TWI555812B - 用於半導體之黏合膜以及使用該黏合膜之半導體元件 - Google Patents
用於半導體之黏合膜以及使用該黏合膜之半導體元件 Download PDFInfo
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- TWI555812B TWI555812B TW101147518A TW101147518A TWI555812B TW I555812 B TWI555812 B TW I555812B TW 101147518 A TW101147518 A TW 101147518A TW 101147518 A TW101147518 A TW 101147518A TW I555812 B TWI555812 B TW I555812B
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- adhesive film
- curing agent
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- semiconductor
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Classifications
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
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Description
本發明有關一種用於半導體之黏合膜,其含有胺固化劑以及酚類固化劑二者,以及在空隙特徵以及可靠度方面展現極佳的特性。更特別地,本發明有關一種用於半導體之黏合膜,其在固化前之貯存模數與80%固化後170℃下之貯存模數間,展現1.5至3.0之高變異率;具有可撓性,以便在晶粒黏貼時,抑制空隙產生;幫助移除空隙,以便控制EMC(環氧化物封膠化合物)封膠時,黏貼界面上之空隙面積;以及固化後具有硬度,以便提供良好的晶片抗剪強度以及回流阻力,藉此確保高可靠度。
近年來,隨著半導體二極體的尺寸有越來越小或容量越來大之趨勢,使用黏合膜來將半導體二極體彼此黏貼或黏貼到支撐元件上。用於半導體組裝之黏合膜係與切割膜一起使用,以便在切割製程中抓住半導體晶圓。
在半導體晶圓之組裝方面,當切割膜以及黏合膜安裝在半導體晶圓上時,於切割製程中將半導體晶圓切成
個別晶片,然後在晶粒黏著中之高溫下堆疊晶片。為抓住堆疊的晶片,在125℃至150℃下進行預固化一段預定時間,然後使完成的半導體二極體經EMC封膠之處理。
其上堆疊半導體晶圓之電路板,由於線路之關係而具有不平整的表面,如此在晶粒黏著期間,晶粒與黏合膜之間以及半導體晶片之間的黏著界面中,可能會產生空隙。在黏著界面中當產生大量的空隙時,可能會有諸如黏著強度降低、熱與導電性降低、晶粒破裂等等之問題,其在元件之品質以及可靠度方面可能具有負面的影響。
為了解決此問題而使用具有高流動性之黏合膜時,其可能可以抑制晶粒黏著製程中空隙之產生。然而在此情況下,減低了晶粒抗剪強度,從而引起加工性能降低。另一方面,具有高貯存模數之黏合膜可提供高的抗剪強度,但其使得不僅很難在晶粒黏著製程中移除空隙,且很難在EMC封膠製程中移除空隙。
雖然在此領域中,典型地使用丙烯基結合劑以及酚類固化劑作為晶粒黏著膜(DAF)之組成物(韓國專利公開案第10-2009-0103434號、韓國專利案第10-0942356號等),但酚類固化系統會使得空隙不易移除,以及提供固化產物低的模數以及晶粒抗剪強度,因此提供非常低的可靠度。
因此,需要有一種黏合膜,其能展現極佳晶粒抗剪強度,且可抑制晶粒黏著製程中空隙的形成,同時容許在EMC封膠期間(若有的話)容易移除空隙。
為解決此技藝中用於半導體之黏合膜之問題,諸如在黏著界面中產生大量的空隙,以及由於低晶粒抗剪強度以及衝擊抗性產生之低可靠度,本發明開發出一種用於半導體之黏合膜,其在該黏合膜之製造時,使用適當比率之胺固化劑以及酚類固化劑,在空隙特徵以及可靠度方面展現極佳的特性。
本發明之目的在於提供一種用於半導體之黏合膜,其在固化前之貯存模數與80%固化後170℃下之貯存模數間,具有1.5至3.0之高變異率。
更明確地,本發明之目的在於提供一種用於半導體之黏合膜,其展現可撓性,以便在晶粒黏貼時,抑制空隙的產生;幫助移除空隙,以便控制EMC封膠時,黏貼界面上之空隙面積;以及固化後具有硬度,以便提供良好的晶片抗剪強度以及回流阻力,藉此確保高可靠度。
本發明之一態樣提供一種用於半導體之黏合膜,其含有胺固化劑以及酚類固化劑二者,其中該黏合膜具有80%或更多固化後170℃下之貯存模數(b),對固化前40℃下之貯存模數(a)之比率(b/a),在1.5至3.0之範圍內;固化後貯存模數為5.0×106dyne/cm2或更大;固化後抗剪強度為9 kgf或更高;和/或在黏合膜黏貼面積中,封膠後空隙面積比率為5%或更低。
在一具體例中,在4個固化循環後170℃下之貯存模數(b),對固化前40℃下之貯存模數(a)之比率(b/a),可在
從1.5至3.0之範圍內。在此,各固化循環包含在125℃下固化1個小時以及在150℃下固化10分鐘。
在一具體例中,該胺固化劑可包括二胺基二苯基碸。
在一具體例中,該酚類固化劑可為雙酚A或雙酚F。
在一具體例中,在125℃下1個小時、在150℃下10分鐘以及在175℃下1個小時之固化後,該黏合膜可具有晶粒抗剪強度為9kgf或更高。
在一具體例中,該黏合膜在125℃下1個小時以及在150℃下1個小時之固化,在175℃下封膠60秒以及在175℃下封膠固化1個小時後,在黏合膜黏貼面積中,具有空隙面積比率為5%或更少。
在一具體例中,該黏合膜可具有固化後晶粒抗剪強度為9kgf或更高,以及固化後170℃下之貯存模數為5.0×106 dyne/cm2或更高。
在一具體例中,該黏合膜在黏合膜黏貼面積中,可具有封膠後空隙比率為5%或更小。
本發明之另一態樣提供一種用於半導體之黏合膜,其包括:結合樹脂;環氧樹脂;填料;胺固化劑;以及酚類固化劑,其中該胺固化劑(y)對該酚類固化劑(x)之莫耳%比率(y/x)範圍從0.3至10。
在一具體例中,在80%固化後170℃下之貯存模數(b),對固化前40℃下之貯存模數(a)之比率(b/a),範圍可
從1.5至3.0。
在一具體例中,該黏合膜可具有封膠後晶粒抗剪為9kgf或更高。
在一具體例中,以該黏合膜之固體含量100重量份為基準,該黏合膜可包括40至80重量份之該結合樹脂;1至30重量份之該環氧樹脂;1至30重量份之該填料;0.1至20重量份之該胺固化劑;以及0.1至20重量份之該酚類固化劑。
在一具體例中,該結合樹脂可為彈性體樹脂。
本發明之另外的態樣提供一種半導體元件,其包括一配線基材以及一半導體晶片,以及由該用於半導體之黏合膜連接。
如本發明之用於半導體之黏合膜,可抑制黏貼界面中空隙之產生,且具有高晶粒抗剪強度以及回流阻力,藉此確保高可靠度。
更明確地,如本發明之用於半導體之黏合膜含有胺固化劑以及酚類固化劑二者,可提供高的固化後之貯存模數對固化前之貯存模數之比率,在1.5至3.0之範圍內;展現可撓性,以便在晶粒黏貼時,抑制空隙產生;幫助EMC封膠時(若有的話),移除空隙;以及固化後具有硬度,以便提供良好的晶粒抗剪強度以及回流阻力,藉此確保良好的空隙特徵以及高可靠度。
現在將詳細的說明本發明之具體例。應了解,下列具體例僅供例示用,任何情況下不能解釋為本發明之範疇之限制。
根據本發明,用於半導體之黏合膜可包括聚合物樹脂、環氧樹脂、固化劑、填料以及其它添加物。應了解,此等組份之種類以及數量沒有特別限制,可依此技藝中使用之情況作決定。接著,將描述適合用於本發明之黏合膜之組份的詳細例子。
可使用在此技藝中使用之任何典型的聚合物樹脂,此沒有限制。適合用於本發明之黏合膜之聚合物樹脂之例子,可包括聚醯亞胺樹脂、聚苯乙烯樹脂、聚乙烯樹脂、聚酯樹脂、聚醯胺樹脂、丁二烯橡膠、丙烯酸橡膠、(甲基)丙烯酸酯樹脂、胺基甲酸酯樹脂、聚苯醚樹脂、聚醚醯亞胺樹脂、苯氧基樹脂、聚碳酸酯樹脂、改質的聚苯醚樹脂以及其等之混合物。此等樹脂可單獨使用或以其之二或多種混合物之形式使用。
另外,可使用含官能單體之聚合物樹脂,例如,含有官能單體之含環氧基團(甲基)丙烯酸共聚物,諸如丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯等等。可使用(甲基)丙烯酸酯共聚物或丙烯基橡膠,作為該含環氧基團(甲基)丙烯酸共聚物。此等可單獨使用或以其二或多種混合物之
形式使用。
該聚合物樹脂可為彈性體樹脂。可使用此技藝中使用之任何典型的彈性體樹脂,此沒有限制。彈性體樹脂之例子,包括丙烯腈、丁二烯、苯乙烯、丙烯基、異戊二烯、乙烯、丙烯、聚胺基甲酸酯以及矽樹脂,但不限於此。此等可單獨使用或以其二或多種混合物之形式使用。
該彈性體樹脂較佳地具有重量平均分子量從50,000g/mol至5,000,000g/mol,更佳地從100,000g/mol至800,000g/mol。
該聚合物樹脂存在之數量,以該黏合膜之固體含量100重量份為基準,較佳地為40至80重量份,更佳地50至70重量份。在此範圍內,該黏合膜具有良好的空隙特徵以及高可靠度。
可使用此技藝中使用之任何典型的環氧樹脂,此沒有限制。該環氧樹脂可包括液態環氧樹脂以及固態環氧樹脂中之至少一種。
適合的液態環氧樹脂之例子,包括雙酚A類液態環氧樹脂、雙酚F類液態環氧樹脂、三或更高級多官能液態環氧樹脂、橡膠改質的液態環氧樹脂、胺基甲酸酯改質的液態環氧樹脂、丙烯酸改質的液態環氧樹脂以及光敏性液態環氧樹脂。此等液態環氧樹脂可單獨使用或以其二或多種混合物之形式使用。
該液態環氧樹脂可具有環氧當量從約100至約
1500g/eq,更佳地從約150g/eq至約800g/eq,又更佳地從約150g/eq至約400g/eq。在此範圍內,可獲得具良好黏合性以及熱抗性,同時維持高玻璃轉移溫度之固化產物。
該液態環氧樹脂可具有重量平均分子量在100g/mol至1,000g/mol之範圍內。此範例具提供高流動性之優點。
該固態環氧樹脂可為一種在室溫下為固相或準固相,且具有一或多種官能基團之樹脂。適合的固態環氧樹脂之例子,包括雙酚類環氧樹脂、酚醛類環氧樹脂、鄰甲酚醛類環氧樹脂、雙酚醛環氧樹脂、多官能環氧樹脂、胺環氧樹脂、雜環環氧樹脂、取代的環氧樹脂、萘基環氧樹脂以及其等之衍生物,但不限於此。
市售可得之環氧樹脂包括下列。雙酚類環氧樹脂之例子包括YD-017H、YD-020、YD020-L、YD-014、YD-014ER、YD-013K、YD-019K、YD-019、YD-017R、YD-017、YD-012、YD-011H、YD-011S、YD-011、YDF-2004、YDF-2001(Kukdo Chemical Co.,Ltd.)等。酚醛類環氧樹脂之例子包括EPIKOTE 152以及EPIKOTE 154(Yuka Shell Epoxy Co.,Ltd.);EPPN-201(Nippon Kayaku Co.,Ltd.);DN-483(Dow Chemical Company);YDPN-641、YDPN-638A80、YDPN-638、YDPN-637、YDPN-644、YDPN-631(Kukdo Chemical Co.,Ltd.)等。鄰甲酚醛類環氧脂之例子包括YDCN-500-1P、YDCN-500-2P、YDCN-500-4P、YDCN-500-5P、YDCN-500-7P、
YDCN-500-8P、YDCN-500-10P、YDCN-500-80P、YDCN-500-80PCA60、YDCN-500-80PBC60、YDCN-500-90P、YDCN-500-90PA75(Kukdo Chemical Co.,Ltd.);EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、EOCN-1025、EOCN-1027(Nippon Kayaku Co.,Ltd.);YDCN-701、YDCN-702、YDCN-703、YDCN-704(Tohto Kagaku Co.,Ltd.);Epiclon N-665-EXP(Dainippon Ink and Chemicals,Inc.)等。雙酚醛環氧樹脂之例子包括KBPN-110、KBPN-120、KBPN-115(Kukdo Chemical Co.,Ltd.)等。多官能環氧樹脂之例子包括Epon 1031S(Yuka Shell Epoxy Co.,Ltd.);Araldite 0163(Ciba Specialty Chemicals);Detachol EX-611、Detachol EX-614、Detachol EX-25-12614B、Detachol EX-622、Detachol EX-512、Detachol EX-521、Detachol EX-421、Detachol EX-411、Detachol EX-321(NAGA Celsius Temperature Kasei Co.,Ltd.);EP-5200R、KD-1012、EP-5100R、KD-1011、KDT-4400A70、KDT-4400、YH-434L、YH-434、YH-300(Kukdo Chemical Co.,Ltd.)等。胺環氧樹脂之例子包括EPIKOTE 604(Yuka Shell Epoxy Co.,Ltd.);YH-434(Tohto Kagaku Co.,Ltd.);TETRAD-X以及TETRAD-C(Mitsubishi Gas Chemical Company Inc.);ELM-120(Sumitomo Chemical Industry Co.,Ltd.)等。雜環環氧樹脂之例子包括PT-810(Ciba Specialty Chemicals)。取代的環氧樹脂之例子包括:ERL-4234、ERL-4299、ERL-4221、ERL-4206(UCC Co.,Ltd.)
等。萘基環氧樹脂之例子包括Epiclon HP-4032、Epiclon HP-4032D、Epiclon HP-4700以及Epiclon HP-4701(Dainippon Ink and Chemicals,Inc.)。
該環氧樹脂存在之數量,以該黏合膜之固體含量100重量份為基準,較佳地為1至30重量份,更佳地5至20重量份。在此範例內,可獲得高可靠度以及良好空隙移除作用。
可使用此技藝中使用之任何典型的胺固化劑,此沒有限制。
胺固化劑之例子包括3,3'-二胺基聯苯胺、4,4'-二胺基二苯甲烷、4,4'-或3,3'-二胺基二苯基碸、4,4'二胺基苯酮、對苯二胺、間苯二胺、間甲苯二胺、4,4'-二胺基二苯醚、3,3'-二胺基苯酮、1,4'-或1,3'-雙(4-或3-胺枯基)苯、1,4'-雙(4-或3-胺基苯氧基)苯、2,2'-雙[4-(4-或3-胺基苯氧基)苯基]丙烷、雙[4-(4-或3-胺基苯氧基)苯基]碸、2,2'-雙[4-(4-或3-胺基苯氧基)苯基]六氟碸、2,2'-雙[4-(4-或3-胺基苯氧基)苯基]六氟丙烷、4,4'-二胺基-3,3',5,5'-四丁基二苯酮、4,4'-二胺基-3,3',5,5'-四乙基二苯酮、4,4'-二胺基-3,3',5,5'-四-正-丙基二苯酮、4,4'-二胺基-3,3',5,5'-四異丙基二苯酮、4,4'-二胺基-3,3',5,5'-四甲基二苯酮、4,4'-二胺基-3,3',5,5'-四-正-丙基二苯甲烷、4,4'-二胺基-3,3'5,5'-四甲基二苯甲烷、4,4'-二胺基-3,3'5,5'-四異丙基二苯甲烷、4,4'-二胺基-3,3'5,5'-四乙基二苯甲烷、4,4'-二胺基-3,3'-二甲基-5,5'-二乙基二苯甲
烷、4,4'-二胺基-3,3'-二甲基-5,5'-二異丙基二苯甲烷、4,4'-二胺基-3,3'-二乙基-5,5'-二乙基二苯甲烷、4,4'-二胺基-3,5-二甲基-3',5'-二乙基二苯甲烷、4,4'-二胺基-3,5-二甲基-3',5'-二異丙基二苯甲烷、4,4'-二胺基-3,5-二乙基-3',5'-二丁基二苯甲烷、4,4'-二胺基-3,5-二異丙基-3',5'-二丁基二苯甲烷、4,4'-二胺基-3,3'-二異丙基-5,5'-二丁基二苯甲烷、4,4'-二胺基-3,3'-二甲基-5,5'-二丁基二苯甲烷、4,4'-二胺基-3,3'-二乙基-5,5'-二丁基二苯甲烷、4,4'-二胺基-3,3'-二甲基二苯甲烷、4,4'-二胺基-3,3'-二乙基二苯甲烷、4,4'-二胺基-3,3'-二-正-丙基二苯甲烷、4,4'-二胺基-3,3'-二異丙基二苯甲烷、4,4'-二胺基-3,3'-二丁基二苯甲烷、4,4'-二胺基-3,3',5-三甲基二苯甲烷、4,4'-二胺基-3,3',5-三乙基二苯甲烷、4,4'-二胺基-3,3',5-三-正-丙基二苯甲烷、4,4'-二胺基-3,3',5-三異丙基二苯甲烷、4,4'-二胺基-3,3',5-三丁基二苯甲烷、4,4'-二胺基-3-甲基-3'-乙基二苯甲烷、4,4'-二胺基-3-甲基-3'-異丙基二苯甲烷、4,4'-二胺基-3-甲基-3'-丁基二苯甲烷、4,4'-二胺基-3-異丙基-3'-丁基二苯甲烷、2,2-雙(4-胺基-3,5-二甲基苯基)丙烷、2,2-雙(4-胺基-3,5-二乙基苯基)丙烷、2,2-雙(4-胺基-3,5-二-正-丙基苯基)丙烷、2,2-雙(4-胺基-3,5-二異丙基苯基)丙烷、2,2-雙(4-胺基-3,5-二丁基苯基)丙烷、4,4'-二胺基-3,3',5,5'-四甲基二苯基苯醯替苯胺、4,4'-二胺基-3,3',5,5'-四乙基二苯基苯醯替苯胺、4,4'-二胺基-3,3',5,5'-四-正-丙基二苯基苯醯替苯胺、4,4'-二胺基-3,3',5,5'-四異丙基二苯基苯醯替苯胺、4,4'-二胺基-3,3',5,5'-四丁基二苯基苯醯替苯
胺、4,4'-二胺基-3,3',5,5'-四甲基二苯碸、4,4'-二胺基-3,3',5,5'-四乙基二苯碸、4,4'-二胺基-3,3',5,5'-四-正-丙基二苯碸、4,4'-二胺基-3,3',5,5'-四異丙基二苯碸、4,4'-二胺基-3,3',5,5'-四甲基二苯醚、4,4'-二胺基-3,3',5,5'-四乙基二苯醚、4,4'-二胺基-3,3',5,5'-四-正-丙基二苯醚、4,4'-二胺基-3,3',5,5'-四異丙基二苯醚、4,4'-二胺基-3,3',5,5'-四丁基二苯醚、3,3'-二胺基苯酮、3,4-二胺基苯酮、3,3'-二胺基二苯醚、3,3'-二胺基二苯甲烷、3,4'-二胺基二苯甲烷、2,2'-二胺基-1,2-二苯乙烷或4,4'-二胺基-1,2-二苯乙烷、2,4-二胺基二苯胺、4,4'-二胺基辛氟二苯基、鄰聯茴香胺等等,但不限於此。此等可單獨使用或以其二或多種混合物之形式使用。
較佳地可使用二胺基二苯基碸作為該胺固化劑。
該胺固化劑存在之數量,以該黏合膜之固體含量100重量份為基準,較佳地為0.1至20重量份,更佳地1至10重量份。在此範圍內,其可能在封膠時,抑制空隙產生以及獲得有效的空隙移除。
可使用此技藝中使用之任何典型的酚類固化劑,此沒有限制。
酚類固化劑之例子包括雙酚類樹脂,諸如雙酚A、雙酚F、雙酚S等等;酚醛樹脂;雙酚A線型酚醛樹脂;以及酚類樹脂,諸如二甲苯、鄰甲酚醛、聯苯樹脂等等,但不限於此。
市售可得之酚類固化劑包括下列。酚固化劑之例
子包括H-1、H-4、HF-1M、HF-3M、HF-4M以及HF-45(Meiwa Plastic Industries Co.,Ltd.);對二甲苯酚類固化劑之例子包括MEH-78004S、MEH-7800SS、MEH-7800S、MEH-7800M、MEH-7800H、MEH-7800HH以及MEH-78003H(Meiwa Plastic Industries Co.,Ltd.)、KPH-F3065(Kolong Industries Co.,Ltd.);聯苯固化劑之例子包括MEH-7851SS、MEH-7851S、MEH7851M、MEH-7851H、MEH-78513H以及MEH-78514H(Meiwa Plastic Industries Co.,Ltd.)以及KPH-F4500(Kolong Industries Co.,Ltd.);以及三苯基甲基固化劑之例子包括MEH-7500、MEH-75003S、MEH-7500SS、MEH-7500S、MEH-7500H(Meiwa Plastic Industries Co.,Ltd.)等。此等可單獨使用或以其混合物之形式使用。
可使用具有環氧當量從100g/eq至150g/eq之雙酚A或雙酚F,作為該酚類固化劑。
該酚類固化劑存在之數量,以該黏合膜之固體含量100重量份為基準,較佳地為0.1至20重量份,更佳地1至10重量份。當該酚類固化劑之數量不在此範圍內時,該黏膜合在黏合性以及固化特性會變差。該酚類固化劑在此範圍內時,其可能在封膠時,抑制空隙產生以及在移除空隙上獲得所欲的作用。
該胺固化劑(y)對該酚類固化劑(x)之莫耳%比率(y/x)較佳地範圍從0.3至10,更佳地從0.5至10。在此範圍內,可獲得該酚類固化劑與該胺固化劑之有效的酸催化反
應,以便達到適合的固化反應,以及可提供適當數量之胺固化劑,藉此使能夠在封膠時有效的移除空隙。
如本發明之黏合組成物可包括填料,以便藉由提供觸變特性而調整熔融黏度。可使用此技藝中使用之任何典型的填料,此沒有限制。依需要,可使用無機或有機填料作為該填料。無機填料之例子包括金屬粉末,諸如金、銀、銅以及鎳粉;以及非金屬類,諸如二氧化鋁、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、二氧化矽、氮化硼、二氧化鈦、玻璃、氧化鐵、陶瓷等等。有機填料之例子包括碳、橡膠、聚合物填料等等。雖然對於填料之形狀與大小沒有特別的限制,但填料可為球形填料,且具有平均粒徑範圍從約500nm至10μm。
較佳地,該填料係具有平均粒徑為5至20μm之球形二氧化矽填料。
該填料存在之數量,以該黏合膜之固體含量100重量份為基準,較佳地為1至30重量份,更佳地5至20重量份。在此範圍內,其可能獲得足夠作用的填料,同時防止與被黏物之黏合性變差。另外,在此範圍內,可獲得高流動性、成膜性以及黏合性。
本發明之黏合膜可進一步包括矽烷偶合劑,以便在組成物之摻合期間,透過其間之化學偶合,提高諸如二
氧化矽之無機材料與有機材料之表面間的黏合性。
可使用此技藝中使用之任何典型的矽烷偶合劑,其沒有限制。矽烷偶合劑之例子包括:含環氧基團之矽烷偶合劑,諸如2-(3,4-環氧環己基)-乙基三甲氧基矽烷、3-環氧丙烷基丙基三甲氧基矽烷以及3-環氧丙烷基丙基三乙氧基矽烷;含胺基團之矽烷偶合劑,諸如N-2-(胺乙基)-3-胺丙基甲基二甲氧基矽烷、N-2-(胺乙基)-3-胺丙基三甲氧基矽烷、N-2-(胺乙基)-3-胺丙基三乙氧基矽烷、3-胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-三乙氧矽基-N-(1,3-二甲亞丁基)丙胺以及N-苯基-3-胺丙基三甲氧基矽烷;含巰基之矽烷偶合劑,諸如3-巰基丙甲基二甲氧基矽烷以及3-巰基丙基三乙氧基矽烷;以及含異氰酸基之矽烷偶合劑,諸如3-異氰酸丙基三乙氧基矽烷。此等矽烷偶合劑可單獨使用或以其二或多種混合物之形式使用。
該偶合劑存在之數量,以該黏合膜之固體含量100重量份為基準,較佳地為0.01至10重量份,更佳地0.1至5重量份。在此範圍內,可獲得高黏合可靠度以及減少泡泡之發生。
適合用於本發明之黏合膜之固化加速劑,作用係縮短半導體製程期間,環氧樹脂之固化時間。雖然可使用此技藝中任何典型的固化加速劑,但最好是使用三聚氰胺、咪唑或三苯基膦固化催化劑。市售可得之咪唑固化加速劑之例子包括PN-23、PN-40(Ajinomoto Fine Technology
Co.,Inc.)、2P4MZ、2MA-OK、2MAOK-PW、2P4MHZ(Shikoku Chemicals Corp.)、TPP-K、TPP-MK(HOKKO Chemical Industry Co.,Ltd.)等。此等可單獨使用,或以其二或多種混合物之形式使用。
該固化加速劑存在之數量,以該黏合膜之固體含量100重量份為基準,較佳地為0.01至10重量份,更佳地0.03至5重量份。在此範圍內,可獲得高熱抗性以及維護安定性,同時確保環氧樹脂足夠的反應。
該用於半導體之黏合膜,可進一步包括離子吸附劑,以便吸附離子性雜質,同時在濕氣吸收時,獲得絕緣可靠度。可使用此技藝中任何典型的離子吸附劑,其沒有限制。離子吸附劑之例子包括三嗪硫醇化合物、鋯化合物、銻鉍化合物、鎂鋁化合物等等,但不限於此。
如本發明之用於半導體之黏合膜,可進一步包括有機溶劑。該溶劑作用為減少黏合組成物之黏度,藉此促進膜的形成。有機溶劑之例子包括甲苯、二甲苯、醋酸丙二醇甲醚酯、苯、丙酮、甲基乙基酮、四氫呋喃、二甲基甲醯胺以及環己酮,但不限於此。
形成如本發明之用於半導體之黏合膜,不需使用特別的裝置或設備,可使用此技藝中任何通用之方法來製造該黏合膜。
例如,可以下列方法製造該黏合膜。在此方法方
面,將以上所述之各別組份溶於溶劑中,使用珠磨機充份地揉合,接著將產物沈積在經離型處理之聚乙烯對苯二甲酸酯(PET)膜上,然後在100℃烤箱中乾燥10~30分鐘,製得具適合厚度之黏合膜。
該黏合膜較佳地具有厚度5μm至200μm,更佳地從10μm至100μm,又更佳地15至60μm。在此範圍內,該黏合膜藉由確保極佳的PCB(印刷電路板)間隙填充能力,在封膠後,防止空隙特徵變差,同時提供經濟可行性。
在一態樣中,本發明提供一種用於半導體之黏合膜,其含有胺固化劑以及酚類固化劑二者,其中在4個固化周期後170℃下之貯存模數(b),對固化前在40℃下之貯存模數(a)之比率(b/a)的範圍從1.5至3.0。在此,各固化周期包含在125℃下固化1個小時以及在150℃下固化10分鐘。
在此,固化前40℃下之貯存模數(a),意指黏合膜在40℃下之貯存模數的值,其係藉由在60℃下層疊該黏合膜至厚度400~500μm,接著使用ARES,在溫度增加速率為50℃/分、應變5%以及頻率1雷得之條件下測量而得。
在此,固化後之貯存模數(b)意指黏合膜在170℃下之貯存模數的值,其係藉由在60℃下層疊該黏合膜至厚度400~500μm,固化該樣本歷時全部4個周期,各周期包含在125℃之烤箱中半固化1個小時以及在150℃熱盤上10分鐘,接著使用ARES,在溫度增加速率為50℃/分、應變5%以及頻率1雷得之條件下測量而得。
固化前後之貯存模數的比率(b/a)之範圍可從1.5
至3.0。在此範圍內,其可能抑制晶粒黏貼期空隙之產生,以及促進EMC封膠期間空隙之移除,同時提供極佳的封膠後晶粒抗剪強度以及可靠度。
在一具體例中,該用於半導體之黏合膜在125℃下1個小時,在150℃下10分鐘以及在175℃下1個小時之固化後,具有固化後晶粒抗剪強度為9kgf或更高。當該黏合膜之晶粒抗剪強度為9kgf或更高時,該黏合膜具有高強度,因此可降低熱衝擊條件下因膨脹之失敗,藉此提供高可靠度。
該固化後之晶粒抗剪強度係以下列程序測量。將720μm厚之晶圓切成具尺寸5×5mm之晶片。在60℃下將該等晶片與該用於半導體之黏合膜疊在一起,然後切割,只留下黏合的部分。之後,將上面具尺寸5×5mm之晶片置於具尺寸10×10mm之晶圓上,接著在120℃烤盤上施以10kgf之力量,歷時5秒。之後,使樣本在125℃烤箱中經歷半固化處理1個小時,留在150℃烤盤上10分鐘,模擬金線焊連條件,然後在像EMC固化之條件,175℃下固化1個小時。之後在250℃下,使用Dyse 4000,100N棒,高度10μm,100 mm/s下測量該黏合膜之晶粒抗剪強度。
在另一具體例中,在125℃下1個小時以及在150℃下1個小時之固化,在175℃下封膠60秒以及在175℃下封膠固化1個小時後,該黏合膜在黏合膜黏貼面積中,可具有空隙面積比率為5%或更小。
假如在黏合膜黏貼面積中,空隙面積比率超過
5%,則該黏合膜在黏合強度以及熱與電氣導電度上可能會減低,且可能會導致晶粒碎裂,從而對元件之品質以及可靠度有不好的影響。因此,在黏合膜黏貼面積中,該黏合膜較佳地具有空隙面積比率為5%或更小。
段落“空隙面積比率為5%或更小”並不是意指空隙面積比率數值包括0以及小於0之負值,而是意指空隙面積比率具有接近0之低正值極限。
在測量空隙面積比率方面,在60℃下將黏合膜與10×10mm之蓋玻片疊在一起,然後作切割,僅留下黏合部分。之後,在1 kgf之力量下1秒,將樣本壓在PCB上,在125℃下固化1個小時以及在150℃下固化1個小時,然後用EMC(SG-8500B,Cheil Industries Co.,Ltd.,Korea),在175℃下封膠60秒。在175℃下封膠固化1個小時後,使用研磨器,磨掉樣本上蓋住蓋玻片之封膠,使用低倍率顯微鏡觀察空隙。在此,空隙面積比率意指封膠後空隙面積相對於黏合膜黏貼面積之數位量值,單位為百分比((空隙面積/黏合膜黏貼面積)×100%))。
在一具體例中,在125℃下1個小時,在150℃下10分鐘以及在175℃下1個小時之固化後,該用於半導體之黏合膜具有晶粒抗剪強度為9kgf或更高,以及在170℃下之固化後貯存模數為5.0×106 dyne/cm2或更大。
當黏合膜在170℃下具有固化後貯存模數為5.0×106 dyne/cm2或更大時,其可充分地忍受在170℃下施予該封膠1噸的壓力,如此晶片不會脫離封膠,藉此排除封膠
失敗。在此情況下,該黏合膜具有極佳的晶粒抗剪強度以及回流阻力,從而提供高可靠度。
在此,該固化後之貯存模數意指在170℃下之貯存模數值,其係藉由在60℃下層疊黏合膜至厚度400~500μm,固化該樣本歷時全部4個周期,各周期包含在125℃之烤箱中半固化1個小時以及在150℃熱盤上10分鐘,接著使用ARES,在溫度增加速率為50℃/分、應變5%以及頻率1雷得之條件下測量而得。
在另外的態樣中,本發明提供一種半導體元件,其由如本發明之用於半導體之黏合膜連接。
該半導體元件包括一配線基材;一用於半導體之黏合膜,其貼至該配線基材之晶片安裝表面;以及一半導體晶片,其安裝在該黏合膜上。
可使用此技藝中任何典型的配線基材以及半導體晶片,此沒有限制。
另外,可使用此技藝中已知之任何製造半導體元件之方法,此沒有限制。
再者,將參照下列範例詳細說明本發明,需了解,下列範例僅供例示說明用,不作為本發明之範疇的限制。
以黏合膜之固體含量100重量份為基準,將67.7
重量份之彈性體樹脂(AD-102S,Cheil Industries Co.,Ltd.)、13.5重量份之環氧樹脂(EPPN-502H,Japan Chemical Co.,Ltd.)、7.8重量份之胺固化劑(DDS,Wako)、1.5重量份之酚類固化劑(BPA,Kukdo Chemical Co.,Ltd.)(羥基基團當量:114g/eq)、0.5重量份之矽烷偶合劑(S-510,Chisso)以及9重量份之填料(R-972,Degussa)之混合物,溶於作為有機溶劑之環己酮中,使用珠磨機充份地揉合,然後使用塗佈器,沈積在經離型處理之PET膜上。之後,使混合物在100℃烤箱中乾燥20分鐘,如此製得60μm厚之用於半導體之黏合膜。
以與範例1相同之方法製備該用於半導體之黏合膜,但使用以該黏合膜之固體含量100重量份為基準,12.3重量份之環氧樹脂(EPPN-502H,Japan Chemical Co.,Ltd.)、5.5重量份之胺固化劑(DDS,Wako)以及5.0重量份之酚類固化劑(BPA,Kukdo Chemical Co.,Ltd.)。
以與範例1相同之方法製備該用於半導體之黏合膜,但使用以該黏合膜之固體含量100重量份為基準,11.7重量份之環氧樹脂(EPPN-502H,Japan Chemical Co.,
Ltd.)、3.9重量份之胺固化劑(DDS,Wako)以及7.2重量份之酚類固化劑(BPA,Kukdo Chemical Co.,Ltd.)。
以與範例1相同之方法製備該用於半導體之黏合膜,但使用以該黏合膜之固體含量100重量份為基準,13.8重量份之環氧樹脂(EPPN-502H,Japan Chemical Co.,Ltd.)以及9重量份之胺固化劑(DDS,Wako),沒有使用酚類固化劑。
以與範例1相同之方法製備該用於半導體之黏合膜,但使用以該黏合膜之固體含量100重量份為基準,10.1重量份之環氧樹脂(EPPN-502H,Japan Chemical Co.,Ltd.)以及12.7重量份之酚類固化劑(BPA,Kukdo Chemical Co.,Ltd.),沒有使用胺固化劑。
以與範例1相同之方法製備該用於半導體之黏合膜,但使用以該黏合膜之固體含量100重量份為基準,11.1重量份之環氧樹脂(EPPN-502H,Japan Chemical Co.,Ltd.)、2.5重量份之胺固化劑(DDS,Wako)以及9.2重量份之
酚類固化劑(BPA,Kukdo Chemical Co.,Ltd.)。
下表1顯示範例1至3以及比較例1至3中製得之各黏合膜之組成(重量份)。
將在範例1至3以及比較例1至3中製得之黏合膜在60℃下層疊至400~500μm,接著使用ARES,在溫度增加速率為50℃/min,應變5%以及頻率1雷得之條件下,測量40℃下之貯存模數。
將範例1至3以及比較例1至3中製得之各黏合膜在60℃下層疊至厚度450μm,接著經歷全部4個固化循環,各循環包括在125℃烤箱中半固化1個小時,然後在150℃熱盤上10分鐘。之後,接著使用ARES,在溫度增加速率為50℃/min,應變5%以及頻率1雷得之條件下,測量170℃下
之貯存模數。
將範例1至3以及比較例1至3中製得之各黏合膜與10×10mm之蓋玻片在60℃下疊在一起,在1kgf之力量下壓在PCB上1秒,在125℃下固化1個小時以及在150℃下固化1個小時,然後用EMC(SG-8500B,Cheil Industries Co.,Ltd.,Korea),在175℃下封膠60秒。在175℃下封膠固化1個小時後,用拋光器將樣本拋光,接著觀察空隙。使用網格比例尺,測量相對於黏合膜黏貼之PCB面積,空隙面積比率為5%或更小評估為非常良好的空隙特徵、空隙面積比率大於5%且不超過10%評估為良好空隙特徵,而空隙面積比率大於10%評估為粗劣空隙特徵。
將720μm厚塗怖二氧化物層之晶圓切成具有尺寸5×5mm之晶片。在60℃下使晶片與在範例1至3以及比較例1至3中製得之各黏合膜疊在一起,然後切割至僅留下黏合的部分,將上面具有尺寸5×5mm之晶片置於具有尺寸10×10mm之晶圓上,接著在120℃熱盤上施予10kgf之力量5秒,使晶片黏貼於黏合膜,接著在125℃烤箱中1個小時,在150℃熱盤上10分鐘進行固化,或在125℃烤箱中1個小時以及在150℃熱盤上10分鐘以及在175℃下1個小時進行固化。之後,使用Dage 4000,用100 N棒,在高度10μm以及
100 mm/s下,測量250℃下之晶粒抗剪強度。
將範例1至3以及比較例1至3中製得之各黏合膜安裝在150μm厚,塗佈二氧化物層以及具有尺寸10×10mm之晶圓上,以1 kgf 1秒壓在PCB上,接著在125℃下1個小時,然後在150℃下1個小時進行固化。之後,產物用EMC(SG-8500BC,Cheil Industries,Korea),在175℃下封膠60秒,接著在175℃下後固化1個小時。固化後,使所製得之試樣在85℃,85%RH恆溫/濕箱中吸收濕氣4個小時,在260℃最大值下進行IR回流三次。之後,透過SAT之t-scan技術(Sonix quantum 350),評估試樣之脫皮現像。發生脫皮評估為粗劣,而沒脫皮評估為良好。
下表2以及3顯示範例1至3以及比較例1至3中製得之黏合膜中,胺/酚類固化劑之莫耳%比率,以及實驗範例1至5之測量結果。
比較範例1至3以及比較例1與2,可見到含有胺固化劑以及酚類固化劑二者之黏合膜,在固化前後之貯存模數間,展現大的差異。此外,含有胺固化劑以及酚類固化劑二者之黏合膜,展現非常好的空隙特徵,且具有高固化後貯存模數,從而提供極佳的晶粒抗剪強度以及回流阻力。
另一方面,範例1至3以及比較例1與2之比較,可見到當胺固化劑(y)對酚類固化劑(x)之莫耳%比率小於0.3時,固化前後貯存模數間沒有差異之結果係不利的。此外,當莫耳%比率小於0.3時,黏合膜展現良好的空隙特徵,但具低固化後貯存模數,如此提供了不符合要求的晶粒抗剪強度以及回流阻力。
雖然提供了一些具體例以及圖式,但對熟悉此技藝之人士而言,很清楚地,該等具體例僅供例示用,且可在不逸離本發明之技術思想之範圍內,製造各種改質物、變化、改變以及相等具體例。本發明之範疇應僅受所附之申請專利範圍以及其相等物之限制。
Claims (16)
- 一種用於半導體之黏合膜,其含有結合樹脂;環氧樹脂;填料;胺固化劑以及酚類固化劑二者,該黏合膜具有80%或更多固化後170℃下之貯存模數(b),對固化前40℃下之貯存模數(a)之比率(b/a),在1.5至3.0之範圍內,其中該黏合膜在125℃下1個小時、在150℃下10分鐘以及在175℃下1個小時之固化後具有封膠後晶粒抗剪強度為9kgf或更高,並且其中該胺固化劑(y)對該酚類固化劑(x)之莫耳%比率(y/x)範圍從0.3至10。
- 如申請專利範圍第1項之黏合膜,其中該胺固化劑係二胺基二苯基碸。
- 如申請專利範圍第1項之黏合膜,其中該酚類固化劑係雙酚A或雙酚F。
- 如申請專利範圍第1至3項中任一項之黏合膜,其中該黏合膜在125℃下1個小時以及在150℃下1個小時之固化,在175℃下封膠60秒以及在175℃下封膠固化1個小時後,在黏合膜黏貼面積中,具有空隙面積比率為5%或更少。
- 一種用於半導體之黏合膜,其含有結合樹脂;環氧樹脂;填料;胺固化劑以及酚類固化劑二者,該黏合膜在125℃下1個小時以及在175℃下1個小時之固化後,具有晶粒抗剪強度為9kgf或更高,以及80%固化後170℃下之 貯存模數為5.0×106dyne/cm2或更高,其中該胺固化劑(y)對該酚類固化劑(x)之莫耳%比率(y/x)範圍從0.3至10。
- 如申請專利範圍第5項之黏合膜,其中該黏合膜在125℃下1個小時以及在150℃下1個小時之固化,在175℃下封膠60秒以及在175℃下封膠固化1個小時後,在黏合膜黏貼面積中,具有空隙面積比率為5%或更少。
- 如申請專利範圍第5或6項之黏合膜,其中該胺固化劑係二胺基二苯基碸。
- 如申請專利範圍第5或6項之黏合膜,其中該酚類固化劑係雙酚A或雙酚F。
- 一種用於半導體之黏合膜,其包含結合樹脂;環氧樹脂;填料;胺固化劑;以及酚類固化劑,其中該胺固化劑(y)對該酚類固化劑(x)之莫耳%比率(y/x)範圍從0.3至10。
- 如申請專利範圍第9項之黏合膜,其中在80%固化後170℃下之貯存模數(b),對固化前40℃下之貯存模數(a)之比率(b/a),範圍從1.5至3.0。
- 如申請專利範圍第9項之黏合膜,其中該黏合膜在125℃下1個小時、在150℃下10分鐘以及在175℃下1個小時之固化後,具有晶粒抗剪強度為9kgf或更高。
- 如申請專利範圍第9項之黏合膜,其中以該黏合膜之固體含量100重量份為基準,該黏合膜包括40至80重量份之該結合樹脂;1至30重量份之該環氧樹脂;1至30重量份之該填料;0.1至20重量份之該胺固化劑;以及0.1至 20重量份之該酚類固化劑。
- 如申請專利範圍第9項之黏合膜,其中該結合樹脂係彈性體樹脂。
- 如申請專利範圍第9項之黏合膜,其中該胺固化劑係二胺基二苯基碸。
- 如申請專利範圍第9至14項中任一項之黏合膜,其中該酚類固化劑係雙酚A或雙酚F。
- 一種半導體元件,其包含一配線基材;一如申請專利範圍第1-3和5-15項中任一項之用於半導體之黏合膜,其貼至該配線基材之晶片安裝表面;以及一半導體晶片,其安裝在該用於半導體之黏合膜上。
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CN103160220B (zh) | 2016-03-02 |
US9169425B2 (en) | 2015-10-27 |
TW201336958A (zh) | 2013-09-16 |
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