Compositions and methods for preventing collapse of high aspect ratio structures during drying

Patent metadata

Field	Value
Publication number	US-10954480-B2
Application number	US-201816141735-A
Country	US
Kind code	B2
Filing date	Sep 25, 2018
Priority date	Sep 29, 2017
Publication date	Mar 23, 2021
Grant date	Mar 23, 2021

Abstract

Described herein is an aqueous composition for treating a substrate including patterns having line-space dimensions of 50 nm or below to prevent collapse of the patters, the composition comprising: a solvent system comprising water and a water-miscible organic solvent; a surface modifier that is a reaction product between an alkylamine and an organic acid; and an optional pH adjusting agent.

First claim

The invention claimed is:

1. An aqueous composition for treating a substrate including patterns having line-space dimensions of 50 nm or below to prevent collapse of the patterns, the composition comprising:
a solvent system comprising water and a water-miscible organic solvent;
a surface modifier that is a reaction product between an alkylamine and an organic acid;
and optional pH adjusting agent;

wherein said organic acid is selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, amino carboxylic acids, sulfonic acids and aminosulfonic acids;
the pH of the composition is from about 1 to about 5;
wherein the alkylamine is selected from a primary amine or a secondary amine;
and the composition is free of corrosion inhibitors.

2. The aqueous composition of claim 1 wherein the solvent system comprises water and dipropylene glycol methyl ether.

3. The aqueous composition of claim 2 wherein the water is present at 70 wt % based on the total weight of the solvent system and the dipropylene glycol methyl ether is present at 30 wt % based on the total weight of the solvent system.

4. The aqueous composition of claim 1 wherein the organic acid is p-toluenesulfonic acid.

5. The aqueous composition of claim 1 wherein the alkylamine is a primary amine.

6. The aqueous composition of claim 1 wherein the alkylamine is a secondary amine.

7. The aqueous composition of claim 1 wherein the organic acid is selected from the group consisting of sulfonic acids and aminosulfonic acids.

8. The aqueous composition of claim 5 wherein the alkylamine is dodecylamine.

9. The aqueous composition of claim 1 wherein the pH adjusting agent comprises excess organic acid.

10. The aqueous composition of claim 8 , wherein said organic acid is selected from the group consisting of sulfonic acids and aminosulfonic acids.

11. A method for treating a substrate including patterns having line-space dimensions of 50 nm or below, the method comprising rinsing the substrate with an aqueous composition comprising:
a solvent system comprising water and a water-miscible organic solvent;
a surface modifier that is a reaction product between an alkylamine and an organic acid; and
optional pH adjusting agent;

wherein said organic acid is selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, amino carboxylic acids, sulfonic acids and aminosulfonic acids;
wherein the alkylamine is selected from a primary amine or a secondary amine;
the pH of the composition is from about 1 to about 5;
and the composition is free of corrosion inhibitors, and further
wherein collapse of the patterns is substantially prevented.

12. The method of claim 11 wherein the contacting step occurs at a temperature of from about 25 to 125° C.

13. The method of claim 11 wherein the contacting step occurs at a temperature of from about 25 to 80° C.

14. The method of claim 11 wherein the solvent system comprises water and dipropylene glycol methyl ether.

15. The method of any of claim 11 wherein the water is present at 70 wt % based on the total weight of the solvent system and the dipropylene glycol methyl ether is present at 30 wt % based on the total weight of the solvent system.

16. The method of any of claim 11 wherein the organic acid is p-toluenesulfonic acid.

17. The method of claim 11 wherein the alkylamine is a primary amine.

18. The method of claim 11 wherein the alkylamine is a secondary amine.

19. The method of claim 11 wherein the organic acid is selected from the group consisting of sulfonic acids and aminosulfonic acids.

20. The method of claim 16 wherein the alkylamine is dodecylamine.

21. The method of claim 11 wherein the pH adjusting agent comprises excess organic acid.

22. The method of claim 20 wherein the organic acid is selected from the group consisting of sulfonic acids and aminosulfonic acids.

23. The aqueous composition of claim 1 wherein the alkylamine is selected from methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, icosylamine, eicosylamine, henicosylamine, heneicosylamine, docosylamine, tricosylamine, tetracosylamine, 1-methylbutylamine, 2-methylbutylamine, cyclopropylmethylamine, cyclohexylmethylamine, benzylamine, 2-methylbenzylamine, 4-methylbenzylamine, 1-phenylethylamine, 2-phenylethylamine, 3-aminomethylpyridine, 1-(4-chlorophenyl)ethylamine, 2-(2-chlorophenyl)ethylamine, 1-(3-methoxyphenyl)ethylamine, 1-(4-methoxyphenyl)ethylamine, 2-(2-methoxyphenyl)ethylamine, 2-(3-methoxyphenyl)ethylamine, 2-(4-methoxyphenyl)ethylamine, 1-[3-(trifluoromethyl)phenyl]ethylamine, 1-(1-naphthyl)ethylamine, 1-(2-naphthyl)ethylamine, 1-phenylpropylamine, and 3-phenylpropylamine, and mixtures thereof.

24. The method of claim 11 wherein the alkylamine is selected from methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, icosylamine, eicosylamine, henicosylamine, heneicosylamine, docosylamine, tricosylamine, tetracosylamine, 1-methylbutylamine, 2-methylbutylamine, cyclopropylmethylamine, cyclohexylmethylamine, benzylamine, 2-methylbenzylamine, 4-methylbenzylamine, 1-phenylethylamine, 2-phenylethylamine, 3-aminomethylpyridine, 1-(4-chlorophenyl)ethylamine, 2-(2-chlorophenyl)ethylamine, 1-(3-methoxyphenyl)ethylamine, 1-(4-methoxyphenyl)ethylamine, 2-(2-methoxyphenyl)ethylamine, 2-(3-methoxyphenyl)ethylamine, 2-(4-methoxyphenyl)ethylamine, 1-[3-(trifluoromethyl)phenyl]ethylamine, 1-(1-naphthyl)ethylamine, 1-(2-naphthyl)ethylamine, 1-phenylpropylamine, and 3-phenylpropylamine, and mixtures thereof.

Assignees

• Versum Mat Us Llc

Inventors

• Ge Jhih Kuei
• Lee Yi-Chia
• Liu Wen Dar
• Chen Tianniu Rick

Classifications

• H10P70/20

  Cleaning during device manufacture · CPC title

• C11D7/5022

  containing oxygen · CPC title

• C11D7/5009

  containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide · CPC title

• C11D7/50 Primary

  Solvents · CPC title

• C11D7/3209

  Amines or imines with one to four nitrogen atoms; Quaternized amines · CPC title