Amino sulfonic acid based polymers for copper electroplating

Patent metadata

Field	Value
Publication number	US-9725816-B2
Application number	US-201414585229-A
Country	US
Kind code	B2
Filing date	Dec 30, 2014
Priority date	Dec 30, 2014
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

Amino sulfonic acid based polymers are reaction products of amino sulfonic acids, an amine, polyepoxide compounds and epihalohydrin. The polymers may be used as levelers in copper electroplating baths, to provide good throwing power. Such reaction products may plate copper or copper alloys with good surface properties and good physical reliability.

First claim

What is claimed is:

1. A composition comprising one or more sources of copper ions, an electrolyte and a reaction product comprising one or more amino sulfonic acids or salts thereof, one or more amines, one or more polyepoxides and one or more epihalohydrins, wherein the one or more amino sulfonic acids or salts thereof has a formula:

wherein X comprises hydrogen or an alkali metal ion; R′ comprises hydrogen, hydroxyl, linear or branched (C 1 -C 5 )alkyl, hydroxy(C 1 -C 5 )alkyl, substituted or unsubstituted aryl; R comprises linear, branched, substituted or unsubstituted (C 1 -C 20 )alkylene moiety; substituted or unsubstituted (C 5 -C 10 )alicyclic, or substituted or unsubstituted aromatic moiety of 6 to 18 carbons.

2. The composition of claim 1 , wherein R has a formula:

wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be the same or different and comprise —NHR′, —SO 3 X, hydrogen, hydroxyl, hydroxy(C 1 -C 10 )alkyl, linear or branched, substituted or unsubstituted (C 1 -C 10 )alkyl, (C 1 -C 5 )alkoxy, alkoxy(C 1 -C 5 )alkyl, substituted or unsubstituted phenyl, linear or branched, substituted or unsubstituted phenyl(C 1 -C 5 )alkyl with the proviso that at least one of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is —NHR′ and at least one is —SO 3 X.

3. The composition of claim 1 , wherein R has a formula:

wherein R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 and R 10 may be the same or different and comprise —NHR′, —SO 3 X, hydrogen, hydroxyl, hydroxy(C 1 -C 10 )alkyl, linear or branched, substituted or unsubstituted (C 1 -C 10 )alkyl, (C 1 -C 5 )alkoxy, alkoxy(C 1 -C 5 )alkyl, substituted or unsubstituted phenyl, linear or branched, substituted or unsubstituted phenyl(C 1 -C 5 )alkyl with the proviso that at least one of R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 and R 10 is —NHR′ and one is —SO 3 X.

4. The composition of claim 1 , wherein the one or more amines are chosen from primary amines, secondary amines and heterocyclic amines.

5. The composition of claim 4 , wherein the heterocyclic amines are chosen from imidazoles, triazoles, tetrazoles, pyrazines, benzimidazoles, benzotriazoles, purines, piperazines, pyridazines, pyrazoles, triazines, tetrazines, pyrimidines, benzoxazoles, oxazoles, pyridines, morpholines, pyrrolidines, pyrroles, quinolines, isoquinolines and benzothiazoles.

6. The composition of claim 1 , wherein the one or more polyepoxides are chosen from

wherein R 16 and R 17 may be the same or different and are chosen from hydrogen and (C 1 -C 4 )alkyl, A=OR 21 or A=R 22 ; R 21 =((CR 23 R 24 ) m O), (aryl-O) p , CR 23 R 24 —Z—CR 23 CR 24 , or OZ′ t O; R 22 =(CH 2 ) y ; B is (C 5 -C 12 )cycloalkyl; Z=a 5- or 6-membered ring; Z′=R 25 OArOR 25 , Z′=(R 26 O) b Ar(OR 26 ), Z′=(R 26 O) b , or Z′=Cy(OR 26 ), wherein Cy=(C 5 -C 12 )cycloalkyl; R 23 and R 24 are independently chosen from hydrogen, methyl, or hydroxyl, R 25 represents (C 1 -C 5 )alkyl, R 26 represents a (C 2 -C 6 )alkyleneoxy; R 18 is a hydrogen atom, a formyl group, or one or two glycidyl ether groups optionally containing a carbonyl group comprising C 4 -C 8 and C 2 -C 4 , R 19 is a hydrogen atom, a methyl group or an ethyl group, and R 20 is a hydrogen atom, a formyl group, or one or two glycidyl ether groups optionally containing a carbonyl group comprising C 4 -C 8 and C 2 -C 4 , and b=1-10, m=1-6, n=1-4, p=1-6, t=1-4 and y=0-6.

7. The composition of claim 1 , wherein the one or more polyepoxides are chosen from 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, poly(ethyleneglycol) diglycidyl ether and poly(propyleneglycol) diglycidyl ether.

8. The composition of claim 1 , wherein the one or more polyepoxides are chosen from glycerin triglycidyl ether, trimethylolpropanetriglycidyl ether, diglycerol tetraglycidyl ether, erythritol tetraglycidyl ether, arabinose tetraglycidyl ether, triglycerol pentaglycidyl ether, fructose pentaglycidyl ether, xylitol pentaglycidyl ether, tetraglycerol hexaglycidyl ether, and sorbitol hexaglycidyl ether.

9. The composition of claim 1 , wherein the one or more polyepoxides are chosen from dicyclopentadiene dioxide and 1,2,5,6-diepoxycyclooctane.

10. The composition of claim 1 , wherein the one or more epihalohydrin compounds are chosen from epichlorohydrin and epibromohydrin.

Assignees

• Rohm & Haas Elect Mat

Inventors

• Lu Weijing
• Niazimbetova Zuhra I
• Rzeznik Maria Anna

Classifications

• C25D3/58

  containing more than 50% by weight of copper · CPC title

• C25D3/38 Primary

  of copper · CPC title

• C08G65/333

  containing nitrogen · CPC title

• H05K3/241

  characterised by the electroplating method; means therefor, e.g. baths or apparatus · CPC title

• H05K3/188

  by direct electroplating · CPC title