TWI790194B - 清潔組成物、用於製造半導體裝置之方法、清潔方法及半導體封裝 - Google Patents
清潔組成物、用於製造半導體裝置之方法、清潔方法及半導體封裝 Download PDFInfo
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- TWI790194B TWI790194B TW105124418A TW105124418A TWI790194B TW I790194 B TWI790194 B TW I790194B TW 105124418 A TW105124418 A TW 105124418A TW 105124418 A TW105124418 A TW 105124418A TW I790194 B TWI790194 B TW I790194B
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002966 varnish Substances 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
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
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Abstract
本發明係關於一種組成物(例如清潔及/或剝離組成物),其含有(a)0.5-25重量百分比之鹼性化合物;(b)1-25重量百分比之醇胺化合物;(c)0.1-20重量百分比之羥銨化合物;(d)5-95重量百分比之有機溶劑;(e)0.1-5重量百分比之腐蝕抑制劑化合物;及(f)2-25重量百分比之水。
Description
相關申請案之交叉引用
本申請案主張於2015年8月3日申請之美國臨時申請案第62/200,236號的優先權,該臨時申請案以全文引用的方式併入本文中。
本發明係有關於一種清潔組成物。
在聚合物膜之雷射剝蝕期間,總形成碎片,且量及類型視膜之組成及剝蝕之加工條件而定。此碎片大部分沈積在露台上,但一些可到達結構底部及壁。澈底移除對能夠進行進一步之組件建立步驟,諸如焊接及金屬沈積而言為必不可少的。在不影響膜下對此類碎片進行化學清潔為本發明之焦點之一。此外,本發明之組成物之設計允許組成物在高溫下充當有效剝離劑。
本發明描述一種清潔組成物,其用於室溫(例如25℃)下雷射剝蝕後清潔製程,其亦可用作再加工製程及/或在高溫(例如65-85℃)下後續加工後聚合物層之剝離組成物。
在一些實施例中,組成物包含(或基本上由其組成或由其組成):(a)0.5-25重量百分比之鹼性化合物;(b)1-25重量百分比之醇胺化合物;(c)0.1-20重量百分比之羥銨化合物;(d)5-95重量百分比之有機溶劑;(e)0.1-5重量百分比之腐蝕抑制劑化合物;及(f)2-25重量百分比之水。
在一些實施例中,本發明之特徵在於一種組成物,其包含(或基本上由其組成或由其組成):(a)鹼性化合物;(b)醇胺化合物;(c)羥銨化合物;(d)有機溶劑;(e)腐蝕抑制劑化合物;及(f)水,其中組成物之pH值為至少約12,且有機溶劑相對於水具有約0.5至約0.8之相對能差(RED)。在此類實施例中,組成物可具有約5cSt至約12cSt之25℃下動態黏度。
本發明亦描述一種用於雷射剝蝕後清潔之方法及一種用於剝離聚醯亞胺或聚醯亞胺前驅物組成物之方法。
本發明之組成物之設計中的一獨特態樣為在室溫下,此組成物用作清潔劑來移除雷射剝蝕後碎片,且在高溫下用作極有效之剝離劑。
本發明之一些實施例係關於適於在雷射剝蝕製程後及在不同處理條件下清潔殘渣之組成物,其亦適於剝離聚合物層。當在雷射剝蝕後製程後用作清潔組成物時,基本上半導體基板上很少(若有)聚合物層經移除。當用於剝離製程時,關鍵為移除所有聚合物層且清潔下層基板。本發明者意外地發現本文所述之組成物可有效用於上述清潔與剝離製程。
在一些實施例中,本文所述之清潔/剝離組成物包括:(a)0.5-25重量百分比之鹼性化合物;(b)1-25重量百分比之醇胺化合物;(c)0.1-20重量百分比之羥銨化合物;(d)5-95重量百分比之有機溶劑;(e)0.1-5重量百分比之腐蝕抑制劑化合物;及(f)2-25重量百分比之水。
可用於本發明之清潔/剝離組成物之鹼性化合物(a)不受具體限制。在一些實施例中,鹼性化合物包括無機鹼,諸如氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸氫鈉、碳酸鉀及碳酸氫鉀;及有機鹼,諸如氫氧化四級銨。較佳鹼性化合物為氫氧化四級銨。氫氧化四級銨之實例包括(但不限於)可選自由以下各物組成之群的氫氧化四級銨:氫氧化四甲基銨(TMAH)、氫氧化2-羥基三甲基銨、氫氧化四乙基銨(TEAH)、氫氧化四丙基銨(TPAH)、氫氧化四丁基胺(TBAH)及其混合物。較佳氫氧化四級銨為氫氧化四甲基銨及氫氧化2-羥基三甲基銨。一更佳氫氧化四級銨為氫氧化四甲基銨。
用於本發明之清潔/剝離組成物之鹼性化合
物(a)以相對於本發明組成物之總量至少約0.5重量%(例如至少約1重量%、至少約2.5重量%或至少約5重量%)至至多約25重量%(例如至多約20重量%、至多約17.5重量%、至多約15重量%、至多約12.5重量%或至多約10重量%)之量存在。
用於本發明之清潔/剝離組成物之醇胺化合物(b)不受具體限制。此等醇胺化合物包括(但不限於)單乙醇胺(MEA)、二乙醇胺、三乙醇胺、2-(2-胺基乙氧基)乙醇、3-胺基-1-丙醇、胺基-2-丙醇、2-胺基-1-丁醇、5-胺基-1-戊醇、2-胺基-2-甲基-1-丙醇、3-甲基胺基-1-丙醇、4-胺基-1-丁醇、參(羥甲基)胺基乙烷、1-二甲基胺基-2-丙醇、1-胺基-1-環戊烷甲醇、單異丙醇胺、二異丙醇胺、三異丙醇胺、2-異丙胺基乙醇、2-丙基胺基乙醇、2-(第三丁基胺基)乙醇、5-胺基-2,2-二甲基戊醇、2-胺基-3-甲基-1-丁醇、N-甲基胺基乙醇、N-甲基二乙醇胺、N-乙基乙醇胺、N-丁基乙醇胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N,N-二丁基乙醇胺、N-甲基-N-乙基乙醇胺及此等醇胺中之兩者或超過兩者的混合物。
用於本發明之清潔/剝離組成物之醇胺化合物(b)以相對於組成物之總量至少約1重量%(例如至少約2重量%、至少約3重量%或至少約4重量%)至至多約25重量%(例如至多約22.5重量%、至多約20重量%、至多約17.5重量%、至多約15重量%、至多約12.5重量%、至多約10重量%、至多約7.5重量%或至多約5重量%)之量存在。
可用於本發明之清潔/剝離組成物之羥銨化合物(c)不受具體限制。羥銨化合物之實例包括(但不限於)硫酸羥銨、鹽酸羥銨、硝酸羥銨、磷酸羥銨、過氯酸羥銨、檸檬酸羥銨及乙酸羥銨。
用於本發明之清潔/剝離組成物之羥銨化合物以相對於組成物之總量至少約0.1重量%(例如至少約0.5重量%、至少約1重量%、至少約1.5重量%或至少約2重量%)至至多約20重量%(例如至多約17重量%、至多約14重量%、至多約11重量%、至多約8重量%或至多約5重量%)之量存在。
本發明組成物中之有機溶劑(d)(例如水溶性有機溶劑)可包括高度與水相容之有機溶劑,其為例如N-甲基吡咯啶酮(NMP)、N-乙基吡咯啶酮(NEP)、γ-丁內酯、甲基乙基酮(MEK)、二甲亞碸(DMSO)、二甲碸、二甲基甲醯胺、N-甲基甲醯胺、甲醯胺、四甲基脲、四氫糠醇(THFA)及其混合物。在一些實施例中,有機溶劑選自相對於水具有至多約0.8(例如至多約0.75、至多約0.7)及/或至少約0.5(例如至少約0.55、至少約0.6或至少約0.65)之相對能差(RED)。RED為漢森空間中漢森參數與漢森空間中相互作用半徑(Ro)之間的距離比(Ra)。Ra由下式定義:(Ra)2=4(δd2-δd1)2+(δp2-δp1)2+(δh2-δh1)2,其中δd、δp及δh分別為分散之間的能量、分子間力及分子之間的氫鍵。關於漢森參數之更多細節可見於以下參考文獻:「Hansen,Charles(2007).Hansen Solubility
Parameters:A user's handbook,第二版.Boca Raton,Fla:CRC Press.ISBN 978-0-8493-7248-3」。
在某些實施例中,有機溶劑(例如水溶性有機溶劑)可為二醇醚。二醇醚可包括二醇單(C1-C6)烷基醚及二醇二(C1-C6)烷基醚,包括(但不限於)(C1-C20)烷二醇、(C1-C6)烷基醚及(C1-C20)烷二醇二(C1-C6)烷基醚。二醇醚之實例包括乙二醇單甲醚、乙二醇單乙醚、乙二醇單丁醚、乙二醇二甲醚、乙二醇二乙醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丙醚、二乙二醇單丙醚、二乙二醇單丁醚、二乙二醇單異丁醚、二乙二醇單苯甲醚、二乙二醇二甲醚、二乙二醇二乙醚、三乙二醇單甲醚、三乙二醇二甲醚、聚乙二醇單甲醚、二乙二醇甲基乙基醚、三乙二醇乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、丙二醇單甲醚、丙二醇二甲醚、丙二醇單丁醚、丙二醇、單丙醚、二丙二醇單甲醚、二丙二醇單丙醚、二丙二醇單異丙醚、二丙二醇二異丙醚、三丙二醇單甲醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基丁醇、1,1-二甲氧基乙烷及2-(2-丁氧基乙氧基)乙醇。二醇醚之更典型實例為丙二醇單甲醚、丙二醇單丙醚、三(丙二醇)單甲醚及2-(2-丁氧基乙氧基)乙醇。
本發明之組成物中之較佳溶劑為二甲亞碸(DMSO)及四氫糠醇(THFA)。更佳溶劑為四氫糠醇(THFA)。
用於本發明之清潔/剝離組成物之溶劑以相
對於本發明組成物之總量至少約5重量%(例如至少約10重量%、至少約15重量%、至少約20重量%、至少約25重量%、至少約30重量%、至少約35重量%、至少約40重量%或至少約45重量%)至至多約95重量%(例如至多約90重量%、至多約85重量%、至多約80重量%、至多約75重量%、至多約70重量%、至多約65重量%、至多約60重量%、至多約55重量%或至多約50重量%)之量存在。
用於本發明之清潔/剝離組成物之腐蝕抑制劑化合物(e)包括(但不限於)芳族羥基化合物、炔醇、含有羧基之有機化合物及其酸酐以及三唑化合物。
芳族羥基化合物之實例包括(但不限於)苯酚、甲酚、二甲苯酚、焦兒茶酚、間苯二酚、氫醌、連苯三酚、1,2,4-苯三酚、水楊醇、對羥基苯甲醇、鄰羥基苯甲醇、對羥基苯乙醇、對胺基苯酚、間胺基苯酚、二胺基苯酚、胺基間苯二酚、對羥基苯甲酸、鄰羥基苯甲酸、2,4-二羥基苯甲酸、2,5-二羥基苯甲酸、3,4-二羥基苯甲酸及3,5-二羥基苯甲酸。
炔醇之實例包括(但不限於)2-丁炔-1,4-二醇、3,5-二甲基-1-己炔-3-醇、2-甲基-3-丁炔-2-醇、3-甲基-1-戊炔-3-醇、3,6-二甲基-4-辛炔-3,6-二醇、2,4,7,9-四甲基-5-癸炔-4,7-二醇及2,5-二甲基-3-己炔2,5-二醇。
含有羧基之有機化合物及其酸酐之實例包括(但不限於)甲酸、乙酸、丙酸、丁酸、異丁酸、乙二酸、丙二酸、丁二酸、戊二酸、順丁烯二酸、反丁烯二酸、苯
甲酸、鄰苯二甲酸、1,2,3-苯三甲酸、乙醇酸、乳酸、蘋果酸、檸檬酸、乙酸酐及水楊酸。
三唑化合物可包括三唑、苯并三唑、經取代之三唑及經取代之苯并三唑。三唑化合物之實例包括(但不限於)1,2,4-三唑、1,2,3-三唑或經諸如C1-C8烷基(例如5-甲基三唑)、胺基、硫醇、巰基、亞胺基、羧基及硝基之取代基取代的三唑。特定實例包括苯并三唑、甲苯基三唑、5-甲基-1,2,4-三唑、5-苯基-苯并三唑、5-硝基-苯并三唑、3-胺基-5-巰基-1,2,4-三唑、1-胺基-1,2,4-三唑、羥基苯并三唑、2-(5-胺基-戊基)-苯并三唑、1-胺基-1,2,3-三唑、1-胺基-5-甲基-1,2,3-三唑、3-胺基-1,2,4-三唑、3-巰基-1,2,4-三唑、3-異丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、鹵基-苯并三唑(鹵基=F、Cl、Br或I)、萘并三唑及其類似物。
在一些實施例中,腐蝕抑制劑為結構(I)之肟化合物:
其中R1係選自由以下各基組成之群:氫、經取代或未經取代之C1-C12直鏈或分支鏈烷基、經取代或未經取代之C5-C10環烷基或雜環烷基及經取代或未經取代之C6-C12芳基或雜芳基;且R2至R5各獨立地選自由以下各基組成之
群:氫、鹵素、經取代或未經取代之C1-C12直鏈或分支鏈烷基、經取代或未經取代之C5-C10環烷基或雜環烷基及經取代或未經取代之C6-C12芳基或雜芳基;或任兩個相鄰R2至R5(例如R2及R3、R3及R4或R4及R5)連同其附接之環碳原子一起形成六員環。
在一些實施例中,R1為氫、經取代或未經取代之C1-C12直鏈或分支鏈烷基或經取代或未經取代之C6-C12芳基。R1基團之實例包括(但不限於)氫、甲基及苯基。在一些實施例中,R2至R5各獨立地為氫、鹵素、經取代或未經取代之C1-C12直鏈或分支鏈烷基、經取代或未經取代C5-C10環烷基或雜環烷基或經取代或未經取代之C6-C12芳基或雜芳基。R2-R5基團之實例包括(但不限於)氫、鹵素、壬基、十二烷基、苯基、異丙基、第三丁基、環戊基、1,3-二甲基環己基及甲苯基。結構(I)之化合物上之取代基經選擇以最佳化多種參數,包括(但不限於)既定組成物中肟化合物之溶解性及活性以及組成物之儲存穩定性。
適合結構(I)之化合物之實例包括(但不限於)
用於本發明之清潔/剝離組成物之腐蝕抑制劑化合物以相對於組成物之總量至少約0.1重量%(例如至
少約0.2重量%、至少約0.4重量%、至少約0.6重量%、至少約0.8重量%或至少約1重量%)至至多約5重量%(例如至多約4重量%、至多約3重量%、至多約2重量%、至多約1.5重量%、至多約1重量%、至多約0.5重量%或至多約0.3重量%)之量存在。在一些實施例中,腐蝕抑制劑之較佳量為相對於組成物之總量0.2重量%至0.4重量%。
用於本發明之清潔/剝離組成物之水(諸如去離子水、純水、超純水等)之量為相對於組成物之總量至少約2重量%(例如至少約4重量%、至少約6重量%或至少約8重量%)至至多約25重量%(例如至多約20重量%、至多約17.5重量%、至多約15重量%、至多約12.5重量%或至多約10重量%)。
本發明之清潔/剝離組成物亦可包括一或多種以下添加劑,其條件為此等添加劑不會不利地影響組成物之剝離及/或清潔效能,亦不會破壞下層基板表面:界面活性劑、螯合劑、偶合劑、化學改質劑、染料、抗微生物劑及/或其他添加劑,總量多達以組成物之總重量計5重量百分比。
本發明之清潔/剝離組成物中適合界面活性劑包括不限於:氟烷基界面活性劑;聚乙二醇;聚丙二醇;聚乙二醇醚;聚丙二醇醚;羧酸鹽;十二烷基苯磺酸及其鹽;聚丙烯酸酯聚合物;二壬基苯基聚氧乙烯;矽氧烷聚合物;經改質之矽氧烷聚合物;炔二醇;經改質之炔二醇、烷基銨鹽;經改質之烷基銨鹽;烷基銨磺酸內鹽及上述兩
者或超過兩者之組合。適合界面活性劑之實例包括(但不限於)JP-A-62-36663、JP-A-61-226746、JP-A-61-226745、JP-A-62-170950、JP-A-63-34540、JP-A-7-230165、JP-A-8-62834、JP-A-9-54432及JP-A-9-5988(以引用的方式併入本文中)中描述之界面活性劑。
螯合劑之實例包括(但不限於)乙二胺四乙酸(EDTA)、羥乙基乙二胺三乙酸(HEDTA)、青黴胺、2,3-二巰基-1-丙磺酸(DMPS)、二巰基丁二酸(DMSA)、葡糖酸、丙烯酸、次氮基三乙酸(NTA)、麩胺酸二乙酸(GLDA;DISSOLVINE(R)GL,來自AkzoNobel,Chicago,Ill.)、亞胺基二丁二酸四鈉、亞胺基丁二酸、二伸乙三胺五乙酸五鈉及聚天冬胺酸酯。舉例而言,螯合劑可為EDTA。
本發明之清潔/剝離組成物可進一步包括偶合劑。偶合劑可幫助穩定化組成物,諸如維持貨架期。偶合劑之實例包括(但不限於)二甲苯磺酸鈉(SXS)、異丙苯磺酸鈉(SCS)及乙基己基磺酸酯(EHS)。在某些實施例中,偶合劑為二甲苯磺酸鈉。
在一些實施例中,一或多種以下物質可自本發明之清潔/剝離組成物驅除。實例包括活性含氟化合物,其進行水解以釋放氟(例如潛在HF源,諸如羧基氟化物);氟化物鹽,諸如氟化銨或氟化四級銨;氧化劑,諸如過氧化物及無機氧化劑;脒鹽,諸如胍鹽、乙醯胺鎓鹽及甲醯胺鎓鹽;脲及脲衍生物;以及酚類化合物。
本發明之清潔/剝離組成物可具有鹼性pH
值。pH值可為至少約12(例如至少約12.2、至少約12.4、至少約12.6、至少約12.8、至少約13、至少約13.2、至少約13.4、至少約13.6、至少約13.8或至少約14)及/或至多約16.0(例如至多約15.8、至多約15.6、至多約15.4、至多約15.2、至多約15.0、至多約14.8、至多約14.6、至多約14.4或至多約14)。較佳pH值範圍為13.5至15.5。最佳pH值範圍為14至15.3。組成物之pH值可藉由可使用標準水性緩衝溶液校準之pH計量測。不希望受理論束縛,咸信相對較高之pH值(亦即強鹼性條件)可促進組成物在清潔製程中移除雷射剝蝕後碎片或在剝離製程中移除聚合物層。舉例而言,在移除雷射剝蝕後碎片之清潔製程中,鹼性條件可中和酸性物質且使其可溶於水溶液。在移除聚合物層之剝離製程中,鹼性條件可促進聚合體鏈或交聯網路斷裂,因此幫助移除聚合物層。
在一些實施例中,本發明之清潔/剝離組成物可具有相對較低之動態黏度。在一些實施例中,本發明中清潔/剝離組成物之動態黏度可為至少約5.0cSt(例如至少約5.3cSt、至少約5.6cSt、至少約6.0cSt、至少約6.3cSt、至少約6.6cSt、至少約7.0cSt、至少約7.3cSt、至少約7.6cSt、至少約8.0cSt、至少約8.3cSt或至少約8.6cSt)及/或至多約12cSt(例如至多約11.6cSt、至多約11.3cSt、至多約11.0cSt、至多約10.6cSt、至多約10.3cSt、至多約10cSt、至多約9.6cSt、至多約9.3cSt或至多約9.0cSt)。如本文所用,動態黏度在25℃下藉由使用經校準之
Cannon-Fenske常規黏度計量測。不希望受理論束縛,咸信具有相對較高動態黏度之組成物可具有較低清潔/剝離能力,至少因為組成物中之活性成分擴散至聚合物層中可具有相對較低速率(與具有相對較低動態黏度之組成物比較),此可引起剝離及/或清潔能力較低。
本發明之清潔/剝離組成物可藉由使用習知混合法以任何適合次序混合各種組分來製備。組分可冷混合,不加熱。
在一些實施例中,本發明之清潔/剝離組成物可用於半導體基板上聚合物膜之雷射剝蝕後清潔之製程中。在一些實施例中,此組成物亦可用於剝離半導體基板上未曝光之感光性聚合物膜、曝光之交聯聚合物膜或非感光性聚合物膜的製程中。
半導體基板可為圓形(諸如晶圓)或可為長條。在一些實施例中,半導體基板可為矽基板、銅基板、鋁基板、氧化矽基板、氮化矽基板、玻璃基板、有機層壓基板或介電材料基板。
除聚合物膜在用於雷射剝蝕之微粒波長下的吸光度外,用於在半導體基板上形成聚合物膜之聚合物組成物不受具體限制。聚合物層可為聚醯亞胺層、聚醯亞胺前驅物層、聚(甲基)丙烯酸酯層、聚胺基甲酸酯層、聚苯并噁唑層、聚苯并噻唑層、酚醛清漆層、環氧樹脂層、聚醯胺層或聚酯層。聚合物層可為感光性或非感光性,且可藉由含有聚合物組成物之溶液旋塗、噴塗、輥塗、浸塗
或感光性或非感光性乾膜組成物使用層壓機層壓來形成。較佳聚合物層為感光性聚醯亞胺層及感光性聚醯亞胺前驅物層。可用於形成此類層之感光性聚醯亞胺組成物或感光性前驅物組成物不受具體限制且包括(但不限於)以引用的方式併入本文中之US5449588、US4661435、US8932801、US2009202793、US6160081、US7648815、US6875554及US2014178823中揭示之組成物。
在一些實施例中,較佳聚合物組成物包括:(a)至少一種可溶性聚醯亞胺聚合物,其選擇性地具有含有至少一個選自經取代或未經取代之直鏈烯基(例如C2-C6直鏈烯基)及經取代或未經取代之直鏈烯基(例如C2-C6直鏈炔基)的官能基的封端基團;(b)至少一種反應性官能化合物(RFC);(c)至少一種引發劑;及(d)至少一種溶劑。
可溶性聚醯亞胺聚合物定義為在諸如γ-丁內酯(GBL)、己內酯、環丁碸、N-甲基-2-吡咯啶酮(NMP)、N-乙基-2-吡咯啶酮、N-丁基-2-吡咯啶酮、N-甲醯基嗎啉、二甲基咪唑啶酮、N-甲基己內醯胺、N-甲基丙烯醯胺、N,N-二甲基乙醯胺(DMAc)、二甲亞碸(DMSO)、N,N-二甲基甲醯胺(DMF)、N,N-二乙基甲醯胺、二乙基乙醯胺、四氫糠醇(THFA)、碳酸伸丙酯、2-苯氧基乙醇、丙二醇苯基醚、苯甲醇、甲基乙基酮(MEK)、甲基異丁基酮(MIBK)、2-庚酮、環戊酮(CP)、環己酮、丙二醇單甲醚乙酸酯(PGMEA)、乳酸乙酯(EL)、乙酸正丁酯(n-BA)或其混合物之有機溶劑中之溶解度為5wt%或更高的聚合
物。
本文所述之聚合物組成物中反應性官能化合物(RFC)一般具有至少一個能夠與聚醯亞胺聚合物上選擇性地存在之封端官能基(例如上述聚醯亞胺聚合物上封端官能基)或與聚醯亞胺聚合物上另一反應性官能基反應的官能基。RFC可為單體或寡聚物。寡聚物可含有許多單體單元且能夠進一步反應以併入最終物質中。此類單體單元/寡聚物之實例基於一或多種以下類型:丙烯酸酯、酯、乙烯醇、胺基甲酸酯、脲、醯亞胺、醯胺、咔唑、碳酸酯、哌喃糖、矽氧烷、尿素-甲醛及三聚氰胺-甲醛。RFC一般含有至少一個末端及/或側接反應性官能基,其能夠與聚醯亞胺聚合物上至少一個選自經取代或未經取代之直鏈烯基及經取代或未經取代之直鏈炔基的官能基進行自由基、熱或酸催化反應。在一個實施例中,RFC上反應性官能基包括不飽和雙鍵或參鍵。
RFC上反應性官能基之適合實例包括(但不限於)乙烯基、烯丙基、乙烯醚基、丙烯醚基、(甲基)丙烯醯基、環氧基、-SiH基及-SH(硫醇)基。
在一個實施例中,RFC之一適合實例包括(但不限於)胺基甲酸酯丙烯酸酯寡聚物。術語「胺基甲酸酯丙烯酸酯寡聚物」係指含有胺基甲酸酯鍵且具有(甲基)丙烯酸酯(例如丙烯酸酯或甲基丙烯酸酯)官能基之一類化合物,諸如胺基甲酸酯多(甲基)丙烯酸酯、多胺基甲酸酯(甲基)丙烯酸酯及多胺基甲酸酯多(甲基)丙烯酸酯。胺基
甲酸酯(甲基)丙烯酸酯寡聚物類型已藉由例如Coady等人之美國專利第4,608,409號及Chisholm等人之美國專利第6,844,950號(以引用的方式併入本文中)描述。RFC之其他特定實例包括1,6-己二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、二乙烯基苯、乙氧基化雙酚A-二(甲基)丙烯酸酯、二乙二醇雙(烯丙基碳酸酯)、三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、異戊四醇三(甲基)丙烯酸酯、異戊四醇四(甲基)丙烯酸酯、二異戊四醇五/六(甲基)丙烯酸酯、異氰尿酸酯三(甲基)丙烯酸酯、雙(2-羥乙基)-異氰尿酸酯二(甲基)丙烯酸酯、1,3-丁二醇三(甲基)丙烯酸酯、1,4-丁二醇三(甲基)丙烯酸酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苯甲酯、新戊二醇二(甲基)丙烯酸酯、(甲基)丙烯酸酯改質之尿素-甲醛樹脂、(甲基)丙烯酸酯改質之三聚氰胺-甲醛樹脂及(甲基)丙烯酸酯改質之纖維素。
在一些實施例中,RFC化合物為含矽二(甲基)丙烯酸酯化合物。
含有硫醇基之RFC化合物之實例包括(但不限於)三羥甲基丙烷參(巰基乙酸酯)、異戊四醇肆(巰基乙酸酯)、二異戊四醇六(3-巰基丙酸酯)及乙氧基化三羥甲基丙烷三-3-巰基丙酸酯。含有乙烯醚基之RFC化合物之實例包括(但不限於)1,4-丁二醇二乙烯基醚、1,4-環己烷二甲醇二乙烯基醚、二(乙二醇)乙烯醚、聚(乙二醇)二乙烯基醚及雙[4-(乙烯基氧基)丁基](4-甲基-1,3-伸苯基)雙胺基
甲酸酯。含有SiH基團之RFC化合物之一個實例為可購自Hybrid Plastics之八矽烷POSS® SH1310。
用於聚合物組成物中之組分(c)中的引發劑(例如光引發劑)為當組成物或一部分組成物曝露於光及/或熱時,能夠起始聚醯亞胺聚合物上之官能基與反應性官能化合物之間的反應之化合物。用於組成物中之一些引發劑藉由在加熱時產生自由基或藉由在曝露波長下吸收光來起作用。用於組成物中之其他引發劑藉由在加熱時產生酸或藉由在曝露波長下吸收光來起作用。用於組成物中之其他引發劑藉由在加熱時產生鹼性化合物或藉由在曝露波長下吸收光來起作用。在一些實施例中,本文所述之引發劑亦可催化聚醯亞胺聚合物上之官能基與反應性官能化合物之間的反應,因此亦用作催化劑。
在加熱時產生自由基之引發劑的特定實例包括(但不限於)過氧化物(諸如過氧化苯甲醯、過氧化環己酮、過氧化物月桂醯、過氧苯甲酸第三戊酯、氫過氧化叔丁基、過氧化二異丙苯、氫過氧化異丙苯、過氧化丁二酸或二(正丙基)過氧化二碳酸酯)、偶氮化合物(例如2,2-氮雜雙(異丁腈)、2,2-氮雜雙(2,4-二甲基戊腈)、二甲基-2,2-氮雜雙異丁酸酯、4,4-氮雜雙(4-氰基戊酸)、氮雜雙環己烷甲腈或2,2-氮雜雙(2-甲基丁腈))、α-羥基酮(例如1-羥基-環己基-苯基-酮(Irgacure 184))及其混合物。
在該聚合物膜中含有開口通孔之圖案化聚合物膜可藉由用雷射束照射該聚合物膜來形成。此過程稱
為雷射鑽孔或雷射剝蝕。用雷射束直接雷射剝蝕為根據具有高縱橫比之細通孔之遮罩圖案的乾式單步材料移除。此項技術通常用於行業中。在一些實施例中,雷射剝蝕可使用一或多種基於遮罩之投影準分子雷射實現。在一些實施例中,此製程可藉由無遮罩之直接剝蝕固態雷射進行。在一些實施例中,雷射波長為355nm或更少。在一些實施例中,雷射波長為308nm或更少。適合雷射剝蝕方法之實例包括(但不限於)US7598167、US6667551及US6114240(以引用的方式併入本文中)中描述之方法。
該雷射剝蝕製程之副產物為殘渣或灰塵(碎片),其作為雷射剝蝕製程之結果產生。碎片累積在通孔之側壁及底部中。其亦累積在雷射成像裝置之鏡子及光學裝置上。此可對雷射剝蝕製程之效能具有不利影響。裝配至成像器中之真空裝置可在光學裝置及鏡子上捕捉大量殘渣。若干技術用於雷射剝蝕後通孔清潔。此等技術包括使用犧牲層、溶劑清潔、氧電漿清潔、CO2雪清潔及使用皮秒DPSS雷射之DPSS清潔(二極體泵固態)。適合雷射剝蝕後清潔法之實例包括(但不限於)US7994450、US20120168412、US20020170894、US20030052101及US8716128(以引用的方式併入本文中)中描述之方法。
在一個實施例中,用於製造半導體裝置之方法包含以下:(i)在剝蝕條件下將聚合物膜曝露於雷射;及(ii)使用一或多種本發明之組成物清潔雷射剝蝕碎片。
除聚合物膜在用於雷射剝蝕之微粒波長下
的吸光度外,聚合物組成物不受具體限制。材料吸收雷射能量之能力限制彼能量可進行適用剝蝕之深度。剝蝕深度藉由例如材料之吸收深度及加工材料之汽化熱來確定。深度亦為射束能密度、雷射脈衝持續時間及雷射波長之函數。加工材料上每單位面積之雷射能量根據能量流量量測。在一個實施例中,聚合物組成物可調至具有248nm下每微米0.007至每微米0.015之吸光度。在另一個實施例中,聚合物組成物可調至具有308nm下每微米0.6至每微米0.9之吸光度。在又一個實施例中,聚合物組成物可調至具有355nm下每微米0.1至每微米0.2之吸光度。在一些實施例中,吸收之量可藉由添加染料調整。在所有此三個實施例中,能量流量為至多2000mJ/cm2(例如至多1900mJ/cm2、至多1800mJ/cm2、至多1700mJ/cm2或至多1600mJ/cm2)及/或至少1200mJ/cm2(例如1300mJ/cm2、至少1400mJ/cm2或至少1500mJ/cm2)。藉由此類聚合物組成物形成之聚合物層的膜厚度可為至少約1微米(例如至少約2微米、至少約5微米、至少約10微米、至少約15微米、至少約20微米、至少約25微米、至少約30微米、至少約35微米、至少約40微米或至少約45微米)至至多約80微米(例如至多約75微米、至多約70微米、至多約65微米、至多約60微米、至多約55微米或至多約50微米)。
雷射剝蝕後清潔製程可藉由使用已知技術,諸如浸入、離心噴霧、超高速清潔及超音波清潔,用本發明之組成物處理待清潔之目標實現。此類清潔程序之
實例揭示於以引用的方式併入本文中之US6766813、US5100476及US5368054中。
用於清潔製程中之溫度可為至少約15℃(例如至少約16℃、至少約17℃、至少約18℃、至少約19℃、至少約20℃、至少約21℃、至少約22℃或至少約23℃)及/或至多約30℃(例如至多約29℃、至多約28℃、至多約27℃、至多約26℃或至多約25℃)。用於清潔製程中之時間可為至少約2分鐘(例如至少約4分鐘或至少約5分鐘)及至多約10分鐘(例如至多約8分鐘或至多約6分鐘)。
清潔製程中之選擇性地選用之步驟包括清洗及乾燥步驟。半導體基板可用水或水溶液清洗。可用於此製程中之水溶液可為DI水與界面活性劑之混合物、含有界面活性劑之微鹼性水溶液或含有直鏈或分支鏈C1-C4醇之水溶液以移除本發明中描述之組成物及/或其他殘渣。此步驟亦可藉由使用已知技術,諸如浸入、離心噴霧、超高速清潔及超音波清潔來實現。經清潔之半導體基板可使用熟習此項技術者已知之乾燥方式乾燥。
意外地,本發明中描述之組成物展示在低溫下意外有效地自該圖案化聚合物膜完全移除雷射剝蝕後碎片,而對該膜無任何破壞。
在一些實施例中,在高溫下,本發明之組成物亦可用於自半導體基板剝離未曝光之感光性聚合物膜、曝光之交聯聚合物膜或非感光性聚合物膜的製程中。剝離製程可藉由使用已知技術,諸如浸入、離心噴霧、超高速
清潔及超音波清潔,處理將剝離聚合物膜之目標實現。
用於剝離製程中之溫度可為至少約65℃(例如至少約67℃或至少約70℃)至至多約85℃(例如至多約80℃或至多約75℃)。剝離時間可為至少約15分鐘(例如至少約30分鐘、至少約40分鐘、至少約50分鐘或至少約60分鐘)及/或至多約120分鐘(例如至多約110分鐘、至多約100分鐘、至多約90分鐘、至多約80分鐘或至多約70分鐘)。
剝離製程中之選擇性地存在之步驟包括如上在清潔製程中所述之清洗及乾燥步驟。
本發明之組成物之設計中的一獨特態樣為本發明之組成物可用作在室溫下雷射剝蝕後碎片之清潔劑,且可用作在高溫下完全剝離聚合物膜之非剝蝕區域的極有效剝離劑。
當前揭示內容之一個實施例的特徵在於一種用於製造半導體裝置之方法。此方法可例如藉由以下進行:(i)將基板上之感光性聚合物層(例如含有聚醯亞胺聚合物或聚醯亞胺前驅物聚合物之層)圖案化(例如藉由用聚合物組成物塗佈基板形成)以形成圖案化之聚合物層;(ii)用離子移植(例如以形成電晶體)、電漿或濕式蝕刻(例如在感光性聚合物層中形成圖案)或金屬沈積(例如以形成裝置之間的導電連接)處理圖案化基板;及(iii)使用本文所述之組成物剝離該聚合物層。以上三個步驟每一者可藉由此項技術中已知之方法進行。在一些實施例中,聚合物層可藉由聚醯亞胺組成物或聚醯亞胺前驅物組成物形成。在一些
實施例中,聚醯亞胺組成物或聚醯亞胺前驅物組成物可為感光性的。
本發明之一個實施例之特徵在於一種包括以下之方法:(i)提供含有聚合物膜之半導體基板;(ii)選擇性地藉由使用光或其他輻射源,將該聚合物膜整片曝露;(iii)選擇性地使曝光處理後之該聚合物膜經受曝露後烘烤處理;(iv)選擇性地使經曝露後烘烤之膜經受硬性烘烤;(v)藉由雷射剝蝕製程,使用雷射在該聚合物膜中打開通孔以形成圖案化之聚合物膜;(vi)使用本發明之清潔/剝離組成物自該圖案化之聚合物膜移除雷射剝蝕後碎片;(vii)藉由將熔融導電膏塗覆在通孔上,在包括通孔內側之區域中形成導電柱;(viii)選擇性地用導電膏移除溶液清洗圖案化之聚合物膜,以自聚合物膜頂部移除導電膏;(ix)在高溫下使用本發明之清潔/剝離組成物移除聚合物膜之非剝蝕區域;以及(x)選擇性地用水或水溶液清洗圖案化聚合物膜以移除本發明之任何殘留清潔/剝離組成物及其他殘渣。用於清潔步驟(vi)之清潔/剝離組成物可與剝離步驟(ix)中所用之清潔/剝離組成物相同或不同。
在此製程之一些實施例中,聚合物膜為感光性的。在一些實施例中,感光性膜為負型色調。在一些實施例中,感光性負型色調膜由聚醯亞胺組成物或聚醯亞胺前驅物組成物形成。
在此製程之一些實施例中,在步驟(ii)中感光性聚合物塗佈基板曝露於放射線。曝露通常為整片曝
露,在非剝蝕條件下進行。一般而言,此曝露步驟引起曝露區域中感光性聚合物塗層固化或交聯。此曝露步驟使用光或其他輻射源(例如紫外光、可見光、電子束放射線或X射線),如適於特定聚合物組成物中之引發劑。使用i-線(365nm)、h-線(405nm)或g-線(436nm)紫外光為較佳。熟習此項技術者將已知何種類型高能輻射適於既定應用。用於本發明中之能量劑量可為至少約200mJ/cm2(例如至少約300mJ/cm2、至少約400mJ/cm2、至少約500mJ/cm2、至少約600mJ/cm2、至少約700mJ/cm2或至少約800mJ/cm2)至至多約2000mJ/cm2(例如至多約1800mJ/cm2、至多約1600mJ/cm2、至多約1400mJ/cm2、至多約1200mJ/cm2或至多約1000mJ/cm2)。
在一些實施例中,進行短暫曝露後烘烤。曝露後烘烤溫度可為至少約50℃(例如至少約60℃、至少約70℃或至少約80℃)及/或至多約120℃(例如至多約110℃、至多約100℃、至多約100℃及至多約90℃)。曝露後烘烤時間可為至少約120秒(例如至少約150秒或至少約180秒)及/或至多約300秒(例如至多約270秒或至多約240秒)。
在一些實施例中,可併入硬性烘烤步驟。在一些實施例中,硬性烘烤溫度可為至少約150℃(例如至少約170℃或至少約190℃)至至多約250℃(例如至多約230℃或至多約210℃)。硬性烘烤時間可為至少約30分鐘(例如至少約45分鐘或至少約60分鐘)及/或至多約120分鐘
(例如至多約105分鐘或至多約90分鐘)。
雷射剝蝕步驟及雷射剝蝕後清潔步驟可如先前所述進行。
在此製程之下一步中,可藉由在由雷射剝蝕製程產生之通孔中形成導電層來提供半導體基板之一個表面與另一基板之一個表面之間的電連接。在不必用熔融材料(例如熔融導電膏或焊膏)填充通孔下形成該導電層為一種確保高度可靠電連接之可能方式。導電膏或焊膏包括金屬或合金,諸如鎳、銅、鈹銅、鎳合金、銅合金、鈹銅合金、鎳鈷鐵合金及鐵鎳合金與聚合物黏合劑。組成物及導電膏應用之更多細節描述於以引用的方式併入本文中之US2013069014、US4789411、US5204025及US7081214中。用於在回流後移除導電膏之清潔組成物描述於以引用的方式併入本文中之US5888308及US6277799中。清潔製程可藉由使用已知技術,諸如如先前所述之浸入、離心噴霧、超高速清潔及超音波清潔來實現。
可藉由在包括選擇性地選用之清洗及乾燥步驟的剝離製程中,使用如上所述的本發明之清潔/剝離組成物完全移除(剝離)聚合物膜。
經清潔之半導體基板準備用於隨後整合製程以產生半導體裝置,諸如半導體封裝(例如存儲器封裝、微處理器封裝、平板封裝及用於移動裝置之封裝)。在一些實施例中,半導體封裝可藉由多步製程製備,該多步製程包括至少一個使用本文所述之清潔/剝離組成物移除雷射
剝蝕或鑽孔後碎片之步驟。在一些實施例中,半導體封裝可藉由多步製程製備,該多步製程包括至少一個使用本文所述之清潔/剝離組成物剝離或移除聚合物膜之步驟。
本發明現將參考以下非限制性實例進一步闡明。
合成實例1(Poly-1)
聚合反應在一公升三頸夾套圓底燒瓶中進行,該燒瓶裝備有機械攪拌器、熱電偶及氮入口以保持整個反應中正氮氣壓力。向燒瓶饋入203.7公克二苯甲酮-3,3',4,4'-四甲酸二酸酐(BTDA)、70.2公克六氟亞異丙基二鄰苯二甲酸酐(6FDA)及300公克無水NMP。將內含物在18-20℃下攪動。使106.55公克1-(4-胺基苯基)-1,3,3-三甲基茚滿-5-胺(DAPI)及60.4公克2,4-二胺基-1,3,5-三甲苯(DAM)溶於瓶中700公克無水NMP中。在室溫下將二胺溶液藉由泵添加至燒瓶,歷時1小時。混合物升溫至60℃且攪動3小時,以產生聚醯胺酸。
為將以上形成之聚醯胺酸封端,將16.5公克1,3-二側氧基-1,3-二氫-2-苯并呋喃-5-甲酸3-丙烯醯基氧基-2,2-雙[(丙烯醯基氧基)甲基]丙酯(PETA)及1.58g吡啶饋入燒瓶中。將混合物在60℃下攪動3小時,以形成封端之聚醯胺酸。
為進行以上封端聚醯胺酸之亞胺化反應,將100.0公克乙酸酐及35.0公克吡啶饋入燒瓶。使反應混合物升溫至110℃且攪動12小時。抽出少量樣品(1g)且在50:50甲醇:水(10ml)中沈澱。固體藉由過濾分離且乾燥。FTIR分析展示亞胺化反應完成(展示不存在醯胺及酸酐峰)。
溶液冷卻至室溫且逐滴添加至18公升用力攪拌之去離子水以使聚合物沈澱。聚合物藉由過濾收集且用一公升去離子水洗滌。餅狀物用四公升甲醇重新形成漿液且過濾。濕餅狀物在空氣中乾燥12小時,接著聚合物在真空下在70℃下乾燥12小時。所得聚醯亞胺聚合物之分子量藉由GPC量測。
組成物實例1
調配聚合物溶液用於製備乾膜(F-1)
向裝備有機械攪拌器之三頸圓底燒瓶添加645份GBL、205.4份合成實例1中獲得之聚合物、6.6份(3-縮水甘油基氧基丙基)三甲氧基矽烷、6.16份NCI-831(商品名,可購自ADEKA公司)、4.11份氧化(2,4,6-三甲基苯甲醯基)膦、69.32份二丙烯酸四伸乙酯、23.11g異戊四醇三丙烯酸酯及30.81g結構PAE-1之聚醯胺酸酯。將組成物機械攪拌18小時。接著藉由使用0.2μm過濾器(來自Meissner Filtration Product,Inc.之Ultradyne,目錄號CFTM10.2-44B1)過濾此組成物。
乾膜實例DF-1
經過濾之感光性溶液(F-1)經由來自Frontier Industrial Technologies(Towanda,PA)之槽模塗佈機以5呎/分鐘(每分鐘150cm)之線速度塗覆至用作載體基板的未經線上電暈處理之厚度為36μm之聚對苯二甲酸伸乙酯(PET)膜TA 30(Toray Plastics America,Inc.製造)上,且在180-200℉下乾燥以獲得厚度為37微米之聚合物層。層壓壓力為30psi且真空為0.7托。在此聚合物層上,雙軸定向聚丙烯(BOPP)膜(藉由IMPEX GLOBAL LLC製造,商品名80ga BOPP)藉由輥壓層壓以充當保護層。
乾膜實例之層壓(L-1)
在藉由剝落移除保護層後,乾膜結構DF-1之聚合物層(6"×6")位於4"銅晶圓(Wafernet)上。藉由在80℃下真空層壓,接著經受25psi之壓力,將聚合物層層壓至Cu塗佈之晶圓上。藉由使用OPTEK,NJ製造之DPL-24A分壓層壓機進行層壓製程。
乾膜實例之層壓(L-2)
在藉由剝落移除保護層後,乾膜結構DF-1之聚合物層(12"×12")位於8"銅晶圓(Wafernet,條目號
S45102)上。藉由在80℃下真空層壓,接著經受25psi之壓力,將聚合物層層壓至Cu塗佈之晶圓上。藉由使用OPTEK,NJ製造之DPL-24A分壓層壓機進行層壓製程。
乾膜實例之雷射剝蝕(LA-1)
層壓乾膜(L-2)使用SUSS寬帶曝露工具在1000mJ/cm2下整片曝露。接著晶圓在50℃下加熱180秒。層壓乾膜接著在220℃下在真空下烘烤1小時。
藉由EPL300 Gen2,在308nm波長下,使用通孔直徑為65微米且間距為90微米之通孔遮罩,對曝露之烘烤晶圓進行雷射剝蝕程序。308nm雷射之印刷能量固定在800mJ/cm2及N=60脈衝。
清潔/剝離組成物之實例
組成物藉由使用2.5份氫氧化四甲基銨(TMAH)、4.3份單乙醇胺、0.5份硫酸羥銨、85份四氫糠醇(THFA)、0.2份5-甲基-1H-苯并三唑及7.5份水製備。藉由使用裝備有Metrohm pH電極部件號6.0233/100之Metrohm型號716基本單元,測得此清潔/剝離組成物之pH值為14.9。藉由使用Cannon Fenske黏度計尺寸150,在25℃下量測清潔/剝離組成物之動態黏度。動態黏度為8.5cSt。
清潔程序之實例
將層壓晶圓LA-1切成1"×2"片,且垂直置於含有300mL以上獲得之清潔/剝離組成物之600mL燒杯中。燒杯內含物使用磁棒在25℃下攪拌。藉由使用調溫器
維持溫度恆定。5分鐘後,移除晶圓片且立刻用水清洗且藉由使用氮氣吹洗來乾燥。在濺鍍金後,藉由使用光學顯微鏡及藉由SEM測定清潔有效性。晶圓之俯視圖及橫截面影像揭露清潔後無殘渣。膜厚度損失程度藉由使用Dektak表面光度儀量測殘餘膜之厚度來測定。完全移除剝蝕碎片,未對膜有任何破壞。未觀測到膜厚度損失。
剝離程序之實例
將層壓晶圓LA-1切成1"×2"片,且垂直置於含有300mL以上獲得之清潔/剝離組成物之600mL燒杯中。燒杯內含物使用磁棒在85℃下攪拌。藉由使用調溫器維持溫度恆定。60分鐘後,移除晶圓片且立刻用水清洗且藉由使用氮氣吹洗來乾燥。在濺鍍金後,藉由使用光學顯微鏡及藉由SEM測定剝離有效性。晶圓之俯視圖及橫截面影像揭露清潔後無殘渣。膜厚度損失程度藉由使用Dektak表面光度儀量測殘餘膜之厚度來測定。觀測到雷射剝蝕後殘留之聚合物層完全剝離。
Claims (25)
- 一種清潔組成物,其包含:(a)0.5-25重量百分比之鹼性化合物;(b)1-25重量百分比之醇胺化合物;(c)0.1-20重量百分比之羥銨化合物;(d)5-95重量百分比之有機溶劑;(e)0.1-5重量百分比之腐蝕抑制劑化合物;及(f)2-25重量百分比之水;其中該組成物具有至少約12.4的pH值。
- 如請求項1之組成物,其中該鹼性化合物係選自由以下所組成之群:氫氧化四甲基銨(TMAH)、氫氧化2-羥基三甲基銨、氫氧化四乙基銨(TEAH)、氫氧化四丙基銨(TPAH)、氫氧化四丁基胺(TBAH)及其混合物。
- 如請求項1之組成物,其中該醇胺化合物係選自由以下所組成之群:單乙醇胺(MEA)、二乙醇胺、三乙醇胺、2-(2-胺基乙氧基)乙醇、單異丙醇胺、二異丙醇胺、三異丙醇胺、N-甲基二乙醇胺、N-乙基乙醇胺、N-丁基乙醇胺、二乙醇胺、二甘醇胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N,N-二丁基乙醇胺、N-甲基-N-乙基乙醇胺及其混合物。
- 如請求項1之組成物,其中該羥銨化合物係選自由以下所組成之群:硫酸羥銨、鹽酸羥銨、硝酸羥銨及磷酸羥銨。
- 如請求項4之組成物,其中該羥銨化合物為硫酸羥銨。
- 如請求項1之組成物,其中該有機溶劑係選自由以下所組成之群:N-甲基吡咯啶酮(NMP)、N-乙基吡咯啶酮(NEP)、γ-丁內酯、甲基乙基酮(MEK)、二甲亞碸(DMSO)、二甲碸、二 甲基甲醯胺、N-甲基甲醯胺、甲醯胺、四甲基脲、四氫糠醇(THFA)及其混合物。
- 如請求項6之組成物,其中該有機溶劑為二甲亞碸(DMSO)或四氫糠醇(THFA)。
- 如請求項1之組成物,其中該腐蝕抑制劑化合物為三唑、苯并三唑、經取代之三唑或經取代之苯并三唑。
- 如請求項8之組成物,其中該腐蝕抑制劑化合物為5-甲基-1H-苯并三唑。
- 如請求項9之組成物,其中該腐蝕抑制劑化合物之量為至多該總組成物之約0.5重量%。
- 如請求項9之組成物,其中該腐蝕抑制劑化合物之量為至多該總組成物之約0.3重量%。
- 如請求項1之組成物,其中該組成物具有13.5至15.5的 pH值。
- 如請求項1之組成物,其中該組成物具有至多約16的pH值。
- 一種用於製造半導體裝置之方法,其包含在約65℃至約85℃之溫度下用如請求項1至15中任一項之組成物處理半導體基板上未曝光之感光性聚合物膜、曝光之交聯聚合物膜或非感光性聚合物膜。
- 一種用於製造半導體裝置之方法,其包含以下步驟:(i)使半導體基板上包含至少一種聚醯亞胺聚合物或聚醯亞胺前驅物聚合物之感光性聚合物膜圖案化以形成圖案化膜;(ii)用離子移植、電漿或濕式蝕刻或金屬沈積處理該圖案化膜,以及(iii)使用如請求項1至15中任一項之組成物剝離該感光性聚合物膜。
- 一種用於製造半導體裝置之方法,其包含以下步驟:(i)在剝蝕條件下將聚合物膜曝露於雷射;及(ii)使用如請求項1至15中任一項之組成物清潔該雷射剝蝕碎片。
- 一種清潔方法,其包含:(i)提供含有聚合物膜之半導體基板;(ii)選擇性地藉由使用光或另一其他輻射源整片曝露(flood exposing)該聚合物膜;(iii)選擇性地在該曝光處理後使該聚合物膜經受曝露後烘烤處理;(iv)選擇性地使經曝露後烘烤之聚合物膜經受硬性烘烤;(v)藉由使用雷射之雷射剝蝕製程在該聚合物膜中打開通孔,以形成圖案化聚合物膜;(vi)藉由使用組成物,自該圖案化聚合物膜移除雷射剝蝕後 碎片;(vii)藉由將熔融導電膏塗覆在通孔上,在包括通孔內側之區域中形成導電柱;(viii)選擇性地用導電膏移除溶液清洗該圖案化聚合物膜以自聚合物膜頂部移除該導電膏,(ix)在高溫下使用組成物移除該圖案化聚合物膜之非剝蝕區域;以及(x)選擇性地用水或水溶液清洗該圖案化聚合物膜以移除殘渣,其中用於步驟(vi)及(ix)之該等組成物為如請求項1至15中任一項之組成物。
- 如請求項19之方法,其中該基板為銅且該聚合物膜自包含以下之組成物獲得:(a)至少一種可溶性聚醯亞胺聚合物,其具有含有至少一個選自經取代或未經取代之直鏈烯基及經取代或未經取代之直鏈炔基之官能基的封端基團;(b)至少一種反應性官能化合物(RFC);(c)至少一種引發劑;及(d)至少一種溶劑。
- 如請求項20之方法,其中雷射剝蝕藉由使用基於遮罩之投影準分子雷射實現。
- 如請求項20之方法,其中該雷射波長為355nm或更少。
- 如請求項20之方法,其中該雷射波長為308nm或更少。
- 如請求項1至15中任一項之組成物,其中該有機溶劑相對於水具有約0.5至約0.8之相對能差(RED)。
- 如請求項1至15中任一項之組成物,其中該組成物具有約5cSt至約12cSt之25℃下動態黏度。
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JP2018526495A (ja) | 2018-09-13 |
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WO2017023677A1 (en) | 2017-02-09 |
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