Composition for metal plating comprising suppressing agent for void free filing

Patent metadata

Field	Value
Publication number	US-11926918-B2
Application number	US-201716468467-A
Country	US
Kind code	B2
Filing date	Dec 19, 2017
Priority date	Dec 20, 2016
Publication date	Mar 12, 2024
Grant date	Mar 12, 2024

Abstract

The invention relates to a polyamine-based or polyhydric alcohol-based suppressing agent. The suppressing agent is modified by reaction with a compound that introduces a branching group into the suppressing agent before they are reacted with an alkylene oxide. The suppressing agent shows extraordinary superfilling properties, particularly when used to fill in features having extremely small aperture sizes and/or high aspect ratios.

First claim

The invention claimed is:

1. An aqueous composition, comprising at least one metal ion and at least one compound of formula I

X 1 is independently a linear or branched C 1 -C 12 alkanediyl, which is substituted or unsubstituted, and optionally interrupted by O, S or NR 40 ;
R 11 is Z, X 5 —Z, or X 4 —N(Z) 2 ;
Z is a branching group of formula III

R 12 is H, R 11 , or R 40 ;
R 13 , R 14 are (a) independently H, R 11 , or R 40 , or (b) R 13 and an adjacent group R 14 together form a bivalent group X 13 , wherein, for (a) or (b), with the provision that n>2, two adjacent groups R 14 optionally together form a bivalent group X 13 ;
R 31 , R 32 are independently a monovalent C 2 to C 6 polyoxyalkylene group, wherein a further branching group is optionally present in R 31 and/or R 32 to form a multiple branching group (Z p ) p (R 31 R 32 ) 2p ;
Z p is

R 40 is (a) a linear or branched C 1 -C 20 alkyl, which optionally is substituted by hydroxyl, alkoxy or alkoxycarbonyl, or (b) a linear or branched C 1 -C 20 alkenyl, which is optionally substituted by hydroxyl, alkoxy or alkoxycarbonyl;
each X 3 is independently a linear or branched C 1 to C 12 alkanediyl, which optionally is interrupted by O and S atoms or substituted by O—R 31 ;
each X 4 is independently a linear or branched C 1 to C 12 alkanediyl;
each X 5 is independently a divalent group of at least one C 2 to C 6 polyoxyalkylene;
X 13 is a linear or branched C 1 -C 12 alkanediyl, which optionally is interrupted by O, S or NR 40 ;
n is an integer of from 0 to 6; and
p is an integer of from 2 to 4;
wherein the aqueous composition is for metal electroplating; and
wherein the at least one metal ion comprises copper ions, cobalt ions, or tin ions.

2. The composition according to claim 1 , wherein X 1 is a C 1 -C 6 alkanediyl.

3. The composition according to claim 1 , wherein
R 31 and R 32 are independently a monovalent C 2 to C 6 polyoxyalkylene group.

4. The composition according to claim 1 , wherein X 3 and X 4 are independently methanediyl, ethanediyl, propanediyl or butanediyl.

5. The composition according to claim 1 , wherein in formula I
n is 0; and
R 11 , R 12 and R 13 are independently X 4 —N(Z) 2 .

6. The composition according to claim 1 , wherein the composition comprises a compound of formula Ia

wherein
s is 0, 1, 2 or 3;
R 11 , R 12 , R 13 and R 14 are Z; and
R 15 is R 11 or R 40 .

7. The composition according to claim 1 , wherein the composition comprises a compound of formula Ia

wherein
s is 0, 1, 2 or 3;
R 11 and R 12 are Z;
R 13 and R 14 are R 40 ; and
R 15 is R 11 or R 40 ;
or
s is 0, 1, 2 or 3;
R 11 and R 13 are Z; and
R 12 , R 14 , and R 15 are R 40 .

8. The composition according to claim 1 , comprising a compound of formula Ib

or a compound of formula Ic

or a compound of formula 1d

wherein
R 11 is Z, and
R 12 , R 13 and R 14 are R 11 or R 40 .

9. The composition according to claim 1 , wherein in formula I
n is 0; and
R 11 , R 12 and R 13 are independently Z.

10. The composition according to claim 1 , wherein in formula I
n is 1, 2, or 3; and
R 11 , R 12 , R 13 , and R 14 are X 5 —Z.

11. The composition according to claim 1 , wherein the at least one metal ion comprises copper ions.

12. The composition according to claim 11 , wherein
R 31 , R 32 and X 5 are each independently a copolymer of ethylene oxide and at least one further C 3 to C 6 alkylene oxide; and
the content of ethylene oxide in R 31 , R 32 and X 5 is from 25 to 70% by weight.

13. The composition according to claim 1 , wherein the at least one metal ion comprises tin ions.

14. The composition according to claim 13 , wherein
R 31 , R 32 and X 5 are each independently a copolymer of ethylene oxide and at least one further C 3 to C 6 alkylene oxide; and
the content of ethylene oxide in R 31 , R 32 and X 5 is from 5 to 30% by weight.

15. A method for depositing copper on a substrate, the method comprising:
applying a metal plating bath comprising the composition according to claim 11 to the substrate, which contains an aperture with a size of 30 nanometers or less.

16. A method for depositing tin or tin alloy on a substrate, the method comprising:
applying a metal plating bath comprising the composition according to claim 13 to the substrate, which contains an aperture with a size of 1 to 200 μm.

17. A process for depositing a metal layer on a substrate, the process comprising
a) contacting the composition according to claim 1 with the substrate, and
b) applying a current to the substrate for a time sufficient to perform a deposition depositing a metal layer onto the substrate,
wherein the substrate comprises micrometer or nanometer sized features and the deposition is performed to fill the micrometer or nanometer sized features.

Assignees

• Basf Se

Inventors

• Kienle Marcel Patrik
• Mayer Dieter
• Arnold Marco
• Haag Alexandra
• Emnet Charlotte
• Fluegel Alexander

Classifications

• H10P14/47

  Electrolytic deposition, i.e. electroplating; Electroless plating · CPC title

• C25D3/32 Primary

  characterised by the organic bath constituents used · CPC title

• C25D3/02 Primary

  from solutions (C25D5/34 - C25D5/46 take precedence) · CPC title

• C25D3/38

  of copper · CPC title

• C25D7/123

  Semiconductors first coated with a seed layer or a conductive layer · CPC title