TSV mold underfill composition

Abstract

To provide a liquid epoxy resin composition which has good injection property, gives a cured product providing an electronic component preventing short circuit in a bias HAST test, and can impart sufficient reliability to an electronic component including high-density wiring formed by a technique such as TSV.SOLUTION: A mold underfill composition for TSV contains (A) an epoxy resin, (B) a curing agent, (C) a filler, and (D) carbon black, in which (A) the epoxy resin contains a specific aliphatic epoxy resin, (C) the filler has specific particle size distribution, and contents of the carbon black and chloride ions (Cl-) are within predetermined ranges. An electronic component including a cured product obtained by curing the mold underfill composition for TSV prevents short circuit for a long time in a bias HAST test performed under a predetermined condition.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a liquid epoxy resin composition suitable for use as a mold underfill composition for TSVs.

Background Art

[0002] In recent years, in order to further improve the performance of electronic devices, there has been a demand to increase the wiring density on chips in electronic components that make up the electronic devices. However, increasing the wiring density per unit area of the chip by further miniaturization of the wiring is approaching its limit. Therefore, it has generally become common to further increase the wiring density per unit area of the chip by three-dimensionally stacking a plurality of chips (see, for example, Patent Document 2).

[0003] In such a technique, connection between the stacked chips is required. In such a connection, the Through Silicon Via (TSV) technology is increasingly being adopted. The TSV technology is a technology in which an electrode that penetrates a silicon semiconductor chip in the thickness direction is provided, and the connection between the stacked chips is made by this electrode.

[0004] In the manufacturing of electronic components containing multiple stacked chips, conventionally, after stacking each chip, sealing was performed between the wafer and the chip, or between the chips themselves. Then, the entire stacked chip assembly was covered with a liquid curable resin composition and subjected to compression molding to form the outer shape of the electronic component (overmolding). However, in recent years, in order to improve manufacturing efficiency, a technique is increasingly being used in which all chips are stacked without sealing, and then the entire stacked chip assembly is covered with a liquid curable resin composition and subjected to compression molding to perform sealing between the wafer and the chips, between each chip, and the formation of the outer shape of the electronic component in a single step. The curable resin composition used in this technique is called a TSV mold underfill composition or TSV mold underfill material (see, for example, Patent Document 1). Liquid epoxy resin compositions are mainly used as TSV mold underfill compositions.

[0005] Such mold underfill compositions often contain fillers and / or colorants. The former are mainly added to reduce the coefficient of thermal expansion and improve the strength of the cured product provided by the mold underfill composition. The latter are added to reduce the effect of light on wiring within electronic components, but the former may also be added in combination with the latter to assist the function of the latter (see, for example, Patent Documents 4 and 5). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Patent Publication No. WO2019 / 146617 [Patent Document 2] Japanese Patent Publication No. 2010-074120 [Patent Document 3] Japanese Patent Publication No. 2-88629 [Patent Document 4] Japanese Patent Publication No. 2020-015873 [Patent Document 5] Patent No. 5579764 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, it has been found that electronic components manufactured using conventional liquid epoxy resin compositions as mold underfill compositions for TSV (Total Smoking Vehicle) applications have low reliability. Various reliability tests for electronic components are known, but one of them is the High-Speed ​​Accelerated Life Test (HAST test), which is a reliability test performed under high temperature and high humidity conditions (e.g., 130°C, 85% relative humidity) that accelerate corrosion of the inside of electronic components (especially metal parts). HAST tests include those performed under conditions where no bias voltage is applied to the electronic component being tested (unbiased HAST test) and those performed under conditions where a bias voltage is applied (biased HAST test). It has been found that electronic components manufactured using a technique in which a conventional liquid epoxy resin composition is used as a mold underfill composition for TSV (Total Smoking Vehicle), and sealing between wafers and chips, and between each chip, as well as forming the outer shape of the electronic component, are prone to short circuits in a short time when subjected to reliability tests, particularly biased HAST tests. This problem was previously unknown and was discovered for the first time by the inventors.

[0008] The present invention aims to provide a liquid epoxy resin composition suitable for use as a mold underfill composition for TSV (Total Stability Vessel) applications, which solves the problems of the prior art described above, provides a cured product that exhibits good injectability and does not cause short circuits in bias HAST tests, enables the efficient manufacture of electronic components including high-density wiring formed by techniques such as TSV, and can provide sufficient reliability to such electronic components. [Means for solving the problem]

[0009] The inventors of this invention arrived at this present invention as a result of diligent research to solve the above problems.

[0010] In other words, the present invention is not limited to the following inventions, but encompasses the following inventions.

[0011] 1. A mold underfill composition for TSV, comprising the following (A) to (D): (A) An epoxy resin; (B) A curing agent; (C) A filler; and (D) Carbon black wherein the (A) epoxy resin contains an aliphatic epoxy resin represented by the following formula (I): [Chemical formula] [In the formula, n is an integer from 1 to 15.] and the (C) filler contains a filler having an average particle diameter of 0.1 μm to 1.0 μm, when the mass of the (A) epoxy resin is 100 parts by mass, the content of the (D) carbon black is 0.1 part by mass or more and 1.5 parts by mass or less, and the content of chloride ions (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. A mold underfill composition for TSV.

[0012] 2. The mold underfill composition for TSV according to item 1 above, wherein when the total mass of the (C) filler is 100 parts by mass, the content of particles having a particle diameter larger than 1 μm in the (C) filler is less than 1.0 part by mass.

[0013] ) 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. 3. The mold underfill composition for TSV according to item 1 or 2 above, wherein when the total mass of the mold underfill composition for TSV is 100 parts by mass, the content of the (C) filler is 65 to 90 parts by mass.

[0014] 4. The mold underfill composition for TSV according to any one of items 1 to 3 above, wherein the (A) epoxy resin further contains an epoxy resin having an aromatic ring in the molecule.

[0015] 5. (B) The mold underfill composition for TSV according to any one of the preceding items 1 to 4, wherein the hardener contains at least one selected from the group consisting of a phenolic compound, an acid anhydride, an acyclic amine compound, and a nitrogen-containing heterocyclic compound.

[0016] 6. (E) The mold underfill composition for TSV according to any one of the preceding items 1 to 5, further containing a silicone-based additive.

[0017] 7. (F) The mold underfill composition for TSV according to any one of the preceding items 1 to 6, further containing a coupling agent.

[0018] 8. (G) The mold underfill composition for TSV according to any one of the preceding items 1 to 7, further containing a migration inhibitor.

[0019] 9. 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 part by mass. The mold underfill composition for TSV according to any one of the preceding items 1 to 8.

[0020] 10. A semiconductor package having a semiconductor element sealed with the mold underfill composition for TSV according to any one of the preceding items 1 to 9.

Advantages of the Invention

[0021] The mold underfill composition for TSV of the present invention exhibits good injectability and appropriate sealing properties. Further, an electronic component including a 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. Therefore, when the mold underfill composition for TSV of the present invention is used, sufficient reliability can be imparted to an electronic component including a high-density wiring formed by a technique such as TSV.

Brief Description of the Drawings

[0022] [Figure 1]This figure shows the procedure for sealing and overmolding using a mold underfill composition for TSVs. [Figure 2] These are schematic diagrams showing the positions of the silicon wafer, silicon chips, and spacers used to evaluate the injection properties of the TSV mold underfill composition. (A) A schematic diagram showing the position of the silicon chips placed on the silicon wafer. (B) A schematic diagram showing the positions of the silicon chips and spacers on the silicon wafer. [Figure 3] These are micrographs showing the results of the evaluation of the injectability of TSV mold underfill compositions. (A) Micrograph of the polished surface of a test specimen prepared using a TSV mold underfill composition with insufficient injectability. (B) Micrograph of the polished surface of a test specimen prepared using a TSV mold underfill composition with good injectability. [Figure 4] This is a schematic diagram showing the shape of the comb-shaped electrode used in the bias HAST test. [Modes for carrying out the invention]

[0023] Embodiments of the present invention will be described in detail below. The present invention relates to the following (A) to (D): (A) Epoxy resin; (B) Hardener; (C) Filler; and (D) Carbon Black The present invention relates to a mold underfill composition for TSVs containing the following: In this composition, the epoxy resin (A) is the following formula (I): [ka] [In the formula, n is an integer between 1 and 15.] It contains an aliphatic epoxy resin as shown. The (C) filler contains fillers with an average particle size of 0.1 μm to 1.0 μm. When the mass of the (A) epoxy resin is 100 parts by mass, the content of the (D) carbon black is 0.1 parts by mass or more and 1.5 parts by mass or less. Also contains chloride ions (Cl- The content of ) is 0.1 ppm or more and less than 11.0 ppm relative to the total mass of the TSV mold underfill composition. The above components (A) to (D) contained in the TSV mold underfill composition of the present invention will be described below.

[0024] (A) Epoxy resin The TSV mold underfill composition of the present invention contains an epoxy resin. It is preferable to use an epoxy resin that is liquid at room temperature. Furthermore, it is preferable to use a liquid epoxy resin with a viscosity in the range of 10 to 5000 mPa·s. By using a liquid epoxy resin, a TSV mold underfill composition with low viscosity and excellent fluidity can be obtained. Furthermore, in the TSV mold underfill composition of the present invention, the epoxy resin content is preferably 10 to 35 parts by mass, more preferably 12 to 32 parts by mass, and particularly preferably 15 to 30 parts by mass, when the total mass of the TSV mold underfill composition is 100 parts by mass. By keeping the content within this range, it is possible to suppress the increase in viscosity of the TSV mold underfill composition and to reduce the thermal expansion coefficient of the cured product of the TSV mold underfill composition. This epoxy resin is based on the following formula (I): [ka] [In the formula, n is an integer between 1 and 15.] The material contains an aliphatic epoxy resin ((poly)tetramethylene glycol diglycidyl ether). In this aliphatic epoxy resin, n can be calculated from the molecular weight of the epoxy resin (number-average molecular weight in terms of standard polystyrene, obtained by gel permeation chromatography (GPC) using tetrahydrofuran as the elution solvent). By including this aliphatic epoxy resin, the occurrence of warping after curing of the TSV mold underfill composition applied to a wafer on which a semiconductor chip is mounted can be suppressed.

[0025] As the aliphatic epoxy resin represented by formula (I) above, commercially available products such as "YX7400" (manufactured by Mitsubishi Chemical Corporation) and "Epogose PT (general grade)" (manufactured by Yokkaichi Gosei Co., Ltd.) may be used.

[0026] In the TSV mold underfill composition of the present invention, the epoxy resin may include, in addition to the aliphatic epoxy resin represented by formula (I), other epoxy resins. As the other epoxy resin, epoxy resins used as encapsulating materials can be used. This epoxy resin is preferably a bifunctional or polyfunctional epoxy resin. Examples of polyfunctional epoxy resins include: Monocyclic aromatic epoxy resins such as catechol diglycidyl ether, resorcinol diglycidyl ether, diglycidyl phthalate ester, 2,5-diisopropylhydroquinone diglycidyl ether, and hydroquinone diglycidyl ether; Alicyclic epoxy resins such as 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexylcarboxylate, bis(3,4-epoxycyclohexyl) adipate, vinylcyclohexene monoepoxide, and diepoxylimonene; Bisphenol-type epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, and bisphenol S; A mixture of oligomers obtained by partial polymerization of bisphenol-type epoxy resins; A bisphenol-type epoxy resin with a hydrogenated ring; Tetramethylbis(4-hydroxyphenyl)methane diglycidyl ether; Tetramethylbis(4-hydroxyphenyl) ether diglycidyl ether; Biphenyl-type or tetramethylbiphenyl-type epoxy resins and resins in which these rings are hydrogenated; Fluorene-type epoxy resins such as bisphenol fluorene-type epoxy resins and biscresol fluorene-type epoxy resins; Naphthalene-type epoxy resin Examples include:

[0027] Furthermore, examples of polyfunctional epoxy resins include, Polyfunctional glycidylamine epoxy resins such as aminophenol-type epoxy resins including triglycidyl-p-aminophenol, aniline-type epoxy resins including diglycidylaniline, toluidine-type epoxy resins including diglycidylorthotoluidine, and diaminodiphenylmethane-type epoxy resins including tetraglycidyldiaminodiphenylmethane; Dicyclopentadiene type epoxy resin; Polyfunctional glycidyl ethers such as trimethylolpropane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, and other trimethylolalkane type epoxy resins. These are some examples.

[0028] Furthermore, other epoxy resins, such as aliphatic epoxy resins, silylated epoxy resins, heterocyclic epoxy resins, diallylbisphenol A type epoxy resins, and polyarylene ether diglycidyl ethers, can also be used in combination. In the TSV mold underfill composition of the present invention, these epoxy resins may be used individually or in combination of two or more.

[0029] The other epoxy resins mentioned above are preferably epoxy resins having aromatic rings in their molecules. In one embodiment of the present invention, the epoxy resin further comprises an epoxy resin having aromatic rings in its molecule in addition to the aliphatic epoxy resin represented by formula (I). By using an epoxy resin having aromatic rings in its molecule, the curability of the TSV mold underfill composition is improved, and the heat resistance is improved, resulting in better bias HAST test results. Furthermore, the mass ratio of the aliphatic epoxy resin represented by formula (I) to the epoxy resin having an aromatic ring is preferably 5:95 to 50:50, more preferably 10:90 to 45:55, and particularly preferably 20:80 to 40:60. By setting the mass ratio within this range, it is possible to suppress the occurrence of warping after the TSV mold underfill composition applied to the wafer on which the semiconductor chip is mounted has cured, and to obtain good bias HAST test results. As epoxy compounds having an aromatic ring in the molecule, known or conventional aromatic epoxy compounds can be used, and are not particularly limited. Specific examples of epoxy compounds having an aromatic ring in the molecule include: Glycidyl ethers of phenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, catechol, and resorcinol: Glycidyl ether esters of hydroxycarboxylic acids such as p-hydroxybenzoic acid; Monoglycidyl esters or polyglycidyl esters of carboxylic acids such as benzoic acid, phthalic acid, and terephthalic acid; Glycidylamine-type epoxy compounds such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, and tetraglycidyl-m-xylylenediamine; Epoxy compounds having a naphthalene skeleton, such as glycidyl esters of naphthol and glycidyl ether esters of β-hydroxynaphthoic acid. These are some examples. In addition, novolac compounds obtained by novolacizing phenols such as phenol, catechol, and resorcinol may be used. Among these, glycidylamine-type epoxy compounds are preferred.

[0030] (B) Hardener The TSV mold underfill composition of the present invention contains a curing agent. This curing agent is not particularly limited as long as it can cure the epoxy resin (A) described above. Examples of curing agents that can be used in the TSV mold underfill composition of the present invention include phenol compounds, acid anhydrides, amine compounds (especially acyclic amine compounds), nitrogen-containing heterocyclic compounds (especially imidazole compounds), phosphorus compounds, and organometallic compounds. In some embodiments, basic curing agents among these are used.

[0031] Examples of the above-mentioned phenolic compounds include phenolic resins, particularly novolac resins obtained by condensing phenols or naphthols (e.g., phenol, cresol, naphthol, alkylphenol, bisphenol, terpenephenol, etc.) with formaldehyde. Examples of novolac resins include phenol novolac resin, o-cresol novolac resin, p-cresol novolac resin, α-naphthol novolac resin, β-naphthol novolac resin, t-butylphenol novolac resin, bisphenol A type novolac resin, xylylene-modified novolac resin, decalin-modified novolac resin, etc. Examples of other phenolic resins include dicyclopentadiene cresol resin, poly-p-vinylphenol, poly(di-o-hydroxyphenyl)methane, poly(di-m-hydroxyphenyl)methane, and poly(di-p-hydroxyphenyl)methane.

[0032] Examples of the above acid anhydrides include phthalic anhydride; hexahydrophthalic anhydride; alkylhexahydrophthalic anhydride such as methylhexahydrophthalic anhydride; tetrahydrophthalic anhydride; alkyltetrahydrophthalic anhydride such as trialkyltetrahydrophthalic anhydride and 3-methyltetrahydrophthalic anhydride; Hymic anhydride; succinic anhydride; trimellitic anhydride; pyromellitic anhydride, etc. Of these, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride are preferred.

[0033] Examples of the above (acyclic) amine compounds include 2,4,6-tris(dimethylaminomethyl)phenol, diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, tetramethyldiaminodiphenylmethane, tetraethyldiaminodiphenylmethane, diethyldimethyldiaminodiphenylmethane, dimethyldiaminotoluene, diaminodibutyltoluene, diaminodipropyltoluene, diaminodiphenylsulfone, diaminoditolylsulfone, diethyldiaminotoluene, bis(4-amino-3-ethylphenyl)methane, polytetramethylene oxide-di-p-aminobenzoate, and 4,4-dimethylaminopyridine. The amine compound may also be an amine adduct.

[0034] Examples of nitrogen-containing heterocyclic compounds include imidazoles such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, as well as diazabicycloundecylimidazole. Examples include sen (DBU), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-formate, DBU-orthophthalate, DBU-phenol novolac resin salt, DBU-tetraphenylborate salt, diazabicyclononene (DBN), DBN-phenol novolac resin salt, diazabicyclooctane, pyrazole, oxazole, thiazole, imidazoline, pyrazine, morpholine, thiazine, indole, isoindole, benzimidazole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, and pteridine. Nitrogen-containing heterocyclic compounds can be used in the form of adducts with epoxy resins or isocyanate compounds, or in microencapsulated form.

[0035] Examples of the phosphorus compounds mentioned above include trialkylphosphine compounds such as tributylphosphine and triarylphosphine compounds such as triphenylphosphine.

[0036] Examples of the organometallic compounds mentioned above include zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, bisacetylacetonatocobalt(II), and trisacetylacetonatocobalt(III).

[0037] In the present invention, the curing agent preferably contains at least one selected from the group consisting of phenol compounds, acid anhydrides, acyclic amine compounds, and nitrogen-containing heterocyclic compounds, and more preferably contains a nitrogen-containing heterocyclic compound. The nitrogen-containing heterocyclic compound may be latent, and a microencapsulated latent curing agent can also be used. The nitrogen-containing heterocyclic compound is particularly preferably an imidazole compound. Examples of imidazole compounds include 2-substituted imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, 1-isobutyl 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 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, and 1-cyanoethyl-2-phenylimidazole; and trimelates such as 1-cyanoethyl-2-undecylimidazolium trimelates. Examples include triazine compounds such as litates; 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, and 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine; isocyanuric acid adducts of 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, isocyanuric acid adducts of 2-phenylimidazole, isocyanuric acid adducts of 2-methylimidazole, isocyanuric acid adducts of 2-phenyl-4,5-dihydroxymethylimidazole, and isocyanuric acid adducts of 2-phenyl-4-methyl-5-dihydroxymethylimidazole.

[0038] As the above-mentioned microencapsulated curing agent, for example, a dispersion in which a powder of an amine compound (including nitrogen-containing heterocyclic compounds) is dispersed in a liquid epoxy resin can be used. This amine compound can be 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. This amine compound may also be used in the form of a reaction product with a carboxylic acid, sulfonic acid, isocyanate, epoxide, etc. These compounds may be used alone or in combination of two or more. For example, the above-mentioned amine compound can be used in combination with its reaction product with a carboxylic acid, sulfonic acid, isocyanate, or epoxide. The volume-average particle size of the above-mentioned amine compound powder is preferably 50 μm or less, and more preferably 10 μm or less. Furthermore, it is preferable that the above-mentioned amine compound powder has a melting point or softening point of 60°C or higher from the viewpoint of suppressing thickening at 25°C.

[0039] In the TSV mold underfill composition of the present invention, the curing agent may be used alone or in combination of two or more types. In the present invention, the curing agent is preferably an imidazole compound, and more preferably an imidazole compound and a phenol compound are used in combination. By using an imidazole compound and a phenol compound in combination, it is possible to improve storage stability while enhancing curability.

[0040] In the TSV mold underfill composition 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 particularly preferably 3 to 10% by mass, relative to (A) the epoxy resin. By setting the content within this range, the curing time of the TSV mold underfill composition is not made too long, the productivity of electronic components including high-density wiring formed by techniques such as TSV is improved, the occurrence of warping after curing of the TSV mold underfill composition applied to a wafer on which a semiconductor chip is mounted is suppressed, and the storage stability of the TSV mold underfill composition is improved.

[0041] (C) Filler The TSV mold underfill composition of the present invention contains a filler. Examples of fillers used in the present invention include, but are not limited to, fillers consisting of silica (fused silica, crystalline silica, etc.), alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride (BN), glass beads, etc. However, carbon black is not a filler in the present invention. In the TSV mold underfill composition of the present invention, the fillers may be used alone or in combination of two or more types. Furthermore, the filler may be surface-treated with a surface treatment agent, such as a silane coupling agent (which may have substituents such as phenyl groups, vinyl groups, or methacryloyl groups). Using a surface-treated filler can reduce the viscosity of the TSV mold underfill composition and improve its injectability.

[0042] From the viewpoint of reducing the coefficient of thermal expansion of the cured product provided by the TSV mold underfill composition of the present invention, it is preferable to use silica powder as a filler, and more preferable to use fused silica powder. Examples of fused silica powder include spherical fused silica powder and crushed fused silica powder, but from the viewpoint of the fluidity of the TSV mold underfill composition, it is more preferable to use spherical fused silica powder (especially one consisting of particles with high sphericity) as a filler.

[0043] The filler used in this invention includes fillers with an average particle size 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 include fillers with an average particle size of 0.1 μm to 1.0 μm, the mold underfill composition will exhibit inappropriate viscosity and / or injectability. The viscosity of the mold underfill composition, measured using a rotational viscometer at 20 rpm and 25°C, is preferably 20 to 400 Pa·s, more preferably 40 to 300 Pa·s, and particularly preferably 60 to 200 Pa·s. A viscosity within this range improves the injectability of the TSV mold underfill composition and suppresses the outflow of the TSV mold underfill composition from the mold during compression molding. Furthermore, "injectability" in this application refers to the degree of ease of filling the silicon chip-silicon wafer with the TSV mold underfill composition during compression molding. The average particle size of the filler is the particle size at 50% of the cumulative volume of the volume particle size distribution (D 50 It can be determined as follows: More specifically, a sample arbitrarily selected from the population is used, the particle size distribution is measured using a laser diffraction scattering particle size distribution analyzer, and the average particle size, etc., can be determined based on this particle size distribution. In the present invention, from the viewpoint of injectability, it is particularly preferable that, when the total mass of the filler is 100 parts by mass, the content of particles with a particle size larger than 1 μm in the filler is less than 1.0 part by mass. The TSV mold underfill composition of the present invention may further contain, as an optional component, fillers with an average particle size of less than 0.1 μm, to the extent that it does not adversely affect the properties of the composition.

[0044] In the TSV mold underfill composition of the present invention, the filler content is preferably 65 to 90 parts by mass, more preferably 68 to 88 parts by mass, and particularly preferably 70 to 85 parts by mass, when the total mass of the TSV mold underfill composition is 100 parts by mass.

[0045] (D) Carbon Black The TSV mold underfill composition of the present invention contains carbon black. The use of carbon black is important considering the possibility that wiring within electronic components may be affected by light. The carbon black is not particularly limited, and any carbon black commonly used in epoxy resin compositions can be appropriately selected and used. Examples of such carbon blacks include acetylene black, furnace black, Ketjen black, channel black, lamp black, and thermal black. These may be used alone or in combination of two or more.

[0046] In the present invention, carbon black may be used in combination with other black pigments. Other black pigments that can be used include black organic pigments, mixed organic pigments, and black inorganic pigments. Examples of black organic pigments include perylene black and aniline black. Examples of mixed organic pigments include those obtained by mixing at least two pigments selected from red, blue, green, purple, yellow, magenta, cyan, etc., to create a pseudo-black color. Examples of black inorganic pigments include graphite, as well as fine particles of metals and their oxides (including complex oxides), sulfides, nitrides, etc. Examples of these metals include titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver. Furthermore, carbon black may be used in combination with other colorants such as dyes.

[0047] In the TSV mold underfill composition of the present invention, the carbon black content is 0.1 parts by mass or more and 1.5 parts by mass or less when the mass of (A) epoxy resin is 100 parts by mass. Preferably, the carbon black content is 0.1 parts by mass or more and 1.3 parts by mass or less, and more preferably 0.1 parts by mass or more and 1.1 parts by mass or less. Furthermore, when the total mass of the TSV mold underfill composition is 100 parts by mass, the carbon black content is preferably 0.01 parts by mass or more and 0.60 parts by mass or less, more preferably 0.01 parts by mass or more and 0.45 parts by mass or less, and even more preferably 0.01 parts by mass or more and 0.30 parts by mass or less. If the carbon black content falls below the above range, light shielding will be insufficient, and wiring within electronic components may be affected by light. If the carbon black content exceeds the above range, electronic components obtained by packaging multiple chips stacked using TSV technology with a TSV mold underfill composition are prone to short circuits in bias HAST testing. In other words, the reliability of such electronic components decreases. The fact that the carbon black content in a TSV mold underfill composition affects the reliability of electronic components manufactured using TSV technology was discovered for the first time by the inventors.

[0048] Furthermore, the TSV mold underfill composition of the present invention contains chloride ions (Cl - The content of chloride ions is 0.1 ppm or more and less than 11.0 ppm relative to the total mass of the TSV mold underfill composition. Preferably, this content is 0.1 ppm or more and less than 10.8 ppm, more preferably 0.1 ppm or more and less than 10.0 ppm, and even more preferably 0.1 ppm or more and less than 7.0 ppm. If the chloride ion content is 11.0 ppm or more, the electronic component obtained by packaging multiple chips stacked using TSV technology with the TSV mold underfill composition is prone to short circuits in bias HAST tests. In other words, the reliability of such electronic components is reduced. On the other hand, from the viewpoint of commercial availability, it is preferable that the chloride ion content is 0.1 ppm or more.

[0049] As mentioned earlier, in the manufacturing of electronic components containing multiple stacked chips, the conventional process involved sealing the gaps between the wafer and the chips, or between the chips themselves, after each chip was stacked, followed by overmolding. In this process, a resin composition with a lower chloride ion content than the resin composition used for overmolding was used for sealing.

[0050] In contrast, when using a TSV mold underfill composition to perform sealing and overmolding in a single process, the same resin composition must be used for both sealing and overmolding. Conventional sealing resin compositions are unsuitable as TSV mold underfill compositions due to reasons such as moisture resistance and ion elution resistance. On the other hand, when conventional overmolding resin compositions are used as TSV mold underfill compositions to manufacture electronic components containing multiple stacked chips, the resulting electronic components are prone to short circuits in bias HAST tests. In other words, such electronic components exhibit low reliability.

[0051] Under these circumstances, the inventors, after various studies, found that when the chloride ion content in addition to the carbon black content in the TSV mold underfill composition is within the above range, electronic components containing the cured product obtained by curing the TSV mold underfill composition do not short-circuit for a long period of time in bias HAST tests, and that the low reliability described above is due to the excessively high chloride ion content in conventional TSV mold underfill compositions. This discovery was made by the inventors for the first time.

[0052] The chloride ion content can be measured by extracting the sample with pure water under high heat and pressure (for example, 121°C and 2 atmospheres for 20 hours) and analyzing the resulting extract by ion chromatography. However, if it is difficult to measure the chloride ion content of the TSV mold underfill composition of the present invention, this content shall be considered equal to the chloride ion content measured by the above method in the cured product obtained by curing the TSV mold underfill composition.

[0053] The TSV mold underfill composition of the present invention may, if desired, contain optional components, such as those described below, in addition to the essential components (A) to (D) listed above.

[0054] (E) Silicone-based additives The TSV mold underfill composition of the present invention may optionally contain a silicone-based additive. In one embodiment, the TSV mold underfill composition of the present invention further contains a silicone-based additive. The inclusion of a silicone-based additive is preferable from the viewpoint of improving the fluidity of the TSV mold underfill composition. The silicone-based additive is preferably a dialkylpolysiloxane (the alkyl group bonded to Si can be methyl, ethyl, etc.), particularly dimethylpolysiloxane. Alternatively, the silicone-based additive may be a modified dialkylpolysiloxane, such as epoxy-modified dimethylpolysiloxane. Specific examples of silicone-based additives include KF69 (dimethyl silicone oil, manufactured by Shin-Etsu Silicone) and SF8421 (epoxy-modified silicone oil, manufactured by Toray Dow Silicone). The silicone-based additive may be used alone or in combination of two or more types.

[0055] When the TSV mold underfill composition 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, and more preferably 0.25 to 1 part by mass, per 100 parts by mass of (A) epoxy resin.

[0056] (F) Coupling agent The TSV mold underfill composition of the present invention may optionally contain a coupling agent. In one embodiment, the TSV mold underfill composition of the present invention further contains a coupling agent. The inclusion of a coupling agent, particularly a silane coupling agent, is preferable from the viewpoint of improving adhesive strength. Various silane coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, and mercapto-based agents can be used as the coupling agent. Specific examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatetopropyltriethoxysilane. These silane coupling agents may be used alone or in combination of two or more.

[0057] When the TSV mold underfill composition of the present invention contains a coupling agent, the amount of the coupling agent is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of (A) epoxy resin.

[0058] (G) Migration inhibitors The TSV mold underfill composition of the present invention may optionally contain a migration inhibitor. In one embodiment, the TSV mold underfill composition of the present invention further contains a migration inhibitor. Migration is a phenomenon in which the metal of the wiring pattern dissolves due to an electrochemical reaction, resulting in a decrease in resistance. The inclusion of a migration inhibitor is preferable from the viewpoint of improving the reliability of electronic components. Specific examples of migration inhibitors include xanthines such as caffeine, theophylline, theobromine, and paraxanthine; tocols such as 5,7,8-trimethyltochol (α-tocopherol), 5,8-dimethyltochol (β-tocopherol), 7,8-dimethyltochol (γ-tocopherol), and 8-methyltochol (δ-tocopherol); and 5,7,8-trimethyltocotrienol (α-tocotrienol), 5,8-dimethyltocotrienol (β-tocotrienol), and 7,8-dimethyltocotrienol (γ-tocotrienol). Examples include tocotrienols such as 8-methyltocotrienol (δ-tocotrienol); benzotriazoles such as benzotriazole, 1H-benzotriazole-1-methanol, and alkylbenzotriazoles; triazines such as 2,4-diamino-6-vinyl-S-triazine, 2,4-diamino-6-[2'-ethyl-4-methylimidazole-(1)]-ethyl-S-triazine, and 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.

[0059] When the TSV mold underfill composition of the present invention contains a migration inhibitor, the amount of the migration inhibitor is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of (A) epoxy resin.

[0060] (H) Stabilizer The TSV mold underfill composition of the present invention may optionally contain a stabilizer. The stabilizer may be included in the TSV mold underfill composition of the present invention to improve its storage stability and extend the pot life. Various stabilizers known as one-component adhesives mainly composed of epoxy resin can be used, but at least one selected from the group consisting of liquid borate ester compounds, aluminum chelates, and organic acids is preferred due to its high effectiveness in improving storage stability.

[0061] Examples of liquid borate ester compounds include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxowndecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxowndecyl)borane, trimenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, and the like. Liquid borate ester compounds are preferred because they are liquid at room temperature (25°C), thus allowing for a low viscosity of the TSV mold underfill composition. For example, aluminum chelate A can be used as the aluminum chelate. For example, barbituric acid can be used as the organic acid.

[0062] If a stabilizer is included, the amount of stabilizer is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 25 parts by mass, and even more preferably 0.1 to 20 parts by mass, per 100 parts by mass of (A) epoxy resin.

[0063] (I) Other additives The TSV mold underfill composition of the present invention may optionally contain other additives, such as ion trapping agents, leveling agents, antioxidants, defoaming agents, thixotropes, viscosity modifiers, flame retardants, solvents, etc., as long as they do not impair the spirit of the present invention. The type and amount of each additive are as per conventional methods.

[0064] In the TSV mold underfill composition of the present invention, one or more of the components contained therein (including components (A) to (D)) may exist as particulate solids. In the present invention, from the viewpoint of injectionability, when the total mass of the TSV mold underfill composition is 100 parts by mass, it is preferable that the content of particles with a particle size larger than 1 μm is less than 1.0 part by mass.

[0065] The method for producing the TSV mold underfill composition of the present invention is not particularly limited. For example, the TSV mold underfill composition of the present invention can be obtained by simultaneously or separately introducing components (A) to (D) and, if desired, other components into a suitable mixer, stirring and mixing them while melting them by heating if necessary, to obtain a homogeneous composition. The mixer is not particularly limited, but a Leikai mixer 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. These devices may also be used in appropriate combinations.

[0066] The TSV mold underfill composition obtained in this manner is thermosetting, and under conditions of a temperature of 100 to 170°C, it preferably hardens in 0.1 to 3 hours, and more preferably in 0.25 to 2 hours.

[0067] The composition of the present invention can be used, for example, as an adhesive, encapsulant, or raw material for semiconductor devices containing various electronic components, or for fixing, joining, or protecting components that make up electronic components. The composition of the present invention is suitable as an underfill material for protecting electronic components and fixing them to a substrate, and in particular as a TSV mold underfill composition used in a technique that seals between wafers and chips and between each chip, and forms the outer shape of electronic components in a single step. As an example of an electronic component manufacturing process using such a technique, a compression molding process is shown in Figure 1. A wafer on which a plurality of stacked semiconductor chips are mounted (Figure 1(A)) is placed in a compression molding apparatus equipped with a mold, and the TSV mold underfill composition is applied to this wafer (Figure 1(B)). This wafer is subjected to compression molding under heating, and then the mold underfill composition is cured by heating (Figure 1(C)). Through such a process, sealing between wafers on which semiconductor chips are mounted and between chips, and between each chip, as well as forming the outer shape of electronic components, can be achieved in a single step.

[0068] Furthermore, the present invention also provides a cured product obtained by curing the TSV mold underfill composition of the present invention. The present invention also provides an electronic component containing the cured product of the present invention.

[0069] The present invention also provides a semiconductor element sealed with the TSV mold underfill composition of the present invention. Furthermore, the present invention also provides a semiconductor package having a semiconductor element sealed with the TSV mold underfill composition of the present invention. [Examples]

[0070] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following description, parts and % refer to parts by mass and mass%, respectively, unless otherwise specified.

[0071] Examples 1-6, Comparative Examples 1-5 A resin composition was prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulation shown in Table 1. In Table 1, the amount of each component is expressed in parts by mass (unit: g).

[0072] (A) Epoxy resin In the examples and comparative examples, the compounds used as (A) epoxy resin are as follows: (A-1): Aminophenol-type epoxy resin (product name: jER630, manufactured by Mitsubishi Chemical Corporation) (epoxy resin containing aromatic rings) (A-2): Aminophenol-type epoxy resin (product name: jER630LSD, manufactured by Mitsubishi Chemical Corporation) (epoxy resin containing aromatic rings) (A-3): Aliphatic epoxy resin (product name: YX7400, manufactured by Mitsubishi Chemical Corporation)

[0073] (B) Hardener In the examples and comparative examples, the compounds used as curing agents (B) are as follows: (B-1): Liquid phenol novolac resin (product name: MEH-8005, manufactured by Meiwa Kasei Co., Ltd.) (B-2): 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine (product name: Curazole 2MZ-A, manufactured by Shikoku Chemicals Co., Ltd.)

[0074] (C) Filler The compounds used as fillers (C) in the examples and comparative examples are as follows: (C-1): Silica filler (Product name: SE2200SME, manufactured by Admatex Co., Ltd., average particle size: 0.6 μm, maximum particle size: 3 μm) (C-2): Silica filler (Product name: SE1050SMO, manufactured by Admatex Co., Ltd., average particle size: 0.3 μm, maximum particle size: 1 μm) (C-3): Silica filler (Product name: Admanano YA050C, manufactured by Admatex Co., Ltd., average particle size: 50 nm, surface treated) (C-4): Silica filler (Product name: SE5200SME, manufactured by Admatex Co., Ltd., average particle size: 1.5 μm, maximum particle size: 10 μm)

[0075] (D) Carbon Black In the examples and comparative examples, the compounds used as (D) carbon black are as follows: (D-1): Carbon Black (Product name: Special Black 4, manufactured by Orion Engineered Carbons Co., Ltd.) In Table 1, "(D) Carbon Black Content" represents the amount (parts by mass) of (D) carbon black when the mass of (A) epoxy resin is 100 parts by mass.

[0076] (E) Silicone-based additives In the examples and comparative examples, the compounds used as (E) silicone additives are as follows: (E-1): Epoxy-modified silicone oil (Product name: SF8421, manufactured by Toray Dow Corning Silicone Co., Ltd.)

[0077] (F) Coupling agent In the 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 Co., Ltd.)

[0078] (G) Migration inhibitors In the examples and comparative examples, the compounds used as (G) migration inhibitors are as follows: (G-1): Caffeine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0079] (I) Ion trap material In the examples and comparative examples, the compounds used as (I) ion trap materials are as follows: (I-1): Zr·Bi-based ion trap material (product name: IXE6136, manufactured by Toagosei Co., Ltd.)

[0080] In the examples and comparative examples, the properties of the resin composition and cured product were measured as follows.

[0081] (Viscosity of the composition) The viscosity (in Pa·s) of each prepared resin composition was measured using a Brookfield HB viscometer (with spindle SC4-14) at 25°C and 10 revolutions / minute. The results are shown in Table 1.

[0082] (Gel time of composition) Each prepared resin composition was dropped onto a stainless steel plate heated to 120±2℃ in a size of approximately 5mmΦ. A metal needle was then applied to the resin composition at regular intervals, and the time (in seconds) until stringiness disappeared was measured using a stopwatch. In addition, the gel time for the TSV mold underfill composition of the present invention 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, poor injection properties due to gelation of the TSV mold underfill composition can be suppressed, and the molding time during compression molding does not become too long, thereby improving productivity.

[0083] (Evaluation of the injectability of mold underfill compositions for TSV) A silicon chip (18mm long, 18mm wide, 300μm thick) was placed on a silicon wafer (300mm in diameter, 760μm thick) via nine spacers (1-2mm in diameter, 20μm thick, disc-shaped). The spacers were arranged at equal intervals along the diagonals of the silicon chip (see Figure 2(B)). Four silicon chips were then arranged at equal intervals near the outer edge of the silicon wafer using the same method (see Figure 2(A)).

[0084] The silicon wafer, along with the silicon chips and spacers, was placed in a compression molding apparatus (model number: WCM-300, manufactured by Apic Yamada Co., Ltd.) equipped with a mold. Next, the mold was filled with a TSV mold underfill composition, and compression molding was performed under conditions of a temperature of 120°C and a pressure of 250kN. After that, the TSV mold underfill composition was cured by heating at this temperature for 400 seconds, thereby forming a 500μm thick layer of cured TSV mold underfill composition (with the silicon chips and spacers enclosed within) that covered the entire silicon wafer.

[0085] A encapsulation was obtained by cutting a silicon wafer coated with a layer of cured material, removed from a compression molding apparatus, at a position slightly away from the outer edge of the silicon chip. The silicon chip, cured material, and spacer were removed from the encapsulation by planar polishing until the thickness of the cured material layer measured from the silicon wafer was approximately 10 μm, thereby obtaining a test specimen for injection performance evaluation. The polished side of the obtained test specimens was observed visually or under a microscope (magnification: 100x). If no voids were found in the test specimen, or if the maximum width of any voids found in the test specimen was less than 100 μm, the injectability was evaluated as ○ (see Figure 3(B)). If the maximum width of any voids found in the test specimen was 100 μm or more, the injectability was evaluated as × (see Figure 3(A)).

[0086] (Preparation of hardened material) Each prepared resin composition was heated in a dryer at 150°C for 1 hour to obtain a cured product.

[0087] (Biased HAST test of cured material) Figure 4 shows a schematic diagram of the comb-shaped electrode used to evaluate insulation reliability by bias HAST testing. This comb-shaped electrode consists of a polyimide film substrate (38 μm thick) and patterned copper wiring (15 μm wiring width, 30 μm inter-wire pitch, 8 μm thickness, tin-plated (0.2 ± 0.05 μm thickness)) on it. A TSV mold underfill composition was applied to this comb-shaped electrode to a thickness of 150 μm, and the mold underfill composition on the comb-shaped electrode was cured by heating in a dryer at 150°C for 1 hour to obtain a test specimen. This test specimen was mounted in a HAST apparatus (model number: PC-422R8, manufactured by Hirayama Seisakusho Co., Ltd.), and the electrical resistance value was continuously monitored under conditions of relative humidity of 85% and temperature of 130°C while applying a bias voltage of 3 V. The time (in hr) from the start of the test until a short circuit occurred (electrical resistance value became 10 kΩ or less) was measured. The results are shown in Table 1. However, if no short circuit occurs within 168 hours, it will display "Pass".

[0088] (Chloride ions in hardened products (Cl - (Content of) The prepared resin composition was cured by heating at 150°C for 60 minutes, and the resulting sample was pulverized to approximately 5 mm cubes. 2.5 g of this sample was mixed with 25 cm³ of deionized water. 3 The following ingredients were added and the mixture was placed in a PCT test chamber (EHS-221M, manufactured by ESPEC Corporation, at 121°C ± 2°C / 100% humidity / 2 atm) for 20 hours. After cooling to room temperature, the resulting extract was used as the test solution. The chloride ion concentration of the test solution obtained using the above procedure was measured using an ion chromatograph (CLASS-VP, manufactured by Shimadzu Corporation, using column IC-A3). The evaluation results of the chloride ion content are shown in Table 1.

[0089] [Table 1]

[0090] As is clear from Table 1, in all of Examples 1 to 6, where (i) the content of (D) carbon black was 0.1 parts by mass or more and 1.5 parts by mass or less when the mass of (A) epoxy resin was 100 parts by mass, and (ii) the content of chloride ions was 0.1 ppm or more and less than 11.0 ppm relative to the total mass of the mold underfill composition, no short circuit occurred within 168 hours from the start of the test in the biased HAST test conducted under the above conditions. Furthermore, in all of these examples, the mold underfill composition showed good injectability. In contrast, in Comparative Examples 1-3, which did not satisfy either or both of the above requirements (i) and (ii), a short circuit occurred within 168 hours of the start of the biased HAST test. Furthermore, in Comparative Example 4, which did not contain filler (C) with an average particle size of 0.1 μm to 1.0 μm, the injection properties of the mold underfill composition were poor. In Comparative Example 5, the injection properties of the mold underfill composition were also poor, which is thought to be because (I) the ion trap material contained many particles with a particle size larger than 1 μm. In Comparative Example 5, despite the excessive carbon black content, no short circuit occurred within 168 hours in the biased HAST test. This is presumed to be because chloride ions were captured by (I) the ion trap material. [Industrial applicability]

[0091] The TSV mold underfill composition of the present invention exhibits good injectability and appropriate sealing properties. Furthermore, electronic components containing a cured product obtained by curing the TSV mold underfill composition of the present invention do not experience short circuits over long periods in bias HAST tests. Therefore, by using the TSV mold underfill composition of the present invention, electronic components containing high-density wiring formed by techniques such as TSV can be efficiently manufactured, and sufficient reliability can be provided to such electronic components. [Explanation of Symbols]

[0092] 10 silicon wafers 11 Silicone Chips 12 Bump 13. Mold underfill composition for TSV 14 molds 20 Silicon wafers (300mm diameter) 21 Silicone Chips 22 Spacer (thickness 20 μm) 23. Cured product of mold underfill composition for TSV Cured product of mold underfill composition for 30 TSVs 31 Spacer 32 Void

Claims

1. A mold underfill composition for TSV, comprising the following (A) to (D): (A) Epoxy resin; (B) Hardener; (C) Filler; and (D) Carbon Black Includes, The epoxy resin (A) is of the following formula (I): 【Chemistry 4】 [In the formula, n is an integer between 1 and 15.] It contains an aliphatic epoxy resin indicated by The curing agent (B) comprises an imidazole compound and a phenol compound, The (C) filler comprises fillers with an average particle size of 0.1 μm to 1.0 μm. When the total mass of the TSV mold underfill composition is 100 parts by mass, the content of (A) epoxy resin is 10 to 35 parts by mass, and the content of (C) filler is 65 to 90 parts by mass. The content of the curing agent (B) is 1 to 20% by mass relative to the epoxy resin (A), 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 Chloride ions (Cl － A TSV mold underfill composition in which the content of ) is 0.1 ppm or more and less than 11.0 ppm relative to the total mass of the TSV mold underfill composition.

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

3. (A) The TSV mold underfill composition according to claim 1 or 2, wherein the epoxy resin further comprises an epoxy resin having an aromatic ring in its molecule.

4. (E) A mold underfill composition for TSV according to any one of claims 1 to 3, further comprising a silicone-based additive.

5. (F) A TSV mold underfill composition according to any one of claims 1 to 4, further comprising a coupling agent.

6. (G) A mold underfill composition for TSV according to any one of claims 1 to 5, further comprising a migration inhibitor.

7. The TSV mold underfill composition according to any one of claims 1 to 6, wherein when the total mass of the TSV mold underfill composition is 100 parts by mass, the content of particles with a particle size larger than 1 μm is less than 1.0 part by mass.

8. A semiconductor package having a semiconductor element sealed with a TSV mold underfill composition according to any one of claims 1 to 7.

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