TWI483304B - 剝離方法、基板之黏著劑、及含基板之層合物 - Google Patents
剝離方法、基板之黏著劑、及含基板之層合物 Download PDFInfo
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- TWI483304B TWI483304B TW098132961A TW98132961A TWI483304B TW I483304 B TWI483304 B TW I483304B TW 098132961 A TW098132961 A TW 098132961A TW 98132961 A TW98132961 A TW 98132961A TW I483304 B TWI483304 B TW I483304B
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Description
本發明係有關由貼合支撐板之基板,剝離該支撐板之剝離方法,及基板之黏著劑與含基板之層合物。
伴隨著行動電話、數據AV機器及IC卡等的高機能化,而要求藉由搭載之半導體矽晶片(以下稱為晶片)小型化及薄板化,提高封裝內晶片的高積體化之需求增加。為了實現封裝內晶片的高積體化,需使晶片厚度薄化為25至150μm之範圍。
但藉由研削晶片之基體用的半導體晶圓(以下稱為晶圓)而薄化時會減弱其強度,而易使薄化發生斷裂或反撓。又難自動搬運因薄化而強度減弱之晶圓,故需人工搬運而使其處理性雜煩。
因此曾開發將稱為支撐板之玻璃、硬質塑料等所構成的板物貼合於研削之晶圓上,以保持晶圓強度而防止發生斷裂及晶圓反撓的晶圓支撐系統。因晶圓支撐系統可維持晶圓強度,故可使搬運薄化後之半導體晶圓自動化。
晶圓與支撐板係使用黏著膠帶、熱塑性樹脂、黏著劑等貼合。將貼合支撐板後之晶圓薄化後,於晶圓切粒前需由基板剝離支撐板。例如使用黏著劑貼合晶圓及支撐板時,可溶解黏著劑而由支撐板剝離晶圓。
先前溶解黏著劑而由支撐板剝離晶圓時,需耗時使溶劑浸透於黏著劑而溶解黏著劑等,結果由晶圓剝離支撐板需長時間。為了解決該問題專利文獻1曾記載,使用易剝離之黏著劑的方法。
專利文獻1係記載使用,含有分散著內包降低第1黏著材料之黏著力的離模劑,藉由熱熔融之微膠囊的第1黏著材料之第1黏著劑層上,具有含有分散著藉由熱膨脹之熱膨脹性粒子的第2黏著材料之第2黏著劑層的黏著劑,貼合工件。
其中記載使用該黏著劑貼合工件時,藉由加熱黏著劑而由微膠囊將離模劑放出於第1黏著劑層內,再利用熱膨脹性粒子之熱膨脹藉由壓力使第1及第2黏著劑層產生龜裂,而於工件不殘留黏著劑殘渣之情形下進行剝離。
文獻
專利文獻1:日本國公開專利公報「特開2008-94957號公報(2008年4月24日)」
由薄化後之晶圓剝離支撐板時,需注意薄化後之晶圓不會破損。但專利文獻1所記載之方法中,係利用加熱及熱膨脹性粒子之熱膨脹所產生的壓力,因此會提高晶圓破損之可能性。又會有因離模劑而污染晶圓,及含有熱膨脹性粒子而降低黏著性之問題。因此需求開發不會使晶圓污染及破損,且能以更短時間由支撐板剝離晶圓之剝離方法及黏著劑。
有鑑於上述課題,本發明之目的為,提供易以更短時間由晶圓剝離支撐板之剝離方法、層合物及黏著劑。
本發明之剝離方法為,特徵係由介有第1黏著劑層,及比第1黏著劑層更快溶解於溶劑之第2黏著劑層,或可溶解於不同於溶解第1黏著劑層之溶劑的溶劑之第2黏著劑層貼合支撐板的基板,剝離該支撐板之剝離方法中,包含溶解位於上述支撐板側之第2黏著劑層而由上述基板剝離上述支撐板之剝離步驟。
本發明之層合物為,特徵係含有基板,及形成於上述基板上之第1黏著劑層,及形成於上述第1黏著劑層上,比第1黏著劑層更快溶解於溶劑之第2黏著劑層,或可溶解於不同於溶解第1黏著劑層之溶劑的溶劑之第2黏著劑層,及貼合於上述第2黏著劑層之支撐板。
本發明之黏著劑為,特徵係形成上述層合物所含的第2黏著劑層用。
因本發明之剝離方法為,由介有第1黏著劑層,及比第1黏著劑層更快溶解於溶劑之第2黏著劑層,或可溶解於不同於溶解第1黏著劑層之溶劑的溶劑之第2黏著劑層貼合支撐板的基板,剝離該支撐板之剝離方法中,包含溶解位於上述支撐板側之第2黏著劑層而由上述基板剝離上述支撐板之剝離步驟,故易以更短時間由貼合支撐板之基板剝離支撐板。
下面將參考圖1及圖2說明本發明之一實施形態的剝離方法。圖1為,本發明之剝離方法所使用的,本發明之層合物1的剖面圖,圖2(a)至(e)為,本發明之一實施形態的剝離方法之各步驟剖面圖。如圖1及圖2中(a)至(e)所示,層合物1係由含有晶圓(基板)2、支撐板3、第1黏著劑層4及第2黏著劑層5構成。層合物1中,係第1黏著劑層4及第2黏著劑層5為黏著層合物6,貼合晶圓2及支撐板3。
本發明之剝離方法為,由介有第1黏著劑層4,及比第1黏著劑層4更快溶解於溶劑之第2黏著劑層5,或可溶解於不同於溶解第1黏著劑層4之溶劑的溶劑之第2黏著劑層5貼合支撐板3的晶圓2,剝離支撐板3之剝離方法中,包含溶解位於支撐板3側之第2黏著劑層5而由上述晶圓2剝離上述支撐板3之剝離步驟。
又,本實施形態所使用的支撐板3為,厚度方向具有貫穿孔之多孔支撐板3,但本發明非限定於此。使用多孔支撐板3,可介由孔將溶劑供給第2黏著劑層5。
第1黏著劑層4為,接合晶圓2及第2黏著劑層5。第1黏著劑層4可為,由含有介由第2黏著劑層5可充分接合晶圓2及支撐板3之黏著化合物的第1黏著劑材料形成,適用先前已知之黏著劑材料。形成第1黏著劑層4之第1黏著劑材料如,含有丙烯酸-苯乙烯系樹脂、馬來醯亞胺系樹脂之物。
丙烯酸-苯乙烯系樹脂如,以苯乙烯或苯乙烯之衍生物,及(甲基)丙烯酸酯等為單體,聚合而得之樹脂。
(甲基)丙烯酸酯如,由鏈式構造形成之(甲基)丙烯酸烷酯、具有脂肪族環之(甲基)丙烯酸酯、具有芳香族環之(甲基)丙烯酸酯。由鏈式構造形成之(甲基)丙烯酸烷酯如,具有碳數15至20之烷基的丙烯酸基系長鏈烷酯、具有碳數1至14之烷基的丙烯酸基系烷酯等。丙烯酸基系長鏈烷酯如,烷基為n-十五烷基、n-十六烷基、n-十七烷基、n-十八烷基、n-十九烷基、n-二十烷基等之丙烯酸或甲基丙烯酸之烷酯。又該烷基可為支鏈狀。
具有碳數1至14之烷基的丙烯酸基系烷酯如,既存的丙烯酸基系黏著劑所使用之已知的丙烯酸基系烷酯。例如烷基為甲基、乙基、丙基、丁基、2-乙基己基、異辛基、異壬基、異癸基、十二烷基、月桂基、十三烷基等所形成之丙烯酸或甲基丙烯酸之烷酯。
具有脂肪族環之(甲基)丙烯酸酯如,環己基(甲基)丙烯酸酯、環戊基(甲基)丙烯酸酯、1-金剛基(甲基)丙烯酸酯、降莰基(甲基)丙烯酸酯、異冰片基(甲基)丙烯酸酯、三環癸烷基(甲基)丙烯酸酯、四環十二烷基(甲基)丙烯酸酯、二環戊烷基(甲基)丙烯酸酯等,較佳為異冰片基甲基丙烯酸酯、二環戊烷基(甲基)丙烯酸酯。
具有芳香族環之(甲基)丙烯酸酯並無特別限定,芳香族環如,苯基、苄基、甲苯基、二甲苯基、聯苯基、萘基、蒽基、苯氧基甲基、苯氧基乙基等。又芳香族環可具有碳數1至5之鏈狀或支鏈狀的烷基。具體上較佳為苯氧基乙基丙烯酸酯。
馬來醯亞胺系樹脂如,以N-甲基馬來醯亞胺、N-乙基馬來醯亞胺、N-n-丙基馬來醯亞胺、N-異丙基馬來醯亞胺、N-n-丁基馬來醯亞胺、N-異丁基馬來醯亞胺、N-sec-丁基馬來醯亞胺、N-tert-丁基馬來醯亞胺、N-n-戊基馬來醯亞胺、N-n-己基馬來醯亞胺、N-n-庚基馬來醯亞胺、N-n-辛基馬來醯亞胺、N-月桂基馬來醯亞胺、N-硬脂醯馬來醯亞胺等具有烷基之馬來醯亞胺、N-環丙基馬來醯亞胺、N-環丁基馬來醯亞胺、N-環戊基馬來醯亞胺、N-環己基馬來醯亞胺、N-環庚基馬來醯亞胺、N-環辛基馬來醯亞胺等具有脂肪族碳化氫基之馬來醯亞胺、N-苯基馬來醯亞胺、N-m-甲基苯基馬來醯亞胺、N-o-甲基苯基馬來醯亞胺、N-p-甲基苯基馬來醯亞胺等具有芳基之芳香族馬來醯亞胺等為單體,聚合而得之樹脂。
為了維持晶圓2及支撐板3之接合及耐熱性,第1黏著劑層4之層厚較佳為15至30μm,特佳為15μm,但非限定於此。第1黏著劑層4可由,將含有上述接合化合物之第1黏著劑材料塗佈於晶圓2後,層狀固化於晶圓2上而形成。又可由,將預先層狀固化第1黏著劑材料而得之物移動至晶圓2上而形成。
第2黏著劑層5為,位於支撐板3側接合第1黏著劑層4及支撐板3。第2黏著劑層5係以比第1黏著劑層4更快溶解於溶劑,或可溶解於不同於溶解第1黏著劑層4之溶劑的溶劑之形態形成。本發明之黏著劑為形成第2黏著劑層5用之物,又其為含有後述第2黏著劑材料之物。
企圖由高溶解性之第2黏著劑材料形成比第1黏著劑層4更快溶解於溶劑之第2黏著劑層5時,可由含有平均分子量比上述第1黏著劑材料所含的黏著化合物更小之黏著化合物的第2黏著劑材料形成。
藉由以比第1黏著劑層4更快溶解於溶劑之形態形成第2黏著劑層5,而可由晶圓2剝離支撐板3時,係介由支撐板3之孔將溶劑供給第2黏著劑層5,而以更短時間溶解溶解速度較快之第2黏著劑層5,故可以更短時間剝離接合於第2黏著劑層5之支撐板3。又剝離支撐板3後溶解第1黏著劑層4時,因不存在支撐板3故無妨礙溶劑浸透之問題,而可以短時間溶解第1黏著劑層4。
比第1黏著劑層4更快溶解於溶劑之第2黏著劑層5較佳由,含有平均分子量相當於第1黏著劑層4所含的黏著化合物之平均分子量的10%至30%之黏著化合物的第2黏著劑材料形成。如此可得充分縮短剝離時間用之溶解速度。第1黏著劑層4係由先前所使用一般的第1黏著劑材料形成時,可使用含有平均分子量5000至10000之黏著化合物的第2黏著劑材料形成第2黏著劑層5。例如使用含有平均分子量40000之黏著化合物的第1黏著劑材料形成第1黏著劑層4時,可使用含有平均分子量10000之黏著化合物的第2黏著劑材料形成第2黏著劑層5。
企圖由對溶解第1黏著劑層4之溶劑具有耐性的第2黏著劑材料形成,可溶解於不同於溶解第1黏著劑層4之溶劑的溶劑之第2黏著劑層5時,較佳由對不同於溶解第1黏著劑層4之溶劑的溶劑具有較快溶解速度之第2黏著劑材料形成。
藉由以溶解於不同於溶解第1黏著劑層4之溶劑的溶劑之形態形成第2黏著劑層5,而可由晶圓2剝離支撐板3時,係介由支撐板3之孔將溶劑供給第2黏著劑層5,故可利用溶解第2黏著劑層5之溶劑僅溶解第2黏著劑層5,而剝離以第2黏著劑層5接合之支撐板3。又剝離支撐板3後溶解第1黏著劑層4時,因不存在支撐板3故無妨礙溶劑浸透之問題,而可快速溶解第1黏著劑層4。
因本實施形態係使用多孔支撐板3,故晶圓2之薄化過程中,例如光微影步驟的背洗液等溶劑可介由支撐板3之孔接觸第2黏著劑層5。第1黏著劑層4般貼合晶圓2及支撐板3用一般的黏著劑層為,對PGMEA(propylene glycol monomethyl ether acetate)、HP(2-庚酮)等含有有機溶劑之溶劑無耐性,於薄化過程中該類溶劑會介由支撐板3的孔入浸而溶解黏著劑層。因此支撐板3會發生脫層,而有無法良好進行薄化步驟之問題。為了解決該問題,先前接觸溶劑之過程中,係以背膠阻塞支撐板3的孔,以防止溶劑浸入支撐板3的孔內,因此會降低處理效率及提高成本而不宜。
因本發明藉由支撐板3側設有對上述般含有有機溶劑之溶劑具有耐性的第2黏著劑層5,以對上述溶劑具有耐性之第2黏著劑層5被覆第1黏著劑層4,故既使上述溶劑介由支撐板3的孔浸入,也不會溶解第1黏著劑層4及第2黏著劑層5,因此支撐板3不會發生脫層,而無需使用背膠阻塞支撐板3的孔。
第2黏著劑層5可以能溶解於不同於第1黏著劑層4之溶劑的形態形成,又由可溶解於有機溶劑之第1黏著劑材料形成第1黏著劑層4時,可由對有機溶劑具有耐性之第2黏著劑材料形成第2黏著劑層5。該類第2黏著劑材料所含的黏著化合物可使用碳化氫樹脂或極性溶劑溶解性(例如水溶性)化合物。
碳化氫樹脂如,環烯烴系聚合物(以下稱為「樹脂(A)」)、萜烯樹脂、松香系樹脂及石油樹脂群中所選出之至少1種樹脂(以下稱為「樹脂(B)」)等,但非限定於此。
前述樹脂(A)為,由含有環烯烴系單體(a1)之單體成份聚合而得的樹脂。具體例如,含有環烯烴系單體(a1)之單體成份的開環(共)聚合物、含有環烯烴系單體(a1)之單體成份附加(共)聚的樹脂。
構成前述樹脂(A)之單體成份所含的前述環烯烴系單體(a1)如,降莰烯、降莰二烯等二環物、二環戊二烯、二羥基戊二烯等三環物、四環十二烯等四環物、環戊二烯三聚物等五環物、四環戊二烯等七環物、或此等多環物之烷基(甲基、乙基、丙基、丁基等)取代物、鏈烯基(乙烯基等)取代物、亞烷基(亞乙基等)取代物、芳基(苯基、甲苯基、萘基等)取代物等。其中特佳如下述一般式(1)所示般,由降莰烯、四環十二烯、及此等之烷基取代物群中所選出的降莰烯系單體。
【化1】
(式(1)中,R1
至R2
各自獨立為氫原子或碳數1至6之烷基,n為0或1)。
構成前述樹脂(A)之單體成份可含有能與前述環烯烴系單體(a1)共聚合之單體,較佳如含有下述一般式(2)所示之鏈烯單體(a2)。鏈烯單體(a2)如,乙烯、丙烯、1-丁烯、異丁烯、1-己烯、α-烯烴等。前述鏈烯單體(a2)可為直鏈狀或支鏈狀。
【化2】
(式(2)中,R3
至R6
各自獨立為氫原子或碳數1至4之烷基)。
構成前述樹脂(A)之單體成份較佳為,其中50質量%以上為前述環烯烴系單體(a1),更佳為60質量%以上為前述環烯烴系單體(a1)。環烯烴系單體(a1)為單體成份全體之50質量%以上時,可得高溫環境下具有良好黏著強度之物。
又前述樹脂(A)較佳如高溫下可抑制氣體發生,由上述式(1)所示之環烯烴系單體(a1)及上述式(2)所示之鏈烯單體(a2)所形成之單體成份聚合而得的樹脂般,不具有極性基之樹脂。
聚合前述單體成份時之聚合方法及聚合條件等並無特別限制,可依常法適當設定。
可作為前述樹脂(A)用之市售品如,聚塑料公司製「TOPAS」、三井化學公司製「APEL」、日本傑翁公司製「ZEONOR」及「ZEONEX」、JSR公司製「ARTON」等。
前述樹脂(A)之玻璃化點(Tg)較佳為60℃以上,樹脂(A)之玻璃化點特佳為70℃以上。樹脂(A)之玻璃化點為60℃以上時,將黏著劑組成物暴露於高溫環境下可抑制黏著層軟化。
前述樹脂(B)為萜烯系樹脂、松香系樹脂及石油樹脂群中所選出之至少1種樹脂。具體之前述萜烯系樹脂如,萜烯樹脂、萜烯酚樹脂、改性萜烯樹脂、氫化萜烯樹脂、氫化萜烯酚樹脂等,前述松香系樹脂如,松香、松香酯、氫化松香、氫化松香酯、聚合松香、聚合松香酯、改性松香等,前述石油樹脂如,脂肪族或芳香族石油樹脂、氫化石油樹脂、改性石油樹脂、脂環族石油樹脂、香豆酮─茚石油樹脂等。其中較佳為氫化萜烯樹脂、氫化石油樹脂。
前述樹脂(B)之軟化點並無特別限制,較佳為80至160℃。樹脂(B)之軟化點為80℃以上時,將黏著劑組成物暴露於高溫環境下時可抑制軟化,不會發生黏著不良。又樹脂(B)之軟化點為160℃以下時,可得剝離黏著劑組成物時具有良好剝離速度之物。
前述樹脂(B)之分子量並無特別限定,較佳為300至3000。前述樹脂(B)之分子量為300以上時,可得具有充分耐熱性之物,可減少高溫環境下之脫氣量。又樹脂(B)之分子量為3000以下時,可得剝離黏著劑組成物時具有良好剝離速度之物。本發明之樹脂(B)的分子量係指,由凝膠滲透色譜法(GPC)測定之聚苯乙烯換算的分子量。
又可混合使用前述樹脂(A)及前述樹脂(B)。混合後可得具有良好耐熱性及剝離速度之物。例如前述樹脂(A)與前述樹脂(B)之混合比為(A):(B)=80:20至55:45(質量比)時,可得優良剝離速度、高溫環境下之耐熱性,及柔軟性而為佳。
又,極性溶劑溶解性化合物如,膠原肽、纖維素、聚乙烯醇(PVA)、澱粉等,但非限定於此。
膠原肽可由,藉由螺旋狀會合聚肽鏈之膠原分子加熱改性,解開部分螺旋而明膠化後加水分解而生成。膠原分子適用來自哺乳類之膠原分子及來自魚類之膠原分子。又可使用一般市售之膠原分子,但較佳為,所生成的膠原肽相對於極性溶劑之溶解速度為100至300nm/sec之膠原分子,特佳為200nm/sec之膠原分子。
形成第2黏著劑層5之第2黏著劑材料可適當選用適合於層合物1實施處理之物。例如晶圓2之薄化過程中使用大量水,而所使用的第2黏著劑材料為水溶性化合物時,可能溶解第2黏著劑層5,因此第2黏著劑材料較佳使用碳化氫樹脂。
為了維持晶圓2及支撐板3之接合性及耐熱性,第2黏著劑層5之層厚較佳為,比第1黏著劑層4更薄,又以相當於黏著層合物6之總層厚的10至20%之層厚為佳,但非限於此。例如第1黏著劑層4之層厚為15μm時,第2黏著劑層5之層厚可為3μm。第2黏著劑層5可由,將含有上述黏著化合物之第2黏著劑材料塗佈於第1黏著劑層4後,層狀固化於第1黏著劑層4上而形成。又可將預先層狀固化第2黏著劑材料而得之物移動至第1黏著劑層4上而形成。
又,藉由將混合第1黏著劑材料及第2黏著劑材料而得之物塗佈於晶圓2後雙層狀固化於晶圓2,可形成第1黏著劑層4及第2黏著劑層5。此時第1黏著劑材料及第2黏著劑材料,可選用相互混合但不乳膠化之物中,藉由分子量的不同,而於晶圓2側形成第1黏著劑層4後,可於第1黏著劑層4上形成第2黏著劑層5般之材料。
本發明之層合物1可由,於晶圓2上形成第1黏著劑層4後,於第1黏著劑層4上形成第2黏著劑層5,再於第2黏著劑層5上接合支撐板3而形成。又可於支撐板3上形成第2黏著劑層5後,於第2黏著劑層5上形成第1黏著劑層4,再於第1黏著劑層4上接合晶圓2而形成。另外可於晶圓2上形成第1黏著劑層4之物,及支撐板3上形成第2黏著劑層5之物後,藉由接合第1黏著劑層4與第2黏著劑層5而形成。
其次將參考圖2中(a)至(e)說明本發明之剝離方法的處理流程。本發明之剝離方法至少包含上述剝離步驟即可,但以該剝離步驟後另包含溶解第1黏著劑層4之溶解步驟為佳。本實施形態係以包含該溶解步驟之本發明的剝離方法為例進行說明。
首先,本發明之剝離步驟為,如圖2(a)所示準備剝離處理對象之本發明的層合物1。其次如圖2(b)所示,由支撐板3未接觸第2黏著劑層5側,注入溶解第2黏著劑層5用之溶劑。注入之溶劑係介由支撐板3之貫穿孔浸入而浸透於第2黏著劑層5,以溶解第2黏著劑層5。
此時溶解第2黏著劑層5之溶劑可因應第2黏著劑層5之特性適當選擇。第2黏著劑層5係由含有平均分子量小於第1黏著劑材料所含的黏著化合物之黏著化合物的第2黏著劑材料形成時,可使用與溶解第1黏著劑材料用之溶劑相同的溶劑。該類溶劑較佳為,溶解度參數(SP值)大於8小於10之溶劑,例如PGMEA、HP等。
又,第2黏著劑層5係由碳化氫樹脂形成時,適用非極性溶劑,該類溶劑如碳化氫系溶劑。前述碳化氫系溶劑如,直鏈、支鏈或環狀碳化氫。具體例如,己烷、庚烷、辛烷、壬烷、甲基辛烷、癸烷、十一烷、十二烷、十三烷等直鏈狀碳化氫、碳數3至15之支鏈狀碳化氫;香葉醇、橙花醇、沉香醇、檸檬醛、香茅醇、p-烷、o-烷、m-烷、二苯基烷、薄荷醇、異薄荷醇、新薄荷醇、檸檬烯、α-萜品烯、β-萜品烯、γ-萜品烯、α-萜品醇、β-萜品醇、γ-萜品醇、萜品烯-1-醇、萜品烯-4-醇、1,4-萜品、1,8-萜品、黃蒿萜酮、紫羅酮、酮、樟腦、莰烷、冰片、降莰烷、蒎烷、α-蒎烯、β-蒎烯、烷、α-烯、β-烯、蒈烷、樟腦、長葉烯、1,4-桉樹腦、1,8-桉樹腦等一萜烯類、松香烷、松香酸等二萜烯類等之環狀碳化氫(萜烯類)。
其中較佳為使用具有環狀骨格之碳化氫的萜烯系溶劑。該類萜烯系溶劑具體上又以易取得之一萜烯類為佳,其中較佳為可具有較高溶解性能的檸檬烯、蒎烯、蒎烷及p-烷中所選出之至少1種。又適用此等中SP值為8以下之非極性溶劑,更佳為使用SP值為7.4以下之非極性溶劑。
另外第2黏著劑層5係由極性溶劑溶解性(例如水溶性)化合物形成時,適用先前已知之極性溶劑作為溶劑,但以使用SP值為10以上之極性溶劑為佳,更佳為使用SP值為12以上之極性溶劑。SP值為12以上之極性溶劑如,水、甲醇、乙醇、異丙醇等。
接著如圖2(c)所示,溶解第2黏著劑層5後剝離支撐板3。剝離支撐板3後,洗淨去除第1黏著劑層4上殘存之第2黏著劑層5。
其後如圖2(d)所示,將溶解第1黏著劑層4之溶劑注入第1黏著劑層4全面溶解第1黏著劑層4後,如圖2(e)所示,得剝離支撐板3,且去除第1黏著劑層4及第2黏著劑層5之晶圓2。溶解第1黏著劑層4之溶劑可使用,與溶解由含有平均分子量小於上述第1黏著劑材料所含的黏著化合物之黏著化合物的第2黏著劑材料形成之第2黏著劑層5用的溶劑相同之溶劑。
如上述使用本發明之剝離方法由晶圓2剝離支撐板3時,係介由支撐板3之孔將溶劑供給第2黏著劑層5,故可藉由溶解第2黏著劑層5之溶劑以短時間溶解第2黏著劑層5,可剝離接合於第2黏著劑層5之支撐板3。剝離支撐板3後溶解第1黏著劑層4,因不存在支撐板3故無妨礙溶劑浸透之問題,因此可更快速溶解第1黏著劑層4。
本發明中作為第1黏著劑材料及第2黏著劑材料用之黏著劑組成物可含有熱聚合禁止劑。熱聚合禁止劑為,可有效防止熱產生之自由基聚合反應之物質。熱聚合禁止劑對自由基具有較高反應性,可比單體更優先進行反應,因此可禁止聚合。故含有熱聚合禁止劑之黏著劑組成物於高溫環境下(特別是250℃至350℃)可抑制黏著劑組成物之聚合反應。因此既使經歷250℃下加熱1小時之高溫步驟,也易溶解黏著劑組成物,故高溫步驟後也易剝離由黏著劑組成物形成之黏著劑層,及抑制殘渣發生。
熱聚合禁止劑若為能有效防止因熱而自由基聚合反應之物,並無特別限定,但以酚系熱聚合禁止劑為佳。
熱聚合禁止劑如,焦棓酚、苯醌、氫醌、甲烯藍、tert-丁基兒茶酚、一苄醚、甲基氫醌、戊醌、戊氧基氫醌、n-丁基苯酚、苯酚、氫醌一丙醚、4,4’-(1-甲基亞乙基)雙(2-甲基苯酚)、4,4’-(1-甲基亞乙基)雙(2,6-二甲基苯酚)、4,4’-[1-[4-(1-(4-羥基苯基)-1-甲基乙基)苯基]亞乙基]雙酚、4,4’,4”-亞乙基三(2-甲基苯酚)、4,4’,4”-亞乙基三酚、1,1,3-三(2,5-二甲基-4-羥基苯基)-3-苯基丙烷、2,6-二-tert-丁基-4-甲基苯酚、2,2’-伸甲基雙(4-甲基-6-tert丁基苯酚)、4,4’-亞丁基雙(3-甲基-6-tert丁基苯酚)、4,4’-硫雙(3-甲基-6-tert丁基苯酚)、3,9-雙[2-(3-(3-tert丁基-4-羥基-5-甲基苯基)-丙醯氧基)-1,1-二甲基乙基]-2,4,8,10-四噁螺(5,5)十一烷、三乙二醇-雙-3-(3-tert丁基-4-羥基-5-甲基苯基)丙酸酯、n-辛基-3-(3,5-二-tert丁基-4-羥基苯基)丙酸酯、季戊四醇基四[3-(3,5-二-tert丁基-4-羥基苯基)丙酸酯(商品名IRGANOX 1010,吉巴斯公司製)、三(3,5-二-tert丁基羥基苄基)三聚異氰酸酯、硫二伸乙基雙[3-(3,5-二tert丁基-4-羥基苯基)丙酸酯],其中較佳為酚系熱聚合禁止劑。
熱聚合禁止劑之含量可因應主成份所含的聚合物、黏著劑組成物之用途及使用環境適當決定。但相對於主成份所含的聚合物較佳為0.1質量%以上10.0質量%以下,更佳為0.5質量%以上7.0質量%以下,最佳為1.0質量%以上5.0質量%以下。上述範圍內可良好發揮抑制因熱而聚合之效果,且高溫步驟後更易剝離黏著劑層。又上述範圍內可防止斷裂發生。
支撐板3之剝離時間係以由最初注入溶劑開始,至去除支撐板3及溶解全部黏著劑層之時間為基準,進行評估。
以下述表1所示添加量,藉由已知之自由基聚合合成樹脂1至2。
表1中質量平均分子量為,藉由GPC測定之標準聚苯乙烯換算的質量平均分子量。
將上述樹脂1(100質量份)溶解於PGMEA,調整樹脂1之濃度為40質量%的黏著劑組成物1。又將上述樹脂2(100質量份)溶解於PGMEA,調整樹脂2之濃度為40質量%的黏著劑組成物2。
將黏著劑組成物1塗佈於5英寸矽晶圓2上,以80℃乾燥5分鐘後,形成層厚15μm之第1黏著劑層4。其次將黏著劑組成物2塗佈於第1黏著劑層4上,以80℃乾燥5分鐘後,形成層厚3μm之第2黏著劑層5。接著將多孔支撐板3接合於第2黏著劑層5上。
由支撐板3未接觸第2黏著劑層5側將HP注入上述製作之層合物1。又相對於HP之第2黏著劑層5的溶解速度為200nm/sec。溶解第2黏著劑層5後剝離支撐板3,再將HP注入第1黏著劑層4全面。又相對於HP於第1黏著劑層4的溶解速度為100nm/sec,溶解第1黏著劑層4所需的時間約為60秒。支撐板3之剝離時間約為2分30秒。
同實施例1將黏著劑組成物1塗佈於5英寸矽晶圓2上,以80℃乾燥5分鐘後,形成層厚15μm之第1黏著劑層4。其次將膠原肽之水溶液(30質量%)塗佈於第1黏著劑層4上,以80℃乾燥5分鐘後,形成層厚3μm之第2黏著劑層5。接著將多孔支撐板3接合於第2黏著劑層5。
由支撐板3未接觸第2黏著劑層5側將水注入上述製作之層合物1。又相對於水之第2黏著劑層5的溶解速度為340nm/sec。溶解第2黏著劑層5後剝離支撐板3,再將HP注入第1黏著劑層4全面。又相對於HP之第1黏著劑層4的溶解速度為100nm/sec,溶解第1黏著劑層4所需的時間約為60秒。支撐板3之剝離時間約為1分30秒。
同黏著劑組成物1塗佈於6英寸矽晶圓2上,以110℃乾燥3分鐘後以150℃再乾燥6分鐘,形成層厚30μm之第1黏著劑層4。其次將含有氫化萜烯樹脂(雅斯哈公司製)之p-烷溶液(30質量%)塗佈於第1黏著劑層4上,以120℃乾燥3分鐘後,形成層厚7μm之第2黏著劑層5。接著將多孔支撐板接合於第2黏著劑層5上。
由支撐板3未接觸第2黏著劑層5側將p-烷注入上述製作之層合物1。又相對於p-烷之第2黏著劑層5的溶解速度為400nm/sec。溶解第2黏著劑層5後剝離支撐板3,再將HP注入第1黏著劑層4全面。又相對於HP之第1黏著劑層4的溶解速度為100nm/sec,溶解第1黏著劑層4所需的時間約為60秒。支撐板3之剝離時間為1分鐘。
將黏著劑組成物1塗佈於6英寸矽晶圓2上,以110℃乾燥3分鐘後,以150℃再乾燥6分鐘,形成層厚30μm之第1黏著劑層4。其次各自準備含有於表2至4記載之單獨聚合物,單獨低聚物,或以一定比率混合此等之物的p-烷溶液(30質量%)作為黏著劑組成物2用,將其塗佈於第1黏著劑層4後,以120℃乾燥3分鐘,形成層厚7μm之第2黏著劑層5。接著將多孔支撐板接合於第2黏著劑層5上。
又本實施例所使用的以金屬芳香類觸媒共聚合降莰烯及乙烯而得之環烯烴共聚物(環烯烴─乙烯A)為,以化學式(3):化學式(4)=35:65之質量比含有下述化學式(3)及化學式(4)所表示的重覆單位之Tg=70℃、質量平均分子量(Mw)=98200、分散度(Mw/Mn)=1.69、玻璃化點70℃的環烯烴乙烯系聚合物A(TOPAS8007COC、聚塑料公司製)。
【化3】
【化4】
又,所使用的低聚物為軟化點為135℃、分子量820之萜烯樹脂A(雅斯哈公司製,庫里亞P135、氫化萜烯樹脂)、及軟化點115℃、分子量650之萜烯樹脂B(雅斯哈公司製,庫里亞P115,氫化萜烯樹脂),及軟化點105℃、分子量630之萜烯樹脂C(雅斯哈公司製,庫里亞P105,氫化萜烯樹脂)。
對上述形成之層合物1進行下述試驗項目之試驗。結果如表2所示。
將各層合物1浸漬於p-烷中(23℃下5分鐘),並以浸漬於p-烷後可完全溶解第2黏著劑層5之物為「○」,殘存之物為「×」。另外完全溶解第2黏著劑層5時,由層厚與溶解時間之關係算出溶解速度(nm/sec)。又就生產性觀點溶解速度較佳為60nm/sec。
如表2至4所示,實施例2至24之第2黏著劑層5均可完全溶解於p-烷。又溶解速度為51.4至520nm/s。
以230℃將各層合物1加熱1小時後,浸漬於p-烷。浸漬於p-烷後以目視觀察第2黏著劑層5有無溶解,並以發生溶解之物為「○」,以未發生溶解之物為「×」。
如表2至4所示,實施例3至24之第2黏著劑層5於加熱後可溶解於p-烷。又如表2至4所示,實施例3、5至10、12至17、19至24之第2黏著劑層5的溶解速度為60nm/sec有利於生產性觀點。
將各層合物1浸漬於PGMEA中(23℃下5分鐘)。浸漬於PGMEA後以目視觀察第2黏著劑層5有無裂化,並以無裂化之物為「○」,以有裂化之物為「×」。
如表2至4所示,實施例4至7、11至14及18至21之第2黏著劑層5未發生裂化,但實施例8至10、15至17及22至24之第2黏著劑層5發生裂化。
以目視觀察形成於各層合物1之膜厚50μm的第2黏著劑層5有無裂化,並以無裂化之物為「○」,以有裂化之物為「×」。
如表2至4所示,實施例4至7、11至14及18至21之第2黏著劑層5未發生裂化,塗佈後具有良好柔軟性,但實施例8至10、15至17及22至24之第2黏著劑層5發生裂化。
將各層合物1各自浸漬於水、IPA(異丙醇)、PGME(丙二醇一甲醚)、NMP(N-甲基吡咯烷酮)、DMSO(二甲基亞碸)、2.38質量%之TMAH水溶液、5質量%氫氧化鈉水溶液、1質量%氫氟酸及3質量%氫氟酸(23℃下5分鐘)。浸漬於此等溶劑後以目視觀察第2黏著劑層5有無裂化及溶解,並以未發生裂化及溶解之物為「○」,以發生裂化及溶解之物為「×」。
如表2至4所示,實施例4至7、11至14及18至21浸於溶劑後,第2黏著劑層5未發生裂化及溶解,對溶劑具有良好耐性,但實施例8至10、15至17及22至24之第2黏著劑層5發生裂化。
將各層合物1由40℃升溫至250℃後,測定第2黏著劑層5之氣體發生量(脫氣量),再藉由該脫氣量評估各黏著劑組成物2之耐熱性。
可藉由脫氣量評估耐熱性之理由如下所述。即,至100℃測得的脫氣量係來自水蒸氣或其共沸氣體之物。又水蒸氣或其共沸氣體係來自黏著劑組成物2吸濕之水分。另外100℃以上測得之脫氣量係來自黏著劑組成物2本身藉由熱而分解生成的氣體之物。因此藉由100℃以上,特別是200℃附近之脫氣量,可評估黏著劑組成物2之耐熱性。
測定脫氣量係使用TDS法(Thermal Desorption Spectroscopy法,升溫脫離分析法)。所使用的TDS測定裝置(放出氣體測定裝置)為EMD-WA1000(電子科學股份公司製)。TDS裝置之測定條件為,Width: 100、Center Mass Number: 50、Gain: 9、Scan Speed: 4、Emult Volt: 1.3kV。
評估脫氣量之基準為,200℃下由上述TDS測定裝置求取之強度(Indensity)未達10000時為「○」,10000以上時為「×」。
又,評估耐熱性之基準為,200℃下由TDS測定裝置求取之強度未達10000,且金屬顯微鏡未觀察到殘渣時為「○」,強度10000以上但金屬顯微鏡觀察到殘渣時為「△」,強度10000以上但金屬顯微鏡未觀察到殘渣時為「×」。
如表2至4所示,實施例4至9、11至16及18至23之脫氣量評估為良好,耐熱性良好。
實施例4之黏著劑組成物2各自添加相對於黏著劑組成物2之全體樹脂為1%或5%的熱聚合禁止劑(IRGANOX1010(吉巴斯公司製))作為實施例25及26用。使用實施例4、實施例25及實施例26之黏著劑組成物2,於實施例3所形成的第1黏著劑層4上形成第2黏著劑層5。其次將多孔支撐板接合於第2黏著劑層5上,形成層合物1。
以250℃將各層合物1加熱1小時後,浸漬於p-烷。浸漬於p-烷後,算出第2黏著劑層5之溶解速度(nm/sec),結果如表5所示。
如表5所示,實施例4、25及26於加熱前之溶解速度為50至58nm/sec。實施例4及25以240至250℃加熱後不溶化,但實施例26於加熱後之溶解速度為60nm/sec。因此藉由添加熱聚合禁止劑可提升耐熱性。
同實施例1將黏著劑組成物1塗佈於5英寸矽晶圓2上,以80℃乾燥5分鐘後,形成層厚15μm之黏著劑層。其次將多孔支撐板3接合於該黏著劑層上。即黏著劑層為單層構造。由支撐板3未接觸黏著劑層側,將HP注入上述製作之層合物上。相對於溶劑的黏著劑層之溶解速度為100nm/sec,但係介由支撐板3的孔注入溶劑,因此會降低溶劑之浸透速度,溶解黏著劑層所需的時間約為5分鐘。即支撐板3之剝離時間約為5分鐘。
本發明非限定於上述各實施形態及實施例,可於申請專利範圍所表示之範圍內作各種變更,又由適當組合不同實施形態及實施例各自揭示之技術性方法而得的實施形態也包含於本發明之技術性範圍。
本發明之剝離方法易以短時間由基板剝離支撐板,例如適用於製造微細化之半導體裝置。
1...層合物
2...晶圓(基板)
3...支撐板
4...第1黏著劑層
5...第2黏著劑層
6...黏著層合物
圖1為,本發明之一實施形態的層合物1之剖面圖。
圖2為,圖中(a)至(e)為本發明之一實施形態的剝離方法中各步驟剖面圖。
1...層合物
2...晶圓(基板)
3...支撐板
4...第1黏著劑層
5...第2黏著劑層
6...黏著層合物
Claims (14)
- 一種剝離方法,其特徵為,由介有第1黏著劑層,及比第1黏著劑層更快溶解於溶劑之第2黏著劑層,或可溶解於不同於溶解第1黏著劑層之溶劑的溶劑之第2黏著劑層貼合支撐板的基板,剝離該支撐板之剝離方法中,包含溶解位於上述支撐板側之第2黏著劑層,而由上述基板剝離上述支撐板之剝離步驟。
- 如申請專利範圍第1項之剝離方法,其中上述剝離步驟之後,另包含溶解第1黏著劑層之溶解步驟。
- 如申請專利範圍第1項之剝離方法,其中上述支撐板設有複數貫穿厚度方向之貫穿孔。
- 如申請專利範圍第1項之剝離方法,其中形成第2黏著劑層之黏著化合物的平均分子量為,形成第1黏著劑層之黏著化合物的平均分子量之10%至30%。
- 如申請專利範圍第1項之剝離方法,其中形成第2黏著劑層之黏著化合物為,含有碳化氫樹脂或極性溶劑溶解性化合物。
- 如申請專利範圍第5項之剝離方法,其中上述碳化氫樹脂為環烯烴共聚物或環烯烴聚合物。
- 如申請專利範圍第5項之剝離方法,其中上述極性溶劑溶解性化合物為由膠原肽、纖維素及聚乙烯醇(PVA)所成群中所選出。
- 如申請專利範圍第1項之剝離方法,其中第2黏著劑層之層厚比第1黏著劑層之層厚更薄。
- 一種層合物,其特徵為,含有基板,及形成於上述基板上之第1黏著劑層,及形成於上述第1黏著劑層上之比第1黏著劑層更快溶解於溶劑之第2黏著劑層,或可溶解於不同於溶解第1黏著劑層之溶劑的溶劑之第2黏著劑層,及貼合於上述第2黏著劑層之支撐板。
- 一種黏著劑,其為形成如申請專利範圍第9項之層合物所含的第2黏著劑層用。
- 如申請專利範圍第10項之黏著劑,其中含有平均分子量為5000至10000之黏著化合物。
- 如申請專利範圍第10項之黏著劑,其中含有碳化氫樹脂或極性溶劑溶解性化合物。
- 如申請專利範圍第12項之黏著劑,其中上述碳化氫樹脂為由,環烯烴系聚合物、萜烯樹脂、松香系樹脂及石油樹脂所成群中所選出。
- 如申請專利範圍第12項之黏著劑,其中上述極性溶劑溶解性化合物為由膠原肽、纖維素及聚乙烯醇(PVA)所成群中選出。
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JP2009140223A JP5476046B2 (ja) | 2008-10-03 | 2009-06-11 | 剥離方法、基板の接着剤、および基板を含む積層体 |
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JP (1) | JP5476046B2 (zh) |
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JP5489546B2 (ja) * | 2009-06-11 | 2014-05-14 | 東京応化工業株式会社 | 貼付方法及び貼付装置 |
JP5308524B2 (ja) * | 2009-06-11 | 2013-10-09 | 東京応化工業株式会社 | 接着剤組成物 |
JP5619481B2 (ja) | 2010-06-15 | 2014-11-05 | 東京応化工業株式会社 | 接着剤組成物 |
JP6159050B2 (ja) | 2010-07-26 | 2017-07-05 | 東京応化工業株式会社 | 接着剤組成物及び接着フィルム |
US9263314B2 (en) | 2010-08-06 | 2016-02-16 | Brewer Science Inc. | Multiple bonding layers for thin-wafer handling |
JP5681501B2 (ja) * | 2010-09-02 | 2015-03-11 | 東京応化工業株式会社 | 接着剤組成物 |
JP5681502B2 (ja) | 2010-09-30 | 2015-03-11 | 東京応化工業株式会社 | 接着剤組成物 |
JP5632761B2 (ja) * | 2011-01-24 | 2014-11-26 | 東京応化工業株式会社 | 積層体 |
JP5728243B2 (ja) * | 2011-02-16 | 2015-06-03 | 東京応化工業株式会社 | 積層体 |
JP5956224B2 (ja) * | 2011-05-24 | 2016-07-27 | 東京応化工業株式会社 | 剥離用組成物および剥離方法 |
KR101638655B1 (ko) * | 2011-05-24 | 2016-07-11 | 도오꾜오까고오교 가부시끼가이샤 | 박리용 조성물 및 박리 방법 |
JP5410644B2 (ja) * | 2011-09-16 | 2014-02-05 | リンテック株式会社 | ダイシングシート用基材フィルムおよびダイシングシート |
JP5661669B2 (ja) * | 2011-09-30 | 2015-01-28 | 東京応化工業株式会社 | 接着剤組成物、接着フィルムおよび基板の処理方法 |
EP2810300A4 (en) * | 2012-01-30 | 2016-05-11 | 3M Innovative Properties Co | DEVICE, HYBRID LAMINATED BODY, METHOD AND MATERIALS FOR TEMPORARY SUBSTRATE CARRIER |
KR101777895B1 (ko) * | 2012-03-12 | 2017-09-12 | 도쿄 오카 고교 가부시키가이샤 | 접착제 조성물, 접착 필름 및 기판의 처리 방법 |
JP6006569B2 (ja) * | 2012-07-23 | 2016-10-12 | 東京応化工業株式会社 | 積層体及び積層体の製造方法 |
JP6014455B2 (ja) * | 2012-10-19 | 2016-10-25 | 富士フイルム株式会社 | 半導体装置の製造方法 |
JP5993103B2 (ja) | 2013-03-14 | 2016-09-14 | ブリヂストン アメリカズ タイヤ オペレーションズ、 エルエルシー | 再生剤 |
JP6182491B2 (ja) * | 2013-08-30 | 2017-08-16 | 富士フイルム株式会社 | 積層体およびその応用 |
JP6159220B2 (ja) * | 2013-10-17 | 2017-07-05 | 東京応化工業株式会社 | 剥離用組成物及び剥離方法 |
CN115939263A (zh) * | 2023-03-09 | 2023-04-07 | 浙江晶科能源有限公司 | 太阳能电池制备方法、太阳能电池及光伏组件 |
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TW200807536A (en) * | 2006-07-28 | 2008-02-01 | Tokyo Ohka Kogyo Co Ltd | Wafer bonding method, thinning method and detaching method |
TW200835979A (en) * | 2007-02-21 | 2008-09-01 | Fujifilm Corp | Method for manufacturing transparent polymer film, transparent polymer film made therefor, phase difference film, sheet polarizer and liquid crystal display device |
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US7473331B2 (en) * | 2003-10-08 | 2009-01-06 | General Electric Company | Method of applying an optical coating to an article surface |
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JP2006135272A (ja) * | 2003-12-01 | 2006-05-25 | Tokyo Ohka Kogyo Co Ltd | 基板のサポートプレート及びサポートプレートの剥離方法 |
US7232740B1 (en) * | 2005-05-16 | 2007-06-19 | The United States Of America As Represented By The National Security Agency | Method for bumping a thin wafer |
US7826113B2 (en) * | 2007-03-28 | 2010-11-02 | Konica Minolta Holdings, Inc. | Joined optical member, image display apparatus, and head-mounted display |
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- 2009-09-28 KR KR1020090091546A patent/KR101486597B1/ko active IP Right Grant
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TW200807536A (en) * | 2006-07-28 | 2008-02-01 | Tokyo Ohka Kogyo Co Ltd | Wafer bonding method, thinning method and detaching method |
TW200835979A (en) * | 2007-02-21 | 2008-09-01 | Fujifilm Corp | Method for manufacturing transparent polymer film, transparent polymer film made therefor, phase difference film, sheet polarizer and liquid crystal display device |
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JP5476046B2 (ja) | 2014-04-23 |
US20100086799A1 (en) | 2010-04-08 |
JP2010109324A (ja) | 2010-05-13 |
KR20100038144A (ko) | 2010-04-13 |
KR101486597B1 (ko) | 2015-01-26 |
TW201030836A (en) | 2010-08-16 |
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