TWI675797B - 用於進階圖案化之軟著陸奈米層 - Google Patents

用於進階圖案化之軟著陸奈米層 Download PDF

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TWI675797B
TWI675797B TW107127482A TW107127482A TWI675797B TW I675797 B TWI675797 B TW I675797B TW 107127482 A TW107127482 A TW 107127482A TW 107127482 A TW107127482 A TW 107127482A TW I675797 B TWI675797 B TW I675797B
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layer
nano
substrate
core
deposited
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TW107127482A
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TW201840463A (zh
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Ｌ 帕斯果法蘭克
Frank L. Pasquale
史旺明內森珊卡
Shankar Swaminathan
拉芙依艾里恩
Adrien Lavoie
莎瑪納德
Nader Shamma
狄克西吉里什
Girish Dixit
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美商諾發系統有限公司
Novellus Systems, Inc.
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Priority claimed from US14/074,617 external-priority patent/US9287113B2/en
Application filed by 美商諾發系統有限公司, Novellus Systems, Inc. filed Critical 美商諾發系統有限公司
Publication of TW201840463A publication Critical patent/TW201840463A/zh
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
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    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • C23C16/45542—Plasma being used non-continuously during the ALD reactions
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
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  • Microelectronics & Electronic Packaging (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Electromagnetism (AREA)
  • Formation Of Insulating Films (AREA)
  • Chemical Vapour Deposition (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Drying Of Semiconductors (AREA)

Abstract

提供方法，用於在核心層上沉積奈米層疊保護層，而允許在該核心層上沉積高品質保形膜，以用於先進多重圖案化方案。在若干實施例中，該等方法包含以低的高頻射頻（HFRF）電漿功率使用基於電漿的原子層沉積技術沉積薄的矽氧化物或鈦氧化物膜，接著以高HFRF電漿功率，沉積保形鈦氧化物膜或間隔部。

Description

用於進階圖案化之軟著陸奈米層
本發明係關於半導體基板處理方法。
先進積體電路製造經常涉及在大批量半導體生產中圖案化1x nm半節距特徵部。多重圖案化技術可允許基於例如193nm浸微影之微影技術的特徵部大小尺度。自對準雙重圖案化係多重圖案化技術的例子。發展多重圖案化技術等級至11nm或更小之半節距存在挑戰。
此處提供處理半導體基板的方法，以允許沉積高品質保形膜，用於多重圖案化積體方案。
一個實施態樣包含一種半導體基板處理方法，其係藉由在基板上沉積一奈米層疊層以及在該奈米層疊層上沉積一鈦氧化物層。該奈米層疊層可具有介於約15Å與約200Å之間的厚度，且可具有低於該鈦氧化物層密度的密度。在各種實施例中，該方法亦包含沉積一非晶碳層。在一些實施例中，該非晶碳層係圖案化的。在各種實施例中，該奈米層疊層包含一堆疊，該堆疊包含 二層以上的子層。在一些實施例中，該二層以上的子層包含矽氧化物、或鈦氧化物、或其組合。在若干實施例中，該堆疊僅包含二層子層。在一些實施例中，該奈米層疊層包含矽氧化物第一子層及鈦氧化物第二子層。
在各種實施例中，該奈米層疊層係矽氧化物或鈦氧化物。在若干實施例中，該奈米層疊層係使用例如電漿輔助原子層沉積法(PEALD)之基於電漿的製程加以沉積，其係藉由以下步驟進行：暴露該基板於一含鈦先質或一含矽先質；暴露該基板於一氧化劑；及在該基板暴露於該氧化劑之時，啟動電漿。在若干實施例中，該奈米層疊層係在介於約50℃與約150℃之間的溫度下加以沉積，且電漿係在介於每平方公釐約1.768×10-4W與約1.768×10-3W之間的每平方公釐基板面積高頻射頻(HFRF)功率下加以啟動。在若干實施例中，該奈米層疊層係在低於約100℃的溫度下加以沉積。可用於此處揭露實施例之方法的含鈦先質的例子係肆二甲基胺基鈦(TDMAT)。含矽先質的例子係雙(叔丁基胺基)矽烷(SiH2(NHC(CH3)3)2(BTBAS)。
在各種實施例中，該鈦氧化物層係藉由PEALD加以沉積，其係藉由以下步驟進行：暴露該基板於一含鈦先質；暴露該基板於一氧化劑；及在至少約每平方公釐1.768×10-3W的每平方公釐基板面積HFRF功率下，在該基板暴露於該氧化劑的同時，啟動電漿。氧化劑的例子包含氧化亞氮、氧、二氧化碳、或其混合物。在一些實施例中，該鈦氧化物層可在介於約50℃與約400℃之間的溫度下加以沉積。
另一實施態樣包含一種半導體基板處理方法，其係藉由：沉積一核心層；在該核心層上沉積一奈米層疊層；及在該奈米層疊層上沉積一金屬氮化物或金屬氧化物層。在一些實施例中，該核心層係圖案化的。在若干實施例 中，該核心層可為非晶碳或光阻。在各種實施例中，該奈米層疊層可為矽氧化物或鈦氧化物。在一些實施例中，所沉積奈米層疊層的厚度係介於約15Å與約200Å之間。
在若干實施例中，該奈米層疊層係使用PEALD加以沉積，其係藉由：暴露基板於一含鈦先質或一含矽先質；暴露該基板於一氧化劑；及在該基板暴露於該氧化劑時，將電漿啟動。在各種實施例中，該奈米層疊層係在介於約50℃與約150℃之間的溫度下加以沉積，且電漿係在介於每平方公釐約1.768×10-4W與約1.768×10-3W之間的每平方公釐基板面積HFRF功率下加以啟動。在若干實施例中，該奈米層疊層係在低於約100℃的溫度下加以沉積。
在各種實施例中，金屬氮化物或金屬氧化物層包含鈦氧化物或矽氧化物。該金屬氮化物或金屬氧化物層可相對於核心具有蝕刻選擇性。在若干實施例中，該金屬氮化物或金屬氧化物層係使用PEALD加以沉積，其係藉由：暴露基板於一含金屬先質；露該基板於一氧化劑；及在每平方公釐至少約1.768×10-3W的每平方公釐基板面積HFRF功率下，在該基板暴露於該氧化劑的同時，啟動電漿。氧化劑的例子包含氧化亞氮、氧、二氧化碳、或其組合。在一些實施例中，該金屬氮化物或金屬氧化物層係在介於約50℃與約400℃之間的溫度下加以沉積。
另一實施態樣包含一種半導體基板處理方法，其係藉由(a)暴露基板於一第一含鈦先質或一含矽先質；(b)暴露該基板於一第一氧化劑；(c)以介於每平方公釐約1.768×10-4W與約1.768×10-3W之間的每平方公釐基板面積HFRF功率，在該基板暴露於該第一氧化劑時，啟動第一電漿；(d)暴露該基板於一第二含鈦先質；(e)暴露該基板於一第二氧化劑；及(f)以至少每平 方公釐約1.768×10-3W的每平方公釐基板面積HFRF功率，在該基板暴露於該第二氧化劑時，啟動第二電漿。
在一些實施例中，(a)到(c)係在介於約50℃與約150℃之間的溫度下加以處理。在一些實施例中，(d)到(f)係在介於約50℃與約400℃之間的溫度下加以處理。在一些實施例中，(d)到(f)係在較(a)到(c)為高的溫度下加以處理，使得自(c)過渡至(d)包含升高基板溫度至少約50℃、至少約100℃、至少約150℃、或至少約200℃。
該第一含鈦先質和第二含鈦先質可為相同先質，例如TDMAT。在一些實施例中，第一氧化劑可相同於第二氧化劑(例如氧化亞氮、氧、二氧化碳、或其組合)。在一些實施例中，使用不同的氧化劑或混合物可能是有益的。在一些實施例中，基板包含非晶碳。在一些實施例中，非晶碳係圖案化的。
在各種實施例中，該方法亦包含在啟動第二電漿之後，平坦化該基板以暴露非晶碳，且選擇性蝕刻該非晶碳以形成一遮罩。
另一實施態樣包含半導體基板圖案化方法，其係藉由：在沉積保形膜於一核心層之前，在一圖案化的核心層上沉積一奈米層疊保護層；沉積一保形膜於該奈米層疊保護層之上；平坦化該保形膜以暴露核心；及選擇性蝕刻該核心以形成一遮罩。
在若干實施例中，核心層包含非晶碳。在各種實施例中，奈米層疊保護層包含矽氧化物或鈦氧化物。在若干實施例中，奈米層疊保護層的厚度係介於約15Å與約200Å之間。在許多實施例中，該奈米層疊保護層係使用PEALD加以沉積，其係藉由：暴露該基板於一含鈦先質或一含矽先質；暴露該基板於一氧化劑；及在該基板暴露於該氧化劑時，啟動第一電漿。
在一些實施例中，奈米層疊保護層係在低於約100℃的溫度下沉積。在各種實施例中，奈米層疊保護層係在介於約50℃與約150℃之間的溫度下加以沉積，且第一電漿係在介於每平方公釐約1.768×10-4W與約1.768×10-3W之間的每平方公釐基板面積HFRF功率下加以啟動。
在一些實施例中，鈦氧化物層係使用PEALD加以沉積，其藉由：暴露基板於一含鈦先質；暴露該基板於一氧化劑；及在至少每平方公釐約1.768×10-3W的每平方公釐基板面積HFRF功率下，在基板暴露於氧化劑時，啟動第二電漿。
另一實施態樣包含一種半導體基板處理設備，其包含：一個以上製程腔室；進入該等製程腔室的一個以上氣體入口和相關聯的流量控制硬體；一HFRF產生器；及一控制器，具有至少一處理器及一記憶體，使得該至少一處理器及該記憶體係彼此通訊連接，該至少一處理器係至少操作性連接該流量控制硬體及HFRF產生器，且該記憶體儲存電腦可執行指令，用於：暴露基板於一含金屬先質；暴露該基板於一第一氧化劑；以介於約12.5W與125W之間的HFRF功率，在該基板暴露於該第一氧化劑時，啟動第一電漿；暴露該基板於一含鈦先質；暴露該基板於一第二氧化劑；及以至少約125W的HFRF功率，在該基板暴露於該第二氧化劑時，啟動第二電漿。
這些和其他實施態樣，以下將參照圖式進一步說明。
103‧‧‧第一核心
104‧‧‧硬遮罩(蓋層)
105‧‧‧第二核心層
105’‧‧‧第二核心
107‧‧‧層
107a‧‧‧硬遮罩層(蝕刻終止層)
107b‧‧‧蓋層
107c‧‧‧遮罩層
107c’‧‧‧遮罩
109‧‧‧保形膜
109’‧‧‧間隔部
111‧‧‧奈米層疊(保護)層
119‧‧‧保形膜
119’‧‧‧間隔部
129‧‧‧保形膜
129’‧‧‧間隔部
150‧‧‧目標層
2100‧‧‧反應器
2102‧‧‧低頻RF產生器
2104‧‧‧高頻射頻產生器
2106‧‧‧匹配網路
2108‧‧‧歧管
2110‧‧‧氣體管線
2112‧‧‧入口
2114‧‧‧噴淋頭
2116‧‧‧基板
2118‧‧‧晶圓支座
2120‧‧‧加熱塊
2122‧‧‧出口
2124‧‧‧製程腔室
2130‧‧‧系統控制器
2140‧‧‧泵
2200‧‧‧處理機台
2202‧‧‧入站負載鎖室
2204‧‧‧出站負載鎖室
2206‧‧‧機器人
2208‧‧‧晶圓盒
2210‧‧‧大氣埠
2212‧‧‧支座
2214‧‧‧處理腔室
2216‧‧‧腔室搬運埠
2218‧‧‧支座
2250‧‧‧系統控制器
2252‧‧‧處理器
2254‧‧‧大量儲存裝置
2256‧‧‧記憶體裝置
2258‧‧‧系統控制軟體
2290‧‧‧晶圓搬運系統
2302a‧‧‧保形膜層
2302b‧‧‧保形膜
2302c‧‧‧保形膜
2304a‧‧‧核心層
2304b‧‧‧核心芯軸
2304c‧‧‧核心芯軸
2306‧‧‧奈米層疊層
2308‧‧‧奈米層疊層
圖1-11係根據所揭露實施例之積體方式的示意圖。
圖12-18係根據所揭露實施例之積體方式的示意圖。
圖19係根據所揭露實施例之方法的製程流程圖。
圖20A及20B係根據所揭露實施例的方法的製程流程圖。
圖21係一反應腔室的圖示，該反應腔室用於執行根據所揭露實施例的方法。
圖22係一多站式設備的圖示，其可用於根據所揭露實施例執行操作。
圖23A-23C係所沉積膜的影像，取自執行根據所揭露實施例之方法的實驗。
在以下說明中，描述許多特定細節，以提供所述實施例的完整理解。所揭露實施例可在沒有若干或全部這些特定細節的情況下加以實施。另一方面，眾所周知的製程操作不再詳細描述，以免不必要地混淆所揭露實施例。雖然所揭露實施例將配合這些特定實施例加以描述，吾人理解這無意限定所揭露的實施例。
半導體元件製造通常包含在一積體生產製程中沉積一層以上薄膜，且可包含圖案化步驟。多重圖案化技術係用以製造先進積體電路，例如具有較小特徵部或較高深寬比者、或小至2x或1x節點者。術語「1x」節點意指介於10nm與19nm之間的製程節點，且術語「2x」節點意指介於20nm與29nm之間的製程節點。多重圖案化的例子係自對準雙重圖案化，其產生雙倍數量之習知微影法所形成圖案特徵部。隨著元件變得較小，較窄的半節距特徵部可利用先進的多重圖案化技術達成，例如四倍圖案化或「四重圖案化」。
在圖1-11中提供四重圖案化方式的例子。圖1提供在多層堆疊中可包含之各種層的例子的示意圖，例如在適用於半導體處理之晶圓之上。在圖1中的多層堆疊包含一第一核心層，其形成為硬遮罩104之上的第一核心(亦稱為第一芯軸(mandrel))103，該第一核心可在一先前的製程中微影形成。硬遮罩104可在一第二核心層105之上，該第二核心層105係沉積在層107之上。層107可包含一硬遮罩層107a、一蓋層107b、及一遮罩層107c，其可用作一遮罩以圖案化後續的目標層150。阻障層、蓋層、或蝕刻終止層可介於遮罩層107c與目標層150之間。熟習此技藝者將瞭解，可能有一層以上沉積在上述層其中任意者之間，且目標層150可包含一個以上額外的層。
第一核心層(且因而第一核心103)可相對於堆疊中的其他材料(例如矽及/或矽基氧化物或氮化物)為高蝕刻選擇性，且可為透明的。第一核心層可為光阻，或可由非晶碳材料或非晶矽材料製成。在一些實施例中，第一核心層可藉由例如電漿輔助化學汽相沉積(PECVD)之沉積技術沉積在硬遮罩104之上，且該沉積技術可包含在沉積腔室中自包含烴先質的沉積氣體產生電漿。烴先質可由化學式CxHy定義，其中x係介於2與10之間的整數，且y係介於2與24之間的整數。例子包含甲烷(CH4)、乙炔(C2H2)、乙烯(C2H4)、丙烯(C3H6)、丁烷(C4H10)、環己烷(C6H12)、苯(C6H6)、及甲苯(C7H8)。可使用包含高頻(HF)功率及低頻(LF)功率之雙重射頻(RF)電漿源。或者是，可使用單一RF電漿源。典型上，此一電漿源將是HFRF電漿源。
一第二核心層105係在形成為第一核心103之第一核心層的下方。一硬遮罩104可介於第一核心層與第二核心層105之間。硬遮罩104相對於第一核心層及第二核心層105可具有高蝕刻選擇性，以在圖案化第一核心層之時不 蝕刻第二核心層105。第二核心層105可由非晶碳材料或非晶矽材料製成。沉積方法及沉積先質可為以上就第一核心層所述任一者。一旦圖案化，第二核心層係形成為第二核心(亦稱為第二芯軸)105’(顯示於圖5)，且可用於在後續層中蝕刻一遮罩，例如遮罩層107c，其可接著用以圖案化目標層150。在若干實施例中，遮罩層107c可由非晶碳材料或非晶矽材料製成。在四重圖案化方式中，例如圖1-11所述者，遮罩層107c可為光阻圖案的四重圖案，使得在光阻中的一個特徵部係加以圖案化及轉移而在目標層150中形成四個特徵部。
其他層可在第二核心層105與目標層150之間，上述其他層係例如一硬遮罩層107a、或蓋層107b、或用以圖案化目標層150的遮罩層107c。目標層150可為最終加以圖案化的層。目標層150可為半導體、介電質、或其他層，且可由例如矽(Si)、矽氧化物(SiO2)、矽氮化物(SiN)、或鈦氮化物(TiN)製成。目標層150可藉由原子層沉積法(ALD)、電漿輔助ALD(PEALD)、化學汽相沉積法(CVD)、或其他適合的沉積技術加以沉積。
在一個範例中，例如圖1所顯示之四重圖案化堆疊的成分及厚度可如下：400Å的非晶碳第一核心103、150Å四乙基正矽酸鹽(TEOS)的硬遮罩層104、350Å非晶碳第二核心層105、150Å TEOS硬遮罩層107a、100Å非晶矽蓋層107b、300Å非晶碳遮罩層107c，上述層皆在一矽目標層或基板150之上，其可包含一選擇性的200Å鈦氮化物阻障層及一選擇性的300Å TEOS硬遮罩層。在一個例子中，以下者可沉積在400Å的非晶碳第一核心層之上以在微影圖案化之前定義如圖1範例所示之第一核心層：100Å-150Å SiON蝕刻終止層、300Å底部抗反射塗佈(BARC)層、及1000Å光阻第一核心層。
在圖2中，保形膜109係沉積在第一核心103之上。保形膜109亦可稱為「間隔部」，且可加以沉積而符合多層堆疊上圖案的形狀，以在該圖案上產生一均勻分布的層。如以下進一步描述的，保形膜109可形成為多個個別間隔部，其每一者係鄰接第一核心103的一側壁。保形膜109相對於核心具有高蝕刻選擇性。舉例來說，保形膜109相對於一非晶碳層具有大於3：1的蝕刻選擇性。在若干實施例中，保形膜109在鹵化物蝕刻化學品中相對於多晶矽具有大於15：1的蝕刻選擇性。
保形膜109可由例如SiO2之介電材料製成。保形膜109亦可為氧化物，例如鈦氧化物(TiO2)，或可為矽氮化物(SiN)。在一些實施例中，保形膜109係由較緻密的材料製成，以承受多「次(pass)」的圖案化，且可藉由如以下簡述之ALD、PEALD、或保形膜沉積(CFD)方法加以沉積。
ALD製程使用表面介導沉積反應以逐層地沉積膜。在一個例示ALD製程中，包含一群表面活性部位的基板表面，係暴露於第一膜先質(P1)的氣相分布。P1的一些分子可在基板表面上形成凝相，包含P1的化學吸附物種及物理吸附分子。反應器接著加以排空，以移除氣相及物理吸附的P1，使得僅化學吸附物種留存。一第二膜先質(P2)接著導入反應器，使得若干P2分子吸附至基板表面。反應器可再度加以排空，此次係用以移除游離的P2。隨後，提供至基板的熱能活化所吸附P1和P2分子之間的表面反應，形成一膜層。最後，將該反應器排空，以移除反應副產物和可能之未反應的P1和P2，結束此ALD循環。可包含額外的ALD循環以建立膜厚度。在PEALD製程的例子中，在將第二膜先質P2導入反應器時將電漿啟動，以活化P1與P2之間的反應。
CFD可用以沉積保形膜109。一般而言，CFD不需要在形成膜的反應之前完全沖洗一個以上反應物。舉例來說，當電漿(或其他活化能量)點燃時可能有一個以上反應物以汽相存在。因此，在一ALD製程中所描述的製程步驟其中一者以上，在一例示CFD製程中可加以縮短或取消。此外，在若干實施例中，沉積反應的電漿活化可導致較熱活化反應低的沉積溫度，可能降低積體製程的熱預算。基於上下文需要，提供CFD簡短說明。CFD循環的概念係相關於此處各種實施例的探討。如同ALD製程，一般而言一循環係用以執行一表面沉積反應一次所需的最小操作集合。一個循環的結果，係在一基板表面產生至少一局部的膜層。典型上，一CFD循環僅包含將各反應物輸送及吸附至基板表面且接著使那些吸附的反應物反應形成局部膜層所需的那些步驟。該循環可包含若干輔助步驟，例如掃除此等反應物或副產物其中一者以上及/或處理原沉積的局部膜。一般而言，一循環僅含有一獨特操作順序的一個實例。舉例來說，一循環可包含以下操作：(i)反應物A的輸送/吸附；(ii)反應物B的輸送/吸附；(iii)將B掃出反應腔室；及(iv)施加電漿以驅動A與B的表面反應，以在表面上形成局部膜層。當使用於此處，術語PEALD包含CFD製程。
以下條件係適於藉由一CFD製程沉積一矽氧化物保形膜109之條件的例子。沉積可發生在介於約50℃與約400℃之間的溫度，介於約0.5托與約10托之間壓力，及介於約100W與10kW之間用於四個站的RF功率。RF活化頻率可對於各種實施例變化於約13.56MHz與40MHz之間。對於矽氧化物保形膜109，可使用的製程氣體包含：作為矽來源的矽醯胺(例如BTBAS、BDEAS(雙二乙基胺基矽烷)或DIPAS(二異丙基氨基矽烷))、及作為氧來源的氧或氧化亞氮或二氧化碳(獨立或共同地)，其以例如氬或氮之惰性載體氣體稀釋。製 程氣體流率可如下：對於(液態)矽先質(例如BTBAS、BDEAS、及DIPAS)，介於約1sccm與3sccm之間，舉例來說，於約2.5sccm的BTBAS；對於氧先質(O2、N2O)，介於約5000sccm與10,000sccm，舉例來說，於5000sccm的N2O；及對於載體氣體(Ar或N2)，介於約0sccm與10,000sccm之間，舉例來說，約5000sccm的Ar。
在圖3中，保形膜109係加以回蝕刻或平坦化，以暴露第一核心103。在各種實施例中，保形膜109可藉由一多步驟製程加以平坦化。在一個例子中，保形膜109可藉由流動約30秒首先約10sccm至約100sccm的氯(Cl2)，接著約10sccm至約100sccm的甲烷(CH4)，接著約10sccm至約100sccm的氮(N2)，而加以回蝕刻。在一些實施例中，可在介於約10℃與約20℃之間的溫度以及介於約2毫托與約20毫托之間的壓力，將保形膜109蝕刻約30秒。在一些實施例中，基板可在介於約40℃與約60℃之間的溫度以及介於約5毫托與約100毫托之間的壓力加以蝕刻。在許多實施例中，執行非等向性電漿蝕刻以暴露該核心，且自保形膜109形成間隔部109’的結構。
在圖4中，第一核心103係加以剝離或蝕刻，在基板上留下獨立的間隔部109’。若該第一核心層係光阻，第一核心103可藉由，在介於約5毫托與約20毫托之間的壓力，於介於約40℃與約60℃之間的溫度，以介於約100sccm與約200sccm之間的流率流動氧(O2)，而加以蝕刻。
若第一核心層係由非晶碳材料製成，第一核心103可使用灰化方法加以剝除或蝕刻。一灰化方法可依靠化學反應進行材料移除，而非高能離子的方向性運動。舉例來說，暴露於一灰化操作中所使用製程氣體的任一表面，可受到由於暴露所導致的材料移除，因此在第一核心103中所使用的非晶碳材料 相對於間隔部109’可具有高蝕刻選擇性，使得在灰化第一核心103之時間隔部109’係未被蝕刻。此外，不同於一些化學蝕刻製程，灰化操作可產生完全氣態的反應產物。舉例來說，碳膜的灰化操作可利用解離的氫(H2)或氧(O2)作為製程氣體，其可與碳膜反應而形成此氣相反應副產物。在一些實施例中，殘留的間隔物109’可利用各種蝕刻條件加以形塑用於後續處理。
在圖5中，第二核心層105係利用間隔部109’作為遮罩加以向下蝕刻，藉此轉移圖案而形成第二核心105’。第二核心層105，可在介於約50℃與約70℃之間的溫度於介於約5毫托與約100毫托之間的壓力，利用適於蝕刻第二核心層105但不蝕刻間隔部109’的化學品加以蝕刻。第二核心層105因此相對於間隔部109’為高蝕刻選擇性。第二核心層105可為非晶碳層，或非晶矽層。在第二核心層105上方可為蓋層104，其可為矽抗反射塗層、或PECVD介電層、或旋塗式玻璃。
在圖6中，間隔部109’及蓋層104係加以蝕刻或以其他方式移除，留下圖案化的第二核心105’。在一些實施例中，間隔部109’可在約10℃與約20℃之間的溫度，以及介於約2毫托與約20毫托之間的壓力，以約30秒時間加以移除。在一些實施例中，基板可在約40℃與約60℃之間的溫度以及介於約5毫托與約100毫托之間的壓力加以蝕刻。在許多實施例中，執行非等向性電漿蝕刻。在一個範例中，藉由以約30秒首先流動約10sccm至約100sccm的氯(Cl2)，接著約10sccm至100sccm的甲烷(CH4)，接著約10sccm至約100sccm的氮(N2)，將間隔部109’蝕刻。
在圖7中，一第二保形膜119係沉積在圖案化的第二核心105’之上。在許多實施例中，第二保形膜119可為一鈦氧化物層，其可藉由PEALD方法沉積。
在圖8中，第二保形膜119係加以蝕刻或平坦化，以暴露第二核心105’。條件及方法可為以上就圖3所述任何一者。
在圖9中，第二核心105’係加以蝕刻或移除，留下獨立的第二間隔部119’。條件及方法可為以上就圖4所述任何一者。
在圖10中，遮罩層107c係利用第二間隔部119’作為遮罩加以向下蝕刻，藉此自第二間隔部119’轉移圖案以形成圖案化遮罩107c’。遮罩層107c相對於第二保形膜119可為高蝕刻選擇性的，且可取決於遮罩層107c的化學性質藉由以上就圖5所述任何方法加以蝕刻。
在圖11中，第二間隔部119’以及蝕刻終止層107a和蓋層107b係加以移除，留下圖案化的遮罩107c’。移除第二間隔部119’的條件及方法可為以上就圖6所述任何一者。遮罩107c’可接著用以圖案化後續的層，例如目標層150。圖1至11所述製程步驟的結果係一四重圖案化方式，使得一單一微影定義特徵部(例如圖1中的第一核心103)形成在基板上的四個較小特徵部。四重圖案化方式可用以形成特徵部，其具有小至10nm的半節距，或介於10nm與20nm之間的半節距，這藉由目前的雙重圖案化方式是無法達成的。
由於形成較小特徵部的本質，第二保形膜119所使用的材料，可相對於在較寬核心的間隔部中所使用之保形膜具有較高品質，以維持強韌性且在後續圖案化步驟中暴露於嚴酷條件時防止翹曲。較高品質的保形膜材料可具有接近理想的化學計量比，例如若保形膜為鈦氧化物，較高品質的鈦氧化物保 形膜可具有接近理想的Ti：O化學計量比(例如1：2)以及低的碳含量。較高品質保形膜可藉由ALD加以沉積，其可自氧化半反應執行一完全轉化，藉此形成接近理想的化學計量比。因此，較高品質保形膜材料可從而具有低蝕刻速率及高蝕刻選擇性，且亦係相對於氧化物及氮化物為無限選擇性。這些膜亦可具有較高模量，例如大於約150MPa，其有助於改善作為間隔部的保形膜的機械穩定性，藉此改善關鍵尺寸均勻性(CDU)。此處揭露的較高品質保形膜材料亦可為緻密的，以耐受後續的積體步驟。
此處提供薄的保形奈米層疊保護層之沉積方法。亦提供可用作間隔部之高品質膜的形成方法，其利用包含沉積一奈米層疊層之方法。該奈米層疊層可改善間隔部強韌性，且在沉積保形膜期間保護下方核心層免於劣化。
直接在一核心層上沉積高品質膜，例如高品質鈦氧化物，可能造成由於在間隔部沉積期間嚴酷環境導致的核心劣化或消耗，從而損傷下層的圖案化核心。舉例來說，在沉積高品質保形膜期間，一圖案化核心層可能暴露於氧自由基，例如以至少約1000W的高HFRF功率自N2O/O2順序型電漿所產生者。由於較高功率，更多氧自由基形成，這增加在核心層上的自由基轟擊以及隨後的核心圖案劣化。氮化物若使用作為核心層上的蓋層，可能能夠耐受此轟擊，但由於氮化物相對於若干核心材料係非選擇性的，氮化物並不適合。在沉積保形膜後，基板可接著加以平坦化以暴露核心及移除核心，但由於核心已耗損或劣化，間隔部之間所產生的寬度可能縮減，這導致在半導體基板中不規則圖案。此處所揭露方法，不使用低品質保形膜防止核心劣化，而是使高品質間隔部材料能夠使用。
奈米層疊保護層，由於在沉積期間所使用的較低HFRF功率，與保形膜相比較不緻密。因此奈米層疊保護層可能以充分保護該核心的最小厚度加以沉積。最小化奈米層疊保護層可能有助於後續的積體。奈米層疊保護層，可以較高品質保形膜可沉積於其上的程度保護一下層。核心耗損和劣化因而降低，且核心可耐受在高品質保形膜沉積期間的較嚴酷條件。在後續圖案化步驟中，高品質保形膜可耐受其他嚴酷條件且仍維持作為獨立結構的高強韌性。奈米層疊保護層亦可防止間隔部傾斜而允許關鍵尺寸變異性，這是藉由維持核心幾何結構的完整性並對獨立間隔部結構提供機械式支撐，從而增進在半導體處理中形成較低半節距之較精細特徵部的能力。
使用奈米層疊保護層之例示方法，可開始於提供一多堆疊半導體基板，其具有微影定義或圖案化的第一核心層，例如以上就圖1所述者。在一些實施例中，一奈米層疊保護層。在一些實施例中，奈米層疊保護層可在沉積保形膜109之前沉積在第一核心103之上，如以下就圖13所述實施例。在各種實施例中，保形膜109可沉積在第一核心103之上，例如在圖2中之情形。在保形膜109加以平坦化後，例如圖3所顯示，第一核心103可加以蝕刻或移除，以暴露剩餘的間隔部109’，例如圖4所顯示。一第二核心層105可使用間隔部109’作為遮罩加以向下蝕刻，從而轉移圖案而形成第二核心105’，例如圖5所顯示。間隔部109’可加以移除而暴露圖案化的第二核心105’，例如圖12所顯示。第二核心層105可為非晶碳層，或非晶矽層。
在圖13中，奈米層疊保護層111可在第二核心105’上加以保形沉積。奈米層疊層111的例示厚度，係介於約15Å與約200Å厚之間、介於約15Å 與約100Å厚之間、或介於約15Å與約50Å厚之間。要注意到，圖13所述厚度係以說明為目的誇大且僅作為範例。
在一些實施例中，奈米層疊層111可包含一堆疊，其可具有二層以上的子層(未顯示)。舉例來說，該堆疊可為雙層。在一些實施例中，此等子層具有相同的成分，且在一些實施例中，此等子層具有不同的成分。在一些實施例中，奈米層疊層111係一層。在一個實施例中，奈米層疊層111係一矽氧化物層。在另一例子中，奈米層疊層111係一鈦氧化物層。在雙層奈米層疊層111的一個例子中，上層係矽氧化物，且下層係鈦氧化物。在雙層奈米層疊層111的另一例子中，上層係鈦氧化物，且下層係矽氧化物。
由於可能用以沉積奈米層疊層111的較低HFRF功率，奈米層疊層111亦可能與保形膜中所沉積材料相比較不緻密。在一些實施例中，奈米層疊層111可為一ALD氧化物，例如矽氧化物(SiO2)或鈦氧化物(TiO2)，且稱為「軟」ALD氧化物。當設定圖案化方案的處理條件及決定蝕刻的圖案時，奈米層疊層111的厚度可加以考慮。在各種實施例中，奈米層疊層111係藉由保形膜沉積(CFD)或PEALD加以沉積。
在圖14中，第二保形膜129係沉積在奈米層疊層111之上。在若干實施例中，第二保形膜129係高品質鈦氧化物膜，例如一鈦氧化物層，其具有低濕式蝕刻速率以及相對於氧化物(例如矽氧化物(SiO2))及氮化物(例如矽氮化物(SiN))具有無限選擇性的高乾式蝕刻選擇性。舉例來說，第二保形膜129相對於非晶碳層可具有大於3：1的蝕刻選擇性。在一些實施例中，第二保形膜129在鹵化物蝕刻化學品中相對於多晶矽層具有大於15：1的蝕刻選擇性。在一個範例中，沉積至約15Å厚度的奈米層疊層111可足以保護第二核心105’免受沉積約110 Å之第二保形膜129的影響。在各種實施例中，第二保形膜129係藉由CFD或PEALD加以沉積。在一些實施例中，第二保形膜129係較奈米層疊層111緻密。
在圖15中，基板係加以平坦化，暴露具有奈米層疊層111側壁的第二核心105’且產生側壁第二間隔部129’。平坦化的條件可為以上就圖3所述任意一者。
在圖16中，第二核心105’係加以蝕刻並移除。條件及方法可為以上就圖9所探討任意一者。在一些實施例中，由於蝕刻步驟的本質，一小部分奈米層疊層111可能被蝕刻。在一些實施例中，奈米層疊層111係充分蝕刻選擇性的，而在移除第二核心105’時未被蝕刻。要注意到，第二間隔部129’係位於奈米層疊層111的一薄層之上，具有一薄的奈米層疊層111在其側壁上，這可從而加強其穩定性並防止傾斜。更進一步的是，在一些實施例中，奈米層疊材料可隨第二核心105’一起完全移除。如上所述，在一些實施例中，奈米層疊層111的厚度及其受移除的程度，在計畫圖案化方案以達成所欲尺寸時可加以考慮。然而，在一些實施例中，奈米層疊層111的厚度可在圖案化尺寸的容限之內，且可能不需要考慮。
在圖17中，遮罩層107c係利用第二間隔部129’作為遮罩加以向下蝕刻。由於較高品質第二間隔部129’之提高的穩定性及強韌性，此操作可更容易且更有效率地完成，形成具有高深寬比之精細、穩定的特徵部。
在圖18中，奈米層疊層111及第二間隔部129’係加以蝕刻或移除，以暴露所產生的圖案化遮罩107c’。條件及方法可為以上就圖5所述任意一者。圖案化遮罩107c’可接著使用，以圖案化一後續的層，其可用以圖案化目標層150。在一些實施例中，圖案化的遮罩107c’可用以圖案化目標層150。
圖19係根據各種實施例的一方法之步驟的製程流程圖。此處所述循環及暴露時間可取決於所使用設備及平台，且熟習此技藝者可據此調整循環和暴露時間。在操作1901中，一基板可暴露於第一先質，例如含鈦先質或含矽先質。在一些實施例中，基板包含一核心層。在各種實施例中，核心層係非晶碳、非晶矽、或光阻。在一些實施例中，核心層係加以微影定義或圖案化。在若干實施例中，基板包含一圖案化非晶碳層。
含鈦先質的例子包含肆二甲基胺基鈦(TDMAT)、四乙氧基鈦、肆(二甲基胺基)鈦、異丙氧化鈦(titanium isopropoxide)、四異丙氧化鈦、及四氯化鈦。含矽先質可例如矽烷、鹵代矽烷、或胺基矽烷。矽烷含有氫及/或碳基團，但不含有鹵素。矽烷的例子為甲矽烷(SiH4)、乙矽烷(Si2H6)、及有機矽烷，例如甲基矽烷、乙基矽烷、異丙基矽烷、叔丁基矽烷、二甲基矽烷、二乙基矽烷、二叔丁基矽烷、烯丙基矽烷、仲丁基矽烷、叔己基矽烷(thexylsilane)、異戊基矽烷、叔丁基二矽烷、二叔丁基二矽烷、四乙基正矽酸鹽(亦稱為四乙氧基矽烷或TEOS)及類似者。鹵代矽烷含有至少一鹵素基團，且可含有或可不含有氫及/或碳基團。鹵代矽烷的例子係碘矽烷、硼矽烷、氯矽烷、及氟矽烷。雖然鹵代矽烷，特別是氟矽烷，可形成能夠蝕刻矽材料的反應性鹵化物物種，在此處所述的若干實施例中，當電漿點燃時含矽反應物是不存在的。特定的氯矽烷為四氯矽烷(SiCl4)、三氯矽烷(HSiCl3)、二氯矽烷(H2SiCl2)、一氯矽烷(ClSiH3)、氯烯丙基矽烷、氯甲基矽烷、二氯甲基矽烷、氯二甲基矽烷、氯乙基矽烷、叔丁基氯矽烷、二叔丁基氯矽烷、氯異丙基矽烷、氯仲丁基矽烷、叔丁基二甲基氯矽烷、叔己基二甲基氯矽烷(thexyldimethylchlorosilane)、及類似者。胺基矽烷包含與一矽原子鍵結的至 少一氮原子，且亦可含有氫、氧、鹵素及碳。胺基矽烷的例子係一、二、三、及四胺基矽烷(分別為H3Si(NH2)4、H2Si(NH2)2、HSi(NH2)3、及Si(NH2)4)，以及經取代的一、二、三、及四胺基矽烷，例如叔丁基胺基矽烷、甲基胺基矽烷、叔丁基矽烷胺、雙(叔丁基胺基)矽烷(SiH2(NHC(CH3)3)2(BTBAS)、叔丁基甲矽烷基胺基甲酸酯、SiH(CH3)-(N(CH3)2)2、SiHCl-(N(CH3)2)2、(Si(CH3)2NH)3等等。胺基矽烷的另一例子係三甲矽烷基胺(N(SiH3)3)。
在操作1901後，可在一掃除階段以一注入器沖洗或一泵出步驟，將沉積腔室加以沖洗。一般而言，一沖洗階段將汽相反應物之一者自反應腔室移除或沖洗，且通常僅發生在此反應物輸送完成之後。換言之，那個反應物在掃除階段期間不再輸送至反應腔室。然而，該反應物在掃除階段期間維持吸附於基板表面上。通常，掃除係用以在反應物吸附至基板表面上達所欲程度之後移除在腔室中的任何殘留汽相反應物。一掃除階段亦可自基板表面移除弱吸附物種(例如若干先質配體或反應副產物)。在ALD中，掃除階段已被視為必要的，用以防止二個反應物的氣相交互作用或一反應物與表面反應之熱、電漿、或其他驅動力的交互作用。一般而言，且除非此處另行具體指明，可藉由(i)排空一反應腔室，及/或(ii)流動不含待掃出物種的氣體通過此反應腔室，達成一掃除/沖洗階段。在(ii)的情況中，此氣體可為例如惰性氣體。
在操作1903中，基板可暴露於第二先質或氧化劑。在一些實施例中，氧化劑係氧化亞氮(N2O)或氧(O2)或二氧化碳(CO2)或一混合物或以上組合。在一些實施例中，氧化劑可為氧(O2)與一弱氧化劑的混合物，該弱氧化劑係例如N2O、CO、CO2、NO、NO2、SO、SO2、CxHyOz、及/或H2O。在 其他實施方式中，氧化反應物可全然為弱氧化劑。或者，氧化反應物可包含O3。在一些實施例中，氧化反應物係約0-50%的O2及約50-100%的弱氧化劑。
在一些實例中，反應物其中一者可連續輸送(例如縱使在其他反應物輸送期間及/或在電漿暴露期間)。舉例來說，一氧化反應物可連續輸送。持續流入的反應物可與例如氬之載體氣體一起輸送至反應腔室。在一些實例中，向反應腔室持續流動的反應物之輸送，係利用分流閥/入口閥切換而加以控制。氣流變化可為轉向式或協流式。在一個範例中，持續流動的反應物係週期性自反應腔室加以轉向，使得它僅在若干時間輸送至反應腔室。連續流動的氣體可使用適當的閥轉向至出口/卸放部。舉例來說，一氧化反應物可連續流動，但僅週期性輸送至反應腔室。當氧化反應物未輸送至反應腔室時，它可能被轉向至一出口、回收系統等等。
在操作1905中，電漿可以低HFRF功率起始，同時將基板暴露於氧化劑。在一些實施例中，單位晶圓面積的低HFRF功率係介於每mm2約1.768×10-4W與每mm2約1.768×10-3W，其中mm2代表晶圓表面面積的單位。電漿功率可隨晶圓表面面積線性縮放。舉例來說，對於300mm晶圓低HFRF功率可介於每站約12.5W至約125W之間，或者對於450mm晶圓低HFRF功率可介於約28W至約280W之間。沉積溫度可介於約50℃與約150℃之間。在操作1905之後，沉積腔室可再度加以沖洗。這些步驟可重複，直到沉積所欲的膜厚度為止。
在一些實施例中，操作1905可以HFRF功率在低溫進行，例如低於約100℃的溫度，同時將300mm基板在一四站式基台中介於約50W與約500W之間暴露於氧化劑，該功率係施加至四站式機台的總功率。
在操作1907中，基板可暴露於含鈦先質。含鈦先質的例子可為就操作1901所述任一者。舉例來說，基板可暴露於TDMAT約2秒，這可描述為「用劑」。在操作1907之後，沉積腔室可以一注入器沖起或泵出步驟加以沖洗。舉例來說，沖洗可持續約10秒。
在操作1909中，基板可暴露於另一先質或氧化劑。在許多實施例中，該氧化劑係氧化亞氮(N2O)或氧(O2)或二氧化碳(CO2)或其混合物。舉例來說，操作1909可約30秒，使得在開始的25秒，沒有氧化劑流入且僅載體氣體或惰性氣體流入，且氧化劑在該25秒後開始流入且持續至下一操作。載體氣體的例子包含氬(Ar)及氮(N2)。這些載體氣體的流率可介於約0sccm與約10,000sccm之間。
在操作1911中，電漿可以高HFRF功率起始，且同時將基板暴露於氧化劑。在許多實施例中，對於300mm晶圓HFRF功率可介於每站約125W與約1500W之間。舉例來說，HFRF功率可約為每站625W。電漿可加以起始約0.25秒與約3秒之間的時間，或約0.5秒。操作1907至1911可進行於：介於約50℃與約400℃之間的溫度，或介於約50℃與約200℃之間的溫度，或約150℃的溫度；以及介於約3托與約3.5托之間的壓力。在操作1911之後，電漿可關閉，且腔室可加以沖洗或抽至基底。在操作1901、1903、1905、1907、1909、及1911之後使用的例示沖洗氣體，可為氬(Ar)或氮(N2)或任何其他適合的沖洗氣體。在一些實施例中，在操作1901至1905中所沉積的膜密度，可與在操作1907至1911中所沉積的膜相比較不緻密。
根據各種實施例，操作1901至1905可與操作1907至1911相比在較低溫度、及/或較低RF功率、及/或較短RF時間、及/或較低壓力、及/或使用較弱 氧化劑而加以執行。這些沉積條件可協助防止損傷下層基板且產生一可運作的元件。
圖20A提供根據各種實施例使用奈米層疊層之方法的製程流程圖。在操作2001中，一核心層可加以沉積，例如就圖1所述者。該核心層可為非晶碳層或非晶矽層，或可為光阻。在一些實施例中，核心層係加以圖案化。在操作2003中，奈米層疊層係沉積在核心層上。奈米層疊層可藉由CFD或PEALD方法加以沉積。奈米層疊層可使用以上就圖19所述操作1901-1905加以沉積。在一些實施例中，奈米層疊層可為矽氧化物(SiO2)或鈦氧化物(TiO2)。所沉積奈米層疊層的厚度可介於約15Å與約200Å之間、或介於約15Å與約100Å之間。在操作2005中，一金屬氮化物或金屬氧化物層可沉積在奈米層疊層上。該金屬氮化物或金屬氧化物層可使用關於以上圖19之操作1907至1911加以沉積。在一些實施例中，該金屬氮化物或金屬氧化物層係矽氧化物或鈦氧化物層。在一些實施例中，該金屬氮化物或金屬氧化物層係高品質鈦氧化物層。在各種實施例中，該金屬氮化物或金屬氧化物層相對於核心具有高蝕刻選擇性。在許多實施例中，金屬氮化物或金屬氧化物層係較奈米層疊層緻密。
圖20B係根據各種實施例使用奈米層疊層之方法範例的製程流程圖。在操作2011中，一薄的奈米層疊層係沉積在基板上。一奈米層疊層可為以上就圖13及20A所探討之任一者。奈米層疊層可使用關於以上圖19之操作1901-1905加以沉積。在操作2013中，鈦氧化物層可沉積在奈米層疊層上。沉積在奈米層疊層上的鈦氧化物層的例子係以上就圖14加以描述。鈦氧化物層可使用關於以上圖19之操作1907至操作1911加以沉積。
設備
此處所提供沉積技術可實現在電漿輔助化學汽相沉積(PECVD)反應器或保形膜沉積(CFD)反應器之中。此反應器可為多種型式，且可為一設備的部分，該設備包含較多個腔室或「反應器」(有時包含多個站)，其可各自容納一片以上晶圓且可用以執行各種晶圓處理操作。該一個以上腔室可維持晶圓於一個以上定義位置(在於此位置運動或不運動(例如轉動、振動、或其他擾動)的情況下)。在一個實施方式中，承受膜沉積之晶圓，在製程期間，可自反應器腔室內的一站轉移至另一站。在其他實施方式中，晶圓可於設備內於腔室間轉移，以執行不同的操作，例如蝕刻操作或微影操作。整個膜沉積可全部發生於單一站或對於任何沉積步驟進行總膜厚度的任何分率。在製程期間，各晶圓可藉由支座、晶圓夾頭、及/或其他晶圓固持設備，固持於適當位置。對於其中加熱晶圓的若干操作，該設備可包含一加熱器，例如一加熱板。由Fremont,CA的Lam Research Corp.所製造的VectroTM(例如C3 Vector)或SequelTM(例如C2 Sequel)，皆為可用以實施此處所述技術的適合反應器之範例。
圖21提供一簡單方塊圖，描繪配置用於實現此處所述方法的各種反應器元件。如所顯示，反應器2100包含一製程腔室2124，其包圍反應器的其他元件且用以容納由一電容放電式系統所產生的電漿，該電容放電式系統包含一噴淋頭2114，其與接地加熱塊2120結合而運作。高頻(HF)射頻(RF)產生器2104及低頻(LF)RF產生器2102可連接至匹配網路2106及噴淋頭2114。由匹配網路2106所提供的功率及頻率，可足以自供應至製程腔室2124之製程氣體產生電漿。舉例來說，匹配網路2106可提供50W至500W的HFRF功率。在一些範例中，匹配網路2106可提供100W至5000W的HFRF功率以及100W至5000W的 LFRF功率之總能量。在典型製程中，HFRF分量可通常介於5MHz至60MHz之間，例如13.56MHz。在具有LF分量的操作中，LF分量可為約100kHz至2MHz，例如430kHz。
在反應器內，一晶圓支座2118可支撐一基板2116。晶圓支座2118可包含夾頭、叉、或升降銷(未顯示)，用以在沉積及/或電漿處理反應期間及之間固持及搬運基板。該夾頭可為靜電夾頭、機械式夾頭、或可用於工業和/或研究的各種其他類型夾頭。
各種製程氣體可經由入口2112導入。多條來源氣體管線2110係連接至歧管2108。氣體可加以預先混合或不預先混合。可使用適當的閥調及質量流量控制機構，以確保在製程的沉積及電漿處理階段期間輸送正確的製程氣體。在化學先質以液態型式輸送的情況下，液體流量控制機構可加以使用。此等液體可接著加以汽化，且在抵達沉積腔室之前於一歧管在輸送期間與製程氣體混合，該歧管係加熱至高於以液體型式供應之該化學先質的汽化點。
製程氣體可經由出口2122離開腔室2124。可使用一真空泵，例如一或二階機械乾式泵及/或渦輪分子泵2140，將製程氣體抽出製程腔室2124，且藉由使用一封閉迴路受控流量限制裝置(例如節流閥或鐘擺閥)在製程腔室2124之內維持適合的低壓。
如以上所探討，此處所探討用於沉積的技術，可實現在一多站式機台或單站式機台上。在特定實施方式中，可使用具有4站沉積方案的300mm的Lam VectroTM機台或具有6站沉積方案的200mm的SequelTM機台。在一些實施方式中，可使用處理450mm晶圓之機台。在各種實施方式中，晶圓可在每次沉積及/或沉積後電漿處理之後加以分度；或者，若蝕刻腔室或站亦為相同機台的部 分，晶圓可在蝕刻步驟之後加以分度；或者，多個沉積及處理可在分度晶圓之前於單一站執行。
在一些實施例中，可設置一設備，用以執行此處所述技術。適合的設備可包含用於執行各種製程操作的硬體，以及一系統控制器2130，其具有用於根據所揭露實施例控制製程操作的指令。系統控制器2130通常包含一個以上記憶體裝置，以及一個以上處理器，其通訊連接至各種製程控制裝置，例如閥、RF產生器、晶圓搬運系統等等，且用以執行指令，使得該設備執行根據所述實施例的技術，例如提供於圖19沉積步驟中的技術。含有根據本揭露內容控制製程操作之指令的機器可讀媒體，可連接至系統控制器2130。控制器2130可通訊連接各種硬體裝置，例如質量流量控制器、閥、RF產生器、真空泵等等，以協助與如此處所述沉積操作相關聯的各種製程參數的控制。
在一些實施例中，一系統控制器2130可控制反應器2100的所有活動。系統控制器2130可執行系統控制軟體，該軟體係儲存在大容量儲存裝置，載入記憶體裝置，且在處理器上執行。該系統控制軟體可包含用於控制氣流時序、晶圓移動、RF產生器活動等等的指令，以及控制氣體混合物、腔室及/或站壓力、腔室和/或站溫度、晶圓溫度、目標功率位準、RF功率位準、基板支座、夾頭、及/或接受器位置、以及反應器2100執行之特定製程的其他參數的指令。系統控制軟體可以任何適合方式設定。舉例來說，各種製程機台元件子程式或控制物件可加以撰寫，以控制執行各種製程機台製程所需的製程機台元件的操作。系統控制軟體可以任何適合的電腦可讀程式語言編碼。
系統控制器2130通常可包含一個以上記憶體裝置及一個以上處理器，該處理器用以執行指令，使得該設備執行根據本揭露內容的技術。含有 用於根據所揭露實施例控制製程操作之指令的機器可讀媒體，可連接至系統控制器2130。
此處所揭露方法和設備可與微影圖案化機台或製程(例如以下所述用於半導體元件、顯示器、LED、光伏面板等之製造或生產者)結合使用。通常，雖非必然，此等機台/製程可在一共同的製造設施中一起加以使用或執行。膜的微影圖案化通常包含一些或全部以下步驟，每一步驟係以若干個可能的機台進行：(1)利用旋塗或噴塗機台，塗佈光阻於工件(即基板或如所揭露實施例提供的多層堆疊)之上；(2)使用一熱板或爐或UV固化機台固化光阻；(3)使用例如晶圓步進器之機台，將光阻暴露於可見光或UV或x光；(4)使用例如濕台之機台，將光阻顯影以選擇性移除光阻且藉此將其圖案化；(5)藉由使用乾式或電漿輔助蝕刻機台，例如以下所述者，將光阻圖案轉移至下層膜或工件之中；及(6)使用例如RF或微波電漿光阻剝除器之機台，將光阻移除。在一個實施方式中，晶圓上的一個以上間隙特徵部係使用此處所述技術填充以碳膜。該碳膜可接著用於例如此處所述目的其中一者。此外，該實施方式可包含上述步驟(1)至(6)其中一者以上。
一個以上製程站可包含於一多站式處理機台之中。圖22顯示一多站式處理機台2200實施例的示意圖，該處理機台2200具有一入站負載鎖室(load lock)2202和一出站負載鎖室2204，其任一者或二者可包含一遠程電漿源。在大氣壓力下的一機器人2206係用以將晶圓自透過一晶圓盒2208裝載的卡匣，經由一大氣埠2210，移動至入站負載鎖室2202之中。一晶圓係藉由機器人2206置放到入站負載鎖室2202之中的支座2212之上，大氣埠2210可加以關閉，且接著負載鎖室可加以抽真空。在入站負載鎖室2202包含一遠程電漿源的情況下，晶圓 可在導入處理腔室2214之前暴露於在負載鎖室之中的遠程電漿處理。此外，舉例來說，晶圓亦可在入站負載鎖室2202之中加熱，以移除濕氣和吸附的氣體。接下來，可將通至處理腔室2214的一腔室搬運埠2216開啟，且另一機器人(未顯示)將晶圓置放進反應器而在此反應器中所顯示的一第一站的支座之上以進行處理。雖然所示實施例包含負載鎖室，吾人將了解在若干實施例中可使晶圓直接進入一製程站。
所述處理腔室2214包含四個製程站，在圖22所示實施例中編號為1至4。各站具有一加熱的支座(對於站1顯示為2218)，以及氣體管線入口。吾人將了解，在若干實施例中，各製程站可具有不同的或多個目的。例如，在若干實施例中，一製程站可在CFD和PECVD製程模式之間切換。額外地或替代地，在若干實施例中，處理腔室2214可包含匹配的一對以上CFD和PECVD製程站。雖然所述處理腔室2214包含四個站，吾人將理解根據本揭露內容的一處理腔室可具有任何適合數量的站。舉例來說，在若干實施方式中，一處理腔室可具有五個以上的站，而在其他實施例中一個處理腔室可具有三個以下的站。
圖22亦描述一晶圓搬運系統2290的實施例，晶圓搬運系統2290用於在處理腔室2214之內搬送晶圓。在若干實施例中，晶圓搬運系統2290可在各種製程站之間及/或在一製程站和一負載鎖室之間搬送晶圓。吾人將了解可使用任何適合的晶圓搬運系統。非限定的範例包含晶圓轉盤(wafer carousel)和晶圓搬運機器人。圖22亦描述一系統控制器2250的實施例，用以控制處理機台2200的製程條件和硬體狀態。系統控制器2250可包含一個以上記憶體裝置2256、一個以上大量儲存裝置2254、及一個以上處理器2252。處理器2252可包含CPU或電腦、類比和/或數位輸入/輸出連接部、步進馬達控制器板等等。
在一些實施例中，系統控制器2250控制處理機台2200的所有活動。系統控制器2250執行系統控制軟體2258，其儲存於大量儲存裝置2254之中，載入記憶體裝置2256，且執行於處理器2252。或者是，控制邏輯可加以硬編碼於系統控制器2250之中。特定應用積體電路、可程式邏輯元件(例如現場可程式閘陣列或FPGA)等等可用於這些目的。在以下探討中，無論何處使用「軟體」或「程式碼」，功能可比擬之硬編碼邏輯可替代使用。系統控制軟體2258可包含指令，用於控制時序、氣體混合物、腔室和/或站壓力、腔室和/或站溫度、晶圓溫度、目標功率位準、RF功率位準、RF暴露時間、基板支座、夾頭和/或接受器位置、及由處理機台2200所執行的特定製程的其他參數。系統控制軟體2258可以任何適合方式加以建構。例如，可撰寫各種製程機台元件子程式或控制物件，以控制執行各種製程機台製程所需的製程機台元件的操作。系統控制軟體2258可以任何適合的電腦可讀程式語言編碼。
在若干實施例中，系統控制軟體2258可包含輸入/輸出控制(IOC)序列指令，用於控制各種上述參數。例如，CFD製程的各階段可包含一個以上指令，以供系統控制器2250執行。用於設定CFD製程階段的製程條件的指令，可包含於對應的CFD配方階段。在若干實施例中，該CFD配方階段可循序配置，使得CFD製程階段的所有指令係與該製程階段同時執行。
關聯於系統控制器2250儲存於大量儲存裝置2254及/或記憶體裝置2256的其他電腦軟體及/或程式，可在一些實施例中加以使用。用於此目的之程式或程式片段的例子，包含基板定位程式、製程氣體控制程式、壓力控制程式、加熱器控制程式、及電漿控制程式。
基板定位程式可包含用以裝載基板至支座2218之上及控制介於基板和處理機台2200的其他部件之間的間距的處理機台元件的程式碼。
製程氣體控制程式可包含程式碼，用於控制氣體成分和流率，且選擇性地在沉積之前將氣體流入一個以上製程站以穩定在製程站之中的壓力。在一些實施例中，控制器包含指令，用於在一核心層上沉積一奈米層疊保護層，以及在該保護層上沉積一保形層。
壓力控制程式可包含程式碼，用於藉由調節(舉例來說，在製程站排氣系統中的節流閥)進入製程站的氣流而控制製程站中的壓力。在一些實施例中，控制器包含指令，用於在一核心層上沉積一奈米層疊保護層，以及在該保護層上沉積一保形層。
加熱器控制程式可包含程式碼，用於控制流至用以加熱基板的加熱單元的電流。或者是，加熱器控制程式可控制對基板之傳熱氣體(例如氦)輸送。在若干實施方式中，控制器包含指令，用於在第一溫度沉積一奈米層疊保護層，且在第二溫度於該保護層上沉積一保形層，其中第二溫度係高於第一溫度。
電漿控制程式可包含程式碼，用於根據此處實施例設定在一個以上製程站之中的RF功率位準及暴露時間。在若干實施例中，控制器包含指令，用於以第一RF功率位準及RF持續時間沉積一奈米層疊保護層，且以第二RF功率位準及RF持續時間於該保護層上沉積一保形層。該第二RF功率位準及/或第二RF持續時間可較該第一RF功率位準/持續時間為高/長。
在若干實施例中，可具有與系統控制器2250相關聯的一使用者介面。該使用者介面可包含顯示螢幕、設備和/或製程條件的圖形化軟體顯示、及使用者輸入裝置，例如指向裝置、鍵盤、觸控螢幕、麥克風等等。
在若干實施例中，由系統控制器2250所調整的參數可關於製程條件。非限定範例包含製程氣體成分及流率、溫度、壓力、電漿條件(例如RF偏壓功率位準及暴露時間)等等。這些參數可以配方形式提供給使用者，該配方可利用使用者介面加以輸入。
監測製程的訊號可從各種製程機台感測器藉由系統控制器2250的類比及/或數位輸入連接部加以提供。用於控制製程的訊號可在處理機台2200的類比和數位輸出連接部加以輸出。可加以監測的製程機台感測器的非限定例子包含質量流量控制器、壓力感測器(例如壓力計)、熱電偶等等。適當程式化的回授和控制演算法可與來自這些感測器的資料一起使用，以維持製程條件。
系統控制器2250可提供程式指令，以實施上述沉積製程。程式指令可控制各種製程參數，例如DC功率位準、RF偏壓功率位準、壓力、溫度等等。此等指令可控制該等參數，以根據此處所述各種實施例操作膜堆疊的原位沉積。
系統控制器通常包含一個以上記憶體裝置和用以執行指令的一個以上處理器，俾使此設備執行根據所揭露實施例的方法。含有用於根據所揭露實施例控制製程操作的指令的機器可讀非暫時性媒體可連接至該系統控制器。
實驗
實驗1
進行實驗，以比較在未受保護核心上所沉積的間隔部或保形膜與在由奈米層疊保護層所保護的核心上所沉積者。在第一試驗中，提供一基板，其具有由非晶碳構成之圖案化核心層。高品質鈦氧化物係藉由電漿輔助原子層沉積(PEALD)或保形膜沉積(CFD)方法直接沉積在該核心層上。腔室壓力係約3托且溫度約150℃。基板暴露於第一先質(TDMAT)2秒，接著進行10秒的沖洗。基板接著在30秒的暴露操作中暴露於N2O/O2氧化劑混合物，其中開始的25秒僅流入載體氣體N2(流率上達9500sccm)，而在最後的5秒，開啟N2O/O2流動且維持開啟直到電漿起始0.5秒。起始電漿係使用每站625W的高頻射頻(HFRF)功率，或四站2500W。在0.5秒電漿暴露後，將N2O/O2流動及電漿同時關閉，且最後將腔室抽至基底以淨化腔室。所沉積保形膜及下層核心層的影像係顯示於圖23A中。劣化的核心層2304a係顯示於鈦氧化物(TiO2)保形膜層2302a的下方。
在第二試驗中，亦提供一基板，其具有由非晶碳構成之圖案化核心層。矽氧化物(SiO2)奈米層疊保護層係藉由PEALD沉積在該核心層上。沉積腔室溫度係50℃，且腔室壓力係1.8托。基板係暴露於含矽先質0.2秒，接著進行0.2秒的沖洗。基板接著在一0.3秒的第二暴露操作中暴露於N2O/O2氧化劑混合物。電漿對於四站式腔室以1000W加以起始，或每站約500W。將N2O/O2流動及電漿關閉，且將腔室加以沖洗。隨後，基板暴露於TDMAT 2秒，接著進行10秒的沖洗。在沖洗之後，基板在30秒的第二暴露操作中暴露於氧化劑N2O/O2，使得該混合物僅在最後的5秒流入，且於該30秒之後在每站625W或四站2500W起始電漿0.5秒時持續流動0.5秒。在電漿與氧化劑N2O/O2皆關閉之後，將腔室加以再度沖洗。所沉積保形膜、奈米層疊層、及下方核心層的影像係顯示於圖23B。 如所顯示，所沉積保形膜2302b係沉積在奈米層疊層2306上方，奈米層疊層2306係如此薄使得它與保形膜及其相鄰的核心層無法區分。要注意到，與圖23A相比，核心芯軸2304b具有非常少的劣化或耗損。
在第三試驗中，亦提供一基板，其具有由非晶碳構成之圖案化核心層。鈦氧化物(TiO2)奈米層疊保護層係藉由PEALD沉積在該核心層上。沉積腔室溫度係150℃，且腔室壓力係3托。基板係暴露於TDMAT 2秒，接著進行10秒的沖洗。基板接著在一30秒的第二暴露操作中暴露於N2O/O2氧化劑混合物，使得該混合物僅在最後的5秒流入，且在該30秒後，在對於四站式腔室以1000W或每站約500W起始電漿時持續流入0.5秒。將N2O/O2流動及電漿關閉，且將腔室加以沖洗。隨後，基板暴露於TDMAT 2秒，接著進行10秒的沖洗。在沖洗之後，基板在30秒的第二暴露操作中暴露於N2O/O2氧化劑，使得該混合物僅在最後的5秒流入，且在該30秒後，在以每站625W或四站2500W起始電漿0.5秒時持續流動0.5秒。在電漿與氧化劑N2O/O2皆關閉之後，將腔室加以再度沖洗。所沉積保形膜、奈米層疊層、及下方核心層的影像係顯示於圖23C。如所顯示，所沉積保形膜2302c係沉積在奈米層疊層2308上方，奈米層疊層2308亦係如此薄使得它與保形膜及其相鄰的核心層無法區分。要注意到，核心芯軸2304c具有非常少的劣化或耗損。
實驗2
另一系列的實驗係利用與就以上三個試驗所述相同條件但針對不具特徵部之空白基板而加以進行。在各試驗中，量測非晶碳層厚度，接著沉積間隔部且量測間隔部厚度，且最後量測間隔部沉積之後剩餘非晶碳層的厚 度。碳耗損係藉由自間隔部沉積前的厚度減去間隔部沉積之後的厚度而加以計算。此系列實驗的結果顯示於表1。
如表中所顯示，奈米層疊層的存在，大幅降低碳耗損。在沒有奈米層疊層的情況下，碳耗損為15.4nm，而對於SiO2及TiO2奈米層疊層二者，碳耗損僅約8nm。因此，沉積奈米層疊層在非晶碳層之上，特別是在圖案化的非晶碳層之上，在沉積間隔部時保護非晶碳層，且因此對於間隔部沉積可沉積較高品質的膜。
總結
雖然為了清楚理解已相當詳細描述前述實施例，吾人明白在隨附申請專利範圍的範疇內可實施若干變化及修飾。應注意到，有許多替代方式實現本案實施例的製程、系統、及設備。因此，本案實施例係視為說明性而非限制性，且此等實施例不限定於此處提供的細節。

Claims (14)

  1. 一種基板處理方法，該方法包含：沉積一核心層；在該核心層上沉積一奈米層疊層；及在該奈米層疊層上沉積一金屬氮化物或金屬氧化物層，其中該奈米層疊層包含一堆疊，該堆疊包含二層以上的子層，且其中該奈米層疊層包含矽氧化物或鈦氧化物。
  2. 如申請專利範圍第1項的基板處理方法，其中該核心層為圖案化層。
  3. 如申請專利範圍第1項的基板處理方法，其中該核心層包含碳。
  4. 如申請專利範圍第3項的基板處理方法，其中該核心層包含非晶碳或光阻。
  5. 如申請專利範圍第1項的基板處理方法，其中該奈米層疊層之該二層以上的子層之各者係使用電漿輔助原子層沉積(PEALD)加以沉積，其係藉由以下步驟進行：暴露該基板於一含鈦先質或一含矽先質；暴露該基板於一氧化劑；及在該基板暴露於該氧化劑之時，啟動電漿。
  6. 如申請專利範圍第1項的基板處理方法，其中該金屬氮化物或金屬氧化物層包含鈦氧化物或矽氧化物。
  7. 如申請專利範圍第1項的基板處理方法，其中該金屬氮化物或金屬氧化物層係相對於該核心層具有蝕刻選擇性。
  8. 如申請專利範圍第1項的基板處理方法，其中該奈米層疊層與該金屬氮化物或金屬氧化物層皆包含矽氧化物。
  9. 如申請專利範圍第8項的基板處理方法，其中該金屬氮化物或金屬氧化物層係較該奈米層疊層緻密。
  10. 一種基板處理方法，該方法包含：沉積一核心層；在該核心層上沉積一奈米層疊層；及在該奈米層疊層上沉積一金屬氮化物或金屬氧化物層，其中該金屬氮化物或金屬氧化物層係使用含金屬先質並藉由電漿輔助原子層沉積(PEALD)加以沉積，其中該奈米層疊層包含一堆疊，該堆疊包含二層以上的子層。
  11. 如申請專利範圍第10項的基板處理方法，其中該含金屬先質為含鈦先質或含矽先質，且該PEALD係藉由以下步驟執行：暴露該基板於該含鈦先質或該含矽先質；暴露該基板於一氧化劑；及在該基板暴露於該氧化劑之時，啟動電漿。
  12. 如申請專利範圍第11項的基板處理方法，其中該奈米層疊層係在介於約50℃與約150℃之間的溫度下加以沉積，且該電漿係在介於每平方公釐約1.768×10-4W與約1.768×10-3W之間的每平方公釐基板面積高頻射頻(HFRF)功率下加以啟動。
  13. 如申請專利範圍第11項的基板處理方法，其中該奈米層疊層係在低於約100℃的溫度下加以沉積。
  14. 如申請專利範圍第11項的基板處理方法，其中該金屬氮化物或金屬氧化物層為矽氧化物材料，其較包含矽氧化物之該奈米層疊層緻密。
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