Nickel electroplating compositions for rough nickel

Patent metadata

Field	Value
Publication number	US-12410534-B2
Application number	US-202318466422-A
Country	US
Kind code	B2
Filing date	Sep 13, 2023
Priority date	Sep 26, 2022
Publication date	Sep 9, 2025
Grant date	Sep 9, 2025

Abstract

Nickel electroplating compositions containing mercaptotetrazoles deposit rough nickel on substrates. The rough nickel can be electroplated over wide current density ranges. The rough nickel deposits enable improved adhesion to other metal layers in contrast to many conventional nickel deposits.

First claim

What is claimed is:

1. A nickel electroplating composition comprising nickel ions and a mercaptotetrazole having a formula:

wherein R 1 is chosen from hydrogen, linear or branched (C 1 -C 6 )alkyl, linear or branched hydroxy (C 1 -C 6 )alkyl or salts thereof, linear or branched carboxy (C 1 -C 6 )alkyl or salts thereof, linear or branched sulfo (C 1 -C 6 )alkyl or salts thereof, and X + is H + or an alkali metal ion selected from the group consisting of Na + and K + , wherein the nickel electroplating composition is free of alloying metals.

2. The nickel electroplating composition of claim 1 , wherein R 1 is chosen from hydrogen, linear or branched (C 1 -C 3 )alkyl, linear or branched hydroxy (C 1 -C 3 )alkyl or salts thereof, linear or branched carboxy (C 1 -C 3 )alkyl or salts thereof, linear or branched sulfo (C 1 -C 3 )alkyl or salts thereof, and X + is H + or Na + .

3. The nickel electroplating composition of claim 1 , wherein the mercaptotetrazole is in amounts of 5 ppm or greater.

4. The nickel electroplating composition of claim 1 , wherein a source of the nickel ions is selected from the group consisting of nickel sulfate, nickel sulfate hexahydrate, nickel sulfate heptahydrate, nickel sulfamate, nickel sulfamate tetrahydrate, nickel chloride, nickel chloride hexahydrate, nickel carbonate, nickel methane sulfonate, nickel bromide, nickel fluoride, nickel iodide, nickel oxalate, nickel citrate, nickel tetrafluoroborate, nickel hypophosphite, nickel acetate and mixtures thereof.

5. The nickel electroplating composition of claim 1 , further comprising a source of chloride ions.

6. The nickel electroplating composition of claim 5 , wherein the source of the chloride ions is selected from the group consisting of nickel chloride, nickel chloride hexahydrate, hydrogen chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium chloride, guanidine hydrochloride, ethylenediamine dihydrochloride, trimethylammonium chloride, pyridine hydrochloride, phenylammonium chloride, hydrazine dihydrochloride and mixtures thereof.

7. The nickel electroplating composition of claim 1 , wherein a pH of the nickel electroplating composition is from 2 to 6.

8. The nickel electroplating composition of claim 1 , further comprising a pH adjusting agent.

9. The nickel electroplating composition of claim 8 , wherein the pH adjusting agent is selected from the group consisting sulfuric acid, hydrochloric acid, sulfamic acid, boric acid, acetic acid, amino acetic acid, ascorbic acid, lactic acid, 5-sulfosalicylic acid and salts thereof.

10. The nickel electroplating composition of claim 1 , further comprising a surfactant.

11. The nickel electroplating composition of claim 10 , wherein the surfactant is sodium di(1,3-dimethylbutyl) sulfosuccinate, sodium-2-ethylhexylsulfate, sodium diamyl sulfosuccinate, sodium lauryl sulfate, sodium lauryl ether-sulfate, sodium di-alkylsulfosuccinates, sodium dodecylbenzene sulfonate, perfluorinated quaternary amines thereof, or mixtures thereof.

12. The nickel electroplating composition of claim 1 , wherein the nickel electroplating composition is free of cyanide compounds.

13. A method of electroplating nickel metal on a substrate, comprising:
a) providing the substrate;
b) contacting the substrate with the nickel electroplating composition of claim 1 ; and
c) depositing a nickel layer on the substrate by electroplating, wherein the nickel layer comprises a Sa>70 nm and a Sdr>4%.

14. The nickel electroplating composition of claim 1 , wherein a concentration of nickel salts in the nickel electroplating composition is 20 g/L or greater.

15. A nickel electroplating composition comprising nickel ions and a mercaptotetrazole selected from the group consisting of 5-mercapto-(1H)-tetrazolylacetic acid, sodium salt, 5-mercapto-1H-tetrazol-1-methane sulfonic acid, disodium salt and mixtures thereof, wherein the nickel electroplating composition is free of alloying metals.

16. A method of electroplating nickel metal on a substrate, comprising:
a) providing the substrate;
b) contacting the substrate with the nickel electroplating composition of claim 15 ; and
c) depositing a nickel layer on the substrate by electroplating, wherein the nickel layer comprises a Sa≥70 nm and a Sdr≥4%.

17. A nickel electroplating composition comprising nickel ions and a mercaptotetrazole having a formula:

wherein R 1 is chosen from hydrogen, linear or branched (C 1 -C 6 )alkyl, linear or branched hydroxy (C 1 -C 6 )alkyl or salts thereof, linear or branched carboxy (C 1 -C 6 )alkyl or salts thereof, linear or branched sulfo (C 1 -C 6 )alkyl or salts thereof, linear or branched amino (C 1 -C 6 )alkyl, phenyl or benzyl, and X + is H + , or an alkali metal ion, wherein the mercaptotetrazole is in amounts of 10 ppm to 100 ppm, wherein the nickel electroplating composition is free of alloying metals.

18. A method of electroplating nickel metal on a substrate, comprising:
a) providing the substrate;
b) contacting the substrate with the nickel electroplating composition of claim 17 ; and
c) depositing a nickel layer on the substrate by electroplating, wherein the nickel layer comprises a Sa≥70 nm and a Sdr≥4%.

Assignees

• Rohm & Haas Elect Mat
• Dupont Electronic Mat International Llc

Inventors

• Wu Weigang
• Ting Fai Lung

Classifications

• C25D7/12

  Semiconductors · CPC title

• C25D5/605

  Surface topography of the layers, e.g. rough, dendritic or nodular layers · CPC title

• C25D3/18 Primary

  Heterocyclic compounds · CPC title

• C25D3/12 Primary

  of nickel or cobalt · CPC title

• H10W20/4403

  based on metals, e.g. alloys, metal silicides (H10W20/4484 takes precedence) · CPC title