TW201213477A - Adhesive composition and film for manufacturing semiconductor - Google Patents

Adhesive composition and film for manufacturing semiconductor Download PDF

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Publication number
TW201213477A
TW201213477A TW099138784A TW99138784A TW201213477A TW 201213477 A TW201213477 A TW 201213477A TW 099138784 A TW099138784 A TW 099138784A TW 99138784 A TW99138784 A TW 99138784A TW 201213477 A TW201213477 A TW 201213477A
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TW
Taiwan
Prior art keywords
adhesive
resin
adhesive composition
epoxy resin
semiconductor
Prior art date
Application number
TW099138784A
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English (en)
Other versions
TWI512070B (zh
Inventor
Jin-Won Kim
Sung-Su Kim
Kwang-Ho Shin
Kyung-Nam Cho
Kyo-Sung Hwang
Chang-Bum Chung
Original Assignee
Kcc Corp
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Application filed by Kcc Corp filed Critical Kcc Corp
Publication of TW201213477A publication Critical patent/TW201213477A/zh
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Publication of TWI512070B publication Critical patent/TWI512070B/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09J133/18—Homopolymers or copolymers of nitriles
    • C09J133/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
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    • H01—ELECTRIC ELEMENTS
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
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    • 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
    • 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
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • 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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    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
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    • H01L2224/93—Batch processes
    • H01L2224/94—Batch processes at wafer-level, i.e. with connecting carried out on a wafer comprising a plurality of undiced individual devices

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Computer Hardware Design (AREA)
  • Health & Medical Sciences (AREA)
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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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201213477 · 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種製造半導體之黏著組成物及膜。尤 其，本發明係有關一種製造半導體之黏著絚成物，其包括 含有丙烯腈之丙烯酸樹脂、環氧化合物與酚醛樹脂之混合 物、及填充劑，且在半導體製造期間具有晶圓取晶製程之 良好特性並對晶圓、導線架和PCB基板具有良好黏著性， 以及包括此黏者組成物之塗佈層之製造半導體之黏著膜。 【先前技術】 隹牛等體裝造過程中，單層晶片封裝已使用液體型黏 著劑作為將得自晶圓切割程序之各晶片接合至導線架或軟 性印刷電路板(FPCB)之加工材料。隨著半導體製程的發 展，已廣泛利用使用多層晶片堆疊技術之半導體安裝 (mounting)封裝。在該種多層晶片堆疊封裝中，由於使用 液體黏著劑會使製程難以操控，故採㈣型黏㈣。'該種 膜型黏著_在其研磨程序完成後塗敷至財隨化電路 上’再藉由熱顯現黏著性質。結果，不像液體黏著 :’夕層之晶片可經由將貼附至黏著膜之晶圓切割成晶片 刀抽序，延伸，將經切割之晶片分隔成個別晶片之取 曰曰(⑽’程序以及將被取晶程序分隔之晶片絲至美板 上之接合料W輯疊。_賴等 二 屬配線程序以使其電氣地連接以心 二=形(expoxy_mo〗ding)程序。在如上述說明之製程中， 所採用之黏著膜係要在晶圓切割成晶片後之程序使用之。 95047 3 201213477 將晶片貼附至基板之習知方法包含將液體環氧樹脂 組成物以某種圖案塗敷至所準備之導線架或軟性印刷電路 板，再安裝藉由使用保護晶圓之黏合片予以預先加工 日白 片。然而，塗敷液體環氧樹脂組成物有控制塗敷厚度之均 勻度及晶片貼附所施加之壓力可能輕易地發生滲漏的問 題。可調整液體黏著組成物之搖變值（Thixotr〇py inde幻藉 以控制其流動性，但其限於單晶製造，因其難以應用至多 層晶片製造。 為了解決液體黏著劑所造成之上述問題，已有建議將 液體黏著劑改質成適當的樹脂組成物並以板片形式提供 之。該種板片型黏著劑係以類似於晶片的尺寸製備成細條 形式（rillfom) ’然後以將黏著片切割成晶片尺寸再藉由使 用特尤裝置接合至基板，再使分隔之晶片貼附至其上之方 式，用之。然而，由於此方法需要特定裝置及切割和接合 黏著片之額外程序，其利用性因而下降中。 在目前之半導體接合程序中，係將黏著片（膜）事先地 接合至晶圓的背面然後進行切割以使晶片接合 軟性印刷f路板。在該種接合程序巾，#其在㈣前與;曰 圓層合時黏著膜應無孔洞地貼附至晶圓。再者，黏著膜與 晶圓或切割膜之背面之間的脫層或浸潰不應因切割程^ 所使用的加I水及潔淨水和空氣而發生。此外，在由切割 程序所單離之晶片的取晶程序中，自㈣膜取晶應無困 難’且在接合程序巾，㈣^及導線架妹性印刷電路 板顯示良好黏著性。 95047 4 201213477 對需要向處理速度及高記憶、容量的產品而言，在半導 體晶片製造過程中，晶粒接合之黏著膜應在晶片與軟性印 刷電路板之間展現高黏著強度。若晶片與印刷電路板之間 的黏著強度不足，則在晶片製造過程中晶片可能會自軟性 印刷電路板分離。 韓國專利第10-0826420號提供一種使用在其主鍵具 有雙鍵之橡膠基樹脂之黏著膜組成物。然而，如這專利之 在樹脂的主鏈中存在雙鍵可能造成雙鍵的交鏈，其可能降 低對軟性印刷電路板的黏著強度。 韓國專利第10-0447014號提供一種使用耐熱性聚醯 亞胺型黏著組成物之黏著膜。然而，此專利之組成物雖然 具有高耐熱性但顯示低黏著強度。 【發明内容】 [欲解決的問題] 為了解決如上述說明之習知技藝的問題，本發明之目 的係提供一種對半導體製造期間之晶圓取晶製程具有良好 特性並對晶圓、導線架和PCB基板具有良好黏著性之製造 半導體之黏著組成物，以及包括此組成物之塗佈層之製造 半導體之黏著膜。 [技術手段] 為了達到如上述說明之目的，本發明提供—種製造半 導體之黏著組成物，包括：15至75重量份含有15至 重量％丙烯腈單體單元之丙烯酸樹脂；5至60重量份環氧 化合物與酚醛樹脂之混合物；以及10至80重量份填充劑。 5 95047 201213477 本發明之另-態樣係提供-種包括本發明之黏著组 成物之塗佈層之製造半導體之黏著膜。 [發明功效] 使用本發明之黏著組成物及黏著膜於半 提供㈣點有在與日3圓層㈣間對_具有良好貼附性和 黏合性，自切割膜之良好取晶特性及接合製程中 著性，因此可改良半導體封裝製程的操作效；及：f 半導體產品的可靠度。 【實施方式】 本發明詳述如下。 本發明之黏著組成物包括含有丙埽腈之丙締酸樹 脂。以100重量％樹脂計之，丙烯酸樹脂成分含 40重量％，較佳為20至40重量％丙烯腈單體^元5至 發明之-實例中，可使用藉由聚合15至4〇重量 化合物與60至85重量份丙烯酸酿化合物，如丙烯酸乙二 或丙烯酸丁 S旨所獲得之㈣酸樹脂成分。若丙烯腈單^ 元的含量小於15重量_環氧化合物的相容性會降 低:若丙烯腈單體單元的含量大於4〇重量％，貝情脂的分 子量增加太快。 本發明中，含有丙烯腈單體單元之丙烯酸樹脂具有較 佳為J〇G，_至2，_，_，更佳為漏，_至15。〇 〇〇〇 ST:均分子量。又’含有丙烯腈單體單元之丙烯酸樹 移二ί為_2〇C至5〇C ’更佳為〇。。至40。。之玻璃轉 右丙稀酸樹月日的重量平均分子量小於3〇〇,〇〇〇， 95047 6 201213477 則樹脂的黏度可能太低，因此t構成黏著_樹脂可能太 軟，導致難以構成黏著膜。若重量平均分子量大於 2,000,000，則樹脂的黏度可能太高，導致難以製造膜。若 丙烯酸樹脂的玻璃轉移溫度低於·抓，則㈣膜的表面潤 濕性可能太高，因此膜加工期間黏著膜與黏合膜的分離可 能變得更糟。若玻璃轉移溫度高於抓，則半導體封農製 程中與晶圓的減性可能變得更差，因此可能發生黏著膜 的脫層。 ' 本黏著組成物包括15至75重量份含有丙烯腈之兩稀 酸樹脂。若組成物中之含有丙烯腈之__脂的含量低 於此，則膜的塗佈性質可能劣化而膜可能太容易破裂。相 反地，若含量高於上述範圍，則雖可良好地形成膜但勘著 f生會不^ ’因此半導體晶片的可靠度會變得更差。 本黏著組成物包括環氧化合物與祕樹脂之混合物。 可使用於本發明之環氧化合物包含那些習知者，包 含’例如雙紛A型環氧樹脂，雙驗f型環氧樹脂，雙紛$ 型％氧，知’脂環族環氧樹月旨，脂肪族直鍵環氧樹脂，酚 酿/月漆％氧樹脂，甲崎漆環氧樹脂，㈣A清漆環氧樹 脂’雙紛之二縮水甘油基鍵，萘二醇之二縮水甘油基鱗， 紛化合物之二縮水甘油基鱗，醇化合物之縮水甘油基越及 =、’乂烧基取代’鹵化或氫化之化合物，多官能化之環氧樹 月曰3雜％之％氧樹脂等。這些環氧化合物可單獨或者以 ”兩，或更夕種之混合物使用之。更具體地說，可使用市 售商叩又酚A型環氧樹脂如Epic〇AT8〇7, Epic〇AT8i5 201213477 EPICOAT825, EPICOAT827, EPICOAT828, EPICOAT834, EPICOAT1001, EPICOAT1002, EPICOAT1003, EPICOAT1055, EPICOAT1004, EPICOAT1004AF, EPICOAT1007, EPICOAT1009, EPICOAT1003F, EPICOAT1004F (市售商品名，日本環氧樹脂公司），YD011， YD-012, YD-013K, YD-014, YD-017, YD-112, YD-113, YD-114, YD-115, YD-127, YD-128(市售商品名，Kuk-do 化 學公司），SE-187, SE-187P(市售商品名，Shin-wha T&C 公 司）等；雙酚F型環氧樹脂如YDF-161，YDF-162， YDF-170(市售商品名，Kuk-do化學公司），SE-187， SE-187P(市售商品名，Shin-wha T&C公司）等；盼趨清漆 環氧樹脂如 EPPN-201，EPPN-501, EPPN-501HY, EPPN-502(市售商品名，Nippon Kayaku 公司），YDPN-631， YDPN-636，YDPN-638(市售商品名，Kuk-do化學公司）等； 以及甲酚清漆環氧樹脂如YDCN-500-1P，YDCN-500-4P， YDCN-500-5P, YDCN-500-7P, YDCN-500-10P, YDCN-500-80P (市售商品名，Kuk-do化學公司）， EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1020, EOCN-1025, EOCN-1027(市售商品名，Nippon Kayaku公司）。這些環氧化合物可單獨或者以其兩種或更 多種之混合物使用之。 對於可使用於本發明之酚醛樹脂並無特別限制而較 佳為具有100當量/公斤（eq/kg)至300eq/kg之經基當量值 之盼膝樹脂。 8 95047 201213477 在其混合物中之環氧化合物與酚醛樹脂的混合比 率，如環氧化合物中之環氧基當量：酚醛樹脂中之經基當 量之比率，較佳為1:0.8至1:1.2。若混合比率逾越此範圍， 則由於缺乏環氧•酚固化系統而可能發生過固化或未固 化’其可能導致在半導體晶片製程之後可靠度評估上的問 題。 本黏著組成物包括5至60重量份環氧化合物與齡酸 樹脂之混合物。若組成物中環氧化合物與盼醛樹脂之混合 物的含量小於此，則固化產物在高溫的性質可能劣化，因 此可能有長期使用上的問題。相反地，若含量大於上述範 圍’則膜可能太硬，因此可能難以進行獏塗佈。 本黏著組成物包括填充劑。至於填充劑，與丙烯酸樹 月曰成分難混溶之環氧聚合物化合物，球狀或聚集狀 (agglomerated)之顆粒等可單獨或以其混合物使用之。 至於與丙烯酸樹脂成分難混溶之環氧聚合物化合 物’較佳為那些具有50,000或更大之重量平均分子量者， 仁不特別限定於此。依據本發明之一實例，雙酚A型，F 型或A型與？型之混合物可使用作為環氧聚合物填充劑， 且其重里平均分子量為10,000至100,000。 〆狀填充劑的實例包含二氧化石夕（例如，炼融二氧化 矽、乾一氣化矽）、氧化鋁（例如，球狀，角狀，板狀或片 狀氧化鋁）、# A 1 ^ 銀、金塗佈之球珠、聚矽氧境球珠、碳黑、氫 乳化鋁、虱氧化鎂、氮化硼、二氧化鈦、陶瓷等之顆粒。 顆粒狀填充_平_粒大小較佳為 10奈米至10微米， 9 95047 201213477 更佳為20奈米至5微米。可使用球狀或聚集狀之顆粒狀填 充劑。依據本發明曰之1例，當使用氧化_，可使用具 有至1:6之重量tb之球狀：角狀氧化紹之混合物。 本黏著組成物包括1G至8G重量料錢。若組成物 中填充劑的含量小於此’則黏著產物的強度可能下降。相 反地’右含量大於上述範圍，則與黏合膜的黏著性降低， 因此製程操作效率可能下降。 除了則述成分外，本黏著組成物可進一步包括適量之 習知使用於半導體加卫之黏著組成物之額外成分 ，包含溶 劑如丙酮、曱基乙基_、曱苯、乙酸乙酯等。 本黏著組成物的製備方法並無特別限制。其可藉由使 用製備黏著組成物之習知設備以習知方法製備之。依據本 發明之一實例，本黏著組成物可藉由使用混合裝置如球研 磨機在室溫或適當升溫下分散或混合上述之含有丙烯腈之 丙烯酸樹脂，環氧化合物，酚醛樹脂和填充劑，以及額外 成分如溶劑而製備之。 依據本發明之另一態樣，製造半導體之黏著膜包括如 上述之本發明之黏著組成物之塗佈層。 本發明之製造半導體之黏著膜的特徵在於包括本發 明之黏著組成物之塗佈層，及若有需要，可進一步包括亦 可稱為脫膜層或保護（膜）層之一種或多種基板（膜）層，以及 一種或多種黏合(膜)層。依據本發明之一實例之製造半導 體之黏著膜可具有層結構如黏著組成物層+黏合層；基板 層+黏著組成物層+基板層；黏著組成物層+基板層；基板 10 95047 201213477 層+黏著組成物層+黏合層等，但不限於此。 半導體之黏著膜之基板層的材料並 …、特別限制。可使用習知上可作為 料如聚對苯-甲酸？ 言膘中之基板膜的材 丁本一甲酉夂乙一酯、聚烯烴或聚氯 =，可使用習知上使用於黏著膜中之黏合材料如含有;; 應性募聚物之丙騎材料。 3有先反 厚;造半導體之黏著財，黏著組成物之塗佈層的 f度並無特別關，其可依據具㈣層結構改變，通常在 ^_微米（"_範_。例如’當其絲合層組合時 者，.且成物之塗佈層的厚度可為5至8()_，當其被放置 兩2板層之間時為2u_m，及當其與 層組合時為40至300"m，但不限於此。 板 本黏著膜的製備方法並無特別限制。其可藉由使 ，多層黏著膜之習知㈣以f知方法製備之。依據本 -實例，本黏著膜可藉由在聚對苯二甲酸乙二酉旨之 上塗佈本黏著組成物，及若有需要 土 酸點合材料之黏合膜層合^”之。使，、與塗佈著兩烯 藉由下述實施例及比較例更加詳細說明本發明 而’本發明的範圍不侷限於此。 d 在下述實施例及比較财，係 犋的性質。 riL万忐。子估黏著 黏著性質評估 實施例及比較例所製備之㈣膜㈣著性質 依據JIS 2： 0237及KSA 1107之測士式植^ 9由 、州忒模式使用萬能測試機 11 95047 201213477 以180°剝離測試評估之。 為了評估uv輻射曝光後之黏著性，對使用uv輻射 裝置在150毫焦耳/平方公分（mJ/cm2)以8〇毫瓦特/平方公 分(mW/cm2)的強度曝露於uv輻射然後在室溫保持2〇分 鐘的試樣進行180 °剝離測試。 晶圓與黏著膜間之孔洞觀察 藉由使用帶狀安裝裝置（DT-MWM 1230A，Dynatech 公司）經由滾筒式條棒在65t：壓榨實施例及比較例所製備 之黏著膜後，觀察晶圓與黏著膜間之孔洞的存在與否。 削片與掉片評估 使所製備之黏著膜貼附於8吋之2〇〇/im晶圓，再使 用切割裝置（DFD6361，Disco公司）予以切割及沖洗，然後 以裸眼及光學顯微鏡觀察之。切割程序係在晶片尺寸X 10mm，70mm/s之進料速度，7〇ym之刀片高度及 30,000rpm之刀片旋轉速度的條件下進行之。沖洗程序係 藉由當旋轉晶圓時對其嘴灑超純水及壓縮之空氣而進行 之。記錄削片的數目（其為晶片邊緣破壞的缺陷），及掉片。 取晶特性評估 在切割及沖洗程序完成後，使用uv輻射裝置使晶圓 曝露於150mJ/cm2之UV輻射然後在室溫保持2〇分鐘。然 後使用晶粒貼附裝置（SDB-30US，SeCron公司）評估取晶特 性。在設定於10mm X 10mm之晶片尺寸，1〇之接腳數目 及5mm之延伸，200/zm至800/zm之接腳衝程（pinstr〇ke) 範圍内的條件下進行取晶製程至晶圓的中央區域中之1〇〇 95047 12 201213477 片晶片。在任何接腳衝程中，評估係分類成—次取晶取回 所有晶片的情形為〇，兩次或三次取晶取回所有晶片的产 形為△，需要超過三次取晶的情形為X。 月 實施例1至3 藉由使用球研磨機分散60重量份以如表丨所示之經 控制含量之丙烯腈（AN)單體所製備之丙烯酸聚合物樹脂 CS-200(市售商品名，Tae_wha公司），2()重量份環氧樹脂 YDCN-500-4P(市售商品名，Kuk_d〇化學公司，2㈨之環^ 基當量，62°C之軟化點）與酚醛樹脂MEH 78〇〇ss(Me=ha 么! /75之輕基當量）之混合物（10 4量份環氧樹脂+10 重量份轉樹脂)及在2G重量份甲基乙基_溶劑中之 劑之Γ顆粒狀之二氧化珍，再將所製備之 :二s厚度塗佈在具有38"m厚度之聚對笨 一甲酸乙一酯之脫膜上。 个 使所製備之黏著膜與塗佈著厚度10/zm 性寡聚物之丙烯酸黏合材料 有先反應 層合。對此層合膜施加2 =圓=心之聚烯烴膜 果示於表5。 心日⑽之黏纽質評估。結 95047 13 201213477 [表i] 成分 實施例 1 實施例 2 實施例 3 丙烯酸 松t月曰 AN單體單元含量 (wt%) 20 30 40 重量平均分子量（MW) 700,000 900,000 1,000,000 玻璃轉移溫度（Tg，°C) 5 15 20 用量（重量份） 60 60 60 環氧/酚醛樹脂混合物用量 (重量份） 20 20 20 填充劑用量 (重量份） 20 20 20 實施例4至8 使用具有20重量％丙埽腈單體單元含量，赃之玻璃 轉移溫度及900，_之重量平均分子量之丙賴聚合物樹 脂二’實_ 1至3所使用之環氧/祕樹脂混合物 =為:真充劑之平均顆粒直徑為2。奈米之燦二氧化梦 (R-972，Degussa 公司）以表 — 至3之相同方法製備料膜 $ ’藉由實施例1 如實施例1至3之相同方法進行評估。結果=表5 95047 14 201213477 [表2](單位：重量份) 成分 實施例 4 實施例 5 實施例 6 實施例 7 實施例 8 丙烯酸樹脂 20 30 50 65 75 環氧/酚_脂混合物 60 50 30 15 5 填充劑 20 20 20 20 20 實施例9至15 使用具有20重量％丙烯腈單體單元含量，l〇°C之玻璃 轉移溫度及900,000之重夏平均分子量之丙稀酸聚合物樹 脂CS-200，實施例1至3所使用之環氧/酚醛樹脂混合物 以及各種填充劑以表3所示之用量，藉由實施例1至3之 相同方法製備黏著膜。對此所製備之黏著膜，藉由如實施 例1至3之相同方法進行評估。結果示於表6。 [表3](單位：重量份) 成分 實施例 9 實施例 10 實施例 11 實施例 12 實施例 13 實施例 14 實施例 15 丙稀酸樹脂 60 60 50 40 20 15 15 環氧/酚醛樹 脂混合物 30 30 25 20 20 5 5 填充劑 10* 10** 25* 40* 60* 80*** 本氺氺氺 二氧化矽[具有1.2/zm之平均顆粒直徑之熔融二氧化矽 (SO-31R，Datsumori 公司）] :高分子量環氧（苯氧樹脂）（YP-50，YP-70, Kuk-do化學 15 95047 201213477 公司） 氺氺氺 •氧化铭[具有0 · 5 “ m之平均顆粒直徑之球狀 (ASFP-20，Denka公司）：具有l#m之平均顆粒直^化銘 狀氧化鋁（A-43-M，Showa Denko公司）之！ . ς去a λ , . 3篁量比的 混合物] ****:銀[具有1至5#m之平均顆粒直徑之銀薄片 (KSDF-50300, Konatec 公司）] 比較例1至6 使用如表4所示之丙烯酸聚合物樹脂CS-200及實施 例1至3所使用之環氧/酚醛樹脂混合物和填充劑，藉由實 施例1至3之相同方法製備黏著膜。對此所製備之黏著膜， 藉由如實施例1至3之相同方法進行評估。結果示於表7。 [表4](用量單位：重量份） 成分 比較例 1 比較例 2 比較例 3 比較例 4 比較例 5 比較例 6 丙 烯 酸 樹 脂 AN (wt%) 10 50 20 20 20 20 MW 200,000 250 900,000 900,000 900,000 900,000 Tg -30 60 10 10 10 10 用量 60 60 10 77 70 7 環氧/酚麵 脂混合物用量 20 20 70 3 25 3 填充劑用量 20 20 20 20 5 90 95047 16 201213477 [表5] 實 實 實 實 實 實 實 實 性 質 施 施 施 施 施 施 施 施 例 例 例 例 例 例 例 例 1 2 3 4 5 6 7 8 黏著性υ 240 180 220 200 150 250 250 250 黏著性 黏著性* 16 9 12 11 10 11 18 15 ㈣叶） 黏著性** 150 160 130 170 150 160 140 130 黏著性*** 170 180 160 200 170 190 170 160 孔洞觀察 孔洞 無 無 無 無 無 無 無 無 切割製程 削片（ea) 0 0 0 0 0 0 0 0 評估 掉片（ea) 0 0 0 0 0 0 0 0 取晶(接腳 200 0 0 0 0 〇 0 0 0 衝程，"m) 400 0 0 0 0 〇 0 0 0 黏著性υ:υν輻射前黏著組成物層與黏合材料層間之黏著 強度 黏著性* : UV輻射後黏著組成物層與黏合材料層間之黏著 強度 黏著性**:晶圓與黏著膜間之黏著強度 黏著性*** :軟性電路板與黏著膜間之黏著強度 17 95047 201213477 [表6] 性 質 實施 例9 實施 例10 實施 例11 實施 例12 實施 例13 實施 例14 實施 例15 黏著性u 240 180 220 200 200 50 150 黏著性 黏著性* 16 9 12 11 15 5 10 (gf/吋） 黏著性** 150 160 130 170 150 140 130 黏著性*** 170 190 160 200 170 160 160 孔洞觀察 孔洞 無 無 無 無 無 無 無 切割製程 削片㈣ 0 0 0 0 0 0 0 評估 掉片（ea) 0 0 0 0 0 0 0 取晶（接腳 200 0 0 0 0 0 0 0 衝程，/im) 400 0 0 0 0 0 0 0 黏著性n:UV輻射前黏著組成物層與黏合材料層間之黏著 強度 黏著性* : UV輻射後黏著組成物層與黏合材料層間之黏著 強度 黏著性:晶圓與黏著膜間之黏著強度 黏著性***:軟性電路板與黏著膜間之黏著強度 18 95047 201213477 [表7] 性質 比較 例1 比較 例2 比較 例3 比較 例4 比較 例5 比較 例6 黏著性 (g沒吋） 黏著性υ 350 80 220 200 150 250 黏著性* 60 9 12 11 10 11 黏著性** 300 10 130 170 150 10 黏著性*** 350 無法 測試 150 180 160 無法 測試 孔洞觀察 孔洞 益 有 有 益 無 有 切割製程 評估 削片（ea) 0 0 0 30 30 0 掉片（ea) 0 100 0 0 0 100 取晶（接腳 衝程，"m) 200 X 無法 測試 0 X X 無法 測試 400 X 0 〇 0 黏著性υ:υν輻射前黏著組成物層與黏合材料層間之黏著 強度 黏著性* : UV輻射後黏著組成物層與黏合材料層間之黏著 強度 黏著性**:晶圓與黏著膜間之黏著強度 黏著性***:軟性電路板與黏著膜間之黏著強度 由上述評估結果可看出，依據本發明之黏著膜對晶圓 及印刷電路板顯示高黏著強度以防止晶圓切割製程期間可 能發生的晶片破壞，而具有良好取晶特性。 19 95047 201213477 【圖式簡單說明】 第1圖係示意表示其中將依據本發明之黏著膜塗敷至 晶圓之狀態的實例。 第2圖係示意表示依據本發明之黏著膜之實例的層結 構（上圖）及其中即將使用之前自其移除脫膜層的狀態（下 圖）。 第3圖係示意表示包括依據本發明之黏著膜之切割/ 晶粒接合膜之實例的層結構。 【主要元件符號說明】 1 晶圓 2 黏著組成物塗佈層 3 黏合材料層 4 基板層（脫膜層） 20 95047

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  1. 201213477 七、申請專利範圍： 1. -種製造半導體之黏著組成物，包括：15至 含有15至40重量%丙烯腈單體單元之丙歸酸樹二 至60重量份環氧化合物與祕樹脂之混合物:， 至80重量份填充劑。 & 1G 300,000至2,000,000之重量平均分子量 2·如申請專利範_ i項所述之製造半導體的點著 物，其中該含有丙烯腈單體單元之丙烯酸樹脂且 ΊΠΠ 5 9 nnn nrm 土曰θ ^ 3.如申請專利範圍第1項所述之製造半導體的㈣ 物’其中該含有丙烯腈單體單元之丙稀酸樹月旨具 。(：至50°C之玻璃轉移溫度。 〃 ' 4. 如申請專祕1項所敎製造半導料_著組成 物，其中該環氧化合物係選自雙酚A型環氣樹脂'、，雙 酚F型環氧樹脂，雙酚S型環氧樹脂，脂環族環氧^脂， 脂肪族直鏈環氧樹脂，酚醛清漆環氧樹脂，甲酚清漆環 氧樹脂，雙酚A清漆環氧樹脂，雙酚之二縮水甘油基 醚，萘二醇之二縮水甘油基醚，酚化合物之二縮水甘油 基醚，醇化合物之縮水甘油基趟及其經烧基取代，鹵化 或氫化之化合物，多官能化之環氧樹脂，含雜環之環氧 樹脂，及其混合物。 5. 如申請專利範圍第1項所述之製造半導體的黏著組成 物，其中該酚醛樹脂具有100當量/公斤（eq/kg)至300 當量/公斤之羥基當量值。 6. 如申請專利範圍第1項所述之製造半導體的黏著組成 1 95047 201213477 物，其中該填充劑為環氧聚合物化合物、球狀或聚集狀 之顆粒或其混合物。 7. 如申請專利範圍第6項所述之製造半導體的黏著組成 物，其中該顆粒為二氧化矽、氧化鋁、銀、金塗佈之球 珠、聚矽氧烷球珠、碳黑、氫氧化鋁、氮化硼、二氧化 鈦、陶瓷或其混合物。 8. —種製造半導體之黏著膜，包括如申請專利範圍第1至 7項中任一項所述之黏著組成物的塗佈層。 2 95047
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CN103642408A (zh) * 2013-11-27 2014-03-19 常熟市富邦胶带有限责任公司 一种以bn为导热剂导热双面胶带及其制备工艺
CN103642415A (zh) * 2013-11-27 2014-03-19 常熟市富邦胶带有限责任公司 一种导热双面胶带
CN104726032A (zh) * 2013-12-24 2015-06-24 日东电工株式会社 粘接薄膜、切割/芯片接合薄膜、半导体装置的制造方法以及半导体装置
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