JP5309886B2 - Film-like adhesive for semiconductor sealing, method for manufacturing semiconductor device, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition of an adhesive for sealing semiconductor devices, wherein the adhesive exhibits high insulation reliability by allowing the adhesive to have effects of suppressing occurrence of voids in connecting a semiconductor chip and a substrate at a high temperature of 200&deg;C or above and suppressing formation of electrically conductive substances by oxidation of tin plated on wiring lines of the substrate. <P>SOLUTION: The composition of the adhesive for sealing semiconductor devices includes (a) an epoxy resin, (b) a curing agent, and (c) an oxidation inhibitor. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

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

  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 the demands for miniaturization, thinning, and high functionality of semiconductor devices, A flip chip connection method in which conductive protrusions called bumps are formed on a semiconductor chip and a substrate electrode and the semiconductor chip are directly connected via the bumps is becoming widespread.

  As a flip chip connection method, a method of metal bonding using solder or tin, a method of metal bonding by applying ultrasonic vibration, a method of maintaining mechanical contact by the shrinkage force of the resin, etc. are known. From the viewpoint of the reliability of the connecting portion, a method of metal bonding using solder or tin is common.

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

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

In COF, the connection part is protected from the external environment, external stress is not concentrated on the connection part, and the gap between the semiconductor chip and the substrate is sealed with a resin in order to ensure insulation reliability between narrow pitch wirings. It is necessary to fill up. As a current sealing and filling method, a method of injecting and curing a liquid resin by capillary action after connecting a semiconductor chip and a substrate is generally used. It is feared that a long time is required for the injection due to the decrease in productivity and productivity is lowered. As a method for solving the above-mentioned concern, there is a method of connecting the chip and the substrate after supplying an adhesive to the chip or the substrate (see Patent Document 1 and Non-Patent Document 1).
JP 2006-188573 A Matsushita Electric Engineering Technical Report (vol.54 No.3, P53-58)

  However, in COF, since the chip and the substrate are connected at a high temperature of 200 ° C. or higher, if a method of connecting the chip and the substrate after supplying the adhesive to the chip or the substrate is used, depending on the volatile components in the adhesive, etc. The adhesive foams and bubbles called voids may be generated. The generated voids may cause a decrease in adhesion and separation between the underfill (resin filled in the gap between the semiconductor chip and the substrate) and the semiconductor chip and the substrate, thereby reducing connection failure and insulation reliability. In addition, the accumulation of moisture in the voids may promote the diffusion and migration of impurity ions in the system, which may reduce the insulation reliability.

  Other causes of lowering insulation reliability are generally used for underfill, semiconductor chip, corrosion of semiconductor device connection parts due to impurity ions on polyimide substrate, tin plated on substrate wiring, adhesive layer between wiring and substrate Examples thereof include generation of conductive substances (for example, tin oxide) by oxidation of nickel, chromium, copper used for wiring, gold used for bumps, and the like.

  The present invention is for solving the above-described problems of the prior art, suppresses the generation of voids when connecting a semiconductor chip and a substrate at a high temperature of 200 ° C. or higher, and is plated on a substrate wiring. Semiconductor sealing adhesive composition, semiconductor sealing film adhesive, and semiconductor device manufacturing method exhibiting high insulation reliability by imparting an effect of suppressing the generation of conductive substances due to oxidation of tin Another object is to provide a semiconductor device.

In order to achieve the above object, the present invention provides an adhesive composition for semiconductor encapsulation, which contains (a) an epoxy resin, (b) a curing agent, and (c) an antioxidant. The semiconductor sealing adhesive composition is a semiconductor sealing adhesive composition that seals a gap between a semiconductor chip and a substrate, and includes (a) an epoxy resin, and (b) a curing agent. (C) an antioxidant and (d) a polymer component having a weight average molecular weight of 10,000 or more, (c) the antioxidant is a hindered phenol, and (d) the polymer component is The adhesive composition for semiconductor sealing which is a polyimide resin may be sufficient.

  According to such a semiconductor sealing adhesive composition, by having the above-described configuration, it is possible to suppress the generation of voids when connecting a semiconductor chip and a substrate at a high temperature of 200 ° C. or higher. In addition, it is possible to suppress the generation of a conductive substance that deposits on the wiring and to exhibit high insulation reliability.

  The semiconductor sealing adhesive composition of the present invention preferably further contains (d) a polymer component having a weight average molecular weight of 10,000 or more. Thereby, the film formation property in the case of forming the adhesive composition for semiconductor sealing into a film shape can be made favorable.

  Here, the polymer component (d) is preferably a polyimide resin. Thereby, while being able to make the film formation property in the case of forming the adhesive composition for semiconductor sealing into a film form more favorable, heat resistance can be improved.

  Furthermore, the polyimide resin preferably has a weight average molecular weight of 30000 or more and a glass transition temperature of 100 ° C. or less. When the weight average molecular weight of the polyimide resin is 30000 or more, good film formability can be exhibited. Moreover, when the glass transition temperature of the polyimide resin is 100 ° C. or less, good stickability to a substrate or a semiconductor chip can be obtained.

  Moreover, in the adhesive composition for semiconductor encapsulation of the present invention, the (b) curing agent is preferably a phenol compound. This is because the phenol compound has a performance excellent in curability and moldability as a curing agent for the epoxy resin.

  Moreover, in the adhesive composition for semiconductor encapsulation of the present invention, the (c) antioxidant is preferably a hindered phenol. If hindered phenol with a bulky functional group around the hydroxyl group of phenol is less likely to be taken into the curing reaction with epoxy, etc. Metal oxidation can be prevented. This dramatically improves HAST resistance.

  This invention also provides the film-form adhesive for semiconductor sealing formed by forming the adhesive composition for semiconductor sealing of the said this invention in a film form.

  According to such a film-like adhesive for semiconductor sealing, the semiconductor chip and the substrate are connected at a high temperature of 200 ° C. or higher by having the configuration using the adhesive composition for semiconductor sealing of the present invention. Generation of voids can be suppressed, and generation of a conductive substance that deposits on a substrate, bump, or wiring can be suppressed, and high insulation reliability can be exhibited.

  The film-like adhesive for semiconductor encapsulation of the present invention preferably has a melt viscosity at 350 ° C. of 2000 Pa · s or less. Thereby, the continuity, connectivity, and insulation reliability are improved when the semiconductor chip and the substrate are connected at a high temperature of 200 ° C. or higher.

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

  In the present invention, when the semiconductor chip having bumps and the substrate having metal wiring are connected at a temperature of 200 ° C. or higher, the semiconductor chip is connected via the adhesive composition 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 adhesive composition for semiconductor sealing.

  In the present invention, when the semiconductor chip having bumps and the substrate having metal wiring are connected at a temperature of 200 ° C. or higher, the semiconductor chip is connected via the film-like 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 these semiconductor device manufacturing methods, since the semiconductor chip and the substrate are connected using the semiconductor sealing adhesive composition or the semiconductor sealing film adhesive of the present invention, the semiconductor chip Generation of voids between the wiring and the substrate is sufficiently suppressed, and a semiconductor device having sufficient insulation reliability between wirings can be efficiently manufactured. In addition, (c) an antioxidant is contained in the semiconductor sealing adhesive composition and the semiconductor sealing film adhesive, whereby a semiconductor device with improved HAST resistance can be efficiently manufactured. it can.

  In the semiconductor device manufacturing method of the present invention, the bump is a gold bump, the metal wiring is a tin-plated metal wiring, the substrate is a polyimide substrate, the semiconductor chip and the substrate Are preferably formed by forming a gold-tin eutectic at a temperature of 200 ° 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 semiconductor device manufacturing method of the present invention, the generation of voids between the semiconductor chip and the substrate is sufficiently suppressed, and sufficient insulation reliability between the wirings is obtained. It is done.

  According to the present invention, it is possible to suppress the generation of voids when connecting a semiconductor chip and a substrate at a high temperature of 200 ° C. or higher, and to provide an antioxidation effect, so that the conductivity deposited on the substrate, bumps and wirings can be reduced. Therefore, it is possible to provide a semiconductor sealing adhesive composition, a semiconductor sealing film adhesive, a semiconductor device manufacturing method, and a semiconductor device that exhibit high insulation reliability. it can.

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

(Semiconductor sealing adhesive composition, semiconductor sealing film adhesive and manufacturing method thereof)
The adhesive composition for semiconductor encapsulation of the present invention contains (a) an epoxy resin, (b) a curing agent, and (c) an antioxidant, and preferably (d) a weight average. It contains a polymer component having a molecular weight of 10,000 or more. Moreover, the film-form adhesive for semiconductor sealing of this invention forms the said adhesive composition for semiconductor sealing of this invention in a film form, Comprising: (a) Epoxy resin, (b) It contains a curing agent and (c) an antioxidant, and preferably further contains (d) a polymer component having a weight average molecular weight of 10,000 or more. Hereinafter, each component will be described.

(A) Epoxy Resin The (a) 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. Also, for example, bisphenol A type and bisphenol F type liquid epoxy resins have a 1% thermogravimetric reduction temperature of 250 ° C. or less, and therefore may decompose during high-temperature heating and generate volatile components. It is desirable to use an epoxy resin.

(B) Curing agent Examples of the (b) curing agent used in the present invention include phenol compounds, acid anhydride curing agents, amine curing agents, imidazoles, and phosphines.

  The phenol compound is not particularly limited as long as it has two or more phenolic hydroxyl groups in the molecule. For example, phenol novolak, cresol novolak, phenol aralkyl resin, cresol naphthol formaldehyde polycondensate, triphenylmethane type polycondensate. Functional phenol, various polyfunctional phenol resins, etc. can be used. These can be used alone or as a mixture of two or more. Moreover, since liquid phenol 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 phenol compound at room temperature. (A) The equivalent ratio of the epoxy resin to the phenol compound (phenol compound / (a) epoxy resin) is preferably set to 0.3 to 1.5 from the viewpoints of curability, adhesiveness, storage stability, and the like. . More preferred is 0.4 to 1.0, and even more preferred is 0.5 to 1.0. If the equivalent ratio is less than 0.3, the curability may be reduced and the adhesive force may be reduced. If the equivalent ratio is more than 1.5, an unreacted phenolic hydroxyl group remains excessively, and the water absorption increases. Insulation reliability may be reduced.

  Examples of the acid anhydride-based curing agent include methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bisanhydro trimellitate, etc. be able to. 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. The equivalent ratio of (a) epoxy resin to acid anhydride (acid anhydride / (a) epoxy resin) should be set to 0.3 to 1.5 from the viewpoint of curability, adhesiveness, storage stability, and the like. Is desirable. More preferred is 0.4 to 1.0, and even more preferred is 0.5 to 1.0. 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, the unreacted acid anhydride remains excessively, and the water absorption rate increases. Insulation reliability may be reduced.

  As the amine-based curing agent, for example, dicyandiamide can be used. Moreover, since liquid amine decomposes | disassembles at the time of high temperature heating and a volatile component may generate | occur | produce, it is desirable to use a solid amine at room temperature. The equivalent ratio of (a) epoxy resin to amine (amine / (a) epoxy resin) is preferably set to 0.3 to 1.5 from the viewpoints of curability, adhesiveness, storage stability, and the like. More preferred is 0.4 to 1.0, and even more preferred is 0.5 to 1.0. If the equivalent ratio is less than 0.3, the curability may be reduced and the adhesive force may be reduced. If the equivalent ratio is more than 1.5, unreacted amine may remain excessively and insulation reliability may be reduced. is there.

  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′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2 ′ -Ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-dia No-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole, adducts of epoxy resin and imidazoles. Among these, in the present invention, from the viewpoint of curability, storage stability, and connection reliability, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenyl Imidazolium 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-phenylimidazole Isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole is preferable. These may be used alone or in combination of two or more. Moreover, you may use what microencapsulated these and raised the potential. As a compounding quantity, the ratio of 0.001-0.1 is desirable with respect to (a) epoxy resin by mass ratio, More desirably, it is a ratio of 0.001-0.05. If it is less than 0.001, the curability may be reduced, and if it exceeds 0.1, it may be cured before the metal-metal connection is formed, resulting in poor connection. There is. Imidazoles may be used alone with (a) an epoxy resin, but may be used as a curing accelerator together with a phenol compound, an acid anhydride curing agent, and an amine curing agent.

  Examples of the phosphines include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (4-methylphenyl) borate, tetraphenylphosphonium (4-fluorophenyl) borate and the like. As a compounding quantity, the ratio of 0.001-0.1 is desirable with respect to (a) epoxy resin by mass ratio, More desirably, it is a ratio of 0.001-0.05. If it is less than 0.001, the curability may be reduced, and if it exceeds 0.1, it may be cured before the metal-metal connection is formed, resulting in poor connection. There is. The phosphines may be used alone with (a) the epoxy resin, but may be used as a curing accelerator together with the phenol compound, the acid anhydride curing agent, and the amine curing agent.

(C) Antioxidant (c) Antioxidant of this invention should just be selected according to the composition of the adhesive composition for semiconductor sealing. (C) The antioxidant is preferably one or more antioxidants selected from the group consisting of phenolic antioxidants, phosphite antioxidants, and sulfur antioxidants.

  The phenolic antioxidant is preferably a compound having a substituent having a large steric hindrance such as a t-butyl group (tert-butyl group) or a trimethylsilyl group at the ortho position of the phenolic hydroxyl group. The phenolic antioxidant is also referred to as a hindered phenolic antioxidant.

  This phenolic antioxidant includes 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-4-ethylphenol, 2,2′- Methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-thiobis- (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) ), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t) -Butyl-4-hydroxybenzyl) benzene and tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane selected from the group consisting of methane Preferably, the above compound is 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) and / or 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl) More preferred is phenyl) butane. In particular, when it is desired to increase the insulation reliability, the phenolic antioxidant is preferably 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane. Of these, a mixture comprising 2-t-butyl-4-methoxyphenol and 3-t-butyl-4-methoxyphenol is generally referred to as butylated hydroxyanisole and used as an antioxidant.

  Phosphite antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-t-butylphenylditridecyl) phosphite, Click neopentanetetrayl bis (nonylphenyl) phosphite, cyclic neopentanetetrayl bis (dinonylphenyl) phosphite, cyclic neopentanetetrayl tris (nonylphenyl) phosphite, cyclic neopentanetetrayl tris ( Dinonylphenyl) phosphite, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diisodecylpentaerythritol diphosphite and tris (2 It is preferably one or more compounds selected from the group consisting of 4-di-t-butylphenyl) phosphite and 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene. More preferably, it is -10-oxide.

  The sulfur-based antioxidant is selected from the group consisting of dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, N-cyclohexylthiophthalimide, and Nn-butylbenzenesulfonamide. One or more compounds are preferred. Dilauryl 3,3′-thiodipropionate is sometimes referred to as dilauryl thiodipropionate, and distearyl 3,3′-thiodipropionate is referred to as distearyl thiodipropionate. There is also.

  (C) Antioxidants may be synthesized and / or prepared by conventional methods, and commercially available products may be obtained. Examples of commercially available antioxidants include “Yoshinox BB”, “Yoshinox BHT”, and “Yoshinox 425” (trade names, manufactured by API Corporation), which are one type of phenolic antioxidants. , “TTIC”, “TTAD” (trade name, manufactured by Toray Industries, Inc.), “IRGANOX L107” (trade name, manufactured by Ciba Specialty Chemicals), “AO-20”, “AO-30”, “AO-” 40 "," AO-50 "," AO-50F "," AO-60 "," AO-60G "," AO-70 "," AO-80 "," AO-330 "(above, manufactured by ADEKA) , Product name). Among them, “AO-60”, which is a compound having t-butyl groups on both sides of the ortho position of the phenolic hydroxyl group and including four skeletons thereof, is more preferable. A compound in which the phenolic hydroxyl group is surrounded by more bulky substituents, has a high steric hindrance, and contains more of its skeleton, is expected to improve the insulation reliability. Further, as available phosphite antioxidants, “PEP-4C”, “PEP-8”, “PEP-8W”, “PEP-24G”, “PEP-36”, “PEP-36Z”, “HP-10”, “HP-2112”, “HP-2112RG” (above, trade name, manufactured by ADEKA) may be mentioned. Furthermore, examples of the available sulfur-based antioxidants include “AO-412S” and “AO-503” (above, trade name, manufactured by ADEKA).

  These antioxidants may be used alone or in combination of two or more.

(D) Polymer component having a weight average molecular weight of 10,000 or more (d) The polymer component having a weight average molecular weight of 10,000 or more is a phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, phenol resin, cyanate ester resin, Acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, polyetherimide resin, polyvinyl acetal resin, urethane resin, acrylic rubber, etc. Among them, phenoxy resin, polyimide resin, cyanate which are excellent in heat resistance and film formability are mentioned. An ester resin, a polycarbodiimide resin, an acrylic rubber, or the like is desirable, and a phenoxy resin, a polyimide resin, or an acrylic rubber is more preferable. These polymer components can be used alone or as a mixture or copolymer of two or more.

  (D) The polyimide resin used as the polymer component 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 nearly equimolar amount (the order of addition of each component is arbitrary), and the addition reaction is carried out 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 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'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) ) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracar Acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetra Carboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2, 3, 6, 7- Trachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Anhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetra Carboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) Methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1, 3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2 , 3,4-Butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid Dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2 , 2]-Oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2, -bis [4- (3 , 4-Dicarboxyphenyl) phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2, -bis [4- (3,4-di Carboxyphenyl) phenyl] hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (tri Merit acid anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic acid anhydride), 5- (2,5-dioxotetrahydride) Furyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, tetracarboxylic acid represented by the following general formula (I) Examples thereof include acid dianhydrides and tetracarboxylic dianhydrides represented by the following 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, the tetracarboxylic dianhydride represented by the general 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 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 extremely 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′-diaminodiphenylmethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4- Amino-3,5-diisopropylphenyl) methane, 3,3′-diaminodiphenyldifluoromethane, 3,4′-diaminodiphenyldifluoromethane, 4,4′-diaminodiphenyldifluoromethane, 3,3′-diaminodiphenylsulfone, 3, '-Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone 3,4′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 ′-(3,4′-diaminodiphenyl) propane, 2, 2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4 -Aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benze 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3, 4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3 -Aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis ( 4- (3-aminoenoxy) phenyl) sulfide, bis (4- (4-aminoenoxy) phenyl) sulfide, bis (4- (3-aminoenoxy) Ci) phenyl) sulfone, bis (4- (4-aminoenoxy) phenyl) sulfone, aromatic diamines such as 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4 -Aminophenoxyphenyl) propane, aliphatic ether diamine represented by the following general formula (III), aliphatic diamine represented by the following general formula (IV), siloxane diamine represented by the following general formula (V), etc. Can be mentioned.

［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, the diamine represented by the above general formula (III) or (IV) is preferable in that low stress properties, low-temperature laminating properties, 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 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 said general formula (V) is 20-79 mol% of all the diamines. 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の他、下記一般式（ＶＩ）で表される脂肪族エーテルジアミンが挙げられる。これからの中でも、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。 Moreover, as aliphatic ether diamine represented by the said general formula (III), specifically, following formula;

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

［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. And aliphatic diamines such as polyoxyalkylene diamines such as 900, ED-2001, EDR-148, BASF (manufactured) polyetheramine D-230, D-400, D-2000.

  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 and the like.

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

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

  The weight average molecular weight of the polyimide resin is preferably 30000 or more, more preferably 40000 or more, and further preferably 50000 or more in terms of polystyrene in order to exhibit good film-formability independently. If the weight average molecular weight is less than 30000, the film formability may be reduced. In addition, said weight average molecular weight is a weight average molecular weight when measured in polystyrene conversion using a high performance liquid chromatography (Shimadzu Corporation make, brand name: C-R4A).

(D) The mass ratio of the polymer component having a weight average molecular weight of 10,000 or more and the (a) epoxy resin and (b) curing agent mixture is not particularly limited, but in order to maintain the film shape, (d) the weight average It is preferable that (a) epoxy resin and (b) hardener mixture are 0.01-4 mass parts with respect to 1 mass part of high molecular components with a molecular weight of 10,000 or more, and 0.1-4 mass parts. Is more preferable, and it is still more preferable that it is 0.1-3 mass parts. When this mass ratio is smaller than 0.01 parts by mass, the curability of the film adhesive is lowered and the adhesive force may be lowered, and when it is larger than 4 parts by mass, the film formability may be lowered.

  It is also preferable to mix a curing accelerator in the adhesive composition and film adhesive of the present invention. The curing accelerator may be selected according to the composition of the semiconductor sealing adhesive composition and the semiconductor sealing film adhesive.

  Examples of the curing accelerator include phosphines and imidazoles. Examples of the phosphines include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (4-methylphenyl) borate, tetraphenylphosphonium (4-fluorophenyl) borate and the like. 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-hydroxymethyl imidazole, and the like adducts of epoxy resins and imidazoles. Among these, in the present invention, from the viewpoint of curability and storage stability, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimethylate, which is an adduct of imidazoles and organic acids. Meritite, 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-phenylimidazole isocyanuric acid addition And 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxy, which is a high melting point imidazole Chill imidazole is preferable. More preferred is 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole. These may be used alone or in combination of two or more. Moreover, you may use what microencapsulated these and raised the potential.

  As a compounding quantity of a hardening accelerator, the ratio of 0.001-0.1 mass part is preferable with respect to 1 mass part of mixture of (a) epoxy resin and (b) hardening | curing agent by mass ratio, 0.001- A proportion of 0.05 parts by mass is more preferred, and a proportion of 0.001 to 0.03 parts by mass is still more preferred. When this mass ratio is less than 0.001 part by mass, the curability of the adhesive composition and the film adhesive may be lowered, and when it exceeds 0.1 part by mass, a gold-tin eutectic crystal It may be hardened before the connection part is formed, resulting in poor connection.

  In the adhesive composition and film adhesive of the present invention, in order to control the viscosity and physical properties of the cured product, and to suppress the generation of voids and moisture absorption when the semiconductor chip and the substrate are connected, It is also preferable to blend a filler.

  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, silica, alumina, titanium oxide, and boron nitride are preferable, and silica, alumina, and nitride are used. Boron is more preferred. Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride. For example, polyurethane, polyimide, or the like can be used as the resin filler. These fillers and whiskers can be used alone or as a mixture of two or more. There is no particular limitation on the shape, particle size, and blending amount of the filler.

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

  The film-like adhesive of the present invention preferably has a melt viscosity at 350 ° C. of 2000 Pa · s or less, more preferably 200 to 1800 Pa · s, and particularly preferably 500 to 1500 Pa · s. . When the melt viscosity exceeds 2000 Pa · s, when the semiconductor chip and the substrate are connected via the film adhesive, the film adhesive is likely to remain between the bump and the wiring, causing an initial conduction failure. It will be.

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

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

  An example of a method for producing the film adhesive of the present invention is shown below. (A) an epoxy resin, (b) a curing agent, (c) an antioxidant, (d) a polyimide resin as a polymer component, an additive (a curing accelerator, a filler, etc.) is added to an organic solvent, and stirred and mixed. A resin varnish is prepared by dissolving or dispersing by kneading or the like. Then, after applying the resin varnish using a knife coater, roll coater or applicator on the base film subjected to the release treatment, the organic solvent is removed by heating, and a film adhesive is applied on the base film. Form. In addition, (d) the polyimide resin as a polymer component is used in the state of a polyimide resin varnish containing a solvent without isolation after synthesis, and each component is added to the polyimide resin varnish to prepare a resin varnish. May be.

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

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

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

(Method for manufacturing semiconductor device)
The method for producing a semiconductor device of the present invention comprises the above-described adhesive composition for semiconductor encapsulation or semiconductor encapsulation of the present invention when connecting a semiconductor chip having bumps and a substrate having metal wiring at a temperature of 200 ° C. or higher. A step of sealing and filling a gap between the semiconductor chip and the substrate with an adhesive composition for semiconductor sealing or a film adhesive for semiconductor sealing. It is.

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

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

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

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

  After pasting the film adhesive on the substrate or the semiconductor chip, the wiring pattern of the substrate and the bump of the semiconductor chip are aligned, and the connection temperature of 200 ° C. or higher, preferably 300 to 450 ° C., at 0.5 to Pressurize for 5 seconds. The connection load depends on the number of bumps, but is set in consideration of absorption of bump height variations and control of the amount of bump deformation. After the semiconductor chip and the substrate are connected, heat treatment may be performed in an oven or the like. Also when using an adhesive composition, an adhesive composition is interposed between a board | substrate and a semiconductor chip, and a semiconductor chip and a board | substrate are connected by the method similar to the above.

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

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

(Synthesis example: Synthesis of polyimide resin)
In a 300 ml flask equipped with a thermometer, a stirrer, and a calcium chloride tube, 2.10 g (0.035 mol) of 1,12-diaminododecane, polyether diamine (trade name: D2000, molecular weight: 1923, manufactured by BASF) 31 g (0.03 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: LP-7100) 2.61 g (0.035 mol) and N-methyl- 150 g of 2-pyrrolidone (manufactured by Kanto Chemical Co., Inc.) was charged and stirred. After dissolution of the diamine, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic dianhydride) (made by ALDRICH, Inc.) was recrystallized and purified with acetic anhydride while cooling the flask in an ice bath. , Trade name: BPADA) 15.62 g (0.10 mol) was added in small portions. After reacting at room temperature for 8 hours, 100 g of xylene was added and heated at 180 ° C. while blowing nitrogen gas, and xylene was removed azeotropically with water to obtain a polyimide resin solution. The obtained polyimide resin had a Tg of 27 ° C., a weight average molecular weight of 47000, and an SP value of 10.2.

Example 1
In a 20 ml glass screw tube, 1.00 g (solid content) of the polyimide resin synthesized in the synthesis example, 0.11 g of epoxy resin (YDCN-702), 0.11 g of epoxy resin (VG3101L), 0 hardener (Kayahard NHN) 0.08 g, silica filler (R972) 0.07 g, boron nitride (HPP1-HJ) 0.46 g, curing accelerator (2MAOK-PW) 0.002 g, and antioxidant (AO-60) 0.055 g , N-methyl-2-pyrrolidone (NMP) was added so that the solid content was 40% by mass, and the mixture was stirred and degassed with a stirring and defoaming device (trade name: AR-250, manufactured by Shinky Co., Ltd.). A varnish was obtained. The obtained resin varnish was coated on a film (Teijin DuPont Films Co., Ltd., trade name: Purex A53) subjected to a release treatment, and a coating machine (Tester Sangyo Co., Ltd., trade name: PI-1210 FILMCOATER). ) And dried in a clean oven (manufactured by ESPEC) at 80 ° C. for 30 minutes and then at 120 ° C. for 30 minutes to obtain a film adhesive.

(Examples 2-3 and Comparative Examples 1-4)
In the preparation of the resin varnish, the film-like adhesions of Examples 2-3 and Comparative Examples 1-4 were made in the same manner as in Example 1 except that the composition of the materials used was changed as shown in Tables 1 and 2 below. An agent was obtained. In Table 1, the amount of each material is expressed in parts by mass.

Moreover, the detail of each material used by the Example and the comparative example is shown below.
(A) Epoxy resin Cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: YDCN-702).
Multifunctional special epoxy resin (manufactured by Printec Co., Ltd., trade name: VG3101L).
(B) Curing agent Cresol naphthol formaldehyde polycondensate (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayahard NHN).
(C) Antioxidant Hindered phenol 1 (made by ADEKA Corporation, trade name: AO-60).
Hindered phenol 2 (product name: Yoshinox BB, manufactured by API Corporation).
(D) Polymer component having a weight average molecular weight of 10,000 or more Polyimide resin synthesized in Synthesis Example (hereinafter referred to as “synthetic polyimide”).
(E) Curing accelerator 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct (manufactured by Shikoku Kasei Co., Ltd., trade name: 2MAOK-PW) .
(F) Filler Boron nitride (manufactured by Mizushima Alloy Iron Co., Ltd., trade name: HPP1-HJ, average particle size: 1.0 μm, maximum particle size: 5.1 μm).
Silica filler (Nippon Aerosil Co., Ltd., trade name: R972, average particle size 20 nm).
(G) Inorganic ion scavenger Cation scavenger (manufactured by Toagosei Co., Ltd., trade name: IXE100).
Anion scavenger (manufactured by Toagosei Co., Ltd., trade name: IXE500).
(H) Solvent N-methyl-2-pyrrolidone (NMP) (manufactured by Kanto Chemical Co., Inc.).

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

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

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

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

  When a semiconductor device was fabricated by mounting a chip with gold bumps (daisy chain connection) on the polyimide substrate with FCB3 without using a film adhesive, the connection resistance value between the chip with gold bumps and the copper wiring was About 155Ω. From this, the connection resistance value between the chip with the gold bump and the copper wiring in the semiconductor device manufactured using the film-like adhesives of the example and the comparative example is measured, and the initial value is when the value is less than 170Ω. Conductivity was allowed (“A”), and the case of 170Ω or more was determined to be initial continuity impossible (“B”). The results are shown in Table 2.

<Insulation reliability test (HAST test: Highly Accelerated Storage Test)>
The film adhesives (thickness: 30 μm) produced in the examples and comparative examples are attached to a comb-type electrode evaluation TEG (manufactured by Shindo Electronics Co., Ltd., perflex-S, wiring pitch: 30 μm), and in a clean oven (manufactured by ESPEC) And cured at 180 ° C. for 1 hour. After curing, sample C (FIG. 5) was taken out and placed in an accelerated life test apparatus (manufactured by HIRAYAMA, trade name: PL-422R8, condition: 110 ° C./85% RH / 100 hours), and the insulation resistance was measured. As shown in FIG. 5, the sample C is obtained by pasting the cured film adhesive 12 on the tin-plated copper wiring (comb-type electrode evaluation TEG) 13. The evaluation method is “A” when the insulation resistance is 1 × 10 ⁸ Ω or more over 100 hours, and “B” when the minimum insulation resistance is 1 × 10 ⁷ Ω or more and less than 1 × 10 ⁸ Ω. “C” is the case where the minimum value of the insulation resistance is less than 1 × 10 ⁷ Ω. In addition, a case where the evaluation result is “C” has a practical problem. The results are shown in Table 2.

Further, a sample mounted with the same device, procedure and conditions as in the above <Manufacturing of semiconductor device (conductivity and appearance evaluation)> was cured at 180 ° C. for 1 hour. After curing, the sample was taken out and placed in an accelerated life test apparatus (manufactured by HIRAYAMA, trade name: PL-422R8, condition: 110 ° C./85% RH / 100 hours), and the insulation resistance was measured. The evaluation method is “A” when the insulation resistance is 1 × 10 ⁸ Ω or more over 100 hours, and “B” when the minimum value of the insulation resistance is 1 × 10 ⁷ Ω or more and less than 1 × 10 ⁸ Ω. The case where the minimum value of the insulation resistance is less than 1 × 10 ⁷ Ω is defined as “C”. In addition, a case where the evaluation result is “C” has a practical problem. The results are shown in Table 2.

<Impurity ion concentration measurement>
As a comparison of the impurity ion concentration (acetate ion, formate ion) of Example 1 (with antioxidant) and Comparative Example 1 (without antioxidant), a film cured at 180 ° C. for 1 hour in a clean oven (manufactured by ESPEC) About 1 g of a thin adhesive (thickness: 30 μm) was cut out at 5 mm × 5 mm, placed in a Teflon crucible with a stainless steel jacket, and diluted 10 times with pure water. Thereafter, the diluted solution was put into a small constant temperature tester (manufactured by ETAC) and subjected to ion extraction (121 ° C./20 hours). After extraction, it was filtered, and the impurity ion concentration was measured with an ion chromatograph (manufactured by Dionex Corporation). The results are shown in Table 3.

  In Examples 1 to 3, the initial conduction is “OK” because the melt viscosity at 350 ° C. is 2000 Pa · s or less, but Comparative Example 2 is the initial because the viscosity at 350 ° C. is greater than 2000 Pa · s. The conduction is “impossible”.

  In Examples 1 to 3 to which the antioxidant was added, it was confirmed that the insulation resistance value was high and stable compared to Comparative Examples 1 to 4.

  From the results shown in Table 3, it was confirmed that Example 1 had a lower concentration of acetate ion / formate ion, which is considered to be the cause of thermal oxidation deterioration, than that of Comparative Example 1.

It is a schematic cross section which shows the state before pressure bonding of the sample A for melt viscosity measurement. It is a schematic cross section which shows the state before the crimping | compression-bonding of the sample B for void incidence rate measurement. 4 is a photograph showing the entire semiconductor device manufactured using the film adhesive of Example 3. It is a photograph which shows the cross section of the chip mounting part in the semiconductor device produced using the film adhesive of Example 3. FIG. It is a photograph which shows the general view of the sample C installed in an accelerated life test apparatus by an insulation reliability test.

Explanation of symbols

DESCRIPTION OF SYMBOLS 3 ... Glass chip, 4 ... Film adhesive, 7 ... Cover glass, 5, 9 ... Semiconductor chip, 6, 10 ... Gold bump, 8 ... Polyimide substrate, 11 ... Cured material of film adhesive, 12 ... Polyimide substrate + Film adhesive after curing, 13 ... Tin plated copper wiring.

Claims (7)

A semiconductor sealing film-like adhesive formed by forming a semiconductor sealing adhesive composition for sealing a gap between a semiconductor chip and a substrate into a film,
The adhesive composition for semiconductor encapsulation contains (a) an epoxy resin, (b) a curing agent, (c) an antioxidant, and (d) a polymer component having a weight average molecular weight of 10,000 or more. Is,
The (c) antioxidant is a hindered phenol,
(D) the polymer component is a polyimide resin,
The melt viscosity at 350 ° C. for encapsulating a semiconductor film-like adhesive is not more than 2000 Pa · s, semiconductors sealing film adhesive. The film-like adhesive for semiconductor encapsulation according to claim 1, wherein the polyimide resin has a weight average molecular weight of 30000 or more and a glass transition temperature of 100 ° C. or less. The film-like adhesive for semiconductor encapsulation according to claim 1 or 2, wherein the (b) curing agent is a phenol compound. The film-form adhesive for semiconductor sealing as described in any one of Claims 1-3 whose void generation rate at the time of crimping | bonding at 350 degreeC and 1 Mpa for 5 second is 5% or less. When connecting a temperature substrate and the above 200 ° C. with a semiconductor chip and the metal wire having a bump, connected via the semiconductor encapsulation film-like adhesive according to any one of claims 1 to 4 A method for manufacturing a semiconductor device, comprising sealing and filling a gap between the semiconductor chip and the substrate with the film-like adhesive for semiconductor sealing. The bump is a gold bump, the metal wiring is a metal wiring whose surface is tin-plated, the substrate is a polyimide substrate, and the semiconductor chip and the substrate are bonded to a gold-tin eutectic at a temperature of 200 ° C. or more. The method of manufacturing a semiconductor device according to claim 5 , wherein the semiconductor device is formed and connected. A semiconductor device manufactured by the method for manufacturing a semiconductor device according to claim 5 .

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