Aqueous cleaning composition containing copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrate

1. A post CMP cleaning formulation comprising an organic amine, a fluoride source and from 70% to 98% water by weight, based on the total weight of the formulation, wherein the pH of the post CMP cleaning formulation is between about 7 and about 9.

2. The post CMP cleaning formulation according to claim 1 , wherein said formulation further comprises a metal chelating agent.

3. The post CMP cleaning formulation according to claim 2 , wherein said formulation further comprises a nitrogenous component.

4. The post CMP cleaning formulation according to claim 1 , wherein said fluoride source comprises from about 0.1% to about 5.0% fluoride source by weight, based on the total weight of the formulation.

5. The post CMP cleaning formulation according to claim 1 , wherein said fluoride is selected from the group consisting of:

any combination of ammonia gas or ammonium hydroxide and hydrogen fluoride gas or hydrofluoric acid,

ammonium fluoride,

ammonium bifluoride,

triethanolammonium fluoride, (TEAF),

diglycolammonium fluoride, (DGAF),

tetramethylammonium fluoride, (TMAF),

methyldiethanolammonium fluoride, (MDEAF) and

triethylamine tris(hydrogen fluoride) (TREAT-HF).

6. The post CMP cleaning formulation according to claim 1 , wherein said formulation comprises from about 1% to 15% organic amine by weight, based on the total weight of the formulation.

7. The post CMP cleaning formulation according to claim 1 , wherein said organic amine is selected from the group consisting of:

diglycolamine (DGA),

methyldiethanolamine (MDEA),

pentamethyldiethylenetriamine (PMDETA),

triethanolamine (TEA),

triethylenediamine (TEDA),

hexamethylenetetramine,

3,3-iminobis (N,N-dimethylpropylamine),

monoethanolamine,

2-(methylamino)ethanol,

4-(2-hydroxyethyl)morpholine,

4-(3-aminopropyl)morpholine, and

N,N-dimethyl-2-(2-aminoethoxy)ethanol.

8. The post CMP cleaning formulation according to claim 2 , wherein said formulation comprises from about 0 to about 5.0% metal chelating agent by weight, based on the total weight of the formulation.

9. The post CMP cleaning formulation according to claim 2 , wherein said metal chelating agent is selected from the group consisting of:

acetoacetamide,

ammonium carbamate,

ammonium pyrrolidinedithiocarbamate (APDC),

dimethyl malonate,

methyl acetoacetate,

N-methyl acetoacetamide,

2,4-pentanedione,

1,1,1,5,5,5-hexafluoro-2,4-pentanedione H(hfac),

2,2,6,6-tetramethyl-3,5-heptanedione H(thd),

tetramethylammonium thiobenzoate,

tetramethylammonium trifluoroacetate,

tetramethylthiuram disulfide (TMTDS),

trifluoracetic acid,

lactic acid,

ammonium lactate,

malonic acid,

formic acid,

acetic acid,

propionic acid,

gama-butyrolactone,

methyldiethanolammonium trifluoroacetate, and

trifluoroacetic acid.

10. The post CMP cleaning formulation according to claim 3 , wherein said formulation comprises from about 0 to about 10% nitrogenous component by weight, based on the total weight of the formulation.

11. The post CMP cleaning formulation according to claim 3 , wherein said nitrogenous component is selected from the group consisting of:

iminodiacetic acid (IDA),

glycine,

nitrilotriacetic acid (NTA),

hydroxyethyliminodiacetic acid,

1,1,3,-tetramethylguanidine (TMG),

ethylenediaminetetracetic acid (EDTA),

CH 3 C(═NCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NCH 2 CH 2 OCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NH)CH 2 C(O)CH 3 ,

(CH 3 CH 2 ) 2 NC(═NH)N(CH 3 CH 2 ) 2 ,

HOOCCH 2 N(CH 3 ) 2 , and

HOOCCH 2 N(CH 3 )CH 2 COOH.

12. The post CMP cleaning formulation according to claim 1 , wherein said formulation comprises the following components in the percentage by weight shown, based on the total weight of such formulation:

triethanolamine

4.5%,

ammonium Fluoride

0.5%, and

water

 95%.

13. The post CMP cleaning formulation according to claim 1 , wherein said formulation comprises the following components in the percentage by weight ranges shown, based on the total weight of such formulation:

PMDETA

3.8-4.5%,

ammonium fluoride

0.5%,

2,4-Pentanedione

  1%, and

water

 94-94.7%.

14. The post CMP cleaning formulation according to claim 1 , wherein said formulation comprises the following components in the percentage by weight shown, based on the total weight of such formulation:

TEA

 1.7%

PMDETA

 1.5%

TEAF

  2%,

iminodiacetic Acid

 0.4%,

ammonium bifluoride

 0.5%, and

water

93.9%.

15. The post CMP cleaning formulation according to claim 1 , wherein said formulation comprises the following components in the percentage by weight shown, based on the total weight of such formulation:

TEA

 3.5%,

PMDETA

 1.5%,

2,4-Pentanedione

 1.35%,

ammonium fluoride

 1.2%, and

water

92.45%.

16. The post CMP cleaning formulation according to claim 1 , wherein said formulation comprises the following components in the percentage by weight shown, based on the total weight of such formulation:

TEA

  7%,

PMDETA

  3%,

2,4-Pentanedione

 2.7%,

ammonium fluoride

 2.4%, and

water

84.9%.

17. A semiconductor wafer cleaning formulation comprising the following components in the percentage by weight ranges shown, based on the total weight of such components:

fluoride source

 1-35%

organic amine(s)

20-60%

a nitrogenous component, selected from the group

0.1-40% 

consisting of nitrogen-containing carboxylic acids and

imines

water

20-50%

and

metal chelating agent(s)

 0-21%

TOTAL

100%.

18. The cleaning formulation of claim 17 , wherein said fluoride source comprises a fluoride species selected from the group consisting of:

any combination of ammonia gas or ammonium hydroxide and hydrogen fluoride gas or hydrofluoric acid,

ammonium bifluoride,

ammonium fluoride,

triethanolammonium fluoride (TEAF),

diglycolammonium fluoride (DGAF),

tetramethylammonium fluoride (TMAF),

methyldiethanolammonium fluoride (MDEAF), and

triethylamine tris(hydrogen fluoride) (TREAT-HF).

19. The cleaning formulation of claim 17 , wherein said organic amine(s) comprise an amine(s) selected from the group consisting of:

diglycolamine (DGA),

methyldiethanolamine (MDEA),

pentamethyldiethylenetriamine (PMDETA),

triethanolamine (TEA),

triethylenediamine (TEDA),

hexamethylenetetramine,

3,3-iminobis (N,N-dimethylpropylamine),

monoethanolamine,

2-(methylamino)ethanol,

4-(2-hydroxyethyl)morpholine,

4-(3-aminopropyl)morpholine, and

N,N-dimethyl-2-(2-aminoethoxy)ethanol.

20. The cleaning formulation of claim 17 , wherein said nitrogenous component comprises a species selected from the group consisting of:

iminodiacetic acid (IDA),

glycine,

nitrilotriacetic acid (NTA),

hydroxyethyliminodiacetic acid,

1,1,3,-tetramethylguanidine (TMG),

ethylenediaminetetracetic acid (EDTA),

CH 3 C(═NCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NCH 2 CH 2 OCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NH)CH 2 C(O)CH 3 ,

(CH 3 CH 2 ) 2 NC(═NH)N(CH 3 CH 2 ) 2 ,

HOOCCH 2 N(CH 3 ) 2 , and

HOOCCH 2 N(CH 3 )CH 2 COOH.

21. The cleaning formulation of claim 17 , including at least one metal chelating agent selected from the group consisting of:

acetoacetamide,

ammonium carbamate,

ammonium pyrrolidinedithiocarbamate (APDC),

dimethyl malonate,

methyl acetoacetate,

N-methyl acetoacetamide,

2,4-pentanedione,

1,1,1,5,5,5-hexafluoro-2,4-pentanedione H(hfac),

2,2,6,6-tetrammethyl-3,5-heptanedione H(thd),

tetramethylammonium thiobenzoate,

tetramethylammonium trifluoroacetate,

tetramethylthiuram disulfide (TMTDS),

trifluoracetic acid,

lactic acid,

ammonium lactate,

malonic acid,

formic acid,

acetic acid,

propionic acid,

gamma-butyrolactone,

iminodiacetic acid,

methyldiethanolammonium trifluoroacetate, and

trifluoroacetic acid.

22. The cleaning formulation of claim 17 , wherein said fluoride source comprises a species selected from the group consisting of:

any combination of ammonia gas or ammonium hydroxide and hydrogen fluoride gas or hydrofluoric acid,

ammonium fluoride,

ammonium bifluoride,

triethanolammonium fluoride (TEAF),

diglycolammonium fluoride (DGAF),

methyldiethanolammonium fluoride (MDEAF),

tetramethylammonium fluoride (TMAF), and

triethylamine tris(hydrogen fluoride) (TREAT-HF);

said organic amine(s) comprise a species selected from the group consisting of:

diglycolamine (DGA),

methyldiethanolamine (MDEA),

pentamethyidiethylenetriamine (PMDETA),

triethanolamine (TEA),

triethylenediamine (TEDA),

hexamethylenetetramine,

3,3-iminobis (N,N-dimethylpropylamine),

monoethanolamine,

2-(methylamino)ethanol,

4-(2-hydroxyethyl)morpholine,

4-(3-aminopropyl)morpholine, and

N,N-dimethyl-2-(2-aminoethoxy)ethanol;

said nitrogenous component comprises a species selected from the group consisting of:

iminodiacetic acid (IDA),

glycine,

nitrilotriacetic acid (NTA),

hydroxyethyliminodiacetic acid,

1,1,3,-tetramethylguanidine (TMG),

ethylenediaminetetracetic acid (EDTA),

CH 3 C(═NCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NCH 2 CH 2 OCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NH)CH 2 C(O)CH 3 ,

(CH 3 CH 2 ) 2 NC(═NH)N(CH 3 CH 2 ) 2 ,

HOOCCH 2 N(CH 3 ) 2 , and

HOOCCH 2 N(CH 3 )CH 2 COOH; and

said formulation includes a metal chelating agent comprising a species selected from the group consisting of:

acetoacetamide,

ammonium carbamate,

ammonium pyrrolidinedithiocarbamate (APDC),

dimethyl malonate,

methyl acetoacetate,

N-methyl acetoacetamide,

2,4-pentanedione,

1,1,1,5,5,5-hexafluoro-2,4-pentanedione H(hfac),

2,2,6,6-tetrammethyl-3,5-heptanedione H(thd),

tetramethylammonium thiobenzoate,

tetramethylammonium trifluoroacetate,

tetramethylthiuram disulfide (TMTDS),

trifluoracetic acid,

lactic acid,

ammonium lactate,

malonic acid,

formic acid,

acetic acid,

propionic acid,

gamma-butyrolactone,

iminodiacetic acid,

methyldiethanolammonium trifluoroacetate, and

trifluoroacetic acid.

23. The cleaning formulation of claim 17 , wherein said fluoride source comprises a compound having the general formula R 1 R 2 R 3 R 4 NF in which each of the R groups is independently selected from hydrogen atoms and aliphatic groups, and wherein said formulation includes a metal chelating agent of the formula:

X—CHR—Y,

in which R is either hydrogen or an aliphatic group and X and Y are functional groups containing multiply bonded moieties having electron-withdrawing properties.

24. The cleaning formulation of claim 23 , wherein each of X and Y is independently selected from CONH 2 , CONHR′, CN, NO 2 , SOR′, and SO 2 Z in which R′ is alkyl and Z is hydrogen, halo, or alkyl.

25. The cleaning formulation of claim 17 , wherein said fluoride source comprises a compound having the formula R 1 R 2 R 3 R 4 NF in which each of the R groups is hydrogen or aliphatic, and wherein said formulation includes a metal chelating agent of the formula, R 1 R 2 R 3 R 4 N +−O 2 CCF 3 in which each of the R groups is independently hydrogen or aliphatic.

26. The cleaning formulation of claim 17 , wherein said nitrogenous component includes a compound having the formula:

COOH—CH 2 —NRR′

wherein each of R and R′ is independently selected from the group consisting of hydrogen, alkyl, aryl, and carboxylic acids.

27. A method for fabricating a semiconductor wafer, comprising:

plasma etching a metallized layer from a surface of the wafer;

plasma ashing a resist from the surface of the wafer; and

cleaning the wafer by contacting same with a cleaning formulation, comprising the following components in the percentage by weight ranges shown, based on the total weight of such components:

fluoride source

 1-35%

organic amine(s)

20-60%

a nitrogenous component, selected from the group

0.1-40% 

consisting of nitrogen-containing carboxylic acids and

imines

water

20-50%

metal chelating agent(s)

 0-21%

TOTAL

100%.

28. The method of claim 27 , wherein said fluoride source comprises a fluoride species selected from the group consisting of:

any combination of ammonia gas or ammonium hydroxide and hydrogen fluoride gas or hydrofluoric acid,

ammonium fluoride,

ammonium bifluoride,

triethanolammonium fluoride (TEAF),

diglycolammonium fluoride (DGAF),

methyldiethanolammonium fluoride (MDEAF),

tetramethylammonium fluoride (TMAF), and

triethylamine tris(hydrogen fluoride) (TREAT-HF).

29. The method of claim 27 , wherein said organic amine(s) comprise an amine(s) selected from the group consisting of:

diglycolamine (DGA),

methyldiethanolamine (MDEA),

pentamethyldiethylenetriamine (PMDETA),

triethanolamine (TEA),

triethylenediamine (TEDA),

hexamethylenetetramine,

3,3-iminobis (N,N-dimethylpropylamine),

monoethanolamine,

2-(methylamino)ethanol,

4-(2-hydroxyethyl)morpholine,

4-(3-aminopropyl)morpholine, and

N,N-dimethyl-2-(2-aminoethoxy)ethanol.

30. The method of claim 27 , wherein said nitrogenous component comprises a species selected from the group consisting of:

iminodiacetic acid (IDA),

glycine,

nitrilotriacetic acid (NTA),

hydroxyethyliminodiacetic acid,

1,1,3,-tetramethylguanidine (TMG),

ethylenediaminetetracetic acid (EDTA),

CH 3 C(═NCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NCH 2 CH 2 OCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NH)CH 2 C(O)CH 3 ,

(CH 3 CH 2 ) 2 NC(═NH)N(CH 3 CH 2 ) 2 ,

HOOCCH 2 N(CH 3 ) 2 ,

HOOCCH 2 N(CH 3 )CH 2 COOH.

31. The method of claim 27 , including at least one metal chelating agent selected from the group consisting of:

acetoacetamide,

ammonium carbamate,

ammonium pyrrolidinedithiocarbamate (APDC),

dimethyl malonate,

methyl acetoacetate,

N-methyl acetoacetamide,

2,4-pentanedione,

1,1,1,5,5,5-hexafluro0-2,4-pentanedione H(hfac),

2,2,6,6-tetrammethyl-3,5-heptanedione H(thd),

tetramethylammonium thiobenzoate,

tetramethylammonium trifluoroacetate,

tetramethylthiuram disulfide (TMTDS),

trifluoracetic acid,

lactic acid,

ammonium lactate,

malonic acid,

formic acid,

acetic acid,

propionic acid,

gamma-butyrolactone,

iminodiacetic acid,

methyldiethanolammonium trifluoroacetate, and

trifluoroacetic acid.

32. The method of claim 27 , wherein said fluoride source comprises a species selected from the group consisting of:

any combination of ammonia gas or ammonium hydroxide and hydrogen fluoride gas or hydrofluoric acid,

ammonium fluoride,

ammonium bifluoride,

triethanolammonium fluoride (TEAF),

diglycolammonium fluoride (DGAF),

methyldiethanolammonium fluoride (MDEAF),

tetramethylammonium fluoride (TMAF), and

triethylamine tris(hydrogen fluoride) (TREAT-HF);

said organic amine(s) comprise a species selected from the group consisting of:

diglycolamine (DGA),

methyldiethanolamine (MDEA),

pentamethyldiethylenetriamine (PMDETA),

triethanolamine (TEA),

triethylenediamine (TEDA),

hexamethylenetetramine,

3,3-iminobis (N,N-dimethylpropylamine),

monoethanolamine,

2-(methylamino)ethanol,

4-(2-hydroxyethyl)morpholine

4-(3-aminopropyl)morpholine, and

N,N-dimethyl-2-(2-aminoethoxy)ethanol;

said nitrogenous component comprises a species selected from the group consisting of:

iminodiacetic acid (IDA),

glycine,

nitrilotriacetic acid (NTA),

hydroxyethyliminodiacetic acid,

1,1,3,-tetramethylguanidine (TMG),

ethylenediaminetetracetic acid (EDTA),

CH 3 C(═NCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NCH 2 CH 2 OCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NH)CH 2 C(O)CH 3 ,

(CH 3 CH 2 ) 2 NC(═NH)N(CH 3 CH 2 ) 2 ,

HOOCCH 2 N(CH 3 ) 2 , and

HOOCCH 2 N(CH 3 )CH 2 COOH; and

said formulation includes a metal chelating agent comprising a species selected from the group consisting of:

acetoacetamide,

ammonium carbamate,

ammonium pyrrolidinedithiocarbamate (APDC),

dimethyl malonate,

methyl acetoacetate,

N-methyl acetoacetamide,

2,4-pentanedione,

1,1,1,5,5,5-hexafluro-2,4-pentanedione H(hfac),

2,2,6,6-tetramethyl-3,5-heptanedione H(thd),

tetramethylammonium thiobenzoate,

tetramethylammonium trifluoroacetate,

tetramethylthiuram disulfide (TMTDS),

lactic acid,

ammonium lactate,

malonic acid,

formic acid,

acetic acid,

propionic acid,

gamma-butyrolactone,

methyldiethanolammonium trifluoroacetate, and

trifluoroacetic acid.

33. The method of claim 27 , wherein said fluoride source comprises a compound having the general formula R 1 R 2 R 3 R 4 NF in which each of the R groups is independently selected from hydrogen atoms and aliphatic groups, and wherein said formulation includes a metal chelating agent of the formula:

X—CHR—Y,

in which R is either hydrogen or an aliphatic group and X and Y are functional groups containing multiply bonded moieties having electron-withdrawing properties.

34. The method of claim 33 , wherein each of X and Y is independently selected from CONH 2 , CONHR′, CN, NO 2 , SOR′, and SO 2 Z in which R′ is alkyl and Z is hydrogen, halo, or alkyl.

35. The method of claim 27 , wherein said fluoride source comprises a compound having the formula R 1 R 2 R 3 R 4 NF in which each of the R groups is hydrogen or aliphatic, and wherein said formulation includes a metal chelating agent of the formula, R 1 R 2 R 3 R 4 N +−O 2 CCF 3 in which each of the R groups is independently hydrogen or aliphatic.

36. The method of claim 27 , wherein said nitrogenous component includes a compound having the formula:

COOH—CH 2 —NRR′

wherein each of R and R′ is independently selected from the group consisting of hydrogen, alkyl, aryl, and carboxylic acids.

37. A method for fabricating a semiconductor wafer including the steps comprising:

plasma etching a metallized layer from a surface of the wafer;

plasma ashing a resist from the surface of the wafer;

cleaning the wafer by contacting same with a cleaning formulation, comprising the following components in the percentage by weight ranges shown, based on the total weight of such components:

a fluoride source;

 1-35%

at least one organic amine;

20-60%

a nitrogen-containing carboxylic acid or imine

0.1-40% 

water;

20-50%

at least one metal chelating agent

 0-21%

TOTAL

100%.

38. The method of claim 37 , wherein said fluoride source is selected from the group consisting of:

any combination of ammonia gas or ammonium hydroxide and hydrogen fluoride gas or hydrofluoric acid,

ammonium fluoride,

ammonium bifluoride,

triethanolammonium fluoride (TEAF),

diglycolammonium fluoride (DGAF),

methyldiethanolammonium fluoride (MDEAF),

tetramethylammonium fluoride (TMAF), and

triethylamine tris(hydrogen fluoride) (TREAT-HF).

39. The method of claim 37 , wherein said organic amine is selected from the group consisting of:

diglycolamine (DGA),

methyldiethanolamine (MDEA),

pentamethyldiethylenetriamine (PMDETA),

triethanolamine (TEA),

triethylenediamine (TEDA),

hexamethylenetetramine,

3,3-iminobis (N,N-dimethylpropylamine),

monoethanolamine,

2-(methylamino)ethanol,

4-(2-hydroxyethyl)morpholine,

4-(3-aminopropyl)morpholine, and

N,N-dimethyl-2-(2-aminoethoxy)ethanol.

40. The method of claim 37 , wherein said nitrogen-containing carboxylic acid or imine is selected from the group consisting of:

iminodiacetic acid (IDA),

glycine,

nitrilotriacetic acid (NTA),

hydroxyethyliminodiacetic acid,

1,1,3,-tetramethylguanidine (TMG),

ethylenediaminetetracetic acid (EDTA),

CH 3 C(═NCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NCH 2 CH 2 OCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NH)CH 2 C(O)CH 3 ,

(CH 3 CH 2 ) 2 NC(═NH)N(CH 3 CH 2 ) 2 ,

HOOCCH 2 N(CH 3 ) 2 , and

HOOCCH 2 N(CH 3 )CH 2 COOH.

41. The method of claim 37 , wherein said metal chelating agent is selected from the group consisting of:

acetoacetamide,

ammonium carbamate,

ammonium pyrrolidinedithiocarbamate (APDC),

dimethyl malonate,

methyl acetoacetate,

N-methyl acetoacetamide,

2,4-pentanedione,

1,1,1,5,5,5-hexafluro0-2,4-pentanedione H(hfac),

2,2,6,6-tetramethyl-3,5-heptanedione H(thd),

tetramethylammonium thiobenzoate,

tetramethylammonium trifluoroacetate,

tetramethylthiuram disulfide (TMTDS),

lactic acid,

ammonium lactate,

malonic acid,

formic acid,

acetic acid,

propionic acid,

gamma-butyrolactone,

methyldiethanolammonium trifluoroacetate, and

trifluoroacetic acid.

42. The method of claim 37 , wherein said fluoride source is selected from the group consisting of:

any combination of ammonia gas or ammonium hydroxide and hydrogen fluoride gas or hydrofluoric acid,

ammonium fluoride,

ammonium bifluoride,

triethanolammonium fluoride (TEAF),

diglycolammonium fluoride (DGAF),

methyldiethanolammonium fluoride (MDEAF),

tetramethylammonium fluoride (TMAF), and

triethylamine tris(hydrogen fluoride) (TREAT-HF);

said organic amine(s) is selected from the group consisting of:

diglycolamine (DGA),

methyldiethanolamine (MDEA),

pentamethyldiethylenetriamine (PMDETA),

triethanolamine (TEA),

triethylenediamine (TEDA),

hexamethylenetetramine,

3,3-iminobis (N,N-dimethylpropylamine),

monoethanolamine,

2-(methylamino)ethanol,

4-(2-hydroxyethyl)morpholine,

4-(3-aminopropyl)morpholine, and

N,N-dimethyl-2-(2-aminoethoxy)ethanol;

said nitrogen-containing carboxyl acid or imine is selected from the group consisting of:

iminodiacetic acid (IDA),

glycine,

nitrilotriacetic acid (NTA),

hydroxyethyliminodiacetic acid,

1,1,3,-tetramethylguanidine (TMG),

ethylenediaminetetracetic acid (EDTA),

CH 3 C(═NCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NCH 2 CH 2 OCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,

CH 3 C(═NH)CH 2 C(O)CH 3 ,

(CH 3 CH 2 ) 2 NC(═NH)N(CH 3 CH 2 ) 2 ,

HOOCCH 2 N(CH 3 ) 2 , and

HOOCCH 2 N(CH 3 )CH 2 COOH; and

said formualation includes a metal chelating agent comprising a species selected from the group consisting of:

acetoacetamide,

ammonium carbamate,

ammonium pyrrolidinedithiocarbamate (APDC),

dimethyl malonate,

methyl acetoacetate,

N-methyl acetoacetamide,

2,4-pentanedione,

1,1,1,5,5,5-hexafluro-2,4-pentanedione H(hfac),

2,2,6,6-tetrammethyl-3,5-heptanedione H(thd),

tetramethylammonium thiobenzoate,

tetramethylammonium trifluoroacetate,

tetramethylthiuram disulfide (TMTDS),

trifluoracetic acid,

ammonium lactate,

malonic acid,

formic acid,

acetic acid,

propionic acid,

gamma-butyrolactone,

methyldiethanolammonium trifluoroacetate, and

trifluoroacetic acid.

43. The method of claim 37 , wherein said fluoride source comprises a compound having the formula R 1 R 2 R 3 R 4 NF in which each of the R groups is hydrogen atoms or aliphatic, and wherein said metal chelating agent has the formula:

X—CHR—Y,

in which R is either hydrogen or an aliphatic group, and X and Y are functional groups containing multiply-bonded moieties having electron-withdrawing properties.

44. The method of claim 37 , wherein said fluoride source comprises a compound having the formula R 1 R 2 R 3 R 4 NF in which each of the R groups is hydrogen or aliphatic, and wherein said metal chelating agent has the formula, R 1 R 2 R 3 R 4 N + *O 2 CCF 3 in which each of the R groups is hydrogen or aliphatic.

45. The method of claim 37 , wherein said nitrogen-containing carboxylic acid has the formula:

 COOH—CH 2 —NRR′

Wherein each of R and R′ is independently selected from the group consisting of hydrogen, alkyl, aryl, and carboxylic acid.

46. A method of removing residue from a wafer following a resist plasma ashing step on said wafer, comprising contacting the wafer with a cleaning formulation, including (i) a fluoride source, (ii) at least one organic amine, (iii) a nitrogen-containing carboxylic acid or an imine, (iv) water, and optionally at least one metal chelating agent.

47. A wafer cleaning formulation, including (i) a fluoride source, (ii) at least one organic amine, (iii) a nitrogen-containing carboxylic acid or an imine, (iv) water, and optionally at least one metal chelating agent, wherein the pH of the wafer cleaning formulation is between 7 and about 9.

48. A semiconductor wafer cleaning formulation comprising the following components in the percentage by weight ranges shown, based on the total weight of such components:

fluoride source

 1-35%

organic amine(s)

20-60%

a nitrogenous component, selected from the group

0.1-40% 

consisting of nitrogen-containing carboxylic acids and

imines

water

20-50%

and

metal chelating agent(s)

 0-21%

TOTAL

100%,

wherein said fluoride source comprises a compound having the formula R 1 R 2 R 3 R 4 NF in which each of the R groups is hydrogen or aliphatic, and wherein said formulation includes a metal chelating agent of the formula, R 1 R 2 R 3 R 4 +−O 2 CCF 3 in which each of the R groups is independently hydrogen or aliphatic.

49. A semiconductor wafer cleaning formulation comprising the following components in the percentage by weight ranges shown, based on the total weight of such components:

fluoride source

 1-35%

organic amine(s)

20-60%

a nitrogenous component, selected from nitrogen-containing

0.1-40% 

carboxylic acids and imines

water

20-50%

and

metal chelating agent(s)

 0-21%

TOTAL

100%,

wherein said nitrogenous component includes a compound having the formula:

COOH—CH 2 —NRR′

wherein each of R and R′ is independently selected from the group consisting of hydrogen, alkyl, aryl, and carboxylic acids.