WO2015048621A1 - Conductive die attach film for large die semiconductor packages and compositions useful for the preparation thereof - Google Patents

Conductive die attach film for large die semiconductor packages and compositions useful for the preparation thereof Download PDF

Info

Publication number
WO2015048621A1
WO2015048621A1 PCT/US2014/058000 US2014058000W WO2015048621A1 WO 2015048621 A1 WO2015048621 A1 WO 2015048621A1 US 2014058000 W US2014058000 W US 2014058000W WO 2015048621 A1 WO2015048621 A1 WO 2015048621A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
die attach
conductive
nadimide
maleimide
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2014/058000
Other languages
French (fr)
Inventor
Pukun Zhu
Gina V. HOANG
Shashi K. Gupta
Andrew LAIB
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel IP and Holding GmbH
Original Assignee
Henkel IP and Holding GmbH
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 Henkel IP and Holding GmbH filed Critical Henkel IP and Holding GmbH
Priority to JP2016545261A priority Critical patent/JP6378346B2/en
Priority to CN201480042671.2A priority patent/CN105473657B/en
Priority to EP14847431.5A priority patent/EP3052566B1/en
Priority to KR1020167007600A priority patent/KR101909353B1/en
Publication of WO2015048621A1 publication Critical patent/WO2015048621A1/en
Priority to US15/010,531 priority patent/US9449938B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/34—Epoxy compounds containing three or more epoxy groups obtained by epoxidation of an unsaturated polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • 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
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/01—Manufacture or treatment
    • H10W72/013—Manufacture or treatment of die-attach connectors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/01—Manufacture or treatment
    • H10W72/013—Manufacture or treatment of die-attach connectors
    • H10W72/01321—Manufacture or treatment of die-attach connectors using local deposition
    • H10W72/01325—Manufacture or treatment of die-attach connectors using local deposition in solid form
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/01—Manufacture or treatment
    • H10W72/013—Manufacture or treatment of die-attach connectors
    • H10W72/01331—Manufacture or treatment of die-attach connectors using blanket deposition
    • H10W72/01333—Manufacture or treatment of die-attach connectors using blanket deposition in liquid form, e.g. spin coating, spray coating or immersion coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/01—Manufacture or treatment
    • H10W72/013—Manufacture or treatment of die-attach connectors
    • H10W72/01365—Thermally treating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H10W72/073—Connecting or disconnecting of die-attach connectors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H10W72/073—Connecting or disconnecting of die-attach connectors
    • H10W72/07331—Connecting techniques
    • H10W72/07332—Compression bonding, e.g. thermocompression bonding
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H10W72/073—Connecting or disconnecting of die-attach connectors
    • H10W72/07331—Connecting techniques
    • H10W72/07337—Connecting techniques using a polymer adhesive, e.g. an adhesive based on silicone or epoxy
    • H10W72/07338—Connecting techniques using a polymer adhesive, e.g. an adhesive based on silicone or epoxy hardening the adhesive by curing, e.g. thermosetting
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H10W72/073—Connecting or disconnecting of die-attach connectors
    • H10W72/07351—Connecting or disconnecting of die-attach connectors characterised by changes in properties of the die-attach connectors during connecting
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/30—Die-attach connectors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/30—Die-attach connectors
    • H10W72/321—Structures or relative sizes of die-attach connectors
    • H10W72/325—Die-attach connectors having a filler embedded in a matrix
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/30—Die-attach connectors
    • H10W72/351—Materials of die-attach connectors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/30—Die-attach connectors
    • H10W72/351—Materials of die-attach connectors
    • H10W72/352—Materials of die-attach connectors comprising metals or metalloids, e.g. solders
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/30—Die-attach connectors
    • H10W72/351—Materials of die-attach connectors
    • H10W72/353—Materials of die-attach connectors not comprising solid metals or solid metalloids, e.g. ceramics
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/30—Die-attach connectors
    • H10W72/351—Materials of die-attach connectors
    • H10W72/353—Materials of die-attach connectors not comprising solid metals or solid metalloids, e.g. ceramics
    • H10W72/354—Materials of die-attach connectors not comprising solid metals or solid metalloids, e.g. ceramics comprising polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/90—Bond pads, in general
    • H10W72/951—Materials of bond pads
    • H10W72/952—Materials of bond pads comprising metals or metalloids, e.g. PbSn, Ag or Cu
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W90/00—Package configurations
    • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
    • H10W90/731—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors
    • H10W90/734—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors between a chip and a stacked insulating package substrate, interposer or RDL
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W90/00—Package configurations
    • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
    • H10W90/731—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors
    • H10W90/736—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors between a chip and a stacked lead frame, conducting package substrate or heat sink

Definitions

  • the present invention relates to conductive die attach films and formulations useful for the preparation of such films.
  • the invention relates to methods for making such formulations.
  • the invention relates to conductive networks prepared from compositions according to the present invention, and methods for making same.
  • the invention relates to articles comprising invention conductive die attach films adhered to a suitable substrate therefor, and methods for making same.
  • conductive die attach films having advantageous properties for use in large die semiconductor packages. Also provided are formulations useful for the preparation of such films, as well as methods for making such formulations.
  • conductive networks prepared from compositions according to the present invention.
  • the invention relates to articles comprising such conductive die attach films adhered to a suitable substrate therefor.
  • compositions comprising:
  • a first maleimide, nadimide or itaconimide wherein said first maleimide, nadimide or itaconimide has an aromatic backbone, and the degree of substitution of imide moieties on the backbone of said first maleimide, nadimide or itaconimide is at least 0.5 imide moieties per repeat unit of said backbone , a second maleimide, nadimide or itaconimide, wherein said second maleimide, nadimide or itaconimide has a flexible aliphatic or aliphatic/aromatic backbone, wherein the backbone of said second maleimide, nadimide or itaconimide includes straight or branched chain hydrocarbyl segments, wherein each hydrocarbyl segment has at least 20 carbons,
  • first epoxy resin wherein said first epoxy resin is rubber or elastomer-modified
  • second epoxy resin wherein said second epoxy resin has a flexible aliphatic or aliphatic/aromatic backbone, wherein the backbone of said second epoxy resin includes straight or branched chain hydrocarbyl segments, wherein each hydrocarbyl segment has at least 20 carbons, backbone,
  • composition when cured, has a modulus less than about lGPa when tested by dynamic mechanical analysis (DMA) at 260°C.
  • DMA dynamic mechanical analysis
  • the degree of substitution of imide moieties on the backbone of the first maleimide, nadimide or itaconimide is at least 0.8 imide moieties per repeat unit of said backbone; in certain embodiments, the degree of substitution on the backbone of the first maleimide, nadimide or itaconamide is at least 1 imide moiety per repeat unit of said backbone.
  • the first maleimide, nadimide or itaconimide contemplated for use in the practice of the present invention has the structure:
  • n 1-15
  • p 0-15
  • each R 2 is independently selected from hydrogen or lower alkyl
  • J is a monovalent or a polyvalent radical selected from:
  • aromatic hydrocarbyl or substituted aromatic hydrocarbyl species having in the range of about 6 up to about 300 carbon atoms, where the aromatic hydrocarbyl species is selected from aryl, alkylaryl, arylalkyl, aryalkenyl, alkenylaryl, arylalkynyl or alkynylaryl;
  • aromatic hydrocarbylene species are selected from arylene, alkylarylene, arylalkylene, arylalkenylene, alkenylarylene, arylalkynylene or alkynylarylene,
  • heterocyclic or substituted heterocyclic species having in the range of about 6 up to about 300 carbon atoms
  • linker selected from a covalent bond, -O- , -S-, -NR-, -NR-C(O)-, -NR-C(0)-0-, -NR-C(0)-NR-, -S-C(O)-, -S-C(0)-0-, -S-C(O)- NR-, -0-S(0) 2 -, -0-S(0) 2 -O, -0-S(0) 2 -NR-, -O-S(O)-, -0-S(0)-0-, -0-S(0)-NR-, -O-NR-C(O)-, -0-NR-C(0)-0-, -0-NR-C(0)-NR-, -NR-O-C(O)-, -NR-0-C(0)-0-, -NR-C(0)-NR-, -NR-O-C(O)-, -NR-0-C(0)-0-, -NR-0-C(0)-NR-, -NR-O-C(O)-,
  • J of the above-described maleimide, nadimide or itaconimide is heterocyclic, oxyheterocyclic, thioheterocyclic, aminoheterocyclic, carboxyheterocyclic, oxyaryl, thioaryl, aminoaryl, carboxyaryl, heteroaryl, oxyheteroaryl, thioheteroaryl, aminoheteroaryl, carboxyheteroaryl, oxyalkylaryl, thioalkylaryl, aminoalkylaryl, carboxyalkylaryl, oxyarylalkyl, thioarylalkyl, aminoarylalkyl, carboxyarylalkyl, oxyarylalkenyl, thioarylalkenyl, aminoarylalkenyl, carboxyarylalkenyl, oxyalkenylaryl, thioalkenylaryl, aminoalkenylaryl,
  • oxyheteroatom-containing di- or polyvalent cyclic moiety t oheteroatom-containing di- or polyvalent cyclic moiety, ammoheteiOatom-containing di- or polyvalent cyclic moiety, or a carboxyheteroatom-containing di- or polyvalent cyclic moiety.
  • first maleimide nadimide, or itaconamide contemplated for use herein include:
  • the backbone of the second maleimide, nadimide or itaconimide contemplated for use herein contains straight or branched chain hydrocarbyl segments, wherein each hydrocarbyl segment has at least 30 carbons, thereby enhancing the flexibility thereof.
  • the second maleimide, nadimide or itaconimide contemplated for use herein has the structure:
  • n 1-15
  • p 0-15
  • each R 2 is independently selected from hydrogen or lower alkyl
  • J is a monovalent or a polyvalent radical selected from:
  • non-aromatic hydrocarbyl or substituted non-aromatic hydrocarbyl species having in the range of about 20 up to about 500 carbon atoms, where the non- aromatic hydrocarbyl species is selected from alkyl, alkenyl, alkynyl, cycloalkyl, or cycloalkenyl;
  • non-aromatic hydrocarbylene or substituted non-aromatic hydrocarbylene species having in the range of about 20 up to about 500 carbon atoms, where the non-aromatic hydrocarbylene species are selected from alkylene, alkenylene, alkynylene, cycloalkylene, or cycloalkenylene,
  • heterocyclic or substituted heterocyclic species having in the range of about 20 up to about 500 carbon atoms
  • linker selected from a covalent bond, -O- , -S-, -NR-, -NR-C(O)-, -NR-C(0)-0-, -NR-C(0)-NR-, -S-C(O)-, -S-C(0)-0-, -S-C(O)- NR-, -0-S(0) 2 -, -0-S(0) 2 -0-, -0-S(0) 2 -NR-, -O-S(O)-, -0-S(0)-NR-, -O-NR-C(O)-, -0-NR-C(0)-0-, -0-NR-C(0)-NR-, -NR-O-C(O)-, -NR-0-C(0)-0-, -0-NR-C(0)-NR-, -NR-O-C(O)-, -NR-0-C(0)-0-, - R-0-C(0)-NR-, -O-NR-C(S)-, -0-NR-C(
  • J of the above-described maleimide, nadimide or itaconimide is oxyalkyl, thioalkyl, aminoalkyl, carboxylalkyl, oxyalkenyl, thioalkenyl, aminoalkenyl, carboxyalkenyl, oxyalkynyl, thioalkynyl, aminoalkynyl, carboxyalkynyl, pxycycloalkyl, thiocycloalkyl, aminocycloalkyl, carboxycycloalkyl, oxycloalkenyl, thiocycloalkenyl, aminocycloalkenyl, carboxycycloalkenyl, heterocyclic, oxyheterocyclic, thioheterocyclic, aminoheterocyclic, carboxyheterocyclic, oxyalkylene, thioalkylene, aminoalkylene, carboxyalkylene, oxyalkenylene,
  • carboxycycloalkenylene heteroatom-containing di- or polyvalent cyclic moiety, oxyheteroatom-containing di- or polyvalent cyclic moiety, thioheteroatom-containing di- or polyvalent cyclic moiety, aminoheteroatom-containing di- or polyvalent cyclic moiety, or a carboxyheteroatom-containing di- or polyvalent cyclic moiety.
  • Examples of second maleimide, nadimide, itaconamide contemplated for use herein include:
  • the first epoxy resin contemplated for use herein is an epoxidized carboxyl-terminated butadiene-acrylonitrile (CTBN) oligomer or polymer.
  • CBN carboxyl-terminated butadiene-acrylonitrile
  • the epoxidized CTBN oligomer or polymer is an epoxy- containing derivative of an oligomeric or polymeric precursor having the structure:
  • each Bu is a butylene moiety (e.g., 1 ,2-butadienyl or 1,4-butadienyl), each ACN is an acrylonitrile moiety,
  • epoxidized CTBN oligomers or polymers can be made in a variety of ways, e.g., from (1) a carboxyl teiminated butadiene/acrylonitrile copolymer, (2) an epoxy resin and (3) bisphenol A:
  • Examples of the first epoxy resin include epoxidized CTBN oligomers or polymers made from (1) a carboxyl terminated butadiene/acrylonitrile copolymer, (2) an epoxy resin and (3) bisphenol A as described above; HyproTM Epoxy-Functional Butadiene-Aciylonitrile Polymers (formerly Hycar® ETBN), and the like.
  • Rubber or elastomer-modified epoxies include epoxidized derivatives of:
  • conjugated diene butyl elastomers such as copolymers consisting of from 85 to 99.5% by weight of a C 4 -C 5 olefin combined with about 0.5 to about 15% by weight of a conjugated multi-olefin having 4 to 14 carbon atoms, copolymers of isobutylene and isoprene where a major portion of the isoprene units combined therein have conjugated diene unsaturation (see, for example, U.S. Pat. No.
  • the second epoxy resin is an epoxidized polybutadiene diglycidylether oligomer or polymer.
  • epoxidized polybutadiene diglycidylether oligomers contemplated for use herein have the structure:
  • R 1 and R 2 are each independently H or lower alkyl
  • R 3 is H, saturated or unsaturated hydrocarbyl, or epoxy
  • At least 1 epoxy-containing repeating unit set forth above, and at least one olefinic repeating unit set forth above are present in each oligomer, and, when present, in the range of 1-10 of each repeating unit is present, and
  • n falls in the range of 2 - 150.
  • epoxidized polybutadiene diglycidylether oligomer or polymer contemplated for use in the practice of the present invention has the structure:
  • R is H, OH, lower alkyl, epoxy, oxirane-substituted lower alkyl, aryl, alkaryl, and the like.
  • Examples of the second epoxy resin contemplated for use herein i.e., epoxy having a flexible backbone
  • examples of the second epoxy resin contemplated for use herein include:
  • additional epoxy materials may be included in invention formulations.
  • epoxy- functionalized resins are contemplated for use herein, e.g., epoxy resins based on bisphenol A (e.g., Epon Resin 834), epoxy resins based on bisphenol F (e.g., RSL-1739), multifunctional epoxy resins based on phenol-novolac resin, dicyclopentadiene-type epoxy resins (e.g., Epiclon HP-7200L), naphthalene-type epoxy resins, and the like, as well as mixtures of any two or more thereof.
  • bisphenol A e.g., Epon Resin 834
  • epoxy resins based on bisphenol F e.g., RSL-1739
  • multifunctional epoxy resins based on phenol-novolac resin e.g., dicyclopentadiene-type epoxy resins (e.g., Epiclon HP-7200L), naphthalene-type epoxy resins, and the like, as well as mixtures
  • Exemplary epoxy-functionalized resins contemplated for use herein include the diepoxide of the cycloaliphatic alcohol, hydrogenated bisphenol A (commercially available as Epalloy 5000), a difunctional cycloaliphatic glycidyl ester of
  • Conductive fillers contemplated for use in the practice of the present invention include silver, nickel, cobalt, copper, gold, palladium, platinum, carbon black, carbon fiber, graphite, carbon nanotubes, aluminum, indium tin oxide, silver-coated copper, silver-coated aluminum, silver-coated graphite, nickel-coated graphite, bismuth, tin, bismuth-tin alloy, metal-coated glass spheressilver-coated fiber, silver-coated spheres, antimony doped tin oxide, carbon nanotubes, conductive nanofiUers, alloys of such metals, and the like, as well as mixtures of any two or more thereof.
  • Curing agents contemplated for use in the practice of the present invention include ureas, aliphatic and aromatic amines, polyamides, imidazoles, dicyandiamides,
  • Exemplary free radical initiators include peroxy esters, peroxy carbonates, hydroperoxides, alkylperoxides, arylperoxides, azo compounds, and the like.
  • Non-reactive diluents when present, include aromatic hydrocarbons (e.g., benzene, toluene, xylene, and the like), saturated hydrocarbons (e.g., hexane, cyclohexane, heptane, tetradecane), chlorinated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethylene, and the like), ethers (e.g., diethyl ether, tetrahydrofuran, dioxane, glycol ethers, monoalkyl or dialkyl ethers of ethylene glycol, and the like), esters (e.g., ethyl acetate, butyl acetate, methoxy propyl acetate, and the like); dibasic esters, alpha-terpineol, beta-terpineol,
  • the amount of non-reactive diluent contemplated for use in accordance with the present invention can vary widely, so long as a sufficient quantity is employed to dissolve and/or disperse the components of invention compositions.
  • the amount of non-reactive diluent employed typically falls in the range of about 2 up to about 25 weight percent of the composition. In certain embodiments, the amount of non-reactive diluent falls in the range of about 5 up to 20 weight percent of the total composition. In some embodiments, the amount of non-reactive diluent falls in the range of about 10 up to about 18 weight percent of the total composition.
  • invention compositions contain substantially no diluent therein. Even if diluent is, at one time, present, it is typically removed once manipulation of invention compositions (e.g., by coating as a film on a suitable substrate) has been completed.
  • compositions according to the present invention further comprise up to about 4 wt % acrylic polymer.
  • Acrylates contemplated for use in the practice of the present invention are well known in the art. See, for example, US Pat. No. 5,717,034, the entire contents of which are hereby incorporated by reference herein.
  • acrylic polymers have a molecular weight in the range of about 100,000 up to about 1,000,000 and a Tg in the range of about -40°C up to about 20°C.
  • acrylic polymers contemplated for optional use herein have a molecular weight in the range of about 200,000 up to about 900,000 and a Tg in the range of about -40°C up to about 20°C.
  • compositions according to the present invention further comprise up to about 4 wt % polyurethane, polysiloxane, or the like.
  • polyurethane refers to polymers composed of a chain of organic units joined by carbamate (also known as “urethane") linkers.
  • Polyurethane polymers can be formed by reacting an isocyanate with a polyol. Both the isocyanates and polyols used to make polyurethanes typically contain on average two or more functional groups per molecule.
  • compositions according to the present invention optionally further comprise one or more flow additives, adhesion promoters, conductivity additives, rheology modifiers, or the like, as well as mixtures of any two or more thereof.
  • flow additives refers to silicon polymers, ethyl acrylate/2- ethylhexyl acrylate copolymers, alkylol ammonium salt of phosphoric acid esters of ketoxime, and the like, as well as combinations of any two or more thereof.
  • compositions comprise: at least 1 wt % of said first maleimide, nadimide or itaconimide, at least 1 wt % of said second maleimide, nadimide or itaconimide, at least 2 wt % of said first epoxy resin (i.e., said rubber or elastomer- modified epoxy),
  • said second epoxy resin i.e., said epoxy resin having a flexible aliphatic or aliphatic/aromatic backbone
  • the amount of each component of invention compositions falls in the range of about:
  • said first epoxy resin i.e., said rubber or elastomer-modified epoxy
  • said second epoxy resin i.e., said epoxy resin having a
  • the amount of each component of invention compositions falls in the range of about:
  • said first epoxy resin i.e., said rubber or elastomer-modified epoxy
  • said second epoxy resin i.e., said epoxy resin having a flexible aliphatic or aliphatic/aromatic backbone
  • invention compositions provide a number of useful performance properties. For example, when applied at a thickness of 0.2mm on a suitable 10x10mm copper substrate pad and cured at 200°C for 60 minutes, invention compositions undergo less than 58 micron warpage.
  • inventions described herein comprise subjecting the contemplated combination of components to high shear mixing for a time sufficient to obtain a substantially homogeneous blend.
  • compositions as described herein are applied to a suitable substrate (e.g., a release liner), then b-staged at elevated temperature to remove substantially all of the solvent therefrom.
  • a suitable substrate e.g., a release liner
  • conductive die attach films comprising the reaction product obtained upon removing substantially all of the solvent/diluent from the above-described b-staged compositions.
  • Exemplary conductive die attach films contemplated herein include films produced when said composition is cured at a temperature in the range of about 160 - 230°C for a time in the range of about 30 minutes - 2 hours.
  • conductive die attach films include those produced when compositions according to the present invention are cured at a temperature in the range of about 175-200°C for about 1 hour.
  • Conductive die attach films according to the present invention after cure, typically absorb less than about 1.2 % by weight moisture when exposed to 85°C at 85% relative humidity in a Dynamic Vapor Sorption Analyzer. In some embodiments, conductive die attach films according to the present invention, upon cure, absorb less than about 0.7% by weight moisture when exposed to 85°C at 85% relative humidity in a Dynamic Vapor Sorption Analyzer.
  • Conductive die attach films according to the present invention upon cure, typically have a Tg (as determined by thermomechanical analysis; TMA) of less than about 40°C; in some embodiments, the Tg as determined by TMA is less than about 20°C.
  • TMA thermomechanical analysis
  • TMA Thermomechanical analysis
  • conductive die attach films according to the present invention upon cure, typically have a Tan Delta Tg (as determined by dynamic mechanical analysis; DMA) of less than about 100°C; in some embodiments, the Tan Delta Tg is less than about 80°C.
  • Dynamic mechanical analysis is a technique used to determine the viscoelasticity of polymers. See an exemplary protocol therefor in Example 1 herein.
  • Conductive die attach films according to the present invention can also be characterized, upon cure, with reference to the tensile modulus thereof; in some embodiments, the tensile modulus of invention films (at 260°C) is less than IGPa; in some embodiments, the tensile modulus (at 260°C) is less than 500 Mpa.
  • Conductive die attach films according to the present invention, upon cure, can also be characterized with reference to the hot die shear thereof; in some embodiments, the hot die shear of said cured film at 260°C is at least 0.5 kg/mm 2 ; in some embodiments, the hot die shear of said film is at least 0.8 kg/mm 2 .
  • Conductive die attach films according to the present invention upon cure, can also be characterized with reference to the hot, wet die shear thereof at 260°C after exposure to 85°C at 85% relative humidity for about 3 days; in some embodiments, the hot, wet die shear of said film after exposure to such conditions is at least 0.5 kg/mm 2 ; in some embodiments, the hot, wet die shear of said film after exposure to such conditions is at least 0.65 kg/mm 2 .
  • methods for preparing conductive die attach films comprising curing the above-described compositions after application thereof to a suitable substrate, after optional b-staging thereof.
  • b-staging is carried out prior to curing of the above-described compositions.
  • Suitable substrates contemplated for use herein include lead-frame(s), laminate substrate(s) designed for semiconductor packages (e.g., BT substrate, FR4 substrate, and the like), polyethylene terephthalate, polymethyl methacrylate, polyethylene,
  • polypropylene polycarbonate, an epoxy resin, polyimide, polyamide, polyester, glass, and the like.
  • lead-frame(s) comprise a base plate consisting of copper or copper alloys, and a protective coating formed on the upper (or both) surface(s) of the base plate.
  • the protective coating is composed of at least one metal selected from the group consisting of gold, gold alloy, silver, silver alloy, palladium or palladium alloy, and has a thickness of about 10-500 angstrom.
  • the protective coating is formed by suitable means, e.g., by vapor deposition. It is possible to form an intermediate coating of nickel or nickel alloys between the surface of the base plate and the protective coating, by means of vapor deposition or wet plating. A suitable thickness for the intermediate coating is within the range of about 50-20,000 angstrom. See, for example, U.S. Pat. No. 5,510,197, the entire contents of which are hereby incorporated by reference herein.
  • articles comprising conductive die attach films as described herein adhered to a suitable substrate therefor.
  • Articles according to the present invention can be characterized in terms of the adhesion of the cured conductive die attach film to the substrate; typically the adhesion is at least about 0.5 kg/mm 2 at 260°C; in some embodiments, the adhesion is at least about 0.8 kg/mm 2 at 260°C.
  • Articles according to the present invention can also be characterized in terms of the Tg of the cured conductive die attach film, with a Tg (as determined by thermomechanical analysis; TMA) typically being less than about 40°C; in some embodiments, the Tg is less than about 20°C.
  • Tg as determined by thermomechanical analysis
  • Articles according to the present invention can alternatively be characterized with reference to the Tan Delta Tg of the cured conductive die attach film; typically, the conductive die attach film of invention articles has a Tan Delta Tg (as determined by dynamic mechanical analysis; DMA) of less than about 100°C; in some embodiments, the Tg is less than about 80°C.
  • DMA dynamic mechanical analysis
  • Articles according to the present invention can be further characterized with reference to the tensile modulus of said cured conductive die attach film at 260°C;
  • the tensile modulus is less than about lGPa; in some embodiments, the tensile modulus is less than about 500 MPa.
  • invention articles can vary over a wide range.
  • a particular advantage of invention formulations is their suitability for preparation of large dies.
  • Exemplary articles typically have a surface area of at least 6 mm 2 , and can be 2.5x2.5 mm, or 3x3 mm, or 4x4 mm, or 5x5 mm, or 6x6 mm, or 7x7mm, or 8x8 mm, or 9x9 mm, or 10x10 mm, or the like.
  • methods for preparing a conductive network comprising: applying a composition as described herein to a suitable substrate in a
  • Comparison formulations and formulations according to the invention were prepared by combining the components set forth in Table 1, as follows.
  • Solid resins were pre-dissolved in suitable solvent as follows. The required amounts of the organic components were weighed into a container, hand mixed for about 5 minutes, then sufficient solvent was added to fill 5-25 % of the container. Pre-mixing continued for about 5-10 minutes with a high speed mixer. The required amount of fillier was then added to the container, and the contents thereof subjected to high speed mixing (about 1000-3000 rpm) for about one hour. The resulting slurry was de-gassed by subjecting same to reduced pressure for about 1-10 minutes.
  • Conductive films were prepared by pouring the slurry onto a clean, prepared surface using a coating machine. The slurry was subsequently heated in a retort oven to produce a stable coating film that is well bonded to the substrate (the release liner). A cover liner is than applied onto the film to protect the surface thereof. In some circumstances, it may be desirable to laminate the film under heat and pressure to promote the formation of substantially even film coatings.
  • thermomechanical analysis (TMA) on a Perkin-Elmer Instrument with an expansion fixture with an applied force of 20mN.
  • TMA thermomechanical analysis
  • Tg glass transition temperature
  • CTE1 coefficient of thermal expansion 1
  • CTE2 coeffecient of thermal expansion 2
  • DMA analysis of tensile modulus was performed on film samples employing a TA Instruments, TA-Q800 using a flat edge tension film fixture on the TA -Q800. Sample dimensions were approximately (24 x 8 x 0.2 mm). Samples were cured by subjecting them to a 30-45min ramp from room temperature to 200°C, then soaked for about lhr at 200°C.
  • DMA was carried out at a ramp rate of 5.0°C/min starting at -70°C up to 300°C.
  • the frequency was 10 Hz and 5 microns was applied for strain amplitude. Results are presented in Table 2. Table 2
  • MSL moisture sensitivity levels
  • MSL1 85°C and 85% relative humidity for 168 hours;
  • MSL2 85°C and 60% relative humidity for 168 hours
  • MSL3 30°C and 60% relative humidity for 192 hours. The results are summarized below:
  • invention formulations e.g., Formulation C
  • e.g., Formulation C perform very well when subjected to multiple temperature cycles, providing far better adhesion than comparative formulations lacking one or more of the components required by invention formulations.
  • Patents and publications mentioned in the specification are indicative of the levels of those skilled in the art to which the invention pertains. These patents and publications are incorporated herein by reference to the same extent as if each individual application or publication was specifically and individually incorporated herein by reference.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Conductive Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

Provided herein are conductive die attach films having advantageous properties for use in a variety of applications, e.g., for the preparation of large die semiconductor packages. Also provided are formulations useful for the preparation of such films, as well as methods for making such formulations. In additional aspects of the present invention, there are provided conductive networks prepared from compositions according to the present invention. In additional aspects, the invention further relates to articles comprising such conductive die attach films adhered to a suitable substrate therefor.

Description

CONDUCTIVE DIE ATTACH FILM FOR LARGE DIE SEMICONDUCTOR PACKAGES AND COMPOSITIONS USEFUL FOR THE PREPARATION
THEREOF
FIELD OF THE INVENTION
[0001] The present invention relates to conductive die attach films and formulations useful for the preparation of such films. In one aspect, the invention relates to methods for making such formulations. In another aspect, the invention relates to conductive networks prepared from compositions according to the present invention, and methods for making same. In yet another aspect, the invention relates to articles comprising invention conductive die attach films adhered to a suitable substrate therefor, and methods for making same.
SUMMARY OF THE INVENTION
[0002] In accordance with the present invention, there are provided conductive die attach films having advantageous properties for use in large die semiconductor packages. Also provided are formulations useful for the preparation of such films, as well as methods for making such formulations.
[0003] In accordance with another aspect of the present invention, there are provided conductive networks prepared from compositions according to the present invention. In certain aspects, the invention relates to articles comprising such conductive die attach films adhered to a suitable substrate therefor.
DETAILED DESCRIPTION OF THE INVENTION
[0004] In accordance with the present invention, there are provided compositions comprising:
a first maleimide, nadimide or itaconimide, wherein said first maleimide, nadimide or itaconimide has an aromatic backbone, and the degree of substitution of imide moieties on the backbone of said first maleimide, nadimide or itaconimide is at least 0.5 imide moieties per repeat unit of said backbone , a second maleimide, nadimide or itaconimide, wherein said second maleimide, nadimide or itaconimide has a flexible aliphatic or aliphatic/aromatic backbone, wherein the backbone of said second maleimide, nadimide or itaconimide includes straight or branched chain hydrocarbyl segments, wherein each hydrocarbyl segment has at least 20 carbons,
a first epoxy resin, wherein said first epoxy resin is rubber or elastomer-modified, a second epoxy resin, wherein said second epoxy resin has a flexible aliphatic or aliphatic/aromatic backbone, wherein the backbone of said second epoxy resin includes straight or branched chain hydrocarbyl segments, wherein each hydrocarbyl segment has at least 20 carbons, backbone,
a conductive filler,
a curing agent; and
optionally a non-reactive organic diluent therefore;
wherein:
said composition, when cured, has a modulus less than about lGPa when tested by dynamic mechanical analysis (DMA) at 260°C.
[0005] In certain embodiments, the degree of substitution of imide moieties on the backbone of the first maleimide, nadimide or itaconimide is at least 0.8 imide moieties per repeat unit of said backbone; in certain embodiments, the degree of substitution on the backbone of the first maleimide, nadimide or itaconamide is at least 1 imide moiety per repeat unit of said backbone.
[0006] In certain embodiments, the first maleimide, nadimide or itaconimide contemplated for use in the practice of the present invention has the structure:
Figure imgf000004_0001
respectively, wherein:
m is 1-15,
p is 0-15,
each R2 is independently selected from hydrogen or lower alkyl, and
J is a monovalent or a polyvalent radical selected from:
- aromatic hydrocarbyl or substituted aromatic hydrocarbyl species having in the range of about 6 up to about 300 carbon atoms, where the aromatic hydrocarbyl species is selected from aryl, alkylaryl, arylalkyl, aryalkenyl, alkenylaryl, arylalkynyl or alkynylaryl;
- aromatic hydrocarbylene or substituted aromatic hydrocarbylene species
having in the range of about 6 up to about 300 carbon atoms, where the aromatic hydrocarbylene species are selected from arylene, alkylarylene, arylalkylene, arylalkenylene, alkenylarylene, arylalkynylene or alkynylarylene,
- heterocyclic or substituted heterocyclic species having in the range of about 6 up to about 300 carbon atoms,
- polysiloxane, or
- polysiloxane-polyurethane block copolymers, as well as
combinations of one or more of the above with a linker selected from a covalent bond, -O- , -S-, -NR-, -NR-C(O)-, -NR-C(0)-0-, -NR-C(0)-NR-, -S-C(O)-, -S-C(0)-0-, -S-C(O)- NR-, -0-S(0)2-, -0-S(0)2-O, -0-S(0)2-NR-, -O-S(O)-, -0-S(0)-0-, -0-S(0)-NR-, -O-NR-C(O)-, -0-NR-C(0)-0-, -0-NR-C(0)-NR-, -NR-O-C(O)-, -NR-0-C(0)-0-, -NR-0-C(0)-NR-, -O-NR-C(S)-, -0-NR-C(S)-0-, -0-NR-C(S)-NR-, -NR-O-C(S)-, -NR-0-C(S)-0-, -NR-0-C(S)-NR-, -O-C(S)-, -0-C(S)-0-, -0-C(S)-NR-, -NR-C(S)-, -NR-C(S)-0-, -NR-C(S)-NR-, -S-S(0)2-, -S-S(0)2-0-, -S-S(0)2-NR-, -NR-O-S(O)-, -NR-0-S(0)-0-, -NR-0-S(0)-NR-, -NR-0-S(0)2-, -NR-0-S(0)2-0-, -NR-0-S(0)2-NR-, -O-NR-S(O)-, -0-NR-S(0)-O, -0-NR-S(0)-NR-, -0-NR-S(0)2-0-, -0-NR-S(0)2-NR-, -0-NR-S(0)2-, -0-P(0)R2-, -S-P(0)R2-, or -NR-P(0)R2-; where each R is independently hydrogen, alkyl or substituted alkyl.
[0007] In some embodiments of the present invention, J of the above-described maleimide, nadimide or itaconimide is heterocyclic, oxyheterocyclic, thioheterocyclic, aminoheterocyclic, carboxyheterocyclic, oxyaryl, thioaryl, aminoaryl, carboxyaryl, heteroaryl, oxyheteroaryl, thioheteroaryl, aminoheteroaryl, carboxyheteroaryl, oxyalkylaryl, thioalkylaryl, aminoalkylaryl, carboxyalkylaryl, oxyarylalkyl, thioarylalkyl, aminoarylalkyl, carboxyarylalkyl, oxyarylalkenyl, thioarylalkenyl, aminoarylalkenyl, carboxyarylalkenyl, oxyalkenylaryl, thioalkenylaryl, aminoalkenylaryl,
carboxyalkenylaryl, oxyarylalkynyl, thioarylalkynyl, aminoarylalkynyl,
carboxyarylalkynyl, oxyalkynylaryl, thioalkynylaryl, aminoalkynylaryl or
carboxyalkynylaryl, oxyarylene, thioarylene, aminoarylene, carboxyarylene,
oxyalkylarylene, thioalkylarylene, aminoalkylarylene, carboxyalkylarylene,
oxyarylalkylene, thioarylalkylene, aminoarylalkylene, carboxyarylalkylene,
oxyarylalkenylene, thioarylalkenylene, aminoarylalkenylene, carboxyarylalkenylene, oxyalkenylarylene, thioalkenylarylene, aminoalkenylarylene, carboxyalkenylarylene, oxyarylalkynylene, thioarylalkynylene, aminoarylalkynylene, carboxy arylalkynylene, oxyalkynylarylene, thioalkynylarylene, mninoalkynylarylene, carboxyalkynylarylene, heteroarylene, oxyheteroarylene, thioheteroarylene, aminoheteroarylene,
carboxyheteroarylene, heteroatom-containing di- or polyvalent cyclic moiety,
oxyheteroatom-containing di- or polyvalent cyclic moiety, t oheteroatom-containing di- or polyvalent cyclic moiety, ammoheteiOatom-containing di- or polyvalent cyclic moiety, or a carboxyheteroatom-containing di- or polyvalent cyclic moiety.
[0008] Examples of first maleimide, nadimide, or itaconamide contemplated for use herein include:
Figure imgf000006_0001
Figure imgf000006_0002
Figure imgf000006_0003
Figure imgf000006_0004
Figure imgf000006_0005
[0009] In certain embodiments, the backbone of the second maleimide, nadimide or itaconimide contemplated for use herein contains straight or branched chain hydrocarbyl segments, wherein each hydrocarbyl segment has at least 30 carbons, thereby enhancing the flexibility thereof. [0010] In certain embodiments, the second maleimide, nadimide or itaconimide contemplated for use herein has the structure:
Figure imgf000007_0001
respectively, wherein:
m is 1-15,
p is 0-15,
each R2 is independently selected from hydrogen or lower alkyl, and
J is a monovalent or a polyvalent radical selected from:
- non-aromatic hydrocarbyl or substituted non-aromatic hydrocarbyl species having in the range of about 20 up to about 500 carbon atoms, where the non- aromatic hydrocarbyl species is selected from alkyl, alkenyl, alkynyl, cycloalkyl, or cycloalkenyl;
- non-aromatic hydrocarbylene or substituted non-aromatic hydrocarbylene species having in the range of about 20 up to about 500 carbon atoms, where the non-aromatic hydrocarbylene species are selected from alkylene, alkenylene, alkynylene, cycloalkylene, or cycloalkenylene,
- heterocyclic or substituted heterocyclic species having in the range of about 20 up to about 500 carbon atoms,
- polysiloxane, or
- polysiloxane-polyurethane block copolymers, as well as
combinations of one or more of the above with a linker selected from a covalent bond, -O- , -S-, -NR-, -NR-C(O)-, -NR-C(0)-0-, -NR-C(0)-NR-, -S-C(O)-, -S-C(0)-0-, -S-C(O)- NR-, -0-S(0)2-, -0-S(0)2-0-, -0-S(0)2-NR-, -O-S(O)-, -0-S(0)-O, -0-S(0)-NR-, -O-NR-C(O)-, -0-NR-C(0)-0-, -0-NR-C(0)-NR-, -NR-O-C(O)-, -NR-0-C(0)-0-, - R-0-C(0)-NR-, -O-NR-C(S)-, -0-NR-C(S)-0-, -0-NR-C(S)-NR-, -NR-O-C(S)-, -NR-0-C(S)-0-, -NR-0-C(S)-NR-, -O-C(S)-, -0-C(S)-0-, -0-C(S)-NR-, - R-C(S)-, -NR-C(S)-0-, -NR-C(S)-NR-, -S-S(0)2-, -S-S(0)2-0-, -S-S(0)2-NR-, -NR-O-S(O)-, -NR-0-S(0)-0-, -NR-0-S(0)-NR-, -NR-0-S(0)2-, -NR-0-S(0)2-0-, -NR-0-S(0)2-NR-, -O-NR-S(O)-, -0-NR-S(0)-0-, -0-NR-S(0)-NR-, -0-NR-S(0)2-0-, -0-NR-S(0)2-NR-, -0-NR-S(0)2-, -0-P(0)R2-, -S-P(0)R2-, or -NR-P(0)R2-; where each R is independently hydrogen, alkyl or substituted alkyl.
[0011] In certain embodiments, J of the above-described maleimide, nadimide or itaconimide is oxyalkyl, thioalkyl, aminoalkyl, carboxylalkyl, oxyalkenyl, thioalkenyl, aminoalkenyl, carboxyalkenyl, oxyalkynyl, thioalkynyl, aminoalkynyl, carboxyalkynyl, pxycycloalkyl, thiocycloalkyl, aminocycloalkyl, carboxycycloalkyl, oxycloalkenyl, thiocycloalkenyl, aminocycloalkenyl, carboxycycloalkenyl, heterocyclic, oxyheterocyclic, thioheterocyclic, aminoheterocyclic, carboxyheterocyclic, oxyalkylene, thioalkylene, aminoalkylene, carboxyalkylene, oxyalkenylene, thioalkenylene, aminoalkenylene, carboxyalkenylene, oxyalkynylene, thioalkynylene, aminoalkynylene, carboxyalkynylene, oxycycloalkylene, thiocycloalkylene, aminocycloalkylene, carboxycycloalkylene, oxycycloalkenylene, thiocycloalkenylene, aminocycloalkenylene,
carboxycycloalkenylene, heteroatom-containing di- or polyvalent cyclic moiety, oxyheteroatom-containing di- or polyvalent cyclic moiety, thioheteroatom-containing di- or polyvalent cyclic moiety, aminoheteroatom-containing di- or polyvalent cyclic moiety, or a carboxyheteroatom-containing di- or polyvalent cyclic moiety.
[0012] Examples of second maleimide, nadimide, itaconamide contemplated for use herein include:
Figure imgf000008_0001
Figure imgf000008_0002
Figure imgf000009_0001
Figure imgf000010_0001
[0013] In certain embodiments, the first epoxy resin contemplated for use herein is an epoxidized carboxyl-terminated butadiene-acrylonitrile (CTBN) oligomer or polymer.
[0014] In certain embodiments, the epoxidized CTBN oligomer or polymer is an epoxy- containing derivative of an oligomeric or polymeric precursor having the structure:
HOOC[(Bu)x(ACN)y]mCOOH
wherein:
each Bu is a butylene moiety (e.g., 1 ,2-butadienyl or 1,4-butadienyl), each ACN is an acrylonitrile moiety,
the Bu units and the ACN units can be arranged randomly or in blocks, each of x and y are greater than zero, provided the total of x + y = 1, the ratio of x:y falls in the range of about 10:1 - 1:10, and m falls in the range of about 20 about 100.
[0015] As readily recognized by those of skill in the art, epoxidized CTBN oligomers or polymers can be made in a variety of ways, e.g., from (1) a carboxyl teiminated butadiene/acrylonitrile copolymer, (2) an epoxy resin and (3) bisphenol A:
Figure imgf000011_0001
BisphenolA Chein Extender Reactive Epoxy R»Cerboxyl Groups
by reaction between the carboxylic acid group of CTBN and epoxies (via chain-extension reactions), and the like.
[0016] Examples of the first epoxy resin (i.e., rubber or elastomer-modified epoxy) include epoxidized CTBN oligomers or polymers made from (1) a carboxyl terminated butadiene/acrylonitrile copolymer, (2) an epoxy resin and (3) bisphenol A as described above; Hypro™ Epoxy-Functional Butadiene-Aciylonitrile Polymers (formerly Hycar® ETBN), and the like.
[0017] Rubber or elastomer-modified epoxies include epoxidized derivatives of:
(a) homopolymers or copolymers of conjugated dienes having a weight average molecular weight (Mw) of 30,000 to 400,000 or higher as described in U.S. Pat. No. 4,020,036 (the entire contents of which are hereby incorporated by reference herein), in which conjugated dienes contain from 4-11 carbon atoms per molecule (such as 1,3 -butadiene, isoprene, and the like);
(b) epihalohydrin homopolymers, a copolymer of two or more epihalohydrin
monomers, or a copolymer of an epihalohydrin monomer(s) with an oxide monomer(s) having a number average molecular weight (Mn) which varies from about 800 to about 50,000, as described in U.S. Pat. No. 4,101,604 (the entire contents of which are hereby incorporated by reference herein); (c) hydrocarbon polymers including ethylene/propylene copolymers and copolymers of ethylene/propylene and at least one nonconjugated diene, such as
ethylene/propylene/hexadiene/norbornadiene, as described in U.S. Pat. No.
4,161,471; or
(d) conjugated diene butyl elastomers, such as copolymers consisting of from 85 to 99.5% by weight of a C4 -C5 olefin combined with about 0.5 to about 15% by weight of a conjugated multi-olefin having 4 to 14 carbon atoms, copolymers of isobutylene and isoprene where a major portion of the isoprene units combined therein have conjugated diene unsaturation (see, for example, U.S. Pat. No.
4,160,759; the entire contents of which are hereby incorporated by reference herein).
[0018] In certain embodiments, the second epoxy resin is an epoxidized polybutadiene diglycidylether oligomer or polymer.
[0019] In certain embodiments, epoxidized polybutadiene diglycidylether oligomers contemplated for use herein have the structure:
Figure imgf000012_0001
wherein:
R1 and R2 are each independently H or lower alkyl,
R3 is H, saturated or unsaturated hydrocarbyl, or epoxy,
at least 1 epoxy-containing repeating unit set forth above, and at least one olefinic repeating unit set forth above are present in each oligomer, and, when present, in the range of 1-10 of each repeating unit is present, and
n falls in the range of 2 - 150.
[0020] In certain embodiments, epoxidized polybutadiene diglycidylether oligomer or polymer contemplated for use in the practice of the present invention has the structure:
Figure imgf000013_0001
wherein R is H, OH, lower alkyl, epoxy, oxirane-substituted lower alkyl, aryl, alkaryl, and the like.
[0021] Examples of the second epoxy resin contemplated for use herein (i.e., epoxy having a flexible backbone) include:
Figure imgf000013_0002
Figure imgf000013_0003
and the like.
[0022] In some embodiments, additional epoxy materials may be included in invention formulations. When included in invention formulations, a wide variety of epoxy- functionalized resins are contemplated for use herein, e.g., epoxy resins based on bisphenol A (e.g., Epon Resin 834), epoxy resins based on bisphenol F (e.g., RSL-1739), multifunctional epoxy resins based on phenol-novolac resin, dicyclopentadiene-type epoxy resins (e.g., Epiclon HP-7200L), naphthalene-type epoxy resins, and the like, as well as mixtures of any two or more thereof.
[0023] Exemplary epoxy-functionalized resins contemplated for use herein include the diepoxide of the cycloaliphatic alcohol, hydrogenated bisphenol A (commercially available as Epalloy 5000), a difunctional cycloaliphatic glycidyl ester of
hexahydrophthallic anhydride (commercially available as Epalloy 5200), Epiclon EXA- 835LV, Epiclon HP-7200L, and the like, as well as mixtures of any two or more thereof.
[0024] Additional examples of conventional epoxy materials which are suitable for use as optional additional com onent of invention formulations include:
Figure imgf000014_0001
and the like.
[0025] Conductive fillers contemplated for use in the practice of the present invention include silver, nickel, cobalt, copper, gold, palladium, platinum, carbon black, carbon fiber, graphite, carbon nanotubes, aluminum, indium tin oxide, silver-coated copper, silver-coated aluminum, silver-coated graphite, nickel-coated graphite, bismuth, tin, bismuth-tin alloy, metal-coated glass spheressilver-coated fiber, silver-coated spheres, antimony doped tin oxide, carbon nanotubes, conductive nanofiUers, alloys of such metals, and the like, as well as mixtures of any two or more thereof.
[0026] Curing agents contemplated for use in the practice of the present invention include ureas, aliphatic and aromatic amines, polyamides, imidazoles, dicyandiamides,
hydrazides, urea-amine hybrid curing systems, free radical initiators, organic bases, transition metal catalysts, phenols, acid anhydrides, Lewis acids, Lewis bases, and the like. See, for example, U.S. Pat. No. 5,397,618, the entire contents of which are hereby incorporated by reference herein.
[0027] Exemplary free radical initiators include peroxy esters, peroxy carbonates, hydroperoxides, alkylperoxides, arylperoxides, azo compounds, and the like.
[0028] Non-reactive diluents, when present, include aromatic hydrocarbons (e.g., benzene, toluene, xylene, and the like), saturated hydrocarbons (e.g., hexane, cyclohexane, heptane, tetradecane), chlorinated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethylene, and the like), ethers (e.g., diethyl ether, tetrahydrofuran, dioxane, glycol ethers, monoalkyl or dialkyl ethers of ethylene glycol, and the like), esters (e.g., ethyl acetate, butyl acetate, methoxy propyl acetate, and the like); dibasic esters, alpha-terpineol, beta-terpineol, kerosene, dibutylphthalate, butyl carbitol, butyl carbitol acetate, carbitol acetate, ethyl carbitol acetate, hexylene glycol, high boiling alcohols and esters thereof, glycol ethers, polyols (e.g., polyethylene glycol, propylene glycol, polypropylene glycol, and the like), ketones (e.g., acetone, methyl ethyl ketone, and the like), amides (e.g., dimethylformamide, dimethylacetamide, and the like), heteroaromatic compounds (e.g., N-methylpyrrolidone, and the like).
[0029] The amount of non-reactive diluent contemplated for use in accordance with the present invention can vary widely, so long as a sufficient quantity is employed to dissolve and/or disperse the components of invention compositions. When present, the amount of non-reactive diluent employed typically falls in the range of about 2 up to about 25 weight percent of the composition. In certain embodiments, the amount of non-reactive diluent falls in the range of about 5 up to 20 weight percent of the total composition. In some embodiments, the amount of non-reactive diluent falls in the range of about 10 up to about 18 weight percent of the total composition.
[0030] As readily recognized by those of skill in the art, in certain embodiments, invention compositions contain substantially no diluent therein. Even if diluent is, at one time, present, it is typically removed once manipulation of invention compositions (e.g., by coating as a film on a suitable substrate) has been completed.
[0031] In certain embodiments, compositions according to the present invention further comprise up to about 4 wt % acrylic polymer. Acrylates contemplated for use in the practice of the present invention are well known in the art. See, for example, US Pat. No. 5,717,034, the entire contents of which are hereby incorporated by reference herein.
Exemplary acrylic polymers have a molecular weight in the range of about 100,000 up to about 1,000,000 and a Tg in the range of about -40°C up to about 20°C. In certain embodiments, acrylic polymers contemplated for optional use herein have a molecular weight in the range of about 200,000 up to about 900,000 and a Tg in the range of about -40°C up to about 20°C.
[0032] In certain embodiments, compositions according to the present invention further comprise up to about 4 wt % polyurethane, polysiloxane, or the like.
[0033] As used herein," polyurethane" refers to polymers composed of a chain of organic units joined by carbamate (also known as "urethane") linkers. Polyurethane polymers can be formed by reacting an isocyanate with a polyol. Both the isocyanates and polyols used to make polyurethanes typically contain on average two or more functional groups per molecule.
[0034] As used herein, "polysiloxane" refers to silicone resins, oligomers and polymers, silicone-bridged polymers, and mixed inorganic-organic polymers with the chemical formula [R2SiO]„, where R is an organic group such as methyl, ethyl, phenyl, or the like. These materials consist of an inorganic silicon-oxygen backbone (••-Si-O-Si-O-Si-Ο- ··) with organic side groups (R) attached to the tetra-coordinate silicon atoms. [0035] In certain embodiments, compositions according to the present invention optionally further comprise one or more flow additives, adhesion promoters, conductivity additives, rheology modifiers, or the like, as well as mixtures of any two or more thereof.
[0036] As used herein, "flow additives" refers to silicon polymers, ethyl acrylate/2- ethylhexyl acrylate copolymers, alkylol ammonium salt of phosphoric acid esters of ketoxime, and the like, as well as combinations of any two or more thereof.
[0037] The amount of each component of invention compositions can vary widely.
Exemplary compositions comprise: at least 1 wt % of said first maleimide, nadimide or itaconimide, at least 1 wt % of said second maleimide, nadimide or itaconimide, at least 2 wt % of said first epoxy resin (i.e., said rubber or elastomer- modified epoxy),
at least 0.5 wt % of said second epoxy resin (i.e., said epoxy resin having a flexible aliphatic or aliphatic/aromatic backbone),
at least 70 wt % of said conductive filler,
at least 0.3 wt % of said curing agent,
optionally up to 4 wt % of an acrylic polymer, and
optionally, up to 25 wt % of a non-reactive organic diluent therefore.
[0038] In some embodiments, the amount of each component of invention compositions falls in the range of about:
1-6 wt % of said first maleimide, nadimide or itaconimide,
1- 8 wt % of said second maleimide, nadimide or itaconimide,
2- 15 wt % of said first epoxy resin (i.e., said rubber or elastomer-modified epoxy),
0.5-8 wt % of said second epoxy resin (i.e., said epoxy resin having a
flexible aliphatic or aliphatic/aromatic backbone),
70-95 wt % of said conductive filler,
0.3-4 wt % of said curing agent, optionally up to 4 wt % of an acrylic polymer, and
optionally up to 25 wt % of a non-reactive organic diluent therefore.
[0039] In some embodiments, the amount of each component of invention compositions falls in the range of about:
2- 4 wt % of said first maleimide, nadimide or itaconimide,
3- 6 wt % of said second maleimide, nadimide or itaconimide,
6-12 wt % of said first epoxy resin (i.e., said rubber or elastomer-modified epoxy),
1-5 wt % of said second epoxy resin (i.e., said epoxy resin having a flexible aliphatic or aliphatic/aromatic backbone),
80-85 wt % of said conductive filler,
0.5-3 wt % of said curing agent,
optionally up to 4 wt % of an acrylic polymer, and
optionally up to 25 wt % of a non-reactive organic diluent therefore.
[0040] Invention compositions provide a number of useful performance properties. For example, when applied at a thickness of 0.2mm on a suitable 10x10mm copper substrate pad and cured at 200°C for 60 minutes, invention compositions undergo less than 58 micron warpage.
[0041] In certain embodiments of the present invention, there are provided methods of making the composition described herein. Invention methods comprise subjecting the contemplated combination of components to high shear mixing for a time sufficient to obtain a substantially homogeneous blend.
[0042] In certain embodiments of the present invention, compositions as described herein are applied to a suitable substrate (e.g., a release liner), then b-staged at elevated temperature to remove substantially all of the solvent therefrom. [0043] In certain embodiments of the present invention, there are provided conductive die attach films comprising the reaction product obtained upon removing substantially all of the solvent/diluent from the above-described b-staged compositions.
[0044] Exemplary conductive die attach films contemplated herein include films produced when said composition is cured at a temperature in the range of about 160 - 230°C for a time in the range of about 30 minutes - 2 hours. In some embodiments, conductive die attach films include those produced when compositions according to the present invention are cured at a temperature in the range of about 175-200°C for about 1 hour.
[0045] Conductive die attach films according to the present invention, after cure, typically absorb less than about 1.2 % by weight moisture when exposed to 85°C at 85% relative humidity in a Dynamic Vapor Sorption Analyzer. In some embodiments, conductive die attach films according to the present invention, upon cure, absorb less than about 0.7% by weight moisture when exposed to 85°C at 85% relative humidity in a Dynamic Vapor Sorption Analyzer.
[0046] Conductive die attach films according to the present invention, upon cure, typically have a Tg (as determined by thermomechanical analysis; TMA) of less than about 40°C; in some embodiments, the Tg as determined by TMA is less than about 20°C.
Thermomechanical analysis (TMA) is a technique used to study the properties of materials as they change with temperature. See an exemplary protocol therefor in Example 1 herein.
[0047] Alternatively, conductive die attach films according to the present invention, upon cure, typically have a Tan Delta Tg (as determined by dynamic mechanical analysis; DMA) of less than about 100°C; in some embodiments, the Tan Delta Tg is less than about 80°C. Dynamic mechanical analysis is a technique used to determine the viscoelasticity of polymers. See an exemplary protocol therefor in Example 1 herein.
[0048] Conductive die attach films according to the present invention can also be characterized, upon cure, with reference to the tensile modulus thereof; in some embodiments, the tensile modulus of invention films (at 260°C) is less than IGPa; in some embodiments, the tensile modulus (at 260°C) is less than 500 Mpa. [0049] Conductive die attach films according to the present invention, upon cure, can also be characterized with reference to the hot die shear thereof; in some embodiments, the hot die shear of said cured film at 260°C is at least 0.5 kg/mm2; in some embodiments, the hot die shear of said film is at least 0.8 kg/mm2.
[0050] Conductive die attach films according to the present invention, upon cure, can also be characterized with reference to the hot, wet die shear thereof at 260°C after exposure to 85°C at 85% relative humidity for about 3 days; in some embodiments, the hot, wet die shear of said film after exposure to such conditions is at least 0.5 kg/mm2; in some embodiments, the hot, wet die shear of said film after exposure to such conditions is at least 0.65 kg/mm2.
[0051] In accordance with another embodiment of the present invention, there are provided methods for preparing conductive die attach films, said method comprising removing substantially all of the solvent/diluent from the above-described compositions after application thereof to a suitable substrate.
[0052] In accordance with yet another embodiment of the present invention, there are provided methods for preparing conductive die attach films, said method comprising curing the above-described compositions after application thereof to a suitable substrate, after optional b-staging thereof. In some embodiments, it is preferable that b-staging is carried out prior to curing of the above-described compositions.
[0053] Suitable substrates contemplated for use herein include lead-frame(s), laminate substrate(s) designed for semiconductor packages (e.g., BT substrate, FR4 substrate, and the like), polyethylene terephthalate, polymethyl methacrylate, polyethylene,
polypropylene, polycarbonate, an epoxy resin, polyimide, polyamide, polyester, glass, and the like.
[0054] As used herein, "lead-frame(s)" comprise a base plate consisting of copper or copper alloys, and a protective coating formed on the upper (or both) surface(s) of the base plate. The protective coating is composed of at least one metal selected from the group consisting of gold, gold alloy, silver, silver alloy, palladium or palladium alloy, and has a thickness of about 10-500 angstrom. The protective coating is formed by suitable means, e.g., by vapor deposition. It is possible to form an intermediate coating of nickel or nickel alloys between the surface of the base plate and the protective coating, by means of vapor deposition or wet plating. A suitable thickness for the intermediate coating is within the range of about 50-20,000 angstrom. See, for example, U.S. Pat. No. 5,510,197, the entire contents of which are hereby incorporated by reference herein.
[0055] hi accordance with yet another embodiment of the present invention, there are provided articles comprising conductive die attach films as described herein adhered to a suitable substrate therefor.
[0056] Articles according to the present invention can be characterized in terms of the adhesion of the cured conductive die attach film to the substrate; typically the adhesion is at least about 0.5 kg/mm2 at 260°C; in some embodiments, the adhesion is at least about 0.8 kg/mm2 at 260°C.
[0057] Articles according to the present invention can also be characterized in terms of the Tg of the cured conductive die attach film, with a Tg (as determined by thermomechanical analysis; TMA) typically being less than about 40°C; in some embodiments, the Tg is less than about 20°C.
[0058] Articles according to the present invention can alternatively be characterized with reference to the Tan Delta Tg of the cured conductive die attach film; typically, the conductive die attach film of invention articles has a Tan Delta Tg (as determined by dynamic mechanical analysis; DMA) of less than about 100°C; in some embodiments, the Tg is less than about 80°C.
[0059] Articles according to the present invention can be further characterized with reference to the tensile modulus of said cured conductive die attach film at 260°C;
typically the tensile modulus is less than about lGPa; in some embodiments, the tensile modulus is less than about 500 MPa.
[0060] As readily recognized by those of skill in the art, the dimensions of invention articles can vary over a wide range. A particular advantage of invention formulations is their suitability for preparation of large dies. Exemplary articles typically have a surface area of at least 6 mm2, and can be 2.5x2.5 mm, or 3x3 mm, or 4x4 mm, or 5x5 mm, or 6x6 mm, or 7x7mm, or 8x8 mm, or 9x9 mm, or 10x10 mm, or the like.
[0061] In accordance with yet another embodiment of the present invention, there are provided methods for preparing a conductive network, said method comprising: applying a composition as described herein to a suitable substrate in a
predefined pattern, and thereafter
curing said composition.
[0062] In accordance with still another embodiment of the present invention, there are provided conductive networks prepared as described herein.
[0063] Various aspects of the present invention are illustrated by the following non- limiting examples. The examples are for illustrative purposes and are not a limitation on any practice of the present invention. It will be understood that variations and
modifications can be made without departing from the spirit and scope of the invention. One of ordinary skill in the art readily knows how to synthesize or commercially obtain the reagents and components described herein.
EXAMPLE 1
Sample preparation
[0064] Comparison formulations and formulations according to the invention were prepared by combining the components set forth in Table 1, as follows.
Slurry Preparation
[0065] Solid resins were pre-dissolved in suitable solvent as follows. The required amounts of the organic components were weighed into a container, hand mixed for about 5 minutes, then sufficient solvent was added to fill 5-25 % of the container. Pre-mixing continued for about 5-10 minutes with a high speed mixer. The required amount of fillier was then added to the container, and the contents thereof subjected to high speed mixing (about 1000-3000 rpm) for about one hour. The resulting slurry was de-gassed by subjecting same to reduced pressure for about 1-10 minutes.
Film Preparation
[0066] Conductive films were prepared by pouring the slurry onto a clean, prepared surface using a coating machine. The slurry was subsequently heated in a retort oven to produce a stable coating film that is well bonded to the substrate (the release liner). A cover liner is than applied onto the film to protect the surface thereof. In some circumstances, it may be desirable to laminate the film under heat and pressure to promote the formation of substantially even film coatings.
Table 1
Figure imgf000023_0001
[0067] Each of formulations A, B and C were subjected to a number of analyses. TMA
[0068] For example, 5 x 5 mm samples, approximately 1-2 mm thick, were subjected to a 30-45 minute ramp-up from room temperature to 200°C, maintained for one hour at 200°C, then subjected to thermomechanical analysis (TMA) on a Perkin-Elmer Instrument with an expansion fixture with an applied force of 20mN. The heat/cool/hold parameters are summarized below:
1. Heat from 5° to 200°C at 20°C/min
2. Cool from 200°C to -85°C at 50°C/min
3. Hold 5min @-85°C
4. Heat from -85oC to 250oC at l0°C/min.
[0069] Data collection was carried out on the second heating run; data collected were used for determination of glass transition temperature (Tg), coefficient of thermal expansion 1 (CTE1), and coeffecient of thermal expansion 2 (CTE2).
DMA
[0070] DMA analysis of tensile modulus was performed on film samples employing a TA Instruments, TA-Q800 using a flat edge tension film fixture on the TA -Q800. Sample dimensions were approximately (24 x 8 x 0.2 mm). Samples were cured by subjecting them to a 30-45min ramp from room temperature to 200°C, then soaked for about lhr at 200°C.
[0071] DMA was carried out at a ramp rate of 5.0°C/min starting at -70°C up to 300°C. The frequency was 10 Hz and 5 microns was applied for strain amplitude. Results are presented in Table 2. Table 2
Figure imgf000025_0001
[0072] The results set forth in Table 2 demonstrate that excellent performance properties (e.g., low moisture absorption, good adhesion, low warpage, low Tg, low modulus) are obtained with test films based on formulations according to the present invention.
EXAMPLE 2
Warpage test method
[0073] A test vehicle (QFN12xl2 PPF leadframe with 8mm x 8mm x 300 μπι thick dies on a 9.9 mm x 9.9 mm pad was subjected to a 30 min. ramp + 60 min. hold at 200°C cure, and the resulting waipage measured. Results are presented in Table 3.
Table 3
Figure imgf000026_0001
[0074] The results set forth in Table 3 demonstrate that invention formulations are far less prone to warpage than are formulations lacking one or more of the components contemplated for use herein.
EXAMPLE 3
MSL Testing
[0075] MSL (moisture sensitivity levels) were determined according to JEDEC Standard J-STD-20 under the following conditions:
MSL1 : 85°C and 85% relative humidity for 168 hours;
MSL2: 85°C and 60% relative humidity for 168 hours; and
MSL3: 30°C and 60% relative humidity for 192 hours. The results are summarized below:
Figure imgf000027_0001
[0076] Review of the results above reveals that only invention formulations (e.g., Formulation C) are capable of meeting the more stringent conditions required by the MSL1 standard.
EXAMPLE 4
Thermal cycle testing
[0077] 12x12 mm packages with 8x8x0.3 mm dies thereon were subjected to board-level temperature cycling for 2000 cycles between room temperature and 200°C with a 30 minute ramp up and 60 minute hold at 200°C. Results are summarized below.
Figure imgf000027_0002
[0078] Review of the results above reveals that invention formulations (e.g., Formulation C) perform very well when subjected to multiple temperature cycles, providing far better adhesion than comparative formulations lacking one or more of the components required by invention formulations.
[0079] Various modifications of the present invention, in addition to those shown and described herein, will be apparent to those skilled in the art of the above description. Such modifications are also intended to fall within the scope of the appended claims.
[0080] Patents and publications mentioned in the specification are indicative of the levels of those skilled in the art to which the invention pertains. These patents and publications are incorporated herein by reference to the same extent as if each individual application or publication was specifically and individually incorporated herein by reference.
[0081] The foregoing description is illustrative of particular embodiments of the invention, but is not meant to be a limitation upon the practice thereof. The following claims, including all equivalents thereof, are intended to define the scope of the invention.

Claims

That which is claimed is:
1. A composition comprising: a first maleimide, nadimide or itacoriimide, wherein said first maleimide,
nadimide or itaconimide has an aromatic backbone, and the degree of substitution of imide moieties on the backbone of said first maleimide, nadimide or itaconimide is at least 0.5 imide moieties per repeat unit of said backbone ,
a second maleimide, nadimide or itaconimide, wherein said second maleimide, nadimide or itaconimide has a flexible aliphatic or aliphatic/aromatic backbone, wherein the backbone of said second maleimide, nadimide or itaconimide includes straight or branched chain hydrocarbyl segments, wherein each hydrocarbyl segment has at least 20 carbons,
a first epoxy resin, wherein said first epoxy resin is rubber or elastomer-modified, a second epoxy resin, wherein said second epoxy resin has a flexible aliphatic or aliphatic/aromatic backbone, wherein the backbone of said second epoxy resin includes straight or branched chain hydrocarbyl segments, wherein each hydrocarbyl segment has at least 20 carbons, backbone,
a conductive filler,
a curing agent; and
optionally a non-reactive organic diluent therefore;
wherein:
said composition, when cured, has a modulus less than about IGPa when tested by dynamic mechanical analysis (DMA) at 260°C.
2. The composition of claim 1 optionally further comprising one or more flow additives, adhesion promoters, conductivity additives, rheology modifiers, or mixtures of any two or more thereof.
3. The composition of claim 1 wherein the degree of substitution of imide moieties on the backbone of said first maleimide, nadimide or itaconimide is at least 0.8 imide moieties per repeat unit of said backbone.
4. The composition of claim 1 wherein said first maleimide, nadimide or itaconimide has the structure:
Figure imgf000030_0001
respectively, wherein:
m is 1-15,
p is 0-15,
each R2 is independently selected from hydrogen or lower alkyl, and
J is a monovalent or a polyvalent radical selected from:
- aromatic hydrocarbyl or substituted aromatic hydrocarbyl species having in the range of about 6 up to about 300 carbon atoms, where the aromatic hydrocarbyl species is selected from aryl, alkylaryl, arylalkyl, aryalkenyl, alkenylaryl, arylalkynyl or alkynylaryl;
- aromatic hydrocarbylene or substituted aromatic hydrocarbylene species having in the range of about 6 up to about 300 carbon atoms, where the aromatic hydrocarbylene species are selected from arylene, alkylarylene, arylalkylene, arylalkenylene, alkenylarylene, arylalkynylene or
alkynylarylene,
- heterocyclic or substituted heterocyclic species having in the range of about 6 up to about 300 carbon atoms,
- polysiloxane, or
- polysiloxane-polyurethane block copolymers, as well as
combinations of one or more of the above with a linker selected from a covalent bond, -
0-, -S-, -NR-, -NR-C(O)-, -NR-C(0)-0-, -NR-C(0)-NR-, -S-C(O)-, -S-C(0)-0-,
-S-C(0)-NR-, -0-S(0)2-, -0-S(0)2-0-, -0-S(0)2-NR-, -O-S(O)-, -0-S(0)-0-, -O-S(O)-
NR-, -O-NR-C(O)-, -0-NR-C(0)-0-, -0-NR-C(0)-NR-, -NR-O-C(O)-, -NR-0-C(0)-0-, -NR-0-C(0)-N -, -O-NR-C(S)-, -0-NR-C(S)-0-, -0-NR-C(S)-NR-, -NR-O-C(S)-, -NR-0-C(S)-0-, -NR-0-C(S)-NR-, -O-C(S)-, -0-C(S)-0-, -0-C(S)-NR-, -NR-C(S)-, -NR-C(S)-0-, -NR-C(S)-NR-, -S-S(0)2-, -S-S(0)2-0-, -S-S(0)2-NR-, -NR-O-S(O)-, -NR-0-S(0)-0-, -NR-0-S(0)-NR-, -NR-0-S(0)2-, -NR-0-S(0)2-0-, -NR-0-S(0)2-NR-, -O-NR-S(O)-, -0-NR-S(0)-0-, -0-NR-S(0)-NR-, -0-NR-S(0)2-0-, -0-NR-S(0)2-NR-, -0- R-S(0)2-, -0-P(0)R2-, -S-P(0)R2-, or -NR-P(0)R2-; where each R is independently hydrogen, alkyl or substituted alkyl.
5. The composition of claim 4 wherein J is heterocyclic, oxyheterocyclic, thioheterocyclic, aminoheterocyclic, carboxyheterocyclic, oxyaryl, thioaiyl, aminoaryl, carboxyaryl, heteroaryl, oxyheteroaryl, thioheteroaryl, aminoheteroaryl,
carboxyheteroaryl, oxyalkylaryl, thioalkylaryl, aminoalkylaryl, carboxyalkylaryl, oxyarylalkyl, thioarylalkyl, aminoarylalkyl, carboxyarylalkyl, oxyarylalkenyl, thioarylalkenyl, aminoarylalkenyl, carboxyarylalkenyl, oxyalkenylaryl, thioalkenylaiyl, aminoalkenylaryl, carboxyalkenylaryl, oxyarylalkynyl, thioarylalkynyl,
aminoarylalkynyl, carboxyarylalkynyl, oxyalkynylaryl, thioalkynylaryl,
aminoalkynylaryl or carboxyalkynylaryl, oxyarylene, thioarylene, aminoarylene, carboxyarylene, oxyalkylarylene, thioalkylarylene, aminoalkylarylene,
carboxyalkylarylene, oxyarylalkylene, thioarylalkylene, aminoarylalkylene,
carboxyarylalkylene, oxyarylalkenylene, thioarylalkenylene, aminoarylalkenylene, carboxyarylalkenylene, oxyalkenylarylene, thioalkenylarylene, aminoalkenylarylene, carboxyalkenylarylene, oxyarylalkynylene, thioarylalkynylene, aminoarylalkynylene, carboxy arylalkynylene, oxyalkynylarylene, thioalkynylarylene, aminoalkynylarylene, carboxyalkynylarylene, heteroarylene, oxyheteroarylene, thioheteroarylene,
aminoheteroarylene, carboxyheteroarylene, heteroatom-containing di- or polyvalent cyclic moiety, oxyheteroatom-containing di- or polyvalent cyclic moiety, thioheteroatom- containing di- or polyvalent cyclic moiety, am oheteroatom-containing di- or polyvalent cyclic moiety, or a carboxyheteroatom-containing di- or polyvalent cyclic moiety.
6. The composition of claim 1 wherein the backbone of said second maleimide, nadimide or itaconimide contains straight or branched chain hydrocarbyl segments, wherein each hydrocarbyl segment has at least 30 carbons, thereby enhancing the flexibility thereof.
7. The composition of claim 1 wherein said second maleimide, nadimide or itaconimide has the structure:
Figure imgf000032_0001
respectively, wherein:
m is 1-15,
p is 0-15,
each R2 is independently selected from hydrogen or lower alkyl, and
J is a monovalent or a polyvalent radical selected from:
- non-aromatic hydrocarbyl or substituted non-aromatic hydrocarbyl species having in the range of about 20 up to about 500 carbon atoms, where the non- aromatic hydrocarbyl species is selected from alkyl, alkenyl, alkynyl, cycloalkyl, or cycloalkenyl;
- non-aromatic hydrocarbylene or substituted non-aromatic hydrocarbylene species having in the range of about 20 up to about 500 carbon atoms, where the non-aromatic hydrocarbylene species are selected from alkylene, alkenylene, alkynylene, cycloalkylene, or cycloalkenylene,
- heterocyclic or substituted heterocyclic species having in the range of about 20 up to about 500 carbon atoms,
- polysiloxane, or
- polysiloxane-polyurethane block copolymers, as well as combinations of one or more of the above with a linker selected from a covalent bond, - 0-, -S-, -NR-, -NR-C(O)-, -NR-C(0)-0-, -NR-C(0)-NR-, -S-C(O)-, -S-C(0)-0-, -S-C(0)-NR-, -0-S(0)2-, -0-S(0)2-0-, -0-S(0)2-NR-, -O-S(O)-, -0-S(0)-0-, -O-S(O)- NR-, -O-NR-C(O)-, -0-NR-C(0)-0-, -0-NR-C(0)-NR-, -NR-O-C(O)-, -NR-0-C(0)-0-, -NR-0-C(0)-NR-, -O-NR-C(S)-, -0-NR-C(S)-0-, -0-NR-C(S)-NR-, -NR-O-C(S)-, -NR-0-C(S)-0-, -NR-0-C(S)-NR-, -O-C(S)-, -0-C(S)-0-, -0-C(S)-NR-, -NR-C(S)-, -NR-C(S)-0-, -NR-C(S)-NR-, -S-S(0)2-, -S-S(0)2-0-, -S-S(0)2- R-, -NR-O-S(O)-, -NR-0-S(0)-0-, -NR-0-S(0)-NR-, -NR-0-S(0)2-, -NR-0-S(0)2-0-, -NR-0-S(0)2-NR-, -O-NR-S(O)-, -0-NR-S(0)-0-, -0-NR-S(0)-NR-, -0-NR-S(0)2-0-, -0-NR-S(0)2-NR-, -0-NR-S(0)2-, -0-P(0)R2-, -S-P(0)R2-, or -NR-P(0)R2-; where each R is independently hydrogen, alkyl or substituted alkyl.
8. The composition of claim 7 wherein J is oxyalkyl, thioalkyl, aminoalkyl, carboxylalkyl, oxyalkenyl, thioalkenyl, aminoalkenyl, carboxyalkenyl, oxyalkynyl, thioalkynyl, aminoalkynyl, carboxyalkynyl, oxycycloalkyl, thiocycloalkyl,
aminocycloalkyl, carboxycycloalkyl, oxycloalkenyl, thiocycloalkenyl,
aminocycloalkenyl, carboxycycloalkenyl, heterocyclic, oxyheterocyclic,
thioheterocyclic, aminoheterocyclic, carboxyheterocyclic, oxyalkylene, thioalkylene, aminoalkylene, carboxyalkylene, oxyalkenylene, thioalkenylene, aminoalkenylene, carboxyalkenylene, oxyalkynylene, thioalkynylene, aminoalkynylene,
carboxyalkynylene, oxycycloalkylene, thiocycloalkylene, aminocycloalkylene, carboxycycloalkylene, oxycycloalkenylene, thiocycloalkenylene, aminocycloalkenylene, carboxycycloalkenylene, heteroatom-containing di- or polyvalent cyclic moiety, oxyheteroatom-containing di- or polyvalent cyclic moiety, thioheteroatom-containing di- or polyvalent cyclic moiety, aniinoheteroatom-containing di- or polyvalent cyclic moiety, or a carboxyheteroatom-containing di- or polyvalent cyclic moiety.
9. The composition of claim 1 wherein said first epoxy resin is an epoxidized carboxyl-terminated butadiene-acrylonitrile (CTBN) oligomer or polymer.
10. The composition of claim 9 wherein said epoxidized CTBN oligomer or polymer is an epoxy-containing derivative of an oligomeric or polymeric precursor having the structure:
HOOC[(Bu)x(ACN)y]mCOOH
wherein:
each Bu is a butylene moiety (e.g., 1,2-butadienyl or 1,4-butadienyl), each ACN is an acrylonitrile moiety,
the Bu units and the ACN units can be arranged randomly or in blocks, each of x and y are greater than zero, provided the total of x + y = 1, the ratio of x:y falls in the range of about 10:1 - 1:10, and m falls in the range of about 20 - about 100.
11. The composition of claim 1 wherein said second epoxy is an epoxidized polybutadiene diglycidylether oligomer.
12. The composition of claim 11 wherein said epoxidized polybutadiene diglycidylether oligomer has the structure:
Figure imgf000034_0001
wherein:
R1 and R2 are each independently H or lower alkyl,
R3 is H, saturated or unsaturated hydrocarbyl, or epoxy,
at least 1 epoxy-containing repeating unit set forth above, and at least one olefinic repeating unit set forth above are present in each oligomer, and, when present, in the range of 1-10 of each repeating unit is present, and
n falls in the range of 2 - 150.
13. The composition of claim 11 wherein said epoxidized polybutadiene diglycidylether oligomer has the structure:
Figure imgf000035_0001
wherein R is H, OH, lower alkyl, epoxy, oxirane-substituted lower alkyl, aryl or alkaryl.
14. The composition of claim 1 wherein said conductive filler is selected from silver, nickel, cobalt, copper, gold, palladium, platinum, carbon black, carbon fiber, graphite, aluminum, indium tin oxide, silver-coated copper, silver-coated aluminum, silver-coated graphite, nickel-coated graphite, bismuth, tin, bismuth-tin alloy, metal- coated glass spheressilver-coated fiber, silver-coated spheres, antimony doped tin oxide, carbon nanotubes, conductive nanofillers, alloys of such metals, as well as mixtures of any two or more thereof.
15. The composition of claim 1 wherein said curing agent comprises ureas, aliphatic and aromatic amines, amine hardeners, polyamides, imidazoles,
dicyandiamides, hydrazides, urea-amine hybrid curing systems, free radical initiators organic bases, transition metal catalysts, phenols, acid anhydrides, Lewis acids, and/or Lewis bases.
16. The composition of claim 1 wherein said diluent, when present, is an aromatic hydrocarbon, a chlorinated hydrocarbon, an ether, a polyol, a ketone, an amide, or a heteroaromatic compound.
17. The composition of claim 1 further comprising up to about 4 wt % of an additional polymeric moiety selected from an acrylic polymer, a polyurethane or a polysiloxane.
18. The composition of claim 17 wherein said additional polymeric moiety is an acrylic polymer having a molecular weight in the range of about 100,000 up to about 1,000,000 and a Tg in the range of about -40°C up to about 20°C.
19. The composition of claim 1, wherein said composition, when applied at a thickness of 0.2mm on a suitable 10x10mm copper substrate pad and cured at 200°C for 60 minutes, undergoes less than 58 micron warpage.
20. The composition of claim 1 wherein the water absorption of said composition upon cure, when exposed to a relative humidity of 85 at 85°C in a Dynamic Vapor Sorption Analyzer is less than 1 wt %.
21. The composition of claim 1 wherein the water absorption of said composition upon cure, when exposed to a relative humidity of 85 at 85°C in a Dynamic Vapor Sorption Analyzer, is less than 0.5 wt %.
22. The composition of claim 1 wherein said composition comprises: at least 1 wt % of said first maleimide, nadimide or itaconimide, at least 1 wt % of said second maleimide, nadimide or itaconimide, at least 2 wt % of said first epoxy,
at least 0.5 wt % of said second epoxy,
at least 70 wt % of said conductive filler,
at least 0.3 wt % of said curing agent,
optionally up to 4 wt % of an additional polymeric moiety selected from an acrylic polymer, a polyurethane or a polysiloxane, and
optionally, up to 25 wt % of a non-reactive organic diluent therefore.
23. The composition of claim 22 wherein said composition comprises:
1-6 wt % of said first maleimide, nadimide or itaconimide,
1-8 wt % of said second maleimide, nadimide or itaconimide, 2-15 wt % of said first epoxy,
0.5-8 wt % of said second epoxy,
70-95 wt % of said conductive filler,
0.3-4 wt % of said curing agent,
optionally up to 4 wt % of an additional polymeric moiety selected from an acrylic polymer, a polyurethane or a polysiloxane, and
optionally up to 25 wt % of a non-reactive organic diluent therefore.
24. A method of making the composition of claim 1, said method comprising subjecting the combination of components to high shear mixing for a time sufficient to obtain a substantially homogeneous blend.
25. A conductive die attach film comprising the reaction product obtained upon removing substantially all of the solvent/diluent from the composition of claim 1.
26. The conductive die attach film of claim 25 wherein said composition is cured at a temperature in the range of about 160 - 230 °C for a time in the range of about 30 minutes - 2 hours.
27. The conductive die attach film of claim 26 wherein said film absorbs less than 1.2 % by weight moisture when exposed to 85°C at 85% relative humidity in a Dynamic Vapor Sorption Analyzer.
28. The conductive die attach film of claim 26 wherein the film has a Tg (as determined by thermomechanical analysis; TMA) of less than about 40°C.
29. The conductive die attach film of claim 26 wherein the film has a Tan Delta Tg (as determined by dynamic mechanical analysis; DMA) of less than about 100°C.
30. The conductive die attach film of claim 26 wherein the tensile modulus of said film at 260°C is less than lGPa.
31. The conductive die attach film of claim 26 wherein the die shear of said film at 260°C is at least 0.5 kg/mm2.
32. The conductive die attach film of claim 26 wherein the die shear of said film at 260°C after exposure to 85°C at 85% relative humidity for about 3 days is at least 0.5 kg/mm2.
33. A method for preparing a conductive die attach film, said method comprising b-staging the composition of claim 1 after application thereof to a suitable substrate.
34. The method of claim 33 wherein said suitable substrate is selected from lead-frame(s), laminate substrate(s) designed for semiconductor packages, a polyethylene terephthalate, a polymethyl methacrylate, a polyethylene, a polypropylene, a
polycarbonate, an epoxy resin, a polyimide, a polyamide, a polyester, or glass.
35. The method of claim 33 further comprising curing said conductive die attach film.
36. An article comprising a conductive die attach film according to claim 25 adhered to a suitable substrate therefor.
37. The article of claim 36 wherein the adhesion of said conductive die attach film to said substrate is at least 0.5 kg/mm2 at 260°C.
38. The article of claim 36 wherein the conductive die attach film, upon curing, has a Tg (as determined by thermomechanical analysis; TMA) of less than about 40°C.
39. The article of claim 36 wherein the conductive die attach film, after curing, has a Tan Delta Tg (as deteraiined by dynamic mechanical analysis; DMA) of less than about 100°C.
40. The article of claim 36 wherein the tensile modulus of said conductive die attach film at 260°C, after curing, is less than lGPa.
41. The article of claim 36 further comprising a die, wherein the dimensions of said die are at least 2.5x2.5 mm.
42. A method for preparing a conductive network, said method comprising: applying a composition according to claim 1 to a suitable substrate in a predefined pattern,
optionally removing solvent/diluent therefrom, and thereafter curing said composition.
43. A conductive network prepared by the method of claim 42.
44. A method for preparing a conductive network, said method comprising: applying a composition according to claim 1 to a suitable substrate in a predefined pattern,
removing solvent/diluent therefrom, and thereafter
curing said composition.
45. A conductive network prepared by the method of claim 44.
PCT/US2014/058000 2013-09-30 2014-09-29 Conductive die attach film for large die semiconductor packages and compositions useful for the preparation thereof Ceased WO2015048621A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2016545261A JP6378346B2 (en) 2013-09-30 2014-09-29 Conductive die attach films for large die semiconductor packages and compositions useful for their preparation
CN201480042671.2A CN105473657B (en) 2013-09-30 2014-09-29 Composition for the conductive wafer adhesive film of larger wafers package semiconductor and for preparing conductive wafer adhesive film
EP14847431.5A EP3052566B1 (en) 2013-09-30 2014-09-29 Conductive die attach film for large die semiconductor packages and compositions useful for the preparation thereof
KR1020167007600A KR101909353B1 (en) 2013-09-30 2014-09-29 Conductive die attach film for large die semiconductor packages and compositions useful for the preparation thereof
US15/010,531 US9449938B2 (en) 2013-09-30 2016-01-29 Conductive die attach film for large die semiconductor packages and compositions useful for the preparation thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361884844P 2013-09-30 2013-09-30
US61/884,844 2013-09-30

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/010,531 Continuation US9449938B2 (en) 2013-09-30 2016-01-29 Conductive die attach film for large die semiconductor packages and compositions useful for the preparation thereof

Publications (1)

Publication Number Publication Date
WO2015048621A1 true WO2015048621A1 (en) 2015-04-02

Family

ID=52744560

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/058000 Ceased WO2015048621A1 (en) 2013-09-30 2014-09-29 Conductive die attach film for large die semiconductor packages and compositions useful for the preparation thereof

Country Status (7)

Country Link
US (1) US9449938B2 (en)
EP (1) EP3052566B1 (en)
JP (1) JP6378346B2 (en)
KR (1) KR101909353B1 (en)
CN (1) CN105473657B (en)
TW (1) TWI651387B (en)
WO (1) WO2015048621A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017066563A1 (en) 2015-10-15 2017-04-20 Henkel IP & Holding GmbH Use of nickel and nickel-containing alloys as conductive fillers in adhesive formulations

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9672798B1 (en) * 2012-11-29 2017-06-06 Flexcon Company, Inc. Systems and methods for providing decorative drum shell wraps
JP2019511587A (en) * 2016-02-04 2019-04-25 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング Peelable adhesive and its high temperature use
US9892999B2 (en) * 2016-06-07 2018-02-13 Globalfoundries Inc. Producing wafer level packaging using leadframe strip and related device
CN120003120A (en) * 2017-03-17 2025-05-16 汉高股份有限及两合公司 Improved working life of multilayer articles and method for preparing and using the same
KR102351843B1 (en) * 2017-06-07 2022-01-18 쇼와덴코머티리얼즈가부시끼가이샤 Film adhesive for semiconductor, semiconductor device manufacturing method and semiconductor device
KR102156470B1 (en) * 2017-09-11 2020-09-15 주식회사 엘지화학 Selection method of adhesive agents having improved folding stability
US11791237B2 (en) * 2018-06-27 2023-10-17 Intel Corporation Microelectronic assemblies including a thermal interface material
JP7164386B2 (en) * 2018-10-04 2022-11-01 タツタ電線株式会社 conductive paint
CN109971175B (en) * 2019-03-18 2021-09-21 苏州生益科技有限公司 Modified maleimide resin composition, prepreg and laminated board prepared from same
US12166004B2 (en) 2019-05-08 2024-12-10 Intel Corporation Solder thermal interface material (STIM) with dopant
US12272614B2 (en) 2019-05-28 2025-04-08 Intel Corporation Integrated circuit packages with solder thermal interface materials with embedded particles
US11682605B2 (en) 2019-05-28 2023-06-20 Intel Corporation Integrated circuit packages with asymmetric adhesion material regions
CN112011181A (en) * 2019-05-31 2020-12-01 台光电子材料(昆山)有限公司 Resin composition and product thereof
JP7442669B2 (en) * 2020-03-12 2024-03-04 ドゥーサン コーポレイション Adhesive composition, coverlay film containing the same, and printed circuit board
WO2025106944A1 (en) * 2023-11-16 2025-05-22 Henkel Ag & Co. Kgaa Flexible conductive adhesive compositions
TW202547929A (en) * 2024-03-28 2025-12-16 德商漢高股份有限及兩合公司 Thermal conductivity promoter for electrically conductive compositions

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4020036A (en) 1976-04-22 1977-04-26 Phillips Petroleum Company Thermosetting polyester composition containing normally solid carboxy-containing diene polymer
US4101604A (en) 1977-07-18 1978-07-18 The B. F. Goodrich Company Unsaturated polyester molding compositions
US4160759A (en) 1978-01-30 1979-07-10 Exxon Research & Engineering Co. Elastomer modified polyester molding compound
US4161471A (en) 1978-04-13 1979-07-17 E. I. Du Pont De Nemours And Company Elastomer modified unsaturated molding compositions
US5397618A (en) 1991-07-11 1995-03-14 The Dexter Corporation Multilayer composite article containing a multimodal combination of filler particles
US5510197A (en) 1993-04-28 1996-04-23 Mitsubishi Shindoh Co., Ltd. Lead frame material and lead frame for semiconductor device
US5717034A (en) 1996-07-29 1998-02-10 Quantum Materials, Inc. Perfluorinated hydrocarbon polymer-filled adhesive formulations and uses therefor
US20050288457A1 (en) * 2002-10-22 2005-12-29 Puwei Liu Co-curable compositions
US7037447B1 (en) * 2003-07-23 2006-05-02 Henkel Corporation Conductive ink compositions
EP1715004A1 (en) 2005-04-18 2006-10-25 National Starch and Chemical Investment Holding Corporation Die attach adhesives with improved stress performance
WO2012022011A1 (en) * 2010-08-20 2012-02-23 Ablestik (Shanghai) Limited Stabilized, silver coated filler-containing curable compositions
WO2013015469A1 (en) 2011-07-28 2013-01-31 Protavic Korea Co., Ltd. Flexible bismaleimide, benzoxazine, epoxy-anhydride adduct hybrid adhesive

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57205413A (en) * 1981-06-11 1982-12-16 Mitsui Toatsu Chem Inc Curable resin composition
US6750301B1 (en) * 2000-07-07 2004-06-15 National Starch And Chemical Investment Holding Corporation Die attach adhesives with epoxy compound or resin having allyl or vinyl groups
US6583201B2 (en) * 2001-04-25 2003-06-24 National Starch And Chemical Investment Holding Corporation Conductive materials with electrical stability for use in electronics devices
US6831132B2 (en) 2002-03-28 2004-12-14 Henkel Corporation Film adhesives containing maleimide compounds and methods for use thereof
US7176044B2 (en) 2002-11-25 2007-02-13 Henkel Corporation B-stageable die attach adhesives
US7326369B2 (en) 2005-03-07 2008-02-05 National Starch And Chemical Investment Holding Corporation Low stress conductive adhesive
JP5228320B2 (en) * 2006-12-13 2013-07-03 住友ベークライト株式会社 Resin composition, insulating material with supporting substrate, and metal-clad laminate for flexible printed circuit board
US7422707B2 (en) * 2007-01-10 2008-09-09 National Starch And Chemical Investment Holding Corporation Highly conductive composition for wafer coating
KR20140143430A (en) * 2007-07-26 2014-12-16 헨켈 아게 운트 코. 카게아아 Alcohols containing imide moieties and reactive oligomers prepared therefrom
WO2009117345A2 (en) * 2008-03-17 2009-09-24 Henkel Corporation Adhesive compositions for use in die attach applications
KR101990258B1 (en) * 2008-08-08 2019-06-17 헨켈 아이피 앤드 홀딩 게엠베하 Low temperature curing compositions
JP5482077B2 (en) * 2009-10-09 2014-04-23 住友ベークライト株式会社 Resin composition and semiconductor device produced using resin composition
JP5356326B2 (en) * 2010-07-20 2013-12-04 日東電工株式会社 Manufacturing method of semiconductor device
SG188309A1 (en) * 2010-09-07 2013-04-30 Sumitomo Bakelite Co Resin composition and semiconductor device produced using resin composition
CN102199413A (en) * 2011-03-26 2011-09-28 舟山维特新材料科技有限公司 Modified epoxy resin adhesive used for polyimide flexible copper-clad plate
TWI569381B (en) * 2011-05-27 2017-02-01 住友電木股份有限公司 Semiconductor device
US20140120356A1 (en) * 2012-06-18 2014-05-01 Ormet Circuits, Inc. Conductive film adhesive
JP6272729B2 (en) * 2014-05-16 2018-01-31 日東電工株式会社 Dicing tape-integrated film for semiconductor back surface and method for manufacturing semiconductor device

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4020036A (en) 1976-04-22 1977-04-26 Phillips Petroleum Company Thermosetting polyester composition containing normally solid carboxy-containing diene polymer
US4101604A (en) 1977-07-18 1978-07-18 The B. F. Goodrich Company Unsaturated polyester molding compositions
US4160759A (en) 1978-01-30 1979-07-10 Exxon Research & Engineering Co. Elastomer modified polyester molding compound
US4161471A (en) 1978-04-13 1979-07-17 E. I. Du Pont De Nemours And Company Elastomer modified unsaturated molding compositions
US5397618A (en) 1991-07-11 1995-03-14 The Dexter Corporation Multilayer composite article containing a multimodal combination of filler particles
US5510197A (en) 1993-04-28 1996-04-23 Mitsubishi Shindoh Co., Ltd. Lead frame material and lead frame for semiconductor device
US5717034A (en) 1996-07-29 1998-02-10 Quantum Materials, Inc. Perfluorinated hydrocarbon polymer-filled adhesive formulations and uses therefor
US20050288457A1 (en) * 2002-10-22 2005-12-29 Puwei Liu Co-curable compositions
US7037447B1 (en) * 2003-07-23 2006-05-02 Henkel Corporation Conductive ink compositions
EP1715004A1 (en) 2005-04-18 2006-10-25 National Starch and Chemical Investment Holding Corporation Die attach adhesives with improved stress performance
WO2012022011A1 (en) * 2010-08-20 2012-02-23 Ablestik (Shanghai) Limited Stabilized, silver coated filler-containing curable compositions
WO2013015469A1 (en) 2011-07-28 2013-01-31 Protavic Korea Co., Ltd. Flexible bismaleimide, benzoxazine, epoxy-anhydride adduct hybrid adhesive

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017066563A1 (en) 2015-10-15 2017-04-20 Henkel IP & Holding GmbH Use of nickel and nickel-containing alloys as conductive fillers in adhesive formulations
CN108779373A (en) * 2015-10-15 2018-11-09 汉高知识产权控股有限责任公司 Nickel and contain purposes of the alloy of nickel as conductive filler in adhesive formulation
EP3362530A4 (en) * 2015-10-15 2019-06-05 Henkel IP & Holding GmbH USE OF NICKEL AND ALLOYS CONTAINING NICKEL AS CONDUCTIVE LOADS IN ADHESIVE FORMULATIONS

Also Published As

Publication number Publication date
TW201512367A (en) 2015-04-01
US9449938B2 (en) 2016-09-20
KR101909353B1 (en) 2018-10-17
TWI651387B (en) 2019-02-21
JP2016533422A (en) 2016-10-27
CN105473657B (en) 2017-12-22
EP3052566B1 (en) 2018-11-07
EP3052566A4 (en) 2017-05-31
JP6378346B2 (en) 2018-08-22
KR20160065828A (en) 2016-06-09
US20160148894A1 (en) 2016-05-26
EP3052566A1 (en) 2016-08-10
CN105473657A (en) 2016-04-06

Similar Documents

Publication Publication Date Title
EP3052566B1 (en) Conductive die attach film for large die semiconductor packages and compositions useful for the preparation thereof
US12042883B2 (en) Sinterable films and pastes and methods for use thereof
US20120172495A1 (en) Underfill for high density interconnect flip chips
US10242923B2 (en) Formulations containing mixed resin systems and the use thereof for wafer-level underfill for 3D TSV packages
TWI790188B (en) Methods for improving performance properties of thermoset polymer resins
US20180340102A1 (en) Use of nickel and nickel-containing alloys as conductive fillers in adhesive formulations
KR20020038532A (en) Liquid Epoxy Resin Compositions and Semiconductor Devices
KR20060048870A (en) Composition for semiconductor package containing oxetane compound
JP2008274090A (en) Adhesive composition and method of using the same
US10927249B2 (en) Resin compositions for underfill film for three dimensional through silica via (TSV) packages and compositions useful for the preparation thereof
JP5099850B2 (en) Semiconductor element sealing composition
US20110166258A1 (en) Resin composition for no-flow underfill, no-flow underfill flim using the same and manufacturing method thereof
WO2025106944A1 (en) Flexible conductive adhesive compositions
TWI752195B (en) Worklife improvement for multilayer articles comprising at least one underfill film and methods for the preparation and use thereof
KR20260025081A (en) Thermally conductive die attach film

Legal Events

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

Ref document number: 201480042671.2

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14847431

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2014847431

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2014847431

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20167007600

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2016545261

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE