TWI233648B - Semiconductor device fabrication method - Google Patents

Semiconductor device fabrication method Download PDF

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Publication number
TWI233648B
TWI233648B TW092116648A TW92116648A TWI233648B TW I233648 B TWI233648 B TW I233648B TW 092116648 A TW092116648 A TW 092116648A TW 92116648 A TW92116648 A TW 92116648A TW I233648 B TWI233648 B TW I233648B
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Taiwan
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film
oxide film
insulating film
metal oxide
semiconductor device
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TW092116648A
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English (en)
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TW200408005A (en
Inventor
Hiroshi Shinriki
Kazumi Kubo
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Tokyo Electron Ltd
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    • H—ELECTRICITY
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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    • H01L21/28194—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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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    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
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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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Formation Of Insulating Films (AREA)
  • Insulated Gate Type Field-Effect Transistor (AREA)
  • Chemical Vapour Deposition (AREA)

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1233648 五、發明說明（1) 、【發明所屬之技術領域】 介電ί:明ΐ體係關於半導體製造裝置，尤有關於具有高 化半導體F ^所ί的high_K(高介電率）介電質膜之超精細 化千¥體裝置之製造方法。 I库Ϊ ί之超高速半導體裝置除了製程更精細化外，閘極 置：’:二:斬7達到ο·1 ^以下。一般說來，隨著半導體裝 半導其動作速度會提高，’這般非常精細化之 "中，伴隨精細化所導致之閘極長度之縮短，必 ;:卜例法則（scaling rule}，減少閘極絕緣膜之膜 仁閘極長度在〇 ·丨# m以下時，閘極絕緣膜若使用 厚气需設定在"㈣、甚至是低於卜2nm ;閘極 桎之馮J t細薄時’穿隧電流會增加，而發生無法避免閘 極之漏電流增加之情形。 尤m 提幸針：土 2 ί形’以往有將以下材料用於閘極絕緣膜之 厚作拖吊數遠超過於Si〇2膜，實際物理膜厚雖柄當 當拓+如一士 1 丨從疋閑極長度在〇· 1 //m以下之非 之閑if裝置’亦可使用10_左右之物理膜厚 情㈣’可抑制穿隨效果所導致之問極之漏電流之 中，：h將？igXK介電質膜做為閑極絕緣膜之半導體裝置 將high爾質膜直接形成於石夕基板上時，於可減ϊ 1233648 五、發明說明（2) r，S i 〇2之絕緣膜之實際膜厚方面雖然是一較理想之方 將high—κ介電質膜直接形成於矽基板上時，金屬元 由i # ^gh — K介電質膜處擴散至矽基板中，導致穿隧區域 中有載體散亂之問題。 毛^ :门牙隧區域中之載體可動性（Mob i 1 i t y )之觀點 、/ π / i K ^電質閘極氧化膜與矽基板間最好配置有1 nm 1 _至疋〇·8nm以下之非常薄之底層氧化膜。該底層 „ ^ , ^ /#右疋較厚之氧化膜，將high-K介電 貝膜做為閘極絕緣膜時之效果會被抵銷。 二、【先前技術】 圖1Α〜1C顯示的暑春义t & € m # 則被提案之具有high-K介電質閘 松、毛緣膜之+導體裝置之製造步驟。 下之ZUc所示’石夕基板11上有一非常薄、最好是1⑽以 使用仞士 ί :〇i所構成之底層氧化膜12，此氧化膜12是由 紫外光激發氧自由基(Radicai)之自由基氧化處
ZrO等合属，/圖^之f驟中，該底層氧化膜12上之Hf〇2、 化i 1 匕膜13是利用原子層沉積（ALD)法或有機金屬 化學*1相沉積（M0CVD)法所形成。 圖1A步驟中，該自士 # 90 0 ? 1ΠΠΑ97 ^ v .自由基氧化處理可使用例如特開 2 0 0 2 -1 〇 〇 6 2 7號公報所却# ^ ^ i i ^ °己载之方法。利用矽基板之紫外光 激發自由基氧化處理可忠& ^ ^ ^ m, ^ 女疋地、再現性良好地形成一相當 於2〜3層分子層之膜厘> + ^ ?nn? in〇R97 ^ 之底層氧化膜。另外使用該特開 Z (J 0 Z - 1 0 〇 6 2 7號公報所却# 丄 m W σ己栽之方法時，可將氮原子導入以
第7頁 1233648 五、發明說明（3) 此方法形成之非常薄之矽氧化膜中，而該底層氧化膜1 2亦 可使用矽酸氮化膜。 圖1 B之步驟中，該金屬氧化膜1 3之沉積可使用特開 2 0 0 2- 1 5 1 48 9號公報所記載之ALD法、或MOCVD法。
該金屬氧化膜13是被當做high-K介電質膜，為發現該 金屬氧化膜1 3做為h i gh - K介電質膜之功能，需要的是結晶 化、而非S i 02膜般之非晶質膜。因此，如圖1 C所示般，以 往是將以圖1 B步驟所獲得之構造進行熱處理，進行將金屬 氧化膜1 3結晶化之步驟。由於金屬氧化膜1 3被形成於非晶 質之底層氧化膜1 2上，當其結晶化時會成為由微結晶之集 合所構成之多結晶體，該結晶化之金屬氧化膜1 3被使用為 高速半導體裝置之hi gh_K介電質閘極絕緣膜。 誠如前述，形成於該h i gh -K介電質閘極絕緣膜1 3與石夕 基板1 1之交界之底層氧化膜1 2被要求越薄越好。該底層氧 化膜1 2之膜厚增加時，使用h i gh - K介電質閘極絕緣膜1 3之 效果會被抵銷。 另外，圖1 B之金屬氧化膜1 3之沉積步驟中，特別是使 用MOCVD法時，由於是於氧氣中進行處理，沉積時之基板 溫度較高時，該底層氧化膜12之膜厚會因為基板之氧化而 有增加之可能性。該底層氧化膜1 2之膜厚於圖丨c之結晶化 熱處理時亦會增加。 圖1 C之結晶化步驟中，除了金屬氧化膜丨3之氧化外， 該金屬氧化膜1 3中之微結晶之結晶粒會成長，當氧化膜j 3 中之結晶粒成長時，其與下方之底層氧化膜12之交界處會
1233648 五、發明說明（4) 變得不規則或不安 三、【發明内容】 為解決上述問 穎、有效之半導體 本發明更具體 緣膜之半導體裝置 極絕緣膜之結晶化 法。 另外，本發明 極絕緣膜之半導體 絕緣膜結晶化時， 膜中之金屬氧化物 本發明其次之 膜之半導體製造裝 質閘極絕緣膜之膜 本發明其次之 包含矽與氧之絕緣 有機金屬原料之化 驟等半導體裝置之 裝置之製造方法： 該金屬氧化膜於沉 藉由本發明， 化膜於沉積剛結束 定
導致閘極漏電流之增加等問題。 題’本發明之概括性課題為提供一新 裝置之製造方法。 之課題是：於具有high —K介電質閘極絕 之製造中，提供一於該h i gh-K介電質閑 時可避免底層氧化膜膜厚增加之製造方 其—人之課題是：於具有high-K介電質間 ^置之製造中，當該high-K介電質閘極 ，供一可抑制該high-K介電質閘極絕緣 微結晶之結晶粒成長之製造方法。 課題是：於具有high-κ介電質閘極絕緣 置中，提供一可有效控制該high—κ 厚之製造方法。 々、υ W〜饮丞板上形片 膑，步驟、（2)於該絕緣膜上藉由使月 f氣相沉積法進行金屬氧化膜之沉積 衣造方法中，提供一特徵如下之半導 該金屬氧化膜沉積步驟之實行 積剛結束之狀態下會成為結晶質二X f成high~K介電質閘極絕緣膜之金 時，已經是結晶質之狀態，本發明： 1233648 五、發明說明（5) 5玄金屬氧化膜之社曰 屬氧化物結晶之= 即使是結晶化步驟後，金 金屬氧化膜之沉積，底1 ::1〇nm。其次，即使進行該 加。特別是本發明在3 2膜之膜厚亦不會有實質之增 + ¾月在使用含有酉先 原料時，該金屬氣彳( mide)基之有機金屬 田乳化膜中之氮會偏析至晶界，該傯紅衣曰 界之虱被認為可抑制原子沿著晶界移動。 曰曰 細之=參照圖示針對本發明之其他課題及特徵進行更詳
四、【實施方式】 本發明之最佳實施型態 [第1實施例] 圖2顯示的是本發明所使用之M〇CV])設備2〇之構成。 如圖2所示，MOCVD裝置20具備以泵（PUMP)21進行排氣 之反應谷裔2 2 ’該反應容器2 2中設置有保持被處理基板w 之保持台22A。
圖2之MOCVD裝置20設置有將氧氣供給至該反應容器22 之管線（LINE)22a，並設置有將被保存於起泡器（Bubbler) 23A之Hf [N(C2H5)2 ]4等液體有機金屬原料透過氣相原料控制 器22b及管線22c供給至該反應容器22之原料供給系統I 。 其次，該MOCVD裝置20設置有一將被保存於瓶筒23B之Hf[N (C2H5)2]4等液體有機金屬原料透過液體流量控制器22d及氣 化器22e供給至該反應容器22之原料供給系統Π。該原料 供給系統I與原料供給系統Π間是以切換活門（VALVE) 1及
1233648 五、發明說明（6) 活門2之方式進行切換。 圖3顯示的是該原料供給季續τ之裔士 之構成。 、口系、、死丄之乱相原料控制器22b ^如圖3所示，該氣相原料控制器22b包含有負責供終紅 :ΪΑ之質Γί量控制器（以下簡稱為MFC)31、32 ,該MF⑶ 屬=Ar軋體s做載氣（Carrier Gas)供給至保存該有 屬原料之起泡器23A。 该起泡器2 3 A會形成有機金屬原料之蒸氣，該有機金 屬原料蒸氣與該MFC32所提供之Ar載氣一起被供給至濃产 感應器3 3處。 又 ^ 该浪度感應裔33針對被提供之Ar載氣之有機金屬原料 /辰度進行量測，並將結果之輸出訊號供給至控制器34。另 外，該控制器34依據規定之軟體形成對應該濃度感應器33 輸出sfL號之第1及第2控制訊號，並分別將之供給至該 MFC31及MFC32兩處。藉此可將該濃度感應器33中之載氣與 有機金屬原料之濃度比控制在規定值内。有機金屬原料之 濃度比被控制在規定範圍内之氣相原料氣體經由壓力計3 5 及活門3 6設定為規定之壓力後，再透過該管線2 2 c供給至 反應容器22。 圖4顯示的是，圖2之MOCVD裝置20中，以Hf [N(C2H5)2]4 為原料’在4 8 0 C之基板溫度下將h f 〇2膜沉積於石夕基板上 時，於使用圖2所示之原料供給系統I及原料供給系統π 之情形下之沉積速度之比較。 如圖4所示，使用原料供給系統η時，沉積時之基板
第11頁 1233648 五、發明說明（7) ----- 溫度越高、沉積速度越快；w48(rc之基板溫度進 時，可獲得每分鐘10〇11111之高量級（〇rder)之沉積速度。積以 該非常高速之沉積速度來說，要以高精度形成膜厚 nm之金屬氧化膜是非常困難的。 相對地’若系統為使用起泡器23A之原料供給系統 I旦即使!?積時之基板溫度為480 °C，亦可獲得每分鐘lnm 之量級之沉積速度，可高精度地形成非常薄之金屬氧化 ^圖員示的是，於圖2之MOCVD裝置中，使用原料供給 系、·先I日$透過管線2 2 C被供給至該反應容器2 2之氣相原 料中之Hf [Ν((：2Η5八h分壓及基板上之沉積速度兩者之關 係。但圖5之關係係將基板溫度設定在48(Γ〇時之情形。 如圖5所示，使用圖2之原料供給系統I時，基板上之
Hf Ο?膜之沉積速度會伴隨Hf L分壓之降低而減緩， 但利用圖3所示之氣相原料控制器2 2b控制
Hf[N(C2H5)2]4分壓後，可控制被處理基板w上之Hf 積速度。 2 ^儿
圖6 ,、、、員示的疋’於沉積剛結束（a s — d e p 〇 s i t e ^ )之狀態 下’以^述方式形成之Hf%膜之繞射型態（pattern)之結 果。同時圖6亦是，於氮氣中以5〇〇〜7〇〇。〇之溫度範圍内針 1以上述方式所形成之Hf〇2膜進行各種不同溫度之熱處理 時之X射線之繞射型態之結果。但圖6之實驗係於以HF洗淨 後之石夕基板表面上，以前述之特開2〇〇2 —1〇〇627號公報所 記載之方法形成〇· 8nm左右之由Si%膜或Si〇N膜所構成之底 1233648 五、發明說明（8) 層氧化膜，再於i 之π并。山t 方法形成之底層氧化膜上進行Hf 〇2膜 為原二沉id前述，削2膜之沉積是以Hf[N(c2H5)2]4 矛貝守之基板溫度設定在4 8 〇 °c。 示HfS; : Ϊ糾：使是沉積剛結束後之狀態，Hf〇2膜仍顯 i 繞射峰部（Peak)，處於結晶化之狀態。
Hf〇膜圖UC)之步驟，針對利用上述方式形成之 n ^ 1 ,'、、、處理時，Hf(m)之繞射峰部稍微升高、並展 二：曰之f;二：峰部之強度變化並不顯著，即使針對 中造進行熱處理，亦無太大變化。實.際針對膜 行沉ϋ二二之粒彳i分布進行量測之結果顯示，以480。〇進 5〇〇 °C逸—敎未之狀態下.\其平均粒徑約為4.7nm，而以 仃…、处理後之狀恶下約為8 · 5nm，以6 0 0 °c進行埶 M it慮進來’㈣2膜中幾乎沒有因為熱處理而產生粒 位赵過1 〇nffl之粒子之情形。 rJ”圖几分別顯示的是’以穿透式電子顯微鏡觀察 ^ , 2 、不久後之樣本之剖面之結果，以及同樣以穿透 式電子顯微鏡觀察將Hf〇2膜於氮氣中以7〇〇 t進行敎處理時 之剖面之結果。但圖7A、7B是以相同的比例尺(sJie)表 不。石夕基板中每個矽原子均被解析出來。 如圖7A所示，Μ膜形成後不久，Si〇2底層氧化膜大 、.勺疋i.3nm之膜厚，與初期膜厚（0 8nm)比較膜厚增加約 U·5nm 〇 相對地，以圖7B來說，Si%底層氧化膜約為〇.9nm之膜
1233648 五、發明說明（9) 厚，與圖7A之狀態比較，膜厚約增加了〇lnm。 另外，圖7C顯示的是，於膜厚約為〇8nmiSi〇N底層 氧化膜上以48CTC形成Hf〇2膜，再將之於氮氣中以5〇〇。〇進 行熱處理時之樣品之剖面之情況，可確認的是，此時之 SiON底層氧化膜之膜厚幾乎沒有增加。 藉由本發明，利用以Hf [N(C2H5 )2 ]4為原料iM0CVD法、 以481TC基板溫度進行Hf〇2膜之沉積時，即使是沉積剛結束 時亦可獲得結晶化之刚2膜’且將該方式獲得之叫膜進 行熱處理後，H f 〇2結晶並無實質之結晶粒之成長，且其下 方之底層氧化膜之膜厚實質上亦無增加。 了以獲侍上述效果的理由目前尚不明瞭，可能與原料 :於㈣2膜中被偏析至晶界，而牽制(Pin_)沿 =、ΌΒΒ0Β界移動之氧原子或以原子有關。此氮 為〇·5〜5原子％。 =顯示的是，使用以該方式在48〇 t下進行 :之刚2膜形成電容，並測量c_v特性之結果。為進行比 :48。圖C8 ::亦=示有以35° °C進行沉積之Hf〇2膜之Cl特性。 350 =12膜之沉積時，氧濃度設定為87%，而以 C進仃该Hf〇2膜之沉積時，氧濃度則設定為56% 。 所开於基板溫度480 t、氧濃度87%之條件下 度3;0。。X'之漏電流較少、Η特性較佳，而以基板溫 多6 %之條件所形成之㈣2膜之漏電流較 濃度這是因為兩者於膜中含有之不純物元素之
1233648 五、發明說明（10) "' ' - 圖9顯示的是以350〜480 °c之範圍内以種種基板溫度進 行沉積之Hf〇2膜之膜中碳濃度之結果。 如圖9所不，以56%氧濃度之條件所沉積之Hf〇2膜當中 之碳濃度在任何基板溫度下，其膜中之碳濃度均超過ΐχ 103/cm3 ;而84%氧濃度之條件下所沉積之Hf〇2膜中，特別 是以480。(：之基板溫度進行沉積時，其膜中碳濃度在ΐχ iOVon3以下，因為其對圖8之^ν特性有貢獻。圖8之^^寺 性反，以下情況：以ΗΠΝ^Η5)2]4為原料進行^〇2膜之沉積 日守，藉由於咼溫、咼氧濃度之條件下沉積，可低 留之碳濃度量。 _ 圖10顯示的是，於350〜480 t範圍内之各種基板溫度 所沉積之Hf〇2膜之膜中氮濃度之結果。 如圖10所示，以氧濃度56%之條件所沉積之“…膜 中，在任何基板溫度下，其膜中氮濃度均超過丨X丨〇3/⑽3 ; 而84% ft濃度之條件下所沉積之叫膜中，特別是以48〇它 士基板溫度進行沉積時，其膜中碳濃度在1χ Μ"-以下。 這反映以下兩件事：（丨）因為熱而使得具有以下結構式之 Hf [N(C2H5)2]4原料中之Hf_N之鍵結容易被切斷，（2)該Hf [N (C2H5)2]4原料中不含有氧。
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1233648
五、發明說明（11) 誠如上述，本發明當中，特別是以含有H f [ N (Q] 般酰胺基之有機金屬化合物為原料時，即使在膜之2沉5 ‘ k 於結晶化之狀態下進行之條件下進行金屬氧化膜之沉積疋 時，金屬氧化膜下方之底層氧化膜膜厚之增加在（一）金屬 氧化膜之沉積時及（二）針對沉積後之金屬氧化膜進行熱處 理時等兩種情況下均可被有效控制。另外，針對金屬^ = 膜進行熱處理時’膜中之結晶粒之成長會被控制，與細薄 之底層氧化膜之界面之狀態（Morph 〇 logy)會安定化。其/ 次，以咼溫、咼氧濃度之條件進行沉積時，可將膜中所含 _ 有之不純物濃度降至最低限度。 [第2實施例] 圖11 A〜11 E顯示的是本發明第2實施例之半導體裝置之 製造步驟。 如圖11 A所示，使用例如紫外光激發氧自由基 (Radical)之自由基氧化處理，或繼上述自由基氧化處理 後進行電漿自由基氮化處理時，石夕基板4 1上會形成由1 nm 以下之Si02膜或SiON膜所構成之底層氧化膜42 ;圖1B之步 驟中，利用含有Hf [N(C2H5)2]4、Hf [N(CH3)2]4、Zr[N(C2H5)2] 4、2]：^((：113)2]4等、最好是含有酰胺基之有機金屬原料之 有機金屬化學氣相沉積（MOCVD)法，在400〜600 °C之基板溫 度、8 0 °/。以上之氧濃度之條件下，類似上述之金屬氧化膜 43於結晶質狀態下沉積之型態般，Hf 02膜或Zr02等金屬氧
第16頁 1233648 五、發明說明（12) 化膜會被沉積於該底層氧化膜4 2上。 …其次，圖UC。之步驟中，卩上述方式所獲得之構造於 氮虱中、500〜700 c之溫度下接受熱處理後，該金 膜43 :被充分地結晶化。此時’ f亥金屬氧化膜43於沉積剛 ηΐ是結晶化之狀態，原料中之氮原子會被偏析至 晶界，金屬乳化膜中之結晶粒之成長會被 化膜42之殘留氧所導致之膜厚增加之情形會被抑制氏2 = 是以S:iON膜形成該底層氧化膜42之情形，可岡 、lic步驟中之底層氧化膜之膜厚增加之情；避免圖 其次，圖11D之步驟中’該金屬氧化膜43上 晶矽膜44，將之於圖11E之步驟中進行圖型化 、 ;閘極電極44A會被形成。將該閘極電極 44A以將離子（I〇n)注入至光罩之方式處理後，該矽 之該”44八兩側會形成擴散領域41A、41B。 化膜3 = t:，例’可對應閘極長度之縮短而減少底層氧 見」能= ί = 所構成之間極絕緣膜之膜厚：可實 見此以非㊉间速進行動作之半導體裝置。 以上針對本發明$ _ 明並不侷限於上述= 態進行则’但本發 行各種變形、變更。 〜而疋可於本發明之要點内進 產業上利用性 藉由本發明可達| 絕緣膜之金屬氧化下效果：構成hlgh-K介電質閘極 膜係以該金屬氧化膜剛結束沉積時已經 第17頁 1233648
五、發明說明（13) 是結晶質之型態被形成’本發明可抑制該金屬 結晶粒之成長，即使是結晶化步驟後，金屬氧化b聪中之 =徑亦不會超過10nm。另外，即使進行該金屬晶之 =層氧化暝亦不會有實質上之膜厚增沉 氮备偏把s 土 有拽金屬原料時，該金屬It仆賊士 移動之情形。 析至晶界之氮可抑制原子沿著晶界
第18頁 1233648 明 圖式簡單說明 五、【圖式簡單說 、固1 a〜1 c為顯示以往之高介電係數之閘極絕緣膜之形 成步驟的圖式。 圖2為顯示於本發明第1實施例中使用之MOCVD裝置之 構成的圖式。 圖3為將圖2之MOCVD裝置中之一部分詳細顯示的圖 式。 圖4為顯示依本發明第1實施例之H f 〇2膜之沉積速度與 基板溫度之關係的圖式。 ^ 圖5為顯示依本發明第1實施例中“仏膜之沉積速度與 亂相原料分壓之關係的圖式。 妓μ = 為顯示依本發明第1實施例所獲得之Hf %膜之X射線 繞射型態的圖式。 膜M ^ ^ Μ為顯不包含依本發明第1實施例所獲得之1^ 02 膜的樣本之剖面TEM影像的圖式。 2
特性=圖為广。不依本發明第1實施型態所獲得之Hf〇2膜之C-V ，9為顯不依本發明第丨實施型態所獲得之膜 石反）辰度的圖式。 圖10 士顯示依本發明第】實施型態所獲得之膜 中之氮濃度的圖式。 A二】1為說明依本發明第2實施例之半導體裝置之 I le步驟的圖式。
1233648 圖式簡單說明 元件符號說明： 11 矽基板 12 氧化膜 13 金屬氧化膜 20 MOCVD裝置 21 泵 22 反應容器 22A 保持台 22a 管線 22b 氣相原料控制 器 22c 管線 22d 液體流量控制 器 22e 氣化器 23A 起泡器 23B 瓶筒 31 ^ 32 質量流量控制 器 33 濃度感應器 34 控制器 35 壓力計 36 活門 41 矽基板 42 底層氧化膜 43 金屬氧化膜 44 多晶石夕膜
第20頁 1233648 圖式簡單說明 4 4 A 閘極電極 1111 第21頁

Claims (1)

  1. '1 gj昏· 11月 ΐ 0日 I 案號 92116648 六、申請專利範圍 1 . 一種半導體裝置之閘極絕緣膜的形成方法，包含如下步 驟： 於基板上形成底層絕緣膜之步驟；及 '藉由使用含有氮之有機金屬原料的化學氣相沉積法， 於該絕緣膜上沉積金屬氧化膜之步驟； 其中， 該金屬氧化膜沉積步驟是以該金屬氧化膜剛結束沉積 之狀悲係為結晶質且含有既定濃度的氛之方式來進行的。
    2. —種半導體裝置之閘極絕緣膜的形成方法，包含如下步 驟： 於基板上形成底層絕緣膜之步驟；及 藉由使用含有氮之有機金屬原料的化學氣相沉積法 於，該絕緣膜上沉積金屬氧化膜之步驟； 其中： 該金屬氧化膜沉積步驟是以該金屬氧化膜剛結束沉積 之狀態係為結晶質且含有既定濃度的氮之方式，並在該底 層絕緣膜實質上膜厚不會增大的溫度下來進行的。
    3.如申請專利範圍第1項之半導體裝置之閘極絕緣膜的形成 方法，其中該金屬氧化膜包含Hf或Zr之其中之一元素。 4.如申請專利範圍第2項之半導體裝置之閘極絕緣膜的形成
    第22頁 _3_圳 年月曰 修正 9次：：U.:月]:案號 92116648 六、申請專利範圍 方法，其中該金屬氧化膜包含Hf或Zr之其中之一元素。 5 ·如申請專利範圍第1項或第4項之半導體裝置之閘極絕緣 膜的形成方法’其中該金屬氧化膜之沉積步驟係在4 Q Q〜β 〇 〇 °c之基板溫度進行。 6_如申請專利範圍第1項或第4項之半導體裝置之閘極絕緣 膜的形成方法，其中該有機金屬原料包含酰胺（Amide)基。 7 ·如申請專利範圍第1項或第4項之半導體裝置之閘極絕緣 膜的形成方法，其中該有機金屬原料係選自於由Hf[N((：2H5) 2]4、ΙΠ[Μ((：ίΙ3)2]4、Zit[N(C2H5)2]4、Zr[N(CH3)2]4 等所構成之 群組。 8 ·如申明專利範圍第丨項或第4項之半導體裝置之閘極絕緣 膜的形成方法’其中該有機金屬原料係由保存液體原料之 起泡所供給。 9:如申凊專利範圍第丨項或第4項之半導體裝置之閘極絕緣 膜的形成方法，其中該金屬氧化膜沉積步驟係於含氧之環 境中進行。 ' 1〇·如申請專利範圍第1項或第4項之半導體裝置之閘極絕緣 膜的形成方法’其中該金屬膜沉積步驟係於氧濃度超過8 〇
    第23頁 1233細 r ill 案號 92116648_年月日_«_ 六、申請專利範圍 %之環境中進行。 11.如申請專利範圍第1項或第4項之半導體裝置之閘極絕緣 膜的形成方法，其中該金屬氧化膜係由於沉積剛結束後之 狀態下為1 Onm以下粒徑之微結晶所構成。
    1 2.如申請專利範圍第1項或第4項之半導體裝置之閘極絕緣 膜的形成方法，其中，更包含將所沉積之該金屬氧化膜施 以熱處理之步驟，該金屬氧化膜係由於熱處理後之狀態下 成1 0 n m以下粒徑之微結晶所構成。 1 3.如申請專利範圍第1項或第4項之半導體裝置之閘極絕緣 膜的形成方法，其中該金屬氧化膜含有5原子％以下範圍之 氮。
    第24頁
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