TWI716347B - 感光性元件、積層體、永久抗蝕罩幕及其製造方法以及半導體封裝的製造方法 - Google Patents
感光性元件、積層體、永久抗蝕罩幕及其製造方法以及半導體封裝的製造方法 Download PDFInfo
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- TWI716347B TWI716347B TW104113215A TW104113215A TWI716347B TW I716347 B TWI716347 B TW I716347B TW 104113215 A TW104113215 A TW 104113215A TW 104113215 A TW104113215 A TW 104113215A TW I716347 B TWI716347 B TW I716347B
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Abstract
本發明的感光性元件具備:支撐膜、及設置於所述支撐膜上且由感光性樹脂組成物形成的感光層,且支撐膜與感光層接觸的面的表面粗糙度以Ra計為200nm~4000nm。
Description
本發明是有關於一種感光性元件、積層體、以及使用所述感光性元件的永久抗蝕罩幕、其製造方法及半導體封裝的製造方法。特別是有關於用作在半導體封裝用途中所使用的感光性絕緣材料的較佳的感光性元件。
隨著各種電子設備的高性能化,半導體的高積體化取得進展。伴隨於此,對形成於印刷配線板、半導體封裝基板等的永久抗蝕罩幕(阻焊劑)要求各種性能。
例如在專利文獻1中,藉由使用在無機填充材料中包含奈米尺寸的二氧化矽的感光性樹脂組成物的永久抗蝕罩幕,而達成高解析性與低熱膨脹化的兼顧。
現有技術文獻
專利文獻
專利文獻1:日本專利特開2011-013622號公報
然而,隨著半導體的高積體化,如在永久抗蝕罩幕上進
一步積層其他材料般的例子增加。因此,可用作永久抗蝕罩幕的材料理想為與所積層的其他材料、例如密封材料、底部填料、銅等的密接性優異。然而,關於專利文獻1等先前的感光性樹脂組成物,關於與其他材料的密接性,有改善的餘地。
因此,本發明的目的是提供一種可形成與不同種材料的密接性優異的永久抗蝕罩幕的感光性元件。而且,本發明的目的是提供一種使用所述感光性元件的永久抗蝕罩幕、永久抗蝕罩幕的形成方法、積層體及半導體封裝的製造方法。
本發明提供一種感光性元件,其具備:支撐膜、及設置於所述支撐膜上且由感光性樹脂組成物形成的感光層,且支撐膜與感光層接觸的面的表面粗糙度以Ra計為200nm~4000nm。
根據所述感光性元件,形成永久抗蝕罩幕時與不同種材料的密接性優異。
所述支撐膜的霧度可為60%以上。
所述感光性樹脂組成物可含有多官能環氧樹脂。藉此,因支撐膜上的表面粗糙度引起的凹凸容易直接殘留,而容易進一步發揮出本發明的效果。
所述感光性樹脂組成物可含有10質量%~90質量%的平均粒徑為1μm以下的無機填充材料。在高填充小粒徑的無機填充材料時,密接性容易降低,但若與本發明的支撐膜組合,則可充分地防止密接性的降低。
所述感光性樹脂組成物可含有具有(甲基)丙烯醯基的光反應性化合物,可進一步含有醯基膦系化合物。在含有具有(甲基)丙烯醯基的光反應性化合物的感光性樹脂組成物中,醯基膦系化合物具有底部硬化性優異、且難以受到氧抑制的特徵。因此,在後述的形成感光層的步驟後、且形成光硬化部的步驟前,具備將支撐膜剝離的步驟,可較佳地應用於相對容易受到因氧氣引起的影響的永久抗蝕罩幕的形成方法。此外,由於底部硬化性優異,因此在根據顏料等使用著色的感光性樹脂組成物時亦有效,亦可較佳地應用於在半導體封裝用基板的最外層所使用的阻焊劑。
本發明另外提供一種永久抗蝕罩幕的形成方法、及藉由所述方法形成的永久抗蝕罩幕,所述永久抗蝕罩幕的形成方法包括:使用所述感光性元件,在基板上形成感光層的步驟;對感光層的特定部分照射活性光線,形成光硬化部的步驟;將光硬化部以外的區域除去的步驟。
根據所述形成方法,由於使用本發明的感光性元件,因此可形成與不同種材料的密接性優異的永久抗蝕罩幕。
在所述永久抗蝕罩幕的形成方法中,在形成感光層的步驟後、且所述形成光硬化部的步驟前,可進一步具備:將支撐膜剝離的步驟。另外,在所述永久抗蝕罩幕的形成方法中,在形成光硬化部的步驟中,可使用直接描繪方式、投影曝光方式或以不與感光層直接接觸的方式配置負性罩幕的曝光方式,照射活性光線。
本發明的感光性元件可特佳地應用於如此在曝光前將支撐膜剝離、且藉由不使用罩幕的曝光方式或罩幕不與感光層接觸的曝光方式進行曝光的情形。
在所述永久抗蝕罩幕的形成方法中,在將光硬化部以外的區域除去的步驟後,可進一步具備:進行加熱的步驟。藉此,可使環氧樹脂硬化,而提高作為永久抗蝕罩幕的可靠性。
本發明另外提供一種半導體封裝的製造方法,其包括:在藉由所述永久抗蝕罩幕的形成方法,形成永久抗蝕罩幕的基板上,形成其他構件的步驟。
根據所述形成方法,由於使用本發明的永久抗蝕罩幕的形成方法,因此與其他構件(不同種材料)的密接性優異。
本發明提供一種積層體,其具備:基板、及在所述基板上使感光性樹脂組成物硬化而得的硬化物,且與基板相反側的面的硬化物的表面粗糙度以Ra計為200nm~4000nm。此種積層體與其他構件(不同種材料)的密接性優異。
根據本發明,可提供一種能形成與不同種材料、特別是密封材料、底部填料、濺鍍銅等的密接性優異的永久抗蝕罩幕的感光性元件。根據本發明,可進一步提供一種使用所述感光性元件的永久抗蝕罩幕、永久抗蝕罩幕的形成方法、積層體及半導體封裝的製造方法。
1‧‧‧密接體
3‧‧‧感光性絕緣膜
5‧‧‧基板
7‧‧‧支撐台
9‧‧‧工具
10‧‧‧半導體封裝
20‧‧‧半導體封裝基板
50‧‧‧半導體晶片搭載用基板
80‧‧‧銅配線
90‧‧‧永久抗蝕劑層
100、100a、100b‧‧‧絕緣基板
110‧‧‧打線接合用配線端子
111‧‧‧焊料連接用連接端子
112‧‧‧開口部
114‧‧‧焊球
115‧‧‧金線
116‧‧‧半導體用密封樹脂
117‧‧‧黏接劑
118‧‧‧底部填料劑
120‧‧‧半導體晶片
a‧‧‧方向
圖1是半導體封裝基板的示意剖面圖。
圖2是覆晶型封裝基板的示意剖面圖。
圖3是用於評價感度、解析性的曝光圖案的概略立體圖。
圖4是表示藉由晶片接合試驗機評價密接性的方法的概略立體圖。
以下,根據需要,一邊參照圖式,一邊對用以實施本發明的形態進行詳細地說明。但本發明並不限定於以下實施形態。另外,在本說明書中所謂「(甲基)丙烯酸酯」,是指「丙烯酸酯」或與其對應的「甲基丙烯酸酯」。關於「(甲基)丙烯酸」等類似的表述,亦相同。另外,關於「層」的用語,在以俯視圖觀察時,除了形成於整個面的形狀的結構外,亦包括形成於一部分面的形狀的結構。另外,使用「~」表示的數值範圍,表示包含「~」的前後所記載的數值分別作為最小值及最大值的範圍。另外,本說明書中階段性地記載的數值範圍中,某個階段的數值範圍的上限值或下限值,可以置換成其他階段的數值範圍的上限值或下限值。另外,本說明書中所記載的數值範圍中,所述數值範圍的上限值或下限值可置換成實施例所示的值。
本實施形態的感光性元件具備:支撐膜、及設置於所述支撐膜上的感光層。感光性元件在感光層的與支撐膜相反側的面可具有保護膜。
支撐膜與感光層接觸的面的表面粗糙度以Ra計為200nm~4000nm,可為200nm~2000nm,亦可為250nm~1000nm。若Ra小於200nm,則無法獲得充分的密接性。另一方面,若Ra大於4000nm,則將支撐膜剝離時的黏性變大,而難以剝離。另外,支撐膜與感光層接觸的面的表面粗糙度以Ra計可大於500nm且4000nm以下。
另外,在本說明書中,所謂「表面粗糙度」,是指算術平均粗糙度Ra。算術平均粗糙度Ra是指:根據粗糙度曲線在其平均線的方向僅抽取基準長度(L),在所述抽取部分的平均線的方向取X軸,在縱倍率的方向取Y軸,在以y=f(x)表示粗糙度曲線時,以奈米(nm)表示藉由下式求出的值者。即,Ra為下述式(1)所示的值。
支撐膜的表面粗糙度可藉由先前公知的方法進行調整,但例如可藉由捏合粗化(matting)式(在支撐膜中捏合潤滑材料的方法)、噴砂式或金屬壓印加工式進行調整。
另外,所使用的支撐膜的厚度並無限制,可為10μm~200μm的範圍,而且可為12μm~100μm的範圍。藉由厚度為10
μm以上,而在塗敷時生產性提高,若厚度為200μm以下,則有經濟性提高的傾向。
作為支撐膜,例如可列舉:聚對苯二甲酸乙二酯膜、聚乙烯膜、聚丙烯膜、聚碳酸酯膜等具有耐熱性及耐溶劑性的聚合物膜。就更容易發揮出本發明的效果的觀點而言,支撐膜的霧度可為60%以上、光澤度可為10%以上,霧度亦可為70%以上、光澤度亦可為20%以上。
繼而,對感光層進行說明。作為形成感光層的感光性樹脂組成物,可使用:光自由基聚合方式、光陽離子聚合方式、其他方式的所有感光性樹脂組成物。其中可特佳地使用氧抑制少的光陽離子聚合系樹脂組成物。作為此種樹脂組成物,可列舉光陽離子聚合起始劑、包含環氧樹脂或氧雜環丁烷樹脂的化合物為例。特別是包含環氧樹脂的樹脂組成物在密接性及耐熱性的方面有效,適宜滿足半導體封裝用途的各種可靠性。
另外,光自由基聚合系樹脂組成物亦有效。作為此種樹脂組成物,例如可列舉包含以下成分的樹脂組成物:(a)在分子內具有至少一個乙烯性不飽和基與羧基的感光性預聚物、(b)光聚合起始劑、(c)光反應性化合物、(d)多官能環氧樹脂、(e)無機填充材料。
對(a)在分子內具有至少一個乙烯性不飽和基與羧基的感光性預聚物(以下亦稱為「(a)感光性預聚物」)進行說明。(a)感光性預聚物若為在分子內具有至少一個乙烯性不飽和基與
羧基的樹脂,則任意者均可,例如可使用:在環氧樹脂(a1)與不飽和單羧酸(a2)的酯化物中加成飽和或不飽和多元酸酐(a3)而成的反應物等。所述反應物等可藉由如下的二階段的反應而得。在最先的反應(以下為了方便而稱為「第一反應」)中,環氧樹脂(a1)與不飽和單羧酸(a2)反應。在其後的反應(以下為了方便而稱為「第二反應」)中,第一反應中所生成的酯化物、與飽和或不飽和多元酸酐(a3)反應。作為所述環氧樹脂(a1),並無特別限制,例如可列舉:雙酚型環氧樹脂、酚醛清漆型環氧樹脂、聯苯型環氧樹脂、多官能環氧樹脂等。作為雙酚型環氧樹脂,適宜為使雙酚A型、雙酚F型、雙酚S型與表氯醇反應而得者,較佳為使用:巴斯夫(BASF)公司製造的GY-260、GY-255、XB-2615、三菱化學公司製造的愛皮克特(Epikote)828、愛皮克特(Epikote)1007、愛皮克特(Epikote)807等雙酚A型、雙酚F型、氫化雙酚A型、含有胺基、脂環式或聚丁二烯改質等的環氧樹脂。
作為所述不飽和單羧酸(a2),可列舉:(甲基)丙烯酸、丁烯酸、桂皮酸、飽和或不飽和多元酸酐與1分子中具有1個羥基的(甲基)丙烯酸酯類或飽和或不飽和二元酸與不飽和單縮水甘油基化合物的半酯化合物類的反應物。作為所述反應物,例如可列舉:藉由常法使鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、順丁烯二酸、琥珀酸等、與(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、三(羥基乙基)異氰脲酸酯二(甲基)丙烯酸酯、(甲基)
丙烯酸縮水甘油酯等以等莫耳比反應而得的反應物等。所述不飽和單羧酸可單獨使用或混合而使用。所述中,亦可使用丙烯酸。
作為飽和或不飽和多元酸酐,例如可列舉:琥珀酸酐、順丁烯二酸酐、四氫鄰苯二甲酸酐、鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、乙基四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、乙基六氫鄰苯二甲酸酐、衣康酸酐、偏苯三甲酸酐等。
作為所述感光性預聚物,在商業上可獲得:CCR-1218H、CCR-1159H、CCR-1222H、PCR-1050、TCR-1335H、ZAR-3035、ZAR-2001H、ZFR-1185及ZCR-1569H、UXE-3024(以上,日本化藥股份有限公司製造、商品名)、EXP-2810(大日本油墨化學(Dainippon Ink and Chemicals,DIC)股份有限公司製造、商品名)等。
(a)感光性預聚物可單獨使用或組合兩種以上而使用。樹脂的折射率因所用的樹脂的結構而多種多樣,在使用所述結構者時為1.4~1.7,大多為作為雙酚A型環氧樹脂的折射率的1.57左右,在使用1.5~1.6者時,可最大地發揮出本實施形態的效果。
(a)感光性預聚物的酸值可為20mgKOH/g~180mgKOH/g,亦可為30mgKOH/g~150mgKOH/g,還可為40mgKOH/g~120mgKOH/g。藉此,感光性樹脂組成物的藉由鹼性水溶液的顯影性變得良好,而獲得優異的解析度。
此處,酸值可藉由以下方法測定。首先,精確秤取測定樹脂溶液約1g後,在所述樹脂溶液中添加丙酮30g,將樹脂溶液均勻地溶解。繼而,在所述溶液中添加適量的作為指示劑的酚酞,使用0.1N的KOH水溶液進行滴定。並且,藉由下式算出酸值。
A=10×Vf×56.1/(Wp×1)
另外,式中,A表示酸值(mgKOH/g),Vf表示酚酞的滴定量(mL),Wp表示測定樹脂溶液重量(g),l表示測定樹脂溶液的非揮發成分的比例(質量%)。
另外,就塗膜性的觀點而言,(a)感光性預聚物的重量平均分子量可為3000~30000,亦可為5000~20000,還可為7000~15000。
另外,重量平均分子量(Mw)可根據藉由凝膠滲透層析法(Gel Permeation Chromatography,GPC)的標準聚苯乙烯換算值而求出。
作為(b)光聚合起始劑,例如可列舉:二苯甲酮、N,N,N',N'-四烷基-4,4'-二胺基二苯甲酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮-1,2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-丙酮-1、4,4'-雙(二甲基胺基)二苯甲酮(米其勒酮)、4,4'-雙(二乙基胺基)二苯甲酮、4-甲氧基-4'-二甲基胺基二苯甲酮等芳香族酮類,烷基蒽醌、菲醌等醌類,安息香、烷基安息香等安息香化合物,安息香烷醚、安息香苯醚等安息香醚化合物,苄基二甲基縮酮等苄基衍生物,2-(鄰氯苯基)-4,5-二苯基咪唑二聚物、2-(鄰氯苯
基)-4,5-二(間甲氧基苯基)咪唑二聚物、2-(鄰氟苯基)-4,5-二苯基咪唑二聚物、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚物、2,4-二(對甲氧基苯基)-5-苯基咪唑二聚物、2-(2,4-二甲氧基苯基)-4,5-二苯基咪唑二聚物等2,4,5-三芳基咪唑二聚物,N-苯基甘胺酸、N-苯基甘胺酸衍生物,9-苯基吖啶等吖啶衍生物,1,2-辛烷二酮,1-[4-(苯硫基)-,2-(O-苯甲醯基肟)]等肟酯類,7-二乙基胺基-4-甲基香豆素等香豆素系化合物,2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等噻噸酮系化合物,2,4,6-三甲基苯甲醯基-二苯基-氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦等醯基膦系化合物,9-苯基吖啶、9-胺基吖啶、9-戊基胺基吖啶、1,2-雙(9-吖啶基)乙烷、1,3-雙(9-吖啶基)丙烷、1,4-雙(9-吖啶基)丁烷、1,5-雙(9-吖啶基)戊烷、1,6-雙(9-吖啶基)己烷、1,7-雙(9-吖啶基)庚烷、1,8-雙(9-吖啶基)辛烷、1,9-雙(9-吖啶基)壬烷、1,10-雙(9-吖啶基)癸烷、1,11-雙(9-吖啶基)十一烷、1,12-雙(9-吖啶基)十二烷等雙(9-吖啶基)烷烴,9-苯基吖啶、9-吡啶基吖啶、9-吡嗪基吖啶、9-單戊基胺基吖啶、1,3-雙(9-吖啶基)-2-氧雜丙烷、1,3-雙(9-吖啶基)-2-硫雜丙烷、1,5-雙(9-吖啶基)-3-硫雜戊烷等具有吖啶環的化合物,(2-(乙醯氧基亞胺基甲基)噻噸-9-酮)、N-[1-[4-(苯硫基)苯甲醯基]亞庚基]-O-苯甲醯基羥基胺、O-乙醯基-1-[6-(2-甲基苯甲醯基)-9-乙基-9H-咔唑-3-基]乙酮肟等具有肟酯的化合物等。所述光聚合起始劑亦可組合而使用。所
述中,亦可使用醯基膦系化合物。
作為(b)光聚合起始劑,例如能以如下市售品獲得:豔佳固(IRGACURE)651、豔佳固(IRGACURE)184、豔佳固(IRGACURE)1173、豔佳固(IRGACURE)2959、豔佳固(IRGACURE)127、豔佳固(IRGACURE)907、豔佳固(IRGACURE)369、豔佳固(IRGACURE)379EG、豔佳固(IRGACURE)819、路科恩特普(LUCIRIN TPO)(均為巴斯夫公司製造)、德羅酷銳特普(DAROCURE-TPO)(巴斯夫公司製造、商品名)、卡亞庫(KAYACURE)DETX-S(日本化藥股份有限公司製造、商品名)。
作為(c)光反應性化合物,就感度、解析性的方面而言,可含有在分子內具有2個以上乙烯性不飽和基(可為(甲基)丙烯醯基)的光聚合性單體。光聚合性單體可單獨使用或組合兩種以上而使用,特別理想為含有至少一種以上在1分子內具有3個以上乙烯性不飽和基的多官能光聚合單體。其中,在1分子內具有6個以上乙烯性不飽和基的多官能光聚合單體對回焊安裝時的耐龜裂性的提高有效。作為此種化合物,有二季戊四醇六丙烯酸酯及其類似結構體者,商業上能以如下市售品獲得:卡亞拉得(KAYARAD)DPHA、卡亞拉得(KAYARAD)D-310、卡亞拉得(KAYARAD)D-330、卡亞拉得(KAYARAD)DPCA-20、卡亞拉得(KAYARAD)DPCA-30、卡亞拉得(KAYARAD)DPCA-60、卡亞拉得(KAYARAD)DPCA-120(均為日本化藥股份有限公司
製造、商品名)。作為在1分子內具有3個以上乙烯性不飽和基的多官能光聚合單體,在商業上能以如下市售品獲得:三羥甲基丙烷三乙氧基三丙烯酸酯(SR-454、日本化藥股份有限公司製造、商品名)等。
作為本實施形態的感光性樹脂組成物中可使用的其他(c)光反應性化合物,並無特別限制,可使用如以下者,所述中,可使用具有(甲基)丙烯醯基者。
例如可列舉:雙酚A系(甲基)丙烯酸酯化合物、使α,β-不飽和羧酸與多元醇反應而得的化合物、使α,β-不飽和羧酸與含有縮水甘油基的化合物反應而得的化合物、在分子內具有胺基甲酸酯鍵的(甲基)丙烯酸酯化合物等胺基甲酸酯單體、胺基甲酸酯寡聚物等。另外,除了所述化合物以外,亦可列舉:壬基苯氧基聚氧乙烯丙烯酸酯,γ-氯-β-羥基丙基-β'-(甲基)丙烯醯氧基乙基-鄰苯二甲酸酯、β-羥基烷基-β'-(甲基)丙烯醯氧基烷基-鄰苯二甲酸酯等鄰苯二甲酸系化合物,(甲基)丙烯酸烷基酯,環氧乙烷(Ethylene Oxide,EO)改質(甲基)丙烯酸壬基苯酯等。
就使鹼顯影性變得良好的觀點而言,可包含雙酚A系(甲基)丙烯酸酯化合物。作為雙酚A系(甲基)丙烯酸酯化合物,例如可列舉:2,2-雙(4-((甲基)丙烯醯氧基聚乙氧基)苯基)丙烷、2,2-雙(4-((甲基)丙烯醯氧基聚丙氧基)苯基)丙烷、2,2-雙(4-((甲基)丙烯醯氧基聚丁氧基)苯基)丙烷、2,2-雙(4-((甲基)丙烯醯氧基聚乙氧基聚丙氧基)苯基)丙烷等。所述化合物可單獨使用或組合兩種以上而
使用。
作為雙酚A系(甲基)丙烯酸酯化合物,2,2-雙(4-(甲基丙烯醯氧基五乙氧基)苯基)丙烷在商業上能以如下市售品獲得:FA-321M(日立化成股份有限公司製造、商品名)或BPE-500(新中村化學工業股份有限公司製造、商品名),2,2-雙(4-(甲基丙烯醯氧基十五乙氧基)苯基)丙烷在商業上能以BPE-1300(新中村化學工業股份有限公司製造、商品名)獲得。
作為(d)環氧樹脂,例如可列舉:雙酚A二縮水甘油醚等雙酚A型環氧樹脂、雙酚F二縮水甘油醚等雙酚F型環氧樹脂、雙酚S二縮水甘油醚等雙酚S型環氧樹脂、聯苯二酚二縮水甘油醚等聯苯二酚型環氧樹脂、聯二甲苯酚二縮水甘油醚等聯二甲苯酚型環氧樹脂、氫化雙酚A縮水甘油醚等氫化雙酚A型環氧樹脂、及所述的二元酸改質二縮水甘油醚型環氧樹脂、聯苯芳烷基型環氧樹脂、三(2,3-環氧丙基)異氰脲酸酯等。所述成分可單獨使用或組合兩種以上而使用。
作為所述化合物,可使用市售品。例如,作為雙酚A二縮水甘油醚,可列舉:愛皮克特(Epikote)828、愛皮克特(Epikote)1001、愛皮克特(Epikote)1002(均為三菱化學股份有限公司製造、商品名)等。作為雙酚F二縮水甘油醚,可列舉:愛皮克特(Epikote)807(三菱化學股份有限公司製造、商品名)、YSLV-80(新日鐵住金化學股份有限公司製造、商品名)等,作為雙酚S二縮水甘油醚,可列舉:EBPS-200(日本化藥股份有限公司製造、
商品名)、艾比克隆(EPICLON)EXA-1514(大日本油墨化學股份有限公司製造、商品名)等。另外,作為聯苯二酚二縮水甘油醚,可列舉:YL6121(三菱化學股份有限公司製造、商品名)等,作為聯二甲苯酚二縮水甘油醚,可列舉:YX4000H(三菱化學股份有限公司製造、商品名)等。而且,作為氫化雙酚A縮水甘油醚,可列舉:ST-2004、ST-2007(均為新日鐵住金化學股份有限公司製造、商品名)等,作為所述二元酸改質二縮水甘油醚型環氧樹脂,可列舉:ST-5100及ST-5080(均為新日鐵住金化學股份有限公司製造、商品名),作為聯苯芳烷基型環氧樹脂,可列舉:NC-3000、NC-3000H(均為日本化藥股份有限公司製造、商品名),作為三(2,3-環氧丙基)異氰脲酸酯,可列舉:TEPIC-S、TEPIC-VL、TEPIC-PASB26(日產化學工業股份有限公司製造)、AralditePT810(巴斯夫公司製造、商品名)等。另外,此外可列舉:雙酚A酚醛清漆型環氧樹脂的JER157S(三菱化學股份有限公司製造、商品名)等、四酚基乙烷型環氧樹脂的JERYL-931(三菱化學股份有限公司製造、商品名)、Araldite163(巴斯夫公司製造)等、四縮水甘油基二甲苯醯基乙烷樹脂的ZX-1063(新日鐵住金化學股份有限公司製造)等、含有萘基的環氧樹脂的ESN-190、ESN-360(新日鐵住金化學股份有限公司製造、商品名)、HP-4032、EXA-4750、EXA-4700(大日本油墨化學股份有限公司製造、商品名)等、具有二環戊二烯骨架的環氧樹脂的HP-7200、HP-7200H(大日本油墨化學股份有限公司製造、商品名)等、甲基丙烯酸
縮水甘油酯共聚合系環氧樹脂的CP-50S、CP-50M(日油股份有限公司製造、商品名)等、環氧改質的聚丁二烯橡膠衍生物的PB-3600、PB-4700(大賽璐(Daicel)股份有限公司製造、商品名)等、端羧基丁腈像膠(Carboxyl Terminated Butadiene-acrylonitrile,CTBN)改質環氧樹脂的YR-102、YR-450(新日鐵住金化學股份有限公司、商品名)等,但並不限定於所述市售品。所述環氧樹脂可單獨使用或組合兩種以上而使用。
作為(e)無機填充材料,例如可使用:硫酸鋇、鈦酸鋇、粉狀氧化矽、不定形二氧化矽、滑石、黏土、煅燒高嶺土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、雲母粉等。所述中,可含有硫酸鋇或二氧化矽填料。
(e)無機填充材料的平均粒徑可為1μm以下,亦可為30nm~800nm,還可為50nm~600nm。另外,(e)無機填充材料的最大粒徑可為10μm以下,亦可為5μm以下。無機填充材料的平均粒徑及最大粒徑例如可在分散於感光性樹脂組成物中的狀態下,藉由雷射繞射法或動態散射法進行測定。
關於(e)無機填充材料的含量,將感光性樹脂組成物總量作為基準,可為10質量%~90質量%,亦可為20質量%~80質量%,還可為30質量%~70質量%。
本實施形態的感光性樹脂組成物根據需要包含顏料成分。例如可使用:酞菁藍、酞菁綠、碘綠、二重氮黃、孔雀綠、結晶紫、氧化鈦、炭黑、萘黑、偶氮系有機顏料等著色劑、染料
等。
本實施形態的感光性樹脂組成物在不對感光性樹脂組成物的所期望的特性造成影響的範圍內,可進一步包含:對苯二酚、對苯二酚單甲醚、第三丁基鄰苯二酚、鄰苯三酚、酚噻嗪(phenothiazine)、亞硝基化合物等聚合抑制劑,膨润土(bentone)、蒙脫石(montmorillonite)、氧相二氧化硅(aerosil)、醯胺蠟等觸變性賦予劑,矽酮系、氟系、高分子系等消泡劑,勻平劑、三聚氰胺等密接性提高劑,二氰基二醯胺等硬化促進劑等。
本實施形態的感光性樹脂組成物理想為根據需要包含溶劑。另外,本實施形態的感光性樹脂組成物根據需要可含有彈性體成分。作為溶劑,例如可單獨使用甲醇、乙醇、丙酮、甲基乙基酮、丙二醇單乙酸酯、乙二醇二甲醚、甲苯、石油腦等通常的溶劑,或組合兩種以上而使用。
另外,在直接以液態使用感光性樹脂組成物時,溶劑的含量可為總重量中的5質量%~60質量%。
作為保護膜,例如可使用:聚對苯二甲酸乙二酯、聚丙烯、聚乙烯、聚酯等具有耐熱性及耐溶劑性的聚合物膜。作為市售品,例如可列舉:王子製紙股份有限公司製造的製品名「阿爾法(ALPHAN)MA-410]、「E-200C」、信越膜股份有限公司製造等的聚丙烯膜、帝人股份有限公司製造的製品名「PS-25」等PS系列等的聚對苯二甲酸乙二酯膜等,但並不限定於所述保護膜。所述保護膜的厚度可為1μm~100μm,亦可為5μm~50μm,還可
為5μm~30μm,又可為15μm~30μm。藉由所述厚度為1μm以上,而在層壓時有保護膜難以破壞的傾向,若所述厚度為100μm以下,則有經濟性優異的傾向。另外,保護膜可為與感光層及支撐膜的黏接力相比,感光層及保護膜的黏接力小者,並且可為低魚眼(fisheye)的膜。所謂魚眼,是在將材料進行熱熔融,藉由混練、擠出、雙軸延伸、澆鑄法等製造膜時,材料的異物、未溶解物、氧化劣化物等進入膜中而成者。
所述感光層可藉由以下方式形成:將所述感光性樹脂組成物溶解於如上所述的溶劑中製成固體成分為30質量%~70質量%左右的溶液(塗佈液)後,將所述溶液(塗佈液)塗佈於支撐膜上進行乾燥。所述塗佈例如可藉由使用輥塗機、缺角輪塗佈機(comma coater)、凹版塗佈機(gravure coater)、氣刀塗佈機、模塗機、棒塗機等的公知的方法進行。另外,所述乾燥可在70℃~150℃下進行5分鐘~30分鐘左右。就防止其後步驟中的有機溶劑的擴散的方面而言,相對於感光性樹脂組成物的總量,感光性樹脂組成物中的殘存有機溶劑量可設為3質量%以下。所述感光層的厚度根據用途而不同,以乾燥後的厚度計可為10μm~100μm,亦可為15μm~60μm,還可為20μm~50μm。在所述厚度為10μm以上時,有在工業上塗敷變得容易的傾向,若所述厚度為100μm以下,則有感光層內部的感度及解析度提高的傾向。
繼而,對使用本實施形態的感光性膜的抗蝕劑圖案(永久抗蝕罩幕)的形成方法進行說明。
首先,在應形成抗蝕劑圖案的基板上,使用所述感光性元件形成感光層。具體而言,將所述感光性膜的保護膜自感光層剝離,藉由層壓等,以覆蓋形成於基板上的具有電路圖案的導體層的方式,使所露出的面密接。就密接性、追隨性提高的觀點而言,可藉由在減壓下積層的方法形成感光層。
繼而,根據需要進行自所述感光性膜除去支撐膜的除去步驟,並進行對感光層的特定部分照射活性光線,使照射部的感光層光硬化的曝光步驟。本實施形態的感光性膜可特佳地應用於在曝光前除去支撐膜的形態。另外,作為對感光層的特定部分照射活性光線的方法,可應用先前公知的方法,但可較佳地應用:直接描繪方式、投影曝光方式等不使用罩幕的方式或以不與感光層直接接觸的方式配置負性罩幕的曝光方式。
而且,在感光層上存在支撐膜時,在將所述支撐膜除去後,藉由濕式顯影或乾式顯影除去未光硬化的部分(未曝光部)進行顯影,從而可形成抗蝕劑圖案。
在為所述濕式顯影時,作為顯影液,可根據感光性樹脂組成物的種類而使用:鹼性水溶液、有機溶劑顯影液等安全且穩定並且操作性良好者。另外,作為顯影方法,可適當採用:噴霧、摇動浸漬、刷洗、擦洗等公知的方法。
作為所述鹼性水溶液的鹼,可使用:作為鹼金屬、例如鋰、鈉、鉀的氫氧化物的氫氧化鋰、氫氧化鈉、氫氧化鉀等,作為鹼金屬、銨等的碳酸鹽或碳酸氫鹽的碳酸鹼或碳酸氫鹼,作為
鹼金屬的磷酸鹽的磷酸鈉、磷酸鉀等,作為鹼金屬的焦磷酸鹽的焦磷酸鈉、焦磷酸鉀等,硼砂,偏矽酸鈉,氫氧化四甲基銨,乙醇胺,乙二胺,二乙三胺,2-胺基-2-羥基甲基-1,3-丙二醇,1,3-二胺基丙醇-2,嗎啉等安全且穩定、並且操作性良好者。
另外,作為此種鹼性水溶液,例如可使用:0.1質量%~5質量%碳酸鈉的稀溶液、0.1質量%~5質量%碳酸鉀的稀溶液、0.1質量%~5質量%氫氧化鈉的稀溶液、0.1質量%~5質量%四硼酸鈉的稀溶液,其pH值可設為9~11的範圍。另外,此種鹼性水溶液的溫度根據感光層的顯影性進行調節,可設為20℃~50℃。而且,在所述鹼性水溶液中,為了促進顯影,可混入界面活性劑、消泡劑等少量的有機溶劑。
作為所述有機溶劑顯影液中所用的有機溶劑,例如可使用:丙酮、乙酸乙酯、具有碳數為1~4的烷氧基的烷氧基乙醇、乙醇、異丙醇、丁醇、二乙二醇單甲醚、二乙二醇單乙醚及二乙二醇單丁醚。此種有機溶劑的濃度通常可為2質量%~90質量%。另外,此種有機溶劑的溫度可根據顯影性進行調節。此種有機溶劑可單獨使用或組合兩種以上而使用。作為單獨使用的有機溶劑顯影液,例如可列舉:1,1,1-三環乙烷、N-甲基吡咯啶酮、N,N-二甲基甲醯胺、環己酮、甲基異丁基酮及γ-丁內酯。
在本實施形態的抗蝕劑圖案的形成方法中,根據需要可併用所述兩種以上顯影方法而使用。顯影的方式有浸泡方式、覆液方式、噴霧方式、高壓噴霧方式、刷洗、擦洗等,為了提高解
析度,最佳為高壓噴霧方式。顯影後所進行的金屬面的蝕刻例如可使用:氯化銅溶液、氯化鐵溶液、鹼性蝕刻溶液等。
繼而,對使用本實施形態的感光性膜的永久抗蝕罩幕的較佳的實施形態進行說明。
在所述顯影步驟結束後,為了提高焊料耐熱性、耐化學品性等,可進行藉由高壓水銀燈的紫外線照射或加熱。在照射紫外線時,根據需要可調整其照射量,例如能以0.05J/cm2~10J/cm2左右的照射量進行照射。另外,在將抗蝕劑圖案加熱時,可在130℃~200℃左右的範圍中進行15分鐘~90分鐘左右。
紫外線照射及加熱可進行兩者。此時,可同時進行兩者,亦可實施任一者後再實施另一者。在同時進行紫外線照射與加熱時,就更良好地賦予焊料耐熱性及耐化學品性的觀點而言,可加熱至60℃~150℃。
本實施形態中的永久抗蝕罩幕(硬化膜)的表面粗糙度以Ra計可為200nm~4000nm,亦可為250nm~3000nm,還可為300nm~2000nm。另外,本實施形態中的永久抗蝕罩幕(硬化膜)的表面粗糙度以Ra計可大於500nm且4000nm以下。
如此形成的永久抗蝕罩幕可兼作對基板實施焊接後的配線的保護膜,具有阻焊劑的各特性而用作印刷配線板用途、半導體封裝基板用途、或可撓性配線板用途的阻焊劑。
所述阻焊劑例如在對基板實施鍍敷或蝕刻時,除了用作鍍敷抗蝕劑或蝕刻抗蝕劑外,還可直接殘留在基板上而用作用以
保護配線等的保護膜(永久抗蝕罩幕)。
另外,在所述曝光步驟中,在使用前期導體層的特定部分具有未曝光的圖案的罩幕或描繪資料進行曝光時,藉由將其顯影,而將未曝光部分除去,而獲得形成於基板上的導體層的一部分露出、且具有開口圖案的抗蝕劑。然後,可進行形成所述永久抗蝕罩幕所必需的處理。
亦可在形成有所述永久抗蝕罩幕的基板上,形成其他構件、例如密封材料、底部填料、銅等,而製造半導體封裝。
例如在所述永久抗蝕罩幕上,藉由濺鍍、鍍敷等形成銅層,並對其進行蝕刻處理,藉此可形成銅(導體)圖案,即藉由增層進行再配線。根據本實施形態的永久抗蝕罩幕,可形成密接性優異的銅圖案。
另外,在應用本實施形態的感光性元件作為感光性阻焊劑時,在半導體封裝基板上將半導體晶片進行覆晶連接後,在阻焊劑上形成密封材料或底部填料,藉由所述效果,可獲得兩者良好的密接性。
[半導體封裝]
本實施形態的感光性元件可較佳地用於半導體封裝用印刷配線板的永久抗蝕罩幕(永久抗蝕劑層)的形成。圖1是表示半導體封裝的一實施形態的示意剖面圖。半導體封裝10具備:半導體晶片搭載用基板50、搭載於半導體晶片搭載用基板50的半導體晶片120。半導體晶片搭載用基板50與半導體晶片120藉由包含黏
晶膜或黏晶膏的黏接劑117黏接。半導體晶片搭載用基板50具備絕緣基板100,在絕緣基板100的一個面上,設置打線接合用配線端子110、及形成有配線端子110的一部分露出的開口部的永久抗蝕劑層90,在相反側的面上,設置永久抗蝕劑層90及焊料連接用連接端子111。永久抗蝕劑層90是包含使用所述本實施形態的感光性膜而形成的硬化物的層。焊料連接用連接端子111為了進行與印刷配線板的電性連接,而搭載焊球114。半導體晶片120與打線接合用配線端子110使用金線115進行電性連接。半導體晶片120藉由半導體用密封樹脂116進行密封。藉由使用本實施形態的感光性膜、永久抗蝕罩幕或其製造方法或半導體封裝的製造方法而形成,與不同種材料(即,半導體用密封樹脂116)的密接性提高。另外,所述基板與相反側的面上的所述硬化物的「基板與相反側的面」,是指與不同種材料接觸的面。另外,本實施形態的感光性元件亦可應用於覆晶型半導體封裝。
圖2是表示覆晶型半導體封裝基板的示意剖面圖。覆晶型半導體封裝基板20具備:半導體晶片搭載用基板50、搭載於半導體晶片搭載用基板50的半導體晶片120。在半導體晶片搭載用基板50與半導體晶片120之間,填充有底部填料劑118。半導體晶片搭載用基板50具有:依序積層絕緣基板100b、絕緣基板100a、永久抗蝕劑層90的構成。永久抗蝕劑層90是包含使用所述本實施形態的感光性膜而形成的硬化物的層。絕緣基板100b在絕緣基板100a側的表面具有經圖案化的銅配線80,絕緣基板100a
在永久抗蝕劑層90側的表面具有經圖案化的銅配線80。絕緣基板100b上的銅配線80、與絕緣基板100a上的銅配線80的至少一部分,藉由以貫通絕緣基板100a及絕緣基板100b的方式形成的焊料連接用連接端子111而電性連接。另外,永久抗蝕劑層90以覆蓋絕緣基板100a上的銅配線80的方式形成,在與焊料連接用連接端子111對應的銅配線80上,以銅配線80露出的方式形成開口部112。絕緣基板100a上的銅配線80與在半導體晶片120的和半導體晶片搭載用基板50相對的面上所形成的銅配線80,經由設置於所述開口部112的焊球114而電性連接。藉由使用本實施形態的感光性膜、永久抗蝕罩幕或其製造方法或半導體封裝的製造方法而形成,而與不同種材料(即,底部填料劑118)的密接性提高。
具備本實施形態的永久抗蝕罩幕的基板然後進行半導體元件等的安裝(例如打線接合、C4焊料連接),繼而安裝於電腦等電子設備。
另外,使用本實施形態的感光性膜而形成的硬化物,可較佳地用作層間絕緣膜。藉由用作層間絕緣膜,而可提高與其他材料的密接性。
實施例
以下,藉由實施例對本發明進行更詳細地說明,但本發明並不限定於所述實施例。
首先,以表1所示的調配量(重量份)將下述成分混合,
而獲得感光性樹脂A~感光性樹脂F的溶液。
(感光性樹脂A)
作為在分子內具有至少一個乙烯性不飽和基與羧基的感光性預聚物,使用酸改質甲酚酚醛清漆型環氧丙烯酸酯「EXP-2810」(大日本油墨化學股份有限公司製造、商品名)。重量平均分子量為10000,酸值為70mgKOH/g。
作為光反應性化合物,使用二季戊四醇五丙烯酸酯及二季戊四醇六丙烯酸酯混合物「卡亞拉得(KAYARAD)DPHA」(日本化藥股份有限公司製造、商品名)。
另外,作為光聚合起始劑,使用2,4,6-三甲基苯甲醯基-二苯基-氧化膦「德羅酷銳特普(DAROCURE-TPO)」(巴斯夫公司製造、商品名)、2,4-二乙基噻噸酮「卡亞庫(KAYACURE)DETX-S」(日本化藥股份有限公司製造、商品名)。
作為環氧樹脂,使用作為聯苯芳烷基型環氧樹脂的「NC-3000H」(日本化藥股份有限公司製造、商品名)與作為雙酚F型環氧樹脂的「YSLV-80」(新日鐵住金化學股份有限公司製造、商品名)。
無機填充材料使用:作為硫酸鋇的「B30」(堺化學工業股份有限公司製造、商品名)、作為二氧化矽的「MEK漿料(1)」(雅都瑪特科(Admatechs)股份有限公司製造、樣品名)。無機填充材料的分散在感光性樹脂組成物中的狀態下的平均粒徑及最大粒徑,使用雷射繞射散射式麥奇克(Microtrac)粒度分佈計
「MT-3100」(日機裝公司製造)進行測定。B30的平均粒徑為0.3μm、MEK漿料(1)的平均粒徑為0.5μm。另外,包含B30及MEK漿料的無機填充材料的最大粒徑為3μm以下。
另外,膜化後的無機填充材料的粒徑是在硬化後藉由電子顯微鏡(Scanning Electron Microscopy,SEM)對膜的剖面進行觀察而確認。確認到分散在膜中的無機填充材料的最大粒徑為5μm以下。
作為其他成分,使用以下成分。作為丁二烯系彈性體的「艾波利得(EPOLEAD)PB3600」(大賽璐股份有限公司製造、商品名)、作為聚合抑制劑的「安塔積(Antage)500」(川口化學工業股份有限公司製造、商品名)、作為硬化促進劑、及密接性提高劑的三聚氰胺與二氰基二醯胺,顏料使用酞菁藍。溶劑使用甲基乙基酮與丙二醇單甲醚乙酸酯。
(感光性樹脂B)
作為光聚合起始劑,使用「豔佳固(IRGACURE)907」(2-甲基-1-(4-(甲硫基)苯基)-2-嗎啉基丙烷-1-酮)(巴斯夫公司製造、商品名),來代替「德羅酷銳特普(DAROCURE-TPO)」(巴斯夫公司製造、商品名),除此以外,藉由以與感光性樹脂A相同的方式進行調配,而獲得感光性樹脂B。
(感光性樹脂C)
作為無機填充材料,使用「樣品2-N」(雅都瑪特科股份有限公司製造、樣品名、使藉由矽烷化合物進行表面處理的奈米二氧
化矽分散於甲基乙基酮中而成的漿料)。樣品2-N中的經表面處理的二氧化矽的分散狀態,使用動態光散射式耐恩奇克(Nanotrac)粒度分佈計「UPA-EX150」(日機裝股份有限公司製造)進行測定,確認到平均粒徑為0.05μm、最大粒徑為1μm以下。此外,藉由以與感光性樹脂A相同的方式進行調配,而獲得感光性樹脂C。
(感光性樹脂D)
除了不調配無機填充材料以外,藉由以與感光性樹脂A相同的方式進行調配,而獲得感光性樹脂D。
(感光性樹脂E)
作為光反應性化合物,使用「FA-321M」(日立化成股份有限公司製造、商品名)來代替「卡亞拉得(KAYARAD)DPHA」(日本化藥股份有限公司製造、商品名),除此以外,藉由以與感光性樹脂A相同的方式進行調配,而獲得感光性樹脂E。
(感光性樹脂F)
作為在分子內具有至少一個乙烯性不飽和基與羧基的感光性預聚物,使用UXE-3024(日本化藥股份有限公司製造、商品名)來代替「EXP-2810」(大日本油墨化學股份有限公司製造、商品名),除此以外,藉由以與感光性樹脂A相同的方式進行調配,而獲得感光性樹脂F。
(實施例1~實施例12、比較例1~比較例3)
將所述感光性樹脂A~感光性樹脂F的溶液均勻地塗佈於與感光層接觸的面的表面粗糙度不同的以下支撐膜上,而形成感光層。
支撐膜A:PET X42-26(捏合粗化型)東麗(Toray)股份有限公司製造
膜厚:26μm、表面粗糙度Ra:370nm、霧度:80%
支撐膜B:PET X44-26(捏合粗化型)東麗股份有限公司製造
膜厚:26μm、表面粗糙度Ra:265nm、霧度:77%
支撐膜C:PET A型加工(噴砂加工)開成工業股份有限公司製造
膜厚:50μm、表面粗糙度Ra:572nm、霧度:72%
支撐膜D:PE T-5N(壓印加工型)大倉工業股份有限公司製造
膜厚:34μm、表面粗糙度Ra:3500nm、霧度:88%
支撐膜E:OPP MA-420王子特殊紙股份有限公司製造
膜厚:35μm、表面粗糙度Ra:100nm、霧度:7.5%
支撐膜F:PET HPE(高透明型)杜邦帝人薄膜(Teijin Dupont Films)股份有限公司製造
膜厚:25μm、表面粗糙度Ra:<50nm、霧度:0.9%
支撐膜G:PET B型加工(噴砂加工)開成工業股份有限公司製造
膜厚:50μm、表面粗糙度Ra:1022nm、霧度:76%
支撐膜H:PET C型加工(噴砂加工)開成工業股份有限公司製造
膜厚:50μm、表面粗糙度Ra:2339nm、霧度:84%
支撐膜I:PE試作品(壓印加工)大倉工業股份有限公司製造
膜厚:34μm、表面粗糙度Ra:4875nm、霧度:92%
在形成感光層後,使用熱風對流式乾燥機在100℃下將所述感光層乾燥約10分鐘。感光層在乾燥後的膜厚為25μm。繼而,在與感光層的和支撐膜接觸之側的相反側的表面上,貼合OPP雙軸延伸聚丙烯膜(MA-411、王子特殊紙股份有限公司製造、商品名)作為保護膜,而獲得感光性膜。
表2中表示實施例1~實施例7、以及比較例1及比較例2中所用的感光性樹脂與支撐膜的組合。另外,實施例8與實施例1相同,為感光性樹脂與支撐膜的組合,是在評價基板的製作中,在曝光前不將支撐膜剝離,而與通常的感光性膜的使用法相同,在曝光後將支撐膜剝離的例子。另外,表3中表示實施例9~實施例12、及比較例3中所用的感光性樹脂與支撐膜的組合。
[感度、解析性的評價]
藉由粗化預處理液CZ-8100(邁克(MEC)股份有限公司製造),對將厚度為12μm的銅箔積層於玻璃環氧基板而得的印刷配線板用基板(MCL-E-679、日立化成股份有限公司製造、商品名)的銅表面進行處理,在水洗後進行乾燥。在所述印刷配線板用基板上,使用壓製式真空貼合機(MVLP-500、名機製作所股份有限公司製造、商品名),在壓製熱板溫度為70℃、抽成真空時間為20秒鐘、層壓壓製時間為30秒鐘、氣壓為4kPa以下、及壓接壓力為0.4MPa的條件下,將感光性膜的保護膜剝離進行積層,而獲得評價用積層體。
然後,在室溫下放置1小時以上後,將支撐膜剝離、除去,並設置41格曝光格數片(step tablet),使用將超高壓水銀燈作為光源的直接成像曝光裝置DXP-3512(奧珂製作所(ORC MANUFACTURING)股份有限公司製造)進行曝光。作為曝光圖案,使用以10μm刻度計具有Φ30μm~100μm的點的圖案。所述曝光圖案在各直徑(30μm~100μm的10μm刻度計的直徑)的每個直徑具有將如圖3所示的特定直徑(圖中的X μm)的點呈格子狀排列的區塊。
自曝光後在室溫下放置30分鐘後,藉由30℃的1質量%碳酸鈉水溶液將未曝光部的感光性樹脂組成物進行60秒鐘噴霧顯影。顯影後,將41格曝光格數片的光澤殘存曝光格數成為10.0的曝光能量作為感光層的感度(單位;mJ/cm2)。使用藉由所述感度進行曝光的圖案,而進行感光層的評價。
感度的評價是藉由曝光格數成為10.0的曝光能量,將200mJ/cm2以下設為「A」,將超過200mJ/cm2且300mJ/cm2以下設為「B」,將超過300mJ/cm2的情形設為「C」。另外,曝光能量越小,則以高感度曝光所需要的時間變得越短,特別是直接成像曝光時的產量變得越佳。
另外,解析性的評價是藉由曝光格數成為10.0的曝光能量進行曝光、噴霧顯影,在顯影處理後使用光學顯微鏡觀察抗蝕劑圖案而評價。將點圖案無殘渣而開口的最小的孔徑(μm)作為最小的解析性。將結果表示於表2及表3。
[支撐膜剝離性的評價]
在感度、解析性評價的項目記載的條件下,將感光性膜層壓於基板上後,在室溫下放置1小時以上。然後,不進行曝光,而將支撐膜剝離、除去時,將感光層貼附於支撐膜側,並自基板上剝離者評價為「C」,將一部分自基板上剝離者評價為「B」,將未自基板上剝離者評價為「A」。將結果表示於表2及表3。
[熱膨脹係數(coefficient of thermal expansion,CTE)的評價]
對所述評價用積層體的整個面進行曝光,進行至顯影、紫外線照射、加熱處理,藉此在厚度為16μm的聚對苯二甲酸乙二酯膜(G2-16、帝人股份有限公司製造、商品名)(支撐膜)上,形成感光性樹脂組成物的硬化物,繼而,藉由截切刀切出成寬度為3mm、長度為30mm後,將硬化物上的聚對苯二甲酸乙二酯剝離,而獲得熱膨脹係數評價用永久抗蝕罩幕。
使用TMA裝置SS6000(精工電子股份有限公司製造),進行藉由拉伸模式的熱膨脹係數的測定。拉伸負荷為2g、跨距(夾頭間距離)為15mm、升溫速度為10℃/分鐘。首先,將樣品安裝於裝置,自室溫(25℃)加熱至160℃,並放置15分鐘。然後,冷卻至-60℃,在升溫速度為10℃/分鐘的條件下自-60℃進行測定至250℃為止。將25℃~200℃的範圍中所見到的反曲點設為Tg。CTE是使用在Tg以下的溫度下而得的曲線的切線的斜率。將CTE的值為30ppm/℃以下者設為「3」,將超過30ppm且60ppm以
下者設為「2」,將超過60ppm者設為「1」。將結果表示於表2及表3。
[密封材料、底部填料、銅配線密接性的評價]
使用奧坷製作所公司製造的紫外線照射裝置,以1J/cm2的能量對感度、解析性評價的項目記載的評價用積層體進行紫外線照射,繼而在160℃下進行60分鐘加熱處理,藉此獲得在表面形成有感光性絕緣膜的評價用基板。
在所述基板的感光性絕緣膜上,將密封材料CEL-C-9700系列(日立化成股份有限公司製造、商品名)形成為圓柱狀,而獲得密封材料密接性評價用試驗樣品。
另外,在所述基板的感光性絕緣膜上,將底部填料CEL-C-3730S(日立化成股份有限公司製造、商品名)形成為圓柱狀,而獲得底部填料密接性評價用試驗樣品。
另外,在所述基板上使用濺鍍銅,繼而在其上將底部填料CEL-C-3730S(日立化成股份有限公司製造、商品名)形成為圓柱狀,而獲得濺鍍銅密接性評價用試驗樣品。
密接性是藉由晶片接合試驗機(力世科(RHESCA)股份有限公司製造),在測定高度為50μm、測定速度為50μm/秒鐘、室溫下,測定各試驗樣品的黏接強度。將藉由晶片接合試驗機評價密接性的方法表示於圖4。圖4中,符號1表示形成為圓柱狀的密封材料或底部填料(以下亦稱為「密接體1」),符號3表示感光性絕緣膜,符號5表示基板。將基板固定於晶片接合試驗機的支
撐台7,藉由工具9將密接體朝著方向a加壓,藉此將試驗樣品破壞。
關於密封材料及底部填料的密接性評價,在藉由晶片接合試驗機將試驗樣品破壞時,將在銅與感光性絕緣膜3的界面破壞者、或因基板5的凝聚破壞而破壞者評價為「A」,將在密接體1與感光性絕緣膜3的界面破壞者評價為「C」,將在兩者破壞者評價為「B」。
關於濺鍍銅密接性,將以剝離強度計出現1MPa以上的值者評價為「A」,將0.5MPa以上且小於1MPa者評價為「B」,將小於0.5MPa者評價為「C」。將結果表示於表2及表3。
[高加速應力試驗(High Accelerated Stress Testing,HAST)耐性的評價]
核心材料使用將厚度為12μm的銅箔積層於玻璃環氧基材而得的印刷配線板用基板(MCL-E-679FG、日立化成股份有限公司、商品名)、半加成配線形成用增層材料(AS-ZII、日立化成股份有限公司製造、商品名),製作線/間隙為8μm/8μm的梳型電極,並將其作為評價基板。
在所述評價基板的梳型電極上,以與所述「感度、解析性的評價」及「密接性」相同的方式,形成包含抗蝕劑的硬化物的感光性絕緣膜(以在梳型電極部分殘留阻焊劑的方式進行曝光並進行顯影、紫外線照射、加熱處理而形成),然後,在130℃、85%RH、6V條件下暴露200小時。然後,藉由100倍的金屬顯微
鏡觀察電阻值的測定及遷移(migration)的產生程度,按照如下的基準進行評價。即,將電阻值保持1.0×1010Ω以上、且在感光性絕緣膜上未產生遷移者設為「A」,將電阻值保持1.0×1010Ω以上、但產生少量遷移者設為「B」,將電阻值小於1.0×1010Ω、且大幅產生遷移者設為「C」。將結果表示於表2及表3。
[耐龜裂性的評價]
以與所述「評價基板的製作」相同的方式,將形成有感光性絕緣膜的評價用積層體在-65℃的大氣中暴露15分鐘後,以180℃/分鐘的升溫速度進行升溫,繼而在150℃的大氣中暴露15分鐘後,以180℃/分鐘的降溫速度進行降溫,將所述的熱循環重複1000次。在此種環境下暴露後,藉由100倍的金屬顯微鏡觀察評價用積層體的永久抗蝕罩幕的龜裂及剝離程度,按照如下的基準進行評價。即,將確認2mm見方的開口部的10個部位而完全無法觀察到永久抗蝕罩幕的龜裂及剝離者設為「A」,將在10個部位中在2個部位以下觀察到龜裂及剝離者設為「B」,將在10個部位中在3個部位以上觀察到龜裂及剝離者設為「C」。將結果表示於表2及表3。
[硬化物的表面粗糙度的評價]
使用顯微鏡(基恩士(KEYENCE)股份有限公司製造、商品名「雷射掃描顯微鏡VK-8500」),在測定範圍為100μm×100μm的條件下,測定藉由所述方法而得的硬化物的表面粗糙度Ra。
根據實施例1~實施例12及比較例1~比較例3的試驗
結果,藉由在與感光層接觸的面的表面粗糙度(Ra)為200nm~4000nm的範圍內的支撐膜上塗佈感光性絕緣層,而可轉印支撐膜的粗糙度。
若將支撐膜的粗糙度轉印至感光層,則感光層的表面粗糙度增大。即認為可獲得良好的錨定效果,並且底部填料或密封材料等與半導體材料的密接性提高。
10‧‧‧半導體封裝
50‧‧‧半導體晶片搭載用基板
90‧‧‧永久抗蝕劑層
100‧‧‧絕緣基板
110‧‧‧打線接合用配線端子
111‧‧‧焊料連接用連接端子
114‧‧‧焊球
115‧‧‧金線
116‧‧‧半導體用密封樹脂
117‧‧‧黏接劑
120‧‧‧半導體晶片
Claims (11)
- 一種感光性元件,其具備:支撐膜、及設置於所述支撐膜上且由感光性樹脂組成物形成的感光層,所述支撐膜與感光層接觸的面的表面粗糙度以Ra計為大於500nm且4000nm以下,且所述感光性樹脂組成物含有10質量%~90質量%的平均粒徑為1μm以下的無機填充材料、以及醯基膦系化合物,所述無機填充材料含有硫酸鋇以及二氧化矽填料中的至少一者。
- 如申請專利範圍第1項所述之感光性元件,其中所述支撐膜的霧度為60%以上。
- 如申請專利範圍第1項或第2項所述之感光性元件,其中所述感光性樹脂組成物含有多官能環氧樹脂。
- 如申請專利範圍第1項或第2項所述之感光性元件,其中所述感光性樹脂組成物含有具有(甲基)丙烯醯基的光反應性化合物。
- 一種永久抗蝕罩幕的形成方法,其包括:使用如申請專利範圍第1項至第4項中任一項所述之感光性元件,在基板上形成感光層的步驟;對感光層的特定部分照射活性光線,而形成光硬化部的步驟;將所述光硬化部以外的區域除去的步驟。
- 如申請專利範圍第5項所述之永久抗蝕罩幕的形成方法, 其中在所述形成感光層的步驟後、且所述形成光硬化部的步驟前,進一步包括:將支撐膜剝離的步驟。
- 如申請專利範圍第5項或第6項所述之永久抗蝕罩幕的形成方法,其中在所述形成光硬化部的步驟中,使用直接描繪方式、投影曝光方式或以不與感光層直接接觸的方式配置負性罩幕的曝光方式,照射活性光線。
- 如申請專利範圍第5項或第6項所述之永久抗蝕罩幕的形成方法,其中在將光硬化部以外的區域除去的步驟後,進一步包括:進行加熱的步驟。
- 一種永久抗蝕罩幕,其藉由如申請專利範圍第5項至第8項中任一項所述之永久抗蝕罩幕的形成方法而形成。
- 一種半導體封裝的製造方法,其包括:在藉由如申請專利範圍第5項至第8項中任一項所述之永久抗蝕罩幕的形成方法,形成永久抗蝕罩幕的基板上,形成其他構件的步驟。
- 一種積層體,其具備:基板、及在所述基板上使感光性樹脂組成物硬化而得的硬化物,且與基板相反側的面的所述硬化物的表面粗糙度以Ra計為200nm~4000nm。
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- 2015-04-24 TW TW111120150A patent/TWI829181B/zh active
- 2015-04-24 TW TW109145893A patent/TWI769637B/zh active
- 2015-04-24 US US15/306,408 patent/US11054744B2/en active Active
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Publication number | Publication date |
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JP6683125B2 (ja) | 2020-04-15 |
TW202413119A (zh) | 2024-04-01 |
KR20160146700A (ko) | 2016-12-21 |
TW202241712A (zh) | 2022-11-01 |
US20170045817A1 (en) | 2017-02-16 |
KR102444451B1 (ko) | 2022-09-19 |
CN106233205A (zh) | 2016-12-14 |
JP6879348B2 (ja) | 2021-06-02 |
CN106233205B (zh) | 2020-06-23 |
JPWO2015163455A1 (ja) | 2017-04-20 |
US11054744B2 (en) | 2021-07-06 |
KR20220130832A (ko) | 2022-09-27 |
KR20240100483A (ko) | 2024-07-01 |
TWI769637B (zh) | 2022-07-01 |
WO2015163455A1 (ja) | 2015-10-29 |
TWI829181B (zh) | 2024-01-11 |
TW201604655A (zh) | 2016-02-01 |
JP2020076961A (ja) | 2020-05-21 |
TW202116568A (zh) | 2021-05-01 |
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