Cleaning formulations

Patent metadata

Field	Value
Publication number	US-9536730-B2
Application number	US-201314010748-A
Country	US
Kind code	B2
Filing date	Aug 27, 2013
Priority date	Oct 23, 2012
Publication date	Jan 3, 2017
Grant date	Jan 3, 2017

Abstract

A composition and method for removing copper-containing post-etch and/or post-ash residue from patterned microelectronic devices is described. The removal composition includes water, a water-miscible organic solvent, an amine compound, an organic acid, and a fluoride ion source. The compositions effectively remove the copper-containing post-etch residue from the microelectronic device without damaging exposed low-k dielectric and metal interconnect materials.

First claim

What is claimed is:

1. A composition useful for removing residue from a semiconductor substrate, the composition consisting of:
a) from about 15% to about 50% by weight of water;
b) from about 10% to about 65% by weight of a water-miscible organic solvent;
c) from about 1% to about 50% by weight of an amine compound selected from the group consisting of a at least one alkanolamine and aminopropylmorpholine;
d) from about 1% to about 25% by weight of an organic acid;
e) from about 0.01% to about 8% by weight of a fluoride ion source, wherein the water-miscible organic solvent is not an ether; and
f) optionally, from about 0.1% to about 15% b weight of a corrosion inhibitor selected from the group consisting of benzotriazole, amino-benzotriazole, L-ascorbic acid, gallic acid, vanillin, diethylhydroxylamine, and mixtures thereof.

2. The composition of claim 1 wherein the water-miscible organic solvent is selected from the group consisting of propylene glycol, glycerol, dimethylacetamide, tetrahydrofuryl alcohol, ethylene glycol, hexylene glycol, and mixtures thereof.

3. The composition of claim 2 wherein the water-miscible organic solvent is dimethylacetamide.

4. The composition of claim 2 wherein the water-miscible organic solvent is propylene glycol.

5. The composition of claim 2 wherein the water-miscible organic solvent is glycerol.

6. The composition of claim 1 wherein the fluoride ion source is selected from the group consisting of ammonium fluoride and a quaternary ammonium compound.

7. The composition of claim 6 wherein the fluoride ion source is ammonium fluoride.

8. The composition of claim 6 wherein the fluoride ion source is a quaternary ammonium compound selected from the group consisting of tetramethylammonium fluoride and tetrabutylammonium fluoride.

9. The composition of claim 1 wherein the amine compound is an alkanolamine selected from the group consisting of N-methylethanolamine (NMEA), monoethanolamine (MEA), diethanolamine, mono-, di- and triisopropanolamine, 2-(2-aminoethylamino)ethanol, 2-(2-aminoethoxy)ethanol, triethanolamine, N-ethyl ethanolamine, N,N-dimethylethanolamine, N,N-diethyl ethanolamine, N-methyl diethanolamine, N-ethyl diethanolamine, cyclohexylaminediethanol, and mixtures thereof.

10. The composition of claim 9 wherein the alkanolamine is monoethanolamine.

11. The composition of claim 9 wherein the amine compound is aminopropylmorpholine.

12. The composition of claim 9 wherein the amine compound is triethanolamine.

13. The composition of claim 9 wherein the amine compound is a mixture of triethanolamine and 2-(2-aminoethoxy)ethanol.

14. The composition of claim 1 wherein the composition consists of:
a) from about 35% to about 50% by weight of water;
b) from about 10% to about 30% by weight of the water-miscible organic solvent;
c) from about 8% to about 50% by weight of the amine compound selected from the group consisting of a at least one alkanolamine and aminopropylmorpholine;
d) from about 6% to about 10% by weight of the organic acid;
e) from about 1% to about 8% by weight of the fluoride ion source; and
f) optionally, from about 0.1% to about 15% by weight of a corrosion inhibitor selected from the group consisting of benzotriazole, amino-benzotriazole, L-ascorbic acid, gallic acid, vanillin, diethylhydroxylamine, and mixtures thereof.

15. A method for removing residue from a semiconductor substrate, the method comprising the steps of:
contacting the semiconductor substrate with a cleaning composition of claim 1 , wherein the semiconductor substrate comprises a porous dielectric material having a dielectric constant;
rinsing the cleaning composition from the semiconductor substrate; and
drying the semiconductor substrate,

wherein the dielectric constant of the porous dielectric material does not increase more than 0.50.

16. The method of claim 15 wherein the dielectric constant of the porous dielectric material does not increase more than 0.25.

17. The method claim 15 wherein the cleaning composition provides a copper etch rate of 4 Å/min or less.

18. A replenishment composition to be added to a cleaning composition, said replenishment composition consisting of: a) from about 20% to about 84% by weight of water; b) from about 15% to about 40% by weight of a water-miscible organic solvent, wherein the water-miscible solvent is not an ether; c) from about 1% to about 5% by weight of an amine compound selected from the group consisting of at least one alkanolamine; at least one aminopropylmorpholine; and optionally, from about 4% to about 35% by weight of diethyl hydroxylamine, and said water is from about 20 to about 80% of the replenishment composition.

19. A method for removing unwanted residues from a semiconductor substrate comprising the steps of: contacting the semiconductor substrate with a cleaning composition consisting of: a) from about 15% to about 50% by weight of water; b) from about 10% to about 65% by weight of a water-miscible organic solvent, wherein the water-miscible solvent is not an ether; c) from about 1% to about 20% by weight of an amine compound selected from the group consisting of at least one alkanolamine and at least one aminopropylmorpholine; d) from about 1% to about 25% by weight of at least one organic acid; e) from about 0.01% to about 8% by weight of a fluoride ion source; and f) from about 1 to about 15% by weight of diethyl hydroxylamine, wherein said contacting step results in a loss of a portion of said cleaning composition; and adding a replenishment composition to said cleaning composition; said replenishment composition consisting of a composition of claim 18 .

20. The method of claim 19 further comprising the steps of rinsing the cleaning composition from the semiconductor substrate; and drying the semiconductor substrate, wherein the semiconductor substrate comprises a porous dielectric material having a dielectric constant; and wherein after said contacting, rinsing and drying steps the dielectric constant of the porous dielectric material does not increase more than 0.50.

21. The method of claim 20 wherein the dielectric constant of porous dielectric material does not increase more than 0.25.

Assignees

• Air Prod & Chem
• Air Prod & Chem

Inventors

• Lee Yi Chia
• Rao Madhukar Bhaskara
• Banerjee Gautam
• Liu Wen Dar
• Wu Aiping
• Inaoka Seiji

Classifications

• H10P70/15 Primary

  by wet cleaning only (H10P70/52 takes precedence) · CPC title

• C11D7/5013

  containing nitrogen · CPC title

• G03F7/426

  containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides · CPC title

• C11D7/5022

  containing oxygen · CPC title

• C11D7/10 Primary

  Salts · CPC title