COPPER CLEANING AND PROTECTION FORMULATIONS
A cleaning composition and process for cleaning post-chemical mechanical polishing (CMP) residue and contaminants from a microelectronic device having said residue and contaminants thereon. The cleaning compositions include novel corrosion inhibitors. The composition achieves highly efficacious cleaning of the post-CMP residue and contaminant material from the surface of the microelectronic device without compromising the low-k dielectric material or the copper interconnect material.
1 . A cleaning composition comprising at least one solvent, at least one corrosion inhibitor, at least one amine, and at least one quaternary base, wherein the corrosion inhibitor comprises a species selected from the group consisting of: ribosylpurines and methylated or deoxy derivatives thereof;
degradation products of adenosine and adenosine derivatives; purine-saccharide complexes; methylated or deoxy purine derivatives, and reaction or degradation products thereof; and combinations thereof.
2 . The cleaning composition of claim 1 , wherein the at least one corrosion inhibitor comprises a species selected from the group consisting of: N-ribosylpurine, adenosine, guanosine, 2-aminopurine riboside, 2-methoxyadenosine, N-methyladenosine, N,N-dimethyladenosine, trimethylated adenosine, trimethyl N-methyladenosine, C-4′-methyladenosine, 3-deoxyadenosine; adenine, methylated adenine, dimethylated adenine, N4,N4-dimethylpyrimidine-4,5,6-triamine, 4,5,6-triaminopyrimidine, allantoin, hydroxylated C—O—O—C dimers, C—C bridged dimers, ribose, methylated ribose, tetramethylated ribose, xylose, glucose, purine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, triaminopyrimidine, amino-substituted pyrimidines, and combinations thereof.
3 . The cleaning composition of claim 1 , wherein the at least one corrosion inhibitor comprises a species selected from the group consisting of adenosine, adenosine degradation products, and derivatives thereof.
4 . The cleaning composition of claim 1 any of the preceding claims, wherein the solvent comprises water.
5 . The cleaning composition of claim 1 , wherein the at least one quaternary base is selected from the group consisting of tetraethylammonium hydroxide (TEAH), tetramethyammonium hydroxide (TMAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), and combinations thereof any of the preceding claims, further comprising residue and contaminants, wherein the residue comprises post CMP residue, post etch residue, post ash residue, or combinations thereof.
6 . The cleaning composition of claim 1 any of the preceding claims, wherein the composition is diluted in a range from about 5:1 to about 200:1.
7 . The cleaning composition of claim 1 any of the preceding claims, wherein the composition is substantially devoid of at least one of oxidizing agents; fluoride-containing sources;
abrasive materials; an alcohol having an ether-bond in the molecule; alkylpyrrolidones; surface interaction enhancing agents; alkali and alkaline earth metal bases; sugar alcohols; corrosion inhibiting metal halides and combinations thereof; and wherein the cleaning compositions do not solidify to form a polymeric solid.
8 . The cleaning composition of claim 1 any of the preceding claims, wherein the at least one amine comprises at least one species selected from the group consisting of aminoethylethanolamine, N-methylaminoethanol, aminoethoxyethanol, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, monoethanolamine, triethanolamine, 1-amino-2-propanol, 2-amino-1-butanol, isobutanolamine, triethylenediamine, other C 1 -C 8 alkanolamines, tetraethylenepentamine (TEPA), 4-(2-hydroxyethyl)morpholine (HEM), N-aminoethylpiperazine (N-AEP), ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA), glycine/ascorbic acid, iminodiacetic acid (IDA), 2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, uric acid, glycine, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, 1-methoxy-2-aminoethane, and combinations thereof; and
9 . The cleaning composition of claim 1 , further comprising at least one additional component selected from the group consisting of at least one reducing agent, at least one complexing agent, at least one supplemental corrosion inhibitor, at least one alcohol, at least one surfactant, and NR 1 R 2 R 3 R 4 OH, where R 1 , R 2 , R 3 and R 4 can be the same as or different from one another and are selected from the group consisting of H, a methyl and an ethyl group, with the proviso that at least one of R 1 , R 2 , R 3 and R 4 must be H.
10 . The cleaning composition of claim 1 , further comprising at least one reducing agent selected from the group consisting of ascorbic acid, L(+)-ascorbic acid, isoascorbic acid, ascorbic acid derivatives, gallic acid, glyoxal, and combinations thereof.
11 . The cleaning composition of claim 1 , further comprising at least one complexing agent and at least one supplemental corrosion inhibitor.
12 . The cleaning composition of claim 1 , further comprising at least one reducing agent and at least one supplemental corrosion inhibitor.
13 . The cleaning composition of claim 12 , wherein the at least one supplemental corrosion inhibitor comprises a species selected from the group consisting of ascorbic acid, L(+)-ascorbic acid, isoascorbic acid, ascorbic acid derivatives, benzotriazole, citric acid, ethylenediamine, gallic acid, oxalic acid, tannic acid, 1,2,4-triazole (TAZ), tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5 -mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1,2,3-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazoles (halo=F, Cl, Br, I), naphthotriazole, 2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-aminotetrazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine, methyltetrazole, 1,3-dimethyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, imidazoline thione, mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl phosphate, imidazole, indiazole, benzoic acid, ammonium benzoate, catechol, pyrogallol, resorcinol, hydroquinone, cyanuric acid, barbituric acid and derivatives such as 1,2-dimethylbarbituric acid, pyruvic acid, phosphonic acid and derivatives thereof, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), propanethiol, benzohydroxamic acids, heterocyclic nitrogen inhibitors, potassium ethylxanthate, and combinations thereof.
14 . The cleaning composition of claim 11 , wherein the at least one complexing agent comprises a species selected from the group consisting of acetic acid, acetone oxime, acrylic acid, adipic acid, alanine, arginine, asparagine, aspartic acid, betaine, dimethyl glyoxime, formic acid, fumaric acid, gluconic acid, glutamic acid, glutamine, glutaric acid, glyceric acid, glycerol, glycolic acid, glyoxylic acid, histidine, iminodiacetic acid, isophthalic acid, itaconic acid, lactic acid, leucine, lysine, maleic acid, maleic anhydride, malic acid, malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic acid, phenylalanine, phthalic acid, proline, propionic acid, pyrocatecol, pyromellitic acid, quinic acid, serine, sorbitol, succinic acid, tartaric acid, terephthalic acid, trimellitic acid, trimesic acid, tyrosine, valine, xylitol, salts and derivatives thereof, and combinations thereof.
15 . A kit comprising, in one or more containers, one or more of the following reagents for forming a cleaning composition, wherein the cleaning composition comprises at least one solvent, at least one corrosion inhibitor, at least one amine, and at least one quaternary base, wherein the corrosion inhibitor comprises a species selected from the group consisting of: ribosylpurines and methylated or deoxy derivatives thereof; degradation products of adenosine and adenosine derivatives; purine-saccharide complexes; methylated or deoxy purine derivatives, and reaction or degradation products thereof; and combinations thereof.
16 . A method of removing residue and contaminants from a microelectronic device having said residue and contaminants thereon, said method comprising contacting the microelectronic device with a cleaning composition for sufficient time to at least partially clean said residue and contaminants from the microelectronic device, wherein the cleaning composition includes at least one solvent, at least one corrosion inhibitor, at least one amine, and at least one quaternary base, wherein the corrosion inhibitor comprises a species selected from the group consisting of: ribosylpurines and methylated or deoxy derivatives thereof; degradation products of adenosine and adenosine derivatives; purine-saccharide complexes; methylated or deoxy purine derivatives, and reaction or degradation products thereof; and combinations thereof.
17 . The method of claim 16 , wherein the at least one corrosion inhibitor comprises a species selected from the group consisting of: N-ribosylpurine, adenosine, guanosine, 2-aminopurine riboside, 2-methoxyadenosine, N-methyladenosine (C 11 H 15 N 5 O 4 ), N,N-dimethyladenosine (C 12 H 17 N 5 O 4 ), trimethylated adenosine (C 13 H 19 N 5 O 4 ), trimethyl N-methyladenosine (C 14 H 21 N 5 O 4 ), C-4′-methyladenosine, 3 -deoxyadenosine; adenine (C 5 H 5 N 5 ), methylated adenine, dimethylated adenine, N4,N4-dimethylpyrimidine-4,5,6-triamine (C 6 H 11 N 5 ), 4,5,6-triaminopyrimidine, allantoin (C 4 H 6 N 4 O 3 ), hydroxylated C—O—O—C dimers ((C 5 H 4 N 5 O 2 ) 2 ), C—C bridged dimers ((C 5 H 4 N 5 ) 2 and (C 5 H 4 N 5 O) 2 ), ribose (C 5 H 10 O 5 ), methylated ribose, tetramethylated ribose, xylose, glucose, purine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, triaminopyrimidine, amino-substituted pyrimidines, and combinations thereof.
18 . The method of claim 16 , further comprising diluting the cleaning composition with solvent at or before a point of use, wherein said solvent comprises water.