TWI400300B - 以矽為主之硬質罩幕組成物（Ｓｉ－ＳＯＨ；以Ｓｉ為主之旋塗硬質罩幕）以及使用該組成物製造半導體積體電路裝置的方法 - Google Patents

以矽為主之硬質罩幕組成物（Ｓｉ－ＳＯＨ；以Ｓｉ為主之旋塗硬質罩幕）以及使用該組成物製造半導體積體電路裝置的方法 Download PDF

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TWI400300B
TWI400300B TW098100849A TW98100849A TWI400300B TW I400300 B TWI400300 B TW I400300B TW 098100849 A TW098100849 A TW 098100849A TW 98100849 A TW98100849 A TW 98100849A TW I400300 B TWI400300 B TW I400300B
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tetrabutylammonium
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TW200940651A (en
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Sang Kyun Kim
Hyeon Mo Cho
Sang Ran Koh
Mi Young Kim
Hui Chan Yun
Yong Jin Chung
Jong Seob Kim
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Cheil Ind Inc
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Description

以矽為主之硬質罩幕組成物(Si-SOH；以Si為主之旋塗硬質罩幕)以及使用該組成物製造半導體積體電路裝置的方法 發明領域
本發明係關於一種可藉旋塗法(spin-on coating)施用之以矽為主之硬質罩幕組成物(後文也稱作為「以矽為主之旋塗硬質罩幕(Si-based spin-on hardmask；Si-SOH)組成物」)、一種用於使用該硬質罩幕組成物製造半導體積體電路裝置之方法、及一種使用該方法所製造之半導體積體電路。
發明背景
隨著半導體微電路中所使用之線寬的縮窄，由於圖樣之縱橫比原故，要求使用具有較小厚度之光阻。但太薄的光阻可能發生於隨後圖樣轉印(亦即蝕刻)過程中執行光罩角色的困難。換言之，因薄的光阻於蝕刻期間容易被磨耗，下方基材無法被蝕刻至期望的厚度。
欲解決此等問題，導入硬質罩幕方法。硬質罩幕為具有高度蝕刻選擇性特徵之材料。典型的硬質罩幕係由兩層所組成(參考第1圖)。參考第1圖，循序於基材上形成以碳為主之硬質罩幕及以矽為主之硬質罩幕，及於以矽為主之硬質罩幕組成物上塗覆一光阻。雖然光阻厚度極小，但因以矽為主之硬質罩幕對光阻之蝕刻選擇性比對基材之蝕刻選擇性更高故，薄的光阻圖樣容易轉印至以矽為主之硬質罩幕。使用已製作圖樣之以矽為主之硬質罩幕作為罩幕，進 行以碳為主之硬質罩幕的蝕刻，來將該圖樣轉印至以碳為主之硬質罩幕。最後，使用已製作圖樣之以碳為主之硬質罩幕作為罩幕，進行基材之蝕刻，來將該圖樣轉印至基材。結果儘管使用薄的光阻，基材可被蝕刻至期望的厚度。
大致上，硬質罩幕係以工業規模於半導體製造方法中藉化學氣相沉積(CVD)製造。大半情況下，於CVD期間粒子的形成為無可避免。此等粒子嵌入硬質罩幕內，造成其難以檢測。於具有寬大線寬的圖樣中，粒子的存在無關緊要。但即使小量粒子也大為影響線寬縮窄的最終元件之電氣性質，造成元件量產上的困難。此外，鑑於CVD之特性，CVD之缺點在於製造硬質罩幕需要長時間與昂貴的成本。
於此等情況下，需要有可藉旋塗法施用之硬質罩幕材料。旋塗法之優點在於容易控制粒子的形成，處理時間短且可使用既有的塗覆機，不會招致相當高的額外投資成本。但欲製備旋塗硬質罩幕材料有若干嚴重問題有待解決。舉例言之，屬於本發明之多個面相中之一者之以矽為主之硬質罩幕材料就蝕刻選擇性而言必須具有夠高的矽含量。但矽含量過高造成硬質罩幕材料之塗覆性變差及儲存不安定。亦即難以找出適合用於硬質罩幕量產之材料的最佳矽含量。無法控制材料之表面物理性質可能導致以另一種材料塗覆時的缺陷。
發明概要
本發明致力於解決前述問題，本發明之目的係提供具有高度蝕刻選擇性及良好儲存安定性且可修飾其表面物理性質之一種以矽為主之旋塗硬質罩幕組成物。
本發明之另一目的係提供一種使用以矽為主之硬質罩幕組成物製造半導體積體電路裝置之方法。
根據本發明之一個實施例，提供一種以矽為主之旋塗硬質罩幕組成物，其包含具有端末羥基(-OH)及烷氧基(-OR)且含有連接兩個相鄰矽原子之鏈接基之聚矽倍半氧烷作為基本樹脂。
特定言之，本發明之以矽為主之硬質罩幕組成物包含(a)式1表示之有機矽烷聚合物：{(SiO 1.5 -Y-SiO 1.5 ) x (R 3 SiO 1.5 ) y (XSiO 1.5 ) z }(OH) e (OR 6 ) f (1)
其中x、y及z表示聚合物中之重複單元(SiO1.5-Y-SiO1.5)、(R3SiO1.5)及(XSiO1.5)之相對比且滿足關係式0.05x0.9、0.05y0.9、0z0.9及x+y+z=1；e及f分別表示鍵結至矽(Si)原子之端末-OH基數目及端末-OR基數目對聚合物中之2x+y+z矽(Si)原子數目之比，且滿足關係式0.03e0.2及0.03f0.25；X為含有至少一個經取代或未經取代之芳香環之C6-C30官能基；R3為C1-C6烷基；Y為選自於由芳香環、經取代或未經取代之線性或分支C1-C20伸烷基、主鏈中含有至少一個芳香環或雜環系環或具有至少一個脲基或異三聚氰酸酯基之C1-C20伸烷基及含有至少一個多重鍵之C2-C20烴基所組成之組群之鏈接基；及R6為C1-C6烷 基，及(b)溶劑。
根據本發明之另一個實施例，提供一種使用該硬質罩幕組成物製造半導體積體電路裝置之方法。
本發明之硬質罩幕組成物具有良好儲存安定性且可用於蝕刻期間對氧電漿氣體具有良好耐蝕刻性之硬質罩幕之製造。使用該硬質罩幕組成物所製造之硬質罩幕儘管其厚度極小仍然容易轉印圖樣。此外，該硬質罩幕之表面親水性係經改性，故可改良該硬質罩幕與上方覆蓋薄膜及下方覆蓋薄膜間之可相容性。此外，該硬質罩幕由於可吸光，故於暴露於半導體製造程序期間可協助準確地製成光阻圖樣。
特別，該硬質罩幕之高蝕刻選擇性有助於薄光阻層圖樣通過該硬質罩幕而轉印至期望的基材。此外，其表面物理性質可經改性之硬質罩幕容易塗覆以薄光阻或抗反射塗層(ARC)。
圖式簡單說明
第1圖為由以碳為主之硬質罩幕、以矽為主之硬質罩幕及阻劑層於基材上所組成之多層膜之示意剖面圖；第2圖顯示式5化合物之特定實例；及第3圖顯示式7化合物之特定實例。
較佳實施例之詳細說明
本發明提供一種以矽為主之硬質罩幕組成物包含(a)式1表示之有機矽烷聚合物：{(SiO 1.5 -Y-SiO 1.5 ) x (R 3 SiO 1.5 ) y (XSiO 1.5 ) z }(OH) e (OR 6 ) f (1)
其中x、y及z表示聚合物中之重複單元(SiO1.5-Y-SiO1.5)、(R3SiO1.5)及(XSiO1.5)之相對比且滿足關係式0.05x0.9、0.05y0.9、0z0.9及x+y+z=1；e及f分別表示鍵結至矽(Si)原子之端末-OH基數目及端末-OR基數目對聚合物中之2x+y+z矽(Si)原子數目之比，且滿足關係式0.03e0.2及0.03f0.25；X為含有至少一個經取代或未經取代之芳香環之C6-C30官能基；R3為C1-C6烷基；Y為選自於由芳香環、經取代或未經取代之線性或分支C1-C20伸烷基、主鏈中含有至少一個芳香環或雜環系環或具有至少一個脲基或異三聚氰酸酯基之C1-C20伸烷基及含有至少一個多重鍵之C2-C20烴基所組成之組群之鏈接基；及R6為C1-C6烷基，及(b)溶劑。
有機矽烷聚合物(a)為式2、3及4表示之化合物之縮聚物：(HO) a (R 1 O) (3-a) Si-X (2)
其中R1為C1-C6烷基，0a3，及X為含有至少一個經取代或未經取代之芳香環之C6-C30官能基；(HO) b (R 2 O) (3-b) Si-R 3 (3)
其中R2為C1-C6烷基，0b3，及R3為C1-C12烷基；及(HO) c (R 4 O) (3-c) Si-Y-Si(OH) d (R 5 O) (3-d) (4)
其中R4及R5分別為C1-C6烷基，0c3，0d3，及Y為選自於由芳香環、經取代或未經取代之線性或分支C1-C20伸烷基、主鏈中含有至少一個芳香環或雜環系環或具有至少一個脲基或異三聚氰酸酯基之C1-C20伸烷基及含有至少一個多重鍵之C2-C20烴基所組成之組群之鏈接基。
有機矽烷聚合物(a)係經由於酸催化劑存在下，式5、6及7表示之化合物之水解產物縮聚合而製備：(R 1 O) 3 Si-X (5)
其中X為含有至少一個經取代或未經取代之芳香環之C6-C30官能基，及R1為C1-C6烷基；(R 2 O) 3 Si-R 3 (6)
其中R2為C1-C6烷基及R3為C1-C12烷基；及(R 4 O) 3 Si-Y-Si(OR 5 ) 3 (7)
其中R4及R5分別為C1-C6烷基，及Y為選自於由芳香環、經取代或未經取代之線性或分支C1-C20伸烷基、主鏈中含有至少一個芳香環或雜環系環或具有至少一個脲基或異三聚氰酸酯基之C1-C20伸烷基及含有至少一個多重鍵之C2-C20烴基所組成之組群之鏈接基。
有機矽烷聚合物(a)具有2,000至90,000之重量平均分子量。
式5化合物之特定實例如下(Me=甲基，R=C1-C6烷基)。
式7化合物之特定實例如下。
有機矽烷聚合物之製備方法係經由相對於100重量份式5、6及7化合物，混合0至90重量份式5化合物，5至90重量份式6化合物及5至90重量份式7化合物，且允許5至90重量份該混合物於0.001至5重量份酸催化劑存在下於100至900重量份反應溶劑反應而製備。
該酸催化劑可選自於由硝酸、硫酸、鹽酸、對甲苯磺酸一水合物、硫酸二乙酯、及其組合所組成之組群。
水解反應或縮合反應適合藉改變酸催化劑之類別、數量及添加模式而適當地控制。酸催化劑之用量為0.001至5重量份。酸催化劑用量小於0.001重量份顯著減慢反應速率，而酸催化劑之用量大於5重量份造成反應速率之過度加 快，因而不可能製備具有期望分子量的縮聚合產物。
反應溶劑可選自於由丙酮、四氫喃、苯、甲苯、***、氯仿、二氯甲烷、乙酸乙酯、丙二醇甲醚、丙二醇***、丙二醇丙醚、乙酸丙二醇甲醚、乙酸丙二醇***、乙酸丙二醇丙醚、乳酸乙酯、γ-丁內酯、及其混合物所組成之組群。
式2、3及4化合物可經由於酸催化劑存在下分別水解式5、6及7化合物而製備。
利用式5化合物所含括之經取代或未經取代之芳香族基吸收深紫外光(DUV)區之紫外光的能力，本發明之硬質罩幕組成物具有優異的抗反射性。本發明之硬質罩幕組成物藉由控制有機矽烷聚合物中之經取代或未經取代之芳香族基之數目而具有於特定波長期望的吸光率及折射率。以100重量份式5、6及7化合物為基準，較佳式5化合物之用量為0至90重量份。當式5化合物之用量不大於90重量份時，由於經取代或未經取代之芳香族基故，硬質罩幕組成物之抗反射性令人滿意，如此避免需要施用額外抗反射塗層。為了達成硬質罩幕組成物改良之吸光率及光學輪廓資料，可額外使用抗反射塗層。若未使用式5化合物(亦即0%)，需要額外抗反射塗層。同時，若式5化合物之用量超過90重量份，則因矽含量的減低無法確保硬質罩幕組成物具有足夠蝕刻選擇性。經由控制式5化合物之相對用量可達成適當抗反射性。
另一方面，式6化合物相對用量的增高導致硬質罩幕組 成物之較佳儲存安定性。以100重量份式5、6及7化合物為基準，較佳使用5至90重量份之式6化合物。若式6化合物之用量少於5重量份，則硬質罩幕組成物之儲存安定性可能受損。同時，若式6化合物之用量超過90重量份，則硬質罩幕組成物之吸光率降低。
式7化合物之相對含量增高導致硬質罩幕組成物之親水性改良。以100重量份式5、6及7化合物為基準，較佳式7化合物之用量為5至90重量份。式7化合物之用量少於5重量份無法確保親水性之有效改性。同時，式7化合物之用量超過90重量份可能造成硬質罩幕組成物之儲存安定性的降級。式7化合物之相對用量的增高，由於存在於矽原子間之鏈接基增加暴露於表面之Si-OH基團數目，減低鍵結之自由度，使得使用該硬質罩幕組成物所形成之薄膜高度親水。結果，藉改變式7化合物之用量可控制硬質罩幕之親水性。硬質罩幕之親水性為控制與該硬質罩幕頂上薄膜之可相容性之一大重要因素。
硬質罩幕組成物之儲存安定性可藉由改變經由式5、6及7化合物之水解產物之縮聚合所製備之終產物縮聚物中之烷氧基數目而決定。較佳有機矽烷聚合物中之烷氧基含量係控制為相對於聚合物之重複單元最高達25莫耳%。烷氧基含量的增加促成儲存安定性的改良，但造成塗覆性變差及耐溶劑性不佳，因而使得塗層品質不均或造成難以塗覆另一層薄膜於該硬質罩幕上。
以100重量份硬質罩幕組成物為基準，有機矽烷聚合物 (a)較佳係以1至50重量份且更佳1至30重量份之數量存在。超出此範圍，造成硬質罩幕組成物之塗覆性不良。
適合用於本發明之硬質罩幕組成物之溶劑之實例包括丙酮、四氫喃、苯、甲苯、***、氯仿、二氯甲烷、乙酸乙酯、丙二醇甲醚、丙二醇***、丙二醇丙醚、乙酸丙二醇甲醚(PGMEA)、乙酸丙二醇***、乙酸丙二醇丙醚、乳酸乙酯、及γ-丁內酯。該溶劑可與反應溶劑相同或相異。
本發明之硬質罩幕組成物進一步包含選自於由有機鹼之磺酸鹽類諸如對甲苯磺酸吡啶鎓、醯胺基磺基菜鹼-16及(-)-樟腦-10-磺酸銨鹽、甲酸銨、甲酸三乙基銨、甲酸三甲基銨、甲酸四甲基銨、甲酸吡啶鎓、甲酸四丁基銨、硝酸四甲基銨、硝酸四丁基銨、乙酸四丁基銨、疊氮化四丁基銨、苯甲酸四丁基銨、硫酸氫四丁基銨、溴化四丁基銨、氯化四丁基銨、氰化四丁基銨、氟化四丁基銨、碘化四丁基銨、硫酸四丁基銨、亞硝酸四丁基銨、對甲苯磺酸四丁基銨、磷酸四丁基銨、及其混合物所組成之組群之交聯催化劑。交聯催化劑扮演促進有機矽烷聚合物交聯之角色來改良硬質罩幕之耐蝕刻性及耐溶劑性。以100重量份有機矽烷聚合物為基準，交聯催化劑較佳以0.0001至0.01重量份之數量使用。若交聯催化劑之用量低於0.0001重量份，則無法預期前述效果。若交聯催化劑之用量大於0.01重量份則硬質罩幕組成物之儲存安定性降級。
任選地，本發明之硬質罩幕組成物進一步包含選自於交聯劑、自由基安定劑、及界面活性劑中之至少一種添加 劑。添加劑與交聯催化劑之組合物可用於本發明之硬質罩幕組成物。
本發明也提供一種使用該硬質罩幕組成物製造半導體積體電路裝置之方法。
特定言之，該方法包含(a)形成一以碳為主之硬質罩幕層，(b)於該以碳為主之硬質罩幕層上塗覆該硬質罩幕組成物而形成一以矽為主之硬質罩幕層，(c)於該以矽為主之硬質罩幕層上形成一光阻層，(d)通過一罩幕將該光阻層之部分曝光於來自一光源之光，(e)選擇性移除該光阻層之已曝光部分而形成一圖樣，(f)使用該已製作圖樣之光阻層作為蝕刻罩幕來將該圖樣轉印至該以矽為主之硬質罩幕層而將該以矽為主之硬質罩幕層製作圖樣，(g)使用該已製作圖樣之以矽為主之硬質罩幕層作為蝕刻罩幕而將該圖樣轉印至以碳為主之硬質罩幕層來將該以碳為主之硬質罩幕層製作圖樣，及(h)使用該已製作圖樣之以碳為主之硬質罩幕層作為蝕刻罩幕而將該圖樣轉印至該基材。
本發明方法進一步包含於步驟(c)之前於該以矽為主之硬質罩幕層上形成一抗反射塗層。
特定言之，本發明方法可根據下述程序進行。首先，欲製作圖樣之材料(例如氮化鋁或氮化矽(SiN))藉任何適當技術施用至矽基材。該材料可為導電性、半導性、磁性及絕緣性材料中之任一者。
隨後，以碳為主之硬質罩幕組成物旋塗至500埃至4,000埃之厚度及於100-300℃烤乾10秒至10分鐘來形成以 碳為主之硬質罩幕層。然後本發明之硬質罩幕組成物於該以碳為主之硬質罩幕層上旋塗至500埃至4,000埃之厚度及於100-300℃烤乾10秒至10分鐘而形成以矽為主之硬質罩幕層。若有所需，可於該以矽為主之硬質罩幕層上形成抗反射塗層(BARC)。
輻射敏化成像層(光阻層)係形成於該以矽為主之硬質罩幕層上。進行曝光及顯影而於該成像層上形成一圖樣。下層之已曝光部分使用氣體混合物典型為CHF3/CF4乾蝕刻而於該以矽為主之硬質罩幕層上形成一圖樣。於乾蝕刻後，該以碳為主之硬質罩幕層之已曝光部分使用氣體混合物諸如BCl3/Cl2蝕刻而將該以碳為主之硬質罩幕層製作圖樣。
該材料層之已曝光部分使用氣體混合物諸如CHF3/CF4乾蝕刻而將該材料層製作圖樣。使用電漿(例如氧電漿)來移除剩餘材料，只留下該已製作圖樣之材料層。本發明方法可應用於半導體積體電路裝置之製造。
如此，本發明組成物及所得微影結構可用於積體電路裝置之製造與設計。舉例言之，本發明組成物可用於已製作圖樣之材料層結構之形成，諸如金屬佈線、接點孔及通孔、絕緣區段(例如鑲嵌溝渠(DT)及淺渠絕緣(STI))、及用於電容器結構之溝渠。須瞭解本發明並未限於任何特定微影技術及元件結構。
發明模式
後文將參照下列實例以進一步細節解說本發明。但此 等實例僅供舉例說明之用而非解譯為限制本發明之範圍。
實例 [實例1]
於裝配有機械攪動器、冷凝器、滴液漏斗及氮氣進氣管之3升四頸瓶內，449.8克甲基三甲氧基矽烷，41.8克苯基三甲氧基矽烷及138.4克貳(三乙氧基矽烷基)乙烷溶解於1,470克乙酸丙二醇一甲醚(PGMEA)。於室溫於該溶液內添加162.5克水性硝酸溶液(1,000 ppm)。允許混合物於50℃反應1小時後，於減壓下由反應混合物中去除甲醇及乙醇。持續反應5日同時將反應溫度維持於80℃，獲得式8聚矽氧聚合物：{(SiO1.5-CH2CH2-SiO1.5)0.10(MeSiO1.5)0.846(PhSiO1.5)0.054}(OH)0.05(OMe)0.15(OEt)0.07(8)(其中Me、Et及Ph分別表示甲基、乙基及苯基)。
2.0克聚合物以50克PGMEA稀釋及0.002克對甲苯磺酸吡啶鎓添加至其中。所得溶液旋塗於矽晶圓上，接著於240℃烤乾60秒而形成500埃厚膜。
[實例2]
於裝配有機械攪動器、冷凝器、滴液漏斗及氮氣進氣管之3升四頸瓶內，265.4克甲基三甲氧基矽烷，28.9克苯基三甲氧基矽烷及325.8克貳(三乙氧基矽烷基)乙烷溶解於1,470克乙酸丙二醇一甲醚(PGMEA)。於室溫於該溶液內添加150.7克水性硝酸溶液(1,000 ppm)。允許混合物於50℃反應1小時後，於減壓下由反應混合物中去除甲醇及乙醇。持續反應7日同時將反應溫度維持於50℃，獲得式9聚矽氧聚 合物：{(SiO1.5-CH2CH2-SiO1.5)0.30(MeSiO1.5)0.636(PhSiO1.5)0.064}(OH)0.06(OMe)0.13(OEt)0.09(9)(其中Me、Et及Ph分別表示甲基、乙基及苯基)。
2.0克聚合物以50克PGMEA稀釋及0.002克對甲苯磺酸吡啶鎓添加至其中。所得溶液旋塗於矽晶圓上，接著於240℃烤乾60秒而形成500埃厚膜。
[實例3]
於裝配有機械攪動器、冷凝器、滴液漏斗及氮氣進氣管之3升四頸瓶內，146.2克甲基三甲氧基矽烷，37.0克苯基三甲氧基矽烷及446.8克貳(三乙氧基矽烷基)乙烷溶解於1,470克乙酸丙二醇一甲醚(PGMEA)。於室溫於該溶液內添加143.0克水性硝酸溶液(1,000 ppm)。允許混合物於50℃反應1小時後，於減壓下由反應混合物中去除甲醇及乙醇。持續反應3日同時將反應溫度維持於50℃，獲得式10聚矽氧聚合物：{(SiO1.5-CH2CH2-SiO1.5)0.50(MeSiO1.5)0.426(PhSiO1.5)0.074}(OH)0.04(OMe)0.10(OEt)0.12(10)(其中Me、Et及Ph分別表示甲基、乙基及苯基)。
2.0克聚合物以50克PGMEA稀釋及0.002克對甲苯磺酸吡啶鎓添加至其中。所得溶液旋塗於矽晶圓上，接著於240℃烤乾60秒而形成500埃厚膜。
[實例4]
於裝配有機械攪動器、冷凝器、滴液漏斗及氮氣進氣管之2升四頸瓶內，271.4克甲基三甲氧基矽烷，58.5克苯基三甲氧基矽烷及90.1克貳(三乙氧基矽烷基)乙烷溶解於980 克乙酸丙二醇一甲醚(PGMEA)。於室溫於該溶液內添加105.8克水性硝酸溶液(1,000 ppm)。允許混合物於50℃反應1小時後，於減壓下由反應混合物中去除甲醇及乙醇。持續反應13日同時將反應溫度維持於80℃，獲得式11聚矽氧聚合物：{(SiO1.5-CH2CH2-SiO1.5)0.10(MeSiO1.5)0.784(PhSiO1.5)0.116}(OH)0.06(OMe)0.18(OEt)0.03(11)(其中Me、Et及Ph分別表示甲基、乙基及苯基)。
2.0克聚合物以50克PGMEA稀釋及0.002克對甲苯磺酸吡啶鎓添加至其中。所得溶液旋塗於矽晶圓上，接著於240℃烤乾60秒而形成500埃厚膜。
[實例5]
於裝配有機械攪動器、冷凝器、滴液漏斗及氮氣進氣管之3升四頸瓶內，136.4克甲基三甲氧基矽烷，49.7克苯基三甲氧基矽烷及444.0克貳(三乙氧基矽烷基)乙烷溶解於1,470克乙酸丙二醇一甲醚(PGMEA)。於室溫於該溶液內添加142.1克水性硝酸溶液(1,000 ppm)。允許混合物於50℃反應1小時後，於減壓下由反應混合物中去除甲醇及乙醇。持續反應7日同時將反應溫度維持於50℃，獲得式12聚矽氧聚合物：{(SiO1.5-CH2CH2-SiO1.5)0.50(MeSiO1.5)0.40(PhSiO1.5)0.10}(OH)0.06(OMe)0.11(OEt)0.11(12)(其中Me、Et及Ph分別表示甲基、乙基及苯基)。
2.0克聚合物以50克PGMEA稀釋及0.002克對甲苯磺酸吡啶鎓添加至其中。所得溶液旋塗於矽晶圓上，接著於240℃烤乾60秒而形成500埃厚膜。
[實例6]
於裝配有機械攪動器、冷凝器、滴液漏斗及氮氣進氣管之4升四頸瓶內，170.5克甲基三甲氧基矽烷，63.8克苯基三甲氧基矽烷及570.8克貳(三乙氧基矽烷基)乙烷溶解於1,890克乙酸丙二醇一甲醚(PGMEA)。於室溫於該溶液內添加260.1克水性硝酸溶液(1,000 ppm)。允許混合物於50℃反應1小時後，於減壓下由反應混合物中去除甲醇及乙醇。持續反應2日同時將反應溫度維持於50℃，獲得式13聚矽氧聚合物：{(SiO1.5-CH2CH2-SiO1.5)0.50(MeSiO1.5)0.040(PhSiO1.5)0.10}(OH)0.11(OMe)0.08(OEt)0.06(13)(其中Me、Et及Ph分別表示甲基、乙基及苯基)。
2.0克聚合物以50克PGMEA稀釋及0.002克對甲苯磺酸吡啶鎓添加至其中。所得溶液旋塗於矽晶圓上，接著於240℃烤乾60秒而形成500埃厚膜。
[實例7]
於裝配有機械攪動器、冷凝器、滴液漏斗及氮氣進氣管之4升四頸瓶內，160.2克甲基三甲氧基矽烷，59.1克苯基三甲氧基矽烷及528.5克貳(三乙氧基矽烷基)乙烷溶解於1,750克乙酸丙二醇一甲醚(PGMEA)。於室溫於該溶液內添加480.3克水性硝酸溶液(1,000 ppm)。允許混合物於50℃反應1小時後，於減壓下由反應混合物中去除甲醇及乙醇。持續反應1日同時將反應溫度維持於50℃，獲得式14聚矽氧聚合物：{(SiO1.5-CH2CH2-SiO1.5)0.50(MeSiO1.5)0.040(PhSiO1.5)0.10}(OH)0.18(OMe)0.04(OEt)0.03(14)(其中Me、Et及Ph分別表示甲 基、乙基及苯基)。
2.0克聚合物以50克PGMEA稀釋及0.002克對甲苯磺酸吡啶鎓添加至其中。所得溶液旋塗於矽晶圓上，接著於240℃烤乾60秒而形成500埃厚膜。
[實驗例1]
實例1-3所形成之薄膜使用接觸角測量系統(鳳凰(Phoenix)300加，SEO公司)測量與水之接觸角。10微升水滴至各薄膜表面上(5點)。測定薄膜表面與水滴之接觸角。結果示於表1。
表1結果驗證具有期望之表面特性之聚合物容易藉由適當改變式5-7化合物之進給比例而容易合成。特別，隨著聚合物中式7化合物比例的增加，聚合物之表面特性為更加親水。
[實驗例2]
實例1-4所形成之薄膜使用橢圓計(J.A.Woollam)測量折射率(n)及消光係數(k)。結果顯於表2。
由表2結果可知，利用含括於聚合物中之經取代或未經取代之芳香族基吸收深紫外光(DUV)區之紫外光之能力，可製造具有優異抗反射性之材料，經由改變所使用之化合物之含量可獲得材料之最佳抗反射性。
[實驗例3]
實例5-7所製備之溶液測試安定性。三種溶液於40℃儲存30日。觀察溶液狀態及測量塗覆後之薄膜厚度。結果示於表3。
已規度化之分子量係指經由將儲存30日後測得相對應聚合物之分子量除以於聚合物製備後即刻測得之該聚合物之分子量所得之數值。表3結果顯示本發明所定義之具有烷氧基(-OR)於預定含量範圍內之聚合物於儲存期間高度安定。烷氧基含量愈高，於儲存給定時間後分子量及厚度之變化愈少，指示儲存安定性較佳。此等結果獲得結論為經由改變水解後剩餘之烷氧基數量，可改良溶液之儲存安定性。
[實驗例4]
ArF光阻塗覆於實例1-3所形成之各薄膜上，於110℃烤乾60秒，使用ArF曝光系統(ASML1250、FN70 5.0活性、NA 0.82)曝光及以TMAH水溶液(2.38 wt%)顯影而形成80奈米線與間圖樣。以曝光能之函數測定圖樣之曝光寬容度(EL)邊際，以距光源之距離之函數測定圖樣之焦深(DoF)邊際。結果記錄於表4。
就EL邊際及DoF邊際而言各圖樣皆顯示良好光學輪廓資料。結果驗證以矽為主之旋塗硬質罩幕組成物可實際上應用於半導體製造方法。
[實驗例5]
實驗例4所得已製作圖樣之試驗件循序使用CFx電漿、O2電漿及CFx電漿乾蝕刻。剩餘有機材料使用O2完全移除，藉FE-SEM觀察已蝕刻試驗件之截面。結果列舉於表5。
蝕刻後圖樣具有垂直形狀，指示試驗件之蝕刻特性良 好。結果顯示以矽為主之旋塗硬質罩幕組成物可實際應用於半導體製造方法。
第1圖為由以碳為主之硬質罩幕、以矽為主之硬質罩幕及阻劑層於基材上所組成之多層膜之示意剖面圖；第2圖顯示式5化合物之特定實例；及第3圖顯示式7化合物之特定實例。

Claims (12)

  1. 一種以矽為主之硬質罩幕組成物，包含(a)式1表示之一有機矽烷聚合物：{(SiO 1.5 -Y-SiO 1.5 ) x (R 3 SiO 1.5 ) y (XSiO 1.5 ) z }(OH) e (OR 6 ) f (1)其中x、y及z表示聚合物中之重複單元(SiO1.5-Y-SiO1.5)、(R3SiO1.5)及(XSiO1.5)之相對比且滿足關係式0.05x0.9、0.05y0.9、0z0.9及x+y+z=1；e及f分別表示鍵結至矽(Si)原子之端末-OH基數目及端末-OR基數目對該聚合物中之2x+y+z矽(Si)原子數目之比，且滿足關係式0.03e0.2及0.03f0.25；X為含有至少一個經取代或未經取代之芳香環之C6-C30官能基；R3為C1-C6烷基；Y為選自於由芳香環、經取代或未經取代之線性或分支C1-C20伸烷基、主鏈中含有至少一個芳香環或雜環系環或具有至少一個脲基或異三聚氰酸酯基之C1-C20伸烷基及含有至少一個多重鍵之C2-C20烴基所組成之組群之鏈接基；且R6為C1-C6烷基，及(b)一溶劑。
  2. 如申請專利範圍第1項之硬質罩幕組成物，其中該有機矽烷聚合物(a)為式2、3及4表示之化合物之縮聚物：(HO) a (R 1 O) (3-a) Si-X (2)其中R1為C1-C6烷基，0a3，且X為含有至少一個經取代或未經取代之芳香環之C6-C30官能基；(HO) b (R 2 O) (3-b) Si-R 3 (3)其中R2為C1-C6烷基，0b3，且R3為C1-C12烷基；及 (HO) c (R 4 O) (3-c) Si-Y-Si(OH) d (R 5 O) (3-d) (4)其中R4及R5分別為C1-C6烷基，0c3，0d3，且Y為選自於由芳香環、經取代或未經取代之線性或分支C1-C20伸烷基、主鏈中含有至少一個芳香環或雜環系環或具有至少一個脲基或異三聚氰酸酯基之C1-C20伸烷基及含有至少一個多重鍵之C2-C20烴基所組成之組群之鏈接基。
  3. 如申請專利範圍第1項之硬質罩幕組成物，其中該有機矽烷聚合物(a)係於酸催化劑存在下，經由式5、6及7表示之化合物或者式6及7表示之化合物的水解產物縮聚合而製備：(R 1 O) 3 Si-X (5)其中X為含有至少一個經取代或未經取代之芳香環之C6-C30官能基，且R1為C1-C6烷基；(R 2 O) 3 Si-R 3 (6)其中R2為C1-C6烷基且R3為C1-C12烷基；及(R 4 O) 3 Si-Y-Si(OR 5 ) 3 (7)其中R4及R5分別為C1-C6烷基，且Y為選自於由芳香環、經取代或未經取代之線性或分支C1-C20伸烷基、主鏈中含有至少一個芳香環或雜環系環或具有至少一個脲基或異三聚氰酸酯基之C1-C20伸烷基及含有至少一個多重鍵之C2-C20烴基所組成之組群之鏈接基。
  4. 如申請專利範圍第1項之硬質罩幕組成物，其中該有機矽烷聚合物(a)具有2,000至90,000之重量平均分子量。
  5. 如申請專利範圍第3項之硬質罩幕組成物，其中該有機矽烷聚合物之製備方法係經由相對於100重量份式5、6及7化合物，混合0至90重量份式5化合物，5至90重量份式6化合物及5至90重量份式7化合物，且允許5至90重量份該混合物於0.001至5重量份酸催化劑存在下反應而製備。
  6. 如申請專利範圍第3項之硬質罩幕組成物，其中該酸催化劑選自於由硝酸、硫酸、鹽酸、對甲苯磺酸一水合物、硫酸二乙酯、及其組合所組成之組群。
  7. 如申請專利範圍第1項之硬質罩幕組成物，其中以100重量份該硬質罩幕組成物為基準，該有機矽烷聚合物(a)係以1至50重量份之數量存在。
  8. 如申請專利範圍第1項之硬質罩幕組成物，進一步包含選自於由對甲苯磺酸吡啶鎓、醯胺基磺基菜鹼-16及(-)-樟腦-10-磺酸銨鹽、甲酸銨、甲酸三乙基銨、甲酸三甲基銨、甲酸四甲基銨、甲酸吡啶鎓、甲酸四丁基銨、硝酸四甲基銨、硝酸四丁基銨、乙酸四丁基銨、疊氮化四丁基銨、苯甲酸四丁基銨、硫酸氫四丁基銨、溴化四丁基銨、氯化四丁基銨、氰化四丁基銨、氟化四丁基銨、碘化四丁基銨、硫酸四丁基銨、亞硝酸四丁基銨、對甲苯磺酸四丁基銨、磷酸四丁基銨、及其混合物所組成之組群之化合物。
  9. 如申請專利範圍第1項之硬質罩幕組成物，進一步包含選自於交聯劑、自由基安定劑、及界面活性劑中之至少 一種添加劑。
  10. 如申請專利範圍第8項之硬質罩幕組成物，進一步包含選自於交聯劑、自由基安定劑、及界面活性劑中之至少一種添加劑。
  11. 一種製造半導體積體電路裝置之方法，該方法包含(a)形成一以碳為主之硬質罩幕層，(b)於該以碳為主之硬質罩幕層上塗覆申請專利範圍第1至10項中任一項之硬質罩幕組成物而形成一以矽為主之硬質罩幕層，(c)於該以矽為主之硬質罩幕層上形成一光阻層，(d)通過一罩幕將該光阻層之部分曝光於來自一光源之光，(e)選擇性移除該光阻層之已曝光部分而形成一圖樣，(f)使用該已製作圖樣之光阻層作為一蝕刻罩幕，將該圖樣轉印至該以矽為主之硬質罩幕層而將該以矽為主之硬質罩幕層製作圖樣，(g)使用該已製作圖樣之以矽為主之硬質罩幕層作為一蝕刻罩幕，將該圖樣轉印至該以碳為主之硬質罩幕層來將該以碳為主之硬質罩幕層製作圖樣，及(h)使用該已製作圖樣之以碳為主之硬質罩幕層作為一蝕刻罩幕，將該圖樣轉印至基材。
  12. 如申請專利範圍第11項之方法，進一步包含於步驟(c)之前於該以矽為主之硬質罩幕層上形成一抗反射塗層。
TW098100849A 2008-01-11 2009-01-10 以矽為主之硬質罩幕組成物（Ｓｉ－ＳＯＨ；以Ｓｉ為主之旋塗硬質罩幕）以及使用該組成物製造半導體積體電路裝置的方法 TWI400300B (zh)

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