WO2017056994A1 - Thermosetting composition, sheet, and method for manufacturing device - Google Patents

Thermosetting composition, sheet, and method for manufacturing device Download PDF

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Publication number
WO2017056994A1
WO2017056994A1 PCT/JP2016/077116 JP2016077116W WO2017056994A1 WO 2017056994 A1 WO2017056994 A1 WO 2017056994A1 JP 2016077116 W JP2016077116 W JP 2016077116W WO 2017056994 A1 WO2017056994 A1 WO 2017056994A1
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Prior art keywords
thermosetting composition
sheet
electronic component
weight
composite
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PCT/JP2016/077116
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French (fr)
Japanese (ja)
Inventor
豪士 志賀
智絵 飯野
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日東電工株式会社
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Priority to SG11201802323SA priority Critical patent/SG11201802323SA/en
Priority to CN201680052778.4A priority patent/CN108026354A/en
Publication of WO2017056994A1 publication Critical patent/WO2017056994A1/en

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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
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/568—Temporary substrate used as encapsulation process aid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/02—Bonding areas; Manufacturing methods related thereto
    • H01L2224/04—Structure, shape, material or disposition of the bonding areas prior to the connecting process
    • H01L2224/04105—Bonding areas formed on an encapsulation of the semiconductor or solid-state body, e.g. bonding areas on chip-scale packages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/12105—Bump connectors formed on an encapsulation of the semiconductor or solid-state body, e.g. bumps on chip-scale packages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/16235—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation the bump connector connecting to a via metallisation of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/81001—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector involving a temporary auxiliary member not forming part of the bonding apparatus
    • H01L2224/81005—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector involving a temporary auxiliary member not forming part of the bonding apparatus being a temporary or sacrificial substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/83001—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector involving a temporary auxiliary member not forming part of the bonding apparatus
    • H01L2224/83005—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector involving a temporary auxiliary member not forming part of the bonding apparatus being a temporary or sacrificial substrate

Definitions

  • the present invention relates to a thermosetting composition, a sheet, and a method for producing an apparatus.
  • the step of placing a sheet-like thermosetting composition on the electronic component, the step of softening the thermosetting composition, covering the electronic component with the thermosetting composition, and the electronic component with the thermosetting composition can be manufactured by a method including a step of causing curing of the thermosetting composition by heating the composite formed by the covering step.
  • thermosetting composition When the electronic component is covered with the thermosetting composition, gas may be trapped between the electronic component and the thermosetting composition. The gas moves, and irregularities and pinholes may be generated on the surface of the thermosetting composition after curing.
  • thermosetting composition may be generated on the surface of the thermosetting composition after curing.
  • the present invention solves the above-mentioned problems, and provides a thermosetting composition that can reduce the gas trapped between the electronic component and the thermosetting composition and can suppress the generation of flow marks. With the goal. Another object of the present invention is to provide a sheet that can reduce the gas trapped between the electronic component and the thermosetting composition and can suppress the generation of flow marks. It is another object of the present invention to provide a method for manufacturing a device having few internal voids and irregularities / pinholes / flow marks.
  • the present invention relates to a sheet-like thermosetting composition containing a phenol resin, an inorganic filler, and silicone-based particles.
  • thermosetting composition of the present invention the gas trapped between the electronic component and the thermosetting composition can be reduced. This is because the thermosetting composition has a high viscosity when the electronic component is covered with the thermosetting composition.
  • thermosetting composition of the present invention the generation of flow marks can also be suppressed. This is probably because the silicone particles suppress the gloss of the package surface.
  • the silicone-based particles have an epoxy group. This is because the strength of the thermosetting composition after curing can be increased.
  • the phenolic resin will bind to the silicone particles and bind the silicone rubber particles.
  • the present invention also relates to a sheet containing the thermosetting composition. Both sides of the thermosetting composition are defined by a first surface and a second surface facing the first surface.
  • the sheet of the present invention further includes a first separator provided on the first surface and a second separator provided on the second surface.
  • the present invention also relates to a device manufacturing method.
  • the manufacturing method of the apparatus of this invention includes the process of arrange
  • the composite includes an electronic component and a thermosetting composition that covers the electronic component.
  • the step of forming the composite includes a step of causing softening of the thermosetting composition.
  • the manufacturing method of the apparatus of this invention further includes the process of raise
  • FIG. 3 is a schematic cross-sectional view of a sheet according to Embodiment 1.
  • FIG. It is a schematic sectional drawing of the manufacturing process of an apparatus. It is a schematic sectional drawing of the manufacturing process of an apparatus. It is a schematic sectional drawing of the manufacturing process of an apparatus. It is a schematic sectional drawing of the process in the 1st manufacture example of a semiconductor device. It is a schematic sectional drawing of the process in the 1st manufacture example of a semiconductor device. It is a schematic sectional drawing of the process in the 1st manufacture example of a semiconductor device. It is a schematic sectional drawing of the process in the 2nd manufacture example of a semiconductor device. It is a schematic sectional drawing of the process in the 2nd manufacture example of a semiconductor device. It is a schematic sectional drawing of the process in the 2nd manufacture example of a semiconductor device. It is a schematic sectional drawing of the process in the 2nd manufacture example of a semiconductor device. It is a schematic sectional drawing of the process in the 2nd
  • the sheet 1 includes a sheet-like thermosetting composition 11. Both surfaces of the thermosetting composition 11 are defined by the first surface and the second surface facing the first surface.
  • the sheet 1 further includes a first separator 12 provided on the first surface. Examples of the first separator 12 include a polyethylene terephthalate (PET) film.
  • the sheet 1 further includes a second separator 13 provided on the second surface. Examples of the second separator 13 include a polyethylene terephthalate (PET) film.
  • thermosetting composition 11 examples include 100 ⁇ m and 200 ⁇ m.
  • examples of the upper limit of the thickness of the thermosetting composition 11 include 2000 ⁇ m and 1500 ⁇ m.
  • the minimum melt viscosity of the thermosetting composition 11 is preferably 100 Pa ⁇ s to 10,000 Pa ⁇ s. When it is 100 Pa ⁇ s or more, there is a tendency that the gas trapped between the electronic component and the thermosetting composition 11 is small. When the pressure is 10,000 Pa ⁇ s or less, there is a tendency that no space—an unfilled region—is generated between the electronic component and the thermosetting composition 11 during molding.
  • the thermosetting composition 11 includes silicone particles.
  • the silicone-based particles are preferably silicone elastomer particles.
  • the silicone-based particles have a group that reacts with at least one of a phenol resin and an epoxy resin.
  • the group that reacts with at least one of a phenol resin and an epoxy resin include an epoxy group.
  • the shape of the silicone-based particles is preferably spherical.
  • the average particle size of the silicone-based particles is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less. Examples of the lower limit of the average particle diameter of the silicone particles include 0.5 ⁇ m and 1 ⁇ m.
  • the total weight of the silicone-based particles is preferably 0.5% or more, more preferably 1%. That's it.
  • the total weight of the silicone-based particles is preferably 50% or less, more preferably 45% or less. is there. If it exceeds 50%, a space—an unfilled region—may remain between the electronic component and the thermosetting composition 11.
  • the thermosetting composition 11 includes an epoxy resin that is liquid at 25 ° C. and an epoxy resin that is solid at 25 ° C. By blending a liquid epoxy resin at 25 ° C., the thermosetting composition 11 can be produced by kneading extrusion using a roll kneader or the like.
  • the epochine equivalent of the epoxy resin that is liquid at 25 ° C. is preferably 100 g / eq or more, more preferably 120 g / eq or more.
  • the epoxy equivalent of the epoxy resin that is liquid at 25 ° C. is preferably 500 g / eq or less, more preferably 300 g / eq or less.
  • the epoxy equivalent can be measured by the method defined in JIS K 7236-2009.
  • Examples of the epoxy resin that is liquid at 25 ° C. include bisphenol A type epoxy resin.
  • Examples of the epoxy resin solid at 25 ° C. include an epoxy resin having an epoxy equivalent of 100 to 180 g / eq, an epoxy resin having an epoxy equivalent of 200 g / eq or more, and the like.
  • the thermosetting composition 11 preferably contains an epoxy resin having an epoxy equivalent of 100 to 180 g / eq and an epoxy resin having an epoxy equivalent of 200 g / eq or more. By blending an epoxy resin having an epoxy equivalent of 100 to 180 g / eq, the glass transition temperature of the thermosetting composition 11 after thermosetting can be increased.
  • Examples of the epoxy resin having an epoxy equivalent of 200 g / eq or more include a dicyclopentadiene type epoxy resin.
  • the total weight of the epoxy resin is preferably 20% or more.
  • the total weight of the epoxy resin is preferably 80% or less.
  • the thermosetting composition 11 contains a phenol resin.
  • the phenol resin include a phenol novolak resin, a phenol aralkyl resin, a biphenyl aralkyl resin, a dicyclopentadiene type phenol resin, a cresol novolac resin, and a resole resin. These phenolic resins may be used alone or in combination of two or more.
  • the hydroxyl equivalent of the phenol resin is preferably 70 to 250.
  • the softening point of the phenol resin is preferably 50 to 110 ° C.
  • the blending ratio of the epoxy resin and the phenol resin is blended so that the total of hydroxyl groups in the phenol resin is 0.7 to 1.5 equivalents with respect to 1 equivalent of the epoxy group in the epoxy resin from the viewpoint of curing reactivity. It is preferable to use 0.9 to 1.2 equivalents.
  • the total weight of the phenol resin is preferably 5% or more, more preferably 10% or more.
  • the total weight of the phenol resin is preferably 60% or less, more preferably 40% or less.
  • the thermosetting composition 11 contains an inorganic filler.
  • the inorganic filler include quartz glass, talc, silica, alumina, boron nitride, aluminum nitride, and silicon carbide.
  • silica is preferable because the thermal expansion coefficient can be satisfactorily reduced.
  • fused silica is preferred, and spherical fused silica is more preferred.
  • Alumina, boron nitride, and aluminum nitride are preferred because of their high thermal conductivity.
  • the thermosetting composition 11 can contain one kind of inorganic filler. Two or more inorganic fillers can also be included.
  • the average particle diameter of the inorganic filler is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more.
  • the average particle diameter of the filler is preferably 30 ⁇ m or less.
  • the average particle diameter can be derived by, for example, using a sample arbitrarily extracted from the population and measuring it using a laser diffraction / scattering particle size distribution measuring apparatus.
  • the content of the inorganic filler in the thermosetting composition 11 is 55% by volume or more, more preferably 60% by volume or more, and still more preferably 70% by volume or more. By increasing the content of the inorganic filler, it is possible to bring the linear expansion coefficient of the cured thermosetting composition 11 closer to the linear expansion coefficient of the substrate or the like.
  • the content of the inorganic filler in the thermosetting composition 11 is preferably 85% by volume or less, more preferably 80% by volume or less. It is easy to shape
  • the content of the inorganic filler can be explained in units of “% by weight”. Typically, the silica content will be described in terms of “% by weight”.
  • the content of silica in the thermosetting composition 11 is preferably 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and further preferably 85% by weight or more.
  • the upper limit of the content of silica in the thermosetting composition 11 is, for example, 95% by weight.
  • the content of alumina is also described in “% by weight”.
  • the content of alumina in the thermosetting composition 11 is preferably 72% by weight or more, more preferably 80% by weight or more, and further preferably 87% by weight or more.
  • the content of alumina in the thermosetting composition 11 is preferably 95% by weight or less, more preferably 93% by weight or less.
  • the thermosetting composition 11 contains a silane coupling agent.
  • silane coupling agents include 3-glycidoxypropyltrimethoxysilane.
  • the thermosetting composition 11 includes a curing accelerator.
  • the curing accelerator is not particularly limited as long as it can cure the epoxy resin and the phenol resin.
  • 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11-Z) ), 2-heptadecylimidazole (trade name; C17Z), 1,2-dimethylimidazole (trade name; 1.2 DMZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-phenylimidazole (product) Name; 2PZ), 2-phenyl-4-methylimidazole (trade name; 2P4MZ), 1-benzyl-2-methylimidazole (trade name; 1B2MZ), 1-benzyl-2-phenylimidazole (trade name; 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name; 2MZ-CN), 1-cyanoethyl 2-Undecylim
  • 2-phenyl-4,5-dihydroxymethylimidazole 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl) is preferable because the progress of the curing reaction at the kneading temperature can be suppressed.
  • -(1 ')]-Ethyl-s-triazine is more preferred, and 2-phenyl-4,5-dihydroxymethylimidazole is more preferred.
  • the content of the curing accelerator is preferably 0.2 parts by weight or more, more preferably 0.5 parts by weight or more, further preferably 0.8 parts by weight or more with respect to 100 parts by weight of the total of the epoxy resin and the phenol resin. It is.
  • the content of the curing accelerator is preferably 5 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the total of the epoxy resin and the phenol resin.
  • thermosetting composition 11 contains carbon black.
  • the thermosetting composition 11 can be manufactured, for example, by a method including a step of forming a mixture obtained by kneading a phenol resin, an inorganic filler, silicone-based particles and the like into a sheet shape.
  • the upper limit of the temperature in kneading is, for example, 140 ° C or 130 ° C.
  • the lower limit of the temperature is, for example, 30 ° C. or 50 ° C.
  • the kneading time is preferably 1 to 30 minutes. It is preferable to knead under reduced pressure conditions (under reduced pressure atmosphere).
  • the pressure in the reduced pressure atmosphere is, for example, 1 ⁇ 10 ⁇ 4 to 0.1 kg / cm 2 .
  • thermosetting composition 11 phenol resin, inorganic filler, silicone particles, etc.
  • a solvent for preparing a varnish
  • this varnish is applied onto a support, and a coating film
  • the thermosetting composition 11 can also be manufactured by drying.
  • the solvent include methyl ethyl ketone, ethyl acetate, toluene and the like.
  • the thermosetting composition 11 can be used for sealing electronic components.
  • the electronic component include a sensor, a MEMS (Micro Electro Mechanical Systems), a SAW (Surface Acoustic Wave) chip, a semiconductor element, a capacitor, and a resistor.
  • the sensor include a pressure sensor and a vibration sensor.
  • the semiconductor element include a semiconductor chip, an IC (integrated circuit), and a transistor.
  • the thermosetting composition 11 can be particularly preferably used for sealing a semiconductor element.
  • the device manufacturing method includes a step of disposing the thermosetting composition 11 on the electronic component 21. As shown in FIG. 3, the device manufacturing method further includes a step of forming the electronic component 21 and the composite 2 including the thermosetting composition 11 covering the electronic component 21. The device manufacturing method further includes a step of causing the thermosetting composition 11 to cure by heating the composite 2.
  • the device manufacturing method further includes a step of peeling the first separator 12 from the thermosetting composition 11 before the step of disposing the thermosetting composition 11 on the electronic component 21.
  • the step of disposing the thermosetting composition 11 on the electronic component 21 specifically includes the thermosetting composition 11 and the second separator 13 provided on the second surface of the thermosetting composition 11. This is a step of disposing the containing sheet on the electronic component 21.
  • the process of forming the composite 2 includes a step of causing the thermosetting composition 11 to soften.
  • the thermosetting composition 11 is preferably heated at 40 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 60 ° C. or higher.
  • the thermosetting composition 11 is preferably heated at 150 ° C. or lower, more preferably 100 ° C. or lower, and further preferably 90 ° C. or lower.
  • the process of forming the composite 2 further includes a step of covering the electronic component 21 with the thermosetting composition 11.
  • the step of covering the electronic component 21 with the thermosetting composition 11 is a step of embedding the electronic component 21 in the thermosetting composition 11 under a reduced pressure atmosphere.
  • the reduced pressure atmosphere is, for example, an atmosphere of 0.1 kPa to 5 kPa, an atmosphere of 0.1 Pa to 100 Pa, or the like.
  • the composite 2 is preferably heated at 100 ° C. or higher, more preferably 120 ° C. or higher.
  • the composite 2 is preferably heated at 200 ° C. or lower, more preferably 180 ° C. or lower.
  • the composite 2 after the step of causing the thermosetting composition 11 to cure includes an electronic component 21 and a cured thermosetting composition 31 that covers the electronic component 21.
  • the device manufacturing method includes a step of forming a wiring.
  • the laminated body 101 includes a temporary fixing body 141, a thermosetting composition 11 disposed on the temporary fixing body 141, and a second separator 13 disposed on the thermosetting composition 11. Including.
  • the laminate 101 is disposed between the lower heating plate 161 and the upper heating plate 162.
  • the temporarily fixed body 141 includes a support plate 142, an adhesive layer 143 disposed on the support plate 142, and a semiconductor chip 121 fixed to the adhesive layer 143.
  • Examples of the material of the pressure-sensitive adhesive layer 143 include a heat-peelable pressure-sensitive adhesive such as a heat-foamable pressure-sensitive adhesive.
  • the chip composite 102 is formed by heat-pressing the laminated body 101 in a reduced pressure atmosphere by a parallel plate method using a lower heating plate 161 and an upper heating plate 162.
  • the chip composite 102 includes a semiconductor chip 121 and the thermosetting composition 11 that covers the semiconductor chip 121.
  • the chip composite 102 is in contact with the adhesive layer 143.
  • the chip composite 102 is in contact with the second separator 13.
  • the second separator 13 is peeled from the chip composite 102. Curing of the thermosetting composition 11 occurs.
  • the pressure-sensitive adhesive layer 143 is heated, and the chip composite 102 is peeled from the pressure-sensitive adhesive layer 143.
  • wirings 171 and the like are formed. After the wiring 171 is formed, the chip composite 102 is diced. The semiconductor device is obtained by the above procedure.
  • the laminated structure 201 includes a mounting wafer 241, a thermosetting composition 11 disposed on the mounting wafer 241, and a second separator 13 disposed on the thermosetting composition 11. including.
  • the laminated structure 201 is disposed between the lower heating plate 261 and the upper heating plate 262.
  • the mounting wafer 241 includes a semiconductor wafer 242, a semiconductor chip 221, and an underfill material 243 sandwiched between the semiconductor wafer 242 and the semiconductor chip 221.
  • the semiconductor wafer 242 has electrodes.
  • a wafer composite 202 is formed by hot-pressing the laminated structure 201 by a parallel plate method using a lower heating plate 261 and an upper heating plate 262.
  • the wafer composite 202 includes a semiconductor wafer 242, a semiconductor chip 221, an underfill material 243 sandwiched between the semiconductor wafer 242 and the semiconductor chip 221, and the thermosetting composition 11 that covers the semiconductor chip 221.
  • Wafer composite 202 is in contact with second separator 13.
  • the second separator 13 is peeled from the wafer composite 202. Curing of the thermosetting composition 11 occurs. As shown in FIG. 10, the wafer composite 202 is ground. As shown in FIG. 11, wirings 271 and the like are formed. After forming the wiring 271 and the like, the wafer composite 202 is diced. The semiconductor device is obtained by the above procedure.
  • thermosetting composition 11 has a multilayer structure having a plurality of layers.
  • Epoxy resin 1 EPPN-501HY (Epokin equivalent 162 g / eq. To 172 g / eq. Epoxy resin having a softening point of 51 ° C. to 57 ° C.) manufactured by Nippon Kayaku Co., Ltd.
  • Epoxy resin 2 jER828 (Epkin equivalent 184 g / eq. To 194 g / eq., Bisphenol A type epoxy resin liquid at 25 ° C.)
  • Epoxy resin 3 HP7200 (dicyclopentadiene type epoxy resin having an epkin equivalent of 254 g / eq.
  • Silicone particles EP-2601 manufactured by Toray Dow Corning (spherical silicone elastomer particles having an epoxy group and an average particle diameter of 2 ⁇ m) Carbon black: # 20 manufactured by Mitsubishi Chemical Catalyst: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • Silane coupling agent KBM-403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
  • thermosity A circular sample having a diameter of 25 mm was obtained by hollowing out the resin sheet.
  • the melt viscosity of the sample was measured using a viscoelasticity measuring device ARES (manufactured by Rheometrics Scientific). Specifically, the sample was sandwiched between parallel plates having a plate diameter of 25 mm, and the melt viscosity was measured at a heating rate of 10 ° C./min, a strain of 10%, and a frequency of 1 Hz. The lowest melt viscosity at 50 ° C. to 150 ° C. was defined as the minimum melt viscosity.
  • a laminated body was formed by laminating a disk-shaped resin on a “wafer with chips”. By pressing the laminated body with a flat plate pressing apparatus, a mirror wafer, 150 silicon chips with adhesive sheet fixed to the mirror wafer, and a protective resin with a thickness of 700 ⁇ m covering 150 silicon chips with adhesive sheet are provided. A structure was obtained.
  • the protective resin was cured by heating the structure at 180 ° C. for 2 hours using a hot air circulating dryer.
  • a hot air circulating dryer When at least one of the unevenness having a diameter of 1 mm or more and the pinhole having a diameter of 0.5 mm or more is on the surface of the protective resin after curing, it was determined as x. In the case where neither the unevenness having a diameter of 1 mm or more and the pinhole having a diameter of 0.5 mm or more were present, it was judged as “good”.
  • the protective resin was cured by heating the structure at 180 ° C. for 2 hours using a hot air circulating dryer. With respect to the heated structure, the internal voids and the unfilled region-internal space- were observed with an ultrasonic imaging device (FS200II manufactured by Hitachi Finetech). Observation was performed in the reflection mode using a 25 MHz probe. When there was at least either an internal void of 0.5 mm or more or an unfilled region of 0.5 mm or more, it was determined as x. When there was neither a void of 0.5 mm or more and an unfilled region of 0.5 mm or more, it was determined as ⁇ .
  • the protective resin was cured by heating the structure at 180 ° C. for 2 hours using a hot air circulating dryer.
  • the surface (hymen) of the protective resin after curing was visually observed. When a pattern was recognized, it determined with x. When the pattern was not recognized, it was judged as “good”.

Abstract

Provided are a thermosetting composition and a sheet, whereby gas trapped between an electronic component and the thermosetting composition can be decreased and the occurrence of flow marks can be suppressed. Provided is a method for manufacturing a device having few internal voids and minimal unevenness/pinholing/flow marks. The present invention relates to a sheet-shaped thermosetting composition including a phenol resin, an inorganic filler, and silicone-based particles. The present invention relates to a sheet including a thermosetting composition. The present invention relates to a method for manufacturing a device including a step for arranging a thermosetting composition on an electronic component, a step for forming a complex, and a step for causing curing of the thermosetting composition by heating the complex.

Description

熱硬化性組成物およびシート・装置の製造方法Thermosetting composition and sheet / device manufacturing method
　本発明は、熱硬化性組成物とシートと装置の製造方法とに関する。 The present invention relates to a thermosetting composition, a sheet, and a method for producing an apparatus.
　電子部品上にシート状の熱硬化性組成物を配置する工程と、熱硬化性組成物の軟化を起こし、熱硬化性組成物で電子部品を覆う工程と、熱硬化性組成物で電子部品を覆う工程により形成された複合体を加熱することにより熱硬化性組成物の硬化を起こす工程とを含む方法により装置を製造できる。 The step of placing a sheet-like thermosetting composition on the electronic component, the step of softening the thermosetting composition, covering the electronic component with the thermosetting composition, and the electronic component with the thermosetting composition The apparatus can be manufactured by a method including a step of causing curing of the thermosetting composition by heating the composite formed by the covering step.
特開２００６－１９７１４号公報JP 2006-19714 A
　熱硬化性組成物で電子部品を覆うときに電子部品と熱硬化性組成物との間に気体が閉じ込められることがある。気体は移動し、硬化後における熱硬化性組成物の表面に凹凸やピンホールが発生することがある。 When the electronic component is covered with the thermosetting composition, gas may be trapped between the electronic component and the thermosetting composition. The gas moves, and irregularities and pinholes may be generated on the surface of the thermosetting composition after curing.
　いっぽう、硬化後における熱硬化性組成物の表面にフローマークが発生することもある。 On the other hand, a flow mark may be generated on the surface of the thermosetting composition after curing.
　本発明は前記課題を解決し、電子部品と熱硬化性組成物との間に閉じ込められる気体を減らすことが可能で、フローマークの発生を抑制することができる熱硬化性組成物を提供することを目的とする。本発明はまた、電子部品と熱硬化性組成物との間に閉じ込められる気体を減らすことが可能で、フローマークの発生を抑制することができるシートを提供することを目的とする。本発明はまた、内部ボイドおよび凹凸・ピンホール・フローマークが少ない装置を製造するための方法を提供することを目的とする。 The present invention solves the above-mentioned problems, and provides a thermosetting composition that can reduce the gas trapped between the electronic component and the thermosetting composition and can suppress the generation of flow marks. With the goal. Another object of the present invention is to provide a sheet that can reduce the gas trapped between the electronic component and the thermosetting composition and can suppress the generation of flow marks. It is another object of the present invention to provide a method for manufacturing a device having few internal voids and irregularities / pinholes / flow marks.
　本発明は、フェノール樹脂と無機充填剤とシリコーン系粒子とを含む、シート状の熱硬化性組成物に関する。本発明の熱硬化性組成物により、電子部品と熱硬化性組成物との間に閉じ込められる気体を減らすことができる。熱硬化性組成物で電子部品を覆うときの熱硬化性組成物の粘度が高いからだろう。本発明の熱硬化性組成物により、フローマークの発生を抑制することもできる。シリコーン系粒子がパッケージ表面の艶を抑えるからだろう。 The present invention relates to a sheet-like thermosetting composition containing a phenol resin, an inorganic filler, and silicone-based particles. With the thermosetting composition of the present invention, the gas trapped between the electronic component and the thermosetting composition can be reduced. This is because the thermosetting composition has a high viscosity when the electronic component is covered with the thermosetting composition. With the thermosetting composition of the present invention, the generation of flow marks can also be suppressed. This is probably because the silicone particles suppress the gloss of the package surface.
　シリコーン系粒子がエポキシ基を有することが好ましい。硬化後の熱硬化性組成物の強度を高められるからである。フェノール樹脂がシリコーン系粒子と結合し、シリコーンゴム粒子を拘束するのだろう。 It is preferable that the silicone-based particles have an epoxy group. This is because the strength of the thermosetting composition after curing can be increased. The phenolic resin will bind to the silicone particles and bind the silicone rubber particles.
　本発明はまた、熱硬化性組成物を含むシートに関する。熱硬化性組成物は、第１面と第１面に対向した第２面とで両面が定義される。本発明のシートは、第１面上に設けられた第１セパレータと、第２面上に設けられた第２セパレータとをさらに含む。 The present invention also relates to a sheet containing the thermosetting composition. Both sides of the thermosetting composition are defined by a first surface and a second surface facing the first surface. The sheet of the present invention further includes a first separator provided on the first surface and a second separator provided on the second surface.
　本発明はまた、装置の製造方法に関する。本発明の装置の製造方法は、熱硬化性組成物を電子部品上に配置する工程と、複合体を形成する工程とを含む。複合体は、電子部品および電子部品を覆う熱硬化性組成物を含む。複合体を形成する工程は、熱硬化性組成物の軟化を起こすステップを含む。本発明の装置の製造方法は、複合体を加熱することにより熱硬化性組成物の硬化を起こす工程をさらに含む。 The present invention also relates to a device manufacturing method. The manufacturing method of the apparatus of this invention includes the process of arrange | positioning a thermosetting composition on an electronic component, and the process of forming a composite_body | complex. The composite includes an electronic component and a thermosetting composition that covers the electronic component. The step of forming the composite includes a step of causing softening of the thermosetting composition. The manufacturing method of the apparatus of this invention further includes the process of raise | generating the thermosetting composition by heating a composite_body | complex.
実施形態１に係るシートの概略断面図である。3 is a schematic cross-sectional view of a sheet according to Embodiment 1. FIG. 装置の製造工程の概略断面図である。It is a schematic sectional drawing of the manufacturing process of an apparatus. 装置の製造工程の概略断面図である。It is a schematic sectional drawing of the manufacturing process of an apparatus. 装置の製造工程の概略断面図である。It is a schematic sectional drawing of the manufacturing process of an apparatus. 半導体装置の第１製造例における工程の概略断面図である。It is a schematic sectional drawing of the process in the 1st manufacture example of a semiconductor device. 半導体装置の第１製造例における工程の概略断面図である。It is a schematic sectional drawing of the process in the 1st manufacture example of a semiconductor device. 半導体装置の第１製造例における工程の概略断面図である。It is a schematic sectional drawing of the process in the 1st manufacture example of a semiconductor device. 半導体装置の第２製造例における工程の概略断面図である。It is a schematic sectional drawing of the process in the 2nd manufacture example of a semiconductor device. 半導体装置の第２製造例における工程の概略断面図である。It is a schematic sectional drawing of the process in the 2nd manufacture example of a semiconductor device. 半導体装置の第２製造例における工程の概略断面図である。It is a schematic sectional drawing of the process in the 2nd manufacture example of a semiconductor device. 半導体装置の第２製造例における工程の概略断面図である。It is a schematic sectional drawing of the process in the 2nd manufacture example of a semiconductor device.
　以下に実施形態を掲げ、本発明を詳細に説明するが、本発明はこれらの実施形態のみに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to embodiments, but the present invention is not limited only to these embodiments.
　［実施形態１］
　（シート１）
　図１に示すように、シート状の熱硬化性組成物１１をシート１は含む。第１面と第１面に対向した第２面とで熱硬化性組成物１１の両面は定義される。シート１は、第１面上に設けられた第１セパレータ１２をさらに含む。第１セパレータ１２としてポリエチレンテレフタレート（ＰＥＴ）フィルムなどを挙げることができる。シート１は、第２面上に設けられた第２セパレータ１３をさらに含む。第２セパレータ１３としてポリエチレンテレフタレート（ＰＥＴ）フィルムなどを挙げることができる。 [Embodiment 1]
(Sheet 1)
As shown in FIG. 1, the sheet 1 includes a sheet-like thermosetting composition 11. Both surfaces of the thermosetting composition 11 are defined by the first surface and the second surface facing the first surface. The sheet 1 further includes a first separator 12 provided on the first surface. Examples of the first separator 12 include a polyethylene terephthalate (PET) film. The sheet 1 further includes a second separator 13 provided on the second surface. Examples of the second separator 13 include a polyethylene terephthalate (PET) film.
　熱硬化性組成物１１の厚みの下限として１００μｍ、２００μｍなどを例示できる。熱硬化性組成物１１の厚みの上限として２０００μｍ、１５００μｍなどを例示できる。 Examples of the lower limit of the thickness of the thermosetting composition 11 include 100 μm and 200 μm. Examples of the upper limit of the thickness of the thermosetting composition 11 include 2000 μm and 1500 μm.
　熱硬化性組成物１１の最低溶融粘度は好ましくは１００Ｐａ・ｓ～１００００Ｐａ・ｓである。１００Ｐａ・ｓ以上であると、電子部品と熱硬化性組成物１１との間に閉じ込められる気体が少ない傾向がある。１００００Ｐａ・ｓ以下であると、成型時に電子部品と熱硬化性組成物１１との間に空間―未充填の領域―が生じない傾向がある。 The minimum melt viscosity of the thermosetting composition 11 is preferably 100 Pa · s to 10,000 Pa · s. When it is 100 Pa · s or more, there is a tendency that the gas trapped between the electronic component and the thermosetting composition 11 is small. When the pressure is 10,000 Pa · s or less, there is a tendency that no space—an unfilled region—is generated between the electronic component and the thermosetting composition 11 during molding.
　熱硬化性組成物１１はシリコーン系粒子を含む。シリコーン系粒子は、好ましくはシリコーンエラストマー粒子である。 The thermosetting composition 11 includes silicone particles. The silicone-based particles are preferably silicone elastomer particles.
　フェノール樹脂またはエポキシ樹脂の少なくともどちらかと反応する基をシリコーン系粒子が有することが好ましい。フェノール樹脂またはエポキシ樹脂の少なくともどちらかと反応する基としてエポキシ基などを挙げることができる。 It is preferable that the silicone-based particles have a group that reacts with at least one of a phenol resin and an epoxy resin. Examples of the group that reacts with at least one of a phenol resin and an epoxy resin include an epoxy group.
　シリコーン系粒子の形状は、好ましくは球状である。シリコーン系粒子の平均粒子径は、好ましくは２０μｍ以下、より好ましくは１０μｍ以下である。シリコーン系粒子の平均粒子径の下限として０．５μｍ、１μｍなどを例示できる。 The shape of the silicone-based particles is preferably spherical. The average particle size of the silicone-based particles is preferably 20 μm or less, more preferably 10 μm or less. Examples of the lower limit of the average particle diameter of the silicone particles include 0.5 μm and 1 μm.
　熱硬化性組成物１１の重量から無機充填剤の合計重量を減じることにより求められた重量を１００％としたとき、シリコーン系粒子の合計重量は好ましくは０．５％以上、より好ましくは１％以上である。熱硬化性組成物１１の重量から無機充填剤の合計重量を減じることにより求められた重量を１００％としたとき、シリコーン系粒子の合計重量は好ましくは５０％以下、より好ましくは４５％以下である。５０％をこえると、電子部品と熱硬化性組成物１１との間に空間―未充填の領域―が残ることがある。 When the weight obtained by subtracting the total weight of the inorganic filler from the weight of the thermosetting composition 11 is 100%, the total weight of the silicone-based particles is preferably 0.5% or more, more preferably 1%. That's it. When the weight obtained by subtracting the total weight of the inorganic filler from the weight of the thermosetting composition 11 is defined as 100%, the total weight of the silicone-based particles is preferably 50% or less, more preferably 45% or less. is there. If it exceeds 50%, a space—an unfilled region—may remain between the electronic component and the thermosetting composition 11.
　２５℃で液状のエポキシ樹脂と２５℃で固形のエポキシ樹脂とを熱硬化性組成物１１が含む。２５℃で液状のエポキシ樹脂を配合することにより、ロール混練機などを用いた混練押出による熱硬化性組成物１１の製造が可能となる。 The thermosetting composition 11 includes an epoxy resin that is liquid at 25 ° C. and an epoxy resin that is solid at 25 ° C. By blending a liquid epoxy resin at 25 ° C., the thermosetting composition 11 can be produced by kneading extrusion using a roll kneader or the like.
　２５℃で液状をなすエポキシ樹脂のエポキン当量は、好ましくは１００ｇ／ｅｑ以上、より好ましくは１２０ｇ／ｅｑ以上である。２５℃で液状をなすエポキシ樹脂のエポキシ当量は、好ましくは５００ｇ／ｅｑ以下、より好ましくは３００ｇ／ｅｑ以下である。エポキシ当量は、ＪＩＳ Ｋ ７２３６－２００９に規定された方法で測定できる。２５℃で液状のエポキシ樹脂としてビスフェノールＡ型エポキシ樹脂などを挙げることができる。 The epochine equivalent of the epoxy resin that is liquid at 25 ° C. is preferably 100 g / eq or more, more preferably 120 g / eq or more. The epoxy equivalent of the epoxy resin that is liquid at 25 ° C. is preferably 500 g / eq or less, more preferably 300 g / eq or less. The epoxy equivalent can be measured by the method defined in JIS K 7236-2009. Examples of the epoxy resin that is liquid at 25 ° C. include bisphenol A type epoxy resin.
　２５℃で固形のエポキシ樹脂としてエポキシ当量１００～１８０ｇ／ｅｑのエポキシ樹脂、エポキシ当量２００ｇ／ｅｑ以上のエポキシ樹脂などを挙げることができる。エポキシ当量１００～１８０ｇ／ｅｑのエポキシ樹脂とエポキシ当量２００ｇ／ｅｑ以上のエポキシ樹脂とを熱硬化性組成物１１が好ましくは含む。エポキシ当量１００～１８０ｇ／ｅｑのエポキシ樹脂を配合することにより、熱硬化後における熱硬化性組成物１１のガラス転移温度を上げることができる。エポキシ当量２００ｇ／ｅｑ以上のエポキシ樹脂としてジシクロペンタジエン型エポキシ樹脂などを挙げることができる。 Examples of the epoxy resin solid at 25 ° C. include an epoxy resin having an epoxy equivalent of 100 to 180 g / eq, an epoxy resin having an epoxy equivalent of 200 g / eq or more, and the like. The thermosetting composition 11 preferably contains an epoxy resin having an epoxy equivalent of 100 to 180 g / eq and an epoxy resin having an epoxy equivalent of 200 g / eq or more. By blending an epoxy resin having an epoxy equivalent of 100 to 180 g / eq, the glass transition temperature of the thermosetting composition 11 after thermosetting can be increased. Examples of the epoxy resin having an epoxy equivalent of 200 g / eq or more include a dicyclopentadiene type epoxy resin.
　熱硬化性組成物１１の重量から無機充填剤の合計重量を減じることにより求められた重量を１００％としたとき、エポキシ樹脂の合計重量は好ましくは２０％以上である。熱硬化性組成物１１の重量から無機充填剤の合計重量を減じることにより求められた重量を１００％としたとき、エポキシ樹脂の合計重量は好ましくは８０％以下である。 When the weight obtained by subtracting the total weight of the inorganic filler from the weight of the thermosetting composition 11 is taken as 100%, the total weight of the epoxy resin is preferably 20% or more. When the weight obtained by subtracting the total weight of the inorganic filler from the weight of the thermosetting composition 11 is 100%, the total weight of the epoxy resin is preferably 80% or less.
　熱硬化性組成物１１はフェノール樹脂を含む。フェノール樹脂としてフェノールノボラック樹脂、フェノールアラルキル樹脂、ビフェニルアラルキル樹脂、ジシクロペンタジエン型フェノール樹脂、クレゾールノボラック樹脂、レゾール樹脂などを挙げることができる。これらフェノール樹脂は単独で用いてもよいし、２種以上併用してもよい。フェノール樹脂の水酸基当量は好ましくは７０～２５０である。フェノール樹脂の軟化点は好ましくは５０～１１０℃である。 The thermosetting composition 11 contains a phenol resin. Examples of the phenol resin include a phenol novolak resin, a phenol aralkyl resin, a biphenyl aralkyl resin, a dicyclopentadiene type phenol resin, a cresol novolac resin, and a resole resin. These phenolic resins may be used alone or in combination of two or more. The hydroxyl equivalent of the phenol resin is preferably 70 to 250. The softening point of the phenol resin is preferably 50 to 110 ° C.
　エポキシ樹脂とフェノール樹脂の配合割合は、硬化反応性という観点から、エポキシ樹脂中のエポキシ基１当量に対して、フェノール樹脂中の水酸基の合計が０．７～１．５当量となるように配合することが好ましく、より好ましくは０．９～１．２当量である。 The blending ratio of the epoxy resin and the phenol resin is blended so that the total of hydroxyl groups in the phenol resin is 0.7 to 1.5 equivalents with respect to 1 equivalent of the epoxy group in the epoxy resin from the viewpoint of curing reactivity. It is preferable to use 0.9 to 1.2 equivalents.
　熱硬化性組成物１１の重量から無機充填剤の合計重量を減じることにより求められた重量を１００％としたとき、フェノール樹脂の合計重量は好ましくは５％以上、より好ましくは１０％以上である。熱硬化性組成物１１の重量から無機充填剤の合計重量を減じることにより求められた重量を１００％としたとき、フェノール樹脂の合計重量は好ましくは６０％以下、より好ましくは４０％以下である。 When the weight obtained by subtracting the total weight of the inorganic filler from the weight of the thermosetting composition 11 is 100%, the total weight of the phenol resin is preferably 5% or more, more preferably 10% or more. . When the weight obtained by subtracting the total weight of the inorganic filler from the weight of the thermosetting composition 11 is taken as 100%, the total weight of the phenol resin is preferably 60% or less, more preferably 40% or less. .
　熱硬化性組成物１１は無機充填剤を含む。無機充填剤として石英ガラス、タルク、シリカ、アルミナ、窒化ホウ素、窒化アルミニウム、炭化珪素などを挙げることができる。なかでも、熱膨張係数を良好に低減できるという理由からシリカが好ましい。流動性に優れるという理由から、溶融シリカが好ましく、球状溶融シリカがより好ましい。熱伝導率が高いという理由から、アルミナ、窒化ホウ素、窒化アルミニウムが好ましい。１種の無機充填剤を熱硬化性組成物１１は含むことができる。２種以上の無機充填剤を含むこともできる。 The thermosetting composition 11 contains an inorganic filler. Examples of the inorganic filler include quartz glass, talc, silica, alumina, boron nitride, aluminum nitride, and silicon carbide. Among these, silica is preferable because the thermal expansion coefficient can be satisfactorily reduced. For reasons of excellent fluidity, fused silica is preferred, and spherical fused silica is more preferred. Alumina, boron nitride, and aluminum nitride are preferred because of their high thermal conductivity. The thermosetting composition 11 can contain one kind of inorganic filler. Two or more inorganic fillers can also be included.
　無機充填剤の平均粒子径は、好ましくは０．５μｍ以上、より好ましくは１μｍ以上である。フィラーの平均粒子径は、好ましくは３０μｍ以下である。平均粒子径は、たとえば、母集団から任意に抽出される試料を用い、レーザー回折散乱式粒度分布測定装置を用いて測定することにより導き出すことができる。 The average particle diameter of the inorganic filler is preferably 0.5 μm or more, more preferably 1 μm or more. The average particle diameter of the filler is preferably 30 μm or less. The average particle diameter can be derived by, for example, using a sample arbitrarily extracted from the population and measuring it using a laser diffraction / scattering particle size distribution measuring apparatus.
　熱硬化性組成物１１中の無機充填剤の含有量は、５５体積％以上、より好ましくは６０体積％以上、さらに好ましくは７０体積％以上である。無機充填剤の含有量を高めることにより、硬化後の熱硬化性組成物１１の線膨張係数を基板などの線膨張係数に近づけることが可能である。熱硬化性組成物１１中の無機充填剤の含有量は、好ましくは８５体積％以下、より好ましくは８０体積％以下である。８５体積％以下であると、シート状に成形しやすい。 The content of the inorganic filler in the thermosetting composition 11 is 55% by volume or more, more preferably 60% by volume or more, and still more preferably 70% by volume or more. By increasing the content of the inorganic filler, it is possible to bring the linear expansion coefficient of the cured thermosetting composition 11 closer to the linear expansion coefficient of the substrate or the like. The content of the inorganic filler in the thermosetting composition 11 is preferably 85% by volume or less, more preferably 80% by volume or less. It is easy to shape | mold into a sheet form as it is 85 volume% or less.
　無機充填剤の含有量は、「重量％」を単位としても説明できる。代表的にシリカの含有量を「重量％」で説明する。熱硬化性組成物１１中のシリカの含有量は、好ましくは６０重量％以上、より好ましくは７０重量％以上、さらに好ましくは８０重量％以上、さらに好ましくは８５重量％以上である。熱硬化性組成物１１中のシリカの含有量の上限はたとえば９５重量％である。 The content of the inorganic filler can be explained in units of “% by weight”. Typically, the silica content will be described in terms of “% by weight”. The content of silica in the thermosetting composition 11 is preferably 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and further preferably 85% by weight or more. The upper limit of the content of silica in the thermosetting composition 11 is, for example, 95% by weight.
　アルミナの含有量も「重量％」で説明する。熱硬化性組成物１１中のアルミナの含有量は、好ましくは７２重量％以上、より好ましくは８０重量％以上、さらに好ましくは８７重量％以上である。熱硬化性組成物１１中のアルミナの含有量は、好ましくは９５重量％以下、より好ましくは９３重量％以下である。 The content of alumina is also described in “% by weight”. The content of alumina in the thermosetting composition 11 is preferably 72% by weight or more, more preferably 80% by weight or more, and further preferably 87% by weight or more. The content of alumina in the thermosetting composition 11 is preferably 95% by weight or less, more preferably 93% by weight or less.
　熱硬化性組成物１１はシランカップリング剤を含む。シランカップリング剤として３－グリシドキシプロピルトリメトキシシランなどを挙げることができる。 The thermosetting composition 11 contains a silane coupling agent. Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane.
　熱硬化性組成物１１は硬化促進剤を含む。硬化促進剤としては、エポキシ樹脂とフェノール樹脂の硬化を進行させるものであれば特に限定されず、たとえば、２－メチルイミダゾール（商品名；２ＭＺ）、２－ウンデシルイミダゾール（商品名；Ｃ１１－Ｚ）、２－ヘプタデシルイミダゾール（商品名；Ｃ１７Ｚ）、１，２－ジメチルイミダゾール（商品名；１．２ＤＭＺ）、２－エチル－４－メチルイミダゾール（商品名；２Ｅ４ＭＺ）、２－フェニルイミダゾール（商品名；２ＰＺ）、２－フェニル－４－メチルイミダゾール（商品名；２Ｐ４ＭＺ）、１－ベンジル－２－メチルイミダゾール（商品名；１Ｂ２ＭＺ）、１－ベンジル－２－フェニルイミダゾール（商品名；１Ｂ２ＰＺ）、１－シアノエチル－２－メチルイミダゾール（商品名；２ＭＺ－ＣＮ）、１－シアノエチル－２－ウンデシルイミダゾール（商品名；Ｃ１１Ｚ－ＣＮ）、１－シアノエチル－２－フェニルイミダゾリウムトリメリテイト（商品名；２ＰＺＣＮＳ－ＰＷ）、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン（商品名；２ＭＺ－Ａ）、２，４－ジアミノ－６－［２’－ウンデシルイミダゾリル－（１’）］－エチル－ｓ－トリアジン（商品名；Ｃ１１Ｚ－Ａ）、２，４－ジアミノ－６－［２’－エチル－４’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン（商品名；２Ｅ４ＭＺ－Ａ）、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジンイソシアヌル酸付加物（商品名；２ＭＡ－ＯＫ）、２－フェニル－４，５－ジヒドロキシメチルイミダゾール（商品名；２ＰＨＺ－ＰＷ）、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール（商品名；２Ｐ４ＭＨＺ－ＰＷ）などのイミダゾール系硬化促進剤を挙げることができる（いずれも四国化成工業（株）製）。なかでも、混練温度における硬化反応の進行を抑えることができるという理由から、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２，４－ジアミノ－６－［２’－エチル－４’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジンがより好ましく、２－フェニル－４，５－ジヒドロキシメチルイミダゾールがさらに好ましい。 The thermosetting composition 11 includes a curing accelerator. The curing accelerator is not particularly limited as long as it can cure the epoxy resin and the phenol resin. For example, 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11-Z) ), 2-heptadecylimidazole (trade name; C17Z), 1,2-dimethylimidazole (trade name; 1.2 DMZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-phenylimidazole (product) Name; 2PZ), 2-phenyl-4-methylimidazole (trade name; 2P4MZ), 1-benzyl-2-methylimidazole (trade name; 1B2MZ), 1-benzyl-2-phenylimidazole (trade name; 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name; 2MZ-CN), 1-cyanoethyl 2-Undecylimidazole (trade name; C11Z-CN), 1-cyanoethyl-2-phenylimidazolium trimellitate (trade name; 2PZCNS-PW), 2,4-diamino-6- [2'-methylimidazolyl- (1 ′)]-Ethyl-s-triazine (trade name; 2MZ-A), 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine (trade name) C11Z-A), 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (trade name; 2E4MZ-A), 2,4- Diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct (trade name; 2MA-OK), 2-phenyl-4,5-dihydroxymethyl ester Examples include imidazole curing accelerators such as dazole (trade name; 2PHZ-PW) and 2-phenyl-4-methyl-5-hydroxymethylimidazole (trade name; 2P4MHZ-PW). Made by Co., Ltd.). Among them, 2-phenyl-4,5-dihydroxymethylimidazole, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl) is preferable because the progress of the curing reaction at the kneading temperature can be suppressed. -(1 ')]-Ethyl-s-triazine is more preferred, and 2-phenyl-4,5-dihydroxymethylimidazole is more preferred.
　硬化促進剤の含有量は、エポキシ樹脂およびフェノール樹脂の合計１００重量部に対して、好ましくは０．２重量部以上、より好ましくは０．５重量部以上、さらに好ましくは０．８重量部以上である。硬化促進剤の含有量は、エポキシ樹脂およびフェノール樹脂の合計１００重量部に対して、好ましくは５重量部以下、より好ましくは２重量部以下である。 The content of the curing accelerator is preferably 0.2 parts by weight or more, more preferably 0.5 parts by weight or more, further preferably 0.8 parts by weight or more with respect to 100 parts by weight of the total of the epoxy resin and the phenol resin. It is. The content of the curing accelerator is preferably 5 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the total of the epoxy resin and the phenol resin.
　熱硬化性組成物１１はカーボンブラックを含む。 The thermosetting composition 11 contains carbon black.
　熱硬化性組成物１１は、たとえば、フェノール樹脂、無機充填剤、シリコーン系粒子などを混練して得られる混合物をシート状に成形する工程を含む方法により製造できる。混練における温度の上限はたとえば１４０℃、１３０℃である。温度の下限はたとえば３０℃、５０℃である。混練の時間は、好ましくは１～３０分である。減圧条件下（減圧雰囲気下）で混練することが好ましい。減圧雰囲気の圧力は、たとえば１×１０－４～０．１ｋｇ／ｃｍ２である。 The thermosetting composition 11 can be manufactured, for example, by a method including a step of forming a mixture obtained by kneading a phenol resin, an inorganic filler, silicone-based particles and the like into a sheet shape. The upper limit of the temperature in kneading is, for example, 140 ° C or 130 ° C. The lower limit of the temperature is, for example, 30 ° C. or 50 ° C. The kneading time is preferably 1 to 30 minutes. It is preferable to knead under reduced pressure conditions (under reduced pressure atmosphere). The pressure in the reduced pressure atmosphere is, for example, 1 × 10 −4 to 0.1 kg / cm 2 .
　熱硬化性組成物１１を形成するための成分（フェノール樹脂、無機充填剤、シリコーン系粒子など）を溶剤に溶解または分散させてワニスを調整し、このワニスを支持体上に塗布し、塗布膜を乾燥させることにより熱硬化性組成物１１を製造することもできる。溶剤としてメチルエチルケトン、酢酸エチル、トルエンなどを挙げることができる。 Components for forming the thermosetting composition 11 (phenol resin, inorganic filler, silicone particles, etc.) are dissolved or dispersed in a solvent to prepare a varnish, and this varnish is applied onto a support, and a coating film The thermosetting composition 11 can also be manufactured by drying. Examples of the solvent include methyl ethyl ketone, ethyl acetate, toluene and the like.
　熱硬化性組成物１１は電子部品を封止するために使用できる。電子部品としてセンサー、ＭＥＭＳ（Ｍｉｃｒｏ　Ｅｌｅｃｔｒｏ　Ｍｅｃｈａｎｉｃａｌ　Ｓｙｓｔｅｍｓ）、ＳＡＷ（Ｓｕｒｆａｃｅ　Ａｃｏｕｓｔｉｃ　Ｗａｖｅ）チップ、半導体素子、コンデンサ、抵抗などを挙げることができる。センサーとして圧力センサー、振動センサーなどを挙げることができる。半導体素子としては、半導体チップ、ＩＣ（集積回路）、トランジスタなどを挙げることができる。熱硬化性組成物１１は半導体素子を封止するために特に好適に使用できる。 The thermosetting composition 11 can be used for sealing electronic components. Examples of the electronic component include a sensor, a MEMS (Micro Electro Mechanical Systems), a SAW (Surface Acoustic Wave) chip, a semiconductor element, a capacitor, and a resistor. Examples of the sensor include a pressure sensor and a vibration sensor. Examples of the semiconductor element include a semiconductor chip, an IC (integrated circuit), and a transistor. The thermosetting composition 11 can be particularly preferably used for sealing a semiconductor element.
　（装置の製造方法）
　図２に示すように、装置の製造方法は、熱硬化性組成物１１を電子部品２１上に配置する工程を含む。図３に示すように、装置の製造方法は、電子部品２１および電子部品２１を覆う熱硬化性組成物１１を含む複合体２を形成する工程をさらに含む。装置の製造方法は、複合体２を加熱することにより熱硬化性組成物１１の硬化を起こす工程をさらに含む。 (Device manufacturing method)
As shown in FIG. 2, the device manufacturing method includes a step of disposing the thermosetting composition 11 on the electronic component 21. As shown in FIG. 3, the device manufacturing method further includes a step of forming the electronic component 21 and the composite 2 including the thermosetting composition 11 covering the electronic component 21. The device manufacturing method further includes a step of causing the thermosetting composition 11 to cure by heating the composite 2.
　熱硬化性組成物１１を電子部品２１上に配置する工程の前に、熱硬化性組成物１１から第１セパレータ１２を剥離する工程を装置の製造方法はさらに含む。 The device manufacturing method further includes a step of peeling the first separator 12 from the thermosetting composition 11 before the step of disposing the thermosetting composition 11 on the electronic component 21.
　熱硬化性組成物１１を電子部品２１上に配置する工程は、具体的には、熱硬化性組成物１１と熱硬化性組成物１１の第２面上に設けられた第２セパレータ１３とを含むシートを電子部品２１上に配置する工程である。 The step of disposing the thermosetting composition 11 on the electronic component 21 specifically includes the thermosetting composition 11 and the second separator 13 provided on the second surface of the thermosetting composition 11. This is a step of disposing the containing sheet on the electronic component 21.
　複合体２を形成する工程は、熱硬化性組成物１１の軟化を起こすステップを含む。熱硬化性組成物１１の軟化を起こすステップでは、好ましくは４０℃以上、より好ましくは５０℃以上、さらに好ましくは６０℃以上で熱硬化性組成物１１を加熱する。熱硬化性組成物１１の軟化を起こすステップでは、好ましくは１５０℃以下、より好ましくは１００℃以下、さらに好ましくは９０℃以下で熱硬化性組成物１１を加熱する。複合体２を形成する工程は、電子部品２１を熱硬化性組成物１１で覆うステップをさらに含む。電子部品２１を熱硬化性組成物１１で覆うステップは、具体的には、減圧雰囲気下で電子部品２１を熱硬化性組成物１１に埋め込むステップである。減圧雰囲気は、たとえば０．１ｋＰａ～５ｋＰａの雰囲気、０．１Ｐａ～１００Ｐａの雰囲気などである。 The process of forming the composite 2 includes a step of causing the thermosetting composition 11 to soften. In the step of causing softening of the thermosetting composition 11, the thermosetting composition 11 is preferably heated at 40 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 60 ° C. or higher. In the step of causing softening of the thermosetting composition 11, the thermosetting composition 11 is preferably heated at 150 ° C. or lower, more preferably 100 ° C. or lower, and further preferably 90 ° C. or lower. The process of forming the composite 2 further includes a step of covering the electronic component 21 with the thermosetting composition 11. Specifically, the step of covering the electronic component 21 with the thermosetting composition 11 is a step of embedding the electronic component 21 in the thermosetting composition 11 under a reduced pressure atmosphere. The reduced pressure atmosphere is, for example, an atmosphere of 0.1 kPa to 5 kPa, an atmosphere of 0.1 Pa to 100 Pa, or the like.
　熱硬化性組成物１１の硬化を起こす工程では、好ましくは１００℃以上、より好ましくは１２０℃以上で複合体２を加熱する。熱硬化性組成物１１の硬化を起こす工程では、好ましくは２００℃以下、より好ましくは１８０℃以下で複合体２を加熱する。 In the step of curing the thermosetting composition 11, the composite 2 is preferably heated at 100 ° C. or higher, more preferably 120 ° C. or higher. In the step of causing the thermosetting composition 11 to cure, the composite 2 is preferably heated at 200 ° C. or lower, more preferably 180 ° C. or lower.
　図４に示すように、熱硬化性組成物１１の硬化を起こす工程後の複合体２は、電子部品２１と電子部品２１を覆う硬化後の熱硬化性組成物３１とを含む。熱硬化性組成物１１の硬化を起こす工程の後に、装置の製造方法は配線を形成する工程などを含む。 As shown in FIG. 4, the composite 2 after the step of causing the thermosetting composition 11 to cure includes an electronic component 21 and a cured thermosetting composition 31 that covers the electronic component 21. After the step of causing the thermosetting composition 11 to harden, the device manufacturing method includes a step of forming a wiring.
　以下では、半導体装置の製造方法の一例を代表的に説明する。 Hereinafter, an example of a method for manufacturing a semiconductor device will be representatively described.
　図５に示すように、積層体１０１は、仮固定体１４１と、仮固定体１４１上に配置された熱硬化性組成物１１と、熱硬化性組成物１１上に配置された第２セパレータ１３とを含む。下側加熱板１６１と上側加熱板１６２との間に積層体１０１は配置されている。仮固定体１４１は、支持板１４２と、支持板１４２上に配置された粘着剤層１４３と、粘着剤層１４３に固定された半導体チップ１２１とを含む。粘着剤層１４３の材料として熱発泡性粘着剤などの熱剥離性粘着剤などを挙げることができる。 As shown in FIG. 5, the laminated body 101 includes a temporary fixing body 141, a thermosetting composition 11 disposed on the temporary fixing body 141, and a second separator 13 disposed on the thermosetting composition 11. Including. The laminate 101 is disposed between the lower heating plate 161 and the upper heating plate 162. The temporarily fixed body 141 includes a support plate 142, an adhesive layer 143 disposed on the support plate 142, and a semiconductor chip 121 fixed to the adhesive layer 143. Examples of the material of the pressure-sensitive adhesive layer 143 include a heat-peelable pressure-sensitive adhesive such as a heat-foamable pressure-sensitive adhesive.
　図６に示すように、下側加熱板１６１と上側加熱板１６２とを用いて平行平板方式で積層体１０１を減圧雰囲気下で熱プレスすることにより、チップ複合体１０２を形成する。チップ複合体１０２は、半導体チップ１２１と、半導体チップ１２１を覆う熱硬化性組成物１１とを含む。チップ複合体１０２は粘着剤層１４３と接する。チップ複合体１０２は第２セパレータ１３と接する。 As shown in FIG. 6, the chip composite 102 is formed by heat-pressing the laminated body 101 in a reduced pressure atmosphere by a parallel plate method using a lower heating plate 161 and an upper heating plate 162. The chip composite 102 includes a semiconductor chip 121 and the thermosetting composition 11 that covers the semiconductor chip 121. The chip composite 102 is in contact with the adhesive layer 143. The chip composite 102 is in contact with the second separator 13.
　チップ複合体１０２から第２セパレータ１３を剥離する。熱硬化性組成物１１の硬化を起こす。粘着剤層１４３を加熱し、粘着剤層１４３からチップ複合体１０２を剥離する。図７に示すように、配線１７１などを形成する。配線１７１などを形成した後にチップ複合体１０２のダイシングをなす。以上の手順により、半導体装置を得る。 The second separator 13 is peeled from the chip composite 102. Curing of the thermosetting composition 11 occurs. The pressure-sensitive adhesive layer 143 is heated, and the chip composite 102 is peeled from the pressure-sensitive adhesive layer 143. As shown in FIG. 7, wirings 171 and the like are formed. After the wiring 171 is formed, the chip composite 102 is diced. The semiconductor device is obtained by the above procedure.
　半導体装置の製造方法についてもうひとつの例を説明する。 Another example of a semiconductor device manufacturing method will be described.
　図８に示すように、積層構造体２０１は、実装ウェハ２４１と、実装ウェハ２４１上に配置された熱硬化性組成物１１と、熱硬化性組成物１１上に配置された第２セパレータ１３とを含む。下側加熱板２６１と上側加熱板２６２との間に積層構造体２０１は配置されている。実装ウェハ２４１は、半導体ウェハ２４２と、半導体チップ２２１と、半導体ウェハ２４２と半導体チップ２２１の間に挟まれたアンダーフィル材２４３とを含む。半導体ウェハ２４２は電極を有する。 As shown in FIG. 8, the laminated structure 201 includes a mounting wafer 241, a thermosetting composition 11 disposed on the mounting wafer 241, and a second separator 13 disposed on the thermosetting composition 11. including. The laminated structure 201 is disposed between the lower heating plate 261 and the upper heating plate 262. The mounting wafer 241 includes a semiconductor wafer 242, a semiconductor chip 221, and an underfill material 243 sandwiched between the semiconductor wafer 242 and the semiconductor chip 221. The semiconductor wafer 242 has electrodes.
　図９に示すように、下側加熱板２６１と上側加熱板２６２とを用いて平行平板方式で積層構造体２０１を熱プレスすることにより、ウェハ複合体２０２を形成する。ウェハ複合体２０２は、半導体ウェハ２４２と、半導体チップ２２１と、半導体ウェハ２４２と半導体チップ２２１の間に挟まれたアンダーフィル材２４３と、半導体チップ２２１を覆う熱硬化性組成物１１とを含む。ウェハ複合体２０２は第２セパレータ１３と接する。 As shown in FIG. 9, a wafer composite 202 is formed by hot-pressing the laminated structure 201 by a parallel plate method using a lower heating plate 261 and an upper heating plate 262. The wafer composite 202 includes a semiconductor wafer 242, a semiconductor chip 221, an underfill material 243 sandwiched between the semiconductor wafer 242 and the semiconductor chip 221, and the thermosetting composition 11 that covers the semiconductor chip 221. Wafer composite 202 is in contact with second separator 13.
　ウェハ複合体２０２から第２セパレータ１３を剥離する。熱硬化性組成物１１の硬化を起こす。図１０に示すように、ウェハ複合体２０２を研削する。図１１に示すように、配線２７１などを形成する。配線２７１などを形成した後にウェハ複合体２０２のダイシングをなす。以上の手順により、半導体装置を得る。 The second separator 13 is peeled from the wafer composite 202. Curing of the thermosetting composition 11 occurs. As shown in FIG. 10, the wafer composite 202 is ground. As shown in FIG. 11, wirings 271 and the like are formed. After forming the wiring 271 and the like, the wafer composite 202 is diced. The semiconductor device is obtained by the above procedure.
　（変形例１）
　変形例１では、熱硬化性組成物１１は複数の層を有する多層構造をなす。 (Modification 1)
In Modification 1, the thermosetting composition 11 has a multilayer structure having a plurality of layers.
　以下に、この発明の好適な実施例を例示的に詳しく説明する。ただし、この実施例に記載されている材料や配合量などは、特に限定的な記載がない限りは、この発明の範囲をそれらのみに限定する趣旨のものではない。 Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, blending amounts, and the like described in the examples are not intended to limit the scope of the present invention only to those unless otherwise specified.
　［樹脂シートの作製］
　樹脂シートを作製するために使用した成分について説明する。
　エポキシ樹脂１：日本化薬社製のＥＰＰＮ－５０１ＨＹ（エポキン当量１６２ｇ／ｅｑ．～１７２ｇ／ｅｑ．軟化点５１℃～５７℃のエポキシ樹脂）
　エポキシ樹脂２：三菱化学社製のｊＥＲ８２８（エポキン当量１８４ｇ／ｅｑ．～１９４ｇ／ｅｑ．の２５℃で液状のビスフェノールＡ型エポキシ樹脂）
　エポキシ樹脂３：ＤＩＣ社製のＨＰ７２００（エポキン当量２５４ｇ／ｅｑ．～２６４ｇ／ｅｑ．、軟化点５６℃～６６℃のジシクロペンタジエン型エポキシ樹脂）
　フェノール樹脂：群栄化学社製のＬＶＲ－８２１０ＤＬ（水酸基当量１０４ｇ／ｅｑ．、軟化点６０℃のノボラック型フェノール樹脂）
　フィラー：電気化学工業社製のＦＢ－９４５４ＦＣ（溶融球状シリカ）
　シリコーン系粒子：東レダウコーニング社製のＥＰ－２６０１（エポキシ基を有する、平均粒径２μｍの球状シリコーンエラストマー粒子）
　カーボンブラック：三菱化学社製の＃２０
　触媒：四国化成工業社製の２ＰＨＺ－ＰＷ（２－フェニル－４，５－ジヒドロキシメチルイミダゾール）
　シランカップリング剤：信越化学社製のＫＢＭ－４０３（３－グリシドキシプロピルトリメトキシシラン） [Production of resin sheet]
The components used for producing the resin sheet will be described.
Epoxy resin 1: EPPN-501HY (Epokin equivalent 162 g / eq. To 172 g / eq. Epoxy resin having a softening point of 51 ° C. to 57 ° C.) manufactured by Nippon Kayaku Co., Ltd.
Epoxy resin 2: jER828 (Epkin equivalent 184 g / eq. To 194 g / eq., Bisphenol A type epoxy resin liquid at 25 ° C.)
Epoxy resin 3: HP7200 (dicyclopentadiene type epoxy resin having an epkin equivalent of 254 g / eq. To 264 g / eq., Softening point of 56 ° C. to 66 ° C.) manufactured by DIC
Phenol resin: LVR-8210DL manufactured by Gunei Chemical Co., Ltd. (a novolak type phenol resin having a hydroxyl group equivalent of 104 g / eq. And a softening point of 60 ° C.)
Filler: FB-9454FC (fused spherical silica) manufactured by Denki Kagaku Kogyo Co., Ltd.
Silicone particles: EP-2601 manufactured by Toray Dow Corning (spherical silicone elastomer particles having an epoxy group and an average particle diameter of 2 μm)
Carbon black: # 20 manufactured by Mitsubishi Chemical
Catalyst: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Kasei Kogyo Co., Ltd.
Silane coupling agent: KBM-403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
　［樹脂シートの作製］
　表１の記載にしたがい各成分を配合し、ロール混練機により６０～１２０℃、１０分間、減圧条件下（０．０１ｋｇ／ｃｍ２）で溶融混練し、混合物を調製した。平板プレス法で混合物をシート状に成形することにより、厚み１ｍｍの樹脂シートを調整した。 [Production of resin sheet]
Each component was blended according to the description in Table 1, and melt kneaded in a roll kneader at 60 to 120 ° C. for 10 minutes under reduced pressure conditions (0.01 kg / cm 2 ) to prepare a mixture. A resin sheet having a thickness of 1 mm was prepared by forming the mixture into a sheet by a flat plate pressing method.
　［評価］
　以下の評価をおこなった。結果を表１に示す。 [Evaluation]
The following evaluations were made. The results are shown in Table 1.
　（粘度）
　樹脂シートをくり抜くことにより直径２５ｍｍの円形状のサンプルを得た。粘弾性測定装置ＡＲＥＳ（レオメトリックス・サイエンティフィック社製）を用いてサンプルの溶融粘度を測定した。具体的には、プレート径２５ｍｍのパラレルプレートでサンプルを挟み、昇温速度１０℃／ｍｉｎ、ひずみ１０％、周波数１Ｈｚで溶融粘度を測定した。５０℃～１５０℃における溶融粘度の最低値を最低溶融粘度とした。 (viscosity)
A circular sample having a diameter of 25 mm was obtained by hollowing out the resin sheet. The melt viscosity of the sample was measured using a viscoelasticity measuring device ARES (manufactured by Rheometrics Scientific). Specifically, the sample was sandwiched between parallel plates having a plate diameter of 25 mm, and the melt viscosity was measured at a heating rate of 10 ° C./min, a strain of 10%, and a frequency of 1 Hz. The lowest melt viscosity at 50 ° C. to 150 ° C. was defined as the minimum melt viscosity.
　（凹凸・ピンホール）
　８インチのミラーウエハと、ミラーウエハ上に等間隔に貼り付けられた１５０個の接着シート付シリコンチップ―厚み５００μｍ、７ｍｍ角―とを有する「チップ付きウエハ」を準備した。直径８インチ、厚み１０００μｍの円盤状樹脂を樹脂シートから切り出した。円盤状樹脂を「チップ付きウエハ」上に積層することにより積層体を形成した。平板プレス装置で積層体をプレスすることにより、ミラーウエハと、ミラーウエハに固定された１５０個の接着シート付シリコンチップと、１５０個の接着シート付シリコンチップを覆う厚み７００μｍの保護樹脂とを備える構造物を得た。熱風循環式乾燥機を用いて１８０℃で２時間 構造物を加熱することにより保護樹脂を硬化させた。直径１ｍｍ以上の大きさの凹凸または直径０．５ｍｍ以上のピンホールの少なくともどちらかが硬化後の保護樹脂の表面（ひょうめん）にある場合は×と判定した。直径１ｍｍ以上の大きさの凹凸および直径０．５ｍｍ以上のピンホールの両者がない場合は○と判定した。 (Uneven / Pinhole)
A “wafer with chips” having an 8-inch mirror wafer and 150 silicon chips with an adhesive sheet affixed on the mirror wafer at equal intervals—thickness 500 μm, 7 mm square—was prepared. A disc-shaped resin having a diameter of 8 inches and a thickness of 1000 μm was cut out from the resin sheet. A laminated body was formed by laminating a disk-shaped resin on a “wafer with chips”. By pressing the laminated body with a flat plate pressing apparatus, a mirror wafer, 150 silicon chips with adhesive sheet fixed to the mirror wafer, and a protective resin with a thickness of 700 μm covering 150 silicon chips with adhesive sheet are provided. A structure was obtained. The protective resin was cured by heating the structure at 180 ° C. for 2 hours using a hot air circulating dryer. When at least one of the unevenness having a diameter of 1 mm or more and the pinhole having a diameter of 0.5 mm or more is on the surface of the protective resin after curing, it was determined as x. In the case where neither the unevenness having a diameter of 1 mm or more and the pinhole having a diameter of 0.5 mm or more were present, it was judged as “good”.
　（内部ボイド・未充填領域）
　熱風循環式乾燥機を用いて１８０℃で２時間 構造物を加熱することにより保護樹脂を硬化させた。加熱後の構造物について内部ボイドと未充填領域―内部空間―とを超音波映像装置（日立ファインテック社製のＦＳ２００II）で観察した。２５ＭＨｚのプローブを使用し、反射モードで観察した。０．５ｍｍ以上の内部ボイドまたは０．５ｍｍ以上の未充填領域の少なくともどちらかがある場合は×と判定した。０．５ｍｍ以上のボイドおよび０．５ｍｍ以上の未充填領域の両者がない場合は○と判定した。 (Internal void / unfilled area)
The protective resin was cured by heating the structure at 180 ° C. for 2 hours using a hot air circulating dryer. With respect to the heated structure, the internal voids and the unfilled region-internal space- were observed with an ultrasonic imaging device (FS200II manufactured by Hitachi Finetech). Observation was performed in the reflection mode using a 25 MHz probe. When there was at least either an internal void of 0.5 mm or more or an unfilled region of 0.5 mm or more, it was determined as x. When there was neither a void of 0.5 mm or more and an unfilled region of 0.5 mm or more, it was determined as ◯.
　（フローマーク）
　熱風循環式乾燥機を用いて１８０℃で２時間 構造物を加熱することにより保護樹脂を硬化させた。硬化後の保護樹脂の表面（ひょうめん）を目視で観察した。模様を認める場合は×と判定した。模様を認めない場合は○と判定した。 (Flow mark)
The protective resin was cured by heating the structure at 180 ° C. for 2 hours using a hot air circulating dryer. The surface (hymen) of the protective resin after curing was visually observed. When a pattern was recognized, it determined with x. When the pattern was not recognized, it was judged as “good”.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　　　　１    シート
　　　１１    熱硬化性組成物
　　　１２    第１セパレータ
　　　１３    第２セパレータ
　　　２１    電子部品
　　　　２    複合体
　　　３１    硬化後の熱硬化性組成物 DESCRIPTION OF SYMBOLS 1 Sheet | seat 11 Thermosetting composition 12 1st separator 13 2nd separator 21 Electronic component 2 Composite 31 Thermosetting composition after hardening
　　　１０１  積層体
　　　１４１  仮固定体
　　　１４２  支持板
　　　１４３  粘着剤層
　　　１２１  半導体チップ
　　　１６１  下側加熱板
　　　１６２  上側加熱板
　　　１０２  チップ複合体
　　　１７１  配線 DESCRIPTION OF SYMBOLS 101 Laminated body 141 Temporary fixing body 142 Support plate 143 Adhesive layer 121 Semiconductor chip 161 Lower side heating plate 162 Upper side heating plate 102 Chip complex 171 Wiring
　　　２０１  積層構造体
　　　２４１  実装ウェハ
　　　２４２  半導体ウェハ
　　　２４３  アンダーフィル材
　　　２２１  半導体チップ
　　　２６１  下側加熱板
　　　２６２  上側加熱板
　　　２０２  ウェハ複合体
　　　２７１  配線 201 Laminated Structure 241 Mounting Wafer 242 Semiconductor Wafer 243 Underfill Material 221 Semiconductor Chip 261 Lower Heating Plate 262 Upper Heating Plate 202 Wafer Composite 271 Wiring

Claims (8)

  1. 　フェノール樹脂と無機充填剤とシリコーン系粒子とを含む、シート状の熱硬化性組成物。 A sheet-like thermosetting composition containing a phenol resin, an inorganic filler, and silicone-based particles.
  2. 　エポキシ樹脂をさらに含む請求項１に記載の熱硬化性組成物。 The thermosetting composition according to claim 1, further comprising an epoxy resin.
  3. 　前記熱硬化性組成物の重量から前記無機充填剤の合計重量を減じることにより求められた第１重量を１００％としたとき、前記シリコーン系粒子の合計重量が０．５％～５０％である請求項１または２に記載の熱硬化性組成物。 When the first weight obtained by subtracting the total weight of the inorganic filler from the weight of the thermosetting composition is 100%, the total weight of the silicone-based particles is 0.5% to 50%. The thermosetting composition according to claim 1 or 2.
  4. 　前記シリコーン系粒子がエポキシ基を有する請求項１～３のいずれかに記載の熱硬化性組成物。 The thermosetting composition according to any one of claims 1 to 3, wherein the silicone-based particles have an epoxy group.
  5. 　最低溶融粘度が１００Ｐａ・ｓ～１００００Ｐａ・ｓである請求項１～４のいずれかに記載の熱硬化性組成物。 The thermosetting composition according to any one of claims 1 to 4, wherein the minimum melt viscosity is 100 Pa · s to 10,000 Pa · s.
  6. 　電子部品を封止するための請求項１～５のいずれかに記載の熱硬化性組成物。 The thermosetting composition according to any one of claims 1 to 5, for sealing an electronic component.
  7. 　請求項１～６のいずれかに記載の熱硬化性組成物を含み、
    　前記熱硬化性組成物は、第１面と前記第１面に対向した第２面とで両面が定義され、
    　前記第１面上に設けられた第１セパレータと、
    　前記第２面上に設けられた第２セパレータとをさらに含むシート。     Comprising the thermosetting composition according to any one of claims 1 to 6,
    Both sides of the thermosetting composition are defined by a first surface and a second surface facing the first surface,
    A first separator provided on the first surface;
    A sheet further comprising a second separator provided on the second surface.
  8. 　請求項１～６のいずれかに記載の熱硬化性組成物を電子部品上に配置する工程と、
    　前記電子部品および前記電子部品を覆う前記熱硬化性組成物を含む複合体を形成する工程と、
    　前記複合体を加熱することにより前記熱硬化性組成物の硬化を起こす工程とを含み、
    　前記複合体を形成する工程は、前記熱硬化性組成物の軟化を起こすステップを含む装置の製造方法。     Disposing the thermosetting composition according to any one of claims 1 to 6 on an electronic component;
    Forming a composite comprising the electronic component and the thermosetting composition covering the electronic component;
    Causing the thermosetting composition to cure by heating the composite,
    The method of forming the composite includes a step of causing softening of the thermosetting composition.
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