WO2008085144A1 - Low shrinkage polyester thermosetting resins - Google Patents

Low shrinkage polyester thermosetting resins Download PDF

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Publication number
WO2008085144A1
WO2008085144A1 PCT/US2006/007943 US2006007943W WO2008085144A1 WO 2008085144 A1 WO2008085144 A1 WO 2008085144A1 US 2006007943 W US2006007943 W US 2006007943W WO 2008085144 A1 WO2008085144 A1 WO 2008085144A1
Authority
WO
WIPO (PCT)
Prior art keywords
die
compound
substituted
aliphatic
bondline
Prior art date
Application number
PCT/US2006/007943
Other languages
French (fr)
Inventor
Dershem Stephen
Original Assignee
Designer Molecules, Inc.
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 Designer Molecules, Inc. filed Critical Designer Molecules, Inc.
Priority to PCT/US2006/007943 priority Critical patent/WO2008085144A1/en
Publication of WO2008085144A1 publication Critical patent/WO2008085144A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
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Definitions

  • the present invention relates to low shrinkage, b-stageable thermosetting adhesive compositions, methods of preparation and uses therefor.
  • the present invention relates to b-stageable thermosetting compounds and compositions containing polymerizable polyester compounds.
  • Adhesive compositions are used for a variety of purposes in the fabrication and assembly of semiconductor packages and microelectronic devices. The more prominent uses include bonding of electronic elements such as integrated circuit chips to lead frames or other substrates, and bonding of circuit packages or assemblies to printed wire boards. Adhesives useful for electronic packaging applications typically exhibit properties such as good mechanical strength, curing properties that do not affect the component or the carrier, and rheological properties compatible with application to microelectronic and semiconductor components.
  • a b-stageable material is a material that is usually dispensed onto a substrate as a liquid, then is b-staged to achieve a first solid phase.
  • the material acts like a thermoplastic, i.e., the material flows at an elevated temperature. At an even higher temperature, the material irreversibly crosslinks and becomes a thermoset material.
  • the transition from the thermoplastic stage to the second solid phase is thermosetting.
  • the material behaves similarly to a thermoplastic material. Thus, such a material would permit low lamination temperatures while providing high thermal stability.
  • b-stageable adhesives eliminate many of the storage, handling, dispensing, and processing issues that exist when dispensing an adhesive in a flowable form.
  • the invention is based on the discovery that a certain polyester compounds are useful as b-stageable adhesives for the microelectonic packaging industry.
  • the polyester compounds described herein contain ring-opening or ring- forming polymerizable moieties and therefore exhibit little to no shrinkage upon cure.
  • R and Q are each independently substituted or unsubstituted aliphatic, aryl, or heteroaryl; each E is independently a ring-opening or ring-forming polymerizable moiety; and n is 1 to about 10.
  • R and Q are each independently substituted or unsubstituted aliphatic, aryl, or heteroaryl;
  • each E is independently a ring-opening or ring-forming polymerizable moiety; and m is 3 or 4; and n is 1 to about 10.
  • adhesive compositions including at least one of the above described compounds, and at least one curing initiator.
  • b-stageable die-attach pastes including a) 2 weight percent to about 98 weight percent (wt %) of at least one of the above-described compounds, or combinations thereof, based on total weight of the composition, b) 0 to about 90 wt% of a filler; d) 0.05 wt % to about 5 wt % of at least one curing initiator, based on total weight of the composition; e) 0.05 wt% to about 4 wt%, of at least one coupling agent, based on total weight of the composition.
  • assemblies including a first article permanently adhered to a second article by a cured aliquot of the die-attach pastes according to the invention.
  • the invention provides assemblies wherein the b-stageable adhesive encapsulates a portion of the wiring members contained within the bondline gap between the stacked die.
  • the b-stageable adhesive has the ability to flow through (i.e., encapsulate) the wires as the adhesive fills the bondline gap, thereby preventing any mold compound from covering the wires. This situation is quite advantageous since it is known that mold compound encapsulation of the wiring members creates a CTE (coefficient of thermal expansion) mismatch.
  • the b-stageable adhesives of the invention include at least one polyester compound described herein.
  • a semiconductor die assembly including: a) a substrate having wiring members extending from pads on the substrate for electrically connecting a die to the substrate, b) a bottom die having a bottom surface and a top surface, wherein the bottom surface contacts the substrate, and wherein the top surface of the bottom die has electrical pads for attaching a wiring member from the substrate, and wherein a first die-attach adhesive is disposed between the substrate and the bottom die, c) a first top die having a bottom surface and a top surface, wherein the first top die is positioned above the bottom die so that the bottom surface of the first top die is facing the top surface of the bottom die, thereby creating a first bondline gap between the bottom die and the top die, wherein a portion of the wiring members extending from the electrical pads on the top surface of the bottom die are located within the first bondline gap, and d) a second die-attach adhesive disposed between the bottom die and the top die, thereby filling the first bondline gap and creating
  • Figure 1 depicts a cross-section of a semiconductor die assembly according to the invention.
  • the assembly is a stacked die assembly containing 4 die, with a b-stageable adhesive according to the invention disposed between each die.
  • Figure 2 is a cross-section in greater detail showing the adhesive of the invention encapsulating the gold wire bonds within the bondline, thereby preventing mold compound from flowing into the bondline and damaging the wire bonds.
  • Figure 3 depicts a stacked die package containing a dummy die. As shown in the Figure, the wire bonds are not encapsulated by the die attach adhesive, and therefore are susceptible to damage when the mold compound is applied to the package.
  • Figure 4 depicts a stacked die package using spacer paste as die attach adhesive.
  • R and Q are each independently substituted or unsubstituted aliphatic, aryl, or heteroaryl; each E is independently a ring-opening or ring-forming polymerizable moiety; and n is 1 to about 10.
  • aliphatic refers to any alkyl, alkenyl, cycloalkyl, or cycloalkenyl moiety.
  • alkyl refers to straight or branched chain hydrocarbyl groups having from 1 up to about 100 carbon atoms. Whenever it appears herein, a numerical range, such as “1 to 100" or “C 1 -CiQo”, refers to each integer in the given range; e.g., "C 1 -C 100 alkyl” means that an alkyl group may comprise only 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 100 carbon atoms, although the term “alkyl” also includes instances where no numerical range of carbon atoms is designated).
  • Substituted alkyl refers to alkyl moieties bearing substituents including alkyl, alkenyl, alkynyl, hydroxy, oxo, alkoxy, mercapto, cycloalkyl, substituted cycloalkyl, heterocyclic, substituted heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, substituted aryloxy, halogen, haloalkyl, cyano, nitro, nitrone, amino, amido, -C(O)H, -C(O)-, -C(O)-, -S-, -S(O) 2 , -OC(O)-O-, -NR-C(O), - NR-C(O)-NR, -OC(O)-NR, wherein R is H or lower alkyl, acyl, oxyacyl, carboxyl, carbamate, sulfonyl,
  • cycloalkyl refers to cyclic ring-containing groups typically containing in the range of about 3 up to about 8 carbon atoms
  • substituted cycloalkyl refers to cycloalkyl groups further bearing one or more substituents as set forth above.
  • aryl refers to aromatic groups having in the range of 6 up to 14 carbon atoms and "substituted aryl” refers to aryl groups further bearing one or more substituents as set forth above.
  • heterocyclic refers to cyclic (i.e., ring-containing) groups containing one or more heteroatoms (e.g., N, O, S, or the like) as part of the ring structure, and having in the range of 3 up to 14 carbon atoms and "substituted heterocyclic” refers to heterocyclic groups further bearing one or more substituents as set forth above.
  • heterocyclic is also intended to refer to heteroaromatic moieties.
  • alkenyl refers to straight or branched chain hydrocarbyl groups having at least one carbon-carbon double bond, and having in the range of about 2 up to about 100 carbon atoms
  • substituted alkenyl refers to alkenyl groups further bearing one or more substituents as set forth above.
  • alkylene refers to a divalent alkyl moiety
  • oxyalkylene refers to an alkylene moiety containing at least one oxygen atom instead of a methylene (CH 2 ) unit.
  • substituted alkylene and substituted oxyalkylene refer to alkylene and oxyalkylene groups further bearing one or more substituents as set forth above.
  • arylene refers to a divalent aryl moiety.
  • substituted arylene refers to arylene moieties bearing one or more substituents as set forth above.
  • polymerizable moiety refers to a moiety that undergoes ring-opening polymerization, such as, for example, epoxy, oxetane, oxazoline, benzoxazine, and the like.
  • polymerizable moiety refers to a moiety that forms a ring upon polymerization, such as, for example, cyanate esters, propargyl ethers, and the like.
  • crosslinkable refers to any moiety that has the ability to crosslink with another moiety.
  • crosslink refers to the attachment of two or more polymer chains by bridges of an element, a molecular moiety, or a compound. In general, crosslinking of the compounds of the invention takes place upon heating. As cross-linking density is increased, the properties of a material will be changed from thermoplastic to thermosetting.
  • R is a substituted or unsubstituted cycloalkyl having from 5 to about 20 carbon atoms. In other embodiments, R is a substituted or unsubstituted cycloalkyl having from 5 to about 12 carbon atoms. In some embodiments, R is a substituted or unsubstituted cyclopentyl, cyclohexyl, norbornyl, tetracyclododecyl, or dicyclopentadienyl.
  • R is a substituted or unsubstituted aliphatic. In some embodiments, R is C 2 to about C 500 aliphatic, m other embodiments, R is C 2 to about C 250 aliphatic. In still other embodiments, R is C 2 to about C 1 Oo aliphatic. In some embodiments, R is C 2 to about C 5 0 aliphatic. In still further embodiments, R is C 36 aliphatic.
  • Q is a substituted or unsubstituted aryl or heteroaryl having from 6 to about 14 carbon atoms.
  • Q is a substituted or unsubstituted phenyl or naphthyl.
  • Q is a substituted or unsubstituted cycloalkyl, such as, for example, norbornyl.
  • Q is a substituted or unsubstituted aliphatic. In some embodiments, Q is C 2 to about C 500 aliphatic.
  • Q is C 2 to about C 2 5o aliphatic. In still other embodiments, Q is C 2 to about C 10O aliphatic. In some embodiments, Q is C 2 to about C 50 aliphatic. In still further embodiments, Q is C 36 aliphatic.
  • Ring opening moieties include, for example, epoxy (such as glycidyl ethers of aliphatic alcohols, glycidyl esters, cylcoaliphatic epoxies such as cycloaliphatic epoxies derived from oligomers of cyclopentadiene, and the like) oxetane, oxazoline, benzoxazine, and the like.
  • Ring forming moieties include, for example, cyanate ester, propargyl ether, and the like.
  • esters and described herein are typically prepared by condensation of the appropriate acid and alcohols to the corresponding ester under acid catalysis; or alternatively, the compounds are prepared via transesterif ⁇ cation under acid or base catalysis.
  • Another synthetic route to the compounds described herein is a condensation reaction of the appropriate alcohols and acid chlorides in the presence of a tertiary amine.
  • Exemplary compounds according to the invention are set forth below:
  • polyester compounds of the invention may be used independently in adhesive compositions, or may be combined with other adhesive compounds and resins, hi one embodiment, a polyester compound of the invention may be used as the sole thermoset monomer of the adhesive composition. In another embodiment, the polyester compound of the invention may be combined with other thermoset monomers to make a fully formulated adhesive, hi still another embodiment, the polyester compounds of the invention may be combined with thermoplastic polymers and/or oligomers to form interpenetrating networks. [0038] In one embodiment, there is provided an adhesive composition including at least one invention polyester compound and optionally at least one curing initiator.
  • the polyester compound is present in the composition from 2 weight percent to about 98 weight percent (wt %) based on total weight of the composition.
  • the at least one curing initiator is typically present in the composition from 0.05 wt % to about 5 wt % based on total weight of the composition.
  • Suitable curing agents contemplated for use in the practice of the invention include, phenols, polyphenols, anhydrides, and the like.
  • catalysts contemplated include for example, compounds which can be employed to catalyze the reaction between a phenolic hydroxyl group and a vicinal epoxide group include, for example, tertiary amines such as, triethylamine, tripropylamine, tributylamine; 2-methylimidazole (such as, for example, the CurezolTM imidazoles available from Air Products), N-methylmorpholine, combinations thereof and the like; quaternary ammonium compounds such as, benzyl trimethyl ammonium chloride, tetrabutylammonium chloride, combinations thereof and the like; phosphines such as triphenylphosphine, tributylphosphine, trilaurylphosphine, trichlorobutylphosphine, trinaphthylphosphine, and the like; and phosphonium compounds such as, ethyltriphenylphosphonium chloride, e
  • catalysts contemplated for use include alkali metal hydroxides such as, sodium hydroxide, potassium hydroxide, lithium hydroxide, combinations thereof and the like.
  • die-attach pastes including 2 weight percent to about 98 weight percent (wt %) of at least one polyester compound described herein, or combinations thereof, based on total weight of the composition; optionally, 10 wt% to about 90 wt% of at least one additional compound selected from the group consisting of acrylates, methacrylates, maleimides, vinyl ethers, vinyl esters, styrenic compounds, and allyl functional compounds, and the like, based on total weight of the composition; 0 to about 90 wt% of a filler; 0.05 wt % to- about 5 wt % of at least one curing initiator, based on total weight of the composition; and 0.05 wt% to about 4 wt%, of at
  • the additional compound includes, for example, phenolics epoxies, novalac epoxies, imides, cyanate esters, vinyl ethers, vinyl esters, amides, polyolefins (such as polyethylenes, polypropylenes, and the like) siloxanes, cyanoacrylates, and the like, or combinations thereof.
  • a b-stageable die-attach paste including: a) 2 weight percent to about 98 weight percent (wt %) based on total weight of the composition, of a polyester compound having the structure:
  • R and Q are each independently substituted or unsubstituted aliphatic, aryl, or heteroaryl; each E is independently a ring-opening or ring-forming polymerizable moiety; and n is 1 to about 10; b) 0 to about 90 wt% of a filler; d) 0.05 wt % to about 5 wt % of at least one curing initiator, based on total weight of the composition; e) 0.05 wt% to about 4 wt%, of at least one coupling agent, based on total weight of the composition.
  • thermoplastic stage means that the adhesive has a first solid phase followed by a thermoplastic stage at elevated temperature, followed by another solid irreversibly crosslinked phase at an even higher temperature.
  • the transition from the thermoplastic stage to the second solid phase is thermosetting.
  • the material behaves similarly to a thermoplastic material.
  • such an adhesive allows for low lamination temperatures while providing high thermal stability.
  • Fillers contemplated for use in the practice of the present invention are typically thermally conductive, and/or fillers which act primarily to modify the rheology of the resulting composition.
  • suitable thermally conductive fillers which can be employed in the practice of the present invention include graphite, aluminum nitride, silicon carbide, boron nitride, diamond dust, alumina, and the like.
  • Compounds which act primarily to modify rheology include polysiloxanes (such as polydimethyl siloxanes) silica, fumed silica, alumina, titania, calcium carbonate, polytetrafluoroethylene, and the like.
  • the term "coupling agent” refers to chemical species that are capable of bonding to a mineral surface and which also contain polymerizably reactive functional group(s) so as to enable interaction with the adhesive composition. Coupling agents thus facilitate linkage of the die-attach paste to the substrate to which it is applied.
  • Exemplary coupling agents contemplated for use in the practice of the present invention include silicate esters, metal acrylate salts (e.g., aluminum methacrylate), titanates (e.g., titanium methacryloxyethylacetoacetate triisopropoxide), or compounds that contain a copolymerizable group and a chelating ligand (e.g., phosphine, mercaptan, acetoacetate, and the like).
  • the coupling agents contain both a co-polymerizable function (e.g., glycidyl ether, cycloaliphatic epoxy, and the like), as well as a silicate ester function.
  • the silicate ester portion of the coupling agent is capable of condensing with metal hydroxides present on the mineral surface of substrate, while the co-polymerizable function is capable of co-polymerizing with the other reactive components of invention die-attach paste.
  • both photoinitiation and thermal initiation may be desirable.
  • curing of a photoinitiator-containing adhesive can be started by UV irradiation, and in a later processing step, curing can be completed by the application of heat to accomplish a free-radical cure.
  • Both UV and thermal initiators may therefore be added to the adhesive composition.
  • these b-stageable compositions will cure within a temperature range of 80-220 0 C, and curing will be effected within a length of time of less than 1 minute to 180 minutes.
  • the b-stageable die-attach paste may be preapplied onto either a semiconductor die or onto a substrate.
  • the time and temperature curing profile for each adhesive composition will vary, and different compositions can be designed to provide the curing profile that will be suited to the particular industrial manufacturing process.
  • the adhesive compositions may contain compounds that lend additional flexibility and toughness to the resultant cured adhesive.
  • Such compounds may be any thermoset or thermoplastic material having a Tg of 50° C or less, and typically will be a polymeric material characterized by free rotation about the chemical bonds, the presence of ether groups, and the absence of ring structures.
  • Suitable such modifiers include polyacrylates, poly(butadiene), hydrogenated polybutadiene, polyTHF (polymerized tetrahydrofuran, also known as poly(l,4-butanediol)), CTBN (carboxy-terminated butadiene-acrylonitrile) rubber, and polypropylene glycol.
  • toughening compounds may be in an amount up to about 15 percent by weight of the total composition.
  • compositions will perform within the commercially acceptable range for die attach adhesives.
  • Commerically acceptable values for die shear for the adhesives on a 80 x 80 mil 2 silicon die are in the range of greater than or equal to 1 kg at room temperature, and greater than or equal to 0.5 kg at 240° C.
  • Acceptable values for warpage for a 500 x 500 mil 2 die are in the range of less than or equal to 70 Nm at room temperature.
  • assemblies of components adhered together employing the above-described b-stageable adhesive compositions and/or die attach pastes.
  • assemblies comprising a first article permanently adhered to a second article by a cured aliquot of the above-described adhesive composition are provided.
  • Articles contemplated for assembly employing invention compositions include memory devices, ASIC devices, microprocessors, flash memory devices, and the like.
  • assemblies comprising a microelectronic device permanently adhered to a substrate by a cured aliquot of the above-described die attach paste.
  • Microelectronic devices contemplated for use with invention die attach pastes include copper lead frames, Alloy 42 lead frames, silicon dice, gallium arsenide dice, germanium dice, and the like.
  • Organic substrates contemplated for use include polyamide, FR4, bismaleimide-triazine (BT), and the like.
  • the substrate is metal, such as, for example, copper, alloy 42, Ag-plated copper, and the like, hi other embodiments, the substrate is Ni-plated copper, Pd-plated copper, Au-plated copper, Ni-Pd- Au-plated copper, and the like. In other embodiments, the substrate includes nickel, palladium, and gold.
  • the substrate is organic, such as for example, polyamide, FR4, bismaleimide-triazine (BT), BT-glass, and the like.
  • the adhesive compositions can be prepared from (or at least contain a higher percentage of) mono-functional compounds to limit the cross-link density.
  • a minor amount of poly-functional compounds can be added to provide some cross-linking and strength to the composition, provided the amount of poly-functional compounds is limited to an amount that does not diminish the desired thermoplastic properties.
  • Cross-linking refers to the attachment of two or more polymer chains by bridges of an element, a molecular group, or a compound. In general, crosslinking of the compounds of the invention takes place upon heating. As cross- linking density is increased, the properties of a material will be changed from thermoplastic to thermosetting.
  • the b-stageable die attach adhesive encapsulates a portion of the wiring members contained within the bondline gap between the stacked die.
  • the b-stageable adhesive has the ability to flow through (i.e., encapsulate) the wires (prior to thermosetting) as the adhesive fills the bondline gap, thereby preventing any mold compound from covering the wires.
  • Figure 1-3 show cross-sectional views of an assembly containing 4 stacked die, with a well-defined b-stageable die attach adhesive described herein disposed between each of the die.
  • the bondline thickness is 1 to 10 mils. In other embodiments, the bondline thickness is 1 to 5 mils. In still other embodiments, the bondline thickness is 1 to 3 mils. In the assembly shown in Figures 1- 3, the die thickness and bondline thickness is 3 mils. This clearly demonstrates that the b-stageable die attach adhesive described herein is useful for producing stacked die packages with very thin die and bondlines.
  • the assembly includes 2 die. In other embodiments, the assembly includes 3 die. In other embodiments, the assembly includes 4 die.
  • the invention described herein has particular advantages over other stacked die assemblies using spacer pastes or dummy die.
  • spacer pastes see Figure 6
  • the invention described herein provides uniform bondline thickness and . die attach coverage.
  • there is no die shift and no overflowing to the die top especially for thin die.
  • the present invention is ideal for tight tolerance packages.
  • reaction mixture was washed with brine (3 x 50 ml) and water (3 x 50 mL), and then passed over MgSo 4 (15 g) and SiO 2 (15 g). Toluene was removed by rotary evaporation. The product was a dried in an oven at 8O 0 C for 3 days to afford Compound 3 (29.6 g, 69.2 % yield) as an orange, friable solid.

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Abstract

The invention is based on the discovery that a certain polyester compounds are useful as b-stageable adhesives for the microelectonic packaging industry. The polyester compounds described herein contain ring-opening or ring-forming polymerizable moieties and therefore exhibit little to no shrinkage upon cure. In addition, there are provided well-defined b-stageable adhesives useful in stacked die assemblies. Li particular, there are provided assemblies wherein the b-stageable adhesive encapsulates a portion of the wiring members contained within the bondline gap between the stacked die.

Description

LOW SHRINKAGE POLYESTER THERMOSETTING RESINS
RELATED APPLICATION DATA
[0001] This application claims the benefit of priority of U.S. Provisional
Application Ser. No. 60/657,889 filed March 2, 2005, the entire disclosure of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to low shrinkage, b-stageable thermosetting adhesive compositions, methods of preparation and uses therefor. In particular, the present invention relates to b-stageable thermosetting compounds and compositions containing polymerizable polyester compounds.
BACKGROUND OF THE INVENTION
[0003] Adhesive compositions, particularly conductive adhesives, are used for a variety of purposes in the fabrication and assembly of semiconductor packages and microelectronic devices. The more prominent uses include bonding of electronic elements such as integrated circuit chips to lead frames or other substrates, and bonding of circuit packages or assemblies to printed wire boards. Adhesives useful for electronic packaging applications typically exhibit properties such as good mechanical strength, curing properties that do not affect the component or the carrier, and rheological properties compatible with application to microelectronic and semiconductor components.
[0004] Recently, there has been an increased interest in b-stageable adhesives. A b-stageable material is a material that is usually dispensed onto a substrate as a liquid, then is b-staged to achieve a first solid phase. In this first solid phase the material acts like a thermoplastic, i.e., the material flows at an elevated temperature. At an even higher temperature, the material irreversibly crosslinks and becomes a thermoset material. The transition from the thermoplastic stage to the second solid phase is thermosetting. However, prior to that, the material behaves similarly to a thermoplastic material. Thus, such a material would permit low lamination temperatures while providing high thermal stability. In addition, b-stageable adhesives eliminate many of the storage, handling, dispensing, and processing issues that exist when dispensing an adhesive in a flowable form.
[0005] Moreover, a continuing challenge in the microelectronics packaging industry is the issue of shrinkage upon cure of the adhesives contained within the package. In many cases, the adhesive(s) used in a package shrinks when cured, thereby creating stress at the various interfaces inside the package. This leads to package failure and device failure and/or unreliability. Accordingly, there is a continuing need for b- stageable adhesives in the electronic packaging industry, and a particular need for adhesives with little to no shrinkage upon cure.
SUMMARY OF THE INVENTION
[0006] The invention is based on the discovery that a certain polyester compounds are useful as b-stageable adhesives for the microelectonic packaging industry. The polyester compounds described herein contain ring-opening or ring- forming polymerizable moieties and therefore exhibit little to no shrinkage upon cure. In one embodiment of the invention there are provided compounds having the structure:
Figure imgf000003_0001
wherein:
R and Q are each independently substituted or unsubstituted aliphatic, aryl, or heteroaryl; each E is independently a ring-opening or ring-forming polymerizable moiety; and n is 1 to about 10. [0007] In one embodiment, there are provided compounds having the structure:
O O O
RH -O— C— Q— C— O T R O— C- -Q C— θ4~R — E n - 1 m
wherein:
R and Q are each independently substituted or unsubstituted aliphatic, aryl, or heteroaryl;
' each E is independently a ring-opening or ring-forming polymerizable moiety; and m is 3 or 4; and n is 1 to about 10.
[0008] In another embodiment, there are provided adhesive compositions including at least one of the above described compounds, and at least one curing initiator.
[0009] In yet another embodiment, there are provided b-stageable die-attach pastes including a) 2 weight percent to about 98 weight percent (wt %) of at least one of the above-described compounds, or combinations thereof, based on total weight of the composition, b) 0 to about 90 wt% of a filler; d) 0.05 wt % to about 5 wt % of at least one curing initiator, based on total weight of the composition; e) 0.05 wt% to about 4 wt%, of at least one coupling agent, based on total weight of the composition. [0010] In another embodiment, there are provided assemblies including a first article permanently adhered to a second article by a cured aliquot of the die-attach pastes according to the invention.
[0011] In another embodiment, there are provided methods for attaching a first article to a second article. Such methods can be performed, for example, by
(a) applying an aliquot of the adhesive composition of the invention to the first article,
(b) bringing the first and second article into intimate contact to form an assembly wherein the first article and the second article are separated only by the adhesive composition applied in (a), and thereafter,
(c) subjecting the assembly to conditions suitable to cure the adhesive composition.
[0012] In another embodiment, there are provided methods for attaching a semiconductor die to a substrate. Such methods can be performed, for example, by
(a) applying the die attach paste of the invention to the substrate and/or the microelectronic device,
(b) subjecting the substrate and/or the microelectronic device to conditions suitable to form a b-staged curable film,
(c) exposing the b-staged curable film to temperature conditions suitable to melt the film,
(d) bringing the substrate and the device into intimate contact to form an assembly wherein the substrate and the device are separated only by the die-attach paste, and
(e) subjecting the b-staged curable film to conditions suitable to cure the melted film.
[0013] In another embodiment of the invention, there are provided well-defined b-stageable adhesives useful in stacked die assemblies. In particular, the invention provides assemblies wherein the b-stageable adhesive encapsulates a portion of the wiring members contained within the bondline gap between the stacked die. Li other words, the b-stageable adhesive has the ability to flow through (i.e., encapsulate) the wires as the adhesive fills the bondline gap, thereby preventing any mold compound from covering the wires. This situation is quite advantageous since it is known that mold compound encapsulation of the wiring members creates a CTE (coefficient of thermal expansion) mismatch. The b-stageable adhesives of the invention include at least one polyester compound described herein.
[0014] In one embodiment of the invention, there is provided a semiconductor die assembly including: a) a substrate having wiring members extending from pads on the substrate for electrically connecting a die to the substrate, b) a bottom die having a bottom surface and a top surface, wherein the bottom surface contacts the substrate, and wherein the top surface of the bottom die has electrical pads for attaching a wiring member from the substrate, and wherein a first die-attach adhesive is disposed between the substrate and the bottom die, c) a first top die having a bottom surface and a top surface, wherein the first top die is positioned above the bottom die so that the bottom surface of the first top die is facing the top surface of the bottom die, thereby creating a first bondline gap between the bottom die and the top die, wherein a portion of the wiring members extending from the electrical pads on the top surface of the bottom die are located within the first bondline gap, and d) a second die-attach adhesive disposed between the bottom die and the top die, thereby filling the first bondline gap and creating a first bondline, and encapsulating the portion of the wiring members located within the first bondline.
BRIEF DESCRIPTION OF THE FIGURES
[0015] Figure 1 depicts a cross-section of a semiconductor die assembly according to the invention. In this Figure, the assembly is a stacked die assembly containing 4 die, with a b-stageable adhesive according to the invention disposed between each die. [0016] Figure 2 is a cross-section in greater detail showing the adhesive of the invention encapsulating the gold wire bonds within the bondline, thereby preventing mold compound from flowing into the bondline and damaging the wire bonds.
[0017] Figure 3 depicts a stacked die package containing a dummy die. As shown in the Figure, the wire bonds are not encapsulated by the die attach adhesive, and therefore are susceptible to damage when the mold compound is applied to the package.
[0018] Figure 4 depicts a stacked die package using spacer paste as die attach adhesive.
DETAILED DESCRIPTION OF THE INVENTION
[0019] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention claimed. As used herein, the use of the singular includes the plural unless specifically stated otherwise. As used herein, "or" means "and/or" unless stated otherwise. Furthermore, use of the term "including" as well as other forms, such as "includes," and "included," is not limiting. The section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described.
[0020] Unless specific definitions are provided, the nomenclatures utilized in connection with, and the laboratory procedures and techniques of analytical chemistry, synthetic organic and inorganic chemistry described herein are those known in the art. Standard chemical symbols are used interchangeably with the full names represented by such symbols. Thus, for example, the terms "hydrogen" and "H" are understood to have identical meaning. Standard techniques may be used for chemical syntheses, chemical analyses, and formulation. [0021] The invention is based on the discovery that certain polyester compounds are useful as b-stageable adhesives for the microelectonic packaging industry. In one embodiment of the invention there are provided compounds having the structure:
Figure imgf000008_0001
wherein:
R and Q are each independently substituted or unsubstituted aliphatic, aryl, or heteroaryl; each E is independently a ring-opening or ring-forming polymerizable moiety; and n is 1 to about 10.
[0022] As used herein, "aliphatic" refers to any alkyl, alkenyl, cycloalkyl, or cycloalkenyl moiety.
[0023] As used herein, "alkyl" refers to straight or branched chain hydrocarbyl groups having from 1 up to about 100 carbon atoms. Whenever it appears herein, a numerical range, such as "1 to 100" or "C1-CiQo", refers to each integer in the given range; e.g., "C1-C100 alkyl" means that an alkyl group may comprise only 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 100 carbon atoms, although the term "alkyl" also includes instances where no numerical range of carbon atoms is designated). "Substituted alkyl" refers to alkyl moieties bearing substituents including alkyl, alkenyl, alkynyl, hydroxy, oxo, alkoxy, mercapto, cycloalkyl, substituted cycloalkyl, heterocyclic, substituted heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, substituted aryloxy, halogen, haloalkyl, cyano, nitro, nitrone, amino, amido, -C(O)H, -C(O)-, -C(O)-, -S-, -S(O)2, -OC(O)-O-, -NR-C(O), - NR-C(O)-NR, -OC(O)-NR, wherein R is H or lower alkyl, acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide, sulfuryl, and the like. [0024] As used herein, "cycloalkyl" refers to cyclic ring-containing groups typically containing in the range of about 3 up to about 8 carbon atoms, and "substituted cycloalkyl" refers to cycloalkyl groups further bearing one or more substituents as set forth above.
[0025] As used herein, "aryl" refers to aromatic groups having in the range of 6 up to 14 carbon atoms and "substituted aryl" refers to aryl groups further bearing one or more substituents as set forth above.
[0026] As used herein, "heterocyclic" refers to cyclic (i.e., ring-containing) groups containing one or more heteroatoms (e.g., N, O, S, or the like) as part of the ring structure, and having in the range of 3 up to 14 carbon atoms and "substituted heterocyclic" refers to heterocyclic groups further bearing one or more substituents as set forth above. The term heterocyclic is also intended to refer to heteroaromatic moieties. As used herein, "alkenyl" refers to straight or branched chain hydrocarbyl groups having at least one carbon-carbon double bond, and having in the range of about 2 up to about 100 carbon atoms, and "substituted alkenyl" refers to alkenyl groups further bearing one or more substituents as set forth above.
[0027] As used herein, "alkylene" refers to a divalent alkyl moiety, and
"oxyalkylene" refers to an alkylene moiety containing at least one oxygen atom instead of a methylene (CH2) unit. "Substituted alkylene" and "substituted oxyalkylene" refer to alkylene and oxyalkylene groups further bearing one or more substituents as set forth above.
[0028] As used herein, "arylene" refers to a divalent aryl moiety. "Substituted arylene" refers to arylene moieties bearing one or more substituents as set forth above. [0029] As used herein, the term "polymerizable moiety" refers to a moiety that undergoes ring-opening polymerization, such as, for example, epoxy, oxetane, oxazoline, benzoxazine, and the like. In other embodiments, the term "polymerizable moiety" refers to a moiety that forms a ring upon polymerization, such as, for example, cyanate esters, propargyl ethers, and the like.
[0030] As used herein, the term "crosslinkable" refers to any moiety that has the ability to crosslink with another moiety. As used herein, the term "crosslink" refers to the attachment of two or more polymer chains by bridges of an element, a molecular moiety, or a compound. In general, crosslinking of the compounds of the invention takes place upon heating. As cross-linking density is increased, the properties of a material will be changed from thermoplastic to thermosetting.
[0031] In certain embodiments, R is a substituted or unsubstituted cycloalkyl having from 5 to about 20 carbon atoms. In other embodiments, R is a substituted or unsubstituted cycloalkyl having from 5 to about 12 carbon atoms. In some embodiments, R is a substituted or unsubstituted cyclopentyl, cyclohexyl, norbornyl, tetracyclododecyl, or dicyclopentadienyl.
[0032] In some embodiments, R is a substituted or unsubstituted aliphatic. In some embodiments, R is C2 to about C500 aliphatic, m other embodiments, R is C2 to about C250 aliphatic. In still other embodiments, R is C2 to about C1Oo aliphatic. In some embodiments, R is C2 to about C50 aliphatic. In still further embodiments, R is C36 aliphatic.
[0033] A wide variety of aryl and heteroaryl moieties are contemplated for Q in the practice of the invention. In some embodiments, Q is a substituted or unsubstituted aryl or heteroaryl having from 6 to about 14 carbon atoms. In other embodiments, Q is a substituted or unsubstituted phenyl or naphthyl. In further embodiments, Q is a substituted or unsubstituted cycloalkyl, such as, for example, norbornyl. [0034] In some embodiments, Q is a substituted or unsubstituted aliphatic. In some embodiments, Q is C2 to about C500 aliphatic. In other embodiments, Q is C2 to about C25o aliphatic. In still other embodiments, Q is C2 to about C10O aliphatic. In some embodiments, Q is C2 to about C50 aliphatic. In still further embodiments, Q is C36 aliphatic.
[0035] A wide variety of ring opening and/or ring forming polymerizable moieties are contemplated for use in the practice of the invention. Ring opening moieties include, for example, epoxy (such as glycidyl ethers of aliphatic alcohols, glycidyl esters, cylcoaliphatic epoxies such as cycloaliphatic epoxies derived from oligomers of cyclopentadiene, and the like) oxetane, oxazoline, benzoxazine, and the like. Ring forming moieties include, for example, cyanate ester, propargyl ether, and the like.
[0036] The compounds of the invention are readily prepared according to organic chemistry techniques well-known to those skilled in the art. For example, the esters and described herein are typically prepared by condensation of the appropriate acid and alcohols to the corresponding ester under acid catalysis; or alternatively, the compounds are prepared via transesterifϊcation under acid or base catalysis. Another synthetic route to the compounds described herein is a condensation reaction of the appropriate alcohols and acid chlorides in the presence of a tertiary amine. Exemplary compounds according to the invention are set forth below:
Figure imgf000012_0001
Compound 1
Figure imgf000012_0002
Compound 2
Figure imgf000013_0001
Compound 3
Figure imgf000013_0002
Compound 4
[0037] The polyester compounds of the invention may be used independently in adhesive compositions, or may be combined with other adhesive compounds and resins, hi one embodiment, a polyester compound of the invention may be used as the sole thermoset monomer of the adhesive composition. In another embodiment, the polyester compound of the invention may be combined with other thermoset monomers to make a fully formulated adhesive, hi still another embodiment, the polyester compounds of the invention may be combined with thermoplastic polymers and/or oligomers to form interpenetrating networks. [0038] In one embodiment, there is provided an adhesive composition including at least one invention polyester compound and optionally at least one curing initiator.
[0039] In some embodiments, the polyester compound is present in the composition from 2 weight percent to about 98 weight percent (wt %) based on total weight of the composition.
[0040] The at least one curing initiator is typically present in the composition from 0.05 wt % to about 5 wt % based on total weight of the composition. Suitable curing agents contemplated for use in the practice of the invention include, phenols, polyphenols, anhydrides, and the like. Certain catalysts contemplated, include for example, compounds which can be employed to catalyze the reaction between a phenolic hydroxyl group and a vicinal epoxide group include, for example, tertiary amines such as, triethylamine, tripropylamine, tributylamine; 2-methylimidazole (such as, for example, the Curezol™ imidazoles available from Air Products), N-methylmorpholine, combinations thereof and the like; quaternary ammonium compounds such as, benzyl trimethyl ammonium chloride, tetrabutylammonium chloride, combinations thereof and the like; phosphines such as triphenylphosphine, tributylphosphine, trilaurylphosphine, trichlorobutylphosphine, trinaphthylphosphine, and the like; and phosphonium compounds such as, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium phosphate, ethyltriphenylphosphonium acetate.acetic acid complex, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium phosphate, tetrabutylphosphonium acetate.acetic acid complex, butyltriphenylphosphonium tetrabromobisphenate, butyltriphenylphosphonium bisphenate, butyltriphenylphosphonium bicarbonate, combinations thereof and the like. In addition, for applications outside the microelectronic packaging industry, catalysts contemplated for use include alkali metal hydroxides such as, sodium hydroxide, potassium hydroxide, lithium hydroxide, combinations thereof and the like. [0041] In another embodiment of the invention, there are provided die-attach pastes including 2 weight percent to about 98 weight percent (wt %) of at least one polyester compound described herein, or combinations thereof, based on total weight of the composition; optionally, 10 wt% to about 90 wt% of at least one additional compound selected from the group consisting of acrylates, methacrylates, maleimides, vinyl ethers, vinyl esters, styrenic compounds, and allyl functional compounds, and the like, based on total weight of the composition; 0 to about 90 wt% of a filler; 0.05 wt % to- about 5 wt % of at least one curing initiator, based on total weight of the composition; and 0.05 wt% to about 4 wt%, of at least one coupling agent, based on total weight of the composition. In some embodiments, the additional compound includes, for example, phenolics epoxies, novalac epoxies, imides, cyanate esters, vinyl ethers, vinyl esters, amides, polyolefins (such as polyethylenes, polypropylenes, and the like) siloxanes, cyanoacrylates, and the like, or combinations thereof.
[0042] In one embodiment, there is provided a b-stageable die-attach paste including: a) 2 weight percent to about 98 weight percent (wt %) based on total weight of the composition, of a polyester compound having the structure:
Figure imgf000015_0001
wherein:
R and Q are each independently substituted or unsubstituted aliphatic, aryl, or heteroaryl; each E is independently a ring-opening or ring-forming polymerizable moiety; and n is 1 to about 10; b) 0 to about 90 wt% of a filler; d) 0.05 wt % to about 5 wt % of at least one curing initiator, based on total weight of the composition; e) 0.05 wt% to about 4 wt%, of at least one coupling agent, based on total weight of the composition.
[0043] As used herein, "b-stageable" means that the adhesive has a first solid phase followed by a thermoplastic stage at elevated temperature, followed by another solid irreversibly crosslinked phase at an even higher temperature. The transition from the thermoplastic stage to the second solid phase is thermosetting. However, prior to that, the material behaves similarly to a thermoplastic material. Thus, such an adhesive allows for low lamination temperatures while providing high thermal stability.
[0044] Fillers contemplated for use in the practice of the present invention are typically thermally conductive, and/or fillers which act primarily to modify the rheology of the resulting composition. Examples of suitable thermally conductive fillers which can be employed in the practice of the present invention include graphite, aluminum nitride, silicon carbide, boron nitride, diamond dust, alumina, and the like. Compounds which act primarily to modify rheology include polysiloxanes (such as polydimethyl siloxanes) silica, fumed silica, alumina, titania, calcium carbonate, polytetrafluoroethylene, and the like.
[0045] As used herein, the term "coupling agent" refers to chemical species that are capable of bonding to a mineral surface and which also contain polymerizably reactive functional group(s) so as to enable interaction with the adhesive composition. Coupling agents thus facilitate linkage of the die-attach paste to the substrate to which it is applied.
[0046] Exemplary coupling agents contemplated for use in the practice of the present invention include silicate esters, metal acrylate salts (e.g., aluminum methacrylate), titanates (e.g., titanium methacryloxyethylacetoacetate triisopropoxide), or compounds that contain a copolymerizable group and a chelating ligand (e.g., phosphine, mercaptan, acetoacetate, and the like). In some embodiments, the coupling agents contain both a co-polymerizable function (e.g., glycidyl ether, cycloaliphatic epoxy, and the like), as well as a silicate ester function. The silicate ester portion of the coupling agent is capable of condensing with metal hydroxides present on the mineral surface of substrate, while the co-polymerizable function is capable of co-polymerizing with the other reactive components of invention die-attach paste.
[0047] In some embodiments, both photoinitiation and thermal initiation may be desirable. For example, curing of a photoinitiator-containing adhesive can be started by UV irradiation, and in a later processing step, curing can be completed by the application of heat to accomplish a free-radical cure. Both UV and thermal initiators may therefore be added to the adhesive composition.
[0048] In general, these b-stageable compositions will cure within a temperature range of 80-2200C, and curing will be effected within a length of time of less than 1 minute to 180 minutes. The b-stageable die-attach paste may be preapplied onto either a semiconductor die or onto a substrate. As will be understood by those skilled in the art, the time and temperature curing profile for each adhesive composition will vary, and different compositions can be designed to provide the curing profile that will be suited to the particular industrial manufacturing process.
[0049] In certain embodiments, the adhesive compositions may contain compounds that lend additional flexibility and toughness to the resultant cured adhesive. Such compounds may be any thermoset or thermoplastic material having a Tg of 50° C or less, and typically will be a polymeric material characterized by free rotation about the chemical bonds, the presence of ether groups, and the absence of ring structures. Suitable such modifiers include polyacrylates, poly(butadiene), hydrogenated polybutadiene, polyTHF (polymerized tetrahydrofuran, also known as poly(l,4-butanediol)), CTBN (carboxy-terminated butadiene-acrylonitrile) rubber, and polypropylene glycol. When present, toughening compounds may be in an amount up to about 15 percent by weight of the total composition.
[0050] These compositions will perform within the commercially acceptable range for die attach adhesives. Commerically acceptable values for die shear for the adhesives on a 80 x 80 mil2 silicon die are in the range of greater than or equal to 1 kg at room temperature, and greater than or equal to 0.5 kg at 240° C. Acceptable values for warpage for a 500 x 500 mil2 die are in the range of less than or equal to 70 Nm at room temperature.
[0051] In yet another embodiment of the invention, there are provided assemblies of components adhered together employing the above-described b-stageable adhesive compositions and/or die attach pastes. Thus, for example, assemblies comprising a first article permanently adhered to a second article by a cured aliquot of the above-described adhesive composition are provided. Articles contemplated for assembly employing invention compositions include memory devices, ASIC devices, microprocessors, flash memory devices, and the like. Also contemplated are assemblies comprising a microelectronic device permanently adhered to a substrate by a cured aliquot of the above-described die attach paste. Microelectronic devices contemplated for use with invention die attach pastes include copper lead frames, Alloy 42 lead frames, silicon dice, gallium arsenide dice, germanium dice, and the like. Organic substrates contemplated for use include polyamide, FR4, bismaleimide-triazine (BT), and the like.
[0052] In another embodiment of the invention, there are provided methods for attaching a first article to a second article. Such methods can be performed, for example, by
(a) applying an aliquot of the adhesive composition of the invention to the first article,
(b) bringing the first and second article into intimate contact to form an assembly wherein the first article and the second article are separated only by the adhesive composition applied in (a), and
(c) subjecting the assembly to conditions suitable to cure the adhesive composition.
[0053] In another embodiment of the invention, there are provided methods for attaching a semiconductor die to a substrate. Such methods can be performed, for example, by
(a) applying the b-stageable die attach paste of the invention to the substrate and/or the microelectronic device,
(b) subjecting the substrate and/or the microelectronic device to conditions suitable to form a b-staged curable film,
(c) exposing the b-staged curable film to temperature conditions suitable to melt the film,
(d) bringing the substrate and the device into intimate contact to form an assembly wherein the substrate and the device are separated only by the die-attach paste, and
(e) subjecting the b-staged curable film to conditions suitable to cure the melted film.
[0054] hi some embodiments, the substrate is metal, such as, for example, copper, alloy 42, Ag-plated copper, and the like, hi other embodiments, the substrate is Ni-plated copper, Pd-plated copper, Au-plated copper, Ni-Pd- Au-plated copper, and the like. In other embodiments, the substrate includes nickel, palladium, and gold.
[0055] In some embodiments, the substrate is organic, such as for example, polyamide, FR4, bismaleimide-triazine (BT), BT-glass, and the like.
[0056] It is understood that using the compounds and methods of the present invention, it is possible to prepare adhesives having a wide range of cross-link density by the judicious choice and amount of polyester compounds. The greater proportion of polyfunctional compounds reacted, the greater the cross-link density. If thermoplastic properties are desired, the adhesive compositions can be prepared from (or at least contain a higher percentage of) mono-functional compounds to limit the cross-link density. A minor amount of poly-functional compounds can be added to provide some cross-linking and strength to the composition, provided the amount of poly-functional compounds is limited to an amount that does not diminish the desired thermoplastic properties. Within these parameters, the strength and elasticity of individual adhesives can be tailored to a particular end-use application.
[0057] "Cross-linking," as used herein, refers to the attachment of two or more polymer chains by bridges of an element, a molecular group, or a compound. In general, crosslinking of the compounds of the invention takes place upon heating. As cross- linking density is increased, the properties of a material will be changed from thermoplastic to thermosetting.
[0058] In another embodiment of the invention, there are provided stacked die assemblies wherein the b-stageable die attach adhesive encapsulates a portion of the wiring members contained within the bondline gap between the stacked die. In other words, the b-stageable adhesive has the ability to flow through (i.e., encapsulate) the wires (prior to thermosetting) as the adhesive fills the bondline gap, thereby preventing any mold compound from covering the wires.
[0059] For example, Figure 1-3 show cross-sectional views of an assembly containing 4 stacked die, with a well-defined b-stageable die attach adhesive described herein disposed between each of the die. In some embodiments, the bondline thickness is 1 to 10 mils. In other embodiments, the bondline thickness is 1 to 5 mils. In still other embodiments, the bondline thickness is 1 to 3 mils. In the assembly shown in Figures 1- 3, the die thickness and bondline thickness is 3 mils. This clearly demonstrates that the b-stageable die attach adhesive described herein is useful for producing stacked die packages with very thin die and bondlines. In certain embodiments, the assembly includes 2 die. In other embodiments, the assembly includes 3 die. In other embodiments, the assembly includes 4 die. [0060] The invention described herein has particular advantages over other stacked die assemblies using spacer pastes or dummy die. With respect to spacer pastes (see Figure 6), the invention described herein provides uniform bondline thickness and . die attach coverage. In addition, in contrast to assemblies using spacer pastes, there is no die shift and no overflowing to the die top (especially for thin die). Thus, the present invention is ideal for tight tolerance packages.
[0061] With respect to assemblies containing dummy die (see Figure 5), the assemblies described herein have a significantly reduced bondline gap. hi addition, the additional die attach process for the dummy die is eliminated, thus reducing all oven cure processes down to one (prior to molding).
[0062] The invention will now be further described with reference to the following non-limiting examples.
EXAMPLES
Example 1
Figure imgf000022_0001
Compound 1
[0063] To a 500 niL flask was added isophthalic acid (33.2 g, 200 mmol), 4,8- bis(hydroxymethyl)tricyclo[5.2.1.0 2>6]decane (58.8 g, 300 mmol), Empol 1008 (hydrogenated dimmer acid, available from Cognis) (28.3 g, 50 mmol), and toluene (150 mL). The reaction mixture was heated to 7O0C5 at which time methanesulfonic acid (3 g) was added. The flask was equipped with a reflux condenser and Dean-Stark trap, and the reaction mixture was refluxed for 21 hrs yielding the expected amount of water (9.0 mL). After cooling, toluene (110 mL) and Siθ2 (10 g) were added to the flask and the mixture was stirred for 30 min. The mixture was then passed over SiO2 (20 g). After removal of toluene by rotary evaporation, Dow ERL 4140 (17.2 g, 1 lOmmol) and DMAP (0.76 g) were added to the mixture. The Dean-Stark trap was filled with octane and an additional aliquot of octane (8 mL) was added to the reaction mixture, and the mixture was refluxed for 2.5 days. Removal of octane by rotary evaporation afforded Compound 1 (92.1 g, 74.4 % yield) as a viscous, red-brown liquid. Example 2
Figure imgf000023_0001
Compound 2
[0064] To a 500 niL flask was added isophthaloyl dichloride (20.3 g, 100 mmol) and toluene (100 niL). A mixture containing the dimer diol Solvermol 908 (Cognis, 26.8 g, 50 mmol) and triethylamine (15.2 g, 150 mmol) was added over a 90 min period. The reaction mixture was stirred at room temperature for 30 min and then cooled to -150C. Glycidol (8.2 g, 110 mmol) was added to the mixture over a 20 min period. The reaction mixture was stirred at room temperature for 3 hrs. Next, the reaction mixture was washed with brine (3 x 50 ml) and water (3 x 50 mL), and then passed over MgSO4 (15 g) and SiO2 (15 g). Rotary evaporation of toluene afforded Compound 2 (37.3 g, 79 % yield).
Example 3
Figure imgf000024_0001
Compound 3
[0065] To a 500 mL flask was added isophthaloyl dichloride (20.3 g, 100 mmol) triethylamine (22.3 g, 220 mmol), and toluene (100 mL). A solution of bisphenol-M (26.0 g, 75 mmol) in toluene (100 mL) was added dropwise over a 10 minute period. The mixture stirred for 45 minutes, and then was cooled to 2O0C. Glycidol (4.5 g, 60 mmol) was added dropwise over a 10 minute period, and the reaction was allowed to stir overnight. The reaction mixture was washed with brine (3 x 50 ml) and water (3 x 50 mL), and then passed over MgSo4 (15 g) and SiO2 (15 g). Toluene was removed by rotary evaporation. The product was a dried in an oven at 8O0C for 3 days to afford Compound 3 (29.6 g, 69.2 % yield) as an orange, friable solid.
Example 4
Figure imgf000025_0001
Compound 4
[0066] To a 1 L flask was added isophthalic acid (16.6 g, 100 mmol), 4,8- bis(hydroxymethyl)tricyclo[5.2.1.02>6]decane (39.2 g, 200 mmol), Empol 1008 (hydrogenated dimmer acid, available from Cognis) (56.5 g, 100 mmol), Pripol 2033 (Cognis, 26.8, 50 mmol) and toluene (300 niL). The reaction mixture was heated to 7O0C, at which time methanesulfonic acid (5 g) was added. The flask was equipped with a reflux condenser and Dean-Stark trap, and the reaction mixture was refluxed for 20.5 hrs. After cooling, triethylamine (22.3 g, 220 mmol) and isophthaloyl dichloride (20.3 g, 100 mmol) were added and the mixture was stirred at room temperature for 3 hrs. The reaction mixture was washed with brine and water, and then passed over MgSO4 and SiO2 Toluene was removed by rotary evaporation and the product was dried at 8O0C for 6.5 hrs to afford Compound 4 (148.5 g, 97.5 % yield)
[0067] While this invention has been described with respect to these specific examples, it should be clear that other modifications and variations would be possible without departing from the spirit of this invention.
WHAT IS CLAIMED IS:

Claims

1. An compound having the structure:
Figure imgf000026_0001
wherein:
R and Q are each independently substituted or unsubstituted aliphatic, aryl, or heteroaryl; each E is independently a ring-opening or ring-forming polymerizable moiety; and n is 1 to about 10.
2. The compound of claim 1 , wherein R is substituted or unsubstituted aliphatic.
3. The compound of claim 1, wherein R is a C2 to about C500 aliphatic.
4. The compound of claim 1, wherein R is a C2 to about C25O aliphatic.
5. The compound of claim 1, wherein R is a C2 to about C100 aliphatic.
6. The compound of claim 1, wherein R is a C2 to about C50 aliphatic.
7. The compound of claim 1, wherein R is a C36 aliphatic.
8. The compound of claim 1 , wherein R is a substituted or unsubstituted cycloalkyl having from 5 to about 20 carbon atoms.
9. The compound of claim 1, wherein R is a substituted or unsubstituted cycloalkyl having from 5 to about 12 carbon atoms.
10. The compound of claim 1, wherein R is a substituted or unsubstituted cyclopentyl, cyclohexyl, norbornyl, tetracyclododecyl, or dicyclopentadienyl.
11. The compound of claim 1 , wherein Q is a substituted or unsubstituted aryl or heteroaryl having from 6 to about 14 carbon atoms.
12. The compound of claim 1 , wherein Q is a substituted or unsubstituted phenyl or naphthyl.
13. The compound of claim 1 , wherein Q is a substituted or unsubstituted cycloalkyl.
14. The compound of claim 1, wherein Q is a substituted or unsubstituted norbornenyl.
15. The compound of claim 1, wherein Q is a substituted or unsubstituted aliphatic.
16. The compound of claim 1, wherein Q is C2 to about C500 aliphatic.
17. The compound of claim 1, wherein Q is C2 to about C250 aliphatic.
18. The compound of claim 1, wherein Q is C2 to about C100 aliphatic.
19. The compound of claim 1, wherein Q is C2 to about C50 aliphatic.
20. The compound of claim 1 , wherein Q is C36 aliphatic.
21. The compound of claim 1 , wherein substituted aliphatic, aryl, or heteroaryl moieties comprise substituents selected from alkyl, alkenyl, alkynyl, hydroxy, oxo, alkoxy, mercapto, cycloalkyl, substituted cycloalkyl, heterocyclic, substituted heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, substituted aryloxy, halogen, haloalkyl, cyano, nitro, nitrone, amino, amido, --C(O)H,
-C(O)-, -C(O)-, -S-, -S(O)2, -OC(O)-O-, -NR-C(O), -NR-C(O)-NR, -OC(O)-NR, wherein R is H or lower alkyl, acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide, or sulfuryl.
22. The compound of claim 1 , wherein E is epoxy, oxetane, oxazoline, or benzoxazine.
23. The compound of claim 1 , wherein E is cyanate ester or propargyl ether.
24. An adhesive composition comprising at least one compound of claim 1, and optionally at least one curing initiator.
25. The adhesive composition of claim 24, wherein the at least one curing initiator comprises 0.05 wt % to about 5 wt % based on total weight of the composition.
26. The adhesive composition of claim 24, further comprising a reactive diluent.
27. The adhesive composition of claim 24, further comprising a filler.
28. The adhesive composition of claim 27, wherein the filler is conductive.
29. The adhesive composition of claim 27, wherein the filler is thermally conductive.
30. The composition of claim 29, wherein the filler is aluminum nitride, silicon carbide, boron nitride, diamond dust, alumina, polysiloxanes, silica, calcium carbonate, fumed silica, alumina, titania, polytetrafluoroethylene, or silicone.
31. The adhesive composition of claim 27, wherein the filler is non-conductive.
32. A b-stageable die-attach paste comprising: a) 2 weight percent to about 98 weight percent (wt %) of at least one compound of claim 1, or combinations thereof, based on total weight of the composition. b) 0 to about 90 wt% of a filler; d) 0.05 wt % to about 5 wt % of at least one curing initiator, based on total weight of the composition; e) 0.05 wt% to about 4 wt%, of at least one coupling agent, based on total weight of the composition. '
33. An assembly comprising a first article permanently adhered to a second article by a cured aliquot of the die-attach paste of claim 32.
34. A method for attaching a semiconductor die to a substrate comprising:
(a) applying the die attach paste of claim 32 to the substrate and/or the microelectronic device,
(b) subjecting the substrate and/or the microelectronic device to conditions suitable to form a b-staged curable film,
(c) exposing the b-staged curable film to temperature conditions suitable to melt the film, (d) bringing the substrate and the device into intimate contact to form an assembly wherein the substrate and the device are separated only by the die-attach paste, and
(e) subjecting the b-staged curable film to conditions suitable to cure the melted film.
35. A semiconductor die assembly comprising: a) a substrate having wiring members extending from pads on the substrate for electrically connecting a die to the substrate, b) a bottom die having a bottom surface and a top surface, wherein the bottom surface contacts the substrate, and wherein the top surface of the bottom die has electrical pads for attaching a wiring member from the substrate, and wherein a first die-attach adhesive is disposed between the substrate and the bottom die, c) a first top die having a bottom surface and a top surface, wherein the first top die is positioned above the bottom die so that the bottom surface of the first top die is facing the top surface of the bottom die, thereby creating a first bondline gap between the bottom die and the top die, wherein a portion of the wiring members extending from the electrical pads on the top surface of the bottom die are located within the first bondline gap, and d) a second die-attach adhesive disposed between the bottom die and the top die, thereby filling the first bondline gap and creating a first bondline, and encapsulating the portion of the wiring members located within the first bondline.
36. The semiconductor die assembly of claim 35, further comprising a second top die having a bottom surface and a top surface positioned above the first top die as in claim 35(c), wherein the second die-attach adhesive is disposed between the second top die and the first top die, thereby filling a second bondline gap and creating a second bondline, and encapsulating the portion of the wiring members located within the second bondline.
37. The semiconductor die assembly of claim 36, further comprising a third top die having a bottom surface and a top surface positioned above the second top die as in claim 35(c), wherein the second die-attach adhesive is disposed between the third top die and the second top die, thereby filling a third bondline gap and creating a third bondline, and encapsulating the portion of the wiring members located within the third bondline.
38. The semiconductor die assembly of claim 35, wherein the second die-attach adhesive comprises a compound having the structure:
Figure imgf000031_0001
wherein:
R and Q are each independently substituted or unsubstituted aliphatic, aryl, or heteroaryl; each E is independently a ring-opening or ring-forming polymerizable moiety; and n is 1 to about 10.
39. The semiconductor die assembly of claim 38, wherein n is 1 to about 5.
40. The semiconductor die assembly of claim 38, wherein n is 1 to about 3.
41. The semiconductor die assembly of claim 35, wherein the bondline is 1 to about 10 mils.
42. The semiconductor die assembly of claim 35, wherein the bondline is 1 to about 5 mils.
43. A compound having the structure: 0 O O
RH -O — C — Q — C-O- -R O— C — Q — C— O+-R — E n - 1 m
wherein:
R and Q are each independently substituted or unsubstituted aliphatic, aryl, or heteroaryl; each E is independently a ring-opening or ring-forming polymerizable moiety; and m is 3 or 4; and n is 1 to about 10.
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