TWI669363B - Reagent composition, adhesive sheet, and method of manufacturing semiconductor device - Google Patents

Reagent composition, adhesive sheet, and method of manufacturing semiconductor device Download PDF

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Publication number
TWI669363B
TWI669363B TW102109175A TW102109175A TWI669363B TW I669363 B TWI669363 B TW I669363B TW 102109175 A TW102109175 A TW 102109175A TW 102109175 A TW102109175 A TW 102109175A TW I669363 B TWI669363 B TW I669363B
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Taiwan
Prior art keywords
adhesive layer
wafer
group
adhesive
resin
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TW102109175A
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English (en)
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TW201339265A (zh
Inventor
土山佐也香
市川功
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琳得科股份有限公司
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Publication of TW201339265A publication Critical patent/TW201339265A/zh
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Publication of TWI669363B publication Critical patent/TWI669363B/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
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • C09J133/04—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
    • 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
    • C09J133/04—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
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C09J133/04—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
    • 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
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • 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
    • C09J143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • 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
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • 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
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
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    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
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    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
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Abstract

提供一種接著劑組合物，能夠於接著劑層中將耦合劑均勻的混合，即使在多段封裝的製造時對接著劑層採用一次全部硬化製程的情形，能夠在一次全部硬化前穩定的進行打線，硬化後顯示優良的接著強度，特別是於半導體裝置達成高封裝信賴性。本發明的接著劑組合物，其特徵在於包含丙烯酸聚合物(A)、具有不飽和烴基的熱硬化性樹脂(B)以及具有反應性雙鍵基的耦合劑(C)。

Description

接著劑組合物、接著片及半導體裝置的製造方法
本發明是有關於一種接著劑組合物，特別適合使用於將矽晶圓等切割且得到的半導體晶片接著於(晶粒結著(die bonding))有機基板、導線架或其他半導體晶片的步驟，並有關於具有該接著劑組合物所構成的接著劑層的接著片以及使用該接著片的半導體裝置的製造方法。
矽、砷化鎵等的半導體晶圓以大直徑的狀態製造，此晶圓被切割分離(dicing)為元件小片(半導體晶片)後，移行至作為下一步驟的安裝步驟。此時，半導體晶圓以預先貼附於接著片的狀態施加切割、洗淨、乾燥、擴展、拾取的各步驟後，移送至下個步驟的結著步驟。
於此些步驟中，為了簡化拾取步驟以及結著步驟的製程，提出有種種的同時兼具有晶圓固定功能與晶粒接著功能之切割．晶粒結著用接著片(專利文獻1等)。專利文獻1所揭示的接著片，能夠進行所謂的直接晶粒結著，並能夠省略晶粒接著用接著劑的塗佈步驟。此接著劑包含丙烯酸聚合物、含有不飽和烴基的環氧樹脂以及熱硬化劑，因應需要含有矽烷耦合劑等的耦合劑。
對於近年的半導體裝置，所要求的物性變得非常嚴苛。例如是於電子元件的連接中，進行封裝全體都暴露於焊料熔點以上的高溫的表面封裝法(回流)。而且，近年來由於移行至不含鉛的焊料，封裝溫度上升至260℃的程度。因此，封裝時的半導體封裝內部所發生的應力變得比以往來的更大，產生接著界面的剝離或封裝破裂等不良狀況的可能性高。此處，於前述專利文獻1，作為環氧樹脂使用含有不飽和烴基的環氧樹脂，藉由提昇丙烯酸樹脂與環氧樹脂的相溶性，改善接著可靠性。
而且，為了高密度封裝，提出有將晶片多段層積的封裝結構。此封裝結構不僅必須連接基板與晶片，亦必須接著晶片與晶片。多段封裝是在晶片上經由接著劑層而層積晶片，並於接著劑層硬化後進行打線(wire bonding)，進而依序進行晶片的層積、接著劑層的硬化、打線，以將晶片層積。然而，由於此方法於每次層積晶片時進行接著劑層的硬化，如晶片的層積數增大，製造步驟會增加，因而追求生產效率的改善。
此處，檢討在層積晶片時不進行接著劑層的硬化，於接著劑層未硬化或半硬化的狀態進行層積或打線，在所有的晶片層積後，利用模密封步驟時長時間暴露於高溫，將接著劑層一次全部進行完全硬化。藉由採用此種的一次全部硬化，能夠省略進行接著劑層的逐次硬化的時間，改善生產效率。但是，採用此製法時，於打線時接著劑層為未硬化或半硬化的狀態。因此，打線時會晶片震動、位移，特別是晶片與晶片彼此層積時，晶片間的密接性降低，有可能在打線時產生故 障。為了提升晶片與晶片的密接性，在接著劑層中調配有耦合劑被認為是有希望的。
【先前技術文獻】 【專利文獻】
【專利文獻1】日本特開2008-133330號公報
但是，於接著劑中均勻的混合耦合劑並不見得容易。如接著劑中的耦合劑的分散性差，接著力變得不安定，製品間的散亂變大。
而且，即使如同上述的接著劑層採用一次全部硬化製程的情形，由於打線時需要150℃以上的高溫，接著劑層有可能部分硬化。在此種不期望的硬化時，由於未進行加壓，如接著劑硬化的話則成為僅失去接著力，導致接著強度的降低。接著劑層如部分硬化，特別是對於凹凸表面的追隨性降低，對於凹凸較大的基板表面或晶粒墊的接著性顯著降低。因此，於製造多段封裝時，為了確實進行基板與晶片的接著，有必要使用與晶片與晶片接著所用的接著劑不同的接著劑，或是基板與晶片的接著硬化與上述的一次全部硬化分開進行，而被認為是生產性降低的原因。
因此，本發明的目的為提供一種接著劑組合物，能夠於接著劑層中將耦合劑均勻的混合，即使在多段封裝的製造時對接著劑層採用一次全部硬化製程的情形，能夠在一次全 部硬化前穩定的進行打線，在硬化後顯示優良的接著強度，特別是於半導體裝置達成高封裝可靠性。並提供具有該接著劑組合物所構成的接著劑層的接著片以及使用該接著片的半導體裝置的製造方法。
為了解決上述課題的本發明包含以下的要旨。
(1)一種接著劑組合物，包含丙烯酸聚合物(A)、具有不飽和烴基的熱硬化性樹脂(B)以及具有反應性雙鍵基的耦合劑(C)。
(2)如(1)所述的接著劑組合物，前述耦合劑(C)為具有反應性雙鍵的矽烷耦合劑。
(3)如(1)或(2)所述的接著劑組合物，其含有填料(G)。
(4)一種單層接著膜，由如(1)~(3)中任一項所述的接著劑組合物所構成。
(5)一種接著片，將如(1)~(3)中任一項所述的接著劑組合物所構成的接著劑層形成於支撐體上而成。
(6)如(5)所述的接著片，支撐體為樹脂膜。
(7)如(5)所述的接著片，支撐體為切割片。
(8)一種半導體裝置的製造方法，包括下述步驟：將上述(5)~(7)中任一項所述的接著片的接著劑層貼附於半導體晶圓；切割前述半導體晶圓以及接著劑層以形成半導體晶片；使接著劑層固著殘存於前述半導體晶片而從支撐體剝離；以及將前述半導體晶片經由前述接著劑層接著於晶粒墊 部上或其他半導體晶片上。
如依本發明，能夠於接著劑層中均勻的混合耦合劑，於未硬化或半硬化狀態，晶片彼此之間或是晶片與基板互相密接。因此，即使是於多段封裝的製造時採用將接著劑層一次全部硬化製程的情形，亦能夠穩定的進行打線，並且以優良的接著強度將半導體晶片與其他半導體晶片或基板接合，即使是在嚴苛的環境下，亦能夠得到顯示高封裝可靠性的半導體裝置。
以下，對本發明的接著劑組合物、接著片以及使用該片的半導體裝置的製造方法進一步具體的說明。
(接著劑組合物)
本發明的樹脂組合物，包含丙烯酸聚合物(A)(以下亦稱為「(A)成分」。其他成分亦相同。)、熱硬化性樹脂(B)、耦合劑(C)作為必須成分，為了改良各種物性，亦可以因應需要包含其他成分。以下，對此些以各成分具體的說明。
(A)丙烯酸聚合物
作為丙烯酸聚合物(A)可使用以往公知的丙烯酸聚合物。丙烯酸聚合物(A)的重量平均分子量(Mw)較佳為1萬~200萬，更佳為10萬~150萬。丙烯酸聚合物(A)的重量平均分子量過低的話，接著劑層與支撐體的接著力變高而可能會產生 晶片的拾取不良。丙烯酸聚合物(A)的重量平均分子量過高的話，接著劑層有可能無法對被著體的凹凸進行追隨，有可能成為空洞等的產生要因。丙烯酸聚合物(A)的重量平均分子量為使用凝膠滲透層析(GPC)法所測定的聚苯乙烯換算值。
丙烯酸聚合物(A)的玻璃轉移溫度(Tg)較佳為-60~70℃，更佳為-30~50℃。丙烯酸聚合物(A)的Tg過低的話，可能會因接著劑層與支撐體的剝離力變大而產生晶片的拾取不良。丙烯酸聚合物(A)的Tg過高的話，用於固定晶圓的接著力有變得不充分的疑慮。
作為構成丙烯酸聚合物(A)的單體，例如是可舉出(甲基)丙烯酸酯及其衍生物。作為具體例可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯等的烷基的碳數為1~18之(甲基)丙烯酸烷基酯；(甲基)丙烯酸環烷酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯基氧基乙酯、醯亞胺(甲基)丙烯酸酯等的具有環狀骨架的(甲基)丙烯酸酯；(甲基)丙烯酸酯羥基甲酯、(甲基)丙烯酸酯2-羥基乙酯、(甲基)丙烯酸酯2-羥基丙酯等含有羥基的(甲基)丙烯酸酯；丙烯酸環氧丙酯、(甲基)丙烯酸環氧丙酯等。而且，亦可以使用丙烯酸、甲基丙烯酸、亞甲基丁二酸等。此些可單獨使用1種，亦可併用兩種以上。
此些之中，作為構成丙烯酸聚合物(A)的單體，由得到與後述的熱硬化性樹脂(B)相溶性良好的丙烯酸聚合 物的觀點來看，較佳是使用至少含有羥基的(甲基)丙烯酸酯。於此情形，於丙烯酸聚合物(A)中，源自含有羥基的(甲基)丙烯酸酯的構成單元，較佳是以1~20質量%的範圍含有，更佳是以3~15質量%的範圍含有。作為丙烯酸聚合物(A)，具體而言較佳是(甲基)丙烯酸烷基酯與含有羥基的(甲基)丙烯酸酯的共聚物。
而且，在不損及本發明的目的的範圍內，亦可以與上述(甲基)丙烯酸酯及其衍生物一起而將乙酸乙烯酯、丙烯腈等作為丙烯酸聚合物(A)的原料單體使用。
在接著劑組合物的全重量中，丙烯酸聚合物(A)較佳是以50質量%以上的比例含有。藉由此構成，使用於將接著劑層一次全部硬化製程時成為較佳的性狀。這是因為即使硬化前的接著劑暴露於高溫之際亦能夠保持某程度的硬度，因而能夠進行打線。亦即是，接著劑組合物的丙烯酸聚合物(A)的含量較多的話，即使在熱硬化前接著劑層的儲藏彈性模數亦能夠高。因此，即使接著劑層為未硬化或半硬化的狀態，亦成為抑制打線時的晶片的振動、位移，而穩定的進行打線。依此，為了確保步驟適性而增加丙烯酸聚合物(A)的含量時，相對的熱硬化性樹脂(B)的量變少。因此有硬化不足的可能性，但是本發明的接著劑組合物能夠經由反應性雙鍵將熱硬化性樹脂(B)與具有反應性雙鍵基的耦合劑結合，因而能夠消除此種的硬化不足的問題。在接著劑組合物的全重量中，丙烯酸聚合物(A)更佳是以50~90質量%的比例含有，更較佳是以50~80質量%的比例含有。
(B)具有不飽和烴基的熱硬化性樹脂
熱硬化性樹脂(B)由環氧樹脂以及熱硬化劑所構成，本發明在環氧樹脂以及熱硬化劑的任一方或是兩方具有不飽和烴基。作為環氧樹脂為具有不飽和烴基的環氧樹脂(B1)以及不具有不飽和烴基的環氧樹脂(B1')，作為熱硬化劑為具有不飽和烴基的熱硬化劑(B2)以及不具有不飽和烴基的熱硬化劑(B2')。於本發明的熱硬化性樹脂(B)中，須包含具有不飽和烴基的環氧樹脂(B1)以及具有不飽和烴基的熱硬化劑(B2)的其中之一作為必須成分。而且，包含具有不飽和烴基的環氧樹脂(B1)以及不具有不飽和烴基的環氧樹脂(B1')的其中之一作為必須成分，包含具有不飽和烴基的熱硬化劑(B2)以及不具有不飽和烴基的熱硬化劑(B2')的其中之一作為必須成分。但是，環氧樹脂以及熱硬化性樹脂的兩方不具有不飽和烴基的情形，亦即是僅由成分(B1')與成分(B2')的組合除外。
由於熱硬化性樹脂(B)具有不飽和烴基，與不具有不飽和烴基的熱硬化性樹脂相較之下，與丙烯酸聚合物(A)以及後述的耦合劑(C)的相溶性高。因此，本發明的接著劑組合物與僅包含不具有不飽和烴基的熱硬化性樹脂作為熱硬化性樹脂之接著劑組合物相較之下，可靠性更為提昇。
不飽和烴基為具有聚合性的不飽和基，作為具體例可舉出乙烯基、烯丙基、丙烯醯基、甲基丙烯醯基、丙烯醯胺基、甲基丙烯醯胺基等，較佳是可舉出丙烯醯基。因此，本發明的不飽和基並不是不具有聚合性的雙鍵。例如是，於成分 (B)可含有芳香環，但芳香環的不飽和結構並不是本發明的不飽和烴基。
作為具有不飽和烴基的環氧樹脂(B1)，為了提升接著劑的熱硬化後的強度或耐熱性，較佳為具有芳香環的樹脂。而且，作為此種具有不飽和烴基的環氧樹脂(B1)，例如是可舉出多官能環氧樹脂的環氧基的一部分變換為包含不飽和烴基的基之化合物。此種化合物例如是可藉由使丙烯酸對環氧基加成反應而合成。或者是可舉出於構成環氧基的芳香環等直接鍵結包含不飽和烴基的基之化合物。
此處，作為具有不飽和烴基的環氧樹脂(B1)，可舉出下述式(1)所表示的化合物、下述式(2)所表示的化合物或是使丙烯酸對後述的不具有不飽和烴基的環氧樹脂(B1')的一部分的環氧基加成反應所得的化合物等。
〔R為H-或是CH3-，n為0~10的整數。〕
【化2】
〔X為或是，R為H-或是CH3-，n為0~10的整數。〕
而且，藉由使不具有不飽和烴基的環氧樹脂(B1')與丙烯酸反應所得的具有不飽和烴基的環氧樹脂(B1)，具有成為未反應物與環氧基完全被消費的化合物之混合物的情形，但是於本發明中，只要是實質的包含上述化合物者即可。
作為不具有不飽和烴基的環氧樹脂(B1')，可使用以往公知的環氧樹脂。作為此種的環氧樹脂，具體而言可舉出多官能系環氧樹脂、或聯苯化合物、雙酚A二環氧丙基醚或其氫化物、甲酚酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、聯苯型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、伸苯基骨架型環氧樹脂等，分子中具有2官能以上的環氧化合物。此些可單獨1種或是組合2種以上使用。
環氧樹脂(B1)以及(B1')的數量平均分子量並沒有特別的限制，由接著劑的硬化性或硬化後的強度或耐熱性的觀點來看，較佳為300~30000，更佳為400~10000，特佳為500~3000。而且，相對於該環氧樹脂總量中的環氧基100莫耳，該環氧樹脂的總量[(B1)+(B1')]中的不飽和基的含量 期望為0.1~1000莫耳，較佳為1~500莫耳，更較佳為10~400莫耳。如為0.1莫耳以下則沒有提昇封裝可靠性的效果，如為1000莫耳以上則有熱硬化性變得不充分的疑慮。
熱硬化劑是相對於環氧樹脂(B1)以及(B1')作為硬化劑的功能，且於本發明，使用具有不飽和烴基的熱硬化劑(B2)以及不具有不飽和烴基的熱硬化劑(B2')，在環氧樹脂僅使用不具有不飽和烴基的環氧樹脂(B1')時，具有不飽和烴基的熱硬化劑(B2)作為必須成分使用。在環氧樹脂具有不飽和烴基時，使用熱硬化劑(B2)以及熱硬化劑(B2')的何者皆可以。
具有不飽和烴基的熱硬化劑(B2)具有聚合性的不飽和烴基，較佳可舉出乙烯基、烯丙基、丙烯醯基、甲基丙烯醯基、丙烯醯胺基、甲基丙烯醯胺基等，更佳包含甲基丙烯醯基、丙烯醯胺基。而且，再更佳為在此些之外包含可與環氧基反應的官能基。作為可與環氧基反應的官能基較佳為可舉出苯酚性羥基、醇性羥基、胺基、羧基以及酸酐等，此些之中更佳為苯酚性羥基、醇性羥基、胺基，特佳為苯酚性羥基。
作為具有不飽和烴基的熱硬化劑(B2)，例如是可舉出苯酚樹脂的羥基的一部分以包含不飽和烴基的基取代而成的化合物，或者是在苯酚樹脂的芳香環直接鍵結包含不飽和烴基的基的化合物等。此處作為苯酚性樹脂，可舉出下述式(化3)所示的酚醛清漆型苯酚樹脂、(化4)所示的二環戊二烯型苯酚樹脂、(化5)所示的多官能系苯酚樹脂等，特別是較佳為酚醛清漆型苯酚樹脂。因此，作為具有不飽和烴基的熱硬化劑 (B2)，較佳為將酚醛清漆型苯酚樹脂的羥基的一部分以包含不飽和烴基的基取代而成的化合物，或者是在酚醛清漆型苯酚樹脂的芳香環直接鍵結包含不飽和烴基的基的化合物。
作為具有不飽和烴基的熱硬化劑(B2)的特佳例，可舉出如下述式(a)所示的在含有苯酚性羥基的重複單元的一部分中導入不飽和烴基之結構，下述式(b)或(c)所示的包含重複單元的化合物，其中重複單元具有包含不飽和烴基的 基。特佳是具有不飽和烴基的熱硬化劑(B2)包含下述式(a)的重複單元與下述式(b)或(c)的重複單元。
(式中n為0或1。)
(式中n為0或1，R1為可具有羥基的碳數1~5的烴基，X為-O-、-NR2(R2為氫或甲基)，或是R1X為單鍵，A為丙烯醯基或甲基丙烯醯基)
重複單元(a)所代表的苯酚性羥基為可與環氧基反應的官能基，具有作為接著劑組合物的熱硬化時與環氧樹脂的環氧基反應硬化之硬化劑的功能。而且，重複單元(b)或(c)所代表的不飽和烴基，具有於接著劑組合物的能量線硬化時聚合硬化，並使接著劑層與支撐體的接著力降低的作用。而且，重複單元(b)或(c)所代表的不飽和烴基，使丙烯酸聚合物(A)與熱硬化性樹脂(B)的相溶性提昇。依此結果，接著劑組合物的硬化物成為更強韌的性質，依此提昇作為接著 劑的可靠性。此熱硬化劑(B2)的前述(a)式所示的重複單元的比例為5~95莫耳%，更佳為20~90莫耳%，特佳為40~80莫耳%，前述(b)或(c)式所示的重複單元的比例合計為5~95莫耳%，更佳為10~80莫耳%，特佳為20~60莫耳%。
作為不具有不飽和烴基的熱硬化劑(B2')，可舉出1分子中具有2個以上可與環氧基反應的官能基之化合物。作為此官能基可舉出苯酚性羥基、醇性羥基、胺基、羧基以及酸酐等。此些之中較佳可舉出苯酚性羥基、胺基、酸酐等，更佳可舉出苯酚性羥基、胺基。
作為苯酚系硬化劑的具體例，可舉出多官能系苯酚樹脂、聯苯酚、酚醛清漆型苯酚樹脂、二環戊二烯系苯酚樹脂、芳烷基苯酚樹脂等。作為胺系硬化劑的具體例，可舉出DICY(二氰二胺)。此些可單獨1種或是混合使用2種以上。
上述的熱硬化劑(B2)以及(B2')的數量平均分子量較佳為300~30000，更佳為400~10000，特佳為500~3000。
相對於環氧樹脂[(B1)以及(B1')]100質量份，接著劑組合物的熱硬化劑[(B2)以及(B2')]的含量較佳為0.1~500質量份，更佳為1~200質量份。熱硬化劑的含量少的話，可能會硬化不足而無法得到接著性，過剩的話則有可能接著劑層的吸濕率高而使封裝的可靠性降低。而且，相對於丙烯酸聚合物(A)100質量份，熱硬化劑[(B2)以及(B2')]的含量較佳為5~50質量份，更佳為10~40質量份。熱硬化劑的含量少的話，可能會硬化不足而無法得到接著性，過剩的話則有可能接著劑層的吸濕率高而使封裝的可靠性降低。
於接著劑組合物中，相對於丙烯酸聚合物(A)100質量份，熱硬化性樹脂(B)(環氧樹脂與熱硬化劑的合計)較佳為含有1~1500質量份，更佳為含有3~1200質量份。熱硬化性樹脂(B)的含量未滿1質量份的話有可能無法得到充分的接著性，超過1500質量份的話有可能使接著劑層與支撐體的剝離力變高，產生拾取不良。
(C)具有反應性雙鍵的耦合劑
具有反應性雙鍵基的耦合劑(C)只要具有反應性雙鍵基的話則沒有特別的限定。反應性雙鍵基較佳為具有反應性的乙烯基、烯丙基、苯乙烯基或(甲基)丙烯酸基。
上述具有反應性雙鍵基的耦合劑並沒有特別的限定。作為該耦合劑，例如是適合使用具有乙烯基的耦合劑、具有苯乙烯基的耦合劑、具有(甲基)丙烯酸氧基((meth)acryloxy group)的耦合劑。由與丙烯酸樹脂的相溶性的觀點來看，上述耦合劑較佳為矽烷耦合劑。
作為上述耦合劑的具體例，可舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯酸氧基丙基二甲氧基矽烷、3-甲基丙烯酸氧基丙基三甲氧基矽烷、3-甲基丙烯酸氧基丙基三乙氧基矽烷、3-甲基丙烯酸氧基丙基甲基二乙氧基矽烷以及3-丙烯酸氧基丙基三甲氧基矽烷等。作為此些的市售品，例如是可舉出KBM-1003、KBE-1003、KBM-1403、KBM-502以及KBM-503、KBE-502、KBE-503、KBM-5103(以上均為信越矽酮公司製)。
相對於丙烯酸聚合物(A)以及熱硬化性樹脂(B) 的合計100質量份，上述耦合劑較佳以0.001~10質量份，更佳以0.005~10質量份，特佳以0.01~5質量份的範圍含有。上述耦合劑的量過多的話，有可能成為接著劑組合物加熱時耦合劑揮發而產生空洞的原因。另一方面，耦合劑的量過少的話有可能無法充分發揮添加耦合劑的效果。
以此種範圍而於接著劑層含有耦合劑(C)的話，即使接著劑層為未硬化或半硬化的狀態，晶片彼此或是晶片與基板的密接性高，且耐受打線時的震動。因此，打線時晶片不會震動、位移，而穩定的進行打線。
其他成分
接著劑組合物除了上述成分之外，可以包含下述成分。
(D)光聚合起始劑
接著劑組合物較佳是含有光聚合起始劑。藉由含有光聚合起始劑，例如是本發明的接著片作為切割．晶粒接著片使用時，在貼附於晶圓後，藉由在切割步驟前照射紫外線，使具有反應性雙鍵基的耦合劑以及熱硬化性樹脂所具有的不飽和烴基反應，而能夠使其預備硬化。藉由進行預備硬化，於硬化前接著劑層為比較軟化，因此對於晶圓的密接性佳，而且於切割時具有適當的硬度而能夠防止對切割刀的接著劑附著等其他的不良狀況。而且，支撐體(樹脂膜或切割帶)與接著劑的界面之密接性的控制等亦成為可能。而且，由於預備硬化狀態比未硬化狀態的硬度高，提昇了打線時的穩定性。
作為光聚合起始劑(D)，具體而言可舉出二苯基酮、苯乙酮、苯偶姻、苯偶姻甲醚、苯偶姻乙醚、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、2,4-二乙基噻吨酮(2,4-diethyl thioxanthone)、α-羥基環己基苯基酮、苄基二苯基硫醚(benzyl diphenyl sulfide)、四甲基硫蘭單硫醚(tetramethyl thiram monosulfide)、偶氮雙異丁腈、聯苯甲醯、二聯苯甲醯、丁二酮、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膦氧化物以及β-氯蒽醌等。光聚合起始劑(D)可單獨使用1種或組合2種以上使用。
使用光聚合起始劑(D)時，其調配比例只要是基於前述耦合劑(C)所具有的反應性雙鍵基、熱硬化性樹脂(B)以及後述任意成分的能量線聚合性化合物(H)所具有的不飽和烴基的合計量適當設定即可。雖然並沒有限定，但例如是相對於熱硬化性樹脂(B)、耦合劑(C)、能量線聚合性化合物(H)合計100質量份，通常為0.1~10質量份，較佳為1~5質量份。光聚合起始劑(D)的含量低於上述範圍的話，光聚合不足而有可能無法得到滿足的反應，高於上述範圍的話，有可能生成未用於光聚合的殘留物，接著劑組合物的硬化性變得不充分。
(E)硬化促進劑
硬化促進劑(E)用於調整接著劑組合物的硬化速度。作為硬化促進劑較佳是可舉出三伸乙基二胺、苄基二甲胺、三乙醇胺、二甲基胺基乙醇、參(二甲基胺基甲基)苯酚等的三級胺類；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等的咪唑類；三丁基膦、二苯基膦、三苯基膦等的有機膦類；四苯基 鏻四苯基硼酸酯、三苯基膦四苯基硼酸酯等的四苯基硼酸鹽等。可單獨使用1種或組合2種以上使用。
使用硬化促進劑(E)時，相對於熱硬化性樹脂(B)的合計100質量份，硬化促進劑(E)較佳為含有0.01~10質量份的量，更佳為含有0.1~1質量份的量。藉由使硬化促進劑(E)以上述範圍的量含有，即使暴露於高溫度高濕度下亦具有優良的接著特性，即使暴露於嚴苛的回流條件時亦能夠達成高封裝可靠性。硬化促進劑(E)的含量少的話則硬化不足而無法得到充分的接著特性，過剩的話則具有高極性的硬化促進劑在高溫度高濕度下於接著劑層中向接著界面側移動、分凝而導致封裝的可靠性降低。
(F)交聯劑
為了調節接著劑層的初期接著力以及凝集力，於接著劑組合物中亦可以添加交聯劑(F)。而且，在調配有交聯劑時，於前述丙烯酸聚合物(A)含有與交聯劑反應的官能基。作為交聯劑(F)可舉出有機多價異氰酸酯化合物、有機多價亞胺化合物等。
作為上述有機多價異氰酸酯化合物，可舉出芳香族多價異氰酸酯化合物、脂肪族多價異氰酸酯化合物、脂環族多價異氰酸酯化合物以及此些的有機多價異氰酸酯化合物的三聚物、以及此些有機多價異氰酸酯化合物與聚醇化合物反應所得的末端異氰酸酯胺基甲酸酯預聚物等。
作為有機多價異氰酸酯化合物，例如是可舉出2,4-甲伸苯基二異氰酸酯、2,6-甲伸苯基二異氰酸酯、1,3-苯二甲 基二異氰酸酯、1,4-苯二甲基二異氰酸酯、二苯甲烷-4,4'-二異氰酸酯、二苯甲烷-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伸苯基二異氰酸酯以及賴胺酸異氰酸酯。
使用異氰酸酯系的交聯劑時，作為丙烯酸聚合物(A)較佳是使用含有羥基的聚合物。如交聯劑具有異氰酸酯基，且丙烯酸聚合物(A)具有羥基，則交聯劑與丙烯酸聚合物(A)產生反應，能夠簡便地於接著劑中導入交聯結構。
作為上述有機多價亞胺化合物，可舉出N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶羧基醯胺)、三羥甲基丙烷-三-β-氮丙啶基丙酸酯、四羥甲基丙烷-三-β-氮丙啶基丙酸酯以及N,N'-甲苯-2,4-雙(1-氮丙啶羧基醯胺)三伸乙基三聚氰胺等。
使用交聯劑(F)時，相對於丙烯酸聚合物(A)100質量份，交聯劑(F)通常以0.01~20質量份，較佳以0.1~10質量份，更佳以0.5~5質量份的比例使用。
(G)填料
為了調整未硬化時、半硬化時以及硬化後的接著劑層的硬度，在接著劑組合物中亦可以含有填料。填料可為無機填充劑、有機填充劑的任一種，但由耐熱性的觀點來看較佳使用無機填充劑。
作為填料的材質可舉出二氧化矽(silica)、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。其中較佳為二氧化矽。
上述填料的平均粒徑較佳為在0.005~2μm的範圍內。上述填料的平均粒徑在此較佳範圍內時，能夠不損及與半導體晶圓的貼附性而發揮接著性。而且，上述「平均粒徑」是藉由雷射繞射．散射法測定所示的體積平均直徑。
相對於丙烯酸聚合物(A)與熱硬化性樹脂(B)的合計100質量份，上述填料較佳是以5~100質量份的範圍含有。上述填料的量過多的話，有可能對晶圓或基板的密接性變差。上述填料粒子的量過少的話，有可能無法充分發揮添加填料的效果。
以此等的範圍使接著劑層含有填料(G)的話，即使接著劑層處於未硬化或半硬化的狀態，亦能夠表現出能耐受打線時的震動程度的彈性模數。因此，打線時晶片不會震動、位移而穩定的進行打線。
(H)能量線聚合性化合物
於接著劑組合物中亦可以調配有能量線聚合性化合物。能量線聚合性化合物(H)包含能量線聚合性基，受到紫外線、電子線等的能量線照射則聚合硬化。作為此種的能量線聚合性化合物(H)的具體例，可舉出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、寡酯丙烯酸酯、胺基甲酸酯丙烯酸酯系寡聚物、環氧基改質丙烯酸酯、聚醚丙烯酸酯以及亞甲基丁二酸寡聚物等的丙烯酸酯系化合物。此種的化合物在分子內至少具有1個聚合性雙鍵，通常重 量平均分子量在100~30000、較佳在300~10000的程度。在使用能量線聚合性化合物(H)時，其調配量並沒有特別的限定，較佳是相對於接著劑組合物的固體成分總量100質量份使用1~50質量份程度的比例。
(I)熱可塑性樹脂
於接著劑組合物中亦可以使用熱可塑性樹脂(I)。熱可塑性樹脂(I)是為了保持硬化後接著劑層的可撓性而加以調配。作為熱可塑性樹脂(I)，重量平均分子量較佳為1000~10萬，更佳為3000~8萬。藉由含有熱可塑性樹脂(I)，能夠使半導體晶片的拾取步驟中的支撐體與接著劑層的層間剝離容易進行，進而能夠使接著劑層追隨基板的凹凸而抑制空洞等的發生。
熱可塑性樹脂(I)的玻璃轉移溫度較佳為-30~150℃，更佳為-20~120℃的範圍。熱可塑性樹脂(I)的玻璃轉移溫度過低的話，有可能使接著劑層與支撐體的剝離力變大而產生晶片的拾取不良，過高的話具有用於固定晶圓的接著力不充分的疑慮。
作為熱可塑性樹脂(I)，可舉出聚酯樹脂、胺基甲酸酯樹脂、苯氧基樹脂、聚丁烯、聚丁二烯、聚苯乙烯等。此些可單獨1種或混合2種以上使用。
在使用熱可塑性樹脂(I)時，相對於丙烯酸樹脂(A)與熱硬化性樹脂(B)的合計100質量份，其調配量較佳為1~300質量份、更佳為2~100質量份的範圍。藉由使熱可塑性樹脂(I)的含量於此範圍內，能夠得到上述的效果。
(J)其他的耦合劑
而且，除了前述耦合劑(C)以外，在接著劑組合物中亦可以調配有不具有反應性雙鍵的耦合劑。作為此種的耦合劑(J)，可舉出不具有反應性雙鍵的矽烷耦合劑。具體可舉出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-環氧基環己基)乙基三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-6-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-6-(胺基乙基)-γ-胺基丙基甲基二乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、γ-脲基丙基三乙氧基矽烷、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(3-三乙氧基矽基丙基)四硫化氫、甲基三甲氧基矽烷、甲基三乙氧基矽烷、咪唑矽烷等。此些可單獨1種或混合2種以上使用。
(K)泛用添加劑
除上述之外，於接著劑組合物中亦可以因應需要調配各種添加劑。作為各種添加劑，可舉出塑化劑、抗靜電劑、抗氧化劑、顏料、染料、捕獲劑(gettering agent)等。
(接著片)
由上述各成分所構成的接著劑組合物所形成的接著劑層，具有感壓接著性與加熱硬化性，能夠於未硬化狀態輕按壓於各種被著體而貼附。而且，由於在接著劑層均勻分散有耦合劑(C)，晶片彼此或晶片與基板互相密接。因此，即使在多段封裝的製造之際採用一次全部硬化製程的情形，能夠進行穩定的打線，並且能夠以優良的接著強度將半導體晶片與其他的半導體晶片或基板接合，即使在嚴苛的環境下，亦能夠得到顯示 出高封裝可靠性的半導體裝置。於含有光聚合起始劑(D)時，亦具有能量線硬化性，能夠在完全硬化之前藉由照射能量線而預備硬化。藉由預備硬化增加接著劑層的硬度，提昇打線時的穩定性。
雖然接著片可為由上述接著劑組合物製膜而成之單層的接著片，但較佳為上述接著劑組合物所構成的接著劑層可剝離的形成於支撐體上而成之接著片。
以下，以接著劑層可剝離的形成於支撐體上而成之接著片為例，以對其較佳態樣以及使用態樣進行說明。在使用接著劑層可剝離的形成於支撐體上而成之接著片時，接著劑層接著於晶圓、晶片等的被著體，並剝離支撐體以將接著劑層轉移於被著體。本發明的接著片的形狀，可為帶狀等的所有形狀。接著片可為表面不具有接著性的樹脂膜，亦可為所謂的切割片。
作為用作為接著片的支撐體的樹脂膜，例如是使用聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯化乙烯膜、氯化乙烯共聚物膜、聚對苯二甲酸乙二酯膜、聚萘二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜、聚胺基甲酸酯膜、乙烯-醋酸乙烯基共聚物膜、多離子聚合物樹脂膜、伸乙基．(甲基)丙烯酸共聚物膜、伸乙基．(甲基)丙烯酸酯共聚物膜、聚苯乙烯膜、聚碳酸酯膜、聚醯亞胺膜、氟樹脂膜等的透明膜。亦或是使用此些的交聯膜。進而亦可以為此些的層積膜。而且，亦可以使用將此些著色的膜、不透明膜等。
本發明的接著片貼附於各種的被著體，對被著體 施加所需要的加工後，接著劑層以固著殘存於被著體的狀態由支撐體剝離。亦即是，對接著劑層使用了包含由支撐體轉移至被著體之步驟的製程。因此，支撐體(樹脂膜)的與接著劑層接觸的面之表面張力，較佳為40mN/m以下，更佳為37mN/m以下，特佳為35mN/m以下。下限值通常為25mN/m的程度。此種表面張力低的樹脂膜，能藉由適當選擇材質而得到，亦能夠藉由在樹脂膜表面塗佈剝離劑施加剝離處理而得到。
作為樹脂膜的剝離處理所使用的剝離劑，使用醇酸系、矽酮系、氟系、不飽和聚酯系、聚烯烴系、石蠟系等，特別是醇酸系、矽酮系、氟系的剝離劑具有耐熱性因而較佳。
為了使用上述剝離劑以對樹脂膜的表面進行剝離處理，亦可以將剝離劑直接無溶劑，或是以溶劑稀釋或乳化，並藉由凹版塗佈機、繞線棒塗佈機、氣刀塗佈機、輥塗佈機等進行塗佈，藉由常溫或加熱或電子線硬化，並藉由濕層積或乾層積、熱熔融層積、熔融擠壓層積、共擠壓層積等以形成層積體。
支撐體亦可為切割片。切割片於如上所述的樹脂膜上具有黏著劑層，在黏著劑層上可剝離地層積前述接著劑層。因此，切割片的黏著劑層能夠以具有再剝離性的公知黏著劑所構成，藉由選擇紫外線硬化型、加熱發泡型、水膨脹型、弱黏性型等的黏著劑，能夠使接著劑層的剝離容易。
而且，接著片亦可以預先將支撐體以及接著劑層模切為與被著體(半導體晶圓)相同形狀。特別是較佳為支撐體以及接著劑層所構成的積層體為保持於長的剝離膜上的型 態。
支撐體的厚度通常為10~500μm，較佳為15~300μm，特佳為20~250μm程度。而且，接著劑層的厚度通常為2~500μm，較佳為6~300μm，特佳為10~150μm程度。
接著片的製造方法並沒有別的限定，在支撐體為樹脂膜時，亦能夠以下述方法製造：在樹脂膜上塗佈乾燥接著劑組合物，以形成接著劑層。亦能夠以下述方法製造：將接著劑層設置於另外的剝離膜上，然後將其轉移至上述樹脂膜或切割片。
而且，在接著片的使用前為了保護接著劑層，亦可以於接著劑層的上面層積剝離膜。該剝離膜可使用在聚對苯二甲酸乙二酯或聚丙烯膜等的塑膠材料上塗佈有矽酮樹脂等的剝離劑者。而且，於接著片的表面外周部亦可以另外設置黏著劑層或黏著帶，用以固定環狀框架等的其他夾具。
其次對於本發明的接著片的利用方法，以該接著片適用於半導體裝置的製造的情形為例加以說明。
(半導體裝置的製造方法)
本發明的半導體裝置的製造方法，包括下述步驟：將上述接著片的接著劑層貼附於半導體晶圓；切割該半導體晶圓以及接著劑層以形成半導體晶片；使接著劑層固著殘存於該半導體晶片裡面而從支撐體剝離；將該半導體晶片經由接著劑層接著於有機基板或導線架的晶粒墊部上或其他半導體晶片上。
以下，對本發明的半導體裝置的製造方法進行詳述。
於本發明的半導體裝置的製造方法中，首先，準備於表面形成電路、於裡面經研磨的半導體晶圓。
半導體晶圓可為矽晶圓，亦可為鎵．砷等的化合物半導體晶圓。對晶圓表面的電路形成，可利用包含蝕刻法、剝離法(lift off)等以往泛用的方法之各種方法以進行。其次，對半導體晶圓的電路面之相反面(裡面)進行研磨。研磨法並沒有特別的限定，亦可以使用研磨器(grinder)等的公知手段進行研磨。在裡面研磨時，為了保護表面的電路而於電路面貼附稱作為表面保護片之黏著片。裡面研磨是將晶圓的電路面側(亦即是表面保護片側)以夾頭座(chuck table)等固定，對未形成電路的裡面側以研磨器進行研磨。晶圓的研磨後厚度並沒有特別的限定，通常為20~500μm程度。
其次，將環狀框架以及半導體晶圓的裡面側載置於本發明的接著片的接著劑層上，輕輕按壓以將半導體晶圓固定。其次，於接著劑層中調配有光聚合起始劑(D)時，從支撐體側對接著劑層照射能量線，使具有反應性雙鍵基的耦合劑(C)以及熱硬化性樹脂(B)所具有的不飽和烴基反應、硬化，提昇接著劑層的凝集力，降低接著劑層與支撐體之間的接著力。作為照射的能量線，可舉出紫外線(UV)或電子線(EB)，較佳使用紫外線。其次，使用切割機(dicing saw)等切斷手段，將上述半導體晶圓切斷以得到半導體晶片。此時的切斷深度，為半導體晶圓的厚度與接著劑層的厚度的合計再加上切割機的磨耗量之深度，接著劑層亦與晶片同尺寸的切斷。而且，能量線的照射亦可以在半導體晶圓的貼附後、半導體晶片的剝 離(拾取)前的任意階段進行，例如是亦可以於切割後進行，或者亦可於下述擴展步驟之後進行。而且，能量線照射亦可以分多次進行。
其次，如因應需要進行接著片的擴展，則半導體晶片的間隔擴張，半導體晶片的拾取變得更容易進行。此時，接著劑層與支撐體之間產生滑動，接著劑層與支撐體之間的接著力減少，半導體晶片的拾取性提昇。如依此進行半導體晶片的拾取，則能夠使切斷的接著劑層固著殘存於半導體晶片的裡面而從支撐體剝離。
其次，經由接著劑層而將半導體晶片載置於作為晶片搭載部之導線架的晶粒墊上或其他的半導體晶片(下段晶片)表面。晶片搭載部於載置半導體晶片前加熱或是在剛載置後加熱，以將晶片暫時接著。加熱溫度通常為80~200℃，較佳為100~180℃，加熱時間通常為0.1秒~5分鐘，較佳為0.5秒~3分鐘，載置時的壓力通常為1kPa~200MPa。
較佳是於晶片暫時接著的狀態依次層積晶片、打線之後，利用封裝製造中通常進行之樹脂密封的加熱，以將接著劑層完全硬化。藉由經過此等的步驟，能夠將接著劑層一次全部硬化而提昇製造效率。而且，於打線時接著劑層為預備硬化的狀態，而穩定的進行打線。而且，由於接著劑層於晶粒結著條件下為軟化，即使是晶片搭載部的凹凸亦能夠充分的埋入，能夠防止空洞的發生而封裝的可靠度變高。
本發明的接著劑組合物以及接著片，除了上述的使用方法之外，亦能夠使用於半導體化合物、玻璃、陶瓷、金 屬等的接著。
【實施例】
以下藉由實施例說明本發明，但是本發明並不限定於此些實施例。而且，於以下的實施例以及比較例中，〈分散性評估〉、〈對基板的埋入性評估〉以及〈封裝可靠性評估〉如下述進行。
〈分散性評估〉
將實施例以及比較例所製備的接著劑組合物，以於剝離膜上成為20μm的厚度之方式塗佈，目視確認有無發生條紋。填料的分散性差、凝集的情形會產生條紋。
〈對基板的埋入性評估〉
將實施例以及比較例所製備的接著劑組合物，以於剝離膜上乾燥後厚度成為20μm的厚度之方式塗佈、乾燥，以得到接著膜。於覆銅箔層積板(三菱氣體化學股份有限公司製CCL-HL830)的銅箔(18μm厚)形成電路圖案，且於圖案上具有抗鍍劑(太陽墨水製PSR-4000 AUS303)之基板(股份有限公司Chino技研製LN001E-001 PCB(Au)AUS303)上，將貼附有接著膜的玻璃晶片(8mm×8mm，厚度150μm)經由接著膜以150℃、100gf、1秒鐘的條件壓著，其後，假設模密封步驟並以熱封測試機(Tester產業公司製TP-701)以每一個晶片施加壓力6.9MPa、175℃、2分鐘以進行熱壓著。其後使用數位顯微鏡(Keyence公司製VHX-200)以倍率20倍觀察玻璃晶片上面以確認埋入性。埋入性的判斷如下：將包含空洞等的空氣層的部分除外，如晶片面積95%以上被埋入的話，則埋 入性為良好。
〈封裝可靠性評估〉 (半導體晶片的製造)
於乾研磨精加工的矽晶圓(150mm直徑，厚度75μm)的研磨面，以膠帶貼合機(Lintec公司製，Adwill RAD2500)進行實施例以及比較例的接著片之貼附，固定於晶圓切割用環狀框架。其後，使用紫外線照射裝置(Lintec公司製，Adwill RAD2000)從支撐體面照射紫外線(220mW/cm2，160mJ/cm2)。其次，使用切割裝置(股份有限公司Disco製，DFD651)切割為8mm×8mm的晶片尺寸。切割時的切入量，以切入支撐體20μm的方式而設定。
(半導體封裝的製造)
使用於覆銅箔層積板(三菱氣體化學股份有限公司製CCL-HL830)的銅箔(18μm厚)形成電路圖案，且於圖案上具有抗鍍劑(太陽墨水製PSR-4000 AUS303)之基板(股份有限公司Chino技研製LN001E-001 PCB(Au)AUS303)作為基板。將上述所得的接著片上的晶片與接著劑層一起由支撐體取出，經由接著劑層以120℃、250gf、0.5秒鐘的條件壓著於基板上。其後，再將其他的晶片經由接著劑層再度以120℃、250gf、0.5秒鐘的條件壓著於已接著的晶片上，以2段層積半導體晶片。其後，以密封厚度成為400μm的方式而以模封樹脂(京瓷化學股份有限公司製KE-1100AS3)進行密封(密封裝置Apic Yamada股份有限公司製MPC-06M TriAl Press)，並以175℃、5小時使樹脂硬化。接著，將已密封的基板貼附於切割 帶(Lintec股份有限公司製，Adwill D-510T)，使用切割裝置(股份有限公司Disco製，DFD651)切割為8mm×8mm的晶片尺寸，以得到可靠性評估用的半導體封裝。
(評估)
將所得的半導體封裝於60℃、濕度60%RH條件下以及85℃、濕度60%RH條件下放置120小時、吸濕後，以預熱160℃而最高溫度成為260℃之加熱時間1分鐘的紅外(IR)回流(回流爐：相模理工製WL-15-20DNX型)進行3次時的接合部的浮起．剝離的有無、封裝破裂發生的有無，以掃瞄型超音波探傷裝置(日立建機Finetec股份有限公司製Hye-Focus)以及斷面研磨機(Refinetec股份有限公司製，Refine．PolisherHV)切割出斷面，並使用數位顯微鏡(Keyence公司製VHX-100)藉由觀察斷面以進行評估。在基板/半導體晶片接合部觀察到長度0.5mm以上的剝離時則判斷為剝離，並計數將封裝投入27個至試驗且未發生剝離的個數。
〈接著劑組合物〉
構成接著劑組合物的各成分如下所示。
(A)丙烯酸聚合物：日本合成化學工業公司製N-4617(含羥基)
(B)熱硬化性樹脂：
(B-1)丙烯醯基加成甲酚酚醛清漆型環氧樹脂(日本化藥股份有限公司製CNA-147)
(B-2)熱硬化劑：芳烷基苯酚樹脂(三井化學股份有限公司製MilexXLC-4L)
(C)耦合劑：
(C-1)具有甲基丙烯酸基的矽烷耦合劑(信越Silicone公司製KBM-5103)
(C-2)具有環氧基的矽烷耦合劑(信越Silicone公司製KBM-402)
(C-3)具有環氧基的矽烷耦合劑(信越Silicone公司製KBM-403)
(C-4)具有硫醇基的矽烷耦合劑(信越Silicone公司製KBM-803)
尚且，耦合劑的使用量，以接著劑組合物所含的來自耦合劑的甲氧基的莫耳數在實施例以及比較例大約相等的方式進行調整。
(D)光聚合起始劑(Ciba Specialty Chemicals股份有限公司製Irgacure184)
(E)硬化促進劑：咪唑(四國化成工業股份有限公司製Curezol2PHZ)
(F)交聯劑：芳香族性多價異氰酸酯(日本Polyurethane工業股份有限公司製CoronateL)
(G)填料：日產化學工業股份有限公司製SilicasilMEK-ST平均填料粒徑12nm
(實施例以及比較例)
上述各成分以表1所記載的量(質量比)調配，得到接著劑組合物。使用所得的組合物的甲基乙基酮溶液(固體成分濃度30質量%)以評估分散性。結果如表1所示。而且，以乾燥 後的厚度為20μm的方式，將接著劑組合物溶液塗佈、乾燥(乾燥條件：以烘箱100℃、1分鐘)於經矽酮剝離處理的剝離膜(Lintec股份有限公司製，SP-PET381031)的剝離處理面上，其後貼合於支撐體(聚乙烯膜，厚度100μm，表面張力33mN/m)，藉由將接著劑層轉移至支撐體上以得到接著片。使用所得的接著片製作半導體封裝，評估其可靠性。結果如表1所示。表1中PKG可靠性表示封裝可靠性，以上述評估中未發生剝離個數/27(投入試驗的封裝個數)而表示。
根據上述結果，可瞭解藉由採用本發明的構成，改善了耦合劑的分散性，晶片彼此或晶片與基板密接，且接合時的埋入性良好，打線時即使暴露於高溫亦能夠維持半導體封裝的可靠性。因此，藉由提供本發明接著劑組合物以及接著片，多段堆疊的半導體封裝的製造變得容易，且生產性提昇。

Claims (5)

  1. 一種半導體裝置的製造方法，包括下述步驟：將由包含丙烯酸聚合物(A)，由環氧樹脂及熱硬化劑所形成、環氧樹脂及熱硬化劑之任一方或雙方具有不飽和烴基的熱硬化性樹脂(B)以及具有反應性雙鍵基的矽烷耦合劑(C)的接著劑組合物所形成的接著劑層形成於支撐體上而成之接著片的接著劑層貼附於半導體晶圓；切割前述半導體晶圓以及前述接著劑層以作為半導體晶片；使前述接著劑層固著殘存於前述半導體晶片而從前述支撐體剝離；以及將前述半導體晶片經由前述接著劑層接著於其他半導體晶片上，以樹脂封裝藉由加熱將前述接著劑層一次全部硬化。
  2. 如申請專利範圍第1項所述的半導體裝置的製造方法，其中前述接著劑組合物中，前述具有不飽和烴基的熱硬化性樹脂(B)相對於前述丙烯酸聚合物(A)100質量份，含有1~1500質量份。
  3. 如申請專利範圍第1或2項所述的半導體裝置的製造方法，其中前述接著劑組合物含有填料(G)。
  4. 如申請專利範圍第1或2項所述的半導體裝置的製造方法，前述支撐體為樹脂膜。
  5. 如申請專利範圍第1或2項所述的半導體裝置的製造方法，前述支撐體為切割片。
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