WO2000034032A1 - Compositions de films de sous-remplissage - Google Patents

Compositions de films de sous-remplissage Download PDF

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Publication number
WO2000034032A1
WO2000034032A1 PCT/US1999/028768 US9928768W WO0034032A1 WO 2000034032 A1 WO2000034032 A1 WO 2000034032A1 US 9928768 W US9928768 W US 9928768W WO 0034032 A1 WO0034032 A1 WO 0034032A1
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Prior art keywords
film
chip
matrix material
filler
epoxy
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Application number
PCT/US1999/028768
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English (en)
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WO2000034032A9 (fr
Inventor
David K. Klapprot
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Dexter Corporation
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Publication date
Application filed by Dexter Corporation filed Critical Dexter Corporation
Priority to AU21651/00A priority Critical patent/AU2165100A/en
Publication of WO2000034032A1 publication Critical patent/WO2000034032A1/fr
Publication of WO2000034032A9 publication Critical patent/WO2000034032A9/fr

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
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    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50Assembly 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
    • H01L21/56Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/563Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
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    • H01L2224/732Location after the connecting process
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    • H01L2224/83192Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body
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Definitions

  • This invention pertains to uncured and unreinforced, thin, uniform, high viscosity films.
  • the films are capable of curing in a quick, steady and uniform manner to form void free, isotropic materials that exhibit exceptionally high thermal cycle resistance. More specifically, this invention relates to films for use in adhering and underfilling soldered chips to a printed board, methods for doing the same, and products generated thereby.
  • Background Art Integrated circuit assemblies are utilized in virtually every electrical product ranging from computers to hair dryers.
  • the basic components of an integrated circuit assembly are a printed board (PB) and a semiconductor chip.
  • PB is a general term that embraces any printed wiring or printed circuit configuration. The term includes both rigid and flexible boards made from any organic or ceramic material.
  • a printed wiring board is a subset of PB which only contains printed point-to-point connections (wiring).
  • a printed circuit board (PCB) is another subset of PB which contains printed components (circuits) as well as point-to-point connections (wiring).
  • any reference to a PB is intended to encompass both PWBs and PCBs.
  • Each semiconductor chip contains input/output points (I/Os), or leads, on its surface. These I/O's are connected to the wiring or circuit pattern on the PB at specific points on the PB called "lands.” For a long time, die mounting was the primary means for connecting the I/Os on the chips to the lands on the PB.
  • the chip is positioned against the non-printed side of the PB, with the I/O's facing up. Wires are then run through holes in the PB to the printed side which contains the lands. One end of each wire is soldered to an I/O on the chip and the other end is soldered to a land. Finally, a plastic covering is molded over the entire assembly to protect both the chips and the wires from environmental damage. Die mounting has proven expensive, cumbersome, unreliable, time consuming and generates a bulky product. Therefore, the industry has turned to other approaches. A popular alternative to die mounting is direct attachment by a technique called "flip- chip.” In the flip-chip approach, solder bumps are placed over the I/Os on the chip.
  • the chip is then inverted and placed directly onto the printed side of the PB so that the solder bumps on the I/O's align with the lands on the PB. Heat is then applied to reflow the solder, thereby forming solder joints. In the final product, a gap remains between the chip and the PB due to the height of the solder joints (hereafter referred to as "chip/PB separation").
  • Chip/PB separation the height of the solder joints
  • solder joints are susceptible to thermal stress and failure.
  • the coefficients of thermal expansion (CTE) for the chip, the PB, and the solder joint are all different. These means that the materials swell and contract at substantially different rates as the temperature rises and falls, thereby subjecting the solder joints to stress. Over time the solder joints fatigue and fail. A failure in circuit continuity can occur within as few as 50 thermal cycles.
  • circuit continuity is defined herein as a state wherein all of the circuit connections between the I/O's on a chip and the lands of a PB are fully formed and unimpeded.
  • thermal cycle is defined herein as a temperature ramp that starts with a 30 minute plateau at -55 °C, then rises to 125 °C at a rate sufficient to make the transition within 5 to 10 seconds, remains at 125°C for 30 minutes, and then descends back to -55 °C at a rate sufficient to make the transition within 5 to 10 seconds.
  • underfilling Generally, a low viscosity polymer or polymeric composition is utilized.
  • low viscosity as used in this application includes any liquid or near liquid that possesses a viscosity that allows for complete underfilling of the flip-chip gap in 60 seconds or less. In practice this viscosity appears to be 1000 poise or less at room temperature, and 100 poise or less at an application temperature that is typically 45°C but may be as high as 80°C. For example, a current liquid system (Dexter's FP4450) is 530 poise at room temperature and 40 poise at 40°C.
  • Common low viscosity compositions are epoxy, urethane, acrylic and silicon (STYCAR) resins, as well as bismaleimide fluids.
  • the low viscosity composition is dispensed onto two sides of the solder bonded chip and "wicked" into the chip/PB separation at a controlled rate.
  • the composition's temperature may be increased a temperature between 70 °C and 100°C to further reduce the viscosity and thereby speed the wicking action.
  • a current "fast flow” system has a spreading rate of 2.5 to 3.0 cm per minute at 80°C.
  • U.S. Patent No. 5,386,624 teaches a method of mounting an electromechanical device onto a substrate that comprises: (1) placing a pre-cut film between an electromechanical device and a substrate; and (2) treating the film with heat, and optionally pressure, so that it flows to fill all of the voids between the electromechanical device and the substrate.
  • the underencapsulant film is vaguely described as "a non-conductive resin or epoxy film.”
  • the underencapsulant may comprise other types of underencapsulant materials, such as at least one of the following materials including urethane and silicone.”
  • the reference fails to recognize the importance of cure kinetics in regulating the void content of the cured underfill. Additionally, the reference fails to effects of filler volume fraction, geometry and particle size on the electrical continuity of the solder joints. Summary of Invention The invention is directed to uncured films that have been developed to meet industry's need for faster processing underfill materials.
  • the guiding concept behind the invention is that the time required to underfill a chip can be greatly reduced by using solid films that can be placed between the chip and the PB, flowed to the edges of the assembly, and cured during the soldering step.
  • the uncured films all comprise a polymeric or polymer forming matrix material, a curing agent, and a filler.
  • the matrix material is present in the amount of 0.5 to 50% by weight of the uncured film and is, preferably, an epoxy resin, such as a blend of phenol novolac epoxy, liquid bisphenol epoxy and solid bisphenol epoxy.
  • the curing agent is present in the amount of 0.01 to 10% by weight of the uncured film, and is soluble in the matrix material at a temperature no greater than 100°C.
  • the filler is present in the amount of 50 to 80% by volume of the uncured film, and is substantially spherical, inert, and has a maximum particle size no greater than 30 ⁇ m.
  • the uncured films are also defined by a number of important physical and kinetic parameters. First, the films must have a smooth and uninterrupted surface. Second, the films must have a uniform thickness of 5 mils or less with a deviation of + 0.5 mils or less and a Cpk higher than 1.0. Third, the films must possess a high viscosity, meaning that the viscosity is at least 50,000 poise at room temperature. Fourth, the films must exhibit little to no tack so that they may be die-cut and machine placed. Fifth, the films must exhibit sufficient flexibility to be handled without breaking.
  • the films must possess an activation energy no greater than 300 KJ/mol. Seventh, and finally, the films must retain more than 50% of their theoretical heat of reaction when tested at a heating rate of 200°C/min.
  • the aforementioned uncured films can be placed between a chip and PB, and then cured, to form a product that adheres the chip to the PB and, simultaneously, fills the separation between the chip and the PB without undermining the electrical continuity of the solder joints.
  • the aforementioned uncured films When the aforementioned uncured films are cured, they exhibit a number of beneficial properties. For example, the cured films are void free, have a CTE between 20 and 25 ppm/°C, and exhibit an isotropic modulus, fracture strength, CTE, and thermal conductivity.
  • FIG. 1 illustrates the underfilling process of the instant invention
  • FIG. 2 illustrates the desired geometry of a flip-chip underfilled assembly made in accordance with the instant invention
  • FIG. 3 is a graph plotting heat of reaction versus the heat up rate for three epoxy resin films utilizing three different curing agents
  • FIG. 4 is a graph plotting the heating rate of two films
  • FIG. 1 illustrates the underfilling process of the instant invention
  • FIG. 2 illustrates the desired geometry of a flip-chip underfilled assembly made in accordance with the instant invention
  • FIG. 3 is a graph plotting heat of reaction versus the heat up rate for three epoxy resin films utilizing three different curing agents
  • FIG. 4 is a graph plotting the heating rate of two films
  • FIG. 1 illustrates the underfilling process of the instant invention
  • FIG. 2 illustrates the desired geometry of a flip-chip underfilled assembly made in accordance with the instant invention
  • FIG. 3 is a graph plotting heat of reaction versus the heat up rate for three epoxy resin films utilizing three different
  • FIG. 5 is a graph illustrating the particle size distribution of two filler mixes. Disclosure of Invention The invention is directed to uncured and unreinforced films that can be employed between a soldered chip and a PB and cured to form an adhesive that binds the soldered chip to the PB and, simultaneously, fills the separation between the soldered chip and the PB. Said films comprise the following components: (a) a polymeric or polymer forming matrix material; (b) a curing agent that is soluble in the matrix material at a temperature no greater than 100°C; and (c) a substantially spherical and inert filler that has a maximum particle size no greater than 30 ⁇ m.
  • the matrix material is present in an amount ranging from 0.5% to 50%, more preferably 2.5% to 15%, and most preferably 5% to 10%, based on the weight of the entire film. It is chosen from thermosetting or thermoplastic polymeric or polymer forming materials. Preferably, a thermosetting material is employed. Suitable materials include epoxy resins, cyanate ester resins, bismaleimide resins, vinyl ester resins, phenoxy resins, polyethersulfones, polyphenyleneoxides, polyesters, polyimides, polyamides (most notably nylons), and polyurethanes.
  • a preferred matrix material is a bis-maleimide (BMI) resin. BMI resins are also known as "polymerization of monomer reactants" (PMR) systems. BMI resins are formed by the reaction of an unsubstituted or substituted maleic anhydride, or a similar anhydride such nadic
  • BMI resins correspond to the following formula:
  • R may be any divalent organic radical
  • R 2 may be any tetravalent organic radical
  • X M are, independently, any monovalent organic radical
  • n is 0 or a positive integer of 1 to 20.
  • R is a substituted or unsubstituted phenyl, naphthalene, or diphenyl radical.
  • Ri is a diphenyl radical
  • the two phenyl groups may be bonded directly together or bonded indirectly through a di- or higher valent organic radical such as an alkyl, alkene, carbonyl, oxygen, sulfur, sulfone, substituted or monosubstituted amine, organosilane, organosiloxane, organophosphite, and organphosphoryl unit.
  • R 2 is a substituted or unsubstituted phenyl, naphthalene, or diphenyl compound.
  • R 2 is a diphenyl radical
  • the two phenyl groups may be bonded directly together or bonded indirectly through a higher valent organic radical such as an alkyl, alkene, carbonyl, oxygen, sulfur, sulfone, substituted or monosubstituted amine, organosilane, organosiloxane, organophosphite, and organphosphoryl unit.
  • a higher valent organic radical such as an alkyl, alkene, carbonyl, oxygen, sulfur, sulfone, substituted or monosubstituted amine, organosilane, organosiloxane, organophosphite, and organphosphoryl unit.
  • BMI resins include resins according to the preceding formula wherein n equals zero.
  • Suitable BMIs wherein n equals zero include the following: N,N'-p- phenylene-bis-maleimide; N,N-m-phenylene-bis-maleimide; N,N-'4,4'-diphenylmethane-bis- maleimide; N,N'-4,4'-diphenylether-bis-maleimide; N,N'-4,4'-diphenylsulphone-bis-maleimide; N,N'-m-xylene-bis-maleimide; and N,N'-4,4'-diphenylcyclohexane-bis-maleimide.
  • the preferred BMI is PMR-15.
  • PMR-15 is a reaction product of 4,4'- methylenedianiline, benzophenone, a dianhydride and nadic anhydride.
  • a second preferred matrix material is a cyanate ester resin.
  • Cyanate ester resins comprise cyanate ester monomers and/or oligomers that have two or more cyanate ester (-OCN) functional groups per molecule. The molecular weight of cyanate ester monomers and oligomers typically ranges from 150 to 2000.
  • the cyanate ester resin preferably includes one or more bis-aryl cyanate esters having the general formula: wherein R 3 is any substituted or unsubstituted, aliphatic, aromatic or cycloaliphatic structure including, but not limited to, linear and branched alkyls, sulfur, and fluorocarbons, and wherein X 5 . 8 are, independently, hydrogen or C alkyls.
  • Suitable cyanate ester compounds include the following: 1,3 and 1,4 dicyanatobenzene, 2-tert-butyl- 1 ,4-dicyanatobenzene, 2,4-dimethyl- 1 ,3-dicyanatobenzene, 2,5- di-tert-butyl-l,4-dicyanatobenzene, tetramethyl-l,4-dicyanatobenzene, 4-chloro-l,4- dicyanatobenzene, 1,3,5-tricyanatobenzene, 2,2- or 4,4-dicyanatobiphenyl; 3,3',5,5-tetramethyl- 4,4-dicyanatobiphenyl; 1,3,- 1,4-, 1,5-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene; 1,3,6- tricyanatonaphthalene; bis(4-cyanatophenyl)methane; bis(3,5-dimethyl-4- cyantophenyl)methane;
  • cyanated novolac resins cyanated bisphenol polycarbonate oligomers, cyanato-terminated polyarylene ethers, dicyanate esters free of ortho hydrogen groups, mixtures of di- and tricyanates, polyaromatic cyanates containing polycyclic aliphatic groups, fluorocarbon cyanates and other cyanate derivatives.
  • a third preferred matrix material is an epoxy acrylate resin.
  • Epoxy acrylate resins, or vinyl ester resins as they are more commonly called, are produced by reacting an epoxy compound with an ethylenically unsaturated acid such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid.
  • vinyl ester resins An alternative method of forming vinyl ester resins is to react glycidyl (meth)acrylate with a multifunctional phenol. The most infamous of these materials is made from the diglycidyl ether of bisphenol- A (DGEBPA) and methacrylic acid.
  • the epoxy compound is preferably an epoxy resin. Because of the variety of epoxy compounds and unsaturated acids that may be employed, vinyl ester resins vary considerably in viscosity, high-temperature properties and toughness. For example, vinyl ester resins produced from novolac epoxy resins have better high-temperature properties than the DGEBPA based resins. Examples of suitable vinyl ester resins include the following:
  • w is a positive value of from about 1 to about 20, preferably from about 2 to about 10.
  • the vinyl esters resins may be used alone or in combination with monoethylenically unsaturated monomers, oligomers and polymers.
  • suitable monoethyleneically unsaturated monomers are styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ethylstyrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, ethylstyrene, ⁇ -vinyl-xylene, ⁇ -chlorostyrene, ⁇ -bromostyrene, vinylbenzylchloride, p-tert-butylstyrene, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate,
  • a fourth preferred matrix material is an epoxy resin.
  • Epoxy resins are characterized as having two or more three membered rings, known as epoxy, epoxide, oxirane, or ethoxyline groups, that have the following structure:
  • Epoxy resins are thermosetting resins that react with curing agents to yield insoluble and infusible three dimensional networks. Generally these resins have a theoretical heat of reaction ranging from 20 to 25 Kcal/eq when measured at 10°C/min using a DSC. Epoxy resins are prepared by the reaction of active hydrogen containing compounds with an epihalohydrin followed by dehydro-halogenation. The simplest epoxy resin is prepared by the reaction of a bisphenol, such as bisphenol A, with an epichlorohydrin to form a diglycidyl ether of bisphenol A (DGEBPA).
  • a DGEBPA has the following formula:
  • Epoxy resins can be obtained in either liquid or solid states. Liquid states are obtained by reacting an active hydrogen containing compounds with an excess of epihalohydrin in a caustic soda solution or other equivalent basic medium. The ratio of active hydrogen containing compound to epihalohydrin in the formation of liquid epoxy resins is generally 10: 1, respectively. An excess of epihalohydrin is used in order to minimize polymerization of the reactants to higher molecular weight species. In example, the reaction of epichlorohydrin and bisphenol A in a 10: 1 ration in the presence of caustic soda would yield a liquid epoxy resin in accordance with the preceding formula wherein m is nearly zero (around 0.2).
  • Solid epoxy resins are obtained by reacting an active hydrogen containing compounds with epihalohydrin in theoretical molar ratio with little excess epihalohydrin.
  • a caustic soda or equivalent basic medium is utilized.
  • the reaction of epichlorohydrin and bisphenol A is a 1 : 1 ratio in the presence of caustic soda would yield a high molecular weight solid epoxy resin in accordance with the preceding formula wherein m is ranges from 2 to about 30.
  • Epoxy resins include numerous modified adducts.
  • This adducts are formed by further reacting the epoxy resins with comonomers and copolymers including vinyl compounds, acrylics, bis-aryl cyanate esters, polyesters, phenol and/or cresol novolacs, bis- [4(2,3-epoxy propyoxy)phenyl]methane, carboxyl rubbers and amines.
  • the most predominant adducts are epoxy-carboxyl rubber adducts, epoxy-amine adducts and epoxy phenol novolac resins (EPNs).
  • EPNs are made by glycidylation of an acid catalyzed condensation product of a phenol and excess aldehyde. The product has random ortho- and/or para- methylene bridges.
  • the phenol may be chosen from any known member of the phenol group however the compounds phenol and cresol are preferred. When cresol is used the adduct is called an epoxy cresol novolac (ECN).
  • EPNs and ECNs have the
  • R is a hydrogen for EPNs and methyl for ECNs, and p is greater than or equal to zero.
  • EPN is bisphenol F.
  • Y ⁇ are, independently, any organic radical.
  • the most preferred epoxy resin comprises a blend of the following components: (1) an epoxy phenol novolac, (2) a liquid bisphenol epoxy; and (3) a solid bisphenol epoxy.
  • a blend of these three components produces superior tack, drape, flow, and void resistance compared to conventional underfill materials.
  • the epoxy phenol novolac is present in an amount of 1 to 50%, and most preferably 20 to 30% based on the weight of the non filler portion of the underfill composition.
  • Any phenol, aldehyde and epoxy functional compound may be utilized to form the epoxy phenol novolac, but the preferred phenol is cresol, the preferred aldehyde is formaldehyde and the preferred epoxy functional compound is epichlorohydrin.
  • the liquid bisphenol epoxy is present in an amount of 1% to 50%, and most preferably 35 to 45% based on the non-filler portion of the underfill composition.
  • Any epoxy functional compound and bisphenol may be employed to form the liquid bisphenol epoxy but the preferred epoxy functional compound is epichlorohydrin and the preferred bisphenol is bisphenol A in a ratio ranging from between 2: 1 to 20: 1 , respectively.
  • the solid bisphenol epoxy is present in an amount of 1% to 30%, and most preferably 12% to 17% based on the non-filler portion of the underfill composition.
  • the second component in the uncured film is one or more curing agent/catalysts.
  • the curing agents are also known as hardening agents because they cause the formation of a hard infusible product.
  • the curing agents are utilized in an amount ranging from 0.01 to 10% by weight of the film.
  • the curing agent must be soluble in the matrix material at a temperature less than or equal to 100°C, and preferably is completely soluble in the matrix material at room temperature.
  • the solubility of the curing agent in the matrix material is important because the diffusion kinetics of insoluble cure catalysts are much slower than their curing kinetics. This results in the formation of a gel layer around the catalyst that hinders its dispersion and, thereby hinders its ability to cause a quick, steady and uniform cure.
  • Virtually any conventional class of curing agent may be employed as long as it is a species that is soluble in the matrix material at a temperature less than or equal to 100°C.
  • the preferred matrix materials include: (a) bismaleimide resins; (b) cyanate ester resins; (c) vinyl ester resins; and epoxy resins.
  • BMI resin curing agents include: alkali metal salts of monocarboxylic acids, dicarboxylic acids, cyanides or carbonates; secondary, tertiary and quartenary amines; organophosphine and organophosphonium compounds; and peroxyketal compounds.
  • BMI resins may be reacted with amines, sulphides and adoximes to form extended polymer structures.
  • amines, sulphides and adoximes to form extended polymer structures.
  • the reaction is carried out with a deficiency of amine, the polymer will have terminal double bonds which can be further crosslinked with a multiunsaturated isocyanate.
  • Typical multiunsaturated agents include divinyl benzene and triallyl isocyanate.
  • Catalysts for the reacting the cyanate ester include metal salts such as zinc octoate and cobalt naphthanate, amines, and organometallic compounds such as cyclopentadienyl iron dicarbonyl dimer [(C 5 H 5 Fe(CO)) 2 ] and cyclopentadienyl manganese tricarbonyl [C 5 H 5 Mn(C ⁇ ,].
  • Ninyl esters are polymerized by a free radical reaction that is usually initiated by a thermal or catalytic decomposition of peroxides or a decomposition of a photoinitiator.
  • Illustrative of typical curing agents in the art are the following: benzoyl peroxide; dicumyl peroxide; methyl ethyl ketone peroxide; ditertiary butyl peroxide; tertiary butyl hydroperoxide; tertiary butyl perbenzoate; Luperoxi 118 (sold by Wallace and Tieman, Lucidol Division, 1740 Military Road, Buffalo, ⁇ .Y. 14240); cumene hydroperoxide; or other peroxides or a mixture thereof. It is common to combine metal salts of naphthenates, e.g.
  • Epoxy resin curing agents are either catalytic or coreactive.
  • a catalytic curing agent functions as an initiator for the epoxy resin polymerization, whereas a coreactive curing agent acts as a comonomer in the polymerization process.
  • the catalytic curing agents include Lewis acids, Lewis bases and tertiary amines and may function by either an ionic or cationic mechanism.
  • the coreactive curing agents include active hydrogen containing compounds such as primary and secondary amines, phenols, phenoplasts, aminoplasts, alcohols, thiols, carboxylic acids and carboxylic anhydrides. Except for acid anhydrides, these active hydrogen containing compounds leave pendant hydroxyl groups in the cured resins.
  • Common epoxy resin curing agents include anhydrides, imidazoles, and diamides and diamines such as dicyandiamide, m- and p-phenylenediamine, 4,4'-methylenedianiline, 3,3'-diaminodiphenyl sulfonne (3,3'-DDS) and 4,4'-diaminodiphenyl sulfone (4,4' -DDS).
  • the amount of the coreactive curing agent used in an epoxy resin is generally such that one curing agent reactive group is present per epoxy group. It should be noted that anhydrides are not preferred curing agents. Anhydrides easily undergo hydrolysis to diacid when subjected to environmental moisture resulting in significant performance reduction.
  • Preferred epoxy resin curing agents for use in the invention are selected from the group consisting of imidazoles, imidazole salts, primary and secondary amines, tertiary amines, "urons" (dimethylamine-aromatic amine ureas), novolac resins and boron compounds. More preferably, the curing agents are selected from liquid imidazoles.
  • the curing agents are chosen from the group consisting of 1-benzylimidazole, 2-ethyl-4-methylimidazole, l-cyanoethyl-2-ethyl-4-methyl imidazole, 1-methylimidazole, 1- heptadecylimidazole and phenylimidazole.
  • the total amount of preferred curing agent utilized is 0.01 to 0.1 moles of imidazole per equivalent of epoxy (M/eq), preferably 0.025 to 0.075 M/eq , and most preferably 0.06 to 0.07 M/eq.
  • the third component of the uncured film is one or more fillers that are inert and insoluble in the matrix material.
  • the objective is to include as high a volume fraction of filler as practically possible, as this reduces the coefficient of thermal expansion in the final cured film.
  • the level of stress in the bonds formed between the chip and the PB is a function of the difference in CTE between the solder bonds, the I/O's, the bonding lands, and the cured underfill.
  • a lower adhesive CTE reduces this difference and produces lower levels of thermal stress and, consequently, improved durability.
  • the filler needs to be substantially spherical.
  • substantially spherical is intended to convey the fact that the particles are chosen from those fillers generally referred to as "spheres" in the art while, at the same time, recognizing that there is really no such thing as a perfectly spherical particle.
  • the maximum volume fraction possible is on the order of 63% for a uni-modal distribution of filler, 73% for a bi-modal distribution, and approximately 80% for a tri- or higher modal distribution.
  • formulations containing the maximum amount of filler are not practical because the viscosity of the resulting mixture often becomes too high. As a result, practical formulations are usually 3 to 10% v/v lower than the theoretical maximum.
  • the filler should be present in a volume fraction of from 50 to 80%, preferably 60 to 75%, and most preferably 63 to 72%. Volumes less than 50% will not provide a sufficiently low CTE. It has been found that the maximum particle size of the filler component is critically related to the ability to obtain and maintain 100% electrical continuity within all of the circuit connections during the underfilling process. The particle size distribution is chosen so that the film flows around and between the forming solder joints when heated and does not get caught under or between the descending solder balls. The solder bails must be able to push the filler away from the solder joint area. The required maximum particle size is best defined in terms of the ratio between the maximum particle size to the solder bump gap or chip/PB separation distance (d/s).
  • the d/s ratio is 1/2, preferably 1/4 and most preferably 1/10.
  • a d/2 ratio of less than or equal to 1/2 prevents the filler from getting caught under the solder or jamming between the solder bumps.
  • the solder bump spacing is 25 ⁇ m. Therefore, the maximum particle size is typically no greater than 12.5 ⁇ m, preferably no greater than 8.25 ⁇ m, and most preferably no greater than 2.5 ⁇ m. Microscopic examination shows that larger filler particles get trapped at or near individual solder bumps, precluding bonding of these bumps to the associated PB bonding land. These portions of the circuits, of course, do not exhibit any electrical continuity.
  • the filler's CTE should be as low as possible - and certainly less than 10 ppm/°C.
  • the filler may be inorganic or organic.
  • inorganic spherical filler are amorphous silica, alumina (AL ⁇ ), ceramic microspheres, (i.e. the Zeospheres produced by Zeeland corporation), and solid and hollow glass spheres.
  • Organic spheres can be formed from cured and crosslinked rubber and thermoset resins as well as thermoplastic polymeric materials.
  • Such fillers may have a coating on their surface to maximize thermal conductivity.
  • Silica is the preferred filler because of its low coefficient of thermal expansion, its spherical shape, and the fact that it is commercially available in several particle size distributions.
  • a number of other additives can also be present in the uncured film.
  • Preferred additives include, but are not limited to, tougheners, colorants, processing aids, thixotropic compounds, internal mold release agents, and minor amounts of a temperature expandable filler.
  • Acceptable tougheners include high molecular weight reactive resins, core/shell rubbers and other soluble and reactive rubber materials. The tougheners may be used alone or in combination.
  • Two preferred tougheners are a high weight average molecular weight Bisphenol A epoxy resin sold under the Trademark PHENOXY PKHH (Phenoxy Associates) and a particulate silicone rubber sold under the Trademark X5-8452 (Dow Corning). These tougheners improve the crack resistance of the cured underfill and play a role in raising the thermal cycle resistance of the cured underfill.
  • the total amount of toughener utilized in the underfill is 0 to 20%, preferably 2.5 to 15%, and most preferably 10 to 15%, based on the non-filler portion of the underfill composition. If colorants are used, they are selected from both soluble dies and insoluble organic and inorganic pigments.
  • a preferred colorant is the blue phthalocyanine pigment sold as a dispersion in epoxy resin as PDI 22-38010 by the Ferro Corporation. Such colorants are added to aid machine optical recognition characteristics during underfilling operations.
  • the total amount of colorant dispersion utilized in the underfill is 0 to 7.5%, preferably 0.5 to 5% and most preferably 1.0 to 3.0 %, based on the non-filler portion of the underfill formulation.
  • Acceptable processing aids include wetting agents, manufacturing aids, bubble breakers and surfactants.
  • the total amount of processing aid utilized in the underfill is 0 to 1.0%, preferably 0.01% to 0.5%, more preferably 0.1% to 0.25%, and most preferably 0.12%.
  • Wetting agents are added to aid both the dispersion of the filler materials into the resin and to release air included into the system by the addition of the filler.
  • Manufacturing aids are added to the formulation to support quality assurance audits of system composition during the manufacturing process.
  • Preferred processing agents include a polymeric acrylic material sold under the Tradename of PC- 1344 (Monsanto).
  • Acceptable thixotropic compounds include, but are not limited to, pyrogenic silicas, clays and both organic and inorganic fibrous materials.
  • a preferred thixotrope is Pyrogenic silica.
  • Thixotropic compounds are added to modify and control behavior of the underfill formulation and to retard the separation and setting of the filler materials.
  • the total amount of thixotrope utilized in the underfill is 0 to 10%, preferably 0.5 to 5%, and most preferably 1 to 3% of the non-filler portion of the underfill formulation.
  • Acceptable internal mold release agents include, but are not limited to, natural and synthetic waxes. Internal mold release agents serve to reduce the environmental moisture adsorption at the air/underfill interfaces.
  • the total amount of internal mold release agent is 0 to 5%, preferably 0.25 to 2.5%, and most preferably 0.5 to 1% of the non-filler portion of the underfill formulation.
  • Acceptable temperature expandable fillers include those materials which possess hollow thermoplastic shells containing a low molecular weight organic liquid therein, such as a propellant.
  • Typical shell materials include, but are not limited to polyvinyl chloride, polyacrylonitrile and their copolymers thereof.
  • Temperature expandable fillers serve to reduce the dielectric constant of the cured underfill.
  • the total amount of temperature expandable filler utilized in the underfill is 0 to 15%, preferably 1 to 10%, and most preferably 5 to 10% by weight of the total underfill.
  • the uncured film must comply with certain physical and kinetic parameters.
  • the film must contain a smooth, uninterrupted surface. It must have a uniform thickness of 5 mils or less with a deviation of + 0.5 mils or less and a Cpk higher than 1.0.
  • the film must have a viscosity of at least 50,000 poise at room temperature.
  • the film must exhibit sufficiently low tack to permit die-cutting and machine placement and sufficient flexibility to be handled without breaking.
  • the film must have an activation energy no greater than 300 KJ/mol.
  • the film must retain more than 50% of its theoretical heat of reaction when tested a heating rate of 200°C/min.
  • the film must have a smooth and uninterrupted surface. Any interruption or pocket on the surface of the film can trap air which may form voids at the surface when the film melts and cures. These voids reduce adhesion and trap water vapor and other environmental hazards
  • the film also must have a consistent and low film thickness 5 mils or less with a deviation of + 0.5 mils or less and a process capability index (Cpk) higher than 1.0. Cpk measures the ability to create a product within specified limits.
  • a Cpk greater than 1.0 means that there is a 99.9% chance that every area of the film is within the prescribed limits.
  • the film thickness is 2-4 mils and most preferably 3-4 mils. Such requirements regarding the thickness and uniformity of the film are necessary to ensure that the film can be utilized to fill the thin chip/PB separation and provide enough resin to fiHet around the edges of the chip.
  • the film must have a viscosity of at least 50,000 poise at room temperature. Generally, these high viscosity films also have an uncured glass transition temperature in the range of 25°C to 40°C.
  • the high viscosity of the inventive films is an essential difference between the prior art relating to liquid underfills and the invention.
  • the high viscosity diminishes the tack of the film permitting die cutting and mechanical placement. It also prevents resin creep and the resulting shape distortion. Furthermore, the high viscosity allows the film to remain in one plane without breaking during placement.
  • the kinetics of the film's cure are critical to its success. A successful film must cure completely during the soldering cycle utilized to attach the I/O's on the chip to the PB in a steady manner that does not generate voids in the cured product. Typical soldering cycles last 30 seconds at temperatures ranging from 200°C to 325°C. The heating rates used in these processes are often greater than 600°C/min. It has been discovered that the void content is controlled by the cure kinetics of the film.
  • the film In order to form a void free product under the aforementioned curing conditions, the film must have an activation energy that is less than 300 KJ/mol, preferably less than 225 KJ/mol, and most preferably less than 200 KJ/mol, as defined by analysis of DSC curves at 10°C/min. In addition, the film must retain greater than 50%, preferably greater than 65%, and most preferably greater than 70%, of its theoretical heat of reaction, as measured using a DSC cure scan at 10°C/min, when tested at a heating rate of 200°C/min. In the case of epoxy resins, the theoretical heat of reaction is around 25 Kcal/eq.
  • the liners provide a protective support for the film during storage and are peeled away from the film immediately prior to application.
  • the release liners may be selected from a wide variety of materials including metal foil, plastics such as polyethylene, polypropylene, polyester, and the like, and paper.
  • the release layers may be coated to aid separation from the film.
  • the aforementioned uncured film can be placed between a chip and PB, and then cured, to form a product that adheres the chip to the PB and, simultaneously, fills the separation between the chip and the PB without undermining the electrical continuity of the solder joints. When the aforementioned uncured film is cured, it exhibits a number of beneficial properties.
  • the cured film is void free, has a CTE between 20 and 25 ppm/°C, and has an isotropic modulus, fracture strength, CTE and thermal conductivity.
  • the cured film can withstand more than 2,000 thermal cycles and often can withstand 5,000 thermal cycles.
  • a thermal cycle resistance of 5,000 thermal cycles is a 250% increase compared to conventional processes wherein a low viscosity product is wicked into place and cured.
  • a typical underfill process employing the films of this invention is set forth in FIG. 1. In FIG. 1, a PB 10 containing two or more bonding lands 20' and 20" is placed on a surface.
  • the PB 10 is formed from a nonconductive substance which may comprise compounds such as reinforced polyimides, reinforced polyesters, fluoropolymers, paper phenolics such as NEMA-XXP, KAPTON, Teflon film, silicone rubbers, epoxies and ceramic materials.
  • a nonconductive substance which may comprise compounds such as reinforced polyimides, reinforced polyesters, fluoropolymers, paper phenolics such as NEMA-XXP, KAPTON, Teflon film, silicone rubbers, epoxies and ceramic materials.
  • point-to-point connections (wiring) and/or components (circuits) made from highly conductive materials such as copper and gold that are connected to bonding lands 20' and 20" .
  • An uncured film 30, made in accordance with the instant invention is then die cut to a size that is slightly smaller than the chip 40 that is going to be attached to the PB 10.
  • the uncured film 30 has a thickness that is slightly thicker than the desired chip/PB separation.
  • the sizing and thickness of the uncured film 30 is critical toward insuring that the film's volume is sufficient to make the underfill and flow about the bonds without flowing outside the bonding area on the surface of the PB 10.
  • the uncured film 30 is manually or mechanically placed between the bonding land 20' and 20" on the PB 10. Mechanical placement is obviously favored in order to insure accuracy and consistency in the procedure.
  • a silicon chip 40 is then provided. Solder bumps 50' and 50" are placed over the I/O's on the chip 40. These solder bumps may be formed from a variety of known solders. For example a tin/lead mixture that reflows between 200°C and 240°C may be utilized. This is the type of solder that is generally used for in-house electronic applications.
  • a tin lead mixture that contains a high concentration of lead (-95%) and reflows around 325°C can be used.
  • This is the type of solder that is generally used by the automotive industry for high heat applications.
  • the chip 40 containing solder bumps 50' and 50" is then lowered onto the uncured film 30 so that the solder bumps 50' and 50" align with bonding lands 20' and 20" on the PB 10.
  • Sandwiched between the chip 40 and PB 10 is the uncured film 30.
  • the entire assembly is then subjected to heat and pressure. The heat and pressure cause the uncured film 30 to flow to the edges of the assembly. Simultaneously, the solder bumps 50' and 50" descend to contact the bonding lands 20' and 20".
  • the heat and pressure parameters are selected to so that the uncured film 30 cures simultaneously with the formation of the solder joints 75' and 75" .
  • cure is effected at a temperature around 325°C (which is the solder reflow temperature of tin/lead solder mixtures having a high lead content).
  • no pressure is needed.
  • the time necessary to fully cure the material is generally less than 2.5 minutes and, most preferably, is less than 30 seconds.
  • the final product is an underfilled circuit assembly 60 wherein the cured film 70 fills the entire area around and between the solder joints 75' and 75".
  • the underfilled circuit assembly 60 comprises a chip 40 whose I/O's are bonded by solder bumps 50' and 50" to bonding leads 20' and 20" on the PB 10.
  • the chip 40 is further adhered to the PB 10 by a cured underfill film 70 that fills the separation between the chip and the PB 10.
  • FIG. 2 illustrates the desired geometry of the cured film 70 which forms the adhesive bond in the underfilled circuit assembly 60.
  • an underfilled circuit assembly 60 is split by a center line 80.
  • the illustrated left half of the underfilled circuit assembly 60 comprises a PB 10 containing a bonding land 20 attached by a solder joint 75 to a chip 40.
  • the area around the solder joint 75 is filled by a cured film 70.
  • a concave fillet 85 at the edge of the assembly 60 is formed by excess film 70 which flowed and cured outside of the joint 75.
  • a well shaped and sized fillet 85 will improve the adhesive properties of the bond.
  • One of the benefits of the aforementioned process is that the chips are underfilled in a very short time frame. Furthermore, since the size of the underfill films are cut to closely approximate the size of the chips, the impact of increasing chip size on production time is eliminated. An additional benefit of the technology is that the films cure concurrently with the soldering of the chips to the PB. Thus the separate cure cycle required by the state of the art liquid underfill materials is eliminated. Finally, the technology demonstrates improved durability. The underfills have been tested to 5000 cycles before failure compared to the 2000 thermal cycles characteristic of liquid systems.
  • Example 1 The superiority of matrix soluble curing agents over matrix insoluble curing agents for underfilling can be observed by Differential Scanning Calorimetry (DSC) measurements taken during cure. DSC measurements were taken at temperatures up to 200 °C (the limit of the instrument) for three samples of an epoxy resin. The three samples were identical in every way with the exception that each sample contained a different curing agent. The three curing agents tested were as follows:
  • CURTMID CN l-cyanoethyl-2-ethyl-4-methylimidazole
  • DDS/Dicy 4,4'-diaminodiphenylsulfone/ dicyandiamide
  • FIG. 3 sets forth the data obtained from this experiment.
  • FIG. 3 plots the heat of reaction, in Kcal/eq, for each of the three systems, versus the heating rate, in degrees Celsius.
  • CURTMID CN generates -85% of the theoretical epoxy heat of reaction (which is around 25 Kcal eq) at 10°C/min and retains -70% of this value when cured at 200° C/min.
  • the aromatic amine system, 4, 4'-DDS/Dicy generates 100% of the theoretical heat of reaction when heated at 10°C/min and retains 85% of this value when heated at 200°C/min.
  • 2-methylimidazole (2MZ- Azine) the insoluble imidazole curing agent exhibits a very low heat of reaction (-40% of the theoretical) both at high and low heating rates.
  • the room temperature soluble catalysts in Table 1 are 2-ethyl-4-methylimidazole,l- benzyl-2-methylimidazole and l-(2-cyanoethyl-ethyl-4-methylimidazole.
  • the low temperature soluble catalysts (soluble at less than 100°C) in the table are bis 4,4'- diaminodiphenylsulfone/dicyandiamide and isophthalic acid dihydrazide.
  • the insoluble catalysts in the table are l-2(diaminotriazine)ethyl-2-methylimidazole, benzimidazole, and 2-mercaptobenzimidazole.
  • the cure kinetics of the underfill film is critical to its success.
  • the film should exhibit a heat of reaction that is, most preferably, 90% of the theoretical heat of reaction when tested at heating rate of 10°C/min, and that is 70% of the theoretical heat of reaction when tested at a heating rate of 200°C/min.
  • Room temperature soluble curing agents are best able to meet the requisite cure kinetics. To demonstrate this point, the high temperature curing rates of two films from Example 1 were measured.
  • FIG. 4 graphs the peak reaction temperature in degrees Celsius versus the log of the heating rate for the two films.
  • the room temperature soluble imidazole system is the fastest curing system. It generates the lowest peak reaction temperature at the same heating rate.
  • the aromatic amine system is the slowest system, demonstrating a peak reaction temperature of 70 °C or more greater than the soluble imidazole.
  • Underfill processing problems arise when slower curing compositions are used because the composition does not fully cure in the short time it takes to reach the processing temperature. Large voids are then produced due to volatilization of the uncured resin.
  • Room temperature soluble catalysts are, therefore, the preferred curing agent for use in the invention. These catalysts generally, and room temperature imidazoles specifically, cure more fully in the same amount of time and generate fewer volatiles. As a result, the products exhibit fewer voids.
  • test specimens made using the aromatic amine curing agent generated a higher void content.
  • Example 3 The particle size of the fillers employed in the underfill film is critical to its ability to ensure electrical continuity within the solder joints.
  • the particle size distribution is chosen so that the descending solder ball can push the filler away from the solder joint and, thereby, prevent the filler from getting caught between the solder ball and the bonding pad. Filler caught between the solder ball and bonding pad can disrupt the electrical continuity of the bond.
  • two filler mixes of different particle size distributions were added to two identical samples of an epoxy resin composition.
  • the particle size distributions of two filler mixes is set forth in FIG. 5. Also shown in FIG. 5 is the 25 ⁇ m bump spacing that represents the typical separation between solder joints in an integrated circuit assembly.
  • the first filler mixture has a median particle size of approximately 25 ⁇ m.
  • the resultant underfilled chip exhibited low levels of circuit continuity. Microscopic examination of these assemblies showed that the larger filler particles were being trapped at or near individual solder bumps, precluding bonding of these bumps to the associated PB bonding land. These portions of the circuits, of course, did not exhibit any electrical continuity.
  • the second filler mixture has a median particle size of approximately 4 to 5 ⁇ m. Underfilled chips using this filler mix exhibited 100% circuit continuity. Microscopic examination of the underfilled chips showed that the filler, in this case, "flowed" around and away from the solder bumps, allowing all solder joints to be successfully bonded.
  • the significant difference between these two filler packages is the size and proportion of the largest particle size fillers.
  • the smallest distribution filler package is greater that 90% less than the 25 ⁇ m bump spacing and 100% less than 30 ⁇ m.
  • the unsuccessful filler blend has a maximum particle size of 80-90 ⁇ m and 10% are greater than 50 ⁇ m.
  • 'Phenoxy PKHH is a high molecular weight bisphenol A epoxy manufactured by Phenoxy Associates.
  • Epon 828 is a liquid bisphenol A epoxy resin manufactured by Shell Chemical.
  • Tactix 742 is a trifunctional epoxy resin manufactured by Ciba.
  • ⁇ Tactix 695 is a toughened multifunctional epoxy resin manufactured by Ciba.
  • Epon 164 is an epoxidized cresol novolac manufactured by Shell.
  • Epichlon 830S is a liquid bisphenol F epoxy resin manufactured by Dainippon.
  • ECN 1873 is an epoxidized cresol novolac manufactured by Ciba.
  • RSL 1462 is a liquid bisphenol A epoxy resin manufactured by Shell.
  • DEN 438 is an epoxidized phenol novolac manufactured by Dow.
  • MY 721 is an epoxidized methylene dianiline manufactured by Ciba.
  • n MYO500 is a triglycidyl-para-aminophenol manufactured by Ciba.
  • Epon 100 IF is a solid bisphenol A epoxy manufactured by Shell.
  • PC 1344 is a nonionic surfactant manufactured by Monanto.
  • Blendex 311 is an ABS toughener manufactred by General Electric.
  • X5-8452 is a silicone toughener manufactured by Dow Corning.
  • Teco-Sil 200F is an electronics grade silica produced by Combustion Engineering.
  • 18 GP-31 is an electronics grade silica produced by Harbison Wlaker.
  • 19 FB-74 is an electronics grade silica produced by Denka.
  • 20 FB-6S is an electronics grade silica produced by Denka.
  • 21 FB-3S is an electronics grade silica produced by Denka.
  • TS 720 is a fumed silica thixotrope produced by Cabot.
  • 4,4'-DDS is a diaminodiphenylsulfone produced by Ciba.
  • 24 Dicy is a dicyandiamide produced by Air products.
  • 25 2MX- Azine is a 2-methylimidazole-azine produced by Air Products.
  • Curimid CN is a 1 cyanoethyl-2-ethyl-4-methylimidazole produced by PolyOrganix.
  • Color Dispersion is a phthalocyanine pigment/epoxy milled dispersion available from a variety of manufacturers.
  • compositions E and G form high viscosity films that have proven useful in the instant invention.
  • Compositions A, C and D should also form high viscosity films that are useful in the instant invention.
  • Compositions B and F are compositions that have been proven ineffective for use in the instant invention. The properties of each of the aforementioned compositions A through F were examined. The results of this examination are set forth in Table 3 below:
  • composition G which is a high viscosity composition comprising an epoxy phenol novolac, asolid bisphenol epoxy and a liquid bisphenol epoxy, exhibits a 250% improvement in thermal cycle resistance when compared to the commercial liquid underfill.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Wire Bonding (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

L'invention concerne un film (30) mince, uniforme, à haute viscosité, non renforcé et non durci. Ledit film (30) comprend : (a) de 0,5 à 50 %, selon le poids du film (30), d'un matériau polymère ou d'un matériau matriciel de formation de polymère ; (b) de 0,01 à 10 %, selon le poids du film (30), d'un agent de durcissement soluble dans le matériau matriciel à une température ne dépassant pas 100 °C ; et (c) de 50 à 80 %, selon le volume du film (30), d'une charge sensiblement sphérique et inerte ayant une granulométrie maximum inférieure ou égale à 30 νm. Ledit film (30) présente certaines propriétés cinétiques lui permettant de durcir très rapidement et de façon à ne pas produire de substances volatiles produisant des vides. Le film (30) peut être placé entre une puce (40) de silicium et une carte imprimée (10) au cours d'un procédé d'assemblage de puces à bosses, puis durci pour former un matériau de sous-remplissage (70). La phase de durcissement peut être réalisée au cours du même cycle thermique utilisé pour la formation des soudures (75' et 75') lors du procédé des puces à bosses. Les ensembles (60) de sous-remplissage obtenus grâce audit film (30) présentent une résistance au cycle thermique supérieure de 250 % à celle des ensembles obtenus par utilisation de matériaux de sous-remplissage classiques à faible viscosité.
PCT/US1999/028768 1998-12-07 1999-12-07 Compositions de films de sous-remplissage WO2000034032A1 (fr)

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AU21651/00A AU2165100A (en) 1998-12-07 1999-12-07 Underfill film compositions

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US20731698A 1998-12-07 1998-12-07
US09/207,316 1998-12-07

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WO2002065542A2 (fr) * 2001-02-12 2002-08-22 International Business Machines Corporation Compositions de remplissage sous-jacent
DE10209915A1 (de) * 2002-01-11 2003-07-24 Hesse & Knipps Gmbh Verfahren zum Flip-Chip-Bonden
US6632523B1 (en) 2000-09-28 2003-10-14 Sumitomo Bakelite Company Limited Low temperature bonding adhesive composition
WO2004106454A2 (fr) * 2003-05-23 2004-12-09 National Starch And Chemical Investment Holding Corporation Agent d'encapsulation expansible partiellement rempli
US6833629B2 (en) 2001-12-14 2004-12-21 National Starch And Chemical Investment Holding Corporation Dual cure B-stageable underfill for wafer level
WO2004114374A2 (fr) * 2003-05-23 2004-12-29 National Starch And Chemical Investment Holding Corporation Methode d'utilisation d'un agent d'encapsulation de type underfill pre-applique
US6946745B2 (en) 2002-01-11 2005-09-20 Hesse & Knipps Gmbh Method and components for flip-chip bonding
US6978540B2 (en) 2003-05-23 2005-12-27 National Starch And Chemical Investment Holding Corporation Method for pre-applied thermoplastic reinforcement of electronic components
WO2006036505A1 (fr) * 2004-09-28 2006-04-06 Intel Corporation Materiau de remplissage visant a reduire le potentiel de delaminage et de fissuration d'un traitement applique sous les bosses
US7041331B2 (en) 2003-04-05 2006-05-09 Rohm And Haas Electronic Materials Llc Electronic device manufacture
JP2007056070A (ja) * 2005-08-22 2007-03-08 Fujitsu Ltd フリップチップ型半導体装置用アンダーフィル材、並びにそれを用いたフリップチップ型半導体装置及びその製造方法
JP2007523967A (ja) * 2003-05-23 2007-08-23 ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレーション 発泡性アンダーフィル封入剤
US7327039B2 (en) 2002-05-23 2008-02-05 3M Innovative Properties Company Nanoparticle filled underfill
WO2009012442A1 (fr) * 2007-07-18 2009-01-22 Lord Corporation Formulations thermiquement conductrices de remplissage interne
CN101752279B (zh) * 2008-12-09 2012-02-01 台湾积体电路制造股份有限公司 接合第一和第二基板的方法、印刷模板和堆叠基板的系统
US9275879B1 (en) 2014-08-11 2016-03-01 International Business Machines Corporation Multi-chip module with rework capability
EP3450479A1 (fr) * 2017-09-01 2019-03-06 Henkel AG & Co. KGaA Composition latente à durcissement rapide, son utilisation et article ayant une composition durcie obtenue à partir de celle-ci

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US5814401A (en) * 1997-02-04 1998-09-29 Motorola, Inc. Selectively filled adhesive film containing a fluxing agent
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US4437235A (en) * 1980-12-29 1984-03-20 Honeywell Information Systems Inc. Integrated circuit package
US5248710A (en) * 1991-05-29 1993-09-28 Shin-Etsu Chemical Co., Ltd. Flip chip encapsulating compositions and semiconductor devices encapsulated therewith
US5391924A (en) * 1992-09-14 1995-02-21 Kabushiki Kaisha Toshiba Plastic package type semiconductor device
US5386624A (en) * 1993-07-06 1995-02-07 Motorola, Inc. Method for underencapsulating components on circuit supporting substrates
US5972739A (en) * 1995-04-28 1999-10-26 Nec Corporation Method of manufacturing a tab semiconductor device
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Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6632523B1 (en) 2000-09-28 2003-10-14 Sumitomo Bakelite Company Limited Low temperature bonding adhesive composition
WO2002065542A3 (fr) * 2001-02-12 2003-07-31 Ibm Compositions de remplissage sous-jacent
WO2002065542A2 (fr) * 2001-02-12 2002-08-22 International Business Machines Corporation Compositions de remplissage sous-jacent
US6833629B2 (en) 2001-12-14 2004-12-21 National Starch And Chemical Investment Holding Corporation Dual cure B-stageable underfill for wafer level
US6946745B2 (en) 2002-01-11 2005-09-20 Hesse & Knipps Gmbh Method and components for flip-chip bonding
DE10209915A1 (de) * 2002-01-11 2003-07-24 Hesse & Knipps Gmbh Verfahren zum Flip-Chip-Bonden
US7482201B2 (en) 2002-05-23 2009-01-27 3M Innovative Properties Company Nanoparticle filled underfill
US7327039B2 (en) 2002-05-23 2008-02-05 3M Innovative Properties Company Nanoparticle filled underfill
US7041331B2 (en) 2003-04-05 2006-05-09 Rohm And Haas Electronic Materials Llc Electronic device manufacture
CN100366697C (zh) * 2003-05-23 2008-02-06 国家淀粉及化学投资控股公司 可起泡性底层填料密封剂
WO2004114374A2 (fr) * 2003-05-23 2004-12-29 National Starch And Chemical Investment Holding Corporation Methode d'utilisation d'un agent d'encapsulation de type underfill pre-applique
US7004375B2 (en) 2003-05-23 2006-02-28 National Starch And Chemical Investment Holding Corporation Pre-applied fluxing underfill composition having pressure sensitive adhesive properties
WO2004106454A2 (fr) * 2003-05-23 2004-12-09 National Starch And Chemical Investment Holding Corporation Agent d'encapsulation expansible partiellement rempli
WO2004114374A3 (fr) * 2003-05-23 2005-08-11 Nat Starch Chem Invest Methode d'utilisation d'un agent d'encapsulation de type underfill pre-applique
US7047633B2 (en) 2003-05-23 2006-05-23 National Starch And Chemical Investment Holding, Corporation Method of using pre-applied underfill encapsulant
CN100414677C (zh) * 2003-05-23 2008-08-27 国家淀粉及化学投资控股公司 预先施用的底层填料密封剂的应用方法
JP2007523967A (ja) * 2003-05-23 2007-08-23 ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレーション 発泡性アンダーフィル封入剤
WO2004106454A3 (fr) * 2003-05-23 2005-03-03 Nat Starch Chem Invest Agent d'encapsulation expansible partiellement rempli
US6978540B2 (en) 2003-05-23 2005-12-27 National Starch And Chemical Investment Holding Corporation Method for pre-applied thermoplastic reinforcement of electronic components
KR100855114B1 (ko) * 2004-09-28 2008-08-28 인텔 코오퍼레이션 반도체 디바이스에서 볼 리미팅 메탈러지 박리와 균열 포텐셜을 감소시키는 언더필 재료
WO2006036505A1 (fr) * 2004-09-28 2006-04-06 Intel Corporation Materiau de remplissage visant a reduire le potentiel de delaminage et de fissuration d'un traitement applique sous les bosses
JP2007056070A (ja) * 2005-08-22 2007-03-08 Fujitsu Ltd フリップチップ型半導体装置用アンダーフィル材、並びにそれを用いたフリップチップ型半導体装置及びその製造方法
WO2009012442A1 (fr) * 2007-07-18 2009-01-22 Lord Corporation Formulations thermiquement conductrices de remplissage interne
CN101752279B (zh) * 2008-12-09 2012-02-01 台湾积体电路制造股份有限公司 接合第一和第二基板的方法、印刷模板和堆叠基板的系统
US9275879B1 (en) 2014-08-11 2016-03-01 International Business Machines Corporation Multi-chip module with rework capability
EP3450479A1 (fr) * 2017-09-01 2019-03-06 Henkel AG & Co. KGaA Composition latente à durcissement rapide, son utilisation et article ayant une composition durcie obtenue à partir de celle-ci
WO2019042799A1 (fr) * 2017-09-01 2019-03-07 Henkel Ag & Co. Kgaa Composition à durcissement latent et rapide, son utilisation et article comportant une composition durcie pouvant être obtenue à partir de cette première

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