1276161 玖、發明說明 月/兒月應敘明·舍明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說 本發明概括言之係關於半導體材料基板之配製，特別是 、製远電子組件之矽晶圓為然。質言之，本發明乃關於 、種石夕處理過私’其於實質上任何電子裝置製程之熱處理 月間使曰曰圓形成氧析出物之理想不均勻深度分佈。 製造半導體電子組件大半過程之起始材料的單晶矽通常 :所謂之"切克勞斯基”(czochralski)法配置，其中將單籽晶 士熔夕Θ 後以緩慢萃取法而生成。在熔矽盛於坩堝 、/=’即與各種雜質混合’主要與氧混合。氧在熔晶體之 -又上進入晶格，直到達到由晶中炼體溫度上氧之溶度以 ΐ由固化石夕中氧的實際分凝係數所決定之濃度為止。此等 展度大於氧在固體石夕中於電子裂置製程之標準溫度上的溶 度Ό曰自溶體生成並冷卻時’其中氧的溶解度即迅速降 低：攸而合成片或晶圓中’氧呈超飽和濃度。 ^電子衣置通中所抹之熱處理週期能導致石夕晶圓中氧 超飽和。析出物的有害或有益端視其在晶圓 ::位置而疋。氧析出物位於晶圓之有源裝置區中有損於 :接：㈣、:而位於晶圓主體中之氧析出物卻能捕捉與晶 :之無盈的金屬雜質。利用晶圓主體中氧析出物以捕 捉至屬通常稱為内部或内在吸收雜質QG)。 二：電:裝置製程含有一系列步驟，設計以生產之秒， 曰二之近表面之區並無氧析出物(一般稱為裸露區 )’晶圓其餘主體含充分氧析出物以供内在吸收雜質 82769-950127.doc 1276161 (2)1276161 玖, invention description month/child month should be clarified · semming belongs to the technical field, prior art, content, implementation and schema. The general description of the invention relates to the preparation of semiconductor material substrates, especially, far-reaching The silicon wafer of electronic components is the same. In summary, the present invention relates to the ideal non-uniform depth distribution of oxygen precipitates formed by the rounding process during the heat treatment of virtually any electronic device process. Single crystal germanium, which is the starting material for the majority of semiconductor electronic components, is usually prepared by the so-called "czochralski" method, in which a single seed crystal is formed by a slow extraction method. The smelting is contained in 坩埚, /= 'that is mixed with various impurities' is mainly mixed with oxygen. Oxygen enters the crystal lattice in the molten crystal until it reaches the solubility of oxygen at the temperature of the refining body in the crystal to obtain the solidified stone. The concentration determined by the actual segregation coefficient of oxygen in the evening is greater than the solubility of oxygen in the solid stone at the standard temperature of the electron cleavage process. When the autolysis solution is formed and cooled, 'the oxygen The solubility is rapidly reduced: 攸 and the oxygen in the synthetic sheet or wafer is supersaturated. ^The heat treatment cycle in the electronic coating can cause oxygen supersaturation in the stone wafer. The harmful or beneficial end of the precipitate It is located at the wafer:: position. The oxygen precipitates are located in the active device region of the wafer, which is detrimental to: (4), and the oxygen precipitates in the wafer body can capture and crystallize: Metal impurities. Use oxygen precipitates from the wafer body to capture The genus is usually called internal or internal absorbing impurity QG). 2: Electricity: The process of the device contains a series of steps designed to produce seconds, and there is no oxygen precipitate (generally called bare zone) in the vicinity of the surface of the 曰2' The remaining body of the wafer contains sufficient oxygen precipitates for internal absorption of impurities 82769-950127.doc 1276161 (2)
之用。裸露區可以高-低-高熱次序形成，諸如··⑷於高溫 下（攝氏一千一百度以上）惰性環境中氧外擴散熱處理至少 四小時；（b)於低溫下（攝氏六百度至七百五十度）氧析出核 形成；及（c)在高溫下（攝氏一千度至一千一百五十度）氧 (Si〇2)析出物之生成。請參閱1989年加州聖地亞哥AcademicUse. The exposed area can be formed in a high-low-high heat order, such as (4) at least 40 hours in an inert environment at a high temperature (one thousand and one hundred degrees Celsius) in an inert environment; (b) at a low temperature (six degrees to seven hundred degrees Celsius) Fifty degrees) oxygen evolution nucleation; and (c) formation of oxygen (Si〇2) precipitates at high temperatures (from one thousand to one hundred and fifty degrees Celsius). See 1989 San Diego, California
Press公司之F· Shimura君所著，，半導體矽晶技術"第361-367頁 以及其中所列之參考資料。 不過最近之先進電子裝置如動態隨機存取記憶器之製程 已開始盡量減少採鬲溫法步驟。雖然若干製程保留足夠的 高溫法步驟以生產裸露區及大批析出物之充分密度，但材 料的容限過嚴而無法提供商用產品。其它現行高度先進電 子裝置製程皆不含外擴散步驟。由於有源裝置區中氧析出 物的相關問題，故此等電子裝置製造商必須採用在其製程 條件下，晶圓中任何處皆無形成氧析出物之矽晶圓。結果 一切内在吸收雜質之潛在能力於焉喪失。 發明内容 故在本發明之諸目的中乃提供一種單晶矽晶圓，其於任 何實質上電子裝置製程之熱處理週期 物之理想不均勻深度的分佈；提供此種晶圓會優 製地形分深度之裸露區及晶圓^内充分密度之氧析 出物；提供此種之晶圓，其中裸露區之形成及晶圓體中氧 析出物之形成皆與此晶圓區中氧濃度之差異無m;提供此 種晶圓，纟中合成裸露區之厚度實質上與積體電路製程的 細節無關；提供此種之晶圓’其中晶目主體中裸露區及氧 析出物之形成不受切克勞斯基生成單晶秒錠之敎過程盥氧 82769-950127.doc (3) 1276161 的t響，晶因係自該…鍵切割出者; =2中裸露區之形成並不依氧之外擴散Ml ， ;:t法’其"乃以充分漢度之氮及/或碳摻雜，以释定 虱析出物成核中心，使之能承受後續 ^ 妨礙裸露區的形成。 熱處理而不會 簡言之，本發明係針對具有兩主要之 晶矽晶圓，其中之一為曰圓之二主 致千仃表面之早 面H sa®^表面另—為晶圓之後表 表面之周緣，-表面層包括前表面與自=二；合前後 所測量之至少約十微米距剛 :至：二：面i 括中央平面與maSB__ Λ及—主體層包 中心之濃产大於饰’即以主體層中氧析出物成核 之痕度大於表面層中氧析出物成核中 析出物成核中心具有一濃度截辰度以乳 中心之峯值密度在中央平面 1 、”中乳析出物成核 度位置循晶圓前# 、 处5 /、附近，而濃度自峯值密- 1偈日日«月丨J表面方向降低。 曰 碳或其混合物詛人之狹她仏 日日® S有選自氮、· 約在每立方公分= 採用氮播雜物時，氮之濃度 在每立方公分i 1016至約5x1014原子之間，而碳的濃度約· 万A刀^〇16至約4χ1〇17原子之間。 本發明並針斜_括& 圓的方法。此方法控制之氧析出作用之單晶石夕晶 旋所切割且含2声括選定自切克勞斯基法生成之單晶石夕 之曰圓 Β引、面和後表面及前後表面間一中央平面 爻日日0，此晶圓並含一 r天十面 表面層涵蓋前I 乂 g、一主體層及摻雜物；前 ，，兩者間的表二與自前表面至中央平面間w 門的-固區；主體層涵蓋中央平面與前表面層間的· 82769-950127.doc (4) 1276161 晶圓區域；而換雜物 〆 時，其濃度約為每立方公的组合;當摻雜物為氮 雜物為碳時，J1濃产約刀—X至約5x1014原子，而若摻 子。所、$ > ，、又、，、勺為母立方公分1x10丨6至約4x101、 ♦:選…圓加熱至約攝氏一千一 =主體層中形成晶格空位。經加熱之晶圓迅速冷卻： 成晶圓中空位濃度截面曲 、迷7 P形 中m发括6 奪值空位密度在主體層 Μ ^ ^ , 依日日0表面方向大致遞減，且前 表面層與主體層中空位、、麄 析出物忐仿由 /又差”使前表面層中並不形成氧 啊出物成核中心，氧柝屮 曰认 析出物成核中心於主體層中形成。而 於加熱之晶圓冷卻時，夺空中 片 φ ^ ^ ^ %疋之虱析出物成核中心即於 主體層中形成，主體層φ * 士 ^疋之乳析出物成核中心的濃度 主要依空位的濃度而定。 本發明之其它目的與特徵將明示於下文中。 方式 又據本U業已發現_種理想的沈積晶圓，其於實際 土任何電子裝置製程期間，會形成充分深度之裸露區及含 内在吸收雜質用之充分密度氧析出物的晶圓主體。此一 理想之沈積晶圓之優點在於可利料導體”造業通用工 具在片刻間配製之。此法創建一種矽模板，確定或"印製" 於電子裝置製程期間氧析出之方式。 本發明理想沈積晶圓之原始材料乃屬依照傳統性切克勞 斯基晶體生成法所生成之單晶錠中所切割之單晶石夕晶圓。 此等方法以及標準石夕的切片’研磨，姓刻和拋光等技術載 於1989年—c Press中F· Shi_所著之，，半導體石夕晶體技 術”及1982年紐約SPdnger_Verlag中"石夕化學姓刻"(j. 82769-950127.doc (5) (5)1276161 ed·)，錄於此以供參考。 切克勞斯基法生成之石夕通常所含氧濃度在約每立方公分 5xl〇17至約9xl017原子的範圍内（ASTM標準！^_121_83)。由於氧 析出作用實質上呈現自理想沈積晶圓中氧濃度的退耦性， 故原始晶圓可具有切克勞斯基法所獲範圍以内或以外之氧 濃度。 依據單晶矽錠自矽熔點（約攝氏1410度）經攝氏約七百五 十度至約三百五十度範圍之冷卻速率，氧析出物成核中心 y形成於晶圓所切割之單晶矽錠中。原始材料中是否有此 等成核中心存在對本發明無關緊要，但此等中心卻能由在 約攝氏-千三百度以内溫度矽熱處理所分解情形。某些埶 處理，諸如石夕於約攝氏八百度退火四小時等，能穩定此等 中心使之不能在未超過約攝氏一千一百五十度下分解。氧 析出物的探測極限目前約為每立方公分5χΐ〇6析出物。氧析 :物成核中〜的存在(或密度尚無法利用現有技術直接測 量。但可用各種技術間接探測其存在。如前所述，石夕中先 :在之氧析出物成核中心可由將矽經氧析出熱處理而獲穩 定，且可在此等位置生成析出物。故此等成核中心可於氧 析出熱處理後間接測得，例如將晶κ於攝氏人百度退火四 小時’然後於攝氏一千度退火十六小時之熱處理。 現在請參考圖卜本發明理想沈積晶圓的原始材料單晶石夕 曰曰圓n别表面3，後表面5及—前與後表面間假想之中 央平面7。本文中”前”與”後”詞語乃用以區別晶圓之兩主要 大致同平表面，所採用之晶圓前表面一詞並非一定指而後 %子衣置裝於其上之表面，而所採晶圓後表面一詞亦非指 82769-950127.doc (6) (6)!276161 晶圓之與電子震置所在表面相對的主… :晶圓通常有些總厚度變化如突出 '，故卜面由於 平面:;2面上的每一點間的中點可能不在同-準確的 言，諸中：了際上’背曲之總厚度變化通常極微，近似而 表面間居於假想之中央平面内，該平面約為前後 氧之ί ::方法的第一具體實例中，晶圓1於步驟Sl中在含 一衣=做熱處理，以生成包圍晶圓1之外表氧化層9。 埃、又IV氧化層厚度大於矽上形成之原生氧化層(約為15 至小3么氧化層至少厚約二十埃為宜，而在某些具體實例中 二厚、力一十五埃或甚至約三十埃。目前所獲之實驗證據 不大於約三十埃之氧化層，雖不干擾所要求效應，也並 不會提供附力σ益處。 7在步驟S2中，晶圓承受熱處理，其中晶圓加熱至高溫以 幵=成曰曰圓1中晶格空位13並增加空位數密度。此一熱處理步 騄且於速熱退火器中實施，將晶圓加熱至目標溫度並於該 酿度上做較短時間之退火。一般而言，晶圓承受之溫度至 J超過攝氏一千一百五十度，較宜至少一千一百七十五 度，更佳至少約一千二百度，及更佳之一千二百度至一千 二百七十五度之間。 在本舍明苐一具體實例中，速熱退火步驟在氮化環境中 實施’亦即含氮氣體N2或含氮之氨等化合物使暴露之石夕表 面氮化者。故該環境可僅含氮或氮化合氣體，或另含如氬 之非氮化氣體。達成增加全晶圓中空位濃度泰半有賴達成 退火溫度。晶圓通常維持於此一溫度至少一秒，數秒（至少 82769-950127.doc -11 -Press, F. Shimura, Press, Semiconductor Crystal Technology, pp. 361-367 and references listed therein. However, recent processes for advanced electronic devices such as dynamic random access memory have begun to minimize the steps of the picking process. While several processes retain sufficient high temperature process steps to produce a sufficient density of exposed areas and bulk precipitates, the material tolerance is too tight to provide commercial products. Other current highly advanced electronic device processes do not contain an external diffusion step. Due to the problems associated with oxygenate in the active device region, such electronic device manufacturers must use a silicon wafer that does not form oxygen precipitates anywhere in the wafer under the process conditions. The result is the potential loss of all intrinsic absorption of impurities. SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a single crystal germanium wafer having a desired uneven depth distribution of heat treatment cycles of any substantially electronic device process; a sufficient density of oxygen precipitates in the exposed area and the wafer; providing such a wafer in which the formation of the exposed regions and the formation of oxygen precipitates in the wafer are different from the oxygen concentration in the wafer region. Providing such a wafer, the thickness of the synthetic bare region in the crucible is substantially independent of the details of the integrated circuit process; providing such a wafer in which the exposed portion of the crystal body and the formation of oxygen precipitates are not subject to Cekla The process of generating a single crystal second ingot is 盥 oxygen 82769-950127.doc (3) The t-ring of 1276161, the crystal factor is cut from the ... bond; the formation of the bare zone in =2 does not diffuse according to oxygen. , ;: t method 'its " is fully doped with nitrogen and / or carbon, in order to release the nucleation center of the cesium precipitate, so that it can withstand the subsequent ^ hinder the formation of the exposed area. Heat treatment, but in a nutshell, the present invention is directed to wafers having two main wafers, one of which is the first surface of the two-dimensional surface of the dome, the surface of the surface, and the surface of the wafer. The periphery, the surface layer includes the front surface and the self = two; at least about ten micrometers measured before and after the combination: just: two: face i including the central plane and maSB__ Λ and - the main layer of the package center is greater than the decoration ' That is, the nucleation of oxygen precipitates in the main layer is greater than the nucleation center of the precipitates in the nucleation of oxygen precipitates in the surface layer has a concentration cutoff at the peak density of the milk center in the central plane 1 , "milk precipitates" The nucleation position follows the front of the wafer #, at 5 /, near, and the concentration decreases from the peak density - 1 偈 day « month 丨 J surface direction. 曰 carbon or its mixture 诅 之 仏 仏 ® ® ® ® 有It is selected from nitrogen, · about every cubic centimeter = nitrogen is used, the concentration of nitrogen is between i 1016 and about 5x1014 atoms per cubic centimeter, and the concentration of carbon is about 10,000 A 〇 16 to about 4 χ 1 〇 Between 17 atoms. The present invention is also a method of slanting & circle. This method controls the oxygen evolution The single crystal stone of the action is cut and contains 2 sounds selected from the Czochralski method. The single crystal stone is formed by the Β 、, the surface and the back surface and a central plane between the front and back surfaces. The wafer includes a r-day ten-face surface layer covering the front I 乂 g, a body layer and a dopant; before, between the two, and the solid-state region from the front surface to the central plane; The main layer covers the area between the central plane and the front surface layer, and the concentration is about a combination per cubic centimeter; when the dopant is a nitrogen impurity, In the case of carbon, J1 is rich in about knives - X to about 5 x 1014 atoms, and if the bristles, $ > , , and , , scoops are from the parent cube centimeter 1x10 丨 6 to about 4 x 101, ♦: About one thousand one Celsius = the formation of lattice vacancies in the main layer. The heated wafer is rapidly cooled: the wafer has a hollow concentration cross section, and the 7 P shape contains 6 vacancy vacancy density in the bulk layer Μ ^ ^ , in the surface direction of day 0, the surface direction is approximately decreasing, and the front surface layer and the main layer are hollow, and the precipitates are imitation/difference" to make the front surface Does not form an oxide nucleation centers ah, Che watchman said oxygen precipitate nucleation centers recognize formed in the body layer. When the heated wafer is cooled, the nucleation center of the precipitate φ ^ ^ ^ % 夺 is formed in the main layer, and the concentration of the nucleation center of the main layer φ * 士 疋 乳 is mainly based on The concentration of the vacancy depends. Other objects and features of the present invention will be apparent from the following. Means, according to the U.S., it has been found that an ideal deposited wafer, during the process of any electronic device in the actual soil, forms a substantially deep exposed region and a wafer body containing a sufficient density of oxygen precipitates for the internal absorption of impurities. The advantage of this ideal deposited wafer is that it can be formulated in a momentary manner. This method creates a ruthenium template that determines or "prints" the way oxygen is deposited during electronic device processing. The original material of the ideal deposition wafer of the present invention is a single crystal silicon wafer cut in a single crystal ingot generated by the conventional Czochralski crystal generation method. These methods and the standard Shi Xi's slice 'grinding Techniques such as surname engraving and polishing were published in 1989-C Press, F. Shi_, "Shenzhen Crystal Technology" and 1982 New York SPdnger_Verlag "Shi Xi Chemical Surname" (j. 82769- 950127.doc (5) (5) 1276161 ed·), for reference. The Czochralski method generally produces a concentration of oxygen in the range of about 5 x 1 〇 17 to about 9 x 017 atoms per cubic centimeter (ASTM standard! ^_121_83). Since the oxygen evolution substantially exhibits a decoupling of the oxygen concentration from the ideal deposited wafer, the original wafer may have an oxygen concentration within or outside the range obtained by the Czochralski method. According to the cooling rate of the single crystal germanium ingot from the melting point of the crucible (about 1410 degrees Celsius) in the range of about 750 degrees Celsius to about 350 degrees Celsius, the nucleation center y of the oxygen precipitate is formed on the single crystal cut by the wafer. In the ingots. Whether or not such nucleation centers are present in the original material is not critical to the present invention, but such centers can be decomposed by heat treatment at temperatures in the range of about -10 mils. Some 埶 treatments, such as Shi Xi, which is annealed for about four hours in about eight degrees Celsius, can stabilize these centers so that they cannot be decomposed at less than about 1,150 degrees Celsius. The detection limit of oxygen precipitates is currently about 5.6 precipitates per cubic centimeter. Oxygenation: The presence of ~ in the nucleation of the material (or the density cannot be directly measured by the prior art. However, it can be indirectly detected by various techniques. As mentioned above, Shi Xizhong first: in the nucleation center of the oxygen precipitate can be The ruthenium is stabilized by the oxygenation heat treatment, and precipitates can be formed at such positions. Therefore, the nucleation centers can be indirectly measured after the oxygen evolution heat treatment, for example, the crystal κ is annealed in Celsius Baidu for four hours and then in Celsius. Annealing for a period of sixteen thousand degrees. Now refer to the original material of the ideal deposited wafer of the present invention. The single crystal 3, the back surface 5 and the imaginary central plane 7 between the front and back surfaces. The terms “before” and “after” are used to distinguish the two main substantially flat surfaces of a wafer. The term “front surface of the wafer” does not necessarily refer to the surface on which the sub-coat is placed. The term "post surface of the wafer" is not used to refer to 82769-950127.doc (6) (6)! 276161 The main surface of the wafer opposite to the surface on which the electron is placed is located: the wafer usually has some total thickness variation as prominent, so Bu surface due to plane:; every 2 faces The midpoint between the points may not be the same - the exact word, in the middle: the total thickness of the 'back bend' is usually very small, similar to the surface between the imaginary central plane, the plane is about before and after oxygen :: In a first specific example of the method, the wafer 1 is subjected to heat treatment in step S1 to form a surface oxide layer 9 surrounding the wafer 1. The thickness of the oxide layer is greater than that of the native oxide layer formed on the wafer. (About 15 to 3, the oxide layer is at least about 20 angstroms thick, and in some specific examples, it is 2 thick, 15 angstroms or even about 30 angstroms. The experimental evidence obtained is currently no more than about The 30 angstrom oxide layer does not interfere with the required effect, and does not provide the attached σ benefit. 7 In step S2, the wafer is subjected to heat treatment, in which the wafer is heated to a high temperature to 曰曰=曰曰曰曰1 The lattice vacancy 13 increases the vacancy density. This heat treatment step is performed in a rapid thermal anneal to heat the wafer to the target temperature and anneal for a shorter time on the sinter. Generally, the wafer Withstand the temperature to J more than one hundred and fifty degrees Celsius, it is better to Less than 1,175 degrees, better than at least 1,200 Baidu, and better one of the two thousand two to one hundred and two hundred and seventy-five degrees. In this specific example, the rapid heat The annealing step is carried out in a nitriding environment, that is, a compound containing nitrogen gas N2 or nitrogen-containing ammonia to nitride the surface of the exposed stone. Therefore, the environment may contain only nitrogen or a nitrogen gas, or another atom such as argon. Non-nitriding gas. Achieving an increase in the full-wafer hollow concentration depends on the annealing temperature. The wafer is usually maintained at this temperature for at least one second, a few seconds (at least 82769-950127.doc -11 -
三秒），較佳數十秒（二十，三十，四十，或五十秒），或依 所要之晶圓特性而達約六十秒（其接近商用速熱退火器之 1276161 極限）。如此產生之晶圓即具有相當均勻空位濃度（數字密 度）的斷面曲線。 根據目前所獲之實驗證據，速熱退火步驟中之環境最好 少含部分氧，水蒸汽及其它氧化氣體之壓力，亦即，環境 無氧化氣體或此等氣體之壓力，即不足以注入抑制空位濃 度集結之石夕自填空位原子。雖然氧化氣體濃度的下限尚未 確切決定’但已顯示（0·01)大氣壓之氧的分壓力或百萬分之 一萬份原子（ppma)並不增加空位濃度且無任何效應。因此， 該壤境所含氧或其它氧化氣體之壓力宜小於（〇 〇1)大氣壓 (10,000 PPma)，最好不大於約〇·〇〇5大氣壓（5,〇〇〇ppma)，而在 約0.002或約0·〇〇ι大氣壓（2,〇〇〇或^麵ppma)則更佳。 速熱退火步驟除形成晶格空位外，尚導致矽原材中不穩 定之氧析出物成核中心分解。此等成核中心會於切割晶圓 之單晶石夕旋生成期間形成，或由於晶圓或矽錠以前熱經歷 之其它場合中形成。故衹要此等中心能在速熱退火步驟期 間分解，其是否存在於原始材料中即無關緊要。 速熱退火可於任何商用速熱退火爐中實施，其中諸晶圓 由同功率燈排而個別加熱。速熱退火爐能將矽晶圓迅速加 熱’例如在數秒鐘内將晶圓自室溫加熱至攝氏一千二百 度。此等商用速熱退火爐之一為61〇型爐，由AG Ass〇咖叫加 州山景市）產製。 内在點缺陷（空位及矽自填空位）能經由單晶矽擴散，擴 散速度依溫度而定。故内在點缺陷為内在缺陷擴散率的函 82769-950127.doc -12- ⑻ 1276161 數，且重結合率為溫度的函數。例如，内在點、於晶圓 速熱退火步驟中退火溫度附近移動，而其於攝氏七百度上 在任何商界實用時段大致不移動。目前所獲之實驗證據顯 不在攝氏七百度以下溫度，空位之有效擴散大為減緩，且 即使温度高至攝氏八百纟，九百度或—千度時，亦認為空 位於任何商界實用時段不會移動。 完成步驟从，晶圓在步驟S3中自晶格空位於單晶石夕内相 對移動之溫度範圍迅速冷卻。在晶圓溫度經此溫度範圍下 降時’空位擴散至氧化層9而趨於澄滅，從而導致空位濃度 斷面中之變化，變化程度依晶圓在範圍内該溫度下之時長 而定。如果晶圓處於此範圍内該溫度下無限長時間時，晶 圓主體^中空位濃度會再度呈大致均句，濃度大致小於剛 完成熱處理步驟時晶格空位濃度之均衡值。不過，由於晶 圓迅速冷卻，可達成晶格空位分佈不均勻。最高空位濃度 在中央平面7附近，而空格濃度循前表面3及後表面5方向^ 減《—般而言，在此溫度範圍内之平均冷卻速度至少約為 每秒攝氏五度，而以每秒至少約二十度為宜。依據裸露區 的深度，平均冷卻率宜為每秒至少約攝氏五十度，最好每 秒至少約一百度，就現行若干應用而言，以每秒約攝氏一 百度至二百度為最宜。一旦晶圓冷卻至晶格空位於單晶矽 中相對移動之溫度範圍以外時，則冷卻速度不太影響晶圓 之沈積特性，從而不呈極端重要。就方便言之’冷卻步驟 可與加熱步驟在同一環境中實施。 在步驟S4中，晶圓承受氧析出熱處理。例如，晶圓可在 攝氏八百度下退火四小時，然後在攝氏一千度下退火十六 82769-950127.doc -13- (9) 1276161 小時。另外亦宜將晶圓置約摄“百声瞻 置製程的第一步驟。心攝氏八百度爐内，做為電子袭 ^ 田置入此溫度之爐内時，弈又、古也 火之晶圓會有不同氧析出則速熱退 ^ 下用之刀隔區。在空位區域 主體)中’於晶圓置人爐内後，氧即快速結集。战(曰曰固 溫ΐ時，結集過程結束且達到結集之分佈，端賴空：負载 始浪度而定。在低空位區域（晶圓表面附 初 一如正常之欠缺先存在之氧日日回作用 結集並不顯著。當達到据 w，亦即氧 作定十 攝氏八百度以上時，或若溫度唯捭 卜旦疋，則畐於空位區中之姓 又、准持 ^ , ΘΙ σ木生成析出物而耗盡，而* # 貝中則無任何作用。將晶圓分成各空位 工 效創建一種模板，由 £，即可有 如圖1所示，晶圓中氣：：圓置入爐内所定之氧圖案。 出物材料清除區(裸露區)(15，15,)，自：由無氧析 分別延伸至深产丨 、及後表面5 τ王冰度（t，t )予以特性化。在| 15，）兩者間之區域17含 ;：、乳析出物區（15， 巴⑴… 度大致均勻之氧析出物。 =中氧析出物的濃度主要為加 為冷部率的函數。總之，氧析出物 欠要 上升與退火時間遞增，而以„般所 ；；=中溫度 斫出物乾圍之析出物的密度為準據。 主 無氧析出物材料（裸露區）（15，15，）之 深度（t，t’）主要為θ故办 自則轉後表面的 主要為晶格空位在矽中相對 的 邠率的函數。一妒山夕一命， 動之，皿度乾圍内冷 叙a之，珠度（t，f)隨冷 而以所獲裸露區深度至少約10,2。，羊咸低而遞增， 微米為準。顯妙、 5〇，7〇或一百 ㈣顯然，裸露區的深度大體上百 闕，且亦盥值從垂扣 /、电子衣置製程盔 傳統實用之氧的外擴散無關。 ’，，、 82769-950127.doc -14- (10) (10)1276161 小11明方法中所採速熱處理固會導致自晶圓之前：表面 少量氧：外擴散’但外擴散的量遠少於傳統之裸露區形成 法2之s。如此，本發明之理想沈積晶圓具有相當均勻之 填空位氧濃度’為自矽表面距離之函數。例如，在氧析出 ’、、、 之引曰曰圓會具有自晶圓中心至矽表面約十五微米 内晶圓區域之填空位氧的相當均勻濃度，π以自矽中心至 晶圓區域約為矽表面約十微米者較宜，甚且最好自石夕中心 至晶圓諸區域之約矽表面的約五微米，且以自矽中心至晶 圓诸區域約及三料·丰Iy土 i ~ 更佳。本文中之相當均勻氧濃度係 乳浪度變化不《過約百分之五+，最好不超過百分之二 十，且以不超過百分之十者更宜。 乳析出熱處理通常不會造成大量氧自熱處理之晶圓中向 ^ 口此裸路區中自晶圓表面數微米距離之填空位 乳之濃度不會由於沈積處理而有顯著改變。例如，如果裸 露:包括石夕表面與自前表面至中央平面所測得之距離 π 乂為約十微米）兩者間之晶圓區域時，則自矽表面等 於”D”的一半距離處之裸露區内位置上的氧濃度 ?為裸露區中任何處填空氧漢度的百分之七十五。就若干 氧析出熱處理而言，此仞罢古 卜 南 此位置之填空位氧濃度會更高而至裸 &任何處攻高氧濃度的至少百分之八十五，％十甚至九 十五。 —在本發明之第二具體實例中，採非氮化環境以代替在第 具，貫例之加熱（熱退火）及冷卻步驟中所採用之氮 它此箄非气朴非产 衣兄匕括虱、乱、氖，碳化物及其 匕此等非乳化非氮化之元素與化合氣體，或此等氣體的混 82769-950127.doc •15- 00 1276161 否物…非氮化環境亦似氮化環境，可含小部分氧壓，亦即 =刀>Ε力小於0.01大氣壓（1〇,〇〇〇卯削），而以小於㈣仍大氣 壓（5,〇〇〇 ppma)為宜，小於 〇 〇〇2 或 〇 〇〇1 大氣壓（2,〇〇〇/ι，_ ppma)更佳〇 在本發明之第三具體實例中，省略去步驟⑻（熱氧化步 驟），故起始晶圓僅具固有氣化層。然而當此一晶圓於氣環 境中退火产時，其效應即異於具有比固有氧化層更厚氧化層 (增大的氧化層）之晶圓於氮令退火時所見者。當含增大氧 化層之晶圓在氮環境中退火時’幾乎在到達退火溫度時， 即完成大致均句之空位濃度增加。此外，空位濃度並不以 -疋退火溫度上退火時的函數方式而呈現顯著增加。不過 :晶圓缺少大於固有之氧化層，且若晶圓之前後表面於氮 合=,1’則所獲得之晶圓’其空位濃度（數量密度）曲線 曰…：之橫切面’亦即’最大濃度在前後表面數微米 w U疋且較小辰度在晶圓全體，最小濃度在晶圓 主體，起始約等於且i龄士各& _ …曰大乳化層晶圓中所獲得之濃度。尤 其缺沙大於固有氣化屏夕Θρ1 虱化層之晶®中，退火時間增加會導致处 位濃度的增加。 j s刀θ V欽工 貫驗證據進一步顯示此種 声大4彳h厗B T不，、大於固有氧化層之晶圓及 立日大乳化層晶圓，兩者作用 或另-氧化气用之差異可由於環境中含分子氧 次另Kbi體而^避免。轉另 固有氣化#之曰m —人 云於不具大於 U有虱化層之曰曰固在含小部 圓作用與具增大氧化声曰圓夕你田^鼠仏中退火時，晶 平續日日圓之作用相同。 理，厚度大於固有氧化屏夕&主p 不拘泥於任何原 屏蔽。故此-氧化Γ 表氧化層用做抑制石夕氮化之 开献故Λ 1化層可能存在 _圓，或於退火步驟 82769-950127.doc -16- 1276161Three seconds), preferably tens of seconds (twenty, thirty, forty, or fifty seconds), or up to about sixty seconds depending on the desired wafer characteristics (which is close to the 1271161 limit of commercial rapid thermal annealing) . The wafer thus produced has a cross-sectional curve with a fairly uniform vacancy concentration (digital density). According to the experimental evidence obtained so far, the environment in the rapid thermal annealing step preferably contains less pressure of partial oxygen, water vapor and other oxidizing gases, that is, the environment is free of oxidizing gas or the pressure of such gases, that is, insufficient for injection suppression. The vacancy concentration is assembled by the stone occlusion self-filling vacancy atom. Although the lower limit of the concentration of the oxidizing gas has not been determined deterministically, it has been shown that the partial pressure of oxygen at atmospheric pressure (ppm) or 10,000 parts per million (ppma) does not increase the vacancy concentration and has no effect. Therefore, the pressure of the oxygen or other oxidizing gas contained in the soil is preferably less than (〇〇1) atmospheric pressure (10,000 PPma), preferably not more than about 〇·〇〇5 atmosphere (5, 〇〇〇ppma), and 0.002 or about 0·〇〇ι atmospheric pressure (2, 〇〇〇 or ^ face ppma) is even better. In addition to the formation of lattice vacancies, the rapid thermal annealing process also leads to the decomposition of the unstable nucleation center of the oxygen precipitate in the bismuth material. Such nucleation centers may be formed during the formation of the monocrystalline swarf of the diced wafer, or in other instances where the wafer or bismuth ingot was previously subjected to thermal experience. Therefore, as long as these centers can be decomposed during the rapid thermal annealing step, it does not matter whether they are present in the original material. The rapid thermal annealing can be carried out in any commercial rapid thermal annealing furnace in which the wafers are individually heated by the same power lamp row. The rapid thermal annealing furnace can rapidly heat the tantalum wafer, for example, heating the wafer from room temperature to 1,200 degrees Celsius in a matter of seconds. One of these commercial rapid thermal annealing furnaces is a 61-inch furnace, which is produced by AG Ass, a coffee shop called Mountain View, Canada. Intrinsic point defects (vacancies and 矽 self-filling vacancies) can diffuse through single crystal germanium, and the diffusion rate depends on the temperature. Therefore, the internal point defect is the internal defect diffusion rate of 82769-950127.doc -12- (8) 1276161, and the recombination rate is a function of temperature. For example, the intrinsic point moves around the annealing temperature in the wafer rapid thermal annealing step, while it does not move at any commercial useful time on seven hundred degrees Celsius. At present, the experimental evidence obtained is not below the temperature of seven hundred degrees Celsius, the effective spread of vacancies is greatly slowed down, and even if the temperature is as high as 800 degrees Celsius, nine Baidu or - thousand degrees, it is considered that it will not be in any commercial time. mobile. The completion step is such that the wafer is rapidly cooled in the temperature range in which the crystal lattice is located in the opposite phase of the single crystal in the step S3. As the wafer temperature drops across this temperature range, the vacancies diffuse into the oxide layer 9 and tend to smear, resulting in a change in the vacancy concentration profile, depending on the length of time the wafer is at that temperature. If the wafer is in this range for an indefinite time at this temperature, the concentration of the hollow body of the crystal body will again be approximately uniform, and the concentration is substantially smaller than the equilibrium value of the lattice vacancy concentration just after the heat treatment step is completed. However, due to the rapid cooling of the crystal circle, uneven distribution of lattice vacancies can be achieved. The highest vacancy concentration is near the central plane 7, and the space concentration is reduced in the direction of the front surface 3 and the rear surface 5. In general, the average cooling rate in this temperature range is at least about five degrees Celsius per second, and each A minimum of about twenty degrees is appropriate. Depending on the depth of the exposed area, the average cooling rate should be at least about 50 degrees Celsius per second, preferably at least about one hundred degrees per second. For some current applications, about one bai to two hundred degrees per second is optimal. Once the wafer is cooled to a temperature outside the relative range of movement of the crystal lattice in the single crystal germanium, the cooling rate does not affect the deposition characteristics of the wafer and is not extremely important. It is convenient to say that the cooling step can be carried out in the same environment as the heating step. In step S4, the wafer is subjected to an oxygen evolution heat treatment. For example, the wafer can be annealed for four hours at eight degrees Celsius and then annealed at 180 degrees Celsius for sixteen 82769-950127.doc -13- (9) 1276161 hours. In addition, it is also advisable to put the wafer in the first step of the “Baishengzhao process.” In the heart of the eight Baidu furnace, as the electronic attack ^ Tian placed in the furnace of this temperature, Yi and Gu also fire crystal The circle will have different oxygen precipitation, and the hot knife will be used to retreat. In the vacant area main body), after the wafer is placed in the furnace, the oxygen is quickly assembled. End and reach the distribution of the knot, depending on the load start wave. In the low vacancy area (the wafer surface is attached to the first day as the normal lack of oxygen first day, the effect of the back is not significant. When the data is reached , that is, when oxygen is set at ten degrees Celsius or more than eight hundred degrees, or if the temperature is only 捭 疋 疋 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , There is no effect in the process. The wafer is divided into various vacancies to create a template, which can be as shown in Figure 1. The gas in the wafer: is placed in the furnace to set the oxygen pattern. Exposed area) (15,15,), from: anaerobic precipitation extended to deep calving, and the back surface 5 τ Wang Bing (t, t) is characterized. The region 17 between the two is contained in the range of |15);:, the precipitate of the milk (15, Ba (1)... the oxygen precipitate is substantially uniform. The concentration of the oxygen precipitate is mainly In order to increase the rate of cold fraction. In short, the oxygen precipitates are rising and the annealing time is increasing, and the density of the precipitates in the middle of the temperature is determined as the standard. The main anaerobic precipitation The depth (t, t') of the material (naked area) (15, 15,) is mainly θ. Therefore, the surface of the material is mainly a function of the relative enthalpy rate of the lattice vacancies in the sputum. One life, the movement, the degree of dryness in the inner circumference of the dish, the degree of pearl (t, f) with the cold and the depth of the bare area obtained is at least about 10, 2. The saltiness of the sheep is low and the increment is micron. Miao, 5〇, 7〇 or 100(4) Obviously, the depth of the exposed area is generally one hundred feet, and it is also worthy of the external diffusion of the traditional practical oxygen from the drapery/electronic dressing helmet. ',,, 82769 -950127.doc -14- (10) (10) 12761161 The method of heat treatment in the small 11 method will lead to the self-wafer: a small amount of oxygen on the surface: external expansion 'But the amount of out-diffusion is much less than that of the conventional bare-area formation method. Thus, the ideal deposited wafer of the present invention has a fairly uniform fill-vacancy oxygen concentration' as a function of the self-tanned surface distance. For example, in oxygen evolution The circle of ',,, and has a fairly uniform concentration of fill-space oxygen in the wafer area from the center of the wafer to the surface of the crucible of about fifteen micrometers. π is about ten from the center of the wafer to the wafer area. Preferably, the micron is preferably about five microns from the center of the stone to the surface of the wafer, and preferably from the center of the crucible to the areas of the wafer and the three materials. The fairly uniform oxygen concentration in this paper is not more than about five percent +, preferably no more than twenty percent, and more preferably no more than ten percent. The emulsion precipitation heat treatment usually does not cause a large amount of oxygen to be filled from the heat-treated wafer to the fill hole in the bare zone from the wafer surface by a distance of a micron distance. The concentration of the milk does not change significantly due to the deposition process. For example, if bare: including a wafer area between the surface of the stone and the distance measured from the front surface to the central plane of π 乂 is about ten micrometers, the bare surface is at half the distance of "D". The oxygen concentration in the area is 75% of the oxygen filling in any part of the bare area. In the case of some oxygen evolution heat treatment, the oxygen concentration in the fill space of this position will be higher to at least 85% of the high oxygen concentration of the naked & anywhere, 10% or even 95%. . - in a second embodiment of the present invention, a non-nitriding environment is used instead of the nitrogen used in the heating, thermal annealing and cooling steps of the first, the example, which is not a non-family虱, chaos, 氖, carbides and their non-emulsified non-nitriding elements and chemical gases, or the mixing of such gases 82769-950127.doc • 15-00 1276161 No matter... non-nitriding environment also like nitrogen The environment may contain a small part of oxygen pressure, that is, = knife > Ε force is less than 0.01 atmosphere (1 〇, boring), and less than (four) still atmospheric pressure (5, 〇〇〇 ppma) is appropriate, less than 〇〇〇2 or 〇〇〇1 atm (2, 〇〇〇/ι, _ ppma) is more preferable. In the third embodiment of the present invention, the step (8) (thermal oxidation step) is omitted, so the starting wafer Only has an inherent gasification layer. However, when the wafer is annealed in a gas atmosphere, the effect is different from that of a wafer having a thicker oxide layer (increased oxide layer) than the intrinsic oxide layer. When the wafer containing the enlarged oxide layer is annealed in a nitrogen atmosphere, the vacancy concentration of the substantially uniform sentence is increased almost when the annealing temperature is reached. In addition, the vacancy concentration does not increase significantly as a function of the annealing at the annealing temperature. However, the wafer lacks more than the inherent oxide layer, and if the front surface of the wafer is nitrided, the wafer obtained by '1' has a vacancy concentration (number density) curve 曰...: cross section 'is also' The maximum concentration is a few micrometers w U 前后 on the front and rear surfaces and the smaller brightness is in the whole wafer, the minimum concentration is in the wafer body, and the initial is about equal to and is obtained in the wafer of the aging layer and the emulsifier layer. concentration. Especially in the crystals of the inherently vaporized screen Θ Θ 1 1 虱 , , , , , , , , , 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The js knife θ V 工 贯 验证 验证 验证 验证 验证 验证 验证 验证 验证 钦 θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ It can be avoided because the environment contains molecular oxygen followed by another Kbi body. Turning to the intrinsic gasification #之曰m - the human cloud is not more than U has a sputum layer of tamping in the small circle and the oxidized sound 曰 你 你 你 田 ^ ^ ^ ^ ^ ^ ^ ^ 退火 退火 退火 退火The role of the Japanese yen is the same. The thickness is greater than the intrinsic oxidation screen & main p does not stick to any original shielding. Therefore, the oxidized ruthenium oxide layer is used to suppress the lithium nitridation. The crystallization layer may exist in the _ circle, or in the annealing step 82769-950127.doc -16- 1276161
期間產生增大氧化層而形成之。 因此’依據本發明，速熱退火步驟期間，大氣環境宜含 至少約0.0001大氣壓（1〇〇 ppma)之分壓力，而以至少約〇 〇〇〇2 大氣壓（200 ppma)則更佳。不過，就前述諸原因言之，氧的 分壓力不宜超過〇·〇1大氣壓（1〇,〇〇〇 ppma)，而以小於〇 〇〇5大 氣壓（5,000 ppma)較好，且0·002或〇 〇〇1大氣壓（2,〇〇〇 ppma/l，000 pprna)者更佳。 在本發明之其它具體實例中，晶圓之前與後表面可暴露 於不同之裱境中，各含一或多種氮化或非氮化氣體。例如， 晶圓之後表面可暴露於氮化環境而前表面暴露於非氮化環 境中。另外，多個（2，3或更多晶圓）可面對面疊置而同時 退火；以此方式退火時，面對面接觸之諸面於退火期間機 ，性地防護環境影響。此外，依據速熱退火期間所採用之 2境及所期晶圓的氧濃度斷面，氧化層可僅於晶圓所欲裸 露區的一面上形成，例如晶圓的前表面（3)(參見圖丨）。 本發明方法所用之原始材料可為一種拋光之矽晶圓，或 屬研磨亚蝕刻之晶圓而未經拋光者。此外，晶圓可具空位 或自填空位點缺陷做為主要内在點缺陷。例如，晶圓可自 中心至邊緣屬空位或自填空位佔冑，或其含有一空位為主 材料之中央核心圍繞以自填空位為主之材料的軸向對稱環 若要將磊晶層澱積於 可於外延附生澱積之前 宜於本發明方法後及外 圓中氧析出物成核中心 理想沈積晶圓上，則本發明之方去 或其後貫施。若在其前實施時，則 延附生澱積前，以熱退火法穩定晶 。不過，熱退火法歷時頗長（在約攝 82769-950127.doc •17- (13) !276161 氏八百度需約 既降低：產量且二？ ’隨之於約攝氏一千度需約十小時)， 之太、、h 令晶圓製造成本大大增高。準此，本發明 / 。於外延附生澱積後實施，但如此仍需另辦處理牛 驟’並增高製造成本。 而另〜處理步 另：:氧析出物成核中心可用矽晶的氮摻雜加以參 =Shlmufa等之應用物理48(3)第以頁⑽6)。 摻雜之晶體的最姑山1 ^ 出核咼達約攝氏一千二百五十度時仍呈 : 乂 發明，矽晶中氮的濃度須嚴加控制以實現釋 :之、^料保持形成裸露區的能力。若氮的濃度太㈣ -於母立方公分1χ1〇12原子K約㈣搬ρρ·)，即無法實現 % 應。另—方面，若氮的濃度太高（高於約每立方公分 + )_·〇2 ppma)，則晶體生成期間所形成之氧析出 、核中心於步驟S2中不會分解。㈤時，若矽晶含太多氮， 7在晶圓中會形成氧化引起累積瑕疵（〇ISF)，其對外延附生 7曰圓的品質有不良影響（參見曰本專利局公告第1999-189493 "夕a曰圓表面上之氧化引起累積瑕疲與其它空位式缺陷 不同，未為外延附生矽層之澱積所掩蓋。〇1卯持續於磊晶 層中生成而導致通常稱為外延附生累積瑕疵之内生成缺 ^外延附生累積瑕疵之最大橫切面寬度，以現有探測極 限之雷射自動觀察裝置測之，其範圍自約〇.米至約職 米以上。故依據本發明，矽晶體宜含之氮摻雜劑原子濃度 約為每立方公分1χ1〇12至5χ1〇14原子（〇1 ppma) 而以約每立方公分1)<1012至lxl〇u原子（約〇 〇〇〇2卯·)更佳。 矽錠可利用數種方法以氮摻雜，例如將氮氣介入生成室 及/或將氮添加至聚合矽熔化物等。加至生成中晶體之氮量 82769-950127.doc -18- (14) 1276161 由添加氮至來八 法。尤制，^^ 梦晶圓二積二氮量迅：決定，例如’於既知直徑之 化物之前％人且:子又之^化物⑽4)層’其於形成石夕熔 公分3.18克 掛銷内者_4)之密度約為每立方 氣：=:明’氧析出物成核中心可用碳以代替氮，或碳 =摻雜以獲穩定。石夕鍵中碳的濃度宜在約 1x10原子（0.2ppma)至約域、子（8ppma)之間。 …、關特疋原理，目前認為氮/碳摻雜；^U P 1 空位的擴散而敎稃定氧析出〃= 夕晶體中 體冷卻昧，二: 尤其，已知當生成中晶 凝~，、Λ位底度相臨界超飽和位準（即在此點上產生 會在約摄Γ 凝聚之空位缺陷或微空白。例如，凝聚 115iMi)5G度發生。晶體冷卻時，由於 只政至诸指，故微空白增λ。雖& :空:在於繼續冷卻時大大減低晶體中之非凝：:::； 在_冷卻時’達到臨界超飽和之第二位準，其中 之自由空位和氧相互作用而形成氧析出核心。就非 ::了雜的晶體而言，臨界超飽和的第二位準乃於晶 體至約攝氏七百度時發生。在氮/碳摻雜之石夕晶中，於 =聚❹期間之空白形成’由於空位擴散率減慢而稍受抑 制。如此即導致在第-凝聚作用後’留存於晶體中之空位 濃度更高。說/碳換雜之石夕中所增加之自由空位滚度亦增高 了晶體超飽和第二位準發生之溫度，例如於約攝氏八百度 至約一千零五十度。在此增高之溫度上’晶體中氧原子更 活躍’更多氧原子與自由空位作用而使氧之析出核;;更趨 82769-950127.doc -19-It is formed by increasing the oxide layer during the period. Thus, in accordance with the present invention, the atmosphere preferably contains a partial pressure of at least about 0.0001 atmospheres (1 〇〇 ppma) during the rapid thermal annealing step, and more preferably at least about 〇 2 atmospheres (200 ppma). However, for the above reasons, the partial pressure of oxygen should not exceed 〇·〇1 atm (1〇, 〇〇〇ppma), and preferably less than 〇〇〇5 atm (5,000 ppma), and 0·002 or 〇〇〇 1 atmosphere (2, 〇〇〇ppma / l, 000 pprna) is better. In other embodiments of the invention, the front and back surfaces of the wafer may be exposed to different environments, each containing one or more nitriding or non-nitriding gases. For example, the surface behind the wafer can be exposed to a nitriding environment while the front surface is exposed to a non-nitriding environment. In addition, a plurality of (2, 3 or more wafers) may be stacked face to face while being annealed; when annealed in this manner, the faces of the face-to-face contacts are mechanically protected from the environment during the annealing. In addition, depending on the oxygen concentration profile of the wafer and the wafer used during the rapid thermal annealing, the oxide layer may be formed only on one side of the exposed area of the wafer, such as the front surface of the wafer (3) (see Figure 丨). The starting material used in the method of the present invention may be a polished tantalum wafer or a micro-etched wafer without polishing. In addition, wafers can have vacancies or self-filling vacancy defects as the main inherent point defects. For example, the wafer may be vacant from the center to the edge of the vacancy or self-filling vacancy, or it may contain a vacancy as the central core of the main material surrounding the axially symmetric ring of the material based on the self-filling vacancy. The present invention can be applied to the wafer which is ideally deposited on the nucleation center of the oxygen precipitate in the outer circle before the epitaxial epitaxial deposition and in the outer circle. If it is carried out before it, the crystal is stabilized by thermal annealing before the deposition. However, the thermal annealing method takes a long time (in about 82,769-950,127.doc •17-(13)!276161, the eight-dollar demand is reduced: the output and the second? 'It takes about ten hours to reach about 1,000 degrees Celsius. ), too, h, so that wafer manufacturing costs are greatly increased. With this in mind, the invention /. It is implemented after epitaxial epitaxy, but it still requires additional processing of the cows and increases manufacturing costs. And another ~ processing step Another:: Oxygen precipitate nucleation center can be doped with the nitrogen doping of the crystal = Shlmufa et al. Applied Physics 48 (3) page (10) 6). The most common crystal of the doped crystal is still about 1:250 degrees Celsius: 乂Invented, the concentration of nitrogen in the twin crystal must be strictly controlled to achieve the release: The ability of the bare area. If the concentration of nitrogen is too (four) - in the mother cubic centimeter 1 χ 1 〇 12 atom K (4) moving ρρ ·), that is, can not achieve % should. On the other hand, if the concentration of nitrogen is too high (above about about cubic centimeters + ) _ 〇 2 ppma), the oxygen formed during the crystal formation precipitates and the core center does not decompose in step S2. (5) If the twin crystal contains too much nitrogen, 7 will form an oxidation-induced cumulative enthalpy (〇ISF) in the wafer, which has an adverse effect on the quality of the epitaxial epicenter 7 (see the Patent Office Notice 1999- 189493 "The oxidation on the surface of the 曰 a曰 causes the cumulative fatigue to be different from other vacancy defects, which is not covered by the deposition of the epitaxial epitaxial layer. 〇1卯 continues to be generated in the epitaxial layer and is commonly referred to as The maximum cross-sectional width of the epitaxial accumulation in the epitaxial epitaxial accumulation is measured by the laser automatic observation device of the existing detection limit, and the range is from about 〇.m to about two meters. Inventively, the atomic concentration of the nitrogen dopant to be contained in the germanium crystal is about 1χ1〇12 to 5χ1〇14 atoms per cubic centimeter (〇1 ppma) and about 1) <1012 to lxl〇u atoms per square centimeter (about 〇 〇〇〇2卯·) Better. The ruthenium ingot can be doped with nitrogen using several methods, such as interposing nitrogen into the formation chamber and/or adding nitrogen to the polymerized ruthenium melt or the like. The amount of nitrogen added to the crystals in the formation 82769-950127.doc -18- (14) 1276161 From the addition of nitrogen to the eight methods. In particular, ^^ Dream wafers, the amount of dinitrogen and the amount of nitrogen: decide, for example, 'before the known diameter of the compound, and the number of the compound (10) 4) layer, which is formed in the 3.18 gram of the stone The density of _4) is about every cubic gas: =: Ming 'oxygen nucleation center can use carbon instead of nitrogen, or carbon = doping to stabilize. The concentration of carbon in the Shi Xi bond is preferably between about 1 x 10 atoms (0.2 ppma) to about the domain and between the sub-bands (8 ppma). ..., Guan Tei principle, currently considered nitrogen / carbon doping; ^UP 1 vacancies diffusion and 氧 oxygen precipitation 〃 = 夕 crystal body cooling 昧, two: In particular, it is known that when the formation of crystal condensate ~, The critical bottom supercritical saturation level (ie, at this point, a vacancy defect or micro-blank that would condense at about 。, for example, condensing 115iMi) occurs at 5G degrees. When the crystal is cooled, the micro-blank is increased by λ because it is only politically directed. Although & : empty: in the continuous cooling, greatly reduce the non-condensation in the crystal::::; _ cooling when 'reaching the second level of critical supersaturation, where the free vacancy and oxygen interact to form the oxygen precipitation core . In the case of non-memory crystals, the second level of critical supersaturation occurs when the crystal is about seven hundred degrees Celsius. In the nitrogen/carbon doped stellite crystal, the blank formation during the polyfluorene period is slightly suppressed due to the slowing of the vacancy diffusivity. This results in a higher concentration of vacancies remaining in the crystal after the first coagulation. The free vacancy rolling increased by the carbon-to-carbon shovel also increases the temperature at which the second level of crystal supersaturation occurs, for example, from about eight degrees Celsius to about one thousand and fifty degrees. At this elevated temperature, the oxygen atoms in the crystal are more active. More oxygen atoms interact with free vacancies to cause oxygen to precipitate out of the nucleus; more preferably 82769-950127.doc -19-
1276161 (15) 穩定。穩定之氧析出核心， 矽層等期間，更能阻滯分解 在後續之熱處理諸如生成外延 〇 依據本發明以氮/碳摻雜的氧濃度核心之穩定亦可併入 於絕緣體上以離子植入而產生矽的方法中，離子植入具有 内在吸收能力而非2001年6月22日提出之美國申請案第 60/300,208號所揭示之熱穩定法，或與之合併行之，茲錄於 此以供參考。 依據本發明以氮/碳摻雜的氧濃度核心之穩定亦可併入 第6,236，104號美國專利案所揭示之於絕緣體上產生石夕的方 法中，茲錄於此以供參考。 單晶石夕中晶格空位之測量可以翻擴散分析法實施。一般 言之，於允宜選定之擴散時程與溫度上將鉑澱積於樣品上 並於水平表面擴散，而使Frank-Turnbull機制支配鉬之擴散， 但其充分達到鉑擴散所飾空位的穩定狀態。就具有本發明 典型空位濃度之晶圓而言，可採攝氏七百三十度及二十分 鐘之擴散，於較低溫度上，例如約攝氏六百八十度，顯示 可獲更精確執跡。此外，為將矽化過程之可能影響減至最 低’翻澱積法最好少於一單層之表面濃度。顧擴散技術在 其它著述中亦有闡釋，例如：Jacob等所著J. Appl· Phvs.·第82 卷第 182 頁（1997) ; J. Electrochemical Society 第 139 卷第 256 頁 (1992) ，Zimmermann及Ryssel所著：11於不均衝狀況下石夕中溶 化翻的擴散”；Journal of Crystal Growth 第 129 卷第 582 頁 (1993) ，Zimmermann，Goesele，Seilenthal 及 Eichiner等所著，， 矽之空位濃度晶圓製圖π ; Appl. Phvs. Lett第60卷第3250頁 (1992)，Zimmermann及Falster所著11初階段切克勞斯基石夕中氧 82769-950127.doc -20- 1276161 (16)1276161 (15) Stable. Stable oxygen precipitation core, ruthenium layer, etc., can block decomposition in subsequent heat treatment such as generating epitaxial 〇. According to the present invention, nitrogen/carbon doped oxygen concentration core stability can also be incorporated into the insulator for ion implantation. In the method of generating enthalpy, the ion implantation has an intrinsic absorbing capability, and is not disclosed in the heat stabilization method disclosed in U.S. Application Serial No. 60/300,208, which is incorporated herein by reference. for reference. The stabilization of the oxygen concentration core doped with nitrogen/carbon in accordance with the present invention is also incorporated in the method for the production of a slab on the insulator disclosed in U.S. Patent No. 6,236,104, the disclosure of which is incorporated herein by reference. The measurement of the lattice vacancies in the single crystal can be carried out by diffusion diffusion analysis. Generally speaking, in the diffusion time duration and temperature selected by Yunyi, platinum is deposited on the sample and diffused on the horizontal surface, so that the Frank-Turnbull mechanism dominates the diffusion of molybdenum, but it fully satisfies the stability of the platinum diffusion vacancy. status. For wafers having a typical vacancy concentration of the present invention, a diffusion of 730 degrees Celsius and 20 minutes can be taken, and at a lower temperature, for example, about 680 degrees Celsius, the display can be more accurately falsified. . In addition, in order to minimize the possible effects of the deuteration process, the devolatilization method is preferably less than the surface concentration of a single layer. Gu diffusion techniques are also explained in other writings, for example: Jacob et al., J. Appl. Phvs., Vol. 82, pp. 182 (1997); J. Electrochemical Society, Vol. 139, 256 (1992), Zimmermann and Ryssel: "The spread of melting and melting in Shi Xizhong under uneven conditions"; Journal of Crystal Growth, Vol. 129, p. 582 (1993), Zimmermann, Goesele, Seilenthal and Eichiner et al., vacancy concentration Wafer drawing π ; Appl. Phvs. Lett Vol. 60, p. 3250 (1992), Zimmermann and Falster, 11 early stage, Czochralski, Shih, Oxygen 82769-950127.doc -20- 1276161 (16)
析出物成核的研究π ;以及Appl. Phvs. A.第55卷第121頁 (1992)，Zimmermann 及 Ryssel之著作等。 圖式簡單說明 圖1為本發明方法的簡圖。 82769-950127.doc -21 -Study of precipitate nucleation π; and Appl. Phvs. A. Vol. 55, p. 121 (1992), Zimmermann and Ryssel's work. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a simplified diagram of the method of the present invention. 82769-950127.doc -21 -