Sealing glass compositions

• US 5,013,360 A
• Filed: 09/15/1989
• Issued: 05/07/1991
• Est. Priority Date: 09/15/1989
• Status: Expired due to Fees

• Current Assignee: VLSI Packaging Materials
• Original Assignee: VLSI Packaging Materials
• Inventors: Tetschlag, Richard R., Finkelstein, Leo, Dumesnil, Maurice E.
• Primary Examiner(s): BELL, MARK LEE
• Application Number:
  US07/407,470
• Time in Patent Office: 599 Days
• Field of Search: 501/15, 501/32, 501/17, 501/41, 501/44, 501/46, 428/426, 428/432, 428/433, 428/434, 106/1.23
• US Class Current: 106/1.23
• CPC Class Codes: C03C 14/004 the non-glass component being in the form of particles or flakes
• CPC Class Codes: C03C 2214/04 Particles; Flakes
• CPC Class Codes: C03C 2214/08 Metals
• CPC Class Codes: C03C 3/122 containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
• CPC Class Codes: C03C 8/24 Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
• CPC Class Codes: H01L 2224/8319 Arrangement of the layer connectors prior to mounting
• CPC Class Codes: H01L 2224/8385 using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
• CPC Class Codes: H01L 2224/8389 using an inorganic non metallic glass type adhesive, e.g. solder glass
• CPC Class Codes: H01L 23/10 characterised by the material or arrangement of seals between parts, e.g. between cap and base of the container or between leads and walls of the container
• CPC Class Codes: H01L 24/28 Structure, shape, material or disposition of the layer connectors prior to the connecting process
• 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 2924/01005 Boron [B]
• CPC Class Codes: H01L 2924/01006 Carbon [C]
• CPC Class Codes: H01L 2924/01012 Magnesium [Mg]
• CPC Class Codes: H01L 2924/01013 Aluminum [Al]
• CPC Class Codes: H01L 2924/01015 Phosphorus [P]
• CPC Class Codes: H01L 2924/01019 Potassium [K]
• CPC Class Codes: H01L 2924/0102 Calcium [Ca]
• CPC Class Codes: H01L 2924/01023 Vanadium [V]
• CPC Class Codes: H01L 2924/01024 : Chromium [Cr]
• CPC Class Codes: H01L 2924/01025 : Manganese [Mn]
• CPC Class Codes: H01L 2924/01027 : Cobalt [Co]
• CPC Class Codes: H01L 2924/01029 : Copper [Cu]
• CPC Class Codes: H01L 2924/0103 : Zinc [Zn]
• CPC Class Codes: H01L 2924/01033 : Arsenic [As]
• CPC Class Codes: H01L 2924/01038 : Strontium [Sr]
• CPC Class Codes: H01L 2924/0104 : Zirconium [Zr]
• CPC Class Codes: H01L 2924/01041 : Niobium [Nb]
• CPC Class Codes: H01L 2924/01042 : Molybdenum [Mo]
• CPC Class Codes: H01L 2924/01047 : Silver [Ag]
• CPC Class Codes: H01L 2924/0105 : Tin [Sn]
• CPC Class Codes: H01L 2924/01051 : Antimony [Sb]
• CPC Class Codes: H01L 2924/01055 : Cesium [Cs]
• CPC Class Codes: H01L 2924/01056 : Barium [Ba]
• CPC Class Codes: H01L 2924/01073 : Tantalum [Ta]
• CPC Class Codes: H01L 2924/01074 : Tungsten [W]
• CPC Class Codes: H01L 2924/01079 : Gold [Au]
• CPC Class Codes: H01L 2924/01082 : Lead [Pb]
• CPC Class Codes: H01L 2924/01322 : Eutectic Alloys, i.e. obtained by a liquid transforming into two solid phases
• CPC Class Codes: H01L 2924/014 : Solder alloys
• CPC Class Codes: H01L 2924/07802 : not being an ohmic electrical conductor
• CPC Class Codes: H01L 2924/09701 : Low temperature co-fired ceramic [LTCC]
• CPC Class Codes: H01L 2924/10253 : Silicon [Si]
• CPC Class Codes: H01L 2924/14 : Integrated circuits
• CPC Class Codes: H01L 2924/15787 : Ceramics, e.g. crystalline carbides, nitrides or oxides
• CPC Class Codes: H01L 2924/3512 : Cracking

Abstract

Fluid, stable glasses useful for low-temperature sealing applications are made by adding jointly bismuth oxide, zinc oxide, phosphorus pentoxide, titania and/or zirconium oxide to the lead oxide vanadium oxide binary. The phosphorus pentoxide may be replaced partially or entirely with niobium pentoxide and/or tantalum oxide.

Sealing glass compositions comprising these low-melting lead-vanadia glasses in powder form and refractory fillers of lower thermal expansion for use in hermetically sealing semiconductor devices in ceramic packages are disclosed. Group V metal oxides, particularly niobium-containing oxides, are preferred fillers. Silver metal is a preferred filler for making die-attach compositions.

Claims

1. A low-melting glass composition comprising, in weight percent calculated on an oxide basis:

(a) PbO;

35-50%

(b) V₂ O₅ ;

35-50%

(c) Bi₂ O₃ ;

0.1-6%

(d) P₂ O₅, Nb₂ O₅, Ta₂ O₅, or combinations thereof;

0.1-8%

(e) ZnO, MgO, CaO, BaO, SrO, or combinations thereof;

0.1-5%

(f) TiO₂, ZrO₂, or combinations thereof;

0.1-5%

wherein the combined weight percent of (c)+(d)+(e)+(f) is in the range of 0.4-24%.

2. The low-melting glass of claim 1 wherein the composition includes at least one additive selected from the group consisting of:

up to 3% by weight B₂ O₃,

up to 3% by weight F.,

up to 3% by weight FeO, CoO, NiO, MnO, and/or CrO,

up to 3% by weight WO₃,

up to 3% by weight MoO₃, and

up to 3% by weight Cs₂ O.

4. The glass of claim 1 mixed with about 1% to about 50% by weight, based on the mixture, of a refractory filler powder with a low coefficient of linear expansion.

5. The glass of claim 4 wherein the filler is a Group V metal oxide.

6. The glass of claim 5 wherein the filler is a niobium-containing oxide, a phosphate, or a tantalum-containing oxide.

7. The glass of claim 5 wherein the filler is niobium pentoxide.

8. The glass of claim 2 mixed with about 1% to about 50% by weight, based on the mixture, of a refractory filler powder with a low coefficient of linear expansion.

9. The glass of claim 8 wherein the filler is a Group V metal oxide.

10. The glass of claim 9 wherein the filler is a niobium-containing oxide, a phosphate, or a tantalum-containing oxide.

11. The glass of claim 9 wherein the filler is niobium pentoxide.

16. The glass of claim 1 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

17. The glass of claim 2 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

19. The glass of claim 4 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

20. The glass of claim 5 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

21. The glass of claim 6 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

22. The glass of claim 7 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

23. The glass of claim 8 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

24. The glass of claim 9 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

25. The glass of claim 10 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

26. The glass of claim 11 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

31. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 1.

32. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 2.

34. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 4.

35. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 5.

36. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 6.

37. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 7.

38. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 8.

39. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 9.

40. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 10.

41. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 11.

3. A low-melting glass composition comprising, in weight percent calculated on an oxide basis:

space="preserve" listing-type="tabular">______________________________________ (a) PbO 35-45% (b) V.sub.2 O.sub.5 35-45% (c) ZnO 2-4% (d) Bi.sub.2 O.sub.3 3-5% (e) Nb.sub.2 O.sub.5 3-5% (f) TiO.sub.2 0-4% (g) ZrO.sub.2 0-4% (h) P.sub.2 O.sub.5 0-4% (i) B.sub.2 O.sub.3 0-2% (j) CoO 0-3% (k) F 0-1% ______________________________________

wherein the combined weight percent of (f)+(g) is in the range of 0.1-4%.

12. The glass of claim 3 mixed with about 1% to about 50% by weight, based on the mixture, of a refractory filler powder with a low coefficient of linear expansion.

13. The glass of claim 12 wherein the filler is a Group V metal oxide.

14. The glass of claim 13 wherein the filler is a niobium-containing oxide, a phosphate, or a tantalum-containing oxide.

15. The glass of claim 13 wherein the filler is niobium pentoxide.

18. The glass of claim 3 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

27. The glass of claim 12 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

28. The glass of claim 13 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

29. The glass of claim 14 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

30. The glass of claim 15 mixed with up to 90% by weight, based on the mixture, of silver or gold powder.

33. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 3.

42. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 12.

43. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 13.

44. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 14.

45. An article of manufacture for use in sealing an electronic part comprising a metal, glass, or ceramic body coated with a pattern of the glass composition of claim 15.