TWI791029B - 沉積半導體膜的方法 - Google Patents

沉積半導體膜的方法 Download PDF

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TWI791029B
TWI791029B TW107123761A TW107123761A TWI791029B TW I791029 B TWI791029 B TW I791029B TW 107123761 A TW107123761 A TW 107123761A TW 107123761 A TW107123761 A TW 107123761A TW I791029 B TWI791029 B TW I791029B
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gas
layer
substrate
hydrogen
film
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TW107123761A
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TW201917771A (zh
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徐翼
倉富敬
艾夫傑尼諾斯Ｖ 傑拉多斯
維卡許 班西亞
鎂 張
大東和也
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美商應用材料股份有限公司
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Abstract

一種用於在半導體處理腔室中於基板上形成膜的方法，包括使用電漿增強製程以及基於氯化物的氣體、氫氣、及惰氣之氣體化合物在基板上形成第一層。之後沖洗該處理腔室，且以基於氫的前驅物氣體熱浸泡該第一層。之後再度沖洗該處理腔室，且可用該電漿增強製程或不用該電漿增強製程重複該製程，直到在基板上達成一定的膜厚度為止。

Description

沉積半導體膜的方法
本案原理的實施例大致上關於用在半導體製造中的半導體製程。
用於半導體製造的矽基板經常具有氧化矽，該氧化矽是在處理期間形成於表面上，而大幅度地增加基板上形成的任何接觸件的電阻率。能夠使用反應性矽化物與該氧化矽交互作用，而形成更好的接觸區域。鋁經常用作為接觸件，不利的是鋁與矽化物及下面的矽反應，而引發接面失效。然而，發現矽化鈦產生卓越的接觸區域，同時能夠使用氮化鈦阻障層，而減少與鋁相關的矽吸附問題。
基於該等理由，常使用矽化鈦形成歐姆接觸件，且減少原位電晶體連接的接觸電阻。在基板上形成矽化鈦層期間，經常從基板消耗矽，引發矽材料減少，並且在基板中矽對氧化矽的選擇比降低。大致上，在矽化鈦沉積製程期間經常使用高溫(例如，攝氏700度)。
因此，發明人已開發用於在基板上沉積矽化鈦與其他類型的膜的改良製程。
提供用於在半導體處理腔室中於基板上形成增強膜的方法與設備。
在一些實施例中，用於在基板上形成膜的方法包括：以低於攝氏500度的處理溫度在基板上沉積膜，這是透過下述方式達成：使用電漿增強製程以及基於氯化物的氣體、氫氣、及惰氣之氣體化合物在該基板上形成第一層，以及以至少基於氫的前驅物氣體熱浸泡該第一層。在一些實施例中，該方法進一步包括，不使用該電漿增強製程且使用基於氯化物的氣體、氫氣、及惰氣之氣體化合物而在該第一層上形成第二層，以及以至少基於氫的前驅物氣體熱浸泡該第二層。
在一些實施例中，該方法進一步包括：不使用該電漿增強製程且使用基於氯化物的氣體、氫氣、及惰氣之氣體化合物而在該第一層上形成第二層；以及以至少基於氫的前驅物氣體熱浸泡該第二層；使用該電漿增強製程及基於氯化物的氣體、氫氣、及惰氣之氣體化合物在該第一層上形成第二層；以及以至少基於氫的前驅物氣體熱浸泡該第二層；以低於大約0.283瓦/cm2 供能給該電漿增強製程；以低於大約0.141瓦/cm2 供能給該電漿增強製程；以該至少基於氫的前驅物氣體熱浸泡達一持續持間，該持續時間為大約100毫秒至大約10秒；其中該惰氣是氬氣；其中該電漿增強製程是電漿增強原子層沉積製程以及電漿增強化學氣相沉積製程的其中一者；於大約1毫托耳至大約100托耳的壓力沉積該膜；其中該膜的沉積發生在大約50托耳的壓力；及/或重複該膜的沉積，直到在該基板上達成一定的厚度為止。
在一些實施例中，用於在半導體處理腔室中於基板上形成膜的方法包括：在基板上沉積膜，這是透過下述方式達成：使用電漿增強製程以及基於氯化物的氣體、氫氣、及惰氣之氣體化合物在該基板上形成第一層；從該半導體處理腔室沖洗氣體；以至少基於氫的前驅物氣體熱浸泡該第一層達大約100毫秒至大約10秒的持續時間；從該半導體處理腔室沖洗氣體；以及重複該膜的沉積，直到在該基板上達成一定的厚度為止。在一些實施例中，該方法進一步包括，不使用該電漿增強製程且使用基於氯化物的氣體、氫氣、及惰氣之氣體化合物而在該第一層上形成第二層，以及以至少基於氫的前驅物氣體熱浸泡該第二層。
在一些實施例中，該方法進一步包括：使用基於氯化物的氣體、氫氣、及惰氣之該氣體化合物而在該第一層上形成第二層，不使用該電漿增強製程形成該第二層；以及以至少基於氫的前驅物氣體熱浸泡該第二層；以低於大約0.283瓦/cm2 供能給該電漿增強製程；以低於大約0.141瓦/cm2 供能給該電漿增強製程；以該至少基於氫的前驅物氣體熱浸泡達一持續持間，該持續時間為大約100毫秒至大約10秒；其中該電漿增強製程是電漿增強原子層沉積製程以及電漿增強化學氣相沉積製程的其中一者；於大約1毫托耳至大約100托耳的壓力沉積該膜；及/或其中該膜的沉積發生在大約50托耳的壓力。
在一些實施例中，用於在半導體處理腔室中於基板上形成膜的方法包括：在基板上沉積膜，這是透過下述方式達成：使用功率密度為小於約0.283瓦/cm2 的電漿增強製程以及基於氯化物的氣體、氫氣、及惰氣之氣體化合物在該基板上形成第一層；從該半導體處理腔室沖洗氣體；以至少基於氫的前驅物氣體熱浸泡該第一層；從該半導體處理腔室沖洗氣體；以及不使用該電漿增強製程而在該基板上形成後續的層；以及以至少基於氫的前驅物氣體熱浸泡該後續的層。
下文揭露其他及進一步之實施例。
半導體元件的製造製程期間使用許多不同類型的膜。該等製程的效能不僅僅影響最終半導體產品的成本，也影響製程的時間、熱預算、及消耗的材料量。本案原理的方法及設備的一些實施例能夠用於製造含有過渡金屬及其他物種（諸如在例如原位摻雜中使用的鍺、磷、硼等）的膜。為了簡潔起見，在下文將會基於含矽物種討論一些實施例的特定範例。然而，該等方法與設備不限於含矽物種。該等方法也可在小於攝氏500度執行，而有利地減少基板之熱預算。也可以低於200瓦的用於在300mm晶圓上使用電漿增強製程進行膜沉積的射頻功率（或是小於0.283瓦/cm2 ）執行該等方法，而有利地減少製程的操作成本。該等方法也有利地達成較低的氯化物雜質水準。
在一些半導體製程中，使用矽化鈦（TiSix ，其中x≦3）以例如產生歐姆接觸及減少接觸電阻。基於氯化鈦的氣體（TiClx ，其中x≦4）用在沉積製程中，以在矽晶圓上形成TiSix 。該TiClx 與基板中的矽交互作用，而形成TiSix 。該交互作用在製程期間消耗基板的表面矽的其中一些矽，而比起氧化矽上的沉積矽化鈦的量，減少了矽上的沉積矽化鈦的量（例如厚度）。矽上沉積的TiSix 的量相對於氧化矽上沉積的TiSix 的量的差異可稱作矽對氧化矽（Si:SiO2 ）的選擇比（針對TiSix 的沉積而言）。矽上相對於氧化矽上的沉積速率愈高，會有利地造成高選擇比。習知製程經常具有低於3:1的低選擇比。在一些實施例中，本案原理之方法有利地產生大於約5:1的選擇比。在一些實施例中，該等方法有利地在沉積期間保留基板中的矽，同時在基板上產生高品質的TiSix 膜。在一些實施例中，可與其他過渡金屬（除了Ti之外）一併使用其他過渡金屬鹵化物（除了TiClx 以外），諸如鉭以及氯化鉭（TaCl4 ）及類似物。
在TiSix 的範例中，TiSix 膜是使用依序TiClx （H2 ）電漿增強沉積以及基於矽之前驅物熱浸泡（例如，甲矽烷（SiH4 ）或其他基於矽之氣體）而形成。在一些利用例如其他過渡金屬之實施例中，可使用其他過渡金屬鹵化物以取代TiClx 。在一些利用基於鍺、基於磷、或基於硼、或其他受摻雜的膜的實施例中，舉例而言，可使用非基於矽的前驅物熱浸泡，該熱浸泡可包括例如鍺烷（GeH4 ）、膦（PH3 ）、及/或二硼烷（B2 H6 ）。在一些實施例中，非基於矽的前驅物可包括鹵化物，諸如，舉例而言三氯化硼（BCl3 ）、三氯化磷（PCl3 ）、各種氯矽烷、及各種氯鍺烷、及類似物。圖1描繪根據本案原理之一些實施例在基板上沉積膜（諸如，舉例而言矽化鈦（TiSix ））的方法100之流程圖。第一層206（圖2B）（例如，矽化鈦（TiSix ））沉積在基板202（諸如，舉例而言用在形成TiSix 膜的矽基板）上，這是透過下述方式達成：在電漿增強製程中使基於氯化物的氣體（諸如，舉例而言用於TiSix 膜的氯化鈦（TiClx ））與氫氣（H2 ）及惰氣之處理氣體混合物204流動（流程圖方塊102），如圖2A所說明。在一些實施例中，該惰氣為氬氣。該處理氣體混合物204與該惰氣可預先混合，之後才流動或在流動期間混合（例如，氣體到進入處理腔室為止都是分開的）。
該電漿增強製程可包括電漿增強化學氣相沉積製程或是電漿增強原子層沉積製程。該電漿增強沉積製程與熱浸泡是在低於攝氏500度的溫度執行。在一些實施例中，該溫度可為大約攝氏300度，以用於沉積及熱浸泡。在一些實施例中，溫度可在方法100的持續期間中維持住。透過將製程維持在低溫，方法100的效能增加。透過使製程在大約一般的溫度，該等製程可有利地在單一處理腔室中執行，且有利地增加製造產率且減少處理成本。
在一些實施例中，針對電漿增強製程供應的射頻（RF）功率可小於0.283瓦/cm2 。在其他實施例中，在電漿增強製程期間供應的電力可小於0.141瓦/cm2 。較佳的選擇性可在更低的功率層級達成。較低的功率層級也造就更有效率的製程。在一些實施例中，所供應的RF能量在頻率上範圍是從約2MHz至約60MHz，或舉例而言，可使用非限制性的頻率，諸如2MHz、13.56MHz、27.12MHz、或60MHz。在一些實施例中，可設置複數個RF電源以提供複數個上述頻率的RF能量。
在一些實施例中，可在膜沉積及熱浸泡期間於大約1毫托耳至大約100托耳的壓力執行方法100。在其他實施例中，在膜沉積及熱浸泡期間於大約50托耳的壓力執行方法100。在一些實施例中，在抽空或沖洗期間，壓力可達到0或負壓（真空）。
圖2A描繪基板202的剖面視圖200A，處理氣體混合物204流動以沉積第一層206（圖2B）。使用RF電力以由處理氣體混合物204形成電漿205，該電漿205與基板202交互作用，而形成第一層206，如圖2B的剖面視圖200B所示。TiClx 氣體分子鍵被電漿205所斷裂。來自斷裂的TiClx 氣體分子的鈦分子更容易於較低的溫度由例如基板202中的矽分子所吸附，而從基板202消耗矽。該反應引發沉積的TiSix 膜的Si:SiO2 之選擇比降低。
來自該反應的分子中的一些分子可能不會被吸附。執行沖洗製程以從基板202移除任何未吸附的分子，以及任何殘餘氣體（圖1的流程圖方塊104）。該沖洗製程可包括：於基板202上方流動惰氣，及/或在基板202附近泵抽移除任何氣體。基於氫的前驅物208隨後於基板202上方流動，以熱浸泡第一層206（圖1的流程圖方塊106），如圖2C之剖面視圖200C所說明。在一些實施例中，該基於氫的前驅物208可包括甲矽烷（SiH4 ）、鍺烷（GeH4 ）、膦（PH3 ）、及/或二硼烷（B2 H6 ）及/或其他前驅物。舉例而言，鍺基板可使用鍺烷作為基於氫的前驅物，磷基板可使用膦作為基於氫的前驅物，且硼基板可使用二硼烷作為基於氫的前驅物。
在一些實施例中，熱浸泡可具有大約100毫秒至大約10秒的持續時間。在TiSix 的範例中，矽分子（例如來自甲矽烷（SiH4 ））吸附至第一層206中，而補充在電漿增強沉積製程期間被消耗掉的矽。該熱浸泡增加第一層206的生長、電阻率和結晶率，且若該製程為基於矽且有矽基板，則該熱浸泡增加基板202的矽選擇比。熱浸泡的持續時間愈長，生長、電阻率、及結晶率的影響愈大。相較於不使用基於氫的前驅物208時，利用基於氫的前驅物208的熱浸泡也降低氯化物雜質。該基於氫的前驅物208也可與惰氣共同流動，或可與惰氣及氫氣（H2 ）共同流動。在一些實施例中，該惰氣可為氬氣。
熱浸泡第一層206之後，執行沖洗製程以從基板202移除基於氫的前驅物208及/或任何未吸附的分子（圖1之流程圖方塊108）。該沖洗製程可包括，於基板202上方流動惰氣及/或泵抽移除基板202附近的任何氣體。第二層212（如圖2E之剖面視圖200E所描繪）可視情況任選地沉積在第一層206上，這是透過下述方式達成：利用或不利用電漿增強製程，使基於氯化物之氣體與氫氣（H2 ）及惰氣的處理氣體混合物210流動（流程圖方塊110），如圖2D之剖面視圖200D所示。對於使用電漿增強製程的一些實施例而言，已針對流程圖方塊102於上文描述該電漿增強製程。
在圖2D中以虛線說明電漿211，以顯示形成電漿211是視情況任選的。在無電漿增強製程的一些實施例中，處理氣體混合物210於基板202上方流動，而無電漿所提供的分子鍵弱化效應。儘管鍵結並未被電漿弱化，但處理氣體混合物210被第一層及基板202吸附。在不使用電漿211的情況下，第二層212會具有與第一層206不同的膜性質。無論是利用或不利用電漿增強製程的情況，於基板上形成膜的同時都會進一步增強沉積膜的選擇比。
隨後執行沖洗製程，以從基板202移除任何非吸附的分子以及任何氣體（圖1之流程圖方塊112）。該沖洗製程可包括於基板202上方流動惰氣及/或泵抽移除基板202附近的任何氣體。隨後基於氫的前驅物214於基板202上方流動，以熱浸泡第二層212（圖1之流程圖方塊114），如圖2F之剖面視圖200F所說明。在一些實施例中，用於第二層212的基於氫的前驅物214以及用於第一層206的基於氫的前驅物208可為不同氣體或不同的氣體混合物。在一些實施例中，該基於氫的前驅物214可包括甲矽烷（SiH4 ）或其他矽衍生氣體、鍺烷（GeH4 ）或其他鍺衍生氣體、膦（PH3 ）或其他磷衍生氣體、及/或二硼烷（B2 H6 ）或其他硼衍生氣體、及/或其他前驅物。在一些實施例中，可使用該基於氫的前驅物214執行原位摻雜，這是透過下述方式：使用B2 H6 或PH3 與SiH4 ，而提供遍及整個TiSix 膜（此為舉例）分佈的摻雜劑。在一些實施例中，砷可用作為n型摻雜劑。在一些實施例中，可使用鎵摻雜劑取代硼摻雜劑。
當執行熱浸泡時，持續時間可變化或可為大約相同。在一些實施例中，熱浸泡可具有大約100毫秒至大約10秒的持續時間。熱浸泡增加第二層212的生長、電阻率、及結晶度。熱浸泡第二層212之後，可視情況任選地執行沖洗製程，以從基板202移除基於氫的前驅物214及/或任何非吸附的分子，之後基板202才移除，或是之後才進行基板202的任何額外後續處理（圖1的流程圖方塊116）。該沖洗製程可包括使惰氣於基板202上方流動及/或泵抽移除基板202附近的任何氣體。
在一些實施例中，可視情況任選地重複方法100的上述方塊，直到符合標準為止（圖1的流程圖方塊118）。舉例而言，可重複方法100，直到達成一定的膜厚度或達到一定的選擇比（諸如，對TiSix 而言例如為Si:SiO2 ＞3:1）及類似情況為止。在本案原理的一些實施例中，可不執行方法100的該等方塊的一些方塊。在本案原理的一些實施例中，可也可執行方法100的方塊超過一次及/或以不同順序執行該等方塊。對於基於矽的物種（諸如，舉例而言TiSix ）而言，透過執行該方法100超過一次，則能夠達成大於5:1的Si:SiO2 選擇比。在一些實施例中，例如基於TiSix 的實施例中，進一步重複方法100可達成大約10:1至大約20:1的Si:SiO2 之更高的選擇比。在一些實施例中，該選擇比可大約為15:1。
圖3說明根據本案原理的一些實施例的處理腔室300。該處理腔室300具有腔室主體302及處理空間322。基板308安置於基板支撐件306上，該基板支撐件306由底座304所撐托。在電漿增強沉積期間，處理氣體混合物311從處理氣體源310流動，在一些實施例中，該處理氣體源310提供基於氯化物的氣體與氫氣（H2 ）及惰氣的氣體混合物。在一些實施例中，該惰氣為氬氣。該處理氣體混合物311及該惰氣可預先混合，之後才流動或在流動期間混合（例如，氣體到進入腔室主體302之前都是分開的）。
對一些實施例而言，可藉由使用來自RF電源316的RF電力將處理氣體混合物311點燃成電漿320。在處理空間322中，電漿320與基板308交互作用。沉積後，由泵318沖洗處理空間，以移除沉積氣體與分子。該沖洗製程可包括流動惰氣。基於氫的前驅物315隨後從前驅物源314流進處理空間322。以基於氫的前驅物315在基板上308執行熱浸泡。在沉積與熱浸泡過程期間，溫度控制器324維持處理腔室300內大約一般的溫度。
之後透過泵318從處理空間322沖洗基於氫的前驅物315。該沖洗製程可包括流動惰氣。隨後能夠於處理腔室300中重複該等製程，直到達成一定膜厚度及/或達成一定選擇比為止。在一些實施例中，在第一沉積之後不使用電漿320。在一些實施例中，在後續熱浸泡製程中使用不同前驅物。
處理腔室300為代表性且可為電漿增強原子層沉積（PEALD）腔室或是電漿增強化學氣相沉積（PECVD）腔室及類似腔室。以上述方法使用單一腔室的能力減少了半導體製造期間的處理時間、可消耗的材料、及複雜度。
儘管前述內容涉及本案原理之實施例，但在不背離本案原理之基本範疇的情況下可設計其他及進一步之該等原理之實施例。
100‧‧‧方法102-118‧‧‧步驟200A-200F‧‧‧剖面視圖202‧‧‧基板204‧‧‧氣體混合物205‧‧‧氣體混合物206‧‧‧第一層208‧‧‧前驅物210‧‧‧氣體混合物211‧‧‧電漿212‧‧‧層300‧‧‧處理腔室302‧‧‧腔室主體304‧‧‧底座306‧‧‧基板支撐件308‧‧‧基板310‧‧‧氣體源311‧‧‧氣體混合物314‧‧‧前驅物源315‧‧‧前驅物316‧‧‧RF電源318‧‧‧泵320‧‧‧電漿322‧‧‧處理空間324‧‧‧溫度控制器
透過參考附圖描繪的本案原理之說明性實施例，可了解上文簡要總結且於下文更詳細論述的本案原理之實施例。然而，應注意，附圖僅說明本案原理之典型實施例，因此不應將該等附圖視為限制本案原理之範疇，因為本案原理可容許其他等效實施例。
圖1描繪根據本案原理的一些實施例的在基板上沉積膜的方法之流程圖。
圖2A至圖2F描繪根據本案原理的一些實施例的在基板上的膜沉積。
圖3描繪根據本案原理的一些實施例的代表性半導體處理腔室。
為了助於理解，在可能的情況下，已使用相同元件符號來表示圖中共有的相同元件。該等圖式並未按照比例尺繪製，且可能為了明確起見而經過簡化。一個實施例的元件及特徵可有利地合併於其他實施例中，而無須贅述。
國內寄存資訊 (請依寄存機構、日期、號碼順序註記) 無
國外寄存資訊 (請依寄存國家、機構、日期、號碼順序註記) 無
100‧‧‧方法
102-118‧‧‧步驟

Claims (17)

  1. 一種用於在基板上形成膜的方法，包括：以低於攝氏500度的處理溫度在該基板上沉積一膜，透過下述方式達成：使用一電漿增強製程以及第一氣體在該基板上形成一第一層，該第一氣體具有一基於氯化物的氣體、一氫氣、及一惰氣，以至少一第一基於氫的前驅物氣體熱浸泡該第一層；不使用一電漿增強製程且使用第二氣體在該第一層上形成一第二層，該第二氣體具有一基於氯化物的氣體、一氫氣、及一惰氣，以及以至少一第二基於氫的前驅物氣體熱浸泡該第二層。
  2. 如請求項1所述之方法，進一步包括：以低於大約0.283瓦/cm2供能給該電漿增強製程。
  3. 如請求項1所述之方法，進一步包括：以低於大約0.141瓦/cm2供能給該電漿增強製程。
  4. 如請求項1所述之方法，其中熱浸泡該第一層及/或熱浸泡該第二層執行達一持續持間，該持續時間為大約100毫秒至大約10秒。
  5. 如請求項1所述之方法，其中該惰氣是氬氣。
  6. 如請求項1所述之方法，其中該電漿增強製程是一電漿增強原子層沉積製程以及一電漿增強化學氣相沉積製程的其中一者。
  7. 如請求項1所述之方法，其中於大約1毫托耳至大約100托耳的壓力沉積該膜。
  8. 如請求項7所述之方法，其中沉積該膜是發生在大約50托耳的壓力。
  9. 如請求項1所述之方法，進一步包括：重複沉積該膜，直到在該基板上達成一定的厚度為止。
  10. 一種用於在半導體處理腔室中於基板上形成膜的方法，包括：在該基板上沉積一膜，透過下述方式達成：使用一電漿增強製程以及第一氣體在該基板上形成一第一層，該第一氣體具有一基於氯化物的氣體、一氫氣、及一惰氣；從該半導體處理腔室沖洗氣體；以至少一第一基於氫的前驅物氣體熱浸泡該第一層達大約100毫秒至大約10秒的持續時間；從該半導體處理腔室沖洗氣體； 不使用一電漿增強製程，使用第二氣體在該第一層上形成一第二層，該第二氣體具有一基於氯化物的氣體、一氫氣、及一惰氣；以至少一第二基於氫的前驅物氣體熱浸泡該第二層；以及重複該膜的沉積，直到在該基板上達成一定的厚度為止。
  11. 如請求項10所述之方法，其中該電漿增強製程是使用低於大約0.283瓦/cm2的電力執行。
  12. 如請求項10所述之方法，進一步包括：該電漿增強製程是使用低於大約0.141瓦/cm2的電力執行。
  13. 如請求項10所述之方法，其中熱浸泡該第一層及/或熱浸泡該第二層執行達一持續持間，該持續時間為大約100毫秒至大約10秒。
  14. 如請求項10所述之方法，其中該電漿增強製程是一電漿增強原子層沉積製程以及一電漿增強化學氣相沉積製程的其中一者。
  15. 如請求項10所述之方法，其中沉積該膜是於大約1毫托耳至大約100托耳的一壓力執行。
  16. 如請求項10所述之方法，其中沉積該膜是發生在大約50托耳的壓力。
  17. 一種用於在半導體處理腔室中於基板上形成膜的方法，包括：在該基板上沉積一膜，透過下述方式達成：使用功率密度為小於約0.283瓦/cm2的一電漿增強製程以及第一氣體在該基板上形成一第一層，該第一氣體具有一基於氯化物的氣體、一氫氣、及一惰氣；從該半導體處理腔室沖洗氣體；以至少一第一基於氫的前驅物氣體熱浸泡該第一層；從該半導體處理腔室沖洗氣體；以及不使用一電漿增強製程，而在該第一層上形成一後續的層；以及以至少一第二基於氫的前驅物氣體熱浸泡該後續的層。
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