Title of Invention

A COMPOSITION FOR CLEANING MICROELECTRONIC SUBSTRATES

Abstract Alkaline-containing cleaning compositions and method of using the cleaning compositions for cleaning microelectronic substrates, particularly FPD microelectronic substrates, which compositions are able to essentially completely clean such substrates and produce essentially no metal corrosion of the metal elements of such substrates. The alkaline-containing cleaning compositions of this invention have (a) a nucleophilic amine, (b) a moderate to weak acid having a strength expressed as a "pKa" for the dissociation constant in aqueous solution of from about 1.2 to about 8. (c) a compound selected from an aliphatic alcohol, diol, polyol or aliphatic glycol ether, and (d) an organic co-solvent preferably having a solubility parameter of from about 8 to about 15. The cleaning compositions of this invention will have an amount of weak acid such that the equivalent mole ratio of acid groups to amine groups is greater than .75 and may range up to and beyond a ratio of 1, such as for example a ratio of 1.02 or more. The pH of the alkaline-containing cleaning compositions of this invention will be from about pH 4.5 to 9.5.
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STRIPPING AND CLEANING COMPOSITIONS FOR MICROELECTRONICS
FIELD OF THE INVENTION
[0001] This invention relates to methods and alkaline-containing photresst
stripping and cleaning compositions for cleaning microelectronics substrate and particularly such compositiors useful with and compatible with metal electronics stacks used in the flat panel display (FPD) markets. The compositions of this invention provide enhanced protection of metal, i.e.. inhibition of corrosion, when such microelectronic substrates are subjected to an aqueous rinse.
BACKGROUD TO THE INVENTION
[0002] Many photoresist strippers and residue removers have been proposed
for use in the microelectronics field as downstream or back end of tne manufacturing line cleaners. In the manufacturing process a thin film of photoresist is deposited on a
substrate material, and then circuit design is imaged on the thin film. Following baking, the exposed resist is removed with a photoresist developer. The resulting image is then transfenred to the underlying material, which is generally a die electric or metal, by way of plasma etch gases or chemical etchant solutions. Trie etchant gases or chemical etchant solutions selectively attack the photoresist-unprotected ansa of the substrate. As a result of the plasma etching process, photoresist and etched matal by-products are deposited as residues around or on the sidewall of the openings on the substrate and the photoresist.
[0003] Additionally, following the termination of the etching step, the rest
mask must be removed from the protected area of the substrate so that the next process operation can take place. This can be accompished in a plasma ash ng step by the use of suitable plasma ashing gases or wet chemical strippers. Finding














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The exposure temperature was 70oC and the exposure time was three minutes These conditions yielded a complete clean. A five-minute, 5% solution rinse showed complete corrosion of the visible Al/Nd layer such that the molybdenum overlayer was undercut considerably.
[0024] While the invention has been described herein with reference to the
specific embodiments thereof, it will be appreciated that changes, rnodifcation and variations can be made without departing from "he spirit and scope of the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modification and variations that fall with the spirit and scope of the appended claims.




We claim:
1. A composition for cleaning microelectronic substrates comprising the
following components:
(a) a nucleophilic amine,
(b) a moderate to weak acid having a strength expressed as a "pKa " for the dissociation constant in aqueous solution of from about 1.2 to about 8,
(c) a compound selected from the group consisting, of an aliphatic
alcohol, diol, polyol or glycol ether, and
(d) an organic co-solvent,
and the weak acid component (b) is present in the composition in an amount such that the equivalent mole ratio of acid/amine is greater than .75 and the pH of the composition is from about pH 4.5 to 9.5.
2. A composition according to claim 1 comprising from about 1% to about 50% component (a), from about 10% to about 80% of component (c), and from about 20% to about 80%) component (d), the percentages being weight % based on the total weight of the composition.
3. A composition according to claim 1 wherein the nucleophilic amine component is at least one amine selected from the group consisting of 1-amino-2-propanol, 2-(2-aminoethoxy)ethanol, 2-aminoethanol, 2-(2-aminoethylamino)ethanol, 2-(2-aminoethylamino)ethylamine, diethanolamine and triethanolamine.
4. A composition according to claim 1 wherein component (c) is at least one compound selected from the group consisting of isopropanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol,

2-methyl-1,3-propanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, hexanediol, glycerol, ethylene glycoil monomethyl ether diethylene glycol monomethyl ether, propylene glycol dimethyl ether, and 2-(2-butxyethoxy)-ethanol.
5. A composition according to claim 1 wherein the organic co-solvent is a co-solvent having a solubility parameter of from about 8 to about 15.
6. A composition according to claim 5 wherein the co-solvent is at least one compound selected from the group consisting of 2-pyrrolidinone, 1-methyl-2-pyrrolidinone, 1 -ethyl-2-pyrrolidinone, 1 -propyl-2-pyrrolidinone, 1 -hydroxyethyl-2-pyrrolidinone, a dialkyi sulfone, dimethyl sulfoxide, a tetrahydrothiophene-1-,1-dioxide, dimethylacetamide and dimethylformamide.
7. A composition according to Claim 6 wherein the solvent is selected from the group consisting of sulfolane and 1-methyl-2-pyrrolidinone, the nucleophilic amine is selected from the group consisting of monoethanolamine and 1-amino-2-propanol, component (c) is selected from the group consisting of ethylene glycol, propylene glycol, 2-methyl-2,4-pentanediol, glycerol, 2-butene-1,diol, isopropanol and 2-(2-butoxyethoxy)ethanol.
8. A composition according to claim 1 wherein the acid component (b) is at least one acid having a pKa value of from 2 to 5.
9. A composition according to claim 7 wherein the acid component (b) is at least one acid having a pKa value of from 2 to 5.
10. A composition according to claim 1 wherein component (b) comprises at least one acid selected from the group consisting of acetic acid, propanoic acid, malonic acid, phenylacetic acid and hypophosphorus acid.

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11. A composition according to claim 7 wherein component (b) comprises at least one acid selected from the group consisting of acetic acid, propanoic acid, malonic acd, phenylacetic acid and hypophosphorus acid.
12. A composition according to claim 1 wherein the nucleophilic amine comprises monoethanolamine, the co-solvent comprises 1-methyl-2-pyrrolidinone, the compound of component (c) is ethylene glycol and the acid of component (b) is acetic acid.
13. A process for cleaning a microelectronic substrate without producing any substantial metal corrosion, the substrate containing photoresist polymeric material and a metal, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the substrate, wherein the cleaning composition comprises:

(a) a nucleophilic amine,
(b) a moderate to weak acid having a strength expressed as a "pKa" for the dissociation constant in aqueous solution of from about 1.2 to about 8,
(c) a compound selected from the group consisting of an aliphatic
alcohol, diol, polyol or glycol ether, and
(d) an organic co-solvent,
and the weak acid component (b) is present in the cleaning composition in an amount such that the equivalent mole ratio of acid/amine is greater than .75 and the pH of the composition is from about pH 4.5 to 9.5.
14. A process according to claim 13 wherein the cleaning composition comprises
from about 1% to about 50% component (a), from about 10% to about 80% of
component (c), and from about 20% to about 80% component (d), the
percentages being weight % based on the total weight the composition.

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15. A process according to claim 13 wherein the nucleophilic amine component is at least one amine selected from the group consisting of 1-amino-2-propanol, 2-(2-aminoethoxy)ethanol, 2-aminoethanol, 2-(2-aminoethylamino)ethanol, 2-(2-aminoethylamino)ethylamine, diethanolamine and triethanolamine.
16. A process according to claim 13 wherein component (c) is at least one compound selected from the group consisting of isopropanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, hexanediol, glycerol, ethylene glycol monomethyl ether diethylene glycol monomethyl ether, propylene glycol dimethyl ether, and 2-(2-butxyethoxy)-ethanol.
17. A process according to claim 13 wherein the organic co-solvent is a co-solvent having a solubility parameter of from about 8 to about 15.
18. A process according to claim 17 wherein the co-solvent is at least one compound selected from the group consisting of 2-pyrrolidinone, 1-methyl-2-pyrrolidinone, 1 -ethyl-2-pyrrolidinone, 1 -propyl-2-pyrrolidinone, 1 -hydroxyethyl-2'pyrrolidinone, a dialkyi sulfone, dimethyl sulfoxide, a tetrahydrothiophene-1-,1-dioxide, dimethylacetamide and dimethylformamide.
19. A process according to Claim 18 wherein the solvent is selected from the group consisting of sulfolane and 1-methyl-2-pyrrolidinone, the nucleophilic amine is selected from the group consisting of monoethanolamine and 1-amino-2-propanol, component (c) is selected from the group consisting of ethylene glycol, propylene glycol, 2-methyl-2,4-pentanediol, glycerol, 2-butene-1,diol, isopropanol and 2-(2-butoxyethoxy)ethanol.


20. A process according to claim 13 wherein the acid component (b) is at least one acid having a pKa value of from 2 to 5.
21. A process according to claim 19 wherein the acid component (b) is at least one acid having a pKa value of from v 2 to 5.
22. A process according to claim 13 wherein component (b) comprises at least one acid selected from the group consisting of acetic acid, propanoic acid, malonic acid, phenylacetic acid and hypophosphorus acid.
23. A process according to claim 19 wherein component (b) comprises at least one acid selected from the group consisting of acetic acid, propanoic acid, malonic acd, phenylacetic acid and hypophosphorus acid.
24. A process according to claim 13 wherein the nucleophilic amine comprises monoethanolamine, the co-solvent comprises 1-methyl-2-pyrrolidinone, the compound of component (c) is ethylene glycol and the acid of component (b) is acetic acid.
25. A process according to claim 13 wherein the microelectronic substrate is a substrate for a flat panel display.
26. A process according to claim 25 wherein the substrate has an aluminum/neodymium layer.

27. A composition for cleaning microelectronic substrates substantially as herein described and exemplified.



Documents:

956-che-2003-abstract.pdf

956-che-2003-claims duplicate.pdf

956-che-2003-claims original.pdf

956-che-2003-correspondence others.pdf

956-che-2003-correspondence po.pdf

956-che-2003-description complete duplicate.pdf

956-che-2003-description complete original.pdf

956-che-2003-form 1.pdf

956-che-2003-form 26.pdf

956-che-2003-form 3.pdf

956-che-2003-form 5.pdf

956-che-2003-other documents.pdf


Patent Number 201490
Indian Patent Application Number 956/CHE/2003
PG Journal Number 08/2007
Publication Date 23-Feb-2007
Grant Date 28-Jul-2006
Date of Filing 21-Nov-2003
Name of Patentee MALLINCKRODT BAKER INC
Applicant Address 675 MCDONNELL BOULEVARD, P O BOX 5840, ST. LOUIS MO 63134, USA.
Inventors:
# Inventor's Name Inventor's Address
1 SEAN MICHAEL KANE 84 VALLEY PARK SOUTH BETHLEHEM, PA 18018, USA.
2 SANG IN KIM YOUNG APT 931-1401, YOUNG-TONG DONG, PAL-DAL SU-WON, KYONG-KI DO , KOREA.
PCT International Classification Number G03F7/008
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60,493,089 2003-08-06 U.S.A.