TW201602138A - 經引導之自組裝圖案形成方法及組成物 - Google Patents
經引導之自組裝圖案形成方法及組成物 Download PDFInfo
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- TW201602138A TW201602138A TW103146518A TW103146518A TW201602138A TW 201602138 A TW201602138 A TW 201602138A TW 103146518 A TW103146518 A TW 103146518A TW 103146518 A TW103146518 A TW 103146518A TW 201602138 A TW201602138 A TW 201602138A
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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Abstract
一種以經引導自組裝方式形成圖案之方法,包含:(a)提供半導體基板,其包含待圖案化之一或多層;(b)施加可交聯之下方層組成物於該待圖案化之一或多層上,以形成可交聯下方層,其中該可交聯下方層組成物包含可交聯聚合物,其包含具通式(I-A)或(I-B)之第一單元:
□□
其中:P為可聚合官能基;L為單鍵,或m+1-價連結基;X1為單價電子提供基團;X2為二價電子提供基團;Ar1與Ar2分別為三價與二價芳基,以及環丁烯環上之碳原子係鍵結至在Ar1或Ar2之同一芳香環上之相鄰碳原子;m與n各者為1或更大之整數;以及各R1係獨立地為單價基團;(c)
加熱該可交聯下方層,以形成經交聯下方層;(d)於該經交聯下方層上形成含有嵌段共聚物之自組裝層;以及(e)退火(annealing)該自組裝層。該方法與組成物特別適用於製造半導體裝置或數據儲存裝置,以形成高解析度圖案。
Description
本申請案係依據35 U.S.C.§119(e),請求美國臨時專利申請案61/922,767(於2013年12月31日申請)之優先權,其完整內容在此併入本案以作為參考資料。
本發明一般相關於電子裝置之製造。更具體的是,本發明相關於一種以經引導自組裝方式形成圖案之方法,並相關於使用於此方法之下方層組成物。該方法與組成物可應用於舉例來說半導體裝置之製造中,以用於形成微細圖案,或用於資料儲存如硬碟之製造。
在半導體製造產業中,使用光阻材料之光微影製程已成為轉移影像至一或多層下方層,如置於半導體基板上之金屬、半導體與介電層,及轉移影像至基板本身,之標準方法。為了增加半導體裝置之積體密度,並允許形成具有奈米範圍尺寸之結構,目前已發展出具高解析度能力之光阻與光微影加工工具。目前先進光微影之製造標準為193nm浸沒式光微影技術。然而,由於此製程之物理解析度極限,使其難以直接創造超越約36nm半間距與
空間之圖案。儘管已發展出EUV曝光工具,創造較高解析度之圖案,但此工具的成本過高,且該技術之適用性仍不明朗。
目前已提出經引導自組裝(DSA)製程,以拓展解析度極限而超出現有電流光微影技術之解析度極限,例如,小於15nm。DSA製程依賴於特定類型嵌段共聚物在退火時,於基板表面上重排為有序結構的能力。此種嵌段共聚物的重排,係基於其中一嵌段與下方表面上之預圖案間之親和性。
已知可用於DSA下方層之可交聯聚合物系統包括含有乙烯基苯並環丁烯(BCB)與苯乙烯隨機共聚物,此種聚合物揭示於如Du Yeol Ryu等人("A Generalized Approach to the Modification of Solid Surfaces," Science308,236(2005))。含乙烯基BCB之聚合物之DSA下方層係被廣泛使用,然而,其受到需要相對較高之退火溫度(如約250℃)及/或長退火時間,以誘發環丁烯環異構化為反應性o-醌二甲烷中間物而交聯之限制。使用高交聯溫度會不利地衝擊含有如抗反射塗層與硬遮罩層之下層,由於會導致這些層之熱降解及/或氧化。該高交聯溫度還會去濕潤,導致不良之圖案形成,以及氧化引發之表面能量改變。此外,較高之交聯溫度會限制不然可用於DSA下方層組成物之功能性單體種類。高交聯溫度之另一缺點為需要較複雜之加熱工具以加工基板,需提供惰性氣體環境以預防不希望之氧化,其會導致下方層之表面能量增加。因此,希望提
供一種DSA方法,其可使下方層組成物進行低溫交聯,在合理之短時間內完成,以及用於該方法之可交聯聚合物與下方層組成物。
目前持續需要一種經引導自組裝方法,以及可交聯聚合物,與含有此種聚合物之DSA下方層組成物,其可解決與本技術領域相關之一或多個問題。
依據本發明之第一觀點,係提供一種以經引導自組裝方式形成圖案之方法。該方法包含:(a)提供半導體基板,其包含待圖案化之一或多層;(b)施加可交聯之下方層組成物於該待圖案化之一或多層上,以形成可交聯下方層,其中該可交聯下方層組成物包含可交聯聚合物,其包含具通式(I-A)或(I-B)之第一單元:
本文所用的術語僅為了描述特定實施例,而非用於限制本發明。如此所使用的,單數形式“一(a)”、一(an)”與該(the)”亦包括複數形式,除非內文另外明確指出。當使用於聚合物時,單元比例係以莫耳%(rnol%)表示,除非另有指出。
100‧‧‧基板
102‧‧‧下方層
102'‧‧‧導引圖案
104‧‧‧光阻圖案
106‧‧‧刷層
108‧‧‧經引導自組裝層
110‧‧‧第一區域
112‧‧‧第二區域
本發明將參照附圖描述,其中相同的附圖標記表示相同的特徵,以及其中:第1圖(A)至(F)為本發明示範性DSA製程流程之橫截面與俯視圖;以及第2圖(A)至(C)為原子力顯微鏡(AFM)影像,顯示本發明下方層組成物上之自對齊DSA層。
本發明之經引導自組裝(DSA)方法涉及在待圖案化之一或多層上施加可交聯下方層組成物。該可交聯下方層組成物包括可交聯聚合物與溶劑,並可包括一或多種額外之視需要成分。
可用於該組成物之可交聯聚合物可為同元聚合物,或可為共聚物,具有複數個不同之重複單元,如二、三、四或更多個不同之重複單元。一般而言,該可交
聯聚合物為共聚物。該共聚物可為隨機共聚物、嵌段共聚物,或梯度共聚物,其中一般為隨機共聚物。
該可交聯聚合物包含第一單元,其包括融合至環丁烯環上之芳香基,後文稱之為“芳基環丁烯”。芳香族可包括單一或複數個芳香環,例如,一、二、三、四或更多個芳香環。當複數個芳香環存在於該單元內時,芳香環本身可形成融合(如萘基、蒽基、芘基)及/或連結(如聯苯基)結構。芳香族基團係視需要經如烷基、環烷基或鹵素之一或多者取代。該環丁烯基視需要經羥基、烷氧基、胺或醯胺取代。
可交聯聚合物包括具下列通式(I-A)或(I-B)之單元:
可聚合官能基P可選自如下列通式(II-A)與(II-B):
其中R4選自氫、氟、C1-C3烷基與C1-C3氟烷基;以及X為氧或由式NR5代表,其中R5選自氫,以及經取代與未經取代之C1至C10直線形、分支與環狀烴;以及
其中R6選自氫、氟、C1-C3烷基與C1-C3氟烷基。其他適用之可聚合官能基包括如降冰片烯、環矽氧烷、環狀醚、烷氧基矽烷、酚醛清漆,官能基如酚及/或醛、羧酸、醇與胺。
使用於本發明之芳基環丁烯單體可以任何適當方法製備,如描述於M.Azadi-Ardakani等人(3,6-Dimethoxybenzocyclobutenone:A Reagent for Quinone Synthesis,Tetrahedron,Vol.44,No.18,pp.5939-5952,1988;J.Dobish et al,Polym.Chem.,2012,3,857-860(2012));美國專利號4540763、4812588、5136069與5138081;以及公開之國際專利申請案號WO 94/25903。可用於製造單體之芳基環丁烯可購自商標名CycloteneTM,由The Dow Chemical Company販售。
適當之芳基環丁烯單體包括如可形成下列聚合單元者:
該第一單元一般存在於自可交聯聚合物中之含量為1至100mol%,如1至50mol%、2至20mol%,或3至10mol%,以聚合物為基準。
該可交聯聚合物可包括一或多個額外單元。該聚合物可包括如用於調整自可交聯聚合物之表面能量、光學特性(如n與k值)及/或玻璃轉換溫度之一或多種額外單元。藉由篩選適當之聚合物單元,該聚合物可製為對待塗覆於下方層上之DSA嵌段共聚物之特定嵌段具有親和性,或對於DSA嵌段共聚物之每一嵌段呈中性。適當之單元包括如一或多種選自於下列通式(III)與(IV)之單元:
其中R11獨立地選自於氫、氟、C1-C3烷基與C1-C3氟烷基,R12選自於視需要經取代之C1至C10烷基;以及Ar3為芳基。較佳Ar3包括1、2或3個芳香族碳環及/或雜芳環。較佳該芳基包含單一芳環,更佳為苯環。該芳基視需要經如(C1-C6)烷基、(C1-C6)烷氧基或鹵素取代。較佳該芳基未經取代。
額外單元之示範性適用結構包括下列:
若存在於自可交聯聚合物中,該一或多個額外單元之使用量至多99mol%,較佳為80至98mol%,以聚合物為基準。
該可交聯聚合物較佳具有重量平均分子量Mw小於100,000,較佳Mw為1,000至50,000。該可交聯聚合物一般具有聚合分散度指數(PDI=Mw/Mn)小於2.0,更佳小於1.8。分子量,Mw與Mn二者,皆可以如使用通
用校準法之凝膠通透層析法測定,並以聚苯乙烯標準品校正。
較佳為,聚合物之交聯啟動溫度(To)小於250℃,較佳為100至225℃,更佳為100至200℃。此相對低之啟動溫度可允許聚合物於相對低之溫度與時間下進行交聯,因而可避免或最小化如上述使用具較高啟動與交聯溫度之聚合物之問題。
該可交聯聚合物一般存在於下方層組成物之量為80至100wt%,例如,90至100wt%,或95至100wt%,以組成物之總固體量為基準。
適當之隨機可交聯聚合物包括如下列各者(莫耳%比例):
其中單元比例為莫耳%計,以聚合物為基準。
該下方層組成物更包括溶劑,其可包括單一溶劑或溶劑混合物。用於配製並鑄形下方層組成物之適當溶劑材料,其對於組成物中之非溶劑成分具有相當良好之溶解特性,但不會明顯溶解將與該下方層組成物接觸之基板表面之下方材料。該溶劑一般選自水、水性溶液、有機溶劑,及其混合物。適用於下方層組成物之有機溶劑包括如:醇類如直線形、分支或環狀C4-C9單元醇,如1-丁醇、2-丁醇、異丁醇、第三-丁醇、2-甲基-1-丁醇、1-戊醇、2-戊醇、4-甲基-2-戊醇、1-己醇、1-庚醇、1-辛醇、2-己醇、2-庚醇、2-辛醇、3-己醇、3-庚醇、3-辛醇與4-辛醇;2,2,3,3,4,4-六氟-1-丁醇、2,2,3,3,4,4,5,5-八氟-1-戊醇,與2,2,3,3,4,4,5,5,6,6-十氟-1-己醇,以及C5-C9氟化二醇如2,2,3,3,4,4-六氟-1,5-戊二醇、2,2,3,3,4,4,5,5-八氟-1,6-己二醇與2,2,3,3,4,4,5,5,6,6,7,7-十二氟-1,8-辛二醇;烷基酯,如乙酸烷基酯,例如乙酸正丁酯、丙酸酯如丙酸正丁酯、丙酸正戊酯、丙酸正己酯與丙酸正庚酯,以及丁酸烷基酯,例如丁酸正丁酯、丁酸異丁酯與異丁酸異丁酯;酮如2,5-二甲基-4-己酮與2,6-二甲基-4-庚酮;脂肪烴,如正庚烷、正壬烷、正辛烷、正癸烷、2-甲基庚烷、3-甲基庚烷、3,3-二甲基己烷與2,3,4-三甲基戊烷,以及氟化脂肪烴,如全氟庚烷;醚如異戊醚與二丙二醇單甲醚;以及含有這些溶劑之一或多者之混合物。在這些有機溶劑中,較佳為醇類、脂肪烴及醚類。該組成物之溶劑成分一般存在量為80至
99wt%,更特別的是,為90至99wt%或95至99wt%,以下方層組成物之總重量為基準。
該下方層組成物可包括一或多種視需要添加物,包括如界面活性劑與抗氧化劑。典型的界面活性劑包括具有兩親性(amphiphilic)特性者,亦即其同時具有親水性與疏水性。兩親性界面活性劑具有一或多個親水性頭部基團,其對水具有強親和性,以及長斥水性尾部,其為親有機溶劑性且排斥水。適當之界面活性劑可為離子性(即陰離子性、陽離子性)或非離子性。界面活性劑之其他範例包括矽界面活性劑、聚(環氧烷)界面活性劑,以及氟化學界面活性劑。適當之非離子性界面活性劑包括但不侷限於,辛基和壬基酚乙氧化物,如TRITON®X-114、X-100、X-45、X-15,與分支二級醇乙氧化物,如TERGITOLTMTMN-6(The Dow Chemical Company,Midland,Michigan USA)。又一示範性界面活性劑包括醇(一級與二級)乙氧化物、胺乙氧化物、葡糖苷、葡萄糖胺、聚乙二醇類、聚(乙二醇-共-丙二醇),或揭示於McCutcheon's Emulsifiers and Detergents,North American Edition for the Year 2000 published by Manufacturers Confectioners Publishing Co.of Glen Rock,N.J之其他界面活性劑。炔二醇衍生物之非離子性界面活性劑亦適用。此界面活性劑可購自Air Products and Chemicals,Inc.of Allentown,PA,商標名為SURFYNOL®與DYNOL®。其他適當之界面活性劑包括其他聚合性化合物,如三嵌段EO-PO-EO共聚物PLURONIC® 25R2、L121、L123、L31、
L81、L101與P123(BASF,Inc.)。此界面活性劑與其他視需要添加物一般於組成物中存在少量,如0.01至10wt%,以下方層組成物之總固體量為基準。
抗氧化劑可加入下方層組成物中,以預防或最小化下方層組成物中之有機材料氧化。適當之抗氧化劑包括如酚系抗氧化劑、由有機酸衍生物組成之抗氧化劑、含硫抗氧化劑、磷系抗氧化劑、胺系抗氧化劑、由胺-醛縮合物組成之抗氧化劑,以及由胺-酮縮合物組成之抗氧化劑。酚系抗氧化劑之範例包括經取代酚類,如1-氧基-3-甲基-4-異丙基苯、2,6-二-第三丁基酚、2,6-二-第三丁基-4-乙基酚、2,6-二-第三丁基-4-甲基酚、4-羥基甲基-2,6-二-第三丁基酚、丁基羥基苯甲醚、2-(1-甲基環己基)-4,6-二甲基酚、2,4-二甲基-6-第三-丁基酚、2-甲基-4,6-二壬基酚、2,6-二-第三丁基-α-二甲基胺基-對-甲酚、6-(4-羥基-3,5-二-第三丁基苯胺基)2,4-雙辛基-硫基-1,3,5-三嗪、正十八烷基-3-(4'-羥基-3',5'-二-第三-丁基苯基)丙酸酯、辛基化酚、經芳烷基取代之酚、烷基化對-甲酚與受阻酚;雙-、三-和多-酚如4,4'-二羥基聯苯、亞甲基-雙(二甲基-4,6-酚)、2,2'-亞甲基-雙-(4-甲基-6-第三丁基酚)、2,2'-亞甲基-雙-(4-甲基-6-環己基酚)、2,2'-亞甲基-雙(4-乙基-6-第三丁基酚)、4,4'-亞甲基-雙-(2,6-二-第三丁基酚)、2,2'-亞甲基-雙-(6-α-甲基-苄基-對-甲酚)、亞甲基經交聯之多價烷基酚、4,4'-亞丁基雙-(3-甲基-6-第三丁基酚)、1,1-雙-(4-羥基苯基)-環己烷、2,2'-二羥基-3,3'-二-(α-甲基環己基)-5,5'-二甲基二苯基甲
烷、烷基化雙酚、受阻雙酚、1,3,5-三甲基-2,4,6-三(3,5-二-第三丁基-4-羥基苄基)苯、三-(2-甲基-4-羥基-5-第三丁基苯基)丁烷、以及四[亞甲基-3-(3',5'-二-第三丁基-4'-羥基苯基)丙酸酯]甲烷。適當之抗氧化劑可購自如IrganoxTM抗氧化劑(Ciba Specialty Chemicals Corp.)。若使用氧化劑,則其一般於下方層組成物中之存在量為0.01至10wt%,以下方層組成物之總固體量為基準。
當該聚合物為自可交聯時,該下方層組成物不需添加劑交聯劑使聚合物交聯。較佳為,該下方層組成物不含此類添加劑交聯劑。
該下方層組成物可依據已知流程製備。例如,該組成物可將組成物中之固體成分溶解於溶劑成分中而製備。組成物所欲之總固體含量取決於因素如所需之最終層厚度。一般而言,下方層組成物之固體含量為0.05至10wt%,更特別的是0.1至5wt%,以組成物總重量為基準。
該下方層組成物可在將之沈積於基板上之前進行純化步驟。純化可涉及如離心、過濾、蒸餾、傾析、蒸發,以離子交換微珠處理,以及類似方法。
本發明之下方層組成物特別適用於在DSA製程中作為下方層,其對於上塗之DSA嵌段共聚物之嵌段具有親和性,或對於DSA嵌段共聚物之諸嵌段為中性。例如,該組成物可用於需要使用此下方層之化學外延(化學磊晶)製程。
為了說明,本發明將參照第1圖(A)至(F)說
明,其為本發明之示範性DSA化學磊晶製程流程圖。第1圖之示範性製程使用本發明之下方層組成物作為墊層(mat layer),應注意到其可替代地用於形成刷層或其他類型之下方層。
第1圖(A)說明基板100,其表面上包括待圖案化之一或多層。該待圖案化之一或多層可為下方基底基板材料本身,及/或與基底基板材料不同並形成於其上之一或多層。該基板可為半導體材料,如矽或化合物半導體(如III-V或II-VI)、玻璃、石英、陶瓷、銅及類似材料。一般而言,該基板可為半導體晶圓,如單晶矽或化合物半導體晶圓,並可具有一或多層,以及圖案化特徵形成於其表面上。基板上之各層包括如一或多導體層如鋁、銅、鉬、鉭、鈦、鎢、合金、氮化物,或這些金屬之矽化物層、摻雜非晶矽或摻雜多晶矽、非晶碳,一或多個電介質層如氧化矽、氮化矽、氮氧化矽,或金屬氧化物層,半導體層例如單晶矽層,以及其組合。各層可包括硬遮罩層,如含矽或碳之硬遮罩層,或抗反射塗佈層如底抗反射塗覆(BARC)層。各層可以各種技術形成,如化學蒸氣沈積(CVD)如電漿強化CVD、低壓CVD或外延生長、物理蒸氣沈積(PVD)如濺鍍或蒸氣化、電鍍或旋轉塗佈。
此述之下方層組成物可施加至基板表面,以形成下方層102。下方層組成物可施加至基板上,如,藉由旋轉塗佈、浸沒、滾輪塗佈或其他傳統塗佈技術。其中,旋轉塗佈為較典型與較佳。就旋轉塗佈而言,下方層
組成物之固體含量可經調整,以提供所需之膜厚度,依據所利用之特定塗佈裝置、溶液黏度、塗覆工具之旋轉速度,以及可允許旋轉之時間量。下方層組成物之典型厚度為2至15nm,較佳為5至10nm。
視需要,下層102之後可進行軟烘烤,以使該層之溶劑含量最小化,因而形成不黏(tack-free)塗覆層,並增進該層對基板之黏附性。軟烘烤可於加熱板或烤箱中進行,一般為加熱板。軟烘烤之溫度與時間取決於如光阻使用之特定材料與厚度。典型軟烘烤係於溫度約90至150℃進行,時間約30至120秒。
下方層組成物層102係於可有效導致可交聯聚合物進行交聯,形成經交聯聚合物網絡之溫度與時間下進行加熱。該交聯烘烤可於加熱板或烤箱中進行。該交聯烘烤可於如用於塗覆下方層組成物之同一晶圓軌道的加熱板上進行。交聯烘烤之溫度與時間取決於如下方層之特定材料與厚度。該交聯烘烤一般於溫度約100至250℃進行,時間約30秒至30分鐘,較佳為30秒至5分鐘,更佳為30至120秒。該交聯烘烤可藉由於如單一溫度、斜面溫度,或使用梯型加熱曲線,加熱該下方層而進行。由於交聯反應可於相對低之溫度下進行,該烘烤便可於空氣環境下進行,儘管其可視需要於另一大氣環境,如惰性氣體下進行。
經交聯下方層之後進行圖案化以形成導引圖案。導引圖案之圖案化可使用光微影與蝕刻製程完成,
如第1圖(B)與(C)所示。圖案化亦可替代地以化學方式進行,如對應於導引圖案之下方層區域,或未對應導引圖案的區域之酸催化極性變換。適當之極性變換製程與組成物,描述於美國專利案公開號US2012/0088188A1。
該圖案化一般經由光微影製程完成,其中光阻組成物塗覆於經交聯下方層上,並進行軟烘烤,以由該層移除溶劑。光阻層一般塗覆至厚度50nm至120nm。適當之光阻材料為技術上已知,及/或可購得。光阻層經由圖案化光罩曝光於活化輻射下而形成圖案,該影像以適當之顯影劑如鹼水溶液(如2.38wt% TMAH)或有機溶劑顯影劑顯影。光阻一般經化學放大,並可以短波長輻射或電子束影像化(如200nm以下輻射,包括193nm與EUV輻射(如13.5nm))。光阻可為正型或負型。較佳該由負型顯影(NTD)形成之光阻圖案,傳統上為正型光阻,係經成像並於有機溶劑顯影劑中顯影。所得之光阻圖案104形成於經交聯下方層102上,如第1圖(B)所示。
光阻圖案104之後藉由蝕刻轉移至下方層102,以形成導引圖案102',由下方基板上之開口隔開,如;第1圖(C)所示。該蝕刻法一般為乾蝕刻,使用適當之蝕刻化學。適當之蝕刻化學包括如電漿法,使用O2、CHF3、CF4、Ar、SF6,及其組合。其中,氧與氟化電漿蝕刻為較佳。視需要,該蝕刻可包括修整蝕刻(trim etch),以進一步降低導引圖案之寬度,以製造更微細之圖案。該導引圖案一般具有寬度如1至30nm,以及5至500nm之中心至中心節距。
此為釘扎墊(pinning mat)層典型之情況。若該施加是用於中性墊(neutral mat)層,該導引圖案一般具有如寬度5至300nm,以及12至500nm之中心至中心節距。
剩餘之光阻圖案104使用適當之剝除劑由基板上移除,如第1圖(D)所示。適當之剝除劑可購得,包括如乳酸乙酯、γ-戊內酯、γ-丁內酯或N-甲基-2-吡咯烷酮(NMP)。
之後刷狀物組成物係塗覆於基板上,而使得其位於導引圖案之間形成的凹陷內,以形成刷層106,如第1圖(E)所示。為了允許刷層與基板間形成共價鍵,該基板一般具有羥基鍵結至上方表面。共價鍵一般由基板之羥基團,如Si-OH(其中該基板包括SiO2)或Ti-OH基團(其中該基板包括TiO2),以及刷狀物聚合物之羥基團間之縮合反應而產生。刷狀物聚合物共價連結至基板上,一般係由如旋轉塗佈刷狀物聚合物溶液而達成,該溶液包含具至少一個羥基作為聚合物骨架之末端基團或聚合物側鏈之末端基團之連結基。應瞭解到,可使用額外或其他技術鍵結聚合物,如經由環氧基、酯基、羧酸基、醯胺基、矽氧烷基或(甲基)丙烯酸酯基連結,其中這些官能基亦可存在於聚合物中,或可經由表面處理連結至基板表面。該刷狀物聚合物一般為隨機共聚物,選自如羥基-末端聚(2-乙烯基吡啶)、羥基-末端聚苯乙烯-隨機-聚(甲基丙烯酸甲基酯),或可含有羥基苯乙烯或甲基丙烯酸2-羥基乙基酯單元,作為末端羥基之替代。
加熱該刷狀物組成物層以移除溶劑,並使聚合物鍵結至基板表面上。加熱以鍵結該刷狀物層,可於任何適當溫度與時間下進行,例如,一般於溫度70至250℃,與時間30秒至2分鐘下進行。
之後經引導自組裝層108於刷層106與導向圖案102'上形成,如第1圖(F)所示。該自組裝層包含嵌段共聚物,其具有對下方層導引圖案102'具親和性之第一嵌段,以及對導引圖案不具親和性之分散(亦稱之為“中性”)嵌段。使用於此,“具親和性”係指該第一嵌段為表面能量相符並吸引導引圖案,使得在鑄形與退火時,可動之第一嵌段選擇性地沈積於導引圖案上並與其對齊。此時,於下方層上該第一嵌段會形成第一區域,其與導引圖案對齊。類似地,該嵌段共聚物之第二、分散嵌段,其與下方層導引圖案具較低之親和性,於下方層上形成與該第一區域相鄰對齊之第二區域。該區域一般具有最短之平均尺寸1至100nm,例如5至75nm或10至50nm。
該嵌段一般可為任一適當之區域形成嵌段,其可連結另一種不類似之嵌段。嵌段可衍生自不同之可聚合單體,該嵌段可包括但不侷限於:包括聚二烯之聚烯烴、包括聚(環氧烷)之聚醚類,如聚(環氧乙烷)、聚(環氧丙烷)、聚(環氧丁烷),或這些之隨機或嵌段共聚物;聚((甲基)丙烯酸酯)、聚苯乙烯、聚酯類、聚有機矽氧烷、聚有機鍺烷,或製備自可聚合之Fe、Sn、Al或Ti系有機金屬單體之有機金屬聚合物,如聚(有機苯基矽基二茂鐵)。
嵌段共聚物之嵌段可包含如單體C2-30烯烴單體、衍生自C1-30醇類之(甲基)丙烯酸酯單體、含無機物單體包括Fe、Si、Ge、Sn、Al、Ti系單體,或包含前述單體至少一者之組合物。使用於嵌段中之示範性單體可包括如C2-30烯烴單體、乙烯、丙烯、1-丁烯、1,3-丁二烯、異戊二烯、乙酸乙烯酯、二氫吡喃、降冰片烯、馬來酸酐、苯乙烯、4-羥基苯乙烯、4-乙醯氧基苯乙烯、4-甲基苯乙烯或α-甲基苯乙烯;並可包括如(甲基)丙烯酸酯單體、(甲基)丙烯酸甲基酯、(甲基)丙烯酸乙基酯、(甲基)丙烯酸正丙基酯、(甲基)丙烯酸異丙基酯、(甲基)丙烯酸正丁基酯、(甲基)丙烯酸異丁基酯、(甲基)丙烯酸正戊基酯、(甲基)丙烯酸異戊基酯、(甲基)丙烯酸新戊基酯、(甲基)丙烯酸正己基酯、(甲基)丙烯酸環己基酯、(甲基)丙烯酸異冰片基酯,或(甲基)丙烯酸羥基乙基酯。亦可使用這些單體之二或多者之組合。
可使用之嵌段共聚物包括至少二嵌段,且可為二嵌段、三嵌段、四嵌段等具不連續嵌段之共聚物。示範性嵌段共聚物包括聚苯乙烯-b-聚乙烯基吡啶、聚苯乙烯-b-聚丁二烯、聚苯乙烯-b-聚異戊二烯、聚苯乙烯-b-聚甲基丙烯酸甲基酯、聚苯乙烯-b-聚烯芳香族,聚異戊二烯-b-聚環氧乙烷、聚苯乙烯-b-聚(乙烯-丙烯)、聚環氧乙烷-b-聚己內酯、聚丁二烯-b-聚環氧乙烷、聚苯乙烯-b-聚((甲基)丙烯酸第三丁基酯)、聚甲基丙烯酸甲基酯-b-聚(甲基丙烯酸第三丁基酯)、聚環氧乙烷-b-聚環氧丙烷、聚苯乙烯-b-
聚四氫呋喃、聚苯乙烯-b-聚異戊二烯-b-聚環氧乙烷、聚(苯乙烯-b二甲基矽氧烷)、聚(甲基丙烯酸甲基酯-b二甲基矽氧烷)、聚((甲基)丙烯酸甲基酯-r-苯乙烯)-b-聚甲基丙烯酸甲基酯、聚((甲基)丙烯酸甲基酯-r-苯乙烯)-b-聚苯乙烯、聚(對-羥基苯乙烯-r-苯乙烯)-b-聚甲基丙烯酸甲基酯、聚(對-羥基苯乙烯-r-苯乙烯)-b-聚環氧乙烷、聚異戊二烯-b-聚苯乙烯-b-聚二茂鐵矽烷,或包含前述嵌段共聚物之至少一者之組合。
該嵌段共聚物較佳具有適合進一步加工之總分子量與聚合分散度。嵌段共聚物一般具有重量平均分子量(Mw)1,000至200,000g/mol。該嵌段共聚物一般具有聚合分散度(Mw/Mn)1.01至6、1.01至1.5、1.01至1.2或1.01至1.1。分子量,Mw與Mn二者皆可以如使用通用校正法之凝膠通透層析法測定,並以聚苯乙烯標準品校正。
嵌段共聚物一般以旋轉塗覆法,將溶液塗覆於下方層(導引圖案與刷層)表面上,以形成自組裝層108於下方層表面上。嵌段共聚物進行退火,以於退火過程中形成各區域。該退火條件取決於DSA層之特定材料。退火一般於溫度100至380℃進行30秒至2小時。退火一般可於恆溫或可變化溫度進行,如動態梯度加熱,以幫助嵌段共聚物中所欲之自組裝型態形成。另一幫助嵌段共聚物中所欲之自組裝型態形成之適當退火技術,涉及膜以溶劑蒸氣接觸,不論是於室溫或高溫下。溶劑蒸氣可來自如單一溶劑或溶劑摻合物。溶劑蒸氣之組成物可隨時間變化。溶
劑蒸氣退火技術描述於如Jung及Ross,(“Solvent-Vapor-Induced Tunability of Self-Assembled Block Copolymer Patterns," Adv.Mater.,Vol.21,Issue 24,pp.2540-2545,Wiley-VCH,pp.1521-4095(2009)),以及美國專利申請公開號2011/0272381中。
第一嵌段於下方層上對齊導引圖案而形成第一區域110,而第二嵌段於下方層上相鄰於第一區域而形成第二區域112對齊,如此形成各區域。其中,該下方層之導引圖案形成稀疏的圖案,由大於第一與第二區域間之間距的間距隔開,額外之第一和第二區域形成於下方層上,以填充該稀疏圖案的間距,如圖所示。該額外第一區域無導引圖案可對齊下,而是對齊先前形成之第二(分散)區域,以及額外第二區域對齊該額外第一區域。
之後藉由移除第一或第二區域,以及視需要之下方層之下方部分而形成浮雕圖案(relief pattern)。移除步驟可藉由如濕式蝕刻法或乾式蝕刻法而達成,如使用氧電漿或其組合。
上述方法與結構可用於製造半導體裝置,包括需要密集線/空間圖案之記憶裝置,如動態隨機存取記憶體(DRAM)、同步動態隨機存取記憶體(SDRAM),或密集特徵之資料儲存如硬碟。應瞭解到此裝置僅用於說明,不應受限於此。
可進行基板之進一步加工,以形成最終裝置。進一步加工包括如,於基板上形成一或多個額外層、
研磨、化學-機械平坦化(CMP)、離子植入、退火、CVD、PVD、磊晶生長、電鍍、蝕刻與微影技術如DSA與光微影技術。
下列非限制性實施例係用於說明本發明。
在圓底頸狀燒瓶中,於室溫下加入N-溴化琥珀醯亞胺(102克,0.573莫耳)與600ml氯化苯。之後加入過氧化苯甲醯(1.2克,0.005莫耳),之後加入雙環[4.2.0]辛-1(6),2,4-三烯(1.1)(50克,0.48莫耳)。反應混合物於85℃攪拌2日。冷卻至室溫後,加入400ml庚烷,混合物於室溫下攪拌20分鐘。混合物經矽膠短墊過濾,並以庚烷清洗。減壓濃縮之後,所得油於約2托(torr)真空度,70至74℃蒸餾,得呈油之產物(1.2)(64g,73%產率)。
在圓底頸狀燒瓶中,加入1-溴-1,2-二氫環丁并苯(1.2)(30克,0.164莫耳)與乙二醇(150ml)。之後緩慢加入四氟
硼酸銀(I)(35克,0.18莫耳),同時使用冰浴將溫度維持於約30℃。添加後,反應混合物於50℃攪拌3小時。一旦冷卻至室溫後,加入200ml水與400ml醚類。所得混合物經矽藻土過濾。有機層以水清洗三次(每次300ml),之後以Na2SO4乾燥並濃縮,得產物(1.3)呈油(21.8g,產率79%)。
2-(1,2-二氫環丁并苯-1-基氧基)乙醇(1.3)(20克,0.122莫耳)溶於具三乙基胺(37克,0.366莫耳)以及約100ppm丁基化羥基甲苯(BHT)之500ml二氯甲烷(DCM)中。混合物以冰浴冷卻至0℃。之後滴加入甲基丙烯醯氯(1.4)(15.27克,0.146莫耳)。所得混合物於約0℃攪拌4小時。經水性處理後,該有機相以10% NH4OH與水清洗。有機相以Na2SO4乾燥並濃縮。以EA/庚烷0至40%進行快速層析法,得所欲之產物(1.5)(21g,74%產率)。
苯乙烯與4-乙烯基苯並環丁烯(VBCB)單體,係通過氧化鋁管柱,以移除所有抑制劑。28.883g苯乙烯、1.116g之VBCB、0.225g之N-第三丁基-N-(2-甲基-1-苯基丙基)-O-(1-苯基乙基)羥基胺,以及0.011g之2,2,5-三甲基-4-苯基-3-氮雜己烷-3-氮氧化物,注入100mL舒倫克(Schlenk)燒瓶中。反應混合物以三次冷凍-泵唧-解凍循環除氣,之後燒瓶注入氮氣並密封。之後,反應瓶於120℃加熱19小時。於甲醇/水(80/20)中產生沈澱。沈澱出之聚合物經過濾收集、空氣乾燥整夜、再溶解於THF中,並再沈澱於甲醇/水(80/20)中。最終聚合物經過濾、空氣乾燥整夜,並進一步於25℃真空下乾燥48小時,得可交聯聚合物1(CP1)。
苯乙烯與4-乙烯基苯並環丁烯(VBCB)單體係通過氧化鋁管柱,以移除所有抑制劑。26.341g苯乙烯、3.658g之VBCB、0.229g之N-第三丁基-N-(2-甲基-1-苯基丙基)-O-(1-苯基乙基)羥基胺,以及0.011g之2,2,5-三甲基-4-苯基-3-氮雜己烷-3-氮氧化物,注入100mL Schlenk燒瓶中。反應混合物以三次冷凍-泵唧-解凍循環除氣,之後燒瓶注
入氮氣並密封。之後,反應瓶於120℃加熱19小時。於甲醇/水(80/20)中產生沈澱。沈澱出之聚合物經過濾收集、空氣乾燥整夜、再溶解於THF中,並再沈澱於甲醇/水(80/20)中。最終聚合物經過濾、空氣乾燥整夜,並進一步於25℃真空下乾燥48小時,得可交聯聚合物2(CP2)。
17.899g苯乙烯與2.101g之甲基丙烯酸2-(1,2-二氫環丁并苯-1-基氧基)乙基酯(BCBMA),係溶於30.000g丙二醇甲基醚乙酸酯(PGMEA)中。單體溶液係以氮氣起泡20分鐘而除氣。PGMEA(15.097g)注入250mL三頸瓶中,其裝配有濃縮器與機械式攪拌器,以氮氣起泡20分鐘而除氣。之後,將反應瓶中之溶劑帶至溫度80℃。V601(二甲基-2,2-偶氮二異丁酸酯)(1.041g)係溶於4.000g之PGMEA中,起始劑溶液以氮氣起泡20分鐘而除氣。起始劑溶液加至反應瓶中,之後單體溶液滴加入反應器中,歷時3小時,且在劇烈攪拌與氮氣環境下。待單體進料完成後,聚合混合物額外於80℃維持1小時。總共4小時之聚合反應之後(3小時進料以及1小時進料後攪拌),聚合混合物冷卻至室溫。於甲醇/水(80/20)中產生沈澱。沈澱出之聚合物經過濾收集、空氣乾燥整夜、再溶解於THF中,並再沈澱於甲醇/
水(80/20)中。最終聚合物經過濾、空氣乾燥整夜,並進一步於25℃真空下乾燥48小時,得可交聯聚合物3(CP3)。
16.028g苯乙烯與3.972g之甲基丙烯酸2-(1,2-二氫環丁并苯-1-基氧基)乙基酯(BCBMA),係溶於30.000g丙二醇甲基醚乙酸酯(PGMEA)中。單體溶液係以氮氣起泡20分鐘而除氣。PGMEA(14.694g)注入250mL三頸瓶中,其裝配有濃縮器與機械式攪拌器,以氮氣起泡20分鐘而除氣。之後,將反應瓶中之溶劑帶至溫度80℃。V601(二甲基-2,2-偶氮二異丁酸酯)(0.984g)係溶於4.000g之PGMEA中,起始劑溶液以氮氣起泡20分鐘而除氣。起始劑溶液加至反應瓶中,之後單體溶液滴加進料至反應器中,歷時3小時,且在劇烈攪拌與氮氣環境下。待單體進料完成後,聚合混合物額外於80℃維持1小時。總共4小時之聚合反應之後(3小時進料以及1小時進料後攪拌),聚合混合物冷卻至室溫。於甲醇/水(80/20)中產生沈澱。沈澱出之聚合物經過濾收集、空氣乾燥整夜、再溶解於THF中,並再沈澱於甲醇/水(80/20)中。最終聚合物經過濾、空氣乾燥整夜,並進一
步於25℃真空下乾燥48小時,得可交聯聚合物4(CP4)。
15.901g甲基丙烯酸甲基酯(MMA)與4.099g之甲基丙烯酸2-(1,2-二氫環丁并苯-1-基氧基)乙基酯(BCBMA),溶於30.000g丙二醇甲基醚乙酸酯(PGMEA)。單體溶液係以氮氣起泡20分鐘而除氣。PGMEA(15.037g)注入250mL三頸瓶中,其裝配有濃縮器與機械式攪拌器,以氮氣起泡20分鐘而除氣。之後,將反應瓶中之溶劑帶至溫度80℃。V601(二甲基-2,2-偶氮二異丁酸酯)(1.016g)係溶於4.000g之PGMEA中,起始劑溶液以氮氣起泡20分鐘而除氣。起始劑溶液加至反應瓶中,之後單體溶液滴加進料至反應器中,歷時3小時,且在劇烈攪拌與氮氣環境下。待單體進料完成後,聚合混合物額外於80℃維持1小時。總共4小時之聚合反應之後(3小時進料以及1小時進料後攪拌),聚合混合物冷卻至室溫。於甲醇/水(80/20)中產生沈澱。沈澱出之聚合物經過濾收集、空氣乾燥整夜、再溶解於THF中,並再沈澱於甲醇/水(80/20)中。最終聚合物經過濾、空氣乾燥整夜,並進一步於25℃真空下乾燥48小時,得可交聯
聚合物5(CP5)。
17.445g甲基丙烯酸苄基酯(BZMA)與2.555g之甲基丙烯酸2-(1,2-二氫環丁并苯-1-基氧基)乙基酯(BCBMA),溶於30.000g丙二醇甲基醚乙酸酯(PGMEA)。單體溶液係以氮氣起泡20分鐘而除氣。PGMEA(14.144g)注入250mL三頸瓶中,其裝配有濃縮器與機械式攪拌器,以氮氣起泡20分鐘而除氣。之後,將反應瓶中之溶劑帶至溫度80℃。V601(二甲基-2,2-偶氮二異丁酸酯)(0.633g)係溶於4.000g之PGMEA中,起始劑溶液以氮氣起泡20分鐘而除氣。起始劑溶液加至反應瓶中,之後單體溶液滴加進料至反應器中,歷時3小時,且在劇烈攪拌與氮氣環境下。待單體進料完成後,聚合混合物額外於80℃維持1小時。總共4小時之聚合反應之後(3小時進料以及1小時進料後攪拌),聚合混合物冷卻至室溫。於甲醇/水(80/20)中產生沈澱。沈澱出之聚合物經過濾收集、空氣乾燥整夜、再溶解於THF中,並再沈澱於甲醇/水(80/20)中。最終聚合物經過濾、空氣乾燥整夜,並進一步於25℃真空下乾燥48小時,得可交聯
聚合物6(CP6)。
17.254g甲基丙烯酸苯基酯(PHMA)與2.746g之甲基丙烯酸2-(1,2-二氫環丁并苯-1-基氧基)乙基酯(BCBMA),溶於30.000g丙二醇甲基醚乙酸酯(PGMEA)。單體溶液係以氮氣起泡20分鐘而除氣。PGMEA(14.254g)注入250mL三頸瓶中,其裝配有濃縮器與機械式攪拌器,以氮氣起泡20分鐘而除氣。之後,將反應瓶中之溶劑帶至溫度80℃。V601(二甲基-2,2-偶氮二異丁酸酯)(0.680g)係溶於4.000g之PGMEA中,起始劑溶液以氮氣起泡20分鐘而除氣。起始劑溶液加至反應瓶中,之後單體溶液滴加進料至反應器中,歷時3小時,且在劇烈攪拌與氮氣環境下。待單體進料完成後,聚合混合物額外於80℃維持1小時。總共4小時之聚合反應之後(3小時進料以及1小時進料後攪拌),聚合混合物冷卻至室溫。於甲醇/水(80/20)中產生沈澱。沈澱出之聚合物經過濾收集、空氣乾燥整夜、再溶解於THF中,並再沈澱於甲醇/水(80/20)中。最終聚合物經過濾、空氣乾燥整夜,並進一步於25℃真空下乾燥48小時,得可交聯
聚合物7(CP7)。
16.415g之4-甲基苯乙烯(4MS)、3.585g之甲基丙烯酸2-(1,2-二氫環丁并苯-1-基氧基)乙基酯(BCBMA),與0.178g之V601(二甲基-2,2-偶氮二異丁酸酯),溶於20.000g丙二醇甲基醚乙酸酯(PGMEA)中,注入250mL三頸瓶中,其裝配有濃縮器與機械式攪拌器。單體溶液以氮氣起泡20分鐘而除氣。之後,將反應溶液帶至溫度60℃。24小時聚合反應之後,反應混合物冷卻至室溫。於甲醇/水(80/20)中產生沈澱。沈澱出之聚合物經過濾收集、空氣乾燥整夜、再溶解於THF中,並再沈澱於甲醇/水(80/20)中。最終聚合物經過濾、空氣乾燥整夜,並進一步於25℃真空下乾燥48小時,得可交聯聚合物8(CP8)。
18.125g之4-甲基苯乙烯(4MS)、1.875g之甲基丙烯酸2-(1,2-二氫環丁并苯-1-基氧基)乙基酯(BCBMA)與0.130g之V601(二甲基-2,2-偶氮二異丁酸酯),溶於20.000g丙二醇甲基醚乙酸酯(PGMEA)中,注入250mL三頸瓶中,其裝配有濃縮器與機械式攪拌器。單體溶液以氮氣起泡20分鐘而除氣。之後,將反應溶液帶至溫度60℃。24小時聚合反應之後,反應混合物冷卻至室溫。於甲醇/水(80/20)中產生沈澱。沈澱出之聚合物經過濾收集、空氣乾燥整夜、再溶解於THF中,並再沈澱於甲醇/水(80/20)中。最終聚合物經過濾、空氣乾燥整夜,並進一步於25℃真空下乾燥48小時,得可交聯聚合物9(CP9)。
18.258g之甲基丙烯酸正-丙基酯(nPMA)、1.742g之甲基丙烯酸2-(1,2-二氫環丁并苯-1-基氧基)乙基酯(BCBMA)與0.121g之V601(二甲基-2,2-偶氮二異丁酸酯),溶於20.000g丙二醇甲基醚乙酸酯(PGMEA)中,注入250mL三頸瓶中,其裝配有濃縮器與機械式攪拌器。單體溶液以氮氣起泡20分鐘而除氣。之後,將反應溶液帶至溫度60℃下。24小時聚合反應之後,反應混合物冷卻至室溫。於甲醇/水(80/20)中產生沈澱。沈澱出之聚合物經過濾收集、空氣乾燥整夜、再溶解於THF中,並再沈澱於甲醇/水(80/20)中。最終聚合物經過濾、空氣乾燥整夜,並進一步於25℃真空下乾燥48小時,得可交聯聚合物10(CP10)。
可交聯聚合物之熱交聯反應,係間接地以溶劑剝除測試監測。實施例1至10製備之可交聯聚合物各者溶於丙二醇甲基醚乙酸酯(PGMEA)中,並旋轉塗覆於裸矽(Si)晶圓上。經塗覆之晶圓係於氮氣環境下加熱,於表1所列之各種溫度與時間下加熱,以研究熱交聯效果。之後,該膜以
PGMEA徹底潤洗,以移除未經交聯之材料。測量殘留在基板上之不溶性經交聯聚合物之厚度。結果列於下表1。
表1顯示比較例之可交聯聚合物1與2之有效交聯,只有在高溫下退火可達成,如CP1於250℃退火30分鐘,CP2於250℃退火5分鐘。本發明之可交聯聚合物3至10每一者之有效交聯,則在較低溫度與較短時間下退火便可達成。
可交聯下方層組成物,係於PGMEA中溶解可交聯聚合物CP4、CP5與CP8之每一者而製備。所得組成物係旋
轉塗覆於各別之矽晶圓上,以形成具厚度8至9nm之下方層。於下表2所列之條件下,將下方層退火而誘發交聯反應。包括聚苯乙烯-嵌段-聚甲基丙烯酸甲基酯(PS-b-PMMA)嵌段共聚物於PGMEA中之DSA組成物,係塗覆於下方層上,對於CP4與CP59使用之厚度為32nm,對於CP8使用之厚度為50nm,並於250℃退火2分鐘。於所得晶圓上進行原子力顯微鏡(AFM)成像,以觀察表面上形成之圖案。聚合物CP4所得之AFM影像為指紋(fingerprint)圖案,代表其為對於DSA聚合物之聚苯乙烯與聚甲基丙烯酸甲基酯二嵌段皆為中性之下方層。聚合物CP5與CP8之AFM影像分別為聚甲基丙烯酸甲基酯-偏好,以及聚苯乙烯-偏好之島/洞圖案。這些結果顯示下方層組成物之表面能量可精調為偏好DSA嵌段共聚物之不同嵌段,或對二嵌段皆為中性。
Claims (10)
- 一種以經引導自組裝方式形成圖案之方法,包含:(a)提供半導體基板,其包含待圖案化之一或多層;(b)施加可交聯之下方層組成物於該待圖案化之一或多層上,以形成可交聯下方層,其中該可交聯下方層組成物包含可交聯聚合物,其包含具通式(I-A)或(I-B)之第一單元:
- 如申請專利範圍第1項所述之方法,更包含圖案化該 經交聯下方層。
- 如申請專利範圍第2項所述之方法,其中該圖案化之經交聯下方層係以光微影與蝕刻形成,其中暴露出基板之凹陷位於經交聯下方層之相鄰圖案之間。
- 如申請專利範圍第3項所述之方法,更包含於相鄰圖案間之該凹陷內形成刷層,其中該自組裝層形成於該圖案與該刷層上。
- 如申請專利範圍第2項所述之方法,其中該圖案係以化學性改變該經交聯下方層上之經選定區域而形成。
- 如申請專利範圍第1至5項中任一項所述之方法,其中該可聚合官能基P選自下列通式(II-A)與(II-B):
- 如申請專利範圍第1至6項中任一項所述之方法,其中該第一單元為通式(I-A),其中X1選自C1-C10烷氧基、胺、硫、-OCOR9、-NHCOR10,及其組合,其中R9選自於經取代與未經取代之C1至C10直線形、分支與環狀烴且,其中R10選自於經取代與未經取代之C1至C10直線形、分支與環狀烴。
- 如申請專利範圍第1至6項中任一項所述之方法,其中,該第一單元為通式(I-B),其中X2為-O-、-S-、-COO-、-CONR11-、-CONH-與-OCONH-,其中R11選自氫,以及經取代與未經取代之C1至C10直線形、分支與環狀烴,較佳為烷基、較佳為-O-,及其組合。
- 如申請專利範圍第1至8項中任一項所述之方法,其中該第一單元由選自於下列之一或多種單體而形成:
- 如申請專利範圍第1至9項中任一項所述之方法,其中該聚合物更包含第二單元,其係選自通式(III)與(IV):
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EP3095127B1 (en) * | 2014-01-16 | 2020-05-20 | Brewer Science, Inc. | High-chi block copolymers for directed self-assembly |
KR20160133511A (ko) * | 2014-03-15 | 2016-11-22 | 보드 오브 리전츠, 더 유니버시티 오브 텍사스 시스템 | 블록 공중합체의 정돈 |
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KR102651697B1 (ko) * | 2015-09-07 | 2024-03-27 | 아이엠이씨 브이제트더블유 | 트렌치 보조 케모에피탁시(trac) dsa 흐름 |
JP6346132B2 (ja) * | 2015-09-11 | 2018-06-20 | 株式会社東芝 | パターン形成方法 |
US9574104B1 (en) * | 2015-10-16 | 2017-02-21 | Az Electronic Materials (Luxembourg) S.A.R.L. | Compositions and processes for self-assembly of block copolymers |
TWI612108B (zh) * | 2015-10-31 | 2018-01-21 | Rohm And Haas Electronic Materials Llc | 嵌段共聚物及圖案處理組合物以及方法 |
KR102402958B1 (ko) * | 2015-11-11 | 2022-05-27 | 삼성전자주식회사 | 반도체 장치의 패턴 형성 방법 및 반도체 장치의 제조 방법 |
EP3500637B1 (en) * | 2016-08-18 | 2022-06-22 | Merck Patent GmbH | Polymer compositions for self-assembly applications |
JP6926939B2 (ja) * | 2017-10-23 | 2021-08-25 | 東京エレクトロン株式会社 | 半導体装置の製造方法 |
US20190127506A1 (en) * | 2017-11-02 | 2019-05-02 | Rohm And Haas Electronic Materials Llc | Low temperature curable addition polymers from vinyl arylcyclobutene-containing monomers and methods for making the same |
US20190127505A1 (en) * | 2017-11-02 | 2019-05-02 | Rohm And Haas Electronic Materials Llc | Addition polymers from nitrogen heterocycle containing monomers and vinyl arylcyclobutene-containing monomers |
US10529552B2 (en) | 2017-11-29 | 2020-01-07 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method for manufacturing a semiconductor device and a coating material |
US10513568B2 (en) * | 2017-12-01 | 2019-12-24 | Rohm and Haas Electronic Materials | Methods of making stable and thermally polymerizable vinyl, amino or oligomeric phenoxy benzocyclobutene monomers with improved curing kinetics |
KR102484630B1 (ko) * | 2018-08-16 | 2023-01-04 | 주식회사 엘지화학 | 패턴화 기판의 제조 방법 |
KR102498631B1 (ko) * | 2018-08-16 | 2023-02-10 | 주식회사 엘지화학 | 패턴화 기판의 제조 방법 |
CN109206605B (zh) * | 2018-08-31 | 2020-11-24 | 江苏汉拓光学材料有限公司 | 用于定向自组装的嵌段共聚物和使用其的定向自组装方法 |
TW202307048A (zh) * | 2021-05-18 | 2023-02-16 | 德商馬克專利公司 | 用於圖案化苯乙烯-嵌段-甲基丙烯酸甲酯(ps-b-pmma)型嵌段共聚物之定向自組裝之具有改良乾蝕刻能力的疏水性可交聯釘壓底層 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4661193A (en) * | 1984-08-27 | 1987-04-28 | The Dow Chemical Company | Adhesive compositions for arylcyclobutene monomeric compositions |
US4965329A (en) | 1984-08-27 | 1990-10-23 | The Dow Chemical Company | N-substituted arylcyclo butenyl-unsaturated cyclic imides |
US4540763A (en) * | 1984-09-14 | 1985-09-10 | The Dow Chemical Company | Polymers derived from poly(arylcyclobutenes) |
US4698394A (en) * | 1985-12-23 | 1987-10-06 | Shell Oil Company | Reactive styrene polymers |
US5198527A (en) * | 1990-12-24 | 1993-03-30 | The Dow Chemical Company | Arylcyclobutene terminated carbonate polymer |
US5318827A (en) * | 1992-06-15 | 1994-06-07 | The Dow Chemical Company | Carbonate polymer laminate structure |
US6565968B1 (en) * | 2000-04-12 | 2003-05-20 | Avery Dennison Corporation | UV-curable pressure-sensitive adhesives and protective coatings |
US6780567B2 (en) | 2001-08-02 | 2004-08-24 | Fuji Photo Film Co., Ltd. | Lithographic process using reaction of o-quinodimethane |
WO2004073018A2 (en) * | 2003-02-05 | 2004-08-26 | Dow Global Technologies Inc. | Sacrificial benzocyclobutene/norbornene polymers for making air gaps within semiconductor devices |
US8999492B2 (en) | 2008-02-05 | 2015-04-07 | Micron Technology, Inc. | Method to produce nanometer-sized features with directed assembly of block copolymers |
PL2389852T3 (pl) * | 2010-05-25 | 2015-03-31 | Electrolux Home Products Corp Nv | Układ ramienia myjącego do zmywarki |
JP6035017B2 (ja) | 2010-10-04 | 2016-11-30 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | 下層組成物および下層を像形成する方法 |
JP6038134B2 (ja) * | 2011-07-04 | 2016-12-07 | ケンブリッジ ディスプレイ テクノロジー リミテッド | ポリマー、モノマーおよび、ポリマーを形成する方法 |
US8691925B2 (en) * | 2011-09-23 | 2014-04-08 | Az Electronic Materials (Luxembourg) S.A.R.L. | Compositions of neutral layer for directed self assembly block copolymers and processes thereof |
JP2013174766A (ja) * | 2012-02-27 | 2013-09-05 | Toshiba Corp | マスクパターン作成方法、マスクパターン作成プログラムおよび半導体装置の製造方法 |
WO2013158527A1 (en) | 2012-04-16 | 2013-10-24 | Brewer Science Inc. | Silicon hardmask layer for directed self-assembly |
JP5710546B2 (ja) | 2012-04-27 | 2015-04-30 | 信越化学工業株式会社 | パターン形成方法 |
US8940810B2 (en) * | 2012-06-07 | 2015-01-27 | Canon Kabushiki Kaisha | Optical component, electronic board, method for producing the optical component, and method for producing the electronic board |
CN104701238B (zh) * | 2013-11-14 | 2019-10-08 | 罗门哈斯电子材料有限公司 | 间隙填充方法 |
US20150210793A1 (en) * | 2013-12-31 | 2015-07-30 | Rohm And Haas Electronic Materials Llc | Crosslinkable polymers and underlayer compositions |
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