TWI390675B - A gate insulating film forming method, a semiconductor device, and a computer recording medium - Google Patents

A gate insulating film forming method, a semiconductor device, and a computer recording medium Download PDF

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TWI390675B
TWI390675B TW094137895A TW94137895A TWI390675B TW I390675 B TWI390675 B TW I390675B TW 094137895 A TW094137895 A TW 094137895A TW 94137895 A TW94137895 A TW 94137895A TW I390675 B TWI390675 B TW I390675B
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plasma
insulating film
gate insulating
nitriding treatment
processing
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TW200620565A (en
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Tatsuo Nishita
Shuuichi Ishizuka
Yutaka Fujino
Toshio Nakanishi
Yoshihiro Sato
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Tokyo Electron Ltd
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Description

閘絕緣膜之形成方法、半導體裝置及電腦記錄媒體
本發明係關於半導體裝置之閘絕緣膜之形成方法、半導體裝置及電腦記錄媒體。
於以矽氧化膜作為閘絕緣膜的半導體裝置中,為防止所謂「硼穿透現象」,亦即閘極中之硼將矽氧化膜所構成之閘絕緣膜穿透而到達基板之現象,而對於矽氧化膜,藉由電漿來進行氮化處理,其後再進行急速熱回火(Anneal)處理(專利文獻1)。
專利文獻:日本特開2004-48001號公報然而,前述以往之技術矽關於MOSFET之技術,而須有另外的回火處理來作為後續處理。然而,若進行回火處理,則有因而使膜之厚度增大之虞。因此,縱使對構成其他半導體裝置,例如DRAM(Dynamic Random Access Memory)之閘絕緣膜的氧化膜進行電漿氮化處理,亦以一面可謀求硼穿透現象之防止,一面又不需要其後之回火處理之技術,較為理想。並且,此際亦必須留意使裝置之驅動能力下降的原因,亦即氧化膜中的氮濃度。
鑑於上述問題點,本發明之目的在於,一方面防止閘絕緣膜中之硼穿透現象,一方面又不需要電漿氮化處理後的回火處理,且抑制裝置之驅動能力的下降。
為達成上述目的,本發明之閘絕緣膜之形成方法之特徵為,對於構成前述絕緣膜的氧化膜,將氬氣與氮氣予以電漿化而施以電漿氧化處理之際,依使用了平板天線之微波電漿來進行電漿氮化處理;並且,依前述電漿氮化處理,使閘絕緣膜之氧化膜中之氮濃度為5~20%原子濃度。
於使用了前述平板天線之微波電漿氮化處理中,電漿處理之際用來作為處理氣體的氬氣與氮氣之流量比為2:1~30:1;較佳為2.5:1~25:1最佳為;2.5:1~5:1更佳。
依本發明,則依據使用了平板天線之微波電漿來進行電漿氮化處理,可實現低電子溫度且高密度之電漿氮化處理;縱使不進行回火處理,亦可有效防止例如DRAM中之硼穿透現象。並且亦可抑制裝置之驅動能力下降的原因,亦即膜中之捕捉阱(Trap)。前述平板天線上亦可形成多數的透孔。
又,前述電漿氮化處理可具有:將基板搬入處理容器內之工程;和其後,對處理容器內進行真空抽取,以除去處理容器內之殘留氧氣之工程;和其後,將前述基板加熱之工程;和其後,將氮化處理所必須之處理氣體導入處理容器內之工程;和其後,在處理容器內產生電漿,而進行電漿氮化處理之工程。
並且,於本發明中,於進行電漿氮化處理之際,可控制處理壓力與處理時間,來將閘絕緣膜中之氮濃度控制在一定濃度。
依電漿處理裝置來實行這些方法時,可將其以控制裝置進行控制所需之軟體的形式,儲存於電腦記錄媒體。
又,依本發明之另一觀點,則本發明,係於基板上使由氧氮化膜所構成之閘絕緣膜介於中間地具備閘極之半導體裝置,其特徵為:前述閘絕緣膜,係依使用了形成多數透孔之平板天線的微波電漿,以對氧化膜進行電漿氮化處理之氧氮化膜;且閘絕緣膜中之氮濃度為5~20%原子濃度。
依上述構成之半導體裝置,則可有效防止閘絕緣膜中之硼穿透現象,且可抑制裝置之驅動能力的下降原因,亦即膜中的捕捉阱。
依本發明,則一方面可防止半導體裝置中之硼穿透現象,一方面又不需要電漿氮化處理後的回火處理,且抑制裝置之驅動能力的下降。
以下說明本發明之實施形態。第1圖係表示,將本實施形態中之閘絕緣膜的形成方法予以實施所需之電漿處理裝置1的縱斷面;此一電漿處理裝置1係由例如鋁所構成,其並具備上部開口之有底圓筒狀處理容器2。處理容器2係被接地。此處理容器2之底部上,設有載具3,以作為載放台;此載放台係用於載放作為基板之例如半導體晶圓(以下稱晶圓)W。此載具3係由例如氮化鋁而構成;其內部設有加熱器4a。加熱器4a可以例如電阻體而構成,因設於處理容器2之外部的交流電源4所供給之電力而發熱,而可將載具3上之晶圓加熱至特定溫度。
處理容器2之底部上,設有排氣管12,其係依真空幫浦等排氣裝置11而將處理容器2內之周圍氣體予以排除所需。又,處理容器2之側壁上,設有氣體導入部13,其係供給由處理氣體供應源而來的處理氣體所需。於本實施形態中,處理氣體供應源方面,準備了氬氣供應源15、氮氣供應源16;其透過分別之閥(Valve)15a、16a,質量流量(Mass flow)控制器15b、16b,以及閥15c、16c,而連接至氣體導入部13。
處理容器2之上部開口上,透過確保氣密性所需之O型環(O-ring)等密封材料14,而設有例如由石英玻璃等介電體所構成之透過窗20。不使用石英玻璃,而代之以其他介電體材料,例如AlN、Al2 O3 、藍寶石(Sapphire)、SiN、陶瓷(Ceramics)等,亦無不可。依此透過窗20,於處理容器2內形成處理空間S。透過窗20之平面形態係圓形。
透過窗20之上方設有天線構件、例如圓板狀之平面縫隙天線(Slot Antenna)30;並且,於此縫隙天線30之上面上,設有介電體之緩波板31、以及覆蓋在緩波板31上之鋁等金屬製之天線蓋32。天線蓋32上設有將透過窗20、縫隙天線30等予以冷卻之冷卻部。縫隙天線30係由具有導電性之材質,例如銅、鋁等金屬導電體薄圓板或多角形板而構成;其表面上被鍍上金或銀。並且,縫隙天線30上,形成作為透孔之多數狹縫33,且排列為例如渦卷狀或同心圓狀。透孔之形狀本身並無限制,可使用各種形態之孔。
具有導電性之材質,例如金屬等導電體所構成之內側導體35a被連接至縫隙天線30之中心。內側導體35a之端部的縫隙天線30側係形成圓錐形(喇叭狀)34,目的在於使微波有效率地傳播至縫隙天線30。此內側導體35a、與位於該外側之外管35b,構成同軸導波管35。而,於微波供給裝置36所產生之例如2.45GHz之微波係透過矩形導波管38、負荷整合器37、同軸導波管35、緩波板31,而被傳播至縫隙天線30,再透過狹縫33、透過窗20而被供給至處理容器2內。然後,因該能量,而於處理容器2內之透過窗20之下面形成電磁場,而將依氣體導入部13而被供給至處理容器2內之處理氣體均一地電漿化,再對載具3上之晶圓W進行均一之電漿處理,例如進行電漿氮化處理。
又,處理容器2之側壁5之上方,前述氣體導入部13之下方處,水平地配置了沖淋板(Shower Plate)51。此沖淋板51係由介電體,例如石英材料所構成;且多數之透孔52在其面內均一地形成。依此沖淋板51,處理容器2內之處理空間被區分為上方處理空間S1、與下方處理空間S2。且依此沖淋板51,可捕捉(Trap)上方處理空間S1所產生之離子而僅讓游離基(Radical)通過。依此,可抑制離子轟擊效應(Ion Damage)。
處理容器2之內壁表面上設有石英內襯(Liner)39,於處理容器2內產生電漿之際,依據離子等之濺鍍,而防止從處理容器2之內壁表面產生金屬污染(Metal Contamination),以在處理容器2內形成乾淨的環境。依此,則不會有不純物質混入裝置,而可對基板進行氮化處理。
具有上述構成之電漿處理裝置1被控制裝置71所控制。控制裝置71具有中央處理裝置72、支撐電路73、以及含有相關之控制軟體的記憶媒體74。此一控制裝置71係控制自噴嘴13之氣體的供給、停止、流量調整,加熱器4a之溫度調節,排氣裝置11之排氣,以及微波供給裝置36等,以進行於電漿處理裝置1中,實施電漿處理之各流程中所必要的控制。
控制裝置71之中央處理裝置72可是用一般電腦的處理器。記憶媒體74可使用例如RAM、ROM、磁碟片、硬碟、MO、DVD等各種形式之記憶媒體。又,支撐電路73為了以各種方法來支撐處理器,而與中央處理裝置72連接。
電漿處理裝置1具有以上之構成;其對於依其他氧化處理裝置而在表面上形成矽氧化膜之晶圓W,進行電漿氮化處理之際,將晶圓W載放於處理容器2內之載具3上,而一面從氣體導入部13,將特定處理氣體,例如氬氣/氮氣之混合氣體供給至處理容器2內,另一方面則由排氣管12進行排氣,以將處理空間S內設定為特定之壓力。然後,以加熱器4a來將晶圓W加熱至特定溫度,再依微波供給裝置36來產生微波,並使透過窗20之下方的處理空間S內產生電磁場,再依將前述處理氣體予以電漿化,來對晶圓W上之矽氧化膜進行電漿氮化處理。而且,因透過細縫天線30之微波的能量所產生之處理氣體的電漿乃係低電子溫度而高密度之電漿;於此電漿下,可對晶圓W全體進行均一的電漿氮化處理,而沒有向晶圓之電漿損壞(Plasma Damage)。
以下基於第2圖、第3圖而詳述前述電漿氮化處理的處理過程;將晶圓W運入處理容器2內,並載放於載具3上(步驟S1)。然後,依排氣裝置11之動作來對處理容器2內進行真空抽取,以除去處理容器2內的殘留氧氣(步驟S2)。其後,依加熱器4a來將晶圓W加熱至特定溫度(步驟S3)。然後,從氣體導入部13將處理氣體,亦即氬氣與氮氣,導入處理容器2內(步驟S4)。使微波供給裝置36動作,以將處理容器2內之處理氣體予以電漿化(步驟S5);並進行特定之電漿氮化處理(步驟S6)。
電漿氮化處理後,則如第3(A)圖所示之於基板81上形成之係氧化膜82會如第3(B)圖所示,被因電漿而產生之氮游離基所氮化,其結果如第3(C)圖所示,可於例如係氧化膜82之表面側上進行氮濃度高之氮化處理。又,可依對壓力與時間之控制,來正確地控制氮濃度。
然後,於經過特定處理時間後,停止供給微波以停止電漿(步驟S7)。接著停止處理氣體之供給(步驟S8)。依排氣裝置11而對處理容器2內進行真空抽取,以排除殘留氣體等(步驟S9);然後,將晶圓W從處理容器2運出(步驟S10)。
其中,電漿之理想範圍係,將電漿之電子溫度控制在2eV以下,若能在0.7eV~1.5eV則更佳。又,電漿密度應控制在101 1 ~101 3 cm 3
處理空間S內之壓力應在1~66.65Pa,若能在7~12Pa則更佳;晶圓W之溫度應在100~600℃,若能在200℃~400℃則更佳;微波供給裝置36之功率輸出應在500~5000W,若能在1000~2000W則更佳。
第4圖係基於上述之電漿氮化處理之際的配方(Recipe)之一例的表格。首先,於加熱晶圓W之步驟中,以流量2000SCCM來將氬氣供給至處理容器2內,並將處理容器2內之壓力調整至126.66Pa,而將晶圓W加熱70秒。
其次,於電漿著點火(產生)步驟中,將處理容器2內之壓力調整為例如126.66Pa,若能在氮化處理壓力以上則更好;而電漿著點火用之氣體,例如氬氣之流量則調整為2000SCCM,若能在氮化處理時之流量以上則更好;並將微波之功率以2000W供給至縫隙天線30。依此,此步驟中,較氮化處理之際的壓力為高,且氬氣的流量亦較多,則不但可使電漿容易著點火,同時還可安定地產生電漿。此處理係於例如5秒間進行完成,只要在1~10秒間均可。電漿著點火用氣體亦可使用Kr、Xe、He等其他稀有氣體。
接著使處理容器2內之壓力下降至6.7Pa,並將氬氣的流量減為1000SCCM,並使電漿用之功率下降為1500W。此階段中,調整氮化處理條件,以求安定化。此處理在5秒間進行完成。
然後,使處理容器2內之壓力維持在6.7Pa,並將氬氣的流量維持在1000SCCM,並使電漿用之功率維持在1500W,而使氮氣以40SCCM流動,以於特定時間內進行電漿氮化處理。氮化處理後,將微波關閉,並停止供給氬氣與氮氣,並對處理容器2內進行真空抽取。氮化處理工程中之氣體流量方面,氬氣以500~3000SCCM為佳;氮氣以5~1000SCCM為佳。又,氮氣/氬氣之流量比以0.0016~2為佳;相對於全部氣體流量之氮氣之比則係,以全部氣體流量為1時,0.0016~0.67為佳。
以下說明,形成第5圖所示之DRAM40之閘絕緣膜41之際,對於構成閘絕緣膜41之矽氧化膜,依本發明之方法而進行電漿氮化處理之際的裝置特性等。而,第5圖中,42係閘極,43係矽基板,44係電容部。
第6圖係表示,依本發明而進行電漿氮化處理所得閘絕緣膜41中之氮的原子濃度(Atomic%),與△D(膜中之Vt 閾值開始變動之際的捕捉阱數/cm2 )的關係;亦表示改變作為處理氣體之氬氣與氮氣之流量、與處理空間S之壓力而加以實施之情形下的資料。氮化處理條件係,氬氣/氮氣之流量為500~3000/5~1000(SCCM);壓力為1~66.65Pa;晶圓W之溫度全部均為400℃;微波供給裝置36之功率為2000W。
依此,若將氮之原子濃度(Atomic%)調整為12.5~20%,則可將△D抑制再1.0E+12以下,而可確定,對於膜中之電子捕捉阱的增加之抑制,於該當範圍中係最大。而,此時之矽氧化膜的膜厚為21~40埃(Angstrom)。
而,第7圖係表示,此時之氮原子濃度在膜的深度方向上的濃度分布。第7圖係表示前述閘絕緣膜41中之深度方向上的氮原子濃度(Atomic%)的SIMS資料。由此資料可知,高濃度之氮的高峰係在閘絕緣膜之表面側(電極側)上。此係導因於低溫度且可控制表面側上之氮分布之電漿處理。又,可進行氮幾乎不擴散之界面之界面控制氮化處理。依此,洩漏電流之防止效果高,而可確定,對於硼穿透之防止,亦有相當高之效果。
甚且,依據控制電漿氮化處理之際的壓力與處理時間,可控制絕緣膜中之氮濃度。第8圖表示發明者所檢證之結果。
作為對象之絕緣膜,係依於水蒸汽中之熱處理所形成之厚度3nm的矽氧化膜(依WVG:Water Vapor Generation法所形成之熱氧化膜)。又,電漿氮化處理之際的條件係:(1)處理容器2內之壓力為12Pa之時Ar/N2 =1000/200cc微波功率:1200W晶圓溫度:400℃(2)處理容器2內之壓力為45Pa之時Ar/N2 =1000/200cc微波功率:1800W晶圓溫度:400℃
以上述條件來對晶圓進行電漿氮化處理,處理時間與氮化處理後之矽氧化膜中的氮濃度之關係則如第8圖之曲線圖所示。依此,處理壓力為12Pa、處理時間為5秒、15秒、40秒之時,氮濃度分別為8.85、14.67、19.95(原子%)。又,處理壓力為45Pa、處理時間為15秒、35秒、110秒、250秒之時,氮濃度分別為7.74、10.90、15.77、20.02(原子%)。
依此,於處理壓力為12Pa時,短時間內氮濃度增高;而於45Pa時,則須花較多時間。例如,達到約20(原子%)之氮濃度,45Pa之時所需時間約為12Pa之時的六倍。此係因為,低壓時的離子密度較高,電子的移動速度較快,使得較多的氮離子被游離基加速而被導入氧化膜中,而相對於此,高壓時的離子密度較低,電子移動速度較慢,使得氮離子被導入氧化膜中的量較低壓時為少之故。
從而,適當調整電漿氮化處理之際的處理時間、處理壓力,則可正確地控制被氮化處理之氧化膜中的氮濃度。亦即,處理時間方面在1~280秒,處理壓力方面則在1~66.65Pa之間作調整,依此可將氮濃度在1~30原子%濃度之範圍內進行控制。
而,將絕緣膜中之氮濃度作最適當的控制,可防止從基板而來的摻雜物(Dopant)穿透,而提升裝置特性。
又,將半導體裝置之閘絕緣膜予以氮化之時,雖然DRAM與邏輯裝置之閘絕緣膜已可薄膜化,但薄膜化之後,依以往技術則於進行氮化之際,氮會擴散至Si/SiON界面,而無法控制界面的粗糙現象,固有洩漏電流變高的問題。關於此點,若依本發明,則如前所述,可使氮不會擴散至界面,而將高濃度之氮導入表面側。從而,由此點亦可抑制裝置能力之下降。
並且,於前述電漿處理裝置1中,雖採用沖淋板51,而使離子被捕捉,僅讓游離基通過;而依發明者所見可知,採用此種沖淋板51,有助於將高濃度之氮導入表面側。
首先,第9圖係表示,例如將微波功率設為2kW,氬氣/氮氣流量設為1000/40sccm,晶圓W之溫度設為400℃,而於10秒~20秒間進行電漿氮化處理,以使氧化膜中之氮濃度為11%(原子%)之時的,處理容器2內之壓力與電漿電位-浮動電位(Vp-Vf)的關係,分別在無沖淋板51與有沖淋板51之時的情形。而,若將電漿鞘(Plasma sheath)電位設定在3.0~3.5(V)之範圍內,則於沒有沖淋板51之時,將處理容器2內之壓力設定為約950mTorr;而於有沖淋板51之時,則將處理容器2內之壓力設定為約50mTorr。此時,由於將SiO2 膜加以氮化而產生SiN之際,Si-N結合之能量為3.5eV,故而,若係高於此之能量,則會將所產生之SiN再度切斷,所以,電漿鞘電位最好能較SiN結合能量亦即3.5eV為低。
於此,為使沒有沖淋板51時以及有之時,二者的電漿電位之條件相同,故而,於沒有沖淋板51之時,將處理容器2內之壓力設定為約950mTorr,而於有沖淋板51之時,則將處理容器2內之壓力設定為約50mTorr;並分別以下述共通條件來對晶圓W之氧化膜進行電漿氮化處理,並依絕緣膜的深度方向來調查各情形下絕緣膜中之SiO與SiN之比例。
氬氣/氮氣流量:1000/40sccm微波功率:1500W晶圓溫度:400℃
於沒有沖淋板51之情形,如第10圖所示之結果。第10圖係表示依電漿氮化處理而形成之閘絕緣膜之深度方向上的SiO與SiN之比例。從而,二者合起來為100%。依此,從絕緣膜的表面起約0.9nm為止,SiN之比例約為35%,亦即約為SiO之一半。
相對於此,於有沖淋板51之情形,則如第11圖所示之結果。依此,從絕緣膜之表面起約0.2~0.4nm為止,SiN之比例約為40%,亦即可得到表面側之SiN的比例比沒有沖淋板51之時更高的特性。亦即,較沒有沖淋板51之時,更能將高濃度氮導入表面側。
而,本發明亦可適用於堆疊(Stack)型細胞構造之半導體裝置、快閃記憶體(Flash memory)等之邏輯裝置之絕緣膜。而若係DRAM,則氮濃度以10~20%原子濃度、氧化膜厚度以20~40埃為佳;若係邏輯裝置,則氮濃度以5~15%原子濃度、氧化膜厚度以10~20埃為佳。而,以上之例中,雖係使用熱氧化膜作為絕緣膜,但亦可使用,以前述電漿處理裝置1產生氬氣與氧氣之混合氣體的電漿,而將Si基板予以氧化所形成之氧化膜,或以其他電漿,例如ECR電漿、磁控(Magnetron)電漿、ICP電漿、平行平板型電漿、表面反射波電漿等之電漿裝置來進行電漿氧化所形成之氧化膜,來進行電漿氮化處理。又,電漿氧化處理之際的電漿源方面,除了前述實施形態中之微波電漿之外,亦可使用例如ECR電漿、磁控電漿、ICP電漿、平行平板型電漿、表面反射波電漿等各種電漿。
[產業上的可利用性]
本發明可用於半導體裝置之閘絕緣膜的氮化處理。
1...電漿處理裝置
2...處理容器
3...載具(Susceptor)
20...透過窗
30...縫隙天線(Slot Antenna)
33...狹縫(Slit)
36...微波供給裝置
W...晶圓
第1圖係將實施形態中之相關方法予以實施所需之電漿處理裝置的縱斷面說明圖。
第2圖係實施形態中之電漿氮化處理的流程圖。
第3圖係對矽氧化膜進行電漿氮化處理之際的矽氧化膜的情形之說明圖。
第4圖係電漿氮化處理之配方之一例的表格。
第5圖係實施形態中之DRAM之構造的概略說明圖。
第6圖係依本發明而形成之絕緣膜之氮的原子濃度(Atomic%)與△D之關係的曲線圖。
第7圖係依本發明而形成之絕緣膜中的深度方向上之氮原子濃度的曲線圖。
第8圖係於電漿氮化處理之際改變處理壓力之時,處理時間與矽氧化膜中之氮濃度之間的關係的曲線圖。
第9圖係因沖淋板之有無所致之壓力-電漿電位之關係的曲線圖。
第10圖係無沖淋板之時,絕緣膜之深度方向上之SiO與SiN之比例的曲線圖。
第11圖係有沖淋板之時,絕緣膜之深度方向上之SiO與SiN之比例的曲線圖。

Claims (10)

  1. 一種閘絕緣膜之形成方法,其特徵為:對於構成前述絕緣膜的氧化膜,將氬氣與氮氣予以電漿化而施以電漿氮化處理之際,依使用了平板天線之微波電漿來進行電漿氮化處理;並且依前述電漿氮化處理,將閘絕緣膜中之氮濃度,以5~20%原子濃度導入氧化膜中;前述電漿氮化處理具有:將基板搬入處理容器內之工程;和其後,對處理容器內進行真空抽取,以除去處理容器內之殘留氧氣之工程;和其後,將前述基板加熱之工程;和其後,將氮化處理所必須之處理氣體導入處理容器內之工程;和其後,在處理容器內產生電漿,而進行電漿氮化處理之工程;於在處理容器內產生電漿而進行電漿氮化處理之工程中,具有不但使處理容器內之壓力較氮化處理之際的壓力為高,同時還使氬氣之流量也較氮化處理之時為多,而使電漿點火之工程。
  2. 如申請專利範圍第1項所記載之閘絕緣膜之形成 方法,其中:前述氧化膜之膜厚為10~40埃(Angstrom)。
  3. 如申請專利範圍第1項所記載之閘絕緣膜之形成方法,其中:氬氣與氮氣之流量比為2:1~30:1。
  4. 如申請專利範圍第1項所記載之閘絕緣膜之形成方法,其中:於進行電漿氮化處理之際,控制處理壓力與處理時間,來將閘絕緣膜中之氮濃度控制在一定濃度。
  5. 如申請專利範圍第1項所記載之閘絕緣膜之形成方法,其中:前述平板天線上,形成多數透孔。
  6. 如申請專利範圍第1項所記載之閘絕緣膜之形成方法,其中:電漿氮化處理之際的壓力為1~66.65Pa。
  7. 一種半導體裝置,係於基板上使由氧氮化膜所構成之閘絕緣膜介於中間地具備閘極之半導體裝置,其特徵為:前述閘絕緣膜,係利用如申請專利範圍第1項所記載之閘絕緣膜之形成方法,以對氧化膜進行電漿氮化處理之氧氮化膜。
  8. 如申請專利範圍第7項所記載之半導體裝置,其中:前述半導體裝置係DRAM;且 前述氮濃度為10~20%原子濃度,而前述氧化膜之膜厚為20~40埃。
  9. 如申請專利範圍第7項所記載之半導體裝置,其中:前述半導體裝置係邏輯裝置;且前述氮濃度為5~10%原子濃度,而前述氧化膜之膜厚為10~20埃。
  10. 一種電腦記錄媒體,係含有使閘絕緣膜之形成方法在電漿處理裝置中實行所需之軟體的電腦記錄媒體,其特徵為:前述閘絕緣膜之形成方法係對於構成前述絕緣膜之氧化膜,將氬氣與氮氣予以電漿化而施以電漿氮化處理之際,依使用了平板天線之微波電漿來進行電漿氮化處理;並且依前述電漿氮化處理,將閘絕緣膜中之氮濃度,以5~20%原子濃度導入氧化膜中;前述電漿氮化處理具有:將基板搬入處理容器內之工程;和其後,對處理容器內進行真空抽取,以除去處理容器內之殘留氧氣之工程;和其後,將前述基板加熱之工程;和其後,將氮化處理所必須之處理氣體導入處理容器內之工程;和其後,在處理容器內產生電漿,而進行電漿氮化處理 之工程;於在處理容器內產生電漿而進行電漿氮化處理之工程中,具有不但使處理容器內之壓力較氮化處理之際的壓力為高,同時還使氬氣之流量也較氮化處理之時為多,而使電漿點火之工程。
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Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200511430A (en) * 2003-05-29 2005-03-16 Tokyo Electron Ltd Plasma processing apparatus and plasma processing method
CN1926670B (zh) * 2004-03-03 2011-05-18 东京毅力科创株式会社 等离子体处理方法
JP2006186245A (ja) * 2004-12-28 2006-07-13 Tokyo Electron Ltd トンネル酸化膜の窒化処理方法、不揮発性メモリ素子の製造方法および不揮発性メモリ素子、ならびにコンピュータプログラムおよび記録媒体
JP4864661B2 (ja) * 2006-11-22 2012-02-01 東京エレクトロン株式会社 太陽電池の製造方法及び太陽電池の製造装置
US8404135B2 (en) * 2008-08-26 2013-03-26 Taiwan Semiconductor Manufacturing Co., Ltd. Plasma cleaning for process chamber component refurbishment
JP2012069674A (ja) * 2010-09-22 2012-04-05 Hitachi Kokusai Electric Inc 半導体装置の製造方法及び基板処理装置
JP6344639B2 (ja) * 2011-05-09 2018-06-20 学校法人トヨタ学園 窒化処理方法及び窒化処理装置
DK2720862T3 (en) 2011-06-17 2016-09-19 Fiberweb Inc Vapor permeable, water impervious TOTAL MAJOR MULTI-LAYER ARTICLE
EP2723568B1 (en) 2011-06-23 2017-09-27 Fiberweb, LLC Vapor permeable, substantially water impermeable multilayer article
US9765459B2 (en) 2011-06-24 2017-09-19 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
TW201400173A (zh) * 2012-06-27 2014-01-01 Ascend Top Entpr Co Ltd 絕緣膜之黏貼設備及其黏貼方法
CN107275339B (zh) * 2017-04-20 2020-06-12 惠科股份有限公司 主动开关阵列基板及制造方法与应用的显示面板
US20180308876A1 (en) * 2017-04-20 2018-10-25 HKC Corporation Limited Active switch array substrate, manufacturing method therefor, and display panel using the same
JP2022112423A (ja) * 2021-01-21 2022-08-02 東京エレクトロン株式会社 プラズマ処理装置

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6136654A (en) 1996-06-07 2000-10-24 Texas Instruments Incorporated Method of forming thin silicon nitride or silicon oxynitride gate dielectrics
US6110842A (en) 1996-06-07 2000-08-29 Texas Instruments Incorporated Method of forming multiple gate oxide thicknesses using high density plasma nitridation
EP0847079A3 (en) 1996-12-05 1999-11-03 Texas Instruments Incorporated Method of manufacturing an MIS electrode
JP4255563B2 (ja) * 1999-04-05 2009-04-15 東京エレクトロン株式会社 半導体製造方法及び半導体製造装置
US6450116B1 (en) 1999-04-22 2002-09-17 Applied Materials, Inc. Apparatus for exposing a substrate to plasma radicals
JP2001015505A (ja) * 1999-07-01 2001-01-19 Sony Corp 絶縁膜の形成方法及び半導体装置の製造方法
JP2002170825A (ja) * 2000-11-30 2002-06-14 Nec Corp 半導体装置及びmis型半導体装置並びにその製造方法
JP5068402B2 (ja) 2000-12-28 2012-11-07 公益財団法人国際科学振興財団 誘電体膜およびその形成方法、半導体装置、不揮発性半導体メモリ装置、および半導体装置の製造方法
CN101399198A (zh) 2001-01-22 2009-04-01 东京毅力科创株式会社 电子器件材料的制造方法
JP2003215891A (ja) 2002-01-25 2003-07-30 Sharp Corp 帯電装置
US7560396B2 (en) * 2002-03-29 2009-07-14 Tokyo Electron Limited Material for electronic device and process for producing the same
US6780720B2 (en) 2002-07-01 2004-08-24 International Business Machines Corporation Method for fabricating a nitrided silicon-oxide gate dielectric
JP2004087865A (ja) * 2002-08-28 2004-03-18 Hitachi Ltd 半導体装置の製造方法
JP4443818B2 (ja) * 2002-10-02 2010-03-31 パナソニック株式会社 プラズマドーピング方法
US20050176191A1 (en) * 2003-02-04 2005-08-11 Applied Materials, Inc. Method for fabricating a notched gate structure of a field effect transistor
US20060048857A1 (en) * 2004-09-09 2006-03-09 Cooper Clark V Method for processing alloys via high-current density ion implantation
US7501352B2 (en) * 2005-03-30 2009-03-10 Tokyo Electron, Ltd. Method and system for forming an oxynitride layer
US20070065593A1 (en) * 2005-09-21 2007-03-22 Cory Wajda Multi-source method and system for forming an oxide layer

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