Electroless plating method
View Patent ↗A conductive metal pattern is formed in a polymeric layer that has a polymer that comprises (1) pendant groups that are capable of providing pendant sulfonic acid groups upon exposure of the reactive polymer to radiation, and (2) pendant groups that are capable of reacting in the presence of the sulfonic acid groups to provide crosslinking. The polymeric layer is patternwise exposed to form non-exposed regions and exposed regions, which are contacted with a reducing agent to incorporate reducing agent therein. These exposed regions are then contacted with electroless seed metal ions to oxidize the reducing agent to form corresponding electroless seed metal nuclei that can be then electrolessly plated with a conductive metal.
1. A method for forming a pattern in a polymeric layer, the method comprising:
providing a polymeric layer comprising a reactive composition that comprises a reactive polymer that comprises (1) pendant groups that are capable of providing pendant sulfonic acid groups upon exposure of the reactive polymer to radiation having a λ max of at least 150 nm and up to and including 450 nm, and (2) pendant groups that are capable of reacting in the presence of the sulfonic acid groups to provide crosslinking in the reactive polymer,
patternwise exposing the polymeric layer to radiation having a λ max of at least 150 nm and up to and including 450 nm, to provide a polymeric layer comprising non-exposed regions and exposed regions comprising a polymer comprising pendant sulfonic acid groups,
contacting the exposed regions of the polymeric layer with a reducing agent to incorporate reducing agent in the exposed regions of the polymeric layer,
contacting the exposed regions of the polymeric layer with electroless seed metal ions to oxidize the reducing agent in the exposed regions of the polymeric layer and to form corresponding electroless seed metal nuclei in the exposed regions of the polymeric layer, and
electrolessly plating the corresponding electroless seed metal nuclei in the exposed regions of the polymeric layer with a metal that is the same as or different from the corresponding electroless seed metal nuclei,
wherein the reactive polymer comprises a backbone and at least -A- and -B- recurring units, arranged randomly along the backbone, wherein:
the -A- recurring units comprise pendant aromatic sulfonic acid oxime ester groups, which recurring units are capable of providing the (1) pendant aromatic sulfonic acid groups upon irradiation with radiation having a λ max of at least 150 nm and up to and including 450 nm, the -A- recurring units being present in the reactive polymer in an amount of at least 25 mol % and up to and including 98 mol % based on total reactive polymer recurring units, and
the -B- recurring units comprise the (2) pendant groups that can provide crosslinking upon generation of the pendant aromatic sulfonic acid groups in the -A- recurring units, the -B- recurring units being present in an amount of at least 2 mol % and up to and including 75 mol % based on total reactive polymer recurring units.
2. The method of claim 1 , wherein the -A- recurring units are present in the reactive polymer in an amount of at least 40 mol % and up to and including 95 mol % based on total reactive polymer recurring units, and the -B- recurring units are present in the reactive polymer in an amount of at least 5 mol % and up to and including 60 mol % based on total reactive polymer recurring units.
3. The method of claim 1 , wherein the -A- recurring units are present in the reactive polymer in an amount of at least 60 mol % and up to and including 95 mol % based on total reactive polymer recurring units, and the -B- recurring units are present in the reactive polymer in an amount of at least 5 mol % and up to and including 40 mol % based on total reactive polymer recurring units.
4. The method of claim 1 , wherein the -B- recurring units comprise pendant crosslinking epoxy groups.
5. The method of claim 1 , wherein the reactive polymer further comprises one or more additional recurring units that are different from all -A- and -B- recurring units.
6. The method of claim 5 , wherein the reactive polymer further comprises one or more additional recurring units that are derived from one or more ethylenically unsaturated polymerizable monomers selected from the group consisting of alkyl acrylates, alkyl methacrylates, (meth)acrylamides, vinyl esters, (meth)acrylonitrile, maleic anhydrides, maleic imides, and styrene and styrene derivatives.
7. The method of claim 5 , wherein the one or more additional recurring units are present in an amount of at least 1 mol % and up to and including 25 mol % based on the total reactive polymer recurring units.
8. The method of claim 1 , wherein the reactive polymer comprises at least 50 weight % and up to and including 100 weight % of the total dry weight of the polymeric layer.
9. The method of claim 1 , comprising contacting the exposed regions of the polymeric layer with electroless seed metal ions selected from the group consisting of silver ions, platinum ions, palladium ions, gold ions, tin ions, rhodium ions, iridium ions, nickel ions, and copper ions.
10. The method of claim 1 , wherein the electroless seed metal ions are provided as a metal salt or metal-ligand complex.
11. The method of claim 1 , comprising electrolessly plating with a metal that is selected from the group consisting of copper(II), silver(I), gold(IV), palladium(II), platinum(II), nickel(II), chromium(II), and combinations thereof.
12. The method of claim 1 , comprising providing the polymeric layer on a substrate.
13. The method of claim 1 , comprising patternwise exposing the polymeric layer to radiation having a λ max of at least 150 nm and up to and including 330 nm.
14. The method of claim 1 , comprising contacting the polymeric layer with a reducing agent that is a borane, aldehyde, hydroquinone, or sugar (or polysaccharide) reducing agent.
15. An intermediate article comprising a substrate and having disposed thereon a polymeric layer comprising exposed regions and non-exposed regions,
the exposed regions comprising a pattern of a de-blocked and crosslinked polymer into which a reducing agent has diffused, the de-blocked and crosslinked polymer being derived from a reactive polymer that comprises (1) pendant groups that are capable of providing pendant sulfonic acid groups upon exposure of the reactive polymer to radiation having a λ max of at least 150 nm and up to and including 450 nm, and (2) pendant groups that are capable of reacting in the presence of the sulfonic acid groups to provide crosslinking in the reactive polymer, and
the non-exposed regions comprising a reactive composition that comprises the reactive polymer,
wherein the reactive polymer further comprises a backbone and at least -A- and -B- recurring units, arranged randomly along the backbone, wherein:
the -A- recurring units comprise pendant aromatic sulfonic acid oxime ester groups, which recurring units are capable of providing the (1) pendant aromatic sulfonic acid groups upon irradiation with radiation having a λ max of at least 150 nm and up to and including 450 nm, the -A- recurring units being present in the reactive polymer in an amount of at least 25 mol % and up to and including 98 mol % based on total reactive polymer recurring units, and
the -B- recurring units comprise the (2) pendant groups that can provide crosslinking upon generation of the pendant aromatic sulfonic acid groups in the -A- recurring units, the -B- recurring units being present in an amount of at least 2 mol % and up to and including 75 mol % based on total reactive polymer recurring units.