TW394970B - The formation of semiconductor substrate surface insulation film and its related processes - Google Patents

The formation of semiconductor substrate surface insulation film and its related processes Download PDF

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TW394970B
TW394970B TW087109635A TW87109635A TW394970B TW 394970 B TW394970 B TW 394970B TW 087109635 A TW087109635 A TW 087109635A TW 87109635 A TW87109635 A TW 87109635A TW 394970 B TW394970 B TW 394970B
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Taiwan
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insulating film
semiconductor substrate
forming
patent application
scope
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TW087109635A
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English (en)
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Hikaru Kobayashi
Kenji Yoneda
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Matsushita Electronics Corp
Japan Science & Tech Corp
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  • Formation Of Insulating Films (AREA)
  • Insulated Gate Type Field-Effect Transistor (AREA)

Description

A7 B7 五、發明說明（I ) 在半導體裝置、特別是MNOS (金屬氧氮化半導體 )電晶體、MN 0 S電容之閘極絕緣膜以及電容絕緣膜， 當採用矽裝置的情形，會使用到氮化矽膜。由於該等絕緣 膜係被要求著高絕緣擊穿耐壓及高絕緣擊穿電荷量，因此 晶圓之洗淨爲一非常重要之過程。又，於洗淨晶圓的同時 ，亦要求著低固定電荷密度、低界面態(interface state)密度 〇 另一方面，伴隨著裝置的精細化、高集積化，閘極絕 緣膜以及電容絕緣膜亦隨之薄膜化，例如在0.1#m的設計 準則下要求著3nm之薄膜閘極絕緣膜。 以往形成MN 0 S電晶體之閘極絕緣膜所使用之方法 係於1000°C左右之高溫中，將半導體基板暴露一氧化二氮 (N2〇)或一氧化氮(NO)的周圍氣氛中，或是於氨氣周圍氣氛 中將晶圓加熱至700°C左右》 除此之外，做爲以低溫形成氧氮化膜的方法，有一邊 照射紫外線一邊進行熱氧氮化之方法、藉由將矽暴露於氮 化合物或氮氣之電漿中直接氧氮化之方法，但無論何種方 法，皆無法以良好之控制性以及再現性來形成厚度薄且高 品質的氧氮化膜。 以往使用^^2〇氣體行熱氧氮化時需高溫加熱，又有 氧氮化膜所內含之氮原子的量少與二氧化矽膜的薄膜性質 並未十分改善之問題。又，使用N 0氣體行熱氧氮化時， 雖然加熱溫度降至900°C左右，且氧氮化膜所內含之氮原 子的量有若干增加，但有無法成長具既定以上薄膜厚度之 3 (請先閱讀背面之注意事項再填寫本頁) I n II ϋ 一：eJ· n ϋ n 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4-規格（210 X 297公釐） 經濟部智慧財產局員工消费合作社印製 A7 ___B7____ 五、發明說明（Y) 氧氮化膜的問題。又，使用氨氣行熱氧氮化時，氧氮化膜 中將含大量的氫，由於氫扮演著捕集電子的角色，因而薄 膜性質變差，從而造成之問題爲，爲了去除氫，必須於氧 氮化膜形成之後加熱至i〇〇〇°c左右或進行氧化。 又，藉由電漿將矽直接氧氮化時，有因電漿衝擊造成 薄膜性質不良的問題，特別是界面態的發生，不僅造成電 晶體之熱載子特性變差，亦會引起電晶體之臨限電壓 (threshold voltage)的不安定、載子之移動度的降低等對細微 裝置而言致命性的問題。 再者，伴隨元件的細微化，是以亦要求於熱處理過程 之低溫化，其理由係以高溫加熱時將會有摻質的擴散與缺 陷的形成等問題β就以R F電漿將二氧化矽膜氧氮化而言 ，當使用ΝΗ3電漿之時，雖然可於薄膜中摻入大量之氮原 子，但同時於薄膜中亦含有大量之氫原子，而有薄膜性質 變差的問題。 又，使用Ν2電漿的情形，有薄膜中之氮原子含有量少 、薄膜性質未十分改善之問題〔例如可參照P. Fazan，Μ. Dutoit and Μ· Ilegems，（Appl. Surf. Sci.) 30 章，224 頁 ’ 1987 年〕。 〔發明摘要〕 爲解決上述習知之含氮原子絕緣膜的形成方法所具有 的問題，本發明之目的乃提供一種半導體基板表面的絕緣 膜之形成方法以及其形成裝置，其不需高溫加熱，即可高 控制性地於半導體基板的表面上形成含大量氮原子之高品 4 _ 本紙張尺度適用t國國家標準（CNS)A4規格（210 X 297公釐） ---1--------^褒--------訂---------線f . (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 _______B7___ 五、發明說明（j ) 質的絕緣膜。 爲求達成上述目的’本發明特徵係提供一種至少於半 導體基板表面含絕緣膜之半導體裝置，且絕緣膜之厚度介 於1〜20nm之範圍。 又，於半導體裝置中’暴露於以電子衝擊所產生之電 漿的絕緣膜以二氧化矽膜爲佳，二氧化矽膜可使用以熱氧 化、化學氣相成長、化學氧化、物理氣相成長及電發促使 化學氣相成長等所形成之物。 又，於上述半導體裝置中，半導體基板以擇自單結晶 砂、多結晶矽、非結晶砂、砷化鎵、磷化銦、碳化砂、鍺 化矽、碳化矽鍺中至少一種材料爲佳。 其次，本發明之特徵在於，先於半導體基板表面形成 厚度介於1〜20nm範圍的二氧化矽膜，接著將其暴露於 以電子衝擊所產生之電漿中，藉以改善二氧化矽膜之品質 。此時較佳爲，藉由於電子放出源、或是於柵形電極與半 導體基板間施加適當的電壓，以防止暴露於電漿中所生成 之絕緣膜發生充電現象。 於上述方法中，以電子衝擊產生電漿時所使用之氣體 較佳者係擇自下述A〜Η中至少一種。 A ·氮氣 B·—氧化二氮氣體 C·氧化氮氣體 D ·氨氣 E·上述氣體中二種以上之混合氣體 5 11 ^装--------訂------1·線·->. (請先閱讀背面之注咅？事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（φ) F ·上述氣體與氬、氖等鈍性氣體之混合氣體 G·上述氣體與乾燥氧之混合氣體 Η·上述氣體與含水蒸氣之氧的混合氣體 使用上述Α〜η的氣體之理由係其適於對例如矽表面 具二氧化砍膜之半導體進行氮化以改善薄膜特性。 又’於上述方法電漿處理中的熱處理溫度以〇°c〜7〇〇 °C的範圍爲佳。這是因爲藉由低溫氧氮化處理的進行可達 成本發明的目的。 又’於上述半導體及其絕緣膜的形成方法中，半導體 基板以擇自單結晶矽、多結晶矽、非晶形矽、砷化鎵、磷 化銦、碳化矽、鍺化矽、碳化矽鍺中至少—植材料爲佳， 這是因爲其作爲半導體基板之應用範圍很廣。 又’於上述方法，進行電漿處理之絕緣膜，以膜厚介 於1〜20nm範圍之二氧化矽膜爲佳。這是因如在上述的 範圍’最後獲得之絕緣膜之厚度可用於MIS電晶體、MIS 電容的極薄閘極絕緣膜及電容絕緣膜等方面。 依據本發明之半導體基板表面的絕緣膜之形成 方法’係於半導體基板上形成厚度介於丨〜2〇11111範圍之 絕緣膜’然後’將半導體基板溫度保持於70(TC以下之溫 度狀態的半導體基板上之絕緣膜暴露於以電子衝擊所生成 之電漿中’藉此’乃可有效率、合理地在半導體基板上形 成兼具高品質及高控制性之均一品質的絕緣膜。 於此時所形成之絕緣膜，在絕緣膜與半導體基板的界 面以及絕緣膜的最表面處，含有較高濃度氮原子，由於界 6 本紙張尺度適用中國國豕標準（CNS)A4規格（210 X 297公釐） ----1.--------裝------— —訂---------線(-· (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消费合作社印製 A7 ___B7_ 五、發明說明（(） 面附近存在有氮原子，所獲得之物乃具有優異的界面特性 ，而可形成低界面態密度、高品質的絕緣膜。 再者，由於絕緣膜的表面附近存在有氮原子，故此時 所形成之絕緣膜具有優異之表面特性，並可緻密地形成可 防止硼等之不純物向內擴散之絕緣膜。 此時形成之絕緣膜的薄膜性質，首先，可依照在半導 體基板上最初形成絕緣膜所採用之形成方法加以改變，另 外，氧氮化速度、絕緣膜中之含氮量、於絕緣膜中之深度 方向的氮分佈，可依據進行熱處理時之溫度與時間、氣體 氣氛的種類、爲進行電子衝擊之熱電子源的溫度、以及爲 加速電子而於柵形電極與燈絲間所施加之電壓而變化。於 本發明的更佳條件下，於半導體基板上所形成之絕緣膜可 在0°C至範圍的溫度進行氮化。 [圖式之暴明〕 圖示本發明之第1實施例之使用半導體基板上_ 的絕緣膜良方法來形成MN CLSJt容之胜成過程截面_ 圖。 圖2爲表示本發明之第1實施例之進行晶圓的洗淨將 自然氧化膜去除後，在含水蒸氣之氧周圍氣氛中以850°C 加熱12分鐘後所測定之X射線光電子能譜》 圖3爲表示本發明之第1實施例之在矽基板上形成熱 氧化膜後，於以電子衝擊所生成之氮電漿中以_25°(：暴露1 小時後所測定之X線光電子能譜。 圖4爲表示本發明之第一實施例之在矽基板上形成熱 7 本及張尺度適用中國國家標準 1CNS)A4規袼⑵G X 297公餐> 一 ---Γ--------^裝--------訂---------線~ , (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消费合作社印製 A7 B7 五、發明說明（t) 氧r、化膜後所測定之同步加速紫外線光電子能譜。> '圖5爲表示本發明之第一實施例之在矽.基上形成熱 氧化膜後於以電子衝擊所生成之氮電漿中以25°C暴露1小 時後所測定之同步加速紫外線光電子能譜。 圖6爲表示本發明之第一實施例之在矽基板上形成熱 氧化膜後於以電子衝擊所生成之氮電漿中以25°C暴露1小 時後所測定之氮原子量/(氧原子與氮原子量之和―)的比値對 離開絕緣膜表面的距離所繪製之圖表。 ，圖7爲表示本發明之第一實施例之在矽基板上形成熱 氧化膜後於以電子衝擊所生成之氮電漿中以700°C暴露1小 時後所測定之X射線光電子能譜。 圖8爲表示本發明之第一實施例之在矽基板上形成熱 氧化膜後於以電子衝擊所生成之氮電漿中以700°C暴露1小 時後所測定之氮原子量/(氧原子與氮原子量之和)的比値對 離開絕緣膜之表面的距離所繪製之圖表。 圖9爲表示本發明之第一實施例之在矽基板上形成熱 氧化膜後於以電子衝擊所生成之氮電漿中以7〇〇°C暴露1小 時後所測定之氮原子量/(氧原子與氮原子量之和)的比値對 離開絕緣膜表面的距離所繪製之圖表。 圖10爲表示本發明之第二實施例絕緣膜的形成裝置 之槪略構成圖。 〔發明之較佳實施形態〕 以下，參照圖面同時詳細說明本發明之實施的形態。 圖1爲表示本發明之第一實施例之半導體基板上的絕 8 本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公爱) ---Γ--------^ 衮--------- 訂---------線 A . (請先閱讀背面之注意事項再填寫本頁) A7 A7 經濟部智慧財產局員工消費合作社印製 ____Β7_ 五、發明說明（Ί) 緣膜之形成過程截面圖。本實施例取作爲半導體基板之矽 基板爲例，說明MN 0 S電容之形成過程。 (1) 首先，矽基板上以習知的選擇氧化技術，形成隔離 區域2與活性區域4。活性區域4的表面上存在自然氧化 膜8〔圖1 (a)〕°也就是說’作爲砂基板係使用P型 (100)、10〜15Ω c m之基板’作爲隔離區域2係形成膜 厚 500 nm 之區域氧化（LOCOS : local oxidation of silicon)氧化膜。 (2) 其次，爲洗淨活性區域4的表面，依眾知之R C A 洗淨（參照 W. Kevn，D. A. Plutien，RCA 回顧 31,187 頁’ 1970年）方法，將晶圓洗淨後，在稀H F溶液（0.5v ο 1 .% H F水溶液）浸漬5分鐘，去除矽基板表面的自然氧化 膜8〔圖1 ( b )〕。爲在矽基板表面上形成高品質之二 氧化矽膜，淸淨的矽表面3是必要的’因此矽基板表面之 自然氧化膜8的完全去除以及矽基板表面之不純物的去除 是重要的。 (3) 其次，用超純水將晶圓淸洗(洗淨)5分鐘後’在含 水蒸氣之氧周圍氣氛中以850°C進行氧化，以於矽基板1上 形成厚度8n m之二氧化矽膜5〔圖1 ( c )〕。作爲半導 體基板表面的絕緣膜之形成方法，除本實施例之熱氧化外 ，尙有將甲矽烷熱分解以於基板表面進行堆積之氣相成長 法、濺鍍法、電子束蒸鍍法、電阻加熱蒸鍍法、陽極氧化 法，將半導體浸漬於硝酸與過鹽酸等化學藥品中以化學地 形成二氧化矽膜之方法等。 9 紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公釐） ---1丨.--------^裝--------訂------_!線{"- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（ί) 上述之自然氧化膜8的完全去除，在之後將形成之二 氧化矽膜5的特性上扮演重要之角色，以符合形成淸淨且 均質之二氧化矽膜的要求。 (4) 其次，在1.5X10_2托的氮周圍氣氛中，將鎢絲加 熱至1400°C，在鎢絲與柵形電極之間施加53V之電壓，以 加速從鎢絲上放出熱電子使其衝撞氮分子來產生氮電漿， 將其暴露在二氧化矽膜5上以形成改良之絕緣膜6〔圖1 ( d )〕。此時，半導體基板係加熱至700°C或維持於室溫 下。又，針對柵形電極，乃在半導體基板上施加-10V之電 壓。這是因藉施加此電壓，將電漿中之相同數量的陽離子 與電子打入半導體試料中，於試料位置上之電流量將消失 ，故可防止因充電造成對絕緣膜之損害。 (5) 其次，爲形成電極，乃以濺鍍法將鋁膜7堆積1μ m〔圖1 (e)〕，接著以眾知微影技術將閘電極圖案化後 ，再以眾知的乾蝕刻技術將鋁膜蝕刻，形成閘電極9〔圖1 (f )〕。 圖2爲表示本發明之第1實施例之進行矽晶圓之洗淨 將自然氧化膜去除後，在含水蒸氣之氧周圍氣氛中以850 °C加熱12分鐘後所測定之X射線光電子能譜。 X線光電子能譜是用VG SCIENTIFIC社所製之 ESCALAB 220 i-XL測定。此時，使用能量1487 e V的鋁K α射線作爲X射線源。又，光電子是以表面垂直方向觀測 。波峰（1)是依據從二氧化矽膜的氧之1S軌道來的光電 子而成。於此試料並未存在來自氮1S軌域波峰，可知在 10 ---^1-------^ · 111---—til! — — — · I f ** (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消费合作社印製 A7 B7__ 五、發明說明（^ ) 二氧化矽膜中並無氮原子。 圖3爲上述之二氧化矽膜在以電子衝擊所生成之氮電 漿中以25°C暴露1小時後所觀測到之X射線光電子能譜。 從此圖可明瞭’波峰（2)是依據由氮之is軌道來的 光電子。從波峰（2)和由氧的1S軌道來的光電子波峰（ 1)之面積強度比，可計算出從表面到光電子的脫離深度3 n m之表面區域所含氮原子數/(氧原子數與氮原子數和)之 比値爲29%。此事可表示，藉由將二氧化矽膜暴露於因電 子衝擊所生成之氮電漿中，薄膜中將可含有氮原子，而使 二氧化矽膜改良。 圖4爲矽基板上形成之熱氧化膜的同步加速紫外線光 電子能譜。 此同步加速紫外線光電子能譜是用高能量物理學硏究 所，放射光實驗設施之射束B L - 3B所測定。此時，入射 光的能量爲65e V。因爲以吸收此入射光能量而放出之光 電子的脫離深度爲6〜7A，是以觀測係從表面至6〜7埃 之深度。能量基準爲費米能等級。波峰（2)是依據來自氧 2S軌道之光電子。 圖5爲在矽基板上形成熱氧化膜，其試料在以電子衝 擊而生成之氮電漿中以暴露1小時，之後所觀測到之 同步加速紫外線光電子能譜。 此時，入射光之能量爲65e V。此時可歸類波峰（2 )爲來自四氮化三矽的氮2S軌道之光電子，波峰（3)爲 來自四氮化三矽的氮2P軌道與矽3S軌道的混成軌道之光 11 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱1 (請先閲讀背面之注意事項再填寫本頁) 裝--------訂---------線f 經濟部智慧財產局員工消費合作社印製 B7_ 五、發明說明（
電子，波峰（4)爲來自四氮化三矽的氮2P軌道與矽3P 軌道的混成軌道之光電子，波峰（5)爲來自氮2P非結合 性軌道之光電子。〔例如參照（：.56!^1^11山厘.〇1^-
Khodja，A· Gheorghiu，S. Harel，G. Dufour，and H. Roulet 應用 物理學雜誌 U. Appl. Phys ) 74 卷（1993 年）5042 頁〕。 此顯示藉由將二氧化矽膜暴露在因電子衝擊所生成之 氮電漿中，表面將變化成四氮化三矽層，薄膜受到了改良 〇 圖6係就藉由將二氧化矽膜暴露於室溫下之以電子衝 擊所生成之氮電漿中而改良之絕緣膜，其氮原子量/(氧原 子與氮原子量之和)之比値對離開絕緣膜表面的距離所繪製 而成之圖表。 此圖表是以動能爲2K e V之氬離子將絕緣膜的表面 慢慢地蝕刻，之後藉由測定X射線光電子能譜而得。從此 圖表可得知，氮原子的量在絕緣膜之表面附近爲最多，其 次爲在絕緣膜與矽基板之界面。 界面附近上之氮原子的增加，並非因氬離子的打入所 造成之氮原子的導入現象，亦即不是藉撞出而成，因如爲 撞出而成則具有與氮原子相近質量數之氧原子也應該在界 面附近增加，但結果在界面附近氧原子的存在量卻減少了 〇 表面附近之氮原子有防止在雙閘C Μ 0 S裝置之P通 道電晶體之閘電極上所含的硼等之不純物侵入薄膜內部的 效果。 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---L—--------^裝--------訂---------線f 丨 (請先閲讀背面之注意事項再填寫本頁) A7 —___B7 _ 五、發明說明uh (請先閱讀背面之注意事項再填寫本頁) 又，此表面附近之氮原子係視爲終止氧化膜/上部電 極（就本實施例而言爲鋁，亦有爲多結晶矽等的情形）界 面附近之懸空鍵與彎曲鍵等，而有降低界面態、增加絕緣 擊穿電荷量、提昇絕緣擊穿耐壓性等效果。 另一方面，在氧化膜與矽基板的界面附近也觀察氮原 子的波峰。於MNO S構造中，氧化膜/矽基板界面在絕 緣擊穿特性、界面特性等電氣特性上扮演極重要之角色， 藉由以氮原子強固地終止界面附近之懸空鍵、不規則鍵、 彎曲鍵，不僅可降低界面態密度，亦可藉由施加電流應力 等防止界面附近之惡化。亦即，如依據本發明的絕緣膜之 形成方法，絕緣膜的特性可由表面及界面等兩面來改良， 進而可實現高性能之超薄絕緣膜。 圖7爲在矽基板上形成熱氧化膜，將該半導體試料在 以電子衝擊所生成之氮電漿中用700°C暴露1小時，而後觀 測到之X射線光電子能譜。波峰（2)爲來自氮的1S軌道 之光電子。 經濟部智慧財產局員工消费合作社印製 從波峰（2)與來自氧的1S軌道之光電子波峰（1) 之面積強度比，可計算出從表面到約3nm之表面區域上 所含氮原子數/(氧原子數與氮原子數之和)的比値爲11% » 從波峰（1)之結合能可得知1個氮原子上面結合著3個的 矽原子。 圖8爲在矽基板上形成熱氧化膜，將該半導體試料在 以電子衝擊所生成之氮電漿中用700°C暴露1小時，而後觀 測到之同步加速紫外線光電子能譜。 13 參&張尺度適用令國國家標準（CNS)A4規格（210 x297公釐） 經濟部智慧財產局員工消費合作社印製 A7 ____—_B7____ 五、發明說明（/1) 此處，可歸類波峰（1)爲來自氧2 s軌道之光電子’ 波峰（2)爲來自氮2 s軌道之光電子。結合能從〇e V至 15e V的區間之能譜的形狀，會因將二氧化矽膜暴露在氮 電漿上而發生若干變化，但並未觀測到因四氮化三矽產生 之波峰。又，從氮的含有量11%此較爲少量的結果可得知 在表面區域已形成氧氮化膜。 圖9爲關於在矽基板上形成熱氧化膜，將該半導體試 料在以電子衝擊所生成之氮電漿中用700°C暴露而改良之 薄膜，其氮原子、氧原子、矽原子的存在量對離開薄膜表 面之距離繪製而成之圖表。從此圖表可得知大量的氮原子 係於薄膜表面附近、薄膜與矽基板的界面上存在。 這些結果爲半導體基板之加熱溫度如果愈低，可在絕 緣膜的表面上含有愈高濃度的氮，此含有量可藉由加熱溫 度來控制。又，關於表面附近與界面附近之氮濃度，相較 於在室溫之電漿暴露表面濃度明顯高於界面，在700°C則 是界面的氮濃度比表面濃度高，此點亦無庸置疑的說明了 可控制薄膜中氮的分布。 其次，說明本發明之第2實施例。 圖10爲表示本發明之第2實施例所示之半導體基板 表面的絕緣膜之形成裝置的槪略構成圖。 如圖所示，藉由不銹鋼S U S 316構成之容積約 18000 cm3的橫向延伸之反應室101內，半導體基板1〇2 係以水平狀態被支持在撐桿101A上。 在反應室101的上部設有熱電子放出源（鎢絲）104、 14 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---- I I I------^裝！ ！| 訂·11!!·線(· (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局具工消費合作社印製 A7 B7 五、發明說明（/1]) 柵形電極105、網狀電極106，於鎢絲104之兩端可施加電 壓，又鎢絲104受到加熱將放出熱電子。在柵形電極105 上施加電壓將可加速自鎢絲104放出之熱電子。 在網狀電極106、半導體基板102上亦可施加電壓， 藉由調整施加在這些上面之電壓，可使射入絕緣膜表面之 電荷量歸零，進而防止絕緣膜之充電。又，在反應室101 之上部與下部，設有鹵素燈泡103，於鹵素燈泡103的部 分，係在反應室101上設有石英玻璃所製之窗。藉由鹵素 燈泡103可加熱半導體102。 於此絕緣膜之形成裝置中，係以從反應室的左端分別 設置氧氣導入管107、水蒸氣導入管108、氮氣導入管109 、一化二氮氣體導入管110、氧化氮氣體導入管111、氬氣 導入管112、氟化氫氣體導入管113的方式所構成。這些 氣體，在反應室101內之半導體基板102的表面反應後， 由反應室101之右端的排氣口排出。再者，實際裝置上備 有半導體基板搬送機構和控制部、電源部及溫度測量部等 ，於本實施例中，只表示實際上製程進行時反應室附近及 電壓施加部。 其次，用備有上述構成之絕緣膜的形成裝置，說明關 於絕緣膜形成情況。此時，作爲半導體基板，係使用表面 積314 c m 2之直徑200mm單結晶矽基板。 首先，將半導體基板（單結晶矽基板）102配置在既 定之位置後，爲去除半導體基板（單結晶矽基板）102表 面之自然氧化膜，乃在反應室101內導入約30秒之20c c 15 本紙張尺度適用令國國家標準（CNS)A4規格（210 X 297公釐） --j—-------^裝--------訂---------線f - (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明說明（（十） /分之流量的無水氟化氫氣體。 依此，可完全去除半導體基板（單結晶矽基板）102 表面的自然氧化膜，進而露出淸淨的矽表面。 其次，將氧氣以5000 c c/分之流量導入反應室101 的同時，藉由鹵素燈泡103將半導體基板（單結晶矽基板 )102之表面溫度達到1000°C般地加熱之。在此狀態加熱 到120秒時，半導體基板（單結晶矽基板）102的表面上 將形成膜厚8n m之二氧化矽膜。此時，若改爲導入氧或 同時導入水蒸氣以及氧，將可以更低溫度得到既定的膜厚 〇 其次，將反應室101排氣後，在其中導入氮氣，使反 應室101內之壓力成爲0.5托。此時氮氣之流量爲50c c /分。 其次，藉由在鎢絲104上流入電流以加熱至1300°C， 其次，相對鎢絲104在柵形電極105上施加23 V之電壓， 使氮分子藉由電子衝擊來產生氮電漿。 此時，相對柵形電極105在網狀電極106上施加-5V 電壓，於半導體基板102上施加-10V之電壓。又，藉由鹵 素燈泡103使半導體基板（單結晶矽基板）102之表面溫 度加熱至400°C。藉由暴露在氮電漿狀態下1小時，將二氧 化矽膜改良。 於本實施之形態中，亦可藉由調整半導體基板（單結 晶矽基板）102的加熱溫度、導入反應室101中氮氣的流 量、絕緣膜在電漿中暴露的時間、鎢絲104的溫度、施加 16 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝--------訂----- 線(！ 經濟部智慧財產局員工消費合作社印製 B7 B7 經濟部智慧財產局員工消费合作社印製 五、發明說明（/0 在柵形電極105上之電壓，可對存在於絕緣膜中之氮原子 含有量、絕緣膜中之氮原子在深度方向的分布簡單地進行 控制。 依以上所述，在半導體基板（單結晶矽基板）102的 表面上形成氧氮化膜後，可依照上述第1之實施例的圖1 所示之MN 0 S電容之製作流程來製作MN 0 S裝置。 再者，於本實施例之形態中，係以使用氮氣之情況舉 例說明，但只要係含有一氧化二氮氣體、氧化氮氣體、氨 氣等含氮原子之化合物氣體，即可達成所期待之目的。此 時，氣體中亦可混入氬氣及氖氣等氣體。 又，於本實施例之形態中，半導體基板之加熱溫度係 設定爲400°C，但溫度未必受限於此，只要半導體基板之 加熱溫度爲〇°C以上、700°C以下即可。 又，於本實施之形態中，係藉由鹵素燈泡使半導體基 板102之表面加熱，但構成未必受限於此，亦可用電阻加 熱方式。 又，於上述第1及第2實施例中，作爲半導體基板， 係以使用單結晶矽基板的情況舉例說明，但未必限定在單 結晶矽板上，亦可適用在多結晶矽、非晶形矽、砷化鎵、 磷化銦、鍺矽、碳化鍺矽、碳化矽等由其他半導體所構成 之基板上。 再者，本發明並不限定僅爲上述實施例，基於本發明 之宗旨之種種的變形亦可，這些並未排除在本發明的範圍 之外。 17 ---r---------^裝--------訂---------線f 丨 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用^國國家標<(CNS)A4規格（210><297公^| ) " A7 _B7_ 五、發明說明（丨k) 如以上詳細之說明般，根據本發明，藉由將絕緣膜暴 露在以電子衝擊所生成之電漿中，可以700°C以下之低溫 來進行絕緣膜之改良，藉由將這些絕緣膜作爲閘極絕緣膜 來使用，可實現高性能之Μ N 0 S裝置。 -------------^裝！----訂-----! — I 線(— (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）

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  1. 六、申請專利範圍 經濟部智慧財產局員工消費合作社印製 1 .一種半導體基板表面的絕緣膜之形成方法，其特 徵在於，係將形成於半導體基板表面之絕緣膜暴露於以電 子衝擊所產生之電漿中。 2 ·如申請專利範圍第1項之半導體基板表面的絕緣 膜之形成方法，其中，形成於上述半導體基板表面之絕緣 膜係膜厚介於1〜2〇n m範圍之二氧化砍。 3 ·如申請專利範圍第1項之半導體基板表面的絕緣 膜之形成方法，其中，上述所產生之電漿係藉由對含有氮、 原子之化合物、單體，亦即對氮分子、一氧化二氮（N 2 0 )、一氧化氮（NO)、氨等進行電子衝擊所產生之電漿 0 4 ·如申請專利範圍第丨項之半導體基板表面的絕緣 膜之形成方法，其中.，上述半導體基板係擇启單結晶砂一、 多結晶矽、非晶形矽、砷化鎵、磷化銦、碳化矽、鍺化矽 、碳化砂鍺·中至少一者之材料。 5 .如申請專利範圍第1項之半導體基板表面的絕緣 膜之形成方法，其中，形成於上述半導體基板之絕緣膜係 藉由熱氧化或化學氣相成長、化學氧化膜、電漿促使化學 氣相成長以及物理氣相成長等所成長者。 6 ·如申請專利範圍第1項之半導體基板表面的絕緣 膜之形成方法，其中，上述絕緣膜的表勝附近以及該絕緣 膜與上述半導體基板的界面附近有兩個氮濃度的波峰，且 波峰之氮濃度爲0.1原子％至60原子％。 7 · —種絕緣膜之形成裝置，係用以實現申請專利範 (請先閱讀背面之注$項再填寫本頁) -*·
    本紙張尺度逍用中國國家榡準（CNS ) A4規格（il〇X297公釐）
    六、申請專利範圍 經濟部智慧財產局員工消費合作社印製 1 .一種半導體基板表面的絕緣膜之形成方法，其特 徵在於，係將形成於半導體基板表面之絕緣膜暴露於以電 子衝擊所產生之電漿中。 2 ·如申請專利範圍第1項之半導體基板表面的絕緣 膜之形成方法，其中，形成於上述半導體基板表面之絕緣 膜係膜厚介於1〜2〇n m範圍之二氧化砍。 3 ·如申請專利範圍第1項之半導體基板表面的絕緣 膜之形成方法，其中，上述所產生之電漿係藉由對含有氮、 原子之化合物、單體，亦即對氮分子、一氧化二氮（N 2 0 )、一氧化氮（NO)、氨等進行電子衝擊所產生之電漿 0 4 ·如申請專利範圍第丨項之半導體基板表面的絕緣 膜之形成方法，其中.，上述半導體基板係擇启單結晶砂一、 多結晶矽、非晶形矽、砷化鎵、磷化銦、碳化矽、鍺化矽 、碳化砂鍺·中至少一者之材料。 5 .如申請專利範圍第1項之半導體基板表面的絕緣 膜之形成方法，其中，形成於上述半導體基板之絕緣膜係 藉由熱氧化或化學氣相成長、化學氧化膜、電漿促使化學 氣相成長以及物理氣相成長等所成長者。 6 ·如申請專利範圍第1項之半導體基板表面的絕緣 膜之形成方法，其中，上述絕緣膜的表勝附近以及該絕緣 膜與上述半導體基板的界面附近有兩個氮濃度的波峰，且 波峰之氮濃度爲0.1原子％至60原子％。 7 · —種絕緣膜之形成裝置，係用以實現申請專利範 (請先閱讀背面之注$項再填寫本頁) -*·
    本紙張尺度逍用中國國家榡準（CNS ) A4規格（il〇X297公釐） A8 B8 C8 D8 夂、申請專利範圍 圍第1項之半導體基板表面的絕緣膜之形成方法；該裝置 具有：用以產生電漿之可施加電壓之燈絲，位於該燈絲上 部之可施加電壓之柵形電極，以及位於燈絲極下部之可施 加電壓之網狀電極；該網狀電極、燈絲、柵形電極係位於 晶圓表面之上部，晶圓係具有得以藉由於反應室上下所配 置之虜素燈泡來加熱之構造，上述反應室爲一於上述鹵素 燈泡部份具有石英窗的金屬反應室’並具有可自該反應室 之一端導入氣體、再由另一端進行真空排氣之構造。 8 .如申請專利範圍第7項之絕緣膜之形成裝置，其 中，可自氣體導入口導入之氣體係無水H F、氧、水蒸氣 、N2〇、N〇、NH3、N2。 (請先聞讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 準 梂 家 A4 If 公 97 2
TW087109635A 1997-06-20 1998-06-17 The formation of semiconductor substrate surface insulation film and its related processes TW394970B (en)

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KR19990007161A (ko) 1999-01-25
JP3222404B2 (ja) 2001-10-29
EP0886308A2 (en) 1998-12-23
US6265327B1 (en) 2001-07-24
KR100391840B1 (ko) 2003-11-28
EP0886308B1 (en) 2007-10-10
DE69838532D1 (de) 2007-11-22
EP0886308A3 (en) 1999-09-22
DE69838532T2 (de) 2008-02-07
JPH1116900A (ja) 1999-01-22

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