JP2003347358A - Semiconductor adhesion film, semiconductor device and manufacturing method of semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor adhesion film which enables thermocompression to the electrode side of a semiconductor wafer with a bump electrode, enables direct junction to an electrode by flip chip connection after dicing for separation to a discrete semiconductor element, and can obtain high mounting reliability by fixing a substrate firmly. <P>SOLUTION: The semiconductor adhesion film has the wetting outgrowth of resin of 20% or less at 150°C and 100% or more at 250°C or higher and a shearing bonding strength of 4 MPa or more under an atmosphere of 240°C after being cured by heat treatment, and preferably comprises a composition of (A) a 100 pts.wt. thermoplastic polyimide resin which is soluble to an organic solvent, (B) a 50 to 150 pts.wt. thermosetting resin containing an epoxy resin and/or a cyanate ester resin and (C) a 0.1 to 5 pts.wt. hardening accelerator. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
An adhesive film for a semiconductor when a bump electrode of a semiconductor element such as C or LSI is directly joined by flip chip connection;
And a semiconductor device using the same and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, as electronic devices have become smaller and thinner, there has been a demand for the establishment of further high-density mounting techniques for semiconductor devices. A method using a lead frame, which has been conventionally used as a method for mounting a semiconductor device, cannot meet such a demand for high-density mounting. At present, a method mainly using a resin paste among the die bonding materials for bonding them is mainly used.

Therefore, flip-chip mounting has been proposed as a method for mounting a semiconductor device having substantially the same size as a semiconductor element. Flip-chip mounting has attracted attention as a method for mounting a semiconductor element with a minimum area in response to recent miniaturization and higher density of electronic devices. A bump is formed on an aluminum electrode of a semiconductor element used for flip-chip mounting, and the bump is electrically connected to a wiring on a circuit board. Solder is mainly used as the composition of these bumps, and these solder bumps are formed on the exposed aluminum terminals connected to the internal wiring of the chip by vapor deposition or plating. Other examples include gold stud bumps formed by a wire bonding apparatus.

When such a flip-chip connected semiconductor device is used as it is, the electrodes of the connecting portions 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 heat history, a large stress is applied to the connection portion of the bump, and there is a problem in mounting reliability.

In order to solve this problem, after connecting the bump and the substrate, the gap between the semiconductor element and the substrate is filled with a resin paste and cured to improve the reliability of the bonding portion, thereby bonding the semiconductor element and the substrate. The method of fixing is adopted.

[0006]

However, in general, a semiconductor element which is flip-chip mounted has a large number of electrodes, and the electrodes are arranged around the semiconductor element due to circuit design problems. If the liquid resin is poured between the electrodes of these semiconductor elements with a reduced number of capillaries during filling, the resin does not spread sufficiently and unfilled parts are likely to be formed, causing malfunctions such as unstable operation of the semiconductor elements and moisture resistance reliability. Was low. Furthermore, when the chip size is small, the liquid resin overflows to contaminate the substrate, and when the pitch between the electrodes is narrow, it becomes difficult to flow the resin. In addition, since it takes too much time to fill the resin into each of the flip-chip connected semiconductor elements, it can be said that there is a problem in productivity in consideration of the curing step.

An object of the present invention is to be able to thermocompression-bond to the electrode side of a semiconductor wafer with bump electrodes, cut and separate into individual semiconductor elements by dicing, and then directly connect the electrodes by flip-chip connection, and An object of the present invention is to provide a semiconductor adhesive film capable of firmly fixing a substrate and obtaining high mounting reliability, a semiconductor device using the same, and a method of manufacturing the same.

[0008]

According to the present invention, there is provided (1) a resin having a wetting spread of not more than 20% at 150 ° C., not less than 100% at not less than 250 ° C., and not less than 4 MPa in an atmosphere of 240 ° C. after curing by heat treatment. An adhesive film for a semiconductor having a shear adhesive strength, (2) The adhesive film for a semiconductor according to (1), containing the following composition. (A) 100 parts by weight of a thermoplastic polyimide resin soluble in an organic solvent, (B) 50 to 150 parts by weight of a thermosetting resin containing an epoxy resin and / or a cyanate ester resin, (C) a curing accelerator 0.1 to 5 parts by weight, the equivalent ratio r between the acid component and the amine component in the polycondensation reaction of the thermoplastic polyimide resin of the component (A) is 0.3.
The adhesive film for a semiconductor according to item (2), wherein 950 ≦ r <1.00 (where r = [equivalent number of all acid components] / [equivalent number of all amine components]), component (4) The thermoplastic polyimide resin (A) is soluble in the phenyl ether represented by the general formula (1) or polymerizable using the phenyl ether as a reaction solvent (2).
Item or the adhesive film for a semiconductor according to the item (3),

Embedded image (In the formula, R1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R2 is a monovalent hydrocarbon group having 1 to 6 carbon atoms.) (5) Phenyl ether is No. 4 which is anisole
The adhesive film for a semiconductor according to the item, (6) No. (1) to
(5) The semiconductor adhesive film according to any one of (5) is thermocompression-bonded to the bump side of a semiconductor wafer with a bump electrode, and the semiconductor wafer obtained by simultaneously exposing the bump electrode portion to the surface is cut into semiconductor element pieces by dicing. (7) The semiconductor device according to any one of (1) to (5), wherein the bump electrode is cut and separated, and the bump electrode is directly bonded to a circuit board or the like by flip-chip connection via an adhesive film of the semiconductor element. A method of manufacturing a semiconductor device, in which the adhesive film for use is heated and pressure-bonded to the bump electrode side of the semiconductor wafer at a temperature not lower than the glass transition temperature of the film and at least 70 ° C. lower than the temperature at the time of flip chip connection of the semiconductor element,
It is.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The adhesive film used in the present invention is mainly composed of a thermoplastic polyimide resin and a thermosetting resin comprising a repeating unit of the general formula (2) obtained by reacting a tetracarboxylic dianhydride with a diamine. It is preferable that

[0010]

Embedded image (Wherein R4 and R9 are divalent aliphatic or aromatic groups having 1 to 4 carbon atoms, R5, R6, R7 and R8 are monovalent aliphatic or aromatic groups, R3 and R10 are tetravalent R11 represents a divalent aliphatic or aromatic group, and k is an integer of 1 to 100. The ratio of m and n is such that m is 5 to 95 mol%, n
Is 5 to 95 mol%. )

The acid dianhydride used in the polymerization of the thermoplastic polyimide resin used in the present invention includes, for example, 3,3 ′,
4,4′-biphenyltetracarboxylic dianhydride, 3,
3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,
3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, ethylene glycol bistrimellitic dianhydride, 2,2 ′, 3 , 3'-benzophenonetetracarboxylic dianhydride, 4,4'-bisphenol A carboxylic dianhydride, pyromellitic anhydride, 4,4'-
(Hexafluoroisopropylidene) phthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 1,2,5 6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-naphthalenetetracarboxylic dianhydride, and the like. These can be used alone or 2
Used as a mixture of more than one species.

As the diamine component used in the present invention, 2,2-bis (4- (4-aminophenoxy) phenyl) propane and 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 can be mentioned. In particular, 2,2-bis (4- (4
When (aminophenoxy) phenyl) propane is used, it is possible to improve solubility while maintaining a high glass transition temperature. When 1,3-bis (3-aminophenoxy) benzene is used, the adhesiveness can be improved. Further, aliphatic diamines include 1,2-diaminocyclohexane, 1,12-diaminododecane, 1,3-diaminocyclohexane,
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′-tetramethyldicyclohexyl, 4,4′-diaminodicyclohexyl ether and the like, and further as another diamine component, 4,4 ′
-Methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xylidine, 4,4'-methylenedi-2,6
-Diethylaniline, 4,4'-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
-Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4 diaminodiphenylsulfone, 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'-diaminobiphenyl and the like can be mentioned.

Further, diaminopolysiloxane represented by the general formula (3) can be used as one of the diamine components of the polyimide resin. Examples of the diaminopolysiloxane include 1,3-bis (3-aminopropyl) tetramethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, and 1,3-bis (4-aminophenyl) tetramethylsiloxane , Α, ω-bis (4-aminophenyl) polydimethylsiloxane, 1,
3-bis (3-aminophenyl) tetramethylsiloxane, α, ω-bis (3-aminophenyl) polydimethylsiloxane, 1,3-bis (3-aminopropyl) tetraphenylsiloxane, α, ω-bis (3 -Aminopropyl) polydiphenylsiloxane and the like, and these may be used alone or as a mixture of two or more. Equation (4)
Is preferably used in an amount of 5 to 50 mol% of the total amount of all amine components. If it is less than 5 mol%, the solubility in an organic solvent is reduced, and if it is more than 50 mol%, the glass transition temperature is remarkably lowered, and there is a problem in heat resistance.

Embedded image (Wherein, R4 and R9 represent a divalent aliphatic or aromatic group having 1 to 4 carbon atoms, R5, R6, R7 and R8 represent a monovalent aliphatic or aromatic group, and k represents 1 to 4) It is an integer of 100.)

The reaction between the tetracarboxylic dianhydride and the diamine is carried out by a known method in an aprotic polar solvent. Aprotic polar solvents include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (D
MAC), N-methyl-2-pyrrolidone (NMP), anisole, tetrahydrofuran (THF), diglyme, cyclohexanone, gamma-butyrolactone (GB
L), 1,4-dioxane (1,4-DO) and the like. As the aprotic polar solvent, only one kind may be used, or two or more kinds may be used as a mixture. As the solvent used in the present invention, it is more preferable to use anisole having a relatively low boiling point and low harmfulness to the human body. This is because the drying temperature of the solvent can be greatly reduced, and various thermosetting components can be added.

At this time, a non-polar solvent compatible with the aprotic polar solvent may be mixed and used. As the non-polar solvent, aromatic hydrocarbons such as toluene, xylene, and solvent naphtha are often used. The proportion of the non-polar solvent in the mixed solvent is preferably 50% by weight or less. This is because if the amount of the non-polar solvent exceeds 50% by weight, the reaction rate of thermal imidization by azeotropic distillation may be remarkably reduced, and it may be difficult to obtain a polyimide resin having a target molecular weight.

The polyamic acid solution thus obtained is subsequently subjected to thermal dehydration cyclization in an organic solvent to give imidized polyimide. Since water generated by the imidization reaction interferes with the ring closure reaction, an organic solvent that is incompatible with water is added to the system and azeotroped, and the water is removed from the system using a device such as a Dean-Stark tube. Discharge. Dichlorobenzene and the like are known as organic solvents incompatible with water,
It is preferable to use the above-mentioned aromatic hydrocarbons for electronics because chlorine components may be mixed. Further, compounds such as acetic anhydride, β-picoline and pyridine may be used as a catalyst for the imidization reaction.

In the present invention, an epoxy resin, a cyanate ester resin, a compound having an active hydrogen group capable of reacting with the epoxy resin, a reaction accelerator, a catalyst and the like can be added to the obtained polyimide solution as it is. Alternatively, it is also possible to throw this solution into a poor solvent to reprecipitate and precipitate the polyimide resin to remove and purify the unreacted monomer, and to dry and dissolve it again in an organic solvent for use. In particular, in applications that dislike volatiles, impurities, foreign substances, and the like, it is preferable that the polyimide solution thus purified is further filtered and used. The solvent used at this time is preferably a solvent having a low boiling point in consideration of workability. It is preferable to select a solvent having a boiling point of 200 ° C. or lower. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone as a ketone solvent, 1,4-dioxane, tetrahydrofuran, diglyme, anisole as an ether solvent,
N, N-dimethylformamide as an amide solvent,
N, N-dimethylacetamide can be mentioned.
These solvents may be used alone or as a mixture of two or more. In the present invention, it is particularly preferable to use anisole, which can be synthesized by itself and can lower the drying temperature, as the solvent.

By greatly lowering the drying temperature as described above, a processing process at a temperature sufficiently lower than the curing start temperature of the thermosetting component can be established, and an adhesive film can be obtained without curing the curing component. . In addition, the adhesive film is semi-cured during thermocompression bonding onto a wafer, and the film-like resin flows during flip-chip connection, so that the electrodes can be joined and the semiconductor element can be fixed. The adhesive film for semiconductors of the present invention can solve the conventional problems of connection reliability by remarkably improving wet heat resistance with thermoplastic polyimide and fluidity and adhesive characteristics with thermosetting resin.

The thermoplastic polyimide (A) in the present invention
In the polycondensation reaction, the equivalent ratio r between the acid component and the amine component is preferably 0.950 ≦ r <1.000. If the r value is less than 0.950, the molecular weight of the polyimide by the polycondensation reaction does not sufficiently increase, so that sufficient mechanical properties cannot be obtained. When the molecular weight is 1.000 or more, the molecular weight similarly becomes small and becomes brittle, so that the adhesive strength is reduced. Further, unreacted carboxylic acid is undesirably decarbonated during heating at the time of flip chip connection, causing gas generation and foaming.
When the equivalent ratio r is in the above range, the amine having an active hydrogen group is in excess, and a thermosetting resin such as an epoxy resin is further crosslinked with a polyimide resin as a main component to form a tough film.

The adhesive film used in the present invention has a wetting spread of not more than 20% at the time of lamination at 150 ° C., and 100% at the temperature of 250 to 300 ° C. at the time of flip chip connection.
It is preferable that this is the case. If the wetting spread at 150 ° C. exceeds 20%, the thickness of the film after lamination is greatly changed, the uniformity is reduced, and a failure at the time of flip chip connection is caused. For example, if the resin thickness becomes extremely large and the penetration of the stud bumps becomes insufficient, the connection resistance increases and the reliability decreases. Also, 250-300
If the wetting spread at 100 ° C. is less than 100%, the fluidity of the resin at the time of connection is poor and unfilled or a large number of voids are generated, and the reflow resistance and the temperature cycle resistance are reduced, thereby causing a problem in connection reliability. Becomes Furthermore, the adhesive strength is 24
The pressure is preferably 4 MPa or more in a 0 ° C. atmosphere. 4
If it is less than MPa, reflow resistance is remarkably reduced, which is not preferable.

The thermosetting resin (B) in the present invention can fill the gap between the semiconductor element and the substrate by flowing at the time of flip chip connection. Further, after the pressure bonding, the curing reaction proceeds by heating, forming a three-dimensional network, and firmly adheres to the circuit board with the adherend. Specific examples include epoxy resin, cyanate ester, phenol, resorcinol resin, unsaturated polyester, silicone resin, urea resin, melamine resin and the like. Among them, epoxy resins and cyanate ester resins are preferred.

As the thermosetting resin, an epoxy oligomer or the like can be used in addition to the above-mentioned components. This compound has at least one epoxy group in the molecule and usually has a molecular weight of about 1,000 to 50,000, preferably about 3,000 to 10,000.

As the epoxy resin, various epoxy resins are used, and those having a molecular weight of about 300 to 2,000 are preferable. Particularly preferably, a normal temperature liquid epoxy resin having a molecular weight of 300 to 800 and / or a molecular weight of 400
It is desirably used in a form containing room temperature solid epoxy resin of 2,000 to 2000, preferably 500 to 1500. The epoxy equivalent of the epoxy resin particularly preferably used in the present invention is usually 100 to 2000 g / eq. Specific examples of such an epoxy resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and a polyethylene glycol type epoxy resin. These are 1
Species can be used alone or in combination of two or more. Among them, in the present invention, it is particularly preferable to use a bisphenol-type epoxy resin, a cresol novolak-type epoxy resin, or a phenol novolak-type epoxy resin.

The content of the thermosetting resin component (B) is from 50 to 150 per 100 parts by weight of the component (A).
It is preferred that it be contained in a proportion by weight. If the content of the component (B) is less than 50 parts by weight, sufficient fluidity cannot be obtained at the time of flip chip connection, so that an unfilled portion of the resin is formed and mounting reliability is undesirably reduced. Furthermore, sufficient adhesive strength cannot be obtained even after the main curing.
On the other hand, if it exceeds 150 parts by weight, the flexibility is lowered and the handling as a film becomes difficult, and further the brittleness of the cured product is increased and the reliability of moisture absorption is unpreferably reduced.

In the present invention, a curing accelerator can also be used, and there is no particular limitation as long as it is used for accelerating the curing of the epoxy resin. As these curing accelerators, for example, dicyandiamide derivatives, imidazoles, triphenylphosphine and the like are used. These may be used in combination of two or more. Among them, it is preferable to use imidazoles. For example, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methyl -Imidazole,
1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole,
1-cyanoethyl-2-phenylimidazole and the like.

In the thermosetting resin that can be used in the present invention, the curing accelerator is an epoxy resin 100
It is preferably used in an amount of 0 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight based on parts by weight.

Further, a reaction product of an epoxy resin and an amine compound can also be used. This is called a microcapsule-type curing agent, in which the amine compound added by heating is released from the epoxy resin and acts on the epoxy resin. For example, there is a resin obtained by adding an isocyanate to a bis-F epoxy resin and 2-methylimidazole.

Further, additives such as a coupling agent can be used in the adhesive film of the present invention, if necessary. Examples of the coupling agent include silane-based, titanate-based, and aluminum-based coupling agents. Among them, a silane coupling agent having good adhesion at the interface with the silicon chip is preferable. For example, γ-glycidoxypropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like can be mentioned. The amount of the coupling agent is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the resin.

In the method for producing an adhesive film for a semiconductor according to the present invention, first, each of the above-mentioned components is mixed in an organic solvent such as N-methyl-2-pyrrolidone or anisole to form a varnish. Form a film. Specifically, for example, a heat-resistant film substrate is used as a support, and a similar film layer is formed on one or both sides thereof to obtain an adhesive film together with the support, or a roll, a metal sheet, a polyester sheet, etc. On the mold sheet,
A film can be formed by a method such as forming a film with a flow coater, a roll coater, a comma coater, or the like, drying by heating, and then peeling to form a single-layer adhesive film.

The adhesive film for a semiconductor thus obtained can be obtained without curing the curing component. This adhesive film can be semi-cured (B-stage state) during thermocompression bonding onto a wafer, and has sufficient fluidity even during flip-chip connection, so that resin can be filled together with electrode connection. The adhesive film for a semiconductor according to the present invention is characterized by improving connection reliability, which has been a conventional problem, and having both high moisture-heat resistance and adhesive properties.

The glass transition temperature Tg after curing of the adhesive film for semiconductor used in the present invention is preferably 100 ° C. or higher. If the glass transition temperature is lower than 100 ° C., mounting reliability due to flip-chip connection is significantly reduced, which is not preferable. In the present invention, it is preferable that the condition for bonding to the wafer is a temperature higher than the glass transition temperature of the adhesive film and lower than the temperature at the time of flip chip connection of the semiconductor element by 70 ° C. or higher. The bonding temperature of the adhesive film is T
If it is less than g, the sticking property is lowered, and if the temperature is less than 70 ° C. than the temperature at the time of flip chip connection, the curing of the hardened component proceeds, so there is not sufficient fluidity at the time of flip chip connection, so that an unfilled portion of the resin is not preferable. . The pressure applied to the wafer is preferably 0.1 to 1 MPa. If the pressure is less than 0.1 MPa, the pressure is too weak, voids are generated, and the wettability of the resin at the bonding interface is not sufficient.
If the pressure exceeds, the pressure may be too strong and the wafer may be broken.

According to the semiconductor device of the present invention, the semiconductor device with the adhesive separated by dicing is bonded to the substrate by bump bonding with the substrate by flip-chip bonding after the thermocompression bonding of the semiconductor adhesive film to the bump electrode surface of the wafer is carried out. It is characterized in that the electrodes are directly bonded and a film adhesive is embedded in the gap between the semiconductor element and the substrate.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

Example 1 Silicone-modified polyimide resin: In a four-necked separable flask equipped with a thermometer, a stirrer and a raw material inlet, 4,4'-oxydiphthalic dianhydride 18.1 was used as an acid component.
5 g (0.0585 mol), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride 17.21 (0.05
85 mol), 130.81 g of anisole and 7
Suspend to 3.75 g. And, as the diamine component, 24.63 g (0.06 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane and α, ω-
A solution prepared by heating and dissolving 50.16 g (0.06 mol) of bis (3-aminopropyl) polydimethylsiloxane (average molecular weight: 836) in 164.2 g of anisole at 70 ° C. is placed in a dropping funnel. Then, a Dean-Stark reflux condenser was attached and the suspension was dissolved by heating with an oil bath, and the suspension became transparent. When heating to reflux started, the diamine solution was slowly added dropwise for 1 hour. At this time, water generated during the imidization was removed from the system by azeotropic distillation with toluene. The reaction was terminated when the mixture was heated under reflux for 3.0 hours after the completion of the dropwise addition. Thus, a polyimide resin soluble in anisole was obtained. The molecular weight is Mw = 35000.

With respect to 100 parts by weight of the obtained polyimide resin, 50 parts by weight of a cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-1020-90), and a cyanate ester resin (manufactured by Asahi Kasei Epoxy Co., Ltd.) Trade name AROCY L-10) 12.5 parts by weight,
1-cyanoethyl-2-ethyl-4-methylimidazole (trade name 2E4MZ-C, manufactured by Shikoku Chemicals Co., Ltd.)
N) 0.5 parts by weight, 3-glycidoxypropyltrimethoxysilane (trade name KBM, manufactured by Shin-Etsu Silicone Co., Ltd.)
-403E) 4 parts by weight, N-phenyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.
After adding 5 parts by weight of trade name KBM-573) and stirring and mixing, the mixture was degassed under vacuum. This resin varnish was applied on a 38 μm-thick polyethylene terephthalate support base material by a roll coater so that the film thickness after drying was 40 μm.
For 2 minutes, at 80 ° C. for 2 minutes, and at 90 ° C. for 2 minutes in a hot air circulating drier to obtain a polyimide resin film with a release film.

Next, the adhesive strength of the obtained adhesive film for semiconductor was measured.

[Heat shear strength at 240 ° C.] 7 × 7 mm
The film is punched out with a mold and temporarily pressed at a pressing temperature of 160 ° C., a pressure of 2 MPa and a pressing time of 0.3 second, and then the film is subjected to a 42-alloy at a pressing temperature of 160 ° C., a pressure of 1 MPa and a pressing time of 1.0 second. To the lead frame. Next, a 4 mm square silicon chip is mounted on the 7 × 7 mm film at a pressing temperature of 180 ° C., a pressure of 1 MPa and a pressing time of 1.0 second, and cured at 180 ° C. for 1 hour. After curing, use a push-pull gauge at 240 ° C-2
The hot die shear strength after 0 seconds was measured.

Next, the wet spread rate of the obtained adhesive film for semiconductor was measured.

[Wet Spreading Ratio] A circular film punched with a 2.5 mmφ mold was used to form a 42 alloy plate and a glass plate (thickness 2).
00 μm, 150 mmφ), and the glass side is heated with a heater to a compression temperature of 150 or 250 ° C.
The two-plate alloy side is pressed at a normal temperature at a pressure of 1 MPa, a pressure bonding time of 10 seconds, and a load of 5 kgf. The diameter of the pressed resin was measured with a stereoscopic microscope, and the wet spreading ratio was calculated.
[Wet spread rate] = {[Area after crimping]-[Initial area]} /
[Initial area] × 100 (%).

Example 2 Silicone-modified polyimide resin: 4,4'-bisphenol A dianhydride as an acid component in a four-necked separable flask equipped with a thermometer, a stirrer, and a raw material inlet.
75 (0.0975 mol) to anisole 143.34
g, 60.83 g of toluene. And, as the diamine component, 23.39 g (0.080 mol) of 1,3-bis (3-aminophenoxy) benzene and α, ω
A solution obtained by heating and dissolving 23.38 g (0.020) mol of bis (3-aminopropyl) polydimethylsiloxane (average molecular weight: 836) in 100 g of anisole at 70 ° C. is placed in a dropping funnel. Then, a Dean-Stark reflux condenser was attached and the suspension was dissolved by heating with an oil bath, and the suspension became transparent. When heating to reflux started, the diamine solution was slowly added dropwise for 0.5 hour. At this time, water generated during the imidization was removed from the system by azeotropic distillation with toluene. The reaction was completed when the mixture was heated under reflux for 2.0 hours after completion of the dropwise addition. Thus, a polyimide resin soluble in anisole was obtained. The molecular weight is Mw = 27000.

Cresol novolak type epoxy resin (trade name: EOCN-1020-90, manufactured by Nippon Kayaku Co., Ltd.) is used with respect to 100 parts by weight of the obtained polyimide resin.
Parts by weight, high-purity bis-F type epoxy resin (epoxy equivalent 1
75, manufactured by Nippon Kayaku Co., Ltd., trade name RE403S) 3
4.8 parts by weight, novolak type cyanate ester resin (manufactured by Lonza Japan Co., Ltd., trade name: PRIMASET)
PT-30) 65.2 parts by weight, 1-benzyl-2-phenylimidazole (trade name 1 manufactured by Shikoku Chemicals Co., Ltd.)
(B2PZ) 0.35 parts by weight, cobalt acetylacetonate (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name Nercem Cobalt Cobalt), 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name KBM-403)
E) 1 part by weight, N-phenyl-γ-aminopropyltrimethoxysilane (trade name K, manufactured by Shin-Etsu Silicone Co., Ltd.)
BM-573) 0.5 part by weight was added, mixed with stirring, and then degassed in vacuo. This resin varnish was applied on a 38 μm-thick polyethylene terephthalate support base material by a roll coater so that the film thickness after drying was 40 μm.
For 2 minutes at 80 ° C. and 2 minutes at 90 ° C. in a hot-air circulation dryer to obtain a polyimide resin film with a release film.

The obtained adhesive film for a semiconductor was used in Example 1.
The shear adhesive strength at 240 ° C. hot and the spread ratio of wetness were measured in the same manner as in the above.

Comparative Example 1 Silicone-modified polyimide resin: In a four-neck separable flask equipped with a thermometer, a stirrer, and a raw material inlet, 4,8.6′-oxydiphthalic dianhydride 18.6 was used as an acid component.
133 g of anisole (1 g, 0.06 mol), 13.65 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 74.36 g of toluene
g. And, as the diamine component, 2,2
-Bis (4- (4-aminophenoxy) phenyl) propane (24.63 g, 0.06 mol) and α, ω-bis (3
(Aminopropyl) polydimethylsiloxane (average molecular weight: 836) 50.16 g (0.06 mol) dissolved in 164.2 g of anisole by heating at 70 ° C. is placed in a dropping funnel. Then, a Dean-Stark reflux condenser was attached and the suspension was dissolved by heating with an oil bath, and the suspension became transparent. When heating and refluxing begin, diamine solution 1
It was dripped slowly over time. At this time, water generated during the imidization was removed from the system by azeotropic distillation with toluene. The reaction was terminated when the mixture was heated under reflux for 3.0 hours after the completion of the dropwise addition.
Thus, a polyimide resin soluble in anisole was obtained. The molecular weight is Mw = 65000.

With respect to 100 parts by weight of the obtained polyimide resin, 50 parts by weight of a cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-1020-90), and a cyanate ester resin (manufactured by Asahi Kasei Epoxy Co., Ltd.) Trade name AROCY L-10) 12.5 parts by weight,
1-cyanoethyl-2-ethyl-4-methylimidazole (trade name 2E4MZ-C, manufactured by Shikoku Chemicals Co., Ltd.)
N) 0.5 parts by weight, 3-glycidoxypropyltrimethoxysilane (trade name KBM, manufactured by Shin-Etsu Silicone Co., Ltd.)
-403E) 4 parts by weight, N-phenyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.
After adding 5 parts by weight of trade name KBM-573) and stirring and mixing, the mixture was degassed under vacuum. This resin varnish was applied on a 38 μm-thick polyethylene terephthalate support base material by a roll coater so that the film thickness after drying was 40 μm.
For 2 minutes, at 80 ° C. for 2 minutes, and at 90 ° C. for 2 minutes in a hot air circulating drier to obtain a polyimide resin film with a release film.

The obtained adhesive film for a semiconductor was prepared in Example 1.
The shear adhesive strength at 240 ° C. hot and the spread ratio of wetness were measured in the same manner as in the above.

Comparative Example 2 Silicone-modified polyimide resin: 4,4'-bisphenol A dianhydride as an acid component in a four-neck separable flask equipped with a thermometer, a stirrer, and a raw material inlet.
05 (0.10 mol) is suspended in 146.82 g of anisole and 61.71 g of toluene. As the diamine component, 23.39 g (0.080 mol) of 1,3-bis (3-aminophenoxy) benzene and 23.38 g of α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight: 836) are used. A solution obtained by heating and dissolving (0.020) mol in 100 g of anisole at 70 ° C. is placed in a dropping funnel. Then, a Dean-Stark reflux condenser was attached and the suspension was dissolved by heating with an oil bath, and the suspension became transparent. When heating to reflux started, the diamine solution was slowly added dropwise for 0.5 hour. At this time, water generated during the imidization was removed from the system by azeotropic distillation with toluene.
The reaction was completed when the mixture was heated under reflux for 2.0 hours after completion of the dropwise addition. Thus, a polyimide resin soluble in anisole was obtained. The molecular weight is Mw = 51000.

Cresol novolak type epoxy resin (trade name: EOCN-1020-90, manufactured by Nippon Kayaku Co., Ltd.) is used with respect to 100 parts by weight of the obtained polyimide resin.
Parts by weight, high-purity bis-F type epoxy resin (epoxy equivalent 1
75, manufactured by Nippon Kayaku Co., Ltd., trade name RE403S) 3
4.8 parts by weight, novolak type cyanate ester resin (manufactured by Lonza Japan Co., Ltd., trade name: PRIMASET)
PT-30) 65.2 parts by weight, 1-benzyl-2-phenylimidazole (trade name 1 manufactured by Shikoku Chemicals Co., Ltd.)
(B2PZ) 0.35 parts by weight, cobalt acetylacetonate (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name Nercem Cobalt Cobalt), 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name KBM-403)
E) 1 part by weight, N-phenyl-γ-aminopropyltrimethoxysilane (trade name K, manufactured by Shin-Etsu Silicone Co., Ltd.)
BM-573) 0.5 part by weight was added, mixed with stirring, and then degassed in vacuo. This resin varnish was applied on a 38 μm-thick polyethylene terephthalate support base material by a roll coater so that the film thickness after drying was 40 μm.
For 2 minutes at 80 ° C. and 2 minutes at 90 ° C. in a hot-air circulation dryer to obtain a polyimide resin film with a release film.

The obtained adhesive film for semiconductors was prepared in Example 1.
The shear adhesive strength at 240 ° C. hot and the spread ratio of wetness were measured in the same manner as in the above.

The adhesive film for semiconductor of Example 1 was replaced with 180
When cured by heat treatment for 1 hour, the glass transition temperature is 110 ° C and the elastic modulus is 240 ° C by dynamic viscoelasticity measurement.
MPa, the shear strength at 240 ° C. hot shear was 4.5 MPa, and the wetting and spreading ratio was 15% at 150 ° C. and 130% at 250 ° C. On the other hand, the adhesive film for a semiconductor of Comparative Example 1 was subjected to the same heat treatment to have a glass transition temperature of 108 ° C., an elastic modulus of 14 MPa at 240 ° C., a shear adhesive strength at 240 ° C. hot of 2.0 MPa, and a wet spreading rate of 150 ° C. 12% in 2
It was 145% at 50 ° C. When the adhesive film for a semiconductor of Example 2 was cured by heat treatment at 180 ° C. for 1 hour, the glass transition temperature was 128 ° C., the elastic modulus was 95 MPa at 240 ° C. by dynamic viscoelasticity measurement, and the adhesive strength at 240 ° C. hot was 5. 3
MPa, the wetting and spreading ratio were 10% at 150 ° C. and 105% at 250 ° C. On the other hand, the adhesive film for a semiconductor of Comparative Example 2 was subjected to the same heat treatment to have a glass transition temperature of 130.
C., the elastic modulus is 40 MPa at 240 ° C., the adhesive strength at 240 ° C. heat is 3.5 MPa, and the wetting and spreading rate is 12 at 150 ° C.
% At 250 ° C.

The adhesive films of Examples 1 and 2 were thermocompression-bonded to the bump side of a semiconductor wafer with gold bump electrodes, and the bump electrodes were simultaneously exposed to the surface. When cutting and separating,
Defects such as chipping and chip cracks did not occur and were very good. The semiconductor element with the adhesive film was satisfactorily connected by flip-chip bonding at 270 ° C. for 10 seconds.

[0051]

The adhesive film of the present invention can be thermocompression-bonded to the bump side of a wafer with bump electrodes and the bump electrode portion can be exposed to the surface, and subsequently has good dicing properties. When the bump electrode and the circuit board are flip-chip connected using the semiconductor element with the adhesive film, the adhesive resin flows without voids and voids, and can be filled between the semiconductor element and the substrate. Furthermore, the adhesive film of the present invention is excellent in strong adhesiveness and high moisture and heat resistance, and a flip chip package using the same relieves thermal stress generated at the time of heating and cooling,
Excellent reflow resistance and temperature cycle resistance due to high elastic modulus. Thus, the present invention can provide an adhesive film most suitable for a flip chip package.

Claims (7)

[Claims] 1. A semiconductor characterized in that the resin has a wetting spread of not more than 20% at 150 ° C., not less than 100% at not less than 250 ° C., and having a shear adhesive strength of not less than 4 MPa in an atmosphere of 240 ° C. after curing by heat treatment. Adhesive film. 2. The adhesive film for a semiconductor according to claim 1, which comprises the following composition. (A) 100 parts by weight of a thermoplastic polyimide resin soluble in an organic solvent, and (B) a thermosetting resin 50 containing an epoxy resin and / or a cyanate ester resin.
To 150 parts by weight, (C) 0.1 to 5 parts by weight of a curing accelerator. 3. An equivalent ratio r between an acid component and an amine component in the polycondensation reaction of the thermoplastic polyimide resin of the component (A) is 0.1.
3. The adhesive film for a semiconductor according to claim 2, wherein 950 ≦ r <1.00 (where r = [equivalent number of all acid components] / [equivalent number of all amine components]). 4. The thermoplastic polyimide resin of the component (A) is soluble in phenyl ether represented by the general formula (1) or is polymerizable using phenyl ether as a reaction solvent. 4. The adhesive film for a semiconductor according to 3. Embedded image (In the formula, R1 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R2 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.) 5. The adhesive film for a semiconductor according to claim 4, wherein the phenyl ether is anisole. 6. A semiconductor wafer obtained by thermocompression bonding the adhesive film for a semiconductor according to any one of claims 1 to 5 to a bump side of a semiconductor wafer with a bump electrode and simultaneously exposing the bump electrode portion to the surface. A semiconductor device, which is cut and separated into individual semiconductor element pieces, and the bump electrodes are directly bonded to a circuit board or the like by flip-chip connection via an adhesive film of the semiconductor element. 7. The bump electrode of a semiconductor wafer, wherein the adhesive film for a semiconductor according to claim 1 is at a temperature not lower than the glass transition temperature of the film and at least 70 ° C. lower than the temperature at the time of flip chip connection of the semiconductor element. A method of manufacturing a semiconductor device in which dicing is performed after heat-pressing to the side.