TWI721271B - 矽氮化膜之成膜方法及成膜裝置 - Google Patents

矽氮化膜之成膜方法及成膜裝置 Download PDF

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TWI721271B
TWI721271B TW107116356A TW107116356A TWI721271B TW I721271 B TWI721271 B TW I721271B TW 107116356 A TW107116356 A TW 107116356A TW 107116356 A TW107116356 A TW 107116356A TW I721271 B TWI721271 B TW I721271B
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gas
silicon nitride
nitride film
processing container
film
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TW107116356A
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TW201900919A (zh
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戶根川大和
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日商東京威力科創股份有限公司
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    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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Abstract

本發明之課題係提供一種技術，可以在以ALD法(原子層堆積法)對複數片被處理基板形成矽氮化膜之際，降低所形成之矽氮化膜的應力。 其解決手段係於以ALD法一併對複數片被處理體進行矽氮化膜之成膜處理之際，於各個該循環中，在成膜原料吸附步驟、與氮化步驟之間，實施在處理容器內產生氫自由基以進行氫自由基吹洗的步驟，藉以促進已形成之矽氮化膜的Si-N鍵結，降低所要形成之矽氮化膜的拉伸應力。

Description

矽氮化膜之成膜方法及成膜裝置
本發明係有關於矽氮化膜之成膜方法及成膜裝置。
於半導體裝置的製造次序(sequence)中，存在一種成膜處理，係對於以矽晶圓為代表之半導體晶圓(基板)，形成矽氮化膜(SiN膜)等氮化膜以作為絶緣膜。
就SiN膜之成膜手法而言，在習知技術，多採用電漿CVD。另一方面，也逐步採用能低溫、且以均勻而良好之覆蓋率成膜，電子性質亦良好的原子層堆積法(Atomic Layer Deposition；ALD法)所形成的SiN膜。作為採用ALD法的SiN膜之成膜方法，於專利文獻1記載著：在對於複數片半導體晶圓一併進行處理的批次式縱型成膜裝置，藉由作交互重複作為Si(矽)原料氣體的二氯矽烷(DCS)氣體、以及作為氮化氣體之NH3 (氨)氣體，並附帶進行吹洗(purge)，以形成SiN膜。
在使用批次式縱型成膜裝置而藉由ALD法來形成SiN膜時，會在既定成膜條件下，使用例如作為原料氣體的二氯矽烷(DCS；SiH2 Cl2 )氣體、以及作為氮化氣體的NH3 氣體，而藉由以下步驟來形成一個分子層厚的SiN單位膜：首先對於作為基板的半導體晶圓供給DCS氣體，而化學性吸附單原子層的Si的步驟、藉由惰性氣體以吹洗DCS氣體的步驟、供給NH3 氣體之電漿而使所吸附之Si進行氮化的步驟、藉由惰性氣體以吹洗NH3 氣體的步驟；藉由重複這些步驟既定次數，而可以製得既定膜厚的SiN膜。
走筆至此，就SiN膜的用途而言可舉出：可以製得在光微影技術之解析極限以下之微細圖案的雙重圖案技術中的側壁(間隙子)(例如專利文獻2)。於專利文獻2，係在非晶矽圖案上形成SiN膜，之後蝕刻SiN膜以使得僅在非晶矽圖案之側壁部殘留SiN膜之間隙子(SiN間隙子)；之後去除非晶矽圖案，而形成SiN膜的圖案。
在此種雙重圖案中，隨著圖案更進一步地微細化，需要SiN間隙子更嚴格的均勻性，再者，還要求低溫成膜及高度覆蓋率性能等，因此在構思以例如專利文獻1所記載之ALD來製成SiN膜。 [習知技術文獻] [專利文獻]
[專利文獻1]日本特開2004-281853號公報 [專利文獻2]日本特開2014-11357號公報
[發明所欲解決的問題]
走筆至此，SiN膜一般而言係具有高度拉伸應力的薄膜，而由於裝置之微細化使得SiN間隙子益發薄膜化，所以間隙子彼此拉近所導致之彎曲(bending)就逐漸演變成一個問題。
電漿CVD法所製得之SiN膜，可以透過氣體比例及壓力等，來調整薄膜中的氫濃度或組成，藉此可以調整薄膜應力。
然而，以ALD法所製得之SiN膜非常緻密，雜質比電漿CVD法所製得之SiN膜來得少，而在所需之低溫成膜下，會難以控制薄膜應力。此種薄膜應力問題，並不限於雙重圖案的間隙子，都會發生在ALD法所製得之SiN膜。
因此，本發明的課題係提供一種技術，可以在以ALD法對複數片被處理基板形成矽氮化膜之際，降低所形成之矽氮化膜的應力。 [解決問題之技術手段]
為了解決上述課題，本發明的第1層面，提供一種矽氮化膜之成膜方法，係在處理容器內配置複數片被處理基板，並對這些複數片被處理基板，重複進行包括第1吹洗步驟、成膜原料氣體吸附步驟、第2吹洗步驟、以及氮化步驟在內的循環複數次，而一併對複數片被處理基板形成既定膜厚之矽氮化膜；該第1吹洗步驟係將該處理容器內加熱至既定溫度，並且使該處理容器內成為既定之減壓狀態，再以惰性氣體將該處理容器內加以吹洗；該成膜原料氣體吸附步驟係對該處理容器內供給由含氯之矽化合物所構成的成膜原料氣體，而使其吸附於被處理基板；該第2吹洗步驟係以惰性氣體對處理容器內進行吹洗；該氮化步驟係對該處理容器內供給氮化氣體，而使構成該被處理基板之元素氮化；該矽氮化膜之成膜方法，於各個該循環中，在該成膜原料氣體吸附步驟、與該氮化步驟之間，實施在該處理容器內產生氫自由基以進行氫自由基吹洗的氫自由基吹洗步驟，藉以促進已形成之矽氮化膜的Si-N鍵結，降低所要形成之矽氮化膜的拉伸應力。
於上述第1層面，相鄰之被處理基板之間的間距，係16mm以上較佳，32mm更佳。
該氮化步驟，可以係以電漿產生該氮化氣體的活性物種，再藉由該活性物種來進行氮化。
該氫自由基吹洗步驟，可以在該成膜原料氣體吸附步驟、與該第2吹洗步驟之間實施。該氫自由基吹洗步驟，較佳係使所供給之氣體中的H2 氣體之比例為50%以上而進行。再者，該氫自由基，可以係藉由使氫氣電漿化而產生。於該氫自由基吹洗步驟，使該氫氣電漿化之際的高頻功率，係100W以上較佳。該氫自由基吹洗步驟的時間，係10～60秒較佳。
該含氯之矽化合物，可以係由二氯矽烷、單氯矽烷、三氯矽烷、四氯化矽、及六氯乙矽烷所構成之群組中所選出之至少一種；該氮化氣體，可以係由NH3 氣體及N2 氣體所構成之群組中所選出之至少一種。
本發明之第2層面係提供一種矽氮化膜之成膜裝置，係一併對複數片被處理基板形成既定膜厚之矽氮化膜；該矽氮化膜之成膜裝置，包括：處理容器，容納將要形成該矽氮化膜的複數片被處理基板；氣體供給機構，對該處理容器內，供給惰性氣體、矽成膜原料氣體、氮化氣體、以及氫氣；加熱裝置，加熱該處理容器內所容納之複數片被處理基板；氫自由基產生機構，產生氫自由基；排氣裝置，使該處理容器內排氣；以及控制部，進行控制，以重複進行包括第1吹洗步驟、成膜原料氣體吸附步驟、第2吹洗步驟、以及氮化步驟在內的循環複數次，而一併對複數片被處理基板形成既定膜厚之矽氮化膜；該第1吹洗步驟係將該處理容器內加熱至既定溫度，並且使該處理容器內成為既定之減壓狀態，再以惰性氣體將該處理容器內加以吹洗；該成膜原料氣體吸附步驟係對該處理容器內供給由含氯之矽化合物所構成的成膜原料氣體，而使其吸附於被處理基板；該第2吹洗步驟係以惰性氣體對處理容器內進行吹洗；該氮化步驟係對該處理容器內供給氮化氣體，而使構成該被處理基板之元素氮化；於各個該循環中，在該成膜原料氣體吸附步驟、與該氮化步驟之間，實施在該處理容器內藉由該氫自由基產生機構而產生氫自由基以進行氫自由基吹洗的氫自由基吹洗步驟，藉以促進已形成之矽氮化膜的Si-N鍵結，降低所要形成之矽氮化膜的拉伸應力。
本發明之第3層面係提供一種記錄媒體，在電腦上動作，並儲存著用以控制矽氮化膜之成膜裝置的程式；該程式在執行時，使電腦控制該矽氮化膜之成膜裝置，以進行如上述第1層面之矽氮化膜之成膜方法。 [發明之效果]
若藉由本發明，在以ALD法對複數片被處理體一併進行形成矽氮化膜之處理之際，由於在各循環中，會在成膜原料吸附步驟與氮化步驟之間，實施氫自由基吹洗步驟，其係在處理容器內產生氫自由基以進行氫自由基吹洗，藉此以促進已成膜之矽氮化膜的Si-N鍵結，而可以降低已成膜之矽氮化膜的拉伸應力，因此能以ALD法製得降低應力的矽氮化膜。
以下將參照隨附圖式以說明本發明之實施形態。 於本實施形態，係以形成矽氮化膜(SiN膜)以作為氮化膜之情況為例，進行說明。
＜成膜裝置之一例＞ 圖1係繪示能用以實施本發明一實施形態之氮化膜之成膜方法的成膜裝置之一例的縱剖面圖，圖2係圖1所示之成膜裝置的水平剖面圖。
本例之成膜裝置100，具有下端開口且有頂棚之圓筒體狀的處理容器1。此處理容器1之整體，例如係以石英形成；而在此處理容器1內的上端部附近，設有石英製之頂棚板2，封住其下側的區域。再者，在此處理容器1之下端開口部，隔著O環等的密封構件4，連結著成形為圓筒體狀之金屬製的分歧管3。
分歧管3支撐著處理容器1的下端；由此分歧管3的下方，石英製的晶舟5插入處理容器1內，該晶舟5分成多層地載置著作為被處理基板的複數片半導體晶圓(矽晶圓)W，例如50～150片。此晶舟5具有3支桿體6(參照圖2)，並以桿體6上所形成之凹槽(未圖示)來支撐複數片晶圓W。
此晶舟5係隔著石英製的保溫筒7而載置於承座(stage)8上，此承座8係被支撐在旋轉軸10上，該旋轉軸10貫穿金屬(不鏽鋼)製之蓋部9，該蓋部9使分歧管3之下端開口部開閉。
然後，於此旋轉軸10的貫通部，設有磁性流體密封11，將旋轉軸10氣密性地密封，並以使其可旋轉的方式加以支撐。再者，在蓋部9的周邊部及分歧管3的下端部之間，中隔設置著密封構件12，用以保持處理容器1內的密封性。
旋轉軸10係安裝在例如晶舟升降器等的升降機構(未圖示)所支撐之臂體13的前端，而與晶舟5及蓋部9等一體升降，並相對於處理容器1內進行插入或脫離。又，亦可將承座8固定設置於蓋部9上，而在不旋轉晶舟5的情況下進行晶圓W之處理。
再者，成膜裝置100具有：含Cl(氯)之Si化合物氣體供給機構14，對處理容器1內供給含Cl之Si化合物氣體，例如DCS氣體；氮化氣體供給機構15，對處理容器1內供給氮化氣體，例如NH3 氣體；H2 (氫)氣體供給機構16，對處理容器1內供給氫氣(H2 氣體)；以及惰性氣體供給機構17，對處理容器1內供給作為吹洗氣體等的惰性氣體，例如N2 (氮)氣體或Ar(氬)氣體。
含Cl之Si化合物氣體供給機構14具有：含Cl之Si化合物氣體供給源18、從含Cl之Si化合物氣體供給源18引導含Cl之Si化合物氣體的氣體配管19、以及連接此氣體配管19並將含Cl之Si化合物氣體引導至處理容器1內的氣體分散噴嘴20。作為含Cl之Si化合物氣體，除了DCS氣體以外，還可以列舉：單氯矽烷(MCS；SiH3 Cl)、三氯矽烷(TCS；SiHCl3 )、四氯化矽(STC；SiCl4 )、六氯乙矽烷(HCD；Si2 Cl6 )等。
氮化氣體供給機構15具有：氮化氣體供給源21、從氮化氣體供給源121引導氮化氣體的氣體配管22、以及將氮化氣體引導至處理容器1內的氣體分散噴嘴23。作為氮化氣體，除了NH3 氣體以外，還可以列舉N2 氣體等。
H2 氣體供給機構16具有：H2 氣體供給源24、從H2 氣體供給源24引導H2 氣體的氣體配管25、以及將H2 氣體引導至處理容器1內的氣體分散噴嘴26。
氣體分散噴嘴20、23、及26，係由石英所構成，並且往內側貫穿分歧管3的側壁而朝向上方屈曲再垂直延伸。這些氣體分散噴嘴20、23、及26的垂直部分，在對應於晶舟5之晶圓支撐範圍的上下方向長度之範圍內，分別以既定之間隔，形成對應於各晶圓W的複數個氣體釋出孔20a、23a、及26a(26a僅繪示於圖2)。從各氣體釋出孔20a、23a、及26a，可以在水平方向上對處理容器1大致均勻地釋出氣體。氣體分散噴嘴20設有2支，氣體分散噴嘴23及26則分別設有1支。
惰性氣體供給機構17具有：惰性氣體供給源27、從惰性氣體供給源27引導惰性氣體的氣體配管28、以及此氣體配管28所連接的氣體噴嘴29，該氣體噴嘴29貫穿分歧管3之側壁而設置，且係由短石英管所構成。
於氣體配管19、22、25、28，分別設有開閉閥19a、22a、25a、28a，以及流量控制器19b、22b、25b、28b。
於處理容器1之側壁的局部，形成有電漿產生機構30。電漿產生機構30，係用以使NH3 氣體等氮化氣體電漿化以產生用於氮化的活性物種，更進一步地使H2 氣體也電漿化以產生氫自由基。
電漿產生機構30具備焊接在處理容器1外壁的電漿隔間板32。電漿隔間板32例如由石英形成。電漿隔間板32的剖面呈凹狀，並覆蓋住處理容器1的側壁上所形成之開口31。開口31係在上下方向上形成為細長形，而得以在上下方向上涵蓋晶舟5所支撐的所有半導體晶圓W。在以電漿隔間板32所規定出的內側空間，亦即電漿產生空間的內部，配置有上述用以釋出NH3 氣體等氮化氣體的分散噴嘴23、以及用以釋出H2 氣體的分散噴嘴26。又，用以釋出DCS氣體等的含Cl之Si化合物氣體的2支氣體分散噴嘴20，係設在包夾處理容器1的內側壁之開口31的位置。
再者，電漿產生機構30，更進一步地在電漿隔間板32的兩片側壁的外表面，具有：配置成沿著上下方向而彼此相向又細長的一對電漿電極33、以及經由供電線34而分別連接至一對電漿電極33並且向一對電漿電極33供給高頻電力的高頻電源35。高頻電源35向一對電漿電極33施加例如13.56MHz的高頻電壓。藉此，在電漿隔間板32所規定出的電漿產生空間內，施加高頻電場。從分散噴嘴23釋出之氮化氣體、以及從分散噴嘴26釋出之H2 氣體，在施加有高頻電場的電漿產生空間內被電漿化，藉此所產生之用於氮化的活性物種、及氫自由基，就會經由開口31而供給至處理容器1內部。
在電漿隔間板32外側，安裝著將其加以包覆的絶緣保護罩36。在絶緣保護罩36的內側部分，設有冷媒通路(未圖示)，藉由在此處使已冷卻之氮氣等冷媒流通，而使電漿電極33受到冷卻。
在相向於開口31的處理容器1之側壁部分，設有用以使處理容器1內真空排氣的排氣口37。此排氣口37係對應於晶舟5而形成為上下細長。在對應於處理容器1之排氣口37的部分，安裝著排氣口遮蓋構件38，其成形為剖面U字狀以覆蓋排氣口37。此排氣口遮蓋構件38，係沿著處理容器1的側壁而往上方延伸。在排氣口遮蓋構件38的下部，經由排氣口37而連接著用以使處理容器1排氣的排氣管39。排氣管39連接著包含控制處理容器1內之壓力的壓力控制閥40及真空泵等的排氣裝置41，並藉由排氣裝置41而經由排氣管39使處理容器1內進行排氣。
再者，設有筒體狀的加熱機構42，包圍著此處理容器1的外周，而對此處理容器1及其內部的晶圓W進行加熱。
成膜裝置100具有控制部50。控制部50進行成膜裝置100之各構成部位的控制，例如以閥19a、22a、25a、28a之開閉所進行的各氣體之供給・停止的控制，流量控制器19b、22b、25b、28b所進行之氣體流量的控制，排氣裝置41所進行之排氣控制，高頻電源35所進行之高頻電力的開・關控制，及加熱機構42所進行之晶圓W的溫度的控制等。控制部50具有：中央處理器(電腦)、進行上述控制的主控制部、輸入裝置、輸出裝置、顯示裝置、以及記憶裝置。於記憶裝置，設置了記錄媒體，其儲存了對於在成膜裝置100執行之處理加以控制的程式，亦即儲存了製程配方；主控制部進行控制，叫出記錄媒體所記憶的既定處理配方，而基於該處理配方而使成膜裝置100進行既定之處理。
＜成膜方法＞ 接著，針對藉由此種成膜裝置100所實施的本發明一實施形態之成膜方法，進行說明。
在此以使用DCS氣體作為含Cl之Si化合物氣體、使用NH3 氣體作為氮化氣體、使用N2 氣體作為吹洗氣體，並透過ALD法而形成SiN膜(ALD-SiN膜)為例，進行敍述。
首先，使處理容器1內的溫度成為400～600℃，並將搭載了50～150片晶圓W的晶舟5搬入處理容器1內，再藉由排氣裝置41使處理容器1內排氣，而將處理容器1內調壓至13～665Pa。
在此狀態下，如圖3的次序圖所示，以N2 氣體所進行之吹洗步驟(步驟S1)、供給DCS氣體(Si吸附)步驟(步驟S2)、氫自由基吹洗步驟(步驟S3)、以N2 氣體所進行之吹洗步驟(步驟S4)、NH3 氣體供給(氮化)步驟(步驟S5)，會重複既定次數，以形成既定膜厚的ALD-SiN膜。
於步驟S1及步驟S4的吹洗步驟之進行，係一邊以排氣裝置41使處理容器1內排氣，一邊從惰性氣體供給源27對處理容器1內供給N2 氣體以作為惰性氣體。藉此而將處理容器1內的環境氣體置換成N2 氣體。此時的條件較佳係——N2 氣體流量：500～5000sccm，時間：3～10秒。
於步驟S2的DCS氣體供給步驟，係從含Cl之Si化合物氣體供給源18對處理容器1內供給DCS氣體以作為含Cl之Si化合物氣體，而使晶圓W之表面吸附Si。此時的條件較佳係——DCS氣體流量：500～3000sccm，時間：1～10秒。
於步驟S3的氫自由基吹洗步驟，係一邊使處理容器1內排氣，一邊從H2 氣體供給源24對處理容器1內供給H2 氣體，一邊以電漿產生機構30使H2 氣體電漿化以產生氫自由基，並使氫自由基作用於步驟S2後的晶圓W。關於氫自由基吹洗步驟之詳情，將於後文敍述。
於步驟S5的NH3 氣體供給步驟，係從氮化氣體供給源21對處理容器1內供給NH3 氣體以作為氮化氣體，並以電漿產生機構30使NH3 氣體電漿化以產生用於氮化的活性物種，再使步驟S2時所吸附的Si氮化。此時的條件較佳係——NH3 氣體流量：500～5000sccm，時間：5～120秒。
又，步驟S3的氫自由基吹洗步驟、與步驟S4的吹洗步驟，亦可對調順序。
接著，針對步驟S3的氫自由基吹洗步驟，進行詳細說明。 於習知之ALD-SiN膜的成膜，係如圖4般，不進行氫自由基處理(步驟S3)，僅重複：N2 氣體所進行之吹洗步驟(步驟S1)、DCS氣體供給步驟(步驟S2)、N2 氣體所進行之吹洗步驟(步驟S4)、NH3 氣體供給(氮化)步驟(步驟S5)。
由於ALD-SiN膜能低溫、且以均勻而良好之覆蓋率成膜，所以會用在基於圖案之微細化而需要非常嚴格之均勻性等等的雙重圖案所使用的SiN間隙子。然而，一般而言，SiN膜係具有高拉伸應力的薄膜，若隨著裝置進一步微細化而使SiN間隙子更加薄膜化，則間隙子彼此之間會拉近，導致發生彎曲。
亦即，若是藉由雙重圖案以形成圖案，則如圖5所示，要在矽基板101上，形成被蝕刻膜102，並於其上準備具有硬遮罩層103、及形成為既定圖案的非晶矽膜105之結構(圖5(a))，再於非晶矽膜105上形成SiN膜106(圖5(b))，並藉由SiN膜106之蝕刻及非晶矽膜105之去除，而成為殘留SiN間隙子107的狀態(圖5(c))。若於此狀態下如圖5(d)所示，以SiN間隙子107為遮罩進行蝕刻，則會成為殘留被蝕刻膜102、硬遮罩層103、及SiN間隙子107所構成之薄層圖案的狀態；而由於SiN間隙子107之拉伸應力，導致間隙子彼此拉近，發生如圖6所示的彎曲。
此種薄膜應力，在習知技術，如圖7所示，已知於ALD-SiN膜，係會隨著成膜溫度調高而降低，而在所需的低溫成膜，如400～500℃之下應力會很高。如圖7所示，電漿CVD法所製得之SiN膜(PECVD-SiN膜)也呈現高度的應力，但可以透過調整氣體比例及壓力來降低。然而，由於ALD-SiN膜非常地緻密，相較於PECVD-SiN膜較少雜質，因此在所需的低溫成膜下，要降低薄膜應力實屬不易。
有鑑於此，在本實施形態，係藉由步驟S3的氫自由基吹洗步驟，以降低ALD-SiN膜之薄膜應力。
此情況下機制，將參照圖8以進行說明。 於習知之ALD-SiN膜的成膜，如圖8(a)所示，在供給過DCS氣體之際，會使得化學性吸附到的Si上，團簇狀地物理性吸附住DCS所含有的Cl或H等雜質、或多餘的Si，而變成要在此狀態下供給NH3 氣體。因此，所形成的SiN，會含有Cl或H等的雜質、或多餘的Si等，還會含有氣孔，而無法充分形成Si-N鍵結。因而已究明係由於此種因素，才導致薄膜的拉伸應力加大。
有鑑於此，於本實施形態，係如圖8(b)所示，藉由進行氫自由基吹洗，而使身為雜質的Cl、H及多餘的Si，視同HCl及SiH4 等而受到去除。藉此，會成為所吸附的乃是幾乎Si單原子層之狀態；再藉由於此狀態下供給NH3 氣體，而成為少有雜質及氣孔、會充分形成Si-N鍵結的狀態，得以縮小膜的拉伸應力。
基於充分發揮氫自由基吹洗所帶來的應力降低效果起見，晶舟5所搭載之晶圓與晶圓之間的間距，係以較大為佳。如圖9(a)所示，若晶圓間的間距小，則有氫自由基容易去活化、無法到達晶圓W的中心之虞。相對地，如圖9(b)所示，若晶圓間的間距大，氫自由基就不會去活化，而易於到達晶圓W的中心，氫自由基就會充分地作用於晶圓W。
基於此種觀點，晶圓間的間距，較佳係比習知之8mm間距更大，更佳係16mm間距以上。但間距若過度加大，會導致單次的處理片數降低，使效果受侷限，因此以4倍間距，即32mm間距為最佳。
氫自由基吹洗步驟時的H2 氣體之比例，係越高越佳，以50%以上為佳。亦可為H2 氣體係100%。與H2 氣體一同使用的氣體係以惰性氣體為佳。再者，高頻功率較佳係50～300W，更佳係100W以上，又以200W尤佳。更進一步地，較佳係——H2 氣體流量：500～2000sccm，時間：10～60秒。
如上所述，透過晶圓W的間距及氫自由基吹洗步驟的條件，而可以控制ALD-SiN膜的應力，藉由對這些進行適當的設定，可以製得所需的低應力之ALD-SiN膜。
＜實驗例＞ 接著，針對本發明之實驗例，進行說明。 在此，藉由圖1所示的裝置，使用DCS氣體以作為含Cl之Si化合物氣體，使用NH3 氣體以作為氮化氣體，並使溫度：550℃、壓力：400Pa，再變更晶圓的間距及氫自由基吹洗條件，藉由重複上述步驟S1～S5，進行SiN膜之成膜，並量測所製得之SiN膜的應力。
使晶圓間的間距，設為標準的8mm、2倍間距的16mm、4倍間距的32mm；並使氫自由基吹洗的基本條件，設為H2 氣體比例：50%(H2 氣體：1000sccm，N2 氣體：1000sccm)；使高頻功率：設為100W；並使氫自由基吹洗的時間變化。
其結果繪示於圖10。如圖10所示，在晶圓間之間距為8mm及16mm時，若不進行氫自由基吹洗，則SiN膜的拉伸應力會在1200MPa以上。
在8mm間距的情況下，即使進行了20秒(秒)的氫自由基吹洗，拉伸應力也會在1000MPa以上，幾乎未能降低。在16mm間距的情況下，氫自由基吹洗若為20秒，則拉伸應力會降低到800MPa左右；若為60秒則會降低到600MPa。在32mm間距的情況下，20秒會是700MPa以下，30秒會是600MPa，60秒會是500MPa，能獲得一定程度的應力降低效果。
有鑑於此，為了得到更進一步的應力降低效果，於32mm間距下，使氫自由基吹洗條件變更為H2 氣體比例：80%(H2 氣體：1000sccm，N2 氣體：250sccm)，高頻功率：200W，再加上60秒的氫自由基吹洗。其結果亦一併繪示於圖10，確認到藉由如此這般地增加H2 氣體比例及高頻功率，使得拉伸應力降低到200MPa以下。
＜其他套用＞ 以上針對本發明之實施形態進行了說明，但此發明並不限定於上述實施形態，只要在不脫離其趣旨的範圍內，可進行各種變形，該等變更亦包含在本發明之範圍內。
例如，於上述實施形態，係以藉由縱型批次式裝置來實施本發明之成膜方法為例而陳述，但並不限定於此，亦可藉由橫型批次式裝置來實施。
再者，於上述實施形態，係以藉由向一對電漿電極施加高頻電力來產生電漿，再藉由該電漿來產生氫自由基為例而陳述；但產生氫自由基的方法，並不限定於此，亦可使用其他的感應耦合電漿或微波電漿等其他電漿，再者亦可使用以氫氣接觸發熱燈絲之處理等的方法。
1‧‧‧處理容器2‧‧‧頂棚板3‧‧‧分歧管4‧‧‧密封構件5‧‧‧晶舟6‧‧‧桿體7‧‧‧保溫筒8‧‧‧承座9‧‧‧蓋部10‧‧‧旋轉軸11‧‧‧磁性流體密封12‧‧‧密封構件13‧‧‧臂體14‧‧‧含Cl之Si化合物氣體供給機構15‧‧‧氮化氣體供給機構16‧‧‧H2 氣體供給機構17‧‧‧惰性氣體供給機構18‧‧‧含Cl之Si化合物氣體供給源19‧‧‧氣體配管20‧‧‧氣體分散噴嘴21‧‧‧氮化氣體供給源22‧‧‧氣體配管23‧‧‧氣體分散噴嘴24‧‧‧H2 氣體供給源25‧‧‧氣體配管26‧‧‧氣體分散噴嘴20a、23a、26a‧‧‧氣體釋出孔27‧‧‧惰性氣體供給源28‧‧‧氣體配管29‧‧‧氣體噴嘴19a、22a、25a、28a‧‧‧開閉閥19b、22b、25b、28b‧‧‧流量控制器30‧‧‧電漿產生機構31‧‧‧開口32‧‧‧電漿隔間板33‧‧‧電漿電極34‧‧‧供電線35‧‧‧高頻電源36‧‧‧絶緣保護罩37‧‧‧排氣口38‧‧‧排氣口遮蓋構件39‧‧‧排氣管40‧‧‧壓力控制閥41‧‧‧排氣裝置42‧‧‧加熱機構50‧‧‧控制部100‧‧‧成膜裝置101‧‧‧矽基板102‧‧‧蝕刻膜103‧‧‧硬遮罩層105‧‧‧非晶矽膜106‧‧‧SiN膜107‧‧‧SiN間隙子W‧‧‧半導體晶圓(被處理基板)S1～S5‧‧‧步驟
【圖1】繪示能用於本發明一實施形態的氮化膜之成膜方法之實施的成膜裝置之一例的縱剖面圖。 【圖2】圖1所示之成膜裝置的水平剖面圖。 【圖3】繪示本發明一實施形態之氮化膜之成膜方法的次序的圖式。 【圖4】繪示習知之氮化膜之成膜方法的次序的圖示。 【圖5】(a)～(d)用以說明使用矽氮化膜以作為間隙子之雙重圖案的圖式。 【圖6】繪示在圖5之雙重圖案，因為矽氮化膜的應力而發生彎曲之狀態的圖式。 【圖7】繪示習知之ALD-SiN膜及與其應力相關知識的圖式。 【圖8】(a)～(b)用以說明藉由氫自由基吹洗以降低薄膜應力之機制的圖式。 【圖9】(a)～(b)繪示晶圓間的間距所造成的氫自由基之狀態的圖式。 【圖10】繪示實驗例之結果的圖式。

Claims (12)

  1. 一種矽氮化膜之成膜方法，係在處理容器內配置複數片被處理基板，並對這些複數片被處理基板，重複進行包括第1吹洗步驟、成膜原料氣體吸附步驟、第2吹洗步驟、以及氮化步驟在內的循環複數次，而一併對複數片該被處理基板形成既定膜厚之矽氮化膜；該第1吹洗步驟係將該處理容器內加熱至既定溫度，並且使該處理容器內成為既定之減壓狀態，再以惰性氣體將該處理容器內加以吹洗；該成膜原料氣體吸附步驟係對該處理容器內供給由含氯之矽化合物所構成的成膜原料氣體，而使其吸附於該被處理基板；該第2吹洗步驟係以惰性氣體對該處理容器內進行吹洗；該氮化步驟係對該處理容器內供給氮化氣體，而使構成該被處理基板之元素氮化；於各個該循環中，在該成膜原料氣體吸附步驟與該氮化步驟之間，實施在該處理容器內產生氫自由基以進行氫自由基吹洗的氫自由基吹洗步驟，藉以促進所形成之該矽氮化膜的Si-N鍵結，降低所形成之該矽氮化膜的拉伸應力；且相鄰之該被處理基板之間的間距，係16mm以上。
  2. 如申請專利範圍第2項之矽氮化膜之成膜方法，其中，相鄰之該被處理基板之間的間距，係32mm。
  3. 如申請專利範圍第1或2項之矽氮化膜之成膜方法，其中，該氮化步驟，係以電漿產生該氮化氣體的活性物種，再藉由該活性物種來進行氮化。
  4. 如申請專利範圍第1項之矽氮化膜之成膜方法，其中，該氫自由基吹洗步驟，係在該成膜原料氣體吸附步驟、與該第2吹洗步驟之間實施。
  5. 如申請專利範圍第1項之矽氮化膜之成膜方法，其中，該氫自由基吹洗步驟，係使所供給之氣體中的H2氣體之比例為50%以上而進行。
  6. 如申請專利範圍第1項之矽氮化膜之成膜方法，其中，於該氫自由基吹洗步驟，該氫自由基係藉由使氫氣電漿化而產生。
  7. 如申請專利範圍第6項之矽氮化膜之成膜方法，其中，於該氫自由基吹洗步驟，使該氫氣電漿化之際的高頻功率係100W以上。
  8. 如申請專利範圍第1項之矽氮化膜之成膜方法，其中，該氫自由基吹洗步驟的時間係10~60秒。
  9. 如申請專利範圍第1項之矽氮化膜之成膜方法，其中，該含氯之矽化合物，係由二氯矽烷、單氯矽烷、三氯矽烷、四氯化矽、六氯乙矽烷所構成之群組中所選出之至少一種。
  10. 如申請專利範圍第1項之矽氮化膜之成膜方法，其中，該氮化氣體，係由NH3氣體及N2氣體所構成之群組中所選出之至少一種。
  11. 一種矽氮化膜之成膜裝置，一併對複數片被處理基板形成既定膜厚之矽氮化膜，包括：處理容器，用以容納待形成該矽氮化膜的複數片該被處理基板；氣體供給機構，對該處理容器內，供給惰性氣體、矽成膜原料氣體、氮化氣體、以及氫氣；加熱裝置，加熱該處理容器內所容納之複數片該被處理基板；氫自由基產生機構，產生氫自由基；排氣裝置，使該處理容器內排氣；以及控制部，進行控制，以重複進行包括第1吹洗步驟、成膜原料氣體吸附步驟、第2吹洗步驟、以及氮化步驟在內的循環複數次，而一併對複數片該被處理基板形成既定膜厚之該矽氮化膜；該第1吹洗步驟係將該處理容器內加熱至既定溫度，並且使該處理容器內成為既定之減壓狀態，再以該惰性氣體將該處理容器內加以吹洗；該成膜原料氣體吸附步驟係對該處理容器內供給由含氯之矽化合物所構成的成膜原料氣體，而使其吸附於該被處理基板；該第2吹洗步驟係以該惰性氣體對該處理容器內進行吹洗；該氮化步驟係對該處理容器內供給該氮化氣體，而使構成該被處理基板之元素氮化； 於各個該循環中，在該成膜原料氣體吸附步驟與該氮化步驟之間，實施在該處理容器內藉由該氫自由基產生機構而產生該氫自由基以進行氫自由基吹洗的氫自由基吹洗步驟，藉以促進已形成之該矽氮化膜的Si-N鍵結，降低所要形成之該矽氮化膜的拉伸應力；且相鄰之該被處理基板之間的間距，係16mm以上。
  12. 一種記錄媒體，儲存有在電腦上動作以控制矽氮化膜之成膜裝置的程式；該程式在執行時，使電腦控制該矽氮化膜之成膜裝置，以進行如申請專利範圍第1至10項中任一項的矽氮化膜之成膜方法。
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JP6653308B2 (ja) * 2017-11-15 2020-02-26 株式会社Ｋｏｋｕｓａｉ Ｅｌｅｃｔｒｉｃ 半導体装置の製造方法、基板処理装置、およびプログラム
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JP7126468B2 (ja) 2019-03-20 2022-08-26 株式会社Ｓｃｒｅｅｎホールディングス 基板処理方法および基板処理装置
JP7278123B2 (ja) * 2019-03-22 2023-05-19 東京エレクトロン株式会社 処理方法
JP7209568B2 (ja) 2019-03-27 2023-01-20 東京エレクトロン株式会社 基板処理方法及び基板処理装置
WO2021053987A1 (ja) * 2019-09-20 2021-03-25 株式会社Ｋｏｋｕｓａｉ Ｅｌｅｃｔｒｉｃ 半導体装置の製造方法、基板処理装置、およびプログラム
JP7321085B2 (ja) 2019-12-26 2023-08-04 東京エレクトロン株式会社 膜形成方法及びシステム
JP2021150382A (ja) * 2020-03-17 2021-09-27 東京エレクトロン株式会社 基板処理方法及び基板処理装置
JP7455013B2 (ja) 2020-07-10 2024-03-25 東京エレクトロン株式会社 プラズマ処理装置及びプラズマ処理方法
US11646195B2 (en) * 2020-10-22 2023-05-09 Nanya Technology Corporation Method for fabricating semiconductor device having etch resistive nitride layer
TWI806261B (zh) * 2020-12-24 2023-06-21 日商國際電氣股份有限公司 基板處理方法、半導體裝置之製造方法、基板處理裝置及程式

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004281853A (ja) * 2003-03-18 2004-10-07 Hitachi Kokusai Electric Inc 基板処理装置
US20140273530A1 (en) * 2013-03-15 2014-09-18 Victor Nguyen Post-Deposition Treatment Methods For Silicon Nitride

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100567564C (zh) * 2002-12-20 2009-12-09 应用材料有限公司 形成高质量的低温氮化硅层的方法和设备
JP5054890B2 (ja) * 2004-12-15 2012-10-24 ルネサスエレクトロニクス株式会社 半導体装置の製造方法
JP4607637B2 (ja) * 2005-03-28 2011-01-05 東京エレクトロン株式会社 シリコン窒化膜の形成方法、シリコン窒化膜の形成装置及びプログラム
JP4456533B2 (ja) * 2005-06-14 2010-04-28 東京エレクトロン株式会社 シリコン酸化膜の形成方法、シリコン酸化膜の形成装置及びプログラム
CN101165205A (zh) * 2006-10-18 2008-04-23 甘国工 在晶体硅太阳能电池片上镀抗反射钝化膜的方法及设备
JP6022166B2 (ja) * 2011-02-28 2016-11-09 株式会社日立国際電気 半導体装置の製造方法、基板処理装置およびプログラム
JP5792550B2 (ja) * 2011-08-02 2015-10-14 ルネサスエレクトロニクス株式会社 半導体装置およびその製造方法
JP5842750B2 (ja) 2012-06-29 2016-01-13 東京エレクトロン株式会社 成膜方法、成膜装置及び記憶媒体
JP2014082322A (ja) * 2012-10-16 2014-05-08 Tokyo Electron Ltd シリコン窒化物膜の成膜方法および成膜装置
US9824881B2 (en) * 2013-03-14 2017-11-21 Asm Ip Holding B.V. Si precursors for deposition of SiN at low temperatures
JP2015185837A (ja) * 2014-03-26 2015-10-22 東京エレクトロン株式会社 成膜装置
KR102146542B1 (ko) * 2015-09-30 2020-08-20 주식회사 원익아이피에스 질화막의 제조방법

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004281853A (ja) * 2003-03-18 2004-10-07 Hitachi Kokusai Electric Inc 基板処理装置
US20140273530A1 (en) * 2013-03-15 2014-09-18 Victor Nguyen Post-Deposition Treatment Methods For Silicon Nitride

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