PH12014502374B1 - Composition for film adhesives, method for producing same, film adhesive, semiconductor package using film adhesive and method for manufacturing semiconductor package using film adhesive - Google Patents

Composition for film adhesives, method for producing same, film adhesive, semiconductor package using film adhesive and method for manufacturing semiconductor package using film adhesive Download PDF

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Publication number
PH12014502374B1
PH12014502374B1 PH12014502374A PH12014502374A PH12014502374B1 PH 12014502374 B1 PH12014502374 B1 PH 12014502374B1 PH 12014502374 A PH12014502374 A PH 12014502374A PH 12014502374 A PH12014502374 A PH 12014502374A PH 12014502374 B1 PH12014502374 B1 PH 12014502374B1
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Philippines
Prior art keywords
film adhesive
silica filler
spherical silica
epoxy resin
film
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PH12014502374A
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PH12014502374A1 (en
Inventor
Minoru Morita
Hiroyuki Yano
Shinji Ohira
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Furukawa Electric Co Ltd
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Publication of PH12014502374A1 publication Critical patent/PH12014502374A1/en
Publication of PH12014502374B1 publication Critical patent/PH12014502374B1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—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
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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    • H01L24/83—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
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    • H01L2224/48151—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
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    • H01L2224/48225—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
    • H01L2224/48227—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 connecting the wire to a bond pad of the item
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    • H01L2224/732—Location after the connecting process
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    • H01L2924/181—Encapsulation

Abstract

A method for producing a film adhesive composition which comprises an epoxy resin (A), an epoxy resin curing agent (B), a phenoxy resin (C), and a surface-treated spherical silica filler (D) obtained by subjecting a spherical silica filler having an average particle diameter of 0.01 to 2.0 mm to a surface treatment with a silane coupling agent, and which has a content of the surface-treated spherical silica filler (D) of 30 to 70 pcnt by mass relative to a total amount of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C), and the surface-treated spherical silica filler (D), an elastic modulus at 200oC after thermal curing of 20 to 300 MPa, a saturated water absorption rate after thermal curing of 1.5 pcnt by mass or less, the method comprising: a step of obtaining a surface-treated spherical silica filler dispersion liquid by dispersing the surface-treated spherical silica filler (D) in an organic solvent; and a step of obtaining the film adhesive composition by mixing the surface-treated spherical silica filler dispersion liquid with the epoxy resin (A), the epoxy resin curing agent (B), and the phenoxy resin (C).

Description

andaphenoxyresinsuchthatacontentofthesurface-treated spherical silica filler iswithina specific range. thas, afilmadhesivecompositionandafilmadhesiveareobtained, inwhichthe sphericalsilicafillerisuniformlydispersed. ~ Moreover, the followings have been found out.
Althoughthesphericalsilicafillerhasanaverageparticle diameter as small as 0.01 to 2.0 pm, the film adhesive obtained as described above does not aggregate when the film is formed. Even when the thickness is made small, the appearance of the filmsurface is favorable. Further, the adhesiveness to an adherend is also excellent because the melt viscosity is sufficiently low. Moreover, the inventors have found out chat the above-described film adhesive is capable of retaining itselasticmodulus after curingatasufficientlyhighlevelevenatahightemperature of approximately 200°C, so that a semiconductor chip and awiringboardcanstablyadheretoeachother, and a bonding wirecanbebondedwithasufficientstrength. Furthermore, {hasbeen foundout that the £1 madhes vehasasugEiciently " low water absorption rate after curing, so that formation of a package crack can be suppressed sufficiently when a semiconductor package is mounted. These discoveries have led to the completion of the present invention.
Specifically, amethod for producing a filmadhesive composition of the present invention is a method for : producing a film adhesive composition which comprises an epoxy resin (A), an epoxy resin curing agent (B), a phenoxy resin (C), and a surface-treated spherical silica filler (D) obtainedbysubjectinga spherical silica filler having an average particle diameter of 0.01 to 2.0 um to a surface treatment with a silane coupling agent, and which has a content of the surface-treated spherical silica filler (D) of 30 to 70% by mass relative to a total amount of the epoxy resin (A), the epoxy resin curing agent ny the phenoxy resin (C), and the surface-treated spherical silica filler (D), \melasticmodalusat200°Cafter thermal curing of 20 to 3000 MPa, and asaturatedwaterabsorptionrateafterthermal curing of 1.5% by mass or less, the production method comprising: astepofobtainingasurface-treatedsphericalsilica fillerdispersionliquidbydispersingthesurface~-treated spherical silica filler (D) in an organic solvent; and a step of obtaining the film adhesive composition by mixing the surface-treated spherical silica filler dispersion liquid with the epoxy resin (A), the epoxy resin curing agent (B), and the phenoxy resin ©). oo
The method for producing a filmadhesive composition oo of the present invention preferably comprises:
a step of obtaining a silane coupling agent : | solution by dissolving the silane ceupLing agent in an organic solvent; and a step of obtaining the surface-treated spherical silica filler dispersion liquid in which the surface-treated spherical silica filler (D) is dispersed in the organic solvent by dispersing the spherical silica - filler in the silane coupling agent solution to thereby subject thesphericalsilicafillertothesurfacetreatment with the silane coupling agent. An amount of the silane coupling agent blended is preferably 1 to 5 parts by mass relative to 100 parts by mass of an amount of the spherical silica filler blended.
Moreover, inthe method for producing a filmadhesive composition of the present invention, the silane coupling agent is preferably a vinyl-based silane coupling agent represented by the following general formula (1):
R3-n—=S1i (CH3),~CH=CH, -++ (1) [in the formula (1), R represents any one hydrolyzable functional group selected from the group consisting of a methoxy group, an ethoxy group, and a 2-methoxyethoxy group, and n represents an integer of any one of 0 and 1].
A filmadhesive composition of the present invention is obtained by the method for producing a film adhesive composition of the present invention.
Moreover, a film adhesive of the present invention is a film adhesive obtained by forming the film adhesive composition of the present invention into a film shape, the film adhesive having a melt viscosity at 80°C of 10000
Pa*s or less observed using a rheometer when heated from 20°C at a rate of temperature rise of 10°C/minute. The film adhesive of the present invention preferably has a thickness of 1 to 50 pm.
: A method for manufacturing a semiconductor package of the present smvention is a manufacturing method comprising: a first step of providing an adhesive layer on a bottom surface of a wafer having a top surface on which at least one semiconductor circuit is formed, the adhesive layer being formed by thermocompression bonding from the film adhesive of the present invention; a second step of simultaneously dicing the wafer and the adhesive layer after the wafer and a dicing tape adhere to each other with the adhesive layer therebetween to thus obtain an adhesive layer-provided semiconductor chip including the wafer and the adhesive layer; a third step of detaching the dicing tape from the adhesive layer, and thermocompression bonding a wiring "board and the adhesive layer-provided semiconductor chip to each other with the adhesive layer therebetween; and a fourth step of thermally curing the film adhesive.
Additionally, a semiconductor package of the present invention is obtained by the method for manufacturing a semiconductor package of the present invention.
Incidentally, although it is not exactly clear why the above object is achieved by the aspects of the present invention, the present inventors presume the reason as follows. Specifically, in a conventional method for producing a film adhesive composition containing a silica filler, a so-called integrant method, in which a silica filler and, as necessary, a silane coupling agent are directly blended with resin components, has been widely . used because of its easiness. Nevertheless, in such a method, a lot of silanol groups remain on the surface of the silica filler, so that the silica filler is likely to aggregate with one another particularly in a case where a silica filler used has a small particle diameter. As
‘ ' . ' a result, the present inventors presume that the surface : appearance of the obtained film adhesive is deteriorated, and the water absorption rate after curing is increased.
Meanwhile, in order to prevent the deterioration of the surface appearance or the like due to such aggregation of silica fillers, a step such as roll kneading may be : adopted in the integrant method so that the aggregate can be broken apart byapplyingastrong shear force. However, thepresentinventorspresumethatthisincreasesthenumber of steps and makes it difficult to obtain a film adhesive composition having a sufficient quality particularly in the case where a silica filler used has a small particle © diameter. :
In contrast, according to the method for producing a film adhesive composition of the present invention, the silica filler used is a surface-treated spherical silica filler obtained by subjecting a spherical silica filler
‘ ; y \ to a surface treatment with a silane coupling agent.
Accordingly, che use of the resulting film adnesive composition makes it possible to obtain a film adhesive which comprises the surface-treated spherical silica filler with a silanol group on a surface thereof having been sufficiently treated the silane coupling agent, and which sufficiently suppresses package crack formationdue to an increase in the water absorption rate.
Moreover, a surface-treated spherical silica filler sufficiently subjecting to a surface treatment is readily dispersedinanorganicsolvent. Accordingly, thepresent inventors presume that mixing a surface-treated spherical silica filler dispersion liquid, in which such a filler is dispersed in an organic solvent, with resin components such as an epoxy resin, an epoxy resin curing agent, and phenoxy resinenables evenasphericalsilicafillerhaving s smallparticle diameter tobe uniformly dispersedwithout :
aggregating in the resin components, so that the resulting filmadhesivehasafavorablesurface appearance. Further, the present inventors presume that dispersing the surface-treated spherical silica filler in the resin components in such a specific combination makes the melt viscosity of the obtained film adhesive sufficiently low.
Furthermore, the suppression of aggregation according to the method for producing a film adhesive compositionofthepresentinventionenablesalargeramount of the spherical silica filler to be incorporated in a filmadhesive. Accordingly, thepresentinventorspresume that the elastic modulus at high temperature after curing canberetainedatahighlevel. Thus, thepresentinventors presume that particularly when a semiconductor chip is made thinner and smaller, such a film adhesive enables the semiconductor chip and a wiring board to adhere to a cach other with high precision, enables a bonding wire
COMPOSITION FOR FILM ADHESIVES, METHOD FOR PRODUCING SAME,
FILM ADHESIVE, SEMICONDUCTOR PACKAGE USING FILM ADHESIVE
AND METHOD FOR MANUFACTURING SEMICONDUCTOR PACKAGE USING :
R em
FILM ADHESIVE : : [Technical Field] > ; or Ud
The present invention relates to a film adhesive composition, a method for producing the same, a film adhesive, a semiconductor package using the film adhesive, and a method for manufacturing the semiconductor package. [Background Art]
Heretofore, a paste-like adhesive has been used to make a semiconductor chip and a wiring board adhere to each other in the manufacturing process of a semiconductor package. However, recently, as semiconductor packages have functions more and more, more compact (high-density) mounting is required inside packages. In order to prevent resin flow, resin migration, or the like from contaminating to retain the bonding strength at a high level, and makes it possible to sufficiently suppress a package crack. [Advantageous befects of Invention]
The present invention makes it possible to provide: a film adhesive composition which makes it possible to obtain a film adhesive having a favorable surface appearance, asufficientlylowmeltviscosity, anexcellent adhesivenesstoanadherend, andasufficientlyhighelastic modulus and a sufficiently lowwater absorption rate after curing; a method for producing the film adhesive composition;afilmadhesive; asemiconductorpackageusing the film adhesive; and a method for manufacturing the semiconductor package.
Co Therefore, even when a semiconductor chip is made thinner and smaller, the present invention enables the . semiconductor chip and a wiring board to adhere to each other with high precision in the manufacturing process of asemiconductorpackage, enablesabondingwiretoretain the bonding strength at a high Level, and makes it possible to sufficiently suppress formation of a package crack. [Brief Description of Drawings] [Fig. 1] Fig. 1 is a schematic longitudinal sectional view for illustrating a preferred embodiment of a first step in amethod for manufacturing a semiconductor package of the present invention. [Fig. 2] Fig. 2 is a schematic longitudinal sectional view for illustrating a preferred embodiment of a second stepinthemethod formanufacturingasemiconductorpackage of the present invention. (Fig. 3] Fig. 3 is a schematic longitudinal sectional view for illustrating a referred embodiment of a third stepinthemethod formanufacturingasemiconductorpackage of the present invention. : [Fig. 4] Fig. 4 is a schematic longitudinal sectional view for illustrating a preferred embodiment of a step of connecting abonding wiz in themethod fornanufacturing a semiconductor package of the present invention. [Fig. 5] Fig. 5 is a schematic longitudinal sectional view for illustrating a preferred embodiment of a semiconductor package manufactured by the method for manufacturing a semiconductor package of the present invention. [Description of Embodiments]
Hereinafter, the present inventionwillbedescribed in detail on the basis of preferred embodiments thereof.
First, a film adhesive composition of the present invention and a method for producing the same will be described. The method for producing a film adhesive composition of the present invention is a method for producing a film adhesive composition which comprises an epoxy resin (A), an epoxy resin curing agent (B), a phenoxy resin (C), and a surface-treated spherical silica filler (D) obtainedbysubjectinga spherical silica filler having an average particle diameter of 0.01 to 2.0 ym to a surface treatment with a silane coupling agent, and which has a content of the surface-treated spherical silica filler (D) of 30 to 70% by mass relative to a total amount of the epoxy resin (A), the epoxy resin curing agent (8), the phenoxy resin (C), and the surface-treated spherical silica filler ({(D}, anelasticmodulusat200°Cafterthermal curing of 20 to 3000 MPa, and asaturatedwaterabsorptionrateafter thermal curing of 1.5% by mass or less, the production method comprising: astepofobtainingasurface~treatedsphericalsilica fillerdispersionliquidbydispersingthesurface-treated spherical silica £1007 (D) in an organic solvent; and a step of obtaining the film adhesive composition by mixing the surface-treated spherical silica filler dispersion liquid with the epoxy resin (A), the epoxy resin curing agent (B), and the phenoxy resin (C).
The epoxy resin (A) accordingtothepresentinvention is a thermosetting resin having an epoxy group. Such an epoxy resin (A) has a weight average molecular weight of preferably 300 to 2000, more preferably 300 to 1500. IE the weight average molecular weight is less than the lower limit, thisresults inlargernumbers ofmonomersanddimers, thereby increasing the crystallinity. Hence, the resulting filmadhesive tends tobe fragile. On the other hand, if the weight average molecular weight exceeds the upper limit, this increases the melt viscosity of the film adhesive. Hence, whencompressionbondedtoawiringboard, the film adhesive cannot fill up the irregularity on the board sufficiently, and the adhesiveness to the wiring boardtendstobelower. Notethat, inthepresent invention, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) (product name:
HLC-82A (manufacturedbyTosohCorporation) withasolvent: tetrahydrofuran, columns: TSKgelG2000HXL (manufactured by Tosoh Corporation) (two), G4000HXL (manufactured by
Tosoh Corporation) (one), atemperature: 38°C, and a speed: 1.0 ml/min), and converted by using standard polystyrene (productname: A-1000, manufacturedbyTosohCorporation).
The epoxy resin (A) may be either liquid, solid, or semi-solid. In the present invention, the term liquid refers to one having a softening point of lower than 50°C, the solid refers to one having a softening point of 60°C oo 15 orhigher, andthesemi-solidreferstoonehavingasoftening point between the softening point of a liquid and the softening point of a solid (50°C or higher but lower than
60°C). The epoxy resin (A) preferably has a softening soint of 100°C or Lower fron the viewpoint of obtaining a film adhesive having a low melt viscosity in a suitable temperature range (for example, 60 to 120°C). Note that, in the present invention, the softening point is a value measured by a testing method for a softening point (ring and ball method) (measurement conditions: in accordance with JIS-2817).
The epoxy resin (A) has an epoxy equivalent of - preferably 500 g/eq or less, more preferably 150 to 450 g/eq, from the viewpoints that the cross-link density of the cured product is high, which resultsinahigherelastic modulus Jrter thermal curing, and even in a case where asmaller semiconductor chip is used, the bonding strength : ofabondingwirebetweenawiringboardandthesemiconductor chip tends to be retained at a high level. Note that, in the present invention, the epoxy equivalent refers to the number of grams (g/eq) of a resin containing 1 gram equivalent of an epoxy group.
Examplesof thebackboneoftheepoxyresin (A) include phenol novolac type, orthocresol novolac type, cresol novolac type, dicyclopentadiene type, biphenyl type, fluorene bisphenol type, triazine type, naphthol type, naphthalenediol type, triphenylmethane type, tetraphenyl type, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, trimethylolmethane type, and the like. From the viewpoints that the crystallinity of the resin is low and a film adhesive having a favorable surface appearance is obtained, preferable are triphenylmethane type, bisphenol A type, cresol novolac type, orthocresol -novolac type, and dicyclopentadiene type. | One type of the epoxy resin (A) may be used alone, or two or more types thereof may be used in combination.
Inthecaseofusingtwoormoretypesthereofincombination,
itispreferabletouse inepory resin (al) havingasoftening
Point of 50501007 Candanepoxy resin (a2) havinga softening . point of lower than 50°C in combination fromtheviewpoints, for example, that it is easy to adjust the viscosity of the composition, and that the adhesiveness between a wafer and a film adhesive tends to be demonstrated sufficiently even in a case where a step of thermocompression bonding the film adhesive and the wafer (wafer lamination step) is performed at low temperature (preferably 40 to 80°C).
The epoxy resin (al) is solid or semi-solid at room temperature and has a softening point of preferably 50 to 100°C, more preferably 50 to 80°C. If the softening point is less than the lower limit, the resulting film adhesive hasalowviscosity, sothatittendstobedifficult to keep the film shape at normal temperature. On the other hand, if the softening point exceeds the upper limit, it tends to be difficult to obtain a film adhesive having a low melt viscosity in a suitable temperature range (for example, 60 to 120°C)
The epoxy resin (al) has a weight average molecular weight of preferably higher than 500 but not higher than 2000, more sreferably 600 to 1200. If the weight average molecular weight is less than the lower limit, this results inlargernumbersofmonomersanddimers, therebyincreasing the crystallinity. Hence, the resulting film adhesive tends to be fragile. On the other hand, if the weight average molecular weight exceeds the upper limit, this increases themelt viscosity of the filmadhesive. Hence, when compressionbondedtoawiringboard, the filmadhesive cannot fill up the irregularity on the board sufficiently, and the adhesiveness to the wiring board tends to be lower. 15 . From the viewpoints that the crystallinity of the resinislowandafilmadhesivehavingafavorableappearance is obtained, the backbone of such an epoxy resin (al) is other members such as a semiconductor chip and a wire pad, a film adhesive (die attach film) is increasingly used. ’ Particularly, a smaller semiconductor chip is used in a ) semiconductor package for an analog application than that in a semiconductor package for a digital application such oo asamemorywhichperformsastorage function. Furthermore, a finer wiring rule is applied inside a package. Hence, there has been a demand for a development of a film adhesive capableofmakingasemiconductorchipadhereinarestricted : region of a wiring board with high precise.
When a semiconductor chip adheres to a wiring board while being face up, the wiring board and the semiconductor chip are normally connected to each other with a bonding wire made of a metal such as gold, silver, or aluminium. ‘However, the recent drastic increase in the gold price has increased the use of a copper wire which can be prepared at relatively low cost among bondingwires made of the above
' , . , preferablytriphenylmethane type, bisphenolAtype, cresol novolac type. orthocresol novolac type, | and : dicyclopentadiene type, morepreferably triphenylmethane type epoxy resin, bisphenol A type epoxy resin, and cresol novolac type epoxy resin.
The epoxy resin (a2) preferablyhas a softening point of lower than 50°C, more preferably has a softening point of 40°C or lower, fromthe viewpoint that the adhesiveness betweenawaferanda filmadhesive tends tobe demonstrated sufficiently even in the case where the step of thermocompression bonding the filmadhesive and the wafer (wafer lamination step) is performed at low temperature (preferably 40 to 80°C). Such an epoxy resin (a2) has a weight average molecular weight of preferably 300 to | 500, more preferably 350 to 450. If the weight average molecular weight is less than the lower limit, this results in a larger number of monomers, thereby increasing the crystallinity. Hence, the resulting film adhesive tends to be fragile. On the other hand, if the weight average molecular weight exceeds the upper limit, this increases : the melt viscosity. Hence, the adhesiveness between the wafer and the film adhesive tends to be Lower at the time of the wafer lamination step.
From the viewpoints that the crystallinity of the resinislowandafilmadhesivehavingafavorableappearance is obtained, the backbone of such an epoxy resin (a2) is preferably oligomer type liquid epoxy resin bisphenol A, bisphenolA/Fmixture type, bisphenol Ftype, andpropylene oxide-modified bisphenol A type. From the viewpoints of lowmelt viscosityand lower crystallinity, the epoxyresin (a2) is more preferably bisphenol A type epoxy resin and bisphenol A/E mixture type epoxy resin.
A ratio of the epoxy resin (al) and the epoxy resin (a2) is preferably 85:5 to 30:70, more preferably 70:30 to 40:60, in terms of mass ratio (al:a2). If a content of che epoxy resin (al) is less than the Lower limit, this increasesthefilmtackinessoftheresulting filmadhesive, and there is a tendency that the film adhesive is hardly peeled off from a cover film and a dicing tape. On the other hand, if the content exceeds the upper limit, this increasestheviscosityofthecomposition, andtheobtained film adhesive tends to have a fragile characteristic.
As the epoxy resin curing agent (B) according to the present invention, known curing agents such as amines, acid anhydrides, and polyhydric phenols can be used.
Nevertheless, a latent curing agent is preferably used fromthe viewpoints ofobtainingafilmadnesive composition demonstrating a curability at high temperature exceeding atemperature rangewheretheepoxyresin (A) and thephenoxy resin (C) have a low melt viscosity, the film adhesive compositionhavinganimmediatecurability, andalsohaving such a high storage stability that the composition can be stored for a Long period at room temperature. Examples + of the latent curing agent include dicyandiamide, imidazoles, hydrazides, boron trifluoride-amine complexes, amine imides, polyamine salts, modified products thereof and microcapsules thereof. One of these may be used alone, or two or more of these may be used in combination. : The phenoxy resin (C) according to the present invention is a thermoplastic resinhavingaweight average molecular weight of 10000 or higher. The use of such a } phenoxy resin (C) eliminates the tackiness and fragility of the resulting film adhesive at room temperature.
The phenoxy resin (C) has a weight average molecular weight of preferably 30000 to 100000, more preferably 40000 to 70000. If the weight average molecular weight is less than the lower limit, the supportability of the resulting film adhesive is weakened, and the fragility tends to increase. Ontheotherhand, i fthowsightaveragenolecular weight exceeds the upper limit, the melt viscosity tends to increase. Moreover, the phenoxy resin (C) has a glass transition temperature (Tg) of preferably 40 to 100°C, more preferably 50 to 90°C. If the glass transition temperature is less than the lower limit, this increases the filmtackiness of the resulting filmadhesive at normal temperature, and there is a tendency that the filmadhesive is hardly peeled off from a cover film and a dicing tape.
On the other hand, if the glass transition temperature exceeds the upper limit, this increases themelt viscosity of the film adhesive. Hence, when compression bonded to a wiring board, the film adhesive cannot fill up the irregularity on the board sufficiently, and the adhesiveness to the wiring board tends to be lower.
Examples of the backbone of the phenoxy resin (C)
include bisphenol A type, bisphenol A/F type, bisphenol
Ftype, bisphenol S type, bisphenol A/s type, cardobackbone type, and the like. Nevertheless, bisphenol A type is preferable from the viewpoints that it is well compatible. with the epoxy resin (A) because the structure is similar, and that the melt viscosity is low and the adhesiveness is also favorable. From the viewpoint of obtaininga film adhesive having a low melt viscosity in a suitable temperature range (for example, 60 to 120°C), bisphenol
A/F type is preferable. From the viewpoint of having a high heat resistance, cardo backbone type is preferable.
Examples of such a phenoxy resin (C) include a bisphenol
A type phenoxy resin obtained from bisphenol A and epichlorohydrin, and a bisphenol A/F type phenoxy resin obtained from bisphenol A, bisphenol F, and epichlorohydrin. One of these phenoxy resins (C) may be usedalone, ortwoormoreofthesemaybeusedincombination.
Alternatively, commercially-available phenoxy resins such as, for example, ve-505 (bisphenol A type phenoxy resin, manufacturedbyNSCCEpoxyManufacturingCo., Ltd.) ,
YP-70 (bisphenol A/F type phenoxy resin, manufactured by
NSCC Epoxy Manufacturing Co., Ltd.), FX-316 (bisphenol : F type phenoxy resin, manufactured by NSCC Epoxy
ManufacturingCo., Ltd.), and FX-280S (cardo backbone type phenoxy resin, manufactured by NSCC Epoxy Manufacturing
Co., Ltd.) may be used as the phenoxy resin (C).
The surface-treated spherical silica filler (D) . . accordingtothepresentinventionisobtainedbysubjecting a spherical silica filler having an average particle diameter of 0.01 to 2.0 um to a surface treatment with a silane coupling agent.
The average particlediameterof the sphericalsilica filler needs tobe 0.01 to 2.0 um. If the average particle diameter is less than the lower limit, the specific surface area of the silica filler is larger, which increases the interaction with the cesins to be blended, and increase themelt viscosity of the resulting film adhesive, so that the adhesiveness to an adherend is likely to be lowered.
On the other hand, if the average particlediameter exceeds the upper limit, when a thin film adhesive is produced using a coater such as a roll knife coater, a streak is likely to be formed on the appearance of the film surface, and the wear rate of a processing blade is increased by the film adhesive in a step of cutting a wafer provided with the filmadhesive into semiconductor chips. Further, theaverageparticlediameterofthesphericalsilicafiller is particularly preferably 1.0 um or smaller from the viewpoint of forming anextremely thin filmadhesive having a thickness of 5 pum or smaller.
Note that, in the present invention, the average particle diameter refers to a particle diameter measured whenanaccumulative value reaches 50%, whereatotalvolume of particles in the particle size distribution is set to 100%. The average particle diameter can be obtained from © acumulativecurveofvolumefractionsofparticlediameters in a particle diameter distribution measured by a laser diffraction-scattering method (measurement conditions: dispersion medium- sodium hexametaphosphate, laser wavelength: 780 nm, measurement device: MICROTRAC®
MT3300EX). Additionally, in the present invention, the term spherical refers to a perfect ball or anearly perfect ball rounded with substantially no corners.
Such a spherical silica filler is not particularly limited. Nevertheless, fromthe viewpoints that the shape of silica particles to be obtained is nearly perfectly spherical and it is easy to adjust the particle diameter, preferable is one obtained by combusting a silicon powder according toa VMC (VaporizedMaterial Combustion) method.
: The VMC method utilizes the principle of a dust explosion. . In the method, a chemical flame is formed using a burner in an atmosphere containing oxygen, and a metal powder constituting the target oxideparticlesisintroducedinto ~this chemical flame in such an amount that a dust cloud is to be formed, followed by a deflagration to obtain the oxide particles. By the VMC method, a large amount of oxideparticles (silicaparticles)areinstantlyobtained. : Moreover, by adjusting the particle diameter and amount of a silicon powder introduced, flame temperature, and so on, the particle diameter of silica particles to be obtained can be adjusted.
Thesilanecouplingagentisnotparticularlylimited.
It is possible to use, for example, silane monomer-based, vinyl silane-based, methacrylic silane-based, epoxy silane-based, mercapto silane-based, sulfur silane-based, amino silane-based, ureido silane-based,
described materials. For the connection using a bonding wire, normally, a bonding wire is heated to 100°C or higher tomelt the metal , so that awiringboard and a semiconductor chip are bonded together with the metal. In a case of using the copper wire, the wire has to be heated to particularly high temperature. Meanwhile, if a wiring board and a ‘semiconductorchipadhere toeachotherunstably, thebonding strength of the bonding wire tends to be insufficient especially when a small semiconductor chip is used. There has been a demand for a development of a film adhesive having : a higher elastic modulus at high temperature after curing.
Further, generally, in a semiconductor package, a wiring board thereof is directly mounted together with a lead on adevice or the like with solder by a reflow process.
In this event, however, the entire semiconductor package is exposed to a temperature as high as 210 to 260°C.
Accordingly, if water is present inside a film adhesive and isocyanate silane-based coupling agents.
Nevertheless, fronthevieupsints thet thewater absorption rateofthefilmadhesiveaftercuringcanbe furtherlowered and formation of a package crack canbe further suppressed, preferable is a silane coupling agent with no functional group havingahighaffinity forwater, andmore preferable is a vinyl-based silane coupling agent represented by the following general formula (1):
R3-n=S1i(CH3),~CH=CH, +--+ (1) [in the formula (1), R represents any one hydrolyzable functional group selected from the group consisting of a methoxy group, an ethoxy group, and a 2-methoxyethoxy group, and n represents an integer of any one of 0 and 17.
Examples of the method for subjecting the spherical silica filler to the surface treatment with the silane coupling agent include a treatment method in which the silane coupling agent vaporized is allowed to react with a powder ot the spherical silica filler with stirring (treatment method I), and a treatment method in which the silane coupling agent is added and allowed to react with the spherical silicafillerdissolvedinanorganic solvent (treatment method II). In the present invention, it is preferable to adopt the treatment method II from the viewpoints that the surface-treated spherical silica filler (D) accordingtothepresent inventioncanbeobtained while being dispersed in an organic solvent and can be directly used in the production method of the present invention.
The treatment method II preferably comprises: a step of obtaining a silane coupling agent solution by dissolving the silane coupling agent in an organic solvent; and a step of obtaining the surface-treated spherical silica filler dispersion liquid in which the urface-treated spherical silica filler (D) is dispersed in the organic solvent by dispersing the spherical silica filler in the silane coupling agent solution to thereby subject thesphericalsilicafillertothesurface treatment with the silane coupling agent.
The organic solvent is not particularly limited.
Examples thereof include aromatic hydrocarbons such as toluene and xylene; ketones such asmethyl isobutyl ketone (MIBK) and methyl ethyl ketone (MEK); ethers such as monoglyme and diglyme; and mixtures of these. The organic solvent can be selected as appropriate in accordance with the resins used in the film adhesive composition of the present invention. Moreover, the concentration of the ~ silanecouplingagent inthesilanecouplingagent solution is also not particularly limited, but is preferably 20 to 90% by mass.
» ‘ : \ ,
The amount of the silane coupling agent and the spherical silica fillerblended canbe nozmally calculated froma specific surface areaof the sphericalsilica filler used and a minimum coverage area of the silane coupling agent according the following formula: amount of silane coupling agent blended [g] = (amount of spherical silica filter blended [g] x specific surface area of spherical silica filler [m?/g])/ (minimum coveragearea of silane coupling agent [m2/g]) .
However, in the present invention, fromthe viewpoint that a silanol group on the surface of the spherical silica fillercanbesufficientlytreated, theamountofthesilane ~ coupling agent blended is preferably an excessive amount.
The amount of the silane coupling agent blended is more preferably 1 co 5 parts by mass, further preferably 1 to 3 parts bymass, relative to 100 parts by mass of the amount of the spherical silica filler blended. If the amount of the silane coupling agent blended is less than the lower init, there is a tendency that a silanol group on the surface of the spherical silica filler isnot sufficiently : treated. On the other hand, if the amount of the silane coupling agent blended exceeds the upper limit, the extra silane coupling agent volatilizes by heat in the manufacturing process and the mounting process of a semiconductor package, or the Like, and nay contaminate other members such as a semiconductor chip and a wire pad.
Themethod fordispersingthesphericalsilicafiller in the silane coupling agent solution is not particularly limited. An example thereof includes a method in which stirring is carried out using a mechanical stirrer, a magneticstirrer, ahomogenizer, orthelike atatemperature ot 25 to 70°C for approximately 1 to 100 hours. By such a method, the surface~treated spherical silica filler dispersion liquid in which the surface-treated spherical silica filler (D) according to the present invention is dispersed in the organic solvent can be obtained.
The method for producing a filmadhesive composition of the present invention comprises: astepofobtainingasurface-treatedsphericalsilica fillerdispersionliquidbydispersingthesurface-treated spherical silica filler (D) in an organic solvent; and a step of obtaining the film adhesive composition by mixing the surface-treated spherical silica filler dispersionliquidwith the epoxy resin (A), the epoxy resin curing agent (B) ) and the phenoxy resin (C).
Inthestepofobtainingthesurface-treatedspherical silica filler dispersion liquid according to the present invention, the surface-treated spherical silica filler | (D) is dispersed inthe organic solvent. Suchadispersing method is not particularly limited. A spherical silica filler having been subjected to the surface treatment in advancemaybedispersedintheorganicsolventbystirring.
Alternatively, the cus facet reatnentnaybe per forneduhile a spherical silica filler is being dispersed in the organic solvent. From the viewpoint that the number of steps is small, it is preferable to adopt the treatment method II as the method for subjecting the spherical silica filler to the surface treatment with the silane coupling agent to directly use the obtained surface-treated spherical silicafillerdispersionliquid. Inaddition, theorganic solvent is not particularly limited, and examples thereof include those listed for the treatment method II.
The concentration of the surface-treated spherical silica filler (D) in the surface-treated spherical silica filler dispersion liquid is not particularly limited.
Nevertheless, the concentration is preferably 40 to 80% by mass from the viewpoint that if the percentage of the organic solvent increases, the viscosity of the resulting filmadhesivecompositionislowered,andthereisatendency that anappearancedefect such e bump (repelling) ororange peel is likely to occur when a film adhesive is formed.
Inthestepofobtainingthe filmadhesive composition according to the present invention, the surface-treated : spherical silica filler dispersion liquid is mixed with the epoxy resin (A), the epoxy resin curing agent (B), and the phenoxy resin (C). Such a mixing method is not particularlylimited. Anexamplethereofincludesamethod in which stirring is carried out using a heatable device such as a planetary mixer and a mechanical stirrer under conditions: a rotation speed of a stirring blade of 10 to 300 rpm for approximately 0.5 to 5.0 hours.
The amount of the epoxy resin (A) blended is such an amount that a content thereof in the resulting film adhesive composition is preferably 10 to 60% by mass, more preferably 20 to 50% by-mass. If the content is less than the lower limit, the adhesive force of the resulting film adhesive tends to be Lower. on the other hand, if the content exceeds the upper limit, the main component of the resulting film adhesive is an oligomer; hence, there is a tendency that the state of the film (the filmtackiness and so forth) is likely to change even by a little change in the temperature. ~The amount of the epoxy resincuringagent (B) blended is normally 0.5 to 50 parts by mass, preferably 1 to 10 parts by mass, relative to 100 parts by mass of the epoxy resin (A). If the blended amount is less than the lower limit, the curing period tends to be longer.
On the other hand, if the blended amount exceeds the upper limit, the excessive curing agent remains in the resulting film adhesive, and water is adsorbed to the remaining curing agent.
Hence, there is a tendency that a defect is likely to occur in a reliability rest after the film adhesive
I is incorporated into a semiconductor package.
The amount of che phenoxy resin (C) blended is such an amount that a content thereof in the resulting film adhesive composition is preferably 1 to 30% by mass, more preferably 3 to 20% by mass. If the content is less than the lower limit, this increases the film tackiness of the resulting film adhesive, and there is a tendency that the film adhesive is hardly peeled off from a cover film and a dicing tape. On the other hand, if the content exceeds the upper limit, this increases the melt viscosity of the resulting film adhesive. Hence, when compression bonded to a wiring board, the film adhesive cannot fill up the irregularity on the board sufficiently, and the adhesiveness to the wiring board tends to be lower.
The amount of the surface-treated spherical silica filler (D) blended needs tobe such an amount that a content of the surface-treated spherical silica filler (D) is 30 after curing, the water explosively vaporizes, so that a package crack may be forned. Particularly, as the area where the semiconductor chip adheres to a wiring board is made smaller by reducing the size of a semiconductor chip in a semiconductor package, there is a trend that a package crack is likely to be formed. Accordingly, a development of a film adhesive having a lower water absorption rate after curing has been demanded.
As a film adhesive produced in order to suppress such a package crack, for example, Japanese Unexamined
Patent Application Publication No. 2000-200794 (PTL 1) describes a film adhesive (die-bonding material) having awater absorptionrateofl.5%byvolumeorless. However, the filmadhesive described inthis literaturehasaproblem that the elastic modulus at high temperature is low and it is difficult to bond a bonding wire with a sufficient strength.
J to 70% by mass relative to a total amount of the epoxy resin (A), the epory resin curing agent (B), the phenoxy resin (C), and the surface-treated spherical silicafiller (D). If the content is less than the lower limit, this increases the water absorption rate of the resulting film adhesive, so that a package crack is likely to be formed.
In addition, the elastic modulus after curing at high temperature is lowered, so that a defect is likely to occur in connecting with a bonding wire, lowering the bonding strength. on the other hand, if the content exceeds the upperlimit, this reducestheamountofthe resincomponents, so that the adhesive force to an adherend is lowered.
Moreover, the content of the surface-treated spherical silica filler (D) is particularly preferably 35 to 50% bymass fromthe viewpoints of lowering thewaterabsorption rateof theresultingfilmadhesive, increasingthe elastic modulus after curing at high temperature, and improving properties such as adhesive force owing to the blended oo epoxy cesin.
As described above, the film adhesive composition of the present invention can be obtained, in which the surface-treated spherical silica filler (D) is uniformly dispersed. The film adhesive composition of the present invention comprises an epoxy resin (A), an epoxy resin curingagent (B), aphenoxyresin (C), andasurface-treated spherical silica filler (D) obtained by subjecting a sphericalsilicafillerhavinganaverageparticlediameter of 0.01 to 2.0 pm to a surface treatment with a silane coupling agent.
A content of the surface-treated spherical silica filler (D) is 30 to 70% by mass relative to a total amount of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C), and the surface-treated spherical silica filler (D).
An lastic modulus at 200°C after thermal curing is 20 to 3000 MPa.
Asaturatedwaterabsorptionrateafterthermalcuring is 1.5% by mass or less. : Moreover, sincethesurface-treatedsphericalsilica filler (D) is uniformly dispersed in the film adhesive compositionofthepresentinvention, thismakesitpossible to obtain a film adhesive having a favorable surface appearance. When a grind meter including a gauge and a scraper as defined in JISK5600-2-5 (1999) is used to place such a £ilm adhesive composition of the present invention as a sample in a groove of the gauge and move the scraper : | thereon by dragging, it is preferable that substantially no line be observed. Tobemore specific, morepreferably, when a gauge of 10 to 100 pm is used, substantially no line is observed. Particularly preferably, when a gauge of 2.5 to 25 pm is used, substantially no line is observed.
Note that, in the present invention, the phrase ‘substantially noline is observed" refers to state where no line is observed at all, or where the depth in the gauge at the starting point of a line appearing on the sample surface is less than the minimum value of the gauge.
In addition, the production method of the present invention preferably further comprises a step of removing the organic solvent. The method for removing the organic solvent is not particularly limited. An example thereof includes a method in which stirring is carried out while the film adhesive composition is further heated. The heating conditions cannot be specified because: the temperature shouldbe lower thanacuringstart temperature of the film adhesive composition, the concentration of anon-volatile component in the film adhesive composition shouldberoughlyaconcentrationasdesired, andtheheating conditions differ depending on a method for producing a film adhesive and the types of the organic solvent and the resins used. However, the heating conditions are preferably, for example, 50 to 150°C for approximately 0.1 to 10.0 hours . Furthermore, the film adhesive composition obtained as described above preferably has a non-volatile component concentration of approximately : 40 to 90% by mass.
The filmadhesivecompositionofthepresentinvention may further comprise the organic solvent; an additive such asafillerother thanthe surface-treatedsphericalsilica filler (D), a viscosity modifier, an antioxidant, a flame retardant, a colorant, and a stress relaxation agent such as a butadiene-based rubber and a silicone rubber, in such arangeasnottoinhibittheeffectsofthepresentinvention, in addition to the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C), and the surface-treated spherical silica filler (D).
ee ——————————— eee
Thefilmadhesivecompositionofthepresentinvention preferably comprises a viscosity modifier among the aforementioned additives from the viewpoint that if the melt viscosity. of the resulting film adhesive is too low, there is a tendency that other members and the like are i | likely to be contaminated by resin flow, resin migration, or the like when a wafer is thermocompression bonded to © awiringboard. Examplesoftheviscositymodifierinclude polycarboxylic acid amide-based, modified urea-based, urea-modified urethane-based, urea-modified bolyanide-based, and wurea-modified polyamide-based surfactants; hydrophobic fumed silica; and the like. In a case where the film adhesive composition of the present : invention comprises such an additive, the additive is preferably added at the same timing as that of the epoxy resin (A), the epoxyresincuring agent (B), and the phenoxy resin (C). Theamountoftheadditiveblendedispreferably suchanamountthatacontentoftheadditiveintheresulting film adhesive composition is 3% by mass or less.
Next, a film adhesive of the present invention will be described. The film adhesive of the present invention is a film adhesive obtained by forming the film adhesive composition of the present invention into a film shape, and the film adhesive has a melt viscosity at 80°C of 10000
Pass or less observed using a rheometer when heated from 20°Catarateoftemperatureriseof10°C/minute. Moreover, ‘in the film adhesive of the present invention, the surface-treated spherical silica filler (D) is uniformly dispersed.
An example of a preferred embodiment of a method for producing the film adhesive of the present invention includes a method in which the film adhesive composition isappliedtoonesurfaceofabasefilmhavingbeensubjected to amold-release treatment, followed by heat~drying, but
’ . , , is not particularly Limited to nie method.
As the base film having been subjected to the moLd-release treatment, any known base £ilncanbe employed as appropriate, as long as it functions as a cover film of the film adhesive to be obtained. Examples thereof include bolypropylene (PP) ining been subjected to the mold-release treatment, polyethylene (PE) having been subjected to themold-release treatment, and polyethylene terephthalate (PET) having been subjected to the mold-release treatment. As the applicationmethod, known methods can be adopted as appropriate. Examples thereof includemethodsusingarollknifecoater, agravurecoater, a die coater, a reverse coater, or the like.
The heat-drying is performed at a temperature lower than the curing start temperature of the film adhesive composition. Such a temperature cannot be specified because it differs depending on the type of the resins
CT
’ . , . used. However, the temperature Lspreferably, for example, oo 40£0100°C, nore preferably 60ta 100°C. Ifthetemperature is less thanthe lower limit, a Larger amount of the solvent remains in the film adhesive, so that the film tackiness tends to increase. On the other hand, if the temperature is equal to or higher than the curing start temperature, the film adhesive composition is cured, so that the adhesiveness of the film adhesive tends to be lowered.
Additionally, theperiodof theheat-dryingispreferably, for example, 10 to 60 minutes. Note that the non-volatile component concentration when the film adhesive is formed is preferably approximately 95.0 to 99.8% by mass.
The film adhesive of the present invention obtained as described above preferably has a thickness of 1 to 50 pm, more preferably 5 to 40 pm, further preferably 10 to pm, from the viewpoint that the film adhesive can fill up the irregularity on the top surface of a wiring board
’ oo , . more sufficiently. If the thickness is less than the lower limit, the irregularity on the top surface of the wiring board cannot be filled up sufficiently, and there is a tendency that a sufficient adhesiveness cannot be guaranteed. On the other hand, if the thickness exceeds the upper limit, this makes it difficult to remove the organic solvent at the time of the production. Hence, the solvent remains in a larger amount, so that the film tackiness tends to increase. Note that since the surface-treated spherical silica filler (D) is uniformly dispersed in the film adhesive composition of the present
Co invention, even when the film adhesive of the present invention has a thickness of approximately 1 to 10 pm, it is possible to make the surface appearance favorable. | Such a film adhesive of the present invention has a sufficiently low melt viscosity and an excellent adhesiveness to an adherend. The melt viscosity is
Meanwhile, asamethodforimprovingtheelasticmodulus of a film adhesive and towering the water absorption rate thereof, a technique is knownbywhichalotofsilicafillers © areincorporated. For example, Japanese Unexamined Patent
Application Publication No. 2005-19516 (PTL 2) states in : Examplesthataddingspherical fusedsilicahavinganaverage particle diameter of 0.5 ym as a filler to a film adhesive (die-bonding adhesive film) containing an epoxy resin, a phenol resin, and a synthetic rubber increases the elastic modulus at high temperature.
Nonetheless, since a silica filler having a small particle diameter such as the spherical fused silica described in PTL 2 has a Large specific surface area, the silica filler strongly interacts with one another and tends to aggregate when mixed with a resin. Particularly, in acasewherethe thicknessofafilmadhesiveistobereduced, there is a problem that the appearance of the film surface specifically a melt viscosity at 80°C of 10000 Pae*s or less observed using a rheometer when the film adhesive is heated from 20°C at a rate of temperature rise of 10°C/minute. The melt viscosity is more preferably 10 to 10000 Paes. If the melt viscosity is less than the lower limit, there is a tendency that other members are contaminated by resin flow, resin migration, or the like when the film adhesive adheres to a bottom surface of a wafer. On the other hand, if the melt viscosity exceeds the upper limit, there is a tendency that when the film adhesive adheres to a bottom surface of a wafer or a top . surface of a wiring board with an irregularity, air is likely to be entrapped at interfaces with the adherends.
Since having such a melt viscosity property, the ~~ film adhesive of the present invention is capable of compressionbondingtoanadherendinasuitabletemperature range (for example, 60 to 120°C), and demonstrates an excellent adhesiveness to the adherend. Note that, in hepresent invention, themelt viscosity isavalusabtained by measuring a viscous resistance at a predetermined temperature of a molten resin. The melt viscosity at 80°C refers to a viscous resistance at a temperature of 80°C : inatemperature-viscousresistancecurvewhichisobtained by measuring a change in a viscous resistance within a temperature range of 20 to 100°C at a rate of temperature rise of 10°C/min wsing a rheometer (product name: RS150, : 10 manufactured by Haake).
Moreover, the filmadhesive of the present invention has an elastic modulus at 200°C after thermal curing of 20 to 3000 MPa. The elastic modulus is more preferably 50 to 1000 MPa. If the elastic modulus is less than the = lower limit, the adhesion between a wiring board and a : semiconductor chip is unstable. Particularly when a semiconductor chip is made smaller, there is a tendency that the bonding strength to a bonding wire is likely to be insufficient. On the other hand, if the elastic modulus exceeds theupper limit, this reduces thestress relaxation ability under high temperature condition, and there is a tendency that a peeling defect is likely to occur at the time of a reliability test. Note that, in the present invention, the elastic modulus at 200°C refers to a value at200°Cmeasuredusingadynamicviscoelasticitymeasuring apparatus (product name: Rheogel-E4000F, manufactured by
UBMCo., Ltd.) under conditions: ameasurement temperature range of 30 to 300°C, arate of temperature rise of 5°C/min, and a frequency of 1 Hz.
Furthermore, the film adhesive of the present invention has a saturated water absorption rate after thermal curing of 1.5% by mass or less. The saturated water absorption rate is more preferably 1.3% by mass or less. If the saturated water absorption rate exceeds the
: upper limit value, there is a tendency that a package crack is Likely to be formed by an explosive vaporization of water insideadie attach filmwhen a semiconductor package : is soldered by a reflow process. Note that, inthe present invention, the saturated water absorption rate can be calculated by measuring a mass before and after a film adhesive after thermal curing absorbs moisture for 100 hours at a temperature 85°C and a relative humidity RH of 85% using a temperature & humidity chamber (product name: PR-1J, manufactured by ESPEC Corp.). -
The thermal curing is performed by heating at a temperature equal to or higher than the curing start temperature of the film adhesive composition. Such a temperature cannot be specified because it differs depending on the type of the resins used. However, the temperature is preferably, for example, 120 to 180°C, more preferably 120 to 140°C. If the temperature is lower than the curing start temperature, the chormal curing does not proceed sufficiently, and the strength of the filmadnesive after thermal curing tends to be lower. On the other hand, ifthetemperatureexceeds theupperlimit, theepoxyresin, | thecuringagent, theadditive, andsooninthe £ilnadnesive volatilize during che curing, and there is a tendency that the film adhesive is likely to foam. Moreover, such a heatingperiodispreferably, forexample, 10tol180minutes.
Further, in the thermal curing, it is more preferable to apply a pressure of approximately 0.1 to 10 MPa.
Next, a preferred embodiment of a method for : manufacturing a semiconductor package of the present invention will be described in detail with reference to the drawings. Note that, in the following description and drawings, the same or corresponding components are denoted by the same reference numerals, and overlapping description thereof isomitted. Figs. 1lto5are schematic longitudinal sectional views forillustrating a preferred embodinent of each step in the nethod for manufacturing a semiconductor package of the present invention.
In the method for manufacturing a semiconductor package of the present invention, first, as a first step, an adhesive layer 2 is provided on a bottom surface of a wafer 1 having a top surface on which at least one : | semiconductor circuit is formed as shown in Fig. 1, the adhesive layer 2being formedby thermocompressionbonding from the fim adhesive of the present invention.
As the wafer 1, a wafer having a top surface on which at least one semiconductor circuit is formed can be used as appropriate. Examples thereofincludeasiliconwafer, : a SiC wafer, and a GaS wafer. As the adhesive layer 2, asingle layer of the filmadhesive of the present invention may be used alone, two ormore layers thereof may be stacked for use.
As the method for providing such an adhesive layer : 2 on the bottom surface of the wafer . a method by which the film sdhesive can be stacked on the bottom surface of the wafer 1 can be adopted as appropriate. In a case where the film adhesive is pasted on the bottom surface of the wafer 1 and then two or more layers are further : | | stacked, examples of the method includes a method in which the film adhesives are sequentially stackeduntil the film adhesives have a desired thickness, a method in which the filmadhesives are stacked toatarget thickness in advance and then pasted on the bottom surface of the wafer 1, and thelike. Moreover, anapparatususedwhensuchanadhesive layer 2 is provided on the bottom surface of the wafer 1 is not particularly limited. For example, known spparatuses such asaroll laminatoranda manual laminator can be used as appropriate.
When the adhesive layer 2 is provided on the bottom surface of the wafer 1, the film adhesive is laminated on the bottom surface of ‘the wafer 1 preferably at a temperature withina temperature range equal to or higher than a temperature at which ‘the film adhesive has a melt viscosity of 10000 Pass or less, but lower than a thermal curing start temperature of the film adhesive.
Such a temperature condition cannot be specified because it differs dependingon the type of ens resins used.
However, the temperature is preferably, for example, 40 to 100°C, more preferably 40 to 80°C.
If the temperature is less thanthelowerlimit, airtendstobeentrappedataninterface between the adhesive layer 2 and the wafer 1. In the case where twoormore layers of the adhesive layer 2 are stacked, the adhesion between the layers of the film adhesive tends to be insufficient.
On the other hand, if the temperature is equal to or higher than the thermal curing start temperature, the film adhesive is cured, so that the adhesiveness when the film adhesive adheres to a wiring board tends to be lowered.
In addition, the period of suchthermocompressionbondingispreferably, forexample, approximately 1 to 180 seconds. | Moreover, when the adhesive layer 2 is provided on the bottom surface of the wafer 1, it is preferable to apply a pressure of approximately 0.1 to 1 MPa.
If the pressure is less than the lower limit, it takes time to paste the adhesive layer 2 on the wafer 1. Further, there is a tendency that void formation cannot be prevented sufficiently.
On the other hand, if the pressure exceeds the upper limit, there is a tendency that sticking-out of the adhesive layer 2 cannot be controlled. ~ Subsequently, in the method for manufacturing a semiconductor package of the present invention, as a second step, after the wafer 1 and a dicing tape 3 adhere to each other with the adhesive layer 2 therebetween, the wafer
1 and the adhesive layer 2 are simultaneously diced as shown in Fig. 2. | Thus, an adhesive layer-provided semiconductor chip 4 including the wafer 1 and the adhesive layer 2 is obtained.
The dicing tape 3 is not particularly limited, and known dicing tapes can be used as appropriate. Further, anapparatusused forthedicingisnotparticularlylimited,either, and known dicing apparatuses can be used as appropriate.
Thereafter, in the method for manufacturing a semiconductor package of the present invention, as a third step, the dicing tape 3 is detached from the adhesive layer 2, and a wiring board 5 and the adhesive layer-provided semiconductor chip 4 are thermocompression bonded to each other with the adhesive layer 2 therebetween as shown in ‘Fig. 3. Thus, the adhesive layer-provided semiconductor chip 4 is mounted on the wiring board 5.
isdeteriorated. Inaddition, waterisadsorbedtoasilanol group on the surface ot the silica filler, and the water absorption rate is rather increased. As a result, there : isaproblemthat the water absorptionrateofafilmadhesive after curing cannot be sufficiently lowered.
Further, generally, thesmallertheparticle diameter of asilicafillertobe incorporated, the lower the fluidity of the film adhesive; in other words, the melt viscosity tends tobe higher. Nevertheless, since the bottom surface of a wafer and the top surface of a wiring board, which are adherends of a filmadhesive, arenot necessarily smooth surfaces, if the melt viscosity of a film adhesive is high, the adhesion between the film adhesive and the adherends "is low at the time of adhering to the adherends by heating, and air is entrapped at an interface between the two. This brings about a problem that the adhesive force of the film ~adhesiveaftercuringis lowered, possibly forming apackage
. , , .
As the wiring board 5, a board having a top surface on which a semi conductor circuit is formed can be asad : as appropriate. Examples thereof include printed circuit boards (PCBs), various lead frames, and boards whose top surface has an electronic component such as a resistance element or a capacitor mounted. Moreover, another : semiconductor chip may be used as the wiring board 5 so that multiple semiconductor chips can be stacked with the : | adhesive layer 2 therebetween.
The method for mounting the adhesive layer-provided semiconductor chip 4 on such a wiring board 5 is not particularlylimited. Itispossibletoadoptconventional methods as appropriatewhichcanutilize the adhesive layer 2 to make the adhesive layer-provided semiconductor chip . 15 4 adhere to the wiring board 5 or an electronic component mounted on the top surface of the wiring board 5. Examples of such a mounting method include conventionally known
. , . heating and pressing methods such as a method utilizing : oun ing techn iquesusinga fl ipehipbondorhavingaheating function from the above, amethod using adie bonder having a heating function only from below, and a method using a laminator.
As described above, the adhesive layer-provided semiconductor chip 4 is mounted on the wiring board 5 with the adhesive layer 2 formed from the film adhesive of the present invention therebetween. Hence, the filmadhesive can conform with the irregularity attributable to the electronic component on the wiring board 5. This enables the wafer 1 and the wiring board 5 to adhere and fix to } each other.
Whenthewiringboard5andtheadhesivelayer-provided semiconductor chip 4 are toadhere toeachother, thewiring board 5 and the adhesive layer-provided semiconductor chip 4 preferably adhere to each other at a temperature equal
: to or higher than a cemperature at which the film adhesive : has a melt viscosity of 10000 Paes or less, but owes than the thermal curing start temperature of the film adhesive .
If thewiringboaxrd5 and the semiconductor device 4 adhere to each other under such a temperature condition, there is a tendency that air is unlikely to be entrapped at an interface between the adhesive layer 2 andthewiringboard 5. Such conditions regarding temperature, period, and pressure are as described in the first step.
After that, in the method for manufacturing a semiconductor package of thepresentinvention, asa fourth step, thefilmadhesiveisthermallycured. Thetemperature of thethermalcuringcannotbespecifiedbecauseitdiffers ~ depending on the type of the resins used and is not | particularly limited as long as being equal to or higher than the thermal curing start temperature of the film adhesive. However, the temperature is preferably, for example, 120 to 180°C, more preferably 120 to 130°C. If the comperature is lower than the thermal curing start temperature, the thermal curing does not proceed sufficiently, and the strength of the adhesive layer 2 tends to be lower. On the other hand, if the temperature exceeds the upper limit, there is a tendency that the epoxy resin, the curing agent, ‘the additive, and so on in the film adhesive are likely to volatilize and foam during the curing process. Moreover, the period of the curing treatment is preferably, for example, 10 to 180 minutes.
Further, in the thermal curing, it is more preferable to apply a pressure of approximately 0.1 to 10 MPa. In the presentinvention, theadhesivelayer2havingsufficiently high elastic modulus and low water absorption rate is obtained by thermally curing the film adhesive, and a semiconductor package can be obtained, inwhich the wiring board 5 and the wafer 1 firmly adhere to each other.
Then, inthemethod for manufacturing a semiconductor package of the present invention, the wizing board 5 and the adhesive Layer-provided semiconductor chip 4 are : preferably connected to each other with a bonding wire + 6 as shown in Fig. 4. Such a connecting method is not particularly limited, and conventionally known methods, for example, a wire bonding method, a TAB (Tape Automated
Bonding) method, andthelike, canbeadoptedasappropriate.
Since the adhesive layer 2 formed from the film adhesive of the present invention demonstrates a sufficiently high : ‘elastic modulus after thermal curing, even when a small semiconductor chip having a size of 1 mm x 1 mm or less is used, the bonding wire can be connected stably. As aresult, abondingwirewithasufficient bonding strength can be obtained.
Then, in the method for manufacturing a semiconductor package of the present {avention, the wiring board 5 and the adhesive layer-provided semiconductor chip 4 are preferably sealed with a sealing resin 7 as shown in Fig. 5. Inthismanner,asemiconductorpackage8canbeobtained.
The sealing resin 7 is not particularly limited, and known sealing resins usable for manufacturing a semiconductor package canbe used as appropriate. Moreover, the sealing methodusingthesealingresin7isnotparticularlylimited, either, and known methods can be adopted as appropriate. : According to the nethod for manufacturing a semiconductorpackageofthepresentinventionasdescribed above, the adhesive layer 2 formed from the film adhesive can sufficiently fill up the interface with the wafer 1 and the interface with the irregularity onthewiringboard 5. This makes it possible to fix thewafer 1 and the wiring : board 5 to each other without forming spaces between the wafer 1 and the adhesive layer 2 and between the adhesive layer 2 and the wiring board 5.
Moreover, the method for manufacturing a semiconductor package of the present invention uses the film adhesive of the present invention formed from the film adhesive composition of the present invention.
Accordingly, evenwhena semiconductor chip ismade thinner and smaller, the semiconductor chipcanadheretothewiring board 5 with high precision; in addition, a bonding wire with a sufficient bonding strength can be obtained.
Furthermore, since the adhesive layer 2 between the wafer 1 and the wiring board 5 has a sufficiently low water absorption rate, even if a semiconductor package of the present invention obtained by such amanufacturing method is soldered by a reflow process when mounted on a device or the like, package crack formation is sufficiently suppressed. [Examples]
Hereinafter, thepresent inventionwillbedescribed more specifically based on Examples and Comparative
Examples. However, the present invention is not limited to Examples below. Note that, in each of Examples and
Comparative Examples, measurements of melt viscosity, elastic modulus, and saturated water absorption rate, as well as grind gauge evaluation, film surface appearance evaluation, wire bonding evaluation, and package crack evaluation vere respectively conducted by methods ~ illustrated below. (Grind Gauge Evaluation)
A film adhesive composition, 2 g, obtained in each
Example and Comparative Example was placed in a groove ofagaugeofagrindmeter (particle sizegauge, manufactured by Dai-Ichi Sokuhan Works Co.) including a scraper and gauges of 10 to 100 pum as defined in JISK5600-~2-5 (1999).
A value of a depth in the gauge at the starting point of : a line appearing on the surface of the composition was measured when the scraper was moved thereon by dragging.
Bb | : (Film Surface Appearance Evaluation) : A filmadhesive composition obtained in each Example and Comparative Example was applied to a PET film having athicknessof50pumhavingbeensubjectedtothemold-release : treatment, and then heat-dried at a temperature of 100°C forlOminutes. Thereby, afilmadhesivehavingathickness of 5 ym was prepared. The appearance of the surface of the film adhesive thus obtained was visually observed for the evaluation according to the following criteria:
A: no streak or aggregate was observed on the surface
B: streak or aggregate was observed on the surface. ~ (Measurement of Melt Viscosity)
A film adhesive obtained in each Example and
Comparative Example was cut into pieces each having a size of 2.5 cm x 2.5 cm, which were stacked and pasted on each other using a vacuum laminator (product name: MVLP-500,
¢ . ‘ ’ manufactured by Meiki Co., Ltd.) at a cemperature of 50°C : and a pressure of 0.3 MPa for 10 seconds. Thereby, a test piece having a thickness of 300 pm was obtained. The melt viscosity (Pass) at 80°C of this test piece was calculated from a temperature-viscous resistance curve obtained by measuring a change in a viscous resistance within a temperature range of 20 to 100°C at a rate of temperature rise of 10°C/min using a rheometer (RS150, manufactured by Haake). (Measurement of Elastic Modulus)
A film adhesive obtained in each Example and
Comparative Example was cut into a size of 5 mm x 17 mm and heated at a temperature of 180°C for 1 hour using a dryertothermallycurethefilmadhesive. Valuesofelastic moduli at 100°C, 200°C, and 250°C of the film adhesive after the thermal curing were determinedby themeasurement using a dynamic viscoelasticity measuring apparatus 7s crack. [Citation List] [Patent Literature] [PTL 1] Japanese Unexamined Patent Application
Publication No. 2000-200794 [PTL 2] Japanese Unexamined Patent Application
Publication No. 2005-19516 [Summary of Invention] [Technical Problem]
The present invention has beenmade in consideration of the above-described problems of the conventional i techniques. An object of the present invention is to provide: afilmadhesivecompositionwhichmakesitpossible to obtain a film adhesive ‘having a favorable surface appearance, asufficientlylowmeltviscosity, anexcellent adhesivenesstoanadherend, andasufficientlyhighelastic modulus and a sufficiently lowwater absorption rate after
) , A ’ oo (product name: Rheogel-E4000F, manufactured by UBM Co.,
Ltd.) under conditions: a measurement temperature range - of 30 to 300°C, a rate of temperature rise of 5°C/min, and a frequency of 1 Hz. : 5 | (Measurement of Saturated Water Absorption Rate)
A film rdhesive obtained in each Example and : Comparative Example was cut into square pieces each 50 mm or longer on one side, which were stacked on each other to a thickness of 5 mm or larger. The laminate was placed on a disk-shaped mold having a diameter of 50 mm and a thickness of 3 mm, and heated using a compression molding machine (product name: ETA-D, manufacturedby SHINTO Metal
Industries Corporation) at a temperature of 150°C and a pressure of 2 MPa for 10 minutes. Then, this was placed in a heat dryer and heated at a temperature of 180°C for 1 hour to thermally cure the film adhesive. Thereby, a disk-shaped test piece having a diameter of 50 mm and a thickness of 3 mm was obtained. The mass (Wl) of this test piece was measured, and themass (W2) was also measured after water was absorbed for 100 hours at a temperature of 85°C anda relative humidity Ri of 85% usingatemperature & humidity chamber (product name: PR-1J, manufactured by
ESPEC Corp.). The saturated water absorption rate was : | determined according to the following formula:
Saturated water absorption rate (% by mass) = { (W2-W1)/W1l}x100. (Wire Bonding Evaluation)
A film adhesive obtained in each Example and
Comparative Example was first made to adhere toone surface of a dummy silicon wafer (aluminium vapor-deposition silicon wafer, size: 8 inches, thickness: 100 pm) at a temperature 70°C and a pressure of 0.3 MPa using a manual laminator (product name: FM-114, manufactured by
Technovision, Inc.}. Then, a dicing tape (product name:
G-11, manufactured by Lintec Corporation) and a dicing : frame (produce name: DTF2-8-1H001, manufactured by psco
Corporation) were made adhere to on a surface of the film adhesive on a side opposite to the dummy silicon wafer at room temperature and a pressure of 0.3 MPa using the same manual laminator. Subsequently, a dicing apparatus (product name: ‘DFD-6340, manufactured by DISCO
Corporation) equipped with dual-axis dicing blades (21:
NBC~-ZH2030-SE (DD), manufacturedbyDISCOCorporation/Z2:
NBC-ZH127F-SE (BB), manufactured by DISCO Corporation) was used for dicing into a size of 0.5 mm x 0.5 mm. Thus, a semiconductor chip was obtained.
Then, the semiconductor chip was thermocompression bonded to a lead frame board (42 Alloy type, manufactured by Toppan Printing Co., Ltd.) using a die bonder (product name: SPA-300, manufactured by Shinkawa Ltd.) under conditions: a temperature of 120°C, a pressure of 4.1 MPa
} » , ’ (load: 100 gf), and a period of 1.0 seconds. This was placed in a dryer and heated at a emperature of 120°C for 1 hour to thermally cure the film adhesive.
Subsequently, the semiconductor chip and the lead frame board were connected toeachotherwithagoldwire (product name: AT Series, 25 um®, manufactured by Nippon Steel
Materials Co., Ltd.) using a wire bonderx (product name:
UTC-3000, manufactured by Shinkawa Ltd.) at a stage Co temperature of 200°C. The ball shear strength at the top surface of the semiconductor chip was measured using a bondtester (product name: Series 5000, Dage Co., Ltd.) and evaluated according to the following criteria:
A: ball shear strength of 10 mg / pm’ or higher
B: ball shear strength between 10 to 5 mg/pm?
C: ball shear strength of 5 mg/pm® or lower. (Package Crack Evaluation)
Atestplecewaspreparedhy Connect ings semiconductor
} “ ’ ’ ’ chip and a wiring board with a gold wire by the same method as that in the wire bonding evaluation. The cast piece was sealed with a mold compound (manufactured by Kyocera
Corporation, KE-3000F5-2) using amolding system (product name: V1R, manufacturedbyTOWACorporation), andthermally cured by heating at a temperature of 180°C for 5 hours.
Thus, asemiconductorpackagewasobtained.Afterabsorbing ’ water for 100 hours at temperature of 85°C and a relative humidity RH of 85% using a temperature & humidity chamber (product name: PR-1J, manufactured by ESPEC Corp.), the resulting semiconductor package was heated in an IRreflow oven at a temperature of 240°C for 10 seconds. After the heating, the semiconductor package was cut with a diamond cutter, and observed to check whether or not any package crack was formed by a microscope observation. Thirty semiconductor packages wore prepared and evaluated according to the following criteria:
- . | , y
A: no package crack formation was observed in all sentoonductor packages 'B: a package crack was formed in one or more semiconductor packages. (Example 1)
First, in a 100-ml separable flask, 1.5 parts by mass (2 parts by mass relative to 100 parts by mass of a spherical silica filler) of 3-glycidoxypropyltrimethoxysilane (product name:
KBM-403, manufactured by Shin-Etsu Silicone) was weighed and stirred in 32 parts bymass of a solvent methyl isobutyl ketone (MIBK) at a temperature of 50°C for 2 Hours. This was blended with 74 parts by mass of the weighed spherical silica filler (product name: S0O-C2, average particle diameter: 0.5 pm, manufactured by Admatechs Co. Ltd.), and further stirred for 2 hours. Thus, a surface-treated . | spherical silica filler dispersion liquid was obtained.
Then, the surface-treated spherical silica filler dispersion liquid thus obtained was blended with 55 parts by mass of a solid bisphenol A type epoxy resin (product name: YD-011, weight average molecular weight: 1000, softening point: 70°C, solid, epoxy equivalent: 450, manufactured by NSCC Epoxy Manufacturing Co., Ltd.), 49 parts by mass of . liquid bisphenol A type epoxy resin (product name: YD-128, weight average molecular weight: 400, softening point: 25°C or lower, liquid, epoxy equivalent: 190, nana Ee Cured by NSCC Epoxy Manufacturing
Co., Ltd.), 28 parts by mass of a bisphenol A type phenoxy resin (product name: YP-50S, weight average molecular weight: 60000, Tg: 84°C, manufactured by NSCC Epoxy
Manufacturing Co., Ltd.), and 40 parts by mass of a solvent
Fatiyl Losiutyl Felons Sis wold. Thisblendwas heated and stirred at a temperature of 110°C for 2 hours in a 500-mlseparableflask. Thus, aresinmixturewasobtained.
Then, 280 parts by mass of this resin mixture was transferred to an 800~ml planetary mixer, towhich 9 parts by mass of an imidazole-type curing agent (product name: 2PHZ-PW, manufactured by Shikoku Chemicals Corporation) was added, andminedtogetherbystirringat roontenperature for 1 hour. After bubbles were removed under vacuum, a film adhesive composition was obtained. Subsequently, : the obtained film adhesive composition was applied to a
PET film having a thickness of 50 pm having been subjected to the mold-release treatment, and then heat-dried at a temperature of 100°C for 10minutes. Thus, afilm adhesive of 200 mm x 300 mm with a thickness of 5 ym was obtained. (Example 2) :
A film adhesive composition and a film adhesive were obtained in the same manner as in Example 1 except that: vinyltrimethoxysilane (product name; KBM-1003, manufactured by Shin-Etsu Silicone) was used in place of
) ‘ ‘ - 3-glycidoxypropyltrimethoxysilane. (Example 3)
A film adhesive composition and a film adhesive were obtained in the same manner as in Example 1 except that: vinyltriethoxysilane (product name ; KBE-1003, manufactured by Shin~Etsu Silicone) was used in place of 3-glycidoxypropyltrimethoxysilane. (Example 4) : Afilmadhesive composition and a film adhesive were obtained in the same manner as in Example 2 except that: a cresol novolac type epoxy resin (product name:
ECON-1020-80, weight average molecular weight: 1200, softening point: 80°C, solid, epoxy equivalent: 200, manufactured by Nippon Kayaku Co., Ltd.) was used in place of the solid bisphenol a type epoxy resin. (Example 5)
A film adhesive composition and a film adhesive were obtained in the same manner as in Example 2 except that: a triphenylmethane type epoxy resin (product name: : EPPN-501H, weight average molecular weight: 1000, oo softening point: 55°C, solid, epoxy equivalent: 167, manufactured by Nippon Kayaku Co., Ltd.) was used in place of the solid bisphenol A type epoxy resin. (Example 6)
A film adhesive composition and a £ilm adhesive were obtained in the same manner as in Example 2 except that: a dicyclopentadiene type epoxy resin (product name:
XD-1000, weight averagemolecularweight: 1200, softening point: Joc, solid, epoxy equivalent: 250, manufactured by Nippon cayaku Co., Ltd.) was used in place ot the solid bisphenol A type epoxy resin. (Example 7) .
A film adhesive composition and a film adhesive were obtained in the same manner as in Example 2 except that:
curing; a method for producing the film adhesive composition; a filnadnesive; a seniconductozpackage using the film adhesive; and a method for manufacturing the semiconductor package. - 5 [Solution to Problem]
The present inventors haveearnestlystudiedinorder to achieve the above object. As a result, the inventors have found out the following facts. Specifically, in a method for producing a film adhesive composition, first, a surface-treated spherical silica filler obtained by subjecting a spherical silica filler having an average particle diameter of 0.01 to 2.0 ym to a surface treatment with a silane coupling agent is dispersed in an organic solvent to thus obtain a surface-treated spherical silica filler dispersion liquid. Then, the surface-treated spherical silica filler dispersion liquid thus obtained is mixed with an epoxy resin, an epoxy resin curing agent,
the surface-treated spherical silica filler dispersion liquid was Further blended with 3 parts by mass of a | i hydrophobic fumed silica (product name: RY-200, manufactured by Nippon Aerosil Co., Ltd.) as an additive. (Example 8)
A in adhesive composition and a film adhesive were obtained in the same manner as in Example 2 except that: the blended amount of vinyltrimethoxysilane used in the surface-treated spherical silicafillerdispersionliquid was 2.8 partsbymass, theblended amount of methyl isobutyl ketone was 60 parts by mass, and the blended amount of the spherical silica filler was 137 parts by mass. (Example 9)
A film adhesive composition and a £ilm adhesive were obtained in the same manner as in Example 2 except that: the blended amount of vinyltrimethoxysilane used in the surface-treatedsphericalsilicafillerdispersion Liquid was 4.2 parts by mass, theblended amount of methyl isobutyl cetons was 90 pares by mass, and the blended amount of the spherical silica filler was 206 parts by mass. (Example 10)
A film adhesive composition and a film adhesive were obtained in the same manner as in Example 2 except that: the blended amount of vinyltrimethoxysilane used in the surface-treatedspherical silicafillerdispersionliquid was 6.5partsbymass, theblended amount of methyl isobutyl ketone was 140 parts by mass, and the blended amount of the spherical silica filler was 320 parts by mass. . {Comparative Example 1)
First, in a 500-ml separable flask, 1.5 parts by mass (2 parts by mass relative to 100 parts by mass of asphericalsilicafiller) ofvinyltrimethoxysilane (name;
KBM-1003, manufactured by Shin-Etsu Silicone), 74 parts bymassofthesphericalsilicafiller (productname: SO-C2,
average particle diameter: 0.5 um, manufactured by
Admatechs co. Ltd.), 55 parts by mass of a solid bisphenol
A type epoxy resin (product name: ¥YD-01l, weight average molecularweight:1000, softeningpoint: 70°C, solid, epoxy equivalent: 450, manufactured by NSCC Epoxy Manufacturing
Co., Ltd.), 49 parts by mass of a liquid bisphenol A type epoxyresin (productname: YD-128, weightaveragemolecular weight: 400, softening boint: 25°C or lower, liquid, epoxy equivalent: 190, manufactured by NSCC Epoxy Manufacturing
Co., Ltd.), 28 parts by mass of a bisphenol A type phenoxy resin (product name: YP-50S, weight average molecular weight: 60000, Tg: 84°C, manufactured by NSCC Epoxy
Manufacturing Co., Ltd.), 9 parts by mass of an imidazole-type curing agent (product name: 2PHZ-PW, manufactured by Shikoku Chemicals Corporation), and 40 parts by mass of methyl isobutyl ketone thus weighed were blended together. This blend was heated and stirred at a temperature of 110°C for 2 hours. Thus, a resin mixture was obtained. . : Then, 280 parts by mass of the resin mixture thus obtained was transferred to an 800-ml planetary mixer, and mixed by stirring at roomtemperature for 1 hour. After bubbles were removed under vacuum, a film adhesive compositionwasobtained. Subsequently, the obtained Film adhesive composition was applied to a PET film having a thicknessof 50pmhavingbeensubjectedtothemold~release treatment, and then heat-dried at a temperature of 100°C for 10 minutes. hus, a film adhesive of 200 mm x 300 mm with a thickness of 5 pum was obtained. (Comparative Example 2)
A film adhesive composition and a film adhesive were obtained in the same manner as in Comparative Example 1 except that: the blended amount of vinyltrimethoxysilane was 11 parts by mass, the blended amount of methyl isobutyl ketone was 100 parts by mass, and the blended amount of the spherical silica filler was 549 parts by mass. (Comparative Example 3)
A film adhesive composition and a film adhesive were obtained in the same nanner as in example 2 except that: the blended amount of oinyltrinethoxysilane blended in the surface-treated spherical silica filler dispersion liquid was 0.3 parts by mass, the blended amount of methyl isobutyl ketone was 7 parts by mass, and the blended amount of the spherical silica filler was 15 parts by mass. : (Comparative Example 4)
A film adhesive composition and a film adhesive were obtained in the same manner as in Example 2 except that: the blended amount of vinyltrimethoxysilane blended in the surface-treated spherical silica filler dispersion liquid was 0.7 parts by mass, the blended amount of methyl isobutyl ketone was 15 parts by mass, and the blended amount
] of the sonerical silica filler was 34 parts by mass.
Table 1 shows the results of conducting the grind gaugeevaluationand the £ilmsurfaceappearanceevaluation using the film adhesive compositions obtained in Examples l to 10 and Comparative Examples 1 to 4, as well as the measurements of melt viscosity, elastic modulus, and saturated water absorption rate, and the wire bonding evaluationandthepackagecrackevaluationoftheresulting film adhesives, together with the compositions of the £ilm adhesive compositions. Note that "<10" in the grind gauge evaluation indicates that no line was observed. [Table 1]
EE ————————————————————————————————— — ———————————————————————————————
Composition “Comparative Example 1 {23 4s] 6) 7]8folis] 1] 213] 4] surface- treated spherical silica filler 74 | 74 | 74 | 74 | 74 | 74 | 74 | 137 320 34 } spherical
Toots oy | EyGiGoRpropylimethogstane] 18 | — | — | — J ~~ ~~] JT | I as [vinyitimethoxysilane | _- | 15) - | 156] 151 15 | 1.5] 281 421651 - | - 103] 07 vinyltriethoxysilane | - 1 -1+7{ -r-1-1-71-71-4-1- 1 - TT 1 - 1
SPU bisphenol A type (solid | 55 1 55 | 65 1 - | - | - | 55] 55] 55] 55] 55 | 65 | 55 | 55 resin | _cresolnovolactype(sotid) | - I - 1 - Iss -1 -1T -0L-T-1-1-"1 -"1T-1T1.-1 [parts by [—tophenylmethaneype (solid) f - | - I - { - 165 { - 1 - 1 -f - 1 -1 - 1 - 1-1} - mass] |—dicyclopentadienetype(sotig) 1 - { - 1 - | - | - 15st - 1 - J -1 -1 - 1 - 1-1 - bisphenol A type (liquid | 49 | 49 | 49 [ 49 | 49 [ 49 | 49 | 40 | 40 | 40 | 49 | 49 | 49 | 49 phenoxy resin i 2 28 28 - [parts by bisphenol A type 28 | 28 | 28 | 28 | 28 | 28 | 28 | 28 28 8 mad 8 oor rnoumasgmposmmos | oo ola] ol ololololol alo ]o]s] = - mores seamen | | [Te meron | | |] ||| Te et: itd 0 IE EI IE EE EY KC A EE EE EER % by mass] (*1 | ss | 35 | 35 [ as | as | 35 70 |35(2)| 80("2) grind gauge evaluation [um] | <to[<to] <tof <tof<to|<tof<iof<tof<to]<t0] oo | 100 | 80 | 90 fim surface appearance evaluation | A | A | A | A [A | A | A| A| AA] B | B [A[ A melt viscosity at 80°C [Pa-s] 1500] 1550] 1500 1600] 1700] 1200] 3000 2000] 2500] 5000] 2200 | 12000 | 700 | 1000 elastic modutus (100°C) [MPa] [2000] 1900] 2000] 2000] 2000] 1900] 2100] 2400] 2800] 3300] 1900 | 4800 | 1900] 1900 elastic modulus (200°C) [MPa] | 37 | 35 | 36 J1400]1700[1500] 38 | 40 | 50 | 70 | 35 | 80 | 9 | 20 elastic modulus (250°C) [MPa] 35 [33 | 35 [230780110] 35 | 38 [40 | 50 | 33 [ 70 | 10] 15 res vatr sotto ym | 14 13] 12] va] va [12 [10] + Joa va | or [ro] 07] wire bonding évaiuation [6 |6|B6|AlAlB[B|B]B]B|B] 8B [C|B package crack evaluation [Al AlAlAlAlAlAlAlAlAl A] B |B] 5 *1: a content relative to a total amount of a surface-treated spherical silica filler, an epoxy resin, a phenoxy resin, and an epoxy resin curing agent *2: a content of sum of a spherical silica filler and vinyitrimethoxysilane relative to a total amount of the spherical silica filler, vinyltrimethoxysilane, an epoxy resin, a phenoxy resin, and an epoxy resin curing agent
As apparent from the results shown in Table 1, it was verified that the film adhesive compositions obtained in Examples 1 to 10 each had the surface~treated spherical silica filler quite uniformly dispersed therein, and the : 5 film adhesive formed from the film adhesive composition obtained using this had a favorable surface appearance andasufficientlylowmeltviscosityats0oc. Furthermore, it was verified that after the thermal curing, the elastic modulus was sufficiently high and the water absorption rate was sufficiently low, the bonding strength of the bondingwireinthemanufacturingprocessofasemiconductor packagewasalsoatahighlevel, andpackagecrackformation was. sufficiently suppressed. [Industrial Applicability]
As describedhereinabove, thepresentinventionmakes it possible to provide: a film adhesive composition which makesitpossibletoobtainafilmadhesivehavingafavorable surface appearance, a sufficiently low melt viscosity, anexcellentadnesivenesstoanadherend, andasufficiently highelasticmodulusandasufficientlylowwaterabsorption rate after curing; amethod for producing the £ilm adhesive composition; afilmadhesive; asemiconductorpackageusing the film adhesive; and a method for manufacturing the semiconductor package.
Therefore, even when a semiconductor chip is made thinner and smaller, the present invention enables the | semiconductor chip and a wiring board to adhere to each other with high precision in the manufacturing process of a semiconductor package, enables abondingwire toretain the bonding strength at a high level, and makes it possible to sufficiently suppress formation of a package crack.
Accordingly, the present invention is extremely useful oo as a technique for bonding between a semiconductor chip and a wiring board, and bonding between a semiconductor chip and a semiconductor chip, in a semiconductor package. [Reference Signs List] 1: wafer 2: adhesive layer
3: dicing tape 4: adhesive layer-provided semiconductor chip 5: wiring board 6: bonding wire
71: sealing resin 8: semiconductor package

Claims (1)

1. A method for producing a film adhesive composition which comprises an epoxy resin (A), an epoxy resin curing agent (B), a phenoxy resin (C), and a surface-treated spherical silica filler (D) obtained by subjecting a spherical silica fillerhavinganaverageparticlediameter of 0.01 to 2.0 pm to a surface treatment with a silane coupling agent, and which has a content of the surface-treated spherical silica filler (D) of 35 to 50% by mass relative to a total amount of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C) and the surface-treated spherical silica filler (D), anelasticmodulus at 200°Cafter thermal curing of 20 to 3000 MPa, and a saturated water absorption rate after thermal curing of 1.5% by mass or less,
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