Cleaning agent for semiconductor provided with metal wiring
View Patent ↗A cleaning agent for a microelectronic device provided with metal wiring, which has an excellent ability to remove polishing particle residues derived from a polishing agent and an excellent ability to remove metallic residues on an insulating film, and has excellent anticorrosiveness to the metal wiring. The cleaning agent is used at a step subsequent to chemical mechanical polishing in a manufacturing process of a microelectronic device in which a metal wiring, e.g., copper or tungsten, is formed.
1. A composition comprising a cyclic polyamine, a polyphenol based reducing agent having 2 to 5 hydroxyl groups, a quaternary ammonium hydroxide, ascorbic acid, and water, wherein said composition is useful for the removal of material from a surface of a microelectronic device, wherein said microelectronic device comprises copper or copper alloy wiring, and wherein said cyclic polyamine is selected from the group consisting of N-ethylpiperazine, N-isobutylpiperazine, N-aminomethylpiperazine, N-aminopropylpiperazine, N-hydroxypropylpiperazine, 1 ,4-dimethylpiperazine, 1,4-diethylpiperazine, 1 ,4-diisopropylpiperazine, 1 ,4-dibutylpiperazine, 1 -aminomethyl-4-methylpiperazine, 1 -hydroxymethyl-4-methylpiperazine, 1 -aminoethyl-4-ethylpiperazine, 1-hydroxyethyl-4-ethylpiperazine, 1,4-(bisaminoethyl)piperazine, 1 ,4-bishydroxyethyl)piperazine, 1, 4-(bisaminopropyl)piperazine, 1 ,4-(bishydroxypropyl)piperazine, 1 -aminoethyl-4-hydroxyethylpiperazine, 1 -aminopropyl-4-hydroxypropylpiperazine, N-aminoisobutylmorpholine, and combinations thereof.
2. The composition of claim 1 , wherein the material comprises post-CMP residue and/or contaminants.
3. The composition according to claim 1 , wherein the polyphenol based reducing agent is selected from the group consisting of catechol, caffeic acid, alizarin, endocrocin, urushiol, flavone, resorcinol, hydroquinone, gallic acid, emodin, pyrogallol, quercetin, catechin, and anthocyanin.
4. The composition according to claim 1 , wherein the quaternary ammonium hydroxide is a quaternary ammonium hydroxide represented by the following general formula (6)
wherein, R 4 to R 7 each independently represent an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms.
5. The composition according to claim 4 , wherein the quaternary ammonium hydroxide comprises a species selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and (hydroxyethyl)trimethylammonium hydroxide.
6. The composition according to claim 1 , further comprising at least one corrosion inhibitor.
7. The composition according to claim 6 , wherein the corrosion inhibitor comprises at least one 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, methylated hydrolyzed diribose compounds; xylose, glucose, purine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, triaminopyrimidine, and combinations thereof
8. A method of removing post-CMP residue and/or contaminants from a microelectronic device having said residue and contaminants thereon, said method comprising contacting the microelectronic device with a composition for sufficient time to at least partially clean said residue and contaminants from the microelectronic device, wherein the microelectronic device comprises copper or copper alloy wiring, wherein said composition comprises a cyclic polyamine, a polyphenol based reducing agent having 2 to 5 hydroxyl groups, a quaternary ammonium hydroxide, ascorbic acid and water, wherein said cyclic polyamine is selected from the group consisting of N-ethylpiperazine, N-isobutylpiperazine, N-aminomethylpiperazine, N-aminopropylpiperazine, N-hydroxypropylpiperazine, 1,4-dimethylpiperazine, 1,4-diethylpiperazine, 1,4-diisopropylpiperazine, 1,4-dibutylpiperazine, 1 -aminomethyl-4-methylpiperazine, 1-hydroxymethyl-4-methylpiperazine, 1 -aminoethyl-4-ethylpiperazine, 1 -hydroxyethyl-4-ethylpiperazine, 1,4-(bisaminoethyl)piperazine, 1,4-(bishydroxyethyl)piperazine, 1,4-bisaminopropyl)piperazine, 1 ,4-(bishydroxypropyl)piperazine, 1 -amino ethyl-4-hydroxyethylpiperazine, 1 -aminopropyl-4-hydroxypropylpiperazine, N-aminoisobutylmorpholine, and combinations thereof.
9. A composition consisting of an organic amine, a quaternary ammonium hydroxide, a chelating agent, and water, having pH in the range of about 7.0 to about 14.0, wherein said organic amine comprises a species selected from the group consisting of ethylenediamine, propylenediamine, trimethylenediamine, tetramethlenediaine, hexamethylenediamine, 2-hydroxethlaminorolamine, diethanolaminopropylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine (TEP), hexamethyleneheptamine, iminobispropylamine, bis(hexamethylene)triamine, pentaethylenehexamine, and combinations thereof, wherein the chelating agent comprises a species selected from the group consisting of sodium pyrophosphate, sodium tripolyphosphate, potassium trimetaphosphate, sodium tetrametaphosphate, 1 -hydroxyethylidene-1,1-diphosphonic acid, dimethlglyoxime, 8-oxquinoline, phyrin, ethylenediamine diacetate and neutralized products of metal salts thereof (the metal is sodium, and potassium, for example), ethylenediamine tetraacetate (EDTA) and neutralized products of metal salts thereof, hexylenediamine diacetate and neutralized products of metal salts thereof, hydroxyethylimino diacetate and neutralized products of metal salts thereof, trisodium nitrilotriacetate, trisodium hydroxyethylethylenediaminetriacetate (HEDTA), pentasodium diethylenetriaminepentaacetate, hexasodium triethylenetetraminehexaacetate, dihydroxyethyl glycine, glycine, tetrasodium L-glutamate diacetate, oxalic acid, disodium malate, ethylene dicarboxylic acid, adipic acid, sebacic acid, gluconic acid, sodium gluconate, acetylacetone, hexane-2,4-dione, 3-ethylnonane-4,7-dione, sodium polyacrylate, poly[2-hydroxyacrylate sodium], and combinations thereof, and wherein said composition is useful for the removal of material from a surface of a microelectronic device, wherein said microelectronic device comprises tungsten or tungsten alloy wiring.
10. The composition of claim 9 , wherein the material comprises post-CMP residue and/or contaminants.
11. The composition according to claim 9 , wherein the organic amine is tetraethylenepentamine.
12. The composition of claim 9 , wherein the quaternary ammonium hydroxide is a quaternary ammonium hydroxide represented by a following general formula (3):
wherein, R 9 to R 12 each independently represent an alkyl group having 1 to 3 carbon atoms and that may be partially substituted by a hydroxyl group.
13. The composition according to claim 12 , wherein the quaternary ammonium hydroxide comprises a species selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and (hydroxyethyl)trimethylammonium hydroxide.
14. The composition according to claim 9 , wherein the chelating agent is ethylenediamine tetraacetate.
15. A method of removing post-CMP residue and/or contaminants from a microelectronic device having said residue and contaminants thereon, said method comprising contacting the microelectronic device with the composition of claim 9 for sufficient time to at least partially clean said residue and contaminants from the microelectronic device, wherein the microelectronic device comprises tungsten or tungsten alloy wiring.