TW202116833A - 包含具有硬化性官能基之化合物之階差基板被覆組成物 - Google Patents
包含具有硬化性官能基之化合物之階差基板被覆組成物 Download PDFInfo
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Abstract
Description
本發明係關於用於在具有階差的基板上被光照射或加熱而硬化以形成平坦化膜的階差基板被覆組成物、與使用所述階差基板被覆組成物之經平坦化的積層基板的製造方法。
近年來,半導體積體電路裝置係以被加工成細微設計規則之方式而完成。為了藉由光微影術技術形成更細微的阻劑圖案,需要將曝光波長進行短波長化。
但是,因伴隨著曝光波長的短波長化而焦點深度會降低,故變得需要使形成在基板上的被膜的平坦化性提升。亦即,為了製造具有細微設計規則的半導體裝置,基板上的平坦化技術逐漸變得重要。
至今,作為平坦化膜的形成方法,已揭示例如藉由光硬化而形成在阻劑膜下所形成之阻劑下層膜的方法。
已揭示一種阻劑下層膜形成組成物,其包含在側鏈具有環氧基、氧環丁烷基(oxetanyl)的聚合物與光陽離子聚合開始劑,或一種阻劑下層膜形成組成物,其包含具有能自由基聚合的乙烯性不飽和鍵之聚合物與光自由基聚合起始劑(參照專利文獻1)。
又,已揭示一種阻劑下層膜形成組成物,其包含具有環氧基、乙烯基等能陽離子聚合的反應性基之矽系化合物、光陽離子聚合起始劑、及光自由基聚合起始劑(參照專利文獻2)。
又,已揭示一種半導體裝置的製造方法,其使用含有在側鏈具有交聯性官能基(例如羥基)的聚合物、交聯劑及光酸產生劑之阻劑下層膜(參照專利文獻3)。
又,已揭示一種阻劑下層膜,其雖非光交聯系的阻劑下層膜,但在主鏈或側鏈具有不飽和鍵(參照專利文獻4、5)。
又,已揭示一種阻劑下層膜,其係由在側鏈具有環氧基的聚合物所構成(參照專利文獻6)。
[先前技術文獻]
[專利文獻]
[專利文獻1]國際公開手冊WO2006/115044
[專利文獻2]國際公開手冊WO2007/066597
[專利文獻3]國際公開手冊WO2008/047638
[專利文獻4]國際公開手冊WO2009/008446
[專利文獻5]日本特表2004-533637
[專利文獻6]國際公開手冊WO2019/054420
[發明概要]
[發明所欲解決的課題]
在以往的光交聯材料中,例如在包含具有羥基等熱交聯形成官能基的聚合物、交聯劑及酸觸媒(酸產生劑)之阻劑下層膜形成組成物中,已填充形成在基板上的圖案(例如,孔洞或溝槽結構)之方式加熱該組成物之際,進行交聯反應而產生黏度上升,其結果,對圖案的填充不良會成為問題。再者,因產生由脫氣所致之熱收縮,故平坦性受損會成為問題。
因此,本發明的課題係提供一種階差基板被覆組成物,其係用於在基板上形成對圖案的填充性高、不發生脫氣及熱收縮且具有能形成塗膜之平坦化性的被膜。
[用於解決課題的手段]
本發明,作為第1觀點,係一種階差基板被覆組成物,其係包含主劑的化合物(A)與溶劑之階差基板被覆組成物,
該化合物(A)係包含由下述式(A-1)、式(A-2)或式(A-3)所表示之部分結構的化合物,且被光照射或加熱會硬化:
(式中,虛線表示與芳香族環的鍵結,芳香族環為構成聚合物骨架的芳香族環或構成單體的芳香族環,n表示1至4的整數)。
(式中,鏈線表示構成聚合物骨架的鏈狀碳鏈、與脂環式碳環或芳香族環的鍵結,Q表示單鍵、或者具有醚鍵、酯鍵、胺基甲酸酯鍵、碳數1至3的亞烷基鍵或醯胺鍵的有機基,惟,在式(A-3)中,不包含式(A-1)。m表示1);
作為第2觀點,係如第1觀點所記載之階差基板被覆組成物,其中,上述芳香族環為苯環、萘環或蒽環;
作為第3觀點,係如第1觀點或第2觀點所記載之階差基板被覆組成物,其中,包含上述芳香族環的聚合物係包含羥基芳基酚醛結構的聚合物,且係其羥基被式(A-1)或式(A-2)的部分結構所取代之聚合物;
作為第4觀點,係如第1觀點或第2觀點所記載之階差基板被覆組成物,其中,包含上述芳香族環的單體係芳香族環的羥基被式(A-1)或式(A-2)的部分結構所取代之單體;
作為第5觀點,係如第1觀點至第4觀點中任一個所記載之階差基板被覆組成物,其中,更包含酸產生劑;
作為第6觀點,係如第1觀點至第5觀點中任一個所記載之階差基板被覆組成物,其中,更包含界面活性劑;
作為第7觀點,係一種被覆基板的製造方法,其包含:步驟(i),其在具有階差的基板塗布如第1觀點至第6觀點中任一個所記載之階差基板被覆組成物;及步驟(ii),其將由步驟(i)所塗布之組成物進行曝光或在曝光中至曝光後加熱;
作為第8觀點,係如第7觀點所記載之被覆基板的製造方法,其中,在上述步驟(i),在上述進行曝光的步驟(ii)之前,加上步驟(ia),其以70℃至400℃的溫度將具有階差的基板上的階差基板被覆組成物加熱10秒鐘至5分鐘;
作為第9觀點,係如第7觀點或第8觀點所記載之被覆基板的製造方法,其中,在上述步驟(ii)中,曝光所用的光係波長為150nm至700nm的光;
作為第10觀點,係如第7觀點至第9觀點中任一個所記載之被覆基板的製造方法,其中,在上述步驟(ii)中,曝光光量為10mJ/cm2
至5000mJ/cm2
;
作為第11觀點,係如第7觀點所記載之被覆基板的製造方法,其中,在上述步驟(ii)中,以100℃至500℃的溫度進行加熱;
作為第12觀點,係如第7觀點至第11觀點中任一個所記載之被覆基板的製造方法,其中,上述具有階差的基板具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,圖案的縱橫比為0.1至100;
作為第13觀點,係如第7觀點至第12觀點中任一項所記載之被覆基板的製造方法,其中,上述具有階差的基板具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,開放區域與圖案區域之Bias(塗布階差)為1nm至50nm;
作為第14觀點,係一種半導體裝置的製造方法,其包含:具有階差的基板上形成如第1觀點至第6觀點中任一個所記載之階差基板被覆組成物所構成之下層膜的步驟;在其上形成阻劑膜的步驟;接下來將此進行光或者電子射線的照射,或者在光或電子射線的照射中至照射後進行加熱,藉由之後的顯影而形成阻劑圖案的步驟;藉由所形成之阻劑圖案將該下層膜進行蝕刻的步驟;及藉由經圖案化的下層膜將半導體基板進行加工的步驟;
作為第15觀點,係如第14觀點所記載之半導體裝置的製造方法,其中,上述形成下層膜的步驟包含:步驟(i),其在上述具有階差的基板塗布如第1觀點至第6觀點中任一個所記載之階差基板被覆組成物;及步驟(ii),其將由步驟(i)所塗布之組成物進行曝光或加熱;
作為第16觀點,係如第15觀點所記載之半導體裝置的製造方法,其中,在上述步驟(i),在上述進行曝光的步驟(ii)之前,加上步驟(ia),其以70℃至400℃的溫度將具有階差的基板上的階差基板被覆組成物加熱10秒鐘至5分鐘;
作為第17觀點,係如第15觀點或第16觀點所記載之半導體裝置的製造方法,其中,在上述步驟(ii)中,曝光所用的光係波長為150nm至700nm的光;
作為第18觀點,係如第15觀點至第17觀點中任一個所記載之半導體裝置的製造方法,其中,在上述步驟(ii)中,曝光光量為10mJ/cm2
至5000mJ/cm2
;
作為第19觀點,係如第15觀點所記載之半導體裝置的製造方法,其中,在上述步驟(ii)中,以100℃至500℃的溫度進行加熱;
作為第20觀點,係如第14觀點至第19觀點中任一個所記載之半導體裝置的製造方法,其中,上述具有階差的基板具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,且係圖案的縱橫比為0.1至100基板;
作為第21觀點,係如第14觀點至第20觀點中任一個所記載之半導體裝置的製造方法,其中,上述具有階差的基板具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,由上述階差基板被覆組成物所得之下層膜具有1nm至50nm的開放區域與圖案區域之Bias(塗布階差);
作為第22觀點,係一種半導體裝置的製造方法,其包含:在具有階差的基板形成由如第1觀點至第6觀點中任一個所記載之階差基板被覆組成物所構成之下層膜的步驟;在其上形成硬遮罩(hard mask)的步驟;再在其上形成阻劑膜的步驟、接下來將此進行光或者電子射線的照射,或者在光或電子射線的照射中至照射後進行加熱,藉由之後的顯影而形成阻劑圖案的步驟;藉由所形成之阻劑圖案將硬遮罩進行蝕刻的步驟;藉由經圖案化的硬遮罩將該下層膜進行蝕刻的步驟;及藉由經圖案化的下層膜將半導體基板進行加工的步驟;
作為第23觀點,係如第22觀點所記載之半導體裝置的製造方法,其中,上述形成下層膜的步驟包含:步驟(i),其在上述具有階差的基板塗布如第1觀點至第6觀點中任一個所記載之階差基板被覆組成物;及步驟(ii),其將由步驟(i)所塗布之組成物進行曝光或加熱;
作為第24觀點,係如第23觀點所記載之半導體裝置的製造方法,其中,在上述步驟(i),在上述進行曝光的步驟(ii)之前,加上步驟(ia),其以70℃至400℃的溫度將具有階差的基板上的階差基板被覆組成物加熱10秒鐘至5分鐘;
作為第25觀點,係如第23觀點或第24觀點所記載之半導體裝置的製造方法,其中,在上述步驟(ii)中,曝光所用的光係波長為150nm至700nm的光;
作為第26觀點,係如第23觀點至第25觀點中任一個所記載之半導體裝置的製造方法,其中,在上述步驟(ii)中,曝光光量為10mJ/cm2
至5000mJ/cm2
;
作為第27觀點,係如第23觀點所記載之半導體裝置的製造方法,其中,在上述步驟(ii)中,以100℃至500℃的溫度進行加熱;
作為第28觀點,係如第22觀點至第27觀點中任一個所記載之半導體裝置的製造方法,其中,上述具有階差的基板具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,且係圖案的縱橫比為0.1至100的基板;及
作為第29觀點,係如第22觀點至第28觀點中任一項所記載之半導體裝置的製造方法,其中,上述具有階差的基板具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,由上述階差基板被覆組成物所得之下層膜具有1nm至50nm的開放區域與圖案區域之Bias(塗布階差)。
[發明效果]
在本發明的階差基板被覆組成物因光照射而硬化之情形中,首先,因係以低溫進行加熱,故在其溫度下不會引起交聯反應。亦即,在階差基板上能獲得充分的平坦化性。再者,因藉由光而硬化,故可獲得良好的平坦化膜。又,在僅因加熱而硬化之情形,因在聚合物內所具有之交聯基的交聯起始溫度高,故在以高溫使其充分地回流後,交聯反應會開始,藉此能獲得良好的平坦化膜。
又,本發明的階差基板被覆組成物,被塗布於階差基板上,不論階差基板上的開放區域(非圖案區域)、由DENCE(密)及ISO(粗)所構成之圖案區域為何,皆可形成平坦的膜。再者,藉由本發明的階差基板被覆組成物所形成之階差基板被覆膜(平坦化膜),因不需要交聯劑,故在熱回流時不會產生由交聯劑與酸觸媒所致之交聯反應。又,在光照射之情形中,硬化因係不伴隨脫氣的光反應,故不產生熱收縮。
亦即,藉由本發明的階差基板被覆組成物,可提供同時滿足對圖案的良好填充性與填充後的平坦性之優異的平坦化膜。
再者,本發明的階差基板被覆組成物可因加熱或曝光而硬化。尤其,因僅以加熱便可硬化,故操作上便利,可提高生產效率。
[用於實施發明的形態]
本發明係一種階差基板被覆組成物,其係包含主劑的化合物(A)與溶劑之階差基板被覆組成物,該化合物(A)係包含由下述式(A-1)、式(A-2)或式(A-3)所表示之部分結構的化合物,且被光照射或加熱會硬化:
(式中,虛線表示與芳香族環的鍵結,芳香族環為構成聚合物骨架的芳香族環或構成單體的芳香族環,n表示1或2的整數)。
(式中,鏈線表示構成聚合物骨架的鏈狀碳鏈、與脂環式碳環或芳香族環的鍵結,Q表示單鍵、或者具有醚鍵、酯鍵、胺基甲酸酯鍵、碳數1至3的亞烷基鍵或醯胺鍵的有機基,m表示1。惟,在式(A-3)中,不包含式(A-1))。
式(A-1)中,n表示1或2的整數,虛線表示與芳香族環的鍵結,芳香族環係構成聚合物骨架的芳香族環或構成單體的芳香族環。
上述芳香族環可為苯環、萘環或蒽環。
包含芳香族環的聚合物可為包含羥基芳基酚醛結構的聚合物的羥基被式(A-1)的部分結構或式(A-2)的部分結構所取代之聚合物。此等芳基可使用源自苯、萘的芳香族基。此種聚合物未被限定,但可列舉例如如以下般者。
式(a-1)至式(a-13)的聚合物,其製法未被限定,但可遵循公知的方法,例如藉由前驅物聚合物的環氧基與2-呋喃甲酸進行縮合反應而被合成。
上述聚合物的重量平均分子量為600至1000000、或600至200000、或1500至15000。
又,本發明中,包含芳香族環的單體可為芳香族環的環氧丙基醚基被式(A-1)的部分結構或式(A-2)的部分結構所取代之單體。此種單體未被限定,但可列舉例如如以下般者。
式(aa-1)至式(aa-18)的單體化合物,係前驅物單體的環氧基藉由與2-呋喃甲酸的縮合而被取代,進而被合成。
包含上述芳香族環的單體可在分子量200至10000、或200至2000、或200至1000的範圍使用。
又,關於式(A-3),鏈線表示構成聚合物骨架的鏈狀碳鏈、與脂環式碳環或芳香族環的鍵結。Q表示單鍵、或者具有醚鍵、酯鍵、胺基甲酸酯鍵、碳數1至3的亞烷基鍵或醯胺鍵等的有機基。惟,在式(A-3)中,不包含式(A-1)。m表示1。
所列舉的醚鍵(-O-)、酯鍵(-COO-)、胺基甲酸酯鍵(-NHCOO-)、碳數1至3的亞烷基鍵(-CH2
-、-CH2
CH2
-、-CH2
CH2
CH2
-)、醯胺鍵(-CONH-)的鍵結方式,能適用將聚合物骨架與呋喃之間進行直接鍵結的方式、及作為包含該連結基的有機基而使用的方式。
在合成由前述式(A-3)所示的高分子化合物之際,同時使用成為其等原料的單體與能共聚合的其他單體而製造共聚物,並可使用作為本發明的高分子化合物。作為此能共聚合的其他單體,可使用丙烯酸酯、甲基丙烯酸酯、丙烯醯胺、甲基丙烯醯胺、乙烯基化合物、苯乙烯、順丁烯二醯亞胺、順丁烯二酸酐、丙烯腈等加成聚合性單體。此情形,在所得之高分子化合物中,由式(A-3)所示之單元結構與由加成聚合性單體所致之單元結構的比例,以質量比計為10/1~1/10,又為5/1~1/5,又為3/1~1/3。
前述高分子化合物的重量平均分子量(標準聚苯乙烯換算)為100以上,例如1000~200000、或1500~50000、或3000~50000、或4000~30000。此等高分子化合物係例示例如以下者。
本發明可含有酸產生劑。酸產生劑可使用光酸產生劑與熱酸產生劑。
作為光酸產生劑,可列舉例如,雙(4-t-丁基苯基)錪鎓三氟甲磺酸酯、三苯基鋶三氟甲磺酸酯等鎓鹽系光酸產生劑類、苯基-雙(三氯甲基)-s-三等含有鹵素的化合物系光酸產生劑類、甲苯磺酸安息香(benzoin tosylate)、N-羥基琥珀醯亞胺三氟甲磺酸酯等磺酸系光酸產生劑類等。相對於全部固體成分,上述光酸產生劑為0.2至5質量%,或0.4至5質量%,或0.4至4.9質量%,或0.4至4.8質量%。
作為熱酸產生劑,可列舉例如2,4,4,6-四溴環己烷二烯酮、甲苯磺酸安息香、2-硝基苄基甲苯磺酸酯、對甲苯磺酸吡啶鹽、對羥基苯磺酸吡啶鹽、其他有機磺酸烷基酯及其等的鹽等,作為市售品,可列舉K-PURE[註冊商標] CXC-1612、同CXC-1614、同CXC-1742、同CXC-1802、同TAG-2678、同TAG2681、同TAG2689、同TAG2690、同TAG2700(King Industries公司製)、及SI-45、SI-60、SI-80、SI-100、SI-110、SI-150(三新化學工業(股)製)。
此等熱酸產生劑可一種或組合二種以上而使用。相對於前述(A)的呋喃化合物的總質量,該熱酸產生劑的含量例如為0.01質量%至20質量%,較佳為0.1質量%至10質量%。
本發明的階差基板被覆組成物可含有界面活性劑。作為前述界面活性劑,可列舉例如,聚氧乙烯月桂基醚、聚氧乙烯十八基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯油基醚等聚氧乙烯烷基醚類、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚等聚氧乙烯烷基芳基醚類、聚氧乙烯-聚氧丙烯嵌段共聚物類、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、山梨糖醇酐單三油酸酯、山梨糖醇酐三硬脂酸酯等山梨糖醇酐脂肪酸酯類、聚氧乙烯山梨糖醇酐單月桂酸酯、聚氧乙烯山梨糖醇酐單棕櫚酸酯、聚氧乙烯山梨糖醇酐單硬脂酸酯、聚氧乙烯山梨糖醇酐單三油酸酯、聚氧乙烯山梨糖醇酐三硬脂酸酯等聚氧乙烯山梨糖醇酐脂肪酸酯類等的非離子系界面活性劑、Eftop[註冊商標]EF301、同EF303、同EF352(Mitsubishi Materials Electronic Chemicals (股)製)、Megafac[註冊商標]F171、同F173、同R30、同R-30N、R-40、同R-40LM(DIC(股)製)、FluoradFC430、同FC431(住友3M(股)製)、AsahiGuard[註冊商標]AG710、Surflon[註冊商標]S-382、同SC101、同SC102、同SC103、同SC104、同SC105、同SC106(旭硝子(股)製)等氟系界面活性劑、ORGANOSILOXANE POLYMER KP341(信越化學工業(股)製)。可添加選自此等界面活性劑的一種類,亦可組合二種以上而添加。相對於從本發明的階差基板被覆組成物去除後述溶劑的固體成分,前述界面活性劑的含有比例例如為0.01質量%至5質量%,或0.01質量%至2質量%,或0.01質量%至0.2質量%,或0.01質量%至0.1質量%,或0.01質量%至0.09質量%。
作為本發明中使化合物(A)溶解的溶劑,可使用乙二醇單甲醚、乙二醇單乙醚、乙二醇單丁醚、乙二醇單異丙醚、乙二醇甲醚乙酸酯、乙二醇乙基醚乙酸酯、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、二乙二醇、二乙二醇單甲醚、二乙二醇單乙基醚、二乙二醇二甲醚、二乙二醇二乙基醚、二乙二醇單乙醚乙酸酯、丙二醇、丙二醇單甲醚、丙二醇單丁基醚、丙二醇單甲醚乙酸酯、丙二醇單乙基醚、丙二醇單乙醚乙酸酯、丙二醇丙基醚乙酸酯、二丙二醇單甲醚、二丙二醇單乙基醚、三乙二醇二甲醚、甲苯、二甲苯、苯乙烯、甲基乙基酮、環戊酮、環己酮、2-羥基丙酸乙酯、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-3-甲基丁烷酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、丙酮酸乙酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯、1-辛醇、乙二醇、己烯二醇、三亞甲基二醇、1-甲氧基-2-丁醇、環己醇、二丙酮醇、呋喃甲醇、四氫呋喃甲醇、丙二醇、苯甲醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、γ-丁基內酯、丙酮、甲基異丙基酮、二乙基酮、甲基異丁基酮、甲基正丁基酮、乙酸異丙基酮、乙酸正丙酯、乙酸異丁酯、甲醇、乙醇、異丙醇、三級丁醇、烯丙醇、正丙醇、2-甲基-2-丁醇、異丁醇、正丁醇、2-甲基-1-丁醇、1-戊醇、2-甲基-1-戊醇、2-乙基己醇、異丙基醚、1,4-二噁烷、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、1,3-二甲基-2-咪唑啶酮、二甲亞碸、N-環己基-2-吡咯啶酮等。此等有機溶劑係單獨或組合二種以上而被使用。
接著,若針對使用本發明的階差基板被覆組成物之平坦化膜形成法進行說明,則係在被使用於精密集積電路元件的製造之基板(例如矽/二氧化矽被覆、玻璃基板、ITO基板等透明基板)上,藉由旋轉器、塗布機等適當的塗布方法塗布階差基板被覆組成物後,藉由進行烘烤(加熱)或曝光而作成被膜。亦即,包含在具有階差的基板塗布階差基板被覆組成物的步驟(i)、及將由步驟(i)所塗布之組成物進行曝光或加熱步驟(ii)而製造被覆基板。
使用旋轉器進行塗布時,例如可以旋轉數100至5000進行塗布10至180秒鐘。
上述基板可使用具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,且圖案的縱橫比為0.1至10、或0.1至100者。
所謂非圖案區域,表示在基板上無圖案(例如,孔洞或溝槽結構)的部分,DENCE(密)表示在基板上圖案密集的部分,ISO(粗)表示在基板上圖案與圖案之間隔廣且圖案點狀存在的部分。圖案的縱橫比係圖案深度相對於圖案寬度的比例。圖案深度通常為數百nm(例如,100至300nm左右),DENCE(密)係圖案為數十nm(例如30至80nm)左右的圖案且以100nm左右的間隔密集的地方。ISO(粗)係圖案為數百nm(例如200至1000nm左右)的圖案且點狀存在的地方。
於此,作為階差基板被覆膜(平坦化膜)的膜厚,較佳為0.01μm至3.0μm。又,作為步驟(ia),可在塗布後、光照射前進行加熱,作為其條件,係70℃至400℃、或100℃至250℃且10秒鐘至5分鐘、或30秒鐘至2分鐘。藉由此加熱,階差基板被覆組成物會回流而形成平坦的階差基板被覆膜(平坦化膜)。
在步驟(ii)中,曝光的光為近紫外線、遠紫外線等化學射線,例如能使用248nm(KrF雷射光)、193nm (ArF雷射光)、172nm(氙準分子光)、157nm(F2
雷射光)等波長的光。又,曝光可使用波長150nm至700nm的紫外光,而且,可較佳地使用172nm的波長。
藉由此曝光,進行階差基板被覆膜(平坦化膜)的交聯。在步驟(ii)中,曝光光量可設為10mJ/cm2
至3000mJ/cm2
、或10mJ/cm2
至5000mJ/cm2
。以此範圍的曝光光量,產生光反應,形成交聯,產生耐溶劑性。
又,在步驟(ii)中,亦能不光照射而僅以加熱進行階差基板被覆膜(平坦化膜)的交聯。加熱較佳為100℃至500℃、或200℃至400℃的溫度。在此範圍的溫度下,會產生酸,並引起硬化反應,藉此產生耐溶劑性。
如此形成的階差基板被覆膜(平坦化膜),其開放區域與圖案區域的Bias(塗布階差)期望為零,但能以成為1nm至50nm、或1nm至25nm的範圍之方式進行平坦化。開放區域與DENCE區域的Bias為15nm至20nm左右,開放區域與ISO區域的Bias為1nm至10nm左右。
藉由本發明所得之階差基板被覆膜(平坦化膜),可在其上被覆阻劑膜,藉由微影術將阻劑膜進行曝光與顯影而形成阻劑圖案,並依照所述阻劑圖案進行基板加工。所述情形,階差基板被覆膜(平坦化膜)為阻劑下層膜,階差基板被覆組成物亦為阻劑下層膜形成組成物。
在阻劑下層膜上塗布阻劑,通過指定的遮罩進行光或電子射線的照射,並藉由顯影、沖洗、乾燥而可獲得良好的阻劑圖案。因應需要亦可進形光或電子射線的照射後加熱(PEB:Post Exposure Bake)。而且,可藉由乾式蝕刻去除阻劑膜中因前述步驟而被顯影去除的部分的阻劑下層膜,而可在基板上形成所期望的圖案。
所謂使用於本發明的阻劑,係指光阻劑或電子射線阻劑。
作為本發明中之塗布於微影術用阻劑下層膜的上部之光阻劑,可使用負型、正型之任一者,有由酚醛樹脂與1,2-萘二疊氮化醌磺酸酯所構成之正型光阻劑、由具有因酸而分解以使鹼溶解速度上升的基之黏結劑與光酸產生劑所構成之化學增幅型光阻劑、由鹼可溶性黏結劑、因酸而分解以使光阻劑的鹼溶解速度上升之低分子化合物及光酸產生劑所構成之化學增幅型光阻劑、由具有因酸而分解以使鹼溶解速度上升的基之黏結劑、因酸而分解以使光阻劑的鹼溶解速度上升之低分子化合物及光酸產生劑所構成之化學增幅型光阻劑、在骨架具有Si原子的光阻劑等,可列舉例如,Rohm and Haas公司製,商品名APEX-E。
又,作為塗布於本發明中之微影術用阻劑下層膜的上部之電子射線阻劑,可列舉例如由在主鏈包含Si-Si鍵且在末端包含芳香族環之樹脂與因電子射線的照射而產生酸之酸產生劑所構成之組成物、或由羥基被包含N-羧基胺的有機基所取代之聚(p-羥基苯乙烯)與因電子射線的照射而產生酸之酸產生劑所構成之組成物等。在後者的電子射線阻劑組成物中,因電子射線照射而由酸產生劑所產生的酸會與聚合物側鏈的N-羧基氮氧基(N-carboxy aminoxyl)進行反應,聚合物側鏈分解成羥基且表現鹼可溶性並溶解於鹼顯影液,而形成阻劑圖案。藉由此電子射線的照射而產生酸的酸產生劑,可列舉1,1-雙[p-氯苯基]-2,2,2-三氯乙烷、1,1-雙[p-甲氧基苯基]-2,2,2-三氯乙烷、1,1-雙[p-氯苯基]-2,2-二氯乙烷、2-氯-6-(三氯甲基)吡啶等鹵化有機化合物、三苯基鋶鎓鹽、二苯基碘鎓鹽等鎓鹽、硝基苄基甲苯磺酸酯、二硝基苄基甲苯磺酸酯等磺酸酯。
上述光阻劑的曝光的光係近紫外線、遠紫外線、或極紫外線(例如,EUV,波長13.5nm)等化學射線,例如能使用248nm(KrF雷射光)、193nm(ArF雷射光)、172 nm等波長的光。光照射中,只要為可從阻劑膜中的光酸產生劑使酸產生的方法,則可無特別限制地使用,依據曝光光量1至5000mJ/cm2
、或10至5000mJ/cm2
、或10至1000 mJ/cm2
。
又,電子線阻劑的電子射線照射,例如可使用電子射線照射裝置進行照射。
作為具有使用本發明的階差基板被覆組成物而形成之阻劑下層膜的阻劑膜的顯影液,可使用氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨水等無機鹼類;乙胺、n-丙胺等一級胺類;二乙胺、二-n-丁胺等二級胺類;三乙胺、甲基二乙胺等三級胺類;二甲基乙醇胺、三乙醇胺等醇胺類;氫氧化四甲銨、氫氧化四乙銨、膽鹼等四級銨鹽;吡咯、哌啶等環狀胺類;等之鹼類的水溶液。再者,亦可在上述鹼類的水溶液中適當添加異丙醇等醇類、非離子系等界面活性劑而使用。此等之中,較佳的顯影液為四級銨鹽,再佳為氫氧化四甲銨及膽鹼。
又,作為顯影液,可使用有機溶劑。作為例子,可列舉例如,乙酸甲酯、乙酸丁酯、乙酸乙酯、乙酸異丙酯、乙酸戊酯、乙酸異戊酯、甲氧基乙酸乙酯、乙氧基乙酸乙酯、丙二醇單甲醚、乙二醇單乙醚乙酸酯、乙二醇單丙醚乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單苯醚乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單丙醚乙酸酯、二乙二醇單乙醚乙酸酯、二乙二醇單苯醚乙酸酯、二乙二醇單丁醚乙酸酯、2-甲氧基乙酸丁酯、3-甲氧基乙酸丁酯、4-甲氧基乙酸丁酯、3-甲基-3-甲氧基乙酸丁酯、3-乙基-3-甲氧基乙酸丁酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、2-乙氧基乙酸丁酯、4-乙氧基乙酸丁酯、4-丙氧基乙酸丁酯、2-甲氧基乙酸戊酯、3-甲氧基乙酸戊酯、4-甲氧基乙酸戊酯、2-甲基-3-甲氧基乙酸戊酯、3-甲基-3-甲氧基乙酸戊酯、3-甲基-4-甲氧基乙酸戊酯、4-甲基-4-甲氧基乙酸戊酯、丙二醇二乙酸酯、甲酸甲酯、甲酸乙酯、甲酸丁酯、甲酸丙酯、乳酸乙酯、乳酸丁酯、乳酸丙酯、碳酸乙酯、碳酸丙酯、碳酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、丙酮酸丁酯、乙醯乙酸甲酯、乙醯乙酸乙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸異丙酯、2-羥基丙酸甲酯、2-羥基丙酸乙酯、甲基-3-甲氧基丙酸酯、乙基-3-甲氧基丙酸酯、乙基-3-乙氧基丙酸酯、丙基-3-甲氧基丙酸酯等。再者,亦可在此等顯影液中添加界面活性劑等。作為顯影的條件,係適當選自溫度5至50℃、時間10至600秒鐘。
在本發明中,可經過以下步驟而製造半導體裝置:藉由阻劑下層膜形成組成物而在半導體基板形成該阻劑下層膜之步驟;在其上形成阻劑膜之步驟;接著將此藉由光或電子射線照射與顯影而形成阻劑圖案之步驟;藉由阻劑圖案而將該阻劑下層膜進行蝕刻之步驟;及藉由經圖案化的阻劑下層膜而將半導體基板進行加工之步驟。
將來,若進行阻劑圖案的細微化,則產生解析度的問題及阻劑圖案在顯影後顛倒的問題,而開始期望阻劑的薄膜化。因此,難以在基板加工中獲得充分的阻劑圖案膜厚,且不僅阻劑圖案,在阻劑膜與進行加工的半導體基板之間所作成的阻劑下層膜亦變得需要使其具有作為基板加工時的遮罩的功能之製程。作為此種製程用的阻劑下層膜,與以往的高蝕刻速率性阻劑下層膜不同,其變得要求具有與阻劑膜相近的乾式蝕刻速度的選擇比之微影術用阻劑下層膜、具有比阻劑膜小的乾式蝕刻速度的選擇比之微影術用阻劑下層膜、具有比半導體基板小的乾式蝕刻速度的選擇比之微影術用阻劑下層膜。又,此種阻劑下層膜亦能被賦予抗反射能,且可一併具有以往的抗反射膜的功能。
另一方面,為了獲得細微的阻劑圖案,亦開始使用在阻劑下層膜乾式蝕刻時使阻劑圖案與阻劑下層膜比阻劑顯影時的圖案寬度更細之製程。作為此種製程用的阻劑下層膜,與以往的高蝕刻速率性抗反射膜不同,變得要求具有與阻劑膜相近的乾式蝕刻速度的選擇比之阻劑下層膜。又,此種阻劑下層膜亦能被賦予抗反射能,且可一併具有以往的抗反射膜的功能。
本發明中,在基板上將本發明的阻劑下層膜成膜後、在阻劑下層膜上直接或因應需要將1層至數層的塗膜材料在阻劑下層膜上成膜後,可塗布阻劑。藉此,即使在阻劑膜的圖案寬度變窄、為了防止圖案崩塌而被覆薄薄的阻劑膜之情形,亦變得能藉由選擇適當的蝕刻氣體而加工基板。
亦即,可經過以下步驟而製造半導體裝置:藉由阻劑下層膜形成組成物而在半導體基板形成該阻劑下層膜之步驟;在其上形成由含有矽成分等的塗膜材料而成之硬遮罩或由蒸鍍而成之硬遮罩(例如,氮化氧化矽)之步驟;再在其上形成阻劑膜的步驟;藉由光或電子射線的照射與顯影而形成阻劑圖案之步驟;藉由阻劑圖案而以鹵素系氣體蝕刻硬遮罩之步驟;藉由經圖案化的硬遮罩而以氧系氣體或氫系氣體蝕刻該阻劑下層膜之步驟;及藉由經圖案化的阻劑下層膜而以鹵素系氣體將半導體基板進行加工之步驟。
本發明的階差基板被覆組成物,在考慮到作為抗反射膜的效果之情形,因光吸收部位被加入骨架,故在加熱乾燥時無進入光阻劑中的擴散物,又,光吸收部位因具有充分大的吸光性能,故反射光防止效果高。
本發明的階差基板被覆組成物,其熱穩定性高,防止燒成時由分解物所致之對於上層膜的汙染,又,在燒成步驟的溫度限度中可具有餘裕。
再者,本發明的階差基板被覆組成物係依據製程條件而能被使用作為具有以下功能的膜:防止光的反射的功能;以及進一步防止基板與光阻劑的相互作用、或者防止用於光阻劑的材料或對光阻劑進行曝光時所生成之物質對於基板造成不良作用的功能。
[實施例]
<合成例1>
在二口燒瓶中,投入丙烯酸四氫呋喃甲酯(東京化成工業股份有限公司製)5g、甲基丙烯酸甲酯(東京化成工業股份有限公司製)3.01g、2,2’偶氮雙(異丁酸甲酯)(東京化成工業股份有限公司製)0.42g、丙二醇單甲醚乙酸酯48g。之後加熱至120℃,攪拌約6小時。反應結束後,對於甲醇(關東化學股份有限公司製)滴下聚合物溶液,藉此使其再沉澱。將所得之沉澱物進行抽氣過濾後,將過濾物在60℃進行減壓乾燥一晩。然後,獲得5g的化合物1樹脂。所得之化合物的藉由GPC並以聚苯乙烯換算所推算之重量平均分子量Mw為6500。
<合成例2>
在二口燒瓶中,在產品名JER-1031S(Mitsubishi Chemical股份有限公司製)(四苯乙烷型環氧樹脂)7g、2-呋喃甲酸(東京化成股份有限公司製)4.1g、溴化四丁鏻(東京化成股份有限公司製)0.006g中,置入丙二醇單甲醚乙酸酯26g。之後加熱至100℃,攪拌約6小時。在所得之溶液中,添加陽離子交換樹脂(產品名:DOWEX[註冊商標]550A,MUROMACHI TECHNOS(股))11g、陰離子交換樹脂(產品名:Amberlite[註冊商標]15JWET,ORGANO(股))11g,在室溫進行4小時的離子交換處理。將離子交換樹脂進行分離後,獲得化合物2溶液。所得之化合物的藉由GPC並以聚苯乙烯換算所測定之重量平均分子量Mw為1600。
<比較合成例3>
在二口燒瓶中,將商品名EHPE3150(DAICEL CHEMICAL INDUSTRIES(股)製)(2,2-雙(羥基甲基)-1-丁醇的1,2-環氧-4-(2-環氧乙烷基)環己烷加成物)40.0g、9-蒽羧酸20.3g及苯甲酸13.7g溶解於丙二醇單甲醚302.0g後,添加苄基三乙基銨1.5g,使其回流反應24小時。在所得之溶液中,添加陽離子交換樹脂(產品名:DOWEX[註冊商標]550A,MUROMACHI TECHNOS(股))11g、陰離子交換樹脂(產品名:Amberlite[註冊商標]15JWET,ORGANO(股))11g,在室溫進行4小時的離子交換處理。將離子交換樹脂進行分離後,獲得化合物3溶液。所得之化合物的藉由GPC並以聚苯乙烯換算所測定之重量平均分子量Mw為4,100。
<實施例1>
在由合成例1所得之樹脂0.95g中,混合包含5%的TPS-Tf(東洋合成股份有限公司製,光酸產生劑)的丙二醇單甲醚0.95g、包含1%的界面活性劑(DIC(股)製,品名:Megafac [商品名]R-40,氟系界面活性劑)的丙二醇單甲醚乙酸酯0.09g、丙二醇單甲醚1.8g、丙二醇單甲醚乙酸酯6.2g。之後,利用口徑0.1μm的聚四氟乙烯製微米過濾器進行過濾,調整阻劑下層膜形成組成物的溶液。
<實施例2>
在由合成例2所得之樹脂溶液(固體成分為20.4%)8.4g中,混合包含5%的TPS-Tf(東洋合成股份有限公司製,光酸產生劑)的丙二醇單甲醚1.71g、包含1%的界面活性劑(DIC(股)製,品名:Megafac[商品名]R-40,氟系界面活性劑)的丙二醇單甲醚乙酸酯0.17g、丙二醇單甲醚2.4g、丙二醇單甲醚乙酸酯2.3g。之後,利用口徑0.1μm的聚四氟乙烯製微米過濾器進行過濾,調整阻劑下層膜形成組成物的溶液。
<實施例3>
在由合成例2所得之樹脂溶液(固體成分為20.4%)8.4g中,混合包含5%的TAG2689(美國,King(股)製,商品名。成分為三氟甲磺酸的四級銨鹽)的丙二醇單甲醚1.71 g、包含1%的界面活性劑(DIC(股)製,品名:Megafac[商品名]R-40,氟系界面活性劑)的丙二醇單甲醚乙酸酯0.17 g、丙二醇單甲醚2.4g、丙二醇單甲醚乙酸酯2.3g。之後,利用口徑0.1μm的聚四氟乙烯製微米過濾器進行過濾,調整阻劑下層膜形成組成物的溶液。
<實施例4>
在由合成例2所得之樹脂溶液(固體成分為20.4%)8.4g中,混合包含5%的對羥基苯磺酸吡啶鹽的丙二醇單甲醚1.71g、包含1%的界面活性劑(DIC(股)製,品名:Megafac [商品名]R-40,氟系界面活性劑)的丙二醇單甲醚乙酸酯0.17g、丙二醇單甲醚2.4g、丙二醇單甲醚乙酸酯2.3g。之後,利用口徑0.1μm的聚四氟乙烯製微米過濾器進行過濾,調整阻劑下層膜形成組成物的溶液。
<比較例1>
在由合成例1所得之樹脂1.0g中,混合包含1%的界面活性劑(DIC(股)製,品名:Megafac[商品名]R-40,氟系界面活性劑)的丙二醇單甲醚乙酸酯0.1g、丙二醇單甲醚2.7 g、丙二醇單甲醚乙酸酯6.2g。之後,利用口徑0.1μm的聚四氟乙烯製微米過濾器進行過濾,調整阻劑下層膜形成組成物的溶液。
<比較例2>
在由合成例2所得之樹脂8.8g中,混合包含1%的界面活性劑(DIC(股)製,品名:Megafac[商品名]R-40,氟系界面活性劑)的丙二醇單甲醚乙酸酯0.2g、丙二醇單甲醚2.1 g、丙二醇單甲醚乙酸酯4.0g。之後,利用口徑0.1μm的聚四氟乙烯製微米過濾器進行過濾,調整阻劑下層膜形成組成物的溶液。
<比較例3>
在由比較合成例3所得之樹脂溶液(固體成分為16.0%) 4.9g中,混合四甲氧基甲基二醇甘脲0.2g、包含5%的對甲苯磺酸吡啶鹽的丙二醇單甲醚0.2g、包含1%的界面活性劑(DIC(股)製,品名:Megafac[商品名]R-40,氟系界面活性劑)的丙二醇單甲醚乙酸酯0.08g、丙二醇單甲醚2.1g、丙二醇單甲醚乙酸酯2.6g。之後,利用口徑0.1μm的聚四氟乙烯製微米過濾器進行過濾,調整阻劑下層膜形成組成物的溶液。
(熱硬化性試驗)
將由實施例3、4及比較例1、2所調整之阻劑下層膜組成物分別使用旋轉塗布機塗布於矽晶圓上。在熱板上以300℃加熱60秒鐘,形成膜厚200nm的阻劑下層膜。溶劑剝離性係將燒成後的塗布膜浸漬在丙二醇單甲醚與丙二醇單甲醚乙酸酯為7比3的混合溶劑中1分鐘,在離心脫水後以100℃燒成60秒鐘,測定膜厚,藉此算出殘膜率。(表1)
實施例3及4因由熱所產生的酸的影響而引起硬化反應,故獲得對於溶劑的耐性,殘膜率成為100%,相對於此,比較例1及2的殘膜率為0%。
(光硬化性試驗)
將由實施例1、2及比較例1、2所調整之阻劑下層膜組成物分別使用旋轉塗布機塗布於矽晶圓上。在熱板上以170℃加熱60秒鐘,形成膜厚150nm的阻劑下層膜。藉由Ushio(股)製且使用UV照射單元(172nm)的紫外線照射裝置,將此阻劑下層膜進行500mJ/cm2
的紫外線照射後,在熱板上以160℃加熱60秒鐘,確認在光照射(紫外線照射)下的溶劑剝離性。溶劑剝離性係將紫外線照射後的塗布膜浸漬在丙二醇單甲醚與丙二醇單甲醚乙酸酯為7比3的混合溶劑中1分鐘,在離心脫水後以100℃燒成60秒鐘,測定膜厚,藉此算出殘膜率。(表2)
實施例1及2因由光所產生的酸的影響而引起硬化反應,故獲得對於溶劑的耐性,殘膜率成為100%,相對於此,比較例1及2的殘膜率為0%。
(對階差基板的平坦化性及嵌入性評價)
作為對階差基板的平坦化性評價,係利用200nm膜厚的SiO2
基板,進行溝槽寬50nm、間距100nm的緻密圖案區域(DENSE)與未形成圖案的開放區域(OPEN)之被覆膜厚的比較。將由實施例1及實施例2所調整之阻劑下層膜組成物分別使用旋轉塗布機塗布於上述基板後,在熱板上以170℃加熱60秒鐘,形成膜厚150nm及200nm的阻劑下層膜。藉由Ushio(股)製且使用UV照射單元(172nm)的紫外線照射裝置,將此阻劑下層膜進行500mJ/cm2
的紫外線照射後,在熱板上以160℃加熱60秒鐘。又,將由實施例3、實施例4及比較例3所調整之阻劑下層膜組成物分別使用旋轉塗布機塗布於上述基板後,在熱板上以215℃及300℃加熱60秒鐘。使用Hitachi High-Technologies(股)製掃描式電子顯微鏡(S-4800)觀察此等基板的平坦化性,藉由測定階差基板的緻密區域(圖案部)與開放區域(無圖案部)之膜厚差(緻密區域與開放區域之塗布階差,稱為塗布階差)而評價平坦化性。於此,所謂平坦化性,意指在圖案存在的部分(緻密區域(圖案部))與圖案不存在的部分(開放區域(無圖案部)),其上部所存在之經塗布的被覆物的膜厚差(Iso-dense塗布階差)小。(表3)
實施例1及實施例2因在170℃中不會引起交聯反應,故在此階段中能獲得充分的回流性,在階差基板上能獲得充分的平坦化性。再者,因為會因光而硬化,故可獲得良好的平坦化膜。實施例3及實施例4因在聚合物內所具有的交聯基的交聯起始溫度高,故在高溫下使其充分地回流後交聯反應才會開始,因此能獲得良好的平坦化膜。另一方面,比較例3因交聯劑的交聯起始溫度低,無法獲得充分的回流性,故平坦化性低。
本發明的階差基板被覆組成物因具有呋喃基,故在合成階差基板被覆組成物之際,比起以往的環氧基,可穩定地進行由離子交換樹脂所致之精製,最終可獲得高純度的階差基板被覆組成物。又,可利用作為用於在基板上形成對圖案的填充性高且具有平坦化性的被膜之階差基板被覆組成物。
Claims (29)
- 如請求項1之階差基板被覆組成物,其中,上述芳香族環為苯環、萘環或蒽環。
- 如請求項1或2之階差基板被覆組成物,其中,包含上述芳香族環的聚合物係包含羥基芳基酚醛結構的聚合物,且係其羥基被式(A-1)或式(A-2)的部分結構所取代之聚合物。
- 如請求項1或2之階差基板被覆組成物,其中,包含上述芳香族環的單體係芳香族環的羥基被式(A-1)或式(A-2)的部分結構所取代之單體。
- 如請求項1至4中任一項之階差基板被覆組成物,其中,更包含酸產生劑。
- 如請求項1至5中任一項之階差基板被覆組成物,其中,更包含界面活性劑。
- 一種被覆基板的製造方法,其包含:步驟(i),其在具有階差的基板塗布如請求項1至6中任一項之階差基板被覆組成物;及步驟(ii),其將由步驟(i)所塗布之組成物進行曝光或加熱。
- 如請求項7之被覆基板的製造方法,其中,在上述步驟(i),在上述進行曝光的步驟(ii)之前,加上步驟(ia),其以70℃至400℃的溫度將具有階差的基板上的階差基板被覆組成物加熱10秒鐘至5分鐘。
- 如請求項7或8之被覆基板的製造方法,其中,在上述步驟(ii)中,曝光所用的光係波長為150nm至700nm的光。
- 如請求項7至9中任一項之被覆基板的製造方法,其中,在上述步驟(ii)中,曝光光量為10mJ/cm2 至5000mJ/cm2 。
- 如請求項7之被覆基板的製造方法,其中,在上述步驟(ii)中,以100℃至500℃的溫度進行加熱。
- 如請求項7至11中任一項之被覆基板的製造方法,其中,上述具有階差的基板具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,圖案的縱橫比為0.1至100。
- 如請求項7至12中任一項之被覆基板的製造方法,其中,上述具有階差的基板具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,開放區域與圖案區域之Bias(塗布階差)為1nm至50 nm。
- 一種半導體裝置的製造方法,其包含:在具有階差的基板上形成如請求項1至6中任一項之階差基板被覆組成物所構成之下層膜的步驟;在其上形成阻劑膜的步驟;接下來將此進行光或者電子射線的照射,或者在光或電子射線的照射中至照射後進行加熱,藉由之後的顯影而形成阻劑圖案的步驟;藉由所形成之阻劑圖案將該下層膜進行蝕刻的步驟;及藉由經圖案化的下層膜將半導體基板進行加工的步驟。
- 如請求項14之半導體裝置的製造方法,其中,上述形成下層膜的步驟包含:步驟(i),其在上述具有階差的基板塗布如請求項1至6中任一項之階差基板被覆組成物;及步驟(ii),其將由步驟(i)所塗布之組成物進行曝光或加熱。
- 如請求項15之半導體裝置的製造方法,其中,在上述步驟(i),在上述進行曝光的步驟(ii)之前,加上步驟(ia),其以70℃至400℃的溫度將具有階差的基板上的階差基板被覆組成物加熱10秒鐘至5分鐘。
- 如請求項15或16之半導體裝置的製造方法,其中,在上述步驟(ii)中,曝光所用的光係波長為150 nm至700nm的光。
- 如請求項15至17中任一項之半導體裝置的製造方法,其中,在上述步驟(ii)中,曝光光量為10 mJ/cm2 至5000mJ/cm2 。
- 如請求項15之半導體裝置的製造方法,其中,在上述步驟(ii)中,以100℃至500℃的溫度進行加熱。
- 如請求項14至19中任一項之半導體裝置的製造方法,其中,上述具有階差的基板具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,且係圖案的縱橫比為0.1至100的基板。
- 如請求項14至20中任一項之半導體裝置的製造方法,其中,上述具有階差的基板具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,由上述階差基板被覆組成物所得之下層膜具有1nm至50nm的開放區域與圖案區域之Bias(塗布階差)。
- 一種半導體裝置的製造方法,其包含:在具有階差的基板形成由如請求項1至6中任一項之階差基板被覆組成物所構成之下層膜的步驟;在其上形成硬遮罩(hard mask)的步驟;再在其上形成阻劑膜的步驟;接下來將此進行光或者電子射線的照射,或者在光或電子射線的照射中至照射後進行加熱,藉由之後的顯影而形成阻劑圖案的步驟;藉由所形成之阻劑圖案將硬遮罩進行蝕刻的步驟;藉由經圖案化的硬遮罩將該下層膜進行蝕刻的步驟;及藉由經圖案化的下層膜將半導體基板進行加工的步驟。
- 如請求項22之半導體裝置的製造方法,其中,上述形成下層膜的步驟包含:步驟(i),其在上述具有階差的基板塗布如請求項1至6中任一項之階差基板被覆組成物;及步驟(ii),其將由步驟(i)所塗布之組成物進行曝光或加熱。
- 如請求項23之半導體裝置的製造方法,其中,在上述步驟(i),在上述進行曝光的步驟(ii)之前,加上步驟(ia),其以70℃至400℃的溫度將具有階差的基板上的階差基板被覆組成物加熱10秒鐘至5分鐘。
- 如請求項23或24之半導體裝置的製造方法,其中,在上述步驟(ii)中,曝光所用的光係波長為150 nm至700nm的光。
- 如請求項23至25中任一項之半導體裝置的製造方法,其中,在上述步驟(ii)中,曝光光量為10 mJ/cm2 至5000mJ/cm2 。
- 如請求項23之半導體裝置的製造方法,其中,在上述步驟(ii)中,以100℃至500℃的溫度進行加熱。
- 如請求項22至27中任一項之半導體裝置的製造方法,其中,上述具有階差的基板具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,且係圖案的縱橫比為0.1至100的基板。
- 如請求項22至28中任一項之半導體裝置的製造方法,其中,上述具有階差的基板具有開放區域(非圖案區域)、與由DENCE(密)及ISO(粗)所構成之圖案區域,由上述階差基板被覆組成物所得之下層膜具有1nm至50nm的開放區域與圖案區域之Bias(塗布階差)。
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WO2002083415A1 (en) | 2001-04-17 | 2002-10-24 | Brewer Science, Inc. | Anti-reflective coating composition with improved spin bowl compatibility |
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US8048615B2 (en) | 2005-12-06 | 2011-11-01 | Nissan Chemical Industries, Ltd. | Silicon-containing resist underlayer coating forming composition for forming photo-crosslinking cured resist underlayer coating |
JP5083567B2 (ja) | 2006-10-12 | 2012-11-28 | 日産化学工業株式会社 | 光架橋硬化によるレジスト下層膜を用いる半導体装置の製造方法 |
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