JP2013221122A - Interlayer filler composition for three-dimensional multi-layer semiconductor device and coating solution thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an interlayer filler composition for three-dimensional multi-layer semiconductor devices, which can satisfy both void reduction and solder joint.SOLUTION: An interlayer filler composition for three-dimensional multi-layer semiconductor devices includes at least an epoxy resin (A) and a curing agent (B). The curing agent (B) is any of a primary amino group-containing compound, a secondary amino group-containing compound, an acid anhydride-containing compound, a phenolic hydroxy group-containing compound and dicyandiamide. Preferably the interlayer filler composition further includes a curing promoter (C), and an imidazole compound is preferable as the curing promoter (C).

Description

  The present invention relates to an interlayer filler composition for a three-dimensional stacked semiconductor device, a coating liquid containing the composition, a cured product of the composition, a three-dimensional stacked semiconductor device using the same, and a method for manufacturing the same. Is.

  In recent years, in order to improve the performance of semiconductor devices such as higher speed and higher capacity, in addition to miniaturization of transistors and wiring, the performance has been improved by three-dimensional stacking (3D) by stacking two or more semiconductor chips. Research and development is underway.

  Specifically, the B stage is formed after an underfill process (referred to as a post-feed type) in which an interlayer filler composition is poured between substrates after stacking semiconductor chips, or after forming a thin coating film of an interlayer filler composition on a wafer. Next, a semiconductor chip is cut out by dicing, a laminated body is obtained by temporary bonding using this semiconductor chip, and finally final bonding (solder bonding) and resin curing are simultaneously performed under pressure and heating conditions, and three-dimensional A process called a pre-feed type for forming a stacked semiconductor device has been proposed (see Non-Patent Documents 1 and 2).

“Electronics Package Technology (CMC Technical Library)”, CM Publishing (2003), p. 102 Proceedings of the 23rd Electronics Packaging Society Conference, Japan Institute of Electronics Packaging (2009), p. 61

Various problems have been pointed out for the practical application of the three-dimensional stacked semiconductor device as disclosed in Non-Patent Documents 1 and 2, and one of them is the generation of voids in the interlayer filler. This is a phenomenon in which bubbles are generated during bonding or curing of the filler between the semiconductor chip and the substrate, or between the semiconductor chip and the semiconductor chip, and the voids in the filler are the reliability of the semiconductor device, It becomes a factor that impairs the increase in speed and capacity.
Therefore, realizing solder joints for electrical connection while suppressing voids is a major issue for the industrialization of three-dimensional stacked semiconductor devices.
The present invention has been made in view of the above problems, and an object of the present invention is to provide an interlayer filler composition capable of achieving both void reduction and solder bonding in an interlayer filler of a three-dimensional stacked semiconductor device. That is.
Another object of the present invention is to provide a coating liquid containing the interlayer filler composition, a cured product of the interlayer filler composition, and a method for manufacturing a three-dimensional stacked semiconductor device using the interlayer filler composition coating liquid. And a three-dimensional stacked semiconductor device containing a cured product of the interlayer filler composition.

  As a result of intensive studies to solve the above problems, the present inventor has found that the following invention can solve the above problems, and has completed the present invention.

  That is, the gist of the present invention is as follows.

  [1] At least an epoxy resin (A) and a curing agent (B), the curing agent (B) having a primary amino group, a compound having a secondary amino group, a compound having an acid anhydride, a phenolic hydroxyl group An interlayer filler composition for a three-dimensional stacked semiconductor device, wherein the composition is one or more selected from the group consisting of a compound having a dicyandiamide.

[2] The interlayer filler composition for a three-dimensional stacked semiconductor device according to [1], further comprising a curing accelerator (C).

[3] The interlayer filler composition for a three-dimensional stacked semiconductor device according to [2], wherein the curing accelerator (C) is an imidazole compound.

[4] The interlayer filler composition for a three-dimensional stacked semiconductor device, wherein the interlayer filler composition according to any one of [1] to [3] further contains an organic solvent (D). Coating liquid.

[5] A cured interlayer filler for a three-dimensional stacked semiconductor device, wherein the interlayer filler composition according to any one of [1] to [3] is cured.

[6] A tertiary characterized in that after the interlayer filler composition coating solution according to [4] is applied onto a chip, B-staging is performed to reduce tackiness at room temperature, and then chip bonding is performed. A method for manufacturing an original stacked semiconductor device.

[7] A three-dimensional stacked semiconductor device comprising the cured interlayer filler according to [5].

  According to the present invention, there is provided an interlayer filler composition capable of achieving both a reduction in voids in an interlayer filler of a three-dimensional stacked semiconductor device and solder bonding. Further, according to the present invention, a coating solution containing the interlayer filler composition, a cured product of the interlayer filler composition, a method for producing a three-dimensional stacked semiconductor device using the interlayer filler composition, and A three-dimensional stacked semiconductor device containing a cured product of the interlayer filler composition is provided.

  Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

  The present invention first comprises at least an epoxy resin (A) and a curing agent (B), wherein the curing agent (B) has a primary amino group, a compound having a secondary amino group, a compound having an acid anhydride, An interlayer filler composition for a three-dimensional stacked semiconductor device (hereinafter sometimes simply referred to as “interlayer filler composition”), which is selected from a compound having a phenolic hydroxyl group and dicyandiamide. It is concerned.

  Here, the three-dimensional integrated semiconductor device of the present invention is a semiconductor chip stacked body in which at least two semiconductor chips on which semiconductor device layers are formed are stacked. Each semiconductor chip is provided with a through electrode (TSV), and TSVs are connected between the semiconductor chips via bumps. An interlayer filler (interlayer filler composition) is used between the layers of the laminate.

As a process for forming such a three-dimensional stacked semiconductor device, after forming a coating thin film of an interlayer filler composition on a wafer, B-stage is performed to reduce tackiness, and then a semiconductor chip is cut out by dicing, There has been proposed a process in which a laminated body is obtained by temporary bonding using this semiconductor chip, and finally main bonding (solder bonding) is performed under pressure and heating conditions.
In this step, it is important to perform solder bonding without forming voids in the interlayer filler in order to improve the reliability of the semiconductor device and to increase the speed and capacity.

  A compound containing an epoxy resin (A) and a curing agent (B), wherein the curing agent (B) has a primary amino group, a compound having a secondary amino group, a compound having an acid anhydride, a compound having a phenolic hydroxyl group, In view of the point that the interlayer filler composition of the present invention, characterized in that it is selected from any of dicyandiamide, can be B-staged and can suppress voids at high temperatures during solder joining. The composition satisfies the required performance, and further contains a curing accelerator (C), whereby an even better interlayer filler composition can be obtained.

(Interlayer filler composition)
[Epoxy resin (A)]
The epoxy resin (A) used in the interlayer filler composition of the present invention preferably has two or more epoxy groups in the molecule, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene. Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type Epoxy resin, polyfunctional phenol type epoxy resin, trisphenol methane type polyfunctional epoxy resin, bisphenol A type and bisphenol F type solid epoxy resin, phenoxy resin, epoxy resin reactive diluent, etc. It can be used a seed epoxy resin. These can be used alone or as a mixture of two or more.

[Curing agent (B)]
The hardening | curing agent (B) used by this invention shows the substance which contributes to the crosslinking reaction between the epoxy groups of an epoxy resin.
In the present invention, the curing agent (B) is selected from any one of a compound having a primary amino group, a compound having a secondary amino group, a compound having an acid anhydride, a compound having a phenolic hydroxyl group, and dicyandiamide. And

  Specific examples of the compound containing a primary amino group or a secondary amino group include aliphatic amines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, and 2,5-dimethylhexamethylene. Examples include diamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine, and the like. The Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like. Cycloaliphatic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino). Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like. Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4 -Toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) ethylamine , Diaminodiethyl Examples include rudimethyldiphenylmethane, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene.

  Specific examples of the compound containing an acid anhydride include dodecenyl succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) Anhydride, Methyltetrahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Hexahydrophthalic anhydride, Methylhymic anhydride, Tetrahydrophthalic anhydride, Trialkyltetrahydrophthalic anhydride, Methylcyclohexene dicarboxylic anhydride, Methylcyclohexene tetracarboxylic Acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic dianhydride, het anhydride, nadic anhydride, methyl nadic anhydride, 5- ( , 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Examples thereof include acid dianhydride and 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride.

  Specific examples of the compound containing a phenolic hydroxyl group include bisphenol A, bisphenol F, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, 1,3 -Bis (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'- Dihydroxybiphenyl, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak , P-cresol novolak, xylenol novolak, poly-p-hydroxystyrene, hydroquinone, resorcin, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallylated pyrogallol 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphth 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated Examples include pyrogallol.

Among these, it is preferable to use a compound containing a primary amino group or a secondary amino group, or dicyandiamide because of controllability of B-stage formation and void suppression at high temperatures.
These hardening | curing agents (B) may be used individually by 1 type, and 2 or more types may be mixed and used for them in arbitrary combinations and ratios.

The content of the curing agent (B) in the interlayer filler composition of the present invention is preferably 0.05 parts by weight or more and 65 parts by weight or less, more preferably 0, per 100 parts by weight of the epoxy resin (A). .1 to 60 parts by weight.
If the content of the curing agent (B) is less than 0.05 parts by weight per 100 parts by weight of the epoxy resin (A), curing may be insufficient, and if it exceeds 65 parts by weight, the curing agent is excessive. Therefore, desired physical properties may not be obtained.

[Curing accelerator (C)]
In the interlayer filler composition of the present invention, a curing accelerator (C) may be used in combination with the curing agent (B) in order to lower the curing temperature and shorten the curing time.
Examples of the curing accelerator (C) include a compound containing a tertiary amino group, imidazole and its derivatives, organic phosphines, dimethylurea and the like.

  Examples of the compound containing a tertiary amino group include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, etc. Is exemplified.

  Examples of imidazole and derivatives thereof include 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 2-ethyl-4 (5) -methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl -(1 ')]-ethyl-s-triazine, 2,4-di Mino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resin and the above imidazoles, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. Is exemplified.

  Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like, and phosphonium salts include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, Examples include tetrabutylphosphonium / tetrabutylborate, and examples of the tetraphenylboron salt include 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, and the like.

  Among these, it is preferable to use an imidazole compound (imidazole and its derivatives) from the characteristics such as a relatively long pot life, high curability in the middle temperature range, and high heat resistance of the cured resin.

  These curing accelerators (C) may be used alone or in a combination of two or more in any combination and ratio.

The content of the curing accelerator (C) in the interlayer filler composition of the present invention is preferably 0.001 parts by weight or more and 10 parts by weight or less, more preferably 100 parts by weight of the epoxy resin (A). 0.01 parts by weight or more and 5 parts by weight or less.
If the content of the curing accelerator (C) is less than 0.05 parts by weight per 100 parts by weight of the epoxy resin (A), the curing accelerating effect may be insufficient. May become dominant, and void reduction may not be achieved.

[Other additives]
The interlayer filler composition of the present invention may contain various additives within a range not impairing the effects of the present invention for the purpose of further improving the functionality.
Examples of additives include inorganic fillers, fluxes for improving solder jointability, coupling agents for improving adhesion to substrates and matrix resins and inorganic fillers, and for improving storage stability. Examples thereof include an ultraviolet ray inhibitor, an antioxidant, a plasticizer, a flame retardant, a colorant, a dispersant, a fluidity improver, and an adhesion improver with a substrate.
Any of these may be used alone or in a combination of two or more in any combination and ratio. The amount of other additives is not particularly limited, and is used in the usual resin composition to such an extent that necessary functionality is obtained, but the amount of other additive components other than the inorganic filler is The amount is preferably 10 parts by weight or less, more preferably 5 parts by weight or less per 100 parts by weight of the epoxy resin (A).

<Inorganic filler>
The inorganic filler is added for the purpose of improving the thermal conductivity and controlling the linear expansion coefficient, and is mainly intended to improve the thermal conductivity.
Therefore, it is preferable that the inorganic filler used in the present invention has high thermal conductivity. As the inorganic filler, a high thermal conductive inorganic filler having a thermal conductivity of 1 W / m · K or more, particularly 2 W / m · K or more is preferable. preferable.

Examples of the inorganic filler include alumina (Al ₂ O ₃ ), aluminum nitride (AlN), boron nitride (BN), silicon nitride (Si ₃ N ₄ ), silica (SiO ₂ ), and among others, Al ₂ O ₃ , AlN, BN, and SiO ₂ are preferable, and Al ₂ O ₃ , BN, and SiO ₂ are particularly preferable. These inorganic fillers may be used alone or in a combination of two or more in any combination and ratio.

If the inorganic filler has an excessively large particle size, lamination may be hindered. If the particle size is too small, the inorganic filler tends to aggregate and deteriorate dispersibility. It is preferable to use a thing of about 05-1000 micrometers.
Moreover, if it is an agglomerated inorganic filler, it is preferable to use one having an average crystal diameter of 0.01 μm to 5 μm and an average aggregate diameter of 1 to 1000 μm.

  When the interlayer filler composition of the present invention contains an inorganic filler, the content of the inorganic filler is preferably 10 parts by weight or more and 400 parts by weight or less, and 20 parts by weight or more and 300 parts by weight or less per 100 parts by weight of the epoxy resin (A). More preferred are parts by weight or less. When the content of the inorganic filler is less than 10 parts by weight per 100 parts by weight of the total epoxy resin, the effect of adding the inorganic filler is reduced, and the target thermal conductivity may not be obtained, and the amount exceeds 400 parts by weight. And the presence of fillers may impair the bondability.

<Flux>
Specifically, the flux means that the metal electrical signal terminal such as a solder bump and the surface oxide film of the land are dissolved and removed at the time of solder joining of the metal terminal, and the wetting and spreading property on the land surface of the solder bump is further improved. It is a compound having a function of preventing reoxidation of the surface of the metal terminal of the solder bump.

  Examples of the flux used in the present invention include aliphatic carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, citric acid, lactic acid, acetic acid, propionic acid, butyric acid, oleic acid, and stearic acid. Organic carboxylic acids such as benzoic acid, salicylic acid, phthalic acid, trimellitic acid, trimellitic anhydride, aromatic carboxylic acids such as trimesic acid, benzenetetracarboxylic acid, and terpene carboxylic acids such as abietic acid and rosin Organic carboxylic acid esters, glutamic acid hydrochlorides, aniline hydrochlorides, hydrazine hydrochlorides, cetylpyridine bromides, phenylhydrazine hydrochlorides, tetrachlors, which are hemiacetal esters converted by reacting acids and organic carboxylic acids with alkyl vinyl ethers Naphthalene, methylhydrazine hydrochloride, Organic halogen compounds such as tilamine hydrochloride, ethylamine hydrochloride, diethylamine hydrochloride and butylamine hydrochloride, amines such as urea and diethylenetriamine hydrazine, polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and glycerin , Inorganic acids such as hydrochloric acid, hydrofluoric acid, phosphoric acid, borohydrofluoric acid, fluorides such as potassium fluoride, sodium fluoride, ammonium fluoride, copper fluoride, nickel fluoride, zinc fluoride, potassium chloride, sodium chloride , Chlorides such as cuprous chloride, nickel chloride, ammonium chloride, zinc chloride, stannous chloride, bromides such as potassium bromide, sodium bromide, ammonium bromide, tin bromide, zinc bromide, etc. . These compounds may be used as they are or may be microencapsulated using a coating agent made of an organic polymer or an inorganic compound. These compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them in arbitrary combinations and ratios.

  When the interlayer filler composition of the present invention contains a flux, the content thereof is preferably 0.1 parts by weight or more and 10 parts by weight or less, more preferably 0.5 parts by weight per 100 parts by weight of the epoxy resin (A). Part to 5 parts by weight. If the flux content is less than 0.1 parts by weight per 100 parts by weight of the epoxy resin (A), there is a risk of poor solder connection due to reduced oxide film removability, and if it exceeds 10 parts by weight, connection due to an increase in the viscosity of the composition. There is a fear of defects.

<Coupling agent>
Furthermore, the interlayer filler composition of the present invention may contain a coupling agent such as a silane coupling agent and a titanate coupling agent from the viewpoint of improving the adhesion between the epoxy resin component and the inorganic filler.

  Here, as the silane coupling agent, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ, -Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltri Aminosilane such as ethoxysilane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysila And vinyl silanes such as γ-methacryloxypropyltrimethoxysilane, and epoxy, amino and vinyl polymer type silanes.

  On the other hand, titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate It is done.

  These coupling agents may be used alone or in a combination of two or more in any combination and ratio.

  When the interlayer filler composition of the present invention contains a coupling agent, the content thereof is preferably about 0.1 to 2.0% by weight with respect to the total solid content in the interlayer filler composition. If the amount of the coupling agent is small, the effect of improving the adhesion between the epoxy resin (A), which is a matrix resin by blending the coupling agent, and the inorganic filler cannot be sufficiently obtained. There is a problem that the coupling agent bleeds out from the cured product.

<Thermoplastic oligomers>
In addition, thermoplastic oligomers can be added to the interlayer filler composition of the present invention from the viewpoints of improving fluidity during molding and improving adhesion to the substrate. Thermoplastic oligomers include C5 and C9 petroleum resins, styrene resins, indene resins, indene / styrene copolymer resins, indene / styrene / phenol copolymer resins, indene / coumarone copolymer resins, indene / benzothiophene. Examples thereof include copolymer resins. These may be used alone or in combination of two or more. When the interlayer filler composition of the present invention contains these thermoplastic oligomers, the content thereof is usually in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin (A).

[Method for Producing Interlayer Filler Composition]
In the interlayer filler composition of the present invention, the epoxy resin (A), the curing agent (B), the curing accelerator (C) used as necessary, and other additive components are usually mixed uniformly by a mixer or the like. Thereafter, it is manufactured by kneading with a heating roll, a kneader or the like. There is no restriction | limiting in particular in the mixing | blending order of these components. It is also possible to form a film using a press after kneading. Further, after kneading, the melt-kneaded product can be pulverized to be powdered or tableted.

(Interlayer filler composition coating solution)
In the interlayer filler composition of the present invention, an epoxy resin (A), a curing agent (B), a curing accelerator (C) used as necessary, and other additive components are further dispersed in an organic solvent (D). Thus, a coating solution can be obtained.

[Organic solvent (D)]
Examples of the organic solvent (D) used in the interlayer filler composition coating solution of the present invention include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone, esters such as ethyl acetate, and ethylene. Ethers such as glycol monomethyl ether, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, alcohols such as methanol and ethanol, alkanes such as hexane and cyclohexane, and aromatics such as toluene and xylene Etc.

Among these, considering the solubility of the resin and the boiling point of the solvent, ketones such as methyl ethyl ketone and cyclohexanone, esters and ethers are preferable, and ketones such as methyl ethyl ketone and cyclohexanone are particularly preferable.
These organic solvents (D) may be used individually by 1 type, and 2 or more types may be mixed and used for them in arbitrary combinations and ratios.

In the interlayer filler composition coating liquid of the present invention, the mixing ratio of the organic solvent (D) to other components is not particularly limited, but preferably other than the organic solvent (D) in the interlayer filler composition coating liquid. The amount is preferably 5 parts by weight or more and 400 parts by weight or less, particularly preferably 10 parts by weight or more and 200 parts by weight or less, with respect to 100 parts by weight of the component (total solid content). By setting it as such a mixing ratio, a favorable coating film can be formed by arbitrary coating methods using the coating liquid of this invention.
If the mixing ratio of the organic solvent (D) is less than the above lower limit, the viscosity of the coating solution may increase and a good coating film may not be obtained, or if it exceeds the upper limit, a predetermined film thickness cannot be obtained. May come out.

[Other additives]
The interlayer filler composition coating solution of the present invention may further contain various additives.
Examples of such additives include surfactants, emulsifiers, low elasticity agents, and diluents that improve the dispersibility of each component in the coating liquid, in addition to the additives of the interlayer filler composition of the present invention described above. , Antifoaming agents, ion trapping agents and the like.

<Surfactant>
As the surfactant, any of conventionally known anionic surfactants, nonionic surfactants, and cationic surfactants can be used.
For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl Examples include sulfonates, sulfosuccinate esters, alkylbetaines, amino acids, and the like.
As content of surfactant, it is preferable to set it as about 0.001 to 5 weight% with respect to the total solid in the interlayer filler composition coating liquid of this invention. If the surfactant content is less than 0.001% by weight, the predetermined film thickness uniformity may not be obtained, and if it exceeds 5% by weight, phase separation from the epoxy resin component may occur. Absent. Here, the total solid content of the interlayer filler composition coating liquid refers to the total of components other than the organic solvent (D) in the interlayer filler composition coating liquid.

[Method for producing coating liquid]
The production method of the interlayer filler composition coating solution of the present invention is not particularly limited, and may be a conventionally known method, which can be produced by mixing the components of the coating solution. At that time, for the purpose of improving the uniformity of the coating liquid, defoaming, etc., it is possible to mix using a paint shaker, bead mill, planetary mixer, stirring type disperser, self-revolving stirring mixer, three rolls, etc. preferable.
Further, the mixing order is arbitrary as long as there is no particular problem such as reaction or precipitation, and any two components or three or more components of the coating liquid are mixed in advance, and then the remaining components are mixed. You may mix and may mix all at once.

[Interlayer filler cured product]
Hereinafter, the case where a hardened | cured material is obtained from the interlayer filler composition coating liquid of this invention is explained in full detail.
When applying the interlayer filler composition coating liquid of the present invention to the production of a three-dimensional stacked semiconductor device to obtain a cured product, it is usually carried out by the following procedure.

  The interlayer filler composition coating solution of the present invention is applied onto a wafer substrate, the solvent is removed from the formed coating film to form an A stage film, and further semi-cured to form a B stage film. Cut out. The cut-out chip is placed on the substrate, and after positioning and pressurizing and heating to temporarily bond, the semiconductor chip-substrate is pressed and heated to the melting temperature of the solder to perform bonding. Thereafter, the bonded semiconductor chip-substrate is heated in an oven or the like to be cured. The B stage film refers to a thin film with reduced tackiness in which the coating film does not flow at room temperature even when the coating film is tilted so that the film surface is in the vertical direction.

  Although there is no restriction | limiting in particular as the coating method of the coating liquid of this invention, Since a uniform thin film can be formed easily, spin coating, dip coating, spray coating, flow coating, doctor blade method, screen printing method, inkjet It is preferable to adopt a method or the like.

Removal of the solvent when removing the solvent from the formed coating film to obtain an A stage film can be performed by evaporating the solvent at room temperature or under heating. At this time, the pressure can be reduced as necessary. It is important for removing the solvent to obtain adhesiveness to be performed at a temperature lower than the curing temperature of the interlayer filler composition. Here, the curing temperature of the interlayer filler composition is the temperature of the gel point, and is usually about 20 to 200 ° C. The treatment temperature at the time of removing the solvent is preferably a temperature lower by about 10 to 100 ° C. than the curing temperature of the interlayer filler composition.
The A stage film obtained here can be semi-cured to obtain a B stage film.

Instead of obtaining a B-stage film by further heating after forming an A-stage on a wafer substrate or chip as described above, first, after applying a semi-curing reaction in a coating solution, coating on the chip, A B-stage film can also be obtained by removing the solvent.
In addition, after the solvent is distilled off from the coating solution, it is formed into a film using a press or a roll, the obtained film is sandwiched between a semiconductor chip and a substrate, and soldering is performed by pressing and heating, followed by heating. And can be cured.

[Three-dimensional stacked semiconductor device]
The three-dimensional stacked semiconductor device of the present invention has an interlayer filler composition cured product obtained by curing the interlayer filler composition of the present invention between layers, and realizes voidless bonding to improve the reliability of the semiconductor device. It is expected to contribute to the improvement of speed, speed and capacity.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

Below, the compounding component used for preparation of an interlayer filler composition or a coating liquid is as follows.
1) Epoxy resin (A)
Epoxy resin (A1): Bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation
Product name "YL6810"
Epoxy resin (A2): Trisphenol methane type multifunctional manufactured by Mitsubishi Chemical Corporation
Epoxy resin product name “1032H60”
(Preparing a 60 wt% methyl ethyl ketone solution)
Epoxy resin (A3): Mitsubishi Chemical Corporation bisphenol A type solid epoxy resin Trade name “1009”
(Preparation of 30 wt% methyl ethyl ketone solution)
2) Curing agent (B)
Dicyandiamide, trade name “DICY7”, manufactured by Mitsubishi Chemical Corporation
3) Curing accelerator (C)
2-Ethyl-4 (5) -methylimidazole manufactured by Mitsubishi Chemical Corporation
Product name "EMI24"
4) Organic solvent (D)
Methyl ethyl ketone (MEK)

The semiconductor chips and flip chip bonders used in the following examples are as follows.
5) Evaluation semiconductor chip: Test vehicle manufactured by Waltz Co., Ltd.
Product name "FC150 (10mm x 10mm) solder ball type"
Or “CC80 (7.3 mm × 7.3 mm) Cu post + solder mold”
6) Flip chip bonder: Toray Engineering brand name "FC3000S"

[Examples 1 to 3]
The epoxy resins (A1), (A2), (A3), the curing agent (B), the curing accelerator (C), and the organic solvent (D) are mixed by a revolving mixer as a blending weight ratio shown in Table 1. An interlayer filler composition or coating solution was prepared.
When this interlayer filler composition or coating solution is applied onto a semiconductor chip shown in Table 1 with a dropper and does not contain an organic solvent, it is B-staged (semi-cured) under the conditions shown in Table 1 and organic In the case of containing a solvent, after heating at 60 ° C. for 15 minutes, then at 80 ° C. for 15 minutes, then at 120 ° C. for 30 minutes to form an A stage (solvent evaporation), Staged, cooled to room temperature after B-stage.
When the tackiness of the obtained B-stage film was evaluated, no tackiness was confirmed in all cases.
Thereafter, the chip on which the B stage film was placed was pressed against the glass substrate using a flip chip bonder, and then the chip was heated to 250 ° C., held at 250 ° C. for 30 seconds, and then cooled to room temperature. This sample was observed from the glass substrate side using an optical microscope, and the presence or absence of voids around the solder bumps and the fluidity of the solder were evaluated. In all cases, no voids were observed, and the solder was melted. Deformation of solder was observed.
From this result, it was confirmed that the interlayer filler composition of the present invention achieves both suppression of voids and solder bonding at the time of semiconductor chip-substrate bonding.
These results are summarized in Table 1.

  The present invention provides an interlayer filler composition for a three-dimensional stacked semiconductor device that can achieve both void reduction and solder bonding. The three-dimensional stacked semiconductor device using the interlayer filler composition of the present invention is excellent in reliability and is expected to contribute to higher speed and higher capacity of semiconductor devices.

Claims (7)

  A compound having at least an epoxy resin (A) and a curing agent (B), the curing agent (B) having a primary amino group, a compound having a secondary amino group, a compound having an acid anhydride, and a compound having a phenolic hydroxyl group And an interlayer filler composition for a three-dimensional stacked semiconductor device, which is one or more selected from the group consisting of dicyandiamide.   The interlayer filler composition for a three-dimensional stacked semiconductor device according to claim 1, further comprising a curing accelerator (C).   The interlayer filler composition for a three-dimensional stacked semiconductor device according to claim 2, wherein the curing accelerator (C) is an imidazole compound.   An interlayer filler composition coating liquid for a three-dimensional stacked semiconductor device, wherein the interlayer filler composition according to any one of claims 1 to 3 further contains an organic solvent (D).   A cured interlayer filler for a three-dimensional stacked semiconductor device, wherein the interlayer filler composition according to any one of claims 1 to 3 is cured.   A three-dimensional laminate type characterized in that after the interlayer filler composition coating solution according to claim 4 is applied on a chip, B-stage is performed to reduce tackiness at room temperature, and then chip bonding is performed. A method for manufacturing a semiconductor device.   A three-dimensional stacked semiconductor device comprising the cured interlayer filler according to claim 5.