IP Library Granted Patent US 9,790,600
Granted Patent B2
US 9,790,600 · App. 14/929,803 · Granted Oct 17, 2017

Etching agent for copper or copper alloy

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Quick Facts
Patent No.
US 9,790,600
App. No.
14/929,803
Granted
Oct 17, 2017
Kind
B2
Abstract

Object is to provide an etching solution which generates less foam and can etch copper or copper alloy at high selectivity when used in a step of etching copper or 5 copper alloy in an electronic substrate having both of copper or copper alloy and nickel. The etching solution to be used in a step of selectively etching copper or copper alloy in an electronic substrate having both of copper or copper alloy and nickel has, as essential components thereof, (A) a linear alkanolamine, (B) a chelating agent having an acid group in the molecule thereof, and (C) hydrogen peroxide.

Claims (18)

1. A method of manufacturing an electronic substrate, comprising a step of using an etching solution for copper or copper alloy to selectively etch copper or copper alloy in an electronic substrate having both copper or copper alloy and nickel, wherein said etching solution comprises (A) a linear alkanolamine, (B) a chelating agent having an acid group in the molecule thereof, and (C) hydrogen peroxide, wherein the chelating agent (B) is an (i) organic acid having two or more phosphonic acid groups as the acid group or salts thereof, (ii) organic acid having two or more sulfonic acid groups as the acid group or salts thereof, or (iii) organic acids containing one or more carboxyl groups and one or more phosphonic acid groups as the acid group or salts thereof.

2. The method of claim 1 , wherein the linear alkanolamine (A) is a linear alkanolmonoamine (A1) represented by the following formula (1) or a linear alkanolpolyamine (A2) represented by the following formula (2):

wherein each of R 1 to R 3 is independently a hydrogen atom or an alkyl group which may be partially substituted with a hydroxyl group, with the proviso that at least one of R 1 to R 3 is an alkyl group substituted with a hydroxyl group:

wherein each of R 4 to R 8 is independently a hydrogen atom or an alkyl group which may be partially substituted with a hydroxyl group, with the proviso that at least one of R 4 to R 8 is an alkyl group substituted with a hydroxyl group; each of Y 1 and Y 2 is independently an alkylene group having from 1 to 4 carbon atoms; and n is 0 or an integer from 1 to 4.

3. The method of claim 1 , wherein the linear alkanolamine (A) has an HLB of from 12 to 45.

4. The method of claim 1 , wherein a weight ratio of the chelating agent (B) to the linear alkanolamine (A),((B)/(A)) is from 1 to 100.

5. The method of claim 1 , wherein a weight ratio of the chelating agent (B) to the hydrogen peroxide (C),((B)/(C)) is from 1 to 30.

6. The method of claim 1 , wherein the linear alkanolamine (A) comprises a species selected from the group consisting of monoethanolamine, 2-(methylamino)ethanol, 2-(ethylamino) ethanol, 2-(isopropylamino)ethanol, 2-amino-2-methyl-1-propanol, 2-(dimethylamino)ethanol, 2-(diethylamino)ethanol, diethanolamine, triethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, diisopropanolamine, triisopropanolamine, and 3-(diethylamino)-1-propanol.

7. The method of claim 1 , wherein the linear alkanolpolyamine (B) comprises a species selected from the group consisting of 2-[(2-aminoethyl)amino]ethanol, 2-[methyl[2-(dimethylamino)ethyl]amino]ethanol, 2,2′-(ethylenebisimino)bisethanol, N-(2-hydroxyethyl)-N′-(2-aminoethyl)ethylenediamine, N-(3-hydroxypropyl)ethylenediamine, 2,2′-(2-aminoethylimino)diethanol, N-(2-hydroxyethyl)-N′-(2-aminoethyl)ethylenediamine, 2-[bis(2-aminoethyl)amino]ethanol, 1-[2-[(2-aminoethyl)amino]ethyl]amino-2-propanol, 3,3′,3″,3′″-[3-hydroxypropyliminobis(ethylenenitrilo)]tetrakis(1-propanol), N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine, N,N,N′,N′,N″-pentakis(2-hydroxypropyl)diethylenetriamine, N,N,N′,N′-tetrakis(2-hydroxyethyl)trimethylenediamine, N,N-bis(hydroxyethyl)diethylenetriamine, N1,N4-bis(hydroxyethyl)diethylenetriamine, N,N,N′,N′,N″-pentakis(2-hydroxypropyl)diethylenetriamine, N1-(2-hydroxypropyl)triethylenetetramine, N4-(2-hydroxypropyl)triethylenetetramine, and N-(2-hydroxypropyl)triethylenetetramine.

8. The method of claim 1 , wherein the chelating agent (B) is an organic acid having two or more phosphonic acid groups and is selected from the group consisting of methyldiphosphonic acid (salts), aminotri(methylenephosphonic acid) (salts), 1-hydroxyethylidene-1,1-diphosphonic acid (salts), ethylenediaminetetra(methylenephosphonic acid) (salts), hexamethylenediaminetetra(methylenephosphonic acid) (salts), propylenediaminetetra(methylenephosphonic acid) (salts), diethylenetriaminepenta(methylenephosphonic acid) (salts), triethylenetetraminehexa(methylenephosphonic acid) (salts), triaminotriethylaminehexa(methylenephosphonic acid) (salts), trans-1,2-cyclohexanediaminetetra(methylenephosphonic acid) (salts), glycoletherdiaminetetra(methylenephosphonic acid) (salts), and tetraethylenepentaminehepta(methylenephosphonic acid) (salts).

9. The method of claim 1 , wherein the chelating agent (B) is an organic acid having two or more sulfonic acid groups and is selected from the group consisting of methanedisulfonic acid (salts), ethanedisulfonic acid (salts), phenoldisulfonic acid (salts), naphthalenedisulfonic acid (salts), and piperazine-1,4-bis(2-ethanesulfonic acid) (salts).

10. The method of claim 1 , further comprising an additional species selected from the group consisting of an anticorrosive, an antioxidant, a basic compound for pH control, an acidic compound for pH control, an inorganic acid, and an antifoaming agent.

11. The method of claim 1 , wherein the amount of the linear alkanolamine (A) is 0.1 to 3 wt %, based on the total weight of the etching solution upon use.

12. The method of claim 1 , wherein a weight ratio of the chelating agent (B) to the linear alkanolamine (A),((B)/(A)) is from 2 to 50.

13. The method of claim 1 , wherein the chelating agent (B) is an organic acid having two or more carboxyl groups in the molecule thereof.

14. The method of claim 13 , wherein the chelating agent (B) is an organic acid having two or more carboxyl groups are is selected from the group consisting of ethylenediaminetetraacetic acid (salts), diethylenetriaminepentaacetic acid (salts), triethylenetetraminehexaacetic acid (salts), hydroxyethylethylenediaminetriacetic acid (salts), dihydroxyethylethylenediaminetetraacetic acid (salts), nitriloacetic acid (salts), hydroxyethyliminodiacetic acid (salts), β-alaninediacetic acid (salts), aspartic diacetic acid (salts), methylglycinediacetic acid (salts), iminodisuccinic acid (salts), serinediacetic acid (salts), hydroxyiminodisuccinic acid (salts), tartaric acid (salts), citric acid (salts), pyromellitic acid (salts), benzopolycarboxylic acid (salts), and cyclopentanetetracarboxylic acid (salts).

15. The method of claim 1 , further comprising a solvent.

16. The method of claim 15 , wherein the solvent comprises a species selected from the group consisting of water, alcohols, glycol ethers, ethers, esters, ketones, carbonates, and amides.

Assignments (5)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 28, 2021
From: ENTEGRIS, INC.
To: SAMSUNG ELECTRONICS CO., LTD.
Reel/Frame 056686/0538 →
RELEASE OF SECURITY INTEREST Recorded Jun 15, 2021
From: MORGAN STANLEY SENIOR FUNDING, INC.
To: ENTEGRIS, INC.
Reel/Frame 056550/0726 →
ASSIGNMENT OF PATENT SECURITY INTEREST RECORDED AT REEL/FRAME 048811/0679 Recorded Nov 5, 2019
From: GOLDMAN SACHS BANK USA
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 050965/0035 →
SECURITY INTEREST Recorded Nov 13, 2018
From: ENTEGRIS, INC.; SAES PURE GAS, INC.
To: GOLDMAN SACHS BANK USA
Reel/Frame 048811/0679 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 19, 2016
From: ADVANCED TECHNOLOGY MATERIALS, INC.
To: ENTEGRIS, INC.
Reel/Frame 041029/0903 →