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WO1999067324A1 - Compositions de resine thermodurcissable utilisees comme resines de remplissage - Google Patents

Compositions de resine thermodurcissable utilisees comme resines de remplissage Download PDF

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Publication number
WO1999067324A1
WO1999067324A1 PCT/US1999/013625 US9913625W WO9967324A1 WO 1999067324 A1 WO1999067324 A1 WO 1999067324A1 US 9913625 W US9913625 W US 9913625W WO 9967324 A1 WO9967324 A1 WO 9967324A1
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WIPO (PCT)
Prior art keywords
meth
acrylate
composition according
component
epoxy resin
Prior art date
Application number
PCT/US1999/013625
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English (en)
Inventor
Afranio Torres-Filho
Lawrence N. Crane
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 AU46886/99A priority Critical patent/AU4688699A/en
Publication of WO1999067324A1 publication Critical patent/WO1999067324A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • 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
    • H01L2924/01079—Gold [Au]

Definitions

  • thermosetting resin compositions useful as underfill sealants for mounting on a circuit board a semiconductor chip on a carrier substrate particularly for those mounting steps involving flip chip (“FC”) technology, and more particularly those mounting steps involving stud bump bonding ( "SBB” ) technology.
  • underfill sealant a sealing resin
  • DCA direct chip attachment
  • CSP chip scale package
  • BGA ball grid array
  • curable resin compositions generally are known.
  • Loctite Corporation presently offers for sale adhesive products intended to be useful to bond a chip package to a circuit board (such as those products available under the trademark "CHIPBONDER” , for instance, “CHIPBONDER” 348, 368, 3607 and the like) or as an underfill sealant (such as Loctite product No. 3150) .
  • a contact resistance between the stud bump on the chip and the circuit board contacts is important parameter for many resin compositions presently used as underfill sealants, particularly for SBB processing, in microelectronics applications.
  • a high contact resistance may result in electrical disconnection. Such an event is undesirable because it tends to cause intermittent operation of the microelectronic device, causing a failure of the device.
  • the contact resistance itself tends to increase as the local operating temperature increases, and it may be linked to the coefficient of thermal expansion of an underfill sealant.
  • an appropriate physical property of an underfill sealant in that regard would be shrinkage in volume after curing when a thermal compression or lamination step has occurred during the microelectronic device fabrication process. Such a property is believed to reduce contact resistance. While acrylate-based adhesives are known generally to shrink in volume to some extent when cured, such materials would typically be undesirable for microelectronic underfill applications because of their range of coefficients of thermal expansion when cured, which are ordinarily impractical for such applications.
  • thermosetting resin composition useful as an underfilling sealant composition which (1) is capable of shrinking when cured, (2) rapidly fills the underfill space in a semiconductor device, such as a FC assembly which includes a semiconductor chip mounted on a carrier substrate, (3) enables the semiconductor to be securely connected to a circuit board by short-time heat curing and with good productivity, and (4) demonstrates excellent heat shock properties (or thermal cycle properties) .
  • 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, include broadly (a) an epoxy resin component; (b) a (meth) acrylate resin component; (c) an inorganic filler component and (d) a polymerization catalytic component.
  • semiconductor devices such as FC assemblies, may be (1) assembled, for instance using SBB techniques, rapidly 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.
  • FIG. 1 depicts a flow diagram of the assembly of a mounted structure in cross-sectional view with which the thermosetting resin composition of the present invention is used as an underfill sealant.
  • the composition includes of these components about 5 to about 25 parts of the epoxy resin component by weight of the total composition, about 15 to about 25 parts of the (meth) acrylate component by weight of the total composition, about 50 to about 70 parts of the inorganic filler component by weight of the total composition and about 0.01 to about 5 parts of the polymerization catalytic component by weight of the total composition.
  • the epoxy resin component of the present invention may include any common epoxy resin, such as a multifunctional epoxy resin.
  • the multifunctional epoxy resin should be included in an amount within the range of about 20 parts to about 100 parts by weight of the total of the epoxy resin component.
  • the amount thereof should be in the range of from about 1 to 40 parts, such as about 5 to about 30 parts by weight of the total of the epoxy resin component .
  • multifunctional epoxy resin examples include bisphenol-A-type epoxy resin, bisphenol-F-type epoxy resin (such as RE-404-S from Nippon Kayaku, Japan) , phenol novolac-type epoxy resin, and cresol novolac-type epoxy resin.
  • epoxy compounds include polyepoxy compounds based on aromatic amines and epichlorohydrin, such as
  • 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 .
  • epoxy resins suitable for use herein also include polyglycidyl derivatives of phenolic compounds, such as those available commercially under the tradename "EPON”, such as “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.
  • EPON polyglycidyl derivatives of phenolic compounds
  • EPON such as “EPON” 828, "EPON” 1001, "EPON” 1009, and "EPON” 1031
  • DER 331, DER 332, DER 334, and DER 542 from Dow Chemical Co.
  • BREN-S from Nippon Kayaku.
  • 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 tradename "DEN”, such as "DEN” 431, "DEN” 438, and "DEN” 439 from Dow Chemical. Cresol analogs are also available commercially under the tradename "ARALDITE”, such as “ARALDITE” ECN 1235, “ARALDITE” ECN 1273, and "ARALDITE” 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 and PGA-X and PGA-C from the Sherwin-Williams Co.
  • epoxy resin component should be an epoxy monomer capable of forming a high glass transition temperature polymeric network.
  • epoxy monomers are ERL-4221 from Union Carbide Corporation, Danbury, Connecticut, and "ARALDITE" ECN-1871 from Ciba-Geigy.
  • (meth) acrylate component of the compositions of the present invention may be used a wide variety of (meth) acrylate monomers.
  • (meth) acrylate is intended to refer to both acrylate and methacrylate .
  • Additional (meth) acrylate monomers suitable for use herein include polyethylene glycol di (meth) acrylates, tetrahydrofuran (meth) acrylates and di (meth) acrylates, hydroxypropyl (meth) acrylate ("HPMA”), hexanediol di (meth) acrylate, trimethylol propane tri (meth) acrylate (“TMPTA”), diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, di- (pentamethylene glycol) di (meth) acrylate, tetraethylene diglycol diacrylate, diglycerol tetra (meth) acrylate, tetramethylene di (meth) acrylate, ethylene di (meth) acrylate, neopentyl glycol diacrylate, trimethylo
  • (meth) acrylate monomers may also be used, such as reaction products of diglycidylether of bisphenol A with (meth) acrylic acid forming a (meth) acrylate ester corresponding to the structure shown below:
  • R 2 may be selected from hydrogen, alkyl groups having from 1 to about 4 carbon atoms, hydroxyalkyl groups having from 1 to about 4 carbon atoms or
  • R 3 may be selected from hydrogen, halogen, and alkyl groups of from 1 to about 4 carbon atoms;
  • R 4 may be selected from ⁇ ydrogen, hydroxy and
  • R 3 m is an integer equal to at least 1, e.g., from 1 to about 8 or higher, for instance, from 1 to about 4; v is 0 or 1; and n is an integer equal to at least 1, e.g., l to about 20 or more.
  • Higher- functionalized (meth) acrylates such as penta, hexa, septa and the like, may also be used.
  • higher functionalized (meth) acrylates include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and polyester (meth) acrylates [e.g.
  • EBECRYL tetra and hexa (meth) acrylate
  • EBECRYL 264 [aliphatic urethane triacrylate diluted 15% with hexanediol di (meth) acrylate (“HDODA”), for providing non-yellowing, fast curing coatings with excellent arasion and stain resistance, toughness and flexibility]
  • EBECRYL 265 [aliphatic urethane triacrylate diluted 25% with tripropylene glycol diacrylate (“TRGDA”)]
  • 1290 hexafunctional aliphatic urethane acrylate containing an acrylated polyol diluent
  • EBECRYL 8301 (hexafunctional aliphatic urethane acrylate containing an acrylated polyol diluent, for providing fast cure with excellent hardness, solvent and abrasion resistance)
  • EBECRYL 220 (multi-functional aromatic urethane acrylate containing an acrylated polyol diluent, which provides extremely fast cure with excellent hardness and solvent resistance properties
  • (meth) acrylate component which material is of a dual functionality (e.g. , partially-acrylated epoxy resins) .
  • examples of such materials include those which are available from Sartomer under the trade designation SR-379, UCB under the trade designation "EBECRYL” 3605 and from Loctite Corporation, Rocky Hill, Connecticut under the trade designation EQM-672.
  • the inorganic filler component may often include reinforcing silicas, such as fused silicas, and may be untreated or treated so as to alter the chemical nature of their surface. Virtually any reinforcing fused silica may be used. Particularly desirable ones have a low ion concentration and are relatively small in particle size (e.g. , on the order of about 2 microns) , such as the silica commercially available from Admatechs, Japan under the trade designation S0-E5.
  • the inorganic filler component includes those constructed of or containing aluminum oxide, silicon nitride, aluminum nitride and silica-coated aluminum nitride.
  • the polymerization catalytic component should include materials capable of catalyzing the polymerization of the epoxy resin component and the (meth) ' acrylate component portions, and any optional polymerizable components, of the inventive compositions.
  • the materials included in the polymerization catalytic component are designed to catalyze polymerization of the composition, as a whole.
  • an imidizole In order to catalyze polymerization of an epoxy resin as contemplated in the epoxy resin component, an imidizole would be an appropriate material to include. And polymerization catalysts with respect to the (meth) acrylate monomer as contemplated in the (meth) acrylate component may be achieved through the addition of peroxides, or other free radical generating materials, such as azo compounds [e.g. , azo bis-isobutyronitrile (AIBN) ] .
  • azo compounds e.g. , azo bis-isobutyronitrile (AIBN)
  • the polymerization catalytic component of the present invention Of the about 0.01 to about 5 parts by weight of the polymerization catalytic component of the present invention, about 90 to about 50 percent thereof should be allocated to catalyze the polymerization of the epoxy resin component and about 10 to about 50 thereof should be allocated to catalyze polymerization of the (meth) acrylate componen .
  • the imidizole component of the polymerization catalytic component may be chosen from imidizole, isoimidizole, and substituted imidizoles -- such as alkyl-substituted imidizoles (e.g. , 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 -ethyl 4-methylimidizole, l-benzyl-2-methylimidizole, 1-propyl-2 -methylimidizole , 1-cyanoethyl-2 -methyli
  • each alkyl substituent contains up to about 17 carbon atoms and desirably up to about 6 carbon atoms
  • aryl- substituted imidizoles e.g.
  • Examples of commercial imidizoles are available from Air Products, Allentown, Pennsylvania under the trade designation “CUREZOL” 1B2MZ and from Synthron, Inc., Morganton, North Carolina under the trade designation “ACTIRON” NXJ-60.
  • Peroxides suitable for use in the polymerization catalytic component to catalyze the (meth) acrylate component of the compositions of this invention include t-butyl perbenzoate (commercially available from Elf Atochem, Philadelphia, Pennsylvania) , dicumyl peroxide (commercially available from Aztec Peroxides, Inc., Houston, Texas under the trade designation DCP-R) , hydroperoxides such as isopropyl cumene hydroperoxide (commercially available from Nippon Oils and Fats Co., Japan).
  • compositions of the present invention may include a reactive co-monomer component for either or both of the epoxy resin and the (meth) acrylate monomer, such as a reactive diluent and/or an anhydride.
  • a reactive co-monomer component for either or both of the epoxy resin and the (meth) acrylate monomer such as a reactive diluent and/or an anhydride.
  • Appropriate reactive diluents for use herein may include monofunctional or certain multifunctional epoxy resins.
  • the reactive diluent should have a viscosity which is lower than that of the epoxy resin component . Ordinarily, the reactive diluent should have a viscosity less than about 250 cps .
  • such resin should be employed in an amount of up to about 50 parts based on the total of the 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
  • monofunctional epoxy resin reactive diluents include those from Pacific Epoxy Polymers, Richmond, Michigan, under the trade designations PEP-6770 (gycidyl ester of neodecandoic acid) , PEP-6740 (phenyl glycidyl ether) and PEP-6741 (butyl glycidyl ether) .
  • reactive diluents include those from Pacific Epoxy Polymers, under the trade designations PEP-6752 (trimethylolpropane triglycidyl ether) and PEP-6760 (diglycidyl aniline) .
  • anhydrides for use herein include mono- and poly-anhydrides, such as hexahydrophthalic anhydride (“HHPA”) and methyl hexahydrophthalic anhydride (“MHHPA”) (commercially available from Lindau Chemicals, Inc., Columbia, South Carolina, used individually or as a combination, which combination is available under the trade designation "LINDRIDE” 62C) and 5- (2, 5-dioxotetrahydrol) -3-methyl-3-cyclohexene-l, 2-dicar
  • HHPA hexahydrophthalic anhydride
  • MHHPA methyl hexahydrophthalic anhydride
  • boxylic anhydride (commercially available from ChrisKev
  • composition may also include a flowability agent, such as a silane and/or titanate.
  • a flowability agent such as a silane and/or titanate.
  • silanes for use herein include octyl trimethoxy silane (commercially available from OSI Specialities Co., Danbury, Connecticut under the trade designation A-137) , glycidyl trimethoxysilane (commercially available from OSI under the trade designation A-187) , methacryloxy propyl trimethoxy silane (commercially available from OSI under the trade designation A-174) .
  • titanates for use herein include titanium IV tetrakis
  • thermosetting resin composition of the present invention may further contain other additives, such as defoaming agents, leveling agents, dyes, and pigments.
  • 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, (meth) acrylate component, inorganic filler component, and other optional components are included in one part and the polymerization catalytic component is stored separately in a second part, and mixed together only prior to use.
  • thermosetting resin compositions according to the present invention penetrate and flow readily into the space between the semiconductor chip and the circuit board, 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 the various components so that the gel times will be tailored to a specified period of time (such as 15 seconds, or 1 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 semiconductor chip and the circuit board (e.g. , of 25 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.
  • FIG. 1 shows a mounted structure (i.e. , a FC package prepared with SBB technology) in which a thermosetting resin composition of the present invention has been applied and cured.
  • the FC 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.
  • the semiconductor chip 2 is passed over a substrate bearing a conductive adhesive paste (such as a metal-filled epoxy) to form a layer thereof on the studs 11 of the semiconductor chip 2.
  • the layer is ordinarily formed by a printing mechanism.
  • the conductive adhesive paste may be applied on either the carrier substrate or the semiconductor chip. Alternatively, this connection may also be made by an anisotropically conductive adhesive.
  • the semiconductor chip 2 is positioned over the carrier substrate 1 in such a manner so that the studs 11 (often made of gold) of the semiconductor chip 2 are in alignment with the bumps 12 (often made of gold or gold-plated copper) on the carrier substrate 1, which are now coated with a layer of conductive adhesive paste 10.
  • the conductive adhesive paste may be cured by a variety of ways, though ordinarily a heat cure mechanism is employed.
  • 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 and the like. In order to facilitate connections, particularly in SBB technology, the electrodes may be formed as wire bond bumps.
  • 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.
  • 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 1 o
  • 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.
  • Thermosetting resin compositions in accordance with the present invention were prepared by mixing together with stirring for a period of time of about 10 minutes at room temperature in an open vessel the following components in the order noted: 1. an epoxy resin component including
  • an inorganic filler component including 65 parts of fused silica (commercially available from Admatechs under the trade designation SO-E5) ;
  • a polymerization catalytic component including 0.06 parts of imidizole (commercially available from Air Products under the trade designation "CUREZOL” 1B2MZ) , and
  • compositions include:
  • anhydride component comprised of a mixture in an 85:15 ratio of "HHPA” and “MHHPA” anhydrides (commercially available from Lindau under the trade designation “LINDRIDE” 62C) , and a cycloaliphatic dianhydride (commercially available from ChrisKev under the trade designation B-4400) ;
  • a flowability agent including the combination of the following silanes: 0.27 parts of octyl trimethoxy silane (commercially available from OSI under the trade designation A-137) ; and 0.27 parts of a titanate, titanium IV tetrakis
  • compositions have a variety of properties in both the uncured and cured state which are measurable and useful parameters for the end user in choosing a particular formulation for a desired need.
  • the flow rate and viscosity are of interest; in reaching the cured state, the reaction exotherm, as well as peak temperature and onset temperature are of interest .
  • the flow rate allows the end user to determine the rapidity with which the adhesive may be applied during a fabrication process, such as a circuit assembly operation. It may be measured by passing the composition through a 25 ⁇ m gap between glass slides aligned perpendicular to one another, using metal shims as spacers. The time required for the composition to flow between the slides is then measured at lengths of about 0.25 to 1 inches. Values in seconds for the flow rates of the compositions set forth above are presented as an average of three measurements below in Table 2.
  • the value to which reference is ordinarily made is the time necessary to flow 0.5", in this case about 22 to about 24 seconds.
  • the viscosity is a property related to the flow rate, and is helpful for the end user in making appropriate decisions with respect to a particular formulation for a desired application. Viscosity here is measured using a Brookfield viscometer.
  • the reaction exotherm or enthalpy, assists in determining the effectiveness of a (co) polymerization reaction.
  • the reaction exotherm here is measured by differential scanning calorimetry ("DSC").
  • T PEAK peak temperature
  • T 0NSET onset temperature
  • 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 -40 °C without experiencing viscosity increase.
  • composition was transferred to a 10 ml syringe made of non-reactive plastic .
  • the composition When used, the composition may be dispensed through a 12G needle connected to the syringe into the junction between the carrier substrate and semiconductor chip in a previously- formed assembly. As such, the composition acts as an encapsulant for the electrical connection. After such dispensing, the assembly was transferred to an oven while the temperature was maintained at about 165°C. The composition cured initially after about 1 minute, and thereafter cured completely after about 15 minutes at that temperature. In the cured state, a variety of properties are useful depending on the end use for which the composition is destined.
  • the glass transition temperature (“Tg”) which is measured by DSC and by thermal mechanical analysis (“TMA”), provides information on the hardness and strength of the cured reaction product (or, network) , and its behavior with respect to changes in temperature -- that is, a higher Tg should afford a material that is better able to withstand elevated temperatures.
  • TMA thermal mechanical analysis
  • CTE coefficient of thermal expansion
  • Two CTEs are measured: one is measured below the Tg [CTE ( ⁇ l) ] and the other is measured above the Tg [CTE ( ⁇ 2)] .
  • the CTE of a composition destined for use with a chip and circuit board should be about 30 ppm/°C or about 30 ⁇ m/m°C, below the Tg. See below Table 4.
  • Sample No. 5 was observed to experience a slow viscosity increase at room temperature . After a period of time of 5 hours, the viscosity increase was observed to be about 12%.

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Abstract

La présente invention concerne une composition de résine thermodurcissable utilisée comme composition de résine de remplissage, (1) qui est capable de rétrécir lorsqu'elle durcit, (2) qui remplit rapidement l'espace séparant une microplaquette semiconductrice du substrat support dans un dispositif à semiconducteur tel qu'un ensemble de puce à protubérances, (3) qui permet de connecter solidement le semiconducteur à la carte de circuit imprimé par un thermodurcissement de courte durée et ceci en assurant un bon rendement, et (4) qui possède d'excellentes propriétés de résistance aux chocs thermiques (ou aux variations cycliques de température). Les compositions de résine thermodurcissable de l'invention, qui sont utilisées comme résines de remplissage entre un dispositif à semiconducteur et une carte à circuit imprimé à laquelle le dispositif à semiconducteur est électriquement relié, comprennent, d'une façon générale, (a) un composant de résine époxy; (b) un composant de résine méthacrylate; (c) un composant de charge inorganique; et (d) un composant catalyseur de polymérisation.
PCT/US1999/013625 1998-06-22 1999-06-17 Compositions de resine thermodurcissable utilisees comme resines de remplissage WO1999067324A1 (fr)

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AU46886/99A AU4688699A (en) 1998-06-22 1999-06-17 Thermosetting resin compositions useful as underfill sealants

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US9014098P 1998-06-22 1998-06-22
US60/090,140 1998-06-22

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US6833629B2 (en) 2001-12-14 2004-12-21 National Starch And Chemical Investment Holding Corporation Dual cure B-stageable underfill for wafer level
EP1701361A1 (fr) 2005-03-07 2006-09-13 National Starch and Chemical Investment Holding Corporation Adhesif conducteur à faible contrainte
EP2416633A1 (fr) * 2010-08-04 2012-02-08 AT & S Austria Technologie & Systemtechnik Aktiengesellschaft Procédé de fixation et/ou d'intégration d'un composant électronique et colle pour l'utilisation dans un tel procédé

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6548575B2 (en) 2000-12-13 2003-04-15 National Starch And Chemical Investment Holding Corporation High temperature underfilling material with low exotherm during use
US6833629B2 (en) 2001-12-14 2004-12-21 National Starch And Chemical Investment Holding Corporation Dual cure B-stageable underfill for wafer level
EP1461829B2 (fr) † 2001-12-14 2014-04-02 Henkel AG & Co. KGaA Matiere de remplissage sous-jacent pouvant passer a l'etat b a double traitement thermique pour plaquette
EP1701361A1 (fr) 2005-03-07 2006-09-13 National Starch and Chemical Investment Holding Corporation Adhesif conducteur à faible contrainte
US7326369B2 (en) 2005-03-07 2008-02-05 National Starch And Chemical Investment Holding Corporation Low stress conductive adhesive
EP2416633A1 (fr) * 2010-08-04 2012-02-08 AT & S Austria Technologie & Systemtechnik Aktiengesellschaft Procédé de fixation et/ou d'intégration d'un composant électronique et colle pour l'utilisation dans un tel procédé
WO2012016258A3 (fr) * 2010-08-04 2012-06-07 At & S Austria Technologie & Systemtechnik Aktiengesellschaft Colle pour fixer et/ou encastrer un composant électronique ainsi que procédé et utilisation
AT13437U1 (de) * 2010-08-04 2013-12-15 Austria Tech & System Tech Kleber zur Festlegung und/oder Einbettung eines elektronischen Bauteils sowie Verfahren und Verwendung

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