TWI780358B - 製造半導體裝置的方法以及光阻 - Google Patents

製造半導體裝置的方法以及光阻 Download PDF

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TWI780358B
TWI780358B TW108133570A TW108133570A TWI780358B TW I780358 B TWI780358 B TW I780358B TW 108133570 A TW108133570 A TW 108133570A TW 108133570 A TW108133570 A TW 108133570A TW I780358 B TWI780358 B TW I780358B
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Taiwan
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photoresist
semiconductor device
layer
ether
encapsulation
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TW108133570A
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TW202042283A (zh
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郭宏瑞
李明潭
李興傑
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台灣積體電路製造股份有限公司
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    • H01L22/00Testing or measuring during manufacture or treatment; Reliability measurements, i.e. testing of parts without further processing to modify the parts as such; Structural arrangements therefor
    • H01L22/20Sequence of activities consisting of a plurality of measurements, corrections, marking or sorting steps
    • H01L22/24Optical enhancement of defects or not directly visible states, e.g. selective electrolytic deposition, bubbles in liquids, light emission, colour change
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Abstract

使用具有檢測添加劑的光阻,以在顯影後檢查製程期間幫助增大圖像的對比度。所述檢測添加劑在顯影後檢查製程期間發螢光並增加在顯影後檢查製程期間反射的能量,從而在顯影後檢查製程期間增大對比度並幫助識別以其他方式無法檢測到的缺陷。

Description

製造半導體裝置的方法以及光阻
本發明實施例有關於一種製造半導體裝置的方法以及光阻。
由於各種電子組件(例如,電晶體、二極體、電阻器、電容器等)的集成密度的持續提高,半導體行業已經歷快速增長。在很大程度上,集成密度的這一提高是源自最小特徵尺寸(minimum feature size)的連番減小(例如,朝向20nm節點以下(sub-20nm node)縮減半導體製程節點),而使更多的組件能夠整合於所給定的區域中。隨著近來對小型化、提高速度、增加頻寬、降低功率損耗及縮短延遲的需求的增加,對更小且更具創造性的半導體晶粒封裝技術的需要也隨著增加。
隨著半導體技術的進一步推進,經堆疊及接合的半導體裝置已出現作為一種有效的替代選擇,以進一步減小半導體裝置的實體大小。在經堆疊的半導體裝置中,例如邏輯、記憶體、處理器電路等主動電路至少部分地在單獨的基底上製作後,然後再 實體接合及電接合在一起以形成功能裝置(functional device)。此種接合製程利用精密的技術,且期望有所改進。
根據一些實施例,製造半導體裝置的方法包括:在半導體基底之上施加光阻,所述光阻包含檢測添加劑;對所述光阻進行曝光及顯影;以及在對所述光阻進行顯影之後檢查所述光阻,其中所述檢測添加劑在所述檢查所述光阻期間發螢光。
根據一些實施例,製造半導體裝置的方法包括:將光阻聚合物樹脂放置在光阻溶劑中;將光酸產生劑放置在所述光阻溶劑中;將薑黃色素放置在所述光阻溶劑中;以及混合所述光阻聚合物樹脂、所述光酸產生劑、所述薑黃色素以及所述光阻溶劑以形成光阻。
根據一些實施例,光阻包括:光阻聚合物樹脂;光活性化合物;以及檢測添加劑。所述檢測添加劑在所述光阻內的濃度在約0.01重量%與約0.03重量%之間。
101:載體基底
103:黏合劑層
105:聚合物層
107:第一晶種層
109:光阻
111:通孔
201:第一半導體裝置
203:第一基底
205:第一金屬化層
207:第一接觸墊
209:第一外部連接件
211:第一鈍化層
213:晶粒貼合膜(DAF)
301:第二半導體裝置
303:第二基底
305:第二金屬化層
307:第二接觸墊
309:第二外部連接件
311:第二鈍化層
401:包封體
501:第一重布線層
503:第三鈍化層
504:第一開口
505:第二重布線層
506:第二開口
507:第四鈍化層
509:第三重布線層
511:第五鈍化層
513:第六鈍化層
515:第二晶種層
517:光阻
518:晶種層
600:成像裝置
601:曝光區
603:未曝光區
605:支撐板
607:能量源
609:圖案化遮罩
611:能量
615:圖案化能量
617:光學器件
701:顯影劑
801:檢查室
803:同調光源
805:照相機
807:光學平臺
809:處理計算機
811:同調光束
901:第三外部連接部
1101:第四外部連接部
1201:環結構
1203:紫外膠帶
1300:第一封裝
1301:背面球墊
1303:背面保護層
1305:第三基底
1307:第三半導體裝置
1309:第四半導體裝置
1311:第三接觸墊
1313:第二包封體
1315:第五外部連接部
1317:基底穿孔
1319:打線結合
1321:第二封裝
1400:第一集成扇出式堆疊封裝結構
圖1根據一些實施例繪示穿孔的形成。
圖2示出根據一些實施例的半導體裝置。
圖3根據一些實施例繪示放置半導體裝置於穿孔之間。
圖4根據一些實施例繪示包封的步驟。
圖5根據一些實施例繪示光阻的設置。
圖6根據一些實施例繪示對光阻進行成像。
圖7示出根據一些實施例的顯影製程。
圖8示出根據一些實施例的顯影後檢查製程(after development inspection process)。
圖9根據一些實施例示出重布線層的形成。
圖10示出根據一些實施例的剝離製程。
圖11根據一些實施例繪示第一封裝的放置。
圖12示出根據一些實施例的單體化(singulation)製程。
以下公開內容提供用於實作本發明的不同特徵的許多不同的實施例或實例。以下闡述組件及排列的具體實例以簡化本公開。當然,這些僅為實例而非旨在進行限制。舉例來說,在以下說明中,在第二特徵之上或第二特徵上形成第一特徵可包括其中第一特徵與第二特徵被形成為直接接觸的實施例,且也可包括其中第一特徵與第二特徵之間可形成附加特徵從而使得第一特徵與第二特徵可不直接接觸的實施例。另外,本公開在各種實例中可重複使用參考編號和/或字母。此種重複使用是為了簡明及清晰起見,且自身並不表示所討論的各個實施例和/或配置之間的關係。
此外,為易於說明,本文中可能使用例如“在...下方 (beneath)”、“在...下面(below)”、“下部的(lower)”、“上方(above)”、“上部的(upper)”等空間相對性用語來闡述圖中所示的一個元件或特徵與另一(其他)元件或特徵的關係。所述空間相對性用語旨在除圖中所繪示的取向外還囊括裝置在使用或操作中的不同取向。設備可具有其他取向(旋轉90度或其他取向),且本文中所用的空間相對性描述語可同樣相應地進行解釋。
現在將闡述實施例,在所述實施例中在光阻內使用檢測添加劑以便增大後續顯影後檢查製程的對比度。本文中所述的實施例是對於小於20nm(例如,7nm)的技術節點闡述的。然而,所述實施例並不僅限於這些製程節點,且可用於各種應用中。
現在參照圖1,圖1示出了載體基底101,在載體基底101上方具有黏合劑層103、聚合物層105及第一晶種層107。載體基底101包含例如矽系材料(例如玻璃或氧化矽)或其他材料(例如氧化鋁)或這些材料中的任意者的組合等。載體基底101為平面的,以接納例如第一半導體裝置201及第二半導體裝置301(在圖1中未示出,但在以下參考圖2至圖3來說明及論述)等半導體裝置的貼合。
黏合劑層103放置在載體基底101上,以輔助上覆結構(例如,聚合物層105)的黏合。在實施例中,黏合劑層103可包含紫外膠(ultra-violet glue),所述紫外膠在暴露至紫外光時會喪失其黏合性質。然而,也可使用其他類型的黏合劑,例如壓敏(pressure sensitive)黏合劑、可輻射固化(radiation curable)黏 合劑、環氧樹脂或這些的組合等。可將黏合劑層103以在壓力下易於變形的半液體形式或凝膠形式放置在載體基底101上。
聚合物層105放置在黏合劑層103上方,且一旦第一半導體裝置201及第二半導體裝置301已被貼合之後,聚合物層105便用於提供對例如第一半導體裝置201及第二半導體裝置301的保護。在實施例中,聚合物層105可為聚苯並惡唑(polybenzoxazole,PBO),但也可利用例如聚醯亞胺或聚醯亞胺衍生物、阻焊劑(Solder Resistance,SR)或味之素構成膜(Ajinomoto build-up film,ABF)等任意合適的材料。可使用例如旋轉塗布製程將聚合物層105形成至約2μm與約15μm之間(例如約5μm)的厚度,但可使用任何合適的方法及厚度。
第一晶種層107形成在聚合物層105上方。在實施例中,第一晶種層107為導電材料的薄層,其有助於在後續處理步驟期間形成更厚的層。第一晶種層107可包含約1,000Å厚的鈦層,以及約5,000Å厚的銅層。可依據所期望的材料而使用例如濺射製程、蒸鍍製程或等離子體增強型化學氣相沉積(PECVD)製程等製程來形成第一晶種層107。第一晶種層107可被形成為具有約0.3μm與約1μm之間(例如約0.5μm)的厚度。
圖1還示出將光阻109放置在第一晶種層107上方及將光阻109圖案化。在實施例中,可使用例如旋轉塗布技術將光阻109放置在第一晶種層107上而具有約50μm與約250μm之間(例如約120μm)的高度。一旦就位,接著便可通過以下方式將光阻 109圖案化:將光阻109暴露於圖案化能量源(例如,圖案化光源)以引發化學反應,從而引發光阻109的被暴露於圖案化光源的那些部分的物理變化。然後對被暴露光阻109施加顯影劑,以利用所述物理變化並依據所期望的圖案而選擇性地移除光阻109的被暴露部分或光阻109的未暴露部分。
在實施例中,形成到光阻109中的圖案是也被稱為穿孔、基底穿孔、絕緣體穿孔或InFO穿孔的通孔111的圖案。通孔111以此種放置方式被形成為位於例如第一半導體裝置201及第二半導體裝置301等隨後貼合的裝置的不同側上。然而,可利用通孔111的圖案的任何合適的布置,例如被定位成使得第一半導體裝置201及第二半導體裝置301被放置在通孔111的相對側上。
在實施例中,通孔111形成於光阻109內。在實施例中,通孔111包含一種或多種導電材料(例如銅、鎢或其他導電金屬等),且可例如通過電鍍、無電鍍覆等方法來形成。在實施例中,使用電鍍製程,在所述電鍍製程中,將第一晶種層107及光阻109浸沒或浸漬在電鍍溶液中。第一晶種層107的表面電連接到外部直流(DC)電源的負極側(negative side),以使得第一晶種層107在電鍍製程中用作陰極。實心導電陽極(例如銅陽極)也浸漬在所述溶液中並將所述實心導電陽極貼合到電源的正極側。來自陽極的原子溶解在溶液中,陰極(例如,第一晶種層107)從所述溶液獲取所溶解的原子,從而鍍覆第一晶種層107的在光阻109的開口中暴露出來的導電區域。
一旦已使用光阻109及第一晶種層107形成通孔111,便可使用合適的移除製程(在圖1中未示出,但見於以下圖3中)來移除光阻109。在實施例中,可使用等離子體灰化製程來移除光阻109,從而可提高光阻109的溫度直至光阻109經歷熱分解且可被移除。然而,可利用任何其他合適的製程,例如濕式剝離。移除光阻109之後,可暴露出第一晶種層107的下伏部分。
一旦被暴露之後,便可執行第一晶種層107的被暴露部分的移除(在圖1中未示出,但見於以下圖3中)。在實施例中,可通過例如濕式蝕刻製程或乾式蝕刻製程來移除第一晶種層107的被暴露部分(例如,未被通孔111覆蓋的那些部分)。舉例來說,在乾式蝕刻製程中,可使用通孔111作為遮罩將反應劑朝第一晶種層107引導。在另一實施例中,可噴射蝕刻劑或以其他方式使蝕刻劑與第一晶種層107接觸,以移除第一晶種層107的被暴露部分。在已蝕刻掉第一晶種層107的被暴露部分之後,在通孔111之間暴露出聚合物層105的一部分。
圖2示出將貼合到通孔111之間的聚合物層105(在圖2中未示出,但在以下參照圖3示出及闡述)的第一半導體裝置201。在實施例中,第一半導體裝置201包括第一基底203、第一主動裝置(未各別示出)、第一金屬化層205、第一接觸墊207、第一鈍化層211及第一外部連接件209。第一基底203可包含經摻雜或未經摻雜的塊體矽、或絕緣體上覆矽(silicon-on-insulator,SOI)基底的主動層。一般來說,絕緣體上覆矽基底包含一層半導 體材料,例如矽、鍺、矽鍺、絕緣體上覆矽、絕緣體上覆矽鍺(silicon germanium on insulator,SGOI)或其組合。可使用的其他基底包括多層式基底、梯度基底(gradient substrate)、或混合取向基底(hybrid orientation substrate)。
第一主動裝置包括可用來產生第一半導體裝置201的設計的所期望結構需求及功能需求的各種主動裝置及被動裝置(例如電容器、電阻器、電感器等)。可使用任何合適的方法在第一基底203內或第一基底203上形成第一主動裝置。
第一金屬化層205形成在第一基底203及第一主動裝置上方,且被設計成連接所述各種主動裝置以形成功能性電路系統。在實施例中,第一金屬化層205是由交替的介電材料層與導電材料層形成,且可通過任何合適的製程(例如沉積、鑲嵌、雙鑲嵌等)形成。在實施例中,可存在通過至少一個層間介電層(interlayer dielectric layer,ILD)而與第一基底203分離的四個金屬化層,但第一金屬化層205的精確數量相依於第一半導體裝置201的設計。
第一接觸墊207可形成於第一金屬化層205上方且與第一金屬化層205電接觸。第一接觸墊207可包含鋁,但可使用其他材料,例如銅。第一接觸墊207可使用沉積製程(例如濺射)來形成,以形成材料層(圖中未示出),且然後可通過合適的製程(例如光微影及蝕刻)來移除所述材料層的一些部分,以形成第一接觸墊207。然而,可利用任何其他合適的製程來形成第一接觸 墊207。第一接觸墊207可被形成為具有約0.5μm與約4μm之間(例如約1.45μm)的厚度。
第一鈍化層211可形成於第一基底203上、第一金屬化層205及第一接觸墊207上方。第一鈍化層211可由例如氧化矽、氮化矽、低k介電質(例如,摻雜碳的氧化物)、極低k介電質(例如,摻雜多孔碳的二氧化矽)、其組合等一或多種合適的介電材料製成。第一鈍化層211可通過例如化學氣相沉積(chemical vapor deposition,CVD)等製程形成,但可使用任何合適的製程,且第一鈍化層211可具有約0.5μm與約5μm之間(例如,約9.25KÅ)的厚度。
第一外部連接件209可被形成為提供導電區以實現第一接觸墊207與例如第一重布線層501(在圖2中未示出,但在以下參照圖5示出及闡述)之間的接觸。在實施例中,第一外部連接件209可為導電柱,且可通過首先將光阻(圖中未示出)形成在第一鈍化層211上方並形成至約5μm與約20μm之間(例如約10μm)的厚度來形成。可將光阻圖案化以暴露出第一鈍化層的某些部分(導電柱將延伸穿過所述部分)。一旦圖案化之後,便可接著使用所述光阻作為遮罩來移除第一鈍化層211的所期望部分,從而暴露出下伏第一接觸墊207的將與第一外部連接件209接觸的那些部分。
第一外部連接件209可形成於第一鈍化層211及光阻兩者的開口內。第一外部連接件209可由導電材料(例如銅)形成, 但也可使用其他導電材料,例如鎳、金、或金屬合金或這些的組合等。另外,第一外部連接件209可使用例如電鍍等製程來形成,通過所述第一外部連接件209電流流經第一接觸墊207的期望形成第一外部連接件209的導電部分,且將第一接觸墊207浸漬在溶液中。所述溶液及電流將例如銅沉積在開口內以填充及/或過度填充光阻的開口及第一鈍化層211的開口,從而形成第一外部連接件209。然後可使用例如灰化製程、化學機械拋光(chemical mechanical polish,CMP)製程或這些的組合等來移除第一鈍化層211的開口外部的過量導電材料及光阻。
然而,如所屬領域中的普通技術人員將知,用以形成第一外部連接件209的上述製程僅為一個說明,且並不意在將實施例限制於此確切製程。相反,上述製程旨在僅為說明性的,可利用用於形成第一外部連接件209的任何合適的製程。所有合適的製程均旨在包含於本發明實施例的範圍內。
在第一基底203的與第一金屬化層205相對的側上,可形成晶粒貼合膜(die attach film,DAF)213以輔助將第一半導體裝置201貼合到聚合物層105。在實施例中,晶粒貼合膜213為環氧樹脂、酚樹脂、丙烯酸橡膠、氧化矽填料或其組合,且使用層合技術來施加。然而,可利用任何其他合適的材料及形成方法。
圖3示出將第一半導體裝置201與第二半導體裝置301放置在聚合物層105上。在實施例中,第二半導體裝置301可包括第二基底303、第二主動裝置(未各別示出)、第二金屬化層305、 第二接觸墊307、第二鈍化層311以及第二外部連接件309。在實施例中,第二基底303、第二主動裝置、第二金屬化層305、第二接觸墊307、第二鈍化層311及第二外部連接件309可類似於第一基底203、第一主動裝置、第一金屬化層205、第一接觸墊207、第一鈍化層211、及第一外部連接件209,但他們也可彼此相異。
在實施例中,可使用例如拾取及放置製程(pick and place process)將第一半導體裝置201及第二半導體裝置301放置到聚合物層105上。然而,也可利用放置第一半導體裝置201及第二半導體裝置301的任何其他方法。
圖4示出通孔111、第一半導體裝置201及第二半導體裝置301的包封。可在模制裝置(在圖4中未各別示出)中執行包封,所述模制裝置可包括頂部模制部分及可與所述頂部模制部分分離的底部模制部分。當頂部模制部分降低至相鄰於底部模制部分時,可為載體基底101、通孔111、第一半導體裝置201、及第二半導體裝置301形成模制空腔。
在包封製程期間,可相鄰於底部模制部分放置頂部模制部分,從而將載體基底101、通孔111、第一半導體裝置201及第二半導體裝置301封閉在模制空腔內。一旦被封閉之後,頂部模制部分及底部模制部分便可形成氣密密封以控制氣體流入模制空腔及從模制空腔流出。一旦密封之後,便可將包封體401放置在模制空腔內。包封體401可為模制化合物樹脂,例如聚醯亞胺、聚苯硫醚(Polyphenylene sulfide,PPS)、聚醚醚酮 (polyetheretherketone,PEEK)、聚醚碸(Polyethersulfone,PES)、耐熱晶體樹脂或這些的組合等。可在頂部模制部分與底部模制部分對準之前將包封體401放置在模制空腔內,抑或可通過注射口將包封體401注射到模制空腔內。
一旦包封體401已被放置到模制空腔內而使得包封體401包封載體基底101、通孔111、第一半導體裝置201及第二半導體裝置301之後,便可將包封體401固化以硬化包封體401來實現最佳保護。確切固化製程至少部分地相依於為包封體401選擇的特定材料。在選擇模制化合物作為包封體401的實施例中,可通過例如將包封體401加熱到約100℃與約130℃之間(例如約125℃)達約60秒到約3000秒(例如約600秒)的時間等製程而發生固化。另外,在包封體401內可包含引發劑及/或催化劑以更好地控制固化製程。
然而,如所屬領域中的普通技術人員將知,上述固化製程僅為示例性製程,而並不旨在限制當前實施例。可使用其他固化製程,例如輻照或甚至使包封體401在周圍環境溫度下硬化。可使用任何合適的固化製程,且所有此種製程均旨在包含於本文所述實施例的範圍內。
圖4還示出使包封體401薄化以暴露出通孔111、第一半導體裝置201及第二半導體裝置301以供進一步處理。可例如使用機械研磨製程或化學機械拋光(CMP)製程來執行變薄,從而利用化學蝕刻劑及磨料來使包封體401、第一半導體裝置201及第 二半導體裝置301反應並研磨掉包封體401、第一半導體裝置201及第二半導體裝置301,直到通孔111、第一外部連接件209(位於第一半導體裝置201上)及第二外部連接件309(位於第二半導體裝置301上)已被暴露出。如此一來,第一半導體裝置201、第二半導體裝置301以及通孔111可具有也與包封體401共面的平面表面。
然而,儘管上述化學機械拋光製程被呈現為一個說明性實施例,但其並不旨在限制所述實施例。可使用任何其他合適的移除製程來使包封體401、第一半導體裝置201及第二半導體裝置301薄化並暴露出通孔111。舉例來說,可利用一系列化學蝕刻劑。可利用此製程及任何其他合適的製程來使包封體401、第一半導體裝置201及第二半導體裝置301薄化,且所有此種製程均旨在包含於實施例的範圍內。
可選地,在已使包封體401薄化之後,通孔111、第一外部連接件209及第二外部連接件309可凹陷在包封體401內。在實施例中,可使用例如蝕刻製程來使通孔111、第一外部連接件209及第二外部連接件309凹陷,所述蝕刻製程使用對通孔111、第一外部連接件209及第二外部連接件309的材料(例如銅)具有選擇性的蝕刻劑。通孔111、第一外部連接件209及第二外部連接件309可凹陷至約20μm與約300μm之間(例如約180μm)的深度。
圖5示出用於形成第一重布線層(redistribution layer, RDL)501的起始製程的剖視圖。在實施例中,可通過首先經由合適的形成製程(例如化學氣相沉積或濺射)形成鈦銅合金的晶種層518來形成第一重布線層501。一旦晶種層518已被沉積,便可將光阻517置於晶種層518上以準備形成第一重布線層501。在實施例中,光阻517可以是化學增強型光阻,並且包括光阻溶劑中的光阻聚合物樹脂以及一種或多種光活性化合物(photoactive compound,PACs)。在實施例中,光阻聚合物樹脂可包括烴結構(例如,脂環烴結構),所述烴結構含有一個或多個基團,所述基團在與由光活性化合物生成的酸、鹼或自由基混合時將分解(例如,酸不穩定基團(acid labile group))或以其他方式發生反應(如下文參照圖6進一步描述)。在實施例中,烴結構包括形成光阻聚合物樹脂的骨架的重複單元。此重複單元可包括丙烯酸酯類、甲基丙烯酸酯類、巴豆酯類(crotonic esters)、乙烯基酯類、馬來酸二酯類(maleic diesters)、富馬酸二酯類(fumaric diesters)、衣康酸二酯類(itaconic diesters)、(甲基)丙烯腈((meth)acrylonitrile)、(甲基)丙烯醯胺類((meth)acrylamides)、苯乙烯類(styrenes)、乙烯基醚類(vinyl ethers)或這些的組合等。
可用於烴結構的重複單元的具體結構包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸叔丁酯(tert-butyl acrylate)、丙烯酸正己酯(n-hexyl acrylate)、丙烯酸2-乙基己酯(2-ethylhexyl acrylate)、丙烯酸乙醯氧基乙酯(acetoxyethyl acrylate)、丙烯酸苯酯(phenyl acrylate)、丙烯酸2-羥乙酯(2-hydroxyethyl acrylate)、丙烯酸2-甲氧乙酯(2-methoxyethyl acrylate)、丙烯酸2-乙氧乙酯(2-ethoxyethyl acrylate)、丙烯酸2-(2-甲氧基乙氧基)乙酯(2-(2-methoxyethoxy)ethyl acrylate)、丙烯酸環己酯(cyclohexyl acrylate)、丙烯酸苄酯(benzyl acrylate)、(甲基)丙烯酸2-烷基-2-金剛烷酯(2-alkyl-2-adamantyl(meth)acrylate)或(甲基)丙烯酸二烷基(1-金剛烷基)甲酯(dialkyl(1-adamantyl)methyl(meth)acrylate)、甲基丙烯酸甲酯(methyl methacrylate)、甲基丙烯酸乙酯(ethyl methacrylate)、甲基丙烯酸正丙酯(n-propyl methacrylate)、甲基丙烯酸異丙酯(isopropyl methacrylate)、甲基丙烯酸正丁酯(n-butyl methacrylate)、甲基丙烯酸異丁酯(isobutyl methacrylate)、甲基丙烯酸叔丁酯(tert-butyl methacrylate)、甲基丙烯酸正己酯(n-hexyl methacrylate)、甲基丙烯酸2-乙基己酯(2-ethylhexyl methacrylate)、甲基丙烯酸乙醯氧基乙酯(acetoxyethyl methacrylate)、甲基丙烯酸苯酯(phenyl methacrylate)、甲基丙烯酸2-羥乙酯(2-hydroxyethyl methacrylate)、甲基丙烯酸2-甲氧乙酯(2-methoxyethyl methacrylate)、甲基丙烯酸2-乙氧乙酯(2-ethoxyethyl methacrylate)、甲基丙烯酸2-(2-甲氧基乙氧基)乙基(2-(2-methoxyethoxy)ethyl methacrylate)、甲基丙烯酸環己酯(cyclohexyl methacrylate)、甲基丙烯酸苄酯(benzyl methacrylate)、甲基丙烯酸3-氯-2-羥丙酯 (3-chloro-2-hydroxypropyl methacrylate)、甲基丙烯酸3-乙醯氧基-2-羥丙酯(3-acetoxy-2-hydroxypropyl methacrylate)、甲基丙烯酸3-氯乙醯氧基-2-羥丙酯(3-chloroacetoxy-2-hydroxypropyl methacrylate)、巴豆酸丁酯(butyl crotonate)、巴豆酸己酯(hexyl crotonate)等。乙烯基酯類的實例包括乙酸乙烯酯(vinyl acetate)、丙酸乙烯酯(vinyl propionate)、丁酸乙烯酯(vinyl butylate)、甲氧基乙酸乙烯酯(vinyl methoxyacetate)、苯甲酸乙烯酯(vinyl benzoate)、馬來酸二甲酯(dimethyl maleate)、馬來酸二乙酯(diethyl maleate)、馬來酸二丁酯(dibutyl maleate)、富馬酸二甲酯(dimethyl fumarate)、富馬酸二乙酯(diethyl fumarate)、富馬酸二丁酯(dibutyl fumarate)、衣康酸二甲酯(dimethyl itaconate)、衣康酸二乙酯(diethyl itaconate)、衣康酸二丁酯(dibutyl itaconate)、丙烯醯胺(acrylamide)、甲基丙烯醯胺(methyl acrylamide)、乙基丙烯醯胺(ethyl acrylamide)、丙基丙烯醯胺(propyl acrylamide)、正丁基丙烯醯胺(n-butyl acrylamide)、叔丁基丙烯醯胺(tert-butyl acrylamide)、環己基丙烯醯胺(cyclohexyl acrylamide)、2-甲氧乙基丙烯醯胺(2-methoxyethyl acrylamide)、二甲基丙烯醯胺(dimethyl acrylamide)、二乙基丙烯醯胺(diethyl acrylamide)、苯基丙烯醯胺(phenyl acrylamide)、苄基丙烯醯胺(benzyl acrylamide)、甲基丙烯醯胺(methacrylamide)、甲基甲基丙烯醯胺(methyl methacrylamide)、乙基甲基丙烯醯胺(ethyl methacrylamide)、丙基甲基丙烯醯胺(propyl methacrylamide)、 正丁基甲基丙烯醯胺(n-butyl methacrylamide)、叔丁基甲基丙烯醯胺(tert-butyl methacrylamide)、環己基甲基丙烯醯胺(cyclohexyl methacrylamide)、2-甲氧基乙基甲基丙烯醯胺(2-methoxyethyl methacrylamide)、二甲基甲基丙烯醯胺(dimethyl methacrylamide)、二乙基甲基丙烯醯胺(diethyl methacrylamide)、苯基甲基丙烯醯胺(phenyl methacrylamide)、苄基甲基丙烯醯胺(benzyl methacrylamide)、甲基乙烯基醚(methyl vinyl ether)、丁基乙烯基醚(butyl vinyl ether)、己基乙烯基醚(hexyl vinyl ether)、甲氧基乙基乙烯基醚(methoxyethyl vinyl ether)、二甲基氨基乙基乙烯基醚(dimethylaminoethyl vinyl ether)等。苯乙烯類的實例包括苯乙烯、甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、甲氧基苯乙烯、丁氧基苯乙烯、乙醯氧基苯乙烯(acetoxy styrene)、氯苯乙烯、二氯苯乙烯、溴苯乙烯、苯甲酸乙烯基甲酯(vinyl methyl benzoate)、α-甲基苯乙烯(α-methyl styrene)、馬來醯亞胺(maleimide)、乙烯基吡啶(vinylpyridine)、乙烯基吡咯烷酮(vinylpyrrolidone)、乙烯基哢唑(vinylcarbazole)或這些的組合等。
在實施例中,所述烴結構的重複單元也可具有取代入其中的單環或多環烴結構,或者所述單環或多環烴結構可以是所述重複單元,以便形成脂環烴結構。可使用的單環結構的具體實例包括雙環烷、三環烷、四環烷、環戊烷、環己烷等。可以使用的 多環結構的具體實例包括金剛烷(adamantine)、降冰片烷(norbornane)、異莰烷(isobornane)、三環癸烷、四環十二烷(tetracyclododecane)等。
將分解、或者被稱為離去基團(leaving group)、或者在其中光活性化合物是光酸產生劑(photoacid generator)的實施例中被稱為酸不穩定基團的基團貼合到烴結構上,從而使其在暴露期間與光活性化合物生成的酸/鹼/自由基發生反應。在實施例中,將分解的基團可以是羧酸基團、氟化醇基團(fluorinated alcohol group)、酚醇基團(phenolic alcohol group)、磺酸基團(sulfonic group)、磺醯胺基團(sulfonamide group)、磺醯亞氨基團(sulfonylimido group)、(烷基磺醯基)(烷基羰基)亞甲基((alkylsulfonyl)(alkylcarbonyl)methylene group)、(烷基磺醯基)(烷基-羰基)亞氨基((alkylsulfonyl)(alkyl-carbonyl)imido group)、雙(烷基羰基)亞甲基(bis(alkylcarbonyl)methylene group)、雙(烷基羰基)亞氨基(bis(alkylcarbonyl)imido group)、雙(烷基磺醯基)亞甲基(bis(alkylsulfonyl)methylene group)、雙(烷基磺醯基)亞氨基(bis(alkylsulfonyl)imido group)、三(烷基羰基)亞甲基(tris(alkylcarbonyl)methylene group)、三(烷基磺醯基)亞甲基(tris(alkylsulfonyl)methylene group)或這些的組合等。可用於氟化醇基團的具體基團包括氟化羥基烷基(fluorinated hydroxyalkyl group),例如六氟異丙醇基團(hexafluoroisopropanol group)。可用於羧酸基團的具體基團包括丙烯酸基團、甲基丙烯 酸基團等。
在實施例中,光阻聚合物樹脂還可包括貼合到烴結構的其它基團,所述基團有助於改善可聚合樹脂的各種性質。舉例來說,將內酯基團(lactone group)包含在烴結構中有助於減少在光阻517已被顯影後的線邊緣粗糙度(line edge roughness)的量,從而有助於減少在顯影期間發生的缺陷的數量。在實施例中,內酯基團可包括五元環到七元環,但可將任何合適的內酯結構用於內酯基團。
光阻聚合物樹脂還可包括可有助於增大光阻517與下伏結構的黏合性的基團。在實施例中,可使用極性基團來幫助提高黏合性,並且在本實施例中可使用的極性基團包括羥基、氰基(cyano group)等,但可使用任何合適的極性基團。
可選地,光阻聚合物樹脂還可包括一個或多個脂環烴結構(alicyclic hydrocarbon structure),所述脂環烴結構也不含有將分解的基團。在實施例中,不含有將分解的基團的烴結構可包括以下結構,例如1-金剛烷基(甲基)丙烯酸酯(1-adamantyl(meth)acrylate)、三環癸基(甲基)丙烯酸酯(tricyclodecahyl(meth)acrylate)、環己基(甲基丙烯酸酯)(cyclohexayl(methacrylate))或這些的組合等。
此外,光阻517還包括一種或多種光活性化合物。光活性化合物可以是光活性組分,例如光酸產生劑、光鹼產生劑、自由基產生劑等。在光活性化合物為光酸產生劑的實施例中,光活 性化合物可包含鹵化三嗪(halogenated triazines)、鎓鹽(onium salts)、重氮鹽(diazonium salts)、芳族重氮鹽(aromatic diazonium salts)、鏻鹽(phosphonium salts)、鋶鹽(sulfonium salts)、錪鹽(iodonium salts)、醯亞胺磺酸酯(imide sulfonate)、肟磺酸酯(oxime sulfonate)、重氮二碸(diazodisulfone)、二碸(disulfone)、鄰硝基苯甲基磺酸酯(o-nitrobenzylsulfonate)、磺化酯(sulfonated esters)、鹵化磺醯氧基二甲醯亞胺(halogenerated sulfonyloxy dicarboximides)、重氮基二碸(diazodisulfones)、α-氰基氧基胺-磺酸酯(α-cyanooxyamine-sulfonates)、醯亞胺磺酸酯(imidesulfonates)、酮重氮基碸(ketodiazosulfones)、磺醯基重氮酯(sulfonyldiazoesters)、1,2-二(芳基磺醯基)肼(1,2-di(arylsulfonyl)hydrazines)、硝基苯甲酯(nitrobenzyl esters)、及s-三嗪衍生物(s-triazine derivatives)及這些的合適的組合等。在特定實施例中,光酸產生劑具有以下式:
Figure 108133570-A0305-02-0023-1
然而,可利用任何合適的光酸產生劑。
可使用的光酸產生劑的具體實例包括α.-(三氟甲基磺醯氧基)-雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺(α.-(trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarbo-ximide,MDT)、N-羥基-萘二甲醯亞胺 (N-hydroxy-naphthalimide,DDSN)、安息香甲苯磺酸酯(benzoin tosylate)、叔丁基苯基-α-(對甲苯磺醯氧基)-乙酸酯及叔丁基-α-(對甲苯磺醯氧基)-乙酸酯(t-butylphenyl-α-(p-toluenesulfonyloxy)-acetate)、三芳基鋶(triarylsulfonium)及二芳基錪六氟銻酸酯(diaryliodonium hexafluoroantimonates)、六氟砷酸酯(hexafluoroarsenates)、三氟甲磺酸酯(trifluoromethanesulfonates)、錪全氟辛磺酸酯(iodonium perfluorooctanesulfonate)、N-樟腦磺醯氧基萘二甲醯亞胺(N-camphorsulfonyloxynaphthalimide)、N-五氟苯基磺醯氧基萘二甲醯亞胺(N-pentafluorophenylsulfonyloxynaphthalimide)、離子錪磺酸酯(例如二芳基錪(烷基或芳基)磺酸酯)及雙-(二-叔丁基苯基)錪莰基磺酸酯(bis-(di-t-butylphenyl)iodonium camphanylsulfonate)、全氟烷磺酸酯(例如全氟戊烷磺酸酯(perfluoropentanesulfonate)、全氟辛烷磺酸酯(perfluorooctanesulfonate)、全氟甲磺酸酯(perfluoromethanesulfonate))、芳基(例如,苯基或苯甲基)三氟甲磺酸酯(例如三苯基鋶三氟甲磺酸酯(perfluoromethanesulfonate)或雙-(叔丁基苯基)錪三氟甲基磺酸酯(bis-(t-butylphenyl)iodonium triflate));連苯三酚衍生物(例如,連苯三酚的三甲磺酸酯(trimesylate of pyrogallol))、羥基醯亞胺的三氟甲磺酸酯(trifluoromethanesulfonate esters of hydroxyimides)、α,α'-雙-磺醯基-重氮甲烷 (α,α'-bis-sulfonyl-diazomethanes)、經硝基取代的苯甲基醇的磺酸酯(sulfonate esters of nitro-substituted benzyl alcohols)、萘醌-4-二疊氮(naphthoquinone-4-diazides)、烷基二碸(alkyl disulfones)等。
在光活性化合物為自由基產生劑的實施例中,光活性化合物可包含正苯基甘氨酸(n-phenylglycine)、芳族酮(例如苯甲酮(benzophenone))、N,N'-四甲基-4,4'-二氨基苯甲酮(N,N'-tetramethyl-4,4'-diaminobenzophenone)、N,N'-四乙基-4,4'-二氨基苯甲酮(N,N'-tetraethyl-4,4'-diaminobenzophenone)、4-甲氧基-4’-二甲基氨基苯甲酮(4-methoxy-4'-dimethylaminobenzo-phenone)、3,3'-二甲基-4-甲氧基苯甲酮(3,3'-dimethyl-4-methoxybenzophenone)、p,p'-雙(二甲基氨基)苯甲酮(p,p'-bis(dimethylamino)benzo-phenone)、p,p'-雙(二乙基氨基)-苯甲酮(p,p'-bis(diethylamino)-benzophenone)、蒽醌(anthraquinone)、2-乙基蒽醌(2-ethylanthraquinone)、萘醌(naphthaquinone)及菲醌(phenanthraquinone)、安息香類(例如安息香(benzoin)、安息香甲基醚(benzoinmethylether)、安息香乙基醚(benzoinethylether)、安息香異丙醚(benzoinisopropylether)、安息香-正丁醚(benzoin-n-butylether)、安息香-苯基醚(benzoin-phenylether)、甲基安息香(methylbenzoin)及乙基安息香(ethybenzoin))、苯甲基衍生物(例如二苯甲基、苯甲基二苯基二碸(benzyldiphenyldisulfide)、及苯甲基二甲基縮 酮(benzyldimethylketal))、吖啶衍生物(例如9-苯基吖啶(9-phenylacridine)及1,7-雙(9-吖啶)庚烷(1,7-bis(9-acridinyl)heptane))、噻噸酮(例如2-氯噻噸酮(2-chlorothioxanthone)、2-甲基噻噸酮(2-methylthioxanthone)、2,4-二乙基噻噸酮(2,4-diethylthioxanthone)、2,4-二甲基噻噸酮(2,4-dimethylthioxanthone)、及2-異丙基噻噸酮(2-isopropylthioxanthone))、苯乙酮(例如1,1-二氯苯乙酮(1,1-dichloroacetophenone)、對叔丁基二氯-苯乙酮(p-t-butyldichloro-acetophenone)、2,2-二乙氧基苯乙酮(2,2-diethoxyacetophenone)、2,2-二甲氧基-2-苯基苯乙酮(2,2-dimethoxy-2-phenylacetophenone)、及2,2-二氯-4-苯氧基苯乙酮(2,2-dichloro-4-phenoxyacetophenone))、2,4,5-三芳基咪唑二聚物(例如2-(鄰氯苯基)-4,5-二苯基咪唑二聚物(2-(o-chlorophenyl)-4,5-diphenylimidazole dimer)、2-(鄰氯苯基)-4,5-二-(間甲氧基苯基咪唑二聚物(2-(o-chlorophenyl)-4,5-di-(m-methoxyphenyl imidazole dimer)、2-(鄰氟苯基)-4,5-二苯基咪唑二聚物(2-(o-fluorophenyl)-4,5-diphenylimidazole dimer)、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚物(2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer)、2-(對甲氧基苯基)-4,5-二苯基咪唑二聚物(2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer)、2,4-二(對甲氧基苯基)5-苯基咪唑二聚物(2,4-di(p-methoxyphenyl)-- 5-phenylimidazole dimer)、2-(2,4-二甲氧基苯基)-4,5-二苯基咪唑二聚物(2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer)、及2-(對甲基巰苯基)-4,5-二苯基咪唑二聚物(2-(p-methylmercaptophenyl)-4,5-diphenylimidazole dimmer))或這些的合適的組合等。
在光活性化合物為光鹼產生劑的實施例中,光活性化合物可包含季銨二硫代氨基甲酸酯(quaternary ammonium dithiocarbamates)、α氨基酮(α aminoketones)、含肟-尿烷的分子(例如二苯並醯苯肟六亞甲基二尿烷(dibenzophenoneoxime hexamethylene diurethan))、四有機基硼酸銨鹽(ammonium tetraorganylborate salts)、及N-(2-硝基苯甲氧基羰基)環胺(N-(2-nitrobenzyloxycarbonyl)cyclic amines)或這些的合適的組合等。然而,如所屬領域中的普通技術人員將知,本文所列化學化合物僅旨在作為光活性化合物的說明性實例,而並不旨在將實施限制於僅具體闡述的那些光活性化合物。而是,可利用任何合適的光活性化合物,且所有此種光活性化合物均旨在包含於本發明實施例的範圍內。
此外,光阻517還可含有檢測添加劑,所述檢測添加劑有助於提高顯影後檢查(after development inspection,ADI)檢測光阻517中存在缺陷的能力。在一些實施例中,檢測添加劑可以是螢光添加劑,在顯影後檢查期間存在的條件下,所述螢光添加劑發螢光以有助於檢查製程檢測先前未見的缺陷。舉例來說,檢 測添加劑可以是具有不同激發及發射帶(excitation and emission bands)的材料,此使得檢測添加劑能夠吸收第一波長的光且然後發射第二波長的光。
在特定實施例中,檢測添加劑可以是具有高度共軛結構的螢光添加劑。舉例來說,在一些實施例中,檢測添加劑可以是薑黃色素(curcumin)的酮式(keto form),其可具有如下結構:
Figure 108133570-A0305-02-0028-2
利用此種結構,薑黃色素將具有約為420nm的激發帶,但也將具有約為540nm的發射帶。由於此種差異,檢查製程還可拍攝將捕捉發射帶下的波長(例如,540nm)的圖像,所述圖像與捕捉的其他數據一起可用來提供額外的圖像。這些額外的圖像可有助於提供額外的對比度,以識別以其他方式無法檢測到的可能的缺陷。
此外,儘管以上描述及示出了薑黃色素的酮式,但此旨在僅為一種可能的檢測添加劑的說明性實例,而不旨在限於此精確實施例。相反,也可使用任何合適的檢測添加劑,例如薑黃色素的烯醇式,或任何其他具有有助於在顯影後檢查期間增加對比度的合適的激發及發射帶的化學品。舉例來說,還可使用薑黃色 素I、薑黃色素II(去甲氧基薑黃色素(demethoxycurcumin))或薑黃色素III(雙去甲氧基薑黃色素(bis-demoethoxycurcumin)),所述薑黃色素中的每一者的結構分別如下所示:
Figure 108133570-A0305-02-0029-3
所有此種檢測添加劑均旨在包含於實施例的範圍內。
光阻517的各個組分可被放置在光阻溶劑中,以有助於光阻517的混合及放置。為了有助於光阻517的混合及放置,至少部分地基於為光阻聚合物樹脂及光活性化合物選擇的材料來選擇光阻溶劑。具體來說,選擇光阻溶劑使得光阻聚合物樹脂及光活性化合物可均勻地溶解在光阻溶劑中並分配。
在實施例中,所述光阻溶劑可為有機溶劑,且可包含任何合適的溶劑,例如酮、醇、多元醇、醚、乙二醇醚、環醚、芳族烴、酯、丙酸酯、乳酸鹽、乳酸酯、烷二醇單烷基醚(alkylene glycol monoalkyl ethers)、乳酸烷基酯(alkyl lactates)、烷氧基丙酸烷基酯(alkyl alkoxypropionates)、環內酯(cyclic lactones)、包含環的一元酮化合物、碳酸亞烷基酯(alkylene carbonates)、烷 氧基乙酸烷基酯(alkyl alkoxyacetate)、丙酮酸烷基酯(alkyl pyruvates)、乳酸酯、乙二醇烷基醚乙酸酯(ethylene glycol alkyl ether acetates)、二乙二醇(diethylene glycols)、丙二醇烷基醚乙酸酯(propylene glycol alkyl ether acetates)、烷二醇烷基醚酯(alkylene glycol alkyl ether esters)、烷二醇單烷基酯(alkylene glycol monoalkyl esters)等。
可用作光阻517的光阻溶劑的材料的具體實例包括丙酮、甲醇、乙醇、甲苯、二甲苯、4-羥基-4-甲基-2-戊酮(4-hydroxy-4-methyl-2-pentatone)、四氫呋喃(tetrahydrofuran)、甲基乙基酮(methyl ethyl ketone)、環己酮(cyclohexanone)、甲基異戊基酮(methyl isoamyl ketone)、2-庚酮、乙二醇、乙二醇單乙酸酯(ethylene glycol monoacetate)、乙二醇二甲醚(ethylene glycol dimethyl ether)、乙二醇甲***(ethylene glycol methylethyl ether)、乙二醇單***(ethylene glycol monoethyl ether)、甲基溶纖劑乙酸酯(methyl celluslve acetate)、乙基溶纖劑乙酸酯(ethyl cellosolve acetare)、二乙二醇、二乙二醇單乙酸酯、二乙二醇單甲醚、二乙二醇二***、二乙二醇二甲醚、二乙二醇乙甲醚、二乙二醇單***、二乙二醇單丁醚、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-2-甲基丁酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸乙酯、乙酸丁酯、乳酸甲酯及乳酸乙酯、丙二醇、丙二醇單乙酸酯、丙二醇單 ***乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單丙甲醚乙酸酯、丙二醇單丁醚乙酸酯、丙二醇單甲醚丙酸酯、丙二醇單***丙酸酯、丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚、乙二醇單甲醚、乙二醇單***、乳酸甲酯、乳酸乙酯、乳酸丙酯及乳酸丁酯、3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲酯及3-甲氧基丙酸乙酯、β-丙內酯(β-propiolactone)、β-丁內酯(β-butyrolactone)、γ-丁內酯(γ-butyrolactone)、α-甲基-γ-丁內酯(α-methyl-γ-butyrolactone)、β-甲基-γ-丁內酯(β-methyl-γ-butyrolactone)、γ-戊內酯(γ-valerolactone)、γ-己內酯(γ-caprolactone)、γ-辛內酯(γ-octanoic lactone)、α-羥基-γ-丁內酯(α-hydroxy-γ-butyrolactone)、2-丁酮、3-甲基丁酮、頻哪酮(pinacolone)、2-戊酮、3-戊酮、4-甲基-2-戊酮、2-甲基-3-戊酮、4,4-二甲基-2-戊酮、2,4-二甲基-3-戊酮、2,2,4,4-四甲基-3-戊酮、2-己酮、3-己酮、5-甲基-3-己酮、2-庚酮、3-庚酮、4-庚酮、2-甲基-3-庚酮、5-甲基-3-庚酮、2,6-二甲基-4-庚酮、2-辛酮、3-辛酮、2-壬酮、3-壬酮、5-壬酮、2-癸酮、3-癸酮、4-癸酮、5-己-2-酮、3-戊-2-酮、環戊酮、2-甲基環戊酮、3-甲基環戊酮、2,2-二甲基環戊酮、2,4,4-三甲基環戊酮、環己酮、3-甲基環己酮、4-甲基環己酮、4-乙基環己酮、2,2-二甲基環己酮、2,6-二甲基環己酮、2,2,6-三甲基環己酮、環庚酮、2-甲基環庚酮、3-甲基環庚酮、丙 烯碳酸酯、亞乙烯碳酸酯、乙烯碳酸酯、及丁烯碳酸酯、乙酸-2-甲氧基乙酯、乙酸-2-乙氧基乙酯、乙酸-2-(2-乙氧基乙氧)乙酯、乙酸-3-甲氧基-3-甲基丁酯、乙酸-1-甲氧基-2-丙酯、二丙二醇、單甲醚、單***、單丙醚、單丁醚、單苯基醚、二丙二醇單乙酸酯、二噁烷、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、正甲基吡咯烷酮(n-methylpyrrolidone,NMP)、2-甲氧基乙基醚(二甘醇二甲醚)、乙二醇單甲醚、丙二醇單甲醚;乳酸乙酯或乳酸甲酯、丙酸甲酯、丙酸乙酯、及乙氧基丙酸乙酯、甲乙酮、環己酮、2-庚酮、二氧化碳、環戊酮、環己酮、3-乙氧基丙酸乙酯、乳酸乙酯(ethyl lactate)、丙二醇甲醚乙酸酯(propylene glycol methyl ether acetate,PGMEA)、亞甲基溶纖劑(methylene cellosolve)、乙酸丁酯、及2-乙氧基乙醇、N-甲基甲醯胺、N,N-二甲基甲醯胺、N-甲基甲醯苯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮(N-methylpyrrolidone)、二甲基亞碸(dimethylsulfoxide)、苯甲基***、二己醚、丙酮基丙酮、異佛爾酮(isophorone)、己酸、辛酸、1-辛醇、1-壬醇、苯甲醇、乙酸苯甲酯、苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯(diethyl maleate)、γ-丁內酯(γ-butyrolactone)、乙烯碳酸酯、丙烯碳酸酯、苯基溶纖劑乙酸酯(phenyl cellosolve acetate)等。
然而,如所屬領域中的普通技術人員將知,以上所列及所闡述作為可用於光阻517的光阻溶劑組分的材料的實例的材料 僅為說明性的,而並不旨在限制實施例。而是,可利用任何可溶解光阻聚合物樹脂及光活性化合物的合適的材料來輔助混合及施加光阻517。所有此種材料均旨在包含於實施例的範圍內。
此外,雖然上述材料中的個別材料可用作光阻517的光阻溶劑,但在實施例中,可使用多於一種上述材料。舉例來說,光阻溶劑可包含兩種或更多種所述材料的組合混合物。所有此種組合均旨在包含於實施例的範圍內。
視情況,也可將光阻交聯劑添加到光阻517中。光阻交聯劑在暴露後與光阻517內的光阻聚合物樹脂反應,從而輔助提高光阻517的交聯密度,此有助於改善抗蝕劑圖案及抗乾蝕性(resistance to dry etching)。在實施例中,光阻交聯劑可以是三聚氰胺系試劑(melamine based agent)、脲系試劑(urea based agent)、乙烯脲系試劑(ethylene urea based agent)、丙烯脲系試劑(propylene urea based agent)、甘脲系試劑(glycoluril based agent)、具有羥基、羥基烷基或它們的組合的脂肪族環狀烴、脂肪族環狀烴的含氧衍生物、甘脲化合物(glycoluril compounds)、醚化氨基樹脂(etherified amine resins)或這些的組合等。
可用作光阻交聯劑的材料的具體實例包括三聚氰胺、乙醯胍胺(acetoguanamine)、苯並胍胺(benzoguanamine)、脲(urea)、乙烯脲(ethylene urea)或具有甲醛的甘脲、具有甲醛與低級醇的組合的甘脲、六甲氧基甲基三聚氰胺(hexamethoxymethylmelamine)、雙甲氧基甲基脲 (bismethoxymethylurea)、雙甲氧基甲基雙甲氧基乙烯脲(bismethoxymethylbismethoxyethylene urea)、四甲氧基甲基甘脲(tetramethoxymethylglycoluril)及四丁氧基甲基甘脲(tetrabutoxymethylglycoluril)、單-、二-、三-或四羥甲基化甘脲、單-、二-、三-和/或四甲氧基甲基化甘脲、單-、二-、三-和/或四乙氧基甲基化甘脲、單-、二-、三-和/或四-丙氧基甲基化甘脲、以及單-、二-、三-及/或四-丁氧基甲基化甘脲、2,3-二羥基-5-羥基甲基降冰片烷(2,3-dihydroxy-5-hydroxymethylnorbornane)、2-羥基-5,6-雙(羥基甲基)降冰片烷(2-hydroy-5,6-bis(hydroxymethyl)norbornane)、環己烷二甲醇、3,4,8(或9)-三羥基三環癸烷、2-甲基-2-金剛烷醇(2-methyl-2-adamantanol)、1,4-二噁烷-2,3-二醇及1,3,5-三羥基環己烷(1,4-dioxane-2,3-diol and 1,3,5-trihydroxycyclohexane)、四甲氧基甲基甘脲、甲基丙基四甲氧基甲基甘脲及甲基苯基四甲氧基甲基甘脲、2,6-雙(羥甲基)對甲酚、N-甲氧基甲基-或N-丁氧基甲基-三聚氰胺。此外,通過使甲醛或甲醛及低級醇與含氨基的化合物(例如,三聚氰胺、乙醯胍胺、苯並胍胺、脲、乙烯脲及甘脲)反應、並以羥甲基或低級烷氧基甲基取代氨基的氫原子而得到的化合物,其實例為六甲氧基甲基三聚氰胺(hexamethoxymethylmelamine)、雙甲氧基甲基脲(bismethoxymethyl urea)、雙甲氧基甲基雙甲氧基乙烯脲(bismethoxymethylbismethoxyethylene urea)、四甲氧基甲基甘脲 (tetramethoxymethyl glycoluril)及四丁氧基甲基甘脲(tetrabutoxymethyl glycoluril)、3-氯-2-羥丙基甲基丙烯酸酯(3-chloro-2-hydroxypropyl methacrylate)與甲基丙烯酸的共聚物、3-氯-2-羥丙基甲基丙烯酸酯與甲基丙烯酸環己酯及甲基丙烯酸的共聚物、3-氯-2-羥丙基甲基丙烯酸酯與甲基丙烯酸苄酯及甲基丙烯酸的共聚物、雙酚A-二(3-氯-2-羥丙基)醚(bisphenol A-di(3-chloro-2-hydroxypropyl)ether)、苯酚酚醛樹脂的聚(3-氯-2-羥丙基)醚(poly(3-chloro-2-hydroxypro-pyl)ether of a phenol novolak resin)、季戊四醇四(3-氯-2-羥丙基)醚(pentaerythritol tetra(3-chloro-2-hydroxypropyl)ether)、三羥甲基甲烷三(3-氯-2-羥丙基)醚苯酚(trimethylolmethane tri(3-chloro-2-hydroxypropyl)ether phenol)、雙酚A-二(3-乙醯氧基-2-羥丙基)醚(bisphenol A-di(3-acetoxy-2-hydroxypropyl)ether)、苯酚酚醛樹脂的聚(3-乙醯氧基-2-羥丙基)醚(poly(3-acetoxy-2-hydroxypropyl)ethe-r of a phenol novolak resin)、季戊四醇四(3-乙醯氧基-2-羥丙基)醚(pentaerythritol tetra(3-acetoxy-2-hydroxyprop-yl)ether)、季戊四醇聚(3-氯乙醯氧基-2-羥丙基)醚(pentaerythritol poly(3-chloroacetoxy-2-hydroxypropyl)ether)、三羥甲基甲烷三(3-乙醯氧基-2-羥丙基)醚(trimethylolmethane tri(3-acetoxy-2-hydroxypropyl)ether)或這些的組合等。
除了光阻聚合物樹脂、光活性化合物、檢測添加劑、光 阻溶劑及光阻交聯劑之外,光阻517還可包括許多輔助光阻517獲得最高分辨率的其他添加劑。舉例來說,光阻517還可包括表面活性劑、猝滅劑(quenchers)、穩定劑、增塑劑(plasticizers)、著色劑、黏合添加劑、表面平整劑或這些的組合等。可使用任何合適的添加劑。
在實施例中,將光阻聚合物樹脂、光活性化合物、檢測添加劑以及任何所需添加劑或其他試劑加入到光阻溶劑中用於應用。一旦加入,便對所述混合物進行混合以實現整個光阻517的均勻組成,以確保不存在由光阻517的不均勻混合或非恒定組成引起的缺陷。一旦混合在一起,便可將光阻517在其使用之前進行存儲或者立即使用。
在實施例中,光活性化合物可以約0.5重量%的濃度存在於光阻中。此外,檢測添加劑可以約0.01重量%與約0.03重量%之間(例如,約0.015重量%)的濃度存在於光阻中。然而,可利用任何合適的濃度。
一旦準備就緒,便可通過首先將光阻517施加到晶種層518上來使用光阻517。光阻517可被施加到晶種層518使得光阻517塗布晶種層518的上部被暴露表面,且可使用例如旋轉塗布製程、浸塗法、氣刀塗布法(air-knife coating method)、簾塗法(curtain coating method)、絲-杆(wire-bar)塗布法、凹版塗布法、層合法、擠壓塗布法或這些的組合等製程來施加。在實施例中,光阻517可被施加使得其在晶種層518的表面上具有約10nm與約300nm 之間(例如,約150nm)的厚度。
一旦已施加光阻517,便執行光阻517的預烘烤以在曝光以完成光阻517的施加前固化及乾燥光阻517。光阻517的固化及乾燥會移除光阻溶劑組分,同時留下光阻聚合物樹脂、光活性化合物、檢測添加劑、光阻交聯劑及其它選擇的添加劑。在實施例中,可在適於蒸發掉光阻溶劑的溫度下(例如,在約40℃與150℃之間)執行預烘烤,但精確的溫度相依於為光阻517選擇的材料。所述預烘烤被執行達足以固化及乾燥光阻517的時間,例如約10秒與約5分鐘之間(例如約90秒)的時間。
圖6示出了曝光光阻517以在光阻517內形成曝光區601及未曝光區603。在實施例中,曝光可通過在光阻517一經固化及乾燥後便將光阻517放入成像裝置600中進行曝光而開始。成像裝置600可包括支撐板605、能量源607、位於支撐板605與能量源607之間的圖案化遮罩609、以及光學器件617。在實施例中,支撐板605是光阻517可以放置在上面或貼合在上面的表面,且所述表面在光阻517的曝光期間向載體基底101提供支撐及控制。此外,支撐板605可沿著一個或多個軸移動,以及向載體基底101及光阻517提供任何期望的加熱或冷卻,以防止溫度梯度影響曝光製程。
在實施例中,能量源607將能量611(例如光)供應到光阻517以引發光活性化合物的反應,所述光活性化合物繼而與聚合物樹脂反應以使得光阻517的被能量611撞擊的那些部分發生 化學改變。在實施例中,能量611可為電磁輻射(例如g-射線(具有約436nm的波長)、i-射線(具有約365nm的波長))、紫外輻射、遠紫外輻射、極紫外輻射、x-射線、電子束等。能量源607可為電磁輻射源,且可為KrF准分子雷射(具有248nm的波長)、ArF准分子雷射(具有193nm的波長)、F2准分子雷射(具有157nm的波長)等,但也可利用任何其他合適的能量611源,例如汞蒸氣燈、氙燈、碳弧燈等。
圖案化遮罩609位於能量源607與光阻517之間以在能量611實際撞擊在光阻517上之前阻擋能量611的一些部分以形成圖案化能量615。在實施例中,圖案化遮罩609可包括一系列層(例如,基底、吸收層、抗反射塗層、屏蔽層等)以反射、吸收或以其他方式阻擋能量611的某些部分到達光阻517的不期望被照射的那些部分。可通過以所期望的照射形狀形成穿過圖案化遮罩609的開口而在圖案化遮罩609中形成所期望的圖案。
光學器件(在圖6中由標記為617的梯形表示)可用於聚焦、擴展、反射或以其他方式控制離開能量源607、由圖案化遮罩609圖案化並指向光阻517的能量611。在實施例中,光學器件617包括一個或多個透鏡、反射鏡、濾波器、或其組合等,以控制沿著其路徑的能量611。此外,雖然在圖6中將光學器件617示出為位於圖案化遮罩609與光阻517之間,但光學器件617的元件(例如,個別透鏡、反射鏡等)也可位於能量源607(產生能量611之處)與光阻517之間的任何位置處。
在實施例中,光阻517被放置在支撐板605上。一旦圖案已對齊,能量源607便產生所需的能量611(例如,光),所述能量611穿過圖案化遮罩609及光學器件617而進入光阻517。撞擊在光阻517的一些部分上的圖案化能量615會引發光阻517內的光活性化合物的反應。光活性化合物吸收圖案化能量615後的化學反應產物(例如,酸/鹼/自由基)接著與聚合物樹脂反應,從而使光阻517在通過圖案化遮罩609被照射的那些部分中發生化學改變。然而,檢測添加劑不參與在光阻517的圖案化期間發生的其他反應。
在光阻517已被曝光之後,便可使用曝光後烘烤(post-exposure baking)來輔助在曝光期間因圖案化能量615撞擊在光活性化合物上而產生的酸/鹼/自由基的產生、分散及反應。此種輔助有助於產生或加強在光阻517內的曝光區601及未曝光區603之間產生化學差異的化學反應。這些化學差異也導致在曝光區601與未曝光區603之間的溶解度差異。在實施例中,此曝光後烘烤可在約40℃與約200℃之間的溫度下發生並持續約10秒與約10分鐘之間的時間。然而,可利用任何合適的溫度及時間。
圖7示出在曝光光阻517後使用顯影劑701對光阻517進行顯影。在光阻517已被曝光且已發生曝光後烘烤之後,可使用正性(positive tone)顯影劑對光阻517進行顯影。在實施例中,正性顯影劑可以是鹼性水溶液,其用於移除光阻517的暴露於圖案化能量615且其溶解度通過化學反應被修改及改變的那些部 分。此類鹼性水溶液可包括四甲基氫氧化銨(tetra methyl ammonium hydroxide,TMAH)、四丁基氫氧化銨、氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、矽酸鈉、偏矽酸鈉、氨水、單甲胺、二甲胺、三甲胺、單乙胺、二乙胺、三乙胺、單異丙胺、二異丙胺、三異丙胺、單丁胺、二丁胺、單乙醇胺、二乙醇胺、三乙醇胺、二甲基氨基乙醇、二乙氨基乙醇、氨、苛性鈉(caustic soda)、苛性鉀(caustic potash)、偏矽酸鈉(sodium metasilicate)、偏矽酸鉀(potassium metasilicate)、碳酸鈉、氫氧化四乙銨(tetraethylammonium hydroxide)或它們的組合等。
圖7示出使用例如旋塗製程將顯影劑701施加到光阻517。在此製程中,從光阻517的上方將顯影劑701施加到光阻517。在實施例中,可在以約100rpm與約3500rpm之間(例如,約1500rpm)的速度旋轉半導體裝置100的同時以約10ml/min與約2000ml/min之間(例如,約1000ml/min)的流速供應顯影劑701。在實施例中,顯影劑701可處於約10℃與約80℃之間(例如約50℃)的溫度下,且顯影可持續約1分鐘與約60分鐘之間,例如約30分鐘。
然而,儘管本文所述的旋塗法為一種適合於在曝光之後對光阻517進行顯影的方法,但其旨在為說明性的,而並不旨在限制實施例。相反,可使用用於顯影的任何合適的方法,包括浸漬製程、液浸製程(puddle process)、噴塗製程或這些的組合等。所有此種顯影製程均旨在包含於實施例的範圍內。
圖8示出在光阻517已被顯影並且顯影劑701已被移除之後,可執行顯影後檢查製程,以判斷是否存在在光阻517的放置、圖案化及顯影期間已發生的任何缺陷。在實施例中,可將光阻517放置在檢查室801內,所述檢查室801還包括貼合到光學平臺807的同調光源(coherent light source)803及照相機805。在實施例中,同調光源803可以是既可從光阻517反射又可由照相機805檢測到的一個或多個能量源。
在特定的實例中,同調光源803可以是發射以下波長的同調光束811的雷射器,所述波長除了適於缺陷檢查之外,還激發檢測添加劑。因此,當同調光束811撞擊在光阻517及位於光阻517內的檢測添加劑時(下文進一步描述),檢測添加劑(例如,薑黃色素)將吸收在激發波長下的一部分同調光束811,並將被激發。當檢測添加劑隨後返回到正常的非激發態時,檢測添加劑將基於檢測添加劑的發射帶(例如,對於薑黃色素來說為540nm)在不同波長下發射光子。此種激發及隨後的發射將導致檢測添加劑發螢光,從而將螢光的波長加到從光阻517反射的同調光束811的剩餘部分,並增加可實現的對比度的量。
在檢測添加劑為薑黃色素的特定實施例中,同調光束811可以是具有將激發薑黃色素的至少一個波長(例如,在420nm下的至少一個波長)的雷射光束。當同調光束811衝擊薑黃色素時,薑黃色素將吸收420nm波長下的雷射光束並被激發,其中至少有一個電子吸收能量並跳入更高的電子殼(electron shell)中。因此, 一旦薑黃色素返回到其基態(normal state)時,薑黃色素便基於檢測添加劑的發射帶(對薑黃色素來說為540nm)發出不同波長的光。
照相機805用於在同調光束811從光阻517的表面反射出時捕捉同調光束811,並且還用於捕捉從檢測添加劑發螢光的光,從而捕捉被檢查的光阻517的表面的圖像。在實施例中,照相機805可以是一個或多個電荷耦合裝置,其能夠檢測從光阻517反射的能量及從檢測添加劑發螢光的能量。此外,照相機805還可包括例如透鏡或其他光學器件等結構,這些結構有助於將入射的反射雷射分成不同的頻率,並將不同的頻率引導至不同的電荷耦合裝置。這種劃分允許同時采集多幅圖像。
同調光源803及照相機805兩者均可貼合到光學平臺807。在實施例中,光學平臺807安裝在檢查室801內,使得光學平臺807(並且因此同調光源803及照相機805)可相對於光阻517移動。具體來說,光學平臺807可沿任何可能需要的方向(上、下、左、右、進入頁面或離開頁面)移動,以完成對光阻517的全掃描。
此外,雖然已將許多結構描述為檢查室801的一部分,但特別描述的結構並不旨在限制於所述實施例。相反,也可包括任何數量的附加結構(例如,漫射光源、准直器、偏振器、補償器(compensators)、聚焦透鏡或它們的組合等)作為檢查室801的一部分。這些及所有其他合適的結構均旨在包含於實施例的範 圍內。
在操作中,將載體基底101以及光阻517(為了清楚起見,在圖8中僅示出了光阻517)放置在檢查室801內,並且將光學平臺807定位到起始位置。一旦一切就位,同調光源803便產生同調光束811並朝向光阻517引導同調光束811。同調光束811從光阻517反射出,其中光阻517的形貌修改反射並且被捕捉光阻517的表面的圖像的照相機805捕捉。
然而,通過使用檢測添加劑,同調光束不僅從光阻517的表面反射出。除了反射之外,同調光束還將激發光阻517內存在的檢測添加劑。當檢測添加劑返回到其原始的非激發態時,檢測添加劑會發光並發出不同波長的螢光。這種波長的變化也被照相機805獲得,並且可用來幫助提高照相機805記錄的圖像的對比度。
檢查製程通過以下操作從初始位置繼續:通過在光學平臺807及/或光阻517移動時掃描光阻517,或者通過停止照明、移動光學平臺807及/或光阻517、然後照射光阻517的新區段來移動光學平臺807、光阻517或相對於彼此移動所述兩者的組合。此種掃描或步進及掃描(step-and-scan)方法可繼續進行,直到期望被檢查的光阻517的表面的所有圖像都已被照相機805捕捉到。
一旦照相機805已捕捉到了所需的圖像(或者當照相機805捕捉所需的圖像時),照相機805便將所捕捉的光阻517的表面的圖像發送到處理計算機809。處理計算機809獲取各種捕捉的 圖像並識別光阻517的表面上的結構。在一個實施例中,處理計算機809可通過針對給定波長、入射角及結構取向計算反射同調光束811的Rp/Rs比以及來自檢測添加劑的螢光能量來分析來自照相機的圖像,以確定所需的測量值。這種測量可包括光阻517的表面的結構之間的間距、結構的厚度、臨界尺寸、結構的側壁角度或這些的組合等。
在一個非常特定的實施例中,檢查室801可利用來自魯道夫技術(Rudolph Technologies)的法爾弗萊(Firefly)TM系列平臺。在本實施例中,雷射可用於在光阻517上掃描以及激發檢測添加劑(例如,薑黃色素),其中反射雷射及來自檢測添加劑的螢光能量隨後被照相機捕捉及分析。然而,雖然可使用FirefyTM系列平臺,但此僅旨在為說明性的,並非旨在限制實施例,因為可使用可與檢測添加劑一起使用的任何合適的平臺。
通過利用檢測添加劑及檢查製程,可在顯影後檢查期間從對光阻517的表面的成像獲得不同波長的附加能量。在存在附加能量的情況下,可在顯影後檢查製程期間獲得對比度增加的圖像。此種圖像對比度的增加(例如,增加約100%與約300%之間)有助於識別在沒有添加檢測添加劑的情況下無法觀察到的缺陷。
一旦顯影後檢查製程已被完成且如果顯影後檢查製程未發現任何缺陷或發現可能為可接受的若干缺陷,便可將所述結構送交進一步處理(下文將進一步討論)。然而,如果在光阻517內觀察到不可接受數量的缺陷,那麼可通過諸如灰化等製程來移除 光阻517,並且光阻517的放置、曝光、顯影及檢查可重複進行以確保在隨後的處理期間不存在重大缺陷。
圖9示出一旦光阻517已被形成、圖案化及通過檢查,便可通過例如鍍覆(其不受檢測添加劑的存在的影響)等沉積製程在晶種層518(為清楚起見,從圖9移除晶種層518)上形成例如銅等導電材料以形成第一重布線層501。所述導電材料可被形成為具有介於約1μm與約10μm之間(例如約5μm)的厚度。然而,儘管所述材料及方法適合形成導電材料,但這些材料僅為示例性的。可使用任何其他合適的材料(例如AlCu或Au)及任何其他合適的形成製程(例如化學氣相沉積或物理氣相沉積)來形成第一重布線層501。
一旦導電材料已被形成,便可通過合適的移除製程(例如灰化)來移除光阻517。另外,在移除光阻517之後,可通過例如以導電材料作為遮罩的合適的蝕刻製程來移除晶種層518的被光阻517覆蓋的那些部分。
此外,如果需要,那麼可執行剝離器後檢查(after stripper inspection)以確保在執行後續處理之前已充分移除所有光阻517。在實施例中,可以與顯影後檢查類似的方式執行剝離器後檢查,其中將所述結構放置在檢查室801中,並且能量(例如,雷射)從表面反射出且由照相機805捕捉圖像。在此類實施例中,檢測添加劑的存在將再次提高對比度並幫助識別先前未被檢測到的缺陷。一旦剝離器後檢查證實光阻517已被完全移除,便可繼 續進行製造製程。
圖9還示出在第一重布線層501上形成第三鈍化層503,以便為第一重布線層501及其他下伏結構提供保護及隔離。在實施例中,第三鈍化層503可為聚苯並惡唑(PBO),但也可利用例如聚醯亞胺或聚醯亞胺衍生物等任意合適的材料。第三鈍化層503可使用例如旋轉塗布製程而被形成至約5μm與約25μm之間(例如約7μm)的厚度,但可使用任何合適的方法及厚度。
在已形成第三鈍化層503之後,可通過移除第三鈍化層503的一些部分以暴露出下伏第一重布線層501的至少一部分來形成貫穿第三鈍化層503的第一開口504(為清楚起見,在圖9中僅示出了其中的一者)。第一開口504使得能夠實現第一重布線層501與第二重布線層505之間的接觸(下文進一步描述)。可使用合適的光刻遮罩(包括,例如包括檢測添加劑及普斯特(poste)顯影檢查製程)及蝕刻製程來形成第一開口504,但可使用任何合適的製程來暴露出第一重布線層501的一些部分。
第二重布線層505可被形成為提供附加的路由及連接性並且與第一重布線層501電連接。在實施例中,可類似於第一重布線層501來形成第二重布線層505。舉例來說,可形成晶種層,可將具有檢測添加劑的光阻放置及圖案化在晶種層的頂部,可檢查光阻,並且可將導電材料鍍覆到貫穿光阻的圖案化開口中。一旦形成,便可移除光阻,可蝕刻下伏晶種層,可由第四鈍化層507(其可與第三鈍化層503類似)覆蓋第二重布線層505,且可將第 四鈍化層507圖案化以形成第二開口506(為清楚起見,在圖9中僅示出了其中的一者)並暴露出第二重布線層505的下伏導電部分。
第三重布線層509可被形成為提供額外的路由以及與第二重布線層505的電連接。在實施例中,可使用與第一重布線層501類似的材料及製程來形成第三重布線層509。舉例來說,可形成晶種層,可以第三重布線層509的所需圖案將具有檢測添加劑的光阻放置及圖案化在晶種層的頂部,可檢查光阻,將導電材料鍍覆到光阻的圖案化開口中,移除光阻並蝕刻晶種層。
然而,除了簡單地重新路由電連接(類似於第二重布線層505)之外,第三重布線層509還可包括著陸墊(landing pad),所述著陸墊將用於形成與例如上覆第三外部連接部901的電連接(下文進一步描述)。可使著陸墊成形以便與第三外部連接部901進行合適的物理及電連接。
一旦第三重布線層509已被形成,便可由第五鈍化層511覆蓋第三重布線層509。第五鈍化層511類似於第三鈍化層503可由例如PBO等聚合物形成,或可由與第三鈍化層503類似的材料(例如,聚醯亞胺或聚醯亞胺衍生物)形成。第五鈍化層511可被形成為具有約2μm與約15μm之間(例如約5μm)的厚度。
一旦在第三重布線層509之上設置第五鈍化層511,便可使第五鈍化層511與第三重布線層509平坦化。在實施例中,可使用例如化學機械拋光製程來執行平坦化,由此與旋轉壓板一起 使用蝕刻劑及磨料,以便化學及機械地移除第五鈍化層511的一些部分,直到第五鈍化層511與第三重布線層509共面。然而,可使用任何合適的平坦化製程,例如一系列一種或多種蝕刻或機械研磨製程。
在第五鈍化層511已被形成並平坦化後,可將第六鈍化層513放置在第五鈍化層511及第三重布線層509之上並圖案化。在實施例中,第六鈍化層513可以是與第五鈍化層511類似的材料(例如,PBO),並且第六鈍化層513可被圖案化以暴露出第三重布線層509的下伏部分。在實施例中,可使用光微影及蝕刻製程來圖案化第六鈍化層513,由此在蝕刻製程期間沉積並圖案化光阻並隨後將光阻用作遮罩,以移除第六鈍化層513的一些部分並暴露出第三重布線層509的一些部分。然而,可利用任何合適的用於圖案化第六鈍化層513的方法。
在第六鈍化層513已被形成並圖案化之後,在第六鈍化層513上方沉積第二晶種層515。在實施例中,第二晶種層515為導電材料的薄層,其有助於在後續處理步驟期間形成更厚的層。第二晶種層515可包含約1,000Å厚的鈦層、以及約5,000Å厚的銅層。可依據所期望的材料而使用例如濺射製程、蒸鍍製程或等離子體增強型化學氣相沉積(PECVD)製程等製程來形成第二晶種層515。第二晶種層515可被形成為具有約0.3μm與約1μm之間(例如約0.5μm)的厚度。
一旦第二晶種層515已被沉積,便可將光阻置於第二晶 種層515上方並圖案化以準備形成第三外部連接部901。在實施例中,可放置並圖案化被添加檢測添加劑的光阻,且然後可使用顯影後檢查製程以及檢測添加劑對光阻進行檢查。
一旦光阻已被圖案化,便可在光阻的開口內形成第三外部連接部901。在實施例中,第三外部連接部901可為例如銅柱且可包含一種或多種導電材料(例如銅、鎢、其他導電材料等),且可例如通過電鍍、無電鍍覆等形成。在實施例中,使用電鍍製程,在所述電鍍製程中,將第二晶種層515及光阻浸沒或浸漬在電鍍溶液(例如,含硫酸銅(CuSO4)的溶液)中。第二晶種層515的表面電連接到外部直流(DC)電源的負極側(negative side),以使得第二晶種層515在電鍍製程中用作陰極。實心導電陽極(例如銅陽極)也浸漬在所述溶液中並將所述實心導電陽極貼合到電源的正極側。來自陽極的原子溶解於溶液中,陰極(例如,第二晶種層515)從所述溶液獲取所溶解的原子,從而鍍覆在第二晶種層515於光阻的開口內的被暴露之導電區域上。
一旦已利用光阻及第二晶種層515形成了第三外部連接部901,便可利用合適的移除製程移除光阻。在實施例中,可使用等離子體灰化製程來移除光阻,由此可提高光阻的溫度直到光阻經歷熱分解且可被移除。然而,可利用任何其他合適的製程,例如濕式剝離。移除光阻可暴露出第二晶種層515的下伏部分。
圖9示出一旦第二晶種層515已被暴露出,便可執行移除第二晶種層515的被暴露出的部分。在實施例中,可通過例如 濕式蝕刻製程或乾式蝕刻製程來移除第二晶種層515的被暴露出的部分(例如,未被第三外部連接部901覆蓋的那些部分)。舉例來說,在乾式蝕刻製程中,可利用第三外部連接部901作為遮罩來朝向第二晶種層515引導反應物,從而將第二晶種層515形成為具有垂直於第六鈍化層513的表面的直側壁。在另一實施例中,可噴射蝕刻劑或以其他方式使蝕刻劑與第二晶種層515接觸,以移除第二晶種層515的被暴露出的部分。
圖9示出在第三外部連接部901上形成第四外部連接部1101。在實施例中,第四外部連接部1101可為接觸凸塊(例如微凸塊或受控塌縮芯片連接(controlled collapse chip connection,C4)凸塊),且可包含例如錫等材料或例如銀或銅等其他合適的材料。在第四外部連接部1101是接觸凸塊的實施例中,第四外部連接部1101可包含例如錫等材料或例如銀、無鉛錫或銅等其他合適的材料。在第四外部連接部1101是錫焊料凸塊的實施例中,可通過首先經由此類常用方法(例如蒸鍍、電鍍、印刷、焊料轉移、球放置等)將錫層形成至例如約100μm的厚度來形成第四外部連接部1101。一旦已在結構上形成了一層錫,便可執行回焊以使材料成形為所需的凸塊形狀,所述凸塊形狀的臨界尺寸可在約60μm與約100μm之間,並且可形成為圓形形狀或橢圓形形狀。
圖10示出載體基底101從第一半導體裝置201及第二半導體裝置301剝離。在實施例中,可將第四外部連接部1101且因此將包括第一半導體裝置201及第二半導體裝置301的結構貼合 到環結構1201。環結構1201可為金屬環,用以在所述剝離製程期間及在所述剝離製程之後為結構提供支撐及穩定性。在實施例中,使用例如紫外膠帶1203將第四外部連接部1101、第一半導體裝置201及第二半導體裝置301貼合到環結構,但可使用任何其他合適的黏合劑或貼合方式。
一旦第四外部連接部1101且因此包括第一半導體裝置201及第二半導體裝置301的結構貼合到環結構1201之後,便可使用例如用以改變黏合劑層103的黏合性質的熱製程將載體基底101從包括第一半導體裝置201及第二半導體裝置301的結構剝離。在特定實施例中,利用例如紫外(UV)雷射、二氧化碳(CO2)雷射、或紅外(infrared,IR)雷射等能量源來輻照及加熱黏合劑層103,直到黏合劑層103喪失其至少某些的黏合性質中。一旦執行之後,便可使載體基底101及黏合劑層103從包括第四外部連接部1101、第一半導體裝置201及第二半導體裝置301的結構實體分離且自所述結構移除。
圖10另外示出將聚合物層105圖案化以暴露出通孔111(以及相關聯的第一晶種層107)。在實施例中,可使用例如雷射鑽孔方法來圖案化聚合物層105。在此種方法中,首先在聚合物層105上方沉積保護層,例如光-熱轉換(light-to-heat conversion,LTHC)層或保護層(例如是hogomax層,在圖10中未單獨示出)。一旦得到保護之後,便將雷射射到聚合物層105的期望被移除的那些部分以暴露出下伏通孔111。在雷射鑽孔製程期間,鑽孔能量 可處於0.1mJ到約30mJ的範圍內,且鑽孔角度相對於聚合物層105的法線為約0°(垂直於聚合物層105)到約85°。在實施例中,所述圖案化可被形成為將第四開口1205在通孔111上方形成為具有約100μm與約300μm之間(例如約200μm)的寬度。
在另一實施例中,可通過以下方式將聚合物層105圖案化:首先對聚合物層105施加光阻(在圖10中未各別示出),然後將光阻暴露至圖案化能量源(例如,圖案化光源)以引發化學反應,從而引發光阻的被暴露到圖案化光源的那些部分的物理變化。然後對被暴露光阻施加顯影劑,以利用物理變化並依據所期望的圖案而選擇性地移除光阻的被暴露部分或光阻的未被暴露部分,且利用例如乾式蝕刻製程來移除聚合物層105的下伏被暴露部分。然而,可利用任何其他合適的用於圖案化聚合物層105的方法。
圖11示出將背面球墊1301放置在聚合物層105的開口內,以保護現在被暴露出的通孔111。在實施例中,背面球墊1301可包括例如焊料膏(solder on paste)或氧化保焊劑(oxygen solder protection,OSP)等導電材料,但也可利用任意合適的材料。在實施例中,可使用模版(stencil)來施加背面球墊1301,但也可使用任何合適的施加方法,且然後對背面球墊1301進行回焊以形成凸塊形狀。
圖11還示出背面球墊1301上的背面保護層1303的放置及圖案化,背面保護層1303有效地密封背面球墊1301與通孔111 之間的接合處以防止受潮。在實施例中,背面保護層1303可為例如聚苯並惡唑、阻焊劑(SR)、層合化合物(lamination Compound,LC)膠帶、味之素構成膜(ABF)、非導電膏(non-conductive paste,NCP)、非導電膜(non-conductive film,NCF)、圖案化底部填充物(patterned underfill,PUF)、翹曲改善黏合劑(warpage improvement adhesive,WIA)、液體模制化合物V9、或其組合等保護材料。然而,也可利用任意合適的材料。可利用例如絲網印刷(screen printing)、層合、旋轉塗布等製程來將背面保護層1303塗敷到約1μm與約200μm之間的厚度。
圖11還示出一旦已放置了背面保護層1303,便可將背面保護層1303圖案化以暴露出背面球墊1301。在實施例中,可以使用例如雷射鑽孔方法來圖案化背面保護層1303,通過所述雷射鑽孔方法朝向背面保護層1303的期望被移除的那些部分引導雷射,以暴露出背面球墊1301。在雷射鑽孔製程期間,鑽孔能量可處於0.1mJ到約30mJ的範圍內,且鑽孔角度相對於背面保護層1303的法線為約0°(垂直於背面保護層1303)到約85°。在實施例中,所述暴露可形成直徑介於約30μm與約300μm之間(例如,約150μm)的開口。
在另一實施例中,可通過以下方式將背面保護層1303圖案化:首先對背面保護層1303施加光阻(在圖11中未各別示出),然後將光阻暴露至圖案化能量源(例如,圖案化光源)以引發化學反應,從而引發光阻的被暴露至圖案化光源的那些部分的物理 變化。然後對被暴露光阻施加顯影劑,以利用物理變化並依據所期望的圖案而選擇性地移除光阻的被暴露部分或光阻的未被暴露部分,且利用例如乾式蝕刻製程來移除背面保護層1303的下伏被暴露部分。然而,可利用任何其他合適的用於圖案化背面保護層1303的方法。
圖11還示出將背面球墊1301接合到第一封裝1300。在實施例中,第一封裝1300可包括第三基底1305、第三半導體裝置1307、第四半導體裝置1309(接合到第三半導體裝置1307)、第三接觸墊1311、第二包封體1313及第五外部連接部1315。在實施例中,第三基底1305可為例如包括用以將第三半導體裝置1307及第四半導體裝置1309連接到背面球墊1301的內部互連件(例如,基底穿孔1317)的封裝基底。
在另一實施例中,第三基底1305可為用作中間基底的中介層(interposer)以將第三半導體裝置1307及第四半導體裝置1309連接到背面球墊1301。在此實施例中,第三基底1305可為例如經摻雜或未經摻雜的矽基底、或絕緣體上覆矽(SOI)基底的主動層。然而,第三基底1305也可為玻璃基底、陶瓷基底、聚合物基底、或可提供合適的保護和/或互連功能性的任何其他基底。第三基底1305可由這些及任何其他合適的材料構成。
第三半導體裝置1307可為被設計用於預期用途(例如作為邏輯晶粒、中央處理器(central processing unit,CPU)晶粒、記憶體晶粒(例如,動態隨機存取記憶體(DRAM)晶粒)或這 些的組合等)的半導體裝置。在實施例中,根據對於特定功能性來說所需要,第三半導體裝置1307包括集成電路裝置,例如電晶體、電容器、電感器、電阻器、金屬化層(圖中未示出)等。在實施例中,第三半導體裝置1307被設計及製造成與第一半導體裝置201相結合地操作或與第一半導體裝置201同時操作。
第四半導體裝置1309可類似於第三半導體裝置1307。舉例來說,第四半導體裝置1309可為被設計用於預期用途(例如,動態隨機存取記憶體晶粒)且包括用於所期望功能性的集成電路裝置的半導體裝置。在實施例中,第四半導體裝置1309被設計成與第一半導體裝置201和/或第三半導體裝置1307相結合地操作或與第一半導體裝置201和/或第三半導體裝置1307同時操作。
第四半導體裝置1309可接合到第三半導體裝置1307。在實施例中,第四半導體裝置1309僅與第三半導體裝置1307實體接合,例如通過使用黏合劑進行結合。在此實施例中,第四半導體裝置1309及第三半導體裝置1307可使用例如打線結合(wire bond)1319而電連接到第三基底1305,但可利用任何合適的電接合。
在另一實施例中,第四半導體裝置1309可實體及電接合到第三半導體裝置1307。在此實施例中,第四半導體裝置1309可包括外部連接部(在圖11中未單獨示出),所述連接部與第三半導體裝置1307上的外部連接部(在圖11中也未單獨示出)連接以將第四半導體裝置1309與第三半導體裝置1307互連。
第三接觸墊1311可形成於第三基底1305上以形成第三半導體裝置1307與例如第五外部連接部1315之間的電連接。在實施例中,第三接觸墊1311可形成於第三基底1305上方且與第三基底1305內的電路徑(例如基底穿孔1317)電接觸。第三接觸墊1311可包含鋁,但可使用其他材料,例如銅。可使用沉積製程(例如濺射)來形成第三接觸墊1311,以形成材料層(圖中未示出),且然後可通過合適的製程(例如光微影及蝕刻)來移除所述材料層的部分以形成第三接觸墊1311。然而,可利用任何其他合適的製程來形成第三接觸墊1311。第三接觸墊1311可被形成為具有約0.5μm與約4μm之間(例如約1.45μm)的厚度。
可使用第二包封體1313來包封及保護第三半導體裝置1307、第四半導體裝置1309及第三基底1305。在實施例中,第二包封體1313可為模制化合物且可使用模制裝置(在圖11中未示出)來放置。舉例來說,可將第三基底1305、第三半導體裝置1307及第四半導體裝置1309放置在模制裝置的空腔內,且可將所述空腔氣密密封。可在所述空腔被氣密密封之前將第二包封體1313放置在空腔內,或可通過注射口而將第二包封體1313注射到空腔中。在實施例中,第二包封體1313可為模制化合物樹脂,例如聚醯亞胺、PPS、PEEK、PES、耐熱晶體樹脂或這些的組合等。
一旦已將第二包封體1313放置到空腔中以使得第二包封體1313包封第三基底1305、第三半導體裝置1307、以及第四半導體裝置1309周圍的區之後,便可將第二包封體1313固化以硬 化第二包封體1313來實現最佳保護。儘管確切固化製程至少部分地相依於為第二包封體1313所選擇的特定材料,但在選擇模制化合物作為第二包封體1313的實施例中,可通過例如將第二包封體1313加熱到約100℃與約130℃之間(例如約125℃)達約60秒到約3000秒(例如約600秒)的時間的製程來進行固化。另外,可在第二包封體1313內包含引發劑和/或催化劑以更好地控制所述固化製程。
然而,如所屬領域中的普通技術人員將知,上述固化製程僅為示例性製程,而並不旨在限制當前實施例。可使用其他固化製程,例如輻照或甚至使第二包封體1313在周圍環境溫度下硬化。可使用任何合適的固化製程,且所有此種製程均旨在包含於本文所述實施例的範圍內。
在實施例中,可形成第五外部連接部1315以提供第三基底1305與例如背面球墊1301之間的外部連接。第五外部連接部1315可為接觸凸塊(例如微凸塊或受控塌縮芯片連接(C4)凸塊),且可包含例如錫等材料或例如銀或銅等其他合適的材料。在第五外部連接部1315為錫焊料凸塊的實施例中,可通過首先經由任何合適的方法(例如蒸鍍、電鍍、印刷、焊料轉移、球放置等)將錫層形成到例如約100μun的厚度來形成第五外部連接部1315。一旦錫層已形成於所述結構上,便執行回焊以將所述材料成型為期望的凸塊形狀。
一旦已形成第五外部連接部1315,便使第五外部連接部 1315與背面球墊1301對齊並將第五外部連接部1315放置成與背面球墊1301實體接觸,且執行接合。舉例來說,在第五外部連接部1315為焊料凸塊的實施例中,接合製程可包括回焊製程,由此使第五外部連接部1315的溫度升高到使第五外部連接部1315將液化及流動的程度,從而一旦第五外部連接部1315重新凝固之後便將第一封裝1300接合到背面球墊1301。
圖11另外示出將第二封裝1321接合到背面球墊1301。在實施例中,第二封裝1321可類似於第一封裝1300,且可利用類似的製程接合到背面球墊1301。然而,第二封裝1321也可不同於第一封裝1300。
圖12示出將第四外部連接部1101從環結構1201剝離以及將所述結構單體化以形成第一集成扇出式堆疊封裝(integrated fan out package-on-package,InFO-POP)結構1400。在實施例中,可通過首先使用例如第二紫外膠帶將第一封裝1300及第二封裝1321接合到第二環結構而使第四外部連接部1101從環結構1201剝離。一旦接合之後,便可使用紫外輻射來輻照紫外膠帶1203,且一旦紫外膠帶1203已喪失其黏合性,便可使第四外部連接部1101從環結構1201實體分離。
一旦剝離,便執行所述結構的單體化以形成第一集成扇出式堆疊封裝結構1400。在實施例中,可通過使用鋸片(圖中未示出)切穿包封體401及各通孔111之間的聚合物層105來執行單體化,從而使各區段彼此分離以形成具有第一半導體裝置201 的第一集成扇出式堆疊封裝結構1400。然而,如所屬領域中的普通技術人員將知,利用鋸片將第一集成扇出式堆疊封裝結構1400單體化僅為一個說明性實施例,而並不旨在進行限制。也可利用將第一集成扇出式堆疊封裝結構1400單體化的其他方法,例如利用一次或多次蝕刻來分離第一集成扇出式堆疊封裝結構1400。可利用這些方法及任何其他合適的方法來將第一集成扇出式堆疊封裝結構1400單體化。
通過利用光阻內的檢測添加劑(例如,薑黃色素)及檢查製程,可在顯影檢查期間或顯影檢查之後從對光阻517的表面的成像獲得不同波長的附加能量。在存在附加能量的情況下,可在顯影後檢查製程期間獲得對比度增加的圖像。此種圖像對比度的增加(例如,增加約100%與約300%之間)有助於識別在沒有添加檢測添加劑的情況下無法觀察到的缺陷。因此,在缺陷可對後續處理步驟產生影響之前可識別出並處理更多的缺陷,從而使效率及良率整體增加。
在實施例中,一種製造半導體裝置的方法,所述方法包括:在半導體基底之上施加光阻,所述光阻包含檢測添加劑;對所述光阻進行曝光及顯影;以及在對所述光阻進行顯影之後檢查所述光阻,其中所述檢測添加劑在所述檢查所述光阻期間發螢光。在實施例中,所述檢測添加劑是薑黃色素。在實施例中,所述檢測添加劑在約540nm的波長下發螢光。在實施例中,所述檢查所述光阻包括將雷射引導至所述光阻處。在實施例中,所述檢 測添加劑在所述光阻內的濃度在約0.01重量%與約0.03重量%之間。在實施例中,所述檢測添加劑在所述光阻內的濃度為約0.015重量%。在實施例中,所述施加所述光阻包括將所述光阻施加在絕緣體穿孔及包封體之上。
在另一實施例中,一種製造半導體裝置的方法包括:將光阻聚合物樹脂放置在光阻溶劑中;將光酸產生劑放置在所述光阻溶劑中;將薑黃色素放置在所述光阻溶劑中;以及混合所述光阻聚合物樹脂、所述光酸產生劑、所述薑黃色素以及所述光阻溶劑以形成光阻。在實施例中,所述方法還包括將所述光阻分配到半導體基底上。在實施例中,所述方法還包括:對所述光阻進行顯影;以及在對所述光阻進行顯影之後檢查所述光阻。在實施例中,在所述檢查所述光阻期間,所述薑黃色素將發螢光。在實施例中,包封體環繞所述半導體基底。在實施例中,穿孔延伸貫穿所述包封體。在實施例中,所述方法還包括在所述檢查所述光阻之後在所述光阻內鍍覆重布線層。
在又一實施例中,一種光阻包含:光阻聚合物樹脂;光活性化合物;以及檢測添加劑,其中所述檢測添加劑在所述光阻內的濃度在約0.01重量%與約.03重量%之間。在實施例中,所述檢測添加劑是薑黃色素。在實施例中,所述光阻聚合物樹脂位於半導體基底上方。在實施例中,所述光阻聚合物樹脂位於所述半導體基底周圍的包封體之上。在實施例中,所述光阻聚合物樹脂位於從所述包封體的第一側延伸到所述包封體的第二側的穿孔之 上。在實施例中,所述光阻是正性光阻。
以上內容概述了若干實施例的特徵以使所屬領域中的技術人員可更好地理解本公開內容的各個方面。所屬領域中的技術人員應理解,其可容易地使用本公開作為設計或修改其他製程及結構的基礎來施行與本文中所介紹的實施例相同的目的和/或實現與本文中所介紹的實施例相同的優點。所屬領域中的技術人員還應認識到,這些等效構造並不背離本公開的精神及範圍,而且他們可在不背離本公開的精神及範圍的條件下對其作出各種改變、代替及變更。
105:聚合物層
107:第一晶種層
111:通孔
201:第一半導體裝置
401:包封體
501:第一重布線層
505:第二重布線層
509:第三重布線層
513:第六鈍化層
901:第三外部連接部
1101:第四外部連接部
1300:第一封裝
1301:背面球墊
1303:背面保護層
1305:第三基底
1307:第三半導體裝置
1309:第四半導體裝置
1311:第三接觸墊
1313:第二包封體
1315:第五外部連接部
1317:基底穿孔
1319:打線結合
1400:第一集成扇出式堆疊封裝結構

Claims (9)

  1. 一種製造半導體裝置的方法,包括:在半導體基底之上施加光阻,所述光阻包含檢測添加劑,其中所述光阻施加在環繞所述半導體基底的包封體以及貫穿所述包封體的通孔上;對所述光阻進行曝光及顯影;以及在對所述光阻進行顯影之後檢查所述光阻,其中所述檢測添加劑在所述檢查所述光阻期間發螢光。
  2. 如申請專利範圍第1項所述的製造半導體裝置的方法,其中所述檢測添加劑是薑黃色素。
  3. 如申請專利範圍第1項所述的製造半導體裝置的方法,其中所述檢查所述光阻包括將雷射引導至所述光阻處。
  4. 如申請專利範圍第1項所述的製造半導體裝置的方法,其中所述檢測添加劑在所述光阻內的濃度在約0.01重量%與約0.03重量%之間。
  5. 一種製造半導體裝置的方法,包括:將光阻聚合物樹脂放置在光阻溶劑中;將光酸產生劑放置在所述光阻溶劑中;將薑黃色素放置在所述光阻溶劑中;混合所述光阻聚合物樹脂、所述光酸產生劑、所述薑黃色素以及所述光阻溶劑以形成光阻;以及將所述光阻分配到半導體基底上,其中包封體環繞所述半導 體基底。
  6. 如申請專利範圍第5項所述的製造半導體裝置的方法,更包括:對所述光阻進行顯影;以及在對所述光阻進行顯影之後檢查所述光阻。
  7. 一種光阻,包括:光阻聚合物樹脂;光活性化合物;以及檢測添加劑,其中所述檢測添加劑在所述光阻內的濃度在約0.01重量%與約0.03重量%之間,其中所述光阻聚合物樹脂位於半導體上以及所述半導體基底周圍的包封體上。
  8. 如申請專利範圍第7項所述的光阻,其中所述檢測添加劑是薑黃色素。
  9. 如申請專利範圍第7項所述的光阻,其中所述光阻是正性光阻。
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