JP2007157758A - Adhesive film for semiconductor and semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor device wherein a semiconductor element and a supporting member for mounting a semiconductor element, especially an organic substrate can be adhered without any gap while suppressing voids and which is superior in reliability. <P>SOLUTION: An adhesive film for a semiconductor is comprised of (A) thermoplastic resin, (B) epoxy resin, and (C) a curing agent. When the adhesive film therefor is heated at a temperature rising rate of 10°C/min from room temperature; its minimum melting viscosity is ≥0.1 Pa s and ≤500 Pa s in a range between 50°C and 180°C, and its volatile content is 5.0% or less. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  In recent semiconductor packages, the use of organic substrates such as bismaleimide-triazine substrates and polyimide substrates instead of lead frames is increasing.

The semiconductor package includes a semiconductor element, a semiconductor element mounting support member, and a sealing material, and a polyimide semiconductor adhesive film or the like is used to join the semiconductor element and the semiconductor element mounting support member. It was done.
JP-A-6-264035 Japanese Patent Laid-Open No. 2000-200793 JP 2003-96426 A

However, the prior art described in the above literature has room for improvement in the following points.
When a semiconductor device having a structure in which a semiconductor element and an organic substrate are bonded to each other using a conventionally known adhesive film for a semiconductor is produced, there is a problem that the reliability is low because cracks are easily generated.
In the present invention, the minimum melt viscosity in the range of 50 ° C. to 180 ° C. when the temperature is raised from room temperature at a rate of 10 ° C./min is 0.1 Pa · s to 500 Pa · s, and the volatile content is It has been found that the reliability of the semiconductor device can be improved by setting it to 5.0% or less.

The present invention is an adhesive film for a semiconductor comprising (A) a thermoplastic resin, (B) an epoxy resin, and (C) a curing agent, and the rate of temperature increase of the semiconductor adhesive film from room temperature to 10 ° C./min. The minimum melt viscosity in the range of 50 ° C. or higher and 180 ° C. or lower when heated at a temperature of 0.1 Pa · s to 500 Pa · s and the volatile content is 5.0% or less The present invention relates to an adhesive film.
The adhesive film for a semiconductor of the present invention has a minimum melt viscosity within a specific range in a specific temperature range. The temperature range is a temperature that can be set when a film is applied, and when the adhesive film for a semiconductor of the present invention is applied at a temperature near the minimum melt viscosity, a moderately low melt viscosity can be realized. The adhesive fills the irregularities of the circuit board without any gaps. In addition, when the volatile content of the filled material is large, gas is generated and causes cracks. At the same time, the generation of voids due to gas generation can be prevented by setting the volatile content to 5.0% or less.

  By using the semiconductor adhesive film of the present invention, it is possible to bond a semiconductor element and a supporting member for mounting a semiconductor element, in particular, an organic substrate without gaps while suppressing generation of voids, and to provide a highly reliable semiconductor device. Can do.

The adhesive film for a semiconductor of the present invention is
(A) a thermoplastic resin, (B) an epoxy resin, and (C) a semiconductor adhesive film containing a curing agent,
The minimum melt viscosity in the range of 50 ° C. or higher and 180 ° C. or lower when the temperature of the adhesive film for semiconductor is raised from room temperature at a temperature rising rate of 10 ° C./min is 0.1 Pa · s to 500 Pa · s, and A volatile content is 5.0% or less.

  When a semiconductor device is manufactured by bonding a semiconductor element to a support member for mounting a semiconductor element using a polyimide-based semiconductor adhesive film, which is a conventional adhesive film for semiconductors, there is a problem in reliability, such as cracking is likely to occur at the bonding interface. there were. The inventors have conducted extensive research using a cross-sectional analysis or a scanning ultrasonic flaw detector (SAT) analysis of a conventional semiconductor device. As a result, when a conventional adhesive film for a semiconductor is used, the semiconductor device It was found that there was a gap between the semiconductor element and the semiconductor element mounting support member in the state immediately after fabrication.

  This phenomenon was prominent when an organic substrate provided with metal wiring on the surface was used as a semiconductor element mounting support member. When metal wiring is provided on the organic substrate, unevenness due to the thickness of the wiring occurs, and this unevenness cannot be properly filled with the adhesive film for semiconductor when bonded to the semiconductor element, and remains as a void. It is thought that this causes deterioration of reliability.

The inventors believe that the reason why the unevenness is not properly embedded is due to the high melt viscosity of the adhesive film for semiconductors during bonding, and the melting of the polyimide-based semiconductor adhesive film that is a conventional adhesive film for semiconductors. When the viscosity was examined, the melt viscosity at the attaching temperature was about 4000 Pa · s.
In the present invention, the melt viscosity of the adhesive film for semiconductor at the time of bonding is set to 0.1 Pa · s or more and 500 Pa · s or less, which is sufficiently lower than the conventional melt viscosity, and additionally the volatile content is suppressed to 5.0% or less. Thus, it has been found that there is an effect of more appropriately filling the gap and improving the reliability of the semiconductor device. Moreover, the heat damage of a semiconductor element can be prevented by setting the temperature which implement | achieves the said melt viscosity to 50 to 180 degreeC comparatively lower than the conventional adhesion temperature.

  In the present invention, the minimum melt viscosity in the range of 50 ° C. or higher and 180 ° C. or lower when the temperature is raised from room temperature at a rate of 10 ° C./min is measured, and the value is 0.1 Pa · s or higher and 500 Pa · s or lower. If so, it is possible to set an appropriate bonding temperature by employing a temperature in the vicinity of the minimum melt viscosity as the bonding temperature.

  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 sample in a film state at a heating rate of 10 ° C./min.

  FIG. 1 schematically shows an example of 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).

  In this case, the minimum melt viscosity is designed to be 0.1 [Pa · s] or more and 500 [Pa · s] or less in the region of 50 to 180 ° C. of the adhesive film for semiconductor. Further, the melt viscosity is preferably 1 [Pa · s] or more and 100 [Pa · s] or less, and particularly preferably 5 [Pa · s] or more and 50 [Pa · s] or less. When it is 500 [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. When it is 0.1 [Pa · s] or more, it is possible to suppress the semiconductor adhesive film from flowing more than necessary, so that the risk of contaminating the semiconductor element is reduced, and further the semiconductor adhesive film is heated and cured. In addition, it is possible to suppress the generation of voids due to the gas film generated from the organic substrate being involved in the semiconductor adhesive film.

The above-mentioned minimum melt viscosity is (A) a thermoplastic resin, (B) an epoxy resin (C) a curing agent, and (B) an epoxy resin or (C) a curing agent having a low fluidity at 25 ° C. It is obtained by a method using molecular monomers. At this time, when a monomer that is solid at 25 ° C. is used in combination, the tackiness at room temperature of the semiconductor adhesive film can be suppressed and the workability can be improved while designing the minimum melt viscosity within this range.
Or a component which is liquid at 25 ° C. and does not react with (A) a thermoplastic resin such as a monomer having a radiation-polymerizable carbon-carbon double bond in the molecule, or (B) an epoxy resin (C) curing agent. The method of adding is mentioned. 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.
Furthermore, it can be obtained by a method of increasing the content of (B) epoxy resin (C) curing agent relative to (A) thermoplastic resin. Specifically, when (A) thermoplastic resin a part by weight, (B) epoxy resin b part by weight, (C) curing agent c part by weight, 0.1 ≦ a / (a + b + c) ≦ 0.5. It is obtained by.

  The volatile content of the adhesive film for a semiconductor of the present invention is 5.0% or less. For example, when the adhesive film for a semiconductor cut into a square of 50 mm × 50 mm is heat-treated at 200 ° C./2 h, the weight loss before and after heating is measured as the volatile content. In the present invention, the volatile content is preferably 3.0% or less. When the volatile content is lower than the upper limit, when the semiconductor adhesive film is cured by heat treatment, no gas component is generated from the film when the melt viscosity of the semiconductor adhesive film is lowered, and no void is generated from the film. Therefore, when the semiconductor device is mounted on a printed circuit board, the occurrence of cracks due to the thermal expansion of voids in the film can be suppressed when the semiconductor device is brought into a high temperature state by a reflow furnace.

  The die shear strength after bonding of the adhesive film for a semiconductor of the present invention is preferably 1 MPa or more, and more preferably 2 MPa or more. The die shear strength is between a bismaleimide-triazine substrate coated with an adhesive film for semiconductor coated with a silicon chip having a size of 4 × 4 mm and a thickness of 550 μm and a solder resist (manufactured by Taiyo Ink Manufacturing Co., Ltd .: trade name: AUS308). The sample that was thermocompression bonded at 130 ° C, 5N for 1 second and cured by heat treatment was held on a 260 ° C hot platen for 20 seconds, and then at a speed of 0.5 mm / min from the silicon chip side. Measured by shear strength when shear stress is applied. When the die shear strength exceeds the lower limit value, when the semiconductor device is mounted on the printed circuit board, when the high temperature state is caused by the reflow furnace, the peeling due to the decrease in the adhesive force is suppressed, and the reflow crack caused by the peeling can be suppressed. .

  The present invention is an adhesive film for a semiconductor containing (A) a thermoplastic resin, (B) an epoxy resin, and (C) a curing agent. Below, each component of the adhesive film for semiconductors of this invention is demonstrated. The following is an example, and the present invention is not limited to the following.

  The (A) thermoplastic resin used in the present invention has thermoplasticity, and typically means a polymer resin having a main chain skeleton having 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 at 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 component raw material 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.
In the present invention, an acrylic resin (particularly an acrylic ester 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.

  The weight average molecular weight of the (A) thermoplastic resin used in the present invention is preferably 100,000 or more, particularly preferably 150,000 to 1,000,000. 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 a curing behavior by heat treatment.

  Although the glass transition temperature of the (A) thermoplastic resin used by this invention 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.

  The content of (A) thermoplastic resin used in the present invention is not particularly limited, but (A) thermoplastic resin a part by weight, (B) epoxy resin b part by weight (C) curing agent c part by weight 0.1 ≦ a / (a + b + c) ≦ 0.5, more preferably 0.15 ≦ a / (a + b + c) ≦ 0.4 and 0.2 ≦ a / (a + b + c) ≦ 0.3. 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 0.5 or less, the fluidity at the time of application of the film adhesive is improved, and the film adhesive can be filled in the circuit level difference 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 (B) 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 (A) thermoplastic resin. When the content is equal to or higher than the lower limit value, the fluidity at the time of pasting is improved, and when the content is equal to or lower than the upper limit value, the toughness of the adhesive film for a semiconductor can be improved.

The (C) curing agent used in the present invention can be appropriately selected and used as long as it functions as a curing agent for the epoxy resin. Specific examples of the curing agent (C) used in the present invention include, for example, aliphatic polyamines such as diethylenetriamine, triethylenetetramine, and metaxylylenediamine, and aromatics such as diaminodiphenylmethane, m-phenylenediamine, and diaminodiphenylsulfone. Amine curing agents such as polyamine compounds including aromatic polyamine, dicyandiamide, organic acid dihydrazide, etc., aliphatic acid anhydrides such as hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tritometic anhydride, benzophenone tetracarboxylic anhydride Acid anhydride curing agents such as aromatic acid anhydrides, phenol novolac resins, cresol novolac resins, phenol aralkyl (including phenylene and biphenylene skeleton) resins, naphthol aralkyl resins Triphenolmethane resin, dicyclopentadiene type phenol resin, bis (mono or di-t-butylphenol) propane, methylenebis (2-propenyl) phenol, propylenebis (2-propenyl) phenol, bis [(2-propenyloxy) phenyl] Methane, bis [(2-propenyloxy) phenyl] propane, 4,4 ′-(1-methylethylidene) bis [2- (2-propenyl) phenol], 4,4 ′-(1-methylethylidene) bis [2- (1-phenylethyl) phenol], 4,4 ′-(1-methylethylidene) bis [2-methyl-6-hydroxymethylphenol], 4,4 ′-(1-methylethylidene) bis [2- Such as methyl-6- (2-propenyl) phenol], 4,4 ′-(1-methyltetradecylidene) bisphenol Lumpur-based curing agents.
In the present invention, it is preferable to use a liquid curing agent having a viscosity of 30 Pa · s (30,000 cps) or less at 25 ° C. Further, a liquid curing agent having a viscosity of 10 Pa · s (10,000 cps) or less at 25 ° C. is preferable. By setting the viscosity at 25 ° C. of the curing agent used in the present invention to a certain value or less, initial stickability and reliability are improved.

  The (C) curing agent used in the present invention is preferably a liquid phenol compound. Specific examples of the liquid phenol compound include bis (mono- or di-t-butylphenol) propane, methylenebis (2-propenyl) phenol, propylenebis (2-propenyl) phenol, bis [(2-propenyloxy) phenyl] methane, bis [(2-propenyloxy) phenyl] propane, 4,4 ′-(1-methylethylidene) bis [2- (2-propenyl) phenol], 4,4 ′-(1-methylethylidene) bis [2- (1-Phenylethyl) phenol], 4,4 ′-(1-methylethylidene) bis [2-methyl-6-hydroxymethylphenol], 4,4 ′-(1-methylethylidene) bis [2-methyl-6 -(2-propenyl) phenol], 4,4 ′-(1-methyltetradecylidene) bisphenol. The viscosity of these liquid phenol compounds can be controlled by the number of nuclei n and the type of benzene ring substituent.

  The addition amount of (C) curing agent used in the present invention can be determined by calculating the equivalent ratio of epoxy equivalent to curing agent. (B) The ratio of the epoxy equivalent of the epoxy resin to the equivalent of the functional group of the (C) curing agent (for example, hydroxyl equivalent in the case of a phenol resin) is preferably 0.5 or more and 1.5 or less, particularly 0.7 or more 3 or less is 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 (C) curing agent used in the present invention is preferably represented by the formula (1). The compound represented by the formula (1) is obtained by polycondensation of allylphenol with formaldehyde, and a preferred specific example is a polycondensate of 2- (2-propenyl) phenol.

（式中、ｐ、ｑ、ｒは１〜３の整数を表す。Ｒ¹、Ｒ²、Ｒ³はアリル基を表す。）

(In the formula, p, q and r represent an integer of ^{1 to 3.} R ¹ , R ² and R ³ represent an allyl group.)

  In the present invention, it is also possible to add a solid phenol resin as the (C) curing agent. By using the solid phenolic resin in combination, tackiness of the adhesive film for semiconductor at room temperature can be reduced and workability can be improved. The solid phenol resin is a monomer having at least two phenolic hydroxyl groups that are in a solid state at 25 ° C. and normal pressure, which can form a crosslinked structure by curing reaction with the epoxy resin (B). Examples of oligomers and polymers include phenol novolak resins, cresol novolak resins, phenol aralkyl (including phenylene and biphenylene skeleton) resins, naphthol aralkyl resins, triphenolmethane resins, and dicyclopentadiene type phenol resins. These may be used not only alone but also in plural.

  In order to accelerate the curing reaction, the resin composition may contain 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.

  The film adhesive layer of the present invention can further contain a coupling agent as required. Thereby, the adhesiveness of resin, a to-be-adhered body, and resin 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.

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 (A) Acrylate ester copolymer (butyl acrylate-acrylonitrile-ethyl acrylate-glycidyl methacrylate copolymer, Nagase ChemteX Corp., SG-80HDR as thermoplastic resin , Tg: 10 ° C., weight average molecular weight: 350,000) and curable resin as epoxy resin (EOCN-1020-80 (orthocresol novolac type epoxy resin), epoxy equivalent 200 g / eq, Nippon Kayaku ( 97 parts by weight), NC6000 (epoxy equivalent 200 g / eq, manufactured by Nippon Kayaku Co., Ltd.) 146 parts by weight, liquid phenol compound (MEH-8000H, hydroxyl group equivalent 141 g / OH group, manufactured by Meiwa Kasei Co., Ltd.) ) 110 parts by weight, solid phenol resin (PR-HF-3, water) Group equivalent 104g / OH group, Sumitomo Bakelite Co., Ltd.) 47 parts by weight, imidazole compound (2P4MHZ-PW, Shikoku Kasei Co., Ltd.) 0.75 part by weight as curing accelerator, γ-glycid as coupling agent 1.3 parts by weight of xylpropyltrimethoxysilane (KBM403E, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in methyl ethyl ketone (MEK) to obtain a resin varnish having a resin solid content of 49%.

(2) Manufacture of adhesive film for semiconductor Using a comma coater, the above-mentioned resin varnish is converted into a polyethylene terephthalate film (Mitsubishi Chemical Polyester Film Co., Ltd., product number MRX50, thickness 50 μm) as the base film (I). After coating, the film was dried at 90 ° C. for 5 minutes to obtain an adhesive film for semiconductor having a thickness of 25 μm.

(3) Production of base film (II) and pressure-sensitive adhesive layer Clear Tech CT-H717 (manufactured by Kuraray Co., Ltd.) consisting of 60 parts by weight of Hibra and 40 parts by weight of polypropylene was used as the base film (II) with a thickness of 100 μm. A film was formed and the surface was corona treated. Next, a copolymer having a weight average molecular weight of 500,000 obtained by copolymerizing 50 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of butyl acrylate, 37 parts by weight of vinyl acetate, and 3 parts by weight of 2-hydroxyethyl methacrylate. Was applied to a polyester film having a thickness of 38 μm, and the thickness after drying was 10 μm, followed by drying at 80 ° C. for 5 minutes to obtain a pressure-sensitive adhesive layer. Thereafter, the pressure-sensitive adhesive layer was laminated on the corona-treated surface of the base film (II) to obtain a base film (II) and a pressure-sensitive adhesive layer.

(4) Manufacture of a die attach film with a dicing sheet function with a dicing sheet function A protective film is attached to the above-mentioned film adhesive layer with the base film (I), and the base film (I) and the film adhesive layer are attached. Half-cut, affixed to the pressure-sensitive adhesive layer on the above-mentioned base film (II), and peeled off the protective film, whereby the base film (II), the pressure-sensitive adhesive layer, the base film (I) and the film adhesive A die attach film with a dicing sheet function in which layers were formed in this order was obtained.

(5) Manufacturing of Semiconductor Device The die attach film with a dicing function obtained in Examples and Comparative Examples was attached to the back surface of a 5-inch 200 μm wafer at 60 ° C. to obtain a wafer with a die attach film with a dicing function. After that, the wafer with a die attach film with a dicing function is diced (cut) into a size of a semiconductor element of 5 mm × 5 mm square at a spindle rotation speed of 30,000 rpm and a cutting speed of 50 mm / sec using a dicing saw, and then diced. Solder resist (manufactured by Taiyo Ink Manufacturing Co., Ltd .: Trade name) AUS308) coated bismaleimide-triazine resin substrate (circuit level difference 5-10 um), 130 ° C., 5N, 1.0 second pressure bonding, die bonding, 120 ° C., 1 hour heat treatment, semiconductor adhesive film Semi-cured, sealed with resin, and heat treated at 175 ° C for 2 hours The sealing resin was cured to obtain 10 semiconductor devices.

  The details of the evaluation test of the adhesive film for semiconductor of the present invention will be described below.

(Measurement method of minimum melt viscosity)
A sample of several semiconductor adhesive films stacked to a thickness of 100 um was used as a sample, and shear stress shearing at a frequency of 1 Hz was performed at a heating rate of 10 ° C / min using a HAAKE Corporation Rheo Stress RS-150. Measured by giving.

(Measurement method of volatile matter)
A semiconductor adhesive film having a size of 50 × 50 mm is used as a sample, the weight of the sample is measured and set to M1, the sample is heated in a hot air circulating thermostat at 200 ° C. for 2 hours, weighed to M2, and [(M2-M1 ) / M1] × 100 = volatile content (wt%)
As a result, the volatile content was calculated.

(Measurement method of die shear strength after bonding)
The semiconductor adhesive film is sandwiched between bismaleimide-triazine substrates coated with 4 x 4 mm silicon chip (thickness 550 um) and solder resist (manufactured by Taiyo Ink Manufacturing Co., Ltd .: trade name: AUS308). , 130 ° C, 5N, heat-pressed in 1 second, 120 ° C, 1 hour, and further 175 ° C for 2 hours, held on a 260 ° C hot plate for 20 seconds, then 0.5 mm with push-pull gauge The shear strength when shear stress was applied at a rate of / min was defined as die shear strength.

(Circuit fillability)
The circuit filling performance is obtained by filling the semiconductor device before resin sealing obtained in each example and comparative example with a scanning ultrasonic flaw detector (SAT) into a circuit step on an organic substrate with a semiconductor adhesive film. The rate of being 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%

  Details of an evaluation test of a semiconductor device produced using the adhesive film for a semiconductor of the present invention will be described below.

(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, and 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)
The crack resistance was determined by applying a moisture absorption treatment to the semiconductor devices obtained in each of the examples and comparative examples at 85 ° C./85% RH / 168 hours, and then performing an IR reflow at 260 ° C. three times to perform a scanning ultrasonic flaw detector (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)
(B) As an epoxy resin, EOCN-1020-80 (epoxy equivalent 200 g / eq, Nippon Kayaku Co., Ltd.) 99 parts by weight, NC6000 (epoxy equivalent 200 g / eq, Nippon Kayaku Co., Ltd.) 148 parts by weight As a liquid phenol compound (C), 92 parts by weight of MEH-8000H (hydroxyl group equivalent 141 g / OH group, manufactured by Meiwa Kasei Co., Ltd.) and as a solid phenol resin, PR-HF-3 (hydroxyl group equivalent 104 g / OH group, Sumitomo) The experiment was performed in the same manner as in Example 1 except that 62 parts by weight of Bakelite Co., Ltd. was used. The formulation and experimental results are shown in Table 1.

(Example 3)
The experiment was performed in the same manner as in Example 1 except that 110 parts by weight of MEH-8000-4L (hydroxyl equivalent: 141 g / OH group, manufactured by Meiwa Kasei Co., Ltd.) was used as the liquid phenol compound (C). The formulation and experimental results are shown in Table 1.

Example 4
The experiment was performed in the same manner as in Example 1 except that 47 parts by weight of PR53647 (hydroxyl equivalent: 104 g / OH group, manufactured by Sumitomo Bakelite Co., Ltd.) was used as the solid phenol resin. The formulation and experimental results are shown in Table 1.

(Example 5)
(B) As an epoxy resin, EOCN-1020-80 (epoxy equivalent 200 g / eq, Nippon Kayaku Co., Ltd.) 200 parts by weight, as a liquid phenol compound (C), MEH-8000H (hydroxyl equivalent 141 g / OH group, The experiment was performed in the same manner as in Example 1 except that 141 parts by weight of Meiwa Kasei Co., Ltd. was used. The formulation and experimental results are shown in Table 1.

(Example 6)
(B) As an epoxy resin, EOCN-1020-80 (epoxy equivalent 200 g / eq, Nippon Kayaku Co., Ltd.) 60 parts by weight, as a liquid phenol compound (C), MEH-8000H (hydroxyl equivalent 141 g / OH group, The experiment was performed in the same manner as in Example 1 except that 42 parts by weight of Meiwa Kasei Co., Ltd. was used. The formulation and experimental results are shown in Table 1.

(Example 7)
(B) As an epoxy resin, EOCN-1020-80 (epoxy equivalent 200 g / eq, Nippon Kayaku Co., Ltd.) 400 parts by weight, as a liquid phenol compound (C), MEH-8000H (hydroxyl equivalent 141 g / OH group, The experiment was performed in the same manner as in Example 1 except that 282 parts by weight of Meiwa Kasei Co., Ltd. was used. The formulation and experimental results are shown in Table 1.

(Example 8)
The surface of the semiconductor adhesive film prepared in Example 1 was laminated to the back surface of a 5-inch, 200 μm semiconductor wafer under the conditions of 60 ° C., 0.1 MPa, 50 mm / sec, and the semiconductor adhesive film surface was diced into a dicing film (Sumilite FSL-N4003). To 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 30,000 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 transmissive substrate side of the dicing film, the dicing film bonded to the adhesive film for semiconductor was peeled off. And the organic element (circuit level difference 5-10um) which uses bismaleimide triazine as the main material covered with a solder resist (manufactured by Taiyo Ink Co., Ltd., AUS308) on the semiconductor element bonded with the above-mentioned adhesive film for semiconductor, After pressure bonding at 130 ° C., 5N for 1.0 second, die bonding, 120 ° C., 1 hour heat treatment, semi-cured semiconductor adhesive film, sealing with resin, 175 ° C. 2 hours heat treatment, The sealing resin was cured to obtain a semiconductor device. A schematic diagram of the obtained semiconductor device is shown in FIG. This semiconductor device was confirmed to exhibit high reliability in various evaluation tests.

(Comparative Example 1)
(B) An experiment was performed in the same manner as in Example 1 except that the epoxy resin, the liquid phenol compound (C), the solid phenol resin, and the curing accelerator were not used. The formulation and experimental results are shown in Table 1.

(Comparative Example 2)
(B) EOCN-1020-80 (epoxy equivalent 200 g / eq, Nippon Kayaku Co., Ltd.) 200 parts by weight as epoxy resin, PR-HF-3 (hydroxyl equivalent 104 g / OH group, Sumitomo) as solid phenol resin The experiment was performed in the same manner as in Example 1 except that 104 parts by weight of Bakelite Co., Ltd.) was used and the liquid phenol compound (C) was not used. The formulation and experimental results are shown in Table 1.

(Comparative Example 3)
(B) EOCN-1020-80 (epoxy equivalent 200 g / eq, Nippon Kayaku Co., Ltd.) 200 parts by weight as epoxy resin, PR-HF-3 (hydroxyl equivalent 104 g / OH group, Sumitomo) as solid phenol resin 104 parts by weight of Bakelite Co., Ltd.), 120 parts by weight of 1,6-hexanediol dimethacrylate (1,6-HX, manufacturer: Kyoeisha Chemical Co., Ltd.) as a radiation polymerizable monomer, and a liquid phenol compound The experiment was performed in the same manner as in Example 1 except that (C) was not used. The formulation and experimental results are shown in Table 1.

(Comparative Example 4)
(B) As an epoxy resin, NC6000 (epoxy equivalent 200 g / eq, Nippon Kayaku Co., Ltd., 526 parts by weight), as a liquid phenol compound (C), MEH-8000H (hydroxyl equivalent 141 g / OH group, manufactured by Meiwa Kasei Co., Ltd.) ) An experiment was conducted in the same manner as in Example 1 except that 371 parts by weight was used and no solid phenol resin was used, and the blending and experimental results are shown in Table 1.

(Comparative Example 5)
(A) Polyimide resin as a thermoplastic resin (1,3-bis (3-aminophenoxy) benzene (manufactured by Mitsui Chemicals, Inc.) APB as a 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, (B) epoxy resin, EOCN-1020-80 (orthocresol novolac type epoxy resin), epoxy equivalent 200 g / eq, manufactured by Nippon Kayaku Co., Ltd., 10 parts by weight, as coupling agent -Dissolve 5 parts by weight of phenyl-γ-aminopropyltrimethoxysilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) in N-methyl-2-pyrrolidone (NMP) to prepare a resin varnish with 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 to give a 25 μm thick adhesive film for semiconductors. Was prepared and evaluated using this. The experimental results are shown in Table 1.

  As shown in Table 1, in Examples 1-7, both the adhesive film evaluation results and the semiconductor device evaluation results showed good results, but in Comparative Examples 1-5, all of these showed good results. There wasn't. In particular, in Comparative Example 4, since the minimum melt viscosity was as low as 0.1 Pa · s or less, the adhesive film flowed out from the application site when the semiconductor chip was applied, and the semiconductor chip could not be applied appropriately.

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 (5)

(A) a thermoplastic resin, (B) an epoxy resin, and (C) a semiconductor adhesive film containing a curing agent,
The minimum melt viscosity in the range of 50 ° C. or higher and 180 ° C. or lower when the temperature of the adhesive film for semiconductor is raised from room temperature at a temperature rising rate of 10 ° C./min is 0.1 Pa · s to 500 Pa · s, and The adhesive film for semiconductors characterized by having a volatile content of 5.0% or less. The adhesive film for a semiconductor according to claim 1, wherein the die shear strength after bonding is 1 MPa or more. The adhesive film for semiconductor according to claim 1, wherein the (C) curing agent is a phenol resin.   The adhesive film for a semiconductor according to claim 3, wherein the phenol resin is liquid at 25 ° C. 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.

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