JP3158392B2 - Resist coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resist coating composition. More specifically, it relates to a resist coating composition suitable for forming a resist film particularly useful for ultrafine processing.

[0002]

2. Description of the Related Art In the field of fine processing represented by the manufacture of integrated circuits, the processing size in lithography has been further reduced in order to obtain a higher degree of integration of integrated circuits. There is a need for a technique capable of stably performing fine processing of 5 μm or less. Therefore, it is necessary to accurately form a pattern having a size of 0.5 μm or less even in the resist used. However, in the conventional method using visible light (700-400 nm) or near-ultraviolet light (400-300 nm), the method is not suitable.
It is extremely difficult to accurately form a pattern of 5 μm or less. Therefore, a lithography technique using radiation having a shorter wavelength (300 nm or less) is being studied.

[0003] Such radiation includes charged particles such as X-rays represented by the emission line spectrum of a mercury lamp (254 nm), KrF excimer laser (248 nm), synchrotron radiation, and electron beams. Lines and the like can be mentioned, and various resists corresponding to these radiations have been proposed.

[0004] Of these, resists of particular interest are resists that cause a reaction that changes the solubility in a developing solution by the catalytic action of an acid generated by irradiation with radiation. It is called “chemically amplified resist”.

When a resist is used in a manufacturing process of an integrated circuit, a resist solution in which each resist component such as a radiation-sensitive component and a film-forming component is dissolved in a solvent (hereinafter, referred to as a "resist coating composition"). Is prepared and applied on a substrate to be processed using a spin coating apparatus or a roll coater to form a resist film. Therefore, the coating properties and storage stability of the resist coating composition are indispensable performances for performing high-level fine processing stably. In addition, the resist film forms a pattern suitable for fine processing by irradiating radiation, but the shape of the pattern at this time has an important effect on the precision of the fine processing, and a rectangular shape is considered to be preferable. I have.

In a conventional resist using a novolak resin and a naphthoquinonediazide-based photosensitizer used in lithography using visible light, near ultraviolet light, etc., ethyl cellosolve or methyl is used as a solvent for preparing a resist coating composition. It is known that the performance described above can be satisfied by using a cellosolve compound. However, as for the `` chemical amplification type resist '', when an ethyl cellosolve or methyl cellosolve compound is used as a solvent when preparing a resist coating composition, there is a problem in terms of coating properties and storage stability, and further, There is a problem that the formed pattern shape is not rectangular but overhangs.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel resist coating composition. Another object of the present invention is to provide a resist coating composition which can stably perform fine processing, has excellent coating properties, excellent performance such as storage stability, and is suitable as a resist composition which gives a good pattern shape. It is in. Still other objects and advantages of the present invention will be apparent from the following description.

[0008]

According to the present invention, the above objects and advantages of the present invention are as follows: (1) an alkali-soluble resin (hereinafter referred to as "resin (A)"); (3) an alkali-soluble resin having the property of controlling the alkali-solubility of the alkali-soluble resin of (1), and being decomposed in the presence of an acid to control the alkali-solubility of the alkali-soluble resin of (1) (Hereinafter, referred to as "dissolution controlling agent") which exhibits the property of reducing or eliminating the compound or the property of promoting the alkali solubility of the alkali-soluble resin (1), and (4) a solvent represented by the following structural formula (i) R here ^{1 -CO-R 2 (i)} , R 1 and R ² are bonded to each other physician together with the carbon atoms to which they are attached, including the carbon atom
That form a ring of 7 to 11 carbon atoms, in the compound represented
And 2-hexanone, 2-heptanone, 3-heptano
2-octanone, 3-octanone, 3-ethyl pen
Tan-2-one, 3-methylhexane-2-one, 3-
Ethylhexane-2-one, 4-ethylhexane-2-
ON, cyclopentyl ethyl ketone and cyclohexyl
Positive resist coating composition characterized by containing a solvent selected from the group consisting of
"First invention").

Further, according to the present invention, the above objects and advantages of the present invention are as follows: (1) A group consisting of (1) a substituted methyl group, a 1-substituted ethyl group, a silyl group, a germyl group, an alkoxycarbonyl group and an acyl group (2) a resin which is an alkali-insoluble or hardly soluble resin having at least one kind of acid-dissociable group selected and which is alkali-soluble when the above group is acid-dissociated (hereinafter referred to as “resin (B)”); radiation-acid forming agent, and (3) a compound represented by the structural formula as solvent (i) Contact <br/> by beauty 2 - heptanone, 3-heptanone, 2-octanone, 3-octanone, 3-ethyl pentane - 2-one,
3-methylhexane-2-one, 3-ethylhexane-
A positive resist coating composition comprising a solvent selected from the group consisting of 2-one, 4-ethylhexane-2-one, cyclopentylethyl ketone and cyclohexylmethyl ketone (hereinafter referred to as "second invention") Is achieved.

[0010]

Hereinafter, the resist coating composition of the present invention will be described. First, each component will be described.

[0012] Resin (A) resin used in the first inventions (A) are those which have the property of being soluble in an alkaline developer. Therefore,
Any resin may be used as long as it has a functional group having an affinity for an alkali developer, for example, an acidic functional group such as a phenolic hydroxyl group and a carboxyl group. As a suitable resin (A), for example, the following formula (1)

[0013]

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A repeating unit represented by the following formula (2)

[0015]

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Here, the definition of R ⁰¹ is the same as in the above formula (1).

A repeating unit represented by the following formula (3)

[0018]

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And a repeating unit represented by the following formula (4):

[0020]

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Here, R ⁰⁴ , R ⁰⁵ , R ⁰⁶ , R ⁰⁷ and R
⁰⁸ is the same or different and is a hydrogen atom or a carbon number 1 to
An alkyl group of 4,

Resins containing at least one repeating unit represented by the formula (1):

The resin (A) in the present invention is represented by the formula (1):
It may be composed only of the repeating unit represented by the formula (2), (3) or (4), or may have another repeating unit. As other repeating units herein, for example, maleic anhydride, fumaronitrile, acrylamide, acrylonitrile, vinylpyridine, vinylpyrrolidone, vinylimidazole, a repeating unit in which the double bond of a monomer containing a double bond such as vinylaniline is cleaved. Can be mentioned.

Formulas (1), (2), and (3) in the resin (A)
Although the content of the repeating unit represented by the formula (3) and the formula (4) cannot be unconditionally determined by other contained repeating units, it is usually 15 mol% or more, preferably 20 mol% or more. The molecular weight of the resin (A) of the present invention is determined by polystyrene-equivalent weight average molecular weight (hereinafter, referred to as “Mw”) measured by gel permeation chromatography.
However, it is preferably from 1,000 to 150,000, particularly preferably from 3,000 to 100,000.

The resin (A) can be produced, for example, by polymerizing the corresponding vinyl monomer or by polycondensing phenols and aldehydes. Among these resins (A), those containing a repeating unit represented by the formula (1) or (4) have a hydrogenation rate of 70% or less, preferably 50%.
Hereinafter, more preferably, it can be used as a hydrogenated product of 40% or less.

Resin (B) The resin (B) used in the second invention is obtained by substituting a hydrogen atom such as an acidic functional group of the resin (A), for example, a phenolic hydroxyl group or a carboxyl group, with a methyl group, a 1-substituted group. An alkali-insoluble or poorly soluble resin substituted with at least one kind of acid dissociable group (hereinafter, referred to as "substituent B") selected from an ethyl group, a silyl group, a germyl group, an alkoxycarbonyl group, and an acyl group. Here, the acid-dissociable group means a group that can be dissociated in the presence of an acid.

Specific examples of the substituent B include methoxymethyl, methylthiomethyl, methoxyethoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetrahydrothiofuranyl, and benzyloxymethyl. Phenacyl group, bromophenacyl group, methoxyphenacyl group, α-methylphenacyl group, cyclopropylmethyl group, cyclohexyl group, cyclopentyl group, benzyl group, triphenylmethyl group, diphenylmethyl group, bromobenzyl group, nitrobenzyl group, A substituted methyl group such as a methoxybenzyl group or a piperonyl group; a 1-substituted ethyl group such as a 1-methoxyethyl group, a 1-ethoxyethyl group, an isopropyl group, a t-butyl group or a 1,1-dimethylpropyl group; a trimethylsilyl group; Triethylsi Trimethylgermyl group; le group, t- butyl dimethyl silyl group, an isopropyl dimethyl silyl group, a silyl group such as full E sulfonyl butyldimethylsilyl group
Germyl groups such as triethylgermyl group, t-butyldimethylgermyl group, isopropyldimethylgermyl group and phenyldimethylgermyl group; alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and t-butoxycarbonyl group;

Acetyl, propionyl, butyryl, heptanoyl, hexanoyl, valeryl, pivaloyl, isovaleryl, lauryloyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, succinyl, glutaryl , Adipoyl group, piperoyl group, suberoyl group, azelaoyl group, sebacoil group, acryloyl group, propioloyl group, methacryl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, Isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group,
Examples include acyl groups such as hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isonicotinoyl group, p-toluenesulfonyl group, and mesyl group.

Of these, t-butyl, benzyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiofuranyl, tetrahydrothiopyranyl and t-butoxycarbonyl are preferred.

The substituent B is introduced through an acidic functional group of the resin (A). The substituent B is preferably introduced in an amount of 15 to 100%, more preferably 30 to 100%, based on all acidic functional groups of the resin (A). In addition, resin (B)
The molecular weight of Mw is preferably Mw of 1,000 to 150,000.
0, particularly preferably 3,000 to 100,000.

The resin (B) is insoluble in alkali or hardly soluble in alkali. The term “poorly soluble in alkali” refers to the same alkali-decomposable condition that a resin film (B) alone is used instead of the resist film under suitable alkali developing conditions when forming a pattern on a resist film formed using the second invention. When development is performed, the resin (B) has a film thickness of 50% or more of the initial film thickness and refers to a property remaining after the operation.

Radiation-Sensitive Acid-Forming Agent The compound used in the present invention to generate an acid in response to radiation, that is, a radiation-sensitive acid-forming agent is, for example, an onium salt, a halogen-containing compound, a quinonediazide compound, a sulfone compound, a sulfonic acid. And nitrobenzyl compounds, and specific examples thereof include the following compounds.

Examples of the onium salt include an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt, an ammonium salt, and the like.

[0034]

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A compound represented by the following formula (6)

[0036]

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Here, the definitions of R ¹ , R ² and X are the same as in the above formula (5).

A compound represented by the following formula (7):

[0039]

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Here, the definitions of R ¹ , R ² , R ³ and X are the same as in the above formula (5).

Compounds represented by the following formulas can be mentioned.

Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound, and are preferably represented by the following formula (8).

[0043]

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Here, R ⁸ is a trichloromethyl group, a phenyl group, a methoxyphenyl group, a naphthyl group or a methoxynaphthyl group.

A compound represented by the following formula (9):

[0046]

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Here, R ⁹ , R ¹⁰ and R ¹¹ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group.

Compounds represented by the following formulas can be mentioned.

Examples of the quinonediazide compound include a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like.

[0050]

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A compound represented by the following formula (11)

[0052]

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A compound represented by the following formula (12)

[0054]

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And a compound represented by the following formula (13):

[0056]

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Compounds represented by the following formulas can be mentioned.

Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone and the like, and preferably the following formula (14)

[0059]

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Compounds represented by the following formulas can be mentioned.

Examples of the nitrobenzyl compound include a nitrobenzylsulfonate compound and a dinitrobenzylsulfonate compound, and are preferably represented by the following formula (15).

[0062]

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The compounds represented by the following formulas can be mentioned.

Examples of the sulfonic acid compound include an alkyl sulfonic acid ester, a haloalkyl sulfonic acid ester, an aryl sulfonic acid ester and an imino sulfonate.

[0065]

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Here, R ²⁵ and R ²⁶ are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ²⁷ and R ²⁸ are the same or different and have a hydrogen atom and 1 to 4 carbon atoms. 4 alkyl groups or 6-20 carbon atoms
Is an aryl group of

A compound represented by the following formula (17)

[0068]

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Here, R ²⁹ is a hydrogen atom or a group having 1 to 1 carbon atoms.
And R ³⁰ and R ³¹ are the same or different and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 20 carbon atoms, or R ³⁰ and R ³¹ are bonded to each other. May form a ring together with the carbon atom to which they are attached,

A compound represented by the following formula (18):

[0071]

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Here, Z represents a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, or a C 7 to 2
An aralkyl group of 0,

Compounds represented by the following formulas can be mentioned.

Of these, onium salts and quinonediazide compounds are particularly preferred. The compounding amount of these radiation-sensitive acid-forming agents is 100% of the resin (A) or the resin (B).
It is preferably 1 to 70 parts by weight, more preferably 3 to 50 parts by weight, and still more preferably 3 to 2 parts by weight with respect to parts by weight.
0 parts by weight. If the amount is less than 1 part by weight, it is difficult to obtain a sufficient pattern forming ability, and if it exceeds 70 parts by weight, scum tends to occur.

Dissolution Control Agent In the first invention, a dissolution control agent is used. The dissolution controlling agent itself has an effect of controlling the alkali solubility of the alkali-soluble resin, and is decomposed in the presence of an acid, for example, hydrolyzed to reduce or eliminate the alkali-solubility controlling effect on the alkali-soluble resin. It is a compound that exhibits a property of promoting the alkali solubility of the resin (A).

Examples of the dissolution controlling agent include compounds in which a substituent capable of being liberated in the presence of an acid is introduced into an acidic functional group. Examples of the substituent include the substituent B described for the resin (B).

The dissolution controlling agent may be a low molecular compound,
Polymer compounds may be used, for example, the following formulas (19) and (2)
0), Equation (21), Equation (22) and Equation (23)

[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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The compounds represented by the following formulas can be mentioned.

The dissolution controlling agent further includes a resin (B)
Can be advantageously used. The amount of the dissolution controlling agent is preferably 5 to 150 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the resin (A) in the first invention.

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

Solvent The cyclic compound represented by the above structural formula (i) and the following non-cyclic compound
Compounds are used. In the structural formula (i), R ¹ and R ²
Binds to each other physician together with the carbon atoms to which they are attached, including carbon to which R ¹ and R ² are attached
Te, the number of carbon atoms thereof that form a ring of 7 to 11.

[0094]

Specific examples of the cyclic compound of the above formula (i)
It is shea Kuroheputanon, cyclooctanone, cyclononanone, be mentioned such cyclic compounds of Shikudodekanon
it can. Of these, cycloheptanone is particularly preferred.
No.

[0096]

[0097]

[0098]

[0099]

The acyclic compound as a solvent is
2-hexanone (excluding the case of the second invention) , 2-hexanone
Heptanone, 3-heptanone, 2-octanone, 3-octanone, 3-ethylpentan-2-one, 3-methylhexane-2-one, 3-ethylhexane-2-one,
Selected from 4-ethylhexane-2-one, cyclopentyl ethyl ketone and cyclohexyl methyl ketone.

The amount of the solvent is usually 20 to 3,000 per 100 parts by weight of the resin (A) or the resin (B).
0 parts by weight, preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight. In the present invention, another solvent can be mixed with the above-mentioned solvent in a range of, for example, less than 70% by weight, preferably less than 50% by weight, particularly preferably less than 30% by weight of the total amount of the solvent.

Examples of other solvents include ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, benzyl ethyl ether and dihexyl ether; methyl pyruvate, ethyl pyruvate, ethyl acetate, ethyl acetate, butyl acetate and benzyl acetate. , Ethyl benzoate, diethyl oxalate, diethyl maleate,
Esters such as ethylene carbonate, propylene carbonate and γ-butyrolactone; amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide; alcohols such as 1-octanol, 1-nonanol and benzyl alcohol And ethylene glycol
Monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether,
Monoethers of diols such as diethylene glycol monoethyl ether and ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like Ether esters of the diols described above.

[0103] The composition of the present invention may further contain various additives, if necessary. Examples of such additives include surfactants for improving coatability, striation, and developability of a radiation-irradiated portion after formation of a dried coating film. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and commercially available products. Are, for example, F-top EF301, EF303, E
F352 (manufactured by Shin-Akita Chemical Co., Ltd.), Megafax F1
71, F173 (manufactured by Dainippon Ink Co., Ltd.), Florado FC430, FC431 (manufactured by Sumitomo 3M Limited),
Asahi Guard AG710, Surflon S-382, SC
101, SC102, SC103, SC104, SC1
05, SC106 (manufactured by Asahi Glass Co., Ltd.), KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, No. 9
5 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like.

The compounding amount of the surfactant is usually 2 parts by weight or less per 100 parts by weight of the resin (A) or the resin (B). Other additives include an antihalation agent comprising an azo compound and an amine compound, an adhesion aid, a storage stabilizer, an antifoaming agent, and the like.

In the composition of the present invention, the required amounts of the resin (A) or the resin (B), the radiation-sensitive acid forming agent, and various additives to be added as required are specified in the present invention.
It is prepared by dissolving in a solvent containing the aforementioned solvent , and its viscosity is preferably from 8 to 120 cp.

The composition of the present invention is applied in the form of the above solution on a substrate such as a silicon wafer and dried to form a resist film. In this case, the coating on the substrate is performed, for example, by preparing the composition of the present invention, filtering, and then applying the composition by spin coating, flow coating, roll coating, or the like.

The formed resist film is partially irradiated with radiation in order to form a fine pattern. As the radiation used, for example, far-ultraviolet rays such as excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams are used depending on the type of the radiation-sensitive acid forming agent used. Irradiation conditions such as radiation dose are appropriately determined according to the composition of the composition, the type of each additive, and the like.

In the present invention, in order to improve the apparent sensitivity of the resist and the like, it is preferable to perform heating after irradiation with radiation. The heating conditions vary depending on the composition of the composition, the type of each additive, and the like.
To 200 ° C, preferably 50 to 150 ° C.

Examples of the developer used for the subsequent development include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di- n-propylamine, triethylamine, methyldiethylamine, dimethylethanol-
Ruamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrol, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3 .0] -5-nonane or the like and an alkaline aqueous solution having a concentration of 0.1 to 5% by weight.

Further, an alkaline aqueous solution obtained by appropriately adding a water-soluble organic solvent, for example, alcohols such as methanol and ethanol and a surfactant to the above-mentioned developer can also be used as the developer.

[0111]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
In the examples, various characteristics were evaluated as follows. GPC columns manufactured by Mw Tosoh Corporation (G2000H _XL
G3000H _XL, one G4000 _XL ), and gel permeation chromatography using monodisperse polystyrene as a standard under the analysis conditions of a flow rate of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C.

Solubility : When the resist components shown in Table 1 were dissolved, they were completely dissolved, no turbidity or the like, and the case where they were transparent was evaluated as good. The coatable resist coating composition was spin-coated on a silicon wafer, baked, and the formed resist film was observed. A case where there was no coating unevenness, no fogging or foreign matter, and the surface smoothness was high was evaluated as good. The radiation dose at which a line and space pattern having a sensitivity of 0.5 μm can be formed as designed was defined as the sensitivity. The unit was mJ / cm ² .

Using a pattern shape scanning electron microscope, the lower side length A and the upper side length B of the rectangular cross section of the resist pattern were measured, and 0.85 ≦ B / A ≦
When it was 1, it was determined that the pattern shape was good.
However, when the pattern shape is skirted or has an inverse tapered shape, it is determined that the B / A is inferior even if it falls within the above range.

Storage stability The resist coating composition was heated and maintained at 45 ° C., and the period during which no foreign matter was generated and the sensitivity were observed. The determination of the generation of foreign matters was made by observing the occurrence of turbidity and precipitation of the heated and held resist coating composition. In Table 1, the sensitivity in storage stability shows the value of 3 months for the resist coating composition in which no foreign matter was generated, and the value of the day before the foreign matter was generated for the resist coating composition in which the foreign matter was generated. .

Synthesis Example 1 30 g of polyhydroxystyrene was dissolved in tetrahydrofuran, 10 g of potassium t-butoxide was added, 75 g of di-t-butyl-di-carbonate was added dropwise at 0 ° C. with stirring, and the reaction was carried out for 6 hours. I let it. After completion of the reaction, the solution was dropped into water, and the precipitated resin was dried in a vacuum dryer for 5 minutes.
Dry at 0 ° C. overnight. The obtained resin had Mw = 30,0
As a result of NMR measurement, the structure was found to have a structure in which 63% of the hydrogen atoms of the phenolic hydroxyl group were replaced with t-butoxycarbonyl groups. This resin is referred to as resin (A-1).

Synthesis Example 2 54 g of polyhydroxystyrene was dissolved in acetone.
t-butyl-α-bromoacetic acid 27 g, potassium carbonate 10
g and 9 g of potassium iodide were added, and the mixture was reacted for 7 hours while stirring under reflux. After completion of the reaction, this solution was dropped into water, and the precipitated resin was dried at 50 ° C. in a vacuum dryer.
And dried overnight. The obtained resin had Mw = 18,000
As a result of NMR measurement, the structure was such that 22% of the hydrogen atoms of the phenolic hydroxyl group were replaced with t-butylacetic acid residues. This resin is referred to as a resin (B-1).

Examples 1 to 5 and Comparative Examples 1 and 2 The other components shown in Table 1 were mixed with the solvents shown in Table 1, and the solubility was evaluated. Foreign matter was removed by filtration to obtain a resist coating composition. After spin-coating the obtained resist coating composition on a silicon wafer, baking was performed at 100 ° C. for 2 minutes, and the formed resist film was irradiated with radiation through a mask. Here, a KrF excimer laser irradiation device (MBK-400TL-N) manufactured by Admon Science Co., Ltd. was used for irradiation. Then 110 ° C
And baking for 2 minutes in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds.
, And then rinsed with water for 30 seconds to obtain a pattern. Further, with respect to the resist coating composition, these were heated and held, and the storage stability was examined. Table 1 shows the obtained results.

[0118]

[Table 1]

[0119]

The resist coating composition of the present invention can stably perform fine processing and is suitable as a resist coating composition excellent in performance such as coating properties, storage stability and pattern shape. Further, since the resist coating composition of the present invention can cope with radiation such as far ultraviolet rays such as excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams, further miniaturization is expected to progress in the future. It can be advantageously used as a resist for manufacturing semiconductor devices.

Continuation of the front page (56) References JP-A-8-211612 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42 H01L 21/027

Claims (4)

(57) [Claims] (1) an alkali-soluble resin, (2) a radiation-sensitive acid-forming agent, (3) a property of controlling the alkali solubility of the alkali-soluble resin of (1), and in the presence of an acid. A compound which is decomposed to exhibit (1) the property of reducing or eliminating the effect of controlling alkali solubility of the alkali-soluble resin or (1) the property of promoting the alkali solubility of the alkali-soluble resin; Structural formula (i) R ¹ —CO—R ² (i) wherein R ¹ and R ² are bonded to each other and together with the carbon atom to which they are bonded, to form a carbon atom including the carbon atom. A positive resist coating composition comprising a compound represented by the following formula, which forms a ring represented by Formulas 7 to 11. 2. An alkali-soluble resin, (2) a radiation-sensitive acid-forming agent, (3) having the property of controlling the alkali-solubility of the alkali-soluble resin of (1), and in the presence of an acid. (4) 2-hexanone, a compound which is decomposed to exhibit (1) the property of reducing or eliminating the effect of controlling alkali solubility of the alkali-soluble resin or (1) the property of promoting the alkali solubility of the alkali-soluble resin; , 2-heptanone, 3-heptanone, 2-octanone, 3-octanone, 3-ethylpentan-2-one, 3-methylhexane-2-one, 3-
Ethylhexane-2-one, 4-ethylhexane-2-
A positive resist coating composition comprising a solvent selected from the group consisting of ON, cyclopentyl ethyl ketone and cyclohexyl methyl ketone. 3. An alkali-insoluble or poorly soluble resin having at least one kind of acid dissociable group selected from a substituted methyl group, a 1-substituted ethyl group, a silyl group, a germyl group, an alkoxycarbonyl group and an acyl group. A resin which is alkali-soluble when the above group is acid-dissociated, (2) a radiation-sensitive acid-forming agent, and (3) a compound represented by the above structural formula (i) as a solvent. Positive resist coating composition. 4. An alkali-insoluble or poorly soluble resin having at least one kind of acid dissociable group selected from a substituted methyl group, a 1-substituted ethyl group, a silyl group, a germyl group, an alkoxycarbonyl group and an acyl group. A resin which is alkali-soluble when the above group is acid-dissociated, (2) a radiation-sensitive acid-forming agent, and (3) 2 -heptanone, 3-heptanone, 2-octanone, 3-octanone, 3-ethylpentane -2-one,
3-methylhexane-2-one, 3-ethylhexane-
A positive resist coating composition comprising a solvent selected from the group consisting of 2-one, 4-ethylhexane-2-one, cyclopentylethyl ketone and cyclohexylmethyl ketone.