Imidazoyl urea polymers and their use in metal or metal alloy plating bath compositions

Patent metadata

Field	Value
Publication number	US-11066553-B2
Application number	US-201615748203-A
Country	US
Kind code	B2
Filing date	Aug 19, 2016
Priority date	Aug 31, 2015
Publication date	Jul 20, 2021
Grant date	Jul 20, 2021

Abstract

The present invention relates to imidazoyl urea polymers and their use in aqueous acidic plating baths for metal or metal alloy deposition such as electrolytic deposition of copper or alloys thereof in the manufacture of printed circuit boards, IC substrates, semiconducting and glass devices for electronic applications. The plating bath according to the present invention comprises at least one source of metal ions and an imidazoyl urea polymer. The plating bath is particularly useful for filling recessed structures and build-up of pillar bump structures.

First claim

The invention claimed is:

1. An imidazoyl urea polymer comprising a polymeric building block according to formula (I)

wherein A represents a unit of one or both of the following formulae (A1) and (A2)

wherein
X is a divalent residue selected from the group consisting of

wherein Z is selected from —CH 2 —, O, S; z and z′ are integers independently ranging from 1 to 6, R and R′ are monovalent residues each selected independently from the group consisting of hydrogen, alkyl, aryl, aralkyl and —CH 2 —CH 2 —(OCH 2 CH 2 ) y —OH wherein y is an integer from 1 to 4;
R 1 and R 2 are divalent residues each selected independently from the group consisting of —(CH 2 ) b — and —(CH 2 ) b —[CH(R 4 )—CH 2 O] d —(CH 2 ) e — wherein b is an integer ranging from 2 to 12; wherein c is an integer ranging from 0 to 3; d is an integer ranging from 1 to 100; e is an integer ranging from 1 to 3; each R 4 is independently from each other selected from the group consisting of alkyl, aryl and hydrogen;
R 3 is a divalent residue which is selected from the group consisting of alkylene, arylene and —(CH 2 ) f [CH(R 5 )—CH 2 —O] g —(CH 2 ) h —, wherein f is an integer ranging from 0 to 3; g is an integer ranging from 1 to 100; h is an integer ranging from 1 to 3; each R 5 is independently from each other selected from the group consisting of alkyl, aryl and hydrogen;
a is an integer and ranges from 1 to 40; and
D is a divalent residue and is selected from the group consisting of —CH 2 —CH(OH)—CH 2 —, —CH 2 —CH(SH)—CH 2 —, —(CH 2 ) i —[CH(R 6 )—CH 2 —O] j —(CH 2 ) k — and —CH 2 —CH(OH)—(CH 2 ) l —[CH(R 7 )—CH 2 —O] m —(CH 2 ) n —CH(OH)—CH 2 —
wherein i is an integer ranging from 0 to 3; j is an integer ranging from 1 to 100; k is an integer ranging from 1 to 3; each R 6 is independently from each other selected from the group consisting of alkyl, aryl and hydrogen; l is an integer ranging from 1 to 3; m is an integer ranging from 1 to 100; n is an integer ranging from 1 to 3; each R 7 is independently from each other selected from the group consisting of alkyl, aryl and hydrogen;
wherein the individual units A may be the same or different, and
wherein the individual units D may be the same or different.

2. The imidazoyl urea polymer according to claim 1 wherein R 1 and R 2 are selected from 1,2-ethylene (—CH 2 —CH 2 —), 1,3-propylene (—CH 2 —CH 2 —CH 2 —), —(CH 2 ) 2 —O—(CH 2 ) 2 — and —(CH 2 ) 2 —O—(CH 2 ) 2 —O—(CH 2 ) 2 — group and R 3 is selected from 1,2-ethylene —CH 2 —CH 2 —), 1,3-propylene (—CH 2 —CH 2 —CH 2 —), —(CH 2 ) 2 —O—(CH 2 ) 2 —, —(CH 2 ) 2 —O—(CH 2 ) 2 —O—(CH 2 ) 2 — and —(CH 2 ) 2 —O—(CH 2 ) 2 —O—(CH 2 ) 2 —O—(CH 2 ) 2 — group.

3. The imidazoyl urea polymer according to claim 2
wherein X is

and D is selected from —CH 2 —CH(OH)—CH 2 —, —(CH 2 ) i —[CH(R 6 )—CH 2 —O] j —(CH 2 ) k —, and —CH 2 —CH(OH)—(CH 2 ) l —[CH(R 7 )—CH 2 —O] m —(CH 2 ) n —CH(OH)—CH 2 —.

4. The imidazoyl urea polymer according to claim 3 wherein R 1 , R 2 and R 3 are free of nitrogen atoms.

5. The imidazoyl urea polymer according to claim 4 wherein A is selected to be one or more units derived from formula (A1).

6. The imidazoyl urea polymer according to claim 1 wherein X is

and D is selected from —CH 2 —CH(OH)—CH 2 —, —(CH 2 ) i —[CH(R 6 )—CH 2 —O] j —(CH 2 ) k — and —CH 2 —CH(OH)—(CH 2 ) l —[CH(R 7 )—CH 2 —O] m —(CH 2 ) n —CH(OH)—CH 2 —.

7. The imidazoyl urea polymer according to claim 6 wherein D is —(CH 2 ) o —[CH(R 8 )—CH 2 —O] p —(CH 2 ) q —, o is 0 and p is an integer ranging from 1 to 100 and q is an integer ranging from 1 to 3.

8. The imidazoyl urea polymer according to claim 1 wherein R 1 , R 2 and R 3 are free of nitrogen atoms.

9. The imidazoyl urea polymer according to claim 1 wherein A is selected to be one or more units derived from formula (A1).

10. The imidazoyl urea polymer comprising a polymeric building block according to claim 1 wherein the imidazoyl urea polymers are represented by one of the following formulae (IIa) to (IIc)

wherein the imidazoyl urea polymer contains one or two polymer terminating groups (PTG1) and/or (PTG2) that are bound to the unit A represented by formula (A1) and/or (A2) and/or to the divalent residue D in the polymeric building block according to formula (I) and wherein the first polymer terminating group (PTG1) bound to the unit A in the polymeric building block according to formula (I) is selected from the group consisting of
E-G 1 -, R 9 -G 2 -,

and
the second polymer terminating group (PTG2) bound to the divalent residue D in the polymeric building block according to formula (I) is selected from the group consisting of hydroxyl group (—OH), urea compound A according to formula (A1) or (A2),

monovalent residue E, C 1 - to Ca-alkyl, aralkyl, aryl,

wherein G 1 and G 2 are divalent residues represented by the following formula —(CH 2 ) r —[CH(R 10 )—CH 2 —O] s —(CH 2 ) t — wherein r is an integer ranging from 0 to 3; s is an integer ranging from 1 to 100; t is an integer ranging from 1 to 3; each R 10 is independently from each other selected from the group consisting of alkyl, aryl and hydrogen; E is selected from triflate, nonaflate, alkylsulphonates, arylsulphonates and halogenides; and R 9 is a monovalent residue selected from the group consisting of C 1 - to C 8 -alkyl, C 1 - to C 8 -alkenyl, aralkyl and aryl.

11. The imidazoyl urea polymer according to claim 1 wherein the imidazoyl urea polymers have a weight average molecular mass M w of 1000 to 50000 Da.

12. A process for forming an imidazoyl urea polymer, comprising reacting a monomer urea compound of the following formulae (A1′) and (A2′)

wherein
X′ is a monovalent residue selected from the group consisting of

wherein Z′ is selected from —CH 2 —, O, S;
z″ and z′″ are integers independently ranging from 1 to 6;
R″ and R′″ are monovalent residues each selected independently from the group consisting of hydrogen, alkyl, aryl, aralkyl and —CH 2 —CH 2 —(OCH 2 CH 2 ) y —OH, wherein y′ is an integer from 1 to 4;
R 1′ and R 2′ are divalent residues each selected independently from the group consisting of
—CH 2 ) b′ —, wherein b′ is an integer from 2 to 12, and
—CH 2 ) c′ —[CH(R 4 )—CH 2 —O] d′ —(CH 2 ) e′ —, wherein c′ is an integer ranging from 0 to 3; d′ is an integer ranging from 1 to 100; e′ is an integer ranging from 1 to 3; each R 4′ is independently from each other selected from the group consisting of alkyl, aryl and hydrogen;
R 3′ is a divalent residue which is selected from the group consisting of alkylene, arylene and —(CH 2 ) f′ —[CH(R 9 )—CH 2 —O] g′ , —(CH 2

Assignees

• Atotech Deutschland Gmbh

Inventors

• Brunner Heiko
• Kohlmann Lars
• Witczak Agnieszka
• Mann Olivier

Classifications

• C08G71/02 Primary

  Polyureas · CPC title

• C08L75/02 Primary

  Polyureas · CPC title

• C25D3/38

  of copper · CPC title

• C07D233/61

  with hydrocarbon radicals, substituted by nitrogen atoms not forming part of a nitro radical, attached to ring nitrogen atoms · CPC title

• C07C275/22

  containing rings other than six-membered aromatic rings · CPC title