Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2001-02-28
2003-04-29
Mullis, Jeffrey (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S376000, C524S377000, C524S378000, C524S379000, C525S056000, C525S058000, C525S156000, C525S157000
Reexamination Certificate
active
06555607
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a novel water-soluble resin composition and a fine pattern-forming material comprising the water-soluble resin composition. In particular, the present invention relates to a water-soluble resin composition which is coated on resist patterns formed and then crosslinked for thickening the resist patterns to fine effectively trench patterns or hole patterns and reduce the size of a space in the resist patterns without investment in expensive facilities such as an exposure unit for short wavelengths or a phase-shift reticle in a process for producing semiconductor devices etc., and a fine pattern-forming material comprising said water-soluble resin composition.
PRIOR ART
Photolithographic techniques has been traditionally used for the formation of fine elements or the fine processing in many fields such as the fabrication of semiconductor integrated circuits such as an LSI, the production of the display plane of a liquid crystal display device in an LCD panel, and the production of a circuit substrate for a thermal head and the like. To form resist patterns by photolithographic techniques, various positive- or negative-working radiation-sensitive resin compositions have been used. In recent years, as higher integration of semiconductor devices, the width of wires and separation gaps required in a production process become increasingly fine. To cope with this requirement, there are various attempts such as fining resist patterns with a light of shorter wavelength, forming fine resist patterns by means of a phase-shift reticle etc., and developing novel resists. In the conventional photolithographic techniques using exposure, however, formation of fine resist patterns exceeding the limit of wavelength is difficult, and exposure units for short wavelengths and devices using a phase-shift reticle are expensive. Accordingly, a method of forming fine patterns described below has been proposed. That is, after resist patterns are formed in a known method of forming patterns by using a known positive- or negative-working radiation-sensitive resin composition, a coating layer is applied onto the resist patterns formed, and then the resist is heated and/or exposed to generate an acid to be diffused onto the coating layer. By the diffused acid, the coating layer is crosslinked to thicken the resist patterns, and as a result, gaps in the resist patterns are thinned. Thereby the resist patterns make fine and the fine resist patterns below the resolution limit are effectively formed. Various coating layer-forming compositions usable in the above method are known (e.g. JP-A Hei5-241348, JP-A Hei6-250379, JP-A Hei10-73927 etc.).
As the composition for forming said coating layer, a water-soluble resin composition comprising a water-soluble resin, a water-soluble crosslinking agent and as necessary a plasticizer and a surface active agent and generating crosslinking reaction in the presence of an acid has been proposed. However, the conventionally known water-soluble resin composition is poor in the uniformity of coating film on steps of resist patterns and is accordingly poor also in the ability to regulate the dimension of patterns upon fining thereof. Therefore, there is demand for further development in respect of improvement of yield.
The object of the present invention is to provide a water-soluble resin composition which can be used in a pattern-forming method, wherein the composition is coated on resist patterns formed in a conventional method and the resulting coating layer is crosslinked for thickening the resist patterns thereby effectively fining the trench patterns or hole patterns under the resolution limit, and which can form a coating layer excellent in coating characteristics on steps of resist patterns and in dimensional regulation of patterns upon fining thereof.
The other object of the present invention is to provide a fine pattern-forming material comprising the water-soluble resin composition described above.
DISCLOSURE OF INVENTION
As a result of their eager study and investigation, the present inventors found that the above-mentioned objects can be attained and a water-soluble resin composition, which is applied onto resist patterns after formation thereof, excellent in coating characteristics on steps of resist patterns and in dimensional regulation of patterns upon fining thereof can be obtained by the incorporation of a specific surface active agent to a water-soluble resin composition comprising a water-soluble resin and a water-soluble crosslinking agent and generating crosslinking reaction in the presence of an acid, thus having achieved the present invention based on the finding.
That is, the water-soluble resin composition of the present invention comprises a water-soluble resin, a water-soluble crosslinking agent, a surface active agent and a solvent and brings about crosslinking reaction in the presence of an acid, wherein as the surface active agent there is used at least one member selected from the group consisting of acetylene alcohols, acetylene glycols, polyethoxylates of acetylene alcohols and polyethoxylates of acetylene glycols.
Hereinafter, the present invention is described in more detail.
The water-soluble resin used in the water-soluble resin composition of the present invention may be any known conventional polymer having a water solubility of 0.1% by weight or more. Specifically, examples of the water-soluble resin are homopolymers or copolymers containing hydrophilic units which include e.g. polyvinyl alcohol (including partially saponified products), polyacrylic acid, polymethacrylic acid, poly(2-hydroxyethyl acrylate), poly(2-hydroxyethyl methacrylate), poly(4-hydroxybutyl acrylate), poly(4-hydroxybutyl methacrylate), poly(glucosiloxyethyl acrylate), poly(glucosiloxyethyl methacrylate), polyvinyl methyl ether, polyvinyl pyrrolidone, polyethylene glycol, polyvinyl acetal (including partial-acetal products), polyethylene imine, polyethylene oxide, styrene-maleic anhydride copolymer, polyvinyl amine, polyallyl amine, oxazoline group-containing water-soluble resin, water-soluble melamine resin, water-soluble urea resin, alkyd resin, and sulfonamide, as well as salts thereof. These may be used singly or in a combination of two or more thereof.
The molecular weight of the water-soluble resin used is preferably 1,000 to 10,000, more preferably 2,000 to 5,000 in terms of weight average molecular weight. Usually, if the molecular weight of the water-soluble resin is lower than 1,000, the resulting composition is inferior in coating properties to make preparation of a uniform coating difficult, and the coating is poor in stability with time, while if the molecular weight is higher than 10,000, the resulting composition shows the phenomenon of stringing at the time of coating, and is poor in spreadability on the surface of a resist, thus making formation of a uniform coating difficult upon dropping in a small amount.
The water-soluble crosslinking agent used in the water-soluble resin composition of the present invention is not particularly limited insofar as it is a water-soluble compound crosslinking the water-soluble resin by generating an acid. Examples of the water-soluble crosslinking agent which can be used in the present invention include melamine-based low-molecular derivatives, guanamine-based low-molecular derivatives, urea-based low-molecular derivatives, glycoluril, alkoxy alkylated amino resin etc.
The melamine-based low-molecular derivatives include melamine, methoxy methylated melamine, ethoxy methylated melamine, propoxy methylated melamine, butoxy methylated melamine and hexamethylol melamine.
The guanamine-based low-molecular derivatives include acetoguanamine, benzoguanamine and methylated benzoguanamine. The urea-based low-molecular derivatives include urea, monomethylol urea, dimethylol urea, alkoxy methylene urea, N-alkoxy methylene urea, ethylene urea, and ethylene urea carboxylic acid.
The alkoxy alkylated amino resin includes alkoxy alkylated melamine resin, alkoxy alkylated benzoguan
Kanda Takashi
Tanaka Hatsuyuki
Clariant Finance (BVI) Limited
Hanf Scott E.
Mullis Jeffrey
Sayko, Jr. Andrew F.
LandOfFree
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