Ceramic composites with improved interfacial properties and methods to make such composites

• US 6,143,432 A
• Filed: 01/09/1998
• Issued: 11/07/2000
• Est. Priority Date: 01/09/1998
• Status: Expired due to Term

• Current Assignee: L. Pierre Derochemont
• Original Assignee: Derochemont L. Pierre
• Inventors: de Rochemont, L. Pierre, Farmer, Peter H.
• Primary Examiner(s): Jones, Deborah
• Assistant Examiner(s): RESNICK, JASON D
• Application Number:
  US09/004,928
• Time in Patent Office: 1,033 Days
• Field of Search: 428/210, 428/137, 428/209, 428/469, 428/472.2, 428/615, 428/701, 428/702, 428/698, 428/325, 427/96, 427/427, 427/226, 427/126.3
• US Class Current: 428/689
• CPC Class Codes: B32B 15/00 Layered products comprising a layer of metal
• CPC Class Codes: H01L 21/4807 Ceramic parts
• CPC Class Codes: H01L 2221/68377 with parts of the auxiliary support remaining in the finished device
• CPC Class Codes: H01L 2224/45124 Aluminium (Al) as principal constituent
• CPC Class Codes: H01L 2224/48227 connecting the wire to a bond pad of the item
• CPC Class Codes: H01L 2224/48472 the other connecting portion not on the bonding area also being a wedge bond, i.e. wedge-to-wedge
• CPC Class Codes: H01L 23/142 Metallic substrates having insulating layers
• CPC Class Codes: H01L 23/3735 Laminates or multilayers, e.g. direct bond copper ceramic substrates
• CPC Class Codes: H01L 24/45 of an individual wire connector
• CPC Class Codes: H01L 24/48 of an individual wire 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 2924/00014 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 2924/01019 Potassium [K]
• CPC Class Codes: H01L 2924/01039 Yttrium [Y]
• CPC Class Codes: H01L 2924/01057 Lanthanum [La]
• CPC Class Codes: H01L 2924/01068 Erbium [Er]
• CPC Class Codes: H01L 2924/01077 Iridium [Ir]
• CPC Class Codes: H01L 2924/01079 Gold [Au]
• CPC Class Codes: H01L 2924/01322 Eutectic Alloys, i.e. obtained by a liquid transforming into two solid phases
• CPC Class Codes: H01L 2924/01327 Intermediate phases, i.e. intermetallics compounds
• CPC Class Codes: H01L 2924/09701 : Low temperature co-fired ceramic [LTCC]
• CPC Class Codes: H01L 2924/12042 : LASER
• CPC Class Codes: H01L 2924/14 : Integrated circuits
• CPC Class Codes: H01L 2924/3025 : Electromagnetic shielding
• CPC Class Codes: H01L 2924/3511 : Warping
• CPC Class Codes: H05K 3/38 : Improvement of the adhesion between the insulating substrate and the metal
• CPC Class Codes: Y10T 428/24322 : Composite web or sheet
• CPC Class Codes: Y10T 428/24917 : including metal layer
• CPC Class Codes: Y10T 428/24926 : including ceramic, glass, porcelain or quartz layer
• CPC Class Codes: Y10T 428/252 : Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]

Abstract

A ceramic composite having a substrate bonded to a ceramic oxide member through a covalent bond formed at temperatures less than 880° C., and ceramic composites that are so constructed that to control internal stress or increase crack-resistance within the ceramic member under applied thermal or mechanical loads to the composite, such composite with alumina bonded sets of such metal-ceramic computers and end use devices including printed circuit boards, and higher level assemblies including such devices.

Claims

1. A ceramic composite comprising:

a ceramic substrate;

a ceramic bonded directly to said ceramic substrate via a direct covalent bond along an interface between said ceramic and said ceramic substrate, said covalent bond being effected by dispersion of a metal organic precursor of said ceramic and pyrolysis of said metal organic precursor at a temperature of 500°

C. or less to form the ceramic composite;

said ceramic comprising a ceramic medium whose primary phase precursors have been mixed at the molecular level; and

said interface between said ceramic substrate and said ceramic being essentially absent of any intermetallic eutectic or adhesive agent.

2. The ceramic composite as in claim 1 with holes (perforations/cavities) in said ceramic substrate to reduce effects of stress and/or thermal expansion of said substrate.

3. The ceramic composite as in claim 1 wherein said ceramic contains secondary phase material particles dispersed throughout a substantial portion of its volume,

the secondary phase material particles comprising material selected from the group consisting of metals, metal alloys, glass, shape memory alloys, graphite, oxides, non-oxide inert compounds, crystalline ceramics, a single crystalline phase, and combinations of these materials phases.

4. The ceramic composite as in claim 3 wherein the secondary phase material particles have a size defined by a major axis of said particles having a length ranging between 0.05 and 500 microns.

5. The ceramic composite as in claim 3, wherein the secondary phase material particles have a size defined by a major axis having a length ranging between 0.10 and 50 microns.

6. The ceramic composite as in claim 1, wherein the ceramic is constructed and arranged with a gradient composition that causes the coefficient-of-thermal-expansion of the ceramic to be greater at distances further away from said interface between said ceramic and said ceramic substrate and lower at the interface at which the ceramic is covalently bonded to the ceramic substrate.

7. The ceramic composite as in claim 1 where the ceramic is an oxide ceramic.

8. The ceramic composite as in claim 7 wherein the oxide ceramic comprises TiO₂.

9. The ceramic composite as in claim 7 wherein the oxide ceramic comprises Al₂ O₃.

10. The ceramic composite as in claim 1 further comprising adhesion-resistant means dispersed at least at one preselected location along said interface between said ceramic and said ceramic substrate for preventing said covalent bond to take place at said at least one preselected location along said interface between said ceramic and said ceramic substrate.

11. The ceramic composite as in claim 10 further comprising means for removably attaching the adhesion-resistant means to the ceramic substrate.

12. The ceramic composite as in claim 1 made by temporarily attaching an adhesion resistant material to the substrate in selected surface regions, spray pyrolizing said ceramic over the ceramic substrate and the adhesion resistant material and later dissipating the adhesion resistant material to form at least one cavity at the ceramic-ceramic substrate interface.

13. The ceramic composite as in claim 1 in combination with a ceramic component, said ceramic composite and said ceramic component forming two adjacent pieces, the two pieces bonded at respective ceramic surfaces by an intermediate low-melting temperature oxide phase.

14. The ceramic composite combination as in claim 13, wherein the low-melting temperature oxide phase used to bond the two pieces together ceramic-face to ceramic-face comprises a phospho-alumino-borate glass phase.

15. The ceramic composite combination as in claim 14, comprising two such ceramic composites, wherein at least one of said ceramic composites comprises ceramic comprising alumina and a substrate comprising metal bonded together to form a metal-ceramic composite suitable for printed circuit board usage.

16. The ceramic composite as in claim 1 wherein the ceramic substrate portion is an oxide ceramic.

17. The ceramic composite as in claim 1 wherein the ceramic substrate portion is a nitride ceramic.

18. The ceramic composite as in claim 1 wherein the ceramic substrate portion is a carbide ceramic.

19. The ceramic composite as in claim 1 wherein the ceramic substrate portion is a carbon based ceramic.

20. A method of making ceramic composites, comprising the steps of:

providing a substrate;

temporarily bonding an adhesion resistant material to the substrate at preselected surface regions of said substrate;

spray pyrolizing the ceramic over the substrate and the adhesion resistant material to directly covalently bond the ceramic to said substrate at surface regions of said substrate, other than said preselected surface regions, via a direct covalent bond along an interface between said ceramic and said substrate, said covalent bond being effected by dispersion of a metal organic precursor of said ceramic and pyrolysis of said metal organic precursor at a temperature of 500°

C. or less to form the ceramic composite, said ceramic comprising a ceramic medium whose primary phase precursors have been mixed at the molecular level;

dissipating the adhesion resistant material to form at least one cavity at the ceramic-substrate interface; and

said surface regions of said substrate, other than said preselected surface regions, at the interface between said substrate and said ceramic being essentially absent of any intermetallic eutectic or adhesive agent.

21. A ceramic composite comprising:

a substrate;

a ceramic bonded directly to said substrate via a direct covalent bond along an interface between said ceramic and said substrate, said covalent bond being effected by dispersion of a metal organic precursor of said ceramic and pyrolysis of said metal organic precursor at a temperature of 500°

C. or less to form the ceramic composite;

said ceramic comprising a ceramic medium whose primary phase precursors have been mixed at the molecular level;

said interface between said substrate and said ceramic being absent of any intermetallic eutectic or adhesive agent; and

said substrate having holes therein to reduce effects of stress and/or thermal expansion of said substrate.

22. A ceramic composite comprising:

a substrate;

a ceramic bonded directly to said substrate via a direct covalent bond along an interface between said ceramic and said substrate, said covalent bond being effected by dispersion of a metal organic precursor of said ceramic and pyrolysis of said metal organic precursor at a temperature of 500°

C. or less to form the ceramic composite;

said ceramic comprising a ceramic medium whose primary phase precursors have been mixed at the molecular level;

said interface between said substrate and said ceramic being essentially absent of any intermetallic eutectic or adhesive agent; and

wherein said ceramic contains secondary phase material particles dispersed throughout a substantial portion of its volume,

the secondary phase material particles comprising material selected from the group consisting of metals, metal alloys, glass, shape memory alloys, graphite, oxides, non-oxide inert compounds, crystalline ceramics, a single crystalline phase, and combinations of these materials phases.

23. The ceramic composite as in claim 22 wherein the substrate portion is a metal.

24. The ceramic composite as in claim 23 wherein the metal is stainless steel.

25. The ceramic composite as in claim 22 wherein the substrate portion is a metal alloy.

26. The ceramic composite as in claim 22, wherein the secondary phase material particles have a size defined by a major axis of said particles having a length ranging between 0.05 and 500 microns.

27. The ceramic composite as in claim 22, wherein the secondary phase material particles have a size defined by a major axis having a length ranging between 0.10 and 50 microns.

28. The ceramic composite as in claim 22 wherein said substrate is metal.

29. A ceramic composite comprising:

a substrate;

a ceramic bonded directly to said substrate via a direct covalent bond along an interface between said ceramic and said substrate, said covalent bond being effected by dispersion of a metal organic precursor of said ceramic and pyrolysis of said metal organic precursor at a temperature of 500°

C. or less to form the ceramic composite;

said ceramic comprising a ceramic medium whose primary phase precursors have been mixed at the molecular level;

said interface between said substrate and said ceramic being essentially absent of any intermetallic eutectic or adhesive agent; and

adhesion-resistant means dispersed at least at one preselected location along said interface between said ceramic and said substrate for preventing said covalent bond to take place at said at least one preselected location along said interface between said ceramic and said substrate.

30. The ceramic composite as in claim 29 further comprising means for removably attaching the adhesion-resistant means to the substrate.

31. The ceramic composite as in claim 29 wherein said substrate is metal.

32. A ceramic composite comprising:

a substrate;

a ceramic bonded directly to said substrate via a direct covalent bond along an interface between said ceramic and said substrate, said covalent bond being effected by dispersion of a metal organic precursor of said ceramic and pyrolysis of said metal organic precursor at a temperature of 500°

C. or less to form the ceramic composite;

said ceramic comprising a ceramic medium whose primary phase precursors have been mixed at the molecular level;

said interface between said substrate and said ceramic being essentially absent of any intermetallic eutectic or adhesive agent; and

wherein the substrate comprises an electrical and/or thermal conductivity material selected from the group consisting of;

(a) elemental metals,

(b) metal alloys, and

(c) metal composites of aluminum, copper, gold, or silver,

bonded to a constraining-metal member that is 1/20th to 1/3rd the thickness of the high electrical and/or thermal conductivity substrate, wherein the constraining-metal member comprises a metal, metal alloy, or metal composite, of antimony, chromium, iridium, molybdenum, tantalum, tin, titanium, tungsten, or vanadium.

33. The ceramic composite as in claim 32 wherein said ceramic comprises TiO₂.

34. A ceramic composite comprising:

a substrate;

a ceramic bonded directly to said substrate via a direct covalent bond along an interface between said ceramic and said substrate, said covalent bond being effected by dispersion of a metal organic precursor of said ceramic and pyrolysis of said metal organic precursor at a temperature of 500°

C. or less to form the ceramic composite;

said ceramic comprising a ceramic medium whose primary phase precursors have been mixed at the molecular level;

said interface between said substrate and said ceramic being absent of any intermetallic eutectic or adhesive agent; and

the ceramic composite being in combination with a ceramic component, said ceramic composite and said ceramic component forming two adjacent pieces, the two pieces bonded at respective ceramic surfaces by an intermediate low-melting temperature oxide phase.

35. The ceramic composite as in claim 34 wherein said substrate is metal.