JPH04291259A - Resist composition - Google Patents

Abstract

PURPOSE:To improve resist characteristics by incorporating an alkali-soluble phenolic resin, a compd. to crosslink in the presence of an acid and at least one kind of mefonic esten compd. into this compsn. CONSTITUTION:The alkali-soluble phenolic resin, the compd. to cosslink in the presence of the acid and at least one kind of the refomic esten compd. selected from a group consisting of the sulfomic ester compd. of polyvalent phenol and the sulfomic ester compd. expressed by formula I are incorporated into this compd. In the formula I, R1 denotes an aryl group, alkyl group; R2 denotes an alkyl group, aralkyl group, etc. The resist material which has excellent resist characteristics, such as sensitivity, definition, etching resistance, and preservation stability and is suitable for lithography using far UV rays of short wavelength and KrF excimer laser beams is obtd. in this way. Particularly this resist compsn. is adequate as a negative type resist for fine working of semiconductor elements.

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 that can be patterned by irradiation with ultraviolet rays, KrF excimer laser light, or the like. The resist composition of the present invention is particularly suitable as a negative resist for microfabrication of semiconductor devices.

0002

[Prior Art] When manufacturing semiconductors by microfabrication using a resist, a resist is applied to the surface of a silicon wafer to form a photoresist film, a latent image is formed by irradiation with light, and the latent image is then developed to form a negative or Images (patterns) are obtained using lithography technology that forms positive images. After etching is performed using the resist remaining on the silicon wafer as a protective film, the resist film is removed to complete the microfabrication.

By the way, in recent years, IC, LSI, and even V
2. Description of the Related Art As semiconductor devices become more highly integrated, densely packed, and miniaturized in LSIs, there is a need for technology for forming fine patterns of 1 μm or less. However, with conventional photolithography techniques using near-UV or visible light, 1 μm
It is extremely difficult to form the following fine patterns with high precision, and the yield is significantly reduced. For this reason, instead of conventional photolithography that uses light (ultraviolet light with a wavelength of 350 to 450 nm), in order to improve resolution, we have developed a method that uses short-wavelength deep ultraviolet rays, KrF excimer laser light (wavelength 249 nm).
Lithography technology using a krypton fluoride laser (which emits nanometer light) is being researched.

[0004] The resist material, which is the core of this lithography technology, is required to have many advanced properties.
Among these, sensitivity, resolution, etching resistance, and storage stability are important. In other words, the resist material must (1) have good sensitivity to radiation such as light and electron beams used for exposure, and (2) not swell in a developer and have high contrast. (3) resistance to dry etching using plasma or accelerated ions, and (4) storage stability.

However, conventionally developed resist materials are
It does not fully satisfy all of these performances, and there is a strong desire for improved performance. For example, a negative resist such as polyglycidyl methacrylate has high sensitivity but poor resolution and dry etching resistance. Positive resists such as polymethyl methacrylate have good resolution but poor sensitivity and dry etching resistance.

[0006]Recently, resists for microfabrication have been developed which consist of a three-component system of a base polymer, a photoacid generator, and an acid-sensitive substance. This uses acid generated by light as a catalyst,
The acid-sensitive substance reacts and the solubility of the base polymer changes, resulting in a positive or negative resist. For example, a negative resist made of a phenol novolac resin, methylolmelamine, and a photoacid generator is known. Using an acid generated by light as a catalyst, methylolmelamine crosslinks and insolubilizes the phenol novolac resin. Negative resists are also known, which utilize the phenomenon that when a polymer containing a cationically polymerizable functional group such as a novolac resin-epoxy compound is irradiated with light in the presence of a photoacid generator, the epoxy group polymerizes to form a crosslinked structure and become insolubilized. ing. By the way, with conventional novolac resin photoresists, the light absorption of the resist itself is too large, so when exposed to deep ultraviolet rays, the sensitivity and resolution are insufficient, making it impossible to form good fine patterns. Considering the required performance standards, it is still not sufficient. Therefore, there has been a strong desire to develop a new resist that satisfies the above performance.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resist material having excellent resist properties such as sensitivity, resolution, etching resistance, and storage stability. Another object of the present invention is to provide a resist material suitable for lithography using short-wavelength deep ultraviolet rays or KrF excimer laser light. Another object of the invention is to
In particular, it is an object of the present invention to provide a resist composition suitable as a negative resist for microfabrication of semiconductor devices. In order to solve the problems of the above-mentioned prior art, the present inventors have conducted intensive research and found that by combining an alkali-soluble phenol resin, a compound that crosslinks in the presence of an acid, and a specific sulfonic acid ester compound, The present inventors have discovered that a resist composition that can achieve the above object can be obtained, and have completed the present invention based on this finding.

[0008]

[Means for Solving the Problems] Thus, according to the present invention, an alkali-soluble phenolic resin (A), a compound (B) that crosslinks in the presence of an acid, a sulfonic acid ester compound of a polyhydric phenol, and a compound of the following general formula A resist composition comprising at least one sulfonic acid ester compound (C) selected from the group consisting of sulfonic acid ester compounds represented by (1).

[0009]

[Formula 2] General formula (1) [wherein R1 is an aryl group, a substituted (halogen, alkyl, nitro, alkoxy) aryl group, an alkyl group, a substituted (halogen, nitro, alkoxy) alkyl group, R2 represents an alkyl group, a substituted (halogen, alkyl, nitro, alkoxy) alkyl group, an aralkyl group, a substituted (halogen, alkyl, nitro, alkoxy) aralkyl group, an allyl group, a substituted (halogen, alkyl, nitro, alkoxy) allyl group . ] is provided. The present invention will be explained in detail below.

(Alkali-soluble phenolic resin) In the present invention, an alkali-soluble phenolic resin is used as the base polymer, and specific examples thereof include condensation reaction products of phenols and aldehydes, and phenols and Examples include condensation reaction products with ketones, vinylphenol polymers, isopropenylphenol polymers, and hydrogenation reaction products of these phenol resins.

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

Specific examples of aldehydes include formaldehyde, acetaldehyde, benzaldehyde, and terephthalaldehyde. 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 conventional methods.

The vinylphenol polymer is selected from vinylphenol homopolymers and copolymers of vinylphenol and copolymerizable components. Specific examples of copolymerizable components include acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic imide and derivatives thereof, vinyl acetate, acrylonitrile, and the like.

The isopropenylphenol-based polymer is selected from homopolymers of isopropenylphenol and copolymers of isopropenylphenol and copolymerizable components. Specific examples of copolymerizable components include acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic imide and derivatives thereof, vinyl acetate, acrylonitrile, and the like.

The hydrogenation reaction of these phenolic resins can be carried out by any known method, in which the phenolic resin is dissolved in an organic solvent and the hydrogenation reaction is carried out in the presence of a homogeneous or heterogeneous hydrogenation catalyst. , can be achieved by introducing hydrogen. These alkali-soluble phenolic resins may be used alone, or two or more types may be used in combination.

The resist composition of the present invention may contain, if necessary, a copolymer of styrene and acrylic acid, methacrylic acid, or maleic anhydride in order to improve developability, storage stability, heat resistance, etc. Copolymers, copolymers of alkenes and maleic anhydride, vinyl alcohol polymers, vinylpyrrolidone polymers, rosin, shellac, etc. can be added. The amount of these optional components added is usually 0 to 100 parts by weight of the alkali-soluble phenol resin.
~50 parts by weight, preferably 5 to 20 parts by weight.

(Compound that crosslinks in the presence of an acid) The compound that crosslinks in the presence of an acid (acid crosslinking substance) used in the present invention is a compound that crosslinks in the presence of an acid, which is derived from a compound that can be acid-cleaved by irradiation with actinic rays. There are no particular limitations on the substance as long as it crosslinks with the active rays and reduces the solubility of the area irradiated with actinic rays in an alkaline developer, but among these, C-O
A compound having an -R group (R is a hydrogen atom or an alkyl group) or an epoxy group is preferred. C-
Specific examples of compounds having an OR group (R is a hydrogen atom or an alkyl group) include melamine-formaldehyde resins, urea-formaldehyde resins, urethane-formaldehyde resins, and alkyl ether group-containing phenolic compounds. .

Melamine-formaldehyde resin is obtained by condensing melamine and formaldehyde under basic conditions according to a conventional method. The melamine-formaldehyde resin used in the present invention is preferably an alkyl etherified melamine-formaldehyde resin because of its good storage stability. The alkyl etherified melamine-formaldehyde resin is obtained by alkyl etherifying a melamine-formaldehyde resin with alcohol by a conventional method. Instead of melamine in the melamine-formaldehyde resin, acetoguanamine resin or benzoguanamine resin obtained by reacting a melamine compound such as acetoguanamine or benzoguanamine with formaldehyde in a similar manner can also be used.

The urea-formaldehyde resin can be obtained by condensing urea and formaldehyde under basic conditions according to a conventional method. The urea-formaldehyde resin used in the present invention is preferably an alkyl etherified urea-formaldehyde resin because of its good storage stability. The alkyl etherified urea-formaldehyde resin is obtained by alkyl etherifying the urea-formaldehyde resin with alcohol. Instead of urea in the urea-formaldehyde resin, various resins obtained by reacting formaldehyde with urea-based compounds such as glycoluril, uron-based compounds, cyclic urea compounds such as methylene urea, and propylene urea in a similar manner can also be used. It is possible. Examples of the urethane-formaldehyde resin include compounds represented by general formula (2).

[0020]

[Formula 3] General formula (2) (R3 represents a hydrogen atom or an alkyl group.) As the alkyl ether group-containing phenol compound, for example,
Examples include compounds represented by general formula (3).

[0021]

[Formula 4] General formula (3) (However, R4 is an alkyl group, an alkoxy group, an alkenyl group, or an alkenyloxy group, and R5 is a hydrogen atom or an alkyl group.)

Examples of compounds having an epoxy group include glycidyl ether epoxy resins such as bisphenol A epoxy, bisphenol F epoxy, bisphenol S epoxy, bisphenol E epoxy, novolac epoxy, and brominated epoxy; cyclohexene; Cycloaliphatic epoxy resins containing oxide groups, tricyclodecene oxide groups, cyclopentene oxide groups, etc.; glycidyl ester-based epoxy resins; glycidylamine-based epoxy resins; heterocyclic epoxy resins;
Examples include polyfunctional epoxy resins. These epoxy resins can be synthesized according to conventional methods.

[0023] These acid crosslinking substances each independently have the following properties:
Alternatively, two or more types may be used as a mixture, and usually 0.00 parts by weight per 100 parts by weight of the alkali-soluble phenol resin.
The amount is 2 to 50 parts by weight, preferably 3 to 40 parts by weight, and more preferably 5 to 30 parts by weight. This blending ratio is 0.2
If it is less than 50 parts by weight, it will be impossible to form a pattern, and if it exceeds 50 parts by weight, residual development will likely occur.

(Sulfonic Acid Ester Compound) The sulfonic acid ester compound used in the present invention is a sulfonic acid ester compound of polyhydric phenol and/or a sulfonic acid ester compound represented by the above general formula (1).

The polyhydric phenol compound used for the polyhydric phenol sulfonic acid ester compound is a phenolic -O
There are no particular limitations on the compound as long as it has a plurality of H groups, and various known compounds are possible.Specific examples include polyhydroxybiphenyl and its derivatives, polyhydroxybiphenyl and its derivatives, polyhydroxydiphenylalkane and its derivatives. derivatives, polyhydroxybenzophenone and its derivatives, polyhydroxydiphenyl sulfide and its derivatives, polyhydroxydiphenyl sulfoxide and its derivatives, polyhydroxydiphenyl sulfone and its derivatives, 4,4-(p-phenylene diisopropylidene) bisphenol and its derivatives derivatives, 4,4-(m-phenylene diisopropylidene) bisphenol and its derivatives, tris(p-hydroxyphenyl)methane and its derivatives, tris(
p-hydroxyphenyl)ethane and its derivatives, tris(p-hydroxyphenyl)triisopropenylbenzene and its derivatives, 4,4'-(1-(4-(1
-(p-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)biphenyl and its derivatives, tetrakis(p-hydroxyphenyl)ethane and its derivatives, polyhydroxychromones and its derivatives,
Polyhydroxyflapones and their derivatives, polyhydroxyflavonols and their derivatives, polyhydroxyflavanones and their derivatives, polyhydroxyflavans and their derivatives, polyhydroxychromans and their derivatives, polyhydroxycatechins and their derivatives, etc. can be mentioned.

The polyhydric phenol sulfonic acid ester compound used in the present invention is a polyhydric phenol compound, an aliphatic sulfonic acid and its derivatives, an aliphatic sulfonic acid and its derivatives having a substituent, an aromatic sulfonic acid and its derivatives. It can be synthesized by an esterification reaction with a sulfonic acid compound such as a derivative, an aromatic sulfonic acid having a substituent, and a derivative thereof, and it is necessary to have at least one ester group.

Specific examples of the sulfonic acid ester compound represented by the general formula (1) used in the present invention include:
Phenyl benzenesulfonate, phenyl 2-methylbenzenesulfonate, phenyl 4-methylbenzenesulfonate, phenyl 2-chlorobenzenesulfonate, 4-
Phenyl chlorobenzenesulfonate, phenyl 2,5-dichlorobenzenesulfonate, phenyl 3,5-dichlorobenzenesulfonate, phenyl 2-bromobenzenesulfonate, phenyl 4-bromobenzenesulfonate, 2
-Phenyl nitrobenzenesulfonate, phenyl 3-nitrobenzenesulfonate, phenyl 4-hydroxybenzenesulfonate, phenyl naphthalenesulfonate, 5-
Phenyl hydroxynaphthalenesulfonate, methyl benzenesulfonate, methyl 2-methylbenzenesulfonate, methyl 4-methylbenzenesulfonate, methyl 2-chlorobenzenesulfonate, methyl 4-chlorobenzenesulfonate, methyl 2,5-dichlorobenzenesulfonate , methyl 3,5-dichlorobenzenesulfonate, methyl 2-bromobenzenesulfonate, methyl 4-bromobenzenesulfonate, methyl 2-nitrobenzenesulfonate, methyl 3-nitrobenzenesulfonate, methyl 4-nitrobenzenesulfonate, 4- Methyl hydroxybenzenesulfonate, methyl naphthalenesulfonate, methyl 5-hydroxynaphthalenesulfonate, benzyl benzenesulfonate, benzyl 2-methylbenzenesulfonate, benzyl 4-methylbenzenesulfonate, benzyl 2-chlorobenzenesulfonate, 4-chlorobenzene Benzyl sulfonate, Benzyl 2,5-dichlorobenzenesulfonate, Benzyl 3,5-dichlorobenzenesulfonate, Benzyl 2-bromobenzenesulfonate, Benzyl 4-bromobenzenesulfonate, Benzyl 2-nitrobenzenesulfonate, 3-nitrobenzene Benzyl sulfonate, 4-nitrobenzenesulfonate, 4-
Benzyl hydroxybenzenesulfonate, benzyl naphthalenesulfonate, benzyl 5-hydroxynaphthalenesulfonate, ethyl 4-methylbenzenesulfonate, 4
-2-bromoethyl methylbenzenesulfonate, 2-nitroethyl 4-methylbenzenesulfonate, 2-methoxyethyl 4-methylbenzenesulfonate, naphthalene 4-methylbenzenesulfonate, 4-chlorophenyl 4-methylbenzenesulfonate, 4- 4-Methylphenyl methylbenzenesulfonate, 2-nitrophenyl 4-methylbenzenesulfonate, 4-nitrophenyl 4-methylbenzenesulfonate, 4-methylbenzenesulfonate
-methoxyphenyl, 4-methylbenzenesulfonic acid 4
-chlorobenzyl, 4-methylbenzenesulfonic acid 4-
Methylbenzyl, 2-nitrobenzyl 4-methylbenzenesulfonate, 4-nitrobenzyl 4-methylbenzenesulfonate, 4-methoxybenzyl 4-methylbenzenesulfonate, ethyl 4-bromobenzenesulfonate, 4
-2-Bromoethyl bromobenzenesulfonate, 2-nitroethyl 4-bromobenzenesulfonate, 2-methoxyethyl 4-bromobenzenesulfonate, naphthalene 4-bromobenzenesulfonate, 4-chlorophenyl 4-bromobenzenesulfonate, 4- 4-Methylphenyl bromobenzenesulfonate, 2-nitrophenyl 4-bromobenzenesulfonate, 4-nitrophenyl 4-bromobenzenesulfonate, 4-bromobenzenesulfonate
-methoxyphenyl, 4-bromobenzenesulfonic acid 4
-chlorobenzyl, 4-bromobenzenesulfonic acid 4-
Methylbenzyl, 2-nitrobenzyl 4-bromobenzenesulfonate, 4-nitrobenzyl 4-bromobenzenesulfonate, 4-methoxybenzyl 4-bromobenzenesulfonate, ethyl 4-nitrobenzenesulfonate, 4
-2-bromoethyl nitrobenzenesulfonate, 2-nitroethyl 4-nitrobenzenesulfonate, 2-methoxyethyl 4-nitrobenzenesulfonate, naphthalene 4-nitrobenzenesulfonate, 4-chlorophenyl 4-nitrobenzenesulfonate, 4-nitrobenzenesulfonate 4- Methylphenyl, 2-nitrophenyl 4-nitrobenzenesulfonate, 4-nitrophenyl 4-nitrobenzenesulfonate, 4-nitrobenzenesulfonic acid 4
-methoxyphenyl, 4-nitrobenzenesulfonic acid 4
-chlorobenzyl, 4-nitrobenzenesulfonic acid 4-
Methylbenzyl, 2-nitrobenzyl 4-niobenzenesulfonate, 4-nitrobenzyl 4-nitrobenzenesulfonate, 4-methoxybenzyl 4-nitrobenzenesulfonate, and the like.

The sulfonic acid ester compounds used in the present invention may be used alone, or two or more thereof may be used in combination. The blending ratio of the sulfonic acid ester compound is usually 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the alkali-soluble phenol resin.
Parts by weight. If this blending ratio is less than 0.1 part by weight,
It becomes difficult to form a pattern, and conversely, if it exceeds 50 parts by weight, undeveloped residue is likely to occur.

(Resist Composition) The resist composition of the present invention is usually used by dissolving each of the above-mentioned components in a solvent in order to form a resist film by applying it to a substrate. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cyclohexanol, and butyrolactone; n-propyl alcohol;
iso-propyl alcohol, n-butyl alcohol,
Alcohols such as 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 ; Esters such as propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl acetate, ethyl acetate; methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-methoxypropionic acid Methyl, 2-
Monooxycarboxylic acid esters such as ethyl methoxypropionate; cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycols such as propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; halogenated hydrocarbons such as trichloroethylene aromatic hydrocarbons such as toluene and xylene; polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone; and the like. These solvents may be used alone or in combination of two or more. The resist composition of the present invention may include, if necessary,
Compatible additives such as surfactants, storage stabilizers, sensitizers, anti-striation agents, plasticizers, and antihalation agents can be included.

[0030] As the developer for the resist composition of the present invention, an aqueous alkali solution is used, specifically inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia; ethylamine, propylamine; Primary amines such as diethylamine and dipropylamine; Tertiary amines such as trimethylamine and triethylamine; Alcohol amines such as dienylethanolamine and triethanolamine; Tetramethylammonium hydroxide and tetraethyl Examples include quaternary ammonium salts such as ammonium hydroxide, trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, and trimethylhydroxyethylammonium hydroxide. Furthermore, if necessary, suitable amounts of water-soluble organic solvents such as methanol, ethanol, propanol, and ethylene glycol, surfactants, storage stabilizers, resin dissolution inhibitors, and the like can be added to the aqueous alkaline solution.

The resist composition of the present invention can be applied to the surface of a substrate such as a silicon wafer by a conventional method using a solvent solution thereof, and then a resist film can be formed by drying and removing the solvent. In particular, spin coating is preferred. Further, in the exposure, a fine pattern can be formed by using far ultraviolet rays, KrF excimer laser light, i-line (365 nm), or the like as a light source. After exposure, heat treatment (post-exposure bake)
This is preferred because the crosslinking reaction is promoted and sensitivity can be improved and stabilized.

[0032]

[Examples] The present invention will be explained in more detail with reference to Examples below. Note that parts and percentages in each example are based on weight unless otherwise specified.

[Example 1] Polyvinylphenol (Mw
=5000) 100 parts, alkyl etherified melamine-
15 parts of formaldehyde resin (manufactured by Sanwa Chemical Co., Ltd., Nikalac MW-30), 9 parts of -OH group of bisphenol A
8 parts of a compound of which 0% is methanesulfonic acid ester and 0.01 part of a fluorine-based surfactant are dissolved in 380 parts of ethyl 2-methoxypropionate, and a 0.1 μm polytetrafluoroethylene filter Teflon filter (manufactured by Millipore) is dissolved. A resist solution was prepared by filtration using a Teflon filter.

The above resist solution was applied onto a silicon wafer using a spinner, and then baked at 90° C. for 90 seconds to form a resist film with a thickness of 1.0 μm. This wafer was exposed to light using a far ultraviolet irradiation device (manufactured by Canon, PLA-521FA) and a test mask. Next, 120
After exposure, the film was baked at 60 seconds at .degree. C., and developed by dipping in an aqueous solution of tetramethylammonium hydroxide at 23.degree. C. for 1 minute to obtain a negative pattern. The film thickness of the pattern was measured with a film thickness meter (Tenko Corporation, Alpha Step 200) and was 0.95 μm. When the patterned wafer was taken out and observed under an electron microscope, it was found to be 0.45.
The micrometer pattern was resolved.

[Example 2] The wafer on which the pattern of Example 1 was formed was etched using a dry etching device (manufactured by Nichiden Anelva, DEM-451T) at a power of 300 W, a pressure of 0.03 Torr, and a gas of CF4/H2=30. When etching was performed at a frequency of 13.56 MHz and a frequency of 13.56 MHz, it was observed that only the areas where there was no pattern were etched. Observation of the resist pattern after etching revealed that it maintained almost the same shape as before etching.

[Example 3] Polyvinylphenol (Mw
=5000) 100 parts, alkyl etherified melamine-
15 parts of formaldehyde resin (Nicalac MW-30), 8 parts of phenyl 4-methylbenzenesulfonate, and 0.01 part of fluorosurfactant were dissolved in 375 parts of ethyl 2-methoxypropionate, and filtered with a 0.1 μm Teflon filter. It was filtered and a resist solution was prepared.

The above resist solution was applied onto a silicon wafer using a spinner, and then baked at 85° C. for 90 seconds to form a resist film with a thickness of 1.0 μm. This wafer was exposed to light using a far ultraviolet irradiation device PLA-521FA and a test mask. Next, post-exposure baking was performed at 125° C. for 60 seconds, and development was performed using a dipping method at 23° C. for 1 minute in a tetramethylammonium hydroxide aqueous solution to obtain a negative pattern. When the patterned wafer was taken out and observed under an electron microscope, a 0.45 μm pattern was resolved.

[Example 4] Hydrogenated polyvinylphenol (
Hydrogenation rate = 8%, Mw = 4900) 100 parts, alkyl ether group-containing phenol compound (manufactured by General Electric Company, Methylon Resin 751)
25 parts of the methylolated compound of tris(P-hydroxyphenyl)ethane in which 90% of the -OH groups are benzenesulfonic acid esters, 0.01 part of a fluorine-based surfactant, and 350 parts of propylene glycol monomethyl ether acetate. and filtered through a 0.1 μm Teflon filter to prepare a resist solution.

The above resist solution was applied onto a silicon wafer using a spinner, and then baked at 90° C. for 90 seconds to form a resist film with a thickness of 1.0 μm. This wafer was exposed to light using an excimer laser device (manufactured by Hamamatsu Photonics, C2926) filled with krypton/fluorine gas and a test mask. Next, post-exposure baking was performed at 130° C. for 60 seconds, and development was performed using a test methyl ammonium hydroxide aqueous solution at 23° C. for 1 minute by the immersion method to obtain a negative pattern. When the patterned wafer was taken out and observed under an electron microscope, it was found to be 0.55 μm.
pattern was resolved.

[Example 5] Hydrogenated polyvinylphenol (
Hydrogenation rate = 8%, Mw = 4900) 100 parts, alkyl etherified urea-formaldehyde resin (CYANAMI
15 parts of UFR-65 (manufactured by Company D), 5 parts of 2-chlorophenyl 4-nitrobenzenesulfonate, and 0.01 part of a fluorosurfactant were dissolved in 350 parts of propylene glycol monomethyl ether acetate, and filtered with a 0.1 μm Teflon filter. was filtered to prepare a resist solution.

The above resist solution was applied onto a silicon wafer using a spinner, and then baked at 90° C. for 90 seconds to form a resist film with a thickness of 1.0 μm. This wafer was exposed to light using a far ultraviolet irradiation device PLA-521FA and a test mask. Next, post-exposure baking was performed at 130° C. for 60 seconds, and development was performed using a dipping method at 23° C. for 1 minute in a tetramethylammonium hydroxide aqueous solution to obtain a negative pattern. When the patterned wafer was taken out and observed under an electron microscope, a 0.45 μm pattern was resolved.

[Example 6] Hydrogenated polyvinylphenol (
Hydrogenation rate = 8%, Mw = 4900) 100 parts, alkyl etherified urethane-formaldehyde resin 15 parts, tris(P-hydroxyphenyl)triisopropenylbenzene compound in which 80% of the -OH groups are methanesulfonic acid esters 8 parts and 0.01 part of a fluorine-based surfactant were dissolved in 330 parts of cyclohexanone and filtered through a 0.1 μm Teflon filter to prepare a resist solution.

The above resist solution was applied onto a silicon wafer using a spinner, and then baked at 90° C. for 90 seconds to form a resist film with a thickness of 0.8 μm. This wafer was exposed to light using a far ultraviolet irradiation device PLA-521FA and a test mask. Next, post-exposure baking was performed at 130° C. for 60 seconds, and development was performed using a dipping method at 23° C. for 1 minute in a tetramethylammonium hydroxide aqueous solution to obtain a negative pattern. When the patterned wafer was taken out and observed under an electron microscope, a 0.50 μm pattern was resolved.

[Example 7] m-cresol novolak (
Mw=6100), 20 parts of alkyl etherified urethane-formaldehyde resin, 6 parts of methyl 4-bromobenzenesulfonate and 380 parts of ethyl 2-methoxypropionate.
% and filtered through a 0.1 μm Teflon filter to prepare a resist solution.

The above resist solution was applied onto a silicon wafer using a spinner, and then baked at 90° C. for 90 seconds to form a resist film with a thickness of 0.8 μm. This wafer was exposed to light using a far ultraviolet irradiation device PLA-521FA and a test mask. Next, post-exposure baking was performed at 125° C. for 60 seconds, and development was performed using a tetramethylammonium hydroxide aqueous solution at 23° C. for 1 minute by a dipping method to obtain a negative pattern. When the patterned wafer was taken out and observed under an electron microscope, a 0.50 μm pattern was resolved.

[Example 8] m-cresol novolak (
Mw=6100), alkyl etherified urea-formaldehyde resin (manufactured by CYANAMID, CYMEL11
74) 20 parts, 10 parts of a compound in which 50% of the -OH groups of pentahydroxybiphenyl are benzenesulfonic acid esters, and 0.01 part of a fluorosurfactant are dissolved in 330 parts of cyclohexanone, and filtered with a 0.1 μm Teflon filter. was filtered to prepare a resist solution.

The above resist solution was applied onto a silicon wafer using a spinner, and then baked at 90° C. for 90 seconds to form a resist film with a thickness of 1.2 μm. This wafer was exposed to light using a far ultraviolet irradiation device PLA-521FA and a test mask. Next, post-exposure baking was performed at 125° C. for 60 seconds, and development was performed using a tetramethylammonium hydroxide aqueous solution at 23° C. for 1 minute by a dipping method to obtain a negative pattern. When the patterned wafer was taken out and observed under an electron microscope, a 0.45 μm pattern was resolved.

[Example 9] Hydrogenated polyvinylphenol (
Hydrogenation rate = 8%, Mw = 4900) 100 parts, alkyl etherified melamine-formaldehyde resin (Nicalak MW-30) 20 parts, 4-methylbenzenesulfonic acid-
2-nitrophenyl 6 parts, fluorosurfactant 0.01
One part was dissolved in 330 parts of cyclohexanone and filtered through a 0.1 μm Teflon filter to prepare a resist solution.

The above resist solution was applied onto a silicon wafer using a spinner, and then baked at 90° C. for 90 seconds to form a resist film with a thickness of 0.8 μm. This wafer was exposed to light using a far ultraviolet irradiation device PLA-521FA and a test mask. Next, a post-exposure bake was performed at 130° C. for 60 seconds, and a negative pattern was obtained by developing with an aqueous tetramethylammonium hydroxide solution at 23° C. for 1 minute by dipping. When the patterned wafer was taken out and observed under an electron microscope, a 0.45 μm pattern was resolved.

[0050]

[Effects of the Invention] According to the present invention, resist properties such as sensitivity, resolution, etching resistance, and storage stability are excellent;
A resist material suitable for lithography using short-wavelength deep ultraviolet light or KrF excimer laser light is provided. The resist composition of the present invention is particularly suitable as a negative resist for microfabrication of semiconductor devices.

Claims (3)

[Claims] [Claim 1] Alkali-soluble phenolic resin (A)
, a compound (B) that crosslinks in the presence of an acid, a sulfonic acid ester compound of polyhydric phenol, and the following general formula (
A resist composition comprising at least one sulfonic acid ester compound (C) selected from the group consisting of sulfonic acid ester compounds represented by 1). [Formula 1] General formula (1) [wherein R1 is an aryl group, a substituted (halogen, alkyl, nitro, alkoxy) aryl group, an alkyl group, a substituted (halogen, nitro, alkoxy) alkyl group, R2 represents an alkyl group, a substituted (halogen, alkyl, nitro, alkoxy) alkyl group, an aralkyl group, a substituted (halogen, alkyl, nitro, alkoxy) aralkyl group, an allyl group, a substituted (halogen, alkyl, nitro, alkoxy) allyl group . ] [Claim 2] Alkali-soluble phenolic resin (A)
2. The resist composition according to claim 1, wherein is an alkali-soluble hydrogenated phenolic resin. 3. The resist according to claim 1, wherein the compound (B) that is crosslinked in the presence of an acid is a compound having a C-O-R group (R is a hydrogen atom or an alkyl group) or a compound having an epoxy group. Composition.