TW200815562A - Adhesive tape, connected structure and semiconductor package - Google Patents

Adhesive tape, connected structure and semiconductor package Download PDF

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Publication number
TW200815562A
TW200815562A TW096118934A TW96118934A TW200815562A TW 200815562 A TW200815562 A TW 200815562A TW 096118934 A TW096118934 A TW 096118934A TW 96118934 A TW96118934 A TW 96118934A TW 200815562 A TW200815562 A TW 200815562A
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TW
Taiwan
Prior art keywords
adhesive tape
resin
solder powder
substrate
solder
Prior art date
Application number
TW096118934A
Other languages
English (en)
Inventor
Satoru Katsurayama
Tomoe Yamashiro
Tetsuya Miyamoto
Original Assignee
Sumitomo Bakelite Co
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Filing date
Publication date
Application filed by Sumitomo Bakelite Co filed Critical Sumitomo Bakelite Co
Publication of TW200815562A publication Critical patent/TW200815562A/zh

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    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
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    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35Heat-activated
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    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02Electrically-conducting adhesives
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    • H05K3/30Assembling printed circuits with electric components, e.g. with resistor
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    • C08L2666/00Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
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    • C09J2301/40Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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Description

200815562 九、發明說明: 接合體及半導體封裝 【發明所屬之技術領域】 本發明係關於黏著帶、 【先如技術】 =有含有銲錫粒子之黏著帶,作為用於連接電極等導
人=件之㈣黏著帶(專敎獻υ。專利文獻丨中揭示有 各有銲錫粒子作料妹子之異向性導電膜㈤⑽咖C
Conductive Film , ACF)。 :,專利文獻2中所揭示的端子間之連接方法係使用有 包έ導電性粒子、及環氧系樹脂成分的導電性黏著劑,該 導電性粒子係包含具有Sn/In組成之合金。 進而’專敎獻3巾所揭示較,將銲錫球、蘋果酸等 助溶劑以及環氧樹脂混合而製造出黏著劑,並將此黏著劑 塗佈於形成有金屬化圖案之聚醯亞胺電路板上。 專利文獻1 :日本專利特開昭61 — 276873號公報 專利文獻2:曰本專利特開2〇〇4_26〇131號公報 專利文獻3:日本專利特開平4一 26289〇號公報 【發明内容】 (發明所欲解決之問題) >然而’專利文獻!之黏著帶、專利文獻2之導電性黏 '劑、專利文獻3之黏著劑不一定皆能在接合部分穩定地實 »現低電阻,因此於連接可靠度方面存在改善的餘地。、 本發明之目的在於提供可穩定實現低電阻之黏著帶,進 而提供使用有此黏著帶之接合體及半導體封裝。 312/發明說明書(補件)/96-10/96118934 6 200815562 (解決問題之手段) 根據本發明,提供電性連接導體構件之間的 黏著帶包含: 1 m 、 含有熱硬化性樹脂之樹脂層, 鲜錫粉,及 硬化劑; 上述銲錫粉與上述硬化劑存在於上述樹脂層中; •、上述樹脂層之硬化溫度T1與上述銲錫粉之i點τ2滿足 式(1);
Ti^T2+2〇C 式(1) 上述硬化溫度μ利用DSC,以1(rc/分鐘之升溫速度 測定黏著帶時的發熱波峰溫度; 上述樹脂層於上述銲錫粉线點T2的熔融黏度為5〇 Pa · s以上且5000 Pa · s以下。 利用本發明之黏著帶連接導體構件之間時,將黏著帶爽 籲持於導體構件之間,並加熱至既定溫度。鮮錫粉藉由加執 而炫融,炼融後之銲錫粉在樹月旨層中移動並自行對準地移 動至導體構件表面。由於録親如 "、鮮賜相對於金屬的潤濕性較佳, 故而可自4丁對準地移動至Μ Μ& /4· i 观主¥體構件表面。繼而,導體構件 表面與焊錫粉相接合,導辦椹 命聪構件之間得以電性連接。 ’專利文獻1中所揭示之黏著帶,由於難以控制樹脂之硬 ,化行為,因此無法將導電粒子配置於導體構件之間,故會 導致連接電阻變大。 相對於此,因本發明之斑芏册 <黏耆Y中含有硬化劑,故可對含 312/發明說明書(補件)/96-10/96118934 , 200815562 有熱硬化性樹腊之樹脂層的硬化特性加以控制。繼而,因 樹脂層於銲錫粉之熔點I的熔融黏度設在5〇Pa s以上, 故可使加熱炼融後之銲錫於樹脂層移動,且使薛錫聚集於 、 導體構件之間。 /'、 •又,因樹脂層於銲錫粉之熔點心的熔融黏度設在5〇〇〇 Pa.s以下,故可防止銲錫自導體構件之間溢出。 又’於使用專利文獻2中所揭示之黏著劑、專利文獻3 ⑩中所揭示之黏著劑的情況下,難以使銲錫聚集於導體構件 之間’故連接電阻會增大。 相對於此’本發明中’因使熱硬化性樹脂之硬化溫度 Tl與銲錫粉之㈣T2滿足UT2+2(rc的關係,故可使加 熱炼融後之銲錫粉平滑移動於硬化前的樹脂層中。藉此, 可使銲錫粉聚集於導體構件之間。 $外如上所述,因樹脂層於銲錫粉之熔點了2的熔融黏 度叹在50 Pa S以上,故可使加熱熔融後之銲錫移動於樹 _脂層,且使銲錫聚集於導體構件之間。 如上所述因树知層於銲錫粉之熔點L的熔融黏度 設在5000 Pa.s以下,故可防止處於導體構件之間的銲錫 自導體構件之間溢出。 進而’本發明中’黏著劑之形態為帶狀,故可製成易於 刼作者’從而可使導體構件之間的黏著步驟簡化。 •此時,上述銲錫粉之調配量,相對於銲錫粉以外成分的 口计100重量份,較佳為20重量份以上。 藉由將銲錫粉之調配量相對於銲錫粉以外成分的合計 312/發明說明書(補件)/96-10/96118934 〇 200815562 10〇重量份設為20重量份 之間的銲錫粉使導體構件 u利用聚集在導體構件 i構件確實地電性連接。 ,上述銲锡粉之平均粒徑,較佳 以下。 土為l//m以上且 可使銲锡粉 藉由將銲錫粉之平均粒几 滤每从屈人丄 J111 ^叹為1 # m以上 確貝地木合在導體構件表面。 又,藉由將銲錫粉之平均 、 制銲錫粉搭橋於相鄰導體槿株、〃 m以下’可抑 構件之間發生短路艘構件之間’從而可防止相鄰導體 形樹脂,較佳為包含室溫條件下為固 :、曰及至溫條件下為液狀之環氧樹脂者。 含述室溫條件下為固形之環氧樹脂,較佳為包 =二“b環氧樹脂與甲紛祕(⑽㈤膽。⑽型 上述室溫條件下為液狀之環氧樹脂,較佳為 又# i環氧樹脂或雙酚F型環氧樹脂。 猎由製成包含室溫條件下為固形之環氧樹脂與室溫條 下為液狀之環氧樹脂的熱硬化性樹脂,可提高樹脂溶融 A,的設計自由度。亦即,可容易地將含有熱硬化性樹脂 之树脂層於銲錫粉之熔點T2的熔融黏度控制在50 pa.s 以上且5000 Pa · s以下。 進而’較佳的是,上述硬化劑為具有助熔劑活性之硬化 劑。 藉由使树月曰層中存在此種具有助、熔劑活性之活性劑,可 使此具有助熔劑活性之硬化劑,高效率地移動於導體構件 ⑽發明說明書(補件)/964〇/96118934 200815562 與鲜錫之界面間。繼而,去除銲錫粉表面之氧化膜,可提 高鲜錫粉之潤濕性。藉此,能夠確實降低導體構件之間的 連接電阻值。 又’藉由使用具有助熔劑活性之硬化劑,能夠節省助熔 劑清洗(flux cleaning)步驟,因此可簡化製造步驟、降 低製造成本。 進而’上述含有助熔劑之硬化劑,較佳為含有羧基之硬 化劑。 又,根據本發明,可提供使用有如上所述之黏著帶的接 合體。具體而言,本發明之接合體係具備一對導體構件、 配置於此一對導體構件之間且電性連接一對導體構件 間的黏著帶,上述黏著帶係如上所述之黏著帶,係上述具 有助熔劑活性之硬化劑的50%以上的羧基與上述熱硬化性 樹脂產生反應者。 、若大量存在未與熱硬化性樹脂產生反應的具有助熔劑 f生之硬化劑,則如在尚溫條件下保管接合體的情況下會 致使導體構件腐蝕。 、相對於此,於本發明之接合體中,黏著帶中具有助熔劑 活性之硬化劑的5〇%以上的羧基與熱硬化性樹脂產生反 應,因此即便如在高溫條件下保管接合體的情況下,亦可 防止導體構件的腐餘。 (發明效果) ,據本發明,可提供能夠穩定實現低電阻之黏著帶,進 而提供使用有此黏著帶的接合體及半導體封裝。 10 312/發明說明書(補件)/96-10/96118934 200815562 【實施方式】 如上所述之目的、以及其他目的、特徵及優點,可藉由 以下所述之較佳實施形態以及隨附圖式,而得以進一步瞭 解。 、 以下’依據圖式,對本發明之實施形態作說明。 本發明之黏著帶係, 電性連接導體構件之間的黏著帶,其包含: 含有熱硬化性樹脂之樹脂層, 鲜錫粉,及 硬化劑; 銲錫粉與硬化劑存在於樹脂層中; 树脂層之硬化溫度Tl與銲錫粉之熔點I滿足式(丨); Ti^T2+20〇C 式(1) ,化溫度Tl係利用dsc,以i(rc/分鐘之升溫速度測定 黏著帶時的發熱波峰溫度; 樹脂層於銲錫粉之熔點T2的熔融黏度為50 Pa.s以上且 5000 Pa · s 以下。 以下’對各成分作具體說明。 人關於黏著帶之樹脂層’除了熱硬化性樹脂以外,較佳為 含^熱可塑性樹脂。就成膜性以及樹脂之熔融黏度的觀點 而《熱可塑性樹脂與熱硬化性樹脂的混合系為較佳。 t "、、可塱n树知並無特別限制,例如,可使用苯氧基樹 曰來树知、聚胺曱酸酯樹脂、聚醯亞胺樹脂、矽氧烷 改質聚醯亞胺樹脂、聚丁二烯、聚丙烯、苯乙烯-丁二烯- 312/發明說明書(補件)/96•膽6118934 200815562 苯乙烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯共聚物、聚縮 醛樹脂、聚乙烯醇縮丁醛樹脂、聚乙烯醇縮醛樹脂、丁基 橡膠、氯丁二烯橡膠、聚醯胺樹脂、丙烯腈-丁二婦共聚 物、丙烯腈-丁二烯-丙烯酸共聚物、丙烯腈—丁二烯—苯乙 烯共聚物、聚乙酸乙烯酯、尼龍、丙稀酸橡膠等。此等可 單獨使用或混合2種以上使用。 又’以提幵黏著性及與其他樹脂之相溶性為目的,上述 熱可塑性樹脂亦可使用具有腈基、環氧基、羥基、或羧基 者,例如可使用丙烯酸橡膠,作為此種樹脂。 熱硬化性樹脂並無特別限制,可使用環氧樹脂、氧雜環 丁烷樹脂、酚系樹脂、(曱基)丙烯酸酯樹脂、不飽和聚酯 树脂、鄰苯二甲酸二烯丙酯樹脂、馬來醯亞胺樹脂等。尤 其是,較佳使用硬化性與保存性、硬化物<耐熱性、耐濕 性、耐化學性方面優良的環氧樹脂。 …、 %<氧樹脂亦可使用室溫條件下為固形之環氧樹脂與室 溫條件下為液狀之環氧樹脂中的任意一種。又,樹脂 包含室溫條件下為固形之環氧樹脂與室溫條件 氧樹脂。藉此,可進一步提昇樹脂溶融行為的設計自 、室溫條件下為_之環氧樹脂並未❹m定,可舉出雒 岛A型壞氧樹脂、雙酶$型環惫糾匕 又 氧樹月匕、甲酪酪醛、主、央,衣乳树月曰、紛糸盼酸清漆型環 :树月曰〜祕>月漆型環氧樹脂、縮水甘 月曰、縮水甘油酯型環氧樹脂、3 衣虱树 气山 g靶衣乳樹脂、4官台匕芦 虱樹脂等。進一步具體而 4 匕3固形3官能環氧樹 312/發明說明書(補件)/96-10/96118934 ^ 200815562 脂與甲酚酚醛清漆型環負 齡紛_型輪炉曰。固形3官能環氧樹脂與甲 例中所使用的4將敍述之實施 基]仙-Π,丨-雙[4(23%;^氧基)笨 基]丙炫、U-雙[-[U;,丙氧基)苯基]乙基]笨 「 (2,3-環氧基丙氧基)苯 ^苯美一—㈠以-環氧基丙氧基璋基卜卜曱基比 土 J本基]本氧基]一2-丙醇等。 脂 樹月匕、件下為液狀之環氧樹脂為㈣Α型環氧 树月曰或雙㈣型環氧樹脂。又,亦可組合使用此等環氧樹 j ’至溫條件下為固形之環氧樹脂亦可包含固形三官能 =樹脂與甲紛祕清漆型環氧樹脂,而室溫條件下為液 =之環氧樹脂亦可為錢A型環氧樹脂或雙射型環氧樹 脂0 熱可塑性樹脂與熱硬化性樹脂之混合系的具體例,可舉 出的構成為樹脂包含環氧樹脂及丙烯酸橡膠。藉由設為黏 著帶包含丙烯酸橡膠的構成,可提昇製作膜狀黏著帶時的 成臈穩定性。又,由於可使黏著帶之彈性模數降低、使被 黏著物與黏著帶之間的殘留應力減小,因此可提昇對於被 黏著物的密著性。 本發明之黏著帶中熱可塑性樹脂的調配比係相對於除 了銲錫粉以外黏著帶之構成成分的合計,例如丙烯酸橡膠 設為10重量%以上且50重量%以下。藉由將丙烯酸橡膠之 调配比設為1 〇重量%以上,而抑制成膜性的降低,進而, 312/發明說明書(補件)/96-10/96118934 13 200815562 抑制著帶硬化後彈性模數的增加,因此可進一步提昇與 5〇气物的在著性。又,藉由將丙烯酸橡膠的調配比設為 苗〇 f里以下,可抑制樹脂溶融黏度的增加,使得銲錫粉 更確實地向導體構件表面移動。 .又作為熱硬化性樹脂之環氧樹脂的調配比係相對於除 if錫粉以外黏著帶之構成成分的合計,例如設為20、重 2里〇/°以且8〇重量%以下。藉由將環氧樹脂的調配比設為 重里上’可進—步充分確保黏著後的彈性模數,以 會If接可靠度。X ’藉由將環氧樹脂的調配比設為80 以下,可進而提高熔融黏度,因此可抑制 _著物降低連接可靠度的情況。 2熱可塑性樹脂與熱硬化性樹脂之混合系的其他例, 可牛出的構成為樹脂包含環氧樹脂以及苯氧基樹脂。藉 可使得黏著帶硬化後之耐熱性及耐濕性兩者之曰 衡更佳。 環氧樹脂之具體例可舉出如上所述之材料。 又,苯氧基樹脂之具體例,可舉出雙酚八型、雙酚Μ、 又紛S型、及具有苐骨架者。 =昇黏著帶之成膜性的觀點而言,樹脂中苯氧基樹脂 的魏比係將苯氧基樹脂相對於除了銲錫粉以外黏著帶 ,成分合計的比例’例如設為1〇重量%以上,較佳設 :15重量上n可確保因苯氧基樹脂所含經基產 的黏著性更佳。又,為了抑制樹脂熔融黏度的過度增 加’使銲錫粉能夠更4實地向導體構件表面移動,就此觀 312/發明說明書(補件)/96-10/96118934 200815562 點而言,將苯氧基樹脂相對於除了銲錫粉以外黏著帶之構 成成分合計的比例,例如設為50重量%以下,較佳設 40重量%以下。 又土认馬 ,如上所述,本實施形態中,樹脂層之硬化溫度L與鮮錫 •粉之熔點T2滿足ΤαΤ2+20ΐ的關係。 較佳為樹脂層之硬化溫度Tl在銲錫粉之熔點Τ2+ 。以上,更佳為樹脂層之硬化溫度1在銲锡粉之熔點Μ 45 •二上’尤佳為樹脂層之硬化溫度Tl在銲錫粉之熔點τ2 + 50 C以上。 2由設定TQT2+2(rc,可使加熱熔融後之銲錫粉在硬 體層中平滑地移動。藉此,可使銲錫粉聚集於導 。、,f树脂層之硬化溫度Tl設為銲錫粉之熔點 =上’更佳設為銲錫粉之㈣T2 + 45t以上,尤佳設為 :錫,之㈣T2+5(rc以上,藉此除了如上所述之效果以 上體會編相鄰導體構件之間,故可防止相鄰 V體構件之間的短路。 進而、,樹脂層之硬化溫度T1較佳在銲錫粉之熔點T2+ 、悉、以下,進而,尤佳在銲錫粉之熔點T2 + 8(TC以下。 :過此方式’熔融後的銲錫粉可在樹脂層硬化之前平滑地 進行移動。 此處树月曰層之硬化溫度?1係利用舰(耐 nning Cal0riraeter :示差掃描熱卡計),以听/分 之升溫速度測定黏著帶時的發熱波峰溫度。 312/發明說明書(補件)/96·1〇/961ΐ8934 200815562 又,鋅錫粉之熔點I係例如利用DSC,以i〇tt/分鐘之 升溫速度敎_粉單料的吸熱波峰溫度。 又,樹脂層於銲錫粉之溶點Τ2的熔融黏度為50 Pa.s 以上且5000 Pa.s以下。 、因將樹脂㈣銲錫粉之溶點T2的㈣黏度設為Whs 以上,故可使加熱溶融後之銲錫移動於樹脂層 聚集在導體構件之間。 f场 >此處’樹脂層於銲錫粉之溶點T2的熔融黏度尤佳為1〇〇 =.s以上。藉由將樹脂層於銲錫粉之熔點I的炫融黏度 又為100 Pa S以上’除了可使銲錫聚集在導體構件之間 的效果以外,例如,設為將導體構件設置在基板上之電極 的N況下,可抑制自上下連接基板之間溢出樹脂層及鮮錫 粉,因此可防止所謂絕緣不良的有關連接可靠度之問題。 又,、因樹脂層於鮮錫粉之炫點Τ2的熔融黏度設為刚〇 Pa s以下,故可防止銲錫自導體構件之間溢出。 此處,樹脂層於銲錫粉之熔點T2的熔融黏度尤佳為麵 =以1-藉由將樹脂層於銲錫粉之溶點心的溶融黏度 -又為4000 Pa s以下’除了可防止銲錫自導體構件之間溢 ί的效果以外’樹脂層可適度地流動,因此可確保對被黏 耆體的潤濕性,從而獲得充分之黏著性。 樹脂層之炼融黏度係使用黏著帶厚度為1〇〇 “的樣 品,利用動態黏彈性測定裝置,以〇1 Ηζ之頻率、1〇口 分鐘之升溫速度進行測量。 本發明之黏著帶中,可使用例如無錯銲錫作為構成銲錫 312/發明說明書(補件)/96-10/96118934 16 200815562 A粉的銲錫。無鉛銲鍚並未特別限定,但較佳為包含自%、 g以、111、211、及(:11所組成群組中選擇的至少兩種以 上之合金。女甘3 ^ ^ • /、疋’考慮到熔融溫度及機械物性,較佳為 .Sn,气金、Sn_Ag_Cu合金、sn,合金等含%的合金。 就充刀確保進行黏著帶黏著時之樹脂流動性的觀點而 =以銲錫粉之炫點T2例如設為lm:以上,較佳設為13〇 黏S二黏ί時,為抑制例如設於基板或晶片等被 、70件之劣化,就此觀點而言,銲錫粉之熔點 Τ2例如,為25(rc以下,較佳設為23〇〇c以下。 ..、、 又,銲錫粉之平均粒徑可視導體構件的表面面 體構件㈣隔而設定,較佳為…以上且100 ”以^ 就為使&錫粉確實地集合在導體構件表面的觀點而言,例 如《又#錫粉之平均粒徑為5 # m以上較佳為U # m 以上。又,要在導體構件表面選擇性地形成銲錫區域,並 且在電極形成區域等欲使之導通的區域以外的區域中,確 保黏著帶之絕緣性,就此觀點而言,例如,設銲錫粉之平 均粒徑為100 以下’較佳為50 “以下。此處,銲 錫,之平均粒徑係利用例如雷射繞射散射法而進行測定。 藉由將銲錫粉之平均粒徑設為1㈣以上,可使銲鍚粉 確實地集合在導體構件表面。 又,藉由將銲錫粉之平均粒徑設為100 以下,可抑 制銲錫粉搭橋於相鄰導體構件之間,從而可防止相鄰導體 構件之間的短路。 又’本發明之黏著帶中,就提昇連接可靠度的觀點而 312/發明說明書(補件)/96-10/96118934 17 200815562 言,相對於除了銲錫粉以外之成分的合計1〇〇重量份,設 銲錫粉之調配比為20重量份以上,較佳設為4〇重量份二 上。又’就提昇黏著帶之成膜性的觀點而言,相對於黏著 、帶中除了銲錫粉以外之成分的合計100重量份,設銲錫粉 , 之調配比為250重量份以下,較佳設為230重量份以下。 又,本發明之黏著帶中,相對於除了銲錫粉以外之成分 的合計100重量份,銲錫粉之調配比亦可為2〇重量份以 修上,且,銲錫粉之平均粒徑亦可為! "m以上且1〇〇 以下。如此,藉由選擇性地於導體構件表面形成銲錫區 域、及在電極形成區域等欲使之導通的區域以外的區域中 確保黏著帶之絕緣性,可更加提昇黏著帶之成膜性的平 本發明中所用之具有助熔劑活性的硬化劑係表示具有 將銲錫粉表面之氧化膜還原至可與導體構件電性接合的 功能,且,具有與樹脂進行鍵結之官能基的化合物。例如, _樹脂包含環氧樹脂的情況下,具有助熔劑活性的硬化劑, 亦可具有羧基、及與環氧基產生反應的基。與環氧基產生 反應的基,例如,可舉出羧基、羥基、胺基等。 就於黏著時去除銲錫粉表面之氧化膜的觀點而言,具有 助溶?=!]活丨生之硬化劑可視銲錫粉種類加以適當選擇後使 ^ 用。 •具有助熔劑活性之硬化劑,例如為含有絲的化合物。 而S有羧基之化合物,例如,可舉出直鏈狀或具有支鏈之 烷基羧酸、芳香族羧酸等羧酸類。 312/發明說明書(補件)/96-1〇/96118934 18 200815562 烷基羧酸,具體而言,可舉出 H00C-(CH2)n-c〇〇H (1) 下述式(1)所示之化合物。 上述式(1)中,ng〇以上且 以下的整數。 又,考慮到助熔劑活性、黏著時 黏著帶硬化後之彈性模數及麵 ^二gas)、及 ⑴中之讀的转,上述式 卜籍由將η設為 可抑制因環氧樹脂交聯間 又為4以上 -^ ^^ ^ 雕尥短所造成的黏著帶硬化
後之弹性杈數的增加,從而提^ ^ ^ ^ ^ ^ # 心汁,、饭黏者物的黏著性。 又’糟由將η設為1 〇以下,可私制 " , A 抑制因裱氧樹脂交聯間距 離過長所造成的彈性模數之降低 牛低攸而可進一步提昇連接 上述式(1)所不之化合物,例如,可舉出n= 4之己二 (眶-陶广咖)、!^之癸二酸 、及 n=l〇 之 HOOC-(CHA。-COOH。 進一步具體而言,芳香族羧酸,可舉出包含一分子中至 鲁少二個紛性經基、及一分子中至少一個直接鍵結於芳香族 之羧基的化合物。此種化合物,例如,可舉出2 3二羥 基苯甲酸、2,4-二羥基苯甲酸、龍膽酸(2,5_二羥基苯^ 酸)、2, 6-二羥基苯甲酸、3,4_二羥基苯甲酸、五倍子酸 (3, 4’ 5-三羥基苯甲酸),還原酚酞(2_[雙(對羥基苯基) •甲基]苯甲酸)等苯甲酸衍生物;1,4-二羥基-2—萘甲酉1、 .3’ 5-二羥基-2-萘曱酸、3, 7-二羥基-2-萘甲酸等萘甲酸衍 生物;以及雙酚酸(diphenolic acid)等。 進一步具體而言,具有助熔劑活性之硬化劑,可舉出如 312/發明說明書(補件)/96-10/96118934 19 200815562 ^所2之头—酸以及龍膽酸,亦可包含此等其中之-或任 思一種。 〜 =發明之黏著帶中’具有助溶劑活性之硬化劑,可 粉外部,既可為例如銲錫粉與具有 於樹脂中,亦可附著於分散繼中的:錫 硬化劑,存在於銲錫粉 ... 者守具有助熔劑活性之硬化劑可於锃 錫與黏著構件中之導雷 j於鋅 令包材枓的界面間高效率地進行移 動,從而可使導體構件與銲錫直接接觸。藉此,可提曰、查 中,因此可右对^ 劑活性之硬化劑存在於樹脂 戋Tg。 y σ、於樹脂中,從而提高樹脂之彈性模數 配:’ r發明之黏著帶中,具有助熔劑活性之硬化劑的調 就提昇助熔劑活性的觀▼之構成成刀的&計’ =調配比設為例如…量%以上,較佳設為i重量硬: 二又:就降低黏著時樹脂之溶融黏度的觀點而言,相 、除了知錫粉以外黏著帶之構成成分的合計,將 熔劑活性之硬化劑的調配b & ' 設為丨。重量%以下。“為例如3°重量%以下,較佳 進一步具體而言,本發明之激益册 下,相對於黏著帶中的環氧批^有環氧樹脂的情況 仆旬, 衣虱树脂,將具有助熔劑活性之硬 :的:配比设:例如50重量%以下,較佳設為3〇重量% 下。透過此方式,可消除硬化劑過多現象,使硬化性得 312/發明說明書(補件)/96-10/96118934 2〇 200815562 以改善。 再者,本發明之黏著帶,亦可在樹脂中進一步包含與具 有助熔劑活性之硬化劑不同的其他硬化劑,又,亦可含有 , 作為硬化劑而發揮作用的樹脂。 硬化劑並未特別限定,可舉出酚類、胺類、硫醇類,考 慮到與環氧樹脂的反應性及硬化後的物性,較隹使用驗 類。 _ 酚類並未特別限定,考慮到黏著帶硬化後的物性,較佳 為2官能以上。例如,雙酚a、四甲基雙酚A、二烯丙基 雙酚A、聯苯酚、雙酚f、二烯丙基雙酚F、三酚 (trisphenol)、四酚(tetrakisphen〇1)、酚系酚醛清漆 類、甲酚酚醛類等,但考慮到熔融黏度、與環氧樹脂的反 應性以及硬化後的物性,可較佳使用酚系酚醛清漆類以及 甲酚酚酸類。 又,具有助熔劑活性之硬化劑以外的硬化劑之調配比, 籲在將除了銲錫粉以外黏著帶之構成成分的合計設為1〇〇 時,就確實地使樹脂硬化的觀點而言,例如設為5重量% 以上’較佳設為10重量%以上。又,就提昇黏著時樹脂之 流動性的觀點而言,在將除了銲錫粉以外黏著帶之構成成 ^的合計設為100時,將硬化劑之調配量例如設為4〇重 -量%以下,較佳設為30重量%以下。 ,又,本發明之黏著帶,亦可進一步含有硬化觸媒。藉由 設為含有硬化觸媒之構成,於製作黏著帶時,可使樹脂進 一步確實地硬化。 312/發明說明書(補件)/9640/96^34 21 200815562 硬化觸媒可視樹脂之種類作適當選擇,例如, 點為15G°C以上的㈣化合物。若咪唾化合物之溶點過奋 低’則在銲錫粉移向電極表面之前,黏著帶中的樹脂^硬 化而導致連接不敎、或黏著帶之保存性降低。因此: 唑之熔點較佳為丨5{rc以上。熔點為15〇它以上的咪唑化 合物,可舉出2-苯基_峻、2-苯基+甲基經基:米唾、 2-苯基-4, 5-二羥基咪唑、2_苯基_4_甲基咪唑等。再者 咪,化合物熔點的上限並無特別限制,例如可視黏著册之 黏者溫度而作適當設定。 又,硬化觸媒之調配比,在將除了銲錫粉以外黏著帶之 構成成分的合計設為⑽時,就進—步有效發揮環氧㈣ 作為硬化觸媒的作用而提昇黏著帶之硬化性的觀點而曰 言,例如設為〇.〇01重量%以上,較佳設為〇 〇1重量%以 上。又,硬化觸媒之調配比,例如設為5 里0 過此方式’可進一步提昇黏著帶之保存性。° 、 又,本發明之黏著帶,亦可進一步含有石夕燒偶合劑。藉 由設為含有矽烷偶合劑之構成’可進—步提昇黏 : 黏著物的密著性。矽烷偶合劑之具體例,可舉出環氧矽烷 偶合劑、含有芳香族之胺基矽烷偶合劑等,只要含有此= 中至少其中之—即可。χ,例如可設為含有此等兩者之構 成。矽烷偶合劑之調配比’在將除了銲錫粉以外黏著帶之 構成成分的合計設為100時,例如設為〇 〇1〜5重量%程 度。 〇壬 進而’本發明之黏著帶,亦可含有上述以外的成分。例 312/發明說明書(補件)/96·10/96118934 22 200815562 如,為了提昇樹脂之相溶性、 亦可適當添加各種添加劑。 穩定性、作業性等各種特性 明之黏著帶的製作方法作說明。黏著帶係 :由:途方式而獲得…混合樹脂、銲錫粉 及視需要而加入的其他添加劑,並使銲 ^及具有助_活性之硬化劑分散於樹脂中,繼而,將 产::ΓΓ塗佈於聚醋片材等剝離基材上,並在既定溫
度條件下進行乾燥。 所传之膜狀黏著帶係銲錫粉及具有助溶劑活性之硬化 劑存在於樹脂層卜當將此黏著帶配置於被黏著物之間進 行加熱時’樹脂層中的銲錫粉將自行對準地移動至被黏著 物中導體構件的表面,從而形成金屬接合。 參照圖卜進一步具體說明使用有本發明之黏著帶的黏 ^ 一基板109、黏著帶10卜第二基板1〇7、黏著帶1〇1、 及:三基板105依此順序自下而上進行積層。此時,使設 於第一基板109表面的第一電極(導體構件)113與設於第 二基板107表面的第二電極(導體構件)115相對向。又, 使。又於第一基板107表面的第二電極(導體構件)ι2ι與設 於第三基板105表面的第三電極(導體構件)119相對向。 再者,第二基板1〇7中,既可於通道孔117的内部埋設 既定材料,亦可使通道孔丨〗7為通孔。 繼而,以既定溫度加熱積層體使之黏著。藉此形成接合 體。黏著溫度係可視黏著帶1〇1中銲錫粉1〇3之材料以及 312/發明說明書(補件)/96-10/96118934 23 200815562 樹脂材料而作設定。 黏著溫度,設為高於銲錫粉1〇3之熔融溫度且樹脂層 132處於熔融狀態下的溫度。就此觀點而言,黏著溫度曰例 如設為高於loot,較佳設為12(rc以上。又,關於黏著 溫度,較佳為樹脂之熔融黏度低,就此觀點而言,黏著溫 度例如設為25CTC以下,較佳設為20(rc以下。又,就^ 展樹脂熔融黏度低之區域的觀點而言,可降低黏著溫度。 就使銲錫粉103流動於電極表面而進一步高效率地進 行移動的觀點而言,於黏著時,可以既定壓力施壓。就進, 二步確實地形成銲錫區域U1的觀點而言’施壓壓力例如 設為0 MPa以i,較佳設為i胸以上。再者即便有咅 向黏著帶施加的壓力為〇 MPa,亦可藉由黏著帶上所配= ,構件的土重’對黏著帶施加既定壓力…就進一步提 幵連接可靠度的觀點而言,施壓壓力例如設為2〇 Μ%以 下,較佳設為10 MPa以下。 極121與第三電極1J 9 111 俄错由加熱,黏著帶101中之樹脂層132熔融。又,黏著 帶101中之銲錫粉103熔融。熔融後之銲錫粉1〇3,自樹 脂層132中自行對準地移動至設於各基板表面的電極 上。由於鮮錫粉1G3向電極之對向區域進行自動對準因 此在第-電極113與第二電極115之間的區域、及第二電 區域,分別形成銲錫區域 又,存在於樹脂中的具有助熔劑活性之硬化劑(未圖 不),高效率地移動於銲錫粉1G3與電極的界面之間,並 312/發明說明書(補件)/96-i〇/96i 18934 24 200815562 且去除銲錫粉103表面之氧化膜,因此銲錫區域Η〗與各 電,直接金屬接合而電性連接。其後,藉由冷卻積層體, 使得黏著帶中的樹脂硬化,從而電極之間由銲錫區域^ . 接合的狀態得以維持。 . 如此般,當使用帶狀黏著帶101時,只要於黏著時加熱 ,理至既定之單一溫度,基板之間即可簡單地黏著。但 是,黏著時之加熱處理,並非限於單一溫度條件下的處 ❿里例如,亦可進行分步固化(step cure)處理,即,於 150°C加熱1〇〇秒鐘後s2〇(rc再加熱1〇〇秒鐘或後固 化(P〇Stare)處理,即,於18〇。〇進行熱壓接合ι〇秒鐘 後於200 C再烘焙固化(oven cure)1〇分鐘。又藉由構 成銲鍚粉103之銲錫粒子的金屬接合,電極與黏著帶1〇1 中的銲錫相連接,因此連接電阻低、連接可靠度高。 如此所形成之接合體,較佳為黏著帶1〇1中具有助熔劑 活性之硬化劑之羧基的5〇%以上與樹脂層之熱硬化性樹脂 ⑩產生反應。 尤其是,較佳為黏著帶1〇1中具有助熔劑活性之硬化劑 之羧基的70%以上與熱硬化性樹脂產生反應。 藉由黏著帶中具有助熔劑活性之硬化劑之羧基的5〇%以 亡,較佳為70%以上與熱硬化性樹脂產生反應,即便如在 冋μ ir、件下保管接合體的情況下,亦可防止導體構件之腐 ^ ϋ ° 反應率可以如下方式進行測定。 貝細*絰180 C、10分鐘氮取代且藉由烘箱而硬化後的黏 312/發明說明書(補件)/96-10/96118934 25 200815562 著帶與未硬化之黏著帶的IR測定。 出現在羧基源之1600 cnf1附近的硬化前之波峰強度設 為(A),硬化後之波峰強度設為〇)的情況下,利用下述式 、 計算硬化度。 $ 硬化度(%)= {1—(Β)/(Α)} χίοο 本發明之黏著帶的構成係與被黏著物之密著性優良,並 且使導體構件間的電性連接可靠度優良。例如,亦可將本 籲發明之黏著帶用於電子設備中,以使電子或電氣零件之間 接合並使其等電性連接。電子設備具體而言可舉出電腦、 電視機、行動電話、遊戲機、各種通訊設備以及測定設備。 又,本發明之黏著帶即便於被黏著物中導體構件之接合 面積小的情況下亦能夠確實地進行接合,因此例如在半^ 體封裝中,可較佳用於如基板或晶片的連接。 例如,本發明之黏著帶可用於半導體封裝中基板之 黏著。 • 使用有本發明之黏著帶的半導體封裝,例如,係將第一 ,板黏著咿、及第二基板依此順序進行積層,由此設於 基板的第一電極與設於第二基板的第二電極介隔黏、 者▼中之杯錫區域而連接在一起。 黏著帶係於黏著後之狀態下,具有樹脂及貫通樹脂的銲 錫區域於树脂中,具有助溶劑活性之硬化劑殘存與否皆 再,,如後文實施例中所述般,銲錫區域自黏著帶内部 朝向第一電極及第二電極側擴展。由於黏著帶兩面上銲錫 m/__mMm/96-1〇/961l8934 200815562 S域擴大’因此構成為黏者帶中鲜錫區域與樹脂的密著性 優良,並且第一及第二電極與銲錫區域的接觸面積大。 將本發明之黏著帶用於基板的黏著時,於第一及第二基 板的表面上,既可設置阻焊劑,又,亦可不設阻焊劑。 圖2為說明連接無阻焊劑的基板之間的方法之剖面圖。 圖2中,於第一基材133及第二基材131上,分別設有 第一電極(導體構件)137及第二電極(導體構件)135。將 本發明之黏著帶1 〇 1配置於基板之間並加熱至既定溫
度,藉此樹脂層132將基板間彼此黏著,並且銲錫粉自行 對準地移動至第一電極137與第二電極135的表面,使得 此等電極之間藉由銲錫區域111而連接起來。 又’圖3為說明連接具有阻焊劑的基板之間的方法之剖 面圖。圖3之基本構成與圖2相同,但在以下方面不同, 即,於第一基材133及第二基材131上分別設有第一阻焊 劑層141及第二阻焊劑層139,而第一電極137及第二電 極135分別埋設於第一阻焊劑層141及第二阻焊劑層i = 中。繼而,於第一電極137與第二電極135之對向區日域的 既定位置上,設置貫通第一阻焊劑層141及第二阻焊劑芦 139的空隙部143。 曰 於黏著此種基材間之情況時,亦將本發明之黏著帶 配置於基板之間並加熱至既定溫度。藉此,銲錫粉 準地移動至自空隙部143露出的第一電極137與第二電極 135的表面,以填埋空隙部143。由此,佈線之間藉 錫區域111而連接起來。 9 ψ 312/發明說明書(補件)/96-10/96118934 27 200815562 又,本發明之黏著帶亦可用 之間的黏著。 於半導體封裝中半導體晶片 圖4及圖5為表示半導齅曰η ¥體日日片之間由黏著帶黏著後的半 導體封裝(接合體)之構成的剖面圖。 於圖4中,第二半導靜bh 卞♦篮b曰片153、黏著帶i〇1、及第一 半導體晶片151依此順序進行及弟 貝序進仃知層,作為第二半導體晶片 15 3之導體構件的電極^去同 ⑴夕…^ )與作為第-半導體晶片 151之導體構件的電極〔去 A ^ 未圖不),介隔黏著帶101中的銲 錫區域111而相連接。又,筮一 fc 受又第一+導體晶片153背面所設 電極與晶片搭載基板(梦西其士 ^ 槪〔衣配基板155)之電極藉由導線159 =接。弟一半導體晶片15卜第二半導體晶片153、 ¥線159由密封樹月旨163密封。於裝配基板155之背 面’设有多個凸塊電極16 j。 又囷5之基本構成與圖4相同,但於圖5中,第二半 導體晶片153介隔凸塊電極165倒裝⑴ip)連接於裝喊 板155,裝配基板155與第二半導體晶片153之間 第一半導體晶片151。 於圖4及圖5中,第一半導體晶片151與第二半導體晶 片153藉由本發明之黏著帶1〇1而黏著。因此,相比晶片 間由凸塊電極連接的構成,可使封裝厚度變薄。又,藉由 使用,著帶⑻,能夠以簡單步驟進行晶片間之黏著:並 且以高連接可靠度穩定地連接晶片之電極間。 進而,本發明之黏著帶,亦可用於進一步將半導體封裝 之裝配基板搭載於其他基板上時的基板間之黏著。例如: 312/發明說明書(補件)/96-10/96118934 28 200815562 亦可用於將半導體封裝二次裝配於如Pc板(印刷電路板) 上時。 圖6為表示此種半導體封裝之構成的剖面圖。於圖6 中’搭載有半導體晶片(第一半導體晶片151及第二半導 體晶片153)的第一基板(裝配基板155),與搭載裝配基板 155的第二基板(基板157)係藉由黏著帶1〇1而黏著。基 板157可設為例如pc板。第一半導體晶片丨5〗與第二半 導體晶片153之間填充有樹脂167。又,第一半導體晶片 151及第二半導體晶片153上所設電極(未圖示),分別介 隔導線169及導線in連接於裝配基板155上之電極(未 圖示)。 於圖6中,由於裝配基板155與基板157藉由黏著帶 101而黏著,因此基板上所設電極彼此間能夠以高可靠度 穩定地連接。又,藉由使用黏著帶1〇1,可縮小基板間隔二 因此可使封裝的整體厚度變薄。 以上,麥照圖式已對本發明之實施形態加以敍述,但此 等為本發明的例示,亦可採用除了上述構成以外的各種構 成。 (實施例) (黏著帶之製作) 製作出厚40 ”之含有樹脂、銲錫粉、及具有助熔劑 活性之硬化劑的黏著帶(實施例卜⑻。又,料比較例, 製作出厚40 ^之含有樹脂、銲錫粉、及具有 性之硬化劑的黏著帶(比較例1〜4)。 312/發明說明書(補件)/96-10/96118934 29 200815562 於表1〜表4以及表13中’以重ΐ份表示各成分之調 配。針對各實施例以及各比較例,按照表1〜表4以及表 13中所示之調配,將各成分溶解於甲笨、二甲苯等芳夭 族煙系溶劑,乙酸乙醋、乙酸丁酿等醋系有機溶劑,丙^同曰、 甲基乙基酮等酮系有機溶劑中,將所得之清漆塗佈於聚醋 片材上’並以使上述有機溶劑揮發的溫度進行乾燥。
312/發明說明書(補件)/96-10/96118934 200815562[表1]
功能 成分 構造等 實施例 1 實施例 2 實施例 3 實施例 4 實施例 賦予成膜性 低彈性模數化 丙烯酸_ (丙烯酸丁酯)-(丙烯酸乙酯)—(丙稀腈)= 30mol%/30niol%/40inol% 分子量=85萬 25.9 25.9 25.9 25.9 U 25.9 聚乙婦醇縮丁 麵脂 聚合度=1700、乙醢化度=3mol%以下 縮丁略it·度=65船1°/〇以上、流動軟化點=225°C 苯iii封脂 雙酚A骨架、數量平均分子量=30000 硬化成⑽ 環細月旨— 齡名稱記侧1 24.5 24.5 24.5 24· 5 215 硬化成⑽ 環氧樹脂 曱酚祕清漆型環氧樹脂、軟化點80°C 16.3 19.3 6.3 16.3 16.3 硬化成分③ 環氧樹脂 液狀雙酚F型環氧樹脂、環氡基當量=170 7.5 7.5 7.5 7.5 7.5 硬化劑 酚系齡酸清漆 軟化點=100°C、0H當量=104 20.2 20.2 20.2 20.2 20.2 賦予密著性① 矽烧偶合劑 3-縮水甘油氧基丙基三曱氧基石夕烧 0.1 0.1 0.1 0.1 0.1 賦予密著性② 矽烧偶合劑 N-苯基-3-胺基丙基三甲氧基石夕烧 0.35 0.35 0.35 0.35 0.35 硬·媒 咪峻 2-苯基-4,5-二經基味唑 0.15 0.15 0.15 0.15 0.15 咪°坐 2-苯基-4-曱基味唑 具有助熔劑活性 伙化劑 癸二酸 H00C-(CH2)8-C00H 5.0 2.0 15.0 己二酸 H00C-(CH2)4-C00H 5.0 H00C-(CtfcVCOOH 龍膽酸 2,5-二經基苯曱酸 5.0 合計 100.0 100.0 100.0 100.0 100.0 導電性粒子 銲錫粉 Sn/Bi=42/58、溶點=138°C、平均粒徑 35 μ® 60 60 60 60 60 Sn/Bi=42/58、熔點=138°C、平均粒徑 20 μ® Sn/Bi=42/58、溶點=138°C、平均粒徑 12 μιη Sn/In=48/52、熔點=118°C、平均粒徑 35 μιη *1:2-[4-(2,3-環氧基丙氧基)苯基]_2-[4-[1,1-雙[4-(2,3-環氧基丙氧基)苯基]乙基]苯基]丙烷,與1,3-雙 [4-[1-[4-(2, 3-環氧基丙氧基)苯基]—:^4^4-(2,3-環氧基丙氧基)苯基Η-甲基]乙基]苯基]苯氧基]-2-丙 醇的混合物 312/發明說明書(補件)/96-10/96118934 31 200815562 調配 > 功能 成分 構造等 實施例 6 實施例 7 實施例 8 實施例 9 實施例 10 賦予舰性 低彈性模數化 丙烯酸娜 (丙烯酸丁酯)-(丙烯酸乙酷)—(丙烯腈)= 30mol%/30mol%/40mol% 分子量=85萬 25.9 25.9 25.9 25.9 25.9 聚乙稀醇縮丁 麵脂 聚合度=1700、乙酿化度=3mol%以下 縮丁SS化度=65mol%以上、流動軟化點=225°C 雙酚A骨架、數量平均分子量=30000 硬化成 環·^^月旨 構雜稱記 24.5 24.5 24.5 24.5 24.5 硬化成分(D 環細脂 甲驗祕清漆型環氧樹脂、軟化點8(TC 16.3 16.3 16.3 16.3 16.3 硬化成⑽ 王哀月旨 液狀雙紛F型環氧樹脂、環氧基當量=170 7.5 7.5 7.5 7.5 7.5 硬化劑 酚系酸齡清漆 軟化點=100°C、OH當量=104 20.2 20.2 20.2 20.2 20.2 賦予密著性① 矽貌偶合劑 3-縮水甘油氧基丙基三甲氧基石夕烧 0.1 0.1 0.1 0.1 0.1 賦予密著性② 矽烧齡劑 N_苯基-3-胺基丙基三甲氧基石夕烧 0.35 0.35 0.35 0.35 0.35 硬錢媒 咪嗤 2_苯基-4,5-二口米唾 0.15 0.15 0.15 0.15 咪唑 2-苯基-4-甲基咪嗤 0.15 具有助熔劑活 性之硬化劑 癸二酸 H00C-(CH2)8-C00H 5.0 5.0 5.0 5.0 己二酸 H00C-(CH2)4-C00H HOOC-(CH2)i〇-COOH 5.0 麵酸 2,5-二經基苯甲酸 樹脂合計 100· 0 100.0 100.0 100.0 100.0 導電性粒子 銲錫粉 Sn/Bi=42/58、溶點=138°C、平均粒徑 35 pm 60 60 Sn/Bi=42/58、熔點=138ΐ、平均粒徑 20 pm 60 Sn/Bi=42/58、溶點=138°C '平均粒徑12啊 60 Sn/In=48/52、溶點=118°C、平均粒徑 35 pm 60 *1 : 2_[4-(2,3-環氧基丙氧基)苯基]-2-[4-[l,l-雙[4-(2,3-環氧基丙氧基)苯基]乙基]苯基]丙烷,與雙 [4-[H4-(2,3-環氧基丙氧基)苯基]+[4-[1-[4-(2,3-環氧基丙氧基)苯基]+甲基]乙基]苯基]苯氧基]-2_丙醇的 混合物 32 312/發明說明書(補件)/96-10/96118934 200815562 [表3] ^配I功能 成分 構造等 實施例實施例實施例實施例 11 12 13 賦予成膜性 低彈性模數化 丙稀酸橡膠 (丙稀酸丁醋)一(丙烯酸乙§旨)一(丙婦腈)== 30mol%/30mol%/40mol% 分子量=85萬 15· 0 45. 0 聚乙締醇縮丁 駿樹脂 聚合度= 1700、乙酿化度 縮丁酸化度=65mol%以上 3mol%以下 流動軟化點: =225°C 25.9
賦予密著性②矽烷偶合劑 硬化觸媒 π米。坐 Ν-苯基-3-胺基丙基三甲氧基石夕统 2-苯基-4, 5-二經基咪嗤 0.35 0.35 0.35 0.35 ,15 0.15 0.15 0.15 具有助熔劑活 性之硬化劑 2_苯基-4-甲基咪唾
酉复 H00C-(CH2)8-C00H 己二酸
H00C-(CH2)4-C00H
HOOC- (Cffe ) ίο - COOH 5.0 5.0 5.0 5.0 龍膽酸 樹脂合計 2, 5-二羥基苯甲酸 導電性粒子銲錫粉 Sn/Bi=42/58、熔點·°c、平均粒彳 100.0 100.0 100.0 100.0
Sn/Bi =42/58 ^ 熔點=138°C、平均粒彳 Sn/Bi =42/58、熔點=138。(:、平均粒
312/發明說明書(補件)/96-10/961廣34 33 200815562 [表4] 調 配 功能 成分 構造等 比較例1 比較例2 比較例3 比較例4 賦予成膜 性 低彈性模 數化 丙婦酸橡 膠 (丙烯酸丁醋)一(丙烯酸乙g旨)一(丙缔 腈)=3 Omo1%/3 Omo 〖%/4〇mo 分子量=85萬 25.9 5.0 70.0 70.0 聚乙烯醇 縮丁醛樹 脂 聚合度= 1700、乙醯化度=3mol%以下 縮丁醛化度= 65mol%以上、流動軟化點 = 225〇C •一 苯氧樹脂 雙酚A骨架、數量平均分子量=3000〇 硬化成分 ① 環氧樹脂 構造名稱記載於*1 24· 5 35.4 硬化成分 ② 環氧樹脂 曱酚酚醛清漆型環氧樹脂、軟化點8〇。〇 16.3 16.3 10.0 10.0 硬化成分 ③ 壤氧樹脂 液狀雙酚F型環氧樹脂、環氧基當量== 170 7.5 7.5 7.5 7.5 硬化劑 酚系酚醛 清漆 軟化點= 10(TC、0H當量= 104 30.2 6.9 賦予密著 矽烷偶合 劑 3-縮水甘油氧基丙基三曱氧基矽烷 0.1 0.1 0.1 0.1 賦予密著 j±© 矽烷偶合 劑 N-苯基-3-胺基丙基三甲氧基石夕烧 0.35 0.35 0.35 0.35 硬化觸媒 咪峻 2-苯基-4, 5-二經基咪嗤 0.15 0.15 咪嗤 2-苯基-4-曱基咪唑 潛在性硬 化劑 Novacure HX-3941HP*2 20.4 7.1 具有助燦 癸二酸 H00C-(CH2)8-C00H 5.0 5.0 5.0 5·0 劑活性之 己二酸 H00C-(CH2)4-C00H 硬化劑 H00CKCH2)旷 C00H 龍膽酸 2, 5-二經基苯甲酸 避:脂合計 100.05 100.0 100.05 100.0 導電性粒 子 銲錫粉 Sn/Bi=42/58、熔點=138°C、平均粒徑 35 μιη 60.0 60.0 60.0 60.0 Sn/Bi=42/58、熔點=138°C、平均粒徑 20 μιη Sn/Bi=42/58、熔點=138°C、平均粒徑 12 μπι Si^In=48/52、熔點=118°C、平均粒徑 35 m W : 2-[4-(2,3-環氧基丙氧基)苯基]-2-[4-[l,l-雙[4-(2,3-環氧基丙氧基)苯基]乙基]苯基]丙烷,與1,3-雙 U-[l-[4-(2,3-環氧基丙氧基)苯基]-i-[4-[l-[4-(2,3-環氧基丙氧基)苯基]-1-曱基]乙基]苯基]苯氧基]-2-丙醇的 處合物 :咪唑系潛在性化劑,旭化成化學公司製造 312/發明說明書(補件)/96-10/96118934 34 200815562 又,表5〜表8以及表14中展示各實施例、比較例之 樹脂層於樹脂層之硬化溫度L、銲錫粉熔點1的熔融黏 度。 [表5] 實施例1 實施例2 實施例3 實施例4 實施例5 樹脂層之硬化溫度(Tl) 196 202 189 204 200 銲錫粉之熔點(Τ2) 138 138 138 138 138 樹脂層之溶融黏度 430 350 660 450 490 Τι-Τ2 58 64 51 66 62 [表6] 實施例6 實施例7 實施例8 實施例9 實施例10 樹脂層之硬化溫度CL·) 206 186 196 196 196 銲錫粉之熔點(τ2) 138 138 138 138 118 樹脂層之熔融黏度 550 740 810 1110 520 τ「τ2 68 48 58 58 78
[表7] 實施例11 實施例12 實施例13 實施例14 樹脂層之硬化溫度(TO 197 196 194 198 銲錫粉之熔點(T2) 138 138 138 138 樹脂層之熔融黏度 270 150 110 3870 T1-T2 59 58 56 60 [表8] 比較例1 比較例2 比較例3 比較例4 樹脂層之硬化溫度(Ti) 132 192 204 144 銲錫粉之熔點(τ2) 138 138 138 138 樹脂層之熔融黏度 1340 34 6580 7630 Τ1-Τ2 -6 54 66 6 於實施例1〜18中,獲得了成膜性良好之黏著帶。 (基板間的連接評價) 分別使用實施例1〜18及比較例1〜4之黏著帶,進行 圖2所示無阻焊劑之基板間的連接。所用基板為板厚0.4 mm之FR-4、銅箔(第一電極、第二電極)厚12 /z m、Ni/Au 電鍍、電路寬度/電路之間寬度300 /zm/100 /zm、上下 35 312/發明說明書(補件)/96-10/96118934 200815562 電路重豐莧度100 ,於此基板之間配置黏著帶,進而, 以均勻施加壓力之方式在基板之上面配置2〇〇 “瓜厚之矽 橡膠,再藉由220°C、2 MPa、600秒鐘條件下的熱壓接合 ^ 而實施連接。 . 又亦刀別使用實施例1〜18及比較例1〜4之黏著帶, 進行圖3所示有阻焊劑之基板間的連接。所用基板為板厚 0.4随之FR-4、銅箔(第一電極、第二電極)厚12以瓜、 馨阻焊劑厚(自電路(第—電極、第二電極)之上面開始的厚 度)12 、Ni/Au電鍍、電路寬度/電路之間寬度3〇〇 em/100 /ζιη、上下電路重疊寬度1〇〇 ,於此基板之 間配置黏著帶,進而,以均勻施加壓力之方式在基板之上 面配置200 厚之矽橡膠,再藉由18〇。〇、2 Mpa、6⑽ 秒鐘條件下的熱壓接合而實施連接。 利用4端子法對所得接合體之相鄰端子間的連接電阻 值進打12點測定,取平均值為測定值。表9〜表12以及 _表15中,將測定值為3〇 m Ω以下的情況判定為「〇」, 將30 mΩ以上的情況判定為「χ」。 又,測定了各黏著帶中具有助熔劑活性之硬化劑的羧基 相對於熱硬化性樹脂的反應率。反應率之測定方法如同二 述實施形態所述。 • 針對各實施例及各比較例,觀察10個端子的剖面,將 -所有部位皆形成有如圖7及圖8所示之銲錫導電柱的情況 判定為〇,又,將存在1處都未形成導電柱之部位的情況 判定為χ。 312/發明說明書(補件)/96-10/96118934 36 200815562 此處,圖7為表示實施例1中利用掃描式電子顯微鏡 (scanning electron microscope,以下簡稱8£1)觀察無 阻焊劑之積層體而得的結果之剖面圖。如圖7所示,銲錫 厚為2 μ m,顯示出良好的銲錫連接性。 又,圖8為表示實施例1中SEM觀察有阻焊劑之積層體 的結果之剖面圖。如圖8所示,端子間的間隙約為18//111。 又,銲錫厚度為18 //m,顯示出良好的銲錫連接性。又, 連接電極之間的銲錫區域,呈現出於兩電極側擴展的形 狀0 [表9] 評 價 結 果 實施例1 實施例2 實施例3 實施例4 實施例5 相鄰端子連接電阻值 無阻焊劑基板 測定值(in Ω) 14 20 14 22 16 判定 〇 〇 〇 〇 〇 有阻焊劑基板 測定值(πιΩ) 15 19 16 25 15 判定 〇 〇 〇 〇 〇 上下電路之間的導電柱形成性 無阻焊劑基板 判定 〇 〇 〇 〇 〇 有阻焊劑基板 判定 〇 〇 〇 〇 〇 硬化劑之羧基的反應率 83 96 71 69 76 [表 10] 評 價 結 果 實施例 6 實施例 7 實施例 8 實施例 9 實施例 10 相鄰端子連接電阻值 無阻焊劑基板 測定值(ιηΩ) 15 24 22 27 18 判定 〇 〇 〇 〇 〇 有阻焊劑基板 測定值(ιηΩ) 17 22 23 26 17 判定 〇 〇 〇 〇 〇 上下電路之間的導電柱形成性 無阻焊劑基板 判定 〇 〇 〇 〇 〇 有阻焊劑基板 判定 〇 〇 〇 〇 〇 硬化劑之羧基的反應率 67 88 82 84 85
312/發明說明書(補件)/96-10/96118934 37 200815562 [表 11] 評 價 結 果 實施例11 實施例12 實施例13 實施例14 相鄰端子連接電阻值 無阻焊劑基板 測定值 (ιηΩ) 25 24 15 24 判定 〇 〇 〇 〇 有阻焊劑基板 測定值 (ιβΩ) 24 22 14 23 判定 〇 〇 〇 〇 上下電路之間的導電柱形成性 無阻焊劑基板 判定 〇 〇 〇 〇 有阻焊劑基板 判定 〇 〇 〇 〇 硬化劑之缓基的反應率 86 87 79 89 [表 12]
評 價 結 杲 比較例1 比較例2 比較例3 比較例4 相鄰端子連接電阻值 無阻焊劑基板 測定值 (πιΩ) open open open open 判定 X X X X 有阻焊劑基板 測定值 (ιηΩ) open open open open 判定 X X X X 上下電路之間的導電柱形成性; 無阻焊劑基板 判定 X X X X 有阻焊劑基板 判定 X X X X 硬化劑之羧基的反應率 — 78 95 — 312/發明說明書(補件)/96-10/96118934 38 〔001 ί 實施例18 r—H! ◦· 10.1 〇 T—Η S CO 寸· (NI CO <=> T—H cr> C5 LO <=> g r-H § 實施例Π 03 14.2 卜 isi 寸 20.4 0.50 1 〇.〇1 I 〇 ΙΟ !00.0! § 實施例16 10.1 τ—Η ο 〇 τ—Η CD 03 CO 呀· (NI CO CD CD CD in 100.0 〇 C35 實施例15 14.2 14.2 卜 LO 寸 | 0.50 | τ—Η <=> c=i cz> LO 100.01 § 構造等 (丙烯酸丁酯)一(丙烯酸乙酯)_(丙烯腈)= 30mol%/30mol%/40mol% 分子量=85萬 聚合度= 1700、乙醯化度= 3mol%以下 縮丁酿化度= 65mol%以上、流動軟化點= 225°C 雙酚A骨架、數量平均分子量= 30000 雙酚F骨架、重量平均分子量= 50000 苐骨架、重量平均分子量= 50000 構造名稱記載於*1 甲酚酚醛清漆型環氧樹脂、軟化點80°C 液狀雙酚A型環氧樹脂、環氧基當量= 180 軟化點= 100°C、0H當量= 104 3-縮水甘油氧基丙基三甲氧基矽烷 N-苯基_3-胺基丙基三甲氧基矽烷 2-苯基-4, 5~二經基13米嗤 2-苯基-4-甲基咪唑 _C-(CH2)8-COOH hooc-(ch〇4-cooh HOOC-(CH2)i〇-COOH 2, 5-二羥基苯甲酸 樹脂合計 Sn/Bi=42/58、熔點=138°C、平均粒徑 35 μπι Sn/Bi=42/58、熔點=138°C、平均粒徑 20 μιτι Sn/Bi=42/58、熔點=138°C、平均粒徑 12 μιη Sn/In=48/52、熔點=118°C、平均粒徑 35 nm 成分 丙烯酸橡膠 聚乙烯醇縮丁醛樹脂 苯氧樹脂 環氧樹脂 環氧樹脂 環氧樹脂 酚系酚醛清漆 矽烷偶合劑 矽烷偶合劑 咪嗤 味嗤 癸二酸 己二酸 龍膽酸 還原盼酉太 銲錫粉 功能 4i ^ 硬化成分① 硬化成分② 硬化成分④ 硬化劑 賦予密著性① 賦予密著性② 硬化觸媒 1 1 _____ 具有助熔劑活性之硬化劑 導電性粒子 調配 #φ?§^^«—2'^^^〔^^〔^ο〔^δ-'ι〔^^(^^^^^^ιοο(>ί)ΛνΙ〕Λ〕- Ι'Ϋ 6cn寸 ε68ΙΙ96/0Ι-96/ίρ}*)_&^藍激/rslle 200815562 [表 14] --— -----_ 實施例15 實施例16 實施例17 實施例18 樹脂層之硬化溫度(T!) 208 212 210 213 ~~—---- 銲錫粉之熔點(丁2) 138 138 138 138 樹脂層之熔融黏度 130 140 150 170 Τι-Τ2 70 74 72 75 [表 15] 評 價 結 果 實施例15 實施例16 實施例17 實施例18 相鄰端子連接電阻值 無阻焊劑基板 測定值(ιηΩ) 22 20 26 —25 判定 〇 〇 〇 〇 有阻焊劑基板 測定值(ιηΩ) 21 20 27 27 判定 〇 〇 〇 〇 上下電路之間的導電柱形成性 焊劑基板 判定 〇 〇 〇 〇 有阻焊劑某栋 判定 〇 〇^ 〇 〇 硬化劑之羧暴的反應率 ^ 84 86 71 V-/ 72
使用有貫施例之黏著帶的情況下,已將連接電阻壓低。 相對於此’使用有比較例之黏著帶的情況下,連接電阻 變大。 藉此’確認根據本發明能夠穩定實現低電阻。 (相對銅佈線表面之潤濕性的評價) 針對實施例1中所記載之黏著帶,改變表1中銲錫粉及 具有助熔劑活性之硬化劑的種類。繼而,評價對具有助熔 劑活性之硬化劑與銲錫粉的材料之組合,及相對銅佈線表 面之潤濕性所產生的影響。 使用 Sn/Pb、Sn/Bi、Sn/Zn/Bi、及 Sn/Ag/Cu 作為鲜錫 粉。針對各銲錫粉,使用龍膽酸及癸二酸作為具有助熔劑 活性之硬化劑,該硬化劑作為環氧樹脂之硬化觸媒而發揮 312/發明說明書(補件)/9640/96118934 40 200815562 果是,任何組合皆能確保良好的潤濕性。又, η 1,、六—酸的組合具有最佳潤濕性。 (銲鍚粉之粒子徑的討論) 改變黏著帶中銲錫粉之粒子徑,評價相對 潤濕性所受影響。針對實施例1中所記载之面之 錫粉之平均粒徑設為12 ,m、2。㈣、及:者將銲 錫粉以外之成分為〗on 0士 ^# m。將銲 m二 錫粉之添加量設為20重量 。 且、干劑層的基板之間,配置黏著帶,並在 2 MPa條件下實施熱壓接合6〇〇秒鐘。又,1社 、 糾皆能確保相對鋼佈線之潤濕性、、:= 潤濕性自尚而低的順序粒子徑為 、 12 ,m〇 十子…5㈣、20㈣、及 【圖式簡單說明】 圖 面圖 圖 面二1為說明使用有實施形態之黏著帶的黏著方法之剖 2為說明使用有實施形態之黏著帶的黏著方法之剖 ;為說明使用有實施形態之黏著帶的黏著 面圖。 〜 圖4為表示實施形態之半導體封襄的構成之剖面圖。 圖5為表示實施形態之半導體封《的構成之剖面圖。 圖6為表示實施形態之半導體封裝的構成之剖面圖。 圖7為表示實施例之積層體構造的剖面圖。 圖8為表示實施例之積層體構造的剖面圖。 312/發明說明書(補件y96-10/96118934 200815562 【主要元件符號說明】
101 103 105 107 109 111 113 、 137 115、12卜 135 117 119 131 132 133 139 141 143 151 153 155 157 159 、 169 、 171 16卜 165 163 167 黏著帶 銲錫粉 第三基板 第二基板 第一基板 鲜錫區域 弟一電極 第二電極 通道孔 第三電極 第二基材 樹脂層 第一基材 第二阻焊劑層 第一阻焊劑層 空隙部 第一半導體晶片 第二半導體晶片 裝配基板 基板 導線 凸塊電極 密封樹脂 樹脂 312/發明說明書(補件)/96-10/96118934 42

Claims (1)

  1. 200815562 十、申請專利範園: 為 1· 一種黏著帶,係使導體構件 包含: 之間電性連接者,其特徵 含有熱硬化性樹脂的樹脂層; 銲錫粉;以及 硬化劑; 上述銲錫粉與上述硬化㈣存在於上述樹脂層中; 上述樹脂層之硬化溫度盥卜;+、辟力卩丨、 式(1); 度11興上述鲜錫粉之熔點T2滿足 Ti^T2+20°C 式(1) 上述硬化溫度μ利DSC,以1{rc/分鐘之升 測定黏著帶時的發熱波峰溫度; 上述樹脂層於上述銲鍚粉之溶點T2的溶 50Pa.s以上且50〇〇pa.s以下。 馬 2.如申請專利範圍第丨項之黏著 粉以外之成分的合計100重量份,上較錫中於相對於銲錫 20重量份以上。 上料錫粉之調配量為 ==範圍第2項之黏著帶,其中,上述銲錫粉 之十均粒徑為1 Am以上且1〇〇 以下。 =·如中請專利範圍第!項之黏著帶,其中,上述執硬化 有室溫下為固形之環氧樹脂、及室溫下㈣ 5.如申請專利範圍第4項之黏著帶,其中,上述室溫 為固形之環氧樹脂係含有固形三官能環氧樹脂及甲^ 312/發明說明書(補件)/96-10/96118934 43 200815562 搭清漆型環氧樹脂; 上述室温下為液狀之環氧樹脂為㈣A 雙酚F型環氧樹脂。 < 虱树I曰或 6. 如申請專利範圍第i項之黏著帶,其 為具有助熔劑活性之硬化劑。 处 刈 7. 如申請專利範圍第6項之黏著帶,其中 熔劑之硬化劑係含有羧基的硬化劑。 ^助 朽=1請專利範圍第1項之黏著帶,其中,存在於上述 W月曰中的上述銲錫粉#葬ώ 述導體構件表面。 熱而自㈣準地移動至上 9· 一種接合體,係包括以下構成者·· 一對導體構件;以及 黏著帶’其配置於該一針導 τ令體構件之間,使一對導體構 件之間電性連接;其特徵為, 上述黏著帶係申請專利範圍第7項之黏著帶; 、上述具有助熔劑活性之硬化劑之羧基的50%以上係與上 述熱硬化性樹脂產生反應。 10·—種半導體封裝,其特徵為包括: 晶片搭載基板;以及 積層於該晶片搭載基板之一侧的面上的第一及第二半 上述第一半導體晶片與上述第二半導體晶片係藉由申 請專利範圍第1項之黏著帶而黏著。 11. 一種半導體封裝,其特徵為包括·· 312/發明說明書(補件)/96-10/96118934 44 200815562 搭載半導體晶片的第一基板;以及 搭載上述第一基板的第二基板; 上述第一基板與上述第二基板係藉由申請專利範圍第1 項之黏著帶而黏著。
    312/發明說明書(補件)/96-10/96118934 45 200815562 七、指定代表圖: (一) 本案指定代表圖為:第(1 )圖。 (二) 本代表圖之元件符號簡單說明: 101 黏著帶 〜 103 105 - 107 109 111 113 m 115、121 • 117 119 132 銲錫粉 第三基板 第二基板 第一基板 鲜錫區域 第一電極 第二電極 通道孔 第三電極 樹脂層 八、本案若有化學式時,請揭示最能顯示發明特徵的化學式 無 i 312/發明說明書(補件)/96-10/96118934 5
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