TW201915036A - Radiation-sensitive resin composition, semiconductor device, display apparatus, cured film and manufacturing method thereof wherein the radiation-sensitive resin composition is excellent in radiation sensitivity and storage stability - Google Patents

Abstract

The present invention provides a radiation-sensitive resin composition excellent in radiation sensitivity and storage stability and capable of obtaining a patterned film with high resolution and low corrosiveness to metal wiring, and also provides a semiconductor device, a display apparatus, a cured film and a manufacturing method thereof. The radiation-sensitive resin composition is characterized by comprising: a polymer component (A) including a structural unit (I) having an aromatic ring and an alkoxysilyl group directly bonded to the aromatic ring, and a structural unit (II) containing an acidic group in the same or different polymer; a radiation-sensitive compound (B); an organic solvent (D); and water (E), wherein the content of the water (E) is 10 wtppm or more and 800 wtppm or less.

Description

Radiation-sensitive linear resin composition, semiconductor element, display device, cured film, and method of manufacturing the same

The present invention relates to a radiation sensitive resin composition and use thereof.

In the semiconductor element, a cured film such as an interlayer insulating film, a spacer, a protective film, or a patterned coloring film (also referred to as a "colored pattern film" in the present specification) for a color filter is usually used. As a material for forming the cured film, the number of steps for forming a patterned cured film (also referred to as "pattern film" in the present specification) is small and a high surface hardness can be obtained. A radiation sensitive resin composition.

As the radiation-sensitive resin composition, for example, a radiation-sensitive resin composition containing a copolymer containing a carboxyl group and an epoxy group is known (see Patent Document 1). Further, a positive photosensitive composition containing a polymer obtained by radically copolymerizing a radical polymerizable monomer having an alkoxyalkyl group and a radical polymerizable monomer having an acidic group is known (refer to the patent literature). 2). [Prior Art Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-354822 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2013-101240

[Problems to be Solved by the Invention] The present inventors have found that a radiation sensitive resin composition containing a polymer component having alkoxyalkylene group directly bonded to an aromatic ring and a radiation sensitive compound is excellent in radiation sensitivity. As the composition, a pattern film having excellent resolution can be obtained. However, in the composition, there are cases where storage stability and corrosiveness to metal wiring are problematic.

A problem of the present invention is to provide a radiation-sensitive resin composition, a pattern film, a method for producing the same, a semiconductor device, and a display which are excellent in radiation sensitivity and storage stability and which have high resolution and low corrosivity to metal wiring. Device. [Technical means to solve the problem]

The present inventors have made diligent research in order to solve the above problems. As a result, it was found that the above problem can be solved by the radiation sensitive resin composition having the following constitution, and the present invention has been completed.

The present invention relates to the following [1] to [11], for example. [1] A radiation sensitive resin composition comprising: a polymer component (A) having an aromatic ring and an alkoxydecane directly bonded to the aromatic ring in the same or different polymer a structural unit (I) and a structural unit (II) containing an acidic group; a radiation sensitive compound (B); an organic solvent (D); and water (E); and the content of the water (E) is 10 wtppm Above, 800 wtppm or less. [2] The radiation sensitive resin composition according to [1], wherein the content of the water (E) is 550 wtppm or less. [3] The radiation sensitive resin composition according to [1] or [2] wherein the content of the water (E) is 250 wtppm or less. [4] The radiation sensitive resin composition according to any one of [1] to [3] wherein the polymer component (A) has and is selected from the structural unit (I) and The polymer of the same or different polymer of at least one structural unit in the structural unit (II) further has a structural unit (III) having a crosslinkable group. [5] The radiation sensitive resin composition according to any one of [1] to [4] wherein the structural unit (I) is a substituted or unsubstituted benzene ring or a naphthalene ring. Or an anthracene ring and a group represented by -SiR ₃ bonded directly to the ring (the R is independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an aryl group or an alkoxy group; A structural unit in which at least one of R is an alkoxy group. [6] The radiation sensitive resin composition according to any one of [1] to [5] which is a positive type. [7] A patterned cured film formed of the radiation sensitive resin composition according to any one of [1] to [6]. [8] The patterned cured film according to [7], which is an interlayer insulating film. [9] A method of producing a patterned cured film, comprising the step (1) of forming a coating of the radiation sensitive resin composition according to any one of [1] to [6] on a substrate. a film; a step (2) of irradiating a part of the coating film with radiation; a step (3) of developing the film irradiated with radiation; and a step (4) of heating the developed film . [10] A semiconductor element comprising the patterned cured film according to [7] or [8]. [11] A display device comprising the semiconductor element according to [10]. [Effects of the Invention]

According to the present invention, it is possible to provide a radiation-sensitive resin composition, a pattern film, a method for producing the same, a semiconductor device, and a display which are excellent in radiation sensitivity and storage stability and which have high resolution and low corrosivity to metal wiring. Device.

Hereinafter, a method for carrying out the present invention will be described. [The radiation sensitive resin composition] The radiation sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") includes a polymer component (A). a structural unit (I) having an aromatic ring and an alkoxyalkyl group directly bonded to the aromatic ring and a structural unit (II) having an acidic group in the same or different polymer; a radioactive compound (B); organic solvent (D); and water (E).

<Polymer component (A)> The polymer component (A) has a structural unit (I) and a structural unit (II) in the same or different polymer. The structural unit (I) and the structural unit (II) may be contained in the same polymer or in different polymers, respectively.

<<Structural unit (I)>> The structural unit (I) contains an aromatic ring and an alkoxyalkyl group directly bonded to the aromatic ring. The alkoxyalkylalkyl group directly bonded to the aromatic ring means that the fluorene atom in the alkoxy fluorenyl group is bonded to the ring carbon atom of the aromatic ring.

When a radioactive acid generator (to be described later) is used as the radiation sensitive compound (B), the composition of the present invention can exhibit high sensitivity positive radiation characteristics by the structural unit (I). The reason is presumed to be as follows. The structural unit (I) contains an alkoxyalkyl group directly bonded to an aromatic ring. When the coating film of the composition of the present invention is irradiated with radiation, stanol is produced from an alkoxyalkyl group by hydrolysis reaction with water in the atmosphere or in a developing solution using an acid generated by a self-inductive radioactive acid generator as a catalyst. Base (Si-OH). Since the stanol group is bonded to the aromatic ring, the condensation reaction of the stanol group is hindered, so that the stanol group can be stably present. Therefore, the solubility of the radiation irradiation region with respect to the alkaline developer is improved by the stanol group. As described above, the composition of the present invention can exhibit positive radiation characteristics. On the other hand, in the case where the alkoxyalkyl group is not directly bonded to the aromatic ring, the formed stanol group is unstable and condensation to the oxirane is generated. Therefore, the radiation irradiation region is insolubilized (negative), and the positive radiation characteristics are not exhibited. Further, when the structural unit (I) contains an aromatic ring, various properties such as heat resistance of the obtained pattern film can be further improved.

In the case where a radioactive linear alkali generating agent to be described later is used as the radiation sensitive compound (B), the composition of the present invention can exhibit a high sensitivity negative radiation characteristic by the structural unit (I). It is presumed that the reason is that when the coating film of the composition of the present invention is irradiated with radiation, the alkali generated by the self-inductive radioactive alkali generating agent becomes a catalyst to form a polyoxyalkylene oxide.

The structural unit (I) may be a structural unit or a plurality of structural units. The alkoxyalkyl group is preferably a group represented by -SiR ₃ . The R is independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an aryl group or an alkoxy group. Wherein at least one, preferably at least two, more preferably all three of said R are alkoxy groups. In the structural unit (I), the number of alkoxyalkyl groups directly bonded to the aromatic ring is usually from 1 to 9, preferably from 1 to 7, more preferably from 1 to 5, still more preferably 1.

Examples of the aromatic ring to which the alkoxyalkylene group is directly bonded include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.

A substituent other than the alkoxyalkyl group may be bonded to the aromatic ring. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, and an alkoxy group. The substituent may be one type or two or more types, and may be one or plural.

Hereinafter, each of R and a substituent will be described. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, and a third butyl group. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms. More preferably, it is a methyl group.

Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 10. Examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, and an isopropoxy group. The alkoxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. More preferably, it is a methoxy group and an ethoxy group, and further more preferably a methoxy group.

As the group other than the alkoxy group in R, an alkyl group or a hydroxyl group is preferred. The group represented by -SiR ₃ is specifically a trimethoxydecyl group, a triethoxydecyl group, a tripropoxydecyl group, a dimethoxyhydroxydecyl group, or a dimethoxymethyl group. Alkyl group, diethoxyethyl decyl group, methoxy dimethyl decyl group. As the structural unit (I), for example, a structural unit represented by the formula (1) can be cited.

[Chemical 1] In the formula (1), R ^A is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group or a trifluoromethyl group, preferably a hydrogen atom or a methyl group. R ¹ is an aromatic ring to which an alkoxyalkyl group is directly bonded, and the aromatic ring is bonded to X. X is a single bond or a divalent organic group.

Examples of the divalent organic group include a divalent hydrocarbon group such as a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. An ester bond (-COO-), a group in which the divalent hydrocarbon group is bonded to an oxy group (-O-), and a group in which these groups are combined.

X is preferably a single bond and -COO-* (* represents a bonding position with an aromatic ring in R ¹ ), and more preferably a single bond. The structural unit (I) may, for example, be a structural unit represented by the formula (I-1) to the formula (I-20).

[Chemical 2] In the formula (I-1) ~ of formula (I-20), meaning the same as the formula R ^A (1) R ^A.

<<Structural unit (II)>> The structural unit (II) has an acidic group. For example, the polymer component (A) may have a structural unit (II) in the same or different polymer as the polymer having the structural unit (I). The structural unit (II) may be a structural unit or a plurality of structural units. By the structural unit (II), the solubility of the polymer component (A) with respect to the developer can be improved, or the hardening reactivity can be improved.

The acid dissociation constant as the acidic group is, for example, preferably pKa ≦ 12, more preferably pKa ≦ 10, and still more preferably pKa ≦ 8. Examples of the acidic group include, for example, at least one of a hydrogen atom selected from a hydrogen atom bonded to a carbon atom substituted with an electron withdrawing group, and at least one hydrogen atom bonded to a nitrogen atom is substituted as a pull electron. At least one of an amino group, a carboxyl group, a sulfo group, a phenolic hydroxyl group, a phosphoric acid group, a sulfonic acid group, a phosphinic acid group, and a sulfonylamino group. Examples of the electron withdrawing group include a halogen atom such as a fluorine atom or a chlorine atom, a nitro group, a cyano group, and a carbonyl group. The acidic group is preferably at least one selected from the group consisting of a hydroxyfluorinated alkyl group, a maleidino group, a carboxyl group, a sulfo group, a phenolic hydroxyl group, a phosphoric acid group, a sulfonic acid group, and a phosphinic acid group, and more preferably It is at least one selected from the group consisting of a hydroxyfluorinated alkyl group, a maleidino group, a carboxyl group, and a sulfo group. The acid dissociation constant can be determined by providing the acid group in the unitary body of the structural unit (II) in the form of an acid dissociation constant in water (H ₂ O) at 25 ° C.

The hydroxyfluorinated alkyl group is preferably a group represented by the formula (2): -C(R ² )(R ³ )OH. In the above formula, R ² is a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. R ³ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms. The group can exhibit particularly good developability or good crosslinking reactivity with a crosslinkable group in the structural unit (III) to be described later.

Examples of the fluorinated alkyl group having 1 to 4 carbon atoms include difluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetra. Fluoropropyl, perfluoroethylmethyl, 2,2,3,3,4,4-hexafluorobutyl; trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, etc. alkyl.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, and a third butyl group.

R ^{2 is} preferably a fluorinated alkyl group having 1 to 4 carbon atoms, more preferably a perfluoroalkyl group, and still more preferably a trifluoromethyl group. R ^{3 is} preferably a hydrogen atom, a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom and the fluorinated alkyl group, and still more preferably the fluorinated alkyl group. Further preferred is a perfluoroalkyl group, particularly preferably a trifluoromethyl group. In this manner, since it becomes a suitable acidic group, a favorable crosslinking reaction is produced, and the characteristics of the pattern film obtained by chemical resistance etc. are further improved. Examples of the hydroxyl group-containing fluorinated alkyl group-containing monomer include 1,1,1,3,3,3-hexafluoro-2-(4-vinylphenyl)-propan-2-ol.

Examples of the structural unit (II) include a structural unit derived from an unsaturated carboxylic acid, a structural unit derived from maleimide, and a structural unit derived from vinyl sulfonic acid. Examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, itaconic acid, citraconic acid, and fumaric acid. Unsaturated dicarboxylic acid such as meconic acid; mono[2-(methyl)propenyloxyethyl] succinate, mono[2-(methyl)propenyloxyethyl] phthalate, etc. The mono[(meth)acryloxyalkylalkyl] ester of a divalent or higher polycarboxylic acid is preferably an unsaturated monocarboxylic acid, more preferably (meth)acrylic acid.

In one embodiment, the unsaturated carboxylic acid is preferably an unsaturated carboxylic acid having no aromatic ring from the viewpoint of alkali developability, that is, for example, preferably not 4-vinylbenzoic acid and 4- An aromatic unsaturated carboxylic acid such as vinyl phenylpropionic acid. In the case of an aromatic unsaturated carboxylic acid, there is a case where a p-p accumulation phenomenon occurs by the structural unit (I) and the structural unit (II), and it is difficult to develop alkali developability.

<<Structural unit (III)>> The polymer component (A) preferably further has a structural unit (III) having a crosslinkable group. For example, the polymer component (A) may have a structural unit (III) in the same or different polymer as the polymer having the structural unit (I) and/or the structural unit (II). The structural unit (III) may be a structural unit or a plurality of structural units. The hardening reactivity or the heat resistance of the obtained pattern film can be improved by the structural unit (III).

The crosslinkable group refers to a group other than the alkoxyalkyl group and the acidic group, and is, for example, a group which can react with the same group (for example, an epoxy group) to form a covalent bond under heating. Examples of the crosslinkable group include an epoxy group such as an oxyheteropropyl group (1,2-epoxy structure) or an oxetanyl group (1,3-epoxy structure), a cyclic carbonate group, and the like. Hydroxymethyl, (meth) acrylonitrile, vinyl. Among these, an isopropylidene group, an oxetanyl group, and a hydroxymethyl group are preferable, an oxacyclopropyl group and an oxetanyl group are more preferable, and an oxacyclopropyl group is further more preferable.

The structural unit (III) containing an oxopropyl group may, for example, be a structural unit represented by the formula (III-1) to the formula (III-7) or the formula (III-18). The structural unit (III) containing an oxetanyl group is, for example, a structural unit represented by the formula (III-8) to the formula (III-11). The structural unit (III) containing a cyclic carbonate group is, for example, a structural unit represented by the following formula (III-12) to formula (III-16). The structural unit (III) containing a methylol group may, for example, be a structural unit represented by the formula (III-17).

[Chemical 3] In the formula (III-1) to the formula (III-18), R ^C is a hydrogen atom, a methyl group or a trifluoromethyl group.

Examples of the structural unit (III) containing a (meth)acrylonitrile group include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(II). Methyl)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol diacrylate, etc. (meth) acrylate compound; tris(2-hydroxyethyl)isocyanurate tri(meth) acrylate, trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate a tris(meth)acrylate compound such as a pentaerythritol tetra(meth)acrylate; a penta(meth)acrylate compound such as dipentaerythritol penta(meth)acrylate; Structural unit.

The structural unit (III) containing a (meth) acrylonitrile group or a vinyl group may, for example, be a structural unit obtained by reacting an epoxy group-containing unsaturated compound with a structural unit containing a carboxyl group, and (meth) a structural unit obtained by reacting acrylic acid with a structural unit containing an epoxy group, a structural unit obtained by reacting a (meth) acrylate or vinyl compound containing an isocyanate group with a structural unit containing a hydroxyl group, and (meth)acrylic acid A structural unit obtained by reacting with a structural unit containing an acid anhydride.

<<Structural unit (IV)>> The polymer component (A) may further have a structural unit (IV) other than the structural unit (I) to the structural unit (III). For example, the polymer component (A) may have a structural unit (IV) in a polymer which is the same as or different from the polymer having any one of the structural unit (I) to the structural unit (III). The structural unit (IV) may be a structural unit or a plurality of structural units. The glass transition temperature of the polymer component (A) can be adjusted by the structural unit (IV), and the melt flow property at the time of thermosetting or the mechanical strength and chemical resistance of the obtained pattern film can be improved.

Examples of the monovalent body which provides the structural unit (IV) include (meth)acrylic acid chain alkyl ester, (meth)acrylic acid alicyclic ester, (meth)acrylic acid aryl ester, and N-substituted horse. The imide compound, the unsaturated dicarboxylic acid diester, the unsaturated aromatic compound, and, in addition, a bicyclic unsaturated compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton or a pyran skeleton, may also be mentioned. Compounds, other unsaturated compounds.

Examples of the (meth)acrylic chain alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and second butyl (meth)acrylate. , tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, tridecyl (meth)acrylate Ester, n-stearyl (meth)acrylate.

Examples of the (meth)acrylic acid-containing alicyclic ester ester include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and trimethyl (meth)acrylate [5.2.1.0 ^{2 , 6} ]decane-8-yl ester, trimethyl [meth)acrylate [5.2.1.0 ^2,6 ]decane-8-yloxyethyl ester, isobornyl (meth)acrylate.

Examples of the aryl (meth)acrylate include phenyl (meth)acrylate and benzyl (meth)acrylate. Examples of the N-substituted maleimide compound include N-alkane such as N-methylmaleimide, N-ethylmaleimide, and N-t-butylmaleimide. Substituted maleimide; N-cycloalkylmaleimide such as N-cyclohexylmaleimide substituted maleimine; N-phenyl maleimide, N-benzyl maleimide, An N-aromatic ring-containing group such as N-(9-acridinyl)maleimide or N-hydroxyphenylmaleimide is substituted for maleimide.

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconate. Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, vinyltoluene, p-methoxystyrene, and α-methyl-p-hydroxystyrene. Examples of the other unsaturated compound include (meth)acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, and vinyl acetate.

Among these, as the structural unit (IV), it is preferably derived from a (meth)acrylic chain alkyl ester, a (meth)acrylic acid containing alicyclic ester, an N-substituted maleimide compound, and an unsaturated aromatic compound. A structural unit of a family compound.

<<Content ratio of each structural unit>> The lower limit of the content ratio of the structural unit (I) to all the structural units in the polymer component (A) is preferably 10% by mass, more preferably 20% by mass, and furthermore It is preferably 25% by mass. On the other hand, the upper limit thereof is preferably 80% by mass, more preferably 70% by mass, still more preferably 60% by mass. According to this aspect, the composition of the present invention can exhibit more excellent radiation characteristics and can further improve the heat resistance of the obtained pattern film.

The lower limit of the content ratio of the structural unit (II) to all the structural units in the polymer component (A) is preferably 3% by mass, more preferably 5% by mass, still more preferably 7% by mass; The upper limit thereof is preferably 50% by mass, more preferably 40% by mass, and still more preferably 30% by mass. According to this aspect, the composition of the present invention can exhibit more excellent radiation characteristics and can further improve various characteristics and the like of the obtained pattern film.

In the case where the polymer component (A) has the structural unit (III), the lower limit of the content ratio of the structural unit (III) to all the structural units in the polymer component (A) is preferably 5% by mass, more preferably It is preferably 10% by mass, and more preferably 20% by mass; and as the upper limit thereof, it is preferably 70% by mass, and more preferably 60% by mass. In this manner, the composition of the present invention can further improve the radiation characteristics or the characteristics of the obtained pattern film in a well-balanced manner.

In the case where the polymer component (A) has the structural unit (IV), the lower limit of the content ratio of the structural unit (IV) to all the structural units in the polymer component (A) is preferably 5% by mass, more preferably It is preferably 10% by mass; and as the upper limit thereof, it is preferably 50% by mass, and more preferably 40% by mass. In this way, chemical resistance and the like can be effectively improved.

The polymer component (A) may contain, for example, a polymer or two or more types of polymers as long as the content of each structural unit measured by nuclear magnetic resonance (NMR) analysis satisfies the requirements. . In the case where two or more types of polymers are contained (blend), the content ratio (measured value) of each structural unit with respect to the entire blend may satisfy the requirements.

Examples of the polymer component (A) include a copolymer having a structural unit (I) and a structural unit (II); a mixture of a polymer having the structural unit (I) and a polymer having the structural unit (II); a copolymer having structural unit (I), structural unit (II) and structural unit (III); a mixture of a copolymer having structural unit (I) and structural unit (II) and a polymer having structural unit (III); a mixture of a polymer having structural unit (I) and a copolymer having structural unit (II) and structural unit (III); a polymer having structural unit (I), a polymer having structural unit (II), and having a structure a mixture of polymers of unit (III). The polymer or copolymer may also have a structural unit (IV). Further, when it is a copolymer having a structural unit (I) and a structural unit (II), it means that the same polymer has a structural unit (I) and a structural unit (II). The same applies to other copolymers.

Further, a copolymer having the structural unit (I) and the structural unit (II) and a mixture of the copolymer having the structural unit (II) and the structural unit (III) may be contained in different polymers in the same polymer. By. The copolymer may also have a structural unit (IV).

The polymer component (A) is preferably a copolymer having a structural unit (I) and a structural unit (II), and more preferably has a structural unit (I), a structural unit (II) and a structural unit (III). The copolymer is more preferably a copolymer having a structural unit (I), a structural unit (II), a structural unit (III) and a structural unit (IV). Further, from the viewpoint of storage stability, the copolymer having the structural unit (I) and the structural unit (II) is superior to the mixture of the polymer having the structural unit (I) and the polymer having the structural unit (II). In the case of other mixtures, the copolymer having the corresponding structural unit is superior to the mixture in terms of storage stability.

<<Synthesis Method of Polymer Component (A)>> The polymer component (A) can be produced, for example, by using a radical polymerization initiator to make a monomer amount corresponding to each predetermined structural unit in a suitable polymerization solvent. Polymerization is carried out. Further, in general, the blending ratio of each individual body at the time of polymerization is the same as the content ratio of the corresponding structural unit in the obtained polymer component (A). Further, as the polymer component (A), a plurality of polymers may be separately synthesized, and thereafter, these various polymers may be used in combination.

The polymerization temperature can usually be set to 30 ° C to 180 ° C. The polymerization time is usually from 30 minutes to 8 hours. Examples of the radical polymerization initiator include azobisisobutyronitrile (AIBN) and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-A Propionitrile). The radical polymerization initiators may be used alone or in combination of two or more.

The polymerization solvent is exemplified as the organic solvent exemplified as the organic solvent (D) to be described later. The polymerization solvent may be used singly or in combination of two or more. In the case where the polymerization solvent is the same as the organic solvent (D) in the prepared radiation sensitive resin composition, the polymer solution obtained by the polymerization may be used as it is or may be added to the obtained polymer solution. The organic solvent (D) is supplied to the preparation of the radiation sensitive resin composition. In this case, in order to reduce the content of the water (E) in the obtained composition, an organic solvent dried by the method described later may be used as the polymerization solvent.

<<Physical properties and content ratio of the polymer component (A)>> The weight average molecular weight (Mw) in terms of polystyrene obtained by a colloidal osmosis chromatography (GPC) method of the polymer component (A) is preferably 1,000. ~30,000. Further, the ratio (Mw/Mn) of the Mw of the polymer component (A) to the number average molecular weight (Mn) in terms of polystyrene obtained by the GPC method is preferably from 1 to 3.

The lower limit of the content of the polymer component (A) in all the solid components of the composition of the present invention is preferably 50% by mass, more preferably 70% by mass, still more preferably 90% by mass; Preferably, it is 99% by mass, more preferably 97% by mass. In this manner, the composition of the present invention can more effectively improve the radiation characteristics or the characteristics (for example, resolution) of the obtained pattern film. In addition, all solid components mean all components other than the organic solvent (D) and water (E).

<The radiation sensitive compound (B)> The radiation sensitive compound (B) (hereinafter also referred to as "component (B)")) is, for example, a radioactive acid which is a compound which generates an acid by a treatment including radiation irradiation. A generator, a radiation-sensitive alkali generator which is a compound which generates a base by a treatment including radiation irradiation, is preferably the acid generator. Examples of the radiation include ultraviolet rays, far ultraviolet rays, visible rays, X rays, and electron beams. As the treatment, only the radiation component is irradiated depending on the type of the component (B), and a water contact treatment may be required.

By irradiating the coating film formed of the composition of the present invention with a radiation irradiation treatment or the like, an acid or a base is generated in the irradiation portion based on the component (B), and the polymer component (A) is alkali-developed based on the action of the acid or the alkali. The solubility in the liquid changes.

Examples of the radiation-sensitive acid generator include an oxime sulfonate compound, a phosphonium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, an anthraquinone compound, a sulfonate compound, and a carboxylate compound. , bismuth azide compound.

Specific examples of the oxime sulfonate compound, sulfonium salt, sulfonimide compound, halogen-containing compound, diazomethane compound, hydrazine compound, sulfonate compound, and carboxylate compound include, for example, Japanese Patent Laid-Open The compounds described in paragraphs [0078] to [0106] of the publication No. 2014-157252, or the international publication No. 2016/124493, are described in the present specification. Further, these acid generators and quinonediazide compounds may also be used in combination.

The oxime sulfonate compound is exemplified, for example, (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octyl) Sulfomethoxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-A Phenyl phenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (2-[2-(4-methylbenzene) Alkylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene-2-(2-methylphenyl)acetonitrile), 2-(octylsulfonyloxyimino)-2 -(4-Methoxyphenyl)acetonitrile. As a specific example, Irgacure PAG121 manufactured by BASF Corporation can be mentioned.

The sulfonimide compound is exemplified, and examples thereof include N-(trifluoromethylsulfonyloxy) succinimide, N-(camphorsulfonyloxy) succinimide, and N-(4-A). Phenyl sulfonyloxy) succinimide, N-(2-trifluoromethylphenylsulfonyloxy) succinimide, N-(4-fluorophenylsulfonyloxy) amber Amine, N-(trifluoromethylsulfonyloxy) phthalimide, N-(camphorsulfonyloxy) phthalimide, N-(2-trifluoromethylphenyl) Sulfomethoxy) phthalimide, N-(2-fluorophenylsulfonyloxy) phthalimide, N-(trifluoromethylsulfonyloxy)diphenyl醯imine, N-(camphorsulfonyloxy)diphenylmaleimide, 4-methylphenylsulfonyloxydiphenylmaleimide, trifluoromethanesulfonic acid-1, 8-naphthoquinone imine.

Examples of the quinonediazide compound include a naphthoquinonediazide compound, and a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinonediazidesulfonium halide or 1,2-naphthoquinone A condensate of sulfoxamide.

Specific examples of the compound having one or more phenolic hydroxyl groups include the compounds described in paragraphs [0065] to [0070] of JP-A-2014-186300, and these compounds are described in the present specification. . As the 1,2-naphthoquinonediazidesulfonium halide, preferably 1,2-naphthoquinonediazidesulfonium chloride, more preferably 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride. As the 1,2-naphthoquinonediazidesulfonamide, 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonamide is preferred.

Specific examples of the quinonediazide compound include, for example, 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, and tris(p-hydroxyl group). Phenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-( 4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-( 4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methyl-ethyl a compound of phenyl]ethylidene]bisphenol, an ester compound with 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl chloride .

As the radiation-sensitive alkali generating agent, an alkali generating agent which generates an amine by radiation irradiation is preferred. Examples of the amine include an aliphatic amine and an aromatic amine, and may be any of a monofunctional amine and a polyfunctional amine.

Examples of the base generator which generates an amine by radiation irradiation include an o-nitrobenzyl carbamate compound and an α,α-dimethyl-3,5-dimethoxybenzylcarbamate compound. Other carbamate compounds, decyloxyimino compounds, cobalt amine complexes. Specific examples of the alkali generating agent that generates an amine by radiation irradiation include, for example, paragraphs [0104] to [0105] of JP-A-H99-097378, and JP-A-2017-133006. The compounds described in 0045 are described in the present specification.

Specific examples of the radiation-sensitive alkali generating agent include [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine and N-(2-nitrobenzyloxycarbonyl). Pyrrolidine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, N-(2-nitrobenzyloxy)carbonyl-N-cyclohexylamine, 9 - mercaptomethyl N,N-diethylcarbamate, 9-fluorenylmethyl N-cyclohexylcarbamate, 9-fluorenylmethyl N,N-dicyclohexylcarbamate, O-carbamyl hydroxy decylamine, O-carbamyl hydrazine, 4-(methylthiobenzylidene)-1-methyl-1-morpholinoethane, (4-morpholinobenzene) Mercapto)-1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone.

The component (B) may be used alone or in combination of two or more. In the composition of the present invention, the content of the component (B) is usually 0.05 parts by mass to 30 parts by mass, preferably 0.05 parts by mass to 26 parts by mass, more preferably 100 parts by mass based on 100 parts by mass of the polymer component (A). It is 0.05 parts by mass to 20 parts by mass.

<Intimate Aid (C)> The adhesion aid (C) (hereinafter also referred to as "component (C)") is a component that improves the adhesion between the obtained pattern film and the substrate. The component (C) preferably has a reactive function such as a carboxyl group, a (meth)acryloyl group, a vinyl group, an isocyanate group, an isocyanurate group, an oxiranyl group, an oxetanyl group or a fluorenyl group. a functional decane coupling agent. Examples of the functional decane coupling agent include trimethoxydecyl benzoic acid, 3-(methyl) propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, and vinyl trimethoxy. Decane, 3-isocyanate propyl triethoxy decane, tris-(trimethoxydecylpropyl) isocyanurate, 3-glycidoxypropyl trimethoxy decane, 2-(3,4- Epoxycyclohexyl)ethyltrimethoxydecane, 3-ethyl-3-oxetanylmethoxypropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane.

The component (C) may be used alone or in combination of two or more. The content of the component (C) in the composition of the present invention when the component (C) is used is preferably 0.1 part by mass to 10 parts by mass based on 100 parts by mass of the polymer component (A).

<Other components> The composition of the present invention may further contain other components than the polymer component (A) and the component (B). The other component is, for example, at least one selected from the group consisting of an antioxidant, a surfactant, a crosslinkable compound, and a polymerization initiator.

In the composition of the present invention, the upper limit of the total content of the components other than the polymer component (A), the component (B) and the component (C) in all the solid components is preferably 20% by mass, more preferably It is preferably 15% by mass, and more preferably 10% by mass.

<Organic solvent (D)> As the organic solvent (D), an organic solvent in which each component contained in the composition of the present invention is uniformly dissolved or dispersed and does not react with the respective components can be used.

Examples of the organic solvent (D) include isopropanol, butanol, isoamyl alcohol, octanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and propylene glycol monomethyl. Alcohol solvent such as ether; butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, 3-ethoxypropyl An ester solvent such as ethyl acetate; an ether solvent such as ethylene glycol ethyl methyl ether or diethylene glycol methyl ethyl ether; a guanamine solvent such as N,N-dimethylacetamide or N-methylpyrrolidone; A ketone solvent such as methyl isobutyl ketone or cyclohexanone; or an aromatic hydrocarbon solvent such as toluene or xylene.

The organic solvent (D) may be used alone or in combination of two or more. The content of the organic solvent (D) in the composition of the present invention is usually 5% by mass to 95% by mass, preferably 10% by mass to 90% by mass, and more preferably 15% by mass to 85% by mass.

<Water (E)> The composition of the present invention contains water (E). The content of water (E) in the composition of the present invention is 800 wtppm or less, preferably 550 wtppm or less, more preferably 250 wtppm or less. Further, the content of water (E) is 10 wtppm or more, preferably 15 wtppm or more, more preferably 20 wtppm or more, and still more preferably 200 wtppm or more. The content of water (E) can be determined using a Kcal Fisher moisture meter. When the content of the water (E) is at most the above upper limit, the storage stability, the metal wiring corrosion resistance, and the post-coating delay (PCD) margin described later are excellent. When the content of the water (E) is less than the lower limit, the radiation sensitivity is lowered, and the Post Exposure Delay (PED) margin to be described later tends to be small.

Further, when a large amount of water (E) is present in the composition of the present invention, the storage stability of the composition and the adhesion to the substrate are lowered, and for example, when the composition is applied to the metal wiring. Next, there is a case where the metal wiring is easily corroded. The reason for the corrosion is considered to be that the water (E) acts as a medium for the radiation-sensitive acid generator and the metal wiring, whereby the metal wiring is corroded.

In the composition of the present invention, the content of the water (E) is 800 wtppm or less, so that the storage stability of the composition and the adhesion to the substrate are high, and for example, the metal wiring coated with the composition is corrosive, that is, formed of a composition. The metal wiring of the insulating film is less corrosive.

<Method for Producing Radiation-Resistant Resin Composition> The composition of the present invention is, for example, a mixture of a polymer component (A), a component (B), and an optional component (C) and other components in a predetermined ratio and dissolved in an organic solvent. Prepared in solvent (D). The prepared radiation sensitive resin composition is preferably filtered by, for example, a filter having a pore size of about 0.2 μm.

The content of water (E) in the composition of the present invention also includes the amount of water derived from water contained in a raw material such as an organic solvent (D). In order to set the content of the water (E) in the composition of the present invention to 800 wtppm or less, for example, an organic solvent dried by a molecular sieve or an organic solvent which is distilled and dried using calcium hydride is used, and orthoformic acid is used. A method in which a methyl ester is subjected to a distillation-dried organic solvent as an organic solvent (D); a method of azeotropically dehydrating a component containing a solid component or a obtained component using an organic solvent such as toluene; and a method of performing vacuum distillation. Further, the polymer component (A) may be dried by drying under reduced pressure.

<Application of Radiation-Sensitive Resin Composition> The composition of the present invention exhibits excellent radiation-sensing properties, is excellent in radiation sensitivity, and is excellent in storage stability. By using the composition, a pattern film having high resolution, low corrosivity to metal wiring, and excellent adhesion to a substrate can be obtained. In particular, the Post Coating Delay (PCD) margin and the Post Exposure Delay (PED) margin described in the examples of the composition described later are large, and the defect rate of the pattern film can be lowered and improved. Good yield and excellent manufacturing workability.

Therefore, the composition can be suitably used as a material for forming a cured film for a semiconductor element such as an interlayer insulating film, a separator, a protective film, or a coloring pattern film for a color filter, in particular, a material for forming an interlayer insulating film. As the semiconductor element, for example, a display element can be cited.

[Pattern Film] The pattern film of the present invention is formed of the composition of the present invention. Examples of the pattern film include a cured film for a semiconductor element such as an interlayer insulating film, a separator, a protective film, and a colored pattern film for a color filter. As a method of producing the pattern film, the following production method is preferable. The film thickness of the pattern film is usually from 0.1 μm to 10 μm, preferably from 0.5 μm to 5 μm, and more preferably from 0.5 μm to 3 μm.

[Method for Producing Pattern Film] The method for producing a pattern film of the present invention comprises the steps of: (1) forming a coating film of the composition of the present invention on a substrate; and (2), irradiating a part of the coating film with radiation; Step (3), developing the coating film irradiated with radiation; and step (4), heating the developed coating film.

<Step (1)> In the step (1), a coating film is formed on the substrate by using the composition of the present invention. Specifically, the solution-like composition is applied onto the surface of the substrate, preferably pre-baked, thereby removing the organic solvent (D) to form a coating film.

Examples of the substrate include a glass substrate, a tantalum substrate, a plastic substrate, and a substrate in which various metal thin films are formed on the surfaces thereof. Examples of the plastic substrate include resin substrates including plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, polyimine, and polycycloolefin. In order to improve the adhesion to the coating film, the substrate may be subjected to a hydrophobized surface treatment such as Hexamethyl Disilazane (HMDS) treatment.

Examples of the coating method include a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, and an inkjet method. The pre-baking conditions vary depending on the type and content ratio of each component, and may be, for example, about 60 to 130 ° C for about 30 seconds to 10 minutes. The film thickness of the formed coating film is preferably from 0.1 μm to 10 μm in terms of the value after prebaking.

<Step (2)> In the step (2), a part of the coating film is irradiated with radiation. Specifically, the coating film formed in the step (1) is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, visible rays, X rays, and electron beams. Examples of the ultraviolet rays include a g-ray (wavelength 436 nm), an h-ray (wavelength 405 nm), and an i-ray (wavelength 365 nm). Among these radiations, ultraviolet rays and ultraviolet rays are more preferable, and radiation containing at least one of g-rays, h-rays, and i-rays is more preferable. The exposure amount of the radiation is preferably from 0.1 J/m ² to 10,000 J/m ² . In order to achieve high sensitivity, the coating film may be wetted with a liquid such as water before the radiation irradiation.

Further, in the case of using a negative-type radiation sensitive resin composition, heat treatment may be performed after radiation irradiation. Hereinafter, the process is also referred to as "Post Exposure Bake (PEB) process". The PEB condition varies depending on the type of each component in the radiation-sensitive linear resin composition, the blending ratio, the thickness of the resin film, and the like, and is usually carried out at 70 ° C to 150 ° C, preferably 80 ° C to 120 ° C for 1 minute to 60 ° C. Minutes or so.

<Step (3)> In the step (3), the coating film irradiated with radiation is developed. Specifically, the coating film irradiated with radiation in the step (2) is developed using a developing solution, and when it is a positive type, the irradiated portion of the radiation is removed, and when it is a negative type, the radiation is not irradiated. Partially removed. In order to achieve high sensitivity, the coating film may be wetted with a liquid such as water before development.

The developer is usually an alkaline developer, and for example, an aqueous solution of a basic compound can be mentioned. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylamine ethanol, and di-n-propylamine. Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, acridine, 1,8-diazabicyclo[5.4.0 ]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene. The concentration of the basic compound in the aqueous solution is, for example, 0.1% by mass to 10% by mass. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution or an alkaline aqueous solution containing a small amount of various organic solvents capable of dissolving the radiation sensitive resin composition may be used. Developer solution.

Examples of the development method include a liquid coating method, a dipping method, a shaking dipping method, and a shower method. The development temperature and the development time can be, for example, 20 to 30 ° C and 30 to 120 seconds, respectively.

Further, it is preferred that the patterned coating film is subjected to a rinsing treatment by running water after development. In addition, the entire surface may be irradiated with radiation (post exposure) by a high pressure mercury lamp or the like to perform decomposition treatment of the radiation sensitive compound (B) remaining in the coating film. The exposure amount in the post-exposure is preferably 2,000 J/m ² to 10,000 J/m ² .

<Step (4)> In the step (4), the developed coating film is heated. Thereby, the hardening reaction of the polymer component (A) can be promoted to form a cured film. As the heating method, for example, a method of heating using a heating device such as an oven or a hot plate can be mentioned. The heating temperature is, for example, 120 ° C to 250 ° C. The heating time varies depending on the type of the heating apparatus, and is, for example, 5 minutes to 40 minutes when heat treatment is performed on the hot plate, and 10 minutes to 80 minutes when heat treatment is performed in the oven. The target pattern film can be formed on the substrate in the manner as described above. The shape of the pattern in the pattern film is not particularly limited as long as it has a concave-convex structure, and examples thereof include a line and space pattern, a dot pattern, a hole pattern, and a lattice pattern.

[Semiconductor Element] The semiconductor element of the present invention includes the pattern film, preferably an interlayer insulating film including the pattern film. The interlayer insulating film functions as a film that insulates wiring between semiconductor elements. The semiconductor element of the present invention can be produced by a known method. Since the semiconductor element of the present invention includes the pattern film, it can be suitably used in an electronic device such as a display element, a light emitting diode (LED), or a solar cell.

[Display Device] The display device of the present invention includes the semiconductor element. Since the display device of the present invention includes the semiconductor element, it satisfies the usual characteristics required for practical use as a display device. Examples of the display device of the present invention include a liquid crystal display device and an organic electroluminescence (EL) display device.

[Examples] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. As long as it is not specifically mentioned, "parts" means "parts by mass". [Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn)] Mw and Mn of the polymer component were measured by the following methods. ×Measurement method: colloidal permeation chromatography (GPC) method × device: GPC-101 × GPC column of Showa Denko Co., Ltd.: GPC-KF-801, GPC-KF-802, GPC-KF-803 of Shimadzu GLC GPC-KF-804 combined × mobile phase: tetrahydrofuran × column temperature: 40 ° C × flow rate: 1.0 mL / min × sample concentration: 1.0 mass % × sample injection amount: 100 μL × detector: differential refractometer × standard Substance: Monodisperse used in the synthesis of monodisperse polystyrene [single-body] copolymer is as follows. "Providing a single unit of the structural unit (I)" × STMS: Styryl trimethoxy decane × SDMS: Styryl dimethoxy hydroxy decane × STES: Styryl triethoxy decane × TMSPhMA: methyl Trimethoxydecyl phenyl acrylate × VNTMS: vinyl naphthyltrimethoxy decane × VNDMS: vinyl naphthyl dimethoxy hydroxy decane "providing a single unit of structural unit (II)" × MA: methacrylic acid ×HFA: 1,1,1,3,3,3-hexafluoro-2-(4-vinylphenyl)-propan-2-ol × MI: maleimine "providing structural unit (III) Monolithic body × OXMA: OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (3-ethyloxetan-3-yl)methyl methacrylate × GMA: glycidyl methacrylate × VBG: P-vinylbenzyl glycidyl ether × ECHMA: 3,4-epoxycyclohexylmethyl methacrylate × EDCPMA: methacrylic acid [3,4-epoxytricyclo(5.2.1.0 ^2,6 ) decane - 9-yl]ester "providing a single unit of structural unit (IV)" ×MMA: methyl methacrylate × EMA: ethyl methacrylate × PMI: N-phenyl maleimide × MPTS: 3- Methyl propylene methoxypropyl trimethyl Silane-yl

<Synthesis of Polymer Component (A)> [Synthesis Example 1] Synthesis of Polymer Component (A-1) 10 parts of 2,2'-azobis (2,4) was placed in a flask including a cooling tube and a stirrer. - dimethyl valeronitrile) and 200 parts of propylene glycol monomethyl ether acetate which was dried to a moisture content of 50 wtppm using molecular sieve 4A (manufactured by Wako Pure Chemical Industries, Ltd.). Then, 30 parts of styryltrimethoxydecane, 10 parts of methacrylic acid, 30 parts of glycidyl methacrylate, and 30 parts of methyl methacrylate were charged, and after nitrogen substitution, the mixture was slowly stirred. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours, whereby a polymer solution containing the polymer component (A-1) was obtained. The solid content concentration of the polymer solution was 34.1% by mass, the Mw of the polymer component (A-1) was 11,000, and the molecular weight distribution (Mw/Mn) was 2.1.

[Synthesis Example 2 to Synthesis Example 19] The composition of the polymer component or the constituent polymer (A-2) to the polymer component or the constituent polymer (A-19) was used in addition to the type and amount (quality) shown in Table 1. In the same manner as in Synthesis Example 1, a polymer component having a solid content concentration, a weight average molecular weight, and a molecular weight distribution equivalent to the polymer component (A-1) or a constituent polymer thereof was obtained by the same method as in the synthesis example 1 ( A-2) - a polymer component or a polymer solution constituting the polymer (A-19). The polymerization solvent to be used is the same as the organic solvent (D) described in Tables 2 and 3.

[Table 1] Table 1

<Preparation of Radiation-Sensitive Resin Composition> The polymer component (A), the radiation-sensitive compound (B), the adhesion promoter (C), and the organic solvent used in the preparation of the radiation-sensitive resin composition are shown below. D). <<Polymer component (A)>> A-1 to A-19: a polymer component synthesized in Synthesis Example 1 to Synthesis Example 19 or a constituent polymer (A-1) to a polymer component or a constituent polymer (A-19) "Radiation-sensitive compound (B)" B-1: Trifluoromethanesulfonic acid-1,8-naphthyldimethylimine B-2: Irgacure PAG121 (manufactured by BASF) 2-[2-(4-Methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene-2-(2-methylphenyl)acetonitrile) B-3: 4,4'-[1-[4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone Bismuth-5-sulphonium chloride (2.0 mol) condensate B-4: 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinone a condensate of nitrogen-5-sulfonium chloride (2.0 mol) B-5: N-(2-nitrobenzyloxy)carbonyl-N-cyclohexylamine B-6: decyl triflate ( OS17) International Publication No. 2016/124493 B-7: Ethyl methanesulfonate (OS25 described in International Publication No. 2016/124493) "Intimate Adjunct (C)" C-1: 3-glycidoxy Propyltrimethoxydecane C-2: 2-(3,4-epoxycyclohexyl)ethyltrimethyl Base Hydride "Organic Solvent (D)" D-1: Propylene Glycol Monomethyl Ether Acetate (PGMEA) D-Molecular sieve 4A (manufactured by Wako Pure Chemical Industries, Ltd.) and dried to a moisture content of 50 wtppm 2: Diethylene glycol methyl ethyl ether (EDM) D-3: Diethylene glycol methyl ethyl ether was dried using molecular sieve 4A (manufactured by Wako Pure Chemical Industries, Ltd.) to a moisture content of 50 wtppm. Ethyl ether (EDM) D-4: propylene glycol monomethyl ether acetate (PGMEA) D-5: propylene glycol monomethyl ether acetate (PGMEA) distilled by using calcium hydride

<Preparation of Radiation-sensitive Resin Composition> [Example 1] The polymer solution containing the polymer component (A-1) was equivalent to 100 parts (solid content) of the polymer component (A-1). A mixture of one part of the radiation-sensitive linear acid generator (B-1) and three parts of the adhesion promoter (C-1) was dried to a moisture content of 50 wtppm by using a molecular sieve 4A (manufactured by Wako Pure Chemical Industries, Ltd.). The organic solvent (D-1) was diluted so that the final solid content concentration became 30% by mass. Then, filtration was carried out using a membrane filter having a pore size of 0.2 μm to prepare a radiation sensitive resin composition. The moisture content of the radiation sensitive resin composition was measured using a Karl Fischer moisture meter and found to be 250 wtppm.

[Examples 2 to 23, Comparative Example 1 to Comparative Example 2, Comparative Example 4 to Comparative Example 6] Except that each of the components and the blending amount (parts by mass) shown in Tables 2 and 3 were used, The radiation sensitive resin compositions of Examples 2 to 23 and Comparative Examples 4 to 6 were prepared in the same manner as in Example 1. In the same manner as in Example 1, except that each component of the type and the amount (parts by mass) shown in Tables 2 and 3 was used, and the drying treatment of the organic solvent was omitted, Comparative Examples 1 to 2 were prepared in the same manner as in Example 1. A radiation sensitive resin composition.

[Comparative Example 3] In the polymer solution containing the polymer component (A-10), 1 part of the radioactive acid was mixed with an amount corresponding to 100 parts (solid content) of the polymer component (A-10). The agent (B-1) and 3 parts of the adhesion aid (C-1) were removed, and then the organic solvent in the composition was removed under reduced pressure. After 10 parts of toluene was added and azeotropically dehydrated under reduced pressure for 1 hour, the operation was repeated three times, and then dissolved by an organic solvent (D-5) which was subjected to distillation drying using calcium hydride so that the solid content concentration became 30 mass. %. Then, filtration was carried out using a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive resin composition of Comparative Example 3. The moisture content of the radiation sensitive resin composition was measured using a Karl Fischer moisture meter and found to be 3 wtppm. In Tables 2 and 3, the numerical values in parentheses in the columns (A) to (C) are the amounts (parts by mass) of the respective components.

[Table 2] Table 2

[Table 3] Table 3 (*1) "-" indicates that it was not analyzed in the mask evaluation, so it could not be evaluated.

<Evaluation> The cured films were formed from the radiation-sensitive resin compositions of Examples 1 to 23 and Comparative Examples 1 to 6, and the following items were evaluated by the methods described below. The evaluation results are shown in Table 2 and Table 3. In the embodiment 21, a pattern mask for a negative type is used, and in other examples, a pattern mask for a positive type is used.

[Radiation sensitivity] The radiation sensitive resin composition was applied onto a ruthenium substrate subjected to HMDS treatment at 60 ° C for 60 seconds using a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes to form an average film. A film thickness of 3.0 μm. A pattern mask having a line and space pattern having a width of 10 μm was interposed, and the coating film was irradiated with ultraviolet rays of 365 nm using a mercury lamp. Then, the developing solution containing a tetramethylammonium hydroxide (2.38% by mass aqueous solution) was subjected to development treatment at 25 ° C for 60 seconds, and then washed with ultrapure water for 1 minute. At this time, the minimum exposure amount of the line and space pattern in which the width of 10 μm was formed was measured. When the measured value is less than 300 J/m ² , the radiation sensitivity is good, and when it is 300 J/m ² or more, the radiation sensitivity is poor.

[Evaluation of Storage Stability] The prepared radiation sensitive resin composition was sealed in a container having a light-shielding × airtightness. After 7 days passed at 25 ° C, the container was opened, and the [radiation sensitivity] was measured, and the increase rate of the radiation sensitivity (minimum exposure amount) before and after storage for 7 days was calculated. The case where the value is less than 5% is determined as AA, the case where 5% or more and less than 10% is determined as A, and the case where 10% or more and less than 20% is determined as B, and 20% or more is used. Or the case of unresolved is judged as C. When it was AA, A or B, it was evaluated that the storage stability was good, and when it was C, it was evaluated as poor storage stability.

[Evaluation of Substrate Adhesiveness] Using a rotator, the radiation sensitive resin composition was applied onto a ruthenium substrate which was not subjected to HMDS treatment, and then prebaked on a hot plate at 90 ° C for 2 minutes to form an average film thickness of 3.0 μm. Coating film. A pattern mask having a line and space pattern having a width of 1 μm to 50 μm was interposed, and the coating film was irradiated with ultraviolet rays having an exposure amount of 400 J/m ² at 365 nm by a mercury lamp. Then, the developing solution containing a tetramethylammonium hydroxide (2.38% by mass aqueous solution) was subjected to development treatment at 25 ° C for 60 seconds, and then washed with ultrapure water for 1 minute. At this time, the minimum width of the line and space pattern remaining without being peeled off from the substrate was measured. When the measured value is less than 10 μm, it can be evaluated that the substrate adhesion is good (A), and when it is 10 μm or more and less than 15 μm, it can be evaluated that the substrate adhesion is slightly good (B), and when it is 15 μm. When it is the above or not analyzed, it can be evaluated as poor substrate adhesion (C).

[Evaluation of Wiring Corrosion Resistance] Using a rotator, a radiation sensitive resin composition was applied onto a glass substrate having metal wiring patterned at intervals of 10 μm, and then prebaked on a hot plate at 90 ° C for 2 minutes to form A film having an average film thickness of 3.0 μm. Then, the coating film on the outer peripheral portion of the substrate was removed to expose the metal wiring, and the coating film was exposed to a mercury irradiation lamp at a cumulative irradiation amount of 365 nm to be 9,000 J/m ² , and was dried at 200 ° C in a clean oven. The exposed substrate was heated for 30 minutes to form an insulating film on the substrate wiring. The electrode was connected to the metal wiring exposed portion of the substrate, and a voltage of 18 V was applied to the insulating film, and stored in a constant temperature and humidity chamber set to 60 ° C and a humidity of 90% for 30 days, and then the state of the metal wiring was observed using an optical microscope. Observe. In this case, the case where the corrosion rate (area reference) of the metal wiring is less than 15% is determined as A, the case where 15% or more is less than 25% is determined as B, and the case where 25% or more is determined as C. When the corrosion rate of the metal wiring was A or B, it was evaluated that the wiring corrosion resistance was good, and when it was C, it was evaluated that the wiring corrosion resistance was poor.

[Evaluation of PCD Margin and PED Margin] Using a rotator, the radiation sensitive resin composition was applied onto a ruthenium substrate subjected to HMDS treatment at 60 ° C for 60 seconds, and (1a) was 90 ° C on a hot plate. Prebaking for 2 minutes to form a coating film having an average film thickness of 3.0 μm, (2a) a pattern mask having a line and space pattern having a width of 10 μm, and irradiating the coating film with ultraviolet rays of 365 nm using a mercury lamp, ( 3a) Using a developing solution containing a tetramethylammonium hydroxide 2.38 mass% aqueous solution, the coating film after ultraviolet irradiation at 25 ° C was subjected to development treatment for 60 seconds, and then washed with ultrapure water for 1 minute. In addition, in the case of performing a post-coating delay (PCD) margin evaluation, the coating film is allowed to stand at room temperature for 1 hour after the (1a) and before the (2a). In addition, in the case of performing a Post Exposure Delay (PED) margin evaluation, the coating film is additionally left at room temperature for 1 hour after the (2a) and before the (3a). A step of. At this time, the minimum exposure amount of the line and space pattern in which the width of 10 μm was formed was measured. The measured value is compared with the measured value of [radiation sensitivity], and the case where the increase rate of the minimum exposure amount is less than 5% is determined as A, and the case where 5% or more and less than 10% is determined as B, and 10 is determined. The case of % or more or the case of unresolved is judged as C. When it is A or B, it can be evaluated as a PCD margin and a PED margin, and when it is C, it can be evaluated as a PCD margin and a poor PED margin.

[Measurement of Minimum Resolution] The radiation sensitive resin composition was applied onto a tantalum substrate subjected to HMDS treatment at 60 ° C for 60 seconds using a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes. A coating film having an average film thickness of 3.0 μm was formed. A pattern mask having a square pattern of 1 μm to 10 μm was interposed, and the coating film was irradiated with ultraviolet rays of 365 nm with an exposure amount of 1.5 times the minimum exposure amount optimized for each of [radiation sensitivity] using a mercury lamp. Then, the developing solution containing a tetramethylammonium hydroxide (2.38% by mass aqueous solution) was subjected to development treatment at 25 ° C for 60 seconds, and then washed with ultrapure water for 1 minute. At this time, the minimum mask size at which a square pattern can be formed is measured. When the measured value is less than 4 μm, the analytical property is evaluated to be good, and when it is 4 μm or more, the analytical property is evaluated as poor.

As shown in Table 2 and Table 3, it is understood that each of the radiation sensitive resin compositions of the examples has excellent radiation sensitivity, and has radiation characteristics, storage stability, substrate adhesion, wiring corrosion resistance, and PCD margin as practical characteristics. Any one of PED margin and analyticity is good. On the other hand, in the radiation sensitive resin composition of the comparative example, all of the characteristics were not good.

no

no.

Claims (11)

A radiation sensitive resin composition comprising: a polymer component (A) having an aromatic ring and an alkoxyalkyl group directly bonded to the aromatic ring in the same or different polymer Structural unit (I) and structural unit (II) containing an acidic group; a radiation sensitive compound (B); an organic solvent (D); and water (E); and the content of the water (E) is 10 wtppm or more, 800 wtppm or less. The radiation sensitive resin composition according to claim 1, wherein the content of the water (E) is 550 wtppm or less. The radiation-sensitive resin composition according to Item 1 or 2, wherein the content of the water (E) is 250 wtppm or less. The radiation sensitive resin composition according to claim 1 or 2, wherein the polymer component (A) has and is selected from the structural unit (I) and the structural unit (II) The polymer of the same or different polymer of at least one of the structural units has a structural unit (III) having a crosslinkable group. The radiation sensitive resin composition according to claim 1 or 2, wherein the structural unit (I) is a substituted or unsubstituted benzene ring, a naphthalene ring or an anthracene ring, and a structural unit bonded to a ring represented by —SiR ₃ on the ring, wherein each R is independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an aryl group or an alkoxy group; wherein the R At least one of them is an alkoxy group. The radiation sensitive resin composition according to claim 1 or 2, wherein the composition is a positive type. A patterned hardened film, which is formed by the radiation sensitive resin composition according to any one of claims 1 to 6. The patterned cured film according to claim 7, wherein: the interlayer insulating film. A method for producing a patterned cured film, comprising: the step (1), forming a coating film of the radiation sensitive resin composition according to any one of claims 1 to 6 on the substrate; In the step (2), a part of the coating film is irradiated with radiation; in the step (3), the coating film irradiated with radiation is developed; and in the step (4), the developed coating film is heated. A semiconductor element comprising: a patterned cured film as described in claim 7 or 8. A display device comprising: the semiconductor device according to claim 10 of the patent application.