JP2011157529A - Adhesive composition, method for manufacturing semiconductor device and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition which hardly causes voids between bumps upon bonding and can be used for manufacturing a semiconductor device excellent in reflow resistance and reliability, to provide a method of manufacturing a semiconductor device using the adhesive composition and to provide a semiconductor device manufactured by using the method for manufacturing semiconductor device. <P>SOLUTION: The adhesive composition comprises a thermosetting compound, a polymer having a functional group reactive with the thermosetting compound and a thermosetting agent, wherein the melt viscosity at a bonding temperature is 10 to 15,000 Pa s, the gel time at the bonding temperature is 10 s or more and the gel time at 240°C is 1 to 10 s. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to an adhesive composition that can be used to manufacture a semiconductor device that is less likely to cause voids between bumps during bonding and has excellent reflow resistance and reliability. The present invention also relates to a method for manufacturing a semiconductor device using the adhesive composition, and a semiconductor device manufactured using the method for manufacturing the semiconductor device.

2. Description of the Related Art In recent years, flip-chip mounting using a semiconductor chip having connection terminals (bumps) made of solder or the like has been widely used in order to cope with the further miniaturization and higher integration of semiconductor devices.
In flip-chip mounting, generally, a method is used in which a semiconductor chip having a plurality of bumps is connected to another semiconductor chip or a substrate through the bumps and then filled with an underfill. However, in recent years, semiconductor chips have been miniaturized, and the pitch between bumps has become narrower. In addition, the gap between semiconductor chips or between a semiconductor chip and a substrate has become narrower. Therefore, air is easily trapped when filling the underfill, and voids are easily generated.

In order to solve this problem, after forming an adhesive layer on the surface of the wafer having a plurality of bumps on which a bump is formed, the wafer is diced together with the adhesive layer to form individual semiconductor chips with an adhesive layer. A method of dividing is proposed. A semiconductor chip with an adhesive layer separated into pieces by dicing is bonded to another semiconductor chip or a substrate and electrically connected via bumps. Further, after bonding the semiconductor wafer with the adhesive layer before dicing to another semiconductor wafer or substrate to obtain a semiconductor wafer bonded body, the obtained semiconductor wafer bonded body is divided to obtain a semiconductor chip bonded body A method has been proposed (for example, Patent Document 1).

As an adhesive composition used for such an adhesive layer formed on a wafer, for example, Patent Document 2 discloses a pre-applied seal containing (A) an epoxy resin and (B) a curing agent having flux activity. A tackifying resin composition having a tack value after B-staging of 0 gf / 5 mmφ to 5 gf / 5 mmφ and a melt viscosity at 130 ° C. of 0.01 Pa · s to 1.0 Pa · s. A sealing resin composition for pre-application is described.
However, in the pre-applied sealing resin composition described in Patent Document 2, voids between bumps cannot be completely discharged if there are irregularities such as a pre-solder or a bonding pad on a semiconductor chip or substrate. In the adhesive composition, the generation of voids between the bumps has not been sufficiently suppressed.

On the other hand, in order to suppress the generation of voids between the bumps, for example, it is effective to smooth the surface of the adhesive layer formed on the wafer. For example, Patent Document 3 describes a method for manufacturing a semiconductor device including a step of performing a flattening process so that the surface of a bump and the surface of an insulating film are continuously flattened by cutting using a cutting tool. .
However, in the method of manufacturing a semiconductor device described in Patent Document 3, when bonding a semiconductor chip with an adhesive layer separated by dicing to another semiconductor wafer or chip or a substrate, the adhesive layer is a semiconductor. The problem is that it cannot sufficiently protrude around the periphery of the chip, and so-called fillets cannot be sufficiently formed. The fillet is important for dispersing the stress generated when exposed to a temperature cycle or the like in a semiconductor device obtained by joining members having different linear expansion coefficients and improving the reliability. Accordingly, there is a need for an adhesive composition and a method for manufacturing a semiconductor device that can form a sufficient amount of fillets and impart high reliability to the resulting semiconductor device.

JP 2008-294382 A JP 2007-116079 A JP 2009-94545 A

An object of the present invention is to provide an adhesive composition that can be used to manufacture a semiconductor device that is less likely to cause voids between bumps during bonding and has excellent reflow resistance and reliability. Another object of the present invention is to provide a method for manufacturing a semiconductor device using the adhesive composition, and a semiconductor device manufactured using the method for manufacturing a semiconductor device.

The present invention is an adhesive composition containing a thermosetting compound, a polymer having a functional group capable of reacting with the thermosetting compound, and a thermosetting agent, and has a melt viscosity of 10 Pa · at a bonding temperature. The adhesive composition has a gel time at a bonding temperature of 10 seconds or more and a gel time at 240 ° C. of 1 second or more and 10 seconds or less.
The present invention is described in detail below.

The inventors of the present invention provide an adhesive composition containing a thermosetting compound, a polymer having a functional group capable of reacting with the thermosetting compound, and a thermosetting agent, the melt viscosity and gel time at a predetermined temperature. It has been found that an adhesive composition having a value within a predetermined range hardly causes voids between bumps during bonding. The present inventors have found that when the adhesive composition is used, a semiconductor device having excellent reflow resistance and reliability can be produced, and the present invention has been completed.

The adhesive composition of the present invention contains a thermosetting compound.
Although the said thermosetting compound is not specifically limited, It is preferable to contain at least 1 sort (s) selected from the group which consists of an epoxy resin, a benzoxazine resin, and a bismaleimide resin.

The epoxy resin is not particularly limited, and examples thereof include bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD type, and bisphenol S type, novolac type epoxy resins such as phenol novolak type and cresol novolak type, and trisphenolmethane. Aromatic epoxy resins such as triglycidyl ether, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, resorcinol type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine Type epoxy resin, isocyanuric acid derivatives having an epoxy group, and modified products and hydrogenated products thereof. These epoxy resins may be used independently and 2 or more types may be used together.
Among the epoxy resins, an epoxy resin that is solid at 25 ° C. and has a melting point of 50 to 140 ° C. is preferable. Examples of such epoxy resins include anthracene type epoxy resins, biphenyl type epoxy resins, Examples thereof include crystalline epoxy resins such as fluorene type epoxy resin and resorcinol type epoxy resin.

Moreover, it is preferable that the said epoxy resin contains a bifunctional or more functional epoxy resin.
When the adhesive composition of the present invention contains the bifunctional or higher epoxy resin, the content of the bifunctional or higher epoxy resin is not particularly limited, but the preferred lower limit in 100 parts by weight of the thermosetting compound is 60. Parts by weight. When the content of the bifunctional or higher functional epoxy resin is less than 60 parts by weight, sufficient heat resistance may not be exhibited in the adhesive composition.

The benzoxazine resin is not particularly limited, and examples of commercially available products include benzoxazine Fa type (manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine Pd type (manufactured by Shikoku Kasei Kogyo Co., Ltd.), RLV-100 (Air Water) and the like. These benzoxazine resins may be used alone or in combination of two or more.

The bismaleimide resin is not particularly limited. For example, 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4 '-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4' -Diphenyl sulfone bismaleimide etc. are mentioned. These bismaleimide resins may be used alone or in combination of two or more.

The adhesive composition of the present invention contains a polymer having a functional group capable of reacting with the thermosetting compound (hereinafter also referred to as a polymer having a functional group capable of reacting). By containing the polymer which has the said functional group which can react, the hardened | cured material of adhesive composition has toughness, and can express the outstanding impact resistance.

The polymer having the reactive functional group is not particularly limited, and examples thereof include a polymer having an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group, and the like. Among these, a polymer having an epoxy group is preferable.
By containing the polymer having the epoxy group, the cured product of the adhesive composition exhibits excellent toughness, excellent mechanical strength, heat resistance and moisture resistance derived from the thermosetting compound, and the epoxy. Combined with excellent toughness derived from a polymer having a group, high bonding reliability and connection reliability can be expressed.

The polymer having an epoxy group is not particularly limited as long as the polymer has an epoxy group at the terminal and / or side chain (pendant position). For example, an epoxy group-containing acrylic rubber, an epoxy group-containing butadiene rubber, a bisphenol type high molecular weight Examples thereof include an epoxy resin, an epoxy group-containing phenoxy resin, an epoxy group-containing (meth) acrylic resin, an epoxy group-containing styrene resin, an epoxy group-containing urethane resin, and an epoxy group-containing polyester resin. Among these, an epoxy group-containing (meth) acrylic resin and an epoxy group-containing styrene resin are preferable because they contain a lot of epoxy groups and can further improve the mechanical strength, heat resistance, and the like of the cured product of the resulting adhesive composition. The polymer which has these epoxy groups may be used independently, and 2 or more types may be used together.
When the polymer having an epoxy group, particularly an epoxy group-containing (meth) acrylic resin or an epoxy group-containing styrene resin is used as the polymer having a reactive functional group, the preferred lower limit of the epoxy equivalent of the polymer having an epoxy group is 200, the preferred upper limit is 2000. When the epoxy equivalent is less than 200, the cured product of the adhesive composition may be hard and brittle. When the said epoxy equivalent exceeds 2000, the mechanical strength of the hardened | cured material of adhesive composition, heat resistance, etc. may become inadequate. The upper limit with the more preferable epoxy equivalent of the polymer which has the said epoxy group is 1000.
In the present specification, (meth) acryl means both acrylic and methacrylic.

The weight average molecular weight of the polymer having a functional group capable of reacting is not particularly limited, but a preferable lower limit is 9000 and a preferable upper limit is 600,000. When the weight average molecular weight of the polymer having a functional group capable of reacting is less than 9000, the film forming property of the adhesive composition becomes insufficient. For example, even if the adhesive composition is formed into a film, it is shaped as a film. May not be able to hold. When the weight average molecular weight of the polymer having a reactive functional group exceeds 600,000, the minimum melt viscosity of the adhesive composition may be too high. A more preferable upper limit of the weight average molecular weight of the polymer having a reactive functional group is 300,000.

The glass transition temperature (Tg) of the polymer having a reactive functional group is not particularly limited, but a preferable lower limit is 0 ° C. and a preferable upper limit is 150 ° C. When the glass transition temperature of the polymer having a reactive functional group is less than 0 ° C., the resulting adhesive composition is used to manufacture a semiconductor device that does not cause defects even when exposed to a temperature cycle or the like. Can be difficult. When the glass transition temperature of the polymer having a reactive functional group exceeds 150 ° C., the minimum melt viscosity of the adhesive composition may be too high. The more preferable lower limit of the glass transition temperature (Tg) of the polymer having a reactive functional group is 50 ° C., and the more preferable upper limit is 100 ° C.

The blending amount of the polymer having a functional group capable of reacting in the adhesive composition of the present invention is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the thermosetting compound is 1 part by weight, and a preferable upper limit is 500 parts by weight. . When the blending amount of the polymer having a functional group capable of reacting is less than 1 part by weight, the cured product of the adhesive composition has insufficient toughness when heat distortion occurs, resulting in poor bonding reliability. There is. When the compounding quantity of the polymer which has the said functional group which can react is over 500 weight part, the heat resistance of the hardened | cured material of an adhesive composition may fall.

The adhesive composition of the present invention contains a thermosetting agent.
The said thermosetting agent is not specifically limited, For example, the compound etc. which have an amine compound, a modified amine, an acid anhydride, a phenolic hydroxyl group, etc. are mentioned.
The thermosetting agent is preferably a thermosetting agent having a flux property, and examples of such a thermosetting agent include an acid anhydride, a compound having a phenolic hydroxyl group, and the like.

The acid anhydride is not particularly limited, and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and trialkyltetrahydrophthalic anhydride. Of these, methylnadic acid anhydride or trialkyltetrahydrophthalic anhydride is preferable because it is hydrophobized. These acid anhydrides may be used alone or in combination of two or more.
In addition, trifunctional or higher functional acid anhydride particles may be used as the acid anhydride. The trifunctional or higher functional acid anhydride particles are not particularly limited. For example, particles composed of trifunctional acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride. And particles composed of tetrafunctional or higher functional acid anhydrides such as polyazeline acid anhydride.

The average particle diameter of the trifunctional or higher functional acid anhydride particles is not particularly limited, but a preferable lower limit is 0.1 μm and a preferable upper limit is 5 μm. When the average particle diameter of the trifunctional or higher functional acid anhydride particles is less than 0.1 μm, the acid anhydride particles may be aggregated to increase the viscosity of the adhesive composition. When the average particle diameter of the trifunctional or higher functional acid anhydride particles exceeds 5 μm, the acid anhydride particles cannot be sufficiently diffused during curing in the adhesive composition, resulting in poor curing.

Moreover, when the said acid anhydride contains a bifunctional acid anhydride with the said trifunctional or more acid anhydride particle, these compounding ratios are not specifically limited, Content of the said trifunctional or more acid anhydride particle Preferred lower limit of the value obtained by dividing (weight) by the content (weight) of the bifunctional acid anhydride [= (content of trifunctional or higher functional acid anhydride particles) / (content of bifunctional acid anhydride)] Is 0.1, and a preferred upper limit is 10. If the value is less than 0.1, the effect of adding the trifunctional or higher functional acid anhydride particles may not be sufficiently obtained. When the said value exceeds 10, the hardened | cured material of an adhesive composition may become weak, and sufficient adhesive reliability may not be obtained. A more preferred lower limit of the above value is 0.2, and a more preferred upper limit is 8.

The compound having a phenolic hydroxyl group is not particularly limited. For example, bisphenol A, bisphenol F, phenol novolac, cresol novolac, dicyclopentadiene phenol, aralkyl phenol, trisphenol, tetrakisphenol, resol type phenol, biphenyldimethylene type phenol , Phenol resin-silica hybrid, and derivatives and modified products thereof. Of these, phenol novolak, cresol novolak, dicyclopentadiene phenol, biphenyldimethylene type phenol, phenol resin-silica hybrid, and derivatives and modified products thereof are preferable.

The compounding quantity of the said thermosetting agent in the adhesive composition of this invention is not specifically limited. For example, the adhesive composition of the present invention contains an epoxy resin as the thermosetting compound, and has an amine curing agent such as an amine compound or a modified amine, an acid anhydride, or a phenolic hydroxyl group as the thermosetting agent. When it contains, it is preferable that the mole number of the reactive group of the said thermosetting agent is 0.7-1.3 times with respect to the mole number of the epoxy group of the said epoxy resin.

The adhesive composition of the present invention may contain a thermosetting accelerator having a melting point of 120 to 260 ° C.
When the melting point of the thermosetting accelerator is less than 120 ° C., a solvent is added to the adhesive composition, and after applying the adhesive composition to the semiconductor wafer, the solvent is dried, for example, heating at 80 ° C. for 30 minutes. Then, the gel fraction becomes high, and voids are likely to occur during bonding, and the gel time at 140 ° C. is shortened, making it difficult to form a sufficient amount of fillets. When the melting point of the thermosetting accelerator exceeds 260 ° C., the thermosetting accelerator is not completely dissolved by the heat during curing, and the reliability of the semiconductor device may be lowered.

Although the said thermosetting accelerator will not be specifically limited if melting | fusing point is 120-260 degreeC, As a commercial item, for example, 2MZ, 2MZ-P, 2PZ, 2PZ-PW, 2P4MZ, C11Z-CNS, 2PZ-CNS, 2PZCNS -PW, 2MZ-A, 2MZA-PW, C11Z-A, 2E4MZ-A, 2MA-OK, 2MAOK-PW, 2PZ-OK, 2MZ-OK, 2PHZ, 2PHZ-PW, 2P4MHZ, 2P4MHZ-PW, 2E4MZ · BIS , VT, VT-OK, MAVT, MAVT-OK (manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like. Among these thermosetting accelerators, thermosetting accelerators that are stable up to 130 ° C. and activated at 135 to 200 ° C. are particularly preferable. Among these thermosetting accelerators, 2MA− OK, 2MAOK-PW, etc. are mentioned.

When the adhesive composition of the present invention contains an epoxy resin as the thermosetting compound, examples of the thermosetting accelerator include imidazole compounds, imidazole inclusion compounds, imidazole microcapsules, thirds. A phosphorus compound such as a secondary amine compound, dicyandiamide, triphenylphosphine, or the like can be used.
Further, when the adhesive composition of the present invention contains a benzoxazine resin as the thermosetting compound, for example, an imidazole compound can be used as the thermosetting accelerator, and the epoxy resin and the phenol. A compound having a functional hydroxyl group may be used in combination.
Furthermore, when the adhesive composition of the present invention contains a bismaleimide resin as the thermosetting compound, examples of the thermosetting accelerator include a compound having a C—C double bond, a glycidyl ether compound, An imidazole compound or the like can be used.

Although the compounding quantity of the said thermosetting accelerator in the adhesive composition of this invention is not specifically limited, The preferable minimum with respect to 100 weight part of the said thermosetting compounds is 0.1 weight part, and a preferable upper limit is 20 weight part. When the blending amount of the thermosetting accelerator is less than 0.1 parts by weight, the adhesive composition may not be sufficiently cured. When the compounding quantity of the said thermosetting accelerator exceeds 20 weight part, the connection reliability of an adhesive composition may fall. As for the compounding quantity of the said thermosetting accelerator in the adhesive composition of this invention, the more preferable upper limit with respect to 100 weight part of said thermosetting compounds is 15 weight part.

The adhesive composition of the present invention may contain a solvent, if necessary.
By containing the solvent, the preparation of the adhesive composition can be facilitated, and the adhesive composition obtained can be easily applied to a semiconductor wafer or chip to form an adhesive layer. be able to. Furthermore, after achieving these objects, the solvent can be removed by drying. The method for drying the solvent is not particularly limited, but for example, a method using a hot air oven, a heating oven using infrared rays, a vacuum drying oven or the like is preferable.

Although the said solvent is not specifically limited, The solvent which melt | dissolves the said thermosetting compound, the polymer which has a functional group which can react with the said thermosetting compound, and the said thermosetting agent, but does not melt | dissolve the said thermosetting accelerator. Preferred examples include alcohol solvents, aromatic hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, acetate solvents, NMP, DMC, DMF, and limonene.

The residual amount of the solvent after removal is preferably 1% or less.
The boiling point of the solvent is not particularly limited, but it is preferable that the solvent can be dried at a temperature at which the reaction rate of the thermosetting compound is 20% or less.
The solvent preferably has a boiling point of 110 ° C. or higher when the adhesive composition is applied by spin coating.
Furthermore, the solvent preferably has a boiling point of 140 ° C. to 220 ° C. when the adhesive composition is applied by screen printing, slit coating or spray coating. When the boiling point of the solvent is less than 140 ° C., the adhesive composition may be dried when applied to a semiconductor wafer or the like, and workability may be reduced. If the boiling point of the solvent exceeds 220 ° C., heating at a high temperature is required for drying the solvent, the curing reaction proceeds, and it may be difficult to bond a semiconductor wafer or the like satisfactorily.

Although the compounding quantity of the said solvent in the adhesive composition of this invention is not specifically limited, The sum total of the said thermosetting compound, the polymer which has a functional group which can react with the said thermosetting compound, and the said thermosetting agent is 100. A preferable lower limit with respect to parts by weight is 20 parts by weight, and a preferable upper limit is 1000 parts by weight.

The adhesive composition of the present invention may contain an inorganic filler as necessary.
The inorganic filler is not particularly limited, and examples thereof include metals, metal oxides, silica, alumina, aluminum nitride, glass, boron nitride, silicon nitride, and silicon.

The shape of the inorganic filler is not particularly limited, but is preferably spherical.
The average particle diameter of the inorganic filler is not particularly limited, but a preferable upper limit is 3 μm. When the average particle diameter of the inorganic filler exceeds 3 μm, when the bump is bonded using the adhesive composition, the inorganic filler may be bitten and the reliability of the resulting semiconductor device may be lowered. A more preferable upper limit of the average particle diameter of the inorganic filler is 1 μm, and a more preferable upper limit is 0.5 μm. Moreover, in order to suppress the increase in the melt viscosity of the adhesive composition, two or more inorganic fillers having different average particle diameters may be used in combination.

The refractive index of the inorganic filler is not particularly limited, but in order to obtain an adhesive composition having excellent transparency, the thermosetting compound, the polymer having a functional group capable of reacting with the thermosetting compound, and the heat The difference from the refractive index of the curing agent is preferably within ± 0.5.

Although the compounding quantity of the said inorganic filler in the adhesive composition of this invention is not specifically limited, The preferable minimum in the adhesive composition of this invention is 30 weight part, and a preferable upper limit is 80 weight part. When the blending amount of the inorganic filler is less than 30 parts by weight, a linear expansion coefficient after curing of the adhesive composition is increased, and a semiconductor device in which no defect occurs even when exposed to a temperature cycle or the like is manufactured. May be difficult. If the amount of the inorganic filler exceeds 80 parts by weight, it may be difficult to apply the adhesive composition to a semiconductor wafer or the like.

Moreover, the adhesive composition of this invention does not need to contain an inorganic filler substantially.
In the present specification, the phrase “substantially containing no inorganic filler” means that the blending amount of the inorganic filler in the adhesive composition of the present invention is 1% by weight or less. When the blending amount of the inorganic filler exceeds 1% by weight, for example, an adhesive composition is applied to the surface of the semiconductor wafer having bumps on the surface having the bumps to form an adhesive layer, and then the surface of the bumps are bonded. When the surface is flattened so as to be exposed from the agent layer, defects such as tool wear may occur.

The adhesive composition of this invention may contain fillers, such as a polyimide, as needed.
The adhesive composition of the present invention further contains an antifoaming agent, ion trapper, flux, colorant, coupling agent, reactive diluent, rubber component, rubber particles, leveling agent, flame retardant, etc., as necessary. You may contain.

The adhesive composition of the present invention has a melt viscosity at a bonding temperature of 10 Pa · s to 15000 Pa · s. By setting the melt viscosity at the bonding temperature within the above range, the adhesive composition can sufficiently discharge voids between the bumps at the time of bonding, and a semiconductor device manufactured using such an adhesive composition Excellent reliability.
When the melt viscosity at the bonding temperature is less than 10 Pa · s, when bonding the semiconductor wafer or chip coated with the adhesive composition to another semiconductor wafer or chip having unevenness, the other semiconductor wafer having unevenness Alternatively, voids are easily generated on the chip side, and a semiconductor device manufactured using such an adhesive composition is inferior in reliability. If the melt viscosity at the bonding temperature exceeds 15000 Pa · s, the required load becomes too large when bonding the semiconductor wafer or chip coated with the adhesive composition, resulting in bump misalignment or semiconductor chip tilt. It is easy and the semiconductor device manufactured using such an adhesive composition is inferior in reliability.

The adhesive composition of the present invention has a gel time of 10 seconds or more at the bonding temperature. By setting the gel time at the bonding temperature within the above range, voids between the bumps can be sufficiently discharged during bonding, and a semiconductor device manufactured using such an adhesive composition has excellent reliability.
When the gel time at the bonding temperature is less than 10 seconds, the adhesive composition is cured before the void is discharged, and the void remains.

In the present specification, bonding means a step of bonding a semiconductor wafer or chip coated with an adhesive composition to another semiconductor wafer or chip or substrate via the adhesive composition, and thereafter It means a process of applying a weight and heating in order to connect the bumps.
In addition, in this specification, the bonding temperature refers to a process in which a semiconductor wafer or chip to which an adhesive composition is applied is bonded to another semiconductor wafer or chip or a substrate via the adhesive composition. It is a temperature for flowing the adhesive composition to produce a bonded body without voids. Such a bonding temperature is preferably 140 to 180 ° C., for example. If the bonding temperature is lower than 140 ° C., the semiconductor wafer or the like cannot be sufficiently fixed, and positional deviation may occur. If the bonding temperature is higher than 180 ° C., the adhesive composition may be caught between the bumps in the next bonding of the bumps, resulting in poor conduction.

Also, in this specification, the melt viscosity at the bonding temperature is the temperature at which the cone plate is sheared at a frequency of 1 rad second while the temperature is increased from 35 ° C. to 200 ° C. at a temperature increase rate of 5 ° C./min. Means the melt viscosity at the bonding temperature measured in.
Furthermore, in this specification, gel time means the gel time measured based on JISC2161B.

The adhesive composition of the present invention has a gel time at 240 ° C. of 1 second to 10 seconds. By setting the gel time at 240 ° C. within the above range, the semiconductor device manufactured using the adhesive composition is excellent in reflow resistance and reliability.
When the gel time at 240 ° C. is less than 1 second, the adhesive composition tends to bite between the bumps. If the gel time at 240 ° C. exceeds 10 seconds, voids are likely to occur during cooling after bonding the bumps.
In the present specification, the temperature condition of 240 ° C. is a condition normally used when bonding is performed via a bump when a semiconductor device is manufactured using the adhesive composition of the present invention.

The method for producing the adhesive composition of the present invention is not particularly limited, and for example, a predetermined amount of each material such as the thermosetting compound, the polymer having a reactive functional group, and the thermosetting agent is mixed and mixed. The method etc. which obtain an adhesive composition by doing are mentioned.
The method of mixing is not particularly limited, and examples thereof include a method of mixing using a planetary stirrer, homodisper, universal mixer, Banbury mixer, kneader, three rolls, and the like.

Although the use of the adhesive composition of the present invention is not particularly limited, for example, it is used for manufacturing a semiconductor device.
In particular, a semiconductor wafer or chip having a bump and a resin layer formed so that the surface of the bump is exposed on the surface having the bump, and another semiconductor wafer or chip or substrate having the bump, By bonding using the adhesive composition of the invention, a semiconductor device excellent in reflow resistance and reliability can be manufactured while suppressing generation of voids.
In order to obtain a semiconductor wafer or chip having the bump and a resin layer formed so that the surface of the bump is exposed on the surface having the bump, for example, the bump of the semiconductor wafer or chip and the bump are included. For example, a method of flattening the surface of the resin layer formed so that the bumps are buried in the surface by, for example, cutting using a cutting tool so that the surface of the bumps are exposed from the resin layer is used. A sufficient fillet can be formed by further forming a resin layer on the surface flattened surface using the adhesive composition of the present invention.

Using the adhesive composition of the present invention that does not substantially contain an inorganic filler on the surface of the first semiconductor wafer having bumps, the thickness of the first semiconductor wafer is 5 to 50 μm higher than the average bump height. The step of forming the resin layer 1 on the surface, using the cutting tool, the step of cutting the resin layer 1 and the bump so that the average bump height after cutting becomes 97 to 50% before cutting, the first Using the adhesive composition of the present invention substantially containing no inorganic filler or the adhesive composition of the present invention containing 30 to 80% by weight of the inorganic filler on the cut surface of the semiconductor wafer, A step of forming a resin layer 2 having a thickness of 5 to 50 μm, a step of dividing the first semiconductor wafer into semiconductor chips as needed, and a step of forming the first semiconductor wafer or the separated semiconductor chips The second semiconductor A method for manufacturing a semiconductor device having a process of connecting to a body wafer, a chip, or a substrate via a bump is also one aspect of the present invention.
Such a semiconductor device manufacturing method is referred to as a semiconductor device manufacturing method according to the first aspect of the present invention.

The adhesive composition of the present invention containing substantially no inorganic filler on the surface of the first semiconductor wafer having bumps, or the adhesive of the present invention containing 30 to 80% by weight of inorganic filler. By using the composition, the step of forming the resin layer 1 so as to have a thickness 5 to 50 μm higher than the average height of the bump, the step of curing the resin layer 1, and the grinding, the average height of the bump after cutting. The step of cutting the resin layer 1 and the bump so as to be 97 to 50% before cutting, the adhesive of the present invention containing substantially no inorganic filler on the cut surface of the first semiconductor wafer A step of forming a resin layer 2 having a thickness of 5 to 50 μm using the composition or the adhesive composition of the present invention containing 30 to 80% by weight of an inorganic filler, and if necessary, the first semiconductor wafer Individualized A semiconductor chip, and a step of connecting the first semiconductor wafer or the singulated semiconductor chip to a second semiconductor wafer or chip or a substrate via a bump. The manufacturing method is also one aspect of the present invention.
Such a method for manufacturing a semiconductor device is referred to as a method for manufacturing a semiconductor device according to the second aspect of the present invention.

Hereinafter, a method for manufacturing a semiconductor device of the present invention will be described.
First, a method for manufacturing a semiconductor device according to the first aspect of the present invention will be described.
In the manufacturing method of the semiconductor device of the first aspect of the present invention, first, the adhesive composition of the present invention substantially not containing an inorganic filler is used on the surface of the first semiconductor wafer having the bump, which has the bump. The step of forming the resin layer 1 is performed so that the thickness is 5 to 50 μm higher than the average bump height.
When the thickness of the resin layer 1 is less than 5 μm with respect to the average bump height, the resin layer 1 and the bumps on the entire surface of the first semiconductor wafer are cut using a cutting tool in a later step. Is difficult. When the thickness of the resin layer 1 exceeds 50 μm with respect to the average bump height, a cutting tool is used to cut the resin layer 1 and the bumps on the entire surface of the first semiconductor wafer in a later step. It takes time and is inferior in productivity.

In the step of forming the resin layer 1, the adhesive composition of the present invention containing substantially no inorganic filler is used for the resin layer 1. When an adhesive composition containing an inorganic filler is used for the resin layer 1, wear of the cutting tool becomes significant during cutting using the cutting tool in a later step, and the productivity of the semiconductor device decreases.

The method for forming the resin layer 1 is not particularly limited. For example, the adhesive composition is supplied by a coating method such as spin coating, spray coating, screen printing, or slit coating, and then the solvent is dried as necessary. Examples thereof include a method, a method of applying to a place required by a dispensing method such as air dispensing and jet dispensing.
Further, as a method of forming the resin layer 1, the adhesive composition is applied on a release film to form a sheet, and then dried and polymerized to a polymer as necessary. Examples include a method of bonding to a surface having a bump of a semiconductor wafer and peeling the release film. In such a method, the release film may be a BG tape or a DC tape.
In addition, after forming the said resin layer 1, it is preferable that the said resin layer 1 does not show fluidity at room temperature.

In the step of forming the resin layer 1, the polymer having the functional group capable of reacting is mixed in advance with the adhesive composition of the present invention containing substantially no inorganic filler, and the first semiconductor wafer is formed. After the adhesive composition of the present invention containing substantially no inorganic filler may be formed into a sheet, the polymer having some or all of the above functional groups capable of reacting with UV or heat is applied. It may be polymerized and bonded to the first semiconductor wafer, or after the adhesive composition of the present invention containing substantially no inorganic filler is applied to the first semiconductor wafer, UV or heat is applied. Polymerization may be performed.

In the semiconductor device manufacturing method according to the first aspect of the present invention, the resin layer 1 and the bumps are then cut using a tool so that the average bump height after cutting becomes 97 to 50% before cutting. Perform the process.
If the average bump height after cutting exceeds 97% before cutting, it is difficult to cut the bumps on the entire surface of the first semiconductor wafer because the height of the bumps varies. If the average bump height after cutting is less than 50% before cutting, it takes time to cut the bump, resulting in poor productivity.

In the manufacturing method of the semiconductor device of the first aspect of the present invention, the adhesive composition of the present invention substantially containing no inorganic filler on the cut surface of the first semiconductor wafer, or 30 to 80 wt. Using the adhesive composition of the present invention containing% inorganic filler, a step of forming a resin layer 2 having a thickness of 5 to 50 μm is performed.
When the thickness of the resin layer 2 is less than 5 μm, the first semiconductor wafer or the separated semiconductor chip is transferred to the second semiconductor wafer or chip or the substrate via bumps in a later step. Therefore, the generation of voids cannot be sufficiently suppressed. When the thickness of the resin layer 2 exceeds 50 μm, the first semiconductor wafer or the separated semiconductor chip is transferred to the second semiconductor wafer or chip or the substrate via bumps in a later step. At the time of connection, the resin layer 2 or the like bites between the bumps, or the weight necessary for connection becomes too large.

The resin layer 2 preferably has a visible light transmittance of 50% or more. When the visible light transmittance of the resin layer 2 is less than 50%, the first semiconductor wafer or the separated semiconductor chip is replaced with the second semiconductor wafer or chip or the substrate in a later step. When connecting to each other via bumps, alignment may be difficult, and alignment may be deteriorated.
The resin layer 2 preferably has a haze value of 60% or less.

In the method for manufacturing a semiconductor device according to the first aspect of the present invention, the step of dividing the first semiconductor wafer into semiconductor chips is then performed as necessary.

In the semiconductor device manufacturing method according to the first aspect of the present invention, the first semiconductor wafer or the separated semiconductor chip is then connected to the second semiconductor wafer or chip or the substrate via bumps. Perform the process.
In the connecting step, for example, the semiconductor wafers may be connected, the semiconductor chips may be connected, the semiconductor wafer and the semiconductor chip may be connected, or the semiconductor chip and the substrate are connected. Also good.

In the semiconductor device manufacturing method of the first aspect of the present invention, the melt viscosity of the resin layer 1 at the bonding temperature is preferably 1 to 1000 times the melt viscosity of the resin layer 2 at the bonding temperature.
If the melt viscosity at the bonding temperature of the resin layer 1 is less than 1 times the melt viscosity at the bonding temperature of the resin layer 2, the resin layer 1 flows too much during bonding, and voids are generated between the bumps. It may not be sufficiently suppressed. When the melt viscosity at the bonding temperature of the resin layer 1 exceeds 1000 times the melt viscosity at the bonding temperature of the resin layer 2, the resin layer 1 sufficiently follows the deformation of the bump when the bump is bonded. There are things you can't do.
In the semiconductor device manufacturing method according to the first aspect of the present invention, the melt viscosity at the bonding temperature of the resin layer 1 is more preferably 5 times or more the melt viscosity at the bonding temperature of the resin layer 2, and is 100 times higher. More preferably, it is more preferably 50 times or less.
In addition, for example, by adjusting the weight average molecular weight of the polymer having a functional group capable of reacting, the blending amount in the adhesive composition of the present invention, the melt viscosity at the bonding temperature of the resin layer 1 is within the above range. can do.

Next, a method for manufacturing a semiconductor device according to the second aspect of the present invention will be described.
In the method for producing a semiconductor device of the second aspect of the present invention, first, the adhesive composition of the present invention which does not substantially contain an inorganic filler on the surface of the first semiconductor wafer having bumps, which has the bumps, or 30 Using the adhesive composition of the present invention containing -80% by weight of an inorganic filler, a step of forming the resin layer 1 so as to have a thickness 5-50 μm higher than the average bump height is performed.
If the thickness of the resin layer 1 is less than 5 μm with respect to the average bump height, it is difficult to cut the resin layer 1 and the bumps on the entire surface of the first semiconductor wafer by grinding in a later step. . When the thickness of the resin layer 1 exceeds 50 μm with respect to the average bump height, it takes time to cut the resin layer 1 and the bumps on the entire surface of the first semiconductor wafer by grinding in a later step. Takes less productivity.

In the step of forming the resin layer 1, the adhesive composition of the present invention which does not substantially contain an inorganic filler may be used for the resin layer 1, and a book containing 30 to 80% by weight of an inorganic filler. Although the adhesive composition of the present invention may be used, it is preferable to use the adhesive composition of the present invention containing 30 to 80% by weight of an inorganic filler. By using the adhesive composition of the present invention containing 30 to 80% by weight of an inorganic filler, the resin layer 1 and the bumps on the entire surface of the first semiconductor wafer are cut by grinding in a later step. In this case, it is possible to promote the cutting of the grindstone used.

The method for forming the resin layer 1 is not particularly limited, and examples thereof include the same method as the method in the semiconductor device manufacturing method according to the first aspect of the present invention.

In the semiconductor device manufacturing method according to the second aspect of the present invention, a step of curing the resin layer 1 is then performed.
By curing the resin layer 1, the resin layer 1 has a sufficient hardness, and the resin layer 1 and the bumps are cut by a general grind in a later step, and the first semiconductor The surface of the wafer can be planarized.

In the semiconductor device manufacturing method according to the second aspect of the present invention, the step of cutting the resin layer 1 and the bumps by grinding so that the average bump height after cutting becomes 97 to 50% before cutting. Do.
If the average bump height after cutting exceeds 97% before cutting, it is difficult to cut the bumps on the entire surface of the first semiconductor wafer because the height of the bumps varies. If the average bump height after cutting is less than 50% before cutting, it takes time to cut the bump, resulting in poor productivity.

In the semiconductor device manufacturing method according to the second aspect of the present invention, a step of forming solder bumps on the ground bumps may then be performed. Thereby, the variation in the height of the bump can be reduced, and the generation of voids can be suppressed.
The method of forming the solder bump is not particularly limited, and examples thereof include a method of forming by plating using a resist, screen printing, electroless plating, a ball mounting method, and the like.

In the manufacturing method of the semiconductor device of the second aspect of the present invention, the adhesive composition of the present invention substantially containing no inorganic filler on the cut surface of the first semiconductor wafer, or 30 to 80 wt. Using the adhesive composition of the present invention containing% inorganic filler, a step of forming a resin layer 2 having a thickness of 5 to 50 μm is performed.
When the thickness of the resin layer 2 is less than 5 μm, the first semiconductor wafer or the separated semiconductor chip is transferred to the second semiconductor wafer or chip or the substrate via bumps in a later step. Therefore, the generation of voids cannot be sufficiently suppressed. When the thickness of the resin layer 2 exceeds 50 μm, the first semiconductor wafer or the separated semiconductor chip is transferred to the second semiconductor wafer or chip or the substrate via bumps in a later step. At the time of connection, the resin layer 2 or the like bites between the bumps, or the weight necessary for connection becomes too large.

The visible light transmittance and haze value of the resin layer 2 are not particularly limited, but are preferably the same as the visible light transmittance and haze value of the resin layer 2 in the semiconductor device manufacturing method of the first aspect of the present invention.

In the method for manufacturing a semiconductor device according to the second aspect of the present invention, the step of separating the first semiconductor wafer into semiconductor chips is then performed as necessary.

In the semiconductor device manufacturing method according to the second aspect of the present invention, the first semiconductor wafer or the separated semiconductor chip is then connected to the second semiconductor wafer or chip or the substrate via bumps. Perform the process.
In the connecting step, for example, the semiconductor wafers may be connected, the semiconductor chips may be connected, the semiconductor wafer and the semiconductor chip may be connected, or the semiconductor chip and the substrate are connected. Also good.

In such a method of manufacturing a semiconductor device of the present invention, the first semiconductor wafer or the individual semiconductor chip has a plurality of bumps on the surface. In addition, the second semiconductor wafer or chip or the substrate has a plurality of bumps on the surface or an electrode corresponding to the first semiconductor wafer or the separated semiconductor chip.

By using such a method for manufacturing a semiconductor device of the present invention, a semiconductor device having excellent reflow resistance and reliability can be manufactured.
Among them, the obtained semiconductor device is excellent in that the cured product of the resin layer 1 and the resin layer 2 has a predetermined range of elastic modulus, so that stress is dispersed even when exposed to a temperature cycle or the like. Reliability can be maintained.

In the semiconductor device manufactured using the method for manufacturing a semiconductor device of the present invention, the cured product of the resin layer 1 has an elastic modulus of 3 to 9 GPa at 25 ° C., and the cured product of the resin layer 2 is A semiconductor device having an elastic modulus at 25 ° C. of 2 to 5 GPa is also one aspect of the present invention.

When the elastic modulus at 25 ° C. of the cured product of the resin layer 1 is less than 3 GPa, the cured product of the resin layer 1 is greatly deformed when exposed to a temperature cycle or the like. In some cases, the function of protecting the periphery of the bump cannot be performed. When the elastic modulus at 25 ° C. of the cured product of the resin layer 1 exceeds 9 GPa, when exposed to a temperature cycle or the like, for example, a defect such as peeling occurs around the semiconductor chip, and the reliability of the semiconductor device is increased. May decrease.
Moreover, when the elastic modulus at 25 ° C. of the cured product of the resin layer 2 is less than 2 GPa, the cured product of the resin layer 2 may be deformed when exposed to a temperature cycle or the like. It becomes large and may not perform the function of protecting the periphery of the bump. When the elastic modulus at 25 ° C. of the cured product of the resin layer 2 exceeds 5 GPa, the reliability of the semiconductor device may be lowered when exposed to a temperature cycle or the like.

In the present specification, the elastic modulus at 25 ° C. of the cured product of the resin layer 1 and the resin layer 2 is the same as that of the cured product of the resin layer 1 and the resin layer 2 (model “DVA- 200 ”, manufactured by IT Measurement & Control Co., Ltd.), the temperature is raised from −50 ° C. to 300 ° C. at a pulling and gripping width of 24 mm, 10 Hz, and measured at 25 ° C. Value.

ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition which can be used in order to manufacture a semiconductor device which is hard to produce a void between bumps at the time of bonding, and was excellent in reflow resistance and reliability can be provided. Moreover, according to this invention, the manufacturing method of the semiconductor device using this adhesive composition and the semiconductor device manufactured using the manufacturing method of this semiconductor device can be provided.

Examples of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

(Examples 1-9, Comparative Examples 1-3)
(1) Preparation of Adhesive Composition According to the composition shown in Table 1, the following materials were stirred and mixed using a homodisper to prepare an adhesive composition.

(Thermosetting compound)
(Epoxy resin)
HP-7200HH (manufactured by DIC, epoxy equivalent of 275-280 g / eq, softening point 87-92 ° C.)
NC-3000-H (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288 g / eq, softening point 91 ° C.)
EPR-4030 (manufactured by ADEKA, epoxy equivalent 380 g / eq, 60 Pa · s (25 ° C.))
YX-8800 (Japan Epoxy Resin, 205g / eq)
YX-4000HK (Japan Epoxy Resin Co., 187-197g / eq)
807 (bis F type epoxy) (manufactured by Japan Epoxy Resin Co., Ltd., 160 to 175 g / eq)
DAMGIC (manufactured by Shikoku Chemicals)

(Benzoxazine resin)
RLV-100 (manufactured by Air Water Chemical)
Benzoxazine Fa type (manufactured by Shikoku Chemicals, softening point 30 ° C)
(Bismaleimide resin)
BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd., melting point 70-145 ° C.)

(Polymer having reactive functional group)
CP-30 (manufactured by NOF Corporation, weight average molecular weight 9000, epoxy equivalent 530 g / eq)
G-0250M (manufactured by NOF Corporation, weight average molecular weight 20000-25000, epoxy equivalent 310 g / eq)
G-2050M (manufactured by NOF Corporation, weight average molecular weight 200,000 to 250,000, epoxy equivalent 340 g / eq)
Polymer A (13 parts by weight of isobornyl acrylate, 73 parts by weight of 2-ethylhexyl acrylate, 14 parts by weight of glycidyl methacrylate and 0.2 parts by weight of a photopolymerization initiator (Irgacure 651) was dissolved in ethyl acetate and irradiated with ultraviolet rays. (Acrylic copolymer having a weight average molecular weight of 600,000 obtained by polymerization)

(Thermosetting agent)
(Acid anhydride)
YH-307 (manufactured by Japan Epoxy Resin, neutralization equivalent 113-121 g / eq)
(Compound having phenolic hydroxyl group)
GPH-103 (manufactured by Nippon Kayaku Co., Ltd., OH equivalent 231 g / eq, softening point 102 ° C.)
VH-4150 (manufactured by DIC, BPA novolac resin, OH equivalent 118 g / eq, softening point 85-89 ° C.)

(Thermosetting accelerator)
2MAOK-PW (manufactured by Shikoku Chemicals, melting point 260 ° C)
2MZA-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd., melting point 248-258 ° C.)

(Silane coupling agent)
KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Inorganic filler)
MT-10 (manufactured by Tokuyama, primary average particle size 15 nm)
SE-2050-SPJ (manufactured by Admatechs)
(solvent)
MEK (methyl ethyl ketone)

About the obtained adhesive composition, melt viscosity (Pa * s) and gel time (second) in bonding temperature (140 degreeC and 180 degreeC) were measured. Further, the gel time (seconds) at 240 ° C. was measured. The gel time was measured according to JIS C2161 B. The results are shown in Table 1.

(2) Fabrication of semiconductor device (Method 1) (Examples 1, 2, 4, 8, 9, Comparative Examples 1, 2, 3)
(2-1) Formation of resin layer 1 and surface flattening According to the composition of Table 1, the materials shown above were stirred and mixed using a homodisper to prepare an adhesive composition.
WALTS-TEG MB50-0101JY_PAD 15 μm (diameter 200 mm, thickness 725 μm, PI: 4 μm thickness, Cu pillar 30 μmt + solder 15 μmt, manufactured by Waltz Co., Ltd.) Was applied by spin coating so that the bumps were buried. Then, it heated at 80 degreeC for 20 minute (s), the solvent was volatilized, and the silicon wafer which has the bump and the resin layer 1 formed so that a bump might be buried was obtained.
The obtained silicon wafer having the bump and the resin layer 1 was cut using a cutting apparatus (DFS8910, manufactured by DISCO) at 25 ° C. so that the average height of the solder portion was 40 μm. Turned into.

(2-2) Formation of Resin Layer 2 The surface of the silicon wafer having the obtained bump and the resin layer 1 having the bump and the resin layer 1 is coated with the adhesive composition obtained above on the thickness of the dry film. The silicon wafer having the bump, the resin layer 1, and the resin layer 2 was obtained by spin coating.

(2-3) Dicing After reinforcing the back surface of the silicon wafer having the obtained bump, resin layer 1 and resin layer 2 with a dicing tape, it was attached to a dicing apparatus (DFD6362, manufactured by DISCO) at 25 ° C. In step cut (first cut depth = 80 μm from the silicon wafer surface, second cut depth = wafer full cut), the silicon wafer is separated into 7.3 mm × 7.3 mm semiconductor chips, and the semiconductor chips are Obtained.

(3) Fabrication of semiconductor device (Method 2) (Examples 3, 5, 6, and 7)
(3-1) Formation of resin layer 1 and surface flattening According to the composition of Table 1, the materials shown above were stirred and mixed using a homodisper to prepare an adhesive composition.
WALTS-TEG MB50-0101JY_PAD 15 μm (diameter 200 mm, thickness 725 μm, PI: 4 μm thickness, Cu pillar 30 μmt + solder 15 μmt, manufactured by Waltz Co., Ltd.) Was applied by spin coating so that the bumps were buried. Then, it heated at 80 degreeC for 20 minute (s), the solvent was volatilized, and the silicon wafer which has the bump and the resin layer 1 formed so that a bump might be buried was obtained.
Next, the resin layer 1 was cured at 170 ° C. for 30 minutes. The obtained silicon wafer having the bump and the resin layer 1 was cut using a grinding apparatus (DFG8560, manufactured by DISCO) at 25 ° C. so that the average height of the solder portion was 40 μm. Turned into. Further, the resin layer 2 was formed and diced in the same manner as (2-2) and (2-3).

(Examples 10 to 14)
A semiconductor chip was obtained by using Method 1 or 2 as described in Table 2 so that the resin layers 1 and 2 would be the resin layers prepared in the examples described in Table 2, respectively.

<Evaluation>
20 mm × in which copper is wired so that the individual semiconductor chips obtained in the examples and comparative examples are daisy chained with metal wiring in the semiconductor chip when electrically connected via the semiconductor chip. Using a bonding device (FC3000, manufactured by Toray Engineering Co., Ltd.) on a 20 mm × 0.75 mm thick substrate (glass / epoxy FR-4), the actual temperature applied to the bumps is 180 ° C., 10 seconds, 10N + 240 ° C., 10 seconds. Bonding was performed under the condition of 10N. Then, complete curing was performed in an oven at 170 ° C. for 30 minutes.

For the resin layer 1 and the resin layer 2, using a melt viscometer, the melt viscosity at the bonding temperature is 140 ° C. at a heating rate of 5 ° C./minute, 180 ° C. at a constant temperature of 1 rad second, and cone plate shearing. (Melt viscosity of resin layer 1) / (Melt viscosity of resin layer 2) were measured as shown in Tables 1 and 2.
The elastic modulus (MPa) at 25 ° C. of the resin layer 1 and the resin layer 2 after complete curing was as shown in Table 1. The elastic modulus is from −50 ° C. to 300 ° C. using a viscoelasticity measuring machine (model “DVA-200” manufactured by IT Measurement & Control Co., Ltd.) The temperature was raised and measured at 25 ° C. The peak temperature of tan δ was defined as Tg (° C.).
The results are shown in Table 1.

(1) Void observation 1 (SAT)
About the obtained semiconductor device, the presence or absence of the void was confirmed using the ultrasonic imaging device (SAT) (mi-scope hyper, Hitachi Construction Machinery Finetech Co., Ltd.). The case where the area of the void was 1% or more was evaluated as x, and the case where it was less than 1% was evaluated as ◯.
(2) Void observation 2 (optical microscope)
The obtained semiconductor device was polished from the chip side horizontally with the chip until the chip disappeared, and voids between the bumps were observed with an optical microscope. The case where there was one or more voids of 30 μm or more between all the bumps was rated as x, and the case where no voids of 30 μm or more were found was marked as ◯.

(3) Continuity test The conduction of the daisy chain of the obtained semiconductor device was confirmed, and the case where the conduction resistance value was 25 to 35Ω was evaluated as “◯”, and the case where it was less than 25Ω or 35Ω or more was evaluated as “X”.

(4) Reflow test The obtained semiconductor device was absorbed at 60 ° C., 60% RH for 120 hours, passed through a reflow oven at a peak temperature of 260 ° C. three times, and chip-resin layer 1 and resin layer 2-substrate were peeled off. Evaluation and continuity tests were performed.
Regarding the peeling evaluation, the case where the void area was 1% or more was evaluated as x, and the case where it was less than 1% was evaluated as ◯. About the said continuity test, the case where it was (circle) and less than 25 ohms or 35 ohms or more when the conduction resistance value was 25-35 ohms was set as x.

(5) Temperature cycle test The obtained semiconductor device is subjected to a temperature cycle test of −55 to 125 ° C. (30 minutes / 1 cycle) and 1000 cycles, and evaluation of chip-resin layer 1 and resin layer 2-substrate peeling. And a continuity test was performed. About Examples 10-14, the temperature cycle test of 5000 cycles was similarly done.
Regarding the peeling evaluation, the case where the void area was 1% or more was evaluated as x, and the case where it was less than 1% was evaluated as ◯. About the said continuity test, the case where it was (circle) and less than 25 ohms or 35 ohms or more when the conduction resistance value was 25-35 ohms was set as x.

ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition which can be used in order to manufacture a semiconductor device which is hard to produce a void between bumps at the time of bonding, and was excellent in reflow resistance and reliability can be provided. Moreover, according to this invention, the manufacturing method of the semiconductor device using this adhesive composition and the semiconductor device manufactured using the manufacturing method of this semiconductor device can be provided.

Claims (11)

An adhesive composition comprising a thermosetting compound, a polymer having a functional group capable of reacting with the thermosetting compound, and a thermosetting agent,
The melt viscosity at the bonding temperature is 10 Pa · s or more and 15000 Pa · s or less,
The gel time at the bonding temperature is 10 seconds or more, and
An adhesive composition having a gel time at 240 ° C. of 1 second to 10 seconds. The adhesive composition according to claim 1, wherein the thermosetting compound contains at least one selected from the group consisting of an epoxy resin, a benzoxazine resin, and a bismaleimide resin. The adhesive composition according to claim 1 or 2, wherein the thermosetting agent is a compound having an acid anhydride or a phenolic hydroxyl group. The adhesive composition according to claim 1, 2, or 3, wherein the polymer having a functional group capable of reacting with the thermosetting compound has a weight average molecular weight of 9000 to 600,000. The adhesive composition according to claim 1, 2, 3, or 4, which contains substantially no inorganic filler. Furthermore, 30-80 weight% inorganic filler is contained, The adhesive composition of Claim 1, 2, 3 or 4 characterized by the above-mentioned. The resin layer 1 is formed on the surface having the bumps of the first semiconductor wafer having bumps by using the adhesive composition according to claim 5 so that the thickness is 5 to 50 μm higher than the average bump height. The process of
A step of cutting the resin layer 1 and the bumps using a bite so that the average bump height after cutting is 97 to 50% before cutting;
Forming a resin layer 2 having a thickness of 5 to 50 μm on the cut surface of the first semiconductor wafer using the adhesive composition according to claim 5 or 6;
If necessary, the step of dividing the first semiconductor wafer into semiconductor chips, and
A method for manufacturing a semiconductor device, comprising a step of connecting the first semiconductor wafer or the singulated semiconductor chip to a second semiconductor wafer or chip or a substrate via a bump. The method of manufacturing a semiconductor device according to claim 7, wherein the melt viscosity at the bonding temperature of the resin layer 1 is 1 to 1000 times the melt viscosity at the bonding temperature of the resin layer 2. Using the adhesive composition according to claim 5 or 6 on the surface of the first semiconductor wafer having bumps, the resin layer 1 has a thickness 5 to 50 μm higher than the average bump height. Forming a process,
Curing the resin layer 1;
The step of cutting the resin layer 1 and the bumps by grinding so that the average bump height after cutting becomes 97 to 50% before cutting,
Forming a resin layer 2 having a thickness of 5 to 50 μm on the cut surface of the first semiconductor wafer using the adhesive composition according to claim 5 or 6;
If necessary, the step of dividing the first semiconductor wafer into semiconductor chips, and
A method for manufacturing a semiconductor device, comprising a step of connecting the first semiconductor wafer or the singulated semiconductor chip to a second semiconductor wafer or chip or a substrate via a bump. After the step of cutting the resin layer 1 and the bumps by grinding so that the average bump height after cutting becomes 97 to 50% before cutting,
Before the step of forming the resin layer 2 having a thickness of 5 to 50 μm on the cut surface of the first semiconductor wafer, using the adhesive composition according to claim 5 or 6,
10. The method of manufacturing a semiconductor device according to claim 9, further comprising a step of forming a solder bump on the ground bump. A semiconductor device manufactured using the method for manufacturing a semiconductor device according to claim 7, 8, 9 or 10,
The cured product of the resin layer 1 has an elastic modulus at 25 ° C. of 3 to 9 GPa,
The cured product of the resin layer 2 has an elastic modulus at 25 ° C. of 2 to 5 GPa.