2 Example 3 Example 4 Comparative Example 2 (Please read the precautions on the back before filling this page)
本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -18- 575696 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（16) 從表1之實施例2〜4之結果，氮濃度爲1 X 1 ο Η 個/ c m 3 ’ V / G爲0 . 3 m m 2 / Κ · m i η以上之領域 在結晶徑向具9 0 %以上時，在基板就觀察不到轉位環，可 將其密度成爲2 0個/ c m 2以下。其結果，顯著地降低所 得到包含磊晶層之S F缺陷（L P D )，曉得可成爲2 0個 /晶圓以下。又，如實施例4 V / G之面內分布若位於This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -18- 575696 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (16) Example 2 from Table 1 ~ As a result of 4, the nitrogen concentration is 1 X 1 / / cm 3 'V / G is 0.3 mm 2 / κ · mi η or more. When the crystalline radial direction is 90% or more, it is not observed on the substrate. When the index ring is used, the density can be reduced to 20 pieces / cm 2 or less. As a result, the S F defect (L P D) including the epitaxial layer was remarkably reduced, and it was found that the number of defects could be less than 20 per wafer. In addition, if the in-plane distribution of V / G in Example 4 is located at
0 . 4 3 5 ± 〇 ·〇 1 5 m m 2 / K · m i η 範圍時 B M D 之面內分布也變成均勻，曉得具有面內均勻之除氣效果。實 施例5係V / G爲〇 · 3 m m 2/ Κ · m i η以上之領域爲 在結晶徑向低於9 0 %時之例，但是於此例，V / G爲只有 屬於0 · 3 m m 2 / Κ · m i η未滿領域之周邊1 〇 m m附 近之B M D密度爲小之點（3 X 1 〇 8個/ c m 3 )與實施例 2〜4比較雖然效果爲壞，但是於製造裝置所要求之b M d 密度之下限只要具3 X 1 0 8個/ c m 3左右時就無問題。亦 即’曉得V / g爲〇 . 3 m m 2 / K · m i η以上之領域即 使不一定爲9 〇 .%以上，配合所要求B M D密度，而磊晶層 之L P D爲能夠變成2 〇個/ 2〇〇m m晶圓（〇 .〇6 4 個/ c m 2)以下控制v / g即可。 另者’比較例1係V / G爲0 · 3 m m 2/ K · m i η 以上之領域爲4 〇 %左右之例，此情形時於V / G爲降低之 周邊部在基板觀察到摻雜氮基板特有之轉位環，其結果變成 磊晶層之L· P D爲增加之結果。同樣，比較例2，係氮濃度 即使變成1 X 1 〇 14個/ c m 3以上時也變成L P D爲多之結 果0 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X 297公釐） 裝 訂 絲 (請先閱讀背面之注意事項再填寫本頁) -19- 575696 A7 ______ B7 五、發明説明（17) (實施例6 ) (請先閱讀背面之注意事項再填寫本頁} 對於與實施例4同一條件所製作之矽鏡面晶圓在乾燥氧 環境中施加1 1 0 0 °C，1 6小時之熱氧化處理之後，進行 選擇蝕刻，使用光學顯微鏡測定0 S F密度。〇S F密度之 測定，係從晶圓外周端以5 m m間隔測定到晶圓中心（第 1 0 圖）。 又，使用從與製作其晶圓之塊錠之同一塊錠之鄰接位置 切出所製作之另外矽鏡面晶圓，與實施例1同樣，製作磊晶 晶圚測定了磊晶層表面之L P D。所觀察到之L P D係5個 /晶圓之極少L P D。並且，將此磊晶晶圓之b M d密度之 面內分布與實施例1同樣方法測定（第1 1圖）。 從第1 0圖及第1 1圖之結果，若依據本發明，變成在 形成磊晶層之矽晶圓中原本存在之〇S F發生之核之氧化澱 積物爲即使使用1 0 0個/ c m 2未滿之少矽晶圓，曉得具 有高密度之B M D，可得到高除氣能力之磊晶晶圓。 經濟部智慧財產局員工消費合作社印製 按，本發明係並非限定於上述實施形態。上述實施形態 爲只不過是例示而已，具有與本發明之申請專利範圍所記載 之技術思想實質上同一構成，可發揮同樣作用效果者，則任 一皆包括於本發明之技術範圍。 圖式之簡單說明 第1圖係表示拉起摻雜2 X 1 0 13個/ c m 3氮之C Ζ法 矽單結晶時之V / G之面內分布之結果圖（拉起速度係成爲 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ~ " ~ -20- 575696 Α7 Β7 五、發明説明（18) 1 · 1 m m / m 1 η 與 1 · 3 m m / m i η )。 第2圖係表示從以第1圖之拉起條件所拉起之單晶矽塊 錠製作矽鏡面晶圓，對此以1 1 2 5 °C形成5 // m之磊晶層 之後，爲了使B M D成長到可檢測之尺寸施加8 0 0 °C，4 小時及1 0 0 0 °C，1 6小時熱處理，使用〇P P裝置測定 面內之B M D密度之結果之結果圖。 第3圖係於實施例1，表示拉起摻雜3 X 1 0 13 個/ c m 3氮之C Ζ法矽單結晶時之V / G之面內分布之結 果圖（拉起速度係成爲1 · 2 m m/m i η與1 · 〇 m m / m i η ) 〇 第4圖係以第3圖之拉起條件所拉起之單晶矽塊錠製作 砂鏡面晶圓，對此以1 1 2 5 °C形成5 // in之晶晶層之後， 爲了使B M D成長到可檢測之尺寸施加8 0 0 t，4小時及 1〇0 0 °C，1 6小時熱處理，使用〇P P裝置測定面內之 B M D密度之結果之結果圖。 第5圖係於單結晶拉起裝置A (實施例2，5，比較例 1 5 2 ) ，B (實施例3 ) ，C (實施例4 )，表示各個結 晶拉起時之G之結晶徑向之面內分布之圖。 第6圖係表示於實施例2〜5，比較例1，2，拉起摻 雜氮之C Z法單晶矽時之V / G之面內分布之圖。 第7圖係本發明所使用之C Z法之單結晶拉起裝置之槪 略說明圖。 第8圖係本發明所使用之M C Z法之單結晶拉起裝置之 槪略說明圖。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 裝-- (請先閱讀背面之注意事項再填寫本頁) 訂 線 經濟部智慧財產局員工消費合作社印製 -21 - 經濟部智慧財產局員工消費合作社印製 575696 A7 B7 五、發明説明（19) 第9圖係本發明所使用之通常單結晶拉起裝置之槪略說 明圖。 第1 0圖係表示於實施例6所製作之矽晶圓之〇S F密 度分布之圖。 第1 1圖係表示於實施例6所製作之磊晶晶圓之 BMD密度之面內分布之圖。 主要元件對照 1 □口 早 結 晶 棒 2 矽 熔 液 5 種 結 晶 6 種 結 晶 夾 具 7 鋼 索 8 固 液 界 面 隔 熱 材 9 上 部 圍 繞 隔 熱 材 3 0 早 結 晶 拉 起 裝 置 31 拉 起 室 32 坩 堝 33 坩 堝 保持 軸 34 加 埶 UU 3 5 隔 埶 •/Μ N、 材 36 冷卻 裝 置 38 磁 鐵 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 裝 訂,—線 (請先閱讀背面之注意事項再填寫本頁) -22-In the range of 0.4 3 5 ± 〇 · 〇 15 m m 2 / K · m i η, the in-plane distribution of B M D also becomes uniform, knowing that it has a uniform in-plane outgassing effect. The area where the V / G is 0.3 mm 2 / κ · mi η or more in Example 5 is an example when the crystal radial direction is less than 90%, but in this example, V / G only belongs to 0.3 mm 2 / κ · mi η The area where the BMD density is less than 10 mm around the periphery of the unfilled area is a small point (3 X 108 pieces / cm 3). Compared with Examples 2 to 4, although the effect is not good, The lower limit of the required b M d density is no problem as long as it has about 3 X 108 / cm3. In other words, even if the area where V / g is 0.3 mm 2 / K · mi η or more is not necessarily 9 0.% or more, the LPD of the epitaxial layer can be changed to 20 / It is sufficient to control v / g below 200mm wafers (0.054 pieces / cm2). Also, 'Comparative Example 1 is an example in which the V / G is about 0.3 mm 2 / K · mi η or more is about 40%. In this case, doping is observed on the substrate at a peripheral portion where V / G is reduced. The index ring unique to the nitrogen substrate results in an increase in the L · PD of the epitaxial layer. Similarly, in Comparative Example 2, even if the concentration of nitrogen in the system becomes 1 X 1 〇14 counts / cm 3 or more, the result is too much LPD. 0 This paper size applies the Chinese National Standard (CNS) A4 standard (21 0X 297 mm). Binding wire (Please read the precautions on the back before filling this page) -19- 575696 A7 ______ B7 V. Description of the invention (17) (Example 6) (Please read the precautions on the back before filling out this page) Example 4: A silicon mirror wafer fabricated under the same conditions was subjected to a thermal oxidation treatment at 110 ° C for 16 hours in a dry oxygen environment, and then subjected to selective etching to measure a 0 SF density using an optical microscope. It is measured from the outer periphery of the wafer at a 5 mm interval to the center of the wafer (Figure 10). Another silicon mirror crystal produced by cutting from the adjacent position of the same ingot as the ingot from which the wafer was made is used. In the same manner as in Example 1, an epitaxial wafer was fabricated, and the LPD on the surface of the epitaxial layer was measured. The observed LPD was 5 pieces / wafer with very low LPD. Moreover, the b M d density of the epitaxial wafer was measured. The in-plane distribution was measured in the same manner as in Example 1. (Fig. 11). From the results of Figs. 10 and 11, according to the present invention, the oxidized deposits of 0SF generated in the silicon wafers that originally existed in the silicon wafer forming the epitaxial layer are even Using less than 100 wafers per cm 2, we know that BMD with high density can obtain epitaxial wafers with high outgassing capacity. Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. It is not limited to the above-mentioned embodiment. The above-mentioned embodiment is merely an example, and has substantially the same structure as the technical idea described in the scope of patent application of the present invention, and can exert the same effect, any of which is included in the present invention The technical scope of the diagram. Brief description of the diagram. Figure 1 shows the results of the in-plane distribution of V / G when pulling up the C Zn silicon single crystal doped with 2 X 1 0 13 / cm 3 nitrogen (pull up Speed becomes the standard of this paper. Applicable to China National Standard (CNS) A4 specification (210X 297 mm) ~ " ~ -20- 575696 Α7 Β7 V. Description of the invention (18) 1 · 1 mm / m 1 η and 1 · 3 mm / mi η). Figure 2 shows the pull from Figure 1 The monocrystalline silicon ingot pulled up under the conditions is used to make a silicon mirror wafer. After this, an epitaxial layer of 5 // m is formed at 1 12 5 ° C, and 80 ° is applied to grow the BMD to a detectable size. C, 4 hours and 1000 ° C, 16 hours heat treatment, the results of measuring the BMD density in the plane using 〇PP device results. FIG. 3 is the result of Example 1 showing the in-plane distribution of V / G when pulling up a C Zn silicon single crystal doped with 3 X 1 0 13 atoms / cm 3 of nitrogen (the pull-up speed becomes 1) · 2 mm / mi η and 1 · 〇mm / mi η) 〇 Figure 4 is a monocrystalline silicon ingot drawn from the pulling conditions shown in Figure 3 to make a sand mirror wafer, 1 1 2 5 After forming a 5 // in crystal layer at ° C, heat treatment was performed for 8 hours, 4 hours and 100 ° C, 16 hours for BMD to grow to a detectable size. Results graph of BMD density results. FIG. 5 shows the single crystal pulling device A (Examples 2, 5, and Comparative Example 15 2), B (Example 3), and C (Example 4), showing the crystal diameter of G when each crystal is pulled A diagram of the distribution inward. Fig. 6 is a graph showing the in-plane distribution of V / G when the CZ method single crystal silicon doped with nitrogen is pulled up in Examples 2 to 5 and Comparative Examples 1 and 2. Fig. 7 is a schematic explanatory diagram of the single crystal pulling device of the CZ method used in the present invention. Fig. 8 is a schematic explanatory diagram of the single crystal pulling device of the MCZ method used in the present invention. This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) Packing-(Please read the precautions on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economy Staff Consumer Cooperatives-21-Economy Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau 575696 A7 B7 V. Description of the invention (19) Figure 9 is a schematic illustration of the usual single crystal pull-up device used in the present invention. Fig. 10 is a graph showing the FS density distribution of the silicon wafer prepared in Example 6. FIG. 11 is a diagram showing the in-plane distribution of the BMD density of the epitaxial wafer manufactured in Example 6. FIG. Comparison of main components 1 □ Early crystallizing rod 2 Silicon melt 5 crystals 6 crystal fixtures 7 Steel cable 8 Solid-liquid interface heat insulation material 9 Surrounding heat insulation material 3 0 Early crystal pulling device 31 Pulling chamber 32 Crucible 33 Crucible Holding shaft 34 plus UU 3 5 spacers / M N, material 36 cooling device 38 magnet This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) binding, line (please read the note on the back first) (Fill in this page again) -22-