Epoxy resin plastic packaging material and preparation method and application thereof

Abstract

The invention relates to the technical field of semiconductor packaging materials, and discloses an epoxy resin plastic packaging material and a preparation method and application thereof. The method comprises the following steps: mixing 2-40 wt% of epoxy resin, 3-30 wt% of a curing agent, 0.01-10 wt% of a curing accelerator, 20-90 wt% of an inorganic filler, 0.05-5 wt% of a release agent, 0.04-3 wt% of a coupling agent, 0-25 wt% of a flame retardant, 0-3 wt% of a modifier and 0-3 wt% of a coloring agent to obtain a mixture, and then extruding and mixing the mixture; wherein the inorganic filler is selected from one or more than two of silicon dioxide, aluminum oxide and magnesium oxide, and the maximum particle size of the inorganic filler is less than or equal to 20 microns; the extrusion mixing process is carried out in equipment with a non-metal lining. The epoxy resin plastic packaging material has the characteristics of low viscosity, high filling property, high reliability, low warpage and the like, so that the epoxy resin plastic packaging material meets the requirement of flip chip packaging.

Description

Technical Field

[0001] The present invention relates to the technical field of semiconductor packaging materials, and in particular to an epoxy resin plastic packaging material and a preparation method and application thereof. Background Art

[0002] Flip chips interconnect the entire chip with the substrate, which can greatly increase the number of I / Os. With the development of high-performance integrated circuits, the requirements for the number of I / Os are getting higher and higher, and flip chip technology has shown many advantages, such as higher I / O density, short interconnection lines and good heat dissipation. These advantages make flip chips widely used in products such as high-frequency communications, high-performance computers and mobile phones. In traditional flip chips, the narrow gaps between chips or between chips and substrates are filled with underfill glue, but with the continuous increase in the number of chip layers, the requirements for heat dissipation are also getting higher and higher. The thermal conductivity of traditional underfill glue is difficult to meet the requirements for heat dissipation of multi-layer chip stacking. Therefore, the industry proposes to use epoxy resin compositions to fill this narrow gap while encapsulating the outside of the chip. This narrow gap is generally less than 100μm, so higher requirements are put forward for the filler particle size of the epoxy resin composition and the various metal or non-metal particles mixed inside. Summary of the invention

[0003] The purpose of the present invention is to overcome the problems existing in the prior art and provide a method for preparing an epoxy resin molding material. The epoxy resin molding material prepared by the method has the characteristics of low viscosity, high filling property, high reliability and low warpage, so that the epoxy resin molding material meets the requirements of flip chip packaging.

[0004] One aspect of the present invention provides a method for preparing an epoxy resin molding material, the method comprising:

[0005] 2 to 40 wt % of epoxy resin, 3 to 30 wt % of curing agent, 0.01 to 10 wt % of curing accelerator, 20 to 90 wt % of inorganic filler, 0.05 to 5 wt % of release agent, 0.04 to 3 wt % of coupling agent, 0 to 25 wt % of flame retardant, 0 to 3 wt % of modifier and 0 to 3 wt % of colorant are mixed to obtain a mixture, and then the mixture is extruded and kneaded;

[0006] The epoxy resin is selected from one or more of phenolic epoxy resin, bisphenol A epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, dicyclopentadiene phenolic epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin and bisphenol F epoxy resin;

[0007] The curing agent is selected from one or more of XYLOK phenolic resin, bisphenol A phenolic resin, dicyclopentadiene phenolic resin, biphenyl phenolic resin, multifunctional phenolic resin, anhydride curing agent and alicyclic amine curing agent;

[0008] The inorganic filler is selected from one or more of silicon dioxide, aluminum oxide and magnesium oxide, and the maximum particle size of the inorganic filler is ≤20 μm;

[0009] The extrusion mixing process is carried out in a device with a non-metal lining.

[0010] Preferably, the maximum particle size of the inorganic filler is ≤12 μm.

[0011] Preferably, the maximum particle size of the inorganic filler is ≤5 μm.

[0012] Preferably, the physical form of the inorganic filler is selected from one or more of a crystalline form, a molten angular form and a molten spherical form.

[0013] Preferably, the curing accelerator is selected from one or more of organic phosphorus compounds, imidazole compounds, tertiary amine compounds and derivatives thereof, aromatic urea derivatives and aliphatic urea derivatives; and / or

[0014] The release agent is selected from one or more of mineral wax, vegetable wax, polyethylene and polyamide wax; and / or

[0015] The coupling agent is selected from one or more of γ-(2,3-epoxypropyloxy)propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane and γ-methacryloxypropyltriethoxysilane.

[0016] Preferably, the flame retardant is selected from one or more of bromine-containing flame retardants, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate and organic phosphorus compounds; and / or

[0017] The modifier is rubber and / or organic silane.

[0018] Preferably, the equipment with non-metal lining is a twin-screw extruder; and / or

[0019] The non-metal lining is a ceramic lining.

[0020] Preferably, the extrusion mixing conditions include: temperature of 80-130° C. and time of 5-15 min.

[0021] A second aspect of the present invention provides an epoxy resin molding material prepared by the above method.

[0022] The third aspect of the present invention provides the use of the above epoxy resin molding material in semiconductor device packaging materials.

[0023] Preferably, the epoxy resin molding material is used for flip chip packaging.

[0024] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0025] The epoxy resin molding material prepared by the method described in the present invention is characterized by low viscosity, high filling property, high reliability, low warpage, etc. by matching a specific type of epoxy resin, a specific type of curing agent, and an inorganic filler of a specific size and type and controlling the amount of each component, and extruding and kneading the raw material mixture by a device with a non-metallic liner. The epoxy resin molding material can be applied to the packaging of ordinary chips and flip chips by non-metallic liner-containing extrusion and kneading equipment. DETAILED DESCRIPTION

[0026] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0027] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0028] One aspect of the present invention provides a method for preparing an epoxy resin molding material, the method comprising:

[0029] 2 to 40 wt % of epoxy resin, 3 to 30 wt % of curing agent, 0.01 to 10 wt % of curing accelerator, 20 to 90 wt % of inorganic filler, 0.05 to 5 wt % of release agent, 0.04 to 3 wt % of coupling agent, 0 to 25 wt % of flame retardant, 0 to 3 wt % of modifier and 0 to 3 wt % of colorant are mixed to obtain a mixture, and then the mixture is extruded and kneaded;

[0030] The epoxy resin is selected from one or more of phenolic epoxy resin, bisphenol A epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, dicyclopentadiene phenolic epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin and bisphenol F epoxy resin;

[0031] The curing agent is selected from one or more of XYLOK phenolic resin, bisphenol A phenolic resin, dicyclopentadiene phenolic resin, biphenyl phenolic resin, multifunctional phenolic resin, anhydride curing agent and alicyclic amine curing agent;

[0032] The inorganic filler is selected from one or more of silicon dioxide, aluminum oxide and magnesium oxide, and the maximum particle size of the inorganic filler is ≤20 μm;

[0033] The extrusion mixing process is carried out in a device with a non-metal lining.

[0034] The method described in the present invention adopts a specific type of epoxy resin, a specific type of curing agent and an inorganic filler of a specific size and type and controls the amount of each component, and adopts a device with a non-metallic lining to extrude and mix the raw material mixture, so that the prepared epoxy resin plastic packaging material has the characteristics of low viscosity, high filling property, high reliability and low warpage, and can achieve no delamination after the third-level assessment (MSL-3), so that it can be applied not only to the packaging of ordinary chips, but also to the packaging of flip chips.

[0035] In the present invention, the "maximum particle size of the inorganic filler" refers to the "minimum standard sieve size with a sieve pass rate of 100% in the inorganic filler"; for example, "the maximum particle size of the inorganic filler ≤ 20 μm" means that the inorganic filler can pass through a sieve with a size of 20 μm.

[0036] In a preferred embodiment, in order to improve the filling property of the epoxy resin molding material, the maximum particle size of the inorganic filler is ≤12 μm. The smaller the particle size of the inorganic filler, the better its filling property is, and the narrow gaps between chip packages can be better filled.

[0037] In a preferred embodiment, in order to further improve the filling property of the epoxy resin molding material, the maximum particle size of the inorganic filler is ≤5 μm.

[0038] In a preferred embodiment, the physical form of the inorganic filler is selected from one or more of a crystalline form, a molten angular form and a molten spherical form.

[0039] In a preferred embodiment, the inorganic filler is selected from one or more of crystalline silica, fused angular silica, fused spherical silica, crystalline alumina, fused angular alumina, fused spherical alumina, crystalline magnesium oxide, fused angular magnesium oxide and fused spherical magnesium oxide.

[0040] In a preferred embodiment, in order to promote the cross-linking reaction between the epoxy resin and the curing agent within a suitable time, the curing accelerator is selected from one or more of organic phosphorus compounds, imidazole compounds, tertiary amine compounds and their derivatives, aromatic urea derivatives and aliphatic urea derivatives.

[0041] In a preferred embodiment, the release agent is selected from one or more of mineral wax, vegetable wax, polyethylene and polyamide wax.

[0042] In a preferred embodiment, the coupling agent is selected from one or more of γ-(2,3-epoxypropyl)propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane and γ-methacryloxypropyltriethoxysilane.

[0043] In a preferred embodiment, in order to improve the flame retardancy of the epoxy resin molding material, the flame retardant is selected from one or more of bromine-containing flame retardants, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate and organic phosphorus compounds.

[0044] In a preferred embodiment, in order to reduce the stress of the epoxy resin molding material, the modifier is rubber and / or organic silane.

[0045] In the present invention, there is no special requirement for the colorant, and any colorant commonly used in the art can be used. For example, the colorant can be carbon black.

[0046] In the method of the present invention, the use of equipment with a non-metallic lining for extrusion mixing can reduce the mixing of metal particles, so that the prepared epoxy resin molding material has better filling performance.

[0047] In a preferred embodiment, the equipment having a non-metallic liner is a twin-screw extruder.

[0048] In a preferred embodiment, the non-metallic lining is a ceramic lining.

[0049] In a preferred embodiment, the extrusion mixing conditions include: temperature of 80-130° C. and time of 5-15 min.

[0050] In a preferred embodiment, the method for preparing the above epoxy resin molding material further comprises cooling and crushing after extrusion and mixing.

[0051] A second aspect of the present invention provides an epoxy resin molding material prepared by the above method.

[0052] The epoxy resin molding material of the present invention has the characteristics of low viscosity, high filling property, high reliability and low warpage, and can achieve no delamination after the third-level assessment (MSL-3), so that it can be applied not only to the packaging of ordinary chips, but also to the packaging of flip chips.

[0053] The third aspect of the present invention provides the use of the above epoxy resin molding material in semiconductor device packaging materials.

[0054] In a preferred embodiment, the epoxy resin molding material is used for flip chip packaging.

[0055] The following examples further illustrate the epoxy resin molding material and its preparation method and application described in the present invention. The examples are implemented based on the technical solution of the present invention, and provide detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to the following examples.

[0056] The experimental methods in the following examples, unless otherwise specified, are all conventional methods in the art. The experimental materials used in the following examples, unless otherwise specified, are all commercially available, wherein epoxy resins: bisphenol F type epoxy resin (A1) purchased from Shandong Shengquan Resin, biphenyl type epoxy resin (A2) purchased from Japan DIC Co., Ltd., phenolic type epoxy resin (A3) purchased from Shandong Shengquan Resin, multifunctional type epoxy resin (A4) purchased from Shandong Shengquan Resin, naphthalene type epoxy resin (A5) purchased from Japan DIC Co., Ltd., o-cresol type epoxy resin (A6) purchased from Yueyang Petrochemical;

[0057] Curing agent: biphenyl phenolic resin (B1) purchased from Shandong Shengquan Resin, XYLOK phenolic resin (B2) purchased from Shandong Shengquan Resin, multifunctional phenolic resin (B3) purchased from Japan Meiwa Chemical, linear phenolic resin (B4) purchased from Shandong Shengquan Resin;

[0058] Accelerator: 2-methylimidazole (C1) was purchased from Shikoku Chemical, and aromatic urea derivative 3512T (C2) was purchased from Mitsubishi, Japan;

[0059] Inorganic fillers: molten spherical silica (D1) purchased from Jiangsu Lianrui with a maximum particle size of 20 μm, molten spherical silica (D2) purchased from Jiangsu Lianrui with a maximum particle size of 12 μm, molten angular alumina (D3) purchased from Jiangsu Lianrui with a maximum particle size of 20 μm, crystalline magnesium oxide (D4) purchased from Jiangsu Lianrui with a maximum particle size of 20 μm, molten spherical silica purchased from Jiangsu Lianrui (D5) with a maximum particle size of 45 μm;

[0060] Flame retardant: Brominated epoxy (E1) purchased from Nan Ya Resin; aluminum hydroxide (E2) purchased from Nippon Light Metal;

[0061] Release agents: carnauba wax (F1) purchased from Yikeshu, glyceryl monostearate (F2) purchased from aladdin;

[0062] Coupling agent: KH560 (G1) was purchased from Jiangsu Chenguang, KH550 (G2) was purchased from Jiangsu Chenguang;

[0063] Modifier: CTBN (H) was purchased from Dow Chemical, USA;

[0064] Colorant: Carbon black MA600 (I) purchased from Mitsubishi Chemical;

[0065] The types and amounts of the raw materials used in the examples are shown in Table 1;

[0066] Table 1

[0067]

[0068]

[0069] Example 1

[0070] Preparation of epoxy molding material S1:

[0071] Epoxy resin, curing agent, curing accelerator, inorganic filler, release agent, coupling agent, flame retardant, modifier and colorant are mixed to obtain a mixture, and then the mixture is put into a twin-screw extruder including a ceramic liner for extrusion and mixing. The extrusion and mixing temperature is 100° C. and the time is 10 minutes. Then, the mixture is cooled and crushed. The types and amounts of the raw materials are shown in Table 1.

[0072] Example 2

[0073] Preparation of epoxy molding material S2:

[0074] Epoxy resin, curing agent, curing accelerator, inorganic filler, release agent, coupling agent, flame retardant, modifier and colorant are mixed to obtain a mixture, and then the mixture is put into a twin-screw extruder including a ceramic liner for extrusion and mixing. The extrusion and mixing temperature is 100° C. and the time is 10 minutes. Then, the mixture is cooled and crushed. The types and amounts of the raw materials are shown in Table 1.

[0075] Example 3

[0076] Preparation of epoxy molding material S3:

[0077] Epoxy resin, curing agent, curing accelerator, inorganic filler, release agent, coupling agent, flame retardant, modifier and colorant are mixed to obtain a mixture, and then the mixture is put into a twin-screw extruder including a ceramic liner for extrusion and mixing. The extrusion and mixing temperature is 100° C. and the time is 10 minutes. Then, the mixture is cooled and crushed. The types and amounts of the raw materials are shown in Table 1.

[0078] Example 4

[0079] Preparation of epoxy molding material S4:

[0080] Epoxy resin, curing agent, curing accelerator, inorganic filler, release agent, coupling agent, flame retardant, modifier and colorant are mixed to obtain a mixture, and then the mixture is put into a twin-screw extruder including a ceramic liner for extrusion and mixing. The extrusion and mixing temperature is 100° C. and the time is 10 minutes. Then, the mixture is cooled and crushed. The types and amounts of the raw materials are shown in Table 1.

[0081] Example 5

[0082] Preparation of epoxy molding material S5:

[0083] Epoxy resin, curing agent, curing accelerator, inorganic filler, release agent, coupling agent, flame retardant, modifier and colorant are mixed to obtain a mixture, and then the mixture is put into a twin-screw extruder including a ceramic liner for extrusion and mixing. The extrusion and mixing temperature is 100° C. and the time is 10 minutes. Then, the mixture is cooled and crushed. The types and amounts of the raw materials are shown in Table 1.

[0084] Example 6

[0085] Preparation of epoxy molding material S6:

[0086] Epoxy resin, curing agent, curing accelerator, inorganic filler, release agent, coupling agent, flame retardant, modifier and colorant are mixed to obtain a mixture, and then the mixture is put into a twin-screw extruder including a ceramic liner for extrusion and mixing. The extrusion and mixing temperature is 100° C. and the time is 10 minutes. Then, the mixture is cooled and crushed. The types and amounts of the raw materials are shown in Table 1.

[0087] Example 7

[0088] Preparation of epoxy molding material S7:

[0089] Epoxy resin, curing agent, curing accelerator, inorganic filler, release agent, coupling agent, flame retardant, modifier and colorant are mixed to obtain a mixture, and then the mixture is put into a twin-screw extruder including a ceramic liner for extrusion and mixing. The extrusion and mixing temperature is 100° C. and the time is 10 minutes. Then, the mixture is cooled and crushed. The types and amounts of the raw materials are shown in Table 1.

[0090] Comparative Example 1

[0091] The method of Example 1 was followed, except that the inorganic filler was of type D5, i.e., fused spherical silica with a maximum particle size of 45 μm.

[0092] Comparative Example 2

[0093] The method is implemented in the same manner as in Example 1, except that the type of epoxy resin is A6, i.e., o-cresol type epoxy resin.

[0094] Comparative Example 3

[0095] The method is implemented in the same manner as in Example 1, except that the type of curing agent is B4, i.e., linear phenolic resin.

[0096] Comparative Example 4

[0097] The method is implemented in the manner of Example 1, except that the inner liner of the twin-screw extruder is a metal liner.

[0098] Test Case

[0099] (1) The flow properties of the samples prepared in the examples and comparative examples were tested in the following manner: the samples were molded by transfer molding at 175° C. on a flow test mold, and after curing for 110 seconds, the mold was opened and the flow length was read. The results are shown in Table 2.

[0100] (2) Testing the performance of the samples prepared in the embodiments and comparative examples in flip chip packaging, mainly including reliability (MSL-3 assessment) and filling performance;

[0101] The reliability test method is as follows: the sample is packaged by transfer molding process on the flip chip substrate at 175°C, and after demolding, the packaged sample is cured at 175°C for 4 hours and then assessed at MSL-3 level according to IPC J-STD-020C-2004 (humidity reflow sensitivity classification of non-sealed solid phase surface mount components). Then, the delamination is scanned using ultrasonic scanning equipment. The results are shown in Table 2.

[0102] The filling property test method is as follows: the sample is encapsulated by transfer molding process on the flip chip substrate at 175°C, and then the filling condition is scanned by ultrasonic scanning equipment, and the results are shown in Table 2;

[0103] Table 2

[0104]

[0105]

[0106] It can be seen from the results in Table 2 that the epoxy resin molding materials prepared by the method described in the present invention have passed the MSL-3 assessment and have good filling performance, and the fluidity meets the requirements of flip chip molding. By comparing comparative examples 1-4, it can be seen that when the inorganic filler, epoxy resin, curing agent and the lining of the twin-screw extruder are not of the type described in the method described in the present invention, the prepared epoxy resin molding materials do not pass the MSL-3 assessment.

[0107] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing an epoxy resin molding material, characterized in that: The method includes: 2 to 40 wt % of epoxy resin, 3 to 30 wt % of curing agent, 0.01 to 10 wt % of curing accelerator, 20 to 90 wt % of inorganic filler, 0.05 to 5 wt % of release agent, 0.04 to 3 wt % of coupling agent, 0 to 25 wt % of flame retardant, 0 to 3 wt % of modifier and 0 to 3 wt % of colorant are mixed to obtain a mixture, and then the mixture is extruded and kneaded; The epoxy resin is selected from one or more of phenolic epoxy resin, bisphenol A epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, dicyclopentadiene phenolic epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin and bisphenol F epoxy resin; The curing agent is selected from one or more of XYLOK phenolic resin, bisphenol A phenolic resin, dicyclopentadiene phenolic resin, biphenyl phenolic resin, multifunctional phenolic resin, anhydride curing agent and alicyclic amine curing agent; The inorganic filler is selected from one or more of silicon dioxide, aluminum oxide and magnesium oxide, and the maximum particle size of the inorganic filler is ≤20 μm; The extrusion mixing process is carried out in a device with a non-metal lining.

2. The method according to claim 1, characterized in that The maximum particle size of the inorganic filler is ≤12 μm; Preferably, the maximum particle size of the inorganic filler is ≤5 μm.

3. The method according to claim 1 or 2, characterized in that: The physical form of the inorganic filler is selected from one or more of a crystalline form, a molten angular form and a molten spherical form.

4. The method according to claim 3, characterized in that: The curing accelerator is selected from one or more of organic phosphorus compounds, imidazole compounds, tertiary amine compounds and their derivatives, aromatic urea derivatives and aliphatic urea derivatives; and / or The release agent is selected from one or more of mineral wax, vegetable wax, polyethylene and polyamide wax; and / or The coupling agent is selected from one or more of γ-(2,3-epoxypropyloxy)propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane and γ-methacryloxypropyltriethoxysilane.

5. The method according to claim 1 or 4, characterized in that: The flame retardant is selected from one or more of bromine-containing flame retardants, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate and organic phosphorus compounds; and / or The modifier is rubber and / or organic silane.

6. The method according to claim 5, characterized in that The equipment with non-metal lining is a twin-screw extruder; and / or The non-metal lining is a ceramic lining.

7. The method according to claim 1 or 6, characterized in that: The extrusion mixing conditions include: temperature of 80-130° C. and time of 5-15 min.

8. The epoxy resin molding material prepared by the method according to any one of claims 1 to 7.

9. Use of the epoxy resin molding material according to claim 8 in semiconductor device packaging materials.

10. The use according to claim 9, characterized in that: The epoxy resin molding material is used for packaging of flip chips.

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