TWI591140B - An adhesive composition, a sheet, and a method of manufacturing a semiconductor device - Google Patents

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

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Publication number
TWI591140B
TWI591140B TW103118540A TW103118540A TWI591140B TW I591140 B TWI591140 B TW I591140B TW 103118540 A TW103118540 A TW 103118540A TW 103118540 A TW103118540 A TW 103118540A TW I591140 B TWI591140 B TW I591140B
Authority
TW
Taiwan
Prior art keywords
adhesive
semiconductor wafer
adhesive layer
double bond
adhesive composition
Prior art date
Application number
TW103118540A
Other languages
English (en)
Other versions
TW201510136A (zh
Inventor
Sayaka Tsuchiyama
Naoya Saiki
Yuichiro Azuma
Hideaki Suzuki
Original Assignee
Lintec Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2013111974A external-priority patent/JP6029536B2/ja
Priority claimed from JP2013126935A external-priority patent/JP6029544B2/ja
Application filed by Lintec Corp filed Critical Lintec Corp
Publication of TW201510136A publication Critical patent/TW201510136A/zh
Application granted granted Critical
Publication of TWI591140B publication Critical patent/TWI591140B/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08L33/04—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
    • C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
    • 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
    • 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
    • C09J133/06—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
    • C09J133/10—Homopolymers or copolymers of methacrylic acid 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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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    • H01L21/6835—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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    • H01L21/683—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
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
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    • 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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    • H01L24/93—Batch processes
    • H01L24/94—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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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/50—Multistep manufacturing processes of assemblies consisting of devices, each device being of a type provided for in group H01L27/00 or H01L29/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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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
    • 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
    • C09J2301/302—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 pressure-sensitive, i.e. 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
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    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • 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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    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
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Description

接著劑組合物、接著板片及半導體裝置之製造方法
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板片以及使用該接著板片的半導體裝置之製造方法。
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板片的狀態施加切割、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，提出各種同時兼具有晶圓固定功能與晶粒接著功能之切割．晶粒結著用接著板片(專利文獻1等)。專利文獻1所揭示的接著板片，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。該接著劑包含丙烯酸聚合物、含有反應性雙鍵基之環氧樹脂及熱硬化劑，因應必要包含二氧化矽(silica)等的填料。
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(reflow))。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佳狀況的可能性高。因此，於前述專利文獻1，作為環氧樹脂使用含有反應性雙鍵基之環氧樹脂，提升丙烯酸聚合物與環氧樹脂之相溶性，藉此改善接著可靠性。
而且，為了高密度封裝，提出有將晶片多段積層 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積層晶片，並於接著劑層硬化後進行打線(wire bonding)，進而依序進行晶片的積層、接著劑層的硬化、打線，以將晶片積層。
在如同上述晶片被多段積層之封裝結構的半導體 裝置的製造中，檢討以下步驟。首先，於接著劑層未硬化或半硬化的狀態進行積層或打線，在所有的晶片積層後，利用模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。
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，有可能使得導線的位置變為不正確，無法進行打線。為了消除此不佳狀況，在採用上述製法時，使用即使是未硬化狀態亦比較硬的接著劑。作為用以使未硬化狀態的接著劑層的硬度提高的手段，考慮在接著劑中調配較多量的填料。
[先前技術文獻] [專利文獻]
專利文獻1：日本專利公開第2008-133330號公報
但是，於接著劑中均勻的混合填料並不見得容易。如接著劑中的填料的分散性差，填料彼此之間凝集而使外觀的粒徑變大，而成為接著劑層的厚度的精度降低、與半導體晶圓的貼附性或接著性降低的原因。特別是如增加填料的調配量，上述的不佳狀況變得顯著。而且，如於接著劑中調配多量的填料，有可能相對的使硬化性成分(環氧樹脂等)的調配量降低、且硬化後的接著劑層的可靠性降低。
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，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填料均勻的混合，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 的接著劑層的接著板片以及使用該接著板片的半導體裝置之製造方法。
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)、具有反應性雙鍵基的熱硬化性樹脂(B)以及於表面具有反應性雙鍵基的填料(C)，該丙烯酸聚合物(A)的重量平均分子量為50萬以上，該熱硬化性樹脂(B)由環氧樹脂以及熱硬化劑所構成，該環氧樹脂以及該熱硬化劑的其中之一或者兩者具有反應性雙鍵基。
〔2〕一種接著劑組合物，包含丙烯酸聚合物(A)、具有反應性雙鍵基的熱硬化性樹脂(B)以及於表面具有反應性雙鍵基的填料(C)，該填料(C)的平均粒徑為0.01~0.2μm的範圍，該熱硬化性樹脂(B)由環氧樹脂以及熱硬化劑所構成該環氧樹脂以及該熱硬化劑的其中之一或者兩者具有反應性雙鍵基。
〔3〕如〔1〕或〔2〕所記載的接著劑組合物，前述填料(C)為於表面具有反應性雙鍵基的二氧化矽。
〔4〕如〔1〕~〔3〕中任一項所述的接著劑組合物，於接著劑組合物的總質量中，前述丙烯酸聚合物(A)含有比例為50~90質量%。
〔5〕如〔1〕~〔4〕中任一項所述的接著劑組合 物，前述丙烯酸聚合物(A)具有羥基。
〔6〕一種單層接著膜，由〔1〕~〔5〕中任一項所述的接著劑組合物所構成。
〔7〕一種單層接著膜，由〔2〕所記載的接著劑組合物所構成，於250℃硬化後的剪切強度為60N/5mm□以上。
〔8〕一種接著板片，將〔1〕~〔5〕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。
〔9〕一種接著板片，將〔2〕所記載的接著劑組合物所構成的接著劑層形成於支撐體上而成，於250℃硬化後的接著劑層之剪切強度為60N/5mm□以上。
〔10〕如〔8〕或〔9〕所記載的接著板片，前述支撐體為樹脂膜。
〔11〕如〔8〕或〔9〕所記載的接著板片，前述支撐體為黏著板片。
〔12〕一種半導體裝置之製造方法，包括下述步驟：將上述〔8〕~〔11〕中任一項所述的接著板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。
〔13〕一種半導體裝置之製造方法，包括下述步驟：在半導體晶圓的表面形成符合單片化半導體晶片之形狀的外部輪廓的溝；於半導體晶圓的表面貼附保護板片；接著由背面側進行到達溝為止的薄化處理，以將半導體晶圓單片化為半 導體晶片；以及將上述〔8〕~〔11〕中任一項所述的接著板片的接著劑層貼附於前述半導體晶片；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。
如依本發明的第1發明，藉由使用具有規定的重量平均分子量的丙烯酸聚合物，具有反應性雙鍵基的熱硬化樹脂，以及於表面具有反應性雙鍵基的填料；而且，如依本發明的第2發明，藉由使用丙烯酸聚合物，具有反應性雙鍵基的熱硬化樹脂，以及於表面具有反應性雙鍵基、且具有規定的平均粒徑的填料，在提升接著劑組合物中的丙烯酸聚合物、熱硬化樹脂以及填料的相溶性的同時，提升接著劑組合物中的填料的分散性。而且，藉由反應性雙鍵基彼此的加成聚合，在接著劑組合物中形成三維網狀結構。其結果，能夠藉由優良的接著強度將半導體晶片結合於其他的半導體晶片或基板，即使在嚴苛的環境下，亦能夠得到顯示高封裝可靠性的半導體裝置。而且，由於未硬化或半硬化狀態的接著劑層具有某程度的硬度，對接著劑層能夠穩定的進行打線。
以下，對本發明的接著劑組合物、接著板片以及使用該板片的半導體裝置之製造方法進行更具體的說明。
(接著劑組合物)
本發明的接著劑組合物包含丙烯酸聚合物(A)(以下亦稱為「(A)成分」。其他的成分亦相同)、熱硬化性樹脂(B)、填料(C)作為必須成分，為了改良各種的物性，亦可以因應需要含有其他成分。以下對此些的各成分具體的進行說明。
(A)丙烯酸聚合物
第1發明的丙烯酸聚合物(A)的重量平均分子量(Mw)為50萬以上，較佳為50萬~200萬，更佳為50萬~150萬，再更佳為50萬~80萬。丙烯酸聚合物(A)的重量平均分子量未滿50萬的話，成為接著劑層的凝集力降低、且使用該接著劑層所製造的半導體裝置的封裝可靠性降低的原因。丙烯酸聚合物(A)的重量平均分子量過高的話，有可能成為對被著體(半導體晶圓、晶片或基板等)的貼附性降低、且轉印不良或空洞等的發生要因。
第2發明的丙烯酸聚合物(A)的重量平均分子量(Mw)並沒有特別限制，但較佳為50萬以上，更佳為50萬~200萬，再更佳為50萬~150萬，特佳為50萬~80萬。丙烯酸聚合物(A)的重量平均分子量未滿50萬的話，接著劑層的凝集力有可能降低，但藉由使用第2發明中後述的具有規定的平均粒徑之填料，被著體與接著劑層的接著性提升，其結果，半導體裝置的封裝可靠性優良。丙烯酸聚合物(A)的重量平均分子量過高的話，有可能成為對被著體的貼附性降低、且轉印不良或空洞等的發生要因。
而且，丙烯酸聚合物(A)的分子量分布(Mw/Mn、 Mn為數量平均分子量)較佳為1~5，更佳為1~3。藉由使丙烯酸聚合物(A)的分子量分布在上述範圍，本發明所具有的封裝可靠性的提升效果變得更高。
尚且，丙烯酸聚合物(A)的重量平均分子量(Mw)、數量平均分子量(Mn)以及分子量分布(Mw/Mn)的值，是藉由凝膠滲透層析(GPC)法，以後述實施例的測定條件進行測定的情形之值(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-20~50℃，更佳為-10~40℃，再更佳為0~30℃的範圍。丙烯酸高分子(A)之玻璃轉移溫度於此範圍的話，封裝的可靠性具有提升的傾向。作為丙烯酸聚合物(A)的玻璃轉移溫度的調整方法舉出下述的方法。例如是，作為提高玻璃轉移溫度的方法，可舉出當使用後述的烷基的碳數為1~18的(甲基)丙烯酸烷基酯作為構成丙烯酸聚合物(A)的單體的情形，選擇烷基的碳數小的(甲基)丙烯酸烷基酯的方法，或是使烷基的碳數小的(甲基)丙烯酸烷基酯的含有比例增大的方法。
尚且，丙烯酸聚合物(A)的玻璃轉移溫度為由福克斯(FOX)的式所求得的值。
構成本發明的丙烯酸聚合物(A)的單體，至少包含(甲基)丙烯酸酯單體或其衍生物。
作為(甲基)丙烯酸酯單體或其衍生物。例如是可舉出，烷基的碳數為1~18的(甲基)丙烯酸烷基酯、具有環狀骨架的(甲基)丙烯酸酯、具有羥基的(甲基)丙烯酸酯、具有環氧丙烷基的(甲基)丙烯酸酯、具有胺基的(甲基)丙烯酸酯、 具有羧基的(甲基)丙烯酸酯。
作為烷基的碳數為1~18的(甲基)丙烯酸烷基酯， 例如是可舉出，(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、(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)丙烯酸十四烷酯、(甲基)丙烯酸十八烷酯等。
作為具有環狀骨架之(甲基)丙烯酸酯，例如是可舉出，(甲基)丙烯酸環烷酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異冰片酯、二環戊基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、二環戊烯氧乙基(甲基)丙烯酸酯、醯亞胺(甲基)丙烯酸酯等。
作為具有羥基的(甲基)丙烯酸酯，例如是可舉出，(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯等。
作為具有環氧丙基的(甲基)丙烯酸酯，例如是可舉出，(甲基)丙烯酸環氧丙酯。
作為具有胺基的(甲基)丙烯酸酯，例如是可舉出，單乙胺(甲基)丙烯酸酯、二乙胺(甲基)丙烯酸酯等。
作為具有羧基的(甲基)丙烯酸酯，例如是可舉出，2-(甲基)丙烯醯氧基乙基鄰苯二甲酸酯、2-(甲基)丙烯醯氧基丙基鄰苯二甲酸酯等。
此外，丙烯酸聚合物(A)，亦可與(甲基)丙烯 酸、伊康酸等的(甲基)丙烯酸酯以外的具有羧基的單體，乙烯基醇、N-羥甲基(甲基)丙烯醯胺等的(甲基)丙烯酸酯以外的具有羥基的單體，(甲基)丙烯醯胺、醋酸乙烯酯、苯乙烯等共聚合。
接著劑組合物含有後述的交聯劑(G)的情形，丙 烯酸聚合物(A)較佳具有與交聯劑(G)反應的官能基(羥基、胺基、環氧丙基、羧基等)，特別是具有羥基的丙烯酸聚合物(A)，由於其製造容易，使用交聯劑(G)容易導入交聯結構，因而較佳。而且，具有羥基的丙烯酸聚合物與後述的熱硬化性樹脂(B)的相溶性良好。
作為構成丙烯酸聚合物(A)的單體，藉由使用具 有與交聯劑(G)反應之官能基的單體而於丙烯酸聚合物(A)中導入與交聯劑(G)反應的官能基之情形，具有與交聯劑(G)反應之官能基的單體在構成丙烯酸聚合物(A)的單體總質量中之比例較佳為1~20質量%程度，更佳為3~15質量%。在丙烯酸聚合物(A)中，藉由使來自於具有與交聯劑(G)反應之官能基的單體之構成單元在上述範圍，與交聯劑(G)反應的官能基與交聯劑(G)反應而形成三維網狀結構，能夠提高丙烯酸聚合物(A)的交聯密度。其結果，本發明的接著劑組合物能夠形成具有優良的剪切強度的單層接著膜或接著劑層。而且，由於接著劑組合物的吸水性降低，能夠得到封裝可靠性優良的半導體裝置。
於接著劑組合物之總質量中，較佳以50質量%以 上的比例包含丙烯酸聚合物(A)。藉由以如此之構成，將接 著劑層用於一次全部硬化製程時成為較佳的狀態。這是因為即使硬化前的接著劑暴露於高溫時亦能保持某程度的硬度，而能夠進行打線。亦即是，接著劑組合物中的丙烯酸聚合物(A)的含量較多的話，即使在熱硬化前亦能使接著劑層的儲藏彈性模數高。因此，即使接著劑層於未硬化或半硬化的狀態，亦能夠抑制打線接合時的晶片的振動、位移，穩定的進行打線。依此，在為了確保步驟適性而增加丙烯酸聚合物(A)的含量的情形，相對的減少熱硬化樹脂(B)的量。因此，雖然具有硬化不足的可能性，但是由於本發明的接著劑組合物的熱硬化樹脂(B)與填料(C)能夠藉由反應性雙鍵基結合，而能夠克服此種硬化不足的問題。於接著劑組合物的總質量中，較佳以50~90質量%的比例含有丙烯酸聚合物(A)，更佳以50~80質量%的比例含有。於第1發明中，藉由使接著劑組合物中的重量平均分子量(Mw)50萬以上之丙烯酸聚合物(A)的比例於上述範圍，本發明的封裝可靠性(A)的提升效果變得更為顯著。
(B)具有反應性雙鍵基的熱硬化樹脂
熱硬化樹脂(B)由環氧樹脂以及熱硬化劑所構成，於本發明是在環氧樹脂以及熱硬化劑的其中之一或兩者具有反應性雙鍵基。作為環氧樹脂為具有反應性雙鍵基的環氧樹脂(B1)以及不具有反應性雙鍵基的環氧樹脂(B1')，作為熱硬化劑為具有反應性雙鍵基的熱硬化劑(B2)以及不具有反應性雙鍵基的熱硬化劑(B2')。於本發明的熱硬化性樹脂(B)中，須包含具有反應性雙鍵基的環氧樹脂(B1)以及具有反應性雙鍵 基的熱硬化劑(B2)的其中之一作為必須成分。而且，包含環氧樹脂(B1)以及環氧樹脂(B1')的其中之一作為必須成分，包含熱硬化劑(B2)以及熱硬化劑(B2')的其中之一作為必須成分。但是，環氧樹脂以及熱硬化劑的兩方不具有反應性雙鍵基的情形，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)具有反應性雙鍵基，與不 具有反應性雙鍵基的熱硬化性樹脂相較之下，與丙烯酸聚合物(A)以及後述的填料(C)的相溶性高。而且，藉由使接著劑組合物中的反應性雙鍵基彼此加成聚合，於接著劑組合物中形成三維網狀結構。因此，本發明的接著劑組合物與僅包含不具有反應性雙鍵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，能夠提升半導體裝置的可靠性。
反應性雙鍵基為具有聚合性的碳-碳雙鍵的官能 基，作為具體例可舉出乙烯基、烯丙基、(甲基)丙烯醯基、(甲基)丙烯酸氧基((meth)acryloxy group)等，較佳是可舉出丙烯醯基。因此，本發明的反應性雙鍵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反應性雙鍵基。
作為具有反應性雙鍵基的環氧樹脂(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，作為此種具有反應性雙鍵基的環氧樹脂(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反應性雙鍵基的基之化合物。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反應性雙鍵基的基之化合物。
此處，作為具有反應性雙鍵基的環氧樹脂(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反應性雙鍵基的環氧樹脂(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。〕
〔X為或是 R為H-或是CH3-，n為0~10的整數。〕
另外，雖有藉由使不具有反應性雙鍵基的環氧樹脂(B1')與丙烯酸反應所得的具有反應性雙鍵基的環氧樹脂(B1)，成為與未反應物或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。
作為不具有反應性雙鍵基的環氧樹脂(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')]中的反應性雙鍵基的含量期望為0.1~1000莫耳，較佳為1~500莫耳，更較佳為10~400莫耳。
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，使用具有反應性雙鍵基的熱硬化劑(B2)以及不具有反應性雙鍵基的熱硬化劑(B2')的其中之一或兩者作為熱硬化劑。在環氧樹脂僅使用不具有反應性雙鍵基的環氧樹脂(B1')時，具有反應性雙鍵基的熱硬化劑(B2)作為必須成分使用。在環氧樹脂具有反應性雙鍵基時，使用熱硬化劑(B2)以及熱硬化劑(B2')的何者皆可以，亦可以使用兩者。
具有反應性雙鍵基的熱硬化劑(B2)，為具有聚 合性的碳-碳雙鍵基的熱硬化劑。作為反應性雙鍵基，較佳可 舉出乙烯基、烯丙基、(甲基)丙烯醯基以及(甲基)丙烯酸氧基等，更佳包含甲基丙烯醯基。
而且，熱硬化劑(B2)除了上述的反應性雙鍵基之外，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。
作為具有反應性雙鍵基的熱硬化劑(B2)，例如 是可舉出苯酚樹脂的羥基的一部分以包含反應性雙鍵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反應性雙鍵基的基的化合物等。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、下述式(化4)所示的二環戊二烯型苯酚樹脂、下述式(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，作為具有反應性雙鍵基的熱硬化劑(B2)，較佳為將酚醛清漆型苯酚樹脂的羥基的一部分以包含反應性雙鍵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反應性雙鍵基的基的化合物。
作為具有反應性雙鍵基的熱硬化劑(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反應性雙鍵基之結構，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反應性雙鍵基的基。特佳是具有反應性雙鍵基的熱硬化劑(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為甲基丙烯醯基)
重複單元(a)所含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)所含的反應性雙鍵基，藉由使丙烯酸聚合物(A)與熱硬化性樹脂(B)的相溶性提昇，並且反應性雙鍵基彼此加成聚合，而在接著劑組合物中形成三維網狀結構。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。而且，重複單元(b)或(c)所含的反應性雙鍵基，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。
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%。
作為不具有反應性雙鍵基的熱硬化劑(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。
由於含有具有胺基的熱硬化劑(胺系熱硬化劑)的接著劑層之吸濕性，高於含有具有苯酚性羥基的熱硬化劑(苯酚系熱硬化劑)的接著劑層，在濕熱條件投入後的接著劑層的接著性的降低大，但由於含有苯酚系熱硬化劑的接著劑層其耐濕熱性高，投入濕熱條件後的接著劑層的接著性的降低小。因此，作為熱硬化劑(B2')，特佳是在分子中具有2個以上的可與環氧基反應的苯酚性羥基之化合物。
作為苯酚系熱硬化劑的具體例，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40~30000，更佳為60~10000，特佳為80~3000。
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。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。藉由使接著劑組合物中的熱硬化劑的含量或丙烯酸聚合物(A)對熱硬化劑的含量於上述範圍，封裝的可靠性優良。
於接著劑組合物的總質量中，熱硬化性樹脂(B)(環氧樹脂與熱硬化劑的合計[(B1)+(B1')+(B2)+(B2')])較佳以未滿50質量%，更佳以1~30質量%，再更佳以5~25質量%的比例含有。而且，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)較佳以1質量份以上、未滿100質量份，更佳以3~60質量份，再更佳以3~40質量份的範圍含有。熱硬化性樹脂(B)的含量過少的話，有可能無法得到充分的接著性，過多的話接著劑層與支撐體的剝離力變高，有可能產生拾取不良。
(C)於表面具有反應性雙鍵基的填料
於表面具有反應性雙鍵基的填料(C)，只要於表面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乙烯基、烯丙基、(甲基)丙烯醯基或(甲基)丙烯酸氧基。
上述填料較佳為經由具有反應性雙鍵基的化合物進行表面處理的填料。
作為填料(未處理的填料)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。二氧化矽所具有的矽醇基，對於與矽烷耦合劑的結合可發揮有效的作用。
於表面具有反應性雙鍵基的填料，例如是對未處理之填料的表面，藉由具有反應性雙鍵基的耦合劑進行表面處理以得到。
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)丙烯酸氧基的耦合劑。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)。
上述藉由耦合劑表面處理上述填料的方法並沒有 特別的限定。作為此方法，例如是可舉出在漢賽混合機(henschel mixer)或是V型混合機等的可高速攪拌的混合機中添加未處理的填料並攪拌，並且將耦合劑直接添加或是將耦合劑溶解、分散於醇水溶液、有機溶媒或是水溶液而添加的乾式法。而且，可舉出在未處理的填料之漿料中添加耦合劑的漿料法；將未處理的填料乾燥後，以噴塗(spray)賦予耦合劑的噴塗法等的直接處理法，或者是在製備上述組合物時，將未處理的填料與丙烯酸系聚合物混合，於該混合時直接添加的共摻合(Integral Blend)法等。
對上述未處理的填料100質量份進行表面處理之耦合劑的量，較佳下限為0.1質量份，較佳上限為15質量份。
第1發明的上述填料的平均粒徑並沒有特別的限定，較佳為在0.01~2μm的範圍內。上述填料的平均粒徑在此較佳範圍內時，能夠不損及與被著體的貼附性而發揮接著性。而且，特別是用於將晶片載置於基板或其他的晶片等的被著體的情形，顯著的得到本發明之接著劑組合物的可靠性提昇效果。於第1發明，填料的平均粒徑為超過0.2μm、2μm以下的情形，具有本發明的單層接著膜或接著板片的面狀態惡化、且與被著體的貼附性變差的可能性，但藉由使用重量平均分子量為50萬以上的丙烯酸聚合物(A)，接著劑組合物的黏度提升，作為其結果能夠防止與被著體的貼附性降低。上述平均粒徑超過2μm的話，具有本發明的單層接著膜或接著板片的面狀態惡 化、與晶圓的貼附性變差，且接著層的面內厚度散亂的可能性。尚且，上述「平均粒徑」是藉由使用動態光散射法之粒度分布計(日機裝公司製，裝置名：Nanotrac150)所求取(以下相同)。
第2發明的上述填料的平均粒徑在0.01~0.2μm的 範圍內。上述填料的平均粒徑在此範圍內時，能夠不損及與半導體晶圓的貼附性而發揮接著性。而且，特別是用於將晶片載置於基板或其他的晶片等的被著體時，顯著的得到本發明之接著劑組合物的可靠性提昇效果。上述平均粒徑過大的話，具有板片的面狀態惡化、接著層的面內厚度散亂，且接著劑組合物的硬化物的剪切強度降低此等的不佳狀況發生的可能性。
於第2發明中，藉由使填料的平均粒徑於上述範圍，接著劑組合物的可靠性提升效果變得顯著，推測其理由如下。
填料的粒徑大的話，填料彼此之間所埋入的填料以外的成分所形成的結構亦成為大者。填料以外的成分比填料的凝集性低。由填料以外的成分所形成的結構大的話，填料以外的成分產生破裂的情形，具有破裂會擴廣為廣範圍的疑慮。另一方面，填料細微的話，填料以外的成分所形成的結構亦為細微者。依此，即使填料以外的成分產生破裂，混入其細微結構的填料會妨礙其破裂的進行。其結果，破裂具有不擴廣為廣範圍的傾向。進而，本發明的填料所具有的甲基丙烯酸氧基等的反應性雙鍵基與填料以外的成分所含的B1成分等的反應性雙鍵基產生鍵結。填料細微的話，填料與填料以外的成分的接觸面積變大。其結果，具有填料與B1成分等的結合增加的傾向。
於表面具有反應性雙鍵基的填料(C)，與丙烯酸 聚合物(A)、熱硬化性樹脂(B)的親和性優良，能夠均勻的分散於接著劑組合物中。
於接著組合物的總質量中，較佳以未滿50質量 %，更佳以1~30質量%，再更佳以5~25質量%的比例含有上述填料(C)。而且，相對於丙烯酸樹脂(A)與熱硬化性樹脂(B)的合計100質量份，較佳以5質量份以上、未滿100質量份，更佳以8~60質量份，再更佳以10~40質量份的範圍含有上述填料(C)。上述填料的量過多的話，有可能對晶圓的貼附性或對基板的接著性變差。上述填料的量過少的話，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(C)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此等的本申請發明的效果高。
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板片作為切割．晶粒結著板片使用時，在貼附於晶圓後，藉由在切割步驟前照射紫外線，使於熱硬化性樹脂(B)以及填料(C)所具有的反應性雙鍵基反應，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，因此對於晶圓的貼附性佳，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佳狀況。而且，支撐體(樹脂膜或黏著板片)與接著劑的界面之界面剝離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，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。
於使用光聚合起始劑(D)的情形，其調配比例只 要是基於前述填料表面的反應性雙鍵基以及熱硬化性樹脂所具有的反應性雙鍵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)以及填料(C)合計100質量份，光聚合起始劑(D)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。此些可單獨使用1種或組合2種以上使用。
於使用硬化促進劑(E)的情形，相對於熱硬化性樹脂(B)的合計[(B1)+(B1')+(B2)+(B2')]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)耦合劑
耦合劑(F)具有與無機物反應的官能基以及與有機官能基反應的官能基，為了提升對接著劑層的對被著體之貼附性、接著性亦可以使用。而且，藉由使用耦合劑(F)能夠不損及接著劑層硬化所得之硬化物的耐熱性而提昇其耐水性。
作為耦合劑(F)，期望使用矽烷耦合劑。
作為此種的矽烷耦合劑，可舉出γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、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-(甲基丙烯酸氧基丙基)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、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等的具有2個或3個烷氧基的低分子矽烷耦合劑，四甲氧基矽烷、四乙氧基矽烷等的具有4個烷氧基的低分子矽烷耦合劑，雙(3-三乙氧基矽基丙基)四硫化氫、乙烯基三乙醯氧基矽烷、咪唑矽烷等。而且，亦可舉出藉由將具有2個或3個烷氧基的低分子矽烷耦合劑或具有4個烷氧基的低分子矽烷耦合劑的烷氧基水解或脫水縮合而得的生成物，而此生成物為寡聚物形式者。特別是，在上述的低分子矽烷耦合劑之中，藉由將作為具有2個或3個烷氧基的低分子矽烷耦合劑與具有4個烷氧基的低分子矽烷耦合劑脫水縮合而縮合的生成物之寡聚物，烷氧基的反應性富足、且具有有機官能基的充分的數量，因而較佳，例如是可舉出作為3-(2,3-乙氧基丙氧基)丙基甲氧基矽氧烷與二甲氧基矽氧烷的共聚物之寡聚物。
此些可單獨1種或混合2種以上使用。而且此些之中較佳是使用具有可與丙烯酸聚合物(A)、熱硬化性樹脂(B)等所具有的官能基反應之基的化合物。
於使用耦合劑(F)的情形，相對於丙烯酸樹脂(A) 與熱硬化性樹脂(B)的合計100質量份，耦合劑通常以0.1~20質量份，較佳為0.2~10質量份，更佳為0.3~5質量份的比例含有。耦合劑(F)的含量未滿0.1質量份則有可能無法得到上述的效果，超過20質量份則具有成為逸氣原因的可能性。
(G)交聯劑
為了調節接著劑層的初期接著力以及凝集力，亦可以於接著劑組合物中添加交聯劑(G)。而且，在調配交聯劑的情形，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(G)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。
於使用異氰酸酯系的交聯劑的情形，作為丙烯酸 聚合物(A)較佳是使用含有羥基的丙烯酸聚合物。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。
於使用交聯劑(G)的情形，相對於丙烯酸聚合物 (A)100質量份，交聯劑(G)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。
(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)包含反應性雙鍵基，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個具有聚合性的碳-碳雙鍵，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丙烯酸聚合物(A)以外的聚合物。作為此種的聚合物可使用熱可塑性樹脂(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)其他的無機填料
而且，除了前述填料(C)以外，在接著劑組合物中亦可以調配有無機填料(J)以作為不具有反應性雙鍵基的填料。作為無機填料，可舉出二氧化矽、滑石、碳酸鈣、鈦白、紅氧化鐵、碳化矽、氮化硼等的粉末。此些可舉出球形化的珠、單結晶纖維以及玻璃纖維等。
(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。
(接著板片)
由上述各成分所構成的接著劑組合物所形成的接著劑層，具有接著性(例如是熱接著性或感壓接著性)與加熱硬化性。在接著劑層具有感壓接著劑的情形，能夠於未硬化狀態按壓於被著體而貼附。在接著劑具有熱接著性的情形，在按壓於被著體時，能夠加熱接著劑層而貼附。本發明的熱接著性雖然在常溫不具感壓接著性，但藉由熱軟化而成為能夠接著於被著體。
而且，由於在接著劑層均勻分散有填料，即使半導體晶片接合且於高溫進行打線，接著劑層的變形亦少，而穩定的進行打線。然後經由熱硬化最終能夠提供耐衝擊性高的硬化物，剪切強度亦優異，於嚴苛的高溫度高溼度條件下亦能夠保持充分的接著特性。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。
雖然接著板片可為由上述接著劑組合物製膜而成 之單層的接著膜，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板片。特別是，第2發明的接著劑組合物所構成的單層接著膜，於250℃硬化後的剪切強度較佳為60N/5mm□以上，更佳為70N/5mm□~150N/5mm□的範圍，再更佳為80N/5mm□~120N/5mm□的範圍。而且，第2發明的接著劑組合物所構成之具有接著劑層的接著板片，於250℃硬化後的接著劑層之剪切強度較佳為60N/5mm□以上，更佳為70N/5mm□~150N/5mm□的範圍，再更佳為80N/5mm□~120N/5mm□的範圍。
以下，以接著劑層可剝離的形成於支撐體上而成 之接著板片為例，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板片時，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。本發明的接著板片的形狀，可為帶狀等的所有形狀。支撐體可為表面不具有黏著性的樹脂膜，亦可為在樹脂膜上具備黏著劑層的黏著板片。
作為用作為接著板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積層膜。而且，亦可以使用將此些著色的膜、不透明膜等。
本發明的接著板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，將塗佈有剝離劑的樹脂膜供給至常溫下或加熱下，或者是藉由電子線或紫外線硬化以形成剝離層即可。而且，亦藉由濕積層或乾積層、熱熔融積層、熔融擠壓積層、共擠壓加工等以進行膜的積層，藉此調整樹脂膜的表面張力。
於使用黏著板片作為支撐體的情形，此黏著板片亦可為作為切割板片使用的黏著板片。切割板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積層前述接著劑層。因此，切割板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，接著板片亦可以預先將支撐體以及接著劑 層模切為與被著體(半導體晶圓等)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。支撐體為黏著板片的情形，通常由黏著劑所構成的層占支撐體厚度中的1~50μm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。
接著板片的製造方法並沒有特別限定，在支撐體 為樹脂膜的情形，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黏著板片。
而且，在接著板片的使用前為了保護接著劑層， 亦可以於接著劑層的表面積層剝離膜。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，於接著板片的接著劑層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板片的利用方法，以該接 著板片適用於半導體裝置的製造的情形為例加以說明。
(半導體裝置之製造方法)
以下對本發明的半導體裝置之製造方法的範例進行詳述。
本發明的半導體裝置的第1製造方法，包括下述步驟：將上述接著板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。
於本發明的半導體裝置之第1製造方法中，首先，準備於表面形成電路、於背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(背面)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。在背面研磨時，為了保護表面的電路而於電路面貼附稱作為表面保護板片之黏著板片。背面研磨是將晶圓的電路面側(亦即是表面保護板片側)以夾頭座(chuck table)等固定，對未形成電路的背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背面側載置於本發明的接著板片的接著劑層上，輕輕按壓以將半導體晶圓固定。於接著劑層中調配有光聚合起始劑(D)的情形，從支撐體側對接著劑層照射能量線，使熱硬化性樹脂(B)以及填料(C)所具有的反應性雙鍵基反應、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)等，較佳使用紫外線。
其後，藉由使用切割機(dicing saw)的刀切割法或使用雷射光的雷射切割法等，將上述半導體晶圓切斷以得到半導體晶片。於使用切割機的情形之切斷深度，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板片的擴展，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背面而從支撐體剝離。
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，以將晶片暫時接著。晶片搭載部亦可以在載置半導體晶片前加熱，而且，亦可以於載置半導體晶片後加熱。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。
其後，較佳於晶片暫時接著的狀態依次積層晶片、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，於打線時由於接著劑層具有某程度的硬度，因而穩定的進行打線。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性變高。
於本發明的半導體裝置的第2製造方法中，首先，在半導體晶圓的表面形成符合單片化半導體晶片之形狀的外部輪廓的溝；於半導體晶圓的表面貼附保護板片；接著由背面側進行到達溝為止的薄化處理，以將半導體晶圓單片化為半導體晶片，以準備藉由所謂先切割法所得的複數的晶片群。
其次，與第1製造方法相同，將環狀框架以及晶片群的背面側載置於本發明的接著劑層上，輕輕按壓並固定晶片群。其後，僅將接著劑層切割為晶片尺寸。但並不限定為僅切割接著劑層的方法，例如是可以採用雷射切割法。
其後，因應需要進行接著板片的擴展步驟，或使接著劑層固著殘存於半導體晶片而從支撐體剝離，並經由接著劑層將半導體晶片接著於晶粒墊部上或其他半導體晶片上的步驟，如同第1製造方法中的說明以進行。
本發明的接著劑組合物以及接著板片，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，〈丙烯酸聚合物的重量平均分子量以及分子量分布的測定〉、〈填料的平均粒徑〉、〈剪切強度測定〉以及〈封裝可靠性評估〉如下述進行。而且，剪切強度的測定，是以第2發明的實施例(實施例3、4以及比較例3、4)進行。
〈丙烯酸聚合物的重量平均分子量以及分子量分布的測定〉
丙烯酸聚合物(A)的重量平均分子量(Mw)以及分子量分布(Mw/Mn，Mn為數量平均分子量)，以標準聚苯乙烯換算值，以下述的裝置以及條件測定。
．裝置名：HLC-8220GPC，東曹(股)製
．管柱：以TSKgelGMHXL、TSKgelGMHXL以及TSKgel2000HXL此順序連結者
．溶媒：四氫呋喃
．測定溫度：40℃
．流速：1ml/分
．檢測器：示差折射計
〈填料的平均粒徑〉
填料的平均粒徑，藉由使用動態光散射法的粒度分布計(日機裝公司製，裝置名：Nanotrac150)測定
〈剪切強度測定〉
(評估試樣製作)
於#2000研磨矽晶圓(150mm直徑，厚度350μm)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板片之貼附，固定於晶圓切割用環狀框架。其次，使用切割裝置(股份有限公司Disco製，DFD651)切割為5mm×5mm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。
作為暫時接著上述晶片的下段晶片，準備CMP處理完畢的晶片(尺寸：10mm×10mm，厚度：350μm)。於此下段晶片上，經由接著劑層而以150℃，100gf，1秒鐘的條件而壓接上述所得的晶片，暫時固定半導體封裝的模封並以175℃、5小時進行接著劑層的熱硬化，以製作評估試樣。
(評價)
將評估試樣置於預設為回流時溫度之250℃的熱板上，於濕度50%RH的環境條件下，使用接合測試機(dage公司製，dage4000)以測定剪切強度。前述接合測試機的設定條件，頭高為50μm、速度為0.2mm/秒。
〈封裝可靠性評估〉
(半導體晶片的製造)
於乾研磨經加工的矽晶圓(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板片之貼附，固定於晶圓切割用環狀框架。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)
使用於覆銅箔積層板(三菱氣體化學股份有限公司製CCL-HL830，銅箔厚度18μm)的銅箔形成電路圖案，且於圖案上具有抗鍍劑(太陽墨水製PSR-4000AUS303)之基板(股份有限公司Chino技研製LN001E-001 PCB(Au)AUS303)作為基板。將上述所得的接著板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，假設打線時的熱並於175℃的氣體環境下施加2小時的熱，使用密封裝置(Apic Yamada股份有限公司製MPC-06M TriAl Press)而以密封厚度成為400μm的方式，以模封樹脂(京瓷化學股份有限公司製KE-1100AS3)進行密封。其次，以175℃進行6.9MPa的加熱加壓2分鐘，其後，以175℃、進行5小時的加熱使樹脂硬化。
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85℃、濕度60%RH條件下放置168小時、吸濕後，以預熱130℃(嚴苛條件)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。其後，對於接合部的浮起．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-1000)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以上的剝離的情形則判斷為剝離，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-1)丙烯酸聚合物：丙烯酸甲酯95質量份以及丙烯酸2-羥基乙酯5質量份所構成的共聚物(Mw：50萬，Mw/Mn：2.9、Tg：9℃，TOYO CHEM公司製)
(A-2)丙烯酸聚合物：丙烯酸甲酯95質量份以及丙烯酸2-羥基乙酯5質量份所構成的共聚物(Mw：46萬，Mw/Mn：3.2、Tg：9℃，日本合成化學公司製)
(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)填料：
(C-1)甲基丙烯酸氧基修飾的二氧化矽填料(平均粒徑0.05μm，Admatechs公司製3-甲基丙烯酸氧基丙基三甲氧基矽烷處理品)
(C-2)甲基丙烯酸氧基修飾的二氧化矽填料(平均粒徑0.5μm、SO-C2，Admatechs公司製3-甲基丙烯酸氧基丙基三甲氧基矽烷處理品)
(C-3)乙烯基修飾的二氧化矽填料(平均粒徑0.05μm，Admatechs公司製乙烯基三甲氧基矽烷處理品)
(C-4)三甲基修飾的二氧化矽填料(平均粒徑0.07μm、NSS-5N，三甲基矽基處理品，TOKUYAMA公司製)
(F)矽烷耦合劑(三菱化學股份有限公司製MKCSilicateMSEP2)
(G)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)
(J)未處理的二氧化矽填料(平均粒徑0.4μm、Sunsinol SS-04，TOKUYAMA公司製)
(實施例以及比較例)
(接著劑層)
上述各成分以表1以及表2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20質量%)，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板片。使用所得的接著板片製作半導體封裝，評估其可靠性。而且，以表2所記載的量調配所得的接 著劑組合物，如同上述的得到接著板片，除了評價可靠性之外，測定硬化後的接著劑層的剪切強度。結果如表1及表2所示。表1及表2中PKG可靠性表示封裝可靠性，於上述評估中，以「未發生剝離個數/27(投入試驗的封裝個數)」而表示。
第1發明的實施型態之實施例1以及實施例2的 接著劑組合物的任一，相較於作為第1發明的比較型態之比較例1或比較例2的接著劑組合物，半導體裝置的可靠性能夠提 升。其中比較例1未含有於表面具有反應性雙鍵基的填料(C)，比較例2使用重量平均分子量低於50萬的丙烯酸聚合物。
如依本發明的第1發明，藉由使用具有規定的重量平均分子量的丙烯酸聚合物(A)、具有反應性雙鍵基的熱硬化性樹脂(B)以及於表面具有反應性雙鍵基的填料(C)，於接著劑層中填料(C)能夠均勻的混合，而且能夠於接著劑層中導入三維網狀結構。因此，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，即使於嚴苛的環境下，能夠得到顯示高封裝可靠性的半導體裝置。而且，由於能夠賦予未硬化或半硬化狀態的接著劑層某程度的硬度，於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，即使經由長時間的打線，亦能夠穩定的進行打線。
第2發明之實施型態的實施例3以及實施例4的 接著劑組合物所構成的接著劑層的剪切強度，任一皆為60N/5mm□以上。實施例3以及實施例4的接著劑組合物的任一，相較於作為第2發明的比較型態之比較例3或比較例4的接著劑組合物，半導體裝置的可靠性能夠提升。其中比較例3未含有平均粒徑為0.01~0.2μm的填料(C)，比較例4未含有於表面具有反應性雙鍵基的填料(C)。
如依本發明的第2發明，藉由使用丙烯酸聚合物(A)、具有反應性雙鍵基的熱硬化性樹脂(B)以及於表面具有反應性雙鍵基且具有規定的平均粒徑之填料(C)，於接著劑層中填料(C)能夠均勻的混合，而且能夠於接著劑層中 導入三維網狀結構。因此，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，即使於嚴苛的環境下，能夠得到顯示高封裝可靠性的半導體裝置。而且，由於能夠賦予未硬化或半硬化狀態的接著劑層某程度的硬度，於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，即使經由長時間的打線，亦能夠穩定的進行打線。

Claims (15)

  1. 一種接著劑組合物，包含丙烯酸聚合物(A)、具有反應性雙鍵基的熱硬化性樹脂(B)以及於表面具有反應性雙鍵基的填料(C)，該丙烯酸聚合物(A)的重量平均分子量為50萬~150萬，該熱硬化性樹脂(B)由環氧樹脂以及熱硬化劑所構成，該環氧樹脂以及該熱硬化劑的其中之一或者兩者具有反應性雙鍵基。
  2. 一種接著劑組合物，包含丙烯酸聚合物(A)、具有反應性雙鍵基的熱硬化性樹脂(B)以及於表面具有反應性雙鍵基的填料(C)，該填料(C)的平均粒徑為0.01~0.2μm的範圍，該熱硬化性樹脂(B)由環氧樹脂以及熱硬化劑所構成，該環氧樹脂以及該熱硬化劑的其中之一或者兩者具有反應性雙鍵基。
  3. 如申請專利範圍第1或2項所述的接著劑組合物，其中前述填料(C)為表面具有反應性雙鍵基的二氧化矽。
  4. 如申請專利範圍第1或2項所述的接著劑組合物，其中於接著劑組合物的總質量中，前述丙烯酸聚合物(A)的含有比例為50~90質量%。
  5. 如申請專利範圍第1或2項所述的接著劑組合物，其中前述丙烯酸聚合物(A)具有羥基。
  6. 一種單層接著膜，由如申請專利範圍第1至5項中任一項所述的接著劑組合物所構成。
  7. 一種單層接著膜，由如申請專利範圍第2項所述的接著劑組合物所構成，於250℃硬化後的剪切強度為60N/5mm□以上。
  8. 一種接著板片，將如申請專利範圍第1至5項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。
  9. 一種接著板片，將如申請專利範圍第2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，於250℃硬化後的接著劑層的剪切強度為60N/5mm□以上。
  10. 如申請專利範圍第8或9項所述的接著板片，其中前述支撐體為樹脂膜。
  11. 如申請專利範圍第8或9項所述的接著板片，其中前述支撐體為黏著板片。
  12. 一種半導體裝置之製造方法，包括下述步驟：將如申請專利範圍第8至11項中任一項所述的接著板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。
  13. 一種半導體裝置之製造方法，包括下述步驟：在半導體晶圓的表面形成符合單片化半導體晶片之形狀的外部輪廓的溝；於半導體晶圓的表面貼附保護板片；接著由背面側進行到達溝為止的薄化處理，以將半導體晶圓單片化為半導體晶片；以及 將如申請專利範圍第8至11項中任一項所述的接著板片的接著劑層貼附於前述半導體晶片；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。
  14. 如申請專利範圍第1項所述的接著劑組合物，其中前述丙烯酸聚合物(A)的重量平均分子量為50萬~80萬。
  15. 如申請專利範圍第1或2項所述的接著劑組合物，其係使用於將半導體晶片接著於有機基板、導線架、或其他半導體晶片。
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