JP2006219589A - Adhesive film for semiconductor, and semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive film for a semiconductor, sticking the semiconductor element to a supporting member for installing the semiconductor element such as organic substrate at a low temperature, and capable of filling the difference in level of a circuit. <P>SOLUTION: The film for sticking the semiconductor comprises (A) a thermoplastic resin of (a) pts.wt., (B) an epoxy resin of (b) pts.wt., (C) a phenol resin of (c) pts.wt. and (D) a radiation polymerizable monomer of (d) pts.wt., wherein (a) to (d) satisfy the following conditions (I) and (II): (I) 0.1≤(a)/[(b)+(c)+(d)]≤0.7; and (II) 0.02≤(d)/[(b)+(c)+(d)]≤0.5. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

In recent years, there has been an increasing demand for higher density and higher integration of semiconductor devices in response to higher functions of electronic devices, and semiconductor packages have been increasing in capacity and density.
In order to meet such requirements, for example, a lead-on-chip (LOC) structure in which a lead is bonded onto a semiconductor element is employed.

  However, since the semiconductor element and the lead frame are bonded in the LOC structure, the bonding reliability at the bonded portion greatly affects the reliability of the semiconductor package.

Conventionally, a paste-like adhesive has been used for bonding a semiconductor element and a lead frame.
However, it is difficult to apply an appropriate amount of paste adhesive, and the adhesive sometimes protrudes from the semiconductor element.

  For example, in the LOC structure, a film adhesive in which an adhesive is applied to a heat resistant substrate such as a hot-melt adhesive film using a polyimide resin has been used (for example, see Patent Document 1).

  However, since the hot-melt adhesive film needs to be bonded at a high temperature, it may cause thermal damage to a high-density semiconductor element and lead frame.

Particularly in recent semiconductor packages, the chip is stacked in multiple stages on the chip, thereby realizing a reduction in size, thickness and capacity of the package. In such packages, the use of organic substrates such as bismaleimide-triazine substrates and polyimide substrates instead of lead frames is increasing. With the increase in organic substrates, package cracking due to moisture absorption inside the package during infrared reflow for soldering the package has become a technical problem, and it has been found that the contribution of the semiconductor element adhesive is particularly significant.

However, the organic substrate has poor heat resistance compared to the lead frame, and further with the thinning of the package, the thinning of the chip has progressed, and the warping of the chip becomes significant at the past high temperature application temperature, There is an increasing demand for a film adhesive that can be thermocompression bonded at a lower temperature than ever before. As such a film adhesive, a hot melt type adhesive film made of a mixture of a thermoplastic resin and a thermosetting resin is used.
JP-A-6-264035 JP 2000-104040 A JP 2002-121530 A Patent 3562465 JP 2002-256235 A

However, the prior art described in the above literature has room for improvement in the following points.
First, in Patent Documents 2 and 3, a polyimide resin is used as a thermoplastic resin and an epoxy resin is used as a thermosetting resin. Such an adhesive film is excellent in heat resistance and reliability, Because the melt viscosity decreases for the first time in the state and the minimum melt viscosity is high, the wettability at low temperature is insufficient, making it difficult to apply at low temperature, and the chip is thin and stacked in multiple layers It had the problem that it was difficult to apply.
Secondly, in Patent Documents 4 and 5, a resin mainly composed of acrylic rubber is used as a thermoplastic resin having a low glass transition temperature in order to improve wettability at a low temperature, but the molecular weight of the thermoplastic resin is used. When the content is high and the content is high, the fluidity of the film adhesive is poor, the gap between the circuits provided on the organic substrate cannot be filled, and peeling is likely to occur at high temperatures.
Thirdly, a method of increasing the content of the low molecular weight thermosetting component is also conceivable. However, the film adhesive becomes less flexible, and when the film adhesive is cut, the film adhesive cracks. Likely to happen.
The present invention has been made in view of the above circumstances, and its purpose is to bond a semiconductor element and a support member for mounting a semiconductor element such as a lead frame or an organic substrate, thereby achieving low-temperature adhesion and workability. The object is to provide an excellent adhesive film for a semiconductor.

The first adhesive film for a semiconductor according to the present invention is:
(A) thermoplastic resin a parts by weight,
(B) Epoxy resin b parts by weight,
(C) phenol resin c parts by weight, and
(D) radiation-polymerizable monomer d parts by weight,
The a to d are composed of a film for semiconductor adhesion that satisfies the following conditions (I) and (II).
(I) 0.1 ≦ a / (b + c + d) ≦ 0.7
(II) 0.02 ≦ d / (b + c + d) ≦ 0.5
In the first adhesive film for a semiconductor of the present invention, a radiation-polymerizable monomer is added and the thermosetting resin component is limited to a certain blending range with respect to the thermoplastic resin. For this reason, while maintaining the melt viscosity at low temperature low, the brittleness of the film adhesive is reduced, and the workability is excellent.

Moreover, the second adhesive film for a semiconductor according to the present invention is:
(i) an adhesive film for a semiconductor containing a thermoplastic resin and an epoxy resin,
When the temperature is raised from 25 ° C. at a rate of 10 ° C./min, the minimum melt viscosity is 0.1 [Pa · s] or more and 50 [Pa · s] or less in the region of 50 ° C. or more and 180 ° C. or less. It is a feature.
With conventional adhesive films for semiconductors, it has been difficult to achieve both improvement in brittleness of the film adhesive while satisfying (i) of the present invention. By making this (i) and the improvement of the brittleness of the film-like adhesive compatible with each other, the melt viscosity at a low temperature can be kept low, the brittleness of the film can be improved, and the film can be prevented from cracking when the film is cut. The characteristic can be realized. Such an adhesive film for a semiconductor is obtained by, for example, a resin composition containing (A) a thermoplastic resin, (B) an epoxy resin, (C) a phenol resin, and (D) a radiation polymerizable monomer.

  According to the present invention, a semiconductor element and a support member for mounting a semiconductor element such as a lead frame and an organic substrate can be bonded, and low temperature adhesion and workability, particularly workability when a film is transported by a transport roll. An excellent adhesive film for a semiconductor can be provided.

Hereinafter, the 1st adhesive film for semiconductors of this invention is demonstrated.
The first adhesive film for a semiconductor of the present invention comprises (A) thermoplastic resin a part by weight, (B) epoxy resin b part by weight, (C) phenol resin c part by weight, and (D) radiation polymerizable monomer d. The film is composed of a film for semiconductor adhesion that includes parts by weight and that satisfies the following conditions (I) and (II). (I) 0.1 ≦ a / (b + c + d) ≦ 0.7 (II) 0.02 ≦ d / (b + c + d) ≦ 0.5
Hereinafter, each component of the 1st adhesive film for semiconductors of this invention is demonstrated.

The (A) thermoplastic resin used in the present invention means a polymer resin having thermoplasticity and a linear chemical structure.
Specific examples include polyimide resins such as polyimide resins and polyetherimide resins, polyamide resins such as polyamide resins and polyamideimide resins, and acrylic resins such as acrylic ester copolymers.
Among these, acrylic resins are preferable. Since the acrylic resin has a low glass transition temperature, the initial adhesion can be improved.
Here, the initial adhesion refers to adhesion in an initial stage when the semiconductor element and the support member are bonded with the semiconductor adhesive film, that is, adhesion before the semiconductor adhesive film is cured.

The acrylic resin means a resin having acrylic acid and its derivatives as main monomers. Specifically, polymers such as acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, etc., methacrylates such as methyl methacrylate, ethyl methacrylate, acrylonitrile, acrylamide, and other monomers And the like.
An acrylic resin (particularly an acrylic acid copolymer) having a compound having an epoxy group, a hydroxyl group, a carboxyl group, a nitrile group, or the like is preferable. Thereby, the adhesiveness to adherends, such as a semiconductor element, can be improved more. Specific examples of the compound having a functional group include glycidyl methacrylate having a glycidyl ether group, hydroxy methacrylate having a hydroxyl group, carboxy methacrylate having a carboxyl group, and acrylonitrile having a nitrile group.
Among these, an acrylate copolymer containing a compound having a nitrile group is particularly preferable. Thereby, the adhesiveness to a to-be-adhered body can be improved especially.

  The content of the compound having a functional group is not particularly limited, but is preferably 0.5% by weight or more and 40% by weight or less, and particularly preferably 5% by weight or more and 30% by weight or less of the entire acrylic resin. When the content is 0.5% by weight or more, the effect of improving the adhesion is enhanced, and when it is 40% by weight or less, the adhesive force can be suppressed, so that the effect of improving workability is enhanced.

  (A) Although the weight average molecular weight of a thermoplastic resin, especially acrylic resin is not specifically limited, 100,000 or more are preferable and 150,000-1 million are especially preferable. When the weight average molecular weight is within this range, the film forming property of the adhesive film for a semiconductor can be improved. Further, when the weight average molecular weight is within this range, even when the thermoplastic resin contains a thermosetting functional group, the resin alone hardly exhibits the curing behavior by heat treatment.

  (A) Although the glass transition temperature of a thermoplastic resin is not specifically limited, -20 degreeC or more and 60 degrees C or less are preferable, and -10 degreeC or more and 50 degrees C or less are especially preferable. Since the adhesive force of the adhesive film for a semiconductor can be suppressed when the glass transition temperature is −20 ° C. or higher, the effect of improving workability is enhanced. When the glass transition temperature is 60 ° C. or lower, the low-temperature adhesiveness can be improved.

(A) Thermoplastic resin content is (A) thermoplastic resin a part by weight, (B) epoxy resin b part by weight, (C) phenol resin c part by weight, and (D) radiation polymerizable monomer d part by weight. Parts, 0.1 ≦ a / (b + c + d) ≦ 0.7 is preferable, more preferably 0.15 ≦ a / (b + c + d) ≦ 0.6, and 0.2 ≦ a / (b + c + d). ≦ 0.4 is particularly preferred. When it is 0.1 or more, the film formability of the resin composition is improved, and the toughness of the adhesive film for a semiconductor is improved. When it is 0.7 or less, the fluidity at the time of application of the film adhesive is improved, and the film adhesive can be filled into the circuit step of the organic substrate when thermocompression bonding is performed.

  The (B) epoxy resin used in the present invention refers to any of a monomer, an oligomer and a polymer. For example, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic type epoxy resin, stilbene type epoxy resin, orthocresol novolak type epoxy resin, phenol novolak type epoxy resin, Modified phenol type epoxy resin, triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin, triazine nucleus-containing epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, glycidyl Examples include amine type epoxy resins, bisphenol A novolac type epoxy resins, brominated phenol novolac type epoxy resins, and naphthol type epoxy resins. .

  The content of the epoxy resin is preferably 10 to 100 parts by weight, particularly preferably 20 to 50 parts by weight, with respect to 10 parts by weight of the thermoplastic resin. When the content is equal to or higher than the lower limit, fluidity at the time of pasting is improved, and when the content is equal to or lower than the upper limit, the toughness of the adhesive film for a semiconductor can be improved.

Furthermore, when the total weight of the epoxy resin (B), phenol resin (C) and (D) radiation polymerizable monomer is 100 parts by weight, the epoxy resin is 20 parts by weight or more and 80 parts by weight or less, preferably 40 parts by weight or more and 70 parts by weight. It is preferable that the content is not more than part by weight. When the content is equal to or higher than the lower limit value, the fluidity is improved during thermocompression bonding, and it becomes possible to fill a gap between the circuit and the circuit provided on the organic substrate. The toughness of the adhesive film for a semiconductor improves that it is below the upper limit value, and film cracking during film cutting can be suppressed.

The (C) phenolic resin used in the present invention refers to monomers, oligomers, and polymers in general having at least two or more phenolic hydroxyl groups capable of forming a crosslinked structure by a curing reaction with the above epoxy resin. Phenol novolak resin, cresol novolak resin, phenol aralkyl (including phenylene and biphenylene skeleton) resin, naphthol aralkyl resin, triphenolmethane resin, dicyclopentadiene type phenol resin and the like. These may be used alone or in combination.

  The content of the phenol resin is not particularly limited, but the ratio of the epoxy equivalent of the epoxy resin to the hydroxyl equivalent of the phenol curing agent is preferably 0.5 or more and 1.5 or less, particularly 0.7 or more and 1.3 or less. preferable. When the equivalent ratio is not less than the lower limit, the heat resistance of the adhesive film for semiconductor is improved, and when it is not more than the upper limit, the storage stability of the adhesive film for semiconductor is improved.

The (D) radiation polymerizable monomer used in the present invention is a monomer having a radiation polymerizable carbon-carbon double bond in the molecule. As a specific example, at least selected from the group consisting of an ultraviolet curable resin mainly composed of an acrylic compound, an ultraviolet curable resin mainly composed of a urethane acrylate oligomer or a polyester urethane acrylate oligomer, an epoxy resin, and a vinyl phenol resin. Examples thereof include an ultraviolet curable resin mainly composed of one kind.
Among these, an ultraviolet curable resin mainly composed of an acrylic compound is preferable. Thereby, initial adhesiveness can be improved more and the brittleness of a film adhesive can be improved further. Examples of the acrylic compounds include monomers of acrylic acid esters or methacrylic acid esters. Specifically, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, and 1,6 dimethacrylate. -Bifunctional acrylate such as hexanediol, glyceryl diacrylate, glyceryl dimethacrylate, 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Examples include polyfunctional acrylates such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. That. Among these, acrylic acid esters are preferable, and acrylic acid esters, methacrylic acid alkyl esters, and trimethylolpropane trimethacrylate having 1 to 15 carbon atoms in the ester moiety are particularly preferable.

  The content of the (D) radiation polymerizable monomer is 0.02 when (B) epoxy resin b parts by weight, (C) phenol resin c parts by weight, and (D) radiation polymerizable monomer d parts by weight. ≦ d / (b + c + d) ≦ 0.5 is preferable, and 0.05 ≦ d / (b + c + d) ≦ 0.3 is particularly preferable. Further, although not particularly limited, 20 to 55 parts by weight is preferable with respect to 10 parts by weight of the plastic resin, and 30 to 40 parts by weight is particularly preferable. When the content is equal to or higher than the lower limit, the fluidity at the time of thermocompression bonding is improved, and it is possible to fill a gap between the circuit provided on the organic substrate and further improve the toughness of the film adhesive. It becomes possible to suppress film breakage when cutting the film adhesive. Heat resistance improves that it is below the said upper limit, and generation | occurrence | production of the decomposition gas at the time of thermocompression bonding can be suppressed.

  Furthermore, the total weight of the epoxy resin (B), phenol resin (C), and (D) radiation polymerizable monomer is preferably 15 parts by weight or more and 100 parts by weight or less with respect to 10 parts by weight of the thermoplastic resin (A). Further, it is particularly preferably 25 parts by weight or more and 80 parts by weight or less. When the content is equal to or higher than the lower limit, the fluidity at the time of thermocompression bonding is improved, and it is possible to fill a gap between the circuit provided on the organic substrate and further improve the toughness of the film adhesive. It becomes possible to suppress film breakage when cutting the film adhesive. Heat resistance improves that it is below the said upper limit, and generation | occurrence | production of the decomposition gas at the time of thermocompression bonding can be suppressed.

In order to accelerate the curing reaction, the resin composition may contain (E) a curing accelerator as necessary. Specific examples of the curing accelerator include amine catalysts such as imidazoles, 1,8-diazabicyclo (5,4,0) undecene, and phosphorus catalysts such as triphenylphosphine.

  Moreover, it is preferable to use (F) a radiation curing initiator in combination with the (D) radiation polymerizable monomer. Thereby, when it is difficult to peel the adhesive film for a semiconductor from the support base material, the surface of the adhesive film for a semiconductor can be cured by irradiating ultraviolet rays to facilitate the peeling.

The type of (F) radiation curing initiator used in the present invention is not particularly limited. For example, benzophenone, acetophenone, benzoin, benzoin isobutyl ether, methyl benzoin benzoate, benzoin benzoic acid, benzoin methyl ether, benzylfinyl sulfide, Examples include benzyl, dibenzyl, diacetyl and the like.

Although content of the said (F) radiation curing initiator is not specifically limited, 1-30 weight part is preferable with respect to 100 weight part of said radiation polymerizable monomers (D), and 3-15 weight part is especially preferable. When the content is not less than the lower limit, the effect of initiating photopolymerization is enhanced, and when the content is not more than the upper limit, the preservability of the adhesive film for semiconductor is improved.

The film adhesive layer of the present invention can further contain a coupling agent as required. Thereby, the adhesiveness between the resin and the adherend and between the resin and the silica interface can be improved.

  Examples of coupling agents include silane-based, titanium-based, and aluminum-based, among which silane-based coupling agents are preferable. As the coupling agent, for example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Methyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (Aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ Aminopropyltrimethoxysilane, .gamma.-chloropropyl trimethoxy silane, .gamma.-mercaptopropyltrimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-acryloxypropyl and propyl trimethoxy silane.

Although the compounding quantity of the said coupling agent is not specifically limited, 0.01-10 weight part is preferable with respect to 100 weight part of said acrylate ester copolymers, and 0.1-10 weight part is especially preferable. When the blending amount is equal to or higher than the lower limit value, the effect of improving the adhesion is enhanced, and when it is equal to or lower than the upper limit value, generation of outgas and voids can be suppressed.

The resin composition may contain an organic compound having a cyanate group as another component, if necessary. Thereby, the adhesiveness to a to-be-adhered body and heat resistance can be improved more.
Examples of the organic compound having a cyanate group include bisphenol A dicyanate, bisphenol F dicyanate, bis (4-cyanate phenyl) ether, bisphenol E dicyanate, and cyanate novolac resin.

Next, the second adhesive film for a semiconductor of the present invention will be described.
The second adhesive film for a semiconductor of the present invention is
A semiconductor adhesive film containing a thermoplastic resin and an epoxy resin,
(i) When the temperature is raised from 25 ° C. at a rate of 10 ° C./min, the minimum melt viscosity is 0.1 [Pa · s] or more and 50 [Pa · s] or less in the region of 50 ° C. or more and 180 ° C. or less. It is an adhesive film for semiconductors characterized by being.
The second semiconductor adhesive film of the present invention is obtained, for example, by a resin composition containing A) a thermoplastic resin, (B) an epoxy resin, (C) a phenol resin, and (D) a radiation polymerizable monomer.

Configuration (ii) When the temperature is increased from 25 ° C. at a rate of 10 ° C./min, the melt viscosity is 0.1 [Pa · s] or more and 50 [Pa · s in the region of 50 ° C. or more and 180 ° C. or less. The term "below" means a requirement that the melt viscosity should be satisfied in order to bond at a relatively low temperature and a low load and to fill a gap between circuits provided on the organic substrate. In order to prevent thermal damage of the chip and to fill a gap between the circuit provided on the organic substrate, it is necessary to apply the chip at a relatively low temperature and a low load.
The melt viscosity in the present invention can be measured, for example, using a rheometer which is a viscoelasticity measuring device by applying shear shear at a frequency of 1 Hz to a film-like sample at a heating rate of 10 ° C./min.

FIG. 1 schematically shows the relationship of the melt viscosity to the temperature of the adhesive film for semiconductors of the present invention.
As shown in FIG. 1, the adhesive film for semiconductor of the present invention has an initial decrease in melt viscosity when the temperature of the adhesive film for semiconductor is increased from 25 ° C. to a molten state at a temperature increase rate of 10 ° C./min. The arrow A) in the figure has a characteristic of further increasing (arrow B in the figure) after reaching the minimum melt viscosity (η1) at a predetermined temperature (t1).

At this time, the minimum melt viscosity in the region of 50 ° C. to 180 ° C. of the adhesive film for semiconductor is preferably 0.1 [Pa · s] or more and 50 [Pa · s] or less. Furthermore, the melt viscosity is preferably 1 [Pa · s] or more and 30 [Pa · s] or less, and particularly preferably 5 [Pa · s] or more and 15 [Pa · s] or less. When it is 50 [Pa · s] or less, fluidity is improved during thermocompression bonding, and it is possible to fill a gap between the circuit and the circuit provided on the organic substrate. Since it can suppress that the adhesive film for semiconductors flows more than necessary as it is 0.1 [Pa * s] or more, the danger of contaminating a semiconductor element becomes low.

  The minimum melt viscosity is 15 to 100 parts by weight of the total amount of the radiation-polymerizable monomer having a radiation-polymerizable carbon-carbon double bond in the molecule with respect to 10 parts by weight of the thermoplastic resin. Thus, it can be obtained by producing an adhesive film for a semiconductor having a high ratio of low-molecular monomers having high fluidity.

The minimum melt viscosity of a conventional adhesive film for a semiconductor (for example, a polyimide-based adhesive film) was about 3000 [Pa · s]. Therefore, it is necessary to bond the semiconductor element and the semiconductor element mounting support member at a high temperature of about 180 ° C. However, since the semiconductor element and the semiconductor element mounting support member are bonded at such a high temperature, the semiconductor element may be thermally damaged.
On the other hand, since the adhesive film for semiconductors of the present invention has a low minimum melt viscosity, the semiconductor element and the semiconductor mounting support member can be bonded even if the thermocompression bonding temperature is lowered. The thermocompression bonding temperature in the present invention is preferably from 80 ° C to 150 ° C.

The melt viscosity at 250 ° C. after heat treatment at 175 ° C. for 2 hours is 5,000 [Pa · s] or more. Further, it is preferably 10,000 [Pa · s] or more, particularly preferably 20,000 [Pa · s] or more. When the melt viscosity at 250 ° C. is within the above range, the heat resistance and the crack resistance during reflow are particularly excellent.

  In addition to the minimum melt viscosity being 0.1 [Pa · s] or more and 50 [Pa · s] or less in the region of 100 ° C. to 180 ° C., the melt viscosity at 250 ° C. after heat treatment at 175 ° C. for 2 hours is in the above range. If it is inside, it is possible to obtain an adhesive film for a semiconductor having both excellent circuit step filling performance, low-temperature adhesiveness and heat resistance.

The adhesive film for semiconductors of the present invention is prepared by, for example, dissolving the resin composition in a solvent such as methyl ethyl ketone, acetone, toluene, dimethylformaldehyde, etc. to make a varnish, and then using a comma coater, die coater, gravure coater, etc. It can be obtained by coating the release sheet, drying it, and then removing the release sheet.
Although the thickness of the said adhesive film for semiconductors is not specifically limited, 3 micrometers or more and 100 micrometers or less are preferable, and 5 micrometers or more and 70 micrometers or less are especially preferable. When the thickness is within the above range, it is particularly easy to control the thickness accuracy.

First, the Example and comparative example of the adhesive film for semiconductors are demonstrated.
Example 1
(1) Preparation of Adhesive Film Resin Varnish for Semiconductor Acrylic ester copolymer (butyl acrylate-acrylonitrile-ethyl acrylate-glycidyl methacrylate copolymer, manufactured by Nagase ChemteX Corporation, SG-80 HDR as thermoplastic resin (A) , Tg: 10 ° C., weight average molecular weight: 350,000) and epoxy resin (EOCN-1020-80 (orthocresol novolac type epoxy resin) as an curable resin, epoxy equivalent 200 g / eq, Nippon Kayaku ( 27 parts by weight), phenol resin (MEH-7500 (triphenol methane resin), hydroxyl group equivalent 97 g / OH group, Meiwa Kasei Co., Ltd.) 13 parts by weight, radiation polymerizable monomer (TMP (trimethylolpropane) Trimethacrylate), Kyoeisha Chemical Co., Ltd.) 8 layers Parts by weight, 0.1 parts by weight of an imidazole compound (2PHZ-PW, manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator (E), and benzyldimethyl ketal (Ciba Specialty Chemicals Co., Ltd.) as a radiation curing initiator (F) Manufactured by Irgacure 651) 0.7 parts by weight and 0.1 parts by weight of γ-glycidoxypropyltrimethoxysilane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent dissolved in methyl ethyl ketone (MEK) A resin varnish with a content of 37% was obtained.

(2) Manufacture of adhesive film for semiconductor After applying the above-mentioned resin varnish to a polyethylene terephthalate film (manufactured by Oji Paper Co., product number RL-07, thickness 38 μm) as a protective film using a comma coater, It was dried for 10 minutes to obtain an adhesive film for semiconductor having a thickness of 25 μm.

(3) Manufacture of semiconductor device The above-mentioned adhesive film surface for semiconductor is laminated on the back surface of a 5-inch, 100 μm semiconductor wafer under the conditions of 80 ° C., 0.1 MPa, 50 mm / sec, and the adhesive film surface for semiconductor is diced (Sumilite). FSL-N4003, manufactured by Sumitomo Bakelite Co., Ltd.). Then, using a dicing saw, the semiconductor wafer bonded with the semiconductor adhesive film is diced (cut) into a semiconductor element size of 5 mm × 5 mm square at a spindle rotation speed of 50,000 rpm and a cutting speed of 50 mm / sec. A semiconductor element to which an adhesive film was bonded was obtained. Next, after irradiating ultraviolet rays with an integrated light amount of 250 mJ / cm ² in 20 seconds from the light-transmitting substrate side of the dicing film, the dicing film bonded to the adhesive film for semiconductor was peeled off. And the bismaleimide * which coat | covered the semiconductor element which the above-mentioned adhesive film for semiconductors joined with the soldering resist (Taiyo Ink Co., Ltd. product, AUS308).
It is pressure-bonded to an organic substrate (circuit level difference: 10 μm) containing triazine as a main material at 130 ° C., 5 N for 1.0 second, die-bonded, 100 ° C., 1 hour, further 120 ° C., 1 hour, and further 180 ° C. for 1 hour. After heat-treating and curing the semiconductor adhesive film, it was encapsulated with resin and heat-treated at 175 ° C. for 2 hours to cure the encapsulating resin to obtain 10 semiconductor devices.

(4) Evaluation of adhesive film for semiconductors Low temperature adhesion (initial adhesion)
The low-temperature adhesiveness was obtained by bonding a semiconductor adhesive film obtained on a semiconductor element (organic substrate) under conditions of 130 ° C., 5 N, and 1 second, and then measuring die shear strength.
The die shear strength was measured using a push-pull gauge. Each code is as follows.
◎: Die shear strength is 3.0 MPa or more ○: Die shear strength is 2.0 MPa or more and less than 3.0 M △: Die shear strength is 1.0 MPa or more and less than 2.0 MPa ×: Die shear strength is less than 1.0 MPa

Heat resistance Heat resistance was evaluated based on a 5% weight reduction temperature of the adhesive film for semiconductors. Each code is as follows.
A: 5% weight reduction temperature is 300 ° C. or more. ○: 5% weight reduction temperature is 250 ° C. or more and less than 300 ° C. Δ: 5% weight reduction temperature is 200 ° C. or more and less than 250 ° C. ×: 5% weight reduction temperature is Less than 200 ° C

The brittleness of the film The brittleness of the film was evaluated by measuring the number of times until the adhesive film for semiconductors was broken by peeling the adhesive film for semiconductors from the substrate and performing a 180-degree bending test. Each code is as follows.
◎: The number of foldable times is 50 times or more. ○: The number of foldable times is 25 times or more and less than 50 times. △: The number of foldable times is 1 time or more and less than 25 times.

Circuit fillability Circuit fillability is achieved by bonding a semiconductor adhesive film obtained on a semiconductor element (organic substrate) under the conditions of 130 ° C, 5N, and 1 second, and using a scanning ultrasonic flaw detector (SAT) on the organic substrate. The rate at which the adhesive film for a semiconductor was filled in the circuit step was evaluated. Each code is as follows.
A: Filling rate is 100%
○: Filling rate is 80% or more and less than 100% Δ: Filling rate is 40% or more and less than 80% ×: Filling rate is less than 40%

(5) Evaluation of semiconductor device produced using adhesive film for semiconductor Adhesiveness after moisture absorption treatment The semiconductor device before resin sealing obtained in each Example and Comparative Example was subjected to moisture absorption treatment at 85 ° C./85% RH / 168 hours. Then, the shear strength at 260 ° C. between the semiconductor element and the organic substrate was evaluated.
◎: Shear strength is 1.0 MPa or more ○: Shear strength is 0.75 or more and less than 1.0 MPa △: Shear strength is 0.5 or more and less than 0.75 MPa ×: Shear strength is less than 0.5 MPa

Crack resistance Crack resistance is the result of scanning ultrasonic flaw detection by subjecting the semiconductor devices obtained in each of the examples and comparative examples to moisture absorption treatment at 85 ° C./85% RH / 168 hours, followed by IR reflow at 260 ° C. three times. Machine (SAT). Each code is as follows.
A: Generated cracks 0 out of 10 O: Generated cracks 1 to 3 out of 10 Δ: Generated cracks 4 to 9 out of 10 ×: Generated cracks 10 out of 10

Table 1 shows the physical properties of the semiconductor adhesive film obtained in Example 1, various evaluation results, and details of the evaluation results of the semiconductor device using the semiconductor adhesive film.

(Example 2)
The experiment was performed in the same manner as in Example 1 except that NC6000 (epoxy equivalent 200 g / eq, manufactured by Nippon Kayaku Co., Ltd.) and 27 parts by weight were used as the epoxy resin (B). The formulation and experimental results are shown in Table 1.

(Example 3)
Experiments were conducted in the same manner as in Example 1 except that XLC-4L (phenol aralkyl resin), hydroxyl group equivalent 170 g / OH group, manufactured by Mitsui Chemicals, Inc., and 23 parts by weight were used as the phenol resin (C). . The formulation and experimental results are shown in Table 1.

Example 4
The experiment was conducted in the same manner as in Example 1 except that 1,6-hexanediol dimethacrylate (1,6-HX, manufacturer: Kyoeisha Chemical Co., Ltd.) and 18 parts by weight were used as the radiation polymerizable monomer (D). went. The formulation and experimental results are shown in Table 1.

(Example 5)
As the epoxy resin (B), (EOCN-1020-80 (orthocresol novolac type epoxy resin), epoxy equivalent 200 g / eq, manufactured by Nippon Kayaku Co., Ltd.) 9 parts by weight, NC6000 (epoxy equivalent 200 g / eq, Nippon Chemical) Yakuhin Co., Ltd.), 13 parts by weight, except that XLC-4L (phenol aralkyl resin), hydroxyl group equivalent 170 g / OH group, Mitsui Chemicals), 18 parts by weight was used as the phenol resin (C). The experiment was conducted in the same manner as in Example 1. The formulation and experimental results are shown in Table 1.

(Example 6)
As epoxy resin (B), (EOCN-1020-80 (orthocresol novolac type epoxy resin), epoxy equivalent 200 g / eq, manufactured by Nippon Kayaku Co., Ltd.) 54 parts by weight, as phenol resin (C) (MEH-7500) (Triphenolmethane resin), hydroxyl group equivalent 97 g / OH group, 26 parts by weight of Meiwa Kasei Co., Ltd., trimethylolpropane trimethacrylate (TMP, manufacturer: Kyoeisha Chemical Co., Ltd.) 16 as radiation polymerizable monomer (D) Parts by weight, 0.2 parts by weight of an imidazole compound (2PHZ-PW, manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator (E), and benzyldimethyl ketal (Ciba Specialty Chemicals Co., Ltd.) as a radiation curing initiator (F) Manufactured, Irgacure 651) An experiment was conducted in the same manner as in Example 1 except that 2 parts by weight were used. The formulation and experimental results are shown in Table 1.

(Example 7)
As epoxy resin (B), (EOCN-1020-80 (orthocresol novolac type epoxy resin), epoxy equivalent 200 g / eq, manufactured by Nippon Kayaku Co., Ltd.) 9 parts by weight, and phenol resin (C) (MEH-7500) (Triphenolmethane resin), hydroxyl group equivalent 97 g / OH group, 4 parts by weight of Meiwa Kasei Co., Ltd., trimethylolpropane trimethacrylate (TMP, manufacturer: Kyoeisha Chemical Co., Ltd.) 2 as radiation polymerizable monomer (D) The experiment was performed in the same manner as in Example 1 except that 0.2 parts by weight of benzyldimethyl ketal (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 651) was used as the radiation curing initiator (F). The formulation and experimental results are shown in Table 1.

(Example 8)
1 part by weight of trimethylolpropane trimethacrylate (TMP, manufacturer: Kyoeisha Chemical Co., Ltd.) as the radiation polymerizable monomer (D), benzyldimethyl ketal (manufactured by Ciba Specialty Chemicals Co., Ltd.) as the radiation curing initiator (F), Irgacure 651) An experiment was conducted in the same manner as in Example 1 except that 0.1 part by weight was used. The formulation and experimental results are shown in Table 1.

Example 9
40 parts by weight of trimethylolpropane trimethacrylate (TMP, manufacturer: Kyoeisha Chemical Co., Ltd.) as the radiation polymerizable monomer (D), and benzyldimethyl ketal (manufactured by Ciba Specialty Chemicals Co., Ltd.) as the radiation curing initiator (F), Irgacure 651) An experiment was conducted in the same manner as in Example 1 except that 4 parts by weight were used. The formulation and experimental results are shown in Table 1.

(Comparative Example 1)
The experiment was performed in the same manner as in Example 1 except that the epoxy resin (B), the phenol resin (C), the radiation polymerizable monomer (D), the curing accelerator (E), and the radiation curing initiator (F) were not used. It was. The formulation and experimental results are shown in Table 1.

(Comparative Example 2)
As the thermoplastic resin (A), an acrylate copolymer (butyl acrylate-acrylonitrile-ethyl acrylate-glycidyl methacrylate copolymer, manufactured by Nagase ChemteX Corporation, SG-80 HDR, Tg: 10 ° C., weight average molecular weight: 350 , 000) 100 parts by weight, except that 100 parts by weight were used. The formulation and experimental results are shown in Table 1.

(Comparative Example 3)
As epoxy resin (B), (EOCN-1020-80 (orthocresol novolac type epoxy resin), epoxy equivalent 200 g / eq, manufactured by Nippon Kayaku Co., Ltd.) 135 parts by weight, as phenol resin (C) (MEH-7500) The experiment was performed in the same manner as in Example 1 except that 65 parts by weight (triphenolmethane resin), hydroxyl group equivalent of 97 g / OH group, manufactured by Meiwa Kasei Co., Ltd. was used. The formulation and experimental results are shown in Table 1.

(Comparative Example 4)
The experiment was performed in the same manner as in Example 1 except that the radiation polymerizable monomer (D) and the radiation curing initiator (F) were not used. The formulation and experimental results are shown in Table 1.

(Comparative Example 5)
110 parts by weight of trimethylolpropane trimethacrylate (TMP, manufacturer: Kyoeisha Chemical Co., Ltd.) as the radiation polymerizable monomer (D), and benzyldimethyl ketal (manufactured by Ciba Specialty Chemicals Co., Ltd.) as the radiation curing initiator (F), Irgacure 651) An experiment was conducted in the same manner as in Example 1 except that 10 parts by weight were used. The formulation and experimental results are shown in Table 1.

(Comparative Example 6)
Polyimide resin as the thermoplastic resin (A) (1,3-bis (3-aminophenoxy) benzene (made by Mitsui Chemicals, Inc.) APB as the diamine component) 43.85 g (0.15 mol) and α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 837) (G9 manufactured by Fuso Chemical Co., Ltd.) 125.55 g (0.15 mol) and 4,4′-oxydiphthalic dianhydride (Manac ( ODPA-M), a polyimide resin obtained by synthesizing 93.07 g (0.30 mol), Tg: 70 ° C., weight average molecular weight 30,000) 100 parts by weight, and epoxy resin (B), EOCN-1020-80 (orthocresol novolac type epoxy resin), epoxy equivalent 200 g / eq, Nippon Kayaku Co., Ltd. 10 parts by weight, coupling agent (G As a solution, 5 parts by weight of N-phenyl-γ-aminopropyltrimethoxysilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in N-methyl-2-pyrrolidone (NMP) to prepare a resin varnish having a resin solid content of 43%. This was applied to a polyethylene terephthalate film (Mitsubishi Chemical Polyester Film Co., Ltd., product number MRX-50, thickness 50 μm), which was a protective film, and then dried at 180 ° C. for 10 minutes for a semiconductor with a thickness of 25 μm. An adhesive film was prepared and evaluated using the adhesive film. The experimental results are shown in Table 1.

  As shown in Table 1, in Examples 1 to 9, both the adhesive film evaluation results and the semiconductor device evaluation results showed good results, but in Comparative Examples 1 to 6, all of these showed good results. There wasn't. Moreover, although the adhesive film physical properties of Examples 1-9 all satisfy the characteristics of claim 6, none of the comparative examples, which are prior arts, satisfy the characteristics of claim 6.

It is the figure which showed typically the relationship of the melt viscosity with respect to the temperature of the adhesive film for semiconductors of this invention.

It is sectional drawing of the semiconductor device which shows an example of the semiconductor device of this invention typically.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Adhesive film for semiconductors 2 Semiconductor element 3 Support member for semiconductor mounting

Claims (6)

(A) thermoplastic resin a parts by weight,
(B) Epoxy resin b parts by weight,
(C) phenol resin c parts by weight, and
(D) radiation-polymerizable monomer d parts by weight,
A film for semiconductor adhesion, wherein the a to d satisfy the following conditions (I) and (II).
(I) 0.1 ≦ a / (b + c + d) ≦ 0.7
(II) 0.02 ≦ d / (b + c + d) ≦ 0.5   2. The adhesive film for semiconductor according to claim 1, wherein the thermoplastic resin is an acrylate copolymer. The adhesive film for semiconductor according to claim 1 or 2, further comprising (E) a curing accelerator. The adhesive film for semiconductor according to claim 1, further comprising (F) a radiation curing initiator. (A) a thermoplastic resin, (B) an adhesive film for a semiconductor containing an epoxy resin,
When the temperature is raised from 25 ° C. at a rate of 10 ° C./min, the minimum melt viscosity is 0.1 [Pa · s] or more and 50 [Pa · s] or less in the region of 50 ° C. or more and 180 ° C. or less. A characteristic adhesive film for semiconductors. A semiconductor device having a structure in which a semiconductor element and a member to be bonded are bonded using the adhesive film for a semiconductor according to claim 1.