JP7047652B2 - Radiation-sensitive resin compositions and their uses - Google Patents

Description

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

As the semiconductor element, a cured film such as an interlayer insulating film, a spacer, a protective film, and a patterned colored film for a color filter (also referred to as a “colored pattern film” in the present specification) is generally used. As the material for forming the cured film, the number of steps for forming a patterned cured film (also referred to as “patterned film” in the present specification) is small, and high surface hardness can be obtained. Therefore, radiation sensitivity is obtained. Resin compositions are widely used.

As the radiation-sensitive resin composition, for example, a radiation-sensitive resin composition containing a copolymer containing a carboxy group and an epoxy group is known (see Patent Document 1). Further, a positive photosensitive composition containing a polymer obtained by radically copolymerizing a radically polymerizable monomer having an alkoxysilyl group and a radically polymerizable monomer having an acidic group is known (see Patent Document 2). ..

Japanese Unexamined Patent Publication No. 2001-354822 Japanese Unexamined Patent Publication No. 2013-101240

The present inventors have excellent radiation sensitivity in a radiation-sensitive resin composition containing a polymer component having an alkoxysilyl group directly bonded to an aromatic ring and a radiation-sensitive compound, and by using the composition, the resolution can be improved. It has been found that an excellent patterned film can be obtained. However, in the composition, storage stability and corrosiveness to metal wiring may be a problem.

The subject of the present invention is a radiation-sensitive resin composition, a pattern film and its manufacturing method, and a semiconductor device, which are excellent in radiation sensitivity and storage stability, and can obtain a pattern film having high resolution and low corrosion resistance to metal wiring. , As well as providing a display device.

The present inventors have made diligent studies to solve the above problems. As a result, they have found that the above-mentioned problems can be solved by a radiation-sensitive resin composition having the following constitution, and have completed the present invention.

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

According to the present invention, a radiation-sensitive resin composition, a pattern film and a method for manufacturing the same, and a semiconductor device capable of obtaining a patterned film having excellent radiation sensitivity and storage stability, high resolution, and low corrosiveness to metal wiring can be obtained. , As well as display devices can be provided.

Hereinafter, embodiments for carrying out the present invention will be described.
[Radiation-sensitive resin composition]
The radiation-sensitive resin composition of the present invention (hereinafter, also referred to as “composition of the present invention”) is a structural unit containing an aromatic ring and an alkoxysilyl group directly bonded to the aromatic ring in the same or different polymers. It contains (I), a polymer component (A) having a structural unit (II) containing an acidic group, a radiation-sensitive compound (B), an 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 polymers. The structural units (I) and (II) may be contained in the same polymer or different polymers, respectively.

<< Structural unit (I) >>
The structural unit (I) includes an aromatic ring and an alkoxysilyl group directly bonded to the aromatic ring. The alkoxysilyl group directly bonded to the aromatic ring means that the silicon atom in the alkoxysilyl group is bonded to the ring carbon atom of the aromatic ring.

When the radiation-sensitive acid generator described later is used as the radiation-sensitive compound (B), the composition of the present invention can exhibit highly sensitive positive radiation-sensitive radiation characteristics due to the structural unit (I). The reason for this is presumed as follows. The structural unit (I) comprises an alkoxysilyl group directly attached to the aromatic ring. When the coating film of the composition of the present invention is irradiated with radiation, the alkoxysilyl group to the silanol group are subjected to a hydrolysis reaction with water in the atmosphere or a developer catalyzed by an acid generated from a radiation-sensitive acid generator. (Si—OH) is generated. Since the silanol group is bound to the aromatic ring, the condensation reaction of the silanol group is inhibited, and the silanol group can be stabilized and exist. Therefore, the silanol group enhances the solubility of the irradiation region in the alkaline developer. As described above, the composition of the present invention can exhibit positive radiation-sensitive radiation characteristics. On the other hand, in the case of a structure in which the alkoxysilyl group is not directly bonded to the aromatic ring, the silanol group formed is unstable and condensation with siloxane occurs. Therefore, the irradiation region is insolubilized (negative), and the positive radiation characteristic is not exhibited. Further, by including the aromatic ring in the structural unit (I), various properties such as heat resistance of the obtained pattern film can be further enhanced.

Further, when a radiation-sensitive base generator described later is used as the radiation-sensitive compound (B), the composition of the present invention can exhibit highly sensitive negative radiation-sensitive radiation characteristics due to the structural unit (I). .. It is presumed that this is because when the coating film of the composition of the present invention is irradiated with radiation, the base generated from the radiation-sensitive base generator acts as a catalyst to form polysiloxane.

The structural unit (I) may be one kind of structural unit or a plurality of kinds of structural units.
The alkoxysilyl group is preferably a group represented by −SiR ₃ . The R is independently a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an aryl group, or an alkoxy group. However, at least one, preferably at least two, and more preferably all three of the R are alkoxy groups. In the structural unit (I), the number of alkoxysilyl groups directly bonded to the aromatic ring is usually 1 to 9, preferably 1 to 7, more preferably 1 to 5, and even more preferably 1.

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

A substituent other than the above-mentioned alkoxysilyl group may be bonded to the aromatic ring. Examples of the substituent include a halogen atom, a hydroxy group, an alkyl group, and an alkoxy group. The substituent may be one kind, two or more kinds, and may be one or more.

Hereinafter, each group in the R and the 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, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group and a t-butyl group. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. Methyl groups are more preferred.

Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group and an i-propoxy group. The alkoxy group has preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. A methoxy group and an ethoxy group are more preferable, and a methoxy group is further preferable.

As the group of R that is not an alkoxy group, an alkyl group or a hydroxy group is preferable.
-Specifically, the group represented by SiR ₃ includes a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, a dimethoxyhydroxysilyl group, a dimethoxymethylsilyl group, a diethoxyethylsilyl group and a methoxydimethylsilyl group. Groups are preferred.
Examples of the structural unit (I) include a structural unit represented by the formula (1).

式（１）中、Ｒ^Aは、水素原子、メチル基、ヒドロキシメチル基、シアノ基またはトリフルオロメチル基であり、好ましくは水素原子またはメチル基である。Ｒ¹は、前述した、アルコキシシリル基が直接結合した芳香環であり、Ｘに前記芳香環が結合している。Ｘは、単結合または２価の有機基である。

In the formula (1), ^RA is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group or a trifluoromethyl group, and is preferably a hydrogen atom or a methyl group. R ¹ is the above-mentioned aromatic ring to which the alkoxysilyl group is directly bonded, and the aromatic ring is bonded to X. X is a single bond or divalent organic group.

Examples of the divalent organic group include 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 organic group having 6 to 20 carbon atoms. A divalent hydrocarbon group such as an aromatic hydrocarbon group; an ester bond (-COO-), a group formed by bonding the divalent hydrocarbon group and an oxy group (-O-), and a combination of these groups. The group is mentioned.

As X, a single bond and -COO- * (* indicates a bond position with an aromatic ring in R ¹ ) are preferable, and a single bond is more preferable.
Examples of the structural unit (I) include structural units represented by the formulas (I-1) to (I-20).

式（Ｉ－１）～（Ｉ－２０）中、Ｒ^Aは、式（１）中のＲ^Aと同義である。

In formulas (I-1) to (I-20), ^RA is synonymous with ^RA in formula (1).

《Structural unit (II)》
The structural unit (II) has an acidic group. For example, the polymer component (A) can have the structural unit (II) in the same or different polymer as the polymer having the structural unit (I). The structural unit (II) may be one type of structural unit or a plurality of types of structural units. The structural unit (II) can increase the solubility of the polymer component (A) in a developing solution and enhance the curing reactivity.

As the acid dissociation constant of the acidic group, for example, pKa ≦ 12 is preferable, pKa ≦ 10 is more preferable, and pKa ≦ 8 is further preferable. As the acidic group, for example, at least one of the hydrogen atoms bonded to the carbon atom is substituted with an electron-attracting group, and at least one of the hydrogen atoms bonded to the nitrogen atom is substituted with an electron-attracting group. At least one selected from an amino group, a carboxy group, a sulfo group, a phenolic hydroxyl group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group and a sulfonamide group can be mentioned. Examples of the electron-withdrawing group include halogen atoms such as a fluorine atom and a chlorine atom, a nitro group, a cyano group, and a carbonyl group. As the acidic group, at least one selected from a hydroxyfluorinated alkyl group, a maleimide group, a carboxy group, a sulfo group, a phenolic hydroxyl group, a phosphoric acid group, a phosphonic acid group and a phosphinic acid group is preferable, and a hydroxyfluorinated alkyl group, At least one selected from a maleimide group, a carboxy group and a sulfo group is more preferable. The acid dissociation constant can be measured as the acid dissociation constant of the acidic group in the monomer giving the structural unit (II) at 25 ° C. in _H2O (water).

As the hydroxyfluorinated alkyl group, a group represented by the formula (2): —C (R ² ) (R ³ ) OH is preferable. 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 and good crosslinkability with a crosslinkable group in the structural unit (III) described later.

Examples of the fluorinated alkyl group having 1 to 4 carbon atoms include a difluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group and a 2,2,3,3-tetrafluoropropyl group. , Perfluoroethylmethyl group, 2,2,3,3,4,4-hexafluorobutyl group; perfluoroalkyl groups such as trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group Can be mentioned.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group and a t-butyl group. Be done.

As R ² , a fluorinated alkyl group having 1 to 4 carbon atoms is preferable, a perfluoroalkyl group is more preferable, and a trifluoromethyl group is further preferable. As R ³ , a hydrogen atom, a fluorine atom and a fluorinated alkyl group having 1 to 4 carbon atoms are preferable, a hydrogen atom and the fluorinated alkyl group are more preferable, the fluorinated alkyl group is further preferable, and a perfluoroalkyl group is preferable. Particularly preferred, a trifluoromethyl group is particularly preferred. In such an embodiment, since it becomes a suitable acidic group, a good cross-linking reaction occurs, and various properties of the obtained pattern film such as chemical resistance can be further enhanced. Examples of the hydroxyfluorinated alkyl group-containing monomer include 1,1,1,3,3,3-hexafluoro-2- (4-vinylphenyl) -propane-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 silicic acid; maleic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid. Unsaturated dicarboxylic acids such as mono [2- (meth) acryloyloxyethyl] monosuccinate, mono [(meth) acryloyloxyethyl] and other polyvalent carboxylic acids with divalent or higher valence such as mono [2- (meth) acryloyloxyethyl] Acryloyloxyalkyl] esters are preferred, preferably unsaturated monocarboxylic acids, more preferably (meth) acrylic acids.

In one embodiment, from the viewpoint of alkali developability, the unsaturated carboxylic acid is preferably an unsaturated carboxylic acid having no aromatic ring, that is, for example, 4-vinylbenzoic acid and 4-vinylphenylpropionic acid. It is preferably not an aromatic unsaturated carboxylic acid. In the case of an aromatic unsaturated carboxylic acid, a π-π stacking phenomenon may occur in the structural unit (I) and the structural unit (II), making it difficult to develop alkali developability.

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

The crosslinkable group is a group other than the alkoxysilyl group and the acidic group, and refers to a group capable of reacting with each other (for example, epoxy groups) of the same type under heating conditions to form a covalent bond. Examples of the crosslinkable group include an epoxy group such as an oxylanyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure), a cyclic carbonate group, a methylol group, a (meth) acryloyl group, and a vinyl group. Can be mentioned. Among these, an oxylanyl group, an oxetanyl group and a methylol group are preferable, an oxylanyl group and an oxetanyl group are more preferable, and an oxylanyl group is further preferable.

Examples of the structural unit (III) containing an oxylanyl group include structural units represented by the formulas (III-1) to (III-7) and (III-18). Examples of the structural unit (III) containing an oxetanyl group include structural units represented by the formulas (III-8) to (III-11). Examples of the structural unit (III) containing a cyclic carbonate group include structural units represented by the following formulas (III-12) to (III-16). Examples of the structural unit (III) containing a methylol group include structural units represented by the formula (III-17).

式（III－１）～（III－１８）中、Ｒ^Cは、水素原子、メチル基またはトリフルオロメチル基である。

In formulas (III-1) to (III-18), ^RC is a hydrogen atom, a methyl group or a trifluoromethyl group.

Examples of the structural unit (III) containing the (meth) acryloyl group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene di. (Meta) acrylate, tripropylene di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Di (meth) acrylate compounds such as pentyl glycol di (meth) acrylate and tripropylene glycol diacrylate; tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Tri (meth) acrylate compounds such as meta) acrylate; Tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; Dipentaerythritol For monomers such as penta (meth) acrylate compounds such as penta (meth) acrylate The structural unit from which it is derived can be mentioned.

The structural unit (III) containing a (meth) acrylic group or a vinyl group includes, for example, a structural unit obtained by reacting a structural unit containing a carboxy group with an unsaturated compound containing an epoxy group, and a structural unit containing an epoxy group (meth). Meta) A structural unit obtained by reacting acrylic acid, a structural unit containing an isocyanate group in a structural unit containing a hydroxy group, a structural unit obtained by reacting a (meth) acrylic acid ester or a vinyl compound, and a structural unit containing an acid anhydride. A structural unit obtained by reacting (meth) acrylic acid can also be mentioned.

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

Examples of the monomer giving the structural unit (IV) include (meth) acrylic acid chain alkyl ester, (meth) acrylic acid alicyclic-containing ester, (meth) acrylic acid aryl ester, N-substituted maleimide compound, and unsaturated. Examples thereof include saturated dicarboxylic acid diesters and unsaturated aromatic compounds, and other examples include bicyclounsaturated compounds, isocyanate skeletons, furan skeletons, unsaturated compounds having a tetrahydropyran skeleton or pyran skeleton, and other unsaturated compounds.

Examples of the (meth) acrylic acid chain alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-butyl (meth) acrylic acid, sec-butyl (meth) acrylic acid, and (meth) acrylic. Examples thereof include t-butyl acid acid, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, and n-stearyl (meth) acrylate.

Examples of the (meth) acrylic acid alicyclic-containing ester include (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, and (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decane. -8-yl, tricyclo (meth) acrylate [5.2.1.0 ^2,6 ] decane-8-yloxyethyl, isoboronyl (meth) acrylate can be mentioned.

Examples of the (meth) acrylic acid aryl ester include (meth) acrylic acid phenyl and (meth) acrylic acid benzyl.
Examples of the N-substituted maleimide compound include N-alkyl group-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, and N-tert-butylmaleimide; and N-cycloalkyl group-substituted maleimides such as N-cyclohexylmaleimide; N. Examples thereof include N-aromatic ring-containing group-substituted maleimides such as -phenylmaleimide, N-benzylmaleimide, N- (9-acridinyl) maleimide, and N-hydroxyphenylmaleimide.

Examples of unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, and diethyl itaconic acid. Examples of unsaturated aromatic compounds include styrene, α-methylstyrene, vinyltoluene, p-methoxystyrene, and α-methyl-p-hydroxystyrene. Other unsaturated compounds include, for example, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate.

Among these, the structural unit (IV) includes a (meth) acrylic acid chain alkyl ester, a (meth) acrylic acid alicyclic-containing ester, an N-substituted maleimide compound, and a structural unit derived from an unsaturated aromatic compound. preferable.

<< Content ratio of each structural unit >>
The lower limit of the content ratio of the structural unit (I) to the total structural units in the polymer component (A) is preferably 10% by mass, more preferably 20% by mass, still more preferably 25% by mass. On the other hand, as the upper limit, 80% by mass is preferable, 70% by mass is more preferable, and 60% by mass is further preferable. In such an embodiment, the composition of the present invention can further improve the heat resistance of the obtained pattern film while exhibiting better radiation-sensitive characteristics.

The lower limit of the content ratio of the structural unit (II) to the total 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 is 50. It is preferably by mass, more preferably 40% by mass, still more preferably 30% by mass. In such an aspect, the composition of the present invention can further improve various characteristics of the obtained pattern film while exhibiting better radiation-sensitive characteristics.

When the polymer component (A) has a 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, preferably 10% by mass. More preferably, 20% by mass is even more preferable; as the upper limit thereof, 70% by mass is preferable, and 60% by mass is more preferable. In such an embodiment, the composition of the present invention can enhance the radiation-sensitive properties and various properties of the obtained pattern film in a more balanced manner.

When the polymer component (A) has a 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, preferably 10% by mass. More preferably; as the upper limit, 50% by mass is preferable, and 40% by mass is more preferable. In such an embodiment, chemical resistance and the like can be effectively improved.

The polymer component (A) may be composed of one kind of polymer or two or more kinds of polymers as long as the content of each structural unit measured by NMR analysis satisfies the above requirements. .. In the case of two or more kinds of polymers (blended product), the content ratio (measured value) of each structural unit to the entire blended product may satisfy the above requirements.

Examples of the polymer component (A) include a copolymer having structural units (I) and (II), a mixture of a polymer having structural unit (I) and a polymer having structural unit (II), and a structure. Polymers having units (I), (II) and (III), mixtures of polymers having structural units (I) and (II) and polymers having structural unit (III), structural units (I) ) And a mixture of the polymer having the structural unit (II) and (III), the polymer having the structural unit (I), the polymer having the structural unit (II), and the structural unit (III). Examples include a mixture with a polymer. The polymer or copolymer may further have a structural unit (IV).
The copolymer having structural units (I) and (II) means that the same polymer has structural units (I) and (II). The same applies to other copolymers.

Also, different polymers include homologous structural units, such as mixtures of copolymers with structural units (I) and (II) and copolymers with structural units (II) and (III). It may be a thing. The copolymer may further have a structural unit (IV).

As the polymer component (A), a copolymer having structural units (I) and (II) is preferable, and a copolymer having structural units (I), (II) and (III) is more preferable, and structural units. Copolymers having (I), (II), (III) and (IV) are more preferred. Further, from the viewpoint of storage stability, the copolymer having the structural units (I) and (II) is a mixture of the polymer having the structural unit (I) and the polymer having the structural unit (II). Is preferable. In the case of other mixtures as well, from the viewpoint of storage stability, a copolymer having a corresponding structural unit is preferable to the mixture.

<< Method for synthesizing polymer component (A) >>
The polymer component (A) can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in an appropriate polymerization solvent using a radical polymerization initiator. In general, the compounding ratio of each monomer 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 types of polymers may be synthesized, and then the plurality of types of polymers may be mixed and used.

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

Examples of the polymerization solvent include the organic solvents listed as the organic solvent (D) described later. The polymerization solvent can be used alone or in combination of two or more.
When the same as the organic solvent (D) in the radiation-sensitive resin composition in which the polymerization solvent is prepared, the polymer solution obtained by the above polymerization can be used as it is, or the organic solvent (D) can be added to the obtained polymer solution. By adding it, it may be used for preparing a radiation-sensitive resin composition. In this case, in order to reduce the content of water (E) in the obtained composition, an organic solvent dried by a method described later can also be used as the polymerization solvent.

<< Physical characteristics and content ratio of polymer component (A) >>
The polystyrene-equivalent weight average molecular weight (Mw) of the polymer component (A) by the gel permeation chromatography (GPC) method is preferably 1,000 to 30,000. The ratio (Mw / Mn) of the Mw of the polymer component (A) to the polystyrene-equivalent number average molecular weight (Mn) by the GPC method is preferably 1 to 3.

The lower limit of the content of the polymer component (A) in the total solid content of the composition of the present invention is preferably 50% by mass, more preferably 70% by mass, still more preferably 90% by mass; the upper limit is 99% by mass. % Is preferable, and 97% by mass is more preferable. In such an embodiment, the composition of the present invention can more effectively enhance the radiation-sensitive properties and various properties (eg, resolution) of the obtained pattern film. The total solid content refers to all components other than the organic solvent (D) and water (E).

<Radiation-sensitive compound (B)>
The radiation-sensitive compound (B) (hereinafter, also referred to as “component (B)”) includes, for example, a radiation-sensitive acid generator which is a compound that generates an acid by a treatment including irradiation, and a base by a treatment including irradiation. Examples thereof include a radiation-sensitive base generator which is a compound that generates the above-mentioned acid generator. Examples of radiation include ultraviolet rays, far ultraviolet rays, visible rays, X-rays, and electron beams. As the treatment, depending on the type of the component (B), only irradiation may be sufficient, and water contact treatment may be required.

By irradiation treatment or the like on the coating film formed from the composition of the present invention, an acid or a base is generated in the irradiated portion based on the component (B), and the alkali of the polymer component (A) is generated based on the action of the acid or the base. Solubility in developer changes.

Examples of the radiation-sensitive acid generator include an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound, and a quinonediazide compound.

Specific examples of the oxime sulfonate compound, onium salt, sulfonimide compound, halogen-containing compound, diazomethane compound, sulfone compound, sulfonic acid ester compound and carboxylic acid ester compound include, for example, paragraph [0078] of JP-A-2014-157252. ~ [0106] and the compounds described in International Publication No. 2016/124943 are mentioned, and these acid generators are assumed to be described in the present specification. In addition, these acid generators can also be used in combination with a quinonediazide compound.

Examples of the oxime sulfonate compound include, for example, (5-propylsulfonyloxyimino-5H-thiophen-2-iriden)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-iriden). -(2-Methylphenyl) acetonitrile, (Camfersulfonyloxyimino-5H-thiophen-2-iriden)-(2-Methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-iriden) -(2-Methylphenyl) acetonitrile, (2- [2- (4-methylphenylsulfonyloxyimine)]-2,3-dihydrothiophene-3-iriden] -2- (2-methylphenyl) acetonitrile), 2 -(Octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile can be mentioned.
Specific examples include the Irgacure PAG 121 manufactured by BASF.

Examples of sulfonimide compounds include, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (kanfasulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenyl). Sulfonyloxy) Sulfonylimide, N- (4-fluorophenylsulfonyloxy) Sulfonylimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (kanfasulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide , N- (2-Fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (kanfasulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, trifluoromethanesulfonic acid- Examples include 1,8-naphthalimide.

Examples of the quinone diazide compound include a naphthoquinone diazide compound, which is a condensate of a compound having one or more phenolic hydroxyl groups and a 1,2-naphthoquinone diazide sulfonic acid halide or a 1,2-naphthoquinone diazido sulfonic acid amide. ..

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. It shall be stated. As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable, and 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5-sulfonic acid chloride are preferable. More preferred. As the 1,2-naphthoquinone diazide sulfonic acid amide, 2,3,4-triaminobenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid amide is preferable.

Specific examples of the quinone diazide compound include, for example, 4,4'-dihydroxydiphenylmethane, 2,3,4,2', 4'-pentahydroxybenzophenone, tri (p-hydroxyphenyl) methane, 1,1,1-tri. (P-Hydroxyphenyl) Ester, 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 A compound selected from'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-4-sulfonic acid chloride or 1,2. -An ester compound with naphthoquinone diazide-5-sulfonic acid chloride can be mentioned.

As the radiation-sensitive base generator, a base generator that generates an amine by irradiation is preferable. Examples of the amine include aliphatic amines and aromatic amines, and may be either monofunctional amines or polyfunctional amines.

Examples of the base generator that generates an amine by irradiation include orthonitrobenzyl carbamate compounds, α, α-dimethyl-3,5-dimethoxybenzyl carbamate compounds, other carbamate compounds, acyloxyimino compounds, and cobalt amine complexes. Be done. Specific examples of the base generator that generates an amine by irradiation are described in paragraphs [0104] to [0105] of JP-A-2017-09737 and paragraph [0045] of JP-A-2017-133006. These compounds are described herein.

Specific examples of the radiation-sensitive base generator include [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, and bis [[(2-nitro]. Benzyl) oxy] carbonyl] hexane-1,6-diamine, N- (2-nitrobenzyloxy) carbonyl-N-cyclohexylamine, 9-anthrylmethyl N, N-diethylcarbamate, 9-anthrylmethyl N-cyclohexyl Carbamate, 9-anthrylmethyl N, N-dicyclohexylcarbamate, O-carbamoylhydroxyamide, O-carbamoyloxime, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4-morpholinobenzoyl) -1- Benzyl-1-dimethylaminopropane and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone can be mentioned.

The component (B) can 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 to 30 parts by mass, preferably 0.05 to 26 parts by mass, based on 100 parts by mass of the polymer component (A). It is preferably 0.05 to 20 parts by mass.

<Adhesion aid (C)>
The adhesion aid (C) (hereinafter, also referred to as “component (C)”) is a component that improves the adhesiveness between the obtained pattern film and the substrate. As the component (C), a functional silane coupling agent having a reactive functional group such as a carboxy group, a (meth) acryloyl group, a vinyl group, an isocyanate group, an isocyanurate group, an oxylanyl group, an oxetanyl group and a mercapto group is preferable. .. Examples of the functional silane coupling agent include trimethoxysilyl benzoic acid, 3- (meth) acryloxipropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isoxapropyltriethoxysilane, and tris-(. Trimethoxysilylpropyl) isocyanurate, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-ethyl-3-oxetanylmethoxypropyltrimethoxysilane, 3-mercaptopropylmethyl Dimethoxysilane can be mentioned.

The component (C) can be used alone or in combination of two or more.
When the component (C) is used, the content of the component (C) in the composition of the present invention is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer component (A).

<Other ingredients>
The composition of the present invention may further contain other components in addition to the polymer component (A) and the component (B). Other components include, for example, at least one selected from antioxidants, surfactants, crosslinkable compounds and polymerization initiators.

In the composition of the present invention, the upper limit of the total content ratio of the components other than the polymer component (A), the component (B) and the component (C) in the total solid content may be preferably 20% by mass. 15% by weight may be more preferred, and 10% by weight may be even more preferred.

<Organic solvent (D)>
As the organic solvent (D), an organic solvent that uniformly dissolves or disperses each component contained in the composition of the present invention and does not react with each of the above components is used.

Examples of the organic solvent (D) include alcohol solvents such as isopropyl alcohol, butanol, isoamyl alcohol, octanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and propylene glycol monomethyl ether; butyl acetate, ethyl lactate, and γ. -Ester solvents such as butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate; ether solvents such as ethylene glycol ethyl methyl ether and diethylene glycol methyl ethyl ether; N , N-dimethylacetamide, N-methylpyrrolidone and other amide solvents; methylisobutylketone, cyclohexanone and other ketone solvents; and toluene, xylene and other aromatic hydrocarbon solvents.

The organic solvent (D) can 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 to 95% by mass, preferably 10 to 90% by mass, and more preferably 15 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, and more preferably 250 wtppm or less. The content of water (E) is 10 wtppm or more, preferably 15 wtppm or more, more preferably 20 wtppm or more, still more preferably 200 wtppm or more. The content of water (E) can be measured using a Karl Fischer titer. When the content of water (E) is not more than the above upper limit value, it is excellent in storage stability, resistance to metal wiring corrosion, and PCD margin described later. When the content of water (E) is less than the lower limit, the radiation sensitivity tends to decrease and the PED margin described later tends to decrease.

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 on a metal wiring, the composition is used. Metal wiring may be prone to corrosion. It is considered that the corrosion is caused by the water (E) acting as a medium between the radiation-sensitive acid generator and the metal wiring, so that the metal wiring is corroded.

Since the content of water (E) in the composition of the present invention is 800 wtppm or less, the storage stability of the composition and the adhesion to the substrate are high, and for example, the corrosiveness of the metal wiring to which the composition is applied. That is, the metal wiring corrosiveness of the insulating film formed from the composition is low.

<Preparation method of radiation-sensitive resin composition>
In the composition of the present invention, for example, the polymer component (A), the component (B), and if necessary, the component (C) and other components are mixed in a predetermined ratio and dissolved in an organic solvent (D). To prepare. The prepared radiation-sensitive resin composition is preferably filtered with, 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 the raw material such as the organic solvent (D). In order to reduce the content of water (E) in the composition of the present invention to 800 wtppm or less, for example, the organic solvent (D) is distilled using an organic solvent dried with molecular sieves or calcium hydride. A method using a dried organic solvent, a method using an organic solvent distilled and dried using trimethyl orthogeate, a method of azeotropically dehydrating the solid content components and the obtained composition using an organic solvent such as toluene, distillation under reduced pressure. There is a way to do it. Further, the polymer component (A) can also be dried under reduced pressure.

<Use of radiation-sensitive resin composition>
The composition of the present invention exhibits good radiation-sensitive characteristics, is excellent in radiation sensitivity, and is excellent in storage stability. By using the above composition, it is possible to obtain a pattern film having high resolution, low corrosiveness to metal wiring, and excellent adhesion to a substrate. In particular, the composition has a large PCD (Post Coating Delay) margin and PED (Post Exposure Delay) margin described in Examples described later, can reduce the defect rate of the pattern film and improve the yield, and can be used for manufacturing workability. Is excellent.

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 spacer, a protective film, and a colored pattern film for a color filter, particularly as a material for forming an interlayer insulating film. Examples of the semiconductor element include a display element.

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

[Manufacturing method of pattern film]
The method for producing a pattern film of the present invention includes a step (1) of forming a coating film of the composition of the present invention on a substrate, a step (2) of irradiating a part of the coating film with radiation, and irradiation with radiation. It has a step (3) of developing the developed coating film and a step (4) of heating the developed coating film.

<Process (1)>
In step (1), the composition of the present invention is used to form a coating film on a substrate. Specifically, the composition in the form of a solution is applied to the surface of the substrate, and preferably prebaked to remove the organic solvent (D) to form a coating film.

Examples of the substrate include a glass substrate, a silicon substrate, a plastic substrate, and a substrate on which various metal thin films are formed on the surface thereof. Examples of the plastic substrate include a resin substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, and polycycloolefin. The substrate may be subjected to a hydrophobic surface treatment such as HMDS (hexamethyldisilazane) treatment in order to improve the adhesion to the coating film.

Examples of the coating method include a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method, a bar coating method, and an inkjet method.
The prebaking conditions vary depending on the type and proportion of each component, but can be, for example, about 30 seconds to 10 minutes at 60 to 130 ° C. The film thickness of the formed coating film is preferably 0.1 to 10 μm as a value after prebaking.

<Process (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 ultraviolet rays include g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm). Among these radiations, ultraviolet rays are preferable, and among the ultraviolet rays, radiations containing any one or more of g-rays, h-rays and i-rays are more preferable. The exposure amount of radiation is preferably 0.1 to 10,000 J / m ² . For higher sensitivity, the coating film may be wetted with a liquid such as water before irradiation.

Further, when a negative type radiation-sensitive resin composition is used, heat treatment can be performed after irradiation. Hereinafter, this process is also referred to as "PEB process". The PEB conditions vary depending on the type of each component in the radiation-sensitive resin composition, the mixing ratio, the thickness of the resin film, etc., but are usually 70 to 150 ° C., preferably 80 to 120 ° C. for about 1 to 60 minutes. Is.

<Process (3)>
In the step (3), the coating film irradiated with radiation is developed. Specifically, the coating film irradiated with radiation in step (2) is developed with a developing solution, and in the case of the positive type, the irradiated portion is exposed, and in the case of the negative type, the radiation is not applied. Remove the irradiated area. For higher sensitivity, the coating film may be wetted with a liquid such as water before development.

The developer is usually an alkaline developer, and examples thereof include an aqueous solution of a basic compound. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, and triethylamine. Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4] .3.0] -5-Nonan can be mentioned. The concentration of the basic compound in the aqueous solution is, for example, 0.1 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 a radiation-sensitive resin composition may be used as a developer. ..

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

After development, it is preferable to rinse the patterned coating film by washing with running water. Next, the radiation-sensitive compound (B) remaining in the coating film may be decomposed by irradiating the entire surface with radiation from a high-pressure mercury lamp or the like (post-exposure). The exposure amount in the post-exposure is preferably 2,000 to 10,000 J / m ² .

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

[Semiconductor device]
The semiconductor device of the present invention includes the pattern film, preferably an interlayer insulating film made of the pattern film. The interlayer insulating film functions as a film that insulates wiring between wirings in a semiconductor element. The semiconductor device of the present invention can be manufactured by using a known method. Since the semiconductor element of the present invention includes the pattern film, it can be suitably used for electronic devices such as display elements, light emitting diodes (LEDs), and solar cells.

[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 general 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.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. Unless otherwise stated, "parts" means "parts by mass".
[Weight average molecular weight (Mw) and number average molecular weight (Mn)]
The Mw and Mn of the polymer were measured by the following method.
-Measurement method: Gel permeation chromatography (GPC) method-Equipment: Showa Denko GPC-101
-GPC column: GPC-KF-801, GPC-KF-802, Shimadzu GLC,
GPC-KF-803 and GPC-KF-804 bonded ・ Mobile phase: Tetrahydrofuran ・ Column temperature: 40 ° C.
・ Flow velocity: 1.0 mL / min ・ Sample concentration: 1.0 mass%
-Sample injection amount: 100 μL
・ Detector: Differential refractometer ・ Standard material: Monodisperse polystyrene
[Monomer]
The monomers used in the synthesis of the copolymer are as follows.
<< Monomer giving structural unit (I) >>
-STMS: Stylyltrimethoxysilane-SDMS: Stylyldimethoxyhydroxysilane-STES: Stylyltriethoxysilane-TMSPhMA: Trimethoxysilylphenylmethacrylate-VNTMS: Vinylnaphthyldimethoxysilane-VNDMS: Vinylnaphthyldimethoxyhydroxysilane
<< Monomer giving structural unit (II) >>
-MA: Methacrylic acid-HFA: 1,1,1,3,3,3-hexafluoro-2- (4-vinylphenyl) -propane-2-ol-MI: maleimide
<< Monomer giving structural unit (III) >>
・ OXMA: OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(3-Ethyloxetane-3-yl) Methyl Methacrylate ・ GMA: Glycydyl Methacrylate ・ VBG: p-Vinylbenzyl Glycydyl Ether ・ ECHMA: 3,4-Epoxycyclohexylmethylmethacrylate ・ EDCPMA: Methacrylic Acid [3,4-Epoxytri Cyclo (5.2.1.0 ^2,6 ) decane-9-yl]
<< Monomer giving structural unit (IV) >>
-MMA: Methyl methacrylate-EMA: Ethyl methacrylate-PMI: N-phenylmaleimide-MPTS: 3-Methylmethacryloxypropyltrimethoxysilane

<Synthesis of polymer component (A)>
[Synthesis Example 1] In a flask equipped with a synthetic cooling tube for the polymer component (A-1) and a stirrer, 10 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and Molecular Sieves 4A (Wako Pure Chemical Industries, Ltd.) 200 parts of propylene glycol monomethyl ether acetate dried to a water content of 50 wtppm using (manufactured by Yakuhin Kogyo Co., Ltd.) was charged. Subsequently, 30 parts of styryltrimethoxysilane, 10 parts of methacrylic acid, 30 parts of glycidyl methacrylate, and 30 parts of methyl methacrylate were charged, substituted with nitrogen, and then the temperature of the solution was raised to 70 ° C. with gentle stirring. By keeping this temperature for 5 hours, a polymer solution containing the polymer component (A-1) was obtained. The solid content concentration of this 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 Examples 2 to 19] Polymer components or constituent polymers (A-2) to (A-19) synthesis Examples of synthesis except that the types and blending amounts (parts by mass) shown in Table 1 are used. A polymer component having a solid content concentration, a weight average molecular weight and a molecular weight distribution equivalent to that of the polymer component (A-1) or its constituent polymers (A-2) to (A-19) by the same method as in 1. A polymer solution containing the above was obtained. The polymerization solvent used is the same as the organic solvent (D) shown in Tables 2 and 3.

<Preparation of radiation-sensitive resin composition>
The polymer component (A), the radiation-sensitive compound (B), the adhesion aid (C) and the organic solvent (D) used for preparing the radiation-sensitive resin composition are shown below.
<< Polymer component (A) >>
A-1 to A-19: Synthesized in Synthesis Examples 1 to 19
Polymer components or constituent polymers (A-1) to (A-19)
<< Radiation-sensitive compound (B) >>
B-1: Trifluoromethanesulfonic acid-1,8-naphthalimide B-2: Irgacure PAG121 (manufactured by BASF) (2- [2- (4-Methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene- 3-Ilidene] -2- (2-methylphenyl) acetonitrile)
B-3: 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate with sulfonic acid chloride (2.0 mol) B-4: 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensate with chloride (2.0 mol) B-5: N- (2-nitrobenzyloxy) carbonyl-N-cyclohexylamine B-6: Trifluoromethanesulfonic acid oxime ester (International Publication No. 2016/124943). OS17)
B-7: Methanesulfonic acid oxime ester (OS25 described in International Publication No. 2016/124943)
<< Adhesion aid (C) >>
C-1: 3-glycidyloxypropyltrimethoxysilane C-2: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
<< Organic solvent (D) >>
D-1: Propylene glycol monomethyl ether acetate (PGMEA) dried to a water content of 50 wtppm using Molecular Sieves 4A (manufactured by Wako Pure Chemical Industries, Ltd.).
D-2: Diethylene glycol methyl ethyl ether (EDM) dried to a water content of 50 wtppm using Molecular Sieves 4A (manufactured by Wako Pure Chemical Industries, Ltd.).
D-3: Diethylene glycol methyl ethyl ether (EDM)
D-4: Propylene Glycol Monomethyl Ether Acetate (PGMEA)
D-5: Propylene glycol monomethyl ether acetate (PGMEA) distilled and dried using calcium hydride.

<Preparation of radiation-sensitive resin composition>
[Example 1]
Radiation sensitive acid generator (B-1) 1 in an amount corresponding to 100 parts (solid content) of the polymer component (A-1) in the polymer solution containing the polymer component (A-1). Mix 3 parts and 3 parts of adhesion aid (C-1) and dry to 50 wtppm of water content using Molecular Sieves 4A (manufactured by Wako Pure Chemical Industries, Ltd.) so that the final solid content concentration is 30% by mass. It was diluted with the allowed organic solvent (D-1). Then, the radiation-sensitive resin composition was prepared by filtering with a membrane filter having a pore size of 0.2 μm. The water content of this radiation-sensitive resin composition was measured using a Karl Fischer water content meter and found to be 250 wtppm.

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

[Comparative Example 3]
Radiation-sensitive acid generator (B-1) 1 in an amount corresponding to 100 parts (solid content) of the polymer component (A-10) in the polymer solution containing the polymer component (A-10). After mixing the parts and 3 parts of the adhesion aid (C-1), the organic solvent in the composition was removed under reduced pressure. After repeating the operation of adding 10 parts of toluene and azeotropically dehydrating for 1 hour under reduced pressure three times, the solid content concentration was 30% by mass using an organic solvent (D-5) distilled and dried using calcium hydride. It was dissolved so as to become. Next, the radiation-sensitive resin composition of Comparative Example 3 was prepared by filtering with a membrane filter having a pore size of 0.2 μm. The water content of this radiation-sensitive resin composition was measured using a Karl Fischer water content meter and found to be 3 wt ppm.
In Tables 2 and 3, the numerical values in parentheses in columns (A) to (C) are the blending amount (parts by mass) of each component.

<Evaluation>
A cured film was 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 method described below. The evaluation results are shown in Tables 2 and 3. In Example 21, a negative pattern mask was used, and in other examples, a positive pattern mask was used.

[Radiation sensitivity]
A radiation-sensitive resin composition is applied onto a silicon substrate treated with HMDS at 60 ° C. for 60 seconds using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having an average film thickness of 3.0 μm. Formed. This coating film was irradiated with ultraviolet rays of 365 nm using a mercury lamp via a pattern mask having a line and space pattern having a width of 10 μm. Then, using a developer consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development treatment was carried out at 25 ° C. for 60 seconds, and then washing with ultrapure water for 1 minute was carried out. At this time, the minimum exposure amount capable of forming a line-and-space pattern having a width of 10 μm was measured. When this measured value is less than 300 J / m ² , it can be evaluated that the radiation sensitivity is good, and when it is 300 J / m ² or more, it can be evaluated that the radiation sensitivity is poor.

[Evaluation of storage stability]
The prepared radiation-sensitive resin composition was enclosed in a light-shielding and airtight container. After 7 days at 25 ° C., the container was opened, [radiation sensitivity] was measured, and the rate of increase in radiation sensitivity (minimum exposure) before and after storage for 7 days was calculated. If this value is less than 5%, it is judged as AA, if it is 5% or more and less than 10%, it is judged as A, if it is 10% or more and less than 20%, it is judged as B, and if it is 20% or more or the resolution is not reached, it is judged as C. bottom. It can be evaluated that the storage stability is good in the case of AA, A or B, and the storage stability is poor in the case of C.

[Evaluation of substrate adhesion]
After applying the radiation-sensitive resin composition on a silicon substrate that has not been HMDS-treated using a spinner, it is prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film with an average film thickness of 3.0 μm. bottom. This coating film was irradiated with ultraviolet rays having an exposure amount of 400 J / m ² at 365 nm by a mercury lamp via a pattern mask having a line-and-space pattern having a width of 1 to 50 μm. Then, using a developer consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development treatment was carried out at 25 ° C. for 60 seconds, and then washing with ultrapure water for 1 minute was carried out. At this time, the minimum width of the line-and-space pattern remaining without peeling off from the substrate was measured. When the measured value is less than 10 μm, the substrate adhesion is good (A), when the measured value is 10 μm or more and less than 15 μm, the substrate adhesion is slightly good (B), and when the measured value is 15 μm or more or the resolution is not reached. In some cases, it can be evaluated that the substrate adhesion is poor (C).

[Evaluation of wiring corrosion resistance]
A radiation-sensitive resin composition is applied onto a glass substrate in which metal wiring is patterned at intervals of 10 μm using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having an average film thickness of 3.0 μm. Was formed. Next, the coating film on the outer periphery of the substrate is removed to expose the metal wiring, the coating film is exposed to a mercury lamp so that the integrated irradiation amount at 365 nm is 9,000 J / m ² , and the exposed substrate is exposed to a clean oven. An insulating film was formed on the substrate wiring by heating at 200 ° C. for 30 minutes. An electrode is connected to the exposed metal wiring of this substrate, a voltage of 18V is applied to the insulating film, and the metal wiring is stored in a constant temperature and humidity chamber set at 60 ° C. and 90% humidity for 3 days, and then the state of the metal wiring is measured with an optical microscope. Was observed using. At this time, when the corrosion rate (area standard) of the metal wiring was less than 15%, it was determined as A, when it was 15% or more and less than 25%, it was determined as B, and when it was 25% or more, it was determined as C. It can be evaluated that the wiring corrosion resistance is good when the corrosion rate of the metal wiring is A or B, and the wiring corrosion resistance is poor when the corrosion rate is C.

[Evaluation of PCD margin and PED margin]
After applying the radiation-sensitive resin composition on a silicon substrate treated with HMDS at 60 ° C. for 60 seconds using a spinner, (1a) prebaked on a hot plate at 90 ° C. for 2 minutes to have an average film thickness of 3.0 μm. A coating film is formed, and (2a) the coating film is irradiated with ultraviolet rays of 365 nm using a mercury lamp via a pattern mask having a line-and-space pattern having a width of 10 μm, and (3a) after the ultraviolet irradiation. A developer consisting of a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was used as a coating film, and the film was developed at 25 ° C. for 60 seconds and then washed with ultrapure water for 1 minute. In the case of PCD (Post Coating Delay) margin evaluation, after the above (1a) and before the above (2a), and in the case of PED (Post Exposure Delay) margin evaluation, after the above (2a) and above (3a). ), The step of leaving the coating film at room temperature for 1 hour was added. At this time, the minimum exposure amount capable of forming a line-and-space pattern having a width of 10 μm was measured. Comparing this measured value with the measured value of [Radiation Sensitivity], the case where the increase rate of the minimum exposure is less than 5% is A, the case where it is 5% or more and less than 10% is B, and the case where it is 10% or more or the resolution. The case where the result was not reached was determined as C. In the case of A or B, it can be evaluated that the PCD and PED margins are good, and in the case of C, it can be evaluated that the PCD and PED margins are poor.

[Measurement of minimum resolution]
A radiation-sensitive resin composition is applied onto a silicon substrate treated with HMDS at 60 ° C. for 60 seconds using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having an average film thickness of 3.0 μm. Formed. Through a pattern mask having a square pattern with a side of 1 to 10 μm on this coating film, ultraviolet rays of 365 nm are emitted using a mercury lamp at the minimum exposure amount optimized by [radiation sensitivity] × 1.5 times the exposure amount. Irradiated. Then, using a developer consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development treatment was carried out at 25 ° C. for 60 seconds, and then washing with ultrapure water for 1 minute was carried out. At this time, the minimum mask size in which the square pattern can be formed was measured. When this measured value is less than 4 μm, it can be evaluated that the resolution is good, and when it is 4 μm or more, it can be evaluated that the resolution is poor.

As shown in Tables 2 and 3, each radiation-sensitive resin composition of Examples has good radiation sensitivity, and practical characteristics include radiation sensitivity, storage stability, substrate adhesion, wiring corrosion resistance, PCD margin, and the like. It can be seen that both the PED margin and the resolution are good. On the other hand, none of the radiation-sensitive resin compositions of Comparative Examples had good properties.

Claims (10)

A polymer component (A) having a structural unit (I) containing 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. ,
Radiation-sensitive acid generators and
Organic solvent (D) and
Contains water (E),
The content of the water (E) is 10 wtppm or more and 800 wtppm or less.
The radiation-sensitive acid generator is at least one selected from an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, and a carboxylic acid ester compound. A characteristic positive radiation- sensitive resin composition. The positive radiation- sensitive resin composition according to claim 1, wherein the content of the water (E) is 550 wtppm or less. The positive radiation- sensitive resin composition according to claim 1 or 2, wherein the content of the water (E) is 250 wtppm or less. The polymer component (A) contains a crosslinkable group in the same or different polymer as the polymer having at least one structural unit selected from the structural unit (I) and the structural unit (II). The positive radiation- sensitive resin composition according to any one of claims 1 to 3, further comprising a structural unit (III). The structural unit (I) is a substituted or unsubstituted benzene ring, naphthalene ring or ankoxy ring and a group represented by -SiR ₃ directly bonded to the ring (the R is independently a hydrogen atom and a halogen, respectively). 13. Positive type radiation-sensitive resin composition. A patterned cured film formed from the positive radiation- sensitive resin composition according to any one of claims 1 to 5 . The patterned cured film according to claim 6 , which is an interlayer insulating film. A step (1) of forming a coating film of the positive radiation- sensitive resin composition according to any one of claims 1 to 5 on a substrate, and a step (2) of irradiating a part of the coating film with radiation. A method for producing a patterned cured film, comprising a step (3) of developing the coating film irradiated with radiation and a step (4) of heating the developed coating film. A semiconductor device comprising the patterned cured film of claim 6 or 7 . A display device including the semiconductor element of claim 9 .