TWI596185B - 附突起電極之半導體裝置製造用接著劑片及半導體裝置之製造方法 - Google Patents
附突起電極之半導體裝置製造用接著劑片及半導體裝置之製造方法 Download PDFInfo
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- TWI596185B TWI596185B TW102118777A TW102118777A TWI596185B TW I596185 B TWI596185 B TW I596185B TW 102118777 A TW102118777 A TW 102118777A TW 102118777 A TW102118777 A TW 102118777A TW I596185 B TWI596185 B TW I596185B
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- alkali
- film
- group
- soluble
- adhesive sheet
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
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Description
本發明關於一種附突起電極的半導體裝置製造用黏著劑片及使用其之半導體裝置之製造方法。
近年來隨著半導體裝置的小型化與高密度化,作為將半導體晶片安裝在電路基板的方法,倒裝晶片安裝正受到矚目,並且正在急速普及。在倒裝晶片安裝之中,為了黏著半導體晶片,一般的方法是採用半導體晶片上所形成的突起電極與電路基板的焊墊電極之間隔著環氧樹脂系黏著劑。進一步有文獻提出一種技術,其係藉由使用在柔軟性薄膜上積層了黏著劑薄膜的黏著劑片,不覆蓋突起電極而將黏著劑與半導體晶片貼合之後安裝在電路基板上,而提升了半導體晶片與電路基板的電連接可靠性(參照例如專利文獻1及2)。
專利文獻1 日本特開2005-28734號公報
專利文獻2 日本特開2011-171586號公報
然而,在使用如上述般的黏著劑片將黏著劑與半導體晶片貼合的情況,可使突起電極至某程度露出,然而不可能達到突起電極的上部(突起頂部)不存在黏著劑的狀態。其結果,在安裝後,在半導體晶片的突起電極與電路基板的焊墊電極間會隔著黏著劑,因此難以確保充分的連接可靠性。
鑑於這樣的狀況,本發明目的為提供一種黏著劑片,其係使用黏著劑片將黏著劑與半導體晶片貼合的情況,不會對突起電極造成損傷,可達成在突起頂部上不存在黏著劑的狀態,可製造出在倒裝晶片安裝後半導體晶片的突起電極與電路基板的焊墊電極間的連接可靠性優異的半導體裝置。
亦即本發明為一種附突起電極的半導體裝置製造用黏著劑片,其係在軟質薄膜上形成鹼可溶性黏著劑薄膜。
另外,本發明含有一種半導體裝置之製造方法,其係依序包括:將請求項1至7之任一者所記載之附突起電極的半導體裝置製造用黏著劑片的鹼可溶性黏著劑薄膜側的一面貼合在具有突起電極的第一電路構件的突起電極面之步驟;僅使該黏著劑片的鹼可溶性黏著
劑薄膜殘留在前述電路構件上,將該黏著劑片中所含有的其他薄膜剝離之步驟;以鹼水溶液蝕刻該鹼可溶性黏著劑薄膜,除去突起電極上的該黏著劑之步驟;及藉由加熱加壓使前述第一電路構件與具有焊墊電極的第二電路構件電連接之步驟。
使用本發明之黏著劑片將黏著劑與半導體晶片貼合的情況,能夠不對突起電極造成損傷而使突起電極露出。然後進一步藉由使用鹼水溶液對突起頂部上的黏著劑實施濕式蝕刻,可達成在突起頂部上不存在黏著劑的狀態,可製造出倒裝晶片安裝後半導體晶片與電路基板的連接可靠性優異的半導體裝置。
100‧‧‧附突起電極的電路構件
101‧‧‧銅支柱
102‧‧‧焊錫突起
103‧‧‧鹼可溶性黏著劑薄膜
104‧‧‧軟質薄膜
105‧‧‧殘存於突起頂部上的鹼可溶性黏著劑
第1圖(a)~(d)表示使用本發明之附突起電極的半導體裝置製造用黏著劑片,在附突起電極的電路構件形成黏著劑被膜的程序的一例之模式圖。
本發明之附突起電極的半導體裝置製造用黏著劑片,其係在軟質薄膜上形成有鹼可溶性黏著劑薄膜。
本發明之黏著劑片可使用於製造附突起電極的半導體裝置。本發明中所述的半導體裝置,是指所有可藉由利用半導體元件的特性來發揮機能的裝置。將半導體元件連接在基板的物品、或使半導體元件彼此或基板彼此連接的物品、光電裝置、半導體電路基板、及含
有該等的電子零件,全部包括在半導體裝置。本發明之黏著劑片,適合使用作為該等的半導體裝置所使用的構件彼此的黏著或固定、或用來密封半導體元件等的半導體用黏著劑。
使用第1圖來說明本發明之黏著劑片之使用方法的一例。首先準備附突起電極的電路構件100(第1圖(a))。此處,電路構件是指在矽基板等的半導體基板、化合物半導體基板、有機系電路基板、無機系電路基板等的基板配置有電路的構件。矽基板亦可採用半導體晶片。有機系電路基板的例子可列舉玻璃布.環氧敷銅積層板等的玻璃基材敷銅積層板;玻璃不織布.環氧敷銅積層板等的複合敷銅積層板;聚醚醯亞胺樹脂基板、聚醚酮樹脂基板、聚碸系樹脂基板等的耐熱.熱塑性基板;聚酯敷銅薄膜基板;聚醯亞胺敷銅薄膜基板等的可撓基板。無機系電路基板可列舉例如氧化鋁基板、氮化鋁基板、碳化矽基板等的陶瓷基板;鋁基材基板、鐵基材基板等的金屬系基板。電路的構成材料的例子,可列舉含有銀、金、銅等的金屬的導體、含有無機系氧化物等的電阻體、包含玻璃系材料及/或樹脂等的低介電體、含有樹脂或高介電率無機粒子等的高介電體、含有玻璃系材料等的絕緣體等。
附突起電極的電路構件係在該等的基板上形成有突起電極。突起電極的材質可列舉銀、金、銅、焊錫等。由於必須使突起電極與其他電路構件的焊墊電極電連接,因此突起電極的材質係以焊錫為佳。進一步為
了對應於窄節距的突起,焊錫突起宜為形成在金屬的支柱,尤其是在銅支柱上。在第1圖(a)所示的附突起電極的電路構件100之中,在銅支柱上101形成焊錫突起102。
接下來,使前述附突起電極的電路構件之突起電極側的面與本發明之黏著劑片的鹼可溶性黏著劑薄膜側的面成為對向,並藉由熱壓接使其貼合(第1圖(b))。此時,鹼可溶性黏著劑薄膜103的支持體為軟質薄膜104,如第1圖(b)所示般,藉此能夠不對突起電極造成損傷或變形而使突起露出。此處,突起露出,是指貼合後的鹼可溶性黏著劑薄膜厚度低於突起電極的高度的狀態。
接下來,藉由將軟質薄膜104剝離,僅使鹼可溶性黏著劑薄膜103殘留在附突起電極的電路構件上,而得到形成有鹼可溶性黏著劑被膜之附突起電極的電路構件(第1圖(c))。如第1圖(c)所示般,突起電極的上部(突起頂部)會露出,亦即,突起頂部露出於鹼可溶性黏著劑被膜之上,而在突起頂部上附著有少量鹼可溶性黏著劑105。
接下來,藉由蝕刻除去突起頂部上的鹼可溶性黏著劑,而達成在突起頂部上不存在鹼可溶性黏著劑的狀態(第1圖(d))。鹼可溶性黏著劑之蝕刻可藉由使用鹼水溶液的濕式蝕刻來進行。
接下來針對本發明之黏著劑片的材料作說明。本發明之黏著劑片是在軟質薄膜上形成鹼可溶性黏著劑薄膜而成。
軟質薄膜是作為鹼可溶性黏著劑薄膜的支持體的薄膜。軟質薄膜係以在40~80℃時具有1~300MPa的拉伸彈性率為佳。這種軟質薄膜,可採用聚乙烯(PE)薄膜、乙烯醋酸乙烯酯共聚物(EVA)薄膜、聚氯乙烯薄膜、聚乙烯甲基丙烯酸酯薄膜、聚乙烯甲基丙烯酸甲酯薄膜、聚胺甲酸酯薄膜、聚四氟乙烯薄膜、聚乙烯縮醛薄膜等。該等可單獨使用或可併用2種以上。上述軟質薄膜之中,從與鹼可溶性黏著劑薄膜的密著性良好以及將黏著劑片貼合在基材之後的剝離性良好的觀點而言,以PE薄膜或EVA薄膜為佳。
軟質薄膜厚度,並未受到特別限定,而從抑制突起電極的損傷的觀點而言,以5μm以上為佳,更佳為10μm以上。另外,從將鹼可溶性黏著劑由突起電極上排除,容易進行鹼蝕刻的觀點而言,軟質薄膜厚度係以200μm以下為佳,更佳為150μm以下。
鹼可溶性黏著劑薄膜是形成在上述軟質薄膜上。鹼可溶性黏著劑薄膜與軟質薄膜只要相接即可,亦可進一步積層其他薄膜。所以,鹼可溶性黏著劑薄膜的支持體薄膜可單獨為軟質薄膜,或可積層有軟質薄膜與不同種類的薄膜。從製成黏著劑片之後的使用便利性而言,支持體薄膜係以積層有軟質薄膜與硬質薄膜的薄膜為佳。從可抑制使用軟質薄膜的黏著劑片因為加熱或冷卻而產生的黏著劑片的彎曲的觀點而言,更佳為依照軟質薄膜/硬質薄膜/軟質薄膜的順序積層的薄膜。硬質薄膜可採用聚對苯二甲酸乙二酯(PET)薄膜、聚丙烯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜等。
在本發明中,鹼可溶性黏著劑薄膜為鹼可溶性,是指將該薄膜在氫氧化四甲銨的2.38%水溶液中以23℃浸漬10分鐘時,該薄膜的膜厚度會減少0.1μm以上。
從可容易地蝕刻突起頂部上的樹脂,且倒裝晶片安裝後的連接電阻值不易上昇的觀點而言,鹼可溶性黏著劑薄膜的鹼可溶性,係以對23℃的氫氧化四甲銨2.38%水溶液的蝕刻速率為0.5μm/分鐘以上為佳,1.0μm/分鐘以上為更佳。另外,從容易控制欲使黏著劑殘留的部分的蝕刻量的觀點而言,蝕刻速率係以100μm/分鐘以下為佳,50μm/分鐘以下為更佳,10μm/分鐘以下為最佳。鹼可溶性黏著劑薄膜的鹼可溶性,可藉由構成後述鹼可溶性黏著劑薄膜的各成分的種類及含有比率來調整。
鹼可溶性黏著劑薄膜厚度並未受到特別限定,而從可保持使用黏著劑片所製作出的半導體裝置的黏著強度,連接可靠性提升的觀點而言,以5μm以上為佳。另外,在製作鹼可溶性黏著劑薄膜時,可良好地進行溶劑的乾燥,能夠抑制在半導體安裝後殘留的溶劑造成的孔隙,半導體裝置的連接可靠性提升的觀點而言,鹼可溶性黏著劑薄膜的厚度係以100μm以下為佳。
鹼可溶性黏著劑薄膜係以含有(A)鹼可溶性樹脂、(B)環氧化合物、(C)硬化加速劑及(D)無機粒子為佳。
(A)鹼可溶性樹脂,是指對於100g氫氧化四甲銨的2.38%水溶液,在25℃下溶解0.1g以上的樹脂。為了容易利用鹼水溶液進行蝕刻,(A)鹼可溶性樹脂係以具有鹼可溶性的官能基為佳。鹼可溶性的官能基是指具有酸性的官能基,具體而言可列舉酚性羥基、羧基、磺酸基及巰基等。從鹼可溶性黏著劑薄膜之保存安定性、或對導體的銅配線、鋁配線、焊錫突起的腐蝕等的問題而言,鹼可溶性基係以酚性羥基為佳。
上述鹼可溶性樹脂只要是鹼可溶性,則不受特別限定,可列舉例如聚醯亞胺樹脂、聚醯胺樹脂、苯氧基樹脂、聚碸樹脂、聚苯硫醚樹脂、聚酯樹脂、聚醚酮樹脂、聚醚樹脂、(甲基)丙烯酸共聚物等。該等可單獨使用或組合兩種以上來使用。從耐熱性良好,且維持作為黏著劑之良好連接的可靠性優異的觀點而言,上述之中,以鹼可溶性聚醯亞胺為佳。
在聚醯亞胺導入鹼可溶性的官能基,可藉由使二胺、四羧酸二酐、或末端密封劑具有鹼可溶性基來進行。此外,在聚醯亞胺的醯亞胺化率未滿100%的情況下,來自四羧酸二酐的羧基會殘留,而此羧基不包括在此處所謂的鹼可溶性基。
在本發明中適合使用的鹼可溶性聚醯亞胺係具有下述通式(1)所表示之結構單元,且在主鏈的至少一個末端具有下述通式(2)及/或(3)所表示之結構。
上述通式(1)~(3)中,R1表示4~14價的有機基,R2表示2~12價的有機基。R3及R4可相同或可為相異者混合,表示選自包含羧基、酚性羥基、磺酸基及巰基之群組中的至少一個基團。R3及R4係以酚性羥基為最佳。α及β各自獨立地表示0~10之整數。從鹼溶解性提升的觀點而言,以α及β之任一者係1~10之整數為佳,2~10之整數為更佳。Y表示具有至少一個選自包含羧基、酚性羥基、磺酸基及巰基之群組中的基團之1價的有機基。Z表示具有至少一個選自包含羧基、酚性羥基、磺酸基及巰基之群組中的基團之2價的有機基。Y及Z所含有的基團係以酚性羥基為最佳。Y及Z之碳數係以3~20為佳。
鹼可溶性聚醯亞胺的重量平均分子量係以10,000以上100,000以下為較佳。在含有2種以上可溶性聚醯亞胺的情況,只要其中至少1種的重量平均分子量在上述範圍即可。若重量平均分子量在10,000以上,則硬化膜的機械強度提升,熱循環測試時的裂縫發生等會受到抑制,可得到高可靠性。另一方面,若重量平均分子量在100,000以下,則後述的(B)環氧化合物、(C)硬化加速劑之相溶性提升。進一步從蝕刻性提升的觀點而言,50,000以下為較佳。此外,本發明中的重量平均分子量是藉由凝膠滲透層析法(GPC法)來測定,以聚苯乙烯換算來作計算。
鹼可溶性聚醯亞胺,可藉由四羧酸二酐與二胺的反應而得到。在通式(1)之中,R1為四羧酸二酐之殘基。R1係以含有芳香族基或環狀脂肪族基的碳原子數8~40之有機基為佳。
四羧酸二酐具體而言,可列舉焦蜜石酸二酐、3,3',4,4'-聯苯四羧酸二酐、2,3,3',4'-聯苯四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、3,3',4,4'-二苯基酮四羧酸二酐、2,2',3,3'-二苯基酮四羧酸二酐、2,2-雙(3,4-二羧苯基)丙烷二酐、2,2-雙(2,3-二羧苯基)丙烷二酐、1,1-雙(3,4-二羧苯基)乙烷二酐、1,1-雙(2,3-二羧苯基)乙烷二酐、雙(3,4-二羧苯基)甲烷二酐、雙(2,3-二羧苯基)甲烷二酐、雙(3,4-二羧苯基)碸二酐、雙(3,4-二羧苯基)醚二酐、1,2,5,6-萘四羧酸二酐、9,9-雙(3,4-二羧苯基)茀酸二酐、9,9-雙{4-(3,4-二羧苯氧基)苯基}茀酸二酐、2,3,6,7-
萘四羧酸二酐、2,3,5,6-吡啶四羧酸二酐、3,4,9,10-苝四羧酸二酐、2,2-雙(3,4-二羧苯基)六氟丙烷二酐等的芳香族四羧酸二酐、或丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐等的脂肪族之四羧酸二酐、及以下所示結構的酸二酐等。該等可單獨或組合兩種以上來使用。
此處,R5表示選自氧原子、C(CF3)2、C(CH3)2、CO、COO及SO2的基團。R6及R7可相同或可為相異者混合,表示選自氫原子、羥基及巰基的基團。
在通式(1)之中,R2為二胺之殘基。R2係以含有芳香族基或環狀脂肪族基之碳原子數5~40之有機基為佳。
二胺的具體的例子,可列舉3,3'-二胺基二苯基醚、3,4'-二胺基二苯基醚、4,4'-二胺基二苯基醚、3,3'-二胺基二苯基甲烷、3,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基甲烷、3,3'-二胺基二苯基碸、3,4'-二胺基二苯基碸、4,4'-二胺基二苯基碸、3,4'-二胺基二苯基硫醚、4,4'-二胺基二苯硫醚、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、聯苯胺、間苯二胺、對苯二胺、1,5-萘二胺、2,6-萘二胺、雙(4-胺基苯氧基苯基)碸、雙(3-胺基苯氧基苯基)碸、雙(4-胺基苯氧基)聯苯、雙{4-(4-胺基苯氧基)苯基}醚、1,4-雙(4-
胺基苯氧基)苯、2,2'-二甲基-4,4'-二胺基聯苯、2,2'-二乙基-4,4'-二胺基聯苯、3,3'-二甲基-4,4'-二胺基聯苯、3,3'-二乙基-4,4'-二胺基聯苯、2,2',3,3'-四甲基-4,4'-二胺基聯苯、3,3',4,4'-四甲基-4,4'-二胺基聯苯、2,2'-二(三氟甲基)-4,4'-二胺基聯苯、9,9-雙(4-胺基苯基)茀或在該等的芳香族環以烷基或鹵素原子取代而成的化合物、或脂肪族的環己基二胺、亞甲基雙環己基胺及以下所示構造的二胺等。該等可單獨或組合兩種以上來使用。
此處,R8表示選自氧原子、C(CF3)2、C(CH3)2、CO、COO及SO2的基團。R9~R12可相同或可為相異者混合,表示選自羥基及巰基的基團。
該等之中,3,3'-二胺基二苯基醚、3,4'-二胺基二苯基醚、4,4'-二胺基二苯基醚、3,3'-二胺基二苯基甲烷、3,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基甲烷、3,3'-二胺基二苯基碸、3,4'-二胺基二苯基碸、4,4'-二胺基二苯基碸、3,4'-二胺基二苯基硫醚、4,4'-二胺基二苯
基硫醚、間苯二胺、對苯二胺、1,4-雙(4-胺基苯氧基)苯、9,9-雙(4-胺基苯基)茀及以下所示結構之二胺等為佳。
此處,R8表示選自氧原子、C(CF3)2、C(CH3)2及SO2之基團。R9~R12可相同或可為相異者混合,表示選自羥基及巰基之基團。
進一步而言,為了提升與基板的黏著性,亦可在不使耐熱性降低的範圍,與具有矽氧烷結構的二胺共聚合。具體而言,可列舉使雙(3-胺丙基)四甲基二矽氧烷、雙(對胺苯基)八甲基五矽氧烷等1~10莫耳%進行共聚合等。
鹼可溶性聚醯亞胺的至少一部分主鏈末端係以一級單胺或二羧酸酐密封。藉由此末端密封劑,可將鹼可溶性聚醯亞胺的重量平均分子量調整在適當的範圍。進一步從鹼可溶性提升的觀點而言,末端密封劑係以具有鹼可溶性基為佳。
在通式(2)之中,Y為末端密封劑的一級單胺之殘基。關於末端密封劑的具體的例子,一級單胺宜為5-胺基-8-羥基喹啉、1-羥基-7-胺基萘、1-羥基-6-胺基
萘、1-羥基-5-胺基萘、1-羥基-4-胺基萘、2-羥基-7-胺基萘、2-羥基-6-胺基萘、2-羥基-5-胺基萘、1-羧基-7-胺基萘、1-羧基-6-胺基萘、1-羧基-5-胺基萘、2-羧基-7-胺基萘、2-羧基-6-胺基萘、2-羧基-5-胺基萘、2-胺基安息香酸、3-胺基安息香酸、4-胺基安息香酸、4-胺基水楊酸、5-胺基水楊酸、6-胺基水楊酸、2-胺基苯磺酸、3-胺基苯磺酸、4-胺基苯磺酸、3-胺基-4,6-二羥基嘧啶、2-胺基酚、3-胺基酚、4-胺基酚、2-胺基硫酚、3-胺基硫酚、4-胺基硫酚等。
另外,在通式(3)之中,Z為末端密封劑的二羧酸酐之殘基。二羧酸酐的具體例,以4-羧基酞酸酐、3-羥基酞酸酐、順-烏頭酸酐等為佳。該等可單獨或組合兩種以上來使用。
鹼可溶性聚醯亞胺,可藉由將二胺的一部分取代為末端密封劑的一級單胺,或將四羧酸二酐取代為末端密封劑的二羧酸酐,以周知的方法來合成。例如在低溫中使四羧酸二酐、二胺化合物與單胺反應之方法;在低溫中使四羧酸二酐與二羧酸酐與二胺化合物反應之方法;利用藉由四羧酸二酐與醇得到二酯,然後在二胺、單胺與縮合劑的存在下使其反應等的方法,得到聚醯亞胺前驅物。然後利用周知的醯亞胺化反應法,可合成出聚醯亞胺。
鹼可溶性聚醯亞胺亦可僅包含通式(1)所表示之結構單元,或可為與其他結構單元的共聚物。此時,所含有的通式(1)所表示之結構單元係以聚醯亞胺全體
的50mol%以上為佳,含有70mol%以上為較佳。共聚合或混合所使用的結構單元的種類及量,係以在不會損及因為最終加熱處理而得到的聚醯亞胺的耐熱性的範圍作選擇為佳。
另外,鹼可溶性聚醯亞胺的醯亞胺化率可藉由例如以下的方法輕易地求得。此處,醯亞胺化率,如前述般,意指在經過聚醯亞胺前驅物而合成出聚醯亞胺時,聚醯亞胺前驅物之中,幾莫耳%轉換為聚醯亞胺。首先,測定聚合物的紅外線吸收光譜,並確認聚醯亞胺所產生的醯亞胺結構的吸收峰(1780cm-1附近、1377cm-1附近)的存在。接下來,對此聚合物在350℃下熱處理1小時之後,再度測定紅外線吸收光譜,比較熱處理前與熱處理後的1377cm-1附近的峰強度。將熱處理後的聚合物的醯亞胺化率定為100%,而求得熱處理前的聚合物的醯亞胺化率。聚合物的醯亞胺化率係以90%以上為佳。
鹼可溶性聚醯亞胺中所導入的末端密封劑,可藉由以下的方法來偵測。例如使導入了末端密封劑的聚醯亞胺溶於酸性溶液,分解成聚醯亞胺之構成單元的胺成分與羧酸酐成分,使用氣相層析(GC)、或NMR來對其作測定。此外亦可直接對導入了末端密封劑的聚醯亞胺使用熱分解氣相層析(PGC)、紅外線光譜法、13CNMR等作測定。
從鹼蝕刻性的觀點而言,鹼可溶性樹脂的含量係以相對於除去溶劑及無機粒子的鹼可溶性黏著劑薄膜的有機物總量而言的10重量%以上為佳。宜為20重
量%以上50重量%以下。藉由在此範圍使用,鹼可溶性黏著劑薄膜的鹼蝕刻性優異,並且所得到的硬化膜的耐化學性、耐熱性、耐濕性等的特性提升。
(B)環氧化合物可使用液狀環氧化合物或固態環氧化合物。此處液狀環氧化合物,在25℃時會呈現150Pa.s以下的黏度。固態環氧化合物,在25℃時會呈現超過150Pa.s的黏度。液狀環氧化合物可列舉例如JER828、JER1750、JER152、JER630、YL980(以上為商品名,三菱化學股份有限公司製)、EPICLON HP-4032(以上為商品名,DIC股份有限公司製)、EP-4000S、EP-4000L、EP-4003S、EP-4010S(以上為商品名,ADEKA股份有限公司製)等,然而不受該等所限定。亦可將該等2種以上組合。另外,固態環氧化合物可列舉JER1002、JER1001、YX4000H、JER4004P、JER5050、JER154、JER157S70、JER180S70、YX4000H(以上為商品名,三菱化學股份有限公司製)、TEPIC S、TEPIC G、TEPIC P(以上為商品名,日產化學工業股份有限公司製)、EPOTORT YH-434L(商品名,新日鐵化學股份有限公司製)、EPPN502H、NC3000(以上為商品名,日本化藥股份有限公司製)、EPICLON N695、EPICLON HP-7200(以上為商品名,DIC股份有限公司製)等,然而不受該等所限定。亦可將該等2種以上組合。
從黏著強度的觀點而言,(B)環氧化合物的含量係以相對於除去溶劑及無機粒子的鹼可溶性黏著劑薄膜的有機物總量而言的20重量%以上為佳,從將薄膜貼
附在基材時提升熱時流動性的觀點而言,以30重量%以上為較佳。硬化後的耐迴焊性、在高溫條件下的絕緣可靠性的觀點而言,含量係以80重量%以下為佳。
鹼可溶性黏著劑薄膜係以含有(C)硬化加速劑為佳。進一步從硬化加速劑並未溶解而存在於鹼可溶性黏著劑薄膜中,環氧化合物的硬化反應變慢,在室溫下的保存性提升的觀點而言,(C)硬化加速劑係以硬化加速劑粒子為佳。
硬化加速劑粒子可採用不會溶於鹼可溶性黏著劑薄膜中所含有的各成分的物質。另外,若硬化加速劑粒子採用咪唑系硬化加速劑粒子,則產生在該粒子表面(D)無機粒子藉由交互作用而配位的結構,藉此可得到保存性優異的黏著劑薄膜,故為適合。這種硬化加速劑粒子適合採用Curezol 2PZCNS、Curezol 2PZCNS-PW、Curezol C11Z-CNS、Curezol 2MZ-A、Curezol C11-A、Curezol 2E4MZ-A、Curezol 2MZA-PW、Curezol 2MAOK-PW、Curezol 2PHZ-PW(以上為商品名,四國化成工業股份有限公司製)等。
另外,若使用微膠囊型硬化加速劑粒子,則可進一步提高保存性。微膠囊型硬化加速劑粒子適合採用對胺加成物型硬化加速劑實施異氰酸酯處理的微膠囊型硬化加速劑粒子等。
微膠囊型硬化加速劑粒子,係以採用微膠囊型硬化加速劑粒子在分散於液狀環氧化合物的狀態下存在為佳。這種微膠囊型硬化加速劑粒子在分散於液狀環
氧化合物的狀態的物品,可列舉Novacure HX-3941HP、Novacure HXA3922HP、Novacure HXA3932HP、Novacure HXA3042HP(以上為商品名,旭化成E-materials股份有限公司製)等。此情況下微膠囊型硬化加速劑粒子與液狀環氧樹脂的重量比,液狀環氧化合物相對於微膠囊型硬化加速劑粒子100重量份係以100重量份以上500重量份以下為佳。例如在Novacure(商品名,旭化成E-materials股份有限公司製)系列之中,相對於微膠囊型硬化加速劑粒子100重量份含有液狀環氧化合物200重量份。所以,在微膠囊型硬化加速劑粒子採用Novacure(商品名,旭化成E-materials股份有限公司製)系列的情況,鹼可溶性黏著劑薄膜中的(B)環氧化合物一併含有Novacure系列所含有的液狀環氧化合物。然後,由Novacure系列全體的重量減去其中所含有的液狀環氧化合物的重量的值,為硬化加速劑粒子的量。
硬化加速劑粒子的平均粒徑係以0.5μm~5μm為佳。此處平均粒徑,是表示硬化加速劑粒子單獨存在的情況下的粒徑,且表示頻率最高的粒徑。硬化加速劑粒子的形狀為球狀的情況是表示其直徑,橢圓狀及扁平狀的情況是表示形狀最大長度。此外,在形狀為棒狀或纖維狀的情況是表示長邊方向的最大長度。另外,在微膠囊型硬化加速劑粒子的情況,是包括膠囊的厚度的粒徑。
另外,在適合使用的硬化加速劑粒子中亦可併用其他硬化加速劑。該等具體而言可列舉胺系硬化加
速劑、膦系硬化加速劑、鏻系硬化加速劑、鋶系硬化加速劑、錪鎓系硬化加速劑等。
硬化加速劑的適當含量,係相對於除去溶劑及無機粒子的鹼可溶性黏著劑薄膜的有機物總量而言的0.1重量%上20重量%以下。藉由將硬化加速劑的含量定在此範圍,可將鹼可溶性黏著劑薄膜長期保存在室溫下,且可使鹼可溶性黏著劑薄膜的硬化充分進行。另外,藉由將硬化加速劑的含量定在此範圍,後述無機粒子與硬化加速劑能夠充分混合,硬化均勻地發生,使用此鹼可溶性黏著劑薄膜所製作出的半導體裝置的連接可靠性變高。硬化溫度、時間為例如160℃至200℃的溫度及5秒鐘至20分鐘,然而並不受此限制。
鹼可溶性黏著劑薄膜係以含有(D)無機粒子為佳。藉由含有無機粒子,將鹼可溶性黏著劑薄膜加熱硬化時,可將鹼可溶性黏著劑薄膜的熔融黏度調整至不會發泡的程度。再者,無機粒子的分子大小與有機化合物相比為較大,因此在使用本發明之黏著劑片,使突起電極露出時(參照第1圖(b)),會有無機粒子比有機化合物更優先由突起電極物理性地除去的傾向。就結果而言,殘留在突起頂部上的黏著劑殘渣與其他部分的黏著劑相比,鹼可溶性樹脂的含量較高,在以鹼水溶液進行蝕刻時可將突起頂部上的殘渣輕易地除去。
(D)無機粒子可列舉例如滑石、煅燒黏土、未煅燒黏土、雲母、玻璃等的矽酸鹽,氧化鈦、氧化鋁、二氧化矽等的氧化物,碳酸鈣、碳酸鎂等的碳酸鹽,氫
氧化鋁、氫氧化鎂、氫氧化鈣等的氫氧化物,硫酸鋇、硫酸鈣、亞硫酸鈣等的硫酸鹽或亞硫酸鹽,硼酸鋅、偏硼酸鋇、硼酸鋁、硼酸鈣、硼酸鈉等的硼酸鹽,氮化鋁、氮化硼、氮化矽等的氮化物等。該等的無機粒子可含有多種,然而從可靠性及成本的觀點而言,以二氧化矽或氧化鈦為佳。為了改善分散性及沉降性,該等無機粒子係以藉由矽烷偶合劑等實施表面處理為更佳。矽烷偶合劑只要是與鹼可溶性黏著劑薄膜的樹脂成分的相溶性良好的物質即可。宜為乙烯基系、甲基丙烯酸系、丙烯酸系、環氧系或胺基系矽烷偶合劑,從使鹼可溶性黏著劑薄膜加熱硬化時,樹脂與無機粒子發生共價結合的觀點而言,以乙烯基系、甲基丙烯酸系、丙烯酸系或環氧系矽烷偶合劑為更佳。
(D)無機粒子的含量,係以相對於除去溶劑及無機粒子的鹼可溶性黏著劑薄膜的有機物總量100重量份含40重量份以上為佳,100重量份以上為較佳。若(D)無機粒子的該含量在40重量份以上,則在將鹼可溶性黏著劑薄膜加熱硬化時,發泡會受到抑制,伴隨於此,使用此鹼可溶性黏著劑薄膜,所製作出的半導體裝置的連接可靠性提升。特別是在進行如吸濕迴焊處理及熱循環處理般,需要較高耐久性的處理的情況中,能夠保持連接可靠性。另外,若(D)無機粒子之該含量為100重量份以上,則將鹼可溶性黏著劑薄膜加熱硬化之後,線膨脹係數會降低,半導體裝置的連接可靠性更優異。另外,從提升鹼可溶性黏著劑薄膜中的無機粒子的分散性,無
機粒子彼此的凝集受到抑制,使用此鹼可溶性黏著劑薄膜所製作出的半導體裝置的連接可靠性提升的觀點而言,(D)無機粒子之該含量係以400重量份以下為佳。
另外,藉由使用(D)無機粒子的含量為40~100重量份的鹼可溶性黏著劑薄膜,以安裝裝置的真空吸附筒夾來運送附鹼可溶性黏著劑薄膜的半導體晶片時,吸附痕跡不會殘留在鹼可溶性黏著劑薄膜表面。進一步可抑制在將半導體晶片安裝在電路基板時鹼可溶性黏著劑薄膜在晶片側面昇起。藉此,即使因為半導體晶圓的背面研磨等,半導體晶片的厚度成為100μm以下的情況,鹼可溶性黏著劑薄膜也不會附著在半導體晶片背面及安裝裝置的加熱工具,而能夠進行安裝。
(D)無機粒子的形狀可為球狀、破碎狀、碎片狀等的非球狀之任一者,但從在鹼可溶性黏著劑薄膜中容易均勻分散的觀點而言,適合使用球狀無機粒子。另外,球狀無機粒子的平均粒徑係以10nm~3μm為佳,10nm~1μm為較佳。該平均粒徑只要在10nm~3μm,則分散性十分優異,因此能夠以較高濃度填充在鹼可溶性黏著劑薄膜中。因此,在硬化加速劑粒子表面的無機粒子的配位數夠高,保存性提升效果更優異。
另外,在鹼可溶性黏著劑薄膜需要具有透明性的情況,(D)無機粒子的粒徑係以100nm以下為佳,以60nm以下為較佳。例如在基板上形成鹼可溶性黏著劑薄膜之後,為了校準等目的,必須透過鹼可溶性黏著劑薄膜來辨認基板面的標記的情況等。
此外,無機粒子的平均粒徑,在無機粒子單獨存在的情況是表示粒徑,且表示頻率最高的粒徑。形狀為球狀的情況是表示其直徑,橢圓狀及扁平狀的情況是表示形狀的最大長度。此外,在棒狀或纖維狀的情況,是表示長邊方向的最大長度。測定鹼可溶性黏著劑薄膜中的無機粒子的平均粒徑之方法,可藉由使用SEM(掃描式電子顯微鏡)直接對粒子進行觀察,計算出100個粒子的平均粒徑的方法來作測定。
進一步而言,鹼可溶性黏著劑薄膜亦可因應需要含有熱塑性樹脂、有機粒子、交聯促進劑、離子清除劑、抗氧化劑、著色劑、溶解調整劑、界面活性劑、消泡劑等。另外,為了提高與矽晶圓等的基材基板的黏著性,還可含有矽烷偶合劑、鈦螯合劑等。
接下來針對製作本發明之黏著劑片之方法作說明。首先,在作為支持體的軟質薄膜上塗布含有可形成鹼可溶性黏著劑薄膜的成分的鹼可溶性黏著劑組成物(清漆),接下來依照必要使其乾燥,藉此可得到在軟質薄膜上形成有鹼可溶性黏著劑薄膜的黏著劑片。此程序之中,在軟質薄膜因為加熱而發生收縮或延伸等的變形,造成清漆難以塗布的情況,首先將清漆塗布在具有剝離性的聚對苯二甲酸乙二酯(PET)薄膜等的薄膜上,形成鹼可溶性黏著劑薄膜之後,藉由加熱積層將所得到的鹼可溶性黏著劑薄膜轉印在軟質薄膜上,藉此亦可在軟質薄膜上形成鹼可溶性黏著劑薄膜。鹼可溶性黏著劑組成物,可藉由在形成鹼可溶性黏著劑薄膜的成分中添加
有機溶劑而得到。此處所使用的有機溶劑,只要可使形成鹼可溶黏著劑薄膜的成分溶解即可。
有機溶劑具體而言,可列舉乙二醇單甲醚、乙二醇單乙醚、丙二醇單甲醚、丙二醇單乙醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚等的醚類;乙二醇單乙醚醋酸酯、丙二醇單甲醚醋酸酯、丙基醋酸酯、丁基醋酸酯、異丁基醋酸酯、3-甲氧基丁基醋酸酯、3-甲基-3-甲氧基丁基醋酸酯、乳酸甲酯、乳酸乙酯、乳酸丁酯等的酯類;丙酮、甲基乙基酮、乙醯丙酮、甲基丙基酮、甲基丁基酮、甲基異丁基酮、環戊酮、2-庚酮等的酮類;丁醇、異丁醇、戊醇、4-甲基-2-戊醇、3-甲基-2-丁醇、3-甲基-3-甲氧基丁醇、二丙酮醇等的醇類;甲苯、二甲苯等的芳香族烴類;此外還有N-甲基-2-吡咯啶酮、N-環己基-2-吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲亞碸、γ-丁內酯等。
將鹼可溶性黏著劑組成物塗布在軟質薄膜之方法,可列舉使用旋轉檯的旋轉塗布、噴霧塗布、輥塗、網版印刷、刮刀式塗布機、模塗布機、軋輥塗布機、液面彎曲式塗布機(meniscus coater)、棒式塗布機、輥式塗布機、逗點輥塗式塗布機(comma roll coater)、凹版塗布機、網版塗布機、狹縫式模塗布機等。另外,塗布膜厚會依照塗布手段、組成物之固體成分濃度、黏度等而有所不同,而通常乾燥後的膜厚係以0.5μm以上100μm以下為佳。
另外,在塗布鹼可溶性黏著劑組成物之前,亦可使用濾紙或濾膜進行過濾。過濾方法不受特別限定,而以藉由使用保留粒徑為0.4μm~10μm的濾膜並且加壓過濾來進行過濾的方法為佳。
乾燥可使用烘箱、熱板、紅外線等。乾燥溫度及乾燥時間只要在可使有機溶劑揮發的範圍即可,以適當地設定在鹼可溶性黏著劑薄膜未硬化或半硬化狀態的範圍為佳。具體而言,在40℃至120℃的範圍進行1分鐘至數十分鐘為佳。另外還可將這些溫度組合,階段性地昇溫,例如可在70℃、80℃、90℃下進行熱處理各1分鐘。
另外,為了保護本發明之黏著劑片的表面,在鹼可溶性黏著劑薄膜上亦可具有保護薄膜。藉此可保護鹼可溶性黏著劑薄膜表面而不接觸到大氣中的廢屑或塵埃等的污染物質。
保護薄膜可列舉聚酯薄膜等。保護薄膜係以與鹼可溶性黏著劑薄膜的黏著力小者為佳。
接下來針對使用本發明之黏著劑片的半導體裝置之製造方法作說明。另外,近年來有文獻提出各種構造的半導體裝置,本發明之黏著劑片的用途並不受以下所限定。
本發明之半導體裝置之製造方法,依序包括(1)將本發明之黏著劑片的鹼可溶性黏著劑薄膜側的一面貼合在具有突起電極的第一電路構件的突起電極面之步驟;(2)僅使該黏著劑片的鹼可溶性黏著劑薄膜殘留在
前述電路構件上,將該黏著劑片中所含有的其他薄膜剝離之步驟;(3)以鹼水溶液蝕刻該鹼可溶性黏著劑薄膜,除去突起電極上的黏著劑之步驟;(4)藉由加熱加壓使前述第一電路構件與具有焊墊電極的第二電路構件電連接之步驟。
首先準備具有突起電極的第一電路構件與具有焊墊電極的第二電路構件。突起電極及電路構件的形狀及材質如先前所述。焊墊電極是設置於與第一電路構件的突起電極對應的位置,而設置於第二電路構件上的電極。焊墊電極可為平坦的形狀,或可為所謂支柱形狀(柱狀)的突起。另外,焊墊電極的平面形狀可為圓形,亦可為四角形、八角形等的多角形。焊墊電極的材質並無特別限制,鋁、銅、鈦、鎢、鉻、鎳、金、焊錫、使用該等的合金等,可使用在半導體裝置領域一般所能夠使用的金屬,亦可積層多種金屬。
在第一步驟之中,將本發明之黏著劑片的鹼可溶性黏著劑薄膜側的面貼合在具有突起電極的第一電路構件的突起電極面。以下針對將黏著劑片貼合在第一電路構件的情況作詳細說明。
首先,在黏著劑片具有保護薄膜的情況下,將該薄膜剝離。接下來,使黏著劑片的鹼可溶性黏著劑薄膜與第一電路構件的突起電極對向,藉由熱壓接而貼合。此狀態為第1圖(b)所表示的狀態。此時,在突起電極沒有損傷或變形的狀態下,突起電極露出是很重要的。此處的突起電極露出,是指貼合後的鹼可溶性黏著劑薄膜的厚度低於突起電極的高度的狀態。
熱壓接可藉由熱平板壓延處理、熱真空平板壓延處理、熱輥積層處理、熱真空輥積層處理等來進行。該等的熱壓接處理亦可將多種組合使用。從與基板的密著性及壓入能力的觀點而言,貼合的溫度係以40℃以上為佳。另外,在貼合時,鹼可溶熱硬化性樹脂組成物薄膜會硬化,在蝕刻步驟之中,為了防止蝕刻速度降低或蝕刻不均發生,貼合溫度係以150℃以下為佳。在需要平坦的黏著劑被膜的情況,係以在貼合後,進一步進行熱平板壓延處理或熱真空平板壓延處理為佳。
在第二步驟之中,僅使黏著劑片的鹼可溶性黏著劑薄膜殘留在電路構件上,將黏著劑片中所含有的其他薄膜剝離。亦即,在黏著劑片僅包含鹼可溶性黏著劑薄膜與軟質薄膜的情況,僅將軟質薄膜剝離。另外,在黏著劑片除了鹼可溶性黏著劑薄膜與軟質薄膜之外還含有其他薄膜的情況,將軟質薄膜及該其他薄膜剝離。以這種方式,可得到在突起電極沒有損傷或變形的狀態且突起電極露出的狀態形成有鹼可溶性黏著劑被膜的電路構件。但是,在突起電極的上部(突起頂部)仍然殘存有少量的鹼可溶性黏著劑。第1圖(c)對應於此狀態。
在第三步驟之中,藉由鹼蝕刻除去突起頂部上的黏著劑,可達成在突起頂部上不存在鹼可溶性黏著劑的狀態。鹼蝕刻可藉由使用鹼蝕刻液將殘存於突起頂部上的鹼可溶性黏著劑除去來進行。鹼蝕刻液係以四甲基銨、二乙醇胺、二乙基胺基乙醇、氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、三乙胺、二乙胺、甲胺、二甲胺、
醋酸二甲胺乙基、二甲基胺基乙醇、二甲基胺乙基甲基丙烯酸酯、環己基胺、乙二胺、六亞甲基二胺等的鹼化合物之水溶液為佳。另外,依照情況,該等的鹼化合物水溶液可單獨含有N-甲基-2-吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲亞碸、γ-丁內酯、二甲基丙烯醯胺等的極性溶劑;甲醇、乙醇、異丙醇等的醇類;乳酸乙酯、丙二醇單甲醚醋酸酯等的酯類;環戊酮、環己酮、異丁基酮、甲基異丁基酮等的酮類等的有機溶劑或將數種組合而成。
鹼蝕刻可藉由將上述鹼蝕刻液噴霧在鹼可溶性黏著劑被膜的方法、使電路構件旋轉同時噴霧鹼蝕刻液之方法、將整個電路構件浸漬於鹼蝕刻液中之方法、或將整個電路構件浸漬於鹼蝕刻液中同時施加超音波之方法等來進行。
從可容易地蝕刻突起頂部上的樹脂,且容易控制欲使黏著劑殘留的部分的蝕刻量的觀點而言,鹼蝕刻步驟的條件,係以設定為鹼可溶性黏著劑薄膜的蝕刻速率為0.5μm/分鐘以上、100μm/分鐘以下為佳。蝕刻速率係以1.0μm/分鐘以上為更佳。另外,蝕刻速率係以50μm/分鐘以下為更佳,以10μm/分鐘以下為最佳。蝕刻速率可依照鹼蝕刻液的種類、溫度及濃度來調整。蝕刻速率(μm/分鐘),可藉由測定蝕刻步驟前後的鹼可溶性黏著劑薄膜的膜厚(μm)變化,將其除以蝕刻時間(分鐘)而計算出。
鹼蝕刻液的溫度係以20~50℃的範圍為佳。蝕刻時間從程序安定性的觀點而言,以5秒鐘以上為佳,從生產性提升的觀點而言,以5分鐘以內為佳。
在鹼蝕刻後亦能夠以水進行淋洗處理。淋洗處理,能夠藉由鹼蝕刻處理所使用的各種方法,並以鹼蝕刻液代替水來進行。另外,還可將乙醇、異丙醇等的醇類;乳酸乙酯、丙二醇單甲醚醋酸酯等的酯類等的有機溶劑加入水中來進行淋洗處理。
為了調整鹼蝕刻速度,在鹼蝕刻處理前亦可加上對電路構件實施烘烤處理之步驟。烘烤處理的溫度係以在50~180℃的範圍為佳,在60~120℃的範圍為較佳。烘烤處理的時間係以5秒鐘~數小時為佳。
從減少鹼蝕刻處理後殘存於鹼可溶性黏著劑被膜中的溶劑、揮發成分、水等的觀點而言,以在60~200℃的範圍加熱乾燥為佳。加熱乾燥時間係以1分鐘~數小時為佳。
以這樣的方式,藉由鹼蝕刻來除去突起電極上的黏著劑,可得到在突起頂部上不存在鹼可溶性黏著劑的形成有鹼可溶性黏著劑被膜之附突起電極的電路構件。第1圖(d)對應於此狀態。
在第四步驟之中,配置藉由上述方法形成有鹼可溶性黏著劑被膜且具有突起電極的第一電路構件與具有焊墊電極的第二電路構件,使突起電極與焊墊電極對向。然後,將第一電路構件與第二電路構件加熱加壓,使該等電連接。使用在兩面具有連接端子的電路構件,
亦即兩面配線基板,重覆進行如上述般的連接,藉此可得到電路構件為三維積層的半導體裝置。
在以往技術之中,無法完全除去突起頂部上的黏著劑,因此在使第一電路構件與第二電路構件電連接時,突起電極與焊墊電極之間會隔著黏著劑,這會降低半導體裝置的連接可靠性。依據本發明之半導體裝置之製造方法,可完全除去突起頂部上的黏著劑,因此可得到使第一電路構件與第二電路構件電連接時,電極間不會隔著黏著劑的半導體裝置。所以可製造出連接可靠性優異的半導體裝置。
以下基於實施例對本發明作具體說明,然而本發明不受其限定。
<所合成出的聚醯亞胺的醯亞胺化率>
首先測定藉由合成所得到的聚合物之紅外線吸收光譜,並確認聚醯亞胺所產生的醯亞胺構造的吸收峰(1780cm-1附近、1377cm-1附近)的存在。接下來,對此聚合物在350℃下熱處理1小時之後,再度測定紅外線吸收光譜,比較熱處理前與熱處理後的1377cm-1附近的峰強度。將熱處理後的聚合物的醯亞胺化率定為100%,而求得熱處理前的聚合物的醯亞胺化率。
<所合成出的聚醯亞胺之鹼可溶性評估>
對於氫氧化四甲銨的2.38%水溶液100g,所合成出的聚醯亞胺粉體在25℃時溶解0.1g以上的情況評為鹼可溶性,其他情況評為鹼不溶性。
<所合成出的聚醯亞胺之分子量>
使所合成出的聚醯亞胺溶於N-甲基-2-吡咯啶酮(以下稱為NMP),調製出固體成分濃度0.1重量%的溶液,作為測定樣品。使用具有以下所示構造的GPC裝置Waters2690(Waters股份有限公司製),計算出聚苯乙烯換算的重量平均分子量。GPC測定條件,是將移動相定為分別以0.05mol/L的濃度溶有LiCl與磷酸的NMP,並將流量定為0.4mL/分鐘。另外,使用管柱烘箱將管柱加熱至40℃。
偵測器:Waters996
系統控制器:Waters2690
管柱:TOSOH TSK-GEL α-4000
管柱:TOSOH TSK-GEL α-2500。
<蝕刻速率之測定>
鹼可溶性黏著劑薄膜之蝕刻速率的評估如以下方式進行。將保護薄膜由各實施例及比較例所製作出的黏著劑片剝離之後,在裸矽基板上,使用積層裝置(名機製作所股份有限公司製,MVLP600),以熱盤溫度80℃、抽真空時間20秒鐘、加壓壓力:0.5MPa、加壓時間60秒鐘的條件進行積層。此時,黏著劑片的鹼可溶性黏著劑薄膜會與矽基板相接。
接下來,將附軟質層的支持體由黏著劑片剝離,而得到形成有黏著劑被膜的矽基板。使用探針式段差計來測定黏著劑被膜的膜厚(T1)。接下來,使用作為蝕刻液的氫氧化四甲銨的2.38%水溶液,在23℃下進行
浸漬蝕刻30秒鐘之後,利用水來進行淋洗處理。使用探針式段差計,測定蝕刻後的黏著劑被膜之膜厚(T2)。
藉由下式計算出蝕刻速率:
蝕刻速率(μm/分鐘)=(T1-T2)÷0.5
<突起頂部的觀察>
將各實施例及比較例所製作出的黏著劑片的保護薄膜剝離,使用積層裝置(名機製作所股份有限公司製,MVLP600),以熱盤溫度80℃、抽真空時間20秒鐘、壓延壓力:0.5MPa、壓延時間60秒鐘的條件,將該剝離面積層在形成有Cu支柱焊錫突起(Cu高度:20μm、焊帽高度:20μm、突起徑:50μm、突起節距:100μm)的菊鍊矽基板上。
然後,將黏著劑片中的附軟質層的支持體剝離,而得到形成有黏著劑被膜的矽基板。接下來,使用氫氧化四甲銨的2.38%水溶液,在23℃下進行浸漬蝕刻30秒鐘,並以水實施淋洗處理。然後,使用SEM以1500倍的倍率觀察該矽基板的任意突起頂部。以目視觀察在所得到的SEM影像之中,突起的形狀,在突起並未觀測到損傷或變形的情況定為良好,在突起觀測到損傷或變形的情況定為不良。另外,以目視觀察在該SEM影像之中,突起頂部上的黏著劑的殘存,在突起頂部上並未觀測到黏著劑的情況定為良好,觀測到黏著劑的情況定為不良。
<可靠性測試>
將如上述方式形成黏著劑被膜的矽基板固定在貼有膠帶框架的切割膠帶。固定可藉由使用晶圓貼片裝置(Technovision股份有限公司製,FM-114),將切割膠帶(Lintec股份有限公司製,D-650)貼合在與突起電極相反側的晶圓基板面來進行。接下來,採用下述切削條件進行刀片切割,得到個別片的半導體晶片(邊長7.3mm的方形)。
切割裝置:DAD-3350(DISCO股份有限公司製)
半導體晶片大小:7.5×7.5mm
刀片:NBC-ZH2040-SE27HDEF
心軸轉速:30000rpm
切削速度:25mm/s
切削深度:切進切割膠帶的深度10μm為止
切割:單向全切割(one pass full cut)
切割模式:向下切割
切削水量:3.7L/分鐘
切削水及冷卻水:溫度23℃、導電度0.5MΩ.cm(在超純水中注入二氧化碳)。
接下來,使用倒裝晶片接合裝置(東麗工程股份有限公司製,FC-3000),在作為黏著體的PCB(印刷電路板)基板進行附上述鹼可溶性黏著劑被膜的半導體晶片的倒裝晶片接合。倒裝晶片接合是將半導體晶片固定在加熱至100℃的接合台,以溫度100℃、壓力15N/晶片、時間10秒鐘的條件暫時壓接於PCB基板之後,以溫度250℃、壓力200N/晶片的條件並且將時間設定為
20秒鐘,進行正式壓接,得到半導體裝置。然後,將5個所得到的半導體裝置在-50℃下維持5分鐘後,在125℃下維持5分鐘,以此作為1個循環,實施1000循環。然後,測定半導體裝置的電阻值,並且調查可測定的個數。
各實施例及比較例所使用的聚醯亞胺是藉由以下的方法來合成。
合成例1
在乾燥氮氣流下,使30.95g(0.0845莫耳)2,2-雙(3-胺基-4-羥苯基)六氟丙烷(以下稱為BAHF)、及1.24g(0.005莫耳)1,3-雙(3-胺丙基)四甲基二矽氧烷溶於100g N-甲基-2-吡咯啶酮(以下稱為NMP)。於其中同時加入31.02g(0.1莫耳)雙(3,4-二羧苯基)醚二酐(以下稱為ODPA)及30g NMP,在20℃下攪拌1小時,接下來在50℃下攪拌4小時。於其中加入2.5g(0.02莫耳)3-胺基酚,在50℃下攪拌2小時之後,在180℃下攪拌5小時,得到樹脂溶液。接下來,將樹脂溶液倒入3L的水中,得到白色沉澱。藉由過濾收集此沉澱,以水洗淨3次之後,以80℃的真空乾燥機乾燥5小時。所得到的樹脂粉體的醯亞胺化率為94%,且為鹼可溶性。另外,所得到的樹脂的重量平均分子量為25600。
合成例2
在乾燥氮氣流下,使11.41g(0.057莫耳)4,4'-二胺基二苯醚、1.24g(0.005莫耳)1,3-雙(3-胺丙基)四甲基二矽氧烷及作為末端密封劑的6.98g(0.075莫耳)苯胺溶於
100g NMP。於其中同時加入31.02g(0.1莫耳)ODPA與30g NMP,在20℃下攪拌1小時,接下來在50℃下攪拌4小時。然後添加15g二甲苯,使水與二甲苯共沸,同時在180℃下攪拌5小時。攪拌結束後,將溶液倒入3L的水中,得到白色沉澱。藉由過濾收集此沉澱,以水洗淨3次之後,以80℃的真空乾燥機乾燥5小時。所得到的樹脂粉體的醯亞胺化率為94%,且為鹼不溶性。另外,所得到的樹脂的重量平均分子量為11000。
另外,各實施例及比較例所使用的(B)~(D)成分如以下所述。
EP-4000S:PO改質雙酚A型環氧(商品名,ADEKA股份有限公司製)
835-LV:雙酚F型環氧(商品名,DIC股份有限公司製)
N-865:改質酚醛型環氧(商品名,DIC股份有限公司製)
2MAOK-PW:咪唑系硬化加速劑粒子(商品名,四國化成工業股份有限公司製)
HX-3941:微膠囊型硬化加速劑粒子(商品名,旭化成E-materials股份有限公司製)
SE-2050KNK:二氧化矽漿(商品名,Admatechs股份有限公司製,平均粒徑0.5μm、球狀二氧化矽、二氧化矽70重量%之甲基異丁基酮分散液)。
實施例1
將作為(A)成分的合成例1所得到的聚醯亞胺為30g、作為(B)成分的EP-4000S為50g、N865為15g、作為(C)成分的2MAOK-PW為5g及含有(D)成分的分散液SE-2050-KNK為214g(二氧化矽粒子的量為214×0.7=150(g))、作為有機溶劑的甲基異丁基酮為19g加以調合,以溶劑以外的添加物為固體成分,得到固體成分濃度為75%的鹼可溶性黏著劑組成物。使用逗點輥塗式塗布機(塗布機)將所得到的黏著劑組成物塗布在支持體上,在90℃下進行乾燥10分鐘,而得到黏著劑片。支持體採用EVA/PET(商品名,Takara incorporation股份有限公司製),在EVA面塗布黏著劑組成物。EVA/PET為積層有軟質薄膜且厚度為30μm的EVA薄膜與硬質薄膜且厚度為75μm的PET薄膜之附軟質層的支持體,EVA與PET合計厚度為105μm。乾燥後的鹼可溶性黏著劑薄膜厚度為30μm。在鹼可溶性黏著劑薄膜上積層作為保護薄膜且厚度為25μm的聚對苯二甲酸乙二酯薄膜SR-1(商品名,大槻工業股份有限公司製),得到附保護薄膜的黏著劑片。使用所得到的黏著劑片,如前述般實施突起頂部的觀察及可靠性測試。將結果揭示於表2。
實施例2~4
除了將附軟質層的支持體的厚度及(A)~(D)成分的摻合量如表1所記載般作變更以外,以與實施例1同樣的方式製作出黏著劑片,進行突起頂部的觀察及可靠性測試。將結果揭示於表2。
實施例5
除了附軟質層的支持體使用PE/PET(商品名,Fujimori產業股份有限公司製),在PE面塗布黏著劑組成物以外,以與實施例1同樣的方式製作出黏著劑片,進行突起頂部的觀察及可靠性測試。將結果揭示於表2。此外,PE/PET為積層有軟質薄膜且厚度為50μm的PE薄膜及硬質薄膜且厚度為75μm的PET薄膜之附軟質層的支持體,PE與PET合計厚度為125μm。
比較例1
除了使用合成例2之聚醯亞胺代替合成例1之聚醯亞胺以外,以與實施例1同樣的方式,製作出黏著劑片,進行突起頂部的觀察及可靠性測試。將結果揭示於表2。
比較例2
除了使用僅包含PET之支持體代替附軟質層的支持體以外,以與實施例1同樣的方式,製作出黏著劑片,進行突起頂部的觀察及可靠性測試。將結果揭示於表2。
在將本發明之黏著劑片與附突起電極的半導體晶片貼合的情況,能夠不對突起電極造成損傷而使突起電極露出。然後進一步,藉由使用鹼水溶液對突起頂部上的黏著劑實施濕式蝕刻,可達成在突起頂部上不存在黏著劑的狀態。因此可製造出倒裝晶片安裝後半導體晶片與電路基板的連接可靠性優異的半導體裝置。
100‧‧‧附突起電極的電路構件
101‧‧‧銅支柱
102‧‧‧焊錫突起
103‧‧‧鹼可溶性黏著劑薄膜
104‧‧‧軟質薄膜
105‧‧‧殘存於突起頂部上的鹼可溶性黏著劑
Claims (8)
- 一種附突起電極的半導體裝置製造用黏著劑片,其係在軟質薄膜上形成有鹼可溶性黏著劑薄膜之黏著劑片,而該鹼可溶性黏著劑薄膜含有(A)鹼可溶性樹脂、(B)環氧化合物、(C)硬化加速劑及(D)無機粒子,且(D)無機粒子之含量係相對於除去溶劑及無機粒子的鹼可溶性黏著劑薄膜的有機物總量100重量份,為40重量份以上400重量份以下。
- 如請求項1之附突起電極的半導體裝置製造用黏著劑片,其中,該軟質薄膜為聚乙烯薄膜或乙烯醋酸乙烯酯共聚物薄膜。
- 如請求項1之附突起電極的半導體裝置製造用黏著劑片,其中該(A)鹼可溶性樹脂為鹼可溶性聚醯亞胺。
- 如請求項3之附突起電極的半導體裝置製造用黏著劑片,其中,該鹼可溶性聚醯亞胺具有下述通式(1)所表示之結構單元,且主鏈的至少一末端具有下述通式(2)及/或(3)所表示之結構:
- 如請求項3或4之附突起電極的半導體裝置製造用黏著劑片,其中,該鹼可溶性聚醯亞胺含有酚性羥基。
- 如請求項1至4中任一項之附突起電極的半導體裝置製造用黏著劑片,其中,該鹼可溶性黏著劑薄膜對23℃的氫氧化四甲銨2.38%水溶液的蝕刻速率為0.5~100μm/分鐘。
- 一種半導體裝置之製造方法,其係依序包括: 將如請求項1至6中任一項之附突起電極的半導體裝置製造用黏著劑片的鹼可溶性黏著劑薄膜側的面貼合在具有突起電極的第一電路構件的突起電極面之步驟;僅使該黏著劑片的鹼可溶性黏著劑薄膜殘留在該電路構件上,將該黏著劑片所含有的其他薄膜剝離之步驟;以鹼水溶液蝕刻該鹼可溶性黏著劑薄膜,除去突起電極上的該黏著劑之步驟;及藉由加熱加壓使前述第一電路構件與具有焊墊電極的第二電路構件電連接之步驟。
- 如請求項7之半導體裝置之製造方法,其中,蝕刻該鹼可溶性黏著劑薄膜之步驟中的蝕刻速率為0.5~100μm/分鐘。
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