OXIDIZING AQUEOUS CLEANER FOR THE REMOVAL OF POST-ETCH RESIDUES

• US 20090215658A1
• Filed: 10/04/2006
• Published: 08/27/2009
• Est. Priority Date: 10/05/2005
• Status: Active Grant

• Current Assignee: Entegris Incorporated
• Original Assignee: Advanced Technology Materials, Inc. (Entegris Incorporated)
• Inventors: Korzenski, Michael B., Rajaratnam, Martha M., Minsek, David W.
• Granted Patent: US 7,922,824 B2
• Time in Patent Office: Days
• US Class Current: 510/175
• CPC Class Codes: C09G 1/02 containing abrasives or grinding agents abrasives as such C09K3/14; polishing of semi-conductors H01L
• CPC Class Codes: C11D 2111/22 Electronic devices, e.g. PCBs or semiconductors
• CPC Class Codes: C11D 3/33 Amino carboxylic acids
• CPC Class Codes: C11D 3/3942 Inorganic per-compounds C11D3/3902 takes precedence
• CPC Class Codes: C11D 7/06 Hydroxides
• CPC Class Codes: C11D 7/3209 Amines or imines with one to four nitrogen atoms; Quaternized amines
• CPC Class Codes: C23G 1/02 with acid solutions
• CPC Class Codes: C23G 1/061 nitrogen-containing compounds
• CPC Class Codes: C23G 1/103 copper or alloys of copper
• CPC Class Codes: C23G 1/106 refractory metals
• CPC Class Codes: C23G 1/18 Organic inhibitors
• CPC Class Codes: C23G 1/205 refractory metals
• 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: G03F 7/426 containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
• CPC Class Codes: H01L 21/02057 Cleaning during device manufacture
• CPC Class Codes: H01L 21/02063 the processing being the formation of vias or contact holes
• CPC Class Codes: H01L 21/31144 using masks
• CPC Class Codes: H01L 21/3212 by chemical mechanical polishing [CMP]
• CPC Class Codes: H01L 21/32134 by liquid etching only

Abstract

An oxidizing aqueous cleaning composition and process for cleaning post-plasma etch residue and/or hardmask material from a microelectronic device having said residue thereon. The oxidizing aqueous cleaning composition includes at least one oxidizing agent, at least one oxidizing agent stabilizer comprising an amine species selected from the group consisting of primary amines, secondary amines, tertiary amines and amine-N-oxides, optionally at least one co-solvent, optionally at least one metal-chelating agent, optionally at least one buffering species, and water. The composition achieves highly efficacious cleaning of the residue material from the microelectronic device while simultaneously not damaging the interlevel dielectric and metal interconnect material also present thereon.

Claims

1. An aqueous cleaning composition, comprising at least one oxidizing agent, at least one oxidizing agent stabilizer comprising an amine species selected from the group consisting of primary amines, secondary amines, tertiary amines and amine-N-oxides, optionally at least one organic co-solvent, optionally at least one metal-chelating agent, optionally at least one buffering species, and water, wherein said aqueous cleaning composition is suitable for cleaning post-plasma etch residue and/or hardmask material from a microelectronic device having said residue and/or hardmask thereon.

2. The aqueous cleaning composition of claim 1, wherein the pH of the composition is in a range from about 6 to about 8.

5. The aqueous cleaning composition of claim 1, wherein the at least one oxidizing agent comprises hydrogen peroxide.

6. The aqueous cleaning composition of claim 1, wherein the at least oxidizing agent stabilizer comprises an amine species selected from the group consisting of monoethanolamine, aminoethoxyethanol (diglycolamine), monoisopropanolamine, isobutanolamine, C₂-C₈ alkanolamines, methylethanolamine, N-methylaminoethanol, diethanolamine, triethanolamine, methyldiethanolamine, triethylamine, N,N-dimethylglycolamine, N,N-dimethyldiglycolamine, pentamethyldiethylenetriamine, N-methylmorpholine-N-oxide (NMMO), trimethylamine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide, N-ethylmorpholine-N-oxide, N-methylpyrrolidine-N-oxide, N-ethylpyrrolidine-N-oxide, substituted derivatives, and combinations thereof.

9. The aqueous cleaning composition of claim 1, comprising hydrogen peroxide and at least one amine-N-oxide.

10. The aqueous cleaning composition of claim 1, comprising the at least one metal chelating agent, wherein the metal chelating agent comprises a compound selected from the group consisting of 1,2,4-triazole (TAZ), benzotriazole, 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, naphthotriazole, 2-mercaptobenzoimidizole, 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, mercaptobenzothiazole, imidazoline thione, mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl phosphate, indiazole, ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N,N,N′

,N′

-tetraacetic acid (CDTA), and combinations thereof.

11. The aqueous cleaning composition of claim 1, comprising at least one organic co-solvent, wherein said organic co-solvent comprises a species selected from the group consisting of ethylene glycol, propylene glycol (PG), neopentyl glycol, 1,3-propanediol, diethyleneglycol, dipropyleneglycol, glycerol, formamide, acetamide, higher amides, N-methylpyrrolidone (NMP), N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, dimethylsulfoxide (DMSO), γ

-butyrolactone, propylene carbonate, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (i.e., butyl carbitol), triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, and combinations thereof.

13. The aqueous cleaning composition of claim 1, comprising the at least one buffering species, wherein the buffering species comprises a tetralkylammonium cation compound and an acid anion compound.

14. The aqueous cleaning composition of claim 13, wherein the tetralkylammonium cation compound includes a tetralkylammonium cation represented by the formula [NR¹R²R³R⁴]⁺, where R¹, R², R³ and R⁴ may be the same as or different from one another and are selected from the group consisting of straight-chained C₁-C₆ alkyls, branched C₁-C₆ alkyls, substituted C₆-C₁₀ aryls, unsubstituted C₆-C₁₀ aryls, and combinations thereof, and wherein the acid anion compound is selected from the group consisting of lactic acid, maleic acid, ascorbic acid, malic acid, benzoic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, mandelic acid, maleic anhydride, citric acid, phthalic acid, boric acid other aliphatic and aromatic carboxylic acids, and combinations of the foregoing acids.

17. The aqueous cleaning composition of claim 13, comprising a tetralkylammonium salt of boric acid.

19. The aqueous cleaning composition of claim 1, comprising at least one organic co-solvent, at least one metal chelating agent, and at least one buffering species, wherein the aqueous cleaning composition comprises hydrogen peroxide, at least one amine-N-oxide, at least one glycol ether, 1,2-cyclohexanediamine-N,N,N′

,N′

-tetraacetic acid, tetramethylammonium hydroxide and boric acid.

21. The aqueous cleaning composition of claim 1, wherein said aqueous composition further comprises post-plasma etch residue selected from the group consisting of titanium-containing residue, polymeric residue, copper-containing residue, and combinations thereof.

23. The aqueous cleaning composition of claim 1, wherein the aqueous composition is devoid of abrasive material selected from the group consisting of silica, alumina, ceria, and combinations thereof.

3-4. -4. (canceled)

7-8. -8. (canceled)

12. (canceled)

15-16. -16. (canceled)

18. (canceled)

20. (canceled)

22. (canceled)

24. A kit comprising, in one or more containers, one or more of the following reagents for forming an aqueous cleaning composition, said one or more reagents selected from the group consisting of at least one oxidizing agent, at least one oxidizing agent stabilizer comprising an amine species selected from the group consisting of primary amines, secondary amines, tertiary amines and amine-N-oxides, optionally at least one co-solvent, optionally at least one chelating agent, optionally at least one buffering species, and water, and wherein the kit is adapted to form an aqueous cleaning composition suitable for cleaning post-plasma etch residue and/or hardmask material from a microelectronic device having said residue and/or material thereon.

25. A method of removing post-plasma etch residue and/or hardmask material from a microelectronic device having said residue and/or hardmask thereon, said method comprising contacting the microelectronic device with an aqueous cleaning composition for sufficient time to at least partially clean said residue and/or hardmask from the microelectronic device, wherein the aqueous cleaning composition includes at least one oxidizing agent, at least one oxidizing agent stabilizer comprising an amine species selected from the group consisting of primary amines, secondary amines, tertiary amines and amine-N-oxides, optionally at least one organic co-solvent, optionally at least one metal-chelating agent, optionally at least one buffering species, and water.

28. The method of claim 25, wherein said contacting comprises conditions selected from the group consisting of time in a range from about 1 minute to about 60 minutes;

temperature in a range of from about 30°

C. to about 50°

C.; and

combinations thereof.

35. The method of claim 25, wherein the microelectronic device comprises a layer selected from the group consisting of a titanium-containing layer, an interlevel dielectric layer, and combinations thereof.

37. The method of claim 25, wherein the contacting comprises a process selected from the group consisting of:

spraying the aqueous composition on a surface of the microelectronic device;

dipping the microelectronic device in a sufficient volume of aqueous composition;

contacting a surface of the microelectronic device with another material that is saturated with the aqueous composition; and

contacting the microelectronic device with a circulating aqueous composition.

38. The method of claim 25, further comprising rinsing the microelectronic device with deionized water following contact with the aqueous composition.

39. The method of claim 25, further comprising contacting the microelectronic device with dilute hydrofluoric acid.

26-27. -27. (canceled)

29-34. -34. (canceled)

36. (canceled)

40-48. -48. (canceled)