TW201351482A - 半導體薄膜穩定的方法 - Google Patents

半導體薄膜穩定的方法 Download PDF

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TW201351482A
TW201351482A TW102119967A TW102119967A TW201351482A TW 201351482 A TW201351482 A TW 201351482A TW 102119967 A TW102119967 A TW 102119967A TW 102119967 A TW102119967 A TW 102119967A TW 201351482 A TW201351482 A TW 201351482A
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tin
epitaxial layer
gas
chamber
tin alloy
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Yi-Chiau Huang
Yihwan Kim
Errol Antonio C Sanchez
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Abstract

本發明的具體例通常是關於形成可摻雜硼、磷、砷、或其他n型摻雜物或p型摻雜物的矽鍺錫合金磊晶層、鍺錫合金磊晶層、與鍺磊晶層的方法。該方法通常包含將基板定位在製程腔室中。接著將鍺前驅物氣體導入腔室，同時伴隨著壓力源前驅物氣體，如錫前驅物氣體，以形成磊晶層。隨後停止鍺氣體的氣流，且導入蝕刻劑氣體至腔室中。之後在用於形成磊晶薄膜的壓力源前驅物氣體存在下同時進行回蝕。隨後停止蝕刻劑氣體的氣流，且之後可重覆此循環。除了回蝕處理之外，或做為代替回蝕處理，可以進行退火處理。

Description

半導體薄膜穩定的方法
本發明所述是關於半導體元件製造的技術。更特定而言，是描述形成IV族半導體磊晶材料的方法。
鍺是首先使用在半導體應用(如CMOS電晶體)的材料中的其中之一。由於與鍺相較之下矽更豐富，矽已經是製造CMOS的半導體材料的壓倒性選擇。根據摩爾定律(Moore’s Law)，當元件幾何下降時，電晶體元件的尺寸對於致力於製造出更小、更快速、消耗較少能量、和發熱較少的元件的工程師是一項挑戰。舉例而言，當電晶體的尺寸下降，該電晶體的通道區變得更小，且該通道的電子性質因具有更多電阻率和更高的閥電壓而變得較不可行。某些製造者已經在45奈米的節點達成透過使用嵌入於源極/汲極區的矽鍺壓力源，增加在矽通道區的載子遷移率。然而在未來的節點上，仍然需要更高遷移率的元件。
嘗試形成更高遷移率元件的方法，該方法包含形成矽鍺錫合金磊晶層、鍺錫合金磊晶層、或鍺磊晶層。為了改善沉積的磊晶層的品質，可進行循環的沉積/處理製程，如沉 積/蝕刻或沉積/退火。在沉積/蝕刻的例子中，在沉積特定數量的磊晶材料後，進行短暫的回蝕移除遮罩區域的沉積材料，以促進沉積的選擇性。另一個循環製程，在沉積後可以停止沉積氣體的氣流一段時間，例如進行退火，該退火可以改善磊晶層的結晶及/或活化摻雜物。然而在磊晶層的非沉積處理期間，矽、鍺、和錫的組成會由於遷移而改變。另外，在磊晶層中的其他摻雜物，如III族或V族的元素，也可以遷移或釋氣，因此降低薄膜的品質。此外，各個循環一開始的沉積時，結合IV族的元素(舉例為錫)可能延遲其他IV族元素的結合，該其他IV族元素如矽和/或鍺和/或甚至III族和IV族的摻雜物。這些都是造成薄膜劣化與降低薄膜組成均勻性的潛在來源。
第1圖顯示形成在矽基板104上的鍺錫合金層102，該矽基板104之上具有鍺緩衝層106。該鍺錫合金層102是透過四次之沉積/退火製程的循環而形成。然而，該沉積/退火製程無法造成鍺錫合金層具有均勻的錫分布。相反地，由於在退火製程時錫的遷移，沉積的薄膜包含四個非均勻錫濃度的周期層，該遷移可能部分是由於該退火製程時提昇的溫度，或在沉積的起始暫態階段時錫的結合不佳。該非均勻濃度周期層表示在鍺錫合金層102的三個更高階的尖峰102a、102b、和102c。該非均勻錫的深度分布是不良的性質，其降低薄膜的品質。
因此，在此技術領域有對於形成具有均勻組成分布的磊晶層的需求。
本發明的具體例通常是關於形成可摻雜硼、磷、砷、或其他n型摻雜物或p型摻雜物的矽鍺錫合金磊晶層、鍺錫合金磊晶層、與鍺磊晶層的方法。該方法通常包含將基板定位在製程腔室中。鍺前驅物氣體與任選的矽前驅物氣體和III族或V族氣體，隨後被導入該腔室，同時伴隨著合金化前驅物氣體(如錫前驅物氣體)，以形成磊晶層。然後該鍺氣體的氣流被停止，且將蝕刻劑氣體導入腔室。接著當用以形成磊晶薄膜的該合金化前驅物氣體存在下同時進行回蝕。隨後停止蝕刻劑氣體的氣流，且之後可重覆此循環。除了回蝕處理之外，或做為代替回蝕處理，可以在錫前驅物存在下進行退火處理。當利用III族或V族的氣體時，該III族或V族的氣體在蝕刻期間及/或退火期間可被提供至該製程腔室中。
102‧‧‧鍺錫合金磊晶層
104‧‧‧矽基板
106‧‧‧鍺緩衝層
210‧‧‧流程圖
212‧‧‧操作
214‧‧‧操作
216‧‧‧操作
218‧‧‧操作
220‧‧‧操作
222‧‧‧操作
224‧‧‧操作
302‧‧‧鍺錫合金磊晶層
為了詳細理解本發明上述之特徵，可參照某些描繪於圖式中的具體例，來理解簡短概述於前的本發明的更明確描述。然而，需注意圖式僅描繪本發明之典型具體例，因此圖式不被視為本發明之範疇的限制因素，本發明可以涵蓋其他相等有效的具體例。
第1圖是顯示GeSn薄膜成長在矽基板上的X射線繞射資料，該矽基板上具有鍺緩衝層。
第2圖是根據本發明的一個具體例之用於形成鍺錫合金磊晶層的方法的流程圖。
第3圖是顯示鍺錫合金磊晶層形成在矽基板的X射 線繞射資料，該矽基板上具有鍺緩衝層。
為了促進理解，在可能的情形下，已經把圖式中共通的相同元件標示為相同的參考數字。因而在一個具體例中揭露的元件可有利地應用至其他具體例，未再特別詳述。
本發明的具體例通常是關於形成可摻雜硼、磷、砷、或其他n型摻雜物或p型摻雜物的矽鍺錫合金磊晶層、鍺錫合金磊晶層、與鍺磊晶層的方法。該方法通常包含將基板定位在製程腔室中。鍺前驅物氣體與任選的矽前驅物氣體和III族或V族氣體，隨後被導入該腔室，同時伴隨著合金化前驅物氣體(如錫前驅物氣體)，以形成磊晶層。然後該鍺氣體的氣流被停止，且將蝕刻劑氣體導入腔室。接著當用以形成磊晶薄膜的該合金化前驅物氣體存在下同時進行回蝕。隨後停止蝕刻劑氣體的氣流，且之後可重覆此循環。除了回蝕處理之外，或做為代替回蝕處理，可以在錫前驅物存在下進行退火處理。當利用III族或V族的氣體時，該III族或V族的氣體在蝕刻期間及/或退火期間可被提供至該製程腔室中。
本發明的某些具體例中，錫可與鍺及/或矽形成合金以形成矽鍺錫合金磊晶層或鍺錫合金磊晶層。錫和矽及/或鍺的合金化增加合金薄膜的壓應力/應變，特別是當該合金薄膜沉積在鍺緩衝層上的時候。此外，錫和鍺及/或矽的合金化降低矽或鍺的能帶間隙與使得傳導帶中的γ谷(gamma valley)相較於L谷(L valley)更接近於價帶的頂部。由於能帶間隙的架構，在γ谷的載子相較於在L谷的載子具有更高的遷移率。 在某特定點上的錫的合金化，例如約7%的鍺，該合金化由於改變鍺的能帶間隙而允許擁有較高遷移率的載子在電能傳導中處於支配地位而促進高載子遷移率。
本發明的具體例可在Centura® RP EPi腔室進行，Centura® RP EPi腔室可自Applied Materials,Inc.(Santa Clara,加州)取得。然而，可知亦可使用其他設備(包含取自其他製造者的設備)進行本發明的具體例。
第2圖是根據本發明的一個具體例而形成鍺錫合金磊晶層的方法的流程圖210。流程圖210開始於操作212，該操作212中一塊如200毫米或300毫米的矽基板定位於製程腔室內。該矽基板的表面上可以有鍺緩衝層形成。可知該基板可以是任意種類的基板，包含半導體基板。一個例子中，可以使用之後其上將形成電晶體結構的矽基板。基板的表面上可以形成介電區。
操作214中，基板被提升到要求的處理溫度(如約150℃到約500℃)，例如約200℃和400℃之間。操作216中，鍺錫合金磊晶層形成在基板上，例如透過熱化學氣相沉積(CVD)處理。鍺錫合金磊晶層是透過導入鍺前驅物氣體和錫前驅物氣體進入腔室而形成在基板上。載體氣體也可任意地導入腔室。因而鍺前驅物氣體和錫前驅物氣體可在基板上熱分解或化學分解以形成鍺錫合金磊晶層。
適合的鍺前驅物包含鍺氫化物，如鍺烷(GeH4)、二鍺烷(Ge2H6)、或更高階氫化物(GexH2x+2)、或上述的組合。鍺前驅物可與載體氣體混合，該載體氣體可以是非反應性的氣 體，如氮氣、氫氣、或惰性氣體(如氦或氬)、或上述的組合。鍺前驅物的容積流率對於載體氣體的容積流率的比率可以用來控制通過腔室的氣體流速。該比率可以是任意比例從約1%至約99%，取決於要求的流速。某些具體例中，相對高的速度可以改善沉積層的均勻性。腔室的壓力是維持在約5托和約200托之間，如約20托和約80托之間，例如約40托。
錫前驅物氣體被導入腔室，同時伴隨鍺前驅物氣體，以在基板表面上沉積鍺錫合金磊晶層。錫前驅物氣體可包含錫鹵化物氣體。例如，摻雜氣體可以是SnCl4、SnCl2、或一具有式RxMCly之有機金屬氯化物，其中R是甲基或三級丁基，x是1或2，M是Sn，和y是2或3。錫前驅物氣體被供給至製程腔室中，以流率約0.1sccm和約300sccm之間，如約50sccm和約100sccm之間，例如約5sccm。錫前驅物氣體也可與載體氣體混合，以在製程腔室中達到要求的空間速度及/或混合成果。錫前驅物氣體可以從固態晶體來源昇華到流動載體氣體氣流而獲得，該載體氣體氣流如N2、H2、Ar、或He，或者錫前驅物氣體可以透過經過鹵素氣體與任選的上述載體氣體，經過在接觸腔室的固態金屬以進行反應M+2Cl2→MCl4而產生，其中M是Sn。接觸腔室可鄰近於製程腔室，彼此透過導管連接，該導管最好是短的以降低金屬鹵化物顆粒沉積在導管的可能性。
鍺錫合金磊晶層可以沉積至厚度約100埃與約800埃之間。一個例子中，在鍺基質的錫原子的濃度可以是約1%和約12%之間，如約7%和約9%之間。
錫前驅物氣體和鍺前驅物氣體通常透過不同的路徑供給至製程腔室。鍺前驅物氣體透過第一路徑供給，而錫前驅物氣體透過第二路徑供給。二條路徑通常是不同且保持分開一直到進入製程腔室的入口點。一個具體例中，兩條氣流都進入通過鄰近於基材支撐件邊緣的腔室側壁，從一端通過跨越基材支撐件到相對的一端且進入排氣系統。基材支撐件在形成鍺錫合金磊晶薄膜時可以旋轉以改善均勻性。第一路徑通常連接於第一入口點以進入製程腔室，該入口點包括一或多個在腔室壁上的開口或是一氣體分佈器，如連接在腔室壁上的噴頭。一個或多個開口可鄰近於基材支撐件的邊緣或為雙重或多重路徑氣體分佈器的入口。第二路徑同樣地連接於第二入口點，該入口點類似第一入口點。第一和第二入口點被配置成使兩條氣流混合且提供沉積或混合成長層在基板支撐件上方的區域中。某些具體例中，在處理時使用氣體分佈器可降低或消除旋轉基板的需求。
操作218中，停止鍺前驅物氣體的氣流。接著，在操作220，蝕刻劑導入製程腔室中。蝕刻劑氣體可以是，例如Cl2或HCl。操作222中，在錫前驅物氣體的存在下進行沉積材料的回蝕。因而錫前驅物氣體的氣流可以在沉積和蝕刻時始終持續，或錫前驅物氣體的氣流可在沉積處理後停止，然後恢復用於回蝕處理。
回蝕處理期間，錫前驅物氣體持續導入製程腔室中，例如，以實質上與描述於操作216的沉積處理的相同流率。回蝕處理期間，錫前驅物氣體在腔室中的存在降低錫在 鍺錫合金磊晶薄膜的遷移，使薄膜有均勻的錫組成。咸信降低錫的遷移可以至少部分地貢獻到在製程腔室氛圍內錫的分壓。因為降低錫的遷移，每次循環處理的沉積/蝕刻能重覆進行，以形成含有均勻錫組成的鍺錫合金磊晶層。操作224中，停止蝕刻氣體的氣流。隨後可重覆沉積/蝕刻處理。
第2圖顯示一個循環沉積處理的具體例，然而，額外的具體例也被考慮。另一個具體例中，可知鍺錫合金磊晶層也可包括矽。在此具體例中，可以形成矽鍺錫磊晶層。適當的矽前驅物包括矽氫化物如矽烷和二矽烷。另一個具體例中，可知可使用鉛而不是錫。又另一個具體例中，可知III族或V族的摻雜物可提供至腔室，同時伴隨著鍺和錫以形成摻雜的鍺錫合金或摻雜的矽鍺錫合金。適當的摻雜物包括n型和p型摻雜物，如硼、砷和磷。一個例子中，二硼烷可以在沉積時導入腔室，以將硼摻雜至磊晶薄膜。這種具體例中，硼前驅物和錫前驅物兩者都在循環沉積處理的非沉積階段(例如，回蝕或退火)可被供給至製程腔室，以降低釋氣及/或錫和摻雜物的遷移。可知多於一種的摻雜物可以結合到磊晶薄膜。
又另一個具體例中，可知可在不與錫結合下，沉積包括III族或V族摻雜物的鍺磊晶層。此具體例中，在處理期間腔室氛圍中的摻雜物的存在降低釋氣與III族或V族摻雜物的遷移。另一個具體例中，可知發生在退火氣體氛圍的退火處理可以取代蝕刻處理。例如，可以形成摻雜硼的鍺磊晶薄膜，接著該薄膜可被退火以活化摻雜物。此具體例中，在沉積處理和退火處理期間，摻雜物氣體被供給至製程腔室。因 為摻雜物氣體在退火處理期間被供給至腔室，降低釋氣和鍺磊晶層內摻雜物的遷移。
又另一個具體例中，可知在形成磊晶層時使用的錫前驅物氣體或摻雜物氣體和在蝕刻處理使用的錫前驅物氣體或摻雜物氣體可以是不同的氣體。此具體例中，兩種不同的氣體通常包括相同的摻雜物種類(例如，錫)。因此，在非沉積處理時，相同的氣體存在於腔室氛圍中並非必要的；然而，相同物種的存在通常足夠去降低不希望得到的遷移和釋氣。
又另一個具體例中，可知錫前驅物氣體可以在操作216前任意地導入製程腔室，以預先對基板及/或製程腔室進行處理。基板及/或製程腔室的預先處理緩和了錫結合入合金磊晶薄膜的延遲。附加地或替代地，III族摻雜物或V族摻雜物可以類似的方法應用於預先處理腔室。此具體例中，以III族摻雜物或V族摻雜物預先處理的腔室可以進一步降低在沉積磊晶薄膜摻雜物的遷移或釋氣。一個例子中，預先處理可以在沉積前約1秒到約60秒開始。可知預先處理可以在蝕刻及/或退火期間構成前驅物的導入。亦即，錫前驅物的單流可應用於降低退火/蝕刻時的錫的遷移，且同時為了下一次的沉積做製程腔室的預先處理。
第3圖顯示形成於上面具有鍺緩衝層106的矽基板104上的鍺錫合金磊晶層302的X射線繞射資料。鍺錫合金磊晶層302是使用循環沉積/退火處理形成的，其中該退火在錫前驅物氣體存在下進行。沉積/退火處理由四個循環構成。如同第3圖所顯示，只有單一尖峰對應至鍺錫合金磊晶層 302。對照之下，第1圖的鍺錫合金磊晶層102包括3個尖峰，表示了錫濃度的不均勻。第3圖中對應於鍺錫合金磊晶層302的單一尖峰表示鍺錫合金磊晶層302擁有處處均勻的錫濃度。鍺錫合金磊晶層302的均勻錫濃度是藉由在非沉積處理的間隔時(例如，退火)，將鍺錫合金磊晶層302暴露至錫前驅物氣體而被促進的。
除了促進摻雜物濃度的均勻性，在非沉積階段處理時，摻雜物的氣流，如III族或V族摻雜物氣體，也降低薄膜的表面粗糙度。一個例子中，沉積摻雜硼的鍺磊晶薄膜然後退火。在沉積期間，鍺氫化物前驅物氣體和二硼烷流通進入腔室，且形成摻雜硼的鍺磊晶層。該摻雜硼的鍺磊晶層沉積至厚度約140埃。在沉積處理結束時，該摻雜硼的鍺磊晶層具有約2.5埃(算術平均)的表面粗糙度。在沉積之後，該摻雜硼的鍺磊晶層在氫氣氛圍下以590℃進行退火90秒。在退火之後，該摻雜硼的鍺磊晶層的表面粗糙度是32.6埃(算術平均)。增加的表面粗糙度據信是因為提高的退火溫度而產生通過鍺磊晶薄膜的硼的遷移所造成。
對照之下，在不同基板上於相同條件下所沉積具有相同表面粗糙度的類似層在氫氣與二硼烷的氛圍下於590℃進行退火90秒。該層在經二硼烷存在下的退火後的表面粗糙度為約2.6埃(算術平均)。因此，透過在非沉積處理階段供給含有摻雜物氣體至製程腔室氛圍會降低摻雜物遷移，會改善表面粗糙度，且維持整體薄膜的品質。
上述例子中的退火方法可以應用熱或雷射退火。此 外，退火可在與沉積相同的腔室進行，或在不同的腔室。摻雜物的遷移通常在閒置時最小，如由一腔室傳遞基板至另一腔室。然而，在處理期間，如退火時，摻雜物的遷移由於提高的處理溫度而增加。因此，如同上述討論的，希望在提高溫度的期間將含有摻雜物的氣體供給到製程腔室以緩和或降低不想要的摻雜物遷移。
本發明的優點包括形成具有均勻濃度的磊晶層與改善表面粗糙度。本文所述的方法特別有利於包括沉積/蝕刻處理或沉積/退火處理的循環處理。然而，可知本文所述的具體例可以是有利於任何關於希望降低在薄膜內的元素遷移或降低薄膜內摻雜物的釋氣的處理，包括非循環或重覆的沉積處理(例如，只有進行單一沉積操作)。
雖然前述是直接關於本發明的具體例，本發明的其他與更進一步的具體例可以在不悖離本發明的基本範疇設計而得，且本發明的範疇定義於所附的申請專利範圍。
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Claims (18)

  1. 一種形成一磊晶材料的方法，包括以下步驟：定位一基板於一腔室中；導入一鍺前驅物氣體進入該腔室；導入一錫前驅物氣體進入該製程腔室；沉積一鍺錫合金磊晶層於該基板上；停止該鍺前驅物氣體的氣流；以及進行一退火處理或一蝕刻處理的至少其中一者於該鍺錫合金磊晶層上，其中該鍺錫合金磊晶層在該退火處理或該蝕刻處理時被暴露至該錫前驅物氣體。
  2. 如請求項1所述之方法，其中該鍺前驅物氣體包括一或多種的鍺烷或二鍺烷。
  3. 如請求項1所述之方法，其中該腔室被維持在一壓力，該壓力的範圍是約20托到約80托。
  4. 如請求項1所述之方法，其中該錫前驅物氣體包含一鹵化物。
  5. 如請求項1所述之方法，其中該錫前驅物氣體包含SnCl4或SnCl2。
  6. 如請求項1所述之方法，其中當沉積該鍺錫合金磊晶層於 該基板上時，該腔室被維特在一溫度，該溫度的範圍是約200℃到約400℃。
  7. 如請求項1所述之方法，其中該錫前驅物包含具有式RxMCly之一有機金屬氯化物，其中R是甲基或三級丁基，x是1或2，M是錫，且y是2或3。
  8. 如請求項1所述之方法，其中該鍺錫合金磊晶層是沉積至一厚度，該厚度的範圍是約100埃和約800埃之間。
  9. 如請求項8所述之方法，其中該鍺錫合金磊晶層包含錫原子於一鍺基質內，該錫具有一濃度，該濃度在約1%和約12%之間。
  10. 如請求項9所述之方法，其中該錫具有一濃度，該濃度是約7%至約9%。
  11. 如請求項1所述之方法，其中該進行一退火處理或一蝕刻處理的至少其中一者之步驟包括用一蝕刻劑進行一蝕刻處理，該蝕刻劑包括Cl2或HCl。
  12. 如請求項1所述之方法，其中在沉積該鍺錫合金磊晶層於該基板上時的該錫前驅物的一流率實質上等於在該退火處理或該蝕刻處理時的該錫前驅物的一流率。
  13. 如請求項1所述之方法，其中該鍺錫合金磊晶層進一步包括矽。
  14. 如請求項1所述之方法，其中該鍺錫合金磊晶層摻雜入一III族或V族摻雜物。
  15. 如請求項14所述之方法，其中該進行一退火處理或一蝕刻處理的至少其中一者於該鍺錫合金磊晶層上之步驟進一步包括導入一氣體，該氣體含有該III族或V族摻雜物。
  16. 如請求項1所述之方法，其中該III族或V族摻雜物包括硼、砷、和磷。
  17. 如請求項1所述之方法，其中該進行一退火處理或一蝕刻處理的至少其中一者於該鍺錫合金磊晶層上的步驟包括雷射退火該鍺錫合金磊晶層。
  18. 如請求項1所述之方法，進一步包括用一氣體預先處理該腔室，該氣體包含該錫前驅物。
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