Electroless copper plating polydopamine nanoparticles

• US 10,294,567 B2
• Filed: 12/10/2015
• Issued: 05/21/2019
• Est. Priority Date: 12/11/2014
• Status: Active Grant

• Current Assignee: IP3 2017, Series 200 of Allied Security Trust I (Allied Security Trust)
• Original Assignee: The Research Foundation for The State University of New York (State University of New York)
• Inventors: Ma, Siyuan, Liu, Liang, Bromberg, Vadim, Singler, Timothy
• Primary Examiner(s): Tso, Stanley
• Application Number:
  US14/965,468
• Publication Number:
  US 20160168715A1
• Time in Patent Office: 1,258 Days
• Field of Search: 174268
• CPC Class Codes: B41M 3/006 Patterns of chemical products used for a specific purpose, e.g. pesticides, perfumes, adhesive patterns; use of microencapsulated material; Printing on smoking articles
• CPC Class Codes: C09D 11/10 based on artificial resins
• CPC Class Codes: C09D 11/322 Pigment inks
• CPC Class Codes: C23C 18/1607 by direct patterning
• CPC Class Codes: C23C 18/1608 from pretreatment step, i.e. selective pre-treatment
• CPC Class Codes: C23C 18/1689 After-treatment
• CPC Class Codes: C23C 18/1851 of surfaces of non-metallic or semiconducting in organic material
• CPC Class Codes: C23C 18/1893 with use of organic or inorganic compounds other than metals, first
• CPC Class Codes: C23C 18/2006 by other methods than those of C23C18/22 - C23C18/30
• CPC Class Codes: C23C 18/2086 with use of organic or inorganic compounds other than metals, first
• CPC Class Codes: C23C 18/31 Coating with metals
• CPC Class Codes: C23C 18/40 using reducing agents
• CPC Class Codes: C23C 18/44 using reducing agents
• CPC Class Codes: H05K 1/0306 Inorganic insulating substrates, e.g. ceramic, glass
• CPC Class Codes: H05K 1/0346 containing N
• CPC Class Codes: H05K 1/097 Inks comprising nanoparticles and specially adapted for being sintered at low temperature H05K1/095 takes precedence
• CPC Class Codes: H05K 2201/0154 Polyimide
• CPC Class Codes: H05K 2201/09236 Parallel layout layout of balanced signal pairs H05K1/0245; superposed layout H05K2201/09672
• CPC Class Codes: H05K 2203/0709 Catalytic ink or adhesive for electroless plating catalyst filler H05K2201/0236
• CPC Class Codes: H05K 2203/0786 Using an aqueous solution, e.g. for cleaning or during drilling of holes
• CPC Class Codes: H05K 2203/1173 : Differences in wettability, e.g. hydrophilic or hydrophobic areas
• CPC Class Codes: H05K 3/125 : by ink-jet printing
• CPC Class Codes: H05K 3/1275 : by other printing techniques, e.g. letterpress printing, intaglio printing, lithographic printing, offset printing
• CPC Class Codes: H05K 3/182 : characterised by the patterning method

Abstract

Aqueous dispersions of artificially synthesized, mussel-inspired polyopamine nanoparticles were inkjet printed on flexible polyethylene terephthalate (PET) substrates. Narrow line patterns (4 μm in width) of polydopamine resulted due to evaporatively driven transport (coffee ring effect). The printed patterns were metallized via a site-selective Cu electroless plating process at a controlled temperature (30° C.) for varied bath times. The lowest electrical resistivity value of the plated Cu lines was about 6 times greater than the bulk resistivity of Cu. This process presents an industrially viable way to fabricate Cu conductive fine patterns for flexible electronics at low temperature, and low cost.

Claims

1. A patterned substrate having at least one conductive trace, formed by a process comprising:

providing a substrate having a surface wettable with a volatile liquid;

selectively depositing by inkjet printing a suspension of nanoparticles in the volatile liquid, the nanoparticles comprising a catalyst for electroless plating, in a first pattern on the wettable surface of a line having edges;

drying the volatile liquid, to form a second pattern of nanoparticles which is inhomogeneous within the bounds of the first pattern on the wettable surface, the suspension of nanoparticles in the volatile liquid redistributing during drying to produce the second pattern according to a coffee ring effect comprising a first portion having a higher concentration of nanoparticles at the edges of the inkjet printed line comprising a single nanoparticle thick dense distribution of the nanoparticles, and a second portion having a sparse distribution of the nanoparticles between the edges of the inkjet printed line; and

selectively electroless plating the second pattern of nanoparticles which is inhomogeneous within the bounds of the first pattern on the wettable surface, to selectively form an inhomogeneous electrically conductive metal pattern corresponding to the inhomogeneous second pattern of nanoparticles on the wettable surface, corresponding to the first portion of the second pattern having the dense distribution of nanoparticles on the wettable surface, and corresponding to the second portion of the second pattern having the sparse distribution, to form an electrically insulating interruption in the electrically conductive pattern forming a pair of separated electrically conductive traces at the edges of the inkjet printed line with the electrically insulating interruption formed between the pair of separated electrically conductive traces.

2. The patterned substrate according to claim 1, wherein the substrate comprises at least one of a polyimide sheet and a glass sheet.

3. The patterned substrate according to claim 1, wherein the nanoparticles comprise polydopamine.

4. The patterned substrate according to claim 1, wherein the suspension of nanoparticles is selectively deposited by a process selected from the group consisting of inkjet printing, lithography, and a pad printing process.

5. The patterned substrate according to claim 1, wherein the volatile liquid comprises an aqueous suspension of nanoparticles, and is selectively deposited by selectively forming hydrophobic and hydrophilic regions on the substrate, the wettable surface comprising the hydrophilic regions, and wetting the hydrophilic regions with the suspension.

6. The patterned substrate according to claim 1, wherein the electroless plating comprises plating the nanoparticles with at least one of silver and copper.

7. A substrate having electrically interconnecting conductive traces, comprising:

a surface wettable with an aqueous solution;

a plurality of catalytic nanoparticles deposited on the wettable surface by inkjet printing a suspension of the plurality of catalytic nanoparticles in a volatile liquid in a pattern to form a line having edges, and evaporating the volatile liquid to form an inhomogeneous pattern of catalytic nanoparticles within the bounds of the inkjet printed pattern to redistribute the plurality of catalytic nanoparticles according to the coffee ring effect, the inhomogeneous pattern of catalytic nanoparticles having a single catalytic nanoparticle thick pattern of parallel lines comprising a higher concentration of catalytic nanoparticles at edges of the inkjet printed line spaced by a region of sparse catalytic nanoparticle deposition between the edges of the inkjet printed line; and

an electrolessly plated conductive metal pattern, formed on and corresponding to the inhomogeneous pattern of catalytic nanoparticles, selectively forming conductive traces over the parallel lines of catalytic nanoparticles, and being insulating between the respective parallel lines.

8. The substrate according to claim 7, wherein the surface comprises at least one of a surface of a polyimide sheet and a glass surface, the catalytic nanoparticles comprise polydopamine, and the conductive metal comprises at least one of silver and copper.

9. The substrate according to claim 7, wherein the surface wettable with the suspension of the plurality of catalytic nanoparticles comprises selectively formed hydrophobic and hydrophilic regions on the substrate, wherein the hydrophilic regions are wettable with the volatile liquid and the hydrophobic regions resist wetting by the volatile liquid.

10. A device, comprising:

a substrate having a surface with at least one hydrophilic portion;

a parallel line pattern of deposited catalytic nanoparticles on the surface formed by inkjet printing a suspension of the catalytic nanoparticles in a pattern to form a line having edges, and evaporating the suspension to form an inhomogeneous pattern of the catalytic nanoparticles within the bounds of the inkjet printed pattern, to redistribute the plurality of nanoparticles according to the coffee ring effect, the inhomogeneous pattern of catalytic nanoparticles having a single catalytic nanoparticle thick region, wherein the parallel line pattern comprises dense linear catalytic nanoparticle deposition regions within the hydrophilic portion, and a sparse catalytic nanoparticle deposition region between a respective pair of dense linear nanoparticle deposition regions in the hydrophilic portion; and

an electrolessly plated metal selectively formed proximate to the catalytic nanoparticles, forming conductive traces in a pattern corresponding to the inhomogeneous pattern of catalytic nanoparticles in the dense linear catalytic nanoparticle deposition regions, and being electrically insulating between the respective pair of dense linear catalytic nanoparticle deposition regions.

11. The device according to claim 10, wherein the catalytic nanoparticles comprise polydopamine, and the electrolessly plated metal comprises copper.

12. A printed circuit, comprising:

a coffee ring effect distribution of catalytic nanoparticles formed on a wettable portion of a surface of a substrate, formed by inkjet printing of a catalytic nanoparticle suspension in a line pattern having lateral edges, and subsequent evaporation of a volatile liquid to redistribute the catalytic nanoparticles for form an inhomogeneous distribution according to the coffee-ring effect, the inhomogeneous distribution defining at least one pair of parallel lines at the lateral edges comprising a single catalytic nanoparticle thick dense distribution of catalytic nanoparticles separated by a gap having a sparse distribution of catalytic nanoparticles; and

an electrolessly plated metal film, having an inhomogeneous pattern corresponding to and overlying the coffee-ring effect distribution of catalytic nanoparticles, defining a pair of electrically conductive traces separated by an insulating region.

13. The printed circuit according to claim 12, wherein the electrolessly plated metal film comprises at least one of copper, silver and nickel.

14. The printed circuit according to claim 12, wherein the substrate comprises at least one of a polyimide sheet and glass.

15. The printed circuit according to claim 12, wherein the catalytic nanoparticles comprise polydopamine.

16. The printed circuit according to claim 12, wherein the pair of electrically separated parallel conductive traces electrically control a liquid crystal material.

17. The printed circuit according to claim 12, wherein the pair of electrically separated parallel conductive traces electrically control a light emitting material.

18. The printed circuit according to claim 12, the pair of electrically separated parallel conductive traces electrically control an electrochromic material.

19. The printed circuit according to claim 12, wherein the pair of electrically separated parallel conductive traces electrically interface with a sensor.

20. The printed circuit according to claim 12, wherein the pair of electrically separated parallel conductive traces comprise an antenna.