Epoxy resin compositions, solid state devices encapsulated therewith and method

• US 20040067366A1
• Filed: 10/07/2002
• Published: 04/08/2004
• Est. Priority Date: 10/07/2002
• Status: Active Grant

• Current Assignee: General Electric Company
• Original Assignee: General Electric Company
• Inventors: Gorczyca, Thomas Bert
• Granted Patent: US 6,800,373 B2
• Time in Patent Office: Days
• US Class Current: 428/413
• CPC Class Codes: C08G 59/4284 together with other curing agents
• CPC Class Codes: C08G 77/045 containing less than 25 silicon atoms
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/16 to hydroxyl groups
• CPC Class Codes: C08G 77/18 to alkoxy or aryloxy groups
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/70 Siloxanes defined by use of the MDTQ nomenclature
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: H01L 2224/48091 Arched
• CPC Class Codes: H01L 2224/48247 connecting the wire to a bond pad of the item
• 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 2924/00012 Relevant to the scope of the group, the symbol of which is combined with the symbol of this group
• CPC Class Codes: H01L 2924/00014 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 2924/15747 Copper [Cu] as principal constituent
• CPC Class Codes: H01L 2924/181 Encapsulation
• CPC Class Codes: H01L 2924/3025 Electromagnetic shielding
• CPC Class Codes: H01L 33/56 Materials, e.g. epoxy or silicone resin
• CPC Class Codes: Y10T 428/31511 : Of epoxy ether
• CPC Class Codes: Y10T 428/31663 : As siloxane, silicone or silane

Abstract

Epoxy resin compositions are disclosed which comprise (A) at least one silicone resin, (B) at least one epoxy resin, (C) at least one anhydride curing agent, (D) at least one siloxane surfactant, and (E) at least one ancillary curing catalyst. Also disclosed are a packaged solid state devices comprising a package, a chip, and an encapsulant comprising a composition of the invention. A method of encapsulating a solid state device is also provided.

Claims

1. A curable epoxy resin composition for encapsulation of a solid state device, which comprises (A) at least one silicone resin, (B) at least one epoxy resin, (C) at least one anhydride curing agent, (D) at least one siloxane surfactant, and (E) at least one ancillary curing catalyst.

2. The composition of claim 1, wherein the silicone resin comprises a silicone resin of structure (I)

3. The composition of claim 1, wherein the epoxy resin is selected from the group consisting of aliphatic epoxy resins, cycloaliphatic epoxy resins, bisphenol-A epoxy resins, bisphenol-F epoxy resins, phenol novolac epoxy resins, cresol-novolac epoxy resins, biphenyl epoxy resins, biphenyl epoxy resins, 4,4′

-biphenyl epoxy resins, polyfunctional epoxy resins, divinylbenzene dioxide, 2-glycidylphenylglycidyl ether, and combinations thereof.

4. The composition of claim 1, wherein the epoxy resin is selected from the group consisting of epoxy resins in structures (II) to (V)

5. The composition of claim 1, wherein the anhydride curing agent is selected from the group consisting of bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, phthalic anhydride, pyromellitic dianhydride, hexahydrophthalic anhydride, hexahydro-4-methylphthalic anhydride, dodecenylsuccinic anhydride, dichloromaleic anhydride, chlorendic anhydride, tetrachlorophthalic anhydride, and combinations thereof.

6. The composition of claim 1, wherein the anhydride curing agent is a compound of structure (VI), (VII), or combination thereof

7. The composition of claim 1 wherein the siloxane surfactant is a compound of structure (VIII), (IX), or combination thereof

8. The composition of claim 1, wherein the anhydride curing agent (C) is hexahydro-4-methylphthalic anhydride.

9. The composition of claim 1 further comprising refractive index modifiers selected from the group consisting of magnesium oxide, yttria, zirconia, cerium oxides, alumina, lead oxides, zinc selenide, zinc sulphides, alloys made from Zn, Se, S, and Te, gallium nitride, silicon nitride, aluminum nitride, and combinations thereof.

10. The composition of claim 1, wherein the composition is cured in a range between about 100°

C. and about 200°

C.

11. The composition of claim 1, wherein the ancillary curing catalyst (E) is selected from the group consisting of an organometallic salt, a sulfonium salt, an iodonium salt, and combinations thereof.

12. The composition of claim 1, wherein the ancillary curing catalyst (E) is selected from the group consisting of a metal carboxylate, a metal acetylacetonate, zinc octoate, stannous octoate, triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, diaryliodonium hexafluoroantimonate, diaryliodonium tetrakis(pentafluorophenyl)borate, and combinations thereof.

13. The composition of claim 12, wherein the ancillary curing catalyst (E) comprises zinc octoate.

14. The composition of claim 1, comprising at least one of a hindered phenol stabilizer, a phosphite stabilizer, or combinations thereof.

15. The composition of claim 1 wherein the refractive index of the composition is in a range between about 0.1 and about 10.0.

16. The composition of claim 1 wherein the composition is clear, transparent, polishable and crackfree.

17. A curable epoxy resin composition for encapsulation of a solid state device, which comprises (A) a silicone resin comprising a hydroxyfunctional silicone resin, (B) an epoxy resin comprising bisphenol A epoxy resin, (C) an anhydride curing agent comprising hexahydro-4-methylphthalic anhydride, (D) a siloxane surfactant comprising ethylene oxide functionalized siloxane, and (E) an ancillary curing catalyst zinc octoate, wherein component (A) is present at a level of greater than about 40% by weight;

component (B) is present at a level in a range of between about 1% by weight and about 20% by weight;

component (C) is present at a level of less than about 40% by weight; and

component (D) and (E) are present at a level in a range between about 0.008% by weight and about 10% by weight based on the combined weight of silicone resin (A), epoxy resin (B), anhydride curing agent (C), siloxane surfactant (D) and ancillary curing catalyst (E).

18. The composition of claim 17 further comprising at least one of a thermal stabilizer, a UV stabilizer, or combinations thereof.

19. The composition of claim 17 wherein the composition has a glass transition temperature varying in a range between about 24°

C. and about 150°

C.

20. The composition of claim 17 wherein the composition has a refractive index in a range between about 0.1 and about 10.0.

21. A packaged solid state device comprising:

(a) a package;

a chip; and

(c) an encapsulant comprising;

(A) at least one silicone resin, (B) at least one epoxy resin, (C) at least one anhydride curing agent, (D) at least one siloxane surfactant, and (E) at least one ancillary curing catalyst.

22. The packaged solid state device of claim 21, wherein the solid state device is a semiconductor device.

23. The packaged solid state device of claim 21, wherein the solid state device is an opto-electronic device.

24. The packaged solid state device of claim 21, wherein the opto-electronic device is semiconductor device comprising:

a LED, CCD, LSI, photodiode, phototransistor, or opto-electronic coupler.

25. The packaged solid state device of claim 21, wherein the package comprises a shell or lens.

26. The packaged solid state device of claim 21, wherein the silicone resin comprises a silicone resin selected from the silicone resin in structure (I)

27. The packaged solid state device of claim 21, wherein the epoxy resin is selected from the group consisting of aliphatic epoxy resins, cycloaliphatic epoxy resins, bisphenol-A epoxy resins, bisphenol-F epoxy resins, phenol novolac epoxy resins, cresol-novolac epoxy resins, biphenyl epoxy resins, biphenyl epoxy resins, 4,4′

-biphenyl epoxy resins, polyfunctional epoxy resins, divinylbenzene dioxide, 2-glycidylphenylglycidyl ether, and combinations thereof.

28. The packaged solid state device of claim 21, wherein the epoxy resin is a resin selected from the structures (II) to (V)

29. The packaged solid state device of claim 21, wherein the anhydride curing agent is selected from the group consisting of bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, phthalic anhydride, pyromellitic dianhydride, hexahydrophthalic anhydride, hexahydro-4-methylphthalic anhydride, dodecenylsuccinic anhydride, dichloromaleic anhydride, chlorendic anhydride, tetrachlorophthalic anhydride, and combinations thereof.

30. The packaged solid state device of claim 21, wherein the anhydride curing agent (C) is a compound of structure (VI), (VII), or combination thereof

31. The packaged solid state device of claim 21 wherein the anhydride curing agent (C) comprises hexahydro-4-methylphthalic anhydride.

32. The packaged solid state device of claim 21 wherein the siloxane surfactant is a compound of structure (VIII), (IX), or combination thereof

33. The packaged solid state device of claim 21, wherein the ancillary curing catalyst (E) is selected from the group consisting of an organometallic salt, a sulfonium salt, an iodonium salt, and combinations thereof.

34. The packaged solid state device of claim 21, wherein the ancillary curing catalyst (E) comprises at least one member selected from the group consisting of a metal carboxylate, a metal acetylacetonate, zinc octoate, stannous octoate, triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, diaryliodonium hexafluoroantimonate, diaryliodonium tetrakis(pentafluorophenyl)borate, and combinations thereof.

35. The packaged solid state device of claim 21, wherein the ancillary curing catalyst (E) is zinc octoate.

36. The packaged solid state device of claim 21, further comprising at least one of thermal stabilizers, UV stabilizers, cure modifiers, coupling agents, refractive index modifiers, or combinations thereof.

37. The packaged solid state device of claim 21, comprising at least one of a thermal stabilizer, a UV stabilizer, or combinations thereof.

38. The packaged solid state device of claim 21 wherein the encapsulant is clear, transparent, crackfree and polishable.

39. The packaged solid state device of claim 21 wherein the encapsulant has a glass transition varying in a range between about 24°

C. and about 150°

C.

40. The packaged solid state device of claim 22 wherein the encapsulant has a refractive index in a range between about 0.1 and about 10.0.

41. A LED device comprising:

(a) a package;

a LED chip; and

(c) an encapsulant comprising;

(A) a silicone resin comprising a hydroxyfunctional silicone resin, (B) an epoxy resin comprising a bisphenol F resin, (C) an anhydride curing agent comprising hexahydro-4-methylphthalic anhydride, (D) a siloxane surfactant comprising propylene oxide modified siloxane, and (E) a ancillary curing catalyst comprising zinc octoate, wherein component (A) is present at a level of greater than about 40% by weight;

component (B) is present at a level in a range of between about 1% by weight and about 20% by weight;

component (C) is present at a level of less than about 40% by weight; and

component (D) and (E) are present at a level in a range between about 0.008% by weight and about 10% by weight based on the combined weight of silicone resin (A), epoxy resin (B), a siloxane surfactant (D) anhydride curing agent (C), and ancillary curing catalyst (E).

42. The LED of claim 41, in which the encapsulant further comprises at least one of a thermal stabilizer, a UV stabilizer, or combination thereof.

43. The LED of claim 41, in which the encapsulant has a glass transition temperature varying in a range between about 24°

C. and about 150°

C.

44. The LED of claim 41 in which the encapsulant has a refractive index in a range between about 0.1 and about 10.0.

45. A method of encapsulating a solid state device comprising:

placing a solid state device into a package; and

providing an encapsulant comprising;

(A) at least one silicone resin, (B) at least one epoxy resin (C) at least one anhydride curing agent (D) at least one siloxane surfactant, and (E) at least one ancillary curing catalyst.

46. The method of claim 45, wherein the solid state device is a semiconductor device.

47. The method of claim 45, wherein the solid state device is an opto-electronic device.

48. The method of claim 45, wherein the opto-electronic device is semiconductor device comprising:

a LED, CCD, LSI, photodiode, phototransistor, or opto-electronic coupler.

49. The method of claim 45, wherein the package comprises a shell or lens.

50. The method of claim 45, wherein the silicone resin (A) comprises a silicone resin of structure (I)

51. The method of claim 45, wherein the epoxy resin is selected from the group consisting of aliphatic epoxy resins, cycloaliphatic epoxy resins, bisphenol-A epoxy resins, bisphenol-F epoxy resins, phenol novolac epoxy resins, cresol-novolac epoxy resins, biphenyl epoxy resins, biphenyl epoxy resins, 4,4′

-biphenyl epoxy resins, polyfunctional epoxy resins, divinylbenzene dioxide, 2-glycidylphenylglycidyl ether, and combinations thereof.

52. The method of claim 45, wherein the epoxy resin is a resin selected from structures (II) to (V)

53. The method of claim 45, wherein the anhydride curing agent (C) is selected from the group consisting of bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, phthalic anhydride, pyromellitic dianhydride, hexahydrophthalic, anhydride, hexahydro-4-methylphthalic anhydride, dodecenylsuccinic anhydride, dichloromaleic anhydride, chlorendic anhydride, tetrachlorophthalic anhydride, and combinations thereof.

54. The method of claim 45 wherein the anhydride curing agent is a compound of structure (VI), (VII), or combination thereof

55. The method of claim 45, wherein the siloxane surfactant (D) is a compound of structure (VIII), (IX), or combination thereof

56. The method of claim 45, wherein siloxane surfactant (D) comprises an ethylene oxide functionalalized siloxane.

57. The method of claim 45, wherein the anhydride curing agent (C) comprises hexahydro-4-methylphthalic anhydride.

58. The method of claim 45, wherein the ancillary curing catalyst (E) is selected from the group consisting of an organometallic salt, a sulfonium salt, an iodonium salt, and combinations thereof.

59. The method of claim 45, wherein the ancillary curing catalyst (E) is selected from the group consisting of a metal carboxylate, a metal acetylacetonate, zinc octoate, stannous octoate, triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, diaryliodonium hexafluoroantimonate, diaryliodonium tetrakis(pentafluorophenyl)borate, and combinations thereof.

60. The method of claim 45, wherein the ancillary curing catalyst is zinc octoate.

61. The method of claim 45, further comprising at least one of thermal stabilizers, UV stabilizers, cure modifiers, coupling agents, refractive index modifiers, or combinations thereof.

62. The method of claim 45, comprising at least one of a thermal stabilizer, a UV stabilizer, or combination thereof.

63. The method of claim 45, wherein the encapsulant is clear, transparent, crackfree and polishable.

64. The method of claim 45, wherein the encapsulant has a glass transition temperature varying in a range between about 24°

C. and about 150°

C.

65. The method of claim 45, wherein the encapsulant has a refractive index in a range between about 0.1 and about 10.0.

66. A method of encapsulating a LED device comprising:

placing a LED device into a package and providing an encapsulant comprising;

(A) a silicone resin comprising hydroxyfunctionalized silicone, (B) an epoxy resin comprising bisphenol F, (C) an anhydride curing agent comprising hexahydro-4-methylphthalic anhydride, (D) a siloxane surfactant comprising ethylene oxide functionalized siloxane, and (E) an ancillary curing catalyst comprising zinc octoate, wherein component (A) is present at a level of greater than about 40% by weight;

component (B) is present at a level in a range of between about 1% by weight and about 20% by weight;

component (C) is present at a level of less than about 40% by weight; and

component (D) and (E) are present at a level in a range between about 0.008% by weight and about 10% by weight based on the combined weight of the silicone resin (A), epoxy resin (B), siloxane surfactant (C), curing agent (D), and ancillary curing catalyst (E).

67. The method of claim 66, wherein the encapsulant further comprises at least one of a thermal stabilizer, a UV stabilizer, or combination thereof.

68. The method of claim 66, wherein the encapsulant is partially cured.

69. The method of claim 66, wherein the encapsulant is cured.