TW201033739A - Spin-on spacer materials for double-and triple-patterning lithography - Google Patents

Spin-on spacer materials for double-and triple-patterning lithography Download PDF

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TW201033739A
TW201033739A TW099100242A TW99100242A TW201033739A TW 201033739 A TW201033739 A TW 201033739A TW 099100242 A TW099100242 A TW 099100242A TW 99100242 A TW99100242 A TW 99100242A TW 201033739 A TW201033739 A TW 201033739A
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composition
layer
feature
group
patterned surface
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Qian Lin
Rama Puligadda
James Claypool
Douglas J Guerrero
Brian Smith
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Brewer Science Inc
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
    • C—CHEMISTRY; METALLURGY
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H01L21/0338—Process specially adapted to improve the resolution of the mask
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/312—Organic layers, e.g. photoresist
    • H01L21/3121—Layers comprising organo-silicon compounds
    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating

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201033739 六、發明說明： 【相關申請案】 本申請案主張2009年1月7曰申請之標題為用於雙重 圖案化微影術之旋塗間隔材料（SPIN-ON SPACER MATERIALS FOR DOUBLE-PATTERNING LITHOGRAPHY) 之臨時申請案第61/143,013號的優先權，該臨時申請案以 引用之方式併入本文中。 【發明所屬之技術領域】 本發明大體而言係關於一種新穎的多重圖案化方法， 該方法利用可收縮組成物形成間隔結構。 【先前技術】 由於在開發下一代193 nm浸潰技術及超紫外線微影術 (extreme ultraviolet lithography’ EUVL)方面之延遲，使 用現行工具進行雙重囷案化為計劃自2008年至2012年用 於32 nm及22 nm半間距（half-pitch )節點的唯一微影技 術。自對準間隔件技術（Self-aligned spacer technology )為 一種在廣泛研究中之雙重圖案化技術。間隔件方法之優點 在於僅需要一次微影曝露，從而避免連續曝露之間發生重 疊的嚴重問題◊藉由在預先圖案化之特徵上沈積塗層，隨 後蝕刻以移除膜之存在於水平表面上之部分，留下僅鑲襯 側壁之間隔件膜層，形成間隔件。隨後移除原始圖案化特 徵，僅留下間隔件。因為每線形成兩個間隔件，所以線密 度（line density )加倍。因此，可製’造32 nm或更小的密集 201033739 線（dense line )。 先别已嘗试使用基於利用化學氣相沈積（chemical vapor deposition，CVD )法塗覆之膜的間隔件技術。該方法 包括數個CVD步驟以在光阻劑（photoresist )下製備各層 然後進行光微影術。光微影術之後’使用數個触刻步驟打 開下層（underlayer)以製備模板。模板製備後，使用CVD 塗覆保形塗層（conformal coating )，該塗層可進一步經钱 刻形成間隔件。需要如此多的步驟使得該方法成本高且效 〇 率低。此外’各層堆集導致不能控制臨界尺寸（critical dimension，CD )。 已進行其他嘗試以利用材料及稱為化學收縮辅助之解 析度增強微影術（resolution enhancement lithography assisted by chemical shrink，RELACS)的方法來使小特徵 • 之出現率或間距加倍。RELACS方法係基於自抗蝕劑 (resist )向外擴散之酸誘導之交聯反應，且包括四個步驟： 紅塗，全面曝露（blanket exposure);烘烤；及顯影。該技 ® 術主要應用於使接觸孔收縮，收縮係視抗蝕劑誘導之化學 相互作用而定。該方法不適用於形成小型線，而是僅適用 於使由KrF ( 248 nm )技術製造之大型（> ! 〇〇 nm )線之出 現率加倍，因為KrF RELACS方法在相對溫和之條件 120 C )下進行。然而，32 nm線之製造係基於ArF〇93 技術。ArF抗蝕劑中酸之遷移率極低，且ArF relacs方法 需要阿烘烤溫度（> i 2〇。〇)，而此溫度會使原始抗蝕線變 形。因此’該方法無任何實際應用之潛力。 201033739 【發明内容】 本發明藉由提供-種形成微電子結構之方法解決先前 技術之問題。該方法包含提供具有圖案化表面的前驅結 構。圖案化表面包括至少-個具有側壁及上表面之凸起特 徵（raised feature)。在該圖案化表面上塗覆可收縮之組成 物以使之覆蓋特徵之側壁及上表面。加熱可收縮之組成物 以在圖案化表面上及在凸起特徵上方形成該組成物保形 層。移除至少部分保形層以得到包含凸起特徵及緊貼凸起 特徵侧壁之保形層殘留物的前間隔件結構（㈣啊… structure ) 〇 【實施方式】 本發明方法 本發明提供一種新穎的基於塗層收縮之兩步法。 圖1說明本發明之一個具體實例，其中圖1(a)描繪圖案 化前驅結構10。結構10包括第一層12，該層具有上表面 以及背面12be應瞭解，圖i中說明之具體實例為特定微 電子過程之「快照（snapsh〇t)」。亦即，圖i中描述之步驟 可在方法開始時，如此快照描繪所製造之「堆疊。以仏）」 之第一層。或者’該等步驟可在正製造之堆疊令間或為^ 法之最後步驟，如此快照顯示某些參與構建堆疊之最後階 段因此，背面Ub可具有若干與之鄰接的層或基板13, 包括習用微電子基板’諸如選自由以下組成之群的基板： 珍、SiGe、Si〇2、Si3N4、銘、鶴、發化鶴、坤化嫁錯' 鈕、氮化鈕、珊瑚、黑金剛石、磷或硼摻雜玻璃及上述之 201033739 混合物。 第一層12較佳為旋塗碳層（rs〇c」）或非晶形碳層， 且其可根據任何先前技術方法（典型地包括旋塗）塗覆及 形成。基於將組成物中所有固體之總原子數視為1〇〇%，旋 塗碳層較佳應包含至少約8〇%之碳原子，且甚至更佳約8〇% 至約95%之碳原子。基於組成物中所包括之固體之化學結 構，一般熟習此項技術者可容易地計算該百分比。第一層 12之厚度典型地應為約50 nm至約1〇〇〇 nm，且較佳為約 100 nm 至約 300 nm。 結構10進一步包括與上表面12a鄰接之第二層14。第 —層14包括上表面14a，且可利用任何已知塗覆法塗覆且 根據已知條件加工。雖然第二層14較佳為硬遮罩層，但其 亦可為底部有機抗反射塗層。形成第二層14之組成物可利 用任何已知塗覆法塗覆，其中-種較佳方法為以約1〇〇〇 Pm m，GGG rpm (較佳約丨，· ρριη至約2 5⑽rpm)之 ⑩速度旋塗組成物約10秒至約6〇秒（較佳約2〇秒至約6〇 秒）之時間。隨後烘烤經成物以誘導熱交聯"he— ⑽sshnking )。較佳烘烤條件包括溫度為至少約⑽。c，較 佳為約12(TC至約25〇t，且p 且更佳為約1 60 C至約200°C，且 時間為約20秒至約60秒。交聯之第二層以厚…地 應為約2〇nm至約150nm，且較佳為約3〇nm至約1〇〇贈。 第二層14之η值較佳兔的, 佳為約1.4至約2，且更佳為約16 約2’且在使用波長（例如365 nm 248 nm i93nm、 57咖或13·5 nm)下，k值為約〇至約〇6。固化之第二 層丨4宜充分交聯以致其 將實質上不可溶於典型有機溶劑 7 201033739 十’典型有機溶劑諸如乳酸乙g旨、丙二醇甲醚乙酸醋 (PGMEA)、丙二醇甲醚（pGME)、丙二醇正丙醚（pnp)、 環己酮、丙嗣、γ 丁内酯（GBL)及其混合物。因此，當固 化之第二層14經受剝離測試（stripping test)時，其剝離 百分比（percent stripping )應小於約5%，較佳小於約1%， 且甚至更佳為約〇%。剝離測試包括首先藉由求取固化之第 二層14之5個不同位置處的量測值的平均值來確定厚度。 此為初平均膜厚度。接著，將溶劑（例如乳酸乙酯）捣拌 於固化之膜上約20秒，接著在約2,〇〇〇_3,5〇〇 rpm下旋轉乾 燥約20-30秒以移除溶劑。再使用橢圓對稱法在晶片之5 個不同點處量測厚度，且確定該等量測值之平均值。此為 終平均膜厚度。 剝離量為初平均膜厚度與終平均膜厚度之差。剝離百 分比為： 剝離~__lxl〇〇 0 U刀平均膜厚度j 100 在一較佳具體實例中，隨後可在固化之第二層14上塗 覆光敏組成物以形成成像層（未圖示） _形成…。雖然此可由已知方法=像但= 述-種可能的方法。在該方法中，光敏組絲較佳經旋塗， 隨後在至少約80°c、較佳約8(rc至約13(rc且更佳約i〇(rc 至約not之溫度下塗覆後烘烤（ΓρΑΒ」）約6〇秒至約i2〇 秒之時間。適合之光敏組成物包括市售光阻劑或任何其他 光敏組成物。成像層烘烤後之厚度典型地應為約5〇 至 201033739 約1，000 urn ’且更佳為約60 nm至約4〇〇 nm。 隨後將成像層曝露於輻射中，其中光遮罩（ph〇t〇mask ) (未圖不）位於成像層表面上方。該遮罩具有經設計以允許 e
輻射穿過遮罩且接觸成像層表面的敞開區域（叩⑶)。 遮罩之其餘固體部分經設計以阻止輻射在某些區域接觸成 像層之表面。熟習此項技術者應容易地瞭解，敞開區域及 固體部分之布置係基於欲在成像層及最終成像層下方之各 層中开/成之所要圖案來設計。本發明方法所使用之輻射的 大部分波長可低於500 nm，但較佳波長係選自由365 ηιη、 248 nm、193nm、157nm 及 13.5nm 組成之群。 曝露後，成像層冑露於輻射之料變得可溶於光阻顯 影劑中。曝露後’較佳在約8(rc至約l8『c、更佳約⑽。c 至約18代之溫度下使成像層經受曝露後烘烤（PEB)約60 秒至約120秒之時間。隨後使成像層之由上述方法變得可 冷之曝露部分與光阻顯影劑接觸以移除曝露部分 中所示之圖案化層16。 耿圃 t層16包括凸起特徵18(例如線卜雖然 顯不兩個凸起特徵^ 知❹… 瞭解可根據此項技術中之現行 夭識形成方干凸起柱外 上…4 各凸起特徵18包括實質上垂直於 上表面1 4a之JL· C,I .. J第—側壁20a及第二侧壁20b， 上平行於上表面l4a ★々， 及X質 之各別上表面22。此外，特徵18 度呎較佳為約20nm s从 竹锻丨8之寬 m至約100 nm，更佳為約22 ⑽’且甚至更佳為約32nm。 -至約8〇 铁而上法描述由光敏組成物形成凸起特徵18之方法 然而，應瞭解特微18介 I万去。 亦可由多種其他組成物形成。舉 9 201033739 。特徵18亦可在選自由抗反射層、硬遮罩層、非晶形碳 層、石夕層、氧化物（例如金屬氧化物）層組成之群的層中 形成。對於任何該等層類型，特徵18均將根據已知方法形 j舉例而a ’可在第三層14上形成特定層，此後在該特 層形成成像層。成像層隨後將如上所述經圖案化，且 將該圖案轉印（例如經由㈣）至替代層以形成特徵18。 無論形成特徵18之材料如何，關鍵在於提供具有彼等特徵 18之經圖案化之結構1〇。此外，特徵18之間距（_較 佳為約1:2至約1:4,且更佳為約1:3 (參見圖在一 尤佳具體實例中，妒為32 nm ’而為96疆。 旦經圖案化之結構1G由上述方法或所屬領域中已知 之其他方法形成’即可將可收縮組成物24塗覆於第二層Μ 之上表面Ua上以及特徵18之側壁心、鳩及上表面a 上。雖然可收縮組成物24可由任何已知方法塗覆，但較佳 為旋塗。 隨後加熱可收縮組成物24，因釋放許多小分子而使其 顯著收縮’從而形成圖“Ο中所說明之保形塗;| 26。加埶 可收縮組成物所至之溫度應視形成特徵18之材料而定。舉 =而言’當特徵18由光阻組成物形成時，加熱可收縮組成 物24至低於约12(rc之溫度，較佳低於約ii〇t，且更佳 約m：至約⑽。C。當特徵18由不為光阻組成物之材料形 成時’加熱可收縮組成物24至低於約綱。c之溫度，較佳 低於約250t，且更佳為約1〇(rc至約21(rc。 保形塗層26與特徵18之側壁施、鳥或上表面a 之間不宜存在化學相互作用。此允許方法可用於任何類型 201033739 之特徵18。此外，上述烘烤溫度允許方法在避免特徵a變 形之溫和條件下使用。 ❿ ❿ 較佳」等於仍參考圖1(c))，且甚至更佳5小於ρ 從而允許在極少韻刻下形成前間隔件。「心表示保形塗層 26之特徵18頂部最厚點處的厚度，而「万」表示保形塗層 26之特徵18之間最薄點（亦即，特徵之間的「谷」之最低 點）處的厚度。利用位置乂及及作為參考，可收縮組成物 24在該加熱步驟期間應收縮至少約25%，較佳至少約洲， 更佳至夕約50/。’且甚至更佳為約55%至約。
接著#考圖1⑷，使保形塗層26經受钱刻製程以形 成前間隔件28°適合之钱刻劑包括選自由Cl2、CF4、CH3F 及CHF3組成之群的#刻劑，且典型的餘刻速率為約】入〆 私至約1G A/秒’且較佳為約3 A/秒至約8 秒。另外可 經由習用濕式姓刻製程來蚀刻。各前間隔件28包含凸起特 徵18及可收縮組成物殘留物3〇。如圖1⑷中所描繪，殘留 物30緊貼各側壁2〇a、2〇b。 隨後自各前間隔件28移除凸起特徵18 (例如經由〇2 刻）’留下殘留物30f isi w、、 物〇(圖…））。殘留物30充當「間隔件 (—)」以形成極小特徵（例如小於約—、較佳小於 約5〇⑽且更佳小於約32⑽之線）。亦即，使結構㈣ 受钱刻製程，該触刻製程將由殘留物3〇形成之圓案轉印至 第二層14中’從而在第二層14中形成線34。蝕刻製程移 除殘留物30以及未受殘留％ 3〇保護之區域中之第二層 14 °適合之㈣劑包括選自自cl2、CF4、CH3F及咖3组 成之群的蝕刻劑，且典型的蝕刻速率為約ιΑ/秒至約⑽ 201033739 秒，且較佳為約3人/秒至約8 A/秒。必要時，可使用習用 技術將圖案進一步轉印至第一層12及基板13。 以上方法描述本發明之雙重圖案化方法、宜藉由增加 額外蚀刻步驟來修改雙重圖案化方法以得到三重圖案化方 法。該方法顯示於圖2中，其中使用類似編號指定類似材 料。又，除非另作說明，否則將使用關於圖丨所述相同之 加工條件（例如旋轉速度、溫度、蝕刻、時間等）。 參考圖2⑷，可見再次如上所述提供圖案化結構1〇。 ❹ 凸起特徵18典型地應具有前述寬度π。隨後「修整 (trimmed )」彼等特徵i 8，以使其各別寬度至少減少一半;圖 2(b))。亦即，經修整之特徵18，之寬度π較佳應為約⑽㈣ 至約9〇nm，更佳為約6〇nm至約8〇nm，且甚至更佳為約 70 nm。該修整可制任何已知方法實現其中—種適合之 方法包括電漿蝕刻。 α 如圖2(c)中所示，隨後使特徵18，及第二層Μ經受 蚀刻製程以得到拱形特徵18„及部分_之第二層Μ，= ❹ =^包括較低凸起特徵或「結適於 =刻步驟之㈣劑包括選自自c12、CF4、ch3^chf^ 成之群的钮刻劑，且业创的為λ ’· U的蝕刻速率為約1 Α/秒至約1〇Α/ 秒，且較佳為约3 Α/秒至約7Α/秒。 υΑ/ 隨後移除棋形特徵18，.（例如 中所示之圓案化結·38β使用已知)二:：2⑷ 將光敏層…2(e))塗覆於上…(名如…法） . C覆於上表面14a丨及結36上。如圄 2(0中所描繪，隨後圖案 如圖 凸起特徵42。各凸起特徵4…：顯影）感先層40 ’得到 起特徵42包括實質上垂直於上 12 201033739 之各別第一側壁44a及第二侧壁44b，以及實質上平行於上 表面l4a’之各別上表面46。 接著’如先前所述及如圖2(g)中所示，將可收縮組成 物24塗覆於第二層14'之上表面14a’以及特徵42之侧壁 44a、44b及上表面46上。隨後使組成物24經受前述收縮 製程（圖2(h))以形成保形塗層26。圖2(i)-(k)之其餘步驟 與以上關於圖l(d)-(f)所述之步驟類似。然而，應注意圖2 之具體實例使圖案三重化而非雙重化（亦即，圖2之具體 ® 實例之線34比圖1之線多50〇/〇 )。線34亦宜極小，寬度小 於約70 nm，較佳小於約50 nm，且更佳為約16 nm至約32 nm ° 最後，圖2(1)說明將圖案轉印至第一層12之額外步驟。 如同先前具體實例之情況，必要時，可將該圖案進一步轉 ' 印至基板1 3。 應瞭解，上述方法為與光阻劑無關，且如上所述塗層 與基板之間不存在相互作用。因此，該方法可擴展至任何 基板，且可在溫和條件（< 12〇〇c)下塗覆，此避免使原始 線變形。因此，該新穎方法係基於不同於先前技術方法之 不同機制且提供優於先前技術方法之顯著優點。該方法可 用於使密集線之出現率加倍且甚至三倍。如本文所使用之 「密集（dense)」係指至少約5〇%之表面積充滿特徵18之區。 用作可收縮組成物24之組成物 用作可收縮組成物24之組成物較佳為有機或有機金屬 組成物且應展現某些使之適於該應用的性質。舉例而言， 組成物在上述加熱步驟期間必須展現高收縮。此意謂若特 13 201033739 徵18由光阻組成物形成，則可收縮組成物24必須在低於 約1紙、較佳低於約U(rc且更佳約8代至約⑽。c之溫 度下分解，以便組成物在不破壞特徵18之情況下收縮。若 特徵18由不為光阻組成物之材料形成，則可收縮組成物24 必須在低於約300。〇、較佳低於約25〇。〇且更佳約i〇〇t：至約 2UTC之溫度下分解，以便組成物在不破壞特冑18之情況下 收縮。 可收縮組成物24較佳包含可用於將固體溶解或分散於 組成物24内之有機溶劑。溶劑系統較佳經選擇以使得其不 會使光阻圖案變形，其中較佳溶劑係選自由均三甲苯、甲 基異丁基甲醇、d-檸檬烯及其混合物組成之群。此對特徵 18由脆性典型地大於其他基板之光阻組成物形成之具體實 例而言尤其有利。在特徵18不是由光阻組成物形成之具體 實例中，溶劑系統可包括上述溶劑及/或選自由乳酸乙酯、 丙二醇曱㈣、丙二醇甲醚乙酸酯及丙二醇正丙醚組成之群 的溶劑。 亦非常希望可收縮組成物之蝕刻比特徵18慢。因此， 與特徵18相比，可收縮組成物之蝕刻選擇性較佳小於約 0-30,更佳小於約0.25,且更佳為約〇 〇〇1至約〇1〇。當特 徵18由光阻組成物形成時，使用A作為蝕刻劑實現該等數 字。當特徵18由不為光阻組成物之材料形成時，使用、 CF4、CHsF或CHF3作為蝕刻劑實現該等數字。 種適合的可收縮組成物包含分散或溶解於溶劑系统 中之交聯劑。交聯劑因其可自縮合（self_c〇ndense)形成明 顯收縮之網狀結構而為適合的。適合用於本發明之典型交 201033739 聯劑為胺基塑膠（anlin〇plast)’諸如曱基化聚（三聚氰胺_ 共-甲醛）（由 Cytec Industries 以名稱 Cymel® 303 銷售）0 其他適合之交聯劑包括選自由以下組成之群的交聯劑：丁 基化/異丁基化聚（三聚氰胺_共_甲醛）、六曱基三聚氰胺 (HMM )、甘脲（諸如由 cytec Industries 以名稱 powderlink® 銷售者）、1，3-雙（曱氧基曱基）_4,5_雙（曱氧基乙烯脲 (BMNU」）、l，3-雙（甲氡基曱基）腺（「」）及下列衍生 物：
❹ A
Η, ΟχΗ2χ+2, Χ= 1 - 12
收縮度視所釋放之醇的分子量及 組合高釋放莫耳質量之醇（諾&丁藉由 （堵如丁醇）及較高溫度之烘
可達成較大收縮。必要時，可將抗㈣聚合物（諸如聚’ 氧燒）與交聯劑播合以改進㈣選H 對於此類組成物，溶劑系統較佳包含一或多種選自由 15 201033739 以下組成之群的溶劑··丙二醇單甲鍵（「pgmD、均三甲 苯、甲基異丁基甲醇、d_檸檬烯及其混合物。此外，基於將 組成物之總重量視為刚重量％，該具體實例之組成物之固 體含量較佳為約1重量％至約15重量％，且更佳為約3重 量/〇至約10重量％。基於將組成物中之固體總重量視為⑽ 重量％’交聯劑之存在量較佳應為約8G重量％至約99重量 %，且更佳為約90重量％至約95重量％。 組成物亦將包含酸，諸如選自由以下組成之群的酸. 對甲苯續酸、二壬基萘確酸、三氟甲烷硫酸及十七氟辛烧 續酸。基於將組成物中之交聯劑總重量視為⑽重量％，酸 之存在量較佳應為，約i重量％至約2〇重量％，且更佳為約5 重量％至約1 〇重量％。 該含交聯劑之組成物家族更適於特徵18不是由光阻組 成物形成之具體實例’因為該家族之組成物在較高烘烤溫 度下達成較佳收縮。 m 其他適合的組成物包含分散或溶解於溶劑系統中之具 有在鏈聚合反應中酸不敎之侧鏈的聚合物。如先前所述 經由旋塗製備厚膜，且當烘烤膜時，酸使酸不穩定側鏈裂 解，引起揮發性產物釋放。當側鏈釋放時，臈明顯收縮。 收縮度由側鏈之組成及大小決定。侧鍵可經選擇以使之可 由酸在低溫（例如低於約12(rc)下裂解，從而使該家族之 組成物亦適用於特徵18由光阻組成物形成以及特徵 不為光阻組成物之材料形成的情形。 用於該等聚合物中之單體包括選自由苯乙烯、丙烯酸 甲醋及丙烯酸酯衍生物組成之群的單體。一些適合之 於 201033739 - 苯乙烯之單體包括：
❹ 酸酯單體包括：
R
Ο
酸不穩定側鍵之來源可 τ、包括選自由第 醯基家族、金剛燒基家族及内醋家族組成 乙 二丁基家族 之群的來源 要時，亦可使用抗蝕組份製備具有適合之抗蝕性質之共聚 物0 17 201033739 對於此類組成物，溶劑系統較佳包含一或多種選自由 以下組成之群的溶劑：均三甲苯、甲基異丁基甲醇、d檸檬 稀其尾σ物必匕外，基於將組成物之總重量視為⑽重 量％’該具體實例之組成物之固體含量較佳為約2重量％至 約15重量％，且更佳為約3重量％至約ι〇重量％。基於將 組成物中之固體之總重量視為1〇〇重量％，聚合物之存在量 較佳應為約85重量％至約99重量％，且更佳為約9〇重量％ 至約95重量％。
該具體實例之組成物亦將包含酸，諸如選自由以下組 成之群的酸：W苯錢、二壬基萘錢、三氟甲烧硫酸 及十七氟辛烷磺酸。基於將組成物中之聚合物之總重量視 為100重量❶/。，酸之存在量較佳應為約1重量％至約1〇重 量且更佳為約3重量％至約7重量％。 重溶劑與抗蝕性聚合物之摻合物為適合之收縮組成物 24之又一實施例。抗蝕性聚合物可為與上述特徵1 8相比具
有蝕刻選擇性之任何聚合物。較佳該類抗蝕性聚合物為含 碎聚合物。 在旋塗形成均一膜後，重溶劑仍與抗蝕性聚合物在一 起。隨後在烘烤（較佳低於約12(rc，使之適於光阻特徵18 以及非光阻特徵18 )期間，重溶劑完全汽化，且僅留下抗 蝕性聚合物來形成保形塗層。「重溶劑（Heavy s〇lvent)」係 指與抗蝕性聚合物相容且沸點允許在旋塗後保留但在前述 收縮溫度期間汽化的溶劑。重溶劑之典型實例包括選自由 以下組成之群的溶劑：丙烯酸2-乙基-2-金剛烷酯、甲基丙 烯酸2·甲基-2·金剛烷酯、丙烯酸2-甲基·金剛烷酯、κ+ _ 18 201033739 稀及其混合物。 對於此類組成物，基於將組成物之總重量視為〗重 量％，組成物之固體含量較佳為約2重量％至約15重量％， 且更佳為約3重量％至約1G重量％。基於將組成物中之固 體總重量視為100重量％，聚合物之存在量較佳應為約2〇 重量％至約80重量。/。’且更佳為約4〇重量％至約6〇重量 ❹
適於可收縮組成物24之材料之另—家族包括分散或溶 解於溶劑系統中之有機金屬化合物。較佳有機金屬化合物 為在前述收縮溫度下會釋放配位體形成金屬氧化物之化合 物。該揮發性配位體消除可產生保形塗層26。配位體可在 低温（例如低於約12〇。〇下釋放，從而使該家族之組成物 亦適合用於特徵18由光阻組成物形成以及特徵18由不為 光阻組成物之材料形成的情形。 典型實例包括選自由以下組成之群的物質：雙(乙醯乙 酸乙酿）二異丙醇鈦（IV)、雙（乳酸銨）二氫氣化欽（ιν)、（雙 -2,3-戊二酸)二異丙醇鈦(IV)、乙醯乙酸乙醋二異丙醇銘、 雙（M-戊二酸）氧化師v)、雙（2,4戊二酸）二丁醇錯雙（乙 醯乙酸乙醋)戊二酸醋銘、雙(2,4·戊二酸)二丁醇給、2,4-戊 一酸飢III及聚（鈦酸二丁酿）。 、下顯丁备使用雙（乙酿乙酸乙醋）二異丙醇欽（IV)作 為有機金屬化合物時會出現之配位體釋放： 19
I 201033739 Η H3C、 .CH, "CH〇 Η3〇(Η2〇)3〇-,Τΐ^* _^~o(ch2)3ch3 Δ
Tio, Η3(Τ
Y ,c、 、ch3 對於此類組成物，溶劑系統較佳包含一或多種選自由 以下組成之群的溶劑··甲基異丁基甲醇、均三甲苯、i十二 烯及其混合物。此外’基於將組成物之總重量視為⑽重 量。/。’組成物之固體含量較佳為、約2重4%至約15重量％， θ 且更佳為約3重量％至約10重量％。基於將組成物中之固 體總重量視為1〇〇重量％’有機金屬化合物之存在量較佳應 為約40重量％至約90重量％，且更佳為約4〇重量％至約 80重量％。 實施例 以下實施例闡述本發明之較佳方法。然而，應瞭解提 供該等實施例以說明本發明，且其中任何内容均不應視為 對本發明整體範疇之限制。 © 實施例1 於極性溶劑中之交聯劑 藉由將 10 公克 Cymel® 303 (自 Cytec Industries，West
Paterson，NJ獲得之交聯劑）溶解於9〇公克極性溶劑p(JME (自 General Chemical West LLC，Hollister, CA 獲得）中製 備溶液。所得溶液包含〇_25 wt%交聯劑。接著，添加〇 〇25 公克對甲苯績酸（「p-TSA」，自 Sigma-Aldrich，St. Louis，ΜΟ 20 201033739 獲得）作為觸媒。攪拌混合物10分鐘，隨後經0.1 /xm過濾 器過濾。以1,500 rpm將調配物旋塗於平面矽晶片上60秒， 且量測膜或塗層厚度。隨後在205 °C下烘烤晶片60秒，其 中流程A描繪該反應。再量測塗層厚度以獲得收縮。烘烤 期間，厚度減少了 35%。 亦以1，500 rpm將調配物旋塗於具有矽線之晶片上60 秒，且在205°C下烘烤60秒。圖3顯示矽線上所得之保形 塗層。 ❹
流程A
Rxcr^NN//SN'〇/R
R = H, CH3 ^CH2CH2CH2Chb H+ i --聚合物網狀結構+ ROH 1 △ 實施例2 於非極性溶劑中之交聯劑 藉由將10公克Cymel® 303溶解於90公克非極性溶劑 均三曱苯（自Sigma-Aldrich，St. Louis, MO獲得）中製備 溶液。接著，添加0.05公克二壬基萘磺酸溶液（「DNNSA」， 自 Sigma-Aldrich，St. Louis，MO 獲得）以獲得包括 0.5 wt% 交聯劑之溶液。攪拌混合物10分鐘，隨後經0.1 /im過濾器 過遽。 以1,500 rpm將調配物旋塗於平面矽晶片上60秒，且 21 201033739 量測塗層厚度。隨後在2051：下烘烤晶片60秒，且量測塗 層厚度以確定塗層收縮。烘烤期間，塗層厚度減少了 35%。 亦以1 ’5 00 rpm將調配物旋塗於具有矽線之晶片上6〇 秒，隨後在205°C下烘烤60秒。圖4顯示矽線晶片上所得 之由該調配物製成的保形塗層。 實施例3 聚（Adamantate EA) 在該程序中’將1〇公克（4〇 wt% ) Adamantate EA (丙 稀酸2-乙基-2-金剛烷酯；自Idemitsu Kosan有限公司，Chiba, ◎ Japan 獲得）及 〇. 1 公克（Adamantate EA 的 1 wt% )偶氮二 異丁腈（「八18!^」，自81呂11^-八1(11^11，31[〇1^8，崖0獲得之 引發劑）溶解於15公克均三曱苯中。在1001：下聚合24小 時’此後使用均三甲笨稀釋溶液至7.5 wt%。接著，向聚合 物溶液中添加〇.〇5公克DNNSA(聚合物的0.5 wt%)。攪拌 混合物10分鐘，且經〇」μιη過濾器過濾。以1，500 rpm將 調配物旋塗於平面矽晶片上6〇秒，且量測塗層厚度。隨後 在1 l〇°C下烘烤晶片60秒，且再量測塗層之厚度以獲取收 〇 縮資料。烘烤期間，塗層厚度減少了 70%。流程B描繪烘 烤期間揮發性組份之釋放。 亦以1，500 rpm將調配物旋塗於經光阻劑圖案化之晶片 上60秒，且在9〇〇c下烘烤6〇秒。圖5顯示光阻線頂部所 得之保形塗層。 22 201033739
流程B
旋塗後之膜 實施例4 ® 聚（Adamantate EA-聚石夕氧） 藉由將 8 公克（32 wt0/。）Adamantate EA 及 2 公克（8 wt% )聚矽氧甲基丙烯酸酯單體（3_(甲基丙烯醯基氧基）丙 基-參（三甲基矽氧基）-矽烷，自TCI America，Portland, OR 獲得）溶解於15公克均三甲苯中製備溶液。在1〇〇〇c下聚 合24小時。使用1〇8 3公克均三甲苯稀釋溶液至7 5 wt% ’ 且隨後向溶液中添加0 05公克DNNSA (為聚合物的〇5 φ Wt /° )。擾拌混合物10分鐘，且經〇. 1 μπι過濾器過濾。以 1，500 rpm旋塗平面矽晶片60秒，且量測塗層厚度。隨後在 H〇°C下烘烤晶片60秒’且再量測塗層之厚度以獲取收縮資 料。洪烤期間，塗層厚度減少了 55%。 亦以1，500 rpm將調配物旋塗於經光阻劑圖案化之晶片 上60秒，且在9(rc下烘烤6〇秒。圖6顯示光阻線頂部所 得之保形塗層。 在以下條件下，使用Oxford Plasmalab RIE量測塗層在 不同氣體中之蝕刻速率：功率：100 W ;壓力：5〇毫托 (mT〇rr)’ 背面氦氣（backside Helium ) : 3 毫托；及氣體. 23 201033739 50 seem。蝕刻30秒後塗層與市售光阻劑（AR1682J，自JSR Micro，Sunnyvale，CA獲得）及熱氧化層相比之钱刻選擇性 列於表1中。 表1 氣體 〇2 cf4 Cl2 AR1682J 0.25 1.2 1.4 熱氧化物 — 2.4 — 實施例5 ❹ 聚（Adamantate EA-聚石夕氧） 藉由將8公克（32 wt% ) Adamantate EA及2公克（8 wt% )聚矽氧曱基丙烯酸酯單體（MCR-M07，以單甲基丙 烯酸酯封端之聚雙曱基矽氧烷；分子量：600-800 g/mol ; 自Gelest公司，Morrisville，PA獲得）溶解於15公克均三甲 苯中製備溶液。在80°C下聚合24小時。使用108.3公克甲 基異丁 基曱醇（自 Sigma-Aldrich，St. Louis，MO 獲得）稀 釋溶液至7.5 wt%，且隨後向溶液中添加〇 05公克DNNSA Ο (聚合物的0.5 wt%)。攪拌混合物1〇分鐘，隨後經〇丨μιη 過濾器過濾。以1，500 rpm旋塗平面矽晶片60秒，且量測 塗層之厚度。隨後在11(TC下烘烤塗層60秒，且再量測塗 層之厚度以獲取收縮資料。烘烤期間，塗層厚度減少了 55%。 在以下條件下，使用Oxford Plasmaiab RIE量測在不同 氣體中之敍刻速率：功率：100 W;壓力：5〇毫托；背面氛 氣：3毫托；氣體：50 seem ^蝕刻30秒後塗層與市售光阻 劑（AR1682J )及熱氧化層相比之蝕刻選擇性列於表2中。 24 201033739 表2 氣體 〇2 cf4 Cl2 AR1682J 0.10 1.2 1.4 熱氧化物 -- 2.4 —— 如圖7(a)中圖解所描繪’使用經抗蝕劑圖案化之晶片作 為模板。使用底部有機抗反射塗層（ARC® 29A，自Brewer 〇 Science公司，Rolla，MO獲得）作為經圖案化之光阻劑與基 板之間的層。亦以1，〇〇〇 rpm將上述調配物旋塗於經光阻劑 圖案化之晶片上60秒，隨後在90。(：下烘烤60秒。圖7(b) 顯示光阻線頂部所得之保形塗層。 隨後使用氯氣（Cl2 : 50 seem ;氬氣：20 seem ;功率： 200 W ;及壓力：50毫托）钱刻經塗佈之晶片，且圖7(c) 顯示側壁形成。進一步使用氧氣（〇2 : 5〇 sccm ;功率：1〇〇 W ’壓力：1 〇〇毫托）蝕刻晶片以移除抗蝕劑。然而，間隔 © 件因使用底部有機抗反射塗層作為底層而塌陷，該塗層在 氧氣中之蝕刻比間隔件快得多（圖7(d))。 為解決塌陷問題，用圖8(a)中所示之層堆疊製備新模 板。詳言之’將OptiStack SOC 110 (旋塗碳或「SOC」，自 Brewer Science Brewer Science 公司，Rolla” MO 獲得）底層 塗覆於矽晶片上。接著，將底部含矽抗反射塗層 〇PTISTACK®HM710(硬遮罩或「HM」，自 Brewer Science 公司，Rolla，MO獲得）塗覆於旋塗碳之頂部。在硬遮罩層 頂部上形成光阻層（Pi6〇〇1，自TOK，Japan獲得），接著圖 25 201033739 案化以形成線。 以2,000 rpm將上述調配物旋塗於經光阻劑圖案化之晶 片上60秒，接著在贼下烘烤6〇秒（參見圖8(b))。使用 氯氣（Cl2 . 50 secm ;氬氣：20 sccm ;功率：2〇〇 w ;壓力： 50毫托）蝕刻經塗佈之晶片。圖8(c)顯示側壁形成。 進一步由氧氣蝕刻晶片以移除光阻劑（〇2 : 5〇 sccm ; 功率：100W;壓力：100毫托）β圖8(d)顯示抗蝕劑移除之 後，站立之間隔件。使用Cl蝕刻（Ch: 35sccm;功率： 1〇〇 W;壓力：50毫托）將圖案轉印至底部硬遮罩層上（圖 ❹ 8(e))。 實施例6
Adamantate EM與有機聚矽氧共聚物之摻合物 藉由將9公克（36 wt% )聚矽氧甲基丙烯酸酯單體 (3-(甲基丙稀酿基氧基）丙基_參（三曱基碎氧基）碎烧，自tci America, Portland，OR 獲得）、1 公克（溶液的 4 wt〇/〇 )甲基 丙烯酸縮水甘油酯（glycidyl methacrylate )及0.1公克（單 體的1 wt%) AIBN溶解於15公克均三甲苯中製備溶液。在 〇 100°C下聚合24小時’且溶液不經進一步純化即使用。 製備均三甲苯及上述聚合物（6 wt% )及23.3公克（14 wt%)甲基丙稀酸2-乙基-2-金剛烧醋（由Idemitsu Kosan 有限公司，Chiba，Japan以名稱Adamantate EM銷售）之溶 液。攪拌混合物10分鐘，且經0.1 μιη過濾器過濾。以1，500 rpm將混合物旋塗於平面矽晶月上6〇秒，且量測塗層厚度。 隨後在110°C下烘烤塗層60秒，且再量測塗層之厚度以獲 取收縮資料。烘烤期間，塗層厚度減少了 70%。 26 201033739 實施例7 有機金屬化合物 將雙（乙酼乙酸乙酯）二異丙醇鈦（IV) ( 〇5 g，自 Sigma_Alddch，St· Louis，MO 獲得）溶解於 9 5 g 甲基異丁 基曱醇中。攪拌混合物1 〇分鐘，且經〇丨過濾器過濾。 以1，500 rpm將混合物旋塗於平面矽晶片上6〇秒，且量測 塗層厚度。隨後在11 (TC下烘烤塗層60秒，且再量測塗層 之厚度以獲取收縮資料《烘烤期間，塗層厚度減少了 8〇〇/〇。 【圖式簡單說明】 圖1圖解描緣根據本發明之雙重圖案化方法； 圖2為描繪根據本發明之三重圖案化方法之圖解說明； 圖3為實施例1中製備之保形塗層之掃描電子顯微鏡 (scanning electron microscope，SEM)照片； 圖4為顯示實施例2中製備之保形塗層之SEM照片； 圖5為實施例3中製備之保形塗層之SEM照片； 圖6為顯示實施例4中製備之保形塗層之SEM照片； 圖7(a)圖解說明實施例5中所使用之模板堆疊 (template stack)； 圖7(b)為實施例5中製備之保形塗層之SEM照片； 圖7(c)為蝕刻實施例5中之結構之後形成的側壁之 SEM照片； 圖7(d)為顯示進一步蝕刻以移除實施例5之結構的光 阻劑後出現之塌陷的SEM照片； 圖8(a)圖解説明實施例5中所使用以防止圖案塌陷之 27 201033739 替代模板堆叠； 圖8(b)為實施例5中製備之塗層之SEM照片； 圖8(c)為蝕刻實施例5中之替代結構之後形成的側壁 之SEM照片； 圖8(d)為顯示實施例5之替代結構在進一步蝕刻以移 除光阻劑之後的SEM照片；及 圖8(e)為顯示實施例5之替代結構在進一步飯刻以 圖案轉印至硬遮罩層之後的SEM照片。 ' 【主要元件符號說明】
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Claims (1)

  1. 201033739 七、申請專利範圍： 1.一種形成微電子結構之方法，該方法包含·· 提供具有圖案化表面的前驅結構，該圖案化表面包括 至少-個具有第一與第二側壁及上表面之凸起特徵； 將可收縮組成物塗覆於該圖案化表面上，該組成物覆 蓋該特徵側壁及上表面； ,加熱該可收縮組成物以在該圖案化表面上及該特徵上 方形成該組成物之保形層；及 移除至/ 分該保形層以得到__包含該特徵及胃 特徵侧壁之該保形層之殘留物的前間隔件結構。 2.如申請專利範圍第！項之方法，其中該可收縮組成物 在該塗覆之後及該加熱之前具有初厚度，且該保形層在該 加熱之後及該移除之前具有終厚度，該終厚度比該初厚度 小至少約25%。 3·如申請專利範圍第！項之方法，其進一步包含自該前 間隔件結構移除該凸起特徵以在該圖案化表面上留下該殘 留物。 4_如申請專利範圍第3項之方法，其中該圖案化表面在 該塗覆之前具有第一圖案且在移除該凸起特徵之後具有第 二圖案，該第二圖案為該第一圖案的雙倍。 5·如申請專利範圍第3項之方法，在該圖案化表面下方 有-或多$，且該方法進—步包含將由該殘留物形成之圓 案向下轉印至位力該圖案化表面下方之該等層之一或多 者。 6.如申請專利範圍第！項之方法，該圖案化表面包括至 29 201033739 =固彼此緊密鄰接之該凸起特徵，”在該加熱之後， 入徵,表面上有該保形層之最大厚“且該圖案化表面 上介於遠兩個凸起牲Μ 凸起特徵之間的某點處具有最小厚度5，且忍 小於或等於4。 申月專利範圍帛i項之方法，其中該前驅結構包 含： 具有上表面之第一層； 面鄰 具有上表面之第二層，該第二層與該第-層上表 接；且 Ο 5亥圖案化表面與該第二層上表面鄰接。 ::申請專利範圍第7項之方法’該第一層包含旋塗碳 層包含硬遮罩層，且該圖案化表面包含光敏層。 ㈣9·如申請專利範圍第1項之方法，該圖案化表面具有多 個間距為約1:2至約1:4之該凸起特徵。 有多 ❹ =請專利範圍第！項之方法其中該圖案化結構 徵：二含位於該至少一個凸起特徵下方之第二凸起特 :::第二凸起特徵具有第一與第二側壁及上表面，且該 傾"個凸起特徵係與該第二凸起特徵側壁及上表面接 :成該第二凸起特徵及該至少一個凸起特徵係由不同材: 步包含自該 圖案化表面 11.如申請專利範圍第10項之方法，其進一 前間隔件結構移除該至少—個凸起特徵以在該 上留下該殘留物及該第二凸起特徵。
    12·如申請專利範圍 該塗覆之前具有第一 第11項之方法，其中該圖案化表面 圖案且在移除該至少一個凸起特徵 30 201033739 之後具有第二圖案’該第二圖索為該 13,如申請專利範圍第i項之、 圖案的二倍。 物係選自由以下組成之群： 方法’其中該可收縮組成 (〇包含分散或溶解於溶劑 ⑴包含分散或溶解於溶劑系統：交聯：之組成物： 物’該聚合物包含酸不穩定側鏈；、、. < 聚合物之組成 (c )包含分散或溶解於包含六 録聚合物之組成物；& ，合劑之溶劑系統中的抗 ❹ ⑷包含溶解或分散於溶劑系統中之有機金屬化合物 之組成物。 其中該可收縮組成 14_如申請專利範圍第13項之方法， 物為（a)’且該交聯劑係選自由以下組成之群：甲基化聚（三 聚氰胺-共-曱醛）、丁基化聚（三聚氰胺-共·甲醛）、異丁基: 聚（三聚氰胺-共-曱搭）、六甲基三聚氰胺、甘腺、(甲 氧基甲基）-4,5-雙（甲氧基）-乙烯脲、1，3-雙（甲氧基甲基）腺及 下列衍生物：
    31 201033739 A
    、Η· CxH2x+2, X= 1 叫2 B
    r/〇x/n 丫 nV〇、r
    :H2.;
    o 15. 如申請專利範圍第i3 ^ A 峭您方法，其中該可收縮組成 物為（b)’且該聚合物包含選自 史目由本乙烯、甲基丙烯酸酯 及丙烯酸酯組成之群的單體， 一 〃干姐見該酸不穩定側鏈係選自由 第三丁基、乙醯基、金剛烷基及内酯組成之群。 16. 如申請專利範圍第13項之方法，其中： 該可收縮組成物為（c ); 比 〇 當使用〇2作為蝕刻劑時，與該至少—個凸起特徵相 該聚合物具有小於約0.30之蝕刻選擇性；且 該重溶劑係選自由以下組成之群：丙烯酸2_乙基_2•金 剛燒8曰、甲基丙烯酸2_甲基_2-金剛燒酯、丙稀酸2-甲基_ 金剛烧酯、1-十二烯及其混合物。 17. 如申請專利範圍第13項之方法，其中該可收縮組成 物為（d)’且該有機金屬化合物係選自由以下組成之 32 201033739 雙（乙醯乙酸乙酯）二異丙醇鈦（ιν)、雙（乳酸銨）二氫氧化鈦 (IV)、（雙-2,3-戊二酸）二異丙醇鈦（IV)、乙醯乙酸乙酯二異 丙醇鋁、雙（2,4-戊二酸）氧化釩（IV)、雙（2,4-戊二酸）二丁醇 鍺、雙（乙醯乙酸乙酯）戊二酸鋁、雙（2,4-戊二酸）二丁醇铪、 2’4-戊二酸釩III及聚（鈦酸二丁酯）。 18.如申請專利範圍第丨項之方法，其中該加熱包含在 小於約30(TC之溫度下加熱。
    19.如申請專利範圍第18項之方法，其中該加熱包含在 、於約120。(：之溫度下加熱。 包：〇.如申請專利範圍第19項之方法其中該圖案化表面 规層，且該可收縮組成物包含選自由均三 …基甲醇、d韻烯及其混合物組成之群的：劑。、 八 圖式： (如次頁）
    33
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KR20110111473A (ko) 2011-10-11
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US9640396B2 (en) 2017-05-02
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