CN116457387A - Resin composition for sealing semiconductor and semiconductor device - Google Patents
Resin composition for sealing semiconductor and semiconductor device Download PDFInfo
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- CN116457387A CN116457387A CN202180077136.0A CN202180077136A CN116457387A CN 116457387 A CN116457387 A CN 116457387A CN 202180077136 A CN202180077136 A CN 202180077136A CN 116457387 A CN116457387 A CN 116457387A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
A resin composition for sealing a semiconductor, comprising an epoxy resin, a phenolic resin curing agent, a curing accelerator, and an alumina powder, characterized in that: the alpha-ray amount of the cured product of the resin composition for sealing a semiconductor was 0.002count/cm 2 H is less than or equal to 4.0W/m.K, the thermal conductivity of the cured product of the resin composition for sealing a semiconductor is more than or equal to 4.0W/m.K.
Description
Technical Field
The present invention relates to a resin composition for sealing a semiconductor and a semiconductor device manufactured using the same.
Background
The semiconductor device is sealed for the purpose of protecting electronic components such as semiconductor elements, ensuring electrical insulation, facilitating handling, and the like. The sealing of semiconductor devices is mainly performed by transfer molding of an epoxy resin composition, and is preferable in terms of productivity, cost, reliability, and the like. In order to meet the market demands for miniaturization, weight saving, and higher performance of semiconductor devices, not only are the semiconductor elements highly integrated, miniaturized, and highly dense, but also new bonding techniques such as surface mounting have been developed and put into practical use. Such a technical trend is also spreading to epoxy resin compositions, and the performance is demanded to be highly and diversified year by year.
In order to prevent malfunction in devices of electronic component devices such as semiconductor devices for memories, which are susceptible to α -rays, it is necessary to reduce the amount of α -rays emitted from uranium (U), thorium (Th), and their metamorphic substances in constituent materials of the sealing material, and sealing materials corresponding to these have been developed (for example, patent document 1). Patent document 1 proposes a technique for reducing the amount of α -rays in a sealing material by making the total amount of uranium and thorium contained in alumina particles used as an inorganic filler less than 10 ppb.
In addition, with the recent higher functionality and higher speed of electronic devices, the higher density wiring and the higher multilayer wiring of semiconductor element circuits have been advanced, and the heat generation amount of the semiconductor element itself tends to increase. Conventionally, a semiconductor element for a memory, which does not require heat conduction, has been increasingly demanded for high heat conduction because the amount of heat generated by the semiconductor element increases with higher wiring.
Further, since a System In Package (SiP) is a combination of a plurality of semiconductor elements having different functions, and is an electronic component device assembled into 1 unit and having a plurality of functions related to a system and a subsystem, when semiconductor elements having different operation guarantee temperatures are stacked, the highest operation guarantee temperature is different. For example, the maximum operation guarantee temperature of a microprocessor is usually 100 ℃, but the maximum operation guarantee temperature of an electronic component device such as a semiconductor device for a memory is usually 85 ℃. In performing the thermal design of the SiP, the highest operation assurance temperature of all chips must be considered.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2005-248087
Disclosure of Invention
Technical problem to be solved by the invention
The present invention provides a sealing resin composition having high thermal conductivity and low alpha-ray quantity, which can also cope with "a single chip device having a large heat generation amount and being susceptible to alpha-rays, or a system in package or the like in which an element of a logic system having a large heat generation amount and being susceptible to alpha-rays are mixed with a memory, and a semiconductor device using the sealing resin composition.
Means for solving the technical problems
According to the present invention, there is provided a resin composition for sealing a semiconductor, comprising an epoxy resin, a phenolic resin curing agent, a curing accelerator and alumina powder, characterized in that:
the alpha-ray amount of the cured product of the resin composition for sealing a semiconductor was 0.002count/cm 2 The number of the groups is not more than h,
the cured product of the resin composition for sealing a semiconductor has a thermal conductivity of 4.0W/mK or more as measured by a laser flash method (laser flash method).
Further, according to the present invention, there is provided a semiconductor device comprising:
a semiconductor element; and
a sealing material sealing the semiconductor element,
the sealing material is composed of a cured product of the resin composition for sealing a semiconductor.
Effects of the invention
According to the present invention, it is possible to provide a sealing resin composition having high thermal conductivity and low α -rays, and a semiconductor device manufactured using the resin composition and having excellent reliability.
Drawings
Fig. 1 is a view showing a cross-sectional structure of an example of a double-sided sealed semiconductor device manufactured using the resin composition of the present embodiment.
Fig. 2 is a diagram showing a cross-sectional structure of an example of a single-sided sealed semiconductor device manufactured using the resin composition of the present embodiment.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and description thereof is omitted as appropriate. Moreover, all figures are for illustration only. The shapes, the size ratios, and the like of the respective components in the drawings do not necessarily correspond to actual articles. In the present specification, the expression "a to b" in the description of the numerical range means "a or more and b or less" unless otherwise specified. For example, "5 to 90 mass%" means "5 mass% or more and 90 mass% or less".
Hereinafter, embodiments of the present invention will be described.
The sealing resin composition (hereinafter, sometimes simply referred to as "resin composition") of the present embodiment is a resin material used as a sealing material for sealing a semiconductor element mounted on a substrate, and includes an epoxy resin, a phenolic resin curing agent, a curing accelerator, and alumina powder. The alpha-ray quantity of the cured product of the resin composition of the present embodiment was 0.002count/cm 2 H or less. The cured product of the resin composition of the present embodiment has a thermal conductivity of 4.0W/m·k or more as measured by the laser flash method.
The components used in the resin composition of the present embodiment will be described below.
(epoxy resin)
The epoxy resin used in the resin composition for sealing a semiconductor of the present embodiment includes: bisphenol type epoxy resins such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, and tetramethyl bisphenol F type epoxy resin; crystalline epoxy resins such as biphenyl epoxy resins, stilbene epoxy resins, hydroquinone epoxy resins, and the like; novolac type epoxy resins such as cresol novolac type epoxy resin, phenol novolac type epoxy resin, naphthol novolac type epoxy resin and the like; phenol aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a phenylene skeleton, phenol aralkyl type epoxy resins having a biphenylene skeleton, naphthol aralkyl type epoxy resins having a phenylene skeleton, phenol aralkyl type epoxy resins having an alkoxynaphthalene skeleton; 3-functional epoxy resins such as triphenol methane-type epoxy resins and alkyl-modified triphenol methane-type epoxy resins; modified phenolic epoxy resins such as dicyclopentadiene modified phenolic epoxy resins and terpene modified phenolic epoxy resins; heterocyclic epoxy resins such as triazine nucleus-containing epoxy resins, and the like, and these may be used alone or in combination of 1 or more. Among them, biphenyl type epoxy resins are preferable from the viewpoint of maintaining the melt viscosity within an optimum range, improving moldability, and reducing costs. The epoxy equivalent of the epoxy resin is preferably 90 to 300. When the epoxy equivalent is too small, the reactivity with the curing agent tends to decrease. Further, when the epoxy equivalent is excessively large, the strength of the cured product of the resin composition tends to be lowered.
The content of the epoxy resin is not particularly limited, but is preferably 2% by mass or more, more preferably 4% by mass or more, relative to the entire resin composition. When the lower limit value of the blending ratio is within the above range, there is little possibility that the fluidity is lowered or the like in the sealing step. The upper limit of the blending ratio of the entire resin composition is not particularly limited, but is preferably 22 mass% or less, more preferably 20 mass% or less, based on the total amount of the resin composition. When the upper limit of the blending ratio is within the above range, the decrease in glass transition temperature of the resin composition is small.
(phenolic resin curing agent)
Examples of the phenolic resin curing agent used in the resin composition of the present embodiment include novolak type phenolic resins such as phenol novolak resins, cresol novolak resins, bisphenol novolak resins and phenol-biphenyl novolak resins; polyvinyl phenol; multifunctional phenolic resins such as triphenol methane type phenolic resins; modified phenolic resins such as terpene-modified phenolic resins and dicyclopentadiene-modified phenolic resins; phenol aralkyl type phenolic resins such as phenol aralkyl resins having a phenylene skeleton and/or a biphenylene skeleton and naphthol aralkyl resins having a phenylene skeleton and/or a biphenylene skeleton; bisphenol compounds such as bisphenol a and bisphenol F, and the like. As the phenolic resin curing agent, 1 kind of the above specific examples may be used, or 2 or more kinds may be used in combination. As the phenolic resin curing agent, a phenol aralkyl resin containing a phenylene skeleton and/or a biphenylene skeleton in the above specific examples is preferable. Thus, the epoxy resin can be cured well in the resin composition.
The lower limit of the mixing ratio of the phenolic resin curing agent is not particularly limited, but is preferably 2% by mass or more, more preferably 3% by mass or more, relative to the entire resin composition. When the lower limit of the blending ratio is within the above range, sufficient fluidity can be obtained. The upper limit of the blending ratio of the curing agent is not particularly limited, but is preferably 16 mass% or less, more preferably 15 mass% or less, relative to the entire resin composition. When the upper limit of the blending ratio is within the above range, the fluidity and the meltability of the resin composition can be made within desired ranges.
The ratio of the epoxy resin to the phenolic resin curing agent is preferably not less than 0.8 and not more than 1.3 in terms of the equivalent ratio (EP)/(OH) of the epoxy resin number (EP) to the phenolic hydroxyl number (OH) of the phenolic resin curing agent. When the equivalent ratio is within this range, sufficient curability can be obtained at the time of molding the resin composition. When the equivalent ratio is within this range, the fluidity and the meltability of the resin composition can be made within desired ranges.
(curing accelerator)
The curing accelerator used in the resin composition of the present embodiment is not particularly limited as long as it is a substance capable of accelerating the curing reaction between the phenolic resin and the phenolic resin curing agent, and examples thereof include onium salt compounds; organic phosphines such as triphenylphosphine, tributylphosphine, and trimethylphosphine; tetra-substituted phosphonium compounds; a phosphobetaine (phosphobetaine) compound; adducts of phosphine compounds with quinone compounds; adducts of phosphonium compounds with silane compounds; imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole (EMI 24), 2-phenyl-4-methylimidazole (2P 4 MZ), 2-phenylimidazole (2 PZ), 2-phenyl-4-methyl-5-hydroxyimidazole (2P 4 MHZ), and 1-benzyl-2-phenylimidazole (1B 2 PZ); tertiary amines such as 1, 8-diazabicyclo (5, 4, 0) undecene-7 (DBU), triethanolamine, and benzyl dimethylamine. These may be used alone or in combination of 2 or more.
The content of the curing accelerator is preferably 0.1 mass% or more and 2 mass% or less with respect to the total amount of the epoxy resin and the phenolic resin curing agent. When the content of the curing accelerator is less than the above lower limit, the curing accelerator effect may not be improved. Further, when the content of the curing accelerator is more than the above-mentioned upper limit value, there is a tendency that fluidity or moldability may be poor, and there is a case that manufacturing cost may be increased.
(alumina powder)
The alumina powder used in the resin composition of the present embodiment has an effect of imparting thermal conductivity to the resin composition. Alumina powder has higher thermal conductivity than other inorganic fillers such as silica powder, for example, and is easily thermally designed when used as a sealing material. In addition, alumina powder is low in cost compared with other inorganic fillers (for example, magnesium oxide, boron nitride, aluminum nitride, diamond, etc.) having higher thermal conductivity than silica powder, and is easily improved in sphericity and excellent in heat resistance.
In order to prevent malfunctions in devices that are susceptible to α -rays, it is necessary for the alumina powder to reduce α -rays emitted from uranium, thorium, and their metamorphic substances in the inorganic filler blended in the resin composition of the present embodiment. The alumina powder used in the present embodiment preferably has a uranium content of 0.1 to 9.0ppb. In a preferred embodiment, the total content of uranium and thorium contained in the alumina powder is 10.0ppb or less. By using such an alumina powder, the amount of α -rays in the cured product of the obtained resin composition can be reduced.
The average particle diameter of the alumina powder is, for example, 0.5 to 40.0. Mu.m, preferably 1.0 to 30.0. Mu.m. In the case where the average particle diameter of the alumina powder is less than 0.5 μm, the viscosity of the resin composition becomes very high, and thus the filling property and the workability in the sealing step are deteriorated. In addition, in the case where the average particle diameter of the alumina powder is less than 0.5 μm, the elastic modulus of the cured product of the resin composition is lowered, and as a result, warpage of the obtained package occurs. On the other hand, when the average particle diameter of the alumina powder exceeds 40.0. Mu.m, there is a possibility that filling failure occurs. In addition, even if filling is possible, voids (void) are involved in filling, and thus are not suitable.
Preferably, in the alumina powder used in the present embodiment,
an alumina powder having a particle diameter of 106 μm or more and less than 250 μm is present in an amount of 5 mass% or more and 15 mass% or less relative to the entire alumina powder,
an alumina powder having a particle diameter of 250 μm or more and less than 500 μm is present in an amount of 25 mass% or more and 35 mass% or less relative to the entire alumina powder,
an alumina powder having a particle diameter of 500 [ mu ] m or more and less than 710 [ mu ] m in an amount of 20 to 25 mass% based on the entire alumina powder,
the alumina powder having a particle diameter of 710 μm or more and less than 1mm is 20 mass% or more and 25 mass% or less relative to the entire alumina powder.
By using the alumina powder having the above particle size distribution, a resin composition suitable as a sealing material can be obtained which has improved flowability and thus good handleability in the sealing step and reduced filling failure.
The shape of the alumina powder is not particularly limited, and may be any of spherical, phosphonium flake, granular, and powdery. The particle diameter of the alumina powder refers to the average maximum diameter of the alumina filler.
In a preferred embodiment, the alumina powder preferably comprises a spherical alumina powder having a sphericity of 0.8 or more, preferably 0.9 or more. Such spherical alumina powder exists in a state close to the most densely packed state in the sealing material, and therefore the thermal conductivity of the obtained sealing material can be improved. In addition, the resin composition containing such spherical alumina has improved fluidity and good handling properties in the sealing step.
Herein, in the present specification, "sphericity" is defined as "a ratio of a minimum diameter to a maximum diameter of particles" in a two-dimensional image observed using a Scanning Electron Microscope (SEM). That is, in the present embodiment, the ratio of the minimum diameter to the maximum diameter of the alumina particles in the two-dimensional image observed by using a Scanning Electron Microscope (SEM) is 0.8 or more.
The alumina powder containing spherical alumina used in the present embodiment can be produced by using a bayer process from an aluminum hydroxide powder having a small uranium content as a raw material. More specifically, bauxite is washed with a hot solution of sodium hydroxide at 220 to 260 ℃, and aluminum components contained in bauxite are dissolved by alkali and converted into sodium aluminate. Next, the components other than sodium aluminate are removed as solid impurities, and the solution is cooled to precipitate as aluminum hydroxide. Thereafter, the aluminum hydroxide powder is obtained by treatment with a pulverizer using a ball mill. In this case, the uranium and thorium are repeatedly washed with sodium hydroxide 2 to 4 times in consideration of the alkali-insoluble characteristics, and the impurities including uranium and thorium are repeatedly removed, whereby the amount of uranium and the amount of thorium contained in the aluminum hydroxide can be reduced to a desired level. Further, by precipitating at a temperature of 60 to 80 ℃ for 5 to 10 hours during cooling, the sodium (Na) content of the obtained aluminum hydroxide can be reduced.
The production of the alumina powder containing spherical alumina of the present invention is characterized by using the aluminum hydroxide powder obtained by the above method. As a method of melt-spheroidization, a process is performed using equipment composed of a powder supply device, a flame burner, a melting zone, a cooling zone, a powder recovery device, and an air suction fan. As an outline of the spheroidization, a raw material is supplied from a supply device, and a carrier gas is injected into a flame through a burner. The raw material melted in the flame is spheroidized by a melting zone and a cooling zone. The obtained spheroids are transferred to a powder recovery device together with the exhaust gas and collected. The flame is formed by injecting a combustible gas such as hydrogen, natural gas, acetylene gas, propane gas, butane, or the like, and a combustion-supporting gas such as air, oxygen, or the like from a flame burner provided in the furnace body. The flame temperature is preferably maintained at a temperature of 1800 ℃ to 2300 ℃. When the flame temperature is lower than 1800 ℃, sphericity of the produced spherical alumina particles may be deteriorated. When the flame temperature is higher than 2300 ℃, the spherical alumina particles formed are easily adsorbed to each other, and fluidity is lowered when forming a resin composition. As the carrier gas for supplying the raw material powder, air, nitrogen, oxygen, carbon dioxide, or the like can be used.
The content of the alumina powder in the resin composition of the present embodiment is 80 mass% to 97 mass% with respect to the mass of the entire resin composition. The lower limit value of the content of the alumina powder is preferably 82 mass% or more, more preferably 85 mass% or more, and still more preferably 87 mass% or more. The upper limit value of the content of the alumina powder is preferably 95 mass% or less, more preferably 92 mass% or less. By using the alumina powder in the above-described range, fluidity of the obtained resin composition can be improved, and thermal conductivity of the cured product of the obtained resin composition can be improved.
(other Components)
The resin composition of the present embodiment may contain additives such as inorganic fillers other than alumina powder, coupling agents, fluidity imparting agents, mold release agents, ion capturing agents, low-stress agents, colorants, flame retardants, and the like, as necessary. The representative components will be described below.
(inorganic filler)
The resin composition of the present embodiment may contain an inorganic filler in addition to the alumina powder. Examples of the inorganic filler include: silica such as fused silica, fused spherical silica, crystalline silica, and 2-shot silica; silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, titanium white, talc, clay, mica, glass fiber, and the like. The particle shape is not limited, but is preferably spherical, and the amount of filling can be increased by mixing particles having different particle sizes.
(coupling agent)
Specific examples of the coupling agent include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxysilanes such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, and 3-epoxypropoxypropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; methacryloylsilanes such as 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, and 3-methacryloxypropyl triethoxy silane; acrylic silanes such as 3-acryloxypropyl trimethoxysilane; aminosilanes such as N-2- (aminoethyl) -3-aminopropyl methyldimethoxy silane, N-2- (aminoethyl) -3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-triethoxy silicon-N- (1, 3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyl trimethoxy silane, and phenylaminopropyl trimethoxy silane; isocyanurate silanes; an alkylsilane; ureidosilanes such as 3-ureidopropyl trialkoxysilane; mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate silanes such as 3-isocyanate propyltriethoxysilane; a titanium compound; aluminum chelates; aluminum/zirconium compounds, and the like. As the coupling agent, 1 or 2 or more of the above specific examples may be blended.
(fluidity imparting agent)
The fluidity imparting agent can exert the following functions: the curing accelerator having no latent property such as the curing accelerator having a phosphorus atom is inhibited from reacting during melt kneading of the resin composition. This can improve the productivity of the resin composition. Specific examples of the fluidity imparting agent include catechol, pyrogallol, gallic acid esters, 1, 2-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, derivatives thereof, and the like, each of which has a hydroxyl group bonded to 2 or more adjacent carbon atoms constituting an aromatic ring.
(Release agent)
Specific examples of the release agent include: natural waxes such as carnauba wax; synthetic waxes such as montan acid ester wax and oxidized polyethylene wax; higher fatty acid such as zinc stearate and metal salt thereof; paraffin wax; carboxylic acid amides such as erucamide. As the release agent, 1 or 2 or more of the above specific examples may be blended.
(ion scavenger)
Specific examples of the ion scavenger include: hydrotalcite-like substances such as hydrotalcite and hydrotalcite-like substances; hydrous oxides of elements selected from magnesium, aluminum, bismuth, titanium, zirconium, and the like. As the ion scavenger, 1 or 2 or more of the above specific examples may be blended.
(Low stress agent)
Specific examples of the low-stress agent include: silicone oils, silicone rubbers, and other organosilicon compounds; a polybutadiene compound; acrylonitrile-butadiene copolymer compounds such as acrylonitrile-carboxyl terminal butadiene copolymer compounds. As the low-stress agent, 1 or 2 or more of the above specific examples may be blended.
(colorant)
Specific examples of the colorant include carbon black, red lead, and titanium oxide. As the colorant, 1 or 2 or more of the above specific examples may be blended.
(flame retardant)
Specific examples of the flame retardant include: aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, carbon black, and the like. As the flame retardant, 1 or 2 or more of the above specific examples may be blended.
(production of sealing resin composition)
The resin composition of the present embodiment can be produced as follows: mixing is uniformly performed using a mixer such as a tumbler mixer or a Henschel mixer or a stirrer so that the above components and additives to be used as needed are contained in predetermined amounts, and kneading is performed while heating using a kneader, a roll, a disperser, a vacuum emulsifying machine, a planetary mixer, or the like. The temperature during kneading is required to be within a temperature range in which curing reaction does not occur, and is preferably about 70 to 150℃although it depends on the compositions of the epoxy resin and the phenolic resin curing agent. After kneading, the mixture is cooled and solidified, and the kneaded product can be processed into powder, granule, ingot or tablet.
As a method for obtaining a particulate resin composition, for example, a method of pulverizing a kneaded product by a pulverizing device is mentioned. The kneaded material may be formed into a sheet and pulverized. As the pulverizing device, for example, a hammer mill, a stone mill, a roll mill can be used.
As a method for obtaining a particulate or powdery resin composition, for example, a granulation method typified by a hot cut method in which a die having a small diameter is provided at an outlet of a kneading apparatus and a kneaded product in a molten state discharged from the die is cut into a predetermined length by a cutter or the like may be used. In this case, it is preferable to perform deaeration before the temperature of the resin composition is not lowered so much after the resin composition in the form of pellets or powder is obtained by a granulation method such as a thermal cutting method.
The resin composition of the present embodiment, which is produced by the above-described method using the above-described components in a predetermined blending amount, has an α -ray amount of 0.002count/cm as a cured product 2 H is less than or equal to 0.001count/cm 2 H or less. Thus, when the resin composition of the present embodiment is used as a sealing material, malfunction in a device that is susceptible to α -rays can be prevented. The α -ray amount of the cured product of the resin composition of the present embodiment is more preferably 0.0015count/cm 2 H or less, more preferably 0.0010count/cm 2 H or less.
The resin composition of the present embodiment produced by the above-described method using the above-described components in a predetermined blending amount has a thermal conductivity of 4.0W/m·k or more, preferably 4.2W/m·k or more, more preferably 4.4W/m·k or more, and even more preferably 4.6W/m·k or more, when the cured product is measured by a laser flash method. Thus, when the resin composition of the present embodiment is used as a sealing material, thermal design is easy, and reliability of a semiconductor device obtained by sealing a semiconductor element in a high-temperature environment can be improved.
The minimum melt viscosity of the resin composition of the present embodiment is, for example, 30kpa·s or less, preferably 20kpa·s or less, and more preferably 15kpa·s or less. When the above value is exceeded, the filling property is lowered, and voids or unfilled portions may be generated. The resin composition of the present embodiment having the lowest melt viscosity in the above range has good injectability by capillary flow in the sealing step and excellent handleability.
The resin composition of the present embodiment produced by the above-described method using the above-described components in a predetermined blending amount has an elastic modulus at 25℃in the range of 15,000MPa to 40,000 MPa. Thus, the package obtained is free from warpage, and a semiconductor device having excellent reliability can be obtained.
The resin composition of the present embodiment, which is produced by the above-described method using the above-described components in the predetermined blending amounts, when the curing torque value of the resin composition for sealing a semiconductor is measured with the lapse of time at the measurement temperature of 175 ℃ using a vulcanizer, an increase in the curing torque value is observed during a period of 50 seconds to 100 seconds after the start of the measurement. The resin composition having such a behavior of torque variation can efficiently perform the sealing step.
(semiconductor device)
An example of a semiconductor device manufactured by using the sealing resin composition of the present embodiment as a sealing material will be described.
Fig. 1 is a cross-sectional view showing a double-sided sealed semiconductor device 100 according to the present embodiment.
The semiconductor device 100 of the present embodiment includes: an electronic component 20; a bonding wire 40 connected to the electronic component 20; and a sealing material 50, wherein the sealing material 50 is composed of a cured product of the resin composition.
More specifically, the electronic component 20 is fixed to the base material 30 via a die attach (die attach) material 10, and the semiconductor device 100 has an outer lead 34 connected from an electrode pad, not shown, provided on the electronic component 20 via a bonding wire 40. The bonding wire 40 may be set in consideration of the electronic component 20 and the like used, and for example, a Cu wire may be used.
Fig. 2 is a view showing a cross-sectional structure of an example of a single-sided sealed semiconductor device obtained by sealing an electronic component mounted on a circuit board using the resin composition of the present embodiment. The electronic component 401 is fixed on the circuit substrate 408 via the die attach material 402. The electrode pads 407 of the electronic component 401 are connected to the electrode pads 407 on the circuit substrate 408 by bonding wires 404. The surface of the circuit board 408 on which the electronic component 401 is mounted is sealed with a sealing material 406 made of a cured product of the resin composition according to the present embodiment. The electrode pads 407 on the circuit substrate 408 are internally bonded to solder balls 409 on the non-sealing surface side on the circuit substrate 408.
Hereinafter, a method for manufacturing a semiconductor device using the sealing resin composition of the present embodiment will be described.
The semiconductor device of the present embodiment can be manufactured by, for example, the following steps: a step of obtaining a sealing resin composition by the method for producing a sealing resin composition described above; a step of loading an electronic component on a substrate; and sealing the electronic component using the sealing resin composition. As a method for forming the sealing material, for example, a transfer molding method, a compression molding method, an injection molding method, or the like can be used. The step of sealing may be performed by curing the resin composition at a temperature of about 80 to 200 ℃ for a time of about 10 minutes to 10 hours.
Examples of the type of the electronic device to be sealed include, but are not limited to, semiconductor devices such as an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging device. Examples of the semiconductor device obtained include, but are not limited to, dual in-line package (DIP), plastic-attached lead chip carrier (plastic leaded chip carrier, PLCC), quad flat package (quad flat package, QFP), thin quad flat package (1ow profile quad flat package,LQFP), small outline package (small outline package, SOP), small outline J-lead package (SOJ), thin small outline package (thin small outline package, TSOP), thin quad flat package (thin quad flat package, TQFP), tape carrier package (tape carrier package, TCP), ball Grid Array (BGA), chip size package (chip size package, CSP), and the like.
While the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above may be adopted.
Examples (example)
Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
The components used in examples and comparative examples are shown below.
(epoxy resin)
Epoxy resin 1: biphenyl epoxy resin (3, 3', 5' -tetramethyl biphenyl glycidyl ether) (manufactured by Mitsubishi chemical corporation (Mitsubishi Chemical Corporation), YX4000 HK)
Epoxy resin 2: phenol aralkyl type epoxy resin having biphenylene skeleton (manufactured by Nippon Kayaku Co., ltd., NC 3000)
(curing agent)
Curing agent 1: phenol-hydroxybenzaldehyde resin (manufactured by Ming He Chemicals Co., ltd. (MEIWA PLASTIC INDUSTRIES, LTD.), MEH-7500)
Curing agent 2: copolymer type phenol resin of triphenol methane type resin and phenol novolac resin (AIR WATER inc. Manufactured, HE 910-20)
Curing agent 3: p-biphenylene modified phenolic resin (MEH-7851 SS, manufactured by Ming He Chemicals Co., ltd.)
(curing accelerator)
Cure accelerator 1: tetraphenylphosphonium-4, 4' -sulfonyldiphenol esters represented by the following chemical formula
Cure accelerator 2: curing accelerators (tetraphenylphosphonium bis (naphthalene-2, 3-dioxy) phenylsilicate) represented by the following formula
(alumina powder)
Alumina powder 1: alumina filler (DAB-30 FC, manufactured by electric Co., ltd. (Denka Company Limited), uranium content of 7ppb or more, thorium content of less than 1ppb, average particle diameter (D50): 13 μm)
Alumina powder 2: alumina filler (manufactured by Nitro iron chemical Co., ltd. (NIPPON STEEL Chemical & Material Co., ltd.), low alpha-ray alumina, uranium content: 7ppb, thorium content: less than 1ppb, average particle diameter (D50): 15 μm)
Alumina powder 3: alumina filler (manufactured by Kagaku Dou Ma (Admatechs Company Limited), low alpha ray alumina, uranium content of less than 1ppb, thorium content of less than 1ppb, average particle size (D50): 0.2 μm)
(inorganic filler)
Inorganic filler 1: silica filler (manufactured by Kagaku Dou Ma, SD 5500-SQ)
Inorganic filler 2: silica filler (REOLOSIL CP-102 manufactured by Deshan Co., ltd. (Tokuyama Corporation))
(colorant)
Colorant 1: carbon black (Mitsubishi chemical corporation, MA-600)
(coupling agent)
Coupling agent 1: n-phenyl-3-aminopropyl trimethoxysilane (CF-4083, manufactured by Toli Corning Co., ltd. (Dow Corning Toray Co.; ltd.))
(Release agent)
Mold release agent 1: palm wax (TOA KASEI CO., LTD.) manufactured by TOWAX-132)
(ion scavenger)
Ion scavenger 1: magnesium/aluminum/hydroxide/carbonate/hydrate (manufactured by Kyowa Kagaku Co., ltd. (Kyowa Chemical Industry Co., ltd.), DHT-4H)
(Low stress agent)
Low stress agent 1: dimethylsiloxane-alkyl carboxylic acid-4, 4' - (1-methylethylene) bisphenol glycidyl ether copolymer (manufactured by Sumitomo electric Wood Co., ltd., M69B)
Low stress agent 2: silicone resin (KR-480 manufactured by Xinyue Chemical Co., ltd.) (Shin-Etsu Chemical Co., ltd.)
(examples 1 to 4, comparative examples 1 to 2)
After the compounded raw materials shown in Table 1 were pulverized and mixed for 5 minutes by a super mixer, the mixed raw materials were melt-kneaded at a resin temperature of 100℃by a co-rotating twin-screw extruder having a barrel inner diameter of 65mm in diameter at a screw speed of 200 rpm. Next, the resin composition after melt-kneading was supplied at a rate of 2kg/hr from above a rotor having a diameter of 20cm, and the resin composition after melt-kneading was passed through a plurality of small holes (aperture: 1.2 mm) in the cylindrical outer peripheral portion heated to 115 ℃ by a centrifugal force obtained by rotating the rotor at 3000 rpm. Then, the resin composition for sealing in the form of pellets was obtained by cooling. The obtained particulate sealing resin composition was stirred under an air stream having a relative humidity of 55% RH at 15℃for 3 hours. The obtained sealing resin composition was evaluated for the following items by the methods shown below. The measurement results are shown in table 1.
(fluidity (spiral flow))
The resin composition was injected into a spiral flow measuring die according to EMMI-1-66 using a low pressure transfer molding machine (KTS-15, manufactured by Shang Jiuji Co., ltd. (KOHTAKI Corporation)), under the conditions of a die temperature of 175 ℃, an injection pressure of 6.9MPa, and a dwell time of 120 seconds, and the flow length was measured. Spiral flow is an index of fluidity, and the larger the numerical value is, the better the fluidity is. The unit is cm.
(curing Property (gel time))
The gel times of the resin compositions obtained in each example were measured. The gel time was measured by measuring the time until curing (gel time: seconds) while stirring with a spatula after melting the resin composition on a hot plate heated to 120 ℃.
(flexural Strength)
A test piece having a length of 80mm or more, a height of 4mm and a width of 10mm was produced, after post-hardening, bending stress was gradually applied at a crosshead speed of 2mm/min and a distance between fulcrums of 64mm, and the test piece was broken to obtain a load-strain curve, and the bending strength of the test piece was calculated from the maximum point stress. The measurement was performed with n=2, and the average value thereof was taken as a representative value.
(elastic modulus at room temperature (25 ℃ C.))
Test pieces having a length of 80mm or more, a height of 4mm and a width of 10mm were produced, after post-hardening, bending stress was gradually applied at a crosshead speed of 2mm/min and a distance between fulcrums of 64mm, and a load-strain curve was obtained to calculate the flexural modulus of the test pieces. The measurement was performed with n=2, and the average value thereof was taken as a representative value.
(thermal conductivity)
Test pieces having a length of 1em, a width of 1em and a thickness of 1mm were prepared, and thermal diffusivity was measured. Specific heat measurements were performed using powder. The thermal conductivity was determined from the obtained thermal diffusivity, specific heat, and specific gravity.
(5 μm slit burr)
The resin composition was molded in a mold having a cavity with a height of 5 μm, a width of 4mm and a length of 72mm under the conditions of an injection pressure of 10MPa, a mold temperature of 175℃and a curing time of 120 seconds by transfer molding, and the length of intrusion of the resin composition into the cavity was measured as a value of 5 μm slit burrs using calipers.
(alpha ray quantity)
Test pieces (140 mm. Times.120 mm, thickness: 2 mm) were molded from the resin composition by compression molding under conditions of a mold temperature of 175℃and a curing time of 2 minutes. Using the 6 obtained (total 1008 cm) 2 ) The test piece was subjected to measurement of the amount of alpha rays by using a low-order alpha ray measuring device LACS-4000M (applied voltage of 1.9KV, PR-10 gas (argon: methane=9:1) 100M/min, effective counting time of 40 h).
The resin compositions of the examples are all low in alpha-ray amount, excellent in thermal conductivity, and suitable as semiconductor sealing materials in terms of curing characteristics and mechanical characteristics.
The present application claims priority based on japanese patent application publication No. 2020-190154 filed 11/16/2020, and the entire disclosure thereof is incorporated herein.
Description of the reference numerals
10 die attach material, 20 electronic component, 30 substrate, 32 die pad, 34 external lead, 40 bond wire, 50 encapsulant material, 100 semiconductor device, 401 electronic component, 402 die attach material, 404 bond wire, 406 encapsulant material, 407 electrode pad, 408 circuit substrate, 409 solder ball.
Claims (7)
1. A resin composition for sealing a semiconductor, comprising an epoxy resin, a phenolic resin curing agent, a curing accelerator, and an alumina powder, characterized in that:
the alpha-ray amount of the cured product of the resin composition for sealing a semiconductor is0.002count/cm 2 The number of the groups is not more than h,
the cured product of the resin composition for sealing a semiconductor has a thermal conductivity of 4.0W/mK or more as measured by a laser flash method.
2. The resin composition for sealing a semiconductor according to claim 1, wherein:
the aluminum oxide powder is present in an amount of 80 to 97 mass% based on the entire semiconductor sealing resin composition.
3. The resin composition for sealing a semiconductor according to claim 1 or 2, characterized in that:
the alumina powder contains spherical alumina having a sphericity of 0.8 or more.
4. The resin composition for sealing a semiconductor according to any one of claims 1 to 3, characterized in that:
the cured product of the resin composition for sealing a semiconductor has an elastic modulus at 25 ℃ of 15,000MPa to 40,000 MPa.
5. The resin composition for sealing a semiconductor according to any one of claims 1 to 4, characterized in that:
in the case of the powder of the aluminum oxide,
an alumina powder having a particle diameter of 106 μm or more and less than 250 μm is present in an amount of 5 mass% or more and 15 mass% or less relative to the entire alumina powder,
an alumina powder having a particle diameter of 250 μm or more and less than 500 μm is present in an amount of 25 mass% or more and 35 mass% or less relative to the entire alumina powder,
an alumina powder having a particle diameter of 500 [ mu ] m or more and less than 710 [ mu ] m in an amount of 20 to 25 mass% based on the entire alumina powder,
the alumina powder having a particle diameter of 710 μm or more and less than 1mm is 20 mass% or more and 25 mass% or less relative to the entire alumina powder.
6. The resin composition for sealing a semiconductor according to any one of claims 1 to 5, characterized in that:
and also contains a release agent.
7. A semiconductor device, comprising:
a semiconductor element; and
a sealing material sealing the semiconductor element,
the sealing material is composed of a cured product of the resin composition for sealing a semiconductor according to any one of claims 1 to 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020-190154 | 2020-11-16 | ||
| JP2020190154 | 2020-11-16 | ||
| PCT/JP2021/041498 WO2022102697A1 (en) | 2020-11-16 | 2021-11-11 | Resin composition for semiconductor encapsulation, and semiconductor device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116457387A true CN116457387A (en) | 2023-07-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180077136.0A Pending CN116457387A (en) | 2020-11-16 | 2021-11-11 | Resin composition for sealing semiconductor and semiconductor device |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP7355241B2 (en) |
| KR (1) | KR20230107646A (en) |
| CN (1) | CN116457387A (en) |
| TW (1) | TW202225244A (en) |
| WO (1) | WO2022102697A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117511426A (en) * | 2024-01-05 | 2024-02-06 | 深圳市长松科技有限公司 | Film for packaging and blocking water vapor, semiconductor film packaging method and structure |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09286613A (en) * | 1996-04-19 | 1997-11-04 | Nippon Steel Chem Co Ltd | Production of high purity alumina and mullite for electronic material |
| JPH1192136A (en) * | 1997-09-18 | 1999-04-06 | Adomatekkusu:Kk | Production of low alpha-dose alumina powder and low alpha-dose alumina powder |
| JP4004270B2 (en) * | 2001-11-05 | 2007-11-07 | 電気化学工業株式会社 | High thermal conductive inorganic powder and resin composition |
| JP4631296B2 (en) | 2004-03-05 | 2011-02-16 | 住友ベークライト株式会社 | Epoxy resin composition and semiconductor device |
| JP5983085B2 (en) * | 2012-06-25 | 2016-08-31 | 住友ベークライト株式会社 | Epoxy resin composition and electronic component device |
| JP2014197649A (en) * | 2013-03-29 | 2014-10-16 | 株式会社アドマテックス | Three-dimensional mount type semiconductor device, resin composition and method for manufacturing the same |
| JP6287085B2 (en) * | 2013-11-11 | 2018-03-07 | 住友ベークライト株式会社 | Method for producing organic compound-modified inorganic filler |
-
2021
- 2021-11-11 CN CN202180077136.0A patent/CN116457387A/en active Pending
- 2021-11-11 KR KR1020237019844A patent/KR20230107646A/en unknown
- 2021-11-11 WO PCT/JP2021/041498 patent/WO2022102697A1/en active Application Filing
- 2021-11-11 JP JP2022529571A patent/JP7355241B2/en active Active
- 2021-11-16 TW TW110142571A patent/TW202225244A/en unknown
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2023
- 2023-05-29 JP JP2023087477A patent/JP2023109966A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117511426A (en) * | 2024-01-05 | 2024-02-06 | 深圳市长松科技有限公司 | Film for packaging and blocking water vapor, semiconductor film packaging method and structure |
| CN117511426B (en) * | 2024-01-05 | 2024-04-12 | 深圳市长松科技有限公司 | Film for packaging and blocking water vapor, semiconductor film packaging method and structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2022102697A1 (en) | 2022-05-19 |
| WO2022102697A1 (en) | 2022-05-19 |
| KR20230107646A (en) | 2023-07-17 |
| JP2023109966A (en) | 2023-08-08 |
| TW202225244A (en) | 2022-07-01 |
| JP7355241B2 (en) | 2023-10-03 |
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