Epoxy resin composition, semiconductor device, and method for producing semiconductor device

Abstract

The present invention provides: an epoxy resin composition which can be applied by means of a jet dispenser, while having good injectability; a semiconductor device; and a method for producing a semiconductor device.　This epoxy resin composition contains a polytetramethylene glycol-type epoxy resin, a heterocyclic compound that contains a nitrogen atom, and a filler; the filler is surface-treated with at least one of 3-methacryloxypropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; and the content of the filler is not less than 55% by mass but less than 77% by mass relative to the total mass of this epoxy resin composition.

Description

Epoxy resin composition, semiconductor device, and method for manufacturing semiconductor device

[0001] One aspect of the present disclosure relates to an epoxy resin composition, a semiconductor device, and a method for manufacturing a semiconductor device.

[0002] Electronic devices incorporating semiconductor devices are required to be smaller, lighter, and have higher performance. To meet these demands, the mainstream mounting method for semiconductor devices has shifted from wire bonding to flip-chip mounting. Flip-chip mounting is generally performed as follows: First, the electrode (bump) surface of the semiconductor element is brought face-to-face with the electrode (pad) surface of the substrate, and they are electrically connected. Next, the connection between the electrodes is protected and reinforced from the outside. Finally, to alleviate stress caused by differences in the linear expansion coefficients between the semiconductor element and the substrate, a liquid thermosetting adhesive called an underfill material (also called a sealant) is typically used to seal the gap between the semiconductor element and the substrate.

[0003] The most common method for supplying underfill material is capillary flow. In capillary flow, after connecting the bumps and pads, underfill material is applied along the periphery of the semiconductor element and then injected into the gap between them using capillary action. After the underfill material is injected, it is heated and cured to reinforce the connection between them.

[0004] An underfill material is generally a composition containing an epoxy resin and a filler. One example of an underfill material proposed is a composition containing an aminophenol-type epoxy resin, an amine-based curing agent, a silica filler, and a silane coupling agent (see, for example, Patent Document 1). Another example is an underfill material proposed that contains an epoxy resin, a curing agent, a filler, and a modified polysiloxane (see, for example, Patent Document 2). Thus, various underfill materials have been proposed by varying the type of epoxy resin, the type of curing agent, and the like.

[0005] JP 2016-113525 A JP 2001-55488 A

[0006] In recent years, as semiconductor devices have become more powerful, the wiring and other components within the devices have become denser. For this reason, underfill materials are often applied to minute areas. Jet dispensers are often used to apply underfill materials to minute areas. When applying with a jet dispenser, droplets of underfill material are sprayed from a nozzle positioned away from the substrate. For this reason, the viscosity of the underfill material must be relatively low.

[0007] Furthermore, in flip-chip mounting, the time required to inject the underfill material is a bottleneck. Therefore, in order to improve production efficiency, it is preferable to increase the injection speed of the underfill material. One method for increasing the injection speed, i.e., improving injectability, is to increase the filler particle size and reduce the viscosity of the underfill material. However, when the filler particle size is large, clogging by coarse filler particles can cause the injection speed to become uneven, resulting in unfilled areas.

[0008] An object of the present disclosure is to provide an epoxy resin composition that can be applied using a jet dispenser and has good injectability, a semiconductor device, and a method for manufacturing a semiconductor device.

[0009] The inventors of the present invention have investigated what kind of resin would provide good injectability for a resin composition containing a large amount of filler and having a small particle size of filler. As a result, they have found that an underfill material with good injectability can be achieved by using a polytetramethylene glycol-type epoxy resin, which has a high stress relaxation effect as an epoxy resin, a filler, and an appropriate hardener component.

[0010] Specifically, in order to achieve the above object, an epoxy resin composition according to one embodiment of the present disclosure contains a polytetramethylene glycol-type epoxy resin, a nitrogen-containing heterocyclic compound, and a filler, the filler being surface-treated with at least one of 3-methacryloxypropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane, and the content of the filler is 55 mass % or more and less than 77 mass % with respect to the total amount of the epoxy resin composition.

[0011] According to one embodiment of the present disclosure, it is possible to provide an epoxy resin composition that can be applied using a jet dispenser and has good injectability, a semiconductor device, and a method for manufacturing a semiconductor device.

[0012] (Epoxy Resin Composition) The epoxy resin composition according to the embodiment contains a polytetramethylene glycol-type epoxy resin, a heterocyclic compound containing a nitrogen atom, and a filler. The epoxy resin composition according to the embodiment preferably further contains an epoxy resin other than the polytetramethylene glycol-type epoxy resin, and may contain other components as necessary.

[0013] <Polytetramethylene glycol-type epoxy resin> Polytetramethylene glycol-type epoxy resin can reduce the viscosity of the epoxy resin composition and is therefore included to improve injectability. Furthermore, polytetramethylene glycol-type epoxy resin does not have a rigid ring within the molecule and is composed solely of a flexible linear structure. Therefore, polytetramethylene glycol-type epoxy resin is a resin with a high stress relaxation effect, has flexibility, can impart flexibility to the cured product, and can reduce the elastic modulus of the cured product. Furthermore, because polytetramethylene glycol-type epoxy resin has a high stress relaxation effect, it can suppress defects such as cracks occurring in the cured product of the epoxy resin composition or semiconductor elements due to temperature cycling after mounting. In other words, polytetramethylene glycol-type epoxy resin can improve reliability (post-mounting reliability).

[0014] Regarding the molecular weight of the polytetramethylene glycol-type epoxy resin, from the viewpoint of the balance between viscosity and flexibility, the weight-average molecular weight is preferably 500 to 3,000, and more preferably 1,500 to 2,500. In this specification, the weight-average molecular weight refers to a value obtained by gel permeation chromatography (GPC) using a calibration curve with standard polystyrene. If the weight-average molecular weight is less than 500, the effect of imparting flexibility is small, which may result in poor reliability. On the other hand, if the weight-average molecular weight is 3,000 or more, the epoxy resin composition will have a high viscosity, which may lead to concerns about poor workability.

[0015] The number of epoxy groups contained in one molecule of the polytetramethylene glycol-type epoxy resin is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of reliability, it is preferably 2 or more (multifunctional epoxy resin). The upper limit of the number of epoxy groups is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably 5 or less.

[0016] The amount of chlorine contained in the polytetramethylene glycol type epoxy resin is preferably 1,000 ppm or less from the viewpoints of injectability, storage stability, and reliability.

[0017] The polytetramethylene glycol type epoxy resin is preferably used in combination with an epoxy resin other than the polytetramethylene glycol type epoxy resin described below.

[0018] The content of the polytetramethylene glycol-type epoxy resin is preferably 10% by mass to 30% by mass relative to the epoxy resin. If the content of the polytetramethylene glycol-type epoxy resin is less than 10% by mass, the stress relaxation and viscosity-reducing effects may be insufficient. On the other hand, if the content of the polytetramethylene glycol-type epoxy resin is more than 30% by mass, the cured product may become brittle, which may reduce reliability after mounting.

[0019] <Other Epoxy Resins> The other epoxy resins are epoxy resins other than the polytetramethylene glycol-type epoxy resins described above. The other epoxy resins can be any of various epoxy resins commonly used for semiconductor encapsulation, and are not particularly limited. The number of epoxy groups contained in one molecule of the other epoxy resin is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of reliability, it is preferably two or more (multifunctional epoxy resin). The upper limit of the number of epoxy groups is not particularly limited and can be selected appropriately depending on the purpose, but it is preferably five or less. The epoxy equivalent of the other epoxy resin is preferably 50 g / eq. to 10,000 g / eq., more preferably 50 g / eq. to 1,000 g / eq., and even more preferably 100 g / eq. to 500 g / eq. Here, the epoxy equivalent is the mass of a resin containing one equivalent of epoxy groups, as defined in JIS K 7236:2001. It should be noted that "eq." is an abbreviation for "equivalent."

[0020] Examples of epoxy resins other than polytetramethylene glycol-type epoxy resins include glycidylamine-type epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, bisphenol-type epoxy resins, novolac-type epoxy resins, fluorene-type epoxy resins, biphenyl-type epoxy resins, aminophenol-type epoxy resins, and naphthalene-type epoxy resins. Examples of glycidylamine-type epoxy resins include diglycidyl aniline, diglycidyl toluidine, and tetraglycidyl-m-xylylenediaminetetraglycidylbis(aminomethyl)cyclohexane. Examples of alicyclic epoxy resins include vinyl(3,4-cyclohexene) dioxide and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane. Examples of bisphenol-type epoxy resins include bisphenol A-type epoxy resins and bisphenol F-type epoxy resins. Examples of bisphenol A type epoxy resins include p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether. Examples of biphenyl type epoxy resins include biphenyl aralkyl epoxy resins and 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl. Examples of aminophenol type epoxy resins include triglycidyl-p-aminophenol. Examples of monofunctional epoxy resins include p-tert-butylphenyl glycidyl ether. Examples of multifunctional epoxy resins include diepoxy resins such as 1,4-phenyldimethanol diglycidyl ether; and triepoxy resins such as trimethylolpropane triglycidyl ether and glycerin triglycidyl ether.In addition to the above, epoxy resins other than polytetramethylene glycol-type epoxy resins may also include hydantoin-type epoxy resins such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; epoxy resins having a silicone skeleton such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane; and epoxy resins having a plant-derived skeleton. Among these, aminophenol-type epoxy resins, bisphenol-type epoxy resins, and aliphatic epoxy resins are preferred from the viewpoint of crack resistance. It is more preferable to use aliphatic epoxy resins and aromatic epoxy resins in combination. These may be used alone or in combination of two or more.

[0021] The content of the epoxy resin (total amount of polytetramethylene glycol-type epoxy resin and other epoxy resins) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 45% by mass to 23% by mass based on the total amount of the epoxy resin composition. When the content of the epoxy resin falls within this range, good injectability is achieved.

[0022] <Nitrogen-Atom-Containing Heterocyclic Compound> The nitrogen-atom-containing heterocyclic compound is included to cure the epoxy resin composition. When curing the epoxy resin composition, the nitrogen-atom-containing heterocyclic compound undergoes homopolymerization with the epoxy resin or the like. In contrast, the amine-based curing agent undergoes addition polymerization with the epoxy resin or the like. Due to this difference in reaction, the nitrogen-atom-containing heterocyclic compound cures with a lower crosslink density and linear expansion coefficient than the amine-based curing agent. Therefore, by using a nitrogen-atom-containing heterocyclic compound as a curing agent, the linear expansion coefficient of the cured product of the epoxy resin composition can be reduced, particularly at temperatures above the glass transition point. This reduces the gap between the linear expansion coefficient of the cured product of the epoxy resin composition and the linear expansion coefficient of the chip at high temperatures, thereby reducing the generated stress. This improves reliability.

[0023] The nitrogen atom-containing heterocyclic compound is not particularly limited as long as it can cure the resin in the epoxy resin composition, and can be appropriately selected depending on the purpose. Examples of the heterocyclic compound include imidazole derivatives and microencapsulated nitrogen atom-containing heterocyclic compounds. Examples of imidazole derivatives include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-imidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, and 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole. These may be used alone or in combination of two or more. As the imidazole derivative, a commercially available product or an appropriately synthesized product may be used. Examples of commercially available products include 2P4MZ (2-phenyl-4-methylimidazole), 2MZA (2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, and 2-phenyl-4-methylimidazole) (all manufactured by Shikoku Chemicals Corporation).

[0024] The nitrogen-containing heterocyclic compound may be microencapsulated. As the microencapsulated nitrogen-containing heterocyclic compound, a commercially available product may be used, or an appropriately synthesized product may be used. Examples of commercially available products include Novacure HX3941HP, Novacure HXA3042HP, Novacure HXA3922HP, Novacure HXA3792, Novacure HX3748, Novacure HX3721, Novacure HX3722, Novacure HX3088, Novacure HX3741, Novacure HX3742, Novacure HX3613 (all manufactured by Asahi Kasei Corporation), Amicure PN-23J, Amicure PN-40J (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), and Fujicure FXR-1121 (manufactured by Fuji Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more.

[0025] Of these, the nitrogen-containing heterocyclic compound is preferably 2-phenyl-4-methylimidazole from the viewpoints of reactivity and storage stability.

[0026] The content of the nitrogen-containing heterocyclic compound is not particularly limited and can be appropriately selected depending on the purpose. The content of the nitrogen-containing heterocyclic compound is preferably 2.0% by mass to 8.0% by mass, and more preferably 2.5% by mass to 6.0% by mass, based on the epoxy resin composition excluding the filler described below. When the content of the nitrogen-containing heterocyclic compound is 2.0% by mass or more, the curing time of the epoxy resin composition can be shortened, thereby improving the productivity of electronic component devices. When the content of the nitrogen-containing heterocyclic compound is 8.0% by mass or less, the storage stability of the epoxy resin composition is improved. With regard to the content of the microencapsulated nitrogen-containing heterocyclic compound, the content of the active ingredient (nitrogen-containing heterocyclic compound) is preferably 3% by mass to 25% by mass, and more preferably 5% by mass to 20% by mass, based on the epoxy resin composition excluding the filler.

[0027] <Filler> The filler is contained in order to reduce the linear expansion coefficient of the cured product of the epoxy resin composition and to suppress volumetric shrinkage caused by the curing reaction of the epoxy resin composition.

[0028] The filler is not particularly limited as long as it is contained in a typical epoxy resin composition and can be appropriately selected depending on the purpose. Examples of fillers include inorganic particles. Examples of inorganic particles include silica and alumina. The filler may also have other functions such as coloring. Examples of such fillers include inorganic pigments such as white pigments. Examples of inorganic pigments include magnesia, titania, zirconia, boron nitride, aluminum nitride, titanium oxide, magnesium oxide, zinc oxide, aluminum oxide, diamond, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide, barium titanate, and zirconia oxide. These may be used alone or in combination of two or more. Among these, silica filler is preferred because it allows for a high loading.

[0029] The filler is surface-treated with at least one of 3-methacryloxypropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane. By performing this surface treatment, it is possible to suppress filler aggregation and improve dispersibility. Furthermore, the wettability of the filler with the resin component is improved, which strengthens the bond at the interface between the filler and the resin, thereby improving the bonding between the filler and the resin component. This makes it possible to suppress an increase in the viscosity of the epoxy resin composition and a decrease in the injection rate, and also improve the toughness of the cured product of the epoxy resin composition.

[0030] The shape of the filler is not particularly limited and can be appropriately selected depending on the purpose. Examples of the shape of the filler include spherical, irregular, and flaky shapes. However, a spherical shape is preferred in that it can increase the filling amount while maintaining the fluidity of the epoxy resin composition.

[0031] The volume average particle size (hereinafter referred to as "average particle size") of the filler is preferably 2.0 μm or less, more preferably 0.1 μm to 2.0 μm, and even more preferably 0.5 μm to 1.5 μm. If the average particle size of the filler exceeds 2.0 μm, poor injection and nozzle clogging during dispensing may occur, resulting in poor dispensability. If the average particle size of the filler is less than 0.1 μm, the viscosity of the epoxy resin composition may become too high.

[0032] The average particle size of the filler refers to the volume average particle size D50 (the particle size at 50% cumulative from the small diameter side of the particle size distribution) measured using a laser diffraction particle size distribution analyzer (LS13320, manufactured by Beckman Coulter). The average particle size is measured as follows: 5 mg of filler is dispersed in 50 mg of dispersant, and the dispersion is dispersed for 10 minutes using an ultrasonic disperser to prepare a measurement sample. The average particle size of this measurement sample is measured under the following conditions: a flow rate of 50 mL / sec, a measurement time of 90 seconds, a solvent of pure water, and a solvent refractive index of 1.333.

[0033] It is preferable to use a top-cut filler. Top-cut refers to the classification of powder for the purpose of removing coarse particles. The top-cut diameter refers to the mesh size of the sieve used to classify the filler by sieving. That is, the top-cut diameter refers to the mesh size of the sieve such that the proportion of particles larger than the mesh size is 2% or less by volume of the volume particle size distribution measured by laser diffraction. Sieving may be performed using either a wet or dry method. If coarse particles are present in the filler, the nozzle may be clogged with the coarse particles during dispensing of the epoxy resin composition, resulting in a short discharge and an unstable discharge rate. Furthermore, when the epoxy resin composition is injected into the gap between the semiconductor element and the substrate, the coarse particles may clog, causing uneven injection speed, unfilled areas, and interruptions to the injection process. Unfilled areas of the epoxy resin composition may cause cracks in the curable resin composition due to temperature changes (temperature fluctuations) throughout the semiconductor device, resulting in reduced reliability.

[0034] The top cut diameter of the filler is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. When the top cut diameter of the filler falls within this range, poor injection due to coarse particles can be suppressed, thereby improving the injection speed of the epoxy resin composition. In addition, the epoxy resin composition can be applied to dispensers with small nozzle diameters. This allows the epoxy resin composition to be applied to narrow areas.

[0035] The content of the filler is from 55% by mass to less than 77% by mass, preferably from 60% by mass to 76% by mass, more preferably from 70% by mass to 76% by mass, and even more preferably from 73% by mass to 76% by mass, relative to the total amount of the epoxy resin composition. When the content of the filler falls within this range, the viscosity of the epoxy resin composition becomes appropriate, thereby improving workability.

[0036] <Other Components> The other components are not particularly limited as long as they are those commonly used in ordinary sealants and can be appropriately selected depending on the purpose. Examples of other components include curing agents other than heterocyclic compounds having nitrogen atoms, such as liquid acid anhydrides, liquid phenols, and aromatic amines; colorants such as dyes, pigments, and carbon black; silicone oils; surfactants; antioxidants; antimony oxides such as antimony trioxide, antimony tetraoxide, and antimony pentoxide; and conventionally known flame retardants such as brominated epoxy resins; ion trapping agents; leveling agents; antifoaming agents; and reactive diluents. These may be used alone or in combination of two or more types, as long as they do not impair the effects of the technology of the present disclosure. It should be noted that the inclusion of other curing agents is preferable because it can adjust the glass transition temperature and curing speed of the epoxy composition and improve adhesive strength.

[0037] The content of other components is not particularly limited and can be appropriately selected depending on the purpose.

[0038] <Physical Properties of Epoxy Resin Composition> <<Viscosity>> From the viewpoint of injectability, the viscosity of the epoxy resin composition at 25°C is preferably the following value. When the epoxy resin composition immediately after preparation is rotated at 50 rpm for 1 minute using a Brookfield viscometer at 25°C, the viscosity of the epoxy resin composition is preferably 5 Pa·s to 45 Pa·s. When the epoxy resin composition immediately after preparation is rotated at 5 rpm for 1 minute using a Brookfield viscometer at 25°C, the viscosity of the epoxy resin composition is preferably 2 Pa·s to 45 Pa·s. The thixotropic index (TI value: (viscosity at 5 rpm) / (viscosity at 50 rpm)) of the epoxy resin composition is preferably 0.3 to 1.2. When the viscosity value is within the above range, the dispensability and injectability are excellent. Note that this viscosity value is equivalent to the viscosity value of conventional epoxy resin compositions.

[0039] <<Chlorine Amount>> The chlorine amount (total chlorine amount) in the epoxy resin composition is preferably 1,300 ppm or less, and more preferably 1,000 ppm or less. If the total chlorine amount exceeds 1,300 ppm, the injectability and reliability may deteriorate, and storage stability may also deteriorate.

[0040] <Uses of Epoxy Resin Composition> The epoxy resin composition according to the embodiment can achieve both injectability and reliability, and therefore can be suitably used as an underfill material. This epoxy resin composition can be particularly suitably used for mounting semiconductor devices having fine pitches. For example, because of its good injectability, the epoxy resin composition can be injected as an underfill material to seal even a very small gap, such as a distance of 250 μm or less between a substrate and a semiconductor element. That is, the epoxy resin composition can be injected as an underfill material into a gap of 250 μm or less.

[0041] (Method for Producing Epoxy Resin Composition) The method for producing the epoxy resin composition according to the embodiment can be appropriately selected depending on the purpose. For example, the method for producing the epoxy resin composition according to the embodiment includes mixing and stirring the above-mentioned components.

[0042] When the epoxy resin is solid, it is preferable to carry out mixing and stirring after the epoxy resin has been liquefied and fluidized by heating or the like.

[0043] The components may be mixed simultaneously, or some of the components may be mixed first and then the remaining components may be mixed in. If it is difficult to uniformly disperse the filler in the epoxy resin, the epoxy resin and filler may be mixed first and then the remaining components may be mixed in.

[0044] The device used for mixing and stirring is not particularly limited and can be appropriately selected depending on the purpose. Examples of such devices include a roll mill.

[0045] (Semiconductor Device) A semiconductor device according to an embodiment includes a support, a cured product of the epoxy resin composition, and a semiconductor element. Examples of the semiconductor device include a semiconductor device encapsulated with the epoxy resin composition, such as a semiconductor device in which a semiconductor element and a support are encapsulated with the epoxy resin composition.

[0046] <Support> The support is not particularly limited as long as it can fix a semiconductor element, and can be appropriately selected depending on the purpose. Examples of the support include a substrate.

[0047] <<Substrate>> The substrate is not particularly limited and can be appropriately selected depending on the purpose. Examples of the substrate include a lead frame, a pre-wired tape carrier, a wiring board, glass, and a silicon wafer. The size, shape, and material of the substrate are not particularly limited as long as they are the size, shape, and material of commonly used substrates, and can be appropriately selected depending on the purpose.

[0048] <Semiconductor Element> The semiconductor element is not particularly limited and can be appropriately selected depending on the purpose. Examples of the semiconductor element include active elements such as semiconductor chips, transistors, diodes, and thyristors; and passive elements such as capacitors, resistors, resistor arrays, coils, and switches. The size, shape, and material of the semiconductor element are not particularly limited as long as they are the size, shape, and material of commonly used semiconductor elements, and can be appropriately selected depending on the purpose.

[0049] The cured product of the epoxy resin composition is provided between the support and the semiconductor element. The thickness of the cured product of the epoxy resin composition is not particularly limited and can be appropriately selected depending on the purpose. The thickness range is, for example, 10 μm or more and 800 μm or less. The shape of the cured product of the epoxy resin composition is not particularly limited and can be appropriately selected depending on the purpose.

[0050] (Method for Manufacturing Semiconductor Device) A method for manufacturing a semiconductor device according to an embodiment includes a step of filling an epoxy resin composition and a step of curing the epoxy resin composition, and further includes other steps as necessary.

[0051] <Step of Filling with Epoxy Resin Composition> The step of filling with the epoxy resin composition is a step of filling the gap between the support and the semiconductor element disposed on the support with the epoxy resin composition. At this time, mold underfill may be performed to encapsulate the entire semiconductor element. The support may be any of the above. The method of filling with the epoxy resin composition is not particularly limited and can be appropriately selected depending on the purpose. Examples of such methods include a dispense method, a casting method, and a printing method. When filling with the epoxy resin composition using a dispense method, a jet dispenser typically used to inject underfill materials can be used. The amount of epoxy resin composition to be filled is not particularly limited and can be appropriately selected depending on the purpose. Examples of such an amount include an amount that completely fills the gap between the semiconductor element and the support and further covers the side surfaces of the semiconductor element with the epoxy resin composition (an amount that forms a fillet).

[0052] <Step of curing the epoxy resin composition> The step of curing the epoxy resin composition is a step of curing the epoxy resin composition between the support and the semiconductor element. The method of curing the epoxy resin composition is not particularly limited and can be selected appropriately depending on the purpose. This method includes, for example, a method of heating the epoxy resin composition. The heating temperature is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of reliability, it is preferably 120°C to 200°C, more preferably 130°C to 180°C, and even more preferably 140°C to 170°C. The heating time is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of workability, it is preferably 15 minutes to 3 hours, more preferably 30 minutes to 2 hours.

[0053] Examples 1 to 8, Comparative Examples 1 to 4 The compositions shown in Tables 1 to 3 were mixed using a triple roll mill and then homogenized to obtain epoxy resin compositions.

[0054]

[0055]

[0056]

[0057] The polytetramethylene glycol-type epoxy resins used in the examples and comparative examples are as follows: Polytetramethylene glycol-type epoxy resin 1 (YX-7400N, manufactured by Mitsubishi Chemical Corporation, chlorine content: 500 ppm) Polytetramethylene glycol-type epoxy resin 2 (Epogose PT, manufactured by Yokkaichi Chemical Co., Ltd., chlorine content: 18,000 ppm)

[0058] The epoxy resins (epoxy resins other than polytetramethylene glycol-type epoxy resins) used in the examples and comparative examples are as follows: Epoxy resin 1 (RE410S, manufactured by Nippon Kayaku Co., Ltd., bisphenol A-type epoxy resin, chlorine content: 900 ppm) Epoxy resin 2 (jER 630, manufactured by Mitsubishi Chemical Corporation, aromatic amine-type trifunctional epoxy resin, chlorine content: 5,000 ppm) Epoxy resin 3 (EP-3980S, manufactured by ADEKA Corporation, aromatic amine-type bifunctional epoxy resin, chlorine content: 700 ppm)

[0059] The nitrogen atom-containing heterocyclic compounds used in the examples and comparative examples are as follows: 2-phenyl-4-methyl-1H-imidazole (Curezol 2P4MZ, manufactured by Shikoku Chemicals Corporation)

[0060] The fillers used in the examples and comparative examples are as follows. Filler 1 (SE605H-SMG, manufactured by Admatechs Co., Ltd., silicon dioxide surface-treated with 3-methacryloxypropyltrimethoxysilane, average particle size: 2.0 μm, top cut diameter: 5 μm) Filler 2 (SE5050-SME, manufactured by Admatechs Co., Ltd., silicon dioxide surface-treated with 3-methacryloxypropyltrimethoxysilane, average particle size: 1.5 μm, top cut diameter: 5 μm) Filler 3 (20SX-E7, manufactured by Admatechs Co., Ltd., silicon dioxide surface-treated with N-phenyl-3-aminopropyltrimethoxysilane, average particle size: 1.5 μm, top cut diameter: 5 μm) Filler 4 (SE5200-SME, manufactured by Admatechs Co., Ltd., silicon dioxide surface-treated with 3-methacryloxypropyltrimethoxysilane, average particle size: 1.5 μm, top cut diameter: 24 μm) Filler 5 (SE5050, manufactured by Admatechs Co., Ltd., silicon dioxide without surface treatment, average particle size: 1.5 μm, top cut diameter: 5 μm) Filler 6 (20SE-E10, manufactured by Admatechs Co., Ltd., silicon dioxide surface-treated with 3-glycidoxypropyltrimethoxysilane, average particle size 2.0 μm, top cut diameter 5 μm) Filler 7 (silicon dioxide obtained by surface-treating Filler 5 with tris-(trimethoxysilylpropyl)isocyanurate, average particle size: 1.5 μm, top cut diameter: 5 μm) Filler 8 (40SM-E2, manufactured by Admatechs Co., Ltd., silicon dioxide surface-treated with 3-methacryloxypropyltrimethoxysilane, average particle size 4.0 μm, top cut diameter: 10 μm)

[0061] Other components used in the examples and comparative examples are as follows: 3-glycidoxypropyltrimethoxysilane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) 3-isocyanatepropyltriethoxysilane (KBE9007N, manufactured by Shin-Etsu Chemical Co., Ltd.) Carbon black (Black 4, manufactured by Orion Engineered Carbons Co., Ltd.) Modified silicone (SF8421, manufactured by Dow Corning Toray Co., Ltd.)

[0062] The viscosity of the epoxy resin compositions of the Examples and Comparative Examples was measured as follows. Furthermore, the injection speed and dispensability were evaluated. The evaluation results are shown in Tables 1 to 3.

[0063] <Viscosity> The viscosity of each epoxy resin composition immediately after preparation (initial viscosity, unit: Pa s) was measured using a Brookfield viscometer when the epoxy resin composition was rotated at 50 rpm and 5 rpm at 25°C for 1 minute. The thixotropic index (TI: (viscosity at 5 rpm) / (viscosity at 50 rpm)) was calculated from the obtained viscosity values ​​at 50 rpm and 5 rpm.

[0064] <Injectability> Two pieces of gap tape (made of stainless steel (SUS), thickness: 15 μm) were placed on a glass slide, spaced 1 cm apart. Another glass slide was placed on top of them, and the two glass slides were fixed with clips. In this way, a test specimen was prepared, including two glass slides with a gap of 1 cm width and 15 μm height. This test specimen was placed on a hot plate set to 90°C, and each epoxy resin composition was applied to one end of the gap between the glass slides. Then, for each epoxy resin composition, the time (min) until the injection distance reached 20 mm was measured. This procedure was performed twice, and the average of the measured values ​​was used as the evaluation result of injectability.

[0065] <Dispensability> Using a jet dispenser (DJ-9000, Nordson Advanced Technology Co., Ltd.), 1000 dots of each epoxy resin composition were dispensed. Then, the stability (presence or absence of voids, scattering, and misalignment) and the presence or absence of liquid pooling in the nozzle after dispensing 1000 dots were visually confirmed and evaluated based on the following evaluation criteria. -Evaluation criteria- A: No voids, scattering, misalignment, or liquid pooling B: No voids, scattering, or misalignment, but liquid pooling present C: Any of voids, scattering, or misalignment present

[0066] As shown in Tables 1 and 2, it was revealed that the epoxy resin compositions of the Examples were evaluated as having good injectability. In contrast, the epoxy resin composition of Comparative Example 1, which contained 78% by mass of filler, was evaluated as having poor injectability, with a result of 15 minutes. Furthermore, the epoxy resin composition of Comparative Example 1 also had poor dispensability. The epoxy resin composition of Comparative Example 2, which used a filler that had not been surface-treated, was evaluated as having poor injectability, with a result of 25 minutes. Furthermore, the epoxy resin compositions of Comparative Examples 3 and 4, which used 3-glycidoxypropyltrimethoxysilane or tris-(trimethoxysilylpropyl)isocyanurate as the surface treatment agent, were evaluated as having poor injectability, with a result of 20 minutes and over 60 minutes, respectively. From the above, it has been revealed that an epoxy resin composition containing a polytetramethylene glycol-type epoxy resin, a nitrogen-containing heterocyclic compound, and a filler, in which the filler is surface-treated with at least one of 3-methacryloxypropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane, and in which the filler content is 55% by mass or more and less than 77% by mass with respect to the total amount of the epoxy resin composition, can be applied using a dispenser and has good injectability.

[0067] The embodiments and examples of the present disclosure have been described. These are presented as examples and are not intended to limit the technical scope of the present disclosure. The embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made to the embodiments without departing from the spirit of the present disclosure. The embodiments and their modifications are intended to be included within the technical scope and spirit of the present disclosure, as well as within the technical ideas described in the claims and their equivalents.

Claims

1. A polytetramethylene glycol type epoxy resin, a nitrogen-containing heterocyclic compound; A filler and the filler is surface-treated with at least one of 3-methacryloxypropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; The content of the filler is 55% by mass or more and less than 77% by mass based on the total amount of the epoxy resin composition. Epoxy resin composition.

2. The average particle size of the filler is 2.0 μm or less. The epoxy resin composition according to claim 1.

3. The top cut diameter of the filler is 15 μm or less. The epoxy resin composition according to claim 1 or 2.

4. The total amount of chlorine is 1,300 ppm or less based on the total amount of the epoxy resin composition. The epoxy resin composition according to claim 1 or 2.

5. Injected as an underfill material into gaps of 250 μm or less. The epoxy resin composition according to claim 1 or 2.

6. The epoxy resin composition according to claim 1 or 2 is used for sealing. Semiconductor device.

7. A step of filling a gap between a support and a semiconductor element disposed on the support with the epoxy resin composition according to claim 1 or 2; and curing the epoxy resin composition. A method for manufacturing a semiconductor device.