TWI649623B - 微影術用光阻下層膜形成組成物,及製作半導體元件的方法 - Google Patents
微影術用光阻下層膜形成組成物,及製作半導體元件的方法 Download PDFInfo
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- TWI649623B TWI649623B TW103125107A TW103125107A TWI649623B TW I649623 B TWI649623 B TW I649623B TW 103125107 A TW103125107 A TW 103125107A TW 103125107 A TW103125107 A TW 103125107A TW I649623 B TWI649623 B TW I649623B
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Classifications
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Abstract
本發明之課題為提供一種光阻下層膜形成組成物用添加劑及包含其之光阻下層膜形成組成物,該光阻下層膜形成組成物用添加劑係為了使於光阻下層膜上所形成之光阻圖型與該光阻下層膜之密著性增大,將光阻下層膜之表面狀態改質成疏水性狀態。
本發明之解決手段為包含具有下述式(1)所示之構造單位之聚合物的光阻下層膜形成組成物用添加劑,以及包含樹脂黏結劑、有機溶劑及前述添加劑之光阻下層膜形成組成物。
Description
本發明係關於添加於光阻下層膜形成組成物中之添加劑。尤其是關於一種添加劑(改質劑),其係以將所形成之光阻下層膜的表層改質成疏水性,使其與光阻之密著性提升,於該光阻下層膜上形成期望的形狀之圖型作為目的。進而,關於包含該添加劑(改質劑)之光阻下層膜形成組成物。
ArF液浸微影術或極紫外線(EUV)微影術中,追求光阻線寬加工尺寸之微細化。如此微細的光阻圖型之形成中,由於光阻圖型與基底基板之接觸面積變小,有光阻圖型之縱橫比(光阻圖型之高度/光阻圖型之線寬)變大、容易發生光阻圖型塌陷的顧慮。因此,與光阻接觸之光阻下層膜(防反射膜)中,要求不發生光阻圖型塌陷之與光阻的高密著性。
光阻下層膜中,為了表現與光阻之高密著性,已報告有藉由使用內酯構造作為光阻下層膜形成組成物之構成成分,對於所得光阻圖型之密著性提升(專利文獻1)。即,藉由使用如內酯構造之包含極性部位的構造作為光阻下層膜形成組成物之構成成分,期待對光阻圖型之密著性提升,且即使於微細之光阻圖型中亦防止光阻圖型的塌陷。
然而,如ArF液浸微影術、極紫外線(EUV)微影術之,較微細之光阻圖型製作所要求的微影術製程中,僅包含內酯構造作為光阻下層膜形成組成物之構成成分,對於防止光阻圖型塌陷而言並不充分。
另一方面,作為表現與光阻之高密著性的手法,可舉例控制光阻與光阻下層膜間之界面的化學狀態的方法。專利文獻2中記載有一種光阻下層膜形成組成物用添加劑,其使光阻下層膜之表面狀態改質成鹼性狀態,能抑制光阻圖型形狀成為底切形狀。
〔專利文獻1〕 國際公開第03/017002號
〔專利文獻2〕 國際公開第2013/058189號
近年來,為了抑制伴隨光阻圖型微細化之圖型倒塌,藉由使光阻疏水化,使使用純水清洗步驟時的拉普拉斯力減低。因此,藉由使光阻下層膜亦成為疏水性,期待光阻與光阻下層膜之間密著性的提升。
於是,本發明之目的為提供一種光阻下層膜形成組成物用添加劑,其係為了使光阻下層膜上所形成之光阻圖型與該光阻下層膜之密著性增大,而將光阻下層膜之表面狀態改質成疏水性狀態。
本發明之第一態樣為一種光阻下層膜形成組成物用添加劑,其包含具有下述式(1)所示之構造單位的聚合物。
前述聚合物亦可為進而具有下述式(2)所示之1種或2種以上的構造單位之共聚物。
前述二價之連結基,例如,含有選自-C(=O)-基、-CH2-基、-O-基及伸苯基所成群中之至少1種。
本發明之第二態樣為一種微影術用光阻下層膜形成組成物,其包含樹脂黏結劑、有機溶劑及前述第一態樣之光阻下層膜形成組成物用添加劑。前述光阻下層膜形成組成物亦可進而含有交聯劑及交聯觸媒。
前述光阻下層膜形成組成物用添加劑中之聚合物(共聚物),相對於自前述光阻下層膜形成組成物去除前述有機溶劑之固形分而言,可含有例如0.1質量%至30質量%,較佳為1質量%至15質量%,更佳為5質量%至15質量%。
本發明之第三態樣為一種製作半導體元件的方法,其係於具有形成轉寫圖型之加工對象膜的基板上,
塗佈前述第二態樣之光阻下層膜形成組成物並烘烤形成光阻下層膜,於前述光阻下層膜上被覆光阻,對經前述光阻所被覆之前述基板照射選自KrF準分子雷射、ArF準分子雷射、極紫外線及電子束所成群之輻射線,之後顯像形成光阻圖型,將前述光阻圖型做為遮罩藉由乾式蝕刻轉寫圖型至前述基板上。
藉由應用添加有本發明之添加劑的光阻下層膜形成組成物於微影術製程,光阻下層膜之表面狀態不成為鹼性狀態,即光阻圖型形狀不成為椎體形狀,而提升光阻下層膜與光阻圖型之間的密著性。進而,即使是於微細線寬的光阻圖型之形成中,亦能有效抑制所形成之光阻圖型的塌陷。
本發明之第一態樣之添加劑,包含具有前述式(1)所示之構造單位的聚合物,該聚合物可為溶解於後述有機溶劑之溶液狀。前述聚合物可為均聚物及共聚物之任一。作為前述式(1)中L所示之二價之連結基,雖只要是含有選自-C(=O)-基、-CH2-基、-O-基及伸苯基所成群中之至少1種基者即無特別限定,但可舉例例如,-C(=O)O-基、-C(=O)O-CH2-基、伸苯基、伸苯氧基。
作為前述式(1)所示之構造單位,例如為下
述式(1-1)至式(1-16)所示。下述式(1-4)中,n表示1至17之整數。
本發明之第一態樣之添加劑包含具有前述式(1)所示之構造單位及前述式(2)所示之1種或2種以上之構造單位的共聚物時,該式(2)中,作為M所示之
含有選自-C(=O)-基、-CH2-基及-O-基所成群中之至少1種基的連結基,可舉例例如,-C(=O)O-基、-C(=O)O-CH2-基。前述M表示直接鍵結時,Y所示之至少1個氫原子經氟原子所取代之碳原子數2至6的烷基,或是具有至少1個羥基、烷氧基或羧基之碳原子數1至6的烷基,係與主鏈直接鍵結。此處,作為前述烷氧基,可舉例例如甲氧基、乙氧基、tert-丁氧基。作為形成前述式(2)所示之構造單位的單體,可舉例例如,丙烯酸單氟乙酯、甲基丙烯酸單氟乙酯、丙烯酸三氟乙酯、甲基丙烯酸三氟乙酯、丙烯酸四氟丙酯、甲基丙烯酸四氟丙酯、丙烯酸五氟丙酯、甲基丙烯酸五氟丙酯、丙烯酸六氟丙酯、甲基丙烯酸六氟丙酯、丙烯酸六氟異丙酯、甲基丙烯酸六氟異丙酯、丙烯酸六氟丁酯、甲基丙烯酸六氟丁酯、丙烯酸七氟丁酯、甲基丙烯酸七氟丁酯、丙烯酸八氟戊酯、甲基丙烯酸八氟戊酯、丙烯酸羥乙酯、甲基丙烯酸羥乙酯、丙烯酸羥丙酯、甲基丙烯酸羥丙酯、丙烯酸二羥基丙酯、甲基丙烯酸二羥基丙酯、丙烯酸羥丁酯、甲基丙烯酸羥丁酯、丙烯酸羥戊酯及甲基丙烯酸羥戊酯。此等例中較佳為,甲基丙烯酸三氟乙酯及甲基丙烯酸羥丙酯。
為了抑制光阻圖型之塌陷,且藉由導入前述
式(2)所示之構造單位提升光阻下層膜之機能性,相對於形成共聚物之單體的總和,使用形成前述式(2)所示之1種或2種以上之構造單位的單體30質量%至60質量%,較佳為使用40質量%至50質量%。
本發明之光阻下層膜形成組成物用添加劑
為,藉由於有機溶劑中同時含有與樹脂黏結劑,構成本發明之第二態樣之光阻下層膜形成組成物。相對於自前述光阻下層膜形成組成物去除前述有機溶劑之固形分而言,具有前述式(1)所示之構造單位之聚合物,或具有前述式(1)所示之構造單位及式(2)所示之構造單位的共聚物之含有比例,可例如為0.5質量%至30質量%,該聚合物或共聚物之重量平均分子量,可例如為3000至50000,較佳為4000至20000。且,重量平均分子量為藉由凝膠滲透色層分析法(GPC),使用聚苯乙烯作為標準試料所得之值。
作為本發明之光阻下層膜形成組成物所含的
有機溶劑,可舉例例如,丙二醇單甲醚(PGME)、丙二醇單甲醚乙酸酯(PGMEA)、丙二醇單乙醚、丙二醇單丙醚、甲基乙基酮、乳酸乙酯、環己酮、γ-丁內酯、N-甲基吡咯啶酮、及選自此等之有機溶劑2種以上的混合物。
接著,相對於本發明之光阻下層膜形成組成物之上述有機溶劑的比例,可例如為50質量%至99.5質量%。
作為本發明之光阻下層膜形成組成物所含之樹脂黏結劑,例如,可適用後述合成例1所得之聚合物。又,作為該樹脂黏結劑,可適用周知的防反射膜形成用組成物或周知的光阻下層膜形成組成物所含之基聚合物作為樹脂黏結劑。相對於自本發明之光阻下層膜形成組成物去除前述有機溶劑之固形分而言,上述樹脂黏結劑之比例,
可例如為50質量%至99.5質量%,較佳為60質量%至90質量%。
本發明之光阻下層膜形成組成物,可包含交
聯劑作為任意成分。作為如此之交聯劑,可舉例例如,六甲氧基甲基三聚氰胺、四甲氧甲基苯并胍胺、1,3,4,6-肆(甲氧基甲基)乙炔脲(POWDERLINK〔註冊商標〕1174)、1,3,4,6-肆(丁氧基甲基)乙炔脲、1,3,4,6-肆(羥基甲基)乙炔脲、1,3-雙(羥基甲基)尿素、1,1,3,3-肆(丁氧基甲基)尿素及1,1,3,3-肆(甲氧基甲基)尿素。使用上述交聯劑時,該交聯劑之含有比例相對於前述樹脂黏結劑而言,可例如為1質量%至30質量%。
本發明之光阻下層膜形成組成物可包含促進
交聯反應之交聯觸媒作為任意成分。作為如此之交聯觸媒,可舉例例如p-甲苯磺酸、三氟甲烷磺酸、吡啶鎓-p-甲苯磺酸鹽、柳酸、樟腦磺酸、5-磺柳酸、4-氯苯磺酸、4-羥基苯磺酸、苯二磺酸、1-萘磺酸、檸檬酸、苯甲酸、羥基苯甲酸等之磺酸化合物及羧酸化合物。使用上述交聯觸媒時,該交聯觸媒之含有比例相對於前述交聯劑而言,可例如為0.1質量%至10質量%。前述交聯劑及交聯觸媒,在前述樹脂黏結劑為自交聯型聚合物之情形中,於本發明之光阻下層膜形成組成物中為非必要成分。
本發明之第三態樣之製作半導體元件的方法中所使用的基板,雖以矽晶圓具代表性,但亦可使用SOI(Silicon on Insulator)基板、或砷化鎵(GaAs)、磷化
銦(InP)、磷化鎵(GaP)等之化合物半導體晶圓。作為加工對象膜,前述基板上可形成例如,氧化矽膜、含氮之氧化矽膜(SiON膜)、含碳之氧化矽膜(SiOC膜)、含氟之氧化矽膜(SiOF膜)等之絕緣膜。此時,光阻下層膜形成於加工對象膜上。
本發明之方法中,為了塗覆光阻而使用之光
阻溶液可使用正型、負型任一,可使用對於選自KrF準分子雷射、ArF準分子雷射、極紫外線及電子束所成群中之輻射線感光之化學增幅型光阻。
本發明之方法中,作為上述輻射線照射後進
行顯像所使用之顯像液,例如,可使用如四甲基氫氧化銨(TMAH)水溶液之鹼顯像液。
以下藉由合成例及實施例具體說明本發明。惟,本發明並不限定於下述合成例及實施例之記載。
本說明書之下述合成例1至合成例7所示聚合物之重量平均分子量,係藉由凝膠滲透色層分析法(以下簡稱為GPC)之測定結果。測定係使用TOSOH(股)製GPC裝置,測定條件等如下。
GPC管柱:Shodex〔註冊商標〕.Asahipak〔註冊商標〕(昭和電工(股))
管柱溫度:40℃
溶劑:N,N-二甲基甲醯胺(DMF)
流量:0.6mL/分
標準試料:聚苯乙烯(TOSOH(股))
將單烯丙基二環氧丙基異三聚氰酸(四國化成工業(股)製)10.00g、5-羥基異酞酸6.64g、及苄基三乙基氯化銨0.41g溶解於丙二醇單甲醚64.11g中後,於130℃反應4小時,得到含有聚合物之溶液。對於所得聚合物進行GPC分析之結果,以標準聚苯乙烯換算之重量平均分子量為15,000。本合成例所得之聚合物,相當於本發明之光阻下層膜形成組成物所含之樹脂黏結劑。
將於丙二醇單甲醚30.8g中溶解有tert-甲基丙烯酸丁酯5.00g、甲基丙烯酸三氟乙酯3.04g、及甲基丙烯酸羥丙酯2.36g之溶液進行加熱回流。加熱回流後之溶液中,將於丙二醇單甲醚13.2g中溶解有偶氮雙異丁腈0.57g之溶液徐徐滴下,滴下後,加熱回流使其反應24小時,得到含有聚合物之溶液。對於所得聚合物進行GPC分析之結果,以標準聚苯乙烯換算之重量平均分子量為4,200。本合成例所得之聚合物,相當於本發明之添加劑所含之共聚物。
將於丙二醇單甲醚17.2g中溶解有1-金剛烷基甲基丙烯酸酯5.00g、甲基丙烯酸三氟乙酯1.53g、及甲基丙烯酸羥丙酯1.97g之溶液進行加熱回流。加熱回流後之溶液中,將於丙二醇單甲醚18.6g中溶解有偶氮雙異丁腈0.37g之溶液徐徐滴下,滴下後,加熱回流使其反應24小時,得到含有聚合物之溶液。對於所得聚合物進行GPC分析之結果,以標準聚苯乙烯換算之重量平均分子量為5,000。本合成例所得之聚合物,相當於本發明之添加劑所含之共聚物。
將於丙二醇單甲醚16.3g中溶解有tert-丁基苯乙烯5.00g、甲基丙烯酸三氟乙酯2.10g、及甲基丙烯酸羥丙酯2.70g之溶液進行加熱回流。加熱回流後之溶液中,將於丙二醇單甲醚25.6g中溶解有偶氮雙異丁腈0.51g之溶液徐徐滴下,滴下後,加熱回流使其反應24小時,得到含有聚合物之溶液。對於所得聚合物進行GPC分析之結果,以標準聚苯乙烯換算之重量平均分子量為10,000。本合成例所得之聚合物,相當於本發明之添加劑所含之共聚物。
將於丙二醇單甲醚17.2g中溶解有二環戊烯基甲基丙烯酸酯5.00g、甲基丙烯酸三氟乙酯1.96g、及甲基丙烯酸
羥丙酯1.53g之溶液進行加熱回流。加熱回流後之溶液中,將於丙二醇單甲醚18.6g中溶解有偶氮雙異丁腈0.37g之溶液徐徐滴下,滴下後,加熱回流使其反應24小時,得到含有聚合物之溶液。對於所得聚合物進行GPC分析之結果,以標準聚苯乙烯換算之重量平均分子量為14,000。本合成例所得之聚合物,相當於本發明之添加劑所含之共聚物。
將於丙二醇單甲醚17.2g中溶解有甲基丙烯酸異莰酯5.00g、甲基丙烯酸三氟乙酯1.95g、及甲基丙烯酸羥丙酯1.51g之溶液進行加熱回流。加熱回流後之溶液中,將於丙二醇單甲醚18.5g中溶解有偶氮雙異丁腈0.37g之溶液徐徐滴下,滴下後,加熱回流使其反應24小時,得到含有聚合物之溶液。對於所得聚合物進行GPC分析之結果,以標準聚苯乙烯換算之重量平均分子量為11,000。本合成例所得之聚合物,相當於本發明之添加劑所含之共聚物。
將於丙二醇單甲醚16.4g中溶解有甲基丙烯酸四氫呋喃甲酯5.00g、甲基丙烯酸三氟乙酯2.54g、及甲基丙烯酸羥丙酯1.98g之溶液進行加熱回流。加熱回流後之溶液中,將於丙二醇單甲醚24.1g中溶解有偶氮雙異丁腈
0.48g之溶液徐徐滴下,滴下後,加熱回流使其反應24小時,得到含有聚合物之溶液。對於所得聚合物進行GPC分析之結果,以標準聚苯乙烯換算之重量平均分子量為14,000。本合成例所得之聚合物,相當於本發明之添加劑所含之共聚物。
將於丙二醇單甲醚9.8g中溶解有甲基丙烯酸羥丙酯5.00g及甲基丙烯酸三氟乙酯1.46g之溶液進行加熱回流。加熱回流後之溶液中,將於丙二醇單甲醚17.4g中溶解有偶氮雙異丁腈0.36g之溶液徐徐滴下,滴下後,加熱回流使其反應24小時,得到含有聚合物之溶液。對於所得聚合物進行GPC分析之結果,以標準聚苯乙烯換算之重量平均分子量為6,000。
將於丙二醇單甲醚17.4g中溶解有3-羥基-1-金剛烷基甲基丙烯酸酯5.00g、甲基丙烯酸三氟乙酯1.42g、及甲基丙烯酸羥丙酯1.83g之溶液進行加熱回流。加熱回流後之溶液中,將於丙二醇單甲醚17.4g中溶解有偶氮雙異丁腈0.35g之溶液徐徐滴下,滴下後,加熱回流使其反應24小時,得到含有聚合物之溶液。對於所得聚合物進行GPC分析之結果,以標準聚苯乙烯換算之重量平均分子量為5,000。
藉由混合上述合成例1所得之聚合物溶液(樹脂黏結劑)1.00g、上述合成例2所得之聚合物溶液(添加劑)0.10g、四甲氧甲基乙炔脲(製品名:POWDERLINK〔註冊商標〕1174、Nihon Cytec Industries(股)製)0.25g、p-甲苯磺酸0.025g、丙二醇單甲醚191.5g及丙二醇單乙醚82.1g使其溶解,調製本發明之光阻下層膜形成組成物。
藉由混合上述合成例1所得之聚合物溶液(樹脂黏結劑)1.00g、上述合成例3所得之聚合物溶液(添加劑)0.10g、四甲氧甲基乙炔脲(製品名:POWDERLINK〔註冊商標〕1174、Nihon Cytec Industries(股)製)0.25g、p-甲苯磺酸0.025g、丙二醇單甲醚191.5g及丙二醇單乙醚82.1g使其溶解,調製本發明之光阻下層膜形成組成物。
藉由混合上述合成例1所得之聚合物溶液(樹脂黏結劑)1.00g、上述合成例4所得之聚合物溶液(添加劑)0.10g、四甲氧甲基乙炔脲(製品名:POWDERLINK〔註冊商標〕1174、Nihon Cytec Industries(股)製)0.25g、
p-甲苯磺酸0.025g、丙二醇單甲醚191.5g及丙二醇單乙醚82.1g使其溶解,調製本發明之光阻下層膜形成組成物。
藉由混合上述合成例1所得之聚合物溶液(樹脂黏結劑)1.00g、上述合成例5所得之聚合物溶液(添加劑)0.10g、四甲氧甲基乙炔脲(製品名:POWDERLINK〔註冊商標〕1174、Nihon Cytec Industries(股)製)0.25g、p-甲苯磺酸0.025g、丙二醇單甲醚191.5g及丙二醇單乙醚82.1g使其溶解,調製本發明之光阻下層膜形成組成物。
藉由混合上述合成例1所得之聚合物溶液(樹脂黏結劑)1.00g、上述合成例6所得之聚合物溶液(添加劑)0.10g、四甲氧甲基乙炔脲(製品名:POWDERLINK〔註冊商標〕1174、Nihon Cytec Industries(股)製)0.25g、p-甲苯磺酸0.025g、丙二醇單甲醚191.5g及丙二醇單乙醚82.1g使其溶解,調製本發明之光阻下層膜形成組成物。
藉由混合上述合成例1所得之聚合物溶液(樹脂黏結
劑)1.00g、上述合成例7所得之聚合物溶液(添加劑)0.10g、四甲氧甲基乙炔脲(製品名:POWDERLINK〔註冊商標〕1174、Nihon Cytec Industries(股)製)0.25g、p-甲苯磺酸0.025g、丙二醇單甲醚191.5g及丙二醇單乙醚82.1g使其溶解,調製本發明之光阻下層膜形成組成物。
藉由混合上述合成例1所得之聚合物溶液(樹脂黏結劑)1.00g、四甲氧甲基乙炔脲(製品名:POWDERLINK〔註冊商標〕1174、Nihon Cytec Industries(股)製)0.25g、p-甲苯磺酸0.025g、丙二醇單甲醚177.6g及丙二醇單乙醚76.1g使其溶解,調製光阻下層膜形成組成物。本比較例為不包含本發明之添加劑的例。
藉由混合上述合成例1所得之聚合物溶液(樹脂黏結劑)1.00g、上述合成例8所得之聚合物溶液(添加劑)0.10g、四甲氧甲基乙炔脲(製品名:POWDERLINK〔註冊商標〕1174、Nihon Cytec Industries(股)製)0.25g、p-甲苯磺酸0.025g、丙二醇單甲醚191.5g及丙二醇單乙醚82.1g使其溶解,調製光阻下層膜形成組成物。本比較例為包含不符合本發明添加劑的添加劑之例。
藉由混合上述合成例1所得之聚合物溶液(樹脂黏結劑)1.00g、上述合成例9所得之聚合物溶液(添加劑)0.10g、四甲氧甲基乙炔脲(製品名:POWDERLINK〔註冊商標〕1174、Nihon Cytec Industries(股)製)0.25g、p-甲苯磺酸0.025g、丙二醇單甲醚191.5g及丙二醇單乙醚82.1g使其溶解,調製光阻下層膜形成組成物。本比較例為包含不符合本發明添加劑的添加劑之例。
矽晶圓上分別旋塗本發明之實施例1及實施例2、以及於比較例1至比較例3所調製之光阻下層膜形成組成物,於205℃加熱1分鐘,形成光阻下層膜。然後,為了評估各光阻下層膜表面之疏水性,使用協和界面科學(股)製全自動接觸角計DM700測定該光阻下層膜之對水的接觸角。其結果表示於下述表1。對水的接觸角愈大,膜表面之疏水性愈高。於該光阻下層膜上,旋塗EUV用光阻溶液(甲基丙烯酸酯樹脂系光阻),加熱後使用EUV曝光裝置(Exitech社製EUV Micro Exposure Tool(MS-13),以NA=0.35、σ=0.36/0.68〔四極(Quadrupole)〕之條件進行曝光。曝光後,進行PEB,於冷卻板上冷卻至室溫,進行顯像及清洗處理,形成光阻圖型。
形成之光阻圖型的目標線寬定為30nm線和間
隔(line and space),進行DOF(焦點深度)之比較。其結果表示於下述表1。DOF係以最適焦點位置作為基準,將焦點位置以50μm階段上下一邊移動一邊使用上述曝光裝置進行曝光,之後進行顯像及清洗處理並藉由微距量測掃描式電子顯微鏡(CD-SEM)觀察所形成之光阻圖型的線和間隔,沒有圖型塌陷或圖型變形之焦點範圍作為DOF。
依據表1,由於使用包含本發明之添加劑的實
施例1及實施例2之光阻下層膜形成組成物形成光阻下層膜之情形中,DOF較使用比較例1至比較例3之光阻下層膜形成組成物形成光阻下層膜之情形大,故可防止形成微細光阻圖型時光阻圖型之塌陷。即,確認實施例1及實施例2之光阻下層膜形成組成物所含之本發明添加劑,對於防止光阻圖型之塌陷顯示有用的效果。
於蒸鍍有含氮之氧化矽膜(SiON)(膜厚31.5nm)之矽晶圓上,將本說明書實施例3至實施例6、及比較例1所調製之各光阻下層膜形成組成物,以膜厚成為5nm旋塗,藉由於205℃烘烤60秒鐘,形成光阻下層膜。該光阻下層膜上,旋塗ArF準分子雷射用光阻溶液(JSR(股)製、製品名:AR2772JN),於110℃進行90秒鐘烘烤,使用ArF準分子雷射用曝光裝置((股)Nikon製、NSR-S307E),以給定之條件曝光。曝光後,於110℃進行90秒鐘烘烤(PEB),於冷卻板上冷卻至室溫,進行顯像及清洗處理,形成光阻圖型。
目標線寬定為62nm線和間隔,為了研討最適
焦點時曝光量變化與光阻圖型塌陷之關係,藉由微距量測掃描式電子顯微鏡(CD-SEM)確認光阻圖型未塌陷之最高曝光量(極限曝光量)中光阻圖型尺寸(圖型倒塌極限尺寸)。藉此能確認是否藉由使用本發明之添加劑,能防止於高曝光量區域之光阻圖型的塌陷,形成微細光阻圖型。又,目標線寬之62nm線和間隔中光阻圖型的截面形狀,藉由截面SEM確認。光阻圖型是否易塌陷,可由光阻圖型之截面形狀判斷。
所得光阻圖型之,圖型倒塌極限尺寸與圖型
截面形狀的結果表示於下述表2。此圖型倒塌極限尺寸愈小愈佳。
依據表2,由於使用包含本發明添加劑之實施
例3至實施例6的光阻下層膜形成組成物形成光阻下層膜之情形中,圖型倒塌極限尺寸較使用比較例1之光阻下層膜形成組成物形成光阻下層膜之情形小,可防止形成微細光阻圖型時光阻圖型之塌陷。又,使用實施例3至實施例6之光阻下層膜形成組成物形成光阻下層膜之情形中,所有所得光阻圖型之截面形狀皆為直的形狀(大略矩形)。
即,確認實施例3至實施例6之光阻下層膜形成組成物所含之本發明添加劑,對於防止光阻圖型之塌陷顯示有用的效果。
以上雖說明本發明之實施形態,但本發明之
技術範圍不限定於上述實施形態所載範圍。上述實施形態可加上多樣的變更或改良。
Claims (5)
- 一種微影術用光阻下層膜形成組成物,其特徵係包含樹脂黏結劑、有機溶劑及光阻下層膜形成組成物用添加劑,前述光阻下層膜形成組成物用添加劑包含具有下述式(1)所示之構造單位與下述式(2)所示之2種以上之構造單位之共聚物,在前述共聚物中,相對於形成前述共聚物之單體的總和,使用30質量%至60質量%之形成前述式(2)所示之2種以上之構造單位的單體,
- 如請求項1之微影術用光阻下層膜形成組成物,其中,相對於自前述光阻下層膜形成組成物去除前述有機溶劑之固形分,前述光阻下層膜形成組成物用添加劑中之共聚物係包含0.1質量%至30質量%。
- 如請求項1之微影術用光阻下層膜形成組成物,其中,相對於自前述光阻下層膜形成組成物去除前述有機溶劑之固形分,前述樹脂黏結劑係包含60質量%至90質量%。
- 如請求項1至請求項3中任一項之微影術用光阻下層膜形成組成物,其中,進而包含交聯劑及交聯觸媒。
- 一種製作半導體元件的方法,其特徵係於具有形成轉寫圖型之加工對象膜的基板上,塗佈如請求項1至請求項4中任一項之光阻下層膜形成組成物並烘烤形成光阻 下層膜,於前述光阻下層膜上被覆光阻,對經前述光阻所被覆之前述基板照射選自KrF準分子雷射、ArF準分子雷射、極紫外線及電子束所成群之輻射線,之後顯像形成光阻圖型,將前述光阻圖型做為遮罩藉由乾式蝕刻轉寫圖型至前述基板上。
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