JP2661417B2 - Resist composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist composition, and more particularly, to a resist material capable of forming a pattern by irradiation with far ultraviolet rays or KrF excimer laser light. The resist composition of the present invention is particularly suitable as a negative resist for fine processing of a semiconductor device.

[0002]

2. Description of the Related Art When a semiconductor device is manufactured by fine processing using a resist, a resist is applied to the surface of a silicon wafer to form a photosensitive film, and a latent image is formed by irradiating light.
The image (pattern) is then obtained by lithographic techniques that develop it to form a negative or positive image. After performing etching using the resist remaining on the silicon wafer as a protective film, the resist film is removed to complete the fine processing.

In recent years, ICs, LSIs and VLs have recently been developed.
With the high integration, high density, and miniaturization of semiconductor elements in SI, a technique for forming a fine pattern of 1 μm or less is required. However, it is extremely difficult to accurately form a fine pattern of 1 μm or less with conventional photolithography technology using near ultraviolet light or visible light, and the yield is remarkably reduced.

For this reason, instead of the conventional photolithography using light (ultraviolet light having a wavelength of 350 to 450 nm), far ultraviolet light having a short wavelength (200 to 260 nm), KrF excimer laser light is used in order to enhance the resolution of exposure. (Krypton fluoride laser that emits light with a wavelength of 248 nm) and the like have been studied. A resist material, which is the center of this lithography technique, is required to have a number of advanced properties, and among them, important are sensitivity, resolution, etching resistance, and storage stability.

However, conventionally developed resist materials are:
Not all of these performances are fully satisfied, and there has been a strong demand for improved performance. For example, a negative resist such as polyglycidyl methacrylate has high sensitivity, but is inferior in resolution and dry etching resistance. Positive resists such as polymethyl methacrylate have good resolution but poor sensitivity and dry etching resistance.

In recent years, a resist for fine processing comprising a three-component system comprising a base polymer, a photoacid generator (a compound which generates an acid upon irradiation with actinic rays) and an acid-sensitive substance (a compound which crosslinks in the presence of an acid) Is being developed. In this method, an acid-sensitive substance reacts with an acid generated by light as a catalyst, so that the solubility of a base polymer changes and a positive or negative resist is obtained. For example, a negative resist comprising a novolak resin, methylolmelamine, and a photoacid generator is known. Methylolmelamine crosslinks and insolubilizes the novolak resin using an acid generated by light as a catalyst. In addition, a negative resist that utilizes a phenomenon in which a polymer containing a cationically polymerizable functional group such as a novolak resin-epoxy compound is irradiated with light in the presence of a photoacid generator to form a crosslinked structure and insolubilized due to polymerization of the functional group. Are known.

However, when a novolak resin-based photoresist is exposed to far ultraviolet rays, the light absorption of the resist itself is too large, resulting in insufficient sensitivity and resolution, and a fine pattern cannot be formed. In view of the required performance standards, it is still not enough. Therefore, there has been a strong demand for the development of a new resist having the above-mentioned performance balanced.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resist material having excellent resist characteristics such as sensitivity, resolution, etching resistance and storage stability. It is another object of the present invention to provide a device having a short wavelength of deep ultraviolet light or Kr.
An object of the present invention is to provide a resist material suitable for lithography using F excimer laser light. Another object of the present invention is to provide a resist composition particularly suitable as a negative resist for fine processing of a semiconductor device.

The inventors of the present invention have conducted intensive studies to solve the problems of the prior art, and as a result, have found that an alkali-soluble phenol resin, a compound capable of generating an acid upon irradiation with actinic rays, and a compound capable of crosslinking in the presence of an acid In a resist composition containing, by using a specific halogen-containing polyhydric phenol compound as a compound that generates an acid upon irradiation with actinic light, a resist composition excellent in sensitivity, resolution, etching resistance, storage stability, etc. I found that I could get something. This resist composition is suitable as a negative resist for fine processing of a semiconductor device. The present invention
It has been completed based on these findings.

[0010]

Thus, according to the present invention, there is provided a resist composition containing an alkali-soluble phenol resin, a compound capable of generating an acid upon irradiation with actinic light, and a compound capable of crosslinking in the presence of an acid. Compounds that generate an acid upon irradiation with light are represented by the general formulas (I) to (VI).
A resist composition is provided which is at least one halogen-containing polyhydric phenol compound selected from the group consisting of compounds represented by I).

General formula (I)

[0012]

Embedded image General formula (II)

[0013]

Embedded image General formula (III)

[0014]

[10] General formula (IV)

[0015]

Embedded image General formula (V)

[0016]

Embedded image General formula (VI)

[0017]

Embedded image General formula (VII)

[0018]

Embedded image R ₁ to R _8: halogen, hydrogen, hydroxyl, alkyl, amino
A substituted alkyl group substituted with a
Substituted with a oxy group, or an amino or nitro group
Substituted alkoxy groups. However, the general formulas (I) to (VI)
In I), at least one halogen R ₁ to R _8. R _{9 to} R ₁₂ : hydrogen or an alkyl group. A: a single bond, an alkylene group, a substituted alkylene group, an alkenyl group, a substituted alkenyl group, an arylene group, or a substituted arylene group. B: oxygen or a single bond.

Hereinafter, the present invention will be described in detail. (Alkali-soluble phenol resin) Examples of the alkali-soluble phenol resin used in the present invention include a condensation reaction product of phenols and aldehydes,
Examples include a condensation reaction product of a phenol and a ketone, a vinylphenol-based polymer, an isopropenylphenol-based polymer, and a hydrogenation reaction product of these phenol resins.

Specific examples of the phenols used herein include monovalent phenols such as phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, and phenylphenol; resorcinol, pyrocatechol, hydroquinone, bisphenol A, pyrogallol, and the like. Polyhydric phenols; and the like.

Specific examples of aldehydes include formaldehyde, acetaldehyde, benzaldehyde, terephthalaldehyde and the like. Specific examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone, and the like.

These condensation reactions can be carried out according to a conventional method. Further, the vinylphenol-based polymer is selected from a homopolymer of vinylphenol and a copolymer with a component copolymerizable with vinylphenol.

Specific examples of the copolymerizable component include acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic imide, vinyl acetate, acrylonitrile, and derivatives thereof.

The isopropenylphenol-based polymer is selected from a homopolymer of isopropenylphenol and a copolymer of isopropenylphenol and a component copolymerizable with isopropenylphenol.

Specific examples of the copolymerizable component include acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic imide, vinyl acetate, acrylonitrile, and derivatives thereof.

The hydrogenation reaction of the phenolic resin can be carried out by a known method. The phenolic resin is dissolved in an organic solvent, and hydrogen is introduced in the presence of a homogeneous or heterogeneous hydrogenation catalyst. Is achieved by doing

The concentration of the phenol resin solution in the hydrogenation reaction is 1 to 70% by weight, preferably 1 to 40% by weight.
It is. The solvent is not particularly limited as long as it dissolves the phenol resin without adversely affecting the hydrogenation catalyst. The hydrogenation catalyst is not particularly limited as long as it is a metal or nonmetal catalyst having the activity of the hydrogenation reaction. Specific examples include Fe, Co, Ni, Ru, Rh, Pd, and I.
r, Os, Pt, Cr, Te, Mn, Ti, V, Zr,
Mo, W-based hydrogenation catalysts are exemplified. These catalysts can be used alone or in combination.

The reaction temperature of the hydrogenation reaction is usually from 0 to 30.
0 ° C., preferably 20 to 150 ° C. A temperature of 300 ° C. or higher is possible, but is not preferred because side reactions easily occur. The hydrogen pressure is from atmospheric pressure to 400 kg / cm ² , preferably from 5 to 200 kg / cm ² . After the hydrogenation reaction, the catalyst can be removed from the hydrogenation reaction resin solution by reprecipitation purification, sedimentation, centrifugation, filtration, or the like.

In the hydrogenation, the hydrogenation rate is usually 0.1 to 7
0%, preferably 1 to 50%, more preferably 3 to 4
Perform so that the range is 0%. When the hydrogenation rate exceeds 70%, the hydrogenated phenol resin becomes alkali-insoluble, and thus is not suitable as a resist base polymer. On the other hand, if the hydrogenation ratio is too low, the effect of improving the performance by hydrogenation will be small. These alkali-soluble phenol resins can be used alone or in combination of two or more.

In the resist composition of the present invention, if necessary, for example, a copolymer of styrene with acrylic acid, methacrylic acid or maleic anhydride may be used to improve developability, storage stability, heat resistance and the like. And a copolymer of an alkene and maleic anhydride, a vinyl alcohol polymer, a vinyl pyrrolidone polymer, rosin, shellac and the like. The addition amount of these optional components is 0 to 50 parts by weight, preferably 5 to 20 parts by weight based on 100 parts by weight of the alkali-soluble phenol resin.

(Acid-Crosslinkable Compound) The compound used in the present invention which crosslinks in the presence of an acid (hereinafter abbreviated as “acid-crosslinkable compound”) is an acid derived from a compound which generates an acid upon irradiation with actinic rays. Is not particularly limited as long as it is a substance that cross-links in the presence of the compound and reduces the solubility of the phenol resin in the active light-irradiated portion in an alkali developing solution. Among them, a C—O—R group (R Is preferably a compound having a hydrogen atom or an alkyl group) or a compound having an epoxy group.

Specific examples of the compound having a C—O—R group include melamine-formaldehyde resin, alkyl etherified melamine resin, benzoguanamine resin, alkyl etherified benzoguanamine resin, urea resin, alkyl etherified urea resin, urethane-formaldehyde. Resins, phenolic compounds containing an alkyl ether group, and the like.

The melamine-formaldehyde resin is obtained by condensing melamine and formaldehyde under basic conditions according to a conventional method. The alkyl etherified melamine resin is obtained by alkyl etherifying methylol melamine obtained by condensing melamine and formaldehyde under basic conditions with an alcohol. As the alkyl etherified melamine resin, a melamine resin containing a hexaalkyl etherified melamine as a main component is preferable because of good storage stability, and among them, a hexamethyl etherified melamine resin is particularly preferable.

In place of melamine of melamine-formaldehyde resin, a resin obtained by similarly reacting a melamine compound such as acetoguanamine or benzoguanamine with formaldehyde can also be used. The alkyl etherified benzoguanamine resin can be easily synthesized by using benzoguanamine instead of melamine of the alkyl etherified melamine resin. As the alkyl etherified benzoguanamine resin, a tetraalkyl etherified benzoguanamine resin is preferable, and particularly, a tetramethyl etherified benzoguanamine resin is preferable, since storage stability is good.

The urea resin is obtained by condensing urea and formaldehyde according to a conventional method. The alkyl etherified urea resin is obtained by alkyl etherifying methylol urea obtained by condensing urea and formaldehyde with alcohol. The alkyl etherified urea resin is preferably an alkyl etherified product of monomethylol urea, dimethylol urea, trimethylol urea, or a urone compound, and more preferably an alkyl etherified product of trimethylol urea.

Instead of urea as the urea resin, use is made of a resin obtained by reacting urea-based compounds such as glycoluril, urone-based compounds, cyclic urea compounds such as methylene urea and propylene urea with formaldehyde in the same manner. Can also.

Examples of the urethane-formaldehyde resin include compounds represented by the following general formula (VIII). General formula (VIII)

[0038]

Embedded image R ₁ : hydrogen or alkyl group As the phenolic compound containing an alkyl ether group,
The compound represented by the general formula (IX) is exemplified. w General formula (IX)

[0039]

Embedded imageR _Two: Alkyl group, alkoxy group, alkenyl group, al
Kenyloxy group. R_Three: Hydrogen, alkyl group, hydroxyl group. R_Four: Hydrogen, alkyl group. n: 2, 3, 4,

Specific examples of the compound having an epoxy group include glycidyl ether epoxy resins such as biphenol A epoxy, bisphenol F epoxy, bisphenol S epoxy, bisphenol E epoxy, novolak epoxy and brominated epoxy; cyclohexene Alicyclic aliphatic epoxy resin containing an oxide group, tricyclodecene oxide group, cyclopentene oxide group, etc .; glycidyl ester epoxy resin; glycidylamine epoxy resin; heterocyclic epoxy resin; polyfunctional epoxy resin; Can be These epoxy resins can be synthesized according to a conventional method.

These acid-crosslinkable compounds may be used alone or as a mixture of two or more kinds. Usually, 0.2 to 50 parts by weight per 100 parts by weight of the alkali-soluble phenol resin is used.
Preferably it is 3 to 40 parts by weight. If the proportion of the acid-crosslinkable compound is too small, pattern formation becomes impossible,
Conversely, if it is excessively large, residual development tends to occur.

(Halogen-Containing Polyhydric Phenol Compound) In the present invention, the compound capable of generating an acid upon irradiation with actinic rays (also referred to as an acid-cleavable compound) is represented by any of the above formulas (I) to (VII). The halogen-containing polyhydric phenol compound is not particularly limited.

In the halogen-containing polyhydric phenol compounds represented by formulas (I) to (VII), the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and the alkoxy group is preferably an alkyl group having 1 to 4 carbon atoms. An alkoxy group of 8,
The alkylene group is preferably an alkylene group having 1 to 6 carbon atoms, the alkenyl group is preferably an alkenyl group having 2 to 5 carbon atoms, and the arylene group is preferably an arylene group having 6 to 15 carbon atoms. These groups may be substituted with an amino group, a nitro group or the like.

Examples of the method for synthesizing such a halogen-containing polyhydric phenol compound include (1) a method of halogenating a polyhydric phenol compound according to a conventional method, and (2) a method of synthesizing a halogen-containing polyphenol compound as a starting material. However, the former is more common. Specific examples of the polyhydric phenol compound used in the method (1) include the following compounds.

As the raw materials for the halogen-containing polyhydric phenol compound represented by the general formula (I), the following compounds may be mentioned.

[0046]

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[0047]

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[0048]

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[0049]

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The following compounds may be mentioned as raw materials for the halogen-containing polyhydric phenol compound represented by the general formula (II).

[0051]

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[0052]

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As a raw material of the halogen-containing polyhydric phenol compound represented by the general formula (III), the following compounds may be mentioned.

[0054]

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[0055]

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As the raw materials for the halogen-containing polyhydric phenol compound represented by the general formula (IV), the following compounds may be mentioned.

[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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As a raw material of the halogen-containing polyhydric phenol compound represented by the general formula (V), the following compounds can be mentioned.

[0064]

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[0065]

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[0066]

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As a raw material of the halogen-containing polyhydric phenol compound represented by the general formula (VI), there may be mentioned Chemical Formulas 34 to 35.

[0068]

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[0069]

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As a raw material of the halogen-containing polyhydric phenol compound represented by the general formula (VII),
Is mentioned.

[0071]

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[0072]

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These halogen-containing polyhydric phenol compounds preferably have a bromine atom or a chlorine atom bonded to an aromatic carbon atom.

The proportion of the halogen-containing polyhydric phenol compound used as the acid-generating compound is usually 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the alkali-soluble phenol resin. . If the use ratio is less than 0.01 part by weight, it becomes difficult to form a pattern, and if it exceeds 50 parts by weight, residual development tends to occur,
In any case, the resist performance deteriorates.

(Resist Composition) The resist composition of the present invention is usually used by dissolving it in a solvent in order to apply it to a substrate to form a resist film.

Examples of the solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone and butyrolactone; alcohols such as n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol and t-butyl alcohol. Ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane; alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; propyl formate and butyl formate , Propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, etc. Monooxycarboxylic esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, methyl 2-methoxypropionate, and ethyl 2-methoxypropionate; cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate Cellosolve esters such as, propyl cellosolve acetate, butyl cellosolve acetate;
Propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ethyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, etc .; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Diethylene glycols such as methyl ethyl ether; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; dimethylacetamide, dimethylformamide, N
Polar solvents such as -methylacetamide and N-methylpyrrolidone; These may be used alone or in combination of two or more.

The resist composition of the present invention may contain additives such as a surfactant, a storage stabilizer, a sensitizer, a striation inhibitor, a plasticizer, and an antihalation agent, if necessary.

As a developer for the resist composition of the present invention, an aqueous alkali solution is used. Specific examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate and ammonia; ethylamine, propylamine and the like. Secondary amines such as diethylamine and dipropylamine; tertiary amines such as trimethylamine and triethylamine; alcoholamines such as diethylethanolamine and triethanolamine; tetramethylammonium hydroxide and tetraethylammonium hydroxy Quaternary ammonium salts such as trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, and trimethylhydroxyethylammonium hydroxide; It is.

Further, if necessary, a suitable amount of a water-soluble organic solvent such as methanol, ethanol, propanol, ethylene glycol, a surfactant, a storage stabilizer, a resin dissolution inhibitor or the like can be added to the above-mentioned alkaline aqueous solution.

The resist composition of the present invention can be used to form a resist film by applying the solvent solution to a substrate surface such as a silicon wafer by a conventional method, and then removing the solvent by drying. In particular, spin coating is awarded as an application method.

In the exposure, a fine pattern can be formed by irradiating a short-wave ultraviolet ray or a KrF excimer laser beam with a far ultraviolet ray irradiating apparatus or an excimer laser apparatus filled with krypton / fluorine gas.

By performing a heat treatment (post-exposure bake) after the light irradiation, the reaction between the acid and the acid-crosslinkable compound (acid-catalyzed reaction) is promoted, and the sensitivity can be further increased.

[0083]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The parts and percentages in the examples are on a weight basis unless otherwise specified.

Example 1 100 parts of polyvinylphenol (weight average molecular weight 5000), 15 parts of an alkyl etherified melamine-formaldehyde resin (Nikarac MW-30, manufactured by Sanwa Chemical Co., Ltd.), a compound represented by the following chemical formula (1) 1.5 parts, 0.01 part of a fluorine-based surfactant was dissolved in 380 parts of ethyl 2-methoxypropionate,
The solution was filtered through a 0.1 μm polytetrafluoroethylene filter (manufactured by Millipore) to prepare a resist solution.

The resist solution was applied on a silicon wafer by a spinner and baked at 90 ° C. for 90 seconds to form a resist film having a thickness of 1.0 μm. This wafer was irradiated with a far ultraviolet irradiation device (PLA-521F, manufactured by Canon Inc.).
Exposure was performed using A) and a test mask. next,
After baking after exposure at 130 ° C. for 60 seconds, development was performed by immersion in an aqueous solution of tetramethylammonium hydroxide (concentration: 2.38%) at 23 ° C. for 1 minute to obtain a negative pattern.

The film thickness of the pattern was measured with a film thickness meter (manufactured by Tenko Corporation,
It was 0.95 μm as measured in alpha step 200). Take out the wafer with the pattern,
Observation with an electron microscope revealed that a 0.50 μm pattern had been resolved. Chemical formula (1)

[0087]

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Example 2 The wafer on which the pattern of Example 1 was formed was subjected to a dry etching apparatus (DEM-451T, manufactured by Nidec Anelva) at a power of 300 W, a pressure of 0.03 Torr, and a gas CF ₄ / H ₂ =. When etching was performed at 30/10 at a frequency of 13.56 MHz, it was observed that etching was performed only at portions where there was no pattern. When the pattern of the resist after etching was observed, the shape before etching was almost maintained. This proved that the resist composition of Example 1 had excellent dry etching resistance.

Example 3 100 parts of polyvinylphenol (weight average molecular weight 5000), 15 parts of an alkyl etherified melamine-formaldehyde resin (Nikalac MW-30, manufactured by Sanwa Chemical Co., Ltd.), represented by the following chemical formula (2) Dissolve 1.5 parts of the compound and 0.01 part of a fluorosurfactant in 375 parts of ethyl 2-methoxypropionate,
The solution was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a resist solution.

The resist solution was applied on a silicon wafer by a spinner and baked at 85 ° C. for 90 seconds to form a resist film having a thickness of 1.0 μm. This wafer was placed on a KrF excimer laser stepper NSR 1505E.
Exposure was performed using X (manufactured by Nikon Corporation, NA = 0.42) and a test mask. Next, after baking after exposure at 125 ° C. for 60 seconds, development was performed by immersion at 23 ° C. for 1 minute in an aqueous solution of tetramethylammonium hydroxide to obtain a negative pattern. When the wafer on which the pattern was formed was taken out and observed with an electron microscope, a pattern of 0.45 μm was resolved. Chemical formula (2)

[0091]

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Example 4 100 parts of hydrogenated polyvinyl phenol (hydrogenation ratio = 8%, weight average molecular weight 4900),
Alkyl ether group-containing phenol compounds (GENER
Methylon Re, manufactured by AL ELECTRIC
25 parts of methyl compound (sin 75108), 2.5 parts of a compound represented by the following chemical formula (3) and 0.01 part of a fluorine-based surfactant were dissolved in 350 parts of propylene glycol monomethyl ether acetate, and 0.1 μm of The solution was filtered through a fluoroethylene filter to prepare a resist solution.

The above-mentioned resist solution was applied on a silicon wafer by a spinner, and baked at 90 ° C. for 90 seconds to form a resist film having a thickness of 1.0 μm. This wafer was placed on a KrF excimer laser stepper NSR 1505E.
Exposure was performed using X and a test mask. next,
After baking after exposure at 150 ° C. for 60 seconds, development was performed with an aqueous tetramethylammonium hydroxide solution at 23 ° C. for 1 minute by an immersion method to obtain a negative pattern. When the wafer on which the pattern was formed was taken out and observed with an electron microscope, a pattern of 0.40 μm was resolved. Chemical formula (3)

[0094]

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Example 5 100 parts of hydrogenated polyvinyl phenol (hydrogenation ratio = 8%, weight average molecular weight 4900),
Alkyl etherified urea-formaldehyde resin (CY
20 parts of UFR-65 manufactured by ANAMID, 1.5 parts of a compound represented by the following chemical formula (4), and 0.01 part of a fluorine-based surfactant were dissolved in 350 parts of propylene glycol monomethyl ether acetate, and 0.1 μm of The solution was filtered through a polytetrafluoroethylene filter to prepare a resist solution.

The resist solution was applied on a silicon wafer with a spinner, and baked at 90 ° C. for 90 seconds to form a 1.0 μm thick resist film. This wafer was placed on a KrF excimer laser stepper NSR 1505E.
Exposure was performed using X and a test mask. next,
After baking after exposure at 130 ° C. for 60 seconds, the film was developed with an aqueous tetramethylammonium hydroxide solution at 23 ° C. for 1 minute by an immersion method to obtain a negative pattern. When the wafer on which the pattern was formed was taken out and observed with an electron microscope, a pattern of 0.45 μm was resolved. Chemical formula (4)

[0097]

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Example 6 100 parts of hydrogenated polyvinyl phenol (hydrogenation ratio = 8%, weight average molecular weight 4900),
Alkyl etherified urethane-formaldehyde resin 1
5 parts, 2.0 parts of a compound represented by the following chemical formula (5), and 0.01 part of a fluorinated surfactant were added to cyclohexanone 330
The resulting solution was dissolved in the solution and filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a resist solution.

The resist solution was applied on a silicon wafer by a spinner, and baked at 90 ° C. for 90 seconds to form a 0.8 μm thick resist film. The wafer was exposed using a far ultraviolet irradiation apparatus PLA-521FA and a test mask. Next, after baking after exposure at 130 ° C. for 60 seconds, it was developed with an aqueous tetramethylammonium hydroxide solution at 23 ° C. for 1 minute by an immersion method to obtain a negative pattern. When the wafer on which the pattern was formed was taken out and observed with an electron microscope, it was 0.50 μm
Was resolved. Chemical formula (5)

[0100]

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Example 7 100 parts of m-cresol novolak resin (weight average molecular weight: 6100), 20 parts of alkyl etherified urethane-formaldehyde resin, 2.0 parts of a compound represented by the following chemical formula (6), fluorinated surfactant 0.01 part of the agent is ethyl 2-methoxypropionate 38
0 parts, and filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a resist solution.

After applying the above resist solution on a silicon wafer with a spinner, it was baked at 90 ° C. for 90 seconds to form a 0.8 μm thick resist film. The wafer was exposed using a far ultraviolet irradiation apparatus PLA-521FA and a test mask. Next, after baking after exposure at 125 ° C. for 60 seconds, development was performed by immersion at 23 ° C. for 1 minute in an aqueous solution of tetramethylammonium hydroxide to obtain a negative pattern. When the wafer on which the pattern was formed was taken out and observed with an electron microscope, it was 0.50 μm
Was resolved. Chemical formula (6)

[0103]

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Example 8 100 parts of m-cresol novolak resin (weight average molecular weight 6100), alkyl etherified urea-formaldehyde resin (CYANAMID)
Co., Ltd., 20 parts of UFR-65), 0.8 part of a compound represented by the following chemical formula (7), and 0.01 part of a fluorinated surfactant dissolved in 330 parts of cyclohexanone, and 0.1 μm of polytetrafluoroethylene. The solution was filtered through a filter to prepare a resist solution.

The resist solution was applied on a silicon wafer by a spinner and baked at 90 ° C. for 90 seconds to form a 0.8 μm thick resist film. The wafer was exposed using a far ultraviolet irradiation apparatus PLA-521FA and a test mask. Next, after baking after exposure at 125 ° C. for 60 seconds, development was performed by immersion at 23 ° C. for 1 minute in an aqueous solution of tetramethylammonium hydroxide to obtain a negative pattern. The wafer on which the pattern was formed was taken out and observed with an electron microscope.
m was resolved. Chemical formula (7)

[0106]

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Example 9 100 parts of hydrogenated polyvinyl phenol (hydrogenation ratio = 8%, weight average molecular weight 4900),
15 parts of alkyl etherified melamine-formaldehyde resin (manufactured by Sanwa Chemical Co., Nikarac MW-30)
1.0 part of the compound represented by the following chemical formula (8) and 0.01 part of a fluorine-based surfactant are dissolved in 380 parts of ethyl 2-methoxypropionate, and the mixture is filtered through a 0.1 μm polytetrafluoroethylene filter. Then, a resist solution was prepared.

After the resist solution was applied on a silicon wafer with a spinner, it was baked at 90 ° C. for 90 seconds to form a 0.8 μm thick resist film. This wafer was placed on a KrF excimer laser stepper NSR 1505E.
Exposure was performed using X and a test mask. Then, 1
After baking after exposure at 30 ° C. for 60 seconds, development was performed by immersion at 23 ° C. for 1 minute in an aqueous solution of tetramethylammonium hydroxide to obtain a negative pattern. When the wafer on which the pattern was formed was taken out and observed with an electron microscope, a pattern of 0.35 μm was resolved. Chemical formula (8)

[0109]

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[0110]

According to the present invention, a resist composition having an excellent balance among sensitivity, resolution, etching resistance, storage stability and the like can be obtained. The resist composition of the present invention is a pattern forming material suitable for lithography using short-wavelength light, and is particularly suitable as a negative resist for fine processing of semiconductor devices.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Nobunori Abe 1-2-1, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture, Japan Zeon Corporation R & D Center (56) References , A) JP-A-4-367864 (JP, A) JP-A-4-367865 (JP, A)

Claims (4)

(57) [Claims] 1. A resist composition comprising an alkali-soluble phenol resin, a compound capable of generating an acid upon irradiation with actinic light, and a compound capable of crosslinking in the presence of an acid, wherein the compound capable of generating an acid upon irradiation with actinic light has a general formula (I)
A resist composition comprising at least one halogen-containing polyhydric phenol compound selected from the group consisting of compounds represented by formulas (VII) to (VII). General formula (I) Formula (II) General formula (III) General formula (IV) General formula (V) General formula (VI) General formula (VII) R ₁ to R _8: halogen, hydrogen, hydroxyl, alkyl, amino
A substituted alkyl group substituted with a
Substituted with a oxy group, or an amino or nitro group
Substituted alkoxy groups. However, the general formulas (I) to (VI)
In I), at least one halogen R ₁ to R _8. R _{9 to} R ₁₂ : hydrogen or an alkyl group. A: a single bond, an alkylene group, a substituted alkylene group, an alkenyl group, a substituted alkenyl group, an arylene group, or a substituted arylene group. B: oxygen or a single bond. 2. The resist composition according to claim 1, wherein the halogen bonded to the aromatic carbon atom of the halogen-containing polyhydric phenol compound is a bromine atom or a chlorine atom. 3. The resist composition according to claim 1, wherein the alkali-soluble phenol resin is an alkali-soluble hydrogenated phenol resin. 4. A compound which crosslinks in the presence of an acid is C—O—
The resist composition according to claim 1, which is a compound having an R group (R is hydrogen or an alkyl group) or an epoxy group.