JP2817439B2 - Positive 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 positive resist composition, and more particularly to a positive resist composition for fine processing required for manufacturing semiconductor devices, magnetic bubble memory devices, integrated circuits and the like. .

[0002]

2. Description of the Related Art In the manufacture of semiconductors, a photosensitive film is formed by coating a resist on the surface of a silicon wafer, and a latent image is formed by irradiating light, and then developed to form a negative or positive image. 2. Description of the Related Art A semiconductor element is formed by a lithography technique. Conventionally, as a resist composition for forming a semiconductor device, a negative resist comprising a cyclized polyisoprene and a bisdiazide compound has been known. However, since this negative resist is developed with an organic solvent, the swelling is large and the resolution is limited,
It has a disadvantage that it cannot cope with the manufacture of a highly integrated semiconductor.

[0003] On the other hand, a positive resist comprising an alkali-soluble novolak resin and a quinonediazide compound, which undergoes alkali development, does not swell and is essentially excellent in resolution. It has come to be. Further, the resolution has been improved by improving the performance of the positive resist and the performance of the exposure mechanism, and it has become possible to form a fine pattern of 1 μm or less. by the way,
In forming a fine pattern of 1 μm or less, particularly 0.8 μm or less, it is necessary to more strictly control the dimensions of the resist. However, conventional positive resist compositions have not always yielded satisfactory results, and a positive resist composition having good dimensional control has been strongly demanded.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive resist composition having a good balance of various properties such as sensitivity, residual film ratio, and resolution. Another object of the present invention is to provide a positive resist having a small dimensional change with respect to the exposure dose, particularly in a so-called exposure margin, particularly in fine processing of 1 μm or less. The present inventors have conducted intensive studies to overcome the problems of the prior art, and as a result, in a positive resist composition containing an alkali-soluble phenol resin and a photosensitizer, the photosensitizer has a phenolic hydroxyl group. It has been found that the above object can be achieved by containing a mixed esterified product obtained by capping the hydroxyl group of a specific compound together with quinonediazide sulfonic acid ester and a part of the hydroxyl group by sulfonic acid esterification and / or carboxylic acid esterification, Based on the knowledge, the present invention has been completed.

[0005]

Thus, according to the present invention, the hydroxyl group of the alkali-soluble phenolic resin and at least one phenolic compound represented by the following general formula [I] is converted to quinonediazidesulfonic acid ester, and A positive active material comprising a mixed esterified product in which a hydroxyl group is sulfonic acid esterified as represented by the general formula [II] and / or carboxylic acid esterified as represented by the general formula [III] as a photosensitive agent. A resist composition is provided. General formula [I]

[0006]

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(R ¹ -R ⁶ : hydrogen, halogen, hydroxyl group, C
₁ -C ₄ alkyl group, an alkoxy group of C ₂ -C ₅ alkenyl group or C ₁ -C _6,, may be the same or different. R ⁷ to R ^8: hydrogen, an alkyl group of halogen or C ₁ -C _4,, it may be the same or different. R ^{9 to} R ^{11 are} hydrogen or C _{1 to} C ₄ alkyl groups, which may be the same or different. )

Formula [II] -OSO ₂ R ¹² (R ^{12 is} an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group.)

General formula [III] -OCOR ¹³ (R ^{13 is} an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.) The present invention will be described below in detail.

(Alkali-Soluble Phenolic Resin) Examples of the alkali-soluble phenol resin used in the present invention include a condensation reaction product of a phenol and an aldehyde, a condensation reaction product of a phenol and a ketone, and a vinylphenol-based resin. Examples include polymers, isopropenylphenol-based polymers, and hydrogenation products of these phenolic resins.

Specific examples of the phenols used herein include monovalent phenols such as phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, phenylphenol, resorcinol, pyrocatechol, hydroquinone, bisphenol A, phlorog Examples include polyhydric phenols such as lucinol and pyrogallol. 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 performed according to a conventional method.

The vinylphenol-based polymer is selected from a homopolymer of vinylphenol and a copolymer of vinylphenol and 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 with 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.

When a hydrogenation reaction product of a phenolic resin is used, the product can be produced by any known method. For example, it can be achieved by dissolving a phenol resin in an organic solvent and introducing hydrogen in the presence of a homogeneous or heterogeneous hydrogenation catalyst. These alkali-soluble phenol resins may be used alone or in combination of two or more.

If necessary, the positive resist composition of the present invention may be mixed with styrene and acrylic acid, methacrylic acid or maleic anhydride in order to improve developability, storage stability and heat resistance. Polymers, copolymers of alkenes and maleic anhydride, vinyl alcohol polymers, vinylpyrrolidone polymers, rosin, shellac and the like can be added. The addition amount is from 0 to 50 parts by weight, preferably from 5 to 20 parts by weight, based on 100 parts by weight of the alkali-soluble phenol resin.

(Photosensitizer) The photosensitizer used in the present invention is characterized in that a part of the hydroxyl group of the phenol compound represented by the general formula [I] is converted to quinonediazide sulfonic acid ester, and a part of the hydroxyl group is a compound of the general formula [I]. The sulfonic acid esterification represented by the formula [II] and / or the general formula [II
It is a mixed esterified product capped by carboxylic acid esterification represented by I).

Specific examples of the phenol compound represented by the general formula [I] include the following. The phenol compounds are used alone or in combination of two or more.

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The quinonediazidesulfonic acid ester portion in the mixed esterified product is not particularly limited. For example, 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-acid
Sulfonate, 1,2-naphthoquinonediazide-
O-quinonediazidesulfonic acid esters such as 5-sulfonic acid ester, 2,1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, and other quinonediazidesulfonic acid esters. .

The quinonediazidesulfonic acid ester is obtained by converting quinonediazidesulfonic acid into sulphonyl chloride with chlorosulfonic acid according to a conventional method, and condensing the obtained quinonediazidosulphonylchloride with a phenol compound represented by the general formula [I]. Can be For example, a predetermined amount of a phenol compound represented by the general formula [I] and 1,2-naphthoquinonediazide-5-sulfonyl chloride are dissolved in a solvent such as dioxane, acetone or tetrahydrofuran, and triethylamine, pyridine, sodium carbonate, sodium hydrogen carbonate is dissolved. And a basic catalyst such as sodium hydroxide or potassium hydroxide for reaction, and the resulting product is washed with water and dried to prepare the product. In addition, the phenol compound represented by the general formula [1] may be obtained by converting a part of its hydroxyl group into a sulfonic acid ester as shown by the above general formula [II] and / or a carboxylic acid as shown by the general formula [III]. In the case of an acid esterified product, quinonediazidesulfonic acid esterification can be performed in the same manner as described above by reacting the capped phenol compound with quinonediazidosulfonyl chloride.

A part of the hydroxyl group of the phenol compound represented by the general formula [1] is converted to a sulfonic acid ester and / or the general formula [III] as represented by the general formula [II].
As shown in the above, capping by carboxylic acid esterification can be performed by reacting a phenol compound with a sulfonic acid halide and / or a carboxylic acid halide in the same manner as in the method for synthesizing quinonediazidesulfonic acid ester under a basic catalyst. . The capping with a carboxylic acid ester can also be performed by reacting a phenol compound with an acid anhydride according to a known method.

The sensitizer used in the present invention is obtained by converting a phenolic compound of the general formula [1] into (1) a sulfonic acid ester represented by the general formula [II] and / or a general formula [III]. Whether capping by carboxylic acid esterification and quinonediazidesulfonic acid esterification are performed simultaneously, or (2) quinonediazidesulfonic acid esterification after capping first,
Alternatively, it can be synthesized by any method such as (3) capping after quinonediazidesulfonic acid esterification is performed first.

The sulfonic acid halide or carboxylic acid halide used for the sulfonic acid esterification represented by the general formula [II] or the carboxylic acid esterification represented by the general formula [III] is not particularly limited. Examples include the following compounds. As the sulfonic acid halide, for example, methanesulfonic acid chloride,
Alkanesulfonic acid halides such as methanesulfonic acid chloride, ethanesulfonic acid chloride, n-propanesulfonic acid chloride, n-butanoic acid chloride and pentanesulfonic acid chloride; chloromethylsulfonic acid chloride, dichloromethylsulfonic acid chloride, trichloromethylsulfone Substituted alkanesulfonic acid halides such as acid chloride and 2-chloroethylsulfonic acid chloride; alkenesulfonic acid halides such as ethenesulfonic acid chloride and propenesulfonic acid chloride; benzenesulfonic acid chloride, benzenesulfonic acid fluoride and 1-naphthalene sulfone Arylsulfonic acid halides such as acid chloride and 2-naphthalenesulfonic acid chloride; p-toluenesulfonic acid chloride, p-
Ethylbenzenesulfonic acid chloride, p-xylenesulfonic acid chloride, 2,4,6-triisopropylbenzenesulfonic acid chloride, p-styrenesulfonic acid chloride, p-methoxybenzenesulfonic acid chloride, p-dimethylaminobenzenesulfonic acid chloride, p -Acetamidobenzenesulfonic acid chloride, p
Substituted arylsulfonic acid halides such as -phenylazobenzenesulfonic acid chloride, m-nitrobenzenesulfonic acid chloride, p-nitrobenzenesulfonic acid chloride, p-chlorobenzenesulfonic acid chloride, and 2,4,5-trichlorobenzenesulfonic acid chloride. Can be

Examples of the carboxylic acid halide include alkane carboxylic acid halides such as acetic acid chloride, acetic acid bromide, propionic acid chloride, propionic acid bromide, butyric acid chloride, isopropane carboxylic acid chloride, valeric acid chloride and pentane carboxylic acid chloride; Substituted alkanecarboxylic acid halides such as chloroacetic acid chloride, dichloroacetic acid chloride and trichloroacetic acid chloride; alkenecarboxylic acid halides such as acrylic acid chloride and crotonic acid chloride; substituted alkenecarboxylic acids such as methacrylic acid chloride and α-ethylacrylic acid chloride Acid halides; benzoic acid chloride, benzoic acid bromide, 1-naphthoic acid chloride,
Aryl carboxylic acid halides such as 2-naphthoic acid chloride; substituted aryls such as 4-methylbenzoic acid chloride, 4-ethylbenzoic acid chloride, 2,4-dimethylbenzoic acid chloride and 3,4,5-trimethoxybenzoic acid chloride; Carboxylic acid halides; and the like.

The photosensitizer obtained by the above-mentioned method comprises quinonediazidesulfonic acid esterification and capping (sulfonic acid esterification and / or carboxylic acid esterification).
Occur randomly, and are obtained as a mixture (mixed esterified product) of various compounds having different proportions and substituted positions. Each ratio of quinonediazide sulfonic acid esterification and capping is defined as an average value of these mixtures, but in the present invention, it is assumed to be represented by the charging ratio of each raw material.

The ratio of quinonediazide sulfonic acid esterification (esterification ratio) is in the range of 20 to 99 mol%, preferably 50 to 95 mol% on average, of the hydroxyl group of the phenol compound represented by the general formula [I]. If the ratio of quinonediazide sulfonic acid esterification is too low, the pattern shape and the resolution may be deteriorated. On the contrary, if this ratio is too high, the sensitivity may be deteriorated.

The capping ratio (capping ratio) is in the range of 1 to 95 mol%, preferably 5 to 40 mol%, of the average of the hydroxyl groups of the phenol compound represented by the general formula [I]. If the capping ratio is less than 1 mol%, the desired effect cannot be sufficiently obtained. Conversely, if the capping ratio exceeds 95 mol%, the sensitivity is remarkably reduced, and the development residue tends to occur.
The sum of the ratio of the quinonediazide sulfonic acid esterification and the ratio of the capping varies depending on the presence or absence and the combination ratio of other photosensitizers described later, but usually the average of 6 to 100 of the hydroxyl groups of the phenol compound represented by the general formula [I]. Mol%, preferably 40 to
95 mol%, and when used in combination, is 10 to 95 mol%.

The mixing ratio of the photosensitizer used in the present invention is not particularly limited, but is usually 1 to 100 parts by weight based on 100 parts by weight of the alkali-soluble phenol resin.
Preferably it is in the range of 5 to 40 parts by weight. If the compounding ratio is too small, a sufficient residual film ratio cannot be obtained, leading to deterioration in resolution. Conversely, if the compounding ratio is too large, heat resistance deteriorates, which is not preferable.

The photosensitive agents used in the present invention can be used alone or in combination of two or more. Further, it can be used in combination with another type of photosensitive agent. The other type of photosensitive agent to be mixed is not particularly limited, and any known quinonediazidesulfonic acid ester can be used. Specific examples include cresol, xylenol, resorcin, catechol, hydroquinone, pyrogallol, phloroglucinol, phloroglucid, 2,3,4-trihydroxybenzophenone,
2,4,4-trihydroxybenzophenone, 2,3
4,4'-tetrahydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
2,2 ', 3,4,4'-pentahydroxybenzophenone, 2,2', 3,4,5'-pentahydroxybenzophenone, 2,3,3 ', 4,5'-pentahydroxybenzophenone, 2, 3,3 ', 4,4', 5'-hexahydroxybenzophenone, 2,3 ', 4,4',
5 ', 6-hexahydroxybenzophenone, methyl gallate, ethyl gallate, propyl gallate, 2,2-
Bis (4-hydroxyphenyl) propane, 2,2-bis (2,4-dihydroxyphenyl) propane, 2,2
-Bis (2,3,4-trihydroxyphenyl) propane, cresol novolak resin, resorcin-acetone resin, pyrogallol-acetone resin, polyvinyl phenol resin and quinonediazide sulfonic acid ester such as vinyl phenol copolymer. In particular, a quinonediazidesulfonic acid ester of a phenol compound represented by the general formula [1] is preferably used. The ratio of the other photosensitive agent used in combination is usually 0.05 to 20 times the photosensitive agent 1 of the present invention.

(Other Components) The positive resist composition of the present invention is usually used by dissolving it in a solvent in order to form a resist film by coating it on a substrate. As the solvent, ketones such as acetone, methyl ethyl ketone, cyclohexanone and cyclopentanone; n-propyl alcohol,
iso-propyl alcohol, n-butyl alcohol,
Alcohols such as cyclohexanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane; alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate; Esters such as methyl propionate, ethyl propionate, methyl acetate, ethyl acetate, methyl lactate and ethyl lactate; cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate and butyl cellosolve acetate; propylene glycol; Propylene glycol monomethyl ether, prolene 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 dimethyl ether, and diethylene glycol methyl ethyl ether; halogenated hydrocarbons such as trichloroethylene , Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include polar solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide. These may be used alone or in combination of two or more. The positive resist composition of the present invention may contain a compatible additive such as a dye, a surfactant, a storage stabilizer, a sensitizer, a striation inhibitor, and a plasticizer, if necessary. it can.

As the developer for the positive resist composition of the present invention, an aqueous alkali solution is used. Specifically, sodium hydroxide, potassium hydroxide, sodium silicate,
Inorganic amines such as ammonia; primary amines such as ethylamine and propylamine; second amines such as diethylamine and dipropylamine; tertiary amines such as trimethylamine and triethylamine; dimethylmethanolamine and triethanolamine Alcohol amines; tetramethylammonium hydroxide,
Examples include quaternary ammonium salts such as tetraethylammonium hydroxide, trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, and trimethylhydroxyethylammonium hydroxide. Further, if necessary, methanol, ethanol,
An appropriate amount of a water-soluble organic solvent such as propanol or ethylene glycol, a surfactant, a storage stabilizer, or a dissolution inhibitor for a resin can be added.

[0050]

The present invention will be described more specifically below with reference to examples and comparative examples. In the examples, parts and%
Are by weight unless otherwise specified.

[Synthesis Example 1] (Synthesis of alkali-soluble phenolic resin) A mixture of m-cresol / p-cresol (6/4)
A 37% aqueous solution of formalin and oxalic acid were placed in a flask equipped with a condenser and a stirrer at a ratio of 0.70 mol and 0.03 mol of the total amount of cresol, respectively, and kept at 95 to 100 ° C for 1 hour. Reacted. Thereafter, the temperature was raised to 100 ° C. or higher, and water was distilled off over 2 hours.
After distillation under reduced pressure with Hg to remove unreacted monomers and water, the molten resin was returned to room temperature and collected. The polystyrene-equivalent weight average molecular weight of this novolak resin is 980.
It was 0.

[Synthesis Example 2] (Synthesis of Photosensitive Agent A) A compound represented by the formula 11 as a phenol compound and methanesulfonic acid chloride as a capping agent in an amount corresponding to 10 mol% of the hydroxyl groups of the phenol compound, and 1, 2-Naphthoquinonediazide-5-sulfonic acid chloride was dissolved in dioxane in an amount corresponding to 70 mol% of the hydroxyl groups of the phenol compound to obtain a 10% solution. While controlling the temperature at 20 to 25 ° C, triethylamine was added to methanesulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride in the total amount of 1.
Two equivalents were added dropwise over 30 minutes, and the reaction was completed by holding for another 4 hours. The precipitated salt was separated by filtration and poured into a 0.2% aqueous solution of oxalic acid 10 times the amount of the reaction solution. The precipitated solid is filtered, washed with ion-exchanged water, dried,
Photosensitive agent A was obtained.

[Synthesis Example 3] (Synthesis of Photosensitive Agents BG) As capping agents, p-toluenesulfonic acid chloride (photosensitive agent B), p-methoxybenzenesulfonic acid chloride (photosensitive agent C), and acetate chloride ( Synthesis Example 2 except that photosensitive agent D), acrylic acid chloride (photosensitive agent E), benzoic acid chloride (photosensitive agent F), or 3,4,5-trimethoxybenzoic acid chloride (photosensitive agent G) was used. Similarly, each photosensitive agent was obtained.

[Synthesis Example 4] (Synthesis of Photosensitive Agents H to J) As the phenol compound, the compound represented by the above formula (photosensitive agent H), the compound represented by the following formula (photosensitive agent I) or the compound represented by the following formula (photosensitive agent) J) and methanes as a capping agent
Each photosensitizer was obtained in the same manner as in Synthesis Experiment 2 except that the capping ratio and the esterification ratio were changed depending on the type of the photosensitizer using sulfonic acid chloride . Table 1 shows the respective capping rates and esterification rates.

[Synthesis Example 5 ] (Synthesis of Photosensitive Agents K to L) Using a compound of the above formula (11) as a phenol compound, without using a capping agent, 1,2 corresponding to 70 mol% of the hydroxyl groups of this compound. Using -naphthoquinonediazide-5-sulfonic acid chloride, Photosensitive Agent K was obtained in the same manner as in Synthesis Example 2. Similarly, as the phenol compound,
Using 3,4,4'-tetrahydroxybenzophenone, a photosensitive agent L having an esterification rate of 85 mol% was obtained.

Example 1 100 parts of the novolak resin obtained in Synthesis Example 1 and 25 parts of photosensitive agent A were dissolved in 350 parts of ethyl cellosolve acetate, and the solution was filtered through a 0.1 μm Teflon filter (polytetrafluoroethylene filter). Thus, a resist solution was prepared. After applying the resist solution on a silicon wafer with a coater, 90 ° C.
Prebaking was performed for 2 seconds to form a resist film having a film thickness of 1.17 μm. This wafer is placed in a g-line stepper NSR15.
Exposure was performed using a 05G6E (Nikon Corporation, NA = 0.54) and a test reticle while changing the exposure time, and then a post-exposure bake (Post) at 110 ° C. for 60 seconds.
Exposure Banking) was performed. Next, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide by a paddle method at 23 ° C. for 1 minute to form a positive pattern.

The wafer was taken out and observed with an electron microscope, pattern formation and pattern dimensions were measured, and the resist was evaluated. Table 1 shows the results. In Table 1, "Sensitivity"
Represents the exposure time during which a 0.65 μm 1: 1 line & space pattern can be formed as designed, and “resolution” represents the limit resolution under this exposure condition, and “remaining film ratio”.
Represents the ratio of the resist film thickness before and after development, and “exposure margin” is a graph showing the relationship between the exposure time and the pattern dimension of 0.65 μm.
%, Which is a value obtained by calculating the variation of the exposure time that can be maintained within%, and dividing the variation by the sensitivity.

Examples 2 to 10 Instead of the photosensitive agent A,
A resist solution was prepared and evaluated in the same manner as in Example 1 except that photosensitive agents B to J were used. Table 1 shows the results.

[Comparative Examples 1-2] A resist solution was prepared and evaluated in the same manner as in Example 1 except that photosensitive agents KL were used instead of photosensitive agent A, respectively. Table 1 shows the results.

Example 11 The resist solution prepared in Example 1 was applied on a silicon wafer by a coater,
Pre-bake at 0 ° C for 90 seconds, film thickness 1.18 μm
Was formed. This wafer is placed in an i-line stepper NSR1505i6A (manufactured by Nikon Corporation, NA = 0.45).
And exposure using a test reticle while varying the exposure time, followed by baking after exposure at 110 ° C. for 60 seconds. Next, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide by a paddle method at 23 ° C. for 1 minute to form a positive pattern. The wafer was taken out and observed with an electron microscope, pattern formation and pattern dimensions were measured, and the resist was evaluated. Table 2 shows the results.

[Examples 12 to 14] Patterns were formed in the same manner as in Example 11 except that the resist solutions prepared in Examples 8 to 10 were used, and the resist was evaluated. Table 2 shows the results.

Comparative Examples 3 and 4 A pattern was formed in the same manner as in Example 11 except that the resist solutions prepared in Comparative Examples 1 and 2 were used, and the resist was evaluated.
Table 2 shows the results.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

According to the present invention, a positive resist composition excellent in sensitivity, residual film ratio, resolution and dimensional control can be provided. The positive resist composition of the present invention is particularly suitable for fine processing of 1 μm or less.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Kazuko Koito 1-2-1, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Japan Zeon Co., Ltd. Research and Development Center (56) References JP-A-62-178562 (JP, A) JP-A-63-110446 (JP, A) JP-A-63-305348 (JP, A) JP-A-3-48249 (JP, A) JP-A-4-37551 (JP, A) JP-A-4 JP-177352 (JP, A) JP-A-4-211254 (JP, A) JP-A-4-253058 (JP, A) JP-A-4-298749 (JP, A) (58) Fields investigated (Int. . ^6, DB name) G03F 7/00 - 7/18

Claims (2)

(57) [Claims] Claims: 1. An alkali-soluble phenolic resin and at least one phenolic compound represented by the following general formula [I], wherein the hydroxyl group is converted to a quinonediazide sulfonic acid ester, and the hydroxyl group is represented by the general formula [II]. Sulfonate esterification and / or general formula [II
A positive resist composition comprising a carboxylic acid esterified mixed esterified product as a photosensitive agent as shown in I). General formula [I] (R ¹ -R ⁶ : hydrogen, halogen, hydroxyl group, C ₁ -C ₄ alkyl group, C ₂ -C ₅ alkenyl group, or C ₁ -C ₆ alkoxy group, which may be the same or different R ^{7 to} R ^{8 are} hydrogen, halogen, or a C _{1 to} C ₄ alkyl group, which may be the same or different, and R ^{9 to} R ^{11 are} hydrogen or a C _{1 to} C ₄ alkyl group. May be the same or different.) General formula [II] -OSO ₂ R ¹² (R ^{12 is} an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.) General formula [III] -OCOR ¹³ ( R ^{13 is} an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. 2. The mixed esterified product is represented by the general formula [I]
An average of 20 to 99 mol% of the hydroxyl group of at least one phenol compound represented by the formula (1) is esterified with quinonediazide sulfonic acid, and an average of 1 to 95 mol% of the hydroxyl group is a sulfonic acid as represented by the general formula [II]. 2. The positive resist composition according to claim 1, which is a mixed esterified product which is esterified and / or carboxylic acid esterified as shown in the general formula [III].