Epoxy resin composition for encapsulating semiconductor devices and semiconductor device encapsulated using the same

Abstract

Disclosed herein is an epoxy resin composition for encapsulating a semiconductor device and a semiconductor device encapsulated using the same. The epoxy resin composition includes an epoxy resin, a curing agent, an inorganic filler, and a curing catalyst.

Description

[0001] Citations of relevant applications

[0002] This application claims priority to Korean Patent Application No. 10-2024-0180068, filed on December 6, 2024, with the Korean Intellectual Property Office, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] This disclosure relates to an epoxy resin composition for encapsulating a semiconductor device and a semiconductor device encapsulated using the epoxy resin composition. Background Technology

[0004] The integration of semiconductor devices is increasing, and in semiconductor devices in which stacks of high-density semiconductor devices are packaged in small and thin packages, failures such as package breakage or malfunctions may occur frequently due to heat generated during the operation of the semiconductor device.

[0005] As a solution to the challenges associated with heat generation, heat sinks formed from heat-dissipating materials such as metals are incorporated into semiconductor packages during the molding of epoxy resin for encapsulation. However, such heat sinks are only suitable for some packages, such as fine-pitch ball grid arrays (FBGAs) and quad flat packages (QFPs), and result in reduced productivity due to the additional assembly processes required during assembly, as well as increased costs due to the high cost of the heat sinks. Therefore, there is a need for an epoxy resin molding material for encapsulating semiconductor devices that possesses high thermal conductivity and the desired heat dissipation capabilities. Some semiconductor packages include aluminum oxide (aluminum oxide).

[0006] Alumina has a thermal conductivity ranging from about 25 W / m·K to about 30 W / m·K, while resins used for sealing semiconductor devices have a poor thermal conductivity of about 0.2 W / m·K, thus limiting improvements in thermal conductivity. Furthermore, copper, aluminum, and silver particles with high thermal conductivity typically exhibit poor insulating properties, and aluminum nitride, boron nitride, and silicon carbide fillers, which have relatively desirable insulating properties, cannot increase the filling rate due to poor flowability. Despite efforts to improve the thermal conductivity of resins, the commercialization of insulating and thermosetting compressible resin materials for sealing semiconductors has not yet been achieved.

[0007] To impart high thermal conductivity to resin compositions or epoxy molding compounds (EMCs), methods using aluminum oxide (alumina) with a higher thermal conductivity than silicon oxide (in the range of about 25 W / m·K to about 30 W / m·K) are generally known. However, typical resins used in resin compositions for encapsulating semiconductors have a low thermal conductivity of about 0.2 W / m·K, making it difficult to obtain resin compositions with a thermal conductivity of about 6 W / m·K or higher.

[0008] The use of large amounts of inorganic fillers in resin compositions used for semiconductor encapsulation is likely to cause wire sweep due to increased composition viscosity, lead to void defects due to difficulties in package formation caused by reduced composition flowability, and limit improvements in filler rates. Furthermore, since heat generated during the operation of semiconductor devices inevitably passes through the resin in the heat transfer path, the high thermal conductivity of the filler cannot ensure effective heat transfer if the resin has low thermal conductivity. Summary of the Invention

[0009] An exemplary aspect of this disclosure includes an epoxy resin composition for encapsulating semiconductor devices, which provides desired or improved heat dissipation due to its high thermal conductivity, while improving reliability by improving toughness.

[0010] An exemplary aspect of this disclosure includes an epoxy resin composition for encapsulating semiconductor devices.

[0011] Epoxy resin compositions for encapsulating semiconductor devices comprise at least one epoxy resin, a curing agent, an inorganic filler, and a curing catalyst, wherein the epoxy resin includes epoxy resins represented by chemical formula 1: .

[0012] In the above chemical formula 1, R 1 To R 12 Each is independently either hydrogen or includes, substituted or unsubstituted, C1 to C2. 20 Alkyl, substituted or unsubstituted C6 to C 30 Aryl, substituted or unsubstituted C6 to C 30 aryloxy group, substituted or unsubstituted C3 to C4 30 heteroaryl, substituted or unsubstituted C3 to C 30 Heterocyclic alkyl, substituted or unsubstituted C7 to C8 30 arylalkyl, substituted or unsubstituted C1 to C 30 Heteroalkyl groups or groups represented by chemical formula 2, R 1 To R 12 At least two of them are groups represented by chemical formula 2: ; in It is the linking site of the element, and L 11 It includes, or may include, substituted or unsubstituted C4 to C4. 10 Alkylene.

[0013] Another aspect of this disclosure includes semiconductor devices.

[0014] Semiconductor devices are encapsulated using epoxy resin compositions used for packaging semiconductor devices.

[0015] Exemplary embodiments of this disclosure include epoxy resin compositions for encapsulating semiconductor devices, which provide desired or improved heat dissipation due to their high thermal conductivity, while improving reliability by enhancing toughness. Detailed Implementation

[0016] Exemplary embodiments of this disclosure are described in detail below, enabling this disclosure to be readily implemented by those skilled in the art. It should be understood that this disclosure can be embodied in various ways and is not limited to the following exemplary embodiments.

[0017] As used in this article to indicate a specific numerical range, "X to Y" means "greater than or equal to X and less than or equal to Y".

[0018] As used herein, the term "substituted" in the expression "substituted or unsubstituted" means that at least one hydrogen atom of the corresponding functional group is substituted by a hydroxyl, amino, nitro, cyano, C1 to C2 group. 20 Alkyl, C1 to C 20 Haloalkyl, C6 to C 30 Aryl, C3 to C 30 heteroaryl, C3 to C 10 cycloalkyl, C3 to C 10 Heterocyclic alkyl, C7 to C 30 arylalkyl or C1 to C 30 Heteroalkyl substitution.

[0019] Unless otherwise stated, the chemical formulas described herein are assumed to have hydrogen atoms bonded to their structure.

[0020] When the terms “about” or “substantially” are used with numerical values ​​in this specification, it is intended that the relevant numerical value includes a tolerance of ±10% of the specified value. When a range is specified, the range includes all values ​​within that range, such as increments of 0.1%.

[0021] An epoxy resin composition for encapsulating a semiconductor device according to an exemplary embodiment comprises an epoxy resin, a curing agent, an inorganic filler, and a curing catalyst, wherein the epoxy resin includes the epoxy resin represented by chemical formula 1 as described below.

[0022] Epoxy resins represented by chemical formula 1 have high thermal conductivity and improved toughness to ensure the desired heat dissipation while improving reliability.

[0023] Epoxy resin

[0024] Epoxy resins include epoxy resins represented by the following chemical formula 1.

[0025] Epoxy resins represented by chemical formula 1 have high thermal conductivity and improved toughness to achieve the desired heat dissipation while improving reliability.

[0026] The epoxy resin represented by Formula 1 has a benzene-anthracene core instead of a tetraphenyl core having a structure in which phenyl groups are linked to a straight chain, and therefore has relatively high solubility and can be used in compositions according to this disclosure.

[0027] In one exemplary embodiment, the epoxy resin can be represented by the following chemical formula 1: Chemical formula 1.

[0028] In chemical formula 1, R 1 To R 12 Each is independently either hydrogen or includes, substituted or unsubstituted, C1 to C2. 20 Alkyl, substituted or unsubstituted C6 to C 30 Aryl, substituted or unsubstituted C6 to C 30 aryloxy group, substituted or unsubstituted C3 to C4 30 heteroaryl, substituted or unsubstituted C3 to C 30 Heterocyclic alkyl, substituted or unsubstituted C7 to C8 30 arylalkyl, substituted or unsubstituted C1 to C 30 Heteroalkyl groups or groups represented by the following chemical formula 2, R 1 To R 12 At least two of them are groups represented by chemical formula 2: Chemical formula 2.

[0029] In chemical formula 2, It is the linking site of the element, and L 11 It includes, or may include, substituted or unsubstituted C4 to C4. 10 Alkylene.

[0030] The composition may contain at least one of chemical formula 1, such as at least two epoxy resins.

[0031] In one exemplary embodiment, R in chemical formula 1 1 To R 12 Each is independently either hydrogen or includes, substituted or unsubstituted, C1 to C2. 20 Alkyl groups or groups represented by chemical formula 2, and R 1 To R 12 At least two of them can be or include groups represented by chemical formula 2.

[0032] In one exemplary embodiment, R in chemical formula 1 1 To R 4 At least one of them may be or includes a group represented by chemical formula 2. For example, R in chemical formula 1 3 It is or includes a group represented by chemical formula 2.

[0033] In one exemplary embodiment, R in chemical formula 1 8 To R 11 At least one of them may be or includes a group represented by chemical formula 2. For example, R in chemical formula 1 9 It may be or include groups represented by chemical formula 2.

[0034] In one exemplary embodiment, R in chemical formula 1 1 R 2 R 4 To R 8 and R 10 To R 12 Each of these can be, independently, hydrogen or substituted or unsubstituted C1 to C2. 20 Alkyl groups, such as unsubstituted C1 to C5 alkyl groups.

[0035] In another exemplary embodiment, R in chemical formula 1 1 To R 4 At least one of them may be or includes a group represented by chemical formula 2. For example, R in chemical formula 1 3 It is or includes a group represented by chemical formula 2.

[0036] In another exemplary embodiment, R in chemical formula 1 6 To R 7 At least one of them may be or includes a group represented by chemical formula 2. For example, R in chemical formula 1 7 It is or includes a group represented by chemical formula 2.

[0037] In other exemplary embodiments, R in Formula 1 1 R2 R 4 To R 6 and R 8 To R 12 Each of these can be, independently, hydrogen or substituted or unsubstituted C1 to C2. 20 Alkyl groups, such as substituted C1 to C5 alkyl groups.

[0038] For example, an epoxy resin represented by Formula 1 may include at least one of the compounds represented by Formulas 1-1 to 1-6: Chemical formula 1-1: .

[0039] Chemical formula 1-2: .

[0040] Chemical formulas 1-3: .

[0041] Chemical formulas 1-4: .

[0042] Chemical formulas 1-5: .

[0043] Chemical formulas 1-6: .

[0044] The epoxy resin composition may contain at least one epoxy resin represented by Formula 1, and the epoxy resin represented by Formula 1 may be present in the epoxy resin composition in an amount ranging from about 0.1 wt% to about 17 wt%, for example 2 wt% to 17 wt%, for example 2 wt% to 10 wt%. Within the above range, the epoxy resin composition may exhibit improved heat dissipation properties without deteriorating curability.

[0045] The epoxy resin represented by chemical formula 1 can be prepared by any typical method of preparing epoxy resin known to those skilled in the art.

[0046] For example, epoxy resin represented by chemical formula 1 can be prepared according to the following reaction: Reaction 1: .

[0047] In reaction 1, L 11 The definition is the same as that in chemical formula 2 above, and

[0048] R is or includes substituted or unsubstituted C1 to C2. 20Alkyl, substituted or unsubstituted C6 to C 30 Aryl, substituted or unsubstituted C6 to C 30 aryloxy group, substituted or unsubstituted C3 to C4 30 heteroaryl, substituted or unsubstituted C3 to C 30 Heterocyclic alkyl, substituted or unsubstituted C7 to C8 30 arylalkyl or substituted or unsubstituted C1 to C2 30 Heteroalkyl groups, and

[0049] n is an integer in the range of approximately 0 to approximately 10.

[0050] The epoxy resin in an epoxy resin composition may include or consist solely of the epoxy resin represented by Formula 1. However, this disclosure is not limited thereto, and the epoxy resin composition may also contain epoxy resins different from those represented by Formula 1 without affecting the desired effects of this disclosure. For ease of description, the epoxy resin represented by Formula 1 is referred to as the first epoxy resin, and epoxy resins different from those represented by Formula 1 are referred to as the second epoxy resin.

[0051] The second epoxy resin is or includes epoxy resins containing at least two epoxy groups in their molecular structure, and may include at least one of the following: bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, tert-butylcatechol epoxy resin, naphthalene epoxy resin, glycidylamine epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, phenol aralkyl epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, cyclohexanediol epoxy resin, trimethylolpropene epoxy resin, halogenated epoxy resin, etc. These epoxy resins may be used alone or in mixtures thereof as the second epoxy resin.

[0052] Epoxy resin can be present in the epoxy resin composition in an amount ranging from about 2 wt% to about 17 wt%, for example, from 2 wt% to 10 wt%. Within the above range, the composition can avoid a reduction in curability.

[0053] curing agent

[0054] The curing agent may include polyfunctional phenolic resins, comprising at least one of the following: aralkyl phenolic resins, phenolic varnish-type phenolic resins, Xylok-type phenolic resins, cresolnovolac-type phenolic resins, naphthol-type phenolic resins, terpene-type phenolic resins, dicyclopentadiene phenolic resins, and phenolic varnish-type phenolic resins synthesized from bisphenol A and methyl phenolic resins; polyphenolic compounds, including tris(hydroxyphenyl)methane and dihydroxybiphenyl; acid anhydrides, including maleic anhydride and phthalic anhydride; and aromatic amines, including m-phenylenediamine, diaminodiphenylmethane, and diaminodiphenyl sulfone. For example, the curing agent may include Xylok-type phenolic resins or aralkyl phenolic resins.

[0055] The curing agent may be present in the epoxy resin composition in an amount ranging from about 0.5 wt% to about 13 wt%. Within the above range, the composition can avoid a reduction in curability.

[0056] Inorganic packing

[0057] Inorganic fillers improve the mechanical properties of epoxy resin compositions while reducing their internal stress.

[0058] Inorganic fillers may include at least one of fused silica, crystalline silica, calcium carbonate, magnesium carbonate, aluminum oxide, magnesium oxide, clay, talc, calcium silicate, titanium oxide, antimony oxide, and glass fiber.

[0059] For example, inorganic fillers include fused silica with a low coefficient of linear expansion for stress reduction. Fused silica refers to amorphous silica with a specific gravity of about 2.3 or less, and may include amorphous silica obtained by melting crystalline silica or synthesized from various raw materials. Although fused silica is not limited to a specific shape and size, inorganic fillers may include a mixture of about 40 wt% to about 100 wt% of fused silica, comprising about 50 wt% to about 99 wt% of spherical fused silica with an average particle size ranging from about 5 μm to about 30 μm and about 1 wt% to about 50 wt% of spherical fused silica with an average particle size ranging from about 0.001 μm to about 1 μm. Furthermore, the maximum particle size of the inorganic filler may be adjusted to about 45 μm, about 55 μm, about 75 μm, etc., depending on the application.

[0060] The content of inorganic fillers in the composition can be varied depending on desired properties of the composition, such as thermal conductivity, moldability, low stress, and strength at high temperatures. In some exemplary embodiments, the inorganic fillers may be present in the epoxy resin composition in an amount ranging from about 50 wt% to about 95 wt%, for example 70 wt% to 95 wt%, and for example 85 wt% to 95 wt%. Within this range, the epoxy resin composition may have desired properties in terms of flame retardancy, flowability, and reliability.

[0061] Curing catalyst

[0062] The curing catalyst may include at least one of the following: a tertiary amine compound, an organometallic compound, an organophosphorus compound, an imidazole compound, or a boron compound. Tertiary amine compounds may include at least one of, for example, benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tris(dimethylaminomethyl)phenol, 2,2-(dimethylaminomethyl)phenol, 2,4,6-tris(diaminomethyl)phenol, tri-2-ethylhexanoate, etc. Organometallic compounds may include at least one of, for example, chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate, etc. Organophosphorus compounds may include at least one of, for example, triphenylphosphine, tri-4-methoxyphosphine, triphenylphosphine-triphenylborane, triphenylphosphine-1,4-benzoquinone adduct, etc. Imidazole compounds may include at least one of, for example, 2-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, 2-methyl-1-vinylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecanylimidazole, etc. Boron compounds may include at least one of the following: triphenylphosphine tetraphenyl borate, tetraphenylboronic acid, tetraphenylboronic acid, triphenylborane, trifluoroborane-hexylamine, trifluoroborane monoethylamine, tetrafluoroborane triethylamine, tetrafluoroboraneamine, etc. In addition to these compounds, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and phenol novolacresin salt may also be used as curing catalysts.

[0063] The curing catalyst can be provided in the form of an adduct prepared by pre-reacting the curing catalyst with an epoxy resin or a curing agent.

[0064] The curing catalyst may be present in the epoxy resin composition in an amount ranging from about 0.01 wt% to about 5 wt%. Within this range, the curing catalyst can promote the curing of the composition without sacrificing its flowability.

[0065] The epoxy resin composition may also include typical additives used in epoxy resin compositions for encapsulating semiconductor devices. In some exemplary embodiments, the additives may include at least one of coupling agents, release agents, colorants, stress relievers, crosslinking enhancers, and leveling agents.

[0066] Coupling agents increase the interfacial strength between epoxy resin and inorganic fillers through reaction with the epoxy resin and inorganic fillers, and may include, for example, silane coupling agents. Silane coupling agents may include any silane coupling agent that can increase the interfacial strength between epoxy resin and inorganic fillers through reaction with the epoxy resin and inorganic fillers, without limitation. Silane coupling agents may include at least one of, for example, epoxysilanes, aminosilanes, ureosilanes, mercaptosilanes, alkylsilanes, etc. These coupling agents may be used alone or in combination. The coupling agent may be present in the epoxy resin composition for encapsulating semiconductor devices in an amount ranging from about 0.01 wt% to about 5 wt%, for example, from 0.05 wt% to 3 wt%. Within the above range, the cured product of the epoxy resin composition may exhibit enhanced strength.

[0067] The release agent may include at least one of paraffin wax, ester wax, higher fatty acids, metal salts of higher fatty acids, natural fatty acids, and metal salts of natural fatty acids. The release agent may be present in the epoxy resin composition in an amount ranging from about 0.1 wt% to about 1 wt%.

[0068] The colorant may include carbon black. The colorant may be present in the epoxy resin composition in an amount ranging from about 0.1 wt% to about 1 wt%.

[0069] The stress reliever may include, but is not limited to, at least one of modified silicone oil, silicone elastomer, silicone powder, and silicone resin. The stress reliever may optionally be present in the epoxy resin composition in an amount ranging from about 2 wt% or less, for example, 1 wt% or less, for example, from 0.1 wt% to 1 wt%.

[0070] The additive may be present in the epoxy resin composition in an amount ranging from about 0.1 wt% to about 5 wt%, for example from 0.1 wt% to 3 wt%.

[0071] Although the method of preparing the epoxy resin composition is not particularly limited, the epoxy resin composition can be prepared by uniformly mixing the above components in a Henschel mixer or Lödige mixer, melting and kneading the mixture in a roller mill or kneader at a temperature in the range of about 90°C to about 120°C, and cooling and pulverizing the resulting product.

[0072] According to another aspect of this disclosure, a semiconductor device is encapsulated using an epoxy resin composition for encapsulating a semiconductor device according to this disclosure. The semiconductor device can be encapsulated with the epoxy resin composition by any suitable method known in the art, such as, for example, transfer molding, injection molding, casting, or compression molding, but is not limited thereto. In one exemplary embodiment, the semiconductor device can be encapsulated with an epoxy resin composition using low-pressure transfer molding. In another exemplary embodiment, the semiconductor device can be encapsulated with an epoxy resin composition using compression molding.

[0073] The present disclosure is described in more detail below with reference to some embodiments. However, it should be noted that these embodiments are provided for illustrative purposes only and should not be construed as limiting the present disclosure in any way.

[0074] Preparation Example 1: Preparation of Epoxy Resin 1-1

[0075] In the presence of TBAB (tetra-n-butylammonium bromide), benzo[a]anthracene-3,9-diol (26 g, 0.1 mol) and excess (300 g) of 2-(4-chlorobutyl)ethylene oxide were heated (to 90°C) for 6 hours in a solvent-free environment, then cooled to room temperature. The remaining unreacted 2-(4-chlorobutyl)ethylene oxide was then removed using a Kugelrohr distillation apparatus. An aqueous solution of NaOH and toluene were then added to the product obtained by synthesis, followed by heating to 90°C for 4 hours, thereby synthesizing the epoxy resin represented by Formula 1-1 above in 75% yield via intramolecular Williamson ether synthesis. 1 H NMR (400MHz, CDCl3) δ 8.93 (s, 1H), 8.82 (s, 1H), 8.12 (m, 1H), 7.71 (m, 2H), 7.65-7.60 (m, 2H), 7.39 (m, 1H), 7.05-6.97 (m, 2H), 4.04 (m, 4H), 2.60-2.35 (m,6H), 1.71 (m, 4H), 1.42-1.25 (m, 8H) ppm; 13 C NMR (100 MHz, CDCl3) δ 157.3,155.9, 134.0, 133.4, 131.5, 129.8, 129.6, 129.5, 126.6, 126.5, 125.1, 123.1,123.0, 118.0, 111.2, 109.6, 105.9, 68.9, 68.8, 52.3, 47.9, 33.5, 33.2, 29.4,21.6 ppm; GC-MS m / z = 456 (M+); C 30 H 32 Analytical values ​​of O4: C, 78.92; H, 7.06. Measured values: C, 78.53; H, 7.48.

[0076] Preparation Example 2: Preparation of Epoxy Resin 1-2

[0077] In the presence of TBAB (tetra-n-butylammonium bromide), 27 g (0.1 mol) of 7-methylbenzo[a]anthracene-3,9-diol and an excess (300 g) of 2-(4-chlorobutyl)ethylene oxide were heated (to 90°C) for 6 hours in a solvent-free environment, then cooled to room temperature. The remaining unreacted 2-(4-chlorobutyl)ethylene oxide was then removed using a Kugelrohr distillation apparatus. An aqueous solution of NaOH and toluene were then added to the product obtained by synthesis, followed by heating to 90°C for 4 hours, thereby synthesizing the epoxy resins represented by the above chemical formulas 1-2 in 75% yield via intramolecular Williamson ether synthesis. 1 H NMR (400 MHz, CDCl3) δ 8.82 (s, 1H), 8.74 (m, 1H), 7.71 (s, 2H), 7.65-7.60(m, 2H), 7.39 (m, 1H), 7.05 (m, 1H), 6.98 (s, 1H), 4.04 (m, 4H), 2.65-2.35(m, 9H), 1.71 (m, 4H), 1.43-1.25 (m, 8H) ppm; 13 C NMR (100 MHz, CDCl3) δ157.4, 155.7, 137.5, 134.0, 133.4, 131.5, 129.8, 129.6, 129.5, 126.6, 126.5,125.1, 123.1, 123.0, 118.0, 116.2, 111.2, 109.6, 105.9, 68.9, 52.3, 47.9,33.5, 29.4, 21.6, 20.8 ppm; GC-MS m / z = 470 (M+); C 31 H 34 Analytical values ​​of O4: C, 79.12; H, 7.28. Measured values: C, 79.34; H, 7.52.

[0078] Preparation Example 3: Preparation of Epoxy Resins 1-3

[0079] In the presence of TBAB (tetra-n-butylammonium bromide), 27 g (0.1 mol) of 7-methylbenzo[a]anthracene-3,9-diol and an excess (300 g) of 2-(6-chlorohexyl)ethylene oxide were heated (to 90°C) for 6 hours in a solvent-free environment, then cooled to room temperature. The remaining unreacted 2-(6-chlorohexyl)ethylene oxide was then removed using a Kugelrohr distillation apparatus. An aqueous solution of NaOH and toluene were then added to the product obtained by synthesis, followed by heating to 90°C for 4 hours, thereby synthesizing the epoxy resins represented by formulas 1-3 above via intramolecular Williamson ether synthesis in 68% yield. 1 H NMR (400 MHz, CDCl3) δ 8.82 (s, 1H), 8.74 (m, 1H), 7.71 (s, 2H), 7.65-7.60(m, 2H), 7.39 (m, 1H), 7.05 (m, 1H), 6.98 (s, 1H), 4.04 (m, 4H), 2.65-2.35(m, 9H), 1.71 (m, 4H), 1.45-1.20 (m, 16H) ppm; 13 C NMR (100 MHz, CDCl3) δ157.4, 155.7, 137.5, 134.0, 133.4, 131.5, 129.8, 129.6, 129.5, 126.6, 126.5,125.1, 123.1, 123.0, 118.0, 116.2, 111.2, 109.6, 105.9, 68.9, 52.3, 47.9,33.5, 29.4, 25.3, 25.1, 21.6, 20.8 ppm; GC-MS m / z = 526 (M+); C 35 H 42 Analytical values ​​of O4: C, 79.81; H, 8.04. Measured values: C, 79.59; H, 8.50.

[0080] Preparation Example 4: Preparation of Epoxy Resins 1-4

[0081] In the presence of TBAB (tetra-n-butylammonium bromide), 27 g (0.1 mol) of 7-methylbenzo[a]anthracene-3,9-diol and an excess (300 g) of 2-(8-chlorooctyl)ethylene oxide were heated (to 90°C) for 6 hours in a solvent-free environment, then cooled to room temperature. The remaining unreacted 2-(8-chlorooctyl)ethylene oxide was then removed using a Kugelrohr distillation apparatus. An aqueous solution of NaOH and toluene were then added to the product obtained by synthesis, followed by heating to 90°C for 4 hours, thereby synthesizing the epoxy resins represented by formulas 1-4 above in 75% yield via intramolecular Williamson ether synthesis. 1 H NMR (400 MHz, CDCl3) δ 8.82 (s, 1H), 8.74 (m, 1H), 7.71 (s, 2H), 7.65-7.60(m, 2H), 7.39 (m, 1H), 7.05 (m, 1H), 6.98 (s, 1H), 4.04 (m, 4H), 2.65-2.35(m, 9H), 1.71 (m, 4H), 1.42 (m, 4H), 1.32-1.26 (m, 20H) ppm; 13 C NMR (100 MHz, CDCl3) δ 157.3, 155.5, 137.6, 134.1, 133.3, 131.5, 129.8, 129.7, 129.6 129.5,126.6, 126.5, 125.1, 123.1, 123.0, 118.0, 116.2, 111.2, 109.6, 105.9, 68.9,52.3, 47.9, 33.5, 29.4, 29.3, 29.2, 25.3, 25.1, 21.5, 20.7 ppm; GC-MS m / z =582 (M+); C 39 H 50 Analytical values ​​of O4: C, 80.37; H, 8.65. Measured values: C, 80.39; H, 8.27.

[0082] Preparation Example 5: Preparation of Epoxy Resins 1-5

[0083] In the presence of TBAB (tetra-n-butylammonium bromide), 29 g (0.1 mol) of 7-dimethylbenzo[a]anthracene-3,9-diol and an excess (300 g) of 2-(4-chlorobutyl)ethylene oxide were heated (to 90°C) for 6 hours in a solvent-free environment, then cooled to room temperature. The remaining unreacted 2-(4-chlorobutyl)ethylene oxide was then removed using a Kugelrohr distillation apparatus. An aqueous solution of NaOH and toluene were then added to the product obtained by synthesis, followed by heating to 90°C for 4 hours, thereby synthesizing the epoxy resins represented by chemical formulas 1-5 in 75% yield via intramolecular Williamson ether synthesis. 1 H NMR (400 MHz, CDCl3) δ 8.82 (s, 1H), 7.71 (s, 2H), 7.65-7.60 (m, 2H), 7.39(m, 1H), 7.05 (m, 1H), 6.98 (s, 1H), 4.04 (m, 4H), 2.65-2.35 (m, 12H), 1.71(m, 4H), 1.43-1.25 (m, 8H) ppm; 13 C NMR (100 MHz, CDCl3) δ 157.4, 155.7,137.5, 134.0, 133.4, 131.5, 129.8, 129.6, 129.5, 126.6, 126.5, 125.1, 123.1,123.0, 118.0, 116.2, 111.2, 109.6, 105.9, 68.9, 52.3, 47.9, 33.5, 29.4, 21.6,20.8, 20.4 ppm; GC-MS m / z = 484 (M+); C 32 H 36 Analytical values ​​of O4: C, 79.31; H, 7.49. Measured values: C, 79.34; H, 7.58.

[0084] Preparation Example 6: Preparation of Epoxy Resins 1-6

[0085] In the presence of TBAB (tetra-n-butylammonium bromide), benzo[a]anthracene-5,9-diol (26 g, 0.1 mol) and excess (300 g) of 2-(4-chlorobutyl)ethylene oxide were heated (to 90°C) for 6 hours in a solvent-free environment, then cooled to room temperature. The remaining unreacted 2-(4-chlorobutyl)ethylene oxide was then removed using a Kugelrohr distillation apparatus. An aqueous solution of NaOH and toluene were then added to the product obtained by synthesis, followed by heating to 90°C for 4 hours, thereby synthesizing epoxy resins represented by formulas 1-6 in 70% yield via intramolecular Williamson ether synthesis. 1 H NMR (400MHz, CDCl3) δ 8.93 (s, 1H), 8.12 (m, 2H), 7.88 (s, 1H), 7.81 (s, 1H), 7.22(s, 1H), 7.05-6.97 (m, 2H), 4.08 (m, 4H), 2.60-2.35 (m, 6H), 1.71 (m, 4H), 1.42-1.25 (m, 8H) ppm; 13 C NMR (100 MHz, CDCl3) δ 157.3, 150.5, 134.0, 132.4,129.8, 129.6, 129.5, 128.3, 126.6, 125.1, 123.1, 123.0, 122.4, 118.0, 111.2,109.6, 105.9, 68.9, 52.3, 52.1, 47.9, 33.5, 33.2, 29.4, 29.3, 21.6 ppm; GC-MS m / z = 456 (M+); C 30 H 32 Analytical values ​​of O4: C, 78.92; H, 7.06. Measured values: C, 78.77; H, 7.39.

[0086] Details of the components used in the examples and comparative examples are as follows: (A) Epoxy resin (A1)-(A6) Epoxy resins prepared in Preparation Examples 1 to 6 (A7) Epoxy resin represented by the following chemical formula: .

[0087] (A8) Biphenyl epoxy resin (NC-3000, Nippon Kayaku Co. Ltd.)

[0088] (A9) Anthracene epoxy resin (YX-8800, Mitsubishi Chemical Co. Ltd.)

[0089] (B) Curing agent

[0090] (B1) KPH-F3065 (Xylok type phenolic resin, Kolon Industry Co. Ltd.)

[0091] (B2) MEH-7851 (phenol-aralkylphenol resin, Meiwa Co., Ltd.)

[0092] (C) Curing catalyst

[0093] Triphenylphosphine (Hokko Chemical Co. Ltd.)

[0094] (D) Inorganic filler: A mixture of spherical molten alumina with an average particle size (D50) of 20 μm and spherical molten alumina with an average particle size (D50) of 0.5 μm (weight ratio: 9:1).

[0095] (E) Coupling agent

[0096] (E1) Methyltrimethoxysilane (SZ-6070, Dow Corning)

[0097] (E2) KBM-573 (N-Phenylacetyl-3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.)

[0098] (F) Colorant: Carbon black (MA-600B, Mitsubishi Chemical Co. Ltd.)

[0099] Examples 1 to 7 and Comparative Examples 1 to 5

[0100] In a Henschel mixer (KSM-22, Keumsung Machinery Co., Ltd.), the above components were uniformly mixed for 30 min at the amounts (parts by weight) shown in Table 1 below at a temperature ranging from 25°C to 30°C. The mixture was then melt-kneaded in a continuous kneader at a temperature up to 110°C for 30 min, cooled to a temperature of 10°C to 15°C, and pulverized to prepare an epoxy resin composition for encapsulating semiconductor devices. In Table 1 below, "-" indicates that the corresponding component was not used.

[0101] The epoxy resin compositions prepared in the Examples and Comparative Examples were evaluated for the following properties. The results are shown in Table 1 below.

[0102] (1) Flowability (spiral flow length, in inches): Using a low-pressure transfer molding machine, according to EMMI-1-66, at a mold temperature of 175°C and 70 kgf / cm². 2 Under conditions of high load, injection pressure of 9 MPa, and curing time of 90 seconds, each prepared epoxy resin composition was injected into a mold used to measure flowability, and the flow length was subsequently measured. A larger flow length indicates better flowability.

[0103] (2) Toughness (unit: kgf / mm) 2 According to ASTM D-790, standard specimens (dimensions: 125 mm × 12.6 mm × 6.4 mm (length × width × thickness)) are prepared from each of the prepared epoxy resin compositions and cured at 175°C for 4 hours. The toughness of the specimens is then measured at 25°C using a universal testing machine (UTM) via a 3-point bending test.

[0104] (3) Thermal conductivity (unit: W / m·K): Thermal conductivity was measured on specimens prepared from each of the prepared epoxy resin compositions at 25°C, according to ASTM D5470. Specifically, specimens for measuring thermal conductivity were prepared by injecting each epoxy resin composition into a transfer molding machine under the conditions of a mold temperature of 175°C, an injection pressure of 9 MPa, and a curing time of 120 seconds, according to ASTM D5470. The thermal conductivity of the specimens was then measured at 25°C using a flash laser thermal conductivity meter (LFA467, NETZSCH Group).

[0105] (4) Reliability (unit: number): Semiconductor packages made using each prepared epoxy resin composition were dried at 125°C for 24 hours and then subjected to 5 cycles of thermal shock testing (one cycle was defined as placing the package at -65°C for 10 minutes, at 25°C for 10 minutes, and at 150°C for 10 minutes). After this, following a preconditioning treatment, the presence of external cracks was observed under an optical microscope. In this preconditioning treatment, the package was placed at 85°C and 60% RH for 168 hours, followed by a 30-second IR reflow at 260°C, repeated three (3) times. The presence of delamination between the epoxy resin composition and the lead frame was then evaluated using scanning acoustic microscopy (C-SAM) as a non-destructive testing method. The presence of external cracks in the semiconductor package, or delamination between the epoxy resin composition and the lead frame, indicated poor reliability of the corresponding semiconductor package.

[0106] Table 1:

[0107] As shown in Table 1 above, the epoxy resin compositions of the embodiments exhibit high thermal conductivity to ensure desired or improved heat dissipation, and reliability can be improved by improving toughness.

[0108] Conversely, the comparative epoxy resin compositions prepared without using the epoxy resin represented by Formula 1 have significantly lower thermal conductivity and toughness than the epoxy resin compositions of the examples, and therefore do not show any improvement in heat dissipation and reliability.

[0109] It should be understood that those skilled in the art can make various modifications, variations, alterations, and equivalent exemplary implementations without departing from the spirit and scope of this disclosure.

Claims

1. An epoxy resin composition for encapsulating a semiconductor device, the epoxy resin composition comprising: Epoxy resin; Curing agent; Inorganic packing materials; and Solidified catalyst; in, The epoxy resin includes epoxy resin represented by chemical formula 1: Chemical Formula 1 ； Among them, R 1 To R 12 Each is independently hydrogen, substituted or unsubstituted C1 to C2. 20 Alkyl, substituted or unsubstituted C6 to C 30 Aryl, substituted or unsubstituted C6 to C 30 aryloxy group, substituted or unsubstituted C3 to C4 30 heteroaryl, substituted or unsubstituted C3 to C 30 Heterocyclic alkyl, substituted or unsubstituted C7 to C8 30 arylalkyl, substituted or unsubstituted C1 to C 30 Heteroalkyl groups or groups represented by chemical formula 2, R 1 To R 12 At least two of them are groups represented by chemical formula 2: ； in, It is the linking site of the element, and L 11 It is substituted or unsubstituted C4 to C 10 Alkylene.

2. The epoxy resin composition for encapsulating semiconductor devices according to claim 1, wherein: R in chemical formula 1 1 To R 4 At least one of them is a group represented by chemical formula 2; and R in chemical formula 1 8 To R 11 At least one of them is a group represented by chemical formula 2, or R in chemical formula 1. 6 To R 7 At least one of them is a group represented by chemical formula 2.

3. The epoxy resin composition for encapsulating semiconductor devices according to claim 1, wherein: R in chemical formula 1 1 To R 12 Each is independently hydrogen, substituted or unsubstituted C1 to C2. 20 Alkyl groups or groups represented by chemical formula 2, and R 1 To R 12 At least two of them are groups represented by chemical formula 2.

4. The epoxy resin composition for encapsulating semiconductor devices according to claim 1, wherein, The epoxy resin represented by Formula 1 includes at least one of the compounds represented by Formulas 1-1 to 1-6: Chemical formula 1-1: ； Chemical formula 1-2: ； Chemical formulas 1-3: ； Chemical formulas 1-4: ； Chemical formulas 1-5: ； Chemical formulas 1-6: 。 5. The epoxy resin composition for encapsulating semiconductor devices according to claim 1, wherein, The epoxy resin represented by chemical formula 1 is present in the epoxy resin composition for encapsulating semiconductor devices in an amount ranging from 0.1 wt% to 17 wt%.

6. The epoxy resin composition for encapsulating semiconductor devices according to claim 1, wherein, The inorganic filler includes alumina.

7. The epoxy resin composition for encapsulating a semiconductor device according to claim 1, comprising: The epoxy resin, ranging from 2 wt% to 17 wt%; The curing agent is 0.5 wt% to 13 wt% of the amount mentioned above; The inorganic filler comprising 50 wt% to 95 wt%; and The cured catalyst is 0.01 wt% to 5 wt%.

8. A semiconductor device encapsulated using an epoxy resin composition for encapsulating a semiconductor device as described in any one of claims 1 to 7.

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