JP2001194785A - Resist pattern refining material, method for producing semiconductor device using same material and semiconductor device produced by same method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resist pattern scaledown material capable of forming a resist pattern which is finer than the limit determined by the wavelength of light for exposure, a method for producing a semiconductor device using the material and a semiconductor device produced by the method. SOLUTION: An organic film is formed on a negative type resist pattern using the resist pattern scaledown material comprising a resin, a base generating agent and a solvent and a base component is diffused from the organic film into the resist pattern by heat treatment or irradiation with light to form a solubilized layer on the surface of the resist pattern. This solubilized layer and the organic film are removed with a removing solution to form a resist pattern which is finer than the limit determined by the wavelength of light for exposure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist pattern miniaturizing material for miniaturizing an already formed resist pattern, a method of manufacturing a semiconductor device having a fine pattern using the resist pattern miniaturizing material, and a method of manufacturing the same. The present invention relates to a semiconductor device manufactured by the method. More specifically, we possess resist pattern miniaturization material that realizes high-precision and fine negative resist pattern formation beyond the exposure wavelength limit of negative resist patterns of LSI semiconductor elements, and possesses high-precision and fine patterns using this material The present invention relates to a method for manufacturing a semiconductor device and a semiconductor device using the method.

[0002]

2. Description of the Related Art In a conventional method for manufacturing a semiconductor device, when a resist pattern is formed on a negative resist by exposure to light at an optimum focus by a stepper,
Even with a resist pattern having a fine line width equal to or less than the light source wavelength of the stepper, a resist pattern almost faithful to the pattern of the photomask can be formed, similarly to a resist pattern having a line width larger than the light source wavelength.

However, when a negative resist pattern is formed by exposing the stepper to a defocused state, a resist pattern having a line width larger than the wavelength of the light source of the stepper can obtain dimensions almost faithful to the pattern of the photomask without any problem. However, a resist pattern having a fine line width equal to or less than the wavelength of the light source has a problem in that the dimensional variation is large and a desired dimension cannot be obtained.

[0004]

As described above,
Conventionally, it has been difficult to stably form a fine resist pattern exceeding the limit of the exposure wavelength when the focus is deviated by the photolithography technique in the exposure for manufacturing a semiconductor device.

[0005] The present invention provides a resist pattern miniaturizing material capable of stably forming a pattern exceeding the exposure wavelength limit even when the focus is deviated during exposure, and a semiconductor using the resist pattern miniaturizing material. An object of the present invention is to provide a method of manufacturing a device and a semiconductor device having a fine pattern manufactured by the method.

[0006]

A first resist pattern miniaturizing material according to the present invention comprises a resin, a base generator, and a solvent.

[0007] The second resist pattern miniaturizing material according to the present invention is the first resist pattern miniaturizing material, wherein polyvinyl alcohol, polyacrylic acid, polyvinyl acetal, polyethylene oxide, polyvinyl ether, polyvinyl pyrrolidone, Polyethyleneimine, polyacrylimide, polyvinylamine, polyacrylamine, polyethylene glycol,
One of a polyether polyol and a polyester polyol, or a mixture of two or more thereof is used.

A third resist pattern refinement material according to the present invention is the first resist pattern refinement material, wherein the base generator is any one of a transition metal complex, a benzyl carbamate compound and an oxime compound. is there.

A fourth resist pattern miniaturizing material according to the present invention is the above third resist pattern miniaturizing material, wherein the base generator is a base generator that generates organic amines by ultraviolet irradiation. .

A fifth resist pattern miniaturizing material according to the present invention is the first resist pattern miniaturizing material, wherein the solvent is pure water or an organic solvent within a range that does not dissolve the resist pattern. And a mixed solvent of

A sixth resist pattern miniaturizing material according to the present invention is the first resist pattern miniaturizing material which contains a photosensitizer.

A seventh resist pattern miniaturizing material according to the present invention is the above-described sixth resist pattern miniaturizing material, wherein the photosensitizer is an aromatic hydrocarbon compound, an aromatic nitro compound, an aromatic ketone compound, An aromatic amino compound, a phenolic compound, a quinone compound, an anthracene compound, a coumarin derivative, a phthalocyanine compound, a porphyrin compound, an acridine compound or a xanthene compound.

An eighth resist pattern miniaturizing material according to the present invention is the first or sixth resist pattern miniaturizing material which contains a base component.

A ninth resist pattern miniaturizing material according to the present invention is the eighth resist pattern miniaturizing material, wherein the base component is an amino compound, an imino compound,
It is a hydroxide or a pyridine base, or a salt thereof.

A tenth resist pattern miniaturizing material according to the present invention is the first or sixth resist pattern miniaturizing material containing an acid component.

An eleventh resist pattern miniaturizing material according to the present invention is the above-described tenth resist pattern miniaturizing material, wherein the acidic component is any one of an alkyl carboxylic acid, an alkyl sulfonic acid and a salicylic acid.

The twelfth resist pattern miniaturizing material according to the present invention is any of the first, sixth, eighth and tenth resist pattern miniaturizing materials described above, and further contains a surfactant.

According to a first method of manufacturing a semiconductor device according to the present invention, a resist pattern is formed on a semiconductor substrate by using a negative resist, and the first to twelfth steps according to the present invention are formed on the resist pattern. A step of forming an organic film by applying any resist pattern refinement material, a step of generating a base in the organic film by heat treatment or exposure treatment, and diffusing the generated base component into the negative resist by heat treatment And solubilizing the surface layer of the resist pattern, and dissolving and removing the organic film and the surface layer of the resist pattern with a stripping solution.

According to a second method of manufacturing a semiconductor device according to the present invention, in the first method of manufacturing a semiconductor device, the negative resist can be re-dissolved by diffusion of a base component generated in an organic film as the negative resist. Is used.

According to a third method of manufacturing a semiconductor device according to the present invention, in the second method of manufacturing a semiconductor device, a chemically amplified negative resist is used as the negative resist.

According to a fourth method of manufacturing a semiconductor device according to the present invention, in the first method of manufacturing a semiconductor device, a basic solution is used as a stripping solution.

According to a fifth method of manufacturing a semiconductor device according to the present invention, there is provided the method of manufacturing a semiconductor device according to the fourth method, wherein the basic solution contains an alkali salt containing an ammonium salt such as tetramethylammonium hydroxide or triethanolamine. Either an aqueous solution or a solution obtained by adding a water-soluble organic solvent to this alkaline aqueous solution is used.

According to a sixth method of manufacturing a semiconductor device according to the present invention, in the first method of manufacturing a semiconductor device, an organic solvent or a mixed solvent of pure water and an organic solvent is used as a stripping solution.

According to a seventh aspect of the invention, there is provided a method of manufacturing a semiconductor device according to the fourth or fifth aspect, wherein the pattern of the negative resist is an acidic film having a phenolic hydroxyl group remaining. This dissolves and removes only the surface layer of the negative resist pattern.

According to an eighth method of manufacturing a semiconductor device according to the present invention, in the first method of manufacturing a semiconductor device, the exposure process is selectively performed using a photomask.

A ninth method for manufacturing a semiconductor device according to the present invention is the method for manufacturing a semiconductor device according to any one of the first to eighth aspects, wherein a resist pattern is formed on a semiconductor substrate using a negative resist. The surface of the formed resist pattern is treated with a solution or plasma.

A tenth method of manufacturing a semiconductor device according to the present invention is the method of manufacturing a semiconductor device according to any one of the first to ninth aspects, wherein the base is diffused into the negative resist pattern and a crosslinking reaction of the negative resist is performed. And controlling the solubility of the negative resist pattern to partially dissolve the negative resist pattern formed on the semiconductor substrate, thereby stably forming the negative resist pattern finer than the original dimension. Things.

According to the semiconductor device of the present invention,
A semiconductor device manufactured by any one of the tenth to tenth semiconductor device manufacturing methods.

[0029]

Embodiments of the present invention will be described below with reference to the drawings.

Embodiment 1 FIG. 1 shows a method for manufacturing a semiconductor device according to Embodiment 1 of the present invention, and is a partial cross-sectional view of each step in forming a resist pattern using a resist pattern miniaturizing material. FIG. 2 shows the first embodiment.
FIG. 9 is a partial cross-sectional view of each step in the conventional resist pattern formation to be compared with FIG. 1 and 2, 1 is a wafer, 2 is a semiconductor substrate, 3 is a step, 4 is a chemically amplified negative resist for excimer laser, 5 is a photomask, 6a and 6
Reference numerals b, 6c and 8 denote resist patterns, 7 denotes an organic film (abbreviated as an organic film) of a resist pattern miniaturizing material, and 11 denotes a solubilizing layer.

In the present embodiment, as shown in Step 1,
A wafer 1 having a step 3 formed on a semiconductor substrate 2 is used. A chemically amplified negative resist for excimer laser (abbreviated as negative resist for excimer) 4 is applied on the wafer 1 including the step 3 at a thickness of 2000 to 20000 °. Before applying the negative resist 4 for excimer, the surface of the wafer 1 may be treated with hexamethylene disilazane or the like to enhance the adhesion between the negative resist 4 for excimer and the wafer 1. Also, a negative resist 4 for excimer 4
An upper layer material may be applied thereon. Further, heat treatment may be performed after the application. Further, an antireflection film may be formed.

Next, in step 2, a photomask 5 adjusted so as to obtain a pattern having a line width of 0.25 μm is obtained.
(In the case of 5: 1 reduction projection exposure, 1.25 μm line width)
Is used to selectively irradiate light toward the excimer negative resist 4. In step 2 of the conventional method, 0.1
Photomask 5 prepared to obtain a pattern with a line width of 5 μm (0.75 μm in the case of 5: 1 reduction projection exposure)
The light is selectively irradiated toward the negative resist 4 for excimer by using the (m line width).

Next, in step 3, after the post-exposure bake, a development process is performed. In step 2, even if the focus at the time of exposure is adjusted to the lower stage of the step 3 of the wafer 1, the pattern size is large in the present embodiment, so that the resist pattern 6a of 0.25 μm is obtained in both the upper stage and the lower stage of the step 3. Can be On the other hand, in the conventional method, in the lower stage of the step 3, 0.1
Although a resist pattern 6b of 5 μm is obtained, a resist pattern 6c of 0.20 μm is formed in the upper part of the step 3, and the line width of the resist pattern varies.

Next, in step 4, on the wafer 1, a resist pattern refinement material containing a base generator is used.
An organic film 7 for diffusing a base is formed. As a specific example, 10% by weight of polyvinylpyrrolidone as a base resin with respect to the solution, and 300 ppm with respect to the solution.
Of a perfluoroalkyl polyethylene oxide as a surfactant, 3% by weight of a base generator based on a base resin, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, and ethanol and water as solvents. An organic film 7 is formed by spin coating a resist pattern refinement material composed of a mixed solvent (weight ratio of ethanol to water 3: 7).

Next, in step 5, the wafer 1 is placed on a hot plate (not shown), and the organic film 7 formed on the wafer 1 is heat-treated at 90 to 180 ° C. for about 10 seconds to 3 minutes. I do. By this heat treatment, the base generator in the organic film 7 is decomposed, and the generated base is diffused into the resist pattern 6a, so that the solubilized layer 11 is formed on the surface of the resist pattern 6a.

Next, in step 6, the wafer 1 is added at 2% by weight.
The organic film 7 and the solubilized layer 11 of the resist pattern 6a were dissolved in a basic stripping solution composed of an aqueous solution to which monoethanolamine and 10% by weight of ethanol were added to reduce the size by 0.10 μm. Line width 0.15μm
Can be obtained.

When the heat treatment temperature is increased or the heat treatment time is increased in step 5, the thickness of the solubilized layer 11 to be formed increases, and the amount of reduction in the line width in step 6 can be increased.

In this embodiment, polyvinylpyrrolidone is used as the resin for the resist pattern miniaturization material. Other preferable examples include polyvinyl alcohol, polyacrylic acid, polyvinyl acetal, polyethylene oxide, polyvinyl ether, and polyethylene. Imine, polyacrylimide, polyethylene glycol,
One of polyether polyols and polyester polyols, or a mixture of two or more thereof, or a salt thereof can be used. These resins are not limited to the above, and any resin or polymer soluble in a solvent that does not dissolve the resist pattern and that can be uniformly coated on the substrate can be used. In particular, a water-soluble resin is preferable, and the coating film thickness is 100
Å-20 μm is preferred.

In the present embodiment, an oxime compound [[(2-nitrobenzyl) oxy] carbonyl] is used as the base generator contained in the resist pattern miniaturizing material.
Although propylamine is used, any other oxime compound, transition metal complex or benzyl carbamate compound can be used. Here, the base generator refers to a substance that generates a base by an external action.
The external action includes irradiation with an actinic actinic ray, for example, an ultraviolet ray or an electron beam, or a heating action, or exposure to an appropriate gas or liquid. Irradiation with an ultraviolet ray or a heating action is preferable.

Specific examples of the base generator include hexaammonium cobalt perchlorate, hexapropylamine cobalt perchlorate, hexamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, bromopentane Ammonia cobalt perchlorate, bromopentamethylamine cobalt perchlorate, [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] ethylamine, [[(2
-Nitrobenzyl) oxy] carbonyl] hexylamine,
[[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [[(2-nitro Benzyl) oxy] carbonyl]
Hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] Toluenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-dinitrobenzyl) oxy] carbonyl] ethylamine, [[(2,6-
[Dinitrobenzyl) oxy] carbonyl] propylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6 -Dinitrobenzyl) oxy] carbonyl] aniline, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperidine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2 , 6-Dinitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis
[[(2,6-dinitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] Piperazine, [[(α, α-
Dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl]
Methylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] ethylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] propylamine, [[ (α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] cyclohexylamine, [[(α, α -Dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] aniline, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperidine, bis [[(α, α-dimethyl-3, 5-dimethoxybenzyl) oxy] carbonyl] hexamethylenediamine, bis
[[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine, bis [[(α, α-dimethyl
-3,5-dimethoxybenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] toluenediamine,
Bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperazine, propionylacetophenone oxime, propionylbenzophenone oxime, propionylacetone oxime, butyrylacetophenone oxime, butyrylbenzophenone oxime, butyrylacetone oxime, Adipoyl acetophenone oxime, adipoyl benzophenone oxime, adipoyl acetone oxime, acroylacetophenone oxime,
Examples include, but are not limited to, acroylbenzophenone oxime, acroylacetone oxime, and the like. These base generators may be used alone or in combination of two or more. The content of the base generator is preferably 0.01 to 50% by weight in the resin composition used for the resist pattern miniaturizing material. 0.
When the content is less than 01% by weight, the effect of dissolving the surface layer of the resist pattern with the basic stripping solution is poor, and the content is 50% by weight
If the ratio exceeds the above, the storage stability of the resist pattern miniaturization material may be poor.

Further, the generated base may be either an organic or inorganic base. Organic amines are particularly preferred from the viewpoints of generation efficiency and solubility in organic films. The organic amines generated may be aliphatic or aromatic.
It may be functional or multifunctional. Preferred examples of the generated organic amines include ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine,
Cyclohexylamine, decylamine, cetylamine,
Examples include, but are not limited to, hydrazine, tetramethylenediamine, hexamethylenediamine, benzylamine, aniline, naphthylamine, phenylenediamine, toluenediamine, diaminodiphenylmethane, hexamethyltetramine, piperidine, piperazine and the like. These base generators that generate organic amines may be used alone or in combination of two or more.

Further, in this embodiment, the surfactant is contained in the resist pattern miniaturizing material, and the organic film 7 is formed.
Can be improved. The surfactant is added as one kind or a mixture of two or more kinds. If the organic film 7 can be uniformly formed on the substrate by adding a small amount, an anionic surfactant, a cationic surfactant, a nonionic surfactant, Any of amphoteric surfactants, amphoteric surfactants and fluorine-based surfactants may be used.

In this embodiment, a perfluoroalkyl polyethylene oxide is used as a surfactant. For example, ethylene oxide adducts, polyethylene glycol derivatives, lecithin derivatives, propylene glycol fatty acid esters, glycerin fatty acid esters, polyoxyethylene Glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol, polyoxyethylene alkylphenyl formaldehyde condensate, polyoxyethylene Castor oil or hydrogenated castor oil, polyoxyethylene sterol or hydrogenated sterol Polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers,
Polyoxyethylene alkyl phenyl ether, polyoxyethylene lanolin or lanolin alcohol or beeswax derivative, polyoxyethylene alkylamine or fatty acid amide, polyoxyethylene alkyl ether phosphate or phosphate, alkyl ether carboxylate, alkyl phosphate and Polyoxyethylene alkyl ether phosphate, alkylbenzene sulfonate, sulfonate, quaternary ammonium salt, octylpyrrolidone, alkylpyrrolidone, alkylpyridinium salt, ethylene oxide adduct of tetramethyldecinediol, betaine acetate-type amphoteric surfactant Agent, imidazoline type amphoteric surfactant, block polymerization type nonionic surfactant of ethylene oxide and propylene oxide, perfluoroalkyl sulf Emissions salt, perfluoroalkyl carboxylate, perfluoroalkyl polyoxyethylene ethanols, perfluoroalkyl quaternary ammonium iodide, fluorinated alkyl esters, etc. may also be used. Particularly, a water-soluble surfactant is preferable.

In the present embodiment, as the solvent for the resist pattern refining material, a mixed solvent of pure water and ethanol, which is a mixed solvent of pure water and an organic solvent within a range that does not dissolve the resist pattern, is used. However, other than these, an organic solvent or pure water that does not dissolve the resist pattern can also be suitably used.

Further, in the present embodiment, a basic solution such as an alkali developing solution used for ordinary resist development is used as a stripping solution, but an organic solvent or a mixed solution of an organic solvent and pure water is also used. Can be used.

Examples of the basic stripping solution include an aqueous solution, an organic solution, or an organic solvent and pure water to which a basic compound such as an amino compound, an imino compound, a hydroxide, a pyridine base, or a salt thereof is added. Specific examples thereof include an alkaline aqueous solution containing an ammonium salt such as tetramethylammonium hydroxide and triethanolamine, or a solution obtained by adding an alcohol to this alkaline aqueous solution.

Examples of the stripping solution for the organic solvent include alcohols, ketones, ethers, esters, halogenated hydrocarbons, benzenes, alkoxybenzenes, and cyclic ketones, such as toluene, xylene, and methoxybenzene. , Ethoxybenzene, phenol, benzene,
Pyridine, cyclohexane, dioxane, methyl ethyl ketone, methyl isobutyl ketone, acetone, t-butyl acetate, n-butyl acetate, ethyl acetate, tetrahydrofuran, diethyl ether, isopropyl ether, methyl cellosolve, ethyl cellosolve, N-methylpyrrolidone,
Dimethyl sulfoxide, N, N'-dimethylformamide,
Ethanol, methanol, isopropanol, butyl alcohol, ethylene glycol, ethylbenzene, diethylbenzene, n-butylether, n-hexane, n-heptane, methoxybenzene, ethoxybenzene, phenetol, veratrol, γ-butyrolactone, chloroform and the like, Solvents used alone or mixed in a range that does not completely dissolve the resist pattern in accordance with the solubility of the material used for the organic film are used.

As a stripping solution for the mixed solution of the organic solvent and pure water, a mixed solution of a polar organic solvent which is a good solvent for dissolving both the organic film and the resist pattern and pure water which is a poor solvent is used. .

In this embodiment, the resist pattern miniaturizing material is a resin, a base generator, a surfactant,
Although it is composed of a solvent, it is also possible to apply one containing other components.

For example, an acidic component such as an alkyl carboxylic acid, an alkyl sulfonic acid, or a salicylic acid may be added to the resist pattern miniaturizing material. The addition of the acid component has an effect of suppressing the base diffusion length from the organic film 7 to the resist.

Next, a mechanism for performing a heat treatment on the organic film 7 formed of the resist pattern miniaturizing material in the present embodiment to form a solubilized layer 11 which is dissolved in a basic aqueous solution on the surface of the resist pattern 6a. Will be described.

Among the chemically amplified negative resists for excimer lasers, those composed of a novolak resin, melamine (crosslinking agent) and an acid generator are widely used and are alkali-soluble. When this is irradiated with light, an acid is generated,
A cross-linking reaction occurs between the novolak resin and melamine to increase the molecular weight, and becomes insoluble in a developer containing 2.38% by weight of tetramethylammonium hydroxide. That is, the feature of this resist is that the difference in solubility in the alkaline developer between the irradiated part and the unirradiated part is large.

However, since the phenolic hydroxyl group remains in the molecular structure of the portion cross-linked by light irradiation, it may be solubilized depending on the concentration and type of the base. Therefore, when a base generated by the heat treatment of the organic film 7 is allowed to act on the resist pattern 6a, the base layer is supplied with a high concentration of alkali and becomes alkali-soluble, and is treated with a basic stripping solution. Only the part where the base in the base is diffused is dissolved, and the width of the resist pattern can be reduced.

As described above, in this embodiment, first, a resist pattern 6a is formed on a semiconductor substrate by ordinary photolithography using an acid-catalyzed chemically amplified negative resist for excimer laser. Next, an organic film 7 containing a base generator is formed on the resist pattern 6a using a resist pattern refinement material. The base is generated from the base generator in the organic film 7 by the heat treatment, and is diffused into the resist pattern 6a. And
The solubilized layer 11 that dissolves in the stripping solution is formed on the surface of the resist pattern 6a by the base catalysis. Thereafter, the organic film 7 and the solubilized layer 11 are separated by a stripping solution,
A resist pattern 8 having a smaller line width than the initially formed resist pattern 6a is formed. That is, a fine pattern having a wavelength equal to or shorter than the exposure wavelength can be formed stably.

In the above description, the case where the resist pattern 6a is formed on the semiconductor substrate 2 has been described. However, in the manufacture of a semiconductor device, a resist pattern is formed not only on a semiconductor substrate, but also on an insulating film such as a silicon oxide film, or on various films such as a polysilicon film and a metal film. This embodiment can be applied when forming a resist pattern on all of these base films. In the present invention, "on a semiconductor substrate" includes all of these cases.

Embodiment 2 FIG. 3 shows a method of manufacturing a semiconductor device according to Embodiment 2 of the present invention, and is a partial cross-sectional view of each step in forming a resist pattern to be partially reduced. In FIG. 3, 6 is a resist pattern, 9 is an organic film, 10 is a photomask, and 10a is an opening.

In the second embodiment, in step 1, a 0.25 μm-wide line-and-space (abbreviated as “excimer negative resist”) is formed on the semiconductor substrate 2 by a normal photolithography using a chemically amplified negative resist for excimer laser. A resist pattern 6 (abbreviated as L / S) is formed.

In step 2, an organic film 9 made of a resin containing a photobase generator is formed on the semiconductor substrate 2 including the resist pattern 6 using a resist pattern miniaturizing material. Specifically, 7% by weight of polyvinyl alcohol as a base resin based on the solution and 3% by weight of a base generator based on the base resin [[(2,6-dinitrobenzyl) oxy] carbonyl] propyl A resist pattern miniaturizing material composed of an amine and a mixed solvent of isopropyl alcohol and water as a solvent (weight ratio of isopropyl alcohol to water is 3 to 7) is spin-coated, and heated at 50 to 100 ° C. using a hot plate. The heat treatment is performed for about 10 seconds to 3 minutes to form the organic film 9.

In step 3, the opening 1 is formed only in the portion where the line width of the resist pattern 6 having a width of 0.25 μm L / S is to be reduced.
The organic film 9 is covered with a photomask 10 so that 0a overlaps the organic film 9.
Light irradiation of 2000 mJ / cm 2 is performed. By this exposure treatment, a base component is selectively generated only in the exposed portion of the organic film 9.

In step 4, the wafer 1 is heat-treated at 50 to 150 ° C. for about 10 seconds to 3 minutes using a hot plate. As a result, the generated base component is diffused into the pattern 6 of the negative resist for excimer, and the solubilized layer 11 that is dissolved in the stripping solution is formed on the surface of the resist pattern 6 by the base catalysis.

In step 5, the organic film 9 and the solubilized layer 11 are removed with a stripper. Specifically, peeling is performed with an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide. After peeling, heat treatment is performed at 100 to 130 ° C. for about 1 to 3 minutes to remove moisture and the like in the pattern.

As a result, only the dimension of the resist pattern 6 in contact with the exposed portion of the organic film 9 is reduced by 0.1 μm, and the line width of 0.15 μm which cannot be formed by the initial KrF excimer laser photolithography. Thus, the resist pattern 8 having a space width of 0.35 μm can be selectively formed. In step 3, if the entire surface is exposed without using the photomask 10, the solubilized layer 11 is formed on all the resist patterns 6, and all the resist patterns 6 in the plane can be thinned.

As the resin, photobase generator and solvent used for the resist pattern miniaturizing material of the present embodiment, the materials described in the first embodiment can be used in addition to the above-mentioned materials.

In the present embodiment, an aromatic hydrocarbon compound, an aromatic nitro compound, an aromatic ketone compound, an aromatic amino compound, a phenolic compound, a quinone compound, an anthracene compound, a coumarin derivative, A photosensitizer such as a phthalocyanine compound, a porphyrin compound, an acridine compound, or a xanthene compound can be added to improve the sensitivity of the photobase generator and increase the amount of generated base. That is, the photosensitizer is added to improve the sensitivity of the base generator and has a role of increasing the amount of generated base. Further, the photosensitizer also has a role of generating a base in combination when the base generator alone does not generate a base even when irradiated with light.

Specific examples of the photosensitizer include, for example, naphthalene, anthracene, phenanthrene, chrysene, nitrobenzene, p-dinitrobenzene, 1,3,5-trinitrobenzene, p-nitrodiphenyl, nitroaniline, dinitroaniline, picramide , 2-chloro-4-nitroaniline, phenol, p-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol, benzaldehyde, 9-anthraldehyde, acetophenone, benzophenone, dibenzalacetone, Benzyl, p, p'-diaminobenzophenone, p, p'-dimethylaminobenzophenone, p, p'-tetramethyldiaminobenzophenone, benzoquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, anthraquinone, 1,2-benzo Anthraquinone, anthrone, 1,9-benzoanthraquinone, 6-phenyl-1,9- Benzoanthraquinone, 3-phenyl-1,9-benzoanthraquinone, 2-keto-3-aza-1,9-benzoanthraquinone, 3-methyl-1,3-diaza-1,9-benzoanthraquinone, 2-nitro Fluorene, 2,7-dinitrofluorene, 2,5-dinitrofluorene, 1,8-phthaloylnaphthalene, 2-chloro-1,8-
Phthaloylnaphthalene, 4-chloro-1,8-phthaloylnaphthalene, 5-nitroacenaphthene, 5,6-dinitroacenaphthene, 5-benzoylacenaphthene, 1-nitropyrene, N-
Acetyl-4-nitro-1-aminonaphthalene, N-phenylthioacridone, triphenylpyrylium perchlorate, 4-methoxyphenyl-2,6-diphenylpyrylium perchlorate, 4-butoxyphenyl-2,6 -Diphenylpyrylium perchlorate, 4-pentyloxyphenyl-2,6
-Diphenylpyrylium perchlorate, 2,4,6-trimethoxyphenyl-2,6-diphenylpyrylium perchlorate, 4-methoxyphenyl-2,6-diphenylthiopyrylium perchlorate, 4-butoxyphenyl -2,6-diphenylthiopyrylium perchlorate, 4-amyloxyphenyl-2,6-diphenylthiopyrylium perchlorate,
2,4,6-trimethoxyphenyl-2,6-diphenylpyrylium perchlorate, 3-ketocoumarin, allylcoumarin,
Aroyl coumarin, alkoxycarbonylbiscoumarin, dialkylketobiscoumarin, 2-ethyl-9,10-dimethoxyanthracene, 2-carboxy-9,10-dimethoxyanthracene, 2-hydroxy-9,10-dimethoxyanthracene, 2-amino Examples include, but are not limited to, -9,10-dimethoxyanthracene. These photosensitizers may be used alone or in combination of two or more. The amount of the photosensitizer to be added is preferably 0.01 to 20% by weight in the resin composition used for the resist pattern refining material. If the amount is less than 0.01% by weight, the effect of improving sensitivity is low, and if it exceeds 20% by weight, the storage stability of the resist pattern miniaturizing material may be poor.

Also in the present embodiment, an acid component such as an alkyl carboxylic acid, an alkyl sulfonic acid, and a salicylic acid can be added to the resist pattern miniaturizing material to suppress the base diffusion length into the resist pattern 6. . Further, a surfactant may be added to the resist pattern miniaturizing material to improve the film forming property of the organic film 9.

Further, also in the present embodiment, the stripping solution contains
A basic solution such as an alkali developer used for ordinary resist development, an organic solvent or a mixed solution of an organic solvent and pure water can be used, preferably, a tetramethylammonium hydroxide-containing basic aqueous solution, or What added alcohol to this basic aqueous solution can be used.

In the present embodiment, a KrF excimer laser is used as the light for irradiating the organic film 9. However, if the light has a wavelength sensitive to the photobase generator, g-line or i-line of an Hg lamp, ArF excimer laser laser, Deep-UV,
EB (electron beam) or X-ray can also be used.

As described above, in the present embodiment, first, a resist pattern 6 is formed on a semiconductor substrate 2 by ordinary photolithography using a chemically amplified negative resist for excimer laser. Next, an organic film 9 containing a photobase generator is formed on the resist pattern 6 using a resist pattern miniaturizing material, and this is irradiated with light to generate a base. Then, the heat treatment diffuses the generated base into the resist pattern 6 and forms a solubilized layer 11 that can be dissolved in the surface layer of the resist pattern by a stripping solution by the base catalysis. Thereafter, the organic film 9 and the solubilized layer 11 are dissolved and removed with a stripping solution, so that a resist pattern 8 thinner than the initially formed one can be formed.

By controlling the amount of base generation based on the amount of light irradiation and controlling the diffusion length of base by heat treatment, the amount of reduction in the size of the resist pattern can be changed. Further, at the time of light irradiation, a resist pattern 8 which is selectively thinned can be formed by performing selective exposure using a photomask.

Embodiment 3 FIG. 4 shows a method of manufacturing a semiconductor device according to Embodiment 3 of the present invention, and is a partial cross-sectional view of each step in forming a resist pattern having different reduction amounts. In FIG. 4, reference numerals 8a and 8b denote resist patterns.

First, in step 1, a resist pattern 6 having a width of 0.25 μm L / S made of a chemically amplified negative resist is formed on the semiconductor substrate 2 by ordinary photolithography.

Next, in step 2, a basic organic film 9 that generates a base by light irradiation is formed on the semiconductor substrate 2 including the resist pattern 6 using a resist pattern refinement material.
To form In other words, the organic film 9 is formed using a resist pattern refinement material containing a photobase generator and a base component. As a specific example, 8% by weight based on the solution
Polyvinyl alcohol as a base resin, tetramethylammonium hydroxide as a base component in 2% by weight based on the solution, and 3% by weight in base resin
[[(2,6-dinitrobenzyl) oxy]
Carbonyl] propylamine, and a resist pattern refinement material composed of a mixed solvent of N-methylpyrrolidone and water as a solvent (the weight ratio of N-methylpyrrolidone to water is 3 to 97) is spin-coated and hot-coated. 5 depending on the plate
Heat treatment is performed at 0 to 100 ° C. for about 10 seconds to 3 minutes to form the organic film 9.

Next, in step 3, 0.25 μm width L / S
The organic film 9 is covered with a photomask 10 so that the opening 10a overlaps only the portion where the line width of the resist pattern 6 is to be made thinner. Irradiation is performed. The base is selectively generated only in the exposed portion of the organic film 9 by the exposure processing.

Next, in step 4, the wafer 1 is subjected to a heat treatment at 50 to 150 ° C. for about 10 seconds to 3 minutes using a hot plate. Thereby, the base component originally contained and the base component generated by light irradiation are diffused into the resist pattern 6 of the chemically amplified negative resist, and the base catalyst acts on the surface layer of the resist pattern 6 with a stripping solution. A solubilized layer 11 that dissolves is formed.

Next, in step 5, the organic film 9 and the solubilized layer 11 of the resist pattern are peeled off in the same manner as in the second embodiment.

As a result, the size of the resist pattern 6 in contact with the exposed portion of the organic film 9 was reduced by 0.15 μm, and that of the resist pattern 6 in contact with the other portions was reduced by 0.10 μm. That is, it is possible to simultaneously form a resist pattern 8a having a line width of 0.10 μm and a resist pattern 8b having a line width of 0.15 μm, which are thinner than the line width of the original resist pattern and differing in reduction amount.

In this embodiment, tetramethylammonium hydroxide is contained as a base component in the resist pattern miniaturizing material. The base component used in the present embodiment includes an amino compound, an imino compound,
It may be a hydroxide, a pyridine base, or a salt thereof. The addition of these base components has an effect of increasing the amount of the base component diffused into the chemically amplified negative resist 6 and increasing the thickness of the solubilized layer 11 due to the synergistic effect of the base generator with the base component, and the base generation. There is an effect that the solubilized layer 11 is formed by diffusion of the added base component also in a region where the agent does not generate a base component (a region not irradiated with active actinic rays, for example, ultraviolet rays, electron beams, etc.). That is, the region where the base is generated from the base generator by irradiating an active actinic ray, for example, an ultraviolet ray or an electron beam, or the unirradiated region where no base is generated, depends on the amount of the base component to be added. Can be controlled.

Specific examples of the base component added to the resist pattern miniaturizing material include, for example, tetramethylammonium hydroxide, ethanolamine, triethylamine, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, and the like.
Cyclohexylamine, decylamine, cetylamine,
Hydrazine, tetramethylenediamine, hexamethylenediamine, benzylamine, aniline, naphthylamine, phenylenediamine, toluenediamine, diaminodiphenylmethane, hexamethyltetramine, piperidine, piperazine, and the like, but are not limited to the above, and the resist pattern is not limited to the above. The base component is not particularly limited as long as it is a base component that is soluble in a solvent in which is not dissolved.

As described above, in the present embodiment, first, a resist pattern 6 is formed on a semiconductor substrate 2 by ordinary photolithography using a chemically amplified negative resist. Next, an organic film 9 is formed on the resist pattern 6 using a resist pattern miniaturizing material containing a base component and a photobase generator, and this is irradiated with light to generate a base. Then, the heat treatment of the organic film 9 diffuses the base component originally contained and the base component generated in the portion irradiated with light into the resist pattern 6, and the base catalyst acts on the surface layer of the resist pattern 6. The solubilizing layer 11 that is dissolved by the stripping solution is formed. Thereafter, the organic film 9 and the solubilized layer 11 are dissolved and removed with a stripping solution, so that the resist patterns 8a and 8b which are thinner than the initially formed resist pattern 6 and have different line widths can be formed.

In this embodiment, the amount of reduction in the size of the resist pattern can be changed by controlling the solubility of the resist pattern 6 by the amount of light irradiation and controlling the diffusion length of the base by heat treatment. In addition, at the time of light irradiation, a resist pattern having a different reduction width can be formed by performing selective exposure using a photomask.

Embodiment 4 FIG. 5 shows a method of manufacturing a semiconductor device according to the fourth embodiment of the present invention, and is a top view of each step in forming a resist pattern partially narrowed. In FIG. 5, reference numeral 12 denotes a resist pattern;
2a is a resist pattern having a reduced line width.

The formation of the resist pattern in step 1 and the formation of the organic film 9 using the resist pattern miniaturizing material in step 2 were the same as in the second embodiment.

In step 3, the organic film 9 is covered with the photomask 10 so that the opening 10a is located at the portion where the line width of the 0.25 μm wide L / S resist pattern 6 is to be reduced.
10 to 3000 by KrF excimer laser on organic film 9
Light irradiation of mJ / cm 2 is performed. That is, light is applied to the belt-shaped portion having a width 10a at the center of the resist patterns 6 arranged in parallel, and the upper and lower belt-shaped portions shield the light. By this exposure treatment, a base is selectively generated only in the exposed portion of the organic film 9.

In step 4, the same heat treatment as in the second embodiment is performed to form a solubilized layer 11 on the surface of the resist pattern 6.

In step 5, the organic film 9 and the solubilized layer 11 are removed with a stripper. Specifically, the release treatment is performed with an aqueous solution to which 3% by weight of N-methylpyrrolidone is added.

As a result, while the dimension of the resist pattern 6 in contact with the exposed portion of the organic film 9 was reduced by 0.1 μm, the other portion was reduced by 0.01 μm, and the line width was partially reduced. The resist pattern 12 having the changed portion 12a can be formed.

In the present embodiment, when the organic film 9 is formed using a resist pattern refiner containing a photobase generator and a base component as in the third embodiment, the exposed portion of the organic film 9 is reduced. 0.1μ for contacting resist pattern
m, and the rest is reduced by 0.05 μm.
That is, in the same resist pattern, it is possible to form a resist pattern which can be made thinner than the resist pattern originally formed, and in which the amount of reduction in the line width is partially different.

Embodiment 5 FIG. 6 shows a method of manufacturing a semiconductor device according to Embodiment 5 of the present invention, and is a top view of each step in forming a resist hole pattern.
FIG. 7 is a top view of a resist hole pattern formed by a conventional method for comparison. 6 and 7, reference numeral 17 denotes a resist hole pattern, reference numeral 18 denotes a resist hole pattern after enlargement, and reference numeral 19 denotes a dimple.

As shown in FIG. 7, when the conventional technique is used, a halftone photo resist is formed by forming a resist pattern having a narrow hole interval, for example, a hole pattern 17 having a hole size of 0.30 μm and a hole interval of 0.18 μm. When a mask is used, dimples (dents) 19 are generated due to the sub-peaks, and unnecessary holes are formed after etching.

In the present embodiment shown in FIG. 6, first, in Step 1, a hole size of 0.24 μm and a hole interval of 0.24 μm are formed on a semiconductor substrate 2 using a chemically amplified negative resist by ordinary photolithography. 24 .mu.m resist hole pattern 17 is formed. When the hole size is 0.24 μm and the hole interval is 0.24 μm, there is a margin in the focus margin and the hole size is 0.30 μm.
No dimple (dent) observed when the hole interval was 0.18 μm.

In step 2, the resist hole pattern 17
An organic film 9 containing a photobase generator is formed on a semiconductor substrate containing the same using the same resist pattern refinement material as in the second embodiment.

In step 3, a photomask 10 is set on the organic film 9 so that the opening overlaps the position of the resist hole pattern 17 having a diameter of 0.24 μm. Light irradiation of up to 3000 mJ / cm2 is performed. By this exposure treatment, a base is generated in the light-irradiated portion of the organic film.

In step 4, the same heat treatment as in the second embodiment is performed. Thus, the generated base component is diffused into the resist hole pattern 17 of the chemically amplified negative resist, and the base hole catalyzes the resist hole pattern 1.
7 is dissolved in the stripping solution, and the solubilized layer 11
To form

Although not shown in FIG. 6, in step 5, the organic film 9 and the solubilized layer 11 are removed with a stripper. In particular,
A peeling treatment is performed with a solution obtained by adding 5% by weight of isopropyl alcohol to an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide.

As a result, the dimension of the resist hole pattern 17 is increased by 0.06 μm, the hole size is 0.30 μm and the hole interval is 0.18 μm, which cannot be obtained by the prior art.
A resist hole pattern 18 having a small hole interval of μm can be formed.

This embodiment is an application of the resist pattern miniaturizing material and the process of the above-described embodiment to the resist hole pattern 17. Although the generated resist pattern is different, the process and its effects are the same. It is. This process is also applicable to a resist hole pattern formed using a normal photomask.

Embodiment 6 FIG. The method for manufacturing a semiconductor device according to the sixth embodiment is the same as the method for manufacturing a semiconductor device according to the second embodiment shown in FIG.
After the formation of the resist pattern 6 using an excimer negative resist by ordinary photolithography, a step of treating the surface of the formed resist pattern 6 with a solution or plasma is added.

That is, in this embodiment, as shown in step 1 of FIG. 3, 0.25 μm of excimer negative resist is formed on the semiconductor substrate 2 by ordinary photolithography.
A resist pattern 6 having an m width L / S is formed.

Next, in the formed resist pattern 6,
The surface property of the resist pattern 6 is changed by performing one of a surface treatment by immersion in a solution or a spin coating of the solution, and a surface treatment by plasma generated by an asher device.

Next, the same processing as in the second embodiment is performed on the resist pattern 6 that has been subjected to the above surface treatment.
That is, as in step 2 of FIG. 3, an organic film 9 made of a resist pattern miniaturizing material is formed on the resist pattern 6.
To form Specifically, polyvinyl alcohol as a base resin is 8% by weight based on the solution, and a base generator is 5% by weight based on the base resin [[(2-nitrobenzyl)].
A resist pattern miniaturizing material composed of oxy] carbonyl] cyclohexylamine, octylpyrrolidone as a surfactant at 500 ppm with respect to a solution, and water as a solvent is spin-coated, and 50 μm by a hot plate.
A heat treatment is performed at １００100 ° C. for about 10 seconds to 3 minutes to form the organic film 9.

Next, as in step 3 of FIG.
The organic film 9 is covered with the photomask 10 so that the opening 10a overlaps only the portion where the line width of the resist pattern 6 of m width L / S is to be reduced, and the organic film 9 is irradiated with light of 30 to 2000 mJ / cm2 by a KrF excimer laser. Irradiation is performed. By this exposure treatment, a base component is selectively generated only in the exposed portion of the organic film 9.

Next, as in step 4 of FIG.
For about 10 seconds at 50-150 ° C. using a hot plate.
Heat treatment is performed for 3 minutes. The base component generated thereby is diffused into the pattern 6 of the negative resist for excimer, and the solubilized layer 11 that is dissolved in the stripping solution is formed on the surface of the resist pattern 6 by the base catalysis.

Next, as in step 5 of FIG. 3, the organic film 9 and the solubilized layer 11 are removed with a stripper. Specifically, 1.
Stripping is performed with an aqueous solution to which 0% by weight of tetramethylammonium hydroxide and 15% by weight of isopropyl alcohol are added. After peeling, heat treatment is performed at 100 to 130 ° C. for about 1 to 3 minutes to remove moisture in the pattern.

As a result, only the resist pattern 6 in contact with the exposed portion of the organic film 9 has a size of 0.15
It is possible to selectively form a very fine resist pattern 8 having a line width of 0.10 μm, which cannot be formed by the initial photolithography of a KrF excimer laser, by reducing the size by μm. If the entire surface is exposed without using the photomask 10, the solubilized layer 11 is formed on all the resist patterns 6, and all the in-plane resist patterns 6 can be thinned.

The surface treatment solution for the negative resist pattern 6 of this embodiment is a single organic solvent, a mixed organic solvent of two or more types, or an aqueous solution, and does not completely dissolve the negative resist pattern 6. Any solution can be used. As the mixed organic solvent of two or more, for example, a mixed solvent of a good solvent and a poor solvent for the resist pattern 6 is preferable, and as the aqueous solution, for example, a mixed aqueous solution of alcohol and pure water is preferable. Further, a base component, an acid component, and a surfactant may be added to the surface treatment solution.

Although any kind of plasma gas may be used for the surface treatment of the negative resist pattern 6 of the present embodiment, oxygen is particularly preferable. The plasma irradiation time on the surface of the negative resist pattern 6 is 1 second to 5 minutes, preferably 5 seconds to 60 seconds.

As described above, in the present embodiment, the resist pattern 6 made of the negative resist for excimer is formed on the semiconductor substrate 2 by ordinary photolithography.
After the formation of the resist pattern 6, the surface of the formed resist pattern 6 is treated with a solution or plasma to form a resist pattern 6
Changes the surface properties of The change in the surface properties of the resist pattern 6 is caused by the fact that the base component generated in the organic film 9 of the resist pattern miniaturization material by the exposure becomes easy to diffuse, and the addition of the base component and the photosensitizer to the resist pattern miniaturization material,
Alternatively, the selective thick solubilizing layer 11 that cannot be achieved by increasing the amount of light irradiation or increasing the heat treatment temperature for diffusing the base.
Can be formed, the reduction amount of the resist pattern 6 is increased,
An extremely fine resist pattern 8 can be realized.

Next, a description will be given of a semiconductor device manufactured by the resist pattern miniaturizing material of the embodiment described above and a semiconductor device manufacturing method using this resist pattern miniaturizing material.

Embodiment 7 FIG. 8A and 8B show a semiconductor device according to a seventh embodiment of the present invention. FIG. 8A is a partial sectional view of a wafer on which a fine resist pattern is formed, and FIG. It is a partial sectional view. In FIG. 8, reference numeral 13 denotes an insulating film;
Is a conductive film, and 14a is a wiring pattern.

In this embodiment, as shown in FIG. 8A, the semiconductor substrate 2, the insulating film 13 formed on the semiconductor substrate 2, and the insulating film 13 formed on the insulating film 13 are formed. In a wafer 1 composed of a conductive film 14 such as a polysilicon film or an aluminum film, a resist pattern 8 having a line width of 0.15 μm is formed on the conductive film 14 by the method of the second embodiment. The conductive film 14 is etched through the formed resist pattern 8 to form a wiring pattern 14a having a line width smaller than the limit of the exposure wavelength.

That is, the semiconductor device of this embodiment is
As shown in FIG. 8B, the insulating film 13 formed on the semiconductor substrate 2 has a feature that, for example, the wiring pattern has a line width of 0.15 μm and is narrower than the limit of the exposure wavelength. It is a semiconductor device.

Embodiment 8 FIG. 9A and 9B show a semiconductor device according to an eighth embodiment of the present invention, in which FIG. 9A is a partial cross-sectional view of a wafer on which resist patterns having different line widths are formed, and FIG. FIG. 4 is a partial cross-sectional view of a semiconductor device having a pattern. In FIG. 9, 1
4b is a wiring pattern.

In this embodiment, as shown in FIG. 9A, the semiconductor substrate 2, the insulating film 13 formed on the semiconductor substrate 2, and the insulating film 13 formed on the insulating film 13 are formed. In the wafer 1 composed of a conductive film 14 such as a polysilicon film or an aluminum film, a resist pattern 6 having a line width of 0.15 μm and a line width of 0.1 μm are formed on the conductive film 14 by the method of the second embodiment. A resist pattern 8 of 24 μm is formed. This formed resist pattern 6
The conductive film 14 is etched through the resist pattern 8 and the resist pattern 8 to form wiring patterns having different line widths.

That is, the semiconductor device of this embodiment is
As shown in FIG. 9B, on the insulating film 13 formed on the semiconductor substrate 2, for example, a wiring pattern 14a having a line width of 0.15 μm and a line width narrower than the limit of the exposure wavelength is formed. The semiconductor device has a feature that it has a wiring pattern having a line width different from the wiring pattern 14b having a line width of approximately 0.24 μm and a substantially normal line width.

Embodiment 9 FIG. 10A and 10B show a semiconductor device according to a ninth embodiment of the present invention. FIG. 10A is a partial cross-sectional view of a wafer on which a resist pattern with a partially reduced line width is formed, and FIG. FIG. 4 is a partial cross-sectional view of a wafer on which a wiring pattern with a partially reduced line width is formed, and FIG. 4C is a partial cross-sectional view of a semiconductor device.
In FIG. 10, 15 is an interlayer insulating film, 16a is a conductor plug, and 16b is a wiring.

In the present embodiment, as shown in FIG. 10A, the semiconductor substrate 2, the insulating film 13 formed on the semiconductor substrate 2, and the insulating film 13 formed on the insulating film 13 are formed. In the wafer 1 composed of a conductive film 14 such as a polysilicon film or an aluminum film, a resist pattern 12a having a partially reduced line width is formed on the conductive film 14 by the method of the fourth embodiment. I have. The partially narrowed line width of the resist pattern 12a is 0.15 μm. The conductive film 14 is etched through the formed resist pattern 12a, and as shown in FIG. 10B, the wiring pattern having a line width narrower than the limit of the exposure wavelength is partially formed on the insulating film 13 of the wafer 1. 14a are formed.

As shown in FIG. 10C, the semiconductor device according to the present embodiment is different from the wafer 1 in which the wiring pattern 14 a having a small line width is partially formed on the insulating film 13, and the interlayer insulating film 13. It is composed of an insulating film 15, a conductor plug 16 a extending vertically between the interlayer insulating films 15, and a wiring 16 b on the interlayer insulating film 15. That is, in the semiconductor device of the present embodiment, the wiring pattern 14a is a word line,
This is a semiconductor device having characteristics as a semiconductor memory in which the wiring 16b is a bit line.

The semiconductor devices described in the seventh to ninth embodiments are semiconductor devices having a fine wiring pattern having a line width exceeding the limit of the exposure wavelength.

Hereinafter, the resist pattern miniaturizing material of the present invention and a method of manufacturing a semiconductor device using the material will be described in more detail with reference to Examples. However, the present invention is not limited to these Examples. .

[0121]

[Embodiment 1] First, a chemically amplified negative resist was dropped on a silicon wafer and spin-coated, and then heated to 80 ° C.
Is performed for 90 seconds to evaporate the solvent in the resist to form a resist film having a thickness of about 0.75 μm.
Next, a KrF excimer laser reduction projection exposure apparatus is used.
The resist is exposed using an exposure photomask having a 35 μmL / S pattern. Next, a post-exposure bake treatment is performed at 110 ° C. for 90 seconds, followed by development using an alkaline developer (NMD3 manufactured by Tokyo Ohka Kogyo Co., Ltd.).
A resist pattern of 0.35 μmL / S is obtained.

Next, 4% by weight of polyvinylpyrrolidone having a weight average molecular weight of 450,000 and 3% by weight of this resin were used.
Of [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine in an aqueous solution containing 500 ppm of tetramethyldecinediol ethylene oxide adduct, or a resist pattern refinement material Further, a resist pattern refinement material to which a base or an acid described in Table 1 is added is spin-coated on the resist pattern at 3000 rpm, and heat-treated at 90 ° C. for 60 seconds on a hot plate to obtain about 7
An organic film of 00 ° is formed.

Next, the organic film is exposed (500 mJ / cm 2) using a KrF excimer laser reduction projection exposure apparatus and an exposure photomask having an arbitrary pattern to generate a base in the exposed portion. The substrate was placed on a hot plate and subjected to a heat treatment for 60 seconds under the temperature conditions shown in Table 1 (this heat treatment is abbreviated as mixing bake) to diffuse the base component into the resist pattern and form a solubilized layer on the resist pattern surface. After the formation, it is immersed in a stripping solution of an aqueous solution containing 2% by weight of tetramethylammonium hydroxide and 5% by weight of butyl acetate for 60 seconds to dissolve and remove the portion. Further, it is washed with pure water, and
Perform post-bake for 0 seconds.

Table 1 shows the dimensions of the resist pattern obtained by these processes. As the mixing bake temperature increases, the reduction amount of the resist pattern line width increases. In other words, it is shown that an increase in the mixing bake temperature has the effect of forming a finer resist pattern by increasing the generation amount of the base component and increasing the solubilized layer.

In addition, when monoethanolamine is added as a base, the amount of addition of the monoethanolamine increases, the line width reduction amount of the resist pattern between the exposed portion and the unexposed portion increases, and the line width of the resist pattern in the exposed portion increases. The width has shrunk much more. This shows that the base has the effect of forming a solubilized layer also in the resist pattern of the unexposed portion, and forming a larger solubilized layer in the exposed portion, thereby forming a miniaturized resist pattern having a different line width. I have. further,
It is shown that the addition of acetic acid as an acid has the effect of neutralizing the generated base component with the acid, suppressing the increase in the solubilized layer, and forming a controlled fine resist pattern.

Embodiment 2 FIG. A resist pattern is formed in the same manner as in the first embodiment. Next, in the same manner as in Example 1, an organic film is formed using a resist pattern refinement material that does not contain a base component and an acid component. Then, an organic film is formed using a resist pattern refinement material to which a sensitizer 3-ketocoumarin shown in Table 1 is added. These organic films were exposed with an i-line stepper (500 mJ / cm
2), and then the same processing as in the first embodiment is performed. Table 1 shows the dimensions of the resist pattern obtained by these processes.
Shown in When using a resist pattern refinement material to which no sensitizer was added, the line width of the resist pattern in contact with the exposed portion of the organic film was hardly reduced similarly to the resist pattern in contact with the unexposed portion. . However, when a resist pattern refinement material to which a sensitizer is added is used, the line width of the resist pattern in contact with the exposed portion is reduced. In other words, it shows that the sensitizer gives an activity to the base generator and has an effect of generating a base even when it does not generate a base by itself.

Table 1. Results of Examples 1 and 2

[Table 1] 1): Exposure to i-line

Example 3 A photolithography was performed on a semiconductor substrate by ordinary photolithography.
Using an acid-catalyzed chemically amplified negative resist for rF excimer laser, a resist pattern shown in Step 1 of Embodiment 4 (see FIG. 5) having a film thickness of about 0.6 μm and a width of L / S of 0.25 μm is formed.

Next, 5% by weight of polyvinyl alcohol having a weight average molecular weight of 500,000 and 10% by weight of propionyl acetone oxime with respect to the resin were added at 300 ppm.
A resist pattern refinement material in which ethanol and pure water are dissolved in a 30/70 by weight mixed aqueous solution containing perfluoroalkylpolyethylene oxide is spin-coated at 2,000 rpm on the resist pattern to form a film having a thickness of about 6500 ° An organic film is formed.

Next, put on a hot plate and heat at 90 ° C.
And a 50-3000 mJ / cm2 exposure process with a KrF excimer laser using a photomask having an opening only in the pattern portion where the line width is to be reduced, for a resist pattern of 0.25 [mu] m width L / S. To generate a base. Further, the substrate is placed on a hot plate and subjected to a heat treatment at 120 ° C. for 60 seconds as a mixing bake to diffuse the base component into the resist pattern and form a solubilized layer on the surface, followed by 0.5% by weight of tetramethylammonium hydroxide. And 10% by weight
6 to the stripper of the aqueous solution containing isopropyl alcohol
Immerse for 0 seconds to dissolve and remove that part. Further, the substrate is washed with pure water and post-baked at 110 ° C. for 60 seconds.

Table 2 shows the resist pattern dimensions of the exposed part and the unexposed part and the reduction amount thereof. The exposure amount in this embodiment is 50
At 3000 mJ / cm 2, the wiring of the exposed portion is reduced, the exposure amount is increased, and the reduction amount is also increased. However, when the exposure amount is 500 mJ / cm2 or more, the reduction amount is saturated. This is because all the base generators are decomposed at an exposure amount of 500 mJ / cm 2 in this embodiment. The reason why the unexposed portion is slightly reduced is due to the dissolving power of the stripping solution.

Table 2 Relationship between exposure amount and resist pattern reduction amount in Example 3

[Table 2]

Embodiment 4 FIG. First, a chemically amplified negative resist is dropped on siliconware, spin-coated, and then dried.
Pre-baking is performed at 90 ° C. for 90 seconds to evaporate the solvent in the resist to form a resist film having a thickness of about 0.58 μm. Next, a KrF excimer laser reduction projection exposure apparatus,
The resist is exposed using an exposure photomask having a 0.25 μm wide L / S pattern. Next, a post-exposure bake treatment is performed at 110 ° C. for 90 seconds, followed by development using an alkaline developer (NMD3 manufactured by Tokyo Ohka Kogyo Co., Ltd.) to obtain a 0.25 μm-wide L / S resist pattern.

Next, the solution shown in Table 3 was spin-coated on the formed resist pattern, and heat-treated at 60 ° C. for 90 seconds, or 5-1 of oxygen plasma by an asher device.
The property of the surface of the resist pattern is changed by the irradiation treatment for 0 second.

Next, 8% by weight of polyvinyl alcohol having a weight average molecular weight of 150,000 and 5% by weight of this resin were used.
Of [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine in an aqueous solution containing 500 ppm of octylpyrrolidone is spin-coated at 3000 rpm on the resist pattern, and is heated with a hot plate at 95 rpm. Heat treatment at 60 ° C for 60 seconds,
An organic film of about 5000 ° is formed.

Next, the organic film is exposed (300 mJ / cm 2) using a KrF excimer laser reduction projection exposure apparatus and an exposure photomask having an arbitrary pattern to generate a base in the exposed portion. Next, it is placed on a hot plate and subjected to a heat treatment at 120 ° C. for 60 seconds as a mixing bake to diffuse the base component into the resist pattern.
After a solubilizing layer is formed on the surface of the resist pattern, it is immersed in a stripping solution of an aqueous solution containing 1% by weight of tetramethylammonium hydroxide and 15% by weight of isopropyl alcohol for 60 seconds to dissolve and remove the portion.
Further, the substrate is washed with pure water and post-baked at 115 ° C. for 60 seconds.

Table 3 shows the dimensions of the resist pattern obtained by these processes. By the surface treatment with the solvent or the oxygen plasma treatment after the formation of the resist pattern, the resist pattern was greatly reduced, and a very fine resist pattern was obtained.

Table 3. Result of Example 4

[Table 3] Heat treatment conditions: 60 ° C for 60 seconds ET: Ethanol, IPA: Isopropyl alcohol, TMAH: Tetramethylammonium hydroxyoxide, MEA: Monoethanolamine, PFAO: Perfluoroalkylpolyethylene oxide

[0139]

The first resist pattern miniaturizing material according to the present invention is composed of a resin, a base generator, and a solvent. Thus, an organic film containing a base generator can be formed, and there is an effect that a resist pattern exceeding the limit of the exposure wavelength can be realized.

The second resist pattern miniaturizing material according to the present invention is the first resist pattern miniaturizing material, wherein polyvinyl alcohol, polyacrylic acid, polyvinyl acetal, polyethylene oxide, polyvinyl ether, polyvinyl pyrrolidone, Polyethyleneimine, polyacrylimide, polyvinylamine, polyacrylamine, polyethylene glycol,
One of polyether polyols and polyester polyols or a mixture of two or more thereof is used. In the production of a semiconductor device of the present invention, an organic film containing a base generator is formed on a resist pattern. Therefore, there is an effect that a resist pattern exceeding the limit of the exposure wavelength can be realized.

A third resist pattern miniaturizing material according to the present invention is the above first resist pattern miniaturizing material, wherein the base generator is any one of a transition metal complex, a benzyl carbamate compound and an oxime compound. In addition, in manufacturing the semiconductor device of the present invention, there is an effect that a base component is efficiently generated in an organic film by light irradiation.

A fourth resist pattern miniaturizing material according to the present invention is the above third resist pattern miniaturizing material, wherein the base generator is a base generator that generates organic amines upon irradiation with ultraviolet rays. In the manufacture of the semiconductor device of the present invention, there is an effect that the resist pattern can be efficiently reduced.

The fifth resist pattern miniaturizing material according to the present invention is the same as the first resist pattern miniaturizing material, wherein the solvent is pure water or an organic solvent within a range that does not dissolve the resist pattern. And an organic solvent containing a base generator on a resist pattern in the manufacture of the semiconductor device of the present invention.

The sixth resist pattern miniaturizing material according to the present invention is the same as the first resist pattern miniaturizing material described above, but contains a photosensitizer. Has the effect of improving the generation efficiency of the base component. ,

A seventh resist pattern miniaturizing material according to the present invention is the sixth resist pattern miniaturizing material, wherein the photosensitizer is an aromatic hydrocarbon compound, an aromatic nitro compound, an aromatic ketone compound, An aromatic amino compound, a phenolic compound, a quinone compound, an anthracene compound, a coumarin derivative, a phthalocyanine compound, a porphyrin compound, an acridine compound or a xanthene compound; This has the effect of improving the generation efficiency of the base component.

The eighth resist pattern miniaturizing material according to the present invention is the same as the first or sixth resist pattern miniaturizing material described above, and contains a base component. There is an effect that the resist pattern in a portion that is not irradiated can be efficiently reduced.

A ninth resist pattern miniaturizing material according to the present invention is the eighth resist pattern miniaturizing material, wherein the base component is an amino compound, an imino compound,
It is either a hydroxide, a pyridine base, or a salt thereof, and has an effect that a resist pattern in a portion not irradiated with light can be efficiently reduced in the production of the semiconductor device of the present invention.

The tenth resist pattern miniaturizing material according to the present invention is the same as the first or sixth resist pattern miniaturizing material described above and contains an acid component. There is an effect that the amount of pattern reduction can be controlled.

An eleventh resist pattern miniaturizing material according to the present invention is the above-described tenth resist pattern miniaturizing material, wherein the acidic component is any one of an alkyl carboxylic acid, an alkyl sulfonic acid and a salicylic acid. In the manufacture of the semiconductor device of the present invention, there is an effect that the reduction amount of the resist pattern can be controlled.

The twelfth resist pattern miniaturizing material according to the present invention is any of the first, sixth, eighth and tenth resist pattern miniaturizing materials described above, which contains a surfactant. In the manufacture of the semiconductor device of the present invention, there is an effect that the film formability of the organic film is improved.

The first method of manufacturing a semiconductor device according to the present invention comprises the steps of forming a resist pattern on a semiconductor substrate using a negative resist, and forming the first to twelfth steps of the present invention on the resist pattern. A step of forming an organic film by applying any resist pattern refinement material, a step of generating a base in the organic film by heat treatment or exposure treatment, and diffusing the generated base component into the negative resist by heat treatment And the step of solubilizing the surface layer of the resist pattern, and the step of dissolving and removing the surface layer of the organic film and the resist pattern with a stripping solution, the resist pattern exceeding the limit of the exposure wavelength There is an effect that it can be realized stably.

The second method for manufacturing a semiconductor device according to the present invention is the same as the first method for manufacturing a semiconductor device, wherein the negative resist is a resist that can be re-dissolved by diffusion of a base component generated in an organic film. And has an effect that a resist pattern exceeding the limit of the exposure wavelength can be stably realized.

The third method of manufacturing a semiconductor device according to the present invention is the same as the method of manufacturing the second semiconductor device described above, except that a chemically amplified negative resist is used as the negative resist. This has the effect that the resist pattern can be stably realized.

The fourth method for manufacturing a semiconductor device according to the present invention is the same as the first method for manufacturing a semiconductor device, except that a basic solution is used as a stripping solution. This has the effect that a resist pattern exceeding the limit of the exposure wavelength can be stably realized.

The fifth method for manufacturing a semiconductor device according to the present invention is the method for manufacturing a semiconductor device according to the fourth method, wherein the basic solution contains an alkali salt containing an ammonium salt such as tetramethylammonium hydroxide or triethanolamine. An aqueous solution or a solution obtained by adding a water-soluble organic solvent to this alkaline aqueous solution is used, and the organic film and the solubilizing layer can be efficiently removed, and the resist pattern exceeding the limit of the exposure wavelength can be stably formed. There is an effect that it can be realized.

According to a sixth method of manufacturing a semiconductor device according to the present invention, in the first method of manufacturing a semiconductor device, an organic solvent or a mixed solvent of pure water and an organic solvent is used as a stripping solution. There is an effect that the organic film and the solubilized layer can be efficiently removed, and a resist pattern exceeding the limit of the exposure wavelength can be selectively formed.

According to a seventh aspect of the invention, there is provided a method of manufacturing a semiconductor device according to the fourth or fifth aspect, wherein the pattern of the negative resist is an acidic film having a phenolic hydroxyl group remaining. Accordingly, only the surface layer of the negative resist pattern is dissolved and removed, and there is an effect that a resist pattern exceeding the limit of the exposure wavelength can be stably realized.

An eighth method for manufacturing a semiconductor device according to the present invention is the same as the first method for manufacturing a semiconductor device, wherein the exposure process is selectively performed using a photomask. There is an effect that a resist pattern exceeding the resist pattern can be selectively formed.

A ninth method of manufacturing a semiconductor device according to the present invention is the method of manufacturing a semiconductor device according to any one of the first to eighth aspects, wherein a resist pattern is formed on a semiconductor substrate by using a negative resist. The surface of the formed resist pattern is treated with a solution or plasma, the properties of the surface of the resist pattern change, the diffusion of the base component is facilitated, a thick solubilized layer can be formed,
There is an effect that a fine negative resist pattern greatly reduced in size from the original size can be formed stably.

A tenth method of manufacturing a semiconductor device according to the present invention is the method of manufacturing a semiconductor device according to any one of the first to ninth aspects, wherein the base is diffused into the negative resist pattern and a crosslinking reaction of the negative resist is performed. And controlling the solubility of the negative resist pattern to partially dissolve the negative resist pattern formed on the semiconductor substrate, thereby stably forming the negative resist pattern finer than the original dimension. This has the effect that a resist pattern exceeding the limit of the exposure wavelength can be stably realized.

The semiconductor device according to the present invention has the first
The semiconductor device is manufactured by any one of the tenth to tenth semiconductor device manufacturing methods, and a semiconductor device having a fine wiring pattern exceeding the limit of the exposure wavelength is obtained regardless of the conductive film or the insulating film.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view of each step of forming a resist pattern according to Embodiment 1 of the present invention.

FIG. 2 is a partial cross-sectional view of each step of a conventional resist pattern formation compared to the first embodiment.

FIG. 3 is a partial sectional view of each step of forming a resist pattern according to a second embodiment of the present invention.

FIG. 4 is a partial sectional view of each step of forming a resist pattern according to a third embodiment of the present invention.

FIG. 5 is a top view of each step of forming a resist pattern according to a fourth embodiment of the present invention.

FIG. 6 is a top view of each step of forming a resist hole pattern according to a fifth embodiment of the present invention.

FIG. 7 is a top view of a resist hole pattern formed by a conventional method.

FIG. 8A is a partial sectional view of a wafer on which a fine resist pattern is formed, and FIG. 8B is a partial sectional view of a semiconductor device having a fine wiring pattern in a semiconductor device according to a seventh embodiment of the present invention; is there.

9A is a partial cross-sectional view of a wafer on which resist patterns having different line widths are formed in a semiconductor device according to an eighth embodiment of the present invention, and FIG. 9B is a semiconductor having wiring patterns having different line widths; It is a fragmentary sectional view of a device.

10A is a partial cross-sectional view of a wafer on which a resist pattern with a partially reduced line width is formed, and FIG. 10B is a partial sectional view of a semiconductor device according to a ninth embodiment of the present invention; FIG. 4 is a partial cross-sectional view of a wafer on which a wiring pattern having a reduced width is formed, and FIG. 4C is a partial cross-sectional view of a semiconductor device.

[Explanation of symbols]

Reference Signs List 1 wafer, 2 semiconductor substrate, 3 steps, 4 chemically amplified negative resist, 5, 10 photomask, 10a
Opening, 6, 6a, 6b, 6c, 8, 12, 12a resist pattern, 7, 9 organic film, 11 solubilized layer, 13
Insulating film, 14 conductive film, 14a, 14b wiring pattern,
15 interlayer insulating film, 16a conductor plug, 16b wiring, 17, 18 resist hole pattern, 19 dimple

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/027 H01L 21/30 502R (72) Inventor Takeo Ishibashi 2-3 2-3 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Electric Corporation F-term (reference) 2H025 AA02 AB16 AC01 AD01 BE00 BE10 BG00 CA00 CA03 CA22 CA27 CA28 CA39 CB00 CB07 CB13 CB15 CB21 CB41 CB42 CB43 CB45 CC03 CC04 CC17 CC20 DA40 FA12 FA28 FA33 FA48 2H092 HA05 BA24 2 HA30 LA13 2H097 HA05 LA10

Claims (23)

[Claims] 1. A resist pattern miniaturization material comprising a resin, a base generator, and a solvent. 2. As the resin, polyvinyl alcohol, polyacrylic acid, polyvinyl acetal, polyethylene oxide, polyvinyl ether, polyvinylpyrrolidone, polyethyleneimine, polyacrylimide, polyvinylamine, polyacrylamine, polyethylene glycol, polyether polyol, polyester polyol The resist pattern miniaturization material according to claim 1, wherein one of them is used, or a mixture of two or more kinds is used. 3. The resist pattern miniaturizing material according to claim 1, wherein the base generator is any one of a transition metal complex, a benzyl carbamate compound and an oxime compound. 4. The resist pattern miniaturizing material according to claim 3, wherein the base generator is a base generator that generates organic amines upon irradiation with ultraviolet rays. 5. The resist pattern refining material according to claim 1, wherein the solvent is pure water or a mixed solvent of pure water and an organic solvent within a range that does not dissolve the resist pattern. 6. The resist pattern miniaturizing material according to claim 1, further comprising a photosensitizer. 7. A photosensitizer comprising an aromatic hydrocarbon compound, an aromatic nitro compound, an aromatic ketone compound, an aromatic amino compound, a phenolic compound, a quinone compound, an anthracene compound, a coumarin derivative, a phthalocyanine compound,
The resist pattern miniaturizing material according to claim 6, wherein the material is any one of a porphyrin compound, an acridine compound and a xanthene compound. 8. The resist pattern miniaturizing material according to claim 1, further comprising a base component. 9. The resist pattern miniaturizing material according to claim 8, wherein the base component is any one of an amino compound, an imino compound, a hydroxide or a pyridine base, or a salt thereof. 10. The resist pattern miniaturizing material according to claim 1, further comprising an acid component. 11. The resist pattern miniaturizing material according to claim 10, wherein the acidic component is any one of alkyl carboxylic acid, alkyl sulfonic acid and salicylic acid. 12. The resist pattern miniaturizing material according to claim 1, further comprising a surfactant. 13. A step of forming a resist pattern on a semiconductor substrate using a negative resist, and applying the resist pattern miniaturizing material according to claim 1 on the resist pattern. A step of forming an organic film, a step of generating a base in the organic film by heat treatment or exposure treatment, and a step of diffusing the generated base component into the negative resist by heat treatment to solubilize the surface layer of the resist pattern. A method for manufacturing a semiconductor device, comprising: a step of dissolving and removing a surface layer of the organic film and the resist pattern with a stripping solution. 14. The method for manufacturing a semiconductor device according to claim 13, wherein a negative resist that can be redissolved by diffusing a base component generated in the organic film is used as the negative resist. 15. The method according to claim 14, wherein a chemically amplified negative resist is used as the negative resist. 16. The method for manufacturing a semiconductor device according to claim 13, wherein a basic solution is used as the stripping solution. 17. An alkaline aqueous solution containing an ammonium salt such as tetramethylammonium hydroxide or triethanolamine as a basic solution,
17. The method for manufacturing a semiconductor device according to claim 16, wherein any one of a solution obtained by adding a water-soluble organic solvent to the alkaline aqueous solution is used. 18. The method according to claim 1, wherein an organic solvent or a mixed solvent of pure water and an organic solvent is used as the stripping liquid.
4. The method for manufacturing a semiconductor device according to item 3. 19. The method according to claim 16, wherein the pattern of the negative resist is an acidic film having phenolic hydroxyl groups remaining, and only a surface layer of the negative resist pattern is dissolved and removed by a stripping solution. The manufacturing method of the semiconductor device described in the above. 20. The method according to claim 13, wherein the exposure process is selectively performed using a photomask. 21. The semiconductor device according to claim 13, wherein a resist pattern is formed on the semiconductor substrate using a negative resist, and the surface of the formed resist pattern is treated with a solution or plasma. 13. A method for manufacturing a semiconductor device according to 22. The method of controlling the diffusion of a base into a negative resist pattern and the cross-linking reaction of the negative resist to adjust the solubility of the negative resist pattern so that the negative resist pattern formed on a semiconductor substrate can be formed. 2. The method according to claim 1, wherein the negative resist pattern is finely formed by partially dissolving the negative resist pattern.
A method for manufacturing a semiconductor device according to claim 3. 23. A semiconductor device manufactured by the method for manufacturing a semiconductor device according to claim 13.