Materials and methods for immobilization of catalysts on surfaces and for selective electroless metallization

• US 7,087,267 B2
• Filed: 11/29/2001
• Issued: 08/08/2006
• Est. Priority Date: 11/29/2001
• Status: Expired due to Fees

• Current Assignee: GlobalFoundries, Inc.
• Original Assignee: International Business Machines Corporation
• Inventors: Vella, Sarah Jane, Afzali-Ardakani, Ali, Khojasteh, Mahmoud Mostafa, Breen, Tricia Lynn
• Primary Examiner(s): LAM, CATHY FONG FONG
• Application Number:
  US09/998,007
• Publication Number:
  US 20030132121A1
• Time in Patent Office: 1,713 Days
• Field of Search: 428/209, 106/1.18, 205239-250
• US Class Current: 427/304
• CPC Class Codes: B01J 2231/4205 C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
• CPC Class Codes: B01J 2231/4261 Heck-type, i.e. RY + C=C, in which R is aryl
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 2531/824 Palladium
• CPC Class Codes: B01J 31/06 containing polymers organometallic polymers B01J31/123; polymer-bound organometallic complexes B01J31/165; coordination polymers B01J31/1691
• CPC Class Codes: B01J 31/1658 immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
• CPC Class Codes: B01J 31/185 Phosphites ((RO)3P) , their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
• CPC Class Codes: B01J 31/2409 with more than one complexing phosphine-P atom
• CPC Class Codes: B01J 35/56 Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
• CPC Class Codes: B01J 37/0217 Pretreatment of the substrate before coating
• CPC Class Codes: C23C 18/1608 from pretreatment step, i.e. selective pre-treatment
• CPC Class Codes: C23C 18/285 Sensitising or activating with tin based compound or composition
• CPC Class Codes: C23C 18/30 Activating or accelerating or sensitising with palladium or other noble metal
• CPC Class Codes: Y10T 428/24917 including metal layer

Abstract

A method of immobilizing a catalyst on a substrate surface involves providing novel ligating copolymers comprising functional groups capable of binding to a substrate surface and functional groups capable of ligating to catalysts such as metal ions, metal complexes, nanoparticles, or colloids; applying the ligating copolymer to a substrate surface to cause the ligating copolymer to bind thereto, and contacting the modified substrate surface with a solution of a catalyst, causing the catalyst to be ligated by the ligating copolymer and thus immobilized on the substrate surface. The ligating copolymer may be patterned on the substrate surface using a method such as microcontact printing. A method of selectively metallizing a substrate in a desired pattern involves using a ligating chemical agent comprising functional groups capable of binding to a substrate surface and functional groups capable of ligating to electroless plating catalysts; applying the ligating chemical agent to a substrate in a desired pattern using microcontact printing to cause the ligating chemical agent to bind thereto; contacting the modified substrate surface with a solution of an electroless plating catalyst, causing the catalyst to be ligated by the ligating chemical agent and thus bound to the surface; and metallizing the catalyzed regions of the substrate surface using electroless plating.

Claims

1. A method of rendering a substrate catalytic to electroless metal deposition comprising the steps of:

(a) depositing a ligating chemical agent on said substrate, which is capable of both binding to said substrate and ligating to an electroless plating catalyst; and

(b) ligating said electroless plating catalyst to said ligating chemical agent,

wherein said ligating chemical agent is a bifunctional molecular species of the form R₇R₈P(CH₂)_nPO₃R₉R₁₀, wherein n is between 1 and 20, and wherein R₇ and R₈ are substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted heterocyclic groups, and may be the same or different, and wherein R₉ and R₁₀ are hydrogen atoms.

2. The method of claim 1, further comprising, after step (a), the step of contacting said substrate with a chemical reagent capable of reacting with at least one functional group of said ligating chemical agent.

3. The method of claim 1, wherein said substrate is selected from the group consisting of:

silicon oxide, titanium oxide, zirconium oxide, indium tin oxide, indium zinc oxide, tin oxide, zinc oxide, copper oxide, aluminum oxide, nickel oxide, and combinations thereof.

4. The method of claim 1, wherein said substrate comprises a polymer with surface hydroxyl groups.

5. The method of claim 1, wherein said electroless plating catalyst is a palladium catalyst.

6. The method of claim 1, wherein said electroless plating catalyst is a palladium-tin colloid.

7. The method of claim 1, wherein said electroless plating catalyst is selected to deposit metals from the group consisting of:

cobalt, nickel, copper, gold, platinum, palladium, silver, and alloys thereof.

8. An article of manufacture comprising a substrate rendered catalytic according to the method of claim 1, having a metal coating over portions of said substrate in a selected pattern and being bonded to said substrate through an intermediate layer of said catalyzed ligating chemical agent.

9. A method of rendering a substrate catalytic to electroless metal deposition comprising the steps of:

(a) depositing a ligating chemical agent on said substrate, which is capable of both binding to said substrate and ligating to an electroless plating catalyst; and

(b) ligating said electroless plating catalyst to said ligating chemical agent,

wherein said ligating chemical agent has the chemical structure;

10. The method of claim 9, further comprising, after step (a), the step of contacting said substrate with a chemical reagent capable of reacting with at least one functional group of said ligating chemical agent.

11. The method of claim 9, wherein said substrate is selected from the group consisting of:

silicon oxide, titanium oxide, zirconium oxide, indium tin oxide, indium zinc oxide, tin oxide, zinc oxide, copper oxide, aluminum oxide, nickel oxide, and combinations thereof.

12. The method of claim 9, wherein said substrate comprises a polymer with surface hydroxyl groups.

13. The method of claim 9, wherein said electroless plating catalyst is a palladium catalyst.

14. The method of claim 9, wherein said electroless plating catalyst is a palladium-tin colloid.

15. The method of claim 9, wherein said electroless plating catalyst is selected to deposit metals from the group consisting of:

cobalt, nickel, copper, gold, platinum, palladium, silver, and alloys thereof.

16. An article of manufacture comprising a substrate rendered catalytic according to the method of claim 9, having a metal coating over portions of said substrate in a selected pattern and being bonded to said substrate through an intermediate layer of said catalyzed ligating chemical agent.