JPH05281731A - Resist composition - Google Patents

Abstract

PURPOSE:To provide a resist material having good balance of resist characteristics such as sensitivity, resolution, etching resistance, and storage stability. CONSTITUTION:This resist compsn. contains a compd. having acid decomposing groups and a compd. which produces acid by irradiation of active rays. The compd. which produces acid by irradiation of active rays is at least one kind of compd. selected from compds. (1) and (2). (1) 1,2-naphthoquinonediazide-4- sulfonate or/and 1,2-naphthoquinonediazide-4-sulfonic acid imide of a compd. having hydroxyl groups or imide groups and showing <=0.01 absorbance per 1ppm in 248-251nm wavelength (2) 1,2-naphthoquinonediazide-4-sulfonate and/or 1,2-naphthoquinonediazide-4-sulfonic acid imide of a compd. having hydroxyl groups or imide groups and containing halogen.

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, KrF excimer laser light or the like. The resist composition of the present invention is particularly suitable as a positive resist for fine processing of semiconductor devices.

[0002]

2. Description of the Related Art When manufacturing a semiconductor device by fine processing using a resist, a resist solution is applied to the surface of a silicon wafer to form a photosensitive film, which is irradiated with light to form a latent image, which is then developed. An image (pattern) is obtained by a lithographic technique for forming a negative or positive image. The resist remaining on the silicon wafer is used as a protective film, etching is performed, and then the resist film is removed to complete the microfabrication.

By the way, in recent years, IC, LSI, and V
Along with the high integration, high density, and miniaturization of semiconductor elements in LSIs, a technique for forming a fine pattern of 1 μm or less is required. However, in the conventional photolithography technique using near-ultraviolet light or visible light, 1 μm
It is extremely difficult to form the following fine patterns with high precision, and the yield is significantly reduced.

Therefore, in order to improve the resolution of exposure in place of the conventional photolithography using light (ultraviolet light having a wavelength of 350 to 450 nm), far ultraviolet light having a short wavelength (short wavelength ultraviolet light) and KrF excimer laser light ( Wavelength 2
Krypton fluoride laser that emits 48 nm light)
A lithographic technique using such a technique is being researched. The resist materials that are the core of this lithography technology are:
Many high-level properties are required, but the most important ones are sensitivity, resolution, etching resistance and storage stability.

However, conventionally developed resist materials are
Not all of these performances are fully satisfied, and improvement in performance has been strongly desired. 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 polymethylmethacrylate have good resolution but poor sensitivity and dry etching resistance. Also,
When a novolac-based positive photoresist that has been used for UV exposure with a wavelength of 350 to 450 nm is exposed to deep UV light, the resist itself absorbs too much light to the light source, so that a fine pattern cannot be formed well.

In recent years, attention has been focused on increasing the sensitivity of resists using an acid catalyst and a chemical amplification effect. For example, a base polymer, a photo-acid generator (a compound that produces an acid upon irradiation with actinic rays), and an acid-sensitive acid. A resist for microfabrication consisting of a three-component system of substances has been developed. This is a positive or negative resist in which an acid-sensitive substance reacts with an acid generated by light as a catalyst to change the solubility of a base polymer. As a specific example, a positive resist including a novolac resin, a photoacid generator, and a dissolution inhibitor is known. The dissolution inhibiting agent has a dissolution inhibiting effect on the novolak resin, and reacts with an acid to exhibit a dissolution promoting action.

In addition, as a resist aiming at high sensitivity, the functional group that governs the solubility of the base polymer is blocked (protected) to make it insoluble, and the acid generated by light is used as a catalyst for protection. There is also known a positive resist of the type in which the base is removed to restore the solubility of the polymer base material in the phenomenon liquid. However, conventional resists are still insufficient in view of recent high performance requirements. Therefore, there has been a strong demand for the development of a new resist that satisfies the above performance in a well-balanced manner.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resist material in which resist characteristics such as sensitivity, resolution, etching resistance and storage stability are highly balanced. Another object of the present invention is to provide a resist material suitable for lithography using deep ultraviolet rays having a short wavelength or KrF excimer laser light. Another object of the present invention is to provide a resist composition which is particularly suitable as a positive resist for fine processing of semiconductor devices.

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems of the prior art. As a result, a compound having an acid-decomposable group, a compound which produces an acid upon irradiation with actinic rays, and an alkali-soluble compound if desired. In a resist composition containing a phenolic resin, by using a specific 1,2-naphthoquinonediazide-4-sulfonic acid-based compound as a compound that generates an acid upon irradiation with actinic rays, it has been found that the above object can be achieved. The present invention has been completed based on the findings.

[0010]

Thus, according to the present invention, in a resist composition containing a compound having an acid-decomposable group and a compound capable of generating an acid upon irradiation with actinic rays, an acid upon irradiation with actinic rays is used. The compound which produces (a) has a hydroxyl group or an imide group, and 248 to 2
1,2-naphthoquinonediazide-4-, a compound having an absorbance of 0.01 or less per 1 ppm at 51 nm
Sulfonic acid ester, (b) 1,2-naphthoquinonediazide-4-sulfonic acid imide of a compound having a hydroxyl group or an imide group, and having an absorbance of 0.01 or less per 1 ppm at 248 to 251 nm, (c) 1,2-naphthoquinonediazide-4-sulfonic acid ester of a compound having a hydroxyl group or an imide group and containing a halogen, and (d) a compound having a hydroxyl group or an imide group and containing a halogen 1 There is provided a resist composition comprising at least one compound selected from the group consisting of 2,2-naphthoquinonediazide-4-sulfonic acid imide.

The present invention will be described in detail below. (Compound having an acid-decomposable group) The compound having an acid-decomposable group used in the present invention is decomposed in the presence of an acid derived from a compound that generates an acid by irradiation with actinic rays, and the compound is There is no particular limitation as long as it is a substance that improves the solubility in an alkaline developer.

Specific examples of the compound having an acid-decomposable group include a compound having an ether group, a compound having an enol ether group, a compound having an acetal group, a compound having an orthocarbonate group, a compound having an acyliminocarbonate group, A compound having a carbonate group,
Low molecular weight compounds having a C—O—C bond, such as compounds having an orthoformate group, compounds having an orthocarbonyl ester group, compounds having a carbonyl ester group, compounds having a carbonylamide acetal group,
Polymer compounds; low molecular compounds having a Si—O—C bond such as compounds having a silyl ether group, compounds having a silyl enol group, compounds having a silyl ester group, and high molecular compounds; You may mix and use 2 or more types.

The polymer compound having an acid-decomposable group is, for example, a polymer such as a resin obtained by t-butoxycarbonylating a hydroxyl group of polyvinylphenol or a resin obtained by t-butoxycarbonylating a hydroxyl group of hydrogenated polyvinylphenol. A resin obtained by introducing the functional group of 1. by a chemical reaction; vinylphenol / pt-butoxystyrene copolymer, pt-butoxystyrene / p-hydroxystyrene copolymer, pt-butoxystyrene / fumaronitrile Examples of the resin include a copolymer, a styrene / t-butyl methacrylate copolymer, and the like; a resin obtained by copolymerizing a monomer having a protective group that is released by an acid. The polymer compound having an acid-decomposable group has a functional group, and thus the solubility in an alkaline developer is suppressed, but the functional group is decomposed in the presence of an acid,
It becomes alkali-soluble. Further, when a polymer compound having these acid-decomposable groups is used in combination with an alkali-soluble phenol resin such as a novolac resin, it acts as a dissolution inhibitor for the alkali developer of the alkali-soluble phenol resin, and when reacted with an acid, it dissolves. Acts as a promoter.

Examples of the low molecular weight compound having an acid-decomposable group include t-butoxycarbonyl compound of bisphenol A, t-butyl ether compound of bisphenol A,
Etc. can be mentioned. These low molecular weight compounds act as a dissolution inhibitor for the alkali developing solution of the alkali-soluble phenol resin, and act as a dissolution accelerator when reacted with an acid.

These compounds having an acid-decomposable group are high molecular compounds, have a suitable dissolution inhibiting property in an alkali developing solution, and react with an acid to be alkali-soluble with good sensitivity. By combining with a compound that forms an acid upon irradiation with actinic rays, a resist composition having high sensitivity and high resolution can be obtained without using an alkali-soluble resin.

When the compound having an acid-decomposable group is used together with the alkali-soluble phenol resin, it is usually 3 to 10 parts by weight with respect to 100 parts by weight of the alkali-soluble resin.
Used at a rate of 0 parts by weight. If the usage ratio is less than 3 parts by weight, pattern formation becomes impossible. On the contrary, if the usage ratio exceeds 100 parts by weight, the sensitivity is lowered and the development residue tends to occur.

(Compound which produces an acid upon irradiation with actinic rays) In the present invention, a compound which produces an acid upon irradiation with actinic rays (also referred to as a photoacid generator or a compound capable of cleavable acid) is a hydroxyl group or an imide group. And has
1,2-naphthoquinonediazide-4-sulfonic acid ester (a) or 1,2-naphthoquinonediazide-4-sulfonic acid imide (b) of a compound whose absorbance per ppm at 248 to 251 nm is 0.01 or less, or 1,2-naphthoquinonediazide-4 which is a compound having a hydroxyl group or an imide group and containing halogen
-Sulfonic acid ester (c) or 1,2-naphthoquinonediazide-4-sulfonic acid imide (d), at least one 1,2-naphthoquinonediazide-4
-Use sulfonic acid compounds.

Compounds (a) and (b) The 1,2-naphthoquinonediazide-4-sulfonic acid compounds (a) and (b) used in the present invention have a hydroxyl group or an imide group, and are 248 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-4-sulfonic acid imide of a compound whose absorbance per ppm at ˜251 nm is 0.01 or less (however, halogen-containing compound Except).

Examples of the compound having an absorbance of 0.01 or less per 1 ppm at 248 to 251 nm are alcohols such as methanol, ethanol, propanol and cyclohexanol, and diols such as ethylene glycol, propylene glycol and butanediol. A compound having an alcoholic-OH group such as cresol and phloroglucinol, a bisphenol such as bisphenol A and bisphenol F, a chromone, a flavanone, a catechin, and hydrogenation of a dimer of isopropenylphenol And compounds having a phenolic-OH group; compounds having an imide group such as succinimide, maleic acid imide, and phthalic acid imide; and the like. When a compound having an absorbance per ppm of 248 to 251 nm of more than 0.01 is used, the resolution is lowered and the sensitivity is also lowered.

1,2-naphthoquinonediazide-4-sulfonic acid compounds (a) used in the present invention
(B) can be easily synthesized by reacting the above-mentioned compound having a hydroxyl group or an imide group with 1,2-naphthoquinonediazide-4-sulfonic acid, and is described by Mototaro Nagamatsu and Hideo Inui in "Photosensitivity". Polymer "(July 2, 1989)
Issued the 7th printing on the 0th, published by Kodansha) Page 116, 192-
It can be synthesized according to a conventional method described on page 195.

Compounds (c) and (d) The 1,2-naphthoquinonediazide-4-sulfonic acid compounds (c) to (d) used in the present invention have a hydroxyl group or an imide group, and are halogen. 1,2-naphthoquinonediazide-4-sulfonic acid ester of a compound containing, and 1,2-naphthoquinonediazide-4-sulfonic acid imide.

Examples of such a compound include alcohols such as halogen-containing alcohols such as methanol, ethanol, propanol and cyclohexanol, halogen-containing alcohols such as ethylene glycol, propylene glycol and butanediol. Compounds having an OH group; halogen-containing phenols, cresols, xylenols and other phenols,
Bisphenols such as bisphenol A and bisphenol F containing halogen, trisphenols containing halogen, tetrakisphenols, chromones,
Compounds having a phenolic-OH group such as flavanones and catechins; halogen-containing succinimide,
Compounds having an imide group such as maleic acid imide and phthalic acid imide; and the like.

These compounds have a structure in which a halogen atom is introduced as a substituent to the compound having a hydroxyl group, an amino group or an imide group, and the halogen is preferably chlorine, bromine or iodine. Preferred are bromine and iodine.

1,2-naphthoquinonediazide-4-sulfonic acid compounds (c) used in the present invention
(D) can be easily synthesized by the reaction of the compound having a hydroxyl group or an imide group and a halogen with 1,2-naphthoquinonediazide-4-sulfonic acid, and (a) to (a) Like the compound b), it can be synthesized according to a conventional method.

1,2-naphthoquinonediazide-4-sulfonic acid compound (a) used in the present invention,
Each of (b), (c), and (d) can be used alone, or two or more kinds may be used in combination.

The proportion of 1,2-naphthoquinonediazide-4-sulfonic acid compound used as the acid-generating compound is such that it is used in combination with a polymer compound having an acid-decomposable group.
When not using the alkali-soluble phenolic resin together,
Usually 0.1 to 5 relative to 100 parts by weight of the polymer compound.
It is 0 part by weight, preferably 2 to 20 parts by weight. When an alkali-soluble phenol resin is used in combination, it is usually 0.
It is 1 to 50 parts by weight, preferably 2 to 20 parts by weight. If the usage ratio is less than 0.1 parts by weight, pattern formation becomes difficult, and if it exceeds 50 parts by weight, undeveloped residue tends to occur, and in any case, the resist performance deteriorates.

(Alkali-soluble phenol resin) Examples of the alkali-soluble phenol resin used in the present invention include condensation reaction products of phenols and aldehydes, condensation reaction products of phenols and ketones, and vinylphenol-based resins. Examples thereof include polymers, isopropenylphenol-based polymers, and hydrogenation reaction products of these phenolic resins.

Specific examples of the phenols used here include monohydric phenols such as phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol and phenylphenol; resorcinol, pyrocatechol, hydroquinone, bisphenol A, pyrogallol and the like. And polyhydric phenols. Specific examples of the aldehydes include formaldehyde, acetaldehyde, benzaldehyde, terephthalaldehyde and the like. Specific examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone and the like. These condensation reactions can be performed according to a conventional method.

The vinylphenol polymer is selected from a homopolymer of vinylphenol and a copolymer of vinylphenol and a copolymerizable component. 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 isopropenylphenol homopolymers and copolymers with isopropenylphenol-copolymerizable components. Specific examples of the copolymerizable component include acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic imide, vinyl acetate, acrylonitrile, and derivatives thereof.

When a hydrogenated product of a phenol resin is used, the hydrogenation reaction can be carried out by any known method. For example, it is achieved by dissolving a phenol resin in an organic solvent and introducing hydrogen in the presence of a homogeneous or heterogeneous hydrogenation catalyst. Hydrogenation is carried out so that the hydrogenation rate is usually 0.1 to 70%, preferably 1 to 50%, and more preferably 3 to 40%. If the hydrogenation rate exceeds 70%, the hydrogenated phenolic resin becomes insoluble in alkali, which is unsuitable as a base polymer for resists. Further, if the hydrogenation rate is too low, the effect of improving the performance by hydrogenation becomes small. These alkali-soluble phenolic resins may be used alone or in a mixture of two or more.

The resist composition of the present invention may optionally contain, for example, a copolymer of styrene and acrylic acid, methacrylic acid or maleic anhydride in order to improve developability, storage stability, heat resistance and the like. A copolymer of an alkene and maleic anhydride, a vinyl alcohol polymer, a vinylpyrrolidone polymer, rosin, shellac and the like can be added.

(Resist Composition) The resist composition of the present invention is usually used by dissolving each component in a solvent in order to form a resist film by coating on a substrate. 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; ethylene glycol. Ethers such as dimethyl ether, ethylene glycol diethyl ether, dioxane; alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate,
Esters such as butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate; methyl 2-oxypropionate, ethyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, etc. Monooxycarboxylic acid esters; 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 ethyl ether, propylene glycol monoethyl ether Propylene glycols such as acetate and propylene glycol monobutyl ether; diethylene glycol Diethylene glycols such as methyl 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; dimethylacetamide, dimethylformamide, Polar solvents such as N-methylacetamide and N-methylpyrrolidone; and the like. You may use these individually or in mixture of 2 or more types.

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. Specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, and ammonia; ethylamine, propylamine, etc. Secondary amines such as diethylamine and dipropylamine; tertiary amines such as trimethylamine and triethylamine; alcohol amines such as diethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxy And quaternary ammonium salts such as trimethyl hydroxymethyl ammonium hydroxide, triethyl hydroxymethyl ammonium hydroxide, and trimethyl hydroxyethyl ammonium hydroxide; It is.

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

The resist composition of the present invention can be used to form a resist film by applying the solvent solution to the surface of a substrate such as a silicon wafer by a conventional method and then removing the solvent by drying. As a coating method,
Spin coating is recommended.

For the exposure, a fine pattern can be formed by irradiating short wavelength ultraviolet light or KrF excimer laser light using a deep ultraviolet irradiation device or an excimer laser device in which krypton / fluorine gas is enclosed. By performing a heat treatment (post-exposure bake) after the light irradiation, the reaction between the acid and the compound having an acid-decomposable group is promoted, and the sensitivity can be further increased.

[0039]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, parts and% in each example are based on weight unless otherwise specified.

Example 1 100 parts of a resin obtained by t-butoxycarbonylating 30 mol% of the hydroxyl groups of polyvinylphenol (weight average molecular weight 5000), bisphenol F.
1,2-naphthoquinonediazide-4-sulfonic acid ester of 4 parts and 0.01 parts of a fluorine-containing surfactant are dissolved in 330 parts of ethyl 2-methoxypropionate to give 0.1 μm.
Polytetrafluoroethylene filter (PTFE
Filter (manufactured by Millipore) was used to prepare a resist solution.

After coating the above resist solution on a silicon wafer with a spinner, it is baked at 100 ° C. for 90 seconds,
A resist film having a thickness of 1.0 μm was formed. This wafer was exposed using a deep ultraviolet irradiation device PLA-521FA (manufactured by Canon Inc.) and a test mask. Then 1
After exposure at 20 ° C. for 60 seconds and baking, it is washed with tetramethylammonium hydroxide aqueous solution (concentration 2.38%)
It was developed by a dipping method at 3 ° C. for 1 minute to obtain a positive pattern.

The sensitivity was evaluated to be 21 mJ / cm ² , and the film thickness of the pattern was measured with a film thickness meter Alpha step 200.
It was 0.94 μm when measured by (manufactured by Tenko).
When the wafer on which the pattern was formed was taken out and observed with an electron microscope, a pattern of 0.60 μm was resolved.

Example 2 100 parts of a resin obtained by t-butoxycarbonylating 30 mol% of the hydroxyl groups of polyvinylphenol (weight average molecular weight 5000), 1,2-naphthoquinonediazide-4-sulfonic acid ester of p-chlorophenol. 4 parts and 0.01 part of a fluorochemical surfactant are propylene glycol monomethyl ether acetate 300
Part, and filtered through a 0.1 μm PTFE filter to prepare a resist solution.

The resist solution was applied onto a silicon wafer with a spinner and baked at 90 ° C. for 90 seconds to form a resist film having a thickness of 1.0 μm. This wafer is used as a KrF excimer laser stepper NSR 1505E.
Exposure was performed using X (manufactured by Nikon Corporation, NA = 0.42) and a test reticle. Next, after exposure and baking at 110 ° C. for 60 seconds, it was developed by an immersion method in an aqueous tetramethylammonium hydroxide solution at 23 ° C. for 1 minute to obtain a positive pattern.

The sensitivity was evaluated to be 24 mJ / cm ² , and the film thickness of the pattern was 0.94 μm when measured with a film thickness meter Alpha Step 200. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
A 0.45 μm pattern was resolved.

[Example 3] Resin 1 obtained by t-butoxycarbonylating 25 mol% of the hydroxyl groups of hydrogenated polyvinylphenol (hydrogenation rate = 12%, weight average molecular weight 5000).
00 parts, 5 parts of 1,2-naphthoquinonediazide-4-sulfonic acid ester of bisphenol F, and 0.01 parts of a fluorochemical surfactant are ethyl 2-methoxypropionate 33
It was dissolved in 0 part and filtered through a 0.1 μm PTFE filter to prepare a resist solution.

After coating the above resist solution on a silicon wafer with a spinner, it is baked at 100 ° C. for 90 seconds,
A resist film having a thickness of 1.0 μm was formed. This wafer is used as a KrF excimer laser stepper NSR 1505E.
Exposure was performed using X and a test reticle. Then 1
After exposure at 10 ° C. for 60 seconds and baking, it was developed with an aqueous tetramethylammonium hydroxide solution at 23 ° C. for 1 minute by a dipping method to obtain a positive pattern.

The sensitivity was evaluated to be 20 mJ / cm ² , and the film thickness of the pattern was measured with a film thickness meter Alpha Step 200 to be 0.94 m. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
A 0.45 μm pattern was resolved.

Example 4 100 parts of vinylphenol / t-butoxystyrene (50/50 molar ratio) copolymer (weight average molecular weight 5000), 1,2-naphthoquinonediazide-4-sulfonic acid of tetrabromobisphenol A 6 parts of ester, 0.01 part of fluorosurfactant
Dissolve in 330 parts of ethyl methoxypropionate to give 0.1
A resist solution was prepared by filtering through a μm PTFE filter.

The above resist solution was applied onto a silicon wafer with a spinner, and then baked at 100 ° C. for 90 seconds,
A resist film having a thickness of 1.0 μm was formed. This wafer is used as a KrF excimer laser stepper NSR 1505E.
Exposure was performed using X and a test reticle. Then 1
After exposure at 20 ° C. for 60 seconds and baking, it was developed with an aqueous tetramethylammonium hydroxide solution at 23 ° C. for 1 minute by a dipping method to obtain a positive pattern.

When the sensitivity was evaluated, it was 18 mJ / cm ² , and when the film thickness of the pattern was measured by a film thickness meter Alpha Step 200, it was 0.95 μm. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
A 0.50 μm pattern was resolved.

Example 5 100 parts of vinylphenol / t-butoxystyrene (50/50 molar ratio) copolymer (weight average molecular weight 5000) and hydrogenated 1,2-naphtho of isopropenylphenol dimer. Quinone diazide
A resist solution was prepared by dissolving 5 parts of 4-sulfonic acid ester and 0.01 part of a fluorochemical surfactant in 330 parts of ethyl 2-methoxypropionate and filtering with a 0.1 μm PTFE filter.

The above resist solution was applied onto a silicon wafer with a spinner and then baked at 90 ° C. for 90 seconds to form a resist film having a thickness of 1.0 μm. This wafer was exposed using a far-ultraviolet irradiation device PLA-521FA and a test mask. Next, after exposure and baking at 120 ° C. for 60 seconds, it was developed by an immersion method at 23 ° C. for 1 minute in an aqueous solution of tetramethylammonium hydroxide to obtain a positive pattern.

The sensitivity was evaluated to be 22 mJ / cm ² , and the film thickness of the pattern was measured with a film thickness meter Alpha Step 200 to be 0.93 μm. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
The pattern of 0.65 μm was resolved.

Example 6 100 parts of a styrene / t-butyl methacrylate (50/50 molar ratio) copolymer (weight average molecular weight 7800) and 4 parts of 1,2-naphthoquinonediazide-4-sulfonic acid ester of bisphenol F were added. Department,
0.01 part of a fluorine-based surfactant was dissolved in 330 parts of ethyl 2-methoxypropionate and filtered through a 0.1 μm PTFE filter to prepare a resist solution.

The above resist solution was applied onto a silicon wafer with a spinner and then baked at 90 ° C. for 90 seconds to form a resist film having a thickness of 1.0 μm. This wafer is used as a KrF excimer laser stepper NSR 1505EX.
Exposure was performed using a test reticle. Then 1
After exposure at 20 ° C. for 60 seconds and baking, it was developed with an aqueous tetramethylammonium hydroxide solution at 23 ° C. for 1 minute by a dipping method to obtain a positive pattern.

The sensitivity was evaluated to be 20 mJ / cm ² , and the film thickness of the pattern was measured with a film thickness meter Alpha Step 200 to be 0.95 μm. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
A 0.45 μm pattern was resolved.

[Example 7] 100 parts of styrene / t-butyl methacrylate (50/50 molar ratio) copolymer (weight average molecular weight 7800), 1, 2 of p-chlorophenol
-Naphthoquinone diazide-4-sulfonic acid ester
Part, 0.01 part of a fluorine-based surfactant is dissolved in 330 part of ethyl 2-methoxypropionate, and PTF of 0.1 μm is dissolved.
A resist solution was prepared by filtering with a filter made by E.

The above resist solution was applied onto a silicon wafer with a spinner and then baked at 90 ° C. for 90 seconds to form a resist film having a thickness of 1.0 μm. This wafer is used as a KrF excimer laser stepper NSR 1505EX.
Exposure was performed using a test reticle. Next, 13
After exposure at 0 ° C. for 60 seconds and baking, it was developed with an aqueous tetramethylammonium hydroxide solution at 23 ° C. for 1 minute by a dipping method to obtain a positive pattern.

The sensitivity was evaluated to be 16 mJ / cm ² , and the film thickness of the pattern was measured with a film thickness meter Alpha Step 200 to be 0.95 μm. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
A 0.45 μm pattern was resolved.

Example 8 Polyvinylphenol 100
Parts, polyvinylphenol (weight average molecular weight 7,000)
15 parts of a resin obtained by t-butoxycarbonylating 50 mol% of hydroxyl groups of 1, 2, 5-naphthoquinonediazide-4-sulfonic acid ester of bisphenol F, and 0.01 parts of a fluorochemical surfactant are added to 2-methoxypropione. It was dissolved in 330 parts of ethyl acidate and filtered through a 0.1 μm PTFE filter to prepare a resist solution.

After coating the above resist solution on a silicon wafer with a spinner, it is baked at 100 ° C. for 90 seconds,
A resist film having a thickness of 1.0 μm was formed. This wafer is used as a KrF excimer laser stepper NSR 1505E.
Exposure was performed using X and a test reticle. Then 1
After exposure at 20 ° C. for 60 seconds and baking, it was developed with an aqueous tetramethylammonium hydroxide solution at 23 ° C. for 1 minute by a dipping method to obtain a positive pattern.

The sensitivity was evaluated to be 25 mJ / cm ² , and the film thickness of the pattern was measured to 0.93 μm by the film thickness meter Alpha Step 200. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
A 0.50 μm pattern was resolved.

Example 9 Hydrogenated polyvinylphenol (hydrogenation rate = 10%, weight average molecular weight 5000) 100
Parts, polyvinylphenol (weight average molecular weight 7,000)
10 parts of a resin obtained by t-butoxycarbonylating 50 mol% of hydroxyl groups of 1,2-tetrabromobisphenol A
Add naphthoquinonediazide-4-sulfonic acid ester to 5
Part, 0.01 part of a fluorine-based surfactant is dissolved in 330 part of ethyl 2-methoxypropionate, and PTF of 0.1 μm is dissolved.
A resist solution was prepared by filtering with a filter made by E.

The above resist solution was applied onto a silicon wafer with a spinner, and then baked at 110 ° C. for 90 seconds,
A resist film having a thickness of 1.0 μm was formed. This wafer is used as a KrF excimer laser stepper NSR 1505E.
Exposure was performed using X and a test reticle. Then 1
After exposure at 00 ° C. for 60 seconds and baking, it was developed with an aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 1 minute by a dipping method to obtain a positive pattern.

The sensitivity was evaluated to be 20 mJ / cm ² , and the film thickness of the pattern was measured with a film thickness meter Alpha Step 200 to be 0.94 μm. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
A 0.40 μm pattern was resolved.

Example 10 100 parts of vinylphenol / methyl methacrylate (50/50 molar ratio) copolymer (weight average molecular weight 6000) and 50 mol% of the hydroxyl groups of polyvinylphenol (weight average molecular weight 7000) were added to t.
10 parts of butoxycarbonylated resin, 1,2-naphthoquinonediazide-4 of tetrachlorobisphenol F
6 parts sulphonic acid ester, fluorosurfactant 0.
01 part was dissolved in 330 parts ethyl 2-methoxypropionate and filtered through a 0.1 μm PTFE filter to prepare a resist solution.

The above resist solution was applied onto a silicon wafer with a spinner, and then baked at 100 ° C. for 90 seconds,
A resist film having a thickness of 1.0 μm was formed. This wafer is used as a KrF excimer laser stepper NSR 1505E.
Exposure was performed using X and a test reticle. Then 1
After exposure at 20 ° C. for 60 seconds and baking, it was developed with an aqueous tetramethylammonium hydroxide solution at 23 ° C. for 1 minute by a dipping method to obtain a positive pattern.

The sensitivity was evaluated to be 25 mJ / cm ² , and the film thickness of the pattern was measured with a film thickness meter Alpha Step 200 to be 0.94 μm. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
A 0.45 μm pattern was resolved.

Example 11 Polyvinylphenol (weight average molecular weight 5000) 100 parts, polyvinylphenol / t-butoxystyrene (50/50 mole ratio) copolymer (weight average molecular weight 4800) 10 parts, maleimide 1,2 -Naphthoquinonediazide-4-sulfonic acid ester (4 parts) and fluorine-containing surfactant (0.01 part) were dissolved in ethyl 2-methoxypropionate (330 parts) and filtered through a 0.1 µm PTFE filter to prepare a resist solution. did.

The resist solution was applied onto a silicon wafer with 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 exposed using a far-ultraviolet irradiation device PLA-521FA and a test mask. Next, after exposure and baking at 120 ° C. for 60 seconds, it was developed by an immersion method at 23 ° C. for 1 minute in an aqueous solution of tetramethylammonium hydroxide to obtain a positive pattern.

When the sensitivity was evaluated, it was 20 mJ / cm ² , and when the film thickness of the pattern was measured by a film thickness meter Alpha Step 200, it was 0.93 μm. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
The pattern of 0.60 μm was resolved.

Example 12 Hydrogenated polyvinylphenol (hydrogenation rate = 20%, weight average molecular weight 5000) 10
0 part, 20 parts of t-butoxycarbonyl compound of bisphenol A, 4 parts of 1,2-naphthoquinonediazide-4-sulfonic acid ester of tetrachlorobisphenol S, 0.01 part of a fluorochemical surfactant is 2-methoxypropionic acid. It was dissolved in 330 parts of ethyl and filtered through a 0.1 μm PTFE filter to prepare a resist solution.

The above resist solution was applied onto a silicon wafer with a spinner and then baked at 90 ° C. for 90 seconds to form a resist film having a thickness of 1.0 μm. This wafer is used as a KrF excimer laser stepper NSR 1505EX.
Exposure was performed using a test reticle. Next, 11
After exposure at 0 ° C. for 60 seconds and baking, it was developed with an aqueous tetramethylammonium hydroxide solution at 23 ° C. for 1 minute by a dipping method to obtain a positive pattern.

The sensitivity was evaluated to be 20 mJ / cm ² , and the film thickness of the pattern was 0.95 μm when measured with a film thickness meter Alpha Step 200. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
A 0.50 μm pattern was resolved.

Example 13 100 parts of vinylphenol / t-butoxystyrene (70/30 molar ratio) copolymer (weight average molecular weight 5000), t-of bisphenol A
Butoxycarbonyl compound 20 parts, methanol 1,2-
Add naphthoquinone diazide-4-sulfonic acid ester to 5
Parts, 0.01 parts of a fluorochemical surfactant is dissolved in 330 parts of ethyl 2-methoxypropionate to give 0.1 μm PTF.
A resist solution was prepared by filtering with a filter made by E.

The above resist solution was applied onto a silicon wafer with a spinner and then baked at 90 ° C. for 90 seconds to form a resist film having a thickness of 1.0 μm. This wafer was exposed using a far-ultraviolet irradiation device PLA-521FA and a test mask. Next, after exposure and baking at 120 ° C. for 60 seconds, it was developed by an immersion method at 23 ° C. for 1 minute in an aqueous solution of tetramethylammonium hydroxide to obtain a positive pattern.

The sensitivity was evaluated to be 30 mJ / cm ² , and the film thickness of the pattern was 0.93 μm when measured with a film thickness meter Alpha Step 200. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
A 0.45 μm pattern was resolved.

Example 14 Hydrogenated polyvinylphenol (hydrogenation rate = 15%, weight average molecular weight 6000) 10
0 parts, t-butyl ether compound of bisphenol A 20
Parts, 4 parts of 1,2-naphthoquinonediazide-4-sulfonic acid ester of tetrachlorobisphenol F, and 0.01 parts of a fluorine-based surfactant are dissolved in 330 parts of ethyl 2-methoxypropionate to give 0.1 μm PTFE. A resist solution was prepared by filtering with a filter made by Japan.

After coating the above resist solution on a silicon wafer with a spinner, it is baked at 100 ° C. for 90 seconds,
A resist film having a thickness of 1.0 μm was formed. This wafer is used as a KrF excimer laser stepper NSR 1505E.
Exposure was performed using X and a test reticle. Then 1
After exposure at 20 ° C. for 60 seconds and baking, it was developed with an aqueous tetramethylammonium hydroxide solution at 23 ° C. for 1 minute by a dipping method to obtain a positive pattern.

When the sensitivity was evaluated, it was 20 mJ / cm ² , and when the film thickness of the pattern was measured by a film thickness meter Alpha Step 200, it was 0.94 μm. When the wafer on which the pattern was formed was taken out and observed with an electron microscope,
A 0.45 μm pattern was resolved.

[0082]

According to the present invention, a resist composition having a good balance of 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 positive resist for fine processing of semiconductor devices.

Claims (3)

[Claims] 1. A resist composition containing a compound having an acid-decomposable group and a compound which produces an acid upon irradiation with actinic rays, wherein the compound which produces an acid upon irradiation with actinic rays is (a) a hydroxyl group or an imide group. And 248-2
1,2-naphthoquinonediazide-4-, a compound having an absorbance of 0.01 or less per 1 ppm at 51 nm
Sulfonic acid ester, (b) 1,2-naphthoquinonediazide-4-sulfonic acid imide of a compound having a hydroxyl group or an imide group, and having an absorbance of 0.01 or less per 1 ppm at 248 to 251 nm, (c) 1,2-naphthoquinonediazide-4-sulfonic acid ester of a compound having a hydroxyl group or an imide group and containing a halogen, and (d) a compound having a hydroxyl group or an imide group and containing a halogen 1 A resist composition comprising at least one compound selected from the group consisting of 2,2-naphthoquinonediazide-4-sulfonic acid imides. 2. The resist compound according to claim 1, which further contains an alkali-soluble phenol resin. 3. The resist composition according to claim 2, wherein the alkali-soluble phenol resin is an alkali-soluble hydrogenated phenol resin.