TWI583760B - A film-like adhesive, a bonding sheet for semiconductor bonding, and a method of manufacturing the semiconductor device - Google Patents

A film-like adhesive, a bonding sheet for semiconductor bonding, and a method of manufacturing the semiconductor device Download PDF

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Publication number
TWI583760B
TWI583760B TW102127722A TW102127722A TWI583760B TW I583760 B TWI583760 B TW I583760B TW 102127722 A TW102127722 A TW 102127722A TW 102127722 A TW102127722 A TW 102127722A TW I583760 B TWI583760 B TW I583760B
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Taiwan
Prior art keywords
film
adhesive
wafer
semiconductor
sheet
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Application number
TW102127722A
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English (en)
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TW201425511A (zh
Inventor
Yoji Wakayama
Isao Ichikawa
Takashi Akutsu
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Lintec Corp
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Publication of TW201425511A publication Critical patent/TW201425511A/zh
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
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    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
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    • 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
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
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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
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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
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
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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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
    • C—CHEMISTRY; METALLURGY
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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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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
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    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
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    • 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
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    • H01L24/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L24/80 - H01L24/90
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Description

膜狀接著劑、半導體接合用接著片及半導體裝置的製造方法
本發明係關於特別適用於將半導體晶片接著(黏晶)於諸如有機基板、導線架或其他半導體晶片上的步驟中所使用膜狀接著劑、半導體接合用接著片，以及使用該膜狀接著劑、該接著片的半導體裝置之製造方法。
諸如矽、鎵砷等半導體晶圓例依大徑狀態製造，該晶圓在切斷分離(切割)成元件小片(半導體晶片)後，便被移送往下一步驟的黏晶步驟。此時，半導體晶圓利用背面研削步驟而薄化，然後黏貼於接著片上，經切割、洗淨、乾燥、擴展、拾取等各項步驟後，便被移往下一步驟的黏合步驟。
黏合步驟中，將半導體晶片安裝於印刷電路板時，係有採取在半導體晶片的電路面側之連接墊部上形成由共晶焊錫、高溫焊錫、金等構成的導通用突起物(凸塊電極)，再利用所謂「倒置方式」使該等凸塊電極依相對面方式接觸於晶片搭載用基板上的相對應端子部，並施行熔融/擴散接合的覆晶安裝方法。此種安裝方法若近年普及通稱「黏晶薄膜」呈貼附於晶圓的狀態，將晶圓予以個片化而獲得晶片，若在黏晶時使用供將晶片與晶片搭載用基板予以接著用的接著薄膜，便可較其他形態使用填底膠材料的情況更為簡便。
但是，針對黏晶薄膜適用於該安裝方法時，會有如下述問題。即，覆晶安裝方法係藉由光學性讀取在半導體晶片的電路面上所形成對準標記，便可正確地黏晶於既定位置處。所以，當接著薄膜未具有足夠透明性的情況，便會有對準標記讀取困難的問題發生。
專利文獻1有揭示：波長440nm~770nm光的穿透率為74%以上之具接著薄膜的電子零件。此處所揭示的接著薄膜雖未含有填充材，但在接著薄膜之線膨脹係數調整、吸濕性抑制等目的下有添加填充材。在覆晶安裝方法中，當將接著薄膜使用為黏晶薄膜時，因為在晶圓的表面側貼附接著薄膜，因而在接著薄膜未被切割片覆蓋而呈露出狀態施行切割，此情況，露出的接著薄膜暴露於切割時的洗淨水中。所以，在吸濕性控制目的下，期待在接著薄膜中添加填充材。藉由控制吸濕性，便可提升切割時的接著薄膜耐水性、所獲得半導體裝置的封裝可靠度。然而，因構成接著薄膜的其他成分、與填充材間之光學特性不同，導致會有接著薄膜的透明性降低之可能性。所以，因在半導體晶片的電路面上所貼附接著薄膜，會導致對準標記讀取性嫌不足的情形。
[先行技術文獻] [專利文獻]
[專利文獻1]日本專利特開2011-171688
於是，本發明目的在於提供：倒裝安裝方法中能正確地將半導體晶片黏晶於既定位置處，且能製造高封裝可靠度半導體裝置的膜狀接著劑、及使用其之半導體接合用接著片。
解決上述課題的本發明係包括有以下主旨。
[1]一種膜狀接著劑，含有：(A)黏結劑樹脂、(B)環氧樹脂、(C)熱硬化劑及(D)填料；其中，D65標準光源的全光線穿透率係70%以上；霧度值係50%以下。
[2]如[1]所記載的膜狀接著劑，其中，含有(D)填料達5質量%以上。
[3]如[1]或[2]所記載的膜狀接著劑，其中，(D)填料的平均粒徑係50nm以下。
[4]如[1]~[3]中任一項所記載的膜狀接著劑，其中，(A)黏結劑樹脂係含有源自環氧基含有單體之構成單元5~30質量%的丙烯酸聚合物。
[5]如[1]~[4]中任一項所記載的膜狀接著劑，其中，相對於(A)黏結劑樹脂100質量份，(B)環氧樹脂含有量係50~1000質量份。
[6]一種半導體接合用接著片，在支撐片上，可剝離地形成以[1]~[5]中任一項所記載的膜狀接著劑為接著劑層。
[7]如[6]所記載的半導體接合用接著片，其中，支撐片係含有以由胺甲酸乙酯聚合物與乙烯系聚合物所構成的 複合薄膜、或胺甲酸乙酯丙烯酸酯硬化物薄膜為構成層。
[8]一種半導體裝置的製造方法，使用上述[1]~[5]中任一項所記載的膜狀接著劑、或[6]或[7]所記載的半導體接合用接著片，其包括：在晶圓上貼附著膜狀接著劑、或半導體接合用接著片之接著劑層的步驟；將晶圓予以個片化而獲得晶片的步驟；以及經由膜狀接著劑或接著劑層而將晶片予以固定的步驟。
根據本發明的膜狀接著劑、及使用其之半導體接合用接著片，便可適用於覆晶安裝方法，能正確定位地將晶片彼此間、或將晶片與基板相互接著。又，即便嚴苛環境下，仍可獲得高封裝可靠度的半導體裝置。
首先針對本發明的膜狀接著劑進行說明。
(膜狀接著劑)
本發明的膜狀接著劑係含有以：(A)黏結劑樹脂、(B)環氧樹脂、(C)熱硬化劑及(D)填料為必要成分，為改良各種物性，視需要亦可含有其他成分。以下，針對該等各成分進行具體說明。
(A)黏結劑樹脂
黏結劑樹脂係在能對膜狀接著劑賦予造膜性與可撓性之聚合體成分的前提下，其餘並無限定，可例如：丙烯酸聚合物、 聚酯樹脂、聚乙烯醇樹脂、聚乙烯丁醛、聚氯乙烯、聚苯乙烯、聚醯胺樹脂、纖維素、聚乙烯、聚異丁烯、聚乙烯醚、聚醯亞胺樹脂、苯氧樹脂、苯乙烯-異戊二烯-苯乙烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物等。該等黏結劑樹脂係可單獨使用、亦可組合使用2種以上，就從避免因異種黏結劑樹脂彼此間的相溶性低，而造成膜狀接著劑的透明性降低之觀點，最好單獨使用，當組合2種以上時，最好選擇組成類似者等不致使相溶性降低的方式進行選擇。上述所列舉者中，最好使用膜狀接著劑的各種特性(特別係黏結劑樹脂與其他成分的相溶性)較容易調整之丙烯酸聚合物。
丙烯酸聚合物係可使用自習知起便屬公知的丙烯酸聚合物。丙烯酸聚合物的重量平均分子量較佳係1萬~200萬、更佳係10萬~150萬。若丙烯酸聚合物的重量平均分子量過低，在與後述半導體接合用接著片所使用支撐片間之剝離力提高，導致由膜狀接著劑所構成接著劑層與支撐片發生層間剝離不良情形。又，若丙烯酸聚合物的重量平均分子量過高，則膜狀接著劑便無法追蹤基板的凹凸，導致成為發生孔隙等的肇因。
丙烯酸聚合物的玻璃轉移溫度較佳係-30~50℃、更佳係-10~40℃、特佳係0~30℃範圍。若玻璃轉移溫度過低，則由膜狀接著劑所構成接著劑層與支撐片間之剝離力變大，導致接著劑層與支撐片發生層間剝離不良情形；反之若過高，則會有為固定晶圓用的接著力嫌不足之可能性。
構成丙烯酸聚合物的單體(原料單體)，係含有必需 成分的(甲基)丙烯酸酯單體。(甲基)丙烯酸酯單體的具體例係可例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十八烷基酯等烷基碳數1~18的(甲基)丙烯酸烷基酯；(甲基)丙烯酸環烷基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、醯亞胺(甲基)丙烯酸酯等具有環狀骨架的(甲基)丙烯酸酯；(甲基)丙烯酸羥甲酯、(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-2-羥基丁酯等含有羥基的(甲基)丙烯酸酯；(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸-3,4-環氧環己基甲酯等含有環氧基的(甲基)丙烯酸酯；(甲基)丙烯酸單甲胺酯、(甲基)丙烯酸單乙胺酯、(甲基)丙烯酸二乙胺酯等含有胺基的(甲基)丙烯酸酯；2-(甲基)丙烯醯氧基乙基酞酸酯、2-(甲基)丙烯醯氧基丙基酞酸酯等含有羧基的(甲基)丙烯酸酯。該等係可單獨使用1種、亦可併用2種以上。
再者，丙烯酸聚合物的原料單體尚可與(甲基)丙烯酸酯單體一起使用例如：(甲基)丙烯酸、衣康酸等(甲基)丙烯酸酯以外之具羧基的單體；乙烯醇、N-羥甲基(甲基)丙烯醯胺等(甲基)丙烯酸酯以外之具羥基的單體；(甲基)丙烯醯胺、醋酸乙烯酯、丙烯腈、苯乙烯等。
再者，構成丙烯酸聚合物的單體係就從獲得與(B) 環氧樹脂間之相溶性良好的丙烯酸聚合物觀點，最好使用至少含有環氧基的單體。此情況，丙烯酸聚合物中，源自含環氧基之單體的構成單元較佳係依5~30質量%範圍含有、更佳係依10~25質量%範圍含有。藉由丙烯酸聚合物構成單元的含環氧基之單體係依此種範圍含有，便可輕易地避免因丙烯酸聚合物與(B)環氧樹脂間之相溶性降低，所造成的膜狀接著劑透明性降低情形。含環氧基之單體係除上述所列舉含環氧基之(甲基)丙烯酸酯外，尚可例如：環氧丙基乙烯醚、3,4-環氧環己基乙烯醚、環氧丙基(甲基)烯丙醚、3,4-環氧環己基(甲基)烯丙醚等。
再者，丙烯酸聚合物亦可含有：含羥基之(甲基)丙烯酸酯、含胺基之(甲基)丙烯酸酯、(甲基)丙烯酸等源自具有活性氫基之單體的構成單元。藉此，藉由在膜狀接著劑中摻合入後述(I)交聯劑，便可促使丙烯酸聚合物進行交聯，俾可控制膜狀接著劑的初期接著力與凝聚性。此情況，丙烯酸聚合物中，源自具有活性氫基之單體的構成單元較佳係含有1~30質量%左右的範圍。
丙烯酸聚合物係使用上述原料單體，依照習知公知方法便可製造。
(B)環氧樹脂
(B)環氧樹脂係可使用習知公知的各種環氧樹脂。環氧樹脂係可例如：雙酚A型環氧樹脂、雙酚F型環氧樹脂、伸苯骨架型環氧樹脂、酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、二環戊二烯型環氧樹脂、聯苯型環氧樹脂、三酚甲烷型環氧樹脂、雜環型環氧樹脂、茋型環氧樹脂、縮合環芳香族烴改質環 氧樹脂；該等的鹵化物等構造單元中含有2以上官能基的環氧樹脂。又，亦可使用具有不飽和烴基者。此種環氧樹脂已有揭示於例如日本專利特開2008-133330。環氧樹脂的環氧當量並無特別的限定，較佳係150~250(g/eq)。環氧當量係根據JIS K7236；2001所測定的值。該等環氧樹脂係可單獨使用1種、亦可併用2種以上。
本發明的膜狀接著劑中，相對於(A)黏結劑樹脂100質量份，(B)環氧樹脂含有量較佳係50~1000質量份、更佳係100~600質量份、特佳係150~400質量份。藉由(B)環氧樹脂含有量設為上述範圍，便可利用將覆晶安裝於基板的步驟中之焊錫加熱時的熱，使(B)環氧樹脂其中一部分硬化，俾使膜狀接著劑成為B階段狀態，便可輕易地防止焊錫流出。又，若(B)環氧樹脂含有量高於上述範圍，則膜狀接著劑與支撐片間之剝離力會變為過高，導致由膜狀接著劑所構成接著劑層與支撐片發生層間剝離不良情形。
(C)熱硬化劑
(C)熱硬化劑係對(B)環氧樹脂具有熱硬化劑的功能。(C)熱硬化劑係可例如分子中具有2個以上能與環氧基產生反應之官能基的化合物。能與環氧基產生反應的官能基係可例如：酚性羥基、醇性羥基、胺基、羧基、源自酸酐的官能基等，該等之中，較佳係酚性羥基、胺基及源自酸酐的官能基，更佳係酚性羥基及胺基。
(C)熱硬化劑的具體例係可例如：酚醛型酚樹脂、二環戊二烯系酚樹脂、多官能基系酚樹脂、芳烷基酚樹脂等酚 系熱硬化劑；DICY(雙氰胺)等胺系熱硬化劑。又，亦可使用具有不飽和烴基的熱硬化劑。例如可將日本專利特開2008-248129所揭示，1分子中具有能與環氧基進行反應之官能基及不飽和烴基的樹脂，使用為具有不飽和烴基的熱硬化劑。(C)熱硬化劑係可單獨使用1種、亦可併用2種以上。
本發明的膜狀接著劑中，相對於(B)環氧樹脂100質量份，(C)熱硬化劑的含有量通常係0.1~500質量份、較佳係1~200質量份、更佳係10~100質量份。若(C)熱硬化劑含有量較少於上述範圍，硬化性便嫌不足，無法獲得具有充分接著力的膜狀接著劑。
(D)填料
藉由在膜狀接著劑中摻合(D)填料，便有可調整膜狀接著劑之線膨脹係數的情況。又，亦可更加降低膜狀接著劑經硬化後的吸濕率。藉由降低吸濕率，便可提升半導體封裝的可靠度。填料係可為所有的無機填充劑、有機填充劑中之任一者，但就從耐熱性的觀點，較佳係使用無機填充劑。
填料的材質係可例如：二氧化矽、氧化鋁、碳酸鈣、矽酸鈣、氫氧化鎂、氫氧化鋁、氧化鈦、碳黑、滑石、雲母或黏土等。其中，最好係能輕易獲得透明性、分散性呈良好、且平均粒徑小的二氧化矽。填料係可單獨使用1種、亦可併用2種以上。當作填料用的二氧化矽亦可經利用有機化合物施行表面修飾。填料(例如二氧化矽)表面修飾時所使用的有機化合物係可例如(甲基)丙烯醯基等具有不飽和烴基者。藉由表面修飾所使用的有機化合物係具有不飽和烴基，當膜狀接著劑中含 有具不飽和烴基之其他成分時，便可在填料與其他成分間形成鍵結，俾提升填料與其他成分間之相溶性。結果可輕易地控制膜狀接著劑的全光線穿透率與霧度值，且能經由膜狀接著劑，依優異的接著強度將半導體晶片接合於其他半導體晶片或基板。
相對於構成膜狀接著劑的總固形份，膜狀接著劑中的(D)填料含有比例較佳係5質量%以上、更佳係5~50質量%、特佳係10~30質量%。藉由將(D)填料的含有比例設為上述範圍，便可更加降低膜狀接著劑經硬化後的吸濕，且使膜狀接著劑中的填料比率不會過度變大，俾降低損及接著性。
(D)填料的平均粒徑較佳係50nm以下。藉由將(D)填料的平均粒徑設為上述範圍，膜狀接著劑便可在不致損及與晶圓等被黏物間之貼附性的情況下發揮接著性。又，可輕易地將後述膜狀接著劑的霧度值與全光線穿透率調整於所需範圍。能獲得此種效果的理由推測如下。即便使用平均粒徑較小於可見光波長(以360nm程度為下限)的填料，但並無法迴避因該粒子所造成通稱「瑞利散射」(Rayleigh scattering)的可見光散射。然而，藉由將(D)填料的平均粒徑設為上述範圍，便可將瑞利散射抑制於較低程度，並可抑低霧度值，能維持較高的全光線穿透率。
(D)填料的平均粒徑更佳係1~40nm、特佳係10~30nm。藉由將(D)填料的平均粒徑設為此種範圍，即便膜狀接著劑的厚度較厚時，仍可抑低霧度值、並可維持較高的全光線穿透率。
(D)填料的平均粒徑係表示依照雷射繞射‧散射法所測定 的體積平均粒徑。
其他成分
其他成分係可例如下述成分。
(E)硬化促進劑
硬化促進劑(E)係為調整膜狀接著劑的硬化速度而使用。較佳的硬化促進劑係可例如：三伸乙二胺、苄基二甲胺、三乙醇胺、二甲胺基乙醇、三(二甲胺基甲基)酚等三級胺類；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羥甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑等咪唑類；三丁膦、二苯膦、三苯膦等有機膦類；四苯鏻四苯基硼酸鹽、三苯膦四苯基硼酸鹽等四苯硼酸鹽等等。該等係可單獨使用1種、或混合使用2種以上。
使用硬化促進劑(E)時，相對於(B)環氧樹脂100質量份，硬化促進劑(E)較佳係含有0.01~10質量份、更佳係0.1~1質量份量。藉由依上述範圍的量含有硬化促進劑(E)，即便暴露於高溫度高濕度下仍具有優異接著性，即便暴露於嚴苛的迴焊條件情況下，仍可達成高封裝可靠度。若硬化促進劑(E)的含有量較少，便會有硬化不足、無法獲得充分的接著性；反之若過剩，具高極性的硬化促進劑在高溫度高濕度下，會在經硬化後的膜狀接著劑中移往接著界面側並偏析，導致封裝的可靠度降低。
(F)偶合劑
藉由使用具有會與半導體晶圓、晶片等無機物進行反應之官能基、及會與(A)黏結劑樹脂、(B)環氧樹脂等所具有的有機 官能基進行反應之官能基的偶合劑(F)，便可提升膜狀接著劑對被黏物的接著力。又，能在不致損及將膜狀接著劑予以硬化而獲得硬化物的耐熱性情況下，提升其耐水性。偶合劑(F)較佳係矽烷偶合劑。
矽烷偶合劑係可例如：γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-(甲基丙烯醯基丙基)三甲氧基矽烷、γ-胺丙基三甲氧基矽烷、N-6-(胺乙基)-γ-胺丙基三甲氧基矽烷、N-6-(胺乙基)-γ-胺丙基甲基二乙氧基矽烷、N-苯基-γ-胺丙基三甲氧基矽烷、γ-脲丙基三乙氧基矽烷、γ-硫醇基丙基三甲氧基矽烷、γ-硫醇基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽烷丙基)四磺胺、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、咪唑矽烷等。矽烷偶合劑係可單獨使用1種、亦可併用2種以上。
相對於(A)黏結劑樹脂與(B)環氧樹脂合計100質量份，偶合劑(F)的含有量通常係0.1~20質量份、較佳係0.2~10質量份、更佳係0.3~5質量份。若偶合劑(F)的含有量未滿0.1質量份，便無法獲得上述效果；反之，若超過20質量份便會成為逸氣的原因。
(G)能量線聚合性化合物
膜狀接著劑亦可含有能量線聚合性化合物(G)。能量線聚合性化合物(G)係含有不飽和烴基，若接受紫外線、電子束等能量線的照射便會聚合硬化。藉由將能量線聚合性化合物(G) 施行能量線照射而使聚合，便可降低膜狀接著劑的接著力。所以，可輕易地執行支撐片與膜狀接著劑間之層間剝離。
此種能量線聚合性化合物(G)具體係可例如：三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇單羥基五丙烯酸酯、二季戊四醇六丙烯酸酯或1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、寡聚酯丙烯酸酯、胺甲酸乙酯丙烯酸酯系寡聚物、環氧改質丙烯酸酯、聚醚丙烯酸酯及衣康酸寡聚物等丙烯酸酯系化合物。此種化合物係分子內至少具有1個聚合性雙鍵，且通常重量平均分子量係100~30000、較佳係300~10000程度。當使用能量線聚合性化合物(G)時，就摻合量並無特別的限定，但相對於構成膜狀接著劑的總固形份，較佳依1~50質量%程度的比例使用。
(H)光聚合起始劑
當在膜狀接著劑中摻合能量線聚合性化合物(G)時，照射紫外線等能量線，便可提升由膜狀接著劑構成接著劑層從支撐片上的剝離性。藉由使膜狀接著劑中含有光聚合起始劑(H)，便可減少聚合‧硬化時間及光線照射量。
光聚合起始劑(H)具體係可例如：二苯基酮、苯乙酮、苯偶姻、苯偶姻甲醚、苯偶姻***、苯偶姻異丙醚、苯偶姻異丁醚、苯偶姻安息香酸、苯偶姻安息香酸甲酯、苯偶姻二甲基縮酮、2,4-二乙基硫酮、α-羥基環己基苯基酮、苄基二苯硫醚、四甲基硫化甲硫碳醯胺、偶氮雙異丁腈、苄基、二苄基、二乙醯基、1,2-二苯基甲烷、2-羥基-2-甲基-1-[4-(1-甲基 乙烯基)苯基]丙酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、及β-氯化蒽醌等。光聚合起始劑(H)係可單獨使用1種、或組合使用2種以上。
相對於能量線聚合性化合物(G)100質量份，光聚合起始劑(H)的含有量較佳係0.1~10質量份、更佳係1~5質量份。若光聚合起始劑(H)的含有量低於上述範圍，便會因光聚合不足導致無法獲得滿足的層間剝離性；反之，若高於上述範圍，便會生成對光聚合無具貢獻的殘留物，導致膜狀接著劑的硬化性不足。
(I)交聯劑
在膜狀接著劑中，為調節其初期接著力與凝聚力，亦可添加(I)交聯劑。(I)交聯劑係可例如：有機多元異氰酸酯化合物、有機多元亞胺化合物等。
有機多元異氰酸酯化合物係可例如：芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物、脂環族多元異氰酸酯化合物、及該等有機多元異氰酸酯化合物的三聚物、以及使該等有機多元異氰酸酯化合物與多元醇化合物進行反而獲得的末端異氰酸酯胺甲酸乙酯預聚物等。
有機多元異氰酸酯化合物更具體例，係可例如：2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、1,3-伸苯二甲基二異氰酸酯、1,4-二甲苯二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯、二苯基甲烷-2,4'-二異氰酸酯、3-甲基二苯基甲烷二異氰酸酯、六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、二環己基甲烷-2,4'-二異氰酸酯、三羥甲 基丙烷加成甲苯二異氰酸酯、及離胺酸異氰酸酯。
有機多元亞胺化合物的具體例係可例如：N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶羧醯胺)、三羥甲基丙烷-三-β-吖丙啶基丙酸酯、四羥甲基甲烷-三-β-吖丙啶基丙酸酯、及N,N'-甲苯-2,4-雙(1-氮丙啶羧醯胺)三伸乙基三聚氰胺等。
相對於(A)黏結劑樹脂100質量份，(I)交聯劑較佳係依1~40質量份、更佳係8~35質量份、特佳係12~30質量份的比率使用。
(J)通用添加劑
膜狀接著劑中除上述之外，視需要尚可摻合各種添加劑。各種添加劑係可例如：可塑劑、抗靜電劑、抗氧化劑、難燃劑、吸氣劑、鏈轉移劑等。
由上述各成分所構成膜狀接著劑的D65標準光源之全光線穿透率係70%以上，霧度值係50%以下。
若全光線穿透率未滿70%、或霧度值超過50%，則在半導體裝置之製造步驟中，將具膜狀接著劑之晶片固定(黏晶)於基板或其他晶片等之時、或將半導體晶片等固定於具膜狀接著劑之基板時，會有對準(定位)標記的讀取趨於困難，導致無法正確地黏晶。
膜狀接著劑的D65標準光源之全光線穿透率較佳係75~100%，霧度值較佳係1~40%。
膜狀接著劑的全光線穿透率與霧度值係藉由調整(D)填料的平均粒徑、或(D)填料以外的各成分相溶性，便可進行控制。
再者，膜狀接著劑經硬化後的吸濕率較佳係5%以 下、更佳係3%以下、特佳係0~2%。藉由將膜狀接著劑經硬化後的吸濕率設為上述範圍，便可提升半導體封裝的可靠度。另外，吸濕率係依照後述實施例的條件與方法所測定經168小時後的吸濕率。
(半導體接合用接著片)
本發明的半導體接合用接著片係將由上述各成分所構成膜狀接著劑形成的接著劑層，積層於支撐片上而製造。接著劑層係具有感壓接著性或熱接著性、與加熱硬化性。當接著劑層具有感壓接著性的情況，在未硬化狀態下按壓於被黏物上便可進行貼附。又，當接著劑層具有熱接著性的情況，於按壓於被黏物上之時，對接著劑層施行加熱便可貼附。本發明中所謂「熱接著性」係指常溫下雖未呈感壓接著性，但利用熱而軟化便可接著於被黏物。所以，本發明半導體接合用接著片的接著劑層，係具有在未硬化狀態下暫時性保持著各種被黏物的機能。故，在利用半導體接合用接著片保持著被黏物之狀態下，可對被黏物未貼附片的面(背面)施行加工(例如研削加工)。然後，經熱硬化，最終可賦予高耐衝擊性的硬化物，接著強度異優異，即便在嚴苛的高溫度高濕度條件下，仍可保持充分的接著性。構成膜狀接著劑的接著劑組成物係可將上述各成分依適當比例混合而獲得。混合時，可將各成分預先利用溶劑稀釋，亦可在混合時才添加溶劑。
以下，針對半導體接合用接著片的較佳態樣及使用態樣進行說明。接著劑層係當使用在支撐片上呈可剝離形成的半導體接合用接著片時，便將接著劑層接著於晶圓或基板等 被黏物上，再剝離支撐片便將接著劑層轉印於被黏物上。本發明半導體接合用接著片的形狀係可為帶狀、標籤狀等任何形狀。
支撐片係僅由表面未具黏性的樹脂薄膜構成、或者亦可對樹脂薄膜施行適當表面處理等、或者亦可為在樹脂薄膜上設有黏著劑層的黏著片。又，亦可在樹脂薄膜上設置凹凸吸收層。
當作支撐片使用的樹脂薄膜係可使用例如：聚乙烯膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚物薄膜、聚對苯二甲酸乙二酯薄膜、聚萘二甲酸乙二酯薄膜、聚對苯二甲酸丁二酯薄膜、由胺甲酸乙酯聚合物與乙烯系聚合物構成的複合薄膜、胺甲酸乙酯丙烯酸酯硬化物薄膜、乙烯-醋酸乙烯酯共聚物薄膜、離子聚合物樹脂薄膜、乙烯‧(甲基)丙烯酸共聚物薄膜、乙烯‧(甲基)丙烯酸酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜、氟樹脂薄膜等薄膜。又，亦可使用該等的交聯薄膜。又，亦可為該等的積層薄膜。又，可使用該等經著色過的薄膜等。當接著劑層係具有能量線硬化性的情況，最好具有能量線穿透性者。又，當要求在施行支撐片與接著劑層的層間剝離前，亦能檢視被黏物表面的情況，最好具有可見光穿透性(透明或半透明)。
該等之中，樹脂薄膜最好使用23℃下的儲存彈性模數較佳1×107Pa以上、更佳係1×108~1×109Pa的樹脂薄膜。又，最好使用根據拉伸試驗在23℃下的應力緩和率較佳係40%以上、更 佳係70~90%的樹脂薄膜。藉由使用儲存彈性模數與應力緩和率在上述範圍內的樹脂薄膜，在晶圓的背面研削步驟中可抑制晶圓發生翹曲與凹點情形。
此處，根據拉伸試驗在23℃下的應力緩和率係依照以下方法進行測定。將樹脂薄膜切斷為15mm×140mm而形成樣品。在23℃、相對濕度50%的環境下，使用萬能拉伸試驗機(SHIMADZU公司製autograph AG-10kNIS)，抓住該樣品二端20mm，依每分鐘200mm的速度進行拉伸，並測定當10%伸張時的應力A(N/m2)、與自膠帶停止伸張起經1分鐘後的應力B(N/m2)。從該等應力A、B值計算(A-B)/A×100(%)，並設為應力緩和率。
此種薄膜的特性係從由胺甲酸乙酯聚合物與乙烯系聚合物構成的複合薄膜、或胺甲酸乙酯丙烯酸酯硬化物薄膜便可輕易獲得。由胺甲酸乙酯聚合物與乙烯系聚合物構成的複合薄膜係可使用例如日本專利特開2007-84722所揭示者。胺甲酸乙酯丙烯酸酯硬化物薄膜係可使用例如日本專利特開平11-343469所揭示者。
本發明的半導體接合用接著片係貼附於各種被黏物上，經對被黏物施行所需加工後，接著劑層便依固著殘存於被黏物上的狀態被從支撐片上剝離。即，使用於包括有將接著劑層從支撐片轉印於被黏物之步驟的製程。所以，支撐片接觸到接著劑層之一面的表面張力較佳係40mN/m以下、更佳係37mN/m以下、特佳係35mN/m以下。下限值通常係25mN/m左右。此種表面張力較低的支撐片係適當選擇樹脂薄膜的材質 便可獲得，又在樹脂薄膜表面上塗佈剝離劑並施行剝離處理亦可獲得。
樹脂薄膜的剝離處理時所使用剝離劑係可使用醇酸系、聚矽氧系、氟系、不飽和聚酯系、聚烯烴系、蠟系等，特別係醇酸系、聚矽氧系、氟系等剝離劑，因為具有耐熱性故屬較佳。
在為使用上述剝離劑對樹脂薄膜表面施行剝離處理時，只要將剝離劑直接依無溶劑狀態、或經溶劑稀釋、或呈乳液化後，再利用諸如凹版塗佈機、經塗棒塗佈機、氣刀塗佈機、輥塗機等施行塗佈，再將已塗佈剝離劑的支撐片在常溫下或加熱下、或利用電子束使硬化，便可形成剝離劑層。
再者，藉由利用濕式積層、乾式積層、熱熔融積層、熔融擠出積層、共擠出加工等施行薄膜的積層，亦可調整支撐片的表面張力。即，將至少其中一面的表面張力係在當作上述支撐片接觸到接著劑層之一面較佳範圍內的薄膜，依該面成為接觸到接著劑層的方式，製造與其他薄膜進行積層的積層體，亦可形成支撐片。
支撐片亦可在如上述樹脂薄膜上設有黏著劑層的黏著片。在接著劑層可從黏著劑層上剝離之目的下，黏著劑層係可由具再剝離性的公知黏著劑構成，藉由選擇紫外線硬化型、加熱發泡型、水膨潤型、弱黏型等黏著劑，便可輕易進行接著劑層的剝離。特別係當將由胺甲酸乙酯聚合物與乙烯系聚合物構成的複合薄膜、或胺甲酸乙酯丙烯酸酯硬化物薄膜，使用為樹脂薄膜之構成層的情況，因為該等薄膜通常係呈柔軟、 並具有自黏性，因而若構成該等直接接觸接著劑層，便會造成層間剝離趨於困難。所以，為迴避此種情況發生，最好將支撐片設為黏著片。
黏著片的黏著力較佳係10~10000mN/25mm、更佳係50~2000mN/25mm。黏著力係根據JIS Z 0237；2009，貼附於被黏物(SUS)上經30分鐘後的黏著片，利用180°拉剝法測得的黏著力。藉由將黏著片的黏著力設為上述範圍，便可使從黏著劑層上剝離接著劑層之事趨於容易。
再者，黏著劑層的23℃儲存彈性模數較佳係1×104Pa以上、更佳係1×105~1×108Pa。藉由使用儲存彈性模數在上述範圍的黏著劑層，在晶圓的背面研削步驟中可抑制晶圓發生翹曲、凹點情形。
再者，在樹脂薄膜的上面(即靠黏著劑層所設置側的樹脂薄膜表面)上，為提升與黏著劑層間之密接性，亦可施行電暈處理、或設置底漆層。又，亦可在黏著劑層的對向面上塗佈各種塗膜。
在樹脂薄膜上上所設置的凹凸吸收層係可為例如利用自習知起便屬公知的各種黏著劑形成，兼具凹凸吸收層與黏著劑層的層。黏著劑並無任何限定，可使用例如：橡膠系、丙烯酸系、聚矽氧系、聚乙烯醚等黏著劑。又，亦可使用能量線硬化型、加熱發泡型、水膨潤型等黏著劑。又，亦可將由胺甲酸乙酯聚合物與乙烯系聚合物構成的複合薄膜、或胺甲酸乙酯丙烯酸酯硬化物薄膜，使用為凹凸吸收層。又，在由胺甲酸乙酯聚合物與乙烯系聚合物構成的複合薄膜、或由胺甲酸乙酯 丙烯酸酯硬化物薄膜構成的凹凸吸收層上，亦可更進一步設置黏著劑層。另外，當支撐片係複數設有由胺甲酸乙酯聚合物與乙烯系聚合物構成的複合薄膜、或胺甲酸乙酯丙烯酸酯硬化物薄膜的情況，除距黏著劑層最遠位置處之外，由胺甲酸乙酯聚合物與乙烯系聚合物構成的複合薄膜或胺甲酸乙酯丙烯酸酯硬化物薄膜均視為凹凸吸收層。
由胺甲酸乙酯聚合物與乙烯系聚合物所構成複合薄膜、或胺甲酸乙酯丙烯酸酯硬化物薄膜，係除可使用上述者之外，就胺甲酸乙酯丙烯酸酯硬化物薄膜亦可使用由日本專利特開2011-068727所揭示含有胺甲酸乙酯丙烯酸酯系寡聚物、與分子內具硫醇基之化合物的能量線硬化型組成物，施行硬化而構成的片，積層於樹脂薄膜上當作凹凸吸收層。
凹凸吸收層的23℃儲存彈性模數較佳係1×104Pa以上、更佳係3×105~3×106Pa。又，凹凸吸收層施加20%扭轉應力經10秒後的應力緩和率，較佳係50%以上、更佳係80~99.9%。藉由使用儲存彈性模數與應力緩和率在上述範圍內的凹凸吸收層，即便在晶圓貼附半導體接合用接著片之一面上形成具有數十μm程度之高度的突起，凹凸吸收層仍會吸收突起，便可保持半導體接合用接著片的表面呈平坦。又，即便此種突起的高度較低於接著劑層厚度的情況，藉由凹凸吸收層吸收貫通接著劑層的突起，使接著劑層靠近/到達晶圓表面，便可使接著劑層接著於晶圓表面上。
再者，半導體接合用接著片亦可支撐片與接著劑層預先沖模形成與被黏物(半導體晶圓等)相同形狀的形狀。特 別係由支撐片與接著劑層構成的積層體亦可形成在長條工程薄膜上呈連續保持的形態。工程薄膜係可使用上述就支撐片所例示的樹脂薄膜。
支撐片的厚度通常係10~500μm、較佳係15~300μm、更佳係20~250μm左右。當支撐片係黏著片的情況，通常支撐片厚度中之1~50μm左右的厚度係被由黏著劑構成的層佔據。又，當設有凹凸吸收層的情況，通常支撐片厚度中之10~450μm左右的厚度係被凹凸吸收層佔據。又，接著劑層的厚度通常係2~500μm、較佳係6~300μm、更佳係10~150μm左右。接著劑層的厚度最好係與在所貼附晶圓上形成的凸部高度呈略相同。
在半導體接合用接著片上，為能在使用前保護接著劑層，亦可在接著劑層的上面積層著剝離薄膜。該剝離薄膜係可使用在諸如聚對苯二甲酸乙二酯薄膜、聚丙烯薄膜等塑膠材料上，塗佈諸如聚矽氧樹脂等剝離劑者。
半導體接合用接著片的製造方法並無特別的限定，當支撐片係樹脂薄膜的情況，亦可在樹脂薄膜上塗佈接著劑組成物並使乾燥，而形成接著劑層便可製造。又，亦可將接著劑層設置於剝離薄膜上，藉由將其轉印於上述樹脂薄膜或黏著片上而製造。又，半導體接合用接著片亦可依形成與在接著劑層上所貼附晶圓的形狀呈同一形狀、或較晶圓更大同心圓形狀等方式，利用沖孔加工等施行切斷。
其次，相關本發明半導體接合用接著片的利用方法，針對該接著片貼附於晶圓上並使用於半導體裝置的製造的 情況為例進行說明。
(半導體裝置的製造方法)
本發明半導體裝置的製造方法係包括：將上述半導體接合用接著片的接著劑層貼附於晶圓上的步驟、將晶圓施行個片化而獲得晶片的步驟、以及經由接著劑層將晶片予以固定的步驟。
以下，針對本發明半導體裝置的製造方法之部分例進行詳述。
本發明半導體裝置的第1製造方法，首先在表面已有形成電路的半導體晶圓之電路面上，貼附半導體接合用接著片。施行貼附之際，亦可將半導體晶圓的電路面載置於半導體接合用接著片的接著劑層上，輕輕按壓(依情況施加熱)，一邊使接著劑層軟化一邊將半導體晶圓予以固定。接著，視需要在由半導體接合用接著片保護著半導體晶圓之電路面的狀態下，對晶圓背面施行研削而形成既定厚度的晶圓。
半導體晶圓係可為矽晶圓、且亦可為鎵‧砷等化合物半導體晶圓。對晶圓表面上的電路形成係可利用包括諸如蝕刻法、剝脫法等自習知起便通用方法在內的各種方法實施。在半導體晶圓的電路形成步驟中，形成既定電路。此種晶圓研削前的厚度並無特別的限定，通常係500~1000μm程度。又，半導體晶圓的表面形狀並無特別的限定，亦可形成突起狀電極。突起狀電極係可例如圓柱型電極、球狀電極等。又，亦可為具有貫通電極的半導體晶圓。對半導體晶圓貼附半導體接合用接著片的方法並無特別的限定。
背面研削係在保持貼附著半導體接合用接著片的狀態下，利用研磨機、及晶圓步驟中所使用吸附平台等公知手法實施。經背面研削步驟後，亦可施行將因研削而生成的破碎層予以除去之處理。經背面研削後的半導體晶圓厚度並無特別的限定，較佳係10~400μm、更佳係25~300μm程度。根據本發明的半導體接合用接著片，在施行晶圓的背面研削時，可確實保持著晶圓，且能防止切削水滲入電路面，並可防止發生晶圓翹曲與凹點情形。
經背面研削步驟後，在晶圓的背面上貼附著通稱所謂「切割片」的黏著片。切割片的貼附一般係利用通稱「貼片機」的裝置實施，但並無特別的限定。接著，在晶圓的電路面殘留接著劑層，僅剝離支撐片。剝離支撐片的方法並無特別的限定。
然後，施行在切割片上所貼附晶圓的切割，將晶圓予以個片化便獲得晶片。
半導體晶圓的切斷手段並無特別的限定。就其中一例係在晶圓切斷時，利用環形框架固定著切割片的周邊部之後，再使切割機等使用旋轉圓刀等等公知手法施行晶圓晶片化的方法等。此時的切斷深度係設為經加權接著劑層厚度與半導體晶圓厚度的合計、及切割鋸刀磨耗份的深度。又，亦可利用雷射光將接著劑層與晶圓予以切斷。
其次，視需要若施行切割片的擴展，半導體晶片間隔便擴張，俾使半導體晶片的拾取更容易實施。此時，在晶片與切割片之間會發生偏移，減少晶片與切割片間的接著力， 俾提升半導體晶片的拾取性。若依此施行半導體晶片的拾取，便可使被切斷的接著劑層固著殘存於半導體晶片電路面上，並從切割片上剝離。
其次，施行半導體晶片的黏合步驟(黏晶)。黏合步驟係經由接著劑層，將半導體晶片載置於導線架的晶片焊墊上或另一半導體晶片(下層晶片)表面(以下將晶片所搭載的晶片焊墊或下層晶片表面稱「晶片搭載部」)。本發明中，因為在半導體晶片表面上所固著的接著劑層之全光線穿透率與霧度值係在既定範圍內，因而在黏晶時能輕易地讀取晶片表面的對準標記。結果，可將半導體晶片正確地黏晶於晶片搭載部。晶片搭載部亦可在載置半導體晶片前便施行加熱，又亦可在晶片剛載置後便馬上施行加熱。加熱溫度通常係80~200℃、較佳係100~180℃，加熱時間通常係0.1秒~5分鐘、較佳係0.5秒~3分鐘，載置時的壓力通常係1kPa~200MPa。
半導體晶片載置於晶片搭載部之後，視需要亦可施行為使其他接著劑層硬化的加熱(其係不同於下述樹脂密封中利用加熱的接著劑層硬化)。此時的加熱條件係上述加熱溫度的範圍，加熱時間通常係1~180分鐘、較佳係10~120分鐘。
再者，亦可在未施行載置後的加熱處理情況下形成初步黏著狀態，利用封裝製造中通常採行樹脂密封的加熱使接著劑層硬化。藉由經由此種步驟，便使接著劑層硬化，俾將半導體晶片與晶片搭載部牢固地接著，便可將晶片予以固定。因為接著劑層在黏晶條件下會呈流動化，因而就連晶片搭載部的凹凸亦能充分埋藏，俾能防止發生孔隙，而提高封裝可靠度。
本發明半導體裝置的第2製造方法，係與上述第1製造方法同樣地，在半導體晶圓的電路面上貼附著半導體接合用接著片，再對晶圓的背面施行研削。經背面研削步驟之後，亦可施行將因研削所生成的破碎層予以除去之處理。
經背面研削後，從晶圓的背面側朝晶圓內部照射雷射光。雷射光係從雷射光源照射。雷射光源係產生波長與相位經整合過之光的裝置，雷射光的種類係可例如：產生脈衝雷射光的Nd-YAG雷射、Nd-YVO雷射、Nd-YLF雷射、鈦藍寶石雷射等引發多光子吸收者。雷射光的波長較佳係800~1100nm、更佳係1064nm。
雷射光照射於晶圓內部，並沿切斷預定線在晶圓內部形成改質部。雷射光掃描1個切斷預定線的次數係可為1次、亦可為複數次。較佳係一邊監視雷射光的照射位置、與電路間之切斷預定線位置，施行雷射光的對位，一邊施行雷射光的照射。另外，切斷預定線將在晶圓表面上所形成各電路間予以區隔的假想線。
改質部形成後，便在晶圓背面上貼附著切割片。接著，使晶圓的電路面上殘留接著劑層，僅剝離支撐片。
其次，施行在切割片所貼附晶圓的切割，將晶圓予以個片化便獲得晶片。半導體晶圓係藉由將切割片予以擴展而晶片化。即，利用雷射光照射在晶圓內部形成改質部後，若施行擴展，切割片便伸長，半導體晶圓便以晶圓內部的改質部為起點被切斷分離為各個晶片。此時，接著劑層亦切斷分離為各個晶片尺寸。又，在擴展之同時，使用夾具等抓住切割片， 將切割片予以伸長，亦可將接著劑層與晶圓依每個晶片切斷分離。擴展最好在-20~40℃環境下，依5~600mm/分鐘的速度實施。又，經擴展步驟後，為消除經擴展過切割片的鬆弛，亦可施行熱收縮。然後，表面具有接著劑層的晶片便被拾取，經由黏合步驟而製造半導體裝置。黏合步驟係與上述第1製造方法同樣。
以上所詳述的第1製造方法與第2製造方法，充其量只不過本發明製造方法其中一例而已，本發明的製造方法亦可為其他態樣。例如亦可未使用半導體接合用片，僅在晶圓上單獨貼附膜狀接著劑，而將為保護晶圓背面研削用的保護片另行貼附於膜狀接著劑上。
再者，亦可採行在將膜狀接著劑或半導體接合用接著片貼附於晶圓前的階段，便結束晶圓的背面研削，而在膜狀接著劑或半導體接合用接著片貼附後才施行晶圓背面研削的製造方法。
再者，晶圓的個片化方法亦可從晶圓的表面側形成較晶圓厚度更小深度的溝渠，藉由對晶圓背面施行研削直到溝渠而施行個片化，所謂「先切割法」，亦可採行如日本專利特開2004-111428所記載，從晶圓表面使雷射光合致於晶片形狀入射，而於晶圓內部形成改質區域的步驟中，追加對晶圓背面施行研削的步驟之晶圓分割方法。
由上述半導體裝置的製造方法得知，本發明的半導體接合用接著片係能使用為可適用從晶圓背面研削步驟起至晶片黏合步驟的背面研磨‧黏晶片。
[實施例]
以下，針對本發明利用實施例進行說明，惟本發明並不僅侷限於該等實施例。另外，以下實施例與比較例中，各評價係依如下述實施。
<霧度值及全光線穿透率>
使用接著劑組成物(1)~(5)，將各接著劑組成物塗佈於剝離薄膜(Lintec公司製SP-PET381031)後，使乾燥(於烤箱中施行100℃、1分鐘)，便製作厚度20μm的膜狀接著劑。又，另外製作厚度20μm的膜狀接著劑，藉由將膜狀接著劑予以積層，便獲得厚度40μm、60μm、80μm、100μm的膜狀接著劑。接著，將剝離薄膜予以剝離，而形成評價用樣品。使用測霾計(日本電色工業公司製NDH-5000)，根據JIS K7136：2000測定評價用樣品的膜狀接著劑之霧度值(%)。又，根據JIS K7361：2000測定評價用樣品的膜狀接著劑之D65標準光源全光線穿透率(%)。
<吸濕率>
將使用接著劑組成物(1)~(5)所製作的膜狀接著劑(50mm四方)，積層200μm厚度，獲得積層片，並當作評價用樣品。評價用樣品經140℃烤箱施行1小時加熱硬化後，於濕熱條件(85℃、相對濕度85%)下投入既定時間(24小時與168小時)，測定投入前後的硬化物重量變化(%)，獲得24小時後與168小時後的吸濕率。
<對準>
準備WALTS公司製8吋晶圓「WALTS-TEG MB50-0101JY_TYPE-B(具聚醯亞胺膜)、厚度725μm」。在該晶圓上所形成各個片化預定區域上，存在544個墊。對該等各墊製作高度30μm的Cu柱，更於該等Cu柱上依15μm高度設置SnAg焊錫，形成合計高度45μm的凸塊。依照以上的順序，便準備模擬覆晶型晶圓的評價用晶圓。
對評價用晶圓的凸塊設置面，使用全自動背面研磨膠帶用膠帶層壓機(Lintec股份有限公司製RAD-3510F/12)層壓著由實施例與比較例所獲得半導體接合用接著片。
其次，使用晶圓背面研磨裝置(Disc股份有限公司製DGP8760)，施行研磨及乾式拋光處理，獲得厚300μm晶圓。然後，使用全自動多晶圓貼片機(Lintec股份有限公司製RAD-2700F/12)，在乾式拋光面上貼附著紫外線(UV)硬化型切割膠帶(Lintec股份有限公司製Adwill D-678)，並固定於環形框架。
接著，利用同裝置將半導體接合用接著片的支撐片予以剝離，使接著劑層暴露。然後，使用全自動切割鋸刀(Disc股份有限公司製DFD651)施行切割，而將各晶片予以個片化(7.3mm×7.3mm)。
針對經對齊的晶片所附著切割膠帶，使用半自動UV照射裝置(Lintec股份有限公司製RAD-2000m/12)施行UV照射(照度230mW/cm2、光量180mJ/cm2、氮環境下)，而使切割膠帶的黏著力降低。接著，利用手動操作將接著劑層所附著的晶片從切割膠帶上剝離，為防止固著，便在晶片收納部底面上，依接著劑層側朝下方式收納於已貼附剝離薄膜(Lintec股份有限 公司製SP-PET381031)的晶片盤中。
使用覆晶黏晶機(九州松下股份有限公司製、商品名「FB30T-M」)，將經個片化之具接著劑層的晶片從晶片盤中取出，評價該凸塊設置面(已貼附接著劑層之一面)的圖案是否能辨識。施行10個晶片的試驗，將10個均能辨識圖案者評為「A」，將6~9個者評為「B」，將5個以下者評為「C」。
[膜狀接著劑之製造例]
構成膜狀接著劑的接著劑組成物(1)~(5)各成分，係如下述及表1所示。依照下述成分及表1的摻合量，摻合各成分而製備得接著劑組成物(1)~(5)。表1中，各成分的數值係表示固形份換算的質量份，本發明中所謂「固形份」係指溶劑以外的所有成分。
(A)丙烯酸聚合物：由丙烯酸正丁酯55質量份、丙烯酸甲酯10質量份、甲基丙烯酸環氧丙酯20質量份及丙烯酸-2-羥乙酯15質量份構成的丙烯酸聚合物(重量平均分子量：90萬、玻璃轉移溫度：-28℃)
(B1)環氧樹脂：雙酚A型環氧樹脂(Japan Epoxy Resins公司製jER828、環氧當量：235g/eq)
(B2)環氧樹脂：酚醛型環氧樹脂(日本化藥公司製EOCN-104S、環氧當量：218g/eq)
(C)熱硬化劑：酚醛型酚樹脂(DIC公司製TD-2131、酚性羥基當量：103g/eq)
(D1)填料：二氧化矽填料(日產化學公司製MEK-ST、平均粒徑：10~15nm)
(D2)填料：二氧化矽填料(Admatechs製YA050C-MJE、平均粒徑：50nm)
(D3)填料：二氧化矽填料(Admatechs製ADMAFINE SC2050、平均粒徑：500nm)
(D4)填料：碳黑(三菱化學公司製# MA650、平均粒徑：28nm)
(E)硬化促進劑：2-苯基-4,5-二羥甲基咪唑(四國化成工業公司製Curezol 2PHZ-PW)
(F)偶合劑：矽烷偶合劑(信越化學公司製KBE-403)
使用上述接著劑組成物(1)~(5)形成膜狀接著劑，並施行各項評價。結果如表2所示。
(實施例1)
將重量平均分子量5000的胺甲酸乙酯丙烯酸酯系寡聚物(荒川化學公司製)50質量份、丙烯酸異酯50質量份、光聚合起始劑(IRGACURE 184、汽巴嘉基公司製)2.0質量份、及酞菁系顏料0.2質量份予以混合而獲得光硬化型樹脂組成物。將獲得樹脂組成物利用噴射模頭方式，於屬於澆注用工程片之經施行剝離處理過的PET薄膜(Lintec股份有限公司製、SP-PET381031)上，塗佈呈厚度110μm狀態，便形成樹脂組成物層。剛塗佈後，便在樹脂組成物層上更層壓著同樣經剝離處理過的PET薄膜，然後使用高壓水銀燈(160W/cm、高度10cm)，依光量250mJ/cm2的條件施行紫外線照射，而使樹脂組成物層進行交聯、硬化，便獲得由2片剝離薄膜夾持的厚度110μm樹脂薄膜。
其次，另外準備另一剝離薄膜(Lintec股份有限公司製、SP-PET381031)。在由丙烯酸-2-乙基己酯、甲基丙烯酸甲酯、及丙烯酸-2-羥乙酯，依80：10：10質量比進行聚合，而獲得重量平均分子量70萬的丙烯酸酯共聚物之濃度40質量%甲苯溶液100質量份(包含溶劑的量)中，添加異氰酸酯系交聯劑(聚氨酯工業股份有限公司製、CORONATE L)20質量份(包含溶劑的量)，而調製得黏著劑層形成用塗佈液。將該黏著劑層形成用塗佈液在另一剝離薄膜的剝離處理面上塗佈成經乾燥後的厚度10μm狀態，依80℃施行2分鐘乾燥、及緊接著依100℃施行1分鐘乾燥，便獲得在另一剝離薄膜上形成的黏著劑層。
將該黏著劑層轉印於樹脂薄膜上，去除澆注用工程片，藉由在23℃、相對濕度50%環境下保管14天而施行養生，便獲得黏著片(支撐片1)。
將接著劑組成物(1)利用甲乙酮稀釋成固形份濃度50質量%，於經聚矽氧處理過的剝離薄膜(Lintec股份有限公司製SP-PET381031)上塗佈成乾燥後厚度20μm狀態，施行乾燥(乾燥條件：烤箱中，100℃、1分鐘)，便獲得在剝離薄膜上所形成的膜狀接著劑。重複該操作，便獲得在另一剝離薄膜上所形成經乾燥後厚度20μm的膜狀接著劑。接著，將所獲得膜狀接著劑予以積層，便製成厚度40μm的膜狀接著劑。
然後，將膜狀接著劑、與經從上述黏著片上去除另一剝離薄膜而露出的黏著片之黏著劑層予以貼合，藉由將膜狀接著劑轉印於黏著片上，便獲得所需的半導體接合用接著片。各項評 價結果如表3所示。
(實施例2)
使由重量平均分子量4000的聚丙二醇(以下稱「PPG4000」)33g、與異佛爾酮二異氰酸酯5g進行聚合而獲得的末端異氰酸酯胺甲酸乙酯預聚物，與季戊四醇三丙烯酸酯10g進行反應，便獲得重量平均分子量17350的胺甲酸乙酯丙烯酸酯系寡聚物。
添加所獲得胺甲酸乙酯丙烯酸酯系寡聚物100g(固形份)、當作稀釋單體用的丙烯酸異酯66.7g、及當作光聚合起始劑用的2-羥基-2-甲基-1-苯基-丙烷-1-酮(汽巴超級化學公司製：DAROCUR® 1173、固形份濃度100質量%)0.83g、當作具硫醇基之化合物用的季戊四醇四(3-硫醇基丙酸酯)(堺化學工業公司製：PEMP、固形份濃度100質量%)39.2g(80.2mmol)，便獲得常溫液體的能量線硬化型組成物。
在屬於澆注用工程片之經剝離處理過的PET薄膜(Lintec股份有限公司製：SP-PET381031)上，將上述能量線硬化型組成物依噴射模頭方式塗佈成厚度90μm狀態，而形成硬化型組成物層，然後從硬化型組成物層側施行紫外線照射。紫外線照射裝置係使用輸送帶式紫外線照射裝置(EYE GRAPHICS公司製：ECS-401GX)，紫外線源係使用高壓水銀燈(EYE GRAPHICS公司製：H04-L41)[照射條件：燈高度150mm、燈輸出3kW(換算輸出120mW/cm)、光線波長365nm之照度271mW/cm2、光量177mJ/cm2(ORC製作所公司製紫外線光量計：UV-351)]。然後，剛照射後便馬上於硬化型組成物 層上貼合實施例1的樹脂薄膜，再從樹脂薄膜側更施行紫外線照射2次，使組成物進行交聯、硬化[照射條件：燈高度150mm、燈輸出3kW(換算輸出120mW/cm)、光線波長365nm之照度271mW/cm2、光量600mJ/cm2(ORC製作所公司製紫外線光量計：UV-351)]。然後，將經剝離處理過的PET薄膜予以剝離，便獲得經積層著厚度90μm凹凸吸收層的樹脂薄膜。
在該積層體的凹凸吸收層上轉印實施例1的黏著劑層，藉由於23℃、相對濕度50%環境下保管14天而施行養生，便獲得具凹凸吸收層的黏著片(支撐片2)。
接著，除積層厚度20μm的膜狀接著劑，使膜狀接著劑的厚度成為100μm之外，其餘均依照與實施例1相同的順序形成而獲得膜狀接著劑，藉由轉印於具凹凸吸收層之黏著片的黏著劑層上，便獲得半導體接合用接著片。各項評價結果如表3所示。
(實施例3)
除使用接著劑組成物(2)之外，其餘均與實施例1同樣地獲得半導體接合用接著片。各項評價結果如表3所示。
(實施例4)
除使用接著劑組成物(2)之外，其餘均與實施例2同樣地獲得半導體接合用接著片。各項評價結果如表3所示。
(實施例5)
除支撐片係使用厚度100μm低密度聚乙烯膜(支撐片3)之外，其餘均與實施例1同樣地獲得半導體接合用接著片。各項評價結果如表3所示。
(比較例1)
除使用接著劑組成物(3)之外，其餘均與實施例1同樣地獲得半導體接合用接著片。各項評價結果如表3所示。
(比較例2)
除使用接著劑組成物(4)之外，其餘均與實施例1同樣地獲得半導體接合用接著片。各項評價結果如表3所示。
由上述結果得知，本發明半導體接合用接著片在黏晶時的對準優異。又，沒有摻合(D)填料的接著劑組成物(5)，相較於其他接著劑組成物之下，吸濕性較差。

Claims (7)

  1. 一種膜狀接著劑，含有：(A)黏結劑樹脂、(B)環氧樹脂、(C)熱硬化劑及(D)填料；其中，D65標準光源的全光線穿透率係70%以上；霧度值係50%以下，且(D)填料的平均粒徑係50nm以下。
  2. 如申請專利範圍第1項之膜狀接著劑，其中，含有(D)填料達5質量%以上。
  3. 如申請專利範圍第1或2項中任一項之膜狀接著劑，其中，(A)黏結劑樹脂係含有源自環氧基含有單體之構成單元5~30質量%的丙烯酸聚合物。
  4. 如申請專利範圍第1或2項中任一項之膜狀接著劑，其中，相對於(A)黏結劑樹脂100質量份，(B)環氧樹脂含有量係50~1000質量份。
  5. 一種半導體接合用接著片，在支撐片上，可剝離地形成以申請專利範圍第1至4項中任一項之膜狀接著劑為接著劑層。
  6. 如申請專利範圍第5項之半導體接合用接著片，其中，支撐片係含有以由胺甲酸乙酯聚合物與乙烯系聚合物所構成的複合薄膜、或胺甲酸乙酯丙烯酸酯硬化物薄膜為構成層。
  7. 一種半導體裝置的製造方法，使用申請專利範圍第1至4項中任一項之膜狀接著劑、或申請專利範圍第5或6項之半導體接合用接著片，其包括：在晶圓上貼附著膜狀接著劑、或半導體接合用接著片之接著劑層的步驟；將晶圓予以個片化而獲得晶片的步驟；以 及經由膜狀接著劑或接著劑層而將晶片予以固定的步驟。
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