TW202121494A - 形成矽鍺結構之方法 - Google Patents

形成矽鍺結構之方法 Download PDF

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TW202121494A
TW202121494A TW109123520A TW109123520A TW202121494A TW 202121494 A TW202121494 A TW 202121494A TW 109123520 A TW109123520 A TW 109123520A TW 109123520 A TW109123520 A TW 109123520A TW 202121494 A TW202121494 A TW 202121494A
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瑞米 哈莎卡
盧卡斯 彼得森 巴柏沙 立馬
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Abstract

本發明揭示用於形成結構之方法，該等結構包括包含矽鍺的一層。本揭露之例示性實施例提供在該包含矽鍺的層上形成一過渡層的改善方法，其等可減少該包含矽鍺的層與一後續形成之包含矽的層之間的一界面層之任何形成。

Description

形成矽鍺結構之方法
本揭露大致上係關於包括矽鍺層之結構及形成結構之方法。更具體地，本揭露係關於在SiGe層上形成過渡及/或鈍化層之方法，且係關於相關結構。
由於其相對低的能隙及潛在相對高的載子移動率，矽鍺(SiGe)已用於製造各種電子裝置（諸如光偵測器、熱電裝置、雙極性電晶體、及場效電晶體（諸如金氧場效電晶體(MOSFET)））。
近來，由於致力於形成具有增加的裝置密度之裝置，已發展出改善性能及低成本的三維裝置。例如，已發展出鰭式場效電晶體(FinFET)及環繞式閘極場效電晶體（Gate-All-Around FET或GAA FET），該鰭式場效電晶體以鰭片形狀形成通道區，允許至通道區的多個接觸點，該環繞式閘極場效電晶體中的閘極環繞通道區的所有側。
在形成GAA FET期間，可藉由在基材表面上使層循序地磊晶生長來形成交替之包含矽的層（Si層）及包含SiGe的層（SiGe層）之堆疊結構或超晶格。可蝕刻這些層的部分以形成（例如矽）線，其等可形成GAA FET的通道區。
對具有上覆於SiGe層之以磊晶方式形成的Si層之許多裝置而言，可係所欲的是在SiGe層與以磊晶方式形成於其上的Si層之間具有相對小而急遽的過渡。不幸地，SiGe層之表面上的Ge比表面上的Si在能量方面更為有利。因此，若SiGe層的表面在過渡至後續的Si層磊晶生長期間未經鈍化，則會發生Ge分凝，導致形成界面(interfacial/interface)層。接著，隨著Si的第一單原子層生長，Ge會再次分凝至頂部層。此機制在Si層的生長期間可能會重複，製造出數十埃的界面層。
SiGe層可在介於約600 °C與700 °C之間的溫度下使用二氯矽烷(DCS)生長。此類技術導致SiGe層之相對低的生長率（約0.8 nm.min-1 ），並可導致與後續生長的Si層之非所欲的大界面層。
在低於580 °C之溫度下的矽烷(SiH4 )可用以生長上覆於SiGe層的Si層。矽層在此類溫度下的生長係相對低生長率（約0.8 nm.min-1 ），且界面層仍可係非所欲地厚。
因此，所欲的是形成具有SiGe層之結構（諸如，包括上覆於SiGe層之磊晶生長Si層之結構）的改善方法。
本節提出之任何討論（包括問題及解決方案之討論）僅為了提供本揭露背景之目的而包括在本揭露中，且不應視為承認討論之任何或全部內容在完成本發明時已知或以其他方式構成先前技術。
本揭露之各種實施例提供用於形成包括包含SiGe的層（SiGe層）之結構的改善方法。雖然已在下文更詳細地討論先前技術之各種缺點的方式，大致上，例示性方法包括使用複數個矽氣體形成一過渡層，其允許形成一相對薄的界面層，並可允許較高溫度，且從而允許上覆於SiGe層磊晶生長之包含矽的層（Si層）之較快生長率。
根據本揭露之至少一實施例，提供一種形成結構之方法。一種例示性方法包括在反應室內提供包含了包含SiGe的層之基材以及藉由在反應室內提供氣體而在包含SiGe的層上形成過渡及/或鈍化層，氣體包含下列之混合物：第一含矽氣體、含鹵素（例如含氯）氣體、及第二含矽氣體，其中第一含矽氣體不同於第二含矽氣體。第一矽氣體及含鹵素/含氯氣體可在SiGe層的表面上提供所欲的Ge-鹵素或Ge-Cl鍵。諸如當基材溫度高於600 °C時，第二含矽氣體可提供矽至可能存在於表面上的任何空位。第一含矽氣體的化學式可包括鹵素（諸如氯）。例如，第一含矽氣體可包括氯矽烷之一或多者，諸如二氯矽烷(DCS)、一氯五甲基二矽烷(CPMS)、二氯四甲基二矽烷(DTMS)、五氯二矽烷(PCDS)、六氯二矽烷(HCDS)、及/或八氯三矽烷(OCTS)。含鹵素/含氯氣體可係或可包括例如氯化氫(HCl)。第二含矽氣體可包括包含矽及氫之矽烷的一或多者，例如由式Sin H2n+2 表示的矽烷（其中n係從1至4），諸如矽烷(SiH4)、二矽烷(Si2 H6 )、三矽烷(Si3 H8 )、及四矽烷(Si4 H10 )。包含混合物之氣體可包括例如約0.01百分比至約100百分比、或約0.1百分比至約50百分比、或約1百分比至約15百分比的第一含矽氣體；約0.01百分比至約100百分比、或約0.1百分比至約50百分比、或約1百分比至約15百分比的含鹵素氣體；及/或約0.01百分比至約100百分比、或約0.1百分比至約50百分比、或約1百分比至約15百分比的第二含矽氣體。第一含矽氣體對第二含矽氣體之體積流量率的比率之範圍可從約0.001至約10000或約0.1至約10。額外或替代地，含鹵素或含氯氣體對第二含矽氣體之體積流量率的比率之範圍可從約0.001至約10000。例示性方法可額外包括以磊晶方式形成SiGe層及/或在SiGe層上方以磊晶方式形成Si層。SiGe層、過渡、及Si層之二或更多者可在相同反應室內形成，例如在形成SiGe層、過渡、及/或Si層的步驟之間無真空破壞。根據這些一或多個實施例之例示性態樣，方法包括下列步驟：形成SiGe層及形成上覆於SiGe層之Si，其中形成SiGe層的步驟係在第一溫度下執行，且形成Si層的步驟係在第二溫度下執行；第一溫度可相同或不同於第二溫度，例如第二溫度可等於或高於第一溫度。例如，第一溫度可介於約350 ºC與約800 ºC之間，且第二溫度可介於約350 ºC與約800 ºC之間或介於約500 ºC與約700 ºC之間。用以形成SiGe層之氣體可包括0.01百分比至約100百分比、或約0.1百分比至約50百分比、或約1百分比至約15百分比的含矽反應物；及/或約0.01百分比至約100百分比、或約0.1百分比至約50百分比、或約1百分比至約15百分比的含鍺反應物。用以形成Si層之氣體可包括0.01百分比至約100百分比、或約0.1百分比至約50百分比、或約1百分比至約15百分比的含矽反應物。
根據本揭露之另一實施例，一種形成結構之方法包括在反應室內提供基材；使用含矽前驅物在基材之表面上形成包含SiGe的層；及藉由在反應室內提供氣體而在包含SiGe的層上形成過渡及/或鈍化層，氣體包含第一含矽氣體、含鹵素（例如氯）氣體、及第二含矽氣體之混合物。含矽前驅物及第一含矽氣體可係或可包括相同化學式。第一含矽氣體、含鹵素（例如氯）氣體、及第二含矽氣體可係或可包括上文以及本文於別處所提及之第一含矽氣體、含鹵素（例如氯）氣體、及/或第二含矽氣體之任何者。例示性方法可額外包括形成包含矽之層的步驟。可重複形成包含SiGe的層、形成過渡層、及形成包含矽的層之步驟以形成多層或晶格結構，例如適於用在環繞式閘極(GAA)結構及裝置（諸如GAA場效電晶體(GAA FET)）之形成中的結構。
根據本揭露之至少一額外實施例，提供一種結構。結構可根據本文所述之方法形成。一種結構可包括包含矽的第一層或基材；包含矽鍺的層，其上覆於包含矽的第一層或基材；及包含矽的第二層，其上覆於包含矽鍺的層。包含矽的第二層與包含矽鍺的層之間的界面層之厚度可小於0.01 nm、小於0.2 nm、小於20 nm、小於1000 nm、或介於約0.1 nm或1 nm與約5 nm之間。
所屬技術領域中具有通常知識者將從已參照隨附圖式之某些實施例的下列詳細描述輕易明白這些及其他實施例；本發明並未受限於任何已揭示的（多個）特定實施例。
雖然在下文揭示某些實施例及實例，所屬技術領域中具有通常知識者將瞭解本發明延伸超出本發明及其明顯的修改與等同物之具體揭示的實施例及/或用途。因此，意欲使所揭示之本發明的範疇不應受下文所述之具體揭示實施例的限制。
本揭露大致上係關於形成包括包含矽鍺(SiGe)的層之結構之方法及使用該等方法形成之結構。本文所述之例示性方法可用以形成結構，該等結構包括包含SiGe的層及包含矽(Si)的層，該包含矽的層以磊晶方式形成，上覆於包含SiGe的層，使得包含SiGe的層與包含Si的層之間的界面層可相對小，並使得包含SiGe的層與包含Si的層之間的過渡係急遽的。進一步地，例示性方法可包括在相對高的溫度下形成包含矽的層，以允許更快的生長率，同時維持相對小的界面層。
在本揭露中，「氣體(gas)」可指在室溫及壓力下為氣體之材料、汽化固體、及/或汽化液體，並可取決於上下文由單一氣體或氣體混合物構成。有別於製程氣體的氣體（亦即，非通過氣體分配總成、其他氣體分配裝置、或類似者引入的氣體）可用於例如密封反應空間，該氣體包括密封氣體（諸如，稀有氣體）。在一些實施例中，用語「前驅物(precursor)」及「反應物(reactant)」可互換地使用，且大致上可各自指參與生成例如膜或層之化學反應的氣相化合物。
如本文所使用，用語「基材(substrate)」可指可用以形成或在其上可形成裝置、電路、或膜之任何（多個）下伏材料。基材可包括塊材（諸如矽（例如單晶矽））、其他IV族材料（諸如鍺）、或類似者，並可包括上覆或下伏於塊材的一或多層。進一步地，基材可包括各種形貌，諸如形成在基材之一層的至少一部分之內或之上的凹部、線、及類似者。
如本文所使用，用語「磊晶層(epitaxial layer)」可指上覆於實質單晶層或基材之實質單晶層。
如本文所使用，用語「包含矽鍺的層(layer comprising silicon germanium)」或「SiGe層(SiGe layer)」可指包括矽及鍺的層（諸如矽及鍺的合金）。包含矽鍺的層可由通式Si1 − x Gex 表示，其中x大於零且小於一。在一些背景下，包含SiGe的層可包括SiGe塊材。包含矽鍺的層可包括其他元素（諸如，B、As、Ga、P、Sn、In、或類似者的一或多者）。例如，包含矽鍺的層可包括此類其他元素之一或多者的約零或至多約0.01至約95原子百分比。
如本文所使用，用語「包含矽的層(layer comprising silicon)」或「Si層(Si layer)」可指包括矽的層（諸如單晶矽層）。包含矽的層可包括其他元素（諸如摻雜物，包括例如C、P、As、B、Sb、或類似者），例如至多約0.01至約95原子百分比的一或多個其他元素。
如本文所使用，用語「結構(structure)」可指部分或完全製造的裝置結構。舉實例而言，結構可包括具有形成在其上之過渡層及/或鈍化之基材。結構可包括額外的層（諸如包含SiGe的層及/或包含Si的層）。
如本文所使用，除非另有指定，百分比可指體積、質量、或重量百分比，並可指絕對百分比或相對百分比。
除非另有註記，本文所述之方法可用以形成鈍化及/或過渡層。在一些背景下，可將鈍化層及過渡層視為相同的層。除非另有指示，形成過渡層之方法可用以形成過渡層且反之亦然 。
使用DCS及氯化氫(HCl)形成之過渡或鈍化層可用以使鍺分凝穩定，且從而減少SiGe層與Si層之間的鈍化層厚度。Si與Cl之間的鍵比Ge與Cl之間的鍵更為有利。因此，使用DCS及HCl可有助於使Si保持在SiGe層的頂層處。然而，理論上高於600 °C時，Cl與Si鍵結，並可形成SiCl2 且從表面脫附。此將導致Ge可移入其中的空位。
圖1繪示一種製程，其中DCS和鍺烷(GeH4 )係用以磊晶生長SiGe層，DCS和HCl係用以形成過渡層，且SiH4 係用以在SiGe層上生長矽層。使用此一技術可減少SiGe與Si層之間的界面層厚度；然而，界面層厚度仍可非所欲地大。而且，Si層的生長率可非所欲地低。
圖2繪示根據本揭露之至少一實施例之方法200。方法200包括下列步驟：提供包含了包含SiGe的層之基材（步驟202）及形成過渡層（步驟204）。方法200亦可包括形成包含SiGe的層之步驟（步驟206）、及/或形成包含Si的層之步驟（步驟208）、及可選地重複迴圈（步驟210）。
步驟202可包括在反應室內提供如本文所述之基材。舉實例而言，基材可包括塊材矽、包含Si的層、及/或包含SiGe的層。若基材在基材表面上包括包含SiGe的層，則方法200可繼續進行至步驟204。若基材不包括包含SiGe的層，則在繼續進行至步驟204之前，方法200可繼續進行至步驟206。
步驟204包括在包含SiGe的層上形成過渡（及/或鈍化）層。可藉由提供包含二或更多個含矽氣體及含鹵素（例如氯）氣體的混合物之氣體至反應室來形成過渡層。例如，混合物可包括第一含矽氣體、含鹵素（例如氯）氣體、及第二含矽氣體。過渡層的厚度範圍可從約0.01至約20 nm。
在步驟204期間，反應室內的溫度範圍可從約 350 ºC至約800 ºC或約500 ºC至約700 ºC。在步驟204期間，溫度可斜坡升降或變化（例如，從步驟206期間所用的溫度至步驟208期間所用的溫度）。替代地，溫度可相同於步驟206及/或步驟208的溫度或者不同於步驟206或步驟208之任一者中所用的溫度。在步驟204期間，反應室內之壓力範圍可從約1至約760 Torr或約25至約40 Torr。
第一含矽氣體的化學式可包含氯。舉實例而言，第一含矽氣體可係或可包括二氯矽烷(DCS)、一氯五甲基二矽烷(CPMS)、二氯四甲基二矽烷(DTMS)、六氯二矽烷(HCDS)、五氯二矽烷(PCDS)、及/或八氯三矽烷(OCTS)。
含鹵素氣體的化學式可包含鹵素（例如氯）及氫。舉實例而言，含鹵素氣體可係或可包括氯化氫(HCl)。
第二含矽氣體的化學式可包含氫。舉實例而言，第二含矽氣體可係或可包括矽烷（諸如，矽烷(SiH4 )、二矽烷(Si2 H6 )、三矽烷(Si3 H8 )、及/或四矽烷(Si4 H10 )）。
第一含矽氣體、含鹵素/含氯氣體、及第二含矽氣體的流量率可根據一些因素變化，包括基材大小、反應室內的壓力、及反應室大小。根據本揭露之實例，第一含矽氣體至反應室中的流量率可係約0.01至約10000 sccm或約75至約250 sccm；含鹵素氣體至反應室中的流量率可係約0.01至約10000或約200至約300 sccm；且第二含矽氣體至反應室中的流量率可係約0.01至約10000或約50至約75 sccm。第一含矽氣體對第二含矽氣體之體積流量率的比率範圍係從約0.01至約100。額外或替代地，含鹵素或含氯氣體對第二含矽氣體之體積流量率的比率範圍係從約0.01至約100或約0.1至約10。根據進一步的實例，包含混合物的氣體可包括約0.01至約100的第一含矽氣體、約0.01至約100百分比的含鹵素氣體、約0.01至約100百分比的第二含矽氣體、及/或如本文所提出之其他百分比及組成。
再次參照圖2，例如，若在步驟202期間所提供的基材在基材表面上不包括包含SiGe的層，則步驟206包括形成包含SiGe的層。步驟206可包括例如在包含矽的塊材上方或在包含矽的層上方形成包含SiGe的磊晶層。
包含SiGe的（例如磊晶）層可藉由二或更多個反應物至反應室中的共伴流或交替流來形成。例如，包含矽的第一反應物及包含鍺的第二反應物可流入反應室中。包含矽的例示性第一反應物包括DCS、一氯五甲基二矽烷(CPMS)、二氯四甲基二矽烷(DTMS)、六氯二矽烷(HCDS)、五氯二矽烷(PCDS)、及/或八氯三矽烷(OCTS)。包含鍺的例示性第二反應物包括鍺烷(GeH4 )及二鍺烷(Ge2 H6 )。步驟206期間所形成之包含SiGe的層之厚度範圍可從約0.2至約1000 nm或約2至約20 nm。
在步驟206期間，反應室內的溫度範圍可從約 350 ºC至約800 ºC或約500 ºC至約700 ºC。在步驟206期間，反應室內之壓力範圍可從約1 Torr至約760 Torr。
步驟208包括形成例如上覆於包含SiGe的層之包含Si的層。步驟208可包括例如在步驟206期間所形成之包含SiGe的磊晶層上方形成包含Si的磊晶層。步驟208期間所形成之包含SiGe的層之厚度範圍可從約0.2至約1000 nm。
在步驟208期間，反應室內的溫度範圍可從約 350 ºC至約800 ºC或約500 ºC至約700 ºC。在步驟208期間，反應室內之壓力範圍可從約1 Torr至約760 Torr。
根據本揭露之進一步的實例，在步驟204至208的任一者期間，氣體或氣體混合物可進一步包括一或多個載體氣體，其（等）可包括一或多個惰性氣體，以促成反應物至基材表面的輸送。例如，可將氫(H2 )及/或氮(N2 )氣體用作載體氣體。欲減少非所要的反應，步驟204至208或其任一組合可在無真空破壞的情況下於相同反應室內執行。
圖3繪示根據本揭露之說明性實例之方法200的各種步驟。對圖3所繪示之實例而言，形成包含SiGe的層（例如包含SiGe的磊晶層）之步驟係在第一溫度下執行，且形成包含Si的層（例如磊晶層）之步驟係在第二溫度下執行，其中第一溫度可相同或不同於第二溫度；例如，第二溫度可大於或等於第一溫度。在具體說明的實例中，第二溫度高於第一溫度。使用高於第一溫度的第二溫度允許包含矽的層之較高的生長率。藉由使用第二含矽氣體來減少可能發生之界面層生長，咸認為該第二含矽氣體在形成過渡層期間為基材表面貢獻矽原子，以從而減少鍺在形成過渡層期間及/或在形成包含矽的層期間分凝至包含SiGe的層之表面。
圖4繪示根據本揭露之實例之結構400。結構400包括（例如矽）基材402、上覆於基材402之包含SiGe的層404、及上覆於包含SiGe的層404之包含Si的層406。
基材402可係或可包括塊材矽基材。替代地，具有包含矽之單晶層的基材可形成結構400的部分。
包含SiGe的層404可根據上述之步驟206形成。包含SiGe的層404可係形成為上覆於基材402之磊晶層。
包含Si的層406可根據上述之步驟208形成。包含Si的層406可係形成為上覆於包含SiGe的層404之磊晶層。
包含SiGe的層404與包含Si的層406之間的過渡係急遽的（例如，具有如上文提及的厚度）。
上文所述之本揭露之實例實施例並未限制本發明的範疇，因為這些實施例僅為本揭露之實施例之實例；本發明係由隨附之申請專利範圍及其法定等同物定義。任何等效實施例係意欲屬於本發明之範疇內。實際上，除本文中所示及所描述者之外，本揭示案之各種修改(諸如所描述之元件的替代性適用組合)根據描述對熟悉本技藝者而言可變得顯而易見。此等修改及具體例亦意欲屬於所附申請專利範圍之範疇內。
200:方法 202:步驟 204:步驟 206:步驟 208:步驟 210:步驟 400:結構 402:基材 404:包含SiGe的層 406:包含Si的層
當結合下列說明圖式考慮時，可藉由參照實施方式及申請專利範圍而得到對本揭露之例示性實施例的更完整了解。 圖1繪示形成包括過渡層之結構之方法。 圖2繪示根據本揭露之例示性實施例之形成結構之方法。 圖3繪示根據本揭露之例示性實施例之形成結構之方法。 圖4繪示根據本揭露之至少一實施例之結構。 將理解，圖式中之元件係為了簡單及清楚起見而繪示且不一定按比例繪製。例如，圖式中的一些元件之尺寸可相對於其他元件誇大，以幫助提升對本揭露所繪示之實施例的瞭解。
201:方法
202:步驟
204:步驟
206:步驟
208:步驟
210:步驟

Claims (20)

  1. 一種形成一結構之方法，該方法包含下列步驟： 在一反應室內提供一基材，其包含了包含SiGe的一層；及 藉由在該反應室內提供包含下列之一混合物的一氣體而在該包含SiGe的層上形成一過渡層： 一第一含矽氣體； 一含鹵素氣體；及 一第二含矽氣體， 其中該第一含矽氣體不同於該第二含矽氣體。
  2. 如請求項1所述之方法，其中該第一含矽氣體之一化學式包含氯。
  3. 如請求項1所述之方法，其中該第一含矽氣體包含二氯矽烷(DCS)、一氯五甲基二矽烷(CPMS)、二氯四甲基二矽烷(DTMS)、六氯二矽烷(HCDS)、五氯二矽烷(PCDS)、及八氯三矽烷(OCTS)之一或多者。
  4. 如請求項1所述之方法，其中該含鹵素氣體包含氯化氫(HCl)。
  5. 如請求項1所述之方法，其中該第二含矽氣體包含矽烷(SiH4 )、二矽烷(Si2 H6 )、三矽烷(Si3 H8 )、及四矽烷(Si4 H10 )之一或多者。
  6. 如請求項1項所述之方法，其中該包含該混合物之氣體包含約0.01至約100百分比的該第一含矽氣體、約0.01至約100百分比的該含鹵素氣體、及約0.01至約100百分比的該第二含矽氣體。
  7. 如請求項1項所述之方法，其中該第一含矽氣體對該第二含矽氣體之體積流量率的一比率範圍從約0.001至約10000。
  8. 如請求項1項所述之方法，其中該含鹵素氣體對該第二含矽氣體之體積流量率的一比率範圍從約0.001至約10000。
  9. 如請求項1項所述之方法，其中該包含SiGe的層係一磊晶層，且其中該方法進一步包含形成該磊晶層之一步驟。
  10. 如請求項9所述之方法，其中該形成該磊晶層之步驟及該形成該過渡層之步驟係在無真空破壞的情況下於該相同反應室內執行。
  11. 如請求項9所述之方法，其進一步包含形成包含矽的一層之一步驟，該層上覆於該包含SiGe的層， 其中該形成該磊晶層之步驟係在一第一溫度下執行，且該形成該包含矽的層之步驟係在一第二溫度下執行，且 其中該第一溫度不同於該第二溫度。
  12. 如請求項9所述之方法，其進一步包含形成包含矽的一層之一步驟，該層上覆於該包含SiGe的層， 其中該形成該磊晶層之步驟係在一第一溫度下執行，且該形成該包含矽的層之步驟係在一第二溫度下執行，且 其中該第二溫度大於或等於該第一溫度。
  13. 如請求項9所述之方法，其中該形成一過渡層之步驟係在無溫度變化的情況下及/或在一第三溫度下執行。
  14. 一種形成一結構之方法，該方法包含下列步驟： 在一反應室內提供一基材； 使用一含矽前驅物在該基材之一表面上形成包含SiGe的一層；及 藉由在該反應室內提供包含下列之一混合物的一氣體而在該包含SiGe的層上形成一過渡層： 一第一含矽氣體； 一含鹵素氣體；及 一第二含矽氣體。
  15. 如請求項14所述之方法，其中該含矽前驅物及該第一含矽氣體包含相同化學式。
  16. 如請求項14所述之方法，其中該等形成包含SiGe的一層及形成一過渡層之步驟係經重複。
  17. 如請求項14所述之方法，其中該第二含矽氣體包含一矽烷。
  18. 一種結構，其係如請求項1至17項中任一項所述之方法所形成。
  19. 如請求項18所述之結構，其中該結構包含一包含矽的第一層；一包含矽鍺的層，其上覆於該包含矽的第一層；及一包含矽的第二層，其上覆於該包含矽鍺的層。
  20. 如請求項19所述之結構，其中該包含矽的第二層與該包含矽鍺的層之間的一界面層之厚度係約0.01 nm至約20 nm。
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