TWI448524B - 製造半導體封裝件之黏著組成物及黏著片 - Google Patents

製造半導體封裝件之黏著組成物及黏著片 Download PDF

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Publication number
TWI448524B
TWI448524B TW099138786A TW99138786A TWI448524B TW I448524 B TWI448524 B TW I448524B TW 099138786 A TW099138786 A TW 099138786A TW 99138786 A TW99138786 A TW 99138786A TW I448524 B TWI448524 B TW I448524B
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TW
Taiwan
Prior art keywords
adhesive
adhesive composition
epoxy resin
weight
wafer
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TW099138786A
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English (en)
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TW201213478A (en
Inventor
Sung Su Kim
Jin Won Kim
Kwang Ho Shin
Kyung Nam Cho
Kyo Sung Hwang
Chang Bum Chung
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Kcc Corp
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Publication of TW201213478A publication Critical patent/TW201213478A/zh
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Publication of TWI448524B publication Critical patent/TWI448524B/zh

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    • C—CHEMISTRY; METALLURGY
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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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
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    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • H01L23/49513—Lead-frames or other flat leads characterised by the die pad having bonding material between chip and die pad
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
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    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
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    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
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    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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    • C09J2433/00—Presence of (meth)acrylic polymer
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Description

製造半導體封裝件之黏著組成物及黏著片
本發明係關於一種可使用於半導體製程之黏著組成物，及一種包括該組成物且可加工處理成片狀形式之黏著材料。更具體地說，本發明係關於一種黏著組成物，以及包括該組成物之黏著片。該組成物係在半導體製程中施用於晶圓表面及使用於晶片與基板，或晶片與晶片之黏著，特別是在高溫黏著時具有增加的流動性，因此對於諸如凸塊及金屬接線等構造提供良好的嵌入性，且對支持構件具有改進之介面黏著力，因此即使在高溫/高濕狀況下，亦提供半導體元件高可靠性。
半導體製程中，在印製電路圖案於晶圓之程序之後為將該晶圓切成晶片之切割程序，分割該切割之晶片成個別晶片之擴充及取晶程序，將該經由取晶程序分割之晶片固定於基板之黏合程序，晶片與基板電連接用之金屬接線程序，以及用於保護晶片之環氧模製(epoxy-molding)程序。如以上所述之方法中，為了易於切割晶圓及易於撿取晶片，而使用保護晶圓用黏結片及用於撿取晶片之黏著組成物或黏著片。
將晶片接合至基板之慣用方法包含以某種特定圖案施用液態環氧樹脂組成物於備妥之引線框架或軟性印刷電路版(FPCB)並固定晶片，該等晶片係使用保護晶圓用黏合片預先處理及分割。但是，於施用液體環氧樹脂組成物，在控制施用厚度均勻性方面有問題，且施用於晶片接合之壓力易使發生滲出。雖可調整液體黏著組成物之搖變值(thixotropy index)以控制其流動性，但由於應用於多堆疊晶片製造之困難度，因而僅限於單晶片製造。
為解決使用液體黏著劑產生的上述問題，建議修改液體黏著劑成適當的樹脂組成物且以片狀形式提供。此類的片狀型黏著劑係製成與晶片相似尺寸之細條形式(rill form)然後以使用特定裝置將黏著片切成晶片尺寸並黏合於基板，再接合分割之晶片之方式使用。但是，此方法需要特定裝置及額外的程序來切割及黏合黏著片，其利用性因而減低。
近來的半導體製程，因為黏著片先接合於晶圓之背面然後施行切割，所以個別晶片係以晶片與黏著片之結合構造(integrated structure)獲得。此類的黏著片一般可與接合於此之黏結材料以結合形式供應。在此狀況下，不同於黏結片係接合於晶圓背面之切割程序，黏著片與黏結片之結合形式(其中後者層壓於前者之背面)係接合於晶圓，然後進行其後的步驟。
此類以製備成與黏結片形成結合形式之黏著片接合於晶圓之背面以簡化半導體製程中自晶圓切割至晶粒黏合之程序的方法係揭露於韓國專利公開申請案公告(Korea Patent Laid-open Publication) No. 10-2006-0021337及韓國專利(Korea Patent) No. 10-0826420、10-0646069、10-0845092等。
近來慣用的半導體製程中，為提升半導體封裝件之積體程度，使用在特定空間垂直堆疊複數層半導體晶片的方法。利用堆疊半導體元件之技術及使用適用於此類技術之黏著材料，積體程度可改進為堆疊兩層或更多層晶片於由引線框架或軟性電路版構成之封裝件。在使用凸塊作為電連接器之晶片級封裝(CSP)中，使用垂直堆疊晶片於具有焊接凸塊之基板的技術以提升積體程度。此外，當多層堆疊複數之晶片以改進積體程度時，為了有效利用晶片空間主要係使用垂直堆疊相同尺寸晶片的方法。於垂直多層堆疊相同尺寸晶片，接合晶片於引線框架或板以完成元件之電連接然後操作金屬接線以電連接晶片與基板或以事先固定於晶片背面之金屬凸塊接合晶片於基板，之後多層堆疊其他以同尺寸供應之晶片於其上。在此一連串之程序中，為要保證半導體元件之可靠性，使用之黏著片在晶片接合之過程期間須有充分的流動性以嵌入存在於晶片與晶片間之諸如金屬接線或凸塊之構造，或晶片與基板間不會形成空隙或破壞構造。此外，須於接合之後經固化過程顯示高介面黏著度。
半導體之慣用黏著片係藉由下法製成片狀形式：藉由調配提供可撓性之熱塑性橡膠成分以及具良好之耐熱性黏著度之固體環氧樹脂組成物，而製備可在室溫處理之片狀類型之黏著劑，用適當溶劑稀釋該混合物以進行混合，並進行施用程序。彼等係用於一般晶片接合過程。
但是，在堆疊同尺寸晶片之程序中，此類之慣用黏著片具低流動性而不足以完全地嵌入金屬接線或金屬凸塊，因此具有於接合期間產生空隙或因佈置於接合表面之接線受損而產生瑕疵品之問題。此外，熱塑性橡膠成分及環氧樹脂組成物間貧乏的相容性造成微小的相分離，且長期暴露於高溫/高濕狀況下造成橡膠成分之老化由此而減低黏著度。特別是，除了由構成形成引線框架、接線、凸塊等的金屬成分提供半導體元件之特性之外，多種不同的有機材料諸如防焊劑、鈍化劑等形成保護電路嵌入板及晶片係同時暴露於要接合之晶片表面，但彼等一般具有比金屬低之表面能因而使用黏著片之晶片接合可能減低黏著強度。
為解決如上述之先前技術的問題，本發明的目的係提供一種黏著組成物以及包括該組成物之黏著片，該組成物對暴露在欲接合之半導體表面之構造諸如凸塊及金屬接線提供良好之嵌入性，且對半導體支持構件具有改進之介面黏著度，而甚至於在高溫/高濕狀況下亦提供半導體元件之高可靠性。
為達到如上述之目的，本發明提供一種黏著組成物，係包括：(A)含有一個或多個反應基之共聚丙烯酸酯化合物，(B)熱固性環氧樹脂混合物，(C)固化劑，(D)填充料及(E)固化促進劑，其中該成分(A)：(B)之重量比率為95：5至65：35，該成分(B)包括一種或多種於150℃具有0.1泊(Pa‧s)或較低熔體黏度之環氧樹脂，對每100重量份之該等成分(A)+(B)+(C)之總合，該成分(D)的含量為10至80重量份，及對每100重量份之該等成分(A)+(B)+(C)之總合，該成分(E)的含量為0.1至1.4重量份。
本發明另一方面提供製造半導體用之黏著片，其係包括本發明黏著組成物之塗佈層。
當本發明之黏著組成物及黏著片使用於半導體製程時，可改進對接合對象之介面黏著度且甚至於高溫/高濕狀況下仍保持黏著特性，藉此可得到高可靠性。此外，由於高溫流動性，可使暴露於要接合之半導體表面上之構造諸如凸塊及金屬接線得到良好之嵌入性。
詳細說明本發明於下。
(A)　含有一個或多個反應基之共聚丙烯酸酯化合物
本發明之共聚丙烯酸酯化合物含有一個或多個反應基(如，極性基)，藉此可適當調整其表面能而可形成不同化合物之分子問交聯或單一分子之分子內交聯，如此可改進組成物之黏著性能及改進對半導體支持構件中具低表面能之有機材料之介面黏著特性。當測量其與水之接觸角時，共聚丙烯酸酯化合物(A)具有之較佳表面能係40達因/公分(dyne/cm)至50達因/公分(dyne/cm)，較佳重量平均分子量係300,000至1,500,000，及較佳玻璃轉換溫度係-20℃至50℃。
含於共聚丙烯酸酯化合物(A)之反應基的較佳實例包含一個或多個選自丙烯腈基、環氧基、羥基及羧基者。
具體地，當共聚丙烯酸酯化合物含有環氧基及羥基於一分子，可使用樹脂類諸如SG-PT115(環氧值：0.21當量/公斤(eq/kg)，羥值：20毫克(mg)KOH/克(g)，分子量800,000)，SG-PT134(環氧值：0.21當量/公斤，羥值：30毫克KOH/克，分子量800,000)及SG-PT135(環氧值：0.21當量/公斤(kg)，羥值：400毫克KOH/克，分子量800,000)可購自Nagase Chemtex Co.,Ltd.；當共聚丙烯酸酯化合物含有羧基及丙烯腈基於一分子中，可使用樹脂類諸如DN631(丙烯腈：33.5%，密度：0.99)及NBR N34(丙烯腈：27%，密度：0.98)可購自Zeon Co.,Ltd.；及當共聚丙烯酸酯化合物含有丙烯腈基於一分子中，可使用樹脂類諸如那些可購自Hyundai Petrochemical Co.,Ltd.SEETEC系列，但不限於此。
於本發明之黏著組成物中，該共聚丙烯酸酯化合物成分(A)：下述之環氧樹脂混合物(B)之重量比率為95：5至65：35，及較佳為90：10至70：30。如果成分(A)以少於此重量比率所定義之量使用，則黏著組成物變成太硬因而在施用期間或切割過程時可能太容易破損。相反的，如果成分(A)以多於此重量比率所定義之量使用，則不能保證黏著片在黏著及固化後之充分黏著強度，而因此可靠性可能有問題。
(B)　熱固性環氧樹脂混合物
作為含於本黏著組成物之熱固性環氧樹脂混合物，可使用下述(i)及(ii)之混合物；(i)一種或多種以上如下述之於150℃具有0.1泊(Pa‧s)或較低之熔體黏度(如，0.001至0.1泊)之環氧樹脂以及(ii)一種或多種之慣用習知者包含，例如，雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、脂環族環氧樹脂、線型脂肪族環氧樹脂、酚系酚醛環氧樹脂、甲酚酚醛環氧樹脂、雙酚A酚醛環氧樹脂、聯酚之二環氧丙基醚、萘二酚之二環氧丙基醚、酚化合物之二環氧丙基醚、醇化合物之二環氧丙基醚，及該等之烷基取代、鹵化或氫化化合物，多官能環氧樹脂、含雜環之環氧樹脂等。
更具體地，可使用如商業用實例，雙酚A型環氧樹脂諸如EPICOAT807、EPICOAT815、EPICOAT825、EPICOAT827、EPICOAT828、EPICOAT834、EPICOAT1001、EPICOAT1002、EPICOAT1003、EPICOAT1055、EPICOAT1004、EPICOAT1004AF、EPICOAT1007、EPICOAT1009、EPICOAT1003F、EPICOAT1004F(商品名，Japan Epoxy Resin Co.,Ltd.)，YD011、YD-012、YD-013K、YD-014、YD-017、YD-112、YD-113、YD-114、YD-115、YD-127、YD-128(商品名，Kuk-do Chemical Co.,Ltd.)，SE-187、SE-187P(商品名，Shin-wha T&C Co.,Ltd.)等；雙酚F型環氧樹脂諸如YDF-161、YDF-162、YDF-170(商品名，Kuk-do Chemical Co.,Ltd.)，SE-187、SE-187P(商品名，Shin-wha T&C Co.,Ltd.)等；酚系酚醛環氧樹脂諸如EPPN-201、EPPN-501、EPPN-501HY、EPPN-502(商品名，Nippon Kayaku Co.,Ltd.)，YDPN-631、YDPN-636、YDPN-638(商品名，Kuk-do Chemical Co.,Ltd.)等；及甲酚酚醛環氧樹脂諸如YDCN-500-1P、YDCN-500-4P、YDCN-500-5P、YDCN-500-7P、YDCN-500-10P、YDCN-500-80P(商品名，Kuk-do Chemical Co.,Ltd.)，EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、EOCN-1020、EOCN-1025及EOCN-1027(商品名，Nippon Kayaku Co.,Ltd.)。
環氧樹脂混合物成分(B)包括一種或多種於150℃具有0.1泊(Pa.s)或較低(如，0.001至0.1泊)之熔體黏度之環氧樹脂。此類環氧樹脂的實例包含YDC-1312(環氧當量：180克/當量(g/eq)，150℃時之黏度：0.01泊)、YSLV-80XY(環氧當量：195克/當量，150℃時之黏度：0.01泊)及YSLV-120TE(環氧當量：245克/當量，150℃時之黏度：0.1泊)可購自Dong-do Chemical Co.,Ltd.；YX-4000(環氧當量：192克/當量，150℃時之黏度：0.005泊)可購自Yukacel Co.,Ltd.；及XD-1000-2L(環氧當量：240克/當量，150℃時之黏度：0.05泊)以及CER-3000-L(環氧當量：233克/當量，150℃時之黏度：0.03泊)可購自Nippon Kayaku Co.,Ltd.，但不限於此。
環氧樹脂混合物成分(B)中於150℃具有0.1泊(Pa‧s)或較低之熔體黏度的環氧樹脂之含量並沒有特別限制。基於100重量%之環氧樹脂混合物成分(B)之量，較佳可使用5至50重量%，但不限於此。
根據本發明之較佳具體例，於150℃具有0.1泊或較低之熔體黏度的環氧樹脂可以上述量含於環氧樹脂混合物成分(B)中，而使包括本發明黏著組成物之黏著片具有自3.0至5.0之對數阻尼比之間之比率，該比率係以流變計(RPT-3000W，A&D Co.,Ltd.)分別於80℃及120℃於高溫流動性測試進行測量，且於120℃可具有0.01至0.1之對數阻尼比。
於包括本發明黏著組成物之黏著片，如果80℃/120℃之對數阻尼比之比率少於3.0，高溫流動性可能太高因而在同時要均勻地保持上部與底部之間隙時可能在黏合晶片與基板或晶片與晶片方面有困難。如果120℃之對數阻尼比大於0.1，當接合於半導體支持構件時流動性可能不足且因而對暴露於接合表面上之凸塊及金屬接線之嵌入性可能不足。以流變RPT-3000W所特定之性質的意義說明於下述評估黏著片之方法中。
本發明之黏著組成物中，該共聚丙烯酸酯化合物成分(A)：環氧樹脂混合物成分(B)之重量比率為95：5至65：35，較佳為90：10至70：30。如果成分(B)以多於上述重量比率所定義之量使用，則黏著組成物變成太硬且因此在施用期間或切割過程時可能容易破損。相反的，如果成分(B)以少於上述重量比率所定義之量使用，不能保證黏著片在黏著及固化後之足量黏著強度而可靠性可能有問題。
(C)　固化劑
本發明之黏著組成物中，固化劑係使用於固化環氧樹脂。
慣用之固化劑可使用於本發明之黏著組成物。例如，可使用選自酚系化合物類、胺化合物類、酸酐類等慣用的環氧樹脂用固化劑。較佳可使用具有兩個或兩個以上羥基且羥基當量100克/當量至300克/當量之酚系樹脂(例如，酚系酚醛環氧樹脂)，而無特別限制。
本發明之黏著組成物中，固化劑(C)對環氧樹脂混合物(B)之當量比率較佳為0.8至1.3，更佳為0.9至1.1。如果固化劑量遠超出此範圍，未作用之環氧樹脂或固化劑樹脂可能殘留並於高溫劣化，而可能降低該其靠性。
(D)　填充料
本發明之黏著組成物中，填充料係使用於調整黏著片之耐熱性高溫流動性、加工過程操作性等。
可使用於本黏著組成物中之填充料並無特別限制。例如，可使用氧化矽、氧化鋁、銀、鍍金珠粒、矽酮珠、碳黑、氫氧化鋁、氫氧化鎂、氮化硼、二氧化鈦、陶瓷等之顆粒，該等呈球狀且具有10奈米(nm)至10微米(μm)平均粒子尺寸者。較佳實例為球形氧化矽其於黏著組成物中具有良好之分散性並有利於提供高溫流動性。
於每100重量份之該等成分(A)+(B)+(C)中，本黏著組成物中填充料(D)之含量係10至80重量份，較佳為20至60重量份。如果每100重量份之該成分(A)+(B)+(C)中，填充料量少於10重量份，則黏著片之強度減低而可能易於發生高溫熱應力引起之變形。如果填充料量大於80重量份，黏著片之脆度性問題變得嚴重而加工期間可能易發生破損，且與黏合膜之黏著力減低，而減低加工過程之可操作性。
(E)　固化促進劑
本發明之黏著組成物中，固化促進劑係使用於改進固化率。
可使用於本黏著組成物中之固化促進劑並無特別限制。任何固化促進劑均可使用，只要於固化條件之溫度下能減少黏著組成物之固化時間者即可。其較佳係使用在製得黏著片之條件下具低反應性，而在120℃至180℃之固化溫度下具高反應性之化合物。例如，可使用2MZ-A、C11Z-A、2MA-OK、2PHZ及2P4MHZ，現可購自Sa-kuk Chemical Co.,Ltd.；及TPP、TBP、TBP、TPP-K、TPP-MK、TPPO、DPPE及DPPB現可購自Hoko Chemical Co.,Ltd.。
於每100重量份之該等成分(A)+(B)+(C)之總量中，本黏著組成物中固化促進劑(E)之含量係0.1至1.4重量份，較佳為0.2至1.0重量份。如果於每100重量份之該等成分(A)+(B)+(C)之總量中，固化促進劑量少於0.1重量份，於晶片堆疊後之固化過程中之固化率會不足而底部晶片可能因其後之晶片堆疊所施加的熱與負荷而搖動，導至瑕疵品。如果固化促進劑量大於1.4重量份，由於製造黏著片過程期間產生的熱可能會發生一些副反應而當產品保存於室溫時會有減低長期儲藏穩定性之可能性。
除前述成分之外，本黏著組成物可進一步包括其他成分，其等係慣用於半導體製程之黏著組成物中者，該等其他成分包含適當量之溶劑諸如丙酮、丁酮、甲苯、乙酸乙酯等，黏結增強劑、偶合劑、抗靜電劑、快固劑、熱固性助劑、黏著增強劑、潤濕改善劑、調平(leveling)增強劑等。本發明之較佳具體例中，具有可黏合於樹脂混合物及黏著表面兩者之功能基的偶合劑因有助於改進彈性及耐熱性，而於總量每100重量份之混合物中，可使用3.0重量份或較少之量。
製得本黏著組成物之方法沒有特別限制。可以使用慣用來製備黏著組成物之慣用裝置來製備。根據本發明之具體例之一，本黏著組成物係可於室溫或適當提高之溫度下以諸如珠磨機等裝置分散及混合上述成分以製得。
本發明另一方面係提供製造半導體用之黏著片，其係包括如上述之本發明黏著組成物之塗佈層者。
本發明之製造半導體之黏著片之特點為包括本發明黏著組成物之塗佈層，如果必要，可進一步包括一個或多個之基底(膜)層，其亦可指離型(膜)層或保護(膜)層，及一個或多個黏結(膜)層。根據本發明之具體例之一，製造半導體用之黏著片可具有層狀結構諸如基底層+黏著組成物層；基底層+黏著組成物層+基底層；基底層+黏結層+黏著組成物層；基底層+黏結層+黏著組成物層+基底層等，但不限於此。
可包含於本發明製造半導體用之黏著片之基底層之材料並無特別限制。可使用習慣上作為黏著片基底膜之材料諸如聚對苯二甲酸乙二酯、聚烯烴或聚氯乙烯。至於黏結層，可使用慣用於黏著片之黏結材料諸如含有光反應性低聚物之丙烯酸系材料。
製造半導體用之本黏著片中，黏著組成物塗佈層之乾厚度並無特別限制，較佳為10至200微米之範圍內。如果黏著組成物塗佈層之乾厚度小於10微米，黏著效力可能不足。如果乾厚度大於200微米，塗佈操作於塗佈之乾燥過程中可能因殘留之揮發物而不易進行，且在黏合過程中當堆疊程度越高時，黏著劑可能在高溫黏合期間自旁邊滲出。黏著組成物較佳在125℃，60分鐘內顯示50%或更高之固化度。黏著組成物塗佈層中殘留之揮發物量較佳為1重量%或更少。
製得本黏著片之方法並無特別限制。可以使用慣用製備多層黏著片之慣用裝置來製備。根據本發明之具體例之一，可以製得本黏著片，如果必要，可以適當之有機溶劑稀釋並混合本黏著組成物至適當濃度以易於形成塗層，施用於諸如聚對苯二甲酸乙二酯之基底膜上並乾燥之。至於施用及乾燥程序，可使用任何可形成塗佈層的方法諸如棒式塗佈、凹版塗佈、刮刀式塗佈、逆轉滾筒式塗佈、滾刀式塗佈、模具塗佈(die coating)、狹縫式式塗佈等而無限制。
如上述之本發明黏著片具有良好的高溫流動性且因此提供對於諸如暴露於要接合之表面之凸塊及金屬接線構造之良好的嵌入性，及對半導體之支持構件具有改進之介面黏著度因此即使在高溫/高濕狀況下亦提供半導體元件之高可靠性。
本發明係以下述之實施例及比較例更仔細地加以說明。但本發明之範圍並不限於彼等。
實施例1
將含37.4克甲酚酚醛環氧樹脂(B1)與14.0克雙酚F型環氧樹脂(B2)之環氧樹脂混合物加入280.5克之反應性共聚丙烯酸酯化合物(A1)中，並混合之。加入25.7克作為固化劑(C)之酚系酚醛環氧樹脂以使其對環氧樹脂混合物之當量比率為1.0。
於100重量份如上述製備而得的混合物中，依序加入45重量份之球形氧化矽(D1)作為填充料，0.3重量份之固化促進劑(E)及1.5重量份之偶合劑(F)，充分攪拌。攪拌期間，為求適當之黏度及溶解度，進一步加入有機溶劑丁酮使組成物中固體總量為30%至35%之量。完成預攪拌後，組成物以珠磨机充分再分散然後塗佈於38微米厚並經過單面離型處理之聚對苯二甲酸乙二酯離型膜上，使成為60微米之乾厚度而製得黏著片。
說明於下之評估方法中之黏彈儀試驗(Rheovibron test)之樣本係將上述製得之黏著片於60℃層壓至厚度200微米而製得。
實施例2至7
根據顯示於表1之組成比率，黏著組成物及片係以如實施例1中之相同方法製得。
A1：SG-PT115(Nagase Chemtex，環氧值：0.21當量/公斤，羥值：20毫克KOH/克)
A2：SG-PT134(Nagase Chemtex，環氧值：0.21當量/公斤，羥值：30毫克KOH/克)
A3：SG-PT135(Nagase Chemtex，環氧值：0.21當量/公斤，羥值：40毫克KOH/克)
B1：YDCN-500-4P(Kuk-do Chemical，環氧當量：200克/當量，軟化點：62℃)
B2：YSLV-80XY(Dong-do Chemical，環氧當量：195克/當量，150℃時之黏度：0.01泊)
B3：YX-4000(Yukacel，環氧當量：192克/當量，150℃時之黏度：0.005泊)
C：HF-1M(Meiwha，羥基當量：106克/當量，軟化點：84℃)
D1：SO-31R(Datsmori，平均粒徑：1.24微米，比表面積(S.S.A)：4.68平方米/克)
D2：FB-3SDX(Denka，平均粒徑：3.3微米，比表面積(S.S.A)：3.9平方米/克)
E：2MAOK-PW(Sa-kuk Chemical，平均粒徑：2微米，熔點: 260℃)
F：KBM-303(ShinEtsu，環氧當量：222克/當量，密度：1.06)
(A系列：反應性共聚丙烯酸酯化合物，B系列：環氧樹脂，D系列：填充料)
比較例1至9
根據顯示於表2之組成比率，以如實施例1中之相同方法製得比較例之黏著組成物及片。
R1：KNB 40M(Kum-ho Petrochemical,丙烯腈-丁二烯橡膠，丙烯腈：41%,門尼黏度(ML+4,100℃)：60)
R2：KNB 20LM(Kum-ho Petrochemical,丙烯腈-丁二烯橡膠，丙烯腈：28%,門尼黏度(ML+4,100℃)：50)
以上製得之實施例及比較例之黏著片，係根據下述方-法來實行特性評估。
表面能
為評估使用於實施例之反應性共聚丙烯酸酯化合物及使用於比較例之丙烯腈-丁二烯橡膠之表面能，將各種製得之黏著組成物以相同的塗佈厚度塗佈於平面硬支持板，使用接觸角測量儀(SEO300A,Surface Electro Optics Co.,Ltd.)測量與水的表面能。
黏著強度
黏著強度測量係根據試驗模式JIS Z 0237及KSA 1107(黏著帶及片之試驗方法)使用萬能材料試驗機以90°剝離試驗來實行。用於黏著強度測量之試驗樣品係以1密耳(mil)厚之聚醯亞胺膜(IN70,SKC)於65℃熱壓縮於黏著片之兩面並切割成寬10毫米長150毫米之尺寸而製得。評估之試驗速度為50毫米/分鐘。
層壓特性
使用膠帶固定設備(DT-MWM 1230A,Dynatech Co.,Ltd.)於65℃以橡膠滾輪來回循環進行壓縮而使各種於實施例及比較例製得之黏著片與其上具有圖案之8吋晶圓進行層壓。觀察層壓樣品是否在晶圓與黏著片間產生空隙。該評估係產生之空隙為總面積之5%或較多時之狀況歸類為×，產生之空隙少於總面積之5%時之狀況為○。
高溫流動性及固化特性
各種於實施例及比較例製得之黏著片之高溫流動性係以測量聚合物流變之設備之黏彈儀(Rheovibron，RPT-3000W,AND Co.,Ltd.)在25℃至150℃的加熱條件下根據流體流動性測量阻尼比以評估。固化特性係根據黏著片在125℃等溫條件下60分鐘之相轉移(phase transition)來測量振盪週期以評估。
具體地，將製得之具200微米塗佈厚度之黏著片置於黏彈儀(Rheovibron)之加熱板上，並將管狀(RBP020)或刀狀(RBE130)探針浸入黏著片中。然後，在上述測量的條件下以固定的力量移開採針，由此改變黏著層內之流體特性並影響擺錘運動。由相應改變之擺錘週期、振幅及波數之特徵，評估高溫流動性及固化特性。固化特性係以擺錘週期初值與終值間之改變比率(%)計算。高溫流動性係由阻尼比以下列公式1計算。該評估係將於120℃具有0.1或較小對數阻尼比，而於80℃/120℃之阻尼比3.0或較大之黏著片歸類為○，於120℃具有0.1或較小對數阻尼比但具有2.0或較小之80℃/120℃阻尼比之黏著片歸類為△，其他狀況為×。
公式1
Δ對數阻尼比=[ln(A1/A2)+ln(A2/A3)+…+ln(An/A(n+1))]/n
在上列公式中，A1為正弦波中的第一個振幅值，A2為第二個振幅值，An為第n個振幅值，n為總數波。
剪力強度
將各種於實施例及比較例製得之黏著片接合於已完全形成圖案及鈍化之8吋，200微米晶圓背面。然後以切割裝置(DFD6361,Disco Co.,Ltd.)將晶圓切成2毫米×2毫米之晶片。使用黏晶裝置(SDB-30US,Secron Co.,Ltd.)在120℃，0.3兆帕(MPa)及3秒鐘之接合條件下將晶片雙層堆疊，然後在175℃固化2小時以製得測量剪力強度用之樣品。將某些製得的樣品分別保存於85℃具85%相對濕度之恆溫槽24小時以製得暴露於高溫/高濕之樣品。如此製得的樣品之剪力強度係以黏合測試器(DAGE-4000PXY,DAG Co.,Ltd.)測量並比較結果。
此外，當剪力強度在上述條件評估10次時，計數顯示黏結破壞狀態之樣品數，其係在剪切破碎表面上黏著層之破裂，並以%顯示。
金屬接線嵌入性
在具有自晶片頂部50微米高之金接線作為半導體晶片與基板間之金屬接線之半導體晶片上，使用黏晶裝置(SDB-30US,Secron Co.,Ltd.)於130℃，0.5兆帕(MPa)及1秒鐘之條件下，加熱黏合接合有黏著片之第二片晶片，然後在170℃固化2小時以製得堆疊晶片。研磨製得之堆疊晶片切面然後觀察接線是否受損及產生任何直徑5微米或較大之空隙。觀察結果當發生接線受損時以×表示，當空隙產生時為△及當狀況良好時為○。
熱收縮抗性
製得實施例及比較例之各種黏著片使具有60微米之乾厚度及100毫米×100毫米之尺寸並置於聚對苯二甲酸乙二酯膜上，該膜係已經過單面離型處理，然後保持於175℃之固化條件下2小時。測量因熱處理收縮變形之自底面之歪曲高度並記錄之。
抗濕性
使用於實施例及比較例製得之各種黏著片，將雙層堆疊晶片於121℃，100%相對濕度及2大氣壓的條件下進行加壓蒸煮試驗(PCT)達72小時，然後觀察黏著表面以檢查是否產生任何剝離。觀察結果當狀況良好時以○表示，當產生剝離時為×。
根據上述評估方法所得之結果中，表面能及黏著強度顯示於下面表3。於實施例及比較例製得之黏著片之評估結果分別顯示於下面表4及5。
Kgf：公斤力，mm：毫米
剪力強度1)：使用以175℃，2小時固化製得之樣品
剪力強度2)：使用以175℃，2小時固化製得且保存於85℃/85%相對濕度24小時之樣品
mm：毫米
由表3之結果，可見到使用於實施例之反應性共聚丙烯酸酯化合物與使用於比較例之橡膠成分比較顯示出較高的表面能及較高的黏著強度。於是，在使用彼等之黏著片中，對構成半導體支持構件之有機-無機材料於約60℃之固定條件下之初黏性得以改進。
由表4及表5之實施例及比較例之試驗結果，可見到本實施例之所有黏著片於每一評估項目均顯示良好之特性，但比較例者則否。

Claims (4)

  1. 一種製備用於製造半導體之黏著片之黏著組成物，係包括：(A)含有一個或多個環氧反應基以及一個或多個羥基反應基之共聚丙烯酸酯化合物，且當測量其與水之接觸角時，該共聚丙烯酸酯化合物具有自40達因/公分(dyne/cm)至50達因/公分之表面能，(B)熱固性環氧樹脂混合物，(C)固化劑，(D)填充料及(E)固化促進劑，其中該成分(A)：(B)之重量比率為95：5至65：35，該成分(B)包括一種或多種於150℃具有0.1泊(Pa‧s)或較低熔體黏度之環氧樹脂，於每100重量份之該等成分(A)+(B)+(C)之總合中，該成分(D)的含量為10至80重量份，於每100重量份之該等成分(A)+(B)+(C)之總合中，該成分(E)的含量為0.1至1.4重量份，及藉由該黏著組成物製備的該黏著片具有自3.0至5.0之對數阻尼比之間之比率，該比率係分別於80℃及120℃之高溫流動性測試進行測量，且於120℃具有0.01至0.1之對數阻尼比。
  2. 如申請專利範圍第1項所述之黏著組成物，其中，該環 氧樹脂混合物(B)中所含，於150℃具有0.1泊或較低熔體黏度之環氧樹脂量，基於100重量%之該環氧樹脂混合物(B)之量計，為5至50重量%。
  3. 如申請專利範圍第1項所述之黏著組成物，其中，該固化劑(C)對該環氧樹脂混合物(B)之當量比率為0.8至1.3。
  4. 一種用於製造半導體之黏著片，係包括申請專利範圍第1至第3項中任一項所述之黏著組成物之塗佈層者。
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