Use of a composition comprising a polyaminoamide type compound for copper nanotwin electrodeposition

Patent metadata

Field	Value
Publication number	US-2025388725-A1
Application number	US-202318880588-A
Country	US
Kind code	A1
Filing date	Jun 29, 2023
Priority date	Jul 7, 2022
Publication date	Dec 25, 2025
Grant date	—

Abstract

Described herein is a method of using a polyaminoamide including a group of formula N1in a composition for electrodepositing nanotwinned copper, that is obtained by reacting a diamine compound including two primary or secondary amino groups with an aminoacid in a molar ratio of approx. 1:2 to form an aminoamide compound that is afterwards reacted with a coupling agent and optionally with a diamine or other co-monomers.

First claim

1 . A method of using a polyaminoamide comprising a group of formula N1

the method comprising using the polyaminoamide in a composition for electrodepositing nanotwinned copper,
wherein
B, B′ are the same or different, and are aminoacid fragments of formula N2a

or of Formula N2b

or of Formula N2c

A is a diamine fragment independently selected from the group consisting of formula N3a

and of Formula N3b

D N1 is a divalent group selected from the group consisting of
(a) a C 1 -C 20 -alkanediyl which may optionally be substituted by an amino group or interrupted by a double bond or an imino group, and
(b) an ether or polyether group of formula N2c

D N2 is a divalent group selected from the group consisting of
(a) a linear, branched or cyclic C 1 to C 20 alkanediyl, which may optionally be interrupted by one or more NR N10 , or substituted by one or more groups NR N10 R N11 or OR N10 , or
(b) -D N13 -Ar N13 -D N13 -; and
(c) an ether or polyether group of formula N2c;

D N10 is selected from the group consisting of a linear or branched C 1 -C 6 -alkanediyl;
D N13 is selected from the group consisting of a C 1 -C 6 -alkanediyl;
Ar N13 is a C 6 to C 10 aromatic moiety;
D N11 ,D N12 are
(a) independently selected from the group consisting of a linear or branched C 1 to C 6 alkanediyl, or
(b) both, together with the adjacent two N atoms, part of a 5 or 6-membered aromatic heterocyclic ring system;

D N21 ,D N22 are
(a) independently selected from the group consisting of a linear or branched C 1 to C 6 alkanediyl, or
(b) both, together with the adjacent two N atoms, part of a 5 or 6-membered aromatic heterocyclic ring system;

D N23 is a C 1 to C 6 alkanediyl;
R N1 , R N2 are independently selected from the group consisting of a C 1 to C 6 alkyl;
R N3 is selected from the group consisting of H and a C 1 to C 6 alkyl;
R N10 , R N11 are independently selected from the group consisting of H and a linear or branched C 1 to C 6 alkanediyl;
X N2 is N or CR N3 .
Y is a diamine comonomer fragment;
Z is a divalent coupling fragment of formula N4

Z N1 is selected from the group consisting of
(a) a linear or branched C 1 to C 12 alkanediyl, which may be interrupted by one or more O atoms, and
(b) a divalent group -D N11 -Ar N11 -D N11 -;

Z N2 , Z N3 are independently selected from the group consisting of a chemical bond and hydroxyethanediyl;
n is an integer of from 1 to 400;
m is 0 or an integer of from 1 to 400;
o is an integer of from 1 to 6; and
p, r are independently 0 or 1;
wherein the ratio of nim is at least 25:75.

2 . The method according to claim 1 , wherein B and B′ are the same or different, and are aminoacid fragments of formula N2a, wherein D N1 is selected from the group consisting of (i) a linear C 2 to C 10 alkanediyl group, (ii) a C 2 to C 3 oxyalkylene group, (iii) a cyclic C 6 to C 12 alkanediyl group, and (iv) a divalent phenyl or pyridyl group.

3 . The method according to claim 1 , wherein B and B′ are the same or different, and are a fragment of formula N2b, wherein (a) D N11 and D N12 are independently selected from the group consisting of a linear or branched C 1 to C 4 alkanediyl, or (b) D N11 and D N12 , together with the two adjacent N atoms, form an imidazole ring.

4 . The method according to claim 1 , wherein A is a fragment of formula N3a, wherein D N2 is selected from the group consisting of methanediyl, ethanediyl, and 1,3-propanediyl.

5 . The method according to claim 1 , wherein A is a fragment of formula N3a, wherein D N2 is selected from the group consisting of an ether or polyether group of formula N2a

wherein D N10 is selected from the group consisting of a C 1 -C 4 -alkanediyl and o is an integer from 1 to 5.

6 . The method according to claim 1 , wherein the polyaminoamide is

wherein
D N1 is selected from the group consisting of methanediyl, ethanediyl, propanediyl and butanediyl;
R N3 is selected from the group consisting of H, methyl and ethyl;
R N32 is selected from the group consisting of H, methyl and ethyl; and
Z is —CH 2 —CH(OH)—CH 2 —.

7 . The method according to claim 1 , wherein A is a fragment of formula N3b, wherein D N21 , D N22 , and D N23 are independently selected from the group consisting of methanediyl, ethanediyl, and propanediyl.

8 . The method according to claim 1 , wherein A is a fragment of formula N3b, wherein D N21 and D N22 , together with the two adjacent N atoms, form an imidazole ring and D N23 is selected from the group consisting of methanediyl, ethanediyl, propanediyl and butanediyl.

9 . The method according to claim 1 , wherein Z is selected from the group consisting of C 1 to C 12 alkanediyl, a bis(2-ethanediyl)ether group, 2-hydroxypropane-1,3-diyl, and 4,4′-bis(methyl)biphenyl.

10 . The method according to claim 1 , wherein n is an integer from 2 to 200.

11 . The method according to claim 1 , wherein m is 0 or an integer from 1 to 200.

12 . The method according to claim 1 , wherein the ratio of n:m is at least 50:50.

13 . The method according to claim 1 , wherein the mass average molecular weight M w of the polyaminoamide is of from 450 g/mol to 150 000 g/mol.

14 . A composition comprising copper ions, an acid, and the at least one polyaminoamide comprising a group of formula NI as defined in claim 1 , the composition being devoid of any sulfur-containing compounds and any polyalkylene oxide compounds.

15 . The composition according to claim 14 , essentially consisting of copper ions, an acid, halide ions, and the at least one polyaminoamide comprising a group of formula N1.

16 . A process for electrodepositing copper on a substrate comprising a recessed feature comprising a conductive feature bottom and a dielectric feature side wall, the process comprising:

a) contacting a composition comprising a polyaminoamide comprising a group of formula or a composition according to claim 14 with the substrate, and
b) applying a current to the substrate for a time sufficient to deposit nanotwinned copper on the substrate,

wherein
B, B′ are the same or different, and are aminoacid fragments of formula N2a

Assignees

• Basf Se

Inventors

• Arnold Marco
• Fluegel Alexander
• Engelhardt Nadine

Classifications

• C25D3/38 Primary

  of copper · CPC title

• C25D5/617

  Crystalline layers · CPC title

• C08G73/028 Primary

  Polyamidoamines · CPC title

• C25D5/02

  Electroplating of selected surface areas · CPC title