TW202310683A - 形成包括碳化矽層的結構之方法以及填充基材表面上的溝槽之方法 - Google Patents

形成包括碳化矽層的結構之方法以及填充基材表面上的溝槽之方法 Download PDF

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TW202310683A
TW202310683A TW111125997A TW111125997A TW202310683A TW 202310683 A TW202310683 A TW 202310683A TW 111125997 A TW111125997 A TW 111125997A TW 111125997 A TW111125997 A TW 111125997A TW 202310683 A TW202310683 A TW 202310683A
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reaction chamber
substrate
precursor
plasma power
silicon carbide
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須佐圭雄
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荷蘭商Ａｓｍ Ｉｐ私人控股有限公司
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Abstract

所揭示者係用於形成包括碳化矽層的結構之方法及系統及使用前述方法及系統形成之結構。例示性方法包括提供一碳化矽前驅物至反應室；在反應室內形成一電漿，以在基材表面上形成一初始可流動、黏性碳化矽材料，其中初始黏性碳材料變為碳化矽層。例示性方法可包括使用包括一碳-碳三鍵之一碳化矽前驅物及/或使用一相對低電漿功率密度（例如，小於3 W/cm 2）。

Description

形成包括碳化矽層的結構之方法
本揭露大致上係關於形成適於用在電子裝置之製造中的結構之方法。更特定言之，本揭露之實例係關於形成包括碳化矽層的結構之方法、包括此類層的結構、及用於執行方法及/或形成結構之系統。
在裝置（諸如半導體裝置）之製造期間，常係所欲的是在具有絕緣或介電材料之基材表面上填充特徵（例如，溝槽或間隙）。一些填充特徵的技術包括沉積可流動碳材料層。
最近，在碳化矽作為電子裝置形成中的介電材料之用途受到關注。碳化矽對氧化矽及氮化矽可展現相對高的蝕刻選擇性。然而，碳化矽層可展現若干缺點，當欲填充的特徵之大小減小時尤是。例如，在碳化矽材料的沉積期間，可在所沉積的材料內（具體係在基材表面上的間隙內）形成孔洞。進一步地，諸如電漿原子層沉積之技術可相對緩慢且因此相對昂貴。
因此，所欲的是用於形成結構之改善方法，具體係以碳化矽填充基材表面上的間隙之方法，方法緩解碳材料中的孔洞形成及/或相對快速。
本節提出之任何討論（包括問題及解決方案之討論）僅為了提供本揭露脈絡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係關於形成適於用在電子裝置形成中的結構之方法。雖然在下文更詳細地討論本揭露之各種實施例應對先前方法及結構之缺點的方式，大致上，本揭露之例示性實施例提供用於形成包括包括碳化矽的一層之改善方法、包括碳化矽層之結構、及用於執行方法及/或形成結構之系統。本文所述之方法可用以填充一基材表面上的特徵。
根據本揭露之各種實施例，提供形成一結構之方法。例示性方法包括在一反應室內提供一基材、提供一前驅物至反應室、及施加電漿功率以在反應室內形成一電漿，其中電漿功率係小於經暴露至電漿的基材之一平面表面積的約3.0 W/cm 2以形成包含碳化矽的層。根據本揭露之實例，前驅物包括包含矽及碳的一分子。根據本揭露之進一步的實例，分子包含一碳-碳三鍵。分子的一分子量可係相對高（例如，大於150 Da）。如下文更詳細地闡明，使用相對低的功率密度允許一前驅物分子（例如，碳-碳三鍵及/或碳-矽鍵）的大部分在電漿中存活並鍵合或附接至一基材表面。根據這些實施例之進一步的實例，一基材溫度可相對低（例如，小於120°C）。相對低的基材溫度可允許活性物種沿著基材表面遷移。根據又進一步的實例，方法可作為一電漿增強化學氣相沉積方法執行，其允許相對快速及/或較便宜的基材處理。
根據本揭露之進一步的實例，一種方法包括在一反應室內提供一基材；提供一前驅物至反應室；及施加電漿功率以在反應室內形成一電漿，其中前驅物包括包含矽及一碳-碳三鍵的一分子。用以在施加步驟期間形成一電漿之一功率可小於3.0 W/cm 2或介於約0.5與約3.0 W/cm 2之間。
根據本揭露之又進一步的例示性實施例，一種結構係至少部分地根據本文所述之方法形成。
根據本揭露之又進一步的例示性實施例，提供一種系統，其用於執行一方法及/或用於形成一膜結構，如本文所述者。
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所揭示的（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理解本發明延伸超出本發明之具體揭示的實施例及/或用途以及其等之明顯修改與等同物。因此，意欲使所揭示之本發明的範疇不應受下文所述之特定揭示實施例的限制。
本揭露大致上係關於沉積材料之方法、形成結構之方法、使用方法所形成之結構、及用於執行方法及/或形成結構之系統。舉實例而言，本文所述之方法可用以在基材表面上以碳化矽材料填充特徵（諸如，間隙（例如，溝槽或貫孔））。用語間隙(gap)及凹部(recess)可互換地使用。
欲減輕間隙填充製程期間之孔隙及/或接縫的形成，所沉積的碳化矽材料初始可係可流動的，並在間隙內流動以填充間隙。本文所述之例示性結構可用在各種應用中，包括，但不限於3D交叉點記憶體裝置中的單元(cell)隔離、自對準貫孔、虛擬閘極、反相圖案、PC RAM隔離、切割硬遮罩、DRAM儲存節點接觸(SNC)隔離、及類似者。
在本揭露中，「氣體(gas)」可指在常溫及常壓下為氣體之材料、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（諸如噴淋頭）、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，氣體包括密封氣體（諸如，稀有氣體）。在一些情況下（諸如在材料沉積之背景下），用語「前驅物(precursor)」可指參與生成另一化合物之化學反應的化合物，且具體係指構成膜基質或膜之主要架構的化合物，而用語「反應物(reactant)」可指在一些情況下有別於前驅物之化合物，其使前驅物活化、對前驅物進行改質、或催化前驅物之反應。在一些情況下，用語前驅物(precursor)及反應物(reactant)可互換地使用。用語「惰性氣體(inert gas)」係指當例如施加功率（例如，RF功率）時，在可察覺的程度上不參與化學反應的氣體及/或激發前驅物（例如，以促成前驅物聚合）的氣體，但不像反應物，惰性氣體無法在可察覺的程度上變為膜基質之一部分。例示性惰性氣體包括氬或氦。載體氣體可用以輔助前驅物至反應室的輸送。此外，載體氣體可用以在反應室內點燃及/或維持電漿。
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）、或化合物半導體材料（諸如III-V族或II-VI族半導體），並可包括上覆或下伏於塊材的一或多層。進一步地，基材可包括各種特徵（諸如，間隙（例如，凹部或貫孔）、線或突起部（諸如，具有形成於其等之間的間隙之線）、及類似者），特徵經形成在基材之層或塊材的至少一部分之上或之內。舉實例而言，一或多個特徵可具有約10 nm至約100 nm的寬度，約30 nm至約1,000 nm的深度或高度，及/或約3.0至100.0的深寬比。
在一些實施例中，「膜(film)」係指在垂直於厚度方向的方向上延伸的層。在一些實施例中，「層(layer)」係指形成於表面上之具有某一厚度的材料，或者可係膜或非膜結構之同義詞。膜或層可由具有某些特性之離散單一膜或層或者由多個膜或層構成，且相鄰膜或層之間的邊界可或可不明確，且可或可不基於物理、化學、及/或任何其他特性、形成製程或序列、及/或相鄰膜或層之功能或用途而建立。層或膜可係連續的或者不連續的。
如本文所使用，用語「碳化矽(silicon carbide)」或「碳化矽材料(silicon carbide material)」可指其化學式可表示為包括矽和碳的材料。包含碳化矽的層可包括其他元素（諸如，氫）。碳化矽不需是化學計量材料。
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，結構可係基材或包括具有形成在其上之一或多個層及/或特徵的基材。
如本文所使用，用語「化學氣相沉積(chemical vapor deposition)」可指氣相沉積製程，其中基材經暴露至一或多個揮發性前驅物，前驅物在基材表面上起反應及/或分解以產生所欲的層（例如，碳化矽）。
在本揭露中，於一些實施例中且取決於上下文，「連續地(continuously)」可指不中斷真空、在時間線上無中斷、無任何材料插入步驟、未改變處理條件、其後立即、作為下一步驟、或在兩結構間無有別於兩結構之插入的離散物理或化學結構。
流動性（例如初始流動性）可判定如下： 表1
底部/頂部比率(B/T) 流動性
0＜ B/T ＜1 無
1≤ B/T ＜1.5 不良
1.5≤ B/T ＜2.5 良好
2.5≤ B/T ＜3.5 很好
3.5≤ B/T 極好
其中B/T指的是沉積在一凹部底部之膜厚度對（在凹部被填充之前）沉積在形成凹部的一頂面上之膜厚度的比率。一般而言，流動性係利用深寬比為約1或更小之寬凹部來評估，因為一般而言，凹部的深寬比愈高，B/T比率會變得愈高。當凹部的深寬比愈高時，B/T比率大致上變得愈高。如本文所使用，「可流動(flowable)」的膜或材料展現良好或者較佳流動性(flowability)。
如下文更詳細地提出，可在揮發性碳化矽前驅物例如藉由電漿聚合並沉積在基材表面上時暫時地得到膜的流動性，其中氣態前驅物係藉由電漿氣體放電所提供的能量來活化或碎片化以便啟動聚合。所得之聚合物材料可暫時地展現可流動的行為。當沉積步驟完成及/或於一短時段的時間（例如，約3.0秒）後，膜可能不再可流動，而是變為固化，且因此，可不採用分開的固化製程。
在本發明中，變量之任兩個數字可構成變量之可工作範圍，且所指示之任何範圍可包括或排除端值。附加地，所指出的變量之任何數值（不管數值是否以「約」來指示）可指精確值或近似值並包括等效值，且在一些實施例中可指平均值、中間值、代表值、多數值等。進一步言，在本揭露中，於一些實施例中，用語「包括(including)」、「由…構成(constituted by)」、及「具有(having)」可獨立地指「典型或廣泛地包含(typically or broadly comprising)」、「包含(comprising)」、「基本上由…所組成(consisting essentially of)」或「由…所組成(consisting of)」。在本揭露中，於一些實施例中，任何已定義之意義不必然排除尋常及慣例意義。
根據本揭露之例示性實施例之形成一結構之例示性方法包括下列步驟：在一反應室內提供一基材；提供一前驅物至反應室，前驅物包含一分子，分子包含矽及碳；及施加電漿功率以在反應室內形成一電漿。如上文所述，電漿功率可相對低（例如，經暴露至電漿之基材平面表面積的小於3.0 W/cm 2或介於約0.5 W/cm 2與約3.0 W/cm 2之間的功率密度，以形成包含碳化矽的層。雖然前驅物暴露至電漿，相對低的功率密度可允許前驅物的某些化學鍵保持完整。
於在反應室內提供基材的步驟期間，將基材提供至氣相反應器之反應室中。根據本揭露之實例，反應室可形成化學氣相沉積(CVD)反應器（諸如，電漿增強CVD (PECVD)反應器）的部分。本文所述之各種方法步驟可在單一反應室內執行。
在於反應室內提供基材的步驟期間，可使基材處於所欲溫度及/或可使反應室處於所欲壓力（諸如適於後續步驟的溫度及/或壓力）。舉實例而言，反應室內之（例如，基材或基材支撐之）溫度可介於約10°C與約250°C之間。反應室內之壓力可從約100 Pa至約3,000 Pa。根據本揭露之特定實例，基材包括一或多個特徵，諸如凹部。特徵的深寬比可係例如介於約0.5與約15.0之間。
在提供前驅物至反應室之步驟期間，用於形成碳化矽層之前驅物係引入反應室中。例示性前驅物包括化合物或分子，其等包括矽及碳。在一些情況下，分子由碳、矽、及氫組成。根據進一步的實例，分子包含碳-碳三鍵。額外或替代地，分子包含二或更多個矽原子。
進一步地，分子的分子量可大於150 Da（例如，介於150與300 Da之間）。
圖3A及圖3B繪示適於用作前驅物的例示性分子。如圖3A所繪示，分子可包括碳-碳三鍵。在所繪示之實例中，碳-碳三鍵之各碳係鍵接至矽原子。分子進一步包含經結合至矽原子之官能基R1至R6，其等可係經獨立選擇的官能基。根據本揭露之實例，R1至R6可獨立地選自由Cx-Hy烷基組成之群組，其中X的範圍從1至4，且Y的範圍從1至9。
例如，R1至R6之一或多者可包括甲基。圖3B繪示一實例，其中R1至R6之各者係甲基(雙(三甲矽烷基)乙炔)。
前驅物至反應室的流量率可介於約500 sccm與約5,000 sccm之間。
在施加電漿功率以在反應室內形成電漿的步驟期間，足以形成電漿之功率係施加至反應室內之一或多個電極。例示性電極及反應室係在下文連同圖5更詳細地描述。功率的量可取決於基材的表面積（例如，基材的頂表面，針對圓形基材計算為πr²，而未將基材表面上的特徵（例如，間隙、突起部、及類似者）列為因素）。功率密度可係基材表面的小於3.0 W/cm 2或介於約0.5 W/cm 2與約3.0 W/cm 2之間。額外或替代地，功率可小於300 W或介於約50 W與約300 W之間。功率的頻率可小於30 MHz或介於約13.56 MHz與約27.12 MHz之間。
在提供前驅物至反應室之步驟及施加電漿功率以形成電漿之步驟期間，載體氣體可提供至反應室。如上文所述，載體氣體可用以促成前驅物至反應室之輸送、促成電漿點燃、及/或促成電漿維持。載體氣體至反應室的流量率可從約500 sccm至約5,000 sccm。載體氣體可選自例如由氬、氦、氫、氮之一或多者組成的群組。
本文所述之方法可係或可包括PECVD製程。在一些情況下，方法可包括單一非循環沉積製程。
圖1繪示用於PECVD製程之例示性時序。如所繪示，載體氣體可持續流至反應室達週期t1。前驅物可持續流至反應室達週期t2。而且，用以點燃及維持電漿的電漿功率可持續提供達週期t3。如所繪示，提供前驅物之步驟及施加電漿功率之步驟在時間上重疊。進一步地，提供前驅物之步驟可在施加電漿功率之步驟開始之前開始。額外或替代地，施加電漿功率之步驟可在提供前驅物及/或載體氣體之步驟結束之前結束。額外或替代地，t1可在t2及/或t3之前開始及/或在t2及/或t3之後結束。雖然未繪示，在一些情況下，碳化矽前驅物可脈衝至反應室。在這些情況下，各脈衝週期可介於約3.0秒與約1,800.0秒之間。
圖2繪示碳化矽層218在反應室202內於基材204之表面上的沉積。在所繪示之實例中，來自前驅物源206之前驅物208與來自載體氣體源212之載體氣體210的組合214係流至反應室202。在所繪示之實例中，可使用電漿216從前驅物分子移除官能基（例如，R1至R6係圖3A所繪示之分子），使得碳-碳三鍵及碳-矽鍵實質上保持完整。分子之剩餘部分可聚合以形成初始可流動的碳化矽層，其固化為碳化矽層218。
本文所述之方法可用來以無孔隙方式填充基材表面上之特徵。圖4繪示根據本文所述之方法形成之結構400。結構400包括基材402，其具有形成於其上之突起部404及特徵（例如，溝槽、間隙、或凹部）406。碳化矽408係形成在凹部406內。
圖5根據本揭露之例示性實施例繪示反應器系統500。反應器系統500可用以執行如本文所述之一或多個步驟或子步驟及/或用以形成如本文所述之一或多個結構或其等之部分。
反應器系統500在反應室3之內部11（反應區）中包括平行且面向彼此之一對導電平板電極4、2。可藉由從功率源25施加電漿功率至一個電極（例如，電極4）並將另一電極（例如，電極2）電氣接地而在反應室3內激發電漿。溫度調節器可在下部台2（下部電極）中提供，且放置在其上之基材1的溫度可保持在所欲溫度。電極4可充當氣體分配裝置（諸如噴淋板）。前驅物氣體、及載體氣體、及/或類似者可使用氣體管線20及氣體管線22之一或多者引入反應室3中。氣體可流過噴淋板4。儘管繪示有兩個氣體管線，反應器系統500可包括任何合適數目之氣體管線。
在反應室3中，提供具有排氣管線7之圓管13，可通過其排出反應室3之內部11中的氣體。此外，經設置在反應室3下方之傳遞室5設有密封氣體管線24，以經由傳遞室5的內部16（傳遞區）將密封氣體引入至反應室3的內部11中，其中提供用於分開反應區與傳遞區之分隔板14（此圖式省略閘閥，晶圓係通過閘閥傳遞至傳遞室5中或從傳遞室傳遞）。傳遞室亦具備排氣管線6。
在一些實施例中，載體氣體至反應室3之連續流可使用流通系統(FPS)來完成，其中載體氣體管線設有具有前驅物儲槽（瓶）之歧路管線，且主要管線與歧路管線進行切換，其中當僅意欲將載體氣體饋送至反應室時，關閉歧路管線，而當意欲將載體氣體及前驅物氣體兩者均饋送至反應室時，關閉主要管線且載體氣體流通過歧路管線且從瓶與前驅物氣體一起流出。以此方式，載體氣體可連續地流入反應室中，並可持續攜載前驅物達短於載體氣體週期的週期。
所屬技術領域中具有通常知識者將理解，設備包括一或多個控制器26，其經程式化或以其他方式組態以致使施行如本文所述之一或多個方法步驟。如所屬技術領域中具有通常知識者將瞭解的，（多個）控制器係與反應器之各種功率源、加熱系統、泵、機器人及氣體流動控制器、或閥通訊。
在一些實施例中，可使用雙室反應器（經設置為靠近彼此之用於處理晶圓的兩個區段或隔室），其中反應物氣體及稀有氣體可通過共用管線供應，而前驅物氣體係通過非共用管線供應。
前述本發明的實例實施例並未限制本發明的範疇，既然這些實施例僅為本發明之實施例之實例。任何等效實施例均意欲落在本發明之範疇。實際上，除本文中所示及所述者以外，所屬技術領域中具有通常知識者可由本說明書明白本揭露之各種修改（諸如所述元件之替代可用組合）。此類修改及實施例亦意欲落在隨附之申請專利範圍的範疇內。
1:基材 2:導電平板電極/下部台 3:反應室 4:導電平板電極/噴淋板 5:傳遞室 6:排氣管線 7:排氣管線 11:內部 13:圓管 14:分隔板 16:內部 20:氣體管線 22:氣體管線 24:密封氣體管線 25:功率源 26:控制器 202:反應室 204:基材 206:前驅物源 208:前驅物 210:載體氣體 212:載體氣體源 214:組合 216:電漿 218:碳化矽層 400:結構 402:基材 404:突起部 406:特徵 408:碳化矽 500:反應器系統 t1:週期 t2:週期 t3:週期
當結合下列闡釋性圖式考慮時，可藉由參照實施方式及申請專利範圍而對本揭露之例示性實施例有更完整理解。 圖1根據本揭露之例示性實施例繪示方法的時序。 圖2根據本揭露之實例繪示系統及反應機構。 圖3A及圖3B根據本揭露之實施例繪示例示性前驅物分子。 圖4根據本揭露之例示性實施例繪示結構。 圖5根據本揭露之例示性實施例繪示系統。 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，圖式中之一些元件的尺寸可能相對於其他元件而特別放大，以幫助改善對所繪示本揭露實施例的理解。
400:結構
402:基材
404:突起部
406:特徵
408:碳化矽

Claims (20)

  1. 一種形成包含包含碳化矽之一層的一結構之方法，該方法包含下列步驟： 在一反應室內提供一基材； 提供一前驅物至該反應室，該前驅物包含了包含矽及碳之一分子；及 施加電漿功率以在該反應室內形成一電漿，其中該電漿功率小於經暴露至該電漿之該基材表面積每平方公分3.0瓦特（該電漿功率小於3.0 W/cm 2），以形成包含碳化矽之該層。
  2. 如請求項1之方法，其中該分子包含一碳-碳三鍵。
  3. 如請求項1或請求項2之方法，其中該分子之分子量係大於150 Da。
  4. 如請求項1至3中任一項之方法，其中該分子包含二或更多個矽原子。
  5. 如請求項1至4中任一項之方法，其中該分子可由通式表示：
    Figure 03_image001
    其中R1至R6可獨立地選自由Cx-Hy烷基組成之群組，其中X的範圍從1至4，且Y的範圍從1至9。
  6. 如請求項1至5中任一項之方法，其中該分子包含雙(三甲矽烷基)乙炔。
  7. 如請求項1至6中任一項之方法，其中該電漿功率係小於300 W或介於約50與約300 W之間。
  8. 如請求項1至7中任一項之方法，其中該電漿功率係介於該基材之表面每平方公分約0.5瓦特與約3.0瓦特之間（該電漿功率介於約0.5 W/cm 2與約3.0 W/cm 2之間）。
  9. 如請求項1至8中任一項之方法，其中該電漿功率的頻率係小於30 MHz或介於約13.56 MHz與約27.12 MHz之間。
  10. 如請求項1至9中任一項之方法，其進一步包含供應一載體氣體至該反應室，其中該載體氣體係選自由氬、氦、氫、氮之一或多者組成之群組。
  11. 如請求項1至10中任一項之方法，其中該方法係一電漿增強化學沉積方法。
  12. 如請求項1至11中任一項之方法，其中該基材在提供該前驅物之該步驟及施加該電漿功率之該步驟期間的溫度係小於120°C。
  13. 如請求項1至12中任一項之方法，其中提供該前驅物之該步驟及施加該電漿功率之該步驟在時間上重疊。
  14. 如請求項1至13中任一項之方法，其中提供該前驅物之該步驟在施加該電漿功率之該步驟開始之前開始。
  15. 如請求項1至14中任一項之方法，其中施加該電漿功率之該步驟在提供該前驅物之該步驟結束之前結束。
  16. 如請求項1至15中任一項之方法，其中該施加步驟期間之該反應室內的壓力係介於約100 Pa與約3,000 Pa之間。
  17. 如請求項1至16中任一項之方法，其中該施加步驟期間之該反應室內的溫度係介於約10°C與約250°C之間。
  18. 如請求項1至17中任一項之方法，其中該方法並非循環的。
  19. 一種使用如請求項1至18中任一項之方法填充一基材表面上的一溝槽之方法。
  20. 如請求項19之方法，其中該溝槽之一深寬比大於0.5或介於約0.5與約15.0之間。
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