Heat-conducting insulating layer material as well as preparation method and application thereof

Abstract

The invention provides a heat-conducting insulating layer material and a preparation method and application thereof, and relates to the technical field of heat-conducting insulating materials, the heat-conducting insulating layer material comprises the following components: epoxy resin, a curing agent, a heat-conducting filler, film-forming resin, a coupling agent, a curing accelerator and rubber particles; wherein the epoxy resin comprises dicyclopentadiene epoxy resin and / or epoxy resin with a planar aromatic skeleton structure. The heat-conducting insulating layer material provided by the invention can obtain a high heat conductivity coefficient gt; according to the present invention, the resin composition has characteristics of excellent heat resistance, low melt viscosity (1t, 200 Pas), excellent peeling strength (sputtering copper gt, 6 N / cm, chemical copper gt, and 4 N / cm) on a metal layer (especially a metal layer formed by plating), excellent working performance and low warping characteristics when the resin composition is used as an insulating layer, and can pass strict reliability tests such as moisture aging, high temperature aging, and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of heat-conducting insulation materials, in particular to a heat-conducting insulation layer material and a preparation method and application thereof. BACKGROUND

[0002] With the development of electronic devices towards miniaturization and high integration, the packaging density of chips is continuously improved, and effective heat dissipation packaging materials are needed to improve the heat diffusion of chips. Among them, the insulation layer (such as build-up film or plastic packaging film) is a key material for realizing circuit linking and encapsulation protection of chips.

[0003] However, high thermal conductivity of the insulation layer usually requires high thermal conductive filler addition (>80wt%), and accordingly, low viscosity liquid resin is needed to maintain the flowability of the film material to meet the packaging process requirements. However, excessive introduction of low viscosity resin will cause excessive internal stress of the film material, which is prone to warping (cannot be applied, affecting subsequent processing), weak bonding force with the metal plating layer, cracking failure during reliability verification process and other problems. SUMMARY

[0004] One of the purposes of the present application is to provide a heat-conducting insulation layer material to at least solve one of the technical problems existing in the prior art. The heat-conducting insulation layer material provided by the present application can obtain a high thermal conductivity >2W / mK, a low melt viscosity (<200Pas), an excellent peeling strength to a metal layer (especially a metal layer formed by plating) (sputtered copper >6N / cm, chemical copper plating >4N / cm), excellent work performance and low warping characteristics when applied as an insulation layer, and can pass through severe humidity aging, high temperature aging and other reliability tests.

[0005] The second purpose of the present application is to provide a preparation method of a heat-conducting insulation layer material.

[0006] The third purpose of the present application is to provide an application of a heat-conducting insulation layer material in preparing a semiconductor device.

[0007] In order to achieve the above-mentioned purposes of the present application, the following technical solutions are adopted: In a first aspect, the present application provides a heat-conducting insulation layer material, comprising the following components: epoxy resin, curing agent, heat-conducting filler, film-forming resin, coupling agent, curing accelerator and rubber particles. Among them, the epoxy resin comprises dicyclopentadiene-based epoxy resin and / or epoxy resin with a planar aromatic skeleton structure.

[0008] In some preferred embodiments, the thermally conductive insulating layer material comprises, by weight, 5-10 parts epoxy resin, 1-5 parts curing agent, 85-93 parts thermally conductive filler, 0.5-2 parts film-forming resin, 0.2-1 parts coupling agent, 0.05-0.2 parts curing accelerator, and 0.2-1 parts rubber particles.

[0009] In some preferred embodiments, the epoxy resin includes one or more of solid epoxy resin and liquid epoxy resin; Preferably, the solid epoxy resin includes one or more of phenolic epoxy resin, naphthyl tetrafunctional epoxy resin, cresol phenolic epoxy resin, dicyclopentadiene epoxy resin, triphenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, anthracene epoxy resin, bisphenol A epoxy resin, and tetraphenylethane epoxy resin, more preferably one or more of dicyclopentadiene epoxy resin and biphenyl epoxy resin; Preferably, the liquid epoxy resin includes one or more of the following: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenolic aldehyde type epoxy resin, alicyclic epoxy resin with an ester skeleton, cyclohexanediol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin with a butadiene structure; more preferably, one or more of the following: glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, and naphthalene type epoxy resin.

[0010] In some preferred embodiments, the curing agent includes a phenolic resin curing agent; The preferred structural formula of the phenolic resin curing agent is as follows:

[0011] Where n is 1.5-5.

[0012] In some preferred embodiments, the thermally conductive filler includes one or more of alumina, aluminum nitride, silicon carbide, boron nitride, and zinc oxide; Preferably, the alumina has a particle size of 0.2-5 micrometers.

[0013] In some preferred embodiments, the film-forming resin includes one or more of phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide-imide resin, polyether-imide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. Preferably, the weight average molecular weight of the film-forming resin is 8000-70000 in polystyrene conversion; more preferably 10000-60000, and further preferably 20000-60000; Preferably, the phenoxy resin has one or more repeating unit skeletons selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenol formaldehyde resin skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. Preferably, the terminal functional groups of the phenoxy resin are at least one of phenolic hydroxyl groups and epoxy groups.

[0014] In some preferred embodiments, the coupling agent includes one or more of γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and bis(triethoxysilylpropyl)tetrasulfide.

[0015] In some preferred embodiments, the curing accelerator includes an imidazole compound. Preferably, the rubber particles include one or more of acrylic rubber particles, polyamide microparticles, and silicone particles.

[0016] In a second aspect, the present application provides a preparation method of a heat-conducting insulation layer material, comprising: mixing an epoxy resin, a curing agent, a heat-conducting filler, a film-forming resin, a coupling agent, a curing accelerator, and rubber particles to obtain the heat-conducting insulation layer material.

[0017] In a third aspect, the present application provides a use of a heat-conducting insulation layer material in the preparation of a semiconductor device.

[0018] Compared with the prior art, the present application has the following beneficial effects: The heat-conducting insulation layer material provided by the present application, through reasonable formula design, uses dicyclopentadiene epoxy resin and / or epoxy resin with a planar aromatic skeleton structure as the matrix, significantly improves the rigidity and crosslinking density of the resin system, effectively improves the glass transition temperature (Tg) and storage modulus of the material, and endows the material with high glass transition temperature and excellent thermal stability; by adding the film-forming resin, the heat-conducting filler, and the rubber particles, the synergistic optimization of high thermal conductivity, low warpage, and good interfacial adhesion is achieved, solving the technical problems of poor flowability caused by high filler loading, excessive low-viscosity resin causing warpage, and weak metal bonding force in the prior art, and significantly improving the reliability and process adaptability of the material in high-density chip packaging. DETAILED DESCRIPTION

[0019] Unless otherwise defined, scientific and technical terms used in connection with the present application shall have the meanings that are commonly understood by those of ordinary skill in the art. The meaning and scope of the terms should be clear; however, in the event of any latent ambiguity, definitions provided herein take precedent over any dictionary or extrinsic definition. In this application, the use of "or" means "and / or" unless stated otherwise. Furthermore, use of the term "including" as well as other forms such as "include", "includes" or "include(s)", is not limiting.

[0020] The technical solutions of the present application will be clearly and completely described below in combination with the embodiments. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work belong to the scope of protection of the present application.

[0021] The first aspect of the present application provides a heat-conducting insulation layer material, comprising the following components: epoxy resin, curing agent, heat-conducting filler, film-forming resin, coupling agent, curing accelerator and rubber particles; wherein the epoxy resin comprises dicyclopentadiene-based epoxy resin and / or epoxy resin with planar aromatic skeleton structure.

[0022] The heat-conducting insulation layer material provided by the present application can achieve excellent comprehensive performance by using the above components. The material not only has high thermal conductivity (>2 W / mK) and low melt viscosity (<200 Pa·s), which meets the dual requirements of heat dissipation and processing fluidity for advanced packaging process, but also exhibits outstanding peeling strength (sputtered copper >6 N / cm, electroless plated copper >4 N / cm) to the metal layer (especially the copper layer formed by sputtering or electroless plating), while maintaining good work performance and low warping characteristics when used as an insulation layer, and can pass through severe reliability tests such as moisture aging, high temperature aging and multiple reflow. The key lies in the use of special epoxy resin combination (such as dicyclopentadiene-based or epoxy resin with planar aromatic skeleton structure) to optimize rigidity, crosslinking density and thermal dimensional stability, and the use of specific surface coupling technology of heat-conducting filler, which significantly improves the interfacial compatibility and stress transfer ability between the filler and the resin matrix, thereby achieving a technical breakthrough of high thermal conductivity, low internal stress and high bonding reliability.

[0023] In some preferred embodiments, the total weight of the heat-conducting insulation layer material is 100 parts, and the components of the heat-conducting insulation layer material comprise, by weight fraction: 5-10 parts of epoxy resin, 1-5 parts of curing agent, 85-93 parts of heat-conducting filler, 0.5-2 parts of film-forming resin, 0.2-1 part of coupling agent, 0.05-0.2 parts of curing accelerator and 0.2-1 parts of rubber particles.

[0024] The epoxy resin is added in an amount of 5-10 parts, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc. The curing agent is added in an amount of 1-5 parts, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, etc. The thermally conductive filler is added in an amount of 85-93 parts, for example, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, etc. The film-forming resin is added in an amount of 0.5-2 parts, for example, 0.5 parts, 1 part, 1.5 parts, 2 parts, etc. The coupling agent is added in an amount of 0.2-1 parts, for example, 0.2 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, etc., and further preferably 0.2-0.7 parts. The curing accelerator is added in an amount of 0.05-0.2 parts, for example, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, etc. The rubber particles are added in an amount of 0.2-1 parts, for example, 0.2 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, etc.

[0025] In some preferred embodiments, the epoxy resin further comprises one or more of a biphenyl dicyclopentadiene-based epoxy resin, a naphthalene-type epoxy resin, and an aminophenol-based epoxy resin.

[0026] Specifically, the resin composition in the material of the present invention contains epoxy resin (A). As epoxy resins, those capable of thermosetting the resin compositions of the present invention include epoxy resins with fused ring structures such as naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, dicyclopentadiene-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol-type epoxy resins, naphthylene ether-type epoxy resins, and dicyclopentadiene-type epoxy resins; bisphenol A type epoxy resins; bisphenol F type epoxy resins; bisphenol S type epoxy resins; bisphenol AF type epoxy resins; triphenol type epoxy resins; phenolic (novolac) type epoxy resins; naphthol novolac type epoxy resins; phenol novolac type epoxy resins; tert-butyl-catechol type epoxy resins; glycidylamine type epoxy resins; glycidyl ester type epoxy resins; cresol phenolic (cresol) type epoxy resins. Novolac type epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin; epoxy resin with butadiene structure; alicyclic epoxy resin; heterocyclic epoxy resin; epoxy resin containing spirocyclic rings; cyclohexanediol type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination. Component (A) is preferably selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, and epoxy resin with fused ring structure. Of these, from the viewpoint of obtaining an insulating layer with excellent physical properties such as low coefficient of thermal expansion, thermal conductivity, adhesion strength to copper plating, and surface roughness, it is more preferable to include an epoxy resin with a fused ring structure as component (A). Among the examples listed above, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, and dicyclopentadiene-type epoxy resins are preferred as epoxy resins having a fused ring structure. Naphthalene-type epoxy resins and naphthol-type epoxy resins are particularly preferred.

[0027] Preferably, the epoxy resin comprises epoxy resin having two or more epoxy groups per molecule. Furthermore, the epoxy resin preferably has an aromatic structure, and when using two or more epoxy resins, it is more preferable that at least one has an aromatic structure. When the non-volatile component of the epoxy resin is set to 100% by mass, it is preferable that at least 50% by mass is an epoxy resin having two or more epoxy groups per molecule. Preferably, it comprises: an epoxy resin having two or more epoxy groups per molecule and being liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin"), and an epoxy resin having three or more epoxy groups per molecule and being solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resin"). By combining liquid epoxy resin and solid epoxy resin, a resin composition with excellent flexibility can be obtained. Furthermore, the tensile strength of the cured resin composition is also improved. The term "aromatic structure" refers to a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles.

[0028] More preferably, the epoxy resin includes one or more of solid epoxy resin and liquid epoxy resin.

[0029] Specifically: (1) As a solid epoxy resin, phenolic epoxy resin, naphthol tetrafunctional epoxy resin, cresol phenolic epoxy resin, dicyclopentadiene epoxy resin, triphenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, anthracene epoxy resin, bisphenol A epoxy resin, tetraphenylethane epoxy resin are preferred, and phenolic epoxy resin, naphthol tetrafunctional epoxy resin, naphthol epoxy resin and biphenyl epoxy resin are more preferred. Specific examples of solid epoxy resins include: "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), "N-690" (cresol-phenolic epoxy resin), "N-695" (cresol-phenolic epoxy resin), "HP-7200" (dicyclopentadiene epoxy resin), "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether epoxy resin), "EPPN-502H" (triphenol-type epoxy resin), "NC7000L" (naphthyl phenolic epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC31" manufactured by DIC Corporation. 00" (biphenyl type epoxy resin), Nippon Steel & Sumitomo Metal Chemicals' "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol phenolic type epoxy resin), Mitsubishi Chemical's "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracite type epoxy resin), Osaka Gas Chemical Co., Ltd. The following epoxy resins can be used individually or in combination: “PG-100”, “CG-500”, “YL7760” (bisphenol AF type epoxy resin) and “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “jER1010” (solid bisphenol A type epoxy resin) and “jER1031S” (tetraphenylethane type epoxy resin) and “157S70” (phenolic type epoxy resin) manufactured by Mitsubishi Chemical Corporation.

[0030] (2) As a liquid epoxy resin, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenolic aldehyde type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexanediol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin with butadiene structure, more preferably glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin. Specific examples of liquid epoxy resins include: DIC's "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US", "jER828EL" (bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenolic resin), "630", and "630LSD" (glycidylamine type epoxy resin); Nippon Steel & Sumitomo Metal Chemicals' "ZX1059" (a mixture of bisphenol A and bisphenol F type epoxy resins); Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin); and Daicel's "Celloxide". 2021P (alicyclic epoxy resin with an ester skeleton), PB-3600 (epoxy resin with a butadiene structure), ZX1658 and ZX1658GS (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 630LSD (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., and EP-3980S (glycidylamine type epoxy resin) manufactured by ADEKA Co., Ltd., etc. One of these can be used alone, or two or more can be used in combination.

[0031] This invention requires the inclusion of NC3000-type dicyclopentadiene epoxy resin, or epoxy resin with a similar rigid planar aromatic backbone structure. While using only small-molecule epoxy resins such as HP 4032D (naphthalene-based) and / or 630LSD (aminophenol trifunctional group) can achieve high crosslinking density, significant volume shrinkage during curing leads to increased residual stress within the material, resulting in severe warpage and failing to meet the dimensional stability requirements of high-density encapsulation. However, the introduction of NC3000-type resin, with its unique rigid dicyclopentadiene structure, not only helps reduce curing shrinkage but also effectively increases the glass transition temperature (Tg) and modulus, balancing the contradiction between crosslinking density and internal stress. This significantly suppresses warpage while maintaining mechanical properties, thereby achieving a low-warpage, high-reliability thermally conductive insulating layer material.

[0032] In some preferred embodiments, the curing agent includes a phenolic resin curing agent. Specifically, the phenolic resin curing agent is selected from Shandong Shengquan DCDP phenolic resin (DPR) SH-7*** series, mainly including: SH-7090, SH-7110, SH-7117, SH-7, SH-7130 or SH-7140, etc.

[0033] The structural formula of the phenolic resin curing agent is as follows:

[0034] Where n is 1.5-5.

[0035] In some preferred embodiments, the thermally conductive filler includes alumina, aluminum nitride, zinc oxide, boron nitride, silicon carbide, etc. Preferably, the alumina has a particle size of 0.5-5 micrometers, for example, it can be 0.5 micrometers, 1 micrometer, 2 micrometers, 3 micrometers, 4 micrometers, 5 micrometers, etc.

[0036] In some preferred embodiments, the film-forming resin includes phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide-imide resin, polyether-imide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin, preferably phenoxy resin. The thermoplastic resin may be used alone or in combination of two or more.

[0037] Preferably, the weight-average molecular weight of the film-forming resin converted from polystyrene is in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The weight-average molecular weight of the thermoplastic resin converted from polystyrene is determined by gel permeation chromatography (GPC). Specifically, the weight-average molecular weight of the thermoplastic resin converted from polystyrene can be calculated as follows: using an LC-9A / RID-6A manufactured by Shimadzu Corporation as the measuring device, using a Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Corporation as the chromatographic column, using chloroform or the like as the mobile phase, the measurement is performed at a column temperature of 40°C, and the calculation is performed using a standard curve of standard polystyrene. Preferably, the phenoxy resin includes a phenoxy resin having one or more skeletons selected from the following: bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic resin skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal group of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A single phenoxy resin may be used, or two or more may be used in combination. Specific examples of phenoxy resins include: Mitsubishi Chemical Co., Ltd.’s “1256” and “4250” (both phenoxy resins containing a bisphenol A backbone), “YX8100BH30” (phenoxy resin containing a bisphenol S backbone), and “YX6954BH30” (phenoxy resin containing a bisphenol acetophenone backbone). In addition, Nippon Steel & Sumitomo Metal Chemical Co., Ltd.’s “FX280” and “FX293”, Mitsubishi Chemical Co., Ltd.’s “YX6954BH30”, “YX7553BH30”, “YL7769BH30”, “YL6794BH30”, “YL7213BH30”, “YL7290BH30”, and “YL7482BH30”, etc.

[0038] In some preferred embodiments, the coupling agent includes one or more of γ-glycidyl ether propyltrimethoxysilane (Shin-Etsu Chemical KBM4803), γ-methacryloyloxypropyltrimethoxysilane (Shin-Etsu Chemical X-12-981S), and bis(triethoxysilylpropyl)tetrasulfide (Shin-Etsu Chemical X-12-984S).

[0039] In some preferred embodiments, the curing accelerator includes imidazole compounds, specifically selected from Shikoku Chemical Co., Ltd. 1B2MZ or Shikoku Chemical Co., Ltd. 2E4MZ-A.

[0040] In some preferred embodiments, the rubber particles include acrylic rubber particles, polyamide microparticles, organosilicon particles, etc., specifically, Dow Chemical EP2601 or AICA AC-4030 are preferred.

[0041] Specifically, in the thermally conductive insulating layer material of the present invention, the "resin composition" refers to an organic polymer matrix system excluding inorganic thermally conductive fillers (such as alumina), which acts as a binder phase to coat the filler, form a thin film, and provide mechanical strength and interfacial adhesion. The resin composition mainly includes the following components: epoxy resin, curing agent, coupling agent used for surface treatment of the thermally conductive filler, film-forming resin (also known as thermoplastic resin), curing accelerator, and rubber particles.

[0042] The rubber particles used in this invention are granular, insoluble in organic solvents, and incompatible with epoxy resin, curing agents, and other components, forming an independently dispersed second phase within the resin system. This phase-separated structure can induce localized cavitation and shear band deformation under external force or thermal stress, effectively dissipating energy and significantly improving the material's impact resistance and interfacial bonding durability, while avoiding the decrease in glass transition temperature and modulus loss caused by excessive compatibility.

[0043] Preferably, the acrylic rubber particles include: microparticles of resins that exhibit rubber elasticity, such as acrylonitrile butadiene rubber (nitrile rubber), butadiene rubber, and acrylic rubber, which are chemically cross-linked to become resins that are insoluble and infusible in organic solvents. Specifically, they may be "AC3832" manufactured by Agk Industries, Ltd.

[0044] Preferably, when the resin composition contains rubber particles, from the viewpoint of imparting appropriate softness to the material, relieving internal stress, and improving crack resistance, the relative content of the rubber particles in the resin system is preferably controlled. Based on 100% by mass of the total resin composition, the content of the rubber particles is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. However, if the rubber particle content is too high, it may lead to a decrease in the resin matrix modulus and a reduction in heat resistance, affecting overall dimensional stability. Therefore, its upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less. In some preferred embodiments, the content of the rubber particles is further preferably 15% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less.

[0045] A second aspect of the present invention provides a method for preparing a thermally conductive insulating layer material, comprising: mixing epoxy resin, curing agent, thermally conductive filler, film-forming resin, coupling agent, curing accelerator and rubber particles to obtain the thermally conductive insulating layer material.

[0046] A third aspect of the present invention provides the application of a thermally conductive insulating layer material in the fabrication of semiconductor devices.

[0047] The present invention will be further illustrated below by way of examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or purchased directly from the market.

[0048] Example 1 This embodiment provides a thermally conductive insulating layer material, the components of which include: epoxy resin, curing agent, thermally conductive filler, film-forming resin, coupling agent, curing accelerator, and rubber particles. The epoxy resin includes 4032D and NC3000, the curing agent is SH7090, the thermally conductive filler is 1-micron alumina, the film-forming resin is XY-6954BH30, the coupling agent is Shin-Etsu Chemical KBM4803, the curing accelerator is 1B2MZ, and the rubber particles are EP2601. The specific weight proportions are shown in Table 1. The preparation process of the thermally conductive insulating layer material is as follows: After weighing all raw materials, dilute them with a mixed solvent of butanone and cyclohexanone (1:1) to prepare a mixed solution with a solid content of 85%. This solution is then coated onto a PET support film using a desktop coater and baked in a 100℃ oven for 2 minutes to obtain a laminated film material attached to the PET. Subsequently, an OPP carrier film is hot-pressed onto the surface of the laminated film material at 70℃. This results in a film material with a three-layer structure from top to bottom: OPP, laminated film, and PET.

[0049] Example 2 This embodiment provides a thermally conductive insulating layer material, which differs from Embodiment 1 in that: the epoxy resin includes 630LSD and NC3000, and the component weight parts are not exactly the same as those in Embodiment 1. The specific component weight parts of the thermally conductive insulating layer material are shown in Table 1.

[0050] Example 3 This embodiment provides a thermally conductive insulating layer material, which differs from Embodiment 1 in that the coupling agent is X-12-981S, and the weight percentages of the components are not exactly the same as those in Embodiment 1. The specific weight percentages of the components of the thermally conductive insulating layer material are shown in Table 1.

[0051] Example 4 This embodiment provides a thermally conductive insulating layer material, which differs from Embodiment 1 in that the coupling agent is X-12-984S, and the weight percentages of the components are not exactly the same as those in Embodiment 1. The specific weight percentages of the components of the thermally conductive insulating layer material are shown in Table 1.

[0052] Example 5 This embodiment provides a thermally conductive insulating layer material, which differs from Embodiment 1 in that: the coupling agent is X-12-984S, the curing accelerator is 2E4MZ-A, and the component weight parts are not exactly the same as those in Embodiment 1. The specific component weight parts of the thermally conductive insulating layer material are shown in Table 1.

[0053] Example 6 This embodiment provides a thermally conductive insulating layer material, which differs from Embodiment 1 in that: the coupling agent is X-12-984S, the curing accelerator is 2E4MZ-A, the rubber particles are AC-4030, and the component weight parts are not exactly the same as those in Embodiment 1. The specific component weight parts of the thermally conductive insulating layer material are shown in Table 1.

[0054] Example 7 This embodiment provides a thermally conductive insulating layer material, which differs from Embodiment 1 in that the epoxy resin is NC3000 and the component weight parts are not exactly the same as those in Embodiment 1. The specific component weight parts of the thermally conductive insulating layer material are shown in Table 1.

[0055] Example 8 This embodiment provides a thermally conductive insulating layer material, which has the same component selection as that in Embodiment 1, but the component weight parts are different. The specific component weight parts of the thermally conductive insulating layer material are shown in Table 1.

[0056] Example 9 This embodiment provides a thermally conductive insulating layer material, which has the same component selection as that in Embodiment 1, but the component weight parts are different. The specific component weight parts of the thermally conductive insulating layer material are shown in Table 1.

[0057] Comparative Example 1 This comparative example provides a thermally conductive insulating layer material, which differs from Example 1 in that the epoxy resin includes 4032D and 630LSD, and the weight parts of the components are not exactly the same as those in Example 1. The specific weight parts of the components of the thermally conductive insulating layer material are shown in Table 1.

[0058] Comparative Example 2 This comparative example provides a thermally conductive insulating layer material, which differs from Example 1 in that the epoxy resin includes 630LSD and NC3000, and the weight parts of the thermally conductive filler are reduced (the thermally conductive filler is 80 parts). The specific composition and weight parts of the thermally conductive insulating layer material are shown in Table 1.

[0059] Comparative Example 3 This comparative example provides a thermally conductive insulating layer material, which differs from Example 1 in that it does not contain a coupling agent and the weight parts of the components are not exactly the same as those in Example 1. The specific weight parts of the components of the thermally conductive insulating layer material are shown in Table 1.

[0060] Table 1

[0061] The thermally conductive insulating layer materials prepared in Examples 1-9 and Comparative Examples 1-3 were used as samples for testing.

[0062] Test method: (1) Test method for thermal conductivity: After removing the OPP film and PET carrier film from the sample to be tested, a vacuum flatbed hot press was used to press a 100um monolayer film at 80℃ and 0.5MPa pressure for 60s to prepare samples with thicknesses of 0.5mm, 1.0mm and 1.5mm.

[0063] The sample was cured at 90℃ for 30 min and at 180℃ for 60 min to prepare the test sample.

[0064] Cut the sample into 25.4*25.4mm pieces. 2 The thermal resistance of the test samples was measured using a Ruiling LW-9389 thermal conductivity meter at 80℃ and 40psi for three different thicknesses. The thermal conductivity was obtained by fitting the thermal resistance at the three thicknesses.

[0065] (2) Test method for melt viscosity: After removing the OPP film and PET carrier film from the sample to be tested, the 100um thickness is stacked to a thickness of 500um, and the sample is cut into cylinders with a diameter of 25 mm using a sample cutter.

[0066] The prepared sample was placed at the center of the 25 mm parallel plate clamp of the rotational rheometer (TA-DHR20). The vibration frequency of the rotational rheometer (TA-DHR20) was set to 3 Hz, the strain value to 0.01%, and the data acquisition frequency to 3.0 s / pt. Starting at 40℃, after the rotational rheometer reached the set temperature, an oscillating strain was applied, and the temperature was increased to 180℃ at a rate of 5℃ / min. After the test, the minimum melt viscosity of the sample could be determined by the melt viscosity curve obtained from the rotational rheometer.

[0067] (3) Test methods for coefficient of thermal expansion and glass transition temperature (TMA tensile method): The sample was cured at 90℃ for 30 min and at 180℃ for 60 min to prepare the test sample.

[0068] The coefficient of thermal expansion of the 3mm×5mm*100um sample was tested using the TMA 450 tensile method.

[0069] The test is performed along the thickness direction (Z-axis) and a load of 0.05N is applied to ensure close contact between the probe, the sample, and the platform.

[0070] Starting at room temperature (25°C), the temperature was increased to 260°C at a rate of 3°C / min, and then the scan was terminated.

[0071] Within the temperature range before and after the glass transition temperature Tg, tangent lines are drawn respectively, and the temperature corresponding to the intersection of the tangent lines is the glass transition temperature (Tg).

[0072] (4) Test method for storage modulus (DMA tensile method): The storage modulus of the samples was tested using the DMA tensile method. The samples were cured at 90℃ for 30 min and at 180℃ for 60 min to prepare the test samples.

[0073] The specimen was cut into a 5mm × 5mm square sample, and then the specimen was installed in the tensile fixture of the dynamic thermomechanical analyzer (DMA850) and the heating furnace was closed.

[0074] The DMA was set to tensile mode, with a vibration frequency of 1 Hz, an amplitude of 20 μm, an initial temperature of room temperature (25℃), an ending temperature of 260℃, and a heating rate of 3℃ / min for scanning. After the scan, the energy storage modulus curve was plotted, and the value at 40℃ was taken as the energy storage modulus (40℃).

[0075] (5) Test method for warpage: The sample was placed in a vacuum flatbed hot press at 100℃ and 0.5 MPa with a 0.1 μm*515mm*410mm sample. 2 The copper-clad laminate was pressed together for 30 seconds. The pressed samples were then cured at 90℃ for 30 minutes and at 180℃ for 60 minutes. After curing, the samples were placed flat on a granite platform under no-load conditions. The maximum vertical distance between the platform plane and the sample's most bent edge was then measured using a steel ruler, with readings accurate to 0.1 mm.

[0076] (6) Roughness testing methods: The surface roughness of the samples was tested using a white light interferometer (Contour X200). The sample was placed on the stage, and the lens was adjusted to a suitable height before the instrument was started for automatic scanning. At least 10 measurement points were taken for each sample, and the average value was recorded as the surface roughness, expressed in nanometers (nm).

[0077] (7) Test method for peel strength: After removing the OPP film from the sample, the sample was pressed against a roughened copper-clad laminate (0.2 mm thick) at 100°C and 0.5 MPa for 30 seconds using a vacuum flatbed hot press. Following pressing, the sample was cured at 90°C for 30 min and then at 180°C for 90 min. The PET carrier film was then removed, and the sample underwent vacuum sputtering of a copper layer, electroplating to thicken the copper layer, and annealing, ultimately producing a sample with a copper layer thickness of approximately 20 μm. Next, a portion of the copper layer was etched using a chemical method, resulting in a copper foil strip 10 mm wide and 70 mm long.

[0078] The peel strength of the sample was tested using a universal tensile testing machine (KJ-1065 series). First, approximately 10 mm of the copper foil strip was peeled off from the end, and the sample was fixed to a 90° peel test fixture. The upper fixture held the entire width of the peeled portion of the copper foil strip, ensuring it was perpendicular to the test plane. The machine was zeroed and started, peeling the copper foil at a speed of 50 mm / min for a length of at least 25 mm, maintaining the tensile force direction perpendicular to the test plane throughout the process. After the test, the peel force curve was recorded, and its average value is the initial peel strength of the sample.

[0079] The reflow peel strength test method is similar to the PCT peel strength test method. The difference is that the prepared sample is first placed under different environmental conditions before the peel strength test is performed.

[0080] Reflow profile parameters: 1. Preheating conditions: 150~200℃, for 60~120 seconds.

[0081] 2. Heating rate (TL to TP): Maximum 3℃ / second.

[0082] 3. Time above 217℃: 60-90 seconds.

[0083] 4. Time above 230℃: 60 seconds.

[0084] 5. Peak temperature: 260℃.

[0085] 6. Maximum holding time at peak temperature: 10 seconds; for wound products, the holding time is 5 seconds.

[0086] 7. Cooling rate (TP to TL): Maximum 6℃ / second.

[0087] Saturated vapor pressure test (PCT) parameters: 130℃, 100%RH, 168h.

[0088] Among them, a copper plating peel strength greater than 8 N / cm is judged as √, and a peel strength less than 8 N / cm is judged as ⅹ; A warping greater than 10mm is classified as X.

[0089] The test results are shown in Table 2.

[0090] Table 2

[0091] As shown in Table 2, the excellent performance of Examples 1-9 was achieved through the good combination of dicyclopentadiene epoxy resin and liquid 4032D and 630LSD. Specifically, the test data of Examples 1-6 show that the formulation system using dicyclopentadiene epoxy resin (such as NC3000) and liquid naphthalene-type or glycidylamine-type epoxy resin (such as 4032D and 630LSD) achieves a high thermal conductivity of 2.6-2.7 W / mK while maintaining a low melt viscosity (as low as 70 Pa·s). It also exhibits excellent metal layer adhesion, and the initial peel strength of sputtered copper meets the requirements. Furthermore, it maintains good bonding performance even after multiple reflow soldering and PCT damp heat aging. At the same time, its coefficient of thermal expansion is controlled within the range of 12-14 ppm / ℃, the storage modulus generally exceeds 6.2 GPa, and the warpage is less than 6 mm. This indicates that this combination can effectively balance flowability, thermal conductivity, dimensional stability, and interface reliability, making it suitable for high-density semiconductor packaging scenarios. Examples 7-9 also outperformed the comparative examples in overall performance. Example 7 used a single NC3000 epoxy resin, which has a high glass transition temperature (162°C) and good thermal stability, but a high melt viscosity (180 Pa·s) and relatively low fluidity. Examples 8 and 9 maintained key indicators such as thermal conductivity and peel strength within acceptable ranges under different component ratios. Although some samples showed slight warping or roughness, no cracking or interlayer delamination occurred, indicating that the resin system has good film-forming properties and structural reliability over a wide range.

[0092] In contrast, in Comparative Example 1, only liquid epoxy resins 4032D and 630LSD were used, resulting in severe warping after curing, which affected the reliability of subsequent processing. In Comparative Example 2, the insufficient content of thermally conductive filler not only led to a low thermal conductivity but also to insufficient storage modulus of the film material, resulting in severe warping.

[0093] In Comparative Example 3, no coupling agent was added, resulting in insufficient bonding strength between the insulating layer and the sputtered copper layer, leading to insufficient initial peel strength and significant delamination after damp heat aging.

[0094] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A thermally conductive and insulating layer material, characterized in that, It includes the following components: epoxy resin, curing agent, thermally conductive filler, film-forming resin, coupling agent, curing accelerator, and rubber particles; The epoxy resin includes dicyclopentadiene epoxy resin and / or epoxy resin having a planar aromatic backbone structure.

2. The thermally conductive insulating layer material according to claim 1, characterized in that, The thermally conductive insulating layer material comprises, by weight, 5-10 parts epoxy resin, 1-5 parts curing agent, 85-93 parts thermally conductive filler, 0.5-2 parts film-forming resin, 0.2-1 parts coupling agent, 0.05-0.2 parts curing accelerator, and 0.2-1 parts rubber particles.

3. The thermally conductive insulating layer material according to claim 1, characterized in that, The epoxy resin includes one or more of solid epoxy resin and liquid epoxy resin; Preferably, the solid epoxy resin includes one or more of phenolic epoxy resin, naphthyl tetrafunctional epoxy resin, cresol phenolic epoxy resin, dicyclopentadiene epoxy resin, triphenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, anthracene epoxy resin, bisphenol A epoxy resin, and tetraphenylethane epoxy resin, more preferably one or more of dicyclopentadiene epoxy resin and biphenyl epoxy resin; Preferably, the liquid epoxy resin includes one or more of the following: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenolic aldehyde type epoxy resin, alicyclic epoxy resin with an ester skeleton, cyclohexanediol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin with a butadiene structure; more preferably, one or more of the following: glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, and naphthalene type epoxy resin.

4. The thermally conductive insulating layer material according to claim 1, characterized in that, The curing agent includes a phenolic resin curing agent; the structural formula of the phenolic resin curing agent is as follows. Where n is 1.5-5.

5. The thermally conductive insulating layer material according to claim 1, characterized in that, The thermally conductive filler includes one or more of alumina, aluminum nitride, silicon carbide, boron nitride, and zinc oxide; Preferably, the alumina has a particle size of 0.2-5 micrometers.

6. The thermally conductive insulating layer material according to claim 1, characterized in that, The film-forming resin includes one or more of the following: phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide-imide resin, polyether-imide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. Preferably, the weight-average molecular weight of the film-forming resin is 8,000 to 70,000 when converted to polystyrene; more preferably, it is 10,000 to 60,000; and even more preferably, it is 20,000 to 60,000. Preferably, the phenoxy resin has one or more repeating unit skeletons selected from the following: bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic resin skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton and trimethylcyclohexane skeleton. Preferably, the terminal functional group of the phenoxy resin is at least one of phenolic hydroxyl and epoxy groups.

7. The thermally conductive insulating layer material according to claim 1, characterized in that, The coupling agent includes one or more of γ-glycidyl ether propyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and bis(triethoxysilylpropyl)tetrasulfide.

8. The thermally conductive insulating layer material according to claim 1, characterized in that, The curing accelerator includes imidazole compounds; Preferably, the rubber particles include one or more of acrylic rubber particles, polyamide microparticles, and organosilicon particles.

9. The method for preparing the thermally conductive insulating layer material according to any one of claims 1-8, characterized in that, include: The thermally conductive insulating layer material is obtained by mixing epoxy resin, curing agent, thermally conductive filler, film-forming resin, coupling agent, curing accelerator and rubber particles.

10. The use of the thermally conductive insulating layer material as described in any one of claims 1-8 in the fabrication of semiconductor devices.

Images