JP2009151266A - Positive radiation sensitive resin composition - Google Patents

Abstract

Provided is a positive radiation sensitive resin composition which is a resist suitable for application to a large substrate of 100 cm × 100 cm or more with a slit coater.
(A) 100 parts by weight of a polymer having a phenolic hydroxyl group, (B) 10 to 50 parts by weight of a quinonediazide group-containing compound, (C) a polymer having a phenolic hydroxyl group ( A positive radiation sensitive resin containing 100 to 9900 parts by weight with respect to a total of 100 parts by weight of A) and the quinonediazide group-containing compound (B), and (D) 0.01 to 5 parts by weight of a surfactant. A composition comprising a specific compound as the quinonediazide group-containing compound (B), a polyether-modified polysiloxane compound as the surfactant (D), and used for slit coater coating. A positive-type radiation-sensitive resin composition.
[Selection figure] None

Description

  The present invention relates to a composition suitably used for so-called photofabrication using photolithography technology for precision microfabrication, and a pattern forming method using the composition. More specifically, the present invention relates to a positive radiation-sensitive resin composition suitable as a masking agent for dry etching processing used in the field of photofabrication such as formation of wiring and electrodes for semiconductors, electronic parts, display panels, touch panels, etc. And a pattern forming method obtained using the positive radiation sensitive resin composition.

  In recent years, display panels are becoming larger and lower in cost at a rapid pace. Among them, a technique capable of stably forming a wiring on a large substrate by a simple process is required. The technique of patterning a resist film by photolithography and then forming a wiring by dry etching has been widely used in the field of semiconductors as a relatively easy and highly productive process. There is a trend to apply in such fields.

  In order to perform stable dry etching on a large substrate, the resist pattern needs to be formed in the same shape over the entire surface of the substrate. For that purpose, it is important that the film thickness of the coating film is uniform and that the margins of the patterning process such as the exposure margin and the development margin are wide.

  The exposure margin refers to an exposure amount width within which a resist pattern can be formed within ± 10% of the standard CD value in a fixed development time (recommended development time). The development margin refers to the width of development time during which a resist pattern can be formed within ± 10% of the standard CD value at a constant exposure amount (recommended exposure amount).

In order to apply a resist on a large substrate, there is a safety problem such as a rotating coater such as a spin coater that comes off during rotation due to the weight of the substrate. Is required. However, when applying with a slit coater, the so-called “sink” phenomenon, in which the resist can be drawn from the substrate edge toward the center after application, becomes a serious problem. Here, JP-A-2003-233174 discloses a positive photoresist composition in which a specific phenol compound is added to a novolak resin and two specific quinonediazide ester compounds at a specific blending ratio for the purpose of improving sensitivity. Yes. If this composition is used, heating unevenness and development unevenness when applied to a large glass substrate of 500 × 600 mm ² or more by a spin coat method can be improved.

However, when a large substrate of 100 cm × 100 cm or more is used, the positive photoresist composition applied to the spin coating method as described above has insufficient properties such as coating properties and in-plane uniformity. In addition, it is difficult to apply a positive radiation-sensitive resin composition uniformly on the surface of a large substrate while preventing “sinking” due to safety problems.
JP 2003-233174 A

  In order to solve the above-mentioned problems, the present invention is a positive radiation-sensitive resin that is a resist suitable for coating with a slit coater on a large substrate of 100 cm × 100 cm or more, in which the phenomenon of being pulled from the substrate edge to the center after coating does not occur. An object is to provide a composition.

  As a result of intensive studies in view of such circumstances, the present inventors have found that a positive radiation-sensitive resin composition having a specific composition forms a uniform coating film even with a slit coater, and “sinking” does not occur. The present invention has been found to provide a resist having a wide patterning process margin sufficient to obtain a stable pattern shape even on a large substrate of 100 cm × 100 cm or more and suitable for application to a large substrate with a slit coater. It came to be completed.

That is, the gist of the present invention is as follows.
[1]
(A) 100 parts by weight of a polymer having a phenolic hydroxyl group, (B) 10 to 50 parts by weight of a quinonediazide group-containing compound, (C) a solvent, the polymer having a phenolic hydroxyl group (A) and the above A positive radiation-sensitive resin composition containing 100 to 9900 parts by weight with respect to a total of 100 parts by weight of the quinonediazide group-containing compound (B) and (D) 0.01 to 5 parts by weight of a surfactant. And
The quinonediazide group-containing compound (B) contains a compound a represented by the following general formula (I), and contains a polyether-modified polysiloxane compound as the surfactant (D), and is used for slit coater coating. A positive-type radiation-sensitive resin composition.

(In the above general formula (I), R ¹ , R ² and R ³ are each independently a hydrogen atom or the following formula (III
And R ¹ , R ² and R ³ are not all hydrogen. )

[2]
The positive radiation-sensitive resin composition as described in [1] above, further comprising a compound b represented by the following general formula (II) as the quinonediazide group-containing compound (B).

(In the above general formula (II), R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a group represented by the following formula (III), and R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are not all hydrogen.)

[3]
The positive radiation sensitive resin composition according to the above [2], wherein the weight ratio of the compound a to the compound b (compound a / compound b) is 3/1 to 1/3. .

[4]
The compound [2] or [3], wherein the compound a and the compound b are contained in a total amount of 30 to 100 parts by weight with respect to 100 parts by weight of the quinonediazide group-containing compound (B). Positive type radiation sensitive resin composition.

[5]
(I) a step of applying the positive radiation sensitive resin composition according to any one of [1] to [4] to a substrate surface with a slit coater;
(Ii) pattern exposure of the positive radiation sensitive resin composition applied to the substrate surface by exposure with UV light and / or drawing with an electron beam;
(Iii) A resist pattern forming method comprising: forming a resist pattern by developing the positive radiation sensitive resin composition that has undergone the pattern exposure step.

  According to the present invention, a positive radiation-sensitive resin composition that becomes a resist suitable for coating with a slit coater on a large substrate of 100 cm × 100 cm or more, and resist pattern formation using the positive radiation-sensitive resin composition A method is provided.

Hereinafter, the present invention will be specifically described.
[Positive radiation sensitive resin composition]
The positive-type radiation-sensitive resin composition according to the present invention specifies (A) a polymer having a phenolic hydroxyl group, (B) a quinonediazide group-containing compound, (C) a solvent, and (D) a surfactant. A positive-type radiation-sensitive resin composition containing a specific compound (compound a) as the quinonediazide group-containing compound (B), and a polyether-modified polysiloxane as the surfactant (D) It is characterized by containing a compound. Hereafter, each component which comprises the positive radiation sensitive resin composition of this invention is demonstrated.

<(A) Polymer having phenolic hydroxyl group>
The polymer (A) having a phenolic hydroxyl group functions as a positive resist having sensitivity in the wavelength region of g-line and i-line when used in combination with a photosensitizer comprising the quinonediazide group-containing compound (B). To do. Examples of the polymer (A) having a phenolic hydroxyl group include novolak resins, polyhydroxystyrene and derivatives thereof shown below. These can be used alone or in combination.

(Novolac resin)
The novolak resin used in the present invention is alkali-soluble, and is a resin obtained by condensing m-cresol and one or more other phenols (hereinafter also referred to simply as phenols) with an aldehyde compound. And it is a novolak resin whose ratio of m-cresol is 40-90 mass% in all phenols.

  Specific examples of the other phenols used as the raw material for the novolak resin include, for example, o-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3, Examples include 4-xylenol, 3,5-xylenol, and 2,3,5-trimethylphenol. These can be used alone or in combination of two or more.

Of these, p-xylenol, 2,3-xylenol, 2,4-xylenol, 3,4-xylenol and 2,3,5-trimethylphenol are preferred.
Preferred combinations of m-cresol and one or more other phenols include m-cresol / 2,3-xylenol, m-cresol / p-cresol, m-cresol / 2,4-xylenol, m -Cresol / 2,3-xylenol / 3,4-xylenol, m-cresol / 2,3,5-trimethylphenol and m-cresol / 2,3-xylenol / 2,3,5-trimethylphenol Can do.

  Examples of the aldehyde compound to be condensed include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde. . Of these, formaldehyde and o-hydroxybenzaldehyde can be particularly preferably used.

These aldehydes can also be used alone or in combination of two or more. Such an aldehyde compound is preferably used in an amount of 0.4 to 1 mol per 1 mol of the other phenols.
It is used in an amount of 2 mol, more preferably 0.6 to 1.5 mol.

In the condensation reaction between phenols and aldehyde compounds, an acidic catalyst is usually used. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid, and the like. Such an acidic catalyst can usually be used in an amount of 1 × 10 ^{−5 to} 5 × 10 ⁻¹ mol with respect to 1 mol of phenols.

In the condensation reaction, water is usually used as a reaction medium. However, when a heterogeneous system is used from the beginning of the reaction, alcohols such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether, etc. are used as the reaction medium; And cyclic ethers such as dioxane; ketones such as ethyl methyl ketone, methyl isobutyl ketone, and 2-heptanone can be used. These reaction media are usually reaction raw materials 1
Used in an amount of 20 to 1,000 parts by weight per 00 parts by weight.

Although the temperature of a condensation reaction can be suitably adjusted according to the reactivity of a raw material, it is 10 to 200 degreeC normally.
As the reaction method, it is possible to appropriately employ a method of charging phenols, aldehyde compounds, acidic catalysts, etc. in a lump, and a method of adding phenols, aldehyde compounds, etc. as the reaction proceeds in the presence of acidic catalysts. it can.

  As a method for recovering the novolak resin after the completion of the condensation reaction, in order to remove unreacted raw materials, acidic catalyst, reaction medium, etc. existing in the system, the reaction temperature is increased to 130 ° C. to 230 ° C. and volatilized under reduced pressure. The method for removing the novolak resin and recovering the novolak resin, and the obtained novolak resin is ethylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl lactate, methyl isobutyl ketone, 2-heptanone, dioxane, methanol, ethyl acetate, etc. There is a method in which a poor solvent such as water, n-hexane, n-heptane and the like is mixed, and then the resin solution layer to be separated is separated to recover a high molecular weight novolak resin.

  Further, the polystyrene-reduced weight average molecular weight (hereinafter also referred to as “Mw”) of the novolak resin is such that workability when forming a positive radiation-sensitive resin composition, developability when used as a resist, From the viewpoint of sensitivity and heat resistance, it is preferably from 2,000 to 20,000, particularly preferably from 3,000 to 15,000.

<(B) Quinonediazide group-containing compound>
The positive-type radiation-sensitive resin composition of the present invention contains a quinonediazide group-containing compound (B) at a specific ratio, and the quinonediazide group-containing compound (B) is a compound a represented by the following general formula (I): It is characterized by containing.

In the general formula (I), R ¹ , R ² and R ³ are each independently a hydrogen atom or the following formula (III)
And R ¹ , R ² , and R ³ are not all hydrogen.

In the general formula (I), for example, R ¹ is a group represented by the formula (III), and R ² and R ³
When is hydrogen, compound a is a compound as follows.

  Such a compound can be obtained, for example, by bringing a compound represented by the following formula (IV) into contact with naphthoquinone-1,2-diazide-5-sulfonyl chloride for esterification.

  When the quinonediazide group-containing compound (B) contains compound a, a positive radiation sensitive resin composition is coated on a substrate, and the positive radiation sensitive resin composition is exposed and developed. The shape can be precisely controlled.

  Moreover, the positive radiation sensitive resin composition of this invention contains further the compound b represented by the following general formula (II) as said quinonediazide group containing compound (B) from a viewpoint of improving resolution. Is preferred.

In the general formula (II), R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or a group represented by the following formula (III), and R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are not all hydrogen.

In the above general formula (II), for example, when R ⁴ is a group represented by the formula (III) and R ⁵ , R ⁶ , R ⁷ , R ⁸ are hydrogen, the compound b is the following compound It is.

Such compounds include, for example, a compound represented by the following formula (V) and naphthoquinone-1,2
-It can obtain by making a diazide-5-sulfonyl chloride contact and making it esterify.

  As described above, the positive radiation-sensitive resin composition of the present invention contains the compound a as the quinonediazide group-containing compound (B). From the viewpoint of improving the resolution, the compound a is 4- [1- (4- Hydroxyphenyl) -1-methylethyl] -6- (1-methyl-1-phenylethyl) -1,3-benzenediol and naphthoquinone-1,2-diazido-5-sulfonyl chloride 1.0. It is preferably an esterification reaction product with a mole.

  Further, the positive radiation sensitive resin composition of the present invention preferably contains the compound b as described above, but the compound b is 4,6-bis [1-bis (3) from the viewpoint of improving the resolution. -Methyl-4-hydroxyphenyl) methyl] -p-cresol is particularly preferably an esterification reaction product of 1.0 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride.

The weight ratio of the compound a to the compound b (compound a / compound b) is preferably 3/1 to 1/3, more preferably 1/1 from the viewpoint of improving resolution.
The total content of compound a and compound b with respect to 100 parts by weight of the quinonediazide group-containing compound (B) is preferably 30 to 100 parts by weight, more preferably 40 to 40 parts from the viewpoint of improving sensitivity and resolution. 90 parts by weight.

  The positive-type radiation-sensitive resin composition of the present invention may contain other quinonediazide group-containing compounds other than the above-mentioned compound a and compound b as the quinonediazide group-containing compound (B), or two or more kinds. You may contain.

Examples of the other quinonediazide group-containing compounds include polyhydroxybenzophenones, (poly) hydroxyphenylalkanes, bis [(poly) hydroxyphenyl] alkanes, tris (hydroxyphenyl) methanes or methyl-substituted products thereof, and bis (cyclohexyl). Hydroxyphenyl) hydroxyphenylmethanes or methyl-substituted products thereof, or 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl]
Phenyl] ethylidene] diphenol, 7-hydroxy-4- (4′-hydroxyphenyl) -2-methyl-2- (2 ′, 4′-dihydroxy) phenylcoumarin, 4- [1- (4-hydroxyphenyl) -1-methylethyl] -6- (1-methyl-1-phenylethyl) -1,3-benzenediol, 4,6-bis [1-bis (3-methyl-4-hydroxyphenyl) methyl] -p -Cresol, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1-hydroxy-3-methoxybenzene, or a novolak resin, pyrogallol-acetone resin, p-hydroxystyrene homopolymer Or a copolymer of a monomer copolymerizable therewith, or a compound having a hydroxyl group or an amino group;
And quinonediazide group-containing sulfonic acid or naphthoquinone-1,2-diazide-5-sulfonyl chloride; and the like; and complete ester compounds, partial ester compounds, amidated products, and partially amidated products.

Specifically, as the polyhydroxybenzophenones,
2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy- 2′-methylbenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3 ′, 4,4 ′, 6-pentahydroxybenzophenone, 2 , 2 ′, 3,4,4′-pentahydroxybenzophenone, 2,2 ′, 3,4,5-pentahydroxybenzophenone, 2,3 ′, 4,4 ′, 5 ′, 6-hexahydroxybenzophenone, 2, , 3,3 ′, 4,4 ′, 5′-hexahydroxybenzophenone, etc.
Examples of the bis [(poly) hydroxyphenyl] alkanes include bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- ( 4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- ( 2 ', 3', 4'-trihydroxyphenyl)
Propane, etc.
Examples of the tris (hydroxyphenyl) methanes or methyl substitution products thereof include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, and bis (4-hydroxy-). 2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2- Hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, etc.
Examples of the bis (cyclohexylhydroxyphenyl) hydroxyphenylmethanes or methyl substitution products thereof include bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2- Hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl- 4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxy) Phenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxy Phenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2) -Hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4 -Hydroxyfe The Rumetan, etc.,
Examples of the compound having a hydroxyl group or amino group include phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine 4,4′-diaminobenzophenone, etc.
Examples of the quinonediazide group-containing sulfonic acid include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, and orthoanthraquinonediazidesulfonic acid.

  The content of the quinonediazide group-containing compound (B) in the positive radiation sensitive resin composition of the present invention is 10 to 50 parts by weight, preferably 100 parts by weight of the polymer (A) having a phenolic hydroxyl group. 15 to 40 parts by weight, more preferably 20 to 35 parts by weight.

<(C) Solvent>
Specific examples of the solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate. , Propylene glycol monopropyl ether acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate , Ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, butyl acetate, pyrubin It includes methyl, ethyl pyruvate and the like.

  Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether A high boiling point solvent such as acetate can also be used.

These solvents can be used alone or in combination of two or more. Of these, ethyl 2-hydroxypropionate is preferred.
These solvents have a solid content concentration of usually 1 wt.% When the resulting positive radiation-sensitive resin composition is applied on a substrate with a thickness of 5 μm or less. % To 50% by weight, preferably 5% to 25% by weight. That is, the amount of the solvent is usually 100 to 9900 parts by weight, preferably 300 to 1900 parts by weight with respect to 100 parts by weight of the total of the polymer (A) having a phenolic hydroxyl group and the quinonediazide group-containing compound (B). Used in.

<(D) Surfactant>
The positive-type radiation-sensitive resin composition of the present invention contains a surfactant (D) for the purpose of improving applicability, defoaming property, leveling property, etc., and suppressing sink marks of the coating film immediately after application, In order to achieve the purpose of suppressing sink marks of the coating film immediately after coating, it is characterized by containing a polyether-modified polysiloxane compound as a surfactant (D).

By including the polyether-modified polysiloxane compound as the surfactant (D), the coating property of the positive radiation sensitive resin composition by the slit coater was remarkably improved, and the coating film was once applied to the substrate by the slit coater. Later, so-called “sinks” where the resist moves from the edge of the coating film to the center can be eliminated even in a large substrate of 100 cm × 100 cm or more.

  Examples of the polyether-modified polysiloxane compound include KL-245, KL-270 (manufactured by Kyoeisha Chemical Co., Ltd.), and polymers represented by the following general formula (VI).

In the above formula, R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 20, and x and y are each independently an integer of 2 to 100.
Examples of the polyether-modified siloxane compound represented by the general formula (VI) include SH-28PA, SH8400, SH-190, 193, and SF-8428 (manufactured by Toray Dow Corning Co., Ltd.). These can be used alone or in combination of two or more.

Other surfactants include, for example, BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183 (manufactured by Dainippon Ink and Chemicals), Florard FC- 135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 ( Asahi Glass Co., Ltd.), SZ-6032 (Toray Silicone Co., Ltd.), NBX-15 (Neos Co., Ltd.) and other commercially available fluorosurfactants;
Silicon surfactants commercially available under the names SF-8418, SF-8427, SF-8428, SF-8416 (manufactured by Toray Dow Corning);
Nonion S-6, Nonion 0-4, Pronon 201, Pronon 204 (manufactured by NOF Corporation), Emulgen A-60, A-90, A-500 (manufactured by Kao Corporation), KL-600 Nonionic surfactants marketed under names such as (manufactured by Kyoeisha Chemical Co., Ltd.) can be mentioned, and these can be used alone or in combination of two or more.

These surfactants (D) are used in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the polymer (A) having a phenolic hydroxyl group. .
<(E) Other ingredients>
The positive radiation sensitive resin composition of the present invention may contain the following as other components.

(Polynuclear phenol compound)
The polynuclear phenol compound is not an essential component of the positive-type radiation-sensitive resin composition of the present invention, but the inclusion of the polynuclear phenol compound improves the alkali solubility of the positive-type radiation-sensitive resin composition and makes the resist pattern shape more precise. Can be controlled. Here, the polynuclear phenol compound means a compound having two or more independently present benzene rings and two or more phenolic hydroxyl groups in one molecule having a hydroxyl group bonded to a part of the benzene ring. . Specifically, for example, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] diphenol, 2,2-bis (1,5- Dimethyl-4-hydroxyphenyl) propionic acid methyl ester, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-benzenediol, 1,1-bis (2,5- And dimethyl-4-hydroxyphenyl) acetone.

  When these polynuclear phenol compounds are contained in the positive radiation sensitive resin composition of the present invention, the polynuclear phenol compound is usually 5 to 100 parts by weight of the polymer (A) having a phenolic hydroxyl group. It is used in an amount of 40 parts by weight, preferably 10-30 parts by weight. By containing in the above range, the shape of the resist pattern can be controlled precisely.

[Resist pattern forming method of the present invention]
The resist pattern forming method of the present invention is characterized by including the following steps.
(I) Step of applying the positive radiation sensitive resin composition of the present invention to the substrate surface with a slit coater (ii) Exposure of the positive radiation sensitive resin composition applied to the substrate surface with UV light and / or Or the process of pattern exposure by drawing with an electron beam (iii) The process of forming a resist pattern by developing the positive radiation sensitive resin composition which passed through this pattern exposure process.

  In order to form a resist pattern on a large substrate of 100 cm × 100 cm or more, it is necessary to apply a positive radiation sensitive resin composition to the substrate surface with a slit coater. In a device such as a spin coater that rotates the substrate, there is a safety problem such as the substrate coming off during the rotation due to the weight of the substrate. Therefore, apply the positive radiation sensitive resin composition uniformly on the surface of the large substrate. Is difficult.

  The positive radiation sensitive resin composition of the present invention specifies the polymer (A) having a phenolic hydroxyl group, the quinonediazide group-containing compound (B), the solvent (C) and the surfactant (D) as described above. Since it contains a polyether-modified polysiloxane compound as a surfactant (D), so-called “sinks” can be eliminated even in a large substrate of 100 cm × 100 cm or more, and it contains a quinonediazide group. Since a specific compound is contained as the compound (B), a fine resist pattern can be formed.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
[Preparation Example] Preparation of Positive Radiation Sensitive Resin Composition Using the following components (A) to (E), positive radiation sensitive resin compositions ((1-1) to (1-13)) are prepared. Prepared.

<(A) Synthesis of a polymer having a phenolic hydroxyl group (novolak resin)>
Synthesis example 1
m-cresol, 2,3-xylenol and 3,4-xylenol were mixed at a weight ratio of 60:30:10, formalin was added thereto, and propylene glycol monomethyl ether was used as a reaction solvent using oxalic acid catalyst as a reaction solvent. After heating at 0 ° C. for 6 hours, the reaction product was dissolved in ethyl lactate, mixed with water, and the resin layer was recovered to obtain a novolak resin having a weight average molecular weight of 8000. This resin is designated as novolak resin A-1.

Synthesis example 2
m-cresol and p-cresol are mixed at a weight ratio of 50:50, formalin is added thereto, and a condensation reaction is performed in the same manner as in Synthesis Example 1 using an oxalic acid catalyst to obtain a novolak resin having a weight average molecular weight of 5000. It was. This resin is designated as novolak resin A-2.

<(B) Quinonediazide group-containing compound>
The following compounds were used:
B-1: 1.0 mol of 4- [1- (4-hydroxyphenyl) -1-methylethyl] -6- (1-methyl-1-phenylethyl) -1,3-benzenediol (see the following formula) And an esterification reaction product of 1.0 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride (Sanpo Chemical Laboratory Co., Ltd.),

B-2: 1.0 mol of 4,6-bis [1-bis (3-methyl-4-hydroxyphenyl) methyl] -p-cresol (see formula below) and naphthoquinone-1,2-diazide-5 Esterification reaction product with 2.0 mol of sulfonyl chloride (Sanpo Chemical Laboratory),

B-3: 1.0 mol of 4,6-bis [1-bis (3-methyl-4-hydroxyphenyl) methyl] -p-cresol and naphthoquinone-1,2-diazide-5-sulfonyl chloride 3.0 Esterification reaction product with mol (Sanpo Chemical Laboratory Co., Ltd.),
B-4: 1.0 mol of 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1-hydroxy-3-methoxybenzene (see formula below) and naphthoquinone-1,2-diazide Esterification reaction product with 2.0 mol of -5-sulfonyl chloride (Sanpo Chemical Laboratory),

B-5: 1.0 mol of 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] diphenol (see formula below) and naphthoquinone-1 , 2-Diazide-5-sulfonyl chloride with 1.0 mol of esterification product (Sanpo Chemical Laboratory).

<(C) Solvent>
The following were used as the solvent (C).
C-1: Ethyl 2-hydroxypropionate.

<(D) Surfactant>
The following were used.
D-1: SH8400 (manufactured by Dow Corning Toray) Polyether-modified polysiloxane,
D-2: KL-270 (manufactured by Kyoeisha) polyether-modified polysiloxane,
D-3: KL-245 (manufactured by Kyoeisha) polyether-modified polysiloxane,
D-4: NBX-15 (manufactured by Neos) Diglycerin EO adduct perfluorononenyl ether.

<(E) Other ingredients>
The following were used.
E-1: 1,1-bis (2,5-dimethyl-4-hydroxyphenyl) acetone.

<Preparation of Positive Radiation Sensitive Resin Composition (Compositions (1-1) to (1-13))>
(Preparation of composition (1-1))
78 parts of novolak resin A-1, 6 parts of quinonediazide group-containing compound B-1, 3 parts of B-3, 11 parts of B-4, 0.01 part of surfactant D-2, polynuclear phenol compound E −1: 22 parts, 260 parts of C-1 were added and mixed and dissolved, followed by filtration using a membrane filter having a pore size of 1 μm to prepare a composition (1-1).

(Preparation of compositions (1-2) to (1-13))
It prepared in the same procedure as a composition (1-1) using the material shown in Table 1.

[Examples 1 to 9, Comparative Examples 1 to 4]
<Applicability evaluation 1>
The positive radiation sensitive resin composition obtained by the preparation example was applied to a 100 cm × 100 cm glass substrate with a slit coater, dried on a hot plate, and then evaluated for the following criteria by observing the paint film from the substrate edge. The evaluation results are indicated by ◎, ○, Δ, ×. The results are shown in Table 2.

Coating property 1 A: No paint film is observed from the edge of the substrate.
◯: The shrinkage of the coating film from the substrate edge is less than 1 mm.
(Triangle | delta): The shrinkage of the coating film from the board | substrate edge is 1 mm or more and less than 5 mm.

X: The film shrinkage from the edge of the substrate is 5 mm or more.
<Applicability evaluation 2>
The positive type radiation sensitive resin composition obtained by the preparation example was applied to a 100 cm × 100 cm glass substrate with a slit coater, dried with a hot plate, and the thickness difference between the position 5 mm from the edge of the substrate and the central part was observed. Evaluation was performed based on the criteria, and the evaluation results were indicated by ◎, ○, Δ, and ×. The results are shown in Table 2.

Coating property 2 A: The film thickness difference between the position 5 mm from the edge of the substrate and the central portion is less than ± 2%.
○: The film thickness difference between the position 5 mm from the edge of the substrate and the center is ± 2% or more and less than ± 5%
The

Δ: The film thickness difference between the position 5 mm from the edge of the substrate and the center is ± 5% or more and less than ± 10%.
is there.
X: The film thickness difference between the position 5 mm from the substrate edge and the central portion is ± 10% or more.

<Patternability evaluation>
(Resist coating formation)
The positive radiation sensitive resin composition obtained in the preparation example was applied to a 5 cm × 5 cm glass substrate with a slit coater and then baked on a hot plate at 100 ° C. for 1 minute to obtain a resist film.

(Exposure, development)
Of the substrates prepared as described above, a substrate with good coatability was exposed through a mask, then developed with alkali, and subjected to patterning evaluation. The evaluation conditions are as follows.

Exposure machine: Mask Aligner MA150,
(Contact aligner, manufactured by SUSS Microtex)
Exposure amount: 200 mJ / cm ² (around 420 nm),
Exposure style: Hard contact exposure,
Development: Performed by dipping in an aqueous 2.38 mass% tetramethylammonium hydroxide solution. The development time was 60 seconds.

(Patternability evaluation)
About the board | substrate exposed and developed, the resist part of L / S = 3um / 3um pattern was observed with the optical microscope and SEM, and the following references | standards evaluated. The results are shown in Table 2. The resist pattern dimension results at that time are also shown in Table 2.

Patternability ◎: Pattern skipping is not observed at all, and mask dimension standard is less than ± 10%
A pattern can be formed.
○: Pattern skipping is not observed at all, but mask dimension standard ± 10%
A pattern is formed with a dimension of ± 20% or less.

Δ: A part of the pattern is peeled off from the substrate.
X: All patterns are peeled off from the substrate.
<Dry etching resistance>
After dry etching the resist, the L / S = 3 um / 3 um pattern was observed with an optical microscope and evaluated according to the following criteria. The results are shown in Table 2.
Dry etching resistance A: No peeling of resist is observed.

                      X: Resist peeling is observed.

Claims (5)

(A) 100 parts by weight of a polymer having a phenolic hydroxyl group;
(B) 10 to 50 parts by weight of a quinonediazide group-containing compound,
(C) 100-9900 parts by weight of the solvent with respect to a total of 100 parts by weight of the polymer (A) having a phenolic hydroxyl group and the quinonediazide group-containing compound (B);
(D) A positive radiation-sensitive resin composition containing 0.01 to 5 parts by weight of a surfactant,
As the quinonediazide group-containing compound (B), containing a compound a represented by the following general formula (I),
Containing a polyether-modified polysiloxane compound as the surfactant (D),
A positive-type radiation-sensitive resin composition, which is used for slit coater coating.

(In the above general formula (I), R ¹ , R ² and R ³ are each independently a hydrogen atom or the following formula (III
And R ¹ , R ² and R ³ are not all hydrogen. )

The positive radiation sensitive resin composition according to claim 1, further comprising a compound b represented by the following general formula (II) as the quinonediazide group-containing compound (B).

(In the above general formula (II), R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a group represented by the following formula (III), and R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are not all hydrogen.)

  3. The positive radiation-sensitive resin composition according to claim 2, wherein a weight ratio of the compound a to the compound b (compound a / compound b) is 3/1 to 1/3.   The positive feeling according to claim 2 or 3, wherein the compound a and the compound b are contained in a total amount of 30 to 100 parts by weight with respect to 100 parts by weight of the quinonediazide group-containing compound (B). Radiation resin composition. (I) a step of applying the positive radiation sensitive resin composition according to any one of claims 1 to 4 to a substrate surface by a slit coater;
(Ii) pattern exposure of the positive radiation sensitive resin composition applied to the substrate surface by exposure with UV light and / or drawing with an electron beam;
(Iii) forming a resist pattern by developing the positive-type radiation-sensitive resin composition that has undergone the pattern exposure step, and forming a resist pattern.