JP2011014717A - Adhesive film, multilayer circuit board, electronic component and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an adhesive film excellent in reliability of electric connection and ion migration resistance after bonded and simultaneously achieving improved brittleness of the adhesive film and a favorable tucking property; a multilayer circuit board; an electronic component; and a semiconductor device.SOLUTION: The composition of the adhesive film 2 contains (A) a phenol-based novolac resin of 30-70% in total content of 1 to 3 nuclides, (B) an epoxy resin which is liquefied at 20°C, (C) a flux active compound, and (D) a film-depositing resin.

Description

  The present invention relates to an adhesive film, a multilayer circuit board, an electronic component, and a semiconductor device.

  In recent years, electronic devices such as semiconductor packages have been integrated with high density and high density packaging in response to the demands for higher functionality and lighter, thinner and shorter electronic devices. These electronic components have become smaller and more pins. It is out. In order to obtain an electrical connection between these electronic components, solder bonding is used. Examples of the solder bonding include a conductive bonding portion between semiconductor chips, a conductive bonding portion between a semiconductor chip such as a package mounted in a flip chip and a circuit board, a conductive bonding portion between circuit boards, and the like. In order to ensure electrical connection strength and mechanical connection strength, a sealing resin generally called an underfill material is injected into the solder joint portion (underfill sealing).

  When the gap (gap) generated by this solder joint is reinforced with a liquid sealing resin (underfill material), the liquid sealing resin (underfill material) is supplied after the solder joint, and the solder is bonded by curing it. The part is reinforced. However, as the electronic components become thinner and smaller, the solder joints are narrowed in pitch / narrow gap. Therefore, even if liquid sealing resin (underfill material) is supplied after soldering, the liquid sealing between the gaps There is a problem that the stop resin (underfill material) does not spread and it becomes difficult to completely fill the resin.

  In order to solve such a problem, a method is known in which electrical connection and adhesion between terminals are collectively performed through an anisotropic conductive film. For example, an adhesive film containing solder particles is interposed between the members and thermocompression bonded so that the solder particles are interposed between the electrical connection portions of both members and the resin component is filled in the other portions, or metal particles are contacted A method is described in which electrical connection is established by performing the above (for example, Patent Documents 1 and 2).

However, with this method, it is difficult to ensure electrical connection reliability and ion migration resistance of the resin after bonding.

JP-A 61-276873 JP-A-9-31419

  An object of the present invention is to provide an adhesive film, a multilayer circuit board, an electronic component, and a semiconductor device, which are excellent in electrical connection reliability and ion migration resistance after adhesion, and have both improved brittleness of the adhesive film and good tackiness. There is to do.

Such an object is achieved by the following (1) to (17).
(1) An adhesive film for electrically connecting the first terminal of the support and the second terminal of the adherend using solder, and bonding the support and the adherend, (A) a phenolic novolak resin having a total content of 1 to 3 nuclei of 30 to 70%, (B) an epoxy resin that is liquid at 25 ° C., and (C) a flux active compound, (D) a film-forming resin, and an adhesive film,
(2) The adhesive film according to (1), wherein the content of the phenolic novolak resin in which the content of the (A) mononuclear to trinuclear body is 30 to 70% is 3 to 30% by weight. ,
(3) In (1) or (2), the weight-average molecular weight of the phenol-based novolak resin in which the total content of (A) mononuclear to trinuclear is 30 to 70% is 300 to 1500. The adhesive film as described,
(4) The (N) mononuclear content of the phenol-based novolak resin in which the content of the mononuclear to trinuclear body is 30 to 70% is 1% or less, (1) to (3) Any one of the adhesive films,
(5) The total content of the binuclear body and the trinuclear body in the phenolic novolak resin in which the content of the mononuclear body to the trinuclear body is 30 to 70% is 30 to 70%. , The adhesive film according to any one of (1) to (4),
(6) (1) to (5), wherein (A) the phenol novolak resin in which the content of mononuclear to trinuclear is 30 to 70% is a phenol novolac resin and / or a cresol novolac resin. The adhesive film according to any one of
(7) The adhesive film according to any one of (1) to (6), wherein the viscosity of the epoxy resin that is liquid at (B) at 25 ° C is 500 to 50,000 mPa · s,
(8) The adhesive film according to any one of (1) to (7), wherein the content of the (B) epoxy resin that is liquid at 25 ° C. is 10 to 80% by weight,
(9) (B) The blending ratio ((B) / (C)) of the epoxy resin that is liquid at 25 ° C. and the (C) flux active compound is 0.5 to 12.0, (1 ) To the adhesive film according to any one of (8),
(10) The (C) flux active compound is a flux active compound containing two phenolic hydroxyl groups in one molecule and a carboxyl group directly bonded to at least one aromatic group. 9) the adhesive film according to any one of
(11) The adhesive film according to any one of (1) to (10), wherein the (C) flux-active compound contains phenolphthaline,
(12) The adhesive film according to any one of (1) to (11), wherein the film-forming resin (D) includes a phenoxy resin,
(13) The adhesive film according to any one of (1) to (12), which further contains a curing accelerator,
(14) The adhesive film according to any one of claims 1 to 13, further comprising a silane coupling agent,
(15) A multilayer circuit board comprising a cured product of the adhesive film according to any one of (1) to (14),
(16) An electronic component comprising a cured product of the adhesive film according to any one of (1) to (14),
(17) A semiconductor device comprising a cured product of the adhesive film according to any one of (1) to (14).

  According to the present invention, there are provided an adhesive film, a multilayer circuit board, an electronic component, and a semiconductor device, which are excellent in electrical connection reliability and ion migration resistance after adhesion, and have both improved brittleness of the adhesive film and good tackiness. can do.

FIG. 1 is a cross-sectional view schematically showing an example of a method for manufacturing a semiconductor device using the adhesive film of the present invention.

Hereinafter, an adhesive film, a multilayer circuit board, an electronic component, a semiconductor device and a manufacturing method thereof according to the present invention will be described.
The adhesive film of the present invention comprises (A) a phenolic novolak resin having a total content of 1 to 3 nuclei of 30 to 70%, (B) an epoxy resin that is liquid at 25 ° C., and C) containing a flux active compound and (D) a film-forming resin.
The multilayer circuit board, electronic component, and semiconductor device of the present invention electrically connect a support having a first terminal and an adherend having a second terminal using the adhesive film. The support and the adherend are bonded together.

  Hereinafter, the adhesive film, multilayer circuit board, electronic component, and semiconductor device of the present invention and the manufacturing method thereof will be described in detail.

(Adhesive film)

  The adhesive film of the present invention comprises (A) a phenolic novolak resin (hereinafter also referred to as compound (A)) in which the total content of mononuclear to trinuclear is 30 to 70%. Thereby, the glass transition temperature of the hardened | cured material of an adhesive film can be raised, the quantity of the phenol-type novolak resin used as outgas can be reduced, and also it becomes possible to improve ion migration resistance. Moreover, since moderate softness | flexibility can be provided to an adhesive film, it becomes possible to improve the brittleness of an adhesive film. Furthermore, since an appropriate tackiness can be imparted to the adhesive film, an adhesive film excellent in workability can be obtained.

  The compound (A) is not particularly limited, and examples thereof include phenol novolak resins, cresol novolak resins, bisphenol A type novolak resins, bisphenol F type novolak resins, bisphenol AF type novolak resins, and the like. Phenol novolac resins and cresol novolac resins that can effectively increase the glass transition temperature of the cured product and can reduce the amount of phenolic novolak resin that is outgassed are preferred.

  Although content of the said compound (A) is not necessarily limited, It is preferable that 3-30 weight% is contained in an adhesive film, and it is especially preferable that 5-25 weight% is contained. By making content of a compound (A) into the said range, raising the glass transition temperature of the hardened | cured material of an adhesive film effectively, and also reducing the quantity of the phenol-type novolak resin used as outgas effectively. It can be compatible.

  When the total content of mononuclear to trinuclear is less than 30% (the total content of four or more nuclei is 70% or more), (B) reactivity with epoxy resin that is liquid at 25 ° C And the unreacted phenolic novolak resin remains in the cured adhesive film, resulting in a problem that the migration resistance is lowered and the adhesive film becomes brittle and the workability is lowered. Further, when the total content of mononuclear to trinuclear is greater than 70% (the total content of four or more nuclei is 30% or less), the amount of gas increases when the adhesive film is cured. In addition, the surface of the support or the adherend is contaminated, the migration resistance is lowered, the tackiness of the adhesive film is increased, and the workability of the adhesive film is lowered. Problems arise.

Although the total content of the binuclear body and the trinuclear body in the compound (A) is not particularly limited, it is preferably 30 to 70%. By setting it to the above lower limit value or more, it is possible to more effectively prevent the amount of outgas when the adhesive film is cured and contaminate the surface of the support or adherend. Also. By setting it as the upper limit value or less, the flexibility and flexibility of the adhesive film can be more effectively ensured.

  Although the content of the mononuclear substance in the compound (A) is not particularly limited, it is preferably 1% or less, and particularly preferably 0.8% or less in the adhesive film. By setting the content of the mononuclear body within the above range, the amount of outgas when curing the adhesive film can be reduced, contamination of the support or adherend can be suppressed, and further, Migration can be improved.

  Although the weight average molecular weight of the said compound (A) is not necessarily limited, It is preferable that it is 300-1,500, and it is especially preferable that it is 400-1400. By setting it to the above lower limit value or more, it is possible to more effectively prevent the amount of outgas when the adhesive film is cured and contaminate the surface of the support or adherend. Also. By setting it as the upper limit value or less, the flexibility and flexibility of the adhesive film can be more effectively ensured.

  The adhesive film of the present invention contains (B) an epoxy resin that is liquid at 25 ° C. (hereinafter also referred to as compound (B)). Thereby, since a softness | flexibility and a flexibility can be provided to an adhesive film, the adhesive film excellent in handling property can be obtained.

  Although it does not specifically limit as said compound (B), A bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin etc. are mentioned. Among these, bisphenol A-type epoxy resins and bisphenol F-type epoxy resins, which are excellent in adhesion of the adhesive film to the support and adherend, and excellent in mechanical properties after the adhesive film is cured, are preferable.

  The epoxy resin that is liquid at 25 ° C. is more preferably a compound having a viscosity at 25 ° C. of 500 to 50,000 mPa · s, more preferably 800 to 40,000 mPa · s. The thing which is is mentioned. By setting the viscosity at 25 ° C. to the above lower limit or more, the flexibility and flexibility of the adhesive film can be ensured. Moreover, the tack property of an adhesive film becomes strong by making the viscosity in 25 degreeC below the said upper limit, and it can prevent that handling property falls.

  The content of the epoxy resin that is liquid at 25 ° C. is not particularly limited, but is preferably 10 to 80% by weight, and particularly preferably 15 to 75% by weight. By setting it as the said lower limit or more, the softness | flexibility and flexibility of an adhesive film can be expressed more effectively. Moreover, by setting it as the said upper limit or less, the tack property of an adhesive film becomes strong and it can prevent more effectively that handling property falls.

  The adhesive film of the present invention contains (C) a flux active compound (hereinafter also referred to as compound (C)). Thereby, the oxide film on the solder surface of at least one of the first terminal of the support and the second terminal of the adherend is removed, and in some cases, the first terminal of the support or the adherend Since the oxide film on the surface of the second terminal can be removed and the first terminal and the second terminal can be surely soldered together, a multilayer circuit board with high connection reliability, an electronic Parts, semiconductor devices and the like can be obtained.

  The compound (C) is not particularly limited as long as it has a function of removing an oxide film on the solder surface, but either a carboxyl group or a phenolic hydroxyl group, or both a carboxyl group and a phenol hydroxyl group are present. The compound provided is preferred.

The compounding amount of the compound (C) is preferably 1 to 30% by weight, particularly preferably 3 to 20% by weight. When the compounding amount of the compound (C) is in the above range, the flux activity can be improved, and when the adhesive film is cured, the unreacted compound (A), compound (B) and compound (C ) Can be prevented, and migration resistance can be improved.

  Among the compounds that act as curing agents for epoxy resins, there are (C) flux active compounds (hereinafter, such compounds are also referred to as flux active curing agents). For example, aliphatic dicarboxylic acids, aromatic dicarboxylic acids and the like that act as curing agents for epoxy resins also have a flux action. In the present invention, such a flux active curing agent that acts as a flux and also acts as a curing agent for an epoxy resin can be suitably used.

  The (C) flux-active compound having a carboxyl group means a compound having one or more carboxyl groups in the molecule, and may be liquid or solid. The (C) flux active compound having a phenolic hydroxyl group means a compound having one or more phenolic hydroxyl groups in the molecule, and may be liquid or solid. The (C) flux active compound having a carboxyl group and a phenolic hydroxyl group means a compound having one or more carboxyl groups and phenolic hydroxyl groups in the molecule, and may be liquid or solid. .

  Among these, (C) flux active compounds having a carboxyl group include aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, aliphatic carboxylic acids, aromatic carboxylic acids and the like.

  Examples of the aliphatic acid anhydride related to the flux active compound (C) having the carboxyl group include succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, and polysebacic acid anhydride.

  Examples of the alicyclic acid anhydride relating to the flux active compound (C) having a carboxyl group include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, and tetrahydrophthalic anhydride. , Trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, and the like.

  Examples of the aromatic acid anhydride related to the flux active compound (C) having a carboxyl group include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tris Trimellitate and the like.

Examples of the aliphatic carboxylic acid related to the flux active compound (C) having the carboxyl group include compounds represented by the following general formula (1), formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid pivalate, and capryl. Examples include acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, crotonic acid, oleic acid, fumaric acid, maleic acid, oxalic acid, malonic acid, oxalic acid, and the like.
_{HOOC- (CH 2) n -COOH (} 1)
(In formula (1), n represents an integer of 1 or more and 20 or less.)

Examples of the aromatic carboxylic acid related to the flux active compound (C) having a carboxyl group include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, melophanoic acid, planitic acid, pyro Mellitic acid, meritic acid, triylic acid, xylic acid, hemelic acid, mesitylene acid, prenylic acid, toluic acid, cinnamic acid, salicylic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gentisic acid (2 , 5-dihydroxybenzoic acid), 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid (3,4,5-trihydroxybenzoic acid), 1,4-dihydroxy-2-naphthoic acid Naphthoic acid derivatives such as 3,5-dihydroxy-2-naphthoic acid, phenolphthalene, di Such as phenol acid, and the like.

  Among these (C) flux active compounds having the carboxyl group, (C) the activity of the flux active compound, the amount of outgas generated when the adhesive film is cured, and the elastic modulus and glass transition of the adhesive film after curing The compound represented by the general formula (1) is preferable in terms of a good balance of temperature and the like. And among the compounds shown by said general formula (1), while the compound whose n in Formula (1) is 3-10 can suppress that the elasticity modulus in the adhesive film after hardening increases. It is particularly preferable in that the adhesion between the support and the adherend can be improved.

Among the compounds represented by the general formula (1), as the compound in which n in the formula (1) is 3 to 10, for example, n = 3 glutaric acid (HOOC— (CH ₂ ) ₃ —COOH), n = 4 adipic acid (HOOC— (CH ₂ ) ₄ —COOH), n = 5 pimelic acid (HOOC— (CH ₂ ) ₅ —COOH), n = 8 sebacic acid (HOOC— (CH ₂ ) ₈ -COOH) and of _{n = 10 HOOC- (CH 2)} 10 -COOH- , and the like.

  Examples of the (C) flux-active compound having a phenolic hydroxyl group include phenols. Specifically, for example, phenol, o-cresol, 2,6-xylenol, p-cresol, m-cresol, o- Ethylphenol, 2,4-xylenol, 2,5 xylenol, m-ethylphenol, 2,3-xylenol, meditol, 3,5-xylenol, p-tertiarybutylphenol, catechol, p-tertiaryamylphenol, resorcinol, Contains phenolic hydroxyl groups such as p-octylphenol, p-phenylphenol, bisphenol A, bisphenol F, bisphenol AF, biphenol, diallyl bisphenol F, diallyl bisphenol A, trisphenol, tetrakisphenol Nomar, and the like can be mentioned.

  A compound having either a carboxyl group or a phenol hydroxyl group as described above, or a compound having both a carboxyl group and a phenol hydroxyl group is incorporated three-dimensionally by reaction with an epoxy resin.

Therefore, from the viewpoint of improving the formation of a three-dimensional network of the epoxy resin after curing, (C) the flux active compound has a flux action and acts as a curing agent for the epoxy resin. Is preferred. Examples of the flux active curing agent include, in one molecule, two or more phenolic hydroxyl groups that can be added to an epoxy resin, and one or more carboxyls directly bonded to an aromatic group that exhibits a flux action (reduction action). And a compound having a group. Such flux active curing agents include 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gentisic acid (2,5-dihydroxybenzoic acid), 2,6-dihydroxybenzoic acid, 3,4- Benzoic acid derivatives such as dihydroxybenzoic acid and gallic acid (3,4,5-trihydroxybenzoic acid); 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid, 3,7- Examples thereof include naphthoic acid derivatives such as dihydroxy-2-naphthoic acid; phenolphthaline; and diphenolic acid. These may be used alone or in combination of two or more.
Among these, 2,3-dihydroxybenzoic acid, gentisic acid, and phenolphthaline, which are excellent in the effect of removing the oxide film on the solder surface and the reactivity with the epoxy resin, are preferable.

Moreover, 1-30 weight% is preferable and, as for the compounding quantity of a flux active hardening | curing agent in an adhesive film, 3-20 weight% is especially preferable. When the blending amount of the flux active curing agent in the adhesive film is within the above range, the flux activity of the adhesive film can be improved and the epoxy resin and the unreacted flux active curing agent remain in the adhesive film. Is prevented. If unreacted flux active curing agent remains, migration occurs.

  The compounding ratio of the compound (B) and the compound (C) is not particularly limited, but ((B) / (C)) is preferably 0.5 to 12.0. It is especially preferable that it is 0-10.0. By setting ((B) / (C)) to be equal to or higher than the above lower limit value, when the adhesive film is cured, unreacted compound (C) can be reduced, so that the migration resistance can be improved. it can. Moreover, when it makes it below the said upper limit, when hardening an adhesive film, since an unreacted compound (B) can be reduced, migration resistance can be improved.

  The adhesive film of the present invention includes (D) a film-forming resin that improves the film-forming property of the adhesive film. Thereby, it becomes easy to make a film state. Moreover, it is excellent also in the mechanical characteristic of an adhesive film.

The (D) film-forming resin is not particularly limited. For example, (meth) acrylic resin, phenoxy resin, polyester resin, polyurethane resin, polyimide resin, siloxane-modified polyimide resin, polybutadiene, polypropylene, Styrene-butadiene-styrene copolymer, styrene-ethylene-butylene-styrene copolymer, polyacetal resin, polyvinyl butyral resin, polyvinyl acetal resin, butyl rubber, chloroprene rubber, polyamide resin, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene- Acrylic acid copolymer, acrylonitrile-butadiene-styrene copolymer, polyvinyl acetate, nylon and the like can be mentioned. These may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of (meth) acrylic resins, phenoxy resins, and polyimide resins is preferable.

The weight average molecular weight of the film-forming resin (D) is not particularly limited, but is preferably 10,000 or more, more preferably 20,000 to 1,000,000, still more preferably 30,000 to 900,000. When the weight average molecular weight is in the above range, the film formability of the adhesive film can be further improved.

  The content of the film-forming resin (D) is not particularly limited, but is preferably 10 to 50% by weight, more preferably 15 to 40% by weight, and particularly preferably 20 to 35% by weight in the adhesive film. When the content is within the above range, the fluidity of the adhesive film can be suppressed, and the handling of the adhesive film becomes easy.

The adhesive film may further include a curing accelerator. A hardening accelerator can be suitably selected according to the kind etc. of curable resin. As the curing accelerator, for example, an imidazole compound having a melting point of 150 ° C. or higher can be used. When the melting point of the curing accelerator used is 150 ° C. or more, before the curing of the adhesive film is completed, the solder components constituting the solder bumps can move to the internal electrode surface provided in the semiconductor element, The electrical connection between the internal electrodes can be improved. Examples of the imidazole compound having a melting point of 150 ° C. or higher include 2-phenylhydroxyimidazole and 2-phenyl-4-methylhydroxyimidazole.

Although content of the said hardening accelerator is not necessarily limited, It is preferable that it is 0.005 to 10 weight% in an adhesive film, More preferably, it is 0.01 to 5 weight%. By making the compounding quantity of an imidazole compound 0.005 weight% or more, the function as a hardening accelerator can be exhibited more effectively and the sclerosis | hardenability of an adhesive film can be improved. Moreover, by setting the blending amount of imidazole to 10% by weight or less, the melt viscosity of the resin at the melting temperature of the solder component constituting the solder bump does not become too high, and a good solder joint structure can be obtained. Moreover, the preservability of the adhesive film can be further improved.
These curing accelerators may be used alone or in combination of two or more.

  The adhesive film may further include a silane coupling agent. By including a silane coupling agent, the adhesion of the adhesive film to a support or adherend such as a semiconductor element or a substrate can be enhanced. As the silane coupling agent, for example, an epoxy silane coupling agent, an aromatic-containing aminosilane coupling agent and the like can be used. These may be used alone or in combination of two or more. The blending amount of the silane coupling agent may be appropriately selected, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, based on the entire resin composition. More preferably, it is 0.1 to 2% by weight.

The adhesive film may further include an inorganic filler. Thereby, the linear expansion coefficient of an adhesive film can be reduced, and reliability can be improved thereby.
Examples of the inorganic filler include silver, titanium oxide, silica, mica, and the like. Among these, silica is preferable. Moreover, as a shape of a silica filler, although there exists crushing silica and spherical silica, spherical silica is preferable.

  The average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more and 20 μm or less, and particularly preferably 0.1 μm or more and 5 μm or less. By setting it as the said range, aggregation of a filler within an adhesive film can be suppressed and an external appearance can be improved.

  Although content of the said inorganic filler is not specifically limited, 10 to 60 weight% is preferable with respect to the whole said resin composition, and 20 to 50 weight% is especially preferable. By setting the above range, the difference in linear expansion coefficient between the cured adhesive film and the adherend can be reduced, and the stress generated during thermal shock can be reduced. Furthermore, it can suppress reliably. Furthermore, since it can suppress that the elasticity modulus of the adhesive film after hardening becomes high too much, the reliability of a semiconductor device rises.

Apply the varnish obtained by mixing each resin component as described above in a solvent onto a base material that has been subjected to a release treatment such as a polyester sheet, and at a predetermined temperature, substantially free of solvent. The adhesive film can be obtained by drying the film. The solvent used here is not particularly limited as long as it is inert to the components used, but ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, DIBK (diisobutyl ketone), cyclohexanone, DAA (diacetone alcohol), etc. , Aromatic hydrocarbons such as benzene, xylene, toluene, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Cellosolve, NMP (N-methyl-2-pyrrolidone), THF (tetrahydrofuran), DMF (dimethylformamide), DBE (dibasic acid ester), EEP (3-ethoxypropionic acid ester) Le), DMC (dimethyl carbonate), etc. is preferably used. The amount of the solvent used is preferably in the range where the solid content of the components mixed in the solvent is 10 to 60% by weight.

Although the thickness of the obtained adhesive film is not specifically limited, It is preferable that it is 1-300 micrometers, and it is especially preferable that it is 5-200 micrometers. When the thickness is within the above range, the resin component can be sufficiently filled in the gap between the joint portions, and the mechanical adhesive strength after curing of the resin component can be ensured.

  The adhesive film thus obtained has a flux activity. Therefore, it can be suitably used in the connection of members that require solder connection, such as a semiconductor element and a substrate, a substrate and a substrate, a semiconductor element and a semiconductor element, or a semiconductor wafer.

Next, a multilayer circuit board, an electronic component, and a semiconductor device using the above-described adhesive film will be described.
FIG. 1 is a cross-sectional view showing an example of a method for manufacturing a semiconductor device.
As shown in FIG. 1, a semiconductor element 1 having solder bumps 11 is prepared (FIG. 1A). The adhesive film 2 having the above-described flux function is laminated so as to cover the solder bumps 11 of the semiconductor element 1 (FIG. 1B).

  Examples of a method of laminating the adhesive film 2 having the flux function on the semiconductor element 1 include a roll laminator, a flat plate press, a wafer laminator, and the like. Among these, a method of laminating under vacuum (vacuum laminator) is preferable in order to prevent air from being involved during lamination.

Moreover, it does not specifically limit as conditions to laminate | stack, Although it should just be able to laminate | stack without a void, Specifically, 60-150 degreeC x 1 second-120 second are preferable, and 80-120 degreeC x 5-60 second is especially preferable. When the laminating conditions are within the above range, the balance between the sticking property, the effect of suppressing the protrusion of the resin, and the degree of curing of the resin is excellent.
Moreover, although pressurization conditions are not specifically limited, 0.2-2.0 MPa is preferable and 0.5-1.5 MPa is especially preferable.

  Next, a substrate 3 having a pad portion (not shown) is prepared at a position corresponding to the solder bump 11 of the semiconductor element 1 described above, and an adhesive film having a flux function while aligning the semiconductor element 1 and the substrate 3. 2 is temporarily pressed (FIG. 1 (c)). Although the conditions for temporary pressure bonding are not particularly limited, 60 to 150 ° C. × 1 second to 120 seconds are preferable, and 80 to 120 ° C. × 5 to 60 seconds are particularly preferable. Moreover, although pressurization conditions are not specifically limited, 0.2-2.0 MPa is preferable and 0.5-1.5 MPa is especially preferable.

Next, the solder bumps 11 are melted to form solder connection portions 111 that are soldered to the pads (FIG. 1D).
The conditions for solder connection depend on the type of solder used, but in the case of Sn-Ag, for example, it is preferable to perform solder connection by heating at 220 to 260 ° C. for 5 to 500 seconds, particularly 230 to 240 ° C. for 10 to 10. It is preferable to heat for 100 seconds.
This solder bonding is preferably performed under conditions such that the adhesive film 2 is cured after the solder bumps 11 are melted. That is, the solder bonding is preferably performed under the condition that the solder bump 11 is melted but the curing reaction of the adhesive film 2 does not proceed so much. Thereby, the shape of the solder connection part at the time of soldering can be made into the stable shape which is excellent in connection reliability.

  Next, the adhesive film 2 is heated and cured. The conditions for curing are not particularly limited, but are preferably 130 to 220 ° C. × 30 to 500 minutes, and particularly preferably 150 to 200 ° C. × 60 to 180 minutes.

Thus, the semiconductor device 10 in which the semiconductor element 1 and the substrate 3 are bonded with the cured product of the adhesive film 2 can be obtained. Since the semiconductor device 10 is bonded with the cured product of the adhesive film 2 as described above, the electrical connection reliability is excellent.
Moreover, a circuit board and a circuit board can be joined with the hardened | cured material of the adhesive film 2 by the same method, and a multilayer circuit board can be obtained.
Moreover, the electronic component by which the semiconductor element and the semiconductor element were adhere | attached with the hardened | cured material of the adhesive film 2 by the same method can be obtained.
Moreover, the semiconductor device by which the semiconductor element and the semiconductor element were adhere | attached with the hardened | cured material of the adhesive film 2 by the same method can be obtained.
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.

Example 1
<Preparation of adhesive film>
15.0 parts by weight of a phenol novolac resin (Sumitomo Bakelite, PR55617), 45.0 parts by weight of a liquid bisphenol A type epoxy resin (Dainippon Ink and Chemicals, EPICLON-840S), and a phenol that is a flux active compound 15.0 parts by weight of phthalin (manufactured by Tokyo Chemical Industry Co., Ltd.), 24.4 parts by weight of bisphenol A type phenoxy resin (manufactured by Toto Kasei Co., Ltd., YP-50) as a film-forming resin, and 2-phenyl- as a curing accelerator 0.1 parts by weight of 4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) and β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-303) 0 as a silane coupling agent Dissolve 5 parts by weight in methyl ethyl ketone to prepare a resin varnish with a resin concentration of 50%. .

<Manufacture of adhesive film>
The obtained resin varnish is applied to a base polyester film (manufactured by Toray Industries Inc., Lumirror) so as to have a thickness of 50 μm, dried at 100 ° C. for 5 minutes, and an adhesive film having a flux activity of 25 μm in thickness. Got.

<Manufacture of semiconductor devices>
The obtained adhesive film was laminated to a semiconductor element having a solder bump (size 10 mm × 10 mm, thickness 0.3 mm) at 100 ° C. with a vacuum roll laminator to obtain a semiconductor element with an adhesive film.
Next, the semiconductor element was temporarily pressure-bonded to the circuit board at 100 ° C. for 30 seconds while being aligned so that the pads of the circuit board having the pads and the solder bumps were in contact with each other.
Next, the solder bumps were melted by heating at 235 ° C. for 30 seconds to perform solder connection.
And it heated at 180 degreeC for 60 minute (s), the adhesive film was hardened, and the semiconductor device with which the semiconductor element and the circuit board were adhere | attached with the hardened | cured material of the adhesive film was obtained.

(Example 2)
Except having changed 15.0 weight part of phenol novolak resin (the Sumitomo Bakelite company make, PR55617) 15.0 weight part in preparation of resin varnish to 15.0 weight part of phenol novolak resin (the Mitsui Chemicals company make, VR-9305), Example In the same manner as in Example 1, an adhesive film and a semiconductor device were produced.

(Example 3)
In the preparation of the resin varnish, 15.0 parts by weight of phenol novolac resin (Sumitomo Bakelite, PR55617) was changed to 5.0 parts by weight, and liquid bisphenol A type epoxy resin (Dainippon Ink and Chemicals, EPPICLON-840S) 45 Example 1 except that the compounding amount was changed from 0.04 parts by weight to 35.0 parts by weight, and 24.4 parts by weight of bisphenol A type phenoxy resin (manufactured by Tohto Kasei Co., Ltd., YP-50) to 44.4 parts by weight. The adhesive film and the semiconductor device were manufactured in the same manner as described above.

Example 4
In the preparation of the resin varnish, 15.0 parts by weight of phenol novolak resin (Sumitomo Bakelite, PR55617) was changed to 25.0 parts by weight, and liquid bisphenol A type epoxy resin (Dainippon Ink and Chemicals, EPICLON-840S) 45 0.0 parts by weight to 50.0 parts by weight, phenolphthaline (manufactured by Tokyo Chemical Industry Co., Ltd.) 15.0 parts by weight to 10.0 parts by weight, bisphenol A type phenoxy resin (manufactured by Toto Kasei Co., Ltd., YP-50) An adhesive film and a semiconductor device were produced in the same manner as in Example 1 except that 24.4 parts by weight was changed to 14.4 parts by weight.

(Example 5)
In the preparation of the resin varnish, 45.0 parts by weight of liquid bisphenol A type epoxy resin (Dainippon Ink Chemical Co., Ltd., EPPICLON-840S) was changed to 50.0 parts by weight, and bisphenol A type phenoxy resin (manufactured by Tohto Kasei Co., Ltd., YP −50) An adhesive film and a semiconductor device were produced in the same manner as in Example 1 except that the blending amount was changed from 24.4 parts by weight to 19.4 parts by weight.

(Example 6)
In the preparation of the resin varnish, 45.0 parts by weight of liquid bisphenol A type epoxy resin (Dainippon Ink & Chemicals, EPICLON-840S) is used as liquid bisphenol F type epoxy resin (Dainippon Ink & Chemicals, EPICLON-830LVP). An adhesive film and a semiconductor device were produced in the same manner as in Example 1 except that the change was made.

(Example 7)
In the preparation of the resin varnish, adhesion was performed in the same manner as in Example 1 except that 15.0 parts by weight of phenolphthalin (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 15.0 parts by weight of sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). Films and semiconductor devices were manufactured.

(Example 8)
Except that 24.4 parts by weight of bisphenol A type phenoxy resin (manufactured by Toto Kasei Co., Ltd., YP-50) was changed to bisphenol F type phenoxy resin (manufactured by Toto Kasei Co., Ltd., YP-70) in the preparation of the resin varnish. In the same manner as in Example 1, an adhesive film and a semiconductor device were produced.

(Comparative Example 1)
Except that 15.0 parts by weight of phenol novolac resin (manufactured by Sumitomo Bakelite, PR55617) was changed to 15.0 parts by weight of phenol novolac resin (manufactured by Gunei Chemical Industry Co., Ltd., LV70S) in the preparation of the resin varnish. In the same manner as in Example 1, an adhesive film and a semiconductor device were produced.

  Table 1 shows the physical properties of the phenolic novolak resins used in the adjustment of the resin varnishes of the examples and comparative examples.

また、各実施例および比較例で得られた接着フィルム、半導体装置について、以下の評価を行った。評価項目を内容と共に示す。得られた結果を表２に示す。

Moreover, the following evaluation was performed about the adhesive film and semiconductor device which were obtained by each Example and the comparative example. The evaluation items are shown together with the contents. The obtained results are shown in Table 2.

1. Adhesive film workability About the adhesive film obtained by each Example and the comparative example, it wound around a 4 mm diameter cylinder in 25 degreeC atmosphere, and the crack of the adhesive layer of the adhesive film and a chip | tip were confirmed.
○: No cracking or chipping occurs in the adhesive layer of the adhesive film.
X: A part of the adhesive layer of the adhesive film is cracked or chipped.

2. Adhesive film tackiness About the adhesive film obtained in each Example and Comparative Example, the adhesive layers of the adhesive film are overlapped at 25 ° C. and pressed at 0.1 MPa to measure whether or not the adhesive layers of the adhesive film are fused. did. Each code is as follows.
○: When the adhesive film of the adhesive film is peeled off, the adhesive layer surface of the adhesive film is smooth and shiny. ×: When the adhesive film of each other is peeled off, the surface becomes rough and the gloss is lost. When the adhesive layers are fused together and cannot be removed

3. Ion migration properties For the semiconductor devices obtained in each of the examples and comparative examples, the insulation resistance value between adjacent bumps was continuously measured while applying a voltage of 5 V in an environment of 130 ° C. and 85% RH. evaluated. Each code is as follows.
A: The insulation resistance value after 500 hours was 1.0E + 06 or more.
A: The insulation resistance value decreased to 1.0E + 06 or less in 100 to 250 hours.
Δ: The insulation resistance value decreased to 1.0E + 06 or less in 24 hours to less than 100 hours.
X: The insulation resistance value decreased to 1.0E + 06 or less in 0 to less than 24 hours.

4). Connection reliability For each of the 20 semiconductor devices obtained in each of the examples and comparative examples, one cycle is a period of 30 minutes under a condition of −55 ° C. and 30 minutes under a condition of 125 ° C. The temperature cycle test was conducted 100 cycles, and the connection resistance value of the semiconductor element and the circuit board was measured with a digital multimeter for the semiconductor device after the test to evaluate the connection reliability. Each code is as follows.
A: The connection resistance values of all 20 semiconductor devices were 10Ω or less.
X: The connection resistance value of one or more semiconductor devices was 10Ω or more.

DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Adhesive film 3 Board | substrate 10 Semiconductor device 11 Solder bump 111 Solder junction part

Claims (17)

An adhesive film for electrically connecting the first terminal of the support and the second terminal of the adherend using solder, and bonding the support and the adherend,
(A) a phenolic novolak resin in which the total content of mononuclear to trinuclear is 30 to 70%;
(B) an epoxy resin that is liquid at 25 ° C .;
(C) a flux active compound;
(D) a film-forming resin;
An adhesive film comprising:   The adhesive film according to claim 1, wherein the content of the (A) mononuclear to trinuclear body is 30 to 70%, and the content of the phenolic novolak resin is 3 to 30% by weight.   The adhesive film according to claim 1 or 2, wherein the phenolic novolak resin having a total content of (A) mononuclear to trinuclear of 30 to 70% has a weight average molecular weight of 300 to 1500.   4. The mononuclear content of the phenol-based novolak resin in which the content of (A) mononuclear to trinuclear is 30 to 70% is 1% or less. 5. Adhesive film. The total content of the binuclear body and the trinuclear body in the phenolic novolak resin in which the content of the (A) mononuclear body to the trinuclear body is 30 to 70% is 30 to 70%. The adhesive film according to any one of 1 to 4.   The phenolic novolak resin in which the content of (A) mononuclear to trinuclear is 30 to 70% is a phenol novolak resin and / or a cresol novolak resin. Adhesive film.   The adhesive film according to any one of claims 1 to 6, wherein the (B) epoxy resin that is liquid at 25 ° C has a viscosity at 25 ° C of 500 to 50,000 mPa · s.   The adhesive film according to claim 1, wherein the content of the (B) epoxy resin that is liquid at 25 ° C. is 10 to 80% by weight.   The blend ratio ((B) / (C)) of the (B) epoxy resin that is liquid at 25 ° C and the (C) flux active compound is 0.5 to 12.0. An adhesive film according to any one of the above.   The flux active compound (C) is a flux active compound containing two phenolic hydroxyl groups in one molecule and a carboxyl group directly bonded to at least one aromatic group. The adhesive film as described in 2.   The adhesive film according to any one of claims 1 to 10, wherein the (C) flux-active compound contains phenolphthaline.   The adhesive film according to claim 1, wherein the film-forming resin (D) contains a phenoxy resin.   Furthermore, the adhesive film in any one of Claims 1 thru | or 12 which contains a hardening accelerator.   Furthermore, the adhesive film in any one of Claim 1 thru | or 13 which contains a silane coupling agent.   A multilayer circuit board comprising a cured product of the adhesive film according to claim 1.   An electronic component comprising the cured product of the adhesive film according to claim 1.   A semiconductor device comprising a cured product of the adhesive film according to claim 1.

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