TWI512070B - 製造半導體之黏著組成物及膜 - Google Patents

製造半導體之黏著組成物及膜 Download PDF

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Publication number
TWI512070B
TWI512070B TW099138784A TW99138784A TWI512070B TW I512070 B TWI512070 B TW I512070B TW 099138784 A TW099138784 A TW 099138784A TW 99138784 A TW99138784 A TW 99138784A TW I512070 B TWI512070 B TW I512070B
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Taiwan
Prior art keywords
wafer
adhesive
epoxy
adhesive composition
resin
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TW099138784A
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English (en)
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TW201213477A (en
Inventor
Jin Won Kim
Sung Su 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 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
    • 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
    • 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
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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
    • 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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    • C09J7/00—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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    • 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
    • C09J7/30—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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    • 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
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    • 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
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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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    • 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
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    • 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
    • H01L2221/68327—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 used during dicing or grinding
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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

Description

製造半導體之黏著組成物及膜
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組成物，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，以及包括此黏著組成物之塗佈層之製造半導體之黏著膜。
在半導體製造過程中，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，故採用膜型黏著劑。該種膜型黏著劑係在其研磨程序完成後塗敷至具有圖案化電路之晶圓上，再藉由熱顯現黏著性質。結果，不像液體黏著劑，多層之晶片可經由將貼附至黏著膜之晶圓切割成晶片之切割程序，延伸，將經切割之晶片分隔成個別晶片之取晶(pick-up)程序以及將被取晶程序分隔之晶片安裝至基板上之接合程序而予以堆疊。然後對該等堆疊之晶片及基板施加金屬配線程序以使其電氣地連接以及施加保護晶片之環氧成形(expoxy-molding)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。
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之晶片。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(Thixotropy index)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(rillform)，然後以將黏著片切割成晶片尺寸再藉由使用特定裝置接合至基板，再使分隔之晶片貼附至其上之方式使用之。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至導線架或軟性印刷電路板。在該種接合程序中，當其在切割前與晶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漬不應因切割程序中所使用的加工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，自切割膜取晶應無困難，且在接合程序中，應對晶片及導線架或軟性印刷電路板顯示良好黏著性。
對需要高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鏈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。
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。
為了達到如上述說明之目的，本發明提供一種製造半導體之黏著組成物，包括：15至75重量份含有15至40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。
本發明之另一態樣係提供一種包括本發明之黏著組成物之塗佈層之製造半導體之黏著膜。
使用本發明之黏著組成物及黏著膜於半導體製程可提供的優點有在與晶圓層合期間對晶圓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之良好黏著性，因此可改良半導體封裝製程的操作效率及所製得之半導體產品的可靠度。
本發明詳述如下。
本發明之黏著組成物包括含有丙烯腈之丙烯酸樹脂。以100重量%樹脂計之，丙烯酸樹脂成分含有15至40重量%，較佳為20至40重量%丙烯腈單體單元。在本發明之一實例中，可使用藉由聚合15至40重量份丙烯腈化合物與60至85重量份丙烯酸酯化合物，如丙烯酸乙酯或丙烯酸丁酯所獲得之丙烯酸樹脂成分。若丙烯腈單體單元的含量小於15重量%，則與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40重量%，則樹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300,000至2,000,000，更佳為500,000至1,500,000之重量平均分子量。又，含有丙烯腈單體單元之丙烯酸樹脂具有較佳為-20℃至50℃，更佳為0℃至40℃之玻璃轉移溫度。若丙烯酸樹脂的重量平均分子量小於300,000，則樹脂的黏度可能太低，因此當構成黏著膜時樹脂可能太軟，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-20℃，則黏著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50℃，則半導體封裝製程中與晶圓的黏著性可能變得更差，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丙烯酸樹脂。若組成物中之含有丙烯腈之丙烯酸樹脂的含量低於此，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黏著性會不足，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酚醛樹脂之混合物。
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，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醚及其經烷基取代，鹵化或氫化之化合物，多官能化之環氧樹脂，含雜環之環氧樹脂等。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。更具體地說，可使用市售商品，雙酚A型環氧樹脂如EPICOAT807,EPICOAT815,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；酚醛清漆環氧樹脂如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之羥基當量值之酚醛樹脂。
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：酚醛樹脂中之羥基當量之比率，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酚醛樹脂之混合物。若組成物中環氧化合物與酚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，因此可能難以進行膜塗佈。
本黏著組成物包括填充劑。至於填充劑，與丙烯酸樹脂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，但不特別限定於此。依據本發明之一實例，雙酚A型，F型或A型與F型之混合物可使用作為環氧聚合物填充劑，且其重量平均分子量為10,000至100,000。
顆粒狀填充劑的實例包含二氧化矽(例如，熔融二氧化矽、乾二氧化矽)、氧化鋁(例如，球狀，角狀，板狀或片狀氧化鋁)、銀、金塗佈之球珠、聚矽氧烷球珠、碳黑、氫氧化鋁、氫氧化鎂、氮化硼、二氧化鈦、陶瓷等之顆粒。顆粒狀填充劑的平均顆粒大小較佳為10奈米至10微米，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。依據本發明之一實例，當使用氧化鋁時，可使用具有1:3至1:6之重量比之球狀：角狀氧化鋁之混合物。
本黏著組成物包括10至80重量份填充劑。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，若含量大於上述範圍，則與黏合膜的黏著性降低，因此製程操作效率可能下降。
除了前述成分外，本黏著組成物可進一步包括適量之習知使用於半導體加工之黏著組成物之額外成分，包含溶劑如丙酮、甲基乙基酮、甲苯、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，製造半導體之黏著胺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；基板層+黏著組成物層+黏合層等，但不限於此。
可包含於本製造半導體之黏著膜之基板層的材料並無特別限制。可使用習知上可作為黏著膜中之基板膜的材料如聚對苯二甲酸乙二酯、聚烯烴或聚氯乙烯。至於黏合層，可使用習知上使用於黏著膜中之黏合材料如含有光反應性寡聚物之丙烯酸材料。
在本製造半導體之黏著膜中，黏著組成物之塗佈層的厚度並無特別限制，其可依據具體的層結構改變，通常在5至300微米(μm)的範圍內。例如，當其與黏合層組合時黏著組成物之塗佈層的厚度可為5至80μm，當其被放置在兩個基板層之間時為20至100μm，及當其與一個基板層組合時為40至300μm，但不限於此。
本黏著膜的製備方法並無特別限制。其可藉由使用製備多層黏著膜之習知設備以習知方法製備之。依據本發明之一實例，本黏著膜可藉由在聚對苯二甲酸乙二酯之基板層上塗佈本黏著組成物，及若有需要，使其與塗佈著丙烯酸黏合材料之黏合膜層合而製備之。
藉由下述實施例及比較例更加詳細說明本發明。然而，本發明的範圍不侷限於此。
在下述實施例及比較例中，係依據下述方法評估黏著膜的性質。
黏著性質評估
實施例及比較例所製備之黏著膜的黏著性質係藉由依據JIS Z 0237及KSA 1107之測試模式使用萬能測試機以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80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20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65℃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200μm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，70μm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噴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20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，10之接腳數目及5mm之延伸，200μm至800μm之接腳衝程(pin stroke)範圍內的條件下進行取晶製程至晶圓的中央區域中之100片晶片。在任何接腳衝程中，評估係分類成一次取晶取回所有晶片的情形為O，兩次或三次取晶取回所有晶片的情形為△，需要超過三次取晶的情形為X。
實施例1至3
藉由使用球研磨機分散60重量份以如表1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)，20重量份環氧樹脂YDCN-500-4P(市售商品名，Kuk-do化學公司，200之環氧基當量，62℃之軟化點)與酚醛樹脂MEH-7800SS(Meiwha公司，175之羥基當量)之混合物(10重量份環氧樹脂+10重量份酚醛樹脂)及在20重量份甲基乙基酮溶劑中之20重量份作為填充劑之聚集顆粒狀之二氧化矽，再將所製備之混合物以20μm之乾厚度塗佈在具有38μm厚度之聚對苯二甲酸乙二酯之脫膜上。
使所製備之黏著膜與塗佈著厚度10μm之含有光反應性寡聚物之丙烯酸黏合材料之厚度為100μm之聚烯烴膜層合。對此層合膜施加200μm晶圓之黏著性質評估。結果示於表5。
實施例4至8
使用具有20重量%丙烯腈單體單元含量，10℃之玻璃轉移溫度及900,000之重量平均分子量之丙烯酸聚合物樹脂CS-200，實施例1至3所使用之環氧/酚醛樹脂混合物以及作為填充劑之平均顆粒直徑為20奈米之燻二氧化矽(R-972，Degussa公司)以表2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5。
實施例9至15
使用具有20重量%丙烯腈單體單元含量，10℃之玻璃轉移溫度及900,000之重量平均分子量之丙烯酸聚合物樹脂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。
*：二氧化矽[具有1.2μm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化學公司)
***：氧化鋁[具有0.5μm之平均顆粒直徑之球狀氧化鋁(ASFP-20,Denka公司)：具有1μm之平均顆粒直徑之角狀氧化鋁(A-43-M,Showa Denko公司)之1:5重量比的混合物]
****：銀[具有1至5μm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。
黏著性1) ：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
黏著性1) ：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
黏著性1) ：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
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。
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)
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。
1．．．晶圓
2．．．黏著組成物塗佈層
3．．．黏合材料層

Claims (6)

  1. 一種用於製造半導體的晶圓取晶製程之黏著組成物，包括：15至75重量份含有15至40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；其中該含有丙烯腈單體單元之丙烯酸樹脂具有700,000至1,000,000之重量平均分子量；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；以及其中該環氧化合物中之環氧基當量：該酚醛樹脂中之該羥基當量之比率為1：0.8至1：1.2。
  2. 如申請專利範圍第1項所述之用於製造半導體的晶圓取晶製程的黏著組成物，其中該含有丙烯腈單體單元之丙烯酸樹脂具有-20℃至50℃之玻璃轉移溫度。
  3. 如申請專利範圍第1項所述之用於製造半導體的晶圓取晶製程的黏著組成物，其中該環氧化合物係選自雙酚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，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醚及其經烷基取代，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。
  4. 如申請專利範圍第1項所述之用於製造半導體的晶圓 取晶製程的黏著組成物，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。
  5. 如申請專利範圍第4項所述之用於製造半導體的晶圓取晶製程的黏著組成物，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。
  6. 一種製造半導體之黏著膜，包括如申請專利範圍第1至5項中任一項所述之用於晶圓取晶製程之黏著組成物的塗佈層。
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