Electroless plating method using halide
A conductive pattern is formed using a reactive polymer comprising pendant tertiary alkyl ester groups, a compound that provides an acid upon exposure to radiation, and a crosslinking agent. A polymeric layer is patternwise exposed to form first exposed regions with a polymer comprising carboxylic acid groups that are contacted with electroless seed metal ions, and then contacted with a halide to form corresponding electroless seed metal halide. Another exposure converts electroless seed metal halide to electroless seed metal nuclei and forms second exposed regions. A reducing agent is used to develop the electroless seed metal nuclei in the second exposed regions, or to develop the electroless seed metal halide in the first exposed regions. Fixing is used to remove any remaining electroless seed metal halide. The electroless seed metal nuclei are then electrolessly plated in various exposed regions.
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) a reactive polymer comprising -A-recurring units comprising pendant tertiary alkyl ester groups in an amount of at least 25 mol %, based on total (a) reactive polymer recurring units,
(b) a compound that provides an acid upon exposure to radiation having a λ max of at least 150 nm and up to and including 450 nm, which acid has a pKa of less than 2 as measured in water,
(c) a crosslinking agent that is capable of reacting in the presence of the acid provided by the (b) compound to provide crosslinking in the (a) reactive polymer, and
(d) optionally, a photosensitizer,
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 first exposed regions comprising a polymer comprising carboxylic acid groups,
optionally heating the polymeric layer simultaneously with or after patternwise exposing the polymeric layer but before contacting the first exposed regions of the polymeric layer with electroless seed metal ions at a temperature sufficient to generate pendant carboxylic acid groups in the (a) reactive polymer in the first exposed regions of the polymeric layer,
contacting the first exposed regions of the polymeric layer with electroless seed metal ions to form electroless seed metal ions in the first exposed regions of the polymeric layer,
contacting the first exposed regions of the polymeric layer with a halide to react with the 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 to convert at least some of the corresponding electroless seed metal halide in the first exposed regions of the polymeric layer to corresponding electroless seed metal nuclei and to form second exposed regions in the polymeric layer,
optionally contacting the polymeric layer with a reducing agent either: (i) to develop the corresponding electroless seed metal image in the second exposed regions of the polymeric layer to form corresponding electroless seed metal nuclei, or (ii) to develop all of the corresponding electroless seed metal halide in the first exposed regions of the polymeric layer,
optionally contacting the polymeric layer with a fixing agent to remove any remaining corresponding electroless seed metal halide in either the first exposed regions of the polymeric layer, the second exposed regions of the polymeric layer, or both of the first exposed regions and the second exposed regions of the polymeric layer, and
electrolessly plating the corresponding electroless seed metal nuclei in the first exposed regions, any corresponding electroless seed metal nuclei formed in the second exposed regions, or corresponding electroless seed metal nuclei in 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.
2. The method of claim 1 , wherein the (c) crosslinking agent is part of the (a) reactive polymer as —B-recurring units comprising pendant groups that provide crosslinking in the presence of the acid provided by the (b) compound, which —B-recurring units are present in the (a) reactive polymer in an amount of at least 2 mol %, based on the total (a) reactive polymer recurring units.
3. The method of claim 1 , wherein the (c) crosslinking agent is a compound distinct from the (a) reactive polymer.
4. The method of claim 3 , wherein the (c) crosslinking agent is an aziridine, carbodiimide, isocyanate, ketene, glycoluril formaldehyde resin, polycarboxylic acid or anhydride, polyamine, epihalohydrin, diepoxide, dialdehyde, diol, carboxylic acid halide, or mixture thereof.
5. The method of claim 1 , wherein the (a) reactive polymer comprises a backbone and arranged randomly along the backbone,
-A-recurring units comprising pendant tertiary alkyl ester, the -A-recurring units being present in the (a) reactive polymer in an amount of at least 50 mol % and up to and including 98 mol % based on total (a) reactive polymer recurring units, and
—B-recurring units comprising pendant epoxy groups in an amount of at least 2 mol % and up to and including 50 mol % based on total (a) reactive polymer recurring units.
6. The method of claim 5 , wherein the (a) reactive polymer further comprises one or more additional —C-recurring units that are different from all -A- and —B-recurring units, the one or more additional —C-recurring units being present in an amount of at least 1 mol % and up to and including 25 mol % based on the total (a) reactive polymer recurring units.
7. The method of claim 1 , wherein the (a) reactive polymer comprises pendant tertiary alkyl ester groups comprising a tertiary alkyl group having 4 to 8 carbon atoms.
8. The method of claim 1 , wherein the (a) reactive polymer comprises pendant t-butyl ester groups.
9. The method of claim 1 , wherein the (a) reactive polymer comprises at least 50 weight % and up to 97 weight % of the total dry weight of the polymeric layer.
10. The method of claim 1 , wherein the (b) compound is an arylsulfonium salt or aryliodonium salt that provides an acid having a pKa of less than 2 as measured in water.
11. The method of claim 1 , wherein the (d) photosensitizer is present in the polymeric layer in an amount of at least 1 weight % based on the total solids in the polymeric layer.
12. The method of claim 1 , comprising contacting the first exposed regions of the polymeric layer with electroless seed metal ions selected from the groups consisting of silver ions, platinum ions, palladium ions, gold ions, rhodium ions, iridium ions, nickel ions, tin ions, and copper ions.
13. 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.
14. The method of claim 1 , further comprising heating the polymeric layer simultaneously with or immediately after patternwise exposing the polymeric layer at a temperature sufficient to generate carboxylic acid groups in the (a) reactive polymer in first exposed regions of the polymeric layer.
15. 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.
16. 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.
17. The method of claim 1 , comprising contacting the first exposed regions of the polymeric layer with an iodide, chloride, bromide, or a combination of two or more of these halides to form corresponding electroless seed metal halide in the first exposed regions of the polymeric layer.
18. The method of claim 1 , comprising exposing the polymeric layer to convert the corresponding electroless seed metal halide in second exposed regions of the polymeric layer to corresponding electroless seed metal nuclei at a wavelength having a λ max of at least 240 nm and up to and including 450 nm.
19. An intermediate article comprising a substrate and having disposed thereon a polymeric layer comprising first exposed regions and non-exposed regions,
the first exposed regions comprising a pattern of a corresponding electroless seed metal halide in a de-blocked and crosslinked polymer being derived from (a) reactive polymer comprising -A-recurring units comprising pendant tertiary alkyl ester groups in an amount of at least 25 mol %, based on total (a) reactive polymer recurring units, and
the non-exposed regions comprising a reactive composition that comprises:
the (a) reactive polymer comprising -A-recurring units comprising pendant tertiary alkyl ester groups in an amount of at least 25 mol %, based on total (a) reactive polymer recurring units,
(b) a compound that provides an acid upon exposure to radiation having a λ max of at least 150 nm and up to and including 450 nm, which acid has a pka of less than 2 as measured in water,
(c) a crosslinking agent that is capable of reacting in the presence of the acid provided by the (b) compound to provide crosslinking in the (a) reactive polymer, and
(d) optionally, a photosensitizer.
20. A method for forming a pattern in a polymeric layer, the method comprising:
providing a polymeric layer comprising a reactive composition that comprises:
(a) a reactive polymer comprising -A-recurring units comprising pendant tertiary alkyl ester groups in an amount of at least 25 mol %, based on total (a) reactive polymer recurring units,
(b) a compound that provides an acid upon exposure to radiation having a λ max of at least 150 nm and up to and including 450 nm, which acid has a pKa of less than 2 as measured in water,
(c) a crosslinking agent that is capable of reacting in the presence of the acid provided by the (b) compound to provide crosslinking in the (a) reactive polymer, and
(d) optionally, a photo sensitizer,
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 first exposed regions comprising a polymer comprising carboxylic acid groups,
optionally heating the polymeric layer simultaneously with or after patternwise exposing the polymeric layer but before contacting the first exposed regions of the polymeric layer with electroless seed metal ions at a temperature sufficient to generate pendant carboxylic acid groups in the (a) reactive polymer in the first exposed regions of the polymeric layer,
contacting the first exposed regions of the polymeric layer with electroless seed metal ions to form electroless seed metal ions in the first exposed regions of the polymeric layer,
contacting the first exposed regions of the polymeric layer with a halide to react with the electroless seed metal ions and to form corresponding electroless seed metal halide in the first exposed regions of the polymeric layer, and
electrolessly plating the corresponding electroless seed metal halide in the first exposed regions of the polymeric layer with a metal that is the same as or different from the corresponding electroless seed metal nuclei.