KR20230115846A - Molded underfill composition for tsv - Google Patents

Abstract

The present invention provides a cured product that exhibits good injectability and results in an electronic component that does not cause a short circuit in the bias HAST test, and provides sufficient reliability to electronic components including high-density wiring formed by techniques such as TSV. An object of the present invention is to provide a liquid epoxy resin composition that can be applied.
The mold underfill composition for TSV of the present invention includes (A) an epoxy resin, (B) a curing agent, (C) a filler, and (D) carbon black, and the (A) epoxy resin includes a specific aliphatic epoxy resin, The (C) filler has a specific particle size distribution, and the contents of the carbon black and chloride ion (Cl ⁻ ) are within a predetermined range. The mold underfill composition for TSV of the present invention exhibits good injectability. In addition, the electronic component containing the cured product obtained by curing the mold underfill composition for TSV of the present invention does not cause a short circuit over a long period of time in a bias HAST test conducted under predetermined conditions. Therefore, if the mold underfill composition for TSV of the present invention is used, it is possible to efficiently manufacture electronic parts including high-density wiring formed by TSV or the like technique, and to impart sufficient reliability to such electronic parts. can

Description

Mold underfill composition for TSV {MOLDED UNDERFILL COMPOSITION FOR TSV}

The present invention relates to a liquid epoxy resin composition suitable for use as a mold underfill composition for TSV.

In recent years, in order to further enhance the performance of electronic devices, it is required to increase the density of wiring on chips in electronic parts constituting electronic devices. However, increasing the wiring density per unit area of the chip by further miniaturizing the wiring is approaching the limit. Therefore, it has become common to further increase the wiring density per chip unit area by three-dimensionally stacking a plurality of chips (see Patent Document 2, for example).

In such a technique, connections between stacked chips are required. For such a connection, through-silicon via (TSV) technology is increasingly employed. The TSV technology is a technology in which electrodes are provided that pass through semiconductor chips made of silicon in the thickness direction, and connections between the stacked chips are performed by these electrodes.

In the manufacture of an electronic component including such a plurality of stacked chips, conventionally, each time each chip is stacked, sealing is performed between the wafer and the chip or between the chips, and then the entire stacked chip is sealed in a liquid state. A process of molding (overmolding) the outer shape of an electronic component by covering it with a curable resin composition and subjecting it to compression molding for each chip has been used. However, in recent years, in order to improve manufacturing efficiency, after all the chips are stacked without sealing, the entire stacked chips are covered with a liquid curable resin composition and each chip is subjected to compression molding, so that between the wafer and the chip and between each chip. The technique of performing the sealing of the electronic component and the molding of the outer shape of the electronic component in one step is increasingly used. A curable resin composition used in such a technique is called a mold underfill composition for TSV or a mold underfill material for TSV (see Patent Document 1, for example). As a mold underfill composition for TSV, a liquid epoxy resin composition is mainly used.

Such mold underfill compositions sometimes contain fillers and/or colorants. The former is mainly added for the purpose of reducing the thermal expansion coefficient of the cured product provided by the mold underfill composition and improving the strength. The latter is added to reduce the influence of light on wiring in electronic components, but there are cases where the former is added in combination with the latter to assist the function of the latter (for example, see Patent Literatures 4 and 5).

Patent Document 1: Specification of International Patent Publication No. WO2019/146617 Patent Document 2: Japanese Patent Laid-Open No. 2010-074120 Patent Document 3: Japanese Patent Laid-Open No. 2-88629 Patent Document 4: Japanese Patent Laid-Open No. 2020-015873 Patent Document 5: Japanese Patent 5579764

However, it has been found that the reliability of an electronic component manufactured by using a conventional liquid epoxy resin composition as a mold underfill composition for TSV is low.

Various reliability tests of electronic components are known, but one of them is conducted under high temperature and high humidity conditions (e.g., 130°C, 85% relative humidity) where corrosion of the inside of electronic components (particularly, metal parts) is accelerated. There is a high-speed accelerated life test (HAST test), which is a reliability test. The HAST test includes one conducted under conditions in which no bias voltage is applied to the electronic component to be tested (HAST test without applying bias), and one conducted under conditions where bias voltage is applied (bias HAST test). Reliability test of electronic components manufactured by a technique in which a conventional liquid epoxy resin composition is used as a mold underfill composition for TSV, and sealing between wafers and chips and between chips and forming the outer shape of electronic components are performed in one process In particular, when subjected to a bias HAST test, it was found that a short circuit easily occurs in a short time. Such a problem has not been known in the past, and was discovered for the first time by the present inventors.

In order to solve the problems of the prior art, the present invention provides a cured product that exhibits good injectability and results in electronic components that do not cause short circuits in the bias HAST test, and provides a high-density product formed by techniques such as TSV. An object of the present invention is to provide a liquid epoxy resin composition suitable for use as a mold underfill composition for TSVs, which enables efficient production of electronic parts including wiring and can impart sufficient reliability to such electronic parts.

The inventors of the present invention have reached the present invention as a result of intensive studies to solve the above problems.

That is, the present invention is not limited to the following, but includes the following inventions.

1. As a mold underfill composition for TSV, the following (A) to (D):

(A) an epoxy resin;

(B) a curing agent;

(C) filler; and

(D) carbon black

including,

[In the formula, n is an integer of 1 to 15.]

Including an aliphatic epoxy resin represented by

The (C) filler includes a filler having an average particle diameter of 0.1 μm to 1.0 μm,

When the mass of the epoxy resin (A) is 100 parts by mass, the content of the carbon black (D) is 0.1 parts by mass or more and 1.5 parts by mass or less, and

The mold underfill composition for TSV, wherein the content of chloride ions (C1 ⁻ ) is 0.1 ppm or more and less than 11.0 ppm with respect to the total mass of the mold underfill composition for TSV.

2. (C) The mold underfill composition for TSV according to 1 above, wherein the content of particles having a particle size larger than 1 μm in the (C) filler is less than 1.0 parts by mass, when the total mass of the filler is 100 parts by mass.

3. The mold underfill composition for TSV according to 1 or 2 above, wherein the content of (C) the filler is 65 to 90 parts by mass, when the total mass of the mold underfill composition for TSV is 100 parts by mass.

4. (A) The mold underfill composition for TSV according to any one of items 1 to 3, wherein the epoxy resin further contains an epoxy resin having an aromatic ring in its molecule.

5. (B) The mold underfill composition for TSV according to any one of items 1 to 4, wherein the curing agent contains at least one selected from the group consisting of phenolic compounds, acid anhydrides, acyclic amine compounds, and nitrogen-containing heterocyclic compounds. .

6. (E) The mold underfill composition for TSV according to any one of items 1 to 5, further comprising a silicone additive.

7. (F) The mold underfill composition for TSV according to any one of items 1 to 6 further comprising a coupling agent.

8. (G) The mold underfill composition for TSV according to any one of items 1 to 7, further comprising a migration inhibitor.

9. The mold underfill composition for TSV according to any one of 1 to 8 above, wherein the content of particles having a particle size larger than 1 µm is less than 1.0 parts by mass, when the total mass of the mold underfill composition for TSV is 100 parts by mass.

10. A semiconductor package having a semiconductor element sealed with the mold underfill composition for TSV according to any one of 1 to 9 above.

The mold underfill composition for TSV of the present invention exhibits good injectability and appropriate sealing properties. In addition, electronic parts containing a cured product obtained by curing the mold underfill composition for TSV of the present invention do not cause a short circuit over a long period of time in the bias HAST test. Therefore, when the mold underfill composition for TSV of the present invention is used, sufficient reliability can be imparted to electronic components including high-density wiring formed by TSV or the like technique.

1 is a diagram showing the sequence of sealing and overmolding using a mold underfill composition for TSV.
2 is a schematic view showing positions of a silicon wafer, a silicon chip, and a spacer used to evaluate the injectability of a mold underfill composition for TSV. (A) is a schematic diagram showing the position of a silicon chip placed on a silicon wafer. (B) is a schematic diagram showing the positions of silicon chips and spacers on a silicon wafer.
3 is a photomicrograph showing evaluation results of injectability of a mold underfill composition for TSV. (A) is a photomicrograph of the polished surface of a test piece prepared using the mold underfill composition for TSV with insufficient injectability. (B) is a photomicrograph of the polished surface of a test piece prepared using a mold underfill composition for TSV having good injectability.
4 is a schematic diagram showing the shape of a comb-shaped electrode used in the bias HAST test.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

The present invention relates to the following (A) to (D):

(A) an epoxy resin;

(B) a curing agent;

(C) filler; and

(D) carbon black

It relates to a mold underfill composition for TSV comprising a. In this composition,

[In the formula, n is an integer of 1 to 15.]

It includes an aliphatic epoxy resin represented by The (C) filler includes a filler having an average particle diameter of 0.1 μm to 1.0 μm. When the mass of the epoxy resin (A) is 100 parts by mass, the content of the carbon black (D) is 0.1 part by mass or more and 1.5 parts by mass or less. In addition, the content of chloride ions (C1 ^- ) is 0.1 ppm or more and less than 11.0 ppm with respect to the total mass of the mold underfill composition for TSV. The components (A) to (D) contained in the mold underfill composition for TSV of the present invention are described below.

(A) Epoxy resin

The mold underfill composition for TSV of the present invention contains an epoxy resin. As the epoxy resin, it is preferable to use a liquid epoxy resin at room temperature. In addition, it is preferable to use a liquid epoxy resin having a viscosity within a range of 10 to 5000 mPa·s. By using a liquid epoxy resin, a mold underfill composition for TSV having low viscosity and excellent fluidity can be obtained.

Further, in the mold underfill composition for TSV of the present invention, the content of the epoxy resin is preferably 10 to 35 parts by mass, more preferably 12 to 32 parts by mass, based on 100 parts by mass of the total mass of the mold underfill composition for TSV. And it is especially preferable that it is 15-30 mass parts. By setting it within this range, the increase in the viscosity of the mold underfill composition for TSV can be suppressed, and the coefficient of thermal expansion of the cured product of the mold underfill composition for TSV can be reduced.

[In the formula, n is an integer of 1 to 15.]

An aliphatic epoxy resin (diglycidyl ether of (poly)tetramethylene glycol) represented by . n in this aliphatic epoxy resin can be calculated from the molecular weight of the same epoxy resin (number average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent). By including this aliphatic epoxy resin, the occurrence of warpage after the mold underfill composition for TSV applied to the wafer on which the semiconductor chip is mounted is cured can be suppressed.

As the aliphatic epoxy resin represented by the above formula (I), commercially available products such as "YX7400" (manufactured by Mitsubishi Chemical Corporation) and "Epogosei PT (general grade)" (manufactured by Yokkaichi Chemical Co., Ltd.) may be used.

In the mold underfill composition for TSV of the present invention, the epoxy resin may contain other epoxy resins in addition to the aliphatic epoxy resin represented by the formula (I). As another epoxy resin, an epoxy resin used as a sealing material can be used. It is preferable that this epoxy resin is a bifunctional or more multifunctional epoxy resin. As an example of a multifunctional epoxy resin,

monocyclic aromatic epoxy resins such as catechol diglycidyl ether, resorcinol diglycidyl ether, phthalic acid diglycidyl ester, 2,5-diisopropylhydroquinone diglycidyl ether, and hydroquinone diglycidyl ether;

3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexylcarboxylate, alicyclic epoxy resins such as bis(3,4-epoxycyclohexyl) adipate, vinylcyclohexene monoepoxide, and diepoxylimonene;

bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD type, and bisphenol S type;

a mixture of oligomers obtained by partial polymerization of a bisphenol type epoxy resin;

bisphenol-type epoxy resins in which rings were hydrogenated;

tetramethylbis(4-hydroxyphenyl)methane diglycidyl ether; tetramethylbis(4-hydroxyphenyl)ether diglycidyl ether;

biphenyl type or tetramethylbiphenyl type epoxy resins and resins in which rings thereof have been hydrogenated;

fluorene type epoxy resins such as bisphenol fluorene type epoxy resins and biscresol fluorene type epoxy resins;

A naphthalene type epoxy resin etc. are mentioned.

Moreover, as a polyfunctional epoxy resin, for example,

Aminophenol type epoxy resins such as triglycidyl-ρ-aminophenol, aniline type epoxy resins such as diglycidylaniline, toluidine type epoxy resins such as diglycidyl orthotoluidine, tetraglycidyldiaminodiphenylmethane polyfunctional glycidylamine type epoxy resins such as diaminodiphenylmethane type epoxy resins and the like;

Dicyclopentadiene type epoxy resin;

and polyfunctional glycidyl ethers such as trimethylol alkane type epoxy resins such as trimethylolpropane triglycidyl ether, trimethylolmethane triglycidyl ether, and trimethylolethane triglycidyl ether.

In addition, other epoxy resins such as aliphatic epoxy resins, silylated epoxy resins, heterocyclic epoxy resins, diallyl bisphenol A type epoxy resins, polyarylene ether diglycidyl ether and the like can also be used in combination.

In the mold underfill composition for TSV of the present invention, these epoxy resins may be used alone or in combination of two or more.

It is preferable that the said other epoxy resin is an epoxy resin which has an aromatic ring in a molecule|numerator. In one embodiment of the present invention, the epoxy resin further includes an epoxy resin having an aromatic ring in its molecule in addition to the aliphatic epoxy resin represented by the formula (I). By using an epoxy resin having an aromatic ring in the molecule, the curability of the mold underfill composition for TSV is improved, and the heat resistance is improved, resulting in good bias HAST test results.

In addition, the mass ratio of the aliphatic epoxy resin represented by the formula (I) and the epoxy resin having an aromatic ring is preferably 5:95 to 50:50, more preferably 10:90 to 45:55, and 20:80 to 40 :60 is particularly preferred. By setting the above mass ratio within this range, the occurrence of warpage after curing of the mold underfill composition for TSV applied to the wafer on which the semiconductor chip is mounted is suppressed, and good bias HAST test results can be obtained.

As the epoxy compound having an aromatic ring in the molecule, a known or commonly used aromatic epoxy compound can be used, and is not particularly limited.

As specific examples of the epoxy compound having an aromatic ring in the molecule,

glycidyl ethers of phenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, catechol, and resorcinol;

ρ-glycidyl ether esters of hydroxycarboxylic acids such as hydroxybenzoic acid;

monoglycidyl esters or polyglycidyl esters of carboxylic acids such as benzoic acid, phthalic acid, and terephthalic acid;

glycidyl amine type epoxy compounds such as diglycidyl aniline, diglycidyl toluidine, triglycidyl-ρ-aminophenol, and tetraglycidyl-m-xylenediamine;

Epoxy compounds having a naphthalene skeleton, such as glycidyl esters of naphthol and glycidyl ether esters such as β-hydroxynaphthoic acid, are exemplified. Moreover, you may use the novolak compound which made phenols, such as phenol, catechol, resorcinol, etc. into a novolak. Among these, a glycidylamine type epoxy compound is preferable.

(B) curing agent

The mold underfill composition for TSV of the present invention contains a curing agent. This curing agent is not particularly limited as long as it can cure the above (A) epoxy resin. Examples of curing agents that can be used in the mold underfill composition for TSV of the present invention include phenolic compounds, acid anhydrides, amine compounds (especially non-cyclic amine compounds), nitrogen-containing heterocyclic compounds (especially imidazole compounds), phosphorus compounds, and organic compounds. A metal compound etc. are mentioned. In a certain aspect, a basic thing is used among these.

As an example of the phenolic compound, a novolak resin obtained by condensing a phenol resin, particularly phenols or naphthols (for example, phenol, cresol, naphthol, alkyl phenol, bisphenol, terpene phenol, etc.) with formaldehyde is preferably used. . Examples of novolak resins include phenol novolac resin, ο-cresol novolac resin, ρ-cresol novolak resin, α-naphthol novolak resin, β-naphthol novolak resin, t-butylphenol novolac resin, bisphenol A type Novolak resins, xylene-modified novolac resins, decalin-modified novolak resins, and the like are exemplified. Examples of other phenolic resins include dicyclopentadienecresol resin, polyparavinylphenol, poly(di-ο-hydroxyphenyl)methane, poly(di-m-hydroxyphenyl)methane, and poly(di-ρ-hydroxy phenyl) methane; and the like.

Examples of the acid anhydride include phthalic anhydride; hexahydrophthalic anhydride; Alkylhexahydrophthalic anhydride such as methylhexahydrophthalic anhydride; tetrahydrophthalic anhydride; Alkyl tetrahydrophthalic anhydride such as trialkyltetrahydrophthalic anhydride and 3-methyltetrahydrophthalic anhydride; hymic acid anhydride; anhydrous succinic acid; trimellitic anhydride; Anhydrous pyromellitic acid etc. are mentioned. Among these, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. are preferable.

Examples of the (non-cyclic) amine compound include 2,4,6-tris(dimethylaminomethyl)phenol, diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, tetramethyldiaminodiphenylmethane, Tetraethyldiaminodiphenylmethane, diethyldimethyldiaminodiphenylmethane, dimethyldiaminotoluene, diaminodibutyltoluene, diaminodipropyltoluene, diaminodiphenylsulfone, diaminoditolylsulfone, diethyldiamino toluene, bis(4-amino-3-ethylphenyl)methane, polytetramethylene oxide-di-ρ-aminobenzoate, and 4,4-dimethylaminopyridine; and the like. The amine compound may be an amine adduct.

Examples of nitrogen-containing heterocyclic compounds include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-heptadecylimidazole. -Phenyl-4-methylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2-phenyl-4,5-dihydride imidazoles such as oxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2,3-dihydro-1H-pyrrolo[1,2-a]benzoimidazole; Diazabicycloundecene (DBU), DBU-phenol salt, DBU-octylate, DVU-ρ-toluenesulfonate, DBU-formate, DBU-orthophthalate, DBU-phenol novolak resin salt, DVU-based tetraphenyl Borate salt, diazabicyclononene (DBN), DBN-phenol novolak resin salt, diazabicyclooctane, pyrazole, oxazole, thiazole, imidazoline, pyrazine, morpholine, thiazine, indole, isoindole, Benzoimidazole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, etc. are mentioned. As the nitrogen-containing heterocyclic compound, one forming an adduct with an epoxy resin or an isocyanate compound or a microencapsulated compound can be used.

Examples of the phosphorus compound include trialkylphosphine compounds such as tributylphosphine and triarylphosphine compounds such as triphenylphosphine.

Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonatocobalt (II) and trisacetylacetonatocobalt (III).

In the present invention, the curing agent preferably contains at least one selected from the group consisting of phenol compounds, acid anhydrides, non-cyclic amine compounds and nitrogen-containing heterocyclic compounds, and more preferably contains nitrogen-containing heterocyclic compounds do. The nitrogen-containing heterocyclic compound may be latent, and a microcapsule type latent curing agent can also be used.

The nitrogen-containing heterocyclic compound is particularly preferably an imidazole compound. Examples of imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 1-isobutyl 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole. Sol, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl- 2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole 2-substituted imidazole compounds such as the like; trimellitates such as 1-cyanoethyl-2-undecylimidazolium trimellitate and 1-cyanoethyl-2-phenylimidazolium trimellitate; 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, etc. triazine compounds; Isocyanuric acid adduct of 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, isocyanuric acid adduct of 2-phenylimidazole, Isocyanuric acid adducts of 2-methylimidazole, isocyanuric acid adducts of 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethyl An isocyanuric acid adduct of midazole, etc. are mentioned.

As the microcapsule type curing agent, for example, a dispersion in which powder of an amine compound (including a nitrogen-containing heterocyclic compound) is dispersed in a liquid epoxy resin can be used. The amine compound is selected from, for example, aliphatic primary amines, alicyclic primary amines, aromatic primary amines, aliphatic secondary amines, alicyclic secondary amines, aromatic secondary amines, imidazole compounds and imidazoline compounds. good to do This amine compound may be used in the form of a reaction product with carboxylic acid, sulfonic acid, isocyanate, epoxide or the like. These compounds may be used independently or may use 2 or more types together. For example, the amine compound may be used in combination with a reaction product of the carboxylic acid, sulfonic acid, isocyanate, or epoxide. The volume average particle diameter of the powder of the amine compound is preferably 50 μm or less, and more preferably 10 μm or less. In addition, the powder of the amine compound preferably has a melting point or softening point of 60°C or higher from the viewpoint of suppressing the thickening at 25°C.

In the mold underfill composition for TSV of the present invention, the curing agent may be used alone or in combination of two or more. In this invention, it is preferable that a hardening|curing agent is an imidazole compound, and it is more preferable to use an imidazole compound and a phenol compound together. Sclerosis|hardenability can be improved, improving storage stability by using an imidazole compound and a phenol compound together.

In the mold underfill composition for TSV of the present invention, the content of the curing agent is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and preferably 3 to 10% by mass, based on (A) the epoxy resin. particularly preferred. By setting this range, the curing time of the mold underfill composition for TSV does not become excessively long, and the productivity of electronic parts including high-density wiring formed by techniques such as TSV is improved, and the semiconductor chip is applied to the wafer. The occurrence of warpage after curing of the mold underfill composition for TSV is suppressed, and the storage stability of the mold underfill composition for TSV is improved.

(C) filler

The mold underfill composition for TSV of the present invention contains a filler.

Examples of the filler used in the present invention include fillers made of silica (fused silica, crystalline silica, etc.), alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide, boron nitride (BN), glass beads, etc. However, it is not limited to these. However, in the present invention, carbon black is not a filler. In the mold underfill composition for TSV of the present invention, the filler may be used alone or in combination of two or more.

In addition, the filler may be surface treated with a surface treatment agent, for example, a silane coupling agent (which may have a substituent such as a phenyl group, a vinyl group, or a methacryloyl group). By using the surface-treated filler, the viscosity of the mold underfill composition for TSV is reduced, and injectability can be improved.

From the viewpoint of reducing the thermal expansion coefficient of the cured product imparted by the mold underfill composition for TSV of the present invention, it is preferable to use silica powder as a filler, and it is more preferable to use fused silica powder. Examples of the fused silica powder include spherical fused silica powder and crushed fused silica powder. From the viewpoint of the fluidity of the mold underfill composition for TSV, spherical fused silica powder (particularly, particles having high sphericity) It is more preferable to use a) as a filler.

The filler used in the present invention includes a filler having an average particle diameter of 0.1 μm to 1.0 μm, preferably 0.1 μm to 0.6 μm, and more preferably 0.1 μm to 0.3 μm. If the filler does not contain a filler having an average particle diameter of 0.1 μm to 1.0 μm, the mold underfill composition exhibits inadequate viscosity and/or injectability. In addition, the viscosity of the mold underfill composition at 25° C. measured using a rotational viscometer at a rotation speed of 20 rpm is preferably 20 to 400 Pa·s, more preferably 40 to 300 Pa·s, and 60 to 200 Pa·s. is particularly preferred. When the viscosity is within this range, the injectability of the mold underfill composition for TSV is improved, and the outflow of the mold underfill composition for TSV from the mold during compression molding can be suppressed. In this application, "injectability" indicates the degree of ease of filling the mold underfill composition for TSV between a silicon chip and a silicon wafer during compression molding.

The average particle diameter of the filler is obtained as the particle diameter (D ₅₀ ) at 50% of the cumulative volume of the volume particle size distribution. More specifically, the particle size distribution is measured by a laser diffraction scattering type particle size distribution measuring device using a sample randomly selected from the population, and the average particle diameter and the like can be obtained based on this particle size distribution.

In the present invention, from the viewpoint of injectability, when the total mass of the filler is 100 parts by mass, it is particularly preferable that the content of particles having a particle size larger than 1 μm in the filler is less than 1.0 parts by mass. In addition, the mold underfill composition for TSV of the present invention may further contain a filler having an average particle diameter of less than 0.1 μm as an optional component within a range that does not adversely affect the characteristics of the composition.

In the mold underfill composition for TSV of the present invention, the content of the filler is preferably from 65 to 90 parts by mass, more preferably from 68 to 88 parts by mass, based on the total mass of the mold underfill composition for TSV being 100 parts by mass. It is especially preferable that it is -85 mass parts.

(D) carbon black

The mold underfill composition for TSV of the present invention contains carbon black. Considering the possibility that wiring in electronic components is affected by light, the use of carbon black is important. The carbon black is not particularly limited, and those commonly used as the carbon black contained in the epoxy resin composition can be appropriately selected and employed. Examples of such carbon black include acetylene black, furnace black, Ketjen black, channel black, lamp black, and thermal black. These may be used independently and may use 2 or more types together.

In the present invention, carbon black may be used in combination with other black pigments. As another black pigment, a black organic pigment, a mixed color organic pigment, a black inorganic pigment, etc. can be used. Examples of black organic pigments include perylene black and aniline black. Examples of mixed color organic pigments include those obtained by mixing at least two or more pigments selected from red, blue, green, purple, yellow, magenta, cyan, and the like to simulate blackening. Examples of the black inorganic pigment include fine particles of graphite, metals and their oxides (including complex oxides), sulfides, and nitrides. Examples of this metal include titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver.

Further, carbon black may be used in combination with other colorants such as dyes.

In the mold underfill composition for TSV of the present invention, the carbon black content is 0.1 part by mass or more and 1.5 parts by mass or less based on 100 parts by mass of the epoxy resin (A). The carbon black content is preferably 0.1 parts by mass or more and 1.3 parts by mass or less, more preferably 0.1 parts by mass or more and 1.1 parts by mass or less. The carbon black content is preferably 0.01 part by mass or more and 0.60 part by mass or less, more preferably 0.01 part by mass or more and 0.45 part by mass or less, and 0.01 It is more preferable that it is 0.30 mass part or more and 0.30 mass part or less.

When the content of carbon black is less than the above range, there is a fear that light shielding becomes insufficient, and the wiring in the electronic component is affected by light. If the content of carbon black exceeds the above range, an electronic component obtained by packaging a plurality of chips stacked using TSV technology using a mold underfill composition for TSV is liable to short circuit in the bias HAST test. That is, the reliability of such an electronic component deteriorates. It was discovered by the present inventors for the first time that the content of carbon black in the mold underfill composition for TSV affects the reliability of electronic parts manufactured using TSV technology.

Further, in the mold underfill composition for TSV of the present invention, the content of chloride ion (Cl ⁻ ) is 0.1 ppm or more and less than 11.0 ppm with respect to the total mass of the mold underfill composition for TSV. This content is preferably 0.1 ppm or more and less than 10.8 ppm, more preferably 0.1 ppm or more and less than 10.0 ppm, still more preferably 0.1 ppm or more and less than 7.0 ppm. When the chloride ion content is 11.0 ppm or more, an electronic component obtained by packaging a plurality of chips stacked using TSV technology using a mold underfill composition for TSV is liable to short circuit in the bias HAST test. That is, the reliability of such an electronic component deteriorates. On the other hand, from the viewpoint of commercial availability, the chloride ion content is preferably 0.1 ppm or more.

As described above, in the manufacture of electronic components including a plurality of stacked chips, conventionally, each time each chip is stacked, sealing is performed between the wafer and the chip or between the chips, and then overmolding is performed. The process to be carried out was being used. In such a process, a resin composition having a lower chloride ion content than the resin composition used for overmolding was used for sealing.

In contrast, when sealing and overmolding are performed in one process using the mold underfill composition for TSV, the same resin composition must be used for sealing and overmolding. Conventional resin compositions for sealing are unsuitable as mold underfill compositions for TSVs for reasons such as moisture resistance and ion elution resistance. On the other hand, when an electronic component including a plurality of stacked chips is manufactured using a conventional resin composition for overmolding as a mold underfill composition for TSV, the resulting electronic component is prone to short circuit in the bias HAST test. That is, such an electronic component exhibits low reliability.

Under these circumstances, as a result of various investigations, the present inventors have found that, in the mold underfill composition for TSV, when the content of chloride ions in addition to the content of the carbon black is within the above range, a case obtained by curing the mold underfill composition for TSV It has been found that electronic parts containing cargo do not short circuit over a long period of time in the bias HAST test and that the above low reliability is due to an excessively high chloride ion content in the conventional mold underfill composition for TSV. This is the first discovery by the present inventors.

The chloride ion content can be measured by extracting a sample with pure water under high heat and high pressure (for example, 121°C and 2 atmospheres for 20 hours), and analyzing the obtained extract by ion chromatography. However, when it is difficult to measure the content of chloride ions in the mold underfill composition for TSV of the present invention, the chloride ion content measured by the above method for a cured product obtained by curing the mold underfill composition for TSV It is considered equal to the content of

If desired, the mold underfill composition for TSV of the present invention may contain optional components, for example, those described below, as necessary, in addition to the essential components (A) to (D).

(E) silicone-based additives

The mold underfill composition for TSV of the present invention may contain a silicone-based additive, if desired. In one embodiment, the mold underfill composition for TSV of the present invention further includes a silicone-based additive. The inclusion of a silicone-based additive is preferable from the viewpoint of improving the fluidity of the mold underfill composition for TSV. The silicone-based additive is preferably a dialkylpolysiloxane (eg, methyl, ethyl, etc. are exemplified as an alkyl group bonded to Si), particularly dimethylpolysiloxane. Further, the silicone-based additive may be a modified dialkyl polysiloxane such as an epoxy-modified dimethyl polysiloxane. Specific examples of silicone additives include KF69 (dimethyl silicone oil, manufactured by Shin-Etsu Silicone) and SF8421 (epoxy-modified silicone oil, manufactured by Toray Dow Silicone). A silicone type additive may be used independently or may use 2 or more types together.

When the mold underfill composition for TSV of the present invention contains a silicone-based additive, the amount of the silicone-based additive is preferably 0.1 to 1.0 parts by mass, more preferably 0.25 to 1 part by mass, based on 100 parts by mass of the (A) epoxy resin.

(F) Coupling agent

The mold underfill composition for TSV of the present invention may contain a coupling agent, if desired. In one embodiment, the mold underfill composition for TSV of the present invention further includes a coupling agent. It is preferable from a viewpoint of improving adhesive strength that a coupling agent, especially, that a silane coupling agent is contained. As the coupling agent, various silane coupling agents such as epoxy-based, amino-based, vinyl-based, methacrylic-based, acrylic-based, and mercapto-based coupling agents can be used. Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-part Thylidene) propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ρ-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltri Methoxysilane, 8-glycidoxyoctyltrimethoxysilane, 3-ureidpropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanate A propyltriethoxysilane etc. are mentioned. These silane coupling agents may be used independently or may use 2 or more types together.

When the mold underfill composition for TSV of the present invention contains a coupling agent, the amount of the coupling agent is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the (A) epoxy resin.

(G) migration inhibitor

The mold underfill composition for TSV of the present invention may contain a migration inhibitor, if desired. In one embodiment, the mold underfill composition for TSV of the present invention further includes a migration inhibitor. Migration is a phenomenon in which a metal of a wiring pattern elutes by an electrochemical reaction and a decrease in resistance value occurs. Containing a migration inhibitor is preferable from the viewpoint of improving reliability in electronic parts. Specific examples of the migration inhibitor include xanthines such as caffeine, theophylline, theobromine, and paraxanthin; Tocols such as 5,7,8-trimethyltocol (α-tocopherol), 5,8-dimethyltocol (β-tocopherol), 7,8-dimethyltocol (γ-tocopherol), and 8-methyltocol (δ-tocopherol) Ryu; Tocotrienols such as 5,7,8-trimethyltocotrienol (α-tocotrienol), 5,8-dimethyltocotrienol (β-tocotrienol), 7,8-dimethyltocotrienol (γ-tocotrienol), and 8-methyltocotrienol (δ-tocotrienol) Ryu; benzotriazoles such as benzotriazole, 1H-benzotriazole-1-methanol, and alkylbenzotriazoles; 2,4-diamino-6-vinyl-S-triazine, 2,4-diamino-6-[2'-ethyl-4-methylimidazole-(1)]-ethyl-S-triazine, triazines such as 2,4-diamino-6-methacryloyloxyethyl-S-triazine; and isocyanuric acid adducts of the above benzotriazoles or triazines. These migration inhibitors may be used alone or in combination of two or more.

When the mold underfill composition for TSV of the present invention contains a migration inhibitor, the amount of the migration inhibitor is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the (A) epoxy resin.

(H) stabilizer

The mold underfill composition for TSV of the present invention may contain a stabilizer, if desired. A stabilizer may be included in the mold underfill composition for TSV of the present invention to improve its storage stability and lengthen its pot life. Although various known stabilizers can be used as a stabilizer for a one-component adhesive having an epoxy resin as a main agent, it is selected from the group consisting of liquid boric acid ester compounds, aluminum chelates, and organic acids in view of the excellent effect of improving storage stability. At least one is preferred.

Examples of liquid boric acid ester compounds include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, and triisopropyl. Borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, triocta Decylborate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4, 7-trioxaundecyl) borane, tribenzyl borate, triphenyl borate, tri-ο-tolyl borate, tri-m-tolyl borate, triethanolamine borate and the like. Since the liquid boric acid ester compound is liquid at room temperature (25° C.), it is preferable because it can suppress the viscosity of the mold underfill composition for TSV to a low level. As an aluminum chelate, aluminum chelate A can be used, for example. As an organic acid, barubituric acid can be used, for example.

When a stabilizer is included, the amount of the stabilizer is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 25 parts by mass, and still more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the (A) epoxy resin.

(I) other additives

The mold underfill composition for TSV of the present invention, if desired, other additives such as ion trapping agents, leveling agents, antioxidants, antifoaming agents, thixotropic agents, viscosity agents, etc. It may contain an adjusting agent, a flame retardant, a solvent, etc. The type and amount of each additive are as per the usual method.

Further, in the mold underfill composition for TSV of the present invention, one or more of the components (including components (A) to (D)) included therein may exist as fine particulate solids. In the present invention, from the viewpoint of injectability, when the total mass of the mold underfill composition for TSV is 100 parts by mass, the content of particles having a particle size larger than 1 μm is preferably less than 1.0 parts by mass.

The method for preparing the mold underfill composition for TSV of the present invention is not particularly limited. For example, components (A) to (D) and other components, if desired, are simultaneously or separately introduced into an appropriate mixer, and, if necessary, stirred and mixed while melting by heating to obtain a uniform composition, thereby forming the composition of the present invention. A mold underfill composition for TSV can be obtained. Although this mixer is not particularly limited, a mortar machine equipped with a stirring device and a heating device, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc. can be used. there is. Moreover, you may use these apparatuses combining suitably.

The thus-obtained mold underfill composition for TSV is thermosetting, and is cured preferably in 0.1 to 3 hours, more preferably in 0.25 to 2 hours under conditions of a temperature of 100 to 170°C.

The composition of the present invention can be used, for example, as an adhesive, a sealing material, or a raw material for fixing, bonding, or protecting semiconductor devices including various electronic components or components constituting electronic components. The composition of the present invention is an underfill material for protecting electronic components or the like or fixing them to a substrate, in particular, sealing between wafers and chips and between each chip and used in a technique for molding the outer shape of electronic components in one process. It is suitable as a mold underfill composition for TSV. As an example of an electronic component manufacturing process by such a technique, a compression molding process is shown in FIG. 1 . A wafer (FIG. 1(A)) loaded with a plurality of stacked semiconductor chips is placed in a compression molding apparatus equipped with a mold, and a mold underfill composition for TSV is applied to the wafer (FIG. 1(B)). This wafer is subjected to compression molding under heating, and then the mold underfill composition is cured by heating (FIG. 1(C)). Through such a process, it is possible to achieve sealing between wafers and chips on which semiconductor chips are mounted and between chips and forming the outer shape of electronic components in one process.

Further, in the present invention, a cured product obtained by curing the mold underfill composition for TSV of the present invention is also provided. In the present invention, an electronic component containing the cured product of the present invention is further provided.

In the present invention, a semiconductor element sealed with the mold underfill composition for TSV of the present invention is also provided. In the present invention, a semiconductor package having a semiconductor element sealed with the mold underfill composition for TSV of the present invention is also provided.

(Example)

Hereinafter, the present invention will be described by examples, but the present invention is not limited thereto. In addition, in the description below, parts and % represent parts by mass and % by mass, unless otherwise specified.

Examples 1 to 6, Comparative Examples 1 to 5

According to the formulation shown in Table 1, a resin composition was prepared by mixing each component in a predetermined amount using a three roll mill. In Table 1, the amount of each component is shown in parts by mass (unit: g).

(A) Epoxy resin

In Examples and Comparative Examples, the compounds used as (A) epoxy resins are as follows.

(A-1): Aminophenol type epoxy resin (trade name: jER630, manufactured by Mitsubishi Chemical Corporation) (epoxy resin having an aromatic ring)

(A-2): Aminophenol type epoxy resin (trade name: jER630LSD, manufactured by Mitsubishi Chemical Corporation) (epoxy resin having an aromatic ring)

(A-3): Aliphatic epoxy resin (trade name: YX7400, manufactured by Mitsubishi Chemical Corporation)

(B) curing agent

In Examples and Comparative Examples, the compounds used as the (B) curing agent are as follows.

(B-1): Liquid phenol novolac resin (trade name: MEH-8005, manufactured by Maywa Kasei Co., Ltd.)

(B-2): 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine (trade name: Curesol 2MZ-A, manufactured by Shikoku Kasei Industrial Co., Ltd.)

(C) filler

In Examples and Comparative Examples, the compounds used as (C) fillers are as follows.

(C-1): Silica filler (trade name: SE2200SME, manufactured by Admatax Co., Ltd., average particle diameter: 0.6 µm, maximum particle diameter: 3 µm)

(C-2): Silica filler (trade name: SE1050SMO, manufactured by Admatax Co., Ltd., average particle diameter: 0.3 µm, maximum particle diameter: 1 µm)

(C-3): Silica filler (trade name: Admanano YA050C, manufactured by Admatax Co., Ltd., average particle diameter: 50 nm, surface treated)

(C-4): Silica filler (trade name: SE5200SME, manufactured by Admatax Co., Ltd., average particle diameter: 1.5 µm, maximum particle diameter: 10 µm)

(D) carbon black

In Examples and Comparative Examples, the compounds used as (D) carbon black are as follows.

(D-1): Carbon black (trade name: Special Black 4, manufactured by Orion Engineered Carbons Co., Ltd.)

In Table 1, "(D) carbon black content" shows the quantity (mass part) of (D) carbon black when the mass of (A) epoxy resin is 100 mass parts.

(E) silicone-based additives

In Examples and Comparative Examples, (E) compounds used as silicone-based additives are as follows.

(E-1): Epoxy-modified silicone oil (trade name: SF8421, manufactured by Toray Dow Corning Silicone Co., Ltd.)

(F) Coupling agent

In Examples and Comparative Examples, the compounds used as (F) coupling agents are as follows.

(F-1): 3-glycidoxypropyltrimethoxysilane (trade name: KBM403, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

(G) migration inhibitor

In Examples and Comparative Examples, compounds used as (G) migration inhibitors are as follows.

(G-1): Caffeine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

(I) ion trap agent

In Examples and Comparative Examples, the compounds used as (I) ion trapping agents are as follows.

(I-1): Zr/Bi-based ion trapping agent (trade name: IXE6136, manufactured by Donga Chemical Co., Ltd.)

In Examples and Comparative Examples, the properties of the resin composition and cured product were measured as follows.

(viscosity of composition)

The viscosity (unit: Pa·s) of each prepared resin composition was measured at 25°C and 10 rotations/minute using a Brookfield HB viscometer (using spindle SC4-14). The results are shown in Table 1.

(Gel time of composition)

On a stainless steel plate heated to 120 ± 2 ° C, each prepared resin composition is dropped in a size of about 5 mm Φ, and a metal needle is attached to the resin composition at regular intervals, and the time until the sagging is eliminated (unit: second ) was measured by a stopwatch. In the mold underfill composition for TSV of the present invention, the gel time is preferably 30 to 600 seconds, more preferably 60 to 570 seconds, and particularly preferably 90 to 540 seconds. When the gel time is within this range, injectability defects due to gelation of the mold underfill composition for TSV can be suppressed, and the molding time during compression molding does not become excessively long, so productivity can be improved.

(Evaluation of injectability of mold underfill composition for TSV)

A silicon chip (length: 18 mm, width: 18 mm, thickness: 300 μm) is placed on a silicon wafer (diameter: 300 mm, thickness: 760 μm) through 9 spacers (diameter: 1-2 mm, thickness: 20 μm). loaded The spacers were arranged at equal intervals on the diagonal of the silicon chip (see Fig. 2(B)). In the above manner, four silicon chips were placed at equal intervals near the outer periphery of the silicon wafer (see Fig. 2(A)).

This silicon wafer was placed in a compression molding apparatus (model number: WCM-300, manufactured by Apic Yamada Co., Ltd.) equipped with molds for both silicon chips and spacers. Next, the mold underfill composition for TSV is filled in a mold, compression molding is performed under the conditions of a temperature of 120° C. and a pressure of 250 kN, and then the mold underfill composition for TSV is cured by heating at this temperature for 400 seconds, thereby forming the entire silicon wafer was coated, and a layer of a cured product of a mold underfill composition for TSV having a thickness of 500 μm (in which the silicon chip and the spacer were sealed) was formed.

A sealed product was obtained by cutting a silicon wafer covered with a layer of a cured product taken out of the compression molding apparatus at a position slightly away from the outer edge of the silicon chip. The silicon chip, the cured product, and the spacer were removed from the encapsulated material by plane polishing until the thickness of the layer of the cured material measured from the silicon wafer reached about 10 µm to obtain a test piece for evaluation of injectability.

The polished side of the obtained test piece was observed with the naked eye or under a microscope (magnification: 100 times). When no voids were found in the test piece, or when the maximum width of the voids found in the test piece was less than 100 μm, the injectability was evaluated as ○ (see FIG. 3(B)), and the maximum width of the voids found in the test piece was evaluated. When it was 100 μm or more, the injectability was evaluated as × (see FIG. 3(A)).

(Manufacture of cured product)

Hardened|cured material was obtained by heating each prepared resin composition at 150 degreeC for 1 hour using a dryer.

(Bias HAST test of cured product)

Fig. 4 shows a schematic diagram of a comb-shaped electrode used for evaluation of insulation reliability by the bias HAST test. This comb-shaped electrode consists of a polyimide film substrate (thickness: 38 μm) and patterned copper wiring thereon (wiring width: 15 μm, pitch between lines: 30 μm, thickness: 8 μm, and tin plating (thickness: 0.2±0.05 μm)). ) is made up of The mold underfill composition for TSV was applied to the comb-shaped electrode to a thickness of 150 μm, and the mold underfill composition on the comb-shaped electrode was cured by heating at 150° C. for 1 hour using a dryer to obtain a test piece. This test piece was attached to a HAST device (model number: PC-422R8, manufactured by Hirayama Seisakusho), and the electrical resistance value was continuously monitored under conditions of 85% relative humidity and 130°C temperature, with a bias voltage of 3V applied. and measured the time (unit: hr) from the start of the test until a short circuit occurred (the electrical resistance value became 10 kΩ or less). The results are shown in Table 1. However, if a short circuit does not occur within 168 hours, it is indicated as “Pass”.

(Content of chloride ion (Cl ^- ) in cured product)

A sample obtained by curing the prepared resin composition by heating it at 150°C for 60 minutes was pulverized to about 5 mm square. To 2.5 g of this sample, 25 cm 3 of ion-exchanged water was added, placed in a PCT test tank (EHS-221M, 121°C±2°C/100% humidity/2 atm) in a PCT test vessel, and then cooled to room temperature. The obtained extract was used as a test solution. The chloride ion concentration of the test solution obtained in the above procedure was measured using an ion chromatograph (CLASS-VP manufactured by Shimadzu Corporation, using column IC-A3). Table 1 shows the evaluation results of the chloride ion content.

As is clear from Table 1, (i) (A) the content of (D) carbon black when the mass of the epoxy resin is 100 parts by mass is 0.1 parts by mass or more and 1.5 parts by mass or less, and (ii) chloride ion In any of Examples 1 to 6 in which the content was 0.1 ppm or more and less than 11.0 ppm with respect to the total mass of the mold underfill composition, in the bias HAST test conducted under the above conditions, no short circuit occurred within 168 hours from the start of the test. In addition, in all of these Examples, the mold underfill composition exhibited good injectability.

On the other hand, in Comparative Examples 1 to 3 which do not satisfy either or both of the above requirements (i) and (ii), in the bias HAST test, a short circuit occurred within 168 hours from the start of the test.

Further, (C) In Comparative Example 4 in which the filler did not contain a filler having an average particle diameter of 0.1 μm to 1.0 μm, the mold underfill composition was inferior in injectability. In Comparative Example 5, the injectability of the mold underfill composition was also poor, but this is considered to be because the (I) ion trapping agent contains many particles having a particle diameter of more than 1 µm. Further, in Comparative Example 5, despite an excessive amount of carbon black, no short circuit occurred within 168 hours in the bias HAST test. This is presumed to be because the chloride ion was captured by the (I) ion trapping agent.

The mold underfill composition for TSV of the present invention exhibits good injectability and appropriate sealing properties. In addition, the electronic component containing the cured product obtained by curing the mold underfill composition for TSV of the present invention does not cause a short circuit over a long period of time in the bias HAST test. Therefore, if the mold underfill composition for TSV of the present invention is used, it is possible to efficiently manufacture electronic parts including high-density wiring formed by TSV or the like technique, and to impart sufficient reliability to such electronic parts. can

10: silicon wafer
11: silicon chip
12: bump
13: Mold underfill composition for TSV
14: mold
20: silicon wafer (diameter 300 mm)
21: silicon chip
22: spacer (thickness 20 μm)
23: cured product of mold underfill composition for TSV
30: cured product of mold underfill composition for TSV
31: spacer
32: void

Claims (10)

As a mold underfill composition for TSV, the following (A) to (D):
(A) an epoxy resin;
(B) a curing agent;
(C) filler; and
(D) carbon black
including,

[In the formula, n is an integer of 1 to 15.]
Including an aliphatic epoxy resin represented by
The (C) filler includes a filler having an average particle diameter of 0.1 μm to 1.0 μm,
When the mass of the epoxy resin (A) is 100 parts by mass, the content of the carbon black (D) is 0.1 parts by mass or more and 1.5 parts by mass or less, and
The content of chloride ion (C1 ^- ) is 0.1 ppm or more and less than 11.0 ppm with respect to the total mass of the mold underfill composition for TSV
A mold underfill composition for TSV.
According to claim 1,
(C) When the total mass of the filler is 100 parts by mass, the content of particles having a particle size larger than 1 μm in the (C) filler is less than 1.0 parts by mass
A mold underfill composition for TSV.
According to claim 1 or 2,
When the total mass of the mold underfill composition for TSV is 100 parts by mass, (C) the content of the filler is 65 to 90 parts by mass
A mold underfill composition for TSV.
According to any one of claims 1 to 3,
(A) the epoxy resin further comprises an epoxy resin having an aromatic ring in the molecule
A mold underfill composition for TSV.
According to any one of claims 1 to 4,
(B) The curing agent contains at least one selected from the group consisting of phenol compounds, acid anhydrides, non-cyclic amine compounds, and nitrogen-containing heterocyclic compounds.
A mold underfill composition for TSV.
According to any one of claims 1 to 5,
(E) further comprising a silicone-based additive
A mold underfill composition for TSV.
According to any one of claims 1 to 6,
(F) further comprising a coupling agent
A mold underfill composition for TSV.
According to any one of claims 1 to 7,
(G) further comprising a migration inhibitor
A mold underfill composition for TSV.
According to any one of claims 1 to 8,
When the total mass of the mold underfill composition for TSV is 100 parts by mass, the content of particles having a particle size larger than 1 µm is less than 1.0 parts by mass.
A mold underfill composition for TSV.
Having a semiconductor element sealed with the mold underfill composition for TSV according to any one of claims 1 to 9
semiconductor package.