TWI401546B - A patterning agent for patterning and a method for forming a fine pattern using the same - Google Patents

Description

Coating forming agent for forming a fine pattern and forming method of fine pattern using the same

The present invention relates to a coating forming agent for pattern miniaturization in the field of photolithography, and a method of forming a fine pattern using the same. More specifically, the present invention relates to a coating forming agent for pattern refining which can be integrated and miniaturized in recent years, and a method for forming a fine pattern using the same.

In the manufacture of electronic components such as semiconductor elements and liquid crystal elements, photolithography is used when etching a substrate or the like. In the photolithography technique, a film (photoresist layer) is provided on a substrate by using a so-called photoresist material that induces active radiation, and then the film is selectively irradiated with active radiation to expose it, and after development processing, selection is performed. The photoresist layer is dissolved and removed to form an image pattern (resist pattern) on the substrate. Then, the photoresist pattern is etched as a protective layer (mask pattern) to form a wiring pattern on the substrate.

In recent years, the integration and miniaturization of semiconductor elements have been increasing, and the formation of such photoresist patterns has also progressed toward miniaturization. Nowadays, ultrafine processing with a pattern width of 120 nm or less is required in the industry. In addition, the active light used to form the photoresist pattern also uses short-wavelength illumination such as KrF, ArF excimer laser light, EB (Electron Beam), EUV (Extreme Ultraviolet), and soft X-ray. For the photoresist material which is a photoresist pattern forming material, development of materials having physical properties corresponding to the irradiation light is also performed.

In addition to the ultrafine refining method for improving the photoresist material, in the pattern forming method, development of a pattern miniaturization technique that exceeds the resolution limit of the photoresist material has been carried out.

For example, Patent Document 1 (JP-A-5-166717) discloses a method of forming a hollow pattern in which a pattern is formed in a photoresist for pattern formation coated on a substrate, and light is formed in the pattern. After the resist is mixed and applied to the entire surface of the substrate, baking is performed, and a mixed layer is formed on the sidewall of the pattern forming photoresist to the surface, and the non-mixed portion of the photoresist for mixing formation is removed to achieve the above mixing. The miniaturization of the layer size portion. In the method of forming a pattern on a substrate on which a photoresist pattern containing an acid generator is formed, a photoresist containing a resin which is insolubilized in the presence of an acid is coated in the patent document 2 (JP-A-H05-241348). Thereafter, heat treatment is performed to diffuse the acid from the photoresist pattern to form a photoresist film having a certain thickness in the vicinity of the interface of the photoresist pattern, and then develop to remove the resin portion not diffused by the acid, thereby realizing the above-mentioned fixed thickness portion The miniaturization. Further, Patent Document 3 (Japanese Laid-Open Patent Publication No. Hei 10-073927) discloses a method of coating a photoresist pattern containing an acid generator with a material containing a material which crosslinks in the presence of an acid, followed by heating or The exposure process causes an acid to be generated in the photoresist pattern, and the crosslinked layer formed at the interface is formed as a coating layer of the photoresist pattern, and the aperture pattern and the separation width of the photoresist pattern are reduced by enlarging the photoresist pattern.

However, when the above method is used, the thermal dependence of the wafer surface is as high as about ten nm/° C., and it is very difficult to control the film thickness of the film formed on the photoresist pattern in a large-diameter wafer surface. Therefore, there is a problem that the size of the photoresist pattern after the miniaturization treatment is significantly different. In addition, there is a problem that it is difficult to suppress the occurrence of defects (pattern defects) after the miniaturization process, and it is difficult to perform secondary processing when the photoresist pattern is newly formed (the process of temporarily removing the photoresist pattern itself from the wafer) .

On the other hand, there is also known a method of making the pattern size fine by fluidizing the photoresist pattern by heat treatment or the like. For example, Patent Document 4 (JP-A-1-307228) discloses a method in which a photoresist pattern is formed on a substrate, and then heat treatment is performed to form a fine pattern by deforming a cross-sectional shape of the photoresist pattern. Further, Patent Document 5 (JP-A No. 4-364021) discloses a method in which after the photoresist pattern is formed, it is heated to a softening temperature thereof, and then the pattern size is changed by fluidization of the photoresist. To form a fine pattern.

However, the method has the following problems: it is difficult to control the amount of miniaturization caused by the heat flow, and it is difficult to obtain a photoresist pattern that maintains a good rectangular shape after the miniaturization process, and it is difficult to simultaneously exist in the wafer surface. The amount of miniaturization of the dense pattern is controlled to a fixed value.

As a method of further developing the above method, for example, a method of preventing light from being formed on a substrate on which a photoresist pattern is formed on a substrate is disclosed in Patent Document 6 (JP-A-H07-45510). The resin film which is excessively flowed is blocked, and then heat-treated to fluidize the photoresist to change the pattern size, and then the resin is removed to form a fine photoresist pattern.

However, this method has a problem that it is difficult to obtain a photoresist pattern that maintains a good rectangular shape after the miniaturization process, and it is difficult to control the amount of miniaturization of the dense pattern existing in the wafer surface to a fixed value. Further, it is difficult to suppress the variation in the amount of refinement of the photoresist pattern with respect to the fluctuation in the heating temperature.

In addition, Japanese Patent Application Laid-Open No. 2003-084459, JP-A-2003-084460, JP-A-2003-107752, JP-A-2003-142381, and JP-A-2003-142381 A related art of a coating forming agent for pattern refining and a method of forming a fine pattern is proposed in Japanese Laid-Open Patent Publication No. 2003-202679, and the like. According to the techniques shown in the above-mentioned Patent Documents 7 to 12, the controllability of the pattern size can be improved, and a fine pattern having characteristics required for a semiconductor element such as a rectangular shape having a fine resist pattern after the miniaturization can be obtained.

In the fine pattern forming technique using the pattern forming agent for pattern miniaturization, a photoresist layer is first provided on a substrate, and exposed and developed to form a photoresist pattern. Then, the pattern is made fine, and the coating agent is coated on the entire surface of the substrate, and then heated, and the pattern is made fine to refine the photoresist pattern by the heat shrinkage action of the coating agent. Thereby, the interval of the photoresist pattern is narrowed, and the width of the pattern defined by the interval of the photoresist pattern is also narrowed, whereby a fine pattern can be obtained.

In other words, the pattern is made fine, and it is affected by the size control of the resist pattern in the two stages of the heat-shrinking stage (second stage) of the resist pattern forming stage (first stage) and the pattern refining coating forming agent. When the photoresist pattern is formed by such a method, it is necessary to maintain the shape of the photoresist pattern formed in the first step in the heat shrinking step of the second stage and to shrink it at a uniform heat shrinkage rate.

However, in the miniaturization process of the ultra-fine refinement and high aspect ratio photoresist pattern having a pattern size of 120 nm or less, it is necessary to more strictly control the shape of the photoresist pattern after the miniaturization process, and to manage the finer finer. In such a situation, even if such a fine pattern forming technique using a coating forming agent for refining the pattern is used, a slight rounding of the shape of the top and bottom of the resist pattern occurs after the miniaturization process (Rounding, However, the shape is deteriorated, and the amount of fineness is changed due to fluctuations in the heating temperature in the wafer surface, or the amount of miniaturization of the dense pattern existing in the wafer surface is changed. It is difficult to perform nano-scale precision control on these miniaturization processes. It is necessary to solve the above problems while maintaining the required amount of miniaturization, and it is also necessary to eliminate the problem caused by the generation of bacteria or the like in the wafer surface after the coating formation agent is refined. The invention of the present invention is an invention for solving such problems.

Further, a method of coating an acid film formed of a photoresist pattern-reducing material containing a water-soluble resin on a surface of a resist pattern and then illuminating the light is disclosed in Patent Document 13 (JP-A-2001-281886). The surface layer of the resist pattern is converted into an alkali-soluble, and the surface layer and the acidic film are removed by an alkaline solution to reduce the resist pattern. Further, the following method is disclosed in Patent Document 14 (JP-A-2002-184673): Forming a photoresist pattern on the substrate, and forming a coating film containing a water-soluble film forming component on the photoresist pattern, and heat-treating the photoresist pattern and the coating film, and immersing in an aqueous solution of tetramethylammonium hydroxide, The fine photoresist pattern is formed by a dry etching step, and the above methods are all methods for miniaturizing the photoresist pattern itself, and the object thereof is completely different from the present invention.

[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 2003-142381 [Patent Document 11] Japanese Laid-Open Patent Publication No. 2003-195527 [Patent Document 12] Japanese Laid-Open Patent Publication No. 2001-281673 (Patent Document No. 2001-184673)

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a coating forming agent for pattern miniaturization and a fine pattern forming method using the same, which does not cause defects after miniaturization, and is particularly finer than 120 nm. In the refinement treatment of the photoresist pattern having a high aspect ratio, it is possible to suppress and manage the variation in the amount of refinement, and to maintain the desired refinement amount while maintaining the shape of the photoresist pattern after the refining treatment is good. In addition, it is possible to eliminate the problem caused by the generation of bacteria or the like in the wafer surface after the coating forming agent for pattern refining is applied.

In order to solve the above problems, the present invention provides a coating forming agent for pattern refining, which is coated on a substrate having a photoresist pattern for forming a fine pattern, comprising: (a) a water-soluble polymer, and (b) And at least one selected from the group consisting of a compound containing a carboxyl group or a salt or ester thereof, a peroxide, and a peracid.

Further, the present invention provides a coating forming agent for pattern refining, which is coated on a substrate having a photoresist pattern for forming a fine pattern, and the pattern forming agent for pattern refining is characterized by: (a) water-soluble polymerization And (c) from quaternary ammonium hydroxide, ammonium hydroxide, and hydroxide At least one selected from the group consisting of oxazolium.

Moreover, the present invention provides a method of forming a fine pattern, comprising the steps of: coating a pattern forming agent for pattern refining on a substrate having a photoresist pattern, and then miniaturizing the pattern by heat treatment The coating forming agent is thermally shrunk, and then the coating forming agent for pattern refinement is removed.

In a technique in which a coating film formed by a coating forming agent for pattern refining is provided on a substrate having a photoresist pattern to form a fine pattern, defects are not generated after the miniaturization treatment, and in particular, ultrafineness and highness of 120 nm or less are obtained. In the miniaturization process of the aspect ratio resist pattern, it is possible to suppress and manage variations in the heat treatment temperature in the wafer surface, a dense pattern existing in the wafer surface, and manufacturing batch error or manufacturing daytime error. Changes in the amount of miniaturization caused by the like. In addition, the shape of the photoresist pattern after the miniaturization treatment can be maintained and controlled in a good state while maintaining the required amount of miniaturization. Further, it is possible to eliminate the problem caused by the generation of bacteria or the like in the wafer surface after the application of the coating forming agent.

"Coating agent for pattern refinement"

The coating forming agent for pattern refining of the present invention (hereinafter simply referred to as "coating forming agent") contains (a) a water-soluble polymer, and (b) a compound containing a carboxyl group or a salt or ester thereof, At least one selected from the group consisting of peroxides and peracids, or (c) from quaternary ammonium hydroxide, ammonium hydroxide, and hydroxide An aqueous solution of at least one selected from the group consisting of oxonium.

<(a) Water-Soluble Polymer> The water-soluble polymer as the component (a) is not particularly limited as long as it is a polymer which is soluble in water at room temperature. The present invention can be used, for example, from acrylic acid, methyl acrylate, methacrylic acid, N,N-dimethyl acrylamide, N,N-dimethylaminopropyl methacrylamide, N,N-di Methylaminopropyl acrylamide, N-methyl acrylamide, diacetone acrylamide, N,N-dimethylaminoethyl methacrylate, N,N-diethyl methacrylate Ethyl ethyl ester, N,N-dimethylaminoethyl acrylate, N-propylene fluorenyl And a mixed polymer of a polymer or a copolymer composed of at least one selected from the group consisting of N-vinylpyrrolidone, vinyl acetate, and N-vinylimidazolidinone.

Further, in the present invention, as the cellulose resin, for example, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate phthalate, or hydroxypropylmethyl group can be used. Cellulose hexahydrophthalate, hydroxypropyl methylcellulose acetate succinate, hydroxypropyl methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, cellulose hexahydroortho-benzene Dicarboxylate, hydroxymethylcellulose, ethylcellulose, methylcellulose, and the like.

Among them, as the component (a) used in the present invention, a polymer and/or a copolymer of at least one selected from the group consisting of N-vinylpyrrolidone and vinyl alcohol is preferred, and polyvinylpyrrole is particularly preferred. a polymer of ketone.

Moreover, the mass average molecular weight of such a component (a) is preferably from 50,000 to 300,000.

When the coating film is provided on the photoresist pattern, the amount of the component (a) in the present invention is appropriately adjusted in such a range as to obtain a sufficient film thickness necessary for use, but in the total solid content of the coating forming agent, It is preferably adjusted to about 1 to 99% by mass, more preferably about 40 to 99% by mass, and still more preferably about 65 to 99% by mass.

<(b) at least one selected from the group consisting of a compound containing a carboxyl group or a salt or an ester thereof, a peroxide, and a peracid> Examples of the compound containing a carboxyl group include acetic acid, fumaric acid, and Diacid, sorbic acid, benzoic acid, hydroxybenzoic acid, caproic acid, caprylic acid, capric acid, lauric acid, and the like. Further, examples of the salt of the compound containing a carboxyl group include sodium salt and potassium salt of sorbic acid and benzoic acid. Further, examples of the ester compound of the compound containing a carboxyl group include an ester of hexanoic acid, caprylic acid, capric acid, lauric acid and the like with glycerin; methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, and 4-hydroxybenzoic acid; Propyl ester, isopropyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, isobutyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, and the like.

Examples of the peroxide include hydrogen peroxide, ethyl peroxide peroxide, tert-butyl peroxide, diethyl peroxide, dibutyl peroxide, and diethyl ruthenium peroxide.

Examples of the peracid include performic acid, peracetic acid, perpropionic acid, and the like.

Among the components (b) exemplified above, hydrogen peroxide and/or peracetic acid are most preferred. In addition, the component (b) is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the component (a).

<(c) From quaternary ammonium hydroxide, ammonium hydroxide, and hydroxide At least one selected from the group consisting of: quaternary ammonium hydroxide, ammonium hydroxide, and hydroxide as component (c) At least one selected from the group consisting of oxanthene can be exemplified by the following.

The quaternary ammonium hydroxide is quaternary ammonium hydroxide represented by the following formula (c1).

In the above formula (c1), R ^c1 , R ^c2 , R ^c3 and R ^c4 each independently represent an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group.

Specific examples of the quaternary ammonium hydroxide represented by the formula (c1) include tetramethylammonium hydroxide [=TMAH, Tetramethylammonium Hydroxide], tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrahydric hydroxide. Butylammonium, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, trimethylethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide [=choline], hydrogen peroxide (2-hydroxyl) Ethyl)triethylammonium, (2-hydroxyethyl)tripropylammonium hydroxide, (1-hydroxypropyl)trimethylammonium hydroxide, and the like.

In addition, examples of the above-mentioned hydrogenated cyclic ammonium salt include a hydrogenated cyclic ammonium compound represented by the following general formulae (c2) and (c3).

In the above formulae (c2) and (c3), A and B represent an alkyl group having 1 to 6 carbon atoms, k and i represent an integer of 0 to 4, n and m represent an integer of 3 to 7, and R ^c5 and R ^c6 represents an alkyl group having 1 to 8 carbon atoms.

Specific examples of the cation of the hydrogenated cyclic ammonium represented by the above formulas (c2) and (c3) include N,N-dimethylpyrrolidinium ion and N,N-diethylpyrrolidinium ion. , N,N-di-n-propylpyrrolidium ion, N,N-di-n-butylpyrrolidium ion, N,N-dimethylpiperidinium ion, N,N-diethylpiperidinium ion , N,N-di-n-propylpiperidinium ion, N,N-di-n-butylpiperidinium ion, spiro-(1,1')-bias cyclobutyl ion, fluorene cyclopentane Alken-1-spiro-1'-indenylbutyl ion, indole cyclohexane-1-spiro-1'-fluorenylbutyl ion, anthracene heptane-1-spiro-1'-fluorenylbutyl ion , anthracycline-1-oxa-1'-fluorenylbutyl ion, spiro-(1,1')-biguanide cyclopentyl ion, indole cyclohexane-1-spiro-1'-fluorene cyclopentane Base ion, anthracene heptane-1-spiro-1'-indolecyclopentyl ion, anthracycline-octane-1-spiro-1'-fluorenylcyclopentyl ion, spiro-(1,1')-biguanide Cyclohexyl ion, anthracene heptane-1-spiro-1'-nonylcyclohexyl ion, anthracene octane-1-spiro-1'-nonylcyclohexyl ion, spiro-(1,1')-biguanide ring Heptyl ion, anthracycline octane-1-spiro-1'-anthracene heptyl group Sub, spiro-(1,1')-biguanidinium cation.

In addition, as the above hydroxide Examples of the oxonium hydride include hydrogen hydroxide represented by the following general formulae (c4) and (c5). Ammonium hydride.

In the above formulae (c4) and (c5), A and B represent an alkyl group having 1 to 6 carbon atoms, k and i represent an integer of 0 to 4, n represents an integer of 3 to 7, and R ^c7 and R ^c8 It represents an alkyl group having 1 to 8 carbon atoms.

As such a hydroxide represented by the general formulae (c4) and (c5) Examples of the cation of oxonium include N,N-dimethyl Porphyrin ion, N,N-diethyl Porphyrin ion, N,N-dipropyl Ruthenium ion, N,N-dibutyl Ruthenium ion, N,N-dipentyl Porphyrin ion, N,N-diheptyl Ruthenium ion, N,N-dioctyl Porphyrin ion, N, N-ethyl methyl Porphyrin ion, N,N-propylmethyl Porphyrin ion, Porphyrin-4-spiro-1'-fluorenylbutyl ion, Porphyrin-4-spiro-1'-nonylcyclopentyl ion, Porphyrin-4-spiro-1'-nonylcyclohexyl ion, Porphyrin-4-spiro-1'-fluorenylheptyl ion, Porphyrin-4-spiro-1'-anthracycline ion.

The above hydroxide is preferably tetraammonium hydroxide, particularly preferably tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, methyltributylammonium hydroxide or methylated hydroxide. At least one selected from the group consisting of ammonium propylamine and choline.

For 100 parts by mass of the above component (a), it is preferred to formulate 0.001 to 3 parts by mass of such component (c), and particularly preferably 0.01 to 1 part by mass.

In the coating forming agent of the present invention, an aqueous solution containing the above component (a) and component (b) or the components (a) and (c) is usually used. The coating forming agent is preferably an aqueous solution having a solid content of 3 to 50% by mass, more preferably 5 to 20% by mass.

In addition, although the coating agent of the present invention is preferably an aqueous solution, a mixed solvent of water and an alcohol solvent may be used insofar as the effects of the present invention are not impaired. Examples of such an alcohol-based solvent include methanol, ethanol, propanol, isopropanol, glycerin, ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, and 2,3-. Butylene glycol and the like. These alcohol-based solvents are mixed and used in an amount of 30 parts by mass based on 100 parts by mass of water.

The coating forming agent of the present invention can contain no defects after the refining treatment by containing the components (a) and (b) or the components (a) and (c), especially at 120 nm or less. In the miniaturization process of the ultra-fine and high aspect ratio photoresist pattern, it is possible to suppress and manage the variation of the heat treatment temperature in the wafer surface, or the dense pattern existing in the wafer surface, and the manufacturing. Variation in the amount of miniaturization caused by inter-batch errors or manufacturing daytime errors. Further, the shape of the photoresist pattern after the miniaturization treatment can be maintained and controlled in a good state while maintaining the required amount of miniaturization. Further, it is possible to eliminate the problem caused by the generation of bacteria or the like in the wafer surface after the application of the coating forming agent.

Further, in the present invention, the coating agent may be formulated with the following water-soluble crosslinking agent, surfactant, water-soluble fluoride, and guanamine-containing group as needed within a range that does not impair the effects of the present invention. a monomer, a heterocyclic compound having at least an oxygen atom and/or a nitrogen atom, a heterocyclic compound having at least two nitrogen atoms in the same ring, a water-soluble amine compound, and a non-aqueous water-soluble organic solvent. As such an optional component, for example, the following may be mentioned: The water-soluble crosslinking agent is preferably a water-soluble crosslinking agent, and a nitrogen-containing compound having at least two hydrogen atoms substituted with a hydroxyalkyl group and/or an alkoxyalkyl group and containing an amine group and/or an imide group is preferred. Examples of the nitrogen-containing compound include a melamine-based derivative in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group, or both, a urea-based derivative, a guanamine-based derivative, and B. guanidine Derivatives A derivative, an amber amide derivative, or a acetylene halide derivative or a ketamine derivative substituted with a hydrogen atom of an imine group.

Among the nitrogen-containing compounds, from the viewpoint of crosslinking reactivity, at least two hydrogen atoms are substituted with a methylol group or a lower alkoxymethyl group having 1 to 6 carbon atoms, or both. Benzoquinone having an amine group and/or an imine group a derivative, a guanamine derivative, a melamine derivative, etc. One or more of the derivative, the acetylene urea derivative, and the urea derivative are preferred.

The amount of addition of such a water-soluble crosslinking agent is preferably adjusted to about 1 to 35% by mass in the solid content of the coating forming agent.

. The surfactant is required to have a property of being highly soluble in the (a) water-soluble polymer and not causing a suspension as a surfactant. By using a surfactant which satisfies the above characteristics, generation of bubbles (microfoam) when the coating forming agent is applied can be suppressed, and generation of defects associated with the generation of the micro-foam can be more effectively prevented. From the above viewpoints, it is preferred to use one or more of an N-alkylpyrrolidone surfactant, a quaternary ammonium salt surfactant, a polyoxyethylene phosphate surfactant, and a nonionic surfactant. .

The above N-alkylpyrrolidone-based surfactant is preferably represented by the following formula (1).

In the above formula (1), R ²⁰ represents an alkyl group having 6 or more carbon atoms.

Specific examples of the N-alkylpyrrolidone-based surfactant include N-hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, N-octyl-2-pyrrolidone, and N. - mercapto-2-pyrrolidone, N-mercapto-2-pyrrolidone, N-decyl-2-pyrrolidone, N-undecyl-2-pyrrolidone, N-dodecane Base-2-pyrrolidone, N-tridecyl-2-pyrrolidone, N-tetradecyl-2-pyrrolidone, N-pentadecyl-2-pyrrolidone, N-ten Hexaalkyl-2-pyrrolidone, N-heptadecyl-2-pyrrolidone, N-octadecyl-2-pyrrolidone, and the like. Among them, N-octyl-2-pyrrolidone ("SURFADONE LP100"; manufactured by ISP) is preferred.

The quaternary ammonium-based surfactant is preferably represented by the following formula (2).

[Chemical 5]

In the above formula (2), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group or a hydroxyalkyl group (but at least one of them represents an alkyl group having 6 or more carbon atoms or a hydroxyalkyl group). X ^- represents a hydroxide ion or a halogen ion.

Specific examples of the quaternary ammonium-based surfactant include dodecyltrimethylammonium hydroxide, tridecyltrimethylammonium hydroxide, tetradecyltrimethylammonium hydroxide, and pentadecyltrimethylammonium hydroxide. Cetyltrimethylammonium hydroxide, heptadecyltrimethylammonium hydroxide, octadecyltrimethylammonium hydroxide, and the like. Among them, it is preferred to use cetyltrimethylammonium hydroxide.

The phosphate ester surfactant of the above polyoxyethylene is preferably represented by the following formula (3).

In the above formula (3), R ²⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkylallyl group, and R ²⁶ represents a hydrogen atom or (CH ₂ CH ₂ O)R ²⁵ (R ^{25 is} as defined above) ), x represents an integer from 1 to 20.

Specific examples of the phosphate ester-based surfactant of the polyoxyethylene are commercially available products such as "Plysurf A212E" and "Plysurf A210G" (all of which are manufactured by Daiichi Kogyo Co., Ltd.).

As the nonionic surfactant, an alkyl ether compound or an alkyl amine oxide compound of polyoxyalkylene is preferred.

As the alkyl etherate of the above polyoxyalkylene, a compound represented by the following formula (4) or (5) is preferably used.

In the above formulae (4) and (5), R ²⁷ and R ^{28 each} represent a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms, an alkyl group having a hydroxyl group, or an alkyl group. Phenyl. The A ₀ -oxyalkylene group is preferably at least one selected from the group consisting of oxyethylene, oxypropylene, and oxybutylene. y is an integer.

As the alkylamine oxide compound, a compound represented by the following formula (6) or (7) is preferably used.

In the above formulae (6) and (7), R ²⁹ represents an alkyl group or a hydroxyalkyl group having 8 to 20 carbon atoms interrupted by an oxygen atom, and p and q represent an integer of 1 to 5.

Examples of the alkylamine oxide compound represented by the above formulas (6) and (7) include octyldimethylamine oxide, dodecyldimethylamine oxide, decyldimethylamine oxide, and laurel. Methyl dimethyl amine oxide, cetyl dimethyl amine oxide, octadecyl dimethyl amine oxide, isohexyl diethyl amine oxide, mercapto diethyl amine oxide, lauryl diethyl amine oxide , isopentadecylmethylethylamine oxide, octadecylmethylpropylamine oxide, lauryl bis(hydroxyethyl) amine oxide, cetyl diethanol amine oxide, octadecyl di Hydroxyethyl) amine oxide, dodecyloxyethoxyethoxyethyl di(methyl) amine oxide, octadecyloxyethyl bis(methyl) amine oxide, and the like.

Among these surfactants, it is particularly preferable to use a nonionic surfactant in consideration of factors for reducing defects.

The amount of addition of such a surfactant is preferably adjusted to about 1 ppm to 10% by mass in the solid content of the coating forming agent, and more preferably adjusted to about 100 ppm to 2% by mass. .

. The water-soluble fluoride is required to have a high solubility to the water-soluble polymer (a) and to exhibit no suspension or the like as a water-soluble fluoride. The leveling property (the degree of expansion of the coating forming agent) can be further improved by using a water-soluble fluoride which satisfies such characteristics. The leveling property can also be achieved by excessively adding a surfactant to reduce the contact angle. However, when the surfactant is excessively added, not only a certain degree of coating improvement property cannot be confirmed, but also due to excessive addition of the surfactant, At the time of coating, bubbles (microfoam) are generated on the coating film, which causes a problem of causing defects. By formulating the water-soluble fluoride, not only such foaming can be suppressed, but also the contact angle can be lowered and the leveling property can be improved.

As the water-soluble fluoride, fluoroalkyl alcohols, fluoroalkyl carboxylic acids and the like are preferably used. Examples of the fluoroalkyl alcohols include 2-fluoro-1-ethanol, 2,2-difluoro-1-ethanol, trifluoroethanol, tetrafluoropropanol, and octafluoropentanol. Examples of the fluoroalkylcarboxylic acid include trifluoroacetic acid. However, it is not limited to these examples, and it is not limited as long as it has a water-soluble fluoride and exhibits the above effects. In particular, a fluoroalkyl alcohol having 6 or less carbon atoms is preferably used. Among them, trifluoroethanol is particularly preferred in view of factors such as easy availability.

The amount of addition of such a water-soluble fluoride is preferably adjusted to about 0.1 to 30% by mass in the solid content of the coating forming agent, and particularly preferably from about 0.1 to 15% by mass.

. The monomer containing a guanamine group is not particularly limited as the monomer having a guanamine group, but it is necessary to have high solubility to the above-mentioned (a) water-soluble polymer and to exhibit no characteristics such as suspension.

As the amide group-containing monomer, a guanamine compound represented by the following formula (8) is preferably used.

In the above formula (8), R ³⁰ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group, R ³¹ represents an alkyl group having 1 to 5 carbon atoms, and R ³² represents a hydrogen atom or Methyl, z is an integer from 0 to 5. The above alkyl group or hydroxyalkyl group includes any of a straight chain and a branched chain.

It is preferred to use a monomer having a hydrazine group in which R ³⁰ represents a hydrogen atom, a methyl group or an ethyl group and z is 0 in the above formula (8). Specific examples of such a mercapto group-containing monomer include acrylamide, methacrylamide, N,N-dimethylpropenamide, N,N-dimethylmethacrylamide, and N. , N-diethyl acrylamide, N,N-diethyl methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N - Ethyl methacrylamide or the like. Among them, propylene amide and methacrylamide are particularly preferred.

When the amount of the monomer containing the guanamine group is added, it is preferable to adjust the addition amount to about 0.1 to 30% by mass in the solid content of the coating agent, and it is particularly preferable to adjust it to 1 to 15 mass. %about.

. The heterocyclic compound containing at least an oxygen atom and/or a nitrogen atom may be formulated with a heterocyclic compound containing at least an oxygen atom and/or a nitrogen atom. As such a heterocyclic compound, a compound of the oxazolidine skeleton, having a compound of an oxazoline skeleton having a compound of an oxazolone skeleton, and having At least one selected from the compounds of the oxazolidinone skeleton is preferred.

As described above a compound of the oxazolidine skeleton, which is represented by the following chemical formula (9) In addition to the oxazoline, a substituent thereof can be cited.

The substituent may be represented by the above chemical formula (9). A hydrogen atom bonded to a carbon atom or a nitrogen atom of an oxazoline is substituted with a substituted or unsubstituted lower alkyl group, a carboxyl group, a hydroxyl group or a halogen group having 1 to 6 carbon atoms. The substituted lower alkyl group may, for example, be a hydroxyalkyl group or a lower alkoxyalkyl group, but is not limited to these examples.

As described above a compound of the oxazoline skeleton, which is represented by the following formula (8-1): Oxazoline, represented by the chemical formula (8-2) 3- Oxazoline, represented by chemical formula (8-3) 4- In addition to the oxazoline, a substitute such as these may be mentioned.

Examples of the substituent include those represented by the above chemical formulas (8-1) to (8-3). A compound in which a carbon atom or a nitrogen atom bonded to a nitrogen atom of a compound of the oxazoline skeleton is substituted with a substituted or unsubstituted lower alkyl group, a carboxyl group, a hydroxyl group or a halogen group having 1 to 6 carbon atoms. The substituted lower alkyl group may, for example, be a hydroxyalkyl group or a lower alkoxyalkyl group, but is not limited to these examples.

Above In the compound of the oxazoline skeleton, 2-methyl-2- represented by the following chemical formula (8-1-A) is used. Oxazoline is preferred.

As described above The compound of the oxazolidinone skeleton is divided by 5(4)- represented by the following chemical formula (9-1) Oxazolone, 5(2)- represented by the following chemical formula (9-2) Oxazolone, 4(5)- represented by the following chemical formula (9-3) Oxazolone, 2(5)- represented by the following chemical formula (9-4) Oxazolone, 2(3)- represented by the following chemical formula (9-5) In addition to the oxazolone, a substitute such as these may be mentioned.

Examples of the substituent include those represented by the above chemical formulas (9-1) to (9-5). A compound in which a carbon atom or a nitrogen atom bonded to a nitrogen atom of a compound of the oxazolidinone skeleton is substituted with a substituted or unsubstituted lower alkyl group, a carboxyl group, a hydroxyl group or a halogen group having 1 to 6 carbon atoms. The substituted lower alkyl group may, for example, be a hydroxyalkyl group or a lower alkoxyalkyl group, but is not limited to these examples.

As described above a compound of an oxazolidinone skeleton (or having 2 a compound of the oxazolidinone skeleton, which is represented by the following chemical formula (10) Azolidinone (or 2- In addition to the oxazolidinone, a substituent thereof can be cited.

The substituent may be represented by the above chemical formula (10). Azolidinone (or 2- A hydrogen atom bonded to a carbon atom or a nitrogen atom of an oxazolone is substituted with a substituted or unsubstituted lower alkyl group, a carboxyl group, a hydroxyl group or a halogen group having 1 to 6 carbon atoms. The substituted lower alkyl group may, for example, be a hydroxyalkyl group or a (lower alkoxy)alkyl group, but is not limited to these examples.

This has In the compound of the oxazolidinone skeleton, 3-methyl-2- represented by the following chemical formula (10-1) is used. Iazolidinone is preferred.

The addition amount of the heterocyclic compound having at least an oxygen atom and/or a nitrogen atom is preferably adjusted to 1 to 50% by mass based on the amount of the water-soluble polymer (a), and more preferably The adjustment is 3 to 20% by mass.

. A heterocyclic compound having at least two nitrogen atoms in the same ring as a heterocyclic compound having at least two nitrogen atoms in the same ring, and examples thereof include pyrazole and 3,5-dimethylpyrazole. 2-pyrazoline, 5-pyrazolone, 3-methyl-1-phenyl-5-pyrazolone, 2,3-dimethyl-1-phenyl-5-pyrazolone, 2,3 Pyrazole-based compounds such as dimethyl-4-dimethylamino-1-phenyl-5-pyrazolone and benzopyrazole; imidazole, methylimidazole, 2,4,5-triphenylimidazole , an imidazole compound such as 4-(2-aminoethyl)imidazole or 2-amino-3-(4-imidazolyl)propanoic acid; 2-imidazoline, 2,4,5-triphenyl-2- Imidazoline-based compound such as imidazoline or 2-(1-naphthylmethyl)-2-imidazoline; imidazolium, 2-imidazolidone, 2,4-imidazolidinone, 1-methyl Base-2,4-imidazolidinone, 5-methyl-2,4-imidazolidindione, 5-hydroxy-2,4-imidazolidindione-5-carboxylic acid, 5-ureido-2, Imidazole such as 4-imidazolidinone, 2-imino-1-methyl-4-imidazolidinone or 2-thioketo-4-imidazolidinone Compound; Bing benzene, 2-phenyl imidazole Bing benzene, 2-benzyl-imidazolidinone Bing Bing imidazole compounds such as benzene; 1,2-bis 1,3-two 1,4-two 2,5-dimethylpyridyl Wait two a compound; 2,4(1H,3H)pyrimidinedione, 5-methyluracil, 5-ethyl-5-phenyl-4,6-perhydropyrimidinedione, 2-thioketo-4 a hydrogen pyrimidine compound such as 1H,3H)-pyrimidinone, 4-imino-2(1H,3H)-pyrimidine or 2,4,6(1H,3H,5H)-pyrimidinetrione; Porphyrin Quinazoline, quinolin Phenanthine, such as bromine and luminescent amine (Luminol) Compound; benzoquinone Porphyrin, brown (phenazine), 5,10-dihydromorphine Diphenyl hydrazine a compound; a triazole compound such as 1H-1,2,3-triazole, 1H-1,2,4-triazole, 4-amino-1,2,4-triazole; benzotriazole, 5 - benzotriazole-based compounds such as methyl benzotriazole; 1,3,5-three 1,3,5-three -2,4,6-triol, 2,4,6-trimethoxy-1,3,5-three 1,3,5-three -2,4,6-trithiol, 1,3,5-three -2,4,6-triamine, 4,6-diamino-1,3,5-three -2-ol, etc. A compound or the like is not limited to these examples.

Among them, a monomer using an imidazole compound is preferable in view of factors such as ease of use and availability, and it is particularly preferable to use imidazole.

When the amount of the heterocyclic compound having at least two nitrogen atoms in the same ring is added, the amount of addition is preferably from 1 to 15% by mass based on the amount of the water-soluble polymer (a). Jiawei adjusted it to about 2~10% by mass.

. The water-soluble amine compound can further prevent the generation of impurities, adjust the pH, and the like by using such a water-soluble amine compound.

The water-soluble amine compound may, for example, be an amine having a pKa (acid dissociation constant) of 7.5 to 13 in an aqueous solution at 25 °C. Specific examples thereof include monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, and N. N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, etc. Alkanolamines; diethylenetriamine, triethylenetetramine, propylenediamine, N,N-diethylethylenediamine, 1,4-butanediamine, N-ethyl-extension a polyalkylene polyamine such as an amine, 1,2-propylene diamine, 1,3-propylene diamine, 1,6-exexylene diamine; 2-ethyl-hexylamine, dioctylamine, and tributyl An aliphatic amine such as an amine, a tripropylamine, a triallylamine, a heptylamine or a cyclohexylamine; an aromatic amine such as a benzylamine or a diphenylamine; N-methyl-piperidine Hydroxyethyl pipe Such as cyclic amines and the like. Among them, a water-soluble amine compound having a boiling point of 140 ° C or higher (at 760 mmHg) is preferred, and for example, monoethanolamine, triethanolamine or the like is preferably used.

The amount of addition of such a water-soluble amine compound is preferably adjusted to about 0.1 to 30% by mass in the solid content of the coating forming agent, and it is particularly preferably adjusted to about 2 to 15% by mass.

. The non-amine-based water-soluble organic solvent can further suppress the occurrence of defects by blending a non-amine-based water-soluble organic solvent.

The non-amine-based water-soluble organic solvent may be a non-amine organic solvent which is miscible with water, and examples thereof include an anthracene such as dimethyl hydrazine; dimethyl hydrazine, diethyl hydrazine, and a bis Anthraquinones such as (2-hydroxyethyl)hydrazine and tetramethylene sulfone; N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, amide such as N,N-diethylacetamide; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl- Intrinsic amines such as 2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone (1 , 3-dimethyl-2-imidazolidinone), 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidone, and the like, imidazolidinone; ethylene glycol, ethylene Alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, Gan Polyhydric alcohols, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol and the like and derivatives thereof. Among them, polyhydric alcohols and derivatives thereof are preferred in view of factors such as suppression of defects, and glycerin is particularly preferred. The non-amine-based water-soluble organic solvent may be used alone or in combination of two or more.

The addition amount of such a non-amine-based water-soluble organic solvent is preferably adjusted to about 0.1 to 30% by mass based on the amount of the water-soluble polymer (a), and it is particularly preferably adjusted to 0.5 to 15%. About % by mass.

The method for forming a fine pattern of the present invention includes the steps of coating the substrate having the photoresist pattern on the coating forming agent, performing heat treatment to shrink the coating forming agent, and then removing the coating forming agent.

The substrate having the photoresist pattern is not particularly limited, and can be produced by a usual method used in the production of a semiconductor element, a liquid crystal display element, a magnetic head, or a microlens. For example, a photoresist composition such as a spin coater is coated on a substrate such as a tantalum wafer, and a resist composition for a chemically amplified type or the like is applied to form a photoresist layer, and then a desired projection is used by a reduced projection exposure apparatus or the like. Cover pattern, irradiating active light such as ultraviolet light, deep ultraviolet light (Deep-UV), excimer laser light, etc. in a vacuum or through a liquid having a specific refractive index, or by drawing with an electron beam, heating the substrate, and then using the developing solution For example, an alkaline aqueous solution such as a 1 to 10% by mass aqueous solution of tetramethylammonium hydroxide (TMAH, Tetramethylammonium Hydroxide) or the like is subjected to development treatment, whereby a photoresist pattern can be formed on the substrate.

In addition, the composition for the photoresist which is a material of the photoresist pattern is not particularly limited, and a resist composition for i-line or g-line or a photoresist for excimer laser such as KrF, ArF or F ₂ can be used. Further, a photoresist composition such as an EB (Electron Beam) or a photoresist for EUV (Extreme Ultraviolet), which is generally used, can be used.

a. Coating Forming Agent Coating Step Next, a coating forming agent is applied and coated on the entire surface of the substrate having such a photoresist pattern as a mask pattern. Further, after the coating forming agent is applied, the substrate may be pre-baked for 30 to 90 seconds at a temperature of 80 to 100 ° C.

The coating method can be carried out in accordance with a method generally used in the conventional heat flow process. That is, a well-known coating method such as a bar coating method, a roll coating method, a slit coating method, or a spin coating using a spinner can be used. The aqueous solution of the coating forming agent is applied onto a substrate.

b. Heat Treatment Step Next, heat treatment is performed to shrink the coating film formed by the coating forming agent. By the contraction of the coating film, the photoresist pattern connected to the coating film is widened and enlarged to correspond to a portion where the coating film shrinks, and the photoresist patterns are in a state of being close to each other, and the photoresist pattern is narrowed. interval.

The heat treatment temperature is a temperature at which the coating film formed by the coating forming agent shrinks, and is not particularly limited as long as it is sufficient to refine the pattern, and it is preferable to heat the temperature at which the photoresist pattern does not generate heat. . The temperature at which the photoresist pattern does not generate heat flows means that the substrate is formed without forming a coating film formed of the coating forming agent, and only the photoresist pattern is formed, and the photoresist pattern is not made to have a size. The temperature at which changes (eg, dimensional changes caused by naturally occurring flows, etc.). By the heat treatment of the temperature, a fine pattern having a good profile can be formed more effectively, and in particular, a ratio of the inside of the wafer surface, that is, a dependency on the pattern interval in the wafer surface, etc. Very effective in terms of aspects. Considering that the various photoresist compositions used in current photolithography technologies begin to generate heat flow temperatures, the preferred heat treatment is usually in the temperature range of about 80 to 180 ° C, but the photoresist does not generate heat flow. At a temperature of about 30 to 90 seconds, heat treatment is performed.

Further, the thickness of the coating film formed as the coating forming agent is preferably the same as the height of the photoresist pattern or the height of the photoresist pattern covering the left and right.

c. After the coating forming agent removing step, the coating film formed by the coating forming agent remaining on the substrate having the resist pattern is preferably washed by an aqueous solvent or pure water for 10 to 60 seconds to remove The coating film. Further, it may be rinsed with an alkaline aqueous solution (for example, tetramethylammonium hydroxide (TMAH), choline, or the like) as needed before washing with water. The coating forming agent of the present invention can be easily washed away with water and can be completely removed from the substrate and the photoresist pattern.

Then, a substrate having a miniaturized pattern defined between the widened and enlarged photoresist patterns on the substrate can be obtained.

The fine pattern obtained by the present invention has the following physical properties: it has a finer pattern size than the resolution limit obtained by the conventional method, and has a good resist pattern shape, and can sufficiently satisfy the required desired characteristics.

Furthermore, the a~c steps described above may be repeated a plurality of times. By repeating the steps a to c as many times as described above, the photoresist pattern can be gradually widened and enlarged.

The technical field to which the present invention is applied is not limited to the field of semiconductors, and can be widely used for liquid crystal display elements, magnetic head manufacturing, and microlens manufacturing.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited thereto.

[Coating Agent A] Peracetic acid having a total mass of 400 ppm with respect to polyvinylpyrrolidone was blended in a 4% by mass aqueous solution of polyvinylpyrrolidone to prepare a coating forming agent A.

[Coating Agent B] Peracetic acid having a total mass of 600 ppm with respect to polyvinylpyrrolidone was blended in a 4% by mass aqueous solution of polyvinylpyrrolidone to prepare a coating forming agent B.

[Covering agent C]

A peracetic acid having a total mass of 200 ppm based on the polyvinylpyrrolidone was blended in a 4% by mass aqueous solution of polyvinylpyrrolidone to prepare a coating forming agent C.

[Covering agent D]

A coating agent D was prepared by dissolving tetramethylammonium hydroxide in an amount of 400 ppm based on the total mass of the polyvinylpyrrolidone in a 4% by mass aqueous solution of polyvinylpyrrolidone.

[Covering agent E]

A coating agent E was prepared by dissolving tetramethylammonium hydroxide in an amount of 600 ppm based on the total mass of the polyvinylpyrrolidone in a 4% by mass aqueous solution of polyvinylpyrrolidone.

[Covering agent F]

In a 4% by mass aqueous solution of polyvinylpyrrolidone, N,N-dimethylpyrrolidinium hydroxide was added in an amount of 400 ppm based on the total mass of the polyvinylpyrrolidone to prepare a coating forming agent F.

[Covering Agent G]

7.0 g of a copolymer composed of acrylic acid/vinylpyrrolidone (AA/VP, Acrylic Acid/Vinyl Pyrrolidone) (AA: VP = 2: 1.3 (polymerization ratio)), 6 g of triethylamine, and 1 g were used. "Plysurf A210G" (manufactured by Daiichi Kogyo Co., Ltd.), a phosphate ester surfactant of polyoxyethylene, was dissolved in pure water, and the total amount was adjusted to 100 g to prepare a coating forming agent G.

[Coating Agent H] A 4% by mass aqueous solution of polyvinyl alcohol was prepared to prepare a coating forming agent H.

On the other hand, TARF-P7066 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is a positive-type photoresist, was spin-coated on a 8 吋矽 wafer, and baked at 135 ° C for 60 seconds to form a film thickness of 200 nm. The photoresist layer.

The photoresist layer was subjected to exposure treatment using an exposure apparatus NSR-S306 (manufactured by Nikon Co., Ltd.) or NSR-S203 (manufactured by Nikon Co., Ltd.), and subjected to heat treatment at 110 ° C for 60 seconds, followed by using 2.38 mass % of TMAH. An aqueous solution of (tetramethylammonium hydroxide) was subjected to development treatment to form a pore pattern having a diameter of 120 nm (hole pattern diameter: distance between pore patterns = 1:1).

Then, the coating forming agents A to E are applied onto the germanium wafer on which the photoresist pattern is formed, and a coating film having a thickness of 200 nm is formed, and the wafer is heat-treated at 150 ° C for 60 seconds. The micronization process of the hole pattern. Then, the coating forming agent was removed using pure water at 23 °C.

The evaluations 1 to 6 shown below were performed for each of the miniaturization processes. The results are shown in Table 1.

Evaluation 1: Whether or not the defect was generated The substrate after the above-described micronization treatment was observed using KLA (manufactured by KLA Tencor Co., Ltd.) and the number of defects was counted. The number of defects at this time was 100% as a result of the refining treatment using the coating forming agent E. On the other hand, the results when other coating forming agents were used are shown in Table 1.

Evaluation 2: Variation in the amount of miniaturization caused by the fluctuation of the heat treatment temperature The heat treatment in the above-described miniaturization treatment was performed at four points of 130 ° C, 140 ° C, 150 ° C, and 160 ° C, and the respective refining treatments were performed. The size of the photoresist pattern after the miniaturization treatment was measured using a scanning electron microscope. The amount of change in the amount of miniaturization per 1 ° C was calculated from the amount of change in the amount of miniaturization at this time, and is shown in Table 1, respectively.

Evaluation 3: The variation in the amount of miniaturization of the dense pattern is performed by minimizing the pattern in which the distance between the hole patterns of the hole pattern is one time (equal magnification), 1.5 times, two times, and five times the diameter of the hole pattern. . The photoresist pattern after the miniaturization treatment at this time was measured using a scanning electron microscope, and the difference between the minimum amount and the maximum amount of the miniaturization amount is shown in Table 1, respectively.

Evaluation 4: Shape of the photoresist pattern after the micronization treatment The shape of the photoresist pattern after the above-described refining treatment was observed and evaluated using a scanning electron microscope. A good photoresist pattern in which the photoresist pattern has a rectangular shape is referred to as A, and a pattern having a non-rectangular shape is referred to as B, and the results are shown in Table 1.

Evaluation 5: Micronization amount The size of the photoresist pattern after the above-described miniaturization treatment was measured using a scanning electron microscope. The amount of miniaturization when the size of the first resist pattern was miniaturized at this time is shown in Table 1, respectively.

Evaluation 6: The presence or absence of bacteria was filtered by Millpore MX00TT220 which is a filter film for aerobic heterotrophic bacteria before application of the above-mentioned coating agent, and the substrate coated with the coating agent was allowed to stand at room temperature for 3 days, and then visually observed. Evaluate the presence or absence of bacteria. Those who did not produce bacteria were referred to as A, and those who produced bacteria were designated as B, and the results thereof are shown in Table 1.

The positive-type photoresist of the above-mentioned embodiment was made into TARF-P7152 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and the same refinement treatment was carried out by the same method, and the same evaluation as the above evaluations 1 to 6 was performed. . The results are shown in Table 2.

Claims (12)

A coating forming agent for pattern refining, which is characterized in that it is coated on a substrate having a photoresist pattern, and the photoresist pattern is narrowed by heat shrinkage, and then the coating is removed to form a fine pattern. The coating forming agent for miniaturization comprises (a) a water-soluble polymer and (b) a peracid, and does not contain a crosslinking agent, and the component (a) is derived from acrylic acid, methyl acrylate, methacrylic acid, and N. N-Dimethyl acrylamide, N,N-dimethylaminopropyl methacrylamide, N,N-dimethylaminopropyl acrylamide, N-methyl acrylamide, double Acetone acrylamide, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N- Acrylate And a mixed polymer of at least one selected from the group consisting of N-vinylpyrrolidone, vinyl acetate, and N-vinylimidazolidinone, or a mixed polymer thereof, in total solid form The component (a) is contained in an amount of from 1 to 99% by mass, and the component (b) is contained in an amount of from 0.001 to 3 parts by mass based on 100 parts by mass of the component (a). The coating forming agent for pattern miniaturization according to claim 1, wherein the peracid is at least one selected from the group consisting of peracetic acid and perpropionic acid. The coating forming agent for pattern miniaturization according to the first aspect of the invention, wherein the component (b) is contained in an amount of 0.01 to 1 part by mass based on 100 parts by mass of the component (a). A coating forming agent for pattern refining, which is characterized in that it is coated on a substrate having a photoresist pattern, and the photoresist pattern is narrowed by heat shrinkage, and then the coating is removed to form a fine pattern. The coating forming agent for miniaturization comprises (a) a water-soluble polymer and (c) at least one selected from the group consisting of ammonium quaternary ammonium hydroxide and ammonium sulfoxide ammonium halide, and does not contain a crosslinking agent, the above (a The composition is derived from acrylic acid, methyl acrylate, methacrylic acid, N,N-dimethyl acrylamide, N,N-dimethylaminopropyl methacrylamide, N,N-dimethyl Aminopropyl acrylamide, N-methyl acrylamide, diacetone acrylamide, N,N-dimethylaminoethyl methacrylate, N,N-diethylamino methacrylate Ester, N,N-dimethylaminoethyl acrylate, N-propylene fluorenyl And a mixed polymer of at least one selected from the group consisting of N-vinylpyrrolidone, vinyl acetate, and N-vinylimidazolidinone, or a mixed polymer thereof, in total solid form The component (a) is contained in an amount of from 1 to 99% by mass, and the component (c) is contained in an amount of from 0.001 to 3 parts by mass based on 100 parts by mass of the component (a). The coating forming agent for pattern miniaturization according to the fourth aspect of the invention, wherein the component (c) is a quaternary ammonium hydroxide. The coating forming agent for pattern miniaturization according to claim 4, wherein the component (c) is contained in an amount of 0.01 to 1 part by mass based on 100 parts by mass of the component (a). The coating forming agent for pattern miniaturization according to claim 1 or 4, wherein the component (a) is at least one selected from the group consisting of N-vinylpyrrolidone and vinyl acetate. Polymers and/or copolymers. The pattern refinement described in item 1 or item 4 of the patent application scope is A coating forming agent, wherein the component (a) is a polyvinylpyrrolidone. The coating forming agent for pattern miniaturization according to the first or fourth aspect of the invention, wherein the component (a) is a water-soluble polymer having a mass average molecular weight of 50,000 to 300,000. The coating forming agent for pattern refining according to the first or fourth aspect of the invention is an aqueous solution having a solid content of 1 to 50% by mass. A method for forming a fine pattern, comprising the steps of: coating a pattern forming agent for pattern refining according to the first or fourth aspect of the patent application on a substrate having a photoresist pattern; In the heat treatment, the pattern forming agent is thermally shrunk, and the photoresist pattern is narrowed by the heat shrinkage action, and then the pattern forming agent for pattern refining is removed. The method for forming a fine pattern according to claim 11, wherein the heat treatment is performed at a temperature at which the photoresist pattern on the substrate does not generate heat.