TW202129748A - 半導體裝置的製造方法與蝕刻溶液 - Google Patents

半導體裝置的製造方法與蝕刻溶液 Download PDF

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TW202129748A
TW202129748A TW110101268A TW110101268A TW202129748A TW 202129748 A TW202129748 A TW 202129748A TW 110101268 A TW110101268 A TW 110101268A TW 110101268 A TW110101268 A TW 110101268A TW 202129748 A TW202129748 A TW 202129748A
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layer
inhibitor
etching solution
semiconductor device
manufacturing
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TW110101268A
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TWI759071B (zh
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連建洲
林群能
陳玠瑋
江子昂
葉明熙
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台灣積體電路製造股份有限公司
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Abstract

在圖案化介電層(如高介電常數的閘極介電層)上的金屬層(如p型金屬功函數層)的濕蝕刻製程中，可採用抑制劑以增加濕蝕刻溶液對金屬層與對介電層之間的選擇性。這些抑制劑可包括磷酸、羧酸、胺基酸、或羥基。

Description

半導體裝置的製造方法與蝕刻溶液
本發明實施例關於半導體裝置的製造方法，更特別關於採用的蝕刻溶液組成。
半導體裝置用於多種電子應用，比如個人電腦、手機、數位相機、與其他電子設備。半導體裝置的製作方法通常為依序沉積絕緣或介電層、導電層、與半導體層的材料於半導體基板上，接著採用微影圖案化多種材料層已形成電路構件與單元於半導體基板上。
半導體產業持續減少最小結構尺寸以持續改善多種電子構件(如電晶體、二極體、電阻、電容、或類似物)的積體密度，其可整合更多構件至給定面積中。然而隨著最小結構尺寸縮小，將產生需解決的額外問題。
在一實施例中，半導體裝置的製造方法包括：形成p型金屬功函數層於高介電常數的介電層上；以及施加濕蝕刻溶液至p型金屬功函數層，以移除p型金屬功函數層的一部分，且濕蝕刻溶液包括：金屬蝕刻劑；抑制劑，用於高介電常數的介電層；以及溶劑。
在另一實施例中，半導體裝置的製造方法包括：沉積第一p型功函數層於高介電常數的介電層上；以及採用濕蝕刻溶液蝕刻第一p型功函數層，以露出高介電常數的介電層之第一部分，其中高介電常數的介電層與濕蝕刻溶液反應以形成保護層於高介電常數的介電層上。
在又一實施例中，蝕刻溶液包括：溶劑；第一金屬蝕刻劑；氧化劑；以及抑制劑，其包含磷酸、羧酸、或胺基酸的一或多者。
下述詳細描述可搭配圖式說明，以利理解本發明的各方面。值得注意的是，各種結構僅用於說明目的而未按比例繪製，如本業常態。實際上為了清楚說明，可任意增加或減少各種結構的尺寸。
下述內容提供的不同實施例或例子可實施本發明實施例的不同結構。特定構件與排列的實施例係用以簡化本揭露而非侷限本發明。舉例來說，形成第一構件於第二構件上的敘述包含兩者直接接觸，或兩者之間隔有其他額外構件而非直接接觸。此外，本發明之多種實例可重複採用相同標號以求簡潔，但多種實施例及/或設置中具有相同標號的元件並不必然具有相同的對應關係。
此外，空間性的相對用語如「下方」、「其下」、「下側」、「上方」、「上側」、或類似用語可用於簡化說明某一元件與另一元件在圖示中的相對關係。空間性的相對用語可延伸至以其他方向使用之元件，而非侷限於圖示方向。元件亦可轉動90°或其他角度，因此方向性用語僅用以說明圖示中的方向。
此處所述的實施例關於鰭狀場效電晶體裝置的具體例子。然而實施例不限於此處提供的例子，其概念可實施於更多實施例。
圖1係半導體裝置100如鰭狀場效電晶體裝置的透視圖。在一實施例中，半導體裝置100包括基板101與第一溝槽103。基板101可為矽基板，但亦可採用其他基板如絕緣層上半導體、應變的絕緣層上半導體、或絕緣層上矽鍺。基板101可為p型半導體，但其他實施例的基板101可為n型半導體。
初始步驟形成的第一溝槽103，之後可用於形成第一隔離區105。第一溝槽103的形成方法可採用遮罩層(未圖示於圖1)與合適的蝕刻製程。舉例來說，遮罩層可為含氮化矽的硬遮罩，其形成方法可為化學氣相沉積，但亦可採用其他製程(如電漿輔助化學氣相沉積或低壓化學氣相沉積)所形成的其他材料(如氧化物、氮氧化物、碳化矽、上述之組合、或類似物)，甚至可先形成氧化矽後進行氮化。一旦形成遮罩層，可由合適的光微影製程圖案化遮罩層，以露出基板101將移除以形成第一溝槽103的部分。
然而本技術領域中具有通常知識者應理解，形成遮罩層的上述製程與材料並非保護基板101的部分與露出基板101的其他部分以形成第一溝槽103的唯一方法。可採用任何合適製程如圖案化與顯影光阻，露出基板101將移除以形成第一溝槽103的部分。所有的這些方法完全包含於此實施例的範疇中。
一旦形成與圖案化遮罩層，即可形成第一溝槽103於基板101中。可由合適製程如反應性離子蝕刻移除露出的基板101，以形成第一溝槽103於基板101中，但亦可採用任何合適製程。在一實施例中，第一溝槽103自基板101的表面向下的第一深度可小於約5000 Å，比如約2500 Å。
然而本技術領域中具有通常知識者應理解，上述形成第一溝槽103的製程僅為可能的製程之一而非唯一實施例。可採用任何合適製程形成第一溝槽103，其可包含任何數目的遮罩與移除步驟。
除了形成第一溝槽103，遮罩與蝕刻製程可自基板101保留未移除的部分另外形成鰭狀物107。為了方便說明，圖式中的鰭狀物107與基板101隔有虛線，但兩者之間的物理分隔可存在或不存在。這些鰭狀物107可用於形成多閘極鰭狀場效電晶體的通道區。雖然圖1只顯示四個自基板101形成的鰭狀物107，但可採用任何數目的鰭狀物107。
鰭狀物107在基板101的表面之寬度可介於約5 nm至約80 nm之間，比如約30 nm。此外，鰭狀物107彼此分開的距離可介於約10 nm至約100 nm之間，比如約50 nm。以此方式分開的鰭狀物107，可各自形成分開的通道區，且仍近到足以共用共同閘極(如下述)。
一旦形成第一溝槽103與鰭狀物107，可將介電材料填入第一溝槽103，並可使第一溝槽103中的介電材料凹陷，以形成第一隔離區105。介電材料可為氧化物材料、高密度電漿的氧化物、或類似物。在視情況清潔與襯墊第一溝槽103之後可形成介電材料，其形成方法可採用化學氣相沉積法(如高深寬比製程)、高密度電漿化學氣相沉積法、或本技術領域中已知的其他合適形成方法。
可將介電材料超填第一溝槽103與基板101，接著以合適製程如化學機械研磨、蝕刻、上述之組合、或類似方法移除第一溝槽103與鰭狀物107之外的多餘材料。在一實施例中，移除製程可移除鰭狀物107上的任何介電材料，並露出鰭狀物107的表面以用於後續製程步驟。
一旦將介電材料填入第一溝槽103，接著可自鰭狀物107的表面使介電材料向下凹陷。凹陷製程可露出與鰭狀物107的上表面相鄰的鰭狀物107的側壁之至少一部分。使介電材料凹陷的方法可採用濕蝕刻，其將鰭狀物107的上表面浸入蝕刻劑如氫氟酸，但亦可浸入其他蝕刻劑如氫氣，或採用其他方法如反應性離子蝕刻、採用蝕刻劑如氨與三氟化氮的乾蝕刻、化學氧化物移除、或乾式化學清潔。介電材料自鰭狀物107的表面凹陷的距離可介於約50 Å至約500 Å之間，比如約400 Å。此外，凹陷步驟亦可移除任何高於鰭狀物107的介電材料，確保露出鰭狀物107以用於後續製程。
然而如本技術領域中具有通常知識者所知，上述步驟僅為填入介電材料與使介電材料凹陷的完整製程流程的部分。舉例來說，亦可採用襯墊步驟、清潔步驟、退火步驟、填隙步驟、上述之組合、或類似步驟，以形成介電材料並填入第一溝槽103。所有可能的製程步驟完全包含於此實施例的範疇中。
在形成第一隔離區105之後，可形成虛置閘極介電層109、虛置閘極介電層109上的虛置閘極111、與第一間隔物113於每一鰭狀物107上。在一實施例中，虛置閘極介電層109的形成方法可為熱氧化、化學氣相沉積、濺鍍、或本技術領域已知用於形成閘極介電層的任何其他方法。虛置閘極介電層109在鰭狀物107的頂部上的厚度可與在鰭狀物107的側壁上的厚度不同，端視形成閘極介電層的技術而定。
虛置閘極介電層109可包含材料如氧化矽或氮氧化矽，其厚度可為約3 Å至約100 Å (比如約10 Å)。虛置閘極介電層109的組成可為高介電常數材料(其相對介電常數大於約5)，比如氧化鑭、氧化鋁、氧化鉿、氮氧化鉿、氧化鋯、或上述之組合，其等效氧化物厚度為約0.5 Å至約100 Å (比如小於或等於10 Å)。此外，二氧化矽、氮氧化矽、及/或高介電常數材料的任何組合亦可用於虛置閘極介電層109。
虛置閘極111可包含導電或不導電的材料，且可為多晶矽、鎢、鋁、銅、鋁銅、鈦、氮化鈦鋁、碳化鉭、碳氮化鉭、氮化鉭矽、錳、鋯、氮化鈦、鉭、氮化鉭、鈷、鎳、上述之組合、或類似物。虛置閘極111的沉積方法可為化學氣相沉積、濺鍍沉積、或本技術領域中已知用於沉積導電材料的其他技術。虛置閘極111的厚度可為約5 Å至約200 Å。虛置閘極111可具有不平坦的上表面，且可在圖案化虛置閘極111或蝕刻閘極之前先平坦化虛置閘極111的上表面。此時可或可不將離子導入虛置閘極111。舉例來說，導入離子的方法可為離子佈植技術。
一旦形成虛置閘極介電層109與虛置閘極111，即可圖案化上述兩者以形成一系列的堆疊115於鰭狀物107上。堆疊115定義多個通道區於虛置閘極介電層109之下的鰭狀物107的每一側上。堆疊115的形成方法可為沉積與圖案化閘極堆疊(未圖示於圖1)於虛置閘極111上，其可採用本技術領域已知的沉積與光微影技術。閘極遮罩可結合一般採用的遮罩與犧牲材料，比如但不限於氧化矽、氮氧化矽、碳氮氧化矽、碳化矽、碳氧化矽、及/或氮化矽，且其沉積厚度可介於約5 Å至約200 Å之間。可採用乾蝕刻製程蝕刻虛置閘極111與虛置閘極介電層109，以形成圖案化的堆疊115。
一旦圖案化堆疊115，即可形成第一間隔物113。第一間隔物113可形成於堆疊115的兩側上。第一間隔物113的形成方法通常為毯覆性沉積間隔物層(未圖示於圖1)於之前形成的結構上。間隔物層可包含氮化矽、氮氧化物、碳化矽、氮氧化矽、碳氮氧化矽、碳氧化矽、氧化物、或類似物，且其形成方法可用於行程這些層狀物，比如化學氣相沉積、電漿輔助化學氣相沉積、濺鍍、或本技術領域已知的其他方法。間隔物層與第一隔離區105中的介電材料可為不同蝕刻特性的不同材料，或採用相同材料。接著可圖案化間隔物層以自結構的水平表面移除間隔物層，進而形成第一間隔物113，且圖案化方法可為一或多道蝕刻。
在一實施例中，第一間隔物113的厚度可介於約5 Å至約500 Å之間。此外，一旦形成第一間隔物113，與一堆疊115相鄰的第一間隔物113以及與另一堆疊相鄰的第一間隔物113之間相隔的距離，可介於約5 nm至約200 nm之間，比如約20 nm。然而可採用任何合適的厚度與距離。
雖然圖1未顯示，一些實施例可視情況自堆疊115與第一間隔物113未保護的區域移除鰭狀物107，並再成長源極/汲極區。自堆疊115與第一間隔物113未保護的區域移除鰭狀物107，其可採用堆疊115與第一間隔物113作為硬遮罩並進行反應性離子蝕刻或任何其他合適的移除製程。移除步驟可持續到鰭狀物107低於第一隔離區105的表面與與第一隔離區105的表面共平面。
一旦移除鰭狀物107的這些部分，可放置並圖案化硬遮罩(未圖示)，其覆蓋虛置閘極以避免成長，且再成長的源極/汲極區可接觸每一鰭狀物107。在一實施例中，可再成長源極/汲極區以形成應力體，其可施加應力至堆疊115之下的鰭狀物107的通道區。在一實施例中，鰭狀物107包括矽且鰭狀場效電晶體為p型裝置，而源極/汲極區的再成長方法可為選擇性磊晶製程，其材料如矽或矽鍺的晶格常數不同於通道區。磊晶成長製程可採用前驅物如矽烷、二氯矽烷、鍺烷、或類似物，且其可持續約5分鐘至約120分鐘(比如約30分鐘)。
在一實施例中，源極/汲極區的厚度可介於約5 Å至約1000 Å之間，且在第一隔離區105上的高度介於約10 Å至約500 Å之間(比如約200 Å)。在此實施例中，源極/汲極區高於第一隔離區105的上表面之高度介於約5 nm至約250 nm之間(比如約100 nm)。然而可採用任何合適高度。
一旦形成源極/汲極區，可佈植合適的摻質至源極/汲極區中，以完成鰭狀物107中的摻質。舉例來說，可佈植p型摻質如硼、鎵、銦、或類似物以形成p型金氧半裝置。在另一實施例中，可佈植n型摻質如磷、砷、銻、或類似物以形成n型金氧半裝置。這些摻質的佈植方法可採用堆疊115與第一間隔物113作為遮罩。值得注意的是，本技術領域中具有通常知識者應理解可採用許多其他製程、步驟、或類似方法佈植摻質。舉例來說，本技術領域中具有通常知識者應理解可進行多道佈植，其採用多種間隔物與襯墊層的組合，可形成特定形狀或特性的源極/汲極區以適用於特定目的。這些製程的任一者可用於佈植摻質，且上述內容並不侷限此實施例至上述步驟。
此外，此時可移除在形成源極/汲極區時覆蓋虛置閘極111的硬遮罩。在一實施例中，移除硬遮罩的方法可採用濕蝕刻製程或乾蝕刻製程，其對硬遮罩的材料具有選擇性。然而可採用任何合適的移除製程。
圖2A顯示形成層間介電層201，而圖2B顯示圖2A的剖視圖，且圖2B顯示兩個額外鰭狀物107於剖視圖中。此外，圖2A顯示基板101的第一區207與第二區209，而圖2B顯示基板101的第三區211與第四區213。
層間介電層201包含的材料可為硼磷矽酸鹽玻璃，但可採用任何合適的介電材料。層間介電層201的形成方法可採用電漿輔助化學氣相沉積，但亦可改用其他製程如低壓化學氣相沉積。層間介電層201的厚度可介於約100 Å至約3000 Å之間。一旦形成層間介電層201，可採用平坦化製程如化學機械研磨製程平坦化層間介電層201與第一間隔物113 (未圖示於圖2A及2B以求圖式清楚)，但亦可採用任何合適製程。
圖2A及2B亦顯示移除虛置閘極111與虛置閘極介電層109的材料。在一實施例中，虛置閘極111與虛置閘極介電層109的移除方法可採用一或多道濕蝕刻或乾蝕刻製程，其採用的蝕刻劑對虛置閘極111與虛置閘極介電層109的材料具有選擇性。然而可採用任何合適的移除製程。
一旦移除虛置閘極111與虛置閘極介電層109，可沉積一系列的層狀物以置換虛置閘極111與虛置閘極介電層109。在一實施例中，一系列的層狀物可包含視情況形成的界面層(未圖示)、第一介電材料203、與第一p型金屬功函數層205。
在形成第一介電材料203之前，可視情況形成界面層。在一實施例中，界面層的材料可為原位蒸汽產生製程所形成的二氧化矽。在另一實施例中，界面層可為高介電常數的材料如氧化鉿、矽酸鉿、氮氧化鉿矽、氧化鉿鉭、氧化鉿鈦、氧化鉿鋯、氧化鑭、氧化鋯、氧化鉭、上述之組合、或類似物，且其第一厚度可介於約5 Å至約20 Å之間(比如約10 Å)。然而可採用任何合適材料或形成製程。
一旦形成界面層，即可形成第一介電材料203於界面層上。在一實施例中，第一介電材料203為高介電常數的材料如氧化鉿、矽酸鉿、氮氧化鉿矽、氧化鉿鉭、氧化鉿鈦、氧化鉿鋯、氧化鑭、氧化鋯、氧化鉭、上述之組合、或類似物，且其沉積製程可為原子層沉積、化學氣相沉積、或類似製程。第一介電材料203可沉積至第二厚度，其介於約5 Å至約200 Å之間，但亦可採用任何合適的材料與厚度。
第一p型金屬功函數層205可與第一介電材料203相鄰。在一實施例中，第一p型金屬功函數層205可自金屬化材料(如摻雜矽的氮化鈦、氮化鈦、鈦、氮化鈦鋁、碳化鉭、碳氮化鉭、氮化鉭矽、鉭矽化物、鎳矽化物、錳、鋯、鋯矽化物、氮化鉭、釕、鋁、鉬、鉬矽化物、氮化鎢、其他金屬氧化物、金屬氮化物、金屬矽酸鹽、過渡金屬氧化物、過渡金屬氮化物、過渡金屬矽酸鹽、金屬的氮氧化物、金屬鋁酸鹽、矽酸鋯、鋁酸鋯、上述之組合、或類似物)所形成。此外，第一p型金屬功函數層205的沉積製程可採用原子層沉積、化學氣相沉積、濺鍍、或類似製程，其沉積的第四厚度可介於約5 Å至約200 Å，但亦可採用任何合適的沉積製程或厚度。
圖2A及2B另外顯示製程中的初始步驟，其可自第一區207、第三區211、與第四區213移除第一p型金屬功函數層205，但不自第二區209移除第一p型金屬功函數層205。在一實施例中，移除步驟可先將第一光阻215置於第二區209上。第一光阻215可為三層光阻，其具有底抗反射塗層217、中間遮罩層219、與頂光敏層221。形成底抗反射塗層217以準備形成頂光敏層221。底抗反射塗層217如名所述，可在曝光頂光敏層221時避免能量(如光)產生不受控制或不想要的反射回上方的頂光敏層221，進而避免反射光在頂光敏層221其不需要的區域中造成反應。此外，底抗反射塗層217可用於提供平坦表面，有助於減少能量斜向撞擊的副作用。
中間遮罩層219可位於底抗反射塗層217上。在一實施例中，中間遮罩層219為硬遮罩材料如氮化矽、氧化物、氮氧化物、碳化矽、上述之組合、或類似物。中間遮罩層219所用的硬遮罩材料之形成製程可為化學氣相沉積，但亦可改用其他製程如電漿輔助化學氣相沉積、低壓化學氣相沉積、或旋轉塗佈，甚至可先形成氧化矽後進行氮化。可採用任何合適方法或方法的組合以形成或放置硬遮罩材料，且這些方法或組合完全包含於實施例的範疇中。中間遮罩層219的厚度可介於約100 Å至約800 Å之間，比如約300 Å。
在一實施例中，形成頂光敏層221於中間遮罩層219上的方法可採用旋轉塗佈製程，且頂光敏層221可包含光阻聚合物樹脂與一或多個光活性成分於光阻溶劑中。光活性成分可吸收圖案化光源並產生反應物於頂光敏層221的曝光部分，進而與光阻聚合物樹脂進行後續反應以形成可顯影的產物，以複製圖案化的能量源於頂光敏層221中。
一旦形成底抗反射塗層217、中間遮罩層219、與頂光敏層221，則以圖案化的能量源(如光)曝光並顯影頂光敏層221，以覆蓋第二區209而不覆蓋第一區207、第三區211、與第四區213。在一實施例中，圖案化頂光敏層221使其寬度介於約60 nm至約160 nm之間(比如約120 nm)。然而可採用任何合適寬度。
如圖3A及3B所示，一旦圖案化頂光敏層221，則頂光敏層221之後可作為遮罩以延伸圖案至中間遮罩層219中。在一實施例中，延伸頂光敏層221的圖案之方法可採用一或多道蝕刻製程，比如一或多道反應性離子蝕刻。然而可採用任何合適方法以延伸頂光敏層221的圖案。
此外，一旦圖案化中間遮罩層219，可採用中間遮罩層219的圖案作為另一遮罩以延伸圖案置底抗反射塗層217中。在一實施例中，延伸中間遮罩層219的圖案之方法可採用一或多道蝕刻製程，比如一或多道反應性離子蝕刻。然而可採用任何合適方法以延伸中間遮罩層219的圖案。
圖3A及3B另外顯示在圖案化中間遮罩層219及/或底抗反射塗層217時，可能消耗頂光敏層221。舉例來說，圖案化中間遮罩層219及/或底抗反射塗層217所用的蝕刻劑，亦可蝕刻頂光敏層221 (不過蝕刻速率較小)。如此一來，頂光敏層221仍作為遮罩，雖然圖案化底抗反射塗層217的步驟結束時可能完全移除頂光敏層221。若未完全移除頂光敏層221，則可視情況採用灰化製程移除頂光敏層221。然而可採用任何其他合適製程以移除頂光敏層221。
圖4A及4B顯示一旦露出第二區209中露出第一p型金屬功函數層205，即由濕蝕刻溶液401移除第一區207、第三區211、與第四區213中的第一p型金屬功函數層205。在移除第一p型金屬功函數層205之前，可視情況移除中間遮罩層219。在一實施例中，移除中間遮罩層219的方法可採用合適的蝕刻製程如濕蝕刻製程，其採用的蝕刻劑對中間遮罩層219的材料具有選擇性。然而可採用任何合適的移除製程移除中間遮罩層219。
在一實施例中，可採用一或多道蝕刻製程移除第一區207、第三區211、與第四區213中的第一p型金屬功函數層205。蝕刻製程可為對第一p型金屬功函數層205的材料如氮化鈦具有選擇性的濕蝕刻製程或乾蝕刻製程，且其在不明顯移除或損傷下方材料(如第一介電材料203)時即停止。
在一實施例中，採用濕蝕刻製程移除第一p型金屬功函數層205，且濕蝕刻製程不只移除第一p型金屬功函數層205，亦有助於抑制下方的第一介電材料203發生任何不想要的蝕刻及移除。在具體實施例中，濕蝕刻溶液401包括金屬蝕刻劑、氧化劑、抑制劑、與溶劑。
金屬蝕刻劑可為與第一p型金屬功函數層205的露出部分反應並移除露出部分的蝕刻劑。如此一來，精確的金屬蝕刻劑至少部分取決於第一p型金屬功函數層205所用的材料。在一實施例中，第一p型金屬功函數層205為摻雜矽的氮化鈦，而金屬蝕刻既可為氫氧化四甲基銨、氫氧化銨、氫氧化四丁基銨、羥基胺、上述之組合、或類似物。然而亦可採用任何合適的金屬蝕刻劑。
可視情況添加氧化劑至濕蝕刻溶液401中，以調整濕蝕刻製程的蝕刻特性，比如加速蝕刻第一p型金屬功函數層205的材料。在一些實施例中，氧化劑可包含化學劑如過氧化氫、硝酸、氯酸、過氯酸、上述之組合、或類似物。然而可採用任何合適的氧化劑。
然而為了緩解或減少金屬蝕刻劑與氧化劑對第一介電材料203造成的損傷，可添加抑制劑至濕蝕刻溶液401中。在一些實施例中，抑制劑為高介電常數的介電層所用的有機抑制劑。一旦移除第一p型金屬功函數層205而露出第一介電材料203的表面，第一介電材料203的露出表面可吸附抑制劑或與抑制劑反應，有助於保護第一介電材料203。
一旦第一介電材料203的表面吸附抑制劑或與抑制劑反應，抑制劑位於第一介電材料203的表面上，並以多種方法幫助避免損傷下方的第一介電材料203。舉例來說，抑制劑存在於第一介電材料203的表面上，抑制劑的分子尺寸造成的立體障礙，有助於避免金屬蝕刻劑或氧化劑接觸下方的第一介電材料203的材料。
在另一實施例中，可選擇抑制劑以特別轉移第一介電材料203的物理特性，並有助於避免與金屬蝕刻劑或氧化劑反應。舉例來說，一些實施例的第一介電材料203的預反應表面為親水性，且可選擇抑制劑與表面反應，使第一介電材料203的表面自親水性轉變成疏水性。這些調整有助於避免蝕刻劑(其可為親水性)接觸第一介電材料203的表面並與其反應。
在一些實施例中，抑制劑可為酸如磷酸。在具體實施例中，磷酸的結構如下：
Figure 02_image001
其中R與R'各自為烷基、烷氧基、胺基、酯基、或苯基。在具體實施例中，抑制劑可為磷酸、二(2-乙基己基)磷酸、二己基磷酸、乙基十六烷基磷酸鹽、正丁基辛基氫磷酸鹽、二異戊基磷酸、乙基辛基磷酸鹽、上述之組合、或類似物。然而可採用任何合適的磷酸。
一實施例在蝕刻第一p型金屬功函數層205時，磷酸的抑制劑除了可與第一介電材料203的表面反應，亦可與氧化劑如過氧化氫反應。這些反應會造成R-PO3 2- 基團鍵結至第一介電材料203的表面。此基團可提供立體障礙以阻礙第一介電材料203的反應，並使第一介電材料203的表面轉變為疏水性。這些作用一起減少或消除金屬蝕刻劑與第一介電材料203的表面之間的反應，並有助於減少或避免損傷第一介電材料203。
在另一實施例中，抑制劑可為酸如羧酸。在具體實施例中，羧酸可具有下述結構：
Figure 02_image003
其中R可為C2 -C8 的碳鏈或苯基。在具體實施例中，羧酸的抑制劑可為丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、上述之組合、或類似物。然而可採用任何合適的羧酸。
此實施例在蝕刻第一p型金屬功函數層205時，一旦露出第一介電材料203，羧酸的抑制劑即可與第一介電材料203的表面反應。這些反應會造成R-COO- 基團鍵結至第一介電材料203的表面。此基團可提供立體障礙以阻礙第一介電材料203的反應，並使第一介電材料203的表面轉變成疏水性。這些作用一起減少或消除金屬蝕刻劑與第一介電材料203的表面之間的反應，並有助於減少或避免損傷第一介電材料203。
在另一實施例中，抑制劑可為酸如胺基酸。在具體實施例中，胺基酸可具有下述結構：
Figure 02_image005
其中R可為烷基、胺基、酯基、或苯基。在具體實施例中，抑制劑可為胺基酸如甘氨酸、丙氨酸、苯丙氨酸、酪氨酸、谷氨酸、蛋氨酸、半胱氨酸、亮氨酸、上述之組合、或類似物。然而可採用任何合適的胺基酸。
此實施例在蝕刻第一p型金屬功函數層205時，一旦露出第一介電材料203的表面，胺基酸的抑制劑即與第一介電材料203的表面反應。此反應會造成R-NH基團鍵結至第一介電材料203的表面。此基團可提供立體障礙以阻礙第一介電材料203的反應，且可使第一介電材料203的表面轉為疏水性。這些作用一起減少或消除金屬蝕刻劑與第一介電材料203的表面之間的反應，且有助於減少或避免損傷第一介電材料203。
在另一實施例中，抑制劑的分子可具有羥基。在具體實施例中，具有羥基的分子具有下述結構：
Figure 02_image007
其中R可為烷基、烷氧基、胺基、酯基、或苯基。在具體實施例中，抑制劑包括羥基，且抑制劑可為乙二醇、二乙二醇、三乙二醇、乙二醇丁醚、卡必醇、上述之組合、或類似物。然而可採用具有羥基的任何合適分子。
此實施例在蝕刻第一p型金屬功函數層205時，一旦露出第一介電材料203的表面，含羥基的抑制劑即與第一介電材料203的表面產生氫鍵。這些氫鍵會造成R-O-基團鍵結至第一介電材料203的表面。此基團可提供立體障礙以阻礙第一介電材料203的反應，亦可使第一介電材料203的表面轉變成疏水性。這些作用一起減少或消除金屬蝕刻劑與第一介電材料203的表面之間的反應，且有助於減少或避免損傷第一介電材料203。
為了製備濕蝕刻溶液401，可將金屬蝕刻劑、氧化劑、與抑制劑的每一者置入溶劑中以混合成分，並提供傳輸與分散濕蝕刻溶液401的方法。在一些實施例中，溶液可為乙二醇、二乙二醇、N-羥基乙基-2-吡咯烷酮、二甲基亞碸、環丁碸、上述之組合、或類似物。然而可採用任何合適溶劑。
混合濕蝕刻溶液401的個別組成，使其濃度足以移除第一p型金屬功函數層205，而不過蝕刻或損傷下方的第一介電材料203。在一實施例中，金屬蝕刻劑的混合濃度可介於約2體積%至約10體積%之間，比如約4.5體積%。此外，氧化劑的混合濃度可介於約5體積%至約20體積%，比如約12體積%。抑制劑的非零混合濃度可小於約5體積%，比如0.5體積%。將所有成分(與任何其他所需成分)加入溶劑，且溶劑的濃度可介於約30體積%至約90體積% (比如約75體積%)。若金屬蝕刻劑與氧化劑的濃度過高，第一介電材料203可能發生不想要的損失。此外，若抑制劑超出5體積%，則第一p型金屬功函數層205的蝕刻速率會受到不想要的抑制。然而可採用任何合適濃度。
一旦製備濕蝕刻溶液401，即可施加濕蝕刻溶液401至第一p型金屬功函數層205，以開始蝕刻移除第一p型金屬功函數層205。在一實施例中，施加濕蝕刻溶液401至第一p型金屬功函數層205的方法可採用浸入法。然而可採用任何合適製程使濕蝕刻溶液401接觸第一p型金屬功函數層205的材料，比如水坑製程、噴灑製程、上述之組合、或類似製程。
此外，濕蝕刻製程採用的濕蝕刻溶液401之溫度可介於約25℃至約70℃之間(比如約45℃)。此外，濕蝕刻製程可持續到移除第一p型金屬功函數層205並露出第一介電材料203，比如歷時約30秒至約360秒之間(如約120秒)。然而可採用任何合適的溫度與時間。
在一些實施例中，製程時間可延伸至提供過蝕刻，以確保移除第一p型金屬功函數層205。在這些實施例中，過蝕刻比例可介於約100%至約300%之間。在這些實施例中，p型金屬的蝕刻速率為20 Å/分鐘，而第一p型金屬功函數層205為20 Å，因此過蝕刻100%的製程時間為約2分鐘。
然而在濕蝕刻製程時露出第一介電材料203，濕蝕刻溶液401中的抑制劑會與露出的表面反應。此外，隨著抑制劑的個別分子置於第一介電材料203的表面上並與其反應，將形成保護層403於第一介電材料203的露出表面上。保護層403可為單層厚，且一些實施例中的第一介電材料203之表面將自親水性轉變成疏水性。
在一些實施例中，保護層403可結合來自濕蝕刻溶液401的抑制劑的一部分。舉例來說，一實施例的抑制劑為磷酸，則保護層403將結合磷酸的一部分如磷。當實施例的抑制劑為羧酸，則保護層403將結合羧酸的一部分如碳。類似地，當實施例的抑制劑為胺基酸，則保護層403將結合胺基酸的一部分如氮。當實施例的抑制劑包括羥基，則保護層403將結合羥基的一部分如氧。
藉由形成保護層403，濕蝕刻溶液401中的抑制劑可增加第一p型金屬功函數層205與第一介電材料203之間的選擇性。在一些實施例中，第一p型金屬功函數層205與第一介電材料203之間的選擇性介於約1:1至約1:100之間，比如約1:20。選擇性增加會減少損傷第一介電材料203。若第一介電材料203損傷，會使臨界電壓、金屬閘極漏電流、或裝置的整體可信度產生不想要的偏移。
一旦蝕刻第一p型金屬功函數層205並保護第一介電材料203，可自第一介電材料203移除濕蝕刻溶液401並可移除保護層403。在一實施例中，保護層403的移除方法可採用沖洗溶液如水或溶劑沖洗、清潔溶液如去梨子水或異丙醇清潔溶液、或電漿處理如氬電漿處理。然而可採用任何合適的方法移除保護層403。
如圖5A及5B所示，一旦移除第一p型金屬功函數層205，即可移除底抗反射塗層217，並可沉積第一n型金屬功函數層501、黏著層503、與填充材料505於第一區207、第二區209、第三區211、與第四區213上。在一實施例中，可灰化移除底抗反射塗層217，其增加底抗反射塗層217的溫度，直到熱分解且移除底抗反射塗層217。然而可採用任何合適方法移除底抗反射塗層217。
一旦移除底抗反射塗層217，即可形成第一n型金屬功函數層501。在一實施例中，第一n型金屬功函數層501的材料可為鈦、銀、鋁、鉭鋁、碳化鉭鋁、氮化鈦鋁、碳化鉭、碳氮化鉭、氮化鉭矽、錳、鋯、其他合適的n型功函數材料、或上述之組合。舉例來說，第一n型金屬功函數層501的沉積方法可採用原子層沉積製程、化學氣相沉積製程、或類似製程，其沉積至第六厚度如介於約20 Å至約50 Å之間(比如約30 Å)。然而可採用任何合適的材料與製程形成第一n型金屬功函數層501。
一旦形成第一n型金屬功函數層501，即可形成黏著層503以幫助黏著上方的填充材料505與下方的第一n型金屬功函數層501，並提供形成填充材料505所用的成核層。在一實施例中，黏著層503的材料可為氮化鈦或與第一n型金屬功函數層501類似的材料，且其形成方法可採用類似製程如原子層沉積，以達第七厚度如介於約10Å至約100Å之間(比如約50Å)。然而可採用任何合適材料與製程。
一旦形成黏著層503，即可沉積填充材料505以填充採用黏著層503的開口之其餘部分。在一實施例中，填充材料505可為鎢、鋁、銅、鋁銅、鈦、氮化鈦鋁、碳化鉭、碳氮化鉭、氮化鉭矽、錳、鋯、氮化鈦、鉭、氮化鉭、鈷、鎳、上述之組合、或類似物，且其形成方法可採用沉積製程如電鍍、化學氣相沉積、原子層沉積、物理氣相沉積、上述之組合、或類似製程。此外，填充材料505的沉積厚度可介於約1000 Å至約2000 Å之間，比如約1500 Å。然而可採用任何合適材料。
圖6A及6B顯示沉積填充材料505以填入並超填開口之後，平坦化第一區207、第二區209、第三區211、與第四區213的每一開口中的材料。在一實施例中，平坦化材料與第一間隔物113的方法可採用化學機械研磨製程，但亦可採用任何合適製程如研磨或蝕刻。
在形成並平坦化材料之後，可使材料凹陷並覆蓋蓋層601。在一實施例中，使材料凹陷的方法可採用濕蝕刻製程或乾蝕刻製程，其採用的蝕刻劑對材料具有選擇性。在一實施例中，材料凹陷的距離可介於約5 nm至約150 nm之間，比如約120 nm。然而可採用任何合適的製程與距離。
一旦使材料凹陷，即可沉積蓋層601並平坦化蓋層601與第一間隔物113。在一實施例中，蓋層601的材料可為氮化矽、氮氧化矽、碳氮氧化矽、碳化矽、碳氧化矽、上述之組合、或類似物，且其沉積製程可採用原子層沉積、化學氣相沉積、濺鍍、或類似製程。蓋層601的沉積厚度可介於約5 Å至約200 Å之間。接著可採用平坦化製程如化學機械研磨平坦化蓋層601，使蓋層601與第一間隔物113共平面。
藉由採用濕蝕刻溶液401中的抑制劑，可增加高介電常數的介電材料如第一介電材料203與第一p型金屬功函數層205之間的選擇性，因此可在蝕刻製程時保護高介電常數的介電材料如第一介電材料203。在一些實施例中，濕蝕刻製程造成的損傷可改善超過60%。隨著製造製程越來越小(比如小於或等於5奈米製程節點)，這些改善有助於達到更穩健的製程，亦有助於避免任何不想要的臨界電壓偏移、金屬閘極漏電流、與可信度問題。
在一實施例中，半導體裝置的製造方法包括：形成p型金屬功函數層於介電層上；以及施加濕蝕刻溶液至p型金屬功函數層，以移除p型金屬功函數層的一部分，且濕蝕刻溶液包括：金屬蝕刻劑；抑制劑，用於介電層；以及溶劑。在一實施例中，介電層為氧化鉿。在一實施例中，抑制劑為磷酸。在一實施例中，抑制劑為羧酸。在一實施例中，抑制劑為胺基酸。在一實施例中，抑制劑包括羥基。在一實施例中，上述方法更包括在露出介電層之後，形成保護層於介電層的露出表面上。
在另一實施例中，半導體裝置的製造方法包括：沉積第一p型功函數層於高介電常數的介電層上；以及採用濕蝕刻溶液蝕刻第一p型功函數層，以露出高介電常數的介電層之第一部分，其中高介電常數的介電層與濕蝕刻溶液反應以形成保護層於高介電常數的介電層上。在一實施例中，保護層包括磷、氮、或碳。在一實施例中，濕蝕刻溶液包括：溶劑；第一金屬蝕刻劑；氧化劑；以及抑制劑。在一實施例中，抑制劑包括磷酸、羧酸、或胺基酸的一或多者。在一實施例中，保護層形成疏水表面。在一實施例中，高介電常數的介電層包括氧化鉿，而第一p型功函數層包括氮化鈦。在一實施例中，濕蝕刻溶液對氮化鈦與對高介電常數的介電層之間的選擇性為至少100:1。
在又一實施例中，蝕刻溶液包括：溶劑；第一金屬蝕刻劑；氧化劑；以及抑制劑，其包含磷酸、羧酸、或胺基酸的一或多者。在一實施例中，抑制劑包括二(2-乙基己基)磷酸。在一實施例中，抑制劑包括羧酸。在一實施例中，抑制劑包括甘胺酸。在一實施例中，抑制劑的濃度小於約5體積%。在一實施例中，蝕刻溶液對氮化鈦與對氧化鉿之間的選擇性為至少100:1。
上述實施例之特徵有利於本技術領域中具有通常知識者理解本發明。本技術領域中具有通常知識者應理解可採用本發明作基礎，設計並變化其他製程與結構以完成上述實施例之相同目的及/或相同優點。本技術領域中具有通常知識者亦應理解，這些等效置換並未脫離本發明精神與範疇，並可在未脫離本發明之精神與範疇的前提下進行改變、替換、或更動。
100:半導體裝置 101:基板 103:第一溝槽 105:第一隔離區 107:鰭狀物 109:虛置閘極介電層 111:虛置閘極 113:第一間隔物 115:堆疊 201:層間介電層 203:第一介電材料 205:第一p型金屬功函數層 207:第一區 209:第二區 211:第三區 213:第四區 215:第一光阻 217:底抗反射塗層 219:中間遮罩層 221:頂光敏層 401:濕蝕刻溶液 403:保護層 501:第一n型金屬功函數層 503:黏著層 505:填充材料 601:蓋層
圖1係一些實施例中，形成半導體鰭狀物的透視圖。 圖2A及2B係一些實施例中，形成高介電常數的介電層與第一p型金屬功函數層的示意圖。 圖3A及3B係一些實施例中，圖案化抵抗反射層的示意圖。 圖4A及4B係一些實施例中，蝕刻製程的示意圖。 圖5A及5B係一些實施例中，形成閘極結構的示意圖。 圖6A及6B係一些實施例中，形成蓋層的示意圖。
Figure 110101268-A0101-11-0002-1
105:第一隔離區
203:第一介電材料
205:第一p型金屬功函數層
207:第一區
209:第二區
211:第三區
213:第四區
401:濕蝕刻溶液
403:保護層

Claims (20)

  1. 一種半導體裝置的製造方法，包括： 形成一p型金屬功函數層於一介電層上；以及 施加一濕蝕刻溶液至該p型金屬功函數層，以移除該p型金屬功函數層的一部分，且該濕蝕刻溶液包括： 一金屬蝕刻劑； 一抑制劑，用於該介電層；以及 一溶劑。
  2. 如請求項1之半導體裝置的製造方法，其中該介電層為氧化鉿。
  3. 如請求項1之半導體裝置的製造方法，其中該抑制劑為磷酸。
  4. 如請求項1之半導體裝置的製造方法，其中該抑制劑為羧酸。
  5. 如請求項1之半導體裝置的製造方法，其中該抑制劑為胺基酸。
  6. 如請求項1之半導體裝置的製造方法，其中該抑制劑包括羥基。
  7. 如請求項1之半導體裝置的製造方法，更包括在露出該介電層之後，形成一保護層於該介電層的露出表面上。
  8. 一種半導體裝置的製造方法，包括： 沉積一第一p型功函數層於一高介電常數的介電層上；以及 採用一濕蝕刻溶液蝕刻该第一p型功函數層，以露出該高介電常數的介電層之第一部分，其中該高介電常數的介電層與該濕蝕刻溶液反應以形成一保護層於該高介電常數的介電層上。
  9. 如請求項8之半導體裝置的製造方法，其中該保護層包括磷、氮、或碳。
  10. 如請求項8之半導體裝置的製造方法，其中該濕蝕刻溶液包括： 一溶劑； 一第一金屬蝕刻劑； 一氧化劑；以及 一抑制劑。
  11. 如請求項10之半導體裝置的製造方法，其中該抑制劑包括磷酸、羧酸、或胺基酸的一或多者。
  12. 如請求項8之半導體裝置的製造方法，其中該保護層形成一疏水表面。
  13. 如請求項8之半導體裝置的製造方法，其中該高介電常數的介電層包括氧化鉿，而該第一p型功函數層包括氮化鈦。
  14. 如請求項13之半導體裝置的製造方法，其中該濕蝕刻溶液對氮化鈦與對該高介電常數的介電層之間的選擇性為至少100:1。
  15. 一種蝕刻溶液，包括： 一溶劑； 一第一金屬蝕刻劑； 一氧化劑；以及 一抑制劑，其包含磷酸、羧酸、或胺基酸的一或多者。
  16. 如請求項15之蝕刻溶液，其中該抑制劑包括二(2-乙基己基)磷酸。
  17. 如請求項15之蝕刻溶液，其中該抑制劑包括羧酸。
  18. 如請求項15之蝕刻溶液，其中該抑制劑包括甘胺酸。
  19. 如請求項15之蝕刻溶液，其中該抑制劑的濃度小於約5體積%。
  20. 如請求項15之蝕刻溶液，其中該蝕刻溶液對氮化鈦與對氧化鉿之間的選擇性為至少100:1。
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