TWI737693B - 金屬硼化物的沉積 - Google Patents
金屬硼化物的沉積 Download PDFInfo
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Abstract
本發明揭示一種將金屬硼化物膜沉積至基板上的方法。特別地,該方法包含將金屬鹵化物前驅物脈衝至基板上且將硼化合物前驅物脈衝至基板上。金屬鹵化物前驅物與硼化合物前驅物之間的反應形成金屬硼化物膜。詳言之,該方法揭示形成硼化鉭(TaB2)或硼化鈮(NbB2)膜。
Description
本申請案係關於同時提申且命名為「金屬硼化物的沉積(DEPOSITION OF METAL BORIDES)」之美國非臨時專利申請案及同時提申且命名為「金屬硼化物及矽化物的沉積(DEPOSITION OF METAL BORIDES AND SILICIDES)」之美國非臨時專利申請案,該等申請案之揭示以引用之方式全體併入本文中。
本揭示一般關於用於製造電子裝置的方法。更具體地說,本揭示關於通過原子層沉積(ALD)形成金屬硼化物。詳言之,本揭示揭示形成鈮及鉭硼化物的方法。
金屬硼化物膜係使用各種化學氣相沉積(CVD)方法所形成。在CVD方法中,將氣態源化學物質同時引入反應空間,致使金屬膜沉積在基板上。為了熱活化一些氣態源化學物質,CVD方法傾向於在高達1200℃的溫度下進行。高基板溫度對於熱預算,尤其在最先進的半導體製造製程(諸如金屬化)上可能會造成問題。
此外,物理氣相沉積(PVD)方法亦被用於沉積金屬硼化物。PVD方法一般沿著視線沉積。然而,視線沉積導致當涉及複雜的基板輪廓
時在某些區域中薄膜覆蓋不足。此外,視線沉積導致低揮發性前驅物沉積在遇到的第一個固體表面上,致使低正形性(conformality)覆蓋。
原子層沉積(ALD)已被用於形成金屬碳化物膜。例如,Elers的美國專利第7,611,751號揭示了通過金屬源化學物質、還原劑及碳源化學物質的空間及時間分離的氣相脈衝形成金屬碳化物膜的方法。同樣地,Chen等人的美國專利第8,841,182號揭示了通過ALD製程形成碳化鈦膜。然而,並無存在已知的ALD溶液以在低溫下沉積金屬硼化物膜。因此,需要一種使用ALD來形成金屬硼化物膜的方法。
此外,需要一種形成獲得所需介電常數以及顯示可靠性的金屬硼化物膜的方法。
根據本發明至少一個具體實例,揭示一種形成金屬硼化物的方法。該方法包含:提供用於在反應腔室中處理的基板;執行金屬鹵化物前驅物沉積至基板上,該執行金屬鹵化物前驅物沉積步驟包含:將金屬鹵化物前驅物脈衝至基板上;及自反應腔室吹掃過量的金屬鹵化物前驅物;並且執行硼烷化合物前驅物沉積至基板上,該執行硼烷化合物前驅物沉積步驟包含:將硼烷化合物前驅物脈衝至基板上;及自反應腔室吹掃過量的硼烷化合物前驅物;其中金屬鹵化物前驅物包含以下之一者:五氟化鉭(TaF5)、四氟化鈮(NbF4)或五氟化鈮(NbF5);其中金屬鹵化物前驅物與硼烷化合物前驅物之間的反應形成包含以下之至少一者的金屬硼化物膜:硼化鉭(TaB2)或硼化鈮(NbB2);其中金屬鹵化物前驅物沉積步驟重複預定次數;並且其中硼烷化合物前驅物沉積步驟重複預定次數。
根據本發明至少一個具體實例,揭示一種形成金屬硼化物的方法。該方法包含:提供用於在反應腔室中處理的基板;執行金屬鹵化物前驅物沉積至基板上,該執行金屬鹵化物前驅物沉積步驟包含:將金屬鹵化物前驅物脈衝至基板上;及自反應腔室吹掃過量的金屬鹵化物前驅物;並且執行硼烷化合物前驅物沉積至基板上,該執行硼烷化合物前驅物沉積步驟包含:將硼烷化合物前驅物脈衝至基板上;及自反應腔室吹掃過量的硼烷化合物前驅物;其中金屬鹵化物前驅物包含以下之一者:五氟化鉭(TaF5)、四氟化鈮(NbF4)或五氟化鈮(NbF5);其中金屬鹵化物前驅物與硼烷化合物前驅物之間的反應形成包含以下之至少一者的金屬硼化物:硼化鉭(TaB2)或硼化鈮(NbB2)。
為了總結本發明及相對於先前技術所達成的優點,本文上文中已描述了本發明的某些目的及優點。當然,應當理解,不一定所有此等目的或優點都可根據本發明的任何特定具體實例而實現。因此,例如,發明所屬技術領域中具有通常知識者會了解本發明可以以實現或最佳化如本文教示或建議的一個優點或一組優點的方式來體現或實施,而不必實現如本文可教示或建議的其它目的或優點。
此等具體實例皆旨在落入本文所揭示的本發明範圍內。對於發明所屬技術領域中具有通常知識者來說,從以下某些具體實例的詳細描述及所附的參考圖式,此等具體實例及其它具體實例係為顯而易見,本發明不限於所揭示的任何特定具體實例。
100:金屬鹵化物脈衝/吹掃
110:金屬鹵化物脈衝
120:惰性氣體吹掃
200:硼烷化合物脈衝/吹掃
210:硼烷化合物脈衝
220:惰性氣體吹掃
300、310、320:路徑
下面參照某些具體實例的圖式描述本文揭示的本發明此等
及其它特徵、態樣及優點,其旨在說明而非限制本發明。
圖1係為根據本發明至少一個具體實例的方法流程圖。
圖2係為根據本發明至少一個具體實例的步驟流程圖。
圖3係為根據本發明至少一個具體實例的步驟流程圖。
雖然下面揭示了某些具體實例及實施例,但是發明所屬技術領域中具有通常知識者會理解,本發明延伸超出本發明具體揭示的具體實例及/或用途以及其顯而易見的改變及同等物。因此,意欲為所揭示的本發明的範圍不應受下面描述的具體揭示的具體實例所限制。
金屬硼化物由於其特性而在各種應用中展示出潛在用途。例如,金屬硼化物具有低功函數及低電阻率,使其成為非金屬柵極或柵極填充應用的理想選擇。此外,金屬硼化物的高耐化學性使其適用於圖案化層及硬遮罩(hard mask)。此外,金屬硼化物的高功函數及低電阻率提供了p金屬堆疊、柵極填充及MIMCAP電極(SoC)的適用性。
圖1說明一種根據本發明至少一個具體實例的用於沉積金屬硼化物的方法。該方法包括金屬鹵化物脈衝/吹掃步驟100及硼烷化合物脈衝/吹掃步驟200。該等步驟在原子層沉積裝置的反應腔室內進行。此裝置可包括來自ASM International N.V的EmerALD® XP ALD製程模組。在反應腔室內放置待處理的基板。基板可由氧化矽(SiO2)、矽(Si)、矽鍺(SiGe)、鍺(Ge)、砷化鎵(GaAs)或磷化銦(InP)製成。基板也可具有氮化鈦(TiN)、氧化鈦(TiO2)、氧化鉿(HfO2)或另一金屬膜的膜。
金屬鹵化物脈衝/吹掃步驟100可在先前的金屬鹵化物脈衝/
吹掃步驟之後經由路徑300重複。同樣地,硼烷化合物脈衝/吹掃步驟200可在先前的硼烷化合物脈衝/吹掃步驟之後經由路徑310重複。此外,整個製程可經由路徑320重複。為了形成所需厚度的金屬硼化物膜,此為可欲的。例如,50個循環的金屬鹵化物脈衝/吹掃步驟100及50個循環的硼烷化合物脈衝/吹掃步驟200可致使形成具有200埃厚度的金屬硼化物膜。
硼烷化合物可能可發生一些分解,例如,若選擇反應溫度,係可能發生輕微分解的情況。在特定具體實例中,多於單層的硼烷化合物被吸附至表面。在其它具體實例中,多於單層的硼烷化合物被吸附至表面,然後與金屬鹵化物進一步反應形成金屬硼化物。在一些具體實例中,金屬硼化物膜係由ALD型製程所形成。在一些具體實例中,由於硼烷分解,硼烷對於表面的反應可不自限制為對一單層。在一些具體實例中,連續製程可不為ALD製程,而是以例如連續CVD製程作為替代。在一些具體實例中,可省略一或多個吹掃步驟,並且以不使用惰性氣體的排空或移除步驟來取代。在一些具體實例中,一或多個吹掃步驟可以流動具有或不具有惰性氣體的小濃度的硼烷化合物前驅物來取代。在一些具體實例中,硼烷反應或金屬鹵化物反應可不形成層;而是可形成各自包含硼或金屬鹵化物的分開位置的材料或島狀(可能分開的或部分連接)的材料。
圖2說明金屬鹵化物脈衝/吹掃步驟100的步驟。金屬鹵化物脈衝/吹掃步驟包含金屬鹵化物脈衝110及惰性氣體吹掃120。可用於金屬鹵化物脈衝110的金屬鹵化物包含五氟化鉭(TaF5)、四氟化鈮(NbF4)及五氟化鈮(NbF5)。在一些具體實例中,金屬鹵化物可包含至少一種氟配位基,並且金屬選擇為鉭(Ta)或鈮(Nb)。在一些具體實例中,金屬鹵化物
可包含具有氧化態+V的鉭(Ta)或鈮(Nb)。在一些具體實例中,金屬鹵化物可包含具有氧化態+IV的鈮(Nb)。在金屬鹵化物脈衝110期間,金屬鹵化物可通過噴淋頭前驅物輸送系統被引入反應腔室中且被入射至基板上。金屬鹵化物可與基板上的活性部位相互作用以形成金屬鹵化物的單層膜。
為了獲得最佳化成膜,可有最佳化設定以執行製程。例如,金屬鹵化物可在進入反應腔室之前保持80℃的溫度。在金屬鹵化物脈衝110期間反應腔室內的溫度範圍可在200-400℃之間,其可證明對於提供低的熱預算係有利的。此外,在金屬鹵化物脈衝110期間反應腔室內的壓力可在0.5至8托之間。每個金屬鹵化物脈衝110可進行0.1至10秒。
惰性氣體吹掃120用於移除在金屬鹵化物脈衝步驟110期間引入至反應腔室中的任何過量金屬鹵化物前驅物。在惰性氣體吹掃120期間可使用的惰性氣體包括氮(N2)、氬(Ar)、氦(He)、氫(H2)或其他稀有氣體。
圖3說明根據本發明至少一個具體實例的硼烷化合物脈衝/吹掃步驟200。硼烷化合物脈衝/吹掃步驟200包括硼烷化合物脈衝210及惰性氣體吹掃220。
硼烷化合物脈衝210涉及硼烷化合物的脈衝。可使用的硼烷化合物的實例包括硼烷(BH3)、二硼烷(B2H6)、三硼烷(B3H8)、四硼烷(B4H10)、五硼烷、六硼烷、七硼烷、八硼烷、九硼烷、十硼烷及其他僅由硼及氫組成的硼烷化合物。可使用的另外的硼烷化合物包括胺硼烷、環硼化物、硼、不包括碳的其它硼烷化合物及其它含硼前驅物。當硼烷化合
物脈衝210開始時,反應腔室中的基板可具有操作為用於硼烷化合物的活性部位的金屬鹵化物單層。例如,當將二硼烷的脈衝引入反應腔室時,基板可具有五氟化鈮層。不排除任何理論,據信二硼烷係根據下列方程式與五氟化鈮反應,以形成純硼化鈮膜:NbF5+B2H6→NbB2+HF+H2。
同樣地,五氟化鉭與二硼烷的反應會致使形成硼化鉭(TaB2)膜。由於例如在適當相中的耐氧化性、高耐化學性、高剛性及低電阻率等性質,純硼化鈮或純硼化鉭膜的形成係為有利的。此等膜在例如圖案化層、硬遮罩、後段製程(back-end-of-line,BEOL)互連、柵極屏障及柵極填充等方面具有很大的適用性。
類似於金屬鹵化物脈衝110,為了獲得最佳化成膜,可有最佳化設定以執行硼烷化合物脈衝210。例如,硼烷化合物可在進入反應腔室之前保持25℃的溫度。在硼烷化合物脈衝210期間反應腔室內的溫度範圍可在200-400℃之間,其允許低的熱預算。此外,在硼烷化合物脈衝210期間反應腔室內的壓力可在0.5至8托之間。每個硼烷化合物脈衝210可進行0.1至10秒之間。
惰性氣體吹掃220用於移除在硼烷化合物脈衝步驟210期間引入至反應腔室中的任何過量硼烷化合物前驅物。在惰性氣體吹掃220期間可使用的惰性氣體包括氮(N2)、氬(Ar)、氦(He)、氫(H2)或其他稀有氣體。
由於循環,可形成硼化鉭或硼化鈮膜。該膜可包括金屬-硼化物鍵。另一方面,該膜可包括被捕獲在膜內的金屬及硼,而不具有真正
的金屬-硼化物鍵。所得到的膜可用於例如MOS應用中。該膜可包括具有以下原子濃度的元素:(1)約30至約80%,較佳約50至約80%,以及更佳約60至約70%的硼;(2)約20至約70%,較佳約20至約50%,以及更佳約30至約40%的金屬;(3)具有小於約5%,較佳小於1%的氧;(4)具有小於約5%,較佳小於1%的氫;及(5)具有小於約5%,較佳小於1%的氟。
所展示及描述的特定實現係為本發明及其最佳模式的說明,且不旨在以任何方式另外限制態樣及實現的範圍。實際上,為了簡潔起見,可不詳細描述系統的習知製造、關聯、製備以及其它功能性態樣。此外,各圖中所示的連接線旨在表示各種元件之間的例示性功能關係及/或物理耦合。許多替代或附加的功能關係或物理關聯可存在於實際系統中,及/或可不存在於一些具體實例中。
應當理解,因為可能會有許多變化,本文描述的配置及/或方法本質上係為例示性的,並且此等特定的具體實例或實施例不應被認為是限制性的。本文描述的特定例程或方法可表示任何數量中一或多個的處理策略。因此,所示的各種動作可以所示的順序、以其它順序執行,或在一些情況下省略。
本揭示的標的包括本文揭示的各種製程、系統及配置,以及其它特徵、功能、動作及/或性質的所有新穎的及非顯而易見的組合及子組合,以及其任何及所有等同物。
100‧‧‧金屬鹵化物脈衝/吹掃
200‧‧‧硼烷化合物脈衝/吹掃
300‧‧‧路徑
310‧‧‧路徑
320‧‧‧路徑
Claims (23)
- 一種形成金屬硼化物的方法,其包含:提供用於在反應腔室中處理的基板;執行金屬鹵化物前驅物沉積至該基板上,該執行金屬鹵化物前驅物沉積步驟包含:將金屬鹵化物前驅物脈衝至該基板上;及自該反應腔室吹掃過量的該金屬鹵化物前驅物;及執行硼烷化合物前驅物沉積至該基板上,該執行硼烷化合物前驅物沉積步驟包含:將硼烷化合物前驅物脈衝至該基板上;及自該反應腔室吹掃過量的該硼烷化合物前驅物;其中該金屬鹵化物前驅物包含鹵化鈮;其中該金屬鹵化物前驅物與該硼烷化合物前驅物之間的反應形成硼化鈮膜;其中該金屬鹵化物前驅物沉積步驟重複預定次數;及其中該硼烷化合物前驅物沉積步驟重複預定次數。
- 根據申請專利範圍第1項之方法,其中該反應腔室的溫度範圍在200至400℃之間。
- 根據申請專利範圍第1項之方法,其中該反應腔室的壓力範圍在0.5至 8托之間。
- 根據申請專利範圍第1項之方法,其中該將金屬鹵化物前驅物脈衝具有0.1至10秒之間的持續時間。
- 根據申請專利範圍第1項之方法,其中該將硼烷化合物前驅物脈衝具有0.1至10秒之間的持續時間。
- 根據申請專利範圍第1項之方法,其中吹掃過量的該金屬鹵化物前驅物包含以以下之至少一者吹掃該反應腔室:氮(N2)、氫(H2)或稀有氣體。
- 根據申請專利範圍第1項之方法,其中吹掃過量的該硼烷化合物前驅物包含以以下之至少一者吹掃該反應腔室:氮(N2)、氫(H2)或稀有氣體。
- 一種形成金屬硼化物的方法,其包含:提供用於在反應腔室中處理的基板;執行金屬鹵化物前驅物沉積至該基板上,該執行金屬鹵化物前驅物沉積步驟包含:將金屬鹵化物前驅物脈衝至該基板上;及自該反應腔室吹掃過量的該金屬鹵化物前驅物;及執行硼烷化合物前驅物沉積至該基板上,該執行硼烷化合物前驅物沉積步驟包含:將硼烷化合物前驅物脈衝至該基板上;及自該反應腔室吹掃過量的該硼烷化合物前驅物;其中該金屬鹵化物前驅物包含以下之一者:五氟化鉭(TaF5)、四 氟化鈮(NbF4)或五氟化鈮(NbF5);其中該金屬鹵化物前驅物與該硼烷化合物前驅物之間的反應形成包含以下之至少一者的金屬硼化物:硼化鉭(TaB2)或硼化鈮(NbB2)。
- 根據申請專利範圍第9項之方法,其中該反應腔室的溫度範圍在200至400℃之間。
- 根據申請專利範圍第9項之方法,其中該反應腔室的壓力範圍在0.5至8托之間。
- 根據申請專利範圍第9項之方法,其中該將金屬鹵化物前驅物脈衝具有0.1至10秒之間的持續時間。
- 根據申請專利範圍第9項之方法,其中該將硼烷化合物前驅物脈衝具有0.1至10秒之間的持續時間。
- 根據申請專利範圍第9項之方法,其中吹掃過量的該金屬鹵化物前驅物包含以以下之至少一者吹掃該反應腔室:氮(N2)、氫(H2)或稀有氣體。
- 根據申請專利範圍第9項之方法,其中吹掃過量的該硼烷化合物前驅物包含以以下之至少一者吹掃該反應腔室:氮(N2)、氫(H2)或稀有氣體。
- 根據申請專利範圍第9項之方法,其中該金屬硼化物的硼濃度為約30至約80原子%。
- 根據申請專利範圍第9項之方法,其中該金屬硼化物的鈮或鉭濃度為約20至約70原子%。
- 根據申請專利範圍第9項之方法,其中該金屬硼化物的氧濃度為小於約5原子%。
- 根據申請專利範圍第9項之方法,其中該金屬硼化物的氫濃度為小於約5原子%。
- 根據申請專利範圍第9項之方法,其中該金屬硼化物的氟濃度為小於約5原子%。
- 根據申請專利範圍第2項或第10項之方法,其中該僅由硼及氫組成的硼烷化合物選自由硼烷(BH3)、二硼烷(B2H6)、三硼烷(B3H8)、四硼烷(B4H10)、五硼烷、六硼烷、七硼烷、八硼烷、九硼烷、十硼烷組成之群。
- 根據申請專利範圍第7、8、15、16項中任一項之方法,其中該稀有氣體選自由氬(Ar)、氦(He)組成之群。
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