JP5003855B2 - Adhesive composition, method for manufacturing semiconductor device, and semiconductor device - Google Patents

Abstract

The present invention relates to an adhesive composition that seals connection parts in a semiconductor device in which the connection part of a semiconductor chip and the connection part of a wiring circuit board are electrically connected together, or in a semiconductor device in which the connection parts of a plurality of semiconductor chips are electrically connected together, wherein the adhesive composition contains an epoxy resin, a curing agent, and a vinyl-based surface treatment filler.

Description

  The present invention relates to an adhesive composition, a method for manufacturing a semiconductor device, and a semiconductor device.

  In recent years, in order to mount and connect a semiconductor chip to a substrate, a wire bonding method using a fine metal wire such as a gold wire has been widely used. On the other hand, in order to meet the demands for downsizing, thinning, high functionality, high integration, high speed, etc., for semiconductor devices, conductive protrusions called bumps are formed between the semiconductor chip and the substrate, Flip chip connection methods (FC connection methods) for connection are becoming widespread.

  For example, for connection between a semiconductor chip and a substrate, a COB (Chip On Board) type connection method that is actively used in BGA (Ball Grid Array), CSP (Chip Size Package), and the like also corresponds to the FC connection method. The FC connection method is also widely used in a COC (Chip On Chip) type connection method in which connection portions (bumps and wirings) are formed on a semiconductor chip to connect the semiconductor chips (for example, patents). Reference 1).

  However, in order to meet the demands for further miniaturization, thinning, and high functionality, chip stack type packages, POPs (Package On Packages), TSVs (Through-Silicon Vias), etc., in which the above-mentioned connection methods are stacked and multistaged, etc. Has also started to spread widely. Such stacking / multi-stage technology arranges semiconductor chips and the like three-dimensionally, so that the package can be made smaller than the two-dimensional arrangement technique. In particular, the TSV technology is effective for improving semiconductor performance, reducing noise, reducing the mounting area, and saving power, and is attracting attention as a next-generation semiconductor wiring technology.

  By the way, as a main metal used for the connection part (bump or wiring), there are solder, tin, gold, silver, copper, nickel and the like, and a conductive material including a plurality of these is also used. The metal used in the connection part may be oxidized on the surface and an oxide film may be formed, or impurities such as oxide may adhere to the surface, which may cause impurities on the connection surface of the connection part. . If such impurities remain, there is a concern that the connectivity / insulation reliability between the semiconductor chip and the substrate or between the two semiconductor chips is lowered, and the merit of employing the above-described connection method is impaired.

  As a method for suppressing the generation of these impurities and improving the connectivity, there is a method in which a surface of a substrate or a semiconductor chip is subjected to a pretreatment before connection, and a preflux used in an OSP (Organic Solderability Preservatives) process The method of giving a rust preventive agent is mentioned. However, the pre-flux and the rust preventive agent may remain and deteriorate after pretreatment, which may reduce the connectivity.

  On the other hand, according to the method of sealing the connection part between the semiconductor chip and the substrate with a semiconductor sealing material (adhesive for semiconductor sealing), the connection part is sealed simultaneously with the connection between the semiconductor chip and the substrate or the semiconductor chip. It becomes possible to do. Therefore, oxidation of the metal used for the connection part and adhesion of impurities to the connection part can be suppressed, and the connection part can be protected from the external environment. Therefore, it is possible to effectively improve connectivity / insulation reliability, workability, and productivity.

  In addition, in a semiconductor device manufactured by a flip-chip connection method, thermal stress derived from a difference in thermal expansion coefficient between a semiconductor chip and a substrate or a difference in thermal expansion coefficient between semiconductor chips does not concentrate on the connection portion to cause a connection failure. In order to do so, it is necessary to seal the gap between the semiconductor chip and the substrate with a semiconductor sealing material. In particular, components having different thermal expansion coefficients are often used between the semiconductor chip and the substrate, and it is required to improve the thermal shock resistance by sealing with a semiconductor sealing material.

  The above-described sealing methods using a semiconductor sealing material are roughly classified into a capillary-flow method and a pre-applied method (for example, see Patent Documents 2 to 6). The Capillary-Flow method is a method in which a liquid semiconductor sealing material is injected into the gap between the semiconductor chip and the substrate by capillary action after the semiconductor chip and the substrate are connected. The pre-applied method is a method of connecting a semiconductor chip and a substrate after supplying a semiconductor sealing material in a paste or film form to the semiconductor chip or the substrate before connecting the semiconductor chip and the substrate. With these sealing methods, the gap between the semiconductor chip and the substrate is becoming narrower with the progress of miniaturization of semiconductor devices in recent years, and the Capillary-Flow method requires a long time for implantation and decreases productivity. In some cases, when injection is not possible, or even if injection is possible, an unfilled portion may exist and cause voids. Therefore, from the viewpoint of workability, productivity, and reliability, the pre-applied method has become the mainstream as a package manufacturing method capable of high functionality, high integration, and high speed.

JP 2008-294382 A JP 2001-223227 A JP 2002-283098 A JP 2005-272547 A JP 2006-169407 A JP 2006-188573 A

  In the above-mentioned pre-applied method, the gap between the semiconductor chip and the substrate is sealed with the semiconductor sealing material simultaneously with the connection by heating and pressurization. Therefore, the components contained in the semiconductor sealing material are selected in consideration of the connection conditions. There is a need to. In general, metal bonding is used for connection between connection portions from the viewpoint of sufficiently ensuring connectivity and insulation reliability. Since metal bonding is a connection method using a high temperature (for example, 200 ° C. or higher), it is caused by volatile components remaining in the semiconductor sealing material and newly generated volatile components by decomposition of the components contained in the semiconductor sealing material. The semiconductor sealing material may foam. Thereby, bubbles called voids are generated, and the semiconductor sealing material is peeled off from the semiconductor chip and the substrate. In addition, when springback occurs in the void or semiconductor chip during heating and pressurization / pressure release, connection failure such as breakage of the connection portion due to tearing of the connection bump connecting the connection portions occurs. Due to these reasons, there is a concern that the conventional semiconductor encapsulating material may deteriorate in connectivity and insulation reliability.

  Also, if the semiconductor sealing material does not have sufficient flux activity (removal effect of oxide film and impurities on the metal surface), the oxide film and impurities on the metal surface cannot be removed, and a good metal-metal junction is formed. In some cases, continuity cannot be ensured. Furthermore, if the insulation reliability of the semiconductor sealing material is low, it is difficult to cope with the narrow pitch of the connection portion, resulting in insulation failure. For these reasons, there is a concern that the conventional semiconductor encapsulating material may deteriorate in connectivity and insulation reliability.

  A semiconductor device manufactured using a semiconductor sealing material is required to achieve high connection reliability. Connection reliability can be evaluated by, for example, TCT (Thermal Cycle Test) evaluation.

  The present invention has been made in view of the above circumstances, and provides an adhesive composition (adhesive for semiconductor encapsulation) that enables the production of a semiconductor device excellent in connection reliability and insulation reliability, and an adhesive composition thereof. It is an object of the present invention to provide a method of manufacturing a semiconductor device and a semiconductor device used.

  The present invention relates to a semiconductor device in which connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or a connection portion in a semiconductor device in which connection portions of a plurality of semiconductor chips are electrically connected to each other. An adhesive composition containing an epoxy resin, a curing agent, and a vinyl-based surface treatment filler surface-treated with a compound having a group represented by the following general formula (1) A composition is provided.

In formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group or an ethyl group, and R ⁴ represents an alkylene group having 1 to 30 carbon atoms.

  The present invention also provides a connection in a semiconductor device in which the connection portions of the semiconductor chip and the printed circuit board are electrically connected to each other, or a semiconductor device in which the connection portions of the plurality of semiconductor chips are electrically connected to each other. An adhesive composition for sealing a part is provided, which contains an epoxy resin, a curing agent, and a filler having a group represented by the following general formula (1).

In formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group or an ethyl group, and R ⁴ represents an alkylene group having 1 to 30 carbon atoms.

  The adhesive composition of the present invention contains an epoxy resin and a curing agent, and further contains a vinyl-based surface treatment filler or a filler having a group represented by the general formula (1). Even when applied as a fastening adhesive, high connection reliability and high insulation reliability of the semiconductor device can be realized.

  Here, when a silane coupling agent or the like is included in the resin together with a filler that has not been surface-treated, the filler surface is subjected to a silane coupling treatment, and fillers of various surface states are synthesized by substituents of the silane coupling agent. It is known that you can. However, the volatility of the silane coupling agent is high, which causes voids in the manufacturing process of a semiconductor device having a process at a high temperature such as metal bonding that requires high-temperature connection. Similarly, when surface-treating a conventionally used filler, a highly volatile organic substance such as methanol may be generated, which causes a void.

  Further, in the TCT evaluation, a temperature change of −55 to 125 ° C. is applied to the semiconductor package. However, when the solder wettability is insufficient or the metal bonding of the connection portion is incomplete, the semiconductor chip and the substrate are not connected. The connection portion is destroyed due to accumulation of stress in the connection portion due to the difference in thermal expansion coefficient. Here, if the coefficient of thermal expansion of the semiconductor sealing material is low, it is considered that the connection reliability (TCT resistance) of the semiconductor device can be improved because stress on the connection portion can be reduced.

  The inventors apply the adhesive composition as an adhesive for semiconductor encapsulation by incorporating the vinyl-based surface treatment filler or the filler having a group represented by the general formula (1) into the adhesive composition. In this case, it has been found that high connection reliability of the semiconductor device can be realized. In the adhesive composition of the present invention, it is possible to suppress the generation of highly volatile substances by using a vinyl surface-treated filler that has been surface-treated in advance or a filler having a group represented by the above general formula (1). Can do. In addition to this, the vinyl group on the filler surface reacts with other components to form a hardened cured product, thereby reducing the coefficient of thermal expansion of the cured product and exhibiting high connection reliability. They speculate. Further, since the vinyl-based surface treatment filler or the filler having the group represented by the general formula (1) is difficult to reduce the insulation reliability of the connection portion, the connection reliability can be improved, and the present invention. They speculate.

  The compound having a group represented by the general formula (1) is preferably a compound represented by the following general formula (2).

In formula (2), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group or an ethyl group, R ⁴ represents an alkylene group having 1 to 30 carbon atoms, and R ⁵ represents 1 to carbon atoms. 30 alkyl groups are shown.

  The adhesive composition of this invention can further improve connection reliability and insulation reliability by containing the filler surface-treated with the compound represented by the said General formula (2).

  The adhesive composition of the present invention may further contain a polymer component having a weight average molecular weight of 10,000 or more from the viewpoint of improving the film forming property of the adhesive composition.

  From the viewpoint of further improving the adhesive properties and film formability of the adhesive composition, the polymer component preferably has a weight average molecular weight of 30000 or more and a glass transition temperature of 100 ° C. or less.

  The adhesive composition of the present invention may further contain a flux activator to increase the flux activity and remove the oxide film and impurities on the metal surface of the connection part to form a good metal-metal bond. it can.

  Since the workability in the case of sealing a gap between a semiconductor chip and a printed circuit board or a gap between a plurality of semiconductor chips by the pre-applied method can be improved, the adhesive composition of the present invention has a film shape. It is preferable that

  The present invention also provides a semiconductor device in which respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or a semiconductor device in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other. It is a method, Comprising: The manufacturing method of a semiconductor device provided with the process of sealing a connection part using said adhesive composition is provided.

  According to the method for manufacturing a semiconductor device of the present invention, the connection reliability and the insulation reliability of the semiconductor device can be improved by using the adhesive composition.

  When the connection part contains at least one metal selected from the group consisting of gold, silver, copper, nickel, tin and lead as a main component, the electrical conductivity, thermal conductivity and connection reliability of the connection part are further improved. can do.

  The present invention also provides a semiconductor device obtained by the method for manufacturing a semiconductor device.

  Since the semiconductor device of the present invention is manufactured using the method for manufacturing a semiconductor device, the connection reliability and the insulation reliability are sufficiently excellent.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a semiconductor device using the adhesive composition which enables preparation of the semiconductor device excellent in connection reliability and insulation reliability, and the adhesive composition, and a semiconductor device can be provided. .

It is a schematic cross section showing one embodiment of a semiconductor device of the present invention. It is a schematic cross section which shows other one Embodiment of the semiconductor device of this invention. It is a schematic cross section which shows other one Embodiment of the semiconductor device of this invention. It is process sectional drawing which shows typically one Embodiment of the manufacturing method of the semiconductor device of this invention. It is a schematic diagram which shows the external appearance of the sample for an insulation reliability test.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

<Adhesive composition>
The adhesive composition (adhesive for semiconductor encapsulation) of the present embodiment is a semiconductor in which respective connection portions of a semiconductor chip and a printed circuit board (hereinafter simply referred to as “substrate” in some cases) are electrically connected to each other. An adhesive composition for sealing a connection part in a device or a semiconductor device in which each connection part of a plurality of semiconductor chips is electrically connected to each other, and an epoxy resin (hereinafter, “(a) component” ), A curing agent (hereinafter referred to as “component (b)” in some cases), and a vinyl-based surface treatment filler or a filler having a group represented by the general formula (1) (hereinafter referred to as “ (C) component "). In addition, the adhesive composition is optionally composed of a polymer component having a weight average molecular weight of 10,000 or more (hereinafter referred to as “(d) component”) or a flux activator (hereinafter referred to as “(e) component”. "). Hereinafter, each component which comprises the adhesive composition of this embodiment is demonstrated.

(A) Component: Epoxy Resin Any epoxy resin can be used without particular limitation as long as it has two or more epoxy groups in the molecule. Specific examples of the component (a) include 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 polyfunctionalities. 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.).

(B) Component: Curing Agent Examples of the (b) component include a phenol resin curing agent, an acid anhydride curing agent, an amine curing agent, an imidazole curing agent, and a phosphine curing agent. (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.

(I) 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. For example, phenol novolak, cresol novolak, phenol aralkyl resin, cresol A naphthol formaldehyde polycondensate, a triphenylmethane type polyfunctional phenol, and various polyfunctional phenol resins can be used. These can be used alone or as a mixture of two or more.

  The equivalent ratio of the phenol resin-based curing agent to the component (a) (phenolic hydroxyl group / epoxy group, molar ratio) is 0.3 to 1.5 from the viewpoint of good curability, adhesiveness, and storage stability. Preferably, 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is still more preferable. When the equivalence ratio is 0.3 or more, the curability tends to be improved and the adhesive force tends to be improved. When the equivalent ratio is 1.5 or less, the unreacted phenolic hydroxyl group does not remain excessively, and the water absorption is increased. It tends to be kept low and the insulation reliability improves.

(Ii) Acid anhydride curing agent Examples of the acid anhydride curing agent include methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and ethylene glycol bis. Anhydro trimellitate can be used. These can be used alone or as a mixture of two or more.

  The equivalent ratio of the acid anhydride curing agent to the component (a) (acid anhydride group / epoxy group, molar ratio) is 0.3 to 1. in terms of good curability, adhesiveness, and storage stability. 5 is preferable, 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is still more preferable. When the equivalence ratio is 0.3 or more, the curability tends to be improved and the adhesive strength tends to be improved. When the equivalent ratio is 1.5 or less, the unreacted acid anhydride does not remain excessively, and the water absorption is low. The insulation reliability tends to be suppressed.

(Iii) Amine-based curing agent As the amine-based curing agent, for example, dicyandiamide can be used.

  The equivalent ratio of the amine curing agent to the component (a) (amine / epoxy group, molar ratio) is preferably 0.3 to 1.5 from the viewpoints of good curability, adhesiveness, storage stability, etc. .4 to 1.0 is more preferable, and 0.5 to 1.0 is still more preferable. When the equivalence ratio is 0.3 or more, the curability is improved and the adhesive force tends to be improved. When the equivalent ratio is 1.5 or less, the unreacted amine does not remain excessively, and the insulation reliability is improved. Tend.

(Iv) Imidazole-based curing agent Examples of the imidazole-based curing agent 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-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5- Examples include dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins and imidazoles. Among these, from the viewpoint of excellent curability, storage stability, and connection reliability, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimelli Tate, 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-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl -4-Methyl-5-hydroxymethylimidazole is preferred. These can be used alone or in combination of two or more. Moreover, it is good also as a latent hardening | curing agent which encapsulated these.

  0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for content of an imidazole series hardening | curing agent, 0.1-10 mass parts is more preferable. If the content of the imidazole-based curing agent is 0.1 parts by mass or more, the curability tends to be improved, and if it is 20 parts by mass or less, the adhesive composition may be cured before the metal bond is formed. There is a tendency that poor connection is less likely to occur.

(V) Phosphine-based curing agent Examples of the phosphine-based curing agent include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (4-methylphenyl) borate and tetraphenylphosphonium (4-fluorophenyl) borate. Can be mentioned.

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

  The phenol resin curing agent, the acid anhydride curing agent and the amine curing agent can be used singly or as a mixture of two or more. The imidazole-based curing agent and the phosphine-based curing agent may each be used alone, but may be used together with a phenol resin-based curing agent, an acid anhydride-based curing agent, or an amine-based curing agent.

  When the adhesive composition contains a phenol resin curing agent, an acid anhydride curing agent or an amine curing agent as the component (b), it exhibits a flux activity for removing an oxide film and further improves connection reliability. Can do.

Component (c): Vinyl-based surface treatment filler or filler having a group represented by the above general formula (1) (c) As a component, a surface treatment is performed with a compound having a group represented by the above general formula (1). If it is a filler, there is no restriction | limiting in particular, For example, what surface-treated the insulating inorganic filler, the whisker, and the resin filler can be used. That is, as the component (c), a filler having a group represented by the general formula (1) can be used. Here, in formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group or an ethyl group, and a relatively non-bulky group is more reactive, so hydrogen It is preferably an atom or a methyl group, more preferably R ¹ and R ² are hydrogen atoms, and R ³ is a hydrogen atom or a methyl group. R ⁴ represents an alkylene group having 1 to 30 carbon atoms, and preferably has a higher molecular weight because it is less likely to volatilize. R ¹ , R ² , R ³ and R ⁴ can be appropriately selected depending on the ease of surface treatment.

  Examples of the insulating inorganic filler include glass, silica, alumina, titanium oxide, carbon black, mica, and boron nitride. Silica, alumina, titanium oxide, and boron nitride are preferable, and silica, alumina, and boron nitride are more preferable. . Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride. Examples of the resin filler include polyurethane and polyimide. 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. Among these fillers, silica filler is preferable because of easy surface treatment and relatively good compatibility with the resin component.

As the vinyl surface treatment filler, it is preferable to use a filler surface-treated with the compound represented by the general formula (2). In the formula (2), R ¹ , R ² , R ³ and R ⁴ can be selected from the same viewpoint as the formula (1). R ⁵ represents an alkyl group having 1 to 30 carbon atoms and can be appropriately selected depending on the ease of surface treatment, and is preferably a methyl group or an ethyl group.

  The shape and particle size of the component (c) may be appropriately set according to the use of the adhesive composition, and are not particularly limited.

  The amount of component (c) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total solid content of the adhesive composition. If it is 5% by mass or more, the effect of reducing the coefficient of thermal expansion of the adhesive composition after curing tends to be sufficiently exhibited, and if it is 60% by mass or less, the viscosity can be easily adjusted, and the flow of the adhesive composition And the filler is less likely to be trapped (trapping) and the connection reliability tends to be improved.

  There are various causes for the generation of voids in high-temperature processes such as high-temperature connection in flip-chip connection, but the main cause is volatilization of the constituent components of the adhesive composition. Therefore, the constituent component is preferably a solid component rather than a liquid component.

  Moreover, when a silane coupling agent is not surface-treated with a filler in advance and is added as a constituent component of the adhesive composition, and surface treatment is performed in the system, methanol or the like is generated, which causes foaming during a high-temperature process.

Component (d): Polymer component having a weight average molecular weight of 10,000 or more Examples of component (d) include phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, polyethylene resin, poly Examples include ether sulfone resin, polyetherimide resin, polyvinyl acetal resin, urethane resin, and acrylic rubber. Among these, from the viewpoint of excellent heat resistance and film formability, phenoxy resin, polyimide resin, acrylic rubber, cyanate ester resin, and polycarbodiimide resin are preferable, and phenoxy resin, polyimide resin, and acrylic rubber are more preferable. These components (d) can be used alone or as a mixture or copolymer of two or more. However, the (d) component does not include the epoxy resin as the (a) component.

  As the above-described polymer components such as phenoxy resin and polyimide resin, commercially available products may be used, or synthesized products may be used.

  The polyimide resin can be obtained, for example, by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. More specifically, tetracarboxylic dianhydride and diamine are mixed in equimolar or almost equimolar amounts 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 The addition reaction may be set at 60 ° C. The tetracarboxylic dianhydride is preferably recrystallized and purified with acetic anhydride in order to suppress deterioration of various properties of the adhesive composition.

  As the addition reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide precursor, is generated. The polyimide resin can be obtained by dehydrating and ring-closing the polyamic acid. The dehydration ring closure can be performed by a thermal ring closure method in which heat treatment is performed or a chemical ring closure method using a dehydrating agent. The molecular weight of the polyamic acid can be adjusted by heating at 50 to 80 ° C. for depolymerization.

  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 Dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxy) Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetraca Boronic 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 Tetrachloronaphthalene-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 (trimellitate 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] -o To-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-dicarboxy) Phenyl) phenyl] hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimerit Acid anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydro Ryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, tetracarboxylic acid represented by the following general formula (I) Examples thereof include acid dianhydrides and tetracarboxylic dianhydrides represented by the following formula (II).

  In formula (I), a represents an integer of 2 to 20.

  The tetracarboxylic dianhydride represented by the above general formula (I) can be synthesized from trimellitic anhydride monochloride and the corresponding diol, specifically, 1,2- (ethylene) bis (trimellitate). Anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1, 6- (Hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (nonamethylene) Bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecamethylene) bi (Trimellitate anhydride), 1,16 (hexamethylene decamethylene) bis (trimellitate anhydride) and 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. The said tetracarboxylic dianhydride can be used individually or in combination of 2 or more types.

  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% or more based on the total tetracarboxylic dianhydride. Further preferred. When the content is 40 mol% or more, there is a tendency to sufficiently ensure the effect of moisture resistance reliability due to the use of the tetracarboxylic dianhydride represented by the above formula (II).

  There is no restriction | limiting in particular as diamine used as a raw material of the said polyimide resin, For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'- diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-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′-diaminodiphenyl Sulfo 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfide, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 3,3 ′ -Diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 '-(3,4'-diaminodiphenyl) Propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2 -Bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) Zen, 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-aminoethyl) Noxy) 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, an aliphatic ether diamine represented by the following general formula (III) or (IV), an aliphatic diamine represented by the following general formula (V), and the following general formula (VI) Examples include siloxane diamine.

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

In formula (IV), Q ⁴ , Q ⁵ , Q ⁶ and Q ⁷ each independently represent an alkylene group having 1 to 10 carbon atoms, and c, d and e each independently represent an integer of 1 to 50.

  In formula (V), f shows the integer of 5-20.

In formula (VI), Q ⁸ and Q ¹³ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q ⁹ , Q ¹⁰ , Q ¹¹ and Q ¹² are each Independently, it represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and g represents an integer of 1 to 5.

  Among these, the diamine represented by the above general formula (III), (IV) or (V) is preferable in that low stress property, low temperature laminating property and low temperature adhesiveness can be imparted, and has low water absorption and low water absorption. The diamine represented by the said general formula (VI) is preferable at the point which can provide. These diamines can be used alone or in combination of two or more.

  The content of the aliphatic ether diamine represented by the general formula (III) or (IV) is preferably 1 to 50 mol% of the total diamine, and the aliphatic diamine represented by the general formula (V). The content of is preferably 20 to 80 mol% of the total diamine, and the content of the siloxane diamine represented by the general formula (VI) is preferably 20 to 80 mol% of the total diamine. When the content is within the above range, the effect of imparting low temperature laminating properties and low water absorption tends to increase.

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

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

  Among the above aliphatic ether diamines, the above general formula (IV), the following general formula (VII), (VIII) or (IX) is used in that low-temperature laminating properties and good adhesion to a substrate with an organic resist can be secured. The aliphatic ether diamine represented respectively is more preferable.

  In formula (VII), h represents an integer of 2 to 80, more preferably 2 to 70.

  In formula (VIII), c, d and e represent an integer of 1 to 50, more preferably 2 to 40.

  In formula (IX), j and k each independently represent an integer of 1 to 70.

  Specific examples of the aliphatic ether diamine represented by the general formula (VII) include Jeffamine D-230, D-400, D-2000 and D-4000 manufactured by Sun Techno Chemical Co., Ltd., and BASF. Polyether amines D-230, D-400, and D-2000 are exemplified, and as the aliphatic ether diamine represented by the general formula (VIII), specifically, Jeffermin ED manufactured by Sun Techno Chemical Co., Ltd. -600, ED-900, and ED-2001, and specific examples of the aliphatic ether diamine represented by the above formula (IX) include Jeffamine EDR-148 manufactured by Sun Techno Chemical Co., Ltd. .

  Examples of the aliphatic diamine represented by the general formula (V) 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 and 1,2-diaminocyclohexane Is mentioned. Among these, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane are preferable.

  As the siloxane diamine represented by the general formula (VI), when g in the general formula (VI) is 1, 1,1,3,3-tetramethyl-1,3-bis (4-amino) Phenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (2-amino) Ethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (2-amino) Ethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-amino) Butyl) disiloxane and 1,3-dimethyl-1,3- Methoxy-1,3-bis (4-aminobutyl) disiloxane and the like. When g is 2, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3 -Dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1, 1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5- Bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetra Methyl-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- Examples include 1,5-bis (3-aminopropyl) trisiloxane and 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane.

  The said polyimide resin can be used individually or as a mixture of 2 or more types.

  The glass transition temperature (Tg) of the component (d) is preferably 100 ° C. or less and more preferably 75 ° C. or less from the viewpoint of excellent adhesiveness of the adhesive composition to the substrate or chip. When Tg is 100 ° C. or less, bumps formed on the semiconductor chip, and unevenness such as electrodes and wiring patterns formed on the substrate can be easily embedded with the adhesive composition, and no voids remain without voids. Tends to be less likely to occur. In addition, said Tg is Tg when using DSC (DSC-7 type | mold by Perkin-Elmer Co., Ltd.) and measuring on the conditions of sample amount 10mg, temperature increase rate 5 degree-C / min, and measurement atmosphere: air.

  Although the weight average molecular weight of (d) component is 10,000 or more in polystyrene conversion, in order to show favorable film formation independently, 30000 or more are preferable, 40000 or more are more preferable, and 50000 or more are still more preferable. When the weight average molecular weight is 10,000 or more, the film formability tends to be improved. 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 (For example, the product name "C-R4A" by Shimadzu Corporation).

  The content of the component (d) is not particularly limited, but is preferably 1 to 500 parts by mass, and 5 to 300 parts by mass with respect to 100 parts by mass of the component (a) in order to maintain a good film shape. More preferably, it is more preferably 10 to 200 parts by mass. When the content of the component (d) is 1 part by mass or more, there is a tendency that an effect of improving the film formability tends to be obtained, and when it is 500 parts by mass or less, the curability of the adhesive composition is improved and the adhesive strength is increased. There is a tendency to improve.

(E) Component: Flux Activator The adhesive composition of the present invention can contain a component (e), 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.

  Among these, carboxylic acids have a strong flux activity, react easily with the epoxy resin as component (a), and do not exist in a free state in the cured product of the adhesive composition, thus preventing a decrease in insulation reliability. be able to.

  Examples of carboxylic acids include ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid. Fatty saturated carboxylic acids; oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, etc .; aliphatic unsaturated carboxylic acids; maleic acid, fumaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid , Aliphatic dicarboxylic acids such as adipic acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, benzenepentacarboxylic acid and melittic acid Is mentioned. Examples of the carboxylic acid having a hydroxyl group include lactic acid, malic acid, citric acid, and salicylic acid.

  Furthermore, the aromatic carboxylic acid has an electron-withdrawing or electron-donating substituent, and an aromatic carboxylic acid in which the acidity of the carboxylic acid on the aromatic is changed by the substituent can also be used. Although the flux activity tends to improve as the acidity of the carboxylic acid increases, the insulation reliability may decrease if the acidity is too high. Examples of the electron-withdrawing substituent that increases the acidity of the carboxylic acid include a nitro group, a cyano group, a trifluoromethyl group, a halogen group, and a phenyl group. Examples of the electron donating substituent that weakens the acidity of the carboxylic acid include a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, a dimethylamino group, and a trimethylamino group. The number and position of the substituents are not particularly limited as long as the flux activity and the insulation reliability are not lowered.

  Carboxylic acids are preferably used in solid form rather than liquid form at room temperature so as not to decompose and generate volatile components upon heating at high temperature.

(Other ingredients)
In the adhesive composition of this embodiment, in order to control the viscosity and physical properties of the cured product, and to suppress the generation of voids and the increase in the moisture absorption rate when the semiconductor chip and the substrate are connected, (c) In addition to the components, a filler may be further blended.

  As the filler, an insulating inorganic filler, whisker, or resin filler can be used. As the insulating inorganic filler, whisker, or resin filler, the same material as the component (c) can be used. These fillers, whiskers, and resin fillers can be used alone or as a mixture of two or more. The shape, average particle diameter and content of the filler are not particularly limited.

  Furthermore, you may mix | blend additives, such as antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, and an ion trap agent, with the adhesive composition of this embodiment. You may use these individually by 1 type or in combination of 2 or more types. About these compounding quantities, what is necessary is just to adjust suitably so that the effect of each additive may express.

  The adhesive composition of this embodiment can be formed into a film. A method for producing a film adhesive using the adhesive composition of the present embodiment is shown below. First, the component (a), the component (b) and the component (c), and the component (d) or the component (e) added as necessary are added to an organic solvent, and mixed by stirring, kneading, etc. A resin varnish is prepared by dissolving or dispersing. Then, after applying the resin varnish on the base film subjected to the release treatment using a knife coater, roll coater or applicator, the organic solvent is removed by heating, whereby a film adhesive is applied on the base film. Is obtained. In addition, when mix | blending (d) component, you may prepare the said resin varnish by adding each component in the varnish obtained after a synthesis | combination, without isolating after synthesize | combining (d) component.

  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 alone or in combination of two or more. Stir mixing and kneading at the time of preparing the resin varnish can be performed using, for example, a stirrer, a raking machine, a three roll, a ball mill, a bead mill, and a homodisper.

  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. Polyolefin film such as polypropylene film and polymethylpentene film, polyethylene terephthalate film, polyethylene naphthalate Examples thereof include polyester films such as films, polyimide films, and polyetherimide 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.

  It is preferable that the drying conditions for volatilizing the organic solvent from the resin varnish applied to the base film are such that the organic solvent is sufficiently volatilized, specifically, 50 to 200 ° C. and 0.1 to 90 minutes. It is preferable to perform heating.

<Semiconductor device>
The semiconductor device of this embodiment will be described below with reference to FIGS. FIG. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present invention. As shown in FIG. 1A, a semiconductor device 100 includes a semiconductor chip 10 and a substrate (circuit wiring board) 20 that face each other, and wirings 15 that are respectively disposed on mutually facing surfaces of the semiconductor chip 10 and the substrate 20. The connection bump 30 connects the semiconductor chip 10 and the wiring 15 of the substrate 20 to each other, and the adhesive composition 40 is filled in the gap between the semiconductor chip 10 and the substrate 20 without a gap. The semiconductor chip 10 and the substrate 20 are flip-chip connected by wiring 15 and connection bumps 30. The wiring 15 and the connection bump 30 are sealed with an adhesive composition 40 and are shielded from the external environment.

  As shown in FIG. 1B, the semiconductor device 200 includes a semiconductor chip 10 and a substrate 20 that face each other, a bump 32 that is disposed on a surface that faces the semiconductor chip 10 and the substrate 20, respectively, And an adhesive composition 40 filled in the gaps between the substrates 20 without any gaps. The semiconductor chip 10 and the substrate 20 are flip-chip connected by connecting opposing bumps 32 to each other. The bumps 32 are sealed with the adhesive composition 40 and are blocked from the external environment.

  FIG. 2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention. As shown in FIG. 2A, the semiconductor device 300 is the same as the semiconductor device 100 except that two semiconductor chips 10 are flip-chip connected by wirings 15 and connection bumps 30. As shown in FIG. 2B, the semiconductor device 400 is the same as the semiconductor device 200 except that the two semiconductor chips 10 are flip-chip connected by the bumps 32.

  The semiconductor chip 10 is not particularly limited, and an elemental semiconductor composed of the same kind of element such as silicon or germanium, or a compound semiconductor such as gallium arsenide or indium phosphide can be used.

  The substrate 20 is not particularly limited as long as it is a circuit board, and an unnecessary portion of a metal film is etched on the surface of an insulating substrate mainly composed of glass epoxy, polyimide, polyester, ceramic, epoxy, bismaleimide triazine, or the like. Circuit board having wiring (wiring pattern) 15 formed by removing, circuit board having wiring 15 formed on the surface of the insulating substrate by metal plating or the like, wiring by printing a conductive material on the surface of the insulating substrate A circuit board on which 15 is formed can be used.

  The connection parts such as the wiring 15 and the bumps 32 are gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), nickel, tin, lead as main components. Etc., and may contain a plurality of metals.

  Among the metals described above, gold, silver and copper are preferable, silver and copper are more preferable, and silver is still more preferable from the viewpoint of making the package excellent in electrical conductivity and thermal conductivity of the connection portion. From the viewpoint of providing a package with reduced cost, silver, copper and solder are preferable, copper and solder are more preferable, and solder is still more preferable based on the low cost. If an oxide film is formed on the surface of the metal at room temperature, the productivity may decrease or the cost may increase. From the viewpoint of suppressing the formation of the oxide film, gold, silver, copper and solder are preferable, and gold, silver Solder is more preferable, and gold and silver are more preferable.

  Gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc. The metal layer to be formed may be formed by plating, for example. This metal layer may be composed of only a single component or may be composed of a plurality of components. The metal layer may have a structure in which a single layer or a plurality of metal layers are stacked.

  Further, in the semiconductor device of this embodiment, a plurality of structures (packages) as shown in the semiconductor devices 100 to 400 may be stacked. In this case, the semiconductor devices 100 to 400 are bumps or wirings including gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, or the like. They may be electrically connected to each other.

  As a method of stacking a plurality of semiconductor devices, as shown in FIG. 3, for example, a TSV (Through-Silicon Via) technique is cited. FIG. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention, which is a semiconductor device using the TSV technology. In the semiconductor device 500 shown in FIG. 3, the wiring 15 formed on the interposer 50 is connected to the wiring 15 of the semiconductor chip 10 via the connection bumps 30, so that the semiconductor chip 10 and the interposer 50 are flip-chip connected. ing. The gap between the semiconductor chip 10 and the interposer 50 is filled with the adhesive composition 40 without a gap. On the surface of the semiconductor chip 10 opposite to the interposer 50, the semiconductor chip 10 is repeatedly stacked via the wiring 15, the connection bumps 30, and the adhesive composition 40. The wirings 15 on the pattern surface on the front and back sides of the semiconductor chip 10 are connected to each other by through electrodes 34 filled in holes that penetrate the inside of the semiconductor chip 10. In addition, as a material of the penetration electrode 34, copper, aluminum, etc. can be used.

  Such a TSV technique makes it possible to acquire signals from the back surface of a semiconductor chip that is not normally used. Furthermore, since the through electrode 34 passes vertically through the semiconductor chip 10, the distance between the semiconductor chips 10 facing each other and between the semiconductor chip 10 and the interposer 50 can be shortened and flexible connection is possible. The adhesive composition of the present embodiment can be applied as an adhesive for semiconductor sealing between the semiconductor chips 10 facing each other or between the semiconductor chip 10 and the interposer 50 in such TSV technology.

  In addition, in a bump forming method with a high degree of freedom such as an area bump chip technology, a semiconductor chip can be directly mounted on a mother board without using an interposer. The adhesive composition of this embodiment can also be applied when such a semiconductor chip is directly mounted on a mother board. In addition, the adhesive composition of this embodiment can be applied also when sealing the space | gap between board | substrates, when laminating | stacking two wiring circuit boards.

<Method for Manufacturing Semiconductor Device>
A method for manufacturing the semiconductor device of this embodiment will be described below with reference to FIGS. FIG. 4 is a process cross-sectional view schematically showing one embodiment of a method for manufacturing a semiconductor device of the present invention.

  First, as shown in FIG. 4A, a solder resist 60 having openings at positions where connection bumps 30 are formed is formed on a substrate 20 having wirings (for example, gold bumps) 15. The solder resist 60 is not necessarily provided. However, by providing a solder resist on the substrate 20, it is possible to suppress the occurrence of a bridge between the wirings 15 and improve the connection reliability and insulation reliability. The solder resist 60 can be formed using, for example, commercially available solder resist ink for packages. Specific examples of commercially available solder resist for package resist include SR series (trade name, manufactured by Hitachi Chemical Co., Ltd.) and PSR4000-AUS series (trade name, manufactured by Taiyo Ink Manufacturing Co., Ltd.).

  Next, as shown in FIG. 4A, connection bumps (for example, solder bumps) 30 are formed in the openings of the solder resist 60. Then, as shown in FIG. 4B, a film-like adhesive composition (hereinafter sometimes referred to as “film-like adhesive”) 40 is formed on the substrate 20 on which the connection bumps 30 and the solder resist 60 are formed. Affix. The film adhesive 40 can be attached by a hot press, roll lamination, vacuum lamination, or the like. The supply area and thickness of the film adhesive 40 are appropriately set according to the size of the semiconductor chip 10 and the substrate 20 and the height of the connection bump 30.

  After the film-like adhesive 40 is attached to the substrate 20 as described above, the wiring 15 and the connection bumps 30 of the semiconductor chip 10 are aligned using a connection device such as a flip chip bonder. Subsequently, the semiconductor chip 10 and the substrate 20 are pressure-bonded while being heated at a temperature equal to or higher than the melting point of the connection bump 30 to connect the semiconductor chip 10 and the substrate 20 as shown in FIG. The gap between the semiconductor chip 10 and the substrate 20 is sealed and filled with the adhesive 40. Thus, the semiconductor device 600 is obtained.

  In the manufacturing method of the semiconductor device according to the present embodiment, the semiconductor chip 10 and the substrate 20 may be connected by melting the connection bumps 30 by temporarily fixing them after alignment and performing heat treatment in a reflow furnace. Since it is not always necessary to form a metal joint at the temporary fixing stage, it can be crimped with a low load, in a short time, and at a low temperature as compared with the above-mentioned method of crimping while heating. Deterioration of the part can be suppressed.

  Further, after the semiconductor chip 10 and the substrate 20 are connected, heat treatment may be performed in an oven or the like to further improve connection reliability and insulation reliability. The heating temperature is preferably a temperature at which curing of the film adhesive proceeds, and more preferably a temperature at which the film adhesive is completely cured. The heating temperature and the heating time are appropriately set.

  In the semiconductor device manufacturing method of the present embodiment, the substrate 20 may be connected after the film-like adhesive 40 has been applied to the semiconductor chip 10. Further, after the semiconductor chip 10 and the substrate 20 are connected by the wiring 15 and the connection bumps 30, the gap between the semiconductor chip 10 and the substrate 20 may be filled with a paste-like adhesive composition.

  From the viewpoint of improving productivity, the adhesive composition is supplied onto the semiconductor chip 10 by supplying the adhesive composition to a semiconductor wafer connected with a plurality of semiconductor chips 10 and then dicing into individual pieces. The obtained structure may be obtained. Further, when the adhesive composition is in a paste form, it is not particularly limited, but it is sufficient to embed wirings and bumps on the semiconductor chip 10 and make the thickness uniform by a coating method such as spin coating. In this case, since the supply amount of the resin becomes constant, productivity is improved and generation of voids due to insufficient embedding and a decrease in dicing property can be suppressed. On the other hand, when the adhesive composition is in the form of a film, it is not particularly limited. However, the adhesive composition is in a film form so as to embed wirings and bumps on the semiconductor chip 10 by a sticking method such as heating press, roll lamination, and vacuum lamination. What is necessary is just to supply a resin composition. In this case, since the supply amount of the resin is constant, productivity is improved, and generation of voids due to insufficient embedding and a decrease in dicing property can be suppressed.

  The connection load is set in consideration of variations in the number and height of the connection bumps 30, the amount of deformation of the wiring that receives the connection bumps 30 or the bumps of the connection portions due to pressure. The connection temperature is preferably such that the temperature of the connection portion is equal to or higher than the melting point of the connection bump 30, but may be any temperature at which metal connection of each connection portion (bump or wiring) is formed. When the connection bump 30 is a solder bump, it may be about 240 ° C. or higher.

  The connection time at the time of connection varies depending on the constituent metal of the connection part, but a shorter time is preferable from the viewpoint of improving productivity. When the connection bump 30 is a solder bump, the connection time is preferably 20 seconds or less, more preferably 10 seconds or less, and even more preferably 5 seconds or less. In the case of copper-copper or copper-gold metal connection, the connection time is preferably 60 seconds or less.

  The adhesive composition of the present invention exhibits excellent connection reliability and insulation reliability even in the flip chip connection portions having various package structures described above.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example and a comparative example, this invention is not restrict | limited by the following examples.

(Polyimide synthesis)
In a 300 mL flask equipped with a thermometer, a stirrer, and a calcium chloride tube, 2.12 g (0.035 mol) of 1,12-diaminododecane, polyether diamine (trade name “ED2000”, 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., hereinafter referred to as “NMP”) was charged and stirred. After dissolution of the diamine, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic dianhydride) (made by ALDRICH) 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 to azeotropically remove xylene together with water to obtain a polyimide resin. The solvent (NMP) was removed from the obtained polyimide resin, and the “polyimide A” was dissolved in a mixed solvent of toluene and ethyl acetate (mass ratio 1: 1) to a solid content of 50% by mass. Polyimide A had a Tg of 30 ° C., a weight average molecular weight of 50,000, and an SP value (solubility parameter) of 10.2.

The compounds used in each example and comparative example are as follows.
(A) Epoxy resin / polyfunctional solid epoxy containing triphenolmethane skeleton (manufactured by Japan Epoxy Resin Co., Ltd., trade name “EP1032H60”, hereinafter referred to as “EP1032”)
(B) Hardener: 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Co., Ltd., trade name “2PHZ-PW”, hereinafter referred to as “2PHZ”)
(C) Vinyl-based surface-treated filler or filler-vinyl surface-treated silica filler having a group represented by the above general formula (1) (manufactured by Admatechs, trade name “SE2050-SVJ”, average particle size 0.5 μm) Hereinafter referred to as “SV silica”)
(C ′) Other fillers / untreated silica filler (manufactured by Admatechs, trade name “SE2050”, average particle size 0.5 μm, hereinafter referred to as “untreated silica”)
Aminosilane-treated silica filler (manufactured by Admatechs Co., Ltd., trade name “SE2050-SXJ”, average particle size 0.5 μm, hereinafter referred to as “SX silica”)
Epoxy silane-treated silica filler (manufactured by Admatechs Co., Ltd., trade name “SE2050-SEJ”, average particle size 0.5 μm, hereinafter referred to as “SE silica”)
Phenylsilane-treated silica filler (manufactured by Admatechs Co., Ltd., trade name “SE2050-SPJ”, average particle size 0.5 μm, hereinafter referred to as “SP silica”)
Metabrene type organic filler (Made by Mitsubishi Rayon, trade name “W5500”, hereinafter referred to as “W5500”)
(D) Polymer component having a molecular weight of 10,000 or more. Polyimide A synthesized as described above.
(E) Flux activator / diphenolic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Preparation of film adhesive for semiconductor encapsulation>
Example 1
Epoxy resin (EP1032) 100 parts by mass, curing agent (2PHZ) 7.5 parts by mass, filler (SV silica) 175 parts by mass, flux activator (diphenolic acid) 25 parts by mass and a mixed solvent of toluene and ethyl acetate (mass) Ratio 1: 1) was added so that the solid content was 60% by mass, beads having a diameter of 0.8 mm and beads having a diameter of 2.0 mm were added in the same amount as the solid content, and a bead mill (Fritsch Japan KK, planetary type fine) was added. The mixture was stirred with a pulverizer “P-7”) for 30 minutes. Next, 100 parts by mass (in terms of solid content) of polyimide A was added, and the mixture was again stirred for 30 minutes with a bead mill, and then the beads used for stirring were removed by filtration to obtain a resin varnish.

  The resulting resin varnish was applied to a base film (trade name “Purex A53” manufactured by Teijin DuPont Films Ltd.) with a small precision coating device (manufactured by Yanai Seiki Co., Ltd.) Manufactured) and dried at 110 ° C. for 10 minutes to produce a film adhesive.

(Example 2 and Comparative Examples 1-5)
Except having changed the composition of the used raw material as Table 1 below, it carried out similarly to Example 1, and produced the film adhesive of Example 2 and Comparative Examples 1-5.

  Below, the evaluation method of the film adhesive obtained in the Example and the comparative example is shown.

<Evaluation of initial connectivity>
Cut out the produced film adhesive into a predetermined size (length 8 mm × width 8 mm × thickness 0.025 mm) and paste it on a glass epoxy substrate (glass epoxy substrate: 420 μm thickness, copper wiring: 9 μm thickness), Flip chip mounting device "FCB3" (manufactured by Panasonic, products) (Mounting conditions: reaching temperature of film adhesive 180 ° C., 10 seconds, 0.5 MPa. Next, reaching temperature of film adhesive 245 ° C., 10 seconds, 0.5 MPa). As a result, a semiconductor device in which the glass epoxy substrate and the semiconductor chip with solder bumps were daisy chain connected as in FIG. 4 was obtained.

  By measuring the connection resistance value of the obtained semiconductor device using a multimeter (trade name “R6871E” manufactured by ADVANTEST), the possibility of initial conduction after mounting was evaluated. The case where the connection resistance value was 11 to 14Ω was evaluated as “A”, and the connection resistance value other than that or the case where the connection value (Open) occurred and the resistance value was not displayed was evaluated as “B”. .

<Measurement of thermal expansion coefficient>
The film adhesive was cut into a predetermined size (length 37 mm × width 4 mm × thickness 0.025 mm, and cured for 3 hours at 180 ° C. in a clean oven (manufactured by ESPEC Corporation). Thermal expansion was measured under the conditions of a temperature range of 20 to 270 ° C., a temperature increase rate of 5 ° C./min, and a load of 0.5 MPa using a measuring device (manufactured by Seiko Instruments Inc., thermal analysis system TMASS6000). The rate was the average coefficient of thermal expansion (ppm / ° C) up to 25-125 ° C.

<Evaluation of connection reliability (TCT resistance evaluation)>
The above-described semiconductor device was after-cured (180 ° C./3 hours) in a clean oven (Espec Corp.). Then, it is left in a thermal cycle tester (manufactured by ETAC, THERMAL SHOCK CHAMBER NT1200), and a current of 1 mA is supplied, 25 ° C for 2 minutes / -55 ° C for 15 minutes / 25 ° C for 2 minutes / 125 ° C for 15 minutes / 25 ° C The connection resistance was measured with 2 minutes as one cycle. “A” when there is no significant change after 300 cycles compared to the initial resistance value waveform, “B” when a difference of 1 Ω or more occurs in 100 cycles or more and less than 300 cycles is “B”, and a difference of 1 Ω or more is 100 cycles The case where it occurred in less than "C" was designated.

<Evaluation of insulation reliability (HAST resistance evaluation)>
The produced film adhesive was cut out to a predetermined size (length 10 mm × width 5 mm × thickness 25 μm) and attached to a comb-type electrode substrate (wiring pitch: 0.05 mm) in which wiring copper wiring was formed on a polyimide substrate, As shown in FIG. 5, a sample in which the film adhesive 40 was laminated on the substrate 20 on which the comb-shaped electrode 90 was formed was produced. In FIG. 5, the film adhesive is not shown for convenience. Subsequently, the sample was cured by being held at 185 ° C. for 3 hours in a clean oven (manufactured by ESPEC Corporation). After curing, each sample was taken out and placed in an accelerated life test apparatus (trade name “PL-422R8” manufactured by HIRAYAMA, condition: 130 ° C./85% relative humidity / 200 hours / 5 V applied), and the insulation resistance was measured. . Throughout 200 hours, the case where the insulation resistance was 10 ⁸ Ω or more was evaluated as “A”, and the case where it was less than 10 ⁸ Ω was evaluated as “B”.

  Table 1 shows the composition (unit: part by mass) of raw materials of the adhesive compositions of each Example and Comparative Example and the results of each test.

  It was confirmed that Examples 1 and 2 using a vinyl surface treatment filler have a low coefficient of thermal expansion and are excellent in both connection reliability (TCT resistance) and insulation reliability (HAST resistance). It was.

  DESCRIPTION OF SYMBOLS 10 ... Semiconductor chip, 15 ... Wiring (connection part), 20 ... Board | substrate (wiring circuit board), 30 ... Connection bump, 32 ... Bump (connection part), 34 ... Through-electrode, 40 ... Adhesive composition (film adhesive) Agent), 50 ... interposer, 60 ... solder resist, 90 ... comb electrode, 100, 200, 300, 400, 500, 600 ... semiconductor device.

Claims (8)

In a semiconductor device in which respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or in a semiconductor device in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other, the connection portions are sealed. An adhesive composition comprising:
The adhesive composition containing an epoxy resin, a hardening | curing agent, and the vinyl-type surface treatment filler surface-treated with the compound represented by following General formula (2) .
[In Formula (2), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group or an ethyl group, R ⁴ represents an alkylene group having 1 to 30 carbon atoms, and R ⁵ represents 1 carbon atom. -30 alkyl groups are shown. ] Weight average molecular weight further comprises the 10000 or more polymeric components, the adhesive composition according to claim 1. The adhesive composition according to claim 2 , wherein the polymer component has a weight average molecular weight of 30000 or more and a glass transition temperature of 100 ° C. or less. The adhesive composition according to any one of claims 1 to 3 , further comprising a flux activator. The adhesive composition according to any one of claims 1 to 4 , wherein the shape is a film shape. A semiconductor device in which respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or a manufacturing method of a semiconductor device in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other,
The manufacturing method of a semiconductor device provided with the process of sealing the said connection part using the adhesive composition as described in any one of Claims 1-5 . The manufacturing method according to claim 6 , wherein the connection portion contains at least one metal selected from the group consisting of gold, silver, copper, nickel, tin, and lead as a main component. Obtained by the production method according to claim 6 or 7, the semiconductor device.