Composition for cobalt plating comprising additive for void-free submicron feature filling

Patent metadata

Field	Value
Publication number	US-2022018035-A1
Application number	US-201917312737-A
Country	US
Kind code	A1
Filing date	Dec 10, 2019
Priority date	Dec 21, 2018
Publication date	Jan 20, 2022
Grant date	—

Abstract

Described herein is a composition including metal ions consisting essentially of cobalt ions, and a specific monomeric and polymeric suppressing agent including a carboxylic, sulfonic, sulfinic, phosphonic, or phosphinic acid functional groups which show a suppressing effect that is required for void-free bottom-up filling of nanometer-sized recessed features.

First claim

1 . A composition for cobalt electroplating comprising
(a) metal ions consisting essentially of cobalt ions, and (b) a suppressing agent comprising the structure of formula S1
[B] n [A] p   (S1)

or having the structure of formula S2

or comprising the structure of formula S3a or S3b

or having the structure of formula S4
Ø-R 1   (S4)

and their salts,

wherein
R 1 is selected from the group consisting of X 1 —CO—O—R 11 , X 1 —SO 2 —O—R 11 , X 1 —PR 11 O(OR 11 ), X 1 —P(OR 1 ) 2 , X 1 —PO(OR 1 ) 2 , and X 1 —SO—O—R 11 ;
R 2 , R 3 , R 4 are independently selected from the group consisting of R 1 and (i) H, (ii) aryl, (iii) C 1 to C 10 alkyl (iv) arylalkyl, (v) alkylaryl, and (vi) —(O—C 2 H 3 R 12 ) m —OH, with the proviso that if one of R 2 , R 3 or R 4 are selected from the group consisting of R 1 , the other groups R 2 , R 3 or R 4 are different from R 1 ,
Ø is a C 6 to C 14 carbocyclic or a C 3 to C 10 nitrogen or oxygen containing heterocyclic aryl group, which may be unsubstituted or substituted by up to three C 1 to C 12 alkyl groups or up to two OH, NH 2 or NO 2 groups,
R 31 is selected from the group consisting of R 1 , H, OR 32 and R 32 ,
R 32 is selected from the group consisting of (i) H and (ii) C 1 to C 6 alkyl,
X 1 is a divalent group selected from the group consisting of (i) a chemical bond (ii) aryl, (iii) C 1 to C 12 alkanediyl, which may be interrupted by one or more O atoms, (iv) an arylalkyl group —X 12 —X 11 —, (v) an alkylaryl group —X 11 —X 12 —, and (vi) —(O—C 2 H 3 R 12 ) m —,
X 2 is (i) a chemical bond or (ii) methanediyl,
R 11 is selected from the group consisting of H and C 1 to C 4 alkyl,
R 12 is selected from the group consisting of H and C 1 to C 4 alkyl,
X 12 is a divalent aryl group,
X 11 is a divalent C 1 to C 15 alkanediyl group,
A is a co-monomer selected from the group consisting of vinyl alcohol, which may optionally be (poly)ethyoxylated, acrylonitrile, styrene and acrylamide,
B is selected from the group consisting of formula S1a

n is an integer from 2 to 10 000,
m is an integer from 2 to 50,
o is an integer from 2 to 1 000, and
p is 0 or an integer from 1 to 10 000,
wherein the composition is essentially free of any dispersed particles, and
wherein the composition is essentially free of any further suppressing agent.

2 . The composition according to claim 1 , wherein R 2 , R 3 and R 4 are selected from the group consisting of H, methyl, ethyl, and propyl.

3 . The composition according to claim 1 , wherein R 2 and either R 3 or R 4 are selected from the group consisting of H, methyl, ethyl, and propyl, and the other group R 3 or R 4 is selected from the group consisting of R 1 .

4 . The composition according to claim 1 , wherein R 3 and R 4 are selected from the group consisting of H, methyl, ethyl, and propyl, and R 2 is selected from the group consisting of R 1 .

5 . The composition according to claim 1 , wherein the suppressing agent is a compound of formula S4a

wherein R 5 , R 6 , R 7 , R 8 , and R 9 are independently selected from the group consisting of (i) H and (ii) C 1 to C 6 alkyl.

6 . The composition according to claim 1 , wherein R 11 is H.

7 . The composition according to claim 1 , wherein n+p is an integer from 10 to 5000 and m is an integer from 2 to 30.

8 . The composition according claim 1 , wherein the suppressing agent is selected from the group consisting of polyacrylic acid, polyitaconic acid, a maleic acid acrylic acid copolymer, a methacrylic acid acrylic acid copolymer, an itaconic acid acrylic acid copolymer, polyvinylphosphonic acid, and polyvinylsulfonic acid.

9 . The composition according to claim 1 , wherein the suppressing agent is selected from the group consisting of acrylic acid, itaconic acid, vinylphosphonic acid, phenylphosphinic acid, and vinylsulfonic acid.

10 . The composition according to claim 1 , wherein R 1 is a sulfonate group and R 31 is OH.

11 . The composition according to claim 1 , wherein the suppressing agent is selected from the group consisting of p-toluol sulfinate and p-toluol sulfonate.

12 . The composition according to claim 1 , wherein the suppressing agent is present in an amount of from 20 to 1000 ppm.

13 . The composition according to claim 1 , consisting essentially of:
(a) metal ions consisting essentially of cobalt ions, (b) a suppressing agent of formula S1, S2, S3, or S4, (c) boric acid or an ammonium compound, (d) an inorganic or organic acid, (e) optionally a wetting agent, (f) optionally a leveling agent different from the suppressing agent, and (g) water.

14 . A method of using a compound comprising the structural element of formula S1, S2, S3a, S3b or S4
[B] n [A] p   (S1)
or having the structure of formula S2

or comprising the structure of formula S3a or S3b

or having the structure of formula S4
Ø-R 1   (S4)

and their salts,
the method comprising using the compound as a suppressing agent for void-free deposition of a metal comprising cobalt on a semiconductor substrate comprising recessed features having an aperture size below 100 nm,
wherein
R 1 is selected from the group consisting of X 1 —CO—O—R 11 , X 1 —SO 2 —O—R 11 , X 1 —PR 11 O(OR 11 ), X 1 —P(OR 1 ) 2 , X 1 —PO(OR 1 ) 2 , X 1 —SO—O—R 11 ;
R 2 , R 3 , R 4 are independently selected from the group consisting of R 1 and (i) H, (ii) aryl, (iii) C 1 to C 10 alkyl (iv) arylalkyl, (v) alkylaryl, and (vi) —(O—C 2 H 3 R 12 ) m —OH, with the proviso that if one of R 2 , R 3 or R 4 are selected from the group consisting of R 1 , the other groups R 2 , R 3 or R 4 are different from R 1
Ø is a C 6 to C 14 carbocyclic or a C 3 to C 10 nitrogen or oxygen containing heterocyclic aryl group, which may be unsubstituted or substituted by up to three C 1 to C 12 alkyl groups or up to two OH, NH 2 or NO 2 groups,
R 31 is selected from the group consisting of R 1 , H, OR 32 and R 32 ,
R 32 is selected from the group consisting of (i) H and (ii) C 1 to C 6 alkyl,
X 1 is a divalent group selected from the group consisting of (i) a chemical bond (ii) aryl, (iii) C 1 to C 12 alkanediyl, which may be interrupted by O atoms, (iv) arylalkyl group —X 11 —X 12 —, (v) alkylaryl group —X 12 —X 11 —, and (vi) —(O—C 2 H 3 R 12 ) m O—,
X 2 is (i) a chemical bond or (ii) methanediyl,
R 11 is selected from the group consisting of H and C 1 to C 4 alkyl,
R 12 is selected from the group consisting of H and C 1 to C 4 alkyl,
X 12 is a divalent aryl group,
X 11 is a divalent C 1 to C 15 alkanediyl group,
A is a co-monomer selected from the group co

Assignees

• Basf Se

Inventors

• Katayaporn Sathana
• Emnet Charlotte
• Mayer Dieter
• Engelhardt Nadine
• Arnold Marco
• Henderson Lucas Benjamin
• Fluegel Alexander

Classifications

• C25D7/123

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

• C25D5/18

  Electroplating using modulated, pulsed or reversing current · CPC title

• C25D3/12 Primary

  of nickel or cobalt · CPC title

• C25D3/18 Primary

  Heterocyclic compounds · CPC title

• C25D3/16

  Acetylenic compounds · CPC title