JP5484706B2 - COF semiconductor sealing film adhesive, semiconductor device manufacturing method using the adhesive, and semiconductor device - Google Patents

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 (for example, Patent Documents 1 to 3).

  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.

  Also, in a semiconductor device manufactured by the flip chip connection method, in order to protect the connection part from the external environment, and thermal stress derived from the difference in thermal expansion coefficient between the semiconductor chip and the substrate is concentrated on the connection part, connection failure In order to prevent this, it is necessary to seal and fill the gap between the semiconductor chip and the substrate with resin.

  Sealing and filling methods include a method in which a liquid resin is injected by capillary action after connecting the semiconductor chip and the substrate (post-injection method), and a resin for paste filling or film-like sealing filling is applied to the semiconductor chip or the substrate. A method of connecting a semiconductor chip and a substrate after supply (first supply method) is known. With the progress of miniaturization of semiconductor devices in recent years, the gap between the semiconductor chip and the substrate has become narrower, and the post-injection method requires a long time for injection, resulting in decreased productivity or injectability. Since it may disappear, it is expected to shift to a pre-supply system, and material development corresponding to this system is strongly desired.

  In the post-injection method, the process of connecting the semiconductor chip and the substrate and the process of injecting the liquid resin are separated. Therefore, when developing the liquid resin, the connection conditions (particularly the heating temperature) in the connection process are set. Although it is not necessary to consider, in the first supply method, since the sealing filling is performed at the same time as the connection between the semiconductor chip and the substrate, the resin for sealing filling is a material in which the connection conditions (particularly the heating temperature) are taken into consideration It is necessary to be.

For example, Patent Documents 1 and 2 disclose an epoxy resin composition containing an epoxy resin and a curing agent as a resin for sealing and filling used in the first supply method. Patent Document 3 discloses an epoxy resin adhesive containing a filler.
JP 2004-010810 A Japanese Patent Laid-Open No. 2004-247531 JP 2004-349561 A

  By the way, in the flip-chip connection method, for example, there is a method of metal bonding using solder or tin. In this method, since the heating temperature is 200 ° C. or higher, residual volatile components in the resin, resin It is necessary to suppress foaming derived from the volatile components due to decomposition of the so as not to leave bubbles called voids. When the voids are generated, the resin and the semiconductor chip are peeled off, and the resin and the substrate are peeled off. This causes the connection reliability to be lowered and the insulation reliability between the wirings to be lowered.

  Also, in liquid crystal display modules that are becoming smaller in size, a semiconductor chip for driving a liquid crystal having gold bumps formed on a polyimide substrate on which a copper wiring whose surface is tin-plated is formed is bonded to a metal by gold-tin eutectic. Although a semiconductor device called COF (Chip On Film) mounted on the substrate is widely used, the connection pitch is 30 μm or less, and the insulation reliability decreases if voids remain.

  Furthermore, in COF, in order to form a gold-tin eutectic, it is necessary to make the connection part 278 ° C. or higher, which is the eutectic temperature, and from the viewpoint of improving productivity, the connection time is as short as 5 seconds or less. In order to heat the connection part to the eutectic temperature or higher in a short time, the set temperature of the manufacturing apparatus becomes a high temperature of 300 to 400 ° C. Therefore, especially for the resin for sealing filling, foaming at a high temperature must be suppressed. I must.

  However, in the adhesive compositions of Patent Documents 1 to 3, bubbles and voids are generated to such an extent that the connection reliability between the semiconductor chip and the substrate and the insulation reliability between the wires can be sufficiently prevented. It was difficult to suppress.

  When the adhesive is in the form of a paste, the present inventors may contaminate the manufacturing apparatus by scattering the resin whose viscosity has been reduced or by scooping up the side surface of the chip. I found out. Furthermore, special manufacturing conditions are required to eliminate voids, and the process becomes complicated. In addition, when applying a paste-like adhesive, there is also a problem that the supply amount varies greatly due to a change in viscosity.

  Therefore, the present invention can suppress the generation of foaming and voids when connecting the semiconductor chip and the substrate at a heating temperature of 300 ° C. or higher, and can realize sufficient insulation reliability between the wirings, and excellent workability. An object of the present invention is to provide a film-like adhesive for sealing a semiconductor, a method for manufacturing a semiconductor device using the adhesive, and a semiconductor device.

  In order to achieve the above object, the present invention provides a film-like adhesive for encapsulating a semiconductor containing (a) a polyimide resin, (b) an epoxy resin, and (c) a curing agent.

  According to such a film-like adhesive for semiconductor sealing, when a semiconductor chip and a substrate are connected at a heating temperature of 300 ° C. or higher, foaming and voids are suppressed, and sufficient insulation reliability between wirings is realized. In addition, excellent workability can be obtained.

  Moreover, it is preferable that the 1% thermal weight reduction | decrease temperature is 250 degreeC or more as for the film-form adhesive for semiconductor sealing of this invention.

  Such a film-like adhesive for sealing a semiconductor does not cause foaming due to residual volatile components in the resin or volatile components due to decomposition of the resin even when the heating temperature at the time of connection between the semiconductor chip and the substrate is 300 ° C. or higher. It can suppress and generation | occurrence | production of a void can fully be suppressed.

  Moreover, in the film-form adhesive for semiconductor sealing of this invention, it is preferable that the glass transition temperature of (a) polyimide resin is 20-100 degreeC.

  (A) If the glass transition temperature of the polyimide resin is within the above range, bumps formed on the semiconductor chip, or irregularities such as electrodes and wiring patterns formed on the substrate can be embedded satisfactorily. The remaining bubbles can be more sufficiently suppressed. Moreover, it is preferable because it is easy to handle and excellent in workability.

  Moreover, in the film-like adhesive for semiconductor encapsulation of the present invention, the (c) curing agent is preferably a phenol resin.

  (C) When a phenol resin is used as a curing agent, it is possible to form a cured product exhibiting high heat resistance, hydrolysis resistance, and good adhesion, and it is possible to realize excellent connection reliability. Therefore, it is preferable.

  In 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 wirings and sufficient connectivity between a semiconductor chip and a 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, and Sufficient connectivity between the semiconductor chip and the substrate can be obtained.

  According to the present invention, when connecting a semiconductor chip and a substrate at a heating temperature of 300 ° C. or higher, generation of foam and voids can be suppressed, sufficient insulation reliability between wirings can be realized, and excellent workability can be achieved. It is possible to provide a film-like adhesive for sealing a semiconductor, a method for manufacturing a semiconductor device using the adhesive, and a semiconductor device.

(Film adhesive for semiconductor encapsulation and method for producing the same)
The film-like adhesive for semiconductor encapsulation of the present invention contains (a) a polyimide resin, (b) an epoxy resin, and (c) a curing agent. 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, and the following general formula (I) Examples thereof include tetracarboxylic dianhydrides and tetracarboxylic dianhydrides represented by the following general formula (II).

［式中、ｍは２〜２０の整数を示す。］

[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 general 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 general formula (II) is preferably 40 mol% or more, more preferably 50 mol% or more, and more preferably 70 mol% with respect to the total tetracarboxylic dianhydride. The above is particularly preferable. If it is less than 40 mol%, it tends to be difficult to obtain the effect of moisture resistance reliability due to the use of the tetracarboxylic dianhydride represented by the general 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′-diaminodiphenylethermethane, 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'-diaminodiphenylsulfur Fo 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfide, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 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) Benzene, 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-amino Noenoxy) 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.

［式中、Ｑ^１、Ｑ^２及びＱ^３は各々独立に炭素数１〜１０のアルキレン基を示し、ｒは２〜８０の整数を示す。］

[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. ]

［式中、ｑは５〜２０の整数を示す。］

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

［式中、Ｑ^４及びＱ^９は各々独立に炭素数１〜５のアルキレン基又は置換基を有してもよいフェニレン基を示し、Ｑ^５、Ｑ^６、Ｑ^７、及びＱ^８は各々独立に炭素数１〜５のアルキル基、フェニル基又はフェノキシ基を示し、ｐは１〜５の整数を示す。］

[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 mol% of the total diamine, and It is preferable that the siloxane diamine represented by the general formula (V) is 20 to 79 mol% 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;

Among the aliphatic ether diamines represented by the above formula, the aliphatic ether diamine represented by the following general formula (VI) is able to ensure low-temperature laminating properties and good adhesion to a substrate with an organic resist. Is more preferable.

［式中、ｓは２〜８０の整数を示す。］

[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, where p is 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.

  20-100 degreeC is preferable and, as for the glass transition temperature (Tg) of said (a) polyimide resin, 20-80 degreeC is more preferable. When Tg is less than 20 ° C., the adhesiveness of the film increases, and the handleability may decrease. On the other hand, when the temperature exceeds 100 ° C., it becomes difficult to bury unevenness such as bumps formed on the semiconductor chip, electrodes and wiring patterns formed on the substrate, and bubbles tend to remain and cause voids. The Tg is a value read from an endothermic peak temperature measured by differential scanning calorimetry or a tan δ peak temperature obtained by dynamic viscoelasticity measurement.

  The above (a) polyimide resin is desirably capable of forming a film alone, and its weight average molecular weight is preferably controlled within a range of 10,000 to 200,000, more preferably 20,000 to 150,000, and particularly preferably 30,000 to 100,000. preferable. If the weight average molecular weight is less than 10,000, the film formability tends to be reduced, and if it exceeds 200,000, the fluidity during heating is lowered and connection failure may occur. 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 make, product 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) Curing agent (c) The curing agent used in the present invention is not particularly limited, and examples thereof include phenol resins, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, and alicyclic rings. Examples include formula acid anhydrides, aromatic acid anhydrides, dicyandiamide, organic acid dihydrazides, boron trifluoride amine complexes, imidazoles, and tertiary amines. Among these curing agents, imidazoles or phenol resins are preferable, and phenol resins having at least two phenolic hydroxyl groups in the molecule are more preferable.

  Examples of imidazoles include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano. 2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (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- E sulfonyl imidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxy methyl imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and the like adducts of epoxy resin and the imidazoles. These may be used alone or in combination of two or more. Moreover, you may use what microencapsulated these and raised the potential.

  Phenol resins include bisphenol resin, phenol novolak resin, naphthol novolak resin, allylated phenol novolak resin, biphenol resin, cresol novolak resin, phenol aralkyl resin, cresol naphthol formaldehyde polycondensate, triphenylmethane type polyfunctional phenol resin, xylylene Modified phenol novolac resins, xylylene modified naphthol novolac resins, various polyfunctional phenol resins, and the like can be used. These can be used alone or as a mixture of two or more.

  (C) The compounding quantity of a hardening | curing agent is suitably adjusted so that it may become a cure rate which does not raise | generate a connection defect, and the fall of connection reliability by the fall of sclerosis | hardenability does not occur. For example, when (imidazole) is used as the curing agent (c), 0.1 to 20 parts by mass is preferable, 0.1 to 10 parts by mass is more preferable, and 0.1 to 10 parts by mass is preferable with respect to 100 parts by mass of the epoxy resin. 1 to 5 parts by mass is more preferable. If it is less than 0.1 parts by mass, the curability may be reduced and the connection reliability may be reduced. If it exceeds 20 parts by mass, the curing rate may be too high, resulting in poor connection.

  In addition, when (c) a phenol resin is used as a curing agent, (b) the equivalent ratio of epoxy resin to phenol resin ((c) phenol resin / (b) epoxy resin) is curable, adhesive, and storage stability. It is preferable to set to 0.4-1.2 from viewpoints, etc., 0.4-1.1 are more preferable, and 0.5-1.0 are further more preferable. If the equivalent ratio is less than 0.4, the curability may be lowered and the adhesive force may be reduced. If the equivalent ratio is more than 1.2, an unreacted phenolic hydroxyl group remains excessively and the water absorption rate increases. Insulation reliability may be reduced.

  The mass ratio of the (a) polyimide resin and the mixture of (b) epoxy resin and (c) curing agent is not particularly limited, but in order to maintain the film shape, (a) to 100 parts by mass of the polyimide resin The mixture of (b) epoxy resin and (c) curing agent is preferably 5 to 200 parts by mass, more preferably 5 to 150 parts by mass, and even more preferably 10 to 100 parts by mass. If it is less than 5 parts by mass, the curability may be reduced and the adhesive force may be reduced, and if it exceeds 200 parts by mass, the film formability may be reduced.

  The 1% thermal weight loss temperature of the film adhesive of the present invention is preferably 250 ° C or higher, more preferably 270 ° C or higher, and further preferably 300 ° C or higher. If the 1% thermal weight loss temperature is less than 250 ° C., volatile components may be generated due to decomposition of the resin during high-temperature connection, and foaming may become prominent.

  The film adhesive of the present invention may contain a filler in order to control the viscosity of the adhesive composition and the physical properties of the cured product. As the filler, an insulating inorganic filler, whisker, or resin filler 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, glass, silica, alumina, titanium oxide and the like are preferable, and glass, silica, alumina, and the like are preferable. Is 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 as a mixture of two or more.

  The filler preferably has an average particle size of 10 μm or less and a maximum particle size of 25 μm or less, more preferably an average particle size of 5 μm or less and a maximum particle size of 20 μm or less. If the average particle diameter exceeds 10 μm and the maximum particle diameter exceeds 25 μm, fillers may be sandwiched between wirings with a narrow pitch such as COF, which may reduce insulation reliability.

  Furthermore, you may mix | blend a hardening accelerator, 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 individually by 1 type and may be used in combination of 2 or more type. What is necessary is just to adjust about a compounding quantity so that the effect of each additive may express.

  The film adhesive of the present invention is obtained by mixing and kneading the above-mentioned (a) polyimide resin, (b) epoxy resin, (c) curing agent, and, if necessary, a filler and other components in an organic solvent. After preparing a varnish (varnish for coating a film adhesive), a layer of the varnish is formed on a substrate film, dried by heating, and then the substrate can be removed.

  The above mixing and kneading can be carried out by appropriately combining dispersers such as a normal stirrer, a raking machine, a triple roll, and a ball mill. The heating and drying conditions are not particularly limited as long as the solvent used is sufficiently volatilized, but it is usually performed by heating at 60 to 200 ° C. for 0.1 to 90 minutes.

  The organic solvent used for the preparation of the varnish in the production of the film adhesive, that is, the varnish solvent is not limited as long as the material can be uniformly dissolved, kneaded, or dispersed. For example, dimethylformamide, dimethylacetamide, N- Examples include methyl pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, and ethyl acetate. Nitrogen-containing compounds are preferred in that the reaction proceeds effectively. Examples of such a solvent include the above-mentioned dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Among them, N-methylpyrrolidone is preferable in that the solubility of the polyimide resin is excellent.

  The base film used in the production of the film adhesive is not particularly limited as long as it can withstand the heating and drying conditions described above. For example, polyester film, polypropylene film, polyethylene terephthalate film, polyimide film, polyetherimide Examples thereof include a film, a polyether naphthalate film, and a methyl pentene film. Two or more kinds of these base films may be combined to form a multilayer film, or the surface may be treated with a release agent such as silicone or silica. Moreover, it is good also as a film-form adhesive with a base material used as the support body of a film-form adhesive, without removing a base film.

(Semiconductor manufacturing apparatus and semiconductor device manufacturing method)
Then, with reference to FIG. 1, an example of the manufacturing method of the semiconductor device using the film adhesive for semiconductor sealing of this invention is demonstrated.

  The manufacturing method of the semiconductor device using the film-like adhesive for semiconductor sealing of the present invention includes, for example, (a) a substrate preparation step, (b) a resin supply step, (c) an alignment step, (d) a connection step, (E) An after-cure process is provided.

  First, in (a) substrate preparation step, a substrate 2 having a metal wiring 1 formed on its surface is prepared. The material of the substrate is not particularly limited, and examples thereof include inorganic substrates such as ceramics, and organic substrates such as epoxy resins, bismaleimide triazine resins, polyimide resins, and liquid crystal polymers. Among these, in the case of COF, a polyimide resin or a liquid crystal polymer is preferable. Examples of the material for forming the metal wiring 1 of the substrate 2 include copper, aluminum, silver, gold, and nickel. The metal wiring 1 is formed by etching or pattern plating. The surface of the metal wiring 1 is preferably plated with gold, nickel, tin or the like. In particular, in the case of COF, the metal wiring 1 may be a copper wiring whose surface is tin-plated. Is preferred.

  Next, in the (b) resin supply step, for example, as shown in FIG. 1, the film-like adhesive 3 of the present invention cut out to a predetermined size may be attached to the substrate 2, or a semiconductor wafer. A semiconductor chip to which the film adhesive 3 is attached may be manufactured by dicing into individual pieces after being attached to the bump forming surface. The supply amount of the film-like adhesive can be controlled by the area and thickness, and the area to be sealed and filled can be considered from the size of the semiconductor chip 5 described later, the height of the bumps 6 formed on the surface of the semiconductor chip, and the like. It is set appropriately according to the volume.

  After affixing the film adhesive to the substrate 2 or the semiconductor chip 5, in the (c) alignment step, the metal wiring 1 of the substrate 2 and the bumps 6 of the semiconductor chip 5 attached to the bonding head 4 are aligned. To do. In the subsequent (d) connecting step, heating is performed to a temperature at which the metal joint is formed so that the metal joint is formed at the connection between the metal wiring 1 of the substrate 2 and the bump 6 of the semiconductor chip 5. The semiconductor chip 5 and the substrate 2 are connected by applying pressure for 0.5 to 10 seconds. For example, in the case of COF, since the connection time is as short as 5 seconds or less and it is necessary to raise the temperature to 278 ° C. or higher, which is the eutectic temperature, in order to eutectic gold and tin in a short time, it is usually 300 to 500. The semiconductor chip 5 heated to ° C. is pressed against the substrate 2 to be connected. The connection load depends on the number of bumps, but is set in consideration of absorption of variation in the height of the bumps 6 and control of the amount of bump deformation. The material of the bump 6 formed on the semiconductor chip 5 is not particularly limited, and examples thereof include gold, low melting point solder, high melting point solder, nickel, and tin. In particular, gold is suitable for COF.

  Furthermore, after the semiconductor chip and the substrate are connected, a post-cure process may be performed in which a heat treatment is performed in an oven or the like in order to further advance the curing.

  The semiconductor device manufacturing method of the present invention described above is generally called a pre-feeding method, and has a difference in the order of supplying adhesives and the method of supplying adhesives, compared to the post-injection method shown in FIG.

  In the conventional post-injection method shown in FIG. 2, (b) the alignment step is performed after the substrate preparation step, and then the semiconductor chip 8 having the bumps 9 and the substrate 2 are connected (c). A connection process is performed. (C) After the connection step, (d) a liquid resin injection step corresponding to (b) resin supply step of the present invention is performed. Here, the liquid resin 10 is placed in the gap between the semiconductor chip 8 and the substrate 2. Injected. Further, (d) an after-cure process is performed as appropriate.

  With the miniaturization of the semiconductor device, the gap between the semiconductor chip 8 and the substrate 2 is narrowed. With such a post-injection method, it becomes difficult to inject the liquid resin 10 in the (d) liquid resin injection step. However, according to the method of manufacturing a semiconductor device of the present invention, the problem of the post-injection method is overcome. Furthermore, by using the film adhesive of the present invention, when connecting a semiconductor chip and a substrate at a heating temperature of 300 ° C. or higher, it is possible to suppress the generation of foaming and voids, and between wirings A semiconductor device having sufficient insulation reliability can be provided.

  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. The mixture was stirred while being heated at 170 ° C. for 8 hours while blowing nitrogen gas. The produced water was removed to obtain a polyimide resin solution (varnish). The obtained polyimide resin (solid content) had a Tg of 22 ° C., a weight average molecular weight of 47000, and an SP value of 10.2. In the preparation of the film adhesive, the varnish (solid content concentration 40.6% by mass) was used as it was without isolating the polyimide resin from this solution.

Example 1
3.99 g of polyimide resin solution (varnish) synthesized in the synthesis example (polyimide resin (solid content) 1.62 g), cresol novolac-type solid epoxy resin YDCN-702 (trade name, epoxy equivalent 200 manufactured by Tohto Kasei Co., Ltd.) 0.18 g, 0.18 g of triphenylmethane type polyfunctional solid epoxy resin VG3101L (trade name, epoxy equivalent 200, manufactured by Printec Co., Ltd.), phenol novolac resin HP850 (trade name, hydroxyl equivalent 106, manufactured by Hitachi Chemical Co., Ltd.) ) 0.12 g, boron nitride filler (manufactured by Mizushima Alloy Iron Co., Ltd., trade name: HPP1-HJ) 0.70 g, silica filler (manufactured by Nippon Aerosil Co., Ltd., trade name: R972) 0.11 g, curing accelerator (imidazole 2PHZ) -PW, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.0036 g and N It was mixed by stirring methyl-2-pyrrolidone (NMP) 2.0 g, by performing a defoaming treatment to obtain an adhesive composition. The obtained adhesive composition was applied onto a separator film (PET film) using a knife coater, and then dried at 80 ° C. for 30 minutes and then at 120 ° C. for 30 minutes to obtain a film adhesive.

(Comparative Example 1)
Bisphenol type liquid epoxy resin ZX1059 (product name, manufactured by Toto Kasei Co., Ltd.), 12 g, glycidylamine type liquid epoxy resin E-630 (product name, manufactured by Japan Epoxy Resin Co., Ltd.), 8 g, liquid allylated phenol novolac resin MEH8000H (Maywa Kasei) A paste-like adhesive was prepared by mixing 21 g of a product manufactured by Co., Ltd. and 6 g of a microencapsulated imidazole-based latent curing agent HX-3941HP (manufactured by Asahi Kasei Co., Ltd., product name), followed by vacuum defoaming.

(Comparative Example 2)
30 g of bisphenol type liquid epoxy resin ZX1059 (product name, manufactured by Toto Kasei Co., Ltd.), 30 g of glycidylamine type liquid epoxy resin E-630 (product name, manufactured by Japan Epoxy Resin Co., Ltd.), liquid acid anhydride YH306 (stocks of Japan epoxy resin) Company-made, product name) 60 g, solid imidazole 1B2PZ (made by Shikoku Kasei Kogyo Co., Ltd., trade name) 1 g and spherical silica filler SE2050 (manufactured by Admatechs Co., Ltd., trade name) 100 g were kneaded with three rolls, and then vacuum degassed. A paste-like adhesive was prepared by foaming.

(Comparative Example 3)
90 g of bisphenol A type liquid epoxy resin EP828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), 1 g of dicyandiamide, 1 g of solid imidazole 2MZ (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) and spherical silica filler SE2050 (manufactured by Admatechs, Product name) After kneading 10 g with three rolls, a paste adhesive was prepared by vacuum defoaming.

(Comparative Example 4)
25 g of phenoxy resin YP-50 (manufactured by Toto Kasei Co., Ltd., trade name), 30 g of polyfunctional solid epoxy resin EP1032H60 (manufactured by Japan Epoxy Resin Co., Ltd., trade name), 828-type bisphenol A liquid epoxy resin EP828 (manufactured by Japan Epoxy Resin Co., Ltd.) , Trade name) 20 g, microencapsulated imidazole-based latent curing agent HX-3941HP (made by Asahi Kasei Corporation, trade name) 25 g and spherical silica filler SE2050 (manufactured by Admatechs, trade name) 100 g of toluene-ethyl acetate 1 1: Dissolve in a mixed solvent to prepare a varnish, apply this varnish on a separator film (PET film) using a knife coater, and then dry it in an oven at 70 ° C. for 10 minutes to obtain a film adhesive. Produced.

(Comparative Example 5)
15 g of acrylic rubber HTR-860P-3 (trade name, manufactured by Nagase ChemteX Corporation), 25 g of bisphenol F type liquid epoxy resin EXA830CRP (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.), cresol novolac type solid epoxy resin YDCN-702 (Toto Kasei Co., Ltd., trade name) 10 g, Solid phenol novolac resin HP-850 (Hitachi Chemical Industry Co., Ltd., trade name) 20 g, Solid imidazole 2PZ-CN (Shikoku Kasei Kogyo Co., Ltd., trade name) 0. 05 g and 30 g of spherical silica filler SE2050 (manufactured by Admatex Co., Ltd., trade name) were dissolved in cyclohexanone to prepare a varnish, and this varnish was applied onto a separator film (PET film) using a knife coater, and then 110 ° C. Let it dry in the oven for 30 minutes By, to prepare a film adhesive.

<Measurement of 1% thermal weight loss temperature>
About the film-like adhesives of Example 1 and Comparative Examples 4 to 5, using a differential thermothermal gravimetric simultaneous measurement device TG / DTA6300 (product name, manufactured by SII Technology Co., Ltd.), a measurement temperature range of 30 to 500 ° C. is increased. The thermogravimetric decrease was measured at a temperature rate of 10 ° C./min in an air atmosphere, and the 1% thermogravimetric decrease temperature was estimated from the result.

<Evaluation of foamability, initial connectivity and workability>
Polyimide substrate with copper wiring with tin plating on the surface (manufactured by Hitachi ULSI Systems Co., Ltd., product name JKIT COF TEG_30-B, polyimide thickness 38 μm, copper wiring thickness 8 μm, tin plating thickness 0.2 μm, wiring pitch 30 μm) and a semiconductor chip on which gold bumps are formed (manufactured by Hitachi ULSI Systems Co., Ltd., product name JTEG PHASE6_30, size 1.6 mm × 15.1 mm, thickness 400 μm, number of gold bumps 726, bump height 20 μm, bump pitch Flip chip bonder FC-2000 (Toray Engineering Co., Ltd.) equipped with a glass stage and an observation camera. The adhesive prepared in Example 1 and Comparative Examples 1 to 5 was applied or applied to the polyimide substrate. After alignment with the company), the stage temperature is 100 ° C, The semiconductor chip and the substrate were connected at a lid temperature of 350 ° C., a load of 50 N, and a connection time of 3 seconds.

  For the state of foaming, the semiconductor chip mounting area during connection was observed from the polyimide substrate side, and the part where the adhesive was applied or applied was observed. “A” indicates that no foaming was observed, and “A” indicates that foaming was observed. B ".

  In addition, since the polyimide substrate and the semiconductor chip used this time can evaluate the connection resistance by daisy chain connection, the resistance value of daisy chain connection is about the same as the value (250Ω) when connected without adhesive. Some were determined to be initial connectable “A”.

  Furthermore, for workability, the appearance of the sample after connection is observed, and “A” indicates that no resin scattering or resin contamination on the backside of the chip is observed, and “A” indicates that resin scattering or resin contamination on the backside of the chip is observed. “B”.

<Evaluation of insulation reliability>
A connection sample prepared by the same method as the evaluation of foamability was heat-treated at 150 ° C. for 2 hours, and then a 60 V direct current was applied to the parallel wiring (wiring pitch 30 μm) formed in the chip mounting region of the polyimide substrate. A voltage was applied, and the sample was left in a test tank at a temperature of 110 ° C./85% relative humidity for 100 hours. The insulation resistance in the test tank was continuously measured using an ion migration tester MIG-8600B (manufactured by IMV), and the time during which the insulation resistance value of 10 ⁸ Ω or more was maintained during the measurement was measured. The case where it could be maintained for 100 hours was indicated as OK, and the case where it could not be maintained was indicated as NG.

  Table 1 below shows the results of evaluation of 1% thermal weight loss temperature, foamability, initial connectivity, workability, and insulation reliability.

  In FIG. 3, in the part where the adhesives of the samples of Example 1 and Comparative Examples 1 to 5 were affixed or applied, a photograph of the state of the resin being connected with a camera provided on the flip chip bonder, and after the connection The observation photograph by the metallographic microscope of the part which stuck or apply | coated the adhesive agent of the sample is shown. In Example 1, resin foaming and voids were not confirmed. On the other hand, in Comparative Examples 1 to 5, resin foaming and voids were confirmed.

Furthermore, the insulation resistance continuous measurement results are shown in FIGS. The sample of Example 1 was able to maintain an insulation resistance value of 10 ⁸ Ω or higher even after 100 hours had elapsed. On the other hand, in all samples of Comparative Examples 1 to 5, the insulation resistance decreased to 10 ⁸ Ω or less within 100 hours, and insulation reliability could not be ensured.

  Further, in Example 1, resin scattering and chip back surface contamination were not observed, whereas in paste-like Comparative Examples 1 to 3, resin scattering and chip back surface contamination were observed.

  As described above, according to the film-like adhesive for semiconductor encapsulation of the present invention, even when heated at 300 ° C. or higher, it is possible to suppress the generation of voids without causing resin foaming, and the insulation reliability between narrow pitch wirings. Sex can be secured. Moreover, since the manufacturing process of a semiconductor device can be simplified when the film-like adhesive for sealing a semiconductor of the present invention is used, productivity can be improved.

FIG. 1 is a schematic cross-sectional view showing an example of a method for manufacturing a semiconductor device using the film-like adhesive for sealing a semiconductor of the present invention. FIG. 2 is a schematic cross-sectional view for explaining a conventional method of manufacturing a semiconductor device by a post-injection method. FIG. 3 is an observation photograph by a metallographic microscope for evaluating the foamability of the samples of Example 1 and Examples 1-5. 4 is a graph showing the results of continuous measurement of insulation resistance in the insulation reliability evaluation of Example 1. FIG. FIG. 5 is a graph showing the results of continuous measurement of insulation resistance in the insulation reliability evaluation of Comparative Example 1. FIG. 6 is a graph showing the results of continuous measurement of insulation resistance in the insulation reliability evaluation of Comparative Example 2. FIG. 7 is a graph showing the results of continuous measurement of insulation resistance in the insulation reliability evaluation of Comparative Example 3. FIG. 8 is a graph showing the results of continuous measurement of insulation resistance in the insulation reliability evaluation of Comparative Example 4. FIG. 9 is a graph showing the results of continuous measurement of insulation resistance in the insulation reliability evaluation of Comparative Example 5.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Metal wiring, 2 ... Board | substrate, 3 ... Film adhesive, 4, 7 ... Joining head, 5, 8 ... Semiconductor chip, 6, 9 ... Bump, 10 ... Liquid resin.

Claims (5)

When a semiconductor chip having gold bumps and a polyimide substrate having metal wiring plated with tin are connected by forming a gold-tin eutectic at a temperature of 300 ° C. or higher, the semiconductor chip and the polyimide substrate A film-like adhesive for sealing a COF semiconductor interposed therebetween ,
(A) containing a polyimide resin, (b) an epoxy resin, and (c) a curing agent,
A film-like adhesive for sealing a COF semiconductor having a 1% thermal weight loss temperature of 250 ° C. or higher.   The film adhesive for COF semiconductor encapsulation according to claim 1, wherein the glass transition temperature of the (a) polyimide resin is 20 to 100 ° C.   The film adhesive for COF semiconductor sealing according to claim 1 or 2, wherein the (c) curing agent is a phenol resin.   A semiconductor chip having gold bumps and a polyimide substrate having a metal wiring plated with tin are heated to 300 ° C. or higher via the film-like adhesive for sealing a COF semiconductor according to claim 1. A method of manufacturing a semiconductor device, comprising: forming a gold-tin eutectic crystal at a temperature, connecting, and sealingly filling a gap between the semiconductor chip and the substrate with the film-like adhesive for sealing a COF semiconductor .   A semiconductor device manufactured by the method for manufacturing a semiconductor device according to claim 4.

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