JP2011029232A - Adhesive composition, method of manufacturing semiconductor device by using the composition, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition for electrically connecting the connections of each of a semiconductor chip and a printed circuit board. <P>SOLUTION: In a semiconductor device 100 in which the connections 15 of each of the semiconductor chip 10 and the printed circuit board 20 are electrically connected to each other or a substrate in which the connections of a plurality of semiconductor chips are electrically connected to each other, the adhesive composition for sealing the connections contains polymer component having ≥10,000 of weight mean molecular weight, an epoxy resin, a curing agent and an amine-based surface treatment filler. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an adhesive composition, a method for manufacturing a semiconductor device using the adhesive composition, 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 miniaturization, thinning, and high functionality of semiconductor devices, a flip chip connection method (FC connection method) in which conductive protrusions called bumps are formed between a semiconductor chip and a substrate and the two are connected to each other. ) Is spreading.

  For example, regarding a 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 wiring) are formed on semiconductor chips to connect the semiconductor chips (for example, patents). Reference 1).

  However, in order to meet the demands for further miniaturization, thickness reduction, and higher functionality, chip stack type packages, POP (Package On Package), TSV (Through Silicon Via), etc., in which the above connection methods are stacked and multi-staged, are also available. It has begun 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 of suppressing the generation of these impurities and improving the connectivity, there is a method of pre-treating the surface of the substrate or the semiconductor chip before the connection, such as preflux used for OSP (Organic Solderbility Preservatives) processing. 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 sealing method using the semiconductor sealing material described above is roughly divided into a Capillary-Flow method and a Pre-applied method (see, for example, Patent Documents 2 to 6). The Capillary-Flow method is a method in which a liquid semiconductor sealing material is injected into a gap between the semiconductor chip and the substrate by a capillary phenomenon 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, with the recent progress of miniaturization of semiconductor devices, the gap between the semiconductor chip and the substrate has become narrower, 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 method for producing packages 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-described pre-applied method, since the gap between the semiconductor chip and the substrate is sealed with the semiconductor sealing material simultaneously with the connection by heating and pressing, the component contained in the semiconductor sealing material takes into account the connection conditions. Must be selected. 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.

  The present invention has been made in view of the above circumstances, and provides an adhesive composition capable of improving connectivity and insulation reliability, a method of manufacturing a semiconductor device using the adhesive composition, and a semiconductor device The purpose is to do.

  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 a polymer component having a weight average molecular weight of 10,000 or more, an epoxy resin, a curing agent, and an amine-based surface treatment filler is provided.

  In the adhesive composition of the present invention, the adhesive composition contains a polymer component having a predetermined weight average molecular weight, an epoxy resin, and a curing agent, and further contains an amine-based surface treatment filler. Thereby, it is possible to suppress the occurrence of voids in the adhesive composition even in the FC connection method using metal bonding at a high temperature (for example, 200 ° C. or higher), and from the metal surface of the connection portion. Impurities such as oxides can be removed, hardening and viscosity can be easily increased, solder tearing due to springback and the like can be suppressed, and connectivity is improved. It is also possible to improve the insulation reliability of the adhesive composition. Due to these reasons, the adhesive composition of the present invention can improve connectivity and insulation reliability.

  At least one organic component selected from a polymer component, an epoxy resin, and a curing agent is preferably solid at 25 ° C. and atmospheric pressure (101.33 kPa). In this case, it is possible to prevent the components contained in the adhesive composition from decomposing and generate volatile components during high-temperature heating, and the connectivity and insulation reliability can be further improved.

  The content of at least one organic component selected from a polymer component, an epoxy resin and a curing agent is 10% by mass or more, and the thermal weight reduction rate at 250 ° C. of the organic component having the content of 10% by mass or more is 10%. % Or less is preferable. In this case, it is possible to prevent the components contained in the adhesive composition from decomposing and generate volatile components during high-temperature heating, and the connectivity and insulation reliability can be further improved.

  The “thermal weight loss rate at 250 ° C.” is the initial value (35) in the thermogravimetric analysis performed under the conditions of the heating rate: 10 ° C./min, the air flow rate: 400 mL / min, and the measurement temperature: 35 to 400 ° C. The mass reduction rate is calculated by the ratio of the mass volatilized from 35 ° C. to 250 ° C. relative to the mass of (° C.).

  The polymer component is preferably a polyimide resin. In this case, heat resistance and film formability can be further improved. Furthermore, it is preferable that the weight average molecular weight of a polyimide resin is 30000 or more, and the glass transition temperature of a polyimide resin is 100 degrees C or less. In this case, the adhesive property and film formability of the adhesive composition can be further improved.

  The shape of the adhesive composition of the present invention is preferably a film. In this case, connectivity, insulation reliability, and productivity can be further improved.

  In the adhesive composition of the present invention, the melt viscosity (flow viscosity) at 250 ° C. for 10 seconds is preferably 1000 Pa · s or less. In this case, connectivity reliability and embeddability can be further improved.

  In this invention, it is preferable that a connection part contains at least 1 type of metal chosen from the group which consists of gold, silver, copper, nickel, tin, and lead as a main component. In this case, electrical conductivity, thermal conductivity, and connectivity can be improved.

  Moreover, this invention provides the manufacturing method of the semiconductor device using the said adhesive composition.

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

  Moreover, this invention provides the semiconductor device obtained by the manufacturing method of the said semiconductor device.

  In the semiconductor device of the present invention, the connectivity and insulation reliability of the semiconductor device can be improved by using the semiconductor device manufacturing method.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a semiconductor device using the adhesive composition which can improve connectivity and insulation reliability, 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 cross section showing a sample for melt viscosity measurement. 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 portion in a device or a semiconductor device in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other, and a polymer component having a weight average molecular weight of 10,000 or more (hereinafter referred to as a “polymer component”) In some cases, it is referred to as “component (A)”), an epoxy resin (hereinafter, sometimes referred to as “component (B)”), and a curing agent (hereinafter, sometimes referred to as “component (C)”). Contains an amine-based surface treatment filler (hereinafter sometimes referred to as “component (D)”). Hereinafter, the components contained in the adhesive composition of the present embodiment will be described.

((A) component: polymer component having a weight average molecular weight of 10,000 or more)
As the component (A), phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, polyetherimide resin, polyvinyl acetal resin, urethane resin, An acrylic rubber etc. are mentioned. Among these, phenoxy resin, polyimide resin, polycarbodiimide resin, cyanate ester resin, acrylic rubber and the like are preferable from the viewpoint of excellent heat resistance and film formability, phenoxy resin, polyimide resin, and acrylic rubber are more preferable, and polyimide resin Is more preferable. These (A) components can be used alone or as a mixture or copolymer of two or more. However, the (A) component does not include the epoxy resin that is the (B) component.

  The polyimide resin can be obtained, for example, by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. That is, in an organic solvent, tetracarboxylic dianhydride and diamine are used in an equimolar or almost equimolar amount (the order of addition of each component is arbitrary), and the reaction temperature is preferably 80 ° C. or less, more preferably 0 to 60 ° C. As an addition reaction. The tetracarboxylic dianhydride is preferably recrystallized and purified with acetic anhydride in order to suppress deterioration of various properties of the film adhesive.

  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 reaction product (polyamic acid). The dehydration ring closure can be performed by a thermal ring closure method in which heat treatment is performed or a chemical ring closure method using a dehydrating agent. The polyamic acid can be adjusted in molecular weight by depolymerization by heating at a temperature of 50 to 80 ° C.

  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).

［式中、ａは２〜２０の整数を示す。］

[Wherein, a represents an integer of 2 to 20. ]

  The tetracarboxylic dianhydride represented by the general formula (I) can be synthesized from, for example, trimellitic anhydride monochloride and the corresponding diol, specifically 1,2- (ethylene) bis. (Trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- ( Nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodeca) Styrene) bis (trimellitate anhydride), 1,16 (hexamethylene decamethylene) bis (trimellitate anhydride), 1,18 (octadecamethylene) bis (trimellitate anhydride) and the like.

  As said tetracarboxylic dianhydride, the tetracarboxylic dianhydride represented by said Formula (II) is preferable at the point which can provide the outstanding moisture-proof 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 formulas (I) and (II) is preferably 40 mol% or more, more preferably 50 mol% or more, based on the total tetracarboxylic dianhydride, 70 More preferably, it is at least mol%. When the content is less than 40 mol%, there is a tendency that the effect of moisture resistance reliability due to the use of the tetracarboxylic dianhydride represented by the above formulas (I) and (II) cannot be sufficiently ensured. is there.

  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) Benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3 , 4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- ( 3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminoenoxy) phenyl) sulfide, bis (4- (4-aminoenoxy) phenyl) sulfide, bis (4- (3-amino Noenoxy) phenyl) sulfone, bis (4- (4-aminoenoxy) phenyl) sulfone, aromatic diamines such as 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4 -Aminophenoxyphenyl) propane, aliphatic ether diamine represented by the following general formula (III), aliphatic diamine represented by the following general formula (IV), siloxane diamine represented by the following general formula (V), etc. Can be mentioned. Among these, the following general formula (III) or (IV) is preferable in that low stress properties, low temperature laminating properties, and low temperature adhesiveness can be imparted, and the following general formula (V) in terms of imparting low water absorption and low hygroscopicity. ) Is preferred. These diamines can be used alone or in combination of two or more.

［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、ｂ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 b represents an integer of 2 to 80. ]

［式中、ｃは５〜２０の整数を示す。］

[Wherein c represents an integer of 5 to 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、ｄ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 d represents an integer of 1 to 5. ]

  The content of the aliphatic ether diamine represented by the general formula (III) is preferably 1 to 50 mol% of the total diamine, and the content of the aliphatic diamine represented by the general formula (IV) is It is preferable that it is 20-80 mol% of all the diamines, and it is preferable that content of the siloxane diamine represented by the said general formula (V) is 20-80 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 reduced.

Specific examples of the aliphatic ether diamine represented by the general formula (III) include the following aliphatic ether diamines. Among these, aliphatic ether diamines represented by the following general formula (VI) are preferable in that low-temperature laminating properties and good adhesion to a substrate with an organic resist can be secured.

［式中、ｅは２〜８０の整数を示す。］

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

  Examples of the aliphatic diamine represented by the general formula (IV) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6- Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane Etc. 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 (V), for example, when p in the general formula (V) is 1, 1,1,3,3-tetramethyl-1,3-bis (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- Methoxy-1,3-bis (4-aminobutyl) disiloxane and the like, and when p is 2, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-amino) Phenyl) 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, 1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5- Bis (4-aminobutyl) trisiloxy 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 above polyimide resins may be used alone or in combination (blend) of two or more as required.

  The glass transition temperature (Tg) of the component (A) is preferably 100 ° C. or less, and more preferably 75 ° C. or less, from the viewpoint that the adhesive composition is excellent in adhesion to a substrate or a semiconductor chip. When Tg is higher than 100 ° C., bumps formed on the semiconductor chip, and irregularities such as electrodes and wiring patterns formed on the substrate cannot be embedded with the adhesive composition, and bubbles remain and voids are formed. It tends to occur. In addition, said Tg is Tg when using DSC (DSC-7 type | mold by Perkin Elmer Co., Ltd.) and measuring on conditions of sample amount 10mg, temperature increase rate 5 degree-C / min, and measurement atmosphere: air.

  The weight average molecular weight of the component (A) is 10000 or more in terms of polystyrene, and preferably 30000 or more, more preferably 50000 or more in order to exhibit good film formability alone. When the weight average molecular weight is less than 10,000, film formability is lowered. In addition, the said weight average molecular weight is a weight average molecular weight when it measures in polystyrene conversion using a high performance liquid chromatography (Shimadzu C-R4A).

((B) component: epoxy resin)
The component (B) preferably has two or more epoxy groups in the molecule, for example, bisphenol A type, bisphenol F type, naphthalene type, anthracene type, phenol novolak type, cresol novolak type, phenol aralkyl type, biphenyl. Type, triphenylmethane type, dicyclopentadiene type, various polyfunctional epoxy resins and the like can be used. These can be used alone or as a mixture of two or more.

  The content of the component (B) is not particularly limited, but is preferably 1 to 500 parts by weight, more preferably 5 to 300 parts by weight with respect to 100 parts by weight of the component (A) in order to keep the film shape well. 10-200 mass parts is still more preferable. When the content is less than 1 part by mass, the curability tends to decrease and the adhesive strength tends to decrease, and when it is greater than 500 parts by mass, the film formability tends to decrease.

((C) component: curing agent)
Examples of the component (C) include phenol resin curing agents, acid anhydride curing agents, amine curing agents, imidazole curing agents, and phosphine curing agents. When component (C) contains phenolic hydroxyl groups, acid anhydrides, amines, imidazoles, etc., it exhibits flux activity that suppresses the formation of an oxide film at the connection part, and improves connectivity 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, various polyfunctional phenol resins, etc. can be used. These can be used alone or as a mixture of two or more.

  The equivalent ratio (phenolic hydroxyl group / epoxy group, molar ratio) of the phenol resin curing agent to the component (B) is 0.3 to 1.5 from the viewpoint of good curability, adhesiveness, storage stability, and the like. Is preferable, 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is still more preferable. If the equivalent ratio is less than 0.3, the curability tends to decrease and the adhesive strength tends to decrease, and if it exceeds 1.5, the unreacted phenolic hydroxyl group remains excessively, and the water absorption increases. Insulation reliability tends to decrease.

(Ii) Acid anhydride curing agent Examples of acid anhydride curing agents include methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bis Anhydro trimellitate and the like 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 (B) (acid anhydride group / epoxy group, molar ratio) is 0.3 to 1 from the viewpoint of good curability, adhesiveness, storage stability, and the like. 0.5 is preferable, 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is still more preferable. If the equivalent ratio is less than 0.3, the curability tends to decrease and the adhesive strength tends to decrease, and if it exceeds 1.5, the unreacted acid anhydride remains excessively, and the water absorption rate increases. Insulation reliability tends to decrease.

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

  The equivalent ratio (amine / epoxy group, molar ratio) of the amine curing agent to the component (B) is preferably 0.3 to 1.5 from the viewpoint of good curability, adhesiveness, storage stability, etc. 4 to 1.0 is more preferable, and 0.5 to 1.0 is still more preferable. If the equivalent ratio is less than 0.3, the curability tends to decrease and the adhesive strength tends to decrease, and if it exceeds 1.5, the unreacted amine remains excessively and the insulation reliability tends to decrease. is there.

(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, adducts of epoxy resins and imidazoles. Among these, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecyl from the viewpoint of excellent curability, storage stability, connectivity and insulation reliability Imidazole 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-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-Fe Nyl-4-methyl-5-hydroxymethylimidazole is preferred. These may be used alone or in combination of two or more. Moreover, it is good also as a latent hardening | curing agent which encapsulated these.

  0.1-10 mass parts is preferable with respect to 100 mass parts of (B) component, and, as for content of an imidazole type hardening | curing agent, 0.1-5 mass parts is more preferable. If the content is less than 0.1 parts by mass, the curability tends to decrease, and if it exceeds 10 parts by mass, the adhesive composition is cured before the metal bond is formed, Connection failure tends to occur.

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

  0.1-10 mass parts is preferable with respect to 100 mass parts of (B) component, and, as for content of a phosphine type hardening | curing agent, 0.1-5 mass parts is more preferable. If the content is less than 0.1 parts by mass, the curability tends to decrease, and if it exceeds 10 parts by mass, the adhesive composition is cured before the metal bond is formed, Connection failure tends to occur.

  A phenol resin hardening agent, an acid anhydride hardening agent, and an amine hardening agent can be used individually by 1 type or in mixture of 2 or more types. The imidazole curing agent and the phosphine curing agent may be used alone, but may be used together with a phenol resin curing agent, an acid anhydride curing agent, and an amine curing agent as a curing accelerator.

  (A) component, (B) component, and (C) component are contained in the organic component in the adhesive composition of this embodiment. 10 mass% or more is preferable with respect to the whole adhesive composition, as for content of the said organic component, 50 mass% or more is more preferable, and 70 mass% or more is still more preferable. When the content of the organic component is less than 10% by mass, the amount of the inorganic component (for example, filler) tends to increase, the adhesive composition is fragile and easily broken, and the flow rate of the adhesive composition is reduced. However, connectivity tends to decrease.

  The total content of the component (B) and the component (C) with respect to 100 parts by weight of the component (A) is not particularly limited, but is preferably 1 to 400 parts by weight, and preferably 10 to 400 parts by weight in order to maintain a good film shape. Part is more preferable, and 10 to 300 parts by mass is still more preferable. When this content is less than 1 part by mass, the curability of the film adhesive is lowered and the adhesive strength tends to be lowered, and when it is more than 400 parts by mass, the film formability tends to be lowered.

  The thermal weight loss rate at 250 ° C. of the component (A), the component (B) and the component (C) is preferably 10% or less, more preferably 9% or less, and still more preferably 8% or less. When the content of at least one organic component selected from the component (A), the component (B) and the component (C) is 10% by mass or more, the content of the organic component is 250% by mass or more. It is particularly preferred that the thermal weight loss rate at 10 ° C. is 10% or less.

  In addition, since there is a tendency that volatile components are likely to be decomposed when heated at a high temperature, when the temperature of the connection part at the time of connection is about 250 ° C., the thermal weight reduction rate at 250 ° C. of the component (B) is 10% or less is preferable, 5% or less is more preferable, and when the temperature of the connection portion is about 300 ° C., the thermal weight reduction rate at 300 ° C. of the component (B) is preferably 10% or less, and 5% The following is more preferable.

  When component (A), component (B) and component (C) are liquid at room temperature (25 ° C.) and atmospheric pressure (for example, liquid phenol, liquid acid anhydride, liquid amine in component (C)), heating at high temperature Sometimes it tends to decompose and easily generate volatile components. Therefore, at room temperature (25 ° C.) and atmospheric pressure, at least one organic component selected from the component (A), the component (B) and the component (C) is preferably solid, and the component (A), (B) It is more preferable that all of the component and the component (C) are solid. In particular, with regard to the component (B), the liquid epoxy resin of bisphenol A type or bisphenol F type has a 1% thermal weight loss temperature of 250 ° C. or less, and therefore tends to decompose and generate volatile components when heated at high temperatures. Therefore, it is preferable to use a solid epoxy resin at room temperature (25 ° C.) and atmospheric pressure.

((D) component: amine-based surface treatment filler)
The component (D) is a filler that has been surface-treated in advance with an amine compound. Examples of the amine compound that can be suitably used include aminosilane when the filler is a silica filler.

  As the filler subjected to the amine-based surface treatment, 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, and boron nitride. Among these, 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. For example, polyurethane, polyimide, or the like can be used as the resin filler. These fillers, whiskers, and resin fillers can be used alone or as a mixture of two or more.

  The content of the component (D) is preferably 5 to 50 parts by mass, more preferably 5 to 30 parts by mass, and still more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the component (A). If the content is less than 5 parts by mass, the effect of adding the component (D) tends to be difficult to develop, and if it exceeds 50 parts by mass, the flow viscosity of the adhesive composition tends to decrease and the connectivity tends to decrease. is there.

  As the shape of the component (D), a spherical shape or a flake shape can be applied without particular limitation. (D) Although the average particle diameter of a component is not restrict | limited in particular, it is about 0.1-2 micrometers. In addition, you may mix and use the filler from which an average particle diameter differs as (D) component.

  By the way, conventionally used fillers are effective for improving the connectivity and insulation reliability by lowering the moisture absorption coefficient and thermal expansion coefficient, improving the high temperature elastic modulus, etc. Is usually scarce. Here, for example, when a silane coupling agent or the like is included in the resin together with the silica filler, the surface of the filler is subjected to silane coupling treatment, and silica fillers having various surface states can be synthesized by the substituents of the silane coupling agent. it can. However, the volatility of the silane coupling agent is high and causes voids in metal joints that require 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.

  On the other hand, in the adhesive composition of this embodiment, by using an amine surface treatment filler that has been surface-treated in advance, generation of highly volatile substances can be suppressed, and the amine compound exhibits basicity. Therefore, flux activity can be imparted. In addition, since the amine compound has good reactivity with the epoxy resin, a good network is formed between the epoxy resin and the filler, and the viscosity of the adhesive composition during the mounting pressure bonding is also increased. For this reason, breakage of the connection portion such as tearing of the connection bumps is suppressed, and the connectivity and insulation reliability are improved.

  In the adhesive composition of the present 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 moisture absorption when a semiconductor chip and a substrate are connected, (D ) A filler may be blended in addition to the component.

  As the filler, an insulating inorganic filler, whisker, or resin filler can be used. As the insulating inorganic filler, whisker, and resin filler, the same substances as the component (D) 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. These may be used singly or in combination of two or more. About these content, what is necessary is just to adjust suitably so that the effect of each additive may express.

  The melt viscosity at 250 ° C. for 10 seconds of the adhesive composition of the present embodiment is preferably 1000 Pa · s or less, more preferably 900 Pa · s or less, and still more preferably 800 Pa · s or less. When the melt viscosity exceeds 1000 Pa · s, the connectivity tends to decrease. The melt viscosity can be calculated by a parallel plate plastometer method by calculating the volume change of the adhesive composition accompanying heat and pressure by image analysis. The parallel plate plastometer method is described in, for example, Journal of Applied Physics Vol. 17, pages 458-471 of 1946.

  The adhesive composition of the present embodiment can be used as a paste or film when applied to a pre-applied method. Among these, as the tendency of the semiconductor chip to become thinner, the adhesive composition creeps up on the semiconductor chip at the time of crimping connection, the mounting device is deteriorated due to the scattering of the resin component, and the productivity is concerned. Therefore, it is preferable that it is a film form. In addition, the adhesive composition of this embodiment can also be applied to the Capillary-Flow method as long as at least one of the component (A), the component (B), and the component (C) is liquid.

  In the semiconductor device manufacturing method described later, a semiconductor wafer in which a plurality of film-shaped adhesive compositions are connected to a semiconductor chip (when separated into individual pieces, bumps and wirings are similarly arranged and formed on each chip. Alignment of the position to be separated into individual pieces after being attached to a semiconductor wafer designed so as to be separated, and the relative position at the time of connection between the semiconductor chip and the substrate or between the semiconductor chips. May do. In this case, it is necessary to recognize alignment marks (alignment marks) formed on the substrate or semiconductor chip and dicing lines (scribe lines: positions / lines to be singulated) through a film adhesive. Therefore, the transmittance for light having a wavelength of 550 nm of the film adhesive composition is preferably 5% or more, more preferably 10% or more, and further preferably 15% or more. Since the recognition accuracy of the alignment mark differs depending on the recognition device of the mounting device, the transmittance may be set to be appropriately recognized by the recognition device. When the film-like adhesive composition contains an inorganic filler in addition to the component (D), the aforementioned transmittance can be achieved by making the refractive indexes of the inorganic filler and the resin component substantially the same. it can. As such an inorganic filler, a silica filler is preferable because it has a similar refractive index to that of an epoxy resin and contains few impurities and has good HAST resistance.

  A method for producing a film adhesive using the adhesive composition of the present embodiment is shown below. First, the resin varnish is prepared by adding the component (A), the component (B), the component (C), the component (D) and an additive to an organic solvent and dissolving or dispersing them by stirring, mixing, kneading or the like. . 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, without isolating (A) component after a synthesis | combination, you may add each component in the varnish obtained after a synthesis | combination, and may prepare the said resin varnish.

  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, kneading, etc. in the preparation of the resin varnish can be performed using a stirrer, a raking machine, a three roll, a ball mill, a homodisper and the like.

  The base film is not particularly limited as long as it has heat resistance capable of withstanding the heating conditions when the organic solvent is volatilized. The polyester film, polypropylene film, polyethylene terephthalate film, polyimide film, polyetherimide film, poly Examples include ether naphthalate films and methylpentene films. The base film is not limited to a single layer made of these films, and may be a multilayer film made of two or more materials.

  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 various semiconductors such as elemental semiconductors composed of the same kind of elements such as silicon and germanium, and compound semiconductors such as gallium arsenide and indium phosphide can be used.

  The substrate 20 is not particularly limited as long as it is a circuit board, and the main component is glass epoxy, polyimide, polyester, ceramic, epoxy, bismaleimide triazine, polyimide, etc. A circuit board having wiring (wiring pattern) 15 formed by etching away unnecessary portions of the film, a circuit board having wiring 15 formed on the surface of the insulating substrate by metal plating, etc., and conducting on the surface of the insulating substrate A circuit board or the like on which the wiring 15 is formed by printing a conductive material can be used.

  Connection portions 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, 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 (junction) with reduced cost, silver, copper and solder are preferable, copper and solder are more preferable, and solder is still more preferable based on being inexpensive. 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 for 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 a sealing material between the semiconductor chips 10 facing each other or between the semiconductor chip 10 and the interposer 50 in such a 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 bridges between the wirings 15 and improve the connectivity 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 inks for packaging 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 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 it. 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, the height of the connection bump 30, and the like.

  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 pressed 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 is sufficient to perform crimping with a low load, a short time, and a low temperature as compared with the above-described main crimping, which improves productivity and deteriorates the connection 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 connectivity 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 method for manufacturing a semiconductor device according to the present embodiment, the substrate 20 may be connected after the film adhesive 40 is attached 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, if the film-like resin composition is supplied so as to embed wirings and bumps on the semiconductor chip 10 by a sticking method such as lamination. Good. 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 due to pressure, or the bumps of the connection portions. 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 bonding of each connection portion metal (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 metal connection such as copper-copper or copper-gold, the connection time is preferably 60 seconds or less.

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

(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 as a diamine, polyether diamine (manufactured by BASF, trade name: ED2000, weight average molecular weight: 1923) ) 17.31 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 150 g of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Inc.) was added and stirred. After dissolution of the diamine, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic dianhydride) (ALDRICH) was recrystallized and purified with acetic anhydride while cooling the flask in an ice bath. (Product name: BPADA) 15.62 g (0.10 mol) was added little by little. After reacting at room temperature for 8 hours, 100 g of xylene was added, heated at 180 ° C. while blowing nitrogen gas, azeotropically removed xylene together with water, and a polyimide resin having an SP value of 10.2 (hereinafter “polyimide A”). And obtained.

  The Tg of polyimide A was measured using DSC (Perkin Elmer, Inc .: 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. The Tg of polyimide A was around 25 ° C.

  The weight average molecular weight of polyimide A was measured in terms of polystyrene using high performance liquid chromatography (manufactured by Shimadzu Corporation: C-R4A). As an eluent, a mixed solution of DMF / phosphoric acid / lithium bromide was used. The weight average molecular weight of the polyimide A was about 80,000.

The compounds used in each example and comparative example are shown below.
(I) Polymer component having a molecular weight of 10,000 or more Polyimide A synthesized as described above (thermal weight reduction rate at 250 ° C .: 0.5%)
(Ii) Epoxy resin Multifunctional solid epoxy containing triphenolmethane skeleton (manufactured by Japan Epoxy Resin Co., Ltd., trade name: EP 1032H60, thermal weight reduction rate at 250 ° C .: 0.22%, hereinafter referred to as “EP 1032”)
(Iii) Curing agent 1-cyanoethyl-2-phenylimidazolium trimellitate (manufactured by Shikoku Kasei Co., Ltd., trade name: 2PZ-CNS)
(Iv) Silica filler Aminosilane-treated silica filler (manufactured by Admatechs Co., Ltd., trade name: SE5050-SXJ, average particle size 1.5 μm, hereinafter referred to as “SXJ silica”)
-(Untreated) silica filler (manufactured by Admatechs Co., Ltd., trade name: SE5050, average particle size 1.5 μm, hereinafter referred to as “untreated silica”)
Phenylsilane-treated silica filler (manufactured by Admatechs Co., Ltd., trade name: SE5050-SPJ, average particle size 1.5 μm, hereinafter referred to as “SPJ silica”)
Epoxy silane-treated silica filler (manufactured by Admatechs Co., Ltd., trade name: SE5050-SEJ, average particle size 1.5 μm, hereinafter referred to as “SEJ silica”)

  The thermal weight loss rate at 250 ° C. of polyimide A and EP 1032 was measured as follows. That is, a sample is put in a Pt pan, and a thermal weight reduction from 35 ° C. to 400 ° C. at a temperature rising rate of 10 ° C./min in an air stream of 400 ml / min is measured with a TG / DTA measuring device (Seiko Instruments Inc., trade name : EXSTAR6000).

[Example 1, Comparative Examples 1-3]
(Method for producing film adhesive)
In 20 ml of glass screw tube charged with N-methyl-2-pyrrolidone (manufactured by Kanto Chemical), solid content of polyimide A, epoxy resin, curing agent and filler in the ratio (unit: parts by mass) shown in Table 1 below. After charging to 40%, stirring and defoaming were performed using a stirring and defoaming apparatus AR-250 (manufactured by Shinky Co., Ltd.). After defoaming, the obtained adhesive composition was applied to a base film (trade name: Purex A53, manufactured by Teijin DuPont Film Co., Ltd.) with a coating machine “PI1210FILMCOATER” (trade name, manufactured by Tester Sangyo Co., Ltd.). It was coated and dried in a clean oven (manufactured by Espec Co., Ltd.) (after 30 minutes at 80 ° C. and then 20 minutes at 120 ° C.) to prepare a film adhesive (thickness: 30 μm).

  Below, the evaluation method of the film adhesive of an Example and a comparative example is shown.

(1) Method for measuring melt viscosity of film adhesive Cut out the prepared film adhesive (circular, diameter Φ: 6 mm, thickness: about 0.03 mm), glass chip (length 15 mm × width 15 mm × height 0.7 mm) ) After pasting on top, a silicon chip (length 10 mm × width 10 mm × height 0.55 mm) is stacked, and a film adhesive 40 and a silicon chip 80 are sequentially laminated on the glass substrate 70 as shown in FIG. Sample A was prepared. The thickness and area of the film-like adhesive before compression bonding in Sample A were measured, and the volume of the film-like adhesive was calculated. Next, the sample A is pressure-bonded with a thermocompression bonding apparatus (pressure bonding conditions: head temperature at pressure bonding of 278 ° C., stage temperature of 40 ° C., ultimate temperature of the film adhesive 250 ° C., 10 seconds, 0.5 MPa), and film bonding The area after pressure bonding of the agent was measured. Further, assuming that the volume of the film adhesive does not change before and after the pressure bonding, the thickness of the film adhesive after the pressure bonding is calculated by dividing the volume of the film adhesive previously calculated by the area after the pressure bonding. did. In addition, the area of the film portion is obtained by capturing the image of the film-like adhesive with a scanner GT-9300UF (manufactured by EPSON), identifying the film portion by color tone correction and two-level gradation using the image processing software Adobe Photoshop, and by using the histogram. The proportion of the area was calculated and measured.

The melt viscosity was calculated using the above volume change from the following formula (1) based on the parallel plate plastometer method.
(Calculation formula of melt viscosity by 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 : initial thickness of adhesive (m)
Z: Thickness of adhesive after pressing (m)
V: Volume of adhesive (m ³ )

(2) Evaluation of initial conductivity (connectivity), void generation rate, and wettability The produced film adhesive was cut into a predetermined size (11 mm long × 11 mm wide × 0.03 mm high) to obtain a glass epoxy substrate ( Glass epoxy base material: 400 μm thickness, copper wiring: 15 μm thickness, solder ball height: 28 μm thickness, with solder resist, Hitachi Chemical Co., Ltd. semiconductor chip with a gold bump (chip size: vertical 10 mm × 10 mm wide × 0.4 mm high, bump height of about 25 μm, number of bumps 186, manufactured by Hitachi Chemical Co., Ltd.) was mounted with a flip chip mounting device FCB3 (manufactured by Panasonic Corporation, trade name) (mounting condition: film-like adhesion) The ultimate temperature of the agent is 250 ° C., 10 seconds, 0.5 MPa). As a result, a semiconductor device similar to that shown in FIG. 4 was obtained.

  After the glass epoxy substrate and the chip with gold bumps were connected in a daisy chain, the initial continuity (conductivity) after mounting was evaluated based on the connection resistance value measured by a multimeter (manufactured by ADVANTEST). When the connection resistance value is 5 to 20Ω, “A” is set, and when the connection resistance value is other than “B”, the connection resistance value is not displayed due to a complete connection failure even in part. Was evaluated as “C”.

In addition, the sample after mounting is observed with an ultrasonic exploration imaging device (trade name: HYE-FOCUS, manufactured by HITACHI), and color correction and two-gradation are performed on the film part and on the film using the image processing software Adobe Photoshop. The void portion was identified, and the ratio of the area occupied by the void portion on the film to the area of the film portion was calculated as a “void generation rate” using the following formula (2) from the histogram. Samples having a void generation rate of 20% or less were evaluated as “A”, and samples larger than 20% were evaluated as “B”.
Void generation rate = (area of void part) / (area of film part) × 100 (2)

  Moreover, the cross section of the connection part of the sample after mounting was observed with a metal microscope BX60 (manufactured by OLMPUS), and the wettability was evaluated based on the degree of spread of the solder balls on the gold bumps. Samples with 80% or more solder spread on the gold bumps were evaluated as “A”, samples with 20% or more and less than 80% were evaluated as “B”, and samples with less than 20% were evaluated as “C”.

(3) Insulation reliability test (HAST test: Highly Accelerated Storage Test)
Create a film-like adhesive (thickness: 30 μm) with a void on a comb-shaped electrode TEG (manufactured by Shindo Denshi Co., Ltd., trade name: perflex-S, wiring pitch: 30 μm, wiring material: tin-plated copper, substrate material: polyimide). It stuck without generating and produced four samples B which laminated | stacked the film adhesive 40 on the board | substrate 20 with which the comb-shaped electrode 90 was formed, as shown in FIG. In addition, in FIG. 6, illustration of the film adhesive was abbreviate | omitted for convenience. Subsequently, each sample B was cured by being held at 185 ° C. for 1 hour in a clean oven (manufactured by ESPEC). After curing, each sample B 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. Through 100 hours, four of one or more of the insulation resistance of the sample is the case where more than 10 ⁹ Omega of samples "A", the case is less than 10 ⁷ Omega than 10 ⁹ Omega as "B", 10 ⁷ The case of Ω or less was evaluated as “C”.

  Table 1 shows the contents (units: parts by mass) of the formulations of Examples and Comparative Examples and the results of each test.

  Example 1 using the aminosilane surface-treated silica filler is excellent in all the characteristics of initial conductivity, void generation rate, wettability and HAST resistance, and is a comparison using a filler not subjected to amino-based surface treatment. It was confirmed that it has excellent characteristics as compared with Examples 1 to 3.

  DESCRIPTION OF SYMBOLS 10 ... Semiconductor chip, 15 ... Wiring (connection part), 20 ... Board | substrate (wiring circuit board), 32 ... Bump (connection part), 40 ... Adhesive composition, 100, 200, 300, 400, 500, 600 ... Semiconductor apparatus.

Claims (10)

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:
An adhesive composition comprising a polymer component having a weight average molecular weight of 10,000 or more, an epoxy resin, a curing agent, and an amine-based surface treatment filler.   The adhesive composition according to claim 1, wherein at least one organic component selected from the polymer component, the epoxy resin, and the curing agent is solid at 25 ° C. and atmospheric pressure. The content of at least one organic component selected from the polymer component, the epoxy resin and the curing agent is 10% by mass or more,
The adhesive composition according to claim 1 or 2, wherein the organic component having the content of 10% by mass or more has a thermal weight reduction rate at 250 ° C of 10% or less.   The adhesive composition according to any one of claims 1 to 3, wherein the polymer component is a polyimide resin.   The adhesive composition of Claim 4 whose weight average molecular weights of the said polyimide resin are 30000 or more, and whose glass transition temperature of the said polyimide resin is 100 degrees C or less.   The adhesive composition according to any one of claims 1 to 5, wherein the shape is a film shape.   The adhesive composition according to any one of claims 1 to 6, wherein the melt viscosity at 250 ° C for 10 seconds is 1000 Pa · s or less.   The adhesive composition according to any one of claims 1 to 7, 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.   The manufacturing method of a semiconductor device using the adhesive composition as described in any one of Claims 1-8.   A semiconductor device obtained by the manufacturing method according to claim 9.

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