JP2019165125A - Film adhesive for semiconductor - Google Patents

Abstract

To provide a film adhesive for a semiconductor capable of preventing productivity drops due to the fillet adhering to adjacent chips and deterioration of reliability due to lack of fillet at package edge when fillet is suppressed when a pitch between chips of semiconductor devices in which electrodes of each connection part are electrically connected to each other through an adhesive is reduced.SOLUTION: The film adhesive for a semiconductor is used for manufacturing a semiconductor device in which electrodes of each connection part of a semiconductor chip and a printed circuit board are electrically connected to each other via the adhesive or electrodes of each connection part of a plurality of semiconductor chips are electrically connected to each other via the adhesive. A value of a polar component γof surface free energy of the adhesive is 1.3 or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a film adhesive for semiconductors used in the manufacture of semiconductor devices, and is an adhesive that is interposed between a semiconductor chip and a printed circuit board to maintain and fix the bonding between electrodes, or between a plurality of semiconductor chips. The present invention relates to a film-like adhesive that intervenes to maintain and fix the bonding between electrodes.

  Until now, wire bonding methods using fine metal wires such as gold wires have been widely applied to connect semiconductor chips and substrates, but in order to meet demands for high functionality, high integration, high speed, etc. for semiconductor devices, A flip chip connection method (FC connection method) in which conductive protrusions called bumps are formed on a semiconductor chip or a substrate to directly connect the semiconductor chip and the substrate is becoming widespread.

  Flip chip connection methods include metal bonding using solder, tin, gold, silver, copper, etc., metal bonding by applying ultrasonic vibration, method of maintaining mechanical contact by the shrinkage force of the resin, etc. However, from the viewpoint of the reliability of the connection portion, a method of metal bonding using solder, tin, gold, silver, copper, or the like is common.

  For example, in connection between a substrate and a semiconductor chip, a COB (Chip On Board) type connection method actively used for BGA (Ball Grid Array), CSP (Chip Size Package), etc. is also an FC connection method.

  Area array type semiconductor packages used for CPUs, MPUs, and the like are strongly required to have high functionality, such as an increase in the size of a chip, an increase in the number of pins (bumps and wiring), and an increase in density of pitches and gaps.

  The FC connection method is also widely used in a COC (Chip On Chip) type connection method in which bumps or wirings are formed on semiconductor chips to connect the semiconductor chips (for example, see Patent Document 1).

JP 2008-294382 A

  For packages that are strongly demanded for further miniaturization, thinning, and high functionality, chip stack type packages, POP (Package On Package), TSV (Through-Silicon Via), etc., in which the above connection methods are stacked and multi-staged, are widely used. It has begun to spread.

  Since the package can be made smaller by arranging it in a three-dimensional shape instead of a flat shape, the above technology is frequently used, and it is also effective for improving semiconductor performance, reducing noise, reducing mounting area, and reducing power consumption. It is attracting attention as a wiring technology.

As described above, the flip chip package has been improved in functionality and integration. However, as the functionality and integration are increased, the pitch between the wirings is narrowed, and the insulation reliability is lowered.
Also, for the purpose of cost reduction, the pitch between chips at the time of package assembly is becoming narrower. By reducing the distance between chips, productivity is improved and costs are reduced.

As described above, when the pitch between the chips is narrowed, when the adhesive for the semiconductor protrudes around the chip at the time of connection, it reaches the adjacent chip and is likely to be defective.
Therefore, it is required to suppress the amount of the semiconductor adhesive that protrudes during connection.
The protruding portion of the semiconductor adhesive at the time of connection is called a “fillet”. Although it is possible to suppress the fillet by reducing the film thickness, when the film is thinned, the amount of fillet at the end of the package is reduced, which may reduce the reliability.

  The present invention aims at improving productivity in flip chip packages that have advanced functions, high integration, and low costs, and the pitch between chips is narrowed, and accordingly, fillets adhere to adjacent chips. It is an object of the present invention to provide a film-like adhesive for a semiconductor that suppresses a decrease in productivity due to the above and a decrease in reliability due to a fillet shortage at the end of a package when the fillet is suppressed.

The present invention relates to the following.
(1) A semiconductor device in which electrodes of each connection portion are electrically connected to each other via an adhesive between a semiconductor chip and a printed circuit board, or a plurality of semiconductor chips are connected to each connection portion via an adhesive. an adhesive used in manufacturing a semiconductor device electrodes to each other are electrically connected to each other, the semiconductor film-like adhesive for which the value of the polar component gamma _S ^P of the surface free energy of the adhesive is 1.3 or more.
The value of the polar component gamma _S ^P is the surface of the film-shaped semiconductor film-like adhesive for pure water, respectively dropwise diiodomethane, to measure the static contact angle, the value of the static contact angle was measured, Owens -Calculated based on Wendt's method.
(2) The film adhesive for semiconductors according to (1) above, wherein the melt adhesive at 130 ° C. of the film adhesive for semiconductors is 10,000 Pa · s or less.
(3) The semiconductor according to (1) or (2) above, wherein the film adhesive for semiconductor contains (a) an epoxy resin, (b) a curing agent, and (c) a high molecular weight component having a molecular weight of 10,000 or more. Film adhesive.
(4) The semiconductor component according to any one of (1) to (3), wherein the high molecular weight component (c) having a molecular weight of 10,000 or more has a weight average molecular weight of 20,000 or more and a glass transition temperature of 100 ° C. or less. Film adhesive.

  By mounting through the film-like adhesive for semiconductors of the present invention, a semiconductor device can be manufactured in which fillets are suppressed and the fillets at the package ends can be secured.

It is a connection sectional view between a semiconductor chip and a substrate (example COB). It is a connection sectional view between semiconductor chips (example COC). It is sectional drawing of a semiconductor chip lamination type (example TSV).

  The chip | tip, board | substrate, etc. which are used with the manufacturing method of the semiconductor device using the film-form adhesive for semiconductors of this invention are demonstrated below.

  The semiconductor chip is not particularly limited, and various semiconductors such as elemental semiconductors such as silicon and germanium, and compound semiconductors such as gallium / arsenic and indium / phosphorus can be used.

  The wiring circuit board (semiconductor substrate) is not particularly limited as long as it is a normal circuit board, and the main components are insulation such as glass epoxy resin, polyimide resin, polyester resin, ceramic, epoxy resin, bismaleimide triazine resin, etc. The wiring pattern is formed by etching away unnecessary portions of the metal layer formed on the substrate surface, the wiring pattern is formed by metal plating on the insulating substrate surface, and the conductive material is printed on the insulating substrate surface. For example, a wiring pattern can be used.

  On the surface of the wiring pattern, a metal layer composed of gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc. as main components The metal layer may be composed of only a single component or a plurality of components. Moreover, you may have the structure where the some metal layer was laminated | stacked. Copper and solder are generally used because they are inexpensive.

  As materials for the conductive protrusions called bumps, the main components are gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc. May be used, and may be composed of only a single component or a plurality of components. Moreover, you may form so that the structure where these metals were laminated | stacked may be made | formed. The bump may be formed on a semiconductor chip or a substrate. Copper and solder are generally used because they are inexpensive.

1-3 show an example of a semiconductor device manufactured using the semiconductor film adhesive of the present invention.
FIG. 1 shows a cross-sectional structure when a connection is made between a semiconductor chip and a substrate, and FIG. 2 shows a cross-sectional structure when a connection is made between semiconductor chips. The connection part may be either a bump and a wiring, or a metal bonding by a bump and a bump, as long as it is a semiconductor device (flip chip connection) that requires electrical connection via the semiconductor film adhesive of the present invention. .

  These packages as shown in FIG. 1 and FIG. 2 are stacked and gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc. May be electrically connected. Copper and solder are preferred because they are generally used because they are inexpensive.

  For example, as seen in TSV (Through-Silicon Via) technology, the film-like adhesive for semiconductor of the present invention is flip-chip connected or stacked between semiconductor chips to form a hole penetrating the semiconductor chip, You may connect with the electrode of a pattern surface. An example of a cross-sectional structure is shown in FIG. As a result, signals can be exchanged also from the back side of a chip that is not normally used, and wiring is passed vertically in the chip, so that the chip and the chip and the interposer can be connected in a shortest and flexible manner. The film adhesive for semiconductors of the present invention can also be applied between the laminated chip and the interposer.

  In addition, for example, in the bump forming method with improved flexibility, which is known in the area bump chip technology or the like, even when the chip is directly mounted on the mother board without using an interposer, the film for a semiconductor of the present invention is used. Adhesive can be applied.

The method of sticking the semiconductor film adhesive on the substrate can be performed by heating press, roll laminating, vacuum laminating or the like. The supply area and thickness of the film adhesive for semiconductor are appropriately set according to the size of the semiconductor chip or substrate, the bump height, and the like. The semiconductor film adhesive may be attached to a semiconductor chip, and after applying the semiconductor film adhesive of the present invention to a semiconductor wafer, it is diced and separated into semiconductor chips. You may produce the semiconductor chip which stuck the film adhesive. After bonding the film adhesive for semiconductor to the substrate or semiconductor chip, after aligning the solder bumps of the semiconductor chip and the copper wiring of the substrate using a connecting device such as a flip chip bonder, the semiconductor chip and the substrate are soldered Pressing while heating at a temperature equal to or higher than the melting point of the bump (when solder is used for the connecting portion, it is preferable that the solder portion takes 250 ° C. or more) to connect the semiconductor chip and the substrate, and by using a film adhesive for the semiconductor The gap between the semiconductor chip and the substrate is sealed and filled. 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. The connection time is preferably as short as possible from the viewpoint of improving productivity, and it is preferable to melt the solder, remove the oxide film and impurities on the surface, and form a metal joint at the connection portion.
After the alignment, the semiconductor device may be manufactured by temporarily fixing and melting the solder bumps by heat treatment in a reflow furnace and connecting the semiconductor chip and the substrate. Temporary fixing does not significantly require the necessity of forming a metal bond, and therefore may have a lower load, a shorter time, and a lower temperature than the above-described main pressure bonding, and there are merits such as improved productivity and prevention of deterioration of the connection portion. After connecting the semiconductor chip and the substrate, heat treatment may be performed in an oven or the like to cure the semiconductor film adhesive. The heating temperature is that the curing of the film-like adhesive for semiconductor proceeds, preferably almost completely, and the heating temperature and the heating time may be appropriately set.

The short-time connection means that the time required for 250 ° C. or more is 4 s or less if the connection portion is soldered during the connection formation time (main pressure bonding time). Preferably it is 3 s or less, more preferably 2 s or less.
Further, the main pressing time is preferably 10 s or less, more preferably 5 s or less.

  It is preferable to mount through a semiconductor device in a short time, and to manufacture more highly reliable packages without solder scattering or flow.

(Polar component γ _S ^P of surface free energy of adhesive)
In the present invention, the value of the polar component gamma _S ^P of the surface free energy using a film adhesive is 1.3 or more. The film form means a general film.
In the present invention, the surface free energy γ _S is a value determined by the Owens-Wendt method.

The relationship between the intermolecular force and surface free energy components is shown below.
Dispersion force (γ ^d ): A force in which all molecules oscillate constantly, causing an electric charge bias to generate a dipole and pulling the molecules together (surface free energy dispersion component γ ^d ).
Polarity (orientation) force (γ ^p ): a force in which polar molecules are biased by positive and negative charges due to permanent dipoles, and molecules pull each other positively and negatively (surface free energy polarity (dipole) component γ ^p ).
Specifically, the surface free energy γs is obtained from the simultaneous equations of Expression (1) and Expression (2) in the following <Expression 1>. Here, <Expression 1> is obtained from the Owens expression obtained by extending the Fowkes expression and the Young expression.

<Formula 1>
(1) γ _S = γ _S ^d + γ _S ^p
(2) 1 + cos θ = (2 / γ _L ) ((γ _S ^d γ _L ^d ) ^1/2 + (γ _S ^p γ _L ^p ) ^1/2 )

The above equation (1) is a Fowkes-Owens equation in which the components of the surface free energy are separated, and the surface free energy γ _S includes the polar component γ _S ^p of the surface free energy and the dispersion component γ _S ^p of the surface free energy. The above equation (2) is obtained by combining the equation of Young with the equation of the extended Fowkes model for the interfacial tension γ _SL of the interface such as the solid S and the liquid L. It is a formula.
The surface free energy γ _S is obtained by using two liquids whose surface tension γ _L , surface tension polar component (γ _L ^p ) and surface tension dispersion component (γ _L ^d ) are known in the above formula (2), It is obtained by measuring the contact angle θ in these liquids and solving the above simultaneous equations.

  In the present invention, pure water and diiodomethane are used for the two liquids.

The contact angle of water and diiodomethane with known surface tension was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd .: fully automatic contact angle meter, DM-50) under the conditions of 25 ° C. and 50% RH. The contact angle used for the calculation was the contact angle 10 seconds after each solution was dropped.
The resulting contact angle data calculated by the method of Owens-Wendt, variance component gamma _{S d} of the surface free energy of the semiconductor film-like adhesive for ^a polar component gamma _{S ^p,} the hydrogen bond component gamma _S ^h determined, the components Is the surface free energy γ _S. This calculation was performed using calculation software in the contact angle meter software (FAMAS).

  Hereinafter, the film adhesive for semiconductors used in the present invention will be described.

(A) Epoxy resin As an epoxy resin, if it has two or more epoxy groups in a molecule | numerator, it can be especially used without a restriction | limiting. Specifically, as the epoxy resin of component (a), bisphenol A type, bisphenol F type, naphthalene type, phenol novolak type, cresol novolak type, phenol aralkyl type, biphenyl type, triphenylmethane type, dicyclopentadiene type and Various polyfunctional epoxy resins can be used. These can be used alone or as a mixture of two or more.

  (A) From the viewpoint of suppressing generation of volatile components by decomposition at the time of connection at high temperature, when the temperature at the time of connection is 250 ° C., the thermal weight loss rate at 250 ° C. is 5% or less. It is preferable to use an epoxy resin. In the case of 300 ° C., it is preferable to use an epoxy resin having a thermal weight loss rate at 300 ° C. of 5% or less. Further, bisphenol A-type and bisphenol F-type liquid epoxy resins have a 1% thermogravimetric reduction temperature of 250 ° C. or less, and thus may decompose during high-temperature heating and generate volatile components. For this reason, it is preferable to use a solid epoxy resin at room temperature (1 atm, 25 ° C.). When using a liquid epoxy resin, it is preferably used in combination with a solid epoxy resin.

(B) Curing Agent (b) Examples of the curing agent include phenol resin curing agents, acid anhydride curing agents, amine curing agents, imidazole curing agents, and phosphine curing agents. (B) When the component contains a phenolic hydroxyl group, an acid anhydride, an amine or an imidazole, it exhibits a flux activity that suppresses the formation of an oxide film at the connection part, and improves connection reliability and insulation reliability. it can. Hereinafter, each curing agent will be described.

(Bi) Phenolic resin-based curing agent The phenolic resin-based curing agent is not particularly limited as long as it has two or more phenolic hydroxyl groups in the molecule, and is a phenol novolak resin, a cresol novolak resin, a phenol aralkyl resin. Cresol naphthol formaldehyde polycondensate, triphenylmethane type polyfunctional phenol resin, various polyfunctional phenol resins, and the like can be used. These can be used alone or as a mixture of two or more. Further, since the liquid phenolic resin may be decomposed when heated at a high temperature to generate a volatile component, it is desirable to use a solid phenolic resin at room temperature (1 atm, 25 ° C.).

  The equivalent ratio of (b-i) phenolic resin-based curing agent to (a) epoxy resin (phenolic hydroxyl group / epoxy group molar ratio) is 0.3 from the viewpoints of curability, adhesiveness, storage stability, and the like. Is preferably 1.5, more preferably 0.4 to 1.0, and still more preferably 0.5 to 1.0. If the equivalence ratio is less than 0.3, the curability may be lowered and the adhesive force may be lowered. If the equivalent ratio is more than 1.5, an unreacted phenolic hydroxyl group remains excessively, and the water absorption rate increases. Reliability may be reduced. Since the phenolic hydroxyl group exhibits a flux activity for removing an oxide film, the film-like adhesive for semiconductor contains a phenol resin-based curing agent, so that connectivity and reliability can be improved.

(B-ii) Acid anhydride curing agent Examples of the acid anhydride curing agent include methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and ethylene. Glycol bisanhydro trimellitate and the like can be used. These can be used alone or as a mixture of two or more. Moreover, since a liquid acid anhydride may decompose | disassemble at the time of high temperature heating and a volatile component may generate | occur | produce, it is desirable to use a solid acid anhydride at room temperature (1 atmosphere, 25 degreeC).

  The equivalent ratio of (b-ii) acid anhydride curing agent to (a) epoxy resin (molar ratio of acid anhydride group / epoxy group) is 0 from the viewpoints of curability, adhesiveness, storage stability, and the like. .3-1.5 is preferable, 0.4-1.0 is more preferable, and 0.5-1.0 is still more preferable. If the equivalent ratio is less than 0.3, the curability may be lowered and the adhesive force may be reduced. If the equivalent ratio is more than 1.5, an unreacted acid anhydride will remain excessively, the water absorption rate will increase, and the insulation Reliability may be reduced. Since the acid anhydride exhibits a flux activity for removing the oxide film, the film-like adhesive for semiconductor contains the acid anhydride, whereby the connectivity and reliability can be improved.

(B-iii) Amine-based curing agent As the amine-based curing agent, dicyandiamide or the like can be used. In addition, since liquid amines may decompose when heated at high temperature to generate volatile components, it is desirable to use solid amines at room temperature (1 atm, 25 ° C.).

  The equivalent ratio of (b-iii) amine curing agent to (a) epoxy resin (amine / epoxy group molar ratio) is 0.3 to 1. in terms of curability, adhesiveness, storage stability, and the like. 5, preferably 0.4 to 1.0, and more preferably 0.5 to 1.0. If the equivalent ratio is less than 0.3, the curability may be reduced and the adhesive strength may be reduced. If the equivalent ratio is more than 1.5, unreacted amine may remain excessively, and the insulation reliability may be reduced. . Since amines exhibit a flux activity for removing an oxide film, the film-like adhesive for semiconductor contains amines, whereby connectivity and reliability can be improved.

(B-iv) Imidazole-based curing agent (containing nitrogen atom is a tertiary nitrogen atom)
Examples of imidazole curing agents include 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-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'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')] -Ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-tri Jin isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, adduct of an epoxy resin and an imidazole compound and the like. Among these, from the viewpoint of curability, storage stability, and connection reliability, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-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 Adducts and 2-phenylimidazole isocyanuric acid adducts are preferred. These can be used alone or in combination of two or more. Moreover, you may use the latent hardening | curing agent which encapsulated these and raised the latent.

  The content of (b-iv) imidazole-based curing agent is preferably 0.1 to 20 parts by mass, and 0.1 to 10 parts by mass with respect to 100 parts by mass of (a) epoxy resin. More preferred. If this content is less than 0.1 parts by mass, the curability may be lowered, and if it exceeds 20 parts by mass, the film adhesive for semiconductor is cured before the metal-metal connection is formed. As a result, connection failure may occur. The imidazole curing agent may be used alone as the (b) curing agent, but may be used as a curing accelerator together with the curing agents (bi) to (b-iii).

(Bv) Phosphine curing agent Examples of the phosphine curing agent include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (4-methylphenyl) borate, tetraphenylphosphonium (4-fluorophenyl) borate, and the like. Is mentioned.

  (Bv) 0.1-10 mass parts is preferable with respect to 100 mass parts of epoxy resin of (a) component, and, as for content of a phosphine type hardening | curing agent, 0.1-5 mass parts is more preferable. When the content of the phosphine-based curing agent is 0.1 parts by mass or more, the curability tends to be improved, and when it is 10 parts by mass or less, the film adhesive for semiconductor is cured before the metal bond is formed. There is a tendency that poor connection is unlikely to occur.

(C) High molecular weight component having a molecular weight of 10,000 or more (c) High molecular weight components having a molecular weight of 10,000 or more include phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, polyethylene resin, poly Examples include ether sulfone resins, polyether imide resins, polyvinyl acetal resins, urethane resins, and acrylic rubbers. Among these, phenoxy resin, polyimide resin, acrylic rubber, cyanate ester resin, polycarbodiimide resin, and the like are desirable because of excellent heat resistance and film formability, and phenoxy resin, polyimide resin, and acrylic rubber are more preferable. These high molecular weight components can be used alone or as a mixture or copolymer of two or more.

  (C) The mass ratio of a high molecular weight component having a molecular weight of 10,000 or more, (a) an epoxy resin, and (b) a curing agent is not particularly limited, but film formability, film formability by spin coating, etc. is improved. In order to do this, the total mass of (a) the epoxy resin and (b) the curing agent is 0.01 to 4 parts by mass with respect to 1 part by mass of (c) a high molecular weight component having a molecular weight of 10,000 or more. Preferably, it is 0.1 to 4 parts by mass, more preferably 0.1 to 3 parts by mass. If this mass ratio is less than 0.01 parts by mass, the curability of the film-like adhesive for semiconductor may be reduced, and the adhesive force may be reduced. If it exceeds 4 parts by mass, the film formability and film formability may be reduced. May decrease.

  The polyimide resin used as component (c) can be obtained, for example, by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. More specifically, tetracarboxylic dianhydride and diamine are mixed in an equimolar or nearly equimolar amount in an organic solvent (the order of addition of each component is arbitrary), and the reaction temperature is 80 ° C. or lower, preferably 0 to 60. Addition reaction is carried out at ° C. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide precursor, is generated. The tetracarboxylic dianhydride is preferably recrystallized and purified with acetic anhydride in order to suppress deterioration of various properties of the film adhesive for semiconductors.

  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 and 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'-biphenyl tetracarboxylic 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-perylenetetracarbo Acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic Acid dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic Acid dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2 , 3,6,7-tetrac Loronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride , Thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic Acid dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methyl Phenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis ( , 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 dianhydride, 1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2,2] -oct -7-D -2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (3,4-dicarboxy Phenyl) phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2, -bis [4- (3,4-dicarboxyphenyl) phenyl] Hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride) 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3 Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, tetracarboxylic dianhydride represented by the following general formula (I) ( In the formula, n represents an integer of 2 to 20), and tetracarboxylic dianhydrides represented by the following formula (II).

［式（Ｉ）中、ｍは２〜２０の整数を示す。］

[In formula (I), 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.

  As the tetracarboxylic dianhydride, 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 alone 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, and more preferably 70 mol% with respect to the total tetracarboxylic dianhydride. The above is extremely preferable. When the content is less than 40 mol%, the moisture resistance reliability effect due to the use of the tetracarboxylic dianhydride represented by the above formula (II) tends to be insufficient.

  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'-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) benzene, 1, -Bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4'-( 1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) Phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3 -Aminoenoxy) phenyl) sulfide, bis (4- (4-aminoenoxy) phenyl) sulfide, bis (4- (3-aminoenoxy) pheny L) sulfone, bis (4- (4-aminoenoxy) phenyl) sulfone, aromatic diamines such as 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4-amino) Phenoxyphenyl) propane, aliphatic ether diamine represented by the following formula (III), aliphatic diamine represented by the following general formula (IV), and siloxane diamine represented by the following general formula (V).

［式（ＩＩＩ）中、Ｑ１、Ｑ２及びＱ３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。］

[In formula (III), Q1, Q2 and Q3 each independently represent an alkylene group having 1 to 10 carbon atoms, and r represents an integer of 2 to 80. ]

［式（ＩＶ）中、ｑは５〜２０の整数を示す。］

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

［式（Ｖ）中、Ｑ４及びＱ９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、Ｑ５、Ｑ６、Ｑ７、及びＱ８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。］

[In formula (V), Q4 and Q9 each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q5, Q6, Q7 and Q8 each independently represent a carbon number. 1-5 alkyl groups, phenyl groups or phenoxy groups are shown, and p is an integer of 1-5. ]

  Among these, the diamine represented by the above general formula (III) or (IV) is preferable in that low stress property, low temperature laminating property, and low temperature adhesiveness can be imparted. 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 content of the aliphatic ether diamine represented by the general formula (III) is preferably 1 to 50 mol% of the total diamine, and the aliphatic diamine represented by the general formula (IV) The content is preferably 20 to 80 mol% of the total diamine, and the content of the siloxane diamine represented by the general formula (V) is preferably 20 to 80 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.

で表される脂肪族エーテルジアミンが挙げられ、中でも、低温ラミネート性と有機レジスト付き基板に対する良好な接着性を確保できる点で、下記一般式（ＶＩ）で表される脂肪族エーテルジアミンがより好ましい。

［式中、ｓは２〜８０の整数を示す。］ Moreover, as aliphatic ether diamine represented by the said general formula (III), specifically, following formula;

Among them, 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-, 3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane, etc., where p is 2, 1,1,3,3,5,5-hexamethyl-1,5- Bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetra Phenyl-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-aminobuty ) 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, 1,1,3,3,5 , 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.

  The polyimide resin as component (d) has a glass transition temperature (Tg) of preferably 100 ° C. or lower, more preferably 75 ° C. or lower, from the viewpoint of sticking to a substrate or a chip. When Tg is higher than 100 ° C., bumps formed on the semiconductor chip, and irregularities such as electrodes and wiring patterns formed on the substrate cannot be embedded with the semiconductor sealing adhesive, and bubbles remain. , Tend to cause voids. In addition, said Tg is Tg when it measures on DSC (The Perkin-Elmer company make, DSC-7 type | mold) conditions of sample amount 10mg, temperature increase rate 5 degree-C / min, and measurement atmosphere: Air. is there.

  The weight average molecular weight of the polyimide resin as the component (d) is 10,000 or more in terms of polystyrene, but preferably 30,000 or more, preferably 40000 or more in order to exhibit good film formability alone. More preferably, it is more preferably 50000 or more. If the weight average molecular weight is less than 10,000, film formability may be reduced. In addition, in this specification, a weight average molecular weight means the weight average molecular weight when measured in polystyrene conversion using a high performance liquid chromatography (Shimadzu Corporation make, C-R4A).

  The ratio of the content of the component (d) and the component (c) is not particularly limited, but in order to maintain a good film shape, the component (c) is 0.01 parts by weight with respect to 1 part by weight of the component (d). It is preferable to be set to ˜5 parts by mass, and more preferably 0.1 to 2 parts by mass. If the content ratio is less than 0.01 parts by mass, the curability may be reduced and the adhesive strength may be reduced. If the content ratio is more than 5 parts by mass, the film formability and film formability may be reduced.

  The high molecular weight component (c) having a molecular weight of 10,000 or more has a glass transition temperature (Tg) of preferably 100 ° C. or less, more preferably 75 ° C. or less, from the viewpoint of sticking to a substrate or a chip. preferable. When Tg is higher than 100 ° C., bumps formed on the semiconductor chip, and irregularities such as electrodes and wiring patterns formed on the substrate cannot be embedded with the film-like adhesive for semiconductor, and bubbles remain. And tends to cause voids. In addition, said Tg is when using a differential scanning calorimeter (Perkin Elmer Co., Ltd., DSC-7 type) with a sample amount of 10 mg, a heating rate of 5 ° C./min, and a measurement atmosphere: measured under the conditions of air. Tg.

  The weight average molecular weight of the high molecular weight component having a molecular weight of 10,000 or more, which is the component (c), is 10,000 or more in terms of polystyrene, but preferably 20,000 or more, and preferably 30,000 or more in order to exhibit good film-formability independently. It is more preferable that it is 40000 or more. When the weight average molecular weight is less than 10,000, film formability may be lowered. In addition, in this specification, a weight average molecular weight means the weight average molecular weight when measured in polystyrene conversion using a high performance liquid chromatography (Shimadzu Corporation make, C-R4A). The molecular weight of component (c) is 1 million or less, preferably 500,000 or less in consideration of fluidity.

  The ratio of the content of the component (c) and the epoxy resin of the component (a) is not particularly limited, but in order to maintain a good film shape, the component (a) is added to 1 part by mass of the component (c). The amount is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass. If the ratio of this content is less than 0.01 parts by mass, the curability may be lowered and the adhesive force may be reduced, and if it exceeds 5 parts by mass, the film formability and film formability may be reduced.

(D) Flux The film adhesive for semiconductors may contain (d) a flux component, that is, a flux activator that is a compound exhibiting flux activity (activity for removing oxides and impurities). Examples of the flux activator include nitrogen-containing compounds having lone pairs such as imidazoles and amines, carboxylic acids, phenols, and alcohols.

  Compared with alcohol etc., the organic acid expresses flux activity more strongly and the connectivity is improved.

(E) Inorganic filler and (f) Resin filler In order to control the viscosity of the film adhesive for semiconductors and the physical properties of the cured product, and to suppress generation of voids and moisture absorption when the semiconductor chip and the substrate are connected. Therefore, a filler may be blended. Examples of the insulating inorganic filler include glass, silica, alumina, titanium oxide, mica, boron nitride, etc. Among them, silica, alumina, titanium oxide, boron nitride, etc. are preferable, and silica, alumina, boron nitride are more preferable. . Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride.
As the resin filler, polyurethane, polyimide, or the like can be used.
These fillers and whiskers can be used alone or as a mixture of two or more. The shape, particle size, and blending amount of the filler are not particularly limited.

  From the viewpoint of improving dispersibility and adhesive strength, a surface-treated filler is preferable. Examples of the surface treatment include glycidyl (epoxy), amine, phenyl, phenylamino, acrylic, and vinyl.

  Regarding the particle size, the average particle size is preferably 1.5 μm or less from the viewpoint of preventing biting at the time of flip chip connection, and the average particle size is more preferably 1.0 μm or less from the viewpoint of visibility (transparency).

  All of these are preferably silane treatments such as epoxy silanes, amino silanes, and acrylic silanes because of the ease of surface treatment.

  From the viewpoints of dispersibility, fluidity, and adhesive strength, glycidyl, phenylamino, acrylic, and methacrylic are preferred. From the viewpoint of storage stability, phenyl, acrylic, and methacrylic are more preferable.

  (F) Resin fillers are suitable for improving reflow resistance because they can impart flexibility at a high temperature such as 260 ° C. compared to (e) inorganic fillers. Moreover, since flexibility is imparted, it is also effective in improving film formability.

  From the viewpoint of insulation reliability, the filler is preferably insulating. It is preferable not to contain conductive metal fillers such as silver fillers and solder fillers.

  The blending amount of (e, f) filler is preferably 30 to 90% by mass, and more preferably 40 to 80% by mass based on the total solid content of the film adhesive composition for semiconductor. If it is less than 30% by mass, the heat dissipation is low, and the improvement of the adhesive strength tends not to be exerted strongly. If it exceeds 90% by mass, the viscosity becomes high, the fluidity of the adhesive composition is lowered, and the filler is trapped (trapped), and the connection reliability tends to be lowered.

  Furthermore, you may mix | blend an ion trapper, antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, etc. with the film adhesive for semiconductors. 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 for semiconductor can be pressure-bonded at a high temperature of 200 ° C. or higher. In addition, a flip chip package in which a connection is formed by melting a metal such as solder is more effective.

(Method for producing semiconductor film adhesive)
A method for producing a semiconductor film adhesive (film) will be described below.
(C) A high molecular weight component having a molecular weight of 10,000 or more, (a) an epoxy resin, (b) a curing agent, filler, other additives, etc. are added to an organic solvent, and dissolved or dispersed by stirring, mixing, kneading, etc. Prepare varnish. Then, after applying the resin varnish on the base film subjected to the mold release treatment using a knife coater, roll coater, applicator, die coater, comma coater, etc., the organic solvent is reduced by heating, and the base film A film adhesive is formed thereon.

  The base film is not particularly limited as long as it has heat resistance capable of withstanding the heating conditions when the organic solvent is volatilized. The polyester film, the polypropylene film, the polyethylene terephthalate film, the polyimide film, the polyetherimide film, the poly Examples include ether naphthalate films and methylpentene films. 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, the conditions for volatilizing the organic solvent from the resin varnish after coating are specifically preferably 50 to 200 ° C. and heated for 0.1 to 90 minutes. If there is no influence, it is preferable that the organic solvent volatilizes to 1.5% by mass or less.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not restrict | limited by these.

(1) the surface free energy of the polar component gamma _S ^P measurement method filmy pure water to the semiconductor film-like adhesive for on, and added dropwise diiodomethane, static contact angle of the contact angle meter (Kyowa Interface Science Co., Ltd. , DM-50, AD-31s). From the value of the measured contact angle on the basis of the method of Owens-Wendt, and calculates the value of the polar component gamma _S ^P of the surface free energy.

(2) Melt viscosity measurement method Using a rheometer (MCR301, manufactured by Anton Paar Japan Co., Ltd.) under the conditions of sample thickness: 400 μm, temperature rising rate: 10 ° C./min, frequency: 1 Hz (disposable plate ( The melt viscosity at 30 ° C. to 140 ° C. was measured using a diameter 8 mm) and a disposable sample dish), and evaluated using the value at a temperature of 130 ° C.

(3) Manufacturing Method of Semiconductor Device Using a flip chip bonder pressing member (FCB3, manufactured by Panasonic Corporation) having an opposing stage and a pressing head, a semiconductor device was manufactured according to the following procedure.
Using the dicing apparatus, the film-like adhesives (A to F) of the production examples prepared below were attached to a semiconductor wafer with solder bumps and separated into pieces by dicing. The film thickness of the pasted film adhesive was 40 μm. Next, using the flip chip bonder described above, the semiconductor chip with an adhesive film separated into pieces (chip size: 7.3 mm in length, 7.3 mm in width, 0.15 mm in thickness, metal (electrode) of connection part: copper pillar + Solder, copper pillar height 15 μm, solder height 10 μm, number of bumps 1048 pins, pitch 80 μm, product name: WALTS-TEG CC80, manufactured by Waltz Co., Ltd.) and semiconductor chip on the stage of the pressing member (chip size: vertical) 10 mm, width 10 mm, thickness 0.1 mm, metal (electrode) of connection part: Au, product name: WALTS-TEG IP80, manufactured by Waltz Co., Ltd.) were aligned so that the respective connection parts face each other. After that, the semiconductor chips were pressed and heated by being sandwiched between the crimping head and the stage, and the semiconductor chips were crimped so that the connection portions were in contact with each other, and the electrodes of the semiconductor chips were electrically connected. The maximum temperature reached by the pressure-bonding head at the time of pressure-bonding was 260 ° C., and the stage temperature was 80 ° C.

(4) Fillet evaluation (fillet width, coverage)
The sample prepared above was observed from above using a metal microscope (Olympus Co., Ltd., BX60). The distance at which the fillet protrudes outward from the side surface of the chip was defined as the fillet width (A). The fillet width (A) was evaluated as “◯” with a good result of 150 μm or less, and “X” with a case of exceeding 150 μm as a poor result.
The fillet width (B) at the edge portion of the chip was set, and the ratio of (A) and (B) was set as the coverage property (C), and it was evaluated whether the fillet had come out to the end of the package. The coverage property is (C) = (B) / (A), and if it is 0.1 or more, it indicates that the fillet has come out to the end of the package. Since it is preferable that there is no difference in the fillet width between the package end and the center, the closer (C) is to 1, the better.

(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- 150 g of methyl-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) (Sigma-Aldrich) recrystallized and purified with acetic anhydride while cooling the flask in an ice bath. 15.62 g (0.10 mol) (trade name: BPADA) manufactured by the company was added little by little. 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.

(Examples 1-4 and Comparative Examples 1-2)
The compounds used in Examples and Comparative Examples are shown below.
(A) Epoxy resin Trifunctional methane skeleton-containing polyfunctional solid epoxy resin (Mitsubishi Chemical Corporation, EP 1032H60, hereinafter referred to as EP 1032)
Bisphenol F type liquid epoxy resin (Mitsubishi Chemical Corporation, YL983U, hereinafter referred to as YL983)
(B) Curing agent 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2MAOK-PW)
(C) High molecular weight component having a molecular weight of 10,000 or more Polyimide resin (polyimide resin produced in the synthesis example)
Acrylic elastomer (LA4285, manufactured by Kuraray Co., Ltd., weight average molecular weight Mw: about 57000)
Phenoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., ZX1356), Tg: about 71 ° C., weight average molecular weight Mw: about 63000)
(D) Flux agent (carboxylic acid)
Glutaric acid (melting point about 95 ° C)
(E) Inorganic filler Silica filler (manufactured by Admatechs, SE2050, average particle size 0.5 μm)
Methacrylic surface-treated nanosilica filler (manufactured by Admatechs Co., Ltd., YA050C-SM, hereinafter referred to as SM nanosilica, average particle size of about 50 nm)

(Method for producing film adhesive)
According to the formulation shown in Table 1, (a) epoxy resin, (d) flux agent (glutaric acid), (e) inorganic filler (SE2050, SM nanosilica), and (f) resin filler have a solid content of 60% by mass. An organic solvent (methyl ethyl ketone) was added. Thereafter, beads having a diameter of 1.0 mm and a diameter of 2.0 mm were added in the same mass as the solid content, and the mixture was stirred for 30 minutes with a bead mill (Fritch Japan Co., Ltd. planetary pulverizer P-7). Thereafter, (c) a high molecular weight component having a molecular weight of 10,000 or more was added, and the mixture was again stirred with a bead mill for 30 minutes. After stirring, (b) a curing agent was added and stirred, and the beads were removed by filtration. The produced varnish was coated with a table coater and dried (100 ° C./5 min) to obtain a film adhesive.

According to the film-like adhesive for semiconductors of the present invention in which the polar component (γ _S ^P ) of the surface free energy is 1.3 or more, it is confirmed that the fillet can be suppressed and the fillet can be secured to the package end. It was.

DESCRIPTION OF SYMBOLS 1 ... Semiconductor film-like adhesive 2 ... Semiconductor chip 3 ... Board | substrate 4 ... Copper bump 5 ... Connection part (solder)
6 ... Wiring 7 ... Through electrode 8 ... Interposer

Claims (4)

A semiconductor device in which electrodes of each connection part are electrically connected to each other via an adhesive between a semiconductor chip and a printed circuit board, or electrodes of each connection part are connected to each other via an adhesive in a plurality of semiconductor chips. an adhesive used for the production of electrically-connected semiconductor device with each other, a semiconductor film-like adhesive for the value of the polar component gamma _S ^P is 1.3 or more surface free energy of the adhesive.   2. The film adhesive for semiconductor according to claim 1, wherein the melt adhesive at 130 ° C. of the film adhesive for semiconductor is 10,000 Pa · s or less.   The film-like adhesive for semiconductor according to claim 1 or 2, wherein the film-like adhesive for semiconductor contains (a) an epoxy resin, (b) a curing agent, and (c) a high molecular weight component having a molecular weight of 10,000 or more. Agent.   The film-like adhesive for semiconductor according to any one of claims 1 to 3, wherein the high molecular weight component (c) having a molecular weight of 10,000 or more has a weight average molecular weight of 20,000 or more and a glass transition temperature of 100 ° C or less.

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