JP2007148000A - Photoresist composition for spray coating, and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a photoresist film having good thickness uniformity by spray coating even when a shoulder has been formed on a surface of a substrate to be coated. <P>SOLUTION: A photoresist film 2 is formed by spray coating on a substrate with a shoulder 1 having a level difference H of 10-1,000 μm disposed on a surface to be coated using a photoresist composition containing a modified siloxane-based surfactant, whereby a laminate is obtained in which the top face 1a and the side face 1b of the shoulder 1 are continuously covered with the photoresist film 2, a thickness of the photoresist film 2 on the top face 1a of the shoulder is 1-40 μm, and a thickness of the photoresist film 2 on a boundary portion between the top face 1a and the side face 1b of the shoulder is ≥75% of a thickness on the top face 1a adjacent to the boundary portion. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photoresist composition for spray coating and a laminate.

  In lithography technology, for example, a photoresist film made of a photoresist material is formed on a substrate, and the photoresist film is selectively exposed to radiation such as light and electron beams through a mask on which a predetermined pattern is formed. And a development process is performed to form a resist pattern having a predetermined shape on the photoresist film. A photoresist material in which the exposed portion changes to a property that dissolves in the developer is referred to as a positive type, and a resist material that changes to a property in which the exposed portion does not dissolve in the developer is referred to as a negative type.

Conventionally, a spray coating method is known as a photoresist coating method in addition to a spin coating method (Patent Document 1 below).
The spin coating method is suitable for forming a photoresist film having a uniform film thickness on a flat substrate, whereas the spray coating method follows the unevenness of the substrate on a substrate having unevenness on the surface. It is suitable for forming a photoresist film having an uneven shape.
JP 2004-307667 A

However, the spray coating method has a problem that when applied to a substrate having a stepped portion on the surface, the film thickness of the photoresist film tends to be locally thin at the corners of the stepped portion.
The present invention has been made in view of the above circumstances, and a photoresist composition capable of forming a photoresist film with good film thickness uniformity by a spray coating method even when a step portion is formed on a surface to be coated of a substrate. It is an object of the present invention to provide a laminate in which a photoresist film with good film thickness uniformity is formed on a substrate having a product and a stepped portion.

In order to achieve the above object, the present invention employs the following configuration.
A first embodiment of the present invention is a photoresist composition for use in a method of forming a photoresist film on a substrate by spray coating, which contains a modified siloxane surfactant, and is a photoresist for spray coating characterized in that It is a composition.

  In the second embodiment of the present invention, a photoresist film made of a photoresist composition containing a modified siloxane-based surfactant is formed on a substrate having a step of 10 to 1000 μm on the surface to be coated. It is a laminate, and the upper surface and side surfaces of the step portion are continuously covered with the photoresist film, the film thickness of the photoresist film on the upper surface of the step portion is 1 to 40 μm, and the step portion The laminate is characterized in that the film thickness at the boundary between the upper surface and the side surface is 75% or more of the film thickness at the upper surface adjacent to the boundary.

According to the present invention, it is possible to obtain a photoresist composition that can form a photoresist film with good film thickness uniformity by a spray coating method even when a step portion is formed on the surface to be coated of the substrate.
Further, according to the present invention, it is possible to obtain a laminate in which a photoresist film having a good film thickness uniformity is formed on a substrate having a stepped portion.

<Photoresist composition>
[Surfactant]
The photoresist composition of the present invention contains a modified siloxane-based surfactant (hereinafter sometimes simply referred to as a surfactant).
Examples of the modifying group as the modified siloxane surfactant include an alkyl group, an aralkyl group, and an ester group. Specifically, a polyalkyl modified siloxane surfactant, a polyester modified siloxane surfactant, and an aralkyl modified siloxane interface. An activator and an alkylaralkyl-modified siloxane surfactant are preferably used.
For example, SF8416 (manufactured by Dow Corning Toray), XL-121 (manufactured by Clariant), TSF4421 (manufactured by GE Toshiba Silicone), KF-412 as polyalkyl-modified siloxane surfactants. , KF-413, KF-414 (all manufactured by Shin-Etsu Chemical Co., Ltd.); as polyester-modified siloxane surfactants, BYK-310, BYK-315 (all manufactured by Big Chemie), KF-910, X-22 715 (both manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-322 and BYK-323 (both manufactured by Big Chemie) as aralkyl-modified siloxane surfactants; alkylaralkyl-modified siloxane surfactants SH203 and SF8419 (both manufactured by Toray Industries, Inc.) -Dow Corning), WACKER TN (Asahi Kasei Wa) Kicker Silicone).
Further, as the polyalkyl-modified siloxane surfactant, a modified polyalkylsiloxane is suitable. The modified polyalkylsiloxane is, for example, an active hydrogen of methyl hydrogen silicone in which a part of the side chain of polydimethylsiloxane is replaced with hydrogen, [AO- (RO—) n—X ′] (A Represents an allyl group, X ′ represents a terminal substituent, R is a linear or branched alkylene group having 1 to 30 carbon atoms, and n is an integer of 1 to 20. A compound obtained by adding allyl-modified polyether. The terminal substituent X ′ is preferably a monovalent group (—OC—CH ₃ ) derived from an acetate ester and / or an alkyl group such as a butyl group.

The modified siloxane surfactant is usually used in the form of a solution dissolved in an appropriate solvent.
The modified siloxane surfactant may be used alone or in combination of two or more.
The content of the modified siloxane surfactant in the photoresist composition is such that the solid content of the surfactant is 0.01 to 1 solid content / solid content (mass%) with respect to the total solid content excluding the surfactant. It is preferable to be within the range, and a range of 0.05 to 0.50 solid content / solid content (mass%) is more preferable.

[Ingredients other than surfactant]
The component composition other than the surfactant in the photoresist composition of the present invention is not particularly limited, and a known component composition of a photoresist composition can be applied.
The photoresist composition of the present invention may be a positive type or a negative type. For example, it may be a positive-type or negative-type chemically amplified photoresist composition, a diazonaphthoquinone-novolak resin-based positive photoresist composition, or a polymerization-type negative photoresist composition.
Among these, positive or negative chemically amplified photoresist compositions are preferred.

In the case of a chemically amplified photoresist composition, the base resin contains an alkali-soluble resin or a resin that can be alkali-soluble. The former is a negative photoresist composition, and the latter is a positive photoresist composition.
In the case of the negative type, a crosslinking agent is blended in the photoresist composition together with an alkali-soluble resin and an acid generator. When an acid is generated from the acid generator by exposure at the time of forming the photoresist pattern, the acid acts to cause cross-linking between the alkali-soluble resin and the cross-linking agent, thereby changing to alkali-insoluble.
In the case of the positive type, the base resin is an alkali-insoluble resin having a so-called acid dissociable dissolution inhibiting group, and when acid is generated from the acid generator by exposure, the acid dissociates the acid dissociable dissolution inhibiting group. As a result, the base resin component becomes alkali-soluble. Therefore, in the formation of the photoresist pattern, when the photoresist composition applied on the substrate is selectively exposed, the alkali solubility in the exposed portion increases and alkali development can be performed.
In the present invention, a positive chemically amplified photoresist is more preferable.

[First Embodiment]
First, a chemically amplified positive photoresist composition will be described as a first embodiment of the photoresist composition of the present invention.

  The chemically amplified positive photoresist composition of the present embodiment includes (A) a compound that generates an acid upon irradiation with actinic rays or radiation, (B) a resin whose solubility in alkali is increased by the action of the acid, and the surfactant. Containing.

(A) Compound that generates acid upon irradiation with actinic rays or radiation:
(A) Compound that generates acid upon irradiation with actinic rays or radiation (hereinafter referred to as component (A).
) Is an acid generator and is not particularly limited as long as it is a compound that generates an acid directly or indirectly by light.
Specifically, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (2-furyl) ethenyl]- s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-Ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl] -s-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-diethoxyphenyl) ) Ethenyl] -s-tria 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3 -Methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -s-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) ) -S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-butyl) Mo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) ) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, Tris (1,3-dibromopropyl) -1,3,5- Halogen-containing triazine compounds such as triazine and tris (2,3-dibromopropyl) -1,3,5-triazine and halogens represented by the following general formula (I) such as tris (2,3-dibromopropyl) isocyanate Containing triazine compounds;

(Wherein R ^{5 to} R ⁷ may be the same or different and each represents a halogenated alkyl group)

α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2 -Chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, a compound represented by the following general formula (II);

(In the formula, R ⁸ represents a monovalent to trivalent organic group, R ⁹ represents a substituted, unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group, and n is 1 to 3. Indicates a natural number.
Here, the aromatic compound group refers to a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, a furyl group, a thienyl group. And heterocyclic groups such as These may have one or more suitable substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like. R ⁹ is particularly preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
As the monovalent to trivalent organic group of R ⁸ , an aromatic compound group is preferable, and a compound in which R ⁸ is an aromatic compound group and R ⁹ is a lower alkyl group is particularly preferable.

The acid generator represented by the general formula (II) is a compound in which when n = 1, R ⁸ is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ⁹ is a methyl group. Specifically, α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p- Methoxyphenyl) acetonitrile. When n = 2, the acid generator represented by the general formula (II) is specifically an acid generator represented by the following chemical formula. )

  Bissulfonyldiazomethanes such as bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane; p-toluenesulfone 2-nitrobenzyl acid, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate Nitrobenzyl derivatives such as pyrogallotrimesylate, pyrogallotritosylate, benzyltosylate, benzylsulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysk Sulfonic acid esters such as N-imide, N-phenylsulfonyloxymaleimide and N-methylsulfonyloxyphthalimide; trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; diphenyliodonium hexafluorophosphate; (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4- Onium salts such as methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate; - DOO, alpha-methyl benzoin tosylate Le - benzointosylate Les such bets - DOO like; other Jifeniruyo - Doniumu salts, triphenylsulfonium salts, phenyldiazonium salts, benzylcarboxy Ne - DOO and the like.

Among these, as the component (A), the general formula (1):
R—SO ₂ O—N═C (CN) — (1)
Wherein R is a substituted or unsubstituted oxime sulfonate group represented by, for example, an alkyl group having 1 to 8 carbon atoms or an aryl group. Formula (2):
_{R-SO 2 O-N =} C (CN) -A-C (CN) = N-OSO 2 -R (2)
(In the formula, A is a divalent, for example, substituted or unsubstituted alkylene group having 1 to 8 carbon atoms or an aromatic compound group, and R is a substituted or unsubstituted, for example, alkyl group having 1 to 8 carbon atoms. Or an aryl group) is preferred.
Here, the aromatic compound group refers to a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, a furyl group, a thienyl group. And heterocyclic groups such as These may have one or more suitable substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like. Further, in the above general formula, it is more preferable that A is a phenylene group and R is, for example, a lower alkyl group having 1 to 4 carbon atoms.

In this embodiment, (A) component may be used independently and may be used in combination of 2 or more type.
Moreover, the compounding quantity of (A) component shall be 0.1-20 mass parts with respect to 100 mass parts of (B) component, Preferably it is 0.2-10 mass parts. By setting it to 0.1 parts by mass or more, sufficient sensitivity can be obtained, and by setting it to 20 parts by mass or less, solubility in a solvent is good, a uniform solution is obtained, and storage stability tends to be improved. There is.

(B) Resin whose solubility in alkali is increased by the action of acid:
(B) Resin whose solubility in alkali is increased by the action of an acid (hereinafter referred to as component (B)) is not particularly limited as long as it is a resin component used in a chemically amplified positive photoresist composition. Can do.
Among these, since it is excellent in developability, resolution, and plating solution resistance, the shape of the product by the photoresist pattern and plating is good and stable, and suitable for the production of connection terminals and the like, the following general formula (III ) And a resin containing a structural unit represented by the following general formula (VI) (hereinafter referred to as (b2) component). It is preferable to use one or more selected.
The “constituent unit” refers to a monomer unit constituting the polymer.

(B1) Component:
The component (b1) has a structural unit represented by the following general formula (III).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an acid labile group.)
In the general formula (III), R ¹ is a hydrogen atom or a methyl group.
R ² is an acid labile group. The acid labile group is variously selected, and is particularly a group represented by the following formula (IV) or (V), a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a tetrahydropyranyl group, A tetrafuranyl group or a trialkylsilyl group is preferable.

(In the formula, R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ¹² is a linear or branched chain having 1 to 10 carbon atoms. And R ¹³ is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and a is 0 or 1.)

  Examples of linear and branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, etc. Can be exemplified by a cyclohexyl group and the like.

  Here, as the acid labile group represented by the above formula (IV), specifically, for example, methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, iso-propoxyethyl group, n-butoxyethyl group, iso -Butoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methyl-ethyl group, etc. Examples of the acid labile group of the above formula (V) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include those having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

The component (b1) may contain one type of structural unit represented by the general formula (III), but may contain two or more types of structural units having different structures.
Furthermore, the component (b1) can contain a structural unit derived from another polymerizable compound for the purpose of appropriately controlling physical and chemical properties. Here, the “other polymerizable compound” means a polymerizable compound other than the structural unit represented by the general formula (III).

Examples of such polymerizable compounds include known radically polymerizable compounds and anionic polymerizable compounds.
For example, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid and 2-methacryloyloxyethyl Radical polymerizable compounds such as methacrylic acid derivatives having a carboxyl group and an ester bond such as phthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meta ) (Meth) acrylic acid alkyl esters such as acrylate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Meta) Acry (Meth) acrylic acid aryl esters such as benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, Vinyl group-containing aromatic compounds such as vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; acrylonitrile, methacrylate Examples thereof include nitrile group-containing polymerizable compounds such as nitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.
Note that (meth) acrylate represents one or both of methacrylate and acrylate. (Meth) acrylic acid represents one or both of methacrylic acid and acrylic acid.

  (B1) The ratio of the structural unit represented by the general formula (III) in all the structural units constituting the component is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and more preferably 30 to 70 mol%. Is most preferred. By setting it to the lower limit value or more, a pattern can be obtained when the photoresist composition is used, and by setting it to the upper limit value or less, it is possible to balance with other structural units.

The component (b1) can be obtained by polymerizing a monomer for deriving each structural unit by a known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN).
The mass average molecular weight (Mw) of the component (b1) (polystyrene conversion standard by gel permeation chromatography, the same shall apply hereinafter) is not particularly limited, but is preferably 1000 to 20000, more preferably 1000 to 10000, -5000 is most preferred. If it is smaller than the upper limit of this range, it is more preferable to use it as a photoresist, and if it is larger than the lower limit of this range, the dry etching resistance and the cross-sectional shape of the photoresist pattern are better.

(B2) Component:
The component (b2) is a resin having a structural unit represented by the following general formula (VI).

(Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, and X forms a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which it is bonded. .)
In the general formula (VI), R ³ is a hydrogen atom or a methyl group.
The lower alkyl group represented by R ⁴ may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, various pentyl groups, etc., among them, lower alkyl group having 2 to 4 carbon atoms because of high contrast, good resolution, depth of focus, etc. Is preferred.

X forms a monocyclic or polycyclic hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which it is bonded.
Examples of monocyclic hydrocarbon rings include cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like.
Examples of the polycyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. Specific examples include polycyclic hydrocarbon rings such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
Of the above, a cyclohexane ring and an adamantane ring are preferred as the hydrocarbon ring having 5 to 20 carbon atoms formed by X together with the carbon atom to which it is bonded.

  The component (b2) may have one of the structural units represented by the general formula (VI), but may have two or more structural units having different structures.

The component (b2) preferably further contains a structural unit derived from a polymerizable compound having an ether bond. By including the structural unit, adhesion to the substrate during development and plating solution resistance are improved.
Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and 3-methoxy. Butyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate And radical polymerizable compounds such as (meth) acrylic acid derivatives having an ether bond and an ester bond such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl ( (Meth) acrylate and methoxytriethylene glycol (meth) acrylate. These compounds can be used alone or in combination of two or more.

Furthermore, the component (b2) can contain a structural unit derived from another polymerizable compound for the purpose of appropriately controlling physical and chemical properties. Here, the “other polymerizable compound” means a polymerizable unit other than the monomer derived from the structural unit represented by the general formula (VI) and the structural unit derived from the polymerizable compound having an ether bond. Meaning of compound.
Examples of such a polymerizable compound include known radical polymerizable compounds and anion polymerizable compounds similar to those given as specific examples of the other polymerizable compounds in the component (b1).

(B2) The ratio of the structural unit represented by the general formula (VI) in all the structural units constituting the component is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and more preferably 30 to 70 mol%. Is most preferred. By setting it to the lower limit value or more, a pattern can be obtained when the photoresist composition is used, and by setting it to the upper limit value or less, it is possible to balance with other structural units.
When the component (b2) includes a structural unit derived from a polymerizable compound having an ether bond, the content is preferably 10 to 90 mol% with respect to all the structural units constituting the component (b2). 20-80 mol% is more preferable, and 30-70 mol% is the most preferable. By setting it to the lower limit value or more, the effect of containing the structural unit can be obtained satisfactorily, and by setting it to the upper limit value or less, it is possible to balance with other structural units.

The component (b2) can be obtained by polymerizing a monomer for deriving each structural unit by a known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN).
The mass average molecular weight (Mw) of the component (b2) is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 450,000, and most preferably 150,000 to 400,000. When it is smaller than the upper limit of this range, it has sufficient solubility in a photoresist solvent to be used as a photoresist, and the dry etching resistance and photoresist pattern cross-sectional shape which are larger than the lower limit of this range are good.

  In this embodiment, when (B) component contains 1 or more types chosen from (b1) component and (b2) component, the content rate is the point of the effect by using these components, (B) component 20 mass% or more is preferable with respect to the whole, 30 mass% or more is more preferable, and 100 mass% is the most preferable. In the component (B), the content of the resin selected from the component (b2) is preferably 20% by mass or more, more preferably 50% by mass or more from the viewpoint of contrast, plating solution resistance, cracks, and peelability. Mass% is most preferred.

(C) Alkali-soluble resin:
The positive photoresist composition of the present embodiment further contains (C) an alkali-soluble resin (hereinafter referred to as “component (C)”) in order to appropriately control physical and chemical characteristics. Is preferred.
As the component (C), an arbitrary one can be appropriately selected from known alkali-soluble resins in conventional chemically amplified photoresists. Among these, in particular, at least one resin selected from (c1) a novolak resin, (c2) a copolymer having a hydroxystyrene structural unit and a styrene structural unit, (c3) an acrylic resin, and (C4) a vinyl resin. And (c1) a novolak resin and / or (c2) a copolymer having a hydroxystyrene structural unit and a styrene structural unit. This is because it is easy to control the coating property and the development speed.

(C1) Novolac resin:
The novolak resin as component (c1) can be obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenol”) and an aldehyde in the presence of an acid catalyst. .
The phenols used here include, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p- Ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6- Xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcino -Hydroquinone, hydroquinone monomethyl ether, pyrogallol, phlorogricinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, etc. The
Examples of aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.

The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.
In particular, a novolac resin using only m-cresol as a phenol is preferable because the development profile is particularly good.
A preferable mass average molecular weight of the component (c1) is, for example, 3,000 to 50,000.

(C2) Copolymer having hydroxystyrene structural unit and styrene structural unit:
The component (c2) is a copolymer having at least a hydroxystyrene structural unit and a styrene structural unit. That is, a copolymer comprising a hydroxystyrene constituent unit and a styrene constituent unit, or a copolymer comprising a hydroxystyrene constituent unit, a styrene constituent unit and other constituent units.

Examples of the hydroxystyrene structural unit include hydroxystyrene structural units such as hydroxystyrene such as p-hydroxystyrene, and α-alkylhydroxystyrene such as α-methylhydroxystyrene and α-ethylhydroxystyrene.
Examples of the styrene structural unit include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene, and the like.
A preferred mass average molecular weight of the component (c2) is, for example, 1,000 to 30,000.

(C3) Acrylic resin:
The acrylic resin as component (c3) is not particularly limited as long as it is an alkali-soluble acrylic resin, but in particular, from a structural unit derived from a polymerizable compound having an ether bond and a polymerizable compound having a carboxyl group. It is preferable to contain the derived structural unit.
Examples of polymerizable compounds having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, and phenoxy polyethylene glycol. Examples include (meth) acrylic acid derivatives having an ether bond and an ester bond such as (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and preferably 2-methoxyethyl acrylate , Methoxytriethylene glycol acrylate. These compounds can be used alone or in combination of two or more.
(Meth) acrylate indicates one or both of methacrylate and acrylate. (Meth) acrylic acid represents one or both of methacrylic acid and acrylic acid.
These compounds can be used alone or in combination of two or more.

Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, 2-methacryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl. Examples include maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid and other compounds having a carboxyl group and an ester bond, and acrylic acid and methacrylic acid are preferred. These compounds can be used alone or in combination of two or more.
The preferred mass average molecular weight of the component (c3) is, for example, 10,000 to 800,000, preferably 30,000 to 500,000.

(C4) Vinyl resin:
The vinyl resin as component (c4) is poly (vinyl lower alkyl ether), and is obtained by polymerizing a single or lower mixture of vinyl lower alkyl ethers represented by the following general formula (VII). (Co) polymers made.

(In the above general formula (VII), R ¹⁴ represents a linear or branched alkyl group having 1 to 5 carbon atoms.)

In the general formula (VII), examples of the linear or branched alkyl group having 1 to 5 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- A butyl group, n-pentyl group, i-pentyl group, etc. can be mentioned. Of these alkyl groups, a methyl group, an ethyl group, and an i-butyl group are preferable, and a methyl group is particularly preferable. A particularly preferred poly (vinyl lower alkyl ether) is poly (vinyl methyl ether).
The preferred mass average molecular weight of the component (c4) is, for example, 10,000 to 200,000, preferably 50,000 to 100,000.

  The blending amount of the component (C) is 0 to 300 parts by mass, preferably 0 to 200 parts by mass with respect to 100 parts by mass of the component (B). When the amount is 300 parts by mass or less, it is possible to suppress a decrease in contrast between an exposed portion and an unexposed portion for forming a pattern, and a reduction in film thickness.

(D) Acid diffusion controller:
The positive photoresist composition preferably further contains (D) an acid diffusion control agent (hereinafter referred to as “component (D)”) in order to improve the photoresist pattern shape, the stability of holding and the like.
As the component (D), an arbitrary one can be appropriately selected from those known as acid diffusion control agents in conventional chemically amplified photoresists. In particular, (d1) a nitrogen-containing compound is preferably contained, and (d2) an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be further contained as necessary.

(D1) Nitrogen-containing compound:
Examples of the nitrogen-containing compound as component (d1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tribenzylamine, diethylamine, triethanolamine, and n-hexylamine. , N-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4 '-Diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethyla Toamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazo -L, benzimidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholine, 4-methyl Examples include morpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, and the like.
Of these, alkanolamines such as triethanolamine are particularly preferred.
These may be used alone or in combination of two or more.
When the component (B1) is 100% by mass, the component (d1) is usually used in the range of 0 to 5% by mass, and particularly preferably in the range of 0 to 3% by mass.

(D2) Organic carboxylic acid or phosphorus oxo acid or derivative thereof:
As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are preferable, and salicylic acid is particularly preferable.
Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and other phosphoric acid or derivatives thereof such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid- Like phosphonic acids such as di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives thereof, phosphinic acids such as phosphinic acid, phenylphosphinic acid and their esters Among these, phosphonic acid is particularly preferable.
These may be used alone or in combination of two or more.
The component (d2) is usually used in the range of 0 to 5% by mass, particularly preferably in the range of 0 to 3% by mass, when the component (B) is 100% by mass.
The component (d2) is preferably used in the same amount as the component (d1). This is because the component (d2) and the component (d1) form a salt and stabilize.

  Positive photoresist compositions have additional miscible additives, such as additional resins, plasticizers, adhesion aids, stability, to improve the performance of the photoresist film, as long as the essential properties are not impaired. Commonly used agents such as a colorant, a colorant, and a surfactant can be added and contained.

  Further, the positive photoresist composition can be appropriately mixed with an organic solvent for viscosity adjustment. Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, Polyhydric alcohols such as propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether -Cyclic ethers such as dioxane; and methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionate Can be exemplified Le, esters such as ethyl ethoxypropionate. Of these, propylene glycol monomethyl ether acetate (PGMEA) is preferred.

In addition, in order to obtain good coating properties when spray coating, it is preferable to use a highly volatile solvent as a part or all of the organic solvent. Specifically, an organic solvent having a boiling point of 130 ° C. or lower is preferable, and specific examples include acetone, methyl isobutyl ketone (MIBK), propylene glycol monomethyl ether (PGME), and the like.
The blending amount of these highly volatile organic solvents is preferably 10 to 90% by mass, more preferably 10 to 80% by mass, and most preferably 20 to 60% by mass of the total organic solvent contained in the positive photoresist composition. preferable.

In this embodiment, the organic solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.
The amount of the organic solvent used is not particularly limited, but the solid content concentration of the photoresist composition is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and most preferably 5 to 30% by mass. If the solid content concentration is not less than the above lower limit value, good applicability is obtained when spray coating, and if it is not more than the upper limit value, good applicability is obtained when spray coating is performed.

  The positive photoresist composition of the present embodiment can be prepared, for example, by mixing and stirring each component by a usual method. If necessary, it may be dispersed and mixed using a disperser such as a dissolver, a homogenizer, or a three-roll mill. Moreover, after mixing, you may further filter using a mesh, a membrane filter, etc.

[Second Embodiment]
Next, a chemically amplified negative photoresist composition will be described as a second embodiment of the photoresist composition of the present invention.
The chemically amplified negative photoresist composition of this embodiment comprises (A) a compound that generates an acid upon irradiation with actinic rays or radiation (acid generator) (B ′) a novolak resin, (C ′) a plasticizer, (E) It contains a crosslinking agent and the above surfactant.

(A) Acid generator The component (A) in the present embodiment is not particularly limited as long as it is a compound that generates an acid directly or indirectly by light. The same compound as the component (A) in the positive chemically amplified photoresist composition of the first embodiment can be used.
In particular, triazine compounds can be preferably used because of their high performance as an acid generator by light and good solubility even when a solvent is used. Among them, bromo-containing triazine compounds, particularly 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxyphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4 -Methoxy) styryl-s-triazine and tris (2,3-dibromopropyl) isocyanate can be preferably used.

In this embodiment, (A) component may be used independently and may be used in combination of 2 or more type.
The blending amount of the component (A) in this embodiment is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the sum of the components (A), (B ′), (C ′), and (E). 0.05-2 mass parts is more preferable, and 0.1-1 mass part is further more preferable. When the component (A) is 0.01 part by mass or more, crosslinking and curing by heat and light are sufficiently performed, and the plating resistance, chemical resistance, and adhesion of the obtained photoresist film can be improved. By setting the amount to 10 parts by mass or less, it is possible to suppress development failure during development.

(B ′) Novolak Resin The (B ′) novolac resin in the present embodiment is preferably alkali-soluble.
Such a (B ′) novolak resin can be obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst.
Examples of phenols used at this time include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p- Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4 , 5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like. .
Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.
The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, and the like are used as the acid catalyst.

(B ′) The mass average molecular weight (Mw) of the novolak resin is not particularly limited, but is preferably 3,000 to 50,000.
The blending amount of (B ′) novolak resin is preferably 50 to 95 parts by mass, and 65 to 80 parts by mass with respect to 100 parts by mass of the sum of components (A), (B ′), (C ′), and (E). Is more preferable. By setting the component (B ′) within the above range, an effect of suppressing the occurrence of development failure during development can be obtained.

(C ′) Plasticizer (C ′) Examples of the plasticizer include polymers having an ethylenic double bond, and it is preferable to employ an acrylic polymer or a vinyl polymer.
Hereinafter, an example using an acrylic polymer or a vinyl polymer as the component (C ′) will be described.

In the component (C ′), the acrylic polymer is preferably one that is alkali-soluble, a structural unit derived from a polymerizable compound having an ether bond, and a structural unit derived from a polymerizable compound having a carboxyl group. The thing containing is preferable.
Specific examples of the polymerizable compound having an ether bond and the polymerizable compound having a carboxyl group include the same compounds as those exemplified as the monomer of (c3) acrylic resin in the first embodiment.

In the acrylic polymer, the proportion of the structural unit derived from the polymerizable compound having an ether bond is preferably 30 to 90 mol%, more preferably 40 to 80 mol%.
By making it 90 mol% or less, compatibility with (B ′) novolak resin solution can be improved, and Benard cell (non-uniformity generated on the coating film surface due to gravity or surface tension gradient etc. during pre-baking is five to seven. Generation of a rectangular network pattern) can be suppressed, and a uniform photoresist film can be obtained. By making it 30 mol% or more, cracks during plating can be suppressed.

  In the acrylic polymer, the proportion of the structural unit derived from the polymerizable compound having a carboxyl group is 2 to 50 mol%, preferably 5 to 40 mol%. By setting it to 2 mol% or more, the alkali solubility of the acrylic resin can be improved and sufficient developability can be obtained. Further, the peelability is improved, and the photoresist remaining film on the substrate can be suppressed. By adjusting the amount to 50 mol% or less, the remaining film ratio after development can be improved.

The weight average molecular weight of the acrylic polymer is preferably 10,000 to 800,000, more preferably 30,000 to 500,000.
By setting it to 10,000 or more, the photoresist film has sufficient strength, and the expansion of the profile and the occurrence of cracks during plating can be suppressed. By setting it to 800,000 or less, adhesion and peelability can be improved.

Furthermore, the acrylic polymer can contain structural units derived from other radical polymerizable compounds for the purpose of appropriately controlling physical and chemical properties.
Here, the “other radical polymerizable compound” means a radical polymerizable compound other than the above-described polymerizable compound.
Examples of such radically polymerizable compounds include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2- (Meth) acrylic acid hydroxyalkyl esters such as hydroxypropyl (meth) acrylate; (meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic acids such as diethyl maleate and dibutyl fumarate Acid diesters; vinyl group-containing aromatic compounds such as styrene and α-methylstyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; acrylonitrile, methacrylonitrile, etc. Tolyl group-containing polymerizable compound, vinyl chloride, chlorine-containing polymerizable compounds such as vinylidene chloride; acrylamide, and the like can be used amide bond-containing polymerizable compounds such as methacrylamide.
These compounds can be used alone or in combination of two or more.
Of these, n-butyl acrylate, benzyl methacrylate, methyl methacrylate and the like are particularly preferable. The proportion of structural units derived from other radical polymerizable compounds in the acrylic polymer is preferably 5 to 60 mol%, more preferably 5 to 40 mol%.

Examples of the polymerization solvent used in the synthesis of the acrylic polymer include alcohols such as ethanol and diethylene glycol; alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol ethyl methyl ether; ethylene glycol ethyl Alkyl ether acetates of polyhydric alcohols such as ether acetate and propylene glycol methyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone and methyl isobutyl ketone; Esters such as ethyl acetate and butyl acetate Can be used.
Of these, polyhydric alcohol alkyl ethers and polyhydric alcohol alkyl ether acetates are particularly preferred.
As a polymerization catalyst used when synthesizing an acrylic polymer, a normal radical polymerization initiator can be used. For example, azo compounds such as 2,2′-azobisisobutyronitrile; benzoyl peroxide, di-t- Organic peroxides such as butyl peroxide can be used.

Further, an alkali-soluble vinyl polymer can be preferably used as the component (C ′).
In addition, the vinyl polymer here is a polymer obtained from a vinyl compound.
For example, polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, polymaleimide, polyacrylamide, polyacrylonitrile, polyvinylphenol and the like And the like. Among these resins, those having a carboxyl group or a phenolic hydroxyl group in the resin side chain or main chain are preferable because alkali development is possible. In particular, a resin having a carboxyl group is preferable because it has high alkali developability.
Further, the mass average molecular weight of the vinyl polymer is preferably 10,000 to 200,000, more preferably 50,000 to 100,000.

The component (C ′) is in the range of 5 to 30 parts by mass, preferably 10 to 20 parts by mass with respect to 100 parts by mass of the sum of the components (A), (B ′), (C ′), and (E). Can be contained.
By setting the component (C ′) to 5 parts by mass or more, it is possible to suppress the floating of the photoresist, the generation of cracks, and the like during plating, and to improve the plating solution resistance. By setting it to 30 parts by mass or less, the strength of the formed photoresist film is improved, and a clear profile cannot be obtained due to swelling or the like, and the tendency of the resolution to be reduced can be suppressed.

(E) Crosslinking agent As the component (E), amino compounds such as melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin can be used. In particular, alkoxymethylated amino resins such as alkoxymethylated melamine resins and alkoxymethylated urea resins can be suitably used.

The alkoxymethylated amino resin is obtained by, for example, condensing a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution with a lower alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, or isopropyl alcohol. And then the reaction solution is cooled and precipitated.
Specific examples of the alkoxymethylated amino resin include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylated urea resin, ethoxymethylated urea resin, and propoxymethyl. And urea-oxygenated resin, butoxymethylated urea resin, and the like.
A preferable mass average molecular weight of the alkoxymethylated amino resin is, for example, 100 to 500.
The alkoxymethylated amino resin can be used alone or in combination of two or more.
In particular, an alkoxymethylated melamine resin is preferable because it can form a stable photoresist pattern with a small dimensional change of the photoresist pattern with respect to a change in radiation dose. Among these, one or more selected from methoxymethylated melamine resins, ethoxymethylated melamine resins, propoxymethylated melamine resins and butoxymethylated melamine resins are preferable.

  The component (E) is in the range of 1 to 30 parts by mass, preferably 5 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B ′), (C ′), and (E). Can be contained. When the component (E) is 1 part by mass or more, the plating resistance, chemical resistance and adhesion of the photoresist film can be improved. In addition, when the amount is 30 parts by mass or less, it is possible to suppress a tendency to cause development failure during development.

  Further, the negative photoresist composition can be appropriately mixed with an organic solvent for viscosity adjustment. Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl. Ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monophenyl ether, diethylene Recall dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate , Diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Pyrene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3 -Methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl Ketone, methyl isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2 -Methyl, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, ethyl-3-propoxypropionate, propyl-3-methoxypropionate, isopropyl- 3-methoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate Methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, benzyl methyl ether, benzyl ethyl ether, dihexyl ether, benzyl acetate, Examples thereof include ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, benzene, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin.

Also in this embodiment, it is preferable to use a highly volatile solvent as part or all of the organic solvent, as in the first embodiment. Specific examples and preferred blending amounts of the highly volatile solvent are the same as those in the first embodiment.
In this embodiment, the organic solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.
The amount of the organic solvent used is not particularly limited, but it is preferable to set the solid content concentration of the photoresist composition within the same preferable range as in the first embodiment.

In the present embodiment, in addition to the above-described components, it is preferable to further contain (D) an acid diffusion control agent, if necessary, in order to improve the photoresist pattern shape, retention stability, and the like.
As the component (D), an arbitrary one can be appropriately selected from those known as acid diffusion control agents in conventional chemically amplified photoresists. In particular, (d1) a nitrogen-containing compound is preferably contained, and (d2) an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be further contained as necessary.

Specific examples of the (d1) nitrogen-containing compound include the same compounds as the component (d1) in the first embodiment.
Specific examples of the (d2) organic carboxylic acid or phosphorus oxo acid or derivative thereof include the same as the component (d2) in the first embodiment.
The component (d1) is usually used in the range of 0 to 5% by mass, particularly preferably in the range of 0 to 3% by mass, when the component (B ′) is 100% by mass.
The component (d2) is usually used in the range of 0 to 5% by mass, particularly preferably in the range of 0 to 3% by mass, when the component (B ′) is 100% by mass.
Further, as in the first embodiment, the component (d2) is preferably used in the same amount as the component (d1).

In the negative photoresist composition of this embodiment, an adhesion aid can be used to improve the adhesion to the substrate.
A functional silane coupling agent is effective as the adhesion aid to be used. Here, the functional silane coupling agent means a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Specific examples thereof include trimethoxysilyl benzoic acid, γ -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
The blending amount is preferably 20 parts by mass or less per 100 parts by mass of (B ′) novolac resin.

Further, the negative photoresist composition of the present embodiment includes acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, and iso-valeric acid in order to finely adjust the solubility in an alkaline developer. Monocarboxylic acids such as benzoic acid and cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid Cinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, hydroxymonocarboxylic acids such as syringic acid; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid , Isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid Polycarboxylic acids such as trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, Dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4, -butanetetracarboxylic acid, cyclopentanetetracarboxylic dianhydride Acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic anhydride, and glycerin tris anhydrous trimellitate can also be added.
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, phenyl cellosolve acetate, etc. A high boiling point solvent can also be added.
The amount of the compound used for finely adjusting the solubility in the alkali developer can be adjusted as appropriate according to the application, and is not particularly limited as long as the composition can be mixed uniformly. However, it is 60 mass% or less with respect to the composition obtained, Preferably it is 40 mass% or less.

Furthermore, a filler, a colorant, a viscosity modifier and the like can be added to the negative photoresist composition of this embodiment as necessary. Examples of the filler include silica, alumina, talc, bentonite, zirconium silicate, and powdered glass.
Colorants include alumina white, clay, barium carbonate, barium sulfate and other extender pigments; zinc white, lead white, yellow lead, red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, carbon black, etc. Pigments; organic pigments such as brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue, and phthalocyanine green; basic dyes such as magenta and rhodamine; direct dyes such as direct scarlet and direct orange; Examples include acid dyes such as yellow.
Examples of the viscosity modifier include bentonite, silica gel, and aluminum powder. These additives are contained in a range not impairing the essential characteristics of the composition, preferably 50% by mass or less based on the obtained composition.

  The negative photoresist composition of this embodiment can be prepared by mixing and stirring by a normal method when no filler or pigment is added. When adding a filler or a pigment, it is preferable to disperse and mix using a disperser such as a dissolver, a homogenizer, or a three roll mill. Moreover, you may further filter using a mesh, a membrane filter, etc. as needed.

[Third Embodiment]
In addition, (A) an acid generator, (B ″) an alkali-soluble resin, and (E) a crosslinking agent are included as essential components, and (B ″) an alkali-soluble resin includes α- (hydroxyalkyl) acrylic acid, or α A negative photoresist composition using a resin having a unit derived from at least one selected from lower alkyl esters of-(hydroxyalkyl) acrylic acid is preferable in that a good photoresist pattern with less swelling can be formed.
Α- (Hydroxyalkyl) acrylic acid is an acrylic acid in which a hydrogen atom is bonded to the α-position carbon atom to which the carboxy group is bonded, and an α in which the hydroxyalkyl group is bonded to the α-position carbon atom. -Represents one or both of hydroxyalkyl acrylic acids.
(E) An amino crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group is preferably used as the crosslinking agent because a good photoresist pattern with less swelling can be formed. The blending amount of the crosslinking agent is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
(A) The acid generator is the same as in the second embodiment.

The photoresist composition of the present invention is used in a method for forming a photoresist film on a substrate by spray coating. The spray coating method can be performed using any spray coating apparatus.
The photoresist composition of the present invention is particularly suitable for a method of forming a photoresist film on a substrate having a stepped portion on the surface to be coated by spray coating. The coated surface of the substrate is a surface on which the photoresist composition is coated, and is usually the entire surface of the substrate.
As shown in FIG. 1, the step part 1 in this invention points out the shape where the side surface 1b slanted with respect to these surfaces exists between the upper surface 1a and the bottom face 1c. The upper surface 1a, the side surface 1b, and the bottom surface 1c are flat surfaces.
The step H of the step portion 1 is a distance from the top surface 1a to the bottom surface 1c in a direction perpendicular to the top surface 1a of the step portion 1. In the present invention, the step H of the step portion 1 on the coated surface of the substrate is preferably in the range of 10 to 1000 μm. When the step H is 10 μm or more, the effect of using the photoresist composition of the present invention is sufficiently exhibited.
The angle θ formed by the upper surface 1a and the side surface 1b of the step portion 1 is 90 ° or more. As θ is closer to 90 °, the problem that the film thickness of the photoresist film locally decreases at the corner of the step portion 1 in the conventional photoresist composition becomes more prominent. The range of θ at which the effect of using the photoresist composition of the present invention is sufficiently exerted is preferably 90 ° or more and less than 180 °, more preferably 100 ° or more and less than 180 °.

<Laminated body>
As shown in FIG. 1, in the laminate of the present invention, a photoresist film 2 made of the photoresist composition of the present invention is formed on a substrate provided with a step portion 1 having a step H in the above range on the surface to be coated. Is a laminated body. In the laminate of the present invention, the upper surface 1 a and the side surface 1 b of the step portion 1 are continuously covered with the photoresist film 2.

  In the laminate of the present invention, the thickness of the photoresist film 2 on the upper surface 1a of the step portion 1 is 1 to 40 μm. The film thickness here refers to the film thickness (T1) on the upper surface by a measurement method described later. When the film thickness of the photoresist film 2 is 1 μm or more, the exposure dose margin is excellent, and when it is 40 μm or less, sufficient resolution and adhesion are obtained. A more preferable range of the film thickness of the photoresist film 2 is 1.5 to 20 μm, and 2 to 10 μm is more preferable.

In the laminate of the present invention, the film thickness (T2) at the boundary between the upper surface 1a and the side surface 1b of the step portion 1 is a level of 75% or more of the film thickness (T1) at the upper surface adjacent to the boundary. Good film thickness uniformity is achieved.
In the present invention, the film thicknesses (T1) and (T2) are values obtained by the following procedure using an electron micrograph of the cross section of the stepped portion 1.

First, in the electron micrograph of the cross section of the step portion 1, an extension line L1 of the upper surface 1a of the step portion 1 and an extension line L2 of the side surface 1b of the step portion 1 are determined, and the intersection of L1 and L2 is defined as O.
Next, starting from the point O, at least three measurement points are determined at equal intervals of 30 μm along the upper surface 1a of the step portion 1, and the photoresist film 2 on the upper surface 1a of the step portion 1 at each measurement point is determined. The film thicknesses t1, t2, t3... Are measured. And let the average value of each obtained film thickness t1, t2, t3 ... be "the film thickness (T1) in the upper surface of a step part".
Next, let X be a point on the L1 that is separated from the point O to the outside of the step portion 1 by [(T1) / 2]. A straight line L3 passing through the point X and perpendicular to L1 is provided, and a point where the straight line L3 and the surface of the photoresist film 2 intersect is defined as Y. A straight line L4 passing through the point Y and perpendicular to the straight line L2 is provided.
A point where the straight line L4 intersects the surface of the step portion 1 is Z, and a distance from the point Z to the point Y is “a film thickness (T2) at the boundary portion between the upper surface and the side surface of the step portion”.

  According to the photoresist composition for spray coating of the present invention, the film thickness (T2) can be as good as 75% or more of the film thickness (T1). The ratio [(T2) / (T1)] of the film thickness (T2) to the film thickness (T1) indicates that the uniformity of the film thickness is higher as it is closer to 100%, and more preferably 85% or more. . Although it may slightly exceed 100%, a practical upper limit is 100%.

Here, the present inventors changed the film thickness at the position where the film thickness of the photoresist film is the thinnest at the corner of the step when using a conventional photoresist composition to change the cross-sectional shape and film thickness of the step. Regardless, as a result of conducting many experiments to find a suitable method for unambiguous measurement, as in the above measurement method, outward from the intersection O of the extension lines L1 and L2 [(T1) / 2] Obtained by a method of calculating “film thickness (T2) at the boundary between the upper surface and side surface of the step portion” with the point Y where the perpendicular line L3 of L1 and the surface of the photoresist film 2 intersect at a point X separated by a distance as the measurement position. The values obtained are found to be appropriate in good agreement with the experimentally obtained values.
The starting point for measuring the film thicknesses t1, t2, t3... On the upper surface of the stepped portion and the starting point for determining the point X separated by [(T1) / 2] are the highest at the corner of the stepped portion. Although it is preferable, since the starting point is not uniquely determined when the corner of the step is rounded, the starting point is the intersection O of the extension lines L1 and L2. When the corner of the step is an acute angle and a vertex exists in the cross section, the point O coincides with the vertex.

The laminate of the present invention can be obtained by spray-coating the photoresist composition of the present invention on a surface to be coated of a substrate.
That is, when the photoresist composition of the present invention is used to form a photoresist film by spray coating, the above [(T2) / (T1)] even when a step is provided on the substrate. A photoresist film having an excellent film thickness uniformity of 75% or more can be formed. Further, even when the surface of the substrate is flat, a photoresist film having excellent film thickness uniformity can be formed.
The reason for this is not clear, but by including the above-mentioned specific surfactant in the photoresist composition, a uniform film thickness can be obtained even in uneven portions such as corners of steps in the photoresist film applied on the substrate. It is presumed that a suitable balance of surface tension is obtained so that
Conventionally, it has been known that in a photoresist composition applied by spin coating, a surfactant is added for the purpose of preventing striation from generating streak radially from the center. The effect of improving the flatness of the film and the effect of improving the film thickness uniformity at the step portion in the spray coating method are different effects. That is, the addition of the specific surfactant to the photoresist composition used in the spray coating method improves the film thickness uniformity at the corners of the stepped substrate. It is an effect.

<Photoresist pattern forming method>
A method for forming a photoresist pattern using the laminate of the present invention is not particularly limited, and includes a step of selectively exposing a photoresist film, and a step of forming a photoresist pattern by alkali development of the photoresist film after exposure. The photoresist pattern forming method can be used as appropriate.
For example, a photoresist pattern can be formed by the following procedure.

(Exposure process)
Selective exposure is performed by irradiating the photoresist film of the laminate with actinic rays or radiation, for example, ultraviolet rays or visible rays having a wavelength of 300 to 500 nm through a mask having a predetermined pattern. As these actinic rays or radiation sources, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used.
Here, an actinic ray means a ray that activates an acid generator in order to generate an acid. Radiation means ultraviolet rays, visible rays, far ultraviolet rays, X-rays, electron beams, ion rays, and the like. The irradiation amount of actinic rays or radiation can be appropriately set according to the type of each component in the photoresist composition, the blending amount, the film thickness of the photoresist layer, and the like.
And after performing selective exposure, the acid which generate | occur | produces from an acid generator is diffused moderately by performing heat processing (PEB process) preferably.

(Development process)
After selective exposure, development is performed using an alkaline developer.
When a photoresist film is formed using a positive photoresist composition, the exposed portion of the photoresist film is dissolved and removed by the developer, thereby forming a photoresist pattern.
When a photoresist film is formed using a negative photoresist composition, a photoresist pattern is formed by dissolving and removing an unexposed portion of the photoresist film with a developer.

Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethyl. Ethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4, An aqueous solution of an alkali such as 3,0] -5-nonane can be used, and an aqueous TMAH solution having a concentration of about 0.1 to 10% by mass is preferable.
Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an alkaline aqueous solution can also be used as a developer.

The developing method may be any of dipping method, paddle method, spray developing method and the like.
The development time varies depending on conditions, but is usually about 1 to 30 minutes, for example.
After development, washing with running water is preferably performed for 30 to 90 seconds, and then air-dried using an air gun or the like, or dried in an oven.

  In the laminate of the present invention, a photoresist film having a good film thickness uniformity is formed on a substrate having stepped portions. Therefore, in a photoresist pattern formed using this, Excellent in-plane uniformity of film thickness (height).

Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.
[Synthesis Example 1] <(b2) Synthesis of resin whose solubility in alkali is increased by the action of acid>
A flask equipped with a stirrer, a reflux device, a thermometer, and a dropping tank was purged with nitrogen, and then propylene glycol methyl ether acetate was charged as a solvent and stirring was started. Thereafter, the temperature of the solvent was raised to 80 ° C. After charging 2,2′-azobisisobutyronitrile as a polymerization catalyst and 50% by mass of 1-ethylcyclohexyl methacrylate and 50% by mass of 2-ethoxyethyl acrylate as monomers in a dropping tank and stirring until the polymerization catalyst is dissolved, This solution was uniformly dropped into the flask for 3 hours, followed by polymerization at 80 ° C. for 5 hours. Then, it cooled to room temperature and obtained resin as a (b2) component.
The resin was subjected to a fractionation treatment to obtain two types of resins (b2-1) and (b2-2) having different mass average molecular weights as follows.
(B2-1): Mass average molecular weight 250,000
(B2-2): Mass average molecular weight 350,000

[Synthesis Example 2]
<Synthesis of (c1) novolac resin>
m-cresol and p-cresol were mixed at a mass ratio of 60:40, formalin was added thereto, and condensed by an ordinary method using an oxalic acid catalyst to obtain a cresol novolak resin. The resin was subjected to a fractionation treatment, and the low molecular weight region was cut to obtain a novolak resin having a mass average molecular weight of 15,000. This resin is referred to as (C-1).
[Synthesis Example 3]
<Synthesis of (c2) copolymer having hydroxystyrene structural unit and styrene structural unit>
A resin (C-2) having a mass average molecular weight of 3,000 was obtained in the same manner as in Synthesis Example 1 except that 75% by mass of hydroxystyrene and 25% by mass of styrene were used as monomers.

[Synthesis Example 4] <Synthesis of (c3) acrylic resin>
A resin (C-3 having a mass average molecular weight of 250,000) was prepared in the same manner as in Synthesis Example 1 except that 130 parts by mass of 2-methoxyethyl acrylate, 50 parts by mass of benzyl methacrylate, and 20 parts by mass of acrylic acid were used as monomers. )
[Synthesis Example 5] <Synthesis of (c4) Vinyl Resin>
A methanol solution of poly (vinyl methyl ether) (mass average molecular weight 50,000) (manufactured by Tokyo Chemical Industry Co., Ltd., concentration 50 mass%) was solvent-substituted with propylene glycol monomethyl ether acetate using a rotary evaporator to obtain a concentration of 50 (C-4) was obtained as a mass% solution.

[Examples 1 to 4] <Preparation of chemically amplified positive photoresist composition>
Each component shown in Tables 1 and 2 was mixed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 1 μm. This was diluted with acetone to obtain a chemically amplified positive photoresist composition.
As the acid generator as the component (A), the following two types were used.
(A-1): 2,4-bis (trichloromethyl) -6piperonyl-1,3,5-triazine (A-2): a compound represented by the following chemical formula (VIII) As the surfactant, (E -1): SF8416 (product name, manufactured by Toray Dow Corning) and (E-2): BYK-315 (product name, manufactured by Big Chemie) were used. In addition, although surfactant is provided as a solution, the number in a table | surface is the mass of solid content in the solution of surfactant.

  In Tables 1 and 2, (D-1) represents salicylic acid, and (D-2) represents triethanolamine. In addition, the numerical value in Table 1 represents the mass part of each component. (A-1) (A-2) (b2-1) (b2-2) (C-1) (C-2) (C-3) (C-4) (D-1) (D- 2) (E-1) (E-2) (E-3) is solid content.

[Comparative Examples 1 and 3] <Preparation of Chemically Amplified Positive Photoresist Composition Containing No Surfactant>
A chemically amplified positive photoresist composition was prepared in the same manner as in Examples 1 and 3 except that the surfactant was not added. That is, chemically amplified positive photoresist compositions having the compositions shown in Tables 1 and 2 were obtained.

[Comparative Examples 2 and 4] <Preparation of chemically amplified positive photoresist composition using other surfactant>
A chemically amplified positive photoresist in the same manner as in Examples 1 and 3, except that the surfactant was changed to (E-3): alkylbenzenesulfonic acid ammonium salt (product name: New Coal 210, manufactured by Nippon Emulsifier Co., Ltd.) A composition was prepared. That is, chemically amplified positive photoresist compositions having the compositions shown in Tables 1 and 2 were obtained. In addition, although surfactant is provided as a solution, the number in a table | surface is the mass of solid content in the solution of surfactant.

[Evaluation methods]
The photoresist compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were sprayed on the surface of a substrate having a stepped portion on the surface using a spray coating apparatus (manufactured by SUS MicroTec, product name Delta Alta Spray). A photoresist film was formed by coating.
As the substrate, a substrate in which a silicon layer having a step portion was provided on a 4-inch silicon wafer was used. The top surface, side surface, and bottom surface of the step portion were all flat, the step height H of the step portion was 300 μm, and the angle θ formed by the top surface and the side surface of the step portion was 120 °.
For the obtained photoresist film, the film thickness (T1) on the upper surface of the step portion and the film thickness (T2) at the boundary between the upper surface and the side surface of the step portion are measured by the measurement method described above, and the ratio of T2 to T1 [(T2) / (T1)] (unit%) was determined.

[Evaluation results]
Each of the photoresist films formed using the photoresist compositions of Examples 1 to 4 and Comparative Examples 1 to 4 continuously covered the upper surface and side surfaces of the stepped portion. The measurement results of T1, T2, and [(T2) / (T1)] are shown in Table 3 below.

  From the results of Table 3, in Examples 1 to 4, the value of [(T2) / (T1)] is higher than 75%, and it is recognized that the film thickness uniformity of the photoresist film in the step portion is excellent.

It is sectional drawing which shows the example of the laminated body concerning this invention.

Explanation of symbols

1 Step 2 Photoresist film

Claims (4)

A photoresist composition used in a method of forming a photoresist film on a substrate by spray coating,
A spray coating photoresist composition comprising a modified siloxane-based surfactant.   The photoresist composition for spray coating according to claim 1, wherein a stepped portion is provided on a surface to be coated of the substrate. A laminate in which a photoresist film made of a photoresist composition containing a modified siloxane-based surfactant is formed on a substrate on which a step portion having a step of 10 to 1000 μm is provided on the surface to be coated,
The upper surface and side surfaces of the stepped portion are continuously covered with the photoresist film,
The film thickness of the photoresist film on the upper surface of the step portion is 1 to 40 μm, and the film thickness at the boundary portion between the upper surface and the side surface of the step portion is 75% of the film thickness on the upper surface adjacent to the boundary portion. It is the above, The laminated body characterized by the above-mentioned. The laminate according to claim 3, wherein an angle formed between the upper surface and the side surface of the stepped portion is 90 ° or more and less than 180 °.

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