Forming conductive metal patterns with reactive polymers
View Patent ↗A pattern is formed in a polymeric layer comprising a reactive composition that comprises: (a) a polymer comprising pendant -arylene-X—C(═O)—O— t-alkyl groups that comprise a blocking group that is cleavable to provide pendant -arylene-XH groups, (b) a compound that provides a cleaving acid upon exposure to radiation having a λ max of 150 nm and to 450 nm, which cleaving acid has a pKa of 2 or less as measured in water, and (c) optionally, a photosensitizer. The polymeric layer is imagewise exposed to suitable radiation to provide non-exposed regions and exposed regions comprising a de-blocked and crosslinked polymer with pendant -arylene-XH groups. The exposed regions are contacted with electroless seed metal ions in the de-blocked and crosslinked polymer. After reduction, the corresponding electroless seed metal nuclei are electrolessly plated using a suitable metal that is the same as or different from the corresponding electroless seed metal nuclei.
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 comprising pendant
-arylene-X—C(═O)—O-t-alkyl groups wherein X is —NR—, —O—, or —S—, R is hydrogen or an alkyl group, and t-alkyl is a tertiary alkyl group, from which
—C(═O)—O-t-alkyl groups are cleavable using a cleaving acid,
(b) compound that provides a cleaving acid upon exposure to radiation having a λ max of at least 150 nm and up to and including 450 nm, which cleaving acid has a pKa of 2 or less as measured in water, and
(c) optionally, a photosensitizer, and
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 with pendant -arylene-XH groups,
optionally heating the polymeric layer simultaneously with or after patternwise exposing the polymeric layer but before contacting the exposed regions of the polymeric layer with electroless seed metal ions, at a temperature sufficient to generate pendant -arylene-XH groups in the exposed regions of the polymeric layer,
contacting the exposed regions of the polymeric layer with electroless seed metal ions to form a pattern of corresponding electroless seed metal ions in the exposed regions of the polymeric layer,
reducing the pattern of electroless seed metal ions to provide a pattern of 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.
2. The method of claim 1 , wherein t-alkyl is a tertiary alkyl group having 4 to 8 carbon atoms.
3. The method of claim 1 , wherein X is —NR— or —O—, R is hydrogen or methyl, and t-alkyl is a t-butyl group.
4. The method of claim 1 , wherein the (a) reactive polymer is a vinyl polymer comprising pendant -phenylene-NH—C(═O)O-t-butyl groups.
5. The method of claim 1 , wherein the (a) reactive polymer is a homopolymer comprising only recurring units that comprise the -arylene-X—C(═O)—O-t-alkyl groups.
6. The method of claim 1 , wherein the (a) reactive polymer is a copolymer comprising:
-A- recurring units that comprise the same or different pendant pendant -arylene-X—C(═O)—O-t-alkyl groups wherein X is —NR—, —O—, or —S—, R is hydrogen or an alkyl group, and t-alkyl is a tertiary alkyl group, from which
—C(═O)—O-t-alkyl groups are cleavable using a cleaving acid, and
-B- recurring units that are different from the -A- recurring units,
wherein the -A- recurring units comprise at least 50 mol % and up to and including 99 mol % of the total recurring units.
7. The method of claim 1 , wherein the (a) reactive polymer comprises at least 50 weight % and up to 99.5 weight % of the total dry weight of the polymeric layer.
8. The method of claim 1 , wherein the (b) compound is an arylsulfonium salt or aryliodonium salt that provides a cleaving acid having a pKa of less than 2 as determined in water.
9. The method of claim 1 , wherein the (c) photosensitizer is present in the polymeric layer in an amount of at least 1 weight % based on the total polymeric layer dry weight.
10. The method of claim 1 , comprising contacting the exposed regions in 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.
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 , further comprising heating the polymeric layer simultaneously with or immediately after patternwise exposing the polymeric layer at a temperature sufficient to generate pendant -arylene-XH groups.
13. The method of claim 1 , wherein after electrolessly plating the corresponding electroless seed metal nuclei with the electroless plating metal,
further exposing the polymeric layer to radiation having a λ max of at least 150 nm and up to and including 450 nm, and optionally heating during or after this exposing.
14. The method of claim 1 , comprising reducing the electroless seed metal ions in the exposed regions of the polymeric layer with a reducing agent that is a borane, aldehyde, hydroquinone, ascorbic acid, or a sugar.
15. The method of claim 1 , further comprising:
after the patternwise exposing and optional heating, removing the reactive composition in the non-exposed regions of the polymeric layer using a solvent in which the reactive composition is soluble or dispersible.
16. 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 electroless seed metal ions in a de-blocked and crosslinked polymer derived from a (a) reactive polymer comprising pendant -arylene-X—C(═O)—O-t-alkyl groups wherein X is —NR—, —O—, or —S—, R is hydrogen or an alkyl group, and t-alkyl is a tertiary alkyl group, from which —C(═O)—O-t-alkyl groups are cleavable using a cleaving acid, and
the non-exposed regions comprising a reactive composition that comprises:
the (a) reactive polymer comprising pendant -arylene-X—C(═O)—O-t-alkyl groups wherein X is —NR—, —O—, or —S—, R is hydrogen or an alkyl group, and t-alkyl is a tertiary alkyl group, from which —C(═O)—O-t-alkyl groups are cleavable using a cleaving acid,
(b) compound that provides a cleaving acid upon exposure to radiation having a λ max of at least 150 nm and up to and including 450 nm, which cleaving acid has a pKa of 2 or less as measured in water, and
(c) optionally, a photosensitizer.
17. 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 electroless seed metal nuclei in a de-blocked and crosslinked polymer derived from a (a) reactive polymer comprising pendant -arylene-X—C(═O)—O-t-alkyl groups wherein X is —NR—, —O—, or —S—, R is hydrogen or an alkyl group, and t-alkyl is a tertiary alkyl group, from which —C(═O)—O-t-alkyl groups are cleavable using a cleaving acid, and
the non-exposed regions comprising a reactive composition that comprises:
the (a) reactive polymer comprising pendant -arylene-X—C(═O)—O-t-alkyl groups wherein X is —NR—, —O—, or —S—, R is hydrogen or an alkyl group, and t-alkyl is a tertiary alkyl group, from which —C(═O)—O-t-alkyl groups are cleavable using a cleaving acid,
(b) compound that provides a cleaving acid upon exposure to radiation having a λ max of at least 150 nm and up to and including 450 nm, which cleaving acid has a pKa of 2 or less as measured in water, and
(c) optionally, a photosensitizer.
18. A product 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 corresponding electroless seed metal nuclei that has been electrolessly plated with the same or different metal in a de-blocked and crosslinked polymer derived from a (a) reactive polymer comprising pendant -arylene-X—C(═O)—O-t-alkyl groups wherein X is —NR—, —O—, or —S—, R is hydrogen or an alkyl group, and t-alkyl is a tertiary alkyl group, from which —C(═O)—O-t-alkyl groups are cleavable using a cleaving acid, and
the non-exposed regions comprising a reactive composition that comprises:
the (a) reactive polymer comprising pendant -arylene-X—C(═O)—O-t-alkyl groups wherein X is —NR—, —O—, or —S—, R is hydrogen or an alkyl group, and t-alkyl is a tertiary alkyl group, from which —C(═O)—O-t-alkyl groups are cleavable using a cleaving acid,
(b) compound that provides a cleaving acid upon exposure to radiation having a λ max of at least 150 nm and up to and including 450 nm, which cleaving acid has a pKa of 2 or less as measured in water, and
(c) optionally, a photosensitizer.