JP5671778B2 - Film-like adhesive for semiconductor sealing, semiconductor device and method for manufacturing the same - Google Patents

Description

The present invention relates to a semiconductor sealing film adhesive, a semiconductor device, and a method for manufacturing the same.

  Conventionally, a wire bonding method using a fine metal wire such as a gold wire has been widely used to connect a semiconductor chip and a substrate. However, recently, semiconductor devices are required to be reduced in size, thickness, and functionality. In order to meet such demands, a flip chip connection method in which conductive protrusions called bumps are formed on a semiconductor chip and a semiconductor chip and a substrate electrode are directly connected is adopted as a semiconductor device manufacturing process. It is becoming.

  As a method of connecting the bump and the electrode by the flip-chip connection method, a method of metal bonding using solder or tin, a method of metal bonding by applying ultrasonic vibration, a method of maintaining mechanical contact by the shrinkage force of the resin Etc. are known. Among these connection methods, since the reliability of the connection portion is excellent, a method of metal bonding using solder or tin has become the mainstream.

  Recently, a liquid crystal display module, which has been reduced in size and functionality, uses a semiconductor device called COF (Chip On Film) that employs the above-described flip-chip connection method. In such a semiconductor device, a semiconductor chip for driving a liquid crystal having a gold bump formed on a polyimide substrate on which a tin plating wiring is formed is mounted, and the gold bump and the tin plating wiring are a gold-tin eutectic metal joint. Connected with.

  In this connection of COF, in order to form a gold-tin eutectic, it is necessary to heat the connecting portion to a eutectic temperature of 278 ° C. or higher. On the other hand, from the viewpoint of improving productivity, the connection time is required to be able to be connected in a short time, for example, within 5 seconds. Thus, since it is necessary to heat to eutectic temperature (278 degreeC) or more in a short time, the preset temperature of a manufacturing apparatus becomes a high temperature of 300-400 degreeC.

By the way, in the COF, normally, the gap between the semiconductor chip and the substrate is filled with a sealing resin to protect the connection portion from the external environment and prevent external stress from concentrating on the connection portion, and narrow pitch. The insulation reliability between wiring is ensured (for example, refer patent document 1).
JP 2006-188573 A

  Currently, as a sealing resin filling method, a method of injecting a liquid resin by a capillary phenomenon and curing the resin after connecting the semiconductor chip and the substrate is generally used. However, since the gap between the chip and the substrate is reduced along with the narrow pitch connection of the COF, the above method has a problem that it takes a long time to inject the liquid resin. For this reason, there is a demand for a method for forming a sealing resin that is sufficiently excellent in productivity even when the gap between the chip and the substrate is small.

  As a method for forming such a sealing resin, there is a method in which an adhesive is supplied to the chip or the substrate and then the chip and the substrate are connected. However, in this method, since the connection is performed by heating to a high temperature of 300 ° C. or higher in COF as described above, there is a concern that voids (bubbles) due to foaming of volatile components contained in the adhesive or spring back are generated. Is done. Such voids cause a decrease in insulation reliability between narrow pitch wirings.

  The present invention has been made in view of the above circumstances, is sufficiently excellent in workability when used for sealing a semiconductor device, and can sufficiently suppress generation of voids due to high-temperature heating. An object of the present invention is to provide a film-like adhesive for sealing a semiconductor capable of manufacturing a semiconductor device sufficiently excellent in connection reliability and insulation reliability, and a method for manufacturing the semiconductor device. It is another object of the present invention to provide a semiconductor device in which the amount of voids in the sealing resin is sufficiently reduced and the connection reliability and the insulation reliability are sufficiently excellent.

  In order to achieve the above object, the present invention includes (a) an epoxy resin and (b) a curing accelerator, (b) the curing accelerator has a melting point of 120 ° C. or higher, and (b) curing Provided is a film-like adhesive for encapsulating a semiconductor in which the active region of the accelerator is 120 ° C. or higher.

  The film-like adhesive for semiconductor encapsulation of the present invention has the following advantages: (b) The curing accelerator has a melting point of 120 ° C. or higher and an active region at 120 ° C. or higher. In some cases, the progress of the curing reaction can be sufficiently suppressed before the semiconductor chip is mounted, and the increase in viscosity can be suppressed. When the semiconductor chip is mounted, it is heated to 120 ° C. or higher to reach the active region of the (b) curing accelerator, and the film sealing adhesive for semiconductor sealing exhibits immediate curing and increases the melt viscosity. It is possible to ensure a good embedding property and initial conduction. In addition, the generation of voids associated with springback or the like can be suppressed. Therefore, the film-like adhesive for sealing a semiconductor of the present invention is sufficiently excellent in workability when used for sealing a semiconductor device and sufficiently excellent in connection reliability and insulation reliability (HAST resistance). Can be manufactured.

  The film-like adhesive for semiconductor encapsulation of the present invention preferably contains (c) a polymer component having a weight average molecular weight of 10,000 or more.

  Moreover, it is preferable that the film-form adhesive for semiconductor sealing of this invention contains (d) polyimide resin. Thereby, the film formability at the time of formation of the film-like adhesive for semiconductor encapsulation can be improved.

  Moreover, it is preferable that (d) polyimide resin in the film-form adhesive for semiconductor sealing of this invention has a weight average molecular weight of 30000 or more, and has a glass transition temperature of 100 degrees C or less. Thereby, the film formability at the time of formation of the film-like adhesive for semiconductor encapsulation can be further improved.

  Moreover, it is preferable that (b) hardening accelerator in the film-form adhesive for semiconductor sealing of this invention contains imidazoles. Thereby, for example, when heated to about 300 ° C., (a) the curing reaction of the epoxy resin proceeds more smoothly, and the connection reliability can be further improved.

The (b) curing accelerator preferably contains a compound represented by the following general formula (1).

(In the above formula, R ¹ , R ² and R ³ each independently represent hydrogen, an alkyl group, a phenyl group or a hydroxyalkyl group.)

In the compound represented by the general formula (1), R ¹ is preferably hydrogen, and at least one of R ² and R ³ is preferably a hydroxyalkyl group. Usually, in the reaction between an epoxy resin and an imidazole, an electron pair of nitrogen attacks an epoxy group to generate an oxygen anion, and this oxygen anion further reacts with the epoxy group to advance a curing reaction. Here, when R ² and R ³ are hydroxyalkyl groups (hydroxyl groups), the hydroxyl group part is also involved in the reaction, which may cause steric hindrance. Thus, the active region is believed to R ¹ to R ³ is higher than the compound that is not a hydroxyalkyl group (hydroxyl group). Therefore, a large viscosity can be obtained by heating at the time of mounting the semiconductor device, and generation of voids can be further suppressed. In addition, the active region shifts to a high temperature side due to intramolecular bonds such as intramolecular hydrogen bonds, and a large increase in viscosity can be obtained by heating during semiconductor chip mounting. .

  In the present invention, the (a) epoxy resin is preferably solid at room temperature (1 atm, 25 ° C.).

  The present invention also provides a method of manufacturing a semiconductor device comprising a semiconductor chip having bumps and a substrate having metal wiring, wherein the semiconductor chip and the substrate are bumped via the above-mentioned film-like adhesive for semiconductor sealing. Arranged so that the metal wiring faces each other, pressurizes the semiconductor chip and the substrate in the facing direction and heats to cure the film-like adhesive for semiconductor sealing, and electrically connects the bump and the metal wiring A manufacturing method having a connecting step is provided.

  In this manufacturing method, since the semiconductor chip and the substrate are connected using the film-like adhesive for semiconductor sealing having the above-described characteristics, workability at the time of manufacturing the semiconductor device can be made sufficiently excellent. . Moreover, since generation | occurrence | production of a void can fully be suppressed, it becomes possible to manufacture the semiconductor device which is excellent in connection reliability.

  In the connecting step in the method for manufacturing a semiconductor device of the present invention, the semiconductor chip and the substrate are pressurized in the opposing direction and heated to 300 ° C. or higher, and between the bump containing gold and the metal wiring having the tin plating layer It is preferable to form a gold-tin eutectic and electrically connect the bump and the metal wiring. As a result, it is possible to manufacture a semiconductor device having further excellent connection reliability.

  According to the present invention, when used for sealing a semiconductor device, the workability is sufficiently excellent, and even when heated to 300 ° C. or higher, the generation of voids can be sufficiently suppressed, and the connection It is possible to provide a film-like adhesive for sealing a semiconductor capable of manufacturing a semiconductor device sufficiently excellent in reliability and insulation reliability, and a method for manufacturing the semiconductor device. In addition, the amount of voids in the sealing resin is sufficiently reduced, and a semiconductor device that is sufficiently excellent in connection reliability can be provided.

  In the following, preferred embodiments of the present invention will be described with reference to the drawings as the case may be. In the drawings, the same or equivalent elements are denoted by the same reference numerals, and redundant description is omitted. Hereinafter, the detail of each component contained in a film adhesive is demonstrated below.

[(A) Epoxy resin]
The (a) epoxy resin preferably has two or more epoxy groups in the molecule. For example, bisphenol A type, bisphenol F type, naphthalene type, phenol novolak type, cresol novolak type, phenol aralkyl type, biphenyl type, triphenylmethane type, dicyclopentadiene type, various polyfunctional epoxy resins and the like are preferable. One of these epoxy resins can be used alone or in combination of two or more.

  Since bisphenol A type and bisphenol F type liquid epoxy resins have a 5% thermogravimetric reduction temperature of 250 ° C. or less, they may decompose and generate volatile components when heated at high temperatures. For this reason, it is preferable to use a solid epoxy resin at room temperature (1 atm, 25 ° C.). The 5% thermogravimetric temperature can be measured by TG-DTA method using TG-DTA-6200 (temperature increase rate: 10 ° C./min) manufactured by Seiko Instruments Inc.

  The film-like adhesive for semiconductor encapsulation of this embodiment may contain a phenol resin in order to control the viscosity and the physical properties of the cured product. The phenol resin preferably has two or more phenolic hydroxyl groups in the molecule. For example, a phenol novolak resin, a cresol novolak resin, a phenol aralkyl resin, a cresol naphthol formaldehyde polycondensate, a triphenylmethane type polyfunctional phenol resin, Various polyfunctional phenol resins can be used. These can be used alone or in combination of two or more. The equivalent ratio of the epoxy resin to the phenol resin (hydroxyl group / epoxy group) is preferably 0.4 to 1.2 from the viewpoints of curability, adhesiveness, storage stability, and the like. It is more preferable that it is 0.5 to 1.0. When the amount ratio is less than 0.4, the curability of the film adhesive is lowered and the adhesive force tends to be lowered. On the other hand, if the amount ratio exceeds 1.2, the unreacted phenolic hydroxyl group remains excessively, and the water absorption rate tends to increase and the insulation reliability tends to decrease.

[(B) Curing accelerator]
(B) The curing accelerator preferably has a melting point of 120 ° C. or higher and an active region at 120 to 400 ° C. That is, the lower limit of the temperature range of the active region is preferably 120 ° C. or higher, and the upper limit of the temperature range of the active region is preferably 400 ° C. or lower. When the active region exceeds 400 ° C., the curing reaction of the film adhesive at the time of mounting the semiconductor chip tends not to proceed sufficiently. The active region is an exothermic peak temperature when an epoxy resin and a curing accelerator are mixed and heated up. For example, TG-DTA-6200 manufactured by Seiko Instruments Inc. Speed: 10 ° C./min). Those having an active region at 120 to 400 ° C. exhibit excellent curing accelerating ability in the temperature region at the time of mounting a semiconductor chip, so that a semiconductor device having further excellent connection stability can be manufactured.

  (B) The curing accelerator has a melt viscosity at 350 ° C. or higher and 250 Pa · s or lower depending on the composition of the film-like adhesive for semiconductor encapsulation, and the void generation rate when pressure-bonded at 350 ° C. for 5 seconds or longer. Is preferably selected so as to indicate 5% or less. The void generation rate can be obtained as a ratio of the area where voids are generated to the entire area of the contact portion between a member such as a semiconductor chip or a polyimide substrate and the film adhesive in the crimped portion.

  Specifically, the (b) curing accelerator preferably contains imidazoles. Examples of imidazoles include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazole. Lithium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-Ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6 [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric Examples include adducts, 2-methylimidazole isocyanuric acid adducts, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins and imidazoles. .

Among these, from the viewpoint of curability, storage stability, and HAST resistance, 2-phenyl-4 in which at least one of R ^{2 to} R ³ of the imidazole represented by the general formula (1) is a hydroxyalkyl group , 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole are preferred, and 2-phenyl-4,5-dihydroxymethylimidazole is more preferred. You may use these individually by 1 type or in combination of 2 or more types. Moreover, you may use what microencapsulated these and raised the potential.

Further, from the viewpoint of obtaining more excellent curability, storage stability, and HAST resistance, R ^{1 of the} imidazoles represented by the general formula (1) is hydrogen, and both R ² and R ³ are hydroxyalkyl. It is preferably a group.

  (B) As a compounding quantity of a hardening accelerator, it is preferable that it is 0.001-0.1 with respect to (a) epoxy resin by mass ratio, and it is more preferable that it is 0.001-0.05. 0.001 to 0.03 is more preferable. When the mass ratio is less than 0.001, sufficiently excellent curability tends to be impaired, and when it exceeds 0.1, the film adhesive is cured before the connection portion by the gold-tin eutectic is formed. Therefore, the occurrence of poor connection tends to be difficult to suppress sufficiently.

[(C) Polymer component having a weight average molecular weight of 10,000 or more]
The film adhesive of the present embodiment preferably includes (c) a polymer component having a weight average molecular weight of 10,000 or more (hereinafter referred to as “(c) polymer component” for convenience). (C) The polymer component is a resin different from (a) an epoxy resin, for example, (a) an epoxy resin different from the epoxy resin, a phenoxy resin, a polyimide resin, a polyamide resin, a polycarbodiimide resin, a phenol resin, and a cyanate. Examples include ester resins, acrylic resins, polyester resins, polyethylene resins, polyethersulfone resins, polyetherimide resins, polyvinyl acetal resins, urethane resins, acrylic rubbers, and the like. Among them, from the viewpoint of obtaining a film-like adhesive having excellent heat resistance and film formability, (a) an epoxy resin different from the epoxy resin, a phenoxy resin, a polyimide resin, a cyanate ester resin, a polycarbodiimide resin, and the like are preferable. More preferred are polyimide resins different from phenoxy resins and (a) epoxy resins. These polymer components can be used singly or in combination of two or more or as a copolymer of two or more.

[(D) Polyimide resin]
(D) The polyimide resin can be obtained, for example, by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. More specifically, tetracarboxylic dianhydride and diamine are blended in an equimolar ratio or almost equimolar ratio in an organic solvent (the order of addition of each component is arbitrary), and is 80 ° C. or less, preferably The addition reaction is performed at a temperature of 0 to 60 ° C. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide precursor, is generated. The tetracarboxylic dianhydride is preferably subjected to a recrystallization purification treatment with acetic anhydride in order to suppress deterioration of various properties of the film adhesive.

  The molecular weight of the produced polyamic acid can be adjusted by heating at a temperature of 50 to 80 ° C. for depolymerization. The polyimide resin can be obtained by dehydrating and ring-closing the above-described reactant, that is, polyamic acid. Dehydration ring closure can be performed by a thermal ring closure method in which heat treatment is performed and a chemical ring closure method in which a dehydrating agent is used.

  There is no restriction | limiting in particular in the tetracarboxylic dianhydride used as a raw material of a polyimide resin, For example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2' , 3,3′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic acid Anhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic acid Anhydride, 2,3,2 ′, 3′-benzophenonetetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic Acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic acid Anhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3 , 6,7-Tetra Loronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic acid Acid dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methyl Phenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bi (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3 , 4-butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydro Naphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2,2 ]-Oct-7 Ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2, -bis [4- (3,4- Dicarboxyphenyl) phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) phenyl ] Hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride) ), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride can be used tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride.

  Moreover, the tetracarboxylic dianhydride represented by the following general formula (I) and (II) can be used.

  In the general formula (I), r represents an integer of 2 to 20.

  The tetracarboxylic dianhydride represented by the general formula (I) can be synthesized from, for example, trimellitic anhydride monochloride and the corresponding diol. Specifically, 1,2- (ethylene) bis (trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5 -(Pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) Bis (trimellitic anhydride), 1,9- (nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecamethylene) bis (trimellitic anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (tri Riteto anhydride) and the like.

  Among these, a tetracarboxylic dianhydride represented by the following general formula (II) is preferable from the viewpoint of imparting excellent moisture resistance reliability to the film adhesive. These tetracarboxylic dianhydrides can be used individually by 1 type or in combination of 2 or more types.

  The amount of the tetracarboxylic dianhydride represented by the above formula (II) is preferably 40 mol% or more, more preferably 50 mol% or more with respect to the total tetracarboxylic dianhydride. 70 mol% or more is more preferable. When the blending amount is less than 40 mol%, it tends to be difficult to sufficiently obtain the effect of moisture resistance reliability due to the use of the tetracarboxylic dianhydride represented by the above formula (II).

  There is no restriction | limiting in particular as diamine used for the raw material of a polyimide resin, For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino -3,5-diisopropylphenyl) methane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3, , 4'-di Minodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 3 , 4′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 ′-(3,4′-diaminodiphenyl) propane, 2,2- Bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-amino) Phenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1, -Bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4'-( 1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) Phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3 -Aminophenoxy) phenyl) sulfide, bis (4- (4-aminophenoxy) phenyl) sulfide, bis (4- (3-aminophenoxy) ) Phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, aromatic diamines such as 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4 -Aminophenoxyphenyl) propane can be used.

  As the diamine, an aliphatic ether diamine represented by the following general formula (III), an aliphatic diamine represented by the following general formula (IV), or a siloxane diamine represented by the following general formula (V) can also be used. .

In the general formula (III), Q ¹ , Q ² and Q ³ each independently represents an alkylene group having 1 to 10 carbon atoms, and s represents an integer of 2 to 80.

  In the general formula (IV), k represents an integer of 5 to 20.

In the general formula (V), Q ⁴ and Q ⁹ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q ⁵ , Q ⁶ , Q ⁷ , and Q ⁸ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and p represents an integer of 1 to 5.

  Among the diamines described above, the diamine represented by the general formula (III) or (IV) is preferable from the viewpoint of obtaining a film-like adhesive having excellent low stress properties, laminating properties, and low-temperature adhesiveness. Moreover, the diamine represented by the said general formula (V) is preferable from a viewpoint of obtaining the film adhesive which has favorable low water absorption and low hygroscopicity. These diamines can be used alone or in combination of two or more. In this case, the aliphatic ether diamine represented by the general formula (III) is 1 to 50 mol% of the total diamine, the aliphatic diamine represented by the general formula (IV) is 20 to 80 mol% of the total diamine, Or it is preferable that the siloxane diamine represented by the said general formula (V) is 20-80 mol% of the whole diamine. When each said diamine is outside the numerical range of the said mol%, there exists a tendency for favorable low-temperature laminating property and low water absorption to become difficult to be obtained.

  Specific examples of the aliphatic ether diamine represented by the general formula (III) include aliphatic ether diamines of the formulas (III-1) to (III-5). In general formulas (III-4) and (III-5), n represents an integer of 1 or more.

  The weight average molecular weight of the aliphatic ether diamine represented by the general formula (III-4) is preferably, for example, 350, 750, 1100, or 2100. Moreover, it is preferable that the weight average molecular weight of the aliphatic ether diamine represented by the said general formula (III-5) is 230, 400, or 2000, for example.

  Among the aliphatic ether diamines, aliphatic ether diamines represented by the following general formula (VI) are more preferable in that low-temperature laminating properties and good adhesion to a substrate with an organic resist can be ensured.

  In the general formula (VI), m represents an integer of 2 to 80.

  Specific examples of the aliphatic ether diamine represented by the general formula (VI) include Jeffamine D-230, D-400, D-2000, D-4000, ED-600 manufactured by Sun Techno Chemical Co., Ltd. , ED-900, ED-2001 and EDR-148 (above, trade names), and polyoxyalkylene diamines such as BASF polyetheramine D-230, D-400 and D-2000 (above, trade names), etc. Aliphatic diamines may be mentioned.

  Examples of the aliphatic diamine represented by the general formula (IV) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2- Examples include diaminocyclohexane. Among these, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane are preferable.

  Examples of the siloxane diamine represented by the general formula (V) include, in the general formula (V), <when p is 1,> 1,1,3,3-tetramethyl-1,3-bis (4 -Aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (2 -Aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (2 -Aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3 -Aminobutyl) disiloxane, 1,3-dimethyl-1,3 Dimethoxy-1,3-bis (4-aminobutyl) disiloxane, and the like.

  <When p is 2,> 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3 , 3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1, 5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5 -Tetramethyl-3,3-dimethoxy-1,5 Bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5- Examples include hexaethyl-1,5-bis (3-aminopropyl) trisiloxane and 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane.

  You may use the said polyimide resin individually by 1 type or in combination of 2 or more type as needed.

  (D) The glass transition temperature (Tg) of the polyimide resin is preferably 100 ° C. or less, and preferably 75 ° C. or less, from the viewpoint of obtaining a film-like adhesive that is more excellent in adhesion to a substrate or a semiconductor chip. More preferred. When the glass transition temperature exceeds 100 ° C., it tends to be difficult to sufficiently bury unevenness such as bumps formed on the semiconductor chip, electrodes formed on the substrate, wiring patterns, etc. in the film adhesive. For this reason, air bubbles may remain in the formed connection portion and cause voids.

  The glass transition temperature was determined by using DSC (Differential Scanning Thermal Analysis, manufactured by Perkin Elmer, trade name: DSC-7 type), sample amount: 10 mg, heating rate: 5 ° C./min, measurement atmosphere: air conditions It is a value measured by.

  (D) The weight average molecular weight of the polyimide resin is preferably 30000 or more, more preferably 40000 or more, and more preferably 50000 or more in terms of polystyrene in order to have good film-forming properties. Further preferred. When the weight average molecular weight is less than 30000, good film formability tends to be impaired when the film adhesive is formed. In addition, the above-mentioned weight average molecular weight is a value measured by polystyrene conversion using high performance liquid chromatography (manufactured by Shimadzu Corporation, trade name: C-R4A).

  (D) The content of the polyimide resin is not particularly limited. However, from the viewpoint of improving the retention of the film shape, the mass ratio of the (a) epoxy resin to the (d) polyimide resin is preferably 0.01 to 4, and more preferably 0.1 to 4. 0.1 to 3 is more preferable. If the mass ratio is less than 0.01, the curability of the film-like adhesive tends to be reduced, and the excellent adhesive force tends to be impaired. If it exceeds 4, the film-formability at the time of forming the film-like adhesive Tends to decrease.

  The film-like adhesive for semiconductor encapsulation of this embodiment may contain (e) a filler in order to control the viscosity and the physical properties of the cured product. (E) As a filler, an insulating inorganic filler, a whisker, and a resin filler can be used. Examples of the insulating inorganic filler include glass, silica, alumina, titanium oxide, carbon black, mica, and boron nitride. Among these, silica, alumina, titanium oxide, boron nitride, and the like are preferable, and silica, alumina, and boron nitride are more preferable.

  Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride. As the resin filler, polyurethane, polyimide, or the like can be used. These fillers and whiskers can be used alone or in combination of two or more. (E) The shape, particle size, and blending amount of the filler are not particularly limited.

  In addition to the above-mentioned components (a) to (e), the film-like adhesive of the present embodiment contains additives such as a silane coupling agent, a titanium coupling agent, a leveling agent, an antioxidant, or an ion trap agent. You may contain. You may use these individually by 1 type or in combination of 2 or more types. What is necessary is just to adjust about a compounding quantity so that the effect of each additive may express.

  The manufacturing method of the film-like adhesive for semiconductor encapsulation of this embodiment will be described below. First, an epoxy resin and a curing accelerator and, if necessary, a polyimide resin, a phenol resin and / or an additive (such as a filler) are added to an organic solvent and dissolved or dispersed by stirring, mixing, kneading, etc. A resin varnish is prepared. After applying the prepared resin varnish using a knife coater, roll coater or applicator on the base film subjected to the mold release treatment, the organic solvent is removed by heating, and a film adhesive is applied on the base film. Form. In addition, when mix | blending a polyimide resin, it isolate | separates after synthesize | combining a polyimide resin, it uses it as it is in the state of the varnish containing a polyimide resin, and may add each component in this varnish, and may prepare a resin varnish. .

  As the organic solvent used for preparing the resin varnish, those having characteristics capable of uniformly dissolving or dispersing each component are preferable. Examples of such organic solvents include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane. , Cyclohexanone, ethyl acetate and the like. These organic solvents can be used individually by 1 type or in combination of 2 or more types. Mixing, kneading, and the like in preparing the resin varnish can be performed using a stirrer, a raking machine, a three roll, a ball mill, a homodisper, or the like.

  As a base film, what has heat resistance which can endure the heating conditions at the time of volatilizing an organic solvent can be used. Examples of such a base film include a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, and a methylpentene film. The base film is not limited to a single layer film made of only one of the above film materials, and may be a multilayer film in which two or more types of film materials are laminated.

  The conditions for volatilizing the organic solvent from the resin varnish applied to the base film are preferably such that the organic solvent is sufficiently volatilized, specifically 0.1 to 0.1 at a temperature of 50 to 200 ° C. It is preferable to perform heating for 90 minutes. The heating temperature at this time is preferably a temperature at which the curing reaction does not proceed so much.

  Next, a preferred embodiment of a semiconductor device manufacturing method using a semiconductor sealing film adhesive will be described.

  In the method of manufacturing a semiconductor device according to the present embodiment, the above-described film-like adhesive for semiconductor sealing is interposed between the semiconductor chip and the substrate, and the bump on the semiconductor chip and the metal wiring on the substrate are opposed to each other. A first step of arranging and temporarily connecting the semiconductor chip and the substrate, pressurizing and heating the semiconductor chip and the substrate in a direction in which the bump and the metal wiring face each other, and curing the film-like adhesive for semiconductor sealing, A second step of electrically connecting the metal wiring. Details of each step will be described below.

(First step)
FIG. 1 is a process cross-sectional view schematically showing a first process of a semiconductor device manufacturing method according to a preferred embodiment of the present invention. In the first step, first, a semiconductor sealing film adhesive 12 is interposed between the semiconductor chip 14 and the substrate 16.

  Bumps 15 are formed on one surface of the semiconductor chip 14. The material of the bump 15 formed on the semiconductor chip 14 is not particularly limited, and examples thereof include gold, low melting point solder, high melting point solder, nickel, tin and the like. Among these, in the case of COF, it is preferable to contain gold.

  Metal wiring 18 is formed on one surface of the substrate 16. The material of the substrate 16 is not particularly limited, and an inorganic substrate such as ceramic or an organic substrate such as epoxy resin, bismaleimide triazine resin, or polyimide resin can be used. Among these, in the case of COF, a polyimide resin is preferable.

  Examples of the material of the metal wiring 18 include copper, aluminum, silver, gold, and nickel. The wiring is formed by etching or pattern plating. The metal wiring 18 may have a plating layer on the surface by plating with gold, nickel, tin or the like. In the case of COF, a copper wiring having a tin plating layer on the surface by tin plating is preferably used.

  The film-like adhesive 12 for semiconductor sealing may be cut out to a predetermined size and then attached to the substrate 16, or may be attached to the bump 15 forming surface of the semiconductor chip 14 and then diced into individual pieces. The semiconductor chip 14 to which the film-like adhesive 12 for semiconductor sealing is attached may be produced. The area and thickness of the film-like adhesive 12 for semiconductor sealing are appropriately set depending on the size of the semiconductor chip 14 and the height of the bumps 15.

  In the first step, the metal wiring 18 of the substrate 16 and the bump 15 of the semiconductor chip 14 are aligned, and the semiconductor chip 14 and the substrate are arranged in the direction in which the metal wiring 18 and the bump 15 oppose (arrows A and B directions). 16 is pressurized using a pressure head 30 and a stage 32. Thereby, the bump 15 is press-fitted into the film-like adhesive 12 for semiconductor sealing.

  FIG. 2 is a process cross-sectional view schematically showing a second process of the semiconductor device manufacturing method according to the preferred embodiment of the present invention. In the second step, the pressure head 30 and the stage 32 pressurize the bumps 15 and the metal wirings 18 in the opposite direction (arrows A and B directions) and 0.5 to 5 at a connection temperature of 300 to 450 ° C. Heat for seconds. As a result, the bump 15 and the metal wiring 18 are in direct contact and are electrically connected, and the film sealing adhesive 12 for semiconductor encapsulation is cured to become a cured resin 22. The pressurizing pressure (continuous load) can be appropriately adjusted in consideration of the number of bumps, bump height and variation, bump deformation amount, and the like.

  As described above, since the semiconductor chip 14 and the metal wiring 18 are each heated to 300 to 450 ° C., when the semiconductor chip 14 contains gold and there is a tin plating layer on the surface of the metal wiring 18, the gold And tin react to form a gold-tin eutectic at the contact portion between the bump 15 and the metal wiring 18. As a result, the bonding between the bump 15 and the metal wiring 18 becomes stronger, and the connection reliability can be further improved.

  Since the film-like adhesive 12 for semiconductor encapsulation is made of a material that does not easily generate voids even when heated at a high temperature of 300 to 450 ° C., the insulation reliability can be sufficiently maintained. The void generation rate of the semiconductor device obtained by the manufacturing method of the above embodiment is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less. If the void generation rate is greater than 5%, voids remain between the narrow pitch wirings, and the insulation reliability may be reduced.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. For example, in the method for manufacturing a semiconductor device, after the bump 15 and the metal wiring 18 are electrically connected in the second step, a heat treatment step of heating the entire semiconductor device in an oven or the like may be further performed.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to the following Example.

Example 1
<(D) Synthesis of polyimide resin>
To a 300 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, 2.12 g (0.035 mol) of 1,12-diaminododecane, 17.31 g (0, molecular weight: 1923>, polyetherdiamine (manufactured by BASF, ED2000 <molecular weight: 1923>) .03 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: LP-7100) 2.61 g (0.035 mol), and N-methyl- 150 g of 2-pyrrolidone (manufactured by Kanto Chemical Co., Inc.) was charged and stirred to obtain a solution.

  Thereafter, while the flask was cooled in an ice bath, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic dianhydride) (manufactured by ALDRICH) was recrystallized and purified with acetic anhydride. , Trade name: BPADA) 15.62 g (0.10 mol) was added in small portions.

  After reacting at room temperature (25 ° C.) for 8 hours, 100 g of xylene was added, and heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene together with water to obtain a synthetic polyimide resin solution. The Tg of the synthetic polyimide resin was 22 ° C., the weight average molecular weight was 47000, and the SP (solubility parameter) value was 10.2.

<Preparation of raw materials>
Next, the following compounds were prepared as raw materials for producing a film adhesive.

(A) Epoxy resin / cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: YDCN-702)
・ Multifunctional special epoxy resin (product name: VG3101L, manufactured by Printec Co., Ltd.)

(B) Curing accelerator, 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2PHZ-PW, melting point: 240 ° C., active region: 155 to 175 ° C.)
2-phenyl-4-methyl-5-hydroxymethylimidazole (manufactured by Shikoku Chemicals Co., Ltd., trade name: 2P4MHZ-PW, melting point: 193 ° C., active region: 140-150 ° C.)
2-Phenylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2PZ-PW, melting point: 140 ° C., active region: 100-125 ° C.)
2-Phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2P4MZ-PW, melting point: 180 ° C., active region: 110-125 ° C.)
2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2MAOK-PW, melting point: 260 ° C. , Active region: 130-145 ° C.)

Phenol resin / cresol naphthol formaldehyde polycondensate (Nippon Kayaku Co., Ltd., trade name: Kayahard NHN, weight average molecular weight: 730)

(E) Filler / boron nitride [made by Mizushima Alloy Iron Co., Ltd., trade name: HPP1-HJ (average particle size: 1.0 μm, maximum particle size: 5.1 μm)]
Silica filler (Nippon Aerosil Co., Ltd., trade name: R972 <average particle size 20 nm>)

<Method for producing film-like adhesive for semiconductor encapsulation>
In 20 ml of glass screw tube, (c) 1.62 g of synthetic polyimide resin, 0.18 g of epoxy resin (trade name: YDCN-702), 0.18 g of epoxy resin (trade name: VG3101L), silica filler (trade name: R972) 0.11 g, boron nitride (trade name: HPP1-HJ) 0.70 g, curing accelerator 0.0036 g, and N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Inc.) 4.4 g were stirred, stirred and removed Stirring and defoaming were performed with a foaming device AR-250 (trade name, manufactured by Shinky Corporation) to obtain a resin varnish.
The obtained resin varnish was applied to a base film (manufactured by Teijin DuPont Films, trade name: Purex A53) with a coating machine PI1210FILMCOATER (trade name, manufactured by Tester Sangyo Co., Ltd.), and a clean oven ( The film-like adhesive for semiconductor encapsulation was produced by drying (manufactured by Espec Co., Ltd.) (drying at 80 ° C. for 30 minutes and 120 ° C. for 30 minutes).

  The evaluation test of the obtained film adhesive was performed as follows.

<Measurement of melt viscosity>
FIG. 3 is an explanatory diagram for explaining a method for producing Sample A for melt viscosity measurement. First, the produced film adhesive 12 was cut into a predetermined size (diameter 6 mm, thickness about 0.1 mm) and pasted on a 0.7 mm thick glass chip 11 (size: 15 mm × 15 mm). Then, as shown in FIG. 3, the glass chip 11, the film adhesive 12, and the cover glass 13 were laminated | stacked in order, covering the cover glass 13 (size: 18 mm x 18 mm) of thickness 0.12-0.17 mm. Sample A was prepared.

  Next, the sample A is crimped using a flip chip bonder (manufactured by Matsushita Electric Industrial Co., Ltd., trade name: FCB3) under the conditions of a heating temperature of 350 ° C., a pressing pressure of 1 MPa, and a heating and pressing time of 0.5 seconds. A crimped body was prepared. And the volume change of the film adhesive before and behind crimping was measured. The melt viscosity (viscosity) was calculated from the volume change measured by the parallel plate plastometer method by the following viscosity calculation formula. The results are shown in Table 1.

μ = 8πFtZ ⁴ Z ₀ ⁴ / [3V ² (Z ₀ ⁴ −Z ⁴ )]
μ: melt viscosity (Pa · s)
F: Load (N)
t: Heating and pressing time (seconds)
Z ₀ : initial thickness (m)
Z: Thickness after pressing (m)
V: Resin volume (m ³ )

<Evaluation of connection resistance (initial conduction)>
FIG. 4A is a photograph taken from above (semiconductor chip side) of the semiconductor device used for connection resistance evaluation, and FIG. 4B is a photograph taken of a cross section of the semiconductor device used for connection resistance evaluation. It is. A semiconductor device for connection resistance evaluation was manufactured as follows.

  The produced film adhesive was cut into a predetermined size (2.5 mm × 15.5 mm × thickness 0.03 mm), and polyimide substrate 16 (manufactured by Hitachi Ultra LSI Systems, Inc., trade name: JKIT COF TEG — 30-B, polyimide) The thickness of the substrate was 38 μm, the thickness of the copper wiring: 8 μm, the thickness of the wiring tin plating: 0.2 μm).

  Using the above-described flip chip bonder, a chip 14 having a gold bump 15 formed on the surface opposite to the polyimide substrate of the film adhesive attached on the polyimide substrate (manufactured by Hitachi Ultra LSI Systems, Product name: JTEG PHASE6_30, chip size: 1.6 mm × 15.1 mm × thickness 0.4 mm, bump size: 20 μm × 100 μm × height 15 μm, bump number 726) were mounted by pressure bonding. The pressure bonding conditions were a head temperature: 350 ° C., a stage temperature: 100 ° C., a pressure bonding time: 1 second, and a pressure bonding pressure: 50 N. Thus, a semiconductor device in which the polyimide substrate 16 and the chip 14 with the gold bumps were daisy chain connected as shown in FIGS. 4A and 4B was obtained.

  The connection resistance value in the daisy chain connection of the obtained semiconductor device was measured using a multimeter. When the connection resistance value in a daisy chain connection of a semiconductor device manufactured without using a film adhesive was around 160Ω, the case where the connection resistance value is 120 to 190Ω is “A”, less than 120Ω or more than 190Ω Was evaluated as “B”. The evaluation results are shown in Table 1.

<Measurement of void incidence>
FIG. 5 is an explanatory diagram for explaining a method for producing Sample B for measuring the void generation rate. The produced film adhesive was cut into a predetermined size (5 mm × 5 mm × thickness 0.03 mm), and as shown in FIG. 5, the film adhesive 12 was glass chip 11 (15 mm × 15 mm × thickness 0.7 mm). Affixed on top. A sample B was prepared by covering the film adhesive 12 with a chip 14 (4.26 mm × 4.26 mm × thickness 0.27 mm, bump height: 0.02 mm) on which gold bumps 15 were formed.

  Sample B was subjected to predetermined conditions (head temperature: 350 ° C., stage temperature: 100 ° C., pressure bonding time: 5 seconds, pressure bonding pressure: 1 MPa) using a flip chip bonder (manufactured by Matsushita Electric Industrial Co., Ltd., trade name: FCB3). To obtain a pressure-bonded body.

  The void generation rate of the crimped body was calculated as the ratio of the area where voids were generated to the entire area of the chip 14 with gold bumps in the crimped portion. The results are shown in Table 1.

<Insulation reliability test (HAST test: Highly Accelerated Sto
range Test)>
FIG. 6 is a photograph taken from above of Sample C used in the insulation reliability test. Sample C was prepared as follows.

  The film-like adhesive 12 (thickness 30 μm) produced as described above is pasted on the surface having the outer copper wiring 18 of the comb electrode evaluation TEG (30 μm pitch) having the copper wiring 18 plated with tin on the polyimide substrate 16. did. After pasting, the sample C was put in a clean oven (manufactured by Especsk Co., Ltd.) and cured at 180 ° C. for 1 hour to obtain a sample C as shown in FIG.

  Sample C was taken out from the clean oven and placed in an accelerated life test apparatus (manufactured by Hirayama Seisakusho, trade name: PL-422R8, 110 ° C., 85% RH, 100 hours), and the insulation resistance was measured.

The case where the insulation resistance of 10 ⁷ Ω or more was maintained during the measurement period of 100 hours was evaluated as “A”, and the case where the insulation resistance could not be maintained was evaluated as “B”. The evaluation results are shown in Table 5.

( Reference Example 2 and Comparative Examples 1 to 4)
Except for changing the composition of the raw materials used as shown in Table 1 below, the film-like adhesion for semiconductor encapsulation was carried out in the same manner as in the method for producing the film-like adhesive for semiconductor encapsulation of Example 1. Agents were prepared and evaluated. Table 1 summarizes the blending amount (parts by mass) of raw materials of the film-like adhesive for semiconductor encapsulation and the evaluation results.

It is process sectional drawing which shows typically the 1st process of the manufacturing method of the semiconductor device which concerns on suitable embodiment of this invention. It is process sectional drawing which shows typically the 2nd process of the manufacturing method of the semiconductor device which concerns on suitable embodiment of this invention. It is explanatory drawing for demonstrating the preparation methods of the sample A for melt viscosity measurement. It is the photograph of the semiconductor device used for evaluation of connection resistance. It is explanatory drawing for demonstrating the preparation methods of the sample B for void incidence rate measurement. It is the photograph which image | photographed the sample C used for the insulation reliability test from upper direction.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 11 ... Glass chip, 12 ... Film adhesive for semiconductor sealing (film adhesive), 13 ... Cover glass, 14 ... Chip (semiconductor chip), 15 ... Gold bump (bump), 16 ... Substrate (polyimide substrate) , 18 ... metal wiring (copper wiring), 22 ... cured resin, 30 ... pressure head, 32 ... stage.

Claims (10)

(A) an epoxy resin, (b) a curing accelerator, (d) a polyimide resin, and (f) a phenol resin ,
The (b) curing accelerator has a melting point of 120 ° C. or higher,
The active region of the (b) curing accelerator is 120 ° C. or higher,
The film-form adhesive for semiconductor sealing in which the said (b) hardening accelerator contains the compound represented by following General formula (1).

(In the above formula, R ¹ represents hydrogen, an alkyl group, a phenyl group or a hydroxyalkyl group, and R ² and R ³ represent a hydroxyalkyl group.)   (C) The film-like adhesive for semiconductor encapsulation according to claim 1, comprising a polymer component having a weight average molecular weight of 10,000 or more. Wherein (d) the polyimide resin has a weight average molecular weight of 30000 or more, and semiconductor encapsulation film-like adhesive according to claim 1 or 2 wherein has a glass transition temperature of 100 ° C. or less. Semiconductor encapsulation film-like adhesive according to any one of claims 1 to 3, wherein R ¹ is hydrogen in the compound represented by the general formula (1). The said (a) epoxy resin is solid at room temperature (1 atmosphere, 25 degreeC), The film adhesive for semiconductor sealing as described in any one of Claims 1-4 . The film-like adhesive for semiconductor encapsulation according to claim 1, wherein the (d) polyimide resin has a glass transition temperature of 100 ° C. or less. The film-form adhesive for semiconductor sealing as described in any one of Claims 1-6 which electrically connects the bump | vamp containing gold | metal | money and the metal wiring which has a tin plating layer. A method for manufacturing a semiconductor device comprising a semiconductor chip having bumps and a substrate having metal wiring,
The semiconductor chip and the substrate are arranged so that the bumps and the metal wiring are opposed to each other through the film-like adhesive for semiconductor sealing according to any one of claims 1 to 7 , The manufacturing method which has a connection process which pressurizes and heats a semiconductor chip and the said board | substrate to harden the said film-form adhesive for semiconductor sealing, and electrically connects the said bump and the said metal wiring. In the connecting step, the semiconductor chip and the substrate are pressurized in a facing direction and heated to 300 ° C. or more, and gold-tin is formed between the bump containing gold and the metal wiring having the tin plating layer. The manufacturing method according to claim 8 , wherein a eutectic is formed and the bump and the metal wiring are electrically connected. A semiconductor device obtained by the manufacturing method according to claim 8 .