Thermoplastic resin composition for sealing semiconductor device and semiconductor device sealed using the same
阅读说明：本技术 用于密封半导体设备的热塑性树脂组合物及使用其密封的半导体设备 (Thermoplastic resin composition for sealing semiconductor device and semiconductor device sealed using the same ) 是由 韩承 金民兼 于 2018-09-13 设计创作，主要内容包括：本发明涉及用于密封半导体设备的热塑性树脂组合物,该组合物包含马来酰亚胺化合物、苯并噁嗪化合物、化学式4的化合物和无机填料,以及涉及使用该热塑性树脂组合物密封的半导体设备。(The present invention relates to a thermoplastic resin composition for sealing a semiconductor device, the composition comprising a maleimide compound, a benzoxazine compound, a compound of chemical formula 4, and an inorganic filler, and a semiconductor device sealed using the same.)
1. A thermosetting resin composition for encapsulating a semiconductor device, comprising: a maleimide compound, a benzoxazine compound, a compound of formula 4, and an inorganic filler,
< formula 4>
(in formula 4R4、R5、R6And R7Each independently is substituted or unsubstituted C1To C30Aliphatic hydrocarbon group, substituted or unsubstituted C6To C30Aromatic hydrocarbon radical, substituted or unsubstituted C containing hetero atoms1To C30Aliphatic hydrocarbon group, or C containing hetero atom and substituted or unsubstituted1To C30An aromatic hydrocarbon group;
w and Z are each independently substituted or unsubstituted C1To C30Aliphatic hydrocarbon group, substituted or unsubstituted C6To C30Aromatic hydrocarbon radical, substituted or unsubstituted C containing hetero atoms1To C30Aliphatic hydrocarbon group, or C containing hetero atom and substituted or unsubstituted1To C30An aromatic hydrocarbon group;
l is an integer of 0 to 4;
m is an integer of 1 to 6; and is
n is an integer of 1 to 5).
2. The thermosetting resin composition of claim 1, wherein in said thermosetting resin composition, said composition of formula 4 is present in an amount of about 0.01 wt% to about 5 wt%.
3. The thermosetting resin composition of claim 1, wherein the composition of formula 4 comprises at least one of the compounds represented by formulae 4-1 to 4-6:
< formula 4-1>
< formula 4-2>
< formulas 4 to 3>
< formulas 4 to 4>
< formulas 4 to 5>
< formulas 4 to 6>
4. The thermosetting resin composition according to claim 1, wherein the maleimide compound comprises a maleimide compound represented by formula 1,
< formula 1>
(in formula 1, n1Is an integer from 0 to 10;
X1each independently is C1To C10Alkylene, a group represented by formula A, -SO2-, -CO-, an oxygen atom or a single bond,
< formula A >
(in the formula A, Y is C having an aromatic ring6To C30A hydrocarbon radical, and n2An integer of 0 or more),
R1each independently is C1To C6A hydrocarbyl group;
a is each independently an integer of 0 to 4; and is
Each b is independently an integer of 0 to 3).
5. The thermosetting resin composition according to claim 1, wherein the benzoxazine compound comprises at least one or two compounds selected from the group of a compound represented by formula 2, a compound represented by formula 3A, and a compound represented by formula 3B,
< formula 2>
(in the formula 2, the first reaction solution,
X2is C1To C10Alkylene, a group represented by formula A, -SO2-, -CO-, oxy-, single bond or C having an aromatic ring6To C30A hydrocarbyl group;
R2each independently is C1To C6A hydrocarbyl group; and is
c are each independently an integer of 0 to 4)
< formula 3A >
< formula 3B >
(in the formulae 3A and 3B,
X3is C1To C10Alkylene, a group represented by formula A, -SO2-, -CO-, oxy-, single bond or C having an aromatic ring6To C30A hydrocarbyl group;
R3each independently is C1To C6A hydrocarbyl group; and is
d is each independently an integer of 0 to 5).
6. The thermosetting resin composition of claim 1, comprising: about 1 wt% to about 25 wt% of the maleimide compound, about 0.1 wt% to about 10 wt% of the benzoxazine compound, about 0.01 wt% to about 5 wt% of the composition of formula 4, and about 70 wt% to about 95 wt% of the inorganic filler.
7. The thermosetting resin composition of claim 1, further comprising: and (3) epoxy resin.
8. The thermosetting resin composition of claim 7, wherein the epoxy resin is present in the thermosetting resin composition in an amount of about 0.5 wt% to about 10 wt%.
9. A semiconductor device encapsulated with the thermosetting resin composition according to any one of claims 1 to 8.
Technical Field
The present invention relates to a thermosetting resin composition for encapsulating a semiconductor device and a semiconductor device encapsulated using the thermosetting resin composition. More particularly, the present invention relates to a thermosetting resin composition for encapsulating semiconductor devices, which has good properties in terms of curability, flowability and storage stability, and a semiconductor device encapsulated using the same.
Background
In recent years, conversion of the chip specification of a package for a power device from a Si chip to a SiC chip has been studied. Since a semiconductor device for a power device using a SiC chip can stably operate under a high temperature condition of 200 ℃ or more, a material for packaging the semiconductor device is also required to have high heat resistance at a temperature of 200 ℃ or more. Although a resin composition mainly composed of an epoxy resin and a phenol curing agent is generally used as a typical encapsulating material for semiconductor devices, the glass transition temperature of the typical encapsulating material is as high as about 230 ℃, and heat resistance of the encapsulation currently used for power devices cannot be satisfied. In order to satisfy heat resistance of packages for power devices, research and commercialization of a combination of a maleimide compound and a benzoxazine compound or a combination of a maleimide compound, a benzoxazine compound and an epoxy resin have been actively conducted. The cured product of the thermosetting resin composition for encapsulating semiconductor devices has various advantages such as high glass transition temperature, high heat resistance, good electrical and flame retardant properties, low thermal decomposition, low curing shrinkage and low coefficient of thermal expansion. However, since the reactivity of the thermosetting resin composition is much slower than that of the combination of the epoxy resin and the phenol curing agent, the thermosetting resin composition is required to be sufficiently cured even in a short curing time to ensure the rapid curing property of the encapsulating material for semiconductor devices.
Disclosure of Invention
Technical problem
An object of the present invention is to provide a thermosetting resin composition for encapsulating semiconductor devices, which has good properties in terms of curability, flowability and storage stability.
It is another object of the present invention to provide a semiconductor device encapsulated with the above thermosetting resin composition.
Technical scheme
According to one aspect of the present invention, a thermosetting resin composition for encapsulating a semiconductor device includes: a maleimide compound, a benzoxazine compound, a compound represented by formula 4, and an inorganic filler.
< formula 4>
(wherein R is4、R5、R6、R7W, Z, l, m and n are the same as defined in the detailed description).
According to another aspect of the present invention, there is provided a semiconductor device encapsulated with the thermosetting resin composition for encapsulating a semiconductor device according to the present invention.
Advantageous effects
The present invention provides a thermosetting resin composition for encapsulating semiconductor devices, which has good properties in terms of curability, flowability and storage stability.
The present invention provides a semiconductor device encapsulated with the above thermosetting resin composition.
Best mode
In the transfer molding method, it is desirable that the mold curing time of the thermosetting resin composition for encapsulating a semiconductor device is 100 seconds or less. In this case, the thermosetting resin composition has good curing characteristics, and in particular, a cured product of the thermosetting resin composition can be easily obtained by molding the thermosetting resin composition. Therefore, in order to satisfy these characteristics, it is desirable to add a curing catalyst to a combination of a maleimide compound and a benzoxazine compound or to a combination of a maleimide compound, a benzoxazine compound and an epoxy resin. For example, the curing catalyst may include at least one selected from the group consisting of an imidazole-based catalyst, a phosphorus-based catalyst, a boron-based catalyst, a lewis acid, and an acid catalyst. Here, since the thermosetting resin composition has a problem that the reaction speed is very low, an imidazole-based catalyst that promotes a rapid reaction is currently used as the thermosetting resin composition used as the encapsulating material for the semiconductor device. However, the use of an imidazole-based catalyst that promotes a rapid reaction may result in deterioration of storage stability and toughness of the thermosetting resin composition when left at room temperature.
The inventors of the present invention confirmed that a thermosetting resin composition comprising a maleimide compound, a benzoxazine compound, an inorganic filler and a compound represented by formula 4 has good properties in terms of curability, flowability and storage stability, thereby completing the present invention.
Next, the components of the thermosetting resin composition for encapsulating semiconductor devices according to the present invention will be described in detail.
Maleimide compound
The maleimide compound preferably contains at least two maleimide groups therein.
In one embodiment, the maleimide compound may include a maleimide compound represented by formula 1:
< formula 1>
(in the formula 1, the above-mentioned,
n1is an integer from 0 to 10;
X1each independently is C1To C10Alkylene, a group represented by formula A, -SO2-, -CO-, an oxygen atom or a single bond,
< formula A >
(in the formula A, Y is C having an aromatic ring6To C30A hydrocarbon radical, and n2An integer of 0 or more);
R1each independently is C1To C6A hydrocarbyl group;
a is each independently an integer of 0 to 4, and
each b is independently an integer of 0 to 3. )
X1Is C1To C10Alkylene, preferably C1To C7Alkylene, more preferably C1To C3Alkylene groups such as, but not limited to, straight or branched chain alkylene groups. Examples of the linear alkylene group may include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, trimethylene, tetramethylene, pentamethylene, hexamethylene and the like. Examples of branched alkylene groups may include alkylmethylene groups, such as-C (CH)3)2- (isopropylidene), -CH (CH)3)-、-CH(CH2CH3)-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3) -, and-C (CH)2CH3)2-; alkyl ethylene, e.g. -CH (CH)3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-, and-C (CH)2CH3)2-CH2-and the like.
R1Each independently is C1To C6Aliphatic hydrocarbon group, C1Or C2The aliphatic hydrocarbon group, particularly methyl, is preferably ethyl.
Each a is independently an integer of 0 to 4, an integer of 0 to 2, and more preferably 0. In addition, each b is independently an integer of 0 to 3, 0, or 1, more preferably 0.
n1Is an integer of 0 to 10, an integer of 0 to 6, an integer of 0 to 4, particularly preferably an integer of 0 to 3. More preferably, in the maleimide compound represented by formula 1, n1Is an integer of 1 or more.
In formula A, Y is C having an aromatic ring6To C30A hydrocarbon radical, and n2Is 0 or more wholeAnd (4) counting. C having an aromatic ring6To C30The hydrocarbon group may consist of an aromatic ring, or may contain a hydrocarbon group in addition to an aromatic ring. Y may comprise a single aromatic ring or at least two aromatic rings. When Y comprises at least two aromatic rings, these aromatic rings may be the same as or different from each other. Further, the aromatic ring may have one of a monocyclic structure and a polycyclic structure. In particular, C having an aromatic ring6To C30The hydrocarbon group may be a divalent group obtained by removing two hydrogen atoms from the core of a compound having aromatic characteristics, such as benzene, biphenyl, naphthalene, anthracene, fluorene, phenanthrene, indacene, terphenyl, acenaphthylene, phenylene, and the like. In addition, these aromatic hydrocarbon groups may have a substituent. Herein, the aromatic hydrocarbon group having a substituent means an aromatic hydrocarbon group in which a part or all of hydrogen atoms constituting the aromatic hydrocarbon group are substituted with a substituent. The substituent may include, for example, an alkyl group. The alkyl group may be a chain alkyl group. The alkyl group may have 1 to 10 carbon atoms, or 1 to 6 carbon atoms, with 1 to 4 carbon atoms being particularly preferred. Specifically, the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a sec-butyl group, or the like. n is2Is an integer from 0 to 10, from 0 to 6 or from 0 to 4, particularly preferably from 0 to 3.
Y may have a group obtained by removing two hydrogen atoms from benzene or naphthalene, and the group represented by formula a may be a group represented by formula a1 or formula a 2.
< formula A1>
< formula A2>
(in the formulae A1 and A2, R4Each independently is C1To C6And e is each independently an integer of 0 to 4).
In one embodiment, preferably, in the maleimide compound of formula 1，X1Is C1To C3Straight-chain or branched alkylene, R1Is C1Or C2A is an integer of 0 to 2, b is 0 or 1, and n1Is an integer of 0 to 4.
The maleimide compound of formula 1 may include a maleimide compound represented by formula 1-1.
< formula 1-1>
(in the formula 1-1, n1Is an integer of 0 to 10).
The maleimide compound according to the present invention may include a maleimide compound of a different kind from that of formula 1.
In one embodiment, the maleimide compound may include, for example, a compound having two maleimide groups therein, such as 4,4' -diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2-bis [4- (4- (4-maleimidophenoxy)) phenyl ] propane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4-methyl-1, 3-phenylene bismaleimide, N ' -ethylenebismaleimide, N ' -hexamethylenebismaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethane bismaleimide and bisphenol A diphenyl ether bismaleimide, compounds having three maleimide groups therein, such as polyphenylmethane maleimide and the like.
In another embodiment, the maleimide compounds may include aliphatic maleimide compounds, such as 1,6 '-bismaleimide- (2,2, 4-trimethyl) hexane, hexamethylenediamine bismaleimide, N' -1, 2-ethylenebismaleimide, N '-1, 3-propylenedimaleimide and N, N' -1, 4-tetramethylenebismaleimide; and imide-extended bismaleimides and the like. Of these compounds, 1,6' -bismaleimide- (2,2, 4-trimethyl) hexane and imide-extended bismaleimides are particularly preferred. These maleimide compounds may be used alone or in the form of a mixture thereof.
Preferably, the maleimide compound of formula 1 is used.
The maleimide compound may have a weight average molecular weight (Mw) of about 400 to about 4,000, preferably about 800 to about 2,500. Within this range, the maleimide compound can ensure handling properties and flowability of the resin composition.
The maleimide compound may be prepared by the reaction of a maleimide compound with an amine compound, or may be obtained from a commercially available product.
In the thermosetting resin composition for encapsulating semiconductor devices, the maleimide compound may be present in an amount of about 1 wt% to about 25 wt%, for example about 3 wt% to about 20 wt%. Within this range, the maleimide compound can lower the dielectric constant of the thermosetting resin composition while increasing the glass transition temperature thereof.
Benzoxazine compounds
The benzoxazine compound may include at least one or two compounds selected from the group of the compound represented by formula 2, the compound represented by formula 3A, and the compound represented by formula 3B.
< formula 2>
(in the formula 2, the first reaction solution,
X2is C1To C10Alkylene, a group represented by formula A, -SO2-, -CO-, oxy-, single bond or C having an aromatic ring6To C30A hydrocarbyl group;
R2each independently is C1To C6A hydrocarbyl group; and is
c is each independently an integer of 0 to 4. )
< formula 3A >
< formula 3B >
(in the formulae 3A and 3B,
X3is C1To C10Alkylene, a group represented by formula A, -SO2-, -CO-, oxy-, single bond or C having an aromatic ring6To C30A hydrocarbon group,
R3each independently is C1To C6A hydrocarbon group, and
d is each independently an integer of 0 to 5).
X2And X3Each independently is C1To C10Alkylene, preferably C1To C7Alkylene, more preferably C1To C3Alkylene groups, such as, but not limited to, straight or branched chain alkylene groups. Examples of the linear alkylene group may include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, trimethylene, tetramethylene, pentamethylene, hexamethylene and the like. Examples of branched alkylene groups may include alkylmethylene groups, such as-C (CH)3)2- (isopropylidene), -CH (CH)3)-、-CH(CH2CH3)-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3) -, and-C (CH)2CH3)2-; alkyl ethylene, e.g. -CH (CH)3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-, and-C (CH)2CH3)2-CH2-and the like.
X2And X3May include C having an aromatic ring6To C30Hydrocarbon radicals, e.g. phenyl, biphenyl, fluorene, naphthyl and the like。
Preferably, R2And R3Each independently is C1To C6Aliphatic hydrocarbon group, C1Or C2Aliphatic hydrocarbon groups, in particular methyl or ethyl groups.
c and d are each independently an integer of 0 to 5 or an integer of 0 to 2, more preferably 0.
The benzoxazine compound may include, for example, at least one of compounds represented by formulae 2-1, 2-2 and 2-3 and formulae 3-1, 3-2 and 3-3.
< formula 2-1>
< formula 2-2>
< formulas 2 to 3>
(in the formula 2-3, R is C1To C6Alkyl radical)<Formula 3-1>
< formula 3-2>
< formula 3-3>
The benzoxazine compound may be prepared by typical methods known to those skilled in the art, or may be obtained from commercially available products.
In the thermosetting resin composition, the benzoxazine compound may be present in an amount of about 0.1 wt% to about 10 wt%, for example about 0.5 wt% to about 5 wt%. Within this range, the thermosetting resin composition may have a reduced dielectric constant.
A compound of formula 4
The compound of formula 4 is used to improve the curing degree, storage stability and flowability of a composition comprising a maleimide compound, a benzoxazine compound and an inorganic filler. In addition, the compound of formula 4 is used to improve toughness of a composition comprising a maleimide compound, a benzoxazine compound and an inorganic filler.
< formula 4>
(in the formula 4, the above-mentioned,
R4、R5、R6and R7Each independently is substituted or unsubstituted C1To C30Aliphatic hydrocarbon group, substituted or unsubstituted C6To C30Aromatic hydrocarbon radical, substituted or unsubstituted C containing hetero atoms1To C30Aliphatic hydrocarbon group, or C containing hetero atom and substituted or unsubstituted1To C30An aromatic hydrocarbon group;
w and Z are each independently substituted or unsubstituted C1To C30Aliphatic hydrocarbon group, substituted or unsubstituted C6To C30Aromatic hydrocarbon radical, substituted or unsubstituted C containing hetero atoms1To C30Aliphatic hydrocarbon group, or C containing hetero atom and substituted or unsubstituted1To C30An aromatic hydrocarbon group;
l is an integer of 0 to 4;
m is an integer of 1 to 6; and is
n is an integer of 1 to 5).
Preferably, in formula 4, R4、R5、R6And R7Is unsubstituted or hydroxy-substituted C6To C30And (4) an aryl group. For R in formula 44、R5、R6And R7By "substituted" is meant that at least one hydroxyl group is replaced by C6To C10Aryl, hydroxy, Cyano (CN) or C1To C10Alkyl substitution.
Preferably, in formula 4, W is substituted or unsubstituted C6To C30An aromatic hydrocarbon group. For W in formula 4, "substituted" means that at least one hydroxyl group is replaced with C6To C10Aryl, hydroxy, cyano or C1To C10Alkyl substitution. C6To C30The aromatic hydrocarbon group may be C6To C30Aryl or C6To C30An aryl ketone group. In some embodiments, C6To C30The aromatic hydrocarbon group may be a phenyl group or a benzophenone group.
Preferably, in formula 4, Z is substituted or unsubstituted C6To C30And (4) an aryl group. In some embodiments, C6To C30The aryl group may be phenyl, biphenyl, fluorenyl or bis (phenyl) fluorenyl. For Z in formula 4, "substituted" means that at least one hydroxyl group is replaced with C6To C10Aryl, hydroxy, cyano or C1To C10Alkyl substitution.
In one embodiment, the compound of formula 4 may include at least one compound represented by formulae 4-1 to 4-6:
< formula 4-1>
< formula 4-2>
< formulas 4 to 3>
< formulas 4 to 4>
< formulas 4 to 5>
< formulas 4 to 6>
The compound of formula 4 can be prepared by typical methods known to those skilled in the art.
In the epoxy resin composition, the compound of formula 4 may be present in an amount of about 0.01 wt% to about 5 wt%, for example about 0.02 wt% to about 1.5 wt%, for example about 0.05 wt% to about 1 wt%. Within this range, the compound of formula 4 may improve the curability, storage stability and flowability of the thermosetting resin composition.
Inorganic filler
The inorganic filler is used to improve the mechanical properties and stress release of the composition. The inorganic filler may include typical inorganic fillers used in semiconductor encapsulation materials, and is not limited to a specific kind of inorganic filler. For example, the inorganic filler may include fused silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesium oxide, clay, talc, calcium silicate, titanium oxide, antimony oxide, glass fiber, and the like. These may be used alone or in a mixture thereof.
Preferably, the inorganic filler includes fused silica having a low linear expansion coefficient to reduce stress of the resin composition. Fused silica refers to amorphous silica having an absolute specific gravity of 2.3 or less, and may include amorphous silica prepared by fusing crystalline silica or prepared from various materials. Although the shape and particle size of the fused silica are not particularly limited, the fused silica mixture comprising about 50 to about 99 wt% of spherical fused silica having an average particle size of about 5 to about 30 μm and about 1 to about 50 wt% of spherical fused silica having an average particle size of 0.001 to 1 μm is preferably present in an amount of about 40 to about 100 wt% based on the total weight of the inorganic filler. In addition, the maximum particle diameter of the fused silica may be adjusted to any one of 45 μm, 55 μm and 75 μm according to the intended use of the resin composition. Since spherical fused silica may contain conductive carbon as a foreign substance on the surface thereof, it is important to select a material having less polar foreign substances therein.
The content of the inorganic filler may vary depending on the desired properties of the resin composition, such as moldability, low stress property and high temperature strength. In one embodiment, the inorganic filler may be present in the thermosetting resin composition in an amount of about 70 wt% to about 95 wt%, for example about 75 wt% to about 94 wt%, or about 80 wt% to about 93 wt%. Within this range, the thermosetting resin composition can have good properties in terms of flowability and reliability.
The thermosetting resin composition may further comprise at least one selected from the group consisting of a coupling agent, a mold release agent, a colorant, an antioxidant, a flame retardant, and a stress relief agent.
Coupling agent
The coupling agent reacts with the maleimide compound, the benzoxazine compound and the inorganic filler to enhance the interfacial strength between the maleimide compound, the benzoxazine compound and the inorganic filler, and may include, for example, a silane coupling agent. The silane coupling agent is not particularly limited as long as the silane coupling agent can enhance the interfacial strength between the maleimide compound, the benzoxazine compound and the inorganic filler by reacting with the maleimide compound, the benzoxazine compound and the inorganic filler. Examples of the coupling agent may include epoxy silane, amino silane, ureido silane, mercapto silane, and alkyl silane. These coupling agents may be used alone or in a mixture thereof.
In the thermosetting resin composition, the coupling agent may be present in an amount of about 0.01 wt% to about 5 wt%, preferably about 0.05 wt% to about 3 wt%. Within this range, the coupling agent can improve the strength of the cured product of the thermosetting resin composition.
Release agent
The release agent may include at least one selected from the group consisting of paraffin wax, ester wax, higher fatty acid metal salt, natural fatty acid, and natural fatty acid metal salt.
In the thermosetting resin composition, the release agent may be present in an amount of about 0.1 wt% to about 1 wt%.
Coloring agent
The colorant may be used for laser marking of the packaging material of the semiconductor device, and may be selected from typical colorants well known to those skilled in the art. For example, the colorant may include at least one selected from the group of carbon black, titanium nitride, copper hydroxide phosphate, iron oxide, and mica.
In the thermosetting resin composition, the colorant may be present in an amount of about 0.01 wt% to about 1 wt%, for example about 0.05 wt% to about 0.5 wt%.
Stress relieving agent
The stress relief agent may comprise a silicone-based compound, such as silicone oil, and the like.
In the thermosetting resin composition, the stress relief agent may be present in an amount of about 0.01 wt% to about 5 wt%, preferably about 0.05 wt% to about 3 wt%.
The thermosetting resin composition for encapsulating semiconductor devices according to the present invention may further comprise an antioxidant such as tetrakis [ methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] methane or the like, and a flame retardant such as aluminum hydroxide or the like, without affecting the object of the present invention.
The thermosetting resin composition for encapsulating semiconductor devices according to the present invention may further comprise an epoxy resin.
Epoxy resin
The epoxy resin may be selected from typical epoxy resins used for encapsulating semiconductor devices, and is not limited to a specific resin. Specifically, the epoxy resin may be an epoxy compound including at least two epoxy groups. For example, the epoxy resin may include an epoxy resin obtained by epoxidation of a condensate of phenol or alkylphenol and hydroxybenzaldehyde, a phenol aralkyl type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a polyfunctional epoxy resin, a naphthol novolac type epoxy resin, a bisphenol a/bisphenol F/bisphenol AD glycidyl ether, a bishydroxybiphenyl epoxy resin, a dicyclopentadiene epoxy resin, a biphenyl type epoxy resin, and the like. More specifically, the epoxy resin includes at least one selected from the group of a biphenyl type epoxy resin, a phenol aralkyl type epoxy resin, a cresol novolac type epoxy resin, and a multifunctional epoxy resin. Most preferably, the epoxy resin comprises a multifunctional epoxy resin.
The epoxy resin may be an epoxy resin having an epoxy equivalent of 100g/eq to 500g/eq in terms of a degree of cure. Within this range, the epoxy resin may improve the curing degree of the thermosetting resin composition.
These epoxy resins may be used alone or in a mixture thereof. In addition, the epoxy resin may be used in the form of an adduct, such as a melt masterbatch, which is obtained by pre-reacting the above epoxy resin with other components such as a maleimide compound, a benzoxazine compound, a curing accelerator, a mold release agent, a coupling agent and a stress relief agent.
In the thermosetting resin composition, the epoxy resin may be present in an amount of about 20 wt% or less, for example about 0.5 wt% to about 10 wt%, specifically about 0.5 wt% to about 5 wt%. Within this range, the epoxy resin may improve the curing degree of the thermosetting resin composition.
The thermosetting resin composition for encapsulating semiconductor devices can be prepared in the form of a powder product by the following method: wherein a Henschel mixer orThe mixer uniformly and sufficiently mixes predetermined amounts of the above components, followed by cooling and pulverization, followed by melt kneading using a roll mill or a kneader.
The thermosetting resin composition can be advantageously applied to semiconductor devices, particularly semiconductor devices for mobile devices or automobile fingerprint recognition sensors. As a method for encapsulating a semiconductor device using the thermosetting resin composition according to the present invention, low-pressure transfer molding can be generally used. However, it is to be understood that injection molding or casting may also be used for the molding of the thermosetting resin composition.
The semiconductor device according to the present invention may be encapsulated with a thermosetting resin composition for encapsulating the semiconductor device according to the present invention.
The semiconductor device according to the present invention may include a semiconductor device encapsulated with a thermosetting resin composition for encapsulating the semiconductor device according to the present invention.
Next, the present invention will be described in more detail with reference to some examples. It should be understood that these examples are provided for illustrative purposes only and are not to be construed as limiting the invention in any way.
Detailed Description
Preparation of example 1
100g of triphenylphosphine, 60g of 4-bromophenol, and 3.7g of NiBr2Into a 1L round bottom flask, 130g of ethylene glycol was added thereto, and reacted at 180 ℃ for 6 hours, thereby preparing a phenol-substituted phosphonium bromide salt. 21.4g of 2, 4-dihydroxybenzophenone and 18.4g of 2, 2-biphenol were added to 50g of MeOH, and then 21.6g of 25% sodium methoxide solution was added to completely dissolve by reaction at room temperature for 30 minutes. Then, a solution obtained by dissolving 43.5g of a phenol-substituted phosphonium bromide salt in 50g of ethanol was slowly added to the mixture, which was further reacted for 1 hour, and 300g of distilled water was added to the mixture. The obtained white solid was filtered to obtain 68g of a white compound. Based on the NMR data, the compound was identified as a compound represented by formula 4-5. 1HNMR7.87(3H, t),7.77-7.73(6H, m),7.69-7.65(6H, m),7.60(2H, d),7.39(1H, dd),7.32(2H, d),7.28-7.24(3H, m),7.08-7.02(4H, m),6.88(2H, dd),6.79(2H, d),6.55(2H, dd),6.34(1H, d),6.21(1H, s)
< formulas 4 to 5>
Preparation of example 2
23.0g of 2,3, 4-trihydroxybenzophenone and 12.4g of pyrogallol were added to 50g of MeOH, and then 21.6g of a 25% sodium methoxide solution was added to completely dissolve by reacting at room temperature for 30 minutes. Then, a solution obtained by dissolving 41.9g of a phenol-substituted phosphonium bromide salt in 50g of ethanol was slowly added to the mixture, which was further reacted for 1 hour, and 300g of distilled water was further added to the mixture. The obtained white solid was filtered to obtain 61g of a white compound. Based on the NMR data, the compound was identified as the compound represented by formula 4-4. 1HNMR8.00-7.94(4H, dt),7.85-7.70(16H, m),7.60(2H, d),7.32-7.27(3H, m),6.96(1H, d),6.55-6.50(2H, m),6.06(2H, d)
< formulas 4 to 4>
Preparation of example 3
19.8g of terephthalic acid was dissolved in 237mL of a 1M NaOH solution, and a solution obtained by dissolving 30.1g of pyrogallol in 100mL of methanol was slowly added to the mixture while reacting for 1 hour. Then, the resultant precipitate was filtered and dried, thereby preparing 106g of a brown solid compound, which is a tetravalent phosphonium salt represented by formula 5.
< formula 5>
Preparation of example 4
1.7g of catechol were dissolved in 50ml of methanol and stirred at room temperature. 1.8g of NaOMe (20% in MeOH) were added dropwise to the solution prepared. The resulting mixture was stirred at room temperature for 1 hour, and then 1.7g of titanium (IV) butoxide was added. Then, the mixture was stirred at room temperature for 3 hours, and a solution obtained by dissolving 4.3g of (4-hydroxyphenyl) triphenylphosphonium bromide in 5.0mL of MeOH was added to the mixture, followed by reaction at room temperature for about 2 hours. After completion of the reaction, a solution is obtained by filtering insoluble solids from the resulting mixture, and the solvent is removed from the solution, thereby preparing a compound. Based on the NMR data, the compound was identified as the compound represented by formula 6.
< formula 6>
1HNMR(400MHz,DMSO)7.93-7.86(m,6H),7.80-7.63(m,24H),7.20-7.13(m,4H),6,68(m,4H),6.16(m,6H),5.94(m,6H)ppm 13CNMR(100MHz,DMSO)158.0,144.5,138.7,137.4,137.2,128.9,128.8,122.8,117.3,115.9ppm；31PNMR(166MHz,DMSO)24.20ppm；LC-MS m/z＝1082(M+)；C66H52O8P2Analytical calculation of Ti: c, 73.20; h,4.84. find the value: c, 73.38; h,4.59.
Preparation of example 5
41.9g of tetraphenylphosphonium bromide and 55g of ethylenediaminetetraacetic acid chelated iron (III) sodium salt were dissolved in 200mL of ethanol and 200mL of distilled water, respectively, to prepare two solutions, which were then mixed and reacted at 25 ℃ for 24 hours. Thereafter, ethanol and water were removed from the mixture by vacuum distillation, and methylene chloride was added to the resultant mixture, which was then placed at 25 ℃, and then the resultant solid was filtered from the resultant mixture. Then, methylene chloride was removed from the resultant product by vacuum distillation, thereby preparing 54.0g of pale red powder represented by formula 7.
< formula 7>
Preparation of example 6
100g of catechol and 200mL of DCM (dichloromethane) were placed in a 1L round bottom flask and 85mL of TEA (triethylamine) was added and stirred vigorously with it to achieve complete dissolution. A solution prepared by dissolving 63mL of diphenyl chlorophosphate in 200mL of DCM was added dropwise to the prepared solution. After reacting at room temperature for 3 hours, the resultant solid was filtered from the resultant, washed with water and dried, thereby preparing 125g of a white ammonium salt solid (p 1). Thereafter, 50g of solid p1 and 100mL of MeOH were placed in succession in a 1-L round-bottom flask, and 20mL of 5M aqueous NaOH solution was added thereto while mixing therewith, followed by reaction for 30 minutes while heating the mixture to 60 ℃. After solid p1 was completely dissolved, a solution obtained by dissolving 46g of tetraphenylphosphonium bromide in 100mL of MeOH was added dropwise to the solution, and further reacted therewith for 2 hours. Thereafter, the temperature of the resultant solution was lowered to room temperature, and 500mL of distilled water was dropwise added to the resultant solution to obtain a solid, which was sequentially filtered, washed with water, and dried, thereby preparing 61g of a white solid compound, which was a tetravalent phosphonium salt represented by formula 8.
< formula 8>