TWI785196B - 熱硬化性樹脂組成物、膜狀接著劑、接著片及半導體裝置的製造方法 - Google Patents
熱硬化性樹脂組成物、膜狀接著劑、接著片及半導體裝置的製造方法 Download PDFInfo
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- TWI785196B TWI785196B TW108103139A TW108103139A TWI785196B TW I785196 B TWI785196 B TW I785196B TW 108103139 A TW108103139 A TW 108103139A TW 108103139 A TW108103139 A TW 108103139A TW I785196 B TWI785196 B TW I785196B
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Abstract
本發明揭示有一種熱硬化性樹脂組成物,其含有:環氧樹脂;硬化劑;第一彈性體,重量平均分子量為20萬~130萬,具有選自由羧基及羥基所組成的群組中的至少一種官能基;以及第二彈性體,重量平均分子量為20萬~130萬,不具有羧基及羥基;且以熱硬化性樹脂組成物總量為基準,第一彈性體及第二彈性體的合計含量為40質量%以下。
Description
本發明是有關於一種熱硬化性樹脂組成物、膜狀接著劑、接著片及半導體裝置的製造方法。
先前,於半導體晶片與用以搭載半導體晶片的支撐構件的接合中,主要使用銀糊。但是,隨著近年來半導體晶片的小型化.積體化,對於所使用的支撐構件亦開始要求小型化、細密化。另一方面,於使用銀糊的情況下,有時會出現起因於糊的露出或半導體晶片的斜度的於打線接合(wire bonding)時產生的不良、膜厚控制困難、產生空隙等問題。
因此,近年來一直使用用以接合半導體晶片與支撐構件的膜狀接著劑(例如參照專利文獻1)。於使用包括切割帶(dicing tape)及積層於切割帶上的膜狀接著劑的接著片的情況下,藉由於半導體晶圓的背面貼附膜狀接著劑,並藉由切割來使半導體晶圓單片化,而可獲得帶有膜狀接著劑的半導體晶片。所獲得的帶有膜狀接著劑的半導體晶片可經由膜狀接著劑而貼附於支撐構件,並藉由熱壓接而接合。
[現有技術文獻]
[專利文獻]
專利文獻1:日本專利特開2007-053240號公報
然而,隨著半導體晶片的尺寸變小,而於加壓時施加至每單位面積的力變大,因而於高溫加壓處理(例如加壓固化等)中,有時會產生膜狀接著劑自半導體晶片露出的被稱為滲出(bleed)的現象。
另外,於將膜狀接著劑用作作為導線埋入型膜狀接著劑的導線上膜(Film Over Wire,FOW)或作為半導體晶片埋入型膜狀接著劑的晶片上膜(Film Over Die,FOD)的情況下,就提升埋入性的觀點而言,於熱壓接時要求流動性高。因此,有滲出的發生頻率及量進一步增大的傾向。視情況而有時會滲出至半導體晶片上表面,由此而有導致電氣不良或打線接合不良之虞。
本發明是鑒於此種情況而成,主要目的在於提供一種於熱壓接時具有良好的埋入性,並且能夠抑制高溫加壓處理時的滲出量的增加的熱硬化性樹脂組成物。
本發明的一方面提供一種熱硬化性樹脂組成物,其含有:環氧樹脂;硬化劑;第一彈性體,重量平均分子量為20萬~130萬,具有選自由羧基及羥基所組成的群組中的至少一種官能基;以及第二彈性體,重量平均分子量為20萬~130萬,不具有羧基及羥
基;且以熱硬化性樹脂組成物總量為基準,第一彈性體及第二彈性體的合計含量為40質量%以下。根據此種熱硬化性樹脂組成物,於熱壓接時具有良好的埋入性,並且能夠抑制高溫加壓處理時的滲出量的增加。
硬化劑可包含酚樹脂。
第一彈性體可為具有選自由羧基及羥基所組成的群組中的至少一種官能基的丙烯酸樹脂。另外,第二彈性體可為不具有羧基及羥基的丙烯酸樹脂。
環氧樹脂可包含25℃下為液體的環氧樹脂。
熱硬化性樹脂組成物可更含有無機填料。另外,熱硬化性樹脂組成物可更含有硬化促進劑。
熱硬化性樹脂組成物可於將第一半導體元件經由第一導線而以打線接合的方式連接於基板上,並且於第一半導體元件上壓接第二半導體元件而成的半導體裝置中,用來壓接第二半導體元件並且埋入第一導線的至少一部分。
進而,本發明可有關於一種含有環氧樹脂、硬化劑、具有選自由羧基及羥基所組成的群組中的至少一種官能基的第一彈性體、以及不具有羧基及羥基的第二彈性體的熱硬化性樹脂組成物的作為接著劑的應用或用來製造接著劑的應用,其中所述熱硬化性樹脂組成物於將第一半導體元件經由第一導線而以打線接合的方式連接於基板上,並且於第一半導體元件上壓接第二半導體元件而成的半導體裝置中,用來壓接第二半導體元件並且埋入第
一導線的至少一部分。
另一方面中,本發明提供一種膜狀接著劑,其是將所述熱硬化性樹脂組成物形成為膜狀而成。
又一方面中,本發明提供一種接著片,其包括基材及設置於基材上的所述膜狀接著劑。
基材可為切割帶。再者,本說明書中,有時將基材為切割帶的接著片稱為「切割黏晶一體型接著片」。
接著片可更包括積層於膜狀接著劑的與基材為相反側的面上的保護膜。
進而又一方面中,本發明提供一種半導體裝置的製造方法,其包括:打線接合步驟,於基板上經由第一導線而電性連接第一半導體元件;層壓步驟,於第二半導體元件的單面貼附所述膜狀接著劑;以及黏晶(die bond)步驟,經由膜狀接著劑而壓接貼附有膜狀接著劑的第二半導體元件,藉此將第一導線的至少一部分埋入膜狀接著劑中。
再者,半導體裝置可為藉由將第一半導體晶片經由第一導線而以打線接合的方式連接於半導體基板上,並且於第一半導體晶片上,經由接著膜而壓接第二半導體晶片,從而將第一導線的至少一部分埋入接著膜中而成的導線埋入型的半導體裝置;亦可為將第一導線及第一半導體晶片埋入接著膜中而成的晶片埋入型的半導體裝置。
根據本發明,可提供一種於熱壓接時具有良好的埋入性,並且能夠抑制高溫加壓處理時的滲出量的增加的熱硬化性樹脂組成物。因此,將該熱硬化性樹脂組成物形成為膜狀而成的膜狀接著劑可有效用作作為半導體晶片埋入型膜狀接著劑的晶片上膜(Film Over Die,FOD)或作為導線埋入型膜狀接著劑的導線上膜(Film Over Wire,FOW)。另外,根據本發明,可提供使用此種膜狀接著劑的接著片及半導體裝置的製造方法。
10:膜狀接著劑
14:基板
20:基材
30:保護膜
41:接著劑
42:密封材
84、94:電路圖案
88:第一導線
90:有機基板
98:第二導線
100、110:接著片
200:半導體裝置
Wa:第一半導體元件
Waa:第二半導體元件
圖1為表示一實施形態的膜狀接著劑的示意剖面圖。
圖2為表示一實施形態的接著片的示意剖面圖。
圖3為表示另一實施形態的接著片的示意剖面圖。
圖4為表示一實施形態的半導體裝置的示意剖面圖。
圖5為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。
圖6為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。
圖7為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。
圖8為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。
圖9為表示一實施形態的半導體裝置的製造方法的一系列步
驟的示意剖面圖。
以下,適當參照圖式來對本發明的實施形態進行說明。但,本發明並不限定於以下的實施形態。
本說明書中,(甲基)丙烯酸是指丙烯酸或與其對應的甲基丙烯酸。關於(甲基)丙烯醯基等其他的類似表述亦同樣。
[熱硬化性樹脂組成物]
本實施形態的熱硬化性樹脂組成物含有:(A)環氧樹脂、(B)硬化劑、(C)具有選自由羧基及羥基所組成的群組中的至少一種官能基的第一彈性體、以及(D)不具有羧基及羥基的第二彈性體。熱硬化性樹脂組成物經過半硬化(B階段)狀態且於硬化處理後可成完全硬化物(C階段)狀態。
<(A)成分:環氧樹脂>
(A)成分只要為分子內具有環氧基者則可並無特別限制地使用。作為(A)成分,例如可列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂、含二環戊二烯骨架的環氧樹脂、二苯乙烯型環氧樹脂、含三嗪骨架的環氧樹脂、含茀骨架的環氧樹脂、三苯酚甲烷型環氧樹脂、聯苯型環氧樹脂、伸二甲苯基型環氧樹脂、苯基芳烷基型環氧樹脂、聯苯芳烷基型環氧樹脂、萘型環氧樹脂、多官能苯酚類、蒽等多環芳香族類的二縮水甘油醚化合物等。該
些可單獨使用一種或者將兩種以上組合使用。該些中,就流動性的觀點而言,(A)成分較佳為150℃熔融黏度為1.0Pa.s以下者。另外,(A)成分亦可包含環氧樹脂於25℃下為液體的環氧樹脂。
(A)成分的環氧當量並無特別限制,可為90g/eq~300g/eq、或110g/eq~290g/eq。若(A)成分的環氧當量為此種範圍,則有可維持膜狀接著劑的整體強度(bulk intensity)並且確保流動性的傾向。
作為(A)成分的市售品,例如可列舉迪愛生(DIC)股份有限公司製造的HP-7200系列、新日鐵住金化學股份有限公司製造的YDCN系列、日本化藥股份有限公司製造的NC-3000、NC-7000系列等。
<(B)成分:硬化劑>
(B)成分並無特別限制,可使用作為環氧樹脂的硬化劑而通常所使用者。作為(B)成分,例如可列舉:酚樹脂、酯化合物、芳香族胺、脂肪族胺、酸酐等。該些可單獨使用一種或者將兩種以上組合使用。該些中,就反應性及經時穩定性的觀點而言,(B)成分可包含酚樹脂。
酚樹脂只要為分子內具有酚性羥基者則可並無特別限制地使用。作為酚樹脂,例如可列舉:使苯酚、甲酚、間苯二酚(resorcin)、鄰苯二酚、雙酚A、雙酚F、苯基苯酚、胺基苯酚等酚類及/或α-萘酚、β-萘酚、二羥基萘等萘酚類與甲醛等具有醛基的化合物於酸性觸媒下縮合或共縮合而獲得的酚醛清漆型酚樹
脂;由烯丙基化雙酚A、烯丙基化雙酚F、烯丙基化萘二醇、苯酚酚醛清漆、苯酚等酚類及/或萘酚類與二甲氧基對二甲苯或雙(甲氧基甲基)聯苯所合成的苯酚芳烷基樹脂、萘酚芳烷基樹脂、聯苯芳烷基型酚樹脂、苯基芳烷基型酚樹脂等。該些可單獨使用一種或者將兩種以上組合使用。該些中,就耐熱性的觀點而言,酚樹脂較佳為於85℃、85%RH的恆溫恆濕槽中48小時的條件下,吸水率為2質量%以下,且利用熱重量分析儀(thermogravimetric analyzer,TGA)測定出的350℃下的加熱質量減少率(升溫速度:5℃/min,環境:氮)小於5質量%者。
作為酚樹脂的市售品,例如可列舉:芬萊特(Phenolite)KA系列、TD系列(DIC股份有限公司製造);米萊斯(Mirex)XLC系列、XL系列(三井化學股份有限公司製造);HE系列(空氣水(AIR WATER)股份有限公司製造)等。
酚樹脂的羥基當量並無特別限制,可為80g/eq~250g/eq、90g/eq~200g/eq、或100g/eq~180g/eq。若酚樹脂的羥基當量為此種範圍,則有可保持膜狀接著劑的流動性並且更高地維持接著力的傾向。
就硬化性的觀點而言,(A)成分的環氧當量與(B)成分的羥基當量的比(環氧樹脂的環氧當量/酚樹脂的羥基當量)可為0.30/0.70~0.70/0.30、0.35/0.65~0.65/0.35、0.40/0.60~0.60/0.40、或0.45/0.55~0.55/0.45。若該當量比為0.30/0.70以上,則有可獲得更充分的硬化性的傾向。若該當量比為0.70/0.30以
下,則可防止黏度變得過高,可獲得更充分的流動性。
以熱硬化性樹脂組成物總量為基準,(A)成分及(B)成分的合計含量可為10質量%~80質量%。(A)成分及(B)成分的合計含量可為20質量%以上、25質量%以上、或30質量%以上,且可為70質量%以下、60質量%以下、或50質量%以下。若以熱硬化性樹脂組成物總量為基準,(A)成分及(B)成分的合計含量為10質量%以上,則有可獲得充分的接著力的傾向。若以熱硬化性樹脂組成物總量為基準,(A)成分及(B)成分的合計含量為80質量%以下,則有可防止黏度變得過低,可進一步抑制滲出量的傾向。
<(C)成分:第一彈性體>
(C)成分為重量平均分子量為20萬~130萬,且具有選自由羧基及羥基所組成的群組中的至少一種官能基的彈性體。(C)成分可為具有羧基的彈性體。藉由熱硬化性樹脂組成物含有(C)成分,而於熱壓接時進行交聯反應,熱硬化性樹脂組成物增黏,從而能夠抑制高溫加壓處理時的滲出量的增加。(C)成分較佳為構成彈性體的聚合物的玻璃轉移溫度(Tg)為50℃以下者。
(C)成分只要為具有選自由羧基及羥基所組成的群組中的至少一種官能基者則並無特別限制,例如可列舉為丙烯酸樹脂、聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、矽酮樹脂、丁二烯樹脂、丙烯腈樹脂及該些的改質體等,且具有選自由羧基及羥基所組成的群組中的至少一種官能基者。
就對溶劑的溶解性、流動性的觀點而言,(C)成分可為具有選自由羧基及羥基所組成的群組中的至少一種官能基的丙烯酸樹脂。此處,所謂丙烯酸樹脂,是指包含源自(甲基)丙烯酸酯的結構單元的聚合物。丙烯酸樹脂較佳為包含源自具有醇性或酚性羥基、或者羧基的(甲基)丙烯酸酯的結構單元作為結構單元的聚合物。另外,丙烯酸樹脂亦可為(甲基)丙烯酸酯與丙烯腈的共聚物等丙烯酸橡膠。
(C)成分的玻璃轉移溫度(Tg)可為-50℃~50℃或-30℃~30℃。若丙烯酸樹脂的Tg為-50℃以上,則有可防止熱硬化性樹脂組成物的柔軟性變得過高的傾向。藉此,於晶圓切割時容易將膜狀接著劑切斷,能夠防止毛刺的產生。若丙烯酸樹脂的Tg為50℃以下,則有可抑制熱硬化性樹脂組成物的柔軟性下降的傾向。藉此,當將膜狀接著劑貼附於晶圓時,有容易將空隙充分埋入的傾向。另外,能夠防止由晶圓的密接性的下降所導致的切割時的碎化(chipping)。此處,玻璃轉移溫度(Tg)是使用示差掃描熱量計(Differential Scanning Calorimeter,DSC)(例如理學股份有限公司製造的「Thermo Plus 2」)所測定出的值。
(C)成分的重量平均分子量(Mw)為20萬~130萬。(C)成分的Mw可為30萬以上、40萬以上、或45萬以上,且可為110萬以下、100萬以下、或95萬以下。若丙烯酸樹脂的Mw為此種範圍,則可適當地控制膜形成性、膜狀時的強度、可撓性、黏性等,並且回流性優異,可提升埋入性。此處,Mw是指藉由凝
膠滲透層析法(Gel Permeation Chromatography,GPC)進行測定,並使用基於標準聚苯乙烯的校準曲線進行換算而得的值。
就硬化性的觀點而言,具有羧基的(C)成分的酸價可為1mgKOH/g~60mgKOH/g、3mgKOH/g~50mgKOH/g、或5mgKOH/g~40mgKOH/g。若酸價為此種範圍,則有可防止清漆中的凝膠化及B階段狀態的流動性的下降的傾向。
就硬化性的觀點而言,具有羥基的(C)成分的羥基價可為1mgKOH/g~60mgKOH/g、3mgKOH/g~50mgKOH/g、或5mgKOH/g~40mgKOH/g。若羥基價為此種範圍,則有可防止清漆中的凝膠化及B階段狀態的流動性的下降的傾向。
作為(C)成分的市售品,例如可列舉:SG-70L、SG-708-6、WS-023 EK30、SG-280 EK23(均為長瀨化成(Nagase ChemteX)股份有限公司製造)。
<(D)成分:第二彈性體>
(D)成分為重量平均分子量為20萬~130萬,且不具有羧基及羥基的彈性體。(D)成分可為具有羧基及羥基以外的官能基(例如縮水甘油基等)的彈性體。藉由熱硬化性樹脂組成物含有(D)成分,經時穩定性可變良好。(D)成分較佳為構成彈性體的聚合物的玻璃轉移溫度(Tg)為50℃以下者。
(D)成分只要為不具有羧基及羥基者則並無特別限制,例如可列舉為丙烯酸樹脂、聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、矽酮樹脂、丁二烯樹脂、丙烯腈樹脂及該些的改質體等,
且不具有羧基及羥基者。
就對溶劑的溶解性、流動性的觀點而言,(D)成分可為不具有羧基及羥基的丙烯酸樹脂。丙烯酸樹脂的含義與上文相同。丙烯酸樹脂較佳為包含具有縮水甘油基等環氧基的官能性單體((甲基)丙烯酸酯等)的聚合物。另外,丙烯酸樹脂亦可為(甲基)丙烯酸酯與丙烯腈的共聚物等丙烯酸橡膠。
(D)成分的玻璃轉移溫度(Tg)可為-50℃~50℃或-30℃~30℃。若丙烯酸樹脂的Tg為-50℃以上,則有可防止熱硬化性樹脂組成物的柔軟性變得過高的傾向。藉此,於晶圓切割時容易將膜狀接著劑切斷,能夠防止毛刺的產生。若丙烯酸樹脂的Tg為50℃以下,則有可抑制熱硬化性樹脂組成物的柔軟性下降的傾向。藉此,當將膜狀接著劑貼附於晶圓時,有容易將空隙充分埋入的傾向。另外,能夠防止由晶圓的密接性的下降所導致的切割時的碎化。此處,玻璃轉移溫度(Tg)是使用DSC(示差掃描熱量計)(例如理學股份有限公司製造的「Thermo Plus 2」)所測定出的值。
(D)成分的重量平均分子量(Mw)為20萬~130萬。(D)成分的Mw可為30萬以上、40萬以上、50萬以上、或60萬以上,且可為120萬以下、110萬以下、100萬以下、95萬以下、或90萬以下。若丙烯酸樹脂的Mw為此種範圍,則可適當地控制膜形成性、膜狀時的強度、可撓性、黏性等,並且回流性優異,可提升埋入性。此處,Mw是指藉由凝膠滲透層析法(GPC)進行
測定,並使用基於標準聚苯乙烯的校準曲線進行換算而得的值。
作為(D)成分的市售品,例如可列舉:SG-P3、SG-80H、HTR-860P-3CSP(均為長瀨化成(Nagase ChemteX)股份有限公司製造)。
以熱硬化性樹脂組成物總量為基準,(C)成分及(D)成分的合計含量為40質量%以下。(C)成分及(D)成分的合計含量可為35質量%以下、30質量%以下、或28質量%以下。若以熱硬化性樹脂組成物總量為基準,(C)成分及(D)成分的合計含量為40質量%以下,則有埋入性更優異的傾向。(C)成分及(D)成分的合計含量可為1質量%以上、5質量%以上、10質量%以上、或15質量%以上。
(C)成分相對於熱硬化性樹脂組成物中的(C)成分及(D)成分的總量而言的質量比((C)成分的含量/(C)成分及(D)成分的含量的總量)可為0.01~0.50。質量比可為0.02以上、0.03以上、或0.05以上,且可為0.30以下、0.20以下、或0.10以下。若(C)成分相對於(C)成分及(D)成分而言的質量比為0.01以上,則有可進一步抑制高溫加壓處理時的滲出量的增加的傾向。若(C)成分相對於(C)成分及(D)成分而言的質量比為0.50以下,則有可維持更良好的埋入性的傾向。
<(E)成分:無機填料>
本實施形態的熱硬化性樹脂組成物可更含有(E)無機填料。作為無機填料,例如可列舉:氫氧化鋁、氫氧化鎂、碳酸鈣、碳
酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、硼酸鋁晶鬚、氮化硼、結晶性二氧化矽、非晶性二氧化矽等。該些可單獨使用一種或者將兩種以上組合使用。就所獲得的膜狀接著劑的導熱性進一步提升的觀點而言,無機填料可包含氧化鋁、氮化鋁、氮化硼、結晶性二氧化矽或非晶性二氧化矽。另外,就調整熱硬化性樹脂組成物的熔融黏度的觀點及對熱硬化性樹脂組成物賦予觸變性的觀點而言,無機填料可包含氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、結晶性二氧化矽或非晶性二氧化矽。
就接著性進一步提升的觀點而言,(E)成分的平均粒徑可為0.005μm~0.5μm或0.05μm~0.3μm。此處,平均粒徑是指藉由根據布厄特(Brunauer-Emmett-Teller,BET)比表面積進行換算而求出的值。
就其表面與溶劑、其他成分等的相容性、接著強度的觀點而言,(E)成分可藉由表面處理劑進行表面處理。作為表面處理劑,例如可列舉矽烷偶合劑等。作為矽烷偶合劑的官能基,例如可列舉:乙烯基、(甲基)丙烯醯基、環氧基、巰基、胺基、二胺基、烷氧基、乙氧基等。
相對於(A)成分、(B)成分、(C)成分及(D)成分的總量100質量份而言,(E)成分的含量可為10質量份~90質量份或10質量份~50質量份。若相對於(A)成分、(B)成分、(C)成分及(D)成分的總量100質量份而言,(E)成分的含量
為10質量份以上,則有硬化前的接著層的切割性提升,硬化後的接著層的接著力提升的傾向。若相對於(A)成分、(B)成分、(C)成分及(D)成分的總量100質量份而言,(E)成分的含量為90質量份以下,則可抑制流動性的下降,能夠防止硬化後的膜狀接著劑的彈性係數變得過高。
<(F)成分:硬化促進劑>
本實施形態的熱硬化性樹脂組成物可更含有(F)硬化促進劑。硬化促進劑並無特別限定,可使用通常所使用者。作為(F)成分,例如可列舉:咪唑類及其衍生物、有機磷系化合物、二級胺類、三級胺類、四級銨鹽等。該些可單獨使用一種或者將兩種以上組合使用。該些中,就反應性的觀點而言,(F)成分可為咪唑類及其衍生物。
作為咪唑類,例如可列舉:2-甲基咪唑、1-苄基-2-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑等。該些可單獨使用一種或者將兩種以上組合使用。
相對於(A)成分、(B)成分、(C)成分及(D)成分的總量100質量份而言,(F)成分的含量可為0.04質量份~3質量份或0.04質量份~0.2質量份。若(F)成分的含量為此種範圍,則有可兼具硬化性及可靠性的傾向。
<其他成分>
本實施形態的熱硬化性樹脂組成物可更含有抗氧化劑、矽烷偶合劑、流變控制劑等作為其他成分。相對於(A)成分、(B)成
分、(C)成分及(D)成分的總量100質量份而言,該些成分的含量可為0.02質量份~3質量份。
本實施形態的熱硬化性樹脂組成物可作為經溶劑稀釋的接著劑清漆來使用。溶劑只要為可溶解(E)成分以外的成分者則並無特別限制。作為溶劑,例如可列舉:甲苯、二甲苯、均三甲苯、異丙苯(cumene)、對異丙基甲苯等芳香族烴;己烷、庚烷等脂肪族烴;甲基環己烷等環狀烷烴;四氫呋喃、1,4-二噁烷等環狀醚;丙酮、甲基乙基酮、甲基異丁基酮、環己酮、4-羥基-4-甲基-2-戊酮等酮;乙酸甲酯、乙酸乙酯、乙酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯等酯;碳酸伸乙酯、碳酸伸丙酯等碳酸酯;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等醯胺等。該些可單獨使用一種或者將兩種以上組合使用。該些中,就溶解性及沸點的觀點而言,溶劑可為甲苯、二甲苯、甲基乙基酮、甲基異丁基酮、或環己酮。
以接著劑清漆的總質量為基準,接著劑清漆中的固體成分濃度可為10質量%~80質量%。
接著劑清漆可藉由將(A)成分、(B)成分、(C)成分、(D)成分及溶劑、以及視需要的(E)成分、(F)成分及其他成分加以混合、混煉而進行製備。混合及混煉可將通常的攪拌機、擂潰機、三輥磨機(three-rod roll mill)、球磨機(ball mill)、珠磨機(bead mill)等分散機適當組合而進行。於含有(E)成分的情況下,藉由在預先混合(E)成分與低分子量成分後調配高分子
量成分,而可縮短進行混合的時間。另外,於製備接著劑清漆後,可藉由真空脫氣等將清漆中的氣泡去除。
[膜狀接著劑]
圖1為表示一實施形態的膜狀接著劑的示意剖面圖。膜狀接著劑10為將以上所述的熱硬化性樹脂組成物形成為膜狀而成者。膜狀接著劑10可為半硬化(B階段)狀態。此種膜狀接著劑10可藉由將熱硬化性樹脂組成物塗佈於支撐膜而形成。於使用接著劑清漆的情況下,可將接著劑清漆塗佈於支撐膜,並進行加熱乾燥而將溶劑去除,藉此而形成膜狀接著劑10。
支撐膜並無特別限制,例如可列舉:聚四氟乙烯、聚乙烯、聚丙烯、聚甲基戊烯、聚對苯二甲酸乙二酯、聚醯亞胺等的膜。支撐膜的厚度例如可為60μm~200μm或70μm~170μm。
作為將接著劑清漆塗佈於支撐膜的方法,可使用公知的方法,例如可列舉:刮塗法、輥塗法、噴塗法、凹版塗佈法、棒塗法、簾塗法等。加熱乾燥的條件只要為所使用的溶劑充分揮發的條件則無特別限制,例如可為50℃~200℃下0.1分鐘~90分鐘。
膜狀接著劑的厚度可根據用途而適當調整。就將半導體晶片、導線、基板的配線電路等凹凸等充分埋入的觀點而言,膜狀接著劑的厚度可為20μm~200μm、30μm~200μm、或40μm~150μm。
[接著片]
圖2為表示一實施形態的接著片的示意剖面圖。接著片100
包括基材20及設置於基材上的以上所述的膜狀接著劑10。
基材20並無特別限制,可為基材膜。基材膜可為與所述支撐膜相同者。
基材20可為切割帶。此種接著片可用作切割黏晶一體型接著片。該情況下,由於對半導體晶圓的層壓步驟為一次,因此可有效率地作業。
作為切割帶,例如可列舉:聚四氟乙烯膜、聚對苯二甲酸乙二酯膜、聚乙烯膜、聚丙烯膜、聚甲基戊烯膜、聚醯亞胺膜等塑膠膜等。另外,切割帶視需要可進行底塗塗佈、UV處理、電暈放電處理、研磨處理、蝕刻處理等表面處理。切割帶較佳為具有黏著性者。此種切割帶可為對所述塑膠膜賦予黏著性者,亦可為於所述塑膠膜的單面設置有黏著劑層者。
接著片100可與形成以上所述的膜狀接著劑的方法同樣地,藉由將熱硬化性樹脂組成物塗佈於基材膜而形成。將熱硬化性樹脂組成物塗佈於基材20的方法可與將以上所述的熱硬化性樹脂組成物塗佈於支撐膜的方法相同。
接著片100可使用預先製作的膜狀接著劑來形成。該情況下,接著片100可藉由使用輥層壓機、真空層壓機等於規定條件(例如室溫(20℃)或加熱狀態)下進行層壓而形成。接著片100可連續地製造,就效率佳而言,較佳為於加熱狀態下使用輥層壓機來形成。
就半導體晶片、導線、基板的配線電路等凹凸等的埋入
性的觀點而言,膜狀接著劑10的厚度可為20μm~200μm、30μm~200μm、或40μm~150μm。若膜狀接著劑10的厚度為20μm以上,則有可獲得更充分的接著力的傾向,若膜狀接著劑10的厚度為200μm以下,則經濟且能夠響應半導體裝置的小型化的要求。
圖3為表示另一實施形態的接著片的示意剖面圖。接著片110更包括積層於膜狀接著劑10的與基材20為相反側的面上的保護膜30。保護膜30可為與以上所述的支撐膜相同者。保護膜的厚度例如可為15μm~200μm或70μm~170μm。
[半導體裝置]
圖4為表示一實施形態的半導體裝置的示意剖面圖。半導體裝置200是藉由將第一階段的第一半導體元件Wa經由第一導線88而以打線接合的方式連接於基板14,並且於第一半導體元件Wa上,經由膜狀接著劑10而壓接第二半導體元件Waa,從而將第一導線88的至少一部分埋入膜狀接著劑10中而成的半導體裝置。半導體裝置可為將第一導線88的至少一部分埋入而成的導線埋入型的半導體裝置,亦可為將第一導線88及第一半導體元件Wa埋入而成的半導體裝置。另外,半導體裝置200中,進而經由第二導線98而將基板14與第二半導體元件Waa電性連接,並且藉由密封材42而將第二半導體元件Waa密封。
第一半導體元件Wa的厚度可為10μm~170μm,第二半導體元件Waa的厚度可為20μm~400μm。埋入至膜狀接著劑10內部的第一半導體元件Wa為用以驅動半導體裝置200的控制
器晶片。
基板14包括電路圖案84、94分別於表面各形成有兩處的有機基板90。第一半導體元件Wa經由接著劑41而壓接於電路圖案94上。第二半導體元件Waa以覆蓋未壓接有第一半導體元件Wa的電路圖案94、第一半導體元件Wa、及電路圖案84的一部分的方式經由膜狀接著劑10而壓接於基板14。於由基板14上的電路圖案84、94所引起的凹凸的階差中埋入有膜狀接著劑10。並且,利用樹脂製的密封材42而將第二半導體元件Waa、電路圖案84及第二導線98密封。
[半導體裝置的製造方法]
本實施形態的半導體裝置的製造方法包括:於基板上經由第一導線而電性連接第一半導體元件的第一打線接合步驟;於第二半導體元件的單面貼附以上所述的膜狀接著劑的層壓步驟;以及經由膜狀接著劑來壓接貼附有膜狀接著劑的第二半導體元件,藉此將第一導線的至少一部分埋入膜狀接著劑中的黏晶步驟。
圖5~圖9為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。本實施形態的半導體裝置200為將第一導線88及第一半導體元件Wa埋入而成的半導體裝置,可藉由以下程序而製造。首先,如圖5所示,於基板14上的電路圖案94上壓接具有接著劑41的第一半導體元件Wa,且經由第一導線88而將基板14上的電路圖案84與第一半導體元件Wa電性接合連接(第一打線接合步驟)。
其次,於半導體晶圓(例如厚度為100μm、尺寸為8吋)的單面上層壓接著片100,並剝去基材20,藉此而於半導體晶圓的單面貼附膜狀接著劑10(例如厚度為110μm)。並且,於將切割帶貼合於膜狀接著劑10後,切割為規定的大小(例如7.5mm見方),藉此而如圖6所示,獲得貼附有膜狀接著劑10的第二半導體元件Waa(層壓步驟)。
層壓步驟的溫度條件可為50℃~100℃或60℃~80℃。若層壓步驟的溫度為50℃以上,則可獲得與半導體晶圓的良好的密接性。若層壓步驟的溫度為100℃以下,則可抑制膜狀接著劑10於層壓步驟中過度流動,因而可防止引起厚度的變化等。
作為切割方法,例如可列舉:使用旋轉刀刃的刀片切割、藉由雷射而將膜狀接著劑或晶圓與膜狀接著劑的兩者切斷的方法等。
並且,將貼附有膜狀接著劑10的第二半導體元件Waa壓接於經由第一導線88而接合連接有第一半導體元件Wa的基板14。具體而言,如圖7所示,以藉由膜狀接著劑10來覆蓋第一導線88及第一半導體元件Wa的方式載置貼附有膜狀接著劑10的第二半導體元件Waa,繼而,如圖8所示,藉由使第二半導體元件Waa壓接於基板14而將第二半導體元件Waa固定於基板14(黏晶步驟)。黏晶步驟較佳為將膜狀接著劑10於80℃~180℃、0.01MPa~0.50MPa的條件下壓接0.5秒~3.0秒。於黏晶步驟之後,將膜狀接著劑10於60℃~175℃、0.3MPa~0.7MPa的條件下加
壓及加熱5分鐘以上。
繼而,如圖9所示,於將基板14與第二半導體元件Waa經由第二導線98而電性連接後(第二打線接合步驟),利用密封材42將電路圖案84、第二導線98及第二半導體元件Waa密封。藉由經過此種步驟而可製造半導體裝置200。
作為其他實施形態,半導體裝置亦可為將第一導線88的至少一部分埋入而成的導線埋入型的半導體裝置。
[實施例]
以下,列舉實施例來對本發明進行更具體的說明。但本發明並不限定於該些實施例。
(實施例1~實施例7及比較例1~比較例3)
<接著劑片的製作>
將以下所示的各成分以表1所示的調配比例(質量份)混合,並使用環己酮作為溶媒來製備固體成分為40質量%的熱硬化性樹脂組成物的清漆。其次,利用100目的過濾器對所獲得的清漆進行過濾,並進行真空脫泡。將真空脫泡後的清漆塗佈於作為基材膜的厚度38μm的已實施脫模處理的聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)膜上。以90℃下5分鐘、繼而140℃下5分鐘的兩階段對所塗佈的清漆進行加熱乾燥。如此而獲得於基材膜上具有處於半硬化(B階段)狀態的厚度110μm的膜狀接著劑的接著片。
再者,表1中的各成分如下所述。
(A)環氧樹脂
A-1:含二環戊二烯骨架的環氧樹脂,DIC股份有限公司製造,商品名:HP-7200L,環氧當量:242g/eq~252g/eq
A-2:甲酚酚醛清漆型環氧樹脂,新日鐵住金化學股份有限公司製造,商品名:YDCN-700-10,環氧當量:209g/eq
A-3:雙酚F型環氧樹脂(25℃下為液體),DIC股份有限公司製造,商品名:EXA-830CRP,環氧當量:159g/eq
(B)硬化劑
B-1:聯苯芳烷基型酚樹脂,空氣水股份有限公司製造,商品名:HE-200C-10,羥基當量:205g/eq
B-2:苯基芳烷基型酚樹脂,空氣水股份有限公司製造,商品名:HE100C-30,羥基當量:175g/eq
(C)第一彈性體(具有選自由羧基及羥基所組成的群組中的至少一種官能基的彈性體)
C-1:丙烯酸橡膠,長瀨化成股份有限公司製造,商品名:WS-023 EK30,重量平均分子量:50萬,酸價:20mgKOH/g,Tg:-10℃
C-2:丙烯酸橡膠,長瀨化成股份有限公司製造,商品名:SG-708-6,重量平均分子量:70萬,酸價:9mgKOH/g,Tg:4℃
C-3:丙烯酸橡膠,長瀨化成股份有限公司製造,商品名:SG-280 EK23,重量平均分子量:90萬,酸價:30mgKOH/g,Tg:
-29℃
(D)第二彈性體(不具有羧基及羥基的彈性體)
D-1:丙烯酸橡膠,長瀨化成股份有限公司製造,商品名:HTR-860P-3CSP,重量平均分子量:80萬,含縮水甘油基的單體比率:3%,Tg:-7℃
D-2:丙烯酸橡膠,長瀨化成股份有限公司製造,商品名:HTR-860P-30B-CHN,重量平均分子量:23萬,含縮水甘油基的單體比率:8%,Tg:-7℃
D-3:丙烯酸橡膠,長瀨化成股份有限公司製造,HTR-860P-3CSP改良品(商品名:HTR-860P-3CSP,長瀨化成股份有限公司製造的丙烯酸橡膠中,除去源自丙烯腈的結構單元者),重量平均分子量:60萬,Tg:12℃
(E)無機填料
E-1:二氧化矽填料分散液,熔融二氧化矽,雅都瑪(Admatechs)股份有限公司製造,商品名:SC2050-HLG,平均粒徑:0.50μm
(F)硬化促進劑
F-1:1-氰基乙基-2-苯基咪唑,四國化成工業股份有限公司製造,商品名:固唑(Curezol)2PZ-CN
<各種物性的評價>
對所獲得的實施例1~實施例7及比較例1~比較例3的接著片進行埋入性及滲出量的評價。
[埋入性評價]
製作以下評價樣品來對接著片的埋入性進行評價。對於以上所獲得的膜狀接著劑(厚度110μm),剝去基材膜並貼附於切割帶,獲得切割黏晶一體型接著片。其次,將厚度100μm的半導體晶圓(8吋)加熱至70℃而貼附於接著劑側。其後,將該半導體晶圓切割為7.5mm見方,藉此而獲得半導體晶片A。其次,準備切割黏晶一體型接著片(日立化成股份有限公司,商品名:HR9004-10)(厚度10μm),加熱至70℃而貼附於厚度50μm的半導體晶圓(8吋)。其後,將該半導體晶圓切割為4.5mm見方,藉此而獲得帶有黏晶膜的半導體晶片B。繼而,準備塗佈有阻焊劑(太陽日酸股份有限公司,商品名:AUS308)的總厚度為260μm的評價用基板,以帶有黏晶膜的半導體晶片B的黏晶膜與評價用基板的阻焊劑接觸的方式,於120℃、0.20MPa、2秒的條件下進行壓接。其後,以半導體晶片A的膜狀接著劑與半導體晶片B的半導體晶圓接觸的方式,於120℃、0.20MPa、1.5秒的條件下進行壓接,獲得評價樣品。此時,以先前所壓接的半導體晶片B處於半導體晶片A的中央的方式進行位置對準。對以所述方式獲得的評價樣品,利用超音波數位圖像診斷裝置(因賽特(Insight)股份有限公司製造,探針:75MHz)來觀測空隙的有無,於觀測到空隙的情況下算出每單位面積的空隙的面積的比例,並將該些分析結果作為埋入性進行評價。評價基準如下所述。將結果示於表1中。
A:未觀察到空隙。
B:雖觀測到空隙,但其比例小於5面積%。
C:觀察到空隙,且其比例為5面積%以上。
[滲出量評價]
僅對所述埋入性評價中評價為「A」或「B」者進行滲出量評價。藉由與所述埋入性評價中所製作的評價樣品相同的程序來製作評價樣品。將半導體晶片A的膜狀接著劑與半導體晶片B的半導體晶圓,於120℃、0.20MPa、1.5秒的條件下壓接。繼而,使用加壓烘箱,於140℃、0.7MPa、30分鐘的條件下進行高溫加壓處理(加壓固化),於加壓固化前後,利用顯微鏡來觀察評價樣品,自評價樣品的四邊的中心,分別測定膜狀接著劑的滲出量(露出量)。將加壓固化前的滲出量設為L1,將加壓固化後的滲出量設為L2,並基於下式來算出滲出量增加率。將結果示於表1中。
滲出量增加率(%)=(L2-L1)/L1×100
如表1所示,與僅含有第一彈性體或第二彈性體的任一者的比較例1~比較例3相比,含有第一彈性體及第二彈性體的實施例1~實施例7的埋入性優異,高溫加壓處理時的滲出量增加率亦低。根據該些結果而確認到:本發明的熱硬化性樹脂組成物於熱壓接時具有良好的埋入性,並且能夠抑制高溫加壓處理時的滲出量的增加。
[產業上之可利用性]
如以上結果所示,本發明的熱硬化性樹脂組成物於熱壓接時具有良好的埋入性,並且可抑制高溫加壓處理時的滲出量的增加,因此將熱硬化性樹脂組成物形成為膜狀而成的膜狀接著劑可有效用作作為晶片埋入型膜狀接著劑的晶片上膜(Film Over Die,FOD)或作為導線埋入型膜狀接著劑的導線上膜(Film Over Wire,FOW)。
10‧‧‧膜狀接著劑
Claims (11)
- 一種熱硬化性樹脂組成物,其含有:環氧樹脂;酚樹脂;第一彈性體,重量平均分子量為20萬~130萬,具有選自由羧基及羥基所組成的群組中的至少一種官能基;以及第二彈性體,重量平均分子量為20萬~130萬,不具有羧基及羥基;且以熱硬化性樹脂組成物總量為基準,所述環氧樹脂及所述酚樹脂的合計含量為30質量%~70質量%,以熱硬化性樹脂組成物總量為基準,所述第一彈性體及所述第二彈性體的合計含量為10質量%~30質量%。
- 如申請專利範圍第1項所述的熱硬化性樹脂組成物,其中所述第一彈性體為具有選自由羧基及羥基所組成的群組中的至少一種官能基的丙烯酸樹脂。
- 如申請專利範圍第1項或第2項所述的熱硬化性樹脂組成物,其中所述第二彈性體為不具有羧基及羥基的丙烯酸樹脂。
- 如申請專利範圍第1項或第2項所述的熱硬化性樹脂組成物,其中所述環氧樹脂包含25℃下為液體的環氧樹脂。
- 如申請專利範圍第1項或第2項所述的熱硬化性樹脂組成物,其更含有無機填料。
- 如申請專利範圍第1項或第2項所述的熱硬化性樹脂組 成物,其更含有硬化促進劑。
- 一種膜狀接著劑,其是將如申請專利範圍第1項至第6項中任一項所述的熱硬化性樹脂組成物形成為膜狀而成。
- 一種接著片,其包括:基材;以及設置於所述基材上的如申請專利範圍第7項所述的膜狀接著劑。
- 如申請專利範圍第8項所述的接著片,其中所述基材為切割帶。
- 如申請專利範圍第8項或第9項所述的接著片,其更包括積層於所述膜狀接著劑的與所述基材為相反側的面上的保護膜。
- 一種半導體裝置的製造方法,其包括:打線接合步驟,於基板上經由第一導線而電性連接第一半導體元件;層壓步驟,於第二半導體元件的單面貼附如申請專利範圍第7項所述的膜狀接著劑;以及黏晶步驟,經由所述膜狀接著劑而壓接貼附有所述膜狀接著劑的第二半導體元件,藉此將所述第一導線的至少一部分埋入所述膜狀接著劑中。
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CN111630643A (zh) | 2020-09-04 |
JP7283399B2 (ja) | 2023-05-30 |
KR102561428B1 (ko) | 2023-07-31 |
SG11202006827RA (en) | 2020-08-28 |
KR20200115515A (ko) | 2020-10-07 |
TW201940635A (zh) | 2019-10-16 |
WO2019150995A1 (ja) | 2019-08-08 |
JPWO2019150995A1 (ja) | 2021-02-25 |
WO2019150433A1 (ja) | 2019-08-08 |
CN111630643B (zh) | 2023-07-07 |
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