TWI289330B - Method to enhance the initiation of film growth - Google Patents

Method to enhance the initiation of film growth Download PDF

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Publication number
TWI289330B
TWI289330B TW094104658A TW94104658A TWI289330B TW I289330 B TWI289330 B TW I289330B TW 094104658 A TW094104658 A TW 094104658A TW 94104658 A TW94104658 A TW 94104658A TW I289330 B TWI289330 B TW I289330B
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Taiwan
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metal
group
oxide
layer
oxynitride
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TW094104658A
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English (en)
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TW200631082A (en
Inventor
Maes Jan Willem
Annelies Delabie
Yasuhiro Shimamoto
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Asm Internat
Renesas Tech Corp
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    • H01L21/02142—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
    • H01L21/02148—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing hafnium, e.g. HfSiOx or HfSiON
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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Description

•1289330 · 九、發明說明： 【發明所屬之技術領域】 [0001]本發明大體上係關於積體電路（IC)製造方法。 [〇〇〇2]本發明尤係關於譬如二氧化矽或氮氧化矽層之表 面處理，用於後續金屬、金屬氧化物、金屬氮化物、和/或 金屬破化物層之沉積。 : 【先前技術】 [0003]積體電路設計不斷縮小尺寸以便尋求較快速的電 路操作和較低之電源消耗。 參 [〇〇〇4]當半導體裝置變得較小時，則需要較高電介質常數 (高k值）閘極材料。 [0005]已研究出許多高電介f常數電介質材料（高k電 介質）可能代替選用為閘電極材料之二氧化梦。但是尚存的 其中-侧題是，於該基板表面上之該高k材料之沉積，以 獲得可與尋求之性質與應用相容之層厚度。 ^ [〇〇〇6] W〇〇2/43115號說明一種於藉由非沉積電漿產品 - 方式之成核敏感沉積（uncleation-sensitive 參 deP〇sition)與吸附驅動沉積（adSorpti〇n-driven deposition)而製備後續處理基板表面之方法。 [000Ή US 6,62〇。2〇號說明一種於半導體製程中減少 熱預算之方法’其中該遠端熱氣化作用步驟（rem〇te, thermal nitridatiQn step)由遠端雷射氮化作用步 驟所代替。 [〇〇〇8]沒有任何-種該等方法可以在化學穩定基板表面 上形成平滑、均勻和封閉之薄膜（或層）。 5 1289330 · [0009] 的確，一直到本發明，才慢慢開始沉積高k金屬 乳化物於化學穩定基板表面上，並且經由三維（較一個單潛 為高）浮閘（island)之局部成核而分布於所有表面之上。 僅备一旦各浮閘大到足夠生長在一起時，才可能發生薄膜封 閉。結果，在獲得將用於半導體應用之封閉薄膜之前，必須 沉積材料至某一最小厚度（例如，大約l〇nm或更厚）。 : 【發明内容】 [0010] 雖然本發明之方法特別適合用於沉積高k電介質 _ 薄膜，但是在沉積金屬、金屬氮化物、金屬氮氧化物、或金
屬破化物薄膜於化學穩態表面時遭遇相似之問題時，亦能有 利地使用本發明之方法D
[0011] 本發明提供一種增強金屬、金屬氧化物、金屬氮化 物、金屬氮氧化物、和/或金屬破化物層之方法，包括步驟： 沉積該金屬、金屬氧化物、金屬氮化物、金屬氮氧化物、和 /或金屬碳化物層於sixNy層上，其中x和y為實數，其 中X等於大約3或大於3，其中y大於〇和等於或小於大 約4，以及其中x和y可以相等或不同。較理想之情況是， 參 x^3和0〈β4。較理想之情況是，x/y之比例大於大約 〇· 75並可無上限之變化。 [0012] 本發明係基於令人驚異的發現到，當金屬、金屬氧 化物、金屬氮化物、金屬氮氧化物或金屬碳化物薄膜生長於 像Si#4 (ShN4-like)之層上時，該等薄膜之生長抑制 (growth inhibition)強烈地減少，或甚至完全免除。 [0013] 依照本發明之方法，允許增強金屬、金屬氧化物、 金屬氮化物、金屬氮氧化物、和/或金屬碳化物薄膜（或層） 镰
1289330 沉積於該SixNy層上，獲得高品質之超薄膜，尤其是具有小 於8nm厚度之薄膜，較理想之情況是小於（大約）5nm、小 於（大約）4nm、或小於（大約）3nm，而尤其是最好小於 (大約）2nm。 [〇〇14]本發明之用來增強金屬、金屬氧化物、金屬氮化 物、金屬氮氧化物、和/或金屬碳化物層生長之方法，包括 步驟：沉積該金屬、金屬氧化物、金屬氮化物、金屬氮氧化 物、和/或金屬碳化物層於SiXNy層上，其中X和y為實 數，其中X等於（大約）3或大於（大約）3，其中y大於 〇或等於或小於（大約）4，以及其中x*y可以相等或不 同〇 [0015]能夠藉由物理氣相沉積（pVD)製程（譬如濺鍵）、 化學氣相沉積（CVD )製程、金屬有機CVD (M〇CVD )製程、 或原子層_ (ALD)製程，軌積該金屬、韻氧化物、 金屬氮化物、金屬氮氧化物、和/或金屬碳化物。 [〇〇16]於本發明方法中，該高k金屬氧化物能夠是選自 由氧化鈦、氧她、氧她、氧傾、氧化鑭氧化給 ^hafnium oxide)、氧化銳給、氧化矽給，和這些物質 =任何二者、三者、四者、五者或六者之組合所組成之群 = 017]該金屬能夠是選自由组、釘、鈦、鶴 和這些元素中之任何二者、三者、四六 者或更多之組合所組成之群中。 [〇〇叫該金屬氮化物能夠是選自 鶴、氮化銳、氮化一，和這L質中化 1289330 二者、四者、五者或六者之組合所組成之群中。 [0019] 於本發明之方法中，該金屬氮氧化物能夠是選自由 氮氧化鈦、氮氧化鈕、氮氧化鋁、氮氧化鍅、氮氧化網、氮 氧化姶、氮氧化銃铪、氮氧化矽铪，和這些物質中之任何二 者、二者、四者、五者或六者之組合所組成之群中。 [0020] 該金屬碳化物能夠是選自由碳化组、破化鈦、破化 鎢、碳化銳、碳化鉬、碳化給，和這些物質中之任何二者、 三者、四者、五者或六者之組合所組成之群中。再者，能夠 選擇金屬虱化物和金屬碳化物之任何組合，譬如碳化氮化 鎢。 [0〇21]於本發明之較佳方法中，於沉積該金屬、金屬氧化 物、金屬氮化物、金屬氮氧化物、和/或金屬破化物層步驟 之前，該SixNy層沉積在譬如熱氧化物層之金屬生長抑制表 面上’尤指熱Si〇2層或熱SiON層。 [0022] 能夠藉由使用包括至少一個和氨（Μ%)之先驅物 之化學氣相沉積製程方式，或藉由使用包括至少一個矽烧和 氮基以及選用之氨（服3)之先驅物之racvd、rPECVD或 PECVD製程方式，而沉積該SixNy層。 [0023] 該至少一個矽烷能選自由單矽烷、雙矽烷、三矽 烧、單氣矽烧、雙氣碎烧、三氣矽垸、和四氣矽烷所組成之 群中。 [0024] 本發明之其他目的係關於可由本發明之方法所獲 得的高k閘極。 【實施方式】 [0〇29]本發明提供一種增強金屬、金屬氧化物、金屬氮化 1289330 物、金屬氮氧化物、和/或金屬碳化物層之方法，包括步驟·· >儿積该金屬、金属氧化物、金屬氮化物、金屬氣氧化物、和 /或金屬碳化物層於sixNy層上，其中χ和y為實數，其 中X等於大約3或大於3，其巾y大於Q或等於或小於大 約4，以及其中χ和y可以相等或不同β [0〇3〇]較理想之情況是，χ^3和〇<y$4。 [0031] 較理想之情況是，x/y之比例大於大約〇 ·75並可 無上限之變化’各大於（或等於）〇 ·75之值係包含本發 _ 明之範圍内。 [0032] 本發明亦提供一種用來處理（基板）表面之方法， 在製備後續之金屬、金屬氧化物、金屬氮化物、金屬氮氧化 物、和/或金屬碳化物層沉積，包括步称：沉積sixNy層於 該（基板）表面，其中χ和y為實數，其中χ等於（大約） 3或大於（大約）3，其中y大於〇或等於或小於（大約） 4 ,以及其中x和y可以相等或不同。 [〇〇33]該金屬、金屬氧化物、金屬氮化物、金屬氮氧化物、 和/或金屬碳化物係直接沉積於該sixNy層上。 I [0034]於本發明之内容說明中，sixNy層亦能稱之為、、像
Si3N4 之層（Si3N4-like layer ) f’，其中 χ 和 y 為實數， 其中χ等於（大約）3或大於（大約）3，其中y大於〇和 等於或小於（大約）4，以及其中χ和y可以相等或不同。 [0035]於本發明之内容說明中，將要處理之表面，係用於 半導艘製程之任何表面，於該等表面上金屬生長被抑制（阻 礙/妨礙）。於此文中該表面可稱之為、'化學穩定表面"、 '、（金屬生長）抑制表面"、或''困難表面"。 9 1289330 [〇〇36]該等表面能夠是任何具有非常低雜質含量之（實 質）化學計量之材料，於此表面上通常能夠觀察到抑制之薄 膜生長。例如，熱Si02和熱SiON為此等表面。 [〇〇37]用於半導體製程中之任何材料，尤其是製造金屬閘 極或用於障礙層，能夠用於本發明方法。 [0 0 3 8 ]該等金屬能夠藉由譬如減鍵之物理氣相沉積（PVD ) 製程、藉由原子層沉積(ALD)製程、藉由化學氣相沉積(CVD) 製程、藉由金屬有機化學氣相沉積（M0CVD)製程或藉由任 何其他適當的製程所沉積。 [0〇39]舉例而言，钽（Ta)、釕（Ru)、鈦（Ti)、鎮（W)、 鋁（A1)、銅（cu)、鈷（Co)、鑷（Ni)、鉬（Mo),或這 些元素中之任何二者、三者、四者、五者、六者或更多之組 合能使用於本發明方法中。 [0040]半導體裝置之速度直接比例於場效電晶體（FET) 中施加電壓後，閘極電介質之反應。閘極電介質之反應直接 比例於其電介質常數k，並反比於其厚度。因此，依於應用， 能夠高度地期望對於電介質所需之薄的（甚至是超薄的）和 高k之電介質。 [〇〇41]用於半導體製程之任何金屬氧化物，尤其是製造高 k之電介質金屬氧化物閘極，能夠用於本發明方法。 [〇〇42]能夠藉由譬如濺鍍之ρνρ製程、藉由ald製程、 藉由CVD製程、藉由M〇CVD製程或藉由任何其他適當的製 程而沉積該金屬氧化物。 [0〇43]舉例而言’可使用之金屬氧化物（具有高電介質常 數）為二氧化鈦（Ti02)、五氧化鈕（Ta205)、氧化銘 1289330 (Al2〇3 )、氧化鍅（Zr02 )、氧化鑭（La2〇3 )、氧化铪（Hf 〇2 )、 或這些物質中之二者、三者、四者或更多之組合（於多層或 多組件之形式）。再者，各範例為三氧化物，譬如氧化金屬 矽，例如氧化銃铪，尤其是氧化矽給、鈦酸鋇鳃（BST)、 鈦酸鉛鍅（PZT)、和/或矽酸鍅。 [〇〇44]依於所到達之金屬氧化物之厚度，能施行譬如 PVD、ALD、CVD或MOCVD製程之不同的製程，來沉積該 金屬氧化物於SixNy層上。 [〇〇45]於本發明之較佳:實施例中，藉由原子層沉積（ALD) 製程而沉積金屬氧化物材料。 [〇〇46]用於半導體製程之任何金屬氮化物，尤其是製造金 屬閘極，能夠用於本發明方法。 [〇〇47]能夠藉由譬如濺鍍之PVD製程、藉由ALD製程、 藉由CVD製程、藉由MOCVD製程、或藉由任何適當的製程， 而沉積該金屬氮化物。 [〇〇48]舉例而言，氮化钽（TaN)、氮化鈦（TiN)、氮化 鶴（_)、氮化鈮（NbN)、氮化翻（MoN)，或這些物質中 之任何二者、三者、四者或更多之組合，能使用於本發明之 方法。 [〇〇49]用於半導體製程之任何金屬碳化物，尤其是製造金 屬閘極，能夠用於本發明方法。 [0050]該金屬碳化物能夠是選自由碳化钽、碳化鈦、碳化 鑛、破化銳、碳化鉬、和碳化铪所組成之群中。再者，可使 用由金屬氮化物和金屬碳化物所組成之任何組合，譬如碳化 氮化鎢β 1289330 礞 [OOSl]能夠藉由譬如賤鍍之PVD製程、藉由ald製程、 藉由CVD製程、藉由MOCVD製程或鞛由任何其他適當的製 程而沉積該金屬碳化物。 [0〇52]本發明之方法可包括步驟··在沉積該金屬、金屬氧 化物、金屬氮化物、金屬氮軋化物、和/或金屬礙化物層步 驟之前，該SixNy層沉積在表面上，尤其是在譬如氧化梦層 或氮氧化石夕層之金屬生長抑制表面上。 [〇〇53]能用任何適當的製程沉積該：5:^心層，較理想之情 況是使用（熱）化學氣相沉積（CVD)製程、藉由基支援化 ® 學氣相沉積（RACVD)製程，或藉由（遠端）電漿增強化學 氣相沉積（RPECVD或PECVD)製程。 [〇〇54]用來沉積SixNy層之（熱）CVD製程最好是使用 包括至少一個矽烧和氨（NH3)之先驅物來製造。 [〇〇55]用來沉積 SixNy層之 RACVD、RPECVD 或 PECVD 製程最好是使用包括至少一個矽烷和氮基（N* )、和氨（NH3) • 之先驅物來製造。 • [0056]於本發明之方法，該矽烷能夠是選自由單矽烷 Φ (SiH4)、雙矽烷（Si2H6)、三矽烷（Si3H8)、單氣梦烷、 雙氣矽烷（DCS )、三氣矽烷（TCS )、和四氣矽烷（SiCl4， 亦稱之為氣化矽）所組成之群中。 [0057] 依照本發明之較佳方法中，氧化姶層沉積在像 3土3队之層上。 [0058] 直到本發明，在閘極堆疊應用中，沉積在化學氧化 物上之Hf〇2清楚地發現到較之沉積在熱氧化物上之Hf02 具有較好的漏電流和厚度尺寸性質。 1289330 ♦ [0059] 當使用熱氧化物下層時，在閘極堆疊内平行之时〇2 與多晶矽電極之積體發現有問題。 [0060] 此係與Hf〇2能夠在化學氧化物上生長得很好並於 熱氧化物上顯示清楚的抑制生長之事實相關。 [0061] 然而，用於Hf〇2之熱生長下層由於他們的較佳電 性而最好是在閘極堆疊應用中，如此獲得了於半導體裝置 •中之較佳載子遷移率（mobility)。 [0〇62]依照本發明之較佳方法，允許製造高品質Hf〇2薄 0膜於此等熱氧化物下層中。因此於沉積該Hf〇2層之前，處 理該熱氧化物下層，該處理包括或由沉積SixNy層步驟組 成。 [0063] 本發明之較佳方法因此包括沉積sixNy層於金屬生 長抑制表面上之步驟，連績地接著沉積Hf〇2層於該SixNy 層上之步驟。 [0064] 戎SixNy層之最小厚度大約為〇.25nm，對應具有 大約一個SixNy分子層之金屬生長抑制表面之覆蓋 • (coverage)〇 # [0065]於本發明之較佳方法中，藉由ald製程沉積氧化 給層，該ALD製程一般用來沉積奈米厚度範圍之薄膜。 [〇〇66]沉積最好施行於包括（大約）2〇〇°c至（大約）500 °<：間之溫度，較佳地是在（大約）25〇t至（大約）40〇t： 間之溫度，而尤其最理想的是在（大約）3〇〇。〇，具有前驅 物包括或由HfCl4和H20所組成。 [0067]於反應器中之壓力能包括（大約，◦•丄至（大約） 10 托（torr)之間（亦即，（大約）〇·〇〇〇1333224 巴（bar) 13 1289330 ♦ 至（大約）0.01333224巴之間），而較理想的情況是在（大 約）1托（亦即’（大約）0.001333224巴）。 [〇〇68]如第1圖中所示，Hf〇2生長增強依於像釭仇之 沉積時間，換言之，依於像Si3N4之層之厚度。 [0069] 舉例而言，具有大約4nm厚度之像灯洲之層得 到最佳Hf〇2生長性質。而亦然，大約〇 · 25nm之像Si3N4 之層之厚度已經足夠用來產生明顯之增強Hf〇2層生長。 [0070] 於此同時，成功應用於閘極堆疊上之表面處理，沉 積於不同表面之像SioN4之層並不得到閘極堆疊之電厚度 之不可接受之增加（亦稱之為相等氧化物厚度（Ε〇τ))，那 是很重要的。 [0071] 顯示沉積1〇秒鐘後材料量之xps分析（第2圖） 對應於大約〇.25nm之沉積之像si3N4薄膜厚度。如此厚度 獲得於EOT (相等氧化物厚度）之僅大約〇12nm增加。 如此顯著之生長改進能用較少之電厚度增加而達成。用大約 15秒或大約20秒之稍微較長之處理將得到分別大約 0 · 5nm和大約0 · 7nm之像si3^薄骐厚度，在可接受程度 ^内增加電厚度（EOT )限制到達大約〇·18ηιη至大約 0 · 24nm 〇 [0072] 對於相似之理由，Hf〇2層厚度最好是少於8nm , 較佳的是少於（大約）7nm，更理想的是少於（大約）5nm , (大約）4nm或（大約）3nm，和甚至更佳的是少於（大約） 2nm ° [0〇73]像SiW4之層沉積於（熱）氮氧化矽層之上，但是 亦能沉積於（熱）氧化矽層之上。 1289330 [0074] 可以使用不同之方法沉積該像si3N4之層。 [0075] 對於沉積該像si3N4之層，可施行RACVD製程， 使用包括或由至少由一種矽烧，最好是SiH4所組成之先驅 物，具有氮基和和選用之NH3。 [0076] 該氮基最好是產生於基產生器中，該基產生器位於 鄰接反應室（reactionchamber)。適當的基產生器為微 波基產生器（Microwave Radical Generator ; MRG)。
[0077] 或可選擇使用PECVD製程，其中矽烷先驅物和氮先 驅物可由電漿活化。電漿能位於反應室中或位於遠端控制。 [〇〇78]沉積該像Si3N4之層之另一稚方法能夠是熱活化 CVD製程，其中該先驅物由至少一種矽烷，最好是以^和 NH3所組成。 [0079]對於任何施行之製程，像Si3N4之層最好是於包括 (大約）400°C至（大約）800°C間之溫度，更理想的是在 包括（大約）500。(：至（大約）7〇0°C間之溫度，而尤其最 理想的是在（大約> 600。(：沉積。 [〇〇8〇]如第1圖所示，藉由RACVD製程沉積像Si3N4之 層僅10秒鐘（對應於由XPS測量之大約〇.25nm透明厚 度），而獲得Hf02生長抑制之明顯的減少。 [0081] 而沉積較大量之像si#4層（厚度大約4nm),獲 得完全免除Hf02生長抑制，如第4圖所示。 [0082] 的確，第4圖顯示當首先用siH4/N*根據基支援 CVD製程於6〇〇°c處理生長siON層之NO-RTO (RTO於 NO氣體中於looot：)時，Hf〇2之生長抑制強烈地減少， 甚至完全地免除。 15 1289330 < [0083]事實上，僅僅觀察第4圖之生長曲線（具有沉積 層之覆蓋作為ALD反應循環之次數）給予了有效基板之第 —個表示。 [〇〇84]線性生長曲線（固定生長率）通常關聯於好的薄膜 形態和快速層封閉。 [0085] 生長抑制（於第一反應循環之較低生長率）表示於 基板上先驅物之困難成核，以及浮閘生長、低薄膜品質、和 遲的層封閉之點。 [0086] 許多於相同實驗測試之熱生長SiON之其他表面處 理，譬如 SiON 於 NH3、N*、H*、N*/H*、NVNH3、或 SiH4 , 並未成功地免除生長抑制。 [0〇87]用 SiEU/NH3 CVD 製程和 SiH4/N* 或 SiHjNVNI^RACVD製程之表面處理全然能免除於化學非 常穩定之熱生長SiON表面上之生長抑制。 [0088] 有鑑於由本發明之方法所獲得的結果，能夠推論首 先很少埃（A)之Hf〇2之沉積均勻地開始於表面上之每一 個地方，而使得正好封閉之原子單層於沉積之第一階段形 Φ 成，而薄膜生長以均句方式繼續著。 [0089] 本發明之另一目的係關於可由本發明之方法所獲 得的高k閘極堆疊。 [0090] 本發明之高k閘極堆疊能夠是各層之堆疊，包括 生長抑制表面’尤其是熱Si〇2或熱SiON表面，在此表面 上沉積了像ShN4之層，在此表面上沉積了高k金屬氧化物 (封閉）之薄膜。該高k金屬氧化物封閉薄膜具有少於8nm 之厚度’較佳地具有小於（大約）7nm厚度，更較理想之情 1289330 •4 況疋小於（大約）5nm、小於（大約）4nm、或小於（大約） 3ηιπ’而尤其是最好小於（大約）2nm〇 [0091] 本發明之高k閘極堆疊亦能夠是各層之堆疊，包 括生長抑制高k電介質表面，在此表面上沉積了像Si3N4 之層’在此表面上沉積了金屬和/或金屬氮化物（封閉）之 薄膜作為閘電極。於此情況，該高k閘極層生長抑制而像氮 化物之層增強生長金屬或金屬氮化物閔電極。 [0092] 於下列實例中更詳細說明本發明，該實例僅欲作說 嫌明用，而將不以任何方式構成本發明範圍之限制。
JtM
[0093] 於第一步驟，用氫氟酸（抓）浸泡清洗碎（^) 基板。 [0094] 於該矽基板上藉由快速熱氧化作用（Rapid Thermal Oxidation)於氧化氮（NO)環境中於1〇〇〇。匸 (NO-RTO)生長熱 SiON 層。 [0095] 然後藉由從SiH4和氮基之基支援化學氣相沉積 ‘ (RACVD)以及選用之NH3先驅物之方式，或藉由使用siH4 修伴隨著·3先驅物之熱起動CVD製程之方式，於印此沉 積像Si3N4之層。 [0096] 為了具有可比較之結果，以及因為CVD製程之沉 積率與用在表1之範例製程中之RACVD製程之沉積率不 同，因此選用沉積時間而使得si#4層之厚度是在大約4nm 與大約5nm之間。 [0〇97]亦考慮於6〇〇°C之NO-RTO SiON層之其他處理。 [0098]所有之製程參數說明於表1中。 17 1289330 [0111] 120秒像SdoN4層沉積獲得線性的Hf〇2生成曲 線，該曲線相似於所觀察之ALD之Hf 〇2在lnm Si化學氧 化物之生成曲線。化學氧化物包括許多的—OH群，該等群為 容易成核之位址，結果，此氧化物不會受到抑制生長。然而 很令人感到遺憾的是，此種化學氧化物之電性品質不佳，而 使得不能用於半導體裝置構造。 : [0112]此等線性生長曲線相關於二維生長表現和好的
Hf〇2在薄膜品質。 [0113] XPS像Si3N4沉積率於600°C為2·1奈米/分 ^ (nm/minute)。因此，120秒之像Si3N4層沉積對應於 4.3nm之像Si#4層厚度，而獲得最佳Hf〇2生長性質。 [0114] 經過10秒之像Si3N4沉積，於第一週期觀察到顯 著之增強Hf〇2生長率，雖然較之120秒有較小之程度。 [0115] 事實上10秒之像Si3N4沉積已經獲得改進之Hf02 生長，對於閘極堆疊應用非常有幫助。 [0116] 對於目標訂在最小之相等氧化物厚度（E0T)之閘 極堆疊應用，像Si3N4層厚度將為最小。依照xps (第2 痛|圖），10秒之像Si3N4沉積給予約0 · 25nm之厚度，對應僅 大約0 · 12nm EOT。因此，Hf02生長改進能用最小EOT分 佈而已經達成。 [0117] 具有關於用個別之 N*、SiH4、NH3、N*+NH3、 Η★、以及N*+H★之NO-RTO處理，無像Si3N4沉積被觀察 到如由第3圖所顯示。 [0118] 橢圓計（ellipsometer)測量結果（第3圖） 表示於實際之像Si3N4沉積僅三個考慮之製程（處理）獲得 • 1289330 v 於像Si：3lSU層之沉積：siH4和N★之結合（藉由製 程）、S1H4、N★和即3之結合（藉由製程）、和 與NH3之結合（藉由（熱）⑽製程）e S1H4 [0119]於這些情況中，測量之橢圓計厚度為大約4nm至 大約5nm ’要較N〇-RTO開始層（具有大約工· 7咖之厚度） 之厚度厚。 ： [〇12〇]於不同基板上之Hf〇2生長曲線顯示_第4圖中。 [0121] 僅當像Si；3N4層沉積於NO-RTO基板上時，可觀 察到生長改進。 [0122] 藉由使用SiH4、N*和選用之即3先軀物之j^cvd 製程’和藉由使用SiHi與NH3先軀物之CVD製程所獲得的 ，各層，導致生長改進。 [0123] 不沉積像sisN4層之其他處理並不獲得於^^&生 長表現之改進。 [0124] 這些資料啟示該等於siH4/N★或以叫作出或 、SiH4 /Ν*/·3中之處理留下背後表面（behind a surface) ’該表面適合於Hf〇2生長抑制❶ 參[Q125]無任何其他的處理能夠於熱氧化物上達成此功能。 [0126] 本發明之處理，不同於其他的處理，本發明沉積一 些像氣化梦（silicon-nitride_like )之材料於熱氧化 物上’而顯然留下適合與Hf〇2沉積製程之Hfcl4/H2〇先軀 物反應之背後化學群（可能是— [0127] 然而’沉積在不同表面之像氮化石夕材料可完全與如 閘極電介質薄膜之應用相容。 [0128] 總之’於像犯办4基板上之Hf〇2生長，沉積於熱 20 1289330
SiON (MO-RTO)基板上之後者，實質上獲得改進。 [0129]熱與基支援化學氣相沉積（RACVD)像Si3N4層， 沉積於600°C，為用於Hf02 ALD之好的開始基板。 1289330 τ^
SOI SOBβ·Η目/muο。ΜΜΟΕΗ««? oldsHN dd^HTS 齋！W i ΛaHW 目Ηω (mis》 moos 日Hs ®1nHNWTS154 SJm 000〇0、0 3ο、ο Ι^ιητ 300 00-0 00-0 τϋ: 00-0 000 〇οο 000 〇οο τοο οςοί 00-0 τεο τοο 000 000 00-0 00-0 τΓΝΙοτ 00-0 00-0 03、τ 060;
009 009 009 009 009 009 009 009 0S toc: ιηιο ιοοί LOC: ςΟΤ ςς toc:
S §
S ο ο ο ο ο ο ο ς、33Η+3ΝΙο "13 SνοΪΗ ο 〇 30 ζ 30 ο ο CNI ο 〇 ο 〇 ο 〇ς οιη ο ο守 οιη II 0 13 ιη ΓΗ3 0 91 Ιο 91
+Κ+-KS ί ΡΟΗΝ + +S ε目 εκΜ十·ΚΜ-+ Wffi-Hs S-HS ★Μ SN + STS s + S-HS WH/5S NEHH/NVHαΛονπα>ο NVH αΛοαΛονπ (5U7TS 目 V PSSTS¥ T3TPS)^?F«T^"WH 丨 (υοτ-ρΗΡ-Ηΰ-ΗΝ Tmdas p-Hs)BEifqKWW^^"NEHH I -1 丨^s$ -Q>0 I -Q>us I :冢蟀枇蛉wfH^念阳寧 ττ 1289330 【圖式簡單說明】 [0025] 第1圖表示在不同之基板表面上之虹〇2之生長曲 線： -生長在NO環境於100CTC之熱siON層（NO-RTO (使用 氧化氮（NO)作為氧化作用氣體之快速熱氧化作用））， -生長在〇2環境於750°C之熱Si02層（02-RTO)， -使用SiH4和氮基之基支援化學氣相沉積（RACVD)製程 於600°C沉積Si3N4層1〇秒鐘，以及 -使用SiH4*氮基之RACVD製程於600°C沉積Si3N4層 120秒鐘。 [0026] 第2圖表示於NO-RTO基板上對於Si3N4之X射 線光電光譜（XPS)生長曲線。 [0〇27]第3圖表示藉由使用不同的先驅物之RACVD製 程、熱CVD製程對其處理後，或於氨、氮或氫中之熱或電 漿支援處理後，不同基板表面之橢圓計（ellipsometer) 測量厚度。 [0028]第4圖表示使用或不使用對該SiON層之不同的 處理，Hf02於NOHRTO SiON層上之生長曲線。 【主要元件符號說明】 23

Claims (1)

  1. Ϊ289330
    曰修(更)正替換頁 94104658 條正本 Qfi 5· 7 十、申請專利範圍：
    1· 一種增強金屬、金屬氧化物、金屬氮化物、金屬 氮氧化物、和/或金屬碳化物層之方法，包括步驟： 沉積該金屬、金屬氧化物、金屬氮化物、金屬氮氧 化物和/或金屬碳化物層於sixNy層上，其中χ和 y為實數，其中X等於大約3或大於3，其中y大 於0及等於或小於大約4,以及其中x*y可以相 等或不同。 2.如申請專利範圍第i項之方法，其中於沉積該金 屬、金屬氧化物、金屬氮化物、金屬氤氧化物和/ 或金屬碳化物層步騍之前，該sixNy層沉積於金屬 生長抑制表面上。
    3·如申請專利範圍第1項之方法，其中該金屬氧化 物係選自由氧化鈦、氧化鈕、氧化鋁、氧化锆、氧 化鑭、氧化铪（hafnium oxide )、氧化銃铪、 氧化矽铪，和這些物質中之任何二者、三者、二者 或更多個之組合所組成之群中。 4 物如:ΐ自專第2項之方法，其+該金屬氧化 物係選自由氧化欽、氧化组、氧化銘、氧化錯 者、四者 化網' 氧化給（hafnium oxide)、氧化銳給、 氧化矽給，和這些物質中之任何二者、 或更多個之組合所組成之群中。 係 和 24 1289330 一 1 1 _ I,I 月修懷)正替換頁 這些元素中之任何二者、三者、四者、五者 或更多個之組合所組成之群中。 ’、 6·如申請專利範圍第2項中之方法，其 選自由组、釕、鈇、鎮、銘、銅 边些70素中之任何二者、三者、四者、五二 或更多個之組合所组成之群中。 ^ 7 ·如申請專利範圍第1項中之方法，其 化物能夠是選自由氮化钽、氮化鈦、氮化二：化 藏、氣化顧、氣化給，和這些物質中之任何二者、 三者、四者、五者或六者之组合所组成之群中。 8·如申請專利範圍第2項中之方法 化物，選自由氣化纽、氛化欽、氮化鶴= 藏、氮化氣化給’和這些物質中之㈣二者、 三者、四者、五者或六者之組合所组成之群中。 ifr 由氮氧化鈦、氛氧化组、氣氧化 m 、氮氧化鑭、氮氧化姶、氮氧化銃铪、 ’和這些物質中之任何二者、三者、四 或更多個之組合所組成之群中。 10氧利範圍第2項中之方法’其中該金屬氛 ^夠是選自由氮氧化鈦、氮氧化鈕、氮氧化 务® &化錯、氮氧化鑭、氮氧化铪、氮氧化銳給、 給，和這些物質中之任何二者、三者、四 更多個之紐合所組成之群中· 25 1289330 ' Ik All。日修(更)正替換頁 ιι·如申請專利範圍第i項中之方法， 化物能夠是選自由碳化钽、碳化鈦、瑞：：金屬碳 鈮、碳化鉬、碳化铪，和這些物質 =、碳化 三者由：者、五者或六者之组合所組成之群ΐ者、 化物能夠是選自由碳化钽、碳化鈦、碳：：金：碳
    藏、唉化_、竣化給，和這些物質中之任何j化 三者二四者、五者或六者之组合所組成之；。、 如申請專利範圍第2項中之方法，其中該 長抑制表面係選自由氧切和氮氧切所组成^ 中。 14.如申請專利範圍第2項中之方法，其中該呂土 層係藉由化學氣相沉積（CVD)製程而沉積Ά 15·如申請專利範圍第14項之方法，其中該咖 程使用發烧和氨至少其中之一。 16·如申請專利範圍第2項中之方法，其中該s、n 層係藉由基支援化學氣相沉積（RACVD)製程、^ 漿增強化學氣相沉積（PECVD)製程，或遠端電漿 增強化學氣相沉積（RpECVD)製程來沉積。 17·如申請專利範圍第16項之方法，其中該racvd、 RPECVD、或PECVD製程使用至少一個發烧和氮基 以及選用氨。 18·如申請專利範圍第is項之方法，其中該至少一 個碎炫係選自由單梦燒、雙碎炫、三碎燒、單氣碎 燒、雙氣梦炫、三氣發炫、和四氣梦炫所纽成之群 26 1289330 - _ ‘ 曰修(吏)正替換頁 中。 I9·如申請專利範圍第I7項之方法，其中該至少一 個矽烷係選自由單矽烷、雙矽烷、三矽烷、單氣矽 烷、雙氯矽炫、三氣矽烧、和四氯矽烧所組成之群 中。 20·如申請專利範圍第1項中之方法，其中該金眉、 金屬氧化物、金屬氮化物、金屬氮氧化物和/或金 屬礙化物係由CVD製程、MOCVD製程或ALD製程 所沉積。 21·如申請專利範圍第2項中之方法，其中該金屬、 金屬氧化物、金屬氮化物、金屬氮氧化物和/或金 屬碳化物係由CVD製程、MOCVD製程或ALD製程 所沉積° 27
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