JPH0659447A - Positive resist composition - Google Patents

Abstract

PURPOSE:To obtain a positive resist composition well-balanced in various characteristics such as sensitivity, residual film ratio and resolution, particularly small in dimensional change with exposure in fine working of <1mum and excellent in pattern shape. CONSTITUTION:The positive resist composition contains an alkali soluble phenol resin, a sensitizer of quinone diazide sulfonate of a specific polyhydroxy compound and a hydroxy compound expressed by a formula. In the formula, each of R19-R22 is hydrogen atom, halogen atom, hydroxyl group, 1-8C alkyl group, 2-5C alkenyl group or phenyl substituted alkoxyl group and can be the same with or different from each other.

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 used for manufacturing semiconductor devices, magnetic bubble memory devices, integrated circuits and the like. is there.

[0002]

2. Description of the Related Art To form a fine pattern using a resist, a solution containing a photosensitive material is applied onto a substrate,
A lithographic technique is employed in which, after being dried to form a photosensitive film, an actinic ray is irradiated through a mask pattern to form a latent image, and then the latent image is developed to form an image. Resist is generally classified into positive type and negative type,
In the positive type, the irradiated portion has a higher solubility in the developing solution than in the unirradiated portion to give a positive type image, and in the negative type, the solubility of the irradiated portion decreases to give a negative type image.

In the case of manufacturing a semiconductor, a silicon wafer is used as a substrate, an image (pattern) is formed on the substrate by the above-mentioned lithographic technique, and then etching is performed using the resist film remaining on the substrate as a protective film. After that, a semiconductor element is formed by a method of removing the resist film.

Conventionally, as a resist for forming a semiconductor element, a negative resist composed of a cyclized polyisoprene and a bisdiazide compound has been known. However, since the resist is developed with an organic solvent, the resist film swells greatly and the resolution is high. Since it has a limit in the property, it has a drawback that it cannot be applied to the manufacture of highly integrated semiconductor devices.

On the other hand, a positive resist containing an alkali-soluble novolac resin and a quinonediazide compound and using an alkaline aqueous solution as a developing solution is excellent in resolution because it does not swell with the developing solution. Widely used in the manufacture of integrated semiconductor devices. At present, the resolution is improved by improving the performance of the positive resist and the performance of the exposure device, and it is 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 pattern. However, satisfactory results have not always been obtained with conventional positive resists, and positive resists having good dimensional controllability have been strongly demanded.

In forming a fine pattern of 0.8 μm or less, the g-line (436n) which has been widely used in the past.
The exposure method using i-line (365 nm), which has a shorter wavelength and is advantageous in resolution and focus margin, has begun to be used from the microprojection exposure method of (m). However, in exposure by i-line, since the transparency of the resist to exposure light is low, it is difficult to obtain sufficient exposure energy at the resist bottom portion, and as a result, the pattern shape may deteriorate, and improvement is required. It was

[0008]

An object of the present invention is to provide a positive resist composition having an excellent balance of various characteristics such as sensitivity, residual film ratio and resolution. Further, an object of the present invention is to provide a positive resist composition which is excellent in so-called exposure margin (exposure latitude), which has a small dimensional change with respect to an exposure amount particularly in fine processing of 1 μm or less, and which has an excellent pattern shape. is there.

The inventors of the present invention have conducted extensive studies to overcome the above-mentioned problems of the prior art. As a result, an alkali-soluble phenol resin, a photosensitizer which is a quinonediazidesulfonic acid ester of a specific polyhydroxy compound, and It has been found that the above object can be achieved by using a hydroxy compound having a structure in which two aromatic groups having a hydroxyl group are bonded to one carbon atom of cyclohexane, and the present invention is completed based on the finding. Came to.

[0010]

Thus, according to the present invention, at least one selected from the group consisting of alkali-soluble phenolic resins (a) and compounds represented by the following general formulas [I], [II] and [III]. A positive resist composition comprising a photosensitizer (b) which is a quinonediazide sulfonic acid ester of a polyhydroxy compound, and a hydroxy compound (c) represented by the following general formula [IV]. It

[0011]

[Chemical 5] R _{1 to} R ₄ : a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,
They may be the same or different. R ₅ : a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group. However, the total number of OH groups is 3 to 4.

[0012]

[Chemical 6] R _{6 to} R ₉ : hydrogen atom, halogen atom, carbon atom number 1 to 4
And an alkyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, which may be the same or different. R ₁₀ : a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group. However, the total number of OH groups is 5, and R ₆ to
At least one R ₉ is a substituent other than a hydrogen atom.

[0013]

[Chemical 7] R _{11 to} R ₁₈ : a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, each being the same. Or it may be different. A: A single bond, an alkylene group, a substituted alkylene group, an alkenyl group, a substituted alkenyl group, an arylene group, or a substituted arylene group.

[0014]

[Chemical 8] R _{19 to} R ₂₂ : hydrogen atom, halogen atom, hydroxyl group, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 5 carbon atoms, alkoxy group having 1 to 4 carbon atoms, or phenyl-substituted alkoxy group And may be the same or different.

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 monohydric phenols such as phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol and phenylphenol, resorcinol, pyrocatechol, hydroquinone, bisphenol A and phlolog. Examples include polyphenols such as lucinol and pyrogallol. Specific examples of aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, and terephthalaldehyde. 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,
Examples thereof include 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.

The hydrogenation reaction product of the phenol resin is
It can be produced by any known hydrogenation reaction, specifically, a phenol resin is dissolved in an organic solvent,
It can be obtained by introducing hydrogen in the presence of a homogeneous or heterogeneous hydrogenation catalyst.

These alkali-soluble phenolic resins can be used as they are, but those having a controlled molecular weight and a controlled molecular weight distribution may be used. As a method of separating the resin for the purpose of controlling the molecular weight and the molecular weight distribution, the resin is crushed and solid-liquid extracted with an organic solvent having an appropriate solubility, or the resin is dissolved in a good solvent,
Drop it into the poor solvent or drop the poor solvent to
Examples include liquid or liquid-liquid extraction methods.

These alkali-soluble phenolic resins may be used alone or in combination of two or more. Further, in the present invention, among these, an alkali-soluble phenol resin obtained by polycondensing phenols and aldehydes under an acid catalyst is particularly preferable. Furthermore, an alkali-soluble phenol resin using m-cresol and p-cresol as phenol is preferable.

The positive resist composition of the present invention may contain, for example, styrene and acrylic acid, methacrylic acid or maleic anhydride in order to improve developability, storage stability, heat resistance and the like, if necessary. A copolymer, a copolymer of an alkene and maleic anhydride, a vinyl alcohol polymer, a vinylpyrrolidone polymer, rosin, shellac and the like can be added. The addition amount of these is usually 0 to 50 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the alkali-soluble phenol resin.

Photosensitizer (b) In the present invention, as the photosensitizer, the above-mentioned general formula [I],
A quinonediazide sulfonic acid ester of at least one polyhydroxy compound selected from the group consisting of the compounds represented by [II] and [III] is used.

Such quinonediazide sulfonic acid ester can be obtained by converting quinonediazide sulfonic acid to sulfonyl chloride with chlorosulfonic acid according to a conventional method and condensing the obtained quinone diazide sulfonyl chloride with a polyhydroxy compound. For example,
A predetermined amount of the above-mentioned polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride is dissolved in a solvent such as dioxane, acetone or tetrahydrofuran, and triethylamine, pyridine, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide or hydroxide is added. It can be prepared by adding a basic catalyst such as potassium and reacting, and washing the resulting product with water and drying.

The following compounds may be mentioned as specific examples of the polyhydroxy compound represented by the above general formula [I].

[0026]

[Chemical 9]

[0027]

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

[0034]

[Chemical 17]

[0035]

[Chemical 18]

[0036]

[Chemical 19]

[0037]

[Chemical 20]

[0038]

[Chemical 21]

[0039]

[Chemical formula 22]

[0040]

[Chemical formula 23]

[0041]

[Chemical formula 24]

[0042]

[Chemical 25]

[0043]

[Chemical formula 26]

[0044]

[Chemical 27]

[0045]

[Chemical 28]

[0046]

[Chemical 29]

[0047]

[Chemical 30]

[0048]

[Chemical 31]

The following compounds may be mentioned as specific examples of the polyhydroxy compound represented by the above general formula [II].

[0050]

[Chemical 32]

[0051]

[Chemical 33]

[0052]

[Chemical 34]

[0053]

[Chemical 35]

[0054]

[Chemical 36]

[0055]

[Chemical 37]

[0056]

[Chemical 38]

[0057]

[Chemical Formula 39]

[0058]

[Chemical 40]

[0059]

[Chemical 41]

The following compounds may be mentioned as specific examples of the polyhydroxy compound represented by the above general formula [III].

[0061]

[Chemical 42]

[0062]

[Chemical 43]

[0063]

[Chemical 44]

[0064]

[Chemical formula 45]

[0065]

[Chemical formula 46]

[0066]

[Chemical 47]

[0067]

[Chemical 48]

[0068]

[Chemical 49]

[0069]

[Chemical 50]

[0070]

[Chemical 51]

[0071]

[Chemical 52]

[0072]

[Chemical 53]

[0073]

[Chemical 54]

[0074]

[Chemical 55]

[0075]

[Chemical 56]

[0076]

[Chemical 57]

[0077]

[Chemical 58]

The quinonediazide sulfonic acid ester moiety of the photosensitizer of the present invention is not particularly limited, but for example, 1,2-benzoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-4-sulfone. Acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,1-naphthoquinonediazide-4
-O-quinone diazide sulfonic acid ester such as -sulfonic acid ester and 2,1-naphthoquinone diazide-5-sulfonic acid ester, and other quinone diazide sulfonic acid ester.

The photosensitizers used in the present invention may be used alone or in combination of two or more kinds. The compounding amount of the photosensitizer is usually 1 to 100 parts by weight, preferably 3 to 40 parts by weight, based on 100 parts by weight of the alkali-soluble phenol resin. This compounded amount is 1
If it is less than 100 parts by weight, it becomes difficult to form a pattern and
If the amount is more than parts by weight, the sensitivity is lowered and the undeveloped portion is likely to occur.

Hydroxy Compound (c) In the present invention, a positive resist composition having an excellent balance of various properties such as sensitivity, residual film ratio and resolution, and particularly improved exposure margin (exposure latitude) and pattern shape is provided. To obtain the compound, the hydroxy compound represented by the above general formula [IV] is used.

Hydroxy compound (c) used in the present invention
The following compounds may be mentioned as specific examples.

[0082]

[Chemical 59]

[0083]

[Chemical 60]

[0084]

[Chemical formula 61]

[0085]

[Chemical formula 62]

[0086]

[Chemical formula 63]

[0087]

[Chemical 64]

[0088]

[Chemical 65]

[0089]

[Chemical formula 66]

[0090]

[Chemical formula 67]

[0091]

[Chemical 68]

[0092]

[Chemical 69]

[0093]

[Chemical 70]

[0094]

[Chemical 71]

[0095]

[Chemical 72]

[0096]

[Chemical formula 73]

[0097]

[Chemical 74]

[0098]

[Chemical 75]

[0099]

[Chemical 76]

[0100]

[Chemical 77]

[0101]

[Chemical 78]

The hydroxy compound (c) may be used alone or in combination of two or more kinds. Further, it may be used in combination with other hydroxy compounds within a range that does not impair the object of the present invention.

The amount of the hydroxy compound (c) used in the present invention is the same as that of the alkali-soluble phenol resin 1
It is usually in the range of 1 to 100 parts by weight with respect to 00 parts by weight. The preferred blending amount varies depending on the composition of the alkali-soluble phenol resin (a), the molecular weight, the molecular weight distribution, the kind of the photosensitizer (b), etc., but is generally in the range of 3 to 60 parts by weight. If the blending amount is too small, the effect of the present invention cannot be exhibited, and conversely, if it is too large, the resolution and heat resistance may be deteriorated.

Positive Resist Composition The positive resist composition of the present invention is usually used by dissolving each of the above components 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, and cyclopentanone; alcohols such as n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, and cyclohexanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dioxane. Ethers such as; ethylene glycol monomethyl ether, alcohol ethers such as ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate,
Esters such as ethyl lactate; cellosolve acetate,
Cellosolve esters such as methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether. Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether;
Halogenated hydrocarbons such as trichlorethylene; aromatic hydrocarbons such as toluene and xylene; polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide; and the like. These solvents may be used alone or in combination of two or more. The amount of solvent used is sufficient to uniformly dissolve the above components.

Therefore, in a preferred embodiment of the present invention, 100 parts by weight of the alkali-soluble phenolic resin (a), 1 to 100 parts by weight of the photosensitizer (b), and the hydroxy compound (c) 1
To 100 parts by weight, and a solvent in an amount sufficient to dissolve each of these components. If necessary, the positive resist composition of the present invention may contain compatible additives such as dyes, surfactants, storage stabilizers, sensitizers, anti-striation agents, and plasticizers. it can.

As a developer for the positive resist composition of the present invention, an aqueous alkali solution is used. Specifically, sodium hydroxide, potassium hydroxide, sodium silicate,
Inorganic alkalis such as ammonia; primary amines such as ethylamine and propylamine; secondary amines such as diethylamine and dipropylamine; trimethylamine,
Tertiary amines such as triethylamine, alcohol amines such as dimethylmethanolamine, triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium Examples thereof include quaternary ammonium salts such as hydroxide.

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.

[0108]

EXAMPLES The present invention will be specifically described below with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to these examples. The parts and% in these examples are based on weight unless otherwise specified.

The resist evaluation methods in the following examples and comparative examples are as follows. (1) Sensitivity The exposure time (msec) that can form a 1: 1 line & space pattern having a sensitivity of 0.60 μm according to the design dimension is shown. (2) Resolution This represents the limit resolution (μm) under the above exposure conditions. (3) Residual film ratio This represents the ratio (%) of the resist film thickness before and after development. (4) Exposure margin (exposure latitude) The relationship between the exposure time and the pattern dimension of 0.60 μm is graphed, and the variation of the exposure time that can maintain the variation of the pattern dimension within ± 5% of the design dimension is calculated. It is the amount divided by the sensitivity. (5) Pattern shape The results obtained by slicing the wafer on which the resist pattern was formed from the direction perpendicular to the line pattern and observing the cross section of the pattern with an electron microscope were shown. When the side wall of the pattern stood up at an angle of 80 ° or more with respect to the substrate and there was no film reduction, it was judged as “good”. Those with a small amount of film loss are designated as "small film loss", and those with a large amount are designated as "large film loss"
And

[Synthesis Example 1] Synthesis of novolak resin (a-1) In a 2 liter flask equipped with a cooling tube and a stirrer,
m-cresol 392g, p-cresol 320g, 3
380 g of 7% formalin, and oxalic acid dihydrate 2.4
8 g was charged, and the reaction was performed for 2 hours while maintaining the temperature at 95 to 100 ° C. After that, water is distilled off at 100 to 105 ° C. for 2 hours, and the temperature is further raised to 180 ° C. for 10 to 3
The pressure was reduced to 0 mmHg, the unreacted monomer and water were removed, and then the temperature was returned to room temperature to obtain 520 g of a novolac resin. To this resin, 380 g of ethyl cellosolve acetate was added and dissolved. Attach the dropping funnel to the flask and adjust the temperature to 80-9.
Toluene 2500 g from the dropping funnel while controlling at 0 ° C
Was added dropwise and heated for an additional 1 hour. The mixture was gradually cooled to room temperature and left still for 1 hour. After removing the supernatant liquid of the precipitated resin component by decantation, 500 g of ethyl cellosolve acetate was added, and 100 at 100 mmHg was added.
Residual toluene was removed by heating to ° C to obtain an ethyl cellosolve acetate solution of novolak resin (a-1).
The polystyrene-converted weight average molecular weight of this novolak resin measured by gel permeation chromatography (GPC) was 12,500.

[Synthesis Example 2] Synthesis of novolak resin (a-2) In a 2 liter flask equipped with a cooling tube and a stirrer,
356 g of m-cresol, 356 g of p-cresol, 3
348 g of 7% formalin, and oxalic acid dihydrate 2.4
9 g was charged, and the reaction was performed for 2 hours while maintaining the temperature at 95 to 100 ° C. After that, water is distilled off at 100 to 105 ° C. for 2 hours, and the temperature is further raised to 180 ° C. for 10 to 3
After the pressure was reduced to 0 mmHg to remove unreacted monomer and water, the molten resin was returned to room temperature and recovered to obtain 525 g of novolac resin (a-2). GP of this novolac resin
The polystyrene equivalent weight average molecular weight by C was 7,000.

[Synthesis Example 3] As the synthetic polyhydroxy compound of the photosensitizer (b-1) , the above chemical formula [b-1] is used.
1,2-naphthoquinonediazide-5-sulfonic acid chloride in an amount corresponding to 85 mol% of this hydroxyl group was dissolved in dioxane to obtain a 10% solution.
While controlling the temperature at 20 to 25 ° C, 1.2 equivalents of 1,2-naphthoquinonediazide-5-sulfonic acid chloride was added dropwise to triethylamine over 30 minutes, and further 4
Hold for time to complete reaction. The precipitated salt was separated by filtration and put into a 0.2% oxalic acid aqueous solution which was 10 times as much as the reaction solution. The precipitated solid content was filtered, washed with ion-exchanged water, and dried to obtain a quinonediazide sulfonic acid ester-based photosensitizer (b-1).

Synthesis Example 4 Synthesis of Photosensitizer (b-14) As a polyhydroxy compound, the above-mentioned chemical formula [b-1]
[4] and using 1,2-naphthoquinonediazide-5-sulfonic acid chloride in an amount corresponding to 80 mol% of this hydroxyl group, except that the photosensitizer (b- 14) was obtained.

[Synthesis Example 5] Synthesis of Photosensitizer (b-25) As a polyhydroxy compound, the above-mentioned chemical formula [b-2]
5] was used, and except that the amount of 1,2-naphthoquinonediazide-5-sulfonic acid chloride corresponding to 95 mol% of this hydroxyl group was used, the photosensitizer (b- 25) was obtained.

[Synthesis Example 6] Synthesis of Photosensitizer (b-30) As a polyhydroxy compound, the above-mentioned chemical formula [b-3]
[0] and the amount of 1,2-naphthoquinonediazide-5-sulfonic acid chloride corresponding to 90 mol% of this hydroxyl group was used, the sensitizer (b- 30) was obtained.

[Synthesis Example 7] Synthesis of Photosensitizer (b-35) As a polyhydroxy compound, the above-mentioned chemical formula [b-3
5] was used, and except that the amount of 1,2-naphthoquinonediazide-5-sulfonic acid chloride corresponding to 90 mol% of this hydroxyl group was used, the sensitizer (b- 35) was obtained.

[Synthesis Example 8] Synthesis of Photosensitizer (b-40) As a polyhydroxy compound, the above-mentioned chemical formula [b-4]
[0] and the amount of 1,2-naphthoquinonediazide-5-sulfonic acid chloride corresponding to 90 mol% of this hydroxyl group was used, the sensitizer (b- 40) was obtained.

[Synthesis Example 9] 2,3,4,4-tetrahydroxybenzophenone as a synthetic polyhydroxy compound of the photosensitizer (b-0) and 85 mol% of this hydroxyl group
A photosensitizer (b-0) was obtained according to the same formulation as in Synthesis Example 3, except that 1,2-naphthoquinonediazide-5-sulfonic acid chloride in an amount corresponding to was used. This photosensitizer (b
-0) was used as a photosensitizer for the positive resist composition of Comparative Example.

Examples 1 to 11 Alkali-soluble phenolic resins (a), photosensitizers (b), and hydroxy compounds (c) having the compositions shown in Table 1 were dissolved in ethyl cellosolve acetate to form a 1.2 μm film. The compounding amount of the solvent was adjusted so that the solution could be applied thickly. In the case of using the novolac resin (a-1), the solid content concentration of the resin solution was measured in advance, and the solid content was mixed and adjusted based on the solid content. These solutions were filtered with a 0.1 μm polytetrafluoroethylene (registered trademark Teflon) filter to prepare a resist solution.

After coating the above-mentioned resist solution on a silicon wafer with a coater, prebaking was performed at 90 ° C. for 90 seconds to form a resist film having a thickness of 1.17 μm. The wafer on which this resist film is formed is used as an i-line stepper NSR17.
55i7A (manufactured by Nikon Corporation, NA = 0.50) and a test reticle were used to perform exposure while varying the exposure time, and then post-exposure bake (Post) at 110 ° C. for 60 seconds.
Exposure baking) was performed. 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. The wafer was taken out and observed with an electron microscope to measure the resolution and the pattern dimension and evaluate the resist. The results are shown in Table 1.

[Comparative Examples 1 to 3] A positive resist solution having the composition shown in Table 1 was prepared using the photosensitizer b-0, and resist evaluation was carried out in the same manner as in Examples 1 to 11.
The results are shown in Table 1.

[0122]

[Table 1]

[0123]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a positive resist composition having excellent sensitivity, residual film ratio, resolution and dimensional controllability. The positive resist of the present invention is particularly suitable for fine processing of 1 μm or less.

Continued Front Page (72) Inventor Toshiaki Fujii 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Inside Zeon Corporation R & D Center

Claims (1)

[Claims] 1. An alkali-soluble phenolic resin (a),
A photosensitizer (b) which is a quinonediazide sulfonic acid ester of at least one polyhydroxy compound selected from the group consisting of compounds represented by the following general formulas [I], [II] and [III], and the following general formula [IV ] The positive resist composition containing the hydroxy compound (c) shown by these. [Chemical 1] R _{1 to} R ₄ : a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,
They may be the same or different. R ₅ : a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group. However, the total number of OH groups is 3 to 4. [Chemical 2] R _{6 to} R ₉ : hydrogen atom, halogen atom, carbon atom number 1 to 4
And an alkyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, which may be the same or different. R ₁₀ : a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group. However, the total number of OH groups is 5, and R ₆ to
At least one R ₉ is a substituent other than a hydrogen atom. [Chemical 3] R _{11 to} R ₁₈ : a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, each being the same. Or it may be different. A: A single bond, an alkylene group, a substituted alkylene group, an alkenyl group, a substituted alkenyl group, an arylene group, or a substituted arylene group. [Chemical 4] R _{19 to} R ₂₂ : hydrogen atom, halogen atom, hydroxyl group, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 5 carbon atoms, alkoxy group having 1 to 4 carbon atoms, or phenyl-substituted alkoxy group And may be the same or different.