Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – For cleaning a specific substrate or removing a specific...
Reexamination Certificate
2002-10-25
2004-08-10
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...
C510S175000, C510S202000, C510S212000, C510S499000, C134S038000
Reexamination Certificate
active
06774097
ABSTRACT:
CROSS REFERENCE TO RELATED APPLICATION
This application is based on application No. 2000-22221 filed in the Korean Industrial Property Office on Apr. 26, 2000, the content of which is incorporated hereinto by reference.
BACKGROUND OF THE INVENTION
(a) Field of the Invention
The present invention relates to a resist stripper composition for removing resists during a manufacturing process of semiconductor devices, such as large size integrated circuits (LSI) and very large size integrated circuits (VLSI).
(b) Description of the Related Art
Generally, manufacturing processes of semiconductor devices employ dozens of lithography processes which comprise forming a resist pattern on a conductive layer formed on a semiconductor substrate, and then etching a part of the conductive layer that is not covered by the pattern using the pattern as a mask to remove the part, thereby forming a conductive layer pattern. The resist pattern used as a mask must be removed from the conductive layer by a resist stripper during a stripping process after the conductive layer pattern forming process. However, since in recent very large size integrated circuit semiconductor manufacturing, a dry etching process for forming conductive patterns has been conducted, it becomes difficult to remove resists in the subsequent stripping process.
In the dry etching process, which replaces a wet etching process using liquid phase composition of mixed acids, the etching process is conducted using a gas phase-solid phase reaction between plasma etching gases and layers such as the conductive layer. Dry etching forms the main-stream of recent etching processes, because it is easy to control and can obtain sharp patterns. However, since during the dry etching process, ions and radicals of plasma etching gases cause complex chemical reactions with the resist film and rapidly cure the resist, it becomes difficult to remove the resist. Particularly, in the case of dry etching of metal conductive layers such as aluminum, aluminum alloy and titanium nitride, modified and cured resist polymers are generated on side wall parts and they are difficult to remove during the stripping process.
A variety of resist stripper compositions comprising organic amine compounds and organic solvents have been suggested for the stripping process, and particularly, a resist stripper composition comprising monoethanolamine (MEA) as an essential ingredient is most commonly used.
As examples, a two-component system resist stripper composition comprising a) organic amine compounds such as monoethanolamine (MEA), 2-(2-aminoethoxy)ethanol (AEE), etc., and b) polar solvents such as N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), carbitol acetate, methoxyacetoxypropane, etc. (U.S. Pat. No. 4,617,251); a two-component system resist stripper composition comprising a) organic amine compounds such as monoethanolamine (MEA), monopropanolamine, methylamylethanol, etc., and b) amide solvents such as N-methylacetamide (Mac), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N,N-dimethylpropionamide, N,N-diethylbutylamide, N-methyl-N-ethylpropionamide, etc. (U.S. Pat. No. 4,770,713); a two-component system resist stripper composition comprising a) organic amine compounds such as monoethanolamine (MEA), and b) non-protonic polar solvents such as 1,3-dimethyl-2-imidazolidinon (DMI), 1,3-dimethyl-tetrahydropyrimidinon, etc. (German Laid-Open Patent Application No. 3,828,513); a resist stripper composition comprising a) ethylene oxide—introduced alkylene polyamines of alkanol amines such as monoethanolamine (MEA), diethanol amine (DEA), triethanolamine (TEA), etc., and ethylenediamine, b) sulfone compounds such as sulforane, etc., and c) glycol monoalkyl ethers such as diethylene glycol monoethyl ether, diethylene glycolmonobutyl ether, etc., in a specific ratio (Japanese Laid-open Patent Publication No. Sho 62-49355); a resist stripper composition comprising a) water soluble amines such as monoethanol amine (MEA), diethanolamine (DEA), etc., and b) 1,3-dimethyl-2-imidazolidinone (Japanese Laid-open Patent Publication No. Sho 63-208043); a positive resist stripper composition comprising a) amines such as monoethanolamine (MEA), ethylenediamine, piperidine, benzyl amine, etc., b) polar solvents such as DMAc, NMP, DMSO, etc., and c) a surfactant (Japanese Laid-open Patent Publication No. Sho 63-231343); a positive resist stripper composition comprising a) nitrogen-containing organic hydroxy compounds such as monoethanolamine (MEA), b) one or more solvents selected from diethylene glycol monoethyl ether, diethyleneglycol dialkyl ether, &ggr;-butyrolactone and 1,3-dimethyl-2-imidazolinone, and c) DMSO in a specific ratio (Japanese Laid-open Patent Publication No. Sho 64-42653); a positive resist stripper composition comprising a) organic amine compounds such as monoethanol amine (MEA), etc., b) a non-protonic polar solvent such as diethylene glycol monoalkyl ether, DMAc, NMP, DMSO, etc., and c) a phosphate ester surfactant (Japanese Laid-open Patent Publication No. Hei 4-124668); a resist stripper composition comprising a) 1,3-dimethyl-2-imidazolinon (DMI), b) dimethylsulfoxide (DMSO), and c) organic amine compounds such as monoethanol amine (MEA), etc. (Japanese Laid-open Patent Publication No. Hei 4-350660); and a resist stripper composition comprising a) monoethanol amine (MEA), b) DMSO, and c) catechol (Japanese Laid-open Patent Publication NO. Hei 50281753) have been suggested and these resist stripper compositions show relatively good properties in terms of their stabilities, processabilities and resist removing performances.
Meanwhile, one of the recent tendencies of semiconductor device manufacturing processes is treating various substrates including a silicon wafer at a high temperature, i.e., making the temperature conditions of a hard-bake process high. However, said resist strippers do not have sufficient capability for removing resists that are hard-baked at a high temperature. As compositions for removing the hard-baked resists, aqueous resist strippers containing water have been suggested. As examples, a resist stripper composition comprising a) hydroxylamines, b) alkanol amines, and c) water (Japanese Laid-open Patent Publication No. Hei 4-289866; a resist stripper composition comprising a) hydroxylamines, b) alkanol amines, c) water and d) an anti-corrosive (Japanese Laid-open Patent Publication No. Hei 6-266119); a resist stripper composition comprising a) polar solvents such as GBL, DMF, DMAc, NMP, etc., b) aminoalcohols such as 2-methylaminoethanol, and c) water (Japanese Laid-open Patent Publication No. Hei 7-69618); a stripper composition comprising a) aminoalcohols such as monoethanolamine (MEA), b) water, and c) butyldiglycol (Japanese Laid-open Patent Publication No. Hei 8-123043); a resist stripper composition comprising a) alkanolamines, alkoxyamines, b) glycol monoalkyl ether, c) sugar alcohols, d) quaternary ammonium hydroxide, and e) water (Japanese Laid-open Patent Publication No. Hei 8-262746); a stripper composition comprising a) one or more alkanolamines of monoethanolamine (MEA) or AEE, b) hydroxylamine, c) diethyleneglycol monoalkyl ether, d) sugars (sorbitol), and e) water (Japanese Laid-open Patent Publication No. Hei 9-152721); a resist stripper composition comprising a) hydroxylamines, b) water, c) amines having an acid dissociation constant (pKa) of 7.5 to 13, d) water soluble organic solvent, and e) an anticorrosive (Japanese Laid-open Patent Publication No. Hei 9-96911) have been suggested. However, it has been found that these stripper compositions also cannot sufficiently remove side wall resist polymers that are exposed to and modified by plasma gases during dry etching or an ashing process used to manufacture very large size integrated circuits. Accordingly, there is a need for the development of a resist stripper that can be used in the dry etching process so as to solve these problems.
As explained, resists that has been passed dry etching proce
Lee Sang-Dai
Oh Chang-Il
Park Young-Woong
Yoo Chong-Soon
Yoon Suk-Il
Baker & Botts LLP
Dongjin Semichem Co., Ltd.
Webb Gregory
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