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

Abstract

An epoxy resin composition for encapsulating a semiconductor device and a semiconductor device encapsulated using the epoxy resin composition, the epoxy resin composition including an epoxy resin; a curing agent; an inorganic filler; and a curing catalyst, wherein the epoxy resin includes an epoxy resin represented by Formula 1. [Formula 1] # imgabs0 #

Description

[0001] Cross - reference to related applications

[0002] This application claims the priority and benefit of Korean Patent Application No. 10 - 2024 - 0009879, filed with the Korean Intellectual Property Office on January 23, 2024, the entire disclosure of which is incorporated herein by reference. Technical field

[0003] Embodiments relate to an epoxy resin composition for encapsulating a semiconductor device and a semiconductor device encapsulated using the same. Background art

[0004] Recently, the integration degree of semiconductor devices has been improved. In a semiconductor device in which high - density semiconductor devices are stacked and encapsulated in a small and thin package, due to the heat generated during the operation of the semiconductor devices, failures such as package cracking or malfunction may occur.

[0005] As a solution to the problems caused by heat generation, it has been considered to bond a heat sink formed of a heat - dissipating material (such as a metal) to a semiconductor package when molding an epoxy resin for encapsulation. However, such a heat sink can only be used for certain packages, such as fine pitch ball grid array (FBGA) and quad flat package (QFP), and there may be problems of high cost and reduced productivity due to the need for an additional assembly process. Therefore, there is an urgent need for an epoxy resin material for encapsulating a semiconductor device, which has high thermal conductivity and thus good heat - dissipating ability. Summary of the invention

[0006] Embodiments relate to an epoxy resin composition for encapsulating a semiconductor device, the composition including an epoxy resin; a curing agent; an inorganic filler; and a curing catalyst, wherein the epoxy resin includes a compound represented by Formula 1:

[0007] [Formula 1]

[0008]

[0009] R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 and R 10 are each independently hydrogen, a substituted or unsubstituted C1 - C 20 alkyl, a substituted or unsubstituted C1 - C 20Alkoxy, hydroxy, amino, nitro, cyano, substituted or unsubstituted C1 to C 20 Alkenyl, substituted or unsubstituted C1 to C 20 Haloalkyl, substituted or unsubstituted C6 to C 30 Aryl, substituted or unsubstituted C3 to C 30 Heteroaryl, substituted or unsubstituted C3 to C 10 Cycloalkyl, substituted or unsubstituted C3 to C 10 Heterocycloalkyl, substituted or unsubstituted C7 to C 30 Aralkyl, substituted or unsubstituted C1 to C 30 Heteroalkyl or a group represented by Formula 2:

[0010] [Formula 2]

[0011]

[0012] * is the bonding site to the element, R 1 , R 2 , R 3 , R 4 and R 5 at least one of which is a group represented by Formula 2, and R 6 , R 7 , R 8 , R 9 and R 10 at least one of which is a group represented by Formula 2.

[0013] In Formula 1, R 3 may be a group represented by Formula 2, and R 1 , R 2 , R 4 , and R 5 may each independently be hydrogen, substituted or unsubstituted C1 to C 20 alkyl or substituted or unsubstituted C1 to C 20 alkoxy, and R 8 may be a group represented by Formula 2, and R 6 , R 7 , R 9 , and R 10 may each independently be hydrogen, substituted or unsubstituted C1 to C 20 alkyl or substituted or unsubstituted C1 to C 20 alkoxy.

[0014] The epoxy resin represented by Formula 1 may include a compound represented by Formula 1-1, a compound represented by Formula 1-2, a compound represented by Formula 1-3, a compound represented by Formula 1-4, or a compound represented by Formula 1-5:

[0015] [Formula 1-1]

[0016]

[0017] [Formula 1-2]

[0018]

[0019] [Formula 1-3]

[0020]

[0021] [Formula 1-4]

[0022]

[0023] [Formula 1-5]

[0024]

[0025] Based on the total weight of the epoxy resin composition, the epoxy resin represented by Formula 1 may be present in an amount of 0.1% to 17% by weight.

[0026] The inorganic filler may include alumina.

[0027] Based on the total weight of the epoxy resin composition, the epoxy resin may include: 2% to 17% by weight of epoxy resin, 0.5% to 13% by weight of curing agent, 50% to 95% by weight of inorganic filler, and 0.01% to 5% by weight of curing catalyst.

[0028] Examples may be implemented by providing a semiconductor device encapsulated with the epoxy resin composition.

[0029] In Formula 1, R 3 may be a group represented by Formula 2, R 1 , R 2 , R 4 and R 5 may each independently be hydrogen, a substituted or unsubstituted C1 to C 20 alkyl group or a substituted or unsubstituted C1 to C 20 alkoxy group, and R 8 may be a group represented by Formula 2, R 6 , R 7 , R 9 and R 10 may each independently be hydrogen, a substituted or unsubstituted C1 to C 20 alkyl group or a substituted or unsubstituted C1 to C 20 alkoxy group.

[0030] The epoxy resin represented by Formula 1 may include a compound represented by Formula 1-1, a compound represented by Formula 1-2, a compound represented by Formula 1-3, a compound represented by Formula 1-4, or a compound represented by Formula 1-5:

[0031] [Formula 1-1]

[0032]

[0033] [Formula 1-2]

[0034]

[0035] [Formula 1-3]

[0036]

[0037] [Formula 1-4]

[0038]

[0039] [Formula 1-5]

[0040]

[0041] Based on the total weight of the epoxy resin composition, the epoxy resin represented by Formula 1 may be present in an amount of 0.1 wt% to 17 wt%.

[0042] The inorganic filler may include alumina.

[0043] Based on the total weight of the epoxy resin composition, the epoxy resin composition may include: 2 wt% to 17 wt% of an epoxy resin, 0.5 wt% to 13 wt% of a curing agent, 50 wt% to 95 wt% of an inorganic filler, and 0.01 wt% to 5 wt% of a curing catalyst. Detailed Description

[0044] Exemplary embodiments will now be described more fully; however, they may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the exemplary embodiments to those skilled in the art.

[0045] It should also be understood that when referring to a layer or element "on" another layer or substrate, it can be directly on the other layer or substrate or there can also be intervening layers. Further, it will be understood that when referring to a layer "under" another layer, it can be directly underneath and there can also be one or more intervening layers. Additionally, it will also be understood that when referring to a layer "between" two layers, it can be the only layer between the two layers or there can also be one or more intervening layers. As used herein, the term "or" is not an exclusive term, e.g., "A or B" will include A, B, or A and B.

[0046] As used herein, the singular forms "a" and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise.

[0047] As used herein to denote a specific numerical range, the expression "X to Y" means "greater than or equal to X and less than or equal to Y".

[0048] As used herein, "substituted" in the expression "substituted or unsubstituted" means that at least one hydrogen atom of the corresponding functional group is replaced by a hydroxyl group, an amino group, a nitro group, a cyano group, a C1 to C 20 alkyl group, a substituted or unsubstituted C1 to C 20 alkoxy group, a C1 to C 20 haloalkyl group, a C6 to C 30 aryl group, a C3 to C 30 heteroaryl group, a C3 to C 10 cycloalkyl group, a C3 to C 10 heterocycloalkyl group, a C7 to C 30 aralkyl group or a C1 to C 30 heteroalkyl group.

[0049] To impart high thermal conductivity to an epoxy resin composition for encapsulating semiconductor devices, a relatively large amount of inorganic filler may be required. However, using a large amount of inorganic filler may lead to an increase in the viscosity of the composition and a decrease in fluidity, which may make it difficult to form a semiconductor package.

[0050] The use of alumina can be considered. Alumina can be an inorganic filler with relatively high thermal conductivity. However, since the epoxy resin contained in the composition can have a very low thermal conductivity of about 0.2 W / m·K, even when using alumina, there may be limitations in improving the thermal conductivity of the composition.

[0051] According to some embodiments, an epoxy resin composition for encapsulating a semiconductor device may include an epoxy resin, a curing agent, an inorganic filler, and a curing catalyst, wherein the epoxy resin may include an epoxy resin represented by Formula 1. The epoxy resin represented by Formula 1 may help improve the heat dissipation ability of the composition due to its high thermal conductivity, and may help improve the fluidity of the composition due to its low viscosity. As a result, the epoxy resin composition according to some embodiments may help inhibit heat-induced failures or defects of the semiconductor package and may help improve the reliability of the semiconductor package by maintaining the surface temperature of the semiconductor at a low level. In addition, the epoxy resin represented by Formula 1 may help reduce the moisture absorption of the composition while reducing the soldering stress.

[0052] Epoxy resin

[0053] The epoxy resin may include an epoxy resin represented by Formula 1. The epoxy resin represented by Formula 1 may help improve the heat dissipation ability of the composition due to its high thermal conductivity, and may help improve the fluidity and processability of the composition due to its low viscosity.

[0054] [Formula 1]

[0055]

[0056] In Formula 1, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 may each independently be or include, for example, hydrogen, a substituted or unsubstituted C1 to C 20 alkyl, a substituted or unsubstituted C1 to C 20 alkoxy, a hydroxyl group, an amino group, a nitro group, a cyano group, a substituted or unsubstituted C1 to C 20 alkenyl, a substituted or unsubstituted C1 to C 20 haloalkyl, a substituted or unsubstituted C6 to C 30 aryl, a substituted or unsubstituted C3 to C 30 heteroaryl, a substituted or unsubstituted C3 to C 10 cycloalkyl, a substituted or unsubstituted C3 to C 10 heterocycloalkyl, a substituted or unsubstituted C7 to C 30 aralkyl, a substituted or unsubstituted C1 to C 30 heteroalkyl or a group represented by Formula 2.

[0057] [Formula 2]

[0058]

[0059] In Formula 2, * is the linkage site with the element.

[0060] R 1 、R 2 、R 3 、R 4 and R 5 at least one of which may be a group represented by Formula 2, and R 6 、R 7 、R 8 、R 9 and R 10 at least one of which may be a group represented by Formula 2.

[0061] In an embodiment, among R 1 、R 2 、R 3 、R 4 and R 5 ,R 3 may be a group represented by Formula 2, and R 1 、R 2 、R 4 and R 5 may each independently be, for example, hydrogen, substituted or unsubstituted C1 to C 20 alkyl or substituted or unsubstituted C1 to C 20 alkoxy, for example, hydrogen, unsubstituted C1 to C5 alkyl or substituted or unsubstituted C1 to C5 alkoxy.

[0062] In an embodiment, among R 6 、R 7 、R 8 、R 9 and R 10 ,R 8 may be a group represented by Formula 2, and R 6 、R 7 、R 9 and R 10 may each independently be, for example, hydrogen, substituted or unsubstituted C1 to C 20 alkyl or substituted or unsubstituted C1 to C 20 alkoxy, for example, hydrogen, unsubstituted C1 to C5 alkyl or substituted or unsubstituted C1 to C5 alkoxy.

[0063] In an embodiment, the epoxy resin represented by Formula 1 may include, for example, a compound represented by Formula 1-1, a compound represented by Formula 1-2, a compound represented by Formula 1-3, a compound represented by Formula 1-4, or a compound represented by Formula 1-5.

[0064] [Formula 1-1] (1,4-bis(4-(oxiran-2-ylmethoxy)phenyl)buta-1,3-diyne)

[0065]

[0066] [Formula 1-2] (2-((3-methyl-4-(4-(2-methyl-4-(oxiran-2-ylmethoxy)phenyl)buta-1,3-diyne)phenyl)oxy)methyl)oxirane)

[0067]

[0068] [Formula 1-3] (2-((4-(4-(2,6-dimethyl-4-(oxiran-2-ylmethoxy)phenyl)buta-1,3-diyne)-3,5-dimethylphenyl)oxy)methyl)oxirane)

[0069]

[0070] [Formula 1-4] (2-((3-methoxy-4-(4-(2-methoxy-4-(oxiran-2-ylmethoxy)phenyl)buta-1,3-diyne)phenyl)oxy)methyl)oxirane)

[0071]

[0072] [Formula 1-5] (2-((4-(4-(2,6-diethyl-4-(oxiran-2-ylmethoxy)phenyl)buta-1,3-diyne)-3,5-diethylphenyl)oxy)methyl)oxirane)

[0073]

[0074] As the epoxy resin represented by Formula 1, these compounds can be used alone or in combination in an epoxy resin composition. Based on the total weight of the epoxy resin composition, the epoxy resin represented by Formula 1 can be present in an amount of 0.1% by weight to 17% by weight, for example, 2% by weight to 17% by weight or 2% by weight to 10% by weight. Within these ranges, the composition can have improved heat dissipation ability without reducing the curability.

[0075] The epoxy resin represented by Formula 1 can be prepared, for example, by referring to the preparation method of the epoxy resin of Formula 1.

[0076] In an embodiment, the epoxy resin of the epoxy resin composition can consist only of the epoxy resin represented by Formula 1. In an embodiment, based on the total weight of the epoxy resin contained in the epoxy resin composition, the epoxy resin represented by Formula 1 can be present in an amount of 100% by weight.

[0077] In an embodiment, the epoxy resin composition may further include an epoxy resin other than the epoxy resin represented by Formula 1 without affecting the desired effects described herein. For convenience of description, the epoxy resin represented by Formula 1 will be referred to as the first epoxy resin, and the epoxy resin other than the epoxy resin represented by Formula 1 will be referred to as the second epoxy resin.

[0078] The second epoxy resin may be an epoxy resin containing at least two epoxy groups per molecule, and may include, for example, 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, cycloaliphatic epoxy resin, heterocyclic epoxy resin, spiro epoxy resin, cyclohexanedimethanol epoxy resin, trimethylol epoxy resin, halogenated epoxy resin or the like. As the second epoxy resin, these epoxy resins may be used alone or as a mixture thereof.

[0079] Based on the total weight of the epoxy resin composition, the epoxy resin may be present in an amount of 2% to 17% by weight (for example, 2% to 10% by weight). Within these ranges, the composition can avoid a reduction in curability.

[0080] Curing agent

[0081] The curing agent may include: polyphenol compounds, such as polyfunctional phenolic resins, phenol aralkyl phenolic resins, phenol novolac phenolic resins, xylok phenolic resins, cresol novolac phenolic resins, naphthol phenolic resins, terpene phenolic resins, dicyclopentadiene phenolic resins, novolac phenolic resins synthesized from bisphenol A and resol, tris(hydroxyphenyl)methane or dihydroxybiphenyl; acid anhydrides, such as maleic anhydride or phthalic anhydride; or aromatic amines, such as m-phenylenediamine, diaminodiphenylmethane or diaminodiphenylsulfone. Preferably, the curing agent may be a xylok phenolic resin or a phenol aralkyl phenolic resin.

[0082] Based on the total weight of the epoxy resin composition, the curing agent may be present in an amount of 0.5% to 13% by weight. Within this range, the composition can avoid a reduction in curability.

[0083] Inorganic filler

[0084] Inorganic fillers can be used to help improve the mechanical properties of epoxy resin compositions while ensuring low stress in the epoxy resin compositions. In an embodiment, the inorganic fillers can help increase the thermal conductivity and heat dissipation ability of the epoxy resin compositions, can help improve the fluidity of the epoxy resin compositions, and can help reduce the thermal expansion and moisture absorption of the epoxy resin compositions.

[0085] The inorganic fillers can include, for example, fused silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium dioxide, antimony oxide, or glass fiber.

[0086] In an embodiment, the inorganic fillers can include alumina. The alumina can have a thermal conductivity of about 25 W / m·K to 30 W / m·K and can effectively increase the thermal conductivity of the composition.

[0087] The alumina can have a spherical or non-spherical shape. If the alumina has a spherical shape, the composition can have improved fluidity. The alumina can have an average particle size (D50) of 0.5 μm to 50 μm, for example 0.5 μm to 30 μm. Within these ranges, the composition can have good performance in terms of fluidity and thermal conductivity. In an embodiment, the alumina can include, for example, a mixture of two aluminas having different average particle sizes (D50). In an embodiment, the alumina can be a mixture in which a first alumina and a second alumina are present in a weight ratio of 1:1 to 10:1, where the first alumina can have a larger average particle size (D50) than the second alumina. As needed, the alumina can be coated with an epoxy resin or a curing agent before being incorporated into the composition.

[0088] The content of the inorganic fillers in the composition can vary according to the desired properties of the composition, such as thermal conductivity, moldability, reduction of internal stress, and high-temperature strength. In an embodiment, based on the total weight of the epoxy resin composition, the inorganic fillers can be present in an amount of 50 wt% to 95 wt%, for example 70 wt% to 95 wt% or 85 wt% to 95 wt%. Within these ranges, the epoxy resin composition can have good performance in terms of flame retardancy, fluidity, and reliability.

[0089] Curing catalyst

[0090] The curing catalyst can be, for example, a tertiary amine compound, an organometallic compound, an organophosphorus compound, an imidazole compound or a boron compound. The tertiary amine compound can include, for example, benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tris(dimethylaminomethyl)phenol, 2,2-(dimethylaminomethyl)phenol, 2,4,6-tris(diaminomethyl)phenol, tris-2-ethylhexanoate or the like. The organometallic compound can include, for example, chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate or the like. The organophosphorus compound can include, for example, triphenylphosphine, tris(4-methoxy)phosphine, triphenylphosphine-triphenylborane or triphenylphosphine-1,4-benzoquinone adduct or the like. The imidazole compound can include, for example, 2-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, 2-methyl-1-vinylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole or the like. The boron compound can include, for example, triphenylphosphonium tetraphenylborate, tetraphenylborate salt, trifluoroborane-n-hexylamine, trifluoroborane monoethylamine, tetrafluoroborate triethylamine, tetrafluoroborate amine or the like. In an embodiment, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or phenol novolak resin salt can be used as the curing catalyst.

[0091] The curing catalyst can be used in the form of an adduct prepared by pre-reacting the curing catalyst with an epoxy resin or a curing agent.

[0092] Based on the total weight of the epoxy resin composition, the curing catalyst can be present in an amount of 0.01 wt% to 5 wt%. Within this range, the curing catalyst can promote the curing of the composition without sacrificing the fluidity of the composition.

[0093] The epoxy resin composition can further include additives used in some epoxy resin compositions for encapsulating semiconductor devices. In an embodiment, the additives can include, for example, a coupling agent, a release agent, a colorant, a stress relaxant, a crosslinking enhancer or a leveling agent.

[0094] The coupling agent can increase the interfacial strength between the epoxy resin and the inorganic filler by reacting with the epoxy resin and the inorganic filler, and the coupling agent can be, for example, a silane coupling agent. The silane coupling agent can include any silane coupling agent that can help increase the interfacial strength between the epoxy resin and the inorganic filler by reacting with the epoxy resin and the inorganic filler. The silane coupling agent can include, for example, epoxy silane, amino silane, urea silane, mercapto silane, alkyl silane or the like. These can be used alone or in combination. Based on the total weight of the epoxy resin composition for encapsulating semiconductor devices, the coupling agent can be present in an amount of 0.01 wt% to 5 wt%, for example 0.05 wt% to 3 wt%. Within this range, the cured product of the epoxy resin composition can have enhanced strength.

[0095] The mold release agent may include, for example, paraffin wax, ester wax, higher fatty acid, metal salts of higher fatty acid, natural fatty acid or metal salts of natural fatty acid. Based on the total weight of the epoxy resin composition, the mold release agent may be present in an amount of 0.1% by weight to 1% by weight.

[0096] The colorant may include, for example, carbon black. Based on the total weight of the epoxy resin composition, the colorant may be present in an amount of 0.1% by weight to 1% by weight.

[0097] The stress relaxant may include, for example, modified silicone oil, silicone elastomer, silicone powder or silicone resin. Based on the total weight of the epoxy resin composition, the stress relaxant may be present in an amount of 2% by weight or less than 2% by weight (0% by weight to 2% by weight), for example 1% by weight or less than 1% by weight (0% by weight to 1% by weight) or 0.1% by weight to 1% by weight.

[0098] Based on the total weight of the epoxy resin composition, the additive may be present in an amount of 0.1% by weight to 5% by weight, for example 0.1% by weight to 3% by weight.

[0099] The epoxy resin composition may be prepared by the following process: uniformly mixing the above components in a Henschel mixer or Lodige mixer, subsequently melt-kneading in a roll press or kneader at a temperature of 90 °C to 120 °C, and then cooling and pulverizing the resulting product.

[0100] A semiconductor device according to some embodiments may be encapsulated using the epoxy resin composition for encapsulating a semiconductor device according to some embodiments. The semiconductor device may be encapsulated with the epoxy resin composition by any suitable method known in the art, such as transfer molding, injection molding, casting, and compression molding. In an embodiment, the semiconductor device may be encapsulated with the epoxy resin composition by low-pressure transfer molding. In another embodiment, the semiconductor device may be encapsulated with the epoxy resin composition by compression molding.

[0101] The following examples and comparative examples are provided to highlight the features of one or more embodiments, but it should be understood that these examples and comparative examples should not be construed as limiting the scope of the embodiments, nor should the comparative examples be construed as exceeding the scope of the embodiments. In addition, it should be understood that the embodiments are not limited to the specific details described in the examples and comparative examples.

[0102] Preparation Example: Preparation and Analysis of Epoxy Resin

[0103] Epoxy resins represented by Formulas 1-1, 1-2, 1-3, 1-4, and 1-5 were prepared as follows:

[0104] [Formula 1-1] (1,4-bis(4-(oxiran-2-ylmethoxy)phenyl)buta-1,3-diyne)

[0105]

[0106] In a 1000 mL reactor, 500 mL of dimethylformamide as a solvent, 4-iodophenol (30 g, 136.2 mmol), propargylic acid (18.5 mL, 300 mmol), and Et3N (70 mL) were placed, as well as PdCl2(PPh3)2 (5 g, 7.1 mmol), CuI (1.7 g, 9.0 mmol), and Ag2CO3 (83 g, 300 mmol) as catalysts. Subsequently, the reaction was carried out at 130 °C for 24 hours, then the solvent was dried, and then the reaction product was purified by a silica gel column. The solvent used for purification by the silica gel column was a mixture of ethyl acetate and hexane (1:6). After purification by the silica gel column, 17 g of a bright yellow compound powder obtained after removing the solvent under reduced pressure was placed in a 500 mL reactor together with benzyltrimethylammonium bromide (5.0 g, 21.7 mmol) and an excess of epichlorohydrin (300 mL). Subsequently, the reaction was carried out at 110 °C for 1 hour, then NaOH (6 g, 145.0 mmol) was added, and then the reaction was carried out for 2 hours. After the reaction was completed, the solvent was removed under reduced pressure, and then the reaction product was purified with deionized water to obtain 21 g of a bright yellow powder of the compound represented by Formula 1-1 in a yield of 42%. The powder was confirmed to be the compound represented by Formula 1-1 by NMR, LC-MS, and elemental analysis. 1 H NMR (400 MHz, CDCl3) 7.53 (m, 2H), 7.01 (m, 4H), 4.40 (m, 2H), 3.88, (m, 2H), 3.33 (m, 2H), 2.85 (m, 2H), 2.71 (m, 2H)) ppm; 13 C NMR (100 MHz, CDCl3) 159.1, 133.9, 114.9, 112.6, 81.3, 72.6, 69.9, 49.9, 43.3 ppm; LC-MS m / z = 346 (M + ); Elemental analysis calculated values for C 22 H 18 O4: C, 76.29; H, 5.24; Found: C, 76.54; H, 5.39.

[0107] [Formula 1-2] (2-((3-methyl-4-(4-(2-methyl-4-(oxiran-2-ylmethoxy)phenyl)buta-1,3-diyne)phenyl)oxy)methyl)oxirane)

[0108]

[0109] In a 1000 mL reactor, 500 mL of dimethylformamide as a solvent, 4-iodo-3-methylphenol (32 g, 136.2 mmol), propiolic acid (18.5 mL, 300 mmol), Et3N (70 mL), and PdCl2(PPh3)2 (5 g, 7.1 mmol), CuI (1.7 g, 9.0 mmol), and Ag2CO3 (83 g, 300 mmol) as catalysts were placed. Subsequently, the reaction was carried out at 130 °C for 24 hours, then the solvent was dried, and then the reaction product was purified by a silica gel column. The solvent used for purification by the silica gel column was a mixture of ethyl acetate and hexane (1:6). After purification by the silica gel column, 18 g of a bright yellow compound powder obtained after removing the solvent under reduced pressure was placed in a 500 mL reactor together with benzyltrimethylammonium bromide (5.0 g, 21.7 mmol) and an excess of epichlorohydrin (300 mL). Subsequently, the reaction was carried out at 110 °C for 1 hour, then NaOH (6 g, 145.0 mmol) was added, and then the reaction was carried out for 2 hours. After the reaction was completed, the solvent was removed under reduced pressure, and then the reaction product was purified with deionized water to obtain 20 g of a bright yellow powder of the compound represented by Formula 1-2 in a 40% yield. The powder was confirmed to be the compound represented by Formula 1-2 by NMR, LC-MS, and elemental analysis. 1 1H NMR (400 MHz, CDCl3) 7.19 (m, 2H), 6.57 - 6.54 (m, 4H), 4.20 (m, 2H), 3.95, (m, 2H), 3.05 (m, 2H), 2.63 (m, 2H), 2.35 (m, 2H), 2.33 (s, 6H) ppm; 13 13C NMR (100 MHz, CDCl3) 157.1, 142.8, 132.8, 115.2, 112.8, 111.0, 77.0, 74.7, 69.5, 50.0, 44.2, 17.2 ppm; LC-MS m / z = 374 (M + +); Elemental analysis calculated for C 24 H 22 O4: C, 76.99; H, 5.92; Found: C, 76.89; H, 5.74.

[0110] [Formula 1-3] (2-((4-(4-(2,6-dimethyl-4-(oxiran-2-ylmethoxy)phenyl)but-1,3-diyne-1-yl)-3,5-dimethylphenoxy)methyl)oxirane)

[0111]

[0112] In a 1,000 mL reactor, 500 mL of dimethylformamide as a solvent, 4-iodo-3,5-dimethylphenol (34 g, 136.2 mmol), propiolic acid (18.5 mL, 300 mmol), Et3N (70 mL), and PdCl2(PPh3)2 (5 g, 7.1 mmol), CuI (1.7 g, 9.0 mmol), and Ag2CO3 (83 g, 300 mmol) as catalysts were placed. Subsequently, the reaction was carried out at 130 °C for 24 hours, then the solvent was dried, and then the reaction product was purified by a silica gel column. The solvent used for purification by the silica gel column was a mixture of ethyl acetate and hexane (1:6). After purification by the silica gel column, 18 g of a bright yellow compound powder obtained after removing the solvent under reduced pressure was placed in a 500 mL reactor together with benzyltrimethylammonium bromide (5.0 g, 21.7 mmol) and an excess of epichlorohydrin (300 mL). Subsequently, the reaction was carried out at 110 °C for 1 hour, then NaOH (6 g, 145.0 mmol) was added, and then the reaction was carried out for 2 hours. After the reaction was completed, the solvent was removed under reduced pressure, and then the reaction product was purified with deionized water to obtain 20 g of a bright yellow powder of the compound represented by Formula 1-3 in a yield of 39%. The powder was confirmed to be the compound represented by Formula 1-3 by NMR, LC-MS, and elemental analysis. 1 H NMR (400 MHz, CDCl3) 6.35 (m, 4H), 4.20 (m, 2H), 3.95, (m, 2H), 3.05 (m, 2H), 2.63 (m, 2H), 2.38 (m, 2H), 2.35 (s, 12H) ppm; 13 C NMR (100 MHz, CDCl3) 157.1, 142.5, 113.2, 110.1, 109.9, 77.0, 74.7, 69.5, 50.0, 44.2, 17.4 ppm; LC-MS m / z = 402 (M + );Elemental analysis calculated for C 26 H 26 O4: C, 77.59; H, 6.51; Found: C, 77.81; H, 6.58.

[0113] [Formula 1-4] (2-((3-methoxy-4-(4-(2-methoxy-4-(oxiran-2-ylmethoxy)phenyl)but-1,3-diynyl)phenoxy)methyl)oxirane)

[0114]

[0115] In a 1,000 mL reactor, 500 mL of dimethylformamide as a solvent, 4-iodo-3-methoxyphenol (34 g, 136.2 mmol), propiolic acid (18.5 mL, 300 mmol), Et3N (70 mL), and PdCl2(PPh3)2 (5 g, 7.1 mmol), CuI (1.7 g, 9.0 mmol), and Ag2CO3 (83 g, 300 mmol) as catalysts were placed. Subsequently, the reaction was carried out at 130 °C for 24 hours, then the solvent was dried, and the reaction product was purified by a silica gel column. The solvent used for purification by the silica gel column was a mixture of ethyl acetate and hexane (1:6). After purification by the silica gel column, 18 g of a bright yellow compound powder obtained after removing the solvent under reduced pressure was placed in a 500 mL reactor together with benzyltrimethylammonium bromide (5.0 g, 21.7 mmol) and an excess of epichlorohydrin (300 mL). Subsequently, the reaction was carried out at 110 °C for 1 hour, then NaOH (6 g, 145.0 mmol) was added, and the reaction was continued for 2 hours. After the reaction was completed, the solvent was removed under reduced pressure, and the reaction product was purified with deionized water to obtain 20 g of a bright yellow powder of the compound represented by Formula 1-4 in a yield of 38%. The powder was confirmed to be the compound represented by Formula 1-4 by NMR, LC-MS, and elemental analysis. 1 H NMR (400 MHz, CDCl3) 7.20 (s, 2H), 6.32 - 6.25 (m, 4H), 4.20 (m, 2H), 3.95, (m, 2H), 3.73 (s, 6H), 3.05 (m, 2H), 2.63 (m, 2H), 2.35 (m, 2H) ppm; 13 C NMR (100 MHz, CDCl3) 164.01, 158.1, 142.8, 133.9, 133.8, 106.3, 1.6.2, 103.5, 100.1, 100.0, 77.0, 74.7, 69.5, 55.3, 50.0, 44.2 ppm; LC-MS m / z = 408 (M + );Elemental analysis calculated for C 24 H 22 O6: C, 70.92; H, 5.46; Found: C, 70.91; H, 5.71.

[0116] [Formula 1-5] (2 - ((4-(4-(2,6-diethyl-4-(oxiran-2-ylmethoxy)phenyl)but-1,3-diyne-1-yl)-3,5-diethylphenoxy)methyl)oxirane)

[0117]

[0118] In a 1,000 mL reactor, 500 mL of dimethylformamide as a solvent, 3,5 - diethyl - 4 - iodophenol (38 g, 136.2 mmol), propiolic acid (18.5 mL, 300 mmol), Et3N (70 mL), and PdCl2(PPh3)2 (5 g, 7.1 mmol), CuI (1.7 g, 9.0 mmol), and Ag2CO3 (83 g, 300 mmol) as catalysts were placed. Subsequently, the reaction was carried out at 130 °C for 24 hours, then the solvent was dried, and the reaction product was purified by a silica gel column. The solvent used for purification by the silica gel column was a mixture of ethyl acetate and hexane (1:6). After purification by the silica gel column, 18 g of a bright yellow compound powder obtained after removing the solvent under reduced pressure was placed in a 500 mL reactor together with benzyltrimethylammonium bromide (5.0 g, 21.7 mmol) and an excess of epichlorohydrin (300 mL). Subsequently, the reaction was carried out at 110 °C for 1 hour, then NaOH (6 g, 145.0 mmol) was added, and the reaction was continued for 2 hours. After the reaction was completed, the solvent was removed under reduced pressure, and the reaction product was purified with deionized water to obtain 19 g of a bright yellow powder of the compound represented by Formula 1 - 5 in a yield of 35%. The powder was confirmed to be the compound represented by Formula 1 - 5 by NMR, LC - MS, and elemental analysis. 1 H NMR(400MHz,CDCl3)6.42(s,4H),4.20(m,2H),3.95,(m,2H),3.05(m,2H),2.63 - 2.52(m,10H),2.38(m,2H),1.24(m,12H)ppm; 13 CNMR(100MHz,CDCl3)157.1,148.6,148.5,111.1,111.0,109.0,108.9,77.0,74.7,69.5,50.0,44.2,25.6,25.4,14.0ppm;LC - MS m / z=458(M + );Elemental analysis calculated for C 30 H 34 O4:C,78.57;H,7.47;Found:C,78.19;H,7.58.

[0119] Details of the components used in the examples and comparative examples are as follows:

[0120] (A) Epoxy resin

[0121] (A1) Epoxy resins of Preparation Examples (A1 - 1 (Formula 1 - 1), A1 - 2 (Formula 1 - 2), A1 - 3 (Formula 1 - 3), A1 - 4 (Formula 1 - 4), A1 - 5 (Formula 1 - 5))

[0122] (A2) Phenolic aralkyl epoxy resin (NC-3000, Nippon Kayaku Co., Ltd.)

[0123] (A3) An epoxy resin represented by the following formula:

[0124]

[0125] (B) Curing agent

[0126] (B1) KPH-F3065 (siloxylated phenolic resin, Kolon Chemical Co., Ltd.)

[0127] (B2) MEH-7851 (phenolic aralkyl phenolic resin, Meiwafosis Co., Ltd.)

[0128] (C) Curing catalyst: triphenylphosphine (Hokko Chemical Industry Co., Ltd.)

[0129] (D) Inorganic filler: a mixture of spherical fused alumina with an average particle size (D 50 ) of 20 μm and spherical fused alumina with an average particle size (D 50 ) of 0.5 μm (weight ratio: 9:1)

[0130] (E) Coupling agent

[0131] (E1) Methyltrimethoxysilane (SZ-6070, Dow Corning Corporation)

[0132] (E2) KBM-573 (N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.)

[0133] (F) Carbon black (MA-600B, Mitsubishi Chemical Corporation)

[0134] Examples 1 to 6 and Comparative Examples 1 to 4

[0135] The above components were uniformly mixed in a Henschel mixer (KS M-22, KEUM SUNGMACHINERY Co., Ltd.) at 25°C to 30°C for 30 minutes in the amounts (unit: parts by weight) shown in Table 1, and then melt-kneaded in a continuous kneader at a maximum temperature of 110°C for 30 minutes, followed by cooling to 10°C to 15°C and pulverization to prepare an epoxy resin composition for encapsulating semiconductor devices. In Table 1, "-" indicates that the corresponding component was not used.

[0136] Each of the epoxy resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 was evaluated for the following properties. The results are shown in Table 1.

[0137] (1) Fluidity (unit: inch, spiral flow length): Using a low-pressure transfer molding machine, each of the prepared epoxy resin compositions was injected into a mold for measuring fluidity under the conditions of a mold temperature of 175 °C, a load of 70 kgf / cm 2 , an injection pressure of 9 MPa, and a curing time of 90 seconds, carried out in accordance with EMMI-1-66, and then the flow length was measured. A longer flow length indicates better fluidity.

[0138] (2) Thermal conductivity (unit: W / m·K): Samples were prepared from each of the prepared epoxy resin compositions in accordance with ASTM D5470, and then the thermal conductivity of the samples was measured at 25 °C.

[0139] Table 1

[0140]

[0141] As can be seen from Table 1, the epoxy resin compositions of Examples 1 to 6 according to some embodiments exhibited good moldability due to high fluidity. In addition, the epoxy resin compositions of Examples 1 to 6 exhibited good heat dissipation ability due to high thermal conductivity, and thus were confirmed to effectively maintain the surface temperature of the semiconductor device at a low level during the operation of the semiconductor device.

[0142] In contrast, the compositions of Comparative Examples 1 to 4 that did not contain the epoxy resin represented by Formula 1 exhibited poor heat dissipation ability due to low thermal conductivity or poor moldability due to low fluidity.

[0143] One or more embodiments can provide an epoxy resin composition for encapsulating a semiconductor device, which may include an epoxy resin having better performance than other epoxy resins in terms of thermal conductivity and fluidity to ensure high thermal conductivity and improved heat dissipation ability, thereby suppressing heat-induced failures or malfunctions of the semiconductor package.

[0144] Some semiconductor packages may use spherical alumina (aluminum oxide). Alumina may have a thermal conductivity of about 25 W / m·K to about 30 W / m·K. However, since the epoxy resin contained in the epoxy resin composition for encapsulating a semiconductor device may have a very low thermal conductivity of 0.2 W / m·K, there may be limitations in increasing the thermal conductivity of the encapsulation layer formed from the composition to 6 W / m·K or higher even when using alumina. In addition, although copper, aluminum, or silver particles have high thermal conductivity, they may have poor insulation properties, while although aluminum nitride, boron nitride, or silicon carbide fillers have relatively good insulation properties, they may not be able to ensure a high filler loading rate due to their poor fluidity. Although many attempts have been made in recent years to increase the thermal conductivity of epoxy resins, the commercialization of semiconductor materials encapsulated with compression-insulating thermosetting resins has not been achieved.

[0145] On the other hand, according to some embodiments, a semiconductor device may be provided.

[0146] The semiconductor device may be encapsulated using the above-described epoxy resin composition for encapsulating a semiconductor device.

[0147] Some embodiments may provide an epoxy resin composition for encapsulating a semiconductor device, which may have significantly improved heat dissipation ability due to high thermal conductivity while exhibiting improved fluidity.

[0148] Exemplary embodiments have been disclosed herein. Although specific terms are used, they are used and interpreted in a general and descriptive sense only and not for purposes of limitation. In some cases, as will be apparent to those of ordinary skill in the art as of the filing of the present application, features, characteristics, and / or elements associated with a particular embodiment may be used alone or in combination with features, characteristics, and / or elements associated with other embodiments, unless otherwise expressly stated. Accordingly, those skilled in the art will understand that various changes in form and detail may be made without departing from the spirit and scope of the invention as set forth in the claims above.

Claims

1. An epoxy resin composition for encapsulating a semiconductor device, the epoxy resin composition comprising: Epoxy resin; Curing agent; Inorganic filler; And Curing catalyst, Wherein: The epoxy resin comprises a compound represented by Formula 1: [Formula 1] R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 and R 10 each independently represents hydrogen, a substituted or unsubstituted C1 to C 20 alkyl group, a substituted or unsubstituted C1 to C 20 alkoxy group, a hydroxyl group, an amino group, a nitro group, a cyano group, a substituted or unsubstituted C1 to C 20 alkenyl group, a substituted or unsubstituted C1 to C 20 haloalkyl group, a substituted or unsubstituted C6 to C 30 aryl group, a substituted or unsubstituted C3 to C 30 heteroaryl group, a substituted or unsubstituted C3 to C 10 cycloalkyl group, a substituted or unsubstituted C3 to C 10 heterocycloalkyl group, a substituted or unsubstituted C7 to C 30 aralkyl group, a substituted or unsubstituted C1 to C 30 heteroalkyl group or a group represented by Formula 2: [Formula 2] * is the bonding site with the element, R 1 、R 2 、R 3 、R 4 and R 5 at least one of which is a group represented by Formula 2, and R 6 、R 7 、R 8 、R 9 and R 10 At least one of them is a group represented by Formula 2.

2. The epoxy resin composition according to claim 1, wherein in Formula 1: R 3 is a group represented by Formula 2 and R 1 , R 2 , R 4 and R 5 are each independently hydrogen, a substituted or unsubstituted C1 to C 20 alkyl or a substituted or unsubstituted C1 to C 20 alkoxy, and R 8 is a group represented by Formula 2 and R 6 , R 7 , R 9 and R 10 are each independently hydrogen, a substituted or unsubstituted C1 to C 20 alkyl or a substituted or unsubstituted C1 to C 20 alkoxy.

3. The epoxy resin composition according to claim 1, wherein the compound represented by Formula 1 comprises a compound represented by Formula 1-1, a compound represented by Formula 1-2, a compound represented by Formula 1-3, a compound represented by Formula 1-4 or a compound represented by Formula 1-5: [Formula 1-1] [Formula 1-2] [Formula 1-3] [Formula 1-4] [Formula 1-5] 4. The epoxy resin composition according to claim 1, wherein based on the total weight of the epoxy resin composition, the compound represented by Formula 1 is present in an amount of 0.1% by weight to 17% by weight.

5. The epoxy resin composition according to claim 1, wherein the inorganic filler comprises alumina.

6. The epoxy resin composition according to claim 1, wherein based on the total weight of the epoxy resin composition, the epoxy resin comprises: 2% by weight to 17% by weight of the epoxy resin; 0.5% by weight to 13% by weight of the curing agent; 50% by weight to 95% by weight of the inorganic filler; And 0.01% by weight to 5% by weight of the curing catalyst.

7. A semiconductor device encapsulated with the epoxy resin composition according to claim 1.

8. The semiconductor device according to claim 7, wherein in Formula 1: R 3 is a group represented by Formula 2 and R 1 , R 2 , R 4 and R 5 are each independently hydrogen, a substituted or unsubstituted C1 to C 20 alkyl or a substituted or unsubstituted C1 to C 20 alkoxy, and R 8 is a group represented by Formula 2 and R 6 , R 7 , R 9 and R 10 are each independently hydrogen, substituted or unsubstituted C1 to C 20 alkyl or substituted or unsubstituted C1 to C 20 alkoxy.

9. The semiconductor device according to claim 7, wherein the compound represented by Formula 1 comprises a compound represented by Formula 1-1, a compound represented by Formula 1-2, a compound represented by Formula 1-3, a compound represented by Formula 1-4 or a compound represented by Formula 1-5: [Formula 1-1] [Formula 1-2] [Formula 1-3] [Formula 1-4] [Formula 1-5] 10. The semiconductor device according to claim 7, wherein based on the total weight of the epoxy resin composition, the compound represented by Formula 1 is present in an amount of 0.1% by weight to 17% by weight.

11. The semiconductor device according to claim 7, wherein the inorganic filler comprises alumina.

12. The semiconductor device according to claim 7, wherein based on the total weight of the epoxy resin composition, the epoxy resin comprises: 2% by weight to 17% by weight of the epoxy resin; 0.5% by weight to 13% by weight of the curing agent; 50% by weight to 95% by weight of the inorganic filler; And 0.01% by weight to 5% by weight of the curing catalyst.

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