TW202102710A - 形成富碳之含矽膜之方法 - Google Patents

形成富碳之含矽膜之方法 Download PDF

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TW202102710A
TW202102710A TW109115154A TW109115154A TW202102710A TW 202102710 A TW202102710 A TW 202102710A TW 109115154 A TW109115154 A TW 109115154A TW 109115154 A TW109115154 A TW 109115154A TW 202102710 A TW202102710 A TW 202102710A
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film
carbon
oxygen
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趙誠實
張守奉
朴載英
布萊恩 C 漢迪克斯
湯瑪士 Ｈ 邦姆
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美商恩特葛瑞斯股份有限公司
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Abstract

本發明提供一種用於形成具有變化的各元素比例之碳氮氧化矽膜(SiOCN)之方法，該方法使用二矽烷前驅物在氣相沈積條件下進行，其中可藉由利用選自氧氣、氨氣及一氧化二氮氣體之共反應物，使併入至該SiOCN膜中之碳百分比在約5%至約60%之間變化。由此形成之富碳SiOCN膜可藉由用O2 電漿處理在蝕刻終止流程後轉化為純二氧化矽膜。

Description

形成富碳之含矽膜之方法
本發明大體上係關於用於在半導體裝置製造中形成含矽膜之方法，且尤其關於形成其中併入之碳量提高的含矽膜。
在半導體製造中，化學惰性介電材料(諸如氮化矽(Si3 N4 )、氮氧化矽(SiOx Ny )及/或二氧化矽(SiO2 ))薄(例如，＜1,000奈米厚度)鈍態層廣泛用於微電子裝置結構中，充當多層結構之結構件，諸如側壁間隔元件、擴散遮罩、氧化障壁、渠溝隔離塗層、金屬間介電材料、鈍化層及蝕刻終止層。
研究已顯示氮化矽膜中之碳併入有益於電晶體側壁間隔物應用之膜品質。位於低介電常數(低K)層之間的蝕刻終止層及頂蓋層亦受益於碳與氮化矽或氧化矽之混合物。另外，氮化矽金屬前介電(PMD)內襯需要蝕刻選擇性及擴散障壁特性，其可藉由將碳併入至氮化矽中而得到增強。氧化矽在熱磷酸蝕刻中之蝕刻速率低，然而併入碳可顯著增強該選擇性。
總體而言，本發明提供一種用於形成具有變化的各元素比例之碳氮氧化矽膜(SiOCN)之方法，該方法使用二矽烷前驅物在氣相沈積條件下進行。
由此形成之富碳SiOCN膜可在一額外態樣中藉由用O2 電漿處理，在蝕刻終止流程後轉化為純二氧化矽膜。根據本發明之SiOCN之氣相沈積提供的膜相對於SiO2 膜使用稀氫氟酸(dHF)溶液的濕式蝕刻選擇性高(70:1)，且使用H3 PO4 溶液約＞1000:1。用氧電漿處理碳氮氧化矽膜得到純二氧化矽膜之高度純的膜，其洩漏低於SiOCN膜，且使(稀氫氟酸) dHF中之蝕刻速率返回至等於或大於熱生長SiO2 的量。
在一第一態樣中，本發明提供一種在微電子裝置基板上形成碳氮氧化矽膜之方法，其包含使該基板暴露於 (i)具有式(I)之矽前驅化合物
Figure 02_image003
其中R1 、R2 及R3 獨立地選自氫或C1 -C6 烷基，且各X及各Y獨立地選自氫、鹵基、C1 -C6 烷基、C1 -C6 烷胺基、C1 -C6 二烷胺基及C1 -C6 烷基肼基；及 (ii)在氣相沈積條件下之選自氨氣、一氧化二氮及氧氣的共反應物，其中該碳氮氧化矽膜具有約5%至約60%之預先選擇的碳原子百分比。
在一個實施例中，X及Y選自甲基、乙基、丙基及鹵基。在另一實施例中，X及Y中之一或多者選自碘基、氯基及溴基。在另一實施例中，X及Y中之各者為甲基。
在一個實施例中，式(I)化合物為
Figure 02_image005
。
式(I)化合物可藉由使式(R1 )2 XSi--SiX(R1 )2 之對應二矽烷化合物與式R2 R3 NH之二級胺及式R1 R2 R3 N之三級胺反應製備。參見例如美國專利第7,601,860號，其以引用之方式併入本文中。
碳氮氧化矽膜亦可含有變化量之氫(H)，但此將不會作為組成之一部分報告。實際上，膜之組成將以原子百分比(「at%」)為單位報告，其中Si、O、C及N之含量的總和為100 at%。在本發明之方法中，可藉由利用選自氧氣、氨氣及一氧化二氮氣體之共反應物，使併入至SiOCN膜中之碳百分比在約5%至約60%之間變化。共反應物可單獨或以任何組合或比例使用，且在各種情況下，在用如下文所闡述之式(I)化合物處理後，可使共反應物與基板同時或依序反應，處理步驟間具有或不具有吹掃步驟。
一般而言，氣相沈積條件包含被稱為化學氣相沈積、脈衝化學氣相沈積及原子層沈積之反應條件。在脈衝化學氣相沈積情況下，可利用一系列式(I)前驅化合物及(多種)共反應物之交替脈衝，具有或不具有中間(惰性氣體)吹掃步驟，將膜厚度累積至所需終點。
在某些實施例中，式(I)前驅化合物之脈衝時間(亦即，暴露於基板之持續時間)範圍在約1秒與10秒之間。當利用吹掃步驟時，持續時間為約1秒至4秒或1秒至2秒。在其他實施例中，共反應物之脈衝時間在1秒至60秒範圍內。在其他實施例中，共反應物之脈衝時間在約5秒至約10秒範圍內。
在一個實施例中，氣相沈積條件包含約350℃至約750℃之溫度，及約1托至約1000托之壓力。在另一實施例中，氣相沈積條件包含約350℃至約550℃之溫度。
可採用式(I)化合物及共反應物以便藉由化學氣相沈積在微電子裝置上形成碳氮氧化矽膜，化學氣相沈積利用包括約350℃至約550℃之沈積溫度的製程條件，形成厚度為約50埃至約50,000埃之膜。
在本發明之方法中，式(I)化合物與所需共反應物以任何適合方式，例如在單晶圓CVD室中，或在含有多個晶圓之爐中反應。
在本發明之方法中，咸信共反應物之選擇、利用順序及對應流動速率及濃度將使得吾人可製備含有約5%至約60%碳之碳氮氧化矽膜。在某些實施例中，所得膜之碳原子百分比將為約40%至約60%或約45%至約55%。在其他實施例中，所得膜之碳原子百分比將為約5%至10%、10%至15%、15%至20%、20%至25%、25%至30%、30%至35%、35%至40%、40%至45%、45%至50%、50%至55%及55%至60%。以此方式，可藉由分別地或以任何組合利用氨氣、一氧化二氮及氧氣中之任一者作為共反應物，將預先選擇的原子百分比之碳併入至膜中。另外，可同時以預定比例及流動速率利用(多種)共反應物以得到給定原子百分比之碳，或可依序以不同次序添加(多種)共反應物，且具有及不具有吹掃反應器之(多個)中間步驟。
在其他實施例中，本發明提供碳氮氧化矽膜，其包含約40原子%至約60原子%碳、約50原子%至約60原子%碳或約50原子%至約55原子%碳。在其他實施例中，本發明提供微電子裝置，其上沈積有碳氮氧化矽膜，該膜包含約40原子%至約60原子%碳、約50原子%至約60原子%碳或約50原子%至約55原子%碳。此類膜之厚度將為約50埃至約50,000埃。
可通常在蝕刻終止製程後，藉由將該膜暴露於氧電漿使由此產生之碳氮氧化矽膜基本上定量轉化為純二氧化矽膜。就此而言，本發明之方法有利地用以在極高縱橫比微電子裝置上形成純二氧化矽膜，在50:1縱橫比微電子裝置中具有超過95%似型性。在此情形下，膜大體上比藉由習知熱生長製程形成之對應二氧化矽膜更純。在某些實施例中，由此形成之二氧化矽膜將為至少約99%純。
因此，在另一態樣中，本發明提供一種在微電子裝置基板上形成二氧化矽膜之方法，其包含使該基板暴露於 (i)具有式(I)之矽前驅化合物
Figure 02_image007
其中R1 、R2 及R3 獨立地選自氫或C1 -C6 烷基，且各X及各Y獨立地選自氫、鹵基、C1 -C6 烷基、C1 -C6 烷胺基、C1 -C6 二烷胺基及C1 -C6 烷基肼基；及 (ii)在氣相沈積條件下之選自氨氣、一氧化二氮及氧氣的共反應物，以形成碳氮氧化矽膜，其中該碳氮氧化矽膜具有約5%至約60%之預先選擇的碳原子百分比， 接著用氧電漿處理該碳氮氧化矽膜，得到該二氧化矽膜。
在另一實施例中，本發明提供至少約99%純之二氧化矽膜。在另一實施例中，本發明提供其上沈積有至少約99%純之二氧化矽膜的微電子裝置。此類膜之厚度將為約50埃至約50,000埃。
本發明可進一步藉由其某些實施例之以下實例來說明，不過應理解，除非另外特別指示，否則僅出於說明之目的包括此等實例且不意欲限制本發明之範疇。
實驗章節 實例 1. 含 53% C 之碳氮氧化矽。 使用溫熱壁ALD反應器來將碳氮氧化矽膜沈積至矽(100)晶圓表面上，其控制在550℃下，且壓力用Ar惰性氣體連續流控制在1托至2托下。使用一系列交替的前驅物及共反應物脈衝來累積膜厚度。將SiNCH之鼓泡器保持在80℃之溫度下。Ar運載氣體以50 sccm流動通過鼓泡器，將SiNCH蒸氣運載至基板表面，持續10秒脈衝時間。此後為20秒200 sccm Ar脈衝。此後為5秒300 sccm N2 O脈衝，其後為另一20秒Ar吹掃。重複此脈衝序列450次，得到300 Å之膜厚度，組成如表之第一行中所示。
實例 2. 含約 48% C 之 碳氮氧化矽。 使用溫熱壁ALD反應器來將碳氮氧化矽膜沈積至矽(100)晶圓表面上，其控制在550℃下，且壓力用Ar惰性氣體連續流控制在1托至2托下。使用一系列交替的前驅物及共反應物脈衝來累積膜厚度。將SiNCH之鼓泡器保持在80℃之溫度下。Ar運載氣體以50 sccm流動通過鼓泡器，將SiNCH蒸氣運載至基板表面，持續8秒脈衝時間。此後為20秒200 sccm Ar。此後為10秒300 sccm NH3 脈衝，其後為另一20秒Ar吹掃。重複此脈衝序列450次，得到170 Å之膜厚度，組成如表之第二行中所示。
實例 3. 含約 15% C 之碳氮氧化矽。 使用溫熱壁ALD反應器來將碳氮氧化矽膜沈積至矽(100)晶圓表面上，其控制在550℃下，且壓力用Ar惰性氣體連續流控制在1托至2托下。使用一系列交替的前驅物及共反應物脈衝來累積膜厚度。將SiNCH之鼓泡器保持在60℃之溫度下。Ar運載氣體以50 sccm流動通過鼓泡器，將SiNCH蒸氣運載至基板表面，持續10秒脈衝時間。此後為20秒200 sccm Ar。此後為10秒300 sccm O2 脈衝，其後為另一20秒Ar吹掃。重複此脈衝序列450次，得到270 Å之膜厚度，組成如表之最後一行中所示。
製程條件                                                          XPS結果
                                 反應物(sccm) 生長速率
SINCH*鼓泡器溫度(℃) N2 O O2 NH3 (埃/循環) C N O
60-90 300~700 _ _ 0.6~0.74 51.9~53.7 4.3~6.4 8.2~8.8
80 _ _ 300 0.57 48~50 6.5 8.7
60    300~900    0.6~0.77 12~15 2.7~3.1 48.0~50.6
*SINCH=雙二甲基肼基四甲基二矽烷 典型製程條件
加工室 SINCH遞送 反應物
製程溫度(℃) 製程壓力(托) SINCH*鼓泡器溫度(℃) SINCH*運載氣體(He或Ar或N2) N2 O (sccm) O2 (sccm) NH3 (sccm)
350~650 0.01~100 25~120 0~1000 0~1000 0~1000 0~1000
O2 電漿處理之前/之後的XPS結果
製程條件                                                                        XPS結果
                                 反應物(sccm) 生長速率 O2電漿處理 原子%
SINCH*鼓泡器溫度(℃) N2 O O2 NH3 (埃/循環) C N O
80 300       0.6 之前 53.4 5.5 8.6
之後 0 0 67.5
80       300 0.57 之前 48-50 6.5 8.7
之後 0 0 67.6
本發明已特別參考其某些實施例詳細描述，但應理解變化形式及修改可在本發明之精神及範疇內受影響。
圖1為在化學氣相沈積製程中在300 sccm一氧化二氮下使用前驅物雙二甲基肼基四甲基二矽烷(「SINCH」)形成之膜中，矽、碳、氧及氮相對於以秒為單位之蝕刻時間的原子百分比圖。此資料示出碳以約53.4%之量併入至SiOCN膜中。
圖2為在化學氣相沈積製程中在300 sccm氨氣下使用前驅物雙二甲基肼基四甲基二矽烷(「SINCH」)形成之膜中，矽、碳、氧及氮相對於以秒為單位之蝕刻時間的原子百分比圖。此資料示出碳以約48%至50%之量併入至SiOCN膜中。
圖3為在化學氣相沈積製程中在300 sccm氧氣下使用前驅物雙二甲基肼基四甲基二矽烷(「SINCH」)形成之膜中，矽、碳、氧及氮相對於以秒為單位之蝕刻時間的原子百分比圖。此資料示出碳以約12%至15%之量併入至SiOCN膜中。
圖4為SiOCN膜在150℃下在H3 PO4 中之濕式蝕刻速率(WER)的圖。
圖5為SiOCN膜在dHF (100:1)中之WER的圖。以對數格式呈現之資料顯示膜中提高的碳含量對磷酸及稀氫氟酸具有抗性。
圖6為比較在O2 電漿處理之前及之後本發明之膜以埃/分鐘為單位的濕式蝕刻速率之圖，以對數格式呈現。
Figure 109115154-A0101-11-0002-1

Claims (10)

  1. 一種在微電子裝置基板上形成碳氮氧化矽膜之方法，其包含使該基板暴露於 (i)具有式(I)之矽前驅化合物
    Figure 03_image001
    其中R1 、R2 及R3 獨立地選自氫或C1 -C6 烷基，且各X及各Y獨立地選自氫、鹵基、C1 -C6 烷基、C1 -C6 烷胺基、C1 -C6 二烷胺基及C1 -C6 烷基肼基；及 (ii)在氣相沈積條件下之選自氨氣、一氧化二氮及氧氣的共反應物，其中該碳氮氧化矽膜具有約5%至約60%之預先選擇的碳原子百分比。
  2. 如請求項1之方法，其中X及Y係選自鹵基、甲基及丙基。
  3. 如請求項1之方法，其中該式(I)化合物係
    Figure 03_image010
    。
  4. 如請求項1之方法，其中該共反應物包含氨氣。
  5. 如請求項1之方法，其中該共反應物包含一氧化二氮。
  6. 如請求項1之方法，其中該共反應物包含氧氣。
  7. 如請求項1之方法，其中該共反應物包含氧氣、氨氣及一氧化二氮中之至少兩者的任何組合。
  8. 一種在微電子裝置基板上形成二氧化矽膜之方法，其包含使該基板暴露於 (i)具有式(I)之矽前驅化合物
    Figure 03_image012
    其中R1 、R2 及R3 獨立地選自氫或C1 -C6 烷基，且各X及各Y獨立地選自氫、鹵基、C1 -C6 烷基、C1 -C6 烷胺基、C1 -C6 二烷胺基及C1 -C6 烷基肼基；及 (ii)在氣相沈積條件下之選自氨氣、一氧化二氮及氧氣的共反應物，以形成碳氮氧化矽膜，其中該碳氮氧化矽膜具有約5%至約60%之預先選擇的碳原子百分比， 接著用氧電漿處理該碳氮氧化矽膜，得到該二氧化矽膜。
  9. 一種微電子裝置，其上沈積有包含約40原子%至約60原子%碳之碳氮氧化矽膜。
  10. 如請求項9之微電子裝置，其上沈積有至少約99%純的二氧化矽膜。
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