JPH0829978A - Positive type resist composition - Google Patents

Abstract

PURPOSE:To provide the fine processing positive type resist composition, which has the excellent sensitivity, resolution and pattern forming property, by using quinonediazide sulfonic acid ester of the specified polyhydroxy compound as the photo sensing agent in the positive type resist composition, which contains alkali soluble phenol resin and the photo sensing agent. CONSTITUTION:As the photo sensing agent, quinonediazide sulfonic acid ester of the polyhydroxy compound expressed with the formula and/or II, III or IV is used. In the formula I, II, R<1>, R<4>, R<13> and R<16> mean halogen atom, substitutional alkyl group, substitutional cyclolkyl group or the like, R<2>, R<3>, R<5>, R<6> an R<14>, R<15>, R<17>, R<18> mean hydrogen atom, halogen atom, substitutional alkyl group or the like, R<7>-R<12> and R<19>, R<24> mean hydrogen atom, halogen atom, hydroxyl group or the like, X means single connection,-O-,-S-,-SO- or the like, and in the formula III, IV, (n) means the integer at 1-5, and R<27> R<34> mean hydrogen atom or substitutional alkyl group.

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 microfabrication required for manufacturing semiconductor devices, magnetic bubble memory devices, integrated circuits and the like.

[0002]

2. Description of the Related Art As a resist composition for forming a semiconductor device, a positive resist composition has been predominant in recent years. This is because the negative resist composition has high sensitivity, but since the organic solvent is used for development, swelling is large and there is a problem in resolution, and the positive resist composition is excellent in resolution. Therefore, it is considered that it is possible to sufficiently cope with high integration of semiconductors. Conventionally, a positive resist composition generally used in this field comprises an alkali-soluble resin such as a novolac resin and a quinonediazide sulfonic acid compound. Since this positive resist composition is developed with an alkaline aqueous solution, it does not swell and is excellent in resolution. Further, such a positive resist composition has further improved the resolution due to the performance improvement of itself and the high performance of the exposure device, and it has become possible to form a fine pattern of 1 μm or less.

However, conventional positive resist compositions have not always been satisfactory in terms of various characteristics such as sensitivity, residual film ratio, resolution, heat resistance and storage stability.
Further improvement in performance is desired. In particular, in forming a fine pattern of 0.8 μm or less, it is necessary to more strictly control the resist dimension, and therefore, a positive resist composition having higher dimensional accuracy has been strongly demanded. From such a point of view, it has been proposed to use a naphthoquinone diazide sulfonic acid ester of a certain polyhydroxy compound as a photosensitizer (Japanese Patent Application Laid-Open No. HEI 2).
-285351, JP-A-2-296248, JP-A-2-296249). However, the positive resist compositions specifically disclosed in these documents have somewhat insufficient resist properties such as sensitivity, resolution and residual film rate, and further improvement is required.

[0004]

Under such conventional techniques, the inventors of the present invention have conducted diligent research to solve the above-mentioned problems, and as a result, use a quinonediazidesulfonic acid ester of a specific polypolyhydroxy compound as a photosensitizer. As a result, they have found that the above object can be achieved, and have completed the present invention.

[0005]

According to the present invention, in the positive resist composition containing an alkali-soluble phenol resin and a photosensitizer, the photosensitizer is represented by the general formula (1).

Embedded image And / or general formula (2)

[Chemical 6] (In the formula, R ¹ , R ⁴ , R ¹³ and R ¹⁶ are a halogen atom, a substitutable alkyl group, a substitutable cycloalkyl group, a substitutable alkenyl group, a substitutable alkoxy group, a substitutable aryl group or a substitutable acyl group. And R ² , R ³ , R ⁵ , R ⁶ and R ¹⁴ ,
R ¹⁵ , R ¹⁷ and R ¹⁸ are a hydrogen atom, a halogen atom, a replaceable alkyl group, a replaceable cycloalkyl group, a replaceable alkenyl group, a replaceable alkoxy group, a replaceable aryl group or a replaceable acyl group, and R ⁷ To R ¹² and R ¹⁹ R ²⁴ are hydrogen atoms,
A halogen atom, a hydroxyl group, a substitutable alkyl group, a substitutable cycloalkyl group, a substitutable alkenyl group, a substitutable alkoxy group, a substitutable aryl group, a substitutable acyl group, X is a single bond, -O-,- S-, -SO-, -SO
_{2 -, - CO -, -} CO 2 -, cyclopentylidene, cyclohexylidene, ^{phenylene, -C (R 25) (R} 26) -
(In the formula, R ²⁵ and R ²⁶ are a hydrogen atom, a substitutable alkyl group,
They are a substitutable alkenyl group and a substitutable aryl group. ), Formula (3)

[Chemical 7] (In the formula, n is an integer of 1 to 5. R ^{27 to} R ³⁰ are a hydrogen atom or a substitutable alkyl group.) Or Formula (4)

Embedded image (In the formula, R ^{31 to} R ³⁴ are a hydrogen atom or a substitutable alkyl group.). The present invention provides a positive resist composition, which is a quinonediazide sulfonic acid ester of a polyhydroxy compound represented by the formula (1).

The present invention will be described in detail below. Alkali-soluble phenol resin (a) 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 polymers. , Isopropenylphenol-based polymers, hydrogenation reaction products of these phenolic resins, and the like. Specific examples of the phenols used here include phenol, cresol, xylenol, trimethylphenol, ethylphenol, propylphenol, butylphenol, phenylphenol, methoxyphenol, methylmethoxyphenol, and other monovalent phenols; resorcinol, pyrocatechol, Examples include polyphenols such as hydroquinone, bisphenol A, phlorogricinol, and pyrogallol. Specific examples of aldehydes include formaldehyde, paraformaldehyde, benzaldehyde, hydroxybenzaldehyde, terephthalaldehyde and the like. Specific examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone, acetaldehyde, hydroxyacetaldehyde and the like. These condensation reaction products can be obtained by a conventional method, for example, by reacting phenols with aldehydes or ketones in the presence of an acidic catalyst.

The vinylphenol polymer is selected from homopolymers of vinylphenol and isopropylphenol and copolymers of components copolymerizable with vinylphenol and isopropylphenol. Specific examples of the copolymerizable component include acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic imide, vinyl acetate,
Examples thereof include acrylonitrile and derivatives thereof.
The copolymer can be obtained by a known method.

The hydrogenation reaction product of the phenolic resin is
Any known method, for example, dissolving the above phenolic resin in an organic solvent and in the presence of a homogeneous or heterogeneous catalyst,
It can be obtained by hydrogenation.

These alkali-soluble phenol resins can be used by controlling the molecular weight and the molecular weight distribution by known means. As a method for controlling the molecular weight and the molecular weight distribution, the resin is crushed, and solid-liquid extraction is performed with an organic solvent having an appropriate solubility, or the resin is dissolved in a good solvent and then dropped into a poor solvent, or a poor solvent is used. Is added dropwise to perform solid-liquid or liquid-liquid extraction. These alkali-soluble phenolic resins may be used alone or in combination of two or more.

The positive resist composition of the present invention may optionally contain a copolymer of styrene and acrylic acid, methacrylic acid or maleic anhydride in order to improve developability, storage stability and heat resistance. , A copolymer of an alkene and maleic anhydride, a vinyl alcohol polymer, a vinylpyrrolidone polymer, rosin, shellac and the like can be added. The amount of such a polymer added is 0 to 5 with respect to 100 parts by weight of the alkali-soluble phenol resin.
It is 0 part by weight, preferably 5 to 20 parts by weight.

Photosensitizer (b) The photosensitizer used in the present invention is a quinonediazide sulfonic acid ester of a polyhydroxy compound represented by the above formula (1) and / or (2), and The hydroxyl group does not have to be esterified, and may be a partially esterified product. Specific examples of the esterified product used as a photosensitizer include 1,2-benzoquinonediazide-4-sulfonic acid esters of these polyhydroxy compounds, 1,2-naphthoquinonediazide-4-sulfonic acid, and 1,2-naphthoquinonediazide. -5-sulfonic acid, 2,1-naphthoquinonediazide-4
Examples thereof include sulfonic acid ester and 2,1-naphthoquinonediazide-5-sulfonic acid ester. It The quinonediazidesulfonic acid ester of the polyhydroxy compound represented by the formula (1) is prepared by converting the quinonediazidesulfonic acid compound into a quinonediazidesulfonic acid halide according to a conventional method, and then using sodium carbonate, hydrogencarbonate in a solvent such as acetone, dioxane, or tetrahydrofuran. By reacting a quinonediazidesulfonic acid halide with a polyhydroxy compound represented by the above formula (1) in the presence of sodium, sodium hydroxide or potassium hydroxide, the quinonediazidesulfonic acid ester-based photosensitizer used in the present invention can be obtained. Obtainable. The polyhydroxy compound serving as the mother nucleus of the photosensitizer used in the present invention is a compound represented by the above formula (1) or (2). In these formulas, the halogen atom is preferably chlorine or bromine.
The alkyl group preferably has 1 to 4 carbon atoms, and the alkenyl group preferably has 2 to 5 carbon atoms. The alkoxy group preferably has 1 to 6 carbon atoms. Examples of the substituent of the substituted alkyl group, the substituted alkenyl group, and the substituted alkoxy group include a halogen atom and the like. The aryl group preferably has 6 to 15 carbon atoms, and examples of the substituent of the substituted aryl group include a halogen atom and an alkyl group having 1 to 4 carbon atoms. Further, specific examples of the polyhydroxy compound include b-1 to b-78 shown in Tables 1 to 10. R ^{1 to} R in the table
³⁴ , X and n correspond to the substituents in the above formulas (1) to (4).

[0012]

[Table 1]

[0013]

[Table 2]

[0014]

[Table 3]

[0015]

[Table 4]

[0016]

[Table 5]

[0017]

[Table 6]

[0018]

[Table 7]

[0019]

[Table 8]

[0020]

[Table 9]

[0021]

[Table 10]

Among these compounds, especially b-
1, b-25, b-26, b-27, b-29, b-3
3, b-55, b-63, b-73, b-74 and the like are preferable.

In the photosensitizer used in the present invention, the esterification ratio (average esterification ratio) of the quinonediazidesulfonic acid compound to the polyhydroxy compound represented by the above formula (1) or (2) is particularly limited. Although not limited, the lower limit is usually 20%, preferably 45%, and the upper limit is usually 100%, preferably 95% as the mol% of the quinonediazidesulfonic acid compound based on the hydroxyl group of the polyhydroxy compound. If the esterification ratio is too low, the pattern shape and resolution may be deteriorated, and if the esterification ratio is too high, the sensitivity may be deteriorated.

The mixing ratio of the photosensitizer used in the present invention is not particularly limited, but the lower limit is usually 1 part by weight, preferably 3 parts by weight, and more preferably 100 parts by weight of the alkali-soluble phenol resin. 5 parts by weight, and the upper limit is usually 100 parts by weight, preferably 50 parts by weight, more preferably 40 parts by weight. If the blending ratio is too small, a sufficient residual film rate cannot be obtained, leading to deterioration of resolution, and conversely, if the blending ratio is too large, heat resistance is degraded, which is not preferable. The photosensitizers used in the present invention can be used alone or in combination of two or more kinds. Also,
Other types of photosensitizers may be mixed with a small amount (usually 30% by weight or less based on the total amount of the photosensitizers) within a range not impairing the object of the present invention. The other type of photosensitizer to be mixed is not particularly limited, and any known quinonediazide sulfonate can be used.

In the present invention, as an optional component, the alkali solubility of the resist composition of the present invention is promoted, and sensitivity and
A low molecular weight phenol compound can be added for the purpose of improving the residual film rate, resolution and heat resistance. Specific examples of the low molecular weight phenol compound include monophenols such as p-phenylphenol and p-isopropylphenol; biphenol, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxybenzophenone and bisphenol A (Honshu Chemical Industry Co., Ltd.). ), Bisphenol C (made by Honshu Chemical Industry Co., Ltd.), bisphenol E (made by Honshu Chemical Industry Co., Ltd.), bisphenol F (made by Honshu Chemical Industry Co., Ltd.), bisphenol AP (made by Honshu Chemical Industry Co., Ltd.), bisphenol M (Mitsui Petrochemical Industry Co., Ltd.) Company), bisphenol P (manufactured by Mitsui Petrochemical Co., Ltd.), bisphenol Z (manufactured by Honshu Chemical Co., Ltd.), 1,1-bis (4-hydroxyphenyl) cyclopentane, 9,9-bis (4-hydroxyphenyl). Fluorene, 1,1-bis (5-methyl-2)
-Hydroxyphenyl) methane, 3,5-dimethyl-4
-Bisphenols such as hydroxybenzylphenol; 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl)
Ethane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) methane,
1,1-bis (2,5-dimethyl-4-hydroxyphenyl) -1- (2-hydroxyphenyl) methane, 1,
1-bis (3,5-dimethyl-4-hydroxyphenyl) -1- (2-hydroxyphenyl) methane, 2,6
-Bis (5-methyl-2-hydroxybenzyl) -4-
Methylphenol, 2,6-bis (4-hydroxybenzyl) -4-methylphenol, 2,6-bis (3-methyl-4-hydroxybenzyl) -4-methylphenol, 2,6-bis (3,5) -Dimethyl-4-hydroxybenzyl) -4-methylphenol, Trisphenol-PA (manufactured by Honshu Chemical Industry Co., Ltd.), Trisphenol-TC
Trisphenols such as (manufactured by Honshu Chemical Industry Co., Ltd.); 1,
1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methyl-4-)
Hydroxyphenyl) ethane, 1,1,3,3- (4-
Hydroxyphenyl) propane, 1,1,5,5-tetrakis (4-hydroxyphenyl) pentane α, α,
α ′, α′-tetrakis (4-hydroxyphenyl)-
3-xylene, α, α, α ′, α′-tetrakis (4-
Hydroxyphenyl) -4-xylene, α, α, α ′,
Tetrakisphenols such as α'-tetrakis (3-methyl-4-hydroxyphenyl) -3-xylene, α, α, α ', α'-tetrakis (3-methyl-4-hydroxyphenyl) -4-xylene, etc. Is exemplified.

The amount of such a low molecular weight phenol compound added depends on the composition of the alkali-soluble phenol resin, the molecular weight,
Depending on the molecular weight distribution and the type and amount of other additives,
With respect to 100 parts by weight of the alkali-soluble phenol resin,
The upper limit is usually 100 parts by weight, preferably 60 parts by weight, and the lower limit is usually 0 parts by weight, preferably 3 parts by weight.

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. Specific examples of the solvent usable in the present invention include ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and cyclohexanol; ethylene. Ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, dioxane; alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, Methyl butyrate,
Esters such as ethyl butyrate, methyl lactate, ethyl lactate; cellosolve acetates such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether. Propylene glycols such as acetate and propylene glycol monobutyl ether; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; halogenated hydrocarbons such as trichloroethylene; aromatics such as toluene and xylene Hydrogen like; dimethylacetamide, dimethylformamide, such as a polar solvent such as N- methyl acetamide and the like, which may be used by either singly or in combination.

The positive resist composition of the present invention may optionally contain compatible additives such as a surfactant, a storage stabilizer, a sensitizer, an anti-striation agent and a plasticizer. it can.

In the resist composition of the present invention, an alkaline aqueous solution is usually used as an alkaline developing solution. Specific examples thereof include aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate and ammonia; ethylamine and propyl. Aqueous solutions of primary amines such as amines;
Aqueous solutions of secondary amines such as diethylamine and dipropylamine; aqueous solutions of tertiary amines such as trimethylamine and triethylamine; aqueous solutions of alcohol amines such as diethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, Examples thereof include aqueous solutions of quaternary ammonium hydroxide such as trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide and trimethylhydroxyethylammonium hydroxide. Further, if necessary, a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a resin dissolution inhibitor, or the like can be added to the alkaline aqueous solution.

A resist film can be formed by applying a resist solution prepared by dissolving the resist composition of the present invention in a solvent onto 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 at this time, spin coating is particularly preferred. Examples of the exposure source used in the exposure for forming the pattern on the resist film thus obtained include ultraviolet rays, far ultraviolet rays, KrF excimer laser light, electron beam sources such as X-rays and electron beams. Furthermore, it is preferable to perform heat treatment (post-exposure bake) after the exposure because the sensitivity can be improved and stabilized.

[0031]

EXAMPLES The present invention will be described in more detail below with reference to Reference Examples, Synthesis Examples and Examples. In addition, part and% in each example
Is weight basis unless otherwise specified.

(Synthesis Example 1) Synthesis of Novolac Resin A-1 In a 2 liter flask equipped with a cooling pipe and a stirrer,
385 g of m-cresol, 385 g of p-cresol, 3
360 g of 7% formalin and oxalic acid dihydrate 2.49
g was added and the reaction was carried out for 2 hours while maintaining the temperature at 95 to 100 ° C. After that, water was distilled off at 100 to 105 ° C. for 2 hours, and the temperature was raised to 180 ° C. to 10 mmH.
After reducing the pressure to g and removing unreacted monomers and water,
After returning to room temperature and collecting, 515 g of novolak resin A-1
Obtained. About this novolak resin a-1, gel permeation chromatography (hereinafter referred to as GPC)
The weight average molecular weight in terms of polystyrene was measured and found to be 7,000.

Synthesis Example 2 Synthesis of Novolak Resin A-2 380 g of the novolak resin obtained in Synthesis Example 1 and 360 g of ethyl cellosolve acetate were added and dissolved. A dropping funnel was attached to the flask, and 950 g of toluene was added dropwise from the dropping funnel while controlling the temperature at 80 to 85 ° C, and further heated at 80 ° C for 1 hour. The mixture was gradually cooled to room temperature and left still for 1 hour. After the supernatant of the precipitated resin component was removed by decantation, 570 g of ethyl lactate was added and the mixture was heated to 100 ° C. at 100 mmHg to remove residual toluene to obtain an ethyl lactate solution of novolak resin a-2. The polystyrene reduced weight average molecular weight of this novolac resin was measured by GPC and found to be 12,100.

(Synthesis Example 3) Synthesis of Photosensitizers B-1 to B-10 The above compounds b-1 and b-2 were used as polyhydroxy compounds.
5, b-26, b-27, b-29, b-33, b-5
5, b-63, b-73 and b-74, 1,2-naphthoquinonediazide-5-sulfonic acid chloride as a quinonediazidesulfonic acid compound (amount is mol% corresponding to the esterification rate in Table 2) Was dissolved in acetone to give a 10% solution. While controlling the temperature at 20 to 25 ° C, 1.2 equivalents of triethylamine of 1,2-naphthoquinonediazide-5-sulfonic acid chloride was added dropwise over 30 minutes, and the reaction temperature was maintained for 2 hours for reaction. Was completed. The precipitated salt was separated by filtration and put into a 0.2% aqueous solution of oxalic acid in an amount 10 times as much as the reaction solution. The precipitated solid content is filtered, washed with ion-exchanged water, and dried to give a quinonediazidesulfonic acid ester-based photosensitizer B-1 to B-1.
I got 0.

Reference Example 1 Photosensitizer B-11 2,3,4,4'-tetrahydroxybenzophenone was used as a polyhydroxy compound, and the amount of 1,2-naphthoquinonediazide-5-sulfonic acid chloride with respect to this hydroxyl group was adjusted. A photosensitizer B-11 was obtained in the same manner as in Synthesis Example 3 except that the amount was 85 mol%.

(Reference Example 2) Photosensitizer B-12 2,5-di (4-hydroxy-2-methylbenzyl) -4- (α, α-dimethylbenzyl) phenol was used as a polyhydroxy compound, and this hydroxyl group was used. A photosensitizer B-12 was obtained in the same manner as in Synthesis Example 3 except that the amount of 1,2-naphthoquinonediazide-5-sulfonic acid chloride was 80 mol%.

The resist evaluation methods in the following examples and comparative examples are as follows. All resist evaluations were performed on aluminum stepped substrates. (1) Sensitivity 0.60 μm 1: 1 line & space can be formed according to the design dimension, and the exposure energy amount can be defined as exposure time (unit: ms
The value represented by ec). (2) Resolution This represents the limit resolution (μm) under the above exposure conditions. (3) Remaining film ratio This represents the ratio (%) of the resist film thickness before and after the development of the portion where the pattern is not formed on the wafer. (4) Pattern shape The wafer on which the resist pattern was formed was cut from the direction perpendicular to the line pattern, and the result of observation with an electron microscope from the cross-sectional direction of the pattern was shown. The pattern side wall was raised at an angle of 80 degrees or more with respect to the substrate, and a film having no film reduction was judged to be good. The film loss was recognized as "film loss".

(Examples 1 to 11, Comparative Examples 1 and 2) Table 11
1.30 μm by dissolving 30 parts by weight of the resin shown in 1 above, 20 parts by weight of trisphenol PA (manufactured by Honshu Chemical Industry Co., Ltd.) as a low molecular weight phenol compound in ethyl lactate, and
The amount of solvent blended was adjusted so as to be applied to a film thickness of m. These solvents were filtered with a 0.1 μm Teflon filter (polytetrafluoroethylene filter) to prepare a resist solution. However, Example 1, Comparative Example 1 and Comparative Example 2 are examples containing no low molecular weight phenol compound. After coating the above resist solution on a silicon wafer with a coater, prebaking is performed at 90 ° C. for 90 seconds to obtain a film thickness of 1.1.
A 7 μm resist film was formed. This wafer was processed with an i-line stepper NSR1755i7A (manufactured by Nikon Corporation; NA = 0.
50) and a test reticle, while performing exposure while varying the exposure time, post exposure bake was performed at 110 ° C. for 60 seconds. Next, it was developed by a paddle method at 23 ° C. for 1 minute with a 2.38% tetramethylammonium hydroxide aqueous solution to form a positive pattern. This wafer was taken out and observed with an electron microscope to observe the sensitivity, resolution, residual film rate, and pattern shape. The results are shown in Table 11.

[0039]

[Table 11]

[0040]

As described above, according to the present invention, it is suitable as a positive resist for fine processing having a fineness of 1 μm or less, which is excellent in sensitivity, resolution and pattern shape.

Claims (1)

[Claims] 1. In a positive resist composition containing an alkali-soluble phenol resin and a photosensitizer, the photosensitizer is represented by the general formula (1): And / or the general formula (2) (In the formula, R ¹ , R ⁴ , R ¹³ and R ¹⁶ are a halogen atom, a substitutable alkyl group, a substitutable cycloalkyl group, a substitutable alkenyl group, a substitutable alkoxy group, a substitutable aryl group or a substitutable acyl group. And R ² , R ³ , R ⁵ , R ⁶ and R ¹⁴ ,
R ¹⁵ , R ¹⁷ and R ¹⁸ are a hydrogen atom, a halogen atom, a replaceable alkyl group, a replaceable cycloalkyl group, a replaceable alkenyl group, a replaceable alkoxy group, a replaceable aryl group or a replaceable acyl group, and R ⁷ To R ¹² and R ¹⁹ R ²⁴ are hydrogen atoms,
A halogen atom, a hydroxyl group, a substitutable alkyl group, a substitutable cycloalkyl group, a substitutable alkenyl group, a substitutable alkoxy group, a substitutable aryl group, a substitutable acyl group, X is a single bond, -O-,- S-, -SO-, -SO
_{2 -, - CO -, -} CO 2 -, cyclopentylidene, cyclohexylidene, ^{phenylene, -C (R 25) (R} 26) -
(In the formula, R ²⁵ and R ²⁶ are a hydrogen atom, a substitutable alkyl group,
They are a substitutable alkenyl group and a substitutable aryl group. ), Formula (3) (In the formula, n is an integer of 1 to 5. R ^{27 to} R ³⁰ are a hydrogen atom or a substitutable alkyl group.) Or the formula (4): (In the formula, R ^{31 to} R ³⁴ are a hydrogen atom or a substitutable alkyl group.). ) A quinonediazide sulfonic acid ester of a polyhydroxy compound represented by the formula (1), which is a positive resist composition.