Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – For cleaning a specific substrate or removing a specific...
Reexamination Certificate
2002-10-23
2004-12-14
Webb, Gregory (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
For cleaning a specific substrate or removing a specific...
C510S176000, C510S255000, C134S003000, C134S002000
Reexamination Certificate
active
06831048
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a cleaning composition for use in the process of producing a semiconductor. Specifically the invention relates to a composition which can be used in cleaning a metal gate, a contact hole, a via hole, a capacitor or the like, in removing a polymer derived from a resist and in cleaning after CMP. More specifically, the invention relates to a cleaning composition which can be suitably used in producing a semiconductor device or a liquid crystal panel device such as IC, LSI or the like.
BACKGROUND ART
Conventionally poly-Si has been used as a material for a gate electrode in a semiconductor device. With microminiaturization, there is a possibility of using tungsten, copper, aluminum or like metals as a material for a gate electrode. Now SPM (H
2
SO
4
—H
2
O
2
—H
2
O), APM (NH
4
OH—H
2
O
2
—H
2
O), HPM(HCl—H
2
O
2
—H
2
O), DHF(HF—H
2
O), etc. are used as a cleaning composition for cleaning a gate, a contact hole, a capacitor or the like. However, these compositions easily corrode metals so that there is a demand for a cleaning composition which is unlikely to corrode metals and which can remove a polymer derived from a resist, a native oxide and the like.
When a semiconductor device or a liquid crystal panel device such as IC or LSI is produced, the following steps are carried out. A photo-resist is uniformly applied to a film of electroconductive metal such as aluminum, copper, aluminum-copper alloy or the like or to an insulating film such as SiO
2
film, each formed on a substrate. Then a resist pattern is formed by lithography technique, and the electroconductive metal film or the insulating film is selectively etched. After etching, a residual resist is removed by ashing, by polymer removing composition and the like.
Known polymer-removing compositions include, for example, those comprising an aqueous solution of a fluoride salt, a water-soluble organic solvent such as DMF, DMSO or the like and optionally hydrofluoric acid as disclosed in Japanese Unexamined Patent Publications No.197681/1997 and No.47401/2000. However, it is difficult for a polymer-removing composition to satisfy two requirements, i.e. a low property of corroding a metal and a high ability of removing a polymer. Thus, conventional polymer-removing compositions remain to be improved in the balance of the two requirements.
With increased complexity of element structure of IC and progress of multi-level interconnection, single damascene or dual damascene process is carried out in formation of interconnection. The damascene process includes polishing (CMP: Chemical Mechanical Polishing) a surface of the article using an abrasive so that numerous particles derived from the abrasive adhere to the surface of the article after damascene process, and particles may become lodged in the surface of the film during polishing. After conventional CMP of oxide film, the article is cleaned with a brush using a cleaning composition such as DHF(HF—H
2
O), APM (NH
4
OH—H
2
O
2
—H
2
O) or the like. However, metals such as Al, Al—Cu, Cu or TiN exist on the surface of the article in damascene process. Thus the above-mentioned cleaning composition is difficult to use because the composition is likely to corrode the metal surface.
DISCLOSURE OF THE INVENTION
An object of the present invention is to provide a cleaning composition which shows a low property of corroding metals and an ability of removing a polymer, a native oxide and the like and which is usable for cleaning a metal gate, a contact hole, a via hole, a capacitor or the like.
Another object of the invention is to provide a polymer-removing composition which can be suitably used in producing a semiconductor device or a liquid crystal panel device such as IC or LSI and which shows a low property of corroding a metal and a high capacity of removing a polymer.
A further object of the invention is to provide a cleaning composition which can remove slurry particles from the surface of an article after CMP in single damascene and dual damascene process and which shows a low property of corroding metals or substrates of Al, Al—Cu, Cu, TiN and the like which are likely to corrode.
The present invention includes the subject matters defined in the following items.
Item 1. A cleaning composition comprising (1) at least one of fluoride salts and hydrogendifluoride salts; (2) an organic solvent having a hetero atom or atoms; and (3) water.
Item 2. The cleaning composition according to item 1, wherein at least one of fluoride salts and hydrogendifluoride salts is formed from hydrofluoric acid and at least one member selected from the group consisting of ammonia, hydroxylamines, aliphatic amines, aromatic amines and aliphatic or aromatic quaternary ammonium salts.
Item 3. The cleaning composition according to item 1, wherein (2) the organic solvent having a hetero atom or atoms is at least one member selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone; methanol, ethanol, isopropyl alcohol (IPA), 1-propanol, 1-butanol, 2-butanol, t-butanol, 2-methyl-1-propanol, 1-pentanol, 1-hexanol, 1-heptanol, 4-heptanol, 1-octanol, 1-nonylalcohol, 1-decanol, 1-dodecanol and like alcohols; ethylene glycol, 1,2-propanediol, propylene glycol, 2,3-butanediol, glycerin and like polyols; acetone, acetylacetone, methyl ethyl ketone and like ketones; acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and like nitriles; formaldehyde, acetaldehyde, propionaldehyde and like aldehydes; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether and like alkylene glycol monoalkyl ethers; tetrahydrofuran, dioxane and like cyclic ethers; trifluoroethanol, pentafluoropropanol, 2,2,3,3-tetrafluoropropanol and like fluoroalcohols; sulfolane and nitromethane.
Item 4. The cleaning composition according to item 3, wherein (2) the organic solvent having a hetero atom or atoms is at least one oxygen-containing organic solvent selected from the group consisting of alcohols and ketones.
Item 5. The cleaning composition according to item 4, wherein (2) the oxygen-containing organic solvent is at least one member selected from the group consisting of isopropyl alcohol, ethanol and methanol, and the concentration of water is 10% by mass or lower.
Item 6. The cleaning composition according to item 4, wherein (2) the oxygen-containing organic solvent is acetone and the concentration of water is 20 to 40% by mass.
Item 7. The cleaning composition according to item 1, which comprises (1) a fluoride salt represented by NR
4
F (wherein Rs are the same or different and each is a straight-chain or branched-chain alkyl group of 1 to 12 carbon atoms which may be substituted with a fluorine atom or atoms, a phenyl group which may be substituted with a fluorine atom or atoms, or a hydrogen atom) in a concentration of 1% by mass or lower and/or a hydrogendifluoride salt represented by NR
4
HF
2
(wherein Rs are as defined above) in a concentration of 0.001 to 1% by mass; (3) water in a concentration of 10% by mass or lower; and (2) at least one member selected from the group consisting of isopropyl alcohol, ethanol and methanol as the remainder.
Item 8. The cleaning composition according to item 1, wherein a fluoride salt represented by NR
4
F (wherein Rs are the same or different and each is a straight-chain or branched-chain alkyl group of 1 to 12 carbon atoms which may be substituted with a fluorine atom or atoms, a phenyl group which may be substituted with a fluorine atom or atoms, or a hydrogen atom) in a concentration of 1% by mass or lower and/or a hydrogendifluoride salt represented by NR
4
HF
2
(wherein R is as defined above) in a concentration of 0.001 to 1% by mass; (3) water in a concentration of 20 to 40% by mass; and (2) acetone as the remainder.
Item 9. The cleaning composition according to item 1, which further comprises (4) at least one member selected from the group consisting of an anionic surfactant, a c
Itano Mitsushi
Kezuka Takehiko
Armstrong Kratz Quintos Hanson & Brooks, LLP
Daikin Industries Ltd.
Webb Gregory
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