JP2009117813A - Semiconductor sealing film-like adhesive and semiconductor device manufacturing method using the adhesive, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor sealing film-like adhesive having sufficient insulating reliability between wires and sufficient conductivity between a semiconductor chip and a substrate while suppressing the occurrence of void when connecting the semiconductor chip to the substrate at a temperature of 300°C or higher. <P>SOLUTION: The semiconductor sealing film-like adhesive 4 contains (a) a polyimide resin, (b) an epoxy resin, (c) a phenol resin, and (d) hardening accelerator. It has a melting viscosity of 2,000 Pas or lower at 350°C and a curing reaction rate of 50% or more after heated for ten seconds at 350°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  Up to now, wire bonding methods using fine metal wires such as gold wires have been widely applied to connect semiconductor chips and substrates, but to meet the demands for smaller, thinner and higher functionality semiconductor devices. A flip chip connection method in which conductive protrusions called bumps are formed on a semiconductor chip and a substrate electrode and the semiconductor chip are directly connected via the bumps is becoming widespread.

  As a 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. From the viewpoint of the reliability of the connecting portion, a method of metal bonding using solder or tin is common.

  In particular, in a liquid crystal display module that has been especially reduced in size and functionality in recent years, a semiconductor chip for driving a liquid crystal formed with gold bumps on a polyimide substrate formed with a tin-plated wiring is metal-bonded by a gold-tin eutectic crystal. A semiconductor device called COF (Chip On Film) is used.

  In the case of COF, in order to form a gold-tin eutectic, it is necessary to set the connecting portion to 278 ° C. or higher which is the eutectic temperature. In addition, from the viewpoint of improving productivity, the connection time is as short as 5 seconds or less, and heating is performed at or above the eutectic temperature in a short time, so the set temperature of the manufacturing apparatus is as high as 300 to 400 ° C.

In COF, the connection portion is protected from the external environment so that external stress is not concentrated on the connection portion, and the gap between the semiconductor chip and the substrate is made of resin to ensure the insulation reliability between the narrow pitch wirings. It is necessary to fill with sealing. As the current sealing and filling method, after connecting the semiconductor chip and the substrate, a method of injecting and curing the liquid resin into the gap by capillary action is common, but between the chip and the substrate accompanying the narrow pitch connection It is feared that the reduction of the voids requires a long time for the injection and the productivity is lowered. As a method for solving the above-mentioned concern, there is a method of connecting the chip and the substrate after supplying an adhesive to the chip or the substrate (see, for example, Patent Document 1).
JP 2006-188573 A

  However, in COF, since the chip and the substrate are connected at a high temperature of 300 ° C. or higher, if a method of connecting the chip and the substrate after supplying the adhesive to the chip or the substrate is used, depending on the volatile components in the adhesive, etc. There is a problem that the adhesive foams and bubbles called voids are easily generated. Since voids cause a decrease in insulation reliability between narrow pitch wirings, suppression of voids has been an issue.

  The present invention has been made in view of the above-described problems of the prior art, and can suppress generation of voids when connecting a semiconductor chip and a substrate at a high temperature of 300 ° C. or more, and can provide sufficient insulation reliability between wirings. And a semiconductor device manufacturing method and a semiconductor device using the adhesive, and a film-like adhesive for sealing a semiconductor capable of obtaining sufficient conductivity and sufficient electrical conductivity between a semiconductor chip and a substrate .

  In order to achieve the above object, the present invention provides a film shape for semiconductor encapsulation containing (a) a polyimide resin, (b) an epoxy resin, (c) a phenol resin, and (d) a curing accelerator. A film-like adhesive for semiconductor encapsulation, which is an adhesive, having a melt viscosity at 350 ° C. of 2000 Pa · s or less and a curing reaction rate after heating at 350 ° C. for 10 seconds of 50% or more. provide.

  According to such a film sealing adhesive for semiconductor sealing, by having the above-described configuration, it is possible to sufficiently suppress generation of voids when connecting a semiconductor chip and a substrate at a high temperature of 300 ° C. or higher. Sufficient insulation reliability and sufficient conductivity between the semiconductor chip and the substrate can be obtained.

  In the film-like adhesive for semiconductor encapsulation of the present invention, the (a) polyimide resin preferably has a weight average molecular weight of 30000 or more and a glass transition temperature of 100 ° C. or less. (A) When the weight average molecular weight of the polyimide resin is 30000 or more, good film formability can be exhibited. Moreover, (a) When the glass transition temperature of the polyimide resin is 100 ° C. or less, good pastability to a substrate or a semiconductor chip can be obtained.

  Moreover, in the film-like adhesive for semiconductor encapsulation of the present invention, the (d) curing accelerator is preferably an adduct of imidazoles and an organic acid. (D) When the curing accelerator is an adduct of an imidazole and an organic acid, the film adhesive can have better curability, connectivity, and storage stability. In addition, the melt viscosity at 350 ° C. of the film adhesive can be sufficiently lowered compared to the case of using imidazoles not added with an organic acid, thereby ensuring good connectivity. Can do.

  Moreover, in the film-like adhesive for semiconductor encapsulation of the present invention, the organic acid is preferably isocyanuric acid. Thereby, the film adhesive can obtain better curability and storage stability. Moreover, the melt viscosity at 350 ° C. of the film adhesive can be made sufficiently lower.

  Moreover, it is preferable that the void generation rate when the film-like adhesive for semiconductor sealing of the present invention is pressure-bonded at 350 ° C. and 1 MPa for 5 seconds is 5% or less.

  The generated voids may cause a decrease in the adhesive strength and peeling between the underfill (resin filled in the gap between the semiconductor chip and the substrate) and the semiconductor chip and the substrate, leading to poor connection and reduced insulation reliability. is there.

  In addition, the accumulation of moisture in the voids may promote the diffusion and migration of impurity ions in the system, which may reduce the insulation reliability.

  Insulation reliability is good when the void generation rate is 5% or less when pressed at 350 ° C. and 1 MPa for 5 seconds.

  According to the present invention, when the semiconductor chip having bumps and the substrate having metal wiring are connected at a temperature of 300 ° C. or higher, the semiconductor chip is connected via the film sealing adhesive for semiconductor sealing of the present invention. The manufacturing method of a semiconductor device which has the process of sealingly filling the space | gap between the said board | substrate with the said film-form adhesive for semiconductor sealing.

  According to the method for manufacturing a semiconductor device, since the semiconductor chip and the substrate are connected using the film sealing adhesive for semiconductor sealing of the present invention, voids are generated between the semiconductor chip and the substrate. A semiconductor device that is sufficiently suppressed and has sufficient insulation reliability between the wirings and sufficient conductivity between the semiconductor chip and the substrate can be efficiently manufactured.

  In the method for manufacturing a semiconductor device of the present invention, the bump is a gold bump, the metal wiring is a metal wiring with a tin-plated surface, the substrate is a polyimide substrate, the semiconductor chip, the substrate, Are preferably formed by forming a gold-tin eutectic at a temperature of 300 ° C. or higher. With this manufacturing method, it is possible to manufacture a COF in which a semiconductor chip on which gold bumps are formed is mounted on a polyimide substrate by metal bonding using gold-tin eutectic.

  The present invention further provides a semiconductor device manufactured by the method for manufacturing a semiconductor device of the present invention.

  Since such a semiconductor device is manufactured by the method for manufacturing a semiconductor device of the present invention, generation of voids between the semiconductor chip and the substrate is sufficiently suppressed, and sufficient insulation reliability between wirings, Sufficient conductivity between the semiconductor chip and the substrate can be obtained.

  According to the present invention, it is possible to suppress generation of voids when connecting a semiconductor chip and a substrate at a high temperature of 300 ° C. or higher, sufficient insulation reliability between wirings, and sufficient conduction between the semiconductor chip and the substrate. A film-like adhesive for sealing a semiconductor that can be obtained, a method for manufacturing a semiconductor device using the adhesive, and a semiconductor device can be provided.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

(Film adhesive for semiconductor encapsulation and method for producing the same)
The film-like adhesive for semiconductor encapsulation of the present invention is a film for semiconductor encapsulation containing (a) a polyimide resin, (b) an epoxy resin, (c) a phenol resin, and (d) a curing accelerator. It has a melt viscosity at 350 ° C. of 2000 Pa · s or less, and a curing reaction rate after heating at 350 ° C. for 10 seconds is 50% or more. Hereinafter, each component will be described.

(A) Polyimide resin The (a) polyimide resin used in the present invention can be obtained, for example, by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. That is, in an organic solvent, tetracarboxylic dianhydride and diamine are used in an equimolar or almost equimolar amount (the order of addition of each component is arbitrary), and an addition reaction is performed at a reaction temperature of 80 ° C. or lower, preferably 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 acid dianhydride is preferably recrystallized and purified with acetic anhydride in order to suppress deterioration of various properties of the film adhesive.

  The polyamic acid can also be adjusted in molecular weight by heating at a temperature of 50 to 80 ° C. to cause depolymerization.

  The polyimide resin can be obtained by dehydrating and ring-closing the reaction product (polyamic acid). The dehydration ring closure can be performed by a thermal ring closure method in which heat treatment is performed, or a chemical ring closure method using a dehydrating agent.

  There is no restriction | limiting in particular as 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 Anhydride, 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-perylenetetracar Acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetra Carboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2, 3, 6, 7- Trachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Anhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetra Carboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) Methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1, 3-bis (3,4-dicarboxyphenyl) -1,1,3,3-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- Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid 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-di Carboxyphenyl) phenyl] hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (tri Merit acid anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic acid anhydride), 5- (2,5-dioxotetrahydride) Furyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, tetracarboxylic acid represented by the following general formula (I) Examples thereof include acid dianhydrides and tetracarboxylic dianhydrides represented by the following formula (II).

[In formula, m shows the integer of 2-20. ]

  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- (dodeca) Styrene) bis (trimellitate anhydride), 1,16 (hexamethylene decamethylene) bis (trimellitate anhydride), 1,18 (octadecamethylene) bis (trimellitate anhydride) and the like.

  Among the tetracarboxylic dianhydrides described above, a tetracarboxylic dianhydride represented by the above formula (II) is preferable in that it can provide excellent moisture resistance reliability. These tetracarboxylic dianhydrides can be used singly or in combination of two or more.

  Further, the content of the tetracarboxylic dianhydride represented by the above formula (II) is preferably 40 mol% or more, more preferably 50 mol% or more, more preferably 70 mol% or more based on the total tetracarboxylic dianhydride. Is very preferred. When this 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 as a raw material of the said 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, '-Diaminodiphenyl 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 -Aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benze 1,4-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-aminoenoxy) phenyl) sulfide, bis (4- (4-aminoenoxy) phenyl) sulfide, bis (4- (3-aminoenoxy) Ci) phenyl) sulfone, bis (4- (4-aminoenoxy) phenyl) sulfone, aromatic diamines such as 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4 -Aminophenoxyphenyl) propane, aliphatic ether diamine represented by the following general formula (III), aliphatic diamine represented by the following general formula (IV), siloxane diamine represented by the following general formula (V), etc. Can be mentioned.

[Wherein, Q ¹ , Q ² and Q ³ each independently represents an alkylene group having 1 to 10 carbon atoms, and r represents an integer of 2 to 80. ]

[In formula, q shows the integer of 5-20. ]

[Wherein, 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 are 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, diamines represented by the above general formula (III) or (IV) are preferable in that they can impart low stress properties, low-temperature laminating properties, and low-temperature adhesiveness. Moreover, the diamine represented by the said general formula (V) is preferable at the point which can provide 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 79% of the total diamine, and The siloxane diamine represented by the general formula (V) is preferably 20 to 79% of the total diamine. If the content is out of the above range, the effect of imparting low-temperature laminating properties and low water absorption tends to be small, such being undesirable.

Moreover, as aliphatic ether diamine represented by the said general formula (III), specifically, following formula;


In addition to the aliphatic ether diamine represented by the formula, an aliphatic ether diamine represented by the following formula (VI) is exemplified. Among these, 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 secured.

[In formula, s shows the integer of 2-80. ]

  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, ED- manufactured by Sun Techno Chemical Co., Ltd. 900, ED-2001, EDR-148, and aliphatic diamines such as polyoxyalkylene diamines such as polyetheramine D-230, D-400, and D-2000 manufactured by BASF.

  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- Diaminocyclohexane and the like can be mentioned, among which 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 1,1,3,3-tetramethyl-1,3-bis having p of 1 in the general formula (V). (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, and p is 2, and 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-amino Til) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl- 1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3 Examples include 5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane.

  The said polyimide resin can be used individually by 1 type or in mixture (blend) of 2 or more types as needed.

  (A) The glass transition temperature (Tg) of the polyimide resin is preferably 100 ° C. or less, and more preferably 75 ° C. or less, from the viewpoint of stickability to a substrate or a chip. If Tg is higher than 100 ° C., bumps formed on a semiconductor chip, electrodes and wiring patterns formed on a substrate cannot be embedded, and bubbles remain, which tends to cause voids. is there. The above Tg is measured using DSC (manufactured by Perkin Elmer, trade name: DSC-7 type) under the conditions of a sample amount of 10 mg, a heating rate of 5 ° C./min, and a measurement atmosphere: air. Of Tg.

  (A) 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 exhibit good film-formability independently. preferable. If the weight average molecular weight is less than 30000, the film formability may be reduced. In addition, said weight average molecular weight is a weight average molecular weight when measured in polystyrene conversion using a high performance liquid chromatography (Shimadzu Corporation make, brand name: C-R4A).

(B) Epoxy resin The (b) epoxy resin used in the present invention preferably has two or more epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type Use various polyfunctional epoxy resins such as epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, etc. can do. These can be used alone or as a mixture of two or more. In addition, for example, bisphenol A type and bisphenol F type liquid epoxy resins have a 1% thermogravimetric decrease temperature of 250 ° C. or less, and may decompose during high temperature heating to generate volatile components. It is desirable to use a solid epoxy resin.

(C) Phenol resin The (c) phenol resin used in the present invention preferably has two or more phenolic hydroxyl groups in the molecule. For example, phenol novolak resin, cresol novolak resin, phenol aralkyl resin, cresol Various polyfunctional phenol resins such as naphthol formaldehyde polycondensate and triphenylmethane type polyfunctional phenol resin can be used. These can be used alone or as a mixture of two or more.

  In the film adhesive, the equivalent ratio of (b) epoxy resin to (c) phenol resin ((c) phenol resin / (b) epoxy resin) is from the viewpoint of curability, adhesiveness, storage stability, etc. It is desirable to set to 0.4 to 1.2. A more preferred equivalent ratio is 0.4 to 1.0, and a more preferred equivalent ratio is 0.4 to 0.9. If the equivalent ratio is less than 0.4, the curability of the film adhesive may be reduced and the adhesive strength may be reduced. If the equivalent ratio is more than 1.2, an excess of unreacted phenolic hydroxyl groups may remain and absorb water. The rate may increase and insulation reliability may be reduced.

  The mass ratio of (a) polyimide resin to (b) epoxy resin and (c) phenol resin mixture is not particularly limited, but in order to maintain the film shape, (a) 1 part by mass of polyimide resin, (B) The epoxy resin and the (c) phenol resin mixture are preferably 0.01 to 4 parts by mass, more preferably 0.1 to 4 parts by mass, and 0.1 to 3 parts by mass. Is more preferable. When this mass ratio is smaller than 0.01 parts by mass, the curability of the film adhesive is lowered and the adhesive force may be lowered, and when it is larger than 4 parts by mass, the film formability may be lowered.

(D) Curing accelerator With regard to the (d) curing accelerator used in the present invention, the melt viscosity at 350 ° C. of the semiconductor sealing film adhesive is 2000 Pa, depending on the composition of the semiconductor sealing film adhesive. It may be selected so that the curing reaction rate after heating at 350 ° C. for 10 seconds is 50% or more.

  (D) Examples of the curing accelerator include adducts of imidazoles and organic acids. Although there is no restriction | limiting in particular as an organic acid, Trimellitic acid and isocyanuric acid are mentioned. More preferred is isocyanuric acid. Examples of adducts of imidazoles with organic acids include 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric. Acid adduct, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, more preferably 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct. These may be used alone or in combination of two or more. Moreover, you may use what microencapsulated these and raised the potential.

  (D) As a compounding quantity of a hardening accelerator, the ratio of 0.001-0.1 mass part is preferable with respect to 1 mass part of mixture of (b) epoxy resin and (c) phenol resin by mass ratio, A ratio of 0.001 to 0.05 parts by mass is more preferable, and a ratio of 0.001 to 0.03 parts by mass is still more preferable. When this mass ratio is less than 0.001 part by mass, the curability of the film adhesive may be lowered, and when it exceeds 0.1 part by mass, a connection part formed by a gold-tin eutectic is formed. There is a risk that the connection will be hardened before being cured.

  In the film adhesive of the present invention, a filler may be blended in order to control the viscosity and physical properties of the cured product. As the filler, an insulating inorganic filler, whisker, resin filler, or the like can be used. Examples of the insulating inorganic filler include glass, silica, alumina, titanium oxide, carbon black, mica, boron nitride, and the like. Among them, silica, alumina, titanium oxide, and boron nitride are preferable, and silica, alumina, and nitride are used. Boron is more preferred. Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride. For example, polyurethane, polyimide, or the like can be used as the resin filler. These fillers and whiskers can be used alone or as a mixture of two or more. There are no particular limitations on the shape, particle size, and blending amount of the filler.

  Furthermore, you may mix | blend a silane coupling agent, a titanium coupling agent, a leveling agent, antioxidant, and an ion trap agent with the film adhesive of this invention. These may be used singly or in combination of two or more. About these compounding quantities, what is necessary is just to adjust suitably so that the effect of each additive may express.

  The film adhesive of the present invention is required to have a melt viscosity at 350 ° C. of 2000 Pa · s or less, more preferably 200 to 1800 Pa · s, and more preferably 300 to 1500 Pa · s. Particularly preferred. When the melt viscosity exceeds 2000 Pa · s, when the semiconductor chip and the substrate are connected via the film adhesive, the film adhesive is likely to remain between the bump and the wiring, causing an initial conduction failure. It will be. If the melt viscosity is less than 200 Pa · s, the viscosity is too low and voids tend to be generated.

In the present invention, the melt viscosity at 350 ° C. of the film-like adhesive is obtained by performing pressure bonding at a temperature of 350 ° C. by a parallel plate plastometer method (other pressure bonding conditions: stage temperature 100 ° C., connection time 5 seconds, It is a value calculated from the volume (thickness) change of the film adhesive before and after pressure bonding (pressure bonding pressure 1 MPa). In addition, the viscosity calculation formula from the volume change by a parallel plate plastometer method is as the following formula (1).
μ = 8πFtZ ⁴ Z ₀ ⁴ / 3V ² (Z ₀ ⁴ −Z ⁴ ) (1)
μ: melt viscosity (Pa · s)
F: Load (N)
t: Pressurization time (s)
Z ₀ ⁴ : initial thickness (m)
Z ⁴ : Thickness after pressurization (m)
V: Resin volume (m ³ )

  The film adhesive of the present invention needs to have a curing reaction rate of 50% or more after heating at 350 ° C. for 10 seconds, more preferably 60% or more, and 70% or more. It is particularly preferred. When the curing reaction rate is less than 50%, curing / thickening is slow, and the influence of void generation due to spring back of a substrate or metal (chip, bump) due to high-temperature connection becomes large. When curing is fast, the generation of voids due to springback can be reduced. Therefore, if the curing reaction rate is less than 50%, generation of voids when the chip and the substrate are connected at a high temperature of 300 ° C. or higher cannot be sufficiently suppressed, resulting in a decrease in insulation reliability. Become.

  In the present invention, the curing reaction rate after heating the film adhesive at 350 ° C. for 10 seconds is measured by the following method. First, about the hardened | cured material after heating a film adhesive for 10 second at 350 degreeC, it heats up with the temperature increase rate of 10 degree-C / min using a differential scanning calorimeter, and measures calorific value. From this calorific value, the curing reaction rate is calculated by (calorific value of untreated film adhesive / calorific value of cured product after heat-treating film adhesive at 350 ° C. for 10 seconds) × 100. The curing reaction rate can be obtained using a film adhesive as a measurement sample, but among the constituent materials of the film adhesive, a material that causes a curing reaction by heating (for example, (b) epoxy resin, (c) It is also possible to obtain a composition comprising only a phenol resin and (d) a curing accelerator) as a measurement sample.

  Moreover, the void generation rate when the film adhesive of the present invention is pressure-bonded at 350 ° C. and 1 MPa for 5 seconds is preferably 5% or less, more preferably 3% or less, and 1% or less. More preferably it is. If the void generation rate is greater than 5%, voids remain between the narrow pitch wirings, and the insulation reliability may be reduced.

  A method for producing the film adhesive of the present invention will be described below. (A) Polyimide resin, (b) epoxy resin, (c) phenol resin, additives ((d) curing accelerator, filler, etc.) are added to an organic solvent and dissolved or dispersed by stirring, mixing, kneading, etc. A resin varnish is prepared. Then, after applying the resin varnish on the base film subjected to the release treatment using a knife coater, roll coater, applicator, etc., the organic solvent is removed by heating, and a film adhesive is applied on the base film. Form. In addition, when (a) a polyimide resin is synthesized and used, (a) the polyimide resin is used in a state of a polyimide resin varnish containing a solvent without being isolated after synthesis, and each component is added to the polyimide resin varnish. A resin varnish may be prepared.

  As the organic solvent used for preparing the resin varnish, those having properties capable of uniformly dissolving or dispersing each component are preferable. For example, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, Examples include toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, and ethyl acetate. 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.

  In addition, the base film is not particularly limited as long as it has heat resistance that can withstand the heating conditions when the organic solvent is volatilized, and a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film. Polyether naphthalate film, methylpentene film and the like can be exemplified. The base film is not limited to a single layer made of these films, and may be a multilayer film made of two or more materials.

  Furthermore, it is preferable that the conditions for volatilizing the organic solvent from the resin varnish after coating are such that the organic solvent is sufficiently volatilized, specifically, heating at 50 to 200 ° C. for 0.1 to 90 minutes. It is preferable to carry out.

(Semiconductor device and manufacturing method thereof)
In the method for manufacturing a semiconductor device of the present invention, when the semiconductor chip having bumps and the substrate having metal wiring are connected at a temperature of 300 ° C. or higher, the semiconductor device is connected via the film-like adhesive for semiconductor sealing of the present invention. And a step of sealing and filling a gap between the semiconductor chip and the substrate with the film-like adhesive for semiconductor sealing.

  Here, the material of the bump formed on the semiconductor chip is not particularly limited, and examples thereof include gold, low melting point solder, high melting point solder, nickel, and tin. Among these, gold is preferable in the case of COF.

  Although it does not specifically limit as a material of a board | substrate, Organic substrates, such as inorganic board | substrates, such as a ceramic, an epoxy, a bismaleimide triazine, a polyimide, are mentioned. Among these, in the case of COF, polyimide is preferable.

  Examples of the material for forming the wiring on the substrate include copper, aluminum, silver, gold, and nickel. The wiring is formed by etching or pattern plating. The surface of the wiring may be plated with gold, nickel, tin, or the like. Among these, in the case of COF, a copper wiring whose surface is tin-plated is suitable.

  The semiconductor chip and the substrate are connected via the film adhesive of the present invention. At this time, the film-like adhesive of the present invention may be cut out to a predetermined size and then attached to the substrate, or after being attached to the bump forming surface of the semiconductor wafer, the semiconductor wafer is diced into individual pieces. By forming the semiconductor chip, a semiconductor chip to which a film adhesive is attached may be produced. The area and thickness of the film adhesive are appropriately set according to the semiconductor chip size, bump height, and the like.

  After the film adhesive is attached to the substrate or semiconductor chip, the wiring pattern of the substrate and the bumps of the semiconductor chip are aligned, and the connection temperature is 300 ° C. or higher, preferably 0.5 to 300 ° C. Pressurize for ~ 5 seconds. The connection load depends on the number of bumps, but is set in consideration of absorption of bump height variations and control of the amount of bump deformation. After the semiconductor chip and the substrate are connected, heat treatment may be performed in an oven or the like.

  In the semiconductor device manufactured by the above method, generation of voids between the chip and the substrate is sufficiently suppressed, and sufficient insulation reliability is obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Synthesis example: Synthesis of polyimide resin)
In a 300 ml flask equipped with a thermometer, a stirrer, and a calcium chloride tube, 2.10 g (0.035 mol) of 1,12-diaminododecane, polyether diamine (trade name: D2000, molecular weight: 1923, manufactured by BASF) 31 g (0.03 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. After dissolution of the diamine, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic dianhydride) (made by ALDRICH, Inc.) was recrystallized and purified with acetic anhydride while cooling the flask in an ice bath. , Trade name: BPADA) 15.62 g (0.10 mol) was added in small portions. After reacting at room temperature for 8 hours, 100 g of xylene was added and heated at 180 ° C. while blowing nitrogen gas, and xylene was removed azeotropically with water to obtain a polyimide resin solution. The obtained polyimide resin had a Tg of 22 ° C., a weight average molecular weight of 47000, and an SP value of 10.2.

Example 1
In a 20 ml glass screw tube, 1.00 g (solid content) of the polyimide resin synthesized in the synthesis example, 0.1109 g of epoxy resin (YDCN-702), 0.1109 g of epoxy resin (VG3101L), 0 phenol resin (Kayahard NHN) 0.0782 g, silica filler (R972) 0.0684 g, boron nitride (HPP1-HJ) 0.4333 g, curing accelerator (2PZOK) 0.002218 g, and antioxidant (AO-60) 0.04 g were charged and solid N-methyl-2-pyrrolidone (NMP) is added so that the content becomes 40% by mass, and the mixture is stirred and defoamed with a stirring / defoaming device (trade name: AR-250, manufactured by Shinkey Co., Ltd.) Obtained. The obtained resin varnish was applied on a film (trade name: PUREX A53, manufactured by Teijin DuPont Films Co., Ltd.) subjected to a release treatment, and a coating machine (trade name: PI-1210 FILMCOATER, manufactured by Tester Sangyo Co., Ltd.). ) And dried in a clean oven (manufactured by ESPEC) at 80 ° C. for 30 minutes and then at 120 ° C. for 30 minutes to obtain a film adhesive.

(Example 2 and Comparative Examples 1-2)
In the preparation of the resin varnish, the film-like adhesives of Example 2 and Comparative Examples 1-2 were obtained in the same manner as in Example 1 except that the composition of the used material was changed as shown in Table 1 below. . In Table 1, the amount of each material is expressed in parts by mass.

Moreover, the detail of each material used by the Example and the comparative example is shown below.
(A) Polyimide resin Polyimide resin synthesized in Synthesis Example (hereinafter referred to as “synthetic polyimide”).
(B) Epoxy resin Cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: YDCN-702).
Multifunctional special epoxy resin (manufactured by Printec Co., Ltd., trade name: VG3101L).
(C) Phenolic resin Cresol naphthol formaldehyde polycondensate (Nippon Kayaku Co., Ltd., trade name: Kayahard NHN).
(D) Curing accelerator 2-Phenylimidazole isocyanuric acid adduct (manufactured by Shikoku Kasei Co., Ltd., trade name: 2PZOK).
2,4-Diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct (manufactured by Shikoku Kasei Co., Ltd., trade name: 2MAOK-PW).
2,4-Diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (manufactured by Shikoku Kasei Co., Ltd., trade name: 2MZA-PW).
(E) Filler Boron nitride (manufactured by Mizushima Alloy Iron Company, 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).
(F) Solvent N-methyl-2-pyrrolidone (NMP) (manufactured by Kanto Chemical Co., Inc.).
(Additive)
A hindered phenol-based antioxidant (trade name: AO-60, manufactured by ADEKA Corporation).

<Measurement of curing reaction rate>
An epoxy resin, a phenol resin, and a curing accelerator were blended in the same composition as in Table 1, and the solvent was dried to obtain a cured product. About 10 mg of the cured product is weighed in an aluminum pan, and heated using a differential scanning calorimeter (trade name: DSC7, manufactured by Perkin-Elmer Japan Co., Ltd.) at a heating rate of 10 ° C./min. It was measured. Curing reaction rate (%) is calculated from the calorific value according to the following formula:
Curing reaction rate (%) = (Heat generation amount of untreated film adhesive / Heat generation amount of cured product after heating the film adhesive on a hot plate at 350 ° C. for 10 seconds) × 100
Calculated by The results are shown in Table 2.

<Measurement of melt viscosity>
The film-like adhesives produced in Examples and Comparative Examples were cut out (φ6 mm, thickness of about 0.1 mm), and the cut-out film-like adhesive 4 was glass chip 3 (15 mm × 15 mm × 0.7 mm) as shown in FIG. ^t ) and a cover glass 7 (18 mm × 18 mm × 0.12 to 0.17 mm ^t ) was put on to prepare a sample A. Sample A was crimped with a flip chip bonder (FCB3, manufactured by Panasonic Corporation) (crimping conditions: head temperature 350 ° C., stage temperature 100 ° C., 5 seconds, 1 MPa), and the volume change of the film adhesive before and after the crimping was measured. . The melt viscosity was calculated from the volume change by the parallel plate plastometer method based on the following formula (1). The results are shown in Table 2.

(Viscosity calculation formula of parallel plate plastometer method)
μ = 8πFtZ ⁴ Z ₀ ⁴ / 3V ² (Z ₀ ⁴ −Z ⁴ ) (1)
μ: melt viscosity (Pa · s)
F: Load (N)
t: Pressurization time (s)
Z ₀ ⁴ : initial thickness (m)
Z ⁴ : Thickness after pressurization (m)
V: Resin volume (m ³ )

<Measurement of void incidence>
The film-like adhesives produced in Examples and Comparative Examples were cut out (5 mm × 5 mm × 0.03 mm ^t ), and the cut-out film-like adhesive 4 was glass chip 3 (15 mm × 15 mm × 0.00 mm) as shown in FIG. 7 mm ^t ), and a chip 5 with a gold bump 6 (4.26 mm × 4.26 mm × 0.27 mm ^t , bump height 0.02 mm) was placed thereon to produce Sample B. Sample B was pressure-bonded with FCB3 (manufactured by Panasonic) (pressure bonding conditions: head temperature 350 ° C., stage temperature 100 ° C., 5 seconds, 1 MPa), and the void generation rate after pressure bonding was measured. The void generation rate was calculated by the ratio of the generated void area after pressure bonding to the area of the gold bumped chip. The results are shown in Table 2.

<Manufacture of semiconductor devices (conductivity and appearance evaluation)>
Cut out the film-like adhesives prepared in Examples and Comparative Examples (2.5 mm × 15.5 mm × 0.03 mm ^t ), polyimide substrate (polyimide substrate: 38 μm thickness, copper wiring: 8 μm thickness, wiring tin plating: 0 .2 μm thickness, manufactured by Hitachi ULSI Systems Co., Ltd., trade name: JKIT COF TEG — 30-B), chip with gold bumps (chip size 1.6 mm × 15.1 mm × 0.4 mm ^t , bump size: 20 μm × 100 μm × 15 μm ^t , number of bumps 726, manufactured by Hitachi ULSI Systems Co., Ltd., trade name: JTEG PHASE6_30) was mounted with FCB3 (manufactured by Panasonic) (mounting conditions: head temperature 350 ° C., stage temperature 100 ° C., 5 seconds, 50N). Here, FIG. 3 is a photograph showing the entire semiconductor device obtained in Example 2, and shows a state in which the semiconductor chip 9 is mounted on the polyimide substrate 8. FIG. 4 is a photograph showing a cross section of the chip mounting portion in the semiconductor device obtained in Example 2. The tin-plated copper wiring 2 on the polyimide substrate 8 and the gold bumps 10 on the semiconductor chip 9 are gold. -It is connected by tin eutectic, and shows a state in which the gap between the semiconductor chip 9 and the polyimide substrate 8 is sealed and filled with a cured product of the film adhesive 11.

  Further, when a semiconductor device was fabricated by mounting a chip with gold bumps (daisy chain connection) on the polyimide substrate with FCB3 without using a film adhesive, connection resistance between the chip with gold bumps and the copper wiring was obtained. The value was about 155Ω. From this, the connection resistance value between the chip with the gold bump and the copper wiring in the semiconductor device manufactured using the film-like adhesive of the example and the comparative example is measured, and the initial value is when the value is 170Ω or less. It was determined that initial continuity was impossible when conduction was possible and the case was 170Ω or more or connection failure (connection resistance value is not displayed). The results are shown in Table 2.

<Insulation reliability test (HAST test: Highly Accelerated Storage Test)>
Comb-type electrode evaluation TEG (manufactured by Shindo Denshi Co., perflex-S, wiring pitch: a film-like adhesive (thickness: 30 μm) produced in the examples and comparative examples is formed by forming a tin-plated copper wiring on a polyimide film. 30 μm) and cured at 180 ° C. for 1 hour in a clean oven (manufactured by ESPEC). After curing, the sample was taken out and placed in an accelerated life test apparatus (manufactured by HIRAYAMA, trade name: PL-422R8, condition: 110 ° C./85% RH / 100 hours), and the insulation resistance was measured. The evaluation method is “A” when the insulation resistance is 1 × 10 ⁸ Ω or more over 100 hours, and “B” when the minimum value of the insulation resistance is 1 × 10 ⁷ Ω or more and less than 1 × 10 ⁸ Ω. The case where the minimum value of the insulation resistance is less than 1 × 10 ⁷ Ω is defined as “C”. In addition, a case where the evaluation result is “C” has a practical problem. The results are shown in Table 2.

  As is apparent from the results shown in Table 2, in Examples 1 and 2, the curing accelerator was added to satisfy the condition that the curing reaction rate after heating at 350 ° C. for 10 seconds was 50% or more, Compared with the comparative example 1 which does not contain a hardening accelerator and the curing reaction rate is less than 50%, the void generation rate is drastically reduced. In addition, with respect to Examples 1 and 2 and Comparative Example 1, the initial conduction of the semiconductor device is possible. On the other hand, in Comparative Example 2, the condition that the curing reaction rate after heating at 350 ° C. for 10 seconds is 50% or more is satisfied, and the void generation rate is drastically reduced as compared with Comparative Example 1, but the melt viscosity at 350 ° C. Is over 2000 Pa · s, the initial conduction of the semiconductor device is impossible.

  5A and 5B are photographs showing the external appearance (void situation around the wiring) in the semiconductor device manufactured using the film adhesive of Example 2 and Comparative Example 1. FIG. As is clear from FIG. 5, the void 1 is drastically reduced in Example 2 to which the curing accelerator is added as compared with Comparative Example 1.

It is a schematic cross section which shows the state before the crimping | compression-bonding of the sample A for melt viscosity measurement. It is a schematic cross section which shows the state before the crimping | compression-bonding of the sample B for void incidence rate measurement. 4 is a photograph showing the entire semiconductor device manufactured using the film adhesive of Example 2. It is a photograph which shows the cross section of the chip mounting part in the semiconductor device produced using the film adhesive of Example 2. FIG. It is a photograph which shows the external appearance (void situation of wiring periphery) in the semiconductor device produced using the film adhesive of Example 2 and Comparative Example 1.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Void, 2 ... Copper wiring, 3 ... Glass chip, 4 ... Film adhesive, 5, 9 ... Semiconductor chip, 6, 10 ... Gold bump, 7 ... Cover glass, 8 ... Polyimide substrate, 11 ... Film adhesive Hardened material.

Claims (7)

A film-like adhesive for semiconductor encapsulation containing (a) a polyimide resin, (b) an epoxy resin, (c) a phenol resin, and (d) a curing accelerator,
A film-like adhesive for sealing a semiconductor, having a melt viscosity at 350 ° C. of 2000 Pa · s or less and a curing reaction rate after heating at 350 ° C. for 10 seconds of 50% or more.   The film-like adhesive for semiconductor encapsulation according to claim 1, wherein the (a) polyimide resin has a weight average molecular weight of 30000 or more and a glass transition temperature of 100 ° C or less.   The film-like adhesive for semiconductor encapsulation according to claim 1 or 2, wherein the (d) curing accelerator is an adduct of an imidazole and an organic acid.   The film adhesive for semiconductor encapsulation according to claim 3, wherein the organic acid is isocyanuric acid.   When connecting a semiconductor chip having a bump and a substrate having a metal wiring at a temperature of 300 ° C or higher, the semiconductor chip is connected via the film-like adhesive for semiconductor encapsulation according to any one of claims 1 to 4. A method for manufacturing a semiconductor device, comprising sealing and filling a gap between the semiconductor chip and the substrate with the film-like adhesive for semiconductor sealing.   The bump is a gold bump, the metal wiring is a metal wiring whose surface is tin-plated, the substrate is a polyimide substrate, and the semiconductor chip and the substrate are gold-tin eutectic at a temperature of 300 ° C. or higher. The method of manufacturing a semiconductor device according to claim 5, wherein the semiconductor device is formed and connected.   A semiconductor device manufactured by the method for manufacturing a semiconductor device according to claim 5.