AQUEOUS AND SEMI-AQUEOUS CLEANERS FOR THE REMOVAL OF POST-ETCH RESIDUES WITH TUNGSTEN AND COBALT COMPATIBILITY

• US 20170200601A1
• Filed: 06/24/2015
• Published: 07/13/2017
• Est. Priority Date: 06/30/2014
• Status: Active Application

• Current Assignee: Entegris Incorporated
• Original Assignee: Entegris Incorporated
• Inventors: SONG, Lingyan, LIPPY, Steven, COOPER, Emanuel I.
• Application Number:
  US15/324,588
• Publication Number:
  US 20170200601A1
• Time in Patent Office: Days
• CPC Class Codes: B08B 3/08 the liquid having chemical or dissolving effect substances used, see the relevant classes
• CPC Class Codes: C11D 1/008 Polymeric surface-active agents
• CPC Class Codes: C11D 1/667 Neutral esters, e.g. sorbitan esters
• CPC Class Codes: C11D 2111/22 Electronic devices, e.g. PCBs or semiconductors
• CPC Class Codes: C11D 3/042 Acids
• CPC Class Codes: C11D 3/046 Salts
• CPC Class Codes: C11D 3/245 containing fluorine
• CPC Class Codes: C11D 3/30 Amines; Substituted amines ; Quaternized amines
• CPC Class Codes: C11D 3/361 Phosphonates, phosphinates or phosphonites
• CPC Class Codes: C11D 3/3707 Polyethers, e.g. polyalkyleneoxides
• CPC Class Codes: C11D 3/43 Solvents
• CPC Class Codes: C11D 7/08 Acids
• CPC Class Codes: C11D 7/10 Salts
• CPC Class Codes: C11D 7/28 containing halogen
• CPC Class Codes: H01L 21/02063 the processing being the formation of vias or contact holes
• CPC Class Codes: H01L 21/02068 during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers

Abstract

Cleaning compositions and processes for cleaning post-plasma etch residue from a microelectronic device having said residue thereon. The composition achieves highly efficacious cleaning of the residue material, including titanium-containing, copper-containing, tungsten-containing, and/or cobalt-containing post-etch residue from the microelectronic device while simultaneously not damaging the interlevel dielectric, metal interconnect material, and/or capping layers also present thereon.

Claims

1. An aqueous cleaning composition, comprising at least one non-ionic surfactant corrosion inhibitor, at least one etchant source, at least one passivating agent, water, optionally at least one organic solvent, optionally at least one buffering species, optionally at least one additional corrosion inhibitor, and optionally at least one oxidizing agent, wherein said aqueous cleaning composition is suitable for cleaning post-plasma etch residue from a microelectronic device having said residue thereon.

2. The cleaning composition of claim 1, wherein the post-plasma etch residue comprises residue selected from the group consisting of titanium-containing compounds, polymeric compounds, copper-containing compounds, tungsten-containing compounds, cobalt-containing compounds, and combinations thereof.

3. The cleaning composition of any of claim 1 or 2, wherein the at least one etchant comprises a fluoride species selected from the group consisting of hydrofluoric acid, fluoroboric acid, tetramethylammonium hexafluorophosphate, ammonium fluoride, ammonium bifluoride, tetrabutylammonium tetrafluoroborate, tetratnethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, and combinations thereof.

4. The cleaning composition of any of the preceding claims, wherein the at least one etchant comprises a fluoride selected from the group consisting of ammonium bifluoride, ammonium fluoride, and combinations thereof.

5. The cleaning composition of any of the preceding claims, wherein the at least one passivating agent comprises a species selected from the group consisting of boric acid, 3-hydroxy-2-naphthoic acid, malonic acid, iminodiacetic acid, ammonium pentaborate, urea, methyltriethoxysilane, and mixtures thereof.

6. The cleaning composition of any of the preceding claims, wherein the at least one passivating agent comprises boric acid.

7. The cleaning composition of any of the preceding claims, wherein the at least one non-ionic surfactant corrosion inhibitor comprises a species selected from the group consisting of poly(ethylene glycol), poly(propylene glycol), ethylene oxide/propylene oxide block copolymers, a polysorbate, polyoxypropylene/polyoxyethylene block copolymers, and combinations thereof.

8. The cleaning composition of claim 7, wherein the at least one non-ionic surfactant corrosion inhibitor comprises a polysorbate.

9. The cleaning composition of claim 8, wherein the at least one non-ionic surfactant corrosion inhibitor comprises polyoxyethylene (20) sorbitan monooleate (Tween 80), polyoxyethylene (20) sorbitan monostearate (Tween 60), polyoxyethylene (20) sorbitan monopalmitate (Tween 40), polyoxyethylene (20) sorbitan monolaurate (Tween 20)

10. The cleaning composition of any of the preceding claims, comprising at least one additional corrosion inhibitor selected from the group consisting of 5-aminotetrazole, 5-phenyl-benzotriazole, 1H-tetrazole-5-acetic acid, 1-phenyl-2-tetrazoline-5-thione, benzimidazole, methyltetrazole, Bismuthiol I, cytosine, guanine, thymine, pyrazoles, iminodiacetic acid (IDA), propanethiol, benzohydroxamic acids, citric acid, ascorbic acid, 5-amino-1,3,4-thiadiazole-2-thiol (ATDT), benzotriazole (BTA), 1,2,4-triazole (TAZ), tolyltriazole, 5-methyl-benzotriazole (mBTA), 5-phenyl-benzotriazole, 5-nitro-benzotriazole, benzotriazole carboxylic acid, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole (3-ATA), 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-mercaptobenzimidazoic (MBI), 2-mercaptobenzothiazole, 4-methyl -2-phenylimidazole, 2-mercaptothiazoline, 5-amino-1,2,4-triazole (5-ATA), sodium dedecyl sulfate (SDS), ATA-SDS, 3-amino-5-mercapto-1,2,4-triazole, pentylenetetrazole, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, Ablutnine O, 2-benzylpyridine, succinimide, 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, 4-methyl-4H-1,2,4-triazole-3-thiol, 4-amino-4H-1,2,4-triazole, 3-amino-5-methylthio-1H-1,2,4-triazole, benzothiazole, imidazole, indiazole, adenine, succinimide, adenosine, carbazole, saccharin, uric acid, and benzoin oxime. benzalkonium chloride, benzyldimethyldodecylammonium chloride, myristyltrimethylammonium bromide, dodecyltrimethylammonium. bromide, hexadecylpyridinium chloride, Aliquat 336, benzyldimethylphenylammonium chloride, Crodaquat TES, Rewoquat CPEM, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 1-methyl-1′

-tetradecyl-4,4′

-bipyridium dichloride, alkyltrimethylammonium bromide, amprolium hydrochloride, benzethonium hydroxide, benzethonium chloride, benzyldimethylhexadecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzyldodecyldimethylammonium bromide, benzyldodecyldimethylammonium chloride, cetylpyridinium chloride, choline p-toluenesulfonate salt, dimethyldioctadecylammonium bromide, dodecylethyldimethylammonium bromide, dodecyltrimethylammonium chloride, ethylhexadecyldimethylammonium bromide, Girard'"'"'s reagent, hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate, dexadecylpyridinium bromide, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, methylbenzethonium chloride, N,N′

, N′

-polyoxyethylene (10)-N-tallow-1,3-diaminopropane liquid, oxyphenonium bromide, tetraheptylammonium bromide, tetrakis(decyl)ammonium bromide, thonzonium bromide, tridodecylammonium chloride, trimethyloctadecylammonium bromide, 1 -methyl-3-n-octylimidazolium tetrafluoroborate, 1-decyl-3-methylimidazolium tetrafluoroborate, 1-decyl-3-methylimidazolium chloride, tridodecylmethylammonium bromide, dimethyldstearylammonium chloride, cetyltrimethylammonium bromide, myristyltrimethylammonium bromide, hexamethonium chloride, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, dodecylphosphonic acid (DDPA), and combinations thereof.

11. The cleaning composition of any of the preceding claims, wherein the amount of water is in a range from about 50 wt % to about 99.5 wt %, based on the total weight of the composition.

12. The cleaning composition of any of the preceding claims, wherein the pH is in a range from about 6 to about 10.

13. The cleaning composition of any of the preceding claims, wherein the pH is in a range from about 8 to about 13.

14. The cleaning composition of any of the preceding claims, wherein the composition is substantially devoid of abrasive material and alkali and alkaline earth metal hydroxide salts.

15. The cleaning composition of any of the preceding claims, wherein the composition further comprises at least one buffering agent.

16. The cleaning composition of any of the preceding claims, wherein the composition further comprises at least one organic solvent.

17. The cleaning composition of any of the preceding claims, wherein the composition further comprises at least one oxidizing agent.

18. The cleaning composition of any of the preceding claims, wherein said composition further comprises post-plasma etch residue selected from the group consisting of titanium-containing residue, polymeric-residue, copper-containing residue, tungsten-containing residue, cobalt-containing residue, and combinations thereof.

19. A method of removing material from a microelectronic device having said material thereon, said method comprising contacting the microelectronic device with an aqueous cleaning composition of any of claims 1-18 for sufficient time to at least partially remove said material from the microelectronic device.

20. The method of claim 19, wherein the material comprises post-plasma etch residue comprising residue selected from the group consisting of titanium-containing compounds, polymeric compounds, copper-containing compounds, tungsten-containing compounds, cobalt-containing compounds, and combinations thereof.

21. The method as in any of claims 19-20, wherein said contacting comprises conditions selected from the group consisting of:

time of from about 1 minute to about 30 minutes;

temperature in a range of from about 40°

C. to about 70°

C.; and

combinations thereof.