WO2019131669A1 - Sealing composition and semiconductor device - Google Patents

Sealing composition and semiconductor device Download PDF

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Publication number
WO2019131669A1
WO2019131669A1 PCT/JP2018/047642 JP2018047642W WO2019131669A1 WO 2019131669 A1 WO2019131669 A1 WO 2019131669A1 JP 2018047642 W JP2018047642 W JP 2018047642W WO 2019131669 A1 WO2019131669 A1 WO 2019131669A1
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WO
WIPO (PCT)
Prior art keywords
inorganic filler
particle size
sealing composition
alumina
mass
Prior art date
Application number
PCT/JP2018/047642
Other languages
French (fr)
Japanese (ja)
Inventor
健太 石橋
格 山浦
拓也 児玉
実佳 田中
慧地 堀
東哲 姜
Original Assignee
日立化成株式会社
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Publication date
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to CN201880084098.XA priority Critical patent/CN111566163B/en
Priority to KR1020207018215A priority patent/KR20200103682A/en
Priority to JP2019562046A priority patent/JP7238791B2/en
Publication of WO2019131669A1 publication Critical patent/WO2019131669A1/en
Priority to JP2023032122A priority patent/JP2023067951A/en

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present invention relates to a sealing composition and a semiconductor device.
  • a semiconductor package adopting a method called a wire bonding structure in which a semiconductor element and a substrate are connected via a wire uses a resin composition for the semiconductor element, the substrate, and a wire electrically connecting these. It is formed by sealing. At this time, pressure is applied to the wire due to the flow of the sealing material, which may cause displacement of the wire (wire flow) or insufficient protection of the semiconductor element. As described above, it may be difficult to achieve both the flowability of the sealing material and the high thermal conductivity.
  • One aspect of the present invention is made in view of the above-mentioned conventional circumstances, and it aims at providing a sealing composition which is excellent in fluidity and has high thermal conductivity, and a semiconductor device using the same.
  • the specific means for achieving the said subject are as follows. ⁇ 1> containing an epoxy resin, a curing agent, and an inorganic filler, The particle size distribution of the inorganic filler has at least three peaks, The sealing composition in which the said inorganic filler contains an alumina with a particle diameter of 1 micrometer or less. ⁇ 2> The sealing composition according to ⁇ 1>, wherein the particle size distribution of the inorganic filler has a peak in a range of 0.3 ⁇ m to 0.7 ⁇ m, a range of 7 ⁇ m to 20 ⁇ m, and a range of 30 ⁇ m to 70 ⁇ m.
  • ⁇ 3> The sealing composition according to ⁇ 1> or ⁇ 2>, wherein a ratio of alumina in inorganic particles having a particle diameter of 1 ⁇ m or less in the inorganic filler is 1% by volume to 40% by volume.
  • ⁇ 4> The sealing composition according to any one of ⁇ 1> to ⁇ 3>, wherein the average circularity of the inorganic filler is 0.80 or more.
  • a semiconductor device comprising: a semiconductor element; and a cured product of the sealing composition according to any one of ⁇ 1> to ⁇ 4>, wherein the semiconductor element is sealed.
  • the present invention is not limited to the following embodiments.
  • the constituent elements including element steps and the like
  • the constituent elements are not essential unless otherwise specified.
  • numerical values described before and after “to” are included in the numerical range indicated using “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical value range may be replaced with the upper limit value or the lower limit value of the other stepwise description numerical value range in the numerical value range described stepwise in the present disclosure. .
  • each component may contain a plurality of corresponding substances.
  • the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified.
  • a plurality of particles corresponding to each component may be contained.
  • the particle diameter of each component means the value for the mixture of the plurality of particles present in the composition unless otherwise specified.
  • the sealing composition of the present disclosure contains an epoxy resin, a curing agent, and an inorganic filler, and the particle size distribution of the inorganic filler has at least three peaks, and the inorganic filler has a particle diameter. Contains alumina of 1 ⁇ m or less.
  • the sealing composition of the present disclosure has excellent fluidity and high thermal conductivity. Although the reason is not clear, it is guessed as follows.
  • the inorganic filler contained in the sealing composition exhibits a particle size distribution having at least three peaks. That is, the inorganic filler is configured to include at least inorganic particles having a large particle size, inorganic particles having a medium particle size, and inorganic particles having a small particle size.
  • the sealing composition of the present disclosure is considered to be excellent in fluidity.
  • the inorganic filler contains alumina having a particle diameter of 1 ⁇ m or less, and the alumina exhibits high thermal conductivity as described above.
  • alumina having a particle diameter of 1 ⁇ m or less corresponds to inorganic particles having a small particle diameter as the inorganic filler contained in the sealing composition.
  • the thermal conductivity between the large particle size inorganic particles and the medium particle size inorganic particles is promoted by interposing the alumina exhibiting high thermal conductivity between the large particle size inorganic particles and the medium particle size inorganic particles. be able to. As a result, it is assumed that the sealing composition of the present disclosure has high thermal conductivity.
  • the sealing composition of the present disclosure contains an epoxy resin, a curing agent, and an inorganic filler, and may contain other components as needed.
  • the sealing composition contains an epoxy resin.
  • the type of epoxy resin is not particularly limited, and known epoxy resins can be used. Specifically, for example, it is selected from the group consisting of phenol compounds (for example, phenol, cresol, xylenol, resorcine, catechol, bisphenol A and bisphenol F) and naphthol compounds (for example, ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene) Epoxidized novolak resin obtained by condensation or cocondensation of at least one of the following compounds with an aldehyde compound (eg, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde) under an acidic catalyst (eg, phenol Novolac type epoxy resin and ortho cresol novolac type epoxy resin); bisphenol (for example, bisphenol A, bisphenol AD, bisphenol F and bisphenol) At least one diglycidy
  • the purity of the epoxy resin is preferably high, and the amount of hydrolyzable chlorine is preferably small.
  • the amount of hydrolyzable chlorine is preferably 500 ppm or less on a mass basis.
  • the amount of hydrolyzable chlorine is a value determined by potentiometric titration after dissolving 1 g of the epoxy resin as a sample in 30 mL of dioxane, adding 5 mL of 1N-KOH methanol solution and refluxing for 30 minutes.
  • the content of the epoxy resin in the sealing composition is preferably 1.5% by mass to 20% by mass, more preferably 2.0% by mass to 15% by mass, and 3.0% by mass or more More preferably, it is 10% by mass.
  • the content of the epoxy resin in the sealing composition excluding the inorganic filler is preferably 30% by mass to 65% by mass, more preferably 35% by mass to 60% by mass, and 40% by mass to 55% by mass. More preferably, it is mass%.
  • the sealing composition contains a curing agent.
  • the type of curing agent is not particularly limited, and known curing agents can be used. Specifically, for example, it is selected from the group consisting of phenol compounds (eg, phenol, cresol, resorcine, catechol, bisphenol A and bisphenol F) and naphthol compounds (eg, ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene)
  • Novolak resin obtained by condensation or cocondensation of at least one type and an aldehyde compound (eg, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde) under an acidic catalyst; phenol / aralkyl resin; biphenyl / aralkyl resin; And naphthol / aralkyl resins.
  • the curing agent may be used alone or in combination of two or more.
  • a phenol / aralkyl resin is preferable from the viewpoint of improving the reflow resistance.
  • the curing agent may be used alone or in combination of two or more.
  • the curing agent is blended such that the equivalent of the functional group of the curing agent (for example, phenolic hydroxyl group in the case of novolak resin) is 0.5 equivalent to 1.5 equivalents to 1 equivalent of epoxy group of the epoxy resin.
  • the curing agent is preferably blended so as to be 0.7 equivalents to 1.2 equivalents.
  • the sealing composition comprises an inorganic filler.
  • the inorganic filler By including the inorganic filler, the hygroscopicity of the sealing composition is reduced, and the strength in the cured state tends to be improved.
  • the inorganic filler may be used alone or in combination of two or more.
  • two or more types of inorganic fillers are used in combination, there may be mentioned, for example, a case where two or more types of inorganic fillers having different components, average particle diameter, shape and the like are used.
  • the shape of the inorganic filler is not particularly limited, and examples thereof include powder, sphere, and fiber. It is preferable that it is spherical shape from the point of the fluidity
  • the average circularity of the inorganic filler is preferably 0.80 or more, more preferably 0.85 or more, still more preferably 0.90 or more, and particularly preferably 0.93 or more. preferable.
  • the average circularity of the inorganic filler may be 1.0 or less.
  • the circularity of the inorganic filler is the circumference measured from the projected image of the inorganic filler, as the circle equivalent diameter calculated from the equivalent circle diameter which is the diameter of a circle having the same area as the projected area of the inorganic filler It is a numerical value obtained by dividing by the length (length of contour line), and is obtained by the following equation. The roundness is 1.00 for a true circle.
  • Circularity (perimeter of equivalent circle) / (perimeter of particle cross-sectional image) Specifically, the average circularity is observed by a scanning electron microscope at a magnification of 1000 times, an image of 10 inorganic fillers is arbitrarily selected, and the circularity of each inorganic filler is measured by the above method. And the value calculated as the arithmetic mean value.
  • the degree of circularity, the circumferential length of the equivalent circle, and the circumferential length of the projected image of particles can be determined by commercially available image analysis software. When two or more types are used together as an inorganic filler, the average roundness of an inorganic filler says the value as a mixture of two or more types of inorganic fillers.
  • the inorganic filler is not particularly limited with respect to the material, the particle diameter and the like, as long as the inorganic filler has alumina having a particle size distribution having at least three peaks and having a particle diameter of 1 ⁇ m or less.
  • examples of the inorganic filler include spherical silica, silica such as crystalline silica, alumina, zircon, magnesium oxide, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, boron nitride, aluminum nitride, beryllia, zirconia, etc.
  • examples of the inorganic filler having a flame retardant effect include aluminum hydroxide and zinc borate.
  • alumina is preferable from the viewpoint of high thermal conductivity.
  • the proportion of alumina in the inorganic filler is preferably 60% by mass to 95% by mass, more preferably 60% by mass to 92% by mass, and still more preferably 60% by mass to 90% by mass.
  • alumina and silica may be used in combination.
  • the proportion of alumina in the inorganic filler is preferably 80% by mass to 95% by mass, and the proportion of silica is preferably 5% by mass to 20% by mass, alumina Of 82% by mass to 92% by mass, more preferably 8% by mass to 18% by mass of silica, and 85% by mass to 90% by mass of alumina; It is more preferable that the content is 15% by mass.
  • the particle size distribution of the inorganic filler has at least three peaks, preferably three peaks.
  • the position of the peak in the particle size distribution of the inorganic filler is not particularly limited, and preferably has a peak in the range of 0.3 ⁇ m to 0.7 ⁇ m, in the range of 7 ⁇ m to 20 ⁇ m, and in the range of 30 ⁇ m to 70 ⁇ m, It is more preferable to have peaks in the range of 0.3 ⁇ m to 0.6 ⁇ m, in the range of 7 ⁇ m to 15 ⁇ m, and in the range of 40 ⁇ m to 70 ⁇ m.
  • the particle size distribution of the inorganic filler can be determined by the following method.
  • An inorganic filler to be measured is added to a solvent (pure water) in the range of 0.02% by mass to 0.08% by mass, and vibrated for 1 to 10 minutes with a 110 W bath ultrasonic cleaner, Disperse the filler.
  • About 40 mL of the dispersion is injected into the measuring cell and measured at 25 ° C.
  • the measuring apparatus measures the particle size distribution on a volume basis with a laser diffraction / scattering type particle size distribution measuring apparatus (for example, LA920 (trade name) manufactured by Horiba, Ltd.).
  • LA920 laser diffraction / scattering type particle size distribution measuring apparatus
  • the refractive index of alumina is used. Even when the inorganic filler is a mixture of alumina and an inorganic filler other than alumina, the refractive index uses that of alumina.
  • the proportion of alumina in inorganic particles having a particle diameter of 1 ⁇ m or less in the inorganic filler is preferably 1% by volume to 40% by volume, more preferably 10% by volume to 35% by volume, and 15% by volume % To 30% by volume is more preferable.
  • the ratio of alumina to the inorganic particles having a particle diameter of 1 ⁇ m or less contained in the inorganic filler can be measured by the following method. For each inorganic particle whose particle diameter is confirmed to be 1 ⁇ m or less by a scanning electron microscope, constituent elements are identified by Energy dispersive X-ray spectrometry, and the material of the inorganic particle is determined.
  • the ratio of alumina to inorganic particles having a particle diameter of 1 ⁇ m or less can be determined.
  • the particle diameter of each inorganic particle is a circle equivalent diameter which is the diameter of a circle having the same area as the projected area.
  • the proportion of alumina in the inorganic particles having a particle diameter of 10 ⁇ m or more in the inorganic filler is preferably 20% by volume to 60% by volume, more preferably 25% by volume to 55% by volume, and 30% by volume More preferably, it is% to 50% by volume.
  • the ratio of alumina in the inorganic particles having a particle diameter of 10 ⁇ m or more contained in the inorganic filler can be determined in the same manner as the ratio of alumina in the inorganic particles having a particle diameter of 1 ⁇ m or less in the inorganic filler.
  • the compounding amount of the inorganic filler is within the range of 75% by mass to 97% by mass with respect to the whole sealing composition from the viewpoints of hygroscopicity, reduction of linear expansion coefficient, strength improvement and solder heat resistance. Preferably, it is more preferably in the range of 80% by mass to 95% by mass.
  • an inorganic filler having an average particle diameter of 0.3 ⁇ m to 0.7 ⁇ m an inorganic filler having an average particle diameter of 7 ⁇ m to 20 ⁇ m, and an inorganic filler having an average particle diameter of 30 ⁇ m to 70 ⁇ m may be used in combination. .
  • the average particle size of the inorganic filler as a whole is preferably 4 ⁇ m to 30 ⁇ m, more preferably 5 ⁇ m to 25 ⁇ m, and still more preferably 6 ⁇ m to 20 ⁇ m.
  • the average particle size of the inorganic filler is a dispersion liquid of the inorganic filler prepared in the same manner as in the measurement of the particle size distribution of the inorganic filler, and a laser diffraction / scattering particle size distribution measuring apparatus (for example, Horiba, Ltd.
  • the sealing composition may further contain a curing accelerator.
  • a hardening accelerator is not restrict
  • the content of the curing accelerator is preferably 0.1% by mass to 8% by mass with respect to the total amount of the epoxy resin and the curing agent.
  • the sealing composition may further contain an ion trapping agent.
  • the ion trap agent that can be used in the present disclosure is not particularly limited as long as it is a generally used ion trap agent in a sealing material used for semiconductor device manufacturing applications, and hydrotalcite etc. It can be mentioned.
  • As the ion trapping agent a compound represented by the following general formula (II-1) or the following general formula (II-2) may be used.
  • Ion trap agents are commercially available.
  • DHT-4A Korean Chemical Industry Co., Ltd., trade name
  • IXE 500 Toagosei Co., Ltd., trade name
  • ion trap agents other than the above, hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony and the like can be mentioned.
  • the ion trap agent may be used alone or in combination of two or more.
  • the content of the ion trap agent is 1 part by mass with respect to 100 parts by mass of the epoxy resin in the sealing composition from the viewpoint of achieving sufficient moisture resistance reliability. It is preferable that it is more than. From the viewpoint of sufficiently exhibiting the effects of the other components, the content of the ion trap agent is preferably 15 parts by mass or less with respect to 100 parts by mass of the epoxy resin in the sealing composition.
  • the average particle size of the ion trap agent is preferably 0.1 ⁇ m to 3.0 ⁇ m, and the maximum particle size is preferably 10 ⁇ m or less.
  • the average particle size of the ion trapping agent can be measured in the same manner as in the case of the inorganic filler.
  • the sealing composition may further contain a coupling agent.
  • the type of coupling agent is not particularly limited, and known coupling agents can be used.
  • As a coupling agent a silane coupling agent and a titanium coupling agent are mentioned, for example.
  • the coupling agent may be used alone or in combination of two or more.
  • silane coupling agent for example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane ⁇ -Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ - [bis ( ⁇ -hydroxyethyl)] aminopropyltriethoxysilane, N - ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, ⁇ - ( ⁇ -aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl)
  • titanium coupling agent for example, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra ( 2,2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylic iso Stearoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl isostearoyl titanate
  • the content of the coupling agent is preferably 3% by mass or less based on the whole of the sealing composition, and from the viewpoint of exerting the effect, 0
  • the content is preferably 1% by mass or more.
  • the sealing composition may further contain a release agent.
  • a mold release agent is not restrict
  • the mold release agent may be used alone or in combination of two or more.
  • the content of the release agent is preferably 10% by mass or less based on the total amount of the epoxy resin and the curing agent, and from the viewpoint of exerting the effect Is preferably 0.5% by mass or more.
  • the sealing composition may contain a colorant (eg, carbon black).
  • the sealing composition may also contain modifiers such as silicone and silicone rubber.
  • the colorant and the modifier may be used alone or in combination of two or more.
  • electroconductive particles such as carbon black
  • electroconductive particles are 1 mass% or less in content rate of particle
  • the content of the conductive particles is preferably 4% by mass or less based on the total amount of the epoxy resin and the curing agent.
  • the method for producing the sealing composition is not particularly limited, and can be carried out by a known method. For example, after a mixture of raw materials of a predetermined compounding amount is sufficiently mixed by a mixer or the like, it can be manufactured by kneading by a heat roll, an extruder or the like, and subjecting to processing such as cooling or crushing.
  • the state of the sealing composition is not particularly limited, and may be powder, solid, liquid or the like.
  • a semiconductor device of the present disclosure includes a semiconductor element and a cured product of the sealing composition of the present disclosure formed by sealing the semiconductor element.
  • the method for sealing the semiconductor element using the sealing composition is not particularly limited, and a known method can be applied.
  • transfer molding is generally used, but compression molding, injection molding, etc. may be used.
  • the semiconductor device of the present disclosure is suitable as an IC, a large scale integration (LSI) circuit, or the like.
  • LSI large scale integration
  • Examples 1 to 11 and Comparative Examples 1 and 2 After pre-mixing (dry blending) the materials of the formulations shown in Tables 1 to 3, the mixture is kneaded for about 15 minutes with a biaxial roll (roll surface temperature: about 80 ° C.), and is cooled and pulverized to obtain a powdery sealing composition Manufactured.
  • Epoxy resin 1 Biphenyl type epoxy resin, epoxy equivalent: 186 g / eq -Epoxy resin 2: Multifunctional epoxy resin, epoxy equivalent: 167 g / eq
  • Epoxy resin 3 bisphenol type crystalline epoxy resin, epoxy equivalent: 192 g / eq ⁇
  • Epoxy resin 4 Bis-F type epoxy resin, epoxy equivalent: 159 g / eq
  • Curing agent 1 Multifunctional phenolic resin, triphenylmethane type phenolic resin having a hydroxyl equivalent of 102 g / eq
  • Curing agent 2 Multifunctional phenolic resin, biphenyl having a hydroxyl equivalent of 205 g / eq
  • Curing agent 3 Phenol ⁇ Aralkyl resin, hydroxyl equivalent: 170 g / eq
  • Hardening accelerator Phosphorus hardening accelerator
  • Coupling agent Epoxysilane ( ⁇ -glycidoxypropyltrimethoxysilane) -Releasing agent: Montanic acid ester-Coloring agent: Carbon black-Ion trap agent: Hydrotalcite-Modifier: Silicone
  • Inorganic filler ⁇ Inorganic filler 1: Mixture of alumina and silica (average particle size: 8.6 ⁇ m) ⁇ Inorganic filler 2: silica (average particle size: 9.5 ⁇ m) ⁇ Inorganic filler 3: alumina (average particle size: 0.4 ⁇ m) ⁇ Inorganic filler 4: silica (average particle size: 0.8 ⁇ m) ⁇ Inorganic filler 5: silica (average particle size: 0.1 ⁇ m) ⁇ Inorganic filler 6: silica (average particle size: 13.0 ⁇ m) ⁇ Inorganic filler 7: silica (average particle size: 2.2 ⁇ m) ⁇ Inorganic filler 8: silica (average particle size: 0.8 ⁇ m) ⁇ Inorganic filler 9: mixture of alumina and silica (average particle size: 7.4 ⁇ m) ⁇ Inorganic filler 10: silica (average particle size: 1.5 ⁇ m) ⁇ Inorganic filler
  • the positions of peaks in the particle size distribution of the inorganic filler of Examples 1 to 11 are as follows: It had 3 peaks.
  • the sealing compositions according to Examples 1 to 11 all contained alumina having a particle diameter of 1 ⁇ m or less.
  • the average particle size of the entire inorganic filler is shown below.
  • Example 1 0.45 ⁇ m, 10 ⁇ m and 40 ⁇ m (average particle size: 8.1 ⁇ m)
  • Example 2 0.5 ⁇ m, 10 ⁇ m and 50 ⁇ m (average particle size: 8.7 ⁇ m)
  • Example 3 0.5 ⁇ m, 10 ⁇ m and 50 ⁇ m (average particle size: 7.6 ⁇ m)
  • Example 4 0.5 ⁇ m, 10 ⁇ m and 50 ⁇ m (average particle size: 7.7 ⁇ m)
  • Example 5 0.5 ⁇ m, 10 ⁇ m and 50 ⁇ m (average particle size: 6.6 ⁇ m)
  • Example 6 0.5 ⁇ m, 10 ⁇ m and 51 ⁇ m (average particle size: 6.2 ⁇ m)
  • Example 7 0.5 ⁇ m, 10 ⁇ m and 51 ⁇ m (average particle size: 7.7 ⁇ m)
  • Example 8 0.5 ⁇ m, 10 ⁇ m and 51 ⁇ m (average particle size: 6.6 ⁇ m)
  • Example 9 0.5 ⁇ m, 10 ⁇ m and 51
  • the sealing composition which concerns on the comparative example 1 contained the alumina whose particle diameter is 1 micrometer or less.
  • the average particle size of the entire inorganic filler is shown below. Comparative Example 1: 1.5 ⁇ m and 10 ⁇ m (average particle size: 11.3 ⁇ m)
  • the position of the peak in the particle size distribution of the inorganic filler of the comparative example 2 was as follows, and had three peaks.
  • the sealing composition which concerns on the comparative example 2 did not contain the alumina whose particle diameter is 1 micrometer or less.
  • the average particle size of the entire inorganic filler is shown below. Comparative Example 2: 0.5 ⁇ m, 10 ⁇ m and 50 ⁇ m (average particle size: 6.5 ⁇ m)
  • the evaluation of the flowability of the sealing composition was performed by a spiral flow test. Specifically, the sealing composition was molded using a spiral flow measurement die according to EMMI-1-66, and the flow distance (cm) of the molded product of the sealing composition was measured. Molding of the sealing composition was performed using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds. Moreover, fluidity set 160 cm or more to A, 150 cm or more and less than 160 cm as B, and less than 150 cm as C.
  • the evaluation of the thermal conductivity of the sealing composition was performed by the following method. Specifically, transfer molding was performed using the prepared sealing composition under conditions of a mold temperature of 180 ° C., a molding pressure of 7 MPa, and a curing time of 300 seconds, to obtain a molded product having a mold shape. The density of the obtained cured product measured by the Archimedes method was 2.8 g / cm 3 to 3.0 g / cm 3 . Further, the thermal diffusivity of the cured product was measured by a laser flash method using a thermal diffusivity measuring device (LFA 467, manufactured by NETZSCH).
  • LFA 467 thermal diffusivity measuring device
  • the thermal conductivity (W / (m ⁇ K)) was calculated from the product of the thermal diffusivity measured above, the density measured by the Archimedes method, and the specific heat measured by DSC (differential calorimeter). In addition, the thermal conductivity is A at 2.5 W / (m ⁇ K) or more, and B at less than 2.5 W / (m ⁇ K).
  • Comparative Example 2 in which the inorganic filler does not contain alumina having a particle diameter of 1 ⁇ m or less is an example 1, 5, 6, 8, which has particularly large amounts of alumina having a particle diameter of 1 ⁇ m or less in the inorganic filler. Compared to 10 and 11, the flowability was comparable or lower and the thermal conductivity resulted in lower.

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  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
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Abstract

This sealing composition contains an epoxy resin, a curing agent, and an inorganic filler material. The particle size distribution of the inorganic filler material has at least three peaks, and the inorganic filler material includes alumina with a particle diameter of less than or equal to 1 µm.<u> <b/> </u> <u> <b/> </u>

Description

封止組成物及び半導体装置Encapsulation composition and semiconductor device
　本発明は、封止組成物及び半導体装置に関する。 The present invention relates to a sealing composition and a semiconductor device.
　近年、小型化及び高集積化に伴い、半導体パッケージ内部の発熱が懸念されている。発熱により、半導体パッケージを有する電気部品又は電子部品の性能低下が生じる恐れがあるため、半導体パッケージに使用される部材には、高い熱伝導性が求められている。そのため、半導体パッケージの封止材を高熱伝導化することが求められている。
　封止材を高熱伝導化する手法の一つとして、封止材に含まれる無機充填材に高熱伝導性フィラーであるアルミナを用いる方法が挙げられる（例えば、特許文献１参照）。 In recent years, with miniaturization and high integration, there is a concern about heat generation inside the semiconductor package. Since the heat generation may cause a decrease in performance of an electrical part or an electronic part having a semiconductor package, members used for the semiconductor package are required to have high thermal conductivity. Therefore, high thermal conductivity of the sealing material of the semiconductor package is required.
As one of the methods for increasing the thermal conductivity of the sealing material, there is a method of using alumina, which is a high thermal conductivity filler, as the inorganic filler contained in the sealing material (see, for example, Patent Document 1).
特開２００６－２７３９２０号公報JP, 2006-273920, A
　しかし、特許文献１に記載の方法では、封止材の流動性が悪化することがある。例えば、半導体素子と基板とをワイヤを介して接続するワイヤボンディング構造と呼ばれる方法を採用した半導体パッケージは、半導体素子と、基板と、これらを電気的に接続しているワイヤとを樹脂組成物で封止することにより形成される。その際、封止材の流動によりワイヤに圧力がかかり、ワイヤの位置ずれ（ワイヤ流れ）が生じたり、半導体素子の保護が充分にされないことがある。
　このように、封止材の流動性と高熱伝導性とを両立することは、困難な場合がある。 However, in the method described in Patent Document 1, the flowability of the sealing material may be deteriorated. For example, a semiconductor package adopting a method called a wire bonding structure in which a semiconductor element and a substrate are connected via a wire uses a resin composition for the semiconductor element, the substrate, and a wire electrically connecting these. It is formed by sealing. At this time, pressure is applied to the wire due to the flow of the sealing material, which may cause displacement of the wire (wire flow) or insufficient protection of the semiconductor element.
As described above, it may be difficult to achieve both the flowability of the sealing material and the high thermal conductivity.
　本発明の一形態は、上記従来の事情に鑑みてなされたものであり、流動性に優れ高い熱伝導性を有する封止組成物及びそれを用いた半導体装置を提供することを目的とする。 One aspect of the present invention is made in view of the above-mentioned conventional circumstances, and it aims at providing a sealing composition which is excellent in fluidity and has high thermal conductivity, and a semiconductor device using the same.
　前記課題を達成するための具体的手段は以下の通りである。
　　＜１＞　エポキシ樹脂と、硬化剤と、無機充填材とを含有し、
　前記無機充填材の粒度分布が、少なくとも３つのピークを有し、
　前記無機充填材が、粒子径が１μｍ以下のアルミナを含む封止組成物。
　　＜２＞　前記無機充填材の粒度分布が、０．３μｍ～０．７μｍの範囲、７μｍ～２０μｍの範囲及び３０μｍ～７０μｍの範囲にピークを有する＜１＞に記載の封止組成物。
　　＜３＞　前記無機充填材に含まれる粒子径が１μｍ以下の無機粒子に占めるアルミナの割合が、１体積％～４０体積％である＜１＞又は＜２＞に記載の封止組成物。
　　＜４＞　前記無機充填材の平均円形度が、０．８０以上である＜１＞～＜３＞のいずれか１項に記載の封止組成物。
　　＜５＞　半導体素子と、前記半導体素子を封止してなる＜１＞～＜４＞のいずれか１項に記載の封止組成物の硬化物と、を含む半導体装置。 The specific means for achieving the said subject are as follows.
<1> containing an epoxy resin, a curing agent, and an inorganic filler,
The particle size distribution of the inorganic filler has at least three peaks,
The sealing composition in which the said inorganic filler contains an alumina with a particle diameter of 1 micrometer or less.
<2> The sealing composition according to <1>, wherein the particle size distribution of the inorganic filler has a peak in a range of 0.3 μm to 0.7 μm, a range of 7 μm to 20 μm, and a range of 30 μm to 70 μm.
<3> The sealing composition according to <1> or <2>, wherein a ratio of alumina in inorganic particles having a particle diameter of 1 μm or less in the inorganic filler is 1% by volume to 40% by volume.
<4> The sealing composition according to any one of <1> to <3>, wherein the average circularity of the inorganic filler is 0.80 or more.
<5> A semiconductor device comprising: a semiconductor element; and a cured product of the sealing composition according to any one of <1> to <4>, wherein the semiconductor element is sealed.
　本発明の一形態によれば、流動性に優れ高い熱伝導性を有する封止組成物及びそれを用いた半導体装置を提供することができる。 According to one aspect of the present invention, it is possible to provide a sealing composition having excellent fluidity and high thermal conductivity, and a semiconductor device using the same.
　以下、本発明の封止組成物及び半導体装置を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。
　本開示において「～」を用いて示された数値範囲には、「～」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
　本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本開示において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
　本開示においては、各成分に該当する粒子を複数種含んでいてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。 Hereafter, the form for implementing the sealing composition and semiconductor device of this invention is demonstrated in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.
In the present disclosure, numerical values described before and after “to” are included in the numerical range indicated using “to” as the minimum value and the maximum value, respectively.
The upper limit value or the lower limit value described in one numerical value range may be replaced with the upper limit value or the lower limit value of the other stepwise description numerical value range in the numerical value range described stepwise in the present disclosure. . In addition, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the example.
In the present disclosure, each component may contain a plurality of corresponding substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of particles corresponding to each component may be contained. When there are a plurality of particles corresponding to each component in the composition, the particle diameter of each component means the value for the mixture of the plurality of particles present in the composition unless otherwise specified.
＜封止組成物＞
　本開示の封止組成物は、エポキシ樹脂と、硬化剤と、無機充填材とを含有し、前記無機充填材の粒度分布が、少なくとも３つのピークを有し、前記無機充填材が、粒子径が１μｍ以下のアルミナを含む。
　本開示の封止組成物は、流動性に優れ高い熱伝導性を有する。その理由は明確ではないが、以下のように推察される。
　封止組成物に含まれる無機充填材は、少なくとも３つのピークを有する粒度分布を示す。つまり、無機充填材は、少なくとも、大粒子径の無機粒子と中粒子径の無機粒子と小粒子径の無機粒子とを含んで構成される。無機充填材が大粒子径の無機粒子と中粒子径の無機粒子と小粒子径の無機粒子とを含むため、本開示の封止組成物は流動性に優れると考えられる。
　また、無機充填材は、粒子径が１μｍ以下のアルミナを含むところ、アルミナは上述のように、高い熱伝導性を示す。また、粒子径が１μｍ以下のアルミナは、封止組成物に含まれる無機充填材としては、小粒子径の無機粒子に該当する。小粒子径の無機粒子としてアルミナを含むことで、大粒子径の無機粒子及び中粒子径の無機粒子の間に小粒子径の無機粒子であるアルミナが介在しやすくなる。高い熱伝導性を示すアルミナが大粒子径の無機粒子及び中粒子径の無機粒子の間に介在することで、大粒子径の無機粒子及び中粒子径の無機粒子の間の熱伝導を促進することができる。その結果として、本開示の封止組成物は高い熱伝導性を有すると推察される。 <Sealing composition>
The sealing composition of the present disclosure contains an epoxy resin, a curing agent, and an inorganic filler, and the particle size distribution of the inorganic filler has at least three peaks, and the inorganic filler has a particle diameter. Contains alumina of 1 μm or less.
The sealing composition of the present disclosure has excellent fluidity and high thermal conductivity. Although the reason is not clear, it is guessed as follows.
The inorganic filler contained in the sealing composition exhibits a particle size distribution having at least three peaks. That is, the inorganic filler is configured to include at least inorganic particles having a large particle size, inorganic particles having a medium particle size, and inorganic particles having a small particle size. Since the inorganic filler contains large particle size inorganic particles, medium particle size inorganic particles, and small particle size inorganic particles, the sealing composition of the present disclosure is considered to be excellent in fluidity.
In addition, the inorganic filler contains alumina having a particle diameter of 1 μm or less, and the alumina exhibits high thermal conductivity as described above. In addition, alumina having a particle diameter of 1 μm or less corresponds to inorganic particles having a small particle diameter as the inorganic filler contained in the sealing composition. By including alumina as the small particle size inorganic particles, alumina, which is a small particle size inorganic particle, is easily intervened between the large particle size inorganic particle and the medium particle size inorganic particle. The thermal conductivity between the large particle size inorganic particles and the medium particle size inorganic particles is promoted by interposing the alumina exhibiting high thermal conductivity between the large particle size inorganic particles and the medium particle size inorganic particles. be able to. As a result, it is assumed that the sealing composition of the present disclosure has high thermal conductivity.
　以下、封止組成物を構成する各成分について説明する。本開示の封止組成物は、エポキシ樹脂と、硬化剤と、無機充填材とを含有し、必要に応じてその他の成分を含有してもよい。 Hereinafter, each component which comprises a sealing composition is demonstrated. The sealing composition of the present disclosure contains an epoxy resin, a curing agent, and an inorganic filler, and may contain other components as needed.
－エポキシ樹脂－
　封止組成物は、エポキシ樹脂を含有する。エポキシ樹脂の種類は特に限定されず、公知のエポキシ樹脂を使用することができる。
　具体的には、例えば、フェノール化合物（例えば、フェノール、クレゾール、キシレノール、レゾルシン、カテコール、ビスフェノールＡ及びビスフェノールＦ）並びにナフトール化合物（例えば、α－ナフトール、β－ナフトール及びジヒドロキシナフタレン）からなる群より選択される少なくとも１種と、アルデヒド化合物（例えば、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド及びサリチルアルデヒド）と、を酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂をエポキシ化したもの（例えば、フェノールノボラック型エポキシ樹脂及びオルソクレゾールノボラック型エポキシ樹脂）；ビスフェノール（例えば、ビスフェノールＡ、ビスフェノールＡＤ、ビスフェノールＦ及びビスフェノールＳ）及びビフェノール（例えば、アルキル置換及び非置換のビフェノール）からなる群より選択される少なくとも１種のジグリシジルエーテル；フェノール・アラルキル樹脂のエポキシ化物；フェノール化合物とジシクロペンタジエン及びテルペン化合物からなる群より選択される少なくとも１種との付加物又は重付加物のエポキシ化物；多塩基酸（例えば、フタル酸及びダイマー酸）とエピクロルヒドリンの反応により得られるグリシジルエステル型エポキシ樹脂；ポリアミン（例えば、ジアミノジフェニルメタン及びイソシアヌル酸）とエピクロルヒドリンとの反応により得られるグリシジルアミン型エポキシ樹脂；オレフィン結合を過酸（例えば、過酢酸）で酸化して得られる線状脂肪族エポキシ樹脂；並びに脂環族エポキシ樹脂が挙げられる。エポキシ樹脂は、１種類を単独で使用しても、２種類以上を併用してもよい。 -Epoxy resin-
The sealing composition contains an epoxy resin. The type of epoxy resin is not particularly limited, and known epoxy resins can be used.
Specifically, for example, it is selected from the group consisting of phenol compounds (for example, phenol, cresol, xylenol, resorcine, catechol, bisphenol A and bisphenol F) and naphthol compounds (for example, α-naphthol, β-naphthol and dihydroxynaphthalene) Epoxidized novolak resin obtained by condensation or cocondensation of at least one of the following compounds with an aldehyde compound (eg, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde) under an acidic catalyst (eg, phenol Novolac type epoxy resin and ortho cresol novolac type epoxy resin); bisphenol (for example, bisphenol A, bisphenol AD, bisphenol F and bisphenol) At least one diglycidyl ether selected from the group consisting of (S) and biphenols (eg, alkyl-substituted and non-substituted biphenols); epoxidized phenol / aralkyl resins; consisting of phenol compounds and dicyclopentadiene and terpene compounds Epoxides of adducts or polyadducts with at least one selected from the group: glycidyl ester type epoxy resins obtained by the reaction of polybasic acids (for example, phthalic acid and dimer acid) with epichlorohydrin; polyamines (for example, diamino Glycidylamine type epoxy resins obtained by reaction of diphenylmethane and isocyanuric acid with epichlorohydrin; Linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracid (eg, peracetic acid); and Aliphatic epoxy resins It is below. The epoxy resin may be used alone or in combination of two or more.
　集積回路（Ｉｎｔｅｇｒａｔｅｄ　Ｃｉｒｃｕｉｔ、ＩＣ）等の素子上のアルミニウム配線又は銅配線の腐食防止の観点から、エポキシ樹脂の純度は高い方が好ましく、加水分解性塩素量は少ない方が好ましい。封止組成物の耐湿性の向上の観点からは、加水分解性塩素量は質量基準で５００ｐｐｍ以下であることが好ましい。 From the viewpoint of preventing corrosion of aluminum wiring or copper wiring on an element such as an integrated circuit (IC), the purity of the epoxy resin is preferably high, and the amount of hydrolyzable chlorine is preferably small. From the viewpoint of improving the moisture resistance of the sealing composition, the amount of hydrolyzable chlorine is preferably 500 ppm or less on a mass basis.
　ここで、加水分解性塩素量は、試料のエポキシ樹脂１ｇをジオキサン３０ｍＬに溶解し、１Ｎ－ＫＯＨメタノール溶液５ｍＬを添加して３０分間リフラックスした後、電位差滴定により求めた値である。 Here, the amount of hydrolyzable chlorine is a value determined by potentiometric titration after dissolving 1 g of the epoxy resin as a sample in 30 mL of dioxane, adding 5 mL of 1N-KOH methanol solution and refluxing for 30 minutes.
　封止組成物に占めるエポキシ樹脂の含有率は、１．５質量％～２０質量％であることが好ましく、２．０質量％～１５質量％であることがより好ましく、３．０質量％～１０質量％であることがさらに好ましい。
　無機充填材を除く封止組成物に占めるエポキシ樹脂の含有率は、３０質量％～６５質量％であることが好ましく、３５質量％～６０質量％であることがより好ましく、４０質量％～５５質量％であることがさらに好ましい。 The content of the epoxy resin in the sealing composition is preferably 1.5% by mass to 20% by mass, more preferably 2.0% by mass to 15% by mass, and 3.0% by mass or more More preferably, it is 10% by mass.
The content of the epoxy resin in the sealing composition excluding the inorganic filler is preferably 30% by mass to 65% by mass, more preferably 35% by mass to 60% by mass, and 40% by mass to 55% by mass. More preferably, it is mass%.
－硬化剤－
　封止組成物は、硬化剤を含有する。硬化剤の種類は特に限定されず、公知の硬化剤を使用することができる。
　具体的には、例えば、フェノール化合物（例えば、フェノール、クレゾール、レゾルシン、カテコール、ビスフェノールＡ及びビスフェノールＦ）並びにナフトール化合物（例えば、α－ナフトール、β－ナフトール及びジヒドロキシナフタレン）からなる群より選択される少なくとも１種と、アルデヒド化合物（例えば、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド及びサリチルアルデヒド）とを、酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂；フェノール・アラルキル樹脂；ビフェニル・アラルキル樹脂；並びにナフトール・アラルキル樹脂；が挙げられる。硬化剤は１種類を単独で使用しても、２種類以上を併用してもよい。中でも、硬化剤としては、耐リフロー性向上の観点から、フェノール・アラルキル樹脂が好ましい。硬化剤は、１種類を単独で使用しても、２種類以上を併用してもよい。 -Hardener-
The sealing composition contains a curing agent. The type of curing agent is not particularly limited, and known curing agents can be used.
Specifically, for example, it is selected from the group consisting of phenol compounds (eg, phenol, cresol, resorcine, catechol, bisphenol A and bisphenol F) and naphthol compounds (eg, α-naphthol, β-naphthol and dihydroxynaphthalene) Novolak resin obtained by condensation or cocondensation of at least one type and an aldehyde compound (eg, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde) under an acidic catalyst; phenol / aralkyl resin; biphenyl / aralkyl resin; And naphthol / aralkyl resins. The curing agent may be used alone or in combination of two or more. Among them, as the curing agent, a phenol / aralkyl resin is preferable from the viewpoint of improving the reflow resistance. The curing agent may be used alone or in combination of two or more.
　硬化剤の官能基（例えば、ノボラック樹脂の場合にはフェノール性水酸基）の当量がエポキシ樹脂のエポキシ基１当量に対して０．５当量～１．５当量になるように、硬化剤が配合されることが好ましく、特に、０．７当量～１．２当量になるように硬化剤が配合されることが好ましい。 The curing agent is blended such that the equivalent of the functional group of the curing agent (for example, phenolic hydroxyl group in the case of novolak resin) is 0.5 equivalent to 1.5 equivalents to 1 equivalent of epoxy group of the epoxy resin. The curing agent is preferably blended so as to be 0.7 equivalents to 1.2 equivalents.
－無機充填材－
　封止組成物は、無機充填材を含む。無機充填材を含むことで、封止組成物の吸湿性が低減し、硬化状態での強度が向上する傾向にある。 -Inorganic filler-
The sealing composition comprises an inorganic filler. By including the inorganic filler, the hygroscopicity of the sealing composition is reduced, and the strength in the cured state tends to be improved.
　無機充填材は、１種類を単独で使用しても、２種類以上を併用してもよい。
　無機充填材を２種類以上併用する場合としては、例えば、成分、平均粒子径、形状等が異なる無機充填材を２種類以上用いる場合が挙げられる。
　無機充填材の形状は特に制限されず、例えば、粉状、球状、繊維状等が挙げられる。封止組成物の成形時の流動性及び金型摩耗性の点からは、球状であることが好ましい。 The inorganic filler may be used alone or in combination of two or more.
As a case where two or more types of inorganic fillers are used in combination, there may be mentioned, for example, a case where two or more types of inorganic fillers having different components, average particle diameter, shape and the like are used.
The shape of the inorganic filler is not particularly limited, and examples thereof include powder, sphere, and fiber. It is preferable that it is spherical shape from the point of the fluidity | liquidity at the time of shaping | molding of sealing composition, and a mold abrasion property.
　無機充填材の平均円形度は、０．８０以上であることが好ましく、０．８５以上であることがより好ましく、０．９０以上であることがさらに好ましく、０．９３以上であることが特に好ましい。また、無機充填材の平均円形度は、１．０以下であってもよい。
　無機充填材の円形度とは、無機充填材の投影面積と同じ面積を持つ円の直径である円相当径から算出される円としての周囲長を、無機充填材の投影像から測定される周囲長（輪郭線の長さ）で除して得られる数値であり、下記式で求められる。尚、円形度は真円では１．００となる。
　　円形度＝（相当円の周囲長）／（粒子断面像の周囲長）
　具体的に平均円形度は、走査型電子顕微鏡で倍率１０００倍に拡大した画像を観察し、任意に１０個の無機充填材を選択し、上記方法にて個々の無機充填材の円形度を測定し、その算術平均値として算出される値である。なお、円形度、相当円の周囲長及び粒子の投影像の周囲長は、市販されている画像解析ソフトによって求めることが可能である。
　無機充填材として２種類以上が併用される場合、無機充填材の平均円形度は、２種類以上の無機充填材の混合物としての値をいう。 The average circularity of the inorganic filler is preferably 0.80 or more, more preferably 0.85 or more, still more preferably 0.90 or more, and particularly preferably 0.93 or more. preferable. The average circularity of the inorganic filler may be 1.0 or less.
The circularity of the inorganic filler is the circumference measured from the projected image of the inorganic filler, as the circle equivalent diameter calculated from the equivalent circle diameter which is the diameter of a circle having the same area as the projected area of the inorganic filler It is a numerical value obtained by dividing by the length (length of contour line), and is obtained by the following equation. The roundness is 1.00 for a true circle.
Circularity = (perimeter of equivalent circle) / (perimeter of particle cross-sectional image)
Specifically, the average circularity is observed by a scanning electron microscope at a magnification of 1000 times, an image of 10 inorganic fillers is arbitrarily selected, and the circularity of each inorganic filler is measured by the above method. And the value calculated as the arithmetic mean value. The degree of circularity, the circumferential length of the equivalent circle, and the circumferential length of the projected image of particles can be determined by commercially available image analysis software.
When two or more types are used together as an inorganic filler, the average roundness of an inorganic filler says the value as a mixture of two or more types of inorganic fillers.
　無機充填材としては、粒度分布が、少なくとも３つのピークを有し、粒子径が１μｍ以下のアルミナを含むものであれば、材質、粒子径等について特に限定されるものではない。
　無機充填材としては、球状シリカ、結晶シリカ等のシリカ、アルミナ、ジルコン、酸化マグネシウム、珪酸カルシウム、炭酸カルシウム、チタン酸カリウム、炭化珪素、窒化珪素、窒化ホウ素、窒化アルミニウム、ベリリア、ジルコニアなどが挙げられる。さらに、難燃効果のある無機充填材としては水酸化アルミニウム、硼酸亜鉛等が挙げられる。これらの中でも、高熱伝導性の観点からはアルミナが好ましい。
　無機充填材に占めるアルミナの割合は、６０質量％～９５質量％であることが好ましく、６０質量％～９２質量％であることがより好ましく、６０質量％～９０質量％であることがさらに好ましい。
　無機充填材としては、アルミナとシリカとを併用してもよい。無機充填材としてアルミナとシリカとを併用する場合、無機充填材に占めるアルミナの割合が８０質量％～９５質量％であり、シリカの割合が５質量％～２０質量％であることが好ましく、アルミナの割合が８２質量％～９２質量％であり、シリカの割合が８質量％～１８質量％であることがより好ましく、アルミナの割合が８５質量％～９０質量％であり、シリカの割合が１０質量％～１５質量％であることがさらに好ましい。 The inorganic filler is not particularly limited with respect to the material, the particle diameter and the like, as long as the inorganic filler has alumina having a particle size distribution having at least three peaks and having a particle diameter of 1 μm or less.
Examples of the inorganic filler include spherical silica, silica such as crystalline silica, alumina, zircon, magnesium oxide, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, boron nitride, aluminum nitride, beryllia, zirconia, etc. Be Further, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide and zinc borate. Among these, alumina is preferable from the viewpoint of high thermal conductivity.
The proportion of alumina in the inorganic filler is preferably 60% by mass to 95% by mass, more preferably 60% by mass to 92% by mass, and still more preferably 60% by mass to 90% by mass. .
As the inorganic filler, alumina and silica may be used in combination. When alumina and silica are used in combination as the inorganic filler, the proportion of alumina in the inorganic filler is preferably 80% by mass to 95% by mass, and the proportion of silica is preferably 5% by mass to 20% by mass, alumina Of 82% by mass to 92% by mass, more preferably 8% by mass to 18% by mass of silica, and 85% by mass to 90% by mass of alumina; It is more preferable that the content is 15% by mass.
　無機充填材の粒度分布は、少なくとも３つのピークを有するものであり、３つのピークを有することが好ましい。無機充填材の粒度分布におけるピークの位置は特に限定されるものではなく、例えば、０．３μｍ～０．７μｍの範囲、７μｍ～２０μｍの範囲及び３０μｍ～７０μｍの範囲にピークを有することが好ましく、０．３μｍ～０．６μｍの範囲、７μｍ～１５μｍの範囲及び４０μｍ～７０μｍの範囲にピークを有することがより好ましい。 The particle size distribution of the inorganic filler has at least three peaks, preferably three peaks. The position of the peak in the particle size distribution of the inorganic filler is not particularly limited, and preferably has a peak in the range of 0.3 μm to 0.7 μm, in the range of 7 μm to 20 μm, and in the range of 30 μm to 70 μm, It is more preferable to have peaks in the range of 0.3 μm to 0.6 μm, in the range of 7 μm to 15 μm, and in the range of 40 μm to 70 μm.
　無機充填材の粒度分布は、下記方法で求めることができる。
　溶媒（純水）に、測定対象の無機充填材を０．０２質量％～０．０８質量％の範囲内で添加し、１１０Ｗのバス式超音波洗浄機で１分～１０分振動し、無機充填材を分散する。分散液の約４０ｍＬ程度を測定セルに注入して２５℃で測定する。測定装置は、レーザー回折／散乱式粒子径分布測定装置（例えば、株式会社堀場製作所、ＬＡ９２０（商品名））にて、体積基準の粒度分布を測定する。なお、屈折率はアルミナの屈折率を用いる。無機充填材がアルミナとアルミナ以外の無機充填材の混合物である場合においても、屈折率はアルミナの屈折率を用いるものとする。 The particle size distribution of the inorganic filler can be determined by the following method.
An inorganic filler to be measured is added to a solvent (pure water) in the range of 0.02% by mass to 0.08% by mass, and vibrated for 1 to 10 minutes with a 110 W bath ultrasonic cleaner, Disperse the filler. About 40 mL of the dispersion is injected into the measuring cell and measured at 25 ° C. The measuring apparatus measures the particle size distribution on a volume basis with a laser diffraction / scattering type particle size distribution measuring apparatus (for example, LA920 (trade name) manufactured by Horiba, Ltd.). Here, the refractive index of alumina is used. Even when the inorganic filler is a mixture of alumina and an inorganic filler other than alumina, the refractive index uses that of alumina.
　無機充填材に含まれる粒子径が１μｍ以下の無機粒子に占めるアルミナの割合は、１体積％～４０体積％であることが好ましく、１０体積％～３５体積％であることがより好ましく、１５体積％～３０体積％であることがさらに好ましい。
　無機充填材に含まれる粒子径が１μｍ以下の無機粒子に占めるアルミナの割合は、以下の方法により測定することができる。
　走査型電子顕微鏡により粒子径が１μｍ以下と確認された各無機粒子について、エネルギー分散型Ｘ線分析（Ｅｎｅｒｇｙ　ｄｉｓｐｅｒｓｉｖｅ　Ｘ－ｒａｙ　ｓｐｅｃｔｒｏｍｅｔｒｙ）により構成元素を同定し、無機粒子の材質を確定する。１μｍ以下の無機粒子５０個に占めるアルミナの体積基準の割合を求めることで、無機充填材に含まれる粒子径が１μｍ以下の無機粒子に占めるアルミナの割合を求めることができる。各無機粒子の粒子径は、投影面積と同じ面積を持つ円の直径である円相当径とする。 The proportion of alumina in inorganic particles having a particle diameter of 1 μm or less in the inorganic filler is preferably 1% by volume to 40% by volume, more preferably 10% by volume to 35% by volume, and 15% by volume % To 30% by volume is more preferable.
The ratio of alumina to the inorganic particles having a particle diameter of 1 μm or less contained in the inorganic filler can be measured by the following method.
For each inorganic particle whose particle diameter is confirmed to be 1 μm or less by a scanning electron microscope, constituent elements are identified by Energy dispersive X-ray spectrometry, and the material of the inorganic particle is determined. By determining the volume-based ratio of alumina to 50 inorganic particles of 1 μm or less, the ratio of alumina to inorganic particles having a particle diameter of 1 μm or less can be determined. The particle diameter of each inorganic particle is a circle equivalent diameter which is the diameter of a circle having the same area as the projected area.
　無機充填材に含まれる粒子径が１０μｍ以上の無機粒子に占めるアルミナの割合は、２０体積％～６０体積％であることが好ましく、２５体積％～５５体積％であることがより好ましく、３０体積％～５０体積％であることがさらに好ましい。
　無機充填材に含まれる粒子径が１０μｍ以上の無機粒子に占めるアルミナの割合は、無機充填材に含まれる粒子径が１μｍ以下の無機粒子に占めるアルミナの割合と同様にして求めることができる。 The proportion of alumina in the inorganic particles having a particle diameter of 10 μm or more in the inorganic filler is preferably 20% by volume to 60% by volume, more preferably 25% by volume to 55% by volume, and 30% by volume More preferably, it is% to 50% by volume.
The ratio of alumina in the inorganic particles having a particle diameter of 10 μm or more contained in the inorganic filler can be determined in the same manner as the ratio of alumina in the inorganic particles having a particle diameter of 1 μm or less in the inorganic filler.
　無機充填材の配合量としては、吸湿性、線膨張係数の低減、強度向上及びはんだ耐熱性の観点から、封止組成物全体に対して７５質量％～９７質量％の範囲内であることが好ましく、８０質量％～９５質量％の範囲内であることがより好ましい。 The compounding amount of the inorganic filler is within the range of 75% by mass to 97% by mass with respect to the whole sealing composition from the viewpoints of hygroscopicity, reduction of linear expansion coefficient, strength improvement and solder heat resistance. Preferably, it is more preferably in the range of 80% by mass to 95% by mass.
　無機充填材が少なくとも３つのピークを有する粒度分布を示すためには、例えば、平均粒子径の異なる３種類の無機充填材を配合する方法が挙げられるが、これに限定されることはない。例えば、平均粒子径が０．３μｍ～０．７μｍの無機充填材と、平均粒子径が７μｍ～２０μｍの無機充填材と、平均粒子径が３０μｍ～７０μｍの無機充填材とを併用してもよい。
　無機充填材全体としての平均粒子径は、４μｍ～３０μｍであることが好ましく、５μｍ～２５μｍであることがより好ましく、６μｍ～２０μｍであることがさらに好ましい。
　無機充填材の平均粒子径は、無機充填材の粒度分布の測定の場合と同様にして調製した無機充填材の分散液を用い、レーザー回折／散乱式粒子径分布測定装置（例えば、株式会社堀場製作所、ＬＡ９２０（商品名））にて測定される体積基準の粒度分布において、小径側からの累積が５０％となるときの粒子径（Ｄ５０％）として求められる。 In order to show the particle size distribution which an inorganic filler has at least 3 peaks, although the method of mix | blending three types of inorganic fillers from which an average particle diameter differs is mentioned, it is not limited to this, for example. For example, an inorganic filler having an average particle diameter of 0.3 μm to 0.7 μm, an inorganic filler having an average particle diameter of 7 μm to 20 μm, and an inorganic filler having an average particle diameter of 30 μm to 70 μm may be used in combination. .
The average particle size of the inorganic filler as a whole is preferably 4 μm to 30 μm, more preferably 5 μm to 25 μm, and still more preferably 6 μm to 20 μm.
The average particle size of the inorganic filler is a dispersion liquid of the inorganic filler prepared in the same manner as in the measurement of the particle size distribution of the inorganic filler, and a laser diffraction / scattering particle size distribution measuring apparatus (for example, Horiba, Ltd. The particle size distribution (D50%) at which the accumulation from the small diameter side becomes 50% in the volume-based particle size distribution measured by a manufacturing company, LA920 (trade name).
（硬化促進剤）
　封止組成物は、硬化促進剤をさらに含有してもよい。硬化促進剤の種類は特に制限されず、公知の硬化促進剤を使用することができる。
　具体的には、１，８－ジアザ－ビシクロ［５．４．０］ウンデセン－７、１，５－ジアザ－ビシクロ［４．３．０］ノネン、５，６－ジブチルアミノ－１，８－ジアザ－ビシクロ［５．４．０］ウンデセン－７等のシクロアミジン化合物；シクロアミジン化合物に無水マレイン酸、１，４－ベンゾキノン、２，５－トルキノン、１，４－ナフトキノン、２，３－ジメチルベンゾキノン、２，６－ジメチルベンゾキノン、２，３－ジメトキシ－５－メチル－１，４－ベンゾキノン、２，３－ジメトキシ－１，４－ベンゾキノン、フェニル－１，４－ベンゾキノン等のキノン化合物、ジアゾフェニルメタン、フェノール樹脂などのπ結合をもつ化合物を付加してなる分子内分極を有する化合物；ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の３級アミン化合物、３級アミン化合物の誘導体；２－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール等のイミダゾール化合物、イミダゾール化合物の誘導体；トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、トリス（４－メチルフェニル）ホスフィン、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン化合物；有機ホスフィン化合物に無水マレイン酸、上記キノン化合物、ジアゾフェニルメタン、フェノール樹脂等のπ結合をもつ化合物を付加してなる分子内分極を有するリン化合物；テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート、２－エチル－４－メチルイミダゾールテトラフェニルボレート、Ｎ－メチルモルホリンテトラフェニルボレート等のテトラフェニルボロン塩、テトラフェニルボロン塩の誘導体；トリフェニルホスホニウム－トリフェニルボラン、Ｎ－メチルモルホリンテトラフェニルホスホニウム－テトラフェニルボレート等のホスフィン化合物とテトラフェニルボロン塩との付加物などが挙げられる。硬化促進剤は、１種類を単独で使用しても、２種類以上を併用してもよい。 (Hardening accelerator)
The sealing composition may further contain a curing accelerator. The kind in particular of a hardening accelerator is not restrict | limited, A well-known hardening accelerator can be used.
Specifically, 1,8-diaza-bicyclo [5.4.0] undecene-7, 1,5-diaza-bicyclo [4.3.0] nonene, 5,6-dibutylamino-1,8- Cycloamidine compounds such as diaza-bicyclo [5.4.0] undecene-7; and cycloamidine compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethyl Quinone compounds such as benzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, etc., diazo Compounds having an intramolecular polarization formed by addition of compounds having a π bond such as phenylmethane and phenol resin; benzyldimethylamine, triethanolamine Tertiary amine compounds such as methylaminoethanol and tris (dimethylaminomethyl) phenol; derivatives of tertiary amine compounds; imidazole compounds such as 2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole; imidazole compounds Organic phosphine compounds such as tributyl phosphine, methyl diphenyl phosphine, triphenyl phosphine, tris (4-methylphenyl) phosphine, diphenyl phosphine, phenyl phosphine, etc .; Organic phosphine compounds such as maleic anhydride, the above quinone compounds, diazophenyl methane, Phosphorus compounds having an intramolecular polarization formed by adding a compound having a π bond such as a phenol resin; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetranate Tetraphenylboron salts such as hexyl borate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, derivatives of tetraphenylboron salts; triphenylphosphonium-triphenylborane, N-methylmorpholine tetraphenylphosphonium And adducts of phosphine compounds such as tetraphenyl borate with tetraphenyl boronate. The curing accelerator may be used alone or in combination of two or more.
　硬化促進剤の含有率は、エポキシ樹脂と硬化剤の合計量に対して、０．１質量％～８質量％であることが好ましい。 The content of the curing accelerator is preferably 0.1% by mass to 8% by mass with respect to the total amount of the epoxy resin and the curing agent.
（イオントラップ剤）
　封止組成物は、イオントラップ剤をさらに含有してもよい。
　本開示において使用可能なイオントラップ剤は、半導体装置の製造用途に用いられる封止材において、一般的に使用されているイオントラップ剤であれば特に制限されるものではなく、ハイドロタルサイト等が挙げられる。イオントラップ剤としては、下記一般式（ＩＩ－１）又は下記一般式（ＩＩ－２）で表される化合物を用いてもよい。 (Ion trap agent)
The sealing composition may further contain an ion trapping agent.
The ion trap agent that can be used in the present disclosure is not particularly limited as long as it is a generally used ion trap agent in a sealing material used for semiconductor device manufacturing applications, and hydrotalcite etc. It can be mentioned. As the ion trapping agent, a compound represented by the following general formula (II-1) or the following general formula (II-2) may be used.
Ｍｇ１－ａＡｌａ（ＯＨ）２（ＣＯ３）ａ／２・ｕＨ２Ｏ　（ＩＩ－１）
（一般式（ＩＩ－１）中、ａは０＜ａ≦０．５であり、ｕは正数である。）
ＢｉＯｂ（ＯＨ）ｃ（ＮＯ３）ｄ　（ＩＩ－２）
（一般式（ＩＩ－２）中、ｂは０．９≦ｂ≦１．１、ｃは０．６≦ｃ≦０．８、ｄは０．２≦ｄ≦０．４である。） Mg 1-a Al a (OH) 2 (CO 3 ) a / 2 · uH 2 O (II-1)
(In the general formula (II-1), a is 0 <a ≦ 0.5 and u is a positive number.)
BiO b (OH) c (NO 3 ) d (II-2)
(In the general formula (II-2), b is 0.9 ≦ b ≦ 1.1, c is 0.6 ≦ c ≦ 0.8, and d is 0.2 ≦ d ≦ 0.4.)
　イオントラップ剤は、市販品として入手可能である。一般式（ＩＩ－１）で表される化合物としては、例えば、「ＤＨＴ－４Ａ」（協和化学工業株式会社、商品名）が市販品として入手可能である。また、一般式（ＩＩ－２）で表される化合物としては、例えば、「ＩＸＥ５００」（東亞合成株式会社、商品名）が市販品として入手可能である。 Ion trap agents are commercially available. As a compound represented by the general formula (II-1), for example, “DHT-4A” (Kyowa Chemical Industry Co., Ltd., trade name) is commercially available. In addition, as a compound represented by the general formula (II-2), for example, “IXE 500” (Toagosei Co., Ltd., trade name) is commercially available.
　また、上記以外のイオントラップ剤として、マグネシウム、アルミニウム、チタン、ジルコニウム、アンチモン等から選ばれる元素の含水酸化物などが挙げられる。
　イオントラップ剤は、１種類を単独で使用しても、２種類以上を併用してもよい。 In addition, as ion trap agents other than the above, hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony and the like can be mentioned.
The ion trap agent may be used alone or in combination of two or more.
　封止組成物がイオントラップ剤を含有する場合、イオントラップ剤の含有量は、充分な耐湿信頼性を実現する観点からは、封止組成物中のエポキシ樹脂１００質量部に対し、１質量部以上であることが好ましい。他の成分の効果を充分に発揮する観点からは、イオントラップ剤の含有量は、封止組成物中のエポキシ樹脂１００質量部に対し、１５質量部以下であることが好ましい。 When the sealing composition contains an ion trap agent, the content of the ion trap agent is 1 part by mass with respect to 100 parts by mass of the epoxy resin in the sealing composition from the viewpoint of achieving sufficient moisture resistance reliability. It is preferable that it is more than. From the viewpoint of sufficiently exhibiting the effects of the other components, the content of the ion trap agent is preferably 15 parts by mass or less with respect to 100 parts by mass of the epoxy resin in the sealing composition.
　また、イオントラップ剤の平均粒子径は０．１μｍ～３．０μｍであることが好ましく、最大粒子径は１０μｍ以下であることが好ましい。イオントラップ剤の平均粒子径は、無機充填材の場合と同様にして測定することができる。 The average particle size of the ion trap agent is preferably 0.1 μm to 3.0 μm, and the maximum particle size is preferably 10 μm or less. The average particle size of the ion trapping agent can be measured in the same manner as in the case of the inorganic filler.
（カップリング剤）
　封止組成物は、カップリング剤をさらに含有してもよい。カップリング剤の種類は、特に制限されず、公知のカップリング剤を使用することができる。カップリング剤としては、例えば、シランカップリング剤及びチタンカップリング剤が挙げられる。カップリング剤は、１種類を単独で使用しても、２種類以上を併用してもよい。 (Coupling agent)
The sealing composition may further contain a coupling agent. The type of coupling agent is not particularly limited, and known coupling agents can be used. As a coupling agent, a silane coupling agent and a titanium coupling agent are mentioned, for example. The coupling agent may be used alone or in combination of two or more.
　シランカップリング剤としては、例えば、ビニルトリクロロシラン、ビニルトリエトキシシラン、ビニルトリス（β－メトキシエトキシ）シラン、γ－メタクリロキシプロピルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－［ビス（β－ヒドロキシエチル）］アミノプロピルトリエトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルトリメトキシシラン、γ－（β－アミノエチル）アミノプロピルジメトキシメチルシラン、Ｎ－（トリメトキシシリルプロピル）エチレンジアミン、Ｎ－（ジメトキシメチルシリルイソプロピル）エチレンジアミン、メチルトリメトキシシラン、メチルトリエトキシシラン、Ｎ－β－（Ｎ－ビニルベンジルアミノエチル）－γ－アミノプロピルトリメトキシシラン、γ－クロロプロピルトリメトキシシラン、ヘキサメチルジシラン、γ－アニリノプロピルトリメトキシシラン、ビニルトリメトキシシラン及びγ－メルカプトプロピルメチルジメトキシシランが挙げられる。 As a silane coupling agent, for example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Γ-Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N -Β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilyl) Propyl) ethylenediamine, methyltrimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, γ-ani Linopropyltrimethoxysilane, vinyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane can be mentioned.
　チタンカップリング剤としては、例えば、イソプロピルトリイソステアロイルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、イソプロピルトリ（Ｎ－アミノエチル－アミノエチル）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、テトラ（２，２－ジアリルオキシメチル－１－ブチル）ビス（ジトリデシルホスファイト）チタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、ビス（ジオクチルパイロホスフェート）エチレンチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルトリドデシルベンゼンスルホニルチタネート、イソプロピルイソステアロイルジアクリルチタネート、イソプロピルトリ（ジオクチルホスフェート）チタネート、イソプロピルトリクミルフェニルチタネート及びテトライソプロピルビス（ジオクチルホスファイト）チタネートが挙げられる。 As a titanium coupling agent, for example, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra ( 2,2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylic iso Stearoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl isostearoyl diacrylic acid Titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate and tetraisopropyl bis (dioctyl phosphite) titanate and the like.
　封止組成物がカップリング剤を含有する場合、カップリング剤の含有率は、封止組成物の全体に対して３質量％以下であることが好ましく、その効果を発揮させる観点からは、０．１質量％以上であることが好ましい。 When the sealing composition contains a coupling agent, the content of the coupling agent is preferably 3% by mass or less based on the whole of the sealing composition, and from the viewpoint of exerting the effect, 0 The content is preferably 1% by mass or more.
（離型剤）
　封止組成物は、離型剤をさらに含有してもよい。離型剤の種類は特に制限されず、公知の離型剤を使用することができる。具体的には、例えば、高級脂肪酸、高級脂肪酸エステル、カルナバワックス及びポリエチレン系ワックスが挙げられる。離型剤は、１種類を単独で使用しても、２種類以上を併用してもよい。
　封止組成物が離型剤を含有する場合、離型剤の含有率は、エポキシ樹脂と硬化剤の合計量に対して、１０質量％以下であることが好ましく、その効果を発揮させる観点からは、０．５質量％以上であることが好ましい。 (Release agent)
The sealing composition may further contain a release agent. The kind in particular of a mold release agent is not restrict | limited, A well-known mold release agent can be used. Specifically, for example, higher fatty acids, higher fatty acid esters, carnauba wax and polyethylene waxes can be mentioned. The mold release agent may be used alone or in combination of two or more.
When the sealing composition contains a release agent, the content of the release agent is preferably 10% by mass or less based on the total amount of the epoxy resin and the curing agent, and from the viewpoint of exerting the effect Is preferably 0.5% by mass or more.
（着色剤及び改質剤）
　封止組成物は、着色剤（例えば、カーボンブラック）を含有してもよい。また、封止組成物は、改質剤（例えば、シリコーン及びシリコーンゴム）を含有してもよい。着色剤及び改質剤は、それぞれ、１種類を単独で使用しても、２種類以上を併用してもよい。 (Colorant and modifier)
The sealing composition may contain a colorant (eg, carbon black). The sealing composition may also contain modifiers such as silicone and silicone rubber. The colorant and the modifier may be used alone or in combination of two or more.
　着色剤としてカーボンブラック等の導電性粒子を用いる場合、導電性粒子は、粒子径１０μｍ以上の粒子の含有率が１質量％以下であることが好ましい。
　封止組成物が導電性粒子を含有する場合、導電性粒子の含有率は、エポキシ樹脂と硬化剤の合計量に対して４質量％以下であることが好ましい。 When using electroconductive particles, such as carbon black, as a coloring agent, it is preferable that electroconductive particles are 1 mass% or less in content rate of particle | grains of 10 micrometers or more of particle diameters.
When the sealing composition contains conductive particles, the content of the conductive particles is preferably 4% by mass or less based on the total amount of the epoxy resin and the curing agent.
＜封止組成物の作製方法＞
　封止組成物の作製方法は特に制限されず、公知の方法により行うことができる。例えば、所定の配合量の原材料の混合物をミキサー等によって充分混合した後、熱ロール、押出機等によって混練し、冷却、粉砕等の処理を経ることによって作製することができる。封止組成物の状態は特に制限されず、粉末状、固体状、液体状等であってよい。 <Method of Producing Sealing Composition>
The method for producing the sealing composition is not particularly limited, and can be carried out by a known method. For example, after a mixture of raw materials of a predetermined compounding amount is sufficiently mixed by a mixer or the like, it can be manufactured by kneading by a heat roll, an extruder or the like, and subjecting to processing such as cooling or crushing. The state of the sealing composition is not particularly limited, and may be powder, solid, liquid or the like.
＜半導体装置＞
　本開示の半導体装置は、半導体素子と、前記半導体素子を封止してなる本開示の封止組成物の硬化物と、を含む。 <Semiconductor device>
A semiconductor device of the present disclosure includes a semiconductor element and a cured product of the sealing composition of the present disclosure formed by sealing the semiconductor element.
　封止組成物を用いて半導体素子を封止する方法は特に限定されず、公知の方法を適用することが可能である。例えば、トランスファーモールド法が一般的であるが、コンプレッションモールド法、インジェクション成形法等を用いてもよい。 The method for sealing the semiconductor element using the sealing composition is not particularly limited, and a known method can be applied. For example, transfer molding is generally used, but compression molding, injection molding, etc. may be used.
　本開示の半導体装置は、ＩＣ、ＬＳＩ（Ｌａｒｇｅ－Ｓｃａｌｅ　Ｉｎｔｅｇｒａｔｉｏｎ、大規模集積回路）等として好適である。 The semiconductor device of the present disclosure is suitable as an IC, a large scale integration (LSI) circuit, or the like.
　以下に本発明の実施例について説明するが、本発明はこれに限定されるものではない。また、表中の数値は特に断りのない限り「質量部」を意味する。 Examples of the present invention will be described below, but the present invention is not limited thereto. Moreover, the numerical value in a table | surface means a "mass part" unless there is particular notice.
（実施例１～１１並びに比較例１及び２）
　表１～表３に示す配合の材料を予備混合（ドライブレンド）した後、二軸ロール（ロール表面温度：約８０℃）で約１５分間混練し、冷却粉砕して粉末状の封止組成物を製造した。 (Examples 1 to 11 and Comparative Examples 1 and 2)
After pre-mixing (dry blending) the materials of the formulations shown in Tables 1 to 3, the mixture is kneaded for about 15 minutes with a biaxial roll (roll surface temperature: about 80 ° C.), and is cooled and pulverized to obtain a powdery sealing composition Manufactured.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表中の材料の詳細は、それぞれ以下の通りである。また表中の「－」は、該当する成分を含有しないことを示す。 The details of the materials in the table are as follows. Also, "-" in the table indicates that the corresponding component is not contained.
（エポキシ樹脂）
・エポキシ樹脂１：ビフェニル型エポキシ樹脂、エポキシ当量：１８６ｇ／ｅｑ
・エポキシ樹脂２：多官能エポキシ樹脂、エポキシ当量：１６７ｇ／ｅｑ
・エポキシ樹脂３：ビスフェノール型結晶性エポキシ樹脂、エポキシ当量：１９２ｇ／ｅｑ
・エポキシ樹脂４：ビスＦ型エポキシ樹脂、エポキシ当量：１５９ｇ／ｅｑ (Epoxy resin)
Epoxy resin 1: Biphenyl type epoxy resin, epoxy equivalent: 186 g / eq
-Epoxy resin 2: Multifunctional epoxy resin, epoxy equivalent: 167 g / eq
Epoxy resin 3: bisphenol type crystalline epoxy resin, epoxy equivalent: 192 g / eq
・ Epoxy resin 4: Bis-F type epoxy resin, epoxy equivalent: 159 g / eq
（硬化剤）
・硬化剤１：多官能フェノール樹脂、水酸基当量が１０２ｇ／ｅｑのトリフェニルメタン型フェノール樹脂
・硬化剤２：多官能フェノール樹脂、水酸基当量が２０５ｇ／ｅｑのビフェニル・アラルキル樹脂
・硬化剤３：フェノール・アラルキル樹脂、水酸基当量：１７０ｇ／ｅｑ (Hardening agent)
Curing agent 1: Multifunctional phenolic resin, triphenylmethane type phenolic resin having a hydroxyl equivalent of 102 g / eq Curing agent 2: Multifunctional phenolic resin, biphenyl having a hydroxyl equivalent of 205 g / eq, curing agent Curing agent 3: Phenol・ Aralkyl resin, hydroxyl equivalent: 170 g / eq
・硬化促進剤：リン系硬化促進剤
・カップリング剤：エポキシシラン（γ－グリシドキシプロピルトリメトキシシラン）
・離型剤：モンタン酸エステル
・着色剤：カーボンブラック
・イオントラップ剤：ハイドロタルサイト
・改質剤：シリコーン ・ Hardening accelerator: Phosphorus hardening accelerator ・ Coupling agent: Epoxysilane (γ-glycidoxypropyltrimethoxysilane)
-Releasing agent: Montanic acid ester-Coloring agent: Carbon black-Ion trap agent: Hydrotalcite-Modifier: Silicone
（無機充填材）
　・無機充填材１：アルミナとシリカの混合物（平均粒子径：８．６μｍ）
　・無機充填材２：シリカ（平均粒子径：９．５μｍ）
　・無機充填材３：アルミナ（平均粒子径：０．４μｍ）
　・無機充填材４：シリカ（平均粒子径：０．８μｍ）
　・無機充填材５：シリカ（平均粒子径：０．１μｍ）
　・無機充填材６：シリカ（平均粒子径：１３.０μｍ）
　・無機充填材７：シリカ（平均粒子径：２．２μｍ）
　・無機充填材８：シリカ（平均粒子径：０．８μｍ）
　・無機充填材９：アルミナとシリカの混合物（平均粒子径：７．４μｍ）
　・無機充填材１０：シリカ（平均粒子径：１．５μｍ）
　・無機充填材１１：シリカ（平均粒子径：２２．０μｍ）
　・無機充填材１２：アルミナ（平均粒子径：１４．９μｍ）
　・無機充填材１３：アルミナ（平均粒子径：１０．４μｍ）
　・無機充填材１４：アルミナ（平均粒子径：２．０μｍ）
　・無機充填材１５：アルミナとシリカの混合物（平均粒子径：４３．９μｍ） (Inorganic filler)
· Inorganic filler 1: Mixture of alumina and silica (average particle size: 8.6 μm)
· Inorganic filler 2: silica (average particle size: 9.5 μm)
· Inorganic filler 3: alumina (average particle size: 0.4 μm)
· Inorganic filler 4: silica (average particle size: 0.8 μm)
· Inorganic filler 5: silica (average particle size: 0.1 μm)
· Inorganic filler 6: silica (average particle size: 13.0 μm)
· Inorganic filler 7: silica (average particle size: 2.2 μm)
· Inorganic filler 8: silica (average particle size: 0.8 μm)
· Inorganic filler 9: mixture of alumina and silica (average particle size: 7.4 μm)
· Inorganic filler 10: silica (average particle size: 1.5 μm)
· Inorganic filler 11: silica (average particle size: 22.0 μm)
· Inorganic filler 12: alumina (average particle size: 14.9 μm)
· Inorganic filler 13: alumina (average particle size: 10.4 μm)
· Inorganic filler 14: alumina (average particle size: 2.0 μm)
· Inorganic filler 15: mixture of alumina and silica (average particle size: 43.9 μm)
　実施例１～１１の無機充填材の粒度分布におけるピークの位置は、以下の通りであり、
３つのピークを有していた。また、実施例１～１１に係る封止組成物は全て粒子径が１μｍ以下のアルミナを含んでいた。合わせて、無機充填材全体の平均粒子径を以下に示す。
　実施例１：０．４５μｍ、１０μｍ及び４０μｍ　（平均粒子径：８．１μｍ）
　実施例２：０．５μｍ、１０μｍ及び５０μｍ　（平均粒子径：８．７μｍ）
　実施例３：０．５μｍ、１０μｍ及び５０μｍ　（平均粒子径：７．６μｍ）
　実施例４：０．５μｍ、１０μｍ及び５０μｍ　（平均粒子径：７．７μｍ）
　実施例５：０．５μｍ、１０μｍ及び５０μｍ　（平均粒子径：６．６μｍ）
　実施例６：０．５μｍ、１０μｍ及び５１μｍ　（平均粒子径：６．２μｍ）
　実施例７：０．５μｍ、１０μｍ及び５１μｍ　（平均粒子径：７．７μｍ）
　実施例８：０．５μｍ、１０μｍ及び５１μｍ　（平均粒子径：６．６μｍ）
　実施例９：０．５μｍ、１０μｍ及び５１μｍ　（平均粒子径：１０．８μｍ）
　実施例１０：０．４５μｍ、１０μｍ及び５１μｍ　（平均粒子径：６．４μｍ）
　実施例１１：０．４μｍ、９μｍ及び４５μｍ　（平均粒子径：７．８μｍ）
　一方、比較例１の無機充填材の粒度分布におけるピークの位置は、以下の通りであり、２つのピークを有していた。また、比較例１に係る封止組成物は粒子径が１μｍ以下のアルミナを含んでいた。合わせて、無機充填材全体の平均粒子径を以下に示す。
　比較例１：１．５μｍ及び１０μｍ　（平均粒子径：１１．３μｍ）
　また、比較例２の無機充填材の粒度分布におけるピークの位置は、以下の通りであり、３つのピークを有していた。また、比較例２に係る封止組成物は粒子径が１μｍ以下のアルミナを含んでいなかった。合わせて、無機充填材全体の平均粒子径を以下に示す。
　比較例２：０．５μｍ、１０μｍ及び５０μｍ　（平均粒子径：６．５μｍ） The positions of peaks in the particle size distribution of the inorganic filler of Examples 1 to 11 are as follows:
It had 3 peaks. The sealing compositions according to Examples 1 to 11 all contained alumina having a particle diameter of 1 μm or less. In addition, the average particle size of the entire inorganic filler is shown below.
Example 1: 0.45 μm, 10 μm and 40 μm (average particle size: 8.1 μm)
Example 2: 0.5 μm, 10 μm and 50 μm (average particle size: 8.7 μm)
Example 3: 0.5 μm, 10 μm and 50 μm (average particle size: 7.6 μm)
Example 4: 0.5 μm, 10 μm and 50 μm (average particle size: 7.7 μm)
Example 5: 0.5 μm, 10 μm and 50 μm (average particle size: 6.6 μm)
Example 6: 0.5 μm, 10 μm and 51 μm (average particle size: 6.2 μm)
Example 7: 0.5 μm, 10 μm and 51 μm (average particle size: 7.7 μm)
Example 8: 0.5 μm, 10 μm and 51 μm (average particle size: 6.6 μm)
Example 9: 0.5 μm, 10 μm and 51 μm (average particle diameter: 10.8 μm)
Example 10: 0.45 μm, 10 μm and 51 μm (average particle size: 6.4 μm)
Example 11: 0.4 μm, 9 μm and 45 μm (average particle size: 7.8 μm)
On the other hand, the position of the peak in the particle size distribution of the inorganic filler of Comparative Example 1 was as follows, and had two peaks. Moreover, the sealing composition which concerns on the comparative example 1 contained the alumina whose particle diameter is 1 micrometer or less. In addition, the average particle size of the entire inorganic filler is shown below.
Comparative Example 1: 1.5 μm and 10 μm (average particle size: 11.3 μm)
Moreover, the position of the peak in the particle size distribution of the inorganic filler of the comparative example 2 was as follows, and had three peaks. Moreover, the sealing composition which concerns on the comparative example 2 did not contain the alumina whose particle diameter is 1 micrometer or less. In addition, the average particle size of the entire inorganic filler is shown below.
Comparative Example 2: 0.5 μm, 10 μm and 50 μm (average particle size: 6.5 μm)
＜流動性の評価＞
　封止組成物の流動性の評価は、スパイラルフロー試験により行った。
　具体的には、ＥＭＭＩ－１－６６に準じたスパイラルフロー測定用金型を用いて封止組成物を成形し、封止組成物の成形物の流動距離（ｃｍ）を測定した。封止組成物の成形は、トランスファー成形機を用い、金型温度１８０℃、成形圧力６．９ＭＰａ、硬化時間１２０秒の条件下で行った。
　また、流動性は１６０ｃｍ以上をＡとし、１５０ｃｍ以上１６０ｃｍ未満をＢ、１５０ｃｍ未満をＣとした。 <Evaluation of liquidity>
The evaluation of the flowability of the sealing composition was performed by a spiral flow test.
Specifically, the sealing composition was molded using a spiral flow measurement die according to EMMI-1-66, and the flow distance (cm) of the molded product of the sealing composition was measured. Molding of the sealing composition was performed using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds.
Moreover, fluidity set 160 cm or more to A, 150 cm or more and less than 160 cm as B, and less than 150 cm as C.
＜熱伝導率の評価＞
　封止組成物の熱伝導率の評価は、下記の方法により行った。
　具体的には、調製した封止組成物を用いて、金型温度１８０℃、成形圧力７ＭＰａ、硬化時間３００秒間の条件でトランスファー成形を行い、金型形状の硬化物を得た。得られた硬化物をアルキメデス法により測定した密度は２．８ｇ／ｃｍ３～３．０ｇ／ｃｍ３であった。また硬化物の熱拡散率を熱拡散率測定装置（ＮＥＴＺＳＣＨ社、ＬＦＡ４６７）を用いてレーザーフラッシュ法により測定した。上記で測定された熱拡散率、アルキメデス法で測定した密度及びＤＳＣ（示差熱量計）により測定した比熱の積から熱伝導率（Ｗ／（ｍ・Ｋ））を算出した。
　また、熱伝導率は２．５Ｗ／（ｍ・Ｋ）以上をＡとし、２．５Ｗ／（ｍ・Ｋ）未満をＢとした。 <Evaluation of thermal conductivity>
The evaluation of the thermal conductivity of the sealing composition was performed by the following method.
Specifically, transfer molding was performed using the prepared sealing composition under conditions of a mold temperature of 180 ° C., a molding pressure of 7 MPa, and a curing time of 300 seconds, to obtain a molded product having a mold shape. The density of the obtained cured product measured by the Archimedes method was 2.8 g / cm 3 to 3.0 g / cm 3 . Further, the thermal diffusivity of the cured product was measured by a laser flash method using a thermal diffusivity measuring device (LFA 467, manufactured by NETZSCH). The thermal conductivity (W / (m · K)) was calculated from the product of the thermal diffusivity measured above, the density measured by the Archimedes method, and the specific heat measured by DSC (differential calorimeter).
In addition, the thermal conductivity is A at 2.5 W / (m · K) or more, and B at less than 2.5 W / (m · K).
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表４～表６に示されるように、３つのピークを有する実施例１～１１と２つのピークを有する比較例１の結果より、無機充填材に占めるアルミナの割合に関わらず、無機充填材の粒度分布でピークを３つ有さないことにより、流動性は極端に低下し、熱伝導率は低下した。
　また、無機充填材の中に粒子径が１μｍ以下のアルミナを含まない比較例２は、無機充填材の中に粒子径が１μｍ以下のアルミナを特に多く有する実施例１、５、６、８、１０及び１１と比較し、流動性は同等か又は低下し、熱伝導率は低下する結果となった。 As shown in Tables 4 to 6, according to the results of Examples 1 to 11 having three peaks and Comparative Example 1 having two peaks, regardless of the ratio of alumina to the inorganic filler, the inorganic filler By not having three peaks in the particle size distribution, the fluidity dropped extremely and the thermal conductivity dropped.
In addition, Comparative Example 2 in which the inorganic filler does not contain alumina having a particle diameter of 1 μm or less is an example 1, 5, 6, 8, which has particularly large amounts of alumina having a particle diameter of 1 μm or less in the inorganic filler. Compared to 10 and 11, the flowability was comparable or lower and the thermal conductivity resulted in lower.
　２０１７年１２月２８日に出願された日本国特許出願２０１７－２５４８８３号の開示は、その全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosure of Japanese Patent Application 2017-254883 filed on December 28, 2017 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are as specific and distinct as when individual documents, patent applications, and technical standards are incorporated by reference. Incorporated herein by reference.

Claims (5)

  1. 　エポキシ樹脂と、硬化剤と、無機充填材とを含有し、
    　前記無機充填材の粒度分布が、少なくとも３つのピークを有し、
    　前記無機充填材が、粒子径が１μｍ以下のアルミナを含む封止組成物。     Containing epoxy resin, curing agent, and inorganic filler,
    The particle size distribution of the inorganic filler has at least three peaks,
    The sealing composition in which the said inorganic filler contains an alumina with a particle diameter of 1 micrometer or less.
  2. 　前記無機充填材の粒度分布が、０．３μｍ～０．７μｍの範囲、７μｍ～２０μｍの範囲及び３０μｍ～７０μｍの範囲にピークを有する請求項１に記載の封止組成物。 The sealing composition according to claim 1, wherein the particle size distribution of the inorganic filler has peaks in the range of 0.3 μm to 0.7 μm, in the range of 7 μm to 20 μm, and in the range of 30 μm to 70 μm.
  3. 　前記無機充填材に含まれる粒子径が１μｍ以下の無機粒子に占めるアルミナの割合が、１体積％～４０体積％である請求項１又は請求項２に記載の封止組成物。 The sealing composition according to claim 1 or 2, wherein the proportion of alumina in the inorganic particles having a particle diameter of 1 μm or less contained in the inorganic filler is 1% by volume to 40% by volume.
  4. 　前記無機充填材の平均円形度が、０．８０以上である請求項１～請求項３のいずれか１項に記載の封止組成物。 The sealing composition according to any one of claims 1 to 3, wherein the average circularity of the inorganic filler is 0.80 or more.
  5. 　半導体素子と、前記半導体素子を封止してなる請求項１～請求項４のいずれか１項に記載の封止組成物の硬化物と、を含む半導体装置。 A semiconductor device comprising: a semiconductor element; and the cured product of the sealing composition according to any one of claims 1 to 4, which seals the semiconductor element.
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