Immersion tin silver plating in electronics manufacture
View Patent ↗A method is provided for depositing a whisker resistant tin-based coating layer on a surface of a copper substrate. The method is useful for preparing an article comprising a copper substrate having a surface; and a tin-based coating layer on the surface of the substrate, wherein the tin-based coating layer has a thickness between 0.5 micrometers and 1.5 micrometers and has a resistance to formation of copper-tin intermetallics, wherein said resistance to formation of copper-tin intermetallics is characterized in that, upon exposure of the article to at least seven heating and cooling cycles in which each cycle comprises subjecting the article to a temperature of at least 217° C. followed by cooling to a temperature between about 20° C. and about 28° C., there remains a region of the tin coating layer that is free of copper that is at least 0.25 micrometers thick.
1. A method for depositing a whisker resistant tin-based coating layer on a surface of a copper substrate, the method comprising:
contacting the surface of the copper substrate selected from the group of substrates consisting of copper on a printed wiring board, lead frames in electronic devices, connectors in electronic devices, and die pads in under bump metallization with an immersion tin plating composition comprising the following to thereby form, by displacement plating reaction between Sn 2+ ions and Cu metal of the substrate, a tin-based coating comprising at least 80 wt % Sn:
a source of Sn 2+ ions sufficient to provide a concentration of Sn 2+ ions between about 5 g/L and about 20 g/L;
a source of Ag + ions sufficient to provide a concentration of Ag + ions between about 10 ppm and about 24 ppm;
a source of sulfur-based complexing agent sufficient to provide a concentration of sulfur-based complexing agent between about 60 g/L and about 120 g/L;
a source of hypophosphite ion in an amount sufficient to enhance the rate of deposition, wherein the amount of hypophosphite ion is equivalent to that provided by between 70 g/L and about 100 g/L of sodium hypophosphite;
in addition to the hypophosphite source, a source of anti-oxidant sufficient to provide a concentration of anti-oxidant between about 30 g/L and about 110 g/L;
a source of pyrrolidone sufficient to provide a concentration of pyrrolidone of at least about 12 g/L; and
an acid in a concentration sufficient to lower the pH of the composition between about 0 and about 5,
wherein the tin-based coating layer that is deposited onto the copper substrate surface by the immersion tin plating composition has a thickness between 0.5 micrometers and 1.5 micrometers.
2. The method of claim 1 wherein the source of Ag + ions is sufficient to provide a concentration of Ag + ions between about 12 ppm and about 24 ppm.
3. The method of claim 1 wherein the source of Ag + ions is sufficient to provide a concentration of Ag + ions between about 12 ppm and about 20 ppm.
4. The method of claim 1 wherein the source of Ag + ions is sufficient to provide a concentration of Ag + ions between about 10 ppm and about 16 ppm.
5. The method of claim 1 wherein the source of Sn 2+ ions is sufficient to provide a concentration of Sn 2+ ions between about 6 g/L and about 12 g/L.
6. The method of claim 1 wherein the source of Sn 2+ ions is sufficient to provide a concentration of Sn 2+ ions between about 6 g/L and about 10 g/L.
7. The method of claim 1 wherein the source of pyrrolidone comprises polyvinylpyrrolidone.
8. The method of claim 1 wherein the source of pyrrolidone comprises polyvinylpyrrolidone and 1-methyl-2-pyrrolidone.
9. The method of claim 1 wherein the anti-oxidant is sufficient to provide a concentration between about 40 g/L and about 80 g/L.
10. The method of claim 1 wherein contacting the surface of the copper substrate with the immersion tin plating composition causes the oxidation of copper into copper ions.
11. The method of claim 10 wherein additional sulfur-based complexing agent is added to the immersion tin plating composition at a rate of between about 3 g/L and about 9 g/L complexing agent per 1 g of copper ion/L buildup.
12. The method of claim 1 wherein the source of pyrrolidone is sufficient to provide a concentration of pyrrolidone from about 12 g/L to about 18 g/L.
13. The method of claim 1 wherein said contact deposits the tin-based coating layer to a thickness between 0.7 micrometers and 1.2 micrometers.
14. The method of claim 1 wherein said contact deposits the tin-based coating layer to a thickness between 0.7 micrometers and 1.0 micrometers.
15. The method of claim 1 wherein the source of hypophosphite ion comprises sodium hypophosphite.
16. The method of claim 1 wherein the tin-based coating layer remains solderable through at least about 5 lead-free reflow cycles.