TW201335302A - 半導體用黏著劑、助焊劑、半導體裝置的製造方法及半導體裝置 - Google Patents
半導體用黏著劑、助焊劑、半導體裝置的製造方法及半導體裝置 Download PDFInfo
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- TW201335302A TW201335302A TW101138291A TW101138291A TW201335302A TW 201335302 A TW201335302 A TW 201335302A TW 101138291 A TW101138291 A TW 101138291A TW 101138291 A TW101138291 A TW 101138291A TW 201335302 A TW201335302 A TW 201335302A
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Abstract
一種半導體用黏著劑,其含有環氧樹脂、硬化劑及具有下述通式(1-1)或(1-2)所示的基團之化合物,□□[式中,R1表示電子供給基,複數存在的R1彼此可相同亦可不同]。
Description
本發明是關於半導體用黏著劑、助焊劑、半導體裝置的製造方法及半導體裝置。
以往,在連接半導體晶片與基板時,廣泛地採用一種使用金線等的金屬細線之引線接合方式。另一方面,為了因應對於半導體裝置的高機能化、高集積化、高速化等的要求,在半導體晶片或基板上形成被稱為「凸塊(bump)」的導電性突起,直接連接半導體晶片與基板之倒裝晶片連接方式(FC連接方式),持續地普及。
例如,關於半導體晶片及基板之間的連接,球柵陣列(BGA(Ball Grid Array))、晶片尺寸封裝(CSP(Chip Size Package))等被廣為使用的板上晶片封裝(COB(Chip On Board))型連接方式,也屬於FC連接方式的範疇。又,FC連接方式,晶片上晶片封裝(COC(Chip On Chip))型的連接方式也廣泛地被使用,該COC型連接方式是先在半導體晶片上形成連接部(凸塊或配線),然後連接半導體晶片之間(例如,參考專利文獻1)。
又,在被強烈要求更加小型化、薄型化、高機能化的封裝中,將上述連接方式經積層而多段化後的晶片堆疊型封裝、或封裝層疊(POP(Package On Package))、三維晶片
堆疊構裝(TSV(Through-Silicon Via))等的封裝,也開始廣為普及。這樣的積層、多段化技術,是將半導體晶片等配置成立體(三次元)狀,因此與平面(二次元)的配置方式相比,可使封裝變得更小。又,對於半導體的性能提高、改善雜訊、減少構裝面積、省電化方面,也是有效的,因而被認為是新一代的半導體配線技術而備受矚目。
然而,被用於上述連接部(凸塊或配線)的主要金屬,有焊料、錫、金、銀、銅、鎳等,含有數種這些材料的導電材料也被使用。連接部所使用的金屬,因為表面氧化而產生氧化膜、或是表面上附著氧化物等不純物等狀況,有時會使得連接部的連接面上產生不純物。若殘留這樣的不純物,半導體晶片及基板之間或是2個半導體晶片之間的連接性、絕緣可靠性則變得低落,而會有採用上述連接方式的優點受到損害的可能性。
又,作為抑制這些不純物的發生的方法,有已知的有機保焊劑製程(OSP(Organic Solderbility Preservatives))處理等,將連接部以氧化防止膜包覆的方法。但此氧化防止膜,有時是造成連接過程時,焊料濕潤性降低、連接性降低等的原因。
因此,作為去除上述氧化膜或不純物的方法,提出一種使半導體材料中含有助焊劑的方法(例如,參考專利文獻2~5)。
[先前技術文獻]
(專利文獻)
專利文獻1:日本特開2008-294382號公報
專利文獻2:日本特開2001-223227號公報
專利文獻3:日本特開2002-283098號公報
專利文獻4:日本特開2005-272547號公報
專利文獻5:日本特開2006-169407號公報
一般來說,在連接部之間的連接方面,從確保充足的連接性、絕緣可靠性的觀點來看,會選用金屬接合的方式。半導體材料不具有充足的助焊活性(對金屬表面的氧化膜及不純物等的除去效果)時,會有無法去除金屬表面的氧化膜和不純物等,而無法形成良好的金屬-金屬接合,也無法確保通導良好的情況。
又,使用半導體材料所製造的半導體裝置,被要求具有良好的耐熱性及耐濕性,並被要求具有耐迴焊性,該耐迴焊性在260℃左右的迴焊溫度中,可充分抑制半導體材料的剝離、連接部的連接不良等狀況。
本發明的目的在於提供一種半導體用黏著劑,該半導體用黏著劑能製作出耐迴焊性及連接可靠性優異的半導體裝置。又,本發明的目的在於提供一種使用上述半導體用黏著劑之半導體裝置的製造方法及半導體裝置。進而,本發明的目的在於提供一種可實現上述半導體用黏著劑之助
焊劑。
本發明的其中一種態樣,提供一種半導體用黏著劑,其含有環氧樹脂、硬化劑及具有下述通式(1-1)或(1-2)所示的基團之化合物,
[式中,R1表示電子供給基,複數存在的R1彼此可相同亦可不同]。
本態樣的半導體黏著劑,不但含有環氧樹脂及硬化劑,進而含有具有式(1-1)或(1-2)所示的基團(基)之化合物,藉此,在金屬接合的倒裝晶片連接方式中,即使作為半導體黏著劑來應用,也能製作出一種耐迴焊性及連接可靠性優異的半導體裝置。
耐迴焊性的提升,必需將高溫中的吸濕後的黏著力降低情況加以抑制。以往,羧酸被用來作為助焊劑,但是,本發明人認為,在以往的助焊劑中,因為以下的理由而會發生黏著力降低的情況。
通常,環氧樹脂與硬化劑反應而使硬化反應進行,但是,此時作為助焊劑的羧酸卻被該硬化反應納入。亦即,因為環氧樹脂的環氧基與助焊劑的羧基反應,會有形成酯
鍵的情況。該酯鍵,會因為吸濕等原因而容易發生加水分解等狀況,該酯鍵的分解,被認為是吸濕後造成黏著力降低的原因之一。
相對於此,本態樣的半導體黏著劑,含有具有通式(1-1)或(1-2)所示的基團之化合物,也就是含有具有羧基之化合物,該化合物在羧基的近旁具備2個電子供給基。因此,本態樣中,藉由羧基而得到充份的助焊活性,並且就算是形成有上述酯鍵的情況,也可藉由2個電子供給基,使得酯鍵部的電子密度提升,抑制了酯鍵的分解。
又,本態樣中,因為羧基的近旁存在取代基(電子供給基),藉由立體阻礙,可抑制羧基與環氧樹脂之間的反應,酯鍵變得難以生成。
基於這些理由,本態樣的半導體用黏著劑,不易因吸濕等而使組成產生變化,因此可維持優異的黏著力。又,上述的作用,可以使得環氧樹脂與硬化劑的硬化反應不易因助焊劑而被阻礙,藉由該作用,因為環氧樹脂與硬化劑的硬化反應可充分進行,也可期望連接可靠性提升這樣的效果。
具有通式(1-1)或(1-2)所示的基團之化合物,較佳是含有2個羧基之化合物。含有2個羧基之化合物,相較於含有1個羧基之化合物,不易因連接時的高溫而揮發,所以更能夠抑制孔洞的發生。又,使用含有2個羧基之化合物,相較於含有3個羧基之化合物的情況,保管時、連接處理時等情況下,更能抑制半導體用黏著劑的黏度上升,可更
加提升半導體裝置的連接可靠性。
具有通式(1-1)或(1-2)所示的基團之化合物,更佳是下述通式(2-1)或(2-2)所示的化合物。藉由下述通式(2-1)或(2-2)所示的化合物,能更加提升半導體裝置的耐迴焊性及連接可靠性,
[式中,R1表示電子供給基,R2表示氫原子或電子供給基,n1表示0~15的整數,n2表示1~14的整數,複數存在的R1彼此可相同亦可不同,當R2為複數存在時,R2彼此可相同亦可不同]。
又,具有通式(1-1)或(1-2)所示的基團之化合物,進而更佳是下述通式(3-1)或(3-2)所示的化合物。藉由下述式(3-1)或(3-2)所示的化合物,能更加提升半導體裝置的耐迴焊性及連接可靠性,
[式中,R1表示電子供給基,R2表示氫原子或電子供給基,m1表示0~10的整數,m2表示0~9的整數,複數
存在的R1及R2,可分別互為相同亦可為不同]。
通式(3-1)中的m1,較佳是0~8的整數,通式(3-2)中的m2,較佳是0~7的整數。若m1是5以下,m2是4以下,則可得到更加優異的連接可靠性。
具有通式(1-1)或(1-2)所示的基團之化合物的熔點,較佳是150℃以下。這樣的化合物,在環氧樹脂與硬化劑的硬化反應發生前,就展現充分的助焊活性,因此,若藉由含有該化合物之半導體黏著劑,在連接可靠性方面,能實現更良好的半導體裝置。
上述電子供給基,較佳是碳數1~10的烷基。若電子供給基為碳數是1~10的烷基,可使得上述的效果更加顯著。
本態樣的半導體用黏著劑,也可進一步含有重量平均分子量在10000以上的高分子成分。藉由該高分子成分,可使得半導體用黏著劑的耐熱性及薄膜成形性提升。又,在含有高分子成分之半導體用黏著劑中,藉由具有上述通式(1-1)或(1-2)所示的基團之化合物,使得本發明的效果更加顯著。
以預施加(Pre-applied)方式密封半導體晶片與配線電路基板的空隙、或密封複數個半導體晶片之間的空隙時,因為可使密封空隙的作業性提升,所以本態樣的半導體用黏著劑,其形狀較佳是薄膜狀。
本態樣的半導體用黏著劑,能適合用於密封半導體裝置中的前述連接部的至少一部份,該半導體裝置是半導體
晶片及配線電路基板的各個連接部互相電連接而成、或是複數個半導體晶片的各個連接部互相電連接而成。藉由這樣的用途,可實現一種耐迴焊性及連接可靠性優異的半導體裝置。
本發明的其他態樣,提供一種助焊劑,其含有具有下述通式(1-1)或(1-2)所示的基團之化合物,
[式中,R1表示電子供給基,複數存在的R1彼此可相同亦可不同]。
若依照本態樣的助焊劑,藉由組合環氧樹脂及硬化劑,可實現一種半導體黏著劑,該半導體黏著劑能製作出耐迴焊性及連接可靠性優異的半導體裝置。
本態樣的助焊劑中,具通式(1-1)或(1-2)所示基團之化合物,較佳是含有2個羧基之化合物。
又,在本態樣的助焊劑中,具有通式(1-1)或(1-2)所示的基團之化合物,更佳是通式(2-1)或(2-2)所示的化合物,
[式中,R1表示電子供給基,R2表示氫原子或電子供給基,n1表示0~15的整數,n2表示1~14的整數,複數存在的R1彼此可相同亦可不同,當R2為複數存在時,R2彼此可相同亦可不同]。
又,在本態樣的助焊劑中,具有通式(1-1)或(1-2)所示的基團之化合物,進而更佳是下述通式(3-1)或(3-2)所示的化合物,
[式中,R1表示電子供給基,R2表示氫原子或電子供給基,m1表示0~10的整數,m2表示0~9的整數,複數存在的R1及R2,可分別互為相同亦可為不同]。
本態樣的助焊劑中,上述通式(3-1)中的m1,較佳是0~8的整數,通式(3-2)中的m2,較佳是0~7的整數。
本態樣的助焊劑中,上述電子供給基,較佳是碳數1~10的烷基。
本態樣的助焊劑,其作為助焊劑能適合用於調配至半導體用黏著劑中,該半導體用黏著劑含有環氧樹脂及硬化劑。
又,本發明的其他態樣,提供一種半導體裝置的製造方法,是製造半導體裝置的方法,該半導體裝置是半導體
晶片及配線電路基板的各個連接部互相電連接而成、或是複數個半導體晶片的各個連接部互相電連接而成,其中,該半導體裝置的製造方法具備密封步驟,該密封步驟使用上述半導體用黏著劑來密封前述連接部的至少一部分。
若依照本態樣的製造方法,藉由使用上述半導體黏著劑,能提升半導體裝置的耐迴焊性及連接可靠性。
本發明的其他態樣,提供一種藉由上述製造方法所製得的半導體裝置。本態樣的半導體裝置,其耐迴焊性及連接可靠性優異。
若依照本發明,可提供一種半導體黏著劑,其能製作出一種耐焊性及連接可靠性優異的半導體裝置。又。若依照本發明,則可提供一種使用上述半導體用黏著劑之半導體裝置的製造方法及半導體裝置。進而,若依照本發明,可提供一種能實現上述半導體用黏著劑之助焊劑。
以下,依照情狀的不同,一邊參照圖式一邊詳細地說明本發明的較佳實施形態。此外,圖式中,同樣或是相當的部分以同樣的符號表示,而省略重複的說明。又,上下左右等的位置關係,若無特別限制,以圖式所標明的位置關係為基準。進而,圖式的尺寸比例並不被限定於所顯示的尺寸比例。
<半導體用黏著劑>
本實施形態的半導體用黏著劑,含有環氧樹脂(以下,依照狀況,稱為「(a)成分」)、硬化劑(以下,依照狀況,稱為「(b)成分」)、及具有下述通式(1-1)或(1-2)所示的基團之化合物(以下,依照狀況,稱為「(c)成分」)。
通式(1-1)或(1-2)中,R1表示電子供給基,複數存在的R1,彼此可相同亦可不同。
若依照本實施形態的半導體黏著劑,除了含有環氧樹脂及硬化劑以外,藉由進而含有具有通式(1-1)或(1-2)所示的基團之化合物,在金屬接合的倒裝晶片連接方式中,即使作為半導體黏著劑來應用時,也能製作出一種耐迴焊性及連接可靠性優異的半導體裝置。
耐迴焊性的提升,必需將高溫中的吸濕後的黏著力降低情況加以抑制。以往,使用羧酸作為助焊劑,但是,本發明人認為,以往的助焊劑中,會因為以下的理由而造成黏著力降低。
通常,環氧樹脂與硬化劑反應而使硬化反應進行,但是,此時助焊劑也就是羧酸被該硬化反應納入。亦即,因為環氧樹脂的環氧基與助焊劑的羧基反應,會有形成酯鍵的情況。該酯鍵,會因為吸濕等原因而容易發生加水分解
等狀況,該酯鍵的分解,被認為是吸濕後的黏著力降低的原因之一。
相對於此,本實施形態的半導體黏著劑,含有具有通式(1-1)或(1-2)所示的基團之化合物,也就是含有具有羧基之化合物,該化合物在羧基的近旁具備2個電子供給基。因此,本實施形態的半導體用黏著劑中,藉由羧基而得到充份的助焊活性,並且,就算是形成有上述酯鍵的情況,也可藉由2個電子供給基,使得酯鍵部的電子密度提升,抑制了酯鍵的分解。
又,本實施形態中,可認為:因為在羧基的近旁存在著2個取代基(電子供給基),藉由立體阻礙,可抑制羧基與環氧樹脂之間的反應,酯鍵變得難以形成。
基於這些理由,本實施形態的半導體用黏著劑,不易因吸濕等原因而產生組成變化,因此可維持優異的黏著力。又,上述的作用,能使得環氧樹脂及硬化劑的硬化反應不易因助焊劑而被阻礙,藉由該作用,環氧樹脂與硬化劑的硬化反應可充分進行,因此也可期望連接可靠性的提升這樣的效果。
本實施形態的半導體用黏著劑,依據需求,亦可含有重量平均分子量是10000以上的高分子成分(以下,依照狀況稱為「(d)成分」)。又,本實施形態的半導體用黏著劑,依據需求,亦可含有填充劑(以下,依照狀況稱為「(e)成分」)
以下,說明關於構成本發明形態的半導體用黏著劑的各種成分。
(a)成分:環氧樹脂
作為環氧樹脂,只要分子內具有兩個以上的羧基即可,並無特別限制。作為(a)成分,例如,可使用雙酚A型環氧樹脂、雙酚F型環氧樹脂、萘型環氧樹脂、苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、苯酚芳烷型環氧樹脂、聯苯型環氧樹脂、三苯甲烷型環氧樹脂、倍環戊二烯型環氧樹脂及各種多官能環氧樹脂。這些化合物可單獨使用,或以2種以上的混合物使用。
(a)成分,從抑制在高溫連接時分解產生揮發成分的觀點來看,連接時的溫度為250℃時,較佳是使用在250℃時的熱重量減少量比率在5%以下的環氧樹脂,連接時的溫度為300℃時,較佳是使用在300℃時的熱重量減少量比率在5%以下的環氧樹脂。
(a)成分的含量,以半導體用黏著劑的總量為基準,例如是5~75質量%,較佳是10~50質量%,更佳是15~30質量%。
(b)成分:硬化劑
作為(b)成分,例如可舉出:酚樹脂系硬化劑、酸酐系硬化劑、胺系硬化劑、咪唑系硬化劑及膦系硬化劑。若(b)成分中含有酚性羥基、酸酐、胺類或咪唑類,可顯現出抑制連接部產生氧化膜之助焊活性,提升連接可靠性、絕緣可靠性。以下,針對各硬化劑進行說明。
(i)酚樹脂系硬化劑
作為酚樹脂系硬化劑,只要分子內具有2個以上的酚
性羥基即可,並無特別限制,例如可使用苯酚酚醛樹脂、甲酚酚醛樹脂、苯酚芳烷樹脂、甲酚萘酚甲醛聚縮合物、三苯甲烷型多官能酚樹脂及各種多官能酚樹脂。這些化合物可單獨使用、或以2種以上的混合物使用。
酚樹脂系硬化劑相對於上述(a)成分的當量比(酚性羥基/環氧基,莫耳比),從良好的硬化性、黏著性及保存安定性的觀點來看,較佳是0.3~1.5,更佳是0.4~1.0,進而更佳是0.5~1.0。若當量比是0.3以上,則硬化性提升而有黏著力提升的傾向,若當量比是1.5以下,則不會殘留過剩的未反應酚性羥基,吸水率也可壓低,並有提升絕緣可靠性的傾向。
(ii)酸酐系硬化劑
作為酸酐硬化劑,例如可使用甲基環己烷四羧酸二酐、苯偏三酸酐、苯均四酸二酐、二苯甲酮四羧酸二酐及乙二醇雙苯偏三酸酐(ethylene glycol bisanhydrotrimellitate)。這些化合物可單獨使用,或以2種以上的混合物使用。
酸酐系硬化劑相對於上述(a)成分的當量比(酸酐基/環氧基,莫耳比),從良好的硬化性、黏著性及保存安定性的觀點來看,較佳是0.3~1.5,更佳是0.4~1.0,進而更佳是0.5~1.0。若當量比是0.3以上,則硬化性提升而有黏著力提升的傾向,若當量比是1.5以下,則不會殘留過剩的未反應酸酐,吸水率也可壓低,並有絕緣可靠性提升的傾向。
(iii)胺系硬化劑
作為胺系硬化劑,例如,可使用二氰二胺。
胺系硬化劑相對於上述(a)成分的當量比(胺基/環氧基,莫耳比),從良好的硬化性、黏著性及保存安定性的觀點來看,較佳是0.3~1.5,更佳是0.4~1.0,進而更佳是0.5~1.0。若當量比是0.3以上,則硬化性提升而有黏著力提升的傾向,若當量比是1.5以下,則不會殘留過剩的未反應酸酐,並有絕緣可靠性提升的傾向。
(iv)咪唑系硬化劑
作為咪唑系硬化劑,例如可舉出:2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰乙基-2-十一基咪唑、1-氰基-2-苯基咪唑、1-氰乙基-2-十一基咪唑偏苯三甲酸酯、1-氰乙基-2-苯基咪唑偏苯三甲酸酯、2,4-二胺-6-[2’-甲基咪唑-(1’)]-乙基-s-三氮雜苯、2,4-二胺-6-[2’-十一基咪唑-(1’)]-乙基-s-三氮雜苯、2,4-二胺-6-[2’-乙基-4’-甲基咪唑-(1’)]-乙基-s-三氮雜苯、2,4-二胺-6-[2’-甲基咪唑-(1’)]-乙基-s-三氮雜苯異三聚氰酸加成物、2-苯基咪唑三聚氰酸加成物、2-苯基-4,5-二羥甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑,及環氧樹脂與咪唑類的加成物。其中,從優異的硬化性、保存安定性及連接可靠性的觀點來看,較佳是1-氰乙基-2-十一基咪唑、1-氰基-2-苯基咪唑、1-氰乙基-2-十一基咪唑偏苯三甲酸酯、1-氰乙基-2-苯基咪唑偏苯三甲酸酯、2,4-二胺-6-[2’-甲基咪唑-(1’)]-乙基-s-三氮雜苯、2,4-二胺-6-[2’-乙基-4’-甲基咪唑
-(1’)]-乙基-s-三氮雜苯、2,4-二胺-6-[2’-甲基咪唑-(1’)]-乙基-s-三氮雜苯異三聚氰酸加成物、2-苯基咪唑三聚氰酸加成物、2-苯基-4,5-二羥甲基咪唑及2-苯基-4-甲基-5-羥甲基咪唑。這些化合物可單獨使用,或以2種以上的混合物合併使用。又,亦可將這些化合物微膠囊化後,作為潛伏性硬化劑使用。
咪唑系硬化劑的含量,相對於(a)成分100質量份,較佳是0.1~20質量份,更佳是0.1~10質量份。咪唑系硬化劑的含量若為0.1質量份以上,有硬化性提升的傾向,若為20質量份以上,在形成金屬接合前,半導體用黏著劑沒有硬化而有不易發生連接不良的傾向。
(v)膦系硬化劑
作為膦系硬化劑,例如可舉出:三苯基膦、四苯基硼四苯基膦、四(4-甲苯基)硼四苯基膦及四(4-氟苯基)硼四苯基膦。
膦系硬化劑的含量,相對於(a)成分100質量份,較佳是0.1~10質量份,更佳是0.1~5質量份。膦系硬化劑的含量若是0.1質量份以上,有硬化性提升的傾向,若是10質量份以上,在形成金屬接合前,半導體用黏著劑沒有硬化而有不易發生連接不良的傾向。
酚樹脂系硬化劑、酸酐系硬化劑及胺系硬化劑,可以單獨使用1種,亦可使用2種以上的混合物。咪唑系硬化劑及膦系硬化劑可個別單獨使用,亦可與酚樹脂系硬化劑、酸酐系硬化劑或胺系硬化劑共同使用。
從更加提升保存安定性且不易發生因吸濕分解而引起劣化的觀點來看,(b)成分,較佳是從由酚樹脂系硬化劑、胺系硬化劑、咪唑系硬化劑及膦系硬化劑所組成的群組中選擇出來的硬化劑。又,從調整硬化速度的難易度的觀點、及藉由快速硬化性而以提升生產性為目的來實現能於短時間內連接的觀點來看,(b)成分,更佳是從由酚樹脂系硬化劑、胺系硬化劑及咪唑系硬化劑所組成的群組中選擇出來的硬化劑。
作為半導體用黏著劑的(b)成分,含有酚樹脂系硬化劑、酸酐系硬化劑或胺系硬化劑時,顯現去除氧化膜的助焊活性,可更加提升連接可靠性。
(c)成分:含有通式(1-1)或(1-2)所示的基團之化合物。
(c)成分為含有通式(1-1)或(1-2)所示的基團之化合物(以下,依照狀況稱為「助焊化合物」)。(c)成分是具有助焊活性的化合物,於本實施形態的半導體用黏著劑中,發揮作為助焊劑的功能。作為(c)成分,可單獨使用1種的助焊化合物,亦可併用2種以上的助焊化合物。
通式(1-1)或(1-2)中,R1表示電子供給基,複數存在的R1彼此可相同亦可不同。
作為電子供給基,例如可舉出:烷基、羥基、胺基、烷氧基、烷胺基。作為電子供給基,較佳是難以與其他成分(例如,(a)成分的環氧樹脂)進行反應者,具體來說,烷基、羥基或烷氧基較佳,烷基則更佳。
若電子供給基的電子供給能力變強,則有容易獲得抑制上述酯鍵分解效果的傾向。又,若電子供給基的立體阻礙大,則更容易得到抑制上述羧基與環氧樹脂之間的反應的效果。電子供給基,較佳是能具有良好平衡的電子供給能力及立體阻礙。
作為烷基,較佳是碳數1~10的烷基,更佳是碳數1~5的烷基。烷基的碳數越多,則電子供給能力及立體阻礙有越大的傾向。碳數在上述範圍內的烷基,因其電子供給能力與立體阻礙之間具有優異的平衡性,若是藉由該烷基,則可使本發明的效果更加顯著。
又,烷基中,雖然直鏈狀或是分支狀皆可,但其中較佳是直鏈狀。烷基是直鏈狀時,從電子供給能力及立體阻礙的觀點來看,烷基的碳數,較佳是助焊化合物的主鏈的碳數以下。例如,助焊化合物是下述通式(2-1)或(2-2)所示的化合物,電子供給基是直鏈狀的烷基時,該烷基的碳數,較佳是助焊化合物的主鏈的碳數(n1+1或n2+2)以下。
作為烷氧基,較佳是碳數為1~10的烷氧基,更佳是碳數1~5的烷氧基。烷氧基的碳數越多,則電子供給能力及立體阻礙有越大的傾向。碳數在上述範圍內的烷氧基,因其電子供給能力與立體阻礙之間具有優異的平衡性,若
是藉由該烷氧基,則可使本發明的效果更加顯著。
又,烷氧基的烷基部份,雖然直鏈狀或是分支狀皆可,但其中較佳是直鏈狀。烷氧基是直鏈狀時,從電子供給能力及立體阻礙的平衡性的觀點來看,烷氧基的碳數,較佳是助焊化合物的主鏈的碳數以下。例如,助焊化合物是下述通式(2-1)或(2-2)所示的化合物,電子供給基是直鏈狀的烷氧基時,該烷氧基的碳數,較佳是助焊化合物的主鏈的碳數(n1+1或n2+2)以下。
作為烷胺基,可舉出:單烷胺基、二烷胺基。作為單烷胺基,較佳是碳數為1~10的單烷胺基,更佳是碳數1~5的單烷胺基。單烷胺基的烷基部分,直鏈狀或是分支狀皆可,直鏈狀較佳。
作為二烷胺基,較佳是碳數為2~20的二烷胺基,更佳是碳數2~10的二烷胺基。二烷胺基的烷基部分,直鏈狀或是分支狀皆可,直鏈狀較佳。
助焊化合物,較佳是具有2個羧基之化合物(二羧酸)。具有2個羧基之化合物,相較於具有一個羧基之化合物(單羧酸),不易因連接時的高溫而揮發,而能更抑制孔洞的發生。又,使用含有2個羧基之化合物,相較於含有3個羧基之化合物的情況,更能抑制保管時、連接作業時等,半導體用黏著劑的黏度上升,而更加提升了半導體裝置的連接可靠性。
作為助焊化合物,能使用下述通式(2-1)或(2-2)所示的化合物。藉由下述通式(2-1)或(2-2)所示的化合物,能更加
提升半導體裝置的耐迴焊性及連接可靠性。
通式(2-1)中,R1表示電子供給基,R2表示氫原子或電子供給基,n1表示0或1以上的整數。又,複數存在的R1彼此可相同亦可不同,當R2為複數存在時,R2彼此可相同亦可不同。
通式(2-2)中,R1表示電子供給基,R2表示氫原子或電子供給基,n2表示1以上的整數。又,複數存在的R1彼此可相同亦可不同,當R2為複數存在時,R2彼此可相同亦可不同。
通式(2-1)中的n1,較佳是1以上。n1是1以上時,相較於n1是0時,就算是連接時的高溫,助焊化合物也不易揮發,且能更抑制孔洞的發生。又,通式(2-1)中的n1,較佳是15以下,更佳是11以下,進而更佳是9以下,7以下或5以下亦可。若n1是15以下,能得到更優異的連接可靠性。
通式(2-2)中的n2,較佳是14以下,更佳是10以下,進而更佳是8以下,6以下或4以下亦可。若n2是10以下,能得到更優異的連接可靠性。
又,作為助焊化合物,下述通式(3-1)或(3-2)所示的化
合物更為適合。藉由下述通式(3-1)或(3-2)所示的化合物,能更提升半導體裝置的耐迴焊性及連接可靠性。
通式(3-1)中,R1表示電子供給基,R2表示氫原子或電子供給基,m1表示0或1以上的整數,複數存在的R1及R2,各自可互為相同亦可互為不同。
通式(3-2)中,R1表示電子供給基,R2表示氫原子或電子供給基,m2表示0或1以上的整數,複數存在的R1及R2,各自可互為相同亦可互為不同。
通式(3-1)中的m1,較佳是10以下,更佳是8以下,進而更佳是6以下。若m1是10以下,能得到更優異的連接可靠性。
通式(3-1)中的m2,較佳是9以下,更佳是7以下,進而更佳是5以下。若m2是9以下,能得到更優異的連接可靠性。
助焊化合物若是非對稱構造,會有熔點變低的傾向,能更加提升半導體裝置的連接可靠性。若助焊化合物是對稱構造,會有熔點變高的傾向,但是即使如此,仍可充分地獲得本發明的效果。特別是,若熔點在150℃以下的非常低的情況,助焊化合物就算是對稱構造,也可獲得與非
對稱構造同樣程度的連接可靠性。這裡,對稱構造是指,例如在通式(3-1)中,R1與R2為完全相同的基團的情況。
通式(3-1)及(3-2)中,R2較佳是氫原子。這樣的化合物是非對稱的助焊化合物,若藉由這樣的化合物,能更加提升半導體裝置的連接可靠性。
作為助焊化合物,例如,能使用一種化合物,其是從丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸中選出一種二羧酸,而該二羧酸的2位碳被2個電子供給基取代而成。
作為助焊化合物,例如,能使用一種化合物,其是從丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸中選出一種二羧酸,而該二羧酸的3位碳被2個電子供給基取代而成。
上述助焊化合物的熔點,較佳是150℃以下,更佳是140℃以下,進而更佳是130℃以下。這樣的助焊化合物,因為在環氧樹脂與硬化劑的硬化反應發生前,容易充分展現助焊活性。因此,若藉由含有這樣的化合物之半導體黏著劑,能實現在連接可靠性方面更良好的半導體裝置。又,助焊化合物的熔點,較佳是25℃以上,更佳是50℃以上。又,助焊化合物,較佳是室溫(25℃)下為固態之物。
助焊化合物的熔點,能使用一般的熔點測定裝置進行測定。測定熔點的試樣,因為被粉碎成微細粉末且僅使用微量,所以希望能減少試樣內的溫度偏差。作為試樣的容器,雖然經常使用一端為封閉端的毛細管,依照測定裝置
的不同,也可以使用2片顯微鏡用蓋玻片來包夾試樣,作為容器。又,若使溫度急劇上升,則試樣與溫度計之間會出現溫度梯度,因而產生測定誤差,所以處於測定熔點的時間點下的升溫,希望能以每分鐘1℃以下的上升率進行測定。
如前述,由於以微細粉末進行調整的關係,因為微細粉末表面的亂射,熔解前的試樣是不透明的狀態。通常,試樣的外觀開始變得透明的溫度為熔點的下限,熔解完成的溫度為上限。雖然測定裝置有著各種不同的形態,使用最典型的裝置是於雙重管溫度計上,裝設已填入試樣的毛細管,並以溫浴法加溫的裝置。為了將毛細管貼附於雙重管溫度計上之目的,作為溫浴的液體,選用黏性高的液體,而濃硫酸及矽油則經常被使用,可使試樣靠近並貼附於溫度計前端的集中處附近。又,作為熔點設定裝置,可使用一種裝置,該裝置以金屬的熱板來進行加熱,並一邊測定光的透過率,一邊調整加溫程度,自動地決定熔點。
此外,本說明書中,所謂的熔點為150℃以下,是指熔點的上限為150℃以下;所謂的熔點為25℃以上,是指熔點的下限為25℃以上。
(c)成分的含量,以半導體用黏著劑的總量為基準,較佳是0.5~1.0質量%,更佳是0.5~5質量%。
(d)成分:重量平均分子量為10000以上的高分子成分。
本實施形態的半導體用黏著劑,依據需求,亦可含有重量平均分子量為10000以上的高分子成分((d)成分)。含
有(d)成分之半導體用黏著劑,其耐熱性及薄膜成形性更佳良好。
作為(d)成分,例如,從獲得優異的耐熱性、薄膜成形性及連接可靠性的觀點來看,較佳是苯氧基樹脂、聚醯亞胺樹脂、聚醯胺樹脂、聚碳二醯亞胺樹脂、氰酸酯樹脂、丙烯酸酯樹脂、聚酯樹脂、聚乙烯樹脂、聚醚碸樹脂、聚醚醯亞胺樹脂、聚乙烯縮醛樹脂、胺甲酸乙酯樹脂及丙烯酸橡膠。其中,又從更優異的耐熱性及薄膜成形性的觀點來看,更佳是苯氧基樹脂、聚醯亞胺樹脂、丙烯酸橡膠、丙烯酸酯樹脂、氰酸酯樹脂及聚碳二醯亞胺樹脂,進而更佳是苯氧基樹脂、聚醯亞胺樹脂、丙烯酸橡膠、丙烯酸酯樹脂。這些的(d)成分,可單獨使用,亦可以2種以上的混合物或共聚合物來使用。但是,(d)成分中不包含(a)成分的環氧樹脂。
(d)成分的重量平均分子量是10000以上,較佳是20000以上,更佳是30000以上。若藉由這樣的(d)成分,可使半導體用黏著劑的耐熱性及薄膜成型性更加提升。
又,(d)成分的重量平均分子量,較佳是1000000以下,更佳是500000以下。若藉由這樣的(d)成分,可得高耐熱性的效果。
此外,上述重量平均分子量是使用GPC(凝膠滲透層析法,Gel Permeation Chromatography)來測定,經聚苯乙烯換算之重量平均分子量。GPC法測定條件的例子,如以下
所示。
裝置:HCL-8320GPC、UV-8320(產品名,股份TOSOH有限公司製),或HPLC-8020(產品名,TOSOH股份有限公司製)
管柱:TSKgel superMultiporeHZ-M×2、或2 pieces of GMHXL+1 piece of G-2000XL
檢測器:RI或UV檢測器
管柱溫度:25~40℃
析出液:選擇可溶解高分子成分的溶媒。例如,THF(四氫呋喃,tetrahydrofuran)、DMF(N,N-二甲基甲醯胺,N,N-dimethylformamide)、DMA(二甲基乙醯胺,N,N-dimethylacetamide)、NMP(N-甲基吡咯啶酮,N-Methylpyrrolidone)、甲苯。又,選擇具有極性的溶劑時,亦可將磷酸的濃度調整至0.05~0.1mol/L(通常是0.06 mol/L),LiBr的濃度調整至0.5~1.0 mol/L(通常是0.63 mol/L)。
流速:0.30~1.5ml/分鐘
標準品:聚苯乙烯
半導體用黏著劑含有(d)成分時,(d)成分的含量Cd,與(a)成分的含量Ca的比Ca/Cd(質量比),較佳是0.01~5,更佳是0.05~3,進而更佳是0.1~2。若Ca/Cd地比為0.01以上,可得到更良好的硬化性及黏著力,Ca/Cd的比為5以下時,可得到更良好的薄膜成形性。
(e)成分:填充劑
本實施形態的半導體用黏著劑,依據需求,亦可含有填充劑((e)成分)。藉由(e)成分,可控制半導體用黏著劑的黏度,半導體用黏著劑的硬化物的物性等。具體而言,若藉由(e)成分,例如,可謀求抑制連接時的孔洞發生、半導體用黏著劑的硬化物的吸濕率降低等。
作為(e)成分,可使用絕緣性無機填充劑、晶鬚(whisker)、樹脂填充劑等。又,作為(e)成分,可單獨使用1種,亦可2種以上合併使用。
作為絕緣性無機填充劑,例如可舉出:玻璃、二氧化矽、氧化鋁、氧化鈦、碳黑、白雲母及氮化硼。其中,較佳是二氧化矽、氧化鋁、氧化鈦及氮化硼,更佳是二氧化矽、氧化鋁及氮化硼。
作為晶鬚(whisker),例如可舉出:硼酸鋁、鈦酸鋁、氧化鋅、矽酸鈣、硫酸鎂及氮化硼。
作為樹脂填充劑,例如可舉出:由聚胺基甲酸酯(PU橡膠)、聚醯亞胺等樹脂所製成之填充劑。
樹脂填充劑,相較於有機成分(環氧樹脂及硬化劑等),因為熱膨脹率小,所以連接可靠性的提升效果優異。又,若藉由樹脂填充劑,可容易對半導體用黏著劑進行黏度調整。又,樹脂填充劑,相較於無機填充劑,因為在緩和應力的功能上較佳,若藉由樹脂填充劑,更能抑制迴焊試驗等所出現的剝離情形。
無機填充劑,相較於樹脂填充劑,熱膨脹率小,所以
藉由無機填充劑,能實現黏著劑組成物的低熱膨脹率化。又,無機填充劑為通用物品,有許多種被控制粒徑的無機填充劑,因此在黏度調整方面也較理想。
因為樹脂填充劑及無機填充劑,分別具有有利的效果,可依照用途來選擇任一種使用,為了發揮兩方的機能,也可將兩種混合使用。
(e)成分的形狀、粒徑及含量並無特別限制。又,(e)成分亦可是經表面處理而將物性作適當調整者。
(e)成分的含量,以半導體用黏著劑的總量為基準,較佳是10~80質量%,更佳是15~60質量%。
(e)成分,較佳是以絕緣物所構成。若(e)成分是由導電性物質(例如,焊料、金、銀、銅等)所組成,恐怕會有絕緣可靠性(特別是HAST耐性)降低的問題。
(其他的成分)
本實施形態的半導體用黏著劑中,亦可調配抗氧化劑、矽烷偶合劑、鈦偶合劑、均染劑、離子收集劑等的添加劑。這些添加劑可單獨使用1種,亦可組合2種以上使用。關於添加劑的調配量,以能發揮各添加劑的效果的方式來做適當調整即可。
本實施形態的半導體用黏著劑,能成形為薄膜狀。使用本實施形態的半導體用黏著劑,製作薄膜狀黏著劑的方法,以下表示其中一個例子。
首先,將(a)成分、(b)成分及(c)成分,並依據需求將(d)成分、(e)成分等,加入有機溶劑中,經混合攪拌,混練等
步驟,使這些成分溶解或分散於有機溶劑中,來調製樹脂清漆。之後,在已施行脫模處理後的基材薄膜上,使用刀式塗佈機、輥式塗佈機、塗抹器(applicator)等,塗佈樹脂清漆後,藉由加熱去除有機溶劑,可於基材薄膜上形成薄膜狀黏著劑。
薄膜狀黏著劑的厚度,並無特別限制,例如,較佳是連接前凸塊的高度的0.5~1.5倍,更佳是0.6~1.3倍,進而更佳是0.7~1.2倍。
薄膜狀黏著劑的厚度,若是凸塊高度的0.5倍以上,可充分抑制因為黏著劑未填滿而使孔洞產生的情形,並可使連接可靠性更加提升。又,若厚度為1.5倍以下,因為可充分抑制連接時從晶片連接區域被壓擠出的黏著劑的量,而可充分防止不需黏著劑的部分沾附上黏著劑的情況。若薄膜狀黏著劑的厚度比1.5倍大,會變得不得不清除凸塊上多餘的黏著劑,也變得容易產生導通不良的狀況。又,相對於因間距狹窄化、多引腳化造成凸塊的弱化(凸塊徑距的微小化),清除多餘的樹脂會增加凸塊的損傷,因此並不理想。
一般而言,若凸塊的高度是5~100μm,薄膜狀黏著劑的厚度,較佳是2.5~150 μm,更佳是3.5~120 μm。
調製樹脂清漆所用的有機溶劑,較佳是具有能夠使各成分均勻地溶解或分散的特性,例如可舉出:二甲基甲醯胺、二甲基乙醯胺、N-甲基-2-吡咯啶酮、二甲亞碸、二乙二醇二甲醚、甲苯、苯、二甲苯、丁酮、四氫呋喃、乙基
賽璐蘇、乙酸乙賽璐蘇、丁基賽路蘇、二氧陸圜、環己酮及乙酸乙酯。這些有機溶劑,可單獨使用或組合2種以上使用。調製樹脂清漆時的混合攪拌和混練,舉例來說,可使用攪拌機、擂潰機、三輥機、球磨機、珠磨機或高速分散機來進行。
作為基材薄膜,只要具有耐熱性而能承受揮發有機溶劑時的加熱條件,則無特別限制,例如可舉出:聚丙烯薄層、聚甲基戊烯薄層等的聚烯薄層,聚對苯二甲酸乙二酯薄層、聚萘二甲酸乙二酯薄層等的聚酯薄層,聚醯亞胺薄層及聚醚醯亞胺薄層。基材薄膜,並不限於是由這些薄層所構成的單層物,也可是從2種以上的材料所構成多層薄層。
將塗佈於基材薄膜上的樹脂清漆,使其中的有機溶劑揮發時的乾燥條件,較佳是可將有機溶劑充分揮發的條件,具體來說,較佳是以50~200℃的溫度,加熱0.1~90分鐘。有機溶劑,相對於薄膜狀黏著劑總量,較佳是被去除至1.5質量%以下。
又,本實施形態的半導體用黏著劑,也可於晶圓上直接形成。具體來說,例如,將上述樹脂清漆直接旋轉塗佈於晶圓上,形成薄膜後,去除有機溶劑,藉此,將半導體用黏著劑直接形成於晶圓上。
<半導體裝置>
關於本實施形態的半導體裝置,以下使用第1圖及第2圖來進行說明。第1圖是表示本發明的半導體裝置的一
實施形態的示意剖面圖。如第1圖(a)所示,半導體裝置100,具有:彼此對向的半導體晶片10及基板(配線電路基板)20、分別被配置於半導體晶片10及基板20的彼此對向的面上的配線15、將半導體晶片10及基板20的配線15互相接連之連接凸塊30、以及將半導體晶片10及基板20之間的空隙填充的黏著材料40。半導體晶片10及基板20,是藉由配線15及連接凸塊30而藉由倒裝晶片連接法連接在一起。配線15及連接凸塊30,是藉由黏著材料40來進行密封,與外部環境隔絕。
如第1圖(b)所示,半導體裝置200,具有:彼此對向的半導體晶片10及基板20、分別被配置於半導體晶片10及基板20的彼此對向的面上的凸塊32、以及將半導體晶片10及基板20之間的空隙填充的黏著材料40。半導體晶片10及基板20,是藉由對向的凸塊32互相連接,以倒裝晶片連接法連接在一起。凸塊32,是藉由黏著材料40而被密封,與外部環境隔絕。黏著材料40。是本實施形態的半導體用黏著劑的硬化物。
第2圖是表示本發明的半導體裝置的另一種實施形態的示意剖面圖。如第2圖(a)所示,半導體裝置300,除了2個半導體晶片10,藉由配線15及連接凸塊30,以倒裝晶片連接的方式來連接以外,其餘皆與半導體裝置100相同。如第2圖(b)所示,半導體裝置400,除了2個半導體晶片10,藉由凸塊32,以倒裝晶片連接的方式來連接以外,其餘皆與半導體裝置200相同。
作為半導體晶片10,並無特別限定,可使用矽、鍺等的由同一種類元素所構成的元素半導體,也可使用砷化鎵、磷化銦等的化合物半導體。
作為基板20,若為配線電路基板則無特別限制,能使用下述配線電路基板:在以玻璃環氧化合物、聚醯亞胺、聚酯、陶瓷、環氧化合物、雙馬來醯亞胺三氮雜苯等來作為主成分之絕緣基板的表面上,具有配線(配線圖案)15之配線電路基板,該配線是蝕刻去除不需要金屬膜之處而形成;於上述絕緣基板的表面上,經金屬電鍍等方式而形成有配線15之配線電路基板;於上述絕緣基板的表面上,印刷導電性物質而形成有配線15之配線電路基板。
配線15或是凸塊32等的連接部,作為主成分,含有金、銀、銅、焊料(主成分為,例如錫-銀、錫-鉛、錫-鉍、錫-銅、錫-銀-銅)、鎳、錫、鉛等,亦可含有複數種金屬。
上述金屬中,從作成在連接部的導電性、熱傳導性優異的封裝的觀點來看,較佳是金、銀及銅,更佳是銀及銅。從降低成本的封裝觀點來看,基於價格便宜,較佳是銀、銅及焊料,更佳是銅及焊料,進而更佳是焊料。放置於室溫下,若金屬的表面形成氧化膜,有時會造成生產性降低或是成本增加等情況,因此,從抑制氧化膜形成的觀點來看,較佳是金、銀、銅及焊料,更佳是金、銀、焊料,進而更佳是金、銀。
上述配線15及凸塊32的表面上,例如可藉由電鍍來形成金屬層,該金屬層是以金、銀、銅、焊料(主成分為,
例如錫-銀、錫-鉛、錫-鉍、錫-銅)、錫、鎳等做為主成分的金屬層。該金屬層可只由單一成分所構成,亦可由複數成分所構成。又,上述金屬層,可為單層或由複數的金屬層所積層而成之構造。
又,本實施形態的半導體裝置,可重複積層如半導體裝置100~400所示的構造(封裝)。此時,半導體裝置100~400,可藉由含有金、銀、銅、焊料(主成分為,例如錫-銀、錫-鉛、錫-鉍、錫-銅、錫-銀-銅)、錫、鎳等之凸塊或配線,相互地電連接。
作為積層複數個半導體裝置的手段,如第3圖所示,例如可舉出:三維晶片堆疊構裝(TSV(Through-Silicon Via))技術。第3圖是表示本發明的半導體裝置的另一實施形態的示意剖面圖,是使用TSV技術的半導體裝置。在第3圖所示的半導體裝置500中,中介片(interposer)50上所形成的配線15,經由連接凸塊30而與半導體晶片10的配線15連接,藉此,半導體晶片10與中介片50是以倒裝晶片方式來連接。半導體晶片10與中介片50之間的空隙,被黏著材料40充填成無空隙。位於上述半導體晶片10中的中介片50側的相反側的表面上,經由配線15、連接凸塊30及黏著材料40,將半導體晶片10重複積層。半導體晶片10的表面和背面中圖案面的配線15,是藉由貫穿電極34而相互地連接,該貫穿電極34被填充在已貫穿半導體晶片10內部之孔洞內。此外,作為貫穿電極34的材質,可使用銅、鋁等。
藉由這樣的TSV技術,可由通常不被使用的半導體晶片的背面來取得信號。進而,因為半導體晶片10內有貫穿電極34垂直通過,縮短對向的半導體晶片10之間、或半導體晶片10及中介片50之間的距離,而可作靈活對應的連接。本實施形態的半導體用黏著劑,在這樣的TSV技術中,能作為半導體黏著劑而應用於對向的半導體晶片10之間、或半導體晶片及中介片50之間。
又,面陣列晶片封裝(area bump chip)技術等的高自由度凸塊形成方法中,不經由中介片,就可將半導體晶片直接構裝於母板(主機板)上。本實施形態的半導體用黏著劑,也可以適用於這樣直接構裝半導體晶片於母板上的情況。此外,本實施形態的半導體用黏著劑,在積層2個配線電路基板時,能應用於密封基板間的空隙。
<半導體裝置的製造方法>
關於本實施形態的半導體裝置的製造方法,以下利用第4圖來作說明。第4圖是示意地表示本發明的半導體裝置的製造方法的一實施形態的步驟剖面圖。
首先,如第4圖(a)所示,在具有配線15之基板20上,在要形成連接凸塊30的位置上,形成具有開口之焊接光阻(solder resist)60。設置該焊接光阻60並非絕對必要。但是,藉由在基板20上設置焊接光阻,能抑制配線15之間發生電橋(bridge),並提升連接可靠性、絕緣可靠性。焊接光阻60,例如可使用市售的封裝用的焊接光阻用油墨來形成。作為市售的封裝用的焊接光阻用油墨,具體而言,可舉出
SR series(日立化成工業股份有限公司製,商品名)及PSR4000-AUS series(太陽油墨製造股份有限公司製,商品名)。
繼而,如第4圖(a)所示,於焊接光阻60的開口處,形成連接凸塊30。然後,如第4圖(b)所示,於形成有連接凸塊30及焊接光阻60之基板20上,貼附薄膜狀的半導體用黏著劑(以下,依照狀況稱為「薄膜狀黏著劑」)41。薄膜狀黏著劑41的貼附,可經由熱壓、輥壓、真空積層等方式進行。薄膜狀黏著劑41的供給面積和厚度等,則依照半導體晶片10及基板20的尺寸、或連接凸塊30的高度,來進行適當的設定。
如上述的內容,將薄膜狀黏著劑41貼附於基板20後,使用倒裝晶片連接器等的連接裝置,將半導體晶片10的配線15與連接凸塊30定位(對準位置)。繼而,將半導體晶片10與基板20,一邊以高於連接凸塊30的熔點以上的溫度進行加熱,一邊進行壓接,如第4圖(c)所示,連接半導體晶片10與基板20,並藉由薄膜狀黏著劑41的硬化物亦即黏著材料40,將半導體晶片10及基板20之間的空隙進行密封填充。依照以上步驟,可獲得一種半導體裝置600。
本實施形態的半導體裝置的製造方法中,亦可在定位後將其暫時固定(半導體用黏著劑介於其中的狀態),利用迴焊爐進行加熱處理,藉此,使連接凸塊30熔化來連接半導體晶片10與基板20。於暫時固定的階段,並非一定需要形成金屬接合,因此,相較於上述的一邊加熱一邊壓接
的方法相比,只要以低負載、短時間、低溫度便可進行壓接,而能提升生產性並可抑制連接部的劣化。
又,將半導體晶片10與基板20連接之後,亦能以烘箱等進行加熱處理,進而提高其連接可靠性、絕緣可靠性。加熱溫度,較佳是使薄膜狀黏著劑進行硬化的溫度,更佳是使其完全硬化的溫度。加熱溫度、加熱時間則被適當地設定。
本實施形態的半導體裝置的製造方法中,亦可在將薄膜狀黏著劑41貼附於半導體晶片10後,再連接基板20。又,亦可在藉由配線15及凸塊30來將半導體晶片10及基板20連接後,將糊狀的半導體用黏著劑充填至半導體晶片10及基板20之間的空隙中,再使其硬化。
從提升生產性的觀點來看,於連結複數個半導體晶片10而成之半導體晶圓上,供給半導體用黏著劑後,藉由切割為個別的片狀,則可得到一種在半導體晶片10上被供給半導體用黏著劑而成之構造體。又,半導體用黏著劑為糊狀時,並無特別限制,藉由旋轉塗佈等的塗佈方法,將半導體晶片10上的配線和凸塊等埋入,並使厚度均勻化即可。此時,因為樹脂的供給量變成固定,生產性能提升,並能抑制因埋入不足而導致的孔洞的發生及切割性降低的情況。另一方面,半導體用黏著劑為薄膜狀時,並無特別限制,只要藉由熱壓、輥壓及真空積層等貼附方式,提供能使半導體晶片10上的配電或凸塊埋入的薄膜狀半導體用黏著劑即可。此時,因為樹脂的供給量變成固定,能提
升生產性,並能抑制因埋入不足而導致孔洞的發生及切割性降低的情況。
相較於將糊狀的半導體用黏著劑旋轉塗佈的方法,若藉由將薄膜狀的半導體用黏著劑進行疊層(積層)的方法,供給後的半導體用黏著劑的平坦性有變佳的傾向。因此,作為半導體用黏著劑的形態,較佳是薄膜狀。又,薄膜狀黏著劑,於各種製程的適用性、使用性等方面也表現優異。
又,藉由疊層薄膜狀黏著劑來提供半導體用黏著劑的方法,會有變成更容易確保半導體裝置的連接性的傾向。關於這個理由,雖然尚未定論,但本發明人的看法如下。亦即,發明人認為,本實施形態的助焊劑,具有熔點低的傾向、及容易展現助焊活性的傾向。因此,藉由疊層薄膜狀黏著劑於半導體晶圓上時的加熱,表現助焊活性,使半導體晶圓上的凸塊表面的氧化膜的至少一部份被還原除去。藉由此還原除去,在供給薄膜狀黏著劑後的時點,凸塊的至少一部份露出,這被認為有助於連接性的提升。
連接負載,必須考慮連接凸塊30的數量和高度等的偏差、經加壓的連接凸塊30的變形量、或是承受連接部的凸塊之配線的變形量,來加以設定。連接溫度,雖然較佳是連接部的溫度高於連接凸塊30的熔點,但只要是各自的連接部(凸塊、配線),可形成金屬接合的溫度即可。連接凸塊30是焊料凸塊時,較佳是約為240℃以上。
連接時的連接時間,雖然因連接部的構成金屬不同而有差異,從提升生產性的觀點來看,以短時間為較佳。連
接凸塊30為焊料凸塊時,連接時間較佳是20秒以下,更佳是10秒以下,進而更佳是5秒以下。銅-銅或銅-金的金屬連接時,連接時間較佳是60秒以下。
就算是在上述各種不同的封裝構造的倒裝晶片連接部中,本實施形態的半導體用黏著劑,仍展現出優異的耐迴焊性及連接可靠性。
以上,雖然說明了本發明的較佳實施形態,但本發明並未被限定於上述實施形態。
例如,本發明的另一方面是關於含有通式(1-1)或(1-2)所示基團之化合物,作為調配至半導體用黏著劑中的助焊劑的使用。又,本發明的其他方面是關於為了半導體用黏著劑的製造,而使用通式(1-1)或(1-2)所示基團之化合物。
又,本發明的其他方面是關於助焊劑,該助焊劑含有通式(1-1)或(1-2)所示基團之化合物。又,本發明的其他方面,也可為一種助焊劑,其含有通式(1-1)或(1-2)所示基團之化合物,該助焊劑為了製造半導體用黏著劑而使用。
又,本發明的其他方面,也可為一種組成物,其含有環氧樹脂、硬化劑及通式(1-1)或(1-2)所示基團之化合物,該組成物作為半導體用黏著劑來使用。進而,本發明的其他方面,也可為一種組成物,其含有環氧樹脂、硬化劑及通式(1-1)或(1-2)所示基團之化合物,該組成物是為了製造半導體用黏著劑而使用。
以下,藉由實施例來更具體說明本發明,但本發明並未被限定於這些實施例。
各實施例及比較例所使用的化合物如以下所示。
(a)環氧樹脂
.含有三酚甲烷結構多官能固態環氧化合物(Japan Epoxy resin股份有限公司製,商品名「EP1032H60」,以下稱為「EP1032」。)
.雙酚F型液狀環氧樹脂(Japan Epoxy resin股份有限公司製,商品名「YL983U」,以下稱為「YL983」。)
.柔軟性環氧樹脂(Japan Epoxy resin股份有限公司製,商品名「YL7175」,以下稱為「YL7175」。)
(b)硬化劑
.2,4-二胺-6-[2’-甲基咪唑-(1’)]-乙基-s-三氮雜苯異三聚氰酸加成物(四國化成股份有限公司製,商品名「2MAOK-PW」,以下稱為「2MAOK」。)
(c)以具有通式(1-1)或(1-2)所示的基團之化合物所構成的助焊劑
.2,2-二甲基戊二酸(SIGMA-ALDRICH股份有限公司製,熔點約83℃)
.3,3-二甲基丁二酸(SIGMA-ALDRICH股份有限公司製,熔點約100℃)
(c’)其他的助焊劑
.戊二酸(東京化成股份有限公司製,熔點約98℃)
.丁二酸(SIGMA-ALDRICH股份有限公司製,熔點約188℃)
.己二酸(東京化成股份有限公司製,熔點約153℃)
.丙二酸(SIGMA-ALDRICH股份有限公司製,熔點約135~137℃)
.1,3,5-戊三羧酸(東京化成股份有限公司製,熔點約113℃,以下稱為「戊三羧酸」)
(d)分子量10000以上的高分子成分
.苯氧基樹脂(東都化成股份有限公司製,商品名「ZX1356」,Tg:約71℃、Mw:約63000,以下稱為「ZX1356」)
(e)填充劑
(e-1)無機填充劑
.二氧化矽填充劑(ADMATECHS股份有限公司製,商品名「SE2050」,平均粒徑0.5μm,以下稱為「SE2050」。)
.經環氧矽烷處理之二氧化矽填充劑(ADMATECHS股份有限公司製,商品名「SE2050-SEJ」、平均粒徑0.5μm、以下稱為「SE2050-SEJ」)
.經丙烯酸表面處理之奈米二氧化矽填充劑(ADMATECHS股份有限公司製,商品名「YA050C-SM」、平均粒徑50nm、以下稱為「SM-Nanosilica」。)
(e-2)樹脂填充劑
.有機填充劑(Rohm and Haas股份有限公司製,商品
名「EXL-2655」,核殼型有機微粒子,以下稱為「EXL-2655」。)
高分子成分的重量平均分子量(Mw),是藉由GPC法求出的數值。GPC法的詳細條件如下。
HPLC-8020(產品名,TOSOH股份有限公司製)
管柱:2 pieces of GMHXL+1 piece of G-2000XL
檢測器:RI檢測器
管柱溫度:35℃
流速:1ml/分鐘
標準品:聚苯乙烯
<薄膜狀半導體用黏著劑的製作>
(實施例1)
準備環氧樹脂3g(「EP1032」為2.4g、「YL983」為0.45g、「YL7175」為0.15g)、硬化劑「2MAOK」0.1g、2,2-二甲基戊二酸0.11g(0.69mmol)、無機填充劑1.9g(「SE2050」為0.38g、「SE2050-SEJ」為0.38g、「SM-Nanosilica」為1.14g)、樹脂填充物(「EXL-2655」)0.25g,及丁酮(甲基乙基酮,固形份為63質量%之量),加入與固形份等重之直徑0.8mm的顆粒及直徑2.0mm的顆粒,以珠磨機(Fritsch股份有限公司,遊星型微粉碎機P-7)攪拌30分鐘。之後,加入1.7g的苯氧基樹脂(ZX1356),再次以珠磨機攪拌30分鐘後,將使用於攪拌的顆粒以過濾除去,得到樹脂清漆。
將所得到的樹脂清漆,以小型精密塗佈裝置(廉井精機),塗佈於基材薄膜上(帝人杜邦薄膜股份有限公司製,
商品名「Byu-RekkusuA53」),再以無塵烘箱(ESPEC製)進行乾燥(70℃/10min),則可得薄膜狀黏著劑。
(實施例2、比較例1~5)
使用材料的組成,如下述表1所記載的變更之外,以與實施例1相同的方式,製作實施例2及比較例1~5的薄膜狀黏著劑。
以下,表示從實施例及比較例所得到的薄膜狀黏著劑的評價方法
<初期連接性的評價>
將實施例或比較例所製成的薄膜狀黏著劑,裁切成規定的尺寸(長度8mm×寬度8mm×厚度0.045mm)裁切,貼附於玻璃環氧基板(玻璃環氧基材:厚度420μm、銅導線:厚度9 μm)上,將附有焊料凸塊的半導體晶片(晶片尺寸:長度7.3mm×寬度7.3mm×厚度0.15mm,凸塊高度:銅柱+焊料約40μm、凸塊數目328),以倒裝晶片式構裝裝置「FCB3」(Panasonic製,商品名)進行構裝(構裝條件:壓接頭溫度為350℃、壓接時間5秒、壓接壓力0.5MPa)。藉此,與第4圖同樣地,製作出將上述玻璃環氧基板與附有焊料凸塊之半導體晶片,以菊鍊(串鍊,daisy-chain)連接而成的半導體裝置。
所得到的半導體裝置的連接電阻值,藉由使用萬用電表(ADVANTEST製,商品名「R6871E」)測定,評價構裝後的初期導通。連接電阻值為10.0~13.5Ω時,則連接性良
好,評價為「A」;連接電阻值為13.5~20Ω時,則連接性不良,評價為「B」;連接電阻值大於20Ω及連接電阻值未滿10Ω時所致的因連接不良的開路(0pen,無法顯示電阻值)時,皆為連接性不良,評價為「C」。
<孔洞評價>
關於以上述的方法所製作的半導體裝置,以超音波影像診斷裝置(商品名「Insight-300」,INSIGHT股份有限公司製)拍攝外觀影像,再以SCANNER GT-9300UF(EPSON股份有限公司製,商品名)讀取晶片上的黏著材料層的影像(由半導體用黏著劑的硬化物所構成的層),使用影像處理軟體Adobe Photoshop,藉由色調修正、黑白化處理(轉換成黑白,Convert to black and white),辨識出孔洞部分,由分布圖(直方圖,histogram)計算出孔洞部分所佔的比例。以晶片上的黏著材料面積為100%,而孔洞發生率在10%以下時,評價為「A」,10~20%時,評價為「B」,高於20%時,評價為「C」。
<焊料濕潤性評價>
關於以上述的方法所製作的半導體裝置,觀察連接部的剖面,Cu配線電路朝上的表面,90%的焊料為濕潤時,評價為「A」(良好),濕潤的焊料少於90%時,評價為「B」(濕潤性不足)。
<吸濕前於260℃時的黏著力的測定>
將實施例或比較例所製成的薄膜狀黏著劑,裁切成規定的尺寸(長度5mm×寬度5mm×厚度0.045mm),然後
於70℃的環境下貼附於矽晶片(長5mm×寬5mm×厚0.725mm,氧化膜包覆)上,再使用熱壓接試驗機(日立化成techno plant股份有限公司製),壓接於包覆著焊接光阻(太陽油墨股份有限公司製,商品名「AUS308」)之玻璃環氧基板(厚度0.02mm)(壓接條件:壓接頭溫度350℃、壓接時間5秒、壓接壓力0.5MPa)。繼而,於無塵烘箱(ESPEC製)中進行後硬化(175℃、2小時),可獲得作為試驗樣品的半導體裝置。
關於上述試驗樣品(試樣),於260℃的加熱板上,使用黏著力測定裝置(DAGE股份有限公司製,萬能型bond tester DAGE400型),以從基板到工具的高度為0.05mm、工具速度0.05mm/s的條件來進行測定。
<吸濕後於260℃中的黏著力的測定>
將實施例或比較例所製成的薄膜狀黏著劑,裁切成規定的尺寸(長度5mm×寬度5mm×厚度0.045mm),然後於70℃的環境下貼附於矽晶片(長度5mm×寬度5mm×厚度0.725mm,氧化膜包覆)上,再使用熱壓接試驗機(日立化成techno plant股份有限公司製),壓接於包覆著焊接光阻(太陽油墨股份有限公司製,商品名「AUS308」)之玻璃環氧基板(厚度0.02mm)(壓接條件:壓接頭溫度350℃、壓接時間5秒、壓接壓力0.5MPa)。繼而,於無塵烘箱(ESPEC製)中進行後硬化(175℃、2小時),可獲得作為試驗樣品的半導體裝置。
將上述試驗樣品,靜置於85℃、相對溼度60%的恆溫
恆濕器(ESPEC製,PR-2KP)中48小時,取出後於260℃的加熱板上,使用黏著力測定裝置(DAGE股份有限公司製,萬能型bond tester DAGE400型),以從基板到工具的高度為0.05mm、工具速度0.05mm/s的條件來進行測定。
<耐迴焊性的評價>
將利用<初期連接性的評價>中所記載的方法製作而成的半導體裝置,使用密封材料(日立化成工業股份有限公司製,商品名「CEL9750ZHF10」),以180℃、6.75MPa、90秒的條件進行塑模,然後於無塵烘箱(ESPEC製)中,以175℃進行5小時的後硬化,而獲得封裝體。繼而,將該封裝體,以JEDEC level 2的條件高溫吸濕後,使該封裝體通過IR迴焊爐(FURUKAWA ELECTRIC製,商品名「SALAMANDER」)三次。關於迴焊後的封裝體的連接性,以與上述的初期連接性的評價相同的方法進行,來作為耐迴焊性的評價。無剝離且連接良好時,評價為「A」,有剝離或連接不良時,評價為「B」。
<耐TCT評價(連接可靠性的評價)>
將利用<初期連接性的評價>中所記載的方法製作出來的半導體裝置,使用密封材料(日立化成工業股份有限公司製,商品名「CEL9750ZHF10」),以180℃、6.75MPa、90秒的條件進行塑模,然後於無塵烘箱(ESPEC製)中,以175℃進行5小時的後硬化,而獲得封裝體。繼而,將該封裝體連接至冷熱循環試驗機(ETAC製,商品名「THERMAL SHOCK CHAMBER NT1200」),施以1mA的電流,以25
℃ 2分鐘/-55℃ 15分鐘/25℃ 2分鐘/125℃ 15分鐘/25℃ 2分鐘作為1個循環,對重複1000次循環後的連接電阻的變化進行評價。與初期的電阻值波形相比,1000次循環後沒有出現太大變化時,評價為「A」,產生1Ω以上的差異時,評價為「B」。
<絕緣可靠性試驗(HAST試驗:Highly Accelerated Storage Test)>
將以實施例或比較例所製成的薄膜狀黏著劑(厚度:45μm),貼附於梳型電極評價測試元件群(TEG(Test Element Group))(日立化成工業有限公司製,配線間距:50μm)上,於無塵烘箱(ESPEC製)中,以175℃進行2小時硬化。將硬化後的試樣,設置於加速壽命測試裝置(HIRAYAMA股份有限公司製,商品名「PL-422R8」、條件:130℃/85%RH/100小時,施加電壓5V),測定絕緣電阻。100小時後的絕緣電阻為108Ω以上時,評價為「A」;107Ω以上而未滿108Ω時,評價為「B」;未滿107Ω時,評價為「C」。
實施例1及2的半導體黏著劑,吸濕後於260℃中的黏著力高,使用實施例1或2的半導體用黏著劑所製作的半導體裝置,可充分抑制孔洞發生,焊料濕潤性良好,並確認具優異的耐迴焊性、耐連接可靠性及耐絕緣可靠性。
10‧‧‧半導體晶片
15‧‧‧配線(連接部)
20‧‧‧基板(配線電路基板)
30‧‧‧連接凸塊
32‧‧‧凸塊(連接部)
34‧‧‧貫穿電極
40‧‧‧黏著材料
41‧‧‧半導體用黏著劑(薄膜狀黏著劑)
50‧‧‧中介片
60‧‧‧焊接光阻
90‧‧‧梳型電極
100、200、300、400、500、600‧‧‧半導體裝置
第1圖是表示本發明的半導體裝置的一實施形態的示意剖面圖。
第2圖是表示本發明的半導體裝置的另一實施形態的示意剖面圖。
第3圖是表示本發明的半導體裝置的另一實施形態的示意剖面圖。
第4圖是示意地表示本發明的半導體裝置的製造方法的一實施形態的步驟剖面圖。
Claims (19)
- 一種半導體用黏著劑,其含有環氧樹脂、硬化劑及具有下述通式(1-1)或(1-2)所示的基團之化合物,
- 如請求項1所述之半導體用黏著劑,其中,前述化合物是含有2個羧基之化合物。
- 如請求項1或請求項2所述之半導體用黏著劑,其中,前述化合物是下述通式(2-1)或(2-2)所示的化合物,
- 如請求項1~3中任一項所述之半導體用黏著劑,其 中,前述化合物是下述通式(3-1)或(3-2)所示的化合物,
- 如請求項4所述之半導體用黏著劑,其中,m1是0~8的整數,m2是0~7的整數。
- 如請求項1~5中任一項所述之半導體用黏著劑,其中,前述化合物的熔點是150℃以下。
- 如請求項1~6中任一項所述之半導體用黏著劑,其中,前述電子供給基是碳數1~10的烷基。
- 如請求項1~7中任一項所述之半導體用黏著劑,其中,前述化合物是助焊劑。
- 如請求項1~8中任一項所述之半導體用黏著劑,其中,進而含有重量平均分子量是10000以上的高分子成分。
- 如請求項1~9中任一項所述之半導體用黏著劑,其形狀是薄膜狀。
- 一種助焊劑,其含有具有下述通式(1-1)或(1-2)所示的基團之化合物,
- 如請求項11所述之助焊劑,其中,前述化合物是含有2個羧基之化合物。
- 如請求項11或請求項12所述之助焊劑,其中,前述化合物是下述通式(2-1)或(2-2)所示的化合物,
- 如請求項11~13中任一項所述之助焊劑,其中,前述化合物是下述通式(3-1)或(3-2)所示的化合物,
- 如請求項14所述之助焊劑,其中,m1是0~8的整數,m2是0~7的整數。
- 如請求項11~15中任一項所述之助焊劑,其中,前述電子供給基是碳數1~10的烷基。
- 如請求項11~16中任一項所述之助焊劑,其是調配於半導體用黏著劑中之助焊劑,該半導體用黏著劑含有環氧樹脂及硬化劑。
- 一種半導體裝置的製造方法,是製造半導體裝置的方法,該半導體裝置是半導體晶片及配線電路基板的各個連接部互相電連接而成、或是複數個半導體晶片的各個連接部互相電連接而成,其中,該半導體裝置的製造方法具備密封步驟,該密封步驟使用如請求項1~10中任一項所述之半導體用黏著劑來密封前述連接部的至少一部分。
- 一種半導體裝置,其是藉由請求項18所述的製造方法而製得。
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US (1) | US20150035175A1 (zh) |
JP (1) | JP5867584B2 (zh) |
KR (1) | KR20140116216A (zh) |
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TWI596154B (zh) * | 2014-03-25 | 2017-08-21 | Senju Metal Industry Co | Flux and solder paste |
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JP2015030745A (ja) * | 2013-07-31 | 2015-02-16 | 住友ベークライト株式会社 | 樹脂組成物、半導体装置、多層回路基板および電子部品 |
MY186938A (en) | 2015-11-04 | 2021-08-26 | Lintec Corp | Curable resin film and first protective film forming sheet |
KR102351843B1 (ko) * | 2017-06-07 | 2022-01-18 | 쇼와덴코머티리얼즈가부시끼가이샤 | 반도체용 필름형 접착제, 반도체 장치의 제조 방법 및 반도체 장치 |
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JPS5849718A (ja) * | 1981-09-19 | 1983-03-24 | Mitsubishi Electric Corp | 耐熱水性樹脂材料用組成物 |
JP3791403B2 (ja) * | 2000-12-04 | 2006-06-28 | 富士電機ホールディングス株式会社 | 鉛フリーハンダ対応無洗浄用フラックスおよびこれを含有するハンダ組成物 |
JP4961730B2 (ja) * | 2005-12-01 | 2012-06-27 | 富士電機株式会社 | 電子部品実装用接合材料 |
KR101354871B1 (ko) * | 2006-03-10 | 2014-01-22 | 미쓰비시 가가꾸 가부시키가이샤 | 수지 분산체, 도료, 적층체 및 그 제조 방법 |
JP5411503B2 (ja) * | 2006-08-28 | 2014-02-12 | パナソニック株式会社 | 熱硬化性樹脂組成物及びその製造方法並びに回路基板 |
JP5093766B2 (ja) * | 2007-01-31 | 2012-12-12 | 株式会社タムラ製作所 | 導電性ボール等搭載半導体パッケージ基板の製造方法 |
JP5360359B2 (ja) * | 2008-07-01 | 2013-12-04 | 株式会社スリーボンド | エポキシ樹脂組成物 |
US8288591B2 (en) * | 2008-11-20 | 2012-10-16 | Designer Molecules, Inc. | Curing agents for epoxy resins |
JP5069725B2 (ja) * | 2009-07-10 | 2012-11-07 | パナソニック株式会社 | 熱硬化性樹脂組成物及び回路基板 |
JP2011054444A (ja) * | 2009-09-02 | 2011-03-17 | Fujitsu Ltd | 導電材料、電子デバイス及びその製造方法 |
EP2479228A1 (en) * | 2009-09-16 | 2012-07-25 | Sumitomo Bakelite Co., Ltd. | Adhesive film, multilayer circuit board, electronic component, and semiconductor device |
JP6045774B2 (ja) * | 2010-03-16 | 2016-12-14 | 日立化成株式会社 | 半導体封止充てん用エポキシ樹脂組成物、半導体装置、及びその製造方法 |
JP5588287B2 (ja) * | 2010-09-27 | 2014-09-10 | パナソニック株式会社 | 熱硬化性樹脂組成物及び半導体部品実装基板 |
JP5842084B2 (ja) * | 2010-09-27 | 2016-01-13 | パナソニックIpマネジメント株式会社 | 半導体部品実装基板 |
JP2012089750A (ja) * | 2010-10-21 | 2012-05-10 | Hitachi Chem Co Ltd | 半導体封止充てん用熱硬化性樹脂組成物及び半導体装置 |
CN104137246A (zh) * | 2012-02-24 | 2014-11-05 | 日立化成株式会社 | 半导体装置及其制造方法 |
-
2012
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- 2012-10-01 KR KR1020147023546A patent/KR20140116216A/ko not_active Application Discontinuation
- 2012-10-01 CN CN201280070496.9A patent/CN104185666A/zh active Pending
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Cited By (2)
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TWI596154B (zh) * | 2014-03-25 | 2017-08-21 | Senju Metal Industry Co | Flux and solder paste |
US9902022B2 (en) | 2014-03-25 | 2018-02-27 | Senju Metal Industry Co., Ltd. | Flux and solder paste |
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US20150035175A1 (en) | 2015-02-05 |
JP5867584B2 (ja) | 2016-02-24 |
CN104185666A (zh) | 2014-12-03 |
JPWO2013125087A1 (ja) | 2015-07-30 |
KR20140116216A (ko) | 2014-10-01 |
WO2013125087A1 (ja) | 2013-08-29 |
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