Reaction products of amino acids and epoxies

Patent metadata

Field	Value
Publication number	US-10041182-B2
Application number	US-201715485454-A
Country	US
Kind code	B2
Filing date	Apr 12, 2017
Priority date	Dec 30, 2014
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

Reaction products of one or more amino acids and one or more epoxies are included in copper and copper alloy electroplating baths to provide good throwing power. Such reaction products may plate copper and copper alloys with good surface properties and good physical reliability.

First claim

What is claimed is:

1. A method comprising:
a) providing a substrate;
b) providing a composition comprising one or more sources of copper ions, an electrolyte, and one or more compounds consisting of a reaction product of one or more amino acid monomers and one or more polyepoxide monomers and optionally one or more heterocyclic nitrogen compound monomers;
c) contacting the substrate with the composition;
d) applying a current to the substrate and the composition; and
e) depositing copper or copper alloy on the substrate.

2. The method of claim 1 , wherein the one or more amino acids are chosen from α-amino acids, β-amino acids and γ-amino acids.

3. The method of claim 2 , wherein the one or more α-amino acids are chosen from arginine, alanine, glycine, tryptophan, asparagine, lysine, histidine, tyrosine, glutamine, proline and salts thereof.

4. The method of claim 1 , wherein a molar ratio of a moiety from the amino acid monomer to a moiety from the polyepoxide monomer ranges from 0.5:2-2:0.5.

5. The method of claim 1 , wherein the one or more polyepoxide monomers have a formula:

wherein R 2 and R 3 may be the same or different and are chosen from hydrogen and (C 1 -C 4 )alkyl, A =OR 4 or R 5 ; R 4 =((CR 6 R 7 ) m O), (aryl-O) p , CR 6 R 7 —Z —CR 6 CR 7 , or OZ′ t O, R 5 =(CH 2 ) y , B is (C 5 -C 12 )cycloalkyl, Z=a 5- or 6-membered ring, Z′ is R 8 OArOR 8 , (R 9 O) b Ar(OR 9 ), or (R 9 O) b , Cy(OR 9 ), Cy =(C 5 -C 12 )cycloalkyl, R 6 and R 7 are independently chosen from hydrogen, methyl, or hydroxyl, R 8 represents (C 1 -C 8 )alkyl, R 9 represents a (C 2 -C 6 )alkyleneoxy, R 10 is a hydrogen atom, a formyl group, or one or two glycidyl ether groups each optionally containing a carbonyl group constituted by C 4 -C 8 and C 2 -C 4 , R 11 is a hydrogen atom, a methyl group or an ethyl group, and R 12 is a hydrogen atom, a formyl group, or one or two glycidyl ether groups each optionally containing a carbonyl group constituted by C 4 -C 8 and C 2 -C 4, b=1-10, m=1-6, n=1-4, p=1-6, t=1-4 and y=0-6.

6. The method of claim 1 wherein the substrate comprises a plurality of one or more of through-holes, trenches and vias.

7. The method of claim 1 , wherein the one or more polyepoxide monomers 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 method of claim 1 , wherein the one or more polyepoxide monomers are chosen from dicyclopentadiene dioxide and 1,2,5,6-diepoxycyclooctane.

9. The method of claim 1 , wherein the one or more polyepoxide monomers 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.

10. The method of claim 1 , wherein the one or more amino acid monomers are chosen from aromatic compounds having a general formula:
X′—COOH  (I)

wherein X′ is a substituted six membered aromatic ring or a substituted six membered heterocyclic ring wherein the hetero-atom is nitrogen, and substituent groups are —NH 2 and optionally —OH.

11. The method of claim 10 , wherein the one or more amino acid monomers is chosen from 4-aminobenzoic acid, 3-aminobenzoic acid, 2-aminobenzoic acid, 3,5-diaminobenzoic acid, 4-aminosalicylic acid and 5-aminosalicylic acid.

12. The method of claim 10 , wherein the one or more amino acid monomers are chosen from 3-aminoisonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 2-aminonicotinic acid, 6-aminonicotinic acid, 2-aminoisonicotinic acid and 6-aminopicolinic acid.

13. The method of claim 1 , wherein the one or more heterocyclic nitrogen compound monomers are chosen from imidazoles, triazoles, tetrazoles, pyrazines, benzimidazoles, benzotriazoles, purines, piperazines, pyridazines, pyrazoles, triazines, tetrazines and pyrimidines.

14. The method of claim 1 , wherein the composition further comprises one or more sources of tin ions.

15. The method of claim 1 , wherein the electrolyte is acidic.

16. The method of claim 15 , wherein a pH of the electrolyte is <2.

Assignees

• Rohm & Haas Elect Mat

Inventors

• Niazimbetova Zuhra I
• Rzeznik Maria Anna

Classifications

• C25D3/32

  characterised by the organic bath constituents used · CPC title

• C25D3/58

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

• C25D7/123

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

• C25D3/38 Primary

  of copper · CPC title

• C07D303/04

  containing only hydrogen and carbon atoms in addition to the ring oxygen atoms · CPC title