TW202415725A - Epoxy resin composition, semiconductor device, and method for manufacturing semiconductor device - Google Patents

Abstract

[Topic] To provide an epoxy resin composition, a semiconductor device and a method for manufacturing a semiconductor device that can be applied using a spray dispenser and has good injectability. [Solution] The epoxy resin composition contains a polytetramethylene glycol type epoxy resin, a heterocyclic compound containing a nitrogen atom and a filler, wherein the filler is surface-treated with at least one of 3-methacryloyloxypropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane, and the content of the filler is 55% by mass or more and less than 77% by mass relative to the total amount of the epoxy resin composition.

Description

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

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

Electronic equipment with semiconductor devices is required to be miniaturized, lightweight, and high-performance. In order to meet such requirements, the mainstream mounting method in semiconductor devices has shifted from wire bonding to flip-chip mounting. Flip-chip mounting is generally performed by the following operations. First, the electrode (bump) surface of the semiconductor element is made to face the electrode (pad) surface of the substrate, and they are electrically connected. Secondly, the connection between the electrodes is protected and reinforced from the outside. After that, in order to alleviate the stress caused by the difference in the linear expansion coefficient between the semiconductor element and the substrate, a liquid thermosetting adhesive called bottom filling material (also called sealing material) with this effect is usually used to seal the semiconductor element and the substrate.

As a method of supplying bottom fill material, capillary flow is generally used. Capillary flow is to coat the bottom fill material along the periphery of the semiconductor element after the bump and the pad are connected, and inject the bottom fill material into the gap between the two by using the capillary phenomenon. After the bottom fill material is injected, the bottom fill material is hardened by heating to strengthen the connection between the two.

The bottom filling material is generally a composition containing an epoxy resin and a filler. As an example of a bottom filling material, a composition containing an aminophenol type epoxy resin, an amine hardener, a silicon oxide filler, and a silane coupling agent has been proposed (for example, refer to Patent Document 1). In addition, a bottom filling material containing an epoxy resin, a hardener, a filler, and a modified polysiloxane has been proposed (for example, refer to Patent Document 2). Therefore, various bottom filling materials have been proposed so far, in which the type of epoxy resin, the type of hardener, etc. are changed. [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent Publication No. 2016-113525 [Patent Document 2] Japanese Patent Publication No. 2001-55488

[The problem that the invention wants to solve]

In recent years, with the high output of semiconductor devices, the wiring in semiconductor devices has become more dense. Therefore, the application of bottom fill materials to micro areas has become more common. As a method of applying bottom fill materials to micro areas, a jet dispenser is more commonly used. The application using a jet dispenser is to spray droplets of bottom fill materials from a nozzle at a position far away from the substrate. Therefore, the viscosity of the bottom fill material is required to be low to a certain extent.

In flip chip mounting, the time required to inject the bottom filler material becomes a bottleneck. Therefore, in order to improve production efficiency, it is better to increase the injection speed of the bottom filler material. As a method to increase the injection speed, that is, to improve the injectability, there is a method to increase the filler particle size to reduce the viscosity of the bottom filler material. However, if the filler particle size becomes larger, the injection speed becomes uneven due to the blockage of the coarse filler particles, resulting in unfilled areas.

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

The inventors of the present invention have examined what kind of resin should be used to improve the injectability of a resin composition containing a large number of fillers and having a small filler particle size. As a result, it was found that a bottom filling material with good injectability can be realized by using a polytetramethylene glycol type epoxy resin with a high stress relieving effect as an epoxy resin, a filler, and an appropriate hardener component.

Specifically, in order to achieve the above-mentioned purpose, an epoxy resin composition of an embodiment of the present disclosure contains a polytetramethylene glycol type epoxy resin, a heterocyclic compound containing nitrogen atoms and a filler, wherein the filler is surface-treated by at least one of 3-methacryloyloxypropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane, and the content of the filler is 55 mass% or more and less than 77 mass% relative to the total amount of the epoxy resin composition. [Effect of the invention]

According to one embodiment of the present disclosure, an epoxy resin composition that can be applied using a spray dispenser and has good injectability, a semiconductor device, and a method for manufacturing a semiconductor device can be provided.

(Epoxy resin composition)

The epoxy resin composition of the embodiment contains a polytetramethylene glycol type epoxy resin, a heterocyclic compound containing nitrogen atoms, and a filler. The epoxy resin composition of the embodiment preferably contains an epoxy resin other than the polytetramethylene glycol type epoxy resin, and may contain other components as necessary.

<Polytetramethylene glycol epoxy resin> Polytetramethylene glycol epoxy resin is included to improve injectability because it can reduce the viscosity of epoxy resin composition. In addition, polytetramethylene glycol epoxy resin does not have a rigid ring in the molecule and is composed only of a straight chain structure with a soft structure. Therefore, polytetramethylene glycol epoxy resin is a resin with a high stress relieving effect, has softness, can give flexibility to the cured product, and can reduce the elastic modulus of the cured product. In addition, since polytetramethylene glycol epoxy resin is a resin with a high stress relaxation effect, it can suppress the occurrence of defects such as cracks in the cured epoxy resin composition or semiconductor components due to temperature cycles after installation. In other words, polytetramethylene glycol epoxy resin can improve reliability (reliability after installation).

Regarding the molecular weight of polytetramethylene glycol epoxy resin, from the viewpoint of the balance between viscosity and flexibility, the weight average molecular weight is preferably 500~3,000, preferably 1,500~2,500. In this specification, the weight average molecular weight refers to the value of the calibration curve formed by standard polystyrene obtained by gel permeation chromatography (GPC). If the weight average molecular weight is less than 500, the effect of imparting flexibility is small, so there is a possibility that reliability becomes poor. On the other hand, if the weight average molecular weight is more than 3,000, there is a concern that the epoxy resin composition becomes highly viscous and workability deteriorates.

The number of epoxy groups contained in one molecule of the polytetramethylene glycol epoxy resin is not particularly limited and can be appropriately selected according to the purpose. From the perspective of reliability, 2 or more (multifunctional epoxy resin) are preferred. The upper limit of the number of epoxy groups is not particularly limited and can be appropriately selected according to the purpose. 5 or less are preferred.

The chlorine content of polytetramethylene glycol epoxy resin is preferably less than 1,000 ppm from the viewpoint of injectability, storage stability, and reliability.

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.

Compared to epoxy resin, the content of polytetramethylene glycol epoxy resin is preferably 10% to 30% by mass. If the content of polytetramethylene glycol epoxy resin is less than 10% by mass, the effects of reducing stress relief and viscosity will be insufficient. On the other hand, if the content of polytetramethylene glycol epoxy resin exceeds 30% by mass, the cured product will become brittle, and the reliability after installation will be reduced.

<Other epoxy resins> Other epoxy resins are epoxy resins other than the above-mentioned polytetramethylene glycol type epoxy resins. Other epoxy resins can be used without any particular restrictions as long as they are various epoxy resins generally used for semiconductor sealing. There is no particular restriction on the number of epoxy groups contained in one molecule of other epoxy resins, and it can be appropriately selected according to the purpose. From the perspective of reliability, 2 or more (multifunctional epoxy resins) are preferred. There is no particular restriction on the upper limit of the number of epoxy groups, and it can be appropriately selected according to the purpose. 5 or less are preferred. The epoxy equivalent of other epoxy resins is preferably 50g/eq.~10000g/eq., more preferably 50g/eq.~1000g/eq., and even more preferably 100g/eq.~500g/eq. Here, the epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy groups as defined in JIS K 7236:2001. Moreover, "eq." is an abbreviation of "equivalent".

Examples of epoxy resins other than polytetramethylene glycol epoxy resins include epoxy resins of glycidylamine type, 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 epoxy resins of glycidylamine type include diglycidylaniline, diglycidyltoluidine, and tetraglycidyl-m-xylenediamine tetraglycidylbis(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 resin and bisphenol F type epoxy resin. Examples of bisphenol A type epoxy resins include p-glycidoxyphenyl dimethyltrisphenol A diglycidyl ether. Examples of biphenyl epoxy resins include biphenyl aralkyl epoxy resins and 3,3',5,5'-tetramethyl-4,4'-diglycidoxybiphenyl. Examples of aminophenol epoxy resins include triglycidyl-p-aminophenol. Examples of monofunctional epoxy resins include p-tert-butylphenyl glycidyl ether. Examples of polyfunctional epoxy resins include diglycidyl 1,4-phenyldimethanol diglycidyl ether and triglycidyl ether. In addition to the above, epoxy resins other than polytetramethylene glycol type epoxy resins may also be hydantoin type epoxy resins such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; epoxy resins having a siloxy skeleton such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane; and epoxy resins having a skeleton derived from plants. From the perspective of crack resistance, aminophenol type epoxy resins, bisphenol type epoxy resins, and aliphatic epoxy resins are preferred. Moreover, it is preferred to use aliphatic epoxy resins and aromatic epoxy resins together. One of these can be used alone or two or more can be used in combination.

The content of epoxy resin (the total amount of polytetramethylene glycol type epoxy resin and other epoxy resins) is not particularly limited and can be appropriately selected according to the purpose. It is preferably 45% to 23% by mass relative to the total amount of the epoxy resin composition. If the content of epoxy resin is within this range, the injectability becomes good.

<Heterocyclic compounds containing nitrogen atoms> Heterocyclic compounds containing nitrogen atoms are contained in order to cure epoxy resin compositions. When the epoxy resin composition is cured, the heterocyclic compounds containing nitrogen atoms undergo a monopolymerization with the epoxy resin or the like. In contrast, amine-based curing agents undergo an addition polymerization with the epoxy resin or the like. Due to the difference in this reaction, heterocyclic compounds containing nitrogen atoms cure with lower crosslinking density and linear expansion coefficient compared to amine-based curing agents. Therefore, by using heterocyclic compounds containing nitrogen atoms as curing agents, the linear expansion coefficient of the cured epoxy resin composition at a temperature above the glass transition temperature can be reduced. As a result, at high temperatures, the gap between the linear expansion coefficient of the cured epoxy resin composition and the linear expansion coefficient of the chip becomes smaller, and the stress generated becomes smaller. Therefore, reliability can be improved.

The heterocyclic compound containing nitrogen atoms is not particularly limited as long as it can harden the resin in the epoxy resin composition, and can be appropriately selected according to the purpose. Examples of the heterocyclic compound include imidazole derivatives and microencapsulated heterocyclic compounds containing nitrogen atoms. 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 imidazole derivatives, commercial products or those synthesized appropriately can be used. Examples of commercial products include 2P4MZ (2-phenyl-4-methylimidazole), 2MZA (2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, and 2-phenyl-4-methylimidazole) (both manufactured by Shikoku Chemical Industries, Ltd.).

The nitrogen-containing heterocyclic compound may also be microencapsulated. As the nitrogen-containing heterocyclic compound microencapsulated, commercially available products may be used, or those suitably synthesized may be used. As commercially available products, for example, 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 Co., Ltd.), Amicure PN-23J, Amicure PN-40J (all manufactured by Ajinomoto Seiko Co., Ltd.), and Fujicure FXR-1121 (manufactured by Fuji Chemical Industries, Ltd.) may be cited. These may be used alone or in combination of two or more.

Among the nitrogen-containing heterocyclic compounds, 2-phenyl-4-methylimidazole is preferred from the viewpoints of reactivity and storage stability.

The content of nitrogen-containing heterocyclic compounds is not particularly limited and can be appropriately selected according to the purpose. Relative to the epoxy resin composition without the filler described later, the content of nitrogen-containing heterocyclic compounds is preferably 2.0 mass% to 8.0 mass%, preferably 2.5 mass% to 6.0 mass%. If the content of nitrogen-containing heterocyclic compounds is above 2.0 mass%, the productivity of electronic component devices can be improved because the curing time of the epoxy resin composition can be accelerated. If the content of nitrogen-containing heterocyclic compounds is below 8.0 mass%, the storage stability of the epoxy resin composition is improved. Regarding the content of the nitrogen-containing heterocyclic compound after microencapsulation, relative to the epoxy resin composition without fillers, the content of the active ingredient (nitrogen-containing heterocyclic compound) is preferably 3% to 25% by mass, and preferably 5% to 20% by mass.

<Filler> The filler is contained in order to reduce the linear expansion coefficient of the cured epoxy resin composition and to inhibit the volume shrinkage caused by the curing reaction of the epoxy resin composition.

The filler is not particularly limited as long as it is contained in a common epoxy resin composition, and can be appropriately selected according to the purpose. As a filler, for example, inorganic particles can be cited. As inorganic particles, for example, silicon oxide and aluminum oxide can be cited. In addition, the filler can also be a filler with other functions such as coloring. As such a filler, for example, inorganic pigments such as white pigments can be cited. As inorganic pigments, for example, magnesium oxide, titanium oxide, zirconium oxide, boron nitride, aluminum nitride, titanium oxide, magnesium oxide, zinc oxide, aluminum oxide, diamond, potassium titanate, magnesium sulfate, sepiolite, hard silica, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide, barium titanate, and zirconium oxide can be cited. These can be used alone or in combination of two or more. Among them, silica filler is preferred in terms of increasing the filling amount.

The filler is surface treated with at least one of 3-methacryloyloxypropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane. By applying such surface treatment, the aggregation of the filler can be suppressed and the dispersibility can be improved. In addition, since the wettability of the filler with the resin component is improved, the interface bonding between the filler and the resin becomes stronger, and the bonding between the filler and the resin component can be improved. Thereby, the viscosity increase of the epoxy resin composition and the decrease of the injection speed can be suppressed, and the toughness of the cured epoxy resin composition can be improved.

The shape of the filler is not particularly limited and can be appropriately selected according to the purpose. Examples of the shape of the filler include spherical, irregular, and scaly shapes. However, from the perspective of maintaining the fluidity of the epoxy resin composition and increasing the filling amount, a spherical shape is preferred.

The volume average particle size of the filler (hereinafter referred to as the average particle size) is preferably less than 2.0 μm, 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 distribution may occur, resulting in poor distribution. Moreover, 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.

The average particle size of the filler refers to the volume average particle size D50 (the particle size from the small diameter side to the cumulative 50% particle size distribution) value measured using a laser diffraction particle size distribution measuring device (LS13320, manufactured by Beckman Coulter). The average particle size was measured by the following operation. The sample for measurement was prepared by dispersing 5 mg of filler in 50 mg of dispersant and dispersing for 10 minutes using an ultrasonic disperser. The average particle size of the sample for measurement was measured under the conditions of a flow rate of 50 mL/second, a measurement time of 90 seconds, a solvent of pure water, and a solvent refractive index of 1.333.

As fillers, it is better to use top-cut ones. Top-cut refers to the classification of powders for the purpose of removing coarse particles. And, the top-cut diameter refers to the sieve hole of the sieve used to classify fillers by sieving. That is, the top-cut diameter refers to the value of the sieve hole of the sieve so that the proportion of particles larger than the sieve hole becomes less than 2 volume % of the volume particle size distribution measured by laser diffraction method. The classification by sieving method can be wet or dry. In the case of coarse particles in the filler, the coarse particles may clog the nozzle when the epoxy resin composition is distributed, resulting in discharging interruption and unstable discharging amount. In addition, when injecting the epoxy resin composition into the gap between the semiconductor element and the substrate, there may be clogging with coarse particles, uneven injection speed, unfilled areas, and injection stopped in the middle. If there are unfilled areas of the epoxy resin composition, the temperature change (temperature up and down) of the entire semiconductor device may cause cracks in the curing resin composition, thereby reducing reliability.

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. If the top cut diameter of the filler is within this range, the injection speed of the epoxy resin composition can be increased because poor injection due to coarse particles can be suppressed. In addition, the epoxy resin composition can be applied to a distributor with a small nozzle diameter. Therefore, the epoxy resin composition can be applied to a narrow place.

The content of the filler is 55% by mass or more and less than 77% by mass relative to the total amount of the epoxy resin composition, preferably 60% by mass or more and 76% by mass or less, more preferably 70% by mass or more and 76% by mass or less, and even more preferably 73% by mass or more and 76% by mass or less. If the value of the filler content is included in this range, the viscosity of the epoxy resin composition becomes appropriate, thereby improving workability.

<Other components> As other components, there are no particular restrictions as long as they are used in common sealing materials, and they can be appropriately selected according to the purpose. As other components, for example, hardeners other than heterocyclic compounds having nitrogen atoms such as liquid acid anhydrides, liquid phenols, and aromatic amines; coloring agents such as dyes, pigments, and carbon black; silicone oils; surfactants; antioxidants; antimony oxides such as antimony trioxide, antimony tetroxide, and antimony pentoxide, and previously known flame retardants such as brominated epoxy resins; ion collectors; leveling agents; defoaming agents; reactive diluents, etc. As long as the technical effects of the present disclosure are not impaired, these can be used alone or in combination of two or more. Furthermore, it is preferable to contain other hardeners because the glass transition temperature and hardening speed of the epoxy composition can be adjusted, and the subsequent strength can be improved.

The contents of other ingredients are not particularly limited and can be appropriately selected according to the purpose.

<Physical properties of epoxy resin composition> <<Viscosity>> From the perspective of injectability, the viscosity of the epoxy resin composition at 25°C is preferably the following value. Using a Brookfield viscometer, at 25°C, the epoxy resin composition is rotated at 50 rpm for 1 minute. The viscosity of the epoxy resin composition is preferably 5Pa･s~45Pa･s. Using a Brookfield viscometer, at 25°C, the epoxy resin composition is rotated at 5 rpm for 1 minute. The viscosity of the epoxy resin composition is preferably 2Pa･s~45Pa･s. The thixotropic index (TI value: (viscosity at 5rpm)/(viscosity at 50rpm)) of the epoxy resin composition is preferably 0.3~1.2. If the viscosity value is within the above range, the dispensability and injection properties become good. Moreover, the viscosity value is equivalent to the viscosity value of the conventional epoxy resin composition.

＜＜Chlorine content＞＞ The chlorine content (total chlorine content) in the epoxy resin composition is preferably below 1,300 ppm, preferably below 1,000 ppm. If the total chlorine content exceeds 1,300 ppm, injectability and reliability may deteriorate, and storage stability may also deteriorate.

<Use of epoxy resin composition> The epoxy resin composition of the embodiment can be suitably used as a bottom filling material because it can achieve both injectability and reliability. The epoxy resin composition is particularly suitable for mounting semiconductor devices with fine pitches. For example, due to the good injectability, even if the distance between the substrate and the semiconductor element is a fine gap of less than 250μm, the epoxy resin composition can still be injected as a bottom filling material and sealed. That is, the epoxy resin composition can be injected into a gap of less than 250μm as a bottom filling material.

(Method for producing epoxy resin composition) The method for producing the epoxy resin composition of the embodiment can be appropriately selected according to the purpose. As the production method, for example, a method of mixing and stirring the above-mentioned components can be cited.

Furthermore, when the epoxy resin is solid, it is preferred to liquefy and fluidize the epoxy resin by heating or the like, and then perform mixing and stirring.

In addition, the components may be mixed simultaneously, or some components may be mixed first and then the remaining components. In the case where it is difficult to evenly disperse the filler in the epoxy resin, the epoxy resin and the filler may be mixed first and then the remaining components may be mixed.

The device used for mixing and stirring is not particularly limited and can be appropriately selected according to the purpose. Examples of such devices include a roller mill and the like.

(Semiconductor device) The semiconductor device of the embodiment comprises: a support, a cured product of the epoxy resin composition, and a semiconductor element. As the semiconductor device, for example, a semiconductor device sealed by the epoxy resin composition can be cited, in which a semiconductor element and a support are sealed by the epoxy resin composition.

<Support> The support is not particularly limited as long as it can fix the semiconductor element, and can be appropriately selected according to the purpose. Examples of the support include substrates, etc.

＜＜Substrate＞＞ There is no particular restriction on the substrate, and it can be appropriately selected according to the purpose. Examples of the substrate include lead frames, wired tape carriers, wiring boards, glass, and silicon wafers. There is no particular restriction on the size, shape, and material of the substrate, as long as it is the size, shape, and material of a commonly used substrate, and it can be appropriately selected according to the purpose.

<Semiconductor components> Semiconductor components are not particularly limited and can be appropriately selected according to the purpose. Examples of semiconductor components include active components such as semiconductor chips, transistors, diodes, and gates; passive components such as capacitors, resistors, resistor arrays, coils, and switches. The size, shape, and material of semiconductor components are not particularly limited as long as they are the size, shape, and material of commonly used semiconductor components, and can be appropriately selected according to the purpose.

The cured epoxy resin composition is disposed between the support and the semiconductor element. The thickness of the cured epoxy resin composition is not particularly limited and can be appropriately selected according to the purpose. As the thickness range, for example, 10 μm or more and 800 μm or less can be cited. The shape of the cured epoxy resin composition is not particularly limited and can be appropriately selected according to the purpose.

(Method for manufacturing semiconductor device) The method for manufacturing semiconductor device of the embodiment has: a step of filling the epoxy resin composition, a step of hardening the epoxy resin composition, and other necessary steps.

<Step of filling epoxy resin composition> The step of filling epoxy resin composition is a step of filling the gap between the support and the semiconductor element arranged on the support. At this time, mold bottom filling (mold uderfill) can be performed to seal the entire semiconductor element at once. As the support, the above-mentioned ones can be used. The method of filling epoxy resin composition is not particularly limited and can be appropriately selected according to the purpose. As the method, for example, a dispensing method, a casting method, and a printing method can be cited. Moreover, in the case of using the dispensing method to fill the epoxy resin composition, a spray dispenser generally used for injecting bottom filling materials can be used. The amount of epoxy resin composition filled is not particularly limited and can be appropriately selected according to the purpose. Examples of such amount include the amount of epoxy resin composition that completely fills the gap between the semiconductor element and the support, and the amount of the side of the semiconductor element covered by the epoxy resin composition (the amount that forms a rounded corner).

<Step of hardening the epoxy resin composition> The step of hardening the epoxy resin composition is a step of hardening the epoxy resin composition between the support and the semiconductor element. The method of hardening the epoxy resin composition is not particularly limited, and can be appropriately selected according to the purpose. As such a method, for example, a method of heating the epoxy resin composition can be cited. The heating temperature is not particularly limited, and can be appropriately selected according to the purpose. From the perspective of reliability, 120°C to 200°C is preferred, 130°C to 180°C is more preferred, and 140°C to 170°C is more preferred. There is no particular limit to the heating time, and it can be appropriately selected according to the purpose. From the perspective of workability, 15 minutes to 3 hours is preferred, and 30 minutes to 2 hours is preferred. [Example]

(Examples 1 to 8, Comparative Examples 1 to 4) The epoxy resin composition was obtained by blending and homogenizing using a three-roll mill under the blending conditions described in Tables 1 to 3.

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

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: 900ppm) ・Epoxy resin 2 (jER 630, manufactured by Mitsubishi Chemical Co., Ltd., aromatic amine type trifunctional epoxy resin, chlorine content: 5,000ppm) ・Epoxy resin 3 (EP-3980S, manufactured by ADEKA Co., Ltd., aromatic amine type bifunctional epoxy resin, chlorine content: 700ppm)

The heterocyclic compounds containing nitrogen atoms used in the Examples and Comparative Examples are as follows. ・2-phenyl-4-methyl-1H-imidazole (Curezol 2P4MZ, manufactured by Shikoku Chemical Industries, Ltd.)

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

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 Engineering Carbon Co., Ltd.) ・Modified silica (SF8421, manufactured by Toray Dow Corning Co., Ltd.)

For the epoxy resin compositions of the embodiments and comparative examples, the viscosity was measured by the following operation. In addition, the injection speed and dispensability were evaluated. The evaluation results are listed in Tables 1 to 3.

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

<Injectability> On a glass slide, two gap tapes (made of stainless steel (SUS), thickness: 15μm) were placed at an interval of 1cm. Another glass slide was placed on top of it, and the two glass slides were fixed with a clip. This operation produced a test piece containing two glass slides with a gap of 1cm in width and 15μm in height. The test piece was placed on a heating plate set at 90℃, and each epoxy resin composition was applied to one end of the gap in the glass slide. Thereafter, the time (min) until the injection distance reached 20mm was measured for each epoxy resin composition. This procedure was carried out twice, and the average of the measured values was used as the evaluation result of injectability.

<Dispensability> Using a spray dispenser (DJ-9000, Nordson Advanced Technologies Co., Ltd.), 1000 points were dispensed for each epoxy resin composition. Afterwards, the stability (presence of voids, scattering, and positional deviation) and the presence of liquid accumulation at the nozzle after dispensing 1000 points were visually confirmed, and the evaluation was conducted based on the following evaluation criteria. -Evaluation Criteria- A: No voids, scattering, positional deviation, and liquid accumulation B: No voids, scattering, positional deviation, but liquid accumulation C: Any of voids, scattering, and positional deviation

As shown in Tables 1-2, it is clearly found that the injectability evaluation of the epoxy resin composition of the embodiment is good. In contrast, the injectability evaluation result of the epoxy resin composition of Comparative Example 1, in which the filler content is 78 mass%, is 15 minutes, and the injectability is poor. Moreover, the distribution of the epoxy resin composition of Comparative Example 1 is poor. In addition, the injectability evaluation result of the epoxy resin composition of Comparative Example 2, which uses fillers that are not surface treated, is 25 minutes, and the injectability is poor. Moreover, the injectability evaluation results of Comparative Examples 3 and 4, in which the surface treatment agent is 3-glycidoxypropyltrimethoxysilane or tris-(trimethoxysilylpropyl)isocyanurate, are 20 minutes and more than 60 minutes, respectively, and the injectability is poor. From the above, it is clearly found that the epoxy resin composition contains a polytetramethylene glycol type epoxy resin, a heterocyclic compound containing a nitrogen atom, and a filler, and the filler is surface-treated by at least one of 3-methacryloyloxypropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane, and the content of the filler is 55 mass% or more and less than 77 mass% relative to the total amount of the epoxy resin composition. It is an epoxy resin composition that can be applied using a dispenser and has good injectability.

The embodiments and examples of the present disclosure are 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 changes can be made to the embodiments without exceeding the scope of the gist of the present disclosure. The embodiments and their variations are included in the technical scope and gist of the present disclosure, and are also included in the technical ideas and their equivalents recorded in the scope of the patent application.

Claims (7)

An epoxy resin composition comprising a polytetramethylene glycol type epoxy resin, a heterocyclic compound containing nitrogen atoms, and a filler; wherein the filler is surface-treated with at least one of 3-methacryloyloxypropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane, and the content of the filler is 55% by mass or more and less than 77% by mass relative to the total amount of the epoxy resin composition. The epoxy resin composition of claim 1, wherein the average particle size of the filler is less than 2.0 μm. The epoxy resin composition of claim 1 or 2, wherein the top cut diameter of the filler is less than 15 μm. The epoxy resin composition of claim 1 or 2, wherein the total chlorine content is less than 1,300 ppm relative to the total amount of the epoxy resin composition. The epoxy resin composition of claim 1 or 2 is injected into a gap of less than 250 μm as a bottom filling material. A semiconductor device sealed by the epoxy resin composition of claim 1 or 2. A method for manufacturing a semiconductor device, comprising: a step of filling the gap between a support and a semiconductor element disposed on the support with an epoxy resin composition as described in claim 1 or 2, and a step of hardening the epoxy resin composition.