JP2008277796A - Adhesive film for semiconductor, semiconductor device, and method of manufacturing the semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive film for a semiconductor which can achieve high thermal stability and storage stability, and to provide a method of manufacturing a semiconductor device which can simplify the manufacturing process of the semiconductor device using the adhesive film. <P>SOLUTION: In the adhesive film for a semiconductor, a layer 2 of radiation polymerizable adhesive and a substrate layer 3 are sequentially formed. The radiation polymerizable adhesive contains (A) an epoxy resin and an epoxy resin curing agent, (B) a high molecular component containing a functional monomer and having a weight average molecular weight of at least 100,000, and (C) a radioactive ray-polymerizing N-substituted maleimide compound (the substituent is a group having at least one unsaturated double bond of 2 to 30 carbon atoms) expressed by a specific general structural formula. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an adhesive film for semiconductor use, a wiring board for semiconductor mounting provided with the adhesive film, a semiconductor device, and a method for manufacturing the same.

  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 semiconductor wafers used are becoming thinner.

  As an adhesive used for a conventional semiconductor mounting substrate, a liquid or film adhesive is generally used. In addition, along with recent downsizing and higher performance of semiconductor elements, the supporting members used are also required to be downsized and finer. In recent years, adhesive films that are easy to microfabricate have been developed. Many are used.

  Such an 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 attachment method, after cutting the reel-like adhesive film into individual pieces by cutting or punching, the individual pieces are adhered to a support member, and the adhesive film is attached. A semiconductor device is obtained by joining a semiconductor element separated by a dicing process to a support member to produce a support member with a semiconductor element, and then performing a wire bonding process, a sealing process, and the like as necessary. Become. 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. Therefore, there is a problem that the manufacturing cost is increased.

  On the other hand, when manufacturing a semiconductor device using the latter wafer back surface bonding type adhesive film, first, an adhesive film is pasted on the back surface of the semiconductor wafer, and further, an adhesive film for fixing the semiconductor wafer 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 adhesive layer, and it is bonded to a support member, and then heated, cured, and wire A semiconductor device is obtained through a process such as bonding. This wafer back surface bonding type adhesive film joins the semiconductor element with the adhesive film to the support member, so there is no need for an apparatus for separating the adhesive film, 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 generally 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 properties as described above, an operation of switching the adhesive film for each size of semiconductor element and processing conditions has been performed. In addition, since the adhesive force needs to be controlled depending on the size of the element and the processing conditions, the inventory management of the adhesive film has been 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 have been problems such as cracking of the elements when the adhesive film is peeled from the adhesive film.

  On the other hand, the latter UV curable adhesive film has a high adhesive force during dicing, but has a low adhesive force when irradiated with ultraviolet rays before the adhesive film is peeled off from the adhesive film. 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 film and the pressure-sensitive adhesive film are necessary before the dicing step. Therefore, an adhesive sheet in which the adhesive film and the pressure-sensitive adhesive film are laminated in advance, or an adhesive sheet containing a radiation polymerizable compound and a photopolymerization initiator in the adhesive film and the adhesive itself undergoes an ultraviolet curing reaction has been developed ( For example, see Patent Document 1).

  However, if an adhesive sheet obtained by laminating the adhesive film and the pressure-sensitive adhesive film is stored for a long period of time, each curing reaction proceeds and the adhesiveness tends to decrease. This is mainly due to the fact that the photopolymerization initiator contained in the adhesive film gradually reacts with the radiation polymerizable compound. In addition, when the adhesive sheet is used for semiconductor applications, the photopolymerization initiator decomposes when heated to a high temperature in order to completely cure the epoxy resin and epoxy resin curing agent in the package manufacturing process, thereby contaminating the semiconductor element. Therefore, an adhesive film having excellent storage stability and excellent thermal stability is desired.

Japanese Patent No. 3348923

  An object of this invention is to provide the adhesive film for semiconductors which is excellent in thermal stability and storage stability in view of the problem of an above-described prior art. It is another object of the present invention to provide a method for manufacturing a semiconductor device that can simplify the manufacturing process of the semiconductor device.

The present invention relates to the following.
1. An adhesive film for semiconductors formed in the order of a radiation-polymerizable adhesive layer and a substrate layer, wherein the radiation-polymerizable adhesive is (A) an epoxy resin and an epoxy resin curing agent, (B) An adhesive film for semiconductor use, comprising a high molecular weight component having a weight average molecular weight of 100,000 or more, including a functional monomer, and (C) a radiation polymerizable maleimide compound represented by the following general formula (I).

（式中、Ｒ_１は炭素原子数が２〜３０の不飽和二重結合を１つ以上有する基を示す）

(In the formula, R ₁ represents a group having one or more unsaturated double bonds having 2 to 30 carbon atoms)

2. The adhesive film for a semiconductor according to claim 1, wherein the (C) radiation-polymerizable maleimide compound generates a photoradical when irradiated with radiation and has a function as a photopolymerization initiator.
3. The (B) functional monomer-containing high molecular weight component having a weight average molecular weight of 100,000 or more is a glycidyl group-containing (meth) acrylic copolymer, and the amount of the epoxy resin-containing repeating unit is 0.5 to The adhesive film for semiconductors according to claim 1 or 2, which is 6% by weight.
4). In the radiation-polymerizable adhesive, the high molecular weight component having a weight average molecular weight of 100,000 or more containing the functional monomer (B) is 100 parts by weight of the (A) epoxy resin and the epoxy resin curing agent. Item 10. The adhesive film for semiconductor use according to any one of Items 1 to 3, wherein 10 to 400 parts by weight and (C) the radiation polymerizable maleimide compound is contained in an amount of 5 to 120 parts by weight.
5. Item (B) The adhesive film for semiconductor use according to any one of Items 1 to 4, wherein the high molecular weight component containing a functional monomer and having a weight average molecular weight of 100,000 or more is incompatible with the epoxy resin.
6). By irradiating the radiation polymerization type adhesive layer with radiation, the adhesive strength between the adhesive layer (radiation polymerization type adhesive layer) and the base material layer interface can be controlled. The adhesive film for semiconductors in any one of 1-5.
7). The semiconductor device formed by adhere | attaching a semiconductor element and the supporting member for semiconductor element mounting using the adhesive film for semiconductors in any one of claim | item 1 -6.
8). Item 6. A step of attaching a semiconductor wafer to an adhesive layer (a layer of radiation-polymerized adhesive) of the adhesive film for semiconductor use according to any one of Items 1 to 6, and at least the adhesive layer ( The step of forming a semiconductor element with an adhesive layer by dicing together with the radiation-polymerizable adhesive layer), irradiating the adhesive layer of the adhesive film (adhesive film for semiconductor use) with radiation (C) A step of photoradically polymerizing and curing the radiation-polymerizable maleimide compound, a step of peeling the semiconductor element with the adhesive layer from the adhesive film at the interface between the adhesive layer and the base material layer, and the viscosity A method for manufacturing a semiconductor device, comprising: bonding a semiconductor element with an adhesive layer and a semiconductor element mounting support member at a predetermined position.

  According to the present invention, the photopolymerization initiator is incorporated into the reaction system of the film by using a radiation polymerizable compound having a function of generating radicals by irradiating radiation, so there is no dissipation due to the thermal history of each component, It is possible to provide an adhesive film for semiconductor use that is free from contamination in the semiconductor element and assembly process, and has excellent thermal stability and storage stability, and further, it is possible to provide a semiconductor device manufacturing method that can simplify the manufacturing process of the semiconductor device. It became. Moreover, since the adhesive layer using the adhesive composition of the present invention is excellent in storage stability, it has a great effect as compared with conventional adhesive films in terms of a long useful life. Furthermore, by using this adhesive film, it is possible to manufacture a semiconductor device including a semiconductor mounting wiring board and an adhesive layer that are excellent in storage stability.

  The adhesive film for semiconductor use of the present invention (hereinafter abbreviated as an adhesive film) includes a layer of a radiation polymerization type adhesive and a base material layer. The layer of the radiation polymerization type adhesive is (A) an epoxy resin and an epoxy resin curing agent, (B) a high molecular weight component having a weight average molecular weight of 100,000 or more, and (C) the following general formula. A radiation polymerizable maleimide compound represented by (I) is included.

（式中、Ｒ_１は炭素原子数が２〜３０の不飽和二重結合を１つ以上有する基を示す）

(In the formula, R ₁ represents a group having one or more unsaturated double bonds having 2 to 30 carbon atoms)

  In the dicing process, the adhesive film of the present invention has sufficient adhesive strength so that the semiconductor element does not scatter, and when the semiconductor element is bonded to the semiconductor support member, the adhesive layer and the base material layer interface are irradiated by radiation. By satisfying the control of the adhesive strength, the conflicting requirement that the adhesive strength is low enough not to damage each element is satisfied. Furthermore, the adhesive film of the present invention has excellent connection reliability in the die bonding process for joining the semiconductor element and the support member, and each process of dicing and die bonding can be completed with a single adhesive film.

  The epoxy resin used for the adhesive film of the present invention is not particularly limited as long as it is cured and has an adhesive action. For example, bifunctional epoxy resins such as bisphenol A type epoxy, phenol novolac type epoxy resins and cresols are used. Commonly known materials such as a novolak type epoxy resin such as a novolak type epoxy resin, a polyfunctional epoxy resin, a glycidylamine type epoxy resin, a heterocyclic ring-containing epoxy resin, and an alicyclic epoxy resin can be applied. Among them, bifunctional epoxy resins such as bisphenol A type epoxy, novolac type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin, polyfunctional epoxy resins, and alicyclic epoxy resins are preferable, and phenol novolac type epoxy resins and More preferred are novolak epoxy resins such as cresol novolac epoxy resins.

  As said epoxy resin hardening | curing agent used for the adhesive film of this invention, the well-known hardening | curing agent used normally can be used. For example, bisphenols having two or more phenolic hydroxyl groups in one molecule such as amines, polyamides, acid anhydrides, polysulfides, boron trifluoride, bisphenol A, bisphenol F, and bisphenol S, phenol novolac resins, bisphenol A Examples thereof include 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. More preferably, it is a phenol novolac resin or a cresol novolac resin.

  In the high molecular weight component having a weight average molecular weight including the functional monomer (B) used in the adhesive film of the present invention of 100,000 or more, the “functional monomer” means a monomer having a functional group. Examples of the functional group include a glycidyl group, an acryloyl group, a methacryloyl group, a hydroxyl group, a carboxyl group, an isocyanurate group, an amino group, and an amide group, and among them, a glycidyl group is preferable. Among them, the functional monomer having a glycidyl group may include an oligomer as long as the weight average molecular weight is 1000 or less. For example, (meth) acrylic ester copolymer, acrylic rubber, glycidyl acrylate, glycidyl methacrylate, etc. A glycidyl group-containing (meth) acrylic copolymer is more preferable, and glycidyl acrylate and glycidyl methacrylate are particularly preferable.

  Examples of the acrylic rubber include rubbers mainly composed of an acrylate ester and mainly composed of a copolymer such as butyl acrylate and acrylonitrile, a copolymer such as ethyl acrylate and acrylonitrile, or the like.

  The amount of the epoxy resin-containing repeating unit of the glycidyl group-containing (meth) acrylic copolymer is preferably 0.5 to 6.0% by weight, and preferably 0.5 to 5.0% by weight. Is more preferable, and 0.8 to 5.0% by weight is particularly preferable. When the amount of the epoxy resin-containing repeating unit is within this range, the adhesive strength can be secured and gelation can be prevented. Here, the “epoxy resin-containing repeating unit” means the ratio of the monomer weight of the glycidyl group-containing (meth) acrylic copolymer contained in the high molecular weight component. That is, when the total value of the monomers constituting the high molecular weight component is 100 parts by weight, the weight part of the glycidyl group-containing (meth) acrylic copolymer as the monomer is preferably 0.8 to 5.0.

  Examples of the monomer having an acryloyl group or a methacryloyl group include ethyl (meth) acrylate and butyl (meth) acrylate. In the present invention, ethyl (meth) acrylate refers to both ethyl acrylate and ethyl methacrylate.

  These functional monomers may be used alone or in combination of two or more. As a functional monomer, when the glycidyl group-containing (meth) acrylic copolymer and other functional monomers are used in combination, the mixing ratio is the glass transition temperature of the glycidyl group-containing (meth) acrylic copolymer (hereinafter referred to as Tg). It is desirable to decide in consideration of

  Moreover, it is preferable that Tg of the said functional monomer is -10 degreeC or more. When a material having a Tg of −10 ° C. or higher is used, the tackiness of the adhesive layer in the B stage state is appropriate, and there is no problem in handling properties.

  In addition, when a high molecular weight component having a weight average molecular weight of 100,000 or more containing the above functional monomer is produced by polymerizing the monomer, the polymerization method is not particularly limited. For example, a method such as suspension polymerization or solution polymerization Can be used.

  In the present invention, the high molecular weight component containing the functional monomer has a weight average molecular weight of 100,000 or more, preferably 300,000 to 3,000,000, and more preferably 500,000 to 2,000,000. When the weight average molecular weight is 100,000 or more, the strength, flexibility, and tackiness when it is in the form of a member or film are appropriate, and because the flow property is appropriate, the circuit fillability of the wiring is ensured. it can. 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 as will be described later in the column of the evaluation method.

The adhesive layer that forms the adhesive film of the present invention contains (C) a radiation polymerizable maleimide compound represented by the general formula (I). The radiation-polymerizable maleimide compound represented by the general formula (I) is a compound having the general formula (I) that is polymerized and cured when irradiated with radiation such as ultraviolet rays or an electron beam to generate a photoradical. Well, there is no particular limitation, for example, N-maleimidoethyl acrylate, N-maleimidopropyl acrylate, N-maleimidobutyl acrylate, 3-methyl-N-maleimidoethyl acrylate, 3-methyl-N-maleimidoacrylic Propyl acid, 3-methyl-N-maleimidobutyl acrylate, N-phthalimidoethyl acrylate, N-phthalimidopropyl acrylate, N-phthalimidobutyl acrylate, 3-phenyl-N-maleimidoethyl acrylate, 3-phenyl- N-maleimidopropyl acrylate, 3-phenyl-N-maleimidoacrylate Butyl sulfate, N-maleimide ethyl methacrylate, 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-phthalimido ethyl methacrylate, N-phthalimido propyl methacrylate, N-phthalimido butyl methacrylate, 3-phenyl-N-maleimide ethyl methacrylate, 3-phenyl-N-maleimide propyl methacrylate , 3-phenyl-N-maleimide butyl methacrylate and the like can be used. These radiation polymerizable compounds can be used alone or in combination of two or more.
Among them, N-maleimidoethyl acrylate, N-maleimidobutyl acrylate, 3-methyl-N-maleimidoethyl acrylate, 3-methyl-N-maleimidobutyl acrylate, N-phthalimidoethyl acrylate, 3-phenyl-N -Ethyl maleimide acrylate, 3-phenyl-N-butyl maleimide acrylate, N-maleimide ethyl methacrylate, N-maleimide butyl methacrylate, 3-methyl-N-maleimide ethyl methacrylate, 3-methyl-N-maleimide methacrylate Acid butyl, N-phthalimido ethyl methacrylate, N-phthalimido butyl methacrylate, 3-phenyl-N-maleimido ethyl methacrylate, ru and 3-phenyl-N-maleimido butyl methacrylate are preferred. More preferably, N-maleimide ethyl acrylate, N-maleimide butyl acrylate, N-maleimide ethyl methacrylate, N-maleimide butyl methacrylate, 3-methyl-N-maleimide ethyl methacrylate, 3-methyl-N-maleimide They are butyl methacrylate, N-phthalimido ethyl methacrylate, N-phthalimido butyl methacrylate. Particularly preferred are N-maleimidoethyl acrylate, N-maleimidobutyl acrylate, N-maleimidoethyl methacrylate, and N-phthalimidoethyl methacrylate.
(B) A high molecular weight component having a functional monomer and a weight average molecular weight of 100,000 or more and (C) the radiation-polymerizable maleimide compound represented by the general formula (I) are incompatible with each other. It is preferable to select a combination. When a film is formed in an incompatible state, the function of each component is exhibited. For example, the (B) functional monomer improves the reflow resistance of the film, and the (C) component relieves the stress of the entire semiconductor element.

  Moreover, the radiation polymerizable compound which has one or more unsaturated bonds other than the radiation polymerizable maleimide compound shown by general formula (I) can also be used together. The radiation polymerization compound having one or more unsaturated bonds other than those described above 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 acrylate , Methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, pentenyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, diethylene glycol diacrylate, Triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate Trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol Dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, styrene, divinylbenzene, 4 -Vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2- Droxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,2-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide , Tris (β-hydroxyethyl) isocyanurate triacrylate, and the like can be used. These radiation polymerizable compounds can be used alone or in combination of two or more. (C) When using a radiation polymerizable compound having one or more unsaturated bonds other than the radiation polymerizable maleimide compound represented by the general formula (I), (C) the radiation polymerizable property represented by the general formula (I). It is preferable to add 40 to 400 parts by weight with respect to 100 parts by weight of the maleimide compound.

  The amount of each component is 10 to 10 parts by weight of the high molecular weight component having a weight average molecular weight of 100,000 or more including the functional monomer (B) when the epoxy resin and epoxy resin curing agent (A) are 100 parts by weight. 400 parts by weight of the radiation polymerizable maleimide compound represented by the general formula (C) is preferably 5 to 120 parts by weight. Moreover, a photoinitiator can also be added suitably.

  In addition, various coupling agents can be added to the adhesive layer forming the adhesive film of the present invention in order to improve interfacial bonding between different materials. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and among them, a silane-based coupling agent is preferable because it is highly effective.

  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-aminopropyl Limethoxysilane, 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-cyano Propyltriethoxysilane, 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-chloropropylmethyldimethoxysila , Γ-chloropropylmethyldiethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate, methylsilyl triisocyanate, vinylsilyl triisocyanate, phenylsilyl triisocyanate, tetraisocyanate silane, ethoxysilane isocyanate, etc. can be used alone or 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 (n-aminoethyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyl) Oxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, dic Ruphenyloxyacetate 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 chili ethanolamate, Polyhydroxy titanium stearate, Tetramethyl orthotitanate, Tetraethyl orthotitanate, Tetarapropyl orthotitanate, Tetraisobutyl orthotitanate, Stearyl Titanate, cresyl titanate monomer, cresyl titanate , Diisopropoxy-bis (2,4-pentadionate) titanium (IV), diisopropyl-bis-triethanolamino titanate, octylene glycol titanate, tetra-n-butoxy titanium polymer, tri-n-butoxy titanium mono A stearate 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.

  An ion scavenger can be further added to the adhesive layer forming the adhesive film of the present invention in order to adsorb ionic impurities and improve insulation reliability during moisture absorption. Such an ion scavenger is not particularly limited, for example, triazine thiol compound, bisphenol-based reducing agent, etc., a compound known as a copper damage preventing agent for preventing copper ionization and dissolution, zirconium-based And inorganic ion adsorbents such as antimony bismuth-based magnesium aluminum compounds. The amount of the ion scavenger used is, in terms of the effect of addition, heat resistance, cost, etc., when mixed in the adhesive layer, 0.1% with respect to 100 parts by weight of the (A) epoxy resin and epoxy resin curing agent. It is preferable to set it as 1-10 weight part, and when mixing with an adhesive layer, it is preferable to set it as 0.01-100 weight part with respect to 100 weight part of radiation polymerizable compounds.

  In addition, an inorganic filler can be added to the composition constituting the adhesive layer 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 the like, and the shape of the filler is not particularly limited. These 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.

  Further, the average particle size of the inorganic filler is preferably 0.005 μm to 0.1 μm, and the adhesiveness may be lowered even if the average particle size is smaller or larger. As for the compounding quantity of an inorganic filler, 1-20 weight part is preferable with respect to 100 weight part of radiation polymerization type adhesives. If the amount is less than 1 part by weight, the addition effect tends not to be obtained. If the amount exceeds 20 parts by weight, problems such as an increase in storage elastic modulus of the adhesive layer, a decrease in adhesiveness, and a decrease in electrical characteristics due to residual voids are caused. Tend.

  In the production of the varnish when the inorganic filler is added to the adhesive layer of the present invention, in consideration of the dispersibility of the inorganic filler, it is preferable to use a rough machine, a three roll, a ball mill and a bead mill. These can 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. Further, after the varnish is formed, the bubbles in the varnish can be removed by vacuum degassing or the like.

  Although there is no restriction | limiting in particular in the thickness of the adhesive agent layer which forms the adhesive film of this invention, 3-250 micrometers is preferable. If it is thinner than 3 μm, the stress relaxation effect tends to be poor, and if it is thicker than 250 μm, it is not economical and cannot meet the demand for downsizing of the semiconductor device.

  Moreover, in order to obtain desired thickness, the adhesive layer in the adhesive film of this invention can also bond 2 or more layers. In this case, it is necessary to have a bonding condition in which peeling between the adhesive layers is difficult to occur.

  The adhesive layer forming the adhesive film of the present invention preferably has a storage elastic modulus of 10 to 2000 MPa at 25 ° C. and 3 to 50 MPa at 260 ° C. at the stage of heat curing. Further, 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 260 ° 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 support member is maintained, and the occurrence of peeling and cracking can be suppressed, and the handling of the adhesive It is excellent in properties and can suppress the occurrence of reflow cracks. Although the conditions of the said heat-hardening differ also with compositions of an adhesive layer, they are 100-240 degreeC and the range for 5 to 600 minutes normally. This storage elastic modulus is, for example, using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology), applying a tensile load to the cured adhesive (adhesive), a frequency of 10 Hz, and a temperature rising rate. It can be measured by a temperature-dependent measurement mode in which measurement is performed from −70 ° C. to 300 ° C. under a condition of 5 to 10 ° C./min.

  The adhesive film of the present invention is, for example, a solution obtained by dissolving or dispersing the adhesive composition in a solvent to form a varnish, as shown in FIG. By removing, the adhesive layer 2 is formed on the support film 1, and this adhesive layer 2 is bonded to the base material layer 3, whereby the adhesive layer 2 and the support film 1 are combined. An adhesive film in which an adhesive layer is present between the base material layers 3 can also be produced. In this case, the support film can also be used as a cover film.

  Examples of the support film and the base material layer that form the adhesive film of the present invention include a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, a polyimide film, and a polyvinyl acetate film. Such plastic films can also be used after releasing the surface of the plastic film. The support film can be peeled off at the time of use and only the adhesive layer can be used, or it can be used together with the support film and removed later.

  The thickness of the base material layer is not particularly limited, but is preferably 30 to 300 μm, more preferably 40 to 250 μm, and particularly preferably 50 to 200 μm. If it is thinner than 30 μm, it tends to be cut to the base material layer at the time of dicing, and the chip tends to be scattered, and if it is thicker than 300 μm, it is not economical.

  The adhesive film of the present invention is, for example, a solution obtained by dissolving or dispersing the adhesive composition in a solvent to form a varnish, as shown in FIG. By removing, the adhesive layer 2 is formed on the support film 1, and this adhesive layer 2 is bonded to the base material layer 3, whereby the adhesive layer 2 and the support film 1 are combined. An adhesive film in which an adhesive layer is present between the base material layers 3 can also be produced. In this case, the support film can be used as a cover film.

  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.

  As a coating method of the varnish on the base material layer, 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 and the like. It is done.

  When the adhesive film of the present invention is attached to a support member for mounting a semiconductor element, the adhesive film is cut into a predetermined shape, and the cut adhesive film is placed at a desired position on the support member. Although the method of thermocompression bonding is common, it is not limited to this.

  The structure of the semiconductor device of the present invention is a structure in which the electrode of the semiconductor element and the support member are connected by wire bonding, and the electrode of the semiconductor element and the support member are connected by inner lead bonding of tape automated bonding (TAB). However, the present invention is not limited to these structures and is effective in any case. As the semiconductor element, a general semiconductor element such as an IC, LSI, VLSI can be used.

  The wiring shape of the semiconductor device may be a single-sided wiring, double-sided wiring, or multilayer wiring structure, and may be provided with through-holes and non-through-holes that are electrically connected 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 thermal stress generated between the semiconductor element and the support member is significant when the area difference between the semiconductor element and the support member is small, but the semiconductor device of the present invention relieves the thermal stress by using a low elastic modulus adhesive film. To ensure reliability. These effects appear very effectively when the area of the semiconductor element is 70% or more of the area of the support member. In such a semiconductor device having a small area difference between the semiconductor element and the support member, the external connection terminals are often provided in an area.

  In addition, as a characteristic of the adhesive film of the present invention, the volatile matter from the adhesive layer is heated in a process such as a process of thermocompression bonding the adhesive film to a desired position of the support member or a process of connecting by wire bonding. Can be suppressed.

  The wiring board used for the wiring board for a semiconductor mounting board of the present invention 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.

Next, an example of the manufacturing method of the adhesive film and the manufacturing method of the semiconductor device of the present invention will be specifically described with reference to FIGS.
First, an adhesive film provided with the adhesive layer 2 on the base material layer 3 is produced, and when the support film 1 is present on the adhesive layer 2, this is peeled off. Next, after adhering to the upper surface of the adhesive layer 2 to the semiconductor wafer to be diced, the semiconductor wafer is diced, washed and dried. At this time, since the semiconductor wafer is sufficiently held by the adhesive film by the adhesive layer 2, the semiconductor wafer does not fall off during the above steps.

Next, the adhesive layer 2 of the adhesive film is irradiated with radiation, and a part or most of the adhesive layer having radiation polymerization is polymerized and cured. In this case, heating may be used in combination with the purpose of accelerating the curing reaction simultaneously with irradiation or after irradiation. The adhesive film is irradiated with radiation from the surface of the base material layer 3. Therefore, as described above, when UV is used as the radiation, the base material layer 3 needs to be light transmissive, but when EB is used as the radiation, the base material layer 3 is necessarily light transmissive. There is no.
The irradiation of radiation is not particularly limited as long as a lamp that emits light having a wavelength of 365 nm is used. Irradiation dose is preferably 30~700mJ / cm ² at 365nm terms, more preferably ^{100~500mJ / cm 2, 150~350mJ / cm} 2 is particularly preferred.

  After the irradiation, semiconductor elements to be picked up are sequentially picked up by, for example, a suction collet. At this time, the semiconductor element to be picked up can be pushed up from the lower surface of the base material layer by, for example, a needle rod. Since the adhesive strength between the semiconductor element and the adhesive layer is greater than the adhesive strength between the adhesive layer and the base material layer, when the semiconductor element is picked up, the adhesive layer is It peels in the state which adhered to the lower surface of the semiconductor element. Next, 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 exhibits adhesive strength by heating, and the bonding between the semiconductor element 4 and the semiconductor element mounting support member 5 is completed. The heating condition is preferably 40 to 120 ° C, more preferably 50 to 100 ° C, and particularly preferably 60 to 80 ° C.

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

Example 1
62 parts by weight of YDF-8170C (trade name, bisphenol F type epoxy resin, manufactured by Toto Kasei Co., Ltd.) as an epoxy resin, 50 parts by weight of Millex XLC-LL (trade name, manufactured by Mitsui Chemicals) as a curing agent, silane cup A composition comprising 0.85 parts by weight of NUC A-1160 (trade name, γ-ureidopropyltriethoxysilane, manufactured by Nihon Unicar Co., Ltd.) as a ring agent and 35 parts by weight of ethyl N-maleimidoacrylate as a radiation polymerizable compound, Cyclohexanone was added and stirred and mixed, and further kneaded for 90 minutes using a bead mill. This was mixed with 200 parts by weight of acrylic rubber HTR-860P-3 (trade name, manufactured by Teikoku Chemical Industry Co., Ltd., weight average molecular weight 1 million) containing 2 to 6% by weight of glycidyl acrylate or glycidyl methacrylate, and vacuum deaerated. The varnish was applied on a polyethylene terephthalate film having a thickness of 50 μm and subjected to heat drying at 140 ° C. for 5 minutes to form a B-stage coating film having a thickness of 50 μm. An adhesive layer was prepared.
The acrylic rubber HTR-860P-3 is a quaternary copolymer of ethyl acrylate, butyl acrylate, acrylonitrile, and glycidyl methacrylate, and has a weight average molecular weight of about 800,000.

(Example 2)
Except for using 60 parts by weight of ethyl N-phthalimidoacrylate as the radiation-polymerizable compound, the same operation as in Example 1 was performed to prepare an adhesive layer.

(Example 3)
35 parts by weight of 3-methyl-N-maleimide ethyl methacrylate and 35 parts by weight of triacrylate of tris (β-hydroxyethyl) isocyanurate (trade name FA-731A, manufactured by Hitachi Chemical Co., Ltd.) are used as the radiation polymerizable compound. Except that, the same operation as in Example 1 was performed to prepare an adhesive layer.

Example 4
Except for using 35 parts by weight of ethyl 3-methyl-N-maleimidomethacrylate and 20 parts by weight of dipentaerythritol hexaacrylate (trade name Kayrad DPHA, manufactured by Nippon Kayaku Co., Ltd.) as the radiation polymerizable compound, completely the same as Example 1. The same operation was performed to produce an adhesive layer.

(Example 5)
Implemented except that 50 parts by weight of ethyl N-phthalimidoacrylate and 35 parts by weight of triacrylate of tris (β-hydroxyethyl) isocyanurate (trade name FA-731A, manufactured by Hitachi Chemical Co., Ltd.) were used as the radiation polymerizable compound. Exactly the same operation as in Example 1 was performed to produce an adhesive layer.

(Comparative Example 1)
35 parts by weight of triacrylate (β-hydroxyethyl) isocyanurate (trade name FA-731A, manufactured by Hitachi Chemical Co., Ltd.) as a radiation polymerizable compound, and Irgacure 369 (Ciba Geigy Co., Ltd.) as a compound photopolymerization initiator Except that was used), exactly the same operation as in Comparative Example 1 was performed to produce an adhesive layer.

(Comparative Example 2)
Comparison except that 30 parts by weight of dipentaerythritol hexaacrylate (product name: Kayrad DPHA, manufactured by Nippon Kayaku Co., Ltd.) is used as the radiation-polymerizable compound, and Irgacure 369 (manufactured by Ciba-Geigy Corp.) is used as the compound photopolymerization initiator. Exactly the same operation as in Example 1 was performed to produce an adhesive layer.

(Storage stability)
As above-mentioned, the adhesive film provided with the adhesive layer and the base material layer was produced. Furthermore, after adhering to the upper surface of the adhesive layer of the adhesive film on the semiconductor wafer to be diced, the semiconductor wafer was diced, washed and dried to produce a semiconductor device. In addition, the die shear strength (using DAGE D-4000) of the semiconductor device produced using the adhesive film stored in the dark at 25 ± 2 ° C. was measured. The moisture absorption test was performed by observing the peeling from the adhesive film after 168 hours under an atmosphere (pressure cooker test: PCT treatment) of 121 ° C., humidity 100% and 2 atm. The case where the strength declined during storage for 12 months was 10% or less, and the case where the strength was further lowered was rated as x.

(Thermal weight reduction)
The adhesive film was irradiated with radiation to separate the adhesive layer and weighed about 10 mg precisely. The weight reduction rate when the film was heated with a thermobalance (TG-DTA5200 manufactured by SII Nanotechnology) at 175 ° C. for 1 hour was measured. The results are shown in Table 1.

According to Table 1, the adhesive layers of Examples 1 to 5 have a slight decrease in strength at all stages (10% or less), but the adhesives of Comparative Examples 1 and 2 have started after 6 months. The decrease in strength was large (over 10%). In other words, the adhesive layer of the present invention (radiation polymerization type adhesive layer) is excellent in storage stability, and therefore has a longer usable life than a conventional adhesive film (adhesive film for semiconductor use). There is an effect.
In addition, the adhesive layers of Examples 1 to 5 have a slight weight loss due to heat (0.4 to 0.7% by weight) and are very excellent in thermal stability. On the other hand, the weight loss due to heat was very large in the adhesive layers of Comparative Examples 1 and 2 (1.4 to 1.6% by weight).
Therefore, by using the adhesive film of the present invention, it is possible to produce a semiconductor device provided with a semiconductor mounting wiring board and an adhesive layer that are remarkably excellent in thermal stability and storage stability.

It is sectional drawing of an example of the adhesive agent layer provided with the base material layer of the adhesive film which concerns on this invention. It is a figure which shows the state which heat-pressed the semiconductor element with an adhesive bond layer to the support member for semiconductor element mounting.

Explanation of symbols

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

Claims (8)

An adhesive film for semiconductors formed in the order of a radiation-polymerizable adhesive layer and a substrate layer, wherein the radiation-polymerizable adhesive is (A) an epoxy resin and an epoxy resin curing agent, (B) An adhesive film for semiconductor use, comprising a high molecular weight component having a weight average molecular weight of 100,000 or more, including a functional monomer, and (C) a radiation polymerizable maleimide compound represented by the following general formula (I).

(In the formula, R ₁ represents a group having one or more unsaturated double bonds having 2 to 30 carbon atoms)   The adhesive film for a semiconductor according to claim 1, wherein the (C) radiation-polymerizable maleimide compound generates a photoradical when irradiated with radiation and has a function as a photopolymerization initiator.   The (B) functional monomer-containing high molecular weight component having a weight average molecular weight of 100,000 or more is a glycidyl group-containing (meth) acrylic copolymer, and the amount of the epoxy resin-containing repeating unit is 0.5 to The adhesive film for semiconductors according to claim 1 or 2, which is 6% by weight.   In the radiation-polymerizable adhesive, the high molecular weight component having a weight average molecular weight of 100,000 or more containing the functional monomer (B) is 100 parts by weight of the (A) epoxy resin and the epoxy resin curing agent. The adhesive film for a semiconductor according to any one of claims 1 to 3, wherein 10 to 400 parts by weight, and (C) the radiation polymerizable maleimide compound is contained in an amount of 5 to 120 parts by weight.   (B) The high molecular weight component containing a functional monomer and having a weight average molecular weight of 100,000 or more is incompatible with the epoxy resin.   By irradiating the radiation-polymerizable adhesive layer with radiation, the adhesive strength between the adhesive layer (the radiation-polymerizable adhesive layer) and the substrate layer interface can be controlled. Claim | item 1-5 adhesive film for semiconductors in any one.   A semiconductor device formed by bonding a semiconductor element and a support member for mounting a semiconductor element using the adhesive film for semiconductor use according to claim 1.   The process of sticking a semiconductor wafer on the adhesive layer (layer of radiation polymerization type adhesive) of the adhesive film for semiconductor use according to claim 1, at least the adhesive layer of the semiconductor wafer The step of dicing together with the (layer of radiation-polymerizable adhesive) to form a semiconductor element with an adhesive layer, irradiating the adhesive film for semiconductor use with (C) the radiation-polymerizable maleimide compound A step of curing by radical polymerization, a step of peeling the semiconductor element with the adhesive layer from the adhesive film at an interface between the adhesive layer and the base material layer, and the semiconductor element with the adhesive layer And a semiconductor element mounting support member at a predetermined position.

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