Epoxy resin composition and application thereof

Abstract

The invention provides an epoxy resin composition and application thereof. The epoxy resin composition comprises the following components in parts by weight: (a) 12-20 parts of epoxy resin; (b) 5-15 parts of an amine curing agent; (c) 0.05 to 3 parts of an antioxidant; (d) 50-75 parts of filler, wherein the amine curing agent is a composition of a diphenylmethane type amine compound and a sulfur-containing benzene ring type amine compound. After being cured, the epoxy resin composition disclosed by the invention has an improvement effect on cracking of a bump corner (Bmu m p corner) material.

Description

Technical Field

[0001] The present invention relates to the technical field of semiconductor packaging, and in particular to an epoxy resin composition and application thereof. Background Art

[0002] With the continuous development of semiconductor industry technology, 5G networks, artificial intelligence, cloud computing, and big data iteration technologies are constantly improving, which puts forward the requirements of high reliability, low power consumption, miniaturization, light weight, and precision for chip performance. In order to shorten the interconnection distance between the chip and the substrate, the semiconductor packaging method has gradually changed from the traditional lead and substrate interconnection method to the advanced bump and substrate interconnection method, so as to improve the speed and frequency of device information processing and reduce the information transmission loss in the high-frequency area.

[0003] As a method for connecting the electrodes of semiconductor chips and circuit substrates, direct connection through materials such as gold wires and solder is currently widely used. For example, in the flip chip bonding technology commonly used in advanced packaging, the semiconductor chip and the circuit board are directly connected to the electrodes on the circuit board through solder bumps, copper pillars, etc. formed on the electrode part of the semiconductor chip. Due to the mismatch between the linear expansion coefficient of the silicon chip and the linear expansion coefficient of the substrate, stress is easily generated under the conditions of thermal expansion and contraction during the chip packaging reflow process, and crack defects are generated at the interconnection between the chip and the substrate, which will seriously affect the high reliability of the chip substrate interconnection. As a countermeasure to overcome this problem, a packaging technology that fills the bottom filling material between the semiconductor chip and the wiring substrate is adopted. By using an epoxy resin composition bottom filling material, it plays a key role in alleviating the stress problem caused by the mismatch of the thermal expansion coefficient between the chip and the substrate, and can effectively improve the bump connection reliability of the device under thermal stress such as thermal cycling and the bump connection reliability under physical stress such as impact and bending. In particular, the bottom filling material at the bump corner (Bμmp corner) position has filler sedimentation, such as Figure 1 As shown, the resin and filler are unevenly distributed, and the resin gathers at the corners of the bumps, resulting in a large thermal expansion coefficient of the material, insufficient mechanical strength, and greatly reduced protection of the bumps, which leads to cracking, delamination, and breakage of bump connections at the interface between the chip bumps and the bottom filling material. For example, the existing patents CN 104470989B and CN104684957B have reported that the bottom filling material breaks the bump electrode due to thermal stress on the bump electrode, and the mechanical protection of the bump is poor, causing the packaged chip device to fail.

[0004] Therefore, it is necessary to develop a new bottom filling material that can improve the cracking of the bump corner (Bμmp corner) material. Summary of the invention

[0005] In view of this, the object of the present invention is to provide an epoxy resin composition with anti-filler sedimentation to solve the problem of filler sedimentation in the corners of bumps during the flow filling process of the bottom filling material of the epoxy resin composition, uneven distribution of resin and filler, resulting in high stress in the corners of the bumps, bump breakage, and failure of the packaged chip device.

[0006] Another object of the present invention is to provide application of the epoxy resin composition.

[0007] To achieve the above object, the present invention provides an epoxy resin composition comprising the following components in parts by weight:

[0008] (a) 12 to 20 parts of epoxy resin, for example 13, 14, 15, 16, 17, 18, 19 parts by weight;

[0009] (b) 5 to 15 parts of an amine curing agent, for example 6, 7, 8, 9, 10, 11, 12, 13, 14 parts by weight;

[0010] (c) 0.05 to 3 parts of an antioxidant, for example 0.5, 1, 1.5, 2, 2.5 parts by weight;

[0011] (d) 50 to 75 parts of filler, for example 55, 60, 65, 70 parts by weight.

[0012] The epoxy resin composition of the present invention has no special requirements for the epoxy resin described in component (a), and can be, for example, at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene ring epoxy resin, alicyclic epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, and alcohol ether epoxy resin.

[0013] In the epoxy resin composition of the present invention, the amine curing agent described in component (b) is a composition of a diphenylmethane amine compound and a sulfur-containing benzene ring amine compound, wherein the mass ratio of the diphenylmethane amine compound to the sulfur-containing benzene ring amine compound is 0.1 to 10:1, such as 0.5:1, 1, preferably 3 to 6:1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, etc.;

[0014] The diphenylmethane amine compound is at least one of the compounds shown in Formula 1:

[0015]

[0016] In Formula 1, R1 and R2 are each independently hydrogen or a C1-C3 alkyl group, such as a methyl group, an ethyl group, or a propyl group;

[0017] The sulfur-containing benzene ring amine compound is at least one of the compounds shown in Formula 2:

[0018]

[0019] In Formula 2, R1, R2, and R3 are each independently any one of hydrogen, a C1-C3 alkyl group (eg, methyl, ethyl, propyl), an amino group, and a mercapto group.

[0020] In the epoxy resin composition of the present invention, the antioxidant described in component (c) has at least one of the compounds shown in Formula 3:

[0021]

[0022] In formula 3, R1, R2, and R3 are each independently hydrogen, a C1-C12 alkyl group (eg, methyl, ethyl, propyl, butyl, isopropyl, octyl, nonyl, decyl, etc.), a hydroxyl group, or a mercapto group.

[0023] Preferably, the antioxidant is at least one of 6-tert-butyl-2,4-dimethylphenol, 3,5-di-tert-butylcatechol, Shanghai Huayuan Century Trading Co., Ltd., 2,6-di-tert-butyl-4-methylphenol, 4-tert-butylcatechol, Nantong Runfeng Petrochemical Co., Ltd., 3-tert-butylcatechol, and Macklin's reagent;

[0024] Preferably, the purity of the antioxidant is above 99%.

[0025] In the epoxy resin composition of the present invention, the filler described in component (d) is selected from at least one of silicon dioxide, aluminum oxide, and silicon nitride, preferably spherical silicon dioxide;

[0026] Preferably, the average particle size of the filler is 0.1-5 μm, for example, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, etc., more preferably 0.1-3 μm.

[0027] The epoxy resin composition of the present invention further comprises component (e) 0 to 2 parts of a pigment;

[0028] Preferably, there is no special requirement for the pigment, and the pigment can be selected conventionally in the art.

[0029] The epoxy resin composition of the present invention, when using an antioxidant of the general formula 3 structure, the phenolic hydroxyl group on the benzene ring thereof is reactive and can react with the epoxy group on the epoxy resin to form a polymer, so that the viscosity of the bottom filling glue system increases, which is conducive to suppressing the problem of filler sedimentation during the device dispensing flow process. At the same time, due to the steric hindrance effect of the R group on the antioxidant general formula 3, the reactivity of the phenolic hydroxyl group and the epoxy group is relatively low, ensuring that the viscosity of the bottom filling glue system is appropriate and can meet the requirements of the dispensing workability of the packaged device. Therefore, by introducing the antioxidant, the problem of filler sedimentation in the corner of the bottom filling material causing the thermal stress of the material to increase, thereby causing the corner of the bump to crack with the bottom filling material, and the bump connection to break is effectively solved.

[0030] The preparation method of the epoxy resin composition of the present invention can be prepared by physically mixing the components using conventional operations in the art. An exemplary preparation method comprises the following steps:

[0031] The raw materials of each component are weighed according to the formula, mixed evenly and vacuum degassed to obtain the epoxy resin composition.

[0032] The present invention also provides application of the epoxy resin composition in chip packaging, such as (FCBGA, 2.5D chip packaging) and other fields.

[0033] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0034] The epoxy resin composition of the present invention has a significant improvement effect on the cracking and breaking of the bumps at the corners of the bumps and has high reliability in protecting the bumps. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is a schematic diagram of the sedimentation of filler in the corner of the convex point of the present invention. DETAILED DESCRIPTION

[0036] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event of ambiguity, the present specification including definitions will prevail.

[0037] Unless otherwise indicated, all parts, ratios, etc. are by weight.

[0038] The term "at least one" as used herein means that the aforementioned elements may be used alone or in combination of one or more.

[0039] When a certain amount, concentration or other value or parameter is expressed in the form of a range, a preferred range, or a preferred upper numerical limit and a preferred lower numerical limit, it should be understood that it is equivalent to specifically disclosing any range by combining any pair of range upper limits or preferred numerical values ​​with any range lower limits or preferred numerical values, regardless of whether the range is specifically disclosed. Unless otherwise indicated, the numerical ranges listed herein are intended to include the endpoints of the range, and all integers and fractions within the range. For example, "1-8" covers 1, 2, 3, 4, 5, 6, 7, 8 and any sub-range consisting of any two values ​​therein, such as 2-6, 3-5. The term "alkyl" refers to a straight or branched saturated aliphatic hydrocarbon group consisting of carbon atoms and hydrogen atoms, which is connected to the rest of the molecule by a single bond.

[0040] The scheme of the present invention is further described in detail below in conjunction with specific embodiments. It should be noted that the following embodiments are merely examples for clearly illustrating the technical scheme of the present invention, and are not intended to limit the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here, and the obvious changes or modifications derived therefrom are still within the scope of protection created by the present invention.

[0041] The present invention is described in detail below.

[0042] An epoxy resin composition comprising the following components in parts by weight:

[0043] (a) 12 to 20 parts of epoxy resin, for example 12, 13, 14, 15, 16, 17, 18, 19, 20 parts;

[0044] (b) 5 to 15 parts of an amine curing agent, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts;

[0045] (c) 0.05 to 3 parts of an antioxidant, for example 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3 parts;

[0046] (d) 50 to 75 parts of filler, for example 50, 55, 60, 65, 70 parts.

[0047] <Component (a) Epoxy Resin>

[0048] The epoxy resin of component (a) is preferably liquid at room temperature, but even if it is solid at room temperature, it can be used by diluting it with other liquid epoxy resins or diluents to make it liquid. Examples include at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, hydrogenated bisphenol epoxy resin, naphthalene epoxy resin, and liquid alcohol ether epoxy resin, such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, triglycidyl trimesic acid, vinylcyclohexene dioxide, methyl 2-(3,4-epoxycyclohexane)carboxylate, diglycidyl aniline, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolethane glycidyl ether, and trimethylolpropane glycidyl ether.

[0049] Epoxy resins that are solid or have high viscosity at room temperature may also be used. Examples of such epoxy resins include at least one of high molecular weight bisphenol A epoxy resins, novolac epoxy resins, biphenyl epoxy resins, o-cresol epoxy resins, resorcinol epoxy resins, dicyclopentadiene epoxy resins, and brominated bisphenol A epoxy resins. These epoxy resins may be diluted into liquid form with epoxy resins or diluents that are liquid at room temperature and used. Epoxy resins that are solid or have high viscosity at room temperature, preferably low viscosity liquid epoxy resins, may be used for dilution, such as at least one of polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethoxyethane glycidyl ether, and trimethoxypropane glycidyl ether.

[0050] The epoxy resin as component (a) can be used alone or in combination. Considering the viscosity, the epoxy resin is preferably a liquid epoxy resin at room temperature, such as at least one of liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, naphthalene ring epoxy resin, liquid aminophenol epoxy resin, and polysiloxane modified epoxy resin, more preferably bisphenol A epoxy resin, with a viscosity range of 2000 to 8000 mPa.s at 25°C; liquid bisphenol F epoxy resin, with a viscosity range of 1000 to 3000 mPa.s at 25°C; naphthalene ring epoxy resin, with a viscosity range of 15000 to 30000 mPa.s at 25°C.

[0051] <Component (b) Amine Curing Agent>

[0052] The (b) amine curing agent is a composition of a diphenylmethane type amine compound and a sulfur-containing benzene ring type amine compound;

[0053] The diphenylmethane amine compound is at least one of the compounds shown in Formula 1:

[0054]

[0055] In Formula 1, R1 and R2 are each independently hydrogen or C1-C3 alkyl; preferably, R1 and R2 are methyl or ethyl, and more preferably, R1 and R2 are each independently ethyl.

[0056] The sulfur-containing benzene ring amine compound is at least one of the compounds shown in Formula 2:

[0057]

[0058] In formula 2, R1, R2, and R3 are each independently hydrogen, a C1-C3 alkyl group, an amine group, or a thiol group. Preferably, R1, R2, and R3 are each independently methyl, ethyl, an amine group, or a thiol group; more preferably, R1 is a methyl group or an ethyl group; R2 is a methyl group or a thiol group; and R3 is a methyl group or an amine group.

[0059] The amine curing agent is a composition of a diphenylmethane amine compound and a sulfur-containing benzene ring amine compound, and the mass ratio of the two is 0.1-10, for example, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and the preferred ratio is 3-6.

[0060] In the present invention, the selection and combination of the two curing agents are particularly critical to the glass transition temperature and modulus of the material.

[0061] <Component (c) Antioxidant>

[0062] The antioxidant is a product disclosed in the prior art, and can be a commercially available product, or can be prepared based on a method disclosed in the prior art. The present invention has no special requirements.

[0063]

[0064] In Formula 3, R1, R2, and R3 are each independently hydrogen, a C1-C12 alkyl group, a hydroxyl group, or a mercapto group.

[0065] Preferably, R1, R2, and R3 are each independently hydroxyl, methyl, ethyl, propyl, or tert-butyl; more preferably, R1 is hydroxyl, methyl, or tert-butyl, R2 is hydroxyl, methyl, or tert-butyl, and R3 is methyl or tert-butyl.

[0066] Preferably, the purity of the antioxidant is above 99%.

[0067] <Component (d) Filler>

[0068] The epoxy resin composition of the present invention can use silica, alumina, silicon nitride, etc. as filler components in order to adjust the viscosity or thermal expansion coefficient of the epoxy resin composition. When the silica filler is contained, the content is 50 to 75 parts by weight, preferably 55 to 70 parts, and more preferably 60 to 70 parts based on the weight of the epoxy resin composition.

[0069] The shape of the silica filler is not limited, and any form such as granular, powdery, or flake can be used. Powdered silica is preferred, and spherical powdered silica is more preferred.

[0070] In addition, considering the compatibility of the filler with the epoxy resin, the surface of the filler may be treated, and the surface treatment agent may be trimethoxyethyl glycidyl ether or trimethoxypropyl glycidyl ether.

[0071] The average particle size of silica as a filler is not particularly limited, for example, 0.1 to 5 μm, but considering the fluidity of the epoxy resin composition, the average particle size of the filler is preferably 0.1 μm to 3 μm, more preferably 1.0 μm to 2 μm. The above average particle size refers to the median particle size, which can be obtained by testing with a laser particle size analyzer, the instrument model is BECKMAN 2000.

[0072] In addition to the above components, the epoxy resin composition of the present invention further comprises component (e) 0 to 2 parts of a pigment. The type of the pigment is not particularly limited and conventional pigments in the art may be used.

[0073] The present invention will be further described in detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto. In addition, in the following examples, unless otherwise specified, parts represent parts by mass.

[0074] The epoxy resin compositions of the examples were evaluated as follows:

[0075] Viscosity: The viscosity of the epoxy resin composition of the example was measured using a Brookfield viscometer at 25°C and 50 rpm.

[0076] The number of filler sedimentation in the corners of the bumps was taken using a scanning electron microscope from a Japanese electronics manufacturer, equipment model JSM7900F, in 15kv high-voltage scanning mode.

[0077] The sources of the main raw materials in the embodiments and comparative examples of the present invention are as follows. Other raw materials and reagents are purchased from commercial sources unless otherwise specified:

[0078] Bisphenol A epoxy resin: viscosity range at 25°C is 2000~8000mPa.s;

[0079] Bisphenol F epoxy resin: viscosity range at 25°C is 1000-3000 mPa.s;

[0080] Naphthalene ring type epoxy resin: viscosity ranges from 15000 to 30000 mPa.s at 25°C;

[0081] Diphenylmethane type amine curing agent (Formula 1 bisphenol F type amine compound), 3,3'-diethyl-4,4'-diaminodiphenylmethane: viscosity range of 2000-3000mPa.s at 25°C;

[0082] Sulfur-containing amine curing agent (sulfur-containing benzene ring amine compound of formula 2), dimethylthiomethyl-1,3-phenylenediamine: viscosity range of 500 to 1000 mPa.s at 25°C;

[0083] Filler silica: average particle size 0.1μm~3μm;

[0084] Pigment carbon black: average particle size 20-30μm.

[0085] Example 1-5: Preparation of epoxy resin composition

[0086] According to the formula in Table 1, the raw materials of components (a) to (d) were weighed respectively, mixed evenly and vacuum degassed to obtain the epoxy resin composition. The performance test results are shown in Table 2 below.

[0087] Comparative Example 1-2:

[0088] According to the same method as in the above embodiment, the raw materials were weighed according to the formula in Table 1, mixed evenly and vacuum degassed to obtain an epoxy resin composition. The performance test results are shown in Table 2 below:

[0089] Table 1 Composition formula of examples and comparative examples (unit / part by mass)

[0090]

[0091] Table 2 Performance test results of the compositions of the embodiments and comparative examples

[0092]

[0093]

[0094] It can be seen from the test data in Table 2 that by comparing Comparative Example 1 with Examples 1-5, it is shown that by adding an antioxidant, the number of filler sedimentation in the corners of the bumps can be effectively increased. By comparing Example 2 with Comparative Example 2, it can be seen that adjusting the dosage ratio of the antioxidant can significantly reduce the number of filler sedimentation in the corners of the bumps. The epoxy resin composition of Example 4 achieves optimal performance through the combination of the formulations of each component, so that while the number of filler sedimentation in the corners of the bumps is reduced, the viscosity of the epoxy resin composition is low, which is of great significance to the application of the epoxy resin composition.

[0095] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to allow professionals who understand such technologies to understand the contents of the present invention and implement them accordingly. They cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the essential contents of the present invention should be included in the protection scope of the present invention.

[0096] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the embodiments. Any other modifications, replacements, combinations, and simplifications that do not deviate from the essential contents and principles of the present invention should be equivalent replacement modes and are included in the protection scope of the present invention.

Claims

1. An epoxy resin composition, characterized in that Contains the following components in parts by weight: (a) 12 to 20 parts of epoxy resin; (b) 5 to 15 parts of an amine curing agent; (c) 0.05 to 3 parts of an antioxidant; (d) 50 to 75 parts of filler.

2. The epoxy resin composition according to claim 1, characterized in that The epoxy resin described in component (a) is at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene ring epoxy resin, alicyclic epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, and alcohol ether epoxy resin.

3. The epoxy resin composition according to claim 1, characterized in that The amine curing agent described in component (b) is a composition of a diphenylmethane amine compound and a sulfur-containing benzene ring amine compound, and the mass ratio of the diphenylmethane amine compound to the sulfur-containing benzene ring amine compound is preferably 0.1 to 10:1, more preferably 3 to 6:

1.

4. The epoxy resin composition according to claim 1 or 3, characterized in that The diphenylmethane amine compound is at least one of the compounds having the structure shown in Formula 1: In Formula 1, R1 and R2 are each independently hydrogen or a C1-C3 alkyl group.

5. The epoxy resin composition according to claim 1 or 3, characterized in that: The sulfur-containing benzene ring amine compound is at least one of the compounds having the structure shown in Formula 2: In Formula 2, R1, R2, and R3 are each independently any one of hydrogen, a C1-C3 alkyl group, an amino group, and a mercapto group.

6. The epoxy resin composition according to claim 1, characterized in that The antioxidant described in component (c) has at least one of the structural compounds shown in Formula 3: In Formula 3, R1, R2, and R3 are each independently hydrogen, a C1-C12 alkyl group, a hydroxyl group, or a mercapto group.

7. The epoxy resin composition according to claim 1 or 3, characterized in that: The filler described in component (d) is at least one selected from silica, alumina, and silicon nitride, preferably spherical silica.

8. The epoxy resin composition according to claim 7, characterized in that The average particle size of the filler is 0.1 to 5 μm, more preferably 0.1 to 3 μm.

9. The epoxy resin composition according to any one of claims 1 to 8, characterized in that It also contains component (e) 0 to 2 parts of pigment.

10. Use of the epoxy resin composition according to any one of claims 1 to 9 in the field of chip packaging.

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