B-stageable die attach adhesives

• US 7,176,044 B2
• Filed: 06/12/2003
• Issued: 02/13/2007
• Est. Priority Date: 11/25/2002
• Status: Active Grant

• Current Assignee: Henkel IP & Holding GmbH (Henkel AG & Co KGaA)
• Original Assignee: Henkel Corporation (Henkel AG & Co KGaA)
• Inventors: Liu, Puwei, Santos, Benedicto delos, Forray, Deborah Derfelt
• Primary Examiner(s): Lebentritt; Michael
• Assistant Examiner(s): STEVENSON, ANDRE C
• Application Number:
  US10/459,601
• Publication Number:
  US 20040102566A1
• Time in Patent Office: 1,342 Days
• Field of Search: 438/6, 438 10- 15, 438/104, 438107-114, 438/118, 438121-123, 438128-129, 438/135, 438/142, 438/145, 438/149, 438/151, 438/157, 438/176, 438/478, 438/184, 438/193, 438195-198, 438200-203, 438206-211, 438/218, 438/237, 438/165, 438/294, 438/308, 438/337, 438/353, 438/378
• US Class Current: 438/15
• CPC Class Codes: C09J 5/06 involving heating of the applied adhesive
• CPC Class Codes: H01L 2224/29 of an individual layer connector
• CPC Class Codes: H01L 2224/29099 Material
• CPC Class Codes: H01L 2224/29101 the principal constituent melting at a temperature of less than 400°C
• CPC Class Codes: H01L 2224/2919 with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
• CPC Class Codes: H01L 2224/29199 Material of the matrix
• CPC Class Codes: H01L 2224/2929 with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
• CPC Class Codes: H01L 2224/29299 Base material
• CPC Class Codes: H01L 2224/29324 Aluminium [Al] as principal constituent
• CPC Class Codes: H01L 2224/29339 Silver [Ag] as principal constituent
• CPC Class Codes: H01L 2224/29344 Gold [Au] as principal constituent
• CPC Class Codes: H01L 2224/29347 Copper [Cu] as principal constituent
• CPC Class Codes: H01L 2224/29355 Nickel [Ni] as principal constituent
• CPC Class Codes: H01L 2224/29357 Cobalt [Co] as principal constituent
• CPC Class Codes: H01L 2224/29386 with a principal constituent of the material being a non metallic, non metalloid inorganic material
• CPC Class Codes: H01L 2224/29393 with a principal constituent of the material being a solid not provided for in groups H01L2224/293 - H01L2224/29391, e.g. allotropes of carbon, fullerene, graphite, carbon-nanotubes, diamond
• CPC Class Codes: H01L 2224/29439 Silver [Ag] as principal constituent
• CPC Class Codes: H01L 2224/29455 Nickel [Ni] as principal constituent
• CPC Class Codes: H01L 2224/32145 the bodies being stacked
• CPC Class Codes: H01L 2224/32225 the item being non-metallic, e.g. insulating substrate with or without metallisation
• CPC Class Codes: H01L 2224/45015 : being circular
• CPC Class Codes: H01L 2224/45139 : Silver (Ag) as principal constituent
• CPC Class Codes: H01L 2224/48091 : Arched
• CPC Class Codes: H01L 2224/48227 : connecting the wire to a bond pad of the item
• CPC Class Codes: H01L 2224/73265 : Layer and wire connectors
• CPC Class Codes: H01L 2224/83191 : wherein the layer connectors are disposed only on the semiconductor or solid-state body
• CPC Class Codes: H01L 2224/83855 : Hardening the adhesive by curing, i.e. thermosetting
• CPC Class Codes: H01L 2224/83856 : Pre-cured adhesive, i.e. B-stage adhesive
• CPC Class Codes: H01L 24/29 : of an individual layer connector
• CPC Class Codes: H01L 24/73 : Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
• CPC Class Codes: H01L 24/83 : using a layer connector
• CPC Class Codes: H01L 2924/00 : Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/00011 : Not relevant to the scope of the group, the symbol of which is combined with the symbol of this group
• CPC Class Codes: H01L 2924/00012 : Relevant to the scope of the group, the symbol of which is combined with the symbol of this group
• CPC Class Codes: H01L 2924/00013 : Fully indexed content
• CPC Class Codes: H01L 2924/00014 : the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
• CPC Class Codes: H01L 2924/01004 : Beryllium [Be]
• CPC Class Codes: H01L 2924/01005 : Boron [B]
• CPC Class Codes: H01L 2924/01006 : Carbon [C]
• CPC Class Codes: H01L 2924/01013 : Aluminum [Al]
• CPC Class Codes: H01L 2924/01015 : Phosphorus [P]
• CPC Class Codes: H01L 2924/01016 : Sulfur [S]
• CPC Class Codes: H01L 2924/01018 : Argon [Ar]
• CPC Class Codes: H01L 2924/01019 : Potassium [K]
• CPC Class Codes: H01L 2924/01023 : Vanadium [V]
• CPC Class Codes: H01L 2924/01024 : Chromium [Cr]
• CPC Class Codes: H01L 2924/01027 : Cobalt [Co]
• CPC Class Codes: H01L 2924/01029 : Copper [Cu]
• CPC Class Codes: H01L 2924/01032 : Germanium [Ge]
• CPC Class Codes: H01L 2924/01033 : Arsenic [As]
• CPC Class Codes: H01L 2924/01039 : Yttrium [Y]
• CPC Class Codes: H01L 2924/01046 : Palladium [Pd]
• CPC Class Codes: H01L 2924/01047 : Silver [Ag]
• CPC Class Codes: H01L 2924/01048 : Cadmium [Cd]
• CPC Class Codes: H01L 2924/01049 : Indium [In]
• CPC Class Codes: H01L 2924/01074 : Tungsten [W]
• CPC Class Codes: H01L 2924/01075 : Rhenium [Re]
• CPC Class Codes: H01L 2924/01076 : Osmium [Os]
• CPC Class Codes: H01L 2924/01077 : Iridium [Ir]
• CPC Class Codes: H01L 2924/01078 : Platinum [Pt]
• CPC Class Codes: H01L 2924/01079 : Gold [Au]
• CPC Class Codes: H01L 2924/014 : Solder alloys
• CPC Class Codes: H01L 2924/04642 : SiC
• CPC Class Codes: H01L 2924/0503 : 13th Group
• CPC Class Codes: H01L 2924/05032 : AlN
• CPC Class Codes: H01L 2924/0532 : 2nd Group
• CPC Class Codes: H01L 2924/05432 : Al2O3
• CPC Class Codes: H01L 2924/05442 : SiO2
• CPC Class Codes: H01L 2924/0665 : Epoxy resin
• CPC Class Codes: H01L 2924/07802 : not being an ohmic electrical conductor
• CPC Class Codes: H01L 2924/10253 : Silicon [Si]
• CPC Class Codes: H01L 2924/15787 : Ceramics, e.g. crystalline carbides, nitrides or oxides
• CPC Class Codes: H01L 2924/207 : Diameter ranges
• CPC Class Codes: Y10T 156/10 : Methods of surface bonding and/or assembly therefor
• CPC Class Codes: Y10T 428/31504 : Composite [nonstructural laminate]

Abstract

The present invention relates to b-stageable die attach adhesives, methods of preparing such adhesives, methods of applying such adhesives to the die and other substrate surfaces, and assemblies prepared therewith for connecting microelectronic circuitry.

Claims

1. A b-stage curable composition comprising:

a. a solid component heat curable at a first temperature;

b. a liquid component, which is either heat curable at a second temperature or curable upon exposure to radiation in the electromagnetic spectrum; and

c. a heat cure catalyst for the solid curable component, wherein the liquid curable component comprises epoxies, episuldides, maleimides, nadimides, itaconimides, (meth)acrylate, vinyl ethers, vinyl esters, styrene and derivatives thereof, poly(alkenylene)s, allyl amides, norbornenyls, thiolenes, and combinations thereof.

2. The composition of claim 1, wherein the solid curable component has a melting point range that is less than the temperature at which the solid curable component cures.

3. The composition of claim 1, wherein the solid curable component has a melting point range that is substantially the same as the temperature at which the solid curable component cures.

4. The composition of claim 1, further comprising a reactive diluent.

5. The composition of claim 1, wherein the composition is substantially free of non-reactive solvent.

6. The composition of claim 1, further comprising solvent.

7. The composition of claim 1, further comprising a filler.

8. The composition of claim 7, wherein the wherein the filler is conductive.

9. The composition of claim 7, wherein the filler is thermally conductive.

10. The composition of claim 7, wherein the filler is electrically conductive.

11. The composition of claim 7, wherein the filler is nonconductive.

12. The composition of claim 7, wherein me filler has a particle size of less than about 50 microns.

13. The composition or claim 1, further comprising a photoinitiator.

14. The composition of claim 13, wherein the photoinitiator is selected from the group consisting of catalysts triggered by radiation in the UV, UV/VTS VIS, IR, E-beam, X-ray, and microwave ranges of the electromagnetic spectrum.

32. A method of preparing the composition of claim 1, the steps of which comprise

a. providing a solid curable component heat curable at a first temperature, a liquid curable component, which is either heat curable at a second temperature or curable upon exposure to radiation in the electromagnetic spectrum, and a heat cure catalyst for the solid curable component;

and

b. mixing together the solid curable component, liquid curable component and the heat cure catalyst.

33. The method of claim 32, further comprising

c. exposing the composition to conditions favorable to effect cure of the liquid curable component.

34. The method of claim 33, further comprising

d. exposing the composition to a temperature condition sufficient to melt the solid curable component.

35. The method of claim 34, further comprising

e. exposing the compostion to a temperature condition sufficient to cure the melted, solid curable componet.

15. A b-stage curable composition comprising:

a. a solid component heat curable at a first temperature;

b. a liquid component, which is either heat curable at a second temperature or curable upon exposure to radiation in the electromagnetic spectrum; and

c. a heat cure catalyst for the solid curable component, wherein the heat cure catalyst is selected from the group consisting of free radical catalysts, anionic curatives, cationic curatives, and combinations thereof, wherein the tree radical catalyst is a member selected from the group consisting of peroxides, azo compounds, and combinations thereof.

16. The composition of claim 15, wherein the free radical catalyst is a member selected from the group consisting of peroxides, azo compounds, and combinations thereof, wherein the anionic curative is a member selected from the group consisting of aza compounds, amine compounds, imidazole compounds, and combinations thereof.

17. The composition of claim 15, wherein the anionic curative is a member selected from the group consisting of aza compounds, amine compounds, imidazole compounds, and combinations thereof, wherein the aza compounds are members selected from the group consisting of

18. The composition of claim 17, wherein the amine compounds are members selected from the group consisting of aliphatic polyamines, aromatic polyamines, alicyclic polyamines, and combinations thereof.

19. The composition of claim 17, wherein the amine compounds are members selected from the group consisting of diethylenetriamine, triethylenetetraamine, diethylaminopropylamine, benzyl dimethylamine, m-xylenediamine, diaminodiphenylamine, quinoxaline, isophoronediamine, menthenediamine and combinations thereof.

20. The composition of claim 17, wherein the imidazole compounds are members selected from the group consisting of isoimidazole, imidazole, 2ethyl-4-methylimidazole, 2,4dimethylimidazole, butylimidazole, 2-heptadecenyl-4-methylimidazole, 2methylimidazole, 2-undecenylimidazole, 1-vinyl-2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl2methylimidazole, 1-cyanoethyl-2ethyl4 methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl 2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole, addition products of an imidazole and methylimidazole, addition products of an imidazole and trimellitic acid, 2-n-heptadecyl-4-methylimidazole, phenylimidazole, benzylimiclazoie, 2-methyi-4,5-diohenylimidazole, 2,3,5-triphenylimidazole, 2-styrylimidazole, 1-(dodecyl benzyl)-2-methyilmidazole, 2-(2-hydroxyl-4-t-butyiphenyl)-4,5-diphenylimidazole, 2-(2-methoxyphenyl)-4,5-diphenylimidazole, 2-(3-hydroxyphenyl)-4,5-diphenylimidazole, 2-(p-dimethylaminophenyl)-4,5-diphenylimidazole, 2-(2-hydroxyphenyl)-4,5-diphenylimidazole, di(4,5-diphenyl-2-imidazole) benzene-1,4, 2-naphthyl-4,5-diphenylimidazole, 1-benzyl-2-methylimidazole, 2-p-methoxystyrylimidazole, and combinations thereof.

21. A stage curable composition comprising:

a. a solid component heat curable at a first temperature;

b. a liquid component, whicn is either heat curable at a second temperature or curable up on exposure to radiation in the electromagnetic spectrum; and

c. a heat cure catalyst for the solid curable component, wherein the cationic curative is a member selected from the group consisting of organic acids, anhydrides, Lewis acids, and combinations thereof, wherein the heat cure catalyst. is selected from the group consisting of free radical catalysts, anionic curatives, cationic curatives, and combinations thereof.

22. The composition of claim 21, wherein the organic acid is a member selected from the group consisting of phenols, thiophenols, thiols, carboxylic acids, and combinations thereof.

23. A b-stage curable composition comprising:

a. a solid component heat curable at a first temperature;

b. a liquid component, whicn is either heat curable at a second temperature or curable upon exposure to radiation in the electromagnetic spectrum; and

c. a heat cure catalyst for the solid curable component, further comprising a second heat cure catalyst for the liquid curable component.

24. The composition of claim 23, wherein cure of the liquid curable component by the second heat cure catalyst occurs at a temperature within the range of about 50°

C. to about 150°

C. and cure of the solid curable component by the first heat cure catalyst occurs at a temperature wirhin the grange of about 100°

C.to about 300°

C.

25. The composition of claim 23, wherein cure of the lipuid curable component by the second heat cure catalyst occurs at a temperature iess than about 100°

C. and cure of the solid curable component by the first heat cure catalyst occurs at a temperature above about 100°

C.

26. A b-stage curable composition comprising:

a. a solid component heat curable at a first temperature;

b. a liquid component, which is either heat curable at a second temperature or curable upon exposure to radiation in the electromagnetic spectrum; and

c. a heat cure catalyst for the solid curable component, wherein the solid curable component comprises one or more of a group of epoxies, episulfides, maleimides, nadimides, itaconinides, (meth)acrylate, vinyl ethers, vinyl esters, styrene and derivatives thereof, poly(alkenylene)s, allyl amides, norbornenyls, thiolenes, and combinataons thereof.

27. A b-stage curable composition comprising:

a. a solid component heat curable at a first temperature;

b. a liquid component, which is either heat curable at a second temperature or curable up on exposure to radiation in the electromagnetic spectrum; and

c. a heat cure catalyst for the solid curable component, wherein the liquid curable component is a member selected from the group consisting of a maleimide-containing compound, a nadimide-containing compound or a itaconimide-contaning compound comprising

28. A b-stage curable composition comprising:

a. a solid component heat curable at a first temperature;

b. A liquid componet, which is either heat curable at a second temperature or curable upon exposure to radiation in the electromagnetic spectrum; and

c. a heat cure catalyst for the solid curable component, wherein the liquid curable component is a member selected from the group consisting of a maleimide-containing compound, a nadimide-contaning compound or a itaconimide-containing compound comprising structures I, II and III, wherein

m=1–

6,

p=0,

R² is independently selected from hydrogen or lower alkyl, and

J is a monovalent or polyvalent radical selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, polysiloxane, polysiloxane-polyurethane block copolymer, and combinations of two or more thereof, optionally containing one or more linkers selected from a covalent bond, -O-, -S-, -NR-, -O-C(O)-, -O-C(O)-O-, -OC(O)-NR-, -NR-C(O)-, -NR-C(O)-O-, -NR-C(O)-NR-, -S-c(O)-, -S-C(O)-O-, -S-C(O)-NR-, -S(O)-, -S(O)₂-, -O-S(O)₂-, -O-S(O)₂-O-, -OS(O)₂-NR-, -O-S(O)-, -O-S(O)-O-, -O-S(O)-NR-, -O-NR-C(O)-, -O-NR-C(O)-O-, -O-NR-C(O)-NR-, -NR-O-C(O)-, -NR-O-C(O)-O-, -NR-O-C(O)-NR-, -NR-O-C(S)-O_, -NR-O-C(S)-NR-, -O-(S)-, -O-C(S)-O-, -O-C(S)-NR-, -NR-C(S)-, -NR-C(S)-O-, -NR-C(S)-NR-, -S-S(O)₂-, -S-S(O)₂-O-, -S-S(O0₂-NR-, -NR-O-S(O)-, -NR-O-S(O)-O-, -NR-O-S(O)-NR-O-S(O)₂-, -NR-O-S(O)₂-O-, -NR-O-S(O)₂NR-, -O-NR-S(O)-, -O-NR-S(O)-O-, -O-NR-S(O)-NR-, -O_NR-S(O)₂-O-, -O-NR-S(O)₂-NR-, -O-NR-S(O)₂-, -O-P(O)R₂-, -S-P(O)R₂-, -NR-P(O)R₂-, wherein each R is independently hydrogen, alkyl or substituted alkyl, and combinations of any two or more thereof.

29. A b-stage curable composition comprising:

a. a solid component heat curable at a first temperature;

b. a liquid component, which is either heat curable at a second temperature or curable upon exposure to radiation in the electromagnetic spectrum; and

c. a heat cure catalyst for the solid curable componet, wherein the solid curable component is a maleimide-containing compound, a nadimide-containing compound or a itaconimide-contaning compound in the solid state at room temperature.

30. The compositin of claim 29, wherein the maleimide-containing compound, the itaconimide-containing compound or the nadimide-containing compound is a solid and is a member selected from the group consisting of:

31. A b-stage curable composition comprising;

a. a solid component heat curable at a first temperature;

b. a liquid component, which is either heat curable at a second temperature or curable upon exposure to radiation in the electromagnetic spectrum; and

c. a heat cure catalyst for the solid curable component, wherein the liquid component comprises one or more of the maleimide-containing compound, the nadimide-containing compound or the itaconimide-containing compound comprises a maleimide functional group, nadimide functional group or itaconimide functional group respectiveley, attached to a monovalent radical or maleimide functional groups, nadimide functional groups or itaconimide functional groups separated by a polyvalent radical, each of the monovalent radical or the polyvalent radical having sufficient length and branching to render the maleimide-containing compound, the nadimide-containing compound or the itaconimide-containing compound respectively, a liquid.