Semi Conductor Process Residue Removal Composition and Process

• US 20090203566A1
• Filed: 03/13/2009
• Published: 08/13/2009
• Est. Priority Date: 06/06/2002
• Status: Active Grant

• Current Assignee: EKC Technology, Inc (DuPont de Nemours, Inc.)
• Original Assignee: EKC Technology, Inc (DuPont de Nemours, Inc.)
• Inventors: Matsumoto, Takanori, Otake, Atsushi, Kuroda, Akira, Shang, Cass X., Takeda, Hisashi, Lee, Wai Mun
• Granted Patent: US 8,003,587 B2
• Time in Patent Office: Days
• US Class Current: 510/175
• CPC Class Codes: C11D 2111/22 Electronic devices, e.g. PCBs or semiconductors
• CPC Class Codes: C11D 3/30 Amines; Substituted amines ; Quaternized amines
• CPC Class Codes: C11D 7/3218 Alkanolamines or alkanolimines
• CPC Class Codes: G03F 7/425 containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
• CPC Class Codes: H01L 21/02071 the processing being a delineation, e.g. RIE, of conductive layers

Abstract

A composition that includes 2-(2-aminoethylamino)-ethanol, at least one of a chelating agent and a corrosion inhibitor, and water. The composition is capable of removing organic, organometallic and metal oxide residues from semiconductor substrates. The invention also relates to a method of removing etching residue from a semiconductor substrate.

Claims

1. A composition comprising:

(a) 2-(2-aminoethylamino)-ethanol;

(B) at least one of a chelating agent and a corrosion inhibitor; and

(c) water,

wherein said composition is capable of removing organic, organometallic and metal oxide residues from semiconductor substrates,

wherein the corrosion inhibitor is selected from the group consisting of choline hydroxide;

bischoline hydroxide;

trischoline hydroxide;

TMAH;

TMAH pentahydrate;

BTMAH;

TBAH and mixtures thereof,

and wherein the chelating agent is selected from the group consisting of Amino tris(methylenephosphonic acid), phosphonic acid, citric acid, lactic acid, glycolic acid, tartaric acid, formic acid, glyoxylic acid, acetic acid, propionic acid and mixtures thereof.

2. The composition of claim 1 which further comprises an alkanolamine compound other than 2-(2 aminoethylamino)-ethanol.

3. The composition of claim 2, wherein the alkanolamine compound other than 2-(2 aminoethylamino) ethanol is selected from the group consisting of DGA;

MEA;

MMEA;

MIPA;

DEA;

2-[(2-aminoethyl)-(2-hydroxyethyl)-amino]-ethanol;

TEA;

N-aminoethyl-N′

-hydroxyethyl-ethylenediamine;

N,N-dihydroxyethyl-ethylenediamine;

2-[2-(2-aminoethoxy)-ethylamino]-ethanol;

2-[2-(2-aminoethylamino)-ethoxy]-ethanol;

2-[2-(2-aminoethoxy)-ethoxy]-ethanol;

tertiarybutyldiethanolamine;

isopropanolamine;

diisopropanolamine;

NPA;

isobutanolamine;

2-(2-aminoethoxy)-propanol;

1-hydroxy-2-aminobenzene;

methyldiethanolamine;

aminoethylpropanolamine;

diethyl ethanolamine;

monobutylethanolamine and mixtures thereof.

6. The composition of claim 1 further comprising a surfactant.

7. The composition of claim 6 wherein the surfactant is selected from the group consisting, of epoxy polyamide resin;

3,3,4,4,5,5,6,6,7,7,8,8-tridecafluorooctanesulfonic acid, Ftergent 215M;

monoammonium bis(nonafluorobutanesulfonyl)imide;

polyoxyethylene(23)lauryl ether and mixtures thereof.

8. The composition of claim 1 further comprising a polar organic solvent.

9. The composition of claim 1, wherein the composition is substantially free of hydroxyl amine.

21. The composition of claim 1, further comprising an acid, a base or a mixture thereof.

22. The composition of claim 21, wherein the acid or base is organic or inorganic.

23. The composition of claim 1, wherein the composition has a pH between about 1.5 and about 12.

4. The composition of claim further comprising an amine compound that is not an alkanolamine.

5. The composition of claim 4 wherein the amine compound that is not an alkanolamine is selected from the group consisting of o-diaminobenzene;

p-diaminobenzene;

N-(2-aminoethyl)-ethylenediamine;

piperazine, N-substituted piperazine derivatives, piperidine;

N-substituted piperidine derivatives;

2-methyleneaminopropylenediamine;

hexamthylene tetramine;

EDA;

DETA;

PMDPTA;

TETA;

tetramethylethylenediamine and mixtures thereof.

10. A method of removing etching residue from a semiconductor substrate, said method comprising:

(a) providing a substrate comprising metal and/or metal alloy portions and/or layers and a surface having organic, organometallic, and/or metal oxide residue thereon, and

(b) contacting the substrate with a composition comprising 2-(2-aminoethylamino)-ethanol and water and which composition is substantially free of hydroxylamine.

wherein said composition is capable of removing said organic, organometallic, and metal oxide residues, for a time and at a temperature sufficient to remove the residual from the semiconductor substrate, and

wherein 2-(2-aminoethylamino)-ethanol is present in an amount less than about 1.5% by weight.

11. The method of claim 10, wherein the composition further comprises at least one of a chelating agent and a corrosion inhibitor,

wherein the corrosion inhibitor is selected from the group consisting of choline hydroxide;

bischoline hydroxide;

trischoline hydroxide;

TMAH;

TMAH pentahydrate;

BTMAH;

TBAH and mixtures thereof, and

wherein the chelating agent is selected from the group consisting of Amino tris(methylenephosphonic acid), phosphonic acid, citric acid, lactic acid, glycolic acid, tartaric acid, formic acid, glyoxylic acid, acetic acid, propionic acid and mixtures thereof.

12. The method of claim 10, which further comprises an alkanol amine compound other than 2-(2 aminoethylamino)-ethanol.

13. The method of claim 12, wherein the alkanolamine compound other than 2-(2 aminoethylamino)-ethanol is selected from the group consisting of DGA;

MEA;

MMEA;

MIPA;

DEA;

2-[(2-aminoethyl)-(2-hydroxyethyl)-amino]-ethanol;

TEA;

N-aminoethyl-N′

-hydroxyethyl-ethylenediamine;

N,N′

-dihydroxyethyl-ethylenediamine;

2-[2-(2-aminoethoxy)-ethylamino]-ethanol;

2-[2-(2-aminoethylamino)-ethoxy]-ethanol;

2-[2-(2-aminoethoxy)-ethoxy]-ethanol;

tertiarybutyldiethanolamine;

isopropanoloamine;

diisopropanolamine;

NPA;

isobutanolamine;

2-(2-aminoethoxy)-propanol;

1-hydroxy-2-aminobenzene;

methyldiethanolamine;

aminoethylpropanolamine;

diethyl ethanolamine;

monobutylethanolamine and mixtures thereof.

14. The method of claim 10 further comprising an amine compound that is not an alkanolamine.

15. The method of claim 14 wherein the amine compound is selected from the group consisting of o-diaminobenzene;

p-diaminobenzene;

N-(2-aminoethyl)-ethylenediamine;

piperazine, N-substituted piperazine derivatives, piperidine;

N-substituted piperidine derivatives;

2-methyleneaminopropylenediamine;

hexamthylene tetramine, EDA;

DETA;

PMDTA;

TETA;

tetramethylethylenediamine and mixtures thereof.

16. The method of claim 10 further comprising a surfactant.

17. The method of claim 16 wherein the surfactant is selected from the group consisting of epoxy polyamide resin;

3,3,4,4,5,5,6,6,7,7,8,8-tridecafluorooctanesulfonic acid;

Ftergent 215M;

monoammonium bis(nonafluorobutanesulfonyl)imide;

polyoxyethylene(23)lauryl ether and mixtures thereof.

18. The method of claim 10 further comprising a polar organic solvent.

19. The method of claim 10 wherein the composition can further be diluted with deionized water at point of use to a dilution rate up to about 300 to 1.

20. A composition consisting essentially of:

(a) 2-(2-aminoethylamino)-ethanol;

(b) at least one of a chelating agent and a corrosion inhibitor;

(c) water; and

(d) an alkanolamine compound other than 2-(2 aminoethylamino)

wherein said composition is capable of removing organic, organometallic and metal oxide residues from semiconductor substrates,

wherein the corrosion inhibitor is selected from the group consisting of choline hydroxide;

bischoline hydroxide;

trischoline hydroxide;

TMAH;

TMAH pentahydrate;

BTMAH;

TBAH and mixtures thereof

wherein the chelating agent is selected from the group consisting of Amino tris(methylenephosphonic acid), phosphonic acid, citric acid, lactic acid, glycolic acid, tartaric acid, formic acid, glyoxylic acid, acetic acid, propionic acid and mixtures thereof;

wherein the alkanolamine compound other than 2-(2 aminoethylamino)-ethanol is selected from the group consisting of DGA;

MEA;

MIMEA;

MIPA;

DEA;

2-[(2-aminoethyl)-(2-hydroxyethyl)-amino]-ethanol;

TEA;

N-aminoethyl-N′

-hydroxyethyl-ethylenediamine;

N,N′

-dihydroxyethyl-ethylenediamine;

2-[2-(2-aminoethoxy)-ethylamino]-ethanol;

2-[2-(2-aminoethylamino)-ethoxy]-ethanol;

2-[2-(2-aminoethoxy)-ethoxy]-ethanol;

tertiarybutyldiethanolamine;

isopropanolamine;

diisopropanolamine;

NPA;

isobutanolamine;

2-(2-aminoethoxy)-propanol;

1-hydroxy-2-aminobenzene;

methyldiethanolamine;

aminoethylpropanolamine;

diethyl ethanolamine;

monobutylethanolamine and mixtures thereof, and

wherein 2-(2-aminoethylamino) ethanol is present in an amount less than about 1.5% by weight.