JP2001302998A - Adhesive film and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive film with excellent heat resistance after moisture absorption, reflow resistance and adhesion after moisture absorption and a semiconductor device which ensures high liability under high temperature and humidity conditions using the film. SOLUTION: The adhesive film contains a filler which has a pore with an average diameter of 0.01-2.0 μm and a pore content by volume of 0.1-20 volume %. The adhesive film is obtained by coating and drying a composition containing the filler and satisfies the relationship: 0.75>a/b (wherein, (a) is a contact angle between the filler and water and (b) is a contact angle between water and a material obtained by coating and drying the composition except the filler).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an adhesive film and its use. More particularly, the present invention relates to an adhesive film useful for bonding a semiconductor chip and a support substrate in a semiconductor device, a wiring board for mounting a semiconductor using the same, a semiconductor device, and a method of manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, a system mainly containing acrylonitrile-butadiene rubber has been widely used as an adhesive for wiring boards and semiconductor packages. As a printed wiring board-related material having improved moisture resistance, Japanese Unexamined Patent Publication No.
JP-A-243180 discloses an acrylic resin, an epoxy resin, an adhesive containing a polyisocyanate and an inorganic filler, and JP-A-61-138680 discloses an acrylic resin, an epoxy resin, and a urethane bond in a molecule. There is an adhesive having a primary amine compound having both ends and a primary amine compound and an inorganic filler.

[0003] However, these known adhesives are:
When a moisture resistance test was performed under severe conditions such as a PCT (pressure cooker test) treatment, the deterioration was large. In addition, there are disadvantages such as a large decrease in adhesive strength after a long-time treatment at a high temperature and an inferior electric corrosion resistance. In particular, P used for reliability evaluation of semiconductor-related parts
When a moisture resistance test was performed under severe conditions such as CT treatment, the deterioration was large. As described above, in the adhesive containing rubber as a main component, although the filler and the like are reinforced, there is a problem in heat resistance after moisture absorption.

Recently, from the viewpoint of cost reduction, as a method of shortening a semiconductor manufacturing process, an adhesive film is laminated on the back surface of a semiconductor wafer in advance, and the semiconductor wafer is diced together with the adhesive film. As a manufacturing method of picking up and directly bonding to a supporting member is being spread, it is necessary to cope with this manufacturing process.

[0005]

SUMMARY OF THE INVENTION The present invention relates to an adhesive film having excellent heat resistance after moisture absorption, reflow resistance, adhesion after moisture absorption, and the like, and high reliability under high temperature and high humidity conditions using the same. And a semiconductor device having the same. Another object of the present invention is to provide a method of manufacturing a semiconductor device, which does not require any of a step of temporarily stretching a film and equipment used in the process.

[0006]

Means for Solving the Problems The present invention relates to the following inventions. 1) An adhesive film containing pores having an average diameter of 0.01 to 2.0 μm in a volume content of 0.1 to 20% by volume. 2) The adhesive film as described in 1) above, containing a filler.

3) (1) a polymer compound having a weight average molecular weight of 100,000 or more which is incompatible with the following (2) epoxy resin;
(2) epoxy resin, (3) epoxy resin curing agent,
A composition containing (4) a filler and (5) a curing accelerator is applied and dried, and the adhesive containing 0.1 to 20% by volume of pores having an average diameter of 0.01 to 2.0 μm is contained. the film.

4) applying a composition containing a filler,
When the adhesive film obtained by drying, the contact angle between the filler and water is a, when the composition excluding the filler from the composition is applied, and the contact angle between the dried and water is b,
An adhesive film satisfying the relationship of 0.75> a / b.

5) (1) a polymer compound having a weight average molecular weight of 100,000 or more which is incompatible with the following (2) epoxy resin;
(2) epoxy resin, (3) epoxy resin curing agent,
(4) An adhesive film obtained by applying and drying a composition containing a filler and (5) a curing accelerator, wherein the components (1) to (5) have a ratio of 0.75> a / b. (Where (4) the contact angle between the filler and water is a,
Applying the blends of (1), (2), (3) and (5),
The contact angle between the dried product and water is b)) Adhesive film.

6) When the mixing ratio of the components (1) to (5) is (1) the polymer compound is 50.0 to 70.0% by weight,
(2) epoxy resin and (3) epoxy resin curing agent in total of 17.0 to 49.5% by weight; (4) filler
45 to 10.0% by weight and (5) curing accelerator 0.0
The adhesive film according to the above 3) or 5), wherein the amount is 5 to 3.0% by weight.

7) (1) The adhesive film as described in 3), 5) or 6) above, wherein the polymer compound having a weight average molecular weight of 100,000 or more is an acrylic copolymer containing an epoxy group. 8) The adhesive film according to any one of 3), 5) to 7) above, wherein the epoxy resin is an epoxy resin having no mutagenic properties. 9) (4) The adhesive film according to any one of 2) to 8) above, wherein the filler is silica.

10) (4) The filler has an average particle size of 0.0
Any one of the above 2) to 9), wherein the thickness is from 0.05 to 0.1 μm.
The adhesive film according to the above item. 11) The adhesive film according to any one of 1) to 10), which has a single-layer structure. 12) The adhesive film as described in 11) above, wherein the adhesive film has a protective layer on one side or both sides.

[13] An adhesive film with a substrate, wherein the adhesive film according to any one of [1] to [10] is laminated on one or both sides of the substrate layer directly or via another layer. 14) The adhesive film with a substrate according to 13), wherein the adhesive film with a substrate has a protective layer on one or both surfaces.

(15) The adhesive film with a substrate according to the above (13) or (14), wherein the substrate is a heat-resistant film. 16) Using the adhesive film according to any one of the above 1) to 12) or the adhesive film with a base material according to any one of the above 13) to 15), between semiconductor elements or between a semiconductor element and a semiconductor support member. And a semiconductor device formed by bonding.

17) After laminating the adhesive film according to any one of 1) to 12) or the adhesive film with a base material according to any one of 13) to 15) above and a dicing tape on a semiconductor wafer. A method of manufacturing a semiconductor device in which a wafer and an adhesive film are cut into chips, and thereafter the semiconductor elements with an adhesive film picked up from a dicing tape are used to bond the semiconductor elements to each other or the semiconductor element and a semiconductor support member.

(18) A dicing film in which a dicing tape is laminated on the adhesive film according to any one of (1) to (12) or the adhesive film with a base material according to any one of (13) to (15). Integrated adhesive film. 19) The dicing film-integrated adhesive film described in 18) above is laminated on a semiconductor wafer, and the wafer and the adhesive film are simultaneously diced and then picked up as a semiconductor element with an adhesive layer, and the semiconductor elements or the semiconductor element and the semiconductor support member are picked up. A method of manufacturing a semiconductor device to be bonded.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The first adhesive film in the present invention is an adhesive film containing pores having an average diameter of 0.01 to 2.0 μm in a volume content of 0.1 to 20% by volume. Here, the pores of the adhesive film mean pores, spaces, gaps, and the like, and the average diameter of the pores means the diameter of the pores when the volume of the pores is roughly converted into a sphere.

The adhesive film of the present invention has an average diameter of 0.01 to 2.0 from the viewpoint of PCT resistance (prevention of decrease in adhesive strength).
It is necessary to have pores of 0 μm, and 0.03 to
It is preferably 0.1 μm. Further, the volume content of the pores needs to be 0.1 to 20% by volume of the adhesive film from the viewpoint of PCT resistance and reflow resistance. It is preferable that the holes are uniformly dispersed.

The volume content of pores is calculated by the following method. (A) using a scanning electron microscope (SEM), setting a place having a square area having a length of 100 times the average particle diameter of the filler as one side and having 50 holes, SE
Take M photos. (B) The area of the square and the area of the 50 holes are determined by the following method. Transparent film with uniform density and thickness
After placing on the EM photograph and tracing along the shape of all 50 holes with a pen, the traced hole portion is cut off. (C) Similarly, after tracing a fixed square area (including 50 holes) with a pen in the same manner as in (b), the portion excluding the holes is cut off. (D) weigh the separated (b) and (c),
(B) / (c) is calculated. (E) V = [(b) / (c)] ^3/2 is calculated. (F) The steps (a) to (e) are repeated five times, and the average value of the obtained V is defined as the volume content.

The first adhesive film in the present invention may have the above-mentioned pores, and may be made of, for example, epoxy resin, acrylic resin, polyimide resin, silicone resin, polyurethane resin, cyanate. Those containing a resin such as a resin, among others,
Those containing an epoxy resin or an acrylic resin are preferred because they have excellent heat resistance, adhesiveness and the like.

In addition, because of having the above-mentioned voids,
Most preferably, the adhesive film contains a filler. That is, the size of the pores, the volume content of the pores depends on the content of the filler, the particle size, the aggregation form, the larger the filler content, the finer the particle size of the filler, and The more dispersed the form, the larger the pore size and volume content. Such filler content, shape, and form factors can be used alone or in combination of two or more factors as appropriate to control the size and volume content of pores.

Further, the second adhesive film of the present invention is an adhesive film obtained by applying and drying a composition containing a filler, wherein the contact angle between the filler and water is a, and the filler is prepared from the composition. The adhesive film satisfies the relationship of 0.75> a / b, where b is the contact angle between the applied and dried composition and the water, and water.

That is, the second adhesive film contains a filler and has a heat resistance of 0.7% after absorbing moisture.
5> a / b, that is, it is necessary that a / b is less than 0.75, preferably less than 0.66,
More preferably, it is less than 0.50. The lower limit of a / b is about 0.25.

The contact angle a between the filler and water is measured by the following method. A filler is compression-molded to form a flat plate, and a water drop is dropped on the flat plate, and the angle at which the water drop contacts the flat plate is measured by a contact angle meter. As the value of the contact angle, an average value measured ten times is used. Applying the composition excluding the filler,
The contact angle b between the dried product and water is measured in the same manner as in the measurement of a.

The material of the second adhesive film of the present invention also includes a material containing a resin such as an epoxy resin, an acrylic resin, a polyimide resin, or a silicone resin. Among them, a material containing an epoxy resin or an acrylic resin is preferable. , Heat resistance and adhesiveness are preferred. Also,
Since the contact angle a between the filler and water changes depending on the composition of the filler, the treatment of the surface thereof, and the particle size of the filler through the method for producing the filler, for example, using silica, diantimony trioxide, Further, by subjecting the surface of the filler to an affinity (hydrophilic) treatment and using a finer filler, the contact angle a can be reduced.
Such factors affecting the contact angle alone or
The contact angle between the filler and water can be controlled by appropriately combining two or more factors.

The characteristics of the first adhesive film are as follows:
A film having the characteristics of the second adhesive film is more preferable because it has excellent PCT resistance and heat resistance to moisture-absorbing solder.

Hereinafter, items common to the first adhesive film and the second adhesive film of the present invention will be described.

The components of the adhesive film of the present invention include:
(1) the following (2) a polymer compound having a weight average molecular weight of 100,000 or more that is incompatible with the epoxy resin, (2) an epoxy resin, (3) a curing agent for the epoxy resin, (4) a filler, and (5) Those containing a curing accelerator are preferable because they have excellent heat resistance and adhesiveness, can be cured at about 170 ° C. for 1 hour, and can be manufactured under mild conditions.

The polymer compound (1) having a weight average molecular weight of 100,000 or more must be incompatible with the epoxy resin (2). Here, the weight average molecular weight is a value in terms of polystyrene using a calibration curve of standard polystyrene by gel permeation chromatography (GPC). In addition, (1) the high molecular compound is incompatible with the (2) epoxy resin means that after the preliminary curing, the (1) high molecular compound separates from the (2) epoxy resin and separates into two or more phases. Means nature. In this case, even after curing, (2) the epoxy resin is separated from the epoxy resin and remains in two or more phases.

Examples of the polymer compound (1) include rubber such as acrylic rubber, silicone resin, and silicone-modified resin such as silicone-modified polyamideimide. From the viewpoint of high adhesiveness and heat resistance, an epoxy group-containing acrylic copolymer is preferred.

Examples of the epoxy group-containing acrylic copolymer include glycidyl (meth) acrylates 2 to 6
An acrylic copolymer having a Tg of -10 ° C. or higher, obtained by copolymerizing the polymer by weight and the balance of ethyl (meth) acrylate or butyl (meth) acrylate or both, is mentioned as a preferable example. This is because when the copolymerization amount of glycidyl (meth) acrylate is within this range, adhesive strength can be ensured and the copolymer does not gel. When the Tg is -10 ° C or higher, the tackiness of the adhesive film in the B-stage state is appropriate, and the handleability is good. As such a copolymer, Teikoku Chemical Industry Co., Ltd.
Trade name: HTR-860P-3.

(1) A high molecular weight compound having a weight average molecular weight of 1
In the case of producing those having a molecular weight of 100,000 or more, pearl polymerization, solution polymerization and the like are effective as polymerization methods. (1) The compounding amount of the polymer compound is preferably 50.0 to 70.0% by weight. Within this range, it is possible to sufficiently secure a reduction in elastic modulus, suppression of flowability during molding, and the like, and good handleability at high temperatures.

The epoxy resin (2) in the present invention is not particularly limited, and any known epoxy resin may be used. The epoxy resin has a bifunctional or higher molecular weight and a weight average molecular weight of less than 5,000, preferably less than 3,000. Is preferred. Such (2)
Examples of the epoxy resin include a bisphenol A epoxy resin and a bisphenol F epoxy resin.

A bisphenol A type epoxy resin or a bisphenol F type epoxy resin in liquid form is commercially available from Yuka Shell Epoxy Co., Ltd. under the trade names of Epicoat 807, Epicoat 827 and Epicoat 828. In addition, Dow Chemical Japan Co., Ltd. E. FIG.
R. 330, D.I. E. FIG. R. 331; E. FIG. R. 36
It is marketed under the trade name of 1. It is also commercially available from Toto Kasei Corporation under the trade names YD8125 and YDF8170.

(2) As the epoxy resin, a polyfunctional epoxy resin can be used for the purpose of increasing the Tg of the obtained cured product. Examples of the polyfunctional epoxy resin include a phenol novolak epoxy resin and a cresol novolak epoxy resin. Phenol novolak type epoxy resin is available from Nippon Kayaku Co., Ltd.
It is marketed under the trade name 01. The cresol novolak epoxy resin is commercially available from Sumitomo Chemical Co., Ltd. under the trade names ESCN-190 and ESCN-195. In addition, Nippon Kayaku Co., Ltd.
It is commercially available under the trade names CN1012, EOCN1025, and EOCN1027. Y from Toto Kasei Co., Ltd.
DCN701, YDCN702, YDCN703, YD
It is commercially available under the trade name CN704.

As the curing agent for the epoxy resin (3) in the present invention, a known curing agent for the epoxy resin can be used. For example, amine, polyamide, acid anhydride, polysulfide, boron trifluoride, phenolic hydroxyl group can be used. Examples thereof include bisphenol A, bisphenol F, and bisphenol S, which are compounds having two or more in one molecule.
In particular, a phenol resin such as a phenol novolak resin, a bisphenol novolak resin, and a cresol novolak resin is preferable from the viewpoint of excellent electric corrosion resistance when absorbing moisture. For this, phenolite LF2882, phenolite LF2822, phenolite TD-2090, phenolite TD-2149, phenolite VH4150, phenolite VH4170 commercially available from Dainippon Ink and Chemicals, Inc. are used. can do.

As the epoxy resin and the curing agent, compounds having no mutagenicity, for example, those not using bisphenol A, are preferable because they have little effect on the environment and the human body.

The total amount of the curing agents (2) and (3) is preferably 17.0 to 49.5% by weight. When the total of the two is in this range, the adhesiveness, moldability (flowability), etc. can be ensured, and the elastic modulus can be suppressed to an appropriate range.

Here, the ratio of (2) epoxy resin to (3) epoxy resin curing agent [(2) :( 3)] is 3
The ratio is preferably 3:67 to 75:25. When the ratio is within the range, heat resistance and moldability (flow properties) are good.

The (4) filler in the present invention includes:
In addition to oxides such as silica, alumina and antimony oxide, nitrides, carbides and hydroxides can be used. From the viewpoints of heat resistance, moldability (flowability), etc., silica and diantimony trioxide are preferred. (4) The average particle size of the filler is preferably 0.005 to 0.1 μm from the viewpoint of heat resistance, moldability (flowability), and the like. The average particle size of the filler can be measured by a diffraction scattering method using laser light.

Incidentally, as the above-mentioned silica, C.I.
From Nanotech SiO _{2 with} an average particle size of 0.012 μm
PATOX having an average particle size of 0.02 μm from Nippon Seiko Co., Ltd. as diantimony trioxide.
It is commercially available under the trade name -U, and these fillers can be used.

(4) The amount of the filler used is 0.45 to 1
The content is preferably 0.0% by weight, more preferably 1.0 to 5.0% by weight. When the amount of the filler is within this range, moisture resistance, storage elastic modulus of the adhesive film,
Sufficient adhesive strength can be secured.

Various imidazoles can be used as the curing accelerator (5) in the present invention. Examples of the imidazole include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like. Imidazoles were obtained from Shikoku Chemicals Corporation in 2E4MZ, 2PZ-
It is commercially available under the trade name of CN, 2PZ-CNS.

Further, the film preferably has a potential in that the service life of the film is prolonged, and typical examples thereof include dihydrazide compounds such as dicyandiimide and adipic dihydrazide, guanamic acid, melamic acid, epoxy compounds and imidazole compounds. An addition compound, an addition compound of an epoxy compound and a dialkylamine, an addition compound of an amine and thiourea, an addition compound of an amine and isocyanate, and the like can be given. Further, an adduct-type structure is preferable in that the activity at room temperature can be reduced.

(5) The compounding amount of the curing accelerator is from 0.05 to
It is preferably 3.0% by weight. Within this range, the curability, heat resistance, adhesiveness and pot life are good.

The composition of the present invention has (2) compatibility with the epoxy resin from the viewpoint of reducing the tackiness of the adhesive in the B stage (pre-cured state) and improving the flexibility during curing. A resin having a weight average molecular weight of 30,000 or more can be blended in an amount of about 5 to 10% by weight.

Such resins include phenoxy resins, high molecular weight epoxy resins, ultrahigh molecular weight epoxy resins,
Examples of the rubber include a highly polar functional group-containing rubber and a highly polar functional group-containing reactive rubber. The phenoxy resin is commercially available from Toto Kasei Co., Ltd. under the trade names Phenototo YP-40 and Phenototo YP-50. Phenoxy Associates also provided PKHC, PKHH, PK
It is marketed under the trade name HJ.

The high molecular weight epoxy resin has a molecular weight of 30,000 to
80,000 high molecular weight epoxy resin, and ultra high molecular weight epoxy resin having a molecular weight exceeding 80,000 (Japanese Patent Publication No. 7-5961)
7, Japanese Patent Publication No. 7-59618, Japanese Patent Publication No. 7-5
No. 9619, Japanese Patent Publication No. 7-59620, Japanese Patent Publication No. 7-64911, and Japanese Patent Publication No. 7-68327. As a highly polar functional group-containing reactive rubber, a carboxyl group-containing acrylic rubber is commercially available from Teikoku Chemical Industry Co., Ltd. under the trade name of HTR-860P.

The composition of the present invention may contain a coupling agent in order to improve the interfacial bonding between different materials. As such a coupling agent, a silane coupling agent is preferable. Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β-aminoethyl-γ- Aminopropyltrimethoxysilane and the like can be mentioned.

The above-mentioned silane coupling agent is such that γ-glycidoxypropyltrimethoxysilane is NUC A-1.
87, γ-mercaptopropyltrimethoxysilane is N
UCA-189, γ-aminopropyltriethoxysilane is NUC A-1100, γ-ureidopropyltriethoxysilane is NUC A-1160, and N-β-aminoethyl-γ-aminopropyltrimethoxysilane is N
All are commercially available from Nippon Unicar Co., Ltd. under the trade name UC A-1120.

The amount of the coupling agent is from 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of (1), (2) and (3) in view of the effect of the addition, heat resistance and cost. It is preferred that

Further, in order to adsorb ionic impurities and improve insulation reliability at the time of moisture absorption, an ion scavenger can be blended.

The adhesive film in the present invention is formed into a varnish by dispersing each component in a solvent, applied on a carrier film, heated and dried to remove the solvent, thereby forming an adhesive layer formed on the carrier film. can get. The heating conditions at this time are 80 to 250 ° C. for 10 minutes to 20 minutes.
About an hour. As the carrier film, a plastic film such as a polytetrafluoroethylene film, a polyethylene terephthalate film, or a release-treated polyethylene terephthalate film can be used.

At the time of use, the carrier film can be peeled off to use only the adhesive layer (that is, the adhesive film), or it can be used together with the carrier film and removed later. The thickness of the adhesive layer (that is, the adhesive film) is preferably from 3 to 300 μm,
More preferably 200 μm, 20 to 100 μm
Is particularly preferred.

As the above solvent, it is preferable to use a low boiling point solvent such as methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol and 2-methoxyethanol. Further, a high-boiling solvent may be added for the purpose of improving the coating properties. As a high boiling point solvent,
Examples thereof include dimethylacetamide, dimethylformamide, methylpyrrolidone, and cyclohexanone.

The production of the varnish can be carried out by a mill, a three-roll or bead mill, or a combination thereof. Further, it is preferable to mix the filler with the epoxy resin and the curing agent, and then with the polymer compound. By mixing the filler and the low molecular weight material in advance and then blending the high molecular weight material, the time required for mixing can also be reduced.

The adhesive film of the present invention can be used as a single-layer film. Further, it can be used as an adhesive film with a substrate in which the above-mentioned adhesive film is laminated on one or both sides of the substrate directly or via another layer. Further, a protective layer can be formed on one or both sides thereof.

The substrate used in the production of the adhesive film is
There is no particular limitation as long as it can withstand the heating and drying conditions during the production of the adhesive film. 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.

When the adhesive film with a substrate is used as it is as an adhesive for a semiconductor device, the substrate is preferably a heat-resistant film. Examples of the heat-resistant film include a polyimide film, a polyetherimide film, a methylpentene film, and a polyethernaphthalate film.

Next, a method for producing the adhesive film of the present invention will be described. The production of a single-layer adhesive film includes the steps of dissolving, mixing or kneading the components in an organic solvent, forming a layer of the mixture on a substrate, heating and drying, and removing the substrate. Can be performed via Mixing and kneading when using a filler, a normal stirrer, a grinder, a three-roller, a disperser such as a ball mill as appropriate,
It can be performed in combination.

In the production of an adhesive film with a base material, after selecting a heat-resistant film as a base material, the above-described steps except for the step of removing the base material may be performed. In addition, in the production of an adhesive film with a base material in which an adhesive film layer is laminated on both sides, after performing each of the above steps on one side, a layer of the mixture is formed on the other uncoated surface, and heated and dried. You can do it.

When a protective layer is formed on one or both surfaces, a polypropylene film, a polyester film such as polyethylene terephthalate, or the like can be used as the protective layer.

The obtained adhesive film is usually peeled off from the substrate film at room temperature to form a self-supporting adhesive film, which can be used for manufacturing a semiconductor device.
More specifically, for example, after laminating the adhesive film and the dicing tape of the present invention on a semiconductor wafer,
Cut the wafer and adhesive film into chips, then
Using a semiconductor element with an adhesive film picked up from a dicing tape, a semiconductor device can be manufactured by bonding the semiconductor elements or the semiconductor element and the semiconductor support member.

Further, the adhesive film is not peeled off from the substrate, but is directly laminated on a semiconductor wafer, and the wafer and the adhesive film are simultaneously diced and then picked up as a semiconductor element having an adhesive layer. The semiconductor device can be manufactured by adhering the semiconductor device.

Further, by laminating a dicing tape on the adhesive surface of the adhesive film in advance, an adhesive film for a semiconductor in which the adhesive film and the dicing film are integrated can be obtained. This adhesive film for a semiconductor is, for example, laminated on the back surface of the wafer, and simultaneously diced on the wafer and the adhesive film, and then picked up as a semiconductor element with an adhesive film, and bonding the semiconductor elements to each other or the semiconductor element and the semiconductor support member. A semiconductor device can be obtained.

The obtained adhesive film is composed of a semiconductor element such as an IC or an LSI, a lead frame such as a 42 alloy lead frame or a copper lead frame, a plastic film such as a polyimide, an epoxy resin or a polyimide resin, or a substrate such as a glass nonwoven fabric. Impregnated and cured with a plastic such as polyimide, epoxy resin, polyimide resin, or ceramics such as alumina. Further, depending on the type of the package, the semiconductor elements can be used for the joint.

For bonding, the adhesive film of the present invention is sandwiched between the semiconductor element and the support member or between the semiconductor elements as described above, and the two are bonded by heating and pressing. The heating temperature is preferably from 100 to 300 ° C., and the heating time is from 0.
Preferably from 1 to 300 seconds.

[0068]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Note that the filler used here has not been subjected to surface treatment. Example 1 As an epoxy resin, 17.2 g of a bisphenol A type epoxy resin (epoxy equivalent: 190, using Epicoat 828 manufactured by Yuka Epoxy Shell Co., Ltd.), a cresol novolac type epoxy resin (epoxy equivalent: 195, Sumitomo Chemical Co., Ltd.) 5.8 g of phenol novolak resin (Plyofen LF2882 manufactured by Dainippon Ink and Chemicals, Inc.) as a curing agent for epoxy resin.
15.3 g, γ- as a silane coupling agent
0.2 g of glycidoxypropyltrimethoxysilane (using NUC A-187 manufactured by Nippon Unicar Co., Ltd.), silica filler (Nanotech SiO manufactured by C I Kasei Co., Ltd.)
₂ (using an average particle size of 0.012 μm) Methyl ethyl ketone was added to 3.8 g of the composition, mixed with stirring, and kneaded with a bead mill for 90 minutes.

An epoxy-containing acrylic rubber (weight-average molecular weight: about 700,000, manufactured by Teikoku Chemical Industry Co., Ltd.)
860P-3) 57.5 g, 1 as curing accelerator
-Cyanoethyl-2-phenylimidazole (Curesol 2PZ-CN manufactured by Shikoku Chemical Industry Co., Ltd. is used)
2 g was added and mixed with a stirring motor for 30 minutes. The obtained varnish was applied on a release-treated polyethylene terephthalate film having a thickness of 75 μm, and dried by heating at 140 ° C. for 5 minutes. A coating film in a stage state was formed, and an adhesive film provided with a carrier film was formed.

The weight-average molecular weight was measured by a GPC method using a standard polystyrene calibration curve with the following apparatus and column. <GPC measurement> Apparatus: HPLC Model 635, manufactured by Hitachi, Ltd. Column: Gelpack R-440, manufactured by Hitachi Chemical Co., Ltd.
R-450 and R-400M

EXAMPLE 2 Cresol novolak type epoxy resin as epoxy resin
Fat (epoxy equivalent 210, YDCN manufactured by Toto Kasei Co., Ltd.)
1703g, used as a curing agent for epoxy resin
Cresol novolak resin (Dainippon Ink and Chemicals
(Use Plyofen LF2882 manufactured by Co., Ltd.) 1
2.9 g, an epoxy-containing acrylic copolymer
Poxy-containing acrylic rubber (weight average molecular weight of about 700,000
(HTR-860P-3 manufactured by Kokusai Chemical Industry Co., Ltd. is used.) 6
4.3 g, 1-cyanoethyl-2-phenylene as a curing accelerator
Enylimidazole (Cureazo manufactured by Shikoku Chemicals Co., Ltd.)
0.2Pg) and 0.2 g of silane
Γ-ureidopropyl triethoxy as a coupling agent
Silane (NUC A-1160 manufactured by Nippon Unicar Co., Ltd.)
0.3g, silica filler (Sea-I Chemical Co., Ltd.)
Nanotech SiO Co., Ltd. _Two(Average particle size 0.012μ
m)) to a composition consisting of 3.0 g of methyl ethyl ketone.
And mixed with stirring.
Kneaded for 0 minutes.

The obtained varnish was applied on a release-treated polyethylene terephthalate film having a thickness of 75 μm,
The film was heated and dried at 140 ° C. for 5 minutes to form a coating film in a B-stage state having a film thickness of 75 μm, thereby forming an adhesive film provided with a carrier film. The weight average molecular weight was measured in the same manner as in Example 1.

Example 3 A carrier film was provided in the same manner as in Example 1 except that 3.8 g of silica (Aerosil 50 (average particle size: 0.03 μm) of Nippon Aerosil Co., Ltd.) was used as a filler. An adhesive film was produced.

Example 4 As the filler, diantimony trioxide (Nippon Seiko Co., Ltd.
An adhesive film provided with a carrier film was produced in the same manner as in Example 1 except that 3.8 g of ATOX-U (average particle size: 0.02 μm) was used.

Comparative Example 1 An adhesive film having a carrier film was produced in the same manner as in Example 1 except that no filler was added.

Comparative Example 2 Diantimony trioxide (Nippon Seiko Co., Ltd.
ATOX-HS (average particle size is 0.02 μm)) 0.05
Except for using g, an adhesive film provided with a carrier film was produced in the same manner as in Example 1.

The porosity of the adhesive film obtained under each condition was measured by the following method.

(A) SE of Model S-4500 manufactured by Hitachi, Ltd.
The length of 100 times the average particle diameter of the filler is
An SEM photograph is taken of a place having a square area as a side and having 50 holes. (B) On a square photo with 50 holes,
Place a transparent film of uniform density and film thickness
After tracing along the shape of all the holes with a pen, the traced holes are cut off. (C) Similarly, after tracing a fixed square area (including 50 holes) with a pen in the same manner as in (b), the portion excluding the holes is cut off. (D) weigh the separated (b) and (c),
(B) / (c) is calculated. (E) V = [(b) / (c)] ^3/2 is calculated. (F) The steps (a) to (e) are repeated five times, and the average value of the obtained V is defined as the volume content. Table 1 shows the obtained results.

Further, a polyimide film having a thickness of 50 μm was placed on both sides of each adhesive film at a temperature of 80 μm.
At a pressure of 0.3 MPa and a conveying speed of 0.3 m / min using a hot roll laminator.
Cured at 0 ° C. for 1 hour. This sample was examined for heat resistance and PCT (pressure cooker test) resistance.

As a method of evaluating heat resistance, the moisture absorption soldering heat test was conducted by placing a sample left for 48 hours in an environment of 85 ° C./85% relative humidity in a solder bath at 240 ° C., and blistering occurred in less than 40 seconds. The sample was evaluated as x, and the sample with blisters generated for 40 seconds or more and less than 120 seconds was evaluated as ○. Further 120
A sample that did not generate blisters for 2 seconds or longer was evaluated as ◎.

The PCT resistance test was performed by observing the appearance of a sample treated at a temperature of 121 ° C., 2 atm and 100% humidity for a predetermined period of time.

The contact angle a between the filler and water was determined by compression molding the filler to produce a flat plate, and then dropping a water droplet on the flat plate, and measuring the angle at which the water droplet contacts the flat plate with a contact angle meter. . The value of the contact angle was measured 10 times and the average value was adopted. The contact angle b with water of the coated and dried composition containing no filler was also measured in the same manner.

[0083]

[Table 1]

Examples 1 to 4 are adhesive films having pores of 0.01 to 2.0 μm within the scope of the present invention.
The joined body for semiconductors using these adhesive films was excellent in heat resistance to moisture absorption solder and PCT resistance was 400 hours or more. Furthermore, Example 2 uses silica as a filler and does not use a mutagenic bisphenol A-type epoxy resin, so that it is easy to handle.
As in Example 1, it has excellent moisture absorption solder heat resistance and good PCT resistance, while having the characteristic of having a small adverse effect on the environment and the human body.

Comparative Example 1 has no voids, and Comparative Example 2 has voids, but the amount is out of the range of the present invention. In any case, the solder heat resistance during moisture absorption is insufficient, and the PCT resistance is only 100 hours, which is significantly shorter than the PCT resistance of Examples 1 to 4.

In Examples 1 to 4, the contact angle ratio (a /
b) is an adhesive film of <3/4, that is, less than 0.75, and the semiconductor device using these adhesive films has good heat resistance to moisture-absorbing solder and good PCT resistance of 400 hours or more.

Comparative Example 1 is an example containing no filler, and Comparative Example 2 has a contact angle ratio of 3/4 or more, which is out of the range of the present invention. Both have insufficient moisture absorption solder heat resistance,
The PCT resistance was also only 100 hours, which was not long enough.

<< Production Example of Multilayer Structure Film >> An adhesive film was coated on one surface of a polyimide core material (UPILEX 25SGA manufactured by Ube Industries, Ltd., having a thickness of 25 μm) with a hot roll laminator at 100 ° C. and a speed of 0.3 m / m. mi
An adhesive film was formed on both sides of the core material by laminating under the conditions of n and a load of 0.3 MPa and further laminating an adhesive film on the back surface of the polyimide core material under the same conditions. This three-layer film was easy to handle without peeling between the adhesive layer and the core material layer. Further, an adhesive film with a carrier film was used as the adhesive film, and the adhesive layer side was laminated on a polyimide core material to produce an adhesive film having a multilayer structure in which the adhesive layer had a cover film. When the obtained film is stored, transported, used,
No wrinkles or foreign substances were attached to the adhesive layer, and the workability was excellent.

<< Production Example of Semiconductor Device >> As a wiring board for mounting a semiconductor, a polyimide film substrate (polyimide film 50 μm
Thickness, wiring width 30 μm, wiring interval 40 μm, wiring line thickness 20
μm) was used. Cut the adhesive film into a predetermined shape,
The cut single-layer adhesive film of the present invention was placed at a desired position on a wiring board, and was thermocompressed at 140 ° C., 1.5 MPa, for 3 seconds, and attached. Further, the wiring board with the adhesive film and the semiconductor chip were bonded by thermocompression bonding at 160 ° C. and 1.5 MPa for 3 seconds. Thereafter, the temperature was maintained at 170 ° C. for 1 hour to cure the adhesive, and then the semiconductor chip and the wiring of the wiring board were connected with gold wires, and the periphery was sealed with an epoxy resin-based sealing material to manufacture a semiconductor device. . The obtained semiconductor device was excellent in PCT resistance.

<< Example of Use in Wafer Backside Adhesion Method >> An adhesive film and a dicing tape are applied to a semiconductor wafer by a hot roll laminator at 100 ° C. at a speed of 0 ° C.
After bonding at 3 m / min under a load of 0.3 MPa, the wafer and the adhesive film are cut into chips, and then the wiring substrate and the semiconductor chip with the adhesive film are separated at 160 ° C. for 1.5
Atmospheric pressure bonding for 3 seconds, and bonding. Thereafter, the temperature was maintained at 170 ° C. for 1 hour to cure the adhesive, and then the semiconductor chip and the wiring of the wiring board were connected with gold wires, and the periphery was sealed with an epoxy resin-based sealing material to manufacture a semiconductor device. . The obtained semiconductor device was excellent in PCT resistance.

[0091]

The adhesive film of the present invention is excellent in heat resistance after moisture absorption, reflow resistance, adhesiveness after moisture absorption, and the like. Therefore, a semiconductor device using this film is excellent in reliability.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/52 H01L 21/52 E // C09J 133/06 C09J 133/06 (72) Inventor Yasushi Shimada Ibaraki 1500, Ogawa, Shimodate-shi, Hitachi Hitachi Chemical Industries, Ltd. (72) Inventor Yuko Tanaka 1500, Oji, Shimodate-shi, Ibaraki Pref., Hitachi Chemical Co., Ltd. (72) 1500 Ogawa Hitachi Research Institute, Ltd. CA05 CA06 CC02 CC03 CD05 CD06 DB02 FA05 GA01 4J040 DF031 EB042 EC061 EC071 EC231 EF001 EG002 EH031 EK031 EK 111 GA11 GA22 HA076 HA126 HA206 HA306 HA326 HB38 HB47 HC01 HC15 HC16 HC24 HC25 HD05 HD08 JA09 JB02 KA16 KA17 KA42 LA01 LA03 LA06 LA08 NA20 5F047 BA23 BA34 BB03 BB19

Claims (19)

[Claims] 1. An adhesive film containing pores having an average diameter of 0.01 to 2.0 μm in a volume content of 0.1 to 20% by volume. 2. The adhesive film according to claim 1, further comprising a filler. 3. A polymer compound having a weight average molecular weight of 100,000 or more, which is incompatible with the following (2) epoxy resin:
(2) epoxy resin, (3) epoxy resin curing agent,
A composition containing (4) a filler and (5) a curing accelerator is applied and dried, and the adhesive containing 0.1 to 20% by volume of pores having an average diameter of 0.01 to 2.0 μm is contained. the film. 4. An adhesive film obtained by applying and drying a composition containing a filler, wherein the contact angle between the filler and water is a, and a composition excluding the filler from the composition is applied and dried. When the contact angle between an object and water is b,
An adhesive film satisfying the relationship of 0.75> a / b. 5. A polymer compound having a weight average molecular weight of 100,000 or more which is incompatible with the following (2) epoxy resin:
(2) epoxy resin, (3) epoxy resin curing agent,
(4) An adhesive film obtained by applying and drying a composition containing a filler and (5) a curing accelerator, wherein the components (1) to (5) have a ratio of 0.75> a / b. (Where (4) the contact angle between the filler and water is a,
Applying the blends of (1), (2), (3) and (5),
The contact angle between the dried product and water is b)) Adhesive film. 6. The compounding ratio of the components (1) to (5) is as follows:
(1) a polymer compound 50.0 to 70.0% by weight,
(2) a total of 17.0 to 49.5% by weight of epoxy resin and (3) epoxy resin curing agent, (4) filler
0.45 to 10.0% by weight and (5) a curing accelerator
The adhesive film according to claim 3, wherein the amount is 0.05 to 3.0% by weight. 7. The adhesive film according to claim 3, wherein (1) the high molecular compound having a weight average molecular weight of 100,000 or more is an epoxy group-containing acrylic copolymer. 8. The method according to claim 3, wherein (2) the epoxy resin has no mutagenicity.
The adhesive film according to the above item. 9. The adhesive film according to claim 2, wherein (4) the filler is silica. (4) The filler has an average particle size of 0.00.
The adhesive film according to any one of claims 2 to 9, which has a thickness of 5 to 0.1 µm. 11. The adhesive film according to claim 1, which has a single-layer structure. 12. The adhesive film according to claim 11, wherein a protective layer is provided on one or both surfaces of the adhesive film. 13. An adhesive film with a substrate, wherein the adhesive film according to any one of claims 1 to 10 is laminated on one or both surfaces of the substrate layer directly or via another layer. 14. The adhesive film with a substrate according to claim 13, wherein the adhesive film with a substrate has a protective layer on one or both surfaces. 15. The base material is a heat-resistant film,
The adhesive film with a substrate according to claim 13. 16. A semiconductor support between semiconductor elements or a semiconductor element using the adhesive film according to any one of claims 1 to 12 or the adhesive film with a base material according to any one of claims 13 to 15. A semiconductor device formed by bonding members. 17. After laminating an adhesive film according to any one of claims 1 to 12 or an adhesive film with a base material according to any one of claims 13 to 15 and a dicing tape to a semiconductor wafer, the wafer is laminated. And cut the adhesive film into chips, then, using a semiconductor element with an adhesive film picked up from dicing tape,
A method of manufacturing a semiconductor device in which semiconductor elements or a semiconductor element and a semiconductor support member are bonded to each other. 18. A dicing film integrated type wherein a dicing tape is laminated on the adhesive film according to any one of claims 1 to 12 or the adhesive film with a base material according to any one of claims 13 to 15. Adhesive film. 19. The dicing film-integrated adhesive film according to claim 18 is laminated on a semiconductor wafer, and the wafer and the adhesive film are simultaneously diced and then picked up as a semiconductor element with an adhesive layer. A method of manufacturing a semiconductor device for bonding a member.