JP5056350B2 - Sealing film and semiconductor device using the same - Google Patents

Description

  The present invention relates to a sealing film excellent in filling property, adhesion, and shape maintenance of a semiconductor chip, and a semiconductor device using the same.

  Conventionally, electronic devices have been reduced in size and weight, and accordingly, high-density mounting on a substrate has been required, and semiconductor packages mounted on electronic devices have been reduced in size, thickness, and weight. Yes.

  Conventionally, there are packages called LOC (Lead On Chip), QFP (Quad Flat Package), etc., and μBGA (Ball Grid Array), CSP (Chip (Chip), etc., which are smaller and lighter than packages such as LOC, QFP, etc. A package such as Size Package has been developed.

  Further, flip-chips such as so-called face-down packages, WL-CSP (Wafer Level Chip Size Package), and the like, in which the circuit surface of the semiconductor element is directed to the semiconductor wiring substrate side have been developed.

  In the above-described package, a sealed package is obtained by molding a solid epoxy resin sealing material by a transfer molding method, but molding when the package is thin or large is difficult.

  In addition, when the content of the inorganic filler is increased, generally the melt viscosity at the time of transfer molding is increased, and voids remaining at the time of molding, poor cavity filling, increased wire flow and stage shift, and the quality of the molded product are reduced. Problems occur.

In recent years, some flip-chips and WL-CSPs have protruding electrodes, and a sealing material is sometimes used for protecting the protruding portions and filling the protruding portions. Filling with a resin sealing material was difficult. Therefore, a sealing film mainly composed of an epoxy resin and an inorganic filler has been proposed (see, for example, Patent Documents 1, 2, 3, and 4).
Japanese Patent Laid-Open No. 05-283456 Japanese Patent Laid-Open No. 05-190697 Japanese Patent Laid-Open No. 08-73621 JP 2005-060584 A

  However, when a conventional sealing film is used to seal, for example, a package having a protruding electrode or a package having a shape restriction after sealing, it is difficult to control the fluidity, and the filling property and adhesion In some cases, it was not possible to satisfy all the properties and shape maintenance properties.

  In view of the above, the present invention provides a sealing film excellent in all of fillability, adhesion, and shape maintenance, and a semiconductor device using the same.

  The present invention comprises (1) (A1) a high molecular weight resin containing a crosslinkable functional group, a weight average molecular weight of 100,000 or more and a Tg of −50 to 50 ° C., and (A2) an epoxy resin as a main component. A sealing film having a resin layer containing a (A) resin component, (B) filler, and (C) a colorant, and having a shear viscosity of 14,000 to 25000 Pa · s at 80 ° C. About.

  Moreover, this invention is (2) said (A) resin component containing 15-85 weight% of (A1) high molecular weight resin, and (A2) 15-85 weight% of thermosetting components, Said (1) description It is related with the sealing film.

  Further, the present invention includes (3) 1 to 300 parts by weight of the (B) filler and 0.01 to 10 parts by weight of the colorant (C) with respect to 10 parts by weight of the (A) resin component. The present invention relates to the sealing film according to (1) or (2).

  In addition, the present invention provides (4) the above (1) to (3), further comprising a base material layer having a thickness of 5 to 300 μm on one surface of the resin layer, and the resin layer having a thickness of 5 to 800 μm. It is related with the sealing film of any one of these.

  The present invention further includes (5) a base layer having a thickness of 5 to 300 μm on one surface of the resin layer, and a protective layer having a thickness of 5 to 300 μm on the other surface of the resin layer, and It is related with the sealing film of any one of said (1)-(3) whose thickness of the said resin layer is 5-800 micrometers.

  Moreover, this invention relates to the sealing film of any one of said (1)-(5) whose (6) said (B) filler is an inorganic filler.

  Moreover, this invention relates to the sealing film of any one of said (1)-(6) whose (7) said (C) coloring agent is other than white.

  Moreover, this invention is (8) Said (1)-(7) whose storage elastic modulus in the dynamic-viscoelasticity measuring apparatus in 35 degreeC after hardening | curing at 170 degreeC for 1 hour of said resin layer is 500-20000 MPa. It is related with the sealing film of any one of (1).

  The present invention also relates to (9) a semiconductor device using the sealing film according to any one of (1) to (8).

  According to the present invention, it is possible to provide a sealing film that is excellent in filling properties, adhesion, and shape maintainability, and also excellent in laser marking visibility and suitable for protecting semiconductor chips and filling cavities. Moreover, it becomes possible to provide a semiconductor device with excellent reliability by using the sealing film.

  The sealing film of the present invention has at least a resin layer containing (A) a resin component containing (A1) a high molecular weight resin and (A2) a thermosetting component, (B) a filler, and (C) a colorant. In use, the semiconductor element is sealed with the resin layer.

  The (A1) high molecular weight resin has a crosslinkable functional group, and for example, a polymer obtained by polymerizing a functional monomer such as an epoxy group-containing monomer can be used. Preferably, an epoxy group-containing (meth) acrylic copolymer using glycidyl (meth) acrylate as a functional monomer, and further polymerized with a monomer such as ethyl (meth) acrylate or butyl (meth) acrylate Can also be used. The (A1) high molecular weight resin is preferably incompatible with the epoxy resin. In the present invention, “(meth) acryl” means both “acryl” and “methacryl”. In addition, when the (A1) high molecular weight resin is produced by polymerizing a functional monomer, the polymerization method is not particularly limited, and for example, a known method such as pearl polymerization or solution polymerization may be used. In addition, the polymerization conditions may be determined as appropriate in consideration of the monomers used and their concentrations, the weight average molecular weight of the (A1) high molecular weight resin, the glass transition temperature, and the like, and are not particularly limited.

  Examples of the epoxy group-containing (meth) acrylic copolymer include, for example, an epoxy group-containing (meth) acrylic ester copolymer, an epoxy group-containing acrylic rubber, and the use of an epoxy group-containing acrylic rubber is particularly preferable. preferable. The acrylic rubber is mainly composed of an acrylic ester, and is a rubber made of, for example, a copolymer of butyl acrylate or ethyl acrylate and acrylonitrile. As such an epoxy group-containing acrylic rubber, for example, HTR-860P-3DR manufactured by Nagase ChemteX Corporation is commercially available. The amount of the epoxy group-containing monomer in the epoxy group-containing copolymer is preferably 0.5 to 6.0% by weight, more preferably 0.5 to 5.0% by weight, It is particularly preferably 0.8 to 5.0% by weight. When the amount of the epoxy group-containing monomer is within this range, the adhesive force can be ensured and gelation can be prevented.

  The weight average molecular weight of the (A1) high molecular weight resin is 100,000 or more, preferably 300,000 to 3,000,000, more preferably 500,000 to 2,000,000. By using a high molecular weight resin having a weight average molecular weight within this range, it is possible to appropriately control the strength, flexibility and tackiness when formed into a film, and the resin layer and the adherend Can be secured. 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 glass transition temperature (Tg) of the (A1) high molecular weight resin is −50 ° C. or higher and 50 ° C. or lower. By setting the Tg to -50 ° C. or more and 50 ° C. or less, the tackiness in the B-stage state of the resin layer can be appropriately maintained, and the handleability is also improved.

  The blending amount of the (A1) high molecular weight resin is preferably 15 to 85% by weight, more preferably 20 with respect to the total amount of (A1) high molecular weight resin and (A2) thermosetting component. It is -85 weight%, Most preferably, it is 20-80 weight%, Most preferably, it is 25-80 weight%. (A1) If the blending amount of the high molecular weight resin is less than 15% by weight, the resulting resin layer may have insufficient flexibility and become brittle, and if it exceeds 85% by weight, the resulting resin layer has fluidity. May be reduced.

  The (A2) thermosetting component is not particularly limited as long as it is cured by heat and exhibits an adhesive action, but preferably contains an epoxy resin as a main component and contains 60 to 100% by weight of the epoxy resin. Is more preferable. Examples of the epoxy resin include bifunctional epoxy resins such as bisphenol A type epoxy and bisphenol F type epoxy resin, and novolak type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin. Moreover, what is generally known, such as a polyfunctional epoxy resin, a glycidyl amine type epoxy resin, a heterocyclic ring-containing epoxy resin, or an alicyclic epoxy resin, can be applied.

  Examples of the bisphenol A type epoxy resin include Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007, 1009 manufactured by Yuka Shell Epoxy, DER-330, 301, 361 manufactured by Dow Chemical Co., Ltd. Examples include YD8125 and YDF8170 manufactured by Toto Kasei Co., Ltd. Examples of the bisphenol F type epoxy resin include YD-8170C manufactured by Tohto Kasei Co., Ltd. Examples of the phenol novolac type epoxy resin include Epicoat 152 and 154 manufactured by Yuka Shell Epoxy Co., Ltd., EPPN-201 manufactured by Nippon Kayaku Co., Ltd., DEN-438 manufactured by Dow Chemical Co., Ltd., and the cresol novolak type epoxy resin. Examples of the resin include EOCN-102S, 103S, 104S, 1012, 1025, and 1027 manufactured by Nippon Kayaku Co., Ltd., which are o-cresol novolac type epoxy resins, and YDCN701, 702, 703, and 704 manufactured by Toto Kasei Co., Ltd. It is done. As the polyfunctional epoxy resin, Epon 1031S manufactured by Yuka Shell Epoxy Co., Ltd., Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., Denacol EX-611, 614, 614B, 622, 512, 521, 421 manufactured by Nagase Chemical Co., Ltd. , 411, 321 and the like. As the glycidylamine type epoxy resin, Epiquat 604 manufactured by Yuka Shell Epoxy Co., Ltd., YH-434 manufactured by Tohto Kasei Co., Ltd., TETRAD-X, TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., Sumitomo Chemical Co., Ltd. Product ELM-120 etc. are mentioned. Examples of the heterocyclic ring-containing epoxy resin include ERL4234, 4299, 4221, and 4206 manufactured by UCC, such as Araldite PT810 manufactured by Ciba Specialty Chemicals. These epoxy resins can be used alone or in combination of two or more.

  Moreover, when using an epoxy resin as said (A2) thermosetting component, it is preferable to use an epoxy resin hardening | curing agent and a hardening accelerator as the said component further. As the epoxy resin curing agent, known curing agents that are usually used can be used. For example, amines, polyamides, acid anhydrides, polysulfides, boron trifluoride, bisphenol A, bisphenol F, and bisphenol S can be used. Bisphenols having two or more phenolic hydroxyl groups in one molecule, phenol resins such as phenol novolac resin, bisphenol A novolak resin or cresol novolac resin, phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) ) Phenol / aralkyl resins synthesized from biphenyl. In particular, phenol resins such as phenol novolak resin, bisphenol A novolak resin or cresol novolak resin, and phenol-aralkyl resin are preferable in terms of excellent electric corrosion resistance when absorbing moisture. Preferred phenol resin curing agents include, for example, Dainippon Ink & Chemicals, Inc., trade names: Pryofen LF2882, Pryofen LF2822, Pryofen LF4871, Pryofen TD-2090, Pryofen TD-2149, Pryofen VH -4150, priofen VH4170, and the like. Preferable phenol-aralkyl resins include, for example, trade name “Mirex XLC-LL” manufactured by Mitsui Chemicals, Inc.

Moreover, as said hardening accelerator, a quaternary phosphonium salt type | system | group, a quaternary ammonium salt type | system | group, an imidazole type | system | group, a DBU fatty acid salt type | system | group, a metal chelate type | system | group, a metal salt type | system | group, a triphenylphosphine type etc. can be used, for example. . Moreover, the compounding quantity of the said hardening | curing agent and hardening accelerator is although it does not specifically limit, Preferably it is 0.05 to 0.5 weight% in the said (A2) thermosetting component.

  The blending amount of the (A2) thermosetting component is preferably 15 to 85% by weight, more preferably, based on the total amount of the (A1) high molecular weight resin and the (A2) thermosetting component. 15 to 80% by weight, particularly preferably 20 to 80% by weight, and most preferably 20 to 75% by weight. (A2) If the blending amount of the thermosetting component is less than 15% by weight, the heat resistance and fluidity of the resulting resin layer may be reduced, and if it exceeds 85% by weight, the resulting resin layer is flexible. May be reduced.

  Moreover, in this invention, you may mix | blend the resin component other than the above as a resin component in the range which does not deviate from the objective of this invention as needed as said (A) resin component.

  Although it does not specifically limit as said (B) filler, It is preferable that it is an inorganic filler, for example, crystalline silica, amorphous silica, aluminum oxide, titanium oxide, calcium carbonate, magnesium carbonate, aluminum nitride, boron nitride etc. Can be used.

  The blending amount of the (B) filler is preferably 1 to 300 parts by weight, more preferably 3 to 250 parts by weight, and particularly preferably 3 to 200 parts by weight with respect to 10 parts by weight of the (A) resin component. Parts by weight, most preferably 5 to 200 parts by weight. (B) If the blending amount of the filler is less than 1 part by weight, the resulting sealing film may become soft and the reliability of the resulting semiconductor device may be reduced. Adhesion with a semiconductor substrate may be reduced.

  The colorant (C) in the present invention is not particularly limited. For example, carbon black, graphite, titanium carbon, manganese dioxide, phthalocyanine-based pigments or dyes can be used. In consideration of dispersibility and laser marking properties, colorants other than white such as carbon black are preferred.

  The blending amount of the colorant (C) is preferably 0.01 to 10 parts by weight, more preferably 0.2 to 8 parts by weight, particularly preferably 10 parts by weight of the resin component (A). Is 0.3-6 parts by weight, most preferably 0.5-5 parts by weight. (C) When the amount of the colorant used is less than 0.01 parts by weight, the resulting sealing film is not sufficiently colored, and the visibility after laser marking tends to deteriorate. There is a possibility that the adhesion between the sealing film and the semiconductor substrate is lowered.

  The resin layer in this invention may contain additives, such as a coupling agent, as needed other than the said (A) resin component, (B) filler, and (C) coloring agent. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and silane-based coupling agents are most preferable.

  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-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyl-trimethoxysilane, 3-4,5-dihydroimidazole-1 -Yl-propyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-mercaptopropyl-methyldimethoxysilane, 3-chloropropyl-methyldimethoxysilane, 3-chloropropyl-dimethoxysilane , 3-cyanopropyl-triethoxysilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxy Silane, 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-chloropropylme Rudimethoxysilane, γ-chloropropylmethyldiethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate, methylsilyl triisocyanate, vinylsilyl triisocyanate, phenylsilyl triisocyanate, tetraisocyanate silane, ethoxysilane isocyanate, etc. can be used. These 1 type (s) or 2 or more types can also be used together.

  The titanium-based coupling agent is not particularly limited, and examples thereof include isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate. , Isopropyltricumylphenyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltris (n-aminoethyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2 , 2-Diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite , Dicumylphenyloxyacetate 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, cresi Titanate polymer, diisopropoxy-bis (2,4-pentadionate) titanium (IV), diisopropyl-bis-triethanolamino titanate, octylene glycol titanate, tetra-n-butoxy titanium polymer, tri-n-butoxy titanium A monostearate polymer, tri-n-butoxytitanium monostearate, etc. can be used, and these 1 type (s) or 2 or more types can also be used together.

  The aluminum coupling agent is not particularly limited. For example, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate) Aluminum tris (acetylacetonate), aluminum = monoisopropoxymonooleoxyethyl acetoacetate, aluminum-di-n-butoxide-mono-ethylacetoacetate, aluminum-di-iso-propoxide-mono-ethylacetoacetate, etc. Aluminum chelate compound, aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate, aluminum-se - butylate, aluminum alcoholates of aluminum ethylate or the like can be used, may be used in combination one or more of them.

  The additive such as the coupling agent is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the resin component (A). When there are more compounding quantities of the said additive than 50 weight part, the heat resistance of the sealing film obtained may fall.

  Moreover, the shear viscosity in 80 degreeC of the resin layer in this invention is 14000-25000 Pa.s, Preferably it is 16000-23000 Pa.s. If this shear viscosity exceeds 25000 Pa · s, the reliability of the resulting semiconductor device and the adhesion between the sealing film (resin layer) and the semiconductor substrate tend to be reduced, and if it is less than 14000 Pa · s, the resulting sealing is obtained. When sealing a semiconductor element with a stop film (resin layer), resin flows directly into the element, and the desired semiconductor characteristics tend not to be obtained. The “shear viscosity” in the present invention is a measurement frequency of a resin layer (film) in a B stage state of 10 mm × 10 mm × thickness 150 μm, using a shear viscosity measuring device (manufactured by TA Instruments Japan Co., Ltd.). It is a value obtained by measurement under the conditions of 1.0 Hz, a probe diameter of 8.0 mm, and a measurement temperature of 80 ° C. This shear viscosity is, for example, increasing the filling amount of the filler, improving the crosslinking density of the resin layer using a polyfunctional epoxy resin, increasing the thermal history when forming a film, and the degree of cure in the B stage state It can be enlarged by improving.

  Moreover, the storage elastic modulus in the dynamic viscoelasticity measuring apparatus at 35 ° C. after the resin layer in the present invention is cured at 170 ° C. for 1 hour is preferably 500 to 20000 MPa, more preferably 600 to 19000 MPa. Especially preferably, it is 700-18000 MPa, Most preferably, it is 1000-16000 MPa. If the tensile elastic modulus is less than 500 MPa, the adhesion between the obtained sealing film (resin layer) and the semiconductor element may be reduced, and if it exceeds 20000 MPa, the reliability of the semiconductor device may be reduced. In addition, the said storage elastic modulus is measured on the conditions of 35 degreeC and 10 Hz using the dynamic viscoelasticity spectrometer (DVE-4 type) made from a rheology company about the said resin layer film sample of 150 micrometers in thickness in the B stage state. Is obtained. This storage elastic modulus can be increased by increasing the filling amount of the filler or improving the crosslink density of the resin layer using a polyfunctional epoxy resin.

  The thickness of the resin layer in the present invention is preferably 5 to 800 μm, more preferably 10 to 600 μm, particularly preferably 20 to 500 μm, and most preferably 30 to 400 μm. If the thickness of the resin layer is less than 5 μm, the adhesion to the semiconductor element may be reduced or the flow-in amount may be insufficient. If the thickness exceeds 800 μm, the thickness of the semiconductor element increases and the package design is impaired. There is a possibility.

  Moreover, the sealing film of this invention has the base material layer 1 which can support this and can improve the intensity | strength of a film, a handleability, etc. on the single side | surface of the said resin layer 2, as shown in FIG. Also good. The thickness of the base material layer may be appropriately determined in consideration of the thickness and strength of the resin layer, and is not particularly limited, but is preferably 5 to 300 μm, more preferably 5 to 200 μm, and particularly preferably. It is 5-100 micrometers, Most preferably, it is 10-100 micrometers. If the thickness of the base material layer is less than 5 μm, the effect of improving the strength and handleability of the film by supporting the resin layer may not be sufficiently obtained, and the thickness of the base material layer exceeds 300 μm. There is no particular advantage, and the film itself may be expensive.

  The substrate layer is not particularly limited. For example, polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, polyethylene naphthalate film, polyethersulfone film, polyetheramide film, A plastic film such as a polyetheramideimide film, a polyamide film, a polyamideimide film, and a polyimide film can be used. If necessary, surface treatment such as primer application, UV treatment, corona discharge treatment, polishing treatment, etching treatment, mold release treatment may be performed on the surface in contact with the resin layer.

  Moreover, the sealing film of this invention may have the protective layer for protecting this on the single side | surface of the said resin layer. Although the thickness of a protective layer is not specifically limited, Preferably it is 5-300 micrometers, More preferably, it is 5-200 micrometers, Especially preferably, it is 5-100 micrometers, Most preferably, it is 10-100 micrometers. If the thickness of the protective layer is less than 5 μm, the film may not be sufficiently protected. If the thickness of the film exceeds 300 μm, there is no particular advantage, and the film itself may be expensive.

  The protective layer is not particularly limited. For example, polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, polyethylene naphthalate film, polyethersulfone film, polyetheramide film, poly A plastic film such as an etheramideimide film, a polyamide film, a polyamideimide film, and a polyimide film can be used. If necessary, surface treatment such as primer application, UV treatment, corona discharge treatment, polishing treatment, etching treatment, mold release treatment may be performed on the surface in contact with the resin layer.

  Moreover, the sealing film of this invention may have the said base material layer 1 in the one surface of the said resin layer 2, and the said protective layer 3 in the other surface, as shown in FIG.

  Although the method of producing the sealing film of this invention is not specifically limited, For example, after apply | coating the varnish containing at least the said (A) resin component, (B) filler, and (C) coloring agent on a base material layer. It can be produced by removing the solvent by heat drying and forming a B-stage resin layer. Although the said heat-drying conditions change with the components of a resin layer, and the kind of solvent, generally it heats for 3 to 30 minutes at the temperature of 60-200 degreeC. The method for applying the varnish is not particularly limited, but in consideration of workability and the like, it is preferable to apply using a multicoater.

  The semiconductor device of the present invention is characterized by using the sealing film of the present invention. Hereinafter, although the manufacture example and form are demonstrated using figures, this invention is not limited to the following description.

  FIG. 3 is a schematic view showing a process of sealing the electrode on the semiconductor substrate 4 with the sealing film (resin layer 2) of the present invention. Although there is no restriction | limiting in particular as a semiconductor substrate, For example, a silicon wafer etc. are mentioned. Here, when the sealing film of the present invention having the configuration shown in FIG. 1 is used, the sealing film is laminated so that the resin layer 2 is in contact with the electrode surface of the semiconductor substrate 4, and the electrode on the semiconductor substrate is sealed. Stop. In addition, when using the sealing film of the present invention having the configuration shown in FIG. 2, after peeling off the protective layer 3, the sealing film is laminated so that the resin layer 2 is in contact with the electrode surface of the semiconductor substrate 4, The electrode on the semiconductor substrate is sealed. Although the laminating method is not particularly limited, for example, a method using a hot roll laminator is exemplified. As shown in FIG. 3, the roll-shaped sealing film 8 is interposed between the pair of laminator rolls 10 via the roll 9 as shown in FIG. It is done by passing with. The laminating temperature in the laminating step is preferably 180 ° C. or lower, more preferably 140 ° C. or lower, and particularly preferably 120 ° C. or lower in terms of excellent workability without giving a load to the semiconductor substrate. . Moreover, the sealing film of this invention is especially suitable when the said electrode is a protruding electrode.

  In addition, the sealing with the sealing film of the present invention is not limited to the above-described film lamination method, but a method in which the sealing film is thermocompression-bonded or vacuum-bonded to the semiconductor substrate, or the sealing film is directly bonded to the semiconductor element by heat press. It is also possible to use a method or the like. The pressure bonding conditions and the like vary depending on the type of sealing film used, the shape of the semiconductor substrate, or the element.

  FIG. 4 is a schematic view of a semiconductor element 7 having protruding electrodes 5 sealed with the sealing film (resin layer 2) of the present invention. In such a semiconductor element, after sealing the protruding electrodes 5 of the semiconductor substrate as shown in FIG. 3, for example, a step of peeling the base material layer of the sealing film, a step of curing the resin layer 2 by heating A step of mounting the solder ball 6 on the protruding electrode 5, a step of laminating a dicing tape on the surface of the semiconductor substrate opposite to the resin layer side, a step of dicing the semiconductor substrate to a predetermined size, the protruding electrode 5 A semiconductor device having excellent reliability and the like can be obtained by mounting the obtained semiconductor element at a predetermined position on the circuit board. Further, the semiconductor element can be irradiated with a YAG laser or the like from the sealing film side to display identification information for identifying the product.

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

<Preparation of sealing film>
Example 1
(A) Epoxy group-containing acrylic rubber (manufactured by Nagase ChemteX Corporation, trade name HTR-860P-3DR, weight average molecular weight: 800,000, Tg: −7 ° C.) as the high molecular weight resin (A1) of the resin component 4 parts by weight, (A2) As thermosetting component, bisphenol F type epoxy resin (trade name YD-8170C, epoxy equivalent 160, manufactured by Toto Kasei Co., Ltd.) 33.6 parts by weight, phenol / p-xylylene glycol dimethyl ether Polymerization resin (Mitsui Chemicals, trade name: Mirex XLC-LL, hydroxyl group equivalent: 174) 33.8 parts by weight, 1-cyano-1-phenylimidazole (Shikoku Kasei Kogyo Co., Ltd., trade name: CURESOL 2PZ-CN) 0 .1 part by weight, (B) Silica filler (manufactured by Tatsumori Co., Ltd., trade name TFC-24, average particle diameter) (8 μm) 152.6 parts by weight, (C) As a colorant, 8.4 parts by weight of a resin-based processed pigment (manufactured by Sanyo Color Co., Ltd., trade name FP BLACK 308, carbon black content 29.0% by weight), and cup As a ring agent, cyclohexanone was added to a composition consisting of 1.0 part by weight of glycidoxypropyltrimethoxysilane (trade name Z-6040, manufactured by Toray Dow Corning Co., Ltd.), mixed with stirring, degassed by vacuum, and non-volatile. About 60% varnish was obtained (hereinafter abbreviated as NV). The NV value was calculated from the non-volatile content remaining after heating and drying a predetermined amount of varnish (about 1 hour at 170 ° C.) and the varnish weight measured before heating and drying.

  The varnish obtained above was applied on a base material layer (manufactured by Teijin DuPont Films, trade name Purex A31B, surface release treatment polyethylene terephthalate film, film thickness 38 μm), 90 ° C., 5 minutes and 140 ° C., It was heat-dried for 11 minutes to obtain a coating film having a film thickness of 150 μm, and a B-stage sealing film A was obtained.

(Example 2)
The same operation as in Example 1 was performed except that the drying conditions of the varnish applied on the base material layer were changed from 90 ° C, 5 minutes and 140 ° C, 11 minutes to 90 ° C, 5 minutes, 140 ° C and 10 minutes. The sealing film B in the B stage state was obtained.

(Example 3)
The same operation as in Example 1 was performed except that the drying conditions of the varnish applied on the base material layer were changed from 90 ° C., 5 minutes and 140 ° C., 11 minutes to 90 ° C., 5 minutes and 140 ° C., 8 minutes. A sealing film C in a B-stage state was obtained.

Example 4
The same operation as in Example 1 was performed except that the drying conditions of the varnish applied on the base material layer were changed from 90 ° C., 5 minutes and 140 ° C., 11 minutes to 90 ° C., 5 minutes and 140 ° C., 14 minutes. The B-stage sealing film D was obtained.

(Comparative Example 1)
Except for changing the drying conditions of the varnish applied on the base material layer from 90 ° C., 5 minutes and 140 ° C., 11 minutes to 90 ° C., 5 minutes and 140 ° C., 5 minutes, the same operation as in Example 1 was performed. A sealing film E in a B-stage state was obtained.

(Comparative Example 2)
Except that the drying conditions of the varnish applied on the base material layer were changed from 90 ° C., 5 minutes and 140 ° C., 11 minutes to 90 ° C., 5 minutes and 140 ° C., 17 minutes, the same operation as in Example 1 was performed. B stage sealing film F was obtained.

(Comparative Example 3)
A composition was prepared in the same manner as in Example 1 except that it did not contain the component (B) filler, and the amount of the resin-based processed pigment (C) used was changed from 8.4 parts by weight to 8.3 parts by weight. Then, cyclohexanone was added, mixed with stirring, and vacuum degassed to obtain a varnish having an NV of about 60%.

  The obtained varnish was applied onto a base material layer (trade name Purex A31B, surface release treatment polyethylene terephthalate film, film thickness 38 μm, manufactured by Teijin DuPont Films Ltd.), 90 ° C., 20 minutes and 140 ° C., 20 The film was dried by heating to obtain a coating film having a film thickness of 150 μm, and a sealing film G in a B-stage state was obtained.

(Comparative Example 4)
The amount of the silica filler used as the component (B) was changed from 152.6 to 356.2 parts by weight, and the amount of the resin-based processed pigment used as the component (C) was changed from 8.4 to 15.3 parts by weight. Except for the above, a composition was obtained in the same manner as in Example 1, and cyclohexanone was added, mixed with stirring, vacuum degassed to obtain a varnish having an NV of about 70%.

  The obtained varnish was applied onto a base material layer (trade name Purex A31B, surface release treatment polyethylene terephthalate film, film thickness 38 μm, manufactured by Teijin DuPont Films Ltd.), 90 ° C., 5 minutes and 140 ° C., 5 Heat-dry for a minute to obtain a coating film having a film thickness of 150 μm, and a B-stage sealing film H was obtained.

<Evaluation of sealing film (resin layer)>
For the sealing films A to H (resin layers) obtained in Examples 1 to 4 and Comparative Examples 1 to 4, the shear viscosity, storage elastic modulus, glass transition temperature, thermal decomposition start temperature, resin flowability (flow controllability) ) And laser marking visibility were evaluated as follows. The results are summarized in Table 1.

-Shear viscosity Each sealing film obtained above was cut out to 10 square mm, and it measured using the shear viscosity measuring apparatus (TA Instruments Japan Co., Ltd. product). The measurement conditions were a measurement frequency of 1.0 Hz, a probe diameter of 8.0 mm, and a measurement temperature of 80 ° C.

-Storage modulus and glass transition temperature (Tg)
After each sealing film obtained above was cured at 170 ° C. for 1 hour, storage elastic modulus (35 ° C., 10 Hz) and glass transition were measured with a dynamic viscoelastic spectrometer (DVE-4 type, manufactured by Rheology). The temperature (frequency 10 Hz, temperature rising rate 2 ° C./min) was measured.

-Thermal decomposition start temperature The thermal decomposition start temperature of each sealing film was measured with a differential thermal balance (manufactured by Seiko Instruments Inc., model SSC5200) under the conditions of a temperature increase rate of 10 ° C / min and an atmosphere of air. .

-Resin flowability (flow controllability)
Each sealing film obtained above was used as a semiconductor substrate (pitch dimensions: 5.3 mm × 6.3 mm, scribe line: 100 μm, copper post diameter: 300 μm, copper post height: 100 μm) on which wiring and copper posts were formed. ) A hot roll laminator (manufactured by Taisei Laminator Co., Ltd., trade name: VA-400III type) was used (lamination conditions: 80 ° C., 0.2 MPa, 0.5 m / min). After laminating, the semiconductor substrate to which each sealing film is affixed is cut, the cross section is observed with an optical microscope, the amount (flow value) of the resin layer flowing between the copper posts is measured, and within the target flow value range Whether or not (± 5 μm) was included was evaluated according to the following criteria (10 points were measured per sample, and evaluations ○ and Δ passed).

○: Flow values at all measurement points are within the target flow value range (± 5 μm).
Δ: Of the number of measurement points, only one flow value is not within the target flow value range.
X: The flow value of 2-9 points | pieces is not in the target flow value range among the number of measurement points.
XX: Flow values at all measurement points are not within the target flow value range.
・ Visibility of laser marking

  Each sealing film obtained above is pasted to a 300 μm thick silicon wafer mirror surface using a hot roll laminator (trade name VA-400III type, manufactured by Taisei Laminator Co., Ltd.) (lamination conditions: 80 ° C., 0.2 MPa). 0.5 m / min), after obtaining a silicon wafer with a sealing film, the substrate layer was peeled off, and the resin layer side of the silicon wafer with a resin layer cured at 170 ° C. for 1 hour was output 5.0 J / pulse. The YAG laser was used for laser marking to confirm the visibility (number of samples: 100).

  In the visibility evaluation method, an image of a surface after laser marking is captured by a scanner, and a marking portion and a non-marking portion around the marking portion are converted into two gradations by image processing software (trade name manufactured by Adobe, PHOSHOP). This operation can be divided into 256 levels of black and white depending on the brightness. Next, the “threshold threshold value for the two gradations” in which the marking part is displayed in white and the non-marking part in black, and the marking part is also displayed in black and the boundary between the marking / non-marking part is eliminated. The threshold value of the boundary is determined, and when the difference between these values is 40 or more, the visibility is good (evaluation ○), and when the difference is 30 or more and less than 40, the visibility is almost good (evaluation Δ). Visibility was regarded as poor when it was less than 30 (evaluation x). Table 1 shows the number of samples corresponding to the evaluations ◯, Δ, and x.

<Fabrication and evaluation of semiconductor devices>
Each sealing film obtained above was used as a semiconductor substrate (pitch dimensions: 5.3 mm × 6.3 mm, scribe line: 100 μm, copper post diameter: 300 μm, copper post height: 100 μm) on which wiring and copper posts were formed. ) After pasting using a hot roll laminator (trade name VA-400III type, manufactured by Taisei Laminator Co., Ltd.) (lamination conditions: 80 ° C., 0.2 MPa, 0.5 m / min) and peeling off the base material layer , A step of curing the resin layer by heating at 170 ° C. for 1 hour, a step of grinding the resin layer to expose the copper post to the surface, a step of forming an external terminal on the copper post, a step of dicing, and the obtained semiconductor A step of picking up the element and mounting it on an organic substrate was performed to manufacture a semiconductor device.

Next, with respect to this semiconductor device, a heat cycle test in which one cycle is −55 ° C./30 min ← → 125 ° C./30 min was performed for 1000 cycles (number of samples: 10), and defects such as cracks and peeling occurred in the resin layer. Investigate whether or not. The results are shown in Table 1. Table 1 shows (number of semiconductor devices having defects in the resin layer) / (total number of samples).

It is a schematic diagram of the sealing film which consists of the base material layer 1 and the resin layer 2. FIG. It is a schematic diagram of the sealing film which consists of the base material layer 1, the resin layer 2, and the protective layer 3. FIG. It is a schematic diagram of the process of laminating a sealing film on a semiconductor substrate. It is a schematic diagram of the semiconductor element which has the protruding electrode sealed with the sealing film.

Explanation of symbols

1: base material layer 2: resin layer 3: protective layer 4: semiconductor substrate 5: protruding electrode 6: solder ball 7: semiconductor element having protruding electrode 8: roll-shaped sealing film 9: roll 10: laminator roll

Claims (9)

(A1) a high molecular weight resin containing a crosslinkable functional group, having a weight average molecular weight of 100,000 or more and Tg of −50 to 50 ° C., and (A2) a thermosetting component containing an epoxy resin and an epoxy resin curing agent ; Containing (A) a resin component, (B) a filler, and (C) a colorant,
The (A1) high molecular weight resin is an epoxy group-containing (meth) acrylic copolymer, and a resin layer having a shear viscosity of 14,000 to 25000 Pa · s at 80 ° C. ,
A sealing film having
  The sealing film according to claim 1, wherein the (A) resin component comprises (A1) 15 to 85% by weight of a high molecular weight resin and (A2) 15 to 85% by weight of a thermosetting component.   The sealing film according to claim 1 or 2, comprising 1 to 300 parts by weight of the (B) filler and 0.01 to 10 parts by weight of the (C) colorant with respect to 10 parts by weight of the (A) resin component. .   The sealing film according to claim 1, further comprising a base material layer having a thickness of 5 to 300 μm on one surface of the resin layer, and the thickness of the resin layer being 5 to 800 μm.   A base layer having a thickness of 5 to 300 μm is provided on one surface of the resin layer, a protective layer having a thickness of 5 to 300 μm is further provided on the other surface of the resin layer, and the thickness of the resin layer is 5 to 5 μm. It is 800 micrometers, The sealing film of any one of Claims 1-3.   The sealing film according to claim 1, wherein the filler (B) is an inorganic filler.   The sealing film according to claim 1, wherein the colorant (C) is other than white.   The sealing film according to any one of claims 1 to 7, wherein the resin layer has a storage elastic modulus of 500 to 20000 MPa in a dynamic viscoelasticity measuring apparatus at 35 ° C after being cured at 170 ° C for 1 hour.   The semiconductor device using the sealing film of any one of Claims 1-8.

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