TW201806041A - Die bonding film, die bonding film for dicing, and manufacturing method of semiconductor devices capable of suppressing warpage of very slim dies for performing multi-layered lamination - Google Patents

Die bonding film, die bonding film for dicing, and manufacturing method of semiconductor devices capable of suppressing warpage of very slim dies for performing multi-layered lamination Download PDF

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TW201806041A
TW201806041A TW106117528A TW106117528A TW201806041A TW 201806041 A TW201806041 A TW 201806041A TW 106117528 A TW106117528 A TW 106117528A TW 106117528 A TW106117528 A TW 106117528A TW 201806041 A TW201806041 A TW 201806041A
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Taiwan
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film
sticky
crystal film
wafer
viscous
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TW106117528A
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Chinese (zh)
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TWI735584B (en
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福井章洋
大西謙司
宍戶雄一郎
木村雄大
高本尚英
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日東電工股份有限公司
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    • 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
    • H01L21/67—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
    • 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
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • 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
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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—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
    • H01L21/677—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 conveying, e.g. between different workstations
    • H01L21/67703—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 conveying, e.g. between different workstations between different workstations
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    • H—ELECTRICITY
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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
    • H01L21/67—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
    • H01L21/677—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 conveying, e.g. between different workstations
    • H01L21/67703—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 conveying, e.g. between different workstations between different workstations
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    • H—ELECTRICITY
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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
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/43—Manufacturing methods
    • 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
    • H01L24/93—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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured 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
    • 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
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
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    • 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
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
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    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
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    • H01L2224/01—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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
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    • H01L2224/32135—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
    • H01L2224/32145—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
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    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
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    • H01L2224/73265—Layer and wire connectors

Abstract

The present invention provides a die bonding film capable of excellently performing wire bonding on a die bonding film without thermal curing. The die bonding film of the present invention contains filling materials with average particle diameters in a range of 5 nm to 100 nm, a thermoplastic resin, and a phenol resin, and has a tensile storage elastic modulus at 150 deg C before thermal curing, such that the die warpage may be suppressed after die bonding.

Description

黏晶膜、切晶黏晶膜及半導體裝置之製造方法Sticky crystal film, cut crystal sticky film and method for manufacturing semiconductor device

本發明係關於一種黏晶膜、切晶黏晶膜及半導體裝置之製造方法。The invention relates to a method for manufacturing a sticky crystal film, a cut crystal sticky film, and a semiconductor device.

先前，黏晶膜被用於製造半導體裝置。 於使用有黏晶膜之半導體裝置之製造步驟中，有將晶片積層(堆疊)為多層之方法。於此種情形時，存在晶片薄型化之強烈要求(例如參照專利文獻1)。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2008-218571號公報Previously, a die-bond film was used to manufacture semiconductor devices. In the manufacturing steps of a semiconductor device using a sticky crystal film, there is a method of laminating (stacking) a wafer into multiple layers. In such a case, there is a strong demand for thinning a wafer (for example, refer to Patent Document 1). [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2008-218571

[發明所欲解決之問題] 然而，若將形成有聚醯亞胺等鈍化膜之晶圓研削得較薄，則晶圓會大幅翹曲，切割後之晶片會翹曲。若將該翹曲之晶片接合至基板或引線框架等進行堆疊，則存在其翹曲殘留，晶片之端部隆起之問題。 本發明係鑒於上述問題而成者，其目的在於提供一種能抑制翹曲較大之極薄晶片之翹曲，良好地進行多層積層之黏晶膜。 又，本發明之目的在於提供一種具備該黏晶膜之切晶黏晶膜。 又，本發明之目的在於提供一種使用該切晶黏晶膜之半導體裝置之製造方法。 [解決問題之技術手段] 本案發明人等發現，藉由採用下述構成，能夠解決上述問題，從而完成了本發明。 即，本發明之黏晶膜之特徵在於含有： 平均粒徑為5 nm～100 nm之範圍內之填料、 熱塑性樹脂、及 酚樹脂，且 熱硬化前之於150℃下之拉伸儲存彈性模數大於0.3 MPa且為30 MPa以下。 根據上述構成，由於熱硬化前之於150℃下之拉伸儲存彈性模數為0.3 MPa以上，因此即使晶片發生翹曲，亦能夠於黏晶後將該翹曲抑制住。 又，由於熱硬化前之於150℃下之拉伸儲存彈性模數為30 MPa以下，因此向被黏著體之嵌入性變良好，能夠抑制被黏著體與黏晶膜之間之空隙(void)。 又，由於使用平均粒徑為5 nm～100 nm之範圍內之填料作為填料，因此能夠使黏晶膜薄型化。又，由於含有酚樹脂，因此可靠性優異。又，由於含有熱塑性樹脂，因此能夠維持作為膜之形狀。 於上述構成中，較佳為將熱硬化前之玻璃轉移溫度設為T0 、將熱硬化後之玻璃轉移溫度設為T1 時，滿足下述式1。 式1 T0 ＜T1 ＜T0 ＋20 若滿足上述式1，則熱硬化前之玻璃轉移溫度與熱硬化後之玻璃轉移溫度之差較小，可謂於熱硬化前後物性之變化較小。因此，於施加熱歷程後向被黏著體之嵌入性亦良好。 於上述構成中，上述填料較佳為二氧化矽填料。 若上述填料為二氧化矽填料，則較其他無機填料成本低，亦容易獲得。 於上述構成中，上述熱塑性樹脂較佳為具有環氧基之丙烯酸系聚合物。 若上述熱塑性樹脂為具有環氧基之丙烯酸系聚合物，則於被黏著體為有機基板之情形時，藉由與存在於有機基板之未反應之環氧樹脂或酚樹脂進行反應，而實現可靠性之提高。又，亦能與密封樹脂反應，而實現可靠性之提高。 於上述構成中，較佳為包含著色劑。 由於上述構成之黏晶膜使用平均粒徑為5 nm～100 nm之範圍內之填料，因此有黏晶膜具有透明性，而視認性降低之可能性。然而，若包含著色劑，則能夠提高黏晶膜之視認性，而能夠提高作業性。 於上述構成中，上述著色劑較佳為染料。 若上述著色劑為染料，則容易溶於構成黏晶膜之樹脂，能夠均勻地著色。又，於製作黏晶膜時使用溶劑之情形時，容易溶於溶劑，能夠均勻地著色。 於上述構成中，較佳為將上述填料之平均粒徑設為R、將上述黏晶膜之厚度設為T時，滿足下述式2。 式2 10＜T/R 若滿足上述式2，則能夠抑制填料從黏晶膜突起。其結果，能夠防止將黏晶膜貼合於晶圓時晶圓破裂。 又，本發明之切晶黏晶膜之特徵在於具備： 切割片材、及 上述黏晶膜。 上述切晶黏晶膜具備上述黏晶膜。由於上述黏晶膜熱硬化前之於150℃下之拉伸儲存彈性模數為0.3 MPa以上，因此即使晶片發生翹曲，亦能夠於黏晶後將該翹曲抑制住。又，由於熱硬化前之於150℃下之拉伸儲存彈性模數為30 MPa以下，因此向被黏著體之嵌入性變良好，能夠抑制被黏著體與黏晶膜之間之空隙。 又，本發明之半導體裝置之製造方法之特徵在於包括以下步驟： 步驟A，將半導體晶圓貼附於切晶黏晶膜； 步驟B，使上述切晶黏晶膜擴張，至少使上述黏晶膜斷裂，獲得附黏晶膜之晶片； 步驟C，拾取上述附黏晶膜之晶片； 步驟D，將所拾取之上述附黏晶膜之晶片經由黏晶膜黏晶至被黏著體；以及 步驟E，對上述附黏晶膜之晶片進行打線接合；且 上述切晶黏晶膜含有： 平均粒徑為5 nm～100 nm之範圍內之填料、 熱塑性樹脂、及 酚樹脂， 熱硬化前之於150℃下之拉伸儲存彈性模數大於0.3 MPa且為30 MPa以下。 上述切晶黏晶膜具備上述黏晶膜。由於上述黏晶膜熱硬化前之於150℃下之拉伸儲存彈性模數為0.3 MPa以上，因此即使晶片發生翹曲，亦能夠於黏晶後將該翹曲抑制住。又，由於熱硬化前之於150℃下之拉伸儲存彈性模數為30 MPa以下，因此向被黏著體之嵌入性變良好，能夠抑制被黏著體與黏晶膜之間之空隙。[Problems to be Solved by the Invention] However, if a wafer formed with a passivation film such as polyimide is thinned, the wafer will be warped greatly, and the wafer after cutting will be warped. If the warped wafer is bonded to a substrate, a lead frame, or the like and stacked, there is a problem that warpage remains and the end portion of the wafer is raised. The present invention has been made in view of the above problems, and an object thereof is to provide a die-bonding film capable of suppressing warpage of an extremely thin wafer with large warpage and performing multilayer lamination. Moreover, an object of the present invention is to provide a cut crystal sticky film provided with the sticky film. It is another object of the present invention to provide a method for manufacturing a semiconductor device using the cut-die-bond film. [Technical means for solving the problem] The inventors of the present case have found that the above-mentioned problems can be solved by adopting the following configuration, and the present invention has been completed. That is, the viscous crystal film of the present invention is characterized by containing a filler, a thermoplastic resin, and a phenol resin having an average particle diameter in a range of 5 nm to 100 nm, and a tensile storage elastic mold at 150 ° C before heat curing. The number is more than 0.3 MPa and 30 MPa or less. According to the above configuration, since the tensile storage elastic modulus at 150 ° C. before the thermosetting is 0.3 MPa or more, even if the wafer is warped, the warpage can be suppressed after sticking. In addition, since the tensile storage elastic modulus at 150 ° C before the thermosetting is 30 MPa or less, the embedding property to the adherend is improved, and the void between the adherend and the viscous film can be suppressed (void). . In addition, since a filler having an average particle diameter in the range of 5 nm to 100 nm is used as the filler, the slime film can be made thin. Moreover, since it contains a phenol resin, it is excellent in reliability. Moreover, since it contains a thermoplastic resin, it can maintain the shape as a film. In the above configuration, when the glass transition temperature before thermal curing is set to T 0 and the glass transition temperature after thermal curing is set to T 1 , the following formula 1 is satisfied. Formula 1 T 0 <T 1 <T 0 +20 If the above formula 1 is satisfied, the difference between the glass transition temperature before thermal curing and the glass transition temperature after thermal curing is small, and it can be said that the change in physical properties before and after thermal curing is small. Therefore, the embedding property to the adherend after applying the thermal history is also good. In the above configuration, the filler is preferably a silica filler. If the filler is a silicon dioxide filler, the cost is lower than other inorganic fillers, and it is also easy to obtain. In the said structure, it is preferable that the said thermoplastic resin is an acrylic polymer which has an epoxy group. If the thermoplastic resin is an acrylic polymer having an epoxy group, when the adherend is an organic substrate, it can be reliably achieved by reacting with an unreacted epoxy resin or a phenol resin existing on the organic substrate. Sexual improvement. In addition, it can also react with the sealing resin to improve reliability. In the said structure, it is preferable to contain a coloring agent. Since the sticky crystal film having the above-mentioned structure uses a filler having an average particle diameter in a range of 5 nm to 100 nm, there is a possibility that the sticky crystal film has transparency and visibility may be reduced. However, if a coloring agent is included, visibility of a viscous crystal film can be improved, and workability can be improved. In the above configuration, the colorant is preferably a dye. When the colorant is a dye, it is easily soluble in the resin constituting the viscous crystal film, and can be uniformly colored. Moreover, when a solvent is used in the production of a sticky-crystal film, it is easy to dissolve in a solvent and can uniformly color. In the above configuration, when the average particle diameter of the filler is set to R and the thickness of the sticky crystal film is set to T, the following formula 2 is satisfied. Formula 2 10 <T / R When the above formula 2 is satisfied, it is possible to suppress the filler from protruding from the viscous crystal film. As a result, it is possible to prevent the wafer from cracking when the adhesive film is bonded to the wafer. In addition, the cut crystal adhesive film of the present invention includes a dicing sheet and the above-mentioned adhesive film. The cut crystal and sticky film includes the sticky film. Since the tensile storage elastic modulus at 150 ° C. of the above-mentioned viscous crystal film is 0.3 MPa or more before thermal curing, even if the wafer is warped, the warpage can be suppressed after the viscous crystal. In addition, since the tensile storage elastic modulus at 150 ° C before thermal curing is 30 MPa or less, the embedding property into the adherend is improved, and the gap between the adherend and the viscous film can be suppressed. In addition, the method for manufacturing a semiconductor device according to the present invention is characterized by including the following steps: Step A, attaching a semiconductor wafer to a cut crystal sticky film; and step B, expanding the cut crystal sticky film to at least the sticky crystal The film is broken to obtain a wafer with a sticky crystal film; step C, picking up the wafer with a sticky crystal film; step D, sticking the picked up wafer with the sticky crystal film to the adherend through the sticky film; and step E, wire bonding the wafer with a sticky crystal film; and the above-mentioned cut crystal sticky film contains: a filler having an average particle diameter in a range of 5 nm to 100 nm, a thermoplastic resin, and a phenol resin, and is applied before the heat curing. The tensile storage elastic modulus at 150 ° C is greater than 0.3 MPa and less than 30 MPa. The cut crystal and sticky film includes the sticky film. Since the tensile storage elastic modulus at 150 ° C. of the above-mentioned viscous crystal film is 0.3 MPa or more before thermal curing, even if the wafer is warped, the warpage can be suppressed after the viscous crystal. In addition, since the tensile storage elastic modulus at 150 ° C before thermal curing is 30 MPa or less, the embedding property into the adherend is improved, and the gap between the adherend and the viscous film can be suppressed.

以下對本實施形態之黏晶膜及切晶黏晶膜進行說明。對於本實施形態之黏晶膜，可列舉於以下說明之切晶黏晶膜中未貼合有切割片材之狀態者。因此，以下對切晶黏晶膜進行說明，關於黏晶膜，會於其中進行說明。 (切晶黏晶膜) 對本發明之一實施形態之切晶黏晶膜進行以下說明。圖1係表示本發明之一實施形態之切晶黏晶膜之剖視模式圖。 如圖1所示，切晶黏晶膜10具有於切割片材11上積層有黏晶膜3之構成。切割片材11具有於基材1上積層有黏著劑層2之構成。黏晶膜3設置於黏著劑層2上。 再者，於本實施形態中，會對切割片材11中存在未被黏晶膜3覆蓋之部分2b之情形進行說明，但本發明之切晶黏晶膜不限定於該例，亦可將黏晶膜以覆蓋整個切割片材之方式積層於切割片材。 (黏晶膜) 黏晶膜3熱硬化前之於150℃下之拉伸儲存彈性模數大於0.3 MPa且為30 MPa以下，較佳為0.4 MPa～25 MPa之範圍內，更佳為0.5 MPa～20 MPa之範圍內。 由於熱硬化前之於150℃下之拉伸儲存彈性模數為0.3 MPa以上，因此即使晶片發生翹曲，亦能夠於黏晶後將該翹曲抑制住。又，由於熱硬化前之於150℃下之拉伸儲存彈性模數為30 MPa以下，因此向被黏著體之嵌入性變良好，能夠抑制被黏著體與黏晶膜之間之空隙。 如此，根據黏晶膜3，能兼顧積極之翹曲抑制及空隙嵌入性。 又，黏晶膜3熱硬化前之於175℃下之拉伸儲存彈性模數較佳為0.2 MPa～30 MPa之範圍內，更佳為0.3 MPa～25 MPa之範圍內。密封步驟之溫度通常為175℃左右。因此，若熱硬化前之於175℃下之拉伸儲存彈性模數為30 MPa以下，則於密封壓力下之嵌入性變良好，能夠抑制空隙。 黏晶膜3熱硬化前之於150℃及175℃下之拉伸儲存彈性模數例如可藉由使用下述中說明之填料，或調整熱塑性樹脂之分子量而設為上述數值範圍內。 上述拉伸儲存彈性模數之更詳細之測定方法係基於實施例中記載之方法。 黏晶膜3較佳為將熱硬化前之玻璃轉移溫度(Tg)設為T0 、將熱硬化後之玻璃轉移溫度(Tg)設為T1 時，滿足下述式1。 式1 T0 ＜T1 ＜T0 ＋20 若滿足上述式1，則熱硬化前之玻璃轉移溫度與熱硬化後之玻璃轉移溫度之差較小，可謂於熱硬化前後物性之變化較小。因此，於施加熱歷程後向被黏著體之嵌入性亦良好。上述T1 更佳為小於(T0 ＋15)，進而較佳為小於(T0 ＋10)。 為了使黏晶膜3滿足上述式1，例如只要以使硬化物之交聯變少之方式進行調整即可。 於本說明書中，「熱硬化後」係指於175℃下加熱1小時後。 黏晶膜3熱硬化前之玻璃轉移溫度T0 較佳為0～70℃之範圍內，更佳為15～50℃之範圍內。若上述玻璃轉移溫度T0 為0℃以上，則能夠抑制黏晶膜3之黏性。又，若為70℃以下，則能夠容易地貼附於被黏著體。 黏晶膜3熱硬化後之玻璃轉移溫度T1 較佳為0～90℃之範圍內，更佳為15～70℃之範圍內。若上述玻璃轉移溫度T1 位於上述數值內，則能夠容易地滿足上述式1。其結果，熱硬化後向被黏著體之嵌入性亦良好。 上述玻璃轉移溫度T0 、玻璃轉移溫度T1 可藉由選擇構成黏晶膜3之樹脂成分而設為期望之範圍內。 上述玻璃轉移溫度(Tg)之更詳細之測定方法係基於實施例中記載之方法。 黏晶膜3於熱硬化前之狀態下之於-15℃下之斷裂伸長率較佳為20%以下，更佳為15%以下，進而較佳為10%以下。於半導體裝置之製造步驟中，有時使用隱形切割(Stealth Dicing)(註冊商標)或DBG步驟。若上述斷裂伸長率為20%以下，則隱形切割或DBG步驟後之冷擴張性良好。再者，關於隱形切割及DBG步驟，將於後面進行說明。 上述斷裂伸長率可藉由構成黏晶膜3之材料而控制。例如，可藉由適宜選擇構成黏晶膜3之熱塑性樹脂之種類或含量、填料之含量等而控制。 上述斷裂伸長率之測定方法係基於實施例中記載之方法。 如圖1所示，黏晶膜3之層構成可列舉包含單層之接著劑層者。再者，於本說明書中，單層係指由同一組成所構成之層，包括將由同一組成所構成之層積層複數層而成者。 但是，本發明中之黏晶膜不限定於該例。例如，可為將不同組成之2種以上之接著劑層積層而成之多層結構。 黏晶膜3含有平均粒徑為5 nm～100 nm之範圍內之填料、熱塑性樹脂及酚樹脂。 上述填料之平均粒徑為5 nm～100 nm之範圍內，較佳為7 nm～80 nm之範圍內，更佳為10 nm～50 nm之範圍內。由於使用平均粒徑為5 nm～100 nm之範圍內之填料，因此能夠使黏晶膜3薄型化。又，由於使用平均粒徑為5 nm～100 nm之範圍內之填料，因此能夠使黏晶膜3之拉伸儲存彈性模數提高。 上述填料之平均粒徑之測定方法係基於實施例中記載之方法。 上述填料之最大粒徑通常需要未達黏晶膜3之厚度。其原因在於，填料會從黏晶膜突起，將黏晶膜貼合於晶圓時，晶圓會破裂。由於黏晶膜3中所含有之上述填料之平均粒徑為5 nm～100 nm之範圍內，因此粗大填料(直徑較黏晶膜3之厚度大之填料)存在之概率顯著低。因此，例如能使黏晶膜3之厚度為5 μm以下等。 作為上述填料，可列舉無機填料及有機填料，就低線膨脹係數之觀點而言，較佳為無機填料。作為上述無機填料，並無特別限制，例如可列舉：氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、硼酸鋁晶鬚、氮化硼、晶質二氧化矽、非晶質二氧化矽等。該等可單獨使用或併用2種以上。其中，就獲得之容易性或成本之觀點而言，較佳為晶質二氧化矽、非晶質二氧化矽。 將上述填料之平均粒徑設為R、將黏晶膜3之厚度設為T時，較佳為滿足下述式2。 式2 10＜T/R 若滿足上述式2，則能夠抑制填料從黏晶膜3突起。其結果，能夠防止於將黏晶膜3貼合於晶圓時晶圓破裂。上述T/R更佳為15以上，進而較佳為20以上。 黏晶膜3之厚度(T)較佳為1～30 μm，更佳為3～20 μm。若為30 μm以下，則於冷擴張步驟中容易割斷黏晶膜。 上述填料之調配比率相對於黏晶膜3整體，較佳為10～70重量%，更佳為20～60重量%。 若上述填料之調配比率為10～70重量%之範圍內，則彈性模數會提高或割斷性會提高。 作為上述熱塑性樹脂，可列舉：天然橡膠、丁基橡膠、異戊二烯橡膠、氯丁二烯橡膠、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、熱塑性聚醯亞胺樹脂、6-尼龍或6,6-尼龍等聚醯胺樹脂、苯氧基樹脂、丙烯酸系樹脂、PET(polyethylene terephthalate，聚對苯二甲酸乙二酯)或PBT(polybutylene terephthalate，聚對苯二甲酸丁二酯)等飽和聚酯樹脂、聚醯胺醯亞胺樹脂、或氟樹脂等。該等熱塑性樹脂可單獨使用或併用2種以上。該等熱塑性樹脂之中，尤佳為離子性雜質較少、耐熱性較高，能夠確保半導體元件之可靠性之丙烯酸系樹脂。黏晶膜3由於包含熱塑性樹脂，因此能夠維持作為膜之形狀。 作為上述丙烯酸系樹脂，並無特別限定，可列舉將具有碳數30以下、特別是碳數4～18之直鏈或支鏈之烷基的丙烯酸或甲基丙烯酸之酯之1種或2種以上作為成分的聚合物(丙烯酸系共聚物)等。作為上述烷基，例如可列舉：甲基、乙基、丙基、異丙基、正丁基、第三丁基、異丁基、戊基、異戊基、己基、庚基、環己基、2-乙基己基、辛基、異辛基、壬基、異壬基、癸基、異癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基、或十二烷基等。 又，作為形成上述聚合物之其他單體，並無特別限定，例如可列舉：丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸或丁烯酸等之類之含羧基單體；順丁烯二酸酐或伊康酸酐等之類之酸酐單體；(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4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯或丙烯酸(4-羥基甲基環己基)甲酯等之類之含羥基單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯或(甲基)丙烯醯氧基萘磺酸等之類之含磺酸基單體；或2-羥基乙基丙烯醯基磷酸酯等之類之含磷酸基單體。 其中，上述熱塑性樹脂較佳為具有環氧基作為官能基之丙烯酸系聚合物。若上述熱塑性樹脂為具有環氧基之丙烯酸系聚合物，則於被黏著體為有機基板之情形時，藉由與存在於有機基板之未反應之環氧樹脂或酚樹脂進行反應，而實現可靠性之提高。又，亦能與密封樹脂反應，而實現可靠性之提高。 作為上述熱塑性樹脂之調配比率，就提高硬化前之於高溫下之彈性模數之觀點而言，相對於黏晶膜3整體，較佳為10～90重量%之範圍內，更佳為15～60重量%之範圍內。 上述熱塑性樹脂之重量平均分子量較佳為500,000～1700,000，更佳為600,000～1500,000。若黏晶膜3中之熱塑性樹脂之分子量為500,000以上，則聚合物鏈彼此之凝聚力增加。其結果，變得不易伸長，冷擴張時之割斷性提高。另一方面，若分子量為1700,000以下，則聚合物之合成容易。 於本說明書中，重量平均分子量係指藉由以下之方法測定之值。 ＜重量平均分子量Mw之測定＞ 重量平均分子量Mw之測定係藉由GPC(凝膠滲透層析法)而進行。測定條件如下所述。再者，重量平均分子量係藉由聚苯乙烯換算而算出。 測定裝置：HLC-8120GPC(製品名，TOSOH公司製) 管柱：TSKgel GMH-H(S)×2(產品型號，TOSOH公司製) 流量：0.5 ml/ min 注入量：100 μl 管柱溫度：40℃ 溶離液：THF 注入試樣濃度：0.1重量% 檢測器：示差折射計 上述酚樹脂例如可列舉：苯酚酚醛清漆樹脂、苯酚芳烷基樹脂、甲酚酚醛清漆樹脂、第三丁基苯酚酚醛清漆樹脂、壬基苯酚酚醛清漆樹脂等酚醛清漆型酚樹脂；可溶酚醛型酚樹脂、聚對羥基苯乙烯等聚羥基苯乙烯等。該等可單獨使用或併用2種以上。該等酚樹脂之中，尤佳為苯酚酚醛清漆樹脂、苯酚芳烷基樹脂。其原因在於，能夠提高半導體裝置之連接可靠性。由於包含酚樹脂，因此可靠性優異。 作為上述酚樹脂之調配比率，就可靠性之觀點而言，相對於黏晶膜3整體，較佳為1～35重量%之範圍內，更佳為3～20重量%之範圍內。若位於上述數值範圍內，則與其他成分之反應會充分進行，因此能夠提高可靠性。 黏晶膜3較佳為包含著色劑。由於黏晶膜3使用平均粒徑為5 nm～100 nm之範圍內之填料，因此有黏晶膜3具有透明性，而視認性降低之可能性。因此，若包含著色劑，則能夠提高黏晶膜3之視認性，而能夠提高作業性。 作為上述著色劑，可列舉顏料、染料等。上述著色劑可單獨使用或組合2種以上使用。再者，作為染料，可使用酸性染料、反應染料、直接染料、分散染料、陽離子染料等任意形態之染料。又，對顏料之形態亦無特別限制，可從公知之顏料中適當選擇使用。其中，較佳為染料。若使用染料，則容易溶於構成黏晶膜3之樹脂，能夠均勻地著色。又，於製作黏晶膜3時使用溶劑之情形時，容易溶於溶劑，能夠均勻地著色。就無需進行分散之觀點而言，較佳為溶解性優異之染料。 於使本發明之黏晶膜3預先交聯一定程度之情形時，可於製作時，預先添加會與聚合物之分子鏈末端之官能基等反應之多官能性化合物作為交聯劑。藉此，能夠提高於高溫下之接著特性，實現耐熱性之改善。 作為上述交聯劑，可採用先前公知者。特別是甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、對苯二異氰酸酯、1,5-萘二異氰酸酯、多元醇與二異氰酸酯之加成物等多異氰酸酯化合物更佳。作為交聯劑之添加量，較佳為相對於上述聚合物100重量份，通常設為0.05～7重量份。若交聯劑之量多於7重量份，則接著力會降低，因此欠佳。另一方面，若少於0.05重量份，則凝聚力不足，因此欠佳。又，亦可根據需要與此種多異氰酸酯化合物一起含有環氧樹脂等其他多官能性化合物。 再者，於黏晶膜3中，可根據需要適當調配其他添加劑。作為其他添加劑，例如可列舉：阻燃劑、矽烷偶合劑或離子捕捉劑等。作為上述阻燃劑，例如可列舉：三氧化銻、五氧化銻、溴化環氧樹脂等。該等可單獨使用或併用2種以上。作為上述矽烷偶合劑，例如可列舉：β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷等。該等化合物可單獨使用或併用2種以上。作為上述離子捕捉劑，例如可列舉水滑石類、氫氧化鉍等。該等可單獨使用或併用2種以上。 再者，就提高可靠性之觀點而言，亦可使黏晶膜3中含有少量之環氧樹脂。然而，由於環氧樹脂為低分子量，因此若使黏晶膜3中含有大量之環氧樹脂，則熱硬化前之彈性模數會降低。又，由於硬化成分會增加，因此使得熱硬化後之嵌入性降低。因此，黏晶膜3較佳為不含有環氧樹脂。 (切割片材) 本實施形態之切割片材11具有於基材1上積層有黏著劑層2之構成。其中，本發明之切割片材只要於冷擴張步驟中將黏晶膜3斷裂而進行單片化時能夠固定黏晶膜3，則不限定於該例。例如，於基材與黏著劑層之間亦可存在其他層。 (基材) 基材1較佳為具有紫外線透過性者，成為切晶黏晶膜10之強度母體。例如可列舉：低密度聚乙烯、直鏈狀聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、無規共聚聚丙烯、嵌段共聚聚丙烯、均聚聚丙烯、聚丁烯、聚甲基戊烯等聚烯烴、乙烯-乙酸乙烯酯共聚物、離子聚合物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚胺基甲酸酯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯、聚碳酸酯、聚醯亞胺、聚醚醚酮、聚醯亞胺、聚醚醯亞胺、聚醯胺、全芳香族聚醯胺、聚苯硫醚、芳族聚醯胺(紙)、玻璃、玻璃布、氟樹脂、聚氯乙烯、聚偏二氯乙烯、纖維素系樹脂、聚矽氧樹脂、金屬(箔)、紙等。 又，作為基材1之材料，可列舉上述樹脂之交聯體等聚合物。上述塑膠膜可於未延伸之狀態下使用，亦可使用根據需要實施有單軸或雙軸之延伸處理者。根據藉由延伸處理等賦予了熱收縮性之樹脂片材，於冷擴張後使基材1之半導體晶圓之外周部分進行熱收縮(熱擴張)，藉此能夠擴大附黏晶膜3之半導體晶片5彼此之間隔，實現半導體晶片5之回收之容易化。 基材1之表面可實施慣用之表面處理，例如鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、離子化放射線處理等化學或物理處理、利用底塗劑(例如後述之黏著物質)之塗佈處理以提高與鄰接之層之密接性、保持性等。基材1可適當選擇同種或異種者而使用，根據需要可使用摻合數種而成者。又，為了對基材1賦予抗靜電能力，可於基材1上設置包含金屬、合金、該等之氧化物等之厚度為30～500 Å左右之導電性物質之蒸鍍層。基材1可為單層或2種以上之多層。 對基材1之厚度並無特別限制，可適當決定，通常為5～200 μm左右。 (黏著劑層) 作為黏著劑層2之形成中使用之黏著劑，並無特別限制，例如可使用丙烯酸系黏著劑、橡膠系黏著劑等通常之感壓性黏著劑。作為上述感壓性黏著劑，就半導體晶圓或玻璃等避忌污染之電子零件的利用超純水或醇等有機溶劑之清潔洗淨性等方面而言，較佳為將丙烯酸系聚合物作為基礎聚合物之丙烯酸系黏著劑。 作為上述丙烯酸系聚合物，例如可列舉使用以下成分中之1種或2種以上作為單體成分之丙烯酸系聚合物等：(甲基)丙烯酸烷基酯(例如甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、第二丁酯、第三丁酯、戊酯、異戊酯、己酯、庚酯、辛酯、2-乙基己酯、異辛酯、壬酯、癸酯、異癸酯、十一烷基酯、十二烷基酯、十三烷基酯、十四烷基酯、十六烷基酯、十八烷基酯、二十烷基酯等烷基之碳數為1～30、特別是碳數為4～18之直鏈狀或支鏈狀之烷基酯等)及(甲基)丙烯酸環烷基酯(例如環戊酯、環己酯等)。再者，(甲基)丙烯酸酯係指丙烯酸酯及/或甲基丙烯酸酯，本發明之(甲基)全部為同樣之含義。 出於凝聚力、耐熱性等之改質之目的，上述丙烯酸系聚合物亦可根據需要包含能與上述(甲基)丙烯酸烷基酯或環烷基酯共聚合之其他單體成分所對應之單元。作為此種單體成分，例如可列舉：丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸、丁烯酸等含羧基單體；順丁烯二酸酐、伊康酸酐等酸酐單體；(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4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸(4-羥基甲基環己基)甲酯等含羥基單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基單體；2-羥基乙基丙烯醯基磷酸酯等含磷酸基單體；丙烯醯胺、丙烯腈等。該等能共聚合之單體成分可使用1種或2種以上。該等能共聚合之單體之使用量較佳為全部單體成分之40重量%以下。 進而，上述丙烯酸系聚合物根據需要亦可含有多官能性單體等作為共聚合用單體成分以進行交聯。作為此種多官能性單體，例如可列舉：己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯等。該等多官能性單體亦可使用1種或2種以上。就黏著特性等方面而言，多官能性單體之使用量較佳為全部單體成分之30重量%以下。 上述丙烯酸系聚合物可藉由使單一單體或兩種以上之單體混合物聚合而獲得。聚合可以溶液聚合、乳化聚合、塊狀聚合、懸浮聚合等任意方式進行。就防止對清潔之被黏著體之污染等方面而言，較佳為低分子量物質之含量較少。就該方面而言，丙烯酸系聚合物之數量平均分子量較佳為30萬以上，進而較佳為40萬～300萬左右。 又，於上述黏著劑中，為了提高作為基礎聚合物之丙烯酸系聚合物等之數量平均分子量，亦可適當採用外部交聯劑。作為外部交聯方法之具體手段，可列舉：添加多異氰酸酯化合物、環氧化合物、氮丙啶化合物、三聚氰胺系交聯劑等所謂之交聯劑進行反應之方法。於使用外部交聯劑之情形時，其使用量根據與要交聯之基礎聚合物之平衡、進而根據作為黏著劑之使用用途而適當決定。通常，較佳為相對於上述基礎聚合物100重量份，調配約5重量份以下、進而0.1～5重量份。進而，於黏著劑中，根據需要，除上述成分以外，亦可使用先前公知之各種黏著賦予劑、防老化劑等添加劑。 黏著劑層2亦可利用放射線硬化型黏著劑形成。若於貼合有黏晶膜3之狀態下照射紫外線，則能夠於其與黏晶膜3之間產生投錨效應。藉此，能夠提高低溫(例如-15℃)下之黏著劑層2與黏晶膜3之密接性。 再者，溫度越低，則基於投錨效應之密接性越高。雖然於常溫(例如23℃)下亦有投錨效應，但與低溫時相比，於常溫下不會發揮基於投錨效應之密接性。 放射線硬化型黏著劑可並無特別限制地使用具有碳-碳雙鍵等放射線硬化性之官能基且表現黏著性者。作為放射線硬化型黏著劑，例如可例示於上述丙烯酸系黏著劑、橡膠系黏著劑等通常之感壓性黏著劑中調配放射線硬化性之單體成分或低聚物成分而成之添加型放射線硬化型黏著劑。 作為所調配之放射線硬化性之單體成分，例如可列舉：胺基甲酸酯低聚物、(甲基)丙烯酸胺基甲酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等。又，放射線硬化性之低聚物成分可列舉：胺基甲酸酯系、聚醚系、聚酯系、聚碳酸酯系、聚丁二烯系等各種低聚物，適合為其分子量為100～30000左右之範圍者。關於放射線硬化性之單體成分或低聚物成分之調配量，可根據上述黏著劑層之種類適當決定能夠降低黏著劑層之黏著力之量。通常，相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100重量份，例如為5～500重量份，較佳為40～150重量份左右。 又，作為放射線硬化型黏著劑，除了上述說明之添加型放射線硬化型黏著劑以外，亦可列舉將於聚合物側鏈、或者主鏈中或主鏈末端具有碳-碳雙鍵之聚合物用作基礎聚合物之內在型放射線硬化型黏著劑。內在型放射線硬化型黏著劑由於無需含有或者不會較多地含有作為低分子成分之低聚物成分等，因此低聚物成分等不會經時地於黏著劑中移動，能夠形成層結構穩定之黏著劑層，因此較佳。 上述具有碳-碳雙鍵之基礎聚合物可並無特別限制地使用具有碳-碳雙鍵且具有黏著性者。作為此種基礎聚合物，較佳為以丙烯酸系聚合物為基本骨架者。作為丙烯酸系聚合物之基本骨架，可列舉上述例示之丙烯酸系聚合物。 向上述丙烯酸系聚合物中導入碳-碳雙鍵之方法並無特別限制，可採用各種方法，將碳-碳雙鍵導入至聚合物側鏈之方法於分子設計之方面較為容易。例如可列舉如下方法：預先使丙烯酸系聚合物與具有官能基之單體共聚合，然後與具有能與該官能基反應之官能基及碳-碳雙鍵之化合物於維持碳-碳雙鍵之放射線硬化性之狀態下進行縮合或加成反應。 作為該等官能基之組合之例，可列舉羧酸基與環氧基、羧酸基與氮丙啶基、羥基與異氰酸酯基等。就反應追蹤之容易性而言，該等官能基之組合之中，羥基與異氰酸酯基之組合較佳。又，只要為藉由該等官能基之組合而生成上述具有碳-碳雙鍵之丙烯酸系聚合物之組合，則官能基可位於丙烯酸系聚合物及上述化合物中之任一側，於上述較佳之組合中，丙烯酸系聚合物具有羥基且上述化合物具有異氰酸酯基之情況較佳。於該情形時，作為具有碳-碳雙鍵之異氰酸酯化合物，例如可列舉：甲基丙烯醯基異氰酸酯、2-甲基丙烯醯氧基乙基異氰酸酯、間異丙烯基-α,α-二甲基苄基異氰酸酯等。又，作為丙烯酸系聚合物，可使用使上述例示之含羥基單體、或2-羥基乙基乙烯醚、4-羥基丁基乙烯醚、二乙二醇單乙烯醚之醚系化合物等共聚合而成之聚合物。 上述內在型放射線硬化型黏著劑可單獨使用上述具有碳-碳雙鍵之基礎聚合物(特別是丙烯酸系聚合物)，亦可於不會使特性惡化之程度下調配上述放射線硬化性之單體成分或低聚物成分。放射線硬化性之低聚物成分等通常相對於基礎聚合物100重量份為30重量份之範圍內，較佳為0～10重量份之範圍。 上述放射線硬化型黏著劑於藉由紫外線等使之硬化時含有光聚合起始劑。作為光聚合起始劑，例如可列舉：4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α'-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、1-羥基環己基苯基酮等α-酮醇系化合物；甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)-苯基]-2-&#134156;啉基丙烷-1等苯乙酮系化合物；安息香乙醚、安息香異丙醚、大茴香偶姻甲醚等安息香醚系化合物；苯偶醯二甲基縮酮等縮酮系化合物；2-萘磺醯氯等芳香族磺醯氯系化合物；1-苯酮-1,1-丙二酮-2-(o-乙氧基羰基)肟等光活性肟系化合物；二苯甲酮、苯甲醯苯甲酸、3,3'-二甲基-4-甲氧基二苯甲酮等二苯甲酮系化合物；9-氧硫&#134079; 、2-氯-9-氧硫&#134079; 、2-甲基-9-氧硫&#134079; 、2,4-二甲基-9-氧硫&#134079; 、異丙基-9-氧硫&#134079; 、2,4-二氯-9-氧硫&#134079; 、2,4-二乙基-9-氧硫&#134079; 、2,4-二異丙基-9-氧硫&#134079; 等9-氧硫&#134079; 系化合物；樟腦醌；鹵代酮；醯基氧化膦；醯基膦酸酯等。光聚合起始劑之調配量相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100重量份，例如為0.05～20重量份左右。 又，作為放射線硬化型黏著劑，例如可列舉日本專利特開昭60-196956號公報中揭示之橡膠系黏著劑或丙烯酸系黏著劑等，其等含有：具有2個以上不飽和鍵之加成聚合性化合物、具有環氧基之烷氧基矽烷等光聚合性化合物、以及羰基化合物、有機硫化合物、過氧化物、胺、鎓鹽系化合物等光聚合起始劑。 對黏著劑層2之厚度並無特別限定，就晶片切斷面之缺損防止及黏晶膜3之固定保持之兼顧性等方面而言，較佳為1～50 μm左右，更佳為2～30 μm，進而較佳為5～25 μm。 上述切晶黏晶膜10之黏晶膜3較佳為由隔離膜所保護(未圖示)。隔離膜具有作為於供於實際使用之前保護黏晶膜3之保護材料之功能。又，隔離膜進而可作為將黏晶膜3轉印至黏著劑層2時之支持基材使用。隔離膜於將工件貼合於切晶黏晶膜之黏晶膜3上時被剝離。作為隔離膜，亦可使用聚對苯二甲酸乙二酯(PET)、聚乙烯、聚丙烯、或藉由氟系剝離劑、長鏈烷基丙烯酸酯系剝離劑等剝離劑進行了表面塗佈之塑膠膜或紙等。 本實施形態之切晶黏晶膜10例如可以如下方式製作。 首先，基材1可藉由先前公知之製膜方法進行製膜。作為該製膜方法，例如可例示壓延製膜法、於有機溶劑中之流延法(casting)、於密閉系統中之吹脹擠出法、T模擠出法、共擠出法、乾式層壓法等。 繼而，於基材1上塗佈黏著劑組合物溶液而形成塗佈膜後，使該塗佈膜於特定條件下乾燥(根據需要使其加熱交聯)，形成前體層。作為塗佈方法，並無特別限定，例如可列舉：輥塗覆、絲網塗覆、凹版塗覆等。又，作為乾燥條件，例如於乾燥溫度80～150℃、乾燥時間0.5～5分鐘之範圍內進行。又，亦可於隔離膜上塗佈黏著劑組合物而形成塗佈膜後，於上述乾燥條件下使塗佈膜乾燥而形成上述前體層。然後，將上述前體層與隔離膜一起貼合於基材1上。藉此，製作切割片材前體。 黏晶膜3例如可以如下方式製作。 首先，製作作為黏晶膜3之形成材料之接著劑組合物溶液。於該接著劑組合物溶液中，如上所述調配有上述接著劑組合物、填料、其他各種添加劑等。 繼而，將接著劑組合物溶液以成為特定厚度之方式塗佈於基材隔離膜上而形成塗佈膜後，使該塗佈膜於特定條件下乾燥，形成黏晶膜3。作為塗佈方法，並無特別限定，例如可列舉：輥塗覆、絲網塗覆、凹版塗覆等。又，作為乾燥條件，例如於乾燥溫度70～160℃、乾燥時間1～5分鐘之範圍內進行。又，亦可於隔離膜上塗佈黏著劑組合物溶液而形成塗佈膜後，於上述乾燥條件下使塗佈膜乾燥而形成黏晶膜3。然後，將黏晶膜3與隔離膜一起貼合於基材隔離膜上。 繼而，分別自上述切割片材前體及黏晶膜3剝離隔離膜，以黏晶膜3及黏著劑層成為貼合面之方式將兩者貼合。貼合例如可藉由壓接而進行。此時，對層壓溫度並無特別限定，例如較佳為30～50℃，更佳為35～45℃。又，對線壓並無特別限定，例如較佳為0.1～20 kgf/cm，更佳為1～10 kgf/cm。然後，亦可從基材1側照射紫外線。作為紫外線之照射量，較佳為使上述剝離力A及上述剝離力B位於上述數值範圍內之量。具體之紫外線之照射量根據黏著劑層之組成或厚度等不同，例如較佳為50 mJ～500 mJ，更佳為100 mJ～300 mJ。藉由以上方式獲得本實施形態之切晶黏晶膜。 (半導體裝置之製造方法) 繼而，一面參照圖2～圖5、圖7、圖8一面對使用切晶黏晶膜10之半導體裝置之製造方法進行說明。 本實施形態之半導體裝置之製造方法至少包括以下步驟： 步驟A，將半導體晶圓貼附於切晶黏晶膜； 步驟B，使上述切晶黏晶膜擴張，至少使上述黏晶膜斷裂，獲得附黏晶膜之晶片； 步驟C，拾取上述附黏晶膜之晶片； 步驟D，將所拾取之上述附黏晶膜之晶片經由黏晶膜黏晶至被黏著體；以及 步驟E，對上述附黏晶膜之晶片進行打線接合；且 上述切晶黏晶膜含有： 平均粒徑為5 nm～100 nm之範圍內之填料、 熱塑性樹脂、及 酚樹脂， 熱硬化前之於150℃下之拉伸儲存彈性模數大於0.3 MPa且為30 MPa以下。 以下，首先對使切晶黏晶膜擴張，使黏晶膜及改質區域形成後之半導體晶圓同時斷裂，獲得附黏晶膜之晶片之情況(隱形切割)進行說明。 圖2～圖5係用以說明本實施形態之半導體裝置之一製造方法之剖視模式圖。 首先，對半導體晶圓4之分割預定線4L照射雷射光，於分割預定線4L上形成改質區域(參照圖2)。本方法係如下之方法：使聚光點對準半導體晶圓之內部，沿格子狀之分割預定線照射雷射光，藉由基於多光子吸收之剝蝕於半導體晶圓之內部形成改質區域。作為雷射光照射條件，只要於以下條件之範圍內進行適當調整即可。 ＜雷射光照射條件＞ (A)雷射光 雷射光源 半導體雷射激發Nd：YAG雷射 波長 1064 nm 雷射光點截面積 3.14×10-8 cm2 振盪形態 Q開關脈衝 重複頻率 100 kHz以下 脈衝寬度 1 μs以下 輸出 1 mJ以下 雷射光品質 TEM00 偏光特性 直線偏光 (B)聚光用透鏡 倍率 100倍以下 NA 0.55 對雷射光波長之透過率 100%以下 (C)載置半導體基板之裁置台之移動速度 280 mm/s以下 再者，關於照射雷射光而於分割預定線4L上形成改質區域之方法，於日本專利第3408805號公報、日本專利特開2003-338567號公報中進行了詳細敍述，因此省略此處之詳細說明。 繼而，如圖3所示，將改質區域形成後之半導體晶圓4壓接於黏晶膜3上，將其接著保持而固定(安裝(mount)步驟)。該步驟相當於本發明之步驟A。本步驟係一面藉由壓接輥等按壓機構實施按壓一面進行。對安裝時之貼附溫度並無特別限定，較佳為40～80℃之範圍內。其原因在於，能夠有效地防止半導體晶圓4之翹曲，並且能夠減少切晶黏晶膜之伸縮之影響。 繼而，藉由對切晶黏晶膜10施加拉伸張力，使半導體晶圓4與黏晶膜3沿分割預定線4L斷裂，形成半導體晶片5(冷擴張步驟)。該步驟相當於本發明之步驟B。本步驟中例如可使用市售之晶圓擴展裝置。具體而言，如圖4(a)所示，於貼合有半導體晶圓4之切晶黏晶膜10之黏著劑層2周邊部貼附切割環31後，固定於晶圓擴展裝置32。繼而，如圖4(b)所示，使頂起部33上升，而對切晶黏晶膜12施加張力。 上述冷擴張步驟較佳為於0～-15℃之條件下實行，更佳為於-5～ ‑15℃之條件下實行。由於上述冷擴張步驟於0～-15℃之條件下實行，因此能夠使黏晶膜3較佳地斷裂。 又，於上述冷擴張步驟中，擴張速度(頂起部上升之速度)較佳為100～400 mm/s，更佳為100～350 mm/s，進而較佳為100～300 mm/s。若使擴張速度為100 mm/s以上，則能夠容易地使半導體晶圓4與黏晶膜3大致同時斷裂。又，若使擴張速度為400 mm/s以下，則能夠防止切割片材11斷裂。 又，於上述冷擴張步驟中，關於擴張量，較佳為擴張量為4～16 mm。上述擴張量可於上述數值範圍內根據所形成之晶片尺寸進行適當調整。若使擴張量為4 mm以上，則能夠使半導體晶圓4及黏晶膜3之斷裂更容易。又，若使擴張量為16 mm以下，則能夠進一步防止切割片材11斷裂。 如此，藉由對切晶黏晶膜10施加拉伸張力，能夠以半導體晶圓4之改質區域為起點，於半導體晶圓4之厚度方向產生裂紋，並且使與半導體晶圓4密接之黏晶膜3斷裂，從而能夠獲得附黏晶膜3之半導體晶片5。 繼而，根據需要進行熱擴張步驟。於熱擴張步驟中，對切割片材11之較貼附有半導體晶圓4之部分更外側進行加熱而使其熱收縮。藉此，使半導體晶片5彼此之間隔擴大。對熱擴張步驟中之條件並無特別限定，較佳為設為：擴張量4～16 mm、加熱溫度200～260℃、加熱距離2～30 mm、旋轉速度3°/s～10°/s之範圍內。 再者，熱擴張步驟不限定於該例。例如，熱擴張步驟亦可為包含以下之步驟(1)～(3)之步驟。 (1)冷擴張步驟之後，首先，藉由加熱台使切割片材11擴張。藉此，消除切割片材11之鬆弛，使半導體晶片5彼此之間隔擴大。 (2)繼而，將切割片材11之貼附有半導體晶圓4之部分吸附於加熱台，使得能夠維持晶片間隔擴大之狀態。 (3)然後，對切割片材11之較貼附有半導體晶圓4之部分更外側進行加熱使其熱收縮(heat Shrink)。 繼而，根據需要進行清潔步驟。於清潔步驟中，將固定有附黏晶膜3之半導體晶片5之狀態之切割片材11設置於旋塗器。繼而，一面向半導體晶片5滴加洗淨液一面使旋塗器旋轉。藉此，對半導體晶片5之表面進行洗淨。作為洗淨液，例如可列舉水。旋塗器之旋轉速度或旋轉時間根據洗淨液之種類等而不同，例如可設為旋轉速度400～3000 rpm、旋轉時間1～5分鐘。 繼而，為了將接著固定於切晶黏晶膜10之半導體晶片5剝離，進行半導體晶片5之拾取(拾取步驟)。該步驟相當於本發明之步驟C。作為拾取之方法，並無特別限定，可採用先前公知之各種方法。例如可列舉利用針將各個半導體晶片5從切晶黏晶膜10側頂起，藉由拾取裝置拾取被頂起之半導體晶片5之方法等。 繼而，如圖5所示，將所拾取之半導體晶片5經由黏晶膜3黏晶至被黏著體6(暫時固著步驟)。該步驟相當於本發明之步驟D。作為被黏著體6，可列舉：引線框架、TAB膜、基板或另行製作之半導體晶片等。被黏著體6例如可為容易變形之變形型被黏著體，亦可為不易變形之非變形型被黏著體(半導體晶圓等)。 作為上述基板，可使用先前公知者。又，作為上述引線框架，可使用Cu引線框架、42合金引線框架等金屬引線框架、或包含玻璃環氧化物(glass-epoxy)、BT(雙馬來醯亞胺-三&#134116;)、聚醯亞胺等之有機基板。然而，本發明不限定於此，亦包含能將半導體元件接著固定並與半導體元件電性連接而使用之電路基板。 黏晶膜3之暫時固著時之於25℃下之剪切接著力相對於被黏著體6，較佳為0.2 MPa以上，更佳為0.2～10 MPa。若黏晶膜3之剪切接著力為至少0.2 MPa以上，則於打線接合步驟時，很少因該步驟中之超音波振動或加熱而於黏晶膜3與半導體晶片5或被黏著體6之接著面發生偏移變形。即，很少由於打線接合時之超音波振動而導致半導體元件移動，藉此防止打線接合之成功率降低。又，黏晶膜3之暫時固著時之於175℃下之剪切接著力相對於被黏著體6，較佳為0.01 MPa以上，更佳為0.01～5 MPa。 繼而，進行將被黏著體6之端子部(內部引線)之前端與半導體晶片5上之電極墊(未圖示)利用接合線7進行電性連接之打線接合(打線接合步驟)。該步驟相當於本發明之步驟E。作為上述接合線7，例如使用金線、鋁線或銅線等。關於進行打線接合時之溫度，於80～250℃、較佳為於80～220℃之範圍內進行。又，關於其加熱時間，進行數秒～數分鐘。接線係於加熱至成為上述溫度範圍內之狀態下藉由併用基於超音波之振動能量及基於施加加壓之壓接能量而進行。本步驟係於不進行黏晶膜3之熱硬化之狀態下實行。又，於本步驟之過程中，不會由於黏晶膜3導致半導體晶片5與被黏著體6固著。 繼而，利用密封樹脂8將半導體晶片5密封(密封步驟)。本步驟係為了保護搭載於被黏著體6之半導體晶片5及接合線7而進行。本步驟係藉由利用模具將密封用之樹脂成型而進行。作為密封樹脂8，例如使用環氧系之樹脂。關於樹脂密封時之加熱溫度，通常於175℃下進行60～90秒，但本發明不限定於此，例如可於165～185℃下固化數分鐘。藉此，使密封樹脂硬化，並且經由黏晶膜3使半導體晶片5與被黏著體6固著。即，於本發明中，即使於不進行後述之後硬化步驟之情形時，亦能於本步驟中實現基於黏晶膜3之固著，能夠有助於減少製造步驟數量及縮短半導體裝置之製造時間。再者，密封步驟不限定於該例，亦可為使用片狀之密封樹脂(密封用片材)，藉由例如平行板壓製將半導體晶片5嵌埋於該密封用片材中之步驟。 於上述後硬化步驟中，使於上述密封步驟中未充分硬化之密封樹脂8完全硬化。即使於在密封步驟中黏晶膜3未完全熱硬化之情形時，亦能於本步驟中使黏晶膜3與密封樹脂8一同完全熱硬化。本步驟中之加熱溫度根據密封樹脂之種類而不同，例如為165～185℃之範圍內，加熱時間為0.5～8小時左右。 再者，本發明之切晶黏晶膜於將複數個半導體晶片積層而進行三維安裝之情形時亦可適宜地使用。此時，可於半導體晶片間積層黏晶膜及間隔物，亦可於半導體晶片間僅積層黏晶膜而不積層間隔物，可根據製造條件或用途等進行適當變更。 以下，簡單地對積層有複數個半導體晶片之半導體裝置進行說明。圖6係表示本實施形態之半導體裝置之另一例之剖視模式圖。圖6所示之半導體裝置經由黏晶膜3於被黏著體6上積層有半導體晶片5，進而，經由黏晶膜13於半導體晶片5上積層有半導體晶片15。半導體晶片15於俯視下較半導體晶片5小。於半導體晶片5之上表面形成之電極墊(未圖示)於俯視下從半導體晶片15露出。於半導體晶片5之上表面形成之電極墊與被黏著體6之端子部(未圖示)藉由接合線7進行電性連接。又，於半導體晶片15之上表面形成之電極墊(未圖示)與被黏著體6之端子部(未圖示)藉由接合線7進行電性連接。半導體晶片5、半導體晶片15由密封樹脂8所密封。黏晶膜13可為與黏晶膜3同樣之組成，亦可為於上述黏晶膜之項中說明之範圍內與黏晶膜3不同組成。 以上，對積層有複數個半導體晶片之半導體裝置之一例進行了說明。 繼而，對於採用於半導體晶圓之表面形成槽，然後進行背面研削之步驟(DBG步驟：Dicing Before Grinding(切割後研磨步驟))的半導體裝置之製造方法，將於以下進行說明。 圖7、圖8係用以說明本實施形態之半導體裝置之另一製造方法之剖視模式圖。首先，如圖7(a)所示，利用旋轉刀片(blade)41於半導體晶圓4之表面4F形成未到達背面4R之槽4S。再者，於槽4S之形成時，半導體晶圓4由未圖示之支持基材所支持。槽4S之深度可根據半導體晶圓4之厚度或擴張之條件進行適當設定。繼而，如圖7(b)所示，以表面4F抵接之方式使半導體晶圓4由保護基材42所支持。然後，利用研削磨石45進行背面研削，使槽4S從背面4R露出。再者，保護基材42向半導體晶圓之貼附可使用先前公知之貼附裝置，背面研削亦可使用先前公知之研削裝置。 繼而，如圖8所示，於切晶黏晶膜10上壓接露出槽4S之半導體晶圓4，將其接著保持而固定。該步驟相當於本發明之步驟A。然後，剝離保護基材42，藉由晶圓擴展裝置32對切晶黏晶膜10施加張力。藉此，使黏晶膜3斷裂，形成半導體晶片5(晶片形成步驟)。該步驟相當於本發明之步驟B。再者，晶片形成步驟中之溫度、擴張速度、擴張量係與照射雷射光而於分割預定線4L上形成改質區域之情形同樣。以後之步驟由於與照射雷射光而於分割預定線4L上形成改質區域之情形同樣，因此省略此處之說明。 本實施形態之半導體裝置之製造方法只要使半導體晶圓與黏晶膜同時於冷擴張步驟中斷裂，或僅使黏晶膜於冷擴張步驟中斷裂，則不限定於上述實施形態。作為其他實施形態，例如，亦可於如圖7(a)所示般利用旋轉刀片41於半導體晶圓4之表面4F形成未到達背面4R之槽4S後，於切晶黏晶膜上壓接露出槽4S之半導體晶圓4，將其接著保持而固定(暫時固著步驟)。然後，藉由晶圓擴展裝置對切晶黏晶膜施加張力。藉此，於槽4S之部分中，使半導體晶圓4與黏晶膜3斷裂，形成半導體晶片5。 然而，本發明之半導體裝置之製造方法不限定於該例。 例如，亦可為如下之半導體裝置之製造方法，其包括以下步驟： 步驟A，將半導體晶圓貼附於切晶黏晶膜； 步驟X，藉由刀片將上述半導體晶圓與上述黏晶膜一起切割，獲得附黏晶膜之晶片； 步驟C，拾取上述附黏晶膜之晶片； 步驟D，將所拾取之上述附黏晶膜之晶片經由黏晶膜黏晶至被黏著體；以及， 步驟E，對上述附黏晶膜之晶片進行打線接合。 [實施例] 以下，利用實施例對本發明進行詳細說明，但本發明只要不超出其主旨則不限定於以下之實施例。又，各例中，只要無特別說明，則份均為重量基準。 (實施例1) ＜切割片材之製作＞ 於具備冷卻管、氮氣導入管、溫度計及攪拌裝置之反應容器中加入丙烯酸2-乙基己酯(以下，亦稱為「2EHA」)100份、丙烯酸2-羥基乙酯(以下，亦稱為「HEA」)19份、過氧化苯甲醯0.4份及甲苯80份，於氮氣氣流中以60℃進行10小時聚合處理，獲得丙烯酸系聚合物A。 向該丙烯酸系聚合物A中加入2-甲基丙烯醯氧基乙基異氰酸酯(以下，亦稱為「MOI」)1.2份，於空氣氣流中以50℃進行60小時加成反應處理，獲得丙烯酸系聚合物A'。 繼而，相對於丙烯酸系聚合物A' 100份，加入多異氰酸酯化合物(商品名「CORONATE L」，Nippon Polyurethane(股)製)1.3份、及光聚合起始劑(商品名「Irgacure 184」，Ciba Specialty Chemicals公司製)3份，製作黏著劑溶液(亦稱為「黏著劑溶液A」)。 將上述所製備之黏著劑溶液A塗佈於PET剝離襯墊之實施有聚矽氧處理之面上，於120℃下加熱乾燥2分鐘，形成厚度10 μm之黏著劑層A。繼而，於黏著劑層A之露出面貼合厚度125 μm之GUNZE公司製之EVA膜(乙烯-乙酸乙烯酯共聚物膜)，於23℃下保存72小時，獲得切割片材A。 ＜黏晶膜之製作＞ 使下述(a)～(d)溶解於甲基乙基酮，獲得固形物成分濃度為18重量%之接著劑組合物溶液A。 (a)丙烯酸系樹脂(商品名「SG-P3」，Nagase ChemteX公司製，分子量850,000)：100份 (b)酚樹脂(商品名「MEH-7851ss」，明和化成公司製)：12份 (c)填料A(商品名「YA010C-SP3」，Admatechs股份有限公司製，平均粒徑10 nm)：100份 (d)著色劑(商品名「OIL SCARLET 308」，ORIENT CHEMICAL INDUSTRIES股份有限公司製)：1份 將接著劑組合物溶液A塗佈於包含經聚矽氧脫模處理之厚度50 μm之聚對苯二甲酸乙二酯膜之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。藉此，獲得厚度(平均厚度)5 μm及厚度(平均厚度)20 μm之黏晶膜A。 ＜切晶黏晶膜之製作＞ 從切割片材A剝離PET剝離襯墊，使黏晶膜A貼合於露出之黏著劑層。於貼合中使用了手壓輥。繼而，從切割片材側照射300 mJ之紫外線。藉由以上方式獲得切晶黏晶膜A。 (實施例2) ＜黏晶膜之製作＞ 使下述(a)～(d)溶解於甲基乙基酮，獲得固形物成分濃度18重量%之接著劑組合物溶液B。 (a)丙烯酸系樹脂(商品名「SG-P3」，Nagase ChemteX公司製，分子量850,000)：100份 (b)酚樹脂(商品名「MEH-7851ss」，明和化成公司製)：12份 (c)填料B(商品名「YA010C-SV1」，Admatechs股份有限公司製，平均粒徑10 nm)：100份 (d)著色劑(商品名「OIL SCARLET 308」，ORIENT CHEMICAL INDUSTRIES股份有限公司製)：1份 將接著劑組合物溶液B塗佈於包含經聚矽氧脫模處理之厚度50 μm之聚對苯二甲酸乙二酯膜之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。藉此，獲得厚度(平均厚度)5 μm及厚度(平均厚度)20 μm之黏晶膜B。 ＜切晶黏晶膜之製作＞ 準備與實施例1中使用之切割片材A相同之切割片材。繼而，從切割片材A剝離PET剝離襯墊，使黏晶膜B貼合於露出之黏著劑層。於貼合中使用了手壓輥。繼而，從切割片材側照射300 mJ之紫外線。藉由以上方式獲得切晶黏晶膜B。 (實施例3) ＜黏晶膜之製作＞ 使下述(a)～(d)溶解於甲基乙基酮，獲得固形物成分濃度18重量%之接著劑組合物溶液C。 (a)丙烯酸系樹脂(商品名「SG-P3」，Nagase ChemteX公司製，分子量850,000)：100份 (b)酚樹脂(商品名「MEH-7851ss」，明和化成公司製)：12份 (c)填料C(商品名「MEK-ST-40」，日產化學工業股份有限公司製，平均粒徑13 nm)：100份 (d)著色劑(商品名「OIL SCARLET 308」，ORIENT CHEMICAL INDUSTRIES股份有限公司製)：1份 將接著劑組合物溶液C塗佈於包含經聚矽氧脫模處理之厚度50 μm之聚對苯二甲酸乙二酯膜之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。藉此，獲得厚度(平均厚度)5 μm及厚度(平均厚度)20 μm之黏晶膜C。 ＜切晶黏晶膜之製作＞ 準備與實施例1中使用之切割片材A相同之切割片材。繼而，從切割片材A剝離PET剝離襯墊，使黏晶膜C貼合於露出之黏著劑層。於貼合中使用了手壓輥。繼而，從切割片材側照射300 mJ之紫外線。藉由以上方式獲得切晶黏晶膜C。 (實施例4) ＜黏晶膜之製作＞ 使下述(a)～(d)溶解於甲基乙基酮，獲得固形物成分濃度18重量%之接著劑組合物溶液D。 (a)丙烯酸系樹脂(商品名「SG-P3」，Nagase ChemteX公司製，分子量850,000)：100份 (b)酚樹脂(商品名「MEH-7851ss」，明和化成公司製)：12份 (c)填料D(商品名「MEK-ST-L」，日產化學工業股份有限公司製，平均粒徑45 nm)：100份 (d)著色劑(商品名「OIL SCARLET 308」，ORIENT CHEMICAL INDUSTRIES股份有限公司製)：1份 將接著劑組合物溶液D塗佈於包含經聚矽氧脫模處理之厚度50 μm之聚對苯二甲酸乙二酯膜之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。藉此，獲得厚度(平均厚度)5 μm及厚度(平均厚度)20 μm之黏晶膜D。 ＜切晶黏晶膜之製作＞ 準備與實施例1中使用之切割片材A相同之切割片材。繼而，從切割片材A剝離PET剝離襯墊，使黏晶膜D貼合於露出之黏著劑層。於貼合中使用了手壓輥。繼而，從切割片材側照射300 mJ之紫外線。藉由以上方式獲得切晶黏晶膜D。 (實施例5) ＜黏晶膜之製作＞ 使下述(a)～(d)溶解於甲基乙基酮，獲得固形物成分濃度18重量%之接著劑組合物溶液E。 (a)丙烯酸系樹脂(商品名「SG-P3」，Nagase ChemteX公司製，分子量850,000)：100份 (b)酚樹脂(商品名「MEH-7851ss」，明和化成公司製)：12份 (c)填料E(商品名「MEK-ST-ZL」，日產化學工業股份有限公司製，平均粒徑85 nm)：100份 (d)著色劑(商品名「OIL SCARLET 308」，ORIENT CHEMICAL INDUSTRIES股份有限公司製)：1份 將接著劑組合物溶液E塗佈於包含經聚矽氧脫模處理之厚度50 μm之聚對苯二甲酸乙二酯膜之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。藉此，獲得厚度(平均厚度)5 μm及厚度(平均厚度)20 μm之黏晶膜E。 ＜切晶黏晶膜之製作＞ 準備與實施例1中使用之切割片材A相同之切割片材。繼而，從切割片材A剝離PET剝離襯墊，使黏晶膜E貼合於露出之黏著劑層。於貼合中使用了手壓輥。繼而，從切割片材側照射300 mJ之紫外線。藉由以上方式獲得切晶黏晶膜E。 (實施例6) ＜黏晶膜之製作＞ 使下述(a)～(c)溶解於甲基乙基酮，獲得固形物成分濃度18重量%之接著劑組合物溶液F。 (a)丙烯酸系樹脂(商品名「SG-P3」，Nagase ChemteX公司製，分子量850,000)：100份 (b)酚樹脂(商品名「MEH-7851ss」，明和化成公司製)：12份 (c)填料D(商品名「MEK-ST-L」，日產化學工業股份有限公司製，平均粒徑45 nm)：100份 將接著劑組合物溶液F塗佈於包含經聚矽氧脫模處理之厚度50 μm之聚對苯二甲酸乙二酯膜之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。藉此，獲得厚度(平均厚度)5 μm及厚度(平均厚度)20 μm之黏晶膜F。 ＜切晶黏晶膜之製作＞ 準備與實施例1中使用之切割片材A相同之切割片材。繼而，從切割片材A剝離PET剝離襯墊，使黏晶膜F貼合於露出之黏著劑層。於貼合中使用了手壓輥。繼而，從切割片材側照射300 mJ之紫外線。藉由以上方式獲得切晶黏晶膜F。 (比較例1) ＜黏晶膜之製作＞ 使下述(a)～(d)溶解於甲基乙基酮，獲得固形物成分濃度18重量%之接著劑組合物溶液G。 (a)丙烯酸系樹脂(商品名「SG-P3」，Nagase ChemteX公司製，分子量850,000)：100份 (b)酚樹脂(商品名「MEH-7851ss」，明和化成公司製)：12份 (c)填料C(商品名「MEK-ST-40」，日產化學工業股份有限公司製，平均粒徑13 nm)：280份 (d)著色劑(商品名「OIL SCARLET 308」，ORIENT CHEMICAL INDUSTRIES股份有限公司製)：2份 將接著劑組合物溶液G塗佈於包含經聚矽氧脫模處理之厚度50 μm之聚對苯二甲酸乙二酯膜之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。藉此，獲得厚度(平均厚度)5 μm及厚度(平均厚度)20 μm之黏晶膜G。 ＜切晶黏晶膜之製作＞ 從切割片材A剝離PET剝離襯墊，使黏晶膜A貼合於露出之黏著劑層。於貼合中使用了手壓輥。繼而，從切割片材側照射300 mJ之紫外線。藉由以上方式獲得切晶黏晶膜G。 (比較例2) ＜黏晶膜之製作＞ 使下述(a)～(c)溶解於甲基乙基酮，獲得固形物成分濃度18重量%之接著劑組合物溶液H。 (a)丙烯酸系樹脂(商品名「SG-P3」，Nagase ChemteX公司製，分子量850,000)：100份 (b)酚樹脂(商品名「MEH-7851ss」，明和化成公司製)：12份 (c)填料F(商品名「SO-25R」，Adtex股份有限公司製，平均粒徑500 nm)：100份 將接著劑組合物溶液H塗佈於包含經聚矽氧脫模處理之厚度50 μm之聚對苯二甲酸乙二酯膜之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。藉此，獲得厚度(平均厚度)5 μm及厚度(平均厚度)20 μm之黏晶膜H。 ＜切晶黏晶膜之製作＞ 準備與實施例1中使用之切割片材A相同之切割片材。繼而，從切割片材A剝離PET剝離襯墊，使黏晶膜H貼合於露出之黏著劑層。於貼合中使用了手壓輥。繼而，從切割片材側照射300 mJ之紫外線。藉由以上方式獲得切晶黏晶膜H。 (比較例3) ＜黏晶膜之製作＞ 使下述(a)～(c)溶解於甲基乙基酮，獲得固形物成分濃度18重量%之接著劑組合物溶液I。 (a)丙烯酸系樹脂(商品名「SG-P3」，Nagase ChemteX公司製，分子量850,000)：100份 (b)酚樹脂(商品名「MEH-7851ss」，明和化成公司製)：12份 (c)著色劑(商品名「OIL SCARLET 308」，ORIENT CHEMICAL INDUSTRIES股份有限公司製)：1份 將接著劑組合物溶液I塗佈於包含經聚矽氧脫模處理之厚度50 μm之聚對苯二甲酸乙二酯膜之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。藉此，獲得厚度(平均厚度)5 μm及厚度(平均厚度)20 μm之黏晶膜I。 ＜切晶黏晶膜之製作＞ 準備與實施例1中使用之切割片材A相同之切割片材。繼而，從切割片材A剝離PET剝離襯墊，使黏晶膜I貼合於露出之黏著劑層。於貼合中使用了手壓輥。繼而，從切割片材側照射300 mJ之紫外線。藉由以上方式獲得切晶黏晶膜I。 (比較例4) ＜黏晶膜之製作＞ 使下述(a)～(f)溶解於甲基乙基酮，獲得固形物成分濃度45重量%之接著劑組合物溶液J。 (a)丙烯酸系樹脂(商品名「SG-P3」，Nagase ChemteX公司製，分子量850,000)：100份 (b)環氧樹脂A(商品名「JER1010」，三菱化學公司製)：52份 (c)環氧樹脂B(商品名「JER828」，三菱化學公司製)：140份 (d)酚樹脂(商品名「MEH-7851ss」，明和化成公司製)：210份 (e)填料C(商品名「MEK-ST-40」，日產化學工業股份有限公司製，平均粒徑13 nm)：100份 (f)硬化促進劑(商品名「2PHZ-PW」，四國化成工業股份有限公司製)：3份 將接著劑組合物溶液J塗佈於包含經聚矽氧脫模處理之厚度50 μm之聚對苯二甲酸乙二酯膜之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。藉此，獲得厚度(平均厚度)5 μm及厚度(平均厚度)20 μm之黏晶膜J。 ＜切晶黏晶膜之製作＞ 準備與實施例1中使用之切割片材A相同之切割片材。繼而，從切割片材A剝離PET剝離襯墊，使黏晶膜J貼合於露出之黏著劑層。於貼合中使用了手壓輥。繼而，從切割片材側照射300 mJ之紫外線。藉由以上方式獲得切晶黏晶膜J。 [填料之平均粒徑之測定] 將實施例、比較例之黏晶膜於175℃下加熱1小時，然後，將熱硬化後之黏晶膜包埋於樹脂(Struers公司製，EpoFix kit)中。對包埋而成之樣品進行機械研磨而使黏晶膜之截面露出。繼而，藉由CP裝置(截面拋光儀，日本電子股份有限公司製，SM-09010)對截面進行離子研磨(ion milling)加工。然後，實施導電處理，進行FE-SEM(Field-Emission Scanning Electron Microscope，場發射掃描式電子顯微鏡)觀察。FE-SEM之觀察係於加速電壓1～5 kV下進行，觀察反射電子像。利用圖像分析軟體Image-J對所拍攝之圖像進行二值化處理並識別填料粒子。繼而，將圖像內之填料粒子之面積除以圖像內之填料粒子個數，求出填料粒子之平均面積，算出粒徑。 [黏晶膜熱硬化前之於150℃及175℃下之拉伸儲存彈性模數、及黏晶膜熱硬化前之玻璃轉移溫度之測定] 使實施例及比較例之黏晶膜重疊直至厚度變為200 μm。繼而，利用切割刀切出長度40 mm(測定長度)、寬度10 mm之短條狀。繼而，使用固體黏彈性測定裝置(RSAIII，Rheometric Scientific(股)製)，測定-40～260℃下之拉伸儲存彈性模數。測定條件設為：卡盤(chuck)間距離20 mm、拉伸模式、頻率1 Hz、應變0.1%、升溫速度10℃/min。測定係於‑40℃下保持5分鐘後開始。讀取此時於150℃及175℃下之值，作為拉伸儲存彈性模數之測定值。 又，根據所獲得之tanδ之資料製作溫度-Tanδ曲線，讀取最大之峰之Tanδ最大值之溫度，將該溫度作為熱硬化前之玻璃轉移溫度。將結果示於表1。 [黏晶膜熱硬化後之玻璃轉移溫度之測定] 使實施例及比較例之黏晶膜重疊直至厚度變為200 μm。繼而，於175℃下加熱1小時，形成熱硬化後之黏晶膜。繼而，利用切割刀切出長度40 mm(測定長度)、寬度10 mm之短條狀。繼而，使用固體黏彈性測定裝置(RSAIII，Rheometric Scientific公司製)，測定-40～260℃下之拉伸儲存彈性模數。測定條件設為：卡盤間距離20 mm、拉伸模式、頻率1 Hz、應變0.1%、升溫速度10℃/min。測定係於-40℃下保持5分後開始。根據所獲得之tanδ之資料製作溫度-Tanδ曲線，讀取最大之峰之Tanδ最大值之溫度，將該溫度作為熱硬化後之玻璃轉移溫度。將結果示於表1。 [黏晶膜熱硬化前之狀態下之於-15℃下之斷裂伸長率之測定] 使實施例及比較例之黏晶膜重疊直至厚度變為200 μm。繼而，利用切割刀切出長度60 mm(測定長度)、寬度10 mm之短條狀。 使用拉伸試驗機(製造商名：SHIMADZU：附恆溫恆濕槽之3連拉伸試驗機)，測定於-15℃下之斷裂伸長率。測定條件設為：卡盤間距離20 mm、速度100 mm/min、測定溫度-15℃。測定係於-15℃下保持2分鐘後開始。斷裂伸長率係根據下式求出。將結果示於表1。 [斷裂伸長率(%)]＝[(斷裂時之接著片材之長度(mm)－20)/20×100] [視認性評價] 將能夠容易地視認到黏晶膜與脫模處理膜(剝離襯墊)之邊界之情形評價為○、將不容易視認到之情形評價為×。將結果示於表1。 [嵌入性評價] 將各實施例及比較例中獲得之厚度20 μm之黏晶膜於60℃下貼附於研削為50 μm之矽晶圓，並單片化為10 mm見方之晶片，獲得附黏晶膜之晶片。將該附黏晶膜之晶片於溫度150℃、壓力0.1 MPa、時間1 s之條件下安裝於BGA基板。將其進而於乾燥機中以175℃熱處理1小時。繼而，使用成形機(TOWA PRESS公司製，Manual Press Y-1)，於成形溫度175℃、夾持(clamp)壓力184 kN、轉移壓力5 kN、時間120秒、密封樹脂GE-100(日東電工(股)製)之條件下進行密封步驟。密封步驟後，使用超音波成像裝置(Hitachi Fine-Tech公司製，FS200II)對BGA基板與黏晶膜之界面之空隙進行觀察。利用二值化軟體(WinRoof ver.5.6)算出空隙於觀察圖像中所佔據之面積。將空隙所佔據之面積相對於黏晶膜之表面積未達30%之情形評價為「○」，將為30%以上之情形評價為「×」。 [翹曲評價] 將各實施例及比較例中獲得之厚度5 μm之黏晶膜於60℃下貼附於研削為厚度30 μm之矽晶圓，並單片化(切割)為縱15 mm×橫10 mm尺寸之晶片，獲得附黏晶膜之晶片。 將該附黏晶膜之晶片於溫度150℃、壓力0.1 MPa、時間1 s之條件下安裝於BGA基板。 進而，於所安裝之晶片之上以橫向上錯開300 μm之方式安裝第二個晶片。重複該作業，進行積層直至晶片層數變為4層為止。準備5個該積層體。 將所積層之晶片以能看到晶片橫向之側面之方式設置於顯微鏡，將第1層之晶片之中央與BGA基板間之距離設為零，觀察兩端翹起之程度。具體而言，測定BGA基板與各端部之距離。 算出兩端之翹曲量之平均值。進而算出所製作之5個積層體之平均值。將該平均值未達60 μm者評價為○、將為60 μm以上者評價為×。將結果示於表1。 [冷擴張評價] 使用東京精密股份有限公司製之ML300-Integration作為雷射加工裝置，使聚光點對準12英吋之半導體晶圓之內部，沿格子狀(10 mm×10 mm)之分割預定線照射雷射光，於半導體晶圓之內部形成改質區域。關於雷射光照射條件，以如下方式進行。 (A)雷射光 雷射光源 半導體雷射激發Nd：YAG雷射 波長 1064 nm 雷射光點截面積 3.14×10-8 cm2 振盪形態 Q開關脈衝 重複頻率 100 kHz 脈衝寬度 30 ns 輸出 20 μJ/pulse 雷射光品質 TEM00 40 偏光特性 直線偏光 (B)聚光用透鏡 倍率 50倍 NA 0.55 對雷射光波長之透過率 60% (C)載置半導體基板之裁置台之移動速度 100 mm/s 繼而，將背面研磨用保護帶貼合於半導體晶圓之表面，使用DISCO公司製之背面研磨機DGP8760，對背面進行研削以使半導體晶圓之厚度成為25 μm。 繼而，使進行過利用雷射光之前處理之上述半導體晶圓及切割環貼合於實施例及比較例之切晶黏晶膜(黏晶膜厚度5 μm)。 繼而，使用DISCO公司製之晶片分割機(Die Separator)DDS2300，進行半導體晶圓之割斷及切割片材之熱收縮，藉此獲得樣品。具體而言，首先利用冷擴張單元於擴張溫度-15℃、擴張速度100 mm/s、擴張量12 mm之條件下將半導體晶圓割斷。 然後，利用熱擴張單元於擴張量10 mm、加熱溫度250℃、風量40 L/min、加熱距離20 mm、旋轉速度3°/s之條件下使切割片材熱收縮。 使用所獲得之樣品進行拾取評價。具體而言，使用黏晶機(Die bonder)SPA-300(新川公司製)，於以下之條件下進行拾取。將能夠全部拾取之情形記為○，只要有1個無法拾取之晶片則記為×而進行評價。將結果示於表1。 ＜拾取條件＞ 針(pin)數：5 拾取高度：500 μm 拾取評價數：50個晶片 [表1]The following will describe the viscous crystal film and the cut crystal viscous film of this embodiment. The die-bonding film of this embodiment can be exemplified in a state in which a dicing sheet is not bonded to the die-cutting die-bonding film described below. Therefore, the following is a description of the cut-to-crystal die-bonding film. (Cut Crystal Sticky Film) A cut crystal sticky film according to an embodiment of the present invention will be described below. FIG. 1 is a schematic cross-sectional view showing a cut crystal and sticking film according to an embodiment of the present invention. As shown in FIG. 1, the cut crystal sticky film 10 has a structure in which a sticky film 3 is laminated on a dicing sheet 11. The dicing sheet 11 has a structure in which an adhesive layer 2 is laminated on a base material 1. The adhesive film 3 is disposed on the adhesive layer 2. In addition, in this embodiment, a case where there is a portion 2b in the dicing sheet 11 that is not covered by the die attach film 3 will be described, but the die attach film of the present invention is not limited to this example, and the The die-bonding film is laminated on the cutting sheet so as to cover the entire cutting sheet. (Crystalline film) The tensile storage elastic modulus at 150 ° C of the crystalline film 3 before heat curing is greater than 0.3 MPa and 30 MPa or less, preferably in the range of 0.4 MPa to 25 MPa, and more preferably 0.5 MPa Within the range of -20 MPa. Since the tensile storage elastic modulus at 150 ° C before heat curing is 0.3 MPa or more, even if the wafer is warped, the warpage can be suppressed after sticking the crystal. In addition, since the tensile storage elastic modulus at 150 ° C before thermal curing is 30 MPa or less, the embedding property into the adherend is improved, and the gap between the adherend and the viscous film can be suppressed. In this way, according to the viscous crystal film 3, both active warpage suppression and void embedding can be achieved. The tensile storage elastic modulus at 175 ° C. of the viscous crystal film 3 before thermal curing is preferably in a range of 0.2 MPa to 30 MPa, and more preferably in a range of 0.3 MPa to 25 MPa. The temperature of the sealing step is usually around 175 ° C. Therefore, if the tensile storage elastic modulus at 175 ° C before heat curing is 30 MPa or less, the embedding property under the sealing pressure becomes good, and voids can be suppressed. The tensile storage elastic modulus at 150 ° C. and 175 ° C. of the viscous crystal film 3 before thermal curing can be set within the above-mentioned numerical range, for example, by using a filler described below or adjusting the molecular weight of the thermoplastic resin. The more detailed method for measuring the tensile storage elastic modulus is based on the method described in the examples. It is preferable to set the glass transition temperature (Tg) of the viscous crystal film 3 to T 0 Set the glass transition temperature (Tg) after heat curing to T 1 In this case, the following formula 1 is satisfied. Formula 1 T 0 <T 1 <T 0 +20 If the above formula 1 is satisfied, the difference between the glass transition temperature before thermal curing and the glass transition temperature after thermal curing is small, and it can be said that the change in physical properties before and after thermal curing is small. Therefore, the embedding property to the adherend after applying the thermal history is also good. Above T 1 More preferably less than (T 0 +15), and more preferably less than (T 0 +10). In order for the viscous crystal film 3 to satisfy Formula 1 described above, for example, it may be adjusted so as to reduce the crosslinking of the cured product. In this specification, "after thermosetting" means after heating at 175 ° C for 1 hour. Glass transition temperature T 0 It is preferably in the range of 0 to 70 ° C, and more preferably in the range of 15 to 50 ° C. If the above glass transition temperature T 0 When it is 0 ° C or higher, the viscosity of the viscous crystal film 3 can be suppressed. Moreover, when it is 70 degrees C or less, it can adhere easily to an adherend. Glass transition temperature T 1 It is preferably in the range of 0 to 90 ° C, and more preferably in the range of 15 to 70 ° C. If the above glass transition temperature T 1 If it is within the said numerical value, the said Formula 1 can be easily satisfied. As a result, the insertability to the adherend after heat curing is also good. Above glass transition temperature T 0 Glass transition temperature T 1 It can be made into the desired range by selecting the resin component which comprises the sticky film 3. The more detailed measurement method of the said glass transition temperature (Tg) is based on the method described in an Example. The elongation at break of the viscous crystal film 3 at -15 ° C in a state before thermal curing is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. In the semiconductor device manufacturing steps, Stealth Dicing (registered trademark) or DBG steps are sometimes used. When the elongation at break is 20% or less, the cold expansion property after the stealth cutting or the DBG step is good. In addition, the stealth cutting and DBG steps will be described later. The above elongation at break can be controlled by the material constituting the viscous crystal film 3. For example, it can be controlled by appropriately selecting the type or content of the thermoplastic resin constituting the viscous crystal film 3, the content of the filler, and the like. The method for measuring the elongation at break is based on the method described in the examples. As shown in FIG. 1, the layer structure of the die-bonding film 3 includes a single-layer adhesive layer. In addition, in the present specification, a single layer means a layer composed of the same composition, and includes a laminate of a plurality of layers composed of the same composition. However, the viscous crystal film in the present invention is not limited to this example. For example, it may be a multilayer structure in which two or more kinds of adhesives having different compositions are laminated. The viscous crystal film 3 contains a filler, a thermoplastic resin, and a phenol resin having an average particle diameter in a range of 5 nm to 100 nm. The average particle diameter of the filler is in a range of 5 nm to 100 nm, preferably in a range of 7 nm to 80 nm, and more preferably in a range of 10 nm to 50 nm. Since a filler having an average particle diameter in the range of 5 nm to 100 nm is used, the slime film 3 can be made thin. In addition, since a filler having an average particle diameter in the range of 5 nm to 100 nm is used, the tensile storage elastic modulus of the viscous crystal film 3 can be improved. The measurement method of the average particle diameter of the said filler is based on the method as described in an Example. The maximum particle diameter of the filler is usually required to be less than the thickness of the viscous film 3. The reason is that the filler will protrude from the viscous film, and when the viscous film is bonded to the wafer, the wafer will break. Since the average particle diameter of the above-mentioned filler contained in the viscous crystal film 3 is in a range of 5 nm to 100 nm, the probability of the presence of coarse fillers (fillers having a larger diameter than the thickness of the viscous film 3) is significantly lower. Therefore, for example, the thickness of the sticky film 3 can be set to 5 μm or less. Examples of the filler include inorganic fillers and organic fillers. In terms of a low linear expansion coefficient, inorganic fillers are preferred. The inorganic filler is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, and boric acid. Aluminum whiskers, boron nitride, crystalline silicon dioxide, amorphous silicon dioxide, etc. These can be used alone or in combination of two or more. Among these, crystalline silicon dioxide and amorphous silicon dioxide are preferred from the viewpoint of availability or cost. When the average particle diameter of the filler is set to R and the thickness of the viscous crystal film 3 is set to T, it is preferable to satisfy the following formula 2. Formula 2 10 <T / R When the above formula 2 is satisfied, it is possible to suppress the filler from protruding from the viscous crystal film 3. As a result, it is possible to prevent the wafer from cracking when the die-bond film 3 is bonded to the wafer. The T / R is more preferably 15 or more, and still more preferably 20 or more. The thickness (T) of the adhesive film 3 is preferably 1 to 30 μm, and more preferably 3 to 20 μm. If it is 30 μm or less, it is easy to cut the mucoid film in the cold expansion step. The blending ratio of the filler is preferably 10 to 70% by weight, and more preferably 20 to 60% by weight, with respect to the entire viscous crystal film 3. If the blending ratio of the filler is within a range of 10 to 70% by weight, the elastic modulus will be improved or the severability will be improved. Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, and polybutylene Diene resin, polycarbonate resin, thermoplastic polyimide resin, 6-nylon or 6,6-nylon polyamine resin, phenoxy resin, acrylic resin, PET (polyethylene terephthalate, polyterephthalic acid Saturated polyester resins such as ethylene glycol) or polybutylene terephthalate (polybutylene terephthalate), polyimide resins, or fluororesins. These thermoplastic resins can be used alone or in combination of two or more. Among these thermoplastic resins, an acrylic resin which has less ionic impurities and high heat resistance and can ensure the reliability of a semiconductor device is particularly preferred. Since the die-casting film 3 contains a thermoplastic resin, it can maintain the shape of the film. The acrylic resin is not particularly limited, and examples thereof include one or two types of esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms. A polymer (acrylic copolymer) or the like as a component. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, third butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, cyclohexyl, 2-ethylhexyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, ten Octyl, or dodecyl. The other monomers forming the polymer are not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, and fumarate. Carboxyl-containing monomers such as diacid or butenoic acid; anhydride monomers such as maleic anhydride or itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate 2- Hydroxypropyl ester, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, (formyl) Base) hydroxyl-containing monomers such as 12-hydroxylauryl acrylate or (4-hydroxymethylcyclohexyl) methyl acrylate; styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide Sulfonyl group-containing monomers such as 2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate or (meth) acrylic acid naphthalenesulfonic acid, etc. ; Or a phosphate-containing monomer such as 2-hydroxyethylpropenyl phosphonium phosphate and the like. Among them, the thermoplastic resin is preferably an acrylic polymer having an epoxy group as a functional group. If the thermoplastic resin is an acrylic polymer having an epoxy group, when the adherend is an organic substrate, it can be reliably achieved by reacting with an unreacted epoxy resin or a phenol resin existing on the organic substrate. Sexual improvement. In addition, it can also react with the sealing resin to improve reliability. The blending ratio of the thermoplastic resin is preferably in the range of 10 to 90% by weight, and more preferably 15 to 90% by weight based on the viewpoint of increasing the elastic modulus at high temperature before curing. Within 60% by weight. The weight average molecular weight of the thermoplastic resin is preferably 500,000 to 1700,000, and more preferably 600,000 to 1500,000. When the molecular weight of the thermoplastic resin in the die-casting film 3 is 500,000 or more, the cohesive force of the polymer chains increases. As a result, it becomes difficult to extend, and the severability at the time of cold expansion improves. On the other hand, if the molecular weight is 1700,000 or less, the synthesis of the polymer is easy. In this specification, a weight average molecular weight means the value measured by the following method. <Measurement of weight average molecular weight Mw> Measurement of weight average molecular weight Mw was performed by GPC (gel permeation chromatography). The measurement conditions are as follows. The weight average molecular weight is calculated in terms of polystyrene. Measuring device: HLC-8120GPC (product name, manufactured by TOSOH); column: TSKgel GMH-H (S) × 2 (product model, manufactured by TOSOH); flow rate: 0.5 ml / min; injection volume: 100 μl; column temperature: 40 ℃ Eluent: THF Injection sample concentration: 0.1% by weight Detector: Differential refractometer Examples of the above phenol resins are phenol novolac resin, phenol aralkyl resin, cresol novolac resin, third butyl novolac resin Novolac-type phenol resins such as resins, nonylphenol novolac resins; soluble phenol-type phenol resins, polyhydroxystyrenes such as poly-p-hydroxystyrene, etc. These can be used alone or in combination of two or more. Among these phenol resins, phenol novolak resin and phenol aralkyl resin are particularly preferred. This is because the connection reliability of the semiconductor device can be improved. Since it contains a phenol resin, it has excellent reliability. From the viewpoint of reliability, the blending ratio of the phenol resin is preferably in the range of 1 to 35% by weight, and more preferably in the range of 3 to 20% by weight, with respect to the entire sticky film 3. If it exists in the said numerical range, since reaction with another component will fully advance, reliability can be improved. The sticky film 3 preferably contains a colorant. Since the viscous crystal film 3 uses a filler having an average particle diameter in a range of 5 nm to 100 nm, there is a possibility that the viscous crystal film 3 has transparency and visibility may be reduced. Therefore, if a coloring agent is included, visibility of the viscous crystal film 3 can be improved, and workability can be improved. Examples of the colorant include pigments and dyes. These colorants can be used alone or in combination of two or more. In addition, as the dye, a dye in any form such as an acid dye, a reactive dye, a direct dye, a disperse dye, and a cationic dye can be used. The form of the pigment is not particularly limited, and it can be appropriately selected and used from known pigments. Among these, a dye is preferable. When a dye is used, it is easy to dissolve in the resin constituting the viscous crystal film 3, and it is possible to uniformly color. When a solvent is used in the production of the viscous crystal film 3, it is easy to dissolve in the solvent and can uniformly color. From the viewpoint of not requiring dispersion, a dye having excellent solubility is preferred. In the case where the viscous film 3 of the present invention is cross-linked to a certain degree in advance, a polyfunctional compound that reacts with a functional group at the end of the molecular chain of the polymer and the like may be added in advance as a cross-linking agent. Thereby, the adhesion characteristics at high temperatures can be improved, and heat resistance can be improved. As the crosslinking agent, a conventionally known one can be used. In particular, polyisocyanate compounds such as toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, and an adduct of a polyol and a diisocyanate are more preferred. The addition amount of the crosslinking agent is preferably 0.05 to 7 parts by weight based on 100 parts by weight of the polymer. If the amount of the cross-linking agent is more than 7 parts by weight, the adhesive force is lowered, which is not preferable. On the other hand, if the content is less than 0.05 parts by weight, cohesion is insufficient, which is not preferable. Moreover, you may contain other polyfunctional compounds, such as an epoxy resin, with such a polyisocyanate compound as needed. Moreover, other additives may be appropriately blended in the viscous crystal film 3 as needed. Examples of the other additives include a flame retardant, a silane coupling agent, and an ion trapping agent. Examples of the flame retardant include antimony trioxide, antimony pentoxide, and brominated epoxy resin. These can be used alone or in combination of two or more. Examples of the silane coupling agent include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyl Methyldiethoxysilane and the like. These compounds can be used alone or in combination of two or more. Examples of the ion trapping agent include hydrotalcites and bismuth hydroxide. These can be used alone or in combination of two or more. Furthermore, from the viewpoint of improving reliability, a small amount of epoxy resin may be contained in the adhesive film 3. However, since the epoxy resin has a low molecular weight, if a large amount of the epoxy resin is contained in the viscous film 3, the elastic modulus before heat curing is reduced. In addition, since the hardening component increases, the embedding property after heat curing is reduced. Therefore, it is preferable that the die-bond film 3 does not contain an epoxy resin. (Cutting sheet) The dicing sheet 11 of this embodiment has a structure in which an adhesive layer 2 is laminated on a base material 1. Wherein, the dicing sheet of the present invention is not limited to this example, as long as the viscous film 3 can be fractured during the cold expansion step to be singulated. For example, there may be other layers between the substrate and the adhesive layer. (Base material) The base material 1 is preferably one having ultraviolet light permeability, and serves as a strength matrix of the cut-crystal cement film 10. Examples include: low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra-low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolypropylene, polybutylene Polyolefin such as olefin, polymethylpentene, ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid (random, alternating) copolymer , Polyesters such as ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide , Polyether ether ketone, polyimide, polyether imide, polyimide, fully aromatic polyimide, polyphenylene sulfide, aromatic polyimide (paper), glass, glass cloth, fluororesin, Polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, metal (foil), paper, etc. Examples of the material of the substrate 1 include polymers such as a crosslinked body of the above resin. The above plastic film can be used in an unstretched state, and a uniaxial or biaxial stretching process can also be used as required. According to the resin sheet which has been provided with heat shrinkability by a stretching process or the like, the semiconductor wafer on the base material 1 is subjected to heat shrinkage (thermal expansion) after cold expansion, so that the semiconductor with the adhesive film 3 can be enlarged. The interval between the wafers 5 facilitates recovery of the semiconductor wafers 5. The surface of the substrate 1 may be subjected to conventional surface treatments, such as chemical or physical treatments such as chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, and the like, using a primer (such as an adhesive substance described later). Cloth treatment to improve the adhesion and retention with adjacent layers. The base material 1 can be selected from the same kind or different kinds, and can be used by mixing several kinds as needed. In addition, in order to impart antistatic ability to the substrate 1, a vapor-deposited layer containing a conductive material having a thickness of about 30 to 500 Å, including a metal, an alloy, and an oxide thereof, may be provided on the substrate 1. The substrate 1 may be a single layer or a multilayer of two or more types. The thickness of the substrate 1 is not particularly limited, and can be appropriately determined, and is usually about 5 to 200 μm. (Adhesive layer) The adhesive used in the formation of the adhesive layer 2 is not particularly limited. For example, an ordinary pressure-sensitive adhesive such as an acrylic adhesive or a rubber adhesive can be used. As the pressure-sensitive adhesive, it is preferable to use an acrylic polymer as a base in terms of cleaning and decontamination of an electronic component such as a semiconductor wafer or glass that avoids contamination by using ultrapure water or an organic solvent such as alcohol. Polymeric acrylic adhesive. Examples of the acrylic polymer include acrylic polymers using one or two or more of the following components as monomer components: alkyl (meth) acrylates (e.g., methyl esters, ethyl esters, and propyl esters) , Isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl Ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, cetyl ester, octadecyl ester, eicosyl ester Etc. The alkyl group has a carbon number of 1 to 30, especially a linear or branched alkyl ester having a carbon number of 4 to 18, etc.) and a cycloalkyl (meth) acrylate (e.g., cyclopentyl, cyclo Hexyl ester, etc.). In addition, (meth) acrylate means an acrylate and / or a methacrylate, and all (meth) in this invention has the same meaning. For the purpose of improving cohesion, heat resistance, etc., the above-mentioned acrylic polymer may also include units corresponding to other monomer components that can be copolymerized with the (meth) acrylic acid alkyl ester or cycloalkyl ester as required. . Examples of such monomer components include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, and fumaric acid. And carboxyl-containing monomers such as butene acid; anhydride monomers such as maleic anhydride and itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate , (4-hydroxymethylcyclohexyl) methyl (meth) acrylate and other hydroxyl-containing monomers; styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid Sulfonic acid group-containing monomers such as acids, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, and (meth) acrylamidooxynaphthalenesulfonic acid; 2-hydroxyethylacrylamidophosphoric acid Phosphate-containing monomers such as esters; acrylamide, acrylonitrile, and the like. These copolymerizable monomer components may be used singly or in combination of two or more kinds. The amount of these copolymerizable monomers is preferably 40% by weight or less of the total monomer components. Furthermore, the said acrylic polymer may contain a polyfunctional monomer etc. as a monomer component for copolymerization, and may be bridge | crosslinked as needed. Examples of such a polyfunctional monomer include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (methyl) Acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, (meth) acrylate urethane, and the like. These polyfunctional monomers may be used alone or in combination of two or more. In terms of adhesive properties and the like, the use amount of the polyfunctional monomer is preferably 30% by weight or less of the total monomer components. The acrylic polymer can be obtained by polymerizing a single monomer or a mixture of two or more monomers. The polymerization can be performed in any manner such as solution polymerization, emulsion polymerization, block polymerization, and suspension polymerization. In terms of preventing contamination of the clean adherend, etc., it is preferable that the content of the low-molecular-weight substance is small. In this respect, the number average molecular weight of the acrylic polymer is preferably 300,000 or more, and more preferably about 400,000 to 3 million. Moreover, in the said adhesive agent, in order to raise the number average molecular weight of an acrylic polymer etc. which are a base polymer, an external crosslinking agent can also be used suitably. Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, and a melamine-based crosslinking agent to perform a reaction. When an external cross-linking agent is used, the amount used is appropriately determined according to the balance with the base polymer to be cross-linked, and further according to the use application as an adhesive. Usually, it is preferable to mix | blend about 5 weight part or less with respect to 100 weight part of said base polymers, and also 0.1 to 5 weight part. Furthermore, in the adhesive, additives such as various conventionally known adhesion-imparting agents and anti-aging agents may be used in addition to the aforementioned components, if necessary. The adhesive layer 2 may be formed using a radiation-curable adhesive. When the ultraviolet ray is irradiated in a state where the viscous crystal film 3 is bonded, an anchor effect can be generated between the viscous film 3 and the viscous film 3. Thereby, the adhesiveness of the adhesive layer 2 and the adhesive film 3 at low temperature (for example, -15 degreeC) can be improved. Furthermore, the lower the temperature, the higher the adhesion based on the anchoring effect. Although there is an anchoring effect at normal temperature (for example, 23 ° C), compared with low temperature, the adhesion based on the anchoring effect is not exhibited at normal temperature. The radiation-curable adhesive can be used without any particular limitation to those having a radiation-curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness. As the radiation-hardening adhesive, for example, an addition-type radiation curing in which a radiation-hardening monomer component or an oligomer component is blended into a general pressure-sensitive adhesive such as the above-mentioned acrylic adhesive and rubber-based adhesive can be exemplified. Type adhesive. Examples of the radiation-curable monomer component include urethane oligomers, (meth) acrylate urethanes, trimethylolpropane tri (meth) acrylate, and Hydroxymethylmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylic acid Esters, 1,4-butanediol di (meth) acrylate, and the like. Examples of the radiation-hardening oligomer component include various oligomers such as urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based, and the molecular weight thereof is preferably 100. Those in the range of ~ 30,000. Regarding the blending amount of the radiation-curable monomer component or oligomer component, an amount capable of reducing the adhesive force of the adhesive layer can be appropriately determined according to the type of the adhesive layer. Usually, it is 5 to 500 weight part with respect to 100 weight part of base polymers, such as an acrylic polymer which comprises an adhesive agent, Preferably it is about 40 to 150 weight part. In addition, as the radiation-curable adhesive, in addition to the additive-type radiation-curable adhesive described above, there can also be mentioned polymers for which a carbon-carbon double bond is present in a polymer side chain, or in a main chain or a main chain end. Used as a base polymer internal radiation hardening adhesive. Since the internal radiation-hardening adhesive does not need to contain or contains a large amount of oligomer components and the like as low molecular components, the oligomer components and the like do not move in the adhesive over time and can form a stable layer structure. An adhesive layer is preferred. The above-mentioned base polymer having a carbon-carbon double bond can be used without particular limitation as one having a carbon-carbon double bond and having adhesiveness. As such a base polymer, an acrylic polymer is preferably used as a basic skeleton. Examples of the basic skeleton of the acrylic polymer include the acrylic polymers exemplified above. The method of introducing the carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be adopted. The method of introducing the carbon-carbon double bond to the polymer side chain is relatively easy in terms of molecular design. For example, the following method can be cited: an acrylic polymer and a monomer having a functional group are copolymerized in advance, and then a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is used to maintain the carbon-carbon double bond. Condensation or addition reaction proceeds in a state of radiation hardening. Examples of the combination of these functional groups include a carboxylic acid group and an epoxy group, a carboxylic acid group and an aziridinyl group, a hydroxyl group and an isocyanate group, and the like. In terms of ease of reaction tracking, among the combinations of these functional groups, a combination of a hydroxyl group and an isocyanate group is preferred. In addition, as long as the combination of the above-mentioned acrylic polymer having a carbon-carbon double bond is generated by a combination of these functional groups, the functional group may be located on either side of the acrylic polymer and the above-mentioned compound. In a preferred combination, the case where the acrylic polymer has a hydroxyl group and the aforementioned compound has an isocyanate group is preferred. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacrylfluorenyl isocyanate, 2-methacryloxyethyl isocyanate, and m-isopropenyl-α, α-dimethyl. Benzyl isocyanate and the like. In addition, as the acrylic polymer, a hydroxyl group-containing monomer exemplified above, an ether-based compound such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether can be copolymerized. Made of polymers. The above-mentioned intrinsic radiation-hardening adhesive can be used alone as the base polymer (especially an acrylic polymer) having a carbon-carbon double bond, and the radiation-hardening monomer can be blended to the extent that the characteristics are not deteriorated. Ingredient or oligomer ingredient. The radiation-curable oligomer component and the like are generally within a range of 30 parts by weight, and preferably within a range of 0 to 10 parts by weight based on 100 parts by weight of the base polymer. The radiation-curable adhesive contains a photopolymerization initiator when it is cured by ultraviolet rays or the like. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) one, α-hydroxy-α, α'-dimethylacetophenone Α-keto alcohol compounds such as 1,2-methyl-2-hydroxyphenylacetone, 1-hydroxycyclohexylphenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone Ketones, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-&#134156;Compounds; Benzoin ether compounds such as benzoin diethyl ether, benzoin isopropyl ether, and anisin methyl ether; ketal compounds such as benzoin dimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride ; Photoactive oxime compounds such as 1-benzophenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; benzophenone, benzamidinebenzoic acid, 3,3'-dimethylformaldehyde Benzophenone-based compounds such as methyl-4-methoxybenzophenone; 9-oxysulfur &#134079; , 2-chloro-9-oxysulfur &#134079; , 2-methyl-9-oxysulfur &#134079; , 2,4-dimethyl-9-oxysulfur &#134079; , Isopropyl-9-oxysulfur &#134079; , 2,4-dichloro-9-oxysulfur &#134079; , 2,4-diethyl-9-oxysulfur &#134079; , 2,4-diisopropyl-9-oxysulfur &#134079; 9-oxysulfur &#134079; Compounds; camphorquinone; halogenated ketones; fluorenyl phosphine oxide; fluorenyl phosphonate and the like. The blending amount of the photopolymerization initiator is, for example, about 0.05 to 20 parts by weight based on 100 parts by weight of the base polymer such as the acrylic polymer constituting the adhesive. Examples of the radiation-curable adhesive include rubber-based adhesives and acrylic adhesives disclosed in Japanese Patent Laid-Open No. Sho 60-196956. These include the addition of two or more unsaturated bonds. Photopolymerizable compounds such as polymerizable compounds, alkoxysilanes having epoxy groups, and photopolymerization initiators such as carbonyl compounds, organic sulfur compounds, peroxides, amines, and onium salt-based compounds. The thickness of the adhesive layer 2 is not particularly limited, and it is preferably about 1 to 50 μm, and more preferably 2 to, in terms of the prevention of defects on the cut surface of the wafer and the fixation of the adhesive film 3. 30 μm, more preferably 5 to 25 μm. The die-bonding film 3 of the above-mentioned cut-die-bonding film 10 is preferably protected by an isolation film (not shown). The isolation film has a function as a protective material for protecting the die-bond film 3 before being used for actual use. In addition, the release film can be used as a supporting substrate when transferring the adhesive film 3 to the adhesive layer 2. The isolation film is peeled off when the workpiece is attached to the die-bond film 3 of the cut-die-bond film. As the release film, the surface may be coated with polyethylene terephthalate (PET), polyethylene, polypropylene, or a release agent such as a fluorine-based release agent or a long-chain alkyl acrylate-based release agent. Plastic film or paper. The dicing die-bonding film 10 of this embodiment can be produced, for example, as follows. First, the substrate 1 can be formed into a film by a conventionally known film forming method. Examples of the film forming method include a calendering method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a coextrusion method, and a dry layer. Press method and so on. Next, after the adhesive composition solution is applied on the substrate 1 to form a coating film, the coating film is dried under specific conditions (heat-crosslinked as necessary) to form a precursor layer. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. The drying conditions are performed, for example, in a range of a drying temperature of 80 to 150 ° C and a drying time of 0.5 to 5 minutes. Alternatively, after the adhesive composition is applied to the release film to form a coating film, the coating film is dried under the drying conditions to form the precursor layer. Then, the above-mentioned precursor layer is bonded to the substrate 1 together with the separator. Thereby, a dicing sheet precursor is produced. The die attach film 3 can be produced, for example, as follows. First, an adhesive composition solution is prepared as a material for forming the sticky film 3. In this adhesive composition solution, the above-mentioned adhesive composition, filler, various other additives, etc. are prepared as described above. Then, after the adhesive composition solution is applied to the base material separator film to have a specific thickness to form a coating film, the coating film is dried under specific conditions to form a sticky crystal film 3. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. The drying conditions are performed, for example, in a range of a drying temperature of 70 to 160 ° C and a drying time of 1 to 5 minutes. Alternatively, after the adhesive composition solution is applied on the release film to form a coating film, the coating film is dried under the above-mentioned drying conditions to form the viscous crystal film 3. Then, the die-bond film 3 and the release film are bonded together on the substrate release film. Then, the release film is peeled from the above-mentioned dicing sheet precursor and the adhesive film 3, respectively, and the adhesive film 3 and the adhesive layer are bonded to each other in such a manner that they are bonded together. Bonding can be performed, for example, by pressure bonding. In this case, the lamination temperature is not particularly limited, but is preferably 30 to 50 ° C, more preferably 35 to 45 ° C. The line pressure is not particularly limited, but is preferably 0.1 to 20 kgf / cm, more preferably 1 to 10 kgf / cm. Then, ultraviolet rays may be irradiated from the substrate 1 side. As the irradiation amount of ultraviolet rays, it is preferable to set the peeling force A and the peeling force B within the above-mentioned numerical range. The specific amount of ultraviolet radiation varies depending on the composition or thickness of the adhesive layer, and is preferably 50 mJ to 500 mJ, more preferably 100 mJ to 300 mJ. In the above manner, the cut crystal and sticking film of this embodiment is obtained. (Manufacturing Method of Semiconductor Device) Next, a manufacturing method of a semiconductor device using a cut die-bond film 10 will be described with reference to FIGS. 2 to 5, 7, and 8. The method for manufacturing a semiconductor device according to this embodiment includes at least the following steps: step A, attaching a semiconductor wafer to a dicing die-bonding film; step B, expanding the dicing die-bonding film and at least breaking the dicing-die film, Obtain a wafer with a sticky crystal film; Step C, pick up the wafer with a sticky crystal film; Step D, stick the picked up wafer with the sticky crystal film to the adherend through the sticky film; and Step E, The above-mentioned wafer with a sticky crystal film is wire-bonded; and the above-mentioned cut-crystal die-bond film contains: a filler having an average particle diameter in a range of 5 nm to 100 nm, a thermoplastic resin, and a phenol resin, and is heated at 150 ° C before being cured. The tensile storage elastic modulus is greater than 0.3 MPa and less than 30 MPa. In the following, first, the case where the die-cutting die-bonding film is expanded, the die-bonding film and the modified semiconductor wafer are simultaneously fractured to obtain a wafer with a die-attaching film (stealth dicing) will be described. 2 to 5 are schematic cross-sectional views for explaining a method for manufacturing a semiconductor device according to this embodiment. First, laser light is irradiated on the planned division line 4L of the semiconductor wafer 4 to form a modified region on the planned division line 4L (see FIG. 2). This method is as follows: aligning the light-condensing point on the inside of the semiconductor wafer, irradiating laser light along a predetermined grid-shaped division line, and forming a modified region inside the semiconductor wafer by ablation based on multiphoton absorption. The laser light irradiation conditions may be appropriately adjusted within the range of the following conditions. ＜ Laser Light Irradiation Conditions ＞ (A) Laser Light Laser Source Semiconductor Laser Excitation Nd: YAG Laser Wavelength 1064 nm Laser Spot Cross Section Area 3.14 × 10 -8 cm 2 Oscillation type Q switching pulse repetition frequency below 100 kHz Pulse width below 1 μs Laser output quality below 1 mJ Laser quality TEM00 Polarization characteristics Linear polarization (B) Condensing lens magnification of 100 times or less NA 0.55 Transmission of laser light wavelength of 100% or less (C) The moving speed of the cutting table on which the semiconductor substrate is placed is below 280 mm / s. Further, a method for forming a modified region on the predetermined division line 4L by irradiating laser light is disclosed in Japanese Patent No. 3408805, Japanese Patent Special Since it is described in detail in Japanese Patent Publication No. 2003-338567, the detailed description is omitted here. Then, as shown in FIG. 3, the semiconductor wafer 4 after the modified region is formed is crimped to the die-bond film 3, and then it is held and fixed (mounting step). This step corresponds to step A of the present invention. This step is performed while pressing is performed by a pressing mechanism such as a crimping roller. There is no particular limitation on the attaching temperature during installation, but it is preferably within a range of 40 to 80 ° C. The reason for this is that it is possible to effectively prevent warping of the semiconductor wafer 4 and to reduce the influence of the expansion and contraction of the cut-to-die bond film. Then, the semiconductor wafer 4 and the die-bond film 3 are fractured along a predetermined division line 4L by applying a tensile tension to the die-bond die-bond film 10 to form a semiconductor wafer 5 (cold expansion step). This step corresponds to step B of the present invention. In this step, for example, a commercially available wafer expansion device can be used. Specifically, as shown in FIG. 4 (a), a dicing ring 31 is attached to the peripheral portion of the adhesive layer 2 of the die-bonding film 10 to which the semiconductor wafer 4 is bonded, and then fixed to the wafer expansion device 32. Then, as shown in FIG. 4 (b), the raised portion 33 is raised, and tension is applied to the cut-to-size die-bond film 12. The above-mentioned cold expansion step is preferably performed under the condition of 0 to -15 ° C, and more preferably performed under the condition of -5 to -15 ° C. Since the cold expansion step is performed under the condition of 0 to -15 ° C, the viscous crystal film 3 can be preferably broken. In the cold expansion step, the expansion speed (the speed at which the jacking portion rises) is preferably 100 to 400 mm / s, more preferably 100 to 350 mm / s, and even more preferably 100 to 300 mm / s. When the expansion speed is set to 100 mm / s or more, the semiconductor wafer 4 and the die-bond film 3 can be easily fractured at substantially the same time. Further, if the expansion speed is set to 400 mm / s or less, the cutting sheet 11 can be prevented from being broken. In the cold expansion step, the expansion amount is preferably 4 to 16 mm. The above-mentioned expansion amount can be appropriately adjusted according to the size of the formed wafer within the above-mentioned numerical range. If the expansion amount is 4 mm or more, the semiconductor wafer 4 and the die-bond film 3 can be more easily broken. Further, if the expansion amount is 16 mm or less, it is possible to further prevent the dicing sheet 11 from being broken. In this way, by applying a tensile tension to the slicing die-bonding film 10, a crack can be generated in the thickness direction of the semiconductor wafer 4 starting from the modified region of the semiconductor wafer 4, and the adhesion to the semiconductor wafer 4 can be made tight. The crystal film 3 is broken, so that the semiconductor wafer 5 with the adhesive crystal film 3 can be obtained. Then, a thermal expansion step is performed as necessary. In the thermal expansion step, the dicing sheet 11 is heated outside of the portion to which the semiconductor wafer 4 is attached to cause thermal contraction. As a result, the distance between the semiconductor wafers 5 is increased. The conditions in the thermal expansion step are not particularly limited, but are preferably set to: an expansion amount of 4 to 16 mm, a heating temperature of 200 to 260 ° C, a heating distance of 2 to 30 mm, and a rotation speed of 3 ° / s to 10 ° / s Within range. The thermal expansion step is not limited to this example. For example, the thermal expansion step may be a step including the following steps (1) to (3). (1) After the cold expansion step, first, the cutting sheet 11 is expanded by a heating stage. Thereby, the slackness of the dicing sheet 11 is eliminated, and the distance between the semiconductor wafers 5 is increased. (2) Then, the portion of the dicing sheet 11 to which the semiconductor wafer 4 is attached is adsorbed on a heating stage, so that the state where the wafer interval is enlarged can be maintained. (3) Next, the dicing sheet 11 is heated outside the portion to which the semiconductor wafer 4 is attached to cause heat shrink. Then, a cleaning step is performed as necessary. In the cleaning step, the dicing sheet 11 in a state where the semiconductor wafer 5 with the adhesive crystal film 3 is fixed is set in a spin coater. Then, the spin coater was rotated while the cleaning liquid was dropped onto the semiconductor wafer 5. Thereby, the surface of the semiconductor wafer 5 is cleaned. Examples of the washing liquid include water. The rotation speed or rotation time of the spin coater varies depending on the type of the cleaning liquid, and can be set to, for example, a rotation speed of 400 to 3000 rpm and a rotation time of 1 to 5 minutes. Then, the semiconductor wafer 5 is picked up (pickup step) in order to peel off the semiconductor wafer 5 which is then fixed to the die-bonding film 10. This step corresponds to step C of the present invention. There is no particular limitation on the method of picking up, and various conventionally known methods can be adopted. For example, a method may be used in which each semiconductor wafer 5 is lifted from the side of the die-cut die-bond film 10 with a needle, and the lifted semiconductor wafer 5 is picked up by a pick-up device. Then, as shown in FIG. 5, the picked-up semiconductor wafer 5 is die-bonded to the adherend 6 via the die-bond film 3 (temporary fixing step). This step corresponds to step D of the present invention. Examples of the adherend 6 include a lead frame, a TAB film, a substrate, and a separately manufactured semiconductor wafer. The adherend 6 may be, for example, a deformable adherend that is easily deformed, or a non-deformable adherend (such as a semiconductor wafer) that is not easily deformed. As the substrate, a conventionally known one can be used. Further, as the lead frame, a metal lead frame such as a Cu lead frame, a 42 alloy lead frame, or glass-epoxy, BT (bismaleimide-tri &#134116;), Organic substrates such as polyimide. However, the present invention is not limited to this, and also includes a circuit board which can be used for fixing and electrically connecting a semiconductor element to the semiconductor element. The shear adhesive force at 25 ° C. during the temporary fixing of the viscous crystal film 3 is preferably 0.2 MPa or more and more preferably 0.2 to 10 MPa relative to the adherend 6. If the bonding force of the die-bonding film 3 is at least 0.2 MPa or more, in the wire bonding step, the die-bonding film 3 and the semiconductor wafer 5 or the adherend 6 are rarely caused by the ultrasonic vibration or heating in this step. The contact surface is offset and deformed. That is, the semiconductor element rarely moves due to ultrasonic vibration during wire bonding, thereby preventing the success rate of wire bonding from decreasing. In addition, the shear adhesion force at 175 ° C. at the time of temporary fixing of the viscous crystal film 3 is preferably 0.01 MPa or more, and more preferably 0.01 to 5 MPa relative to the adherend 6. Next, wire bonding (wire bonding step) for electrically connecting the front end of the terminal portion (internal lead) of the adherend 6 and an electrode pad (not shown) on the semiconductor wafer 5 with a bonding wire 7 is performed (wire bonding step). This step corresponds to step E of the present invention. As the bonding wire 7, for example, a gold wire, an aluminum wire, or a copper wire is used. The temperature at the time of wire bonding is performed in the range of 80 to 250 ° C, preferably 80 to 220 ° C. The heating time is performed for several seconds to several minutes. The wiring is performed by using the vibration energy based on the ultrasonic wave and the crimping energy based on the application of pressure in a state of being heated to the temperature range described above. This step is performed in a state in which the thermosetting of the viscous crystal film 3 is not performed. In addition, during this step, the semiconductor wafer 5 and the adherend 6 will not be fixed by the adhesive film 3. Then, the semiconductor wafer 5 is sealed with the sealing resin 8 (sealing step). This step is performed to protect the semiconductor wafer 5 and the bonding wire 7 mounted on the adherend 6. This step is performed by molding a sealing resin with a mold. As the sealing resin 8, for example, an epoxy resin is used. The heating temperature at the time of resin sealing is usually performed at 175 ° C for 60 to 90 seconds, but the present invention is not limited to this. For example, it can be cured at 165 to 185 ° C for several minutes. Thereby, the sealing resin is hardened, and the semiconductor wafer 5 and the adherend 6 are fixed to each other via the adhesive film 3. That is, in the present invention, even when the post-hardening step described later is not performed, the fixation by the adhesive film 3 can be achieved in this step, which can help reduce the number of manufacturing steps and shorten the manufacturing time of the semiconductor device. . The sealing step is not limited to this example, and a step of embedding the semiconductor wafer 5 in the sealing sheet by, for example, parallel plate pressing using a sheet-shaped sealing resin (sealing sheet) may be used. In the post-curing step, the sealing resin 8 that is not sufficiently cured in the sealing step is completely cured. Even in the case where the viscous crystal film 3 is not completely thermally cured in the sealing step, the viscous crystal film 3 and the sealing resin 8 can be completely thermally cured together in this step. The heating temperature in this step varies depending on the type of the sealing resin. For example, the heating temperature is in the range of 165 to 185 ° C, and the heating time is about 0.5 to 8 hours. Furthermore, the dicing die-bonding film of the present invention can also be suitably used when a plurality of semiconductor wafers are laminated for three-dimensional mounting. At this time, the adhesive film and the spacer may be laminated between the semiconductor wafers, or only the adhesive film and not the spacer may be laminated between the semiconductor wafers, and may be appropriately changed according to manufacturing conditions or applications. Hereinafter, a semiconductor device in which a plurality of semiconductor wafers are stacked will be briefly described. FIG. 6 is a schematic cross-sectional view showing another example of the semiconductor device of this embodiment. In the semiconductor device shown in FIG. 6, a semiconductor wafer 5 is laminated on an adherend 6 via a die attach film 3, and a semiconductor wafer 15 is laminated on the semiconductor wafer 5 via a die attach film 13. The semiconductor wafer 15 is smaller than the semiconductor wafer 5 in a plan view. An electrode pad (not shown) formed on the upper surface of the semiconductor wafer 5 is exposed from the semiconductor wafer 15 in a plan view. An electrode pad formed on the upper surface of the semiconductor wafer 5 and a terminal portion (not shown) of the adherend 6 are electrically connected by a bonding wire 7. In addition, an electrode pad (not shown) formed on the upper surface of the semiconductor wafer 15 and a terminal portion (not shown) of the adherend 6 are electrically connected by a bonding wire 7. The semiconductor wafer 5 and the semiconductor wafer 15 are sealed with a sealing resin 8. The viscous film 13 may have the same composition as the viscous film 3, or may have a different composition from the viscous film 3 within the range described in the item of the viscous film. An example of a semiconductor device in which a plurality of semiconductor wafers are stacked has been described above. Next, a method for manufacturing a semiconductor device using a step of forming grooves on the surface of a semiconductor wafer and then performing back surface grinding (DBG step: Dicing Before Grinding) will be described below. 7 and 8 are schematic cross-sectional views for explaining another method of manufacturing the semiconductor device according to this embodiment. First, as shown in FIG. 7 (a), a groove 4S that does not reach the back surface 4R is formed on the surface 4F of the semiconductor wafer 4 by using a rotary blade 41. Furthermore, when the groove 4S is formed, the semiconductor wafer 4 is supported by a supporting substrate (not shown). The depth of the groove 4S can be appropriately set according to the thickness or expansion conditions of the semiconductor wafer 4. Then, as shown in FIG. 7 (b), the semiconductor wafer 4 is supported by the protective substrate 42 so that the surface 4F abuts. Then, the back surface is ground using the grinding stone 45 to expose the groove 4S from the back surface 4R. In addition, a conventionally known attachment device can be used for attaching the protective substrate 42 to the semiconductor wafer, and a previously known grinding device can be used for back grinding. Then, as shown in FIG. 8, the semiconductor wafer 4 with the groove 4S exposed is crimped on the die-bonding die film 10 and then held and fixed. This step corresponds to step A of the present invention. Then, the protective substrate 42 is peeled off, and tension is applied to the dicing die-bonding film 10 by the wafer expanding device 32. Thereby, the die-bond film 3 is broken, and a semiconductor wafer 5 is formed (wafer formation step). This step corresponds to step B of the present invention. The temperature, expansion speed, and expansion amount in the wafer formation step are the same as those in the case where a modified region is formed on the planned division line 4L by irradiating laser light. The subsequent steps are the same as those in the case where a modified region is formed on the planned division line 4L by irradiating the laser light, so the description here is omitted. The method for manufacturing a semiconductor device according to this embodiment is not limited to the above embodiment as long as the semiconductor wafer and the die-bond film are simultaneously fractured in the cold expansion step, or only the die-bond film is fractured in the cold expansion step. As another embodiment, for example, as shown in FIG. 7 (a), a groove 4S that does not reach the back surface 4R may be formed on the surface 4F of the semiconductor wafer 4 by using the rotary blade 41, and then bonded to the die-bonding die-bonding film. The semiconductor wafer 4 of the groove 4S is exposed and then held and fixed (temporary fixing step). Then, the wafer die-bonding film is tensioned by the wafer expanding device. Thereby, in the portion of the groove 4S, the semiconductor wafer 4 and the die-bond film 3 are fractured to form a semiconductor wafer 5. However, the manufacturing method of the semiconductor device of the present invention is not limited to this example. For example, the method for manufacturing a semiconductor device may include the following steps: Step A, attaching a semiconductor wafer to a dicing die-bonding film; and step X, attaching the semiconductor wafer and the die-bonding film by a blade. Cutting together to obtain a wafer with a crystal film; step C, picking up the wafer with a crystal film; step D, crystallizing the picked wafer with a film to the adherend through the crystal film; and, In step E, wire bonding is performed on the wafer with the attached crystal film. [Examples] Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to the following examples as long as the gist is not exceeded. In each example, parts are based on weight unless otherwise specified. (Example 1) <Production of cut sheet> 100 parts of 2-ethylhexyl acrylate (hereinafter, also referred to as "2EHA") was added to a reaction vessel provided with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device, 19 parts of 2-hydroxyethyl acrylate (hereinafter, also referred to as "HEA"), 0.4 parts of benzoyl peroxide, and 80 parts of toluene were polymerized at 60 ° C for 10 hours in a nitrogen gas stream to obtain an acrylic polymer A . 1.2 parts of 2-methacryloxyethyl isocyanate (hereinafter, also referred to as "MOI") was added to the acrylic polymer A, and an addition reaction treatment was performed at 50 ° C for 60 hours in an air stream to obtain acrylic acid. Polymer A '. Next, 1.3 parts of a polyisocyanate compound (trade name "CORONATE L", manufactured by Nippon Polyurethane (stock)) and a photopolymerization initiator (trade name "Irgacure 184", Ciba) were added to 100 parts of the acrylic polymer A '. Specialty Chemicals Co., Ltd.) 3 parts to prepare an adhesive solution (also referred to as "adhesive solution A"). The adhesive solution A prepared above was coated on the surface of the PET release liner on which the polysiloxane treatment was performed, and dried at 120 ° C. for 2 minutes to form an adhesive layer A having a thickness of 10 μm. Then, an EVA film (ethylene-vinyl acetate copolymer film) manufactured by GUNZE Co., Ltd. with a thickness of 125 μm was bonded to the exposed surface of the adhesive layer A, and stored at 23 ° C. for 72 hours to obtain a cut sheet A. <Preparation of a Sticky Crystal Film> The following (a) to (d) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution A having a solid content concentration of 18% by weight. (a) Acrylic resin (trade name "SG-P3", manufactured by Nagase ChemteX, molecular weight 850,000): 100 parts (b) phenol resin (trade name "MEH-7851ss", manufactured by Meiwa Chemical Co., Ltd.): 12 parts (c ) Filler A (trade name "YA010C-SP3", manufactured by Admatechs Co., Ltd., average particle size 10 nm): 100 parts (d) colorant (trade name "OIL SCARLET 308", manufactured by ORIENT CHEMICAL INDUSTRIES Co., Ltd.): 1 part of the adhesive composition solution A was applied to a release film (release liner) containing a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a silicone release treatment, and then at 130 ° C. Dry for 2 minutes. Thereby, a viscous crystal film A having a thickness (average thickness) of 5 μm and a thickness (average thickness) of 20 μm was obtained. <Creation of the cut crystal and sticky film> The PET release liner was peeled from the dicing sheet A, and the sticky film A was adhered to the exposed adhesive layer. A hand roller was used for bonding. Then, 300 mJ of ultraviolet rays were irradiated from the cut sheet side. In the above manner, a cut crystal adhesive film A is obtained. (Example 2) <Production of a sticky crystal film> The following (a) to (d) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution B having a solid content concentration of 18% by weight. (a) Acrylic resin (trade name "SG-P3", manufactured by Nagase ChemteX, molecular weight 850,000): 100 parts (b) phenol resin (trade name "MEH-7851ss", manufactured by Meiwa Chemical Co., Ltd.): 12 parts (c ) Filler B (trade name "YA010C-SV1", manufactured by Admatechs Co., Ltd., average particle diameter 10 nm): 100 parts (d) colorant (trade name "OIL SCARLET 308", manufactured by ORIENT CHEMICAL INDUSTRIES Co., Ltd.): 1 part of the adhesive composition solution B was coated on a release film (release liner) containing a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a silicone release treatment, and then at 130 ° C. Dry for 2 minutes. Thereby, a viscous crystal film B having a thickness (average thickness) of 5 μm and a thickness (average thickness) of 20 μm was obtained. <Creation of a cut crystal and sticky film> A cut sheet similar to the cut sheet A used in Example 1 was prepared. Then, the PET release liner was peeled from the dicing sheet A, and the adhesive film B was adhered to the exposed adhesive layer. A hand roller was used for bonding. Then, 300 mJ of ultraviolet rays were irradiated from the cut sheet side. In the above manner, a cut-crystal adhesive film B is obtained. (Example 3) <Production of a sticky crystal film> The following (a) to (d) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution C having a solid content concentration of 18% by weight. (a) Acrylic resin (trade name "SG-P3", manufactured by Nagase ChemteX, molecular weight 850,000): 100 parts (b) phenol resin (trade name "MEH-7851ss", manufactured by Meiwa Chemical Co., Ltd.): 12 parts (c ) Filler C (trade name "MEK-ST-40", manufactured by Nissan Chemical Industries, Ltd., average particle size 13 nm): 100 parts (d) colorant (trade name "OIL SCARLET 308", ORIENT CHEMICAL INDUSTRIES, limited stock (Manufactured by the company): 1 part after applying the adhesive composition solution C on a release treatment film (release liner) containing a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a silicone release treatment. , And dried at 130 ° C for 2 minutes. Thereby, a viscous crystal film C having a thickness (average thickness) of 5 μm and a thickness (average thickness) of 20 μm was obtained. <Creation of a cut crystal and sticky film> A cut sheet similar to the cut sheet A used in Example 1 was prepared. Then, the PET release liner was peeled from the dicing sheet A, and the adhesive film C was adhered to the exposed adhesive layer. A hand roller was used for bonding. Then, 300 mJ of ultraviolet rays were irradiated from the cut sheet side. In the above manner, a cut-to-slice cement film C is obtained. (Example 4) <Production of a sticky crystal film> The following (a) to (d) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution D having a solid content concentration of 18% by weight. (a) Acrylic resin (trade name "SG-P3", manufactured by Nagase ChemteX, molecular weight 850,000): 100 parts (b) phenol resin (trade name "MEH-7851ss", manufactured by Meiwa Chemical Co., Ltd.): 12 parts (c ) Filler D (trade name "MEK-ST-L", manufactured by Nissan Chemical Industry Co., Ltd., average particle diameter 45 nm): 100 parts (d) Colorant (trade name "OIL SCARLET 308", ORIENT CHEMICAL INDUSTRIES, limited shares (Manufactured by the company): 1 part after applying the adhesive composition solution D to a release treatment film (release liner) containing a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a silicone release treatment. , And dried at 130 ° C for 2 minutes. Thereby, a viscous crystal film D having a thickness (average thickness) of 5 μm and a thickness (average thickness) of 20 μm was obtained. <Creation of a cut crystal and sticky film> A cut sheet similar to the cut sheet A used in Example 1 was prepared. Then, the PET release liner was peeled from the dicing sheet A, and the adhesive film D was adhered to the exposed adhesive layer. A hand roller was used for bonding. Then, 300 mJ of ultraviolet rays were irradiated from the cut sheet side. In the above manner, the cut-to-crystal film D is obtained. (Example 5) <Production of a sticky crystal film> The following (a) to (d) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution E having a solid content concentration of 18% by weight. (a) Acrylic resin (trade name "SG-P3", manufactured by Nagase ChemteX, molecular weight 850,000): 100 parts (b) phenol resin (trade name "MEH-7851ss", manufactured by Meiwa Chemical Co., Ltd.): 12 parts (c ) Filler E (trade name "MEK-ST-ZL", manufactured by Nissan Chemical Industry Co., Ltd., average particle size 85 nm): 100 parts (d) colorant (trade name "OIL SCARLET 308", ORIENT CHEMICAL INDUSTRIES shares limited (Manufactured by the company): 1 part after applying the adhesive composition solution E to a release treatment film (release liner) containing a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a silicone release treatment. , And dried at 130 ° C for 2 minutes. Thereby, a viscous crystal film E having a thickness (average thickness) of 5 μm and a thickness (average thickness) of 20 μm was obtained. <Creation of a cut crystal and sticky film> A cut sheet similar to the cut sheet A used in Example 1 was prepared. Then, the PET release liner was peeled from the dicing sheet A, and the adhesive film E was adhered to the exposed adhesive layer. A hand roller was used for bonding. Then, 300 mJ of ultraviolet rays were irradiated from the cut sheet side. In the above manner, a cut-crystal adhesive film E is obtained. (Example 6) <Preparation of a sticky crystal film> The following (a) to (c) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution F having a solid content concentration of 18% by weight. (a) Acrylic resin (trade name "SG-P3", manufactured by Nagase ChemteX, molecular weight 850,000): 100 parts (b) phenol resin (trade name "MEH-7851ss", manufactured by Meiwa Chemical Co., Ltd.): 12 parts (c ) Filler D (trade name "MEK-ST-L", manufactured by Nissan Chemical Industries, Ltd., average particle diameter 45 nm): 100 parts The adhesive composition solution F is applied to After the release film (release liner) of a polyethylene terephthalate film having a thickness of 50 μm was applied, it was dried at 130 ° C. for 2 minutes. Thereby, a viscous crystal film F having a thickness (average thickness) of 5 μm and a thickness (average thickness) of 20 μm was obtained. <Creation of a cut crystal and sticky film> A cut sheet similar to the cut sheet A used in Example 1 was prepared. Then, the PET release liner was peeled from the dicing sheet A, and the adhesive film F was adhered to the exposed adhesive layer. A hand roller was used for bonding. Then, 300 mJ of ultraviolet rays were irradiated from the cut sheet side. In the above manner, a cut crystal cement film F is obtained. (Comparative example 1) <Preparation of a sticky crystal film> The following (a) to (d) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution G having a solid content concentration of 18% by weight. (a) Acrylic resin (trade name "SG-P3", manufactured by Nagase ChemteX, molecular weight 850,000): 100 parts (b) phenol resin (trade name "MEH-7851ss", manufactured by Meiwa Chemical Co., Ltd.): 12 parts (c ) Filler C (trade name "MEK-ST-40", manufactured by Nissan Chemical Industry Co., Ltd., average particle size 13 nm): 280 parts (d) Colorant (trade name "OIL SCARLET 308", ORIENT CHEMICAL INDUSTRIES, limited stock (Manufactured by the company): 2 parts of the adhesive composition solution G was coated on a release film (release liner) containing a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a silicone release treatment. , And dried at 130 ° C for 2 minutes. Thereby, a viscous film G having a thickness (average thickness) of 5 μm and a thickness (average thickness) of 20 μm was obtained. <Creation of the cut crystal and sticky film> The PET release liner was peeled from the dicing sheet A, and the sticky film A was adhered to the exposed adhesive layer. A hand roller was used for bonding. Then, 300 mJ of ultraviolet rays were irradiated from the cut sheet side. In the above manner, a cut-to-crystal film G is obtained. (Comparative example 2) <Preparation of a sticky crystal film> The following (a) to (c) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution H having a solid content concentration of 18% by weight. (a) Acrylic resin (trade name "SG-P3", manufactured by Nagase ChemteX, molecular weight 850,000): 100 parts (b) phenol resin (trade name "MEH-7851ss", manufactured by Meiwa Chemical Co., Ltd.): 12 parts (c ) Filler F (trade name "SO-25R", manufactured by Adtex Co., Ltd., average particle size 500 nm): 100 parts. The adhesive composition solution H is applied to a thickness of 50 μm including polysiloxane release treatment. After the release film (release liner) of the polyethylene terephthalate film was put on, it was dried at 130 ° C for 2 minutes. Thereby, a viscous crystal film H having a thickness (average thickness) of 5 μm and a thickness (average thickness) of 20 μm was obtained. <Creation of a cut crystal and sticky film> A cut sheet similar to the cut sheet A used in Example 1 was prepared. Then, the PET release liner was peeled from the dicing sheet A, and the adhesive film H was adhered to the exposed adhesive layer. A hand roller was used for bonding. Then, 300 mJ of ultraviolet rays were irradiated from the cut sheet side. In the above manner, a cut-crystal-bond film H is obtained. (Comparative Example 3) <Preparation of a sticky crystal film> The following (a) to (c) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution I having a solid content concentration of 18% by weight. (a) Acrylic resin (trade name "SG-P3", manufactured by Nagase ChemteX, molecular weight 850,000): 100 parts (b) phenol resin (trade name "MEH-7851ss", manufactured by Meiwa Chemical Co., Ltd.): 12 parts (c ) Colorant (trade name "OIL SCARLET 308", manufactured by ORIENT CHEMICAL INDUSTRIES Co., Ltd.): 1 part of the adhesive composition solution I was applied to a polyparaphenylene terephthalate having a thickness of 50 μm after being subjected to a polysiloxane release treatment. After the release film (release liner) of the ethylene formate film was applied, it was dried at 130 ° C for 2 minutes. Thereby, a viscous crystal film I having a thickness (average thickness) of 5 μm and a thickness (average thickness) of 20 μm was obtained. <Creation of a cut crystal and sticky film> A cut sheet similar to the cut sheet A used in Example 1 was prepared. Then, the PET release liner was peeled from the dicing sheet A, and the adhesive film I was adhered to the exposed adhesive layer. A hand roller was used for bonding. Then, 300 mJ of ultraviolet rays were irradiated from the cut sheet side. In the above manner, a cut crystal adhesive film I is obtained. (Comparative example 4) <Preparation of a sticky crystal film> The following (a) to (f) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution J having a solid content concentration of 45% by weight. (a) Acrylic resin (trade name "SG-P3", manufactured by Nagase ChemteX, molecular weight 850,000): 100 parts (b) Epoxy resin A (trade name "JER1010", manufactured by Mitsubishi Chemical Corporation): 52 parts (c ) Epoxy resin B (trade name "JER828", manufactured by Mitsubishi Chemical Corporation): 140 parts (d) phenol resin (trade name "MEH-7851ss", manufactured by Meiwa Chemical Co., Ltd.): 210 parts (e) filler C (trade name) "MEK-ST-40", manufactured by Nissan Chemical Industries, Ltd., with an average particle diameter of 13 nm): 100 parts (f) hardening accelerator (trade name "2PHZ-PW", manufactured by Shikoku Chemical Industries, Ltd.): Three parts of the adhesive composition solution J was coated on a release film (release liner) containing a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a silicone release treatment, and then at 130 ° C. Dry for 2 minutes. Thereby, a viscous crystal film J having a thickness (average thickness) of 5 μm and a thickness (average thickness) of 20 μm was obtained. <Creation of a cut crystal and sticky film> A cut sheet similar to the cut sheet A used in Example 1 was prepared. Then, the PET release liner was peeled from the dicing sheet A, and the adhesive film J was adhered to the exposed adhesive layer. A hand roller was used for bonding. Then, 300 mJ of ultraviolet rays were irradiated from the cut sheet side. In the above manner, a cut crystal and sticky film J is obtained. [Measurement of the average particle diameter of the filler] The sticky crystal films of the examples and comparative examples were heated at 175 ° C. for 1 hour, and then the sticky film after heat curing was embedded in a resin (EpoFix kit, manufactured by Struers). . The embedded sample was mechanically polished to expose the cross section of the viscous film. Then, the section was subjected to ion milling by a CP device (cross-section polisher, manufactured by Japan Electronics Co., Ltd., SM-09010). Then, a conductive treatment was performed, and a FE-SEM (Field-Emission Scanning Electron Microscope) was observed. The observation of FE-SEM is performed at an acceleration voltage of 1 to 5 kV, and the reflected electron image is observed. The image analysis software Image-J was used to binarize the captured images and identify filler particles. Then, the area of the filler particles in the image is divided by the number of filler particles in the image, the average area of the filler particles is obtained, and the particle diameter is calculated. [Measurement of the tensile storage elastic modulus at 150 ° C and 175 ° C before the viscous film is hardened and the glass transition temperature before the viscous film is hardened] The viscous films of Examples and Comparative Examples are overlapped until the thickness Becomes 200 μm. Then, a short strip having a length of 40 mm (measured length) and a width of 10 mm was cut with a cutter. Then, a solid viscoelasticity measuring device (RSAIII, manufactured by Rheometric Scientific) was used to measure the tensile storage elastic modulus at -40 to 260 ° C. The measurement conditions were set to a distance of 20 mm between chucks, a tensile mode, a frequency of 1 Hz, a strain of 0.1%, and a heating rate of 10 ° C / min. The measurement was started after holding at -40 ° C for 5 minutes. The values at this time at 150 ° C and 175 ° C were read as the measured values of the tensile storage elastic modulus. In addition, a temperature-Tanδ curve was prepared based on the obtained tanδ data, and the temperature of the Tanδ maximum value of the maximum peak was read, and this temperature was used as the glass transition temperature before heat curing. The results are shown in Table 1. [Measurement of the glass transition temperature of the viscous film after thermal curing] The viscous films of Examples and Comparative Examples were overlapped until the thickness became 200 μm. Then, it was heated at 175 ° C. for 1 hour to form a thermosetting hardened crystal film. Then, a short strip having a length of 40 mm (measured length) and a width of 10 mm was cut with a cutter. Then, a solid viscoelasticity measuring device (RSAIII, manufactured by Rheometric Scientific) was used to measure the tensile storage elastic modulus at -40 to 260 ° C. The measurement conditions were set as follows: the distance between the chucks was 20 mm, the tensile mode, the frequency was 1 Hz, the strain was 0.1%, and the heating rate was 10 ° C / min. The measurement was started after holding at -40 ° C for 5 minutes. According to the obtained tanδ data, a temperature-Tanδ curve was prepared, and the temperature of the maximum Tanδ value of the maximum peak was read, and this temperature was used as the glass transition temperature after heat curing. The results are shown in Table 1. [Measurement of Elongation at Break at -15 ° C in the state before the viscous film was hardened] The viscous films of Examples and Comparative Examples were overlapped until the thickness became 200 μm. Then, a short strip having a length of 60 mm (measured length) and a width of 10 mm was cut with a cutter. A tensile tester (manufacturer's name: SHIMADZU: 3-strand tensile tester with constant temperature and humidity tank) was used to measure the elongation at break at -15 ° C. The measurement conditions were set as follows: the distance between the chucks was 20 mm, the speed was 100 mm / min, and the measurement temperature was -15 ° C. The measurement was started after holding at -15 ° C for 2 minutes. The elongation at break is determined by the following formula. The results are shown in Table 1. [Elongation at break (%)] = [(length of the adhesive sheet at break (mm) -20) / 20 × 100] [Visibility evaluation] The sticky crystal film and the release-treated film () The case of the boundary of the release liner) was evaluated as ○, and the case where it was not easily recognized was evaluated as ×. The results are shown in Table 1. [Embeddedness Evaluation] A 20 μm-thick viscous film obtained in each of the Examples and Comparative Examples was attached to a silicon wafer ground to 50 μm at 60 ° C. and singulated into a 10 mm square wafer to obtain A wafer with a sticky crystal film. The wafer with the attached crystal film was mounted on a BGA substrate at a temperature of 150 ° C, a pressure of 0.1 MPa, and a time of 1 s. This was further heat-treated in a dryer at 175 ° C for 1 hour. Next, using a molding machine (manufactured by TOWA PRESS, Manual Press Y-1) at a molding temperature of 175 ° C, a clamping pressure of 184 kN, a transfer pressure of 5 kN, a time of 120 seconds, and a sealing resin GE-100 (Nitto Denko (Stock) system) under the conditions of sealing step. After the sealing step, an ultrasonic imaging device (Hitachi Fine-Tech, FS200II) was used to observe the void at the interface between the BGA substrate and the die-bond film. The binarization software (WinRoof ver. 5.6) was used to calculate the area occupied by the void in the observed image. The case where the area occupied by the voids with respect to the surface area of the viscous film was less than 30% was evaluated as "○", and the case where it was 30% or more was evaluated as "×". [Warpage evaluation] The 5 μm thick crystal film obtained in each example and comparative example was attached to a silicon wafer ground to a thickness of 30 μm at 60 ° C. and singulated (cut) to 15 mm in length × A wafer with a size of 10 mm across to obtain a wafer with a sticky crystal film. The wafer with the attached crystal film was mounted on a BGA substrate at a temperature of 150 ° C, a pressure of 0.1 MPa, and a time of 1 s. Further, a second wafer was mounted on the mounted wafer so as to be staggered by 300 μm in the lateral direction. This operation is repeated until the number of wafer layers becomes four. Five such laminates were prepared. The stacked wafers were set on a microscope so that the lateral sides of the wafers could be seen. The distance between the center of the first layer of the wafers and the BGA substrate was set to zero, and the extent of both ends of the wafers was observed. Specifically, the distance between the BGA substrate and each end portion was measured. Calculate the average of the amount of warpage at both ends. Furthermore, the average value of the five laminated bodies was calculated. Those whose average value was less than 60 μm were evaluated as ○, and those who were 60 μm or more were evaluated as ×. The results are shown in Table 1. [Cold Expansion Evaluation] Using ML300-Integration made by Tokyo Precision Co., Ltd. as a laser processing device, aligning the focusing point on the inside of a 12-inch semiconductor wafer and dividing it along a grid (10 mm × 10 mm) The predetermined line radiates laser light to form a modified region inside the semiconductor wafer. The laser light irradiation conditions were performed as follows. (A) Laser light Laser light source Semiconductor laser excitation Nd: YAG laser wavelength 1064 nm Laser spot cross-sectional area 3.14 × 10 -8 cm 2 Oscillation mode Q switching pulse repetition frequency 100 kHz Pulse width 30 ns Output 20 μJ / pulse Laser light quality TEM00 40 Polarization characteristics Linearly polarized light (B) 50 times magnification for condenser lens NA 0.55 Transmission rate to laser light wavelength 60% (C ) The moving speed of the cutting table on which the semiconductor substrate is placed is 100 mm / s. Next, the back surface polishing tape is attached to the surface of the semiconductor wafer. The thickness of the circle becomes 25 μm. Next, the above-mentioned semiconductor wafer and dicing ring subjected to the pre-processing using laser light were bonded to the dicing die-bonding film (thickness film thickness 5 μm) of the examples and comparative examples. Next, a wafer separator (Die Separator) DDS2300 manufactured by DISCO was used to cut the semiconductor wafer and heat-shrink the dicing sheet to obtain a sample. Specifically, first, the semiconductor wafer was cut by using a cold expansion unit under the conditions of an expansion temperature of -15 ° C, an expansion speed of 100 mm / s, and an expansion amount of 12 mm. Then, the thermal expansion unit was used to thermally shrink the cut sheet under the conditions of an expansion amount of 10 mm, a heating temperature of 250 ° C, an air volume of 40 L / min, a heating distance of 20 mm, and a rotation speed of 3 ° / s. The obtained samples were used for pick-up evaluation. Specifically, using a die bonder SPA-300 (manufactured by Shinkawa Corporation), picking was performed under the following conditions. A case where all of them can be picked up is marked as ○, and if there is one wafer that cannot be picked up, it is marked as x and evaluated. The results are shown in Table 1. <Pickup conditions> Number of pins: 5 Pickup height: 500 μm Pickup evaluation number: 50 wafers [Table 1]

1‧‧‧基材
2‧‧‧黏著劑層
2b‧‧‧未被黏晶膜3覆蓋之部分
3‧‧‧黏晶膜
4‧‧‧半導體晶圓
4F‧‧‧半導體晶圓之表面
4L‧‧‧分割預定線
4R‧‧‧半導體晶圓之背面
4S‧‧‧槽
5‧‧‧半導體晶片
6‧‧‧被黏著體
7‧‧‧接合線
8‧‧‧密封樹脂
10‧‧‧切晶黏晶膜
11‧‧‧切割片材
13‧‧‧黏晶膜
15‧‧‧半導體晶片
31‧‧‧切割環
32‧‧‧晶圓擴展裝置
33‧‧‧頂起部
41‧‧‧旋轉刀片
42‧‧‧保護基材
45‧‧‧研削磨石1‧‧‧ substrate
2‧‧‧ Adhesive layer
2b‧‧‧Uncovered by the sticky crystal film 3
3‧‧‧ sticky crystal film
4‧‧‧ semiconductor wafer
4F‧‧‧Surface of semiconductor wafer
4L‧‧‧ divided scheduled line
Back of 4R‧‧‧ semiconductor wafer
4S‧‧‧slot
5‧‧‧ semiconductor wafer
6‧‧‧ adherend
7‧‧‧ bonding wire
8‧‧‧sealing resin
10‧‧‧ cut crystal
11‧‧‧cut sheet
13‧‧‧ Sticky Crystal Film
15‧‧‧semiconductor wafer
31‧‧‧ cutting ring
32‧‧‧Wafer expansion device
33‧‧‧ jacking
41‧‧‧rotating blade
42‧‧‧ Protective substrate
45‧‧‧grinding stone

圖1係表示本發明之一實施形態之切晶黏晶膜之剖視模式圖。 圖2係用以說明本實施形態之半導體裝置之製造方法之剖視模式圖。 圖3係用以說明本實施形態之半導體裝置之製造方法之剖視模式圖。 圖4(a)、(b)係用以說明本實施形態之半導體裝置之製造方法之剖視模式圖。 圖5係用以說明本實施形態之半導體裝置之製造方法之剖視模式圖。 圖6係表示本實施形態之半導體裝置之另一例之剖視模式圖。 圖7(a)及(b)係用以說明本實施形態之半導體裝置之另一製造方法之剖視模式圖。 圖8係用以說明本實施形態之半導體裝置之另一製造方法之剖視模式圖。FIG. 1 is a schematic cross-sectional view showing a cut crystal and sticking film according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view for explaining a method for manufacturing a semiconductor device according to this embodiment. FIG. 3 is a schematic cross-sectional view for explaining a method for manufacturing a semiconductor device according to this embodiment. 4 (a) and 4 (b) are schematic cross-sectional views for explaining a method for manufacturing a semiconductor device according to this embodiment. FIG. 5 is a schematic cross-sectional view for explaining a method for manufacturing a semiconductor device according to this embodiment. FIG. 6 is a schematic cross-sectional view showing another example of the semiconductor device of this embodiment. 7 (a) and 7 (b) are schematic cross-sectional views for explaining another method of manufacturing a semiconductor device according to this embodiment. FIG. 8 is a schematic cross-sectional view for explaining another method of manufacturing the semiconductor device according to this embodiment.

1‧‧‧基材 1‧‧‧ substrate

2‧‧‧黏著劑層 2‧‧‧ Adhesive layer

2b‧‧‧未被黏晶膜3覆蓋之部分 2b‧‧‧Uncovered by the sticky crystal film 3

3‧‧‧黏晶膜 3‧‧‧ sticky crystal film

10‧‧‧切晶黏晶膜 10‧‧‧ cut crystal

11‧‧‧切割片材 11‧‧‧cut sheet

Claims (9)

一種黏晶膜，其特徵在於含有： 平均粒徑為5 nm～100 nm之範圍內之填料、 熱塑性樹脂、及 酚樹脂，且 熱硬化前之於150℃下之拉伸儲存彈性模數大於0.3 MPa且為30 MPa以下。A viscous crystal film, comprising: a filler having an average particle diameter in a range of 5 nm to 100 nm; a thermoplastic resin; and a phenol resin, and having a tensile storage elastic modulus at 150 ° C greater than 0.3 before heat curing. MPa is 30 MPa or less. 如請求項1之黏晶膜，其中將熱硬化前之玻璃轉移溫度設為T0 、將熱硬化後之玻璃轉移溫度設為T1 時，滿足下述式1, 式1 T0 ＜T1 ＜T0 ＋20。For example, if the viscous crystal film of claim 1, wherein the glass transition temperature before thermal curing is set to T 0 , and the glass transition temperature after thermal curing is set to T 1 , the following formula 1 is satisfied: Formula 1 T 0 ＜ T 1 <T 0 +20. 如請求項1之黏晶膜，其中上述填料為二氧化矽填料。The crystal film of claim 1, wherein the filler is a silica filler. 如請求項1之黏晶膜，其中上述熱塑性樹脂為具有環氧基之丙烯酸系聚合物。The viscous crystal film according to claim 1, wherein the thermoplastic resin is an acrylic polymer having an epoxy group. 如請求項1之黏晶膜，其包含著色劑。The viscous crystal film as claimed in claim 1, which contains a colorant. 如請求項5之黏晶膜，其中上述著色劑為染料。The viscous crystal film of claim 5, wherein the colorant is a dye. 如請求項1之黏晶膜，其中將上述填料之平均粒徑設為R、將上述黏晶膜之厚度設為T時，滿足下述式2, 式2 10＜T/R。For example, if the sticky crystal film of claim 1 is to set the average particle diameter of the filler as R and set the thickness of the sticky film as T, the following formula 2 is satisfied, and the formula 2 10 <T / R. 一種切晶黏晶膜，其特徵在於具備： 切割片材、及 如請求項1至7中任一項之黏晶膜。A cut crystal sticky film, comprising: a cut sheet; and the sticky film according to any one of claims 1 to 7. 一種半導體裝置之製造方法，其特徵在於包括以下步驟： 步驟A，將半導體晶圓貼附於切晶黏晶膜； 步驟B，使上述切晶黏晶膜擴張，至少使上述黏晶膜斷裂，獲得附黏晶膜之晶片； 步驟C，拾取上述附黏晶膜之晶片； 步驟D，將所拾取之上述附黏晶膜之晶片經由黏晶膜黏晶至被黏著體；以及， 步驟E，對上述附黏晶膜之晶片進行打線接合；且 上述切晶黏晶膜含有： 平均粒徑為5 nm～100 nm之範圍內之填料、 熱塑性樹脂、及 酚樹脂，且 熱硬化前之於150℃下之拉伸儲存彈性模數大於0.3 MPa且為30 MPa以下。A method for manufacturing a semiconductor device, comprising the following steps: step A, attaching a semiconductor wafer to a dicing die-bonding film; and step B, expanding the dicing die-bonding film to at least break the dicing die-bonding film Obtaining a wafer with a sticky crystal film; Step C, picking up the wafer with a sticky crystal film; Step D, sticking the picked up wafer with the sticky crystal film to the adherend through the sticky film; and, Step E, Wire-bond the wafer with a sticky crystal film; and the die-cut crystal film contains: a filler having an average particle diameter in a range of 5 nm to 100 nm, a thermoplastic resin, and a phenol resin, and the temperature is less than 150 before heat curing. The tensile storage elastic modulus at ℃ is more than 0.3 MPa and less than 30 MPa.
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