JP2005175338A - Adhesive film for semiconductor and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive film for semiconductor without permitting an adhesive to squeeze out to a substrate etc., and further to provide a semiconductor device excellent in the productivity and excellent in the connection reliability between a semiconductor element and the substrate. <P>SOLUTION: The adhesive film 3 for semiconductor is an adhesive film 3 for semiconductor used for joining the semiconductor element 1 and a support member 2. The adhesive film 3 for semiconductor comprises a resin composition containing epoxy resin, phenol resin, resin different from the epoxy resin and the phenol resin, and a latent catalyst. The semiconductor device 20 is adapted such that the semiconductor element 1 and the support member 2 are joined via the adhesive film 3 for semiconductor. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an adhesive film for a semiconductor and a semiconductor device.

  With recent downsizing, thinning, and speeding up of electronic devices, flip chip mounting has attracted attention as a method for connecting semiconductor elements to a substrate (such as a printed wiring board). Bumps are formed on the aluminum electrodes of the semiconductor element used for the flip chip mounting, and the bumps and the wiring on the circuit board are electrically joined. As the composition of these bumps, solder is mainly used. The solder bumps are formed on the exposed aluminum terminals connected to the internal wiring of the chip by vapor deposition or plating. There is also a gold stud bump formed by a wire bonding apparatus.

When such a flip chip connected semiconductor device is used as it is, the electrodes of the connecting portion are exposed to the air, and the difference in the coefficient of thermal expansion between the chip and the substrate is large. Due to the history, a large stress was applied to the connection part of the bump, and there was a problem in mounting reliability.
In order to solve this problem, a method of fixing the semiconductor element and the substrate by connecting the bump and the substrate and then filling the gap between the semiconductor element and the substrate with a resin paste using a capillary phenomenon and curing it is adopted. ing. As a result, deterioration of the input / output bumps such as corrosion is prevented, and the bonding stability between the semiconductor element and the substrate is enhanced. (For example, see Patent Documents 1 and 2.)

In general, a semiconductor element that performs flip chip mounting has a large number of electrodes, and filling a resin paste using a capillary phenomenon makes it difficult to fill the resin without sufficient resin, resulting in unstable operation of the semiconductor element. There were problems such as malfunction and low moisture resistance reliability. Furthermore, when various packages are developed and the electrodes are arranged around the semiconductor element at a multi-pin and narrow pitch due to problems in circuit design, it becomes difficult to fill the resin paste by pouring. In addition, when the size of the semiconductor element is reduced, defective products are frequently generated due to the contamination of the substrate due to the overflow of the liquid resin, resulting in a decrease in yield. Furthermore, since it takes too much time to fill each flip-chip connected semiconductor device with a resin, the productivity is insufficient in consideration of the curing process.
JP 2000-336244 A (pages 2 to 4) JP 2001-127215 A (pages 2 to 6)

An object of the present invention is to provide an adhesive film for a semiconductor in which no adhesive sticks out to a substrate or the like.
Another object of the present invention is to provide a semiconductor device having excellent productivity and excellent connection reliability between a semiconductor element and a substrate.

（６） 前記有機溶剤に可溶なポリイミド樹脂は、式（２）で表されるジアミノポリシロキサンをアミン成分総量の５〜７０モル％有するものである上記（５）記載の半導体用接着フィルム。

（７） 前記半導体素子と、支持部材との接合は、フリップチップ接合である上記（１）ないし（６）のいずれかに記載の半導体用接着フィルム。
（８） 半導体素子と、支持部材とが上記（１）ないし（７）のいずれかに記載の半導体用接着フィルムを介して接合されていることを特徴とする半導体装置。
（９） 前記半導体素子は、突起電極を有するものである上記（８）記載の半導体装置。
（１０） 前記支持部材は、突起電極を有するものである上記（８）記載の半導体装置。 Such an object is achieved by the present invention described in the following (1) to (10).
(1) An adhesive film for a semiconductor used for bonding a semiconductor element and a support member,
The said adhesive film for semiconductors is comprised with the resin composition containing an epoxy resin, a phenol resin, resin different from the said epoxy resin and a phenol resin, and a latent catalyst, The adhesive film for semiconductors characterized by the above-mentioned.
(2) The adhesive film for a semiconductor according to (1), wherein the resin composition further contains an inorganic filler.
(3) The adhesive film for a semiconductor according to (2), wherein the inorganic filler is silica.
(4) The adhesive film for a semiconductor according to any one of (1) to (3), wherein the resin different from the epoxy resin and the phenol resin is a resin soluble in an organic solvent.
(5) The adhesive for a semiconductor according to any one of (1) to (4), wherein the resin different from the epoxy resin and the phenol resin is a polyimide resin that is soluble in the organic solvent represented by the general formula (1). the film.

(6) The adhesive film for a semiconductor according to (5), wherein the polyimide resin soluble in the organic solvent has a diaminopolysiloxane represented by the formula (2) in an amount of 5 to 70 mol% of the total amine component.

(7) The adhesive film for a semiconductor according to any one of (1) to (6), wherein the semiconductor element and the supporting member are joined by flip chip joining.
(8) A semiconductor device, wherein a semiconductor element and a support member are joined via the adhesive film for a semiconductor according to any one of (1) to (7).
(9) The semiconductor device according to (8), wherein the semiconductor element has a protruding electrode.
(10) The semiconductor device according to (8), wherein the support member has a protruding electrode.

ADVANTAGE OF THE INVENTION According to this invention, the adhesive film for semiconductors without the protrusion of the adhesive agent to a board | substrate etc. can be obtained.
In addition, according to the present invention, a semiconductor device having excellent productivity and excellent connection reliability between a semiconductor element and a substrate can be obtained.
Moreover, according to this invention, the adhesive film for semiconductors which has the effect | action of underfill can be obtained.
Further, when an epoxy resin is used as the curable resin and a phenol resin is used as the curing agent, connection reliability can be particularly improved.
By curing the curable resin using a latent catalyst, particularly the mechanical properties can be improved.
In addition, when a silicone-modified polyimide resin is used as a polyimide resin soluble in an organic solvent, connection reliability can be particularly improved.
Moreover, when an epoxy resin, a phenol resin, and a latent catalyst are used in combination, the resin filling property at the time of flip chip connection can be improved.
Moreover, when an inorganic filler is used, especially heat resistance can be improved.

Hereinafter, the adhesive film for semiconductor and the semiconductor device of the present invention will be described.
The adhesive film for semiconductor of the present invention is an adhesive film for semiconductor used for bonding a semiconductor element and a support member, and the adhesive film for semiconductor includes an epoxy resin, a phenol resin, the epoxy resin, and phenol. It is comprised by the resin composition containing resin different from resin and a latent catalyst.
Moreover, the semiconductor device of the present invention is characterized in that the semiconductor element and the support member are bonded via the above-described adhesive film for a semiconductor.

Hereinafter, the adhesive film for semiconductor will be described.
The adhesive film for a semiconductor of the present invention is used for joining a semiconductor element and a support member, and the adhesive film for a semiconductor is an epoxy resin, a phenol resin, and a resin different from the epoxy resin and the phenol resin. And a resin composition containing a latent catalyst. Thereby, it is excellent in adhesiveness and can improve the connection reliability of a semiconductor device. Furthermore, since the semiconductor adhesive film of the present invention can supply the resin in a lump in a wafer state first to obtain a semiconductor element with a filling resin separated into pieces, and can be filled simultaneously with flip chip connection. Excellent productivity.
In addition, in the conventional underfill, it is necessary to greatly reduce the melt viscosity of the resin, so that the amount of resin protruding around the chip increases. However, the semiconductor adhesive film of the present invention is supplied in an amount necessary for filling. Since the melt viscosity can be minimized to fill the circuit step and the periphery of the connection terminal, the amount of protrusion of the resin can be reduced.

The epoxy resin makes it easy to adjust the melt viscosity of the adhesive film for a semiconductor and can sufficiently fill the resin, thereby improving connection reliability. Furthermore, the thermal linear expansion coefficient for forming a network-like three-dimensional crosslinked structure by curing can be brought close to the adherend, and the reliability in the temperature cycle test and the heat resistance reliability during reflow can be improved.
The epoxy resin may be a compound having two or more epoxy groups in the molecule. For example, bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolac, etc. Of epoxy resin, novolak epoxy resin such as cresol novolac epoxy resin, brominated epoxy resin such as brominated bisphenol A epoxy resin, brominated phenol novolac epoxy resin, and heterocyclic epoxy resins such as triglycidyl isocyanate In addition, alicyclic epoxy resins, biphenyl epoxy resins, naphthalene epoxy resins, glycidyl ester epoxy resins, and the like can be given. These can be used alone or in combination of two or more. Among these, bisphenol type epoxy resins are particularly preferable. Thereby, the filling property of the resin can be particularly improved.

  Although content of the said epoxy resin is not specifically limited, 5 to 50 weight% of the whole resin composition except the said inorganic filler is preferable, and 10 to 30 weight% is especially preferable. When the content is within the above range, the mechanical strength of the adhesive film for semiconductor is particularly excellent.

The said phenol resin can improve the mechanical strength of the adhesive film for semiconductors, and the cure rate at the time of reaction.
The phenol resin has at least two phenolic hydroxyl groups in the molecule. For example, a novolac phenol resin such as a phenol novolak resin, a cresol novolac resin, a bisphenol A type novolak resin, an allylated bis A type phenol resin, a poly -p-vinylphenol resin, phenol aralkyl resin, etc. are mentioned, but it is not limited to these, and they may be used alone or in combination.

  Although content of the said phenol resin is not specifically limited, 5 to 40 weight% of the whole said resin composition except the said inorganic filler is preferable, and 10 to 30 weight% is especially preferable. When the content is within the above range, the curability of the adhesive film for a semiconductor is particularly excellent.

The resin different from the epoxy resin and the phenol resin can act as a base substrate of the adhesive film for semiconductor.
Examples of the resin different from the epoxy resin and the phenol resin include thermoplastic resins such as polyimide resin, phenoxy resin, polyurethane resin, polybutadiene, acrylic acid copolymer, and acrylonitrile. Among these, a polyimide resin is preferable, and a polyimide resin soluble in an organic solvent described later is particularly preferable. Thereby, the workability | operativity at the time of using a polyimide resin and the preservability of a polyimide resin varnish can be improved. Furthermore, high adhesiveness and high toughness can be imparted to the adhesive film after curing, and an adhesive film for a semiconductor excellent in adhesive strength and connection reliability can be obtained.

The polyimide resin soluble in the organic solvent (thermoplastic polyimide resin soluble in the organic solvent) is, for example, a silicone-modified polyimide resin, or a linear aliphatic or alicyclic structure introduced between imide bonds. Examples thereof include polyimide resins, and polyimide resins having a large number of repeating ether-bonded or meta-substituted aromatics. Among these, a silicone resin-modified polyimide resin is preferable.
Here, being soluble in an organic solvent means that it is transparent even if a 5 wt% polyimide resin is added to the organic solvent.

Specific examples of the silicone-modified polyimide resin include those represented by the following formula (3). Thereby, for example, when connected to an organic hard substrate or a flexible printed circuit board (FPC), since the heat resistance and moisture resistance are excellent, connection reliability in various environments can be obtained. Furthermore, since the silicone-modified polyimide resin exhibits a chemical interaction with a metal, excellent adhesion (adhesiveness) to an organic hard substrate, FPC, or solder resist coated substrate can be obtained.

Examples of the acid dianhydride used for polymerization of the polyimide resin soluble in the organic solvent include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- Benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 1,2,5 Tetracarboxylic dianhydrides such as, 6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-naphthalenetetracarboxylic dianhydride;
4,4′-bisphenol A carboxylic dianhydride, ethylene glycol bistrimellitic dianhydride, pyromellitic anhydride, 4,4 ′-(hexafluoroisopropylidene) phthalic dianhydride, 4,4′-oxydiphthalate Phthalic acid dianhydrides such as acid dianhydrides; and the like. These may be used alone or in combination of two or more.

  As the diamine component used for polymerization of the polyimide resin soluble in the organic solvent, for aromatic diamine, for example, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4 -(4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenoxy) hexafluoropropane, bis-4- (4-aminophenoxy) phenylsulfone, bis-4- (3-aminophenoxy) ) Phenylsulfone, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3 -Aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl and the like. In particular, when 2,2-bis (4- (4-aminophenoxy) phenyl) propane is used, the solubility can be improved while maintaining a high glass transition temperature. Further, when 1,3-bis (3-aminophenoxy) benzene is used, the adhesiveness can be improved.

  Examples of the aliphatic diamine include 1,2-diaminocyclohexane, 1,12-diaminododecane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4. '-Diamino-3,3'-dimethyl-dicyclohexylmethane, 4,4'-diamino-3,3'-diethyl-dicyclohexylmethane, 4,4'-diamino-3,3', 5,5 '-Tetramethyl-dicyclohexylmethane, 4,4'-diamino-3,3', 5,5'-tetraethyl-dicyclohexylmethane, 4,4'-diamino-3,3'-diethyl-5 5'-dimethyl-dicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexyl, 4,4'-diamino-3,3 ', 5,5'-tetramethyldi Examples include cyclohexyl and 4,4'-diaminodicyclohexyl ether.

  Examples of other diamine components include 4,4′-methylenedi-o-toluidine, 4,4′-methylenedi-2,6-xylidine, 4,4′-methylenedi-2,6-diethylaniline, 4′-diamino-3,3 ′, 5,5′-tetramethyldiphenylmethane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) ) Phenyl) hexafluoropropane, 2,2-bis (4-aminophenoxy) hexafluoropropane, bis-4- (4-aminophenoxy) phenylsulfone, bis-4- (3-aminophenoxy) phenylsulfone, 1, 3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) ) Benzene, 1,4-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4 ′-(p-phenylenediisopropylidene) dianiline, 3,4-diamino Diphenyl ether, 4,4′-diaminodiphenyl ether, 3,4 diaminodiphenyl sulfone, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5 diaminotoluene, 2,4 diaminotoluene, 4,6-dimethyl- m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, 4,4'-diaminobenzanilide, 3,3'-dihydroxy-4,4'- And diaminobiphenyl.

前記ジアミノポリシロキサンとしては、例えば１，３−ビス（３−アミノプロピル）テトラメチルシロキサン、α，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン、１，３−ビス（４−アミノフェニル）テトラメチルシロキサン、α，ω−ビス（４−アミノフェニル）ポリジメチルシロキサン、１，３−ビス（３−アミノフェニル）テトラメチルシロキサン、α，ω−ビス（３−アミノフェニル）ポリジメチルシロキサン、１，３−ビス（３−アミノプロピル）テトラフェニルシロキサン、α，ω−ビス（３−アミノプロピル）ポリジフェニルシロキサン等が挙げられ、これらを単独あるいは２種以上混合して用いられる。 Furthermore, it is preferable to use diaminopolysiloxane represented by the following formula (2) as one of the diamine components of the polyimide resin soluble in the organic solvent. Thereby, the solubility to an organic solvent can be improved especially.

Examples of the diaminopolysiloxane include 1,3-bis (3-aminopropyl) tetramethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, and 1,3-bis (4-aminophenyl) tetra. Methylsiloxane, α, ω-bis (4-aminophenyl) polydimethylsiloxane, 1,3-bis (3-aminophenyl) tetramethylsiloxane, α, ω-bis (3-aminophenyl) polydimethylsiloxane, 1, Examples thereof include 3-bis (3-aminopropyl) tetraphenylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, and the like. These may be used alone or in combination of two or more.

  The content of the diaminopolysiloxane component is not particularly limited, but is preferably 5 to 70 mol%, particularly preferably 10 to 60 mol%, based on the total amount of all amine components. When the content is less than the lower limit, the solubility in an organic solvent may be reduced. When the content exceeds the upper limit, the heat resistance may be reduced due to a decrease in the glass transition temperature.

  The reaction between the acid anhydride and the diamine component can be performed by a known method in an aprotic polar solvent (production of polyamic acid which is a precursor of polyimide resin). Examples of the aprotic polar solvent include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methyl-2-pyrrolidone (NMP), anisole, tetrahydrofuran (THF), diglyme, cyclohexanone, Examples thereof include gamma-butyrolactone (GBL) and 1,4-dioxane (1,4-DO). These aprotic polar solvents may be used alone or in combination of two or more.

  Moreover, you may mix and use the nonpolar solvent compatible with the said aprotic polar solvent. Examples of the nonpolar solvent include aromatic hydrocarbons such as toluene, xylene, and solvent naphtha. The proportion of the nonpolar solvent in the mixed solvent is preferably 50% by weight or less. This is because if the nonpolar solvent exceeds the upper limit value, the reaction rate of thermal imidization by azeotropy is remarkably reduced, and it may be difficult to obtain a polyimide resin having a target molecular weight.

  The polyamic acid solution obtained in this manner is heated and dehydrated and cyclized in, for example, an organic solvent to form a polyimide. Since the water generated by the imidization reaction hinders the ring closure reaction, an organic solvent that is incompatible with water is added to the system and azeotroped, and the system is removed from the system using a device such as a Dean-Stark tube. Discharge. Dichlorobenzene or the like is known as an organic solvent that is incompatible with water. However, it is preferable to use the aromatic hydrocarbon because there is a possibility that a chlorine component may be mixed for use in electronics. Moreover, you may use compounds, such as an acetic anhydride, (beta) -picoline, and a pyridine, as a catalyst of imidation reaction.

  The solution obtained by the imidization reaction can be put into a poor solvent to precipitate a polyimide resin soluble in an organic solvent. In this way, unreacted monomers, impurities and foreign matters are removed and purified. The solvent to be redissolved is preferably a solvent having a low boiling point in consideration of workability, and specifically, a solvent having a boiling point of 200 ° C. or less is preferably selected. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, ether solvents such as 1,4-dioxane, tetrahydrofuran, diglyme and anisole, N, N-dimethylformamide, N, N-dimethylacetamide And amide solvents such as toluene, ethyl acetate and the like. These solvents may be used alone or in combination of two or more. In the present invention, since it is necessary to pay particular attention to the drying temperature, it is preferable to use one or more selected from methyl ethyl ketone, cyclohexanone, ethyl acetate, toluene and anisole.

  The weight average molecular weight of the resin different from the epoxy resin and the phenol resin is not particularly limited, but is preferably 20,000 to 100,000, and particularly preferably 30,000 to 80,000. When the weight average molecular weight is less than the lower limit, the toughness of the adhesive film for semiconductor may be lowered, and when the upper limit is exceeded, the connection resistance may be increased due to a decrease in fluidity during thermocompression bonding.

  Although content of the resin different from the said epoxy resin and a phenol resin is not specifically limited, 5 to 60 weight% of the whole said resin composition except the said inorganic filler is preferable, and 15 to 50 weight% is especially preferable. If the content is less than the lower limit, the mechanical strength after curing may decrease, and if the content exceeds the upper limit, the melt viscosity increases remarkably, resulting in an unfilled portion of the resin and lower connection reliability. There is a case.

[式（４）中、Ｒ１は、Ｏ、Ｓ０₂、炭素数１〜６の脂肪族基または芳香族基、Ｒ２は：式(５)で示される基、Ｒ３は炭素数１〜６の脂肪族基または芳香族基] The resin composition includes a latent catalyst. Thereby, it can harden | cure by the postcure after flip chip connection.
The latent catalyst does not promote the reaction of the curable resin at, for example, 100 ° C. or lower, but can accelerate the reaction at 120 ° C. or higher. More specifically, the gel time on the hot plate at 150 ° C. can be 1 minute 30 seconds or more.
Examples of such latent catalysts include phosphine compounds and imidazole derivatives. Phosphine compounds include triphenylphosphine, tricyclohexylphosphine, triisopropylphosphine, tetraphenylphosphonium phenoate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenoxyborate, tetraphenylphosphonium tetraalkoxyborate, tetraphenylphosphonium tetraalkylborate. And tetraphenylphosphonium. Examples of imidazole derivatives include 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, and 2-phenyl-4. -Methyl-5-hydroxydimethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6- [2'-methyl- Examples include imidazolyl- (1 ′)]-ethyl-s-triazine, 1-cyanoethyl-2-undecylimidazole, and the like. Among these, 2,4-diamino-6- [2′-methyl-imidazolyl- (1 ′)]-ethyl-s-triazine and 1-cyanoethyl-2-undecylimidazole are particularly preferable. Thereby, the latency of the catalyst is particularly improved.
Furthermore, the phosphine compound is preferably a compound (phosphonium salt) represented by the following formula (4). Thereby, it can have sufficient latency and curability. These may be used alone or in combination of two or more.

Wherein (4), R1 is, O, S0 _2, an aliphatic group or an aromatic group having 1 to 6 carbon atoms, and R2: a group represented by the formula (5), R3 is 1 to 6 carbon atoms fat Group or aromatic group]

  The content of the latent catalyst is not particularly limited, but is preferably from 0.1 to 3% by weight, particularly preferably from 0.5 to 2% by weight, based on the whole resin composition excluding the inorganic filler. When the content is less than the lower limit, the curable resin may be insufficiently cured, and when the content exceeds the upper limit, the storage stability may be lowered.

The resin composition is not particularly limited, but preferably further contains an inorganic filler. Thereby, heat resistance can be improved.
Examples of the inorganic filler include silicates such as talc, calcined clay, unfired clay, mica and glass, oxides such as titanium oxide, alumina, silica and fused silica, calcium carbonate, magnesium carbonate, hydrotalcite and the like. Carbonates, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, aluminum borate, boron Examples thereof include borates such as calcium oxide and sodium borate, and nitrides such as aluminum nitride, boron nitride, and silicon nitride.
Among these, silica is preferable. Thereby, heat dissipation can be improved.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, particularly preferably 0.1 to 8 μm. When the average particle diameter is within the above range, it is excellent in lowering the viscosity particularly during flow.

  Although content of the said inorganic filler is not specifically limited, 10 to 80 weight% of the whole said resin composition is preferable, and 30 to 70 weight% is especially preferable. When the content is within the above range, the mechanical strength is particularly excellent.

  Additives such as a coupling agent can be used in the resin composition as necessary. Examples of the coupling agent include silane, titanate, and aluminum coupling agents. Among these, a silane coupling agent having good adhesion at the interface with the silicone chip is preferable. For example, γ-glycidoxypropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Examples include trimethoxysilane and γ-methacryloxypropyltrimethoxysilane. Although the compounding quantity of the said coupling agent is not specifically limited, 0.5-10 weight part is preferable with respect to 100 weight part of curable resin and its hardening | curing agent, and 2-6 weight part is especially preferable.

  In the resin composition, various additives such as a non-reactive diluent, a reactive diluent, a thixotropic agent, and a thickener are used to improve various properties such as resin compatibility, stability, and workability. Etc. may be added as appropriate.

  As a method for producing an adhesive film for a semiconductor according to the present invention, for example, the resin composition is mixed in an organic solvent such as anisole, methyl ethyl ketone, ethyl acetate, and tetrahydrofuran to form a varnish, which is applied to form a film. Specifically, using a PET substrate or the like as a support substrate, a film is formed on the support substrate by a flow coater, roll coater, comma coater, etc., and the solvent is heated and dried to produce an adhesive film for semiconductors To do.

  Although the thickness of the said adhesive film for semiconductors is not specifically limited, 10-100 micrometers is preferable and especially 20-50 micrometers is preferable. When the thickness is within the above range, the circuit level difference and the filling property around the protruding electrode are particularly excellent.

  The adhesive film for semiconductor of the present invention can be suitably used when the semiconductor element has a protruding electrode. This is because the adhesive film for a semiconductor of the present invention has an effect as an underfill because it has connection stability, heat dissipation and heat resistance.

Moreover, the adhesive film for semiconductors of this invention can be used suitably when the joining of the said semiconductor element and a supporting member is flip chip joining. The adhesive film for a semiconductor of the present invention not only fixes the semiconductor element and the support member (substrate), but also disperses the stress applied to the bump joint after solder reflow to stabilize the bonding between the semiconductor element and the support member (substrate). This is because it also has an action as an underfill to enhance the properties.
Examples of the support member include a circuit board and a semiconductor element having electrodes.

Next, the semiconductor device of the present invention will be briefly described.
FIG. 1 is a cross-sectional view showing an example of a semiconductor device of the present invention.
In the semiconductor device 20, the semiconductor element 1 having the protruding electrode 11 and the circuit board 2 are bonded via the semiconductor adhesive film 3 as described above.
A wiring circuit 21 is formed on the upper side (semiconductor element 1 side) of the circuit board 2.
The protruding electrode 11 and the wiring circuit 21 are electrically joined.
A via (through hole) 22 is formed below the wiring circuit 21 so as to penetrate the circuit board 2.
The circuit board 2 is joined to a printed wiring board (not shown).
In the present embodiment, the semiconductor element 1 on which the protruding electrode 11 is formed is used. However, the present invention is not limited to this, and for example, the protruding electrode may be formed on the circuit board 2.
In the present embodiment, the circuit board 2 is used as the support member. However, the present invention is not limited to this, and for example, a semiconductor element having electrodes can be used.

Since the semiconductor device of the present invention uses the semiconductor adhesive film as described above, it is excellent in productivity.
Moreover, since the adhesive film for a semiconductor as described above is used, it has an action as an underfill, and therefore has excellent connection reliability.

  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)
1. Synthetic silicone-modified polyimide resin of a resin (silicone-modified polyimide resin 1) different from epoxy resin and phenol resin 1: In a four-necked separable flask equipped with a thermometer, stirrer, and raw material inlet, '-Bisphenol A acid dianhydride 43.38 (0.0833 mol) is suspended in 220.24 g of anisole and 55.06 g of toluene. As the diamine component, 23.39 g (0.05 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane and α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight) 836) 27.87 g (0.0333 mol) was added to form an amic acid.
Next, when a Dean Stark reflux condenser was attached and heated by an oil bath, the suspended solution dissolved and became transparent. At this time, water generated with imidization was removed out of the system by azeotropy with toluene. The reaction was terminated when heated to reflux for 2 hours. After cooling, it was poured into a large amount of methanol to precipitate a polyimide resin. After filtering solid content, it dried under reduced pressure at 70-80 degreeC for 12 hours, the solvent was removed, and the solid polyimide resin 1 was obtained. The weight average molecular weight was Mw = 46,000. This was soluble in methyl ethyl ketone.

2. Preparation of resin varnish 41% by weight of the above-mentioned silicone-modified polyimide resin 1 as a resin different from epoxy resin and phenol resin, and allylated bisphenol A type epoxy resin as epoxy resin (Nippon Kayaku Kogyo Co., Ltd., RE-810NM, epoxy equivalent) : 223 g / eq) 28% by weight, cresol novolac type epoxy resin (manufactured by Nippon Kayaku Kogyo Co., Ltd., EOCN-120-80, epoxy equivalent: 200 g / eq) 12% by weight, allylated phenol novolac resin (phenol resin) Showa Kasei Co., Ltd., MEH-8000H, phenol equivalent: 140 g / eq) 16 wt%, epoxy-based alkoxysilane (Shin-Etsu Silicone Co., Ltd., KBM-403E) 2.0 wt% as a coupling agent, latent catalyst Phosphine compounds (Sumitomo Bakery 1.0 wt% of SBCAT 23) manufactured by Toto Corporation was dissolved in methyl ethyl ketone to obtain a resin solution having a solid content of 60 wt%. Next, silica filler (manufactured by Admatech, SE-5101, average particle size 2 to 4 μm) as an inorganic filler is mixed so as to be 50% by weight of the total composition, and dispersed in the resin by a homomixer, and the solid content is 60% by weight. A resin varnish adjusted to 1 was obtained.

3. Manufacture of adhesive film for semiconductor Using the above-mentioned resin varnish, it is applied onto polyethylene terephthalate (made by Oji Paper Co., Ltd., thickness 38 μm) that has been subjected to a release treatment, dried at 90 ° C. for 5 minutes, and then dried. The adhesive film for semiconductors was obtained so that thickness might be set to 50 micrometers.

4). Manufacture of a semiconductor device A semiconductor element (10 mm × 10 mm, thickness: 325 μm, 120 μm pitch, 256, gold stud bump) having a projecting electrode and an FR4 type resin substrate are bonded together by the above-described adhesive film for semiconductor. Got the device.

(Example 2)
The same procedure as in Example 1 was performed except that the resin varnish was blended as follows without using an inorganic filler.
1. Synthetic silicone-modified polyimide resin 2: a resin different from epoxy resin and phenol resin (silicone-modified polyimide resin 2): 4, 4 as acid components in a four-necked separable flask equipped with a thermometer, stirrer, and raw material inlet '-Bisphenol A acid dianhydride 67.67 (0.13 mol) is suspended in 82.51 g of anisole and 80.63 g of toluene. And as a diamine component, 1,3-bis (3-aminophenoxy) benzene 15.20g (0.052mol) and 2, 2-bis (4- (4-aminophenoxy) phenyl) propane 26.68g (0 0.065 mol) and 10.87 g (0.0013) mol of α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 836) dissolved in 230 g of anisole at 70 ° C. in a dropping funnel. . Next, when a Dean Stark reflux condenser was attached and heated by an oil bath, the suspended solution dissolved and became transparent. When heating to reflux started, the diamine solution was slowly added dropwise for 0.5 hour. At this time, water generated with imidization was removed out of the system by azeotropy with toluene. The reaction was terminated when the mixture was refluxed for 2 hours after completion of the dropping. After cooling, it was poured into a large amount of methanol to precipitate a polyimide resin. After filtering solid content, it dried under reduced pressure at 70-80 degreeC for 12 hours, the solvent was removed, and the solid polyimide resin 2 was obtained. The molecular weight is Mw = 51,000. This was soluble in anisole alone or in anisole / methyl ethyl ketone (50/50).

2. Adjustment of Resin Varnish 50% by weight of the above-mentioned silicone-modified polyimide resin 3 as a resin different from the epoxy resin and the phenol resin, and a high-purity liquid bisphenol F-type epoxy resin (EXA-830LVP, manufactured by Dainippon Ink & Chemicals, Inc. Epoxy equivalent: 175 g / eq) 10% by weight, cresol novolak type epoxy resin (Nippon Kayaku Kogyo Co., Ltd., EOCN-120-80, epoxy equivalent: 200 g / eq) 2% by weight, phenolic resin allylation 10% by weight of phenol novolac resin (Showa Kasei Co., Ltd., MEH-8000H, phenol equivalent: 140 g / eq), 25 wt. Of novolac-type cyanate ester resin (Lonza Japan, PRIMASET PT-30) as other curable resin % As a ring agent, epoxy-based alkoxysilane (manufactured by Shin-Etsu Silicone, KBM-403E) 2.2% by weight, and as a latent catalyst, cobalt acetylacetonate (manufactured by Nippon Kagaku Sangyo Co., Ltd., Nursem Cobalt Co.) 0.05% by weight 0.75% by weight of triphenylphosphine (manufactured by Wako Pure Chemical Industries, Ltd., TPP) was dissolved in anisole to obtain a resin varnish having a solid content of 50% by weight.

(Example 3)
The same operation as in Example 1 was conducted except that the following were used as latent catalysts.
As a latent catalyst, 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) was used. This had a gel time on a hot plate of 150 ° C. of about 4 minutes.

Example 4
Example 1 was repeated except that the following resins were used as resins different from the epoxy resin and phenol resin.
As a resin different from the epoxy resin and the phenol resin, an acrylic acid copolymer (manufactured by Nagase Chemtech, SG-708-DR) was used.

(Example 5)
The following was made as the resin different from the epoxy resin and the phenol resin, and the same as in Example 1 except that tetrahydrofuran was used as a solvent for the resin varnish.
As a resin different from the epoxy resin and the phenol resin, an aliphatic cyclic polyimide resin (manufactured by Maruzen Petrochemical Co., Ltd., PI-100, Mw = 40,000) was used.

(Example 6)
Example 1 was repeated except that the following resins were used as resins different from the epoxy resin and phenol resin.
1. Synthetic silicone-modified polyimide resin 3: resin different from epoxy resin and phenol resin (silicone-modified polyimide resin 3): 4, 4 as acid components in a four-necked separable flask equipped with a thermometer, stirrer, and raw material inlet '-Bisphenol A acid dianhydride 52.05 g (0.1 mol) is suspended in 216 g of anisole and 54 g of toluene. As diamine components, 2,2-bis (4- (4-aminophenoxy) phenyl) propane 2.05 g (0.005 mol), α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight) 836) 12.54 g (0.015 mol) and 1,3-bis (3-aminophenoxy) benzene 23.39 g (0.08 mol) were added to form an amic acid.
Next, when a Dean Stark reflux condenser was attached and heated by an oil bath, the suspended solution dissolved and became transparent. At this time, water generated with imidization was removed out of the system by azeotropy with toluene. The reaction was terminated after 2 hours from heating to reflux. After cooling, it was poured into a large amount of methanol to precipitate a polyimide resin. After filtering solid content, it dried under reduced pressure at 70-80 degreeC for 12 hours, the solvent was removed, and the solid silicone modified polyimide resin 3 was obtained. The weight average molecular weight was Mw = 42,000. It was soluble in anisole or anisole / methyl ethyl ketone (50/50).

(Comparative Example 1)
Instead of the latent catalyst, the same procedure as in Example 1 was performed except that the usual catalyst 2-methylimidazole was used. This had a gel time on a hot plate of 150 ° C. of about 35 seconds.

(Comparative Example 2)
The procedure was the same as Example 1 except that no phenol resin was used.

(Comparative Example 3)
Example 1 was repeated except that a resin different from the epoxy resin and the phenol resin was not used.

(Comparative Example 4)
It changed into the polyimide resin soluble in an organic solvent, and it carried out similarly to Example 1 except having used the polyimide resin insoluble in the following organic solvents.
1. Synthetic polyimide resin resin 4: polyimide resin insoluble in organic solvent (polyimide resin resin 4): 3, 3 ′, 4 as acid components in a four-necked separable flask equipped with a thermometer, stirrer, and raw material inlet , 4'-biphenyltetracarboxylic dianhydride 24.63 g (0.06 mol) N-methyl-2-pyrrolidone 135.3 g and toluene 33.8 g. Then, as the diamine component, 24.63 g (0.06 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane was added to form an amic acid. Next, a Dean-Stark reflux condenser was attached, and water generated during imidization was removed out of the system by azeotropy with toluene. The reaction was terminated at 3.0 hours after the start of heating to reflux. The polyimide resin produced at this time is precipitated because it is insoluble. After cooling, the solid content is filtered and then dried under reduced pressure at 50 to 60 ° C. for 12 hours to remove the solvent and obtain a solid polyimide resin. Furthermore, it was freeze-pulverized and pulverized to about 20 μm. This was insoluble in MEK and anisole.

(Comparative Example 5)
After flip chip bonding to a semiconductor element (10 mm × 10 mm, thickness: 325 μm, 120 μm pitch, 256, gold stud bump) having a protruding electrode and an FR4 type resin substrate, the liquid resin composition for underfill described below A semiconductor device was obtained by pouring things.
Bisphenol F type liquid epoxy resin (epoxy equivalent 175, manufactured by Nippon Kayaku Co., Ltd., RE403S) 43.95% by weight, diethyldiaminodiphenylmethane 15% by weight, curing accelerator 2-phenyl-4-methylimidazole 1% by weight, In addition, 60 wt% silica filler (manufactured by Admatech, SE-5101, average particle size 2 to 4 μm) as an inorganic filler is dispersed and kneaded with three rolls in a three-roll, and vacuum defoaming treatment A liquid sealing resin composition for underfill was obtained.

In addition, the solubility to the organic solvent of the resin different from the epoxy resin and phenol resin used in each Example and each comparative example was evaluated as follows. The obtained results are shown in Table 1.
1. Solubility of the polyimide resin The solubility of the polyimide resin in the organic solvent was evaluated by visual observation of the solution state by adding 5% by weight of the polyimide resin using methyl ethyl ketone, anisole and THF as a solvent. The obtained results are shown in Table 1. Each code is as follows.
◎: Completely transparent ○: Slightly cloudy but uniform and without insoluble part △: Swelled and transparent by heating at 70 ° C. ×: Completely insoluble

  As is clear from Table 1, the silicone-modified polyimide resin was particularly excellent in solubility in a solvent.

The following evaluation was performed about the adhesive film for semiconductors and semiconductor device 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. About the protrusion of the adhesive agent to a semiconductor element The presence or absence of the protrusion of the adhesive agent to a semiconductor element was evaluated visually. Each code is as follows.
A: Less than 5% of the semiconductor element.
A: Less than 5 to 12% of the semiconductor element.
(Triangle | delta): It is less than 12 to 15% of a semiconductor element.
X: More than 15% of the semiconductor element.

2. Flip chip connectivity (fillability)
A semiconductor element (10 mm × 10 mm, thickness: 325 μm, 120 μm pitch, 256, gold stud bump) having a protruding electrode is placed on an evaluation substrate (polyimide double-layer tape substrate) at a temperature of 200 ° C., a time of 30 seconds, and a pressure. A mounting test was performed by pressure bonding with a flip chip bonder apparatus (DB200 manufactured by Kasuya Kogyo) under the condition of 0.5 MPa. At this time, the presence / absence of voids / voids was observed with a microscope, and further evaluated by cross-sectional observation. Each code is as follows.
◎: No voids / voids ○: There are some voids / voids at the end of the chip, but it can be used.
Δ: There are a small amount of voids and voids at the end of the chip, so it cannot be used.
×: Void / void

3. Connection reliability (continuity test)
After curing by heat treatment at 170 ° C. for 60 minutes using a semiconductor device prepared for void / void test, the semiconductor device is placed on a hot plate at room temperature (25 ° C.) and 260 ° C. for 20 seconds and repeated three times. It was. The connection resistance of this sample was measured at room temperature and 150 ° C. Each code is as follows.
A: No conduction failure at all.
×: Conduction failure

4). Productivity of Semiconductor Device The man-hours of the respective examples and comparative examples were evaluated based on the man-hour of the semiconductor device obtained by the method of Comparative Example 4A (100).

As apparent from Table 2, Examples 1 to 6 had no protrusion of the adhesive.
Moreover, Examples 1-6 were excellent also in connectivity and connection reliability.
Moreover, Examples 1-6 were excellent also in the adhesive strength at the time of a heat | fever.
Moreover, Examples 1-6 were excellent also in productivity.

FIG. 1 is a cross-sectional view showing an example of a semiconductor device of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor element 11 Projection electrode 2 Circuit board 21 Wiring circuit 22 Via (through hole)
3 Adhesive Film for Semiconductor 20 Semiconductor Device

Claims (10)

A semiconductor adhesive film used to join a semiconductor element and a support member,
The said adhesive film for semiconductors is comprised with the resin composition containing an epoxy resin, a phenol resin, resin different from the said epoxy resin and a phenol resin, and a latent catalyst, The adhesive film for semiconductors characterized by the above-mentioned. The adhesive film for semiconductor according to claim 1, wherein the resin composition further contains an inorganic filler. The adhesive film for a semiconductor according to claim 2, wherein the inorganic filler is silica. The adhesive film for a semiconductor according to claim 1, wherein the resin different from the epoxy resin and the phenol resin is a resin soluble in an organic solvent. 5. The adhesive film for a semiconductor according to claim 1, wherein the resin different from the epoxy resin and the phenol resin is a polyimide resin soluble in an organic solvent represented by the general formula (1).

The adhesive film for a semiconductor according to claim 5, wherein the polyimide resin soluble in the organic solvent has a diaminopolysiloxane represented by the formula (2) in an amount of 5 to 70 mol% of the total amine component.

The adhesive film for semiconductor according to any one of claims 1 to 6, wherein the semiconductor element and the support member are joined by flip chip joining. A semiconductor device, wherein a semiconductor element and a support member are joined via the semiconductor adhesive film according to claim 1. The semiconductor device according to claim 8, wherein the semiconductor element has a protruding electrode. The semiconductor device according to claim 8, wherein the support member has a protruding electrode.

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