JP2002158239A - Die bonding material and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a die bonding material having good adhesion when heated as an adhesive material of a support member of an electronic component such as a semiconductor element or the like, a lead frame, an insulating support board or the like, and excellent reliability durable against a high-temperature soldering heat history at mounting time and excellent low stress properties and low temperature adhesion properties. SOLUTION: The film-like die bonding material for adhering the semiconductor element to the support member comprises an elastic modulus at 250 deg.C or higher at a stage before adhering of less than 0.1 MPa, and elastic modulus at 250 deg.C after thermally curing of 0.5 to 20 MPa.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive material for an electronic component such as a semiconductor element and a supporting member such as a lead frame or an insulating support substrate, that is, a film-like die bonding material and a film-like die bonding material suitable for die bonding. The present invention relates to a semiconductor device using a die bonding material.

[0002]

2. Description of the Related Art Au-Si eutectic alloys, solders, silver pastes, adhesive films, and the like have been known as adhesive materials between electronic components such as semiconductor elements and supporting members such as lead frames and insulating supporting substrates. ing. Among these, the Au-Si eutectic alloy has the problem of being expensive and having a high elastic modulus, and the solder cannot withstand temperatures above its melting point, and has the problem of having a high elastic modulus. A silver paste or an adhesive film having a low elastic modulus is mainly used. The silver paste is mainly composed mainly of a thermosetting resin from the viewpoint of heat resistance, and the adhesive film is mainly composed of a thermoplastic resin as a main component from the viewpoint of film formability.

[0003]

The demand for high-density packaging due to the miniaturization and thinning of electronic equipment has been rapidly increasing.
2. Description of the Related Art Semiconductor devices (semiconductor packages) have become the mainstream of surface mounting types suitable for high-density mounting instead of conventional pin insertion types. This surface mount package is used to solder leads or bumps directly to a printed circuit board, etc.
The entire package is heated and mounted by infrared reflow, vapor phase reflow, solder dip, or the like. At this time, since the entire package is exposed to a high temperature of about 240 ° C., if moisture is absorbed inside the package, explosive vaporization of the moisture causes a package crack (hereinafter referred to as a reflow crack). The reflow crack significantly reduces the reliability of the semiconductor package, and is a serious problem and technical problem.

[0004] The mechanism of occurrence of reflow cracks due to the die bonding material is as follows. While the semiconductor package is stored, (1) the die bonding material absorbs moisture, (2) the absorbed moisture is vaporized by heating at the time of reflow soldering, and (3) the vapor pressure destroys the die bonding layer. Peeling occurs and (4) reflow cracks occur. While the reflow crack resistance of the sealing member has been improved, the reflow crack caused by the die bonding material has become a serious problem, especially in a thin package.

Further, in recent years, with the environmental protection measures on a global scale, legal regulations on lead have been increasingly strengthened mainly in Europe and the like, and accordingly, lead-free mounting solder has been required. It is said that in fields where high reliability is demanded, the current Sn-Pb system will be replaced by Sn-Ag system solder with a higher melting point. When the mounting solder is switched to the above-mentioned Sn-Ag system, the melting point becomes higher, so that the maximum temperature of the reflow furnace becomes higher by 20 ° C. to 30 ° C. than the current temperature. Therefore,
As an adhesive material for die bonding, a material that can withstand an increase in reflow temperature and has improved reliability more than ever has been required.

[0006] With the silver paste used most commonly in the past, it has become difficult to apply the silver paste uniformly over the entire coating area due to the enlargement of the chip.
Since it is a paste, voids are easily generated in the adhesive layer, and reflow cracks are easily generated.

[0007] In order to solve the above problem, an adhesive film in which a silver paste is formed into a film has been proposed. By forming a film, a uniform bonding area can be secured and voids can be greatly reduced, so that better reflow crack resistance than a paste can be secured.

On the other hand, a copper lead frame (which is easily oxidized by heat) and an insulating supporting substrate (having a low thermal conductivity), which have begun to be used in recent years, have a large thermal expansion coefficient.
When the adhesive film is easily warped at the time of heat bonding and is used for bonding to such a support substrate, a material which can be bonded at low stress and at low temperature is strongly desired.

[0009] Adhesive films are mainly composed of a thermoplastic resin as a main component. If a thermoplastic resin having a low melting point is selected and used, the adhesive temperature can be lowered and the chip can be oxidized to a lead frame. The damage done can be reduced. However, a resin film using a thermoplastic resin having a low melting point has a low adhesive strength when heated, and thus cannot withstand heat treatment (wire bonding step, mounting step, etc.) after die bonding.

An object of the present invention is to provide a film-shaped die bonding material for bonding an electronic component such as a semiconductor element to a lead frame or an insulating support substrate, which can withstand high-temperature soldering heat history during mounting, and Another object of the present invention is to provide a die bonding material having low stress and low temperature adhesiveness which can be suitably used for a copper lead frame or an insulating support substrate.

In order to obtain a die bonding material having low stress, low temperature adhesiveness, and high reliability in high temperature soldering heat history during mounting, control of physical properties during heat is important. It is. The present inventors have completed the present invention as a result of intensive studies on the physical properties and characteristics of the film-shaped die bonding material and the relationship between the low stress property, the low-temperature adhesive property, and the reflow crack resistance in the high-temperature soldering heat history during mounting.

[0012]

That is, the present invention relates to a film-shaped die bonding material for bonding a semiconductor element to a supporting member, wherein the die bonding material has a temperature of 250 ° C. or more before bonding. And a modulus of elasticity at 250 ° C. after heat curing of 0.5 to 20 MPa.

The present invention further provides a semiconductor device including at least a semiconductor element and a support member, wherein the semiconductor element and the support member are bonded by the die bonding material according to any one of claims 1 to 7. Provide equipment.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the die bonding material of the present invention, the reflow temperature of a surface mount type semiconductor device is 24
It is about 0 to 270 ° C., and since the bonding temperature at the time of die bonding is desirably 250 ° C. or less, the elastic modulus at 250 ° C. or more before bonding is less than 0.1 MPa,
The elastic modulus at 250 ° C after heat curing is 0.5 to 20MP
It is necessary to achieve a low temperature adhesiveness, low stress and reflow resistance at the same time and at a high level.
-10 Mpa is preferred. If the elastic modulus at 250 ° C. or higher before bonding is 0.1 Mpa or higher, the bonding temperature is 250 ° C.
There is a problem that it becomes higher or the bonding load becomes larger. Further, if the elastic modulus at 250 ° C. after the heat curing is less than 0.5 MPa, the adhesive strength at the time of heating is weak, and
If it exceeds pa, the stress will increase and the adhesive strength during heating will be weak.

The die bonding material has a Tg of 200 ° C.
It preferably contains the following thermoplastic resin and thermosetting resin, and more preferably contains a silane coupling agent.

The thermoplastic resin contained in the film-shaped die bonding material of the present invention is not limited as long as the Tg is 200 ° C. or lower. For example, a polyimide resin, a polyamide resin, a polyetherimide resin, a polyester resin, Examples thereof include a polyesterimide resin, a phenoxy resin, a polysulfone resin, a polyethersulfone resin, a polyphenylene sulfide resin, and a polyetherketone resin, and a phenoxy resin or a polyimide resin is preferable.
When the Tg of the thermoplastic resin exceeds 200 ° C., the temperature required for bonding the die bonding material increases.

The phenoxy resins that can be used are equivalent to high molecular weight epoxy resins having an average molecular weight of 5,000 or more determined by high performance liquid chromatography (HLC), and like the epoxy resins, bisphenol A type, F type and AD type , AF copolymer type and S type. The higher the molecular weight, the easier the film formability can be obtained. The average molecular weight is 5,
000 to 150,000, and about 10,000 to 80,000 is more preferable in terms of melt viscosity, compatibility with other resins, and the like.

The polyimide resin that can be used can usually be produced by reacting tetracarboxylic dianhydride with diamine. As the tetracarboxylic dianhydride that can be used,
The following are exemplified. Pyromellitic dianhydride,
3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) Propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3 2,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxy) Phenyl) sulfone dianhydride,

3,4,9,10-Perylenetetracarboxylic dianhydride bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride 3 , 4,3 ', 4'-Benzophenonetetracarboxylic dianhydride, 2,3,2', 3-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalene-tetracarboxylic dianhydride 1,4,5,8-naphthalene-tetracarboxylic dianhydride,

2,6-Dichloronaphthalene-1,4,5,8-
Tetracarboxylic dianhydride, 2,7-dichloronaphthalene
-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7
-Tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, funanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid Dianhydride, thiophenin-2,3,4,5-tetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,4,3', 4'-biphenyl Tetracarboxylic dianhydride, 2,3,2 ', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) ) Methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride 1,3-bis ( 3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisc Rohexane dianhydride, p-phenylene bis (trimellitate anhydride),

Ethylenetetracarboxylic dianhydride, 1,
2,3,4-butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7 -Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride,
Cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride , Bis (exobicyclo [2,2,1] heptane-2,
3-dicarboxylic dianhydride) sulfone, bicyclo- (2,
2,2) -oct (7) -ene 2,3,5-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4
-(3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride,
1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic dianhydride), 1,3-
Bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic dianhydride), 5- (2,5-dioxotetrahydrofuryl) -3-cyclohexene-1,2
-Dicarboxylic dianhydride, tetrahydrofuran-2,3,
In addition to 4,5-tetracarboxylic dianhydride,

The following formula (I)

Embedded image (Where n is an integer of 2 to 20), a tetracarboxylic dianhydride represented by the following formula (II):

Embedded image There is a tetracarboxylic dianhydride represented by
More than one species may be used in combination. Particularly preferred tetracarboxylic dianhydrides are the acid dianhydrides of formula (I) above and the acid dianhydrides of formula (II) above. Formulas (I) and (I
More preferably, the content of at least one of the tetracarboxylic dianhydrides of I) is at least 30 mol% of the total tetracarboxylic dianhydride.

As the tetracarboxylic dianhydride of the formula (I), when n is 2 to 5, 1,2- (ethylene) bis (trimellitate dianhydride), 1,3- (trimethylene)
Bis (trimellitate dianhydride), 1,4- (tetramethylene) bis (trimellitate dianhydride), 1,5- (pentamethylene) bis (trimellitate dianhydride), n is 6
-20, 1,6- (hexamethylene) bis (trimellitate dianhydride), 1,7- (heptamethylene) bis (trimellitate dianhydride), 1,8- (octamethylene) bis (trimellitate dianhydride) ), 1,9- (nonamethylene) bis (trimellitate dianhydride), 1,10-
(Decamethylene) bis (trimellitate dianhydride),
1,12- (dodecamethylene) bis (trimellitate dianhydride), 1,16- (hexadecamethylene) bistrimellitate dianhydride, 1,18- (octadecamethylene) bis (trimellitate dianhydride), etc. Yes, two or more of these may be used in combination.

The tetracarboxylic dianhydride of the above formula (I) can be synthesized from trimellitic anhydride monochloride and the corresponding diol. Further, the amount of the tetracarboxylic dianhydride contained in the total tetracarboxylic dianhydride is preferably 30 mol% or more,
This is to maintain the low-temperature adhesiveness of the adhesive film.

The reason why the amount of the tetracarboxylic dianhydride of the formula (II) is preferably at least 30 mol% with respect to all the tetracarboxylic dianhydrides is to maintain the moisture resistance reliability of the adhesive film. is there.

Diamines, one of the other raw materials of the polyimide resin, include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6 Aliphatic diamines such as -diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane,

O-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether,
4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoro Methane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-
Diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide,

3,3'-diaminodiphenyl ketone,
4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 '-(3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane,
2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3 -Bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy)
Benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-(1-phenylenebis (1-methylethyleridene)) bisaniline, 3,4'-(1,4-phenylenebis (1- Methylethylidene)) bisaniline, 4,
4 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4-
(4-aminophenoxy) phenyl) propane, 2,2
-Bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4-
(3-aminophenoxy) phenyl) sulfide, bis (4- (4-aminophenoxy) phenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) In addition to aromatic diamines such as sulfone,

The following formula (III)

Embedded image (Wherein Q ₁ and Q ₂ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group, and Q ₃ , Q ₄ , Q ₅ and
Q ₆ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and m represents an integer of 1 to 50. )), And two or more of these may be used in combination.

When m is 1, 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane;
1,1,3,3-tetraphenoxy-1,3-bis (4
-Aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3 -Aminopropyl) disiloxane, 1,1,3,
3-tetramethyl-1,3-bis (2-aminoethyl)
Disiloxane, 1,1,3,3-tetramethyl-1,3
-Bis (3-aminopropyl) disiloxane, 1,1,
3,3-tetramethyl-1,3-bis (3-aminobutyl) disiloxane, 1,3-dimethyl-1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane and the like,

When m is 2, 1,1,3,3,5,5-
Hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3,
3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3,
3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,
3-dimethoxy-1,5-bis (5-aminopentyl)
Trisiloxane, 1,1,5,5-tetramethyl-3,
3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3
-Dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-
Dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-
1,5-bis (3-aminopropyl) trisiloxane,
1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3
3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane and the like,

Further, when m is 3 to 50, the following formula (III)
-A), the following formula (III-b), the following formula (III-c), and the like.

Embedded image

Embedded image

Embedded image Two or more of these siloxane-based diamines may be used in combination. Preferred siloxane diamines are the siloxane diamines of formula (III). The diamine is a siloxane-based diamine of the formula (III) in an amount of 3 mol% based on the total diamine.
More preferably, it is included. More preferred formula (II
The content of the siloxane-based diamine of I) is 5 mol% or more,
More preferably, it is at least 10 mol%. If the amount is less than 3 mol%, low stress, low temperature adhesiveness and low hygroscopic properties cannot be exhibited.

The condensation reaction between the tetracarboxylic dianhydride and the diamine is carried out in an organic solvent. In this case, the tetracarboxylic dianhydride and the diamine are preferably used in equimolar or almost equimolar, and the order of addition of each component is arbitrary. Examples of the organic solvent used include dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphorylamide, m-cresol, o-chlorophenol and the like.

The condensation reaction temperature is preferably 80 ° C. or lower, more preferably 0 to 50 ° C. As the reaction proceeds, the viscosity of the reaction solution gradually increases. In this case, polyamic acid, which is a precursor of polyimide, is generated.

The polyimide can be obtained by subjecting the above reactant (polyamic acid) to dehydration and ring closure. Dehydration ring closure is 1
The heat treatment can be performed at 20 ° C. to 250 ° C. or a chemical method. In the case of a method of performing heat treatment at 120 ° C. to 250 ° C., the heat treatment is preferably performed while removing water generated in the dehydration reaction outside the system. At this time, water may be azeotropically removed using benzene, toluene, xylene, or the like. In the present invention, the polyimide resin is a general term for polyimide and its precursor. Polyimide precursors include, in addition to polyamic acid, polyamic acid partially imidized.

In the case of ring closure by dehydration by a chemical method, acetic anhydride, propionic anhydride, acid anhydride of benzoic anhydride, carbodiimide compounds such as dicyclohexylcarbodiimide and the like are used as a ring closing agent. At this time, if necessary, a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole and the like may be used. The ring-closing agent or the ring-closing catalyst is preferably used in an amount of 1 to 8 mol per 1 mol of tetracarboxylic dianhydride.

The thermosetting resin contained in the film-shaped die bonding material of the present invention is a reactive compound which causes a crosslinking reaction by heat. Such compounds include epoxy resin, cyanate resin, bismaleimide resin, phenol resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, resorcinol formaldehyde resin, xylene resin , Furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, resin containing tris (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, thermosetting from cyclopentadiene Resin, thermosetting resin by trimerization of aromatic dicyanamide, and the like. Note that two or more kinds of these thermosetting resins may be used.

For curing, a curing agent and a curing accelerator (catalyst) can be appropriately used. For example, when an epoxy resin is used, the curing agent may be a phenolic compound, an aliphatic amine, an alicyclic amine, an aromatic polyamine, a polyamide, an aliphatic acid anhydride, an alicyclic acid anhydride, or an aromatic acid. Anhydride, dicyandiamide, organic acid dihydrazide, boron trifluoride amine complex, imidazoles, tertiary
Secondary amine and the like. The curing accelerator (catalyst) is not particularly limited as long as it cures the thermosetting resin. When using a cyanate resin, cobalt,
A metal salt such as zinc or copper or a metal complex can be used as a catalyst, and a phenolic compound such as an alkylphenol, a bisphenol compound, or phenol novolak can be used as a cocatalyst.

The epoxy resin contains at least two epoxy groups in the molecule, and is preferably a phenol glycidyl ether type epoxy resin from the viewpoint of curability and cured product properties. Such resins include bisphenol A
Glycidyl ether, bisphenol AD glycidyl ether, bisphenol S glycidyl ether, bisphenol F glycidyl ether, water-added bisphenol A glycidyl ether, ethylene oxide adduct bisphenol A glycidyl ether, propylene oxide adduct bisphenol A type glycidyl ether, glycidyl ether of phenol novolak resin, glycidyl ether of cresol novolak resin, glycidyl ether of bisphenol A novolak resin, glycidyl ether of naphthalene resin, 3
Functional glycidyl ether, tetrafunctional glycidyl ether, glycidyl ether of dicyclopentadienephenol resin, glycidyl ester of dimer acid, trifunctional glycidylamine, tetrafunctional glycidylamine, glycidylamine of naphthalene resin, etc. No. Two or more of these may be used.

The epoxy resin curing agent is not particularly limited. For example, the phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines,
Polyamide, aliphatic acid anhydride, alicyclic acid anhydride, aromatic acid anhydride, dicyandiamide, organic acid dihydrazide, boron trifluoride amine complex, imidazoles, tertiary amine, etc. Phenolic compounds having at least two phenolic hydroxyl groups are preferred.
Such materials include phenol novolak resins,
Cresol novolak resin, t-butylphenol novolak resin, dicyclopentadienecresol novolak resin, dicyclopentadienephenol novolak resin, xylylene-modified phenol novolak resin, naphthol novolak resin, trisphenol novolak resin, tetrakisphenol novolak resin, bisphenol A novolak resin , Poly-p-vinylphenol resin, phenol aralkyl resin and the like.

As the cyanate resin, for example, 2,2'-bis (4-cyanatephenyl) isopropylidene 1,1'-bis (4-cyanatephenyl) ethanebis (4-cyanate-3,5-dimethylphenyl) Methane 1,3-bis (4-cyanatephenyl-1- (1-methylethylidene)) benzene cyanated phenol-dicyclopentanedienene adduct cyanated novolak bis (4-cyanatophenyl) thioether bis (4-shear (Natophenyl) ether resorcinol dicyanate 1,1,1-tris (4-cyanatephenyl) ethane 2-phenyl-2- (4-cyanatephenyl) isopropylidene and the like, and two or more of these may be used.

Examples of the compound having a bismaleimide group (bismaleimide resin) include ortho-bismaleimide benzene, metabismaleimide benzene, para-bismaleimide benzene, 1,4-bis (p-maleimidocumyl) benzene, 1,4- In addition to bis (m-maleimidocumyl) benzene, there are imide compounds represented by the following formulas (IV) to (VII).

Embedded image(Wherein X is O, CH_Two, CF_Two, SO_Two, S, CO, C
(CH_Three)_TwoOr C (CF _Three)_TwoAnd R₁, R_Two, R_ThreePassing
And R_FourAre independently hydrogen, a lower alkyl group, a lower
Represents a alkoxy group, fluorine, chlorine or bromine, and D is ethyl
Indicates a dicarboxylic acid residue having an unsaturated double bond
You. )

Embedded image (Where Y is O, CH ₂ , CF ₂ , SO ₂ , S, CO, C
(CH ₃ ) ₂ or C (CF ₃ ) ₂ , wherein R ₅ , R ₆ , R ₇ and R ₈ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine; A dicarboxylic acid residue having an ethylenically unsaturated double bond is shown. )

Embedded image (In the formula, q represents an integer of 0 to 4, and D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond.)

Embedded image (Wherein R ₁₀ and R ₁₁ are each a divalent hydrocarbon group, R
₁₂ , R ₁₃ , R ₁₄ and R ₁₅ each represent a monovalent hydrocarbon group, D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond, and 1 represents an integer of 1 or more. )

Examples of the imide compound of the formula (IV) include 4,4-bismaleimide diphenyl ether,
4-bismaleimidediphenylmethane, 4,4-bismaleimide-3,3′-dimethyl-diphenylmethane,
4,4-bismaleimidodiphenyl sulfone, 4,4-
Bismaleimide diphenyl sulfide, 4,4-bismaleimide diphenyl ketone, 2,2′-bis (4-maleimidophenyl) propane, 3,4-bismaleimide diphenylfluoromethane, 1,1,1,3,3,3- Hexafluoro-2,2-bis (4-maleimidophenyl) propane and the like.

Examples of the imide compound of the formula (V) include bis (4- (4-maleimidophenoxy) phenyl) ether, bis (4- (4-maleimidophenoxy) phenyl) methane and bis (4- (4- Maleimidophenoxy) phenyl) fluoromethane, bis (4- (4
-Maleimidophenoxy) phenyl) sulfone, bis (4- (3-maleimidophenoxy) phenyl) sulfone, bis (4- (4-maleimidophenoxy) phenyl) sulfide, bis (4- (4-maleimidophenoxy) phenyl) ketone, 1,2-bis (4- (4-maleimidophenoxy) phenyl) propane, 1,1,1,
3,3,3-hexafluoro-2,2-bis (4- (4
-Maleimidophenoxy) phenyl) propane and the like.

In order to accelerate the curing of these imide compounds, a radical polymerization agent may be used. Examples of the radical polymerization agent include acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, benzoyl peroxide, octanoyl peroxide, acetyl peroxide, dicumyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, and the like. At this time, the amount of the radical polymerization agent used is preferably about 0.01 to 1.0 part by weight based on 100 parts by weight of the bismaleimide resin.

The content of the thermosetting resin contained in the film die bonding material of the present invention is preferably 0.1 to 200 parts by weight, more preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the thermoplastic resin. Parts by weight. If it exceeds 200 parts by weight, the film-forming properties will be poor.

Further, the adhesive composition of the present invention may contain a silane coupling agent. Examples of the silane coupling agent contained in the film die bonding material of the present invention include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and N- (2-aminoethyl) 3-amino. Propylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycol Sidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysila , 3-ureidopropyltriethoxysilane, N-
(1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N, N'-bis (3-
(Trimethoxysilyl) propyl) ethylenediamine,
There are polyoxyethylene propyl trialkoxysilane, polyethoxydimethylsiloxane and the like, and two or more of these may be used.

The content of the above coupling agent is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin. If it exceeds 50 parts by weight, the storage stability will be poor.

The die bonding material of the present invention may contain a filler as long as the adhesion is not impaired. Examples of such fillers include metal fillers such as silver powder, gold powder, and copper powder, inorganic fillers such as silica, alumina, boron nitride, titania, glass, iron oxide, and ceramics, carbon,
There are rubber-based organic fillers and the like. Among the fillers, the metal filler is added for the purpose of imparting conductivity or thixotropy to the die bonding material, and the inorganic filler is added for the purpose of imparting a low thermal expansion property and low moisture absorption to the die bonding material. The filler is added for the purpose of imparting toughness to the die bonding material. These metal fillers, inorganic fillers, and organic fillers may be used in combination of two or more. Mixing and kneading in the case of using a filler can be performed by appropriately combining ordinary dispersers such as a stirrer, a grinder, a three-roll mill, and a ball mill.

When a filler is contained, the amount of the filler is 0 to 8000 parts by weight, preferably 0 to 4000 parts by weight, based on 100 parts by weight of the thermoplastic resin. 8000
If the amount is more than 10 parts by weight, the adhesiveness decreases.

The die bonding material of the present invention comprises a thermoplastic resin, a thermosetting resin, and preferably a coupling agent and / or a filler mixed in an organic solvent to form a varnish. Form a layer, heat dry,
It is obtained in the form of a film by removing the substrate.

The organic solvent used in the production of the film-shaped die bonding material is not limited as long as it can uniformly dissolve, knead or disperse the thermoplastic resin or the like. Examples thereof include dimethylformamide and dimethylacetamide. , N-methylpyrrolidone, dimethylsulfoxide,
Examples thereof include diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, and ethyl acetate.

Heat drying is carried out under conditions in which the solvent used is sufficiently volatilized, more specifically under conditions in which the weight loss rate (residual volatile matter) before and after heating at 200 ° C. for 2 hours is 2% by weight or less, that is, approximately 60 ° C. 0.1 to 90 in the range of
Heat for a minute. Thereafter, the film-shaped die bonding material is peeled off from the substrate at room temperature and used, or
It can be used with the substrate.

The substrate is not particularly limited as long as it can withstand the heating and drying conditions in the production of the above film die bonding material. For example, there are a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyethernaphthalate film, a methylpentene film, and the like. Two or more of these films may be combined to form a multilayer film. These films may be treated with a silicone-based or silica-based release agent.

The semiconductor device of the present invention can be obtained by using the obtained film die bonding material for bonding a semiconductor element such as an IC or LSI and a supporting member. For example, the die bonding material of the present invention is sandwiched between the above-described semiconductor element and the supporting member, and the two are bonded by heating and pressing. Thermocompression bonding is usually performed at 100 to 300 ° C and 0.1 to
It is preferably 0.005 to 2 MPa for 300 seconds. Thereafter, a semiconductor device is obtained through a wire bonding step and, if necessary, a step of sealing the semiconductor element with a sealing material. As a supporting member, a 42-alloy lead frame, a lead frame such as a copper lead frame, a polyimide resin, a plastic film such as an epoxy resin, a substrate such as a glass nonwoven fabric, which is impregnated and cured with a plastic such as a polyimide resin or an epoxy resin, Ceramics such as alumina may be used.

[0056]

The present invention will be described below with reference to examples and comparative examples. (Examples 1 to 4, Comparative Examples 1 to 3) Varnishes of No. 1 to No. 7 (No. 1 to 4: Nos. 5 to 7 relating to Examples 1 to 4 of the invention and Comparative Examples 1 to 3). Polyimide A: 1,10- (decamethylene) bis (trimellitate dianhydride): 100 mol% and 2,2-bis (4- (4-aminophenoxy) phenyl) propane: 50 mol% and the following formula (VIII) The diamine represented was synthesized from 50 mol%.

Embedded image Polyimide B: bisphenol A bistrimellitate dianhydride: 100 mol% and 2,2-bis (4- (4-aminophenoxy) phenyl) propane: 20 mol% and the following formula (III-
The diamine represented by a): 80 mol%.

Embedded image Polyimide C: Synthesized from 100 mol% of 1,10- (decamethylene) bis (trimellitate dianhydride) and 100 mol% of 2,2-bis (4- (4-aminophenoxy) phenyl) propane. Polyimide D: Synthesized from 100 mol% of 1,2- (ethylene) bis (trimellitate dianhydride) and 100 mol% of 4,4′-diaminodiphenylmethane.

In Tables 1 and 2, various symbols mean the following. ESCN195: Sumitomo Chemical, cresol novolak type epoxy resin (epoxy equivalent 200) YH-434L: Toto Kasei, 4-functional glycidylamine type epoxy resin (epoxy equivalent 116) BEO-60E: Shin Nippon Rikagaku, ethylene oxide 6 mol adduct bisphenol A type Epoxy resin (epoxy equivalent 373) L-10: Asahi Chiba, bisphenol F type cyanate resin XU-366: Asahi Chiba, phenyl-1- (1-methylethylidene)
Benzene type cyanate resin H-1: Meiwa Kasei, phenol novolak (OH equivalent 10
6) TrisP-PA: Honshu Chemical, Trisphenol novolak (OH
Equivalent 140) XL-225: Mitsui Toatsu Chemicals xylylene-modified phenol novolak (OH equivalent 175) A-1310: Nippon Unicar, 3-isocyanatopropyltriethoxysilane A-189: Nippon Unicar, 3-mercaptopropyltrimethoxysilane A- 187: Nippon Unicar, 3-glycidoxypropyltrimethoxysilane DMAc: dimethylacetamide DMF: dimethylformamide NMP: N-methylpyrrolidone

[0058]

[Table 1]

[0059]

[Table 2]

This varnish is applied on a substrate (polypropylene film) to a thickness of 30 to 50 μm,
And then heated at 150 ° C. for 30 minutes, and then peeled off from the substrate at room temperature to obtain a film-shaped die bonding material (hereinafter referred to as an adhesive film).

(Evaluation Test) Examples 1-4, Comparative Examples 1-3
For the film-like adhesive film obtained in the above, the peel adhesive force was measured, and a silicon chip was bonded to a copper lead frame using the adhesive films obtained in Examples 1 to 4 and Comparative Examples 1 to 3. The chip warpage was measured when the chip was warped. The measurement results are shown in Tables 3 and 4.

[0062]

[Table 3]

[0063]

[Table 4]

The methods for measuring the elastic modulus, peel adhesive strength and chip warpage are as follows. <Film elastic modulus measurement method> The dynamic viscoelasticity was measured at a heating rate of 5 ° C / min and a frequency of 1 Hz using a viscoelasticity analyzer RSA-2 manufactured by Rheometrics, and the storage elastic modulus E ′ at 250 ° C was measured. The elastic modulus was used. <Measurement Method of Peel Adhesive Force> The adhesive film was cut into a size of 5 mm × 5 mm, and sandwiched between a 5 × 5 mm silicon chip and a die pad of a copper lead frame, and a load of 1000 g was applied thereto, and 180 ° C. Alternatively, after pressure bonding at 250 ° C. for 5 seconds, the adhesive film was cured by heating at 180 ° C. for 1 hour. The peel strength of the silicon chip when heated at 245 ° C. or 275 ° C. for 20 seconds was measured with a push-pull gauge. <Measurement method of chip warpage> Adhesive film is 10mm x 10mm
This is cut between the die pad of a copper lead frame and a silicon chip of 10 mm x 10 mm in size, pressed under a load of 1000 g, and pressed at 250 ° C for 20 seconds, and then returned to room temperature. , Using a surface roughness meter for this,
The chip surface was scanned 10 mm diagonally in the diagonal direction, and the maximum height (μm) from the base line was obtained to determine the chip warpage.

[0065]

The film-like die bonding material of the present invention can be used as a bonding material for electronic components such as semiconductor elements and supporting members such as lead frames and insulating supporting substrates, with good hot adhesive strength and high-temperature soldering during mounting. It has excellent reliability to withstand application heat history, and also has excellent low stress properties and low-temperature adhesion.
Therefore, it can be suitably used as a die bond material for a copper lead frame and an insulating support substrate.

Continuation of the front page F term (reference) 4J004 AA11 AA12 AA13 AA14 AA15 AA16 AA17 AA18 AA19 AB05 BA02 FA05 4J040 DK021 DK022 DL031 DL032 EB011 EB012 EB021 EB022 EB081 EB082 EB091 EE092 ED092 EB092 ED092 LA02 LA06 NA20 PA23 PA30 4J043 PA01 PA04 PC136 QB15 QB26 RA34 RA35 SA06 SB02 TA22 TB02 UA042 UA052 UA121 UA122 UA131 UA132 UA141 UA151 UA152 UA252 UA262 UA332 UB332 UB012 UB012 UB012 UB012 UB012 UB012 UB012 UB012 UB012 UB0121 UB312 UB321 UB331 UB352 XA13 YA05 ZA12 ZB01 5F047 BA33 BA51 BA54 BB03 BB05

Claims (8)

[Claims] 1. A film-shaped die bonding material for bonding a semiconductor element to a support member, wherein the die bonding material has an elastic modulus of less than 0.1 MPa at a temperature of 250 ° C. or more before bonding. A die bonding material having an elastic modulus at 250 ° C. after heat curing of 0.5 to 20 MPa. 2. The die bonding material according to claim 1, comprising a thermoplastic resin having a Tg of 200 ° C. or lower and a thermosetting resin. 3. The die bonding material according to claim 2, further comprising a silane coupling agent. 4. The die bonding material according to claim 2, further comprising a filler. 5. The die bonding material according to claim 2, wherein the thermoplastic resin is a polyimide resin or a phenoxy resin. 6. A polyimide resin represented by the following formula (I): (Where n is an integer of 2 to 20) and a tetracarboxylic dianhydride represented by the following formula (II): The content of at least one of the tetracarboxylic dianhydrides represented by the formula is 30 mol% of the total tetracarboxylic dianhydrides
The die bonding material according to claim 5, which is a polyimide resin obtained by reacting the above tetracarboxylic dianhydride with a diamine. 7. A polyimide resin comprising tetracarboxylic dianhydride and the following formula (III): (Wherein Q ₁ and Q ₂ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group, and Q ₃ , Q ₄ , Q ₅ and
Q ₆ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and m represents an integer of 1 to 50. 7. The die bonding material according to claim 5, wherein the siloxane-based diamine represented by the formula (1) is a polyimide resin obtained by reacting with a diamine containing at least 3 mol% of all diamines. 8. A semiconductor device including at least a semiconductor element and a support member, wherein the semiconductor element and the support member are bonded by the die bonding material according to claim 1. Semiconductor device.