WO2008111980A1 - Composition containing porphyrin to improve adhesion - Google Patents

Composition containing porphyrin to improve adhesion Download PDF

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Publication number
WO2008111980A1
WO2008111980A1 PCT/US2007/063970 US2007063970W WO2008111980A1 WO 2008111980 A1 WO2008111980 A1 WO 2008111980A1 US 2007063970 W US2007063970 W US 2007063970W WO 2008111980 A1 WO2008111980 A1 WO 2008111980A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive composition
porphyrin
adhesive
porphyrin derivative
resin
Prior art date
Application number
PCT/US2007/063970
Other languages
French (fr)
Inventor
Tadashi Takano
Osama M. Musa
Original Assignee
Henkol Ag & Co. Kgaa
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 Henkol Ag & Co. Kgaa filed Critical Henkol Ag & Co. Kgaa
Priority to CN200780052125A priority Critical patent/CN101702915A/en
Priority to PCT/US2007/063970 priority patent/WO2008111980A1/en
Priority to KR1020087031952A priority patent/KR20100014083A/en
Publication of WO2008111980A1 publication Critical patent/WO2008111980A1/en
Priority to US12/552,331 priority patent/US20100062260A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4238—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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Definitions

  • This invention relates to adhesive compositions, methods for improving adhesion to metal substrates, and assemblies of semiconductor dies joined to metal substrates using adhesive compositions using porphyrin.
  • semiconductor dies are attached to metal substrates, such as lead frames, using resin-based adhesives.
  • resin-based adhesives utilize a variety of resin chemistries and serve to hold the die to the metal lead frame during attachment of the semiconductor package to a circuit board, solder reflow, and throughout the use of the package in its end application.
  • semiconductor packaging technology has evolved, the requirements for the adhesive have similarly changed.
  • adhesives that can withstand re-flow temperatures up to 27O 0 C. Good adhesion at this high temperature has proven very difficult to attain with existing formuiations and there is a need for an adhesive composition that would give improved adhesion to metal surfaces, especially at elevated temperatures. This and other needs are addressed by the various embodiments and configurations of the present invention.
  • this invention is an adhesive composition (hereinafter also referred to as an adhesive) that comprises a curable resin and a prophyrin derivative that has at least one carboxylic acid functional group.
  • this invention is a method of improving the adhesion of an adhesive composition comprising (i) providing a curable resin and (ii) adding to the resin a porphyrin derivative that has at least one carboxylic acid functional group.
  • this invention is an assembly comprising a metal substrate, a semiconductor die mounted thereon, and an adhesive composition disposed between the metal substrate and semiconductor die wherein the adhesive composition comprises (i) a curable resin and (ii) a porphyrin derivative that has at least one carboxylic acid functional group.
  • alkyl refers to a branched or un-branched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (“Me”), ethyl (“Et”), n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like.
  • the term "effective amount" of a compound, product, or composition as used herein is meant a sufficient amount of the compound, product or composition to provide the desired results.
  • the exact amount required will vary from package to package, depending on the particular compound, product or composition used, its mode of administration, and the like. Thus, it is not aiways possible to specify an exact amount; however, an effective amount may be determined by one of ordinary skill in the art using only routine experimentation.
  • suitable refers to a moiety that is compatible with the compounds, products, or compositions as provided herein for the stated purpose. Suitability for the stated purpose may be determined by one of ordinary skill in the art using only routine experimentation.
  • substituted is used to refer, generally, to a carbon or suitable heteroatom having a hydrogen atom or other atom removed and replaced with a further moiety. Moreover, it is intended that “substituted” refer to substitutions which do not change the basic and novel utility of the underlying compounds, products or compositions of the present invention.
  • B-staging (and its variants) is used to refer to the processing of a material by heat or irradiation so that if the material is dissolved or dispersed in a solvent, the solvent is evaporated off with or without partial curing of the material, or if the material is neat with no solvent, the material is partially cured to a tacky or more hardened state. If the material is a flow-able adhesive, B-staging will provide extremely low flow without fully curing, such that additional curing may be performed after the adhesive is used to join one article to another. The reduction in flow may be accomplished by evaporation of a solvent, partial advancement or curing of a resin or polymer, or both.
  • curing agent is used to refer to any material or combination of materials that initiate, propagate, or accelerate cure of the composition and includes but is not limited to accelerators, catalysts, initiators, and hardeners
  • free porphyrin As used herein the terms “free porphyrin”, “free porphin”, and “free porphine” are used to refer to a porphyrin that does not have any meta! ions or atoms bound to the nitrogens in the center
  • the porphyrin derivative of the present invention is characterized by having at least one carboxylic acid functional group, typically pendant from the porphyrin ring
  • carboxylic acid functional group typically pendant from the porphyrin ring
  • carboxylic acid functionality gives improved adhesion over porphyrin rings without the carboxylic acid functionality
  • Carboxylic acid functionality with its polar nature, is known for improving adhesion in adhesive formulations
  • Porphyrin rings are used extensively as chelating agents, as they have a propensity for coordinating with metal ions and metal atoms
  • adhesion strength has been found to improve when and if both the porphyrin ring structure and the carboxylic acid functionalities are present and available for chemical interaction ( ⁇ e they are not bound)
  • the acid functionality and the pophyrin ring work together to give an unexpected, synergistic effect in improving bonding to metal surfaces.
  • porphyrin derivative containing at least one carboxylic acid functional group is:
  • the porphyrin derivative may further have at least one reactive double bond pendant from the porphyrin ring.
  • the reactive double bond combined with the carboxylic acid functionality on the porphyrin ring, provides further enhanced adhesive strength. It is theorized that the double bond participates in the polymerization reaction during cure of the curable resin and that the porphyrin ring becomes part of the polymer matrix.
  • the result is a polymeric structure that has a porphyrin ring with carboxylic acid functionality pendant from the polymer.
  • the porphyrin ring and the carboxylic acid act synergistically to bond the adhesive to the metal. Because the porphyrin and carboxylic acid functionalities are a part of the polymer matrix the adhesion improvement is more pronounced than when those functionalities are simply mixed into the adhesive formulation.
  • porphyrin derivative containing at least one reactive double bond in addition to at least one carboxylic acid functional group is:
  • the porphyrin derivative should be a free pophyrin, that is, it should not have any meta! ions or atoms bound to the nitrogens in the center to block the nitrogen from bonding to a metal substrate.
  • a composition containing the porphyrin derivative should not include any free acid molecules, as these can protonate the nitrogens in the prophyrin ring, making the nitrogen unavailable for bonding to the metal substrate. In both these cases, adhesion to the metal would be inhibited.
  • the porphyrin derivative is present in the adhesive composition in an effective amount.
  • An effective amount will vary depending on the resin system selected, but will typically range between 0.25 and 3.0 wt% of the adhesive formulation, excluding filler content.
  • the adhesive composition will contain at least one curable resin.
  • Curable resins suitable for use in the present invention include any that polymerize to cure and that provide the desired rheology, modulus, coefficient of thermal expansion, and other properties required for the specific industrial application.
  • the resin(s) may be polymers, oligomers, monomers, pre-polymers, or a combination of these.
  • Suitable resins include thermoplastics, thermosets, elastomers, thermoset rubbers, or a combination of these.
  • the adhesive composition may or may not contain solvent, as deemed by the practitioner to be suitable for the particular industrial use.
  • the polymer or curabie resin will generally be a major component, excluding any fillers present.
  • Other components, typically used in adhesive compositions, may be added at the option of the practitioner; such other components include, but are not limited to, curing agents, fluxing agents, wetting agents, flow control agents, adhesion promoters (in addition to the porphyrin derivative), and air release agents.
  • the adhesive composition may also contain filler, in which case the filler will be present in an amount up to 95% of the total composition.
  • Resins and polymers used in the adhesive may be solid, liquid, or a combination of the two.
  • Suitable curabie resins include epoxies, acrylates or methacrylates, maleimides, vinyl ethers, polyesters, poly(butadienes), polyimides, benzocyclobutene, siliconized olefins, silicone resins, styrene resins, cyanate ester resins, polyolefins, or siloxanes.
  • the resin will be present in an effective amount, typically between 5 and 100 wt% of the adhesive composition, excluding filler content
  • solid aromatic bismaleimide (BMI) resin powders are included in the adhesive.
  • Suitable solid BMI resins are those having the structure
  • exemplary aromatic groups include:
  • n 1 - 3
  • Bismaleimide resins having these X bridging groups are commercially available, and can be obtained, for example, from Sartomer (USA) or HOS-Technic GmbH (Austria).
  • maleimide resins for use in the adhesive composition are provided.
  • X 1 is an aliphatic or aromatic group.
  • exemplary X 1 entities include, poly(butadienes), poly(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether. These types of resins are commercially available and can be obtained, for example, from National Starch and Chemical Company and Dainippon Ink and Chemical, Inc.
  • the maleimide resin of the adhesive composition is 3- maleimidopropionic acid/dimethyioctanol adduct.
  • the maleimide resins are selected from the group consisting of in which C 36 represents a linear or branched chain (with or without cyclic moieties) of 36 carbon atoms;
  • Suitable acrylate resins include those having the generic structure
  • X 2 is an aromatic or aliphatic group.
  • exemplary X 2 entities include poiy(butadienes), poiy(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether.
  • Commercially available materials include butyl (meth)acrylate, isobuty!
  • the acrylate resins are selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, poly(butadiene) with acrylate functionality and poly(butadiene) with methacrylate functionality.
  • Suitable vinyl ether resins include those having the generic structure
  • n 1 to 6 and X is an aromatic or aliphatic group.
  • Exemplary X 3 entities include poly(butadienes), poly(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether.
  • resins include cyclohenanedimethanol divinylether, dodecylvinylether, cyclohexyl vinylether, 2-ethylhexyl vinylether, dipropyleneglycol divinylether, hexa ⁇ ediol divinylether, octadecylvinylether, and butandiol divinylether available from International Speciality Products (ISP); Vectomer 4010, 4020, 4030, 4040, 4051 , 4210, 4220, 4230, 4060, 5015 available from Sigma-Aldrich, Inc.
  • ISP International Speciality Products
  • Suitable poly(butadiene) resins include poly(butadie ⁇ es), epoxidized poly(butadienes), maleic poly(butadienes), acrylated poly(butadienes), butadiene- styrene copolymers, and butadiene-acrylonitrile copolymers.
  • Suitable epoxy resins include bisphenol, naphthalene, and aliphatic type epoxies.
  • Commercially available materials include bisphenol type epoxy resins (Epiclon 830LVP, 830CRP, 835LV, 850CRP) available from Dainippon Ink & Chemicals, Inc.; naphthalene type epoxy ⁇ Epiclon HP4032) available from Dainippon Ink & Chemicals, Inc.; aliphatic epoxy resins (Araldite CY179, 184, 192, 175, 179) available from Ciba Specialty Chemicals, (Epoxy 1234, 249, 206) available from Union Carbide Corporation, and (EHPE-3150) available from Daicel Chemical Industries, Ltd.
  • Epiclon 830LVP, 830CRP, 835LV, 850CRP available from Dainippon Ink & Chemicals, Inc.
  • naphthalene type epoxy ⁇ Epiclon HP4032 available from Dainippon
  • epoxy resins include cycloaltphatic epoxy resins, bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, epoxy novolac resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclope ⁇ tadiene-phenol type epoxy resins, reactive epoxy diluents, and mixtures thereof.
  • Suitable siliconized olefin resins are obtained by the selective hydrosilation reaction of silicone and divinyl materials, having the generic structure,
  • n 2 is 1 or more and n ! >n 2 -
  • These materials are commercially available and can be obtained, for example, from National Starch and Chemical Company.
  • Suitable silicone resins include reactive silicone resins having the generic structure
  • n 0 or any integer
  • X 5 are hydrogen, methyl, amine, epoxy, carboxyl, hydroxy, acrylate, methacrylate, mercapto, phenol, or vinyl functional groups
  • R 2 and R 3 can be -H, -CH 3 , vinyl, phenyl, or any hydrocarbon structure with more than two carbons.
  • Suitable styrene resins include those resins having the generic structure
  • n 1 or greater
  • R 4 is -H or -CH 3
  • X ⁇ is an aliphatic group.
  • Exemplary X 6 entities include poiy(butadie ⁇ es), poly(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether. These resins are commercially available and can be obtained, for example, from National Starch and Chemical Company or Sigma-Aldrich Co.
  • Suitable cyanate ester resins include those having the generic structure
  • n 1 or larger
  • X 7 is a hydrocarbon group.
  • X 7 entities include bisphenol, phenol or cresol novolac, dicyclopentadiene, polybutadiene, poiycarbonate, polyurethane, polyether, or polyester.
  • Commercially available materials include; AroCy L-10, AroCy XU366, AroCy XU371 , AroCy XU378, XU71787.02L, and XU 71787.07L, available from Huntsman LLC; Primaset PT30, Primaset PT30 S75, Primaset PT60, Primaset PT60S, Primaset BADCY, Primaset DA230S, Primaset MethylCy, and Primaset LECY, available from Lonza Group Limited; 2-al!yphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis(4- cya ⁇ atophe ⁇ ol)-1 , 1 ,1 ,3,3,3-hexafluoropropane, bisphenol A cyanate ester, dial
  • Suitable polymers for the adhesive composition further include polyamide, phenoxy, polybenzoxazine, acrylate, cyanate ester, bismaleimide, polyether sulfone, polyimide, benzoxazine, vinyl ether, siliconized olefin, polyoiefin, polybenzoxyzole, polyester, polystyrene, polycarbonate, polypropylene, polyvinyl chloride), polyisobutylene, polyacrylonitrile, poly(methyl methacrylate), polyvinyl acetate), poiy(2-vinylpridine), cis-1 ,4-polyisoprene, 3,4-polychloroprene, vinyl copolymer, poly(ethylene oxide), poly(ethylene glycol), polyformaldehyde, polyacetaldehyde, poly(b-propiolacetone), poly(10-decanoate), poly(ethylene terephthalate), polycaproJactam, po!y(1 1-und
  • suitable materials for inclusion in adhesive compositions include rubber polymers such as block copolymers of monovinyl aromatic hydrocarbons and conjugated diene, e.g., styrene-butadiene, styrene-butadiene-styrene (SBS), styrene- isoprene-styrene (SIS), styrene-ethylene-butylene-styrene (SEBS), and styrene- ethylene-propylene-styrene (SEPS).
  • rubber polymers such as block copolymers of monovinyl aromatic hydrocarbons and conjugated diene, e.g., styrene-butadiene, styrene-butadiene-styrene (SBS), styrene- isoprene-styrene (SIS), styrene-ethylene-butylene-styrene (SEBS), and
  • Suitable materials for inclusion in adhesive compositions include ethylene-vinyl acetate polymers, other ethylene esters and copolymers, e.g., ethylene methacrylate, ethylene n-butyl acrylate and ethylene acrylic acid; polyolefi ⁇ s such as polyethylene and polypropylene; polyvinyl acetate and random copolymers thereof; polyacrylates; polyamides; polyesters; and polyvinyl alcohols and copolymers thereof.
  • Thermoplastic rubbers suitable for inclusion in the adhesive composition include carboxy terminated butadiene-nitrile (CTBN)/epoxy adduct, acrylate rubber, vinyl-terminated butadiene rubber, and nitriie butadiene rubber (NBR).
  • CTBN epoxy adduct consists of about 20-80 wt% CTBN and about 20-80 wt% diglycidyl ether bisphenol A: bisphenol A epoxy (DGEBA).
  • a variety of CTBN materials are available from Noveo ⁇ Inc., and a variety of bisphenol A epoxy materials are available from Dainippon Ink and Chemicals, Inc., and Shell Chemicals.
  • NBR rubbers are commercially available from Zeon Corporation.
  • Siloxanes suitable for inclusion in the adhesive formulation include elastomeric polymers comprising a backbone and pendant from the backbone at least one siloxane moiety that imparts permeability, and at least one reactive moiety capable of reacting to form a new covalent bond.
  • siloxanes examples include elastomeric polymers prepared from: 3-(tris(trimethylsilyloxy)silyl)-propyl methacrylate, n-butyl acrylate, glycidyl meth aery late, acryionitrile, and cyanoethyl acrylate; 3-(tris(trimethylsilyloxy)silyl)-propyl methacrylate, n-butyl acrylate, glycidyl methacrylate, and acryionitrile; and 3-(tris(trimethylsilyloxy)silyl)-propyl methacrylate, n-butyl acrylate, glycidyl methacrylate, and cyanoethyl acrylate.
  • curing agent is required for the adhesive composition, its selection is dependent on the polymer chemistry used and the processing conditions employed.
  • the curing agent for the resin system will be present in an effective amount, typically up to 60 wt% of the adhesive composition (excluding filler content).
  • the compositions may use aromatic amines, alycyclic amines, aliphatic amines, tertiary phosphines, triazines, metal salts, aromatic hydroxyl compounds, or a combination of these.
  • Such catalysts include imidazoles, such as 2- methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2- ethyl 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1 - cyanoethyl-2-methylimidazole, 1-cyanoethy!-2-ethy!-4-methylimidazole, 1-cyanoethyl- 2-undecylimidazole, 1 -cyanoethyl-2-phenylimidazole, 1 -guanaminoethyl-2- methyiimidazole and addition product of an imidazole and trimellitic acid; tertiary amines, such as N,N-dimethyl benzylamine, N,N-dimethylanitine, N 1 N- dimethyltoluidine, N,N-d
  • acid anhydrides such as carboxylic acid anhydride, maieic anhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride; hexahydropyromellitic anhydride and hexahydrotrimellitic anhydride, azo compounds, such as azoisobutylonitrile, 2,2'- azobispropane, m.m'-azoxystyrene, hydrozones, and mixtures thereof.
  • acid anhydrides such as carboxylic acid anhydride, maieic anhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride; hexahydropyromellitic anhydride and hexahydrotrimellitic anhydride
  • azo compounds such as azoisobutylonitrile, 2,
  • a curing agent is a cure accelerator and may be selected from the group consisting of triphenylphosphine, alkyl-substituted imidazoles, imidazolium salts, onium salts, quartenary phosphonium compounds, onium borates, metal chelates, 1 ,8-diazacycio[5.4.0]undex-7-ene or a mixture thereof.
  • the curing agent can be either a free radical initiator or an ionic initiator, depending on whether a radical or ionic curing resin is chosen. If a free radical initiator is used, it will be present in an effective amount. An effective amount typically is 0.1 to 10 wt%. of the adhesive composition (excluding any filler content).
  • Free-radical initiators include peroxides, such as butyl peroctoates and dicumyl peroxide, and azo compounds, such as 2,2'-azobis(2-methyl-propanenitrile) and 2,2'-azobis(2-methyl-butanenitrile).
  • an ionic initiator it will be present in an effective amount.
  • An effective amount typically is 0.1 to 10 wt% of the adhesive composition (excluding any filler content).
  • Suitable ionic curing agents include dicyandiamide, adipic dihydrazide, BF3-amine complexes, amine salts and modified imidazole compounds.
  • Metal compounds also can be employed as cure accelerators for cyanate ester systems and include, but are not limited to, metal napthenates, metal acetyl acetonates (chelates), metal octoates, metal acetates, metal halides, metal imidazole complexes, and metal amine complexes.
  • cure accelerators that may be included in the adhesive formulation include triphenylphosphine, alkyl-substituted imidazoles, imidazolium salts, and onium borates.
  • both ionic and free radical initiation may be desirable, in which case both free radical cure and ionic cure resins can be used in the composition.
  • These compositions would contain effective amounts of initiators for each type of resin. Such a composition would permit, for example, the curing process to be started by ionic initiation using LJV irradiation, and in a later processing step, to be completed by free radical initiation upon the application of heat.
  • fillers may be included in the adhesive composition and may be added to adjust numerous properties including rheology, stress, coefficient of thermal expansion, electrical and/or thermal conductivity, and modulus.
  • the particular type of filler is not critical to the present invention and can be selected by one skilled in the art to suit the needs of the specific end use.
  • Fillers may be conductive or nonconductive. Examples of suitable conductive fillers include carbon black, graphite, gold, silver, copper, platinum, palladium, nickel, aluminum, silicon carbide, boron nitride, diamond, and alumina.
  • nonconductive fillers examples include alumina, aluminum hydroxide, silica, vermiculite, mica, woilastonite, calcium carbonate, titania, sand, glass, barium sulfate, zirconium, carbon black, organic fillers, and halogenated ethylene polymers, such as, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, vinylidene chloride, and vinyl chloride.
  • the filler particles may be of any appropriate size ranging from nano size to several mils. The choice of such size for any particular package configuration is within the expertise of one skilled in the art. Filler may be present in an amount from 0 to 95 wt% of the total adhesive composition.
  • the adhesive formulation includes spacers, which are particles added for the purpose of controlling the bondline to a predetermined thickness. Selection of appropriate spacers will depend on the package configuration and adhesive formulation and may be made by one skilled in the art without undue experimentation. Suitable spacers include but are not limited to silver, silica, Teflon, polymeric or elastomeric materials. They may range in size from 25 to 150 microns and will be used in an effective amount. An effective amount typically is from 0.1 to 10 wt% of the adhesive composition (excluding filler content).
  • a coupling agent or adhesion promoter
  • Adhesion promoter selection will depend on the application requirements and resin chemistry employed. Adhesion promoters, if used, will be used in an effective amount: an effective amount is an amount up to 5 wt% of the adhesive composition (excluding filler content).
  • adhesion promoters examples include: epoxy-type silane coupling agent, amine-type silane coupling agent, mercapto-type silane coupling agent; Z6040 epoxy silane or Z6020 amine silane available from Dow Corning; A186 Silane, A187 Silane, A174 Silane, or A1289 available from OSl Silquest; Organosilane SI264 available from Degussa; Johoku Chemical CBT-1 Carbobenzotriazole available from Johoku Chemical; functional benzotriazoles; thiazoles; titanates; and zirconates.
  • a surfactant may be added to the adhesive composition.
  • Suitable surfactants include silicones, polyethylene glycol, polyoxyethylene/polyoxypropylene block copolymers, ethylene diamine based polyoxyethylene/polyoxypropylene block copolymers, polyol-based polyoxyalkylenes, fatty alcohol-based polyoxyalkylenes, and fatty alcohol poiyoxyalkylene alkyl ethers.
  • Surfactants, if used, will be used in an effective amount: a typical effective amount is an amount up to 5 wt% of the adhesive composition (excluding filler content).
  • a wetting agent may be included in the adhesive composition.
  • Wetting agent selection will depend on the application requirements and the resin chemistry utilized. Wetting agents, if used, will be used in an effective amount: a typical effective amount is up to 5 wt% (excluding filler content).
  • wetting agents examples include Fluorad FC-4430 Fluorosurfactant available from 3M, Clariant Fluowet OTN, BYK W-990, Surfynol 104 Surfactant, Crompton Silwet L-7280, Triton X100 available from Rhom and Haas, Propylene glycol with a preferable Mw greater than 240, Gama-Butyrolactone, castor oil, glycerin or other fatty acids, and silanes.
  • a flow control agent may be included in the adhesive composition.
  • Flow control agent selection will depend on the application requirements and resin chemistry employed.
  • Flow control agents, if used, will be present in an effective amount: an effective amount is an amount up to 20 wt% of the adhesive composition (excluding filler content).
  • suitable flow control agents include Cab-O-Sii TS720 available from Cabot, Aerosil R202 or R972 available from Degussa, fumed silicas, fumed aluminas, or fumed metal oxides.
  • an air release agent may be added to the adhesive composition.
  • Air release agent selection will depend on the application requirements and resin chemistry employed. Air release agents, if used, will be used in an effective amount. A typical effective amount will be up to 5% wt% of the adhesive composition (excluding fiiier content). Examples of suitable air release agents include Antifoam 1400 available from Dow Corning, DuPont Modoflow, and BYK A-510.
  • these compositions are formulated with tackifying resins in order to improve adhesion and introduce tack;
  • tackifying resins include naturally-occurring resins and modified naturally-occurring resins; polyterpene resins; phenolic modified terpene resins; coumarons-indene resins; aliphatic and aromatic petroleum hydrocarbon resins; phthalate esters; hydrogenated hydrocarbons, hydrogenated rosins and hydrogenated rosin esters.
  • Tackifying resins if used, will be used in an effective amount. A typical effective amount will be up to 5 wt% of the adhesive composition (excluding filler content).
  • diluents such as liquid polybutene or polypropylene
  • petroleum waxes such as paraffin and microcrystalline waxes, poiyethylene greases, hydrogenated animal, fish and vegetable fats, mineral oil and synthetic waxes, naphthenic or paraffinic mineral oils.
  • additives such as stabilizers, antioxidants, impact modifiers, and colorants, in types and amounts known in the art, may also be added to the adhesive composition.
  • Common solvents with a proper boiling point ranging from 25 0 C to 230 °C may be used in the adhesive composition.
  • suitable solvents include ketones, esters, alcohols, ethers, and other common solvents that are stable and dissolve the resins in the composition.
  • Suitable solvents include ⁇ - butyrolactone, propylene glycol methyl ethyl acetate (PGMEA), and 4-methyl-2- pentanone.
  • the adhesive composition After the adhesive composition is applied to a substrate, which may include a silicon die, it may be dried and/or B-staged in an optional process step.
  • the adhesive is hardened to a non-tacky state so that the substrate, silicon wafer, or silicon die may be stored and/or sent to a separate location before the semiconductor die is attached.
  • the adhesive is hardened sufficiently to enable the adhesive-coated substrates, dies, or wafers, to be stacked on top of one another and stored without the use of interleafs.
  • the hardening of the adhesive may be accomplished in numerous ways, depending on the adhesive formulation employed.
  • the adhesive composition is thermoplastic and applied at a temperature above its melting point such that it is in a flow-able state.
  • the adhesive composition is hardened by cooling it below its melting point and/or softening point.
  • the adhesive composition comprises at least a liquid thermoset resin and a solvent.
  • the adhesive is hardened to a non-tacky, or very low-flow, state, by heating the adhesive and substrate sufficiently to evaporate the solvent and partia ⁇ y cure the thermoset resin or resins.
  • the adhesive contains a solid thermoset resin dissolved in a solvent. After application to the substrate the adhesive will be hardened to a non-tacky, or very low flow, state by heating the adhesive and substrate sufficiently to evaporate the solvent, leaving a non-tacky thermoset resin coating on the substrate.
  • the adhesive contains at least one liquid thermoset resin. After application to the substrate the adhesive will be hardened to a non-tacky, or very low flow, state by heating the adhesive and substrate sufficiently to partially advance the thermoset resin to a non-tacky, or very low flow, state.
  • the adhesive might also contain a combination of resins that could be dried, B-staged, and cured with a combination of mechanisms.
  • the formulation might be B-staged through the use of ultraviolet radiation and, in a downstream manufacturing step after die attach, cured through the use of heat.
  • the formulation might also contain a combination of resins that have two separate cure temperatures such that the adhesive could be hardened by heating the substrate at the first (and lower) temperature, causing the first resin to cure and the overall adhesive formulation to harden to a non-tacky state.
  • the second resin which has a second (and higher) curing temperature, would be cured in a subsequent processing step after the die is attached.
  • the cure may be accomplished either as an individual process step, or in conjunction with another processing operation such as solder reflow or wire bonding.
  • the B-staging temperature will generally be within a range of 8O 0 C to 200 0 C, and B-staging will be effected within a time period ranging from one minute to two hours, depending on the particular adhesive formulation chosen.
  • the time and temperature B-staging profile for each adhesive composition will vary, and different compositions can be designed to provide the B- staging profile that will be suited to the particular industrial manufacturing process.
  • the adhesive is not hardened prior to die attach.
  • the die is mounted onto the substrate while the adhesive is still in a flow- able state. This would enable the formation of a fillet around the die when the die is pressed into the adhesive.
  • the flow of the adhesive and the pressure used to mount the die may be tailored to give the desired amount of fillet for each specific package design. In this embodiment care must be taken to avoid flow of the adhesive into the opening in the substrate, as this would interfere with wire bonding.
  • the adhesive of the present invention may be used to bond any two articles together and is particularly useful in adhering a semiconductor die to a metal substrate, or to an organic substrate which has exposed metal (such as copper circuits) on its surface.
  • the metal surface may be any suitable for use in the particular industrial use of interest including but not limited to copper, silver, stainless steel, Alloy 42, nickel, any solder, or a pre-plated finish (PPF) such as Ni/Pd/Au, either with or without silver strike on top.
  • PPF pre-plated finish
  • the semiconductor die may be any type, size, or shape, as it is not critical to the present invention.
  • the bondline (thickness of adhesive after cure) of the assembly may be any thickness suitable for the specific semiconductor package and typically will range between 10 and 150 ⁇ m.
  • a variety of porphyrin derivatives were tested in a model adhesive formulation, and compared to a similar formulation that contained no porphyrin derivative, in order to identify the molecular features that would provide improved adhesion.
  • the model formulation is listed in Table 1 , below.
  • the composition (excluding filler) was as follows 19 6 wt% oligomer, 78 4 wt% diacrylate, 0 98 wt% silane, 0 098 wt% inhibitor, 0 98 wt% initiator
  • the composition with filler was as follows 4 0 wt% oligomer, 15 9 wt% diacrylate, 0 2 wt% silane, 0 02 wt% inhibitor, 0 2 wt% initiator, and 79 7 wt% silver
  • Each formulation was used to attach 300 x 300 mil silicon die to a bare copper lead frame, with a bond fine thickness of 25 ⁇ m
  • the assemblies were then cured in nitrogen with a 30 minute ramp from room temperature to 175 0 C plus a 30 minute hold at 175 0 C Following cure the specimens were subjected
  • adhesion strength improvement may be tailored to meet the requirements of a specific application by varying the amount of porphyrin derivative included in the formulation. It should be noted that the amount of porphyrin derivative required to yield a specific improvement in adhesion will vary, depending on the specific resin system, porphyrin derivative, and metal substrate employed.
  • EXAMPLE 3 EFFECT OF RESIN CHEMISTRY.
  • Protoporphyrin IX was added to formulations using epoxy, acrylate, and maleimide, and their die shear strength was tested.
  • ABLEBOND 84-1 LMISR4 is an epoxy-based die attach adhesive commercially available from Ablestik Laboratories.
  • Analogous comparative formulations which contained no porphyrin derivative were also tested to determine whether the porphyrin derivative was effective in improving adhesion for a variety of resin systems.
  • Each formulation was used to build assemblies according to the protocol described in Example 1. The assemblies were also cured, thermally conditioned, and tested for die shear strength at 27O 0 C according to the protocol described in Example 1.
  • Formulation compositions and DSS at 27O 0 C are listed in Tables 5-7.
  • the Protoporphyrin IX was effective in improving the adhesion of the epoxy- based formulation, the acrylate-based formulation, and the maleimide-based formulation.
  • EXAMPLE 4 EFFECT OF METAL SURFACE.
  • Inventive Formulation Q and Comparative Formulation N were used to bond silicon die to pre-plated finish (PPF) lead frames, to determine the effectiveness of the inventive formulation on that surface.
  • PPF pre-plated finish
  • Each formulation was used to build assemblies according to the protocol described in Example 1. The assemblies were also cured, thermally conditioned, and tested for die shear strength at 27O 0 C according to the protocol described in Example 1. Results are summarized in Table 8 and show that the presence of Protooporphyrin IX improved adhesion to the PPF lead frame.

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Abstract

An adhesive composition includes a curable resin and a porphyrin derivative, in which the porphyrin derivative has at least one carboxylic acid group that is typically pendant from the porphyrin ring. In another embodiment, this invention is a method for improving adhesion of an adhesive composition to a metal substrate in which a porphyrin derivative is added to a resin, wherein the porphyrin derivative has at least one carboxylic acid group pendant from the porphyrin ring. In a third embodiment, this invention is an assembly in which a semiconductor die is mounted on a metal substrate using an adhesive composition that contains a porphyrin derivative that has at least one carboxyfic acid group. In one embodiment the porphyrin derivative is Protoporphyrin IX, having the structure (I).

Description

COMPOSITION CONTAINING PORPHYRIN TO IMPROVE ADHESION
FIELD OF THE INVENTION
[0001] This invention relates to adhesive compositions, methods for improving adhesion to metal substrates, and assemblies of semiconductor dies joined to metal substrates using adhesive compositions using porphyrin.
BACKGROUND OF THE INVENTION
[0002] Typically, semiconductor dies are attached to metal substrates, such as lead frames, using resin-based adhesives. These adhesives utilize a variety of resin chemistries and serve to hold the die to the metal lead frame during attachment of the semiconductor package to a circuit board, solder reflow, and throughout the use of the package in its end application. As semiconductor packaging technology has evolved, the requirements for the adhesive have similarly changed. In recent years, there has been a growing need for adhesives that can withstand re-flow temperatures up to 27O0C. Good adhesion at this high temperature has proven very difficult to attain with existing formuiations and there is a need for an adhesive composition that would give improved adhesion to metal surfaces, especially at elevated temperatures. This and other needs are addressed by the various embodiments and configurations of the present invention.
SUMMARY OF THE INVENTION
[0003] In one embodiment this invention is an adhesive composition (hereinafter also referred to as an adhesive) that comprises a curable resin and a prophyrin derivative that has at least one carboxylic acid functional group. In a second embodiment this invention is a method of improving the adhesion of an adhesive composition comprising (i) providing a curable resin and (ii) adding to the resin a porphyrin derivative that has at least one carboxylic acid functional group. In a third embodiment this invention is an assembly comprising a metal substrate, a semiconductor die mounted thereon, and an adhesive composition disposed between the metal substrate and semiconductor die wherein the adhesive composition comprises (i) a curable resin and (ii) a porphyrin derivative that has at least one carboxylic acid functional group.
DEFINITIONS
[0004] The term "alkyl" as used herein refers to a branched or un-branched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl ("Me"), ethyl ("Et"), n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like.
[0005] The term "effective amount" of a compound, product, or composition as used herein is meant a sufficient amount of the compound, product or composition to provide the desired results. As will be pointed out below, the exact amount required will vary from package to package, depending on the particular compound, product or composition used, its mode of administration, and the like. Thus, it is not aiways possible to specify an exact amount; however, an effective amount may be determined by one of ordinary skill in the art using only routine experimentation.
[0006] As used herein, the term "suitable" refers to a moiety that is compatible with the compounds, products, or compositions as provided herein for the stated purpose. Suitability for the stated purpose may be determined by one of ordinary skill in the art using only routine experimentation.
[0007] As used herein, "substituted" is used to refer, generally, to a carbon or suitable heteroatom having a hydrogen atom or other atom removed and replaced with a further moiety. Moreover, it is intended that "substituted" refer to substitutions which do not change the basic and novel utility of the underlying compounds, products or compositions of the present invention.
[0008] As used herein, the term "B-staging" (and its variants) is used to refer to the processing of a material by heat or irradiation so that if the material is dissolved or dispersed in a solvent, the solvent is evaporated off with or without partial curing of the material, or if the material is neat with no solvent, the material is partially cured to a tacky or more hardened state. If the material is a flow-able adhesive, B-staging will provide extremely low flow without fully curing, such that additional curing may be performed after the adhesive is used to join one article to another. The reduction in flow may be accomplished by evaporation of a solvent, partial advancement or curing of a resin or polymer, or both. [0009] As used herein the term "curing agent" is used to refer to any material or combination of materials that initiate, propagate, or accelerate cure of the composition and includes but is not limited to accelerators, catalysts, initiators, and hardeners
[0010] As used herein, the term "porphyrin" is a herterocyclic macrocycle made from four pyrrole subunits linked on opposite sides (α position) through four methiπe bridges (=CH-), and has the following structure
Figure imgf000004_0001
[001 1] As used herein the terms "porphine", "porphin", and "porphyrin" are used interchangeably and have the same meaning, as specified above
[0012] As used herein the terms "free porphyrin", "free porphin", and "free porphine" are used to refer to a porphyrin that does not have any meta! ions or atoms bound to the nitrogens in the center
DETAILED DESCRIPTION OF THE INVENTION
[0013] The porphyrin derivative of the present invention is characterized by having at least one carboxylic acid functional group, typically pendant from the porphyrin ring The presence of both the porphyrin ring and the carboxylic acid functionality gives improved adhesion over porphyrin rings without the carboxylic acid functionality Carboxylic acid functionality, with its polar nature, is known for improving adhesion in adhesive formulations Porphyrin rings are used extensively as chelating agents, as they have a propensity for coordinating with metal ions and metal atoms In the present invention, adhesion strength has been found to improve when and if both the porphyrin ring structure and the carboxylic acid functionalities are present and available for chemical interaction (ι e they are not bound) The acid functionality and the pophyrin ring work together to give an unexpected, synergistic effect in improving bonding to metal surfaces.
[0014] An example of a porphyrin derivative containing at least one carboxylic acid functional group is:
Figure imgf000005_0001
[0015] Optionally, the porphyrin derivative may further have at least one reactive double bond pendant from the porphyrin ring. The reactive double bond, combined with the carboxylic acid functionality on the porphyrin ring, provides further enhanced adhesive strength. It is theorized that the double bond participates in the polymerization reaction during cure of the curable resin and that the porphyrin ring becomes part of the polymer matrix. The result is a polymeric structure that has a porphyrin ring with carboxylic acid functionality pendant from the polymer. These two functions, the porphyrin ring and the carboxylic acid, act synergistically to bond the adhesive to the metal. Because the porphyrin and carboxylic acid functionalities are a part of the polymer matrix the adhesion improvement is more pronounced than when those functionalities are simply mixed into the adhesive formulation.
[0016] An example of a porphyrin derivative containing at least one reactive double bond in addition to at least one carboxylic acid functional group is:
Figure imgf000005_0002
[0017] The porphyrin derivative should be a free pophyrin, that is, it should not have any meta! ions or atoms bound to the nitrogens in the center to block the nitrogen from bonding to a metal substrate. For the same reasons, a composition containing the porphyrin derivative should not include any free acid molecules, as these can protonate the nitrogens in the prophyrin ring, making the nitrogen unavailable for bonding to the metal substrate. In both these cases, adhesion to the metal would be inhibited.
[0018] The porphyrin derivative is present in the adhesive composition in an effective amount. An effective amount will vary depending on the resin system selected, but will typically range between 0.25 and 3.0 wt% of the adhesive formulation, excluding filler content.
[0019] The adhesive composition will contain at least one curable resin. Curable resins suitable for use in the present invention include any that polymerize to cure and that provide the desired rheology, modulus, coefficient of thermal expansion, and other properties required for the specific industrial application. The resin(s) may be polymers, oligomers, monomers, pre-polymers, or a combination of these. Suitable resins include thermoplastics, thermosets, elastomers, thermoset rubbers, or a combination of these.
[0020] If the composition is to be used as a die attach adhesive election of a suitable resin or resin combination is dependent upon the die type and size, the substrate type, package geometry, and such downstream manufacturing variables as reflow temperatures and reliability required. The adhesive composition may or may not contain solvent, as deemed by the practitioner to be suitable for the particular industrial use. The polymer or curabie resin will generally be a major component, excluding any fillers present. Other components, typically used in adhesive compositions, may be added at the option of the practitioner; such other components include, but are not limited to, curing agents, fluxing agents, wetting agents, flow control agents, adhesion promoters (in addition to the porphyrin derivative), and air release agents. The adhesive composition may also contain filler, in which case the filler will be present in an amount up to 95% of the total composition.
[0021] Resins and polymers used in the adhesive may be solid, liquid, or a combination of the two. Suitable curabie resins include epoxies, acrylates or methacrylates, maleimides, vinyl ethers, polyesters, poly(butadienes), polyimides, benzocyclobutene, siliconized olefins, silicone resins, styrene resins, cyanate ester resins, polyolefins, or siloxanes. The resin will be present in an effective amount, typically between 5 and 100 wt% of the adhesive composition, excluding filler content
[0022] In one embodiment, solid aromatic bismaleimide (BMI) resin powders are included in the adhesive. Suitable solid BMI resins are those having the structure
Figure imgf000007_0001
in which X is an aromatic group; exemplary aromatic groups include:
Figure imgf000007_0002
Figure imgf000008_0001
in which n is 1 - 3
Figure imgf000008_0002
[0023] Bismaleimide resins having these X bridging groups are commercially available, and can be obtained, for example, from Sartomer (USA) or HOS-Technic GmbH (Austria).
[0024] In another embodiment, maleimide resins for use in the adhesive composition
include those having the generic structure
Figure imgf000008_0003
which n is 1 to 3 and X1 is an aliphatic or aromatic group. Exemplary X1 entities include, poly(butadienes), poly(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether. These types of resins are commercially available and can be obtained, for example, from National Starch and Chemical Company and Dainippon Ink and Chemical, Inc.
[0025] In one embodiment the maleimide resin of the adhesive composition is 3- maleimidopropionic acid/dimethyioctanol adduct.
[0026] In a further embodiment, the maleimide resins are selected from the group consisting of
Figure imgf000009_0001
in which C36 represents a linear or branched chain (with or without cyclic moieties) of 36 carbon atoms;
Figure imgf000009_0002
[0027] Suitable acrylate resins include those having the generic structure
Figure imgf000009_0003
which n is 1 to 6, R1 is -H or -CH3. and X2 is an aromatic or aliphatic group. Exemplary X2 entities include poiy(butadienes), poiy(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether. Commercially available materials include butyl (meth)acrylate, isobuty! (meth)acryiate, tricyclodecanedimethanol diacrylate, 2-ethyl hexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, alkyl (meth)acrylate, tridecy! (meth)acrylate, n-stearyl (meth)acrylate, cyclohexyl(meth)acrylate, tetrahydrofurfuryl(meth)acryjate, 2-phenoxy ethyl(meth)acrylate, isobornyl(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1.6 hexanediol di(meth)acrylate, 1 ,9-nonandiol di(meth)acrylate, perfluorooctylethyl(meth)acrylate, 1 ,10 decandiol di(meth)acrylate, nonylphenol polypropoxylate (meth)acrylate, and polypentoxylate tetrahydrofurfuryl acrylate, available from Kyoeisha Chemical Co., LTD; polybutadieπe urethane dimethacrylate (CN302, NTX6513) and polybutadiene dimethacrylate (CN301 , NTX6039, PRO6270) available from Sartomer Company, Inc; polycarbonate urethane diacrylate (ArtResin UN9200A) available from Negami Chemical Industries Co., LTD; acrylated aliphatic urethane oligomers (Ebecryl 230, 264, 265, 270,284, 4830, 4833, 4834, 4835, 4866, 4881 , 4883, 8402, 8800-20R, 8803, 8804) available from Radcure Specialities, Inc; polyester acrylate oligomers (Ebecryl 657, 770, 810, 830, 1657, 1810, 1830) available from Radcure Specialities, Inc.; and epoxy acrylate resins (CN104, 11 1 , 1 12, 115, 116, 117, 118, 119, 120, 124, 136) available from Sartomer Company, Inc. In one embodiment the acrylate resins are selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, poly(butadiene) with acrylate functionality and poly(butadiene) with methacrylate functionality.
[0028] Suitable vinyl ether resins include those having the generic structure
Figure imgf000010_0001
in which n is 1 to 6 and X is an aromatic or aliphatic group.
Exemplary X3 entities include poly(butadienes), poly(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether. Commercially available resins include cyclohenanedimethanol divinylether, dodecylvinylether, cyclohexyl vinylether, 2-ethylhexyl vinylether, dipropyleneglycol divinylether, hexaπediol divinylether, octadecylvinylether, and butandiol divinylether available from International Speciality Products (ISP); Vectomer 4010, 4020, 4030, 4040, 4051 , 4210, 4220, 4230, 4060, 5015 available from Sigma-Aldrich, Inc.
[0029] Suitable poly(butadiene) resins include poly(butadieπes), epoxidized poly(butadienes), maleic poly(butadienes), acrylated poly(butadienes), butadiene- styrene copolymers, and butadiene-acrylonitrile copolymers. Commercially available materials include homopolymer butadiene (Ricon130, 131 , 134, 142, 150, 152, 153, 154, 156, 157, P30D) available from Sartomer Company, Inc; random copolymer of butadiene and styrene (Ricon 100, 181 , 184) available from Sartomer Company Inc.; maleinized poly(butadiene) (Ricon 130MA8, 130MA13, 130MA20, 131 MA5, 131 MA10, 131 MA17, 131 MA20, 156MA17) available from Sartomer Company, Inc.; acryiated poly(butadienes) (CN302, NTX6513, CN301 , NTX6039, PRO6270, Ricacryl 3100, Ricacryl 3500) available from Sartomer Inc.; epoxydized poly(butadienes) (Polybd 600, 605) available from Sartomer Company. Inc. and Epolead PB3600 available from Daicel Chemical Industries, Ltd; and acrylonttrile and butadiene copolymers (Hycar CTBN series, ATBN series, VTBN series and ETBN series) available from Hanse Chemical.
[0030] Suitable epoxy resins include bisphenol, naphthalene, and aliphatic type epoxies. Commercially available materials include bisphenol type epoxy resins (Epiclon 830LVP, 830CRP, 835LV, 850CRP) available from Dainippon Ink & Chemicals, Inc.; naphthalene type epoxy {Epiclon HP4032) available from Dainippon Ink & Chemicals, Inc.; aliphatic epoxy resins (Araldite CY179, 184, 192, 175, 179) available from Ciba Specialty Chemicals, (Epoxy 1234, 249, 206) available from Union Carbide Corporation, and (EHPE-3150) available from Daicel Chemical Industries, Ltd. Other suitable epoxy resins include cycloaltphatic epoxy resins, bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, epoxy novolac resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopeπtadiene-phenol type epoxy resins, reactive epoxy diluents, and mixtures thereof.
[0031] Suitable siliconized olefin resins are obtained by the selective hydrosilation reaction of silicone and divinyl materials, having the generic structure,
Figure imgf000011_0001
is 2 or more, n2 is 1 or more and n!>n2- These materials are commercially available and can be obtained, for example, from National Starch and Chemical Company.
[0032] Suitable silicone resins include reactive silicone resins having the generic structure
Figure imgf000012_0001
in which n is 0 or any integer, X4 and
X5 are hydrogen, methyl, amine, epoxy, carboxyl, hydroxy, acrylate, methacrylate, mercapto, phenol, or vinyl functional groups, R2 and R3 can be -H, -CH3, vinyl, phenyl, or any hydrocarbon structure with more than two carbons. Commercially available materials include KF8012, KF8002, KF8003, KF-1001 , X-22-3710, KF6001 , X-22-164C, KF2001 , X-22-170DX, X-22-173DX, X-22-174DX X-22-176DX, KF-857, KF862, KF8001 , X-22-3367, and X-22-3939A available from Shin-Etsu Silicone International Trading (Shanghai) Co., Ltd.
[0033] Suitable styrene resins include those resins having the generic structure
Figure imgf000012_0002
in which n is 1 or greater, R4 is -H or -CH3, and Xβ is an aliphatic group. Exemplary X6 entities include poiy(butadieπes), poly(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether. These resins are commercially available and can be obtained, for example, from National Starch and Chemical Company or Sigma-Aldrich Co.
[0034] Suitable cyanate ester resins include those having the generic structure
( N≡C- OH — x7
\ Λi in which n is 1 or larger, and X7 is a hydrocarbon group. Exemplary
X7 entities include bisphenol, phenol or cresol novolac, dicyclopentadiene, polybutadiene, poiycarbonate, polyurethane, polyether, or polyester. Commercially available materials include; AroCy L-10, AroCy XU366, AroCy XU371 , AroCy XU378, XU71787.02L, and XU 71787.07L, available from Huntsman LLC; Primaset PT30, Primaset PT30 S75, Primaset PT60, Primaset PT60S, Primaset BADCY, Primaset DA230S, Primaset MethylCy, and Primaset LECY, available from Lonza Group Limited; 2-al!yphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis(4- cyaπatopheπol)-1 , 1 ,1 ,3,3,3-hexafluoropropane, bisphenol A cyanate ester, diallylbisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1 ,1 ,1-tris(4- cyanatophenyl)ethane, 4-cumylphenol cyanate ester, 1 ,1-bis(4- cyaπateophenyl)ethane, 2,2, 3,4,4,5,5,6, 6, 7, 7-dodecafluorooctanediol dicyanate ester, and 4,4'-bisphenol cyanate ester, available from Oakwood Products, Inc.
[0035] Suitable polymers for the adhesive composition further include polyamide, phenoxy, polybenzoxazine, acrylate, cyanate ester, bismaleimide, polyether sulfone, polyimide, benzoxazine, vinyl ether, siliconized olefin, polyoiefin, polybenzoxyzole, polyester, polystyrene, polycarbonate, polypropylene, polyvinyl chloride), polyisobutylene, polyacrylonitrile, poly(methyl methacrylate), polyvinyl acetate), poiy(2-vinylpridine), cis-1 ,4-polyisoprene, 3,4-polychloroprene, vinyl copolymer, poly(ethylene oxide), poly(ethylene glycol), polyformaldehyde, polyacetaldehyde, poly(b-propiolacetone), poly(10-decanoate), poly(ethylene terephthalate), polycaproJactam, po!y(1 1-undecanoamide), poly(m-phenylene-terephthalamide), poly(tetramethlyene-m-benzenesulfonamide), polyester polyarylate, poly(phenylene oxide), poly(phenylene sulfide), polysulfone, polyimide, polyetheretherketone, polyetherimide, fluorinated polyimide, polyimide siloxane, poly-iosindolo- quinazolinedione, polythioetherimide poly-phenyl-quinoxaline, polyquinixalone, imide- aryl ether phenylquinoxaline copolymer, polyquinoxaline, polybenzimidazole, polybenzoxazole, polynorbornene, poly(arylene ethers), polysilane, parylene, benzocyclobutenes, hydroxy(benzoxazole) copolymer, po!y(silarylene siloxanes), and polybenzimidazole.
[0036] Other suitable materials for inclusion in adhesive compositions include rubber polymers such as block copolymers of monovinyl aromatic hydrocarbons and conjugated diene, e.g., styrene-butadiene, styrene-butadiene-styrene (SBS), styrene- isoprene-styrene (SIS), styrene-ethylene-butylene-styrene (SEBS), and styrene- ethylene-propylene-styrene (SEPS).
[0037] Other suitable materials for inclusion in adhesive compositions include ethylene-vinyl acetate polymers, other ethylene esters and copolymers, e.g., ethylene methacrylate, ethylene n-butyl acrylate and ethylene acrylic acid; polyolefiπs such as polyethylene and polypropylene; polyvinyl acetate and random copolymers thereof; polyacrylates; polyamides; polyesters; and polyvinyl alcohols and copolymers thereof.
[0038] Thermoplastic rubbers suitable for inclusion in the adhesive composition include carboxy terminated butadiene-nitrile (CTBN)/epoxy adduct, acrylate rubber, vinyl-terminated butadiene rubber, and nitriie butadiene rubber (NBR). In one embodiment the CTBN epoxy adduct consists of about 20-80 wt% CTBN and about 20-80 wt% diglycidyl ether bisphenol A: bisphenol A epoxy (DGEBA). A variety of CTBN materials are available from Noveoπ Inc., and a variety of bisphenol A epoxy materials are available from Dainippon Ink and Chemicals, Inc., and Shell Chemicals. NBR rubbers are commercially available from Zeon Corporation.
[0039] Siloxanes suitable for inclusion in the adhesive formulation include elastomeric polymers comprising a backbone and pendant from the backbone at least one siloxane moiety that imparts permeability, and at least one reactive moiety capable of reacting to form a new covalent bond. Examples of suitable siloxanes include elastomeric polymers prepared from: 3-(tris(trimethylsilyloxy)silyl)-propyl methacrylate, n-butyl acrylate, glycidyl meth aery late, acryionitrile, and cyanoethyl acrylate; 3-(tris(trimethylsilyloxy)silyl)-propyl methacrylate, n-butyl acrylate, glycidyl methacrylate, and acryionitrile; and 3-(tris(trimethylsilyloxy)silyl)-propyl methacrylate, n-butyl acrylate, glycidyl methacrylate, and cyanoethyl acrylate.
[0040] If curing agent is required for the adhesive composition, its selection is dependent on the polymer chemistry used and the processing conditions employed. The curing agent for the resin system will be present in an effective amount, typically up to 60 wt% of the adhesive composition (excluding filler content). As curing agents, the compositions may use aromatic amines, alycyclic amines, aliphatic amines, tertiary phosphines, triazines, metal salts, aromatic hydroxyl compounds, or a combination of these. Examples of such catalysts include imidazoles, such as 2- methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2- ethyl 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1 - cyanoethyl-2-methylimidazole, 1-cyanoethy!-2-ethy!-4-methylimidazole, 1-cyanoethyl- 2-undecylimidazole, 1 -cyanoethyl-2-phenylimidazole, 1 -guanaminoethyl-2- methyiimidazole and addition product of an imidazole and trimellitic acid; tertiary amines, such as N,N-dimethyl benzylamine, N,N-dimethylanitine, N1N- dimethyltoluidine, N,N-dimethyl-p-anisidine, p-halogeno-N.N-dimethyianiline, 2-N- ethylanilino ethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholiπe, triethaπolamiπe, triethylenediamine, N.N.N'.N'-tetramethylbutanediamine, N- methyipiperidine; phenols, such as phenol, cresol, xylenol, resorcine, and phloroglucin; organic metal salts, such as lead naphthenate, lead stearate, zinc naphthenate, zinc octolate, tin oleate, dibutyl tin maleate, manganese naphthenate, cobalt naphthenate, and acetyl aceton iron; and inorganic metal salts, such as stannic chloride, zinc chloride and aluminum chloride; peroxides, such as benzoyl peroxide, lauroy! peroxide, octanoyl peroxide, acetyl peroxide, para-chlorobenzoyl peroxide and di-t-butyl diperphthalate, acid anhydrides, such as carboxylic acid anhydride, maieic anhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride; hexahydropyromellitic anhydride and hexahydrotrimellitic anhydride, azo compounds, such as azoisobutylonitrile, 2,2'- azobispropane, m.m'-azoxystyrene, hydrozones, and mixtures thereof.
[0041] In another embodiment, a curing agent is a cure accelerator and may be selected from the group consisting of triphenylphosphine, alkyl-substituted imidazoles, imidazolium salts, onium salts, quartenary phosphonium compounds, onium borates, metal chelates, 1 ,8-diazacycio[5.4.0]undex-7-ene or a mixture thereof.
[0042] In another embodiment the curing agent can be either a free radical initiator or an ionic initiator, depending on whether a radical or ionic curing resin is chosen. If a free radical initiator is used, it will be present in an effective amount. An effective amount typically is 0.1 to 10 wt%. of the adhesive composition (excluding any filler content). Free-radical initiators include peroxides, such as butyl peroctoates and dicumyl peroxide, and azo compounds, such as 2,2'-azobis(2-methyl-propanenitrile) and 2,2'-azobis(2-methyl-butanenitrile).
[0043] If an ionic initiator is used, it will be present in an effective amount. An effective amount typically is 0.1 to 10 wt% of the adhesive composition (excluding any filler content). Suitable ionic curing agents include dicyandiamide, adipic dihydrazide, BF3-amine complexes, amine salts and modified imidazole compounds.
[0044] Metal compounds also can be employed as cure accelerators for cyanate ester systems and include, but are not limited to, metal napthenates, metal acetyl acetonates (chelates), metal octoates, metal acetates, metal halides, metal imidazole complexes, and metal amine complexes.
[0045] Other cure accelerators that may be included in the adhesive formulation include triphenylphosphine, alkyl-substituted imidazoles, imidazolium salts, and onium borates.
[0046] !n some cases, it may be desirable to use more than one type of cure for the adhesive composition. For example, both ionic and free radical initiation may be desirable, in which case both free radical cure and ionic cure resins can be used in the composition. These compositions would contain effective amounts of initiators for each type of resin. Such a composition would permit, for example, the curing process to be started by ionic initiation using LJV irradiation, and in a later processing step, to be completed by free radical initiation upon the application of heat.
[0047] One or more fillers may be included in the adhesive composition and may be added to adjust numerous properties including rheology, stress, coefficient of thermal expansion, electrical and/or thermal conductivity, and modulus. The particular type of filler is not critical to the present invention and can be selected by one skilled in the art to suit the needs of the specific end use. Fillers may be conductive or nonconductive. Examples of suitable conductive fillers include carbon black, graphite, gold, silver, copper, platinum, palladium, nickel, aluminum, silicon carbide, boron nitride, diamond, and alumina. Examples of suitable nonconductive fillers include alumina, aluminum hydroxide, silica, vermiculite, mica, woilastonite, calcium carbonate, titania, sand, glass, barium sulfate, zirconium, carbon black, organic fillers, and halogenated ethylene polymers, such as, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, vinylidene chloride, and vinyl chloride. The filler particles may be of any appropriate size ranging from nano size to several mils. The choice of such size for any particular package configuration is within the expertise of one skilled in the art. Filler may be present in an amount from 0 to 95 wt% of the total adhesive composition.
[0048] In one embodiment the adhesive formulation includes spacers, which are particles added for the purpose of controlling the bondline to a predetermined thickness. Selection of appropriate spacers will depend on the package configuration and adhesive formulation and may be made by one skilled in the art without undue experimentation. Suitable spacers include but are not limited to silver, silica, Teflon, polymeric or elastomeric materials. They may range in size from 25 to 150 microns and will be used in an effective amount. An effective amount typically is from 0.1 to 10 wt% of the adhesive composition (excluding filler content).
[0049] In another embodiment, a coupling agent, or adhesion promoter, may be added to the adhesive composition. Adhesion promoter selection will depend on the application requirements and resin chemistry employed. Adhesion promoters, if used, will be used in an effective amount: an effective amount is an amount up to 5 wt% of the adhesive composition (excluding filler content). Examples of suitable adhesion promoters include: epoxy-type silane coupling agent, amine-type silane coupling agent, mercapto-type silane coupling agent; Z6040 epoxy silane or Z6020 amine silane available from Dow Corning; A186 Silane, A187 Silane, A174 Silane, or A1289 available from OSl Silquest; Organosilane SI264 available from Degussa; Johoku Chemical CBT-1 Carbobenzotriazole available from Johoku Chemical; functional benzotriazoles; thiazoles; titanates; and zirconates.
[0050] In a further embodiment, a surfactant may be added to the adhesive composition. Suitable surfactants include silicones, polyethylene glycol, polyoxyethylene/polyoxypropylene block copolymers, ethylene diamine based polyoxyethylene/polyoxypropylene block copolymers, polyol-based polyoxyalkylenes, fatty alcohol-based polyoxyalkylenes, and fatty alcohol poiyoxyalkylene alkyl ethers. Surfactants, if used, will be used in an effective amount: a typical effective amount is an amount up to 5 wt% of the adhesive composition (excluding filler content).
[0051] In another embodiment a wetting agent may be included in the adhesive composition. Wetting agent selection will depend on the application requirements and the resin chemistry utilized. Wetting agents, if used, will be used in an effective amount: a typical effective amount is up to 5 wt% (excluding filler content). Examples of suitable wetting agents include Fluorad FC-4430 Fluorosurfactant available from 3M, Clariant Fluowet OTN, BYK W-990, Surfynol 104 Surfactant, Crompton Silwet L-7280, Triton X100 available from Rhom and Haas, Propylene glycol with a preferable Mw greater than 240, Gama-Butyrolactone, castor oil, glycerin or other fatty acids, and silanes.
[0052] In a further embodiment, a flow control agent may be included in the adhesive composition. Flow control agent selection will depend on the application requirements and resin chemistry employed. Flow control agents, if used, will be present in an effective amount: an effective amount is an amount up to 20 wt% of the adhesive composition (excluding filler content). Examples of suitable flow control agents include Cab-O-Sii TS720 available from Cabot, Aerosil R202 or R972 available from Degussa, fumed silicas, fumed aluminas, or fumed metal oxides.
[0053] In a further embodiment, an air release agent (defoamer) may be added to the adhesive composition. Air release agent selection will depend on the application requirements and resin chemistry employed. Air release agents, if used, will be used in an effective amount. A typical effective amount will be up to 5% wt% of the adhesive composition (excluding fiiier content). Examples of suitable air release agents include Antifoam 1400 available from Dow Corning, DuPont Modoflow, and BYK A-510.
[0054] In some embodiments these compositions are formulated with tackifying resins in order to improve adhesion and introduce tack; examples of tackifying resins include naturally-occurring resins and modified naturally-occurring resins; polyterpene resins; phenolic modified terpene resins; coumarons-indene resins; aliphatic and aromatic petroleum hydrocarbon resins; phthalate esters; hydrogenated hydrocarbons, hydrogenated rosins and hydrogenated rosin esters. Tackifying resins, if used, will be used in an effective amount. A typical effective amount will be up to 5 wt% of the adhesive composition (excluding filler content).
[0055] In some embodiments other components may be included in the adhesive composition, for example, diluents such as liquid polybutene or polypropylene; petroleum waxes such as paraffin and microcrystalline waxes, poiyethylene greases, hydrogenated animal, fish and vegetable fats, mineral oil and synthetic waxes, naphthenic or paraffinic mineral oils.
[0056] Other additives, such as stabilizers, antioxidants, impact modifiers, and colorants, in types and amounts known in the art, may also be added to the adhesive composition.
[0057] Common solvents with a proper boiling point ranging from 25 0C to 230 °C may be used in the adhesive composition. Examples of suitable solvents that may be utilized include ketones, esters, alcohols, ethers, and other common solvents that are stable and dissolve the resins in the composition. Suitable solvents include γ- butyrolactone, propylene glycol methyl ethyl acetate (PGMEA), and 4-methyl-2- pentanone.
[0058] After the adhesive composition is applied to a substrate, which may include a silicon die, it may be dried and/or B-staged in an optional process step. In one embodiment of the invention the adhesive is hardened to a non-tacky state so that the substrate, silicon wafer, or silicon die may be stored and/or sent to a separate location before the semiconductor die is attached. Typically, the adhesive is hardened sufficiently to enable the adhesive-coated substrates, dies, or wafers, to be stacked on top of one another and stored without the use of interleafs. The hardening of the adhesive may be accomplished in numerous ways, depending on the adhesive formulation employed.
[0059] In one embodiment the adhesive composition is thermoplastic and applied at a temperature above its melting point such that it is in a flow-able state. In this case the adhesive composition is hardened by cooling it below its melting point and/or softening point.
[0060] In another embodiment the adhesive composition comprises at least a liquid thermoset resin and a solvent. In this embodiment the adhesive is hardened to a non-tacky, or very low-flow, state, by heating the adhesive and substrate sufficiently to evaporate the solvent and partiaϋy cure the thermoset resin or resins.
[0061] In another embodiment the adhesive contains a solid thermoset resin dissolved in a solvent. After application to the substrate the adhesive will be hardened to a non-tacky, or very low flow, state by heating the adhesive and substrate sufficiently to evaporate the solvent, leaving a non-tacky thermoset resin coating on the substrate.
[0062] In another embodiment the adhesive contains at least one liquid thermoset resin. After application to the substrate the adhesive will be hardened to a non-tacky, or very low flow, state by heating the adhesive and substrate sufficiently to partially advance the thermoset resin to a non-tacky, or very low flow, state.
[0063] One skilled in the art would appreciate that the adhesive might also contain a combination of resins that could be dried, B-staged, and cured with a combination of mechanisms. For instance, the formulation might be B-staged through the use of ultraviolet radiation and, in a downstream manufacturing step after die attach, cured through the use of heat. The formulation might also contain a combination of resins that have two separate cure temperatures such that the adhesive could be hardened by heating the substrate at the first (and lower) temperature, causing the first resin to cure and the overall adhesive formulation to harden to a non-tacky state. In this case the second resin, which has a second (and higher) curing temperature, would be cured in a subsequent processing step after the die is attached.
[0064] If the adhesive does require initial or immediate curing, the cure may be accomplished either as an individual process step, or in conjunction with another processing operation such as solder reflow or wire bonding.
[0065] If a B-staging step is utilized, the B-staging temperature will generally be within a range of 8O0C to 2000C, and B-staging will be effected within a time period ranging from one minute to two hours, depending on the particular adhesive formulation chosen. The time and temperature B-staging profile for each adhesive composition will vary, and different compositions can be designed to provide the B- staging profile that will be suited to the particular industrial manufacturing process.
[0066] In an alternative embodiment the adhesive is not hardened prior to die attach. In this case the die is mounted onto the substrate while the adhesive is still in a flow- able state. This would enable the formation of a fillet around the die when the die is pressed into the adhesive. The flow of the adhesive and the pressure used to mount the die may be tailored to give the desired amount of fillet for each specific package design. In this embodiment care must be taken to avoid flow of the adhesive into the opening in the substrate, as this would interfere with wire bonding.
[0067] The adhesive of the present invention may be used to bond any two articles together and is particularly useful in adhering a semiconductor die to a metal substrate, or to an organic substrate which has exposed metal (such as copper circuits) on its surface. The metal surface may be any suitable for use in the particular industrial use of interest including but not limited to copper, silver, stainless steel, Alloy 42, nickel, any solder, or a pre-plated finish (PPF) such as Ni/Pd/Au, either with or without silver strike on top. The semiconductor die may be any type, size, or shape, as it is not critical to the present invention. The bondline (thickness of adhesive after cure) of the assembly may be any thickness suitable for the specific semiconductor package and typically will range between 10 and 150μm.
EXAMPLES.
[0068] EXAMPLE 1 - EFFECT OF PORPHYRIN DERIVATIVE STRUCTURE. A variety of porphyrin derivatives were tested in a model adhesive formulation, and compared to a similar formulation that contained no porphyrin derivative, in order to identify the molecular features that would provide improved adhesion. The model formulation is listed in Table 1 , below.
[00691
Figure imgf000020_0001
[0070] In the case where no porphyrin derivative was tested (Formulation A listed below), the parts of each component were held constant, with the adhesion promoter simply eliminated Thus, for that formulation, the composition (excluding filler) was as follows 19 6 wt% oligomer, 78 4 wt% diacrylate, 0 98 wt% silane, 0 098 wt% inhibitor, 0 98 wt% initiator The composition with filler was as follows 4 0 wt% oligomer, 15 9 wt% diacrylate, 0 2 wt% silane, 0 02 wt% inhibitor, 0 2 wt% initiator, and 79 7 wt% silver Each formulation was used to attach 300 x 300 mil silicon die to a bare copper lead frame, with a bond fine thickness of 25μm The assemblies were then cured in nitrogen with a 30 minute ramp from room temperature to 1750C plus a 30 minute hold at 1750C Following cure the specimens were subjected to thermal processing simulation at 24O0C for one minute plus 1750C for four hours Following the thermal simulation, the die shear strength (DSS) was tested at 27O0C on a DAGE 2000 die shear tester The porphyrin derivatives tested, their functional features, and die shear test results are shown in Table 2 below
[0071]
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
[0072] According to these results the Protoporhyrin IX (Inv B), with its porphiπe structure, reactive double bonds, and carboxylic acid functionality, provided the best improvement in adhesion compared to the control formulation (Comp A). Hematoporphyrin (Inv E), which had the porphine structure and carboxylic acid functionality, also gave significant adhesion improvement. However, if either the porphine structure or the carboxylic acid functionality were unavailable, as with comparative formulations C, D, and F to M, the die shear strength was at best the same as the control formulation. This illustrates that the porphyrin ring and the carboxylic functionality are acting in a synergistic way to bond strongly to the metal substrate.
[0073] The presence of free acid molecules, as with comparative formulations J and K, appears to disturb adhesion to the Cu substrate, yielding lower DSS as compared to the control formulation.
[0074] EXAMPLE 2 - EFFECT OF PORPHYRIN DERIVATIVE CONCENTRATION ON DlE
SHEAR STRENGTH. Protoporphyrin IX was added to the model formulation cited in Example 1 at various concentrations and the resulting formulations were tested for die shear strength at elevated temperatures to illustrate the effect of porphyrin derivative concentration on the adhesion improvement. The various formulations were used to assemble test specimens for die shear testing using the assembly protocol and cure profile outlined in Example 1. The specimens for each formulation were then divided into four groups and each group was subjected to a different thermal conditioning treatment, as listed in Table 3 below.
[0075]
Figure imgf000025_0001
[0076] Each group of specimens was tested for die shear strength at 2700C using a DAGE 2000 die shear tester. The concentrations tested and results are summarized in Table 4, below.
[0077]
Figure imgf000025_0002
[0078] These results show that the adhesion strength improvement may be tailored to meet the requirements of a specific application by varying the amount of porphyrin derivative included in the formulation. It should be noted that the amount of porphyrin derivative required to yield a specific improvement in adhesion will vary, depending on the specific resin system, porphyrin derivative, and metal substrate employed.
[0079] EXAMPLE 3 - EFFECT OF RESIN CHEMISTRY. Protoporphyrin IX was added to formulations using epoxy, acrylate, and maleimide, and their die shear strength was tested. ABLEBOND 84-1 LMISR4 is an epoxy-based die attach adhesive commercially available from Ablestik Laboratories. Analogous comparative formulations which contained no porphyrin derivative were also tested to determine whether the porphyrin derivative was effective in improving adhesion for a variety of resin systems. Each formulation was used to build assemblies according to the protocol described in Example 1. The assemblies were also cured, thermally conditioned, and tested for die shear strength at 27O0C according to the protocol described in Example 1. Formulation compositions and DSS at 27O0C are listed in Tables 5-7.
[0080]
Figure imgf000026_0001
10081]
Figure imgf000026_0002
Figure imgf000027_0001
[0082]
Figure imgf000027_0002
[0083] The Protoporphyrin IX was effective in improving the adhesion of the epoxy- based formulation, the acrylate-based formulation, and the maleimide-based formulation.
[0084] EXAMPLE 4. EFFECT OF METAL SURFACE. Inventive Formulation Q and Comparative Formulation N were used to bond silicon die to pre-plated finish (PPF) lead frames, to determine the effectiveness of the inventive formulation on that surface. Each formulation was used to build assemblies according to the protocol described in Example 1. The assemblies were also cured, thermally conditioned, and tested for die shear strength at 27O0C according to the protocol described in Example 1. Results are summarized in Table 8 and show that the presence of Protooporphyrin IX improved adhesion to the PPF lead frame.
[0085]
Figure imgf000028_0001
[0086] Many modifications and variations of this invention can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. The specific embodiments described herein are offered by way of example only, and the invention is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled.

Claims

What is claimed:
1. An adhesive composition comprising (i) a curable resin and (ii) a porphyrin derivative that has at least one carboxylic acid functional group.
2. The adhesive composition of Claim 1 in which the porphyrin derivative also has at least one double bond pendant from the porphyrin structure.
3. The adhesive composition of Claim 1 in which the resin is selected from the group consisting of maleimide, epoxy, or acrylate.
4. The adhesive composition of Claim 1 or Claim 3 in which the porphyrin derivative is selected from the group consisting of
Figure imgf000029_0001
5. The adhesive composition of Claim 1 or Claim 3 in which the porphyrin derivative is present in an amount of greater than 0.25 wt% of the adhesive composition, excluding any filler present.
6. A method of improving the adhesion of an adhesive composition to metal comprising: providing a curable resin, adding to the resin a porphyrin derivative that has at least one carboxylic acid functional group.
7. The method of Claim 6 in which the porphyrin derivative also has at least one double bond pendant from the porphyrin structure.
8. The method of Claim 6 in which the resin is selected from the group consisting of maleimide, epoxy, or acrylate.
9. The method of Claim 6 or Claim 8 in which the porphyrin derivative is
selected from the group consisting
Figure imgf000030_0002
and
Figure imgf000030_0001
10. An assembly comprising a metal substrate, a semiconductor die mounted thereon, and an adhesive disposed between the metal substrate and semiconductor die wherein the adhesive comprises (i) a curable resin and (ii) a porphyrin derivative that has at least one carboxylic acid functional group.
11. The assembly of Claim 10 in which the metal substrate is selected from the group consisting of copper and pre-plated finish.
12. The assembly of Claim 10 in which the porphyrin derivative also has at least one double bond pendant from the porphyrin structure.
13. The assembly of Claim 10 in which the resin is selected from the group consisting of maleimide, epoxy, or acrylate.
14. The assembly of Claim 10 or Claim 13 in which the porphyrin derivative is
selected from the group consisting
Figure imgf000030_0003
and
15. The assembly of Claim 10 or Claim 13 in which the porphyrin derivative is present in an amount of greater than 0.25 wt% of the adhesive composition excluding any filler present.
PCT/US2007/063970 2007-03-14 2007-03-14 Composition containing porphyrin to improve adhesion WO2008111980A1 (en)

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WO2006077960A1 (en) * 2005-01-21 2006-07-27 Asahi Glass Company, Limited Pressure-sensitive adhesive composition and optical filter

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JP2005281536A (en) * 2004-03-30 2005-10-13 Lintec Corp Adhesive composition for discotic liquid crystal layer and optically functional film having visible angle expansion function
WO2006077960A1 (en) * 2005-01-21 2006-07-27 Asahi Glass Company, Limited Pressure-sensitive adhesive composition and optical filter

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