TW201602140A - 添加劑及含該添加劑之阻劑底層膜形成組成物 - Google Patents
添加劑及含該添加劑之阻劑底層膜形成組成物 Download PDFInfo
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Abstract
本發明提供一種阻劑底層膜形成組成物用之添加劑、及含該添加劑之阻劑底層膜形成組成物。
一種包含具有以下述式(1)至式(4)表示之構造單位之共聚物的阻劑底層膜形成組成物用之添加劑、及含前述添加劑之阻劑底層膜形成組成物。
□(式中,R1各獨立表示氫原子或甲基,Ar表示伸芳基,Pr表示保護基或氫原子,X表示直接鍵或-C(=O)O-R2-基,構成該-C(=O)O-R2-基之R2表示碳原子數1至3之
伸烷基,該伸烷基係與硫原子鍵結者,R3表示氫原子、甲基、甲氧基或鹵基,R4表示至少1個氫原子經氟基取代之碳原子數1至3之烷基,Z表示具有4員環至7員環之內酯骨架、金剛烷骨架、或降冰片烷骨架之有機基)。
Description
本發明係關於添加於阻劑底層膜形成組成物中之添加劑。尤其,係關於以在阻劑底層膜上形成期望圖型之阻劑圖型為目的之添加劑。另外,關於含該添加劑之阻劑底層膜形成組成物。
ArF液浸微影或極紫外線(EUV)微影中要求阻劑線寬之加工尺寸之微細化。該微細化之阻劑圖型之形成中,藉由減小阻劑圖型與底層基板之接觸面積,而使阻劑圖型之長寬比(阻劑圖型之高度/阻劑圖型之線寬)增大,會有容易產生阻劑圖型崩塌之顧慮。因此,與阻劑圖型接觸之阻劑底層膜(抗反射膜)要求與阻劑圖型之高的密著性以不產生前述崩塌。
已有報導於阻劑底層膜中,為了展現與阻劑圖型之高的密著性,而藉由使用含內酯構造之阻劑底層膜形成組成物,提高對所得阻劑圖型之密著性(專利文獻
1)。亦即,藉由使用含有如內酯構造之極性部位之阻劑底層膜形成組成物,而提高對阻劑圖型之密著性,且即使在微細之阻劑圖型中仍期待能防止阻劑圖型之崩塌。
然而,如ArF液浸微影、極紫外線(EUV)微影般要求更微細之阻劑圖型製作之微影製程中,僅包含內酯構造作為阻劑底層膜形成組成物用以防止阻劑圖型之崩塌尚不能說已足夠。
為了展現阻劑底層膜與阻劑圖型之高的密著性,專利文獻2中記載將阻劑底層膜之表面狀態改質成鹼性狀態,可抑制阻劑圖型之下擺形狀成為底切形狀之阻劑底層膜形成組成物用添加劑。另一方面,專利文獻3中記載藉由使添加劑成分偏析於阻劑底層膜之表面附近,可抑制阻劑圖型之下擺形狀成為腳底形狀之阻劑底層膜形成組成物用添加劑。
專利文獻4中記載含有具有於末端導入磺基之構造單位之共聚物、交聯劑以及溶劑之微影用阻劑底層膜形成組成物。而且,專利文獻4中記載之發明可提供能發揮在形成阻劑底層膜時抑制源自交聯觸媒成份之昇華物發生之效果,可形成下部幾乎不具有展開形狀之良好形狀之阻劑圖型之阻劑底層膜。
〔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
〔專利文獻3〕國際公開第2010/074075號
〔專利文獻4〕日本特開2010-237491號公報
阻劑圖型形成時,有時並非採用在顯像步驟中,使用鹼性顯像液,去除自正型阻劑溶液形成之阻劑膜之曝光部之方法,而是採用可溶解阻劑膜之溶劑,通常使用有機溶劑去除前述阻劑膜之未曝光部,留下該阻劑膜之曝光部作為阻劑圖型之方法。採用後者之方法時,上述過去之技術難以同時滿足防止阻劑圖型崩塌之效果與阻劑圖型之剖面形狀成為直線形狀之效果。因此,本發明之目的係提供一種可防止阻劑圖型之崩塌,且使阻劑圖型之剖面形狀成為直線形狀之阻劑底層膜形成組成物用添加劑,及含該添加劑之阻劑底層膜形成組成物。
本發明之第一樣態為一種阻劑底層膜形成組成物用添加劑,其包含具有以下述式(1)至式(4)表示之構造單位之共聚物。
(式中,R1各獨立表示氫原子或甲基,Ar表示伸芳基,Pr表示保護基或氫原子,X表示直接鍵或-C(=O)O-R2-基,構成該-C(=O)O-R2-基之R2表示碳原子數1至3之伸烷基,該伸烷基係與硫原子鍵結者,R3表示氫原子、甲基、甲氧基或鹵基,R4表示至少1個氫原子經氟基取代之碳原子數1至3之烷基,Z表示具有4員環至7員環之內酯骨架、金剛烷骨架、或降冰片烷骨架之有機基)。
前述保護基為例如乙醯基、甲氧基甲基、乙氧基乙基、碳原子數4至8之3級烷基、或特戊醯基。本發明中,前述保護基較好為在酸性條件下經加熱而脫離者。
以前述式(2)表示之構造單位為例如以下述式(2a)或式(2b)表示之構造單位。
(式中,R1各自獨立表示氫原子或甲基,R2表示碳原子數1至3之伸烷基,R3表示氫原子、甲基、甲氧基或鹵基)。
以前述式(4)表示之構造單位為例如以下述式(4a)表示之構造單位。
(式中,R1各獨立表示氫原子或甲基,R5表示碳原子數2至5之烴基)。
前述共聚物係使形成以前述式(1)表示之構造單位之單體、形成以前述式(2)表示之構造單位之單體、形成以前述式(3)表示之構造單位之單體、與形成以前述式(4)表示之構造單位之單體共聚合而合成之化
合物,且相對於前述4種單體之合計100莫耳%,形成以前述式(2)表示之構造單位之單體之比例為5莫耳%至40莫耳%,較好為5莫耳%至30莫耳%。形成以前述式(2)表示之構造單位之單體之比例超過40莫耳%時,所合成之共聚物有容易凝膠化之情況。此種共聚物難具有對溶劑之溶解性。另一方面,形成以前述式(2)表示之構造單位之單體之比例未達5莫耳%時,有無法獲得本發明效果之情況。
前述共聚物之重量平均分子量為例如3000至20000,較好為3000至13000。前述共聚物之重量平均分子量在上述範圍外時,所形成之阻劑圖型之下襬狀成為底切形狀或腳底(footing)形狀,前述聚合物之重量平均分子量愈大則前述下襬形狀愈容易成為腳底形狀,故無法獲得本發明之效果。
本發明之第一樣態之添加劑可為進一步含有使前述共聚物溶解之溶劑之溶液狀,亦可進一步含有合成前述共聚物時所用之化合物。
本發明之第二樣態為阻劑底層膜形成組成物,其包含前述本發明之第一樣態之添加劑、與前述共聚物不同之樹脂、有機酸、交聯劑及溶劑。
前述樹脂為例如聚酯。前述添加劑相對於前述樹脂100質量份含有5質量份至20質量份,較好10質量份至15質量份。
於阻劑圖型形成方法中,較好使用本發明之
第二樣態之阻劑底層膜形成組成物,該阻劑圖型形成方法包含:於基板上形成阻劑底層膜之階段、於前述阻劑底層膜上形成阻劑膜之階段、透過光罩使前述阻劑膜曝光之階段、與前述曝光後使用可使前述阻劑膜之未曝光部溶解之溶劑進行顯像並去除前述未曝光部之階段。前述阻劑膜可使用習知之正型阻劑溶液而形成。可使前述阻劑膜之未曝光部溶解之溶劑隨著形成該阻劑膜時所用之阻劑溶液之種類而不同,通常係使用習知之有機溶劑。
藉由於微影製程中應用包含本發明之添加劑之阻劑底層膜形成組成物,可防止阻劑圖型之崩塌,且可使阻劑圖型之剖面形狀成為直線狀。且,可提高由該阻劑底層膜形成組成物形成之阻劑底層膜與阻劑圖型之密著性。
圖1係顯示以掃描型電子顯微鏡(SEM)觀察使用實施例1至實施例13及比較例1至比較例4中調製之阻劑底層膜形成組成物,於矽晶圓上形成之阻劑底層膜上形成之62nm之L/S阻劑圖型之剖面結果之SEM像。
本發明之第一樣態之添加劑係包含具有以前述式(1)至式(4)表示之構造單位之共聚物者。
形成以前述式(1)表示之構造單位之單體列舉為例如對-羥基苯乙烯、對-第三丁氧基苯乙烯、間-第三丁氧基苯乙烯、對-第三戊氧基苯乙烯、對-第三辛氧基苯乙烯、2-第三丁氧基-6-乙烯基萘、對-乙醯氧基苯乙烯、2-乙醯氧基-6-乙烯基萘、及對-(1-乙氧基乙氧基)苯乙烯。
形成以前述式(2)表示之構造單位之單體列舉為例如丙烯酸2-甲苯磺醯基乙酯、甲基丙烯酸2-甲苯磺醯基乙酯、苯基乙烯基碸、及對-甲苯基乙烯基碸。
形成以前述式(3)表示之構造單位之單體列舉為例如丙烯酸2,2,2-三氟乙酯、甲基丙烯酸2,2,2-三氟乙酯、丙烯酸1,1,1,3,3,3-六氟異丙酯、甲基丙烯酸1,1,1,3,3,3-六氟異丙酯、及甲基丙烯酸(1,2-二氟乙酯)。
形成以前述式(4)表示之構造單位之單體列舉為例如γ-丁內酯丙烯酸酯、γ-丁內酯甲基丙烯酸酯、甲羥戊酸內酯甲基丙烯酸酯、丙烯酸1-金剛烷酯、甲基丙烯酸1-金剛烷酯、丙烯酸2-甲基-2-金剛烷酯、甲基丙烯酸2-甲基-2-金剛烷酯、丙烯酸2-乙基-2-金剛烷酯、甲基丙烯酸2-乙基-2-金剛烷酯、丙烯酸異冰片酯、及甲基丙烯酸異冰片酯。
以前述式(1)表示之構造單位列舉為例如以
下述式(1-1)至式(1-8)表示之構造單位。以前述式(1)表示之構造單位之以Ar表示之伸芳基係選自伸苯基或伸萘基。以前述式(1)表示之構造單位成為酸性部位。
以前述式(2)表示之構造單位列舉為例如以下述式(2-1)至式(2-4)表示之構造單位。下述式中僅列示以前述式(2)表示之構造單位之R3表示氫原子或甲基之例,但R3表示鹵基時,係選自由氟基、氯基、溴基、及碘基所組成之群。以前述式(2)表示之構造單位成為光酸產生部位。
以前述式(3)表示之構造單位列舉為例如以下述式(3-1)至式(3-5)表示之構造單位。以前述式(3)表示之構造單位成為使共聚物移行至膜表面之部位。
以前述式(4)表示之構造單位列舉為例如以下述式(4-1)至式(4-16)表示之構造單位。至於以前述式(4)表示之構造單位之Z係選擇具有導入於阻劑溶液中之聚合物的骨架(環狀構造)之有機基。
本發明之添加劑之共聚物具有以前述式(1)至式(4)表示之全部構造單位,藉此可調整由含該添加劑之阻劑底層膜形成組成物形成之阻劑底層膜表面附近之酸性度,提高該阻劑底層膜與阻劑圖型之密著性,結果可抑制該阻劑圖型之崩塌,且可使於該阻劑底層膜上形成之阻劑圖型之剖面形狀成為直線形狀。
本發明之第二樣態之阻劑底層膜形成組成物係包含與
前述添加劑之共聚物不同之樹脂者。前述樹脂只要為使用於阻劑底層膜形成組成物中之聚合物即無特別限制。列舉為例如具有以下述式(5)表示之構造單位之聚合物,及具有以下述式(6)表示之構造單位之聚合物。
前述阻劑底層膜形成組成物係進一步包含交聯劑者。前述交聯劑列舉為例如六甲氧基甲基三聚氰胺、四甲氧基甲基苯并胍、1,3,4,6-肆(甲氧基甲基)甘醇脲(POWDERLINK〔註冊商標〕1174)、1,3,4,6-肆(丁氧基甲基)甘醇脲、1,3,4,6-肆(羥基甲基)甘醇脲、1,3-雙(羥基甲基)脲、1,1,3,3-肆(丁氧基甲基)脲及1,1,3,3-肆(甲氧基甲基)脲。前述交聯劑之含有比例相對於前述樹脂為例如1質量%至30質量%。
前述阻劑底層膜形成組成物係進而包含有機酸者。前述有機酸為促進交聯反應之觸媒成分,列舉為例如對-甲苯磺酸、三氟甲烷磺酸、吡啶鎓-對-甲苯磺酸鹽、水楊酸、樟腦磺酸、5-磺基水楊酸、4-氯苯磺酸、4-苯酚磺酸、4-苯酚磺酸甲酯、苯二磺酸、1-萘磺酸、檸檬酸、苯甲酸、羥基苯甲酸等磺酸化合物及羧酸化合物。該等有機酸可單獨使用,亦可含有2種以上之組合。前述有機酸之含有比例相對於前述交聯劑為例如0.1質量%至20質量%。
前述阻劑底層膜形成組成物係進而包含溶劑者。前述溶劑列舉為例如丙二醇單甲基醚(PGME)、丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇單乙基醚、丙二醇單丙基醚、甲基乙基酮、乳酸乙酯、環己酮、γ-丁內酯、N-甲基吡咯啶酮、及自該等溶劑選出之2種以上之混合物。前述溶劑之比例相對於前述阻劑底層膜形成組成物為例如50質量%至99.5質量%。
前述阻劑底層膜形成組成物亦可視需要進一步含有界面活性劑。界面活性劑係為了提高前述阻劑底層膜形成組成物對基板之塗佈性之添加物,可使用如非離子系界面活
性劑、氟系界面活性劑之習知界面活性劑。前述界面活性劑之具體例列舉為例如聚氧伸乙基月桂基醚、聚氧伸乙基硬脂基醚、聚氧伸乙基晶蠟基醚、聚氧伸乙基油基醚等聚氧伸乙基烷基醚類,聚氧伸乙基辛基苯基醚、聚氧伸乙基壬基苯基醚等聚氧伸乙基烷基芳基醚類,聚氧伸乙基.聚氧伸丙基嵌段共聚物類、山梨糖醇酐單月桂酸酯、山梨糖醇酐單棕櫚酸酯、山梨糖醇酐單硬脂酸酯、山梨糖醇酐單油酸酯、山梨糖醇酐三油酸酯、山梨糖醇酐三硬脂酸酯等山梨糖醇酐脂肪酸酯類,聚氧伸乙基山梨糖醇酐單月桂酸酯、聚氧伸乙基山梨糖醇酐單棕櫚酸酯、聚氧伸乙基山梨糖醇酐單硬脂酸酯、聚氧伸乙基山梨糖醇酐三油酸酯、聚氧伸乙基山梨糖醇酐三硬脂酸酯等聚氧伸乙基山梨糖醇酐脂肪酸酯類等之非離子系界面活性劑,EF TOP〔註冊商標〕EF301、EF TOP EF303、EF TOP EF352(三菱材料電子化成(股)製)、MEGAFAC〔註冊商標〕F171、MEGAFAC F173、MEGAFAC R-30、MEGAFAC R-40、MEGAFAC R-40-LM(DIC(股)製)、FLORARD FC430、FLORARD FC431(住友3M(股)製)、ASAHI GUARD〔註冊商標〕AG710、SURFLON〔註冊商標〕S-382、SURFLON SC101、SURFLON SC102、SURFLON SC103、SURFLON SC104、SURFLON SC105、SURFLON SC106(旭硝子(股)製)等氟系界面活性劑,有機矽氧烷聚合物KP341(信越化學工業(股)製)等。該等界面活性劑可單獨含有,亦可以2種以上之組合含有。前述阻
劑底層膜形成組成物含有界面活性劑時,前述界面活性劑之比例相對於前述樹脂為例如0.1質量%至5質量%,較好為0.2質量%至3質量%。
本說明書之下述合成例1至合成例15所示之聚合物之平均分子量為以凝膠滲透層析儀(以下簡稱為GPC)之測定結果。測定係使用TOSOH(股)製之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/分鐘
標準試料:聚苯乙烯(TOSOH(股)製)
使單烯丙基二縮水甘油基異氰尿酸10.00g、3,3’-二硫代二丙酸7.48g、及溴化乙基三苯基鏻0.66g溶解於丙二醇單甲基醚72.94g後,在125℃反應4小時,獲得含有聚合物(樹脂)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為4800。
使單甲基二縮水甘油基異氰尿酸10.00g、3,3’-二硫代二丙酸7.85g、及溴化乙基三苯基鏻0.66g溶解於丙二醇單甲基醚72.94g後,在105℃反應24小時,獲得含有聚合物(樹脂)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為3400。
於500ml之四頸燒瓶中添加2-甲苯磺醯基乙醇60.00g、三乙胺45.48g、氫醌0.007g及丙酮180g,在5℃攪拌。將甲基丙醯氯46.98g滴加於其攪拌物後,升溫至25℃,再攪拌1小時。過濾所得之鹽後,以丙酮60g洗淨該鹽,回收濾液。將回收之濾液滴加於水300g中而析出固體,以水120g洗淨該固體後,進行減壓乾燥,獲得粗製產物。於所得粗製產物中添加庚烷300g及乙酸乙酯90g,在70℃加熱溶解,以過濾去除不溶解物。於濾液中滴加庚烷60g且緩慢冷卻進行再結晶,以庚烷60g洗淨所得固體,經減壓乾燥,獲得目標物之甲基丙烯酸2-甲苯磺醯基乙酯。
使對-第三丁氧基苯乙烯2.70g(45mol%)、合成例3獲得之甲基丙烯酸2-甲苯磺醯基乙酯0.30g(5mol%)、甲基丙烯酸2,2,2-三氟乙酯1.20g(20mol%)、甲基丙烯酸γ-丁內酯1.80g(30mol%)及偶氮雙異丁腈0.30g溶解
於丙二醇單甲基醚12.60g中。使該溶液緩慢滴加於升溫至100℃之丙二醇單甲基醚12.60g中,滴加後在100℃反應2小時,獲得含有聚合物(共聚物)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為9800。
使對-第三丁氧基苯乙烯2.40g(40mol%)、合成例3獲得之甲基丙烯酸2-甲苯磺醯基乙酯1.50g(10mol%)、甲基丙烯酸2,2,2-三氟乙酯0.60g(20mol%)、甲基丙烯酸γ-丁內酯1.80g(30mol%)及偶氮雙異丁腈0.30g溶解於丙二醇單甲基醚12.60g中。使該溶液緩慢滴加於升溫至100℃之丙二醇單甲基醚12.60g中,滴加後在100℃反應2小時,獲得含有聚合物(共聚物)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為5600。
使對-第三丁氧基苯乙烯1.80g(30mol%)、合成例3獲得之甲基丙烯酸2-甲苯磺醯基乙酯1.20g(20mol%)、甲基丙烯酸2,2,2-三氟乙酯1.20g(20mol%)、甲基丙烯酸γ-丁內酯1.80g(30mol%)及偶氮雙異丁腈0.30g溶解於丙二醇單甲基醚12.60g中。使該溶液緩慢滴加於升溫至100℃之丙二醇單甲基醚12.60g中,滴加後在100℃反
應2小時,獲得含有聚合物(共聚物)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為7800。
使對-第三丁氧基苯乙烯1.50g(25mol%)、合成例3獲得之甲基丙烯酸2-甲苯磺醯基乙酯1.50g(25mol%)、甲基丙烯酸2,2,2-三氟乙酯1.20g(20mol%)、甲基丙烯酸γ-丁內酯1.80g(30mol%)及偶氮雙異丁腈0.30g溶解於丙二醇單甲基醚12.60g中。使該溶液緩慢滴加於升溫至100℃之丙二醇單甲基醚12.60g中,滴加後在100℃反應2小時,獲得含有聚合物(共聚物)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為7400。
使對-第三丁氧基苯乙烯1.20g(20mol%)、合成例3獲得之甲基丙烯酸2-甲苯磺醯基乙酯1.80g(30mol%)、甲基丙烯酸2,2,2-三氟乙酯1.20g(20mol%)、甲基丙烯酸γ-丁內酯1.80g(30mol%)及偶氮雙異丁腈0.30g溶解於丙二醇單甲基醚12.60g中。使該溶液緩慢滴加於升溫至100℃之丙二醇單甲基醚12.60g中,滴加後在100℃反應2小時,獲得含有聚合物(共聚物)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之
重量平均分子量為7300。
使對-第三丁氧基苯乙烯1.50g(25mol%)、合成例3獲得之甲基丙烯酸2-甲苯磺醯基乙酯1.50g(25mol%)、甲基丙烯酸2,2,2-三氟乙酯2.40g(40mol%)、甲基丙烯酸γ-丁內酯0.60g(10mol%)及偶氮雙異丁腈0.30g溶解於丙二醇單甲基醚12.60g中。使該溶液緩慢滴加於升溫至100℃之丙二醇單甲基醚12.60g中,滴加後在100℃反應2小時,獲得含有聚合物(共聚物)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為6300。
使對-第三丁氧基苯乙烯1.50g(25mol%)、合成例3獲得之甲基丙烯酸2-甲苯磺醯基乙酯1.50g(25mol%)、甲基丙烯酸2,2,2-三氟乙酯1.80g(30mol%)、甲基丙烯酸γ-丁內酯1.20g(20mol%)及偶氮雙異丁腈0.30g溶解於丙二醇單甲基醚12.60g中。使該溶液緩慢滴加於升溫至100℃之丙二醇單甲基醚12.60g中,滴加後在100℃反應2小時,獲得含有聚合物(共聚物)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為5500。
使對-第三丁氧基苯乙烯1.50g(25mol%)、合成例3獲得之甲基丙烯酸2-甲苯磺醯基乙酯1.50g(25mol%)、甲基丙烯酸2,2,2-三氟乙酯0.60g(10mol%)、甲基丙烯酸γ-丁內酯2.40g(40mol%)及偶氮雙異丁腈0.30g溶解於丙二醇單甲基醚12.60g中。使該溶液緩慢滴加於升溫至100℃之丙二醇單甲基醚12.60g中,滴加後在100℃反應2小時,獲得含有聚合物(共聚物)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為5900。
使對-第三丁氧基苯乙烯1.50g(25mol%)、合成例3獲得之甲基丙烯酸2-甲苯磺醯基乙酯1.50g(25mol%)、甲基丙烯酸2,2,2-三氟乙酯1.20g(20mol%)、甲基丙烯酸γ-丁內酯1.80g(30mol%)及偶氮雙異丁腈0.45g溶解於丙二醇單甲基醚12.60g中。使該溶液緩慢滴加於升溫至100℃之丙二醇單甲基醚12.60g中,滴加後在100℃反應2小時,獲得含有聚合物(共聚物)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為4700。
使對-第三丁氧基苯乙烯1.50g(25mol%)、合成例3
獲得之甲基丙烯酸2-甲苯磺醯基乙酯1.50g(25mol%)、甲基丙烯酸2,2,2-三氟乙酯1.20g(20mol%)、甲基丙烯酸γ-丁內酯1.80g(30mol%)及偶氮雙異丁腈0.23g溶解於丙二醇單甲基醚12.60g中。使該溶液緩慢滴加於升溫至100℃之丙二醇單甲基醚12.60g中,滴加後在100℃反應2小時,獲得含有聚合物(共聚物)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為9700。
使對-第三丁氧基苯乙烯1.50g(25mol%)、苯基乙烯基碸1.50g(25mol%)、甲基丙烯酸2,2,2-三氟乙酯1.20g(20mol%)、甲基丙烯酸γ-丁內酯1.80g(30mol%)及偶氮雙異丁腈0.30g溶解於丙二醇單甲基醚12.60g中。使該溶液緩慢滴加於升溫至100℃之丙二醇單甲基醚12.60g中,滴加後在100℃反應2小時,獲得含有聚合物(共聚物)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為4300。
使對-第三丁氧基苯乙烯3.00g(50mol%)、甲基丙烯酸2,2,2-三氟乙酯1.20g(20mol%)、甲基丙烯酸γ-丁內酯1.80g(30mol%)及偶氮雙異丁腈0.30g溶解於丙二
醇單甲基醚12.60g中。使該溶液緩慢滴加於升溫至100℃之丙二醇單甲基醚12.60g中,滴加後在100℃反應2小時,獲得含有聚合物(共聚物)之溶液。對所得溶液中所含聚合物進行GPC分析,以標準聚苯乙烯換算之重量平均分子量為19800。本合成例中獲得之聚合物為不具有以前述式(2)表示之構造單位之共聚物。
以下述表1所示之比例混合上述合成例1或合成例2所得之樹脂、作為添加劑之合成例4至合成例15所得之任一共聚物、交聯劑、有機酸、界面活性劑及溶劑,分別調製實施例1至實施例13及比較例1至比較例4之阻劑底層膜形成組成物。表1所示之添加劑之添加量並非聚合物溶液之添加量,而是表示聚合物(共聚物)本身之添加量。表1中,分別將四甲氧基甲基甘醇脲(日本CYTEC INDUSTRIES(股)製,商品名:POWDERLINK〔註冊商標〕1174)簡稱為“PL-LI”,4-苯酚磺酸簡稱為“PSA”,5-磺基水楊酸簡稱為“5-SSA”,4-苯酚磺酸甲酯簡稱為“MSP”,MEGAFAC〔註冊商標〕R-40(DIC(股)製)簡稱為“R-40”,丙二醇單甲基醚乙酸酯簡稱為“PGMEA”,丙二醇單甲基醚簡稱為“PGME”。表1中,實施例1至實施例13及比較例1至比較例4之阻劑底層膜形成組成物中之各成分係以質量份表示,且將溶劑設為100質量份。
[表1]
使用旋轉塗佈器將實施例1至實施例13及比較例1至比較例4中調製之阻劑底層膜形成組成物分別塗佈於矽晶圓上。使該矽晶圓在加熱板上,於205℃加熱1分鐘,形成阻劑底層膜(膜厚28nm)。接著,使用分光橢圓光度計(J.A.Woollam公司製,VUV-VASE VU-302),測定該等阻劑底層膜之於波長193nm、248nm之折射率(n值)及光學吸光係數(k值,亦稱為衰減係數)。下述表2中,n1、k1分別表示波長193nm下之折射率及吸光係數,n2、k2分別表示波長248nm下之折射率及吸光係數。
使用旋轉塗佈器將實施例1至實施例13及比較例1至比較例4中調製之阻劑底層膜形成組成物分別塗佈於矽晶圓上。使該矽晶圓在加熱板上,於205℃加熱60秒,形成膜厚28nm之阻劑底層膜。將ArF準分子雷射用正型阻劑溶液旋轉塗佈於該阻劑底層膜上,在80℃加熱60秒,形成ArF阻劑膜。對該阻劑膜,使用ArF準分子雷射用曝光裝置(NIKON(股)製,NSR S307R),在特定條件下曝光。曝光後,在95℃進行烘烤(PEB)60秒,於冷卻板上冷卻至室溫,以乙酸丁酯顯像後,以乙酸丁酯進行洗滌處理,形成線與間隔之阻劑圖型。此處由於並非使用鹼性水溶液而是使用乙酸丁酯作為顯像液,故洗滌處理中使用水並不適當。使用掃描型電子顯微鏡(Hitachi High-Tech Fielding Corporation(股)製,S-4800)評價可否形成各62nm及45nm之線與間隔(以下簡稱為L/S),以及藉由圖型剖面觀察之62nm之L/S圖型形狀進行評價之結果示於下述表3及圖1。
[表3]
使用實施例1至實施例13中調製之阻劑底層膜形成組成物形成之62nm之L/S之圖型形狀均不為底切、腳底形狀而為直線形狀,未觀察到圖型崩塌。另一方面,使用比較例1至比較例4中調製之阻劑底層膜形成組成物形成之62nm之L/S圖型形狀為底切或腳底形狀。且,僅於使用比較例1及比較例2中調製之阻劑底層膜形成組成物時,無法形成45nm之L/S。
Claims (10)
- 一種阻劑底層膜形成組成物用之添加劑,其包含具有以下述式(1)至式(4)表示之構造單位之共聚物,
- 如請求項1之添加劑,其中,前述保護基為乙醯基、甲氧基甲基、乙氧基乙基、碳原子數4至8之3級烷基、或特戊醯基。
- 如請求項1或2之添加劑,其中,以前述式(2)表示之構造單位係以下述式(2a)或式(2b)表示之構造單位,
- 如請求項1至3中任一項之添加劑,其中,以前述式(4)表示之構造單位係以下述式(4a)表示之構造單位,
- 如請求項1至4中任一項之添加劑,其中,前述共聚物係使形成以前述式(1)表示之構造單位之單體、形成以前述式(2)表示之構造單位之單體、形成以前述式(3)表示之構造單位之單體、與形成以前述式(4)表 示之構造單位之單體進行共聚合而合成之化合物,且相對於前述4種單體之合計100莫耳%,形成以前述式(2)表示之構造單位之單體之比例為5莫耳%至40莫耳%。
- 如請求項1至5中任一項之添加劑,其中,前述共聚物之重量平均分子量為3000至20000。
- 一種阻劑底層膜形成組成物,其包含如請求項1至6中任一項之添加劑、與前述共聚物不同之樹脂、有機酸、交聯劑及溶劑。
- 如請求項7之阻劑底層膜形成組成物,其中,前述樹脂為聚酯。
- 如請求項7或8之阻劑底層膜形成組成物,其中,前述添加劑相對於前述樹脂100質量份含有5質量份至20質量份。
- 一種阻劑圖型之形成方法,其包含下述階段:使用如請求項7至9中任一項之阻劑底層膜形成組成物於基板上形成阻劑底層膜之階段、使用正型阻劑溶液於前述阻劑底層膜上形成阻劑膜之階段、透過光罩使前述阻劑膜曝光之階段、與前述曝光後使用可使前述阻劑膜之未曝光部溶解之溶劑進行顯像並去除前述未曝光部之階段。
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