TWI421319B - 黏接著劑組成物、黏接著片及半導體裝置之製造方法 - Google Patents
黏接著劑組成物、黏接著片及半導體裝置之製造方法 Download PDFInfo
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Description
本發明係有關:在將半導體元件(半導體晶片)黏晶(die bonding)於有機基板和導線架(lead frame)之步驟、與切割矽晶圓(silicon wafer)等且將半導體晶片黏晶於有機基板和導線架之步驟中特別適用的黏接著劑組成物,及具有由該黏接著劑組成物所組成之黏接著劑層的黏接著片,以及使用該黏接著片所得之半導體裝置之製造方法。
矽、砷化鎵等半導體晶圓係在經切割分離(切割)成元件小片(IC晶片)後轉送至下個步驟之接合(bonding)步驟。此時,半導體晶圓係在經預先貼合於黏著片並固定之狀態下,進行切割、洗淨、乾燥、擴大(expanding)、拾取(pick up)之各步驟後,再轉送至下個步驟之接合步驟。此外,從自外部環境保護半導體晶片及製成易安裝於印刷基板之形狀之目的來看,在接合步驟後,也將接合有IC晶片之基板藉由模型樹脂(molded resin)密封而進行製造半導體封裝。
為了簡化此等步驟中之拾取步驟與接合步驟之流程,而提案同時兼具晶圓固定機能與晶粒(die)接著機能之例如記載於專利文獻1至4中之切割/黏晶用黏接著片等。
在專利文獻1至4中揭示以由特定組成物組成之黏接著劑層與基材所構成的黏接著片。此黏接著劑層在進行晶圓切割時,由於具有固定晶圓之機能,並且可經由照射能量線而降低接著力並控制與基材間之接著力,故若在切割結束後進行晶片(chip)之拾取,則黏接著劑層會與晶片一同剝離。若將伴隨有黏接著劑層之IC晶片載置於基板並加熱後,則黏接著劑層中之熱硬化性樹脂會顯現接著力,而完成IC晶片與基板之接著。
只要使用揭示於上述專利文獻中之黏接著片,即可進行所謂直接接合(direct bonding),而可省略晶粒接著用接著劑之塗布步驟。
然而,近年來,對於半導體裝置之物性要求變得非常嚴苛。例如:半導體封裝之品質保證期間之測試係要求在嚴苛之濕熱環境下之封裝可靠性。然而,因半導體晶片本身薄型化,結果晶片強度降低,而在嚴苛之濕熱環境下之封裝可靠性變得不足。
此外,近年來,在接續電子零件時進行之表面安裝,係進行將封裝全體暴露於焊料熔點以上之高溫下之方法(回焊)。最近因顧慮到環境,而改用不含鉛之焊料,因此安裝溫度即從以往之240℃上升至260℃,而在半導體封裝內部產生之應力變大,半導體晶片與黏接著片之接著界面發生剝離和發生封裝破裂之危險性更為升高。
換言之,現今正要求一種黏接著片,其不僅可如同上述進行所謂直接接合,且即使放置於嚴苛的濕熱環境中,接著強度等品質也不會劣化,而且在之後即使暴露於260℃之高溫條件下,也不會發生封裝破裂等(亦即可達成高封裝可靠性)。
用以因應如此嚴苛的物性要求(特別是對於濕熱環境之耐性之要求)之技術,有例如在專利文獻3中揭示的具有由能量線硬化型黏著成分、環氧樹脂、與酚系樹脂所形成之黏接著層的黏著帶。
在專利文獻3中記載有下述內容:上述之能量線硬化型黏著成分可舉例如由衍生自(甲基)丙烯酸酯單體等之構成單元等所組成的(甲基)丙烯酸酯共聚物;環氧樹脂係具有若受熱就會將被著物予以強力接著之性質;酚系樹脂係經由加熱而與環氧樹脂反應並形成硬化物。
此外,在專利文獻5之實施例5中揭示一種含有丙烯酸共聚物、環氧樹脂、與熱活性型潛在性環氧樹脂硬化劑(酚樹脂)之接著劑組成物。另一方面,在專利文獻2、4、5等中揭示(甲基)丙烯酸苯甲酯做為用以構成黏著成分之(甲基)丙烯酸酯單體之一例。
然而,在此等文獻中關於(甲基)丙烯酸苯甲酯之使用量等皆無任何具體記載。
[專利文獻1]日本特開平2-32181號公報
[專利文獻2]日本特開平8-239636號公報
[專利文獻3]日本特開平10-8001號公報
[專利文獻4]日本特開2000-17246號公報
[專利文獻5]日本特開2006-335860號公報
如上述,在安裝有逐漸薄型化之半導體晶片的封裝中,正要求實現即使當放置於如上述之嚴苛的濕熱環境中後,暴露於嚴苛的回焊條件下時,仍不會發生接著界面之剝離和封裝破裂之高封裝可靠性。
本發明係有鑑於上述之先前技術而研創者,其目的係對使用於晶片接合(chip bond)之黏接著劑加以研究,以因應上述要求。
本發明人等為了解決如上述之課題而致力研究後結果發現,若使用由包含含有一定量之衍生自(甲基)丙烯酸苯甲酯之構造單元之丙烯酸共聚物、環氧系熱硬化性樹脂、與熱硬化劑的黏接著劑組成物所組成之黏接著劑層形成於基材上而成之黏接著片製造半導體封裝,則此半導體封裝即使當放置於濕熱環境下,並暴露於嚴苛的回焊條件時,仍不會發生接著界面之剝離和封裝破裂,遂完成本發明。
本發明之要旨如下述:
[1]一種黏接著劑組成物,係包含:含有衍生自(甲基)丙烯酸苯甲酯之構造單元20至95重量%之丙烯酸共聚物(A)、環氧系熱硬化性樹脂(B)、與熱硬化劑(C)。
[2]如上述[1]之黏接著劑組成物,其中,丙烯酸共聚物(A)係含有衍生自具有羥基之(甲基)丙烯酸酯之構造單元3至50重量%者。
[3]一種黏接著片,其由上述[1]或[2]之黏接著劑組成物所組成之黏接著劑層係以可剝離之方式形成於基材上。
[4]一種半導體裝置之製造方法,係具備下述步驟:於上述[3]之黏接著片之黏接著劑層貼合半導體晶圓之步驟;切割該半導體晶圓之步驟;使前述黏接著劑層之至少一部分固著殘留於半導體晶圓上,而將切割後之半導體晶圓從該黏接著片之基材剝離之步驟;隔介固著殘留於該半導體晶圓之黏接著劑層,將剝離之半導體晶圓熱壓合於晶粒墊(die pad)部上之步驟。
根據本發明,可提供:在安裝有逐漸薄型化之半導體晶片的封裝中,即使當放置於濕熱環境下,並暴露於嚴苛的回焊條件下時,仍可達成高封裝可靠性之黏接著劑組成物;具有由該黏接著劑組成物所組成之黏接著劑層的黏接著片;及使用該黏接著片所得之半導體裝置之製造方法。
以下,更詳細說明本發明之黏接著劑組成物、黏接著片及半導體裝置之製造方法。
本發明之黏接著劑組成物(以下,有時僅稱為「黏接著劑組成物」)係含有:含有衍生自(甲基)丙烯酸苯甲酯之構造單元20至95重量%之丙烯酸共聚物(A)、環氧系熱硬化性樹脂(B)、與熱硬化劑(C)。衍生自(甲基)丙烯酸苯甲酯之構造單元如下述式(1)所示。
在上述式(1)中,R表示氫原子或甲基。
為了改良各種物性,本發明之黏接著劑組成物也可含有後述之其他成分。以下,具體說明關於此等各成分。
本發明之黏接著劑組成物中之丙烯酸共聚物(A)係含有衍生自(甲基)丙烯酸苯甲酯之構造單元20至95重量%。(甲基)丙烯酸苯甲酯由於具有疏水性高之苯甲基而吸濕性低,故衍生自(甲基)丙烯酸苯甲酯之構造單元係具有降低丙烯酸共聚物整體之吸濕性之作用。此外,若使(甲基)丙烯酸苯甲酯共聚合,則丙烯酸共聚物與構成本發明之黏接著劑組成物之其他成分的混合性會變良好。
由於(甲基)丙烯酸苯甲酯之熱安定性也優良,故在丙烯酸共聚物中若使(甲基)丙烯酸苯甲酯共聚合,即可維持黏接著劑組成物之耐熱性,同時降低其吸濕率。黏接著片之黏接著劑中所含之水分曝曬於高溫中而急遽蒸發被認為是使封裝發生破裂之主要原因之一,但由於本發明之黏接著劑組成物即使放置於濕熱環境下也幾乎不會吸濕,故使用黏接著劑組成物製得之半導體封裝即使在放置於濕熱環境下後又暴露於嚴苛的回焊條件下,在其半導體封裝也不會發生封裝破裂。因此,可達成高度封裝可靠性。
衍生自(甲基)丙烯酸苯甲酯之構造單元之含量,相對於丙烯酸共聚物(A)全體,為20至95重量%,且以25至90重量%為佳、以30至85重量%較佳。若未達20重量%,則在維持對於黏接著劑組成物之耐熱性和降低吸濕率等方面,有時無法得到充分之效果。此外,若超過95重量%,則有時由黏接著劑組成物組成之黏接著劑層對半導體晶圓之貼合性會變得不良。
前述丙烯酸共聚物(A)以含有衍生自具有羥基之(甲基)丙烯酸酯之構造單元為佳。此係因衍生自具有羥基之(甲基)丙烯酸酯之構造單元與環氧樹脂之相溶性良好,且當黏接著劑組成物含有後述之交聯劑(F)時,與交聯劑(F)之交聯性也良好之故。此外,也因可提高黏接著劑組成物之硬化物對半導體晶圓之接著強度之故。
具有羥基之(甲基)丙烯酸酯可舉例如:丙烯酸2-羥乙酯、甲基丙烯酸2-羥乙酯、丙烯酸2-羥丙酯、甲基丙烯酸2-羥丙酯等。
衍生自具有羥基之(甲基)丙烯酸酯之構造單元之含量,相對於丙烯酸共聚物(A)全體,以3至50重量%為佳、以5至40重量%較佳、以10至30重量%更佳。
丙烯酸共聚物(A)之其他單體可舉例如:(甲基)丙烯酸酯單體或其衍生物。例如:丙烯酸、甲基丙烯酸、伊康酸(itaconic acid)、丙烯酸環氧丙酯、甲基丙烯酸環氧丙酯等。
此外,具有環狀骨架之(甲基)丙烯酸酯也可舉例如:丙烯酸環烷酯、丙烯酸異冰片酯(isobornyl acrylate)、丙烯酸二環戊酯、丙烯酸二環戊烯酯、丙烯酸二環戊烯氧基乙酯、亞胺基丙烯酸酯(imidoacrylate)。
烷基之碳數為1至18之(甲基)丙烯酸烷酯,例如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸丁酯等亦可列舉為丙烯酸共聚物(A)之單體。
除了上述單體以外,丙烯酸共聚物(A)也可與乙酸乙烯酯、丙烯腈、苯乙烯等共聚合。
此等可單獨使用1種或組合2種以上使用。
其他單體之含量,相對於丙烯酸共聚物(A)全體,為0至77重量%,且以0至70重量%為佳、以0至60重量%較佳。
前述「其他單體」在與環氧系熱硬化性樹脂之相溶性良好之觀點上,以丙烯酸甲酯等前述(甲基)丙烯酸烷酯為佳。
丙烯酸共聚物(A)之重量平均分子量以1萬至200萬為佳、以10萬至150萬較佳。再者,在本說明書中,重量平均分子量之值皆為依GPC(gel permeation chromatography,凝膠滲透層析)法所得之換算成苯乙烯之值。若丙烯酸共聚物(A)之重量平均分子量過低,則由黏接著劑組成物所組成之黏接著劑層與基材之黏著力會變高,而在前述之拾取步驟中有時會造成IC晶片之拾取不良,若超過200萬,則在前述之接合步驟中有時黏接著劑層不會埋入基板之凹凸中,而成為產生空隙(void)等之原因。
丙烯酸共聚物(A)之玻璃轉移溫度以-30至50℃為佳、以-15至40℃較佳、以-5至30℃特佳。若玻璃轉移溫度過低,則黏接著劑層與基材之接著力會變大,而有時會造成IC晶片之拾取不良,若過高,則有時用以固定晶圓之接著力會不足。
環氧系熱硬化性樹脂可使用以往已周知之各種環氧樹脂。
黏接著劑組成物中之環氧系熱硬化性樹脂(B)之含量,相對於丙烯酸共聚物(A)100重量份,以1至1500重量份為佳、以3至1000重量份較佳。相對於丙烯酸共聚物(A)100重量份,若環氧系熱硬化性樹脂(B)之含量未達1重量份,則有時無法得到充分之接著性,若超過1500重量份,則由黏接著劑組成物所組成之黏接著劑層與基材之黏著力會變高,而有時會造成拾取不良。
上述環氧樹脂可舉例如:雙酚A二環氧丙基醚或其氫化物、下述式(2)所示之鄰甲酚酚醛(o-cresol novolac)樹脂、下述式(3)所示之二環戊二烯型環氧樹脂、下述式(4)或下述式(5)所示之聯苯型環氧樹脂或是聯苯化合物等在構造單元之分子中含有2個以上之官能基之環氧化合物:
(惟,式中n為0以上之整數)
(惟,式中n為0以上之整數)
(惟,式中n為0以上之整數)
(惟,式中R為氫原子或甲基)。
此等可單獨使用1種或組合2種以上使用。
熱硬化劑(C)係對環氧系熱硬化性樹脂(B)發揮做為熱硬化劑之機能。較佳之熱硬化劑(C)可舉例如在1分子中具有可與環氧基反應之官能基2個以上之化合物,該官能基可舉例如:酚性羥基、醇性羥基、胺基、羧基及酸酐基等。此等之中尤以酚性羥基、胺基及酸酐基為佳,以酚性羥基及胺基較佳。
此等之具體例可舉例如:下述式(6)所示之酚醛型酚樹脂、下述式(7)所示之二環戊二烯系酚樹脂、下述式(8)所示之多官能系酚樹脂、下述式(9)所示之芳烷基酚樹脂等酚性熱硬化劑或DICY(dicyandiamide,雙氰胺)等胺系熱硬化劑。此等熱硬化劑可單獨使用1種或混合2種以上使用:
(惟,式中n表示0以上之整數)
(惟,式中n表示0以上之整數)
(惟,式中n表示0以上之整數)
(惟,式中n表示0以上之整數)。
黏接著劑組成物中之熱硬化劑(C)之含量,相對於環氧系熱硬化性樹脂(B)100重量份,以0.1至500重量份為佳、以1至200重量份較佳。若熱硬化劑(C)之量過少,則黏接著劑組成物之硬化性會不足,而有時無法得到黏接著劑層之接著性,若過多,則黏接著劑組成物之吸濕率會變高,而有時封裝之可靠性會降低。
本發明之黏接著劑組成物係含有上述丙烯酸共聚物(A)、環氧系熱硬化性樹脂(B)、及熱硬化劑(C)做為必須成分,且為了改良各種物性,也可含有下述之成分。
硬化促進劑(D)係使用於調整黏接著劑組成物之硬化速度。較佳之硬化促進劑(D)可舉例如可促進環氧基與酚性羥基或胺等之反應之化合物。具體而言可舉例如:三伸乙二胺、苯甲基二甲基胺、三乙醇胺、二甲胺基乙醇、參(二甲胺基甲基)酚等3級胺類;2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑等咪唑類;三丁基膦、二苯基膦、三苯基膦等有機膦類;四苯基硼酸四苯基鏻、四苯基硼酸三苯基膦等四苯基硼酸鹽等。
此等可單獨使用1種或混合2種以上使用。
從提高接著性之觀點來看,此等之中尤以咪唑類為佳。
當使用硬化促進劑(D)時,黏接著劑組成物中之硬化促進劑(D)之含量,相對於環氧系熱硬化性樹脂(B)100重量份,通常以0.001至100重量份為佳、以0.01至50重量份較佳、以0.1至10重量份更佳。
耦合劑係用以提高黏接著劑組成物對於被著物之接著性、密著性。此外,因使用耦合劑,而可不損害將黏接著劑組成物硬化所得之硬化物之耐熱性,即可提高其耐水性。耦合劑(E)以使用具有會與上述丙烯酸共聚物(A)及環氧系熱硬化性樹脂(B)等所具有之官能基反應之基的化合物為佳。
具體而言,耦合劑(E)以矽烷耦合劑為佳。
如此之耦合劑可舉例如:γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、β-(3,4-乙氧基環己基)乙基三甲氧基矽烷、γ-(甲基丙烯醯氧丙基)三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-6-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-6-(胺基乙基)-γ-胺基丙基甲基二乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、N-脲基丙基三乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽烷基丙基)四硫烷(bis(3-triethoxysilyl propyl)tetrasulfane)、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、咪唑矽烷等。
此等可單獨使用1種或混合2種以上使用。
當使用耦合劑(E)時,黏接著劑組成物中之耦合劑(E)之含量,相對於丙烯酸共聚物(A)與環氧系熱硬化性樹脂(B)之合計100重量份,通常為0.1至20重量份,且以0.2至10重量份為佳、以0.3至5重量份較佳。若未達0.1重量份,則有無法得到效果之可能性,若超過20重量份,則有成為釋氣(outgas)之原因之可能性。
為了調節黏接著劑組成物之初期接著力及凝聚力,也可添加交聯劑(F)。交聯劑(F)可舉例如:有機多價異氰酸酯化合物、有機多價亞胺化合物等。
上述有機多價異氰酸酯化合物可舉例如:芳香族多價異氰酸酯化合物、脂肪族多價異氰酸酯化合物、脂環族多價異氰酸酯化合物、及此等多價異氰酸酯化合物之三聚物、以及使此等多價異氰酸酯化合物與多元醇化合物反應所得之末端異氰酸酯胺甲酸乙酯預聚物(terminal isocyanate urethane prepolymer)等。
有機多價異氰酸酯化合物之更具體之例可舉例如:二異氰酸2,4-甲苯酯(2,4-tolylene diisocyanate)、二異氰酸2,6-甲苯酯、二異氰酸1,3-二甲苯酯(1,3-xylylene diisocyanate)、二異氰酸1,4-二甲苯酯、二苯基甲烷-4,4’-二異氰酸酯、二苯基甲烷-2,4’-二異氰酸酯、3-甲基二苯基甲烷二異氰酸酯、二異氰酸六亞甲酯、異佛酮二異氰酸酯、二環己基甲烷-4,4’-二異氰酸酯、二環己基甲烷-2,4’-二異氰酸酯、三羥甲基丙烷加成二異氰酸甲苯酯、離胺酸異氰酸酯等。
上述有機多價亞胺化合物之具體例可舉例如:N,N’-二苯基甲烷-4,4’-雙(1-氮丙啶甲醯胺)(N,N-diphenylmethane-4,4’-bis(1-aziridine carboxyamide))、三羥甲基丙烷-三-β-氮丙啶基丙酸酯、四羥甲基甲烷-三-β-氮丙啶基丙酸酯、N,N’-甲苯-2,4-雙(1-氮丙啶甲醯胺)三伸乙基三聚氰胺等。
此等可單獨使用或組合2種以上使用。
當使用交聯劑(F)時,黏接著劑組成物中之交聯劑(F)之含量,相對於丙烯酸共聚物(A)100重量份,通常為0.01至10重量份,且以0.1至5重量份為佳、以0.5至3重量份較佳。
在本發明之黏接著劑組成物中,也可調配能量線聚合性化合物(G)。由於經由照射能量線使能量線聚合性化合物(G)硬化,即可降低黏接著劑層之黏著力,故在將IC晶片轉送至接合步驟時可輕易地進行基材與黏接著劑層之層間剝離。再者,由於通常黏接著劑層與晶片間之黏著力係較基材與黏接著劑層間之黏著力大,故在此時IC晶片不會從黏接著劑層剝離。
能量線聚合性化合物(G)係受到如紫外線、電子束等能量線照射後會聚合硬化之化合物。
此能量線聚合性化合物(G)具體而言可舉例如:二環戊二烯二甲氧基二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇單羥基五丙烯酸酯、二季戊四醇六丙烯酸酯;或1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、寡丙烯酸酯(oligoester acrylate)、胺甲酸乙酯丙烯酸酯系寡聚物、環氧改性丙烯酸酯、聚醚丙烯酸酯、伊康酸寡聚物等丙烯酸系化合物。
此類化合物係在分子內具有至少1個聚合性雙鍵,重量平均分子量通常為100至30000(較佳係300至10000)左右。
此等可單獨使用1種、或組合2種以上使用。
當使用能量線聚合性化合物(G)時,黏接著劑組成物中之能量線聚合性化合物(G)之含量,相對於丙烯酸共聚物(A)100重量份,通常為1至400重量份,且以3至300重量份為佳、以10至200重量份較佳。若超過400重量份,則有時會降低黏接著劑層對於有機基板和導線架之接著性。
本發明之黏接著劑組成物在使用時,有時照射紫外線等能量線會降低接著力。此時,在該組成物中添加光聚合起始劑(H),即可減少聚合硬化時間以及光線照射量。
如此之光聚合起始劑(H)具體而言可舉例如:二苯基酮、乙醯苯、安息香(benzoin)、安息香甲基醚、安息香乙基醚、安息香異丙基醚、安息香異丁基醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮、2,4-二乙基噻噸酮(2,4-diethylthioxanthone)、α-羥基環己基苯基酮、苯甲基二苯基硫醚、四甲基胺硫甲醯單硫醚(tetramethylthiuram monosulfide)、偶氮雙異丁腈、聯乙醯(diacetyl)、β-氯蒽醌等。
光聚合起始劑(H)可單獨使用1種、或組合2種以上使用。
光聚合起始劑(H)之調配比例,於理論上應依照存在於黏接著劑中之不飽和鍵量和其反應性、及所使用之光聚合起始劑之反應性來決定,但在複雜之混合物系中此決定方法則並不容易。
當使用光聚合起始劑(H)時,就一般之指標而言,黏接著劑組成物中之光聚合起始劑(H)之含量,相對於能量線聚合性化合物(G)100重量份,通常以0.1至10重量份為佳、以1至5重量份較佳。若未達0.1重量份,則有時會因光聚合不足而無法得到令人滿意的拾取性,若超過10重量份,則會生成無助於光聚合之殘留物,而有時黏接著劑之硬化性會變得不足。
經由將無機填充材(I)調配於黏接著劑組成物中,即可調整熱膨脹係數。對於具有與由金屬或有機樹脂所組成之基板不同之熱膨脹係數之IC晶片,使插入之黏接著劑層硬化後之熱膨脹係數最佳化,即可提高封裝可靠性。此外,也可降低黏接著劑層硬化後之吸濕率。
較佳之無機填充材可舉例如:氧化矽、氧化鋁、滑石、碳酸鈣、鈦白、紅色氧化鐵、碳化矽、氮化硼等粉末;將此等予以球形化而成之小珠(bead)單晶纖維、非晶形纖維等。
此等可單獨使用1種、或混合2種以上使用。
在本發明中,此等之中尤以使用氧化矽粉末、氧化鋁粉末為佳。
無機填充材(I)之使用量,相對於黏接著劑組成物全體,通常可在0至80重量%之範圍內調整。
在本發明之黏接著劑組成物中,除了上述成分以外,也可依需要而調配各種添加劑。
例如,為了維持硬化後黏接著劑層之可撓性,可添加可撓性成分。可撓性成分係在常溫及加熱下具有可撓性之成分,且選擇經加熱或能量線照射後實際上不會硬化者。
可撓性成分可為由熱塑性樹脂或彈性體所組成之聚合物,也可為聚合物之接枝成分、聚合物之嵌段成分。此外,可撓性成分也可為預先經環氧樹脂改性之改性樹脂。
並且,黏接著劑組成物之各種添加劑係亦可使用塑化劑、抗靜電劑、抗氧化劑、顏料、染料等。
由上述之成分組成之黏接著劑組成物係具有壓敏接著性與加熱硬化性,且在未硬化之狀態下具有暫時維持各種被著物之機能。而且,歷經熱硬化,最後可提供耐衝擊性高之硬化物,並且剪切強度(shear strength)與剝離強度之平衡也優良,且即使暴露於嚴苛的濕熱環境中也可維持充分之接著物性。
本發明之黏接著劑組成物可由將上述各成分以適當比例混合而得到。在混合時,可將各成分預先以溶劑稀釋,此外也可在混合時再將溶劑加入。
根據本發明,可提供由使用上述黏接著劑組成物所得之黏接著片。
本發明之黏接著片(以下,有時僅稱為「黏接著片」)係於基材上形成由上述黏接著劑組成物組成之黏接著劑層而成,可採用帶(tape)狀、標籤(label)狀等所有形狀。
黏接著片之基材可舉例如:聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚物薄膜、聚對酞酸乙二酯薄膜、聚萘二甲酸乙二酯薄膜、聚對酞酸丁二酯薄膜、聚胺甲酸乙酯薄膜、乙烯-乙酸乙烯酯共聚物薄膜、離子聚合物(ionomer)樹脂薄膜、乙烯-(甲基)丙烯酸共聚物薄膜、乙烯-(甲基)丙烯酸酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜等透明薄膜。
此外,也可使用此等之交聯薄膜。並且,也可為此等之積層薄膜。
此外,除了上述之透明薄膜以外,也可使用將此等著色之不透明薄膜、氟樹脂薄膜等。惟,在使用本發明之黏接著片時,當從基材面側進行紫外線等能量線照射時,基材係以對於所使用之能量線為透明者為佳。
對於本發明之黏接著片貼合各種被著物,並在被著物上施予所需之加工(例如切割)後,使黏接著劑層固著殘留於被著物上而從基材剝離。因此,與基材之黏接著劑層接觸之面之表面張力係以在40mN/m以下為佳、以在37mN/m以下更佳、以在35mN/m以下特佳。此等表面張力低之基材可適當選擇材質而得到,此外也可經由將剝離劑塗布於基材之表面並施予剝離處理而得到。
基材之剝離處理所使用之剝離劑可舉例如:醇酸(alkyd)系、聚矽氧(silicone)系、氟系、不飽和聚酯系、聚烯烴系、蠟系者等,特別是醇酸系、聚矽氧系、氟系之剝離劑具有耐熱性,故為較佳。
為了使用上述剝離劑將基材之表面施予剝離處理,可不使用溶劑將剝離劑直接或以溶劑稀釋或乳化後,藉由凹版塗布器、絲棒(Meyer Bar)塗布器、氣刀塗布器、輥塗布器等塗布,並在常溫或是藉由加熱或電子束使其硬化,或者藉由濕積層或乾積層、熱熔融積層、熔融擠壓積層、共擠壓加工等而形成積層體。
基材之膜厚通常為10至500μm(較佳係15至300μm、更佳係20至250μm)左右。
此外,黏接著劑層之厚度通常為1至500μm(較佳係5至300μm、更佳係10至150μm)左右。
本發明之黏接著片係由如上述之基材與黏接著劑組成物而製得。
黏接著片之製造方法無特別限定。可經由在基材上塗布構成黏接著劑層之黏接著劑組成物並乾燥而製造,此外也可經由將黏接著劑層設置於剝離薄膜上後轉印至上述基材而製造。再者,在使用黏接著片前,為了保護黏接著劑層,也可在黏接著劑層之上面預先積層剝離薄膜。此外,於黏接著劑層之表面外圍部,為了固定環形框架(ring frame)等其他器具,也可以其他方法設置壓敏性接著劑層。
根據本發明,也可提供使用上述黏接著片所得之半導體裝置之製造方法。
在本發明之半導體裝置之製造方法中,首先,將本發明之黏接著片藉由環形框架固定於切割裝置上,而將矽晶圓之一面載置於黏接著片之黏接著劑層上,並輕輕按壓,而將晶圓固定。
再者,當黏接著劑組成物含有能量線聚合性化合物(G)時,之後預先從基材側照射能量線至黏接著劑層,而提高黏接著劑層之凝聚力,並降低黏接著劑層與基材之間之接著力。所照射之能量線可使用紫外線(UV)或電子束(EB)等,且以使用紫外線為佳。
接著,使用切割機(dicing saw)等切割手段切割上述之矽晶圓,而得到IC晶片。此時之切割深度係由矽晶圓之厚度與黏接著劑層之厚度之合計、以及加上切割機之磨損部分而得之深度。
再者,能量線照射可在貼合半導體晶圓後、剝離IC晶片前之任一階段進行。例如:可在切割後進行,此外也可在下述之擴大(expand)步驟之後進行。並且也可將能量線照射分成複數次進行。
接著,若依需要而進行黏接著片之擴大,則IC晶片之間隔會擴張,而在黏接著劑層與基材之間發生偏移,因此,黏接著劑層與基材之間之接著力會減少,而可輕易地進行IC晶片之拾取。
若如此操作而進行IC晶片之拾取,即可使切割後之黏接著劑層固著殘留於IC晶片之內面而從基材剝離。
接著,隔介黏接著劑層將IC晶片載置於晶粒墊部。晶粒墊部係在將IC晶片載置前加熱、或在剛載置後立刻加熱。加熱溫度通常為80至200℃,且以100至180℃為佳,加熱時間通常為0.1秒至5分鐘,且以0.5秒至3分鐘為佳,晶片裝載(chip mount)壓力通常為1kPa至200MPa。
將IC晶片載置於晶粒墊部後,依需要也可進一步進行加熱。此時之加熱條件係使加熱溫度在上述加熱溫度之範圍,且加熱時間通常為1至180分鐘(較佳係10至120分鐘)。此加熱也可以樹脂密封之加熱取代。該加熱條件係150至180℃、2至8小時左右。
經過如此之步驟,即可製造半導體裝置。可藉由經過前述步驟而將黏接著劑層硬化,並將IC晶片與晶粒墊部強力接著。此外,由於黏接著劑層係在黏晶條件下流動化,故也充分埋入至晶粒墊部之凹凸中,而可防止空隙產生。
換言之,在所得之安裝品中,由於成為使做為IC晶片之固著手段之黏接著劑硬化且也充分埋入至晶粒墊部之凹凸中的構成,故即使在極嚴苛之條件下,仍可達成充分之封裝可靠性與基板安裝性。
再者,本發明之黏接著劑組成物及黏接著片,除了如上述之使用方法以外,也可使用於半導體化合物、玻璃、陶瓷、金屬等的接著。
以下,藉由實施例說明本發明,但本發明並非受限於此等實施例,再者,在以下之實施例及比較例中,「表面安裝性之評估」係按照下述進行。
於#2000經研磨之矽晶圓(直徑150mm,厚度150μm)之研磨面,藉由貼帶機(tape mounter)(Lintec公司製,Adwill RAD2500)進行實施例及比較例之由黏接著劑層形成於基材上而成之黏接著片的貼合後,固定於晶圓切割用環形框架。
之後,使用紫外線照射裝置(Lintec公司製,Adwill RAD2000)從基材面照射(350mW/cm2
,190mJ/cm2
)紫外線。
接著,使用切割裝置(DISCO股份有限公司製,DFD651),將上述矽晶圓切割成8mm×8mm之晶片大小。在切割時之切入量係設定成切入基材20μm。
使用在銅箔積層板(三菱瓦斯化學股份有限公司製CCL-HL830)之銅箔(18μm厚)形成有電路圖案且在圖案上具有阻焊劑(solder resist)(太陽油墨製PSR4000 AUS5)的基板(股份有限公司Chino技研製)作為基板。
將在上述(1)中得到之黏接著片上之IC晶片與黏接著劑層一同從基材拿起後,隔介黏接著劑層在120℃、100gf、1秒之條件下壓合於基板上。之後,以模型樹脂(京瓷化學股份有限公司製KE-1100AS3)將基板密封成密封厚度達400μm(密封裝置:APIC YAMADA股份有限公司製MPC-06M Trial Press),以175℃、5小時使模型樹脂硬化。
接著,將密封後之基板貼合於切割帶(Lintec公司製,Adwill D-510T),並使用切割裝置(DISCO股份有限公司製,DFD651)切割成12mm×12mm大小,而得到可靠性評估用之半導體封裝。
將所得之半導體封裝放置於85℃、60%RH條件下168小時並使其吸濕後,在進行最高溫度260℃、加熱時間1分鐘之IR回焊(回焊爐:相模理工製WL-15-20DNX型)3次後,藉由掃瞄型超音波檢傷裝置(日立建機FineTech股份有限公司製Hye-Focus)及剖面觀察來評估IC晶片有無從黏接著層凸起‧剝落、封裝破裂有無發生。
將在基板/半導體晶片接合部上觀察到剝離0.5mm以上之情形判定為有剝離,並將25個封裝投入測試後計算未發生剝離之個數。
於#2000經研磨之矽晶圓(將直徑150mm分割成1/4者,厚度150μm)之研磨面,使用積層機(大成Laminator製積層機)以40℃、0.5m/min之速度貼合實施例及比較例之黏接著片。之後,將黏接著片之基材剝離後,使用相同之積層機以80℃、0.5m/min之速度在其上貼合厚度150μm之銅板(10mm×50mm,以甲苯擦拭後在室溫乾燥2小時者)。之後在175℃於空氣中加熱硬化5小時。
測定將製得之樣品在85℃、85%RH下放置168小時之前及之後的接著強度。測定係在23℃、50%RH條件下使用萬能測試機(島津製作所股份有限公司製Autograph AG-IS),在固定晶圓側之狀態下,讀取以角度90度、速度50mm/min剝除銅板所需之力(剝離強度)。求出(1-放置後之剝離強度/放置前之剝離強度)×100(%)做為接著強度之濕熱劣化率。
此外,構成黏接著劑組成物之各成分如下述:
將做為單體之丙烯酸苯甲酯85g及丙烯酸2-羥乙酯15g、做為聚合起始劑之α,α’-偶氮雙異丁腈0.2g、與做為溶劑之甲苯60g及乙酸乙酯60g混合,並在60℃、氮氣環境下攪拌24小時,而得到丙烯酸共聚物(A)-1。此外,(A)-2至(A)-7係除了將丙烯酸共聚物之單體之種類、重量比按照下述變更以外,其餘皆依據與獲得(A)-1時同樣之操作而得到。換言之,使用於得到(A)-2至(A)-7之單體之合計重量皆為100g。
(A)-1:由丙烯酸苯甲酯/丙烯酸2-羥乙酯(85重量%/15重量%)組成之丙烯酸共聚物(重量平均分子量約50萬)
(A)-2:由丙烯酸甲酯/丙烯酸苯甲酯/丙烯酸2-羥乙酯(25重量%/60重量%/15重量%)組成之丙烯酸共聚物(重量平均分子量約50萬)
(A)-3:由丙烯酸甲酯/丙烯酸苯甲酯/丙烯酸2-羥乙酯(45重量%/40重量%/15重量%)組成之丙烯酸共聚物(重量平均分子量約50萬)
(A)-4:由丙烯酸甲酯/丙烯酸苯甲酯/丙烯酸2-羥乙酯(55重量%/30重量%/15重量%)組成之丙烯酸共聚物(重量平均分子量約50萬)
(A)-5:由丙烯酸甲酯/丙烯酸2-羥乙酯(85重量%/15重量%)組成之丙烯酸共聚物(重量平均分子量約50萬)
(A)-6:由丙烯酸苯甲酯/丙烯酸2-羥乙酯(98重量%/2重量%)組成之丙烯酸共聚物(重量平均分子量約50萬)
(A)-7:由丙烯酸甲酯/丙烯酸苯甲酯/丙烯酸2-羥乙酯(70重量%/15重量%/15重量%)組成之丙烯酸共聚物(重量平均分子量約50萬)
(B)環氧系熱硬化性樹脂:雙酚A二環氧丙基醚(Japan Epoxy Resin股份有限公司製Epikote 828,環氧當量189g/eq)
(C)熱硬化劑:酚醛型酚樹脂(昭和高分子股份有限公司製SHONOL BRG-556,酚性羥基當量104g/eq)
(D)硬化促進劑:咪唑(四國化成工業股份有限公司製Curezol 2PHZ)
(E)矽烷耦合劑(三菱化學股份有限公司製MKC Silicate MSEP2)
(F)交聯劑:芳香族性聚異氰酸酯(日本POLYURETHANE工業股份有限公司製CORONATE L)
(G)能量線聚合性化合物:2官能性丙烯酸酯(日本化藥股份有限公司製KAYARADR-684)
(H)光聚合起始劑(Ciba Specialty Chemicals股份有限公司製Irgacure 184)
此外,黏接著片之基材係使用聚乙烯薄膜(厚度100μm,表面張力33mN/m)。
使用記載於表1之組成之黏接著劑組成物。黏接著劑組成物係經由將記載於表1之構成成分混合而得到。表中之數值表示換算成固形分之重量份。
將記載於表1之組成之黏接著劑組成物塗布於經聚矽氧處理之剝離薄膜(Lintec股份有限公司製SP-PET3811(S))上後,以烘箱在100℃乾燥1分鐘。乾燥後所得之黏接著劑層之厚度係30μm。之後,將其與厚度100μm之基材貼合,並將黏接著劑層轉印至基材上,而得到黏接著片。
使用所得之黏接著片,進行表面安裝性、接著強度之濕熱劣化率之評估。結果如表2所示。
*:未發生接合部之凸起‧剝落、封裝破裂的個數/測試投入個數
Claims (3)
- 一種黏接著劑組成物,係含有:含有衍生自(甲基)丙烯酸苯甲酯之構造單元25至95重量%、及衍生自具有羥基之(甲基)丙烯酸酯之構造單元10至30重量%之丙烯酸共聚物(A)、環氧系熱硬化性樹脂(B)、與熱硬化劑(C)。
- 一種黏接著片,其由申請專利範圍第1項之黏接著劑組成物所成之黏接著劑層係以可剝離之方式形成於基材上者。
- 一種半導體裝置之製造方法,係具備下述步驟:於申請專利範圍第2項之黏接著片之黏接著劑層貼合半導體晶圓之步驟;切割該半導體晶圓之步驟;使前述黏接著劑層之至少一部分固著殘留於半導體晶圓,而將切割後之半導體晶圓從該黏接著片之基材剝離之步驟;與隔介固著殘留於該半導體晶圓之黏接著劑層,將剝離之半導體晶圓熱壓合於晶粒墊部上之步驟。
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