TWI814931B - 層合體之製造方法以及基板之製造方法 - Google Patents
層合體之製造方法以及基板之製造方法 Download PDFInfo
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- TWI814931B TWI814931B TW108139391A TW108139391A TWI814931B TW I814931 B TWI814931 B TW I814931B TW 108139391 A TW108139391 A TW 108139391A TW 108139391 A TW108139391 A TW 108139391A TW I814931 B TWI814931 B TW I814931B
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Abstract
本發明提供可經由暫時接著材使基板與支撐體容易接合,且熱製程耐性優異,剝離亦容易,且可提高薄型基板之生產性的層合體之製造方法。
本發明之層合體之製造方法係將背面應加工之基板的非加工面與支撐體經由暫時接著材接合的層合體之製造方法,其特徵係具有下述步驟:於前述基板之非加工面及前述支撐體中之任一者或兩者層合前述暫時接著材之步驟(a),於接合開始前預先加熱前述基板與前述支撐體之步驟(b),及將前述基板與前述支撐體經由前述暫時接著材而接合之步驟(c),前述步驟(b)中,將前述基板加熱至50℃以上250℃以下之溫度,將前述支撐體加熱至50℃以上250℃以下且與前述基板不同之溫度,並且於前述步驟(c)中,於預先加熱之前述基板之溫度與前述支撐體之溫度不同之狀態開始接合。
Description
本發明有關層合體之製造方法以及基板之製造方法。
為了實現更進一步之高密度、大容量化,3次元之半導體安裝成為必須。所謂3次元安裝技術係使1個半導體晶片薄型化,進而邊藉由矽貫通電極(TSV:through silicon via)線連結邊以多層層合之半導體製作技術。為了實現該技術,需要如下步驟:將形成有半導體電路之基板藉由非電路形成面(亦稱為「背面」)研削而薄型化,進而於背面進行包含TSV之電極形成。
以往,矽基板之背面研削步驟中,於研削面之相反側貼附保護膠帶,防止研削時之基板破損。然而,該膠帶於支撐基材中使用有機樹脂膜,雖具有柔軟性,但相反地強度或耐熱性不足,並不適於TSV形成步驟或於背面之配線層形成步驟。
因此,已提案藉由將半導體基板經由接著層接合於矽、玻璃等之支撐體,而可充分耐受背面研削、TSV或背面電極形成之步驟之系統。此時重要的是將基板接合於支撐體時之接著層。其被要求可無間隙地將基板接合於支撐體,且需要僅耐受後續步驟之充分耐久性,進而於最後可簡便地自支撐體剝離薄型基板。如此,由於最後會剝離,故於本說明書中,將該接著層稱為暫時接著層,將所用之材料稱為暫時接著材。
作為迄今之使用暫時接著層之習知層合體之製造方法,提案有於基板與支撐體之一者或兩者形成暫時接著層,於接合裝置內根據需要將基板與支撐體預先加熱至相同溫度後進行接合之技術(專利文獻1、2)。藉由該等接合方法,於經由接合溫度下熔融黏度不同之材料接合之情況會有問題。
[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] 日本專利第6059631號
[發明欲解決之課題]
本發明係鑒於上述問題點而完成者,目的在於提供可經由暫時接著材使基板與支撐體容易接合,且CVD(化學氣相成長)等之熱製程耐性優異,剝離亦容易,且可提高薄型基板之生產性的層合體之製造方法。
[用以解決課題之手段]
為了達成上述課題,本發明提供一種層合體之製造方法,其係將背面應加工之基板的非加工面(並非基板背面之面)與支撐體經由暫時接著材接合的層合體之製造方法,其特徵係具有下述步驟:於前述基板之非加工面及前述支撐體中之任一者或兩者層合前述暫時接著材之步驟(a),於接合開始前預先加熱前述基板與前述支撐體之步驟(b),及將前述基板與前述支撐體經由前述暫時接著材而接合之步驟(c),前述步驟(b)中,將前述基板加熱至50℃以上250℃以下之溫度,將前述支撐體加熱至50℃以上250℃以下且與前述基板不同之溫度,並且於前述步驟(c)中,於預先加熱之前述基板之溫度與前述支撐體之溫度不同之狀態開始接合。
依據本發明之層合體之製造方法,可容易地經由暫時接著材接合基板與支撐體,CVD(化學氣相成長)等之熱製程耐性優異,剝離亦容易,可提高薄型基板之生產性。
該情況下,前述步驟(c)中,較佳於前述基板之溫度與前述支撐體之溫度相差10℃以上之狀態開始接合。
依據如此溫度條件之層合體之製造方法,由於對於朝凹凸基板之嵌埋性優異故而較佳。
且本發明中,作為前述暫時接著材較佳使用具有至少位於前述基板側之第一暫時接著材層(A)與比該第一暫時接著材層(A)更位於前述支撐體側之第二暫時接著材層(B)之2層以上之暫時接著材。
依據此等暫時接著材,可根據需要個別選擇熔融黏度等不同特性之暫時接著材層。
該情況下,較佳使用前述第一暫時接著材層(A)與前述第二暫時接著材層(B)之熔融黏度比α/β係於25℃下之熔融黏度比為10以下,且於100℃以上200℃以下之最低熔融黏度比為100以上之暫時接著材。
暫時接著材若為此等熔融黏度比,則可於短時間進行接合處理故而較佳。
且本發明中,較佳於前述步驟(a)中,以鄰接之方式形成前述第一暫時接著材層(A)與前述第二暫時接著材層(B)而層合前述暫時接著材。
又該情況下,較佳使用前述第二暫時接著材層(B)係由熱硬化性樹脂所成,且該熱硬化性樹脂經硬化所成之硬化膜之藉由動態黏彈性測定所測定之彈性率於25℃下為50MPa以上1GPa以下之暫時接著材。
硬化膜若為此等彈性率之第二暫時接著材層(B),則由於暫時固定時,尤其是基板研削後,基板無翹曲故而較佳。
又本發明中,較佳前述第二暫時接著材層(B)係藉由熱硬化性樹脂組成物所形成,該熱硬化性樹脂組成物相對於具有下述通式(1)所示之重複單位之重量平均分子量為3,000~500,000之含矽氧烷鍵之聚合物100質量份,含有0.1~50質量份之作為交聯劑之自藉由甲醛或甲醛-醇改質之胺基縮合物、三聚氰胺樹脂、脲樹脂、1分子中平均具有2個以上羥甲基或烷氧基羥甲基之酚化合物及1分子中平均具有2個以上環氧基之環氧化合物所選出之任1種以上,
[式中,R1
~R4
表示可相同亦可不同之碳原子數1~8之1價烴基,且m為1~100之整數,B為正數,A為0或正數,但A+B=1,X係下述通式(2)所示之2價有機基:
(式中,Z為自
之任一者選出之2價有機基,N為0或1,且R5
、R6
分別為碳原子數1~4之烷基或烷氧基,可相互相同亦可不同,k為0、1、2之任一者)]。
依據此等第二暫時接著材層(B),耐熱性進而更優異故而較佳。
且本發明中,較佳前述第二暫時接著材層(B)係藉由熱硬化性樹脂組成物所形成,該熱硬化性樹脂組成物相對於具有下述通式(3)所示之重複單位之重量平均分子量為3,000~500,000之含矽氧烷鍵之聚合物100質量份,含有0.1~50質量份之作為交聯劑之自1分子中平均具有2個以上酚基之酚化合物及1分子中平均具有2個以上環氧基之環氧化合物所選出之任1種以上,
[式中,R7
~R10
表示可相同亦可不同之碳原子數1~8之1價烴基,且n為1~100之整數,D為正數,C為0或正數,但C+D=1,進而,Y係下述通式(4)所示之2價有機基:
(式中,V為自
之任一者選出之2價有機基,p為0或1,且R11
、R12
分別為碳原子數1~4之烷基或烷氧基,可相互相同亦可不同,h為0、1、2之任一者)]。
依據此等第二暫時接著材層(B),耐熱性進而更優異故而較佳。
且,本發明提供一種基板之製造方法,其特徵係具有下述步驟:藉由上述層合體之製造方法獲得層合體後,進行加工前述基板背面之步驟(d),其後進而自前述層合體去除前述支撐體與前述暫時接著材之後,洗淨前述基板之步驟(e),前述步驟(e)中,基板洗淨後之去除支撐體之側的面的水接觸角未達30°。
依據此等基板之製造方法,可製造於後續步驟不發生源自暫時接著材之不良,可容易地製造具有貫通電極構造或凸塊連接構造之薄型基板的基板。
[發明效果]
如以上,依據本發明之層合體之製造方法,尤其可經由熔融黏度不同之材料容易地製造層合體。藉由可使用如此之熔融黏度不同之材料,可使用各種材料製造層合體。且,可將伴隨層合體製造而發生之空隙等缺陷防範於未然,可大幅提高薄型基板之製造性。
如上述,要求具有可容易暫時接著,對基板或支撐體之暫時接著材形成速度快、尺寸安定性優異、如CVD之基板熱製程之耐性優異、剝離亦容易,且可提高薄型基板之生產性之基板加工用暫時接著材。
本發明人等為達成上述目的而進行積極檢討之結果,發現藉由於接合開始前預先加熱基板與支撐體之步驟中,將前述基板加熱至50℃以上250℃以下之溫度,將前述支撐體加熱至50℃以上250℃以下且與前述基板不同之溫度,並且於經由暫時接著材接合基板與支撐體之步驟中,於預先加熱之前述基板之溫度與前述支撐體之溫度不同之狀態開始接合,可簡單地製造具有貫通電極構造或凸塊連接構造之薄型基板,因而完成本發明。
亦即,本發明係一種層合體之製造方法,其係將背面應加工之基板的非加工面與支撐體經由暫時接著材接合的層合體之製造方法,其特徵係具有下述步驟:於前述基板之非加工面及前述支撐體中之任一者或兩者層合前述暫時接著材之步驟(a),於接合開始前預先加熱前述基板與前述支撐體之步驟(b),及將前述基板與前述支撐體經由前述暫時接著材而接合之步驟(c),前述步驟(b)中,將前述基板加熱至50℃以上250℃以下之溫度,將前述支撐體加熱至50℃以上250℃以下且與前述基板不同之溫度,並且於前述步驟(c)中,於預先加熱之前述基板之溫度與前述支撐體之溫度不同之狀態開始接合。
依據此等本發明之層合體之製造方法,經由熔融黏度不同之材料接合之際,可製造無空隙等缺陷之層合體。因此,本發明中,可容易地獲得經由暫時接著材接合背面應加工之基板之非加工面與支撐體之層合體。
以下針對本發明詳細說明,但本發明並非限定於該等者。
[層合體]
圖1係顯示以本發明之層合體之製造方法所得之層合體之一例的構成圖。如圖1所示,前述層合體係經由暫時接著材2接合基板1與支撐體3者。
基板1係例如一面為電路形成面,應加工之另一面(背面)為電路非形成面之基板。本發明可適用之基板通常為半導體基板。作為該半導體基板之例,舉例為圓盤狀之晶圓或有角基板等。作為晶圓之例,不僅為矽晶圓,亦可舉例為鍺晶圓、鎵-砷晶圓、鎵-磷晶圓、鎵-砷-鋁晶圓等。該基板之厚度並未特別限制,但典型上為600~800μm,更典型上為625~775μm。
作為支撐體3,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。本發明中,並無必要必定通過支撐體對暫時接著材照射放射能量線,支撐體亦可為不具有光線透過性者。
暫時接著材2只要能成為將基板接合於支撐體之際的接著層,可將基板無間隙地接合於支撐體,具有僅耐受後續步驟之充分耐久性,進而最後可簡便地將薄型基板自支撐體剝離者,則未特別限定。又,本發明所用之暫時接著材2可為單層,亦可為由複數層構成。以下,將如此構成暫時接著材之各層稱為暫時接著材層。作為本發明之層合體之製造方法所用之暫時接著材2較佳為具有至少位於前述基板側之第一暫時接著材層(A)與比該第一暫時接著材層(A)更位於前述支撐體側之第二暫時接著材層(B)之2層以上之暫時接著材。
暫時接著材2包含第一暫時接著材層(A)與第二暫時接著材層(B)之情況的層合體示於圖1。
以下,雖以圖1所示之層合體之製造方法為中心加以說明,但本發明並未限定於此。又,本發明之層合體之製造方法所用之暫時接著材雖以具有第一暫時接著材層(A)與第二暫時接著材層(B)之暫時接著材為中心加以說明,但亦可僅具備(A)、(B)中之一者,亦可具備(A)、(B)以外之層。
[層合體之製造方法]
本發明之層合體之製造方法係將背面應加工之基板(具有半導體電路等之基板)的非加工面(並非基板背面之面:形成半導體電路之該面)與支撐體經由暫時接著材接合的層合體之製造方法,其具有以下步驟。
步驟(a):於基板之非加工面及支撐體中之任一者或兩者層合暫時接著材之步驟
步驟(b):於接合開始前預先加熱前述基板與前述支撐體之步驟
步驟(c):將前述基板與前述支撐體經由暫時接著材而接合之步驟
本發明中,前述步驟(b)中,將前述基板加熱至50℃以上250℃以下之溫度,將前述支撐體加熱至50℃以上250℃以下且與前述基板不同之溫度,並且於前述步驟(c)中,於預先加熱之前述基板之溫度與前述支撐體之溫度不同之狀態開始接合。加熱時間並未特別限定,但較佳為30秒~5分鐘左右。暫時接著材係與其所層合之基板及/或支撐體一起被加熱。
又,本發明中,於接合裝置內之腔室內等特定位置設定基板・支撐體後,基板與支撐體接觸之前的狀態稱為接合開始前。
圖2中顯示本發明之接合前實施基板與支撐體之加熱之一例。如圖2所示,將基板1設置於配置於接合裝置內之基板設置板4上,將預先層合有暫時接著材2之支撐體3設置於支撐體設置板5上。各板4、5具備任意之加熱手段,藉此可將基板側及支撐體側分別個別加熱至任意溫度。
本發明之層合體之製造方法中,於步驟(b)中,將基板溫度預先加熱至50℃以上250℃以下,將支撐體溫度預先加熱至50℃以上250℃以下,並且於步驟(c)中,於基板溫度與支撐體溫度不同之狀態同時開始接合。
又,基板溫度與支撐體溫度之溫度差可適當設定,但較佳於相差10℃以上之狀態開始接合。溫度差之上限宜為100℃以下之差,下限並未特別限定,但設為20℃以上之差更佳。再者,期望基板溫度比支撐體溫度更為高溫。
依據此等接合方法,可充分抑制源自接合步驟之空隙等之缺陷發生。
-步驟(a)-
步驟(a)係於基板之非加工面(非背面之面)及支撐體中之任一者或兩者層合暫時接著材之步驟。以下,雖以於支撐體層合暫時接著材之步驟為中心予以說明,但亦可於基板側層合暫時接著材。
暫時接著材可例如將樹脂組成物溶液藉由旋轉塗佈、輥塗佈器等之習知方法,層合(形成)於基板之非加工面及支撐體中之任一者或兩者(以下亦稱為「支撐體等」)。該情況下,旋轉塗佈後,對應於其溶劑之揮發條件,於80~200℃,較佳100~180℃之溫度,預先進行溶劑之揮發後供於使用。
層合包含2層以上之暫時接著材之情況下,各層可分別形成於基板與支撐體,亦可僅於基板或僅於支撐體形成複數層。形成複數層之情況下,可形成第1層後,再度藉由同樣方法形成與第1層鄰接之第2層。各層可藉由上述方法形成。
且,預先於脫模基材上形成為膜狀之暫時接著材亦可藉由層壓而於支撐體等上層合暫時接著材。
作為將暫時接著材層合於支撐體等之裝置,可使用市售裝置。藉由旋轉塗佈層合之情況可使用塗佈裝置例如SUSS公司之XBS300等,藉由層壓而層合之情況舉例為真空層壓機例如TAKATORI公司之TEAM-300等。
-步驟(b)-
步驟(b)係於接合開始前預先加熱前述基板與前述支撐體之步驟。本步驟可於接合裝置內進行。該情況下,加熱手段係內置於接合裝置,於設置基板及支撐體之板(腔室)中內置加熱器。又,加熱器若為習知之加熱裝置,則無特別問題。將前述基板加熱至50℃以上250℃以下之溫度,將前述支撐體加熱至50℃以上250℃以下且與前述基板不同之溫度。
較佳以相差10℃以上之溫度進行加熱,更佳以相差20℃以上之溫度進行加熱。
-步驟(c)-
步驟(c)係將前述基板與前述支撐體經由暫時接著材接合之步驟。較佳於減壓下貼合而接合。例如於步驟(b)加熱之溫度條件下於真空下(減壓下;壓力1Pa以下),藉由將該基板均一壓著並接合,而形成基板與支撐體經由暫時接著材接合之層合體。此時,壓著之時間為10秒至10分鐘,較佳為30秒至5分鐘。
例如如圖2所示,將基板1設置於基板設置板4上,將層合有暫時接著材2之支撐體3設置於支撐體設置板5上之後,於將基板側與支撐體側分別加熱至不同之特定溫度之狀態,如圖3所示,於減壓下將基板1均一壓著於支撐體3之層合有暫時接著材2之側並接合。
作為基板貼合裝置,於晶圓之情況下舉例為市售之晶圓接合裝置例如EVG公司之EVG520IS、850TB、SUSS公司之XBS300等。
[暫時接著材層]
本發明所用之暫時接著材可為單層,但亦可由複數層構成。作為暫時接著材較佳使用具有至少位於基板側之第一暫時接著材層(A)與比該第一暫時接著材層(A)更位於支撐體側之第二暫時接著材層(B)之2層以上之暫時接著材。且亦可進而具有第三暫時接著材層(C)或其他功能性層。
該情況,較佳使用前述第一暫時接著材層(A)與前述第二暫時接著材層(B)之熔融黏度比α/β於25℃下之熔融黏度比為10以下,較佳為0.05~5,更佳為0.05~1,於100℃以上200℃以下之最低熔融黏度比為100以上,較佳100~1000,更佳120~500之暫時接著材。
暫時接著材若為此等熔融黏度比,則由於可於短時間進行接合處理故而較佳。且若為此等熔融黏度比之暫時接著材,則由於接合之際暫時接著材不會附著於基板外周部故而較佳。
以下,針對本發明之層合體之製造方法中使用之暫時接著材(暫時接著材層)加以詳述,但可使用之暫時接著材不限定於此。
-第一暫時接著材層(A)-
第一暫時接著材層(A)係構成暫時接著材之暫時接著材層中位於基板側者。其材料並未特別限定,但基於對具有階差之基板等之適用性,較好使用具有良好嵌埋性之熱塑性樹脂。後文中,針對第一暫時接著材層(A)以熱塑性樹脂構成之例詳細說明,但本發明之層合體之製造方法中使用之暫時接著材不限定於該等。
第一暫時接著材層(A)較好為不具有有機聚矽氧烷,且玻璃轉移溫度-80~150℃左右之熱塑性樹脂,舉例為例如烯烴系熱塑性彈性體、聚丁二烯系熱塑性彈性體、苯乙烯系熱塑性彈性體、苯乙烯・丁二烯系熱塑性彈性體、苯乙烯・聚烯烴系熱塑性彈性體等,尤其較佳為耐熱性優異之氫化聚苯乙烯系彈性體。
作為此等熱塑性樹脂可使用市售品,具體舉例為例如TUFTEC (旭化成化學)、ESPOLEX SB系列(住友化學)、RABARON(三菱化學)、SEPTON(KURARAY)、DYNARON(JSR)等。又可舉例為以ZEONEX(日本ZEON)為代表之環烯烴聚合物及以TOPAS(日本塑膠)為代表之環狀烯烴共聚物。
如上述,作為第一暫時接著材層(A)之熱塑性樹脂,較好為熱塑性彈性體。又,亦可併用2種以上之樹脂。
若如此,則製作薄型基板後,由於可進而更容易自該基板剝離或洗淨暫時接著材,故可更容易處理易破裂之薄型基板。
上述熱塑性樹脂層組成物可溶解於溶劑中作成(A)層溶液,用於暫時接著材層之形成。作為溶劑為烴系溶劑,較佳為壬烷、對-薄荷烷、蒎烯、異辛烷、均三甲苯等,但基於其塗佈性,更佳為壬烷、對-薄荷烷、異辛烷、均三甲苯。再者,亦可根據需要進行過濾。較佳隨後,使用前進式輥塗佈器(forward roll coater)、逆轉式輥塗佈器、缺角輪塗佈器、模嘴塗佈器、唇模塗佈器、凹版塗佈器、浸漬塗佈器、氣刀塗佈器、毛細管式塗佈器、Raging&Rising(R&R)塗佈器、板狀塗佈器、棒塗佈器、敷料器、擠出成形機等塗佈於脫模基材上。隨後,將塗佈有(A)層溶液之脫模基材於產線上進行溶劑之去除,而形成第一暫時接著材層(A)。
此時,對形成之膜厚並未限制,但較佳以0.5~80μm,更佳為0.5~50μm之膜厚形成。且,該熱塑性樹脂中,基於提高其耐熱性之目的,可添加抗氧化劑,或為了提高塗佈性,可添加界面活性劑。作為抗氧化劑之具體例,可較佳地使用二-第三丁基酚等。作為界面活性劑之例可較佳地使用氟矽氧系界面活性劑X-70-1102(信越化學工業股份有限公司製)等。
-第二暫時接著材層(B)-
第二暫時接著材層(B)係構成暫時接著材之暫時接著材層中比上述第一暫時接著材層(A)更位於支撐體側之暫時接著材層。其材料並未特別限定,但較佳包含熱硬化性樹脂者,更好為包含矽氧系樹脂者。特佳為藉由以下述通式(1)及/或(3)所示之熱硬化性矽氧烷改質聚合物(含有矽氧烷鍵之聚合物)為主成分之熱硬化性樹脂組成物而形成。再者,前述樹脂組成物可根據需要含有交聯劑或硬化觸媒。
又,第二暫時接著材層(B)中亦可併用下述通式(1)表示之聚合物與下述通式(3)表示之聚合物。該情況下之比例(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。
<通式(1)之聚合物(酚性矽氧烷聚合物)>
具有下述通式(1)所示之重複單位之藉由凝膠滲透層析儀(GPC)測定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之含矽氧烷鍵之聚合物。
[式中,R1
~R4
表示可相同亦可不同之碳原子數1~8之1價烴基,且m為1~100之整數,B為正數,A為0或正數,X係下述通式(2)所示之2價有機基。A+B=1。又,較佳A為0~0.9,B為0.1~1,且A大於0之情況下,較佳A為0.1~0.7,B為0.3~0.9。
(式中,Z為自
之任一者選出之2價有機基,N為0或1,且R5
、R6
分別為碳原子數1~4之烷基或烷氧基,可相互相同亦可不同,k為0、1、2之任一者)]。
該情況下,作為R1
~R4
之具體例舉例為甲基、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。且B/A較佳為大於0且小於20,特佳為0.5~5。
<通式(3)之聚合物(環氧改質之矽氧烷聚合物)>
具有下述通式(3)所示之重複單位之藉由GPC測定之聚苯乙烯換算重量平均分子量為3,000~500,000之含矽氧烷鍵之聚合物。
[式中,R7
~R10
表示可相同亦可不同之碳原子數1~8之1價烴基,且n為1~100之整數,D為正數,C為0或正數,進而,Y係下述通式(4)所示之2價有機基,C+D=1,且較佳C為0~0.9,D為0.1~1,且C大於0之情況下,較佳C為0.1~0.7,D為0.3~0.9。
(式中,V為自
之任一者選出之2價有機基,p為0或1,且R11
、R12
分別為碳原子數1~4之烷基或烷氧基,可相互相同亦可不同,h為0、1、2之任一者)]。
該情況下,作為R7
~R10
之具體例舉例為與上述通式(1)中之R1
~R4
中例示者相同者。且,n為1~100之整數,較佳為3~60,更佳為8~40之整數。又,較佳D/C大於0且小於20,特佳為0.5~5。
<交聯劑>
以上述通式(1)及/或(3)之熱硬化性矽氧烷改質聚合物為主成分之熱硬化性組成物,為了其熱硬化性,於通式(1)之酚性矽氧烷聚合物之情況下,可含有選自藉由甲醛或甲醛-醇改質之胺基縮合物、三聚氰胺樹脂、脲樹脂、1分子中平均具有2個以上之羥甲基或烷氧基羥甲基之酚化合物及1分子中平均具有2個以上環氧基之環氧化合物之任1種以上之交聯劑。
此處,作為藉由甲醛或甲醛-醇改質之胺基縮合物、三聚氰胺樹脂、脲樹脂,可舉例以下者。例如藉由甲醛或甲醛-醇改質之三聚氰胺樹脂(縮合物)可藉由將改質三聚氰胺單體(例如三甲氧基甲基單羥甲基三聚氰胺)或其多聚物(例如二聚物、三聚物等之寡聚物體)依據習知方法與甲醛加成聚縮合至期望分子量而獲得。該等可使用1種或混合2種以上使用。
又,藉由甲醛或甲醛-醇改質之脲樹脂(縮合物)之調製例如可依據習知方法使期望分子量之脲縮合物以甲醛羥甲基化而改質,或將其進而以醇予以烷氧化並改質而進行。作為藉由甲醛或甲醛-醇改質之脲樹脂之具體例舉例為例如甲氧基甲基化脲縮合物、乙氧基甲基化脲縮合物、丙氧基甲基化脲縮合物等。又,該等可使用1種或混合2種以上使用。
又,作為1分子中平均具有2個以上之羥甲基或烷氧基羥甲基之酚化合物可舉例為例如(2-羥基-5-甲基)-1,3-苯二甲醇、2,2’,6,6’-四甲氧基甲基雙酚A等。又,該等酚化合物可使用1種或混合2種以上使用。
另一方面,於通式(3)之環氧改質矽氧烷聚合物(含矽氧烷鍵之聚合物)之情況下,可含有選自1分子中平均具有2個以上之酚基之酚化合物及1分子中平均具有2個以上環氧基之環氧化合物之任1種以上作為交聯劑。
此處,作為通式(1)及/或(3)中所用之具有多官能環氧基之環氧化合物並未特別限制,但可含有2官能、3官能、4官能以上之多官能環氧樹脂,例如日本化藥(股)製之EOCN-1020、EOCN-102S、XD-1000、NC-2000-L、EPPN-201、GAN、NC6000或如下述式之交聯劑。
上述通式(3)之環氧改質矽氧烷聚合物之情況,作為交聯劑之1分子中平均具有2個以上酚基之酚化合物之具體例,舉例為間,對-系甲酚酚醛清漆樹脂例如旭有機材工業(股)製EP-6030G,或3官能酚化合物例如本州化學工業(股)製Tris-P-PA,或4官能酚化合物例如旭有機材工業(股)製TEP-TPA等。
交聯劑之調配量,相對於上述通式(1)或式(3)之熱硬化性聚合物(含矽氧烷鍵之聚合物)100質量份,可為0.1~50質量份,較佳為0.1~30質量份,更佳為1~20質量份,亦可混合2種類或3種類以上調配。
又,相對於熱硬化性聚合物100質量份,如酸酐之硬化觸媒可含有10質量份以下。
[其他成分]
上述熱硬化性樹脂層組成物,可溶解於溶劑中作成(B)層溶液,可使用於形成暫時接著材層。作為溶劑舉例為例如環己酮、環戊酮、甲基-2-正戊基酮等之酮類;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;丙二醇單甲醚、乙二醇單甲醚、丙二醇單乙醚、乙二醇單乙醚、丙二醇二甲醚、二乙二醇二甲醚等之醚類;丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、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、乙酸第三丁酯、丙酸第三丁酯、丙二醇單-第三丁醚乙酸酯、γ-丁內酯等之酯類等,該等可單獨使用1種或併用2種以上。再者,亦可根據需要進行過濾。隨後,以與(A)層同樣之方法,塗佈於形成於脫模基材上之(A)層上,並去除溶劑而形成(B)層。
又,為了更提高耐熱性,亦可相對於熱硬化性聚合物100質量份,添加50質量份以下之習知抗氧化劑、氧化矽等之填料。再者,為了提高塗佈均一性,亦可添加界面活性劑。
作為可添加於第二暫時接著材層(B)之抗氧化劑之具體例,可舉例為四[亞甲基-(3,5-二-第三丁基-4-羥基氫桂皮酸酯)]甲烷(商品名:ADEKASTAB AO-60)等之受阻酚系化合物。
此時,形成之膜厚並未特別限定,但較佳為5~150μm,更佳為10~120μm。膜厚若為5μm以上,則於基板薄型化之研削步驟中可充分耐受,若為150μm以下,則於TSV形成步驟等之熱處理步驟中,不會有產生樹脂變形之虞,實用上可耐受故而較佳。
-第三暫時接著材層(C)-
本發明之層合體之製造方法中使用之暫時接著材,亦可根據需要進而具有第三暫時接著材層。使用第三暫時接著材層時,尤其較佳為含有下述(c1)、(c2)、(c3)成分之組成物(熱硬化性矽氧烷聚合物組成物)。
(c1)分子中具有烯基之有機聚矽氧烷:100質量份
(c2) 1分子中含有2個以上鍵結於矽原子之氫原子(Si-H基)之有機氫聚矽氧烷:(c2)成分中之Si-H基相對於前述(c1)成分中之烯基之莫耳比成為0.3~15之量
(c3)鉑系觸媒:以有效成分(質量換算)計,為超過0質量份且0.5質量份以下。
以下,針對各成分加以說明。
<(c1)成分>
(c1)成分係分子中具有烯基之有機聚矽氧烷。(c1)成分較佳為以1分子中之烯基莫耳數相對於Si莫耳數(烯基莫耳數/Si莫耳數)為0.3~10莫耳%之含有烯基之直鏈狀或分支狀之有機聚矽氧烷。特佳為以烯基莫耳數相對於上述Si莫耳數為0.6~9莫耳%之含有烯基之有機聚矽氧烷。
作為此等有機聚矽氧烷,具體可舉例為下述式(5)及/或(6)所示者。
(式中,R13
分別獨立為不具有脂肪族不飽和鍵之1價烴基,X1
分別獨立為含烯基之1價有機基,a為0~3之整數。且式(5)中,2a+1係1分子中烯基含量成為0.3~10莫耳%之數。式(6)中,l+2係1分子中烯基含量成為0.3~10莫耳%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之碳原子數1~10之1價烴基,若例示,則為甲基、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
之含烯基之1價有機基,較佳為碳原子數2~10之有機基,舉例為乙烯基、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烯基之1價烴基,工業上特佳為乙烯基。
上述通式(5)中,a為0~3之整數,但若a為1~3,由於分子鏈末端以烯基封端,故藉由反應性良好之分子鏈末端烯基,於短時間即可完成反應故而較佳。再者,就成本面而言,a=1就工業上較佳。該含烯基之有機聚矽氧烷之性狀較佳為油狀或生橡膠狀。該含烯基之有機聚矽氧烷可為直鏈狀,亦可為分支狀。且(c1)成分亦可併用2種以上。
又,上述(c1)成分之藉由GPC測定之數平均分子量(Mn)較佳為100000~500000。
<(c2)成分>
(c2)成分係交聯劑,係1分子中含有2個以上鍵結於矽原子之氫原子(Si-H基)之有機氫聚矽氧烷。(c2)成分係1分子中含有至少2個,較佳2個以上100個以下,更佳3個以上50個以下之鍵結於矽原子之氫原子(Si-H基)者,可使用直鏈狀、分支狀或環狀者。
(c2)成分之有機氫聚矽氧烷之25℃下之黏度較佳為1~5,000mPa・s,更佳為5~500mPa・s。該有機氫聚矽氧烷可為2種以上之混合物。又,黏度係藉由旋轉黏度計測定。
(c2)成分係以(c2)成分中之Si-H基相對於(c1)成分中之烯基之莫耳比(Si-H基/烯基)成為0.3~15,較佳成為0.3~10,特佳成為1~8之範圍而調配。該SiH基與烯基之莫耳比為0.3以上時,由於不會有交聯密度變低之虞,不會引起黏著劑層不硬化之問題之虞故而較佳。若為15以下,則不會有交聯密度變過高之虞,可獲得充分黏著力及觸黏。
<(c3)成分>
(c3)成分係鉑系觸媒(即鉑族金屬觸媒),舉例為例如氯化鉑酸、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、氯化鉑酸與含乙烯基之矽氧烷之反應物等。
(c3)成分之添加量為有效量,通常相對於(c1)、(c2)之合計,以鉑量(質量換算)計,為1~5,000ppm,較佳為5~2,000ppm。若為1ppm以上,則組成物之硬化性亦不會降低,即使交聯密度變低,保持力亦不會降低。若為5,000ppm以下,則可延長處理液之可使用時間。
上述熱硬化性矽氧烷聚合物組成物可溶解於溶劑中作成(C)層溶液,用於形成暫時接著材層。作為溶劑可較佳地使用例如戊烷、己烷、環己烷、異辛烷、壬烷、癸烷、對-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,該等可單獨使用1種或可併用2種以上。又,該熱硬化性矽氧烷聚合物組成物為了提高耐熱性而可添加習知抗氧化劑。再者,亦可進行過濾。隨後,以與(A)層、(B)層同樣方法於(B)層上形成(C)層,或塗佈於保護膜上並去除溶劑後,貼合於(B)層上,而可形成具有(C)層之暫時接著材。
此時,形成之膜厚較佳為0.1~30μm,特佳為1.0~15μm之間。膜厚若為0.1μm以上,則自基板或支撐體之剝離變得進而更容易。另一方面,膜厚若為30μm以下,則可充分耐受形成薄型晶圓時之研削步驟。又,該熱硬化性矽氧烷聚合物層(C)中,為了提高耐熱性,亦可相對於熱硬化性矽氧烷聚合物之各成分(c1)、(c2)、(c3)之混合合計100質量份,添加50質量份以下之氧化矽等之填料。
該(C)層可成為(A)層及(B)層之中間層,但亦可自基板側觀察依(A)層、(B)層、(C)層之順序設置。
[基板之製造方法]
藉由以上步驟所得之層合體可進而實施CVD加工或研磨・切削加工,隨後自支撐體剝離基板,而可獲得薄型晶圓。
又,所得薄型晶圓厚度典型上為5~300μm,更典型上較佳為10~100μm。
亦即,本發明亦提供基板之製造方法。亦即,係藉由上述層合體之製造方法獲得層合體後,進行加工前述基板之背面的步驟(d),隨後,於溶液剝離、機械剝離等之剝離步驟後,進而具有自前述層合體去除前述支撐體與前述暫時接著材後,洗淨前述基板之步驟(e),前述步驟(e)中,洗淨基板後之去除支撐體之側的面之水接觸角為未達30°之基板的製造方法。此時使用之洗淨液可使用利用一般有機溶劑之洗淨液。
加工前述基板背面之步驟(d)並未特別限定,但可舉例為實施CVD加工或研磨・切削加工等之步驟。前述步驟(e)中,自上述層合體去除支撐體與暫時接著材之方法,與洗淨基板之方法亦未特別限定,可使用習知方法。例如作為去除支撐體與暫時接著材之方法,舉例為自基板剝離去除該等之方法,作為洗淨基板之方法,舉例為噴霧可溶解殘留之暫時接著材等之洗淨溶劑後,進而噴霧任意溶劑進行清洗之方法。
又,測定經洗淨之基板的水接觸角時,只要使用習知測定方法即可。例如洗淨性試驗後之基板的水接觸角可使用協和界面科學(股)製接觸角計DM-301測定。
依據如上述之基板之製造方法,可製造不會發生於後續步驟中源自暫時接著材之不良,且可容易製造具有貫通電極構造或凸塊連接構造之薄型基板的基板。
[實施例]
以下顯示實施例及比較例更具體說明本發明,但本發明並非限定於該等實施例者。又,下述例中份為質量份。且Me表示甲基,Vi表示乙烯基。
[樹脂溶液製作例1]
將氫化苯乙烯・異戊二烯・丁二烯共聚物的熱塑性樹脂SEPTON 4033(含有苯乙烯30%,KURARAY製) 24g溶解於異壬烷176g中,獲得12質量%之氫化苯乙烯・異戊二烯・丁二烯共聚物之異壬烷溶液。所得溶液以0.2μm之膜過濾器過濾,獲得熱塑性樹脂之異壬烷溶液(A-1)。
[樹脂溶液製作例2]
將氫化苯乙烯・異戊二烯・丁二烯共聚物的熱塑性樹脂SEPTON 4044(含有苯乙烯32%,KURARAY製) 30g溶解於異壬烷176g中,獲得12質量%之氫化苯乙烯・異戊二烯・丁二烯共聚物之異壬烷溶液。所得溶液以0.2μm之膜過濾器過濾,獲得熱塑性樹脂之異壬烷溶液(A-2)。
[樹脂溶液製作例3]
於具備攪拌機、溫度計、氮氣置換裝置及回流冷卻器之燒瓶內饋入9,9’-雙(3-烯丙基-4-羥基苯基)茀(M-1) 43.1g、以平均構造式(M-3)表示之有機氫矽氧烷29.5g、甲苯135g、氯化鉑酸0.04g,升溫至80℃。隨後,以1小時於燒瓶內滴加1,4-雙(二甲基矽烷基)苯(M-5) 17.5g。此時,燒瓶內溫度上升至85℃。滴加結束後,進而於80℃熟成2小時後,餾除甲苯並且添加環己酮80g,獲得樹脂固形分濃度50質量%之以環己酮為溶劑之樹脂溶液。該溶液之樹脂分的分子量藉由GPC測定後,以聚苯乙烯換算之重量平均分子量為45,000。進而,於該樹脂溶液50g中,添加作為交聯劑之環氧交聯劑的EOCN-1020(日本化藥(股)製) 7.5g、作為硬化觸媒之和光純藥工業(股)製BSDM(雙(第三丁基磺醯基)重氮甲烷) 0.2g,進而添加作為抗氧化劑之四[亞甲基(3,5-二-第三丁基-4-羥基氫桂皮酸酯)]甲烷(商品名:ADEKASATB AO-60) 0.1g,以1μm之膜過濾器過濾,獲得樹脂溶液(B-1)。使前述樹脂硬化所得之硬化膜藉由動態黏彈性測定所測定之彈性率於25℃下為300MPa。
[樹脂溶液製作例4]
於具備攪拌機、溫度計、氮氣置換裝置及回流冷卻器之5L燒瓶內將環氧化合物(M-2) 84.1g溶解於甲苯600g後,添加化合物(M-3) 294.6g、化合物(M-4) 25.5g,加溫至60℃。隨後,投入碳擔持之鉑觸媒(5質量%) 1g,確認內部反應溫度升溫至65~67℃後,進而加溫至90℃,熟成3小時。其次冷卻至室溫後,添加甲基異丁基酮(MIBK) 600g,本反應溶液以過濾器加壓過濾而去除鉑觸媒。將該樹脂溶液中之溶劑減壓餾除並且添加丙二醇單甲醚乙酸酯(PGMEA) 270g,獲得固形分濃度60質量%之以PGMEA為溶劑之樹脂溶液。該樹脂溶液中之樹脂的分子量藉由GPC測定後,以聚苯乙烯換算之重量平均分子量為28,000。進而,於該樹脂溶液100g中,添加4官能酚化合物之TEP-TPA(旭有機材工業(股)製) 9g、四氫鄰苯二甲酸酐(新日本理化(股)製,RIKACID HH-A) 0.2g,以1μm之膜過濾器過濾,獲得樹脂溶液(B-2)。使前述樹脂硬化所得之硬化膜藉由動態黏彈性測定所測定之彈性率於25℃下為500MPa。
[樹脂溶液製作例5]
於由兩末端及側鏈具有3莫耳%之乙烯基之分子末端以SiMe2
Vi基封端之藉由GPC測定之數平均分子量(Mn)為50,000之聚二甲基矽氧烷100份及異十二烷400份所成之溶液中,添加混合下述式(M-7)表示之有機氫聚矽氧烷10份(相對於烯基為2莫耳)。進而添加相對於聚二甲基矽氧烷100份為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之膜過濾器過濾,獲得熱硬化性矽氧烷聚合物溶液(C-1)。
[樹脂溶液製作例6]
於由兩末端及側鏈具有3莫耳%之乙烯基之分子末端以SiMe2
Vi基封端之藉由GPC測定之數平均分子量(Mn)為50,000之聚二甲基矽氧烷100份及異十二烷400份所成之溶液中,添加混合下述式(M-6)表示之有機氫聚矽氧烷5份(相對於烯基為2莫耳)。進而添加相對於聚二甲基矽氧烷100份為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之膜過濾器過濾,獲得熱硬化性矽氧烷聚合物溶液(C-2)。
(實施例1)
使用缺角輪塗佈器作為膜塗佈器,將前述熱塑性樹脂溶液(A-1)以塗佈速度0.4m/min塗佈於作為脫模基材之聚對苯二甲酸乙二酯(PET)膜(厚38μm)上並乾燥,製作第一暫時接著材層的(A-1)層。接著使用缺角輪塗佈器作為膜塗佈器,將前述樹脂溶液(B-1)以塗佈速度0.4m/min塗佈於已形成上述(A-1)層之聚對苯二甲酸乙二酯(PET)膜上並乾燥,製作第二暫時接著材層的(B-1)層。進而,使用缺角輪塗佈器作為膜塗佈器,將前述熱硬化性矽氧烷聚合物溶液(C-1)以塗佈速度0.4m/min塗佈於已形成上述(B-1)層及(A-1)層之聚對苯二甲酸乙二酯(PET)膜上並乾燥,製作第三暫時接著材層的(C-1)層。隨後於製作之膜表面以壓力1MPa貼合作為保護膜之聚乙烯(PE)膜(厚100μm),以速度:0.4m/min、張力:30N,捲取於塑膠管,製作直徑130mm之膜捲筒。
步驟(a):於基板之非加工面或支撐體層合暫時接著材之步驟
將直徑200mm(厚:500μm)之玻璃板作為支撐體,使用真空層壓機TEAM-100(TAKATORI(股)製),將真空腔室內設定為真空度80Pa,邊自上述基板加工用暫時接著膜捲筒剝下保護膜,邊使由(A-1)層、(B-1)層及(C-1)層所成之複合膜狀暫時接著材延伸,以使(C-1)層配置於支撐體之方式層壓後,去除脫模基材。
步驟(b):於接合開始前預先加熱前述基板與前述支撐體之步驟
使用於表面全面形成有高度40μm、直徑40μm之銅柱之直徑200mm矽晶圓(厚:725μm)作為基板,以前述基板之銅柱面與步驟(a)中製作之前述支撐體之暫時接著材層面對向之方式,於真空貼合裝置(EVG520IS)內以表1中記載之溫度進行預加熱。
步驟(c):將前述基板與前述支撐體經由暫時接著材接合之步驟
將步驟(b)中配置之基板與支撐體,於腔室內壓力10-3
mbar以下、荷重為5kN開始接合。接著,將該層合體以表1中記載之溫度,以表1中記載之時間進行加熱,予以接著、接合,其次使用180℃之烘箱加熱層合體1小時,使(B-1)層與(C-1)層硬化,製作試料。
(實施例2~5及比較例1~4)
以表1中記載之條件,與實施例1同樣處理,製作試料。又,表1之暫時接著材之欄中,例如「A-1/B-1/C-1」表示暫時接著材由(A-1)層、(B-1)層及(C-1)層所成,前述(C-1)層配置於支撐體。
又,此處,為了以目視判別基板接著後之異常而使用玻璃板作為支撐體,但亦可使用晶圓等之光不透過之矽基板。
隨後,對經接合之基板(試料)進行下述試驗,將實施例及比較例之結果示於表1。又,以下述順序實施評價,但背面研削耐性試驗以後之評價判定為「×」之時點,終止其以後之評價。
-接著性試驗-
如上述,將使用180℃之烘箱加熱1小時而硬化所得之層合體(試料)冷卻至室溫,隨後以目視確認界面之接著狀況。於界面未發生氣泡等之異常時評價為良好並以「○」表示,發生異常時評價為不良並以「×」表示。
-背面研削耐性試驗-
以研磨機(DISCO(股)製,DAG810)使用金剛石研磨石,針對如上述使用180℃之烘箱加熱1小時而硬化所得之層合體(試料)進行矽晶圓之背面研削。研磨至最終基板厚50μm後,以光學顯微鏡(100倍)調查有無龜裂、剝離等之異常。未發生異常時以「○」表示,發生異常時以「×」表示。
-CVD耐性試驗-
將矽晶圓進行背面研削後之加工體導入CVD裝置,進行2μm之SiO2
膜之生成實驗,調查此時有無外觀異常。未發生外觀異常時以「○」表示,發生孔洞、晶圓鼓起、晶圓破損等時以「×」表示。CVD耐性試驗條件如以下。
裝置名:電漿CVD PD270STL(SAMCO(股)製)
RF500W、內壓40Pa
TEOS(原矽酸四乙酯):O2
=20sccm:680sccm
-剝離性試驗-
基板之剝離性係藉以下方法評價。首先,於結束CVD耐性試驗之晶圓加工體之薄型化至50μm之晶圓側使用切割框架貼合切割膠帶,藉由真空吸附該切割膠帶面而固定於吸附板。隨後,於室溫,以針固定玻璃之1點並拉起,而使玻璃基板剝離。50μm之晶圓無破裂而可剝離之情況以「○」表示,發生破裂等異常時評價為不良以「×」表示。
-洗淨去除性試驗-
將結束上述剝離性試驗後之經由切割膠帶安裝於切割框架之200mm晶圓(已暴露於耐熱性試驗條件者)固定於旋轉塗佈器上,噴霧3分鐘之作為洗淨溶劑之異壬烷後,邊旋轉晶圓邊噴霧異丙醇(IPA)進行清洗。隨後,觀察外觀以目視檢查有無殘存之接著材樹脂。未確認到樹脂殘存者評價為良好並以「○」表示,確認到樹脂殘存者評價為不良以「×」表示。
-接觸角試驗-
使用下述裝置測定上述洗淨性試驗後之晶圓的水接觸角。測定5次之接觸角的平均值示於表1。
測定裝置:協和界面科學(股)製 接觸角計DM-301
-熔融黏度測定-
使用流變計(HAAKE MARS II(英弘精機股份有限公司製)),以間隙500μm、樣品徑8mm、升溫速度10℃/min、頻率1Hz,自25℃至200℃之範圍進行測定。各層之熔融黏度比α/β示於表1。
如表1所示,判斷為滿足本發明要件之接合前之加熱條件下,基板與支撐體之暫時接著容易,剝離亦容易,尤其洗淨去除性優異(實施例1~5)。另一方面,接合前之加熱條件未滿足本發明要件之比較例1~4,接著性或洗淨去除性有問題。
又,本發明並非限定於上述實施形態者。上述實施形態為例示,凡具有與本發明申請專利範圍中記載之技術思想實質上相同之構成,且發揮同樣作用效果者,均包含於本發明之技術範圍。
1:基板
2:暫時接著材
(A):第一暫時接著材層
(B):第二暫時接著材層
3:支撐體
4:基板設置板
5:支撐體設置板
[圖1]係顯示以本發明之層合體之製造方法所得之層合體之一例的構成圖。
[圖2]係顯示本發明之接合前實施基板與支撐體之加熱之一例的構成圖。
[圖3]係顯示本發明之剛接合後之層合體之一例之構成圖。
1:基板
2:暫時接著材
(A):第一暫時接著材層
(B):第二暫時接著材層
3:支撐體
Claims (7)
- 一種層合體之製造方法,其係將背面應加工之基板的非加工面與支撐體經由暫時接著材接合的層合體之製造方法,其特徵係具有下述步驟:於前述基板之非加工面及前述支撐體中之任一者或兩者層合前述暫時接著材之步驟(a),於接合開始前預先加熱前述基板與前述支撐體之步驟(b),及將前述基板與前述支撐體經由前述暫時接著材而接合之步驟(c),前述步驟(b)中,將前述基板加熱至50℃以上250℃以下之溫度,將前述支撐體加熱至50℃以上250℃以下且與前述基板不同之溫度,並且於前述步驟(c)中,於預先加熱之前述基板之溫度與前述支撐體之溫度不同之狀態開始接合,作為前述暫時接著材係使用具有至少位於前述基板側之第一暫時接著材層(A)與比該第一暫時接著材層(A)更位於前述支撐體側之第二暫時接著材層(B)之2層以上之暫時接著材,前述第一暫時接著材層(A)與前述第二暫時接著材層(B)之熔融黏度比α/β係於25℃下之熔融黏度比為10以下,且於100℃以上200℃以下之最低熔融黏度比為100以上。
- 如請求項1之層合體之製造方法,其中前述步驟(c)係於前述基板之溫度與前述支撐體之溫度差10℃ 以上之狀態開始接合。
- 如請求項1之層合體之製造方法,其中前述步驟(a)中,以鄰接之方式形成前述第一暫時接著材層(A)與前述第二暫時接著材層(B)而層合前述暫時接著材。
- 如請求項1之層合體之製造方法,其中使用前述第二暫時接著材層(B)係由熱硬化性樹脂所成,且該熱硬化性樹脂經硬化所成之硬化膜之藉由動態黏彈性測定所測定之彈性率於25℃下為50MPa以上1GPa以下之暫時接著材。
- 如請求項1之層合體之製造方法,其中前述第二暫時接著材層(B)係藉由熱硬化性樹脂組成物所形成,該熱硬化性樹脂組成物相對於具有下述通式(1)所示之重複單位之重量平均分子量為3,000~500,000之含矽氧烷鍵之聚合物100質量份,含有0.1~50質量份之作為交聯劑之自藉由甲醛或甲醛-醇改質之胺基縮合物、1分子中平均具有2個以上羥甲基或烷氧基羥甲基之酚化合物及1分子中平均具有2個以上環氧基之環氧化合物所選出之任1種以上,
- 如請求項1之層合體之製造方法,其中前述第二暫時接著材層(B)係藉由熱硬化性樹脂組成物所形成,該熱硬化性樹脂組成物相對於具有下述通式(3)所示之重複單位之重量平均分子量為3,000~500,000之含矽氧烷鍵之聚合物100質量份,含有0.1~50質量份之作為交聯劑之自1分子中平均具有2個以上酚基之酚化合物及1分子中平均具有2個以上環氧基之環氧化合物所選出之任1種以上,
- 一種基板之製造方法,其特徵係具有下述步驟:藉由如請求項1至6中任一項之層合體之製造方法獲得層合體後,進行加工前述基板背面之步驟(d),其後進而自前述層合體去除前述支撐體與前述暫時接著材之後,洗淨前述基板之步驟(e),前述步驟(e)中,基板洗淨後之去除支撐體之側的面的水接觸角未達30°。
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