TWI796486B - 薄型基板之製造方法 - Google Patents
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- TWI796486B TWI796486B TW108118699A TW108118699A TWI796486B TW I796486 B TWI796486 B TW I796486B TW 108118699 A TW108118699 A TW 108118699A TW 108118699 A TW108118699 A TW 108118699A TW I796486 B TWI796486 B TW I796486B
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
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- H—ELECTRICITY
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Abstract
本發明的課題為提供一種基板與支持體的暫時接著容易且酸、鹼處理可能,與支持體之剝離亦容易之薄型基板之製造方法。
本發明的解決手段為使用用以將應加工背面之基板暫時接著在支持體之基板加工用暫時接著薄膜的薄型基板之製造方法,其特徵為
前述基板加工用暫時接著薄膜係含有10質量份以上100質量份以下之重量平均分子量為3,000~500,000之含有矽氧烷鍵的聚合物,包含下述(a)~(g)步驟全部。
(a)於並非基板之應加工的面之表面或是前述支持體之至少任何一個,層壓基板加工用暫時接著薄膜之步驟、(b)於減壓下接合之步驟、(c)進行研削或研磨,處理基板之步驟、(d)使用酸或是鹼,處理基板之步驟、(e)實施其他加工之步驟、(f)將實施加工之基板從支持體剝離之步驟、(g)洗淨基板之步驟。
Description
本發明係關於薄型基板之製造方法。
3次元之半導體實裝為了實現更一層之高密度、大容量化已成為必須。所謂3次元實裝技術,係薄型化1個半導體晶片,進而邊將此藉由矽貫通電極(TSV;through silicon via)結線邊層合成多層的半導體製作技術。為了實現此,將形成半導體電路之基板藉由非電路形成面(亦稱為「背面」)研削進行薄型化,進而於背面進行包含TSV之電極形成的加工步驟為必要。
以往,於矽基板之背面研削步驟,於研削面的相反側貼上保護膠帶,防止研削時之基板破損。惟,此膠帶已將有機樹脂薄膜使用在支持基材,雖有柔軟性,但強度或耐熱性不夠充分,不適合進行TSV形成步驟或於背面之配線層形成步驟。
因此,提案有藉由將半導體基板於矽、玻璃等之支持體透過接著層接合,可充分耐得住背面研削、TSV或背面電極形成的步驟之系統(例如,參照專利文獻1)。此時重要的是將基板與支持體接合時之接著層。此係尋求可將基板無間隙接合在支持體,僅耐得住之後的步驟之充分的耐久性為必要,進而最後可將薄型基板從支持體簡便地剝離。如此,由於最後剝離,故於本說明書,將此接著層稱為暫時接著層(或暫時接著材層)。例如,在專利文獻2,浸漬在藥劑進行暫時接著層的剝離。
進而,藉由以往於矽等之半導體基板形成暫時接著層,得到接合支持體之層合體基板後,切削・研磨加工半導體基板的背面,藉由將半導體基板定為薄板,剝離暫時接著劑,可製造薄型半導體基板。惟,於最近之半導體加工,除了於薄型化之步驟進行研削・研磨之加工步驟之外,正增加加成各式各樣的作業步驟的情況。對於如此要求,如專利文獻2於浸漬在藥劑進行暫時接著層的剝離之系統,無法加成要求耐藥品性的作業步驟的問題。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2004-64040號公報
[專利文獻2]美國專利第7541264號公報
[發明欲解決之課題]
本發明係鑑於上述問題點而完成者,以提供一種基板與支持體的暫時接著容易,對基板與支持體的暫時接著材層形成速度快,且酸、鹼處理可能,與支持體之剝離亦容易之薄型基板之製造方法作為目的。
[用以解決課題之手段]
為了達成上述課題,於本發明,係提供一種薄型基板之製造方法,其係使用用以將應加工背面之基板暫時接著在支持體之基板加工用暫時接著薄膜的基板之製造方法,其特徵為前述基板加工用暫時接著薄膜係含有10質量份以上100質量份以下之總質量每100質量份之重量平均分子量為3,000~500,000之含有矽氧烷鍵的聚合物,包含下述(a)~(g)步驟全部。
(a)於並非前述基板之應加工的面之表面或是前述支持體之至少任何一個,層壓前述基板加工用暫時接著薄膜之步驟、
(b)將前述基板與前述支持體透過在步驟(a)層壓之基板加工用暫時接著薄膜,於減壓下接合之步驟、
(c)研削或研磨前述基板之應加工的面,處理基板之步驟、
(d)將前述基板之應加工的面使用酸或是鹼,處理基板之步驟、
(e)於前述基板之應加工的面實施研削、研磨、酸處理、鹼處理以外的加工之步驟、
(f)將實施該加工之前述基板從前述支持體剝離之步驟、
(g)洗淨前述基板之步驟。
根據本發明之薄型基板之製造方法,藉由使用特定之基板加工用暫時接著薄膜,於基板與接著劑界面無剝離或發泡等,且基板與支持體的暫時接著容易,對基板或支持體之暫時接著材層形成速度快,且酸、鹼處理可能,剝離亦容易,進而,亦可適應其他各種基板處理步驟,可提高薄型基板的生產性。
於本發明使用之基板加工用暫時接著薄膜,係含有10質量份以上100質量份以下之總質量每100質量份之重量平均分子量為3,000~500,000之含有矽氧烷鍵的聚合物。又,較佳為上述暫時接著薄膜含有50質量份以上之總質量每100質量份之前述含有矽氧烷鍵之聚合物。另一方面,含量未滿10質量份時,有接合基板與支持體時接著性惡化的問題。
若為上述範圍之含有矽氧烷鍵的聚合物含量,相對於各種基板處理步驟一開始將基板之應加工的面使用酸或是鹼,處理基板之步驟,由於耐製程性優異故較佳。
此情況下,較佳為基板加工用暫時接著薄膜係與前述基板或前述支持體之間的剝離力,對在25℃之180°方向的剝離試驗中為20mN/25mm以上500mN/25mm以下者。
若基板加工用暫時接著薄膜為具有這般的剝離力者,由於後加工之耐藥品性更為優異,基板研削時不會有產生基板的偏移之虞,確實剝離變容易故較佳。
又,此情況下,較佳為前述含有矽氧烷鍵之聚合物為具有下述一般式(1)表示之重複單位的聚合物。
[式中,R1
~R4
係表示可相同亦可相異之碳原子數1~8之1價烴基。又,m為1~100之整數,B為正數,A為0或正數。惟,A+B=1。X為下述一般式(2)表示之2價有機基。
(式中,Z為選自
之任一者的2價有機基,N為0或1。又,R5
、R6
分別為碳原子數1~4之烷基或烷氧基,可為相同或相異。k為0、1、2之任一個)]。
若為這般的含有矽氧烷鍵之聚合物,由於耐藥品性更為優異故較佳。
又,此情況下,較佳為前述含有矽氧烷鍵之聚合物為具有下述一般式(3)表示之重複單位的聚合物。
[式中,R7
~R10
係表示可相同亦可相異之碳原子數1~8之1價烴基。又,n為1~100之整數,D為正數,C為0或正數。惟,C+D=1。進而,Y為下述一般式(4)表示之2價有機基。
(式中,V為選自
之任一者的2價有機基,p為0或1。又,R11
、R12
分別為碳原子數1~4之烷基或烷氧基,可為相同或相異。h為0、1、2之任一個)]。
若為這般的含有矽氧烷鍵之聚合物,由於耐藥品性更為優異故較佳。
又,此情況下,含有矽氧烷鍵之聚合物較佳為含有下述(p1)~(p3)之組成物的硬化物,(p1)於分子中具有烯基之有機聚矽氧烷、(p2)於1分子中含有與2個以上之矽原子鍵結之氫原子(Si-H基)的有機氫聚矽氧烷:(p2)成分中之Si-H基相對於前述(p1)成分中之烯基的莫耳比成為0.3至15的量及(p3)鉑系觸媒。
若為這般的含有矽氧烷鍵之聚合物,由於可效率良好地剝離包含含有矽氧烷鍵之聚合物的暫時接著材層、與基板或支持體故較佳。
[發明效果]
如以上,若為本發明之薄型基板之製造方法,由於使用特定之基板加工用暫時接著薄膜,層壓在基板或支持體上,故在(a)~(b)步驟可輕易於基板或支持體上形成暫時接著材層,以短時間進行暫時接著材層形成變可能,對於(c)步驟之研磨處理、(d)步驟之酸・鹼處理的耐性優異。又,根據本發明,提昇形成在基板面或支持體面之暫時接著材的尺寸安定性,減低層合體的扭曲,對於(e)步驟(TSV形成、基板背面配線步驟等)的步驟適合性高。進而,除了嵌入性或耐熱性優異外,於(f)步驟,於薄型基板製作後將基板由支持體剝離時,例如由於可於室溫輕易剝離,故即使是容易破裂的薄型基板亦可輕易製造,於(g)步驟由於可輕易洗淨去除殘存在基板表面之暫時接著材料,故可製造無表面污染的薄型基板。尤其是對於(d)步驟之酸・鹼處理的耐性(耐藥品性)優異的點,將基板接合在支持體時之暫時接著層,不僅具備僅耐得住之後的步驟之充分的耐久性,並且最後由於可將薄型基板從支持體簡便地剝離,可擴散可於(e)步驟選擇之加工的變異。
如上述,正尋求暫時接著容易,對基板或支持體之暫時接著材層形成速度快,尺寸安定性優異,研磨處理或酸・鹼處理的耐性優異,剝離亦容易,可提高薄型基板的生產性之薄型基板之製造方法的開發。
本發明者們為了達成上述目的進行努力研究的結果,發現若為薄型基板之製造方法,其係使用用以將應加工背面之基板暫時接著在支持體之基板加工用暫時接著薄膜的薄型基板之製造方法,其特徵為前述基板加工用暫時接著薄膜係含有10質量份以上100質量份以下之總質量每100質量份之重量平均分子量為3,000~500,000之含有矽氧烷鍵的聚合物,包含下述(a)~(g)步驟全部,可簡單製造具有貫通電極結構或凹凸連接結構之薄型基板,而完成本發明。
亦即,本發明為一種薄型基板之製造方法,其係使用用以將應加工背面之基板暫時接著在支持體之基板加工用暫時接著薄膜的薄型基板之製造方法,其特徵為
前述基板加工用暫時接著薄膜係含有10質量份以上100質量份以下之總質量每100質量份之重量平均分子量為3,000~500,000之含有矽氧烷鍵的聚合物,
包含下述(a)~(g)步驟全部。
(a)於並非前述基板之應加工的面之表面或是前述支持體之至少任何一個,層壓前述基板加工用暫時接著薄膜之步驟、
(b)將前述基板與前述支持體透過在步驟(a)層壓之基板加工用暫時接著薄膜,於減壓下接合之步驟、
(c)研削或研磨前述基板之應加工的面,處理基板之步驟、
(d)將前述基板之應加工的面使用酸或是鹼,處理基板之步驟、
(e)於前述基板之應加工的面實施研削、研磨、酸處理、鹼處理以外的加工之步驟、
(f)將實施該加工之前述基板從前述支持體剝離之步驟、
(g)洗淨前述基板之步驟。
以下,雖針對本發明進行詳細說明,但本發明並非被限定於此等。
(第1態樣)
於本發明使用之基板加工用暫時接著薄膜,係含有10質量份以上100質量份以下之總質量每100質量份之重量平均分子量為3,000~500,000之含有矽氧烷鍵的聚合物,較佳為含有50質量份以上之總質量每100質量份之前述含有矽氧烷鍵之聚合物。本發明之基板加工用暫時接著薄膜,若為含有10質量份以上100質量份以下之總質量每100質量份之重量平均分子量為3,000~500,000之含有矽氧烷鍵的聚合物者,雖並未特別限定,但較佳為將下述一般式(1)及/或(3)表示之含有矽氧烷鍵的聚合物作為主成分之暫時接著薄膜。
尚,含有矽氧烷鍵之聚合物中可併用下述一般式(1)表示之聚合物、與下述一般式(3)表示之聚合物。該情況的比例(質量比),較佳為(1):(3)=0.1:99.9~99.9:0.1,更佳為(1):(3)=1:99~99:1。
一般式(1)之聚合物(酚性矽氧烷聚合物):
藉由具有下述一般式(1)表示之重複單位的凝膠滲透層析(GPC)之聚苯乙烯換算重量平均分子量為3,000~500,000,較佳為10,000~100,000之含有矽氧烷鍵的聚合物。
[式中,R1
~R4
係表示可相同亦可相異之碳原子數1~8之1價烴基。又,m為1~100之整數,B為正數,A為0或正數。X為下述一般式(2)表示之2價有機基。A+B=1。又,較佳為A為0~0.9,B為0.1~1,且A較0更大時,較佳為A為0.1~0.7,B為0.3~0.9。
(式中,Z為選自
之任一者的2價有機基,N為0或1。又,R5
、R6
分別為碳原子數1~4之烷基或烷氧基,可為相同或相異。k為0、1、2之任一個)]。
此情況下,作為R1
~R4
之具體例,可列舉甲基、乙基、苯基等,m為1~100之整數,較佳為3~60,更佳為8~40之整數。又,B/A係較0更大且較20更小,特別為0.5~5。
一般式(3)之聚合物(環氧改質矽氧烷聚合物):
藉由具有下述一般式(3)表示之重複單位的GPC之聚苯乙烯換算重量平均分子量為3,000~500,000之含有矽氧烷鍵的聚合物。
[式中,R7
~R10
係表示可相同亦可相異之碳原子數1~8之1價烴基。又,n為1~100之整數,D為正數,C為0或正數。進而,Y為下述一般式(4)表示之2價有機基。C+D=1。又,較佳為C為0~0.9,D為0.1~1,又,C為較0更大時,較佳為C為0.1~0.7,D為0.3~0.9。
(式中,V為選自
之任一者的2價有機基,p為0或1。又,R11
、R12
分別為碳原子數1~4之烷基或烷氧基,可為相同或相異。h為0、1、2之任一個)]。
此情況下,作為R7
~R10
之具體例,可列舉與於上述一般式(1)中之R1
~R4
所例示者為相同者。又,n為1~100之整數,較佳為3~60,更佳為8~40之整數。又,D/C係較0更大且較20更小,特別為0.5~5。
上述含有矽氧烷鍵之聚合物可溶解在溶劑,可使用在基板加工用暫時接著薄膜的形成。作為溶劑,例如可列舉環己酮、環戊酮、甲基-2-n-戊基酮等之酮類;3-甲氧基丁醇、3-甲基-3-甲氧基丁醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇等之醇類;丙二醇單甲基醚、乙二醇單甲基醚、丙二醇單乙基醚、乙二醇單乙基醚、丙二醇二甲基醚、二乙二醇二甲基醚等之醚類;丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、乳酸乙酯、丙酮酸乙酯、乙酸丁酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸tert-丁酯、丙酸tert-丁酯、丙二醇單-tert-丁基醚乙酸酯、γ-丁內酯等之酯類等,可將此等之1種單獨或併用2種以上。進而,如有必要可進行過濾。
尚,為了更提高耐熱性,可相對於暫時接著薄膜100質量份,添加50質量份以下之公知的抗氧化劑、二氧化矽等之填料。進而,為了提昇塗佈均一性,可添加界面活性劑。
作為可添加在暫時接著薄膜中之抗氧化劑的具體例,可列舉肆[亞甲基-(3,5-二-t-丁基-4-羥基氫化桂皮酸酯)]甲烷(商品名:Adekastab AO-60)等之受阻酚系化合物。
此時,所形成的膜厚雖並未特別限定,但較佳為5~150μm,更佳為10~120μm。若膜厚為5μm以上,可充分耐得住基板薄型化之研削步驟,若為150μm以下,於TSV形成步驟等之熱處理步驟不會有產生樹脂變形之虞,由於可耐於實用故較佳。
(第2態樣)
又,本發明之基板加工用暫時接著薄膜,若為相對於總質量100份,含有10質量份以上之重量平均分子量為3,000~500,000之含有矽氧烷鍵的聚合物,雖並未特別限定,但較佳為前述含有矽氧烷鍵之聚合物為含有下述(p1)~(p3)組成物的硬化物,
(p1)於分子中具有烯基之有機聚矽氧烷、
(p2)於1分子中含有與2個以上之矽原子鍵結之氫原子(Si-H基)的有機氫聚矽氧烷:(p2)成分中之Si-H基相對於前述(p1)成分中之烯基的莫耳比成為0.3至15的量及
(p3)鉑系觸媒。
以下,針對各成分進行說明。
[(p1)成分]
(p1)成分係於分子中具有烯基之有機聚矽氧烷。(p1)成分較佳為含有烯基的莫耳數相對於1分子中之Si莫耳數(烯基莫耳數/Si莫耳數)為0.3~10mol%之烯基的直鏈狀或分枝狀的有機聚矽氧烷。特佳為含有烯基的莫耳數相對於上述Si莫耳數為0.6~9mol%之烯基的有機聚矽氧烷。
作為這般的有機聚矽氧烷,具體而言,可列舉下述式(5)及/或(6)表示者。
(式中,R13
分別獨立為不具有脂肪族不飽和鍵的1價烴基,X1
分別獨立為含有烯基之1價有機基,a為0~3之整數。又,在式(5),2a+l係於1分子中烯基含量成為0.3~10mol%之數。在式(6),l+2係於1分子中烯基含量成為0.3~10mol%之數。l為0或500以下之正數,r為1~10,000之正數)。
上述式中,作為R13
,較佳為不具有脂肪族不飽和鍵的碳原子數1~10之1價烴基,例示時,有甲基、乙基、丙基、丁基等之烷基;環己基等之環烷基;苯基、甲苯基等之芳基等,特佳為甲基等之烷基或苯基。
作為X1
之含有烯基之1價有機基,較佳為碳原子數2~10之有機基,可列舉乙烯基、烯丙基、己烯基、辛烯基等之烯基;丙烯醯基丙基、丙烯醯基甲基、甲基丙烯醯基丙基等之(甲基)丙烯醯基烷基;丙烯醯氧基丙基、丙烯醯氧基甲基、甲基丙烯醯氧基丙基、甲基丙烯醯氧基甲基等之(甲基)丙烯醯氧基烷基;環己烯基乙基、乙烯氧基丙基等之含有烯基之1價烴基,尤其是工業上較佳為乙烯基。
上述一般式(5)中,a雖為0~3之整數,但若a為1~3,由於分子鏈末端被烯基封鎖,故藉由反應性良好之此分子鏈末端烯基,可於短時間結束反應故較佳。進而,在成本面,a=1工業上較佳。含有此烯基之有機聚矽氧烷的性狀較佳為油狀或生橡膠狀。含有此烯基之有機聚矽氧烷可為直鏈狀,亦可為分枝狀。又,(p1)成分可併用2種以上。
尚,藉由上述(p1)成分的GPC之數平均分子量(Mn)較佳為100000~500000。
[(p2)成分]
(p2)成分為交聯劑,係於1分子中含有與2個以上之矽原子鍵結之氫原子(Si-H基)的有機氫聚矽氧烷。(p2)成分至少具有2個於1分子中與矽原子鍵結之氫原子(SiH基),較佳為具有2個以上100個以下,更佳為具有3個以上50個以下者,可使用直鏈狀、分枝狀或環狀者。
(p2)成分之有機氫聚矽氧烷在25℃的黏度較佳為1~5,000mPa・s,更佳為5~500mPa・s。此有機氫聚矽氧烷可為2種以上之混合物。尚,黏度係藉由回轉黏度計測定。
(p2)成分係以(p2)成分中之Si-H基相對於(p1)成分中之烯基的莫耳比(Si-H基/烯基)成為0.3~15,較佳為0.3~10,特佳為1~8的範圍的方式摻合。此SiH基與烯基的莫耳比為0.3以上時,由於不會有降低交聯密度之虞,不會有引起不硬化黏著劑層的問題之虞故較佳。若為15以下,不會有交聯密度變過高之虞,得到充分之黏著力及黏性。
[(p3)成分]
(p3)成分為鉑系觸媒(亦即,鉑族金屬觸媒),例如可列舉氯化鉑酸、氯化鉑酸之醇溶液、氯化鉑酸與醇之反應物、氯化鉑酸與烯烴化合物之反應物、氯化鉑酸與含有乙烯基矽氧烷之反應物等。
(p3)成分之添加量為有效量,通常相對於(p1)、(p2)之合計,作為鉑分(質量換算),為1~5,000ppm,較佳為5~2,000ppm。若為1ppm以上,亦不會降低組成物的硬化性,即使交聯密度降低,保持力亦不會降低。若為5,000ppm以下,可增長處理液的可能使用時間。
上述熱硬化性矽氧烷聚合物組成物溶解在溶劑,作為溶液可使用在暫時接著材層的形成。作為溶劑,例如適合使用戊烷、己烷、環己烷、異辛烷、壬烷、癸烷、p-薄荷烷、蒎烯、異十二烷、檸檬烯等之烴系溶劑或六甲基二矽氧烷或八甲基三矽氧烷等之揮發性低分子矽氧烷,可將此等之1種以單獨或併用2種以上。又,此熱硬化性矽氧烷聚合物組成物中為了提昇耐熱性可添加公知之抗氧化劑。進而,如有必要可進行過濾。
此時,所形成的膜厚為0.1~30μm,特佳為1.0~15μm之間。若膜厚為0.1μm以上,來自基板或支持體的剝離變更為容易。另一方面,若膜厚為30μm以下,可充分耐得住形成薄型晶圓時之研削步驟。尚,此熱硬化性矽氧烷聚合物中為了更提高耐熱性,可將二氧化矽等之填料相對於熱硬化性矽氧烷聚合物之各成分(p1)、(p2)、(p3)之經混合的合計100質量份,添加50質量份以下。
又,基板加工用暫時接著薄膜、與基板或支持體之間的剝離力,在25℃時,作為於180°方向剝離試驗所測定之試驗力,較佳為20mN/25mm以上500mN/25mm以下。若為具有這般的剝離(Peel)剝離力的暫時接著薄膜,由於對於後加工之CVD的耐性更為優異,於晶圓研削時不會有產生晶圓的偏移之虞,確實剝離變容易故較佳。
[基板加工用暫時接著薄膜之製造方法]
以下,雖針對本發明之基板加工用暫時接著薄膜之製造方法進行詳述,但製造方法並非被限定於此。
將前述基板加工用暫時接著薄膜的溶液使用前滾塗佈機、反轉輥塗機、刮刀逗式塗佈機、模具塗佈機、唇塗機、凹版塗佈機、浸塗機、氣刀塗佈機、毛細管塗佈機、Raging & Rising(R&R)塗佈機、刮刀塗佈機、棒塗機、施用機、擠出成形機等,塗佈在脫模基材(脫模薄膜)上。此情況下,較佳為以塗佈速度為0.05~1000m/min,尤其是以0.1~500m/min塗佈在支持薄膜上。
然後,將塗佈基板加工用暫時接著薄膜的溶液之脫模基材通過在線烘乾機(熱風循環烤箱),在40~130℃1~40分鐘,更佳為在50~120℃,以2~30分鐘去除有機溶劑及揮發成分並使其乾燥,形成基板加工用暫時接著薄膜。又,如有必要可將其他保護薄膜(脫模基材)使用輥式層壓機壓著在基板加工用暫時接著薄膜上並層合。此時,基板加工用暫時接著薄膜之製膜後的厚度為0.5~80μm,特佳為0.5~50μm。
如此層合之基板加工用暫時接著薄膜(及如有必要之脫模基材及保護薄膜),藉由直接於紙管、塑膠管等之捲繞核心環繞基板加工用暫時接著薄膜的端部並進行捲繞,而成為基板加工用暫時接著薄膜輥。
此時,基板加工用暫時接著薄膜藉由以張力10~200N/m,較佳為20~150N/m,速度0.05~1000m/ min,較佳為0.1~500m/min進行捲繞,可得到於薄膜全體無扭曲之基板加工用暫時接著薄膜輥。
又,使用保護薄膜時,較佳為最終進行藉由二段式輥之層壓並捲繞。
尚,所得之基板加工用暫時接著薄膜輥之徑,從製造的安定性及相對於捲繞核心之捲曲慣性、所謂防止捲曲的觀點來看,較佳為100mm~300mm。捲繞核心例如可使用芯管。
又,如有必要成為可使用之脫模基材的脫模薄膜、保護薄膜,若為不損害基板加工用暫時接著薄膜的形態,可從基板加工用暫時接著薄膜的表面之層剝離者,則並未特別限定,即使為單一即使為層合複數聚合物薄膜的多層薄膜皆可使用。可使用尼龍薄膜、聚乙烯(PE)薄膜、聚對苯二甲酸乙二酯(PET)薄膜、聚萘二甲酸乙二酯薄膜、聚苯硫醚(PPS)薄膜、聚丙烯(PP)薄膜、聚苯乙烯薄膜、聚甲基戊烯(TPX)薄膜、聚碳酸酯、含有氟之薄膜、特殊聚乙烯醇(PVA)薄膜、實施脫模處理之聚酯薄膜等之塑膠薄膜等。
從此等當中,針對脫模基材(脫模薄膜),較佳為具有適度的可撓性、機械性強度及耐熱性的聚對苯二甲酸乙二酯。又,針對此等之薄膜,可為進行如電暈處理或塗佈剝離劑之各種處理者。此等可使用市售品,例如可列舉Cerapeel WZ(RX)、Cerapeel BX8(R)(以上為東麗薄膜加工(股)製)、E7302、E7304(以上為東洋紡績(股)製)、Purex G31、Purex G71T1(以上為杜邦帝人薄膜(股)製)、PET38×1-A3、PET38×1-V8、PET38×1-X08(以上為NIPPA(股)製)等。
進而,針對保護薄膜,較佳為具有適度的可撓性之聚對苯二甲酸乙二酯及聚乙烯。此等可使用市售品,作為聚對苯二甲酸乙二酯可列舉於上所例示者,又,作為聚乙烯,例如可列舉GF-8(Tamapoly(股)製)、PE薄膜0型(NIPPA(股)製)等。
上述脫模基材及保護薄膜的厚度,從製造的安定性及對於捲繞核心之捲曲慣性、所謂捲曲防止的觀點來看,較佳為皆為10~100μm。
從藉由上述製造方法所製造之基板加工用暫時接著薄膜輥所取出之基板加工用暫時接著薄膜,係暫時接著材層間之密著性優異,例如耐藥品性優異。
本發明之薄型基板之製造步驟係具有(a)~(g)之步驟。
[步驟(a)]
步驟(a)係於並非基板之應加工的面之表面或是前述支持體之至少任何一個,層壓前述基板加工用暫時接著薄膜之步驟。
應加工背面之基板,例如,一側的面為電路形成面,背面為電路非形成面的基板。可適用本發明的基板通常為半導體基板。作為該半導體基板之例,可列舉圓盤狀之晶圓或角基板等。作為晶圓之例,不僅矽晶圓,亦可列舉鍺晶圓、鎵-砷晶圓、鎵-磷晶圓、鎵-砷-鋁晶圓等。該基板的厚度雖並未特別限制,但典型而言為600~800μm,更典型而言為625~775μm。作為支持體,雖並未特別限定,但可使用矽晶圓或玻璃板、石英晶圓等之基板。在本發明,不一定要通過支持體對暫時接著薄膜照射放射能量線,支持體可為不具有光線透過性者。
基板加工用暫時接著薄膜,係以形成在聚乙烯或聚酯等之脫模基材上的狀態,從基板加工用暫時接著薄膜輥取出。然後,層壓在基板或支持體,實施切斷加工成必要的長度等。或是實施切斷加工成必要的長度後,層壓在基板或支持體。此時,視必要可邊將脫模基材從基板加工用暫時接著薄膜剝離(剝離力10~1000mN/25mm),邊形成在基板上。又,亦可邊剝離保護薄膜,或直接形成在支持體上。進而,亦可邊剝離另一側的保護薄膜或脫模材,邊與基板或支持體貼合。作為對基板或支持體層壓基板加工用暫時接著薄膜的裝置,於晶圓的情況下,可列舉真空層壓機,例如Takatori公司之TEAM-100、TEAM-300等。
[步驟(b)]
步驟(b)係將前述基板與前述支持體透過在步驟(a)層壓之基板加工用暫時接著薄膜,於減壓下接合之步驟。以下,邊參照圖1邊針對步驟(b)進行說明。藉由暫時接著薄膜形成暫時接著材層3之基板2及支持體4的層合體1,透過暫時接著材層3,作為經接合之基板形成。此時,較佳為於40~200℃,更佳為於60~180℃之溫度區域,在此溫度真空下(減壓下;壓力1Pa以下),均一壓著此基板,接著暫時接著材層3,形成基板2與支持體4接合之層合體(層合體基板)1。此時,壓著的時間為10秒~10分鐘,較佳為30秒~5分鐘。作為貼合基板之裝置,於晶圓的情況下,可列舉市售之晶圓接合裝置,例如EVG公司之EVG520IS、850TB、SUSS公司之XBS300等。
[步驟(c)]
步驟(c)係研削或研磨與支持體接合之基板之應加工的面(背面)之步驟,亦即,研削或研磨在步驟(b)貼合所得之層合體的基板背面側,薄化該基板的厚度之步驟。基板背面之研削加工的方式並未特別限制,可採用公知之研削方式。研削較佳為於基板與研磨石(金剛石等)邊澆上水冷卻邊進行。作為研削加工基板背面的裝置,例如可列舉(股)DISCO製DAG810等。又,可CMP研磨基板背面側。
[步驟(d)]
步驟(d)係將與支持體接合之基板之應加工的面(背面)使用酸或是鹼,處理基板之步驟。作為使用在處理之酸,可列舉H2
SO4
、H2
O2
、HF、HNO3
,作為鹼,可列舉NH3
、NMe4
OH(Me為甲基)、NH4
OH、H3
PO4
等,可使用1種或是2種以上此等之酸或是鹼來進行處理。使用上述酸或是鹼之處理(酸・鹼處理),可藉由於進行上述a~c步驟的層合體噴霧、塗佈、浸漬處理溶液來進行。此時之處理時間雖並未特別限制,但較佳為以10秒~30分鐘的短時間處理。酸・鹼處理後如有必要進行水洗・乾燥。
[步驟(e)]
步驟(e)係研削背面(電路非形成面)的層合體,亦即,於藉由背面研削而薄型化之層合體之應加工的面實施研削、研磨、酸處理、鹼處理以外的加工之步驟。此步驟中包含於基板級別所使用之各式各樣的製程。作為例,可列舉電極形成、金屬配線形成、保護膜形成等。更具體而言,可列舉用以電極等之形成的金屬濺鍍、蝕刻金屬濺鍍層之濕式蝕刻、藉由用以成為金屬配線形成之遮罩的抗蝕劑之塗佈、曝光及顯影之圖型的形成、抗蝕劑的剝離、乾蝕刻、金屬鍍敷的形成、用以TSV形成之矽蝕刻、矽表面之氧化膜形成等以往公知之製程。
[步驟(f)]
步驟(f)係將於步驟(e)實施加工之基板從支持體剝離之步驟亦即,對經薄型化之基板實施各式各樣加工後,於切割之前將基板2從支持體4剝離之步驟。此剝離步驟,一般而言可列舉從於室溫至60℃程度之比較低溫的條件實施,將層合體1之基板2或支持體4之一者固定在水平,將另一者從水平方向附一定的角度舉起之方法,及於經加工之基板2的加工面貼上保護薄膜,將基板2與保護薄膜以剝離方式從層合體剝離之方法等。本發明中此等之剝離方法的任一種皆可適用。當然不限定於上述之方法。此等之剝離方法通常於室溫實施。
[步驟(g)]
步驟(g)係洗淨殘存在於步驟(f)剝離之基板的表面之暫時接著材料之步驟。藉由步驟(f),由支持體剝離之基板的表面中,雖有殘存暫時接著材層3的情況,但暫時接著材層3之殘存物可藉由洗淨基板去除。
於步驟(g),若為如溶解暫時接著層3之洗淨液,則全部可使用,具體而言,可列舉環己酮、環戊酮、甲基-2-n-戊基酮等之酮類;3-甲氧基丁醇、3-甲基-3-甲氧基丁醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇等之醇類;丙二醇單甲基醚、乙二醇單甲基醚、丙二醇單乙基醚、乙二醇單乙基醚、丙二醇二甲基醚、二乙二醇二甲基醚等之醚類;丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、乳酸乙酯、丙酮酸乙酯、乙酸丁酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸tert-丁酯、丙酸tert-丁酯、丙二醇單-tert-丁基醚乙酸酯、γ-丁內酯等之酯類;戊烷、己烷、環己烷、異辛烷、壬烷、癸烷、p-薄荷烷、蒎烯、異十二烷、檸檬烯等之烴系溶劑;六甲基二矽氧烷、八甲基三矽氧烷等之揮發性低分子矽氧烷等。此等之溶劑可1種單獨亦可組合2種以上使用。又,難以去除時,可於上述溶劑添加鹼類、酸類。作為鹼類之例,可使用乙醇胺、二乙醇胺、三乙醇胺、三乙基胺、氨等之胺類、四甲基氫氧化銨等之銨鹽類。作為酸類,可使用乙酸、草酸、苯磺酸、十二烷基苯磺酸等之有機酸。添加量係以洗淨液中濃度為0.01~10質量%,較佳為0.1~5質量%。又,為了提升殘存物的去除性,可添加既存之界面活性劑。作為洗淨方法,使用上述液進行於槳之洗淨之方法、於噴灑噴霧之洗淨方法、浸漬在洗淨液槽之方法為可能。溫度適合為10~80℃,較佳為15~65℃,若有必要,亦可以此等之溶解液溶解暫時接著材層後,最終進行藉由水洗或醇之清洗,並進行乾燥處理,而得到薄型基板。
[實施例]
以下,雖顯示實施例及比較例,具體說明本發明,本發明並非被限定於此等者。尚,於下述例份為質量份。又,Me表示甲基,Vi表示乙烯基。
[樹脂溶液製作例1]
於具備攪拌機、溫度計、氮取代裝置及回流冷卻器的燒瓶內置入9,9’-雙(3-烯丙基-4-羥基苯基)茀(M-1)43.1g、平均結構式(M-3)表示之有機氫矽氧烷29.5g、甲苯135g、氯化鉑酸0.04g,昇溫至80℃。然後,將1,4-雙(二甲基矽烷基)苯(M-5)17.5g耗費1小時滴下在燒瓶內。此時,燒瓶內溫度上昇至85℃。滴下結束後,進而於80℃熟成2小時後,餾除甲苯,並且添加80g環己酮,而得到將樹脂固體成分濃度50質量%之環己酮作為溶劑之樹脂溶液。將此溶液之樹脂分的分子量藉由GPC測定時,以聚苯乙烯換算重量平均分子量為45,000。進而,作為抗氧化劑,添加0.1g之肆[亞甲基-(3,5-二-t-丁基-4-羥基氫化桂皮酸酯)]甲烷(商品名:Adekastab AO-60),以1μm之膜過濾器進行過濾,而得到樹脂溶液(A-1溶液)。
[樹脂溶液製作例2]
於具備攪拌機、溫度計、氮取代裝置及回流冷卻器之5L燒瓶內,將環氧化合物(M-2)84.1g溶解在甲苯600g後,加入化合物(M-3)294.6g、化合物(M-4)25.5g,加溫至60℃。然後,投入碳載持鉑觸媒(5質量%)1g,確認內部反應溫度昇溫至65~67℃後,進而,加溫至90℃,熟成3小時。其次,冷卻至室溫後,加入甲基異丁基酮(MIBK) 600g,藉由將本反應溶液在過濾器進行加壓過濾,去除鉑觸媒。減壓餾除此樹脂溶液中之溶劑,並且添加丙二醇單甲基醚乙酸酯(PGMEA)270g,而得到將固體成分濃度60質量%之PGMEA作為溶劑之樹脂溶液。將此樹脂溶液中之樹脂的分子量藉由GPC測定時,以聚苯乙烯換算重量平均分子量為28,000。進而將此樹脂溶液以1μm之膜過濾器進行過濾,而得到樹脂溶液(A-2溶液)。
[樹脂溶液製作例3]
於由於兩末端及側鏈具有3莫耳%之乙烯基,且分子末端以SiMe2
Vi基封鎖,藉由GPC之數平均分子量(Mn)為50,000之聚二甲基矽氧烷100份,及異十二烷400份所構成之溶液,添加下述式(M-7)表示之有機氫聚矽氧烷10份(相對於烯基為2莫耳)並混合。進而,相對於聚二甲基矽氧烷100份,添加0.05份之鉑觸媒CAT-PL-5(信越化學工業股份有限公司製),以0.2μm之膜過濾器進行過濾,而得到樹脂溶液(B-1溶液)。
[樹脂溶液製作例4]
將氫化苯乙烯・乙烯・丙烯共聚物之熱塑性樹脂SEPTON 2002(Kuraray製)24g溶解在異壬烷176g,而得到12質量%之氫化苯乙烯・乙烯・丙烯共聚物的異壬烷溶液。將所得之溶液以0.2μm之膜過濾器進行過濾,而得到樹脂溶液(C-1溶液)。
-薄膜製造步驟-
將前述樹脂溶液(A-1溶液)使用刮刀逗式塗佈機作為薄膜塗佈機,於作為脫模基材之聚對苯二甲酸乙二酯(PET)薄膜(厚度38μm)上以塗佈速度0.4m/min塗佈,進行乾燥製作(A-1)層。然後,於經製作之薄膜的表面,作為保護薄膜,係將聚乙烯(PE)薄膜(厚度100μm)以壓力1MPa貼合,以速度:0.4m/min、張力:30N為基礎,捲繞在塑膠管,製作直徑130mm之基板加工用暫時接著薄膜(A-1)之輥。
同樣,藉由分別塗佈(A-2溶液)、(B-1溶液)、(C-1溶液)並捲繞,分別製作(A-2)、(B-1)、(C-1)之輥。
將前述樹脂溶液(A-1溶液)使用刮刀逗式塗佈機作為薄膜塗佈機,於作為脫模基材之聚對苯二甲酸乙二酯(PET)薄膜(厚度38μm)上以塗佈速度0.4m/min塗佈,進行乾燥製作(A-1)層。將接著前述樹脂溶液(B-1溶液)使用刮刀逗式塗佈機作為薄膜塗佈機,於形成上述(A-1)層之聚對苯二甲酸乙二酯(PET)薄膜上以塗佈速度0.4m/min塗佈,進行乾燥製作(B-1)層。然後,於經製作之薄膜的表面,作為保護薄膜,係將聚乙烯(PE)薄膜(厚度100μm)以壓力1MPa貼合,以速度:0.4m/min、張力:30N為基礎,捲繞在塑膠管,製作直徑130mm之基板加工用暫時接著薄膜(D-1)之輥。
同樣,藉由以(A-2溶液)與(C-1溶液)、(B-1溶液)與(C-1溶液)之組合進行塗佈並捲繞,分別製作(E-1)、(F-1)、(F-2)之輥。
(實施例1)
將直徑200mm(厚度:500μm)之玻璃板作為支持體,使用真空層壓機TEAM-100((股)Takatori製),將真空腔內設定在真空度80Pa,邊從上述基板加工用暫時接著薄膜(A-1)之輥剝離保護薄膜,邊延伸基板加工用暫時接著薄膜,層壓後,去除脫模基材。
然後,分別將直徑200mm矽晶圓(厚度:725μm)、與附前述基板加工用暫時接著薄膜之玻璃板,以矽晶圓之銅柱表面、與玻璃板上之暫時接著薄膜相鄰的方式,在真空貼合裝置(EVG520IS)內以表1所示的條件貼合,製作層合體。以接合溫度為表1所記載之值,接合時之腔內壓力為10-3
mbar以下,荷重為5kN實施。而且,將該層合體於120℃進行1分鐘加熱使其接著,並使其接合,來製作試料。
(實施例2~6及比較例1~2)
以表1所記載之條件與實施例1同樣進行處理,製作實施例2~6及比較例1~2之試料。
尚,於此,為了以目視判別基板接著後之異常,作為支持體雖使用玻璃板,但亦可使用不透過晶圓等之光的矽基板。
然後,對於此經接合之基板(試料),進行下述試驗,將實施例及比較例的結果示於表1。又,雖依下述之順序實施評估,但於背面研削耐性試驗以後之評估判定為「×」的時間點,中止其以後之評估。
-接著性試驗-
如上述,以目視確認所得之層合體(試料)之界面的接著狀況。將未發生於界面之氣泡等之異常的情況評估為良好以「○」表示,將發生異常的情況評估為不良以「×」表示。
-背面研削耐性試驗-
針對於磨床((股)DISCO製、DAG810)使用金剛石研磨石,如上述般進行所得之層合體(試料),進行矽晶圓的背面研削。研磨至最終基板厚為50μm為止後,在光學顯微鏡(100倍)調查破裂、剝離等之異常的有無。將未發生異常的情況以「○」表示,將發生異常的情況以「×」表示。
-耐藥品性試驗-
將背面研削性試驗後之層合體(試料)以H2
SO4
/H2
O2
溶液(莫耳比1:1)進行10分鐘浸漬處理,將處理後之試料以純水洗淨。將之後試料以NH4
OH/H2
O2
/H2
O溶液進行10分鐘浸漬處理,將處理後之試料以純水洗淨。將處理後之試料在光學顯微鏡(100倍)調查剝離的有無。將未發生剝離的情況以「○」表示,將發生剝離的情況以「×」表示。
-剝離性試驗-
基板之剝離性係用以下之方法評估。首先,於薄型化至結束耐藥品性試驗之晶圓加工體的50μm為止之晶圓側使用切割框架,貼上切割膠帶,將此切割膠帶面藉由真空吸著,設定在吸著板。然後,在室溫藉由將玻璃之1點以鑷子舉起,剝離玻璃基板。將50μm之晶圓不破裂可剝離的情況以「○」表示,將發生破裂等之異常的情況以「×」表示。
-洗淨去除性試驗-
透過上述剝離性試驗結束後之切割膠帶,將安裝在切割框架之200mm晶圓設定在旋塗機,作為洗淨溶劑,噴霧異壬烷3分鐘後,邊使晶圓回轉邊將異丙基醇(IPA)以噴霧進行清洗。然後,觀察外觀,以目視檢查殘存之接著材樹脂的有無。將未觀察到樹脂之殘存者評估為良好以「○」表示,將觀察到樹脂之殘存者評估為不良以「×」表示。
-耐污染性試驗-
將上述洗淨去除性試驗後之基板表面以光學顯微鏡(100倍)觀察表面狀態。將於表面未觀察到異常者評估為良好以「○」表示,將觀察到異常者評估為不良以「×」表示。
-剝離力試驗-
將直徑200mm矽晶圓A(厚度:725μm)作為支持體,將於上述薄膜製造步驟製作之基板加工用暫時接著薄膜,層壓在矽晶圓A,並去除脫模基材。然後,分別將預先於表面上實施脫模處理的直徑200mm(厚度:725μm)之矽晶圓B、與附前述基板加工用暫時接著薄膜之支持體,以矽晶圓B之脫模處理面與支持體上之暫時接著薄膜相鄰的方式,於真空貼合裝置內以表1所示的條件貼合,製作層合體。然後,而且將該層合體以表1所示的之條件進行加熱,使其接著,並使其接合,從層合體僅去除實施脫模處理之矽晶圓B,製作於矽晶圓A層合基板加工用暫時接著薄膜的層合體。
然後,於上述層合體之基板加工用暫時接著薄膜層上貼附5條150mm長×25mm寬的聚醯亞胺膠帶,去除未貼附膠帶部分的暫時接著材層。使用(股)島津製作所製之AUTOGRAPH(AG-Xplus),於25℃環境下以300mm/min的速度從膠帶的一端,以180°剝離剝離60mm,將此時所施加之力的平均(120mm衝程×5次)定為該暫時接著材層的剝離力。
如表1所示,判斷滿足本發明之要件的基板加工用暫時接著薄膜,係基板與支持體的暫時接著容易,且容易剝離,尤其是耐藥品性優異,即使於加工步驟中,於接著劑界面亦不會產生剝離(實施例1~6)。另一方面,於未滿足本發明之要件的比較例1及2,耐藥品性惡化,於接著劑界面產生剝離,無法進行之後的切削・研磨加工。
從以上之結果即可清楚明白,若為本發明之薄型基板之製造方法,由於使用特定之基板加工用暫時接著薄膜,層壓在基板或支持體上,故在(a)~(b)步驟可輕易於基板或支持體上形成暫時接著材層,以短時間進行暫時接著材層形成變可能,對於(c)步驟之研磨處理、(d)步驟之酸・鹼處理的耐性優異。又,根據本發明,提昇形成在基板面或支持體面之暫時接著材的尺寸安定性,減低層合體的扭曲,對於(e)步驟(TSV形成、基板背面配線步驟等)的步驟適合性高。進而,除了嵌入性或耐熱性優異外,於(f)步驟,於薄型基板製作後將基板由支持體剝離時,例如由於可於室溫輕易剝離,故即使是容易破裂的薄型基板亦可輕易製造,於(g)步驟由於可輕易洗淨去除殘存在基板表面之暫時接著材料,故可製造無表面污染的薄型基板。尤其是對於(d)步驟之酸・鹼處理的耐性(耐藥品性)優異的點,將基板接合在支持體時之暫時接著層,不僅具備僅耐得住之後的步驟之充分的耐久性,並且最後由於可將薄型基板從支持體簡便地剝離,可擴散可於(e)步驟選擇之加工的變異,實用上之利用價值高。
尚,本發明並非被限定於上述實施形態者。上述實施形態為例示,若為具有與本發明之申請專利範圍所記載之技術思想實質上同一之構成,發揮同樣之作用效果者,任何者皆包含在本發明之技術範圍。
1‧‧‧層合體
2‧‧‧基板
3‧‧‧暫時接著材層
4‧‧‧支持體
[圖1]係表示使用本發明之基板加工用暫時接著薄膜製作之基板加工用層合體的一例之概略圖。
1‧‧‧層合體
2‧‧‧基板
3‧‧‧暫時接著材層
4‧‧‧支持體
Claims (5)
- 一種薄型基板之製造方法,其係使用用以將應加工背面之基板暫時接著在支持體之基板加工用暫時接著薄膜的薄型基板之製造方法,其特徵為前述基板加工用暫時接著薄膜係含有10質量份以上100質量份以下之總質量每100質量份之重量平均分子量為3,000~500,000之含有矽氧烷鍵的聚合物,包含下述(a)~(g)步驟全部,(a)於並非前述基板之應加工的面之表面或是前述支持體之至少任何一個,層壓前述基板加工用暫時接著薄膜之步驟、(b)將前述基板與前述支持體透過在步驟(a)層壓之基板加工用暫時接著薄膜,於減壓下接合之步驟、(c)研削或研磨前述基板之應加工的面,處理基板之步驟、(d)將前述基板之應加工的面使用酸或是鹼,處理基板之步驟、(e)於前述基板之應加工的面實施研削、研磨、酸處理、鹼處理以外的加工之步驟、(f)將實施該加工之前述基板從前述支持體剝離之步驟、(g)洗淨前述基板之步驟。
- 如請求項1所記載之薄型基板之製造方法,其中,前述基板加工用暫時接著薄膜係與前述基板或前述支持體之間的剝離力,對在25℃之180°方向的剝離試驗中為20mN/25mm以上500mN/25mm以下者。
- 如請求項1或請求項2所記載之薄型基板之製造方法,其中,前述含有矽氧烷鍵之聚合物為含有下述(p1)~(p3)之組成物的硬化物,(p1)於分子中具有烯基之有機聚矽氧烷、(p2)於1分子中含有與2個以上之矽原子鍵結之氫原子(Si-H基)的有機氫聚矽氧烷:(p2)成分中之Si-H基相對於前述(p1)成分中之烯基的莫耳比成為0.3至15的量及(p3)鉑系觸媒。
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- 2019-05-17 US US16/415,259 patent/US10950481B2/en active Active
- 2019-05-30 TW TW108118699A patent/TWI796486B/zh active
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EP3579267A1 (en) | 2019-12-11 |
CN110556329A (zh) | 2019-12-10 |
JP6998838B2 (ja) | 2022-01-18 |
US20190371644A1 (en) | 2019-12-05 |
JP2019212726A (ja) | 2019-12-12 |
TW202006104A (zh) | 2020-02-01 |
KR20190138278A (ko) | 2019-12-12 |
EP3579267B1 (en) | 2023-07-12 |
US10950481B2 (en) | 2021-03-16 |
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