Antioxidants for post-CMP cleaning formulations
View Patent ↗An 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 method of removing post-chemical mechanical polishing (CMP) residue from a microelectronic device having said post-CMP residue thereon, said method comprising contacting the microelectronic device with a cleaning composition for sufficient time to at least partially clean said post-CMP residue from the microelectronic device, wherein the cleaning composition includes at least one solvent, at least one corrosion inhibitor, and at least one amine, wherein the corrosion inhibitor comprises a species selected from the group consisting of barbituric acid and derivatives thereof, glucuronic acid, squaric acid, alpha-keto acids, adenosine and derivatives thereof, guanine, hypoxanthine, xanthine, theobromine, caffeine, isoguanine, phenanthroline/ascorbic acid, nicotinamide and derivatives thereof, flavonols and derivatives thereof, anthocyanins and derivatives thereof, flavonol/anthocyanin, and combinations thereof.
2. The method of claim 1 , wherein the cleaning composition further comprises at least one quaternary base.
3. The method of claim 1 , wherein said contacting comprises conditions selected from the group consisting of: time of from about 1 second to about 20 minutes; temperature in a range of from about 20° C. to about 90° C.; and combinations thereof.
4. The method of claim 1 , wherein the microelectronic device comprises an article selected from the group consisting of semiconductor substrates, flat panel displays, phase change memory devices, solar panels and other products including solar substrates, photovoltaics, and microelectromechanical systems (MEMS).
5. The method of claim 1 , further comprising diluting the cleaning composition with diluent at or before a point of use, wherein the composition is diluted in a range from about 5:1 to about 200:1.
6. The method of claim 4 , wherein said diluent comprises water.
7. The method of claim 1 , further comprising rinsing the microelectronic device with deionized water following contact with the cleaning composition.
8. The method of claim 1 , wherein the cleaning composition further comprises at least one additional component selected from the group consisting of: at least one quaternary base; at least one complexing agent; at least one surfactant; at least one reducing agent; at least one dispersing agent; at least one sulfonic acid-containing hydrocarbon; at least one alcohol; and combinations thereof.
9. The method of claim 1 , wherein the cleaning composition further comprises at least one embodiment (i) through (viii):
(i) at least one quaternary base, and optionally at least one reducing agent;
(ii) at least one quaternary base, and at least one complexing agent;
(iii) at least one surfactant, and optionally at least one reducing agent;
(iv) at least one reducing agent, optionally at least one surfactant, and optionally at least one quaternary base;
(v) at least one quaternary base, at least one reducing agent, and optionally at least one surfactant;
(vi) at least one quaternary base and uric acid;
(vii) at least one quaternary base, uric acid, and at least one alcohol; and
(viii) at least one quaternary base and at least one alcohol.
10. The method of claim 1 , wherein the solvent comprises water.
11. The method of claim 1 , wherein the pH of the cleaning composition is in a range from about 8.5 to about 11.5.
12. The method of claim 1 , wherein the cleaning composition is substantially devoid of oxidizing agent, fluoride source, and/or abrasive material prior to removal of residue material from the microelectronic device.
13. The method of claim 1 , wherein the cleaning composition further comprises at least one additional corrosion inhibitor, wherein the at least one additional 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, ethylenediaminetetraacetic acid (EDTA), uric 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-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 or 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, alpha-keto acids such as pyruvic acid, adenine, purine, phosphonic acid and derivatives thereof, glycine/ascorbic acid, and combinations thereof.
14. The method of claim 1 , wherein the at least one amine has the general formula NR 1 R 2 R 3 , where R 1 , R 2 and R 3 may be the same as or different from one another and are selected from the group consisting of hydrogen, straight-chained C 1 -C 6 alkyl, branched C 1 -C 6 alkyl, straight-chained C 1 -C 6 alcohol, and branched C 1 -C 6 alcohol.
15. The method of claim 2 , wherein the at least one quaternary base has the formula NR 1 R 2 R 3 R 4 OH, wherein R 1 , R 2 , R 3 and R 4 may be the same as or different from one another and are selected from the group consisting of hydrogen, straight-chained C 1 -C 6 alkyl, branched C 1 -C 6 alkyl, substituted C 6 -C 10 aryl, and unsubstituted C 6 -C 10 aryl.
16. The method of claim 8 , comprising at least one alcohol, wherein the at least one alcohol comprises straight-chained or branched C 1 -C 6 alcohols.
17. The method of claim 14 , wherein the at least one amine comprises a 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 i -C 8 alkanolamines and combinations thereof.
18. The method of claim 15 , wherein the at least one quaternary base comprises a species 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.
19. The method of claim 1 , wherein the at least one corrosion inhibitor comprises adenosine and derivatives thereof.