JP2008277806A - Adhesive member for semiconductor, semiconductor device and method for manufacturing the semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive member for semiconductor, a semiconductor device and a method for manufacturing the semiconductor device, whose reaction speed can be adjusted by irradiating radiant rays, and crosslink density also can be easily adjusted and then the design margin of its film is improved. <P>SOLUTION: The adhesive member comprises an adhesive agent layer and a base material layer. The adhesive agent layer contains: (A) an epoxy resin and an epoxy resin curing agent, (B) a polymer containing a functional group and having 100,000 weight average molecular weight or higher, (C) a proton-donating compound, (D) photoacid producing agent, and (E) a radioactive ray polymerizing compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an adhesive member for a semiconductor, a semiconductor device, and a method for manufacturing the semiconductor device.

  In recent years, with the development of electronic devices, the mounting density of electronic components has increased, and a new type of mounting method such as a semiconductor package in which semiconductor chips are stacked such as a multi-chip stacked package (hereinafter abbreviated as MCP). The thickness of semiconductor wafers used has been further reduced.

  In general, liquid or film adhesives are used as adhesive members used in conventional semiconductor mounting substrates. However, support members are being used as semiconductor devices become smaller and higher performance in recent years. In recent years, there has been a demand for miniaturization and densification, and in recent years, adhesive films that can be easily processed finely are used.

  This adhesive film is used in an individual piece bonding method or a wafer back surface bonding method. When manufacturing a semiconductor device using the former adhesive film of the individual piece pasting method, the reel-like adhesive film is cut into individual pieces by cutting or punching, and then the individual pieces are adhered to a support member, and the support with the adhesive film is supported. A semiconductor device separated by a dicing process is joined to the member to produce a support member with a semiconductor element, and then a semiconductor device is obtained by performing a wire bonding process, a sealing process, and the like as necessary. . However, in order to use the adhesive film of the above-mentioned individual sticking method, a dedicated assembly device that cuts out the adhesive film and adheres it to the support member is necessary, so compared with a method using a liquid adhesive such as silver paste. As a result, the manufacturing cost is high.

  On the other hand, when manufacturing a semiconductor device using an adhesive film of the latter wafer back surface attachment method, first, an adhesive film is attached to the back surface of the semiconductor wafer, and an adhesive film for fixing the semiconductor wafer is attached to the other surface of the adhesive film. After that, the semiconductor element is separated into pieces from the wafer by dicing, the separated semiconductor element with an adhesive film is peeled off from the pressure-sensitive adhesive layer, and it is bonded to the support member, and the subsequent steps such as heating, curing, and wire bonding Through this process, a semiconductor device is obtained. This wafer back surface bonding type adhesive film joins the semiconductor element with the adhesive film to the support member, so it does not require an apparatus for separating the adhesive film into pieces, and the conventional silver paste assembling apparatus is used as it is or with a hot platen. It can be used by modifying a part of the device such as adding. Therefore, it has been attracting attention as a method that can reduce the manufacturing cost relatively low among the assembling methods using the adhesive film.

  The pressure-sensitive adhesive film used together with the wafer back surface bonding type adhesive film is roughly classified into a pressure sensitive type and an ultraviolet curable type. The former pressure-sensitive adhesive film is usually one obtained by applying an adhesive to a polyvinyl chloride or polyolefin base film. This adhesive film is required to have a sufficient adhesive strength so that each element does not scatter due to rotation of the dicing saw or laser irradiation when cutting in the dicing process, and when it is bonded to the semiconductor support member, it does not damage the semiconductor element. The adhesive strength is low enough to be peeled off from the material layer. However, since there was no pressure-sensitive adhesive film having sufficient two conflicting performances as described above, an operation of switching the adhesive film for each size and processing condition of the semiconductor element has been performed. Moreover, since the adhesive force needs to be controlled depending on the element size and processing conditions, the inventory management of the adhesive film is complicated. Furthermore, in recent years, especially as the capacity of CPUs and memories has increased, semiconductor elements tend to increase in size, and in products such as IC cards and memory cards, the memory used has become thinner. Yes. With the increase in size and thickness of these semiconductor elements, there has been a problem that the elements are broken when the adhesive layer is peeled off.

  On the other hand, the latter UV curable pressure-sensitive adhesive film has a high adhesive strength during dicing, but has a low adhesive strength when irradiated with ultraviolet rays before the adhesive layer is peeled off from the adhesive layer. Therefore, it has been widely adopted since the problems of the pressure-sensitive adhesive film are improved.

  Furthermore, in the method using the wafer back surface bonding type adhesive film, two pasting steps such as pasting the adhesive layer and the pressure-sensitive adhesive layer are necessary before the dicing step. Therefore, an adhesive sheet in which an adhesive layer and an adhesive layer are laminated in advance has been developed (see, for example, Patent Documents 1 and 2).

However, if an adhesive sheet obtained by laminating the adhesive layer and the pressure-sensitive adhesive layer is stored for a long period of time, each curing reaction proceeds and the adhesiveness tends to decrease. In addition, the photopolymerization initiator contained in the pressure-sensitive adhesive layer often uses a direct cleavage type in which the substance itself generates a radical upon irradiation with ultraviolet rays or the like, but these compounds are excellent in reactivity but gradually react.・ Deterioration progresses. Moreover, since it decomposes | disassembles when heated to high temperature and there exists a possibility of contaminating a semiconductor element, the adhesive member excellent in storage stability and excellent in heat stability is desired.
Japanese Patent No. 3348923 JP 10-335271 A

  An object of the present invention is to provide an adhesive member for semiconductor, a semiconductor device, and a method for manufacturing the semiconductor device, which can adjust the reaction rate by radiation irradiation, easily adjust the crosslinking density, and improve the film design tolerance.

  The present invention is (1) an adhesive member comprising an adhesive layer and a base material layer, wherein the adhesive layer has (A) an epoxy resin and an epoxy resin curing agent, and (B) a functional group. The present invention relates to a semiconductor adhesive member comprising a polymer having a weight average molecular weight of 100,000 or more, (C) a proton donating compound, (D) a photoacid generator, and (E) a radiation polymerizable compound.

  In the present invention, (2) the polymer having a functional group (B) having a weight average molecular weight of 100,000 or more is an epoxy group- and isocyanate group-containing (meth) acrylic copolymer, and the epoxy group-containing polymer. The amount of the repeating unit is 0.5 to 6% by weight, and the present invention relates to the adhesive member for semiconductor according to the above (1).

  In the present invention, (3) a polymer in which the adhesive layer has (B) a functional group and a weight average molecular weight of 100,000 or more with respect to 100 parts by weight of the (A) epoxy resin and the epoxy resin curing agent. 10 to 400 parts by weight, (C) a proton donating compound 0.1 to 20 parts by weight, (D) a photoacid generator 0.5 to 50 parts by weight, and (E) a radiation polymerizable compound 1 to 50 parts. The semiconductor adhesive member according to (1) or (2), wherein the adhesive member includes a weight part.

  The present invention is also characterized in that (4) the storage elastic modulus after heat curing of the adhesive layer is 10 to 5000 MPa at 25 ° C. and 3 to 50 MPa at 250 ° C. The semiconductor adhesive member according to any one of (3).

  Moreover, this invention controls the adhesive strength of the said adhesive agent layer and a base material layer interface by irradiating a radiation to the said adhesive agent layer, The said (1)-characterized by the above-mentioned. It is related with the adhesive member for semiconductors as described in any one of (4).

  In addition, the present invention provides (6) a semiconductor device in which a semiconductor element and a semiconductor element mounting support member are bonded using the semiconductor bonding member according to any one of (1) to (5). About.

Moreover, this invention is a semiconductor wafer to the adhesive layer of the adhesive member for semiconductors provided with the adhesive agent layer and base material layer as described in any one of (7) said (1)-(5). Affixing step (I),
Dicing the semiconductor wafer to obtain a semiconductor element with a semiconductor adhesive member (II),
Step (III) of irradiating and curing radiation to the adhesive layer of the semiconductor element with the semiconductor adhesive member,
Step (IV) of obtaining a semiconductor element with an adhesive layer by peeling at the interface between the adhesive layer and the base material layer of the semiconductor element with an adhesive member for a semiconductor,
And a step (V) of adhering the semiconductor element with the adhesive layer and the semiconductor element mounting support member, to a method for manufacturing a semiconductor device.

  According to the present invention, it is possible to provide an adhesive member for semiconductor, a semiconductor device, and a method for manufacturing the semiconductor device that can adjust the reaction rate by radiation irradiation, easily adjust the crosslinking density, and improve the film design tolerance.

  The adhesive member for a semiconductor according to the present invention is an adhesive member including an adhesive layer and a base material layer, and the adhesive layer includes (A) an epoxy resin and an epoxy resin curing agent, and (B) a functional group. And a polymer having a weight average molecular weight of 100,000 or more, (C) a proton donating compound, (D) a photoacid generator, and (E) a radiation polymerizable compound.

  The adhesive member for a semiconductor of the present invention has a sufficient adhesive strength so that the semiconductor element does not scatter in the dicing process. When the semiconductor element is picked up to adhere the semiconductor element to the support member for mounting the semiconductor element, radiation irradiation is performed. By controlling the adhesive strength of the interface between the adhesive layer and the base material layer, it acts as a semiconductor adhesive member that satisfies the conflicting requirements of having a low adhesive strength that does not damage each element, In addition, the die bonding process for bonding the semiconductor element and the semiconductor mounting support member acts as an adhesive member that makes the connection reliability excellent, and each process of dicing and die bonding can be completed with one bonding member. .

Each component which comprises the adhesive agent layer in the semiconductor adhesive member of this invention is demonstrated.
(A) Epoxy resin and epoxy resin curing agent The epoxy resin used in the present invention is not particularly limited as long as it is cured and has an adhesive action. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc. Bifunctional epoxy resins: Novolak type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; Multifunctional epoxy resins; Glycidyl amine type epoxy resins; Heterocyclic epoxy resins; Alicyclic epoxy resins, etc. What is being applied can be applied. Among these, a bifunctional epoxy resin is preferable.

  As an epoxy resin hardening | curing agent used in this invention, the well-known hardening | curing agent used normally can be used. For example, amines; polyamides; acid anhydrides; polysulfides; boron trifluoride; bisphenols having two or more phenolic hydroxyl groups in one molecule such as bisphenol A, bisphenol F, and bisphenol S; phenol novolac resin, bisphenol A And phenolic resins such as novolak resin or cresol novolak resin. Phenol resins such as phenol novolac resin, bisphenol A novolak resin, and cresol novolac resin are particularly preferable in terms of excellent electric corrosion resistance when absorbing moisture.

(B) Polymer having a functional group and a weight average molecular weight of 100,000 or more The polymer used as the component (B) in the present invention is a polymer having a functional group and a weight average molecular weight of 100,000 or more. When the weight average molecular weight of the polymer is 100,000 or more, the strength, flexibility and tackiness when the semiconductor adhesive member is made into a sheet or film are appropriate, and the flow property is appropriate. The circuit filling property of the wiring can be ensured. The weight average molecular weight of the polymer is preferably 300,000 to 3,000,000, more preferably 500,000 to 2,000,000. In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

  The polymer has a functional group, and the functional group may be present in the polymer chain or at the end of the polymer chain. Examples of the functional group include an epoxy group, an acryloyl group, a methacryloyl group, a hydroxyl group, a carboxyl group, an isocyanate group, an amino group, and an amide group. Among these, an epoxy group and an isocyanate group are preferable in terms of PCT resistance. The polymer having such a functional group preferably has both an epoxy group and an isocyanate group, and more preferably an epoxy group- and isocyanate group-containing (meth) acrylic copolymer.

  The amount of the functional group-containing repeating unit in the polymer having a functional group-containing weight average molecular weight of 100,000 or more is preferably 0.5 to 6.0% by weight, and 0.5 to 5.0% by weight. More preferably. For example, in the case of an epoxy group-containing (meth) acrylic copolymer, the amount of the epoxy group-containing repeating unit is preferably 0.5 to 6.0% by weight, and preferably 0.5 to 5.0% by weight. It is more preferable that it is 0.8 to 5.0% by weight. When the amount of the epoxy group-containing repeating unit is in the range of 0.5 to 6.0% by weight, it is easy to ensure adhesive strength and to prevent gelation.

  The polymer having a functional group-containing weight average molecular weight of 100,000 or more is preferably incompatible with (A) the epoxy resin and the epoxy resin curing agent and has a sea-island structure.

  Examples of a method for producing a polymer having a functional group-containing weight average molecular weight of 100,000 or more include, for example, a method of polymerizing a polymerizable monomer having a functional group alone, a polymerizable monomer having a functional group, and a copolymerization thereof. It can be obtained by a method of copolymerizing with other polymerizable monomers. The polymerization method is not particularly limited, and for example, methods such as suspension polymerization and solution polymerization can be used.

  The polymerizable monomer having a functional group may have at least one polymerizable group in one molecule, and is preferably a monomer having at least one ethylenically unsaturated bond in one molecule. It is more preferable to use both a polymerizable monomer having a group and a polymerizable monomer having an isocyanate group.

  Examples of the polymerizable monomer having an epoxy group include glycidyl ethers such as allyl glycidyl ether and chalcone glycidyl ether; glycidyl (meth) acrylate, vinyl benzoic acid glycidyl ester, allyl benzoic acid glycidyl ester, cinnamate glycidyl ester, and cinnamylidene Glycidyl ester, dimer acid glycidyl ester, glycidyl or epoxy ester such as epoxidized stearyl alcohol and acrylic acid or methacrylic acid ester; epoxidized unsaturated linear or cyclic olefin such as epoxy hexene or limonene oxide It is done. Among these, glycidyl (meth) acrylate is preferable. Moreover, these may use together 2 or more types.

  As the polymerizable monomer having a (meth) acryloyl group, a polyfunctional (meth) acrylate compound having at least two (meth) acryloyl groups in the molecule is particularly preferable. For example, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, ethylene-modified trimethylolpropane tri (meth) acrylate, tris- (2-hydroxyethyl) -isocyanuric acid ester Trifunctional (meth) acrylates such as tri (meth) acrylate, tetrafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. Two or more of these may be used in combination.

  Examples of the polymerizable monomer having a hydroxyl group include allyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, neo Examples include pentyl glycol mono (meth) acrylate, glycerin mono (meth) acrylate, and vinylphenol. Two or more of these may be used in combination.

  Examples of the polymerizable monomer having a carboxyl group include aliphatic unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, propiolic acid and crotonic acid; aromatic unsaturated monocarboxylic acids such as cinnamic acid; maleic acid and fumaric acid. Aliphatic unsaturated dicarboxylic acids such as acid, itaconic acid and citraconic acid; maleic monoesters such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monohexyl maleate, monooctyl maleate and mono-2-ethylhexyl maleate; Examples thereof include unsaturated dicarboxylic acid monoesters such as fumaric acid monoesters. Moreover, these may use together 2 or more types.

  Examples of the polymerizable monomer having an isocyanate group include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene. Diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4 , 4′-diphenylmethane diisocyanate, 3,3′-dimethylphenylene diisocyanate, 4,4′-biphenylene diisocyanate, 1,6-hexane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Methylenebis (4-cyclohexylisocyanate), 2, , 4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate -Hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, tetramethylxylylene diisocyanate, 2,5 (or 2,6) -bis (Isocyanatemethyl) -bicyclo [2.2.1] heptane, cyclohexane diisocyanate, lysine ester triisocyanate, undecane triisocyanate, hexamethylene triisocyanate, triphenylmethane triisocyanate, and these isocyanate compounds Polymers, derivatives, modified products, hydrogenated products thereof. Examples of the modified body include isocyanurate-modified, burette-modified, and adduct-modified with a polyhydric alcohol such as trimethylolpropane. Among these, hexamethylene diisocyanate, bis (isocyanate methyl) cyclohexane and the like are preferable in terms of reactivity and crosslink density. The preferred functional number of isocyanate in one molecule of the polymerizable monomer having an isocyanate group is 2 or 3.

  Examples of the polymerizable monomer having an amino group include allyl compounds such as allylamine and diallylamine; vinyl compounds such as 4-vinylaniline and N-vinyldiphenylamine; N, N-dimethylaminoethyl (meth) acrylate, N, N— (Meth) acrylates such as diethylaminoethyl (meth) acrylate are exemplified. Moreover, these may use together 2 or more types.

  Examples of the polymerizable monomer having an amide group include acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N, N-dimethylaminopropylacrylamide, and siacetoneacrylamide. (Meth) acrylamide and derivatives thereof; vinylsulfonamides such as vinylsulfonamide, vinylsulfonanilide, vinylsulfonemethylanilide, vinylsulfonacetanilide are included. Preferred polymerizable compounds having an amide group include (meth) acrylamide and N-substituted (meth) acrylamide. Moreover, these may use together 2 or more types.

  Examples of other polymerizable monomer copolymerizable with the polymerizable monomer having a functional group include an ethylenically unsaturated carboxylic acid ester monomer and an ethylenically unsaturated nitrile monomer. The ethylenically unsaturated carboxylic acid ester monomer is preferably a (meth) acrylic acid ester monomer, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, or isopropyl (meth) acrylate. , (Meth) butyl acrylate, (butyl) (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) Octyl acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, undecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic Stearyl acid, dodecyl (meth) acrylate, (me ) Tetrahydrofurfuryl acrylate, phenoxyethyl (meth) acrylate, toluyloxyethyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ( Butoxyethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) acrylic acid Examples include isobornyl, (meth) acrylic acid ethoxylated phenyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid t-butylcyclohexyl, and the like. Of these, lower alkyl esters of (meth) acrylic acid such as (meth) acrylic methyl, (meth) acrylethyl, (meth) acrylpropyl, and (meth) acrylic acid butyl are preferable. Examples of the ethylenically unsaturated nitrile monomer include (meth) acrylonitrile, fumaronitrile, α-chloroacrylonitrile, α-cyanoethylacrylonitrile and the like. Of these, acrylonitrile is preferred. Moreover, these may use together 2 or more types. As another polymerizable monomer copolymerizable with the polymerizable monomer having a functional group, it is preferable to use an ethylenically unsaturated nitrile monomer together with an ethylenically unsaturated carboxylic acid ester monomer as a main component.

(C) Proton donating compound In the present invention, (C) proton donating compound and (D) photoacid generator act as a photopolymerization initiator. (C) The proton-donating compound is not particularly limited as long as it generates protons by irradiation with radiation. For example, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzimidazole, 2-mercapto-5. -Carboxybenzimidazole, 2-mercapto-5-methylbenzimidazole, 1-phenyl-2-mercaptobenzimidazole, 2-hydroxybenzimidazole, 2-mercaptobenzothiazole, 2-methylthiobenzothiazole, 2-mercaptothiazoline, 2- Examples include methylbenzothiazole, 2-chlorobenzothiazole, benzyl mercaptan, and 2-mercaptopyridine. These can be used alone or in combination of two or more. Of these, imidazoles are preferable.

(D) Photoacid generator The (D) photoacid generator used in the present invention is not particularly limited, and examples thereof include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, and N-maleimidoethyl acrylate. N-maleimidopropyl acrylate, N-maleimidobutyl acrylate, 3-methyl-N-maleimidoethyl acrylate, 3-methyl-N-maleimidopropyl acrylate, 3-methyl-N-maleimidobutyl acrylate, N- Ethyl phthalimidoacrylate, N-phthalimidopropyl acrylate, N-phthalimidobutyl acrylate, 3-phenyl-N-maleimidoethyl acrylate, 3-phenyl-N-maleimidopropyl acrylate, 3-phenyl-N-maleimidoacrylic acid Butyl, N-maleimide methacryl Ethyl acetate, N-maleimide propyl methacrylate, N-maleimide butyl methacrylate, 3-methyl-N-maleimide ethyl methacrylate, 3-methyl-N-maleimide propyl methacrylate, 3-methyl-N-maleimide butyl methacrylate, N-phthalimidoethyl methacrylate, N-phthalimidopropyl methacrylate, N-phthalimidobutyl methacrylate, 3-phenyl-N-maleimide ethyl methacrylate, 3-phenyl-N-maleimide propyl methacrylate, 3-phenyl-N-maleimide Butyl methacrylate, 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4′-methoxynaphthyl) -6-triazine, 2,4-trichloro- (piperonyl) ) -6-triazine, 2,4 Trichloromethyl (4'-methoxystyryl) -6-triazine, 2,4-trichloromethyl (3'-methoxystyryl) -6-triazine, 2,4-trichloromethyl (3'-chloro-4'-methoxystyryl) -6-triazine, 2,2-dimethoxy-1,2-diphenylethane-1-one and the like. These can be used alone or in combination of two or more.

(E) Radiation polymerizable compound (E) The radiation polymerizable compound used in the present invention is not particularly limited as long as it is a compound that polymerizes and cures when irradiated with radiation such as ultraviolet rays and electron beams. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, pentenyl acrylate, tetrahydrofurfuryl (meth) acrylate, diethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanedi All di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone 2-hydroxyethyl (meth) acrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,2-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, A triacrylate of tris (β-hydroxyethyl) isocyanurate or the like can be used. These radiation polymerizable compounds can be used alone or in combination of two or more.

  The adhesive layer in the present invention is 10 to 400 parts by weight of the polymer (B) having a functional group-containing weight average molecular weight of 100,000 or more with respect to 100 parts by weight of the (A) epoxy resin and the epoxy resin curing agent. It is preferable that 0.1 to 20 parts by weight of the (C) proton donating compound, 0.5 to 50 parts by weight of the (D) photoacid generator, and 1 to 50 parts by weight of the (E) radiation polymerizable compound. . When the polymer (B) having a functional group-containing weight average molecular weight of 100,000 or more is less than 10 parts by weight, the moldability and PCT resistance when formed into a film tend to be inferior. Film cohesion tends to decrease. When the amount of the (C) proton donating compound is less than 0.1 part by weight, the reaction tends not to proceed sufficiently, and when it exceeds 20 parts by weight, the storage stability is lowered and workability tends to be lowered. Similarly, when the amount of the photoacid generator (D) is less than 0.5 parts by weight, the reaction does not proceed sufficiently, and when it exceeds 50 parts by weight, the storage stability is lowered and workability tends to be lowered. When the (E) radiation polymerizable compound exceeds the range of 1 to 50 parts by weight, the reactivity during photocuring tends to be uncontrollable. The adhesive layer is composed of 100 to 300 parts by weight of (B) a polymer having a functional group-containing weight average molecular weight of 100,000 or more with respect to 100 parts by weight of the (A) epoxy resin and epoxy resin curing agent. It is more preferable that 0.3 to 3 parts by weight of C) a proton donating compound, 10 to 20 parts by weight of (D) a photoacid generator and 10 to 40 parts by weight of (E) a radiation polymerizable compound.

  Although there is no restriction | limiting in particular in the thickness of the adhesive agent layer in the adhesive member for semiconductors of this invention, 5-250 micrometers is preferable. If the thickness of the adhesive layer is less than 5 μm, the stress relaxation effect tends to be poor. If the thickness is more than 250 μm, it is not economical, and there is a possibility that the demand for miniaturization of the semiconductor device cannot be met.

  Moreover, in order to obtain desired thickness, the adhesive layer in the adhesive member for semiconductors of this invention can also laminate | stack two or more adhesive layers. In this case, a bonding condition is required so that peeling between the adhesive layers is difficult to occur.

  On the other hand, as the adhesive layer in the adhesive member for semiconductor of the present invention, an adhesive comprising (A) an epoxy resin and an epoxy resin curing agent, and (B) a polymer having a functional group and a weight average molecular weight of 100,000 or more. It is good also as a 2 layer structure comprised from a layer and the adhesive layer which consists of (C) proton donating compound, (D) photo-acid generator, (E) radiation polymerizable compound, etc.

Moreover, the adhesive layer in the adhesive member for semiconductors of the present invention is irradiated with radiation, for example, ultraviolet rays, and reduced in adhesive strength with the base material layer by photopolymerization and then heated and cured at 25 ° C. The storage elastic modulus is preferably 10 to 5000 MPa, and the storage elastic modulus at 250 ° C. is preferably 3 to 50 MPa. Furthermore, the storage elastic modulus at 25 ° C. is more preferably 20 to 1900 MPa, and particularly preferably 50 to 1800 MPa. Further, the storage elastic modulus at 250 ° C. is more preferably 5 to 50 MPa, and particularly preferably 7 to 50 MPa. When the storage elastic modulus is in the above range, the effect of relaxing the thermal stress generated by the difference in thermal expansion coefficient between the semiconductor element and the semiconductor element mounting support member is maintained, and the occurrence of peeling and cracks can be suppressed, It is easy to handle the adhesive and easily suppress the occurrence of reflow cracks. The irradiation with the ultraviolet rays is usually performed under conditions of about 200 mJ / cm ² with an illuminance of 10 mW / cm ² . Although the conditions of the said heat-hardening differ also with compositions of an adhesive agent layer, they are 170 degreeC and 60 minutes normally. In the present invention, the storage elastic modulus is, for example, a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology), a tensile load is applied to the cured adhesive layer, a frequency of 10 Hz, and a heating rate of 5 It can be measured by a temperature-dependent measurement mode in which measurement is performed from −50 ° C. to 300 ° C. under a condition of −10 ° C./min.

(Coupling agent)
In addition, various coupling agents can be added to the adhesive layer in the adhesive member for semiconductor of the present invention in order to improve interfacial bonding between different materials. Examples of the coupling agent include silane-based, titanium-based, aluminum-based, and the like. Among these, a silane-based coupling agent is preferable because of its high addition effect.

  The silane coupling agent is not particularly limited, and examples thereof include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldi Ethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopro Rutrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltri Methoxysilane, 3-aminopropyl-tris (2-methoxy-diethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyltrimethoxysilane, 3-4,5-dihydroimidazol-1-yl- Propyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyldimethoxysilane, 3-silane Nopropyltriethoxysilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, amyltrichlorosilane , Octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltri (methacryloyloxyethoxy) silane, methyltri (glycidyloxy) silane, N (β-N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane , Octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimethoxy Silane, γ-chloropropylmethyldiethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate, methylsilyl triisocyanate, vinylsilyl triisocyanate, phenylsilyl triisocyanate, tetraisocyanate silane, ethoxysilane isocyanate, etc. can be used alone. Alternatively, two or more types can be used in combination.

  Examples of the titanium-based coupling agent include isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl Phenyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris (aminoethyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl) -1-butyl) bis (ditridecyl) phosphite titanate, dicumyl Phenyloxyacetate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene Glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate ethyl ester, titanium triethanolamate, polyhydroxy titanium stearate, tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, tetraisobutyl orthotitanate, stearyl titanate, Cresyl titanate monomer, cresyl titanate polymer Diisopropoxy-bis (2,4-pentadionate) titanium (IV), diisopropyl-bis-triethanolamino titanate, octylene glycol titanate, tetra-n-butoxytitanium polymer, tri-n-butoxytitanium monostearate A rate polymer, tri-n-butoxy titanium monostearate, etc. can be used, and it can be used individually or in combination of 2 or more types.

  Examples of the aluminum coupling agent include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetylacetate). Nate), aluminum-monoisopropoxy mono-oroxyethyl acetoacetate, aluminum-di-n-butoxide monoethyl acetoacetate, aluminum chelate compounds such as aluminum-di-iso-propoxide-monoethyl acetoacetate, aluminum isopropylate, Mono-sec-butoxyaluminum diisopropylate, aluminum-sec-butyrate, aluminum It can be used such as aluminum alcoholate such Muechireto, alone or in combination of two or more kinds may be used.

  It is preferable that the usage-amount of the said coupling agent shall be 0.01-10 weight part with respect to 100 weight part of (A) epoxy resin and an epoxy resin hardening | curing agent from the surface of the effect, heat resistance, and cost.

(Ion scavenger)
An ion scavenger can be further added to the adhesive layer in the adhesive member for semiconductors of the present invention in order to adsorb ionic impurities and improve insulation reliability when absorbing moisture. Such an ion scavenger is not particularly limited, and examples thereof include compounds such as triazine thiol compounds and bisphenol-based reducing agents known as copper damage inhibitors that prevent copper from ionizing and dissolving, N, Examples thereof include compounds such as N′-di-2-naphthyl-p-phenylenediamine, inorganic ion adsorbents such as zirconium, antimony bismuth, and magnesium aluminum compounds.

  The amount of the ion scavenger used is 0.01 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin and the epoxy resin curing agent, from the viewpoint of the effect of addition, heat resistance, cost, and the like. preferable. Moreover, when it is set as 2 layer structure of an adhesive bond layer and an adhesive layer, the usage-amount of the said ion scavenger is the adhesive layer with respect to 100 weight part of (A) epoxy resin and an epoxy resin hardening | curing agent. 0.1 to 10 parts by weight, and the pressure-sensitive adhesive layer is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the (E) radiation polymerizable compound.

(Inorganic filler)
An inorganic filler can also be added to the adhesive layer in the adhesive member for semiconductors of the present invention for the purpose of improving its handleability, improving thermal conductivity, adjusting melt viscosity and imparting thixotropic properties. The inorganic filler is not particularly limited. For example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, Examples thereof include boron nitride, crystalline silica, amorphous silica, and hydrophobic fumed silica. The shape of the inorganic filler is not particularly limited. These inorganic fillers can be used alone or in combination of two or more. Among these, aluminum oxide, aluminum nitride, boron nitride, crystalline silica, and amorphous silica are preferable for improving thermal conductivity. For the purpose of adjusting melt viscosity and imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, crystallinity Silica, amorphous silica and the like are preferable. In addition, hydrophobic fumed silica is preferred for improving heat resistance and cohesion.

  Moreover, it is preferable that the average particle diameter of an inorganic filler is 0.005 micrometer-1 micrometer, and adhesiveness may fall even if it is smaller than this or larger.

  As for the compounding quantity of an inorganic filler, 1-40 weight part is preferable with respect to 100 weight part of compositions which comprise an adhesive agent layer. If the blending amount of the inorganic filler is less than 1 part by weight, there is a tendency that the addition effect cannot be obtained, and if it exceeds 40 parts by weight, the storage elastic modulus of the adhesive layer is increased, the adhesiveness is decreased, and voids remain. There is a tendency to cause problems such as deterioration of electrical characteristics.

The adhesive member for a semiconductor of the present invention comprises an adhesive layer and a base material layer.
The composition constituting the adhesive layer can be prepared as a varnish by mixing the above components together with a solvent and dissolving or dispersing, but the varnish when an inorganic filler is added to the adhesive layer In the production of, it is preferable to use a raking machine, a three-roll, a ball mill, a bead mill and the like in consideration of the dispersibility of the inorganic filler, and these may be used in combination. In addition, after mixing the inorganic filler and the low molecular weight material in advance, the mixing time can be shortened by blending the high molecular weight material. Moreover, after preparing a varnish, the bubble in a varnish can also be removed by vacuum deaeration.

  Although it does not specifically limit as a solvent which can be used for said varnishing, Considering the volatility at the time of film preparation, for example, methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, It is preferable to use a solvent having a relatively low boiling point such as methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, and xylene. In addition, for the purpose of improving the coating properties, for example, a solvent having a relatively high boiling point such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, cyclohexanone can be used. These solvents can be used alone or in combination of two or more.

  Subsequently, the obtained varnish is applied to a base material layer and dried to obtain an adhesive member for a semiconductor.

  Moreover, the adhesive member for a semiconductor of the present invention is, for example, a polyethylene terephthalate film, a polyethylene film, or a polypropylene film obtained by dissolving or dispersing the composition constituting the adhesive layer in a solvent to obtain a varnish. The adhesive film is formed on the support film by coating, heating and removing the solvent on the support film, and the support film and the base material layer are bonded to the base material layer. It is also possible to produce an adhesive member for a semiconductor in which an adhesive layer is present between them. In this case, the support film can be used as a cover film.

  As a method for applying the varnish on the base material layer or the support film, a known method can be used, for example, knife coating method, roll coating method, spray coating method, gravure coating method, bar coating method, curtain coating method. Law.

  Examples of the base material layer in the semiconductor adhesive member of the present invention include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, polyimide film, and polyvinyl acetate film. These plastic films can be used after releasing the surface of the plastic film. When curing the adhesive layer by irradiating with radiation, the radiation is irradiated from the surface side of the base material layer. Therefore, when using ultraviolet rays, the base material layer must be light transmissive, When used, the substrate layer does not necessarily need to be light transmissive.

  Although there is no restriction | limiting in particular in the thickness of a base material layer, 30-300 micrometers is preferable, 40-250 micrometers is more preferable, 50-200 micrometers is especially preferable. If the thickness of the base material layer is less than 30 μm, the base material layer is likely to be cut during dicing, and the chip tends to be scattered, and if it is thicker than 300 μm, it is not economical.

  The semiconductor device of the present invention is formed by bonding a semiconductor element and a semiconductor element mounting support member using the semiconductor adhesive member of the present invention.

The method for producing a semiconductor device of the present invention comprises a step (I) of attaching a semiconductor wafer to an adhesive layer of an adhesive member for a semiconductor comprising the adhesive layer and the base material layer of the present invention,
Dicing the semiconductor wafer to obtain a semiconductor element with a semiconductor adhesive member (II),
Step (III) of irradiating and curing radiation to the adhesive layer of the semiconductor element with the semiconductor adhesive member,
Step (IV) of obtaining a semiconductor element with an adhesive layer by peeling at the interface between the adhesive layer and the base material layer of the semiconductor element with an adhesive member for a semiconductor,
And a step (V) of adhering the semiconductor element with the adhesive layer to the semiconductor element mounting support member.

  Hereinafter, a method for manufacturing a semiconductor device of the present invention will be described with reference to FIGS.

  As a process (I), a semiconductor wafer is affixed on the adhesive layer of the adhesive member for semiconductors provided with the adhesive layer and base material layer of this invention. The semiconductor to be diced on the upper surface of the adhesive layer 2 by peeling off the support film 3 from the adhesive member for a semiconductor of the present invention (FIG. 1) provided with the base material layer 1, the adhesive layer 2 and the support film 3. Affix the wafer.

  Next, as the step (II), the semiconductor wafer is diced to obtain a semiconductor element with a semiconductor adhesive member. The semiconductor wafer is diced, washed and dried. At this time, since the semiconductor wafer is sufficiently held by the adhesive member for a semiconductor by the adhesive layer 2, the semiconductor wafer does not fall off.

Next, as the step (III), the adhesive layer of the semiconductor element with the semiconductor adhesive member is irradiated with radiation to be cured. The adhesive layer 2 is irradiated with radiation, and a part or most of the adhesive layer 2 having radiation polymerizability is polymerized and cured. The radiation irradiated in the present invention is an actinic ray having a wavelength range of 150 to 750 nm, and includes ultraviolet rays, far ultraviolet rays, near ultraviolet rays, visible rays, electron beams, infrared rays, near infrared rays, and the like. Among these, ultraviolet rays are particularly preferable. Examples of the ultraviolet ray generation source include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and an excimer lamp. The dose of radiation is preferably from 10 to 500 mJ / cm ^2, and more preferably 100 to 500 mJ / cm ^2. When the irradiation amount is less than 10 mJ / cm ² , tackiness does not decrease, and when forming a semiconductor element with an adhesive layer, there is a tendency that peeling of the base material layer and the adhesive layer becomes difficult, Since reaction will advance too much when it exceeds 500 mJ / cm < ² >, there exists a tendency for adhesive force to fall in a subsequent process. Heating may be used in combination with the purpose of accelerating the curing reaction simultaneously with irradiation or after irradiation. Radiation irradiation to the adhesive layer 2 is performed from the surface of the base material layer 1. Therefore, as described above, when ultraviolet rays are used as radiation, the substrate layer 1 needs to be light transmissive, but when using electron beams as radiation, the substrate layer 1 is not necessarily light transmissive. There is no need.

  Subsequently, as process (IV), it peels in the interface of the adhesive agent layer of the said semiconductor element with an adhesive member for semiconductors, and a base material layer, and a semiconductor element with an adhesive layer is obtained. The semiconductor elements 4 to be picked up are sequentially picked up by, for example, a suction collet. At this time, the semiconductor element 4 to be picked up can be pushed up from the lower surface of the base material layer 1 by, for example, a needle rod or the like. Since the adhesive strength between the semiconductor element 4 and the adhesive layer 2 is larger than the adhesive strength between the adhesive layer 2 and the base material layer 1, when the semiconductor element 4 is picked up, the adhesive strength is increased. It peels in the state which the adhesive bond layer 2 adhered to the lower surface of the semiconductor element 4, and a semiconductor element with an adhesive layer can be obtained easily.

  Subsequently, as a process (V), the said semiconductor element with an adhesive agent layer and the support member for semiconductor element mounting are adhere | attached. Each semiconductor element 4 is placed on the semiconductor element mounting support member 5 via the adhesive layer 2 and heated. The adhesive layer 2 develops adhesive strength by heating, and the bonding between the semiconductor element 4 and the semiconductor element mounting support member 5 is completed (FIG. 2). Next, a semiconductor device is obtained by performing bonding or resin sealing. Examples of the support member for mounting a semiconductor include a lead frame, a wiring board, a substrate such as a resist, and a semiconductor chip when stacking semiconductor chips. The wiring board used for the semiconductor mounting board wiring board can be used without being limited to a substrate material such as a ceramic substrate or an organic substrate. As the ceramic substrate, an alumina substrate, an aluminum nitride substrate, or the like can be used. As an organic substrate, an FR-4 substrate in which an epoxy resin is impregnated in a glass cloth, a BT substrate in which a bismaleimide-triazine resin is impregnated, a polyimide film substrate using a polyimide film as a base material, or the like is used. Can do. The shape of the wiring in the wiring board may be a single-sided wiring, a double-sided wiring, or a multilayered wiring structure, and a through hole or a non-through hole that is electrically connected may be provided as necessary. Further, when the wiring appears on the outer surface of the semiconductor device, it is preferable to provide a protective resin layer.

  The structure of the semiconductor device of the present invention thus obtained includes a structure in which the electrode of the semiconductor element and the support member for mounting the semiconductor element are connected by wire bonding, and the electrode of the semiconductor element and the support member for mounting the semiconductor element are tape automated. There is a structure connected by inner lead bonding of Ted Bonding (TAB), but the structure is not limited to these, and any case is effective.

  As the semiconductor element, a general semiconductor element such as an IC, LSI, VLSI can be used.

  The thermal stress generated between the semiconductor element and the semiconductor mounting support member is significant when the area difference between the semiconductor element and the semiconductor mounting support member is small, but the semiconductor device of the present invention has a low elastic modulus adhesive layer. By using the adhesive member for semiconductor having the above, the thermal stress is relaxed and the reliability is ensured. These effects appear very effectively when the area of the semiconductor element is 70% or more of the area of the semiconductor mounting support member. In such a semiconductor device in which the area difference between the semiconductor element and the semiconductor mounting support member is small, the external connection terminals are often provided in an area.

  In addition, as a characteristic of the adhesive member for a semiconductor of the present invention, in the step of heating such as a step of thermocompression bonding the adhesive member to a desired position of the support member for mounting a semiconductor or a step of connecting by wire bonding, Volatile components such as decomposition products from the agent layer can be suppressed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

[Production of adhesive members for semiconductors]
Example 1
Using a 4L glass kettle, pure water and polyvinyl alcohol as a dispersant were added, and 44 parts by weight of butyl acrylate, 27 parts by weight of ethyl acrylate, 3 parts by weight of glycidyl methacrylate, 13 parts by weight of hexamethylene diisocyanate and 13 parts by weight of acrylonitrile were added. In addition, lauroyl peroxide was added as a catalyst, normal octyl mercaptan was added as a chain transfer agent, and the mixture was polymerized in a 60 ° C. hot water bath to obtain an acrylic rubber (1). The weight average molecular weight of the acrylic rubber (1) (value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve) was 500,000.

  YDF-8170C (trade name, manufactured by Tohto Kasei Co., Ltd., bisphenol F type epoxy resin) 55 parts by weight as an epoxy resin, and Millex XLC-LL (trade name, manufactured by Mitsui Chemicals, Inc., xylene-modified cresol novolac type phenol resin) 45 as a phenol resin Parts by weight, 0.7 part by weight of NUC A-1160 (trade name, γ-ureidopropyltriethoxysilane, manufactured by Nihon Unicar Co., Ltd.) as a silane coupling agent, and Antage MB (trade name, manufactured by Kawaguchi Chemical Co., Ltd.) as a proton donating compound , 2-mercaptobenzimidazole) 1.2 parts by weight, Irgacure 651 (trade name, 2,2-dimethoxy-1,2-diphenylethane-1-one) manufactured by Ciba Geigy Co., Ltd. as a photoacid generator Dipentaerythritol as a radiation polymerizable compound Composition comprising 30 parts by weight of ruhexaacrylate (trade name, Shin-Nakamura Chemical Co., Ltd., NK ester A-DPH) and 10 parts by weight of R-972 (trade name, manufactured by Nippon Aerosil Co., Ltd., hydrophobic fumed silica) as an inorganic filler. The product was stirred and mixed with cyclohexanone, and further kneaded for 90 minutes using a bead mill. 200 parts by weight of acrylic rubber (1) was mixed with this and vacuum degassed to obtain a varnish.

  The varnish was coated on a polyethylene terephthalate film having a surface of 75 μm in thickness and subjected to heat drying at 140 ° C. for 5 minutes to form a B-stage coating film having a thickness of 75 μm. A semiconductor adhesive member (1) provided with an adhesive layer was produced.

(Example 2)
Using a 4 L glass kettle, pure water and polyvinyl alcohol as a dispersant were added, 44 parts by weight of butyl acrylate, 27 parts by weight of ethyl acrylate, 3 parts by weight of glycidyl methacrylate, 5 parts by weight of bis (isocyanatomethyl) cyclohexane and acrylonitrile 13 An acrylic rubber (2) was obtained by adding parts by weight, adding lauroyl peroxide as a catalyst, adding normal octyl mercaptan as a chain transfer agent, and polymerizing in a 60 ° C. hot water bath. The weight average molecular weight of the acrylic rubber (2) (value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve) was 300,000.

  A semiconductor adhesive member (2) was produced in the same manner as in Example 1 except that the acrylic rubber (2) was used instead of the acrylic rubber (1).

(Example 3)
Using 4L glass kettle, pure water and polyvinyl alcohol as a dispersant were added, and 44 parts by weight of butyl acrylate, 27 parts by weight of ethyl acrylate, 3 parts by weight of glycidyl methacrylate, 6 parts by weight of hexamethylene diisocyanate and 13 parts by weight of acrylonitrile were added. In addition, lauroyl peroxide was added as a catalyst, normal octyl mercaptan was added as a chain transfer agent, and the mixture was polymerized in a 60 ° C. hot water bath to obtain an acrylic rubber (3). The weight average molecular weight of the acrylic rubber (3) (measured by gel permeation chromatography and converted using a standard polystyrene calibration curve) was 300,000.

  A semiconductor adhesive member (3) was produced in the same manner as in Example 1 except that the acrylic rubber (3) was used instead of the acrylic rubber (1).

(Comparative Example 1)
Using 4L glass kettle, pure water and polyvinyl alcohol as a dispersant are added, 44 parts by weight of butyl acrylate, 27 parts by weight of ethyl acrylate, 3 parts by weight of glycidyl methacrylate and 13 parts by weight of acrylonitrile are added, and lauroyl peroxide is used as a catalyst. And normal octyl mercaptan was added as a chain transfer agent and polymerized in a 60 ° C. hot water bath to obtain an acrylic rubber (4). The weight average molecular weight of the acrylic rubber (4) (measured by gel permeation chromatography and converted using a standard polystyrene calibration curve) was 500,000.

  A semiconductor adhesive member (4) was produced in the same manner as in Example 1 except that the acrylic rubber (4) was used instead of the acrylic rubber (1).

(Comparative Example 2)
A semiconductor adhesive member operated in the same manner as in Example 1 except that HTR-860P (manufactured by Nagase ChemteX Corporation, weight average molecular weight 800,000) was used instead of the acrylic rubber (1) produced in Example 1. (5) was produced.

[Evaluation of adhesive members for semiconductors]
Using the adhesive members for semiconductors (1) to (5) produced as described above, evaluation was performed by the following methods.

(Storage modulus)
Adhesion when the adhesive member for semiconductor cut to a size of 4 mm × 30 mm is irradiated with UV light of 200 mJ / cm ² at an illuminance of 10 mW / cm ² and then cured by a convection dryer at 170 ° C. for 60 minutes. Using a dynamic viscoelasticity measuring device (manufactured by Rheology, “DVE-V4”), a tensile load is applied to the cured adhesive material, a frequency of 10 Hz, and a heating rate of 10 A value at a temperature of 250 ° C. was measured by a temperature dependence measurement mode in which measurement was performed from −50 ° C. to 300 ° C. under the condition of ° C./min.

(Peel strength)
An ultraviolet reaction type dicing tape was bonded to the semiconductor adhesive member, and the T-peel strength of a sample cut to 25 mm × 50 mm was measured using an autograph (manufactured by Shimadzu Corporation) at 300 mm / sec. Further, this sample was irradiated with ultraviolet rays having an illuminance of 10 mW / cm ² and an irradiation amount of 200 mJ / cm ² , and the T-peel strength after irradiation was measured in the same manner as described above.

(Pickup property)
A 75 μm-thick semiconductor wafer on which a test circuit to be diced was formed was attached to the adhesive layer of the adhesive member for semiconductor by laminating at 80 ° C. The semiconductor element with the adhesive member for semiconductors was obtained by fixing on a dicing apparatus, dicing to 5 mm x 5 mm at a speed of 10 mm / sec, washing and drying. Subsequently, the adhesive layer was cured by irradiating ultraviolet rays (365 nm) with an illuminance of 10 mW / cm ² and an irradiation amount of 200 mJ / cm ² from the base material layer side. After the ultraviolet irradiation, the semiconductor element with the adhesive layer was picked up from the base material layer using a suction collet, and the pick-up property was evaluated by the probability (% / chip) of picking up.
(Heat adhesion)
The semiconductor element with an adhesive layer obtained by the evaluation of the pick-up property was die-bonded to an organic substrate (PSR-4000, SR-AUS5, 0.2 mmt) at 120 ° C., 0.1 MPa for 5 seconds. An evaluation sample was obtained by post-curing at 3 ° C. for 3 hours. The evaluation sample was held on a hot plate at 265 ° C. for 20 seconds, and then the thermal adhesive force between the semiconductor element and the organic substrate was measured under the measurement conditions of speed: 50 μm / second, height: 50 μm (“Products 4000”) (product name, Dage). Further, after being left in a constant temperature and humidity chamber at 85 ° C. and 85% for 48 hours, the adhesive strength was measured in the same manner, and this was after moisture absorption.

(PCT resistance)
A semiconductor element with an adhesive member for semiconductor cut to 5 mm square was irradiated with a predetermined amount of ultraviolet light (365 nm) shown in Table 1 from the substrate layer side at an illuminance of 10 mW / cm ² to cure the adhesive layer. . After UV irradiation, a semiconductor element with an adhesive layer obtained by picking up with a suction collet and a wiring board using a polyimide film with a thickness of 25 μm as a base material are bonded together to form a semiconductor device sample (forming solder balls on one side) ) Was produced. The sample was passed through an IR (infrared) reflow oven set at a maximum temperature of 260 ° C. and maintained at this temperature for 20 seconds, and the sample was allowed to cool at room temperature (25 ° C.), and the process of cooling was repeated twice. The occurrence of cracks in the sample was observed visually and with an ultrasonic microscope. In all 10 samples, no crack occurred and ◯ indicates that one or more cracks occurred.

  The present invention provides a semiconductor device having a double bond in a polymer molecule, the reaction rate can be adjusted by heat and UV, the adjustment of the crosslinking density is easy, and the film design margin is improved, and a method for manufacturing the same. Became possible.

It is sectional drawing of an example of the adhesive member for semiconductor provided with the base material layer and adhesive agent layer which concern on this invention. It is a figure which shows the state which carried out the thermocompression bonding of the semiconductor element with an adhesive layer to the supporting member for semiconductor element mounting.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Adhesive agent layer 3 Support film 4 Semiconductor element 5 Support member for semiconductor element mounting

Claims (7)

  An adhesive member comprising an adhesive layer and a substrate layer, wherein the adhesive layer has (A) an epoxy resin and an epoxy resin curing agent, and (B) a weight average molecular weight having a functional group of 100,000 or more. (C) a proton donating compound, (D) a photoacid generator, and (E) a radiation polymerizable compound.   (B) The polymer having a functional group-containing weight average molecular weight of 100,000 or more is an epoxy group- and isocyanate group-containing (meth) acrylic copolymer, and the amount of the epoxy group-containing repeating unit is 0.5 to 0.5. 2. The adhesive member for semiconductor according to claim 1, wherein the adhesive member is 6% by weight.   10 to 400 parts by weight of (B) a polymer having a functional group-containing weight average molecular weight of 100,000 or more with respect to (A) 100 parts by weight of the epoxy resin and the epoxy resin curing agent, and (C) (1) 0.1 to 20 parts by weight of a proton donating compound, (D) 0.5 to 50 parts by weight of a photoacid generator, and (E) 1 to 50 parts by weight of a radiation polymerizable compound. Item 3. The semiconductor adhesive member according to Item 1 or 2.   The storage elastic modulus after heat curing of the adhesive layer is 10 to 5000 MPa at 25 ° C, and 3 to 50 MPa at 250 ° C, The semiconductor according to any one of claims 1 to 3 Adhesive member.   The semiconductor according to any one of claims 1 to 4, wherein the adhesive strength between the adhesive layer and the base material layer is controlled by irradiating the adhesive layer with radiation. Adhesive member.   The semiconductor device formed by adhere | attaching a semiconductor element and the supporting member for semiconductor element mounting using the adhesive member for semiconductors as described in any one of Claims 1-5. A step (I) of attaching a semiconductor wafer to an adhesive layer of an adhesive member for a semiconductor comprising the adhesive layer according to any one of claims 1 to 5 and a base material layer,
Dicing the semiconductor wafer to obtain a semiconductor element with a semiconductor adhesive member (II),
Step (III) of irradiating and curing radiation to the adhesive layer of the semiconductor element with the semiconductor adhesive member,
Step (IV) of obtaining a semiconductor element with an adhesive layer by peeling at the interface between the adhesive layer and the base material layer of the semiconductor element with an adhesive member for a semiconductor,
And a step (V) of bonding the semiconductor element with the adhesive layer and the semiconductor element mounting support member (V).

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