JP2003261834A - Adhesive film for semiconductor, semiconductor device, and method for manufacturing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive film for semiconductors which can effect thermocompressing bonding to the electrode side of a semiconductor wafer with a bump electrode, and can directly bond electrodes by flip chip connection after cutting and separating the wafer into individual semiconductor elements by dicing and, simultaneously, can firmly secure the substrate to obtain high mounting reliability. <P>SOLUTION: The adhesive film for semiconductors comprises (A) a thermoplastic polyimide resin which is soluble in an organic solvent and has a glass transition temperature of ≥100°C and (B) a thermosetting resin with a content of component (B), based on the total components, of 20-70 wt.%, and has a glass transition temperature after curing by heat treatment of ≥100°C, a storage modulus at 25°C of 2,500-6,000 MPa, and a storage modulus at ≥200°C of ≥40 MPa. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
An adhesive film for semiconductor when directly bonding bump electrodes of a semiconductor element such as C or LSI by flip chip connection,
The present invention also relates to a semiconductor device using the same and a manufacturing method thereof.

[0002]

2. Description of the Related Art With the recent miniaturization and thinning of electronic equipment, there is a demand for the establishment of higher density packaging technology for semiconductor elements. A method using a lead frame which has been conventionally used as a semiconductor device mounting method cannot meet such a demand for high-density mounting. In addition, among die-bonding materials for adhering these, at present, a method mainly using a resin paste is predominant.

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 been attracting attention as a method of mounting a semiconductor element in a minimum area in response to recent miniaturization and high density of electronic devices. Bumps are formed on the aluminum electrodes of the semiconductor element used for this flip-chip mounting, and the bumps and the wiring on the circuit board are electrically connected. 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. Others include gold stud bumps formed by wire bonding equipment.

When such a flip-chip connected semiconductor device is used as it is, the electrodes of the connecting portion are exposed in the air, and the difference in the coefficient of thermal expansion between the chip and the substrate is large. Due to the thermal history of the process, a large stress is applied to the bump connection portion, which causes a problem in mounting reliability.

In order to solve this problem, in order to improve the reliability of the joint after connecting the bump and the substrate,
A method of fixing the semiconductor element and the substrate by filling a gap between the semiconductor element and the substrate with a resin paste and curing the resin paste is adopted.

[0006]

However, in general, a semiconductor element for flip-chip mounting has a large number of electrodes, and the electrodes are arranged around the semiconductor element due to problems in circuit design. When filling, liquid resin is poured between the electrodes of these semiconductor elements by reducing the capillaries, and the resin does not spread sufficiently and unfilled parts are easily formed, resulting in unstable operation of semiconductor elements and moisture resistance reliability. There was a problem that was low. Further, when the chip size is reduced, the liquid resin is squeezed out to contaminate the substrate, and when the pitch between the electrodes is narrowed, it becomes difficult to pour the resin. Further, 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 when the step of curing is also taken into consideration.

The object of the present invention is that the electrode side of a semiconductor wafer having bump electrodes can be thermocompression-bonded, the semiconductor element is cut and separated into individual pieces by dicing, and then the electrodes are directly joined by flip-chip connection, and Provided are an adhesive film for a semiconductor capable of firmly fixing a substrate to obtain high mounting reliability, a semiconductor device using the same, and a manufacturing method thereof.

[0008]

According to the present invention, (1) the glass transition temperature after curing by heat treatment is 100 ° C. or higher,
Storage elastic modulus at 25 ° C. is 2500-6000 MPa,
An adhesive film for semiconductors having a pressure of 40 MPa or higher at 200 ° C. or higher, (2) a thermoplastic polyimide resin (A) soluble in an organic solvent and having a glass transition temperature of 100 ° C. or higher, and (B) a thermosetting resin. And the content of (B) is 20 to 70% by weight based on all components, the adhesive film for a semiconductor according to (1), the thermoplastic polyimide resin of (3) component (A) is used as an acid component. 4,1 'represented by (1)
-A semiconductor adhesive film according to item (2), which comprises bisphenol A carboxylic acid dianhydride.

[0009]

[Chemical 3] (4) The thermoplastic polyimide resin of the component (A) is soluble in the phenyl ether represented by the general formula (2) or is polymerizable using phenyl ether as a reaction solvent. Or an adhesive film for semiconductor according to the item (3),

[0010]

[Chemical 4] (In the formula, R7 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R8 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.) (5) Phenyl ether An adhesive film for a semiconductor according to item (4), which is anisole.

(6) Obtained by thermocompression-bonding the semiconductor adhesive film according to any one of items (1) to (5) to the bump side of a semiconductor wafer having bump electrodes, and simultaneously exposing the bump electrode portions on the surface. A semiconductor device characterized in that the semiconductor wafer is cut and separated into individual semiconductor element pieces by dicing, and the bump electrodes are directly bonded to a circuit board or the like by flip-chip connection through an adhesive film of the semiconductor element.
(7) The adhesive film for a semiconductor according to any one of (1) to (5) is applied to a semiconductor wafer at a temperature not lower than the glass transition temperature of the film and not lower than 70 ° C. lower than the temperature at the time of flip chip connection of a semiconductor element. A method of manufacturing a semiconductor device, comprising dicing after thermocompression bonding to the bump electrode side.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive film used in the present invention is a thermoplastic polyimide having a glass transition temperature of 100 ° C. or higher, which is composed of repeating units of the general formula (3) obtained by the reaction of tetracarboxylic dianhydride and diamine. It is preferable to use a resin and a thermosetting resin as main components.

[0013]

[Chemical 5] (In the formula, R1 and R2 are C1 to C4 divalent aliphatic groups or aromatic groups, R3, R4, R5, and R6 are monovalent aliphatic groups or aromatic groups, and R9 and R10 are four groups. A divalent aliphatic group or an aromatic group, R11 represents a divalent aliphatic group or an aromatic group,
k is an integer of 1 to 100. The ratio of m and n is 0 to 100 mol% and n is 0 to 1 in 100 mol% of each component in total.
It is 00 mol%. )

The acid dianhydride used in the polymerization of the thermoplastic polyimide resin used in the present invention is, for example, 3,3 ',
4,4'-biphenyltetracarboxylic dianhydride, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 3,
3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, ethylene glycol bistrimellitic dianhydride, 2,2 ', 3 , 3'-benzophenone tetracarboxylic dianhydride, 4,4'-bisphenol A carboxylic dianhydride, pyromellitic dianhydride, 4,4'-
(Hexafluoroisopropylidene) phthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 1,2,5 6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-naphthalenetetracarboxylic dianhydride, and the like. These alone or 2
Used as a mixture of two or more species. In the present invention, from the viewpoint of adhesiveness, heat resistance and solubility in organic solvents, 4,4 '
-Bisphenol A carboxylic acid dianhydride is preferred.

As the diamine component used in the present invention, aromatic diamines include 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) phenyl sulfone, bis-4- (3-aminophenoxy) Phenyl sulfone, 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. Especially 2,2-bis (4
When-(4-aminophenoxy) phenyl) propane is used, it is possible to improve the solubility while keeping the glass transition temperature high. Further, when 1,3-bis (3-aminophenoxy) benzene is used, it is possible to improve the adhesiveness. Further, in the aliphatic diamine, 1,2-diaminocyclohexane, 1,12-diaminododecane,
1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4′-diaminodisichexylmethane, 4,4′-diamino-3,3′-dimethyl-disichexylmethane, 4,4′-diamino -3,3'-diethyl-disichexylmethane, 4,4'-diamino-
3,3 ', 5,5'-Tetramethyl-disichexylmethane, 4,4'-diamino-3,3', 5,5'-tetraethyl-disichexylmethane, 4,4'-diamino-3 , 3'-diethyl-5,5'-dimethyl-disichexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexyl, 4,4'-diamino-3,
3 ', 5,5'-tetramethyldicyclohexyl, 4,
4'-diamino disichexyl ether etc. are mentioned. Still other diamine components include 4,4'-methylenedi-o-toluidine and 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) phenyl sulfone, bis-4- ( 3-
Aminophenoxy) phenyl sulfone, 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 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'-diaminobiphenyl, etc. can be mentioned.

Further, diaminopolysiloxane represented by the general formula (4) can be used as one of the diamine components of the polyimide resin.

[Chemical 6] (In the formula, R1 and R2 represent divalent aliphatic groups or aromatic groups having 1 to 4 carbon atoms, R3, R4, R5 and R6 represent monovalent aliphatic groups or aromatic groups, and k represents 1 to It is an integer of 100.) Examples of the diaminopolysiloxane include 1,3-bis (3-aminopropyl) tetramethylsiloxane,
α, ω-bis (3-aminopropyl) polydimethylsiloxane, 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,
[alpha], [omega] -bis (3-aminopropyl) polydiphenylsiloxane and the like can be mentioned, and these can be used alone or in combination of two or more kinds. The diaminopolysiloxane represented by the formula (4) is preferably used in an amount of 0 to 50 mol% based on the total amount of all amine components. If it exceeds 50 mol%, the glass transition temperature is remarkably lowered, and there is a possibility that heat resistance may be deteriorated.

The reaction between the tetracarboxylic dianhydride and the diamine is carried out by a known method in an aprotic polar solvent. The aprotic polar solvent is 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. The aprotic polar solvent may be used alone or in combination of two or more. As the solvent used in the present invention, it is more preferable to use anisole, which has a relatively low boiling point and is less harmful to the human body. This is because the drying temperature of the solvent can be significantly lowered 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 nonpolar solvent in the mixed solvent is preferably 50% by weight or less. This is because if the amount of the nonpolar solvent exceeds 50% by weight, the reaction rate of the thermal imidization by azeotropy is remarkably reduced, and it may be difficult to obtain a polyimide resin having a desired molecular weight.

The polyamic acid solution thus obtained is subsequently heated and dehydrated in an organic solvent to form an imidized polyimide. Since the 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 to azeotropically evaporate it and remove it from the system using a device such as Dean-Stark tube. Discharge. Dichlorobenzene and the like are known as organic solvents that are incompatible with water,
For electronics, it is preferable to use the above aromatic hydrocarbons because chlorine components may be mixed therein. In addition, 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 an epoxy resin, a reaction accelerator, a catalyst or the like can be added to the obtained polyimide solution as it is. Alternatively, this solution may be put into a poor solvent to reprecipitate and precipitate the polyimide resin to remove unreacted monomers, purified, and dried, and then dissolved and used again in an organic solvent. Particularly in applications where volatile components, impurities, foreign substances, etc. are disliked, it is preferable to filter the polyimide solution thus produced before use. The solvent used at this time is preferably a solvent having a low boiling point in consideration of workability. Boiling point is 2
It is preferable to select a solvent having a temperature of 00 ° 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, and N, N-dimethylformamide, N, N- as an amide solvent.
Dimethylacetamide can be mentioned. These solvents may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use anisole as the solvent, which can be synthesized by itself and can be dried at a low temperature.

By significantly 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 constructed, and an adhesive film can be obtained without curing the curing component. . Further, this adhesive film is semi-cured during thermocompression bonding onto the wafer, and during flip chip connection, the film-like resin flows to bond electrodes and fix semiconductor elements. INDUSTRIAL APPLICABILITY The adhesive film for a semiconductor of the present invention can remarkably improve the connection reliability, which has been a problem in the past, the wet heat resistance by the thermoplastic polyimide, and the fluidity and the adhesive property by the thermosetting resin.

The glass transition temperature Tg of the thermoplastic polyimide resin (A) used in the present invention (intersection of tangents in the measurement by a thermomechanical analyzer) is the above-mentioned acid anhydride, aromatic or aliphatic diamine, and polyamino acid. The temperature is preferably 100 ° C. or higher depending on the combination of siloxanes. Tg is 10
If the temperature is lower than 0 ° C., the Tg of the film after curing does not sufficiently increase, so that the reliability of the adhesive strength in a hot atmosphere decreases. If Tg exceeds 200 ° C., the solvent cannot be completely removed unless the film drying temperature is raised, and the thermosetting resin is cured during the drying of the solvent, which is not preferable. Further, when a wafer in which this adhesive film is heated and pressure-bonded to the wafer is used, chip cracks and chips that occur during dicing can be reduced. Further, by the main curing, the glass transition temperature of the film is increased to the glass transition temperature of the thermoplastic polyimide resin, which is the main component, or higher, and it has excellent shear strength properties in a hot atmosphere. And

The thermosetting resin (B) in the present invention can flow in the flip chip connection to fill the gap between the semiconductor element and the substrate. Further, the curing reaction proceeds by heating after pressure bonding to form a three-dimensional mesh, and the adherend is firmly adhered to the circuit board. Specific examples include epoxy resin, cyanate ester, phenol, resorcinol resin, unsaturated polyester, silicone resin, urea resin, melamine resin and the like. Of these, epoxy resins and cyanate ester resins are preferable.

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 1,000 to 50,000, preferably about 3,000 to 10,000.

As the epoxy resin, various epoxy resins are used, but those having a molecular weight of about 300 to 2000 are preferable. Particularly preferably, a room temperature liquid epoxy resin having a molecular weight of 300 to 800 and / or a molecular weight of 400
˜2000, preferably 500 to 1500, is preferably used in a form containing a room temperature solid epoxy resin. The epoxy equivalent of the epoxy resin used particularly preferably 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 novolac type epoxy resin, a cresol novolac type epoxy resin, and a polyethylene glycol type epoxy resin. These are 1
They may 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 novolac type epoxy resin or a phenol novolac type epoxy resin.

The content of these thermosetting components (B) is preferably 20 to 70% by weight based on the total components. When the content of the component (B) is less than 20% by weight,
Since sufficient fluidity cannot be obtained at the time of flip chip connection, a resin unfilled portion is formed and mounting reliability deteriorates, which is not preferable. Further, even after the main curing, sufficient adhesive strength cannot be obtained. If the content exceeds 70% by weight, the flexibility decreases, the handling as a film becomes difficult, the brittleness of the cured product increases, and the moisture absorption reliability decreases significantly, which is not preferable.

A curing accelerator can also be used in the present invention, and there is no particular limitation as long as it is used to accelerate the curing of the epoxy resin. As these curing accelerators, for example, dicyandiamide derivatives, imidazoles, triphenylphosphine and the like are used. You may use together 2 or more types of these. 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 can be mentioned.

In the thermosetting resin which can be used in the present invention, the above-mentioned curing accelerator is 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 with respect to 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, and the amine compound added by heating is released from the epoxy resin and acts on the epoxy resin. For example, there is a bis F-type epoxy resin and 2-methylimidazole to which isocyanate is added.

Further, additives such as coupling agents 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). Examples thereof include ethyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane. The compounding amount of the coupling agent is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin.

In the method for producing an adhesive film for a semiconductor of the present invention, first, the above components are mixed in an organic solvent such as N-methyl-2-pyrrolidone or anisole to form a varnish, which is applied. 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 of the support to obtain an adhesive film together with the support, or a roll, a metal sheet, a polyester sheet or the like is separated. On the mold sheet,
A film can be formed by a flow coater, a roll coater, a comma coater, etc., dried by heating, and then peeled to obtain 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 on the wafer, and has sufficient fluidity even during flip-chip connection, so that the resin can be filled together with the connection of the electrodes. The adhesive film for a semiconductor of the present invention is characterized by improving the connection reliability, which has been a problem in the past, and having both high wet heat resistance and adhesive properties.

The semiconductor adhesive film used in the present invention is
It is necessary that the glass transition temperature Tg after curing is 100 ° C. or higher. If the glass transition temperature is less than 100 ° C., the mounting reliability due to flip-chip connection is significantly reduced, which is not preferable. Further, in the present invention, it is preferable that the conditions for sticking to the wafer are a temperature not lower than the glass transition temperature of the adhesive film and not lower than 70 ° C. lower than the temperature at the time of flip chip connection of the semiconductor element. If the pressure-bonding temperature of the adhesive film is less than Tg, the sticking property will deteriorate, and at a temperature of 70 ° C or lower than the temperature at the time of flip-chip connection, the curing of the curing component will proceed, so there will be insufficient fluidity at the time of flip-chip connection and the resin It is not preferable because a filling part is formed. 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 and voids are generated, and the resin wettability at the bonding interface is not sufficient, so the bonding reliability is reduced, and 1MP
This is because if it exceeds a, the pressure may be too strong and the wafer may crack.

When the adhesive film of the present invention is cured,
Storage elastic modulus measured with a dynamic viscoelasticity measuring device is 2 at 25 ° C.
500 to 6000 MPa, 40 at 200 ° C or higher
It must have a high elastic modulus of at least MPa. The storage elastic modulus is measured at a frequency of 10 Hz and a heating rate of 5 ° C / m.
The temperature dependence measurement is performed at -60 to 320 ° C.

If the storage elastic modulus exceeds 6000 MPa at 25 ° C., the effect of alleviating the thermal stress caused by the difference in thermal expansion coefficient between the semiconductor chip and the substrate becomes small, and peeling or cracking may occur. Two
It is not preferable because the elastic modulus of 40 MPa or more cannot be maintained at 00 ° C. or higher, the adhesive strength is significantly reduced at high temperature, and peeling may occur during reflow.

In the semiconductor device of the present invention, the adhesive film for a semiconductor is used to collectively perform thermocompression bonding on the bump electrode surface of the wafer, and then the adhesive-attached semiconductor elements separated by dicing are connected to the substrate by flip chip connection. It can be manufactured by directly bonding the bump electrodes and burying a film adhesive in the gap between the semiconductor element and the substrate.

[0037]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

(A) Thermoplastic polyimide resin (A-1) Silicone-modified polyimide resin: 4,4'-bisphenol as an acid component in a four-neck separable flask equipped with a thermometer, a stirrer, and a raw material inlet. A acid dianhydride 78.08 (0.15 mol) was added to anisole 89.1
The suspension is suspended in 6 g and 79.79 g of toluene. As the diamine component, 1,3-bis (3-aminophenoxy) benzene 35.08 g (0.12 mol) and 1,12
A solution of 6.01 g (0.03 mol) of diaminododecane dissolved in 230 g of anisole by heating at 70 ° C. is placed in a dropping funnel. Next, a Dean-Stark reflux condenser was attached, and heating with an oil bath caused the suspension solution to dissolve and become transparent. When heating under reflux started, the diamine solution was slowly added dropwise for 0.5 hour. At this time, water generated by imidization was removed from the system by azeotropic distillation with toluene.
The reaction was terminated when the mixture was heated under reflux for 1.0 hour after completion of the dropping. Thus, a polyimide resin soluble in anisole was obtained. The molecular weight is Mw = 65,000. (A-2) Silicone-modified polyimide resin: 4,4′-bisphenol A acid dianhydride 78.08 (0) as an acid component in a four-neck separable flask equipped with a thermometer, a stirrer, and a raw material inlet. .15 mol) to anisole 101.
Suspend in 92 g and 82.98 g of toluene. And
As the diamine component, 1,3-bis (3-aminophenoxy) benzene 35.08 g (0.12 mol) and 1,1
4.51 g (0.0225 mol) of 2-diaminododecane
And α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 836) 6.27 g (0.007
5) A solution prepared by heating and dissolving 230 mol of anisole at 70 ° C in a mole is placed in a dropping funnel. Next, a Dean-Stark reflux condenser was attached, and heating with an oil bath caused the suspension solution to dissolve and become transparent. When heating under reflux started, the diamine solution was slowly added dropwise for 0.5 hour. On this occasion,
Water generated by imidization was removed from the system by azeotropic distillation with toluene. The reaction was terminated when the mixture was heated and refluxed for 2.0 hours after completion of the dropping. Thus, a polyimide resin soluble in anisole was obtained. The molecular weight is Mw = 41000. (A-3) Silicone-modified polyimide resin: 4,4′-bisphenol A acid dianhydride 67.67 (0) as an acid component in a four-neck separable flask equipped with a thermometer, a stirrer, and a raw material inlet. .13 mol) to anisole 82.5
Suspend in 1 g and 80.63 g of toluene. And as diamine components, 15.20 g (0.052 mol) of 1,3-bis (3-aminophenoxy) benzene and 2,2
26.68 g (0.065 mol) of -bis (4- (4-aminophenoxy) phenyl) propane and α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 836) 10.87 g (0.0013) ) A mol obtained by heating and dissolving 230 mol of anisole at 70 ° C. is placed in a dropping funnel. Next, a Dean-Stark reflux condenser was attached, and heating with an oil bath caused the suspension solution to dissolve and become transparent. When heating under reflux started, the diamine solution was slowly added dropwise for 0.5 hour. At this time, water generated by imidization was removed from the system by azeotropic distillation with toluene. The reaction was terminated when the mixture was heated under reflux for 2.0 hours after completion of the dropping. Thus, a polyimide resin soluble in anisole was obtained. The molecular weight is Mw = 51000. (A-4) Silicone-modified polyimide resin: In a four-necked separable flask equipped with a thermometer, a stirrer, and a raw material charging port, 18.61 g (0. 06 mol), 3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride 17.65
(0.06 mol) is suspended in 133.23 g of anisole and 74.36 g of toluene. Then, as the diamine component, 24.63 g (0.06 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane and α,
ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 836) 50.16 g (0.06 mol)
What was heated and dissolved in 164.2 g of anisole at 70 ° C. was put in a dropping funnel. Next, a Dean-Stark reflux condenser was attached, and heating with an oil bath caused the suspension solution to dissolve and become transparent. When heating under reflux started, the diamine solution was slowly added dropwise for 1 hour. At this time, water generated by 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 completion of the dropping. Thus, a polyimide resin soluble in anisole was obtained. The molecular weight is Mw = 65,000. (A-5) Silicone-modified polyimide resin: 4,4'-oxydiphthalic acid dianhydride 43.43 g (0.40) as an acid component in a four-neck separable flask equipped with a thermometer, a stirrer, and a raw material inlet. 14 mol), and anisole 19
Suspend in 1.43 g and 81.96 g of toluene. As diamine components, 20.46 g (0.07 mol) of 1,3-bis (3-aminophenoxy) benzene and α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 836) 58.52 g What melt | dissolved (0.07 mol) in 130.42 g of anisole by heating at 70 degreeC is put into the dropping funnel. Next, a Dean-Stark reflux condenser was attached, and heating with an oil bath caused the suspension solution to dissolve and become transparent. When heating under reflux started, the diamine solution was slowly added dropwise for 1 hour. At this time, water generated by 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 completion of the dropping. Thus, a polyimide resin soluble in anisole was obtained. The molecular weight is Mw = 76000.

The above-mentioned thermoplastic polyimide resin (A-1)
Table 1 shows general physical properties of (A-5) to (A-5).

(B) Thermosetting resin (B-1) Cresol novolac type epoxy resin (epoxy equivalent 200, manufactured by Nippon Kayaku Co., Ltd., trade name EOCN-
1020-80) (B-2) Cresol novolac type epoxy resin (epoxy equivalent 210, product name EOCN- manufactured by Nippon Kayaku Co., Ltd.)
104S-90) (B-3) High-purity bis-F epoxy resin (epoxy equivalent 175, trade name RE403S manufactured by Nippon Kayaku Co., Ltd.) (B-4) Novolac cyanate ester resin (trade name PRIMASET PT manufactured by Lonza Japan Co., Ltd.) −
30) (B-5) Bis-F type cyanate ester resin (trade name AROCY L-10 manufactured by Asahi Kasei Epoxy Co., Ltd.) (B-6) isocyanuric acid derivative (trade name DA-MGIC manufactured by Shikoku Chemicals Co., Ltd.)

(Curing Accelerator) (C-1) 1-Cyanoethyl-2-phenylimidazole (trade name 2PZ-CN manufactured by Shikoku Chemicals Co., Ltd.) (C-2) 1-benzyl-2-phenylimidazole (Shikoku Chemicals Kogyo Co., Ltd., trade name 1B2PZ) (C-3) Cobalt acetylacetonate (Nippon Kagaku Sangyo Co., Ltd., trade name Nasem Daini Cobalt)

(Coupling agent) (D-1) N-phenyl-γ-aminopropyltrimethoxysilane (trade name KBM- manufactured by Shin-Etsu Silicone Co., Ltd.)
573) (D-2) 3-glycidoxypropyltrimethoxysilane (KBM-403E manufactured by Shin-Etsu Silicone Co., Ltd.)

Example 1 In the proportions shown in Table 2, (1) a thermosetting resin was added to a thermoplastic polyimide resin solution dissolved in an organic solvent used at the time of synthesis and mixed by stirring, and subsequently a coupling agent was stirred. After mixing and finally adding a curing accelerator, the mixture was deaerated under vacuum. (2) This resin varnish was applied on a polyethylene terephthalate supporting substrate having a thickness of 38 μm by a roll coater so that the film thickness after drying would be 40 m, and the mixture was heated at 60 ° C. for 2 minutes for 80 minutes.
It was heated and dried in a hot air circulation dryer at 2 ° C. for 2 minutes and 90 ° C. for 2 minutes to obtain an adhesive film for a semiconductor with a release film. Further, the cured film after heat treatment at 180 ° C. for 2 hours was measured for glass transition temperature with a thermomechanical analyzer and storage elastic modulus with a dynamic viscoelasticity apparatus. Table 2 shows the measurement results
It was shown to. (3) The adhesive film with release film after drying was cut into pieces larger than the wafer size, and the adhesive resin of the film was placed on the bumps of the wafer with gold bump electrodes and heat-pressed to obtain a wafer with adhesive film. After that, the appearance test of the adhered film was performed. (4) The adhesive surface of the wafer with an adhesive film was attached to a dicing sheet and cut and separated by a dicing device to obtain individual semiconductor elements with an adhesive film. Next, the chipping characteristics and the adhesive strength of the obtained semiconductor element with an adhesive film were measured.

[Appearance test] The adhesive film for a semiconductor with a release film was cut into a size larger than the wafer size, and the adhesive resin of the film was placed on the gold bump electrodes of the wafer.
A wafer with an adhesive resin is obtained by thermocompression bonding at a temperature of 150 ° C., a pressure of 0.25 MPa, and a pressing time of 10 seconds. At this time, an external appearance test was conducted by visually observing voids and foaming in the film on the wafer and observing the resin embedding property around the bumps and the penetration of the bumps with a stereoscopic microscope. After laminating an adhesive film on a 5-inch wafer, when there are 5 or more bubbles or 3 cm or more streaks on the wafer, or when there are voids around the bumps or the bumps are not exposed on the surface, X, so When it was not, it was judged as ○.

[Chipping Characteristics] Dicing Saw (DISC
O made DAD-2H6M) spindle speed 3,00
Twenty individual semiconductor elements with an adhesive film, which were cut and separated at 0 rpm and a cutting speed of 20 / sec, were randomly selected, and chipping and cracks were observed with a stereoscopic microscope. Judgment was made when the number of chipped chips or cracks was 2 or less, and when 3 or more. (Chip width is 30
Those having a size of μm or less were accepted. )

[Adhesive strength when heated at 240 ° C.] The film was punched with a 7 × 7 mm die, and the pressure was 160 ° C. and the pressure was 2M.
Temporarily pressure-bonding is performed at Pa for a pressure time of 0.3 seconds, and then the film is attached to a 42-alloy lead frame at a pressure-bonding temperature of 160 ° C., a pressure of 1 MPa, and a pressure time of 1.0 second. Then 4
A silicon chip of mm square is attached to the above 7 × 7 mm film by a pressure bonding temperature of 250 ° C., a pressure of 1 MPa, and a pressure bonding time of 1.0.
Chip mount in seconds and cure at 180 ° C. for 2 hours.
After curing, the die shear strength under heat was measured at 240 ° C. for 20 seconds using a push-pull gauge.

[Flip chip connectivity: void / void]
Adhesive film on gold bump electrode wafer at 150 ℃, 10
Laminate in seconds, then dice 10 × 10
A semiconductor element with an adhesive resin of mm was obtained. A mounting test of this semiconductor element was performed on a polyimide double-layer tape substrate by a flip chip bonder device (DB200 manufactured by Shibuya Kogyo). After pressure bonding for 30 seconds at 275 ° C using the pulse heater method,
The presence or absence of voids and voids was observed from the back of the substrate, and further confirmed by observing the cross section. When there were voids / voids in the center of the chip, x was judged, and with respect to other voids / voids at the chip end, 1 mm or more was marked as x, and the others were judged as o.

[Flip Chip Connectivity: Continuity Test] The flip chip package prepared for the void / void test was cured by heat treatment at 180 ° C. for 2 hours, and then the package was subjected to room temperature (25 ° C.), 150 ° C., 260 ° C. These were placed on a hot plate and repeated 3 times. If even one conduction failure occurred, x was judged, and if 3 conductions were made, it was judged as o.

Examples 2 to 6 The mixing ratio of each component was changed as shown in Table 2. Except for this, the same operation as in Example 1 was performed.

Comparative Examples 1 and 2 The blending ratio of each component was changed as shown in Table 2. Other than this, the same operation as in Example 1 was performed.

The evaluation results of the adhesive film are shown in Table 2.

The results of the flip chip connectivity test are shown in Table 3.

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

EFFECTS OF THE INVENTION The adhesive film of the present invention can be thermocompression-bonded to the bump side of a wafer with bump electrodes and can expose the bump electrode portion on the surface, and has good dicing property. When the bump electrode and the circuit board are flip-chip connected using this semiconductor element with an adhesive film, the adhesive resin flows without voids or voids and can be filled between the semiconductor element and the substrate. Further, the adhesive film of the present invention is excellent in strong adhesiveness and high resistance to moisture and heat, and a flip chip package using the same relaxes thermal stress generated during heating and cooling, and has a high elastic modulus so that it has reflow resistance and resistance to heat. Excellent temperature cycle property. As described above, the present invention can provide an optimum adhesive film for a flip chip package.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J004 AA11 AA12 AA13 AA14 AA15                       AA17 AB06 BA02 FA05 FA08                 4J040 EB031 EB032 EB131 EB132                       EC001 EC002 EC061 EC062                       EC071 EC072 ED111 ED112                       EF001 EF002 EH031 EH032                       EK031 EK032 JA09 JB02                       LA02 MB03 NA19 NA20                 5F044 KK03 LL11 LL15

Claims (7)

[Claims] 1. A glass transition temperature after curing by heat treatment is 100 ° C. or higher and a storage elastic modulus is 25 ° C.
An adhesive film for a semiconductor, which has a pressure of 6000 MPa and a pressure of 40 MPa or higher at 200 ° C. or higher. 2. A thermoplastic polyimide resin (A) which is soluble in an organic solvent and has a glass transition temperature of 100 ° C. or higher, and (B) a thermosetting resin, and (B) is contained in all components. The adhesive film for semiconductors according to claim 1, which is 20 to 70% by weight. 3. The adhesive for semiconductors according to claim 2, wherein the thermoplastic polyimide resin of the component (A) contains 4,4′-bisphenol A carboxylic acid dianhydride represented by the formula (1) as an acid component. the film. [Chemical 1] 4. The thermoplastic polyimide resin as the component (A) is soluble in the phenyl ether represented by the general formula (2) or is polymerizable using phenyl ether as a reaction solvent. Alternatively, the adhesive film for semiconductor according to the item 3. [Chemical 2] (In the formula, R7 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R8 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 semiconductor adhesive film according to claim 1 on a bump side of a semiconductor wafer with bump electrodes and simultaneously exposing the bump electrode portions on the surface. A semiconductor device characterized in that it is cut and separated into individual semiconductor elements by means of, and the bump electrodes are directly joined to a circuit board or the like by flip-chip connection via an adhesive film of the semiconductor elements. 7. A bump electrode for a semiconductor wafer, comprising the adhesive film for a semiconductor according to claim 1 at a temperature not lower than the glass transition temperature of the film and not lower than 70 ° C. lower than the temperature at the time of flip chip connection of a semiconductor element. A method for manufacturing a semiconductor device, which comprises performing thermocompression bonding to the side and then dicing.