WO1999005196A1 - Thermosetting resin compositions useful as underfill sealants - Google Patents

Thermosetting resin compositions useful as underfill sealants Download PDF

Info

Publication number
WO1999005196A1
WO1999005196A1 PCT/US1998/015578 US9815578W WO9905196A1 WO 1999005196 A1 WO1999005196 A1 WO 1999005196A1 US 9815578 W US9815578 W US 9815578W WO 9905196 A1 WO9905196 A1 WO 9905196A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
epoxy resin
composition
methylimidizole
imidizole
Prior art date
Application number
PCT/US1998/015578
Other languages
French (fr)
Inventor
Mark Konarski
Zbigniew A. Szczepaniak
Original Assignee
Loctite Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Loctite Corporation filed Critical Loctite Corporation
Priority to JP51020999A priority Critical patent/JP2001506313A/en
Priority to DE69833865T priority patent/DE69833865T2/en
Priority to BR9806065-1A priority patent/BR9806065A/en
Priority to KR1019997002498A priority patent/KR100571334B1/en
Priority to AU85959/98A priority patent/AU728193B2/en
Priority to US09/269,067 priority patent/US6342577B1/en
Priority to EP98937187A priority patent/EP0929592B1/en
Priority to CA002266314A priority patent/CA2266314A1/en
Publication of WO1999005196A1 publication Critical patent/WO1999005196A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H01L2224/83855—Hardening the adhesive by curing, i.e. thermosetting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01037—Rubidium [Rb]

Definitions

  • DCA circuit board direct chip attach
  • curable resin compositions generally are known. See e.g. , U.S. Patent No. 4,645,803 (Kohli) which relates to curable epoxy resin compositions of reinforcing filaments and epoxy resins together with a primary amine-funtional curing agent with or without a polyamine curing agent and a curing catalyst which when cured into a fiber matrix is useful in preparing composites and prepreg materials for structural applications.
  • U.S. Patent No. 4,645,803 Kohli
  • 4,499,245 (Ikeguchi) relates to a curable resin composition requiring a mixture and/or a reaction product of (a) a polyfunctional cyanate ester, prepolymer of the cyanate ester or coprepolymer of the cyanate ester and an amine and (b) a polyhydantion resin -- a phenolic-based epoxy curative.
  • a polyfunctional maleimide, prepolymer of the maleimide or coprepolymer of the maleimide and an amine may be included as a component (c) .
  • These compositions are reported to be useful as coating materials for rust prevention, flame resistance, flame retardation; electrical insulation varnish; and laminates for use with furniture, building materials, and sheathing materials.
  • thermosetting compositions of cyanate esters and epoxy resins are also generally known. See e.g., Japanese patent document JP 62-275,123, an English-language abstract of which speaks to a resin composition for preparing prepreg materials with reinforcing fiber for structural applications.
  • the compositions are reported to include certain cyanate esters, bismaleimide, polyether sulfone (as a non-reactive thermoplast whose use is as a toughening agent) and bisphenol F- or A-type epoxy resin.
  • the composition is reported to be optionally hardened by a hardening catalyst, one of which is noted as imidizole.
  • U.S. Patent No. 4,918,157 (Gardner) relates to the use of urea compounds as latent cure accelerators for cyanate esters, and to thermosetting cyanate ester formulations of cyanate esters and urea compounds. More specifically, the '157 patent claims a thermosetting composition of a cyanate ester; a urea compound selected from alkyl aryl ureas, aryl ureas and mixtures thereof; and an epoxy resin.
  • the curable cyanate ester formulations of the '157 patent are reportedly useful as matrix resins, and for the production of prepreg, fiber-reinforced laminates, composites and the like.
  • Epoxy curing systems are also known. See e.g., U.S. Patent No. 3,862,260 (Sellers), in which a curing agent of a trifunctional hardener (such as the reaction product of one mole of bisphenol A with one mole of formaldehyde) and an imidizole is disclosed.
  • a curing agent of a trifunctional hardener such as the reaction product of one mole of bisphenol A with one mole of formaldehyde
  • an imidizole is disclosed.
  • thermosetting resin compositions appear to be directed to structural applications, as contrasted to the microelectronic application to which the compositions of the present invention are directed.
  • the use of epoxy resin compositions as matrix compositions for fiber reinforcement in prepreg, composite and laminate materials for structural materials differs significantly from the use of epoxy resin compositions as an adhesive and encapsulant in microelectronic applications, such as with electrical solder junctions in semiconductor chips, and creates different demands and requirements from the uncured resin as well as cured reaction products thereof.
  • an underfilling sealant composition to provide good adhesive properties while flowing and curing in a sufficiently quick time to be commercially appealing and possessing an extended useful working life.
  • thermosetting resin composition useful as an underfilling sealant composition which (1) rapidly fills the underfill space in a semiconductor device, such as a flip chip assembly which includes a semiconductor chip mounted on a carrier substrate, (2) enables the semiconductor to be securely connected to a circuit board by short-time heat curing and with good productivity, and (3) demonstrates excellent heat shock properties (or thermal cycle properties) .
  • the thermosetting resin compositions of this invention which are used as underfill sealants between such a semiconductor device and a circuit board to which the semiconductor device is electrically connected, includes an epoxy resin component and a latent hardener component.
  • the latent hardener component includes a cyanate ester component and an imidizole component.
  • thermosetting resin compositions of this invention semiconductor devices, such as flip chip assemblies, may be (1) assembled quickly and without production line down time because of improved cure speed and extended useful working life, and (2) securely connected to a circuit board by short-time heat curing of the composition, with the resulting mounted structure (at least in part due to the cured composition) demonstrating excellent heat shock properties (or thermal cycle properties) .
  • compositions of this invention may also be used for microelectronic applications beyond sealing underfill, such as with glob top, die attachment and other applications for thermosetting compositions in which rapid cure time and an extended useful working life are desirable.
  • Figure 1 depicts a cross-sectional view showing an example of a mounted structure with which the thermosetting resin composition of the present invention is used as an underfill sealant.
  • thermosetting resin compositions which are useful as underfill sealants between a semiconductor device and a circuit board to which the semiconductor device is electrically connected, include an epoxy resin component and a latent hardener component .
  • the latent hardener component includes a cyanate ester component and an imidizole component .
  • the composition includes about 100 parts by weight of the epoxy resin component, and 0 to about 30 parts by weight of the latent hardener component, of which 0 to about 15 parts is comprised of the cyanate ester component and 0 to about 15 parts is comprised of the imidizole component.
  • the latent hardener component should include about 4 parts each of the cyanate ester component and the imidizole component.
  • the epoxy resin component of the present invention may include any common epoxy resin.
  • This epoxy resin may be comprised of at least one multifunctional epoxy resin, optionally, together with at least one monofunctional epoxy resin.
  • the multifunctional epoxy resin should be included in amount within the range of about 20 parts to about 100 parts of the epoxy resin component.
  • the amount thereof should be in the range of from about 40 to 80 parts.
  • a monofunctional epoxy resin if present, should ordinarily be used as a reactive diluent, or crosslink density modifier. In the event such a monofunctional epoxy resin is included as a portion of the epoxy resin component, such resin should be employed in an amount of up to about 20% by weight based on the total epoxy resin component.
  • the monofunctional epoxy resin should have an epoxy group with an alkyl group of about 6 to about 28 carbon atoms, examples of which include C 6 -C 28 alkyl glycidyl ethers, C 6 -C 28 fatty acid glycidyl esters and C 6 -C 28 alkylphenol glycidyl ethers.
  • Such epoxy resin (s) include generally, but are not limited to, polyglycidyl ethers of polyvalent phenols, for example pyrocatechol ; resorcinol; hydroquinone ;
  • reaction products of monohydric or polyhydric phenols with aldehydes, formaldehyde in particular, in the presence of acid catalyst polyglycidyl ethers of diphenols obtained by esterifying 2 moles of the ethers of diphenols obtained by esterifying 2 moles of the sodium salt of an aromatic hydrocarboxylic acid with 1 mole of a dihaloalkane or dihalogen dialkyl ether (see U.K. Pat. No.
  • epoxy compounds include polyepoxy compounds based on aromatic amines and epichlorohydrin, such as N, N' -diglycidyl-aniline;
  • N,N,N' ,N' -tetraglycidyl-1, 3-propylene bis-4-aminobenzoate examples include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, and cresol novolac-type epoxy resin.
  • epoxy resins suitable for use herein are polyglycidyl derivatives of phenolic compounds, such as those available commercially under the tradenames EPON 828, EPON 1001, EPON 1009, ' and EPON 1031, from Shell Chemical Co.; DER 331, DER 332, DER 334, and DER 542 from Dow Chemical Co.; and BREN-S from Nippon Kayaku, Japan.
  • Other suitable epoxy resins include polyepoxides prepared from polyols and the like and polyglycidyl derivatives of phenol -formaldehyde novolacs, the latter of which are available commercially under the tradenames DEN 431, DEN 438, and DEN 439 from Dow Chemical Company.
  • Cresol analogs are also available commercially ECN 1235, ECN 1273, and ECN 1299 from Ciba-Geigy Corporation.
  • SU-8 is a bisphenol A-type epoxy novolac available from Interez, Inc.
  • Polyglycidyl adducts of amines, aminoalcohols and polycarboxylic acids are also useful in this invention, commercially available resins of which include GLYAMINE 135, GLYAMINE 125, and GLYAMINE 115 from F.I.C. Corporation; ARALDITE MY-720, ARALDITE 0500, and ARALDITE 0510 from Ciba-Geigy Corporation and PGA-X and PGA-C from the Sherwin-Williams Co.
  • the cyanate esters useful as a component in the latent hardening component may be chosen from aryl compounds having at least one cyanate ester group on each molecule and may be generally represented by the formula Ar(OCN) m , where m is an integer from 2 to 5 and Ar is an aromatic radical.
  • the aromatic radical Ar should contain at least 6 carbon atoms, and may be derived, for example, from aromatic hydrocarbons, such as benzene, biphenyl, naphthalene, anthracene, pyrene or the like.
  • the aromatic radical Ar may also be derived from a polynuclear aromatic hydrocarbon in which at least two aromatic rings are attached to each other through a bridging group. Also included are aromatic radicals derived from novolac-type phenolic resins -- i.e., cyanate esters of these phenolic resins. The aromatic radical Ar may also contain further ring-attached, non-reactive substituents .
  • cyanate esters include, for instance, 1, 3-dicyanatobenzene ; 1, 4-dicyanatobenzene; 1, 3 , 5-tricyanatobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2 , 7-dicyanatonaphthalene; 1,3, 6-tricyanatonaphthalene; 4 , 4 ' -dicyanato-biphenyl ; bis (4 -cyanatophenyl) methane and 3,3' ,5,5' -tetramethyl bis (4 -cyanatophenyl) methane; 2 , 2-bis (3 , 5 -dichloro-4 -cyanatophenyl) propane; 2 , 2-bis (3 , 5-dibromo-4-dicyanatophenyl) propane; bis (4 -cyanatophenyl) ether; bis (4 -cyanatophenyl) sulfide; 2 , 2-bis (4 -cyanatophenyl) propane ; tri
  • cyanate esters include cyanates disclosed in U.S. Patent Nos . 4,477,629 and 4,528,366, the disclosure of each of which is hereby expressly incorporated herein by reference; the cyanate esters disclosed in U.K. Pat. No. 1,305,702, and the cyanate esters disclosed in International Patent Publication WO 85/02184, the disclosure of each of which is hereby expressly incorporated herein by reference.
  • combinations of these cyanate esters within the imidizole component of the compositions of the present invention are also desirably employed herein.
  • a particularly desirable cyanate ester for use herein is available commercially from Ciba Geigy
  • the imidizole component of the latent hardener component include imidizoles, such as imidizole and derivatives thereof, such as isoimidizole, imidizole, alkyl substituted imidizoles, such as 2-methyl imidizole, 2-ethyl-4 -methylimidizole, 2 , 4 -dime hylimidizole, butylimidizole , 2 -heptadecenyl -4 -methylimidizole , 2 -methylimidizole , 2 -undecenylimidizole ,
  • imidizoles such as imidizole and derivatives thereof, such as isoimidizole, imidizole, alkyl substituted imidizoles, such as 2-methyl imidizole, 2-ethyl-4 -methylimidizole, 2 , 4 -dime hylimidizole, butylimidizole , 2 -hepta
  • 2-n-heptadecyl-4-methylimidizole and the like generally where each alkyl substituent contains up to about 17 carbon atoms and desirably up to about 6 carbon atoms; aryl substituted imidizoles, such as phenylimidazole, benzylimidizole, 2 -methyl-4, 5-diphenylimidizole,
  • 2-napnthyl-4 5-diphenylimidizole, l-benzyl-2-methylimidizole, 2-p-methoxystyrylimidizole, and the like generally where each aryl substituent contains up to about 10 carbon atoms and desirably up to about 8 carbon atoms.
  • thermosetting resin compositions of the present invention may be of the one-pack type, in which all the ingredients are mixed together, or of the two-pack type in which the epoxy resin component and latent hardener component are stored separately and mixed together prior to use .
  • thermosetting resin compositions according to the present invention penetrate and flow readily into the space between the circuit board and the semiconductor device, or at least show a reduction in viscosity under heated or use conditions thus penetrating and flowing easily.
  • thermosetting resin compositions of this invention by selecting the types and proportions of various so that the gel times will be tailored to a specified period of time (such as 1 minute or 2 minutes) at a temperature of about 150°C.
  • the inventive compositions should show no or substantially no increase of viscosity after a period of time of about six hours. With such a gel time, the compositions penetrate into the space between the circuit board and the semiconductor device (e.g. , of 100 to 200 ⁇ m) relatively rapidly, and allow for a greater number of assemblies to be filled without observing a viscosity increase in the composition thereby rendering it less effective for application.
  • thermosetting resin composition of the present invention may further contain other additives such as defoaming agents, leveling agents, dyes, pigments and fillers.
  • the compositions may also contain photopolymerization initiators, provided such materials do not adversely affect the desired properties of the composition.
  • filled thermosetting compositions include a filler component.
  • the filler component acts to lower moisture pick up, and tends to increase viscosity.
  • Appropriate filler components include silica, alumina, silica-coated aluminum nitride, silver flake and the like.
  • the filler component may be used, with about 150 to 180 parts being desirable.
  • FIG. 1 shows a mounted structure (i.e. , a flip chip package) in which a thermosetting resin composition of the present invention has been applied and cured.
  • the flip chip package 4 is formed by connecting a semiconductor chip (a bare chip) 2 to a carrier substrate 1 (e.g. , a circuit board) and sealing the space therebetween suitably with a thermosetting resin composition 3.
  • a semiconductor device is mounted at a predetermined position on the carrier substrate 1, and electrodes 5 and 6 are electrically connected by a suitable electrical connection means 7 and 8, such as solder.
  • a suitable electrical connection means 7 and 8, such as solder such as solder.
  • the space between the semiconductor chip 2 and the carrier substrate 1 is sealed with a thermosetting resin composition 3, and then cured.
  • the cured product of the thermosetting resin composition should completely fill that space .
  • Carrier substrates may be constructed from ceramic substrates of A1 2 0 3 , SiN 3 and mullite (Al 2 0 3 -Si0 2 ) ; substrates or tapes of heat-resistant resins, such as polyimides; glass-reinforced epoxy; ABS and phenolic substrates which are also used commonly as circuit boards; and the like. Any electrical connection of the semiconductor chip to the carrier substrate may be used, such as connection by a high-melting solder or electrically (or anisotropically) conductive adhesive, wire bonding, and the like. In order to facilitate connections, the electrodes may be formed as bumps.
  • solder ball (e.g. , in cream or form) may be printed at appropriate positions on a carrier substrate and suitably dried to expel solvent .
  • a semiconductor chip may then mounted in conformity with the pattern on the carrier substrate.
  • This carrier substrate is then passed through a reflowing furnace to melt the solder to connect the semiconductor chip.
  • the solder may be applied or formed on either the carrier substrate or the semiconductor chip. Alternatively, this connection may also be made by an electrically conductive adhesive or an anisotropically conductive adhesive.
  • the resulting structure is ordinarily subjected to a continuity test or the like. After passing such test, the semiconductor chip may be fixed thereto with a thermosetting resin composition, as described below. In this way, in the event of a failure, the semiconductor chip may be removed before it is fixed to the carrier substrate with the thermosetting resin composition.
  • thermosetting resin composition in accordance with this invention is applied to the periphery of the electronically-connected semiconductor chip.
  • the composition penetrates by capillary action into the space between the carrier substrate and the semiconductor chip.
  • thermosetting resin composition is then thermally cured by the application of heat.
  • the thermosetting resin composition shows a significant reduction in viscosity and hence an increase in fluidity, so that it more easily penetrates into the space between the carrier substrate and the semiconductor chip.
  • the thermosetting resin composition is allowed to penetrate fully into the entire space between the carrier substrate and the semiconductor chip.
  • thermosetting resin compositions of the present invention demonstrate excellent adhesive force, heat resistance and electric properties, and acceptable mechanical properties, such as flex-cracking resistance, chemical resistance, moisture resistance and the like, for the applications for which they are used herein.
  • the amount of thermosetting resin composition applied should be suitably adjusted so as to fill almost completely the space between the carrier substrate and the semiconductor chip, which amount of course may vary depending on application.
  • Thermosetting resin compositions of the present invention may ordinarily be cured by heating to a temperature in the range of about 120 to about 180°C for a period of time of about 0.5 to 30 minutes. However, generally after application of the composition, an initial cure time of about 1 minute sets up the composition, and complete cure is observed after about 15 minutes at 150°C.
  • the composition of the present invention can be used in relatively moderate temperatures and short -time curing conditions, and hence achieve very good productivity.
  • compositions in accordance with the present invention were prepared and evaluated for performance in contrast with compositions prepared without the cyanate ester component of the latent hardener component. Results are set forth below.
  • thermosetting resin composition for underfill applications in accordance with the present invention was prepared by mixing together with stirring for a period of time of about 10 minutes at room temperature in an open vessel an epoxy resin component including 92 parts by weight of bisphenol F-type epoxy resin, and a latent hardener component including 4 parts by weight of 2 -ethyl-4 -methylimidizole, and 4 parts by weight of
  • composition While the composition was used upon formation, it may be stored for a period of time of up to about 3 to about 6 months at a temperature of about -20 °C without experiencing viscosity increase.
  • the composition was transferred to a 10 ml syringe made of non-reactive plastic, and the composition was dispensed through the 12G needle of the syringe into the junction between the carrier substrate and semiconductor chip in a previously-formed assembly.
  • the composition acts as an encapulant for the electrical solder connection.
  • the assembly was transferred to an oven while the temperature was maintained at about 150°C.
  • the composition cured initially after about 1 minute, and thereafter cured completely after about 15 minutes at that temperature.
  • the composition was placed between a pair of lap shears and cured in the same way as the assembly above.
  • the bound lap shears were removed from the oven and allowed to reach room temperature, at which point they were evaluated for bond strength.
  • the cured composition was found to possess lap shear strength of about 1660 psi -- which is acceptable for the microelectronic applications which the compositions are designed.
  • the gel time of the composition was tailored to 1 minute at a temperature of 150°C.
  • This composition was observed to experience no viscosity increase at room temperature after a period of time of 6 hours; after a period of time of about 15 hours the viscosity increase was observed to be about 52%; and after a period of time of about 24 hours the viscosity increase was observed to be about 88%.
  • a comparable composition was prepared in which no cyanate ester was added. That composition included 96.5 parts bisphenol F-type epoxy resin and 3.5 parts of 2-ethyl-4-methylimidizole . The composition was also tailored to a gel time of about 1 minute at a temperature of 150°C. The lap shear strength was observed to be about 1670 psi .
  • This composition was applied as above, and demonstrated a viscosity increase at room temperature after a period of time of about 6 hours of about 13%; after a period time of about 15 hours of about 153% and after a period of time of 24 hours of about 267%.
  • the presence of the cyanate ester component in the inventive compositions has a dramatic affect in maintaining a useful working life for the compositions with respect to slowing viscosity increase over time at room temperature.
  • thermosetting resin composition for underfill applications in accordance with the present invention was prepared by mixing together with stirring for a period of time of about 10 minutes at room temperature in an open vessel an epoxy resin component including 88 parts by weight of bisphenol F-type epoxy resin, and a latent hardener component including 8 parts by weight of 2-ethyl-4-methylimidizole, and 4 parts by weight of 1, 3-bis [4 -cyanatophenyl -1- (methylethylidene) ] benzene as a cyanate ester resin (AROCY 366) .
  • composition was used upon formation, it too may be stored for a period of time of up to about 3 to about 6 months at a temperature of about -20°C without experiencing viscosity increase.
  • the composition was transferred to a 10ml syringe made of non-reactive plastic, and the composition was dispensed through the 12G needle of the syringe into the junction between the carrier substrate and semiconductor chip in a previously- formed assembly to act as an encapulant for the electrical solder connection.
  • the assembly was transferred to an oven while the temperature was again maintained at about 150°C.
  • the composition cured initially after about 2 minutes, and thereafter cured completely after about 15 minutes at that temperature.
  • This composition was also placed between a pair of lap shears and cured in the same way as the assembly above, and as in Example 1.
  • the lap shears were removed from the oven and allowed to reach room temperature, at which point they were evaluated for bond strength.
  • the cured composition was found to possess lap shear strength of about 1620 psi -- which is acceptable for the microelectronic applications for which the compositions are designed.
  • the gel time of the composition was tailored to 2 minute at a temperature of 150°C. This composition was observed to experience a viscosity increase at room temperature after a period of time of 6 hours of about 3%; after a period of time of about 15 hours the viscosity increase was observed to be about 10%; and after a period of time of about 24 hours the viscosity increase was observed to be about 20%.
  • a comparable composition was prepared in which no cyanate ester was added. That composition included 97.5 parts bisphenol F-type epoxy resin and 2.5 parts of 2-ethyl-4-methylimidizole . The composition was also tailored to a gel time of about 2 minutes at a temperature of 150°C. The lap shear strength was observed to be about 1600 psi.
  • This composition was applied as above, and demonstrated a viscosity increase at room temperature after a period of time of about 6 hours of about 16%; after a period time of about 15 hours of about 82% and after a period of time of 24 hours of about 162%.
  • the presence of the cyanate ester in the inventive compositions has a dramatic affect in maintaining a useful working life for the compositions with respect to slowing viscosity increase over time at room temperature.

Abstract

The present invention provides a thermosetting resin composition useful as an underfilling sealant composition which rapidly fills the underfill space in a semiconductor device, such as a flip chip assembly which includes a semiconductor chip mounted on a carrier substrate, enables the semi-conductor to be securely connected to a circuit board by short-time heat curing and with good productivity, and demonstrates acceptable heat shock properties (or thermal cycle properties). The thermosetting resin composition which is used as an underfilling sealant between such a semiconductor device and a circuit board to which the semiconductor device is electrically connected, includes an epoxy resin component and a latent hardener component. The latent hardener component includes a cyanate ester component and an imidizole component.

Description

THERMOSETTING RESIN COMPOSITIONS USEFUL AS UNDERFILL SEALANTS
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to thermosetting resin compositions useful as underfill sealants for mounting under a circuit board direct chip attach ("DCA") packages, which have a semiconductor chip on a carrier substrate.
Brief Description of Related Technology
In recent years, the popularity of smaller-sized electronic appliances has made desirable size reduction of semiconductor devices. As a result, chip packages are becoming reduced in size to substantially that of the bare die themselves. Such smaller-sized chip packages improve the characteristics of the microelectronic device in which it is used, while retaining many beneficial operating features. This serves to protect semiconductor bare chips, and increases their reliability and useful life.
Ordinarily, chip assemblies are connected to electrical conductors on a circuit board by use of solder connection or the like. However, when the resulting chip/circuit board structure is subjected to conditions of thermal cycling, reliability becomes suspect due to fatigue of the solder connection between the circuit board and the chip assembly. Recent manufacturing advances provide a sealing resin (often referred to as underfill sealant) in the space created by the mounting of a DCA [such as a chip scale package ( "CSP" ) /ball grid array ("BGA") assembly] onto a circuit board to relieve stresses caused by thermal cycling. Underfill sealants have been seen to improve heat shock properties and enhance the reliability of such structures .
Of course, curable resin compositions generally are known. See e.g. , U.S. Patent No. 4,645,803 (Kohli) which relates to curable epoxy resin compositions of reinforcing filaments and epoxy resins together with a primary amine-funtional curing agent with or without a polyamine curing agent and a curing catalyst which when cured into a fiber matrix is useful in preparing composites and prepreg materials for structural applications. In addition, U.S. Patent No. 4,499,245 (Ikeguchi) relates to a curable resin composition requiring a mixture and/or a reaction product of (a) a polyfunctional cyanate ester, prepolymer of the cyanate ester or coprepolymer of the cyanate ester and an amine and (b) a polyhydantion resin -- a phenolic-based epoxy curative. In addition, a polyfunctional maleimide, prepolymer of the maleimide or coprepolymer of the maleimide and an amine may be included as a component (c) . These compositions are reported to be useful as coating materials for rust prevention, flame resistance, flame retardation; electrical insulation varnish; and laminates for use with furniture, building materials, and sheathing materials.
And more specifically thermosetting compositions of cyanate esters and epoxy resins are also generally known. See e.g., Japanese patent document JP 62-275,123, an English-language abstract of which speaks to a resin composition for preparing prepreg materials with reinforcing fiber for structural applications. The compositions are reported to include certain cyanate esters, bismaleimide, polyether sulfone (as a non-reactive thermoplast whose use is as a toughening agent) and bisphenol F- or A-type epoxy resin. In addition, the composition is reported to be optionally hardened by a hardening catalyst, one of which is noted as imidizole.
U.S. Patent No. 4,918,157 (Gardner) relates to the use of urea compounds as latent cure accelerators for cyanate esters, and to thermosetting cyanate ester formulations of cyanate esters and urea compounds. More specifically, the '157 patent claims a thermosetting composition of a cyanate ester; a urea compound selected from alkyl aryl ureas, aryl ureas and mixtures thereof; and an epoxy resin. The curable cyanate ester formulations of the '157 patent are reportedly useful as matrix resins, and for the production of prepreg, fiber-reinforced laminates, composites and the like.
Epoxy curing systems are also known. See e.g., U.S. Patent No. 3,862,260 (Sellers), in which a curing agent of a trifunctional hardener (such as the reaction product of one mole of bisphenol A with one mole of formaldehyde) and an imidizole is disclosed.
These uses for thermosetting resin compositions appear to be directed to structural applications, as contrasted to the microelectronic application to which the compositions of the present invention are directed. To that end, the use of epoxy resin compositions as matrix compositions for fiber reinforcement in prepreg, composite and laminate materials for structural materials differs significantly from the use of epoxy resin compositions as an adhesive and encapsulant in microelectronic applications, such as with electrical solder junctions in semiconductor chips, and creates different demands and requirements from the uncured resin as well as cured reaction products thereof.
A drawback to resin compositions presently used in microelectronics applications, such as for underfill sealants, is their extended cure schedule. In addition, providing such resins with a commercially acceptable useful working life at room temperature or dispensing temperatures has been problematic.
Generally, at temperatures near room temperature, the resins begin to cure upon introduction of the curing agent or catalyst. This causes viscosity increases which leads to reduced dispensability. While such viscosity increase may be alleviated to some degree by using a liquid curing agent or catalyst, liquid catalysts tend to decrease latency to a point which is not commercially practical with current production demands. And introduction of a solid catalyst, such as imidizole, has limited applicability because its presence often changes the rheological properties of the composition, and decreases flow. Thus, due at least in part to their extended cure schedules and limited useful working life, manufacturing capacity of certain microelectronic production lines has been hampered.
While seemingly simple, the solution to the problem of enhancing the cure speed of recently-used underfill sealants has ordinarily adversely impacted their useful working life. Thus, in the event that presently-used underfill sealants could be rendered more reactive, their useful working life may be further decreased, thereby removing the incentive to prepare a more reactive thermosetting resin composition for underfill sealing.
Accordingly, it would be desirable for an underfilling sealant composition to provide good adhesive properties while flowing and curing in a sufficiently quick time to be commercially appealing and possessing an extended useful working life.
SUMMARY OF THE INVENTION
The present invention provides a thermosetting resin composition useful as an underfilling sealant composition which (1) rapidly fills the underfill space in a semiconductor device, such as a flip chip assembly which includes a semiconductor chip mounted on a carrier substrate, (2) enables the semiconductor to be securely connected to a circuit board by short-time heat curing and with good productivity, and (3) demonstrates excellent heat shock properties (or thermal cycle properties) . The thermosetting resin compositions of this invention which are used as underfill sealants between such a semiconductor device and a circuit board to which the semiconductor device is electrically connected, includes an epoxy resin component and a latent hardener component. The latent hardener component includes a cyanate ester component and an imidizole component.
By using the thermosetting resin compositions of this invention, semiconductor devices, such as flip chip assemblies, may be (1) assembled quickly and without production line down time because of improved cure speed and extended useful working life, and (2) securely connected to a circuit board by short-time heat curing of the composition, with the resulting mounted structure (at least in part due to the cured composition) demonstrating excellent heat shock properties (or thermal cycle properties) .
The compositions of this invention may also be used for microelectronic applications beyond sealing underfill, such as with glob top, die attachment and other applications for thermosetting compositions in which rapid cure time and an extended useful working life are desirable.
The benefits and advantages of the present invention will become more readily apparent after a reading of the "Detailed Description of the Invention" together with the figure.
BRIEF DESCRIPTION OF THE FIGURE
Figure 1 depicts a cross-sectional view showing an example of a mounted structure with which the thermosetting resin composition of the present invention is used as an underfill sealant. DETAILED DESCRIPTION OF THE INVENTION
As noted above, the thermosetting resin compositions which are useful as underfill sealants between a semiconductor device and a circuit board to which the semiconductor device is electrically connected, include an epoxy resin component and a latent hardener component . The latent hardener component includes a cyanate ester component and an imidizole component .
Typically, the composition includes about 100 parts by weight of the epoxy resin component, and 0 to about 30 parts by weight of the latent hardener component, of which 0 to about 15 parts is comprised of the cyanate ester component and 0 to about 15 parts is comprised of the imidizole component. Desirably, the latent hardener component should include about 4 parts each of the cyanate ester component and the imidizole component.
The epoxy resin component of the present invention may include any common epoxy resin. This epoxy resin may be comprised of at least one multifunctional epoxy resin, optionally, together with at least one monofunctional epoxy resin. Ordinarily, the multifunctional epoxy resin should be included in amount within the range of about 20 parts to about 100 parts of the epoxy resin component. In the case of bisphenol F-type epoxy resin, desirably the amount thereof should be in the range of from about 40 to 80 parts.
A monofunctional epoxy resin, if present, should ordinarily be used as a reactive diluent, or crosslink density modifier. In the event such a monofunctional epoxy resin is included as a portion of the epoxy resin component, such resin should be employed in an amount of up to about 20% by weight based on the total epoxy resin component.
The monofunctional epoxy resin should have an epoxy group with an alkyl group of about 6 to about 28 carbon atoms, examples of which include C6-C28 alkyl glycidyl ethers, C6-C28 fatty acid glycidyl esters and C6-C28 alkylphenol glycidyl ethers.
Such epoxy resin (s) include generally, but are not limited to, polyglycidyl ethers of polyvalent phenols, for example pyrocatechol ; resorcinol; hydroquinone ;
4,4' -dihydroxydiphenyl methane
4,4 ' -dihydroxy-3 , 3 ' -dimethyldiphenyl methane;
4 , 4 ' -dihydroxydiphenyl dimethyl methane; 4 , 4 ' -dihydroxydiphenyl methyl methane;
4,4' -dihydroxydiphenyl cyclohexane ;
4,4 ' -dihydroxy-3 , 3 ' -dimethyldiphenyl propane;
4,4' dihydroxydiphenyl sulfone ; tris (4 -hydroxyphyenyl) methane; polyglycidyl ethers of the chlorination and bromination products of the above-mentioned diphenols; polyglycidyl ethers of novolacs (i.e. , reaction products of monohydric or polyhydric phenols with aldehydes, formaldehyde in particular, in the presence of acid catalyst; polyglycidyl ethers of diphenols obtained by esterifying 2 moles of the ethers of diphenols obtained by esterifying 2 moles of the sodium salt of an aromatic hydrocarboxylic acid with 1 mole of a dihaloalkane or dihalogen dialkyl ether (see U.K. Pat. No. 1,017,612, the disclosure of which is hereby expressly incorporated herein by reference) ; and polyglycidyl ethers of polyphenols obtained by condensing phenols and long-chain halogen paraffins containing at least two halogen atoms (see U.K.
Pat. No. 1,024,288, the disclosure of which is hereby expressly incorporated herein by reference) . Other suitable epoxy compounds include polyepoxy compounds based on aromatic amines and epichlorohydrin, such as N, N' -diglycidyl-aniline;
N,N' -dimethyl-N,N' -diglycidyl-4 , ' diaminodiphenyl methane;
N,N,N' ,N' -tetraglycidyl-4 , 4 ' diaminodiphenyl methane; N-diglycidyl-4-aminophenyl glycidyl ether; and
N,N,N' ,N' -tetraglycidyl-1, 3-propylene bis-4-aminobenzoate . Examples of the multifunctional epoxy resin include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, and cresol novolac-type epoxy resin.
Among the epoxy resins suitable for use herein are polyglycidyl derivatives of phenolic compounds, such as those available commercially under the tradenames EPON 828, EPON 1001, EPON 1009, 'and EPON 1031, from Shell Chemical Co.; DER 331, DER 332, DER 334, and DER 542 from Dow Chemical Co.; and BREN-S from Nippon Kayaku, Japan. Other suitable epoxy resins include polyepoxides prepared from polyols and the like and polyglycidyl derivatives of phenol -formaldehyde novolacs, the latter of which are available commercially under the tradenames DEN 431, DEN 438, and DEN 439 from Dow Chemical Company. Cresol analogs are also available commercially ECN 1235, ECN 1273, and ECN 1299 from Ciba-Geigy Corporation. SU-8 is a bisphenol A-type epoxy novolac available from Interez, Inc. Polyglycidyl adducts of amines, aminoalcohols and polycarboxylic acids are also useful in this invention, commercially available resins of which include GLYAMINE 135, GLYAMINE 125, and GLYAMINE 115 from F.I.C. Corporation; ARALDITE MY-720, ARALDITE 0500, and ARALDITE 0510 from Ciba-Geigy Corporation and PGA-X and PGA-C from the Sherwin-Williams Co.
And of course combinations of the different epoxy resins are also desirable for use herein.
In choosing epoxy resins for the epoxy resin component of the compositions of the present invention, consideration should also be given to viscosity and other properties thereof . The cyanate esters useful as a component in the latent hardening component may be chosen from aryl compounds having at least one cyanate ester group on each molecule and may be generally represented by the formula Ar(OCN)m, where m is an integer from 2 to 5 and Ar is an aromatic radical. The aromatic radical Ar should contain at least 6 carbon atoms, and may be derived, for example, from aromatic hydrocarbons, such as benzene, biphenyl, naphthalene, anthracene, pyrene or the like. The aromatic radical Ar may also be derived from a polynuclear aromatic hydrocarbon in which at least two aromatic rings are attached to each other through a bridging group. Also included are aromatic radicals derived from novolac-type phenolic resins -- i.e., cyanate esters of these phenolic resins. The aromatic radical Ar may also contain further ring-attached, non-reactive substituents .
Examples of such cyanate esters include, for instance, 1, 3-dicyanatobenzene ; 1, 4-dicyanatobenzene; 1, 3 , 5-tricyanatobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2 , 7-dicyanatonaphthalene; 1,3, 6-tricyanatonaphthalene; 4 , 4 ' -dicyanato-biphenyl ; bis (4 -cyanatophenyl) methane and 3,3' ,5,5' -tetramethyl bis (4 -cyanatophenyl) methane; 2 , 2-bis (3 , 5 -dichloro-4 -cyanatophenyl) propane; 2 , 2-bis (3 , 5-dibromo-4-dicyanatophenyl) propane; bis (4 -cyanatophenyl) ether; bis (4 -cyanatophenyl) sulfide; 2 , 2-bis (4 -cyanatophenyl) propane ; tris (4-cyanatophenyl) -phosphite ; tris (4 -cyanatophenyl) phosphate; bis (3-chloro-4-cyanatophenyl) methane ; cyanated novolac; 1 , 3 -bis [4 -cyanatophenyl- 1- (methylethylidene) ] benzene and cyanated bisphenol-terminated polycarbonate or other thermoplastic oligomer.
Other cyanate esters include cyanates disclosed in U.S. Patent Nos . 4,477,629 and 4,528,366, the disclosure of each of which is hereby expressly incorporated herein by reference; the cyanate esters disclosed in U.K. Pat. No. 1,305,702, and the cyanate esters disclosed in International Patent Publication WO 85/02184, the disclosure of each of which is hereby expressly incorporated herein by reference. Of course, combinations of these cyanate esters within the imidizole component of the compositions of the present invention are also desirably employed herein.
A particularly desirable cyanate ester for use herein is available commercially from Ciba Geigy
Corporation, Tarrytown, New York under the tradename AROCY 366 (1, 3-bis [4 -cyanatophenyl- 1- (methylethylidene) ] benzene) .
The imidizole component of the latent hardener component include imidizoles, such as imidizole and derivatives thereof, such as isoimidizole, imidizole, alkyl substituted imidizoles, such as 2-methyl imidizole, 2-ethyl-4 -methylimidizole, 2 , 4 -dime hylimidizole, butylimidizole , 2 -heptadecenyl -4 -methylimidizole , 2 -methylimidizole , 2 -undecenylimidizole ,
1-vinyl-2 -methylimidizole, 2 -n-heptadecylimidizole,
2 -undecylimidizole , 2 -heptadecylimidizole ,
2-phenylimidizole, 2-ethyl 4 -methylimidizole, l-benzyl-2-methylimidizole, l-propyl-2-methylimidizole,
1-cyanoethyl -2 -methylimidizole ,
1-cyanoethyl-2-ethyl-4 -methylimidizole,
1-cyanoethyl -2 -undecylimidizole,
1-cyanoethyl-2 -phenylimidizole, 1-guanaminoethyl-2 -methylimidizole and addition products of an imidizole methylimidizole and addition products of an imidizole and trimellitic acid,
2-n-heptadecyl-4-methylimidizole and the like, generally where each alkyl substituent contains up to about 17 carbon atoms and desirably up to about 6 carbon atoms; aryl substituted imidizoles, such as phenylimidazole, benzylimidizole, 2 -methyl-4, 5-diphenylimidizole,
2 , 3 , 5-triphenylimidizole, 2-styrylimidizole, 1- (dodecyl benzyl) -2-methylimidizole, 2- (2-hydroxyl-4-t-butylphenyl) -4 , 5-diphenylimidizole,
2- (2-methoxyphenyl) -4 , 5-diphenylimidizole,
2- (3-hydroxyphenyl) -4- , 5 -diphenylimidizole,
2- (p-dimethylaminophenyl) -4 , 5-diphenylimidizole,
2- (2 -hydroxypheny1) -4 , 5-diphenylimidizole, di (4 , 5 -diphenyl -2 -imidizole) -benzene- 1, 4 ,
2-napnthyl-4 , 5-diphenylimidizole, l-benzyl-2-methylimidizole, 2-p-methoxystyrylimidizole, and the like generally where each aryl substituent contains up to about 10 carbon atoms and desirably up to about 8 carbon atoms.
Of course, combinations of these imidizoles are also desirable as the imidizole component of the latent hardener component of the compositions of the present invention. The thermosetting resin compositions of the present invention may be of the one-pack type, in which all the ingredients are mixed together, or of the two-pack type in which the epoxy resin component and latent hardener component are stored separately and mixed together prior to use .
During application, the thermosetting resin compositions according to the present invention penetrate and flow readily into the space between the circuit board and the semiconductor device, or at least show a reduction in viscosity under heated or use conditions thus penetrating and flowing easily.
Generally, it is desirable to prepare the thermosetting resin compositions of this invention by selecting the types and proportions of various so that the gel times will be tailored to a specified period of time (such as 1 minute or 2 minutes) at a temperature of about 150°C. In such case, the inventive compositions should show no or substantially no increase of viscosity after a period of time of about six hours. With such a gel time, the compositions penetrate into the space between the circuit board and the semiconductor device (e.g. , of 100 to 200 μm) relatively rapidly, and allow for a greater number of assemblies to be filled without observing a viscosity increase in the composition thereby rendering it less effective for application.
Optionally, the thermosetting resin composition of the present invention may further contain other additives such as defoaming agents, leveling agents, dyes, pigments and fillers. Moreover, the compositions may also contain photopolymerization initiators, provided such materials do not adversely affect the desired properties of the composition. In an additional aspect of this invention, there is provided filled thermosetting compositions. These compositions, in addition to the epoxy resin component and latent hardener component, include a filler component. The filler component acts to lower moisture pick up, and tends to increase viscosity. Appropriate filler components include silica, alumina, silica-coated aluminum nitride, silver flake and the like.
Generally, about 0.1 to about 300 parts of the filler component may be used, with about 150 to 180 parts being desirable.
Reference to Figure 1 shows a mounted structure (i.e. , a flip chip package) in which a thermosetting resin composition of the present invention has been applied and cured.
The flip chip package 4 is formed by connecting a semiconductor chip (a bare chip) 2 to a carrier substrate 1 (e.g. , a circuit board) and sealing the space therebetween suitably with a thermosetting resin composition 3. This semiconductor device is mounted at a predetermined position on the carrier substrate 1, and electrodes 5 and 6 are electrically connected by a suitable electrical connection means 7 and 8, such as solder. In order to improve reliability, the space between the semiconductor chip 2 and the carrier substrate 1 is sealed with a thermosetting resin composition 3, and then cured. The cured product of the thermosetting resin composition should completely fill that space . Carrier substrates may be constructed from ceramic substrates of A1203, SiN3 and mullite (Al203-Si02) ; substrates or tapes of heat-resistant resins, such as polyimides; glass-reinforced epoxy; ABS and phenolic substrates which are also used commonly as circuit boards; and the like. Any electrical connection of the semiconductor chip to the carrier substrate may be used, such as connection by a high-melting solder or electrically (or anisotropically) conductive adhesive, wire bonding, and the like. In order to facilitate connections, the electrodes may be formed as bumps.
In a typical mounting process, solder ball (e.g. , in cream or form) may be printed at appropriate positions on a carrier substrate and suitably dried to expel solvent . A semiconductor chip may then mounted in conformity with the pattern on the carrier substrate. This carrier substrate is then passed through a reflowing furnace to melt the solder to connect the semiconductor chip. Moreover, the solder may be applied or formed on either the carrier substrate or the semiconductor chip. Alternatively, this connection may also be made by an electrically conductive adhesive or an anisotropically conductive adhesive.
After the semiconductor chip is electrically connected to the carrier substrate, the resulting structure is ordinarily subjected to a continuity test or the like. After passing such test, the semiconductor chip may be fixed thereto with a thermosetting resin composition, as described below. In this way, in the event of a failure, the semiconductor chip may be removed before it is fixed to the carrier substrate with the thermosetting resin composition.
Using a suitable application means, such as a dispenser, a thermosetting resin composition in accordance with this invention is applied to the periphery of the electronically-connected semiconductor chip. The composition penetrates by capillary action into the space between the carrier substrate and the semiconductor chip.
The thermosetting resin composition is then thermally cured by the application of heat. During the early stage of this heating, the thermosetting resin composition shows a significant reduction in viscosity and hence an increase in fluidity, so that it more easily penetrates into the space between the carrier substrate and the semiconductor chip. Moreover, by preheating the carrier substrate, the thermosetting resin composition is allowed to penetrate fully into the entire space between the carrier substrate and the semiconductor chip.
Cured reaction products of the thermosetting resin compositions of the present invention demonstrate excellent adhesive force, heat resistance and electric properties, and acceptable mechanical properties, such as flex-cracking resistance, chemical resistance, moisture resistance and the like, for the applications for which they are used herein. The amount of thermosetting resin composition applied should be suitably adjusted so as to fill almost completely the space between the carrier substrate and the semiconductor chip, which amount of course may vary depending on application. Thermosetting resin compositions of the present invention may ordinarily be cured by heating to a temperature in the range of about 120 to about 180°C for a period of time of about 0.5 to 30 minutes. However, generally after application of the composition, an initial cure time of about 1 minute sets up the composition, and complete cure is observed after about 15 minutes at 150°C. Thus, the composition of the present invention can be used in relatively moderate temperatures and short -time curing conditions, and hence achieve very good productivity.
The present invention will be more readily appreciated with reference to the examples which follow.
EXAMPLES In these examples, compositions in accordance with the present invention were prepared and evaluated for performance in contrast with compositions prepared without the cyanate ester component of the latent hardener component. Results are set forth below.
Example 1
Thermosetting Resin Composition -- 1 Minute Gel Time A. A thermosetting resin composition for underfill applications in accordance with the present invention was prepared by mixing together with stirring for a period of time of about 10 minutes at room temperature in an open vessel an epoxy resin component including 92 parts by weight of bisphenol F-type epoxy resin, and a latent hardener component including 4 parts by weight of 2 -ethyl-4 -methylimidizole, and 4 parts by weight of
1, 3-bis [4-cyanatophenyl-l- (methylethylidene) ] benzene as a cyanate ester resin (commercially available under the tradename AROCY 366 from Ciba-Geigy) .
While the composition was used upon formation, it may be stored for a period of time of up to about 3 to about 6 months at a temperature of about -20 °C without experiencing viscosity increase.
After formation, the composition was transferred to a 10 ml syringe made of non-reactive plastic, and the composition was dispensed through the 12G needle of the syringe into the junction between the carrier substrate and semiconductor chip in a previously-formed assembly. As such, the composition acts as an encapulant for the electrical solder connection.
After dispensing was complete, the assembly was transferred to an oven while the temperature was maintained at about 150°C. The composition cured initially after about 1 minute, and thereafter cured completely after about 15 minutes at that temperature.
Separately, the composition was placed between a pair of lap shears and cured in the same way as the assembly above. The bound lap shears were removed from the oven and allowed to reach room temperature, at which point they were evaluated for bond strength. The cured composition was found to possess lap shear strength of about 1660 psi -- which is acceptable for the microelectronic applications which the compositions are designed. With respect to shelf-life stability, as noted above the gel time of the composition was tailored to 1 minute at a temperature of 150°C. This composition was observed to experience no viscosity increase at room temperature after a period of time of 6 hours; after a period of time of about 15 hours the viscosity increase was observed to be about 52%; and after a period of time of about 24 hours the viscosity increase was observed to be about 88%.
B. A comparable composition was prepared in which no cyanate ester was added. That composition included 96.5 parts bisphenol F-type epoxy resin and 3.5 parts of 2-ethyl-4-methylimidizole . The composition was also tailored to a gel time of about 1 minute at a temperature of 150°C. The lap shear strength was observed to be about 1670 psi .
This composition was applied as above, and demonstrated a viscosity increase at room temperature after a period of time of about 6 hours of about 13%; after a period time of about 15 hours of about 153% and after a period of time of 24 hours of about 267%.
Accordingly, it is seen that the presence of the cyanate ester component in the inventive compositions has a dramatic affect in maintaining a useful working life for the compositions with respect to slowing viscosity increase over time at room temperature.
Example 2 Thermosetting Resin Composition -- 2 Minute Gel Time A. A thermosetting resin composition for underfill applications in accordance with the present invention was prepared by mixing together with stirring for a period of time of about 10 minutes at room temperature in an open vessel an epoxy resin component including 88 parts by weight of bisphenol F-type epoxy resin, and a latent hardener component including 8 parts by weight of 2-ethyl-4-methylimidizole, and 4 parts by weight of 1, 3-bis [4 -cyanatophenyl -1- (methylethylidene) ] benzene as a cyanate ester resin (AROCY 366) .
While this composition was used upon formation, it too may be stored for a period of time of up to about 3 to about 6 months at a temperature of about -20°C without experiencing viscosity increase. After formation, the composition was transferred to a 10ml syringe made of non-reactive plastic, and the composition was dispensed through the 12G needle of the syringe into the junction between the carrier substrate and semiconductor chip in a previously- formed assembly to act as an encapulant for the electrical solder connection.
After dispensing was complete, the assembly was transferred to an oven while the temperature was again maintained at about 150°C. The composition cured initially after about 2 minutes, and thereafter cured completely after about 15 minutes at that temperature.
This composition was also placed between a pair of lap shears and cured in the same way as the assembly above, and as in Example 1. The lap shears were removed from the oven and allowed to reach room temperature, at which point they were evaluated for bond strength. The cured composition was found to possess lap shear strength of about 1620 psi -- which is acceptable for the microelectronic applications for which the compositions are designed.
With respect to shelf-life stability, as noted above the gel time of the composition was tailored to 2 minute at a temperature of 150°C. This composition was observed to experience a viscosity increase at room temperature after a period of time of 6 hours of about 3%; after a period of time of about 15 hours the viscosity increase was observed to be about 10%; and after a period of time of about 24 hours the viscosity increase was observed to be about 20%. B. A comparable composition was prepared in which no cyanate ester was added. That composition included 97.5 parts bisphenol F-type epoxy resin and 2.5 parts of 2-ethyl-4-methylimidizole . The composition was also tailored to a gel time of about 2 minutes at a temperature of 150°C. The lap shear strength was observed to be about 1600 psi.
This composition was applied as above, and demonstrated a viscosity increase at room temperature after a period of time of about 6 hours of about 16%; after a period time of about 15 hours of about 82% and after a period of time of 24 hours of about 162%.
Accordingly, it is seen that the presence of the cyanate ester in the inventive compositions has a dramatic affect in maintaining a useful working life for the compositions with respect to slowing viscosity increase over time at room temperature.

Claims

What Is Claimed Is;
1. A thermosetting resin composition capable of sealing underfilling between a semiconductor device and a circuit board to which said semiconductor device is electrically connected, said composition comprising:
(a) an epoxy resin component; and
(b) a latent hardener component comprising
(i) a cyanate ester component; and (ii) an imidizole component.
2. The composition of Claim 1, wherein said epoxy resin comprises at least one multifunctional epoxy resin .
3. The composition according to Claim 1, wherein the epoxy resin component includes members selected from the group consisting of C6-C28 alkyl glycidyl ethers; C6-C28 fatty acid glycidyl esters; C6-C28 alkylphenol glycidyl ethers; polyglycidyl ethers of pyrocatechol , resorcinol, hydroquinone , 4,4' -dihydroxydiphenyl methane ,
4,4' -dihydroxy-3 , 3 ' -dimethyldiphenyl methane,
4 , 4 ' -dihydroxydiphenyl dimethyl methane,
4 , 4 ' -dihydroxydiphenyl methyl methane,
4,4' -dihydroxydiphenyl cyclohexane ,
4,4' -dihydroxy-3 , 3 ' -dimethyldiphenyl propane ,
4,4' dihydroxydiphenyl sulfone , and tris (4 -hydroxyphyenyl) methane; polyglycidyl ethers of the chlorination and bromination products of the above-mentioned diphenols; polyglycidyl ethers of novolacs; polyglycidyl ethers of diphenols obtained by esterifying ethers of diphenols obtained by esterifying salts of an aromatic hydrocarboxylic acid with a dihaloalkane or dihalogen dialkyl ether; polyglycidyl ethers of polyphenols obtained by condensing phenols and long-chain halogen paraffins containing at least two halogen atoms;
N,N' -diglycidyl -aniline;
N,N' -dimethyl -N, 1 -diglycidyl -4 , 4 ' diaminodiphenyl methane ; N,N,N' ,N' -tetraglycidyl-4 , 4 ' diaminodiphenyl methane; N-diglycidyl-4-aminophenyl glycidyl ether;
N, N,N' ,N' -tetraglycidyl-1, 3 -propylene bis-4-aminobenzoate; bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, and cresol novolac epoxy resin.
4. The composition according to Claim 1, wherein the epoxy resin component includes bisphenol F epoxy resin and epoxy cresol novalac resin.
5. The composition according to Claim 1, wherein the epoxy resin component includes about 80 parts bisphenol F epoxy resin and about 20 parts epoxy cresol novalac resin.
6. The composition according to Claim 1, wherein the latent hardener component is employed in an amount within the range of from 0 to about 30 parts.
7. The composition according to Claim 1, wherein the cyanate ester component is chosen from aryl compounds having at least one cyanate ester group on each molecule.
8. The composition according to Claim 1, wherein the cyanate ester component is represented by Ar(OCN)m, wherein Ar is an aromatic radical and m is an integer from 2 to 5.
9. The composition according to Claim 1, wherein the cyanate ester component is selected from the group consisting of 1, 3-dicyanatobenzene ; 1 , 4-dicyanatobenzene;
1, 3 , 5-tricyanatobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2 , 7-dicyanatonaphthalene; 1,3, 6-tricyanatonaphthalene; 4 , 4 ' -dicyanato-biphenyl ; bis (4 -cyanatophenyl) methane and 3,3' ,5,5' -tetramethyl bis (4 -cyanatophenyl) methane; 2 , 2-bis (3 , 5-dichloro-4-cyanatophenyl) propane ; 2 , 2-bis (3 , 5-dibromo-4 -dicyanatophenyl) propane; bis (4 -cyanatophenyl) ether; bis (4 -cyanatophenyl) sulfide; 2 , 2-bis (4 -cyanatophenyl) propane; tris (4 -cyanatophenyl) -phosphite; tris (4 -cyanatophenyl) phosphate; bis (3 -chloro-4 -cyanatophenyl) methane ; cyanated novolac;
1, 3 -bis [4 -cyanatophenyl -1- (methylethylidene) ] benzene and cyanated bisphenol-terminated polycarbonate or other thermoplastic oligomer.
10. The composition according to Claim 1, wherein the cyanate ester component is
1, 3 -bis [4-cyanatophenyl-l- (methylethylidene) ] benzene .
11. The composition according to Claim 1, wherein the cyanate ester component is employed in an amount within the range of 0 to about 15 parts.
12. The composition according to Claim 1, wherein the imidizole component is a member selected from the group consisting of imidizole, isoimidizole, 2 -methyl imidizole,
2 -ethyl-4 -methylimidizole, 2 , 4 -dimethylimidizole, butylimidizole , 2 -heptadecenyl-4 -methylimidizole ,
2-methylimidizole , 2 -undecenylimidizole ,
1-vinyl-2 -methylimidizole, 2 -n-heptadecylimidizole,
2 -undecylimidizole, 2 -heptadecylimidizole,
2 -phenylimidizole, 1-benzyl-2 -methylimidizole,
1-propyl-2 -methylimidizole, 1-cyanoethyl -2 -methylimidizole,
1-cyanoethyl-2 -ethyl -4 -methylimidizole,
1-cyanoethyl-2 -undecylimidizole ,
1-cyanoethyl-2 -phenylimidizole, l-guanaminoethyl-2-methylimidizole and addition products of an imidizole methylimidizole and addition products of an imidizole and trimellitic acid,
2 -n-heptadecyl-4 -methylimidizole, phenylimidazol , benzylimidizole, 2 -methyl-4 , 5-diphenylimidizole,
2 , 3 , 5-triphenylimidizole, 2-styrylimidizole, 1- (dodecyl benzyl) -2 -methylimidizole,
2- (2-hydroxyl-4-t-butylphenyl) - , 5 -diphenylimidizole,
2- (2-methoxyphenyl) -4 , 5-diphenylimidizole,
2- (3-hydroxyphenyl) -4- , 5-diphenylimidizole, 2- (p-dimethyl-aminophenyl) -4 , 5-diphenylimidizole, 2- (2-hydroxyphenyl) -4 , 5-diphenylimidizole, di (4 , 5 -diphenyl -2 -imidizole) -benzene- 1, 4 , 2-napnthyl-4 , 5-diphenylimidizole, l-benzyl-2-methylimidizole, 2-p-methoxystyrylimidizole, and the combinations thereof.
13. The composition according to Claim 1, wherein the imidizole component is 2-ethyl-4-methylimidizole .
13. The composition according to Claim 1, wherein the imidizole component is employed in an amount within the range of 0 to about 15 parts.
14. A thermosetting resin composition capable of sealing underfilling between a semiconductor device and a circuit board to which said semiconductor device is electrically connected, said composition comprising:
(a) about 92 parts by weight of an epoxy resin component comprising bisphenol F epoxy resin, and
(b) about 8 parts by weight of latent hardening component, of which 4 parts is comprised of (i) a cyanate ester component comprising
1, 3-bis [4-cyanatophenyl-l- (methylethylidene) ] benzene and 4 parts is comprised of (ii) an imidizole component comprising 2-ethyl-4-methylimidizole .
15. A thermosetting resin composition capable of sealing underfilling between a semiconductor device and a circuit board to which said semiconductor device is electrically connected, said composition comprising:
(a) about 88 parts by weight of an epoxy resin component comprising bisphenol F epoxy resin, and
(b) about 12 parts by weight of latent hardening component, of which 4 parts is comprised of a cyanate ester component comprising
1, 3-bis [4 -cyanatophenyl -1- (methylethylidene) ] benzene and 8 parts is comprised of an imidizole component comprising 2 -ethyl-4 -methylimidizole .
16. The composition of Claim 1, having a viscosity of less than about 50,000 mPa Γûá s at a temperature of 25┬░C.
17. Reaction products according to any one of Claims 1-16.
18. A mounting structure for semiconductor devices, comprising: a semiconductor device comprising a semiconductor chip mounted on a carrier substrate, and a circuit board to which said semiconductor device is electrically connected, wherein the space between the carrier substrate of said semiconductor device and said circuit board is sealed with a reaction product of a thermosetting resin composition comprising an epoxy resin component, and a latent hardener component comprising a cyanate ester component, and an imidizole component.
19. The mounting structure according to Claim 18, wherein the thermosetting resin composition is in accordance with Claims 14 or 15.
20. A process for fabricating semiconductor devices, said process comprising the steps of: electrically connecting a semiconductor device comprising a semiconductor chip mounted on a carrier substrate, to a circuit board; infiltrating a thermosetting resin composition into the space between the carrier substrate of said semiconductor device and said circuit board, wherein the composition comprises an epoxy resin component; and a latent hardener component comprising a cyanate ester component, and an imidizole component; and curing the composition by the application of heat.
PCT/US1998/015578 1997-07-24 1998-07-22 Thermosetting resin compositions useful as underfill sealants WO1999005196A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
JP51020999A JP2001506313A (en) 1997-07-24 1998-07-22 Thermosetting resin composition useful as underfill sealant
DE69833865T DE69833865T2 (en) 1997-07-24 1998-07-22 HEAT-RESISTANT RESIN COMPOSITIONS USES AS UNDER-FILLING SEALING MEASURES
BR9806065-1A BR9806065A (en) 1997-07-24 1998-07-22 Thermosensitive resin compositions · useful as seals between layers
KR1019997002498A KR100571334B1 (en) 1997-07-24 1998-07-22 Thermosetting resin composition useful as an underfill sealant
AU85959/98A AU728193B2 (en) 1997-07-24 1998-07-22 Thermosetting resin compositions useful as underfill sealants
US09/269,067 US6342577B1 (en) 1997-07-24 1998-07-22 Thermosetting resin compositions useful as underfill sealants
EP98937187A EP0929592B1 (en) 1997-07-24 1998-07-22 Thermosetting resin compositions useful as underfill sealants
CA002266314A CA2266314A1 (en) 1997-07-24 1998-07-22 Thermosetting resin compositions useful as underfill sealants

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US5359297P 1997-07-24 1997-07-24
US60/053,592 1997-07-24

Publications (1)

Publication Number Publication Date
WO1999005196A1 true WO1999005196A1 (en) 1999-02-04

Family

ID=21985312

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/015578 WO1999005196A1 (en) 1997-07-24 1998-07-22 Thermosetting resin compositions useful as underfill sealants

Country Status (13)

Country Link
US (1) US6342577B1 (en)
EP (1) EP0929592B1 (en)
JP (1) JP2001506313A (en)
KR (1) KR100571334B1 (en)
CN (1) CN1197893C (en)
AT (1) ATE320460T1 (en)
AU (1) AU728193B2 (en)
BR (1) BR9806065A (en)
CA (1) CA2266314A1 (en)
DE (1) DE69833865T2 (en)
ID (1) ID21928A (en)
RU (1) RU2195474C2 (en)
WO (1) WO1999005196A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1160857A2 (en) * 2000-06-01 2001-12-05 Sony Chemicals Corp. Epoxy-based adhesive for mounting a semiconductor device on a substrate
SG88747A1 (en) * 1999-03-01 2002-05-21 Motorola Inc A method and machine for underfilling an assembly to form a semiconductor package
US6548575B2 (en) 2000-12-13 2003-04-15 National Starch And Chemical Investment Holding Corporation High temperature underfilling material with low exotherm during use
WO2003044089A1 (en) * 2001-11-19 2003-05-30 Henkel Corporation Thermosetting resin compositions useful as underfill sealants
US6833629B2 (en) 2001-12-14 2004-12-21 National Starch And Chemical Investment Holding Corporation Dual cure B-stageable underfill for wafer level
US7012120B2 (en) 2000-03-31 2006-03-14 Henkel Corporation Reworkable compositions of oxirane(s) or thirane(s)-containing resin and curing agent
US8053587B2 (en) 2000-03-31 2011-11-08 Henkel Corporation Reworkable thermosetting resin composition
WO2021193233A1 (en) 2020-03-25 2021-09-30 株式会社Adeka Curable resin composition and method for suppressing curing shrinkage of curable resin composition

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6617399B2 (en) * 1999-12-17 2003-09-09 Henkel Loctite Corporation Thermosetting resin compositions comprising epoxy resins, adhesion promoters, curatives based on the combination of nitrogen compounds and transition metal complexes, and polysulfide tougheners
US6670430B1 (en) * 1999-12-17 2003-12-30 Henkel Loctite Corporation Thermosetting resin compositions comprising epoxy resins, adhesion promoters, and curatives based on the combination of nitrogen compounds and transition metal complexes
JP3566680B2 (en) * 2001-09-11 2004-09-15 富士通株式会社 Method for manufacturing semiconductor device
JP3866591B2 (en) * 2001-10-29 2007-01-10 富士通株式会社 Method for forming interelectrode connection structure and interelectrode connection structure
US6951907B1 (en) 2001-11-19 2005-10-04 Henkel Corporation Composition of epoxy resin, secondary amine-functional adhesion promotor and curative of nitrogen-compound and transition metal complex
US20040094751A1 (en) * 2002-03-25 2004-05-20 Toshiaki Ogiwara Composition for filling through-holes in printed wiring boards
JP2006216720A (en) * 2005-02-02 2006-08-17 Sharp Corp Semiconductor device and its manufacturing method
KR101148051B1 (en) * 2005-12-26 2012-05-25 에스케이케미칼주식회사 Epoxy resin composition
EP2158248B1 (en) * 2007-06-11 2012-08-15 Basf Se Catalyst for curing epoxides
JP5475223B2 (en) * 2007-10-09 2014-04-16 株式会社Ａｄｅｋａ One-component cyanate-epoxy composite resin composition, cured product thereof and method for producing the same, and sealing material and adhesive using the same
US20110237633A1 (en) * 2008-12-11 2011-09-29 Bijoy Panicker Small molecule modulators of hepatocyte growth factor (scatter factor) activity
DE102009012195A1 (en) * 2009-03-06 2010-09-09 Siemens Aktiengesellschaft Cast resin system for insulators with increased heat resistance
DE102009003132A1 (en) * 2009-05-15 2010-11-18 Robert Bosch Gmbh Plastic molding compound and process for its preparation
US8698320B2 (en) * 2009-12-07 2014-04-15 Henkel IP & Holding GmbH Curable resin compositions useful as underfill sealants for use with low-k dielectric-containing semiconductor devices
CN102939316B (en) * 2010-04-21 2016-04-27 三菱瓦斯化学株式会社 Thermoset composition
RU2447093C1 (en) * 2011-01-19 2012-04-10 Открытое акционерное общество "Институт пластмасс имени Г.С. Петрова" Method of producing ortho-cresol novolac epoxy resin and polymer composition based thereon
CN102559119A (en) * 2011-12-13 2012-07-11 北京海斯迪克新材料有限公司 One-component epoxy encapsulating adhesive with good rheological stability and preparation method thereof
RU2492549C1 (en) * 2012-03-20 2013-09-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный технический университет имени Н.Э. Баумана" (МГТУ им. Н.Э. Баумана) Method of assembling three-dimensional electronic module
TWI568764B (en) * 2012-06-08 2017-02-01 Adeka股份有限公司 Curable resin composition, resin composition, resin sheet made of which and curable composition thereof
JP6202857B2 (en) * 2013-04-02 2017-09-27 株式会社東芝 Coating material for electrical equipment
RU2597916C2 (en) * 2014-11-18 2016-09-20 Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" (Госкорпорация "Росатом") Polymer matrix material for conditioning low and medium spent ion-exchange resins
JP6710434B2 (en) * 2015-03-31 2020-06-17 三菱瓦斯化学株式会社 Cyanate ester compound, curable resin composition containing the compound and cured product thereof
CN105356479B (en) * 2015-11-13 2017-12-08 湖南大学 A kind of c-type series filtering formula cascade SVG and its negative sequence compensation control method
KR102246076B1 (en) * 2015-11-17 2021-05-03 한국전자통신연구원 Method of fabricating a semiconductor package
US9988308B1 (en) * 2016-05-05 2018-06-05 Five Star Products, Inc. Epoxy based material and applications therefore
WO2021049390A1 (en) 2019-09-09 2021-03-18 株式会社Adeka Curable resin composition
JPWO2022190745A1 (en) 2021-03-08 2022-09-15
CN114214019A (en) * 2021-12-02 2022-03-22 深圳斯多福新材料科技有限公司 Preparation method of high-temperature and low-temperature resistant single-component adhesive

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4159976A (en) * 1977-03-10 1979-07-03 Loctite Corporation Curable systems containing epoxy resin and methanol or ethanol solvent to suppress the catalytic reaction between epoxy resin and an imidazole catalytic curing agent
US5330684A (en) * 1991-07-12 1994-07-19 Minnesota Mining And Manufacturing Company Anisotropic conductive adhesive film
US5534356A (en) * 1995-04-26 1996-07-09 Olin Corporation Anodized aluminum substrate having increased breakdown voltage

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH448513A (en) 1963-11-14 1967-12-15 Bayer Ag Process for the production of shaped structures based on epoxy resins
GB1305702A (en) 1969-02-20 1973-02-07
US3862260A (en) 1973-05-07 1975-01-21 Union Carbide Corp Epoxy curing system
JPS55112256A (en) * 1979-02-21 1980-08-29 Mitsubishi Electric Corp Thermosetting resin composition
JPS56125449A (en) 1980-01-29 1981-10-01 Mitsubishi Gas Chem Co Inc Curable resin composition
US4528366A (en) 1982-09-28 1985-07-09 The Dow Chemical Company Production of polytriazines from aromatic polycyanates with cobalt salt of a carboxylic acid as catalyst
US4477629A (en) 1983-07-27 1984-10-16 The Dow Chemical Company Cyanate-containing polymers
US4751323A (en) 1983-11-16 1988-06-14 The Dow Chemical Company Novel polyaromatic cyanates
US4645803A (en) 1984-02-29 1987-02-24 American Cyanamid Company Curable epoxy resin compositions
JPS62275123A (en) 1986-05-23 1987-11-30 Toray Ind Inc Resin composition for prepreg
US4732962A (en) * 1987-02-18 1988-03-22 General Motors Corporation High temperature epoxy tooling composition of bisphenol-A epoxy, trifunctional epoxy, anhydride curing agent and an imidazole catalyst
US4742148A (en) 1987-04-17 1988-05-03 Hexcel Corporation Modified imidazole latent epoxy resin catalysts and systems comprising them
US4859528A (en) 1987-04-17 1989-08-22 Hexcel Corporation Composite tooling
US4918157A (en) 1987-07-08 1990-04-17 Amoco Corporation Thermosetting composition comprising cyanate ester, urea compound and epoxy resin
WO1996020242A1 (en) * 1994-12-26 1996-07-04 Ciba Specialty Chemicals Inc. Curable resin compositions
JP3777732B2 (en) * 1996-10-15 2006-05-24 東レ株式会社 Adhesive composition for semiconductor device and adhesive sheet for semiconductor device using the same
US5969036A (en) * 1997-06-20 1999-10-19 The Dexter Corporation Epoxy-containing die-attach compositions
JP3591758B2 (en) * 1997-10-09 2004-11-24 住友ベークライト株式会社 Liquid injection sealing underfill material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4159976A (en) * 1977-03-10 1979-07-03 Loctite Corporation Curable systems containing epoxy resin and methanol or ethanol solvent to suppress the catalytic reaction between epoxy resin and an imidazole catalytic curing agent
US5330684A (en) * 1991-07-12 1994-07-19 Minnesota Mining And Manufacturing Company Anisotropic conductive adhesive film
US5534356A (en) * 1995-04-26 1996-07-09 Olin Corporation Anodized aluminum substrate having increased breakdown voltage

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG88747A1 (en) * 1999-03-01 2002-05-21 Motorola Inc A method and machine for underfilling an assembly to form a semiconductor package
US7012120B2 (en) 2000-03-31 2006-03-14 Henkel Corporation Reworkable compositions of oxirane(s) or thirane(s)-containing resin and curing agent
US8053587B2 (en) 2000-03-31 2011-11-08 Henkel Corporation Reworkable thermosetting resin composition
EP1160857A2 (en) * 2000-06-01 2001-12-05 Sony Chemicals Corp. Epoxy-based adhesive for mounting a semiconductor device on a substrate
EP1160857A3 (en) * 2000-06-01 2004-01-02 Sony Chemicals Corp. Epoxy-based adhesive for mounting a semiconductor device on a substrate
US6548575B2 (en) 2000-12-13 2003-04-15 National Starch And Chemical Investment Holding Corporation High temperature underfilling material with low exotherm during use
WO2003044089A1 (en) * 2001-11-19 2003-05-30 Henkel Corporation Thermosetting resin compositions useful as underfill sealants
US6893736B2 (en) 2001-11-19 2005-05-17 Henkel Corporation Thermosetting resin compositions useful as underfill sealants
US6833629B2 (en) 2001-12-14 2004-12-21 National Starch And Chemical Investment Holding Corporation Dual cure B-stageable underfill for wafer level
WO2021193233A1 (en) 2020-03-25 2021-09-30 株式会社Adeka Curable resin composition and method for suppressing curing shrinkage of curable resin composition

Also Published As

Publication number Publication date
ID21928A (en) 1999-08-12
CN1197893C (en) 2005-04-20
EP0929592B1 (en) 2006-03-15
BR9806065A (en) 1999-08-31
JP2001506313A (en) 2001-05-15
AU8595998A (en) 1999-02-16
AU728193B2 (en) 2001-01-04
US6342577B1 (en) 2002-01-29
KR20000068623A (en) 2000-11-25
CN1237186A (en) 1999-12-01
CA2266314A1 (en) 1999-02-04
DE69833865D1 (en) 2006-05-11
EP0929592A4 (en) 2000-09-13
KR100571334B1 (en) 2006-04-14
EP0929592A1 (en) 1999-07-21
DE69833865T2 (en) 2006-10-05
RU2195474C2 (en) 2002-12-27
ATE320460T1 (en) 2006-04-15

Similar Documents

Publication Publication Date Title
AU728193B2 (en) Thermosetting resin compositions useful as underfill sealants
US6632893B2 (en) Composition of epoxy resin, cyanate ester, imidazole and polysulfide tougheners
US7504460B2 (en) Composition of aromatic or cycloaliphatic amine-derived polyepoxide and polyamine
US6893736B2 (en) Thermosetting resin compositions useful as underfill sealants
JP4718070B2 (en) Underfill sealing and repair method
EP1364979A1 (en) Thermosetting resin composition and semiconductor device obtained with the same
KR101553102B1 (en) A method of improving reliability of a semiconductor device comprising a thermosetting resin composition
JP2007056070A (en) Under fill material for flip chip type semiconductor device, the flip chip type semiconductor device using the same and method for producing the device
US6617399B2 (en) Thermosetting resin compositions comprising epoxy resins, adhesion promoters, curatives based on the combination of nitrogen compounds and transition metal complexes, and polysulfide tougheners
JP2007189210A (en) Method of assembling flip-chip-type semiconductor device and semiconductor device produced by method
US6670430B1 (en) Thermosetting resin compositions comprising epoxy resins, adhesion promoters, and curatives based on the combination of nitrogen compounds and transition metal complexes
WO2000056799A1 (en) Reworkable thermosetting resin compositions
US6572980B1 (en) Reworkable thermosetting resin compositions
US20040155364A1 (en) Reworkable thermosetting resin compositions
MXPA99002815A (en) Thermosetting resin compositions useful as underfill sealants
CN108137786A (en) Fluxing underfill composition

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 98801206.5

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CN ID JP KR MX RU US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

ENP Entry into the national phase

Ref document number: 2266314

Country of ref document: CA

Ref document number: 2266314

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 85959/98

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 1998937187

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 1999 510209

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PA/a/1999/002815

Country of ref document: MX

Ref document number: 1019997002498

Country of ref document: KR

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 09269067

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 1998937187

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1019997002498

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 85959/98

Country of ref document: AU

WWG Wipo information: grant in national office

Ref document number: 1019997002498

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 1998937187

Country of ref document: EP