Electrically conductive compositions and methods for the preparation and use thereof

• US 5,830,389 A
• Filed: 10/17/1994
• Issued: 11/03/1998
• Est. Priority Date: 02/09/1990
• Status: Expired due to Term

• Current Assignee: Ormet Circuits, Inc. (Merck & Co., Inc.)
• Original Assignee: Toranaga Technologies, Inc.
• Inventors: Craig, Hugh P., Todd, Michael George, Manesis, Nicholas John, Capote, Miguel Albert
• Primary Examiner(s): Lieberman, Paul
• Assistant Examiner(s): Kopec, M.
• Application Number:
  US08/324,060
• Time in Patent Office: 1,478 Days
• Field of Search: 252/512, 252/513, 252/514, 252/518, 106/1.13, 106/1.15, 106/1.16
• US Class Current: 252/512
• CPC Class Codes: B22F 3/1035 Liquid phase sintering
• CPC Class Codes: B23K 35/0222 for use in soldering, brazing B23K35/0205 takes precedence
• CPC Class Codes: B23K 35/36 Selection of non-metallic compositions, e.g. coatings, fluxes B23K35/34 takes precedence; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest selection of soldering or welding materials proper B23K35/24
• CPC Class Codes: H01B 1/22 the conductive material comprising metals or alloys
• CPC Class Codes: H01L 2224/293 with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
• CPC Class Codes: H01L 23/49827 Via connections through the substrates, e.g. pins going through the substrate, coaxial cables H01L23/49822, H01L23/49833, H01L23/4985, H01L23/49861 take precedence
• CPC Class Codes: H01L 23/49883 the conductive materials containing organic materials or pastes, e.g. for thick films for printed circuits H05K1/092
• CPC Class Codes: H01L 23/5384 Conductive vias through the substrate with or without pins, e.g. buried coaxial conductors H01L23/5383, H01L23/5385 take precedence; pins attached to insulating substrates H01L23/49811
• CPC Class Codes: H01L 2924/01019 Potassium [K]
• CPC Class Codes: H01L 2924/01068 Erbium [Er]
• CPC Class Codes: H01L 2924/01079 Gold [Au]
• CPC Class Codes: H01L 2924/01087 Francium [Fr]
• CPC Class Codes: H05K 1/095 for polymer thick films, i.e. having a permanent organic polymeric binder
• CPC Class Codes: H05K 1/181 associated with surface mounted components
• CPC Class Codes: H05K 2201/0272 Mixed conductive particles, i.e. using different conductive particles, e.g. differing in shape
• CPC Class Codes: H05K 2201/10378 Interposers
• CPC Class Codes: H05K 2203/0425 Solder powder or solder coated metal powder
• CPC Class Codes: H05K 2203/1105 Heating or thermal processing not related to soldering, firing, curing or laminating, e.g. for shaping the substrate or during finish plating
• CPC Class Codes: H05K 3/1216 by screen printing or stencil printing
• CPC Class Codes: H05K 3/321 by conductive adhesives
• CPC Class Codes: H05K 3/3489 : Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces
• CPC Class Codes: H05K 3/4069 : for via connections in organic insulating substrates
• CPC Class Codes: H05K 3/4623 : the circuit boards having internal via connections between two or more circuit layers before lamination, e.g. double-sided circuit boards H05K3/462 takes precedence
• CPC Class Codes: H05K 3/4664 : Adding a circuit layer by thick film methods, e.g. printing techniques or by other techniques for making conductive patterns by using pastes, inks or powders H05K3/4647 takes precedence

Abstract

Electrically conductive adhesive compositions and methods for the preparation and use thereof, in which a solder powder, a chemically protected cross-linking agent with fluxing properties and a reactive monomer or polymer are the principal components. Depending upon the intended end use, the compositions comprise three or more of the following: a relatively high melting metal powder; solder powder; the active cross-linking agent which also serves as a fluxing agent; a resin; and a reactive monomer or polymer. The compositions are useful as improved conductive adhesives, such as for attaching electrical components to electrical circuits; the compositions comprising metal powder are ideally suited for creating the conductive paths on printed circuits. The compositions for forming conductive paths may first be applied to a substrate in the desired pattern of an electrical circuit, and then heated to cure it. During heating, the action of the cross-linking agent and optional reactive monomer or polymer within the mixture fluxes the metals, enabling sintering to occur between the metal powder and the solder powder.

Claims

1. A composition of matter comprising:

greater than 0 up to 65% of a high melting point metal, wherein the high melting point metal is selected from the group consisting of copper, silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum, and alloys thereof;

6-65% of a solder, wherein said solder is selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ga, In, Te, Hg, To, Sb, Se, and alloys thereof;

0-45% of a resin;

0.01-61% of a chemically protected cross-linking agent with fluxing properties which is reactive only at or near the time at which the solder is melted,

wherein said chemically protected cross-linking agent is an acid or a strong base, wherein said acid or strong base is selected from the group consisting of anhydrides, carboxylic acids, amides, amines and phenols, and

wherein said acid or strong base is protected by a protecting group selected from the group consisting of carboxylic acids, alcohols, glycols and polyols; and

0-50% of a reactive monomer or polymer,

wherein all percentages referred to herein are based on volume.

2. The composition according to claim 1 wherein said solder is a metal mixture that includes a metal additive that alters the melting temperature of the solder, said metal additive being selected from the group consisting of nickel and silver and wherein said metal additive comprises 1 to 10 weight percent of the total metal content of the composition.

3. The composition according to claim 1 wherein said solder is an alloy comprising Sn63Pb37.

4. The composition according to claim 1 wherein the reactive monomer or polymer contains at least one --OH group as reactive site for linking with said cross-linking agent.

5. The composition according to claim 1 wherein said acid or strong base is protected by encapsulating the cross-linking agent in a shell of non-reactive material which releases the cross-linking agent only at or near the time the solder is melted.

6. The composition according to claim 1 wherein said acid or strong base is selected from the group consisting of anhydrides, carboxylic acids, amines, and phenols.

7. The composition according to claim 1 wherein said acid or strong base is an anhydride.

8. The composition according to claim 1 wherein said acid or strong base is protected by a protecting group selected from the group consisting of carboxylic acids, alcohols and polyols.

9. The composition according to claim 1 wherein said protecting group is an alcohol or polyol.

10. The composition according to claim 9, wherein said alcohol or polyol is selected from the group consisting of butyl carbitol, methanol, ethylene glycol, glycerol, meso-erythritol, adonitol and sorbitol.

11. The composition according to claim 1 wherein the high melting point metal comprises 13-65% by volume of said composition.

12. The composition according to claim 11 wherein:

the solder comprises 6-29% by volume of said composition,

the resin comprises 0-15% by volume of said composition,

the cross-linking agent comprises 7-60% by volume of said composition, and

the reactive monomer or polymer comprises 0-32% by volume of said composition.

13. The composition according to claim 11 further comprising a metal additive that comprises a second high melting point metal which readily dissolves in said solder to form a solid solution, wherein said metal additive comprises 1 to 10 weight percent of the total metal content of the composition.

14. The composition according to claim 12 wherein said solder is a metal mixture that includes a metal additive that alters the melting temperature of the solder, said metal additive being selected from the group consisting of nickel and silver and wherein said metal additive comprises 1 to 10 weight percent of the total metal content of the composition.

15. The composition according to claim 11 wherein said acid or strong base is selected from the group consisting of anhydrides, carboxylic acids, amines and phenols.

16. The composition according to claim 11 wherein said acid or strong base is protected by a protecting group selected from the group consisting of carboxylic acids, alcohols, polyols and phenols.

17. The composition according to claim 1 wherein the high melting point metal comprises spherical particles having an average particle diameter of 1-50 microns.

18. The composition according to claim 17 wherein the high melting point metal is copper.

24. The composition according to claim 2 wherein the additive is silver.

25. The composition according to claim 13 wherein the additive is silver.

26. The composition according to claim 14 wherein the additive is silver.

19. A conductive ink formed by a process comprising the steps of:

providing a composition comprising;

greater than 0 up to 65% of a high melting point metal, wherein the high melting point metal is selected from the group consisting of copper, silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum, and alloys thereof;

- 65% of a solder, wherein said solder is selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ga, In, Te, Hg, To, Sb, Se, and alloys thereof;

0-45% of a resin;

0.01-61% of a chemically protected cross-linking agent with fluxing properties which is reactive only at or near the time at which the solder is melted,

wherein said chemically protected cross-linking agent is an acid or a strong base, wherein said add or strong base is selected from the group consisting of anhydrides, carboxylic acids, amides, amines and phenols, and

wherein said acid or strong base is protected by a protecting group selected from the group consisting of carboxylic acids, alcohols, glycols and polyols; and

0-50% of a reactive monomer or polymer,

wherein all percentages referred to herein are based on volume; and

heating the composition to a temperature sufficient to melt the solder and to activate the chemically protected cross-linking agent.

20. The conductive ink according to claim 19 wherein the conductive ink has a bulk electrical resistivity of less than 10^-4 Ohms-cm.

21. The conductive ink according to claim 19 wherein the high melting point metal comprises spherical particles having an average particle diameter of 1-50 microns.

22. The conductive ink according to claim 21 wherein the high melting point metal is copper.

23. The conductive ink according to claim 19 wherein the chemically protected cross-linking agent is a chemically protected anhydride.