Electroless plating method using halide
View Patent ↗A conductive metal pattern is formed using a reactive polymer that can provide pendant sulfonic acid groups upon exposure to radiation, and (2) pendant groups that are capable of providing crosslinking. The polymeric layer is patternwise exposed to radiation to provide first exposed regions that are then contacted with electroless seed metal ions to form a pattern of electroless seed metal ions, followed by contact with a halide. At least some of the electroless seed metal halide can be exposed to form second exposed regions. The polymeric layer can be contacted with a reducing agent either: (i) to develop the electroless seed metal image in the second exposed regions, or (ii) to develop all of the electroless seed metal halide in the first exposed regions, and optionally contacted with a fixing agent. The electroless seed metal nuclei in the first exposed regions can be electrolessly plated with a conductive metal.
1. A method for forming a pattern in a polymeric layer, the method comprising:
providing a polymeric layer on a substrate, the polymeric layer comprising a reactive composition that comprises a reactive polymer that comprises: a polymer backbone, (1) pendant labile groups that are connected to the polymer backbone and the pendant labile groups being capable of being deblocked to provide 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 connected to the polymer backbone, which pendant groups are capable of reacting in the presence of the pendant 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 comprising the reactive polymer and first exposed regions comprising a deblocked and crosslinked polymer,
contacting the first exposed regions comprising the deblocked and crosslinked polymer with electroless seed metal ions to form a pattern of electroless seed metal ions coordinated within the first exposed regions,
contacting the first exposed regions comprising the deblocked and crosslinked polymer and coordinated electroless seed metal ions with a halide to react with the coordinated electroless seed metal ions and to form corresponding electroless seed metal halide in the first exposed regions of the polymeric layer,
exposing the polymeric layer again to radiation having a λ max of at least 150 nm and up to and including 450 nm to convert at least some of the corresponding electroless seed metal halide in the first exposed regions to a corresponding electroless seed metal image and to form second exposed regions in the polymeric layer,
contacting the polymeric layer with a reducing agent either: (i) to develop the corresponding electroless seed metal image in the second exposed regions, or (ii) to develop all of the corresponding electroless seed metal halide in the first exposed regions, to form corresponding electroless seed metal nuclei in either the second exposed regions, the first exposed regions, or both of the first and second exposed regions,
contacting the polymeric layer with a fixing agent to remove any remaining corresponding electroless seed metal halide in either the first exposed regions, the second exposed regions, or both the first exposed regions and the second exposed regions, and
electrolessly plating the corresponding electroless seed metal nuclei in the first exposed regions, second exposed regions, or both the first exposed regions and the second exposed regions, of the polymeric layer with a metal that is the same as or different from the corresponding electroless seed metal nuclei, and
wherein at any time after patternwise exposing the polymeric layer, removing the reactive composition in the non-exposed regions of the polymeric layer.
2. The method of claim 1 , wherein the reactive polymer comprises at least -A- and -B- recurring units, arranged randomly along the polymer backbone, wherein:
the -A- recurring units comprise pendant aromatic sulfonic acid oxime ester groups, which recurring units are capable of providing 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 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.
3. The method of claim 2 , 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.
4. The method of claim 2 , 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.
5. The method of claim 2 , wherein the -B- recurring units comprise pendant crosslinking epoxy groups.
6. The method of claim 2 , wherein the reactive polymer further comprises one or more additional recurring units that are different from all -A- and -B- recurring units.
7. The method of claim 6 , 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.
8. The method of claim 6 , 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.
9. 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.
10. The method of claim 1 , wherein the electroless seed metal ions are 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.
11. The method of claim 1 , wherein the electroless seed metal ions are provided as a metal salt or metal-ligand complex.
12. 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.
13. The method of claim 1 , comprising pattemwise 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 , wherein the reducing agent is a borane, aldehyde, hydroquinone, or sugar reducing agent.
15. The method of claim 1 , wherein the halide is an iodide, chloride, bromide, or a combination of two or more of these halides.
16. The method of claim 1 , comprising exposing again the polymeric layer to convert the corresponding electroless seed metal halide in the first exposed regions to corresponding electroless seed metal image to radiation having a λ max of at least 240 nm and up to and including 450 nm.